Mechanisms of platinum(II) and palladium(II) catalyzed organic transformations : hydration of alkynes and the cope rearrangement by William Charles Hiscox A thesis submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry Montana State University © Copyright by William Charles Hiscox (1993) Abstract: Mechanisms of the platinum (II) catalyzed hydration of alkynes and the palladium (II) catalyzed Cope rearrangement of 2-methy1-3-pheny1-1,5-heptadiene were studied using nuclear magnetic resonance spectrometry (MMR). Kinetic studies were done for both reactions. For both reactions the rate determing steps were found to be ligand substitution reactions of the respective substrates on the active catalysts. The reactions are shown to proceed through metallacycle intermediates. MECHANISMS OF PLATINUM (II) AND PALLADIUM(II) CATALYZED
ORGANIC TRANSFORMATIONS: HYDRATION OF ALKYNES
AND THE COPE REARRANGEMENT
by
William Charles Hiscox
A thesis submitted in partial fulfillment of the requirements for the degree
of
Doctor of Philosophy
in
Chemistry
Montana State University Bozeman, Montana
July 1993 MECHANISMS OF PLATINUM (II) AND PALLADIUM(II) CATALYZED
ORGANIC TRANSFORMATIONS: HYDRATION OF ALKYNES
AND THE COPE REARRANGEMENT
William Charles Hiscox
Advisor: Reed A. Howald, Ph.D.
Montana State University 1993
Abstract
Mechanisms of the platinum (II) catalyzed hydration of alkynes and the palladium(II) catalyzed Cope rearrangement of 2-methyl-3-phenyl-I,5-heptadiene were studied using . nuclear magnetic resonance spectrometry (NMR). Kinetic studies were done for both reactions. For both reactions the rate determing steps were found to be ligand substitution reactions of the respective substrates on the active catalysts. The reactions are shown to proceed through metallacycle intermediates. © COPYRIGHT
by
William Charles Hiscox
1993
All Rights Reserved jyyi?
APPROVAL
of a thesis submitted by-
William Charles Hiscox
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This thesis is dedicated to the memory of Marjorie Nichols, one of the first women ever admitted to a college chemistry course, and the one responsible for my interest in science. V
TABLE OF CONTENTS
Page 1. INTRODUCTION...... I 2. PLATINUM (II) CATALYZED HYDRATION OF ALKYNES AND RELATED REACTIONS ...... 3 Background ...... 5 Experimental Section ...... 13 General...... 13 Preparation of Zeise1s Dimer ...... 14 di- (4,4 - dime thy I -2 -pentyne) -dichloro-di-JLl- dichloroplatinum (II)...... 15 General Method for Hydration of Alkynes- Illustrated for I-Hexyne ...... 16 Recycling of Platinum ...... 18 Monitoring of Reactions by 1H N M R ...... 19 Effect of p-toluenesulfonic acid on reaction r a t e ...... 20 Effect of D2O vs H2O ...... 20 Rate of Reaction with 4,4-dimethyl-2-pentyne dimer vs Zeise1 s D i m e r ...... 21 Michaelis-Menten kinetics ...... 22 Reaction of Zeise's Dimer with 4-Octyne in CHCl3 ...... 23 Dichloroplatinum(II)-tetraalkylyclobutadienes ... 24 Methanol Addition to 1-alkynes ...... 31 Results and Discussion ...... 36 Mechanistic Studies ...... 43 Exchange experiments on Zeise's Dimer ...... 48 The Role of the Ethylene Ligand in the Catalyst...... 51 Kinetics Experiments- IH N M R ...... 56 Michaelis-Menten Catalyst Model ...... 62 Evaluation of Possible Mechanisms ...... 63 Addition of Methanol to I-Alkynes ...... 72 Cyclobutadienes ...... 78 Summary...... 85 3. PALLADIUM CATALYZED COPE REARRANGEMENT OF 2-METHYL-3 -PHENYL-1,5-HEPTADIENE...... 86 Background...... 89 Mechanism of Thermal Cope Rearrangements ...... 91 Palladium(II) Catalyzed Cope Rearrangements .... 98 vi TABLE OF CONTENTS-continued
page
Experimental Section ...... 102 General...... 102 Synthesis of Starting Materials ...... 103 Thermal Rearrangement of trans-2-methyl-3- phenyl-1,5-heptadiene ...... 109 Molecular Modeling ...... 109 bis-Acetonitriledichloropalladium(TI) ...... H O Palladium Catalyzed Cope Rearrangement of trans-2-methyl-3-phenyl-1,5-heptadiene in Tetrahydrofuran ...... Ill Separation of Cis and Trans Isomers of 2- methyl-3-phenyl-1,5-heptadiene and of their Cope Rearrangement Products, Cis and Trans- 2 ,4-dimethyl-I-phenyl-I,5-hexadiene ...... 112 Characterization of diene I I ...... 113 Kinetics- Monitoring of Reactions by IH NMR .... 114 Reactions of purified Cope Products ...... 116 Data Handling, Analysis ...... 116 Viability of the Catalyst at Long Reaction T i m e s ...... 118 Effect of Added Acetonitrile ...... 118 Double-bond Isomerization of 3-heptene ...... 119 Results...... 121 Collecting the Data: Preliminary Results ...... 128 Reactions of Purified Dienes ...... 130 Modeling the Palladium (II) Catalyzed Cope Rearrangement as a Set of Concurrent First Order Reactions...... 135 Effect of Added Acetonitrile...... 139 Molecular Modeling Studies ...... 142 Details of Analysis of the Kinetic Data ...... 143 Kinetic Runs at 308K ...... 155 Thermodynamic Activation Parameters ...... 155 Discussion...... 159 Summary...... 164 4. CONCLUSION...... 166 REFERENCES CITED ...... 168 APPENDIX Data From Kinetic Runs in Chapter 3 ...... 17 6 vii
LIST OF TABLES
Table page
1. Data for Michaelis-Menten Graph ...... 61
2. Thermodynamic Activation Parameters ...... 156 viii
LIST OF FIGURES
Figure page
1. Hydration of 4-Octyne ...... 4 2. Chatt-Dewar-Duncanson Model for olefin-metal bonding ...... 9 3. Synergistic Bonding of Orthogonal JCy and TUj_* Acetylene Orbitals to Platinum ...... 11 4. Correlation Diagram for Acetylene Backbonding to Platinum...... 12 5. Hydration of Dialkylalkynes ...... 37 6. Explanation for Regioselectivity ...... 38 7. 13C and 1H NMR of 2-Heptanone from Hydration of I-Heptyne...... 40 8 . Structure of Zeise's Dimer ...... 44 9. NMR Spectra for D20 Monomer of Zeise's Dimer ...... 45 10. 13C and 1H NMR Spectra of Zeise's Dimer in CD30D.... 46 11. Zeise's Dimer in C D 3 C N ...... 47 12. 1H NMR Spectra for Catalytic Reaction in Tetrahydrofuran-dg ...... 49 13. 1H NMR Spectra for Ethylene Displacement in Chloroform-d ...... 50 14. Top: di-(4,4-dimethyl-2-pentyne)-dichloro- di-m-dichlorodiplatinum(II). Bottom: Addition of 4-octyne and water to the complex...... 54 15. Detailed Mechanism of Platinum(II) Catalyzed Hydration of Alkynes Showing the Michaelis Menten Constants ...... 57 16. First Order Plots at Several Initial Concentrations of Alkyne ...... 58 17. Saturation Kinetics ...... 59 18. Michaelis-Menten Graph ...... 60 19. Cis-Addition of Water and Methanol to an Osmium(II)-Alkyne Complex ...... 67 20. Addition of Protonic Acids to a Platinum(0)- Alkyne Complex ...... 68 21. Mechanism of Hydroxypalladation ...... 70 ix LIST OF FIGURES-continued
Figure page
22. Evidence for External Attack of Water on the Coordinated Ethylene of Zeise's Dimer ...... 71 23. 13C, 1H and Mass Spectra of 2,2-dimethoxyheptane.... 75 24. Top: HETCORR of 2,2-dimethoxyheptane. Bottom: Vinyl Ether? ...... 76 25. Tetrapropylcyclobutadienedichloroplatinum(II) ..... 79 26. ORTEP Plots of (tetrapropylcyclobutadiene)dichloroplatinum(II) ... 80 27. Mechanism of formation of tetrapropylcyclobutadienedichloroplatinum(II) .... 81 28. Other Cyclobutadiene Complexes ...... 84 29. The Cope Rearrangement...... 86 30. Four Products of Palladium(II) Catalyzed Cope Rearrangement of 3-phenyl-2-methyl-1,5- heptadiene...... 88 31. Stereospecificity in the Claisen Rearrangement .... 91 32. Six Atom versus Four Atom Overlap...... 93 33. Argument Against Separated Allyl Fragments ...... 95 34. Support for Minor Boat Transition State in the Thermal Cope Rearrangement ...... 96 35. Rearrangement of cis,trans-1,5-cyclooctadiene on Palladium(II) ...... 99 36. Palladium Catalyzed Cope Rearrangements of Substituted 3-phenyl-1,5-dienes...... 99 37. Analysis of Best Chair for the Rearrangement of (3R, 5E)-2,3-dimethyl-3-phenyl-1,5-heptadiene .... 101 38. Autoprogram KINETll. AU ...... 114 39. Autoprogram FTPKINT . AU ...... 117 40. Synthesis of Cope Starting Materials ...... 120 41. Spectra for Compound I ...... 122 42. Spectra for Compound I I ...... 123 43. 1H Spectrum of Compound I I I ...... 124 44. Nuclear Overhauser Effect in Compound II ...... 125 45. Attempted Rearrangement of Geranyl Compounds ...... 127 46. Summary of Reactions on the Dienes...... 129 47. Stacked Plot for Reaction of III—>1 ...... 132 48. Graph of Integrals for the reaction III->I ...... 133 49. Chromatograph of Cope Product Mixture ...... 134 50. Associative Rate L a w ...... 140 51. The Palladium(II) Catalyzed Cope Rearrangement C y c l e ...... 141 52. Relative Stabilities of the Products from Molecular Modeling ...... 142 53. Output for Rate Constant Matrix at 2 9 8 K ...... 145 X
LIST OF FIGURES-continued
Figure page
54. Fit of Calculated Line to Experimental Line for Compound I ...... 146 55. Fit of Calculated Line to Experimental Line for Compound I I ...... 147 56. Fit of Calculated Line to Experimental Line for Compound III ...... 148 57. Output for the Rate Constant Matrix at 308K...... 152 58. Fit of Calculated Lines at 3 0 8 K ...... 153 59. Energy Diagrams for Formation of Three Products from Compound I ...... * . . . . 158 60. Predicted Stereochemical Outcome Through the Possible Boat and Chair Transition States ...... 160 61. Structure of (Tj4-I, 5-hexadiene)palladium dichloride...... 162 62. Summary...... 163 xi
ABSTRACT
Mechanisms of the platinum (II) catalyzed hydration of alkynes and the palladium (II) catalyzed Cope rearrangement of 2-methyl-3-phenyl-1,5-heptadiene were studied using nuclear magnetic resonance spectrometry (MMR). Kinetic studies were done for both reactions. For both reactions the rate determing steps were found to be ligand substitution reactions of the respective substrates on the active catalysts. The reactions are shown to proceed through metallacycle intermediates. I
CHAPTER I
INTRODUCTION
Platinum and palladium are important strategic metals,
and are used as catalysts for a wide variety of organic
transformations. Knowledge of the mechanisms of these
reactions is essential to the successful design of new
catalysts. The work described here focuses on mechanisms of
catalytic reactions of platinum (II) and palladium (II). The
organic transformations which were studied are the platinum (II) catalyzed hydration of alkynes and the palladium (II) catalyzed Cope rearrangement of 2-methyl-3- phenyl-1 ,5-heptadiene.
Several related reactions were discovered during this
study, including the formation of platinum (II) cyclobutadiene
complexes from Zeise1s Dimer and alkynes, which proceed
through a platinacyclopentadiene intermediate. The study of platinacyclobutanes and pentanes was originally undertaken because of the proposed intermediacy of metallacycles in
transition metal catalyzed olefin metathesis and other
reactions. Several platinum mediated organic transformations 2 have recently been proposed to involve platinacycle intermediates. It will be shown that the reactions discussed here also proceed through platinacycle and palladacycle intermediates. 3
CHAPTER 2
PLATINUM (II) CATALYZED HYDRATION OF ALKYNES AND RELATED REACTIONS
The hydration of alkynes is of great importance in organic synthesis, and for the functionalization of this hydrocarbon resource on an industrial scale. Alternatives to classical mercury catalyzed processes are becoming ever more important, due to the toxicity of mercury compounds and the increasing regulations on their use. Recent studies on addition of water and methanol to the carbon-carbon triple bond of alkynes coordinated to osmium(TI) complexes1, and new results on the mechanisms of Wacker type processes2, among others, have dramatically changed the way mechanisms of late transition metal catalysis are described. With respect to organoplatinum chemistry, nucleophilic addition to alkynes is a long standing problem.
The hydration of alkynes, using Zeise's Dimer as the platinum(TI) catalyst precursor, was first reported in 1989
(figure I)3. This has been developed into an efficient method 4
for the transformation of dialkylalkynes and 1-alkynes into
their corresponding ketones. The complete reaction of these
alkynes requires less than Imol% catalyst in water/tetrahydrofuran solutions, with no added protonic
acid, at room temperature, to proceed without side products.
The ketones are isolable by direct distillation from the reaction flask.
tetrahydrofuran H2O
Figure I Hydration of 4-Octyne
Several fundamental questions arose upon the initial, serendipitous, observation that platinum (II) had catalyzed the hydration of 4-octyne in diethylether. What ligands are bonded to platinum in the active catalyst, and what is their geometry about the metal center? What is the fate of the ethylene on Zeiese's Dimer after reaction with an alkyne?
Does Zeise's Dimer remain in the dimeric form during the reaction? More importantly, how does the active catalyst
"activate" the substrate, and what role do its resident 5
ligands play in this step? Can methanol or other
nucleophiles be added to an alkyne using this catalyst?
These are the questions that will be addressed.
Background
Little mention is made of platinum catalyzed hydration
of alkynes in the literature, except for the observation by
Chatt and Duncanson4 , that hydration of several alkynes was observed in the presence of platinum, which they believed had been reduced to the zero oxidation state during their attempted synthesis of platinum (II)-alkyne complexes in
ethanol solvent. For the most part, such complexes could not be isolated, with the exception of those formed from dialkylacetylenes bearing at least one tertiary butyl group.
The importance of these complexes will be discussed later.
Palladium(II) catalysts have been used for the hydration of alkynes5. However, complex mixtures result from the hydration of terminal acetylenes, such as methyl acetylene^, in strong acid solutions of the metal. Utimoto and coworkers^ have developed a hydration scheme for alkynones such as 5-heptyn-2-one, which employs palladium(II) catalysts, but relies upon intramolecular 6
assistance by the carbonyl oxygen of the alkynone for the
reaction to proceed. Simple alkynes are not hydrated under
the same conditions. Although palladium(II) is an excellent
catalyst for the oxidation of olefins, its reactivity with
alkynes is different from platinum. It is known more for its
use in cyclotrimerizations of alkynes to make benzenes, for
instance8.
Mercury (II) catalysis is the classical method of hydrating alkynes9, and the mechanism of the reaction is
still actively studied. The reaction is usually run in
concentrated acid solutions of mercury (II). Most of the
current literature focuses on specific cases, such as the hydration of alkynes with other functionality, and recently on Nafion-H supports for mercury catalysts10. Mercury has
traditionally been used to hydrate terminal alkynes to the corresponding ketones, in accord with Markovnikov's rules.
However, polymers are often formed in the reaction, as well as mercuration products of the acetylene11. Large amounts of mercury are used because the catalyst is easily poisoned, and workup is also inefficient. The mercury by-products, including metallic mercury and assorted organomercury compounds, are highly toxic. These products constitute a serious environmental hazard, and contamination by these compounds is widespread. Mercury is insidious because it accumulates in the fatty tissues of animals, and moves up 7
the food chain. It will be shown that for simple
alkylalkynes, platinum(II) hydration catalysts have more
longevity than mercury catalysts, can be used in truly
catalytic amounts, and can be recycled easily without
environmental degradation.
Previous attempts at alkyne hydration by platinum (II) catalysts have not been fruitful. Trogler has developed platinum (II) hydration catalysts for nitriles12 and alkenes13, and has proposed their use for the hydration of alkynes. However, success in this last area has not been reported to date. The catalysts developed by Trogler are hydrido-hydroxo platinum (II) complexes formed via the photolysis of bis-triphenylphosphineplatinum(0) in the presence of water.
Hydrido-hydroxotransition metal complexes, in general, can be prepared by oxidative addition of protic compounds to low valent transition metals14. Oxidative addition of water to a transition metal should give a species with the general formula HMOH, disregarding the other ligands. In fact, reaction of water with Os3 (CO)12 gives Os3 (H)(OH)(CO)10 15 and, likewise, [Rh(en)2]+ gives [Rh(H) (OH) (en)2]+ 16. An earlier, but thorough, investigation of the catalytic properties of platinum hydridohydroxy complexes was carried out by Otsuka and company.17 They studied both deuteration reactions and hydration reactions facilitated by these 8
catalysts. It was shown that the addition of water to Pt[P(i-pr)3]2 gives trans-Pt(H)(OH)[P(i-pr)3]2, while Pt[P(i-
Pr )3]3 gives [Pt (H)L3JOH (L = P (i-pr)3, P(Et)3, solvent).
These catalysts, when generated in-situ, efficiently
catalyzed the hydration of both olefins and nitriles.
For the platinum (II) catalyzed hydration of alkynes it
is possible that coordinated water is "split" by platinum in a very fast step, resulting in the addition of the elements of water to the alkyne substrate. It will be shown that the rate of aquo-exchange on platinum (II)-alkyne complexes must be fast with respect to the rate determining step. Rates of
Aquo-exchange on Platinum Complexes in aqueous solution have been measured by Steve Dunham and Edwin Abbott18. They found that the rate of water exchange on platinum(III) in the form of [Pt2 (H2P2O5)Cl2]4- was greater than IO4S-1! Platinum(IV) complexes had much slower exchange rates, on the order of
IO-6S-1. They did not investigate platinum(II) complexes. By the Chatt-Dewar-Duncanson model, one extreme of platinum- olefin bonding is described as the metallacyclopropane extreme. One can look at this as a formal oxidative addition of alkyne accross the platinum center in a 1,2 sense, thereby increasing the oxidation state of platinum over platinum(II), the active catalyst precursor. 9
R
metallacyclopropane extreme
Figure 2 Chatt-Dewar-Duncanson Model for Olefin-Metal Bonding
The Chatt-Dewar-Duncansonis model for olefin and acetylene-transition metal bonding is an excellent template on which to base predictions of structure, reactivity and stability of platinum(II) complexes of unsaturated organic ligands. The model (figure 2) recognizes two types of bonding: sigma donation from the filled pi orbitals on the olefin to empty metal d-orbitals forms the sigma component of the bond, and back donation of electrons from filled metal d-orbitals to the antibonding orbitals of the olefin 10
forms the pi component. The two components together form a
"dative double bond". The picture for alkynes is much the
same with regard to ligand-metal bonding, except for the
extra set of bonding and antibonding orbitals on the alkyne. The orthogonal Ti1 and TC1 * orbitals of acetylenes may also interact with orbitals on the metal20. This "synergistic" bonding is usually weak, however, due to the marginal overlap of the orbitals involved. Nevertheless, this interaction is important in the molecular orbital picture, because the mixing of these orbitals changes the LUMO of the complex. The bonding picture is illustrated in figure 3. The mixing of the orthogonal acetylene orbitals with orbitals on the metal results in an additional set of molecular orbitals, of which the antibonding orbital is now the LUMO of the complex. As shown in the correlation diagram in figure 4, this is where nucleophilic attack should occur. 11 z
A
sx component
Tt1 component
Figure 3 Synergistic Bonding of Orthogonal Ttj_ and Ttj_* Acetylene Orbitals to Platinum 12
• / / / • I •• I / >• / / • / // / / / / # / Ti / / % \ / / % / % / W / /.% / \ T i / \ Ti ---- '< filled metal d orbitals % \ ' s ^ ^ ^
\ Ti
Figure 4 Correlation Diagram for Acetylene Backbonding to Platinum 13
Experimental Section
General
Diethyl ether and tetrahydrofuran were distilled from sodium benzophenone ketyl prior to use. Chloroform was distilled from anhydrous calcium chloride. dg-THF (99.8% D),
CDCI3 (99% D), CD3OD and CD3CN were purchased from Cambridge
Isotope Laboratories and used as received. Alkynes were purchased from Aldrich Chemical Company and Farchan Chemical
Company, and used without further purification. Cyclic diynes were provided graciously by Bruce King, of the
University of Georgia Chemistry Department.
NMR spectra were referenced to the solvent, except for platinum-195 NMR spectra, which were externally referenced to K2PtClg in D2O . ^H, and -^C nuclear magnetic resonance data were collected on 250, 300, and 500MHz Brucker fourier transform instruments. 195Pt spectra were obtained on the
250MHz instrument equipped with a broadband probe. 14
Preparation of Zeise's Dimer
Zeise's Dimer was prepared by dissolving ^PtCl^ (Sg)
in a 3% HCl solution (IOOml). This was transferred to a
glass Parr reaction vessel which had been fitted with a
magnetic stir-bar. The Parr vessel was sealed, then
pressurized to 9Opsi of ethylene and maintained at this
pressure with stirring for approximately 24 hours until the
solution had turned bright yellow. At this time the solution
was transferred to a 250ml round bottom flask, and the
solvent removed by rotary evaporation. The resulting solids
were extracted with 100ml of a 1% HCl in ethanol solution,
the extracts were filtered and evaporated under vacuum.
Finally,, toluene was added to the residue and again
evaporated under vacuum to co-distill any remaining water.
From this process was isolated very bright, orange crystals of Zeise's Dimer(-3.5-4 grams). 300MHz 1H NMR (CDCI3) 54.9
(anti, S , =CH2 , Jpt-H = 70Hz) ppm. 13C NMR (75MHz, CDCl3) 5
71.9 (anti, s, Jpt-C = 205Hz), 71.7 (syn, s, Jpt_c = 193Hz)
ppm. 1H NMR (d8-THF) 5 4.25 (s, Jpt-H = 68.7Hz) ppm. 13C NMR
(75MHz, CD3CN) 5 74.3 (s, JPt_c = 172Hz) ppm. 1H NMR (D2O,
4.65 ppm) 5 4.36 (s , b r , Jpt_H = 70.3Hz), 4.52 (s, br, minor peak unidentified) ppm. 13C NMR (D2O) 5 68.3 (s, sharp, Jpt_c
= 213.6Hz), 72.5 (br, JPt_c = 160.8Hz) ppm. 1H NMR (CD3OD,
3.34 ppm) 5 2.81 (s, br,' Jpt _H = 73.0Hz) ppm. 13C NMR (CD3OD, 15
49.9 ppm) 8 62.5 (s, sharp, JPt_c = 232Hz) ppm. 195Pt NMR
(CDCl3, K2PtCl6 in D2O external standard) 8 -2516.58 ppm.
di- (4,4-dimethyl-2-oentvne) -dichloro-di-fi- dichloroplatinum(II). 4,4-Dimethyl-2-pentyne(Iml) was added to a stirring chloroform (5ml) solution of Zeise's Dimer
(200mg). After several seconds an orange precipitate began to form. The resulting mixture was allowed to stir at room temperature for several hours. The precipitate was isolated by vacuum filtration, washed twice with I ml of pentane, then placed under high vacuum overnight. 1H NMR (CDCl3) 8
2.23 (anti, s, br, CH3, JPt_H = 53Hz), 2.18 (syn, d, CH3),
1.48 (anti, s, br, (CH3)3), 1.45 (syn, d, (CH3)3) ppm. 13C
NMR (CDCl3) 8 79.8 (anti, Jpt_c = 205Hz) , 79.6 (syn, Jpt-C =
205Hz) , 70.2 (anti, Jpt_c = 205Hz) , 70.0 (syn, JPt_c =
205Hz), 30.1 (br, (CH3)3), 26.9 (syn, quaternary), 26.5
(anti, quaternary), 7.91 (br, CH3) ppm. 1H NMR (dg-THF) 8
2.08 (s, 3H, CH3, Jpt_H = 37.2Hz) , 1.42 (s, 9H, (CH3)3) ppm.
13C NMR (dg-THF) 8 57.0 (Jpt-C = 201Hz), 46.9 (Jpt_c = 199Hz),
30.1, 25.9, 7.3 ppm. 16
■General Method for Hydration of Alkvnes-Illnstrated for 1- Hexvne
2-Hexanone. A 250ml round bottom flask was fitted with
a magnetic stir bar and placed into a heating mantel over a
stir plate, and 150ml of tetrahydrofuran and 5ml of
distilled water were introduced. Zeise's Dimer (O.lOOg,
0.34mmol Pt(II)) was added to the solution and stirred for a
few minutes. The reaction flask was fitted with a claisen
adaptor, to which was fitted both a reflux condenser and a
50ml addition funnel. To the addition funnel was added a
solution of 1-hexyne (2.14g, 26.Ommol) in tetrahydrofuran to
make 50 mililiters. The Zeise's Dimer solution was heated to
mild reflux, and then the 1-hexyne solution was added slowly
over 30 minutes. When the addition was complete, the
homogeneous red solution was allowed to reflux for 2 hours,
after which the reaction had gone to completion by 1H NMR.
Most of the tetrahydrofuran was removed by careful
distillation, and the remaining solution was cooled to room
temperature, then extracted three times with 50ml portions
of chloroform. The chloroform extracts were combined, dried
over anhydrous magnesium sulfate, and filtered. The product was isolated by distillation of the solvent, followed by vacuum distillation of the product ('5torr, 30°C) , to yield
2-hexanone (2.46g, 94% yield). 1H NMR: 5 2.32 (t, 2H, CH2), 17
2.01 (s, •3H, CH3), 1.45 (m, 2H, CH2), 1.20 (m, 2H, CH2) , 0.80
(t, 3H, CH3) ppm. 13C MMR: 8 209, 43.8, 29.9, 26.0, 22.2,
13.8 ppm.
2-Heptanone: 1H NMR (CDCl3) 5 2.37 (t, 2H, CH2), 2.08
(s, 3H, CH3), 1.52 (m, 2H, CH2), 1.24 (m, 4H, CH2), 0.83 (tr,
3H, CH3) ppm. 13C NMR (75MHz, CDCl3) 5 209.2, 43.7, 31.3,
29.7, 23.5, 22.4, 13.8 ppm.
4-Octanone: 3OOMHz 1H N M R (CDCl3) 5 2.35 (m, 4H, CH2),
1.55 (m, 4H, CH2), 1.30 (m, 2H, CH2), 0.87 (dt, 6H, CH3) ppm.
13C N M R (75MHz, CDCl3) 5 210.3 (C=O), 44.5 (CH2), 42.3 (CH2),
25.8 (CH2), 22.4 (CH2), 17.2 (CH3), 13.6 (CH3) ppm. Mass spectrum m/z 128 (m+, TIC = 28%), 85 (75), 71 (100), 57
(89), 43 (97).
2,2-Dimethyl-3-pentanone: 1H NMR (CDCl3) 8 2.3 6 (q, 2H,
CH2), 1.00 (s, 3HCH3), 0.88 (tr, 3H, CH3) ppm.
4,4-Dimethyl-2-pentanone: 1H NMR (CDCl3) 8 2.18 (s, 2H,
CH2), 1.99 (s, 3H, CH3), 0.84 (s, 3H, CH3) ppm.
3-Hexanone: 1H NMR (CDCl3) 8 2.38 (t, 4H, CH2), 1.53 (m,
2H, CH2), 0.99 (t, 3H, CH3), 0.87 (t, 3H, CH3) ppm. 18
2- Pentanone: 1H NMR (CDCl3) 5 2.37 (t, 2H, CH2), 2.09
( s , SR, CH3) , 1.57 (m, 2H, CH2) , 0.88 (t, 3H, CH3) ppm.
3- Pentanone: 1H NMR (CDCl3) 5 2.40 (q, 4H, CH2) , 1.02 (t, 6H, CH3) ppm.
Recycling of Platinum
The typical method for recycling platinum after use in reactions involves collection of platinum containing waste, and distillation of the organics from the solid waste to leave a cake of platinum containing sludge. This is ignited in a crucible and heated by a Meeker burner for several days, until only a grey ash is left. The ash is washed with water several times to remove unwanted inorganic salts, and re-ashed. The fine powder obtained contains reduced platinum which is then digested in boiling aqua-regia. The platinum salts obtained from this process are used as starting material for the synthesis of Zeise's Dimer and other products. Caution: Mixing of incompatible chemicals or very reactive chemicals in the waste collection jar is to be avoided. Distillation of unknown mixtures of organics, possibly including inorganics, should be considered very hazardous, and a blast sheild should be used during this 19
process. Avoid vapors from this process and from the ashing process. Boiling aqua-regia is extremely hazardous. Thick rubber gloves and eye protection are minimal protection for all of these procedures.
Monitoring of Reactions bv MMR
For the purpose of monitoring reactions under controlled conditions, reactions were run in matched 5mm ultraprecision thin walled NMR tubes, which were sealed from the surrounding environment with tight fitting plastic caps.
For ligand exchange studies, reaction solutions in deuterated solvents were monitored by 1H and -^C NMR throughout the course of reaction, and monitoring was continued over a period of days to ensure the identity of the equilibrium products.
Kinetics studies were performed with a Brucker 25OMHz
NMR spectrometer, using an automated data collection routine which collected spectra periodically (5 or 10 minute intervals). Machine integration was used, and the relative peak areas for the product and reactant were used to determine the extent of reaction at each acquisition time during a run. 20
Effect of p-toluenesulfonic acid on reaction rat~.fi
Three identical NMR tubes were prepared in the
following way for three side by side experiments. Zeise's Dimer in d8-THF solution (0.40ml) was added to two of the
NMR tubes. To sample I was added 5ul H2O. To sample 2 was added 5ul of a p-toluenesulfonic acid solution (3XlO“4g,
4X10-3M solution in THF sample). A third NMR tube was prepared without Zeise1s Dimer, adding only the acid solution (5ul) to the measured amount of tetrahydrofuran.
4-Octyne was injected into each of the NMR tubes at approximately the same time. The contents were mixed thoroughly and 1H NMR spectra were taken at several reaction times over a period of six hours. Throughout the experiment there was no evidence of significant rate difference between the two samples including Zeise's Dimer catalyst. The sample that did not have Zeise's Dimer showed no reaction.
Effect of D2O vs H2Q
Two identical samples were prepared in matched 5mm NMR tubes. 4,4-dimethyl-2-pentyne (100)11) was delivered to each tube by syringe. H2O (40)1.1) was added to one tube and D2O
(40|il) was added to the other. Aliquots of Zeise's Dimer in 21 d8-THF were delivered to each test tube forcefully to mix the components. The two reactions were monitored periodically by 1H NMR. No difference in the extent of reaction was noted throughout the period in which the reactions were monitored.
Rate of Reaction with 4,4-dimethvl-2-oentvne dimer vs
Zeise's Dimer
Two kinetic runs were performed to compare the rate of hydration of 4-octyne with Zeise's Dimer catalyst to the rate with the 4,4-dimethyl-2-pentyne analog as catalyst. For each experiment an NMR tube was prepared by adding 4-octyne
(IO(Il) and H2O (IO(Il) by syringe. In the first experiment a solution of di- (4,4-dimethyl-2-pentyne) -dichloro-di-|i- dichloroplatinum(II) (0.0SM Pt) in d8-THF was added to the
NMR tube by syringe forcefully, mixing the components thoroughly before starting the acquisition. Data were collected in the usual way. The run for Zeise's Dimer was performed in the same way with the same molar amount of catalyst. First order plots of the data showed the rate constant for the 4,4-dimethyl-2-pentyne analog was 2.72X10'
4S-1, while Zeise's Dimer gave a rate constant of
8.12X10_5s -1. 22
Michaelis-Menten Kinetics
4-Octyne was used as substrate in all of the kinetic
runs taken for the purpose of generating the Michaelis-
Menten graph, A stock solution (5 ml) of Zeise's Dimer in
dg-THF (0.08M Pt) was prepared immediately before the
kinetics runs were started, and this solution was delivered
to the NMR tubes by syringe. Distilled water (10.Oul) and an
aliquot (5.0-50.Oul) of 4-octyne were placed in an NMR tube,
and an aliquot of the Zeise's Dimer solution (0.25ml) was
injected forcefully into the NMR tube, which was immediately
capped and inverted several times to ensure complete mixing.
The sample was placed in the magnetic field of the
instrument, which had been shimmed to another sample of
similar composition, and the kinetic run was started
immediately after the deuterium lock was established. In
this way, data collection was started within one minute of mixing, in most cases. Five data sets were collected for
five different concentrations of 4-octyne.
The initial rate of each reaction was taken from the
first four data points generated in each kinetics run. The
Michaelis-Menten plot was generated by plotting the reciprocal of the initial rate (s/M) vs. the reciprocal of the initial alkyne concentration (1/M). The initial concentration of alkyne was adjusted using the extent of 23
reaction.in order to ensure that the initial concentration
corresponded to the initial rate at the'time data collection
was started. First order plots of the reactions at several
concentrations of alkyne were generated directly from each
data set, graphing ln[4-octyne] vs. time(sec).
Reaction of Zeise's Dimer with 4-Qctvne in CHClo
An NMR experiment was performed which was identical to the kinetic runs described above, except that CDCl3 was
employed as the solvent. 4-Octyne (IOfil) and H2O (Sfil) were delivered to an NMR tube by syringe. A solution of Zeise's Dimer (O.llSSg) and benzene (ISfll) in CDCl3 (10.0ml) was
injected forcefully into the NMR tube (0.3ml delivered). 1H
NMR spectra were taken of the sample periodically. The first
spectrum taken showed that ethylene had been completely displaced from the platinum complex, the' free ethylene resonance was observed at 5.1 ppm. There was no resonance observed for Zeise1s Dimer. Broadened peaks for coordinated alkyne were observed: d 2„27 (broad), 1.62 (broad), 1.00
(sharp triplet). No free alkyne peaks were observed at this point. At a later time, NMR signals for
tetrapropylcyclobutadienedichloroplatinum(II) were observed, as well as signals for the excess free alkyne. No Zeise1s 24
Dimer or free ethylene was observed at the end of reaction.
A very small amount of hydration product was formed.
Dichloroplatinum(II)-tetraalkvIvclobutadienes
Tetrapropylcyclobutadienedichloroplatinum(II). 4-octyhe
(2 equivalents, O .088g, 0 .Smmol) was added to a stirred slurry of Zeise‘s Dimer (O.llVg, O .4mmol platinum) in ether solvent (5ml). The heterogeneous mixture was allowed to stir for I hour, after which the slightly soluble orange solid was isolated by vacuum filtration through a. sinterred glass funnel, was washed with two portions of pentane (2ml each) and dried under vacuum. The remaining solution was concentrated to 0.5ml and treated with 5 mililiters of pentane to precipitate the rest of the platinum complex, which was collected by filtration, then dried under high vacuum at room temperature to yield the orange solid
(0.182g, 94% yield). The product was recrystallized from ethanol. After several days, a suitable crystal for x-ray analysis was obtained from the standing ethanol solution of the complex. 3OOMHz NMR Spectrometry: NMR (CDCI3) 81.93
(triplet), 1.65 (mult), 0.988 (triplet) ppm. -^C NMR (CDCl3, 75MHz): 5105.7 (Jpt-C = 150Hz), 26.51, 20.25, 14.41 ppm. 195Pt NMR (250MHz) : 5 1784.5 U M K2PtCl6. in D2O as 25
external standard) ppm. Crystal data: C16H28Cl2Pt,
FW = 486.4, monoclinic, space group P21/c, a = 9.228(2) A, b = 15.668(2) A, c = 13.536 (2 ) A, a = y = .90°,
P = 100.61(1)°, V = 1923.7(5) A3, Z = 4, Dcalc = 16.8g/cm3,
T = 25°C, radiation MoKa (X = 0.71069 A) , (j, = 7 6 .4cm”1,
R = 0.044, Rw = 0.043, S = 1.28, 172 parameters. Intensity data were taken as omega scans on a Nicolet R3mE four-circle diffractometer for 5580 unique reflections in the range 3° < 20 , 60°, of which 2047 with I > 3a(I) were used for structure solution and refinement. The data were corrected for Lorentz and polarization effects and for a four percent gradual intensity loss observed for check reflections monitored through the course of data collection. Empirical absorption corrections were based on psi scans collected for sixteen reflections (transmission factor range 0.34 to
0.60). No extinction corrections were needed. The structure was solved from a Patterson synthesis for the platinum position. Non-hydrogen atoms were refined by block-cascade least-squares with anisotropic thermal parameters, using statistical weighting (SHELXTL program package, G . M.
Sheldrick; Siemens Analytical X-Ray Instruments, Inc.:
Madison, W I ). Calculated hydrogen positions were used with fixed thermal parameters (1.2 X carbon atom U's). No attempt was made to model the apparent partial disorder of one of the propyl groups for which the thermal parameters of the 26
terminal carbon refined to exceptionally large values. Bond distance constraints were used in refining the carbon positions for the disordered group.
Selected Bond Lengths (A)
Pt-Cl(I) 2 . 3 25(3)
Pt-C(2) 2 .11(1)
C (I)-C (2 ) 1.43(2)
C ( 3 ) - C ( 4 ) 1.48(2)
Pt-Cl(2) 2.321(4)
Pt-C(3) 2 .12(I)
C d ) -C(4) 1.44(1)
Pt-C(I) 2 .11(1)
Pt-C (4) 2.12 (I)
C (2)-C(3) 1.46(2) 27
Selected Bond Angles (°)
Cl(I)-Pt-Cl(2) 92.8(1)
Cl(I)-Pt-C(2) 109.8(3)
Cl(I)-Pt-C(4) 150.6(3)
C l (2)-Pt-C(2) 150.2(4)
C l (2)-Pt-C(4) 109.9(4)
C d ) -C(2) -CO) 92(1)
C(I)-C(4)-CO) 91(1)
C (4)-C(I)-C(5) 137(I)
C(3)-C(2)-C(8) 132(I)
C (4)- C (3)-C(11) 134 Cl)
C (3)- C (4)-C(14) 134(I)
Cl(I)-Pt-C(I) 145.9(4)
Cl(l)-Pt-CO) 111.0(3)
C l (2)-Pt-C(I) 112.2(4)
C l (2)-Pt-C(3) 146.8(3)
C (2 ) -C (I) -C (4) 90(1)
C(2)-C(3)-C(4) 87(1)
C (2 ) -C (I) -C (5) 132(I)
C (I)-C(2)-C(8) 136(I)
C (2)-C(3)-C(11) 137(I)
C (I)-C(4)-C (14) 134(1) 28
Positional Coordinates and Isotropic Thermal Parameters
(A2) with Standard Deviations in Parentheses
x/a y/b z/c U
Pt 0.51796 (6) 0 . 6 7 8 2 4 ( 3 ) 0 . 5 3 7 1 0 (3) 0 . 0638(2)
Cl(I) 0.6511(4) 0 . 6 7 9 8 ( 3 ) 0 . 7 0 0 6 ( 2 ) 0.104(2)
Cl (2) 0.3007 (4) 0 . 6 4 0 4 ( 3 ) 0 . 5 8 9 0 ( 3 ) 0.107 (2)
C d ) 0.479 (I) 0.740(I) 0.396(I) 0.073(5)
C(2) 0.630 (I) 0.750(I) 0 . 4 4 3 (I) 0.071(5)
CO) 0.659(I) 0.659 (I) 0.432(I) 0.062(5)
C(4) 0.502 (I) 0.650(I) 0.383(1) 0.065(5)
C(5) 0.358(2) 0 . 8 04(1) 0.361(1) 0.096(7)
C(6) 0.207(2) 0.776 (I) 0.347(I) 0.13(I)
C(7) 0 . 0 98(2) 0.851(I) 0.317(I) 0.15(I)
C(8) 0.734(2) 0.824(I) 0.479(I) 0.102 (7)
C(9) 0 . 8 74(2) 0 . 8 06(1) 0.546 (I) 0.14(1)
C(IO) 0.957(3) 0.889(2) 0.578(2) 0.24(2)
C(Il) 0 . 7 87(1) 0.603(1) 0.443(I) 0.081(6)
C(12) 0 . 8 61(2) 0.606(1) 0.351(1) 0.107 (7)
C(13) 0.991(2) 0.548 (I) 0.362(1) 0 .12(1) .
C (14) 0 . 4 13(2) 0.581(I) 0.323(1) 0.104 (7)
C (15) 0 . 4 30(3) 0.590(1) 0.213(1) 0.18(1)
C(16) 0.338(3) 0.528(2) 0.139(2) 0.40(3)
Equivalent isotropic U defined as one third of the trace of the orthogonalised U ij tensor. 29
(Dimethvldipropylcvclobutadiene)dichloroplatinum fII)
2-hexyne (Iml) was added to a dry ether slurry of
Zeise's Dimer (0.147g) all at once, giving an immediate yellow precipitate. The mixture was allowed to stir for 3 hours to allow complete reaction of the slightly soluble
Zeise's Dimer, and the product was isolated by vacuum filtration, washed with two portions of pentane (Iml), then dried under vacuum to yield the yellow solid (0.196g, 91% yield), which contained a mixture (-2 :1, not separated) of trans and cis-(dimethyl-dipropylcyclobutadiene)- dichloroplatinum(II). 300MHz MMR: 1HNMR (CDCI3): 61.83
(br), 1.58 (br), 0.93 (br) ppm. 13C NMR (CDCl3, 75MHz): 5
107.8 (Jpt-C = 154Hz), 104.0 (Jpt-C = 149.9Hz), 103.3 (Jpt-C
146.6Hz), 99.5 (JPt_c = 146.0Hz), 26.1, 25.9, 19.8, 19.5,
14.3, 14.26, 9.6, 9.4 ppm.
(7,8-dimethvl-bicvclo (4,2.01 -octa-1.6.7.8-r|"diene) - dichloroplatinum(II)
2,8-Decadiyne ( 1.5ml) was added dropwise to a slurry of Zeise's Dimer (200mg) in ether (25ml), and this was allowed to stir for several hours in order to assure complete reaction of partially soluble Zeise1s Dimer. The bright yellow precipitate was collected by vacuum 30
filtration, washed twice with Iml portions of pentane, then
dried under vacuum. The complex was recrystallized from
chloroform/heptane. 1HNMR (300MHz, CD3CN): 1.9-1.55
(mult), I.5-1.4 (mult), 1.35 (s) ppm. 13C NMR (75MHz, CD3CN): 107.3 (Jpt-C= 158.5Hz), 98.2 (JPt_c= 158.5Hz), 20.2,
19.7, 9.7 ppm.
(tricvclo (6.4.0.01 dodeca-1.2.7.8-T]4-diene) - dichloroplatinum(TI)
1.7- cyclododecadiyne (0.1048g) was dissolved in diethyl ether (100ml), and Zeise's Dimer (0.1905g) was added to the solution, which was allowed to stir for several hours, in which time a yellow solid had formed. The yellow precipitate was collected by vacuum filtration, washed twice with Iml portions of pentane, then dried under vacuum
(0.2487g, 89% yield). The solid was recrystalIyzed from chloroform/pentane. 1HNMR (CDCI3): 52.2-1.95 (br), 1.9-1.75
(br), I.7-1.6 (br) ppm. 13C NMR (CDCI3): 8105.3 (Jpt-C =
172Hz), 20.7, 20.4 ppm.
(tricvclo (7.4.0.01 trideca-1.2.8.9-T|^— diene)dichloroplatinum(II)
1.7- cyclotridecadiyne (0.178g) was dissolved in diethyl ether (20ml). Zeise's Dimer (0.3030g) was added to the stirring solution. Formation of the yellow solid was rapid. 31
The mixture was'allowed to stir for several hours, and the
bright yellow solid was isolated by filtration, dried and weighed (0.4165g, 92.6% yield). 13CNMR (CDCl3): 107.2 (q),
105.5 (q) , 29.4, 26.9, 26.7, 20.5, 20.0, 15.2 ppm.
Methanol Addition to 1-alkvnes
Reagents
I-Heptyne and 1-octyne were purchased from Aldrich
Chemical Company and used as received. Methanol was distilled immediately before use from magnesium turnings under positive pressure of argon. Deuterated methanol was purchased from Cambridge Isotope Laboratories and used as received. Reactions were run under slight positive pressure of argon in flame dried flasks sealed with rubber septa.
2 ,2-dimethoxvheotane(I)
Zeise's 'Dimer (0.08g) was dissolved in freshly distilled methanol (150ml), and the solution was cooled in a dry ice/acetone bath. I-Heptyne (4.0ml) in methanol (30ml) 32
was added dropwise over 20 minutes to the stirring solution
by addition funnel, keeping the contents of the flask under
argon. The solution darkened upon warming to 0°C over I hour. The contents of the flask were concentrated, then extracted into pentane, and the pentane extracts were
filtered through silica gel to remove the platinum catalyst.
The solvent was removed first by simple distillation, then the contents were left under high vacuum for several hours, and the remaining liquid was vacumm distilled (80°C, dtorr) to yield a colorless liquid (2.9g, 78% isolated yield, one product by NMR). NMR peak assignments were made on the basis of 2D-proton correlation (COSEY) and Heteronuclear 2D- correlation (HETCORR). 1HNMR (CDCl3 ) 53.12 (s, 6H, OCH3),
1.55 (tr, 2H, CH2 ), 1.28 (m, 6H, 3 CH2 ), 1.22 (s, 3H, CH3 ),
0.87 (tr, 3H, CH3 ) ppm. 13C NMR (CDCl3 ) 5 101.0 (q, C-
(OCH3 )2 ) 4 8 . 0 (OCH3 ) 36.2 (CH2 ) 3 2 . 0 (CH2 ) 2 4 . 0 (CH2 ) 22.3
(CH2 ) 21.0 (CH3 ) 14.0 (CH3 ) ppm. Gas chromatography/mass spectrometry: GC temperature program 30°C for 5 minutes,
IO0Zmin to 310°C, hold 20 minutes. Retention time (RT) =
12:22 (total ion current (TIC) = 4518), m/z = 145 (%base peak = 2.1, loss of CH3), 129 (10), 128 (14), 85 (92), 72
(100), 55 (53), 42 (48). RT = 8:56 (TIC = 569), m/z = 128
(m+, 3.48), 85 (100), 55 (50), 43 (23), methyIvinylether. RT
= 8:05 (TIC = 416), m/z = 128 (m+, 10.1), 85 (62), 72 (100),
55 (34), 42 (46), methylvinylether. RT = 7:58 (TIC = 3583), 33 m/z = 114 (m+, 7.4), 71 (16), 58 (71), 43 (100), methyl ketone.
2,2-dimethoxvoctane Assignments Based on DEPT Experiment
1H-NMR (CDCI3) 8 3.09 (s, OCH3 ), 1.50 (br, CH2 ), 1.21
(mult, CH2 envelope), 1.18 (s, CH3 ), 0.80 (tr, CH3 ) ppm.
13C-NMR (CDCl3 ) 8 102 (q, C(OCH3 )2 ) 48.0 (OCH3 ), 36.2 (CH2 ),
31.8 (CH2), 29.9 (CH2), 24.1 (CH2), 22.3 (CH2), 21.0 (CH3),
14.0 (CH3 ) ppm.
Reaction of d^-Methanol with I-Ootvne
Zeise's Dimer(0.OlOg) was dissolved in d^- methanol(2ml). I-Octyne(2ml) was added quickly to the solution, and this was allowed to stir overnight. The product was isolated as in the previous examples. 1H-NMR (CDCl3 ) 8 1.5 (br, diminished intensity), 1.20 (br), 0.8
(tr) ppm. 13C-NMR (CDCl3) 8 101.9 (s, C(OCD3 )2 ), 48.1
(heptet, OCD3 ), 35.7 (mult, CD2 ), 31.6 (CH2 ) , 29.5 (CH2 )',
23.8 (CH2 ) , 22.1 (CH2 ) , 20.0 (mult, CHD2 ), 13.8 '(CH3) ppm. 34
Hydrolysis of 2.2-dimethoxvheotane
A sample of 2,2-dimethoxyheptane, prepared as above, was dissolved in d4-methanol in an NMR tube. A spectrum was taken. Dilute hydrocholric acid (0.1M, I drop) was added to the NMR tube. The sample was immediately submitted to NMR analysis. 1H and 13C NMR showed complete conversion to 2- heptanone and methanol had occurred within the time it took to get the sample into the NMR spectrometer.
4-0ctvne Case
4-Octyne was added to a stirred solution of Zeise1s
Dimer in methanol under argon atmosphere. The solution was allowed to stir overnight at room temperature. Only a trace of hydration product was formed with no other organic products detectable.
Attempted Ketal Formation from 2-heptanone
Zeise's Dimer was dissolved in anhydrous methanol and
2-heptanone was added to the solution, which was stirred at room temperature under argon overnight. No reaction was 35
observed by 1H NMR analysis of the organics after
concentration under vacuum.
2-Heptanone was dissolved in anhydrous methanol and was
treated with I drop of concentrated hydrochloric acid. The
mixture was stirred overnight at room temperature under
argon atmosphere. No reaction was observed.
Attempted Synthesis of 6-methvl-3.4-dihvdro-2H-r>vran
5-Hexyn-l-ol (0.5ml) was added all at once to a stirred
solution of Zeise's Dimer (40.Img) in tetrahydrofuran(IOml)
at room temperature. The THF solution turned orange upon
addition, then immediately brown, with evolution of heat.
After the flask had cooled (~10min) the solution was
concentrated under vacuum, and immediately distilled by
Kugelrohr to yield a colorless liquid (~0.3ml). 1H NMR
(CDCl3, tentative assignments based on comparison to spectra of known compounds) 8 4.48 (tr, C=C-H), 3.80 (dt, CH2-O),
1.7 (mult, CH2), 1.25 (s, methyl). 13C NMR (CDCl3) 5 151.9
(q, C-0), 98.3 (C=C-H) ppm. Results and Discussion
It was during the attempted reaction of Hank's ylide21 with 4-octyne, generated in-situ by reaction of Zeise's
Dimer with diazomethane, that adventitious water-from contamination of the ether solvent-was observed to have been added to the alkyne. The ketone produced in this initial experiment, 4-octanone, was identified upon examination of its mass spectrum, when it was evident that something with mass 18 had been added to the alkyne. Evidence of McLafferty rearrangement of the ketone in the mass spectrum was confirmatory. Zeise1s Dimer was found to be the actual catalyst precursor by several control, experiments. When ether was saturated with water, and Zeise's Dimer was used as the catalyst precursor, the hydration of 4-octyne was found to go to completion. Several alkynes were submitted to similar conditions, using ether or THF as solvent (figure
5), and it was found that dialkylalkynes hydrated smoothly to give excellent yields of the corresponding ketones. 37
Zeise's Dimer (cat.) ------E— THF, H2O 93% isloated
-- C=C - x X / 1.6 : I 76%
0 o -- C=C - \JX-x 2 : I 84%
-- C=C
86%
Figure 5 Hydration of Dialkylalkynes
Regioselectivity in these reactions was mild. 2- pentyne, for instance, gave a 1.6:1 mixture of 3-pentanone and 2-pentanone. 2-Hexyne was a little better, giving a 2:1 mixture of ketones, and even 4,4-dimethyl-2-pentyne gave only a 2.7:1 ratio of products using this catalyst. The regioselectivity is explained by steric effects in the alkyne-platinum complex. Upon coordination to the alkyne the platinum slips preferentially toward the smaller alkyl group of the alkyne, due to the steric effect of the trans- 38
dichloroplatinum(II) center. This is illustrated for 4,4-
dimethy1-2-pentyne in figure 6. The acetylenic carbon
bearing the larger group develops a greater partial positive
charge, relative to the other carbon, and attack of water
occurs there. The other carbon has also attained a partial
cation character, though, and the water can also attack at
this site to some extent. Hydration of 1-alkynes leads only
to the corresponding methylketones.
CH3
Figure 6 Explanation for Regioselectivity
Using the current model for the reaction as a starting point, the practical'goal is to design new catalysts which will accelerate the reaction and/or enhance the regioselectivity. Substitution of bulkier alkenes, such as cyclohexene or styrene, for ethylene in Zeise1s Dimer does not increase the regioselectivity of the reaction. Another way of increasing the steric bulk of the platinum catalyst 39
is to substitute bromine (or some other bulky ligand) for ■ chlorine. The bromine analogue of Zeise's Dimer would provide more of a steric effect than with chlorine, but retain the same relative electronic effects. The bromine analog of Zeise's Dimer was found to be very unstable, and could not be isolated for use as a catalyst. However, later studies employed platinum(IX) bromide, which was found to be a good catalyst precursor, and which gave a significant improvement in regioselectivity in the reaction of 4,4- dimethy1-2-pentyne (3.5:1 ratio of hydration products) 22 .
Electron withdrawing groups on an alkyne tend to lower the yield of hydration product substantially in this system.
Dimethylacetylenedicarboxylate was the worst example studied, giving only a complex mixture of products, excluding the expected hydration product. Diphenylacetylene and phenyl-I-propyne gave poor yields of hydration product under similar reaction conditions, and phenylacetylene gave similar results to other 1-alkynes in ether solvent.
Terminal alkynes are polymerized when high concentrations of alkyne are present in solution (in ether solvent) using
Zeise's Dimer catalyst. 40
H-C=C- Zeise s Dimer THF, H2O reflux 97% yield after distillation
ISO 180 170 160 120 HO 100 70 60 PPM
|
Figure 7 13C and 1H NMR of 2-Heptanone from Hydration of I-Heptyne 41
-The hydration of terminal alkynes, exemplified by
1-hexyne and 1-heptyne, was eventually optimized. The problems with this reaction, primarily involving polymerization of the alkyne, were overcome by running the reaction at high dilution of alkyne in water saturated tetrahydrofuran solutions. In a typical preparation, the alkyne is added dropwise to a refluxing tetrahydrofuran/ water solution of Zeise's Dimer over 20 minutes, and the solution allowed to reflux for several hours. In this way, the reaction of 1-heptyne gave only 2-heptanone, which was isolated in very high yield. The NMR spectra in figure 7 were the result of analysis of the hydration product of
1-heptyne. In this case, 2-heptanone was distilled directly from the reaction flask, leaving the catalyst as the only residue. As can be seen from the spectra, the product is very pure.
Some preliminary work was done to explore the mechanism of the reaction. The effect of various solvents was tested, and it was found that the reaction was actually not very efficient in ether, compared to tetrahydrofuran, the best solvent that was tried. In chloroform, hydration did not proceed appreciably, owing in small part to the solubility of water in that solvent. Hydration of 4-octyne was efficient in methanol. It was found that tetrahydrofuran or 42 a similar coordinating solvent was necessary for the reaction to proceed at a reasonable rate.
Several other simple experiments were performed on the
4-octyne system. It was shown that addition of p-toluenesulfonic acid had no effect on the rate of the reaction. Nor did catalytic amounts of mineral acids.
Substitution of DgO for H2O, in a side by side comparison, also showed no effect on the rate. Some comparisons were made to other catalyst systems. When K2PtCl4 was employed as a catalyst precursor in ethanol solution, hydration of the alkyne was observed, however, in much lower yield, and not without side products. A known platina(IV) cycle complex was also tried(in tetrahydrofuran), but no hydration was observed in that case. An interesting aside is the discovery that the (sigma bound)-platinum(II)-cycloolefin complexes elaborated by John Hoberg also catalyzed the hydration of alkynes23. Because hydration of alkynes is classically performed with mercury catalysts, mercuric sulfate was employed as a catalyst under aqueous acid conditions.
Consistent with the literature, this system gave a mixture of products, including the hydration product. 43
Mechanistic Studias
What is the nature of the active catalyst? Puddephatt has shown evidence that Zeise's Dimer remains a dimer in chloroform solutions24, but Orchin showed that it is a monomer in tetrahydrofuran solution25, with THF acting as a ligand. This is supported by proton NMR studies of Zeise's
Dimer and other platinum-alkene and alkyne complexes.
The coordinating ability of several solvents was compared by dissolving Zeise1s Dimer in deuterated solvents and recording the 1H and 13C NMR spectra of each respective solution. The proton spectrum of Zeise1.s Dimer in CDCI3, for example, shows platinum coupled ethylene resonances at 4.8 and 4.7ppm, in a ratio of 4.5:1, indicating the anti and syn complexes, respectively (figure 8). Thus, in chloroform solutions, the dimer is the predominate species. In deuterated tetrahydrofuran, both isomers of the dimer may be observed initially. However, only one 1H resonance for ethylene is observed after several minutes, with a chemical shift of 4.3ppm, upfield from that observed for the dimer in chloroform. In the same way, the solvents D2O, CD3OD, and
CD3CN were found to split the dimer into the corresponding solvent monomers (figures 9, 10 and 11). These results correspond to the excellent solubility of Zeise's Dimer in these solvents. Diethyl ether is slightly better as a 44
coordinating solvent than chloroform; but Zeise's Dimer is presumed to be mostly dimeric in this solvent also, based on its very low solubility.
Zeise's Dimer
and
syn
Figure 8 Structure of Zeise's Dimer 45
Figure 9 NMR Spectra for DgO Monomer of Zeise1s Dimer 46
5 5 5.0 4.5 4.0 3.5 3.0 25 2 0
Figure 10 13C and 1H NMR Spectra of Zeise's Dimer in CD3OD 47
Figure 11 Zeise's Dimer in CD3CN 48
Exchange Experiments on Zeise's Dimer
The reaction of an alkyne with platinum(II) (Zeise's
Dimer) can give strikingly different results depending on
the alkyne, the solvent, and the presence or absence of water. The hydration of 4-octyne was performed in d8-THF/H20, using Zeise's Dimer in a catalytic amount, in order to
observe the reaction throughout its course by proton NMR
(figure 12). It was observed that, at moderate concentration of alkyne, the resonance for platinum-bound ethylene was broadened upon addition of the alkyne and water to a tetrahydrofuran solution of Zeise's Dimer. No free ethylene resonance was observed. Furthermore, the chemical shift of the bound ethylene did not change appreciably from 4.3ppm during the catalytic reaction. When the reaction had proceeded to completion the bound ethylene resonance became sharper, and the peak area had not diminished significantly from that for the starting complex, indicating that the ethylene ligand on the catalyst had not been displaced.
When a control experiment was run in ChloroformZH2O
(figure 13), addition of 4-octyne to the Zeise's Dimer solution resulted in immediate displacement of the ethylene, with free ethylene giving a singlet at 5.Ippm in the proton spectrum. 49
Zeise s Dimer in Ietrahydrofuran before addition of 4-octyne and water LJ
Addition of 4-octyne and water J V -L A_ A
Infinite reaction time Hydration is complete
J t -i_IA a ..i 4.5 4.0 3.5 3.0 2.5 2.0 L5 1.0
Figure 12 1H NMR Spectra for Catalytic Reaction in Tetrahydrofuran-dg 50
Zeise's Dimer in CDCI3
-JU jl
...... 7.» 5.5 5.0 4.5 3.0 PPm
Addition of 4-octyne
Products
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
Figure 13 1H NMR Spectra For Ethylene Displacement in Chloroform-d 51
Tetrapropylcyclobutadienedichloroplatinum(II), the alkyne dimerization product, was formed completely within several minutes, and only a small amount of hydration product was formed. This helps explain a previous observation that the catalytic hydration was much less efficient in non coordinating solvents, such as ether and chloroform.
In tetrahydrofuran/water solutions, addition of alkyne to the solvated monomer of Zeise1s Dimer leads only to hydration products. Furthermore, no free ethylene is detected before, during or after the reaction is initiated by the addition of alkyne to the catalyst solution. At infinite reaction time, the platinum species left in solution is the tCtrahydrofuranZH2O monomer of Zeise1s
Dimer. Although it is possible that ethylene exchange takes place during the reaction, alkyne and solvent exchange predominates over this process. The broadening of the ethylene resonance is probably due to the averaging of signals from the various intermediates in the reaction, and may also be due to water exchange.
The Role of the Ethylene Liaand in the Catalyst
When bis-(4,4-dimethyl-2-pentyne)dichloro-di-u- dichlorodiplatinum(II) was dissolved in CDCl3, it was observed to remain in the dimeric form over several days. 52
even with added water (figure 14). The complex did not react
with water appreciably over a period of days. When 4-octyne
was added to the mixture, however, reaction of the "free"
alkyne with the platinum complex proceeded smoothly to yield
the expected products, as seen before in chloroform
solutions of Zeise's Dimer. This was repeated for
tetrahydrofuran as solvent, with similar results, except
that the 4,4-dimethyl-2-pentyne complex was in the form of
the THF monomer. Considering the previous results, this
reinforced the hypothesis that another unsaturated organic
ligand, capable of backbonding with platinum, had to be on
the metal in order to activate the substrate alkyne to
attack by water.
Bis-(4,4-dimethyl-2-pentyne)dichloro-di-u-
dichlorodiplatinum(II), in the form of its THF monomer, was
found to catalyze the hydration of alkynes in
tetrahydrofuran solutions. Substitution of the acetylenic
ligand in the place of ethylene on the catalyst gave a
significant increase in the rate of hydration of 4-octyne.
The 4,4-dimethyl-2-pentyne dimer gave an observed first
order rate constant for hydration of 4-octyne of kobs =2.72
X IO-4. Zeise's Dimer in an equimolar amount under the same
conditions gave kobs = 8.12 X IO-5. The increased rate of reaction with the 4,4-dimethyl-2-pentyne analogue over that of Zeise's Dimer may be due to the superior backbonding 53
ability of the acetylenic ..ligand. This, may be because of the
extra orbital overlap between the orthogonal (out of the coordination plane) antibonding orbitals of the acetylene and filled metal d orbitals.
In the proposed catalytic cycle, a molecule of the alkyne coordinates to the platinum center of the solvent monomer of Zeise1s Dimer, with loss of THF to form the intermediate trans-(alkyne)(ethylene)dichloroplatinum(II).
This species is presumed to react with water to form the final product, which is then displaced by another substrate molecule. Although trans-alkene-alkynedichloroplatinum(II) complexes have not been synthesized, bis-alkene complexes such as trans-diethylenedichloroplatinum(II) have been prepared by Chatt26, from Zeise's Dimer and excess ethylene.
Other bis-olefin monomers have been prepared similarly27'28'29,30 . Very recently, the first alkynealkene- transitionmetal complex has been synthesized by Taube and co-workers31. They reacted pentaammineosmium(II) first with ethylene, then with acetylene to form the trans- ethylenealkyne osmium complex. They also synthesized an analogous bis-alkyne complex. 54
syn, syn
syn, anti
Te ZT
T 6 2
Figure 14 Top: di-(4,4-dimethyl-2-pentyne)-dichloro-di- |J.-dichiorodiplatinum(II) . Bottom: Addition of 4-octyne and water to the complex. 55
The proposed alkene-alkynedichloroplatinum(II) intermediate, which is formed from the solvent monomer of
Zeise's Dimer, owes its reactivity to the ability of platinum to back-donate electron density into the antibonding orbitals of the alkene on demand. Although
Zeise's Salt, KlPtClg (C2H4) ] -H^O, apparently shows minimal backbonding to the ethylene (bound ethylene C-C distance =
1.375A, free ethylene C-C = 1.337A)32,•more electron rich platinum-olefin complexes, such as Pt (PPI13) 2 (C2H4) , have a much larger backbonding component(C-C = 1 .43A)33 . The lengthening of the C-C bond upon coordination of an alkene is consistent with rehybridization to an sp3 bond. This is referred to as the metallacyclopropane extreme. When an alkyne associates with a platinum-alkene monomer, excess electron density can be dumped from the platinum to the antibonding orbitals of the alkene. This allows activation of the alkyne that is not possible in corresponding complexes where alkene has been replaced by amine or some other non-backbonding ligand.
The alkene or alkyne ligand resident on platinum plays an important role in the active catalyst by accepting excess electron density from the metal. For hydration of an alkyne to occur there must be two alkyne ligands (or one alkyne and one alkene) on the active catalyst. In practical terms the 56 use of alkynes in place of ethylene results in a more efficient catalyst.
Kinetics Experiments- 1H MMR
From the preceding results, it was determined that the active catalyst, in the case of Zeise's Dimer in tetrahydrofuran, is most likely monomeric (ethylene)- dichloro(L)platinum(II) (L = THF, H2O), and that the ethylene is retained in the catalyst throughout the catalytic cycle. On the other hand, the THF ligand undergoes continuous exchange with water, and with the alkyne substrate and product ketone.
In the solvent monomer of Zeise1s Dimer, THF is by far the best leaving group. Furthermore, the trans effect of the ethylene on trans-dichloro(ethylene) (THF)platinum(II) predicts that ligand substitution will result in a trans product. Although two unsaturated ligands are needed for hydration to proceed, one is retained by the catalyst, while the other reacts upon coordination, if it is an acetylene.
Since water is a better nucleophile than tetrahydrofuran, it probably competes strongly for the metal center. So the active catalyst is most likely trans-
(aquo)(ethylene)dichloroplatinum(ll). Acetylene coordinates to this complex by an associative mechanism, and the 57 resulting 5-coordinate intermediate collapses to products.
The water can also attack the metal after coordination of alkyne, in a very fast step. Figure 15 summarizes the proposed mechanism. The catalyst reacts only upon coordination of an alkyne, and the product behaves as a noncompetitive ligand. Enzyme kinetics were considered to be the most applicable model for a chemoselective catalyst with one "active site", such as this.
R I C
Figure 15 Detailed Mechanism of Platinum(II) Catalyzed Hydration of Alkynes Showing the Michaelis- Menten Constants 58
Run 1 [alkyne] = 0.397 V = 1.3703 - 6.6821 e-5x R*2 = 0.995
Run 2 [alkyne] = 0.225 y = - 1.5052 - 6.8115e-5x RA2 = 0.993
Run 6 [alkyne] = .149 ‘-~ - y = - 1.8801 - 6.3518e-5x RA2 = 0.998
Run 4 [alkyne] = 0.041 M y = - 3.1764 - 5.8330e-5x RA2 = 0.962
5000 10000 1 5000 time (s)
Figure 16 First Order Plots at Several Initial Concentrations of 4-Octyne iue 17 Figure k(observed) (1/t(seconds)) 5 6.00e-5 - 6.00e-5 7.006-5 . 5 - 6 0 0 y = 6.8926e-5 + 6.7464e-6*LOG(x) 6.7464e-6*LOG(x) + 6.8926e-5 = y Saturation Kinetics Saturation nta [-cye (molar) [4-octyne] initial 59 R*2 0.984 = iue 18 Figure
1/rate 20000 10000 30000 - 30000 40000 - 40000 50000 - Michaelis-Menten Graph Michaelis-Menten 213 82.O R2 0.96 = RA2 8824. Ox + 3281.3 1 /[4-octy ne] 60 61
run # rate [4-octyne] 1/rate I/[4-octyne]
2 2.35e-5 2.25e-l 4.255e+4 4.44
I 3.61e-5 3.97e-l 2.77e+4 2.52
7 5.34e-5 5.03e-l I. 87e+4 1.99
8 7.42e-5 6.42e-l 1 .35e+4 1.56
9 6 .53e-5 7.61e-l I .53e+4 1.31
10 6.23e-5 8.67e-l I.61e+4 1.15
11 8 .Ole-5 9 . 9 9 e - l I .25e+4 1.00
Table I Data for Michaelis-Menten Graph
Rate _ k 2 [alkyne] [catalyst]0 k_i + k 2 [alkyne] + K m K-m — ki equation I
J _ = K m _ 1 ___ + I rate k2 [catalyst]0 [alkyne] k2 [catalyst]0 62
Michaelis-Menten Catalyst Model
The rate equation for an enzyme catalyzed reaction is derived from a mechanism in which reversible coordination of the substrate to the enzyme is followed by conversion of the substrate to product and dissociation of that product, in what is usually considered an irreversible step. This model assumes a steady state concentration of the enzyme-substrate complex, and is valid only at high concentrations of substrate relative to enzyme. Accordingly, the platinum(II) catalyzed hydration of an alkyne should appear to be first order in alkyne. NMR was used to collect rate data for the hydration of 4-octyne in d8-THF, using Zeise1s Dimer as catalyst precursor. The first order plots of In[4-octyne] vs. time at several initial concentrations of alkyne are shown in figure 16. The catalytic system obeys saturation kinetics, as is shown in figure 17.
Data from seven individual kinetic runs (table I) at high alkyne concentrations relative to total platinum concentration was used to calculate the Michaelis constant and k2 for the reaction from a graph of reciprocal initial rate vs reciprocal initial concentration of alkyne (figure
18). The slope and y-intercept of the line give the constants Km and k2, according to equation I. 63
Runs 3-6 were excluded because the concentration of 4-octyne in these runs was too low for the steady state approximation to hold. The Michaelis constant, Km , can be thought of as a dissociation constant for the .intermediate platinum-alkyne complex, and the value obtained for this reaction, Km =
2.61, indicates that the product formation step is highly favored. This unimolecular step is comprised of several rearrangements of the preceding intermediate alkyne complex, and the transient intermediates formed during these rearrangements cannot be directly observed on the NMR time ' scale. However, literature precedent, as well as evidence obtained in this study, can be used to propose acceptable mechanisms for these events in some detail. The product formation step, with a first order rate constant of k2 =
3. SXlO--3S--1-, is not the rate determining step in the overall reaction. Rather, the association of substrate alkyne to the platinum center is the rate determining step, with a second order rate constant of kx = -SXlO-5M-1S-1.
Evaluation of Possible Mechanisms
The results of outside research in platinum chemistry have helped in evaluating possible mechanisms for the hydration reaction, and the proposed model for how the 64 catalyst works in coordinating solvents is supported by the literature, and by the results of this study. Figure 14 shows the proposed mechanism. There is precedent for all of the intermediates in the mechanism shown in the figure.
Working backward from the product ketones, it is assumed that they arise from dissociation of a ketone complex of platinum(II), which was formed by rearrangement of the reactive intermediate. Aldehydes and ketones are well known to bond as ligands to transition metals34, and have been proposed as intermediates in several catalytic reactions.
There is at least one example of a platinum (II)-acetone complex, reported by Salaun and company35'36. Trans- (C2H4)PyCl2Pt(II) was irradiated in acetone solution to yield the trans-(Ti1-Ucetone) PyCl2Pt (II) complex. While the Pt(II) complex is 1-hapto, stable zero valent transition metal complexes generally bond to carbonyls in a 2-hapto fashion. In the proposed mechanism, formation of a 1-hapto- oc-o- bonded ketone from the tautamerism of the a-bound vinyl alcohol occurs in a very fast step. This rearranges to the product ketone-platinum complex. The free ketone can undergo exchange on platinum (II), but is not competitive with water or alkyne. The platinum-G-bound vinyl alcohol is not expected to be long lived, but there are clear examples of G-vinyl alcohol ligands in platinum chemistry.
Chloro (acetylacetonato) (T]2- vinyl alcohol) platinum(II) has 65 been isolated and fully characterized37. The 2-hapto compound is prepared by reacting vinyl trimethylsilyl ether with chloro(acetylacetonato) (ethylene)-platinum(II) in benzene solution for 60 hours at room temperature, yielding chloro(acetylacetonato)- (pi-vinyl trimethylsilyl ether)platinum (II), which is then exposed to moist argon to form the final product. Treatment of this complex with one equivalent of potassium hydroxide leads to a r^-platinum-P- oxoethyl complex, which can be isolated as the potassium salt. The 1-hapto complex can also be synthesized directly by reaction of chloro(acetylacetonato)(ethylene)platinum(II) with acetaldehyde. It was also shown that 1-hapto-chlorobis- (tripheny!phosphine) (-CH2COH) liberates acetaldehyde when treated with HCl.
The formation of the proposed vinyl alcohol complex in the platinum(II) catalyzed hydration of alkynes proceeds from a pentacoordinate (alkyne)(aquo)(ethylene)- dichloroplatinum(II) intermediate, which is formed in the first step of the catalytic process by association of alkyne onto the platinum center. Pentacoordinate intermediates are a well known feature of ligand substitution reactions on platinum(II), and stable pentacoordinate platinum(II) complexes have been isolated and characterized38. Whether attack of water on the sp carbon of the coordinated alkyne occurs from the outer solvent sphere or, alternatively, from 66
water which resides on platinum cannot be known with
certainty. However, there is evidence which strongly
suggests that water does reside on the platinum. First, the
concentration of water does not seem to affect the rate of
hydration in the catalytic system. Water does not appear in
the rate law for the reaction. The .second step in the
Michaelis mechanism, rearrangement to the ketone-platinum
complex, has a first order rate constant, in agreement with
the proposal that a pentacoordinate intermediate alkyne-
platinum-aquo complex decomposes to products directly.
Zeise1s Dimer has already been shown to have a high affinity
for water.
Water attack from platinum implies formation of a cis-
vinyl alcohol complex as an intermediate. Recent studies by
Taube and company39 on pentaamineosmium(II) in reactions with
unactivated alkynes have revealed that 2-hapto coordinated
cis-vinyl ethers and vinyl alcohols are formed when the
alkyne complex is allowed to stand overnight in the
appropriate solvent (figure 19). However, isomerization
occurs over several days to give the trans-vinyl complexes.
This isomerization is catalyzed by either acid or base.
However, these conditions did not lead to the formation of ketones, as might be expected, even though the corresponding
1-hapto ketone complex was successfully prepared by reaction of the ketone with pentaamineosmium(II). 67
Taube's work represents the first example of a stable
neutral vinyl ether or vinyl alcohol complex arising from an
alkyne coordinated to a late transition metal. Osmium(II) is
known to participate strongly in backbonding to unsaturated
ligands, explaining the stability of the 2-hapto complexes
and the fact that no 1-hapto complexes were observed. The
initial formation of cis-addition products strongly implies
a cis mechanism, with the nucleophile being delivered from
the metal.
[Os[NH3]5 p 2-butai 2-butyne
C = O CH3--- C C - C H 3 ii '>
rOCH3
slow slow
'OH \ / ^OCH3
Figure 19 Cis-Addition of Water and Methanol to an Osmium (II)-Alkyne Complex 68
Cis-attack of ligand on the coordinated alkyne can be thought of as a formal ligand insertion of alkyne into the metal-oxygen bond of a metal-aquo or metal-methanol complex.
This occurs for both osmium(II) and platinum(II) . Bryndza and co-workers40 have demonstrated that coordinated methoxide can be delivered from a platinum(II) center to an activated olefin. In their study (DPPE)Pt(CH3)(OCH3) was reacted with tetrafluoroethylene in tetrahydrofuran at 25°C for 4 hours to yield (DPPE)Pt(CH3)(CF2CF2OCHl) in quantitative yield.
H R R HX
RR X
H
R
H
X
Figure 20 Addition of Protonic Acids to a Platinum(0)- Alkyne Complex 69
There are other examples of cis mechanisms in platinum
chemistry. Reaction of bis(tripheny!phosphine)(2-butyne)-
platinum(0) with protonic acids gives predominately cis-2-
butene41, Acid catalysis of cis-2-butene to the trans product
occurs very slowly in this system. These reactions proceed
through platinum(II) and platinum(IV) intermediates of the
type shown in the reaction scheme in figure 20. The
platinum (II) catalyzed hydration of alkynes probably has a
similar mechanism, in which both alkyne and water are
activated by the metal, leading to platinum intermediates of
higher oxidation state.
The mechanism of platinum catalyzed hydrogenation of
olefins and acetylenes involves platinum hydride
intermediates derived from !^-coordinated dihydrogen; hydride is delivered from the metal to the bound substrate.
There are many examples of stable hydrido and hydroxo platinum complexes, as well as hydrido-hydroxo platinum
complexes, which are thought to-be models of reactive
intermediates in hydrogenation, oxidation and other
catalytic reactions on olefins. Platinum(II) is known to
catalyze proton/deuteron exchange reactions in protic
solvents42.
Cis attack mechanisms have also recently been advanced
for palladium catalyzed oxidation of olefins, and have gained favor, at least in aqueous systems, over formerly 70
accepted trans mechanisms. In the hydroxypalladation of
alkenes, the mechanism is generally agreed to involve the
coordination of the alkene (pi-bond) to palladium, followed
by conversion of this intermediate complex to a beta-
hyroxyalkyl species43. The rate equation for the reaction is
shown in figure 21.
PdCl42' + CnH2n + H2O ------► Pd(O) + CnH2nO + 2 d ' + 2HC1
-d[olefin] _ k[PdCl42'][olefin] dt [H+HCl']2
Figure 21 Mechanism of Hydroxypalladation
Henry, Zaw and Wan44 have shown recently that oxidation
of allyI alcohol (as well as acyclic olefins) proceeds
through cis attack of hydroxide from the metal center, and has the same mechanism as hydroxypalladation of simple
acyclic alkenes. Hosokawa and Murahashi have published an
excellent account of their investigation of the mechanism of
oxypalladation of alkenes. They showed, conclusively, that palladium remains in the 2+ oxidation state throughout the reaction, and that the active catalyst is a Pd-OOH species derived from oxygenation of a Pd-H species. They showed, by 71
oxygen labeling studies, that oxygen is transferred to the
coordinated olefin from this Pd-OOH complex.
threo
Figure 22 Evidence for External Attack of Water on the Coordinated Ethylene of Zeise's Dimer
Trans mechanisms are not entirely ruled out in all palladium and platinum catalyzed olefin oxidations. Very recently, Bercaw and company45 studied reactions of platinum (IV) alkyl complexes as model reactions for the oxidation of olefins by aqueous platinum(IV) chlorides. In a stereochemical study of the oxidation of cis and trans-1,2- dideuterioethylene analogs of Zeise's Dimer, oxidized by
[PtCl6]2-, they claimed that trans dideuterioethylene was converted to -90% erythro- [Pt-Cl6 (CHDCHDOH) ] (3Jhh = 8Hz), based on 3Jhh coupling constants (figure 22). They propose 72 that the stereochemistry must have arisen from external.. attack by water on the platinum (Il) bound olefin of Zeise1s
Dimer. The alcohol complex was then treated with chloride ion, yielding about 90% threo-ClCHDCHDOH (3Jhh = 6Hz). The threo-2-chloroethanol was then treated with sodium hydroxide to form the cis-dideuterioethylene oxide.
Addition of Methanol to I-Alkvnes
One of the first attempts at mechanistic studies related to the hydration reaction was to try to add methanol to the carbon-carbon triple bond of an alkyne bound to platinum. If vinyl ethers could not be made this way, then perhaps a platinum vinyl ether complex could be observed.
The hope was to reveal the mode of attack of the nucleophile by producing either a free cis or trans vinyl ether or, alternatively, a cis or trans platinum-vinyl ether complex.
The problem of adding methanol to an alkyne using platinum catalysts is Over 30 years old. However, repeated attempts to do this have been very marginal in their success. It seems logical that methanol should react with alkynes similarly to water with Zeise's Dimer catalyst.
However, several initial experiments with internal alkynes 73
such as 4-octyne, as well as terminal alkynes, led to the
false conclusion that methanol could not be added this way.
The failure of methanol to add to alkynes under the
conditions described could not be rationalized. William
Nugent suggested in 199046 that an intramolecular alcohol addition might work better than the intermolecular cases that had been tried. This prompted many experiments on the
Zeise1s Dimer catalyzed rearrangement of 5-hexyn-l-ol.
Adding this substrate to a tetrahydrofuran solution of
Zeise1s Dimer resulted in a strongly exothermic reaction.
Immediate workup of the products was followed by NMR analysis. 1H and 13C NMR showed characteristic peaks for
6-methyl-3,4-dihydro-2H-pyran, rather than the expected exocyclic methylene regioisomer. However, gas chromatography-mass spectrometry showed that the major product from the reaction had a mass twice that expected, and this was assumed to be dimerized starting material. A control experiment was run in which commercial 3,4-dihydro-
2H-pyran was submitted to the same reaction conditions. The only product isolated from the reaction was dimerized starting material. There were other products from the reaction of 5-hexyn-l-ol, including carbonyl compounds, which were found to form even under rigorously anhydrous conditions, presumably from rearrangement of the first formed product. It was apparent that the terminal alkynoI 74 was more reactive than had been anticipated. The full analysis of this complicated system was not attempted, returning instead to the study of methanol addition to
1-alkynes.
The 1-heptyne case was tried again and, indeed, methanol did react with the carbon-carbon triple bond of the alkyne. However, the NMR spectra of the final product were not consistent with a vinyl ether, since there were no olefinic resonances in either the carbon or the proton spectra (figure 23). There was a strong methoxy peak in both the 1H and 13C NMR spectra (1H 3.12 ppm, 13C 48.0 ppm) not due to methanol. A sample of this compound in CDCl3 which had already been analyzed was spiked with methanol. 1H and 13C
NMR spectra were recorded, showing a large new peak for methanol in each spectrum (1H 3.35 ppm, 13C 50.5 ppm). It was found from a 13C NMR DEPT experiment and from a heteronuclear correlation experiment (HETCORR, figure 24) that a quaternary center was present in the molecule at the carbon bonded to the methoxy group. Integration of the proton spectrum showed the methoxy peak to be accountable for 6 protons in the molecule. Hence, the product was assigned the structure of 2,2-dimethoxyheptane, as shown in figure 23. 75
170 160 150 140 130 120 lit) 100 90 80 70 BO ' ' SO ' ' 40 ^ ' 3o'^' ‘20 ' ' '10 6 -I.) '
Zeise's Dimer (cat.) CH3Ox ^OCH3
anhydrous CH3- methanol
flL30fl Sin: BG SCAN = 547 12: 22
Figure 23 13C, 1H and Mass Spectra of 2,2-dimethoxyheptane 76
1.0
- 1.6
8 0 T S 7 0 6.3 6.0 5.5 5.0 4 3 4.0 3 3 3 0 2 3 2.0 15
Figure 24 Top: HETCORR of 2,2-dimethoxyheptane. Bottom: Vinyl ether? 77
One mechanism for the formation of ketal under these
conditions may be ruled out entirely. The ketal is not
formed from the corresponding ketone, either with platinum
catalyst or with protonic acid. In this study, 2-heptanone
was prepared by hydration of 1-heptyne in the usual way.
After purification, attempts were made at both H+ and
platinum (II) catalyzed ketal formation in anhydrous
methanol, but only the starting ketone was recovered in each
case. In general, ketals cannot be made from ketones,
although acetals are formed from aldehydes quite easily with
H+ catalyst47. The equilibrium between ketal and ketone
favors the ketone almost exclusively. In another experiment,
pure 2,2-dimethoxyheptane, prepared from 1-heptyne, was
quickly and quantitatively converted to 2-heptanone under
conditions of dilute hydrochloric acid.
In some of the crude product 1H spectra (figure 24,
bottom), taken before workup of the 2,2-dimethoxyheptane,
there are broadened peaks at 5.0-5.3ppm, indicative of vinyl
ether products. In fact, GC-mass spectrometric data taken of
the distilled liquid product indicated that three distinct
products were present after workup. The ketone(m/z 114) was
found as a contaminant arising from hydrolysis of the ketal, which occurred when samples of 2,2-dimethoxyheptane were
left exposed to air. There was an additional peak in the GC 78
trace due to the vinyl ether (m+ = 128). The major product peak represents the ketal (m+ = 145, loss of CH3). The minor
product methyl-vinyl ether is probably an intermediate in
the reaction, and it apparently reacts with a second
molecule of methanol to form the final product. The
possibility of limiting reagent alcohol so that vinyl ethers
are formed preferentially from 1-alkynes is worth looking
a t .
Cvclobutadienes
In coordinating solvents containing water,
dialkylalkynes are hydrated catalytically by Zeise's solvent
monomer without side products. In chloroform or other non
coordinating solvent, or under conditions of concentrated
alkyne, treatment of Zeise's Dimer with dialkylalkyne
results in the formation of platinum stabilized
tetraalkylcyclobutadienes. When 4-octyne (neat) was added to
solid Zeise's Dimer immediate evolution of ethylene was
observed, and a new complex was formed (figure 25). The
major product, tetrapropylcyclobutadienedichloro-
platinum(II), did not react with water, as indicated by the
unchanging intensity of its resonances after addition of
water to the NMR sample. I 79
R
Pt C l ^ n ^CI
Figure 25 Tetrapropylcyclobutadienedichloroplatinum(II)
This experiment was done, however, before the platinum cyclobutadiene complex was characterized, and the major product was tentatively identified as an alkyne derivative complex that did not react with water. Synthesis of this product was scaled up, and reerystalization from ethanol gave large single crystals, suitable for X-ray analysis. The structure was solved, and many conclusions followed from this piece of evidence. Figure 26 shows two ORTEP plots of the platinum complex.
First of all, from the crystallographic data, the platinum was found to reside symmetrically beneath the cyclobutadiene ring, with all four carbon-platinum bond lenghths and bond angles equivalent. The four carbon-carbon bond distances were also equivalent. This is consistent with the NMR data, showing a single, platinum coupled peak at
IOSppm for the Ij4-platinum-carbon bond. In solution, the average bond lengths and angles are equivalent. 80
Figure 26 ORTEP Plots of (tetrapropylcyclobutadiene)- dichloroplatinum(II) 81
Figure 27 Mechanism of Formation of Tetrapropylcyclobutadienedichloroplatinum(II)
The complex was monomeric. This has implications to the mechanism of the formation of this complex from Zeise's
Dimer. The proposed mechanism is shown in figure 27. The first step is the association of alkyne to the platinum 82
center of Zeise's Dimer with dissociation of the bridging
chlorine to produce trans-(ethylene)(alkyne)dichloro-
platinum(II). This is followed very quickly by displacement
of ethylene by a second alkyne ligand to form a trans-bis-
alkyne complex. Exchange of platinum-bound alkyne for free
alkyne gives cis-bis-alkyne complexes which can cyclize to
the final product. The cyclization proceeds through a
platinacyclopentadiene intermediate, as is the case for
several other transition metals48.
In the hydration of alkynes in THFZH2O solutions
coordinated water must intercept alkynes which stray onto
the metal center, since tetraalkyIcyclobutadiene complexes
are not formed appreciably in those systems. This agrees with other observations which point to a very fast exchange
rate of water on the platinum catalyst in this system.
Platinum-195 NMR chemical shifts indicate that the platinum center in tetrapropylcyclobutadienedichloro- platinum(II) (195Pt NMR 5 -1784.5 ppm) has an electronic
environment which is intermediate between known platinum (IV)
(K2PtCl6 in D2O, 5 0 ppm) and platinum(II) (K2PtCN4, 8-4729.9 ppm; Zeise's Dimer, 5 -2516.5 ppm) complexes. Hence, the cyclobutadiene moiety is stabilized by electron donation
from platinum, presumably through backbonding. This means that the cyclobutadiene has eyelobutadienyl anion character, and has therefore achieved stabilization akin to aromatic 83
stabilization. Electron density in this complex lies mainly
in the cyclobutadiene moiety. Nucleophiles, therefore attack
the platinum center, while electrophiles attack the
cyclobutadiene ring.
Reacting dialkylalkyne with platinum (II) in the
presence of carbon monoxide results in the insertion of CO into the Pt-C G-bonds of the palladacyclopentadiene
intermediate, giving tetrasubstituted cyclopentadienone as a
stable organic product (roughly 20% of the overall
products)49. Obviously, ligand-platinum bond insertion
reactions take place easily. In the proposed mechanism for
platinum (II) catalyzed hydration of alkynes the water ligand
inserts into the metal-carbon bond of the reactive
metallacyclopropene intermediate.
A number of alkyl substituted platinum (II) -
cyclobutadiene complexes were synthesized, which include
several bicyclic and polycyclic systems derived from acyclic
and cyclic diynes (figure 28). For instance, addition of
2,8-Decadiene to Zeise's Dimer in dry chloroform gave
(7,8-dimethyl-bicyclo [4.2.0] -octa-1,6,7,8-T)4-diene) -
dichloroplatinum(II). In agreement with previously described
results, running the same reaction in water saturated
chloroform resulted in the formation of hydration products
as well as the cyclobutadiene product. Several cyclic diynes were tried, including I,7-cyclododecadiyne, which gave 84
(tricyclo [6.4.0.0] dodeca-1,2,7,8-T]4-diene) dichloro- • platinum (II). This could lead to a very easy method to synthesize multiple ring carbocycles containing 4, 5 and 6
diynes in the presence of CO to make five-membered ring- containing polycycles.
(T|4-dimethyldipropy]cyclobutadiene)dichloroplatinuni(II)
7,8-dimethyl-bicyclo[4.2.0]-octa-l16,7,8-Tl4-diene
(tricyclo[6.4.0.0]dodeca-l,2,7,8- T|4-diene)dichloroplatinum(II)
tricyc]o[7.4.0.0]trideca-l,2,8,9-'n4-diene)dichlqroplatinum(n)
Figure 28 Other Cyclobutadiene Complexes 85
Summary
In chapter 2 the elucidation of the mechanism of
hydration of dialkylalkynes was described. The extention of
the method to 1-alkynes was also highlighted, as well as the
platinum (II) catalyzed addition of methanol to 1-alkynes to
make 2,2-dimethoxyalkanes. The ability to add water and
methanol quantitatively to an alkyne using platinum as a
catalyst is a great advance in organoplatinum chemistry. It
has never been done before! Platinum promoted dimerizations
of dialkylalkynes to produce (tetraalkylcyclobutadiene)-
dichloroplatinum(II) complexes were also discussed. All of
these transformations are quantitative when performed as
described.
A kinetic model has been demonstrated for the Zeise1s
Dimer catalyzed hydration of alkynes in water/
tetrahydrofuran solutions. The catalyst system obeys a rate
law based on the Michaelis-Menten enzyme model. From the
results of this kinetic study, related studies at Montana i State University, and from recent literature reports it is
I clear that alkyne hydration occurs on platinum(II), ligand
; reactions play a key role in this transformation and,
; therefore, cis-mechanisms involving ligand insertion steps
^ and metallacyclic intermediates are favored in this study. i,
I 86
CHAPTER 3
PALLADIUM CATALYZED COPE REARRANGEMENT OF 2-METHYL-3-PHENYL-I,5-HEPTADIENE
Since its discovery in 194050, the Cope rearrangement
(figure 29) has been used widely in synthesis51, and the study of the mechanism of this reaction continues to be of major interest. Recent studies on the mechanism of the thermal rearrangement, as well as those of metal catalyzed rearrangements, have continued to fuel controversy in this field.
A
Figure 29 The Cope Rearrangement
Our interest in the Cope rearrangement of substituted
I,5-heptadienes was inspired originally as a system with 87 sufficient complexity to test NMR as a method to investigate complex interacting reactions. Dr. Howald was interested in following a set of four concurrent reactions over time, as this technique would be useful in studying "triple pass" or
"plateau region" chemical kinetics. We chose the palladium catalyzed Cope rearrangement because of the facility of running the reactions at room temperature in common solvents, with the aim of monitoring the reactions by nuclear magnetic resonance spectroscopy.
A substituted diene like E-(JE) 2-methyl-3-phenyl-I, 5- heptadiene can give two different Cope products, ignoring optical activity, which are the Z-(IV) and E-(II) isomers of
2,5-dimethyl-1-phenyl-1,5-hexadiene, in this case. Z- (III)-
2-methyl-3-phenyl-I,5-heptadiene gives the same two products. We originally interpreted the Cope rearrangement of these compounds as a system of four interconverting products. Systems with interconverting transition states are possible, and are probably common. We interpreted the reaction mechanism originally, however, as a set of four separate ordinary transition states (figure 30). On this basis, "diagonal" reactions between JL and III. for instance, were predicted to be very slow. 88
Z-IV Z-III
Figure 30 Products of Palladium(II) Catalyzed Cope Rearrangement of 3-phenyl-2-methyl-I,5-heptadiene
Half way through the study this interpretation was
found to be wrong. To our surprise, the formation of
compound I from compound III was found to be much faster
than either I-4II or III->II reactions! We do not yet fully
understand the complex interactions in this system, but it
appears that when any one of the four compounds complexes
with the catalyst it is possible to pass through a variety
of activated complexes and come out with any of the possible
product species. Thus, in this sense, the palladium(II)
S. 89
catalyzed Cope rearrangement turns out, unexpectedly, to be
an example of "plateau region chemical kinetics.
Palladacycle intermediates have gained precedent in the
literature over the last 30 years and, from what is known
about the thermal Cope rearrangement, a palladabicyclo-
[2.2.1Jheptanoid intermediate is a logical thing to propose
for the transition state in this reaction. What follows is
an account of the research done on this.system so far, with
an emphasis on the transition state structure, and finally,
our effort to graph the reaction topology explicitly. It will be shown that the palladium (II) catalyzed Cope rearrangement proceeds through such a bicyclic intermediate, and that there is a transition plateau for the reaction that can be modeled mathematically.
Background
A.C. Cope and E.M: Hardy discovered that when heated at
150°C for four hours, ethyl(1-methylpropenyl)allyl- cyanoacetate was converted to ethyl(l,2-dimethyl-4- pentenylidene)cyanoacetate.1 Further investigations showed that the reaction was facilitated by electron withdrawing 90 groups substituted at the methylene carbons.52 Cope, Foster and Daniels53, and independently, Aldridge and Murphy54 later described the first order kinetics of the reaction.
The scope of the thermal Cope rearrangement is very broad. This reaction and its closely related cousins, oxy-
Cope and the Claisen rearrangement, have been used widely in organic synthesis55. Prediction of the stereochemical outcome of thermal Cope and Claisen rearrangements of substituted
I,5-hexadienes is based on analysis of the best chair intermediate. The best chair limits I,3-diaxial interactions. For example, the Claisen rearrangement of the compound shown in figure 31 proceeds to form only the trans
(E) product. No cis (Z) product is formed. The reaction proceeding through the chair intermediate with the isopropyl group equatorial is the only observed pathway in this rearrangement.
Although the best chair transition state is a good predictive model for most Cope rearrangements, there are cases in which the chair transition state is not favored.
For instance, cis-divinylcyclopropanes and cis- divinylcyclobutanes undergo facile Cope rearrangement, although the orbital overlap in the four centered transition state is not good56. 91
Figure 31 Stereospecificity in the Claisen Rearrangement
Mechanism of Thermal Cooe Rearrangements
There have been several approaches to elucidation of the mechanism of the thermal Cope rearrangement. An underlying theme has been the biradical nature of the transition intermediate in the reaction, with debate focusing on the geometry of this biradical intermediate. 92
It is generally agreed that the reaction proceeds
through a species with higher symmetry than either reactants
or products. Several possibilities exist for the transition
state in this regard. If breaking of a sigma bond precedes
the formation of the new sigma bond, then the transition
state would be composed of two separated allyI radicals. On
the other hand, formation of a sigma bond first would lead
to a cyclohexane diradical, properly named as cyclohexane-
1,4-diyl in the rearrangement of I,5-hexadiene. A third case
exists, in which the transition state is somewhere in
between the two extremes, and is sometimes referred to as an
"aromatic" transition state.57
von E.. Doering and Roth have proposed the transition
state in Cope rearrangements to be composed of separated
allyl radicals4. Two possibilities exist for the arrangement
of the separated allyl radicals in the transition state. A
chair transition state, comprising a four center
interaction, is thought to predominate58, although a boat
transition state, with a six-center interaction, has also been identified59, and presumably plays a minor role in the
stereochemical outcome of the reaction. 93
six atom overlap four atom overlap
rac-
Figure 32 Six Atom versus Four Atom Overlap
To determine whether a chair or a boat transition state is predominant in the Cope rearrangement, Doering and Roth investigated the thermal rearrangements of meso- and rac- 94
3.4- dimethylhexa-1,5-diene (figure 32). If the boat
transition state is favored, with six overlapping atoms, the
rearrangement of the meso isomer should give trans, trans
ect a- 2 ,6-diene or cis, cis-octa-2,6-diene. The rac-isomer,
in this case, would give cis, trans-octa-2,6-diene.
ContrariIy, if the chair transition state is predominate,
the rac-isomer will rearrange to yield either cis, cis- or
trans, trans-octa-2,6-diene, and the meso-isomer will provide cis, trans-octa-2,6-diene. The meso-isomer was heated to 225°C for 6 hours, partially reacting to yield
99.7% cis, trans-octa-2,6-diene and 0.3% trans, trans-octa-
2,6-diene. The rac-isomer, on the other hand, underwent complete rearrangement in 18 hours at ISO0C to afford a mixture of products-90% trans, trans-octa-2,6-diene, 10% cis, cis-octa-2,6-diene, and under 1% cis, trans-octa-2,6- diene. The authors concluded that the chair transition state is kinetically favored in the thermal Cope rearrangement. By this analysis, the difference in free energy of activation between the lower energy chair and the higher energy boat transition states was calculated to be at least 5.7kcal/mol.
Further, in the case of the rac-isomer of 3,4-dimethyIhexa-
1.5- diene, there are two possible chair transition states, one which leads to trans, trans-, and the other to cis, cis- octa-2,6-diene. The trans, trans-product was found to be 95
favored by a difference in the free energy of activation of
approximately 2.Okcal/mol.
The energy difference between the chair and boat
transition states in the thermal Cope Rearrangement closely
resembles that of the chair and boat conformations of
cyclohexane(5-6kcal/mol). Electronic repulsions between the
two allyI radicals of the Cope transition state in the 6-
centered case were invoked to explain why the boat is disfavored in thermal rearrangements.
Figure 33 Argument Against Separated Allyl Fragments
Allyl fragments of bis-(rp-allyl)-palladium complexes can be coupled by reacting the complexes with excess tripheny!phosphine, yielding hexadienes as the organic products60. However, there is substantial evidence that the
Cope rearrangement does not proceed through separated allyI fragments. Deuterium labeling studies by Sunko and company61 have ruled this possibility out. A crossover experiment was 96
run in which biallyl-1,I,6,6-d4 and biallyl-3,3,4,4-d4 were
submitted together to Cope rearrangement conditions (figure
33). If separated allyI fragments were formed during the
reaction, one would expect to find the crossover product biallyl-1,I,4,4-d4. However, there was no evidence for this
product. Furthermore, the energy of activation for the
homoIytic thermal cleavage of biallyl is much higher (Ba =
46.Skcal/mol) than that for the Cope rearrangement (Ba =
33kcal/mol) 62.
D D
not observed not observed
Figure 34 Support for Minor Boat Transition State in the Thermal Cope Rearrangement 97
Dewar63 , 64 and others have proposed biradicaloid
intermediates for the Cope rearrangement based on the
cyclohexylene diyl model. Goldstein and Benzon65 have
presented evidence for biradicaloid intermediates in the
rearrangements of bicyclo[2.2.0]hexane, which support these
contentions (figure 34). The rearrangement of exo-
tetradeuteriobicyclo[2.2.0]hexane at 135°C gave the inverted
endo isomer without cleavage into I,5-hexadiene. Therefore,
the rearrangement must involve breaking of the transannular
bond of the bicyclohexane to form a biradical intermediate which then inverts and reforms to yield the other isomer. At
a higher temperature (180°C) the reaction also yields the
Cope products ESRZ and ERSZ-tetradeuterio-1,5-hexadiene.
Interestingly, the two products one might first expect from
cleavage of exo-tetradeuteriobicyclo[2.2.0]hexane, ERSE and
ZRSZ-tetradeuterio-1,5-hexadiene, were not observed. Dewar
suggests that the observed products must come from another
intermediate. The biradicaloid derived from fission of the
transannular bond of tetradeuteriobicyclo[2.2.0]hexane must
undergo conformational rearrangement to either of the
possible chair forms prior to formation of the observed Cope
products. This strongly implies that the boat biradical is a
minor transition state in the thermal Cope rearrangement.
Dewar concludes that the chair and boat transition states 98
are lumomers, and that the transition from one to the other
is difficult.
Dewar and company have provided confirmation of the
experimental evidence through MINDO/3 calculations of the
various transition states in these reactions. Their work
covers the nature of the biradicaloid intermediates and
arrives at the calculated energies of the major Cope
transition states for the thermal reaction. Singlet
biradicals cannot exist as stable species66. The transition
state intermediates are biradicaloids which are derived from
the corresponding singlet biradicals through interaction
between the radical centers. This interaction is enough to
remove the HOMO/LUMO degeneracy, but less than that required
to form a new bond67. Through bond and through space
interactions are both present.
Palladium(II) Catalyzed Cope Rearrangements
The first example of a palladium mediated Cope
rearrangement was described by Jonassen and co-workers68 in
1966. They showed that excess cis,trans-1,5-cyclooctadiene reacted with bis(benzonitrile)palladium dichloride at room
temperature to give a palladium dichloride complex of cis-
T12-divinylcyclohexane (figure 35). The scope of this 99
reaction was expanded to a series of substituted cis,trans-
1,5-cyclodecadienes and a trans,trans-1,5-cyclodecadiene by
Sutherland69 and Heimbach70. The products were substituted
divinyIcyclohexanes.
Figure 35 Rearrangement of cis,trans-1,5-cyclooctadiene on Palladium(Ii)
(PhCN)2PdCl2 Ph^ \
4 5
Starting material Cope Selectivity, % substituted
2-methyl 93 E 5-methyl 97 E I,2-dimethyl >90 E E-2,6-dimethyl >90 E E-2,3,6-trimethyl 71 E
Figure 36 Palladium Catalyzed Cope Rearrangements of Substituted 3-phenyl-1,5-dienes 100
The first report of a palladium (II) catalyzed Cope
rearrangement was by Overman and Knoll71 in 1980. The rearrangements of several acyclic 3-phenyl-I,5-dienes was
shown to occur with estimated rate increases of IO10 over the corresponding thermal rearrangements. The reactions are summarized in figure 36. In every case the major product was the E-isomer, as shown.
In a later paper by Overman and Jacobsen72 a study of the mechanism was described which involved the rearrangement of chiral (3R, SE)-2,3-dimethyl-3-phenyl-1,5-heptadiene.
They showed, convincingly, that chirality is transferred completely in this rearrangement, so that the major product from the rearrangement of this starting material is 5R-3,5- dimethyl-2-phenyl-2,6-heptadiene. They assigned the double- bond geometry in this product as the Z-isomer. However, in the earlier study of achiral dienes they assigned the same product as the E-isomer. This ambiguity is very important in the discussion, since the mechanistic conclusions which follow the two opposite assignments are very different.
Overman proposed that the reaction proceeds through a six membered chair carbocation intermediate, with palladium residing equatorially on the opposite side of the chair from the carbon upon which the positive charge resides. Analysis of the two possible chair intermediates for the chiral example follows figure 37. The best chair intermediate, in 101
this case, would lead to (2E,5S)-3,5-dimethyl-2-phenyl-2,6-
heptadiene. The chair intermediate proposed by Overman,
however, would lead to (2Z,SR)-3,5-dimethyl-2-phenyl-2,6-
heptadiene, and this is the result that they report. The
major product was probably misassigned as the Z isomer, as
they did not rigorously characterize this compound. On the
basis of their earlier work, and on the basis of work done
in this study, the correct assignment is the E-isomer. It
will be shown later that the predominant intermediate in the
reaction is not a chair, but rather a boat, with the prow
and stern bridged by palladium.
Figure 37 Analysis of Best Chair for the Rearrangement of (3R, SE)-2,3-dimethyl-3-phenyl-1,5-heptadiene 102 -
Experimental Sect .ion
General
Methyl phenylacetate, copper cyanide, lithium chloride
thionyl chloride, and other reagents were purchased from
Aldrich Chemical company and used as received. Crotyl
chloride (70% trans) was purchased from ICN Biomedicals,
Inc. and used as received. Butyllithium and Methylmagnesium
chloride solutions were purchased from Aldrich Chemical
Company, and were titrated prior to use with sec-butanol using I,10-phenanthrene as indicator. Tetrahydrofuran (EM
Science, Inc.) was distilled from sodium benzophenone ketyl under argon atmosphere prior to use. Dichloromethane and chloroform (Fischer) were distilled from anhydrous calcium chloride prior to use in reactions. Air sensitive reactions were run under argon atmosphere in flame dried flasks, and reagents were transferred with syringes or canula which were
flushed with argon prior to use.
Nuclear magnetic resonance spectra were obtained using
Bruker WM250, AC300, and AM500 spectrometers. Kinetic runs were done on the AM500 spectrometer equipped with a proton- 103
selective probe and a Eurotherm temperature control unit.
Matched 5mm ultraprecision NMR tubes (ICN Biomedicals) were
used for the kinetic runs. Mass spectra were obtained using
a Varian VG 7OE-HF Double Sector, medium resolution mass
spectrometer with sample introduction by capillary gas
chromatography.
Synthesis of Starting Materials
trans-methvl-2-phenvl-4,5-hexenoate
Lithium diisopropylamide was prepared in-situ by
treating freshly distilled diisopropylamine(I.2eq., 11.5ml,
6.93g, 82.2mmol) with butyllithium(I.leg., 42.0ml, 1.80M) in
tetrahydrofuran(450ml) at -78°C under a slight positive pressure of argon gas. The LDA solution was allowed to stir at -78°C for I hour, after which methyl phenylacetate(10.3g,
68.Smmol) in tetrahydrofuran was added to the reaction flask by canula at -78°C. The mixture was stirred for one hour, maintaining temperature below 0°C, in order to assure complete deprotonation of the ester. Crotyl chloride(70% trans, 6.2g, 68.Smmol) in tetrahydrofuran was then added by canula, and the resulting mixture was allowed to warm slowly to room temperature overnight with stirring. The reaction was quenched with saturated ammonium chloride, and the 104
organics were isolated by liquid extraction into pentane.
The pentane extracts were washed twice with water, dried
over anhydrous magnesium sulfate, and concentrated under
vacuum to yield the products. Chromatography on a silica gel
column using 10% ethyl acetate in hexane afforded the pure
product as a mixture of trans (70%) and cis isomers (11.3g,
80.8% yield).
1H N M r (CDCI3) 57.32 (m, 5H, ArH), 5.58-5.46 (m, IH, =CH),
5.40-5.29 (m, IH, =CH), 3.65 (s, 3H, OCH3), 3.59 (t, 1H,
CH), 2.82-2.70 (m, 1H, CH2), 2.51-2.40 (m, 1H, CH2), I;62 (d,
3H, CH3)ppm; 13C NMR (CDCl3) 5 174 (C02CH3), 139 (=CH), 129
(ArH), 128 (ArH), 128.5 (=CH), 127.5 (ArH), 52.0 (OCH3),
37.0 (CH), 30.5 (CH2), 17.9 (CH3 )ppm. Mass spectrum (cis and trans) (m/z) M+ 204 (9), 150 (100), 145 (70), 129 (15), 121
(43) , 118 (50), 91(48), 55 (70) .
trans-2-ohenvl-4.5-hexenoic acid
trans-methyl 2-pheny-4,5-hexenoate(2.6g, 12.7mmol) was dissolved in tetrahydrofuran. Aqueous sodium hydroxide(2g/30ml) was added to the tetrahydrofuran solution, and the mixture was heated to gentle reflux for 14 hours. The mixture was cooled slowly to room temperature, then to 0°C in an ice bath. Sulfuric acid was added dropwise until a pH of 6 was reached. The products were extracted into chloroform, the chloroform extracts washed twice with 105
water, dried over anhydrous magnesium sulfate, and
concentrated under vacuum to yield the carboxylic acid(2.Sg, 12.Immol, 95% yield). 1H N M R (CDCl3) 5 11.75 (br, IH, COOH),
7.35 (s, 5H, ArH), 5.55 (m, 1H, =CH), 5.40 (m, 1H, =CH), 3.62 (t, lH, CH), 2.80 (m, 1H, CH2), 2.49 (m, 1H, CH2), 1.10
(d, 3H, CH3)ppm; 13C NMR 5 180.0 (CO2H), 138.0 (=CH), 129.0
(ArH), 128.1 (ArH), 128.0 (=CH), 127.8 (ArH), 127.0 (C), 52.1 (CH), 36.3 (CH2), 18.0 (CH3) ppm.
trans-2-chenvl-4,5-hexenovl chloride
trans-2-phenyl-4,5-hexenoic acid(2.3g, 12.Immol) was
dissolved in distilled dichloromethane(100ml). Thionyl
chloride(5ml), freshly distilled under argon gas, was added
to the solution, and gentle reflux was initiated while
maintaining a slight positive pressure of argon over the
refluxing apparatus. The solution was allowed to reflux for
3 hours with stirring. The flask was cooled, and the
contents were then evaporated under vacuum to remove the
excess thionyl chloride. The product(2.Og, 79% yield) was
left under high vacuum overnight, and no further
purification was done.
I 106
trans-3-phenvl-5-her)ten-2-onft
Anhydrous copper cyanide (leg., 0.86g, 9.6mmol) and
lithium chloride (2eq., 0.81g, 19.2mmol) were placed under
freshly distilled tetrahydrofuran (400ml) in a 1000ml round
bottom flask which was sealed from the atmosphere
immediately with a rubber septum, and purged with argon gas.
The mixture was stirred until the salts had fully dissolved,
and the flask was then cooled to -5°C in a salt/ice bath.
Methylmagnesium chloride(I.leg., 3.5ml, 3.0M) was added to
the solution, and this mixture was allowed to stir at -5°C
for 30 minutes to form the Knochel reagent. The reaction
flask was then cooled to -30°C. trans-2-PhenyI-4-hexenoyI chloride (2.Og, 9.6mmol) in tetrahydrofuran(3Ornl} was cooled to -30°C, then added to the reaction flask by canula. The greenish solution of Knochel reagent immediately went to a lighter yellow color. The flask was allowed to warm slowly to room temperature overnight, after which the solution had turned a deep orange color. The reaction was quenched with distilled water. The products were isolated by batch extraction of the reaction mixture into pentane. The pentane extracts were pooled, washed with distilled water three times, dried over anhydrous magnesium sulfate, and concentrated-under vacuum to yield a green liquid.
Chromatography on silica gel (20% ethyl acetate in hexane) yielded the product as a colorless liquid (I.6g, 89% yield). 107
1H NMR (CDCl3) 5 7.40-7.18 (m, 5H, ArH), 5.42 (m, lH, =CH),
5.28 (m, IH, =CH), 3.61 (t, lH, CH), 2.74 (m, lH, CH2) , 2.32
(m, lH, CH2), 2.03 (s, 3H, -COCH3), 1.55 (d, 3H, CH3)ppm; 13C
NMR (CDCl3) 5 208.0 (C=O), 138.8 (CH), 128.6 (ArH), 128.0
(ArH), 127.2 (ArH), 1 2 6 . 0 (CH), 60.0 (CH), 33.5 (CH3) , 29.1
(CH2), 18.0 (CH3) ppm. Mass spectrum (trans) (m/z) M+ 188
(19), 145 (100), 134 (24), 130 (19), 117 (36), 105 (23), 97
(57), 91 (50), 43 (37); (cis) (m/z) M+ 188 (14), 145 (100),
134 (20), 130 (18), 117 (36), 105 (25), 97 (62), 91 (63), 43
(62).
trans/cis-2-methvl-3-phenvl-l.5-heptadiene
MethyltriphenylphosphoryI bromide (4.58g, 12.Smmol,
I.5eq) was added to freshly distilled tetrahydrofuran
(450ml) in a clean, flame dried 1000ml RB flask purged with argon. The powder did not completely dissolve. The flask was sealed with a rubber septum, purged again with argon, and cooled to -78°C in a dry ice/acetone bath. n-Buty!lithium
(1.28ml, 10m ) was added dropwise over several minutes to the stirring solution. The solids dissolved, and the solution turned a yellow color. The solution was allowed to warm slowly to O0C with stirring, then cooled to -78°C again. In a separate flask was placed 3-methyl-3-phenyl-5,6-hepten-2- one (I.6g, 8.5mmol), which was dissolved in tetrahydrofuran 108
(10ml). The flask was sealed with a rubber septum, purged
with argon, and cooled to -78°C. The ketone solution was
then transferred all at once to the reaction flask by
canula. The reaction solution was allowed to warm slowly to
room temperature. The reaction was quenched with water, then
batch extracted with pentane. The pentane extracts were
pooled, washed twice with water, dried over anhydrous
magnesium sulfate, and concentrated under vacuum to yield
the crude products. The products were separated by silica
gel chromatography using 10% ethyl acetate/hexane as eluent.
The product diene was isolated pure in this manner (0.93g,
58.7% yield). The remainder of the products were found to be mostly starting material. trans-2-methyl-3-phenyl-1,5- heptadiene 1HNMR (CDCl3) 5 7.3-7.I (ArH, 5H), 5.42 (m, 1H,
=CH) , 5.28 (m, lH, =CH), 4.9 (s, 1H, =CHH), 4.82 (s, 1H, =CHH), 3.2 (t, lH, CH), 2.42 (m, 2H, CH2), 1.55 (d, 3H, CH3),
1.22 (S, 3H, CH3) ppm. 13C N M R (CDCl3) 147.7, 143.4, 129.5,
128.1, 127.9, 126.1, 110.5, 53.1, 36.4, 21.0, 17.9 ppm. Mass spectrum (m/z) M+ 186 (9.94% base), 157 (6.26), 132 (14.67),
131 (100), 116 (17.77), 115 (15.68), 91 (39.29), 77 (5.69),
65 (4.73), 53 (5.90). The minor starting material III is identified by its resolved terminal methylene peaks in the
IH spectrum: d 4.92 (s, 1H, =CHH), 4.85 (s, IH, =CHH) ppm.
Mass spectrum (m/z) M+ 186 (7.15% base), 157 (7.24), 132 109
(9.26), 131 (100), 116 (18.14), 115 (12.19), 91 (37.05), 77
(4.92), 65 (5.28), 53 (5.48).
Thermal Rearrangement of trans-2-methvl-3-phenvl-l.5-
heotadiene
Trans/cis-2-methyl-3-phenyl-1,5-heptadiene (70% trans)
(0.0317g) was placed in a thick walled glass tube with one
sealed end. The tube was evacuated under vacuum (0.Itorr) and the other end was flame sealed. The sealed tube was placed in a muffle furnace and heated to 240°C for 16 hours.
The tube was then cooled to room temperature. The tube was opened by first cooling to -78°C, then breaking the glass at one end of the tube. The contents were dissolved in CDCl3, and a proton spectrum was obtained. This indicated the rearrangement had proceeded approximately 50% to completion.
The major products consisted of E and Z isomers of 2,4- dimethyl-1-phenyl-I,5-hexadiene (E/Z = 1.5).
Molecular Modeling
Relative heats of formation for the four products in the reaction were calculated using Discover software on a HO
Silicon Graphics Personal Iris workstation. The structures
were minimized by MMX calculation and the relative energies
were determined to be, for I, AH01 = 49.83715 kJ/mole, AH011
= 48.58317 kJ/mole, AH0111 = 51.52552 kj/mole, and AH0lv =
48.27707 kJ/mole. The program establishes an arbitrary zero potential energy; the absolute energies of the four products were not found by this calculation, therefore, but the relative energies can be compared since these are all based on the same arbitrary zero. No attempt was made to model the relative energies of the proposed intermediate palladabicyclo[2.2.1]heptanes, since the Discover program was not capable of modeling charged transition metal complexes.
bis-Acetonitriledichlorooalladium(II)
Palladium dichloride(2g) was stirred in acetonitrile
(20ml) for 24 hours at room temperature. The solvent was removed by vacuum evaporation. The yellow solid was recrystallized from chloroform to yield bright yellow crystals (I.Sg, 62% yield). 1H NMR (CDCl3) 8 2.38 (CH3, trans), 2.35 (cis, -10%) ppm; free acetonitrile 8 2.0 ppm. Ill
Palladium Catalyzed Cope Rearrangement of trans-2-methylI-
phenvl-1,5-heptadiene in Tetrahvdrofuran
trans-2-methyl-3-phenyl-1,5-heptadiene (4.93mg,
O .0265mmol) was dissolved in tetrahydrofuran (2ml). Bis-
acetonitriledichloropalladium(II) (l.Omg) was added to the
solution and this was allowed to stir at room temperature
for 24 hours. The solvent was removed by vacuum evaporation and the products were redissolved in CDCl3. 1H NMR of this sample showed Cope rearrangement had occurred. The products were in approximately the same distribution as observed for the reaction in acetone.
Chloroform
Trans-2-methyl-3-phenyl-1,5-heptadiene (4.93mg,
O .0265mmol) was dissolved in chloroform-d. Bis- acetonitriledichloropalladium(II) (l.Omg) was added to the solution. 1H NMR spectra were taken periodically of this sample. Within 24 hours no reaction had taken place. 112
Separation of cis and brans Isomers of 2-msthvl-3-r)hRnvl-
JL,_5rheptadiene and of their Cooe Rearrangement Products., oi s
and trans-2,4-dimethvl-l-phenvl-l.5-hexadiene
Dienes used in this study were separated by preparatory
gas chromatography (Chromasorb column, phase OV-17(10%)),
running the following temperature program. The column was
initially held at 120°C for IOmin after injection, then the
temperature was increased IO0Zmin to a final temperature of
3OO0C. The two isomers of the starting material 2-methyl-3- phenyl-1,5-heptadiene were just separable this way, but were not baseline resolved (E-isomer, RT = 11.75min; Z-isomer, RT
= 12.50min).
The product mixture from the palladium (II) catalyzed
Cope rearrangement of 2-methyl-3-phenyl-1,5-heptadiene contained four products, including the two isomers of 2- methyl-3-phenyl-1,5-heptadiene. The major product, E-2,4- dimethyl-l-phenyl-1,5-hexadiene (RT = 13.19min) was easily isolated from the mixture in this way. However, the minor product, Z-2,4-dimethyl-l-phenyl-l,5-hexadiene (RT =
11.88min) was inseparable from the mixture, having a retention time between that of the two isomers of the starting material. 113
Characterization of Diene TT
The major product from palladium(II) catalyzed Cope
rearrangement of 2-methyl-3-phenyl-l,5-heptadiene was
characterized primarily by nuclear magnetic resonance
spectroscopy. Connectivity assignments were based on a
homonuclear correlation experiment (COSEY) and a
heteronuclear correlation experiment (HETCORR). The geometry
of substituents about the carbon-carbon double bond (C1-C2)
was elucidated by measuring the nuclear overhauser effect
between the proton on Cl and the methylene protons on C 3 . An
NOE of 8% was observed between these protons. However, no
NOE was observed to the methyl group on C2. 1H NMR (CDCl3) 5
7.4-7.15 (m, 5H, ArH), 6.3 (s, 1H, =CHAr), 5.82 (m, 1H, H2C=CHR), (ddd, 2H, =CH2), 2.42 (m, IH, CHCH3), 2.15 (m, 2H,
CH2), 1.83 (S, 3H, =C-CH3), 1.0 (d, 3H, CH3) ppm. 13C NMR
(CDCl3) 5 144.3, 138.6, 137.3, 128.9, 128.0, 126.7, 125.9,
112.4, 48,2, 35.9, 19.5, 17.8 ppm. Mass spectrum (m/z) M+
186 (10.23% base), 171 (1.34), 141 (1.10), 132 (13.79), 131
(100), 130 (3.32), 129 (10.89), 128 (6.22), 127 (2.81), 117
(3.66), 116 (14.63), 115, (16.16), 91 (41.60), 77 (5.33), 65
(5.59) , 53 (7.37), 51 (4.58), 41 (4.04), 39 (6.67).
The minor product IV is identified by several resolved peaks in the 1H NMR spectrum: 8 6.4 (s, IH, =CHAr), 1.9 (s,
3H, =CRCH3) , 0.95 (d, 3H, =CHCH3) ppm. mass spectrum (m/z) M+ 114
186 (7.47% base), 171 (2.61), 132 (2.97), 131 (100), 129
(1.10), 128 (6.57), 127 (3.50), 117 (3.31), 116 (8.52), 115,
(16.04), 91 (34.03), 77 (7.46), 65 (4.59), 53 (7.73), 51
(3.26), 41 (6.09), 39 (5.70).
Kinetics- Monitoring of Reactions bv 1H MMR
For the purpose of collecting kinetic data for the palladium (II) catalyzed Cope rearrangement of the dienes in this study reactions were run in 5mm NMR tubes using d6- acetone as solvent. Proton spectra were collected with a
Bruker AM500 spectrometer operating at 500MHz. Temperature was controlled by a Eurotherm controller module. Data were collected at 298.IK and 308.IK. The collection of data at chosen intervals was automated using the autoprogram in figure 38.
Figure. 38 Autoprogram KINET11. AU
1 ZE
2 GO=2
3 WR #1
4 IF #1
5 Dl
6 IN=I
7 EXIT 115
This program collects data at the interval Dl for a total of
NE experiments using preset acquisition parameters. The
spectra were written to a series file.
The reactions were run in the following way. The starting material diene (5|ll) was delivered to a clean, dry
5mm NMR tube by syringe. The density of 2,4-dimethyl-1- phenyl-1,5-hexadiene was determined to be I .06g/ml prior to
these experiments. Reproducible injections, therefore, delivered a known amount of starting material in each run. d6-Acetone (0.50ml) was then delivered by syringe to make an
NMR sample. In most cases a spectrum of the starting material was obtained prior to addition of the catalyst, and the instrument was tuned and shimmed to this sample. Bis- acetonitriledichloropalladium(ll) (l.Omg) was then added to the NMR sample after the instrument was set up for the experiment. The catalyst was thoroughly mixed with the sample by inverting the sealed NMR tube several times. The homogeneous sample was then placed in the magnet of the spectrometer and data collection was started. In each case the sample was brought to the desired reaction temperature in the magnet prior to addition of catalyst, so that the system was as close to thermal equilibrium as possible at the start of each run. Data were collected over a 20 hour period or longer, in most cases, in order for the system to reach a quasi-equilibrium state. 116
Reactions of Purified Cone Products
Reactions of purified products I, II, and III were carried
out in the same way as above. Compound I. was isolated in
sufficient quantity to do several runs with 5|ll reproducible
injections. Compounds JEI and III were isolated from preparatory GC in collection tubes which were weighed before and after collection. The contents were transferred quantitatively to NMR tubes for the kinetics runs.
Data Handling, Analysis
Workup of the data required automated machine integration of each of the spectra collected during the long kinetic runs. A routine was developed to handle this task.
First, the integrals to be applied to each spectrum were defined in the usual way, by working up one of the spectra and integrating it. An integral file was then written
(typically called INTI, INT2, etc.). An autoprogram was written to fourier transform each FID, apply the integrals to each spectrum obtained, and to write the resulting integrations to an ASCII file. The program is shown in figure 39. 117
Figure 39 Autoprogram FTPKINT.AU
1 RE #1
2 IF #1
3 FT
4 PK
5 WR #2
6 RE #2/INPUT
7 SFN #3/REGION
8 LID #4/OUTPUT
9 IF #4
10 IF #2
11 IN=I
12 EXIT
In a typical run 250 acquisitions gave 250 ASCII files, each containing the integrals for a single acquisition. The
ASCII files were transferred (BRUKNET) to the network and then to floppy disk for storage. In order to assemble the data into one file it was necessary to write a translation program (titled H X .EXE) which reads each ASCII file and converts the columns of integrals into a text string. In this way a single text file containing all of the data for a single kinetics run was assembled. The text file was then imported into a spreadsheet (Quatro) for data analysis. 118
Viability of the Catalyst at Long Reaction Timss
The Cope rearrangement of 3-phenyl-2-methyl-1,5-
heptadiene did not go to completion, based on remaining
starting material. The activity of the catalyst at long
reaction times was tested, therefore, to see whether the reactions were reversible, or if the catalyst had been poisoned somehow. After reaction had gone to equilibrium, additional diene was added to the NMR tube in which the reaction was run. Data collection was continued from this point. The reaction was observed to proceed to equilibrium as before.
Effect of Added Acetonitrile
A sample of trans-2,3-dimethyl-3-phenyl-1,5-heptadiene
(5.Oul, 5.3mg, 0.029mmol), purified by preparatory gas chromatography, was delivered by syringe to a 5mm NMR tube.
Acetonitrile (l.Oul, O.OOlg, 0.019mmol) was then added to the NMR tube. d6-acetone (0.50ml) was then added to make the
NMR sample. Bis-acetonitriledichloropalladium(Il) (0.OOllg,
0.003mmol) was added to the solution and mixed thoroughly immediately prior to the start of the kinetics run. 1H NMR spectra were taken every 60 seconds at 298K, in the usual - 119 waY • % initially reacted to form III. with a rate constant kISobs = 17XlO“3s_1. The reaction of I to II proceeded with a rate constant k^gobs = 14. VXlO-4S-1. This was compared to a prior kinetics run in which no added acetonitrile was employed, in which the rate constant was found to be k12obs=
5.OXlO-5S-1.
Double-bond Isomerization of 3-heptene
The rate of isomerization of cis-3-heptene could not be measured at alkene concentrations in the same range as the concentrations of dienes used in the kinetics runs for the
Cope rearrangement studies. This was because the exchange of alkene ligand on palladium led to broadening of the olefinic proton signals in the 1H NMR spectrum, and the peaks for the cis and trans olefins could not be resolved. A much higher concentration of olefin was used, holding the concentration of palladium constant with respect to the Cope rearrangement runs. Cis-3-heptene (30.0|ll) was delivered to an NMR tube by syringe. Acetone-dg (0.50ml) was added to the NMR tube. A spectrum was acquired for this NMR sample. The catalyst
(I.Omg) was added to the NMR tube and the contents were mixed thoroughly before placing the sample in the magnet of the spectrometer. Data was collected in the same way as 120 before. Data for all of the kinetic runs used in this study is presented in appendix A.
1. OH", H2O, reflux 1. LDA1 THF, -78°C 2. H2SO4, pH=4 2. crotyl chloride 0 3. SOCI2, CH2CI2, -78°C— > O0C Jl reflux______3. NH4CI ^ sOC H 3 4. CH3MgCI. CuCN.2LICI, THF, -78=C
Figure 40 Synthesis of Cope Starting Materials 121
Results
Synthesis of starting materials for the Cope
rearrangement is outlined in figure 40. The starting
materials and the method of synthesis were chosen so as to
be consistent with previous studies73. Trans-crotyl chloride
(ICN Biomedicals, 70% trans, remainder cis) was used,
therefore, to incorporate the trans-double bond into trans
(E)-2-methyl-3-phenyl-1,5-heptadiene (I).
The resulting material contained <30% of the cis (Z) isomer
(III). After addition of the crotyl group, the methyl ester was hydrolyzed to the acid, which was in turn converted to
the acid chloride. The acid chloride was converted
quantitatively to the methyl ketone using the method of
Knochel, et.al74. Wittig olefination of the ketone afforded
the products I. and III in overall good yield.
The palladium(II) catalyzed Cope rearrangement of this
starting material is reversible, and yields four products,
as shown in figure 30. Three of the products were separated
and purified by preparatory gas chromatography. 1H and 13C
NMR spectra for products I, II and III are shown in figures
41, 42, and 43 respectively. Product IV was formed only in
trace amounts, and could not be isolated from the mixture. 122
r 8.0 7.0 6.0 ppm5.0 l!cT
Figure 41 Spectra for Compound I 123
8.0 7.0 ppm5.0 2.0 Figure 42 Spectra for Compound II 124
I aU i
7.0 ppm5.0 4.0 3.0
Figure 43 1H Spectrum of Compound III 125
A mixture of I and III (30% III) underwent Cope
rearrangement in tetrahydrofuran at room temperature for 20 hours, using bis-acetonitriledichloropalladium(II) as
catalyst. The reaction went to -55% completion (based on ratio of II to %) under these conditions. The major product was separated from the mixture by preparatory gas chromatography. 2-D homonuclear (COSEY) and heteronuclear
(HETCORR) NMR studies, as well as careful NOE experiments identify the major product unambiguously as E-2,4-dimethyl-
1-phenyl-l,5-hexadiene (IX). A strong NOE (8%) is observed between the proton on Cl (1H NMR, singlet, 6.23ppm) and the methylene protons of C3 (multiplet, 2.15ppm), whereas, there is no NOE with respect to the methyl at C2 (singlet,
I .83ppm) (figure 44).
CH3
Rh
E-2,4-dimethyl-1 -phenyl-1,5-hexadiene
Figure 44 Nuclear Overhauser Effect in Compound %I 126
The reaction was attempted in chloroform solvent, but
Cope rearrangement did not occur under these conditions.
Only starting material was recovered after 24 hours at room temperature in this system. Acetone was also tried. The results were similar to those with tetrahydrofuran. In general, a good coordinating solvent is necessary for efficient catalysis of the Cope rearangement by palladium (II). In another experiment bis-triphenylphosphine- palladium dichloride was used as the catalyst. No Cope rearrangement was observed with this catalyst, even with tetrahydrofuran. This indicates that the acetonitrile ligands play an important role in the catalytic system.
Thermal rearrangement of the mixture of I and III at
24O0C in a sealed tube gave around 50% yield of the products
II and IV in a ratio of 1.5:1. There was evidence of extensive polymerization of the starting material in the product mixture. The thermal rearrangement of substituted dienes is also known to be complicated by double bond migration reactions75.
Substitution on other I,5-diene substrates was found to limit the reaction. Neither geranyl alcohol or geranyl cyanide underwent Cope rearrangement under the aforementioned conditions, even with heating (figure 45).
This may be due to selective coordination of palladium to 127
the alcohol and cyano functions, respectively, or may be due
to the lack of a phenyl group at C3 of the I,5-diene
skeleton. However, it is more likely that the two methyl
substituents on the terminus of the diene, in these cases,
is responsible for the lack of reactivity. It has been shown
that alkyl or aryl substituents at C2 or C3 of a 1,5-
hexadiene are necessary for the rearrangement to occur.
However, dienes with more than two substituents on either
alkene moiety react sluggishly, at best7677 .
(CH3CN)2PdCl2 ------► no reaction THF, reflux
(CH3CN)2PdCI2 ------► no reaction
Figure 45 Attempted Rearrangement of Geranyl Compounds
It is worth mentioning here that platinum(II) complexes
failed to catalyze the Cope rearrangement of the dienes
examined in this study. Zeise1s Dimer was tried, as well as K2PtCl4 under several reaction conditions. There is one case 128
in the literature, however, o.f a platinum mediated Cope
rearrangement of a cyclic diene. This was done
stoichiometrically, the product being the rearranged diene-
platinum complex78.
Collecting the Data: Preliminary Results
Kinetic data for the Cope rearrangement of the dienes were collected using a Brucker AMSOO 500MHz NMR spectrometer. The reactions were run in d6-acetone in 5mm
NMR tubes at two different temperatures, 298K and 308K, and proton spectra were collected at ~6 minute intervals over
the course of 20-24 hours. A representative integrated
spectrum taken during one of the runs is shown in figure 41.
The numerous spectra collected in each run were phased,
scaled and integrated automatically. At the same time the
integrals were stored to disk in the form of ASCII files.
The files were later translated and dumped to a spreadsheet
for data analysis. A typical graph of integrals of the four products is shown in figure 42 for the rearrangement of the
I + III mixture of starting materials at 298K. Preliminary results from the systematic collection of data on this
system revealed some startling details about the mechanism of the reaction. 129
In general, under conditions of 0.02M palladium catalyst in d6-acetone, the rearrangement of I (containing
30% III) afforded 11 (E-isomer) as the kinetic product, and as the major equilibrium product. The cis and trans isomers of starting material. III and I, seemed to react at approximately equal rates. After 24 hours a quasi equilibrium mixture of product isomers was obtained, with the E-isomer U predominating. After several days, buildup of the other product iy was apparent, but the equilibrium concentration was small. The ratio of I to III remained at its equilibrium value (1:0.5). Figure 46 summarizes some of the reactions that were discussed up to this point.
trans and cis 1.5
(CH3CN)2PdCI2 CHCI3 RT No observable reaction
CH3 (CH3CN)2PdCI2 Rh tetrahydrofuran RT
6.5 trans and cis 55%
Figure 46 Summary of Reactions of the Dienes 130
Reactions of Purified Dienes
When purified II was submitted to the catalyst in d6-
acetone, a fast reaction to form III was observed, with
slower formation of I, and with very much slower buildup of
the product IV. It is evident from this result that I and
H I are intermediates in the rearrangement of JEI to IV.
Similarly, I and III are equilibrated through II. The data
are consistent with a negligible initial rate of formation
of IV. We presumed that formation of IV from JTI required two
independent Cope rearrangements: JEI-XE and I—>IV.
When pure compound III was submitted to the reaction
conditions of d6-acetone and bis-(acetonitrile)palladium
dichloride at 308K in a separate kinetic experiment a very
surprising result was obtained. We expected a negligible
initial rate of formation of I. Compound III rearranged
quickly to form only compound JE over one hour of reaction
time, in a comparatively fast reaction (kobs (298k ) = IO-4).
Figure 47 shows a stacked plot of spectra taken during the
first hour of reaction. The graph in figure 48 shows that
compounds JEJE and IV are not formed appreciably during this
time. After complete equilibration of I and III, compounds
II and, finally, IV started to build up in concentration.
The reaction proceeded to yield the same equilibrium
distribution of products as previous runs over 24 hours. 131
There are two possible explanations for this behavior.
One is that palladium (II) catalyzed a fast double bond
isomerization of the Z isomer III to the E isomer JE prior to
Cope rearrangement. This possibility was ruled out based on a control experiment in which cis-3-heptene was submitted to the same reaction conditions as for the Cope rearrangements.
It was found that isomerization of cis-3-heptene to trans-3- heptene proceeded very slowly (rate constant at high concentration of cis-3-heptene, kobs = IO-5S-1) with respect to the fast reaction between III and %. Furthermore, there were more than two double bond isomers of heptene found in the product mixture on workup, indicating migration of the double bond had occurred to some extent.
Figure 49 shows the gas chromatograph of an equilibrium mixture of products from the palladium (II) catalyzed Cope rearrangement of trans-2-methyl-3-phenyl-1,5-heptadiene.
This shows that only the four Cope rearrangement products were formed in the reaction, if classical palladium catalyzed double bond isomerization were contributing in this system, one would expect to find products of double bond migration as well. Compounds JE and III. then, must equilibrate through the very fast Cope rearrangement of their respective palladium bound forms. It was found later that this equilibration proceeds through palladium bound II, and not through IV. 132
660 min IV,II III,I
60 min
20
10 min
I min
time = 0 min
Figure 47 Stacked Plot for Reaction of III—>1 133
7.00-
6. 00-
5.00-
4.00'
2.00-
Figure 48 Graph of Integrals for the Reaction III—>1 134
BjfflK IH512 ffl-JUL-K 13 37 TBf (EW Sns^GCCfF MrTlC Text=Hism SffLEllB EI TBEV (SC/,S OB-HfK HMML
Figure 49 Chromatograph of Cope Product Mixture 135
Modeling the Palladium(II) Catalyzed Cone Rftarranaftnifint AR a
Set of Concurrent First Order React-, i onr
A full analysis of the kinetic data was done using computers. The reaction was modeled as a set of concurrent first order reactions. A rate constant matrix was assembled from the equilibrium product ratios and initial relative rates of reactions, drawing from several individual kinetic runs. This information could not be obtained from a single run. Following the separate reactions of three purified starting materials in the system was crucial for the accurate estimation of the initial rates of individual reactions.
The 4 X 4 matrix contains all twelve of the discreet rate constants for the forward and reverse reactions between the four products in the system. The twelve values are not all independent. The reactions are all reversible, so equilibtium constants must be determined. The equilibrium constants for the system must fit all of the runs at a particular temperature. There are six equilibrium constants, of which three are independent. This leaves six independent rate constants to solve for at a particular temperature.
It was assumed at first that reactions between I and
III, and between JEI and IV, did not play a role in the system. Overman had stated that double-bond isomerization of 136
the dienes they studied did not occur with the palladium
catalysts used for the Cope rearrangement79. On this basis, the initial rates of reaction for and
were arbitrarily set to zero. This reduces the number
of independent rates to four. If dissociation of the
catalyst-substrate complex is the rate determining step in
the reaction, then the branching ratios for the formation of
products will be independent of starting conditions. Thus, ki2/ki4 = k32/k34. Similar relationships would hold for the
other reactions in the system. This again reduces the number
of independent rates to four. This treatment does fit the
data adequately when the starting material is the
- equilibrium mixture of I and III that was used at first in
this study. However, on closer examination of the system,
the rates of the cross reactions was found to be
significant. It must be mentioned that in previous studies
of the Cope rearrangement of substituted I,5-heptadienes
similar starting materials were used without any attempt to
separate the double-bond isomers, and only the final
products were evaluated.
Diagonalization of the symmetrized rate constant matrix
yields four eigenvalues which are the time constants for the
reaction. One of the time constants is zero. The other three
time constants can be extracted from the data. So, there are
three experimental time constants, and six independent rates 137
fit in the 4 x 4 matrix. Some of the rate constants are
not well determined, or cannot be determined at all, and assignment of a value to these depends on simplifying assumptions. The fast reactions were not observed in the first experiments, where I and III mixture was used as starting material. Separation of individual products, and their separate submission to the reaction conditions, was necessary in order to monitor the fast reactions. The tedious separation procedure yielded small amounts of purified materials, and it was necessary to run some of the reactions at a lower concentration than desired. So, it was assumed that the rates of reactions were not affected substantially by the concentration of substrate over the range of concentrations used. In the end, all of the reactions that were monitored for this purpose gave data that fit the model.
The construction of the matrix relied on relative equilibrium constants for the four products, as well as relative initial rates of formation of products. While the relative equilibrium concentrations were better established, the relative initial rates were not known with the same certainty. The relative initial rates of formation of the products were established by using the results of the reactions of the various purified starting materials, and a X
138
matrix was built. The resulting diagonal matrix was
evaluated against the experimental time constants.
This process is done in an iterative manner until the constants from the diagonal matrix are consistent with the data. This is shown by fitting a calculated line for a particular reaction with the actual experimental data. When the best fit of the data is accomplished, the discreet rate constants can be used to evaluate the nature of the system.
The discreet rate constants cannot be observed experimentally. However, the time constants can be evaluated directly from the data. The fast time constant was taken from the initial rate of reaction of purified starting material III. Likewise, the slower time constants were evaluated by subtracting out the fast time constant from an intermediate portion of the curve. This treatment ensures that the derived rate constant matrix is valid, and that the fit is not merely fortuitous.
Qualitatively, the results of this treatment on runs at both temperatures show that the reactions forming compound
IV are very slow with respect to reactions between I, II, and III. The reaction between I and III is the fastest. This is followed by the reaction between II and III. and between
I and II. It is very difficult to distinguish between the direct formation of JEI from JE from an indirect reaction, where JE-KEJEJE is followed by III—»li. because the JE-KEJEI 139
reaction is very fast. The slowest observed time constant is
made up, principally, from the three reactions forming
compound IV.
Effect of Added Acetonitrile
The palladium catalyzed Cope rearrangement is very fast
compared to dissociation of products from the corresponding palladium-diene complexes. The rate determining step in the
formation of free products, which are the species measured by NMR, is the dissociation of diene from the intermediate palladium-diene complexes. For square planar palladium (II)
complexes ligand substitution occurs through an associative mechanism. That is, an incoming ligand attacks an empty d- orbital on palladium forming a pentacoordinate intermediate prior to dissociation of the leaving group. If dissociation of diene ligand from the palladium (II) complex really is
rate determining, then added acetonitrile ligand should
accelerate the reaction. When a sample of compound I. in
d6-acetone was spiked with a small amount of acetonitrile
(1(11, 70mol% based on I.) , the palladium catalyzed Cope
rearrangement proceeded with a dramatic increase in rate
over that without added ligand. This is explained by the mechanism shown in figure 50. From the derived rate expression, it is evident that increasing the concentration
of acetonitrile increases the rate of reaction. This is true
for all of the diene reactions.
Figure 51 shows the Cope rearrangement cycle, in which
palladium (II)-diene complexes interconvert through four boat
intermediates. It is necessary in going from one boat to the next for the palladium-bound diene to undergo conformational
isomerization. The proposed platinum-diene complex
isomerization steps rely on a ligand substitution mechanism '
in which acetonitrile'ligand displaces one arm of the diene.
This allows free rotation about single bonds leading to the opposite boat conformation. Re-association of the free arm of the diene leads to.the palladium bound diene in its new conformation, which can then rearrange accordingly through the next boat.
K (CH3CN^PdCl2 + dienecomplex + 2 CH3CN
RateA = kA [diene] [free catalyst]
[complex] [CH3CN] 2 [free catalyst][diene]
K [diene] [Pd] o - [free], + [complex] [free] [CH3CN]2
Figure 50 Associative Rate Law 141
i * indicates rapid , i conformational ^ isomerization '
Figure 51 The Palladium(II) Catalyzed Cope Rearrangement Cycle 142
Molecular Modeling Studies
Energy minimization was done for the four Cope products
in the rearrangement of 3-phenyl-1,5-heptadiene. The
calculated heats of formation Of the most stable
conformations of each product are shown in figure 52. It can be seen from this analysis that the product IV should be
thermodynamically favored in this system, followed by II, jr, and lastly III.
49.84 48.58 kJ/mol
E -1_ E-II
48.28 kJ/mol 51.53 kJ/mol
Z-IV Z-III
Figure 52 Relative Stabilities of the Products from Molecular Modeling 143
The relative stabilities of compounds jn, II and m are
confirmed by our data. Compound IV never builds up to an appreciable concentration in the palladium catalyzed system.
We attempted to fit the data assuming that IV was the thermodynamically stable product, although its formation was kinetically limited. However, even allowing extra time at
308K the concentration of IV remained small. We were forced to conclude that the equilibrium constant for its formation is small, in direct contradiction to the energy minima calculations.
Details of Analysis of the Kinetic Data
The palladium (II) catalyzed Cope rearrangement was modeled as a set of concurrent first order reactions between the four observed products. The reason for doing this was to extract thermodynamic activation parameters for all of the twelve discreet reactions between the four products. This goal was met by modeling the reaction at two temperatures.
The reactions are all reversible, so there are twelve discreet rate constants to solve for. From the preliminary results of the study, based on reactions of the JE + m mixture, it was assumed that the rate constants k13, k31, k24 and k42 were all zero. These "diagonal" reactions were not I
taken into consideration initially, because it was not obvious that there would be a direct pathway across diagonals that did not involve classical double-bond isomerization. However, when compounds I, II, and m were isolated and submitted separately to the reaction conditions it was found that these diagonal rate constants were significant. The reactions between I and III, specifically, are the fastest in the system, whereas the reactions between
IJE and IV are the slowest. The highest rate of reaction was observed when compound III was submitted to the catalyst in dg-acetone, monitoring the reaction by NMR. The observed time constant (largest eigenvalue of the rate constant matrix) for this reaction was on the order of 4xl0_4s_1.
From information obtained from the separate reactions of JE, JEI? and III at 298k a table of relative rates of product formation and equilibrium product distributions was assembled. With this information and the value for k31 a rate constant matrix was constructed. Iterative processing of this data led to the rate constant matrix reported here.. The output from this calculation is shown in figure 53, and the fit of the calculated lines to the experimental data for three of the four products in a single kinetic run at this temperature is shown in figures 54, 55, and 56. 145
I 1.24 0.5 0.19 equilibrium constants
I 0.12048 2 0.01506 relative rates
3.6715
-1.96016 0.110586 1.83575 0.013823 transposed rate constant matrix 0.089182 -0.26889 0.178364 0.001343 3.6715 0.442342 -4.16914 0.055293 0.072754 0.008765 0.145507 -0.22703
I 1.113553 0.707107 0.43589 KA5
-1.96016 0.099309 2.596143 0.031713 symmetrized matrix 0.099309 -0.26889 0.280888 0.003431 2.596143 0.280888 -4.16914 0.089697 0.031713 0.003431 0.089697 -0.22703
rate constant matrix vector product eigenvalue -1.96016 0.089182 3.6715 0.072754 I -1.96016 -1.9601588 0.110586 -0.26889 0.442342 0.008765 0 0.110586 ERR 1.83575 0.178364 -4.16914 0.145507 0 1.83575 ERR 0.013823 0.001343 0.055293 -0.22703 0 0.013823 ERR R K.5 matrix -0.58421 -0.58421 -0.58421 -0.58421 -0.58421 -0.04995 -0.27482 -0.04685 2.179755 -0.04995 0.594686 -0.62354 0.513767 -0.4123 0.594686 -0.55005 -0.0287 1.1801 -0.0232 -0.55005
R matrix (this one needs to be typed in) 0.341297 0.423208 0.170648 0.06484649 -0.58421 -0.65055 -0.4131 -0.25465 0.002495 0.017021 0.00117 -0.0206853 -0.04995 -0.30603 -0.03313 0.950133 0.353651 -0.45981 0.152765 -0.0465858 0.594686 -0.69435 0.363288 -0.17972 0.302557 0.019576 -0.32456 0.00242471 -0.55005 -0.03196 0.834457 -0.01011 eigenvectors * rate constant matrix eigenvectors (rows) -2.6E-08 2.24E-07 -2.5E-07 5.0162E-08 -0.58421 -0.72442 -0.2921 -0.111 0.011634 0.079377 0.005456 -0.0964671 -0.04995 -0.34078 -0.02343 0.414153 -0.29719 0.38661 -0.12859 0.03917033 0.594686 -0.77319 0.256883 -0.07834 3.241064 0.209708 -3.47675 0.02597501 -0.55005 -0.03559 0.59005 -0.00441 eigenvalues 4.42E-08 -3.1E-07 8.51E-07 -4.519E-07 -0.23293 -0.23293 -0.2329 -0.2329261 -0.49973 -0.50002 -0.50059 -0.5000245 -5.89229 -5.89227 -5.89229 -5.8924911
Figure 53 Output for Rate Constant Matrix at 298K 146
100000
Figure 54 Fit of Calculated Line to Experimental Line for Compound I 147
100000
Figure 55 Fit of Calculated Line to Experimental Line for Compound II 148
100000
Figure 56 Fit of Calculated Line to Experimental Line for Compound III 149
The equilibrium product distributions and relative
rates define the individual rate constants in the matrix as
constructed originally; but the matrix has to be optimized by an iterative process in order to obtain the closest fit of the data. In general, individual rate constants cannot be directly observed, and the forward and reverse reactions are not equal in rate. The first step in the iterative process is to assume a full set of rate constantsi Then one must diagonalize the symmetrized rate constant matrix. The matrix is symmetrized by multiplying rows by the square roots of the equilibrium constants and dividing the columns by the square roots of the equilibrium constants. The diagonalization is done on a computer using a program written by R . Howald titled MATHX.EXE. The matrix notation for diagonalization of a rate constant matrix A is L A R =
D, where L and R are the left matrix and right matrix, respectively, and D is the resulting diagonal matrix. This yields four lambda values, one of which is zero.
The lambda values are time constants for the reaction system and are linear combinations of the discreet rate constants. X0 = O , since this is the rate constant for the reaction at equilibrium. There are three other lambda constants which rule the reaction to different extents at different times. The time constants increase as X 1 , X 2 and
X 2 . The lambda values are evident in the experimental data. 150 and can be evaluated from the experimental data. In this study the fast time constant X3 was evaluated by observation of the reaction of starting material III. The intermediate time constant was observable in all of the reactions.
This analysis ensured the validity of the rate constant matrix, since the lambda values obtained from diagonalization of these matrices could be compared to the observed rate constants directly. The slower time constant,
A1, is difficult to measure from experimental data, and is barely evident in the reactions studied at these temperatures. It might have been set at zero to simplify the problem. Evaluation of the lambda values in this way allowed the repeated readjustment of the matrices in order to get a better fit.
The rate constants obtained in this way are consistent with the experimental data, since they are derived from that data. However, a proposed set of rate constants must fit the data explicitly. The curve fitting is done by calculating the concentration of a particular species in a run over time from a series expansion which is expressed as follows: concentration = C0O-^ot + C1O-^it +C2O-^ t + C3O-^st, where the lambda values are denoted An (n = 0, I, 2, 3), A0 = 0, and time = t in seconds. The coefficients c are scaling factors that determine the relative contributions of the lambda constants in the formation of a particular product or peak 151
in the NMR spectrum. The matrix of coefficients c is
obtained by dividing the columns of the L matrix by the
square roots of the relative equilibrium constants, then multiplying this matrix by an arbitrary initial concentration vector. The product vector thus obtained is multiplied by the eigenvector matrix from diagonalization to get the matrix of coefficients. Thus, the matrix of coefficients can be changed to reflect different starting conditions.
Each of the products formed in a particular run can be modeled separately and the calculated lines can be compared directly to the actual experimental data. When the calculated lines fit the experimental lines reasonably well, the derived rate constant matrix is assumed to be an accurate representation of the actual rates. The rate constant matrix in figure 50 represents the best fit of data obtained at 298.15K within a narrow concentration range. It was possible to fit this rate constant matrix to several runs at this temperature with different starting conditions.
As already mentioned, back reactions of purified III and I were analyzed separately to get the fast time constant in the reaction at this temperature, but the matrix fits all of the reactions at this temperature. Analysis of the final rate constant matrix at 298K lead to conclusions that are in agreement with the earlier qualitative observations. 152
I 1.4 0.5 0.18 equilibrium constants
I 0.21 2 0.035 relative rates
3.6715
-2.06063 0.192754 1.83575 0.032126 transposed rate constant matrix 0.137681 -0.41786 0.275363 0.004819 3.6715 0.771015 -4.57102 0.128503 0.178476 0.03748 0.356951 -0.57291
I 1.183216 0.707107 0.424264 KA.5
-2.06063 0.162907 2.596143 0.075721 symmetrized matrix 0.162907 -0.41786 0.46077 0.013439 2.596143 0.46077 -4.57102 0.214171 0.075721 0.013439 0.214171 -0.57291
rate constant matrix vector product eigenvalue -2.06063 0.137681 3^6715 0.178476 0 0.137681 ERR 0.192754 -0.41786 0.771015 0.03748 I -0.41786 -0.4178626 1.83575 0.275363 -4.57102 0.356951 0 0.275363 ERR 0.032126 0.004819 0.128503 -0.57291 0 0.004819 ERR R K.5 matrix 0.569803 0.569803 0.569803 0.569803 0.569803 -0.11226 0.38183 -0.09584 -2.07992 0.38183 0.620581 -0.49178 0.477601 -0.94939 -0.49178 -0.52688 -0.04437 1.199181 -0.05886 -0.04437
R matrix (this one needs to be typed in) 0.324675 0.454546 0.162338 0.05844156 0.569803 0.6742 0.402912 0.241747 -0.04286 0.204112 -0.0183 -0.1429519 -0.11226 0.451788 -0.06777 -0.88244 -0.30519 0.338587 -0.11744 0.08404026 0.620581 -0.58188 0.337715 -0.40279 0.023377 0.002756 -0.0266 0.0004701 -0.52688 -0.0525 0.847949 -0.02497 eigenvectors * rate constant matrix eigenvectors (rows) 1.72E-08 -5.2E-09 -1.2B-08 -2.061E-10 0.569803 0.797724 0.284901 0.102565 0.062157 -0.29599 0.026534 0.20730012 -0.11226 0.534562 -0.04792 -0.37439 -0.52732 0.585028 -0.20291 0.14520936 0.620581 -0.68849 0.238801 -0.17089 3.276658 0.386294 -3.72885 0.06589349 -0.52688 -0.06212 0.599591 -0.0106 eigenvalues 3.01E-08 -6.5E-09 -4.1E-08 -2.01E-09 -0.55371 -0.55371 -0.55371 -0.5537069 -0.84972 -0.84972 -0.84972 -0.8497243 -6.21899 -6.21899 -6.21899 -6.2189896
Figure 57 ■ Output for the Rate Constant Matrix at 308K 153
0.25-,
0.05- r
10000 20000 30000 50000 60000 7000040000
10000 20000 30000 40000 50000 60000 70000
Figure 58 Fit of Calculated Lines at 308K 154
0.25-
10000 20000 30000 40000 50000 60000 70000
10000 20000 30000 40000 50000 60000 70000
Figure 58 continued 155
Kinetic Runs at 308K
Runs at 308k were more difficult to fit. This was, in part,
due to the faster initial rates of reaction. An assumption
was made that the relative initial rates of reaction of I
and III were the same at 308K and 298K. This simplified the
problem of building the rate constant matrix for this
temperature. The procedure for constructing the matrix was
the same in all other respects. Equilibrium concentrations
of products and the relative rates were established, and the matrix was assembled from this data. The relative rate values were adjusted in an iterative process until a reasonable fit of each product curve was attained for the runs to be compared to the 298K runs. The output from this procedure is shown in figure 57. Figure 58 shows the fit to experimental data for one of the runs at 308K.
Thermodynamic Activation Parameters
From the solved rate constant matrices for similar runs at two temperatures a matrix of activation energies was calculated using the Arrhenius expression. Calculation of the enthalpy, entropy and free energy of the transition states were then calculated. The transition state enthalpies 156
were calculated using the expression AH* = Ea - R T .
Transition state entropies were calculated using the equation As* = R l n (10)*log{k2/ [(kT/h)*10AH*/RTlnl°] }, which
follows from the definition of activation entropy, k2 = (kT/h) eAs /Re~AH /RT, where k2 is the observed rate
constant divided by the concentration of catalyst, k is the
Boltzmann constant, T is the temperature, h is Planck's
constant, and R is the gas constant. The free energies of
activation were calculated by Ag * = Ah * t A s *. The results
are shown in matrix form in table 2. Figure 59 shows the
energy diagrams for the formation of three products from je.
Matrix Definition by Rate Constants kIl k21 k31 k41 k12 k22 k32 k42 k13 k23 k33 k43
H k24 k34 k44
Arrhenius Activation Energy (kJ/mole)
33.1 0 68.5
4 2 . 4 42.4 111.9
0 33.1 68.5
64.4 97.5 64.4
Table 2 Thermodynamic Activation Parameters 157
Enthalpy of Activation (kJ/mole)
30.6 -2.48 66.0
39.9 ----- 39.9 109.4
-2.48 30.6 ----- 66.0
61.9 95.0 61.9 -----
Entropy of Activation (JK-1Mole-1)
---- -193 -273 -76.0
-160 ------149 52.0
-279 -187 ---- -70.2
-104 -11.9 -92.0 -----
Free Energy of Activation (kJ/mole)
---- -135 -192 -53.3
-112 ------105 36.5
-196 -131 ------49.3
-73.0 -8.35 -64.6 -----
Table 2 (cont.) Thermodynamic Activation Parameters 158
(CH3CN)2Cl2Pd
t
61.9kJ/mole
(CH3CN)2Cl2Pd ------h^ A > Rh IY
Figure 59 Energy Diagrams for Formation of Three Products from Compound I 159
Discussion
The results are consistent with a boat transition state
for this Cope rearrangement, with palladium bridging the
prow and stern of the boat. Thermal Cope rearrangements are
known to proceed through the best chair transition state80
and are kinetically controlled. Both the thermal81 and palladium catalyzed82 rearrangements proceed with almost
complete transfer of chirality.
Figure 60 shows the predicted stereochemical outcome of palladium (II) catalyzed Cope rearrangement of chiral I
(shown for the R optical isomer) through all of the possible
chair and boat transition states. In the case of R-I, the best chair transition state would lead to the S optical
isomer of II., in conflict with the results of previous
studies. The best boat transition state for the reaction of
R-I, on the other hand> would lead to IE.4R-II. which is consistent with our results, as well as with previous studies83. It is impossible to completely dismiss either chair or boat transition states in palladium(ll) catalyzed rearrangement of I without preparing and reacting optically 160
pure chiral I. If either the chair or boat transition states
predominate, chirality would be completely transferred.
However, if both mechanisms are operative, racemization
would take place.
best boat
1Z,4S-H
Figure 60 Predicted Stereochemical Outcome Through the Possible Boat and Chair Transition States 161
The measured activation energies for the palladium (II) catalyzed interconversions of compounds I, Il and III are all low (0-33kJ/mol) in comparison to that of the thermal rearrangement (109.5kJ/mol). A carbocation intermediate of the type proposed by Overman would imply a transition state enthalpy similar to a cyclohexyl cation, which is 782kJ/mol!
Palladium sigma bonded to the carbon 3-disposed from the carbocation would not be expected to provide much stabilization of such a cation. Therefore, the measured activation energies for the reaction are too low to be consistent with this type of chair transition state. The very high negative entropy for the reactions is consistent with a highly ordered bicyclic transition state.
A boat transition state is favored for this reaction based on several arguments with respect to palladabicyclo-
[2.2.I]heptane intermediates. First, palladium(II) is known to form complexes with dienes serving as bi-dentate ligands84. Also, the structure of (I,5-hexadiene)dichloro- palldium(II) has been studied85. X-ray crystallography showed that the diene coordinates in a boat conformation as shown in figure 61. Both of the olefin termini are bonded perpendicularly to the coordination plane of the metal, as is expected. Looking along the C3-C4 axis, the olefinic 162
termini are eclipsing each other. This was confirmed in a
later study of the infrared spectra of this compound86.
Figure 61 Structure of (r|4-l, 5-hexadiene)palladium dichloride
The complex is set up for rearrangement through a boat transition state comprising a palladabicyclo[2.2.1]heptane intermediate. Stable pallada(II) cycloheptanes are known87.
Stable palladabicyclo[2.2.I]heptanes have not been synthesized, however. The intermediacy of metallabicyclo- alkanes has been invoked in other reactions, though, particularly for platinum88'89, and stable platinabicyclo- alkane and alkene complexes have been prepared and characterized90,91. 163
Finally, the intermediacy of I,4-cyclohexylene
biradicaloids in the thermal rearrangement of I,5-hexadiene
has been demonstrated92. Palladium would be expected to bridge a boat biradical in order to stabilize both radical
sites in the intermediate, rather than just one radical (or cationic center) in the case of a chair transition state.
Bridging two carbon centers in the boat would also satisfy the coordination sphere about a palladium(IV) intermediate.
E-II
Palladium(ll)-diene complex + 2 CH3CN
lXj
Z-IV Z-III
Figure 62 Summary 164
Summary
The bis-(acetonitrile)dichloropalladium(II) catalyzed
Cope rearrangement of the reversible system starting with 2- methyl-3-phenyl-1,5-heptadiene was difficult to study. The rates of reaction for the system depend on several factors, including diene concentration, acetonitrile concentration, and temperature. It was very surprising to find that there were fast reactions that could not normally be observed in experiments with the I and III mixture, but were only detected upon cross examining the separate components in the system. The rearrangement of the palladium bound dienes turned out to be much faster than ligand exchange reactions leading to formation of the free products, and could not be measured explicitly.
Even though the system is much more complex than was originally anticipated, it was possible to model it as a set of concurrent first order reactions. From this model several broad conclusions follow. The rate of ligand substitution is slower for the dienes with a phenyl group at the terminus. A large part of the activation energy for reaction of these 165
dienes is due to this. It is striking that reactions between
I and III go through an intermediate palladium bound II,
which liberates free JEI only at a slower rate. The
equilibrium between I and III is closely approached early in
the reaction, while the concentrations of both JEI and IV are
small.
The results of the study strongly point to the
intermediacy of palladabicyclo[2.2.1]heptane intermediates, or a boat transition state for this catalyzed rearrangement.
The activation parameters for this reaction are consistent with this view, as is the stereochemistry of the major product in the reaction. While further study of this system is certainly desirable, the weight of evidence for this conclusion is quite satisfactory.
This system shows complex behavior which would not have been evident if we had relied on a few product analyses for kinetic data. This work clearly shows that automated NMR data collection over 24 hours is a suitable technique to distinguish between competing mechanisms in a system with several possible interconverting products. It would be good to get better data on the fast time constant in this system by collecting data at temperatures below 298K, but we believe that study of a different diene should be attempted first. 166
CHAPTER 4
CONCLUSION
Catalytic reactions of platinum (II) and palladium (II) are related by the fact that both metals share the same features with respect to metal ligand bonding and mechanism of ligand substitution. For both metals in the 2+ oxidation state, ligand substitution proceeds by an associative mechanism. For both the platinum(II) catalyzed hydration of alkynes and the palladium(II) catalyzed Cope rearrangement, ligand substitution is the rate determining step. It has been demonstrated in this study that after the substrates are coordinated to the respective metal, rearrangement of the metal-substrate complex to a metal-product complex is very rapid. These rearrangements proceed through metallacycle intermediates. In the case of platinum(II) catalyzed hydration of alkynes the rearrangement proceeds by activation of both water and alkyne, with a fast ligand insertion step.
Besides making this point, this study has led to several useful products. A good predictive model for both catalytic reactions has been established which will allow 167
their wider use in synthesis. The catalytic reactions of platinum elucidated here are especially exciting because of their potential for commercial use on an industrial scale.
It is hoped that the results of this study will be expanded broadly in the coming years. 168
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62Michl, J. Top. Curr. Chem. 1974, 46, I.
68Trebellas, J. C.; Olechowski, J. R.; Jonassen, H. B . J. Organomet. Chem. 19 66, 6., 412.
69Brown, E . D.; Sam, T . W.; Sutherland, J. K.; Torre, A. J. J. Chem. Soc., Perkin Trans 1975, I, 2326.
70Heimbach, P.; Molin, M. J. Organomet. Chem. 1973, 49, 477.
71Overman, L . E.; Knoll, F . M . J. Am. Chem. Soc. 1980, 102, 865.
72Overman, L . E.; Jacobsen, E . J. J. Am. Chem. Soc. 1982, 104, 7225-7231.
73Gilman, N.W., Ph.D . Thesis, Princteton University, 1967. Also, references 71, and 72. 174
74Knoess, H . P.; Furlong, M. T.; Rozema, M. J.; Knochel, P J. Org. Chem. 1991, 56, 5974-5978.
7^Reference 83.
76Bluthe, N.; Malacria, M.; Gore, J. Tet. Lett. 1983, 24, 1157.
77Overman, L .E .; Knoll, J. Am. Chem. Soc. 1980, 102, 865.
78Trebellas, J.C.; Olechowski, J .R .; Jonassen, H.B. J. Organomet. Chem. 1966, 6, 412.
7^see Overman references.
80Boat transition states have been identified for the thermal rearrangement, but play a minor role. Goldstein, M.J; Benzon, M.S. J. Am. Chem. Soc. 1972, 9 4 . 7147-7151.
81Hill, R .K.; Gilman, N.W. J. Chem. soc. Chem. Commun. 1967, 619.
8^Reference 74.
83Overman, L.E.; Knoll, F.M. J. Am. Chem. Soc. 1980, 102. 8 6 5 -867.
84Atkins, R.M. J.Chem. Soc. Chem. Commun. 1975, 764.
85Zakharova, I.A.; Kukina, G.A.; Kuli-Zade, T.S.; Moiseev, I.I.; Pek, G .Yu .; Porai-Koshits, M.A. Russian Journal of Inorganic Chemistry 1966, 11, 1364-1369.
86Zakharova, I.A.; Leites, L.A.; Aleksanyan, V.T. J. Organomet. Chem. 1974, 72, 283-294.
87Diversi, P.; Ingrosso, G.; Lucherini, A.J. J. Chem. Soc. Chem. Commun. 1978, 735.
88Williams, B .D . Unpublished results.
80Waddington, M.D.; Ph.D. Thesis, Montana State University, 1983, pp. 83-91. 175
90Hoberg, J.O. Ph.D. Thesis, Montana State University, 1990.
91Parsons, E.J.; Jennings, P.W. J. Am. Chem. Soc. 1985, 107, 1793.
92Dewar, M.J.S.; Ford, G.P.; McKee, M.L.; Rzepa, H.S.; Wade, L.E. J. Am. Chem. Soc. 1977, 99., 5069-5073. 176
APPENDIX
Data from Kinetic Runs in Chapter 3 177
Data from Kinetic Runs in Chapter I
For each kinetics run data is presented in the following order: I. Starting material identity and concentration in NMR sample, temperature. 2. Table of integrals corresponding to the integrals on the integrated spectrum. 3. Plots of integrals for the four products in the reaction. 178
Filename: 0829BHH.SER
Starting material: trans/cis-2-methyl-3-phenyl-l,5- heptadiene (30% cis)
Concentration: 0.0427M
Temperature: 298K 179
08298HH.S Integrals DE F G H I J K L 1.842 O 0.002 0.004 0.713 -0.004 0.039 0.167 0.078 0.254 1.88 O 0.002 0.005 0.71 -0.002 0.045 0.163 0.083 0247 1.839 O 0.004 0.005 0.705 -0.003 0.048 0.159 0.085 0242 1.845 0.001 0.004 0.008 0.708 -0.002 0.05 0.156 0.088 0239 1.84 0 0.005 0.011 0.7 -0.002 0.053 0.156 0.089 0234 1.84 0 0.005 0.008 0.694 -0.001 0.053 0.152 0.09 0233 1.837 0 0.005 0.011 0.694 •0.001 0.054 0.152 0.089 023 1.819 0 0.008 0.01 0.684 0 0.055 0.151 0.09 0229 1.845 0 0.008 0.012 0.688 -0.001 0.055 0.149 0.09 0226 1.827 0.001 0.008 0.013 0.683 0 0.054 0.148 0.09 0227 1.832 0 0.009 0.015 0.679 0.001 0.056 0.148 0.09 0227 1.843 0.001 0.011 0.014 0.679 0.002 0.055 0.147 0.091 0226 1.842 0.001 0.011 0.016 0.683 0.001 0.054 0.146 0.089 0225 1.835 0.001 0.012 0.018 0.672 0.001 0.055 0.148 0.09 0223 1.835 0.001 0.013 0.017 0.664 0.002 0.053 0.146 0.089 0224 1.842 0.001 0.014 0.02 0.671 0.003 0.055 0.148 0.089 0224 1.838 0 0.015 0.021 0.669 0.003 0.053 0.146 0.088 0223 1.84 0.001 0.015 0.019 0.665 0.003 0.052 0.146 0.088 0222 1.836 0.002 0.016 0.022 0.657 0.004 0.052 0.145 0.087 0.223 1.835 0.001 0.018 0.021 0.654 0.005 0.051 0.144 0.087 0222 1.837 0.002 0.018 0.023 0.653 0.005 0.052 0.144 0.087 0221 1.846 0.001 0.02 0.023 0.653 0.004 0.052 0.144 0.088 0.22 1.849 0.001 0.019 0.024 0.658 0.005 0.05 0.142 0.088 0221 1.836 0.001 0.021 0.025 0.646 0.007 0.05 0.142 0.085 0219 1.845 0.002 0.023 0.026 0.646 0.007 0.051 0.143 0.088 0216 1.83 0.002 0.022 0.026 0.641 0.007 0.049 0.14 0.084 0218 1.845 0.001 0.024 0.03 0.641 0.007 0.049 0.141 0.086 0218 1.851 0.002 0.024 0.029 0.641 0.008 0.05 0.142 0.085 0217 1.852 0.001 0.026 0.03 0.641 0.008 0.049 0.142 0.083 0214 1.853 0.002 0.027 0.032 0.632 0.008 0.049 0.14 0.084 0215 1.856 0.002 0.027 0.032 0.637 0.008 0.05 0.141 0.085 0216 1.841 0.002 0.027 0.034 0.63 0.009 0.047 0.139 0.083 0214 1.846 0.002 0.029 0.034 0.631 0.009 0.048 0.139 0.083 0215 1.845 0.002 0.029 0.035 0.627 0.009 0.047 0.138 0.081 0214 1.86 0.003 0.031 0.036 0.624 0.011 0.047 0.14 0.083 0212 1.846 0.002 0.032 0.036 0.619 0.01 0.046 0.138 0.082 0212 1.837 0.003 0.032 0.033 0.62 0.011 0.047 0.137 0.082 0213 1.857 0.003 0.033 0.036 0.623 0.011 0.047 0.139 0.081 0.21 1.851 0.003 0.033 0.039 0.616 0.011 0.046 0.137 0.082 0211 1.855 0.003 0.034 0.037 0.616 0.012 0.046 0.137 0.082 0212 1.868 0.003 0.035 0.04 0.62 0.012 0.047 0.136 0.081 0209 1.854 0.003 0.035 0.04 0.612 0.013 0.045 0.136 0.081 0208 1.838 0.003 0.036 0.039 0.604 0.013 0.046 0.136 0.081 0209 1.858 0.004 0.037 0.04 0.605 0.013 0.045 0.137 0.081 0.207 1.849 0.003 0.038 0.041 0.606 0.014 0.044 0.135 0.08 0.208 1.853 0.003 0.039 0.04 0.606 0.014 0.044 0.134 0.079 0.207 1.859 0.003 0.038 0.044 0.605 0.014 0.044 0.135 0.079 0.205 1.849 0.003 0.04 0.045 0.602 0.014 0.044 0.135 0.08 0205 1.848 0.004 0.042 0.046 0.592 0.015 0.044 0.133 0.08 0204 1.85 0.004 0.041 0.048 0.595 0.016 0.043 0.133 0.079 0203 180
1.851 0.003 0.044 0.046 0.593 0.016 0.043 0.132 0.079 0204 1.855 0.003 0.042 0.046 0.59 0.017 0.043 0.132 0.078 0202 1.855 0.003 0.043 0.047 0.588 0.016 0.044 0.133 0.079 0202 1.851 0.003 0.044 0.048 0.587 0.016 0.044 0.132 0.078 0201 1.852 0.004 0.044 0.048 0.585 0.017 0.044 0.133 0.079 0201 1.852 0.003 0.046 0.047 0.583 0.017 0.042 0.13 0.077 0.199 1.849 0.003 0.045 0.049 0.583 0.018 0.042 0.131 0.078 02 1.858 0.004 0.047 0.052 0.58 0.018 0.042 0.131 0.077 0.199 1.851 0.004 0.048 0.051 0.577 0.018 0.041 0.129 0.077 0.199 1.88 0.004 0.048 0.053 0.585 0.018 0.042 0.129 0.076 0.196 1.848 0.004 0.048 0.055 0.572 0.018 0.04 0.127 0.076 0.197 1.88 0.004 0.048 0.052 0.577 0.019 0.04 0.127 0.075 0.196 1.848 0.004 0.049 0.051 0.576 0.019 0.04 0.127 0.074 0.195 1.855 0.004 0.05 0.051 0.572 0.019 0.04 0.126 0.076 0.195 1.859 0.004 0.051 0.053 0.574 0.02 0.041 0.127 0.076 0.195 1.856 0.004 0.05 0.055 0.573 0.019 0.04 0.126 0.075 0.195 1.857 0.005 0.051 0.056 0.567 0.02 0.04 0.126 0.075 0.194 1.848 0.004 0.051 0.055 0.567 0.02 0.04 0.126 0.075 0.193 1.856 0.004 0.052 0.058 0.567 0.02 0.04 0.126 0.075 0.192 1.855 0.004 0.053 0.056 0.567 0.02 0.039 0.124 0.074 0.191 1.852 0.005 0.053 0.057 0.568 0.022 0.039 0.124 0.074 0.192 1.847 0.004 0.054 0.058 0.559 0.02 0.038 0.123 0.073 0.192 1.848 0.004 0.054 0.057 0.562 0.021 0.038 0.123 0.073 0.19 1.843 0.005 0.056 0.057 0.557 0.021 0.038 0.123 0.073 0.19 1.844 0.004 0.056 0.061 0.555 0.021 0.038 0.122 0.074 0.19 1.864 0.004 0.056 0.059 0.555 0.021 0.039 0.123 0.073 0.188 1.865 0.004 0.056 0.058 0.559 0.022 0.039 0.123 0.072 0.187 1.855 0.005 0.057 0.06 0.554 0.022 0.037 0.12 0.071 0.187 1.845 0.005 0.058 . 0.061 0.555 0.022 0.037 0.119 0.072 0.188 1.847 0.005 0.058 0.06 0.547 0.022 0.037 0.12 0.072 0.187 1.851 0.004 0.059 0.063 0.549 0.022 0.037 0.12 0.072 0.186 1.864 0.005 0.057 0.063 0.556 0.024 0.037 0.121 0.072 0.185 1.858 0.005 0.059 0.062 0.552 0.023 0.036 0.119 0.07 0.185 1.859 0.005 0.06 0.063 0.545 0.023 0.037 0.12 0.071 0.183 1.853 0.005 0.06 0.062 0.545 0.024 0.035 0.117 0.07 0.185 1.836 oioos 0.061 0.064 0.538 0.024 0.036 0.119 0.071 0.184 1.854 0.005 0.061 0.067 0.542 0.023 0.035 0.119 0.07 0.183 1.845 0.006 0.061 0.067 0.542 0.024 0.036 0.118 0.071 0.184 1.861 0.005 0.063 0.067 0.546 0.024 0.037 0.119 0.07 0.182 1£68 0.005 0.062 0.066 0.541 0.025 0.036 0.118 0.07 0.182 1.866 0.005 0.063 0.067 0.54 0.025 0.035 0.117 0.069 0.182 1.851 0.006 0.064 0.065 0.536 0.026 0.035 0.116 0.069 0.182 1.852 0.006 0.064 0.068 0.533 0.026 0.035 0.116 0.07 0.182 1.85 0.005 0.064 0.069 0.533 0.026 0.035 0.117 0.071 0.181 1.859 0.005 0.065 0.071 0.536 0.026 0.034 0.116 0.068 0.18 1.862 0.006 0.085 0.071 0.534 0.026 0.035 0.115 0.07 0.181 1.843 0.006 0.066 0.068 0.526 0.026 0.034 0.115 0.068 0.18 1.859 0.006 0.066 0.071 0.53 0.026 0.035 0.115 0.069 0.178 1.861 0.005 0.067 0.07 0.532 0.026 0.034 0.115 0.068 0.18 1.847 0.006 0.066 0.07 0.53 0.027 0.034 0.115 0.067 0.178 1.853 0.006 0.068 0.07 0.527 0.027 0.034 0.114 0.068 0.18 1.87 0.006 0.068 0.073 0.53 0.027 0.035 0.115 0.069 0.178 181
1.846 0.006 0.088 0.07 0.527 0.027 0.035 0.115 0.067 0.177 1.854 0.006 0.089 0.075 0.524 0.028 0.034 0.113 0.068 0.178 1.861 0.006 0.087 0.075 0.52 0.027 0.034 0.113 0.067 0.176 1.849 0.006 0.089 0.073 0.518 0.028 0.033 0.113 0.068 0.177 1.848 0.006 0.089 0.072 0.522 0.028 0.033 0.112 0.068 0.176 1.865 0.006 0.089 0.074 0.531 0.028 0.033 0.113 0.067 0.177 1.856 0.007 0.07 0.074 0.519 0.028 0.033 0.111 0.067 0.175 1.85 0.006 0.069 0.074 0.519 0.028 0.032 0.111 0.066 0.175 1.859 0.006 0.07 0.076 0.517 0.028 0.031 0.11 0.065 0.174 1.856 0.006 0.071 0.076 0.515 0.029 0.031 0.11 0.065 0.173 1.847 0.006 0.072 0.072 0.52 0.029 0.031 0.109 0.066 0.175 1.85 0.006 0.072 0.077 0.515 0.029 0.031 0.109 0.067 0.174 1.854 0.006 0.072 0.078 0.518 0.029 0.031 0.108 0.065 0.173 1.857 0.006 0.071 0.075 0.516 0.029 0.032 0.11 0.066 0.172 1.849 0.006 0.071 0.075 0.515 0.029 0.032 0.109 0.066 0.172 1.856 0.005 0.073 0.078 0.512 0.029 0.033 0.109 0.066 0.172 1.855 0.006 0.073 0.076 0.514 0.029 0.032 0.109 0.066 0.17 1.852 0.006 0.073 0.078 0.514 0.03 0.032 0.109 0.065 0.17 1.848 0.007 0.074 0.076 0.512 0.029 0.03 0.106 0.064 0.172 1.861 0.006 0.073 0.077 0.511 0.029 0.031 0.108 0.064 0.17 1.859 0.006 0.074 0.08 0.504 0.029 0.03 0.108 0.065 0.17 1.863 0.006 0.074 0.08 0.507 0.03 0.032 0.109 0.064 0.167 1.858 0.006 0.075 0.08 0.502 0.03 0.03 0.108 0.064 0.169 1.866 0.007 0.075 0.079 0.51 0.03 0.03 0.107 0.063 0.168 1.838 0.006 0.076 0.08 0.501 0.03 0.03 0.108 0.064 0.169 1.873 0.007 0.076 0.084 0.509 0.031 0.03 0.105 0.064 0.169 1.88 0.006 0.076 0.084 0.506 0.031 0.03 0.105 0.064 0.169 1.872 0.006 0.076 0.085 0.505 0.031 0.03 0.108 0.063 0.168 1.872 0.006 0.077 0.081 0.508 0.031 0.03 0.108 0.064 0.169 1.863 0.007 0.078 0.082 0.5 0.032 0.031 0.107 0.063 0.167 1.86 0.006 0.078 0.081 0.5 0.032 0.029 0.105 0.063 0.167 1.857 0.006 0.078 0.083 0.498 0.032 0.03 0.108 0.064 0.168 1.864 0.007 0.078 0.084 0.501 0.032 0.031 0.107 0.064 0.167 1.857 0.007 0.079 0.083 0.499 0.032 0.029 0.105 0.063 0.168 1.862 0.007 0.079 0.082 0.495 0.032 0.029 0.104 0.063 0.167 1.859 0.007 0.08 0.083 0.494 0.033 0.028 0.104 0.063 0.167 1.86 0.006 0.08 0.084 0.497 0.033 0.029 0.105 0.062 0.167 1.866 0.007 0.081 0.085 0.493 0.033 0.029 0.105 0.063 0.167 1.86 0.007 0.081 0.084 0.491 0.033 0.03 0.106 0.062 0.166 1.856 0.007 0.081 0.084 0.489 0.034 0.028 0.104 0.062 0.167 1.857 0.007 0.082 0.087 0.495 0.034 0.028 0.105 0.062 0.167 1.856 0.007 0.083 0.084 0.491 0.034 0.029 0.104 0.063 0.168 1.862 0.007 0.082 0.085 0.491 0.035 0.028 0.105 0.063 0.167 1.875 0.007 0.083 0.084 0.492 0.034 0.028 0.105 0.061 0.166 1.869 0.007 0.082 0.087 0.494 0.035 0.03 0.105 0.063 0.166 1.857 0.008 0.083 0.087 0.489 0.034 0.028 0.105 0.061 0.166 1.864 0.007 0.084 0.087 0.488 0.035 0.027 0.103 0.06 0.167 182
M N O P Q R S T Iimo(S) 0.352 0.791 0.491 0 0.005 2.113 0.005 0 0 0.351 0.788 0.496 0.001 0.006 2.101 0.007 0 357 0.346 0.788 0.501 0 0.007 2.077 0.011 0 714 0.347 0.781 0.507 0.001 0.009 2.065 0.012 0 1071 0.344 0.778 0.513 0.001 0.011 2.065 0.016 0 1428 0.344 0.78 0.516 0.002 0.012 2.058 0.017 0.001 1785 0.339 0.775 0.525 0.002 0.014 2.04 0.02 0 2142 0.336 0.767 0.534 0.003 0:016 2.029 0.022 0.001 2499 0.339 0.778 0.544 0.003 0.017 2.038 0.025 0.001 2856 0.337 0.769 0.551 0.003 0.019 2.019 0.028 0.001 3213 0.338 0.768 .0.564 0.003 0.021 2.013 0.031 0.001 3570 0.336 0.771 0.573 0.003 0.023 2.022 0.034 0.002 3927 0.334 0.768 0.578 0.004 0.024 2.002 0.036 0.002 4284 0.333 0.763 0.591 0.004 0.026 2 0.04 0.003 4641 0.331 0.765 0.594 0.004 0.029 1.988 0.042 0.002 4998 0.331 0.764 0.605 0.005 0.03 1.989 0.046 0.002 5355 0.328 0.764 0.612 0.005 0.033 1.981 0:048 0.002 5712 0.327 0.764 0.613 0.005 0.035 1.975 0.051 0.002 6089 0.324 0.755 0.62 0.005 0.037 1.957 0.054 0.003 6426 0.325 0.755 0.626 0.005 0.039 1.971 0.057 0.003 6783 0.325 0.753 0.627 0.006 0.04 1.949 0.08 0.003 7140 0.324 0.755 0.632 0.007 0.042 1.959 0.063 0.003 7497 0.323 0.758 0.629 0.007 0.045 1.955 0.065 0.003 7854 0.318 0.748 0.632 0.008 .0.048 1.941 0.07 0.003 8211 0.323 0.748 0.638 0.008 0.049 1.95 0.072 0.004 8568 0.317 0.75 0.634 0.008 0.051 1.921 0.075 0.004 8925 0.317 0.753 0.636 0.008 0.052 1.936 0.078 0.004 9282 0.318 0.751 0.64 0.009 0.055 1.936 0.081 0.004 9639 0.317 0.752 ■ 0.635 0.009 0.055 1.913 0.083 0.005 9996 0.315 0.753 0.638 0.009 0.059 1.925 0.087 0.005 10353 0.317 0.754 0.644 0.009 0.061 1.935 0.089 0.005 10710 0.313 0.744 0.64 0.01 0.082 1.904 0.092 0.004 11067 0.315 0.744 0.64 0.01 0.084 1.899 0.095 0.005 11424 0.309 0.736 0.642 0.01 0.086 1.887 0.097 0.005 11761 0.311 0.742 0.645 0.01 0.088 1.909 0.101 0.005 12138 0.309 0.734 0.645 0.011 0.071 1.893 0.103 0.006 12495 0.31 0.732 0.647 0.011 0.072 1.887 0.108 0.006 12852 0.312 0.739 0.648 0.011 0.074 1.886 0.109 0.006 13209 0.307 0.737 0.651 0.011 0.076 1.891 0.111 0.006 13566 0.308 0.739 0.65 0.012 0.077 1.894 0.114 0.006 13923 0.306 0.735 0.65 0.012 0.08 1.877 0.116 0.007 14280 0.305 0.729 0.65 0.012 0.081 1.879 0.119 0.007 14637 0.303 0.728 0.651 0.012 0.082 1.859 0.122 0.006 14994 0.301 0.726 0.653 0.012 0.084 1.869 0.124 0.006 15351 0.303 0.73 0.654 0.012 0.086 1.869 0.128 0.006 15708 0299 0.724 0.649 0.013 0.088 1.848 0.13 0.007 16065 0299 0.73 0.649 0.013 0.09 1.858 0.132 0.007 16422 0297 0.718 0.656 0.013 0.092 1.851 0.134 0.008 16779 0297 0.72 0.657 0.013 0.093 1.834 0.136 0.007 17136 0297 0.718 0.654 0.014 0.094 1.843 0.138 0.007 17493 183
0597 0.723 0.655 0.014 0.096 1.832 0.141 0.008 17850 0595 0.717 0.657 0.014 0.097 1.824 0.142 0.007 18207 0598 0.72 0.658 0.014 0.098 1.825 0.144 0.006 18564 0593 0.715 0:659 0.014 0.1 1.811 0.146 0.008 18921 0592 0.718 0.658 0.015 0.101 1.813 0.149 0.008 19278 0591 0.716 0.656 0,015 0.103 1.802 0.151 0.008 19835 0591 0.714 0.659 0.015 0.104 1.808 0.151 0.008 19992 0593 0.716 0.66 0.015 0.105 1.798 0.155 0.008 20349 059 0.717 0.659 0.016 0.106 1.789 0.157 0.009 20708 0589 0.715 0.659 0.015 0.108 1.772 0.159 0.007 21063 0588 0.707 0.66 0.016 0.109 1.77 0.16 0.008 21420 0587 0.71 0.658 0.017 0.11 1.773 0.163 0.009 21777 0586 0.704 0.661 0.016 0.112 1.756 0.164 0.009 22134 0585 0.708 0.659 0.017 0.113 1.764 0.165 0.01 22491 0587 0.702 0.662 0.017 0.114 1.761 0.167 0.009 22848 0586 0.709 0.664 0.017 0.114 1.745 0.169 0.01 23205 0584 0.707 0.663 0.017 0.116 1.743 0.171 0.01 23562 0582 0.703 0.664 0.017 0.118 1.728 0.172 0.009 23919 0584 0.703 0.664 0.017 0.118 1.737 0.175 0.009 24276 0583 0.703 0.663 0.018 0.12 1.73 0:176 0.01 24633 0582 0.708 0.665 0.018 0.122 1.728 0.179 0.01 24990 0577 0.701 0.666 0.018 0.122 1.711 0.18 0.01 25347 0581 0.698 0.669 0.018 0.123 1.715 0.182 0.011 25704 0578 0.699 0.671 0.018 0.124 1.708 0.184 0.01 26061 0578 0.703 0.67 0.018 0.126 1.713 0.187 0.01 26418 0577 0.698 0.671 0.019 0.127 1.711 0.187 0.01 26775 058 0.703 0.672 0.019 0.128 1.702 0.188 0.011 27132 0574 0.698 0.668 0.019 0.129 1.687 0.19 0.011 27489 0575 0.69 0.669 0.02 0.13 1.688 0.192 0.011 27846 0573 0.689 0.668 0.019 0.131 1.685 0.193 0.011 28203 0574 0.693 0.673 0.019 0.132 1.678 0.194 0.011 28560 0574 0.693 0.674 0.02 0.133 1.684 0.197 0.011 28917 0571 0.695 0.673 0.019 0.134 1.665 0.198 0.011 29274 0572 0.69 0.675 0.02 0.135 1.669 0201 0.011 29831 0569 0.685 0.674 0.02 0.136 1.663 0201 0.01 29988 0569 0.688 0.676 0.02 0.137 1.657 0205 0.012 30345 0569 0.688 0.673 0.02 0.138 1.652 0205 0.011 30702 057 0.686 0.68 0.021 0.139 1.657 0208 0.012 31059 0569 0.689 0.679 0.021 0.141 1.65 0208 0.011 31416 057 0.685 0.681 0.021 0.143 1.659 021 0.012 31773 057 0.692 0.677 0.021 0.143 1.653 0211 0.012 32130 0563 0.685 0.682 0.021 0.143 1.641 0212 0.011 32487 0566 0.686 0.681 0.021 0.145 1.643 0215 0.013 32844 0567 0.681 0.684 0.021 0.145 1.639 0215 0.013 33201 0568 0.683 0.678 0.021 0.148 1.638 0218 0.012 33558 0567 0.683 0.685 0.022 0.148 1.64 0217 0.013 33915 0563 0.676 0.683 0.021 0.149 1.624 022 0.013 34272 0565 0.686 0.688 0.022 0.15 1.627 0221 0.013 34629 0565 0.677 0.683 0.022. 0.152 1.627 0223 0.012 34986 0562 0.674 0.683 0.022 0.152 1.616 0224 0.012 35343 0564 0.68 0.686 0.022 0.153 1.618 0226 0.013 35700 0567 0.685 0.688 0.023 0.154 1.624 0228 0.014 36057 184
0.262 0.678 0.69 0.022 0.154 1.604 0228 0.013 36414 0565 0.677 0.691 0.023 0.156 1.618 023 0.013 36771 0561 0.675 0.688 0.023 0.155 1.603 0231 0.014 37128 0559 0.674 0.692 0.023 0.156 1.6 0231 0.014 37485 0559 0.67 0.691 0.023 0.157 1.587 0233 0.013 37842 0561 0.676 0.697 0.024 0.157 1.598 0233 0.014 38199 0563 0.676 0.693 0.024 0.158 1.59 0235 0.014 38556 0559 0.671 0.691 0.023 0.158 1:574 0235 0.013 38913 0559 0.674 0.692 0.024 0.16 1.578 0237 0.014 39270 0556 0.666 0.692 0.024 0.16 1.568 0238 0.014 39827 0558 0.671 0.693 0.024 0.16 1.566 0239 0.014 39984 0558 0.667 0.697 0.024 0.161 1.57 0241 0.015 40341 0557 0.671 0.697 0.024 0.162 1.558 024 0.014 40898 0556 0.669 0.698 0.024 0.162 1559 0241 0.014 41055 0555 0.664 0.699 0.024 0.162 1.547 0243 0.014 41412 0554 0.671 0.703 0.025 0.162 1.55 0245 0.014 41769 0554 0.669 0.702 0.025 0.163 1.542 0245 0.014 42126 0554 0.668 0.7 0.024 0.163 1.534 0245 0.014 42483 0549 0.667 0.698 0.025 0.164 1.53 0245 0.014 42840 0552 0.67 0.701 0.026 0.165 1.536 0247 0.015 43197 0553 0.664 0.704 0.026 0.165 1.528 0247 0.014 43554 0552 0.667 0.701 0.025 0.167 1.525 0251 0.015 43911 0549 0.661 0.704 0.025 0.167 1.526 025 0.015 44268 0552 0.671 0.7 0.025 0.168 1.523 0251 0.015 44625 055 0.658 0.708 0.026 0.168 1.517 0252 0.015 44982 0552 0.665 0.707 0.026 0.17 1.537 0254 0.016 45339 0551 0.666 0.708 0.027 0.171 1.528 0255 0.016 45698 0552 0.665 0.708 0.026 0.172 1.523 0256 0.015 46053 0552 0.669 0.71 0.026 0.174 1.53 0259 0.015 46410 055 0.665 0.711 0.026 0.174 1.517 026 0.015 46767 0548 0.663 0.71 0.027 0.175 1.52 026 0.016 47124 0549 0.659 0.709 0.026 0.176 1.518 0262 0.015 47481 055 0.662 0.717 0.026 0.176 1.52 0262 0.017 47838 0549 0.662 0.712 0.027 0.179 1.517 0265 0.015 48195 0549 0.656 0.716 0.027 0.179 1.52 0265 0.017 48552 0548 0.658 0.711 0.026 0.18 1.519 0267 0.016 48909 0548 0.661 0.712 0.027 0.182 1.517 0269 0.016 49066 0547 0.663 0.715 0.027 0.183 1.521 0272 0.016 49623 0547 0.661 0.713 0.026 0.185 1.514 0274 0.015 49980 0548 0.659 0.713 0.027 0.186 1.517 0277 0.017 50337 0547 0.661 0.717 0.027 0.186 1.518 0275 0.016 50694 0546 0.655 0.724 0.027 0.187 1.528 0277 0.016 51051 0546 0.659 0.723 0.027 0.19 1.525 0282 0.016 51408 0547 0.659 0.719 0.027 0.19 1.519 028 0.016 51765 0545 0.659 0.724 0.027 0.192 1.52 0284 0.017 52122 0545 0.659 0.722 0.027 0.193 1.508 0286 0.015 52479 0543 0.659 0.719 0.028 0.194 1.506 0286 0.016 52836 185
10000 20000 30000 40000 50000 60000 70000 186
Filename: 02I6BHM.SER
Starting material: trans-2-methyl-3-phenyl-I,5-heptadiene
Concentration: 0.057OM
Temperature: 298K 187
0216BHM.SER Integrals B CD E F G 1923 0.008 0.042 0.163 0.088 2.6 19.349 0.016 0.07 0243 0.198 2.338 19.424 0.012 0.09 0262 0236 2231 19.47 0.023 0.107 0.313 0254 2.158 19.426 0.019 0.12 0.314 026 2.108 19.386 0.021 0.141 0.327 0259 2.084 19.354 0.025 0.153 0.348 0259 2.055 19.309 0.021 0.162 0.361 025 2.012 19252 0.025 0.178 0.388 0248 1.978 19.196 0.024 0.196 0.397 0249 1.977 19246 0.028 0203 0.399 0244 1.953 19286 0.025 0219 0.433 0238 1.936 19288 0.033 0233 0.439 0237 1.927 19.153 0.029 0241 0.468 0234 1.905 19244 0.032 0258 0.476 0227 1.874 1926 0.034 0271 0.511 0229 1.879 19.135 0.038 0284 0.528 0222 1.857 19.192 0.032 0299 0.519 022 1.848 19267 0.039 0.313 0.554 0214 1.83 19.185 0.035 0.32 0.581 0214 1.801 19.181 0.045 0.335 0.561 0209 1.786 19.084 0.039 0.346 0.58 0208 1.777 19.143 0.041 0.353 0.609 02 1.741 19.167 0.041 0.37 0.622 0.193 1.735 19.108 0.042 0.377 0.645 0.192 1.721 19.037 0.041 0.383 0.636 0.191 1.697 19.092 0.046 0.404 0.646 0.19 1.695 19.056 0.043 0.408 0.669 0.183 1.678 19.042 0.046 0.416 0.685 0.178 1.653 19.051 0.05 0.431 0.717 Oj 81 1.661 18.995 0.05 0.441 0.701 0.177 1.645 19.044 0.05 0.45 0.73 0.172 1.625 18.951 0.052 0.466 0.75 0.174 1.628 18.975 0.056 0.473 0.73 0.171 1.613 18.95 0.054 0.487 0.757 0.167 1.605 18.903 0.057 0.5 0.786 0.172 1.601 18.879 0.053 0.502 0.766 0.165 1.583 18.909 0.058 0.516 0.794 0.161 1.578 18.972 0.059 0.532 0.791 0.162 1.576 18.866 0.054 0.54 0.822 0.16 1.566 18.881 0.059 0.552 0.831 0.162 1.556 18.863 0.067 0.565 0.843 0.159 1.565 18.919 0.062 0.576 0.853 0.153 1.548 18.805 0.064 0.585 0.853 0.156 1.545 18.854 0.061 0.602 0.856 0.158 1.55 18.896 0.067 0.614 0.875 0.153 1.531 18.741 0.068 0.614 0.892 0.157 1.528 18.898 0.071 0.628 0.871 0.149 1.519 18.803 0.071 0.64 0.892 0.153 1.526 18.774 0.074 0.653 0.922 0.156 1.516 188
18.882 0.074 0.656 0.924 0.151 1.508 18.605 0.076 0.673 0.941 0.152 1.507 18.772 0.076 0.68 0.907 0.149 1504 18.819 0.079 0.686 0.951 0.149 1.497 18.843 0.073 0.694 0.958 0.143 1.483 18.768 0.075 0.711 0.983 0.149 1.498 18.836 0.079 0.725 0.959 0.15 1.491 18.609 0.079 0.732 0.989 0.148 1.481 18.778 0.079 0.734 0.986 0.145 1.472 18.826 0.084 0.745 0.977 0.146 1.479 18.729 0.082 0.754 1.004 0.148 1.471 18.751 0.082 0.767 1.025 0.144 1.462 18.782 0.086 0.762 1.012 0.143 1.445 18.843 0.086 0.776 1.026 0.144 1.453 18.846 0.086 0.789 1.03 0.14 1.451 18.78 0.084 0.797 1.043 0.145 1.446 18.794 0.085 0.799 1.057 0.142 1.437 18.712 0.087 0.802 1.048 0.142 1.431 18.76 0.087 0.822 1.064 0.142 1.436 18.809 0.09 0.826 1.07 0.141 1.43 18.771 0.091 0.83 1.073 0.138 1.419 18.741 0.093 0.836 1.08 0.136 1.417 18.748 0.093 0.851 1.085 0.142 1.421 18.782 0.086 0.857 1.077 0.138 1.414 18.665 0.093 0.859 1.105 0.144 1.417 18.816 0.095 0.883 1.107 0.143 1.406 18.809 0.095 0.875 1.129 0.141 1.408 18.71 0.095 0.891 1.1 0.141 1.404 18.711 0.095 0.888 1.123 0.139 1.391 18.824 0.1 0.898 1.111 0.137 1.387 18.748 0.099 0.901 1.129 0.133 1.384 18.758 0.097 0.916 1.135 0.133 1.385 18.622 0.096 0.918 1.142 0.138 1.38 18.734 0.1 0.921 1.155 0.136 1.377 18.701 0.103 0.921 1.153 0.138 1.367 18.802 0.102 0.932 1.159 0.134 1.366 18.68 0.099 0.946 1.153 0.134 1.371 18.678 0.104 0.949 1.155 0.133 1.359 18.676 0.106 0.951 1.165 0.132 1.355 18.696 0.105 0.954 1.175 0.136 1.35 18.716 0.104 0.964 1.168 0.131 1.344 18.739 0.103 0.974 1.186 0.13 1.346 18.711 0.105 0.979 12 0.133 1.344 18.733 0.103 0.984 1209 0.132 1.34 18.742 0.104 0.982 1203 0.13 1.333 18.709 0.106 0.987 1211 0.13 1.33 18.655 0.106 1.004 1219 0.133 1.335 18.704 0.112 1.01 1207 0.133 1.332 18.674 0.107 1.018 1218 0.13 1.328 18.67 0.109 1.017 1214 0.13 1.318 18.754 0.107 1.012 122 0.13 1.318 18.625 0.109 1.022 1239 0.131 1.313 189
18.618 0.112 1.031 1244 0.132 1.319 18.665 0.113 1.038 1258 0.132 1.317 18.61 0.113 1.042 1258 0.132 1.309 18.709 0.112 1.044 1239 0.125 1.303 18.646 0.114 1.045 1256 0.128 1.301 18.673 0.116 1.047 1256 0.126 1296 18.743 0.115 1.055 1247 0.126 1291 18.559 0.119 1.069 1254 0.13 1297 18.666 0.114 1.086 1271 0.132 1294 18.682 0.119 1.073 1263 0.129 129 18.647 0.112 1.075 1281 0.129 1285 18.646 0.12 1.079 1266 0.125 1281 18.688 0.117 1.082 127 0.125 128 18.702 0.12 1.081 1295 0.123 1271 18.638 0.116 1.086 1.303 0.123 1269 18.628 0.12 1.088 1.303 0.124 1267 18.669 0.115 1.09 1.302 0.126 1264 18.585 0.116 1.091 1.308 0.127 1263 18.623 0.119 1.094 1.321 0.123 1257 18.666 0.116 1.098 1297 0.122 1251 18.615 0.12 1.094 1.313 0.125 1251 18.624 0.122 1.103 1.326 0.121 1248 18.564 0.122 1.121 1.304 0.125 1255 18.658 0.122 1.13 1.304 0.123 1252 18.607 0.125 1.134 1.32 0.127 1252 18.639 0.127 1.133 1.335 0.124 1247 18.663 0.122 1.14 1.316 0.122 1241 18.689 0.121 1.138 1.33 0.122 124 18.746 0.127 1.138 1.326 0.122 1238 18.651 0.122 1.14 1.322 0.122 1232 18.688 0.124 1.14 1.347 0.121 1232 18.673 0.123 1.145 1.33 0.121 1227 18.647 0.122 1.147 1.354 0.117 1226 18.704 0.125 1.15 1.353 0.119 122 18.616 0.128 1.154 1.363 0.119 122 18.743 0.128 1.154 1.348 0.118 1221 18.654 0.129 1.16 1.346 0.117 1216 18.63 0.127 1.164 1.364 0.117 121 18.64 0.125 1.165 1.371 0.12 1213 18.691 0.128 1.168 1.368 0.112 1203 18.614 0.127 1.177 1.359 0.12 1211 18.659 0.128 1.172 1.355 0.116 1208 18.662 0.132 1.176 1.382 0.114 1.199 18.576 0.128 1.182 1.386 0.117 1204 18.655 0.129 1.184 1.377 0.114 1202 18.611 0.131 1.183 1.394 0.123 1202 18.603 0.129 1.191 1.386 0.118 1.198 18.673 0.13 1.189 1.373 0.114 1.191 18.56 0.131 1.197 1.373 0.121 1.19 18.624 0.129 1.197 1.375 0.118 1.191 18.619 0.131 1203 1.402 0.115 1.19 18.663 0.13 1209 1.391 0.116 1.19 190
18.637 0.134 1.214 1.388 0.114 1.185 18.612 0.129 1.21 1.394 0.119 1.188 18.612 0.132 ISIS 1.381 0.116 1.183 18.656 0.133 1221 1.399 0.117 1.182 18.619 0.133 1221 1.398 0.117 1.183 18.608 0.135 1226 1.409 0.117 1.181 18.631 0.132 1232 1.411 0.115 1.175 18.623 0.138 1231 1.403 0.12 1.18 18.691 0.137 1239 1.429 0.117 1.174 18.642 0.135 1245 1.418 0.116 1.177 18.657 0.135 1247 1.414 0.115 1.176 18.644 0.131 1255 1.426 0.116 1.175 18.642 0.139 1256 1.416 0.113 1.17 18.576 0.139 1263 1.409 0.119 1.171 18.645 0.135 1263 1.429 0.116 1.173 18.722 0.138 1266 1.417 0.115 1.168 18.769 0.135 1271 1.431 0.113 1.168 18.7 0.137 1275 1.414 0.115 1.16 18.651 0.138 1275 1.424 0.115 1.165 18.742 0.137 1.28 1.434 0.112 1.158 18.571 0.145 1283 1.44 0.115 1.162 18.665 0.143 1284 1.448 0.113 1.16 18.67 0.139 1287 1.453 0.117 1.159 18.648 0.142 1293 1.467 0.113 1.16 18.703 0.135 1297 1.442 0.113 1.157 18.625 0.139 1294 1.465 0.117 1.158 18.589 0.142 1.302 1.46 0.117 1.158 18.668 0.142 1.303 1.456 0.119 1.158 18.69 0.145 1.31 1.472 0.111 1.151 18.611 0.143 1.313 1.461 0.116 1.157 18.637 0.142 1.314 1.45 0.115 1.148 18.581 0.141 1.317 1.469 0.115 1.149 18.728 0.146 1.322 1.459 0.114 1.152 18.653 0.147 1.328 1.458 0.116 1.152 18.657 0.141 1.323 .1.461 0.113 1.147 18.717 0.146 1.331 1.457 0.114 1.146 18.663 0.146 1.335 1.471 0.113 1.145 18.594 0.145 1.338 1.491 0.117 1.144 18.664 0.143 1.339 1.479 0:119 1.15 18.688 0.148 1.342 1.473 0.119 1.145 18.627 0.152 1.342 1.482 0.115 1.144 18.635 0.146 1.349 1.478 0.117 1.147 18.762 0.147 1.348 1.47 0.111 1.139 18.68 0.15 1.351 1.486 0.117 1.141 18.666 0.144 1.354 1.509 0.115 1.14 18.754 0.145 1.348 1.496 0.113 1.138 18.648 0.147 1.349 1.523 0.118 1.136 18.691 0.145 1.35 1.486 0.113 1.133 18.659 0.146 1.343 1.495 0.114 1.127 18.678 0.147 1.349 1.51 0.11 1.118 18.716 0.145 1.339 1.5 0.109 1.117 18.693 0.144 1.338 1.475 0.108 1.112 19.1
18.654 0.146 1.333 1.505 0.11 1.111 18.661 0.153 1.338 1.502 0.109 1.111 18.644 0.148 1.348 1.491 0.111 1.113 18.628 0.148 1.347 1.506 0.109 1.109 18.707 0.143 1.349 1.508 0.109 1.108 18.68 0.147 1.344 1.502 0.109 1.104 18.652 0.147 1.336 1.485 0.109 1.103 18.566 0.147 1.323 1.499 0.105 1.101 18.565 0.146 1.33 1.507 0.102 1.099 18.65 0.147 1.332 1.502 0.108 1.1 18.617 0.148 1.319 1.508 0.102 1.095 18.666 0.145 1.308 1.511 0.1 1.087 18.617 0.145 1.307 1.507 0.097 1.08 18.559 0.143 1.311 1.531 0.102 1.08 .18.581 0.144 1.323 1.507 0.101 1.083 18.61 0.149 1.326 1.508 0.1 1.083 18.59 0.149 1.322 1.53 0.1 1.088 18.506 0.145 1.32 1.502 0.097 1.079 18.572 0.143 1.338 1.51 0.103 1.088 18.547 0.147 1.333 1.506 0.104 1.084 18.564 0.145 1.329 1.518 0.1 1.08 18.544 0.146 1.323 1.535 0.098 1.077 18.61 0.147 1.321 1.524 0.099 1.074 18.524 0.145 1.33 1.502 0.097 1.071 18.529 0.147 1.329 1.519 0.098 1.069 18.523 0.144 1.313 1.507 0.092 1.059 18.504 0.141 1.317 1.524 0.094 1.065 18.476 0.147 1.316 1.53 0.096 1.06 18.51 0.146 1.304 1.52 0.091 1.046 18.468 0.145 1.303 1.528 0.089 1.051 18.418 0.145 1.304 1.53 0.092 1.047 18.438 0.141 1292 1.513 0.088 1.034 18.426 0.14 1286 1.539 0.091 1.035 18.449 0.139 1285 1.528 0.089 1.036 18.404 0.141 1275 1.502 0.083 1.02 18.399 0.144 1279 1.516 0.084 1.02 18.404 0.145 . 1279 1.514 0.085 1.015 18.316 0.141 1263 1.511 0.084 1.01 18.341 0.143 1267 1.537 0.088 1.009 18.307 0.145 1261 1.508 0.081 0.998 18265 0.145 1252 1.515 0.08 0.994 18.322 0.142 1259 1.506 0.08 0.997 18279 0.144 1245 1.517 0.08 0.989 18245 0.142 1239 1.518 0.077 0.984 18254 0.143 1.24 1.534 0.078 0.982 18219 0.141 1224 1.524 0.075 0.972 18.344 0.138 1227 1.539 0.072 0.967 18.348 0.141 1227 1.516 0.075 0.968 18.317 0.138 1217 1.527 0.077 0.965 18295 0.139 1224 1.558 0.075 0.969 18216 0.137 1224 1.52 0.074 0.964 18294 0.135 1215 1.528 0.072 0.954 192
18.303 0.136 1225 1.523 0.073 0.964 18.305 0.139 1215 1.532 0.07 0.957 18279 0.139 1214 1.547 0.071 0.955 18293 0.134 1217 1.519 0.07 0.951 18.187 0.139 12 1.537 0.07 0.944 18215 0.13 1206 1.526 0.068 0.945 18294 0.139 1204 1.513 0.069 0.946 18288 0.137 1.196 1.541 0.067 0.941 18293 0.138 1208 1.515 0.068 0.942 18.182 0.14 1208 1.522 0.073 0.944 18211 0.139 1206 1.529 0.069 0.941 18235 0.139 . 122 1.535 0.071 0.948 18.162 0.14 1214 1.546 0.071 0.943 18221 0.136 1209 1.538 0:069 0.94 18.119 0.141 1.22 1.546 0.073 0.94 18.146 0.142 1205 1.545 0.069 0.935 18.153 0.139 121 1.538 0.069 0.937 18.189 0.137 1221 1.555 0.07 0.939 17.575 0.041 0.573 1.461 -0.002 0.383 18.071 0.071 0.723 1.541 0.034 0.5 18211 0.141 1.332 1.569 0.143 1.031 18.198 0.152 1.42 1.566 0.149 1.072 193
H I J K L time (s ) 3.432 0.008 0.08 0.101 0.031 0 3.419 0.024 0.166 0.155 0.04 357 3.418 0.039 0236 0203 0.044 714 3.399 0.042 0287 0235 0.047 1071 3.375 0.043 0.326 027 0.046 1428 3.352 0.047 0.369 0.302 0.054 1785 3.332 0.048 0.409 0.338 0.06 2142 3.323 0.051 0.438 0.369 0.061 2499 3291 0.048 0.468 0.395 0.059 2856 3281 0.054 0.511 0.427 0.068 3213 3249 0.054 0.548 0.463 0.069 3570 3223 0.059 0.583 0.494 0.07 3927 3215 0.08 0.627 0.529 0.073 4284 3.191 0.062 0.66 0.561 0.061 4641 3.156 0.065 0.694 0.588 0.079 4998 3.141 0.071 0.74 0.63 0.084 5355 3.107 0.071 0.776 0.656 0.086 5712 3.094 0.068 0.805 0.692 0.088 6089 3.062 0.07 0.841 0.72 0.088 6426 3.04 0.072 0.877 0.747 0.092 6783 3.024 0.072 0.915 0.779 0.091 7140 2.997 0.084 0.953 0.805 0.102 7497 2.98 0.071 0.975 0.83 0.108 7854 2.985 0.076 1.008 0.863 0.102 8211 2.945 0.086 1.048 0.889 0.108 8568 2.924 0.08 1.072 0.913 0.105 8925 2.912 0.085 1.111 0.944 0.112 9282 2.882 0.078 1.136 0.972 0.116 9639 2.858 0.085 1.169 0.993 0.116 9996 2.854 0.089 1209 1.034 0.124 10353 2.823 0.089 1236 1.058 0.127 10710 2.822 0.091 1263 1.078 0.125 11067 2.81 0.097 1.308 1.11 0.119 11424 2.789 0.097 1.332 1.133 0.13 11781 2.757 0.103 1.363 1.162 0.128 12138 2.762 0.111 1.406 1.194 0.13 12495 2.731 0.1 1.416 1206 0.142 12852 2.727 0.104 1.452 1237 0.139 13209 2.711 0.112 1.487 1265 0.143 13566 2.688 0.108 1.508 1285 0.151 13923 2.673 0.12 1.542 1.316 0.148 14280 2.682 0.118 1.581 1.351 0.152 14637 2.661 0.12 1.604 1.372 0.152 14994 2.64 0.126 1.63 1.393 0.158 15351 2.638 0.136 1.671 1.427 0.165 15708 2.613 0.135 1.692 1.446 0.165 16065 2.606 0.143 1.724 1.465 0.163 16422 2.594 0.134 1.741 1.485 0.173 16779 2.583 0.145 1.789 1.513 0.173 17136 2.581 0.147 1.812 1.538 0.173 17493 194
2.575 0.149 1.827 1.551 0.177 17850 2.565 0.156 1.87 1.591 0.179 18207 2.56 0.154 1.894 1.611 0.182 18564 2.532 0.159 1.916 1.627 0.185 18921 2.529 0.156 1.929 1.643 0.187 19278 2.523 0.168 1.981 1.68 0.186 19635 2.529 0.174 2.013 1.706 0.19 19992 2.506 0.177 2.028 1.718 0.193 20349 2.488 0.166 2.039 1.733 0.193 20706 2.492 0.173 2.08 1.761 0.196 21063 2.489 0.186 2.11 1.778 0501 21420 2.469 0.178 2.113 1.796 0506 21777 2.46 0.186 2.125 1.804 0502 22134 2.456 0.197 2.167 1.826 0508 22491 2.452 0.198 2.197 1.849 0514 22848 2.427 0205 222 1.869 0511 23205 2.424 0208 2229 1.879 0509 23562 2.433 0205 2247 1.892 0507 23919 2.416 0209 2291 1.928 0514 24276 2.401 0218 2.312 1.94 0516 24633 2.393 0213 2.319 1.96 0522 24980 2.377 0214 2.329 1.963 0519 25347 2.39 0225 2.374 1.994 0524 25704 2.367 0228 2.39 2.009 0526 26061 2.367 0238 2.418 2.027 0528 26418 2.356 0229 2.414 2.024 0539 26775 2.358 0232 2.451 2.055 0534 27132 2.344 0233 2.475 2.084 0534 27489 2.334 0238 2.491 2.078 0532 27846 2.328 0242 2.491 2.098 054 28203 2.322 024 2.506 2.109 0537 28560 2.321 025 2.544 2.142 0542 28917 2.322 0251 2.563 2.148 0548 29274 2.32 0248 2.562 2.162 0547 29831 2.301 0261 2.581 2.165 0539 29988 2292 0263 2.602 2.179 0545 30345 2291 0266 2.631 2514 0545 30702 2282 0273 2.648 2514 0546 31059 2279 0262 2.653 2527 0545 31416 2265 0277 2.662 2532 0.251 31773 2269 027 2.673 2549 0552 32130 2254 0291 2.716 2577 0555 32487 2247 0297 2.73 2581 0553 32844 225 0281 2.728 2589 0558 33201 2233 0294 2.744 2594 0559 33558 2229 0287 2.744 2.3 0554 33915 2232 0.303 2.791 2.341 . 0558 34272 2223 0.31 2.807 2.352 0559 34629 2223 0.303 2.82 2.368 0561 34986 2212 0.321 2.832 2.368 0559 35343 2212 0.309 2.819 2.366 0566 35700 2219 0.308 2.839 2.39 0565 36057 195
2.21 0.32 2.88 2.413 0271 36414 2.184 0.324 2.899 2.425 0267 36771 2.191 0.329 2.899 2.432 0269 37128 2.185 0.33 2.902 2.436 0268 37485 2.18 0.321 2.907 2.446 0265 37842 2.177 0.314 2.897 2.448 0274 38199 2.161 0.343 2.934 2.459 0268 38556 2.182 0:347 2.988 . 2.496 027 38913 2.162 0.366 2.99 2.49 0272 39270 2.164 0.345 2.988 2.504 0275 39827 2.151 0.357 3.003 2.507 . 0275 39984 2.143 0.334 2.985 2.527 028 40341 2.145 0.34 3.001 2.535 0283 40698 2.147 0.34 2.997 2.529 0278 41055 2.141 0.336 2.999 2.544 0284 41412 2.146 0.325 3 2.551 0288 41769 2.132 0.334 3.009 2.547 0279 42126 2.123 0.349 3.029 2.564 0279 42483 2.117 0.341 3.027 2.565 0287 42840 2.122 0.342 3.03 2.568 0282 43197 2.126 0.366 3.065 2.582 0285 43554 2.123 0.335 3.057 2.598 0279 43911 2.111 0.36 3.095 2.628 0288 44268 2.108 0.377 3.125 2.646 0293 44625 2.115 0.394 3.154 2.651 0291 44982 2.095 0.38 3.14 2.653 0293 45339 2.099 0.387 3.146 2.669 0291 45698 2.112 0.374 3.139 2.669 0288 46053 2.101 0.376 3.144 2.672 0294 46410 2.096 0.365 3.141 2.675 0287 46767 2.092 0.348 3.134 2.685 0.3 47124 2.086 0.361 3.149 2.69 0291 47481 2.085 0.367 3.152 2.694 0294 47838 2.081 0.364 3.159 2.704 0295 48195 2.08 0.367 3.168 2.713 0293 48552 2.076 0.373 3.173 2.727 0295 48909 2.068 0.365 3.186 2.735 0299 49266 2.07 0.367 3.187 2.743 0295 49623 2.065 0.358 3.191 2.745 0297 49980 2.064 0.353 3.182 2.752 0.303 50337 2.051 0.391 3226 2.76 0.303 50694 2.052 0.383 3224 2.771 0.308 51051 2.06 0.373 322 2.772 0.303 51408 2.048 0.374 3233 2.785 0.302 51765 2.04 0.376 3234 2.792 0.304 52122 2.042 0.383 3254 2.791 0.302 52479 2.039 0.379 3255 2.815 0.308 52836 2.039 0.39 3.27 2.81 0.304 53193 2.022 0.397 3282 2.818 0.307 53550 2.031 0.397 3282 2.826 0.305 53907 2.024 0.386 3282 2.846 0.314 54264 2.02 0.387 3292 2.856 0.311 54621 196
2.023 0.391 3.301 2.862 0.308 54978 2.011 0.409 3.318 2.86 0.308 55335 2.011 0.397 3.317 2.876 0.314 55692 2.005 0.411 3.334 2.877 0.313 56049 2.01 0.412 3.347 2.887 0.312 56408 2.011 0.416 3.358 2.884 0.315 56763 2.016 0.415 3.357 2.902 0.307 57120 2.015 0.436 3.389 2.913 0.314 57477 1.968 0.445 3.392 2.921 0.311 57834 1.996 0.43 3.398 2.937 0.317 58191 1.998 0.447 3.415 2.948 0.32 58548 1.989 0.456 3.428 2.955 0.319 58905 2 0.444 3.425 2.963 0.314 59262 2.004 0.463 3.45 2.971 0218 59619 1.983 0.453 3.448 2.982 0.318 59976 1.989 0.461 3.457 2.982 0.318 60333 1.977 0.469 3.464 2.998 0.328 60690 1.989 0.46 3.475 2.998 0.324 61047 1.985 0.467 3.478 3.006 0.329 61404 1.966 0.471 3.484 3.011 0.321 61761 1.999 0.473 3.501 3.034 0.319 62118 1.972 0.479 3.503 3.04 0.326 62475 1.984 0.487 3.519 3.044 0.327 62832 1.972 0.488 3.529 3.047 0.327 63189 1.952 0.492 3.526 3.056 0.336 63546 1.965 0.519 3.56 3.059 0.331 63903 1.961 0.508 3.557 3.07 0.331 64260 1.97 0.494 3.552 3.083 0.332 64617 1.952 0.51 3.566 3.087 0.331 64974 1.95 0.497 3.564 3.098 0.334 65331 1.664 0.519 3.586 3.1 0.327 65688 1.989 0.518 3.593 3.112 0.336 66045 1.948 0.525 3.6 3.121 0.34 66402 1.946 0.531 3.616 3.132 0.339 66759 1.954 0.531 3.621 3.126 0.336 67116 1.94 0.53 3.62 3.133 0.332 67473 1.945 0.531 3.627 3.142 0.337 67830 1.937 0.551 3.65 3.154 0.337 68187 1.933 0.555 3.654 3.149 0.345 68544 1.939 0.557 3.669 3.17 0.345 68901 1.944 0.547 3.67 3.176 0.331 69258 1.932 0.553 3.669 3.179 0.345 69815 1.923 0.562 3.67 3.182 0.34 69972 1.942 0.56 3.687 3.188 0.341 70329 1.922 0.561 3.684 3.202 0.348 70686 1.923 0.569 3.689 3205 0.341 71043 1.911 0.566 3.695 3.194 0.346 71400 1.918 0.547 3.677 3.19 0.335 71757 1.926 0.541 3.671 3.194 0.339 72114 1.919 0.534 3.653 3.195 0.342 72471 1.91 0.498 3.62 3.183 0.343 72828 1.909 0.489 3.609 3.173 0.34 73185 197
1.904 0.498 3.625 3.176 0.336 73542 1.91 0.47 3.606 3.181 0.346 73899 1.914 0.498 3.635 3204 0.343 74256 1.908 0.523 3.656 3208 0.338 74613 1.905 0.484 3.625 3212 0.35 74970 1.897 0:491 3.629 3.195 0.339 75327 1.885 0.481 3.622 3.179 0.339 75684 1.881 0.454 3.577 3.159 0.339 76041 1.89 0.445 3.578 3.173 0.338 76398 1.884 0.442 3.581 3.184 0.335 76755 1.886 0.407 3.53 3.153 0.344 77112 1.898 0.41 3.509 3.124 0.348 77469 1.883 0.409 3.485 3.116 0.342 77826 1.879 0.415 3.523 3.133 0.343 78183 1.879 0.418 3.534 3.157 0.337 78540 1.872 0.423 3.542 3.156 0.339 78897 1.881 0.421 3.537 3.155 0.341 79254 1.869 0.419 3.527 3.158 0.343 79811 1.859 0.436 3.58 3.198 0.346 79988 1.865 0.448 3.584 3203 0.34 80325 1.864 0.431 3.562 3.178 0.34 80682 1.856 0.42 3.533 3.171 0.347 81039 1.861 0.423 3.53 3.168 0.344 81398 1.852 0.425 3.563 3.197 0.338 81753 1,853 0.417 3.529 3.17 0.343 82110 1.85 0.408 3.484 3.153 0.351 82467 1.839 0.429 3.507 3.153 0.348 82824 1.843 0.41 3.503 3.164 0.348 83181 1.847 0.415 3.461 3.133 0.35 83538 1.833 0.408 3.449 3.135 0.353 83895 1.825 0.403 3.451 3.139 0.354 84252 1.826 0.386 3.404 3.11 0.349 84609 1.825 0.403 3.412 3.109 0.356 84966 1.826 0.388 3.405 3.113 0.354 85323 1.81 0.401 3.378 3.088 0.364 85680 1.81 0.402 3.394 3.1 0.363 88037 1.809 0.409 3.393 3.094 0.355 86394 1.809 0.397 3.372 3.083 0.355 88751 1.824 0.408 3.384 3.09 0.358 87108 1.808 0.394 3.363 3.08 0.359 87465 1.817 0.382 3.354 3.073 0.363 87822 1.797 0.397 3.364 3.087 0.361 88179 1.798 0.38 3.348 3.071 0.365 88536 1.793 0.365 3.338 3.059 0.357 88893 1.801 0.382 3.354 3.067 0.361 89250 1.783 0.36 3.32 3.041 0.355 89607 1.787 0.357 3.316 3.037 0.358 89964 1.79 0.35 3.318 3.045 0.359 90321 1.78 0.35 3.307 3.025 0.359 90678 1.789 0.344 3.316 3.051 0.362 91035 1.781 0.339 3.305 3.045 0.358 91392 1.774 0.334 3298 3.032 0.354 91749 198
1.774 0.36 3.317 3.046 0.358 92106 1.768 0.326 3289 3.032 0.354 92463 1.768 0.325 3288 3.033 0.351 92820 1.762 0.334 3294 3.038 0.357 93177 1.764 0.321 3271 3.004 0.346 93534 1.777 0.307 3273 3.025 0.343 93891 1.767 0.327 3287 3.024 0.344 94248 1.759 0.321 3264 3.002 0.345 94605 1.758 0.319 3284 3.036 0.346 94982 1.766 0.334 3298 3.033 0.351 95319 1.764 0.318 3279 3.029 0.35 95676 1.753 0.334 3.308 3.047 0.359 96033 1.749 0.339 3.3 3.04 0.349 98390 1.745 0.316 328 3.032 0.356 98747 1.758 0.317 3299 3.06 0.354 97104 1.755 0.324 3293 3.027 0.348 97461 1.754 0.32 3294 3.037 0.348 97818 1.751 0.336 3.323 3.065 0.351 98175 1.514 0.489 1.712 1.535 0.083 98532 1.578 0.504 2.054 2.023 0.147 98889 1.72 0.745 3.886 3.484 0.367 99246 1.728 0.752 4.067 3.726 0.385 99803 3
[] 199
O 100000 200
Filename: 020SBHL.SER
Starting material: trang-2-methyl-3-phenyl-1,5-heptadiene
with added acetonitrile (lml, I .9X1O-Smol).
Concentration: 0.0570M
Temperature: 29SK 201
O208BHLSER Integrals BCD E F G H I 229.954 ■0267 -0.017 2.718 81.83 227 26.856 40.025 229.345 -0294 0.083 2.61 81.524 2.436 26.665 39.955 230.398 -0.323 0.087 2.675 81.641 2.632 26.549 39.914 230.59 -0267 0205 2.853 81.583 2.718 26.327 39.942 230512 -0.127 0.527 3.01 81228 2.887 26267 39.958 231.147 -0.133 0.457 3.11 81.196 2.989 26.142 39.903 230.473 -0219 0.357 3.363 812 3.062 26.131 39.876 23021 -0.134 0.617 3229 81.16 3.171 26.008 39.726 230.86 -0.065 0.682 3.057 80.052 3216 25.924 39.86 231.073 -0.164 0.538 3258 80.941 3252 25.797 39.82 231275 -0.038 0.823 3.413 80.737 3279 25.734 39.61 231.446 -026 0.735 3.535 80.639 3.391 25.725 39.767 230.74 -0.081 0.887 3217 80.62 3.339 25.615 39.594 231.463 -0.153 0.801 3.345 79.933 3.481 25.612 39.512 231.447 -0.057 0.878 3.483 80.089 3.456 25.537 39.617 230.975 0.01 1.042 3.541 80217 3.545 25.482 39.572 231.682 0.003 1.086 3.682 80.017 3.498 25.371 39519 231.798 -0.053 1.162 3.637 80.117 3.591 25.434 39.414 231.541 -0.094 0.99 3.811 79.577 3.523 25288 39.308 231.155 -0.154 1.105 3.619 79.682 3.547 25288 39256 231.225 -0.08 1.036 3.802 79.511 3.606 25261 39.327 231.707 -0.116 1.148 3.905 79.323 3.59 25207 39222 231.435 0.104 1.336 4.041 79.449 3.553 25.121 39243 231.457 0.054 1.198 3.965 79.315 3.615 25.133 39.163 231.894 -0.012 1.419 3.932 78.986 3.641 25.008 39.101 231.748 -0.058 1.426 4.183 78.775 3.676 25.027 38.911 232.085 -0.019 1.468 3.944 78.871 3.601 24.988 38.887 232.365 -0.091 1.437 3.838 78.9 3.716 25.07 39.045 232.148 0.067 1.612 3.887 78227 3.678 24.904 38.742 232.154 0.044 1.64 4.174 78.762 3.665 24.919 38.826 232273 0.042 1.642 4244 78.337 3.669 24.917 38.719 231.706 0.093 1.738 4.186 78.521 3.643 24.824 38.769 233.199 -0.059 1.767 4.153 78262 3.616 24.831 38.739 232.383 -0.079 1.64 4.481 77.926 3.603 24.737 38.47 232.174 0.019 1.839 4.399 78.347 3.614 24.794 38.626 232.477 0.072 1.956 4254 77.826 3.586 24.654 38.516 232.567 0.182 1.974 4265 77.627 3.629 24.646 38.337 23321 0.085 2.092 4.64 77.574 3.577 24.57 38.324 23223 -0.062 2.004 4.661 77.605 3.576 24.52 38.306 232275 0.107 2.136 4.54 77.375 3.624 24.54 38242 232.403 0.033 2.077 4.468 77234 3.625 24.491 38.179 233.125 0.032 2.092 4.561 76.984 3.547 24.424 38.047 232.015 -0.03 2.14 4.679 76.864 3.548 24.407 38.124 233.081 0.156 2284 4.784 76.815 3.571 24.324 37.997 233.079 0.044 2.303 5.034 76.64 3.603 24.404 37.91 232.556 0.083 2.379 5.045 76.821 3.552 24.253 37.887 232.391 0.121 2.455 4.961 76.491 3.572 2428 37.858 232.591 0.15 2.557 4.697 76.029 3.545 24.173 37.768 232.998 -0.009 2.419 5.096 76.307 3.56 2423 37.579 232.767 0.042 2.448 4.967 76286 3.551 24.086 37.651
(1 202
232.714 0.149 2.611 5.046 76.18 3517 24.089 37.672 232.782 0.085 2.691 5.132 75.78 3.503 24.059 37515 234.184 0.166 2.76 5.015 75.782 3.469 24.065 37.341 232.342 0.125 2.786 5.06 75.398 3.513 23.984 37.361 232.472 0.188 2.774 5278 75.355 3.494 23.971 37238 232.835 0.172 2.768 5292 75.321 3.498 23.915 37.158 233.173 0.161 2.881 5.523 75.012 3.497 23.848 37.197 233.202 0.108 2.973 5239 74.921 3.477 23.717 37.104 232.748 0.128 3.003 5.464 74.664 3.467 23.742 37.068 233.022 0267 3.142 5.349 75.031 3.392 23.681 36.95 232.722 0.109 2.998 5.436 74.455 3.388 23.623 36.976 233.395 0.105 3226 5.433 74.642 3.356 23.567 36.791 233.168 0.178 3242 5.71 74.512 3.409 23.548 36.897 232.685 0.089 3.022 5.72 74.059 3.377 23.525 36.859 233.37 0205 3.25 5.502 74207 3.38 23.478 36.691 233.207 0265 3.317 5.768 73.786 3.322 23.419 36.589 232.428 0.131 3258 5.816 73.954 3.318 23.37 36.467 233.179 0.188 3.466 6.005 73.689 3.334 23.358 36.485 232.845 0.177 3.479 5.838 73.413 3254 23204 36522 232.854 0.325 3.724 5.758 73.394 3.32 23264 36.462 233.016 0.347 3.695 5.767 73.366 3226 23.179 36219 233.455 021 3.684 6.07 73.489 3278 23.112 36237 234.058 0.189 3.692 5.892 73279 3298 23.045 36.052 233.068 0229 3.737 6.07 72.688 3253 22.939 35.983 233.686 0.197 3.814 6.009 72.941 3239 22.954 36.037 233.378 0255 3.794 6.127 72.367 3272 22.963 36.043 233.643 0.325 4.001 6.175 72.604 3216 22.833 36.024 232.885 0.348 4.07 6.198 72.582 3.169 22.759 35.919 233.498 0.188 3.923 6.392 72253 3213 22.814 35.705 232.595 0268 4.042 6297 72.449 3.136 22.754 35.636 232.387 0.334 4.109 6.312 72.362 3.112 22.719 35.687 232.438 0.372 4.162 6238 72.087 3.094 22.598 35.432 233.218 0.381 4.102 6.54 71.712 3.09 22.525 35.569 233.004 0.388 4.317 6.432 71.98 3.058 22.469 35.587 233.129 0.319 4294 6.401 71.809 3.099 22.418 35.464 233.083 0264 4.303 6.483 71.369 3.057 22.395 35.434 233.43 0.331 4.42 6.614 71.458 3.027 22.363 35.321 232.725 0298 4.425 6.862 71.32 3.066 22.306 35.177 233.06 0227 4.354 6.849 71.064 3.018 22259 35205 233.573 0274 4.459 6.486 70.989 2.998 22209 35.1 233.844 0248 4.463 6.754 71.024 3.007 22.085 35.024 234.245 0.319 4.631 6.512 70.659 2.941 22.094 34.987 233.985 0.347 4.632 6.798 70.683 3.016 22.117 34.837 233.599 0.381 4.658 6.937 70.656 2.898 21.978 34.836 233.036 0.412 4.708 7.016 70.366 2.927 21.941 34.85 232.92 0.401 4.771 6.911 69.984 2.906 21.879 34.811 232.925 0.357 4.785 7.076 70.476 2.917 21.902 34.708 233.371 0.463 4.964 7.005 69.946 2.918 21.748 34.725 233.861 0.352 4.887 7.109 69.949 2.867 21.697 34.614 233.264 0.431 5.042 7.176 69.872 2.894 21.687 34.601 232.871 0.575 5.069 7249 69.622 2.813 21.64 34.381 233.724 0.404 5.057 7.122 69.446 2.874 21.643 34.528 203
233.24 0.459 5.155 7.063 69.496 2.834 21.579 34.368 233.688 0.362 5219 7.332 69.107 2.866 21.512 34.442 234542 0.546 5206 7272 69.047 2.842 21.539 34512 233.063 0.417 524 7.327 68.987 2.826 21.497 34.344 233.613 0.418 5205 7288 68.885 2.784 21.382 34525 233.582 0.414 5.35 7258 68.713 2.727 21.299 33.984 234.137 0.39 5.368 7.638 68.729 2.761 21.299 34.03 233.697 0.564 5.58 7.462 68.521 2.778 21548 33.829 232.97 0.464 5.381 7.119 68.419 2.788 21592 34.02 232.886 0.431 5.471 7.438 68.327 2.765 21.173 33.881 233.07 0.495 5.587 7.4 6826 2.705 21.108 33.702 233.029 0.513 5.6 7.549 68.088 2.684 21.088 33.953 233.301 0.354 5.439 7.634 67.979 2.707 21.007 33.634 232.867 0.471 5.693 7.773 67.904 2.736 21.03 33.504 233.557 0.448 5.662 8.067 67.43 2.694 20.958 33.613 233554 0.554 5.736 7.867 67.521 2.648 20.898 33.593 233.342 0.611 5.877 7.82 67.482 2.633 20.872 33.557 233.614 0.551 5.896 7.643 67.371 2.622 20.827 33.442 233.429 0.562 5.889 7.95 67.318 2.661 20.825 33.449 233.573 0.52 5.853 7.856 67.009 2.628 20.698 33.475 233.946 0.61 6.023 8.072 67.117 2.649 20.751 33.191 234.088 0.46 5.936 8.187 67.194 2.558 20.597 33595 233.339 0.566 6.123 8.009 66.734 2.622 20.67 33547 233.13 0.626 6222 7.943 66.71 2.631 20.624 33.014 232.778 0.529 6.162 8.009 66.689 2.592 20.55 33.092 234561 0.564 6.188 7.793 66287 2.554 20.492 32.925 233.322 0.622 623 8.043 66.543 2.539 20.514 32.956 233.619 0.647 6275 7.748 65.846 2.546 20.413 32.871 233.354 0.487 6.348 8278 66.119 2.476 20.364 32.921 234.518 0.484 6236 8.044 66.022 2.577 20.47 32.873 234.252 0.638 6.43 8.368 65.879 2.578 20.408 32.612 234.566 0.523 6.397 8.534 65:949 2.58 20.307 32.768 233.086 0.603 6.394 8.186 65.917 2.465 20539 32.754 233.018 0.713 6.526 8.329 65.531 2.453 20.149 32.519 233.541 0.585 6.518 8.453 65.332 2.501 20.156 32.658 233.55 0.579 6.57 8.37 65.385 2.449 20.09 32.551 233.56 0.632 6.633 8.386 64.959 2.489 20.055 32.613 233.155 0.698 6.802 8.477 64.919 2.451 20.041 32.56 233.659 0.614 6.762 8.652 65202 2.392 19.967 32.588 233.896 0.695 6.886 8.425 64.718 2.443 19.97 32597 234.65 0.498 6.717 8.542 64.734 2.476 19.913 32551 233.593 0.688 6.871 8.858 64.804 2.421 19.894 32.151 233.611 0.63 6.828 8.637 64.673 2.383 19.788 32.137 234.164 0.651 6.951 8.672 64.557 2.38 19.758 32.085 234.391 0.58 6.957 8.525 64.539 2.381 19.72 32516 233.398 0.686 6.88 8.819 64209 2.402 19.638 32.086 233.714 0.74 7.152 8.645 64.163 2.345 19.636 32.075 233.482 0.645 7.086 8.802 64.173 2.369 19.553 32.097 233.646 0.627 7.082 8.783 64.004 2.335 19.551 31.767 233.448 0.59 7.161 9.013 64237 2.334 19.506 32.001 234.067 0.79 7.191 8.539 63.702 2.347 19.466 31.834 234.587 0.764 7299 9.093 63.766 2.353 19.443 31.75 204
233.643 0.688 7.304 8.9 64.145 2.33 19.425 31.847 233.927 0.671 7233 9.046 63.68 2284 19.351 31.627 234.375 0.788 7.478 9.14 63.607 2268 19.323 31.797 234.304 0.767 7.359 9.146 63.528 228 19249 31.646 233.712 0.756 7.345 8.997 63271 2.303 19298 31.615 233.522 0.633 7.329 8.98 63.079 2.304 19218 31.484 233.398 0.634 7.333 9.097 62.994 2.301 19.112 31.38 233.749 0.622 7.494 8.821 63.173 225 19.094 31.375 233.637 0.823 7.534 9.155 63.609 2241 19.038 31.33 233.607 0.663 7.462 9.36 63.049 222 19.089 31288 233.696 0.797 7.647 9.447 62.636 2222 19.041 31228 233.349 0.777 7.603 9246 62.711 2217 18.911 31.187 234.044 0.782 7.719 9.391 62.464 2224 18.917 31.124 234.185 0.825 7.753 9.431 62.47 2.189 18.828 31.126 233.507 0.9 7.719 9269 62267 2.199 18.861 31:088 233.815 0.642 7.682 9296 62254 2216 18.815 31.12 233.115 0.831 7.793 9.388 61.998 2.15 18.731 30.923 233.772 0.804 7.788 9268 61.924 2.147 18.741 31.004 233.566 0.707 7.82 9.431 61.875 2.165 18.717 30.907 233.728 0.817 7.866 9.44 61.649 2.13 18.668 30.848 232.986 0.703 7.818 9.563 61.851 2.14 18.629 30.864 233.998 0.738 7.915 9.306 61.695 2.108 18.633 30.704 233.507 0.77 8.052 9.412 61.376 2.073 18.513 30.716 233.326 0.75 8.101 9.527 61.752 2.083 18.449 30.634 233.988 0.773 8.063 9.6 61.469 2.115 18.427 30.79 233.763 0.757 8.035 9.483 61;451 2.096 18;501 30.67 233.705 0.751 8.034 9.405 61.484 2.094 18.461 30.69 233.672 0.855 8555 9.642 61.105 2.09 18.372 ■30.737 233.762 0.775 8221 9.598 61.116 2.089 18.366 30.522 233.701 0.795 8.148 9.834 61,15 2.053 1827 30.39 234.446 0.784 8216 9.697 60.921 2.065 18267 30.505 234.084 0.849 8234 9.867 60.855 2.108 18.308 30.54 234.1 0.813 8272 10.016 60.903 2.091 18.194 30.439 234.562 0.85 8.354 9.681 60.653 2.051 18.091 30.341 234.452 1.002 8.531 9.71 60.695 2.049 18.131 30.385 234.671 0.83 8.49 9.612 60.811 2.066 18.083 30.351 234.544 0.892 8281 9.751 60.514 2.055 18.075 30.309 234.452 0.833 8.494 9.793 60.544 2.04 18.064 30241 234.654 0.969 8.514 10.051 60.312 2.049 18.005 30.311 233.796 0.868 8.542 9.798 60.37 2.049 17.988 30.167 234.55 0.802 8.638 10.105 60.171 1.977 17.931 30.03 234.667 1 8.803 9.937 59.932 1.988 17.862 30.162 234.435 0.926 8.608 9.914 59.799 2.021 17.858 30.158 235.119 0.782 8.551 9.936 60.077 1.992 17.809 29.971 234.936 0.912 8.759 10.005 59.528 1.961 17.802 29.985 234.903 0.878 8.727 10.025 59.651 1.964 17.767 29.946 234.402 0.899 8.737 10.377 59.755 1.963 17.678 30.059 234.345 0.943 8.789 10.342 59.836 1.944 17.683 29.915 234.824 0.945 8.725 10.344 59.898 1.955 17.612 29.78 235.014 0.949 8.834 10226 59.361 1.911 17.58 29.836 234.317 0.864 8.85 10.135 59.445 1.926 17.563 29.695 234.344 1.041 9.034 10.194 59.52 1.881 17.473 29.922 205
23421 0.911 8.945 10.172 59239 1.901 17.532 29.702 234.757 0.987 8.975 10.07 59.191 1.883 17.469 29.662 234.818 0.907 8.986 10.343 59.087 1,903 17.487 29.709 234.645 0.956 8.943 10.422 59.086 1.885 17.365 29.587 234.634 1.051 9.038 10.373 58.794 1.879 17.353 29.553 23428 0.946 8.95 10273 58.849 1.883 17.343 29.57 233.959 0.999 9.05 10.309 58.514 1.832 17298 29.449 234.125 1.009 9.097 10.698 58.899 1.858 17234 29.479 235.067 0.943 9213 10.619 58.528 1.855 17.189 29.407 235.738 0.976 9.305 10.616 58.524 1.802 17.139 29.439 234.146 1.062 9274 10.41 58.772 1.828 17.108 29.542 234.702 1.032 9269 10.644 58.705 1.803 17.122 2928 234.603 1.061 9.339 10.557 58.31 1.849 17.057 29239 235.145 0.986 9249 10.503 58.509 1.805 17.095 29291 234.719 1.053 9.454 10.62 58.31 1.88 17.076 29221 234.316 1.053 9.343 10.684 57.89 1.781 16.946 29.138 234.878 0.987 9.406 10.653 58.359 1.743 16.922 29246 235.345 1.049 9.529 10.591 58.128 1.792 16.87 29.088 234.667 0.895 9.503 10.654 57.925 1.783 16.894 28.987 234.367 0.982 9.608 10.608 57.911 1.734 16.81 29238 235.362 0.973 9.454 10.846 57.881 1.73 16.802 29.039 234.647 1.033 9.545 10.638 58.041 1.802 16.774 29.098 234.96 1.102 9.65 10.888 57.564 1.716 16.78 28.871 234.119 1.051 9.646 10,859 57.447 1.772 16.715 29.027 235.147 0.989 9.584 10.834 57.476 1.746 16.663 29.026 235.767 1.165 9.853 10.834 57.83 1.729 16.679 28.976 235.189 1.046 9.686 10.806 57.098 1.705 16.631 28.932 234.471 1.053 9.694 10.735 57.483 1.716 16.548 28.758 234.37 1.083 9.72 10.78 57.303 1.713 16.596 28.776 235.328 1.156 9.813 10.672 57.155 1.716 16.536 28.826 234.592 1.066 9.746 11.036 57.115 1.699 16.477 28.771 235.191 1.104 9.808 10.971 57.01 1.648 16.424 28.7 234.924 1.209 9.947 11.097 56.986 1.703 16.398 28.717 234.9 0.927 9.949 11.01 56.929 1.669 16.389 28.693 234.785 0.966 9.811 11.123 56.826 1.665 16.426 28.8 234.249 1.181 9.97 10.901 57.155 1.684 16.401 28.759 235.081 1.135 9.99 11.098 56.854 1.647 16.302 28.698 235.109 1.062 9.939 10.886 57.114 1.634 16288 28.722 235.339 1.076 10.037 10.776 56.892 1.637 16291 28.656 235.447 1.077 10.127 11.154 56.73 1.635 16232 28.574 235.767 1.027 9.91 11.388 56.779 1.64 16.183 28292 235.223 1.1 10.076 11.025 56.6 1.622 16.174 28.3 234.934 1.041 10.19 11.306 56.727 1.573 16.062 28.52 235.405 1.178 10.11 10.907 56.562 1.545 16.076 28.549 234.764 1.109 10251 11.067 56.373 1.578 16.021 28.305 235.006 1.116 10264 11217 56.14 1.612 16.002 28.472 235.805 1.092 10248 11.115 56283 1.603 16.01 28.433 234.711 1234 10.175 11.316 56.324 1.597 15.928 28286 235.731 1.07 10.336 11.356 56.142 1.574 15.894 28.339 235.242 1.167 10.32 11.148 55.991 1.561 15.832 28249 235.391 1.155 10251 11.125 55.862 1.543 15.836 28.334 235.456 1.107 10.309 11.17 55.832 1.571 15.84 28249 206
235.057 1.116 10.359 11243 55.758 1.548 15.77 28.129 235.328 1.179 10.415 11284 55.568 1.564 15.804 28.15 234.738 1.171 10.378 11.316 55.804 1.521 15.695 28.053 235.353 1.159 10.385 11.332 55.989 1.545 15.695 28.035 235.621 1.12 10.468 11.508 55.948 1.54 15.645 28.045 236.059 1.176 10.427 11.576 55.554 1.518 15.681 28.015 234.955 1.15 10.482 11.535 55.52 1.526 15.593 27.976 235.397 1.121 10.443 11.693 55.748 1.521 15.644 28.099 235.806 1.262 10.627 11.525 55.627 1.461 15.587 28.068 235.336 1.217 10.612 11.439 55.685 1.543 15.528 28.009 235.571 1.159 10.638 11.561 55.376 1.452 15.551 28.015 235.828 1.113 10.528 11.579 55.316 1.497 15.481 28.02 235.051 1255 10.591 11.563 5521 1.491 15.481 27.78 235.837 1.085 10.733 11.458 55.383 1.464 15.411 27.994 236.015 1.174 10.639 11.718 55:159 1.508 15.449 28.031 235.81 1.177 10.743 11.536 54.93 1.399 15.405 27.852 235249 1.108 10.842 11.334 55.102 1.468 15.351 27.834 235.466 1.154 10.764 11.844 54.981 1.47 15.412 27.725 235.042 1.198 10.744 11.63 54.879 1.462 15.434 27.714 235.251 1.163 10.842 11.546 54.8 1.495 15.439 27.767 236.016 1263 10.781 11.665 54.777 1.5 15.418 27.646 235.347 1.161 10.831 11.724 54.604 1.451 15.449 27.471 236.611 1.194 10.913 11.834 54.482 1.498 15.411 27.519 235.599 1.186 10.845 11.817 54.386 1.528 15.427 27.502 235.872 1277 10.974 11.993 54267 1.477 15.398 27.477 235.302 1.312 10.94 11.708 54.564 1.474 15.356 27.463 235.067 1227 10.901 11.643 54.309 1.493 15.345 27.559 235.743 1291 10:999 11.901 54243 1.444 15.324 27.52 235.503 1293 11.005 11.839 54.329 1.514 15.376 27.476 235.731 1268 11.068 11.676 54.164 1.514 15.377 27.462 235.426 1.198 10.962 11.836 54221 1.497 15.355 27.419 235.856 1.367 11.013 11.888 54265 1.489 15.339 27.348 235.789 1288 11.019 12.016 54.196 1.484 15299 27.395 235.607 1203 11.145 11.759 53.933 1.482 15213 27.354 236.017 1266 11.185 11.913 53.97 1.46 15261 27261 235.517 1.328 11.182 12.143 53.975 1.457 15255 27.376 235.425 1284 11.161 11.885 53.469 1,424 15.143 27273 235.379 1.182 11.091 11.804 53.958 1.476 15.144 27225 235.455 1226 11221 12.038 54.028 1.452 15.153 27295 235.537 1217 11.163 12.112 53.654 1.41 15.143 27.342 235.981 1.449 11295 12.013 53.798 1.453 15.064 27223 235.404 1265 11.35 12.12 53.98 1.429 15.008 27279 235.658 125 11296 12.067 53.41 1.412 15.009 27.175 235.5 1.327 11.311 12.191 53.547 1.402 15.012 27.176 235.926 1.332 11.377 12.111 53.396 1.375 14.965 27.192 236.279 1.364 11.37 12.322 53.404 1.408 14.955 26.867 235.478 1287 11.372 12.111 53.431 1.403 14.953 27.037 235.809 1.302 11297 12.305 53.444 1.409 14.953 27.191 236.052 1.316 11.365 12217 53.356 1.379 14.902 26.928 235.198 1.341 11.378 11.992 53.634 1.384 14.865 27.14 235.903 1.406 11.537 12202 53.168 1.369 14.854 27.024 235.838 1285 11.337 12.3 52.972 1.37 14.789 26.774 207
236.052 1.356 11.508 12.149 53.234 1.34 14.757 26.874 235.949 1234 11297 12.188 53.136 1.336 14.743 26.927 235.981 1.339 11.523 12.162 53.35 1.341 14.724 26.926 235.816 1.326 11.591 12226 53.002 1.351 14.739 26.851 235.67 1287 11.48 12.321 52.756 1.336 14.722 26.888 234.667 1.373 11.608 12298 53.236 1.349 14.686 26.754 236.148 1.346 11.624 12298 52.854 1.348 14.633 26.654 235.532 1236 11.535 12292 53.145 1.312 14.59 26.839 235.758 1.34 11.639 12.49 52.907 1.336 14.604 26.802 235.637 1285 11.63 12.302 52.982 1.364 14.617 26.781 236.294 1.347 11.738 12.512 52.991 1.324 14.612 26.601 237.166 1.37 11.673 12.537 52.586 1.31 14.609 26.625 236.092 1.193 11.7 12.305 52.508 128 14.417 26.856 235.112 1.357 11.78 12.484 52.88 1.308 14.464 26.6 236.261 1.361 11.777 12.471 52.58 1264 14.466 26.774 235.982 1.444 11.858 12574 52.719 1.33 14.445 26.67 236.253 1.424 11.957 12.567 52.845 1269 14.369 26.655 235.886 1.421 11.907 12.525 52.652 1257 14;359 26.523 236.802 1.39 11.949 12.447 52.232 1.304 14.367 26.691 236.488 1.327 11.832 12.489 52202 1232 14.315 26.746 235.447 1.405 11.927 12.674 52.73 1252 14298 26.642 236.127 1.354 11.798 12.617 52.127 1255 14.33 26.562 236.306 1.429 11.923 12.371 52.197 1251 14.385 26.525 235.397 1.369 11.914 12.762 52.159 1287 14254 26.487 236.215 1255 11.791 12.512 51.533 1.319 14.428 26.313 236.06 1.43 11.947 12.717 52.031 1298 . 14.367 26.413 234.995 1.435 11.86 12.651 51.72 1267 14.361 26.414 235.459 1.399 11.905 12.768 51.808 1.314 14.364 26.162 235.431 1286 11.98 12.478 51.592 1.316 14.361 26.199 235.601 1.347 12.021 12.721 51.901 1287 14.405 26271 234.723 1.418 11.974 12.723 51.644 1.312 14.351 26208 235.283 1.408 12.084 12.456 51.775 1.31 14.34 26.499 234.994 1.484 12205 12.556 51.567 1.321 14.305 26.342 235.715 1.437 12 12.693 51.348 1299 14.304 26.088 236.567 1.354 12.126 12.717 51.649 1263 14244 26.038 235.122 1.331 12.11 12.798 51.46 1275 14268 2625 235.739 1.338 11.989 13.002 51.314 1.329 14241 26.156 234.617 1.47 12.105 12.99 51.667 1283 14.174 26.32 236.002 1.49 12.169 12.644 51.267 1256 14.138 26.091 236.126 1.417 12202 12.653 51.624 1293 14.157 26.309 236.058 1.481 12237 12.674 51.152 1239 14.122 26279 235.929 1.42 1228 12.598 51.291 1259 14.097 26.153 237.117 1.358 12231 12.682 51217 1239 14.097 26264 235.874 1.393 12222 12.87 51.123 1223 14.043 25.972 236.648 1.567 12266 12.697 51.001 1205 13.954 26.103 235.921 1.386 12242 13.136 50.982 1224 13.982 25.766 235.318 1.505 12.346 12.81 51.159 1223 13.945 25.943 236.545 1.436 12219 12.616 50.839 1277 13.966 25.927 236.286 1.466 1224 13.002 51.025 1203 13.949 25.956 235.187 1.386 12.364 12.954 51213 1236 13.88 25.981 235.999 1.429 12277 13.068 50.994 123 13.902 26.023 236.797 1.439 1227 13.033 50.725 1.168 13.915 25.955 208
236.415 1.46 12291 12.84 50.631 122 13.883 25.863 236.653 1.375 12.38 12.985 50.914 1.189 13.809 25.983 235.686 1.49 12346 12.981 50.916 1.191 13.847 25.95 235.554 1.461 12.467 12.869 51 1.173 13.808 25.847 235.801 1.339 12.404 13.012 50.706 1.199 13.784 25.769 235.418 1.568 12.556 12.934 50.621 1226 13.823 25.735 235.246 1.475 12.415 12.87 50288 1.163 13.725 25.727 235.025 1.514 12.554 12.743 50.593 1.193 13.75 25.729 234.687 1.447 12.411 12.922 50262 1231 13.769 25.553 234.654 1.387 12.314 12.732 50.632 1207 13.842 25.672 233.939 1.362 12.435 12.575 50.389 1202 13.771 25.646 234.278 1.508 12.567 12.893 50.377 1.198 13.793 25.601 234.832 1.389 12.471 13.032 50.16 1218 13.779 25.511 234.799 1.48 12.555 12.959 50.089 1.19 13.799 25.652 235.376 1.544 12.695 13.135 50.09 1221 13.837 25.341 234.084 1.41 12.439 12.945 50.197 1237 13.829 25.744 235.052 1.431 12.423 13.009 50.121 1.167 13.776 25.552 235.014 1.418 12.498 12.998 50.323 1.162 13.769 25.499 234.995 1.557 12.612 13294 50237 1208 13.747 25.522 234.225 1.402 12.548 12.995 50.033 1.185 13.8 25.707 234.941 1.557 12.771 12.936 49.987 1.188 13.705 25.601 234.653 1.489 12.756 12.993 49.922 1228 13.764 25.537 235.303 1.322 12.638 13.117 49.988 1.181 13.631 25.441 235.437 1.562 12.718 13.129 49.953 1.174 13.576 25.489 235.629 1.488 12.628 13258 49.928 1.149 13.563 25.512 235.354 1.459 12.7 13.107 49.82 1.185 13.659 25.271 235.038 1.543 12.745 13213 50.087 1.174 13.587 25.263 235.384 1.572 12.815 13.342 50.029 1.14 13.567 25.36 235.506 1.558 12.8 1324 49.726 1.125 13.493 25.362 236.067 1.468 12.778 13.159 49.893 1.133 13.466 25.337 235.518 1.456 12.702 132 49.619 1.119 13.518 25.357 235.322 1.518 12.848 13.339 49.856 1.164 13.541 25.162 235.561 1.388 12.849 13267 49.807 1.132 13.449 25219 235.384 1.581 12.835 13.17 49.312 1.054 13.392 25241 235.756 1.415 12.746 13.378 49.681 1.125 13.339 25269 235.073 1.363 12.721 13.527 49.673 1.108 13.324 25.156 234.603 1.532 12.964 13.345 49.766 1.105 13.356 25263 234.644 1.562 12.943 13.348 49245 1.085 13.312 25.101 235.773 1.436 12.883 13.535 49223 1,109 13.343 25.31 235.92 1.47 12.922 13.367 49.446 1.141 1329 25238 235.044 1.504 12.968 13297 49.371 1.155 13.351 25.129 234.7 1.48 12.897 13.456 49.11 1.098 13.308 252 236.129 1.586 12.924 13.472 49215 1.105 13.313 25.175 235.097 1.579 12.985 13.389 48.801 1.101 13276 25.039 236.049 1.604 12.978 13263 49.149 1.112 1329 25.088 235.811 1.465 12.933 13.641 49.426 1.094 13251 25.166 235.122 1.463 12.904 13.585 49.137 1.118 13248 25.117 236.096 1.519 12.967 13247 48.931 1.074 13.179 25.085 235.979 1.553 12.979 13.424 49.158 1.074 1321 25.063 234.978 1.492 13.053 13.512 49.072 1.073 13.131 25.115 235.197 1.622 13.062 13.405 48.878 1.095 13.103 24.917 234.658 1.505 13.049 13.366 4921 1.044 13.09 25.075 209
234.532 1.459 13.169 13.643 49.1 1.026 13.053 25.055 234.633 1.57 13.122 13.472 48.444 1.091 13.098 24.945 234.935 1.614 13.191 13.725 48.444 1.069 13.019 24.959 234.902 1.563 13.231 13.494 48.709 1.024 12.99 25.002 235.23 1.462 13.03 13.465 48.711 1.084 13.076 24.888 234.743 1.598 13.125 13.379 48.804 1.051 12.981 24.764 235.1 1.569 18236 13.451 48.393 1.075 13.02 24.783 235.424 1.626 13.195 13.621 48.559 1.082 12.993 24.76 234.449 1.558 13.188 13.434 48.541 1.069 12.948 24.894 234.502 1.572 13245 13.529 48272 1.042 12.97 24.88 234.931 1.491 13.157 13.545 48287 1.071 12.939 24.654 234.671 1.56 13284 13.583 48.636 1.04 12.803 24.873 235.764 1.497 13242 13.467 48.687 1.017 12.881 24.809 235.208 1.538 13.322 13.713 48.435 1.032 12.933 24.828 234.885 1.6 13.309 13.694 48.334 1.012 12.788 24.842 234.766 1.498 13218 13.528 48.558 1.052 12.819 24.761 235.811 1.643 13256 13.77 48.42 1.023 12.768 24.645 235.297 1.639 13.303 13.866 48.432 0.995 12.793 24.754 235.337 1576 13.419 13.66 48.102 0.988 12.823 24.673 234.532 1.509 13298 13.749 48259 1.071 12.891 24.884 234.64 1572 13.375 13.754 48.103 1.05 12.818 24.747 235.553 1579 13.491 13.936 48.38 1.029 12.8 24.484 235.434 1.76 13.597 13.569 48.014 1.013 12.799 24.83 235.216 1.663 13.416 13.645 48214 1.028 12.762 24.608 235.129 1.592 13.487 13.733 47.682 1.029 12.78 24.744 234.761 1.544 13.476 13.8 48.012 1.046 12:823 24.619 234.735 1.575 13.477 13.648 48.53 1.019 12.787 24.597 234.733 1.666 13.491 13.562 48.09 1.035 12.774 24.514 234.684 1.69 13.494 13.718 47.977 1 12.662 24.622 235.551 1.491 13.467 13.866 48204 0.977 12.622 24.663 235.175 1.684 13.381 13.933 48246 1.004 12.684 24.407 235.594 1.55 13.482 13.783 47.863 0.991 12.672 24.54 235.54 1.565 13.565 13.552 48.121 0.999 12.62 24.507 235.618 1.56 13.515 13.798 48.072 0.998 12.642 24.435 235.722 1.634 13.533 13.739 48.33 0.986 12.612 24.385 235.372 1577 13.466 13.706 47.767 0.962 12.623 24.539 236.043 1.65 13.609 13.802 47.688 I 12.605 24.531 235.049 1.519 13.44 13.9 47.715 1.018 12.588 24.417 235.128 1.521 13.64 13.655 47.913 0.984 12.59 24.584 236.099 1.667 13.609 13.658 47.588 0.94 12.607 24.482 235.366 1.607 13.485 13.988 47.643 0.957 12.632 24.468 235.81 1.607 13.542 13.907 47.999 0.987 12.488 24.478 234.93 1.564 13.592 13.883 47.996 0.971 12.516 24.428 235.652 1.525 13.586 14.067 47.68 0.964 12.533 24.36 234.706 1.508 13.615 13.773 47.783 0.989 12.532 24.453 234.956 1.601 13.79 13.804 47.803 0.963 12.538 24.467 235.764 1.643 13.655 13.821 47.316 0.975 12.463 24.349 235.426 1.61 13.69 13.926 47.661 0.972 12.439 24.311 234.947 1.616 13.662 14.043 47.575 0.979 12.448 24259 235.405 1.604 13.655 13.908 47.313 0.944 12.468 24.395 235.392 1.64 13.617 14.017 47.652 0.972 12.376 24.321 235.45 1.643 13.761 13.734 47.59 0.979 12.448 24282 210
236.221 1.736 13.776 13.893 47.303. 0.938 12.433 24513 235.231 1.641 13.689 13.92 47.346 0.985 12.434 24.346 235.521 1.688 13.648 14.109 47.474 0.985 12.441 24.385 236.202 1.499 13.7 13.917 47.732 0.95 12.413 24.129 235.224 1.605 13.702 13.938 47.372 0.972 12.391 24.357 236.839 1.593 13.845 13.746 47.415 0.957 12.402 24.303 235.924 1.537 13.792 14.063 47.643 0.958 12.397 24.35 235.154 1.736 13.768 13.854 47.546 0.953 12561 24.04 235.025 1.567 13.81 14.353 47505 0.931 12.318 24.178 235.951 1.619 13.915 14.069 47.402 0.893 1257 24.09 235.843 1.697 13.82 14.051 47544 0.972 12.37 24.167 236.278 1.671 13.873 14.004 47575 0.942 12.313 24.09 235.32 1.607 13.869 14.151 47535 0.929 12.356 24508 235.737 1.698 13.958 13.842 47.386 0.939 12569 24508 235.33 1.591 13.849 13.921 47.169 0.971 12.32 24:181 235.253 1.616 13.917 13.892 46.942 0.935 12.353 24.054 236.099 1.711 13.94 14505 46.947 0.905 12539 24593 235.494 1.547 13.879 14536 47.099 0.926 12564 24.071 236.012 1.732 14.028 14.131 46.92 0.941 12587 24.022 234.799 1.624 13.897 14517 46.937 0.952 12567 23.992 236.01 1.701 13.95 14.198 47521 0.891 12.146 24.081 235.007 1.656 13.933 14.142 47.153 0.897 12517 24.102 236.268 1.571 13.877 14.107 47 0.862 12.089 24.05 235.882 1.552 13.997 14.366 47.086 0.944 12.176 24.036 236.62 1.649 14.083 14529 46.85 0.9 12.154 24.082 236.223 1.624 13.98 14.123 46.912 0.904 12503 23.968 236.121 1.662 13.961 14586 46.714 0.901 12.155 24.003 235.899 1.643 14.101 14.116 46.893 0.891 12.119 24.113 235.138 1.54 14.111 14.154 46.598 0.897 12.141 24.037 235.684 1.709 14.104 14504 47.075 0.839 12.09 24.116 236.832 1.644 14.032 14585 46.807 0.887 12.08 24.089 235.845 1.695 14.027 14.137 46.634 0.883 12.097 24.1 235.939 1.711 14.029 13.977 46.786 0.9 12.019 24.08 235.69 1.655 14.188 14.122 47.145 0.898 12.05 24.078 211
J K L M N O P time (e) 28.717 157217 0.433 -0.759 2.784 0.652 4269939 0 28.725 156.924 0.37 -0.689 3.048 0.758 4.021108 60 28.736 157.11 0.41 -0.174 3213 0.716 4.48743 120 28.778 157.467 0.483 0.015 3.162 0.682 4.636364 180 28.878 157.436 0.357 0.107 3.407 0.762 4.471129 240 28.738 157.457 0.467 0.485 3.557 0.709 5.016925 300 28.91 157.661 0.478 0.717 3.755 0.802 4.682045 360 28.879 157.79 0.358 0.828 3.686 0.688 5.373178 420 28.77 157.882 0.429 1.043 4.137 0.842 4.913302 480 28.78 158.563 0.481 1.307 4.118 0.849 4.850412 540 28.877 158.088 0.505 1.395 4.312 0.868 4.967742 600 28.775 157.664 0.481 1.571 4.416 0.823 5.365735 660 28.821 159.154 0.473 1.731 4.594 0.898 5.115813 720 28.918 157.448 0.5 1.831 4.853 0.919 528074 780 28.909 158203 0.516 2.115 4.855 0.928 5231681 840 28.759 158.479 0.515 2.199 4.902 0.919 5.334059 900 28.865 158.6 0.562 2.387 4.931 0.917 5.377317 980 28.847 158.049 0.497 2.48 5.129 0.978 5244376 1020 28.776 158204 0.534 2.666 5212 0.97 5.373198 1080 28.848 158257 0.587 2.825 5.391 1.014 5.316568 1140 28.736 158.401 0.592 2.979 5.622 0.951 5.911672 1200 28.877 158.697 0.613 3.156 5.745 0.949 6.053741 1260 28.813 158.979 0.604 3255 5.933 1.001 5.927073 1320 28.665 158.929 0.638 3.393 6.019 0.982 6.129328 1380 28.754 158.805 0.643 3.515 6.027 0.95 6.344211 1440 28.771 158.614 0.55 3.689 628 1.029 6.103013 1500 28.868 159.863 0.598 3.762 6.375 1.127 5.65661 1560 28.84 158.76 0.597 3.971 6.55 1.098 5.976277 1620 28.841 159.139 0.673 4.151 6.786 1228 5.526059 1680 28.732 159.751 0.612 4243 6.874 1209 5.685691 1740 28.772 159.838 0.673 4.449 6.901 1.161 5.944014 1800 28.752 160.019 0.681 4.604 6.642 1.004 6.814741 1880 28.72 160.156 0.664 4.605 723 1.097 6.590702 1920 28.838 160.889 0.718 4.907 7.409 1.067 6.943768 1980 28.783 160.627 0.629 4.898 7.45 1223 6.091578 2040 28.765 160.937 0.716 5.155 7.756 123 6.305691 2100 28.777 161.181 0.744 5299 7.814 1.315 5.942205 2160 28.764 162.024 0.788 5.575 7.9 1.348 5.860534 2220 28.695 161.452 0.755 5.68 8.158 1.305 6251341 2280 28.746 161.033 0.755 5.804 8262 1.416 5.834746 2340 28.76 161.846 0.793 5.923 8.35 1.365 6.117216 2400 28.723 162229 0.756 6.036 8.374 1281 6.53708 2460 28.72 162.67 0.775 6.079 8.468 1246 6.796148 2520 28.684 162223 0.771 6.393 8.788 1.428 6.154062 2580 28.814 162.895 0.76 6.432 8.922 1.401 6.368308 2640 28.658 163.153 0.808 6.582 9.06 1.396 6.489971 2700 28.63 162.912 0.851 6.878 9.12 1273 7.164179 2760 28.76 163.676 0.816 6.988 , 9.417 1.378 6.833817 2820 28.581 163.837 0.835 7.127 9.553 1.472 6.48981 2880 28.611 163.831 0.871 7.468 9.664 1.498 6.459893 2940 212
28538 164.34 0.844 7.323 9.931 1.449 6.853692 3000 28.624 164.545 0.811 7.458 9.946 1.404 7.084046 3080 28.685 165.417 0.857 7.657 1023 1.458 7.016461 3120 28.645 164.877 0.892 7.895 10.189 1.463 6.964457 3180 28.619 165.372 0.9 8.015 10.425 1.516 6.876649 3240 28.705 165.31 0.921 8.073 10.606 1.557 6.811818 3300 28.546 165.539 0.981 8288 10.553 1.609 6.558732 3360 28.534 166.147 0.962 8.482 10.882 1.557 6.976236 3420 28.588 165.464 0.946 8.571 11.082 1.599 6.918074 3480 28.564 166.594 0.889 8.725 11217 1.837 6.106151 3540 28.457 166.919 0.985 8.976 11217 1.66 6.757229 3600 28.584 167.669 0.97 9.132 11.495 1.73 6.644509 3660 28.448 167.302 0.974 9267 11.788 1.827 6.452107 3720 28.524 167.307 0.968 9.364 11.793 1.622 7270654 3780 28.398 168239 1.008 9.56 11.895 1.788 6.652685 3840 28.57 168.425 1.073 . 9.837 11.982 1.653 7248639 3900 28.527 168.618 1.05 9.84 12.161 1.708 7.120023 3980 28.417 168.714 1.055 9.943 12.332 1.72 7.169767 4020 28.393 169.198 1.134 10.164 12.512 1.867 6.70166 4080 28.333 16926 1.096 10.398 12.768 1.888 6.762712 4140 28.329 169.658 0.984 10.41 12.829 1.858 6.904736 4200 28.327 169.723 1.169 10.732 12.928 1.721 7.511912 4260 28.349 169.773 1.107 10.729 13224 1.896 6.974684 4320 28.197 169.483 1.152 10.91 13287 1.824 7284539 4380 28.174 169.921 1.184 11.143 13.546 1.951 6.943106 4440 28297 169.408 1.08 11.124 13.616 2.025 6.723951 4500 28.17 170.388 1.123 11.438 13.676 1.93 7.08601 4560 28.18 171.521 1.165 11.548 13.728 1.963 6.993377 4620 28233 170.593 1.19 11.723 14.023 1.929 726957 4680 28.185 171.362 1.194 11.852 14.087 1.917 7.348461 4740 28.094 171.857 1209 12.128 14.313 1.948 7.347536 4800 28.165 172.166 1.22 12213 14.572 2.025 7.196049 4880 28215 172.508 1254 12.456 14.42 1.928 7.479253 4920 28.093 172.891 1255 12.546 14.903 2.123 7.019783 4980 28.003 172.111 122 12.528 14.95 2.126 7.031985 5040 28.031 172.737 1.29 12.754 15.099 2.116 7.135633 5100 27.993 173213 1274 12.891 15.145 2.102 7205043 5160 28.071 173.528 1261 13.087 15.421 2.159 7.142659 5220 28.005 173.635 1261 13.098 15.437 2.134 7233833 5280 28.029 173.587 1.29 13.404 15.677 2.183 7.181402 5340 28.044 173.435 1.386 13.559 15.744 2.155 7.3058 5400 27.887 174.114 1.301 13.68 16.001 2.166 7.38735 5460 27.932 173.782 1.358 13.83 16.076 2.163 7.43227 5520 27.719 174.824 1.402 13.955 16239 2.334 6.957584 5580 27.845 173.92 1.41 14.094 16.475 2258 729628 5640 27.72 174.061 1.394 14239 16.472 2.326 7.081685 5700 27.745 173.952 1.454 14.303 16.605 2291 7247927 5760 27.684 174.834 1.426 14.443 16.807 2.086 8.057047 5820 27.66 175.844 1.443 14.801 16.954 2.359 7.186944 5880 27.6 174.125 1.491 14.92 17.093 2273 7.520018 5940 27.631 . 175.702 1.432 15.054 17.123 2.398 7.140534 6000 27.64 175.41 1.469 15.066 17.377 2.368 7.33826 6060 213
27.505 175.45 1.48 15238 17.543 2.364 7.420897 6120 27.556 175.485 1.526 15.511 17.532 2.321 7.553641 6180 27.603 176.618 1.487 15.519 17.758 2.401 7.398085 6240 27.286 175.197 1.553 15.669 17.949 2.493 7.199759 6300 27.418 175.958 1.591 15.877 18236 2.482 7.347301 6360 27.321 176248 1.564 16.04 18.175 2.568 7.077492 6420 27.163 176.911 1.522 16.198 18.542 2.547 7279937 6480 27.174 175.772 1.574 16.189 18.393 2.42 7.600413 6540 27.163 175.745 1.583 16.356 18.615 2.504 7.434105 6600 27256 176.647 1.612 16.489 16.937 2.679 7.068682 6660 27.177 176.636 1.636 16.707 18.787 2.518 7.46108 6720 27.087 177.081 1.641 16.774 19.077 2.711 7.036887 6780 27.14 176.708 1.606 16.946 19.103 2.652 7203243 6840 27.088 175.947 1.715 17.1 19.186 2.578 7.442203 6900 27.086 176.817 1.688 17288 19.389 2.553 7.594595 6880 26.883 176.547 1.632 17.311 19.637 2.671 7.351928 7020 26.95 176.688 1.609 17.365 19.706 2.629 7.495626 7080 26.808 176.879 1.629 17.508 19.688 2.583 7.614402 7140 26.922 177.408 1.649 17.636 19.94 2.689 7.415398 7200 26.79 176.868 1.775 17.875 20.156 2.813 7.165304 7260 26.947 176.729 1.773 18.084 20.158 2.674 7.538519 7320 26.731 177.608 1.795 18237 20.438 2.787 7.333333 7380 26.714 177.53 1.761 18231 20.449 2.782 7.350467 7440 26.611 177.123 1.785 18.456 20.605 2.769 7.441315 7500 26.56 177253 1.852 18.515 20.831 2.88 7232986 7560 26.757 177.494 1.752 18.677 20.872 2.805 7.440998 7620 26.583 178255 1.844 18.915 21.147 2.892 7.312241 x 7680 26.531 177.644 1.798 18.907 21.049 2.807 7.498753 7740 26.371 177.877 1.911 19.142 21.173 2.788 7.594333 7800 26.494 177.438 1.84 19.094 21.508 2.909 7.393606 7880 26.491 176.888 1.848 19203 21.522 2.929 7.3479 7920 26.51 177.182 1.922 19.351 21.435 2.695 7.953618 7880 26.462 178.867 1.845 19.498 21.802 2.832 7.698446 8040 26296 177.713 1.905 19.73 22.033 2.866 7.687718 8100 26.398 179.018 1.945 19.821 22.11 2.985 7.407035 8160 26.353 178.987 1.928 19.895 22.338 3.103 7.19884 8220 26262 179.069 1.897 20.016 22.347 3.056 7.3125 8280 26.315 178.381 1.951 20.12 22.379 2.975 7.522353 8340 26269 181268 1.9 20271 22.685 3.049 7.440144 8400 26.35 18023 1.911 20266 22.653 3.016 7.510942 8460 26.407 180.183 1.984 20.543 22.717 2.864 7.931913 8520 26.173 179.792 1.983 20.677 22.997 3.073 7.483567 8580 26.119 181.116 . 1.897 20.723 23.059 3.108 7.419241 8640 26269 180.655 2.029 21.025 23.178 3.035 7.636903 8700 25.94 180238 2.001 20.986 23281 3.145 7.402544 8760 26.159 180.788 2.019 21.153 23264 2.986 7.791025 8820 26.127 181202 2.024 21282 23.508 3.121 7.532201 8880 25.936 181.938 1.942 21.346 23.693 3233 7.328487 8940 25.894 180.844 2.05 21.582 23.691 3201 7.401125 9000 25.967 180.769 2.042 21.668 23.851 3.17 7.523975 9060 25.885 181.056 2.034 21.767 23.953 3.163 7.572874 9120 25.706 180.918 2.109 21.82 24.048 3.126 7.692898 9180 214
25.889 181.681 2.039 21.937 24.361 326 7.472699 9240 25.819 181.48 2.09 22.079 2428 3.18 7.63522 9300 25.798 99 99Q 181.592 2.103 24.432 3241 7.538414 9360 25.625 181207 2.157 22.394 24.535 3.161 7.761784 9420 25.61 181244 2.185 22.493 24.691 3.341 7.390302 9480 25.654 182.015 2201 22.651 24.772 3268 7.580171 9540 25.6 181.797 2.132 22.688 24.882 3268 7.607711 9800 25.641 182.785 2.154 22.921 2521 3.417 7.377817 9680 25.448 181.498 2.28 23.141 25.172 3.315 7.593363 9720 25.371 182.162 2.162 23.035 25293 3.513 7.199829 9780 25.373 181.402 2218 23.116 25.417 3.447 7.373658 9840 25237 182.113 2.189 23214 25.666 3.537 7256432 9900 25201 181.455 2265 23.365 25.498 3.301 7.724326 9980 25253 182.962 2.144 23.422 25.802 3.491 7.391005 10020 25.197 181.715 2.315 23.565 25.738 3.398 7574456 10080 25.152 181.771 2246 23.685 25.953 3.493 7.430003 10140 2522 182.616 2.346 23.858 26.129 3555 7.34993 10200 25.111 183.135 2284 23.99 26.087 3.48 7.490517 10260 25.185 183.374 2291 23.951 2627 3.471 7.568424 10320 25.143 183.405 2297 24.175 26.616 3.544 7510158 10380 25.115 183285 2249 24205 26.636 3.557 7.488333 10440 24.905 183.36 2208 24272 26.624 3.531 7.540074 10500 24.781 183.45 2292 24.429 26.738 3.492 7.65693 10560 24.857 1832 2.328 24.611 26.782 3.651 7.335525 10820 24.948 183.906 2296 24.683 27.024 3.57 7.569748 10880 24.783 183.725 2.381 24.859 26.959 3.576 7.53887 10740 24.65 183.594 2.331 24.824 27.18 3.571 7.611313 10800 24.656 184.088 2.349 25.014 27282 3.606 7.565724 10860 24.755 183.706 2.397 25214 27.392 3.605 7.598336 10920 24.61 183.748 2.361 25246 27.406 3.655 7.498222 10980 24.616 183284 2.434 25.38 27.627 3.775 7.318411 11040 24.645 183.631 2.43 25.32 27.704 3.649 7.592217 11100 24.542 183.595 2.403 25.444 27.724 3.69 7.513279 11160 24.572 183.742 2.498 25.613 27.742 3.641 7.619335 11220 24.374 183.545 2.471 25.585 27.984 3.693 7577579 11280 24.554 184.136 2.495 25.887 27.958 3.675 7.607619 11340 24.385 183.349 2.535 25.838 28.147 3.69 7.627913 11400 24.408 183.784 2.531 25.977 28239 3.646 7.7452 11460 24.421 184.109 2.532 26.04 28.565 3.921 7285131 11520 24.393 183.758 2.564 26.189 28.362 3.586 7.909091 11580 24244 184.388 2.526 26.383 28.578 3.868 7.388314 11640 24.078 184267 2.527 26.343 28.69 3.758 7.63438 11700 24.072 184.653 2.565 26.549 28.673 3.771 7.603553 11760 24.072 184.643 2.511 26.588 28.817 3.796 7.591412 11820 24.125 184.533 2.636 26.623 28.908 3.802 7.603367 11880 23.899 184.357 2.563 26.72 29.119 3.833 7.596921 11940 24.108 185.516 2.613 26.862 292 3.895 7.496791 . 12000 23.951 185.46 2.491 26.918 29.479 3.947 7.46871 12060 23.917 185.335 2.591 27.069 29.333 3.928 7.467668 12120 23.826 184.951 2.644 27249 29.462 4.008 7.350798 12180 23.82 186.131 2.628 27.313 29.76 4.035 7.375465 12240 23.783 186.343 2.592 27.437 29.762 4.06 7.330542 12300 215
23.805 185.812 2.654 27.531 29.834 4.045 7.375525 12360 23.774 185.861 2.628 27.583 29.773 3.946 7.545109 12420 23.663 185.609 2.693 27.67 30.119 4.043 7.449666 12480 23.619 185.979 2.636 27.697 29.98 4.003 7.489383 12540 23.703 186.038 2.705 27.769 30293 4.02 7.535572 12600 23.589 186.501 2.65 27.876 30.155 3.951 7.632245 12660 23.465 186.484 2.682 28.125 30.365 4.09 7.424205 12720 23.461 186.143 2.749 28.082 30.313 3.985 7.645145 12780 23.352 18626 2.712 28.097 30.464 4.012 7.59322 12840 23.385 187.056 2.625 28.256 30.726 4.146 7.410999 12900 23.336 187.353 2.734 28.528 30.777 4.175 7.371737 12960 23.351 186.804 2.718 28.54 30.807 4.078 7.554438 13020 23245 186.583 2.798 28.505 30.904 4.148 7.450338 13080 23.108 187.334 2.724 28.678 31.179 4281 7283111 13140 23211 186.598 2.805 28.646 31.07 4.127 7.528471 13200 23.084 187.51 2.721 28.93 31.336 4.175 7.505629 13260 23.141 187.706 2.769 28.903 31294 4231 7.39836 13320 23.073 187.994 2.782 29.082 31.49 4212 7.476258 13360 22.906 187291 2.849 29.149 31.356 4.063 7.71745 13440 23.028 188.548 2.751 29.193 31.701 4.172 7.588514 13500 22.892 187;868 2.754 29.324 31.581 4.134 7.639332 13560 22.714 187.778 2.764 29.332 31.735 4241 7.482905 13620 22.807 187.805 2.814 29.414 31.775 4.344 7.314687 13680 22.845 187.873 2.847 29.468 31.951 4244 7.528511 13740 22.803 188.57 2.773 29.593 32.112 4.371 7.346603 13800 22.787 188.375 2.808 29.74 32.089 4.325 7.419422 13860 22.58 188.572 2.833 29.771 32296 4.384 7.366788 13920 22.675 188.824 2.795 29.872 32.373 4.483 722128 13980 22.594 188.458 2.845 29.943 32.378 4.39 7.375399 14040 22.573 188.634 2.824 30.047 32.444 422 7.688152 14100 22.666 189249 2.809 30.144 32.66 4.361 7.489108 14160 22.423 189.129 2.848 30.257 32.596 4.405 7.399773 14220 22.449 189.091 2.893 30.373 32.744 4.364 7.503208 14280 22234 189.126 2.856 30.335 32.816 4.421 7.422755 14340 22291 189.077 2.901 30.442 32.903 4.361 7.544829 14400 22253 189.365 2.917 30.517 33.032 4.469 7.391363 14460 22.114 189.993 2.866 30.601 33204 4.56 7281579 14520 22286 189.999 2.896 30.728 33.128 4.457 7.432802 14580 22.066 189.388 2.843 30.587 33239 4.56 7289254 14640 22.08 190.037 2.879 30.895 33258 4.52 7.357985 14700 22.033 189.658 2.887 30.848 33.345 4.477 7.448068 14760 22.094 189.349 2.986 30.906 33.352 4.378 7.61809 14820 22.043 190.486 2.922 31.033 33.71 4.584 7.353839 14880 21.902 190.497 2.873 31.202 33.667 4.401 7.649852 14940 21.931 190.36 2.963 31288 33.817 4.625 7.311784 15000 21.823 190.331 2.966 31.376 33.859 4.558 7.428477 15060 21.695 189.978 3.02 31.334 33.808 4.525 7.471381 15120 21.748 190.142 2.948 31.419 33.941 4.578 7.413936 15180 21.738 190.472 2.91 31.504 34273 4.704 7285927 15240 21.632 190.72 3.011 31.668 34.17 4.661 7.331045 15300 21.471 190.158 2.952 31.662 34.167 4.656 7.338273 15360 21.58 190299 3.005 31.758 34221 4.608 7.426432 15420 216
21.593 190.93 2.945 31.789 34.313 4.569 7.509958 154«) 21.42 189.918 3.042 31.801 34.331 4.458 7.700887 15540 21.377 190.715 3.04 32.092 34.337 4.583 7.492254 15600 21.522 191241 3.019 32.001 34.575 4.569 7.567301 15660 21.375 191.192 3.014 32.133 34.683 4.704 7.373087 15720 21.29 190.905 3.075 32.149 34.74 4.642 7.483843 15780 21.17 190.436 3.043 32258 34.68 4.564 7.588598 15840 21.428 191.782 3.095 32.448 35.138 4.902 7.168095 15900 21.169 191.611 3.031 32.515 35.111 4.736 7.41364 15980 21226 191203 3.113 32.566 35241 4.897 7.188447 16020 21.186 192.366 2.994 32.512 35245 4.872 7234195 16080 21.065 192.135 2.994 32.526 35.401 4.872 7266215 16140 21.017 191.326 3.079 32.605 35.147 4.721 7.444821 16200 20.978 192.399 , 3.021 32.834 35.54 4.88 7.165323 16260 20.987 192.541 3.058 32.828 35.63 4.947 7202345 16320 20.807 191.962 3.145 32.92 35.588 4.879 7294118 16380 20.864 192.111 3.079 32.993 35.766 4.846 7.38052 16440 20.855 191.89 3.12 33.093 35.808 4.97 7204829 16500 20.642 191.53 3.073 33.05 35.762 4.909 7284887 16560 20.852 191.803 3212 33.15 35.778 5.022 7.124253 16620 20.647 190.548 3.187 33.143 35.558 4.795 7.415641 166«) 20.621 191.332 3.095 33244 35.926 4.926 7293136 16740 20.545 190.85 3.199 3328 36.009 4.895 7.356282 16800 20.527 191267 3.145 33.418 35.989 4.834 7.440836 16860 20.472 191288 3218 33.395 36227 4.929 7.349767 16920 20.582 191.912 3.151 33.595 36.35 4.982 7298267 16980 20.552 191.969 3.192 33.635 36229 5.031 7201153 17040 20.419 192.367 3.152 33.738 36.312 4.885 7.433367 17100 20.363 191.069 3232 33.644 36219 4.819 7.515875 17160 20.324 191.909 3238 33.912 36.529 4.957 7.369175 17220 20.307 192.569 3245 33.946 36.833 5.046 7299445 17280 20.341 191.314 3.27 33.921 36.585 4.927 7.425411 17340 20.414 191.946 3245 33.913 36.711 5.025 7.305672 17400 20.056 191.918 3225 34.05 36.811 4.983 7.387317 17460 20.081 192.533 3238 34271 37.011 5.065 7.307206 17520 20.078 192.589 3.19 34256 36.965 5.122 7216907 17580 20.03 192.933 3239 34.325 37.053 5.079 7295334 17640 20.082 192.681 3.316 34.377 37.126 5.025 7.388259 17700 19.983 192.9 3273 34.432 37.067 5.1 7268039 17760 19.856 193.018 3.29 34.547 37249 5.052 7.37312 17820 19.897 192.796 3294 34.572 37.32 5.139 7262113 17880 19.821 193237 3274 34.572 37.444 5.184 7222994 17940 19.893 193.326 3252 34.628 37.492 5232 7.165902 18000 19.708 193255 3255 34.748 37.643 5268 7.145596 18060 19.633 193.308 3269 34.83 37.643 5.168 7283862 18120 19.698 193.671 3291 34.869 37.732 5223 7224201 18180 19.661 193.002 3299 34.684 37.455 5.049 7.418301 18240 19.617 193.056 3.302 34.902 37.767 5.137 7.351956 18300 19.525 193.887 3285 34.985 37.897 5284 7.172029 18360 19.528 193.967 3278 35239 37.891 527 7.189943 18420 19.406 193.928 3267 35.132 38.085 5.142 7.406651 18480 19.447 193.853 3.302 35298 37.972 5256 7224505 18540 217
19.434 194.351 3295 35.366 38.021 5.194 7.320177 18800 19.291 194.095 3229 35.411 38289 5.406i 7.078758 18860 19.332 194.372 3273 35.397 38.372 5282: 7264672 18720 19.16 194296 3.311 35.448 38243 5.312 7.19936 18780 19.117 194.467 3294 35.574 38.374 5.362 7.156658 18840 19.258 194.144 3.372 35.505 38.416 5.303 7244201 18900 19.184 194.601 3.363 35.624 38.587 5.356 7204444 18960 18.991 195.682 3267 35.669 38.813 5.497 7.08076 19020 19.014 194.543 3.34 35.746 38.702 5.453 7.097378 19080 18.924 194.041 3.337 35.755 38.656 5272 7.332322 19140 18.924 194.345 3.379 35.951 38.688 523 7.397323 19200 18.873 194.428 3.354 35.915 38.862 5.501 7.064534 19260 18.733 195.327 3289 36.044 38.947 5273 7.388118 19320 18.886 194.973 3.381 36.086 38.999 5.377 7252929 19380 18.63 194.881 3.401 36.17 39 5.422 7.192918 19440 18.823 194.787 3.511 36264 39.014 5.368 7267884 19500 18.665 195.467 3.38 36.351 39229 5.551 7.067015 19560 18.676 195.55 3.417 36.329 39.319 5.542 7.094731 19820 18.685 195.467 3.472 36.436 39.45 5.549 7.109389 19880 18.521 195298 3.452 36.423 39.352 5.453 7216578 19740 18.604 195.841 3.435 36.472 39.485 5.527 7.14402 19800 18.414 195.119 3.38 36.458 39249 5.428 723084 19860 18.311 194.906 3.397 36.597 39216 5.404 7256847 19920 18.547 196.07 3.398 36.585 39.693 5.625 7.056533 19980 18.324 193.922 3.47 36.499 39.409 5.491 7.177017 20040 18.252 194.404 3.474 36.665 39.391 5.412 7278455 20100 18.192 194.415 3.357 36.508 39.607 5.57 7.110772 20160 18.285 193.954 3.524 36.711 39.696 5.515 7.197824 20220 18.054 194.509 3.448 36.78 39.656 5.499 7211493 20280 18238 194.163 3.53 36.872 39.63 5.434 729297 20340 18.146 194.852 3.531 36.873 39.883 5.57 7.160323 20400 18.023 195.035 3.445 36.956 39.868 5.608 7.10913 20460 18.175 194.85 3.476 36.95 40.023 5.614 7.129141 20520 18.108 194.161 3.555 36.9 39.905 5.512 7239659 20580 17.893 195.104 3.482 37.127 40.136 5.572 7203159 20840 17.889 195.5 3.495 37249 40.09 5.701 7.0321 20700 17.914 194.88 3.544 37235 4021 5.676 7.084214 20760 17.891 195.639 3.515 37282 40.367 5.625 7.176356 20820 17.863 195.382 3.578 37.333 40214 5.472 7.34905 20880 17.888 195.449 3.561 37.426 40.433 5.655 7.149956 20940 17.703 195.526 3.526 37.438 40.409 5.676 7.119274 21000 17.722 195.946 3.529 37.553 40.564 5.72 7.091608 21060 17.625 195.677 3.584 37.558 40.572 5.648 7.183428 21120 17.501 195.983 3.591 37.661 40.569 5.705 7.111131 21180 17.605 196.722 3.527 37.515 40.577 5.516 7.356236 21240 17.504 196.186 3.553 37.677 40.724 5.639 7221848 21300 ' 17.321 195.999 3.535 37.643 40.772 5.732 7.11305 21360 17.364 196.133 3.545 37.792 40.787 5.711 7.141832 21420 17.331 195.766 3.596 37.8 40.842 5.709 7.153967 21480 17.319 196.609 3.59 37.922 41.095 5.849 7.025987 21540 17268 196.501 3.633 38.023 41213 5.843 7.053397 21600 17228 197.461 3.604 38.131 41.151 5.896 6.979478 21660 218
17.13 196215 3.562 38.013 41.098 5.847 7.028904 21720 17.152 196.482 3.578 38.088 41.349 5.935 6.966976 21780 17.12 196.776 3.569 38.156 41.34 5.851 7.065459 21840 16.945 197.044 3.601 38283 41277 5.887 7.011551 21900 16.976 196.409. 3.649 3824 41209 . 5.798 7.109903 21960 16.953 196.18 3.59 38242 41.424 5.855 7.074979 22020 16.983 196.37 3.601 38268 41.32 5.82 7.099856 22080 16.84 196.334 3.556 38286 41251 5.775 7.160346 22140 16.843 196.379 3.582 38.346 41.425 5.886 7.037887 22200 16.836 195.763 3.638 38.354 41.654 5.914 7.043287 22260 16.654 196.809 3.496 38.327 41.674 6.051 6.887126 22320 16.721 196.341 3.577 38.42 41.764 5.969 6.998817 22380 16.74 195.778 3.687 38.473 41.681 5.957 6.998978 22440 16.649 198.829 3.583 38.595 41.761 5.874 7.109465 22500 16.643 195.855 3.681 38.526 41.843 5.842 7.162444 22560 16.555 198.739 3.641 38.6 41.814 6.014 6.952777 22620 16.615 196.66 3.645 38.708 41.903 6.051 6.924971 22680 16.419 197.032 3.609 38.819 41.972 6.029 6.961685 22740 16.469 197227 3.644 38.908 41.995 5.972 7.031983 22800 16.503 196.627 3.672 38.844 42.028 6.019 6.982555 22860 16.359 197.456 3.686 38.944 4224 6.157 6.860484 22920 16.358 197.102 3.719 38.934 42294 6 7.049 22980 16.194 197.772 3.649 39.064 42.464 6.113 6.946507 23040 16.153 197298 3.701 39.195 42.526 6.083 6.990958 23100 16.089 197.406 3.604 39.051 42.414 6235 6.802566 23160 16265 196.976 3.653 39.141 42228 6.012 7.023952 23220 16232 197.485 3.652 39.176 42.576 6.071 7.013013 23280 16.073 197.748 3.687 39.311 42.591 6.129 6.949094 23340 15.875 197.74 3.587 39.182 42.541 6.107 6.985941 23400 15.918 197.143 3.66 39253 42.432 . 5.905 7.112303 23460 15.91 197.686 3.67 39299 42.711 6.164 6.929104 23520 15.952 197.108 3.824 39.436 42.529 6.016 7.069315 23580 15.704 197.616 3.664 39.434 42.692 6.161 6.929395 23640 15.803 197.554 3.63 39.426 42.637 6.098 6.991985 23700 15.761 197.6 3.733 39.527 42.877 6.182 6.935781 23760 15.59 198.022 3.712 39.598 42.891 6.163 6.959435 23820 15.679 198.121 3.721 39.655 43.131 6.18 6.979126 23880 15.514 197.821 3.745 39.734 42.965 6.169 6.964662 23940 15.603 197.89 3.783 39.922 43.081 6259 6.883048 24000 15.71 198217 3.752 39.681 43299 6.347 6.821963 24060 15.616 197.87 3.771 39.815 43.157 6.151 7.016258 24120 15.467 197.769 3.741 39.773 43.056 6.179 6.968118 24180 15.402 197.893 3.741 39.88 43.163 6208 6.952803 24240 15.472 197.83 3.766 39.868 43226 6.179 6.99563 24300 15.359 198.407 3.755 39.952 43253 6.144 7.039876 24360 15.371 198.125 3.787 40.036 43.341 6288 6.892653 24420 15.477 197.317 3.767 39.898 43.068 6.081 7.082388 24480 1527 198.433 3.743 40.135 43.592 6.357 6.857323 24540 15252 199.197 3.751 40229 43.588 6.37 6.8427 24600 15279 198.033 3.773 40.137 43.524 6.302 6.906379 24660 15238 198.965 3.783 40.164 43.516 6.158 7.06658 24720 15.119 198.606 3.808 40258 43.715 625 6.9944 24780 219
15.122 199218 3.754 40.303 43.608 6.309 6.91203 24840 14.899 198.131 3.806 40.451 43.886 6.397 6.860403 24900 14.88 198.622 3.745 40.472 43.837 6.388 6.864547 24960 14.728 198.693 3.686 40.488 43.903 6.446 6.81089 25020 14.841 198.044 3.794 40.381 43.692 6246 6.995197 25080 14.816 198298 3.794 40.325 43.935 6.362 6.905847 25140 14.807 198.078 3.887 40.532 43.829 6242 7.021628 25200 14.906 197.985 3.857 40.52 43.937 6.346 6.923574 25260 14.631 198.349 3.817 40.65 44 6223 7.070545 25320 14.792 198.808 3.841 40.727 43.985 6.334 6.944269 25380 14.692 197.984 3.888 40.766 44.099 6.457 6.829642 25440 14.629 198.9 3.881 40.808 44248 6.308 7.014585 25500 14.48 199.314 3.785 40.791 44.428 6.5 6.835077 25560 14.462 198.888 3.799 40.825 44298 6.441 6.877193 25620 14.559 198.804 3.852 40.932 44.346 6.468 6.856215 25680 14.466 198.893 3.863 40.902 44.36 6.52 6.803681 25740 14.333 199.319 3.885 40.94 44.554 6.498 6.858682 25800 14.35 199.501 3.826 40.96 44.557 6.529 6.824475 25860 14.227 199.556 3.869 41.102 44.541 6.449 6.908652 25920 14.396 198.825 3.933 41212 44.672 6.56 6.809756 25980 14.383 199.141 3.902 41.152 44.584 6.583 6.772596 26040 14.247 199.485 3.863 41.126 44.629 6.569 6.79388 26100 14283 199.037 3.94 41228 44.451 6.411 6.933552 26160 14.338 199.425 3.925 41265 44.742 6.574 6.805902 26220 14237 199.409 3.944 41.402 44.743 6.405 6.985636 26280 14.139 199.853 3.873 41262 44.982 6.75 6.664 26340 14.182 199.867 3.856 41.356 44.997 6.742 6.674132 26400 14.098 199.161 3.978 41.463 44.712 6.457 6.924578 26460 14.074 199.48 3.839 41.477 44.949 6.583 6.828042 26520 14 200.62 3.873 41.517 45239 6.728 6.723989 26580 13.988 200.386 3.906 41.629 45274 6.708 6.751268 26640 13.993 199.412 3.986 41.495 45.083 6.588 6.840164 26700 13.909 199.698 3.995 41.593 45.118 6.601 6.835025 26760 13.799 200.473 3.872 41.657 45.448 6.8 6.683529 26820 13.834 200.004 3.942 41.824 45216 6.586 6.865472 268«) 13.821 199.897 3.931 41.697 45.087 6.499 6.937529 26940 13.723 199.776 4.012 41.818 45.301 6.588 6.87629 27000 13.737 199.578 3.843 41.641 45291 6.588 6.874772 27060 13.705 200.063 3.972 41.846 45.4 6.663 6.813748 27120 13.646 199.917 3.966 41.862 45.048 6.489 6.94221 27180 13.631 199.889 3.985 41.837 45.345 6.584 6.887151 27240 13.699 200.152 3.999 41.883 45.474 6.604 6.885827 27300 13.62 200.034 3.98 41.904 45.554 6.563 6.941033 27360 13.464 201.037 3.861 42.066 45.607 6.633 6.875773 27420 13.541 200.665 3.931 42.023 45.743 6.785 6.741783 27480 13.366 200.739 3.938 4223 45.554 6.671 6.828661 27540 13.35 200.994 3.984 42.32 45.84 6.803 6.738204 27600 13.467 200.557 3.998 42.19 45.848 6.772 6.77023 27660 13.536 200.315 4.02 42.106 45.803 6.871 6.666133 27720 13.307 200.889 4.032 42257 45.957 6.744 6.814502 27780 13.389 200.61 4.03 42289 46.0666.854 6.721039 27840 13212 200.93 3.986 42.315 45.967 6.827 6.733119 27900 220
13.272 200.777 4 42.324 46.035 6.878 6.693079 27980 13.141 200.607 3.996 42.398 45.895 6.654 6.897355 28020 13.104 200.908 3.932 42.414 46.115 6.729 6.853173 28080 13.141 200.75 3.959 42.467 45.983 6.812 6.747358 28140 13.127 201.825 3.986 42.528 46.327 6.846 6.767017 28200 13.191 200.481 4.093 42.497 46.036 6.674 6.897812 28260 13.033 201.487 4.035 42.55 46.185 6.811 6.780943 28320 13.147 200.754 4.055 42.615 46231 6.805 6.793681 28380 12.988 201.662 4.022 42.606 46.38 6.834 6.786655 28440 12.888 201.569 4.047 42.806 46276 6.854 6.751678 28500 13.056 200.836 4.011 42.598 46212 6.843 6.753178 28560 13.002 200.691 4.119 42.698 46.301 6.765 6.844198 28620 12.881 201.312 4.045 42.824 46.532 7.088 6.564898 28880 12.853 201.632 4.002 42.723 46.451 6.982 6.652985 28740 12.844 201.809 4.023 42.865 46.664 6.874 6.788478 28800 12.763 201223 4.1 42.869 46.62 6.983 6.676214 288% 12.729 201287 4.101 42.893 46.404 6.722 6.903303 28920 12.749 200.938 4.107 42.894 46.738 7.004 6.673044 28980 12.649 201217 4.023 42.868 46.508 6.884 6.755956 29040 12.738 201.671 4.101 43.041 46.794 6.955 6.728109 29100 12.59 201.841 4.109 43.071 46.643 6.957 6.70447 29160 12.66 201.61 4.081 43.083 46.983 7.112 6.603346 29220 12.451 202254 4.119 43.198 46.808 6.879 6.804477 29280 12.454 202.366 4.079 43212 47.198 7.185 6.568685 29340 12.449 202266 4.132 43.326 46.802 6.885 6.797676 29400 12.313 202.37 4.03 43276 47.125 6.984 6.747566 29460 12.541 201.345 4.189 432 46.721 6.857 6.813621 29520 12.411 202.108 4.114 43239 47.059 7.017 6.708427 29580 12.495 201.88 4.084 43261 46.862 6.78 6.911799 29840 12296 202.347 4.065 43.367 47.081 6.948 6.773316 29700 12217 . 202.788 4.089 43.427 47204 7.037 6.707972 29760 12272 202.321 4.118 43.507 47.165 6.973 6.763947 298% 12.32 201.952 4.158 43.317 47.048 6.995 6.725947 29880 12.146 203205 4.089 43.55 47.492 7.09 6.698449 29940 50.652
45.652"
40.652-
35.652-
30.652-
25.652 221
20.652-
15.652
10.652
5.652-
0.652 0 222
Filename: 0216BHK.SER
Starting material: cis-2-methyl-3-phenyl-1,5-heptadiene
Concentration: 0.035OM
Temperature: 298K 0126BHX.SER Integrals EFGH IJ K 67.311 0.035 0.108 1.124 18.598 4.171 -0.042 68.183 0.023 0.04 1.144 19.303 4.172 0.13 66.771 •0.026 0.073 0.87 18.904 4.187 0262 68.684 -0.02 0.01 1.052 18.885 4.172 0.483 68.363 -0.011 0.052 1.136 19.118 4.041 0.515 67.817 0.016 0.074 1.145 19.037 4.022 0.712 69.007 0.066 0.174 0.973 19.041 3.988 0.814 68206 -0.006 0.094 0.908 19218 3.923 0.937 67.715 0.034 0.088 1.165 1923 3.804 1.053 68.355 0 0.076 1.144 19.049 3.775 1.143 67.663 0.042 0.133 1.098 19.373 3.724 1283 68.387 0.004 0.117 0.901 19.309 3.708 1.47 68.544 0.01 0.087 1.035 19.816 3.664 1.566 68.504 -0.022 0.084 1203 19216 3.588 1.734 68.32 0.033 0.099 1281 19254 3.478 1.777 68.999 -0.031 0.069 1.129 19.468 3.452 1.986 68.368 0.004 0.151 1.085 19.08 3.361 2.028 68.565 -0.033 0.053 0.937 19282 3.33 2.176 68.337 -0.046 0.115 1.09 19.036 3259 226 69.172 -0.015 0.011 1.117 19.448 3256 2.395 68.516 -0.04 0.135 0.874 19.5 3.174 2.507 68.686 -0.028 0.059 1.092 19.197 3.105 2.604 69.086 -0.016 0.084 1.004 19.781 3.03 2.706 68.609 0.004 0.093 0.895 19.344 2.97 2.76 68.196 0.04 0.092 0.98 19.543 2.942 2.871 68.702 -0.036 0.136 1 19228 2.918 2.941 68.763 -0.032 0.164 1.171 19.198 2.884 3.006 69.534 -0.089 0.156 1.021 19.048 2.818 3.095 69.345 0.019 0.107 1.07 19.412 2.751 3.194 69.315 -0.01 0.109 0.949 19263 2.721 3238 69.594 -0.041 0.105 0.997 18.932 2.678 3.316 68.989 -0.053 0.139 0.908 19238 2.63 3.383 68.727 -0.005 0.139 0.993 19218 2.601 3.41 69209 0.005 0.163 0.976 19.357 2.525 3.488 69.707 -0.012 0211 0.895 18.785 2.533 3.484 69.49 0.006 0.184 0.901 19.133 2.47 3.58 68.74 0.037 0.159 1.18 19.175 2.463 3.626 68.886 -0.043 0.152 1.046 18.773 2.448 3.628 68.815 -0.005 0.166 1.118 19.425 2.384 3.645 69.072 -0.011 0.194 0.957 19.008 2.366 3.697 69.044 0.007 0281 0.967 18.755 2.375 3.771 68.998 0.032 0242 0.815 18.997 2.308 3.787 69.309 0.008 0258 0.97 18.972 2.336 3.78 68.162 -0.024 0.197 1.067 18.49 2291 3.776 68.426 -0.033 0216 0.961 18.738 2282 3.813 68.705 -0.09 0269 1.054 18.483 2216 3.818 69.599 -0.043 0.23 1.004 18.591 2244 3.829 69.307 0.049 0224 1.086 18.811 2223 3.885 69.869 -0.029 0.313 1.132 18.838 2243 3.902 68.371 0.017 0241 1.172 18.661 2.164 3.839 224
68.74 0.003 0.309 1.005 18.752 2213 3.873 68.52 -0.056 0.27 1.013 19.002 2219 3.979 68.566 0.015 0.311 1203 18.702 2216 3.88 69.267 -0.023 0.199 1.18 18.721 2.166 3.923 69.037 0.001 0247 1.018 18.523 2.14 3.944 68.981 0.031 0.379 1.19 18.461 2.159 3.895 68.66 0.008 0.317 0.914 18.497 2.161 3.917 68.994 -0.004 0.372 0.977 18.509 2.165 4.008 69.316 0.028 0.307 0.904 18.814 2.135 3.904 69.292 -0.075 0.33 1.034 18.439 2.154 3.936 225
L M N OP Q timo(s ) 6.638 30.804 -0.098 -0.039 0.301 0.104 60 6.871 30.888 -0.097 -0.014 0267 0.115 120 6.805 31.35 -0.131 -0.111 0224 0.004 180 7.066 31.775 -0.148 -0.15 0.136 0.194 240 7.095 31.554 -0.139 -0.033 0.341 0.161 300 7.184 31.627 -0.086 -0.068 0299 0.191 360 7.194 31.922 -0.09 -0.047 0.193 0.15 420 7215 31.723 • -0.12 -0.026 0.025 0.072 480 7217 31.92 -0.091 -0.053 -0.016 -0.117 540 7.021 31.826 -0.061 -0.057 0.139 0.037 600 7.051 31.92 -0.08 -0.109 0.152 0.009 660 7287 3225 -0.097 -0.045 0.448 0.123 720 7222 32.113 -0.12 -0.077 02 0.037 780 7.176 32.101 •0.139 -0.088 0.312 0.031 840 7.188 32.04 -0.085 -0.151 0.463 0.117 900 7.462 32.343 -0.128 •0.18 0215 0.09 960 722 32.316 -0.124 -0.052 0229 0.051 1020 7.321 32.485 -0.095 -0.025 0.327 0.146 1080 7258 32.563 -0.104 -0.042 0.322 0.081 1140 7215 32.476 -0.087 -0.064 0.155 0.021 1200 7285 32.667 -0.089 -0.054 0277 0.096 1260 7.331 32.399 -0.094 -0.012 0.501 0211 1320 7.365 32.66 -0.084 -0.111 0.406 0206 1380 7267 32.602 -0.068 -0.091 0.385 0.179 1440 7201 32.646 -0.096 -0.09 0.3 0.113 1500 726 32.478 -0.08 -0.133 0.403 0.155 1560 7.325 32.596 -0.07 -0.066 0.395 0.069 1620 7.383 32.817 -0.103 -0.04 0.607 0.161 1680 7.331 32.88 -0.038 -0.044 0.489 0.122 1740 7.39 33.033 -0.024 0.041 0.382 0.08 1800 7203 33.147 -0.026 0.065 0.383 0.159 1860 7297 32.855 -0.004 0.037 027 -0.016 1920 7.395 33.146 0.005 -0.06 0.526 0.112 1980 7.375 33.166 0.017 0.082 0.741 0.139 2040 7.311 32.848 0.008 -0.018 0.649 0.199 2100 7273 33.009 0.028 0.003 0.67 0.057 2160 7.38 33258 -0.021 0.033 0.797 0.181 2220 7.348 33.21 0.017 0.053 0.647 0.045 2280 7.309 33.199 0.032 0.113 0.847 0.081 2340 7.384 33.325 0.063 0.156 0.586 0.183 2400 7.47 33.307 0.025 0.113 0.755 0.079 2460 7243 33265 0.029 0.18 0.536 0.13 2520 7292 33293 0.054 0.156 0.897 0.142 2580 7.189 33.159 0.082 0207 0.798 0.024 -2640 7212 33235 0.081 0205 0.848 0.123 2700 7.48 33.395 0.11 0234 0.706 0.04 2760 7.393 33.463 0.111 0268 0.868 0.144 2820 7.181 33.571 0.094 0235 0.979 0.162 2880 7292 33.732 0.059 0.193 0.685 0.019 2940 7.165 33.829 0.121 0292 0.941 0.158 3000 226
7.312 33584 0.113 0.28 0.99 0.156 3080 7.123 33.665 0.15 0.353 0.98 0.133 3120 7.137 33.787 0.12 0.365 1.172 0257 3180 7274 33.845 0.134 0.356 1.071 0241 3240 7213 33.803 0.116 0.376 1233 0.17 3300 7.146 33.496 0.178 0.456 1201 0.13 3360 7.169 33.84 0.104 0.466 1.172 0.191 3420 7.163 34.385 0.11 0.379 1269 0216 3480 7.197 34.063 0.167 0.447 1.306 0254 3540 7.044 34.189 0.18 0.528 1237 0.102 3600 227
7.00-
6. 00-
5.00-
4.00-
3.00-
2.00- 228
Filename: 0126BK2.SER
Starting material: continuation of. 0126BHK.SER after I hour of data collection.
Temperature: 298K 229
0126BK2.SER Integrals BC D E FG H 69.888 -0.001 0.39 1.113 18.368 2.122 3.913 69.078 -0.009 0.366 1239 18.448 2.102 3.982 69.202 0.049 0.535 1.042 17.904 2.099 3.884 68.512 -0.053 0203 1.347 17.981 2.088 3.919 68.932 0.022 0.566 1246 17.551 2.006 3.786 68.434 0.004 0.654 125 17.324 2.013 3.793 68.911 0.028 0.617 1.424 17.363 1.973 3.808 69.515 0.04 0.648 1.193 17.102 1.92 3.704 68.888 0.042 0.815 1.374 17223 1.976 3.743 68256 0.025 0.828 1.418 17.07 1.88 3.615 70.159 -0.038 0.811 1.448 16.508 1.898 3.638 69.158 0.058 0.865 1.676 16.792 1.884 3.651 69.102 0.058 0.911 1.532 16.605 1.882 3.56 69.172 0.054 0.993 1.519 16.5 1.868 3.577 68.682 -0.002 1.032 1.853 16.134 1.847 3.486 70.084 0.027 1.079 1.463 16.004 1.792 3.468 68.962 0.063 1.045 1.692 1626 1.79 3.422 69.448 0.008 1.172 1.765 15.829 1.765 3.442 69.078 0.12 1213 1.986 16.051 1.759 3.424 68.696 0.025 1256 1.736 15.666 1.742 3.401 69.613 0.03 1.302 1.845 15294 1.741 3.371 68.532 0.04 1264 1.783 15.159 1.708 3.317 68.869 0.074 1273 1.899 15.434 1.69 3.303 69.04 0.104 1.368 2.106 15.681 1.663 3.281 69.434 0.028 1.319 1.85 15225 1.694 3.313 69.354 0.058 1.405 2.008 14.858 1.655 3223 69.037 0.006 1.426 2.03 15.03 1.652 3.181 68.832 0.042 1.509 2.01 14.781 1.626 3.172 69237 0.1 1.475 2.065 14.817 1.636 3223 68.935 0.067 1.585 2.046 14.782 1.607 3.145 68.78 0.071 1.53 2.152 14.777 1.663 3231 68.951 0.086 1.618 2256 14.404 1.635 3.123 68.545 0.067 1.675 2.158 13.968 1.616 3.116 67.945 0.092 1.591 2.325 14.034 1.592 3.122 69.14 0.067 1.634 2.111 14.362 1.55 3.094 69274 0.066 1.7 2.354 14252 1.592 3.097 68.433 0.007 1.751 2.537 14.179 1.538 3.082 69.349 0.086 1.743 2.35 1425 1.548 3.031 68.719 0.062 1.767 2236 14.017 1.524 3.042 69.604 0.082 1.745 2.317 13.937 1.528 2.944 68.631 0.051 1.832 2.422 13.505 1.519 2.996 69.078 0.054 1.808 2.411. 13.873 1.505 3.014 69.585 0.131 1.827 2.369 13.373 1.516 2.968 68.526 0.104 1.89 2.374 13.45 1.448 2.97 69.373 0.066 1.846 2.485 13.391 1.5 2.984 69.117 0.129 1.973 2.531 13.753 1.425 2.916 69.685 0.086 1.989 2.48 13.334 1.468 2.876 69295 0.078 1.977 2.474 13.484 1.439 2.857 67.774 0.128 2.02 2.551 13.474 1.47 2.832 68.61 0.106 1.962 2.679 13.175 1.426 2.843 230
68.572 0.038 1.999 2.359 12.983 1.441 2.903 69.139 0.116 2.083 2.395 13.354 1.446 2.882 68.915 0.125 2.157 2.5 12.957 1.44 2.83 68.839 0.085 2.108 2.564 12.79 1.44 2.836 69.241 0.113 2.104 2.864 12.692 1.392 2.819 69.468 0.087 2.151 2.615 12.536 1.402 2.78 69.207 0.122 2.174 2.557 12.972 1.383 2.791 67.935 0.144 2.144 2.666 12268 1.448 2.812 67.81 0.15 2213 2.72 12.449 1.427 2.765 69.496 0.147 2218 2.806 12.674 1.39 2.739 69.016 0.186 2.158 2.728 12.567 1.383 2.759 69.61 0.1 2283 2.636 12.31 1.328 2.72 69.301 0.136 2226 2.499 12.43 1.387 2.736 68.67 0.087 2222 2.755 12.584 1.329 2.745 69.942 0.146 2.31 2.631 12.184 1.323 2.679 68.92 0.14 2.337 2.701 12.604 1.317 2.698 69.565 0.087 2202 2.78 11.835 1.328 2.683 68.837 0.093 2.317 2.641 12.051 1.325 2.672 69.285 0.154 2.306 2.681 12.137 1.323 2.67 68.72 0.153 2.338 2.806 11.941 1.322 2.654 69.324 0.03 2.37 2.734 11.734 1288 2.642 69.305 0.145 2.371 2.96 11.922 1.323 2.67 69.165 0.163 2.396 2.932 11.792 1298 2.606 68.186 0.142 2.358 2.667 11.988 1.313 2.591 69.798 0.117 2.396 2.838 11.783 1275 2.616 69.181 0.096 2.478 2.95 11.731 1295 2.604 68.624 0.147 2.446 2.605 11.66 1.308 2.636 68.328 0.117 2.426 2.829 11.807 1277 2.585 68.915 0.132 2.479 2.688 11.632 1279 2.549 68.467 0.124 2.533 2.998 11.73 1256 2.558 68.847 0.127 2.452 3.084 11.713 1271 2.558 68.583 0.109 2.52 2.959 11.498 1278 2.595 69.106 0.126 2.57 3.069 11.372 1242 2.543 68.883 0.119 2.54 3.178 11.508 1279 2.55 68.959 0.176 2.585 2.811 11.44 123 2.493 67.512 0.091 2.502 2.985 11.521 1245 2.51 69.11 0206 2.567 3.002 11.319 1238 2.483 68.578 0.162 2.619 2.917 11.18 1221 2.495 68.769 0.116 2.536 3.025 11.102 1229 2.5 68.46 0.132 2.625 2.856 11238 1213 2.418 68.876 0.102 2.653 3.099 11.456 1229 2.475 68.952 0.064 2.59 2.908 11.087 1211 2.424 68.48 0.137 2.627 3.061 11.397 1225 2.47 69.244 0.146 2.732 3.097 10.768 1.199 2.426 68.558 0.151 2.724 3.086 11.069 1.163 2.469 70.367 0.172 2.705 2.891 10.742 1.189 2.465 69.134 0.117 2.676 3.198 10.636 1.19 2.437 68.638 0.147 2.732 3.058 10.591 1205 2.41 68.729 0.068 2.73 3.112 10.614 1.169 2.398 68.616 0224 2.778 3.122 11.079 1.182 2.413 68.302 0.151 2.683 3.013 10.54 1.179 2.416 69.103 0.143 2.783 3223 10.862 1.155 2.385 231
68.291 0.146 2.724 2.998 10.885 1.163 2.409 68.641 022 2.82 3249 10.524 1.179 2.339 69.469 0.134 2.807 3.054 10.493 1.193 2.385 69.341 0.105 2.751 3.132 10.113 1.166 2.36 69.02 0.161 2.804 2.958 10.898 1.154 2.35 68.614 0.165 2.768 3224 10.715 1.138 2.334 68.563 023 2.852 325 10.842 1.152 2.354 68214 0.184 2.752 3.006 10.553 1.133 2.323 69.383 0.11 2.793 3.395 10.346 1.169 2.355 68.701 0.111 2.736 3.053 10.44 1.15 2.367 68.624 0.163 2.804 3.039 10.587 1.148 2.319 68253 0.137 2.899 3.319 10.597 1.12 2.307 67.731 0.177 2.84 3238 10.573 1.108 2.308 68.828 0.173 2.832 3.341 10289 1.081 2264 67.626 0.136 2.828 3.642 10.191 1.14 2273 68.684 0.155 2.87 3.176 9.879 1.158 2277 69.384 0.159 2.915 3.397 9.688 1.098 2244 68.462 0.183 2.956 3.098 10.189 1.12 2238 68.63 0.185 3.034 3.064 10219 1.124 2255 69.041 0.163 2.946 3.17 9.794 1.099 2266 68.514 0.16 2.844 3.077 9.834 1.087 2251 68.374 0.178 2.951 3.322 10.034 1.122 2271 67.758 0.186 2.981 3245 10.054 1.053 2256 68.538 0.152 2.97 3.414 9.997 1.083 2236 68.474 0.127 2.983 3.362 10.307 1.113 2242 69274 0.162 2.938 3.475 10.087 1.058 2209 68.192 0.154 2.993 3233 9.972 1.098 2255 69.166 0.187 3.025 3.397 10.14 1.111 221 68.895 0255 3.02 3222 9.988 1.067 2255 68.782 0.177 2.933 3.446 9.498 1.07 2226 68.708 0.173 3.017 3288 9.888 1.049 2219 68.856 0.147 2.923 3.42 10.035 1.08 2253 69.186 0.182 3.121 3.421 9.415 1.015 2201 68.954 0.146 3.075 3.397 9.884 1.089 2.165 69262 0.177 3.014 3.488 9.705 1.061 2219 68.307 0.167 3.035 3226 9.768 1.062 2.176 68.761 0.103 3.002 3291 9.857 1.058 2.189 68.124 0.18 3.088 3298 9.568 1.05 2.15 6923 0.159 3.089 3218 9.646 1.058 2.181 68.853 0.147 3.108 3.193 9.691 1.055 2.173 69241 0205 3.071 3263 9.465 1.04 2.151 68.792 0.198 3.022 3.324 9.573 1.107 2.168 68.359 0233 3.128 3.47 9.578 1.028 2.153 6823 0.186 3.075 3216 9.504 1.026 2.147 68.91 0.184 3.146 3.546 9.434 1.05 2.124 68295 0.148 3.113 3.464 9.712 1.065 2.157 68257 0219 3.078 3.338 9.855 0.996 2.145 68.482 0.157 3.105 3.377 9.435 1.052 2.122 69.439 0.167 3219 3.422 9.164 1.054 2.111 69.859 0223 3.173 324 9.587 1.029 2.117 68.73 0209 3.123 3.331 9.471 1.012 2.121 68.571 0209 3.081 3.645 9.582 0.984 2.097 232
68.515 0208 3258 3.192 9.529 0.992 2.066 69.143 0.193 3.092 3259 9.741 1.078 2.142 69.043 0225 3.125 3.339 9.395 1.032 2.06 68.467 0.146 3.183 3.381 9.557 1.002 2.056 68.269 0.18 3.108 326 9.693 0.977 2.09 69.171 0236 3.192 3.442 8.969 0.97 2.103 69.547 0242 3203 3.52 9.485 0.997 2.099 68.634 0.185 3.153 3299 9.137 0.988 2.09 68.736 0213 3227 3.519 9.315 0.989 2.057 68.539 0.17 3242 3.647 8.943 1.017 2.06 69.964 0212 3.165 3.477 9294 1.016 2.059 68.922 0231 3227 3.41 9.028 0.984 2.073 68.368 0.181 3246 3.363 9.114 0.994 2.011 69.155 0.173 3.144 3.346 9208 0.991 2.057 68.085 0.198 3.25 3.484 8.991 0.987 2.054 68.303 0224 3.186 3.643 8.999 0.997 2.013 68.133 0.193 3216 3.472 9.068 0.946 1.975 69.162 0217 3.192 3.566 9204 0.988 2.025 68.762 0.197 3.197 3.569 9.137 0.998 2.081 68277 0.138 3.15 3.496 8.945 0.985 2.033 68.987 0.182 3.314 3.671 8.941 0.995 2.054 69.093 0211 3218 3.632 9.018 0.963 1.978 68.788 0205 3.24 3.567 8.871 0.998 2.044 68.902 0.144 3.183 3.542 9.061 0.969 1.977 68.324 0.184 3239 3.368 9.106 0.942 1.982 69278 0.167 3.176 3.509 8.892 0.979 2.009 68.979 0208 3.342 3.609 9.041 0.988 1.983 68.558 0.193 3215 3.439 8.732 0.98 1.971 68.789 0.199 3216 3.54 9.142 0.897 1.981 68.046 0214 3.315 3.643 8.719 0.949 1.976 68.125 0.145 3297 3.684 8.575 0.959 1.938 68.609 0.188 3208 3.459 9.067 0.93 1.95 69.012 0218 3.319 3.7 8.535 0.964 1.982 68.431 0.179 3.323 3.466 8.509 0.977 1.978 68.34 0.174 3272 3.396 8.774 0.936 1.979 69.186 0216 3268 3.427 8.835 0.94 1.924 67.399 0242 3.307 3.609 8.743 0.931 1.93 67.74 0284 3277 3.39 8.723 0.918 1.927 68.124 0.195 3273 3.565 8.313 0.946 1.913 68.714 0.194 3297 3.441 8249 0.961 1.956 68.576 0236 3.304 3.608 8.467 0.909 1.947 68.354 0239 3.366 3.188 8.617 0.961 1.923 68216 0.192 3252 3.651 8214 0.934 1.908 68277 0.188 3.306 3.461 8.324 0.943 1.891 67.362 0228 3.334 3.496 8.667 0.945 1.922 68288 0.168 3.311 3.409 8.486 0.954 1.936 233
I J K L M N (mo (s ) 7.128 34.536 0.152 0.515 1.416 0233 3660 6.994 34.944 0216 0.714 1.498 0.179 4017 7.119 35.378 0259 0.787 1.809 02 4374 6.885 35.788 0.31 0.969 2.009 0.19 4731 6.973 35.952 0265 1.039 1.974 0.154 5088 6.852 36.702 0.385 1229 2.188 0298 5445 6.78 37.472 0.359 1.33 2.429 0.35 5802 6.73 38.118 0.365 1.437 2.41 0268 6159 6.677 38.932 0.483 1.62 3.005 0.343 6516 6.606 39.343 0.486 1.628 2.98 0.389 6873 6.49 40.486 0.508 1.829 3.084 0.343 7230 6.519 41.474 0.565 2.004 3231 0.416 7587 6.51 42.591 0.658 2.088 3.47 0.423 7944 6.394 43.179 0.574 2.157 3.518 0.431 8301 6.414 44236 0.656 2.317 3.505 0.343 8658 6273 45.387 0.606 2.378 3.863 0.578 9015 6283 45.996 0.638 2.496 4.02 0.451 . 9372 6233 47.386 0.656 2.583 4.016 0226 9729 6221 48.358 0.727 2.694 4263 0.366 10088 6242 49.177 0.732 2.758 4.485 0.504 10443 6.326 50279 0.738 2.859 4.528 0.44 10800 5.989 50.843 0.791 2.911 4.584 0.471 11157 6.033 51.729 0.871 3.03 4.717 0.51 11514 6.016 52.794 0.844 3.148 4.911 0.43 11871 6.044 53.883 0.817 3.195 5264 0.576 12228 5.82 54.083 0.877 3.194 5297 0.562 12585 5.973 54.954 0.848 3.344 522 0.457 12942 5.727 55262 0.847 3.404 5.375 0.612 13299 5.816 55.865 0.912 3.573 5.517 0.645 13656 5.834 56.455 0.946 3.56 5.637 0.618 14013 5.761 57.052 1.012 3.739 5.655 0.526 14370 5.659 57.098 0.977 3.663 5.6 0.492 14727 5.725 57.351 0.998 3.805 5.892 0.616 15084 5.688 57.92 1.048 3.844 5.99 0.614 15441 5.658 57.913 0.985 3.878 6.024 0.591 15798 5.771 58.326 1.107 4.011 6.097 0.5 16155 5.744 58.632 1.034 4.105 6.196 0.584 16512 5.611 58.421 1.079 4.181 6.356 0.503 16869 5.537 58.643 1.117 4237 6245 0.512 17226 5.65 58.755 1.107 4246 6.616 0.681 17583 5.44 58.423 1.189 4.376 6.533 0.658 17940 5.49 58.877 1.175 4.414 6.773 0.72 18297 5.501 58.728 1.133 4.447 6.835 0.655 18654 5.338 59.181 1236 4.554 6.864 0.683 19011 5.467 59242 1246 4.562 6.904 0.67 19368 5.448 59.011 1211 4.605 7.137 0.763 19725 5.348 59.086 1.303 4.751 7.032 0.609 20082 5213 58.976 1249 4.678 6.926 0.624 20439 527 58.954 1289 4.782 7.166 0.723 20796 5.457 58.742 1267 4.78 7.539 0.794 21153 234
5.409 59.053 1243 4.833 7.441 0.714 21510 5.448 59274 1.349 4.937 7.548 0.757 21867 5.416 59.157 1.406 4.992 7.534 0.73 22224 5.218 59202 1.328 4.984 7.484 0.648 22581 5.214 59.409 1.387 5.157 7.681 0.752 22938 5.195 58.809 1.334 5.002 7.845 0.856 23295 5.197 59.423 1.389 5.178 7.813 0.682 23652 5.126 . 58.937 1.402 5.193 7.669 0.85 24009 5.175 58.922 1.466 5206 7.913 0.831 24366 5.058 59.34 1.479 5.308 8.151 0.727 24723 5.083 59.3 1.403 5247 8.11 0.903 25080 5.033 59.163 1.546 5.409 7.954 0.708 25437 5.063 58.984 1.448 5.322 8.012 0.843 25794 5.144 59271 1.5 5.397 8.103 0.83 26151 5.087 59.09 1.522 5.48 8279 0.773 26508 5.052 59.309 1.567 5.602 8.432 0.774 26865 4.921 59.311 1.502 5.537 8.498 0.798 27222 4.988 59.135 1.563 5.601 8.545 0.975 27579 4.919 59.444 1.531 5.644 8.465 0.849 27936 4.867 5926 1.612 5.719 8.642 0.856 28293 4.921 59.51 1.629 5.81 8.681 0.767 28850 4.825 59287 1.543 5.726 8.658 0.87 29007 4.964 59.164 1.581 5.724 8.714 0.92 29364 4.902 59.032 1.645 5.779 8.814 0.924 29721 4.95 59.671 1.604 5.929 8.744 0.8 30078 4.955 59.191 1.668 5.879 8.998 0.936 30435 4.798 59.151 1.663 5.923 8.762 0.899 30792 4.839 59.387 1.671 5.926 8.96 0.871 31149 4.815 59.518 1.724 5.997 8.947 0.766 31508 4.875 59.564 1.651 6.022 8.946 0.768 31863 4.771 59.59 1.737 6.08 9.065 1.013 32220 4.636 59.499 1.726 6.074 9.086 0.889 32577 4.604 59.445 1.681 6.121 9.146 0.924 32934 4.88 59.825 1.694 6.136 9.441 1.074 33291 4.794 59.56 1.67 6.184 9.554 1.087 33648 4.567 59.399 1.688 6.156 9.366 0.886 34005 4.726 59.402 1.721 6205 9.414 0.929 34362 4.666 59.765 1.727 6.184 9.437 1.004 34719 4.666 59.611 1.755 6294 9.39 1.069 35076 4.767 59.22 1.803 6.355 9.459 1.047 35433 4.5 59.422 1.743 6271 9.578 0.987 35790 4.577 59.504 1.827 6.381 9.493 1.031 36147 4.543 59.825 1.749 6.386 9.755 0.953 36504 4.575 59.49 1.827 6.408 9.627 0.954 36861 4.698 59.735 1.797 6.417 9.59 0.932 37218 4.655 59.801 1.839 6.534 9.675 0.929 37575 4.507 59:408 1.784 6.449 9.838 1.072 37932 4.45 59.555 1.842 6.529 9.723 0.943 38289 4.477 59.611 1.862 6.569 9.488 1.063 38646 4.41 59.383 1.889 6.529 9.824 1.015 39003 4.302 59.485 1.896 6.52 9.636 0.851 39360 4.464 59.54 1.887 6.642 9.89 1.01 39717 235
4.378 59.407 1.844 6.606 9.852 0.927 40074 4.302 59.757 1.905 6.564 9.997 0.984 40431 4.476 59.653 1.907 6.649 10.092 1.103 40788 4.363 59.363 1.887 6.698 10.126 1.077 41145 4.449 59.882 1.92 6.786 10.134 0.99 41502 4.388 59.831 1.882 6.752 10.166 - 1.051 41859 4.36 59.694 1.906 6.774 10.147 1.071 42216 4.341 59.454 1.989 6.757 10.019 0.867 42573 4.283 59.912 1.905 6.776 10.361 1.047 42930 4.419 59.954 1.908 6.871 10.351 121 43287 4.314 59.662 1.933 6.824 10274 028 43644 4.38 59.696 1.938 6.867 10258 1.091 44001 4277 59.453 1.895 6.791 10:3 1.042 44358 4.438 59.621 1.94 6.862 10.375 1.048 44715 4259 59.692 1.982 6.803 10258 1.067 45072 4.185 59.734 1.985 6.901 10.198 1.041 45429 4.435 59.634 1.941 6.967 10.571 1:127 45788 4.377 60.131 2.023 7.008 10.48 1,133 46143 4237 59.717 1.935 7.003 10.437 0.976 46500 4239 60.137 2.018 7.05 10.523 1.114 46857 4212 59:923 2.062 7.019 10.646 1.101 47214 4224 59.836 2.002 7.047 10.728 124 47571 4.36 59.883 2.067 7.065 10.389 1.103 47928 4201 59.748 2.032 7.133 10.551 1.161 48285 4227 60 2.024 7.104 10.835 1.116 48842 4.184 59.883 1.976 7.115 10.784 1.145 48999 4251 59.834 2.08 7.161 10.666 1.133 49356 4221 59.954 2.054 7225 10.908 1.182 49713 42 60.015 2.09 7.163 10.756 1.169 50070 421 59.722 2.098 7.148 10.54 0.984 50427 4.067 60.078 2.085 7.168 10.845 1.049 50784 4.146 60.186 2.082 7215 10.958 1.119 51141 4.147 60.328 2.098 7262 10.942 1202 51498 , 4.044 59.667 2.078 7298 10.827 1:057 51855 4.05 60.394 2.157 7.3 11.107 1.13 52212 4.013 60.09 2.129 7294 11,162 1.175 52569 4.143 60.086 2.068 7285 10.946 1.105 52926 4.072 60.036 2.141 7.365 11.106 1.066 53283 ' 4.015 60.119 2.139 7.385 11.038 1.098 53640 4.173 60.152 2.167 7.391 11.115 1.159 53997 ( 4.072 59.785 2.147 7.316 10.936 1.111 54354 4.129 59.949 2.153 7.349 11.074 1.132 54711 [ 4.055 60.445 2.126 7.468 11226 1.195 55068 4.06 60299 2.152 7.446 1126 1.37 55425 4.007 59.737 2.166 7.462 -11.15 1.047 55782 " 4.155 60.139 2.185 7.461 11.023 1.107 56139 4 60.142 2.151 7.454 11.326 1.17 56498 ^ 4.075 59.983 2.178 7.494 11286 1231 56853 3.926 60.131 2.188 7.514 11.342 1.172 57210 4.01 60.45 2.148 7.524 11238 1281 57567 4.079 602 2202 7.511 11278 1.277 57924 3.873 59.932 2.173 7.513 11.444 1.336 58281 236
3.982 60.303 2.179 7.5 11.562 1227 58838 4.05 60.549 2.161 7.523 11.548 1.19 58995 3.984 60.49 2253 7.591 11.548 1.3 59352 3.809 59.763 2218 7.578 11.581 1266 59709 3.955 60.314 2.159 7.475 11.467 1299 60066 3.885 60.202 2214 7.566 11.5 - 1.173 60423 3.982 60.192 2.175 7.584 11.556 1267 60780 3.717 60.168 2.185 7.637 11.629 12 61137 3.965 60.138 2.24 7.616 11.656 1.319 61494 3.82 60.052 2245 7.653 11.557 . 1255 61851 3.883 60.166 2205 7.664 11.57 1246 62208 3.89 60.205 2232 7.716 11.512 1259 62565 4.041 60.144 2223 7.651 11.517 1231 62922 3.99 60.121 225 7.727 11.781 127 63279 3.776 59.981 2248 7.74 11.494 1:303 63636 3.886 59.794 2208 7.649 11.477 -1229 63993 3.832 60.122 2274 7.741 11.569 1243 64350 3.992 60.136 2211 7.714 11.664 1291 64707 3.594 60255 2277 7J 69 11.468 1269 65064 3.83 60.012 2.302 7.787 11.695 1282 65421 3.893 60.141 2.309 7.794 11.754 1.402 65778 3.682 60.084 2283 7.762 11.502 1.198 66135 3.857 60.033 2297 7.829 11.558 1.178 66492 3.901 60.31 2.307 7.821 11.688 1.318 66849 3.814 60.081 2295 7.826 11.536 122 67208 3.821 60248 224 7.788 11.838 1.326 67563 3.806 59.996 2267 7.776 11.689 1268 67920 3.671 59.877 2.335 7.837 11.725 126 68277 3.779 60.09 2277 7.85 11.747 1.178 68834 3.756 59.991 2297 7.824 11.837 1.34 68991 3.651 59.718 2:392 7.878 11.854 1.316 69348 3.647 59.674 2.303 7.743 11.614 1223 69705 3.739 59.838 2.326 7.932 11.774 1229 70062 3.797 59.989 2.364 7.872 11.709 1.323 70419 3.56 59.842 2.31 7:916 11.742 1254 70776 3.537 59.847 2248 7.869 11.859 1267 71133 3.719 59.742 2.304 7.881 11.983 1285 71490 3.602 59.993 2.334 7.885 11.816 1.408 71847 3.811 59.809 2.342 7.988 11.994 1.328 72204 3.65 59.619 2.319 7.877 11.619 1.179 .72561 3.608 59.716 2.317 7.968 11.774 1208 72918 3.579 59.752 2.31 7.981 11.933 1.381 73275 3.527 59.638 2292 7.89 11.538 1205 73632 3.63 59.426 2.375 7.948 11.814 1.198 73989 3.634 59.419 2.348 7.876 11.637 122 74346 3.648 59265 2.359 7.917 11.774 1.346 74703 4.94? 237
10.00 30.00 50.00 70.00 (Thousands) 238
Filename: I019BHB.SER'
Starting material: trans/cis-2-methyl-3-phenyl-l,5-
heptadiene (30% cis)
Concentration: 0.045 6M
Temperature: 308K 239
1019BHB.SER Integrate B C D E F G H I J K 21.987 259.177 -1215 -1.154 8.369 94.909 0.031 -2298 12.672 37.546 19.782 26722 -0.428 4.65 11.826 82.012 0.121 -1.728 11.595 33.152 17.57 273.485 -0.169 8.681 14.575 74.163 0.176 -1.583 10.911 30.331 15.215 278.567 0287 11.876 16203 68.171 0287 -1.386 10.426 28.452 12.32 282.146 0.598 14263 18.126 63.726 0.325 -1.183 9.997 27.002 13.688 284.608 0.778 15.974 19.337 59.347 0.409 -1.143 9.728 26.128 13.866 287.343 1.003 17.483 20.363 57.024 0.386 -1.021 9.477 25232 14.285 288.869 1286 18.465 20.922 54.169 0:503 -0.997 9202 24.436 13595 289.543 1.337 19.436 21.565 52.154 0.443 -1.029 9.076 23.569 13.515 290.767 1.465 20.021 22.519 50214 0.489 -0.965 8.883 23.146 14.139 291.109 1.486 20.646 23.021 49.133 0.479 -0.987 8.797 22.455 15.681 291.808 1.788 21241 23.05 47.858 0.502 -1.001 8.695 22.085 15.084 291.385 1.857 21.628 23.685 47299 0.502 -1.047 8.569 21.425 15.173 291.31 1.817 21.858 23.892 45.435 0.515 -0.935 8.446 21.378 17.56 292.695 1.946 22237 24234 44.404' 0.51 -0.999 8.423 20.901 15.903 292.145 2.032 22.713 24.927 44.024 0.39 -1.102 8.322 20.743 16.88 291.976 2.026 22.754 24.805 4221 0.456 -1.066 8268 20224 17513 291.4 2.099 23.029 24.958 42211 0.422 -1.117 8.198 20.03 19.764 291.771 2.043 23.099 25264 41.36 0.424 -1.099 8229 19.708 19205 292.076 2.043 23.347 25.165 40.452 0.438 -1.087 8.156 19.483 19.945 291281 2.19 23.403 25.083 40.178 0.416 -1.127 8.062 19.187 20252 292.067 2.052 23.331 25.756 39259 0.429 -1.13 8.064 18.933 21.476 291.671 2.148 23.441 25.683 39.534 0.481 -1.174 7.973 18.611 22.529 292.307 2.312 23.6 25.004 38.417 0.422 -121 8.034 18.353 23.31 291.958 2277 23.617 25.902 38.378 0.462 -1.177 7.954 18.197 24.517 292.122 2.529 23.95 25.446 37.328 0.394 -1218 7.955 18236 22.777 291.148 2.323 23.883 25.715 37.868 0.36 -124 7.924 18.145 24.839 291.615 2.305 23.856 26.636 37.089 0.453 -1.176 7.872 17.945 23.763 292.147 2.42 23.937 25.922 37.058 0.478 -1221 7.847 17.783 23.882 291229 2.381 24.044 26.11 36.943 0.43 -126 7.797 17.525 25231 291.381 2.581 23.884 26.37 35.973 0.467 -1265 7.744 17.394 26.12 291.984 2.472 23.878 26.405 36287 0.506 -1267 7.744 17259 25.985 291.975 2.485 23.981 26213 35.795 0.48 -1284 7.738 17.079 25.5 291.763 * 2.495 24.098 26.719 35.582 0.442 -1.317 7.692 16.883 25.853 291.362 2.503 24.137 26.497 35.385 0.426 -1.337 7.682 17.165 27.301 291.418 2.471 23.946 26.961 34.564 0.44 -1.324 7.633 16.773 26225 291.092 2.408 24.025 26.332 34.549 0.42 -1.333 7.629 16.48 27.372 291.128 2.512 24.048 26.632 34.373 0.462 -1297 7.623 16.41 26.14 291.002 2.382 24241 26.877 33.789 0.454 -1272 7.571 16.366 27.55 291.046 2.594 24.109 26.614 34.09 0.355 -1287 7.57 16.242 27.831 291.345 2.598 24.095 26.725 33.558 0.434 -1296 7.557 16.003 27.664 290.978 2.66 24.416 26.978 33.455 0.494 -1247 7.465 16.173 28.418 290.541 2.559 24.061 26.612 33.77 0.459 -1.327 7.461 15.992 27.915 290.339 2.569 24.185 26.942 32.803 0.374 -1.378 7.442 15.937 28.545 290.935 2.524 24.166 26.422 33.383 0.412 -1261 7.45 15.978 28.101 290.63 2.519 24.117 26.688 33.057 0.432 -1284 7.496 15.821 28.484 289.635 2.719 24.374 26.359 32.763 . 0.379 -1.306 7.437 15.753 27.543 289.616 2.67 24222 27 32.855 0.482 -1.352 7.36 15.854 28.353 289.382 2.565 24.056 26.981 32.391 0.401 -1.323 7.435 . 15.667 28.831 293228 2.515 24.55 26.882 32.923 0.435 -1.329 7.443 15.955 240
28.805 289.182 2.676 24.236 26.BS 32.725 0.478 -1.333 7.362 15.524 28.084 289.802 2.73 24.119 26.726 31.82 0.431 -1.346 7286 15.659 28.957 290.123 2.666 24.105 27248 31.833 0.489 -1.325 7.3 15.575 28.112 289.755 2.698 24.263 27.551 31.631 0.426 -1.37 7.303 15.305 28.445 289.316 2.892 24.13 27.199 32.024 0.418 -1.363 7268 15.418 27.699 291.609 2.642 24.191 27204 31.949 0.427 -1.355 7257 15.498 28.096 291283 2.757 24.435 2721 31.619 0.39 -1.376 7288 15.391 28.959 290245 2.9 24254 27.11 31.803 0.48 -1.346 7208 15.425 28.736 292.531 2.87 24.401 27.513 31.009 0.461 -1.423 7239 15294 27.81 289.839 2.771 2428 26.808 31285 0.401 -1.368 7.18 15.177 29.982 290.188 2.785 24.304 27.193 30.955 0.465 -1.386 7.182 15.146 28.644 289.535 2.929 24258 27.08 31.376 0.381 -1.357 7.171 15.003 29.613 290.471 2.635 24208 26.84 31274 0.447 -1.427 7.129 15.18 30.449 291.565 2.875 24.342 27225 30.98 0.425 -1.391 7202 14.983 29.76 289.36 2.851 24288 27219 30.889 0.414 -1.402 7.123 14.953 30262 291.675 2.81 24.535 27.375 30.937 0.458 -1.364 7.143 14.791 29.071 290202 2.854 24.344 26.989 30.79 0.424 -1.322 7.036 14.678 30.009 290.496 2.81 24205 27.42 31.026 0.373 -1.31 7.007 14.47 29277 289.612 2.808 2429 27295 30.802 0.377 -1.41 6.955 14.627 29.944 290.343 2.889 2421 27.189 30.794 0.444 -1.443 6.999 14.456 29.762 290.673 2.744 24233 27208 30.578 0.346 -1.392 6.983 14.561 _ 29.344 290.304 2.673 24257 27.484 30.484 0.482 -1.365 7.064 14.502 28.802 290.344 2.652 24.107 26.794 30.808 0.458 -1.377 7.021 14.501 29.402 290.404 2.894 24245 27.323 30.373 0.42 -1.434 6.968 14295 30.819 291278 2.91 24.327 27.177 30.342 0.395 -1.417 7.001 14.083 30.095 289.151 3.006 24.099 27225 30.341 0.389 -1.454 6.942 1426 29.486 289.032 2.825 24.042 27.119 29.993 0.414 -1,443 6.841 14.024 29.083 289.412 2.886 24.063 27,093 30.383 0.447 -1.441 6.858 14.026 28.787 289212 2.809 24.064 27296 30.026 0.451 -1.393 6.832 14.03 30.573 289277 2.979 24.133 27.146 29.893 0.409 -1.424 6.84 14.188 30 289.716 3.008 24.317 26.865 29.882 0.447 -1.401 6.797 14.082 30.333 290.89 2.859 24209 27.136 30.185 0.408 -1.423 6.814 14.348 31.428 291.008 2.914 24.321 27.366 29.885 0.465 -1.451 6.921 14232 30.799 291.035 2.94 24.116 27279 29.785 0.453 -1.391 6.84 14.21 30.501 291225 3.031 24.435 27277 30.15 0.373 -1.431 6.829 14292 3023 291.131 2.987 24271 27.17 30.164 0.352 -1.383 6.839 14.374 31249 290227 2.943 24281 26.584 29.795 0.417 -1.419 6.827 14.142 29.768 288.452 2.958 24.032 26.74 30.068 0.452 -1.47 6.716 14.028 31298 289.37 2.972 24.144 26.988 30.531 0.364 -1.442 6.741 14.052 29.771 289.324 2.906 24.115 26.979 30236 0.386 -1.411 6.723 14.211 30291 289.98 2.904 24.086 26.676 29.38 0.445 -1.435 6.734 14.081 31.43 291.988 3.086 24267 27.008 29.811 0.401 -1.487 6.841 14.029 31.365 291.603 2.848 24241 26.84 30234 ' 0.361 -1.45 6.809 13.944 32.127 290.991 2.972 24.176 26.565 29.442 0.441 -1.449 6.816 13.835 31.458 291.144 2.885 24.115 26.304 29.422 0.419 -1.465 6.8 14.069 32.198 291.646 2.989 24.485 26.861 29.554 0.428 -1.442 6.776 13.962 31.593 289.713 3.084 24.118 26.596 29.779 0.397 -1.502 6.678 13.865 32.465 289.878 2.95 24.133 26.54 29.59 0.414 -1.456 6.664 13.801 32.144 290.492 2.996 24.146 26.723 29.75 0.345 -1.463 6.636 13.807 31.38 290.178 2.995 24.048 26:817 29.675 0.397 -1.41 6.698 13.934 31.067 290.824 2.979 24.133 26.839 29.196 0.447 -1.406 6.677 13.81 32.331 295219 3.013 24.392 27244 29.94 0.426 -1.502 6.804 14.027 241
31.123 290.665 3.114 24221 25.765 29.348 0.395 -1.476 6.746 13.835 31.615 2922 2.913 24.167 26.83 29.388 0.419 -1.486 6.716 13.577 29.683 260.319 2.902 24.03 26.566 29.523 0.443 -1.472 6.624 13.618 31.522 290.456 3.141 24234 26.525 29.631 0.41 -1.49 6.625 13.629 32.887 289.954 2.697 24.027 26.7 29.198 0.372 -1.438 6.602 13.731 32.671 291.128 2.987 24223 27.025 29.194 0.452 -1.468 6.65 13:523 31.759 290.775 3.053 24.156 26.579 28.939 0.379 -1.482 6.627 13.609 32558 295.352 3206 24.783 26.948 30.001 0.449 -1.469 6.611 13.958 32.65 291.929 3262 24.452 26.085 29.34 0.403 -1.489 6.719 13.745 32.843 291.898 3.083 24281 26.194 29.446 0.458 -1.563 6.665 13.732 33.025 289.021 2.976 23.995 25.822 28.778 0.416 -1.43 6.552 13.498 33.433 291.075 3 24232 26.197 - 29.318 0.408 -1.509 6.58 13.497 32.647 290.886 3.086 24.304 26.338 28.567 0.398 -1.532 6.602 13.402 33.24 291.08 3.063 24.151 26.441 29.013 0.368 -1.469 6.562 13.488 33.376 291.771 3.102 24265 26.53 28.814 0.389 -1.515 6.594 13.479 32.635 290.724 3.057 2427 26.001 29.334 0.405 -1.438 6.626 13.479 31.893 291237 2.99 24.358 26.367 29.029 0.4 -1.431 6.652 13.444 32.98 292.672 3.029 24.375 26278 29.076 0.35 -1.469 6.648 13.613 32.735 290.96 2.983 24.104 26.369 28.88 0.392 -1.482 6.512 13.36 33.565 290.673 3.127 23.98 26.373 28.662 0.377 -1.513 6.51 13.476 32.2 290.471 3.165 24.155 26.375 28.686 0.386 -1.536 6.438 13.29 32.93 291.405 3.057 24.175 26234 28.692 0282 -1.46 6.508 13.346 31.491 291.643 2.875 24201 26.492 29.414 0.426 -1.499 6.5 13.345 33215 291.834 2.981 24289 26.503 28.795 0.336 -1.497 6.565 13.396 32.456 292.812 3.142 24274 26.148 28.692 0.422 -1.531 6.55 13.366 33.708 291.53 3.142 24.359 25.913 28.675 0.37 -1.485 6.52 13.398 33.675 290.01 3.195 23.969 26.565 28.491 0.326 -1.485 6.438 13.286 33259 290.677 3.121 24228 26.622 28.772 0.374 -1.511 6.422 13.301 32.875 291.746 3.194 24266 26.507 28.747 0.316 -1.436 6:432 13.38 32.457 291.726 3.131 24.106 26.422 28.922 0.415 -1.482 6.443 13.337 34.545 295.504 3223 24.427 26.552 . 29.26 0.349 -1.563 6.485 13541 34.119 292.542 3.194 24.197 26.384 29.415 0.437 -1.525 6.485 13.35 33.897 29124 3282 24.305 26.433 28.434 0.407 -1.532 6.402 13554 33.994 290.98 3.071 24.134 26232 28.026 0.312 -1.524 6.393 13.125 33.548 290.988 3.193 24244 26.582 28.085 0.398 -1.531 6.362 13.096 33246 292.1 to 3252 24.394 26.445 28.642 0.319 -1.541 6.405 13.435 33.459 292.072 3.088 24251 26.153 28.707 0.306 -1.508 6.422 13.425 33.507 292268 3231 24.525 26.371 28.861 0.422 -1.559 6.467 13.173 33.473 294209 3.045 24.341 26.467 28.907 0.389 -1.498 6.549 13.378 34.432 291.052 3282 24284 26.503 28.544 0.333 -1.497 6.378 13.18 34269 292.058 3.122 24.177 26.47 28.469 0.388 -1.485 6.346 13.102 33.923 291.351 3226 24.148 26242 28.393 0.401 -1.529 .6.372 13.081 33221 292.317 3.144 24268 26215 28.524 0.354 -1.501 6.364 13.153 33.982 292.675 3.186 24.334 26295 28.681 0.381 -1.57 6.406 13.4 31.712 292.741 3.165 24.524 26.543 28.643 0.366 -1.568 6.448 13.213 32.114 293.112 3227 24.559 26207 28.613 0.309 -1.546 6.437 13.322 34.582 291.322 3271 24271 26.507 28.476 0.391 -1.534 6.381 13.058 34209 291.163 3267 24271 26.039 28.375 0.402 -1.548 6.369 13.269 33.934 29222 3264 24262 26.023 28253 0.354 -1.504 6.369 13.032 32.568 292.491 3.166 24.427 26.015 28.79 0.3Q7 -1.541 6.352 13.216 32.986 291.556 3.199 24264 25.774 28.476 0.384 -1.534 6.385 13.105 32.787 293.647 3238 24.509 26.128 29.005 0.38 -1.547 6.463 13543 242
33.888 294.098 3251 24299 25.85 28.554 0.39 -1.574 6.4 13.153 33.678 291.374 3.087 2422 26.346 28.163 0.335 -1.53 6.335 13.161 33.614 291.613 3.156 24231 26298 28.405 0297 -1.522 6.345 13.184 34.059 293.028 3.127 24237 26273 28.571 028 -1:577 6.368 13.023 32.833 293.563 3.082 24.337 25.89 28.75 0.326 -1.539 6.346 13.095 32.853 294.146 3.165 24.603 25.743 29.321 0.419 -1.521 6.456 13.199 32.628 293.19 3.154 24.535 25.603 28.573 0.358 -1.608 6.419 13.073 34.085 291.993 3208 24238 26.17 28.541 0.317 -1.516 6.311 12.947 34.67 292.339 3.35 24.391 26.129 28.6 0.322 -1.547 6.346 13.041 33.659 292.573 3205 24.315 25.736 28299 0.363 -1.581 6.347 12.895 33.983 293.42 3.399 24.504 26.024 28.169 0.341 -1.545 6.355 13.097 34.058 293.959 3.167 24.388 26.019 28.475 0.411 -1.555 6.419 13.302 33.135 294.114 3.161 24.404 26206 28.515 0.364 -1.535 6.474 12.996 33.166 294.42 3254 24.585 25.184 29216 0.353 -1.537 6.435 13.098 33.167 293.112 3.086 2423 25.852 28275 0.371 -1.498 6.401 12.959 33.312 293.143 3211 24265 26.376 28.611 0.339 -1.556 6.345 13.021 32.816 293.454 2.996 24209 26.057 28.686 0.415 -1.55 6.328 13.198 33.103 293.932 3.313 24.46 26206 28.32 0.359 -1.574 6.341 12.917 33.931 293.831 3278 24.374 26.404 28.184 0.372 -1.577 6.315 13.089 35.382 294.603 3238 24.516 26206 28.397 0.371 -1.6 6.326 13.013 33.507 294.748 3266 24263 26.345 28231 0.309 -1.564 6.323 13.076 34.054 293.913 3224 24.457 25.744 28.466 0.409 -1.535 6.316 13.183 33267 294.743 3.195 24.33 25.884 2826 0.353 -1.587 6.362 12.94 33.398 293.278 3.165 24287 26.012 28.446 0.331 -1.581 6.362 12.885 32.938 292.654 3.368 24289 26292 28.426 0.38 -1.588 6.186 12.927 33.564 292.525 3.306 24.499 26.039 28224 0.349 -1.569 6.193 13.081 33.767 292.844 322 24.311 26.481 27.878 0.328 -1.535 6.163 12.821 32.948 292.875 3262 24.455 26.38 28.763 0.316 -1.539 6.19 12.805 34.037 293.587 3.41 24294 26.367 28227 0294 -1.566 6.188 12.728 34.497 293.63 3285 24.429 26285 28.362 0.346 -1.532 6.147 12.946 33.197 293.87 3207 24.558 26.03 28.089 0412 -1.587 6222 12.873 34.668 293.821 3.325 24.393 25.851 28.143 0.338 -1.555 6272 12.987 33.486 294.888 3245 24.425 25.913 27.851 0.358 -1.626 623 12.946 33.682 294.688 3248 " 24.46 26235 28.198 0.302 -1.534 6.122 12.89 35.153 292.727 3252 24.467 26.47 28.333 0.304 -1.624 6.023 12.754 34.848 292.467 3.345 24.409 26.3 28.39 0285 -1.541 6.062 12.685 32.674 293.149 3.332 24.609 26.857 28.601 0.325 -1.468 6.1 12.694 34.326 293.126 3.098 24263 26.434 28.196 0.305 -1.577 6.156 12.688 32.875 29326 3.28 24.382 26.345 28.23 0.329 -1.594 6.118 12.884 35.009 294.655 3.348 24.475 26.723 28.551 0.361 -1.575 6.167 12.778 33.513 293.916 3219 24.444 26.614 28.39 0.358 -1.58 6.111 12.819 33.725 293.927 3278 24.499 26.379 28.337 0298 -1.549 6.13 12.67 31.989 293.851 3.079 24.468 26.514 28.57 0.33 -1.605 6.165 12.731 33.549 294.07 3264 24.553 26.542 28259 0293 -1.609 6.102 12.789 33.097 293.867 3255 24.499 26.043 28.369 0.365 -1.591 6.106 12.726 34.092 294.624 3.313 24.417 26.059 28.508 0.355 -1.572 6.099 12.722 33241 293.39 3.321 24.4 26.342 28.527 0288 -1.57 6.164 12.83 33.354 292.936 3286 24.501 26222 282 0.442 -1.516 6.111 12.522 34.074 293.781 3.362 24.495 25.611 28.139 0.354 -1.624 6.049 12.627 32243 292.6 3256 24.436 25.845 28.372 0.348 -1.596 6.109 12.563 3422 292231 3264 24.464 25.969 28.186 0285 -1.572 6.06 12.663 33.199 292.036 3.133 24211 26.457 28277 0251 -1.598 6.019 12.62 243
35.104 292.35 3.347 24.454 25.827 28.012 0.331 -1.572 6.173 12.558 35.741 292202 3.387 24.509 26251 27.906 0.378 -1.489 6.078 12.624 36.641 290.887 3288 24.137 26.163 27.759 0246 -1.577 6.037 12.562 35.743 290.365 3.304 24209 26.654 27.721 0.327 -1.569 6.012 12.652 35.849 288.904 3.464 24.385 26.586 28.019 0.344 -1.566 5.995 12.508 35.987 289.458 3.326 24.36 26.985 2823 0257 - -1.52 5.978 12.586 35.861 289.433 3.405 24298 26.822 27.853 0236 -1.543 5.919 12.553 36.482 289249 3.42 24.352 26.798 27.015 0248 -1.606 5.983 12.643 37.152 288.308 3.391 24.16 27.61 27.877 0246 -1.563 5.893 12.477 35.691 288.494 3.372 24.008 27.319 27.529 0272 -1.601 5.85 12.621 35.207 288.012 3227 24212 27.671 27.082 0241 -1.551 5.812 12.459 35.891 287.851 3242 24.103 27.636 27.43 0247 -1.482 5.814 12.512 35.53 287.657 3214 24213 27.528 27.378 0259 -1.57 5.766 12.49 36.707 287.004 3.199 23.928 27.419 27.848 024 -1.518 5.734 12366 36.419 287.14 3.108 23.846 27.117 27.475 0287 -1.574 5.762 12.348 37213 287.004 3293 24.017 27.377 27.887 0244 -1.561 5.736 12.157 35.885 285.92 3245 24.033 26.908 27.45 0245 -1.613 5.755 12.424 37.85 286.881 3226 23.931 27.55 27.169 0.19 -1.566 5.784 12.133 37.08 286.963 3.24 24.01 27.312 27.32 0215 -1.597 5.684 12.155 37.087 286298 3.402 24.021 27.523 27.563 0224 -1.621 5.744 12.171 37235 286227 3.26 23.866 27.629 27.128 0205 -1.55 5.685 12306 35.876 285.472 3.132 23.879 27.757 27.131 0229 -1.561 5.681 11.899 37.404 286.18 3269 23.623 27.5 27.424 0212 -1.614 5.702 12.149 36.713 285.939 3208 23.851 26.953 27.384 0.184 -1.593 5.572 11.996 37.706 286.573 3262 23.854 27.335 27256 0.19 -1.605 5.626 12.194 36.665 286237 3272 23.681 27.273 26.751 0.13 -1.647 5.598 12.083 37.672 285.539 3.143 23.425 27.512 26.81 0264 -1.585 5.545 12.071 37.04 285.532 3.335 23.666 27.121 27.395 0.136 -1.663 5.615 11.771 37.414 285.11 3212 23.544 27.451 27.088 0287 -1.551 5.507 12.064 37.419 284.54 3.173 23.654 27215 26.543 0249 -1.626 5.616 11.79 37.305 284.319 3.397 23.632 27291 27.123 0231 -1.625 5.471 11.885 36.436 283.98 3.377 23.825 26.843 26.949 0206 -1.62 5.538 11.981 36.686 284.181 3273 23.586 26.831 27.032 0223 -1.672 5.587 11.898 37255 284.727 3256 23.811 26.948 26.912 0214 -1.643 5.571 12.052 37.173 284.393 3232 23.347 27.106 26.77 0.186 -1.67 5.441 11.871 37.619 284.426 3.23 23.609 27.156 27.334 0.172 -1.574 5.508 11.794 38.759 284.336 . 3.198 23.63 26.714 27.101 0236 -1.6 5.605 11.902 37.421 284.12 3.342 23.583 27.001 27.193 0.183 -1.662 5.5 11.887 39259 284.452 3.331 23.63 26.808 27.173 0221 . -1.615 5.48 11.801 38.661 284.446 3223 23.46 26.493 26.804 0221 -1.627 5.587 11.853 38.561 284.46 3292 23.616 26.873 27.072 0.149 -1.615 5.509 11.935 37.877 283.435 3.342 23.549 26.794 26.549 0206 -1.66 5.49 11.956 37.147 283.082 3271 23293 26.997 26.165 0.194 -1.628 5.593 11.875 38.05 283.417 3.363 23.608 27.129 27.005 0243 -1.628 5.442 11.733 244
LMN O P QRS I time (s ) . 81.362 33.025 0.351 -1.862 283.625 54.849 1.655 3269 34.897 0 76.889 22.923 1.859 16.052 244253 5423 9.574 3.438 33.898 357 75226 27.142 3.307 29.361 219.028 54.648 15.857 3.933 32.697 714 74.038 30.432 4.335 39.186 201.708 55.027 21204 4.037 31.881 1071 72.404 32.65 5203 46.594 188.021 55.526 25.917 4273 31.301 1428 70.811 34.053 5.888 52.095 176.69 55.555 29.578 4.491 30.351 1785 69.907 36.556 6242 56.428 168.639 55.821 33.134 4.58 29.968 2142 68.994 38.693 6.755 60.091 161.896 55.959 36.066 4.802 29.543 2499 68.216 40.525 7215 62.68 155.481 55.916 38.805 4.953 29.38 2856 67.606 43.803 7.318 64.984 151283 56221 41214 4.993 29.071 3213 67.049 45.387 7.612 66.67 146.894 56.466 4324 5.13 28.759 3570 66.127 46.822 7.759 68277 142.853 56228 45.097 5283 28268 3927 65.782 49.035 7.862 69.503 139.872 56.471 46.704 5244 27.998 4284 65.143 49.147 8.28 70.616 136.39 56.337 47.983 5.322 27.475 4641 64.431 51.007 8.193 71.66 134284 56.454 49.452 5285 27.46 4998 64.107 52.811 7.885 72.402 131.979 56.805 50.943 5.37 27283 5355 63.773 51.919 8284 73.191 129.68 56.59 51.952 5231 26.653 5712 63.08 53.303 8259 73.863 127.774 56.517 53.069 5.457 26.747 6069 62.555 52.864 8.496 74.501 125.442 56.734 53.841 5.361 26.624 6426 62.429 52.845 8.81 74.958 123.9 56.872 54.626 5.347 26.181 6783 62.024 53.606 8.736 75.514 122.572 56.941 55.681 5.332 26.087 7140 61.559 51.803 8.988 75.918 120.627 57.114 56.151 5.556 25.961 7497 61.614 52.772 8.774 76205 119.587 56.675 56.988 5.449 25.785 7854 61.096 51.181 9.187 76.755 118.133 56.945 57.607 5.507 25.483 8211 60.882 50.935 9.184 77.056 116.889 56.951 58.141 5.341 25.132 8568 60.775 49.872 9.445 77.598 115.429 56.727 58.803 5.633 25.184 8925 60.499 50.416 9.318 77.875 114.735 57.108 59.41 5.58 25.082 9282 60.191 48.473 9.802 78.141 113.352 57282 59.835 5.532 24.825 9639 59.7 48.446 9.878 78.402 112.917 5725 60.306 5.42 24.775 9996 59.341 48213 9.925 78.815 112.067 57.392 60.942 5.471 24.452 10353 59.39 47.002 10.158 79.178 110.985 57.182 61.185 5.556 24.173 10710 59.097 45.941 10283 79.332 110281 57.329 61.776 5.655 24218 11067 58.951 44.638 10.371 79.854 109.187 57.581 62.068 5.625 24.083 11424 58.816 43.823 10.522 80.014 108.689 57.743 62.613 5.538 23.929 11781 58.557 42.552 10.703 80.445 107.839 57.425 62.858 5.674 23.779 12138 58.028 41.342 10.842 80.82 107297 57.374 63.395 5.495 23.333 12495 57.923 41.033 11.037 80.989 106.873 57.933 63.76 5.573 23.562 12852 57.892 38.908 11.34 81.049 105.636 57.692 63.821 5.609 23.35 13209 57.659 39.11 11.386 81.138 105237 57.596 64.023 5.56 23.126 13566 57.813 37.676 11.39 81.416 104.469 57.893 64274 5.732 23.101 13923 57.343 36.845 11.698 81.726 104232 57.876 64.672 5.627 22.887 14280 57.162 35.61 12.051 81.813 103.137 57.732 64.623 5.619 22285 14637 57.154 34.676 12.131 82.163 102.408 57.449 64.937 5.773 22.566 14994 56.907 34.491 12.039 82.319 102.516 57.836 65297 5.773 22.593 15351 56.772 31.769 12271 82.565 101.85 57.866 65.452 5.819 22.397 15708 56.851 30296 12.338 82.846 101.662 57.795 65.753 5.763 22.408 16065 56.153 29.881 12.669 83.026 100.919 57.781 65.817 5.759 22.074 16422 5623 29.314 12.793 83.049 100.484 57.776 65.898 5.825 22.171 16779 56.524 28.576 12.958 82.976 99.59 57.596 66.056 5.768 21.928 17136 56.97 29.314 13222 84.696 101.183 58.865 67.622 6.046 22246 17493 245
55.888 25.887 13.474 83.789 99.036 57.682 66261 5.935 21.683 17850 55.886 28.482 13287 83.582 98.792 57.643 66.784 6.018 21.442 18207 55.787 27.752 1367 83.859 98.334 57.93 66.832 5.999 21.417 18564 55.809 28.042 13.309 83.842 98.005 57.732 66.975 6.072 21.391 18921 55.57 26.401 13.662 84.162 97.845 57.981 66.901 6.048 21.352 19278 55.953 28.039 13.882 85.069 98.699 58.368 67.863 6.077 21.601 19835 55.593 26.541 14.071 85217 98.025 58.409 67.954 6277 21.665 19992 55.355 25.54 14.127 84.626 98.978 57.803 67.359 6.15 21.189 20349 55.744 25.735 14.197 85.42 97.366 58.564 68.101 6216 21.073 20706 54.989 26.761 14292 84.939 98.411 57.781 67.547 6.194 21.172 21063 54.931 25.097 14.366 84.977 98.152 58.101 67.821 6.135 20.996 21420 54.644 24.448 14.477 84.93 95.571 57.889 67.601 6.157 20.926 21777 54.639 24.155 14.529 85.099 95.433 57.841 67.877 6.324 20.908 22134 55.434 24.494 15.011 85.959 95.794 58.423 68.47 6278 20.821 22491 54.649 24.551 14.819 85.445 94.898 57.679 68.149 6.345 20.673 22848 54.895 23.543 15283 86.141 95.481 58.439 68.689 6.366 20.612 23205 54223 23.572 15.19 85.812 94.135 58.079 68215 6.339 20.171 23562 54.664 23.628 15.064 85.631 94.178 57.912 68258 6.394 20.455 23919 54.683 23.988 15.127 88.11 94.356 57.859 68.531 6.45 20.472 24276 54-238 24293 15.423 86.082 94.042 57.908 68.578 6.453 20205 24633 54.577 23.585 15287 86.381 94.101 58.042 68.79 6.422 20.416 24990 54285 21.749 15.521 86.518 93.717 58.198 68.717 6.414 19.935 25347 54.138 22.51 15.888 87.027 93.847 58298 68.954 6.444 20.009 25704 54275 21.576 15.682 86.922 93.433 58.087 68.986 6.692 20243 26081 54276 20.569 15.873 86.969 93.098 57.982 69.089 6.663 20.041 26418 54.117 22.832 15.615 86.195 92.35 57.514 68.639 6.583 19.999 26775 53.316 26.903 15.651 85.824 91.89 57.351 68.505 6.637 19.97 27132 53.359 25.178 15.866 85.992 91.765 57.641 68.743 6.61 20.123 27489 53.673 26203 15.806 86.027 92.132 57.585 68.836 6.648 20.135 27846 53.189 23.979 16232 86.355 91.78 57.522 69.02 6.768 19.473 28203 53.397 24.532 16.131 86.682 91.694 57.737 69.148 6.756 19.958 28560 53.473 22242 16268 86.935 91.549 57.587 69.14 6.766 19.812 28917 53266 20.411 16.585 87204 91.081 57.694 69.077 6.772 19.62 29274 53.195 21.665 16.415 87.491 91.604 58.157 69.691 6.78 19.598 29631 52.868 21.633 16.484 87.664 91.319 57.928 69.635 6.947 19.645 29988 53.195 19.78 16.627 87.893 91229 57.982 69.765 6.961 19.927 30345 52.844 20.552 16.643 87.344 90.673 57.614 69.422 6.895 19.682 30702 52.892 24.93 16.647 86.952 90.352 57.498 69.169 6.939 19.649 31059 52.39 24.41 16.724 86.879 90.086 57.145 69.172 6.895 19.346 31416 52.448 24.045 16.584 87.09 90.457 57.648 69.444 6.893 19.51 31773 52.77 23.468 17.019 87.464 90.039 57.682 69.431 6.877 19.587 32130 53223 21.547 16.969 88.302 90.909 58.191 70.376 7.108 20.043 32487 52.831 21.607 16.86 87.979 90242 57.987 69.908 7.181 19.656 32844 53246 19.61 17.117 88.351 90.198 57.718 69.939 7.123 19.534 33201 52.767 19.586 17229 88.641 90.017 58.098 70.091 7.112 19.351 33558 52.513 19.104 17223 88.441 89.841 58.078 70.218 7.349 19.65 33915 51.927 21274 17.339 87.678 88.807 57.193 69.51 7.307 19.145 34272 51.941 22.674 17205 87.412 88.801 57.315 69.354 7.053 19.311 34629 51.998 23.41 17201 87.812 89.325 57.528 69.683 7.152 19.148 34986 52.014 21.31 17.452 88.168 89.073 57257 69.808 7272 19262 35343 52.327 19.904 17.664 88284 88.776 57.664 69.996 7256 19.057 35700 53.116 20.394 17.825 90.164 90.732 58.921 71.596 7.476 19.698 36057 246
52.181 19.044 17.755 89.189 88.985 57.725 70.36 7.365 19.104 36414 52.331 19.812 17.602 89.009 89.338 58.077 70.655 7.459 19245 36771 51.808 21.559 17.516 88.442 88.891 57.652 70.132 7254 19.139 37128 51.797 21.872 17.555 88.159 88.368 57.193 69.803 7.314 19.132 37485 51.642 21.589 17.62 88.099 88235 57.087 69.925 7292 18.858 37842 52.076 20.39 17.823 88.379 88.133 57.156 69.877 7.362 18.677 38199 51.735 20.532 17.757 88.634 88289 57.42 70.302 7.428 18.905 38556 52.763 18.875 18.487 90.581 89.609 58.446 71.454 7.512 19.199 38913 51.894 19.365 18.06 89.444 88259 57.818 70.705 7.517 18.88 39270 52276 17.796 18231 89.478 88.011 57.672 70.888 7.648 18.797 39627 51.878 19.606 17.947 88.47 87.582 57.055 70.17 7.516 18.65 39984 51.813 22.509 17.713 88.316 87.524 57.078 70.043 7.45 19.112 40341 51.825 20.824 17.866 88.644 87.186 56.988 70.113 7.557 18.768 40698 52.102 20.737 18.049 88.791 87.489 57.012 70.447 7.53 18.914 41055 52222 20.613 17.873 88.94 87.638 57.513 70.651 7.734 18.769 41412 52.169 18.69 18.128 89.003 87.315 57.603 70.631 7.657 18.991 41769 52.449 19.865 17.973 89296 87.66 57.35 70.75 7.584 18.685 42126 52.113 18.806 18.417 89.539 87.541 57.653 70.98 7.663 18.888 42483 51.518 22215 18.019 88.893 87.35 57.368 70.532 7.538 19.134 42840 51577 23.316 18.1 88254 8826 56.893 70.068 7.516 18.987 43197 51.489 24.116 17.994 88.719 86.889 56.88 70.418 7.705 19.155 43554 52.106 24286 17.907 88.64 87.081 57.389 70.667 7.66 19.057 43911 52.081 25.083 18.329 89.091 87.399 57.7 71.057 7.56 19.331 44268 51.854 22.62 18.441 89221 87.036 57.322 70.857 7.601 18.718 44625 52.391 22.417 18.41 89.601 86.691 57.136 71287 7.832 19.179 44982 52.171 21.139 18.461 89261 88.465 56.937 70.779 7.893 18.602 45339 51.931 26.52 18204 88.185 85.986 56.557 70.469 7.606 18.887 45698 51.8 26.973 18.199 88.319 85.812 56.747 70.666 7.749 19:08 46053 51.733 26.009 18.387 88.55 86.019 56.812 70.864 7.752 18.88 46410 51.714 26.04 18.198 88.895 88.599 57293 71222 7.92 19.359 46767 52.422 24.638 18.441 9023 87229 57.668 71.812 7.975 19.194 47124 51.987 22.758 18.562 89.351 88.11 57.004 71247 7.835 18.559 47481 52254 23.825 18.366 88.649 85.588 56.665 70.474 7.84 19.002 47838 51.874 27.021 18.422 88274 85.382 56.417 70.71 7.827 19.045 48195 52.035 27.199 18.125 88.834 85.709 56.929 70.912 7.82 19.048 48552 52.06 27.627 1823 89.081 86.112 57.177 71.544 7.839 19.109 48909 52.086 25.038 18.649 89.183 85.937 56.771 71.471 8.059 18.986 49266 52.016 24.036 18.761 89.638 85.927 57255 71.306 8.078 18.944 49623 52.63 23.574 19.002 90.502 86.644 57.831 72.168 8.141 18.938 49980 51.806 27.735 18.457 88.555 85.056 56.523 70.659 7.815 19.028 50337 52235 28.684 18.519 88.733 85209 56.607 71.153 8.051 18.99 50694 52209 27226 18.689 88.998 85276 56.71 71.135 7.919 18.684 51051 51.908 26272 18.753 892 85.183 56.732 71.363 8.068 19.116 51408 52.053 25.579 18.767 89.945 85.734 57.143 71.837 8.091 19232 51765 52257 24.672 18.98 90214 85.818 57.446 72.159 8.308 19.097 52122 52.495 24.699 18.751 90.532 8623 57.623 72.361 8.336 19.049 52479 51.728 25.042 18.848 89.154 84.865 56.652 70.803 8.025 18.822 52836 51.942 26.738 18.67 88.953 84.985 56.669 71.394 8.103 18.733 53193 51.941 25.356 18.87 89.69 84.895 56.802 71.573 8.178 18.633 53550. 51.976 25.988 18.957 89.901 85202 56.979 71.954 8247 1922 53907 52.027 24.909 19.116 90.074 85.096 57265 7223 8.354 18.787 54264 51.899 24.096 19.194 90.688 85.892 57267 72.376 8243 18.874 54621 247
51.734 22.998 19.031 90.769 85.496 56.923 72.33 8.312 18.972 54978 51.697 26.343 18.872 89.509 84.809 56.614 71.39 8.026 18.885 55335 51.847 27.059 18.781 89.757 84.859 58.529 71.508 8.113 19.13 55692 51.748 26.327 18.789 89.873 85.12 57.006 71.712 8.131 19.15 56049 51.734 26.991 18.998 90.379 85.386 57.134 72.302 8295 19.08 56408 52.305 24.294 19.309 91.305 88.168 57.88 73.061 8276 18.903 56763 51.976 23.597 18.903 90.784 85235 57.027 72.451 8.378 18.733 57120 51.588 26.499 18.804 89.916 84.629 56.646 71.762 829 18.85 57477 51.998 26.646 18.804 89.852 84.474 56.593 71.928 8.18 18.821 57834 51.891 25.246 19.197 90.41 84.658 56.938 72.145 8.38 18.942 58191 51.723 24.527 19203 90.608 85.095 57.046 72.398 8.49 18.986 58548 51.751 22.582 19.469 91207 84.882 56.991 72.66 8.587 18.833 58905 51.993 22.35 19.409 91.502 85.566 57.779 72.893 8.466 19.064 59262 52.091 21.342 19.492 91.924 85299 57.536 73.024 8.595 18.676 59819 51.941 23.877 19239 90.546 84.707 56.995 72.453 8.378 18.7 59976 51.811 25.823 19.153 90.337 84.327 56.757 72292 8.43 18.985 60333 51.939 26.134 . 19.178 90.533 85.006 56.801 72.643 8.442 18.933 60690 51.728 27.63 19.08 90.686 85.025 57.15 72.888 8.438 19265 61047 52.015 27.93 19.307 90.527 84.569 57.115 72.647 8.365 18.912 61404 51.442 27.46 1923 90.661 84.587 56.986 72.736 8.503 18.914 61761 52.151 27.753 19.37 90.722 84.722 56.881 72.922 8.47 18.992 62118 51.888 26.771 19.525 90.937 84.649 57.073 73.088 8.514 18.803 62475 51.984 27.744 19294 91213 84.82 57.538 73.411 8.629 19282 62832 51.886 26.416 19.479 90.995 84.632 57243 73.017 8.449 18.993 63189 51.714 30.545 19235 90.102 84.01 56.494 72.409 8.47 19.008 63546 51.449 30.888 18.934 89.983 84.114 56.809 72.32 8.458 19.238 63803 51.858 30.963 19.029 89.831 83.862 56.48 72.417 8.484 19.115 64260 51.955 32.643 18.883 89.902 84266 56.873 72.42 8.334 19.07 64617 51.57 32.208 18.877 89.938 83.84 56.56 72.669 8.502 19.136 64974 52.032 31.828 19.059 90.005 84.149 56.624 72.684 8.373 19.395 65331 51.503 31.494 19.09 90.553 84.106 57.318 73.127 8.573 19276 65688 51.756 29.204 19.514 90.787 84.037 57221 73.022 8.422 19.315 66045 51.912 30.522 19.193 90.573 84.357 56.859 72.905 8.597 19.389 66402 51.762 33.196 19.142 90.14 84.124 56.995 73.03 8.554 19.471 66759 51.082 37265 18.667 88.81 83286 56.088 72287 8258 19299 67116 51.522 37.093 18.91 89.114 83.437 56.505 72.419 8.335 19.303 67473 51.404 36.321 18.809 89.171 83.414 56.472 72.5 8.344 19.375 67830 51.084 34.487 18.883 89.54 83.536 56.395 72.769 8.44 19.327 68187 51.461 35.364 18.825 90.059 84.089 56.925 73.185 8.558 19.761 68544 51.316 32.564 19.143 89.978 83.439 56.715 72.898 8.492 19.367 68901 51.84 34.066 18.946 90.125 83.964 56.772 72.996 8.508 19.623 69258 51.712 32.628 1923 90.119 83.488 56.468 73.042 8.54 19.56 69615 51.692 33.662 19.169 90.375 83.626 56.982 73.134 8.685 19:677 69972 51.32 33.557 19.125 90.334 83.799 56.813 73258 8.628 19.711 70329 51.562 34.687 18.964 90.565 83.898 57242 73.44 8.665 19.831 70686 51.687 33.808 19.042 90.079. 83.611 56.955 73.139 8.62 19.55 71043 51.172 33.872 19.103 90.357 83272 56.823 73258 8.713 19.223 71400 51.392 33.669 1929 90.076 83.1 56.823 73.136 8.61 19.363 71757 51.519 34.082 19.069 90.113 82.782 56.56 73239 8.718 19.522 72114 51.059 34.614 19.097 89.719 83.139 56.668 72.745 8.615 19.618 72471 51.433 36211 18.846 89.611 83.067 55.887 72.622 8.49 19.422 72828 51.004 37.535 18.813 89.07 82.771 56.338 72.585 8.5 19.723 73185
v 248
51.306 35.716 . 18.924 89.193 83.047 56.325 74.376 8.585 19206 73542 51.123 34.533 18.91 88.814 82.318 55.721 73.662 8321 19.082 73899 51.147 35.086 18.887 88.714 82.053 55.404 72.928 8.463 18.874 74256 51.191 37.62 18.729 88.058 81.701 55255 72.708 8.406 19.011 74613 51.267 38.856 18.585 87.462 81.593 55.017 72.568 8.419 19.039 74970 51.081 41.421 18.503 87.066 81.314 55.022 71.892 8.187 19.03 75327 51.154 44.587 18.194 86.598 81.414 55.006 72217 8209 19.053 75684 51.119 45.622 18.158 86.014 81.127 54.951 71.834 8.005 18.907 76041 50.872 48.149 17.942 85.573 80.733 54.391 71.72 7.986 19.037 76398 50.671 50.725 17.786 85.179 80.774 54.46 71.797 8.1 19.186 76755 50.843 52.828 17.545 84.679 80.749 54.348 71.79 8.01 19.437 77112 50.698 55.173 17.89 84.311 80.494 54282 71.593 7.755 19.159 77469 50.657 58.23 17.423 83.781 80.393 54209 71.809 7.853 19.332 77826 50.431 60.758 17.479 8323 79.794 53.762 71.714 7.911 19266 78183 50.812 62.263 17.45 82.873 79.871 53.787 71.522 7.869 19292 78540 50.707 64.109 17.159 82.526 79541 53.627 71.599 7.915 19.005 78897 50.341 64.619 16.985 82225 79.452 53.633 71.484 7.793 19.477 79254 50.572 64.938 17.288 81.939 79.376 53.631 7128 7.813 19.093 79811 50.596 66.03 17.138 81.869 79.06 53.537 71.451 7.774 19.114 79988 50.727 66.561 17.15 81.485 78.893 53.381 71266 7.804 18.997 80325 50.413 69.096 16.802 80.913 79.177 53.626 71.332 7.759 19.362 80682 50.349 69.886 16.858 80.871 79.022 53.581 71.514 7.839 19.307 81039 50.607 70.858 16.595 80.344 78.843 53.496 71.335 7.731 18.925 81398 50.161 72.895 16.353 80.052 78.85 53.661 71.521 7.773 19.476 81753 50.108 73.905 16.339 79.441 78.456 53.072 71204 7.749 19.033 82110 49.981 73.507 16.524 79298 77.944 53.087 71.177 7.669 18.908 82467 49.722 73.523 16.598 79.31 77.751 53.181 70.872 7.864 19.364 82824 49.903 74.976 16.297 78.628 76.002 53251 71.173 7.728 19.104 83181 49.907 73.941 16.676 79.142 77261 53.096 70.744 7.76 18.88 83538 49.769 74.613 16.378 78263 77.311 52.934 70.937 7.668 18.628 83895 49.809 75.7 16249 78.381 77.479 53.124 70.794 7.789 19.34 84252 49.568 76.002 16211 78231 77.55 52.984 70.859 7.652 18.699 84609 49.707 75.495 16238 77.482 77.114 53.023 70.853 7.71 18.976 84986 49.683 76.058 16.167 77245 76.982 52.7 70.783 7.71 18.811 85323 49.607 76.891 15.949 77.611 76.819 52.804 70.756 7.691 19.129 85680 49.522 74.849 16294 77.805 76.705 52.839 70.501 7.787 19226 88037 49.815 74.086 16217 77.151 76.563 52.717 70.609 7.587 18.639 88394 49.713 76.576 15.927 77.775 77.327 52.653 70.821 7.687 18.982 86751 49.731 75.372 16.314 77.802 76.612 52.498 70.408 7.612 18.671 87108 49.342 73.994 16.009 77.104 76.614 52.633 70.604 7.672 18.594 87465 49.474 75.129 16.07 77.576 76.52 52.511 70.716 7.726 18.858 87822 49.551 75.484 16.055 77.743 76.758 52236 70.566 7.746 18.842 88179 49.5 74.022 15.969 77.141 76.689 52.552 70.756 7.723 18.537 88536 49.61 74.97 16.156 77.536 76.511 52.555 70.561 7.774 19.189 88893 40
«A w,m ww Ay i 249 250
Filename: I123BHF.SER
Starting material: E-2,4-dimethyl-I-phenyl-I 5-hexadiene
Concentration: 0.0226M
Temperature: 308K 251
I123BHF.SER Integrals B C DE . F G 15257 0212 2.122 0.025 0247 -2228 14.98 0.081 1.993 -0.069 0.198 0.143 15.095 0.071 1.925 -0.071 0.178 0218 15.161 0.062 1.884 -0.074 0.172 0261 15277 0.063 1.828 -0.071 0.161 0297 15.166 0.045 1.795 -0.074 0.16 0.304 15.347 0.057 1.763 -0.069 0.165 0.302 15.361 0.058 1.752 -0.068 0.159 0.336 15.371 0.06 1.718 -0.067 0.154 0.35 15.499 0.08 1.7 -0.063 0.163 0.345 15288 0.08 1.685 -0.067 0.158 0.357 15.334 0.08 1.672 -0.065 0.153 0.366 15.395 0.062 1.66 -0.065 0.155 0.364 15.478 0.069 1.637 -0.062 0.155 0.361 15235 0.06 1.642 -0.065 0.159 0.375 15.326 0.064 1.608 -0.059 0.149 0.37 15.13 0.054 1.603 -0.062 0.148 0.37 15.433 0.067 1.588 -0.059 0.156 0.394 15.491 0.083 1.568 -0.056 0.153 0.388 15.323 0.06 1.565 -0.057 0.149 0.375 15.306 0.068 1.539 -0.058 0.153 0.383 15.35 0.085 1.562 -0.059 0.152 0.379 15.131 0.057 1.54 -0.057 0.143 0.393 15.14 0.077 1.535 -0.056 0.146 0.402 15.182 0.066 1.522 -0.059 0.15 0.386 15.174 0.072 1.508 -0.055 0.147 0.375 15256 0.063 1.506 -0.052 0.149 0.405 15282 0.076 1.497 -0.054 0.15 0.403 15.082 0.077 1.497 -0.053 0.151 0.42 15221 0.077 1.489 -0.056 0.151 0.418 15232 0.082 1.478 -0.051 0.152 0.416 15.162 0.07 1.457 -0.057 0.15 0.408 15.138 0.072 1.467 -0.051 0.148 0.416 15255 0.091 1.454 -0.053 0.151 0.418 15.122 0.078 1.456 -0.048 0.151 0.418 15.173 0.077 1.45 -0.054 0.152 0.408 15.143 0.074 1.45 -0.048 0.152 0.416 15.158 0.075 1.421 -0.05 0.15 0.413 15222 0.075 1.424 -0.049 0.154 0.416 15.196 0.077 1.427 -0.051 0.152 0.416 15.189 0.094 1.441 -0.053 0.154 0.41 15.048 0.074 1.422 -0.049 0.15 0.417 15.072 0.081 1.422 -0.049 0.155 0.412 15.021 0.08 1.426 -0.048 0.157 0.396 15.124 0.082 1.408 -0.047 0.157 0.398 14.878 0.072 1.405 -0.047 0.15 0.404 15.177 0.102 1.407 -0.045 0.156 0.393 15.135 0.087 1.401 -0.047 0.161 0.397 15.082 0.086 1.391 -0.048 0.155 0.393 14.92 0.076 1.394 -0.049 0.156 0.405 252
15.034 0.087 1.387 -0.047 0.163 0.397 15.042 0.083 1.379 -0.048 0.156 0.393 14.857 0.074 1.375 -0.046 0.155 0.408 15.005 0.073 1.376 -0.048 0.155 0.398 15.016 0.081 1.368 -0.048 0.157 0.416 15.037 0.088 1.362 -0.047 0.153 0.407 14.932 0.093 1.387 -0.042 0.156 0.419 14.888 0.092 1.368 -0.046 0.155 0.413 15.04 0.09 1.357 -0.043 0.161 0.409 15.062 0.061 1.365 -0.045 0.157 0.416 14.981 0.08 1.341 -0.05 0.158 0.421 15.048 0.087 1.35 -0.045 0.158 0.407 15.076 0.092 1.356 -0.043 0.155 0.412 14.984 0.095 1.357 -0.047 0.155 0.411 14.889 0.088 1.345 -0.047 0.155 0.414 14.99 0.095 1.349 -0.043 0.151 0.429 15.062 0.099 1.34 -0.042 0.155 0.419 14.857 0.088 1.339 -0.044 0.154 0.41 15.014 0.089 1.336 -0.045 0.153 0.418 14.909 0.093 1.329 -0.05 0.151 0.413 15.026 0.092 1.339 -0.041 0.154 0.406 14.926 0.086 1.322 -0.043 0.149 0.42 14.985 0.089 1.323 -0.043 0.15 0.42 14.976 0.095 1.334 -0.045 0.154 0.424 15.047 0.086 1297 -0.042 0.149 0.419 14.954 0.086 1.305 -0.044 0.153 0.401 14.938 0.094 1.33 -0.043 0.152 0.405 14.99 0.088 1.324 -0.044 0.161 0.4 14.882 0.098 1.323 -0.041 0.152 0.416 14.85 0.088 1.307 -0.044 0.153 0.415 14.884 0.103 1.318 -0.038 0.152 0.419 15.064 0.099 1.302 -0.041 0.152 0.425 14.989 0.095 1296 -0.044 0.152 0.41 14.97 0.107 1.325 -0.042 0.155 0.412 15.005 0.098 1.316 -0.045 0.156 0.411 15.043 0.096 1.303 -0.04 0.152 0.418 14.884 0.092 1286 -0.041 0.149 0.417 14.858 0.107 1.31 -0.042 0.154 0.403 14.808 0.074 1295 -0.038 0.151 0.414 14.823 0.102 1292 -0.04 0.149 0.406 14.938 0.099 1298 -0.039 0.153 0.411 15.139 0.098 1292 -0.038 0.152 0.422 15.104 0.094 1293 -0.043 0.151 0.419 15.009 0.096 1294 -0.044 0.152 0.399 14.901 0.094 1292 -0.038 0.154 0.431 14.912 0.102 1284 -0.043 0.15 0.424 14.91 0.103 1296 -0.041 0.151 0.422 14.979 0.094 1281 -0.044 0.151 0.416 15.023 0.096 1283 -0.039 0.149 0.439 14.833 0.096 1289 -0.041 0.149 0.408 15.024 0.101 1285 -0.042 0.151 0.421 14.897 0.112 1294 -0.039 0.153 0.4 253
14.881 0.097 1277 -0.04 0.147 0.401 14.802 0.088 1288 -0.041 0.15 0.401 14.886 0.097 1286 -0.039 0.151 0.407 14.941 0.1 1291 -0.044 0.145 0.414 14.94 0.097 127 -0.04 0.14 0.417 14.885 0.109 1288 -0.04 0.142 0:408 14.999 0.088 1279 -0.041 0.147 0.401 14.885 0.088 1.28 -0.042 0.14 0.414 14.938 0.1 I z n -0.041 0.139 0.41 14.871 0.102 1.282 -0.04 0.144 0.412 14.779 0.093 1258 -0.042 0.136 0.412 14.897 0.115 1274 -0.041 0.139 0.409 14.93 0.11 1274 -0.042 0.139 0.406 14.885 0.1 1273 -0.044 0.137 0.409 14.792 0.099 1261 -0.047 0.136 0.407 14.919 0.112 1264 -0.04 0.14 0.403 15.023 0.111 1267 -0.038 0.14 0.4 15.09 0.104 1273 -0.043 0.134 0.41 14.913 0.101 127 -0.04 0.13 0.392 14.954 0.108 1252 -0.041 0.131 0.408 15.032 0.114 1265 -0.037 0.135 0.412 14.973 0.092 1257 -0.04 0.133 0.42 14.881 0.11 1276 -0.043. 0.135 0.41 14.887 0.113 1268 -0.041 0.128 0.416 14.804 0.108 1268 -0.046 0.133 0.402 14.814 0.12 1.26 -0.046 0.127 0.418 14.885 0.108 1.259 -0.043 0.127 0.405 14.97 0.105 1251 -0.043 0.13 0.407 14.885 0.11 1246 -0.042 0.122 0.402 15.008 0.109 1259 -0.044 0.122 0.388 15.054 0.108 1252 -0.046 0.121 0.404 15.019 0.117 1252 -0.043 0.121 0.388 14.807 0.107 1247 -0.045 0.112 0.399 15.013 0.107 125 -0.043 0.113 0.388 14.891 0.102 1265 -0.042 0.119 0.414 14.992 0.108 1259 -0.044 0.112 0.407 14.88 0.106 1257 -0.046 0.116 0.39 15.02 0.113 1244 -0.045 0.114 0.401 14.899 0.101 1.23 -0.044 0.109 0.399 14.888 0.102 1233 -0.048 0.104 0.392 14.847 0.108 1.25 -0.048 0.108 0.412 14.955 0.1 1.24 -0.044 0.107 0.404 14.865 0.104 1241 -0.045 0.105 0.407 14.993 0.107 1237 -0.05 0.104 0.397 14.803 0.088 1223 -0.05 0.103 0.402 14.946 0.101 1241 -0.047 0.102 0.395 14.835 0.094 1233 -0.05 0.099 0.402 14.946 0.117 1236 -0.046 0.102 0.398 14.971 0.108 1232 -0.048 0.097 0.393 14.881 0.097 1231 -0.046 0.098 0.388 14.92 0.098 1231 -0.05 0.093 0.399 15.099 0.109 1242 -0.047 0.098 0.385 254
15.008 0.112 1.216 -0.049 0.1 0.382 14.917 0.114 1225 -0.046 0.092 0.388 15.03 0.113 1239 -0.048 0.097 0.4 15.056 0.108 1227 -0.048 0.099 0.389 14.883 0.11 1234 -0.045 0.097 0.394 14.883 0.112 1227 -0.049 0.099 0.387 15.073 0.108 1223 -0.051 0.095 0.402 14.906 0.105 1224 -0.046 0.097 0.394 15.034 0.116 1219 -0.043 0.101 0.398 14.995 0.097 1213 -0.046 0.1 0.407 14.979 0.101 1241 -0.044 0.088 0.393 14.92 0.11 122 -0.045 0.103 0.398 14.971 0.1 1227 -0.043 0.105 0.408 14.945 0.12 1214 -0.044 0.107 0.381 15.129 0.114 1.23 -0.046 0.105 0.397 15.09 0.093 1205 -0.041 0.109 0.394 15.138 0.117 1244 -0.041 0.107 0.389 15.081 0.123 1233 -0.047 0.111 0.38 15.154 0.112 1226 -0.045 0.108 0.39 15.097 0.114 1211 -0.047 0.109 0.399 14.939 0.105 1218 -0.045 0.104 0.402 15.042 0.126 1234 -0.043 0.111 0.408 14.898 0.107 1227 -0.044 0.11 0.398 15.024 0.115 1227 -0.041 0.103 0.401 15.092 0.119 1232 -0.045 0.108 0.388 15.009 0.124 1216 -0.044 0.104 0.388 255
HI J K L M N time (8) 0.888 6.933 1.258 -0.446 2271 -0.05 0 0.457 6.125 1.463 1.407 0.224 3.797 -0.04 357 0.376 5.814 1.765 1.434 0.394 4.092 -0.039 714 0.327 5.603 1.94 1.47 0.487 4.165 -0.037 1071 0299 5.456 2.098 1.476 0.555 4.166 -0.035 1428 0265 5.318 2.174 1.485 0.587 422 -0.037 1785 0281 5221 2275 1.481 0.634 4.197 -0.038 2142 0285 5.112 2.334 1.488 0.638 4.19 -0.031 2499 0.302 5.063 2.408 1.476 0.67 4219 -0.036 2856 0.349 4.962 2.449 1.46 0.664 4.193 -0.032 3213 0292 4.931 2.459 1.481 0.71 4.169 -0.039 3570 0.318 4.885 2.504 1.491 0.719 4.17 -0.038 3927 0.348 4.842 2.535 1.498 0.722 4.168 -0.036 4284 0.406 4.769 2.574 1.469 0.717 4.143 -0.032 4641 0.331 4.771 2.589 1.49 0.774 4.138 -0.041 4998 0.383 4.728 2.621 1.475 0.763 4.139 -0.035 5355 0.354 4.683 2.576 1.494 0.794 4.092 -0.039 5712 0.405 4.644 2.646 1.458 0.772 4.115 -0.036 6069 0.456 4.59 2.672 1.454 0.754 4.113 -0.033 6426 0.429 4.611 2.654 1.471 0.799 4.067 -0.038 6783 0.451 4.564 2.679 1.464 0.777 4.089 -0.034 7140 0.483 4.529 2.699 1.447 0.78 4.109 -0.039 7497 0.438 4.511 2.701 1.48 0.822 4.063 -0.038 7854 0.47 4.479 2.713 1.46 0.817 4.053 -0.034 8211 0.463 4.494 2.691 1.468 0.843 4.059 -0.037 8568 0.503 4.455 2.728 1.444 0.837 4.045 -0.038 8925 0.505 4.474 2.715 1.45 0.838 4.041 -0.039 9282 0.527 4.441 2.74 1.44 0.816 4.045 -0.037 9639 . 0.533 4.433 2.745 1.449 0.828 4.054 -0.035 9998 0.552 4.397 2.745 1.439 0.826 4.039 -0.032 10353 0.597 4.384 2.777 1.421 0.803 4.075 -0.037 10710 0.557 4.407 2.751 1.45 0.863 4.043 -0.035 11067 0.569 4.369 2.741 1.443 0.854 4.019 -0.039 11424 0.617 4.356 2.795 1.435 0.85 4.065 -0.031 11781 0.594 4.337 2.788 1.445 0.844 4.065 -0.037 12138 0.617 4.335 2.779 1.42 0.846 4.043 -0.035 12495 0.619 4.337 2.785 1.444 0.854 4.073 -0.033 12852 0.627 4.316 2.78 1.431 0.873 4.068 -0.034 13209 0.662 4.307 2.779 1.407 0.855 4.077 -0.033 13566 0.667 4283 2.796 1.418 0.86 4.069 -0.032 13923 0.672 4286 2.827 1.395 0.851 4.086 -0.031 14280 0.667 4277 2.821 1.427 0.88 4.065 -0.032 14637 0.7 425 2.812 1.408 0.861 4.067 -0.04 14994 0.669 ' 4283 2.793 1.428 0.894 4.083 -0.024 15351 0.723 4235 2.83 1.402 0.867 4.093 -0.032 15708 0.675 4264 2.813 1.429 0.894 4.061 -0.029 16065 0.745 4231 2.835 1.396 0.867 4.094 -0.024 16422 0.752 4211 2.812 1.398 0.872 4.1 -0.029 16779 0.752 4218 2.83 1.393 0.878 4.069 -0.027 17136 0.722 4236 2.809 1.437 0.903 4.072 -0.032 17493 256
0.757 4.207 2.824 1.377 0.888 4.089 -0.028 17850 0.791 4204 2.831 1.368 0.873 4.077 -0.028 18207 0.774 4208 2.83 1.416 0.891 4.069 -0.028 18564 0.769 4.197 2.822 1.393 0.89 4.088 -0.029 18921 0.819 4.179 2.835 1.393 0.887 4.095 -0.027 19278 0.807 4.186 2.841 1.381 0.887 4.065 -0.026 19835 0.803 4.199 2.845 1.397 0.899 4.098 -0.028 19992 0.803 4.19 2.814 1.391 0.898 4.074 -0.029 20349 0.856 4.14 2.84 1.367 0.878 4.094 -0.023 20708 0.858 4.188 2.839 1.373 0.884 4.073 -0.026 21063 0.841 4.189 2.812 1.405 0.912 4.098 -0.025 21420 0.826 4.163 2.827 1.397 0.924 4.088 -0.026 21777 0.859 4.128 2.827 1.371 0.894 4.08 -0.025 22134 0.855 4.179 2.809 1.388 0.919 4.092 -0.023 22491 0.881 4.148 2.836 1.378 0.887 4.077 -0.018 22848 0.888 4.157 2.847 1.365 0.897 4.065 -0.024 23205 0.924 4.136 2.87 1.376 0.908 4.088 -0.019 23562 0.886 4.18 2.835 1.391 0.927 4.085 -0.026 23919 0.899 4.17 2.818 1.372 0.916 4.062 -0.023 24276 0.89 4.156 2.843 1.359 0.915 4.04 •0.02 24633 0.9 4.162 2.827 1.378 0.912 4.074 -0.016 24990 0.897 4.163 2.848 1.349 0.908 4.065 -0.016 25347 0.926 4.13 2.838 1.347 0.893 4.048 -0.019 25704 0.927 4.161 2.86 1.356 0.891 4.079 -0.021 26061 0.939 4.135 2.861 1.341 0.9 4.085 -0.018 26418 0.947 4.143 2.846 1.363 0.908 4.077 -0.017 26775 0.931 4.144 2.832 1.345 0.921 4.074 -0.017 27132 0.95 4.132 2.85 1.378 0.898 4.09 -0.014 27489 0.961 4.151 2.836 1.349 0.91 4.073 -0.016 27846 0.973 4.134 2.826 1.364 0.895 4.069 -0.015 28203 0.993 4.125 2.863 1.352 0.9 4.1 -0.016 28560 0.987 4.119 2.844 1.318 0.888 4.093 -0.012 28917 0.975 4.146 2.823 1.348 0.908 4.053 -0.017 29274 0.981 4.139 2.843 1.343 0.9 4.079 -0.006 29831 0.998 4.141 2.84 1.338 0.887 4.076 -0.014 29988 1.027 4.118 2.857 1.301 0.887 4.069 -0.009 30345 0.973 4.149 2.816 1.344 0.909 4.08 -0.009 30702 1.027 4.124 2.853 1.332 0.881 4.084 -0.012 31059 0.975 4.126 2.837 1.358 0.93 4.075 -0.009 31416 1.007 4.116 2.81 1.324 0.904 4.052 -0.009 31773 1.028 4.127 2.852 1.337 0.893 4.094 -0.008 32130 1.056 4.09 2.864 1.315 0.876 4.104 -0.009 32487 1.048 4.116 2.841 1.319 0.889 4.07 -0.008 32844 1.017 4.119 2.829 1.34 0.896 4.064 -0.009 33201 1.025 4.111 2.855 1.326 0.902 4.101 -0.005 33558 1.03 4.132 2.842 1.32 0.9 4.061 -0.002 33915 1.021 4.136 2.819 1.329 0.914 4.055 -0.003 34272 1.035 4.123 2.846 1.324 0.911 4.084 -0.007 34629 1.043 4.112 2.825 1.323 0.876 4.073 -0.002 34986 1.039 4.136 2.799 1.323 0.911 4.025 -0.006 35343 1.084 4.092 2.858 129 0.872 4.076 0.002 35700 1.092 4.08 2.871 1.313 0.877 4.081 -0.008 36057 257
1.071 4.102 2.835 1.325 0.909 4.039 -0.003 36414 1.065 4.108 2.834 1.312 0.887 4.043 -0.003 36771 1.084 4.092 2.857 1.329 0.89 4.074 -0.002 37128 1.067 4.104 2.853 1.307 0.876 3.999 -0.001 37485 1.078 4.074 2.842 1288 0.875 4 0.002 37842 1.066 4.114 2.84 1.309 0.904 4.01 0.003 38199 1.091 4.078 2.833 1.338 0.891 4.016 0.001 38556 1.068 4.125 2.819 1.306 0.893 3.958 0 38913 1.068 4.116 2.832 1.32 0.893 3.988 0.002 39270 1.088 4.108 2.848 1.313 0.894 3.994 0.005 39827 1.073 4.108 2.817 1.316 0.906 3.941 0.003 39984 1.104 4.105 2.832 1.311 0.879 3.962 0.005 40341 1.1 4.109 2.831 1.327 0.893 3.987 0.005 40888 1.122 4.076 2.835 1.304 0.871 3.951 0.007 41055 1.072 4.127 2.797 1.302 0.898 3.929 0.002 41412 1.12 4.103 2.83 1294 0.879 3.987 0.005 41769 1.131 4.068 2.843 1281 0.866 3.937 0.008 42126 1.129 4.08 2.845 129 0.871 3.946 0.005 42483 1.085 4.123 2.796 1.312 0.911 3.909 0.008 42840 1.092 4.092 2.826 1.307 0.884 3.876 0.016 43197 1.135 4.064 2.851 1293 0.865 3.903 0.011 43554 1.115 4.092 2.806 1.302 0.869 3.904 0.011 43911 1.124 4.061 2.837 1288 0.853 3.885 0.012 44268 1.11 4.065 2.821 1286 0.876 3.858 0.011 44625 1.097 4.09 2.823 1.322 0.884 3.868 0.011 44982 1.132 4.08 2.814 1291 0.88 3.835 0.01 45339 1.122 4.102 2.834 1289 0.879 3.823 0.014 45698 1.147 4.058 2.828 1291 0.861 3.851 0.012 46053 1.122 4.067 2.794 1287 0.844 3.793 0.012 46410 1.13 4.067 2.812 1287 0.871 3.76 0.014 46767 1.117 4.107 2.801 1281 0.865 3.742 0.015 47124 1.146 4.046 2.814 1276 0.844 3.748 0.017 47481 1.121 4.05 2.795 1.3 0.854 3.684 0.014 47838 1.123 4.055 2.815 1.302 0.848 3.681 0.012 48195 1.108 4.086 2.815 1.301 0.87 3.682 0.02 48552 1.126 4.041 2.8 1288 0.831 3.673 0.019 48909 1.135 4.06 2.807 1279 0.85 3.658 0.015 49266 1.156 4.067 2.804 1296 0.84 3.673 0.023 48823 1.136 4.06 2.791 1293 0.829 3.623 0.019 49980 1.136 . 4.051 2.78 1285 0:838 3.601 0.017 50337 1.123 4.074 2.792 1281 0.838 3.591 0.022 50894 1.144 4.037 2.811 1277 0.819 3.604 0.023 51051 1.131 4.078 2.773 1269 0.835 3.591 0.02 51408 1.113 4.055 2.742 1282 0.838 3.53 0.02 51765 1.123 4.06 2.752 1285 0.824 3.508 0.02 52122 1.126 4.053 2.763 1295 0.822 3.529 0.023 52479 1.107 4.092 2.769 1295 0.847 3.514 0.024 52836 1.119 4.044 2.76 1278 0.826 3.503 0.017 53193 1.132 4.049 2.77 1276 0.822 3.462 0.02 53550 1.108 4.067 2.781 1283 0.828 3.468 0.02 53907 1.081 4.097 2.721 1265 0.845 3.421 0.023 54264 1.119 4.074 2.773 1296 0.838 3.487 0.019 54621 258
1.131 4.04 2.755 1.262 0.812 3.447 0.028 54978 1.129 4.053 2.764 1.291 0.824 3.426 0.023 55335 1.13 4.048 2.75 1279 0.815 3.45 0.024 55692 1.118 4.05 2.761 1294 0.842 3.485 0.028 56049 1.12 4.055 2.768 1277 0.828 3.475 0.026 56406 1.122 4.044 2.745 127 0.824 3.449 0.022 56763 1.115 4.061 2.747 1268 0.815 3.434 0.022 57120 1.119 4.045 2.789 1285 0.813 3.466 0.023 57477 1.135 4.063 2.767 1263 0.817 3.487 0.025 57834 1.135 4.035 2.771 1276 0.829 3.487 0.025 58191 1.13 4.053 2.765 1269 0.817 3.476 0.025 58548 1.15 4.064 2.766 1287 0.832 3.495 0.023 58905 1.155 4.06 2.798 1265 0.824 3.553 0.024 59262 1.149 4.029 2.777 1269 0.824 3.54 0.027 59619 1.168 4.031 2.792 1244 0.807 3.542 0.029 59976 1.126 4.048 2.786 1276 0.818 3.574 0.03 60333. 1.171 4.017 2.781 1259 0.818 3.581 0.03 60890 1.171 4.029 2.813 1272 0.831 3.58 0.028 61047 1.178 4.042 2.797 1258 0.823 3.584 0.033 61404 1.154 4.05 2.776 1278 0.835 3.587 0.031 61761 1.153 4.058 2.784 1283 0.831 3.556 0.028 62118 1.155 4.045 2.8 1277 0.841 3.595 0.032 62475 1.118 4.056 2.783 1285 0.849 3.585 0.035 62832 1.152 4.05 2.794 1267 0.828 3.572 0.032 63189 1.144 4.045 2.772 1261 0.832 3.578 0.033 63546 1.144 4.046 2.799 1256 0.845 3.599 0.031 63903 2.5 259
(Thousands) 260
Filename: I215BHH.SER
Starting material: Z-2-methyl-3-phenyl-1,5-heptadierie
Concentration: 0.0097M
Temperature: 308K 261
I125BHB.SER Integrals BC D E FG H 13.852 -0.021 0.039 -0.017 3.66 0.631 0.165 14.629 -0.006 0.012 0.014 4.096 0.319 0.549 14.488 -0.052 -0.04 -0.048 4.254 0.165 0.702 14.584 -0.019 0.095 0.088 4.233 0.133 0.713 14.743 0.027 0.128 0.209 4.094 0.128 0.727 14.395 0.021 0.177 0.127 3.992 0.137 0.687 14.741 -0.008 0.193 0.136 3.806 0.117 0.663 14.458 -0.011 0.185 0.226 3.921 0.122 0.677 14.293 0.033 0.236 0.224 3.901 0.113 0.679 14.315 0.048 0.368 0.23 3.682 0.117 0.661 14.323 0.086 0.354 0.299 3.637 0.113 0.652 14.433 0.025 0.307 0.265 3.498 0.105 0.626 13.877 0.034 0.408 0.39 3.551 0.115 0.633 14.269 0.06 0.379 0.325 3.531 0.113 0.634 13.633 0.086 0.454 0.353 3.432 0.114 0.619 14.083 0.03 0.422 0.385 3.405 0.111 0.62 13.853 0.049 0.474 0.372 3.319 0.128 0.61 14.149 0.016 0.499 0.354 3.346 0.114 0.589 14.092 0.067 0.55 0.369 3.205 0.107 0.581 13.806 0.051 0.496 0.393 3.137 0.102 0.569 14.055 0.072 0.491 0.423 3.102 0.117 0.578 13.825 0.035 0.529 0.415 3.252 0.101 0.56 13.666 0.072 0.538 0.416 3.101 0.111 0.541 14.06 0.097 0.544 0.525 3.169 0.11 0.575 13.532 0.096 0.606 0.489 3.125 0.11 0.564 13.674 0.066 0.64 0.446 3.177 0.104 0.547 13.855 0.07 0.593 0.517 2.994 0.1 0.551 14.099 0.063 0.566 0.496 2.951 0.091 0.549 14.024 0.071 0.621 0.405 2.866 0.103 0.529 14.264 0.052 0.682 0.53 2.865 0.099 0.525 14.202 0.108 0.66 0.476 2.795 0.091 0.503 13.906 0.076 0.633 0.479 2.799 0.103 0.515 14.008 0.054 0.673 0.461 2.875 0.098 0.52 14.203 0.055 0.744 0.535 2.753 0.101 0.513 14.004 0.087 0.67 0.513 2.798 0.102 0.498 14.072 0.094 0.681 0.525 2.659 0.104 0.489 13.849 0.08 0.681 0.489 2.861 0.092 0.491 14.237 0.08 0.719 0.535 2.737 0.106 0.499 13.311 0.083 0.721 0.449 2.618 0.082 0.475 13.944 0.12 0.763 0.524 2.655 0.09 0.466 14.338 0.02 0.71 0.544 2.637 0.097 0.467 13.803 0.075 0.715 0.562 2.647 0.082 0.473 14.165 0.073 0.759 0.618 2.612 0.079 0.47 14.005 0.064 0.655 0.598 2.709 0.097 0.464 14.123 0.094 0.737 0.626 2.576 0.096 0.454 13.939 0.087 0.746 0.575 2.583 0.072 0.458 14.172 0.081 0.753 0.535 2.516 0.089 0.45 14.083 0.038 0.798 0.542 2.544 0.081 0.436 13.951 0.106 0.764 0.544 2.589 . 0.1 0.432 14.036 0.091 0.8 0.561 2.496 0.093 0.455 262
13.858 0.061 0.776 0.547 2.477 0.085 0.44 13.988 0.107 0.773 0.549 2.34 0.089 0.43 13.952 0.083 0.789 0.604 2.312 0.082 0.432 13.708 0.07 0.829 0.612 2.337 0.088 0.423 14.093 0.085 0.776 0.519 2.459 0.093 0.43 13.847 0.119 0.828 0.591 2.333 0.082 0.414 13.967 0.1 0.828 0.598 2.33 0.083 0.438 14.012 0.104 0.828 0.606 2.44 0.095 0.419 14.055 0.088 0.892 0.595 2.281 0.072 0.413 14.199 0.05 0.837 0.586 2.394 0.085 0.429 14.126 0.049 0.823 0.56 2.317 0.084 0.406 13.68 0.107 0.888 0.593 2.528 0.078 0.407 13.974 0.078 0.873 0.554 2.303 0.097 0.396 14.023 0.082 0.832 0.597 2.309 0.087 0.399 13.747 0.094 0.846 0.584 2.411 0.077 0.4 13.595 0.15 0.92 0.638 2.333 0.087 0.403 14.198 0.083 0.864 0.665 2.312 0.072 0.407 14.028 0.087 0.856 0.599 2.473 0.082 0.417 13.693 0.132 0.905 0.61 2.295 0.079 0.416 13.776 0.098 0.821 0.615 2.165 0.084 0.403 13.938 0.086 0.875 0.617 2.191 0.078 0.386 13.195 0.092 0.862 0.676 2.194 0.086 0.38 13.726 0.101 0.853 0.629 2.26 0.081 0.395 13.843 0.144 0.952 0.664 2.335 0.077 0.385 13.716 0.108 0.868 0.629 2.258 0.082 0.381 13.731 0.074 0.893 0.6 2.157 0.078 0.382 13.641 0.096 0.91 0.564 2.325 0.073 0.402 13.873 0.064 0.887 0.721 2.204 0.079 0.378 13.584 0.146 0.868 0.694 2.174 0.077 0.375 13.854 0.147 0.909 0.698 2.056 0.069 0.387 13.95 0.143 0.937 0.693 2.252 0.082 0.362 14.024 0.106 0.894 0.683 2.261 0.094 0.37 13.697 0.049 0.896 0.541 2.226 0.066 0.367 14.006 0.116 0.91 0.646 1.93 0.087 0.367 14.082 0.077 0.898 0.598 2.05 0.068 0.367 14.002 0.064 0.872 0.681 2.137 0.071 0.373 13.992 0.136 0.94 0.718 2.052 0.078 0.358 13.619 0.069 0.921 0.652 2.117 0.076 0.368 14.047 0.079 0.903 0.619 2.058 0.077 0.379 13.623 0.12 0.902 0.638 2.141 0.074 0.366 13.871 0.072 0.939 0.555 2.125 0.075 0.359 13.782 0.096 0.945 0.701 2.022 0.074 0.347 13.933 0.067 0.932 0.665 2.1 0.078 0.363 14.082 0.111 0.986 0.702 2.029 0.075 0.353 13.533 0.138 0.985 0.739 2.036 0.068 0.323 13.877 0.126 0.957 0.67 1.933 0.068 0.362 13.888 0.091 0.974 0.665 2.05 0.07 0.343 14.173 0.082 0.951 0.66 2.065 0.079 0.354 13.776 0.123 0.952 0.713 2.056 0.073 0.342 13.805 0.09 0.951 0.639 2.091 0.078 0.358 14.22 0.078 0.964 0.686 1.843 0.074 0.324 13.997 0.104 0.976 0.624 2.085 0.066 0.325 263
13.789 0.116 0.942 0.674 2.104 0.072 0.332 13.712 0.135 0.975 0.651 1.992 0.071 0.331 13.683 0.098 0.943 0.577 1.979 0.077 0.331 13.327 0.106 0.97 0.595 2.019 0.064 0.324 14.082 0.094 0.987 0.687 1.932 0.064 0.338 13.875 0.094 0.966 0.673 2.063 0.06 0.35 14.124 0.113 1.003 0.71 2.006 0.062 0.321 13.569 0.095 1.033 0.756 1.962 0.076 0.321 13.848 0.094 1.024 0.646 2.045 0.069 0.336 13.388 0.118 0.947 0.638 2.005 0.067 0.347 13.578 0.119 0.997 0.667 2.015 0.069 0.338 13.6 0.098 1.018 0.707 1.922 0.061 0.31 13.752 0.097 1.019 0.67 2.054 0.045 0331 13.924 0.144 1.018 0.667 1.912 0.072 0.306 13.771 0.169 1.022 0.619 1.895 0.069 0.327 13.706 0.112 1.021 0.687 1.841 0.047 0.336 13.699 0.102 0.998 0.788 1.968 0.068 0.327 13.8 0.105 0.95 0.704 2.03 0.061 0.34 13.432 0.077 0.977 0.621 1.936 0.06 0.305 13.652 0.102 0.997 0.739 1.898 0.071 0.308 13.842 0.091 0.999 0.723 1.964 0.053 0.311 13.751 0.099 0.976 0.689 1.884 0.057 0.324 13.685 0.142 1.021 0.697 1.884 0.067 0.3 13.954 0.118 1.004 0.69 1.79 0.073 0.291 13.801 0.158 1.002 0.642 1.839 0.065 0.286 13.752 0.128 0.997 0.584 1.942 0.063 0.282 14.072 0.141 1.018 0.652 1.828 0.055 0.308 13.938 0.123 0.983 0.642 1.886 0.043 0.299 14.253 0.116 0.972 0.746 1.9 0.046 0.306 13.821 0.081 I 0.75 1.89 0.054 0.299 13.667 0.104 0.984 0.694 1.923 0.061 0.309 13.654 0.143 0.998 0.662 1.832 0.061 0.319 13.911 0.119 0.982 0.711 1.78 0.064 0.3 13.718 0.141 0.989 0.703 1.77 0.058 0.296 13.666 0.105 1.013 0.691 1.807 0.059 0.279 13.775 0.149 0.997 0.702 1.894 0.07 0.295 13.661 0.123 0.988 0.674 1.843 0.055 0.302 13.885 0.133 1.01 0.689 1.866 0.062 0.295 13.968 0.111 1.018 0.655 1.778 0.052 0.295 13.419 0.105 1.043 0.778 1.845 0.06 0.296 13.714 0.143 1.035 0.715 1.758 0.064 0.276 13.849 0.132 1.06 0.664 1.839 0.058 0.307 13.739 0.086 1.011 0.761 1.812 0.059 0.29 13.661 0.154 1.055 0.683 1.71 0.058 0.307 13.634 0.172 1.033 0.734 1.743 0.055 0.294 13.73 0.116 1.069 0.668 1.85 0.059 0.29 13.822 0.14 1.042 0.743 1.685 0.063 0.294 13.638 0.149 1.036 0.7 1.813 0.06 0.283 13.941 0.17 1.053 0.7 1.713 0.047 0.284 13.389 0.099 1.049 0.736 1.827 0.055 0.276 13.489 0.139 1.024 0.683 1.742 0.047 0.277 13.973 0.137 1.069 0.756 1.742 0.052 0.28 264
14.019 0.137 1.021 0.701 1.831 0.057 0.268 13.588 0.12 1.042 0.691 1.855 0.06 0.287 13.833 0.111 1.035 0.716 1.764 0.047 0.289 13.963 0.136 1.02 0.687 1.77 0.047 0.262 13.438 0.16 1.024 0.727 1.839 0.062 0.282 13.967 0.11 1.043 0.716 1.719 0.058 0.269 13.574 0.13 1.028 0.671 1.589 0.048 0.273 13.471 0.121 1.054 0.649 1.729 0.052 0.274 13.85 0.084 1.051 0.682 1.718 0.059 0.294 13.693 0.14 1.054 0.729 1.711 0.055 0.293 14.228 0.113 1.008 0.715 1.808 0.055 0.277 13.838 0.112 1.07 0.727 1.713 0.058 0.276 14.012 0.132 1.044 0.71 1.84 0.055 0.262 13.759 0.133 1.109 0.706 1.704 0.047 0.275 13.786 0.137 1.081 0.714 1.758 0.058 0.276 13.858 0.099 1.064 0.752 1.704 0.062 0.268 13.886 0.142 1.043 0.704 1.853 0.048 0.263 13.32 0.179 1.064 0.74 1.674 0.058 0.28 14.163 0.056 0.998 0.668 1.67 0.057 0.267 14.203 0.148 1.045 0.66 1.741 0.053 0.286 13.722 0.147 1.047 0.733 1.63 0.064 0.29 14.193 0.135 1.076 0.729 1.81 0.061 0.269 14.011 0.135 1.079 0.707 1.758 0.062 0.254 13.741 0.101 1.043 0.721 1.657 0.055 0.274 13.702 0.112 1.084 0.706 1.655 0.054 0.26 13.508 0.111 1.058 0.732 1.746 0.049 0.264 13.799 0.123 1.08 0.666 1.87 0.055 0.253 14.166 0.125 1.031 0.728 1.632 0.049 0.279 13.676 0.157 1.103 0.725 1.676 0.062 0.281 13.668 0.137 1.1 0.678 1.66 0.046 0.252 13.75 0.127 1.072 0.736 1.641 0.053 0.261 13.943 0.143 1.051 0.755 1.715 0.053 0.266 13.919 0.092 1.084 0.758 1.639 0.047 0.265 13.643 0.175 1.061 0.693 1.614 0.036 0.266 14.003 0.121 1.108 0.739 1.815 0.054 0.256 13.741 0.145 1.046 0.705 1.772 0.047 0.238 13.498 0.111 1.071 0.716 1.794 0.037 0.248 13.833 0.093 1.043 0.774 1.668 0.05 0.279 13.766 0.156 1.11 0.729 1.652 0.06 0.261 13.821 0.137 1.036 0.73 1.686 0.045 0.27 14.021 0.127 1.115 0.827 1.817 0.053 0.274 13.221 0.147 1.07 0.782 1.638 0.052 0.241 13.814 0.129 1.06 0.697 1.627 0.046 0.27 13.41 0.125 1.113 0.642 1.772 0.051 0.266 14.027 0.144 1.052 0.78 1.597 0.051 0.248 13.568 0.088 1.074 0.749 1.657 0.06 0.263 13.805 0.133 1.084 0.68 1.818 0.044 0.268 14.089 0.119 1.135 0.75 1.643 0.049 0.253 13.431 0.167 1.126 0.786 1.713 0.051 0.259 13.685 0.16 1.09 0.777 1.737 0.053 0.272 13.983 0.178 1.079 0.729 1.658 0.046 0.266 13.773 0.107 1.026 0.79 1.706 0.065 0.251 265
13.423 0.155 1.073 0.783 1.801 0.047 0.24 13.495 0.113 1.032 0.781 1.561 0.049 0.244 14.194 0.123 1.061 0.737 1.713 0.044 0.257 13.597 0.107 1.065 0.747 1.768 0.047 0.274 13.692 0.129 1.072 0.739 1.721 0.043 0.253 13.722 0.108 1.058 0.701 1.634 0.046 0.244 14.08 0.123 1.083 0.762 1.517 0.053 0.253 14.276 0.122 1.058 0.769 1.608 0.042 021 13.854 0.138 1.102 0.69 1.581 0.052 0.229 13.828 0.141 1.142 0.724 1.609 0.047 0.244 14.118 0.155 1.054 0.722 1.655 0.052 0.242 13.894 0.109 1.042 0.629 1.701 0.046 0.238 13.847 0.119 1.117 0.754 1.637 0.063 0.239 13.692 0.157 1.092 0.707 1.594 0.047 0.245 13.961 0.133 1.137 0.811 1.605 0.042 0.251 14.056 0.156 1.074 0.746 1.606 0.043 0.249 13.389 0.151 1.127 0.754 1.682 0.054 0.239 13.845 0.129 1.091 0.729 1.528 0.047 0.237 13.586 0.161 1.133 0.691 1.662 0.051 0.242 13.927 0.187 1.097 0.784 1.712 0.06 0.238 13.646 0.142 1.098 0.652 1.649 0.042 0.248 13.577 0.165 1.091 0.735 1.535 0.051 0.259 13.683 0.119 1.096 0.674 1.581 0.058 0.256 14.178 0.121 1.05 0.833 1.768 0.045 0.253 13.826 0.146 1.088 0.808 1.682 0.047 0.233 13.593 0.155 1.139 0.764 1.576 0.05 0.26 13.648 0.144 1.106 0.737 1.612 0.036 0.234 14.529 0.135 1.104 0.789 1.609 0.044 0.236 13.432 0.116 1.131 0.761 1.555 0.045 0.243 14.033 0.117 1.069 0.747 1.519 0.052 0.253 14.05 0.159 1.13 0.726 1.651 0.047 0.254 14.421 0.078 1.094 0.773 1.585 0.052 0.252 13.567 0.127 1.126 0.751 1.62 0.064 0.229 13.795 0.122 1.112 0.727 1.576 0.064 0.257 13.725 0.142 1.066 0.757 1.665 0.05 0.232 13.647 0.164 1.146 0.803 1.521 0.055 0.258 13.986 0.101 1.102 0.69 1.694 0.033 0.262 13.591 0.108 1.097 0.742 1.591 0.06 0.257 13.421 0.113 1.092 0.729 1.574 0.052 0.268 13.622 0.125 1.114 0.704 1.575 0.041 0.269 13.661 0.143 1.141 0.785 1.689 0.052 0.254 13.348 0.128 1.097 0.762 1.517 0.056 0.237 13.324 0.159 1.109 0.821 1.532 0.044 0.264 13.786 0.19 1.145 0.781 1.573 0.05 0.265 266
IJ K LM N time (s) 1.631 -0.014 -0.2 13.956 0.02 -1.234 0 2.095 -0.029 -0.21 14.435 0.026 -1.311 357 2.262 -0.031 -0.131 14.361 0.095 -1.348 714 2.187 -0.036 0.011 14.052 0.161 -1.403 1071 2.204 -0.039 0.098 13.889 0.21 -1.488 1428 2.189 -0.046 0.223 13.571 0.291 -1.536 1785 2.129 -0.042 0.292 13.34 0.357 -1.549 2142 2.109 -0.058 0.423 12.993 0.403 -1.638 2499 2.072 -0.066 0.456 12.782 0.429 -1.622 2856 2.092 -0.069 0.521 12.629 0.444 -1.648 3213 2.02 -0.08 0.595 12.391 0.496 -1.685 3570 2.028 -0.092 0.636 12.202 0.55 -1.693 3927 1.999 -0.057 0.697 12.014 0.568 -1.638 4284 1.956 -0.062 0.731 11.873 0.588 -1.619 4641 1.962 -0.063 0.826 11.782 0.604 -1.676 4998 1.882 -0.074 0.854 11.687 0.624 -1.538 5355 1.918 -0.058 0.928 11.548 0.655 -1.529 5712 1.89 -0.052 0.923 11.422 0.665 -1.566 6069 1.856 -0.043 1.001 11.2 0.683 -1.586 6426 1.818 -0.049 1.011 11.136 0.7 -1.563 6783 1.836 -0.047 1.05 11.046 0.721 -1.443 7140 1.761 -0.042 1.082 10.781 0.762 -1.507 7497 1.826 -0.036 1.15 10.801 0.774 -1.566 7854 1.801 -0.046 1.142 10.622 0.797 -1.573 8211 1.771 -0.045 1.183 10.511 0.787 -1.435 8568 1.752 -0.037 1.21 10.498 0.777 -1.449 8925 1.731 -0.053 1.207 10.362 0.804 -1.565 9282 1.732 -0.039 1.246 10.225 0.836 -1.574 9639 1.715 -0.031 1.26 10.165 0.835 -1.535 9996 1.717 -0.019 1.296 10.071 0.846 -1.568 10353 1.718 -0.039 1.306 9.938 0.86 -1.699 10710 1.699 -0.042 1.324 9.933 0.857 -1.69 11067 1.654 -0.019 1.351 9.78 0.862 -1.606 11424 1.635 -0.049 1.355 9.675 0.889 -1.708 11781 1.67 -0.023 1.341 9.778 0.897 -1.734 12138 1.655 -0.035 1.37 9.688 0.882 -1.691 12495 1.628 -0.006 1.373 9.45 0.916 -1.719 12852 1.669 -0.024 1.366 9.424 0.933 -1.805 13209 1.67 -0.042 1.413 9.276 0.927 -1.782 13566 1.645 -0.009 1.452 9.329 0.92 -1.677 13923 1.617 -0.029 1.41 9.264 0.969 -1.784 14280 1.621 -0.041 1.426 9.207 0.945 -1.812 14637 1.614 -0:009 1.499 9.173 0.976 -1.748 14994 1.593 -0.027 1.486 9.041 0.999 -1.781 15351 1.603 -0.026 1.536 9.021 0.987 -1.796 15708 1.547 -0.013 1.54 8.923 0.953 -1.744 16065 1.6 -0.015 1.542 8.955 1.038 -1.775 16422 1.551 -0.027 1.512 8.848 0.984 -1.826 16779 1.574 -0.028 1.531 8.907 0.969 -1.77 17136 1.576 -0.012 1.532 8.764 1.026 -1.747 17493 267
1.549 -0.034 1.54 8.72 0.997 -1.802 17850 1.526 -0.016 1.566 8.612 0.996 -1.761 18207 1.546 -0.003 1.583 8.678 1.009 -1.732 18564 1.536 -0.015 1.596 8.673 1.016 -1.753 18921 1.534 -0.014 1.625 8.58 1.014 -1.767 19278 1.504 -0.019 1.594 8.554 1.009 -1.702 19635 1.538 -0.016 1.61 8.498 1.048 -1.746 19992 1.465 0.002 1.623 8.454 1.045 -1.734 20349 1.479 -0.009 1.61 8.472 1.022 -1.714 20706 1.485 -0.013 1.628 8.423 1.047 -1.759 21063 1.517 -0.004 1.677 8.363 1.054 -1.741 21420 1.429 -0.002 1.677 8.208 1.062 -1.7 21777 1.514 -0.007 1.688 8.295 1.064 -1.715 22134 1.43 -0.011 1.708 8.276 1.077 -1.766 22491 1.467 -0.011 1.712 8.158 1.091 -1.692 22848 1.437 0.002 1.704 8.177 1.07 -1.689 23205 1.443 -0.01 1.697 8.083 1.069 -1.756 23562 1.47 -0.005 1.768 8.133 1.11 -1.76 23919 1.436 0.009 1.745 8.053 1.103 -1.718 24276 1.465 0.001 1.698 8.009 1.109 -1.761 24633 1.452 -0.017 1.762 7.995 1.125 -1.74 24990 1.426 0.007 1.785 7.986 1.117 -1.67 25347 1.44 0.006 1.784 7.907 1.125 -1.683 25704 1.419 0.002 1.722 7.854 1.117 -1.762 26061 1.443 0.005 1.774 7.829 1.133 -1.682 26418 1.439 -0.005 1.783 7.779 1.103 -1.673 26775 1.407 0.006 1.819 7.821 1.148 -1.743 27132 1.424 0.021 1.814 7.819 1.135 -1.736 27489 1.405 -0.015 1.795 7.814 1.12 -1.711 27846 1.416 -0.01 1.779 7.757 1.163 -1.761 28203 1.423 0.011 1,838 7.653 1.148 -1.699 28560 1.396 -0.001 1.81 7.689 1.17 -1.714 28917 1.396 -0.01 1.803 7.644 1.147 -1.773 29274 1.376 0.008 1.84 7.657 1.156 -1.753 29631 1.412 0 1.82 7.518 1.181 -1.695 29988 1.37 0.004 1.843 7.581 1.171 -1.767 30345 1.356 0.006 1.831 7.531 1.153 -1.719 30702 1.374 0.015 1.879 7.485 1.164 -1.681 31059 1.351 -0.005 1.872 7.492 1.149 -1.722 31416 1.354 0.019 1.846 7.461 1.155 -1.726 31773 1.38 0 1.894 7.463 1.181 -1.703 32130 1.331 -0.01 1.868 7.363 1.182 -1.75 32487 1.369 -0.009 1.915 7.37 1.206 -1.732 32844 1.337 0.011 1.893 7.328 1.186 -1.7 33201 1.333 0.01 1.855 7.35 1.216 -1.729 33558 1.325 0.018 1.908 7.283 1.229 -1.718 33915 1.333 0 1.877 7.29 1.195 -1.671 34272 1.288 0.006 1.945 7.258 1.22 -1.679 34629 1.343 0.02 1.903 7.2 1.196 -1.72 34986 1.315 0.003 1.91 7.198 1.211 -1.685 35343 1.335 -0.001 1.895 7.273 1.249 -1.722 35700 1.326 0.004 1.896 7.12 1.195 -1.733 36057 268
1.312 0.019 1.931 7.132 1.214 -1.715 36414 1.287 0.019 1.973 7.078 1.216 -1.664 36771 1.266 0.007 1.939 7.163 1.259 -1.708 37128 1.318 0.014 1.921 7.154 1.226 -1.695 37485 1.318 0 1.944 7.032 1.206 -1.665 37842 1.335 0.021 1.963 6.936 1.215 rl.684 38199 1.25 0.03 1.922 7 1.224 -1.681 38556 1.279 0.024 1.948 7.011 1.218 -1.625 38913 1.28 0.011 1.943 6.973 1.212 -1.688 39270 1.276 0.008 1.947 6.978 1.231 -1.669 39627 1.3 0.006 1.945 6.857 1.225 -1.651 39984 1.282 0.012 1.929 7.007 1.212 -1.693 40341 1.254 0.016 1.963 6.827 1.235 -1.653 40698 1.301 0.032 1.966 6.899 1.22 -1.654 41055 1.239 0.028 1.958 6.841 1.215 -1.625 41412 1.278 0.036 1.961 6.836 1.225 -1.655 41769 1.259 0.012 1.958 6.729 1.236 -1.604 42126 1.26 0.013 1.923 6.796 1.252 -1.633 42483 1.285 0.008 1.932 6.731 1.237 -1.67 42840 1.252 0.005 1.949 6.739 1.231 -1.651 43197 1.227 0.003 1.973 6.712 1.238 -1.572 43554 1.292 0.026 1.969 6.786 1.226 -1.64 43911 1.259 0.013 1.98 6.652 1.246 -1.603 44268 1.236 0.002 1.982 6.608 1.237 -1.609 44625 1.234 0.005 2.018 6.729 1.266 -1.62 44982 1.228 0.022 1.985 6.674 1.256 -1.606 45339 1.245 0.03 2.026 6.718 1.246 -1.604 45696 1.202 0.022 1.992 6.667 1.263 -1.622 46053 1.164 0.024 2.025 6.542 1.267 -1.612 46410 1.229 0.023 1.999 6.59 1.26 -1.616 46767 1.197 0.028 1.996 6.629 1.271 -1.584 47124 1.2 0.061 2.033 6.578 1.25 -1.57 47481 1.221 0.019 2.052 6.511 1.258 -1.621 47838 1.213 0.026 2.032 6.556 1.27 -1.567 48195 1.255 0.008 2 6.574 1.285 -1.625 48552 1.238 0.03 2.01 6.532 1.269 -1.584 48909 1.156 0.04 2.046 6.473 1.24 -1.545 49266 1.203 0.031 2.01 6.5 1.278 -1.585 49623 1.251 0.019 2.029 6.4 1.272 -1.588 49980 1.182 0.031 2.044 6.445 1.28 -1.572 50337 1.219 0.031 2.042 6.476 1.271 -1.547 50694 1.233 0.013 2.013 6.354 1.302 -1.593 51051 1.199 0.041 2.065 6.365 1.266 -1.577 51408 1.215 0.032 2.047 6.413 1.263 -1.565 51765 1.234 0.024 2.072 6.38 1.267 -1.545 52122 1.15 0.037 2.046 6.313 1.269 -1.573 52479 1.175 0.02 2.031 6.365 1.274 -1.545 52836 1.197 0.02 2.068 6.389 1.286 -1.551 53193 1.169 0.029 2.072 6.372 1.268 -1,553 53550 1.208 0.021 2.07 6.348 1.251 -1:527 53907 1.191 0.043 2.094 6.252 1.268 -1.522 54264 1.188 0.025 2.082 6.36 1.284 -1.544 54621 269
1.182 0.021 2.055 6.253 1.284 -1.575 54978 1.177 0.029 2.055 6.197 1.274 -1.55 55335 1.208 0.021 2.067 6.266 1.283 -1.53 55692 1.143 0.01 2.054 6.244 1.313 -1.586 56049 1.111 0.035 2.115 6.255 1.294 -1.514 56406 1.149 0.038 2.078 6.252 1.27 -1.538 56763 1.147 0.037 2.079 6.255 1.315 -1.557 57120 1.192 0.046 2.101 6.21 1.29 -1.562 57477 1.189 0.048 2.063 6.136 1.325 -1.538 57834 1.192 0.017 2.068 6.176 1.282 -1.515 58191 1.198 0.044 2.081 6.16 1.314 -1.565 58548 1.18 0.029 2.07 6.091 1.305 -1.557 58905 1.118 0.015 2.122 6.214 1.341 -1.559 59262 1.184 0.027 2.053 6.165 1.307 -1.543 59619 1.189 0.047 2.093 6.188 1.316 -1.565 59976 1.174 0.047 2.103 6.143 1.32 -1.547 60333 1.133 0.027 2.122 6.101 1.305 -1.551 60690 1.189 0.018 2.059 6.157 1.329 -1.573 61047 1.187 0.019 2.066 6.089 1.312 -1.554 61404 1.118 0.058 2.116 6.133 1.305 -1.522 61761 1.174 0.038 2.078 6.113 1.322 -1.548 62118 1.196 0.032 2.1 6.064 1.315 -1.548 62475 1.19 0.047 2.104 6.071 1.337 -1.524 62832 1.122 0.045 2.101 6.033 1.349 -1.537 63189 1.135 0.038 2.114 6.063 1.298 -1.534 63546 1.181 0.042 2.144 6.045 1.324 -1.529 63903 1.141 0.033 2.086 6.029 1.326 -1.53 64260 1.134 0.041 2.12 6.065 1.34 -1.52 64617 1.158 0.042 2.119 6.077 1.307 -1.523 64974 1.189 0.037 2.101 6.005 1.326 -1.539 65331 1.129 0.026 2.128 5.986 1.319. -1.529 65688 LI 0.046 2.138 6.011 1.331 -1.535 66045 1.146 0.064 2.191 6.096 1.349 -1.501 66402 1.15 0.043 2.151 5.972 1.352 -1.555 66759 1.133 0.065 2.186 6.092 1.357 -1.53 67116 1.117 0.041 2.13 5.901 1.356 -1.529 67473 1.193 0.039 2.156 5.974 1.344 -1.508 67830 1.095 0.036 2.144 5.952 1.349 -1.52 68187 1.139 0.056 2.17 6.011 1.315 -1.485 68544 1.082 0.063 2.178 6 1.332 -1.52 68901 1.16 0.045 2.153 5.997 1.332 -1.503 69258 1.149 0.046 2.187 5.824 1.372 -1.516 69615 1.119 0.054 2.164 5.919 1.37 -1.501 69972 1.115 0.041 2.142 5.963 1.353 -1.507 70329 1.129 0.06 2.217 5.837 1.367 -1.49 70686 1.141 0.049 2.189 5.912 1.337 -1.503 71043 1.144 0.055 2.176 5.948 1.38 -1.485 71400 1.124 0.057 2.159 5.901 1.344 -1.497 71757 1.089 0.051 2.155 5.965 1.357 -1.465 72114 1.074 0.053 2.178 5.823 1.348 -1.47(3 72471 1.155 0.067 2.194 5.884 1.361 -1.445 72828 1.132 0.037 2.14 5.805 1.347 -1.484 73185 270
1.094 0.044 2.147 5.845 1.355 -1.51 73542 1.125 0.063 2.15 5.843 1.343 -1.491 73899 1.087 0.047 2.139 5.778 1.357 -1.478 74256 1.141 0.055 2.175 5.849 1.344 -1.489 74613 1.094 0.049 2.168 5.797 1.329 -1.493 74970 1.101 0.057 2.197 5.905 1.353 -1.452 75327 1.107 0.041 2.161 5.766 1.339 -1.503 75684 1.098 0.065 2.228 5.769 1.321 -1.412 76041 1.107 0.049 2.165 5.742 1.354 -1.518 76398 1.087 0.04 2.138 5.759 1.338 -1.482 76755 1.087 0.042 2.167 5.748 1.347 -1.508 77112 1.102 0.052 2.172 5.688 1.346 -1.468 77469 1.151 0.053 2.22 5.666 1.373 -1.492 77826 1.108 0.039 2.206 5.742 1.338 -1.486 78183 1.033 0.059 2.205 5.73 1.341 -1.495 78540 1.098 0.034 2.183 5.727 1.361 -1.498 78897 1.08 0.034 2.2 5.704 1.36 -1.486 79254 1.12 0.07 2.131 5.727 1.366 -1.507 79611 1.071 0.049 2.212 5.731 1.383 -1.509 79968 1.126 0.038 2.17 5.696 1.374 -1.479 80325 1.119 0.063 2.147 5.75 1.372 -1.5 80682 1.121 0.043 2.182 5.724 1.4 -1.497 81039 1.127 0.068 2.213 5.724 1.378 -1.494 81396 1.102 0.063 2.204 5.72 1.402 -1.553 81753 1.072 0.055 2.196 5.801 1.39 -1.538 82110 1.117 0.049 2.195 5.683 1.387 -1.519 82467 1.1 0.076 2.255 5.735 1.372 -1.524 82824 1.103 0.052 2.191 5.74 1.395 -1.546 83181 1.088 0.033 2.237 5.638 1.412 -1.567 83538 1.105 0.044 2.217 5.721 1.433 -1.575 83895 1.083 0.053 2.223 5.629 1.413 -1.596 84252 1.077 0.05 2.214 5.682 1.412 -1.553 84609 1.085 0.048 2.267 5.751 1.429 -1.544 84966 1.093 0.035 2.279 5.664 1.445 -1.595 85323 1.078 0.072 2.286 5.629 1.455 -1.581 85680 1.078 0.062 2.299 5.682 1.426 -1.505 86037 1.094 0.08 2.33 5.656 1.454 -1.533 86394 1.121 0.064 2.323 5.741 1.442 -1.59 86751 1.087 0.065 2.304 5.68 1.448 -1.488 87108 1.074 0.093 2.36 5.769 1.447 -1.437 87465 1.116 0.081 2.344 5.656 1.444 -1.518 87822 1.086 0.077 2.36 5.692 1.469 -1.514 88179 1.136 0.088 2.414 5.606 1.448 -1.429 88536 1.087 0.08 2.453 5.7 1.458 -1.365 88893 4.5 271 U Z l /4UU 5