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A?“A ENTRY to the {Crthydrclcrrmo ENERGY A? “a ENTRY TO THE {CRthYDRC LCRRMO ENERGY Sb RFACE Dissertatianf orthe Degree of Ph. D. MECHEGAN STATE :xé";ERS!TY THORAS mEL REéTZ .1976 t, ,r ”EARY WHM/M/Iffl/WW Karachi-"53115” ‘ 3 1293 00823 7251 i:L Univen'ty V This is to certify that the _ ._ ‘. thesis entitled A NEW ENTRY TO THE (CH)12 HYDROCARBON ENERGY SURFACE presented by Thomas Joel Reitz has been accepted towards fulfillment of the requirements for Ph. D. degree in Philosophy Major professor Date June 30: 19 76 0‘7 639 Iv “r ABSTRACT A NEW ENTRY TO THE (CH)12 HYDROCARBON ENERGY SURFACE BY Thomas Joel Reitz Pyrolysis of the dry lithium salt of trans-B-[anti-Q-bicyclo- [6.1.0]nona-2,4,6-trienyl]acrolein tosylhyrazone resulted in the formation of three (CH)12 hydrocarbons, characterized as: e§g_and endo- tricyclo[4.4.2.0 2,5 ]dodeca-3,7,9,ll-tetraenes and the previously 2,120.3,704,ll unreported diene, pentacyclo[6.4.0.0. ]dodeca-5,9-diene. The tosylhydrazone deuterated B to the tosyl group was also prepared and its pyrolysis products were studied. Some mechanistic considerations of the formation of the thermolysis products were examined. We have also looked at the thermolysis of some antifg-bicyclo- [6.l.0]nona-2,4,6-triene derivatives. We have found rearrangement to the corresponding bicyclo[4.2.l] system to be general for derivatives Thomas Joel Reitz with extended n-electron withdrawing ability. “—;-—q In the second part of this work we attempted to isomerize anti; 9-(AZ-cyclopropeno)-bicyclo[6.l.0]nona-2,4,6-triene to truncated tetrahedrane. Some photochemical and transition metal catalyzed isomerizations were tried. "W‘W A NEW ENTRY TO THE (CH)12 HYDROCARBON ENERGY SURFACE By Thomas Joel Reitz A DISSERTATION Submitted to Michigan State University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Chemistry 1976 TO MY PARENTS ii Acknowledgements I wish to thank Dr. Donald G. Farnum fbr his help, guidance and continued encouragement throughout the course of this graduate study. Thanks are also give to Dr. Lynn Sousa for his time spent with me in helpful discussions. I acknowledge the financial support of Michigan State University in the form of teaching and research assistantships. Especially I thank all the members (past and present) of the "group", all the friends I have developed here, and Pat, the listening ear, who have made my stay here both enjoyable and bearable. Finally, I thank my parents for their continual support, confidence and prayers. Table of Contents Page List of Tables .......................... vii List of Figures ......................... Introduction ........................... Results and Discussion. Part A ................. Synthesis of Trans- -8- anti- 9- bicyclo[6. l .0]- 2, 4, 6- trienle- acrolein Tosylhydrazone g§) ................ T8 Thermal Decomposition of Tosylhydrazone g§ ......... 20 Endo and exo-Tricyclo[4.4.2.02’5]dodeca-3,7,9,]l-tetraenes (£35 and Egg) ....................... Pentacyclo[6.4.0.02’120. 3’ 70 .4”]]]dodeca-5,9-diene (~§)' A Look at a Possible Mechanism to g; and 33 ......... 27 Some Mechanistic Thoughts on the Formation of 33 ...... 29 Rearrangement to the [4.2.l] System ............. 30 Rearrangements of the [6.l.0] System . .......... 33 A Closer Look at the Pyrazole Formed from Decomposition of fig. ........................... A General Scheme for the Decomposition of fig ........ 35 Deuterium Labeling as a Mechanistic Probe: [1,5] or Cope? .......................... 39 Preparation of Deuterated Tosylhydrazone .......... 4o Thermal Decomposition of Deuterated Tosylhydrazone ggag. 42 Position of Deuterium in Deuterated 32 to fig ........ 42 Interpreting CNMR Spectra of Deuterated Compounds ...... 43 Assignment of Position of Deuterium in Diene ggag ...... 44 iv Table of Contents (Continued) Eggg_ Heating of Tetraene 43: Possibility of Fluxional Character .......................... 47 Summary ........................... 48 Results and Discussion. Part 3. .................. 50 Experimental ........................... 58 General ........................... 58 Bicyclo[6.l.0]nona-2,4,6-triene-9-carboxaldehyde (31). 60 Diethyl-2(cyclohexylamino)vinylphosphonate (Q2). Preparation of the Enamine Reagent ............. 60 Trans-B[anti-9-bicyclo[6.l.0]nona-2,4,6-trienyl]acrolein (gg). Preparation of the Extended Aldehyde Using the Enamine Reagent 32 and Aldehyde gz ..... ....... 6l Trans-B[anti-9-bic clo[6.l.0]nona-2,4,6-trienylJacrolein losyihydrazone (g5) ..................... 63 Lithium Salt 4; of Tosylhydrazone 35 ............ 63 Preliminary Work to Preparative Pyrolyses A. Method of Jones, Reich and Scott. Decomposition of Dry Salt 41 ............. 64 Decomposition of Dry Salt 4; ........... 64 8. Gas Chromatographic Pyrolyses of Tosylhydrazone Salts. ~ Decomposition of Dry Salt 4) ............. 65 Decomposition of Dry Salt 4% ............. 65 C. Pyrolysis in Sand Bath. Decomposition of Dry Salt fig ............. 65 Endo-Tricyclo[4.4.2.02’5]dodeca-3,7,9,ll-tetraene (4 ), Exo-tricyclo[4.4.2.02:5130deca-3,7 9,ll-tetraene ( ‘ , Pentacyclo-[6.4.O.O.2»1 .3’70.“’11]-dodeca-5,9-diene (45). Pyrolysis of Tosylhydrazone Salt 4g ............. 66 Table of Contents (continued) Page Determination of Temperature Dependence of the NMR Spectrum of fig ...................... .. 69 Attempts to Deuterate Tosylhydrazone fig. ...... 69 Preparation of Deuterated Enamine Reagent (325g) ...... 70 Trans-a-[anti-9-bicyclo[6.l.0]nona-2,4,6-trienyl]- propenaldehyde-Z-d (ggag). Preparation of Deuterated Extended Aldehyde ...................... 71 Deuterated Tosylhydrazone - . Preparation of Tosylhydrazone from Deutera e Extended Aldehyde 353g. 71 Lithium Salt 435g of Deuterated Tosylhydrazone gggg ..... 72 Decomposition of the Deuterated Dry Salt $68R° Endo- tricyclo[4.4.2.02:5]dodeca-3,7,9,ll-tetraene-B-d - ), Exo-tricyclo[4.4.2.02a5]dodeca-3,7 9 ll-tetraene-3- m- ), Pentacyclo-E6.4.O.0.2s120.§9’O.“:11]-dodeca— 5, - iene-Z-d (QRER 72 Heating of Endo-tricyclo[4.4.2.ozs5]dodeca-3,7,9,ll- tetraene-3-3 (IQ-d). .............. Anti-9-(A2-cyclopropeno)-bicyclo[6.l.0]nona-2,4,6-triene Low Temperature Decomposition of Tosylhydrazone Pyrolysis of Anti-9-(A2-cyclopropeno)—bicyclo[6.l.O]nona- 2’4’6-triene 22 000000000000 o oooooooooo Preparation of Pyrazoles 5g and . Decomposition of Tosylhydrazone Salt 4% in etrag yme ............ 75 Photolytic Attempts at Isomerizing g1 ............ 76 Treatment of £7 with PdClz(¢CN)2 .............. 77 Attempts at Isomerizing £1 with Mo(C0)5 ........... 77 Preparation of Mo(CO)3-diglyme ............... 78 Att ts at Isomerizing 6A in the Presence of Mo(CO 3-diglyme ............ .......... 79 Footnotes ............................. 80 vi Ljst of Tables_ Table Page 1 Comparison of CNMR Data for Undeuterated and Deuterated Pyrolysis Products .............. 45 vii List of Figures Figure Interconversions of (CH)8 Isomers ............ Interconversions of (CH)10 Isomers ............ Interconversions of (CH)12 Isomers ............ Uncharted (CH)12 Isomers. ................ ThEHMITY Allowed (ll’zs + "ZS + “'25) 01th Interconversions of Truncated Tetrahedrane ........ O5 Preparation of Tosylhydrazone 35. .......... T9 Possible Structures for 45 Based on CNMR Symmetry Considerations ...................... 25 Rearrangement of Some [6.l.0] Derivatives to the Dihydroindene and [4.Z.l] System ............. 34 Course of Carbon-l0 in a [l,5] and Cope Rearrangement of QQ ....................... 39 10 Mechanism for the Reaction of Aldehyde 31 with Deuterated Enamine Reagent (3259) ............ 41 ll Possible Degenerate Rearrangements of 33 ........ 47 12 Pyrolysis Apparatus for Decomposition of Dry Salts. 67 l3 PNMR of Endo-Tricyclo[4.4.2.02’5]dodeca-3,7,9,ll- tetraene (g§) ...................... 79a T4 PNMR of Endo-Tricyclo[4.4.2.02’5]dodeca-3,7,9,ll- tetraene-B-d (ggag) . ................. 79a 15 PNMR of Exo-Tricyclo[4.4.2.02’5]dodeca-3,7,9,ll- tetraene_T§4) . ....... 79b 16 PNMR of gxngricyclo[4.4.2.02’5]dodeca-3,7,9,ll- tetraene-3-d (44-g) ................... 79b T7 PMMR of Pentacyclo[6.4.0.0.2’120.3’704’11]dodeca- 5,9-d18fle (£2) oooooooo o ooooooooooooo 79c 18 PNMR of Pentacyclo[6.4.O.0.2’]20.3’704’11Jdodeca- 5,9-diene-2-d (RRER) ................... 79c viii Introduction Mapping of the interconversions of stable molecules residing on the potential energy surfaces describing (CH)n hydrocarbons has been the goal of various research groups. 1’2’3’4 Some of the findings for (CH)8.] (CH)10 2 and (CH12 3 hydrocarbons are illustrated in Figures l, 2 and 3 respectively. Two recent review articles have helped to organize much of this material. Masamune and Darby 4a reviewed [l0] 4b annulene and other (CH)10 hydrocarbons, and Scott and Jones examined a number of other (CH)n compounds. Also Balaban5 has published a series of computer generated valence isomers of (CH)n cyclOpolyenes (where n = 2, 3, 4 or 5,5a and where n = 6 5b) which conveniently acts as a compendium for these compounds. Much of the work to date in studying (CH)n formations and trans- formations have centered on the (CH)8 and (CH)10 energy surfaces. A few contributions are of particular note. The prediction2c and subsequent synthesis2p of bullvalene (l) validated the concept of "fluxional" molecules. whereby very rapid valence tautomerization results in the interchange of carbon atom positions within a molecule. Fluxional A > Q molecules are members of a repeatedly appearing class of compounds capable of undergoing degenerate rearrangements. They have the distinc- tion of rearranging extremely fast, i.e., too fast for individual 1 ya fl \ /l ’0. \ hi) In) W war A .m “\ V .22.) A Q V MM Figure l. Interconversions of (CH)8 Isomers. (CH=CH)§H 1< [Y5:§I/ hv RT ‘10 hv hv hv -100° ~70° -100° \\\\:700 -7o° h“ -70 T hv hv >300 -70° +20o ./’ “a9 \ . i 1w" 4 \ i / hv -300 ___ hv r—- ? -- Q < 1200 I I -1000; /—— : :J ___ ? /, ‘\\\\Ev L__ ._J 500° hv acetone i h, / ,/’ "500 hv hv acetone 42CO A8 \ <E—*- 580° i".
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