Date of Award

Winter 1985

Project Type


Program or Major


Degree Name

Doctor of Philosophy


Part I. Bis-2-(4'-toluenesulfonyl)methylphenyl disulfide, bis-2-aminophenyl disulfide, 2'-methylsulfonylphenyl 4-toluenesulfonate and N-methyl-N-(2'-aminobenzyl)-4-toluenesulfonamide, all of which appeared capable of undergoing endocyclic nucleophilic substitution at sulfur, were synthesized. Each compound was treated with the strong base (sodium hydride or n-butyllithium) in THF. No trace of the hoped-for base-induced rearrangement products were found. N-methyl-N-(2'-aminophenyl)-4-toluenesulfonamide and some of its derivatives reacted in part with n-butyllithium via an elimination-addition pathway.

Part II. 3-Tosyl-1,2,3-benzoxathiazole-2,2-dioxide and its 5-nitro derivative were synthesized. Their rates of base hydrolysis in aqueous acetonitrile were determined. The reaction of the cyclic sulfamate, 3-tosyl-1,2,3-benzoxathiazole-2,2-dioxide with methylamine and tert-butylamine yielded products arising from ring S-N bond cleavage. Phenyllithium, methyllithium and potassium fluoride gave products from exo S-N bond cleavage. Sodium methoxide yielded products from both exo and endo S-N bond cleavage. An amide synthesis utilizing the cyclic sulfamate as a coupling reagent was also demonstrated.