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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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    A&A 406, 385–391 (2003) Astronomy DOI: 10.1051/0004-6361:20030773 & c ESO 2003 Astrophysics Elementary reactions of the phenyl radical, C6H5, with C3H4 isomers, and of benzene, C6H6, with atomic carbon in extraterrestrial environments R. I. Kaiser1, L. Vereecken2, J. Peeters2, H. F. Bettinger3, P. v. R. Schleyer4,5, and H. F. Schaefer III4 1 Department of Chemistry, University of Hawai’i at Manoa, Honolulu, HI 95622, USA 2 Department of Chemistry, University of Leuven, Celestijnenlaan 200F, 3001 Heverlee, Belgium 3 Lehrstuhl f¨ur Organische Chemie 2, Ruhr-Universit¨at Bochum, 44780 Bochum, Germany 4 Center for Computational Quantum Chemistry, The University of Georgia, Athens, GA, USA 5 Institut f¨ur Organische Chemie, Universit¨at Erlangen-N¨urnberg, 91052 Erlangen, Germany Received 19 February 2003 / Accepted 15 May 2003 3 1 Abstract. Binary collisions of ground state carbon atoms, C( P j), with benzene, C6H6(X A1g), and of phenyl radicals, 2 1 C6H5(X A1), with methylacetylene, CH3CCH(X A1), were investigated in crossed beam experiments, ab initio calculations, and via RRKM theory to elucidate the underlying mechanisms of elementary reactions relevant to the formation of polycyclic aromatic hydrocarbons (PAHs) in extraterrestrial environments. The reactions of phenyl radicals with allene, H2CCCH2, and with cyclopropene, cyc-C3H4, as well as the reaction of benzyl radicals, C6H5CH2, with acetylene, HCCH, were also inves- 3 tigated theoretically. The C( P j) atom reacts with benzene via complex formation to a cyclic, seven membered C7H5 doublet radical plus atomic hydrogen. Since this pathway has neither an entrance nor an exit barrier and is exoergic, the benzene molecule can be destroyed by carbon atoms even in the coldest molecular clouds.
  • The Synthesis of Carbacyclic Silanes Via Organosilicon Reactive Intermediates Michael J

    The Synthesis of Carbacyclic Silanes Via Organosilicon Reactive Intermediates Michael J

    Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1984 The synthesis of carbacyclic silanes via organosilicon reactive intermediates Michael J. Vuper Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Vuper, Michael J., "The synthesis of carbacyclic silanes via organosilicon reactive intermediates " (1984). Retrospective Theses and Dissertations. 7737. https://lib.dr.iastate.edu/rtd/7737 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. INFORMATION TO USERS Tliis reproduction was made from a copy of a document sent to us for microfilming. While the most advanced technology has been used to photograph and reproduce this document, the quality of the reproduction is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help clarify markings or notations which may appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure complete continuity. 2. When an image on the film is obliterated with a round black mark, it is an indication of either blurred copy because of movement during exposure, duplicate copy, or copyrighted materials that should not have been filmed.