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Rearrangements in Carbenoid Decomposition of 2, 2, 2

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Rearrangements in Carbenoid Decomposition of 2, 2, 2 This dissertation has been 63-4699 microfilmed exactly as received SARGEANT, Peter Barry, 1936- REARRANGEMENTS IN CARBENOID DECOMPO­ SITION OF 2,2,2-TRIARYLDIAZOETHANES. The Ohio State University, Ph.D., 1962 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan REARRANGEMENTS IN CARBENOID DECOMPOSITION OF 2,2,2-TRIARYLDIAZOETHANES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Peter Barry Sargeant, B.S. The Ohio State University 1962 Approved by ^ Adviser _ _' Department of Chemistry Dedicated to my wife, Patricia Marie, whose patience, understanding, and sacrifices helped make this possible. ii ACKNOWLEDGMENT I would like to express my appreciation to Professor Harold Shechter for his Inception of this study, for his guidance and suggestions throughout the investigation, for many stimulating discussions, and for his assistance In the preparation of this dissertation. I would also like to thank Professors W. N. White and P. 0. Gassman for helpful discussions and advice* I am grateful to the National Science Foundation for three yearB of financial support, to the Goodyear Tire and Rubber Company and Dr. K. W. Greenlee, to the Department of Chemistry and the DuPont Fund, and to the National Science Foundation and Dr. Harold Shechter for financial assistance. iii CONTENTS Page INTRODUCTION AND HISTORICAL .......................... X DISCUSSION ................................................ 10 EXPERIMENTAL.............................................. 45 General Information ............................... 45 Intermediates Trlphenylacetic A c i d ................................. 46 Triphenylacetyl Chloride ............. 46 2.2.2-Trlphenylethanol ........................... 47 Triphenylacet al d e h y d e ............................ 47 Triphenylacetaldehyde Tosylhydrazone ............ 48 1.2-Diphenyl-l-o-tolylethylene Glycol ........... 48 Dlphenyl-o-tolylacetaldehyde ..................... 49 Dlphenyl-o-tolylacetaldehyde Tosylhydrazone . 49 Triphenylacetonitrlle .......................... 50 2.2.2-Triphenylethylamine ........................ 50 Ethyl N-P, f,P-Triphenylethyl Carbamate ............. 51 Ethyl-N-Nitroso-N-{J,p,p-trlphenylethyl Carbamate . 52 2.2.2-Triphenyldiazoethane ......................... 52 Diphenyl-£-tolylmethanol.............................53 Phenyl-di-£-tolylmethanol.......................... 53 £-Chlorophenyldipnenylmethanol...................... 54 Diphenyl-£-tolylchlororae th a n e ...................... 55 iv Page Phenyl-di-£-tolylchloromethane................. 55 £-Chlorophenyldiphenylchloromethane ............ 55 Diphenyl-£-tolylacetonitrile .................... 56 Phenyl-di-£-tolylacetonltrile .................. 56 £-Chlorophenyldlphenylacefconitrlle .............. 57 Diphenyl-£-tolylacetaldehyde Tosylhydrazone . 57 Phenyl-di-£-tolylacetaldehyde Tosylhydrazone .. 59 £-Chlorophenyldlphenylacetaldehyde Tosylhydrazone. 60 £-Nltrobenzoyl Chloride ........................ 6l £-Nltrobenzophenone ............................ 62 £-Nitrophenylphenyldlchlororaethane .............. 62 £-Nitrophenyldiphenylchloromethane .............. 63 £-Nitrophenyldlphenylacetonitrile .............. 6k £-Nitrophenyldlphenylacetaldehyde Tosylhydrazone . 6k £-Anlsyldiphenylacetlc Acid .................... 66 2-£-Anisyl-2,2-diphenylethanol .................. 66 £-Anlsyldiphenylacetaldehyde .................... 67 £-Anisyldiphenylacetaldehyde Tosylhydrazone . 68 Thermal Decomposition and Rearrangement of Tosylhydrazones General Technique .............................. 69 Reagents....................................... 69 Analysis of Rearrangement Products .............. 70 Gas Chromatography............................. 72 Decomposition of Trlphenylacetaldehyde Tosylhydrazone ................................ 72 v Page Decomposition of 2,2,2-Triphenyldiazoethane . 74 Reduction of Triarylaceton!triles with Diborane . 75 Reduction of Triphenylacetonitrile .............. 75 Reduction of £-Anisyldiphenylacetonitrile .... 76 Structure Proof of Alkylideneamino Boranes .... 77 Reduction of Triarylacetonitriles with Lithium Aluminum Hydride..................... 82 Intermediates Diphenyl-o-tolylmethanol ........................ 82 Diphenyl-o-tolylchlororaethane .................. 82 Diphenyl-o-tolylacetonitrile .................... 83 £-Bromoanisole .................................. 83 £-Anisyldiphenylchlororaethane .................. 84 £-Anisyldiphenylacetonitrile .................... 85 Methyl £-Bromobenzoate....................... 85 £-Bromophenyldiphenylchloromethane .............. 86 £-Bromophenyldiphenylacetonltrile .............. 86 Reduction of Triphenylacetonitrile .............. 87 Reduction of Diphenyl-o-tolylacetonitrile .... 87 Reduction of £-Anisyldiphenylacetonitrile .... 88 Reduction of £-Bromophenyldiphenylacetonitrile . 89 AUTOBIOGRAPHY................................... 91 vi TABLES Table Page 1. Characteristic Infrared Absorption of Tosylhydrazones................................. 26 2. Decomposition of Substituted Triarylacetaldehyde Tosylhydrazones ................................ 32 vii FIGURES Figure Page 1. Hamnett Correlation of Migration Aptitudes with <jp Substituent Constants.................33 2. Hammett Correlation of Migration Aptitudes with <Tp Substituent Constants ............... 39 viii INTRODUCTION AND HISTORICAL Divalent carbon chemistry (l) has been a subject of (l) Confusion and ambiguity exists regarding the nomenclature of gem-divalent radicals. Hie term "carbene" will be used in this study to denote the family of divalent carbon compounds in general. The first member of this homologous series will be named methylene (HgC:); all other gem-divalent radicals will be named by adding "-idene" to the name of the corresponding univalent radical [Inter­ national Union of Pure and Applied Chemistry Report on Nomenclature, J. Am. Chem. Soc., 82, 5545 (I960); R. S. Shank, Ph.D. Dissertation, Hie Ohio State University, 1 9 6 1]. renewed Interest in the past decade. New syntheses of divalent carbon intermediates have been devised and evidence of the presence of carbenes in numerous reactions has been found (2-5). (2) For reviews of the chemistry of divalent carbon see: W. Kirmse, Angew. Chem., J3, 161 (1961); 71, 537 (1959); (3) J* Leitich, Osterr.Chemiker-Ztg., No. 6, 164 (I96 0): ----- (4) R. Huisgen, Angew Chem., 67, 439 (1955); and (5) B. Eistert in Newer Methods of Preparative Organic Chemistry," Interscience Publishers, Inc., New York, New York, 1948, p. 513. Any discussion of divalent carbon must include con­ sideration of the multiplicity of these specieB. Hie two unshared electrons may be unpaired and formally considered to occupy two 2£ orbitals resulting in a triplet, or they 1 2 p may be paired and formally considered to occupy a sp orbital with a 2£ orbital vacant resulting in a singlet molecule. H Triplet Singlet Skell and Woodworth (6) suggested that singlet (6) P. S. Skell and R. C. Woodworth, J. Am. Chem. Soc., 4496 (1956); (7) R. C. Woodworth and P. S. Skell, J. Am. Chem. Soc., 81, 3383 (1959)- methylene should react stereospeclfically with olefins, Whereas triplet methylene should not, and therefore assigned the singlet state to methylene produced from photolysis of diazomethane on the basis of its stereospeclfic addition to els- and trans-2-butene. Extensions (8-12) of this idea (8 ) R. M. Etter, H. S. Skovronek and P. S. Skell, J. Am. Chem. Soc., 81, 1009 (1959); (9) P* S. SkeTl and J. Klebe, J. Am. Chem. Soc., 82, 247 (I960); (10) P. S. Skell and A. Y. Garner, J. Am. Chem. Soc., 18, 5430 (1956); (11) P. S. Skell and R. N. Etter, Chem. and Ind., 624 (1958); (12) W. von E. Doering and W. A. Henderson, Jr., J. Am. Chem. Soc., 80, 5274 (1958). were the basis for the assignment of the singlet state to dibromomethylene (1 0 ), dichloromethylene (10 ), propylldene (9), 3 car bethoxymeth y le ne (11), and 2-ketopropylldene (9), and the triplet state to diphenylmethylene (8) and propargylldene (9)• Detailed quantum mechanical calculations (13-15) for (13) 0* A. Gallup, J. Chem. Phys., 26, 716 (1957)i (14) A. Padgett and N. Kraus, J. Chem. Phys., 32, 189 (I960); (15) J. M. Poster and S. P. Boys, Rev. Mod. Phys., 2£, 305 (I960). methylene indicate a triplet ground state and a close-lying singlet excited state. These calculations are In satisfac­ tory agreement with the report (1 6) of Bpectroscoplc evidence (16) G. Herzberg and J. Shoosmith, Nature, 183, 1801 (1959); G. Herzbersc, Proc. Roy. Soc. (London). Ser. A., 262, 291 (1961). that the vapor phase photolysis of diazomethane produces singlet methylene which decays to the triplet state in the presence of inert gas at high pressures. This result indi­ cates that the ground state of methylene must be triplet. Chemical evidence has been obtained for the singlet-triplet decay of methylene In the gas phase in the presence of argon at high pressures (17) In that triplet methylene reacts with (17) H. M. Prey, J. Am. Chem. Soc., 82, 59*»7 (i9 6 0). cls-2-butene non-stereospecifically. Triplet methylene has been generated (1 8) in solution by photosensitized (18) K. R. Kopecky, G. S. Hammond and P. A. Leermakers, J. Am. Chem. Soc., 84, 1015 (1962); ££, 2397 (1961). decomposition of dlazomethane. Triplet methylene did Indeed react non-stereospeclfically with els- and trans-2-butenes as predicted (3) and as observed in the vapor phase (17)* Thermal decomposition of diazomethane also produces singlet methylene. Application
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