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University Microfilms INFORMATION TO USERS This dissertation was produced from a microfilm copy of the original document. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the original submitted. The following explanation of techniques is provided to help you understand markings or patterns 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 thru an image and duplicating adjacent pages to insure you complete continuity. 2. When an image on the film is obliterated with a large round black mark, it is an indication that the photographer suspected that the copy may have moved during exposure and thus cause a blurred image. You will find a good image of the page in the adjacent frame. 3. When a map, drawing or chart, etc., was part of the material being photographed the photographer followed a definite method in "sectioning" the material. It is customary to begin photoing at the upper left hand corner of a large sheet and to continue photoing from left to right in equal sections with a small overlap. If necessary, sectioning is continued again — beginning below the first row and continuing on until complete. 4. The majority of users indicate that the textual content is of greatest value, however, a somewhat higher quality reproduction could be made from "photographs" if essential to the understanding of the dissertation. Silver prints of "photographs" may be ordered at additional charge by writing the Order Department, giving the catalog number, title, author and specific pages you wish reproduced. University Microfilms 300 North Zeeb Road Ann Arbor, Michigan 48106 A Xerox Education Company ORPHANIDES, Gus George, 1947- THE CHEMISTRY OF 2- AND 3-THENYLIDENES; CARBENIC AND CATIONIC REACTIONS OF flt-DIAZO THIOLESTERS. The Ohio State University, Ph.D., 1972 Chemistry, organic University Microfilms, A XEROX Company, Ann Arbor, Michigan ' THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED. THE CHEMISTRY OP 2- AMD 3 -THENYLIDENES; CARBENIC AMD CATIONIC REACTIONS OP a-DIAZO THIOLESTERS DISSERTATION Presented In Partial Fulfillment of the Requiremen bs for the Degree Doctor of Philosophy in the Graduat School of The Ohio State University By Gus George Orphanides, B.S. * # # # The Ohio State University 1972 Approved hy Advisor Department of Chemistry PLEASE NOTE: Some pages may have indistinct print. Filmed as received. University Microfilms, A Xerox Education Company DEDICATION To ray wife, Jeanne-Marie 11 ACKNOWLEDGMENTS I would like to thank Dr. Harold Shechter for the suggestion of this research problem and his expert guidance in the preparation of this dissertation. I also wish to extend appreciation to Dr. John Swenton for his guidance in the photochemistry in this research. I am grateful to the National Institute of Health and the Depart­ ment of Chemistry of The Ohio State University for financial support. iii VITA.' January 27, 19^-7 Born - Kew Gardens, New York 1967 .................... B.S., Hobart College, Geneva, New York 1967-1969 .......... Teaching Assistant, Department of Chemistry, The Ohio State Univer­ s i t y , Columbus, Ohio 1969-1972 .......... Research Associate, Department of Chemistry, The Ohio State Univer­ s i t y , Columbus, Ohio TABLE OP contents Page DEDICATION.............'................................................ i l ACKNOWLEDGMENTS ............................... i l l VITA.......................................................................................................................... iv SECTION 1 STATEMENT OF THE PROBLEM.................................................................................. 1 HISTORICAL............................................................................................................... 3 DISCUSSION OP RESUITS............................................................... ..................... 16 SUMMARY AND CONCLUSIONS ................................................................................... 31 EXPERIMENTAL.................................................................................................................. 3& General Procedures and Techniques ..................................................... 38 Preparation of 2-Thiophenecarboxaldehyde p-Tosylhydrazone .. 39 P reparation of the Sodium S alt of 2-Thiophenecarhoxaldehyde p-Tosylhydrazone ...................................................... 39 Decomposition of the Sodium S.alt of 2-Thiqphenecarboxalde- hyde j-Tosylhydrazone in Cyclooctane ........................................... *t-0 Gas Phase Pyrolysis of Substituted Thienyldiazomethanes Prepared in Si t u .................................................................................... *t-l Gas Phase Pyrolysis of 2-Thienyldiazomethane Generated in S i t u ....................................................................................... Preparation of 2-Thiophenecarhoxaldehyde Azine ........................ Synthesis of l,2-Di(2-thienyl)ethylene ........................................... UH v Page Preparation of 3-Thiophenecarboxaldehyde |>-Tosylhydrazone .. 46 Preparation and Decomposition of the Sodium Salt of 3-Thio­ phenecarboxaldehyde £-Tosylhydrazone in Cyclooctane 46 Gas Phase Pyrolysis of 3-Thienyldiazomethane Generated In S i t u ...................................................................................................... 4? Preparation of 3-Thiophenecarboxaldehyde Azine ................................ 48 Preparation of 5-Methyl-2-thiophenecarboxaldehyde £-Tosyl- h yd razon e ................................................................................................ 48 Gas Phase Pyrolysis of 5-Methyl-2-Ihienyldiazomethane Generated in S itu ...................................................................................... 49 Preparation of Methyl 2-Thienyl Ketone £-Tosylhydrazone .... 50 Gas Phase Pyrolysis of a-Methyl 2-Thienyldiazomethane Generated in S itu .......................... 51 Preparation of Methyl 2-Thienyl Ketone A zine ................................ 52 Preparation of 2-Thiophenecarhoxaldehyde Hydrazone .................. 53 Preparation of 2-Thienyldiazomethane ..................... 53 Preparation of the Cyclic Trlmer of Prppenthial ......................... 54 SECTION 2 STATEMENT OF THE PROBLEM...................................................................................... 56 HISTORICAL..................................................................................................................... 59 DISCUSSION OF RESUITS............................................................................................. 84 EXPERIMENTAL................................................................................................................ 144 General Procedures and Techniques ........................................................ 146 Preparation of Glyoxylic Acid p-Tosylhydrazone ......................... 146 Preparation of Ethyl o'-Diazothiolacetate ........................................ 146 vi Page Reactions of Ethyl o’-Diazothiolacetate Decomposition in Acidic Methanol ......................................... llj-8 Methanolysis at 65° ........................................................................ 1^8 Photolysis in Methanol .................................................................. 1^9 Decomposition in Glacial Acetic A cid ...................................... 1^9 Decomposition in Trifluoroacetic Acid at 0 ° ........................ 1?0 Decomposition in Silver Nitrate-Acetonitrile-Methanol ... 150 Decomposition in Morpholine ............. 151 Photolysis in 2-Propanol .............................................................. 151 Photosensitization in 2-Propanol .............................................. 152 Photolysis in t-Butanol ............................................................... 153 Photosensitization in t-Butanol ...................................... 153 Decomposition in Acidic 2-Propanethiol ............................... 15^ Photolysis in 2-Propanethlol .......................................... 15^ Photosensitization in 2-Propanethlol ..................................... 155 Photosensitization in Cyclohexane ........................................... 155 Photosensitization in 1,1-Dimethoxyethylene ........................ 156 Photosensitization in Methylenecyclohexane .......................... 157 Preparation of Phenylglyoxylic Acid ^-Tosylhydrazone ............ 159 Preparation of Ethyl a-Diazophenylthiolacetate ......................... 159 Thermolysis of Ethyl a-Dlazophenylthiolacetate in Hexane ... l6l Oxidation of (CioHioSO)s .................................................................... 162 Ammonolysis of (CioHioOS)^ ................................................................ 162 Preparation of a-Thioethoxyphenylacetlc Acid ............................. 165 vii Page Preparation of Phenylthioethoxyketene ............................................. 165 Reactions of Ethyl ctf-Dlazophenylthiolacetate Decomposition in Silver Nitrate - Acetonltrlle and Cuprous Chloride - Acetonitrile . ................................ 166 Methanolysis at 6 5 0 ................................... 168 Decomposition in Acidic Methanol ..............................................
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