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The Chemistry of Azasulfonium Salts INFORMATION TO USERS This material 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 if 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. 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Xerox University Microfilms 300 North Zeeb Road Ann Arbor, Michigan 48106 74-17,777 GRUETZMACHER, Gordon Dwight, 1946- THE CHEMISTRY OF AZASULFONIUM SALTS. The Ohio State University, Ph.D., 1974 Chemistry, organic University Microfilms, A XEROX Company , Ann Arbor, Michigan BEE CHEMISTRY OF AZA.SULFONHJM SALTS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University Gordon Gruetzmacher5 B.S. -jf- * # The Ohio S ta te U n iv e rsity 197]l- Reading Committee: Approved Ry Dr. John S. Swenton Dr. Jack Hine Dr. William G. layers Dr. Paul Go Gassman A dviser Department of Chemistry To Patricia ACKNOWLEDGEMENTS The author -wishes to thank Dr. Paul G. Gassman for suggesting this problem., for his many ideas throughout the course of this work, and for many stimulating discussions about chemistry and sundry other topics. To his collegues in chemistry, the author is indebted for their assistance in solving the day to day problems that arise while doing chemical research. To Clinton Harrington, the author leaves without any remorse the Sfaces. Special mention must be made of Rogie Drewes, who was a good friend of, beer drinker with, and screw-off with the a u th o r. * Finally, the author is also deeply grateful to his wife, Pat, for her patience, understanding, and encouragement during the course of his graduate career. VITA Gordon Gruetzmacher, son of Carl H. and Viola Mueller Gruetzmacher, ■was born on November 7, 19^6 in Columbus, Texas. He attended primary and secondary schools in various small towns in South Texas. For two years, September, 1965 thru May, 1967> he attended Del Mar College in Corpus Christi, Texas. In September, 1967 he entered The University of Texas at Austin where he recieved a B. S. in Chemistry in May, 1969- He married Patricia H ill of Sinton, Texas, on August 22, 1969. Ctoe month later, he entered the Graduate School of The Ohio State University. While at Ohio State, he held the positions of teaching assistant and research associate. He recieved his Ph. D. in organic chemistry from The Ohio State University in March of 197^-- TABLE OF CONTEST IS Page ADKN0WLEDGMEN1S.............................................................................................................. i i Y I T A o............................................................................................................................... i i i TABLESrx ILLUS TRATIONS................................................................... x INTRODUCTION................................................................................................................... 1 PART I. Historical .................................................................... 1 PART I I . The Erohlem . ............................................................................. 26 RESULTS AM) DISCUSSION............................... I ............................................................. 35 PART I. The Synthesis, Thermolysis, and Basic Rearrangement of Azasulfonium Salts ............................... 35 PART II. The ortho-ALkylation of Anilines ....................................... 6 k PART III. Die Reaction of Anilines with Halodimethylsulfonium Halides ......................................... 8l EXPERIMENTAL.................................................................................................................... 90 IT-te rt-Butylaniline (80) ..................................................................... 9° N -ter t -Butyl -p -toluid ine ( 8 3) ................................................................... 90 IT -tert -Butyl -chlor oaniline (102) ......................................................... 90 N-tert -Butyl-4-fluoroaniline (97) ........................................................ 90 p-(N-te rt-Butylamino)nitrohenzene (82) ............................................. „ 9° N-te rt-Butylanilinodimethylsulfonium Chloride ( 8 3) ........... 91 IT-te rt-Butyl-p-toluidinodixaethylsulfonium Chloride ( 83.)............. 91 iv Page II-te rt-Butyl-4 -chloroarxilinodimet hv 1sulfonium Chloride ( 8 8) . 92 H-te rt-Butyl-4-f luor oanilinodlme thylsulf onium Chloride ( 8 6 ) . 99 IT-te rt -Butyl -p-t oluidinotetr amethylene sulf onium Chloride (Sg.). ....................................... ............................. 94 N -te rt -Butylanilinodime thylsulf onium Trifluorpacetate (§4).«.. 95 IT-tert -Butyl -p -t oluidinodimethyls ulf onium IT if luor o - a c e ta te (§5.). T .......................................................... 96 IT -te rt -Butyl -4 -chlor oan ilinodiine thylsulf onium Trifluoroaeetate (25.) ........................................................................................ 96 Thermolysis of N-te rt -Butylanilinod ime thylsulf onium Chloride (&£-)............................................................... 96 Thermolysis of N -tert-Butyl-p-toluidinodimethylsulfonium C hloride ( 8 5).. .......................................................................................... 97 Thermolysis of IT -te rt -Butyl -4 -chlor oanilinodime thylsulf onium C h lorid e (88 ) .......................................... '.............................................................. 98 Ihermoly s i s of IT -te r t -Butyl -4 -f luor oanilin odimethyls ulf oni um C hloride ( 8 6 ) ......................................................................................... .... 99 Kinetic Procedure .......................................................................... .................. 100 Thermolysis of IT-tert -Butyl-p-toluidinotetramethylene - _. Sulf onium Chloride (§2.). ............................................................................... 103 Pyrolysis of 4-Chloro-n-butyl-9 -(4-te rt-butylaminotolyl)- sulfide Hydrochloride. .......................... 10J Bis-3-(4-aminotolyl) Disulfide (10£) ............................................ 104 6 -Amino-m-toluenethiol Hydrochloride (108) ................................... .. 104 4-Chloro-n-hutyl-3-(4-aminotolyl) Sulfide (105) .................... 105 N-te rt -Butyl-(N-methy 1thio) -p-toluidine (122.) ........... 106 Sodium Methoxide Rearrangement of N-te rt -Butylanilino- dimethylsulf onium Chloride ( 8j ) ............. 107 v Page Sodium Methoxide Rearrangement of II -te rt - Butyl -u- toluidinodimethylsulf onium Chloride ( 8^ )......... ........................... 108 Sodium Methoxide Rearrangement of IT-te rt-Butyl-4-chloro- an ilin o d im eth y lsu lfo n iu m C hloride IB5JT7" .............................................. 108 Sodium Methoxide Rearrangement of N-te rt-Butyl-7~fluoro- anilinodimethylsuif onium Chloride ^ 8 6 )... ........................................... 109 Sodium Methoxide Rearrangement of IT -te rt -Butylanilino - dimethylsulfonium Trifluoroaeetate 110 Sodium Methoxide Rearrangement of h-tert-Butyl-p- toluidinotetramethylene sulf onium Chloride(82.) ................................... 110 IT-t e r t -B u ty l-o -to lu id in e ( 1 ^ 6 ) ................................................................. I l l IT-te r t-Butyl -2, ^ -xylidine (l^X) ................................................................. 111 ^•-Methoxy-2-(thiomethoxymethyl)aniline (iB j) ...................................... 112 U-Methyl-2-(thiomethoxymethyl)aniline (16^) ........................................ 115 6 2-(Thiomathoxymetbyl)aniline (160) ....................................... H ^ k -Carhoethoxy-2-( thiomethoxymethyl)aniline (178) ............................. 115 4-Chloro-2-(thiomethoxymethyl)aniline (171) .......................................- 116
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