A Study of the Kinetics Op Neutralization Op Cyclic

A STUDY OF THE KINETICS OP NEUTRALIZATION OP CYCLIC,

BICYCLIC, AND ARYLALKYL NITRO COMPOUNDS

DISSERTATION

Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of the Ohio State University

PAT WAYNE KEITH FLANAGAN, B.S,

The Ohio State University 19<7

Approved by:

Advlser Department of Chemistry ACKNOWLEDGEMENTS

I would like to express my appreciation to Dr. Harold Shechter for suggesting this problem and for his guidance during the course of this investigation. I am grateful to the National Science Foundation and to the Allied Chemical and Dye Company for fellowship funds.

ii TABLE OP CONTENTS Page

I. INTRODUCTION...... 1 II. THEORY AND HISTORY...... 4 Structure and Reactivity.. of Acidic...... Nltro Compounds...... 4 Deuterium Effects on,Kinetics of...... Reaction...... '...... 21 Factors Affecting Reactivities., of ...... Cyclic and Blcycllc Systems ...... 25 III. DISCUSSION OP RESULTS OP THE PRESENT. . . INVESTIGATION ...... 56 Kinetics of Neutralization...... 36 Nltrocycloalkanes, ...... 36 The Deuterium Isotope Effect In Neutralization of Nltro cycloalkanes with Hydroxide Ion...... 51 Blcycllc Nltro Compounds ...... 53 Meta and Para-Sùbstitutod 1-Phenylnltroethanes ...... 59 The Ultraviolet Absorption Spectra of Cyclic and Blcycllc Nltro Compounds. . 64

IV. EXPERIMENTAL...... 71 Preparation and Purification of Nltro Compounds...... 71 Endo-4-nltroblcvclo 2 2 1 heptene-2. . 71 Exo-5-nltrobicvclo 2 2 1 heptene-2 . . 72 Endo-2-nltroblcvclo 2 2 1 heptane. . . ?4 Exo-2-nltroblcvclo 2 2 1 heptane . . . 75 Endo-5-nltroblcyolo 2 2 2 octene-2 . . 76 2-Nltroblcyclo 2 2 2 octane...... 77 Exo-4-nltroblcvclo 2 2 2 octene-2. . . 78 1-Phenylnltreethane...... 79 l_(g_Nltrophenyl)nltroethane ..... 79 l-(E,-Tolyl)nltroethane...... 80 l-(m-Nltrophenyl) nit roe thane. .. . ., ..... 81 Nltrocyclobutane...... 81 Nltrocyclopentane ...... 83 Nltrocyclohexane...... 83 Nltrocycloheptane ...... 84 111 TABLE OP CONTENTS (Continued) Page

Nitrocyclooctane ...... 84 4-Nitrocyolohexene ...... 85 1-d-Nitrocyolobutane ...... 85 1-d-Nitrocyclopentane...... 8? 1-d-Nltrooyclohexane ...... 8? Determination of the. Kinetic Constants. . 88 Equipment...... 88 Constant temperature hath . . . 88 Conductometrio equipment. . . . 91 Conductivity cells...... 93 Hypodermic syringes ...... 95 Kinetic Techniques...... 95 Solvents and solutions...... 95 Preparation and execution of a kinetic experiment...... 97 Calculations...... 101 Kinetic analysis of neutralization of pure nitro compounds...... 101 Kinetic analysis of neutralization of a mixture of two nitro compounds«... lo6 Activation parameters...... 110 Ultraviolet Spectra of Anions of Cyclic and Bicyclic Nitro Compounds. . . Ill

APPENDIX A...... 112 APPENDIX B...... 122 APPENDIX C...... 244

AUTOBIOGRAPHY ...... 259

iv LIST OF FIGURES

Figure Page 1. Hammett Plot for Neutralization of ... .. 1-Phenylnitroethanes 62 2. Heater Control Circuit...... 90 3. Diagram of Conductivity Apparatus ...... 92 Conductivity Cell...... 94- 5.-7. Activation Energy Plots for Neutralization of Cyclic and Bicyclic Nitro Compounds .113-115 8,-13. Representative Plots of t(Rgp-R) versus R for Neutralization of Nitro Compounds.116-121

14.-33. Infrared Spectra of the Nitro Compounds. .245-255

34 .-36. Ultraviolet Absorption Spectra of Anions of Cyclic and Bicyclic Nitro Compounds .256-258

V LIST OP TABLES

Table Page 1. Rates of Reaction of Simple Nitroalkanes.. with Hydroxide Ion...... 12 2. Reaction of 2-Nitropropane with ...... Hydroxide Ion...... 13 3. Reaction of Nitrocycloalkanes..with Hydroxide Ion...... 14 4. Reaction of Aliphatic Nitro Compounds. , with Hydroxide I o n ...... 14 5. Reaction of Nitroalkanes with Hydroxide Ion...... 15 6. Ionization Constants of Nitro Compounds and Nitronic Acids...... 19 7. The Influence of Temperature on the Deuterium Isotope Effect for Rupture of a Bond to Carbon...... 22

8. Kinetics of Neutralization of Nitro- methane and Trideuteronitromethane by Acetate Ion in H2O and D2O at 25°. . 24 9. Approximate Relative Rates of Acetolysis of Cyclic and Bicyclic Tosylates, . . . 32

10. Kinetic Constants and Parameters for Neutralization of Nitro Compounds with Sodium Hydroxide in Dioxan/Water (50:50 by vol.)...... 38 11. A Comparison of the Rate Constants Obtained by Various Investigators for Neutraliza tion of Homologous Nitrocycloalkanes with Hydroxide I o n ...... 4o

vi LIST OP TABLES (Continued)

Table Page

12. The Effects of Ring Size on the Relative Reactivities of Homologous Cyclic.. , . Compounds...... 13. Deuterium Isotope Effects in . . Neutralization of Nitrocycloalkanes. . 52

14. Reaction of Bicyclic Nitro Compounds. ., ., with Hydroxide Ion...... 5^ 15 . Neutralization of m and p-Substituted 1-Phenylnitroethanes with. Hydroxide. , Ion...... 60 16. Absorption Spectra of Anions of Nitro Compounds in Dioxan-Water (5 0 :50 vol. )...... 65 17 .-33. Collected Velocity Constants for the Neutralization of Nitro Compounds.... by Sodium Hydroxide...... 123-139

34 .-I37 . Kinetic Data for the Neutralization of Nitro Compounds by Sodium Hydroxide l4o-243

vii I. INTRODUCTION

The rates of neutralization of primary and secondary nltro compounds (Equation 1) by bases show a marked dependence on both the structures of the nltro compounds H R'-c-A/d, + B: ^ R,-Ç = A/C1 + BH* (i) & 4 and of the bases. Removal of a proton from a nltro com pound Is subject to general basic catalysis, and correla tions of the Bronsted type between the strength of the base and rate of removal of the proton are, In general, applicable. No correlation as yet has been found, however, between the acid strengths of nltro compounds (as deter mined from their Ionization constants In water)' and their rates of reaction with a given base. The subject of ring strain and Its effects on the reactivity of cyclic molecules has received considerable attention during the past decade. Fundamental concepts have been Introduced relating reactivity and structure which have added greatly to the understanding of the fundamental details of organic chemistry. The theories proposed however are qualitative and certain anomalies still exist; furthermore the concepts have not been tested In reactions which involve mechanisms of widely differing types.

Much attention has also been given to effects of structure on the reactivities of bicyclic compounds. Reports of rearrangements and anomalous reactivities in these systems are prevalent in the current literature. However, almost all the quantitative measurements of reactivity of bicyclic compounds have been concerned with reactions of the carbonium ion type and thus interpreta tion of the fundamental effects in these systems is limited. It was therefore the purpose of the present investi gation to determine the influence of structure on the rates and kinetic parameters of neutralization of acidic nitro compounds in the following series: (1) homologous nitrocycloalkanes, in which the size of the ring is varied from cyclobutyl to cyclooctyl, and,* (2) the 5-nitrobicycloC2'2 *lHheptyl and [2"2-2]octyl systems, in which the unsaturation in the carbon skeleton and the configuration of the carbon

atom in position 5 are varied. In order to gain more insight into the fundamental details of the transition state for these neutralizations, it was decided: (1) to determine the isotope effects of deuterium in neutralization of 1-deuteronitrocyclobutane, 1-deuteronitrocyclopentane and l-deuteronitro- cyclohexane, and; (2) to determine the electrical effects of meta and nara substituents on the kinetics of neutrali zation of substituted 1-phenylnitroethanes. II. THEORY AND HISTORY

Structure and Reactivity of Acidic Nitro Compounds

Nitro compounds (1) (R-NOg) are derivatives of

(1) Simple mononitro compounds were first synthesized by reaction of silver nitrite with alkyl halides; V. Meyer and 0. Stuber, Ber., 1, 203 (1872). hydrocarbons in which an electronegative nitro group

(-NOg) is attached to carbon through nitrogen. These compounds are resonance hybrids of the following important structures in which the equal contributions make the nÜrb..g:iouKi

symmetrical. Such derivatives may have a nitro group attached either to primary, secondary, or tertiary carbon atoms. Primary and secondary nitro compounds are usually described as pseudo-acids because they react slowly (and at measurable rates) with bases (Equation 1) to form salts which are strong electrolytes. Acidification of solutions of these salts (Equation 2) at low temperatures yields nitronic acids which are (generally) unstable tautomers

(Equation 3) of true nitro compounds (2), 4 R—CH^— ^ ^ (1 )

'/(nitro compound) (nitronate anion)

R-C//=/)C^f -----> R-C;/=/V(^ +B: (2) '0 (nitronic acid)

R-CH=A^2i ^ R-CH-A/^^ (3)

(2) (a) A* Hantzsch and 0, W, Schultz, Ber,, 2^, 699 (1896); (b) A. P. Holleraan, Bec. trav, chim., jji, 35^ (1896); (c) M. Konovaloff, Ber., 2£, 2193 (.1896).

Nitronic acids differ from their isomeric nitro com pounds in that they react immediately (as do their salts) with bromine or chlorine to yield gem-halonitro compounds; nitro compounds do not react as such, Nitronic acids are neutralized very rapidly by (even) weak bases and give typical enol reactions with ferric chloride. The struc tures of the various forms of nitrocompounds historically have been the subject of marked controversy; the litera ture of this controversy and a discussion of the present knowledge of the structures of nitro and aci-nitro com pounds have been reviewed by Stone (3).

(3) H. Stone, Ph.D. .dissertation. The Ohio State Univer sity, 1950, 6

Holleraan was the first to note that the changes from nltro compound to nitronate ion (commonly called aci anion) or from nitronic acid to nitro compound could he followed by measuring the electrical conductivities of reacting solutions (4). This method was subsequently

(4) A, P. Holleman, Rec, trav. chim., 14, 121 (1895).

used by Hantzsch for the first semiquantitative measure of the kinetics of neutralization of a nitro compound by a base (5). Hantzsch demonstrated that the reaction

(5) A. Hantzsch, Ber., 22, 575 (1899). between nitroethane and hydroxide ion was time dependent and used this to classify nitroethane as a "pseudo acid". Hantzsch felt these "pseudo acids" had to undergo internal rearrangement to their "true acid" forms before reacting with a base. Using modern structures, the ideas of Hantzsch (illustrated by a nitrocompound)' are expressed as :

+ B: — ^ +B:/ (5) In 1929, Junell studied the rates of brominatlon of 2-nltropropane, nltromethane, bromonltromethane, and dibromonitromethane in aqueous hydrobroiiiic and hydro chloric acids (6). In this investigation it was found

(6) R. Junell, Z. physik. Chem., Al4l, 7 I (I929). that the rates did not depend on the concentrations of halogen but were first order with respect to concentra tion of the nitro compounds. Under comparable experimental conditions dibromonitromethane was bromlnated approximately 50 times as fast as bromonltromethane, which was bromlnated approximately 200 times as rapidly as nitromethane, Nitromethane was found to undergo neutralization 4.5 times as fast as 2-nitropropane. In general, rates of broraina- tion (followed by titration of unreacted bromine) decreased slightly as the acid concentration Increased. Pederson extended the studies of Junell by deter mining the rates of brominatlon of nitromethane in water and in buffered solutions containing various basic anions

(7 ). This study led to the discovery of the following

(7) K. J. Pederson, Kgl. Danske Videnskab. Selskab, Math. -fys. Medd., 12., No. 1 (1932). important new facts. The rates of brominatlon were the 8

same in water as in hydrobromic acid; the rates were pro portional to the concentrations of the base and of nitro methane; undissociated acids had no effect; and the rates were dependent on the strength of the base in the manner outlined for general base catalysis by Bronsted in his newly developed theory of catalysis (8), The mechanism

(8) J, N. Bronsted, Chem. Revs., 23I (I928). advanced by Pederson is as follows, in which :

4- B; 3to W > R,C-A/^ 4- B - y (6)

ff^e=/va: (7)

The mechanism postulated requires only incorporation of modern concepts of resonance theory to be equivalent to that presently accepted:

RaCHMQ). 4- 6-' ^ > R3lC=A^^ -h B:H'^ (8) As a result of this study, the theory that neutralization of a nltro compound occurs by attack of the base on the true nitro compound was placed on a firm experimental basis. Shortly afterward, Junell extended his neutralization studies to include the kinetics of reaction of nitro

ethane in hydrobromic acid (9). Meyer and Locher (10a) and Bamberger and Rust (10b) had shown that primary

(9) E, Junell, Arkiv Kemi, IIB. No. 27 (193^). (10) (a) V, Meyer and J, Locher, Ann., 180. 163 (1876); (b) E. Bamberger and E. Rust, Ber., 12., ^5 (1902).

nitroalkanes are isomerized by mineral acids to hydroxamic acids, and then hydrolyzed to hydroxylamine and carboxylic acids. Since the conditions for isomerization and hydrolysis of nitroethane were similar to those used in his neutralization studies, Junell determined the rate of formation of ethanehydroxamic acid or hydroxylamine from nitroethane in hydrochloric acid (11). The rate

(11) R. Junell, Arkiv Kemi, _11B, No. 30 (1934).

constant for isomerization and hydrolysis of nitroethane was found to be almost identical to that of brominatlon of nitroethane. Quantitative brominatlon experiments showed that no etlianehydroxamic acid was formed in the presence of bromine. The results thus clearly indicated that brominatlon of nitroethane and formation of ethane hydroxamic acid from nitroethane proceed from the same 10 intermediate, that is, the aci ion or the nitronic acid formed from the aci ion.

In spite of the work of Junell and Pederson, opinion has prevailed in some of the literature that the conver sion of a nitrocompound to its aci-nitro form can he catalyzed by acids in aqueous solution (3, 12). Perhaps

(12) H. B. Hass and E. P. Riley, Chem. Revs,, 32, 373 (1943). the principle basis for this view was the early work (13)

(13) T. M, Lowry and E. H. Magson, J. Chem. Soc., 23., 107 (1908). on the mutarotation of nitrocaraphor ((+) -3-nitrocamphor). Mutarotation of nitrocamphor undoubtedly occurs through inversion of configuration of carbon atom 3» Traces of

■HO^ Nitrocamphor acids, bases and water, and even neutral salts were found to have marked catalytic effects. It is not at all clear that Lowry and Magson demonstrated acid catalysis in isomerization, since potassium chloride was almost as effective as hydrogen chloride. The racemization of 11

3-nitrocaraphor was reinvestigated by Bell and Sherred and

found to be general acid catalyzed (l4). Since nitro camphor is an o(-nitro ketone, it is probable that inversion

(14J R, P. Bell and J. A. Sherred, J, Chem. Soc., 1202 (1940).

of carbon atom 3 occurs by acid-catalyzed enolization of the keto function. Certainly it is not valid to extend the racemizable properties of this compound to simple nitro compounds. Rates of neutralization of simple nitroalkanes with hydroxide ion have been studied by Junell (15 a,b) using a bromination method, and by Maron and LaMer (15c) using

(15) (a) R. Junell, Arkiv Kemi, IIB. No. 34 (1934); (b) R. Junell, Dissertation, Uppsala, 1935; (c) S. H. Maron and V. K. La Mer, J. Am. Chem. Soc,, 2588 (1938).

a conductivity method. The results of the studies are summarized in Table 1. Maron and La Mer (I5c) pointed out some inherent inaccuracies of the bromination method and suggested that the conductometrio method is better for following neutrali

zation of nitro compounds. The effect of solvent composition on the reaction of 2-nitropropane with hydroxide ion has been investigated Table 1 12 Rates of Reaction of Simple Nitroalkanes with Hydroxide Ion (in water at 0“, k2 's in l./m.-min.)

Coraoound Maron and La Mer (ISc) Junell (15a. b)

Nitromethane 238 1?3 Nitroethane 39.1 35.2 1-Nitropropane 29.2 2-Nitropropane . 2.08 1.94

(Table 2) by Traynham (16); it was found in general that (16) J, G. Traynham, unpublished research, The Ohio State University. 1952.______:______a decrease in the solvating power of the solvent increased the rate of neutralization of 2-nitropropane, The trend in activation parameters is consistent with the premise that the reactants are more solvated than is the tran

sition state. In initial studies of the effects of ring size on

the reactivity of nitro compounds. Stone (3) and Traynham (16) determined the kinetics of reactions of hydroxide ion and various homologous nitrocycloalkanes in 50/50 dioxan-water. The results of these investigations are

included in Table 3. The investigation by Traynham (l6) also included a study (Table 4) of the effects of structure

on the rates of neutralization of various aliphatic nitro compounds. The results are in general accord with induc

tive and steric considerations. 13

Table 2

Reaction of 2-Nitropropane with Hydroxide Ion

Solvent kgfoO)*

Water 2.13 ■ l4.6 -11.5 90 Water/lO Dioxan 2.86 l4.l -12.9 70 Water/30 Dioxan 5.06 13.0 -I5.5 50 Water/50 Dioxan 8.03 13.1 -14.4 30 Water/70 Dioxan 11.4 12.4 -16.4

* in l./m.-min. ** in kcal./mole *** in cal./raole-degree

In 1955 Elving and Lakritz (I7 ) reported the follow ing reaction velocity constants (Table 5) for neutraliza tion of simple nitroalkanes by hydroxide ion in water using a megacycle frequency oscillator method. (This method also depends on changes in conductivity.) Again, the trend in reaction velocity constants is in agreement with that expected in terms of electrical and steric factors in the nitroalkanes; several of these values appear to be somewhat low, however. The reaction velocity

(17) P. J. Elving and J. Lakritz, J. Am. Chem. Soc., ZZ> 3217 (1955). 14-

Table 3 Reaction of Nitrocycloalkanes with Hydroxide Ion (50/50 dioxan-water, 0°, kg's in l./m.-min.)

Comnound Stone (3) Travnham' ( 16/

Nitrocyclopropane 0.0 (250 ) — — —

Nltrocyclobutane 24-7 204- Nltrocyclopentane 85.0 4-6.2 Nltrocyclohexane 7.8 7 .54 -

Nltrocycloheptane 31.7 22.7 Nitrocyclooctane — — 17.3

Table 4- Reaction of Aliphatic Nitro Compounds with Hydroxide Ion (50/50 dioxan-water, 0°, kg's in l./m.-min.)

Compound

2-Nitropropane 8.03 2-Nitrobutane 3.82

2-Nitropentane 2.78

3-Nitropentane 1.69

4-Nitroheptane o'.713 2,2-Dimethyl-3-nitrobutane 0.0 15

Table 5 Reaction of Nitroalkanes with., Hydroxide Ion (in water, 25 °, kg's in l./m.-min.)

Compound kg

Nitromethane 1026 Nitroethane 236 1-Nitropropane 195 2-Nitropropane 16.4-

1-Nitrobutane I92 2-Nitrobutane 8,8 constant for nitromethane when coupled with that determined at 0° by Maron and La Mer (15c) would indicate a very low activation energy (<10 kcal./mole) for neutralization.

Bell and Clunie (18) obtained a higher value, 353> for

(18) R. P. Bell and J. C. Clunie, Proc. Roy. Soc., A212. 16 (1952). nitroethane; the value for 2-nitropropane, 22.5, deter mined by Traynham (I6) is also greater. lé

Because nitroethane is neutralized by various bases at convenient rates to form the stable ethanenitronate anion, it has often been used as a model in acid-base reactions. Bell and Norris studied its neutralization by hydroxide ion in methanol-water at temperatures ranging

from 20° to -32° in an unsuccessful attempt to find a "tunnel effect,*' or non-classical penetration of an energy barrier (19). Pearson (20a) and Pearson and Williams (20b, c) have studied rates of reaction between nitroethane and

(19) B. P. Bell and A. D. Norris, J. Chem, Soc., 85^ (19^1). (20) (a) H. G. Pearson, J. Am. Chem. Soc,,'20.» 204 (1948); (b) R. G. Pearson and F. V. Williams, J. Am. Chem. Soc., 21, 3073 (1953 ); (o) R. G. Pearson and P. V. Williams, J. Am. Chem. Soc., 258 (1954). an extensive series of amine and pyridine bases. It was found that Bronsted relationships held except for sterically hindered bases; in these cases significant deviations were noted. Bell and Clunie (18) studied neutralization of nitroethane by hydroxide ion in water at 0° and 25 ° by analysis of the thermal effects in reaction. The rate constant obtained at 0°, 3 8 . 5 l./m.-min., is in excellent agreement with that reported by Wynne-Jones (21) and by

(21) W, P. K. Wynne-Jones, J. Chem. Phys., 2,, 381 (193^). . 17

Maron and La Mer (15c), 39.1; the rate constant at 25°,

353» does not agree with that obtained by Elving and Lakritz (17), 236, Recently Bell and Panckhurst (22)

(22) R, P. Bell and M. H, Panckhurst, J, Chem, Soc., 2836 (1936).

have used nitroethane as a reference acid In determining the dissociation constants of various complex metal hydroxides. In the previous discussion. It has been demonstrated that neutralization of nitro compounds occurs by the following process:

+■ 8: > + B:H'^ (9)

and Is subject to general base catalysis. Prom the prin ciple of microscopic reversibility. It Is to be expected that formation of a nltro compound from a nitronate Ion

^ -f-b: d o)

(Equation 10) should exhibit general acid catalysis. This has been found to be experimentally true by Junell(15b, 23)

(23) R. Junell, Svensk Kem. Tld., M» 125 (1934). 18

The recombination reactions of alkanenltronate Ions with proton donors have also been studied by Maron and La Mer (24a) and by Pearson and Dillon (24b),

(24) (a) S, H. Maron and. V. K. La Mer, J. Am, Chem. Soc,, 6 1 . 692 (1939); (b) R. G. Pearson and R, L, Dillon, J. Am. Chem. Soc., 23., 357^ (1950),

The acid-base reactions of nitroalkanes and alkanen- Itronates that have been discussed so far may be written as an equilibrium: A 1 wlth an equilibrium constant: Kj^ = 77^ , A similar ex %2 pression may be written for dissociation of the corres- panding nitronic acids. Since a nltro compound and Its nitronic acid are In equilibrium with the same Ion, an

overall scheme for the behavior of these compounds may be represented as:

A , -Âs

K/v The Ionization constants of the lower nitroalkanes

(with B = H2O), Kj^, have been determined by Turnbull and

Maron (25a) and by Wheland and Farr (25 b). Junell (15b) 19

(25) (a) D. Turnbull and S. H. Maron, J. Am. Chem. Soc., 45., 212 (19^3) 5 (b) G. W. Wheland and J, Parr, J, Am. Chem. Soc., 65 , 1433 (1943).

and Turnbull and Maron (25 a) have calculated the disso ciation constants for the corresponding nitronic acids,

^Aci* results of these investigations are summarized in Table 6.

Table 6 Ionization Constants of Nitro Compounds and Nitronic Acids (in water, 25 °) ' " Compound (25a) (15b)

Nitromethane 10.21 10.24 3.25 — — Mitroethane 8.4 6 8.60 — — 4 . 4 1-Mitropropane — — — 8.98 — — —

2-Nitropropane 7.68 7 .7- 7 .8 5.1

It is of interest that the ionization constants of the nitronic acids show a trend that is expected from the inductive (electron-releasing) effects of alkyl groups; the ionization constants of the nitro compounds exhibit an opposite trend. This anomaly has been explained on the basis of electrostatic forces between the nitro group and the proton passing through regions (alkyl groups) of 20

low dielectric corstart (25 b) ard or the basis of hyper- oorjugative stabilization of the ritrcrate ion (26a) ard greater hypercorjugative stabilization of the ritroric acid (26b).

(26) (a) H. M. E. Cardwell, J. Chem. Soc., 2442 (1951); (b) C. K. Irgold, "Structure ard Mechanism in Organic Chemist#^" Cornell University Press, New York, 1953, p. 559.

The rates of ionization and the ionization constants of nitroalkanes have been compiled by Maron and La Mer (27a) and Pearson and Dillon (27b). Prom these data it appears that nitroalkanes are considerably ^stronger acids

(2 7 ) (a) S. H. Maron and V, K. La Mer, J, Am. Chem. Soc., 6 1. 2018 (1939); (b) R. G. Pearson and R. L. Dillon, J. Am. Chem. Soc., 21, 24 3 9 (1953).

(K^) than their rates of ionization (reaction with water) indicate, Nitroalkanes thus deviate markedly in a Bronsted. plot of ionization constants of weak acids versus

the logs of their rates of ionization in water (27b), The deviation is probably to be expected since the charge in the anion is dispersed by resonance in the nitro group. A nitroalkane which contains an electron-withdrawing sub stituent on its aloha-position is a much stronger acid (larger Kj^) than its unsubstituted parent. The increase in the ionization constant results entirely from the 21

greatly increased rate of loss of a proton in the sub stituted derivative, since the rate of recombination of

the proton with the electronegatively-substituted ion is also increased (27b), As yet there is no adequate ex planation for the increased rate of recombination of the

substituted alkanenitronate ion with a proton.

Deuterium Effects on Kinetics of Reaction

Isotope effects in chemical reactions Involving deuterium and tritium often give important information concerning the nature of the mechanics of the processes involved (28). Because of differences in zero-point energy and mass, more energy is required to stretch or

break a bond to deuterium or tritium than for a corres ponding bond to hydrogen. The greater energy required to

(28) K. B. Wiberg, Chem. Revs., Ü , 713 (1955).

completely break a carbon-deuterium bond as compared to carbon-hydrogen is approximately I150 calories per mole. The isotope effect associated with deuterium is usually expressed as a ratio of rates, kjj/k^j. Since the energy portion of the rate equation involves the term, -ZiE/RT, the magnitude of the isotope effect will depend on temperature. The maximum isotope effects which are 22

possible in breaking of a carbon-deuterium bond at various temperatures are summarized in Table

Table 7 The Influence of Temperature on the Deuterium Isotope Effect for Rupture of a Bond to Carbon

Temp., °C. kc_«/kg_2

0 8.3 10 7.7

25 6.9 70 5.4 100 4.7 200 3.4

It is emphasized that these maximum effects are found only when the C-H (C-D) bond is essentially completely broken, and the new bond to H (D) is not yet significantly formed in the transition state. Investigations of the effects of deuterium on the kinetic and equilibrium properties of nitro compounds are limited. Wynne-Jones (21) and Maron and La Mer (15c) studied successive neutralizations of nitroethane by deuteroxide ion in deuterium oxide in the hope of deter mining rate constants for each of the three following 23

reactions (Eqüations 13, l4, and 15).

CH3CH2NO2 + OD- -- CH3CHNO2" ■f HOD (13) CH3CHDNO2 + 0D“ --CH3CDNO2” + HOD (14)

CHoCDgNOg + OD- -— ^ CH3CDNO2- + D2O (15)

Difficulties involving decomposition of the nitro compounds prohibited accurate determination of the rate constant for the third stage (Equation 15). The two in vestigations are not in agreement as to the rate constant (21 or 36 l./m.-min.) for the second stage (Equation 14). An important aspect of these investigations is the demon stration that neutralization of nitroethane by deuteroxide ion in -deuterium oxide occurs approximately ho% faster than that by hydroxide ion in protium oxide. The greater rate of neutralization by deuteroxide ion has been attri buted to its greater basicity. A study of primary isotope effects on the kinetics of neutralization of nitroalkanes has been made by

Reitz (2 9). Rate constants for neutralization of nitro methane and trideuteronitromethane by acetate ion and by

(29) (a) 0. UReitz, Z. physik, Chem., A176. 363 (1936); (b) 0. Reitz, Z. Elektrochem., 582 (I936). chloroacetate ion in water and in deuterium oxide, by 24 water in water, and by deuterium oxide in deuterium oxide were determined. The results obtained using acetate ion

as the neutralizing base in water and in deuterium oxide are illustrated in Table 8.

Table 8 Kinetics of Neutralization of Nitromethane and Trideuteronitromethane by Acetate Ion in HgO and DgO at 25° (29)

Compound Solvent k X 10^(1./m.-min.)

CH3NO2 HgO 198

CH3NO2 D2O 173 CD3NO2 HgO 30 7GD3NO2 DgO 25

Trideuteronitromethane neutralizes 6 .5-7.0 times more slowly under comparable conditions at 25 ° than does triprotionitromethane. This ratio is close to the theoretical maximum possible (6 .9) for the isotope effect at 25 °, and indicates that in the transition state in volving nitromethane and acetate ion, the carbon-hydrogen

(carbon-deuterium) bond is essentially completely broken, whereas the oxygen-hydrogen (oxygen-deuterium) bond is not yet formed significantly. This study also indicated a definite difference in solvent effects associated with pro tium and deuterium oxides; these effects are not to be expected on the basis of the 25

near Identical dielectric constants of the two media.

Factors Affecting Reactivities of Cyclic and Blcycllc Systems

The manner In which the reactivity at a site In a ring structure varies with the size of a ring Is of prime concern In the present Investigation. Since the effects of structure on the chemical and physical properties of ring compounds have been adequately reviewed by Corbin (30a), and by Vogel (30b) and since the status of the theories of factors affecting the reactivity of homologous ring compounds has been recently summarized by Brown and Ham (31), the present discussion of theoretical factors

(30) (a) T, P. Corbin, Jr., Ph.D. dissertation. The Ohio State University, 1956î (b) E. Vogel, Fortsch, chem. Forsch., 2, 430 (1955). (31) H. C.. Brown and G. Ham, J. Am. Chem. Soc., 78. 2735 (1956). which Influence the reactivities of cyclic and blcycllc compounds will be directed toward that relative to Inter pretation of the results of this experimental Investigation, It Is postulated that three principle sources of strain are present In small (3-4), common (5&7), and medlum-slze (8-12) ring compounds: (A) the distortion of 26 bond angles from the normal value, (B) forces arising from non-bonded opposition or "eclipsing interaction" and (C) compression of van der Waals radii. In small rings (cyclopropanes and cyclobutanes), distortions of bond angles are believed to be the major sources of strain; in cyclopentane, cyclohexane, and cycloheptane systems, bond opposition forces can be very important. Strain in medium-size rings (3 2 ) arises from bond oppositions and compression of van der Waals radii.

(3 2 ) V. Prelog, J. Chem. Soc., ^20 (I9 5 0 ).

Reactions in which a ring atom undergoes a change from tetrahedral to trigonal bonding should be strongly hindered in cyclopropanes and cyclobutanes, since the strains in the transition states resulting from increased bond angle distortions are so great. Conversely, reac tions involving a change of a trigonal atom to a tetra hedral one should be strongly favored in 3- ai:d 4-membered ring compounds. Angle strain effects are expected to be relatively unimportant in larger ring compounds since they are capable of adjusting with (relative) ease to the geometrical requirements of a tetrahedral or a trigonal atom. A change in structure of a ring atom from tetrahedral to trigonal should reduce the bond 27

oppositions in cyolopentanes, cycloheptânes, and medium- sized rings and increase bond oppositions in cyclohexanes.

It is to be expected that trigonal bonding will reduce compression of van der Waals radii in medium rings. From these considerations, the following relative reactivities have been predicted for reactions of a given type:

Type of bonding change Predicted order of ring atom of reactivity tetrahedral to trigonal

trigonal to tetrahedral 3)^)6)7^5

The expected orders for 3» 5> and 7-raembered rings have been observed in certain series. Cyclobutane deri vatives, however, often behave erratically. For example, 1-chloro-l-methylcyclobutane solvolyzes (S^l) slowly, as expected (33a), but cyclobutyl chloride and cyclobutyl tosylate solvolyze (S^l) much more rapidly than antici pated (33b). Cyclobutyl chloride and tosylate solvolyze to give rearranged products, and it has been postulated (31, 33b) that the driving force associated with rearrange ment may account for the enhanced reactivity. Cyclopropyl derivatives rearrange to.the very stable allyl cation, however, and there is no apparent accelerative effect on the rate of reaction (33b). 28

(33) (a) H. C, Brown and M, Borkowskl, J. Am. Chem. Soc,., 2ÏL» 189^. (1952 ); (b) J. D, Roberts and V, C. Chambers, J, Am. Chem. Soc., 21, 3034 (1931).

The physical-organic chemistry of bicyclo[2'2'l]- heptyl (norbornyl) and related systems has been a subject of major prominence largely through the publications of J. D. Roberts and S. Winstein and their associates. A comprehensive review of the work in this area is beyond the purposes of this discussion, and only a few represen tative papers will be reviewed. ' In 1949, Winstein and Trifan reported the rates of acetolysis of exo- and endo-norbornyl-p-toluenesulfonates as part of a study of neighboring group participation

(3 4 ). It was found that the exo-derivative undergoes

(3 4 ) S, Winstein and D. S. Trifan, J. Am. Chem. Soc., 2 1 , 2933 (1949).

Exo-Norbornvl Endo-Norbornyl uniraolecular solvolysis in acetic acid 330 times as fast as the endo-isomer. The optically active exo-tosylate 29

is converted into a completely inactive acetate; both the exo- and endo-tosvlates yield the exo-acetate.

It was believed that these facts are best explained if a non-classical "norbornonium" ion is formed during solvolysis. This ion has a plane of symmetry and this accounts for the loss of optical activity. The electrons

Norbornonium Ion of the Cg-C^ bond can participate in ionization of the exo-derivative and account for the enhanced reactivity. The geometry of the endo-derivative does not allow parti cipation in the rate-determining step, Roberts, Lee and Saunders investigated solvolysis "i 11 of exo- and endo-norbornvl - 2 ,3-02 -p-bromobenzene- sulfonates (35). On degradation, the product was found to

(35) J* D, Roberts, C. 0, Lee, and W, H. Saunders, Jr., J, Am, Chem, Soc,, 2Â» 4501 (1954), have the radioactivity scattered over the ring in the manner shown below. The results could not be explained 30

Radioactivity Distribution "Nortrlcyclonlura*' Ion by the "norbornonium" Ion and thus a new, completely symmetrical'"nortrloyclonlum" Ion was postulated as an Intermediate. The name "nortrloyclonlum" Is derived from the resemblance of the ion postulated to the structure of nortrlcyclene. Some credibility for the "postulate of a structure of the nortrloyclonlum type Is derived from the fact that a nortrlcyclene derivative Is obtained (Equation 16) from reaction of norbornene with N-bromosucclnlmlde (36).

(3 6) J, D. Roberts, E. R. Trumbull, Jr., W. Bennett, and R. Armstrong, J. Am. Chem. Soc., 3116 (1950).

Similarly, solvolysis of exo or endo- 5-norbornenyl

~h M b s (16) derivatives results In formation of 3-substltuted nortrlcyclenes (Equation I7 ). 31

(17)

An example of a different type of carbon-slceleton

rearrangement has been obtained (3 7 ) In oxidation of nor bornene with performlc acid (Equation 18).

(37) H. Kwart and W. G. Vosburgh, J, Am, Chem, Soc,, 26., 3400 (1954).

(1 8) 4- HCOjH -h ■oH

The most complete series of kinetic data which has been obtained for the norbornyl and the norbornenyl systems Is that for acetolysis (S|^l) of the tosylates. The results are summarized In Table 9, To account for the greatly enhanced reactivity of . the anti-7-norbornenyl derivative (which does not give rearrangement), it has been postulated (41) that the elec trons. of the 02- Cj double bond participate to form a non-classical anti-7 -norbornenyl ion; on the other hand, s.vn-7 -norbornenyl tosylate undergoes rearrangement upon hydrolysis to yield 2-bicycloC3'2'0]heptenol-4, 32

syn -J- unii

7-Norbornenyl system ■Antl-7-Norbornenyl Ion

Table 9 Approximate Relative Rates of Acetolysis of Cyclic and Blcycllc Tosylates (in glacial acetic acid at 25 °)

Coranound Relative Rate Reference Note

1.4 X 10-7 41, 42 A" A" 2 X 10^ 39, 41, 42 a

a 6 X 10-4 42 b

{j-XoTs 8 X 10^ 39, 41 c é 10-1 39, 41 c 3.5 X 10^ 4o, 43 a, d A ■ 1 4o, 43 d

1 38, 41, 43

[>.7. 2,8 X lol 38

(a) The product retains the initial configuration. (b) The product of hydrolysis is 2-blcyclo[g-2'0]heptenol—^ • (c) The product Is 3-acetoxynortrlcyclene. (d) The product has the exo-confIguratlon. 33

(38) H. C. Brown and G. Ham, J, Am. Chem. Soc., 2Â> 2735 (1956). (39) S. V/instein and M. Shatavslcy, J, Ara. Chem. Soc., 78. 592 (1956). (40) S. Winstein, H. M. Walborsky and K. Schreiber, J. Am. Chem. Soc., 22, 5795 (1950). (4d) S.„Winstein,, M. Shatavsky, C. Norton and E. B. Wood ward, J. Ara. Chem. Soc., 22, 4183 (1955). (42) S. Winstein and E. T, Stafford, J. Am, Chem. Soc,, 22, 505 (1957). ' (43) S, Winstein and D, S, Trifan, J, Ara, Chem. Soc., 21, 2953 (1949).

Norbornyl systems have also been of theoretical interest in connection with the mechanism of acid-catalyzed conversion of nitronic acids to their corresponding alde hydes or ketones (44) (Equation 19). All attempts to

X ^ Rji=o 4- Alo -f- (19)

(44) This general reaction, commonly known as the Nef reaction (W. E. Noland, Chem. Eevs., 25., 137 (1955), Is usually conducted by acidifying salts of primary and., secondary nitro compounds with aqueous mineral acids. effect normal Nef hydrolyses of salts of 5-%ltronorbornenes (45) to their corresponding carbonyl derivatives have failed 34

(Equation 20), Both the bicycloheptane skeleton and the

(2 0 )

(45) (a)..W, E. Parham, W, T, Hunter, and R, Hanson, J. Am, Chem. Soc., 23.» 50^8 (1951) 5 (b) E. E. Van Tamelen and R. J, Thlede, J. Am. Chem. Soc., 74.2616.. (1952) ; (c) W. C. Wlldraan and C. H. Hemminger, J. Org. Chem., 12» 1641 (1952).

unsaturation at carbon atoms 2 and 3 are necessary for failure of this reaction since 4-nitrooyolohexenes (46a), 2-nitronorbornanes, (45b, c) and 5-nitrobicyclo£2*2'2]octene-2 (46b) give the Nef product in good yield.

(46) (a) W. C. Wildman and R. B. Wildraan, J. Org. Chem., 17. 581 (1952 ); (b) W. C. Wildraan and D. R. Saunders, J. Org. Chem., 19, 381 (1954).

Wildman and Saunders (46b) have suggested that the failure of the Nef reaction for nitrobicycloheptenes arises from resonance stabilization in their anions (47) of the type:

/V: 35

(4?) This explanation is, in principle, compatible with the generalization that salts of nitroalkanes least stabilized by resonance effects undergo excessive hydroly sis and decomposition upon acidification; N, Kornblura and G, E. Graham, J, Am, Chem, Soc,, 211> 4^41 (1951).

Resonance stabilization of the above "non-classical" type is'.impossible in nitronorbornanes and thus hydrolysis of the Nef type is expected, 5-Nitrobicyclo[2*2*2]octene-2 gives a typical Nef reaction. To account for the difference in behavior of nitrobicycloheptenes and nitro- bicyclooctene under conditions for Nef hydrolysis, it was suggested (46b) that non-classical stabilization of the type (48) is relatively unimportant.

(48) Synthesis of derivatives containing the homonortri- cyclenyl carbon skeleton has been reported,,by K, Alder, F, Brochhagen, C, Kaiser, and W, Roth, Ann,, 593. 1 (1955) III. DISCUSSION OF RESULTS OP THE PRESENT INVESTIGATION

Kinetics of Neutralization

The rate constants and the kinetic parameters resulting from the present investigation are summarized

in Table 10. The individual rate constants in each ex periment for neutralization of a nitro compound are con tained in Tables 17-33,’Appendix B. The kinetic data obtained in each experiment are included in Appendix B, Plots used in determination of the activation parameters for each cyclic and bicyclic nitro compound are illus trated in Figures 5-7, Appendix A. Some representative plots of t(RoQ-R) versus R are shown in Appendix A.

Nitrocvcloalkanes The kinetics of neutralization of homologous nitro-

cycloalkanes by hydroxide ion in dioxan-water (50:50 vol.) have been studied previously in this laboratory (^9).

(49) (a) H. Stone, Ph.D. dissertation, The Ohio State University, 1950; (b) J. G. Traynham, unpublished research. The Ohio State University, 1952).

The original intention of the present investigation was only to extend the measurements on nitrocyclobutane so

36 37

that accurate activation parameters could he calculated. It was found, however, upon using the techniques developed in the present investigation, that there was disagree ment with the previous studies if a nitro compound was neutralized rapidly. As a result, the kinetics of neutralization of the - Cg nitrocycloalkanes were re investigated. A comparison of the results of the present and of previous studies is made in Table 11. For neutralization of nitrocyclohexane, the results obtained by Traynham and from the present study were in excellent agreement. The rate constants at various tem peratures from the two investigations defined points on the same activation energy line. There was no such agreement for the other nitrocycloalkanes studied. There was, however, a general relationship between the dis agreement" and the magnitude of a rate constant; the dis agreement ranged from 2J>% for nitrocyclobutane to 8^ for nitrocyclooctane. It is believed that the discrepancies arise prin cipally from the kinetic limitations of the conductivity cells used in the earlier investigations. These cells had to be removed from the bath for extended periods (8-14 seconds) to insure mixing; this technique resulted in a temperature increase in the cell in experiments Table 10 Kiuetic Constants and Parameters for Neutralization of Nitro Compounds with Sodium Hydroxide in Dioxan/Water (50:50 by Vol.)

Compound kgCoO)* k2(9"93°)* kg (28°) + 4S****

Nitrocyclobutane 165± 2 383+ 9 1550 + 20 12.5 -10.6 Nltrocyclopentane 39.8+ 0.7 85.0+ 1.5 325 + 7 11.7 -I6 .4 Nitrocyclohexane 7 .62+0.2 0 18.4+ 0.4 7 8.3+ 1 .3 1 3 .1 -14.5 Nitrocycloheptane 20.6+0.3 46.2+1.0 180+2 12.1 -16.2 Nitrocyclooctane 16.0+0 .6 33.9+0.6 130+2 11 .7 -18.1

1-d-Nitrocyclobutane 19.5+0.4 4 5 .8+0 .4 210+2 1 3 .3 -1 1 .9 1-d-Nitrocyclopentane 4.78+0.01 11.2+0.1 4 7 .6+0 .7 12.8 -I6 .5 1-d-Nitrocyclohexane 0.86 2 ,2 9 11.7±0.5 14.6 -13 .3

4— Nitrocyclohexene 21.4+0.3 4 7 .2+0 .7 203+3 12.6 -14.3 Endo-2-nitrobicyclo[2-2-1]heptane . 134+1 289+6 1010+40 11-5 -14.7 Exo-2-nitrobicyolo- [2 - 2 - i] heptane 6.80+0.08 15 .7+0 .1 6 7 .3+0 .8 12.8 -15 .9 Endo-5-nitrobicyclo- [2 ' 2 -1] heptene-2 210+4 455+14 1770+40 11.9 -12.3 Exo-5-nitrobicyclo- [2 ' 2 " 1] heptene-2 7.86+0.07 1 7 .8+0 .3 7 7 .2+1 .0 12 .7 -15 .9

(continued on page 39) w 00 Table 10 (continued)

Compound kgfOO)* 4 3 (9.93°)* kg (280)* 4H***

Endo-S-nitrobicyclo- £2* 2-23octene-2 50.6+0.5 111+2 399±3 11.6 -16.3 Exo-5-nitrobicyclo- [2-2-2]octene-2 47.2+0.8 104.8+0.8 391+1 11.8 -1 5 .7 2-Nitrobicyclo- [2 *2'2] octane 37.9+0.7 84.4+2.0 310+7 11.7 -16.^

1-Phenylnitroethane 9 2.8+1 .0 1- (p.-Tolyl )nitroethane 51.9+0.7 1- (p,-Nitrophenyl ) - nitroethane 4560+130 1-(m-Nitrophenyl)- nitroethane 2110+100

* in liters/mole-min. in kcal./mole *** in cal./mole-deg.

VO ko

Table 11 A Comparison of the Bate Constants Obtained by Various Investigators for Neutralization of Homologous Nitrocycloalkanes with Hydroxide Ion (in 50î50 vol. dioxan-water, 0°, k2 ’s in l./m./mln.)

Compound Stone (49a) Ti^ynham (49b) Flanagan

Ni trocyolopropane 0.0 (25 °) — — — — ——

Nitrocyclobutane 24? 204 165 Nltrocyclopentane 85 46.2 39.8 Nitrocyclohexane 7.8 7.54 7.62

Nitrocycloheptane 31^7 22.7 20.6 Nitrocyclooctane — 17.3 16.0 4-Nitrocyclohexene — — — , 21.4,. conducted at temperatures below that of the laboratory. Such a temperature effect would produce an apparent rate constant that is too large, and the discrepancy would be greater the more rapid the reaction. Both Stone and Traynham found that the early kinetic points for a run deviated from the straight line. No such deviations were noted using the conductivity cells and the techniques

(see Experimental) of the present investigation. With the exception of nitrocyclobutane, the results obtained for the homologous nitrocycloalkanes (5 0 ) are in agreement with the general principles of present theories 41

(50) The measured differences in the activation energies for the homologous nitrocycloalkanes are small; all of the activation energies lie between 1 1 .7 and I3 .I kcal./mole. Since the experimental error in determining the activa tion energies may be as high as 0 .3-0 .5 kcal./mole, some of the differences in activation energy for the nitro cycloalkanes may not be significant. Extrapolations of activation energy plots indicate that the relative order of reactivity shown in Table 11 will be Valid for the entire series between 1250 and -75°. The relative reactivities of the 4, 5, and 6- membered nitrocycloalkanes will be the same between 400° and -125 °. For these reasons, the discussion given here will be based primarily on the relative reactivities. of reactivity of common and medium-sized ring compounds

(3 1 ). Nitrocycloheptane and particularly nltrocyclopentane are expected to react faster than nitrocyclohexane under comparable conditions because reaction leads to a decrease in bond opposition forces in the 5- and 7-membered rings and an increase in these forces in the 6-raembered ring

(5 1 ), The great increase in strain arising from increased

(5 1 ) H. C. Brown, J. H. Brewster, and H. Shechter, J. Am. Chem. Soc., 2Â, ^67 (1954). bond angle deformation should make conversion of nitrocyclopropane into its anion very difficult; reaction of nitrocyclopropane should also be expècted to occur with difficulty because of the electrical and unsaturated properties of a cyclopropane ring. 42

Little is known quantitatively about the importance of eclipsing effects in medium-sized (8-12) ring systems. However, it is expected that saturated 8-membered rings are less rigid (less strained) than are 7-membered rings. If the relative strains in the ground states of these nitro compounds play the major role in controlling their relative reactivities, it is to be anticipated that nitro cyclooctane will be neutralized more slowly than nitro cycloheptane. The reactivity sequence thus predicted for neutralization of nitrocycloalkanes is 5 and ?)^8>6))>3; this sequence is essentially that which has been observed in the present investigation. The high reactivity of nitrocyclobutane was not expected on the basis of I-strain considerations (3 1 ) and thus deserves further discussion. In terms of I- strain effects, nitrocyclobutane should have a reactivity intermediate to those of nitrocyclopentane and nitrocyclo propane. A decreased eclipsing effect and a major increase in bond angle deformation strain should make nitrocyclo butane much less reactive than nitrocyclopentane. The same considerations should make nitrocyclopropane much less reactive than nitrocyclobutane. The fact is, however, that the reaction velocity constant for neutralization of nitrocyclobutane is 4 times as large as that for nitrocyclo pentane at 0° (5 2 ). 4]

(52) This high reactivity is not confined to nitrocyclo butane. Preliminary experiments with 1.l-trans-dlnhenvl-Z. ^-trans-dinitroGVolobutane (prepared by D, B. Miller) revealed that the compound was neutralized too rapidly in dioxan/water (50:50 vol.) at 0° to be measured accurately, It is estimated that the velocity constant for neutrali zation of 1.l-trans-dinhenvl-2.4-trans-dinitrocvclobutane is at least 30 times that of nitrocyclobutane.

A number of investigations of the relative rates of reaction of homologous cyclic compounds have been made which include cyclobutane derivatives. The results of these studies are summarized in Table 12. It can be seen that cyclobutyl derivatives are generally quite reactive. Cyclobutyl chloride and tosylate solvolyze to give rearranged products, and it has been postulated that the rearrangement contributes to the energetics of the transition state and thus accounts for the enhanced reactivity (53, 55). Solvolysis of 1-chlorq-l-methyl- cycloalkanes is undisturbed by rearrangement; in this system the relative reactivity of the cyclobutyl deriva tive is much smaller (54). The present study provides an example in which there is enhanced reactivity in a cyclobutyl derivative in a system undisturbed by rearrangement. To account for the reactivity of nitrocyclobutane, two modifications of the present theory of ring reactivity are proposed; (a) solva tion plays an important role, particularly in small, rigid Table 12 The Effects of Ring Size on the Relative Reactivities of Homologous Cyclic Compounds

Solvolysis of Chlorides, Neutralization of Solvolysis of 50% Aqueous Ethanol, 95° Nitro Compounds by Tosylates, Acetic (55). Hydroxide Ion, 50^.. Acid, 70 ° (53). Aqueous Dioxan, 0°. cyclopropyl 0 0 /-IX 0 cyclobutyl 41 22 1 1 .3 cyclopentyl 15 5 .2 14.0 cyclohexyl 1 1 1 cycloheptyl 2.8 2 5 .3 cyclooctyl 2.1 191

(continued on page ^5) Table 12 (Continued)

Reaction of Bromides Solvolysis of 1-Chloro- with KI, Acetone, 1-methyl Derivatives 90° (55). 80^ Aqueous Ethanol, 25° (54). cyclopropyl no reaction cyclobutyl 1.4 .21 cyclopentyl 20 124. cyclohexyl 1 .0 1 .0 cycloheptyl — —— 108 cyclooctyl 286 '

(53) H. C. Brown and G. Ham, J. Am, Chem. Soc., 78. 2735 (I956). (54) H, C, Brown and M. Borkowski, J. Am. Chem. Soc., 74, 1894 (I952 ). (55) J. D. Roberts and V. C. Chambers, J. Am, Chem. Soc., 73. 5034 (1951).

Ox 46

rings (thus, nitrooyolobutane), and (h) the importance of bond opposition forces is much greater in cyclobutyl derivatives than has been previously proposed.

The case for the Importance of solvation can be seen upon examining the relative rates of cyclobutyl and cyclo hexyl derivatives in Table 12, There appears to be a definite relationship between the "solvating power" of a solvent and the relative rates of a cyclobutyl deriva tive as compared to a cyclohexyl derivative (56).

(56) It should be noted that the activation energies will, in general, not be constant in a reaction series of cycloalkyl derivatives. Thus the relative rates shown in Table 12 will be a function of temperature. The intention of the present discussion is only to establish a general trend.

In 50^ aqueous ethanol, the ratio of reactivities of C^/C^ is 4l; in 50 ^ aqueous dioxan, the reactivity ratio is 22; in acetic acid, the ratio drops to 11,3; and in acetone the ratio is only 1.4, It is not clear where the ratio of reactivities of l-chloro-l~methylcyclobutane and 1-chloro-l-methylcyclohexane should fit in such an analy sis. The 1-methyl substituent should definitely reduce the relative solvation of the transition state; the mag nitude of the effect cannot be stated. If the solvent is tightly bound to the positive center developed in the 4? transition state, the effect of the methyl group might be quite large (57).

(57) For discussions of the role of solvents in ioniza tion reactions see E. Toramila, Suoraen Kemistilehtl, 22À, 205 (1956), (c. A. 51, 6501 (1957); and E. D. Hughes, C. K. Ingold and associates, J. Chem. Soc., 1206-1331 (1957).

The trend in the activation parameters for the neutral ization of .nitrocyclobutane (enthalpy change rather un favorable, entropy change quite favorable) compared to the other nitrocycloalkanes is not in the expected direction if; solvation of the transition state is greater for nitro cyclobutane. Increased solvation of the transition state is expected to be reflected in a decreased activation en thalpy and a decreased (more unfavorable) activation entropy (58). However, several other factors may be contributing

(58) (a) A. A. Frost and R. G. Pearson, "Kinetics and Mechanism", John Wiley and Sons, New York, 1953, Chapter 7; (b) J. E. Leffler, J. Org. Chem., 20,, 1202 (1955). appreciably to the observed trend. Increased bond angle deformation strain in the transition state for neutrali zation of nitrocyclobutane may increase the activation enthalpy considerably; a decrease in bond-opposition might contribute to a decreased activation enthalpy and a more favorable entropy change, since the molecular rigidity is decreased. The aloha-methylene 48

groups in nitrocyclobutane are bent baok and held in a rigid structure; thus the reactive hydrogen is in an exposed position. Because of this, a greater percentage of collisions of nitrocyclobutane with hydroxide ion will result in a geometry suitable to reaction than for the other nitrocycloalkanes. This effect is expected to contribute greatly to a more favorable entropy of activa tion.

It has been stated that bond-opposition in cyclobutanes should be much less important than in cyclopentanes (5^). It is not immediately obvious why this should be so. In cyclobutanes, the bonds attached to adjacent atoms of a ring will be directed away from each other to a greater extent than those on cyclopentanes; this effect will increase the interatomic distances and thus relative ly reduce the bond eclipsing forces in cyclobutanes. A second effect is that one of the carbon atoms of cyclopentane is twisted slightly out of the plane of the ring (59). In a cyclopentane substituted with a bulky group,

(59) J..E. Kilpatrick, K. S. Pitzer, and B. Spitzer, J. Am. Chem. Soc., 6£, 2483 (19^7). the carbon atom bearing the substituent is expected to lie out of the plane of the ring, thus reducing eclipsing interaction about that carbon. Subsequent transformation 49 of such a derivative to one containing a trigonal carbon will result in less relief of strain than if the parent ring were planar. Twisting an atom out of the plane of a small ring will cause a decrease in the internal angles of the ring. Cyclobutanes should thus be more nearly planar (6o) than cyclopentanes and decrease of eclipsing

(6 0) Cyclobutane has been , shown to be..non-planar : J. D. Dunitz and V. Shomalcer, J. Chem. Phys., 20., I703 (1952). interaction by distortion of a ring atom out of the plane of the ring should be much less important. Perhaps the most striking evidence for the existence of an important eclipsing effect in cyclobutanes is, as previously foot noted (5 2 ), the greater rate of neutralization of 1,3- trans-diohenvl-2.4-trans-dinitrocvclobutane than of nitrocyclobutane itself. It is not meant to imply that strain arising from bond angle deformation is not important in cyclobutanes, but rather that the other factors noted here may be of equal or greater importance under the proper circumstances.

The amended theory of ring reactivity now proposed has the advantage, firstly, of explaining the reactivity of nitro- cyclobutanes and, secondly, of obviating the necessity of postulating rearrangement as the major ' driving force in 50

the solvolysis of some cyclobutyl derivatives. It is of

interest with respect to the second point that rearrange ment is postulated to be a driving force in solvolysis of cyclobutyl derivatives but not in the solvolysis of cyclopropyl derivatives, where the product contains only the allyl structure and thus is formed from an inter mediate ion which has many of the characteristics of the very stable allyl cation. Additional evidence for the importance of eclipsing forces in nitrocycloalkanes is derived from the kinetics of neutralization of 4-nitrocyclohexene. The double bond in 4-nitrocyclohexene is expected to have only minor inductive or electrostatic effects on the center con taining the nitro group;the fact is however that the reaction velocity constant for its neutralization by hydroxide ion is approximately 3 times as great as that for nitrocyclohexane at 0°, (In the nitrobicycloheptenes and nitrobicyclooctenes of the present study, the double bonds are geometrically closer to the reacting center than that of ^-nitrocyclohexene; the effects of these trans- annular double bonds are much less.) It is believed that the major factor increasing the reactivity of 4-nitrocyclohexene over that of nitrocyclohexane is the defor mation of i'the cyclohexane ring from a chair form to a 51 more nearly planar structure, with a consequent increase in eclipsing interaction in the ground state (61).

(61).. (a) H. D. Orloff., Chem'. ..Revs'., ^4, 3-4-7 .(195^); (b) E. A. Pasternak, Acta. Cryst., 4, 3l6 (195 I).

The 7- and 8-merabered ring compounds of the present study have a much lower relative reactivity than the two other examples cited in Table 12, This can be explained by either or a combination of the following two effects. Firstly, the two cases cited involve the removal of bulky groups, chloride ion and tosyl anion. Relief of compres sion strain should be considerably greater in those cases than in the present study, in which a proton is being removed. Secondly, solvation appears to play a significant accelerating factor in the present study, and should be less important with bulky 7 - and 8-merabered rings.

The Deuterium Isotope Effect in Neutralization of Nitro- cvcloalkanes with Hydroxide Ion It was originally believed possible that the reactivity of nitrocyclobutane might arise from some subtle change in reaction mechanism from that of the homologous intro- cycloalkanes. A study of the primary isotope effect in 52

neutralization of the 4— , 5- and 6-membered nitrocyclo- aXkanes was made in order to investigate this possibility. The kinetic isotope effects found are summarized as follows; (see also Table 10)

Table 13 Deuterium Isotope Effects in Neutralization of Nitrocycloalkanes

^H/k Effect of Isotopic ,D Change on the Activation Parameters 0° 10° 28° 4(AS*)

Nitrocyclobutane 8.5 8.3 7.3 0.8 -1.3 Nitrocyclopentane 8.3 7.6 6.8 1.1 -0.1 Nitrocyclohexane 8.9 8.0 6.7 1.5 +1.2 Theoretical (62) 8.3 7.7 6.8 1.15 0

(62) K. B. Wiberg, Chem. Revs., jjl, ?13 (1955).

Within the experimental error of the present in vestigation, the data indicate a maximum primary isotope effect for the 3 nitro compounds, and do not indicate any difference in mechanism of neutralization. These results are also in agreement with the deuterium effect obtained by Reitz (29) for neutralization of nitromethane. 53

A maximum isotope effect indicates that the C-H

bond is virtually completely broken and the new 0-PI bond has not significantly formed in a transition state composed of hydroxide ion and an acidic nitro compound. The transition state may then be formulated as:

Bicvclic Nitro Compounds In view of the recent investigations of the solvolytic reactivities (63) of (participating) norbornyl deri vatives and of the postulate of Wildman and Saunders (^6b)

(6 3) For references to the solvolytic reactivities of norbornyl derivatives, see: J. C. Martin and P. D. Bartlett, J. Am. Chem. Soc., 22.» 2533 (1957).

concerning the (non-classical) stability of the 5-rior- bornenenitronate anion, a study of the physical-organic chemistry of the isomeric 5-nitronorbornenes, 2-nitronorbornanes, 5-nitrobicyclo C 2•2'2 3iOctene-2’s, and of 2- nitrobicyclo[2'2*2]octane was of interest. An investiga

tion was thus made of the kinetics of neutralization with hydroxide ion and of the spectral properties of the anions of these systems. The spectra will be discussed in a later section. The principal kinetic results are as 54

follows: (see also Table 10),

Table 14 Reaction of Blcyclio Nitro Compounds with Hydroxide Ion (in 50:50 dioxan-water, kg's in l./m.-min.)

Compound k2(0°) AS*

Endo-2-nitrobicvclo C2•2 -llhentane 134 ., 11.5 -14.7 Exo-2-nitrobicvcloC2-2•13hentane 6.30 12.8 -15.9 Endo-5-nitrobicvclo[2'2•13 hentene-2 210., 11.9 -12.3 Exo-6-nitrobicvcloC2‘2-13heptene-2 7.86 12.7 -15.9 Endo-6-nitrobicvclo 12 * 2 -2loctene-2 50 .6 11.6 -16.3 Exo-5-nitrobicyclof2 *2-2]octene-2 47.2 11.8 -15.7 2-Nitrobicyclo[2-2*2]octane 37.9 11.7 -16.4

The bioyclo[2'2*llheptyl and bicyclot2 *2 •2l octyl systems are unique in that they contain 6-membered rings which are constrained in a boat form. Studies of camphor have shown that carbons 2, 5, 5 and 7 of the bicycloC2-2-iV heptyl system do not lie in the same plane but are .7

A. exo 6 enJo s- '' slightly skewed (64). The bond opposition forces in

these compounds then are expected to be similar to those in nitrocyclopentane.

(64) C. G. LeFevre and R. J. W. LePevre, J. Chem. Soc., 354^ (1956). 55

A bicycloheptyl system contains two 5-membered rings and one 6-membered ring. The 5-membered rings have a stronger tendency to be planar than does the 6-membered ring; this effect forces carbons 2 and 3 to be rather close to carbons 6 and 5j respectively. The net result is that endo substituents are in a crowded or shielded position. (The facile formation of nortrlcyclenes also indicates carbons 2 and 6 are relatively close together). Thus approach of an external species and solvation of incipient charges at an endo position should be sterically hindered.

The effect of strain (if there is any) arising from bond angle deformation is not immediately obvious in this system since the carbon undergoing valency change is part of a 5 and of a 6-membered ring. In view of the earlier discussion concerning nitrocyclobutane, angle strain is not considered to be very important in these

bicyclic systems (65).

(65 ) J. C. Martin and T. D. Bartlett, J. Am. Chem. Soc., Z2.) 2533 (1957 ) have chosen the angle in question to be 103° in 1,4-endoxocyclohexane. On that basis, a small increase in strain might be expected as the carbon atom becomes trigonal. Such an effect iSi.not apparent, how ever, in the present kinetic studies.

It is believed that the reactivities of bicycloheptyl derivatives studied in this investigation can be explained 56 by a combination of. simple steric factors, without ascrib

ing any effects other than steric and electrostatic to the trans-annular double bond. Neutralization of the endo.-derivatives (exo-hydrogen) will be facilitated by the compactness and rigidity,'of the bicyclic cage struc ture, which permit increased solvation of the transition state. Solvation of the transition state of the exo derivatives (endo-hydrogen) will be hindered by the cage structure. Such hindrance can appear either as decreased solvation or as increased rigidity and compression of the transition state (66). Either effect will, of course, lead to decreased reactivity (67).

(66) The experimental differences in reactivity of the exo-endo pairs of the present study are caused by almost equivalent changes in AH* and AS*. These changes in the activation parameters are consistent with the concept of a crowded transition state. A crowded transition state is less probable both because of increased compression forces (primarily ah*) and because of increased rigidity (primarily AS*) of the system.

(67) Relief of compression forces offers an alternate explanation for the greater reactivity of the endo-nitro compounds. However, this effect obviously is not impor tant in the solvolytic reactions studied by others and does not explain the steric course of the Diels-Alder reaction used in preparing some of these compounds or the position of the thermodynamic equilibrium (->'50:50) .. between the exo and endo derivatives (see Experimental)..

Increased bond opposition forces in the ground state will Cause a marked increase in reactivity of all the 57 derivatives (relative to nitrocyclohexane). Introducing a double bond into bicycloheptanes will make the molecules more rigid and more compact. The resulting increased bond opposition forces will cause increased reactivity of the unsaturated molecules. A consideration of models shows that crowding of the endo position should be reduced in the unsaturated com pounds. Thus increased bond opposition forces and in creased solvation should make exo-5-nitrobicvclo[2'2'11- heptene-2 considerably more reactive than exo-2-nitro- bicyclor2*2*IDheptane. Only a small difference is found experimentally. It is possible that electrosatic repul sion between the electron-rich double bond and hydroxide ion account for this discrepancy. It is of interest that introduction of a double bond into the bicycloheptyl system has far less effect than in the cyclohexyl system. The ratios of the rate con stants are 1.16 and 1.57 for the exo- and endo-bicvclo- heptyl derivatives, respectively, and 2.81 for the cyclo hexyl derivatives (all at 0°), with the unsaturated com pound being more reactive in every case. It is expected that the double bond will have more effect on bond oppo sition forces in the cyclohexyl system than in the rigid bicyclic system. The results are thus as would be ex pected. 58

The type of reaction investigated in this research presented an opportunity to determine reactivities in bicycloheptyl systems without introducing the complica tions.of rearrangements in the measured processes (68), With the exception of the exo-unsaturated compound,

(68) Endp-5-nitrobicycloE2-2-l]heptene-2 can be., regenerated from its salt in 60-65^ yield; P. A, McVeigh, M, S. thesis, U. of Minnesota, 195^» The work was successfully repeated in this laboratory. The salt of 2-.nitrobicyclo[2-2 • 1]-.. heptane is transformed to norcamphor in 80^ yield; W. C. Wildman and C. H. Hemminger, J. Org. Chem., 12, l64l (1952).

(exo-5-nitrobicyclo4 2-2-13 hept.ene-2) the reactivities found here closely parallel those found in acetolysis of the corresponding tosylates (Table 12) (although the reactivity ratios are much less). It is believed that the considerations advanced here might also offer at least a partial explanation for the reactivities found in the solvolysis reactions, which have previously been explained solely on the basis of neighboring carbon participation or "anchimeric assistance." In the bicycio[2'2'2]octyl system, all the "rings" are 6-membered, with the result that the ring system is symmetrical for the saturated compound and nearly so for the unsaturated compounds. Under these circumstances, it would be expected that solvation differences in 59

reactions of an exo-endo pair (the unsaturated compounds) will he much less than in the corresponding bicyclohep- tQnes, The fact is that the rate constants for exo- and endo-'5-nitrobicyclo[2• 2' 21 octene-2 are virtually identical In this system, it might be expected that introduction of a double bond will decrease crowding of an endo position and thus increase reactivity of an endo hydrogen. This effect was not found. An opposing effect would be elec trostatic repulsion between the double bond and a hydro xide ion. This effect predominates here just as it did in the bicycloheptyl system. As in the bicycloheptyl system, introduction of a double bond in a bicyclooctane will make the system more rigid and increase bond opposition forces. Both the exo- and endo-unsaturated compounds are more reactive than 2- nitrobicyclo[2-2•21octane; by factors of 1.25 and 1.3^> respectively, at 0°. It is believed significant that 2-nitrobicyclo[2"2"2]octane has virtually the same reac tivity and activation parameters as nitrocyclopentane, in which the bond oppositions are believed similar.

Meta and Para-Substituted 1-Phenylnitroethanes

An investigation of the kinetics of neutralization by hydroxide ion in dioxan/water (50:50 by vol.) of a series of meta and para-substituted 1-phenylnitroethanes 60

was undertaken to obtain information concerning the elec trical requirements of the transition state of the neutrali zation reaction. The data obtained are presented in

Table 15.

Table 15 Neutralization of ra and o-Substituted 1-Phenyl- nitroethanes with Hydroxide Ion . (in 50:50 dioxan/water, 0°, kg’s in l./m.-min.)

Compound kg l-Phenylftitroethane 92.8 + 1,0 l-(’£-Tolyl)nitroethane 51*9 ± 0.7 l_(2_Nitrophenyl)nitroethane &56o + I30 1-(m-Nitrophenyl)nitroethane 2110 + 100

Correlations between the structure (nature and position of G) of compounds of the type:

and reactivity at substituent Y have been obtained for many reaction series (69a) by use of the Hammett Rela tionship (69b), Equation 1.

log k/ko = CTÿ3 (1)

(69).. (a) H. H. Jaffe, Chem. Revs., 51, 191 (1953),• (b) L. P. Hammett, "Physical Organic Chemistry*’, McGraw-Hill Book Company, Inc., New York, 19^0, p. 186, 61

In Equation 1, k and are rate or equilibrium constants for reactions of the substituted (G) and unsubstituted compounds, respectively; o'is a substituent constant which depends on the electrical nature and position of the sub stituent G; and ^ is a constant which depends on the

reaction, the conditions under which It occurs, and the nature of the reacting center Y. The Hammett Equation is not valid for reactions of aromatic compounds in which ortho substituents are varied,

A Hammett plot (log k versus cr ) of the data in

Table I5 is illustrated in Figure 1. As expected, the neutralization is accelerated rather markedly by electron- withdrawing substituents; as a result, the apparent reac tion constant for this series is positive. The tentative value of ^ , 1 .80, is not unusually large, however. (70 )

(70 ) The reaction constant for the ionization of benzoic acids in water at 25 ° has been chosen as 1.0 (69b). The neutralization reaction of the present study is thus con siderably more sensitive to electrical effects than is the standard reaction. Many reaction series have larger reaction constants; as an example, for.,the ionization of anilinium ions in water at 25 ° is + 2 .73 .

It is noted that two values of cr for the o-nitro group have been placed on the graph (Figure 1). The o-nitro group has a substituent constant of O.778 in most reactions. This substituent constant does not give good results. 62

3.3

m - NO

3.0

2.5

2.0

Hammett plot for neutralization ^ “ CH3 of I - ptienylnitroettiones

- 0.25 0.0 0 .5 1.5 (T FIGURE I 63 however, In correlating reactions of substituted phenols and anilines. A special substituent constant, deslg- rated cr (1,270), has been given to the nitro group for these reactions. It Is believed that the larger sub stituent constant required for a nara-nltro group (and some other electron-attracting substituents) Is associated with resonance of the type:

Reactions Involving significant changes In the contribu tion of structures of the type II are correlated better by cr*. The reaction Investigated In the present study can, at least formally, Involve resonance contributions of the type Illustrated;

Q_A/— / -4--- >•. \ = C —

The nitro group attached to the reactant site, however, may decrease the electron charge on the ^-carbon to a point at which resonance Interaction with the p.-nltro group Is unimportant. Unfortunately, the present data Is not extensive At enough to resolve the question of whether

apply to the reaction investigated. Indeed, considering

the uncertainty in the value of C for the pi-nitro group, the data is insufficiently extensive to show rigorously the applicability of the Hammett Relationship in this particular reaction series (69a). (The preliminary decision would be that it does apply.)

The Ultraviolet Absorption Spectra of Anions of Cyclic and Bicyclic Nitro Compounds

In view of the postulate of Wildman and Saunders (71) concerning the stability of the anion of 2-nitrobicyclo-

(71 ) W. C. Wildman and D. R. Saunders, J. Org. Chem., 19. 381 (1934).

[2'2-l]heptene-2 and because of recent interest in the ultraviolet spectra of allcanenitronates (72 ), the ultra violet spectra of the anions of the cyclic and bicyclic

(72 ) (a) P. T, Williams, Jr., P. W. K. Flanagan, W. J. Taylor, and H. Shechter, J.„Org. Chem.,%n^ppe&s;(b) M. F, Hawthorne, J. Am. Chem. Soc., 22., 2510 (1957). nitro compounds of the present study were determined in dioxan/water (50:50 vol.). The spectral characteristics of these anions are listed in Table 16. The spectra are reproduced in the Appendix. 65

Table 16

Absorption Spectra of Anions of Nitro. Compounds in Dioxan Water (50:50 vol.)

Compound Absorption ^max. 9^ ^max.

Nitrocyclobutane 231 10,300 Nitrocyclopentane 228 13,500 Nitrocyclohexane 233 12,000 Nitrocycloheptane 230 12,900 Nitrocyclobctane .233 10,900 4-Nitrooyolohexene 231 11,300 5-Nitrobicyclo[2•2 -'1]heptene-2 240? 9,100 2-Nitrobicyclo[2*2'• heptane 230 13,000 5-Nitrobicyclo[2-2'•2 ]octene-2 24o ll,-4oo 2-Nitrobicyclo[2'2■'2]octane 231 11,600

In a recent paper (?2a), the results of simple molecular orbital calculations on the "pi" electron system of an alkanenitronate have been reported. These calculations indicate that when an alkanenitronate absorbs radiation in the 230 u]/i region there is a considerable transfer of negative charge from the nitro group to the carbon atom and a marked reduction in the carbon-nitrogen double bond character. The results of the calculations may be illustrated as follows:

i-.W)

I Ground State II Excited State 66

where the numbers in parentheses are the calculated formal charges on the atoms and the numbers below the lines are the calculated "pi" bond orders.

Qualitative considerations derived from these models for the ground (I) and excited (II) states of an alkan

enitronate have allowed correlation of a large quantity of spectral data (72a), These considerations may be summarized as follows: (a) electron donating groups stabilize I relative to II and cause hypsochromic (to shorter wavelength) shifts in the absorption maxima: (b) similarly, electron withdrawing groups stabilize II relative to I and cause bathochromic (to longer wavelength) displacements of the absorption maxima; (c) cis-interaction about the C-N double bond between bulky substituents and the oxygen atoms of the nitro group produces strain in the double bond in the ground state which is (partly) relieved on excitation, since excitation reduces the C-N double bond character in the nitronate ion; the spectra of anions in which cis-interaction is important show a bathochromic shift: (d) excitation reduces the C-N double bond character and may allow a measure of rehybridization of the alkanenitronate carbon toward a more nearly tetra hedral electronic structure. In alkanenitronates having the remaining two bonds to carbon constrained in a small 67 ring (e.g. cyclobutanenitronate), this effect will allow

relief of strain on excitation and cause bathochromic shifts in the absorption maxima: and, (e) conjugated substituents (cyclopropyl, phenyl, vinyl) manifest their electron withdrawing properties in lowering the energy of the excited states, thus causing bathochromic shifts in the absorption maxima. The cycloalkanenitronates of the present study do not exhibit a regular order as a function of ring size for their wavelangths of maximum absorption in that Cg ~ Cg > Cij, ^ Cr^ y (Table l6). This order is not obviously interpretable in terms of inductive or other simple electrical effects. The order is reasonable however in terms of various internal strains in the ground states of the cycloalkanenitronates. If cyclopentanenitronate is chosen as the reference anion on the basis of its relatively strain free ground state, cis-interaction about the C-N double bond (consideration c) (51) will then account for the bathochromic shift with cyclohexanenitro- nate and to a lesser extent with cycloheptanenitronate and cyclooctanenitronate ions. Strain arising from bond angle deformation in cyclobutanenitronate is relieved on excitation (consideration d) and results in a bathochromic shift. The extent of the bathochromic shift for the cyclooctanenitronate ion is somewhat unexpected and may 68 result from compression forces about the C-N double bond. The importance of cis-interaction is pointed out in the spectral data just as the importance of bond-opposi tion forces (73) is pointed .out in the kinetic data for neutralization (see Discussion of Kinetic Results) by

(73) Bond-opposition, as discussed in the kinetic section, is the repulsive force between two bonds on adjacent atoms (of a ring). The effect is greatest when the bonds lie in a common plane. Cis-interaction refers to the repulsive forces between two cis groups of a double bond (as in cis-2-butene). Cis-interaction will also be greatest when the double bond lies in the same plane with a bond to an adjacent (ring) atom. Thus the same fac tors which increase the* one effect will also increase the other. the results for 4-nitrocyclohexene. Bond-opposition forces in 4-nitrocyclohexene are believed to be inter mediate between those in nitrocyclopentane and nitro cyclohexane; the rate constant for neutralization is also intermediate. Cis-interaction forces in the anion of 4-nitrocyclohexene are believed to be intermediate between those in the cyclopentanenitronate and cyclo- hexanenitronate anions; it is of consequence that the wavelength of maximum absorption also has an intermediate value. It has been postulated that (a) the anion of 5- nitrobicyclo[2’2'1]heptene-2 is stabilized by resonance 69

of the type;

+•

o" (b) that resonance of this type is unimportant in the 5~ nitrobicyclo[2‘2* 2‘]octene-2 anion; and (c) that the dif ference in resonance stabilization accounts for the difference in reactivity of the two ions in the Nef reac tion (dehydronorcamplior is not formed while bicyclo[2'2*2]-5-octene-2-one is formed in 6 8 % yield (46b)). The present spectral studies do not bear out this postulate. As is shown in Table l6, introduction of a double bond causes a bathochromic shift of almost equal magnitude (74) in both the bicycloheptyl and bicyclooctyl

(74) The absorption maximum for the anion of 5-nitro- bioyclof2*2•1]heptene-2 is quite broad. Thus the wave length reported for this anion may be in error by as much as 2 m/(. systems. Furthermore, consideration of the molecular orbital results for the ground and excited states neces sitates that interaction such as;

o" 70 is more important in stabilizing the excited state than is that postulated by Wildman and Saunders for stabiliz ing the ground state (in order to account for the bath- chromic shift). (75)

(75) Unfortunately, the present data do not allow either acceptance or complete rejection of the postulate of Wildman and Saunders. It is conceivable that introduc tion of a double bond stabilizes both the ground and excited states of the bicycloheptyl system more than in the bicyclooctyl system. After the present investigation was completed, a rearrangement product formed from the anion of 5-%itro- bicyclo[2-2• l]heptene-2 under Nef ■ conditions, was., reported. W, E. Noland, J. H. Cooley,..and P. A. McVeigh, J. Am. Ghem. Soc., 22, 2967 (1957). IV. EXPERIMENTAL

Preparation and Purification of Nitro Compounds

En^~5-Pitrobioyoloheptene-2 (Endo-^-nitronorbornene )

JEi3^ - 5 -nitrobicyclo [2'2 ' 1] heptene-2 was prepared from nitroethylene and cyclopentadiene. In a typical

experiment, 2-nitroethanol (4og., 0.44 mole) was dehy drated with phthalic anhydride (?6). The resulting

(76) G. D, Buckley and C. W, Scaife, J. Chem. Soc., 1471 (1947 ).

nitroethylene was immediately added to freshly distilled

cyclopentadiene (34 g., 0.515 mole) in diethyl ether (loo ml.) in an ice bath. After standing overnight, the mixture was distilled to yield endo-S-nitrobicvclo[2-2•11-

heptene-2, (4o g., 0,288 mole, 65 ^ from nitroethanol),

b.p. 55“58°/3 mm. (77 ) The distillate had no definite

(77 ) The addition was virtually completely stereo specific to give the endo-isomer. The exo isomer has a slightly lower boiling point, but on the basis of infrared evidence, no detectable quantity was found in the., foreruns from distillation of the Dlels-Alder product...... melting point. The ^purity of distillation fractions was determined by the temperature at which the first solid

71 72 material separated from the melt. Repeated distillations through a Clalsen unit yielded the kinetic sample, h. p. 52°/2mm., 99°/8mm., Initial freezing point 44°; lit., b. p. 74-77°A‘.3 ram'. (78), lltl, b‘. pi 92-94°/8 mm". (79)’. The Infrared spectrum (80) of this compound exhibited absorp tion bands which allowed Identification and analysis at

(78) J. D. Roberts, C. C. Lee and W. H. Saunders, Jr., J. Am. Chem. Soc., 2Â) 4501 (1954). (79) W. C. Wildman and C. H. Hemmlnger, J. Org. Chem., IZ, 1641 (1954). (80) The Infrared absorption spectra were obtained with a Perkln-Elmer Model 21 Infrared Recording Spectrophoto meter. The symbols used to describe the absorption bands are: (s) strong, (m) medium, (w) weak, (b) broad. The Infrared spectra are reproduced In Appendix C.

6.4yk(s), 8.7/^(w), ll.O^(m), 11.8 y&c (m), 12.2y^4m), 12.8y U (m), and l4.0y&c(s, b).

Exo-5-nltroblcyclo[2»2>11heptene-2 (Exo-5-nltronorbornene). Endo-5-nltronorbornene (13-33 g-, O .096 mole) and triethylaralne (0. 4 g., 0.004 mole) were placed In a stoppered flask under nitrogen. The mixture was melted and then allowed to stand at room temperature for I3 days. The liquid was then paured into a mixture of acetic acid

(5 ml.), urea (5g.),and water (25 ml.) (81). 73

(81) N. Kornblura and G, E, Graham, J. Am, Chem. Soc., Z2.> 4o4l (1951).

The two-phase system was extracted with diethyl ether (4'x2o ml.), the combined extracts were dried, and the solvent was removed at reduced pressure. The residue was distilled at reduced pressure to give a total dis tillate which contained approximately equal quantities of the exo- and endo-isomers. The products were separated chromatographically in the following manner. Approximately 0,8 g. of the isomeric mixture was dissolved in petroleum ether (50 ml., b. r. 65-80°) and placed on a column (5.5 % 20 cm.) of silicic acid; Celite (2:1). The column was developed with petroleum ether (3 liters), allowed to run dry, and extruded. The column was streaked with conc. sulfuric acid to locate the two bands. The sulfuric acid was removed and the leading band cut out. The material from

20 such columns was extracted with diethyl ether (3 x 900 ml.). The ether was removed at reduced pressure and the residue distilled to yield pure colorless exo-5-nitronorbornene (4.5g. ), b. p. 69-7l°/^.5 mra'l, n^^ 1.4891; calc, for CyHmNOg: C, 60.42; H, 6.52; N, 10.07; found: C, 60.17 ; H,65 .79; N, 9•92. The infrared spectrum of this compound exhibited absorption bands which allowed 74

identification and analysis at 6.4/x. ( s), 11.0/^(w), 11.5^0-

(m), 12.5y(^(w), 12.7^(w) and 13.6/t-(s,Td) . No absorp tion was noted at 8,7y/, 1 1 . ^ , 1 2 , 12 or 14.0; these absorption bands are important in the spectrum of the endo-isomer. No absorption was noted for functional groups other than the nitro group and the double bond.

Endo.-2-nitrobicyclo[2*2-1]heptane (Endo-2-nitronorbornane). Endo-5-nitro'norbornaie(15.3 g.» 0.11 mole), platinum oxide (50 mg.) and glacial acetic acid (éO ml.) were placed in a Parr bomb and shaken with hydrogen at 2 atmospheres. The reduction was stopped after 110^ of the theoretical quantity of hydrogen had been absorbed. The catalyst was filtered and most of the acetic acid removed at reduced pressure. The residue was dissolved in ether and washed twice with water. The solution was dried and the ether removed at reduced pressure. Sub limation yielded endo-2-nitronorbornane (11.7 g*> 0.083 mole, 75^)J a waxy white solid. The kinetic sample was reprecipitated from ethanol/water and resublimed. The material began to soften at 55° and finally melted at 77-78°; lit., m.p. mostly at 64-67° (78).

The infrared spectrum of this compound exhibited absorption bands which allowed identification and analysis at 6.4yk(s), 7.2y&(s), 9.2yc.(w), 11.3/6 (w), 11.8/6(m) and 13.5^ (m). Endo-2-nltronorbornane was reduced with 75

iron and hydrochloric acid in" dioxan/water (78) to endo-2- norbornylamine, isolated as the acetyl derivative (70# yield), m.p. 125 -125 .5 °j lit., m.p. 125-126° (78), liti, m.p. 124° (82).

(82) K. Alder and g’. Stein, Ann., 514,211 (193^)*

Exo-2-nitrobicyclo[2'2"11 heptane (Exo-2-nitronorbornane)

Exo-5-nitronorbornene (3.0 g., 0.0022 mole) was

hydrogenated as described for 2DAa-5 -%itronorbornene. The hydrogenation mixture was allowed to stand 4 days before it was worked up. Under these conditions approxi mately 2-3# of the product was endo-2-nitronorbornane (see kinetic experimental section). The hydrogenation mixture was filtered to remove catalyst and most of the acetic acid removed at reduced pressure. The residue was taken up in diethyl ether (10 ml.) and washed with water (10 ml.). The ether layer was dried, the ether was removed, and the residue was distilled to give exo-2- nitronorbornane (2.37 g., O.OOI7 mole, 78#) colorless liquid, b.p. 57 /1*5 mm., nj^ 1.4895, calc, for C7H11NO2 :

C, 59*55; H, 7 *8 6; N, 9.92; found: C, 59*75: H, 7*94; N, 10.01. The infrared spectrum of this compound exhibited', absorption bands which allowed identification and analysis 76 at 7.2^(s), 9.4yi(w) and. 11 y/.(m). No absor ption was noted at 9.2y^, 11.3y6, or 13.^ A ; all of which are important in the spectrum of the endo-isomer. No absorption was noted for functional groups other than the nitro group. Exo-2-nitronorbornane was reduced with iron and hydrochloric acid in dioxan/water (78) to exo-2-norbornylamine, isolated as the acetyl derivative (70^ yield), m. p. 139.5°-1^1.5°, H t ’. (78) m.p. l4l-l42.4°, lit. (82) m.p. 139°.

Endo-4-nitrobicvclo[2•2•2]octene-2. Nitroethylene prepared from 2-nitroethanol (90 g., 0,99 mole) was added to 1,3-oyclohexadiene (78 g., 0.97 mole). The mixture was heated slowly to ^5-50°; the reaction then became self sustaining and the mixture re- fluxed very rapidly even though cooled ..with an ice bath. After standing overnight, the mixture was distilled to give l,3~cyclohexadiene (20 g.),b.p, 75-80°/7^5ram. and endo-6-nitrobicvclo[2'2-2]octene-2 (38.4 g., 0.38 mole, 38,6# based on nitroethanol). (83) Repeated distillations of the adduct through a Claisen unit yielded the kinetic sample, a waxy white solid, m. p. indistinct, finally liquid at 37°, b. p. 70°/l mm.; lit. (84), b. p. 112-114°/ 11 mm., lit. (85), b. n. 85-87°/l mm.; calc, for CgHi^NOg:

C, 62.69; H, 7.23; N, 9.20; found: c’. 62.91; H, 7.07; N, 77

(83) The residue erupted at the end of the distillation. (84) C, A. Grob, H. Kny, and A. Gagneux, Plelv. Chim. Acta., 130 (1957 ). (85) W, C. Wildman and D, E. Saunders, J. Org, Chem., 15U 381 (1954).

9.10. The infrared spectrum of this compound exhibited absorption bands which allowed identification and analysis at 6. hyU (s), 7.2^(s), 11. lyi(m), 11.5// (m), 11.8yU(m) and l4.2//(s,b). This compound has been shown previously

to have the endo-configuration (84).

2-Nitrobicvclo C2 - 2!loctane Endo-5-nitrobicyclor2*2-23octene-2 (4.12 g., 0,0269 mole) was hydrogenated with platinum oxide in acetic acid by the method described for exo-6-nitronorbornene.

2-Nitrobicyclo[2*2'21octane (3.68 g., O .0237 mole, 88#) was obtained as a waxy solid, m, p., softens at about 80°, completely molten at 109°. After 3 additional sublima tions the physical constants of the kinetic sample were: m. p. finally molten at 111°; calc, for CgHj_2N02: C, 61.88; H, 8.44; N, 9.08; found: C, 62.15; H, 3.40; N,

9.22. The infrared spectrum of this compound exhibited prominent absorption bands at 6.4_/i(s), ll.Oy^(m), 11.4/1

(m), 11.6/6 (m), 12.1/6(m) and 13.6y/(ra). A small sample 78

was reduced as described previously for the uitrouorbor-

nanes to 2-bicyclo[2 '2 "2]octylamlne (58^) ard then con verted to its picrate, ra. p. 221-222°, lit. (86), ra. p.

222- 223°.

(86) G. Komppa, Berl, 6^, 126? (1935).

Exo-5~nitrobicyclo[2 *2-2]octene-2

Endo-^-nitrobicyclo C2•2•2Üoctene-2 was mixed with triethylamine (10 mole %) and maintained at 6o° for 3 days. The isomerized mixture was distilled directly; the distillate was separated chromatographically as described previously to give exo-6-nitrobicvclor2*2-23octene-2.

after 2 distillations as a colorless material, m. p.

indistinct, finally molten at 26°, b. p. 68-69°/l mm.,

u ÿ ’ 1.5029 , calc, for GgH^^NOgî C, 62.69; H, 7.23; N, 9.20; found: C, 62.67; H, 7.15; N, 9.20. The infrared spectrum of this compound exhibited absorption bands which allowed identification and analysis at 6.4y&(s),

(s), 11.6y^(s), 11.9yx(w), 12.3^(s), 13.^ ( m ) and l4.0/x_ (s,b). No absorption was noted at ll.ly^or 11.5/%-;

such absorptions are important in the spectrum of the endo-isomer. No absorption was noted for functional groups other than the nitro group and the double bond. 79

A small sample of this material was hydrogenated In 76% yield to 2-nitrobicyolo[2• 2• 2!Ioctane ever platinum oxide.

l~Phenvlnitroethane

A sample of 1-phenylnitroethane (8 7) was distilled.

(87) Obtained from M. P. Hawthorne, Rohm and Haas Co., Redstone Arsenal, Huntsville, Ala.

The physical constants of the kinetic fraction were: b. p. 680/1 mm., n^° I.52 I8, lit'. (88), b'. p. 92°/2 mm.,

(88).N. Kornblura, L. Fishbein and R. A. Smiley, J. Am, Chem. Soc.; 22, 6265 (1955). n^° 1 .5215 , lit. (89), n^5 1.5212 . The infrared spectrum of this compound showed no absorption bands for functional groups other than the nitro group.

(89) M. Konowalow, J. Russ. Phys. Chem. Soc., 2j2, 514- (1894). l-(p-Hitrophenyl)nitroethane

A crude sample of l-(jo-nitrophenyl)nitroethane (87) was recrystallized 4 times from ligroin (b, r. 80-110°), white crystals, m. p. 66-67°, calc, for C8HgN20^: C, 80

48.94; H, 4.11; N, 14.36; found: C, 49.13; H, 3.95; N, 14.18.

The infrared spectrum of this compound exhibited

no absorption bands for functional groups other than the nitro group.

1- (ja-Tolyl )nitroethane PrMethylacetophenone was reduced in Q6% yield to methyl p_-tolyl carbinol, b.p. 72 1 mm., with lithium aluminum hydride in ether (90). The alcohol was added to excess phosphorus tribromide at (91) to give l-(p.-tolyl) ethyl bromide, b. p. 66°/l.5 mm., in 77^ yield. The bro mide was treated with sodium nitrite in dimethyl formamide according to the directions of Kornblum, et al, (92) for secondary bromides (modified by cooling to <-5°). The products were fractionated in a 25 cm. glass-helix column to give l-(p.-tolyl)nitroethane, b, p. 75-79°/! mm. {36% yield). The product was distilled twice to give the kine tic sample, b. p. 81°/1 ram., n^° 1.5288, calc, for

C, 65.43; H, 6.71; N, 8.48; found: C, 65.38; H, 6.68; N,8.29.

(90) W. G. Broivn, "Organic Reactions," Vol. VI, John Wiley and Son, New York, 1951> pp. 486-489.

(91) K. V. Auwers and H. Kolligs, Ber., 55» 42 (I922). (92) N. Kornblum, H. 0. Larson, B. K. Blackwood., D. D. Mooberry, E. P. Oliveto and G. E. Graham, J. Am. Chem. Soc., 2 a, 1497 (1956)...... 81 The infrared spectrum of this compound showed no

absorption bands for functional groups other than the nitro group.

1~(m-Nltronhenvl)nltroethane

A sample of l-(m-.nitrophenyl) nltroethane (87) was recrystallized 3 times from ligroin (b.r. 80-110°), white

crystals, m.p. 80-80.5°, calc, for CgHgW204 ; C, 48.94; H, 4.11; N, 14 .3 6; found: C, 48.80; H, 3.99; N, 14.19. The infrared spectrum of this compound exhibited no absorption bands for functional groups other than the nitro group.

Nitrocyclobutane A sample of nitrocyclobutane (87, 93) was washed with aqueous sodium chloride, dried, distilled, washed with

(93) The nitrocyclobutane was prepared by oxidation of cyclobutaions oxime with peroxytrifluoroacetic acid accord ing to the procedure of W. D. Emmons and A. S. Pagano, J. Am. Chem. Soc., 22, 4557 (1955). aqueous sodium bicarbonate, dried and redistilled. The kinetic fraction had the following physical constants: b.p.

61°/19.5 mm., nê° 1.4453, lit. (94), b. p. 77°/40 mm., ngO 1.4432 , llti (95), b'. p'. 36.5°/8 mm., ng° 1.4456.

(94), D, C. Iffland, G. X, Criner, M. Koral, P. J.. Lotspeich, Z.. B. Papanastassiou and S, M, White, Jr., J. Am. Chem., Soc., 21, 4o44 (1953). (95) H. Stone, Ph.D. dissertation. The Ohio State Univer- sitv. 1960.______82

The Infrared spectrum of this compound showed slight absorption at 5*6^ (probably cyclobutanone). No other absorption for functional groups except the nitro group was exhibited,

Nitrocyclobutane (0,20 g,, 0.0020 mole) was dissolved

in a solution of potassium hydroxide (0,3 g., 0.0053 mole) in water (15 ml.). Anhydrous magnesium sulfate (1 g.) (96) was added and the mixture was cooled in an

(96) P. Williams, P. Flanagan, W. Taylor and H. Shechter, J, Org, Chem,, in press, ......

ice bath. An aqueous solution of potassium permanganate was added dropwise to a slight visual excess. The mixture

was steam distilled and the distillate (ca, 20 ml.) added to a saturated solution of 2,4-dinitrophenylhydrazine in 2 N, hydrochloric acid (175 ml,). Cooling to 0° and

filtering gave cyclobutanone 2 ,i|—dinitrophenylhydrazone

(0,38g,, 0,00152 mole, ?6^), A small sample purified by chromatography had a m, p, of 144-145°, lit, (97), m, p.

(97) J, D, Roberts and C, W, Sauer, J, Am, Chem, Soc,, 2 1 ^ 3 9 2 5 ( 1 9 4 9 )......

l46-l46.5°• 83

Cyclobutanone 2,4-dlnltrophenylhydrazone has appre ciable solubility in 2 N. hydrochloric acid. Correcting for this solubility leads to a ■■Primary yield of cyclo butanone 2 ,^-dinitrophenj''lhydrazone of 95^* (98)

(98) M. F.- Hawthorne, J. Am, Chem, Soc,, 22, 2510 (1957) reports an uncorrected yield of cyclobutanone 2,4-dinitrophenylhydrazone of 56^ via the Nef reaction from nitrocyclobutane,

Mitrocyclonentane A sample of nitrocyclopentane (bbtained from N, Kornblum) prepared from cyclopentyl bromide and sodium nitrite in dimethyl formamide was redistilled. The kinetic fraction had: ngO 1,4535, lit. (95), ng° 1.4522, lit, (92) n§° 1^4540. The infrared spectrum of this compound exhibited no absorption bands for functional groups other than the nitro group,

Nitrocvclohexane A sample of nitrocyolohexane (E. I, du Pont de

Nemours and Co,) was washed with 35? aqueous potassium acid sulfite and water, dried, and distilled. The physical constants of the kinetic fraction were: b. p.

51-52°/2,5 mm., ng° 1.4615, lit! (99), b'. p. 106-108°/ 4o mm,, ng° 1.4619, lit*. (94), ng° 1.4620, lit. (95), 84

(99) W. D, Emmons and A. S. Pagano, J, Am. Chem. Soc., 22, ^557 (1955). b. p. 96°/25 mm,, n^*^ 1.4626. The infrared spectrum of this compound exhibited no appreciable absorption bands for functional groups other than the nitro group.

Nitrocvclohentane A sample of nitrocycloheptane prepared and purified by Traynham (100) was used directly; I.4723 , lit.

(95), 1 .4722 , lit. (92), ng° 1 .4723 , lit. (99), n§° 1.4720 .

(100) J. G. Traynham, unpublished research, The Ohio State University, 1952.

The infrared spectrum of this compound exhibited no absorption bands for functional groups other than the nitro group.

Nitrocvclooctane A sample of nitrocyclooctane prepared by J. G. Traynham by liquid-phase nitration of cyclooctane was redistilled. The physical constants of the kinetic fraction were: b. p. 79°/2 mm., n£^ 1.4814. 85

The Infrared spectrum of this compound showed no absorption bands for functional groups other than the nitro group.

4-Nitrocvclohexene

«I l i A sample of 4-nitrocyclohexene prepared by R. B.

Kaplan (101) from butadiene and nitroethylene was redis tilled. The physical constants of the kinetic fraction

(101) R. B. Kaplan, unpublished research, The Ohio State University, 1951. were: b. p. 64°/6 mm,, 1.4815. The infrared spectrum of this compound exhibited no absorption bands for functional groups other than the nitro group and the double bond. This spectrum was identical with that obtained by Kaplan.

1-d-Mitrocvclobutane

Freshly cut sodium (0.70 g., 0.03 mole) was placed in a 3~neck flask with purified dioxan (20 ml.) under a slow stream of dry nitrogen. After the mixture had been cooled in an ice bath, a solution of dioxan (10 ml.) and deuterium oxide (15 ml.) (99.8,^, Stuart Oxygen Co.) was added slowly. After the sodium had reacted completely, nitrocyclobutane (2.3 g., 0.023 mole) was added. The Q6

mixture (a salt precipitated) was allowed to stand 5 hours at 0°. A solution was prepared by adding dried sodium acetate (i.g.) and acetic anhydride (2 ml., 2.16 g., .021 mole) to deuterium oxide (5 ml.). After the acetic anhydride had hydrolyzed (to form 0.042 mole acetic acid), the solution was cooled and added slowly (30 min.) to the mixture containing sodium cyclobutanenitronate. The resulting two-phase mixture was extracted with petroleum

e ’t.-.her (3 x 20 ml., b.r. 60-70°); the extracts were com bined and dried. After the solvent had been removed at reduced pressure, the residue was distilled to give 1-d-nitrocyclobutane. The kinetic fraction, b. p. 55“5^°/l6 mm., n§0 1.4415, on the basis of its kinetic analysis, contained approximately 6-8# nitrocyclobutane. The infrared spectrum of 1-d-nltrocyclobutane ex hibited a weak absorption band in the carbonyl region. However, since the kinetic plots for neutralization of this compound closely followed the second-order relation ship (after the nitrocyclobutane had reacted), contamina tion by carbonyl compounds is not considered important. Several differences were noted between the spectra of nitrocyclobutane and 1-d-nitrocyclobutane. The spectrum of nitrocyclobutane showed absorption bands at 7.6/^(m), 87

10 (w ) and 1 2 (s) which were very minor in the spec trum of 1-d-nitrocyclobutane, The spectrum of 1-d-nitro cyclobutane exhibited absorption bands at 11.0/^ (w), 1 1 , ^ (w), 11,;^ (s) and 12.^/<-(w) which did not appear in the spectrum of nitrocyclobutane,

l-d-Nitrocvclonentane By the same general method used for nitrocyclobutane, nitrocyclopentane was converted to 1-d-nitrocyclopentane, b, p, 70-71°/15 mm,, n§° 1,4500, On the basis of its kinetic analysis, the sample contained 7^ nitrocyclopentane. The infrared spectrum of 1-d-nitrocyclopentane exhibited no absorption bands for functional groups other than the nitro group. The spectrum of nitrocyclopentane showed absorption bands at 8,5/^(m), 10,6/6(w, b), ll,g/c (w) and 11,*^ (m) which did not appear in the spectrum of 1-d-nitrocyclopentane, The infrared spectrum of

Ind^nitrocyclopentane exhibited absorption bands at 8,8/^ (m) and 11.]^ (m) which did not appear in the spectrum of n i trocyclopentane,

1-d-Nitrocvclohexane By using the isotope-exchange procedures previously described (the salt mixtures was allowed to stand 17 88

hours), nitrocyolohexane was converted to 1-d-nitrocyclohexane, b. p. ?2-73°/6 ram., n^^ 1.4620. On the basis of its kinetic analysis, the sample contained approximately 8^ nitrocyolohexane. The infrared spectrum of 1-d-nitrocyclohexane ex hibited no absorption bands for functional groups other than the nitro -group.. The infrared spectrum of nitrocyclohexane showed absorption bands at 7 . ^ (w), 8 . ^ (W) and 12.;^ (w) which were very minor in the spectrum of l~d4nitrocyclohexane. The spectrum of 1-d-nitrocyclo hexane showed bands at 9 * ^ (w), 10. ^ (w) and 12.1^ (w) which did not appear in the spectrum of nitrocyolohexane.

Determination of the Kinetic Constants

Equipment Constant temperature bath. The constant temperature bath for all runs was an 11 liter wide-mouth Dewar vessel.

The vessel was insulated and enclosed by a wooden frame-

! work. Thin steel rods across the top of the bath provided support for the conductivity cells. For the experiments at 0°, the bath was filled with crushed ice and distilled water. Occasional manual stirring was sufficient to maintain a constant temperature. For short periods of time the change in temperature was 89

not sufficient to be detected on a Beckmann thermometer;

control was good tp + 0 .01° even with different batches of ice or using tap water Instead of distilled water.

In order to maintain a temperature of 9.93°> the bath was cooled by constantly circulating ice water through a copper coll immersed in the bath, and heated by a

controlled 250 watt heating element. A 4 liter Dewar vessel served as a reservoir for the ice water and cir culation was provided by a centrifugal pump. The heating element was controlled by a thyratron circuit modified by separating the heater and plate circuits and inserting an autotransformer (Variac) in the ac line to the plate circuit (Figure 2). The voltage to the plate circuit

could be varied between ^5 and 130 volts, with a conse quent variation in the voltage imposed on the heating element. Froper variation of the voltage allowed the rate of heating of the bath to be adjusted just slightly above its rate of cooling and prevented wide swings in its tem perature. The thermoregulator was of the standard mercury-, toluene type. The bath was stirred with a Cenco cone- driven stirrer. The temperature of the bath could be controlled within + 0 .01°. In order to maintain a temperature of 28.00°, the system used was the same as that just described except < > < > IIOV AC

5V IIOV AC a is AC 5 5 5 9

6 0 k reg 75 V

FIGURE 2

HEATER CONTROL CIRCUIT VOo 91

that cooling was not necessary. Control of the tempera

ture was excellent in that it was usually within + 0 .005 °. Conductometric equipment. A block diagram of the conductivity apparatus is illustrated in Figure 3» The oscillator (Jaokson^Electrical Equipment Co. Model 652),

located in an adjoining room, was operated at 2000 cycles per second and at an output of approximately 1 volt. The signal from the oscillator was led by shielded wire to a 1:1 isolation transformer and then to the bridge. The bridge was a modified Jones-Joseph type (Leeds and Northrup) (102) with a range of 0-60,000 ohms. The signal from the bridge was brought by shielded wire to. another isolation transformer and then to a preamplifier. Two shielded leads from the bridge made contact with the conductivity cell.

(102) P. H. Dike, Rev. Sci. Inst’., 2, 379 (1931).

The preamplifier was a voltage amplifier employing an EC coupled 6SN7 twin-triode amplifier tube. The power

supply (320 volts do and 6.3 volts ac) was built on a

separate chassis. The preamplifier produced a 240-fold voltage gain. Shielded wire led the signal from the preamplifier to the Y-input of an oscilloscope (DuMont Model 208-B) Osciilotor

Transformer

é L

Cell

Bridge

Oscilloscope Preamp Transformer

FIGURE 3

DIAGRAM OF CONDUCTIVITY APPARATUS VO 93

used as a uull-polnt Indicator. Disappearance of the 2000 cps trace on the oscilloscope indicated when the bridge was in balance. There was a small amount of 60 cps pickup in the preamplifier stage. The sweep frequency of the oscillo

scope was adjusted to form a standing wave from the 60 cps signal. The 2000 cps signal appeared as a modula tion on this wave. The null point was quite easily ob served. Conductivity cells. Preliminary experiments showed that the conductivity cells used previously in this labor atory (103) were not well suited to kinetic measurements of rapid reactions. Horizontal placement of the elec trodes led to frequent entrapment of air bubbles, and adequate mixing was not possible in a short time interval.

(103) (a) H. Stone, Ph.D. dissertation. The Ohio State University, 1950. (b) J. G. Traynham, unpublished research. The Ohio State University, 1952.

The conductivity cell designed for use in this kinetic investigation is diagramed in Figure Vertical placement of the electrodes in this cell virtually elim inated accumulation of bubbles. The second reactant could be introduced rapidly and completely through the slanted 94

-Hg leads

6 cm.

5 cm

2.5 cm. ' -4cm. ------^ 4 cm.-

FIGURE 4 CONDUCTIVITY CELL 95

inlet tube and produced a swirling motion of the contants in the cell. Thirty milliliters of solution (the volume normally used) adequately covered the electrodes and-yet left sufficient air space in the cell that the contents could be thoroughly mixed by shaking the cell in the bath. The ground glass stoppers effectively eliminated absorp tion by the solution of carbon dioxide from the air. The electrodes were not platinized. Hypodermic svringes. The hypodermic syringes (Becton-Dickenson and Co., Yale Luer-Lok type) used had

maximum capacities of 1, 2, ^,and 10 milliliters. They were calibrated from the weight of distilled water which they discharged. The calibrations did not depend on whether or not the syringes were fitted with a needle.

Kinetic Techniques Solvents and solutions. The solvent solution used for all experiments was a mixture of 1,4-dioxan and water (50:50 by volume at 25°). This mixture was chosen so that the results could be compared to those obtained previously in this laboratory. Commercial dioxan (Union Carbide and Carbon) was purified by the method of Fieser (104). (The

(104) L. P. Fieser, "Experiments in Organic Chemistry," 2nd Edition, D. C. Heath and Co. ( 194-1 ) p. 368. 96

nitrogen sweep was eliminated.) The purified dioxan was mixed with water (triple distilled or boiled distilled) soon after distillation to minimize formation of peroxides. Two runs (nos. 41 and 42, endo-^~nitronorbornene at 0°) were intentionally made using solvent which gave a slight positive test for peroxides. The kinetic results did not show any significant deviation from those obtained with solvent which was peroxide free.

Carbonate-free sodium hydroxide was prepared by dissolving sodium hydroxide pellets in an equal weight of distilled water. This solution was allowed to stand overnight, filtered through a sintered-glass funnel, and stored in a Pyrex bottle. Standard solutions in dioxan- water were prepared by diluting the concentrated sodium hydroxide solution with dioxan-water and titration of an aliquot against standard sulfuric acid. The sodium hydroxide solutions were checked periodically by treating the stock solution (10 ml.) with 1 N. barium chloride solution (1 ml.). If the solution developed a noticeable turbidity, the stock solution was discarded. Experiments with sodium carbonate solutions showed this test would detect about 5 x 10~^N. carbonate ion. Since the stock solutions were approximately 0.025 N., carbonate contam inations of greater than Z% could be detected. 97

Considerably greater proportions of carbonate ion produced curvature of a rate line after a short period of reaction. However, the straight initial portion of the rate line gave results in good agreement with those ob tained in uncontaminated experiments. (See notably run

35, endo-5-nitronorbornene at 0°). Standard solutions of the nitro compounds were pre pared by weighing a sample of the nitro compound and dis solving it in the required volume of dioxan-water. The normality was adjusted to equal that of the sodium hydroxide being used. Preparation and execution of a kinetic experiment. Upon completion of a kinetic run, the conductivity cells were rinsed twice with distilled water. If they were not to be used immediately, they were filled with distilled water and stored. In preparation for a run, the cells were washed twice with absolute ethanol and drained. They were then either allowed to air dry or were dried by a a.owisbream{: of filtered air. The required volume of dioxan-water was injected into the dried cell using a hypodermic syringe fitted with a no. 18 needle. The air space in the cell was then purged with a stream of dry nitrogen for 2-3 minutes. With the 98 nitrogen still flowing, the required volume of sodium hydroxide in dioxan-water was injected into the cell with a hypodermic syringe and needle. The cell was immediately stoppered and suspended in the constant temperature bath by wire loops around the inlet tubes. This procedure and the glass stoppers apparently were effective in eliminating .absorption of atmospheric' carbon dioxide during an experiment. A cell which had been filled with sodium hydroxide solution and left in the constant temperature bath for 6 days at 0° changed only 0 .1% in its resistance. Hypodermic syringes were filled with slightly more than the required volume of the dioxan-water solution of the nitrocompound; after the needles had been removed, the syringes were capped with small rubber ampule caps. (The caps were obtained from the Ohio State University Pharmacy Department). The syringes were then suspended tip down through wire loops into the constant temperature bath. The cells and syringes were allowed to equili brate at least if-5 minutes. Equilibration of the cells could be checked upon determining the resistance at various times. The conductivity of a solution decreases about 2% for. each'.'degree decrease in temperature. 99

After a few runs had been made with the various cells,.it was possible to make a reasonably accurate estimate of the values of B® and Rqo which could be expected in a given experiment. Upon knowing these re sistance values, it was simple to calculate roughly what the resistance would be at 50'^ reaction. The interval between Rq and R.| was then divided into 6-12 equal and convenient resistance increments. These resistance values were entered on the data sheet before the run was started. This procedure greatly reduced the manipulation necessary during an experiment. At the start of a run, the hypodermic syringe was removed from the bath, wiped rapidly with a wad of cotton in a motion that also removed the rubber cap, and adjusted to the desired volume. (The volume of 50^50 dioxan-water decreases about 1.5^ and 1% in going from room temperature to 0° and 10°, respectively. Corrections were made for this effect both in determining the volume of the injected solution of the nitro compound and in determining concen trations.) The solution of nitro compound was then quickly injected through the slanted inlet to the conduc tivity cell; and stop-watch was started at the same time. (It is important to note that injection was made using the hypodermic syringe without a needle. This permitted the 100

solution to be injected In approximately 1 second without causing excessive bubbling within the cell.) The ground glass stopper was replaced, and the cell was shaken in the bath for approximately 2-3 seconds. Except in the most rapid runs, the cell was shaken again after 3-5 experimental readings were taken. Prior to starting a run, the bridge was set at a

resistance about higher than the expected Rq J the capacitance was reduced slightly from that required to balance the sodium hydroxide solution. The bridge could be balanced about 8-10 seconds after initiating an experi ment. As soon as the bridge was balanced (evidenced by disappearance or minimization of the 2000 cps trace on the oscilloscope); the time was noted and the bridge reading was advanced to the next higher predetermined resistance. For a sharp null point, it was necessary to adjust the capacitance periodically. Reactions were generally followed to 60-80% completion. The hypodermic syringes were out of the bath for approximately 3-10 seconds before the run was started. To determine the magnitude of the temperature effect caused by this, a 0.01° thermometer was placed in the cell through the vertical inlet. Twenty milliliters of dioxan- water was placed in the cell and it was equilibrated at 0°. loi

Ten milliliters of dioxan-water was injected in the normal manner. The temperature in the cell increased 0.10°, This corresponds to a change in conductivity of about 0.2^; this change is insignificant when compared to that resulting from reaction. For a reaction with an activa tion energy of l4 kcal./mole, this temperature increase will cause an increase of only 1.2# in the rate constant. The increase is considered a maximum effect since the volumes added were almost always less than 10 milliliters. values were determined after 7-3 half-lives of reaction, and were checked to be certain that a constant value had been reached. Most of the anions studied had reasonable stability at 0° and 9•93°* The anions of 4- nitrocyclohexene and 1-phenylnitroethane were somewhat unstable but not enough so as to interfere Seriously with measurement of E^q . Many of the anions were rather unstable at 28.00°, and it was necessary to exercise care in determining E ^ at the correct time.

Calculations

Kinetic analysis of neutralization of pure nitro compounds. The method of calculating the rate constants for neutralization of all compounds except exo-2-nitronorbornane and the 1-deuteronitrocycloalkanes was that used by Marion and La Mer (105). Derivation and limited 102

(105) S. H. Maron and V, K. La Mer, J, Am. Cham. Soc., 2588 (1938). discussion of the mathematical expressions for the kinetic analysis are as follows: For a bimolecular reaction such as:

A + B --- *• C + D, the rate of reaction is expressed by:

"it = it = (1)

where a, b, and c are equal to the concentrations of A, B, and C, respectively. If a = b, then a = b = a^ - c (2) The rate of reaction is then given by:

it = kg (ao - cf , ( 3 )

integration of which yields:

1 = k, t + K. (4) ao-c 2

When t = o, K =-^, Thus ^o

*^3^ =■

or: 1 / _o k2 - a^t ( i‘o ^ ) (6)

_ 1 fO/a 103

The fraction of material reacted at time t is equal to c/ . If the conductivities of the ionic species "O present are additive and vary linearly with concentration;

(8) where ~^— is the fraction of the total conductivity Op A

—^ ^ — - ^oo (§-=-% ) = — (9) — ^CO 2 /^oo" o Incorporation of relationship 9 into Equation 7 gives :

the expression can be rearranged to;

t(H„ - E) = (2°2__) E - Eas. (11) °° ^o''2®o ao%2

Thus a plot of t (Rqo “ versus R will give a straight line with Y intercept (I),

I = f a o , 80^2 and:

ko = “ ^oo

The advantage of this method of conductoraetxL c analysis is that it does not require the determination of Rq. Initial resistance cannot be directly determined in rapid reactions. It is also inherent in this derivation that l<2 does not depend on either the absolute value of the conductance or on the magnitude of the conductance change. It is thus not necessary to determine cell con stants. (This was not done in the present investigation.) 105

Also, the additional conductance resulting from an ex traneous ionic species will make no difference in the

rate expression. The calculations of Stone to correct for conductance of added salts were therefore unnecessary. In general, plots of t (E^^- R) versus R were good straight lines for the first 50^ of reaction. A few runs gave straight lines to 65-75# reaction. In the later stages of neutralization the points obtained curved below the straight line. The deviation in the plots apparently results from small differences in the amounts of the two reactants initially added, to small quantities of car bonate ion in the sodium hydroxide, or to unknown reac tive contaminants. As long as a plot gave a reasonably long straight line, there was no apparent relationship between the length of the straight line and the rate con stant observed. There was no appreciable deviation of the early points in the plots. Extrapolating the plots of t (R^- R) versus E to the point where tCR^^- E) = 0 provides a method for determin ing Rq . Values of Rq obtained in this manner may be compared to the resistance of an equivalent solution of sodium hydroxide. Such comparisons were made for runs involving each of the nitro compounds of the present study.

In general, the values were in agreement to within + 5#. 106

On this basis, none of the nitro compounds used could have contained any appreciable quantity of very

reactive acidic material (e.g. HNO2 ). One set of experiments was conducted to determine the effects of slightly unequal initial concentrations

of the two reactants. Five runs were made with exo-5- nitrobicyclo[2*2-2]octene-2 at 9.93° in which the concen tration of the nitro compound was varied over an S;» range (in 2^ intervals), from 4^ greater than to less than the concentration of the sodium hydroxide. Kinetic plots for the runs in which the concentrations of nitro compound and sodium hydroxide differed by 4^ deviated from the straight lines rather early. However, the rate • constants obtained were spread over only an 8^ range, and were almost directly related to the concentration of the nitro compound. Thus errors in the values of the rate constants (from this source) should be only as great as

the errors in determining concentrations. Kinetic analysis of neutralization of a mixture of two nitro compounds. The samples of exo-2-nitronorbornane

contained small quantities of the endo-isomer and the 1-deuteronitrocycloalkanes were contaminated with 5-8^ of the corresponding nitrocycloalkanes. These impurities are neutralized more rapidly than the principle compounds and thus rate constants for these compounds could not be 107 calculated from the equation derived in the preceding section. Plots of t E) versus R for these compounds were S-shaped curves, in which the center portions were straight. Since the impurities were considerably more reactive than the principle compounds and were present in small amounts, they are essentially completely reacted after a short time. If the rate constants are evaluated be tween consecutive experimental points, the apparent rate constant should decrease steadily until all of the reac tive impurity has been neutralized. The apparent rate constant thus should level off and be equal to the rate constant for the less reactive material. The equation used for these calculations can be derived as follows: Integration of Equation 3,

= %2 (ao - C)2, (3)

between the limits tj_ and tg gives:

ao-cg “ = kg(tg - ti). (12)

Rearrangement of Equation 12 gives:

a_kg(tg— 11 — — —— —— , (13) ° 1-22 1-21 8o So 108

Substitution of 2l = (106) into equation 13 So rtû“ ft"

(106) This relationship holds only when the two species present react to give anions of the same specific conduc tance. In all.,cases studied here the two species gave the same anion, ...

and rearranging yields:

or, in terms of resistance;

Consequently, this method requires the determination of Eq . This was usually done by extrapolating the earliest portion of plots of '^(Rqq - R) versus R, For the rapid reactions at 28.00°, this method was unreliable, and R^ was found by measuring the resistance of an equi valent solution of sodium hydroxide. Where these two methods were used on the same run, they were in excellent agreement. Equation 16 was checked in two ways. A normal run with nitroC'.yolopentane at 9*93° was calculated both by graphing t (R,^ - R) versus R and by Equation 16. The 109

results agreed within 0.7^. Also, a solution containing

10^ 1-phenylnitroethane and 90)% nitrocyolooctane was neutralized at 0°, (The anions of these two nitro com pounds had approximately equal conductances.) This run gave 16.6 l./m.-min. as the rate constant Cor nitrocyclo-

octance, compared to the value 16.0+0 .6 found for the pure compound. This method requires no knowledge of the quan tity. of the more reactive material present. It is only necessary that the more reactive material be completely

reacted before the inequality of amounts of reactants becomes important and that the specific conductatfOs of the anions are approximately equal. (10?)

(107) It should be noted that it is possible, at least in principle, to determine approximately the quantity of each isomer present in a binary mixture and the rate con stant for both isomers from a single kinetic experiment, provided the more reactive isomer is present in small amounts. The approximate quantities of each isomer can be determined in the following manner. A plot of t(R_^-R) versus H(S-shaped) is made. Extrapolation of the earliest portion of the curve gives . Extrapolation of the straight line portion of the curve yields A . The final resistance determines Ac© • The fraction then is the fraction of the more reactive isomer present. (This is the method used to determine the isotopic purity of the 1-d-nitrocycloalkanes,) The successive apparent rate constants obtained from Equation 16 can be extrapolated to zero time. This initial apparent rate constant is then related to the mole fractions ( % and N?) and rate constants (k^ and kg) of the two isomers by the equation:

"ko" = Niki + Ngkg (17) 110

Since the rate constant for the less reactive isomer has been determined from Equation 16, the only unknown quantity in Equation 17 is the rate constant for the more reactive isomer. (This method, of course, does not deter mine which isomer is the more reactive.) This method was applied to some of the data obtained from neutralization of the 1-d-nitrocycloalkanes. The rate constants obtained in this manner for the nitrocycloalkanes were in fair agreement with the rate constants obtained from neutraliza tion of the pure nitrocycloalkanes.

All calculations of rate constants were made with a slide rule. The numbers expressed as + are standard deviations. Activation parameters. The activation parameters were calculated from the "thermodynamic" equation: (108)

(108) A. A. Frost and E. G. Pearson, "Kinetics and Mechanism," John Wiley & Sons, New York, 1953» P* 96.

^ A H ^ ^ R (O (18)

k = Boltzmann constant

h = Planck constant AS* = entropy of activation AH* = enthalpy of activation T = Kelvin temperature

R = Gas constant Plots were made of log versus 4 . (See Appendix A) The slopes of the straight lines obtained are - AH*/2.303R. Ill

AS* was calculated for each of the three temperatures from the equations;

AS* = AK*/T + 2 .303R log M -2 .303R log ^ (19)

AS* = ^ + 4.376 log !f2 -33.36 (20)

and the average value taken.

Ultraviolet Spectra of Anions of Cyclic and Bicyclic Nitro Compounds

• The general technique used in determining the ultra violet spectra of the salts of the various nitro compounds was as follows: Calculated volumes of a standard solution of the nitro compound (1 equivalent) and of a standard sodium hydroxide solution (2 equivalents) were placed in a small volumetric flask under nitrogen. After sufficient time for reaction, dioxan/water (30/30 vol.) was added so that -4 the final concentrations were 0.75 % 10" molar in anion of the nitro compound. The spectra of the anions were determined immediately with a Beckmann DU spectrophoto meter. APPENDIX A

112 113

0.6

0.0

- 0.6

Activation energy plots - 1.2 1. Nitrocyclobutane 2. Nitrocyclopentone 3. Nltrocyclotiexone 4. Nitrocyclotieptone 5. N'itrocyclobctane

- 1.8 3.31 3 4 3 3.55 3.67

FIGURE 5 114

0.2

-0.4

- 1.0

1i-

- 1.6

- 2.2 Activation energy plots

1. l-d-Nitrocyclobutane 2. l-d-Nitrocyclopentane 3t l-d-Nitrocyclohexane

- 2.8 3.43 3.55 3.673.31 3 X

FIGURE 6 11'

1.2 r Activation energy plots Endo-5-nitrobicvclo [2 21] tieptene-2 Exo-5- nitrobicyclo [2 2-1] tieptene -2 £ndo-2-nitrobicycio [2-2'IJ heptane Exo-2- nitrobicycio[2-2-I] heptane Endo -5-nitrobicyclo[2 2 2] octene-2 Exo -5-nitrobicyclo [2 22]octene-2 2- Nitrobicyclo [2 2 2]octone . 4-Nitrocyclohexene

O(T

- 0.6 -

FIGURE 116

3 0 0 0

5 0 % reaction 2200

1400

Nitrocyclobutane R u m 53 Gone- 0 . 0 0 2 7 0 m . Temp: 9.93® kg = 370 L/m.-mln. 6 0 0

3 0 0 0 3 5 0 0 4 0 0 0

FIGURE 8 117

1 4 0 0 0

10000 5 0 % reaction

°r 6 0 0 0

2000

Nitrocyclohexone Run: 73 Conc: O.OIOIm Temp: 0.0“ kg = 7 3 2 l./m-mln.

800 1000 1200

FIGURE 9 lis

2 5 0 0

7 5 % reaction

Endo -2 - nitrobicyclo [2 2 1] tieptone Run: 65 Conc: 0 . 0 0 3 8 6 m. Temp: 9.93® kg = 2 8 4 l./m.-min. 5 0 0

1600 2000 2 4 0 0

FIGURE 10 119

3 2 0 0

5 0 % reaction

2000 8 (r

Endo -5-nitroblcvclo [2 2 1] heptene-2 Run: 176 Conc' 0 . 0 0 0 8 1 5 m. Temp: 28.00" kg = 1830 l./m.-min.

8 0 0

6 5 0 07 5 0 0 8 5 0 0 R FIGURE II 12 0

14000

5 0 % reaction

8 0 0 0

Exo - 5-nitrobicyclo C2-2'2Joctene -2 Run: 250 Cone: 0 . 0 0 2 5 6 m. Temp: 9.93® k 102.8 l./m. -min. 1000

3 2 0 0 4 0 0 0 4 8 0 0

FIGURE 12 121

8 0 0 0

5 0 % reaction t = 0.67 min.

i2000 cr I a?

|-(£-Nitrophenyl) nitrcethone Run: 229 Cone: 0 . 0 0 0 2 8 6 m . Temp: 0.0® kg = 4 3 4 0 i./m.-min.

4 0 0 0

4 0 0 0 0 4 4 0 0 0 4 8 0 0 0

FIGURE 13 APPENDIX B

122 123

Table 1? Velocity Constants for the Neutralization of Nitrocyclobutane by Sodium Hydroxide (in 50?50-by vol. dioxan/Water, kg's in l./m.-min.)

Temp. Run Gone, kg

0.0° 4? 0,00542 163 50 0.00325 164 51 0*00272 166 52 0.00272 168 k2 = 165 ± 2

9.93° 5^ 0.00270 383 53 0.00270 370 55 0.00270 398 57 0.00386 380 58 0.00216 383 kg = 3 8 3 + 9

28.00° 173 0,00815 1544 178 0.000843 1546 182 0.000422 1526 179 0.000422 1573 kg = 1550 ± 20 AH* = 12.5 kcal./raole, = -• 10.6 e.u. 124

Table 18 Velocity Constants for the Neutralization of Nitrocyclopentane by Sodium Hydroxide., (in 50:50 by vol. dioxan/water, kg's in l./m.-min.)

Temp. Run Cone. k2 0 .0° 88 o>oo4o4 39'.3 93 0.00552 40.3 87 0.00505 40.8 92 0.00459 38.9 k2 = 39.8 ±0.7

9.93° 102 0.00552 83.'. 7 101 0.00460 87.0 100 0.00368 83.3 0.00184 85.8 ■ ^2 = 85.0 ± 1-5 28.000 107 0.00365 316 108 0.00457 332 109 0.00457 329 106 0.00183 322

^2 = 325 ± 7 AH* = 11.7 kcal./mole, AS* = — 16.4 e.u. ' 125

Table 19 Velocity Constants for the Neutralization of Nitrooyclohexane by Sodium Hydroxide

(in 50:50 by vol. dioxan/water, kg's in l./m.-min.)

Temp. Run- Cone. k2

0.0° 90 0.^0101 7^70 75 0.00707 7.86 73 0.0101 7.32 7^1- 0.00505 7.61 kg =7.62 + 0.20 ■

9.93° 98 0.00736 18.1 97 0.00552 18.2 96 0.00368 18.9 k2 = 18.^ + 0.4 28.00° 104 0.00364 79.8 103 0.00548 76.8 105 0.00364 . 78.3 kg = 78.3 ± 1.3

AE* = 13.1 kcal./mole , AS"*" = -14.5 e.u. ' - 126

Table 20 Velocity Constants for the Neutralization of Nitrocyololieptane by Sodium Hydroxide. (in 50î50 by vol. dioxan/water, 1^2 1 ^ l./m.-min.)

Temp. Bun Cone. k2

0.0° 118 0.00426 20.4 119 0.00596 20.2 120 0.00852 20.9 227 0.00514 20.8

l<2 = 20.6 + 0.3

9.93° 148 0.00848 47.0 14? 0.00424 47.2 l46 0.00424 44.7 235 0.00244 45.9 Icg = 46.2 + 1.0

26.00° 191 0.00413 179 189 0.00413 180 188 0.00516 182 190 0.00248 180 \^2 ~ 180 +. 2 AH* = 12.1 kcal./mole, AS* =-l6.2 e.u. 127

Table 21 Velocity Constants for the Neutralization of Nitrooyclooctane by Sodium Hydroxide: (in 50:50 by vol. dioxan/water, kg's in l./m.-min.)

Temp. Run Cone. kg 0.0° 128 0.00852 17.1 121 0.00426 15.6 219 0.00257 13.7 220 0.00514 15.8

k2 = 16.0 +0.6 9.95° 158 0.00848 33.'i3 159 0.0042,4 33.5 235 0.00501 34.0 2 # 0.00256 34.9

kg = 33.9 ± 0.6 28.00° 252 0.00231 132 253 0.00154 131 25 ^ 0.000770 130 257 0.00231 128

^2 = 130+2 AH* = 11.7 kcal./mole, AS* = -18.1 e.u. ' ' 128

Table 22 Velocity Constants for the Neutralisation of l-d~Nitrocyclobutane by Sodium Hydroxide (in 50:50 by vol. dioxan/water, kg's in l./m.-min.)

Temp. Run Cone. kg

0 .0° 129 0'.00426 19.1 130 0.00596 19.. 9 131 0.00852 19.4

kg = 19.5 ± 0.4 9.93° 143 0.00424 46,. 1 144 0.00424 45.3 145 0.00848 46.1

k g = 45.8 ± 0 . 4

2 8 . 0 0 0 175 0.00422 212 174 0.00253 210 177 0.00169 208 kg = 210 ± 2

= 13.3 kcal./mole, AS* = -11.9 e.u, 129

Table 23 Velocity Constants for the Neutralization of 1-d-Nitrocyclopentane by Sodium Hydroxide (in 50:50 by vol. dioxan/water, k 's in l./m.-min.)

Temp. Run Cone., k2

0.0° 133 o ‘.o o 596 4,'. 78 13^ O.OO852 4.79 132 0.00426 4.77 k2 = 4.78 + 0.01

9.93° 142 0*00848 ll'.2 141 0.00424 11.2 140 0.00424 11.1 1<2 = 11.2 + 0.1 28.00° 172 0.00422 48.0 171 0.00422 46.7 170 • 0.00253 48.1

^2 = 47.6 + 0.7 AH* = 12.8 kcal./mole, hS* = -16.5 e.u. 130

Table 24 Velocity Constants for the Neutralization of 1-d-Nitrocyclohexane by Sodium Hydroxide (in 50:50 by vol. dioxan/water, kg's in 1 ,-m.-min.)

Temp. Run Cone. kg

0.0° 115 o'.00743 0.86 114 0.00556 0.87 kg = 0 .86

9.93° 117 o'.00736 2'. 20 116 0.00368 2.38

kg = 2^29 28.00° 113 0.00548 11,0 111 0.00548 11.5 112 0.00365 12.2 110 0.00365 12.2 kg = 11.7 ± 0.5 AH* = l4.6 kcal./raole, AS* - .-13.3 e.u. . . . . 131

Table 25 Velocity Constants for the Neutralization of t—Nitrocyclohexene by Sodium Hydroxide (in 50:50 by vol. dioxan/water, k2 *s ini./m.-min.)

Temp, Run Cone. ^'2

0.0° 79 0.00707 21.4 78 0.00606 21.2 77 0.00505 21.0 76 0.00404 21.8 kg = 21.4 + 0.3

9.93° 81 0.00605 4 6 .7 80 0.00504 48.1 83 O.OO806 47/5 82 0.00706 46.5 kg = 47.2 + 0.7

28.00° 192 0.00248 199 193 0.00413 203 194 0.00413 205 193 0.00579 206 kg = 203+3 = 12.6 kcal./mole, = .-14.3 e.u. 132

Table 26 Velooity.Constants for the Neutralization of ËÊldûr2-.nitroblGycloE2-2* heptane by Sodium Hydroxide in 50:50 by vol. dioxan/water, 1^2*® l./m.-min.)

Temp. Run Cone. k2 0.0° # 0.00510 133 45 0.00313 133 43 0.00510 134 46 0.00313 134 k2 = 134 i l

9.93° 65 0.00386 284 60 0.00226 293 66 0.00216 294 62 0.00187 289 61 0.00303 278 64 0.00324 293 kg = 289 ± 6

28.00° 197 0.00165 1054 198 0.00165 1074 201 0.000827 998 199 0.000827 982 196 0.000827 987 200 0.000827 990 k2 = 1010 i 40

^ = 11.5 kcal./mole, = -l4.7 e.u. 133

Table 2? Velocity Constants for the Neutralization of Exo-2-nitrobicvclo f2-2-1]heotane by Sodium Hydroxide (in 50î50 by vol. dioxan/water, k^'s in l./m.-min.)

Temp. Run Cone. kg

0.0° 124 0I00596 6.^89 123 0.00426 6.85 126 0.00852 6.77 12^ 0.00852 6.69 k2 = 6.60 ± 0.08

9.93° 139 0.00848 15 * 6 138 0.00424 15.8 137 0.00593 15.8 136 0.00424 15 • 6

^2 - 15.7 ± 0.1 28.00° 169 0.00253 67.2 168 0.00422 68.2 163 0.00253 67.6 164 0.00422 66.2

kg = 67.3 + 0.8 H*=12.8. kcal./mole, 218* = --15 .9 e. u. 134

Table 28 Velocity Constants for the Neutralization of Endo-5-nitrobioyolo[2*2•1]heptene-2 by .. Sodium Hydroxide (in 50î50 by vol. dioxan/water, 1^2 in l./m.-min. )

Temp. Bun Cone. \^2

0 .0° 4l 0.00510 203 4o 0.00286 216 38 0.00357 212 37 0.00357 211 35 0.00510 210 34 0.00510 209

kg = 210 ± 4

9.93° 152 0.00297 453 151 0.00212 477 150 0.00128 452 153 0.000427 437

1(2 = 455 i l4 28.00° 176 O.OOO8I5 1830 183 0.000422 1732 180 0.000422 1740 202 0.000827 1765 kg = 1770 + 40 AR* = 11.9 kcal./mole, zlS*" = -12.3 e.u. 13^

Table 2^ Velocity Constants for the Neutralization of Eyo-5-nltrobicyclo[2-2 -1]heptene-2 by Sodium Hydroxide (in 50:50 by vol. dioxan/water, k2 *s in l./m.-min.)

Temp. Run Cone. ' ^2....

o'io° 72 0.00700 7.96 71 0.00525 7.76 69 0.00350 7.88 67 0.00350 7.85 k2 = 7.86 + 0.07

9.93° 156 0.00596 17.8 155 0.00424 18.3 154 0.00424 17.6 157 0.00848 17.6 kg — 17 » 8 +_ 0.3 28.00° 162 0 .00422 75.8 167 0.00422 78.4 161 0.00422 76.7 160 0.00253 77.8

kg = 77,2 ± 1.0 AH* = 12.7 kcal./mole, AS* = -I5 «9 e.u. 136

Table 30 Velocity Constants for the Neutralization of Endo-5-nitrobicyolof2*2 *2']octene-2 by .. Sodium Hydroxide , (in 50:50 by vol. dioxan/water, k2 '8 in l./m.-min.)

Temp. Run Cone. . 1^2

0.0° 212 0I00514 ^9i.9 211 0.00257 50 . 6 213 0.00257 30.9 214 0.00514 51.2 k2 = 50.6 + 0.5 9^193° 238 0.00488 110 239 0.00256 111 24o 0.00511 109 241 • 0.00256 114

k2 = 111 ± 2 28.00° 260 0.00154 396 261 0.000770 397 259 0.00154 399 258 0.00231 402

k2 = 399 ± 3 AH * = 11.6 kcal./mole , AS — —16.3 e.u...... ^ . 137

Table 31 Velocity Constants for the Neutralization of Exo-5-nitrobioyolo [2 *2'2,3 octene-2 by .. Sodium Hydroxide ... (in 50:50 by vol. dioxan/water, kg *s in l./m.-min.)

Temp. Cone. Run .^2.... 0.00 21? 0 .0025 ? 48.5 218 0.00514 46..? 222 0 .0025 ? 46.9 222 0.00514 46.?

k2 = 4? .2 ± o'.8 Nitro Hydroxide 9.93° 24"? 0.00266 0.00256 10?'. 9 248 0.00261 0.00256 107.0 249 0.00256 0.00256 103.8 250 0.00251 0.00256 102.8 251 . 0.00246 0.00256 101.3 kg = 104.6 + 2 .5 28.00° 264 0.00154 396 265 0.00154 383 266 0.000??0 386 26? 0.0231 397 k2 = 391 ± 6 AH * = 11.8 kcal./mole, AS* — —15 .? e.u.

•itCalculated using the sodium hydroxide concentration. 138

Table 32 Velocity Constants for the Neutralization of 2-Nitrobicyclol2 • 2 •2]octane by Sodium Hydroxide.. (in 50:50 by vol. dioxan/water, k2 in l./m.-min.)

Temp. Run Cone. ^2

0.0° 205 ol00257 37I5 209 0.00257 38.6 206 0.00514 37.1 210 0.00514 38.4

kg = 37*/9 ± o '.7

9.93° 242 0.00511 82.'. 6 243 0.00256 85.4 245 0.00511 82.7 246 0.00256 87.1 kg = 84.4 ± 2.0

28.00° 255 0.00231 319 256 0.00154 313 262 0.00231 305 263 0.000770 303 kg = 310+7

A H * = 11.7 kcal./mole,. AS* =-l6,.4 e.u. ■■ 139

Table 33 Velocity Constants for the Neutralization of 1-Phenylnltroethanes by Sodium Hydroxide .c (in 50:50 by vol. dioxan/water, 0°, kg's In l./m.-min.)

Compound Run Cone. k2

1-Phenylnltrosthane, 203 O..OO257 93 .'i 7 207 0.00257 91^9 204 0.00514 93^9 203 0.00514 91.8 92.8 ± 1.0 ^2 " 1-(ü-Tolyl)nltroethane 268 0.00924 52 '. 6 269 0.00462 52.4 270 0*00462 51.5 271 0.00277 50.9 k2 = 51.9 ± 0.7 1- (ja-Nltrophenyl )- 278 0.00139 2240 nltroethane 279 0.000285 1980 280 0.000428 204o 281 0.000428 2160 • kg = 2110 + 100

1 - ( T2-N1 trophe nyl ) - 226 0.000857 4600 nltroethane 228 0.00428 4720 229 0.000286 4340 232 0.000428 4600 233 0.000286 4550

^2 4560 ± 130 ... l4o

Table 3^ Nitrooyclobutaae

Run k7 Temp,0° Cell A Cone. 0 .005^2 m. Date 6/14-/56 t(min.) R ^00“® t(Roo“®)

*33 1500 1630 545 .53 1600 1550 822 .75 1700 1450 1090 1*02 1800 1350 1380 1.32 1900 1250 1650 1.67 2000 1150 1920 2.08 2100 1050 2180 0 0 3150 -3568 ko - — :----- = 163 -3568x0.005^2

Run 50 Temp.O° Cell E Cone . 0.00325 ni. Date 6/4/56 t(rain.) R ®oo“^ t(Boo-B)

.35 3200 3600 1260 .48 3300 3500 1680 . 64 3400 3400 2180 .79 3500 3300 2610 .95 3600 3200 30 40 1.12 3700 3100 3470 1.30 3800 3000 3900 1.49 3900 2911 4320 1.70 4000 2800 4760 2.10 4200 2600 5460 CO 6800 -6800 I = -12,730 ko = — — ----- .....= 164 -12730 X 0.00325 1^1

Table 35 Nitrooyclobutaae

Rua 51 Terap.O° Cell F Coac, 0.00272 m. Date 6/5/56 t(mia.) R R^Q-R t(Roo>-R)

.28 3800 4380 1225 .43 3900 4280 184o ^100 4080 2860 *8° 4200 3980 3 3 ^ 1.00 4300 3880 3880 1.33 4500 3680 4900 1*50 4600 3380 3370 1.70 4700 3480 3920 2.13 4900 3280 6990 2.33 5000 3I8O 7480 2.58 5100 3080 7930 2.85 5200 298O 8500 '’•.12 3300 2880 8990 00 8180 I -18120 1. —8 180 . y . ^ - -18120 X 0.00272 - ^6)6

Rua 52 Temp. 0° Cell G Coac. 0.00272 m. 6/5/56 t(mia.) R ^00“^

.42 4100 4470 1873 .33 4200 4370 2400 .70 4300 4270 298O .83 44oo 4170 3460 .97 4500 4070 3930 1.27 4700 3870 4920 1.45 4800 3770 5470 1.63 4900 3670 3980 2.00 5100 3470 6940 2.22 5200 3370 7480 2.44 3300 3270 7980 2.67 5400 3170 8470 CO 8370 -8570 I = -18670 lc2 =-18670 X .00272 = 168 142

Table 36 Nitrocyclobutane

Run 53 Temp. 9.93° Cell F Cone. O.OO270 m. Date 6/7/65

t(min. . R t(Rq q -R)

.23 3000 3000 690 .32 3100 2900 928 .41 3200 2800 1150 .50 3300 2700 1350 .62 3400 2600 1610 .73 3500 2500 1830 .85 3600 2400 2040 ,98 3700 2300 2260 1.13 3800 2200 2490 1.27 3900 2100 2670 00 6000 -6000 = 370 I = -6000 ^2 -6000 X .00270

Run 54 Temp.9.93° Cell G Cone. 0.00270 m. Date 6/7/56 t(min.) R R^^-R tCR^Q-R)

. 64 3300 2600 1660 .88 3700 2400 2110 1.02 3800 2300 2340 1.16 3900 2200 2550 1.32 4000 2100 2770 1.49 4100 2000 2980 1.68 4200 1900 3200 ÛO 6100 -6100 I = -5900 ^2 - -5900 X .00270 = 383 1^3

Table 37 Nltrocyolobutane

Run 55 Temp, 9.93° Cell P Cone. 0.00270 ra. Date 7/9/56 t(min.) R ®oo~^ t(Roo-E)

.23 3000 2850 ■ 655 .41 3200 2650 1090 .51 3300 2550 1300 . 62 3400 2450 1520 .72 3500 2350 1690 .84 3600 2250 1890 .98 3700 2150 2110 1.12 3800 2050 2300 1.27 3900 1950 2488 CO 5850

I = ^2 X 0.00270

Run 57 Temp. 9.93° Cell 0 Cone. O.OO386 m. Date 7/9/56 t (min.) R ^00"^ t(Eoo-R)

.25 I600 1410 352 .39 1700 1310 .55 1800 1210 666 .73 1900 1110 811 .95 2000 1010 960 1.22 2100 910 1110 1.52 2200 810 1230 CO 3010 , -3010 - 380 I = -2050 ■ ^2 - -2050 X .00386 144

Table 38 Nltrocyclobutane

Run 58 Temp. 9.93° Cell D Cone. 0.00216 m. Date 7/9/56 t(rain,) R ®00“® t (Boc-B)

.20 2500 2500 500 .33 2600 2400 790 .46 2700 2300 1060 . 6o 2800 2200 1320 ..7 3 2900 2100 1580 .91 3000 2000 1820 1.10 3100 1900 2090 1.50 3300 1700 2550 1.75 3400 1600 2800 oo 5000 _ -5000 = 383 I = -6050 2 -6050 X .00216 145

Table 39 .Nitrocyolobutane

Run 173 Temp. 28.00° Cell B Cone. 0.00815 m. Date 12/14/56 t(min.) R Reo-E t(Roo-R)

.15 4500 2815 425 .22 4600 2715 600 .35 4800 2515 880 .42 4900 2415 1010 .50 5000 2315 1160 .68 5200 2115 l44 o .77 5300 2015 1550 CO 7315 I = -5815 .000815 “

Run 178 Temp. 28.00° Cell B Cone. 0.000843 m. Date 12/18/56 t(mln.) R EoQ-R t(Roo-R)

.29 4700 2510 730 .37 4800 2410 890 .43 . 4900 2310 995 .60 5100 2110 1270 .70 5200 2010 1410 .79 5300 1910 1510 CO 7 2 1 0 ...... "■72 lO I I = -5520 ^2 = ^5520 X .000843 =1546 146

Table 4o Nltrocyclobutane

Run 179 Temp. 28.00° Cell C Cone. 0.000422 m. Date 12/18/56 t(min.) R B o o “ B t(Roo-B)

.37 9000 4300 1590 .52 9200 4100 2130 .67 9400 3900 2620 .83 9600 3700 3070 1.02 9800 3500 3570 1.22 10000 3300 4030 1.42 10200 3100 44 oo 0 0 13300

I = -20000

Run 182 Temp. 28.00° Cell A Cone. 0.000422 m. Date 12/ 19/56 t(min.) R R^Q-R t(R^^-R)

.35 9000 4340 1520 .49 9200 4 l4 o 2030 .64 9400 3940 2520 .82 9600 3740 3060 .98 9800 3540 3470 1.38 10200 3140 4330 0 3 13340 ^ 1 3 3 4 0 ______I = -20700 2 - .20700 X .000422 “ 1526 14?

Table 41 Nitrocyclopentane

Run 87 Temp, 0° Cell A Gone. 0.00505 m. Date 8/25/56 t(min.) R ®oo“^ t(Roo“K)

.52 1550 1840 933 .8 7 1600 1790 1560 1.23 1650 1740 2l4 o 1 .6 2 1700 1690 2740 2 .0 0 1730 1640 3280 2 .4 2 1600 1390 3850 2 .8 7 1850 1540 4420 3.33 1900 1490 4970 3 .8 3 1930 l44 o 3320 4.37 2000 1390 608O 4 .9 3 2050 1340 6600 5.52 2100 1290 7120 GO 3390 -1650 -16500 X .00505

Run 88 Temp, 00 Cell D Conc. 0 .004 o4 ra. Date 8/25/56 t (min.) R ^00“^ t(Eoo-B) .

.45 1920 2305 lo4 o .67 1930 2273 1330 1.02 2000 2225 2270. 1.37 2050 2173 2980 1.77 2100 2125 3760 2.13 2150 2073 4430 2.53 2200 2025 3170 2.98 2250 2973 3900 3.42 2300 1923 6600 3.88 2330 1873 7280 4.38 2400 1825 8000 4.87 2450 1773 . 8650 aû 4225 ^ ...... I = -26580 ^2 ~ -26580 X .oo4 o4 =39.3...... 148

Table 42

Nitrocyclopentane

Eun 92 Terap.QO Cell A Conc. 0.00459 m. Date 8/5 0/5 6 t(min.) E E&o-E t(Eq^-E)

*35 I630 2060 720 .48 1650 2040 980 .85 1700 1990 1650 1.20 1750 1940 2550 1.58 1800 1890 2990 2.37 1900 1790 4240 2.80 1950 l?4 o . 4880 3.27 2000 I690 5530 3.75 2050 l 64o 6150 4.25 2100 1590 6760 4.80 2150 1540 7390 0 0 5690 kp = r J 6. ^ ------,--- 1.,= ..-20 650 2 -20650 X .00459 = 38.9

Eun 93 Temp, 0° Cell C Conc. 0.00552 m. Date 8/50/56 t(min.) B t(Roo-B)

.32 1350 1750 560 .67 1400 1700 ll4 o 1.02 1450 1650 1685 1.40 1500 1600 2240 1.78 1550 1550 2760 2.20 1600 1500 5500 2.65 1650 1450 3840 3.13 1700 l400 4580 3.65 1750 1350 4900 4.17 1800 1500 5420 4.75 1850 1250 5940 5.37 1900 1200 6450 00 5100 1 —3100 I I = -15960 ^2 = _ i 396o X .00552 149

Table 43 Nitrocyclopentane

Run 99 Temp, 9.93° Cell D Conc, 0,00184 m. Date 8/31/56 t(min.) E .43 2880 3350 1440 .63 2930 3300 2080 .82 2970 3260 2675 .97 3000 3230 314 o 1.45 3100 3130 4540 1.72 3150 3080 5300 1.97 3200 3030 5970 2.25 3250 2980 6700 2,82 3350 2880 8I30 3.10 3400 2830 8770 3.42 3450 2780 9520 3.73 3500 2730 10200 4 .4 o 3600 2630 11600 4,75 3650 2580 12300 5.12 3700 2530 13000 0 0 6230 1. -6230 = 85.8 I = -39450 2 -39450 X ,00184

Run 102 Temp, 9.93Ü Cell G Conc. 0,00552 m, Date 8/31/56 t(min,) R ^00“® t(E*o-E) .30 1500 1775 530 .45 1550 1725 780 .62 1600 1675 lo4 o .80 1650 1625 1300 .98 1700 1575 1550 l,4 o 1800 1475 2065 1,62 1850 1425 2310 1.87 1900 1375 2575 2,12 1950 1325 2810 2 ,4 o 2000 1275 3060 oo 3275 = .-3Â7.1 I = -7085 -7085 X ,00552 = 83.7 150

Table kk- Nitrocyclopentane

Hun 100 Temp. 9.930 Cell E Conc. O.OO368 m. Date 8/31/56 t(rain.) R ^ 00“® t(Boo-E)

.22 2050 2480 ■ 546 .38 2100 2430 9 2 4 .55 2150 2380 1310 .90 2 2 5 0 2280 2 0 5 0 1.10 2300 2230 2450 1.29 2 3 5 0 2180 2810 1.72 2 4 5 0 2030 3380 1.93 2500 2 0 3 0 3 9 2 0 2.17 2 5 5 0 1980 4300 2.68 2 6 5 0 1880 5 o4 o 2.93 2700 2830 3 3 7 0 CO 4530 k o - ...... I = -14760 -14760 X .00368 = 83.3

Run 101 Terap. 9.93° -Cell P Conc. 0.00460 ra. Date 8/31/56 t(rain.) R RoQ—R t(Ro^—R) . .

.24 1700 2 0 3 3 4 9 0 .40 1750 1985 795 .57 1800 1 9 3 3 1100 .93 1900 1833 1710 1.13 1 9 5 0 1783 2020 1.32 2000 1 7 3 3 2 2 9 0 1.77 • 2100 1633 2 9 0 0 2.02 2150 1383 3200 2 . 5 4 2 2 5 0 1485 3 7 7 0 2.82 2300 1433 4050 3 . 4 5 2400 1 3 3 3 4610 3.80 2450 1285 4890 CO 3733

I = -9330 *"2 “ -9330 % .00460: =, 87.0 151

Table 45 Nitrocyclopentane

Run 106 Temp. 28.00° Cell D Gone. 0.00183 m. Date 9/1/56 t(mln.) R R^o-R ' t(R^~R)

.37 1990 1700 630 .63 2100 1590 1000 .78 2150 1540 1200 .92 2200 1490 1370 1.07 2250 l44 o 1540 1.22 2300 1390 1700 1 .4 o 2350 1340 1880 1.60 2400 1290 2060 1.80 2450 1240 2230 2.01 2500 1190 2390 2.23 2550 ll4 o 2520 CD 3690 k o - .-36,2.0 .. ... = 322 I = -6270 -6270 X .00183

Run 107 Temp. 28.00° Cell E Conc. 0.00365 m. Date 9/2/56 t(mln.) R . Rq^—R , , t,(RoQ—R) , ,

.13 1400 1340 174 .30 1500 1240 372 .40 1550 1190 476 .50 1600 1140 570 .60 1650 1090 655 .85 1750 990 842 .98 1800 940 923 1.15 1850 890 1025 1.32 1900 84o lllO 1.51 1950 790 1190 CD 2740 kp - r.2Z 4 p ■ . = 316 I = -2380 . , 2 . -2380 X . 00305. 152

Table 46

Ni trocyclopentane

Eun 108 Temp. 2 8.00° Cell P Conci 0 .00^57 m. Date 9/2 /5 6

t(mln.) E E ^ _ E t(Eoo-E) .

.18 1200 1070 193 .2 7 1250 1020 276 .37 1300 970 338 .47 1330 920 432 .37 1400 870 496 .68 1450 820 338 .83 1300 770 64 o .98 1330 720 703 1.17 1600 670 783 1.3 3 1650 620 838 1.58 1700 370 902 OÛ 2270

I = -1 4 9 4 k2 - ■

Eun 109 Temp. 2 8.00 ° Cell G Conc. 0 .0 0 4 5 7 m. Date 9/2/56

t(min.) E %00-B t(Rao-B) .

.19 1250 1117 212 .2 8 1300 1067 299 .37 1330 1017 376 .43 1400 967 433 .3 7 1450 917 522 .67 1500 867 380 .8 0 1330 817 633 .93 1600 767 728 1.12 1630 717 803 1.3b 1700 667 868 1.32 1730 617 938 ao 2367 y _2367 ' V ' I = -1373. . 2 - -1373. X ..0043.7 = 329 153

Table 4? Nitrocyclohexane

Hun 73 Temp, 0° Cell B Conc. O.OlO m. Date 8/2/56

t(min.) E ^ 00“^

1.25 780 1030 1290 1 .6o 790 1020 I630 1.95 800 1010 1970 2.30 810 1000 2300 2 ,65 820 990 2620 3.38 840 970 3280 4.15 860 950 3940 5.15 885 . 925 4760 5.77 900 910 5250 7.52 940 870 6540 9.40 980 830 7810 10.38 1000 810 8410 12.55 lo4 o 770 9660 CO 1810 _ -1810 ICo — I = -24500 2 -24500 X .0101 -

Run 74 Temp. 0° Cell A Gone. 0.00505 m. Date 8/2/56

t(min.) E Boo"B t(Eoo-E).

.67 1420 1830 1230 2.05 1460 1790 3670 3.48 1500 1750 6090 4.98 1540 1710 8520 6.55 1580 1670 10950 8.53 1628 1622 13860 9.85 1660 1590 15700 11.62 1700 1550 18000 00 3250 k -3250 ... ,.. .. = 7.61 I = -84600 2 - -84600 X .00505. 154-

Table 48 Nitrocyclohexane

Run 75 Temp, 0 ° Cell 0 Conc. O.OO707 m. Date 8/2/56 t(min.) E Rg^-R t(RQQ-R)

.62 1020 1395 865 8 .0 0 1220 1195 9570 8.42 1230 1185 9990 8 . 8? 1240 1175 10430 9.32 1250 1165 10880 : 9.78 1260 , .1155 11300 10.23 1270 1145 11720 11.17 1290 1125 12580 11.67 1300 1115 13010 1 2 .6 3 1320 1105 13970 CO. 2415 k p - =2415 ...... I = -43500 -43500 }: .00707 7 'G6

Run 90 Temp. 0° Cell P Conc. 0.0101 Date 8/25/56 t(min.) R Boo-B t(Roo-E)

.28 1070 1470 410 .78 1090 1450 1130 1.50 1120 1420 2l 40 2.25 1150 1390 3130 3.45 1200 1340 4630 4.85 1250 1290 6260 6.33 1300 1240 7850 7.92 1350 1190 9420 9.62 1400 l l 4o 11000 11.43 1450 1090 12500 13.37 1500 10 40 13900 00 1540 _ Z.2540 . I = -32700 ■ 2 - >32700. X. .0101 = 7.70 155

Table 4$ Nitrocyclohexane

Run 98 Temp'. 9.93° Cell C Conc. 0.00736 m. Date 8/31/56 t(min,) R Boc-a t(Eoo-E)

.43 770 895 385 1,08 800 865 935 1.97 84o 825 1620 2.68 870 795 2130 4.28 930 735 3140 5.15 960 705 3630 6.08 990 675 4110 6.75 1010 655 4420 7.82 lo 4o 625 4880 CO 1665 I = -12520 ^2 - -12520 X .00736 - 18.1

Run 96 ' Temp. 9.930 Cell A Conc. 0.00368 M. Date 8/31/56 t(min.) R Boo-a t(Eoo-E)

.32 1450 1580 506 .75 1470 1560 1170 1.4 o 1500 1530 2140 2,08 1530 1500 i" 3120 2,55 1550 1480 3780 3.15 1580 1450 4580 4 .4 o 1630 i4 oo 6160 5.17 1660 1370 7100 6,25 1700 1330 8320 7,10 1730 1300 9230 8.25 1770 1260 10400 eo 3030 kp = ,r,?,P„?,Q----- w„.— — _ ^ o Q I = -43580 -43580 x, .00368 156

Table 50 Nitrocyclohexane

Eun 97 Terap. 9.93° Cell B Conc. 0.00552 ra. Date 8/31/56 t(min.) E ^oo“® t(Boo-E)

.40 1030 1150 460 1.03 1050 1130 1160 1.67 1080 1100 1840 2.13 1100 1080 2300 2.32 1130 1050 2960 3.30 1150 1030 3400 4.07 1180 1000 4070 4 .5 8 1200 980 4500 5.68 1240 940 5340 6.57 1270 910 5980 7.48 1300 880 6580 00 2180 _ -2180 kr = 1 8 .2 I = -21650 -2I650 X .00552

Run 104 Temp. 2 8.0 0 ° Cell A Conc. 0 .0 0 5 6 4 ra. Date 9/ 1/56 t(rain.) E Rqo“^ ^ (E^^-E)

.42 1000 865 363 .59 1020 845 498 .78 lo4 o 825 644 .98 1060 805 790 1.18 1080 785 927 1.62 1120 745 1208 1.85 ll4 o 725 1340 2.08 1160 705 1465 2.33 1180 685 1600 2.60 1200 665 1730 2.87 1220 645 1850 00 I865 kp - r 1,86.5___ I = -6425 2 -6425 X. .00364 - 157

Table 51 Nitrocyclohexane

Run 105 Temp. 28,00° Cell C Conc. 0.00364 rn. Date 9/1/56

t(min, ) E %00-B tdoo-E)

.30 980 853 256 1000 833 391 .75 1030 803 602 .85 lo4 o 793 674 1.05 1060 773 812 1.26 1080 753 950 1.48 1100 733 1086 1.93 il4 o 693 1340 2.18 1160 673 1470 2.45 1180 653 1600 2*72 1200 633 . 1720 3.00 1220 613 184o CO 1833 ko = -1.8.33 = 78^3 I = -6445 -6445 X .00364

Run 103 Temp. 26.00° Cell B Conc. 0.00548 m. Date 9/1/56 t(min.) E Eqo-R ' t(EoQ-E)

.22 690 64 o 141 .28 700 630 176 .65 740 590 384 .85 760 570 484 1.05 780 550 578 1.27 800 530 673 1.49 820 510 760 1.7 3 84o 490 848 lf99 860 470 936 2.27 880 450 1022 oo 1330 kc> = d m .___ ^ = 76.8 I = -3I6O .3160 X. .00548 158

Table 52

NItrocycloheptane

Run 120 Temp. 0° Cell C Couc, 0.00 8 5 2 m. Date 11/ 12/56

t(min,) E Boo-B t (î^oo“B)

‘.37 880 1255 464 .63 900 1235 780 1.00 930 1205 1205 1 .2 7 950 1185 1510 1.54 . 970 1165 1800 2.38 1030 1105 2630 2.87 10 60 1075 3090 3.37 1090 1045 3520 4.42 1150 985 4350 5.00 1180 955 4780 6 ,2 7 124 o 895 5610 6.95 1270 865 6020 oo 2135 V _ -2135 = 20 Q I = -12000 2 - _12000 X .00852

Run 119 Temp. 0° Cell B Conc. 0.00596 ra. Date 1 1 /1 2 /5 6 t(mln.) E B&o-B

ë52 124 o 1775 924 .75 1260 1755 1320 1.00 1280 1735 1735 1.2 7 1300 1715 2180 2 .9 1 1350 1665 3200 2 ,6 3 l4 oo 1615 4250 3*40 1450 1565 5320 4,20 1500 1515 6370 5.07 1550 1465 7430 5.98 1600 1415 8460 6.97 1650 1365 9510 8 .0 2 1700 1315 10580 I = -24960 %. -3015., ..... ~ -24960 X .00596 = 20.2 00 3015 ^ 139

Table 53 Nitrocycloheptane

Run 118 Temp. 0° Cell A Conc. 0 .0 0 4 2 6 m ’. Date 11/ 1 2 /5 6

t(rain.) R t(Boo-a)

.40 1660 2420 970 .6 5 1680 2400 1560 .9 0 1700 2380 2140 1.33 1730 2330 3620 2.92 1850 2230 6510 3.67 1900 2180 8000 4 .4 2 1930 2130 9410 6.07 2050 2030 12300 6.92 2100 1980 13700 8.82 2200 1880 16600 9.83 2250 1830 18000 00 4080 -4080 I = -47000 ^2 - -47000 X .00426 - .4

Eun 227 Temp. 0 ° Cell D Conc. 0.00514 m. Date 2/27/57 t(min,) R Goc-B t(Eoo-H)

.65 1550 2010 1310 1.25 1600 i960 2450 1.87 1650 1916 3370 2.33 1700 I860 4710 3.-23 1730 1810 3830 3 i 93 1800 1760 6960 3.32 1900 1660 9160 6.37 1930 I&IO 10280 7.28 2000 1560 11360 8.25 2030 1510 12480 9.25 2100 1460 13520 ^ .3 3 2150 1410 14580 CO 3360 -3S 6Q... . I = -33200 *2 = _ 33200 X .00514 - 20.8 l6o

Table 5^ Nitrocycloheptane

Run 146 Temp’ 9.93° Cell C Conc. 0.00424 m. Date 11/28/56

t(min.) R ^00 t(Ro,

.4 o 1300 l64 o 656 .65 1330 1610 1050 1.17 1390 1550 1810 1^44 1420 1520 2190 2,00 1480 l460 2920 2.30 1510 1430 3290 2,63 1540 l4 oo 3680 3 .3 1 1600 1340 4430 3 .6 7 1630 1310 4810 4.43 1690 1250 5540 4.85 1720 1220 5920 5 .7 3 1780 II60 6650 6 ,2 2 1810 1130 7030 6.70 1840 1100 7380 00 2940 -2940 I = -15510 2 ■ - -15510 X .00424 = 44.7

Run 235 Temp. 9.93d Cell A Gone. 0,00244 m. Date 3/4/57

t(min.) R Boo-B t(Roo-R)

,48 2400 2780 1340 1.50 2530 2650 3980 2 ,9 6 2700 2480 7350 3'92 2800 2380 9340 4 .9 7 2900 2280 11350 7,33 3100 2080 15280 8 .6 7 3200 1980 17200 10,15 3300 1880 19100 11.78 3400 1780 21000 00 5 I8O -5.180..... r- I = -46300 kc -46300 X, .00244 = 45.9 161

Table 55 Nitrocycloheptane

Run 148 Temp. 9.93° Cell A Conc. 0.00848 m. Date 11/28/56 t(min,) R ®co”^ t(Boo-R) .

v35 690 84o 294 .62 720 810 502 .87 730 780 678 1.1 7 780 730 878 1.78 84o 690 1230 2.15 870 660 1420 2.97 930 600 1780 3.42 960 370 1950 3.93 990 340 1950 CD 1330 I = -5840 ^2 =-5840 X .00848 ^ ^7.0

Run 147 Temp'. 9. 9 3° Cell B Conc. 0.00424 m. Date 11/28/56 t(min.) R ®oo“® t(Eoo-R) .

ë28 1300 1600 450 .32 1330 1570 816 1.00 1390 1510 1510 1 .5 a 1450 1450 2200 2 .0 9 1510 1390 2910 2 .7 2 1570 1330 . 3620 3*05 1600 1300 3960 3 .7 3 1660 1300 3960 4 .1 3 1690 1210 5000 4392 1750 1150 5660 3 .3 3 1780 1120 6000 CO 2900 -2900 I = -14480 "2 = -14480 X .00424 = 47 “ 2 162

Table 56 Nitrocycloheptane

Run 189 Temp. 2 8 .0 0 ° Cell A Conc. 0 .00413 m'i Date'1 /1 0 /5 7 t(min, ) R R t(RoQ-R) ^ C O -

.27 910 900 243 .38 940 870 330 .50 970 84o 415 .78 1030 780 600 .92 1060 750 680 1 .0 7 1090 720 760 1 .2 7 1120 690 863 1.47 1150 660 955 1*90 1210 600 1122 2 .1 7 1240 570 1216 2.43 1270 540 1290 CO 1810 , -1810 I = -2 4 3 0 ^2 = -2 4 3 0 X .00413 = 180

Run 188 Temp, 2 8 .0 0 ° Cell D Conc. 0.00516 m. Date 1 /9 /5 7 t(min.) R Ro^-R t(Eoo-B)

.35 850 620 217 .5 8 900 570 330 1.00 975 495 495 1 .1 5 1000 470 540 1 .5 2 1050 420 64o 2 .5 3 1150 320 820 00 1470 , -1470 182 I = - I 5 6 4 ^2 - -1564 X .0 0 5 1 6 - 163

Table 57 Nitrocycloheptane

ti H .1 R u n 190 Terap. 28.00° Cell B Conc. 0.00248 ra. Date 1/ 10/57

t (raln.) R ®OC“® t(Eoo-R)

.4 3 1500 1380 594 ^63 1550 1330 838 .75 1580 1300 97^ .88 1610 1270 1120 1.03 l 64o 1240 1280 1.18 1670 1210 1430 1.32 1700 1180 1560 1.4 7 1730 1150 1690 00 2880 -2880 = 180 I = - 6^35 ko = -6435 X .00248

R u n 191 Terap. 28.00° Cell A Conc. 0.00413 ra. Date 1/11/57 t (rain.) R Boo-E t(Roo-E)

.27 910 886 239 .38 940 856 325 .52 970 826 429 .93 1060 736 683 1.12 1090 706 791 1.28 1120 676 865 1.48 1150 646 956 1.70 1180 616 1047 1 .92 1210 586 1125 2.18 1240 556 1213 00 1796 I = -2420 kg = -2Î20 X .00413 = 179 164

Table 58 Nitrooyclooctane

R u n 219 Terap. 0® Cell A Conc. 0.0 0257 m. D a t e 2/26/57

t(raln.) R Roo-B

.85 1600 2065 2760 1.58 1650 2015 3180 2 .3 6 1700 1965 4640 3.19 1750 1915 6120 4.93 1850 I8I5 8950 5.95 1900 1765 10500 7.0 0 1950 1715 12000 8 .1 2 2000 1665 13520 9 .2 9 2050 1615 15000 10.57 2100 1565 16530 13.32 2200 1465 19520 16.48 2300 1365 22500 CO 3665 v_ = -3665______. g q I = -45000 2 _45ooo X .00257 -

R u n 121 Terap. 0 ° Cell P Conc. 0 .0 0 4 2 6 ra. Date 11/ 1 2 /5 6

t(rain.) R B o o ~ B

.6 5 2350 3420 2220 1 .2 0 2400 3370 4050 2 .2 8 2500 3270 7460 3.57 2600 3170 11400 4 .9 3 2700 3070 15150 6.4 0 2800 2970 19000 7 .9 8 2900 2870 22900 9 .5 5 3000 2770 26500 1 1 .4 5 3100 2670 30600 13.42 2200 2570 34500 00 5770 -5770 , ^ = 15.6 I = -8 6 6 0 0 % = -8 6 6 0 0 X .0042é 165

Table 59 Nitrocyclobotane

Run l'28 Temp, o" Cell G Conc. 0 .0 0 8 5 2 m. Date 11/ 1 4 /5 6 t(mln.) B E^-B tCB^o-B)

.42 1330 1640 690 .62 1350 1620 1010 1.17 l4 oo 1570 1840 1.73 1450 1520 2630 2.35 1500 1740 3460 3.00 1550 1420 4260 3.70 1600 1370 5070 4.43 1650 1320 5850 5 .2 2 1700 1270 664o 6.07 1750 1220 7400 6 .9 5 1800 1170 8140 00 2970 , -2970 = 17.1 I = -20410 ^2 - -20410 X .00852

Bun 219 Temp. 0° Cell A Conc. 0 ,0 0 2 5 7 m. Date 2/ 2 6 /5 7 t(min.) B B^^-B t(BoQ-B)

1.70 2800 3580 60 80 3 .4 0 2900 3480 11800 5.23 3000 3380 17700 7 .1 8 3100 3280 23500 9.27 3200 3I8O 29500 11.52 3300 3080 35500 13.88 3400 2980 41300 1 6 .3 3 3500 . 2880 47100 1 9 .0 8 3600 2780 53100 2 1 .9 8 3700 2680 58900 25.12 3800 2580 64800 0 0 6380 V _ -6 3 8 0.... -...... I = -157900 ^2 - -157900 X .00257 = 15.7 166

Table 60 Nitrooyclooctane

Run 158 Terap. 9.93° Cell B Conc. 0.00848 ra. Date 12/5 /5 6

t(min.) R ^oo”® t (Rq q -R)

.45 750 810 364 .73 775 785 573 1.02 800 760 775 1.65 850 710 1170 2.00 875 685 1370 2.38 900 660 1570 3.22 950 610 1965 3.68 975 585 2155 4.18 1000 560 2340 oo 1560 - i 960 I = -5530 ^2 = -5530 X. 00848 = 33.3

Run 159 Terap. 9.93° Cell A Conc. 0.00424 ra. Date 12/5/56 t(raln.) R R q q —R t(RQÇ-R)

.47 1350 1510 710 .73 1375 1485 1085 1.00 l4 oo l46 o l46 o 1.55 1450 l4 lo 2180 2.18 1500 1360 2970 2.87 1550 1310 3760 3.58 1600 1260 4520 4.37 1650 1210 5290 5.22 1700 1160 5050 6.13 1750 1110 6810 7.13 1800 1060 7560 8.22 1850 1010 8310 00 2860 I = -20080 ^2 - -I^O'^Ox .ook6& = 3 3 .5 167

Table 61 Nltrocycloôctane

R u n 236 Temp. 9.93° Cell B Conc. 0.00 5 0 1 m. D a t e 3 / V 5 6

t(mln.) R Boo-B t(Roo-B)

.43 1250 1500 645 ..90 1300 1450 1310 1.93 1400 1350 2610 2.53 1450 1300 3290 3.87 1550 1200 4650 4.62 1600 1150 5320 6.37 1700 1050 6690 8.42 1800 950 8000 11.02 1900 850 9360 14.22 2000 750 IO68O 18.32 2100 650 11920 00 2750 -2750 = 3 4 .0 I = -16110 ^2 = -16110 X .00501

R u n 2 # Temp. 9.93° Cell A Gone. 0.0 0 2 5 6 m. Date 3/6/57

t ( m i n . ) R Boo-B t(Roo-B)

.68 2300 2650 1800 1.65 2400 2550 4200 3.85 2600 2350 9050 5 .1 3 2700 2250 11570 6 .5 2 2800 2150 14030 8 .0 7 2900 2050 16570 9.7 5 3000 1950 19000 11.63 3100 1850 21500 13.72 3200 1750 24000 00 4950 0 I = -55400 55400 X .00256 3 4 .9 168

Table 62 Nltrocyoloôotane

Hun 252 Temp. 28.00° Cell A Conc. O.OO231 m. Date 3/8/57 t(mln.) R Eoo-E t(EQQ-E)

.2 7 1650 1660 450 .48 1700 1610 770 .72 1750 1560 1120 1 .2 3 1850 1460 1800 1.5 2 1900 1410 2l40 2 .1 7 2000 1310 2840 2.93 2100 1210 3540 3.83 2200 1110 4250 4.88 2300 1010 4940 6.18 2400 910 5630 7.78 2500 810 6300 9.80 2600 710 6960 CO 3310. =3.310. 132 I = - 10880 %2 -10880 X .00231

Eun 254 Temp. 28.00° Cell C Conc. O.OOO770 m. Date 3/8/57 t(mln.) E Eg^-E t(Eo^-E)

.45 4700 4265 1920 .92 4800 4165 3830 1.88 5000 3965 7450 3.02 5200 3765 11400 4.28 5400 3565 15250 5 .7 0 5600 3365 19150 7.28 5800 3165 23000 9 .0 5 6000 2965 26800 11.08 6200 2765 30600 ao 8965 8.9 ^ 5 ______= 130 I = -89400 ^2 .89400 X .000770 169

Table 63 Nltrooyclooctane

Run 253 Temp, 28.00° Cell B Conc. 0 .0 0 1 5 4 m. Date 3/8/57

t(min.) R Boo-B

.37 2500 2440 900 • 59 2550 2390 1410 1 .0 6 2650 2290 2430 1.57 2750 2190 3440 1.85 2800 2l4 o 3960 2 .4 3 2900 2040 4960 3.10 3000 1940 6010 3.83 3100 184o 7050 4 .6 5 3200 1740 8040 5.08 3250 1690 8580 00 4940

I = -24330 ^2 - -2^530 X '.00154 “

Run 257 Temp. 28.00° Cell A Conc. 0-.00231 m. Date 3/9/57

t(min.) R Boo”B t ( R(X)-R )

.3 4 1550 1655 560 .57 1600 1605 920 1.08 1700 1505 1630 1.68 1800 1405 2360 2.38 1900 1305 3110 3 .2 0 2000 1205 3860 4 .1 5 2100 1105 4590 5.28 2200 1005 5310 5.93 2250 955 5660 CO 3205 --1205______I = -10800 ^2 = -10800 X .00231 “ 170

Table 64

1-d-Nitrocyclobutane

Run 129 Temp. 0° Cell A Cone. 0,00426 m, Date 11/14/56 R- 1680 ohms R ^ 3580 ohms t(min.) R ®2“^1 Boo-Bi Boo-B2 "k" 5.08 2050 6 .1 5 2100 50 1530 1480 1.0 7 19 .6 7 .3 2 2150 50 1480 1430 1 .17 19.2 8.58 2200 50 1430 1380 1.2 6 19.1 9.9 7 2250 50 1380 1330 1 .3 9 18.7 11.45 2300 50 1330 1280 1.48 18.9 13.03 2350 50 1280 1230 1.58 19.1 14.75 2400 50 1230 1180 1.72 19.0 16,65 2450 50 1180 1130 1.90 18.8 kp = 19.1

Run 131 Temp. 0° Cell C Conc. 0.00852 m. Date 11/ 14/56 R- 865 ohms R» 1835 ohms t(min.) R Rg-Ri Rg^^-R], B00-R2 'At "k"

1 .9 5 1020 2.33 1040 20 815 795 .38 19 .6 2.72 1060 20 795 775 .39 2 0 .0 20 1 9.2 3 .1 5 1080 775 755 .43 3.58 1100 20 755 735 .43 2 0 .2 4 .0 5 1120 20 735 715 .47 1 9 .6 4.58 ll4 o 20 715 695 .53 18.3 5.12 1160 20 695 675 .5 4 19.0 5.68 1180 20 675 655 .56 19.5 6.28 1200 20 655 635 .60 1 9 .4 6.93 1220 20 635 615 .65 19.0 7.60 1240 20 615 595 .67 19 .7 8.32 1260 20 595 575 .72 19 .6 kg = 1 9 .4 171

Table 65

1-d-Nitrooyclobutane

Run 130 Temp, 0° Cell B Conc. 0,00596 m. Date 11/14/56 Rq 1230 ohms Rqo 2590 ohms t(min.) R fioo“^l B cvq-R 2 '^t "k"

1480 3 .1 7 1110 1080 .58 3 .7 5 1510 30 2 0 ,7 4 ,3 7 1540 30 1080 1050 .62 2 0 ,5 5 .0 7 1570 30 1050 1020 .70 19.2 5.78 1600 30 1020 990 .71 20,1 6 .5 5 1630 30 990 960 .77 1 9 .7 7.38 1660 30 960 930 .83 19.4 6,2 5 I690 30 930 900 .87 1 9 .8 9.18 1720 30 900 870 .93 1 9 .8 10,17 1750 30 870 840 .99 19.9 11,23 1780 30 840 810 1 ,0 6 20,0 %2 = 1 9 .9

Run 143 Temp. 9.93° Cell D Conc, 0,00424 Date 11/2 7/5 6 R, 1260 ohms Roo 2525 ohms t(min,) R R2-R1 Boo-^i ®oo“^2 At «k*

2,22 1525 25 1000 975 .3 1 (49.5) 2.53 1550 46.1 2 ,8 8 1575 25 975 950 .35 1600 25 950 925 .37 46.0 3 .2 5 ,40 4 5 ,8 3 .6 5 25 25 925 900 4 .0 6 50 25 900 875 .41 46.3 25 875 850 .45 4 5 .7 4 ,5 1 75 825 .46 46.4 4.97 1700 25 850 825 800 5 .4 7 25 25 .50 4 5 .3 5.98 50 25 800 775 .51 4 7 .2 6.5 3 75 25 775 750 .55 46.7 1800 25 750 725 .60 4 5 .8 7 .1 3 700 . 64 46.1 7 .7 7 25 25 725 k2 = 46,1 172

Table 66 1-d-Nltrocyolobutane

Bun 1 # Temp. 9.93° Cell E Conc. 0.00424- m, Date 11/27/5 6 Eq 1760 ohms 3425 ohms t(mln.) R R2-R1 Roo-Hi Roc-Bg At "k"

2.33 2100 .20 44.2 20 20 1325 1305 2.53 20 .20 2.73 4o 1305 2385 45.7 40 1285 1245 .39 49.0 3.12 80 40.2 2200 20 1245 1225 .25 3.37 20 3.60 20 1225 1205 .23 4 5 .1 20 1205 1185 .23 46.6 3.83 4o 41.1 4.10 60 20 1185 1165 .27 20 1165 4.35 80 1145 .25 4 5 .9 4.62 20 1145 1125 .2 7 44.0 2300 .28 44.0 4 .9 0 20 20 1125 1105 5.20 40 20 1105 1085 .30 42.5 20 1085 1065 .27 4 9 .0 5.47 60 41.7 5.80 80 20 1065 1045 .33 6.10 2400 20 1045 1025 .30 4 7 .6 6.43 20 1025 1005 .33 45 .0 20 44.2 6.78 4o 20 1005 985 .35 20 46.0 7.130 60 985 965 .35 20 965 945 .37 4 5 .4 7.50 80 46.2 7.88 2500 20 945 925 .38 8.28 20 20 925 905 .40 4 5 .7 8.68 4o 20 905 885 .40 4 7 .7 9.12 60 20 885 865 .44 4 5 .4 20 9.55 80 865 845 .43 48.9 kg = 4 5 .3 173

Table 6? 1-d-Nitrocyclobutane

Bun 1^5 Temp. 9.93° Cell F Conc. 0.00848 m. Date 11/27/56 R q 910 ohms R^ 1850 ohms t(mln.) R Rg—R]_ ^oo“®l R^g-R2 ^ t **k**

1.32 1130 1.62 60 30 720 690 .30 45.3 1.95 90 30 690 660 .33 44.0 2.30 1220 30 660 630 .35 45.4 2.67 50 30 630 600 .37 48.2 3.10 80 30 600 570 .43 45.9 3.57 1310 30 570 540 .47 46.7 4.10 4o 30 540 510 .53 46.2 4.68 70 30 510 480 .58 47.4 k2 = 46.1

Run 174 Temp. 28.000 Cell 0 Conc. 0.00253 m. Date 12/14/56 R o 1350 ohms R ^ 244o ohms t(min.) R R2-R1 R(x)-Bl R 00 % At "k"

.77 1580 .87 I600 20 860 840 .'10 216 .97 20 20 840 820 .10 226 1.08 4o 20 820 800 .1 1 216 1.21 60 20 800 780 .13 192 1.33 80 20 780 760 .12 219 1.47 1700 20 760 740 .1 4 203 1.62 20 20 740 720 .15 195 1.77 4o 20 720 700 .15 206 1.92 60 20 700 680 .15 218 2.10 80 20 680 660 .1 8 193 2.28 1800 20 660 64 o .1 8 205 2.45 20 20 64 o 620 .17 231 2.65 40 20 620 600 .20 210 2.87 60 20 600 580 .22 204 ko = 210 174

Table 68

1-d-Nitrocyclobutane

fîun 177 Temp. 2 8.00° Cell A Conc, 0.00169 m, Date 12/ 1 8 /5 6 Rq 2 0 60 ohms Roo3550 ohms t(mln.) R Rg—R]_ ^oo“^l RçjQ-Rg ^ t "k"

1.60 2460 1.78 2490 30 1090 1060 .1 8 21x 9 30 1060 1030 .2 0 20x7 1 .9 8 2520 x 2.20 30 1030 1000 .2 2 20 0 2550 1000 204 2 .4 3 2580 30 970 .23 2.70 2610 30 970 940 .27 185 30 940 910 2 .9 7 2640 .27 197 2700 60 910 850 .5 8 224 3 .5 5 30 204 9.87 2730 850 820 .32 4 .2 0 2760 30 820 790 .3 3 213 30 790 760 4 .5 7 2790 .3 7 205 4.95 2820 30 760 730 .3 8 216 kr 208

Run 175 Temp . 2 8.00 ° Cell D Conc. 0 .0 0 4 2 2 m. Date 12/ 1 4 /5 6 810 ohms 1535 ohms Eo E(>o «k« t(min. ) R Rr -Ri Eoo“^l Boo-Bz At

.3 7 950 .50 980 30 585 555 .13 2 3 .1 .72 1020 4 o 555 515 .2 2 2 0 .7 .90 1050 30 515 485 .1 8 2 1 .7 1.05 1070 20 485 465 .1 5 1 9 .2 1 .2 8 1100 30 465 435 .23 2 0 .9 1.45 1120 20 435 415 .17 2 1 .2 1.73 1150 30 415 385 .2 8 2 1 .8 1.95 1170 20 385 365 .2 2 2 1 .0 2 .3 3 1200 30 365 335 .3 8 2 1 .0

^2 = 212 175

Table 69 1-d-Nitrocyolopentane

Run 134 Temp. 0° Cell G Conc. 0.00852 m, Date 11/15/56 Ro 1230 ohms Ro o 2810 ohms t(min.) R R2-R1 R o o “Rl R0 0 - R 2 A t "k"

1450 7*33 20 1340 4.94 8.25 1470 1360 *92 9*22 1490 20 1340 1320 *97 4.94 10.23 1510 20 1320 1300 1.01 4.90 1300 11.28 1530 20 1280 1.05 4.85 12.38 1550 20 1280 1260 1.10 4.78 13*52 1570 20 1260 1240 1.14 4.76 14.70 1590 20 1240 1220 1.18 4.76 15*92 1610 20 1220 1200 1.22 4.75 17*18 1630 20 1200 1180 1.26 4.76 18.50 1650 20 1180 1160 1.32 4.69 19*87 1670 20 1160 l l 4o 1.37 4.68 21.27 1690 20 ll4o 1120 1.4o 4.74 kp = 4.79

Run 133 Temp. 0 ° Cell F Conc. 0.00596 m. D a t e 11/15/56 R- l 64o ohms Rf^^ 3690 ohms t(min.) R B^-Ei ®oo“®l A t "k"

15*65 2030 17.42 2060 30 1660 I630 1*77 4.85 19*26 2090 30 1630 1600 1.86 4.78 21.22 2120 30 1600 1570 1.94 4.76 1570 1540 23*25 2150 30 2.03 4.73 30 1540 1510 2.08 4.79 25*33 2180

kg = 4.78 176

Table 70 1-d-Nitrocyclopentane

Run 132 Temp, 1° Cell C Conc. 0 .00426 m. Date 11/15/56 R0I58O ohms Roo3580 ohms t(mln.) R R2-R1 Roo”®i R00-R2 At "k"

24.22 1990 26.90 2020 30 1590 1560 2.68 4'. 81 30.18 35 1560 1525 3.28 4.76 2055 2.44 4.76 3 2 .6 2 2080 25 1525 1500 2110 30 1500 1470 3.05 4.75 3 5 .6 7 1470 l 44o 38.83 2l40 30 3.16 4.77 42.10 2170 30 1440 1410 3.27 4.81 1410 1380 ^ 2200 30 3.47 4.73 5 .5 7 30 1380 1350 3.56 4.81 4 9 .1 3 2230 kg = 4 .7 7

Run 142 Temp. 9.93^ Cell C Conc. 0.00848 m. Date 11/27/56 Rq 645 ohms R ohms t(raln.) R R2-R1 ®oo”®l R 00-R2 "k"

3.37 760 4.22 780 20 640 620 .85 11.47 5.13 800 20 620 600 .91 11.43 6.13 820 20 600 580 1.00 11.12 7.22 840 20 580 560 1.09 10.93 8.35 860 20 560 540 1.13 11.32 9.58 880 20 540 520 1.23 11.20 10.92 900 20 520 500 1.23 11.10 12.35 920 20 500 480 1.43 11.28 13.90 940 20 480 460 1:65 10.62 15.57 960 20 460 44o 1.67 11.45 17.38 980 20 44o 420 1.81 11.57

^2 = 11.2 177

Table 71

1-d-Nltrocyclopentane

Run I M Temp. 9.93° Cell B Conc, 0,00^4-24 m. Date 11/27/56 En 1260 ohms Eoq2720 ohms t(min.) E E2-E]_ Eqq-Ej^ E0Q-Ë-Ro2 2!it "k"

9.63 1550 1170 1145 1.24 11.2 10.87 1575 25 12.15 1600 25 1145 1120 1.28 11.3 13.52 1625 25 1120 1095 1.37 11.0 14.95 50 25 1095 1070 1.43 11.1 16.45 75 25 1070 1045 1.50 11.1 18.02 1700 25. 1045 1020 1.57 11.1 19.68 25 25 1020 995 1.66 11.0 21.42 50 25 995 970 1.74 11.1 23.23 75 25 970 945 1.81 11.2 25.12 1800 25 945 920 1.89 11.3 27.12 25 25 920 895 2.00 11.3 k2 = 11.2

Run l4o Temp, 9. 93° Cell A Conc. 0.00424 m. Date 11/26/56 Rq 1230 ohms Hoo 2630 ohms t(min.) R R2-R1 ^oo-^l ^oo“®2 At "k"

9.32 1500 25 1130 1105 1.26 11.2 10.58 25 11.2 11.90 50 25 1105 1080 1.32 13.32 75 25 1080 1055 1.42 10.9 25 1055 1030 1.46 11.1 14.78 1600 11.1 16.32 25 25 1030 1005 1.54 25 1005 980 l.:6l 11.1 17.93 50 10.8 19.67 75 25 980 955 1.74 21.42 1700 25 955 930 1.75 11.4 k2 = 11.1 178

Table ?2 1-d-Nitrocyclopeutane

Eun 171 Temp. 28.00° Cell P Conc. 0.00422 m. Date 12/ 13/56 R 1150 ohms Rqq 2275 ohms t(mln. ) R R2“Rj[ R^Q—R]^ ®oo"®2 «At "k"

1.73 1340 2 .2 7 4o 935 895 .54 46.7 1380 40 .60 2.87 1420 895 855 45.9 4o 855 815 . .65 46.5 3 .5 2 1460 47.0 4 .2 3 1500 4o 815 775 .71 1540 4o 775 735 .80 45.1 5 .0 3 47.4 5 .9 0 1680 4o 735 695 .87 6.88 1620 4o 695 655 .98 47.3 4o 48.0 7 .9 7 1660 655 615 1.09 k£ = 46.7

Run 170 Temp. 28.00° Cell E Conc. 0,00253 m. Date 12/ 13/56 Rq i860 ohms Rqo 3560 ohms t(rain.) R R2-R1 ^00 ^oo”^2 "k"

2 .9 2 2160 3.48 2200 4o l 4oo 1360 .56 48.2 1320 4.07 2240 4o 1360 .59 48.5 4.68 2280 4o 1320 1280 .61 49.8 4o 1280 1240 47.0 5.37 2320 .69 6 ,0 8 2360 4o 1240 1200 .71 48.7 2400 4o 1200 1160 .79 46.8 6.87 47.6 7.7 0 2440 4o 1160 1120 .83 8,58 2480 4o 1120 1080 .88 48.3 k£ = 48.1 179

Table 73 1-d-Nitrocyclopentane

Hun 172 Temp. 28.00° Cell A Conc. 0.00422 m, Date 12/14/36 Rr,, Q 820 W 6, V UXiliiO ohms R 00 ^ 1660 ohmsVJXAUJi t(mln.) R ^2”®i Hoo”^l B0Q-R2

1000 2.35 20 660 64 o .40 4 7 .7 2 .7 5 1020 4 3 .2 3 .2 0 1040 20 64 o 620 .43 20 620 600 3 0 .4 3.63 1060 .43 4.12 1080 20 600 580 .4 9 4 7 .3 20 580 560 4.63 1100 .51 48.3 5.20 1120 20 560 54 o .57 46.7 5.80 1140 20 540 520 .60 4 7 .8 1160 20 520 500 .65 4 7 .7 6 .45 500 470 1 .0 7 7 .5 2 1190 30 48.3 1200 10 470 460 .38 48.3 7 .9 0 4 9 .8 8 .7 0 1220 20 460 44o .80 ^2 = 48.0 180

Table 1-d-Nltrooyclohexane

Run 115 Temp. 0° Cell C Conc. 0.007^3 m. Date 10/5/56 Rq 995 ohms R^g 2390 ohms t(mln. ) R Iî2"“Rj[ ^oo"“®l ^^oo""^2 ^ t *'k“

56.73 1221 1240 19 1169 1150 7.22 .88 6 3 .9 5 32 77.0 3 1272 1150 1118 13.08 .86 80.53 1280 8 1118 1110 3.50 .83

= 0.86

Run 114 Temp. 0° Cell A Conc. 0.00556 m. Date 10/4/56 Rq 1295 ohms R,QQ 3065 ohms t(mln.) R R2-R1 ^oo-^l G 00-^2 "k"

79.50 1603 1462 1445 8 6 .1 7 1620 17 6 .6 7 .91 99.80 1650 30 1445 1415 13.63 .81 1688 38 1415 1377 16.23 .90 116.03 .84 138.50 1734 46 1377 1331 22 .4 7 1304 151.67 1761 27 1331 13.17 .89

k2 = 0.87 181

Table 75 1-d-Nltrooyclohexane

Run 116 Temp. 9.93° Cell A Conc. O.OO368 m. Date 10/ 9 /5 6 Rq l46o ohms R^o 3090 ohms t(rain.) R Ro—R2-^1 R o o "®2 A t "k"

1820 56.92 1230 66.85 I860 40 1270 9.93 2.42 77.60 1900 4 o 1230 1190 10.75 2.38 89.20 1940 4 o 1190 1150 11.60 2.36 101.50 1980 4 o 1150 1110 12.30 2.39 115.00 2020 40 1110 1070 13.50 2.34 129.20 2060 40 1070 1030 14.20 2.4o Cg = 2 ,3 8

Run ll?n Temp. 9.93° Cell C Conc; 0.00 7 3 6 m. Date 10/ 9/5 6 Rq 750 ohms R 1695 ohms t(mln.) R Rg—R^ R^g—R^ Ro o "R2 At "k"

2 7 .6 8 940 30 755 725 7.02 2.27 3 4 .7 0 970 725 692 8.67 2.21 4 3 .3 7 1003 33 1032 29 692 663 8.4 o 2.19 5 1 .7 7 28 663 9.18 2.11 6 0 .9 5 1060 635 ^2 = 2.20 182

Table 76 1-d-Nltrooyclohexane

Run 111 Temp. 28.00° Cell D Conc. 0.00548 ra. Date 10/3 /5 6 Rq 6 # oh R(X) 1310 ohms t{min.) R R 2-R1 B 00-B2 At "k"

6.55 780 8.10 800 20 530 510 1.55 11.8 820 20 510 490 1.73 11.4 9.83 11.4 11.72 840 20 490 470 1.89 860 20 470 450 2 .0 5 11.4 13.77 20 450 430 2.20 11.6 15.97 880 18.48 900 20 430 410 2 .5 1 11.2 21.18 920 20 410 390 2 .7 0 11.4 24.08 940 20% 390 370 2 .9 0 11.8 2 7 .2 7 960 20 370 350 3 .1 9 12.0 ^2 = 11 .5

Run 112 Temp. 28.00® Cell C Conc. 0,00365 m. Date 10/3 /5 6 R o 950 ohms_ Rrv^ I860 ohms t(min.) R ~R2-Ri Roo”^'' Boo-Rg A t "k"

7.58 1105 740 1.02 8.6 0 1120 15 755 12.5 720 12.0 10.10 1140 20 740 1.50

k , = 12:.2 183

Table 77 1-d-Nltrocyclohexane

Run 110 Temp. 28,00° Cell A Conc, 0,00365 m. Date 10/3 /5 6 Rq 950 ohms R^00 1868 ohms Att(mln,) R H. ®oo“^l B 00-B2 Att(mln,) "k"

7 .0 5 1100 12,4 8,44 20 768 748 1 .3 9 1120 20 748 728 1,46 12.4 9 .90 ll4 o 20 728 708 1 .5 7 12,2 1 1,47 1160 11,8 1180 20 708 688 1,7 2 1 3.19 20 668 1,76 12,1 14,97 1200 688 k2 = 12,2

Run 113 Temp, 28,00° Cell E Conc, 0,00548 m. Date 10/3 /5 6 Rq 895 ohms R^xj 1800 ohms t(rain,) R Rg—Rj[ Roo“®l R2 ^t "k"

8,65 1105 680 9.62 1120 15 695 .97 10,7 20 680 660 1.31 11,2 10,93 ll4 o 20 660 640 l,4 o 11,1 12,33 1160 20 o 620 11,0 1180 64 1,50 13.83 30 620 590 2,45 11.0 16,28 1210 560 2,72 19.00 1240 30 590 10,9 30 560 530 2.97 11,1 21,97 1270

k2 = 11,0 184-

Table 78

4--N1 trocyclohexane

Run 76 Temp, o" Cell D Conc. 0.004o4 m. Date 8/3/56 t(mln.) R Rqq—R t(Ro^—R)

.68 I800 2170 14-80 1.18 184-0 2130 2515 1.6 0 I870 2100 3360 2.4-0 1930 204-0 4-900 2.82 i960 2010 5670 3 .2 7 1990 1980 64-80 4.18 1050 1920 804-0 4-.67 2080 1890 884-0 5. 1 5 2110 I860 9580 6 ,16 2170 1800 11100 7.24- 2230 174-0 12600 8.18 2280 1690 1384-0 8 .7 8 2310 1660 14-580 00 3970 -3970 I = -4-5000 K2 - -450 OOX.004-04- ' = 21.8

Run 77 Temp 0° Cell E Conc. 0.00 5 0 5 m. Date 8/3 /5 6 t(min.) R t(Roo“R)

.28 i960 254-5 710 .83 2010 24-95 2070 1.4-2 2070 24-35 34-60 2 .0 3 2130 2375 4-830 2.65 2190 2315 614-0 3 .3 2 23-50 2255 74-80 3.97 2310 2195 8720 4-,72 2370 2135 10100 5 .4-9 24-30 2075 114-00 6 .3 0 24-90 2015 12700 GO 4-505 -4-50 5 = 21.0 I = -4-2500 ^2 -4-2500 X .00505 185

Table 79

^-Nitrocyclohexane

Eun 78 Temp, 0° Cell F Conc. 0,00606 m. Date 8/3/56 t(min,) R t(Bo o ~S)

.35 1680 2120 740 .82 1730 2070 1700 1.38 1790 2010 278O 2.00 1850 1950 3900 2.65 1910 1890 5000 3 .3 2 1970 1830 6070 4 .0 7 2030 1770 7200 4.83 2090 1710 8250 5 .6 5 2150 1650 9330 6 .5 2 2210 1590 10400 00 3800 -3800 = 21.2 I = -29480 % - -29480 X .00606

Hun 79 Temp. 0° Cell G Conc. 0.0 0 7 0 7 m. Date 8/3/56 t(rain.) R Boo-B t (Roo*"®)

.42 1500 2000 84o .95 1560 1940 1840 1 .3 2 1600 1900 2510 2.10 1680 1820 3820 2.95 1760 1740 5140 3.40 1800 1700 5780 4.08 I860 1640 6700 4.85 1920 1580 7660 5 .6 7 1980 1520 ' 8610 6 .5 5 2040 1460 9560 7.48 2100 1400 10500 00 3500 ^ _ =3l500--- I = -23170 % - -23170 X .00707 “ 186

Table 80 ^-Nltrocyclohexane

Run 80 Temp, 9.93° Cell C Conc. 0.00504- m. Date 8/6/56

t(min. R t(Roo“®^

.32 1100 1290 413 .63 ll4 o 1250 788 .88 1170 1220 1075 1.35 1220 1170 1580 1.63 1250 1140 I860 2.15 1300 1090 2340 2.67 1350 lo4 o 278O 3.28 1400 990 3250 3.95 1450 940 3710 4.67 1500 890 4150 oo 2390 , -2390 = 48.1 I = -9860 ^2 - -9860 X .00504

Run 81 Temp. 9.93° Cell D Conc. 0 .00605 m. Date 8/6/56 t(min.) R fîoo“^ t(R^-R)

.5 7 980 1070 610 .73 1000 1050 767 1 .1 7 1050 1000 1170 1 .6 7 1100 950 1585 2.21 1150 900 1990 2.80 1200 850 2380 3 .4 7 1250 800 2780 4.20 1300 750 3150 00 2050 , -2050 I = _7265 = 46.7 ^2 - -7265 X .00605 187

Table 81 4-Nltrooyolohexene

Run 82 Temp. 9.93° Cell E Conc. 0 .00 7 0 6 m. Date 8/6/56 t(mln.) H t(Roo—^)

.27 1130 1330 360 .49 1170 1290 632 .69 1200 1260 870 .93 ' 1240 1220 1135 1.21 1280 1180 1430 1.50 1320 ll4 o 1710 1 .7 8 1360 1100 i960 2.12 1400 1060 2240 2.55 1450 1010 2580 3 .0 5 1500 960 2930 CO 2460 kr -2460 = I = -7500 -7500 X .00706 46.5

R u n 83 Temp. 9.930 Cell G Conc. 0.00806 m. D a t e 8/6/56 t ( m i n . ) E Roo“R t(Boo-R)

.47 1100 1225 577 .75 1150 1175 882 1.07 1200 1125 1205 l.4 o 1250 1075 1505 1.77 1300 1025 1815 2.17 1350 975 2120 2,60 i4 oo 925 2400 3.10 1450 875 2710 00 2325 -2326 I = -6075 kr, = -6075 X .00806 = 47.5 188

Table 82 ^-Nltrocyclohexene

Run 192 Temp. 28.00° Cell B Gone. 0.00248 m. Date 1/11/57 t(min.) E Roo“^^ t(Roo-H)

.28 1500 1257 352 .43 1540 1217 524 .58 1580 1177 683 .7 4 1620 1137 842 .90 1660 1097 987 1.10 1700 1057 1163 1.28 1740 1017 1300 00 2757

I ---5570 k2 - -5570 X .00248 = 199

Eun 193 Temp. 28.00° Cell C Conc. 0.00413 m. Date 1/11/57 t(mln.) E Eqq—E t(Eoo—E)

.22 900 793 174 .30 930 763 229 .43 960 733 315 .57 990 703 401 .70 1020 673 471 1.00 1080 613 613 1 .1 7 1110 583 683 1.35 1140 553 747 1.5 7 1170 523 822 GO 1693

: = kz = . 203 189

Table 83 4-Nltrocyolohexene

Run 194 Temp, 28.00° Cell D Conc. 0.00413 m. Date 1/11/57 t(min.) R R)

.28 930 770 216 .39 960 740 288 .52 990 710 369 .63 1020 680 428 .78 1050 650 507 1.10 1110 590 649 1.28 1140 560 7:17 1.48 1170 530 785 1.71 1200 500 855 00 1700

I 2010 k2 = _2oÎo X .00413 “

Run 195 Temp. 28.00° Cell E Conc. 0.00579 m. Date 1/11/57 t(min.) R Rq^ —R t (R^o—R )

.22 930 800 176 .30 960 770 231 .38 990 740 281 .68 1080 650 442 .80 1110 620 497 .93 1140 590 548 1.23 1200 530 652 l . 4o 1230 500 700 1.60 1260 470 752 00 1730

: = kg = zllll ^ 190

Table 84

Eï]do-2-Ml treble VGlo [2 • 2 • 1] Heptane

Run 43 Temp. 0° Cell A Cone. 0.00510 m. Date 3/17/56 t(min.) R B q q -R t(Roo“B)

.23 1500 1920 44 o .45 l6oo 1820 820 .70 1700 1720 1210 .95 1800 1620 1540 1.26 1900 1520 1910 1.60 2000 1420 2270 2.00 2100 1320 2640 2.97 2300 1120 3330 3.64 2400 1020 3710 4 .4 o 2500 920 4050 5.35 2600 820 4390 00 3420 -3420 I = -4990 k2 = -4990 X .00510 = 134

Bun 44 Temp, 0° Cell B Cone. 0.00510 m. Date 3/17/56 t(min.) R Boo-B t(Roo“B)

.25 1500 1900 470 .47 1600 1800 840 .70 1700 1700 1190 1.00 1800 1600 1600 1.30 1900 1500 1950 1 .6 5 2000 1400 2310 2 .0 3 2100 1300 2640 2 .4 7 2200 1200 2960 CO 3400 I = -5010 ^ = -3400 ------= 133 2 -5010 X .00510 191

Table 85 Endo-2-Nltreblevclo f 2•2 -1]Heptane

Run 45 Temp. 0° Cell B Conc, 0.00313 m. Date 3/ 19/56 t(min.) R & 00-B t(Roo-S)

.29 2500 3150 910 .50 2600 3050 1530 2 .0 5 3200 2450 5030 2 .5 2 3350 2300 5800 2.9 0 3450 2200 6380 3.10 3500 2150 6670 3 .5 2 3600 2050 7230 3 .9 7 3700 1950 7750 4.48 3800 1850 8300 oa 5650 I = -13370 = 135 k2 -13370 X .00313

Run 46 Temp. 0° Cell A Conc. 0.00 3 1 3 m. Date 3/19/56 t(min.) R t(^oo-R)

.15 2400 3150 470 .35 2500 3050 1070 .77 2700 2850 2200 1.00 2800 2750 2750 1.53 3000 2550 3900 1.80 3100 2450 4410 2.12 3200 2350 4980 2 .5 5 3300 2250 5750 2 .9 2 3400 2150 6280 3 .7 5 3600 1950 7320 4 .2 5 3700 1850 7860 4.80 3800 1750 8400 00 5550 -.1 5.50 = 134 I = -13200 %2 = % 13200 X .00313 192

Table 86

Ê33d2,-2-Nltroblcyclo [2 • 2 • 1] Heptane

Run 61 Temp. 9.93° Cell C Conc. 0.00303 m. Date 7/12/56

t (min.) R t(Eoo-B)

.20 1820 2075 420 .35 1920 1975 690 .52 2020 1875 980 .70 2120 1775 1250 .92 2220 1675 1550 1.15 2320 1575 1810 1.4o 2420 1475 2070 o o 3895 I = -4620 kg _ t 3.895...... - . = 278 -4620 X .00303

Bun 62 Temp. 9.93° Cell D Conc. 0.0018? ra. Date 7/12/56 t(min.) R Boo-B t(Roo-B)

.24 2800 3270 790 .38 2900 3170 1210 .53 3000 3070 1630 .88 3200 2870 2530 1 .0 7 3300 2770 2960 1 .4 7 3500 2570 3780 1.70 3600 2470 4200 1.95 3700 2370 4620 00 6070 -6970 I = -11270 ^2 - -11270 X .00187 = 289 193

Table 87 Endo-2~Nltrobioyclo[2*2-1]Heptane

Bun 66 Temp. 9.93° Cell D Conc. 0.0Ô216 m. Date 7/1V 5 6

t(min.) ^oo”^ t (Bq o -B)

.22 2500 2930 650 .37 2600 2830 1050 .69 2800 2630 1810 .85 2900 2530 2150 1.23 3100 2330 2860 1.46 3200 2230 3260 1.70 3300 2130 3620 2 .2 6 3500 1930 4360 2.57 3600 1830 4700 2.94 3700 1730 5080 CO 5430 -6430 = 294 I = -8550 2 - -8550 X .00216

Run 60 Temp. 9.93° Cell P Conc. 0.00 2 2 6 m. Date 7/12/56 t(mln.) R B o o - B t (Rcx)-R)

.22 3120 3670 810 .32 3220 3570 ll4o .55 3420 3370 1850 .68 3520 3270 2230 .95 3720 3070 2920 1.10 3820 2970 3270 1.28 3920 2870 3680 1.45 4020 2770 4020 1.83 4220 2570 4710 2.28 4420 2370 5410 00 6790

I = .10260 k2 = ^-.oo-22i: = 194

Table 88 Éndo~2~Nltroblcyolo[2-2•1]Heptane

Run 65 Temp. 9.93° Cell C Cone. 0.00386 m. Date 7/14/56 t(mln.) R t (Roo“*S )

.32 I60O 1645 530 .48 1700 1545 740 .6 8 1800 1445 980 .88 1900 1345 1190 1.12 2000 1245 1400 1.43 2100 . 1145 1640 1.7 6 2200 1045 1840 2.18 2300 945 2060 2 .6 7 2400 845 2260 0 0 3245 ^ -3245 = 284 I = -2970 ^2 - -2970 X .00386

Run 64 Temp. 9.93° Cell G Cone. 0.00324 m. Date 7/14/56 t(min.) R Roo“S t(Roo-R)

.1 9 2500 2950 560 .28 2600 2850 800 .38 2700 2750 1050 .4 9 2800 2650 1300 .62 2900 2550 1580 .87 3100 2350 2050 1.02 3200 2250 2300 1 .1 9 3300 2150 2560 1.37 3400 2050 2810 00 5450

I -- 5690 k2 - -5690 X .003 24 “ 195

Table 89 Endo-Z-Nltroblcvolo T2*2-llHeptane

Run 196 Temp. 28.00° Cell A Conc. 0.000827 m. Date 1/12/57 t(rain.) R t )

.32 4600 3400 1090 .40 4700 3300 1320 .48 4800 3200 1530 .58 4900 3100 1800 .68 5000 3000 2040 .78 5100 2900 2260 .88 5200 2800 2460 1.00 5300 2700 2700 1 .1 3 5400 2600 2940 1.27 5500 2500 3180 00 8000

I = -9800 k2 - _9800 X .000827

Run 197 Temp. 2 8.00° Cell B Gone. 0.00165 m. Date 1/12/57 t(mln.) R Rqq—R t(R^Q—R)

.20 2400 1840 370 .28 2500 1740 490 .36 2600 1640 590 .47 2700 1540 720 .58 2800 l44o 84o .70 2900 1340 940 co 424o -4240______I = -2435 kg “ -2350 X .OOÏ65 196

Table 90 Endo-2-Nltrobioyolo[2•2•l]Heptane

Run 198 Temp. 28.00° Cell C Conc. 0.00165 m. Date 1/12/57 t(mln.) R Boo-B t(Rq o -R)

.22 2400 1810 400 .31 2500 1710 530 .39 2600 1610 630 .50 2700 1510 750 .62 2800 1410 870 .75 2900 1310 980 CO 4210 -4210 I = -2375 kg = -2375 X .00165 1074

Run 199 Temp. 28.00° Cell D Conc. 0,00 0827 m. Date 1/12/57 t(mln.) R Boo-B t(RqO ”®)

.22 4500 3540 780 .29 4600 3440 1000 .37 4700 3340 1240 .^5 4800 3240 l 46o .55 4900 3140 1730 .64 5000 3o4o 1950 .85 5200 2840 2410 .95 5300 2740 2600 1.07 5400 264o 2820 CO 804o

I = -9900 kg - _92oo X .000827 “ 197

Table 91 Bnao-2-Nltrobioyolo[2-2-Il Heptane

Run 200 Temp. 28.00° Cell A Gone. 0.00082? m. Date 1/14/57

t(rain.) R %00-B t(Roo-R)

.25 4500 3410 850 .33 4600 33I0 1090 .41 4700 3210 1310 .50 4800 3110 1560 .60 4900 3010 1800 .70 5000 2910 2040 .80 5100 2810 2250 .92 5200 2710 2490 00 7910 , -7910 I = -9660 ^2 - -9660 X .000827 = 990

Run 201 Temp, 28.00° Cell B Conc. 0.000827 m. Date 1/14/57 t(mln.) R Roo“R t(Rq o -R)

.18 4500 3630 650 .25 4600 3530 880 .32 4700 3430 1100 .40 4800 3330 1330 .49 4900 3230 1580 .68 5100 3030 2060 .78 5200 2930 2280 .88 5300 2830 2490 1.00 5400 2730 2730 1.12 5500 2630 2950 eo 8130

I 9850 kg - .^9850 x .000827 198

Table 92 Exo-2-Nltroblcvolof2•2-1]Heptane

Run 123 Temp. 0° Cell A Gone. 0.00426 m. Date 11/ 13/5 8 Rq 1690 ohms R^^ 4030 ohms t(min.) R R2-R1 Roo-^1 800-^2 At "k"

1850 5 .3 3 2.04 7.37 1900 50 2180 2130 6 .9 1 9 .5 2 1950 50 2130 2080 2 .1 5 6 .8 8 11.7 8 2000 50 2080 2030 2.26 6.86 14.20 2050 50 2030 1980 2.42 6 .7 4 = 6.85

Run 124 Temp, o'' Cell B Conc. 0.00596 m. Date 11/ 1 3 /56 R( 1280 ohms R^^ 3075 ohms t(min.) R ^2“^1 ®oo"^l ®oo~®2 At "k"

5.53 1450 7.62 50 1625 1575 2 .0 9 6 .7 6 1500 6.84 9.82 1550 50 1575 1525 2 .2 0 12.15 I600 50 1525 1475 2 .3 3 6.90 14.62 1650 50 1475 1425 2 .4 7 6.97 6 .9 6 17.2 7 1700 50 1425 1375 2 .6 5 = 6 .8 9 199,

Table 93 Exo-2-Nltroblc vclo[2 *2•Il Heptane

Run 125 Temp. 0° Cell C Conc. 0.00852 m. Date 11/ 13/56 Hq 870 ohms Rqo 2165 ohms t(mln.) E *'k*'

3.00 960 3 .4 3 1020 60 1205 1145 2 .4 3 6 .7 7 8.20 1080 60 1145 1085 2 .7 7 6.62 11.27 1140 60 1085 1025 3 .0 7 6.66 14.70 1200 60 1025 965 3 .4 3 6.70 = 6 .6 9

Run 126 Temp. 0° Cell D Conc. 0.00852 ra. Date 11/ 13/56 Bo 870 ohms Roo 2175 ohms «•k« t(mln.) R R2-R1 %00-Bl Boo-B'2

3.22 970 60 1205 1145 2 .4 5 6.80 5 .6 7 1030 60 1145 1085 2 .7 6 6.70 8 .4 3 1090 .60 1085 1025 3 .1 2 6.64 11.55 1150 60 1025 965 3 .4 3 6 .7 8 14.98 1210 60 965 905 3.85 6.84 1270 18.83 60 905 845 4.39 6.85 2 3 .2 2 1330

k2 = 6 .7 7 200

Table 94 Exo-2-.Nltrobloyolo F2 «2* 11 Heptane

Bun 136 Temp. 9.93° Cell A Conc. 0.00424 ra. Date 11/ 19/56 Rq 1230 ohms R(X) 2830 ohms t(min.) R R2-R1 "k"

2 .5 5 1350 50 1480 1430 1.3 2 1 5 .5 3.87 1400 1430 1380 1.41 1 5 .6 5.28 50 1450 1380 15 .6 6.80 1500 50 1330 1 .5 2 50 1330 1230 1.63 15.6 8 .4 3 1550 50 1280 1230 1 .7 4 1 5 .8 10.17 1600 k2 = 1 5 .6

Run 137 Temi ,93° Cell B Conc. 0. 00593 m. Date 11/ 19/56 Rr) 915 ohms Boo 2135 ohms t(min.) R R2-R1 R q o ”^ 1 Roo~B 2 "k"

1050 2.97 50 1.38 4 .3 5 1100 1085 1035 15.5 5.85 1150 50 1035 985 1.50 15 .7 7 .5 0 1200 50 985 935 1.65 15 .8 9.33 1250 50 935 885 1.83 1 5 .8 11.38 1300 50 885 835 2 .0 5 1 5 .8 2 .2 9 16.0 13.67 1350 50 835 785 ^2 = 15 .8 201

Table 95 Ë2S2.-2-N1 trobicyclo [2-2*1] Heptane

Run 138 Temp. 9.93 Cell C Conc. 0.00424 m. Datell/19/56 ohms Roc 2865 ohms t(min.) R Roo""^! Roo~^2 A t •'k*'

4.35 1425 50 l44 o 1390 1.43 15.6 5.78 1475 50 1390 1340 1.52 15.8 7.30 1525 50 1340 1290 1.62 15.9 8.92 1575 50 1290 1240 1.80 10.72 1625 15.5 12.62 50 1240 1190 31.90 15.9 1675 50 1190 ll4 o 2.05 16.1 14.67 1725 kg = 15 .8

Run 139 Temp. 9-.93° Cell D Conc. 0.00848 m. Date 11/ 19/56 Hq 644 ohms R(X) 1545 ohms. t(mln.) R Rg“R^ Roo—R ®oo"®2 -4it "k"

1.92 ?4 o 4 o 805 765 1.06 15.4 2.98 780 4 o 765 725 1.19 15.4 4 .1 7 820 4 o 5.48 860 725 685 1.31 15.7 4 o 685 645 1.45 15.8 6 .9 3 900 4 o 645 605 1.67 15.6 8.60 940 4 o 605 1.88 15.8 10.48 980 565 ^2 = 15.6 20g

Table 96 Exo-2-Nltroblovolo[2-2•il Heptane

Run 163 Temp, : t,00° Cell D Conc, 0.00253 m. Date 12/7/56 E. 1345 ohms Eoo 2750 ohms t(min.) R R2-R1 Boo-Bl Roo“®2 A t "k"

.60 1425 1,02 1.62 100 1325 1225 68,6 1525 100 1225 1125 1.25 65.9 2,87 1625 100 1125 1025 1,47 67.0 4,34 1725 100 1025 1,74 68,8 6,08 1825 925 %2 = 67.6

Run 168'.'. Temp, 28,00° Cell C Conc, 0,00422 m. Date 12/ 13/56 Rq 8I3 ohms Rqq 1755 ohms t(mln.) R ®2“®1 Boo-^i B00-B2 At "k"

.28 860 , 64 900 4 o 895 855 .36 70.1 1,07 940 4 o 855 815 .43 64,5 1.52 980 4 o 815 775 .45 68,0 2,02 1020 4 o 775 735 .50 67.8 2.58 1060 40 735 695 .56 67.6 3.20 1100 40 695 655 ,62 68.4 3.88 ll4 o 4 o 655 615 ,68 70.4 4.67 1180 4 o 615 575 .79 69.1 k2 = 68,2 203

Table 97 Exo-2-NltroblcvGlo î 2*2-l]Heptane

Run 164 Temp. 28.00° Cell E Conc. 0.00422 ra. Date 12/7/56 Rq 1122 ohms R q q 2365 ohms t(raln. ) R Rg—R^ Roo”®l '^oo“®2 ^t

.58 1225 100 ll4 o lo4 o .79 66.4 1 .3 7 1325 1425 100 lo4 o 940 .98 64.9 2 .3 5 100 B o 67.2 3 .5 2 1525 940 4 1.17

kg = 66.2

Run 169 Terap. 28.00° Cell D Coho. 0.00253 ra. Date 12/ 13/56 Rq 1350 ohras Rqq 2760 ohras t(raln.) R Rg—R^ R^Q—R^ Rq^—Rg t "k"

1425 .55 50 .48 69.2 1 .0 3 1475 1335 1285 50 1285 1235 .54 66.5 1.57 1525 .60 2 .1 7 1575 50 1235 1185 64.9 2.80 1625 50 1185 1135 .63 67.2 66.1 3 .5 0 1675 50 1135 1085 .70 4.26 50 1085 1035 .76 66.7 1725 .82 68.1 5.08 1775 50 1035 985 5.98 1825 50 985 935 .90 68.7 = 67.2 20À

Table 98 Endo~ 6-Nltreblevclo\2 -2 *l] Heptene-2

Run 4o Temp. 0° Cell A Conc. 0 .0 0 2 8 6 m. Date 2/ 1 8 /5 6 t(mln.) R B o o - B b(Roo“^)

.25 2700 3200 800 .4 0 2800 3100 1240 .5 5 2900 3000 1650 .8 7 3100 2800 2440 1.03 3200 2700 2780 1.23 3300 2600 3200 1.65 3500 2400 3960 1.90 3600 2300 4370 2.43 3800 2100 5110 2.74 3900 2000 5480 00 5900

I = -9 5 0 0 k2 = .9500 X .0 0 2 8 6

Run 41 Temp. 0° Cell A Conc. 0.00510 m. Date 3 /1 5 /5 6 t(min.) R Boo-B t (R(X)“B)

.18 1500 1900 342 .33 1600 1800 595 .50 1700 1700 850 .88 1900 1500 1320 1.12 2000 1400 1570 1.40 2100 1300 1820 1.7 0 2200 1200 204o 00 3400

: = -3295 VC2 = X .00510 = ^°3 20,3

Table 99

Endo-5 -Nltroblcyolo[2 »2 «l]Heptene-2

Run 38 Temp, 0° Cell A Conc, 0,00357 m. Date 2/ 16/56

t(mln,) R Boo-B t (Roo—îi )

.17 2100 2700 450 .30 2200 2600 780 2300 2500 1100 .77 2500 2300 1770 • 95 2600 2200 2090 1.15 2700 2100 2420 1.62 2900 1900 3080 1.68 3000 1800 3380 2 il8 3100 1700 3710 00 4800 -4800 I = -6320 k2 : 212 = -6320 X ,00357

Run 3^ Temp, 0° Cell A Conc, 0,00508 m. Date 2/ 11/56 t(min,) R Boo“B t(R^-R)

.17 1500 1930 330 .31 I6OO 1830 570 .^7 1700 1730 810 .63 1800 1630 1030 .85 1900 1530 1300 1,07 2000 1430 1530 1.33 2100 1330 1770 oo 3430

I = -3235 kg = :|t§^":oogô8 = 20é,-

Table 100 Endo-5-Nltreblevclo[2•2•1]Heptene-2

Run 37 Temp. 0° Cell A Conc. 0.00355 m. Date 2/ 15 /5 & t(mln.) R Boo-B t (R(X)—E )

.31 2200 2650 820 .45 2300 2550 1150 .62 2400 2450 1520 .96 2600 2250 2160 1.17 2700 2150 2520 1.38 2800 2050 2830 1.62 2900 1950 3160 2.18 3100 1750 3820 2.52 3200 1650 4160 2.87 3300 1550 4450 3,i'30 3400 1450 4780 00 4850 I = -644 o k2 ------= 211 -6440 X .00355

Run 35 Temp. 0° Cell A Conc. O.OO508 m. Date 2/I3/56 t(min.) R Roo"B t(Rq o “^)

.19 1600 1830 350 .33 1700 1730 570 .49 1800 1630 800 . 66 1900 1530 1010 .85 2000 1430 1220 CO 3430 -3430 = 210 I = -3215 %2 = :3215 X .00508 207 Table 101 Endo-5-Mltrobiovolor2-2- IlHeptene-2

R u n 153 Temp. 9 .93° Cell A Conc. 0 .00042? m. D a t e 12/ 4/56 t(min.) R Rqq—R t(RoQ—R)

.32 12100 9460 3030 .53 12300 9260 4900 .65 12400 9160 5950 1.01 12700 6860 8940 1.25 12900 8660 10800 2.25 13600 7960 17900 2.57 13800 7760 19900 3.22 14200 7360 23700 3.55 l44 oo 7160 25400 00 21560 . -21560 I = -115600 " -115600 X .000427 = 437

R u n 150 Terap. 9.93° Cell A Conc. 0.00128 ra. D a t e 11/30/56 t ( m i n . ) R Roo-S t (Roo-R)

.20 4200 4275 850 .30 4300 4175 1250 .40 4400 4075 1630 .50 4500 3975 1985 .73 4700 3775 2760 .85 4800 3675 3120 .97 4900 3575 3470 1.11 5000 3475 3860 ce> 8475 I = -14630 _ -8475 = 452 -14630 X .00128 20$

Table 102

Endo-6-Nltroblc.vclo C2 *2 • 1] Heptane -2

Hun 151 Terap. 9.93° Cell D Conc. 0.00212 ra. Date 11/30/56

t(mln,) R Boo-B t ( R o o “B)

.23 2700 2é40 610 .35 2800 2540 890 .45 2900 2440 1100 .70 3100 2240 1570 .82 3200 2l4 o 1760 .98 3300 2040 2000 1.31 3500 1840 2410 1.51 3600 1740 2630 1.73 3700 1640 2840 co 5340

I = -5280 k2 -5340 . . = 477 -5280 X .00212

Run 152 Terap. 9.930 Cell G Conc. 0.00297 ra. Date 11/30/56 t(min.) R t(Roo-B)

.13 2800 2915 380 .21 2900 2815 590 .35 3100 2615 920 .43 3200 2515 1080 .52 3300 2415 1260 .72 3500 2215 1600 .83 3600 2115 1760 c o 5715

I = -4250 kg - = 453 " -^250 X .00297 20?

Table 103 Bado-'^-Nltroblcyolo [2 ' 2 -1] Heptene-2

Run 202 Terap. 2 8.00° Cell C Conc. 0 .00082? ra. Date 1/ 1V 5 ? t(mln.) R R^-R t(Roo-R)

.18 4300 2950 530 .23 4600 2850 660 .35 4800 2650 930 .41 4900 2550 1050 .55 5100 2350 1300 .63 5200 2250 1420 .72 5300 2150 1550 00 7 4 5 0 -?4 so______I = -5100 k2 = _5100 X .00082? = 1765

Run 183 Temp. 2 8.00° Cell B Conc.0 ;Q00422 ra. Date 12/ 19/56 t(raln.) R Rqq—R t(RoQ—R)

.21 9000 5630 1180 .39 9400 5230 2040 .52 9600 5030 2610 .63 9800 4830 304 o .90 10200 4430 3990 1.05 10400 4230 4440 00 14630

I = -20000 k2 = «20000 x ^"00(Ï422~ =1732 2/10

Table 104 Endo-5-Nltroblovolo[2«2•11 Heptene-2

Run 180 Temp. 28.00° Cell D Conc. 0.000422 ra. Date 12/ 18/56 t(raln.) R Rqq—R t (R^Q—R )

.27 9000 5200 1400 .37 9200 5000 1850 .50 9400 4800 2400 .62 9600 4600 2870 .89 10000 4200 3740 1.05 10200 4000 4200 1.22 10400 3800 4640 co 14200 =.l42Qg------_ -19320 k2 - «19320 X .000422

Run 176 Terap. 2 8.00° C'èll G Conc. O.OOO8I5 ra. Date 12/ 14/56 t(raln.) R Rqq—R tCR^^-R)

.21 6600 4550 960 .28 6800 4350 1220 .43 7200 3950 1700 .53 7400 3750 1990 .75 7800 3350 2510 .87 8000 3150 2740 00 11150

I = -7480 k2 = .000815 = 183° 2 U ‘

Table 105 •5-Nltrobioyclo[2•2 ■1]Heptene-2

Run 6? Temp. 0° Cell A Conc. 0.00350 m. Date 7/ 16/56

t(mln. ) Boo-B t(Roo“® )

2.90 2100 2600 7540 4 .2 7 2140 2560 10950 5.67 2180 2520 14300 6.38 2200 2500 16000 7.10 2220 2480 17600 9.42 2280 2420 22800 11.00 2320 2380 26000 12.65 2360 2340 29600 14.33 2400 2300 33000 16.07 2400 2260 36300 00 4700 -4700 I = -171000 k2 = -171000 X .00350

Run 68 Temp. 0° Cell C Conc. 0.00350 m. Date 7/17/56 t(min. ) R %00-B t(Rq o —R)

.98 2050 2630 2580 2.97 2110 2570 7640 5.07 2170 2510 12750 7.97 2250 2430 19400 12.03 2350 2330 28000 16.43 2450 2230 36700 21.17 2550 2130 45000 26.35 2650 2030 53500 (50 4680 -4680 I = -169800 = 7.88 k2 - •-169800 X .00350 21?

Table 106

Exo-.5-NltroblGvclor2 *2 -1] Heptene-2

Run 71 Terap, 0° Cell E Conc. 0.00525 ra. Date 7/17/56 t(raln.) R t (Roo“R)

.68 1920 2480 1690 1.38 1950 2450 3380 2.08 1980 2420 5030 3.88 2050 2350 9120 5.22 2100 2300 12000 6.62 2150 2250 14900 9.60 2250 2150 20600 11.18 2300 2100 23500 12.85 2350 2050 26300 14.58 2400 2000 29200 CO 4400 -4400 I = -108000 k2 = = 7.76 -10800 X .00525

Run 72 Terap. 0° Cell G Conc. O.OO7OO ra. Date 7/I7/56 t(rain.) R Ro^-R tCR^^-R)

.77 1560 2000 1540 1.62 1600 i960 3180 3.95 1700 1860 7350 5.25 1750 1810 9500 6.62 1800 1760 11650 9.58 1900 1660 15900 12.87 2000 1560 20100 16.57 2100 1460 24200 18.60 2150 ' 1410 26200 00 3560 =17.96 I = -64000 k2 = -64000 X .00700 213

Table 107 Ë2o-5-Nltrobicyolo[2*2*1]Heptene-2

R u n 154 Terap. 9 .9 3 ° Cell B Conc, 0.00424 ra. Date 12/ 4/56 t(rain,) R B o o - B t (Roo—R)

.70 1330 l 4oo 980 1 .0 7 1350 1380 1480 1.68 1380 1350 2270 3 .0 3 1440 1290 3910 3 .7 8 1470 1260 4770 4. 5 7 1500 1230 5620 6 .2 5 1560 1170 7320 7 .1 5 1590 1140 8I60 8.08 1620 1110 8970 co 2730 -2730 I = -36600 = 17.6 -36600 X .00424

H u n 155 Terap. 9 .93° Cell C Conc. 0.00424 ra. Da t e 12/ 4/56 t ( m i n . ) R ® o o “ ® t(Roo-H)

.42 1290 1370 580 .93 1320 1340 1270 1.58 1350 1310 2070 2.98 1410 1250 3730 3 .7 7 l 44o 1220 4600 4 .5 0 1470 1190 5360 6 .2 3 1530 1130 7050 7 .1 5 1560 1100 7870 8.1 3 1590 1070 8710 10.22 1650 1010 10320 11.32 1680 980 11100 12.50 1710 950 11900 00 2660 -2660 = 18.3 I = -34300 k2 “ -34300 X .00424 21^

Table 108 Exo-4-Nltroblovolor2'2'l]Heptene-2

Run 156 Temp, 9.93° Cell D Gone. 0.00596 m. Date 12/4/56 t(mln,) R ^ 0 0 " ^ t(Roo-R)

.77 980 1010 780 1.17 1000 990 1160 1.62 1020 970 1570 2 .5 7 1060 930 2390 3.07 1080 910 2790 3.60 1100 890 3200 4 .7 3 .1140 850 4020 5.32 1160 830 4410 5 .9 3 1180 810 4800 7.27 1220 770 5600 7 .98 1240 750 5990 8.73 1260 730 6380 00 1990 --1990 I = -18800 %2 = 17.8 -1880 X .00596

.50 960 io4o 520 1.10 1000 1000 1100 1.77 1040 960 1700 2.48 1080 920 2280 3.27 1120 880 2880 4.10 1160 840 3420 5.03 1200 800 4020 6.05 1240 760 4590 7.17 1280 720 5160 00 2000

I = -«'«>0 kg = ^ -.obsW = 17.6 215

Table 109

g2Ç2.-5 -Nl troblcyclo [2 *2 *1] Heptene-2

Bun l6 o Terap, 2 8.00° Cell A Conc. 0.00253 ra. Date 12/ 7/56 t(raln.) R Boo-B t(BoQ—B )

.50 1430 1135 570 .67 1450 1115 750 .87 1470 1095 950 1.27 1510 1055 1340 1.47 1530 1035 1520 1:68 1550 1015 1710 2.I5 1590 975 2100 2 .4o 1610 955 2290 2.91 1650 915 2660 3 .1 8 1670 895 2850 3 .6 2 1700 865 3130 co 2565

I = -13040 42 = ^ .00253 = 77.8

Bun 162 Terap. 28.00° Cell C Conc. 0.00422 ra. Date 12/ 7/56 t(raln.) B B q o -B t (Boo"*K)

.40 900 740 300 .58 920 720 420 .77 940 700 540 1.20 980 660 790 1.42 1000 64 o 910 1 .90 lo4o 600 l l 4o 2.18 1060 580 1260 2 .7 7 1100 540 1500 00 l 64 o

I 5120 k2 -= _5120 X .00422 = 75.8 216

Table 110 Exo-4-Nltroblovolo[2•2•1]Heptene-2

Hun l6l Temp. 2 8.00° Cell B Conc. 0.00424 m. Date 12/ 7/56 t(mln.) R Boo“R t(Roo“B )

.62 940 735 460 .81 960 715 580 1.00 980 695 700 1.22 1000 675 820 1.43 1020 655 940 1.92 1060 615 1180 2.18 1080 595 1300 2.47 1100 575 1420 2.75 1120 555 1530 co 1675

: ' -5 “ 0 kg . îlfg— = 76.7

Hun 167 Temp. 28.00° Cell B Conc. 0.00424 m. Date 12/13/56 t(min.) R Roo“B 4 (Roo-R)

.30 900 770 230 .46 920 750 350 .63 940 730 460 .83 960 710 590 1.45 1020 650 940 1.68 10 40 630 1060 1.93 1060 610 1180 2.47 1100 570 1410 2.77 1120 550 1520 co 1670

I - -5040 k2 _ -1670 = 7 8 .4 -5040 X .00424 217

Table 111 Endo-^~Nltroblcvclor2 «2•2lOctene~2

Run 211 Temp. 0° Cell E Conc. 0.00257 m. Date %/18/57 t(min.) R t(Boo-R)

A5 4000 5310 2400 1.22 4200 511.0 6230 2.03 4400 4910 9950 2 .8 8 4600 4710 13550 3.83 4800 4510 17250 4 .8 8 5000 4310 21000 6.00 5200 4110 24600 7.23 5400 3910 28300 CP 9310 I = -71700 i- —9310 = 50.6 2 -71700 X .00257

Run 212 Terap. 0° Cell F Conc. 0.00514 ra. Date 2/ 18/56 t(rain.) R ®oo“® t(Roo-E)

.23 2100 2950 680 .58 2200 2850 1650 .97 2300 2750 2670 1.37 2400 2650 3630 1.82 2500 2550 4640 2.30 2600 2450 5640 2.80 2700 2350 6580 3.37 2800 2250 7590 3 .9 7 2900 2150 8540 4.63 3000 2050 9500 5.35 3100 1950 10430 co 5050

I 19700 lC2 = -.19700 X .0051^ - ^9.9 218

Table 112 Endo~6-Nitrobiovolof 2•2•2]Octene-2

Run 213 Temp, 0° Cell A Conc. 0.00257 m. Date 2/ 20/57 t(mln.) R Boo-B t(Boo-B)

.33 3000 3870 1280 .83 3100 3770 3130 1.33 3200 3670 4880 2.43 3400 3470 8430 3.03 3500 3370 10200 3 .6 ? 3600 3270 12000 5.03 3800 3070 15400 5 .7 8 3900 2970 17200 oo 6870

I = -52500 k2 = -.0 0 257 “

Run 214 Temp, 0° Cell B Conc. 0.00514 m. Date 2/ 20/56 t(mln.) R Rqq—R t(RoQ—R)

.27 1600 2140 580 .50 1650 2090 1050 .75 1700 2040 1530 1.28 1800 1940 2480 1.53 1850 1890 2890 1.83 1900 1840 3370 2.47 2000 1740 4300 3 .1 8 2100 l64 o 5220 3.55 2150 1590 5650 co 3740

I = -14210 = 51.2 % " -14210 X .00514 219

Table II3 Endo~^~NltrobicyGlof2-2*2J Octene-2

Eun 238 Temp, 9.930 Cell D Conc. 0.00488 m. Date 3/4/57 t(min.) E Roo-B t(Eoo-E)

.38 1350 1450 550 .55 1400 1400 770 .73 1450 1350 990 .92 1500 1300 1200 1.13 1550 1850 1410 1.35 1600 1200 1620 1.60 1650 1150 184o 00 2800

I - -5190 k2 = _|i90 x~.004-88 ~

Eun 239 Temp, 9 .93° Cell A Corne. O.OO256 m. Date 3/5/57 t(mln.) S Eqo—E tCE^Q—E)

.28 2300 2700 700 .60 2400 2600 1560 .95 2500 2500 2380 1.32 2600 2400 3170 1.72 2700 2300 3960 2.16 2800 2200 4760 2.63 2900 2100 5520 3.17 3000 2000 6340 00 5000

I = -17600 kg = Il^600 X .00256 ^ 220

Table ll4

Eûâ2.-5 -Nl troblcyclo [2 • 2 • 2 ] Octene-2

Hun 24o Temp. 9 .93° Cell B Gone. 0.00511 m. Date 3/5/57

H Roo-H t (Roo“E )

1300 1450 460 1350 1400 670 .67 1400 1350 900 1.05 1500 1250 1310 1.49 1600 1150 1710 1 .74 1650 1100 1920 2 .0 2 1700 1050 2120 00 1750 -2760 = 109 I = -4930 k2 = -4930 X. .00511

Hun 24l Temp. 9.930 Cell C Conc. 0 ,Q02SS ra. Date 3/5/57 t(min,) H Eoo”® t(Boo-E)

.24 2300 2720 650 .57 2400 2620 1490 .90 2500 2520 2270 1.27 2600 2420 3070 1.67 2700 2320 3880 2 .0 4 2800 2220 4530 2.50 2900 2120 5300 3.00 3000 2020 6060 00 5020 -6020 I = -16800 k2 = = ll4 ■ -16800 X ,00256 221

Table 115 Endo-9-Nitroblcyolo[2-2-2]Octene-2

Run 258 Temp, 28.000 Cell B Conc. 0.00231 m. Date 3 .9/57 t(min.) R B o o - B t (Roo“ ^)

.22 1650 1585 350 .30 1700 1535 460 .48 1800 1435 690 .58 1850 1385 800 .69 1900 1335 920 .93 2000 1235 1150 1.07 2050 1185 1270 1.37 2150 1085 1490 1.53 2200 1035 1590 00 3235 = 402 I = -3480 k2 = Ÿ 3480 X .00231

Run 259 Temp. 28.00° Cell C Gone. 0.00154 m. Date 3/ 9/57 t(mln.) R Rqq—R t(Roo—R)

.18 2300 2300 410 .37 2400 2200 810 .56 2500 2100 1180 .76 2600 2000 1520 .97 2700 1900 1850 1.23 2800 1800 2210 1.50 2900 1700 2550 00 4600 222

Table 116

Bnd2.-5-Nltrobloyclo[2 ‘2 •2]ootene-2

Run 260 Temp. 2 8.00° Cell D Conc. 0.00154 m. Date 3/ 9/57 t(min.) R Boo-B t(Rqo”®)

.21 2300 2280 480 .38 2400 2180 • 830 .57 2500 2080 1190 .77 2600 1980 1530 1.00 2700 1880 1880 1.25 2800 1780 2220 1.52 2900 1680 2560 00 4580 I = -7510 k = .4680______= 396 2 .7510 X .00154

Run 261 Temp. 28.00° Cell E Conc. 0.000770 m. Date 3/ 9/57 t(mln«) R Rqq—R t(RoQ—E)

.35 6200 5840 2o4o .47 6300 5740 2700 .60 6400 5640 3380 .73 6500 5540 4o4o .88 6600 5440 4780 1.15 6800 5240 6030 1.31 6900 5140 6740 1.47 7000 50 40 7400 1 .6 4 7100 4940 8100 1.8 1 7200 4840 8760 1.98 7300 4740 9390 2.17 7400 4640 10070 2.56 7600 4440 11370 CO 12040 __ -12040 I = -39420 = 397 - 39420 X .000770 223

Table II7

Exo-5-Nltroblovolo[2 *2 *2 ]Octene-2

Run 217 Temp, 0° Cell E Conc. 0.00257 m. Date 2/20/57

t(mln,) R t(Roo-E)

,4o 4200 5220 2080 • 77 4300 5120 3940 1.18 4400 5020 5920 2.02 4600 4820 9730 2.42 4700 4720 11400 2 .8 9 4800 4620 13350 3 .8 7 5000 4420 17100 4 .3 8 5100 4320 I8900 5.47 5300 4120 22600 6.05 5400 4020 24300 00 9420

I -- 75600 k2 - «75600 X .00257 ~

Run 218 Temp. 0° Cell P Conc. 0.00504 m. Date 2/20/57 t(min.) R Eoo"E t(Roo—R)

.35 2200 2860 1000 .74 2300 2760 2040 1.16 2400 2660 3090 1.57 2500 2560 4020 2.07 2600 2460 5100 2 .5 8 2700 2360 6090 2.85 2750 2310 6590 3.43 2850 2210 7590 3.75 2900 2160 8100 4 .4o 3000 2060 9070 00 5060

I - -21120 k2 = «21120 x .00514" 224-

Table 118 Exo~6-Nltrobicvclor2 »2 •2.l0Qtene-2

Run 221 Temp. 0° Cell C Cone. 0.00257 ra. Date 2/26/57

t(mln.) E Roo-B t(Eoo-E)

.32 3000 3870 124-0 .86 3100 3770 324-0 1 .4-3 3200 3670 5250 2 .6 2 34-00 34-70 9080 3 .2 8 3500 3370 11050 3 .9 8 3600 3270 13000 5.51 3800 3070 16900 6.35 3900 2970 18850 8.18 4-100 2770 22650 9.19 4-200 2670 24-550 CO 6870

I = -57080 k2 = «57080 X .00257 " 4 6 .9

Bun 222 Temp, 0° Cell D Conc. 0 .00514 - m. Date 2/ 26/57 t(raln. ) R t(Rq o —E)

.4-2 1600 2060 870 .99 1700 i960 1940 1.61 1800 I860 3000 2.28 1900 1760 4020 3.00 2000 1660 4980 3 .8 5 2100 1560 6010 4 .8 1 2200 l46 o 7020 5.88 2300 1360 8000 CO 3660 . -3660 = 46.7 I - -1524-0 ^2 = -1524-0 X .00514 225

Table 119 Exo-5-Nitroblovclo[2'2-2l Octene-2

Run 24-7 Temp. 9 .93° Cell D Cone. 0.00256 m'.* Date 3/7/57 t(min.) R R(X)-R t(Rg^-R)

.19 2300 2740 520 .52 2400 2640 1370 .87 2500 2540 2210 1,22 2600 2440 2980 1.63 2700 2340 3820 2.06 2800 2240 4620 2.52 2900 2140 5400 3.03 3000 2040 6180 CO 5 o4o

: = *'2 " X .00256 = ^“7 .9

■«•Concentration of the nitro compound was 0.00266 m.

Run 248 Temp. 9 .93° Cell B Conc. 0.00256 m.* Date 3/ 7/57 t(min.) R %oo-: t(Roo-B)

.37 24oo 2725 1010 .72 2500 2625 1890 1.08 2600 2525 2730 1 .4 4 2700 2425 3490 1.87 2800 2325 4350 2.32 2900 2225 5160 2.82 3000 2125 6000 3.35 3100 2025 6790 3 .9 3 3200 1925 7570

00 5125 . I = -18710 = 107'.0

* Concentration of the nitro compound was O.OO26I m. 226

Table 120 Exo-5-Nltroblcvclor2-2'2lOotene-2

Run 249 Temp. 9 .93° Cell C Conc. O.OO256 m'. Date 3/ 7/57 t(min.) R t(Roo-B)

2300 2650 720 2400 2550 1580 2500 2450 2430 i f / ? 2600 2350 3220 1.82 2700 2250 4100 2 .2 8 2800 2150 4910 2.81 2900 2050 5760 3.37 3000 1950 6570 00 4950 -4990 103.8 I = -18620 ko — -18620 X .00256

Run 250 Temp. 9 .93° Cell E Conc. 0.00256 m.* Date 3/ 7/57 t(min. ) R Boo-B t(Ro o “B)

.32 3200 3610 1160 .58 3300 3510 2040 .85 3400 3410 2900 1.42 3600 3210 4560 1.75 3700 3110 5440 2 .0 8 3800 3010 6260 2.83 4000 2810 7960 3.25 4100 2710 8810 3.68 4200 2610 9610 4 .1 6 4300 2510 10440 4.67 4400 2410 11270 ao 6810

= 102.8 I = -25950 ko — -25950 X .00256

* Concentration of the nitro compound was 0.0025I m. 227

Table 121

Exo-S-Nitroblovolo[2 *2 •2 ]0ctene-2

Run 251 Temp. 9.93° Cell P Conc. 0.00256 m.* Date 3/7/57 t(mln.) R B&o-B

.23 3200 3600 830 .48 3300 3500 1680 .76 3400 3400 2580 .98 3500 3300 3240 1.31 3600 3200 4190 1.63 3700 3100 5060 1.97 3800 3000 5910 S . 33 3900 2900 6760 2.72 4000 2800 7620 3.12 4100 2700 8420 3 .5 5 4200 2600 9240 CO 6800 . - 6 8 0 0 ...... I = -26270 =■ -26270 X .00256 = 101.3

* Concentration of the nitro compound was 0.00246 m. 228

Table 122 Exo-5-Nltrobicvolo T2*2 *2]Octene-2

Run 264 Temp, 28.00° Cell C ^ono. 0.00154 m. Date 3/ 11/57 t(mln.) R ®CX5"® t(R^-R)

.18 2300 2240 4oo .37 2400 2140 790 -.57 2500 2040 II60 .77 2600 1940 1490 1.01 2700 1840 1830 1.27 2800 1740 2210 1.55 2900 1640 1540 1.87 3000 1540 2880 2.23 3100 1440 3210 2 .65 3200 1340 3560 CO 4540 I = -7440 kg = -.4540 .7440 X .00154 396

Run 265 Temp. 2 8.00° Cell D Conc. 0.00154 m. Date 3/ 11/57

R t (rain.) .. .. t ( R ^ _ R )

.33 2400 2180 720 .52 2500 2080 1090 .72 2600 1980 \ 1430 .95 2700 1880 1790 1.19 2800 1780 2120 1.47 2900 1680 2480 1.77 3000 1580 2800 oo 4580 -4580 I = -7770 k2 =’ -7770 X .00154 = 383 229

Table 123

jEpco- '7-M trobloyolo [2 *2 '230ctene-2

Run 266 Temp, 2 8.00° Cell E Conc. 0.000770 m. Date 3/ 11/57 t(mln.) R B&o-R t(Eoo-R)

,27 6200 5800 1570 .40 6300 5700 2280 .53 6400 5600 2960 .62 6660 5400 4430 • 97 6700 5300 5l 4o 1.25 6900 5100 6380 1.42 7000 5000 7100 2.13 7400 4600 9800 2.52 7600 4400 11100 2.95 7800 4200 12400 CO 12000 I = -40400 kg = -12000 - 4o4oo X .000770 = 386

Run 267 Temp. 2 8.00° Cell P Gone. O.OO231 m. Date 3/ 11/57 t(mln.) R Boo-B t(Roo-H)

.27 2300 2090 570 .40 2400 1990 800 .55 2500 1890 lo4o .72 2600 1790 1290 .88 2700 1690 1490 1.09 2800 1590 1730 1.32 2900 1490 i960 1.57 3000 1390 2180 00 4390 —4390 30” I = -4780 ^2 ” -4780 X .00231 230

Table 124 2-Nitrobloyolo[2 *2'2]0otane

Run 205 Temp, 0° Cell C Conc. 0.00257 m. Date 2/ 16/57 t(min.) R Boo-B 't(Roo-R)

.39 2800 3880 1510 1.07 2900 3780 4050 1.80 3000 3680 6630 3 .4 2 3200 3480 11900 4.30 3300 3380 14500 3.23 3400 3280 17200 7.10 3600 30 80 21900 8 .18 3700 298O 24400 9.32 3800 2880 26900 CO 6680

I - -69200 k2 - _ 69200 "x' .00257

Run 206 Temp, 0° Cell D Cono. 0.00514 m. Date 2/ 16/57 t(min.) R R(^-R t(RjjQ-R)

.50 1500 2090 1050 1.22 1600 1990 2430 1.60 1650 1940 3100 2 .3 8 1750 1840 4380 3.78 1900 1690 6400 4 .8 3 2000 1590 7680 6.03 2100 1490 9000 7.37 2200 1390 10250 CO 3590

: = >'2 = X .0051g' = 37.1 231

Table 125 2-Nitroblcyclor2*2-2]0ctane

Eun 209 Temp. 0° Cell C Conc. 0.00257 m. Date 2/18/57

t{min,) R Boo-a t(Eoo-E)

.73 2900 3890 2840 1.42 3000 3790 5380 2.13 3100 3690 7860 2.90 3200 3590 10400

3.70 3300 3490 , 12900 4.48 3400 3390 15200 5 .3 8 3500 3290 17700 6.32 3600 3190 20200 7.32 3700 3090 22600 8 .3 7 3800 2990 25000 9.48 3900 2890 27400 10.67 4 ooo 2790 29800 oo 6790

I = -68400 k2 = = 38.6 -68400 X .00257

Run 210 Temp. 0° Cell D Conc. 0.00514 m. Date 2/ 18/57 t(min.) E E^-E t(E(^-E)

.28 1500 2l4 o 600 .93 1600 2040 1900 1.67 1700 1940 3240 2.45 1800 1840 4520 3.30 1900 1740 5750 4.25 2000 l64 o 6980 5.33 2100 1540 8210 ao 3640 , -8640 I = -18400 ^2 - -18400 X .00514 = 38.4 232

Table 126

2-Nltrobioyclo[2 *2•2]Octane

E u n 242 Temp. 9 . 93® Cell D Conc', o’.00511 m'. D a t e 3/ 5 / 5 ? t(min.) R t(Eoo-E)

. 45 1250 1410 630 .6 8 1300 1360 920 .92 1350 1310 1210 1 .1 9 l 4oo 1260 1500 1.46 1450 1210 1770 1 .7 5 1500 1160 2030 2.08 1550 1110 2310 2 .4 3 1600 1060 2580 2.82 1650 1010 2850 3 .2 5 1700 960 3120 00 2660

kg = ^ .00511 =

R u n 245 Temp. 9 . 93° Cell B Conc. 0 .00511 m. D a t e 3/ 6/57 t ( m i n . ) R ® o o " ® t(Roo-H)

.35 1250 1450 510 .57 1300 l 4oo 800 .80 1350 1350 1080 1.03 l 4oo 1300 1340 1.30 1450 1250 I630 1.58 1500 1200 1900 1.88 1550 1150 2160 2.22 1600 1100 2440 00 2700 _ r 2ZQ.Q,,...... - = 82.7 I = -6400 kg ” -6400 X .00511 233

Table 12? 2-Nltroblcyclo[2 *2-2]Octane

Run 243 Temp, 9 .93° Cell E Conc. 0.00256 ra. Date 3/5/57 t(raln,) E t(Roo-R)

3200 3770 , 1320 .66 3300 3670 2420 .97 3400 3570 3460 1.67 3600 3370 5630 2 .03 3700 3270 6650 2.83 3900 3070 8700 3 .2 7 4000 2970 9700 4 .25 4200 2770 11800 4.7 8 4300. 2670 12800 oo 6970 I = -31840 = -6970 ______k k2 -31840 X .00256 - 8 5 .4

Run 246 Terap. 9 .93° Cell C Conc. 0.00256 ra. Date 3/ 6/57 t(rain,) R ®oo“® t(RoQ-R)

.37 2300 2670 990 .78 2400 2570 2000 1 .24 2500 2470 3060 1.72 2600 2370 4080 2.25 2700 2270 5110 2.81 2800 2170 6110 3.43 2900 2070 7110 4.10 3000 1970 8080 CO 4970

I = -22290 k'' — “4970 _' 87.1 -22290 X .00256 234

Table 128 2-Nitrobicyclo[2*2•2]0ctane

Hun 255 Temp, 28.00° Cell D Conc. 0.00231 m. Date 3/8/57

t(min.) R S q o -R t (Roo“8 )

.20 1700 1620 320 .40 1800 1520 610 .52 1850 1470 760 .63 1900 1420 890 .77 1950 1370 1060 .90 2000 1320 1190 l.o4 2050 1270 1320 1.20 2100 1220 1460 1.37 2150 1170 1600 1.55 2200 1120 1740 CO 3320

" = X :o-23i = 319

Run 263 Temp. 28.00° Cell B Conc. 0.000770 m. Date 3/ 11/57 t(mln.) R Rjyj—R tCRoQ-^R)

.39 4600 4370 1700 .62 4700 4270 2650 .85 4800 4170 3540 1.33 5000 3970 5280 1.60 5100 3870 6190 1.87 5200 3770 7050 2.47 5400 3570 8820 2.78 5500 3470 9650 3.48 5700 3270 ll4 oo 3.85 5800 3170 12200 oo 8970

I = k2 = lleTyo X:ob077Q .... = 303 235

Table 129

2-Nltrobicyclo[2*2*2]Octane

Run 256 Temp. 28.00° Cell E Conc. 0.00154 m. Date 3/8/57 t(mln.) R Boo-B t (Rqo”R )

.25 3400 3200 800 .40 3500 3100 1240 .56 3600 3000 1680 .72 3700 2900 2090 .90 3800 2800 2520 1.10 3900 2700 2970 1.30 4000 2600 3380 1.52 4100 2500 3800 1.77 4200 2400 4250 2 .0 2 4300 2300 4650 2.30 4400 2200 5060 CO 6600

: = -^3700 kg = — ooB? = 3:3

Run 262 Temp. 2 8.00° Cell A Conc. 0.00231 m. Date 3/11/57 t(min.) R B o o - B t(R^-R)

.34 1650 1500 510 .47 1700 1450 680 .59 1750 l4 oo 830 .73 1800 1350 990 .87 1850 1300 1130 1.03 1900 1250 1290 1.18 1950 1200 1420 1.37 2000 1150 1580 1.58 2050 1100 1740 00 3150 . -3150 I = -4475 k2 = = 305 ■ -4475 X .00231 236

Table 130 1-Phenylnltroethane

Run 203 Temp. 0° Cell A Conc, 0.00257 m. Date 2/ 16/57

t(mln.) H ®oo“^ t(Roo-R)

.48 2900 3530 1700 .81 3000 3450 2800 1.48 3200 3250 4810 2.02 3350 . 3100 6260 2.63 3500 2950 7760 3.07 3600 2850 8750 4.03 3800 2650 10700 5.13 4000 2450 12600 ao 6450

^ , .0033,- = 53.7

R u n 207 Temp. 0° Cell A Conc. 0.00257 m. D a t e 2/ 18/57 t(min. ) R B o o - B t(Rao-B)

.33 2900 3610 1190 .65 3000 3510 2280 .96 3100 3410 3270 1.30 3200 3310 4300 1.63 3300 3210 5420 2.02 3400 3110 6280 2 .4 2 3500 3010 7280 2.83 3600 2910 8240 3 .2 8 3700 2810 9230 3.77 3800 2710 10230 4 .2 8 3900 2610 11200 OO 6510

I = -27610 kg = - - ;ôô 257 = 91.9 237

Table 131 1-Phenylnltreethane

Run 2o4 Temp, 0° Cell B Conc, 0,00314 m. Date 2/ 16/57 t(min, ) E Roo“^ t (Eoo—B )

1330 1900 610 .48 I600 1830 890 .63 1650 1800 1130 ,81 1700 1750 1420 1.15 1800 1630 1900 1.57 1900 1330 2430 2,03 2000 1450 2940 2 ,3 3 2100 1330 3440 3.13 2200 1230 3920 00 3450

I = -71ko k2 = X .00514 93-9

E u n 208 Temp, 0° Cell B Cono, 0,00514 m, Da t e 2/ 18/37 t(min, ) E Boo-B t ( E q o —E)

.27 1330 1950 330 ,42 1600 1900 800 .75 1700 1800 1330 .92 1730 1750 1610 1,27 1830 1630 2100 1,48 1900 1600 2370 1.93 2000 1500 2900 2,43 2100 i4 oo 3400 3,02 2200 1300 3920 3.68 2300 1200 4420 00 3300

I = _7%0 kg = X .00514 = 91-8 238

Table I32 1-(p,-Tolyl)Nitroethane

Run 268 Temp. 0° Cell A Conc. 0.00924 m. Date 5 /3/57 t(mln.) R B&0-R t(Rq o —R)

.23 850 1020 230 .52 900 970 500 .80 950 920 740 1.15 1000 870 1000 1.50 1050 820 1230 1.90 1100 770 l 46 o 2 .3 8 1150 720 1710 2.90 1200 670 1940 CD I87O

" = -38^5 % = = 52.6

Run 269 Temp. 0° Cell B ^onc, 0.00462 m. Date 5 /3/57 t(min.) R B&o" t(Roo“S)

.42 1650 1950 820 .68 1700 1900 1290 .97 1750 1850 1800 1.27 1800 1800 2290 1.58 1850 1750 2760 1.92 1900 1700 3260 2.60 2000 1600 4l60 3 .4 2 2100 1500 5130 4.33 2200 l 4oo 6060 CO 3600

I - -14880 k2 = I i ^880 x .00462 " ^2.4 239

Table 133 1- (E,-Tolyl)Nltroethane

Run 270 Temp. 0° Cell D Conc. 0.00462 m. Date 5 /3/57

t(mln.) R RoQ-R t(Roo-R)

.53 1650 1940 1020 .80 1700 1890 1510 1.10 1750 1840 2020 1.70 1850 1740 2960 2.05 1900 1690 3470 2.80 2000 1590 4450 3 .6 3 2100 1490 5420 4.57 2200 1390 6350 CO 3590

I = - 15“ ° = ZlUlo X .OOWZ = 51.5

Run 271 Temp. 0° Cell E Conc. 0.00277 m. Date 5 /3/57 t(rain.) R t(Roo-R)

.63 3600 4200 2650 1.05 3700 4100 4310 1.47 3800 4000 5880 1.93 3900 3900 7530 2 .2 4 4000 3800 8520 2.90 4100 3700 10720 3.43 4200 3600 12360 3 .9 7 4300 3500 13910 00 7800

I = . 5 5 3 0 0 k g . = 5 0 . 9 24o

Table 134

l-(^-Nltrophenyl)Nitroethane

Run 232 Temp, 0° Cell C Conc. 0.00428 m. Date 3/2/57 t(min, ) R ®oo“^ t(Roo-B3

20000 17200 2900 :ll 21000 16200 4200 22000 15700 5320 A 5 23000 14200 6400 .57 24000 13200 7500 .72 25000 12200 8800 .86 26000 11200 9600 00 37200

I = -18900 w. -37200 = 46 oo -18900 X .000428

Run 228 Temp. 0° Cell C Conc. 0,000428 ra. Date 2/28/57 t(mln,) R ® 0O “^ t (R(X)~R )

.27 21000 14900 4020 22000 13900 5150 [47 23000 12900 6070 .60 24000 11900 7150 .75 25000 10900 8200 .92 26000 9900 9100 CO 35900 I = -I78OO k2 = -35 ,9,00...... = 4720 -17800 X .000428 241 Table 135 l-(ü-Nitrophenyl)Nltreethane

Run 229 Temp, 0° Cell E Conc. 0,00286 m, Date 2/28/57 t(min.) R Rrvn-R t(R^ -R) .15 40000 29800 4470 .22 41000 28800 6340 .28 42000 278OO 7650 .33 43000 268OO 8850 .42 44000 25800 10820 .50 45000 24800 12400 .58 46000 23800 13900 .67 47000 22800 15300 oo 69800 I = -56300 ko = -69800 = 4340 -56300 X .000286 Run 226 Temp, 0° Cell C Conc. 0,000857 ra. Date 2/27/57 t(min.) R Roo~® t(Roo”I^) .38 12500 6700 2540 .55 13500 5700 314o CJO 19200 I = -4880 ko = = 4600 -4880 X .000857

Run 233 Temp. 0° Cell E Conc. 0.00286 m. Date 3/2/57 t(mln.) R Rqq—R t(Roo-R)

.13 40000 34800 4500 .21 42000 32800 6900 44000 30800 10180 ‘.47 46000 28800 13500 .60 48000 26800 16100 .80 50000 24800 19800 .98 52000 22800 22400 00 74800 = I = -57450 k2 -74800 = 4550 -57450 X .000286 242

Table 136 1-(ra-Nltrophenyl)Nitroethane

Euti 278 Temp. 0° Cell E Cono. 0.00139 m. Date 6/ 11/57 t(mln.) R & 00-B t(Eoo-E)

.1 6 8000 7900 1260 .29 9000 6900 2000 .38 9500 6400 2400 .59 10500 54 oo 3180 .73 11000 4900 3580 .88 11500 CO IJ^oo I = -5100 k2 - = i m o _ = 2240 -5100 X .00139

Run 279 Terap. 0° Cell A Conc. 0.00285 ra. Date 7/23/57 t(mln.) R Boc-a

.38 28000 20400 7800 .57 29000 19400 11000 .80 30000 18400 14700 1.03 31000 17400 17900 1.28 32000 16400 21000 1.57 33000 15400 24200 1.93 34000 14400 278OO 2.33 35000 13400 31200 CO 48400

I = -85800 _ -48400 2 -85800 X .000285 ^980 243

Table 137 1-(ia-Nltrophenyl )Nifcroethane

Run 280 Temp. 0° Cell B Conc. 0.000428 m. Date 7/23/57

t(min.) R t

.33 19000 15200 5000 .42 19500 14700 6200 .62 20500 13700 8500 .73 21000 13200 9600 .83 21500 12700 10800 .98 22000 12200 12000 1.12 22500 11700 13100 1.27 23000 11200 14200 CO 34200

I = -3900 1, _ -34200 , — om/iy) -39000 X ,.000428

Run 281 Temp, 0° Cell D Conc. 0.000428 m'. Date 7/23/57

t(mln.) R t(Roo-R)

.32 18500 13500 4300 .43 19000 13000 5600 .53 19500 12500 6600 .75 21500 11500 8600 .90 21000 11000 9900 1.03 21500 10500 10800 1.20 22000 10000 12000 1.37 22500 9500 13000 CO 32000 -32000 = 2l6 o I = -34600 ^2 -34600 X .000428 APPENDIX C

244 s a

l-d - Nitrocydobutone NOg

L iq u id

F IG U R E 15

Nitrocydobutone I—

L iq u id ro jr Ln

FIGURE W :

l-d-N itrocyciopentone

NO,

L iquid

F IG U RE 17

Nitrocyclopentone

L iq u id fo o\

FIGURE 16 I:

l-d- Nitrocyclohexane

o c L iq u id

F IG U R E 19

Nitroqrclohexane

NO;

L iq u id

FIGURE 18 Nitrocycloheptane

F IG U R E 2 0

0 0 I i I- 4 - Nilfocyclohexene j

L iq u id

NOj

L iq u id

FIGURE 21 ê

40 Exo~S-nitrobicvcIo - [22' I] heptene - 2

( h L iq u id

F IG U R E 2 4 "

Endo-5-nilfobiCYClo - [ 2 2 1] h e p te n e - 2

Amorphous solid Vjx o

FIGURE 23 3?

Exo’ 2~nilrobicyclo [2-2I1 hepton«

L iq u id

Endo -2 - nitrobicydo [2 2 1] h e p to n e

w Amorphous solid Vji

FIGURE 25 !

1 I I

^ Exg - 5- nitrobicycto [222]- o c t e n c - 2

•NO;

L iq u id

FIG U R E 2 6

Endo •5-nilrobicvcto 12221- o c f e n e - 2

0/i to Amorphous solid to 2-Nilrobicyclo ÏZ2-2} o c to n e

NOg N u jo t m u ll

FIGURE 2Sr

to Vj\ VjJ il l"(fi“ToIyl)nitroethone

CH.

L iq u id

F IG U R E 31 JSa.

I- Phenylnitroethone

L iq u id to -P-

FÎÔJRE 30’ WAVE NUMBERS IN CM * WAVE NUMBERS IN CM-i 5000 4000 3000 2500 2000 1500 1400 1300 1200 1100 900 800

I. I - ( m - ni trophenyi ) n I f ro - ethane

.2- - ’3 Nujol mull

t 7 12 13 14 15 LENGTH IN MICRONS WAVE LENGTH IN MICRONS FIGU RE 3 3

40-i l-(£-Nitrophenyljnitro- e th o n e

C-NOj. CHj ro Nujol mull Ln La

FEURE Ultraviolet absorption spectra of onions of ni fro compounds

Nitro compound ^max ^mox Nitrocydobutone ------231 10,300 Nitrocyclopentone • ------228 13,500 Nitrocyclotiexcne - — ------233 12,000 0.75 X iO"*’ m. in dioxon/woter (50- 50 vol.)

>» tn c0> T3 O O O. O

210 2 3 0 2 5 0 270 Wave lengtti, millimicrons ro o\ FIGURE 34 Ultraviolet absorption spectra of onions of nitro compounds

Nitro compound Nitrocyclotieptone 2 3 0 12.900 Nitrocyclobctane ------233 10.900 4- Nitrocyclotiexene 231 11,300 0.75 X IO”^m. dioxon/woter (50 50 vol.)

250 N5 Wove lengtti, millimicrons FIGURE 35 Ultraviolet absorption spectra of anions of nitro compounds

Nitro compound ^ max 2- Nitronorbornone 2 3 0 13,000 5 - Nitronorbornene 240? 9,100 231 11,600 2 240 11,400 0.75 X I0"4 m. in dioxon/woter (50=50 vol.l

« 0.6

250 270 Wove lengtti, millimicrons Ln CO FIGURE 36 AUTOBIOGRAPHY

I, Pat Wayne Keith Flanagan, was horn in Camargo,

Douglas County, Illinois, on June 2 0 , 1 9 3 1» I received my elementary school education ini the public schools of Dayton, Ohio, and my secondary education from Roosevelt High School in Dayton, Ohio. After graduating from high school in 19^9, I attended Miami University, Oxford, Ohio, from which I was granted the degree Bachelor of Science, magna cum laude, in June, 1 9 5 3 » I entered the Graduate

School of the Ohio State University in September, 1 9 5 3 » I held appointments as a Fellow of the National Science

Foundation (1953 -5 6 ) and of the Allied Chemical and Dye

Company (1956 -5 ?) while completing the requirements for the degree Doctor of Philosophy.

259