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.
","abstract_html":"<p>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.</p><p>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.</p>","abstract_has_math":false,"creators":["CHUMPRADIT, SUMALEE"],"institution":null,"degree_name":"Doctor of Philosophy","degree_level":"Dissertation","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1985,"date_issued":"1985-01-01T08:00:00Z","date_published":"1985-01-01T08:00:00Z","updated_at":"2026-07-24T05:23:21Z","subjects":["Chemistry","Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://scholars.unh.edu/dissertation/1465","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["CHUMPRADIT, SUMALEE"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry","Organic"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://scholars.unh.edu/dissertation/1465"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["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.
"]},{"key":"dc:title","label":"Title","values":["PART I: INVESTIGATION OF ENDOCYCLIC NUCLEOPHILIC SUBSTITUTION AT DI- AND TETRA-COORDINATE SULFUR PART II: SYNTHESIS OF 3-TOSYL-1,2,3-BENZOXATHIAZOLE-2,2-DIOXIDE AND ITS REACTIONS WITH NUCLEOPHILES"]}]}],"canonical_facts":{"dc:creator":["CHUMPRADIT, SUMALEE"],"dc:description.abstract":["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.
"],"dc:identifier":["https://scholars.unh.edu/dissertation/1465"],"dc:subject":["Chemistry","Organic"],"dc:title":["PART I: INVESTIGATION OF ENDOCYCLIC NUCLEOPHILIC SUBSTITUTION AT DI- AND TETRA-COORDINATE SULFUR PART II: SYNTHESIS OF 3-TOSYL-1,2,3-BENZOXATHIAZOLE-2,2-DIOXIDE AND ITS REACTIONS WITH NUCLEOPHILES"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Doctor of Philosophy"]},"updated_at":"2026-07-24T05:23:21Z"}