{"id":{"repo_id":"vt","oai_identifier":"oai:vtechworks.lib.vt.edu:10919/114394"},"canonical_url":"https://search.dev.ndltd.org/etd/vt/oai:vtechworks.lib.vt.edu:10919/114394","repository":{"repo_id":"vt","name":"Virginia Tech","base_url":"https://vtechworks.lib.vt.edu/oai/request"},"display":{"title":"Preparation of N,N'-Dialkyl bis(diamino) diphenylmethanes and N,N'-Dialkyl bis(diamino) benzophenones: preparation of B-hydroxy sulfonamides and B-hydroxy sulfinamides","abstract":"N,N'-Dimethyldiaminodiphenylmethanes and N,N'-dialkyldiaminobenzophenones were successfully prepared from the respective primary amines via alkylation of their methanesulfonamide derivatives. Initially N,N'-diaminodiphenylmethanes and N,N'-diaminobenzophenones were treated 0 with 2.2 equivalents of methanesulfonyl chloride in pyridine at 80° to afford the corresponding bis methanesulfonamide derivatives in 79-91% yields. Alkylation was accomplished by reacting the sulfonamides with 2.2 equivalents of dry potassium hydroxide in hexamethylphosphoramide at 75°, followed by addition of 2.2 equivalents of alkylating agent (methyl iodide, ethyl iodide, and benzyl chloride) to afford 70-84% of the alkylated sulfonamides. Subsequently the N,N'-dialkylsulfonamides were cleanly cleaved using a mixture of concentrated sulfuric/acetic acids (40-60%, vol/vol) to afford N,N'-dimethyldiaminodiphenylmethanes and N,N'-dialkyldiaminobenzophenones in 68-87% and 64-85% yields, respectively. β-Hydroxy sulfonamides were prepared by treating N-methyl methanesulfonanilide with a 10% excess of n-butyllithium in tetrahydrofuran at -78°, followed by addition of benzophenone or acetone to afford the corresponding β-hydroxy sulfonanilides in 76% yield. Upon heating the sulfonanilide-benzophenone adduct in refluxing toluene, water was eliminated to form the corresponding unsaturated sulfonanilide in 89% yield. The attempted preparation of β-hydroxy sulfinamides involved initially the synthesis of N-methanesulfin-p-toluidide following the procedure of Corey and Durst. This compound was subsequently alkylated with sodium hydride and methyl iodide in 1.2-dimethoxyethane in 76% yield. Treatment of the resulting methylated sulfinamide with lithium 0 diisopropylamide at - 78° followed by addition of water, resulted in elimination of the methanesulfine group to afford N-methyl-p-toluidine as the major product.","abstract_html":"N,N'-Dimethyldiaminodiphenylmethanes and N,N'-dialkyldiaminobenzophenones were successfully prepared from the respective primary amines via alkylation of their methanesulfonamide derivatives. Initially N,N'-diaminodiphenylmethanes and N,N'-diaminobenzophenones were treated 0 with 2.2 equivalents of methanesulfonyl chloride in pyridine at 80° to afford the corresponding bis methanesulfonamide derivatives in 79-91% yields. Alkylation was accomplished by reacting the sulfonamides with 2.2 equivalents of dry potassium hydroxide in hexamethylphosphoramide at 75°, followed by addition of 2.2 equivalents of alkylating agent (methyl iodide, ethyl iodide, and benzyl chloride) to afford 70-84% of the alkylated sulfonamides. Subsequently the N,N'-dialkylsulfonamides were cleanly cleaved using a mixture of concentrated sulfuric/acetic acids (40-60%, vol/vol) to afford N,N'-dimethyldiaminodiphenylmethanes and N,N'-dialkyldiaminobenzophenones in 68-87% and 64-85% yields, respectively. β-Hydroxy sulfonamides were prepared by treating N-methyl methanesulfonanilide with a 10% excess of n-butyllithium in tetrahydrofuran at -78°, followed by addition of benzophenone or acetone to afford the corresponding β-hydroxy sulfonanilides in 76% yield. Upon heating the sulfonanilide-benzophenone adduct in refluxing toluene, water was eliminated to form the corresponding unsaturated sulfonanilide in 89% yield. The attempted preparation of β-hydroxy sulfinamides involved initially the synthesis of N-methanesulfin-p-toluidide following the procedure of Corey and Durst. This compound was subsequently alkylated with sodium hydride and methyl iodide in 1.2-dimethoxyethane in 76% yield. Treatment of the resulting methylated sulfinamide with lithium 0 diisopropylamide at - 78° followed by addition of water, resulted in elimination of the methanesulfine group to afford N-methyl-p-toluidine as the major product.","abstract_has_math":false,"creators":["Kahley, Richard Allan"],"institution":"Virginia Polytechnic Institute and State University","degree_name":"M.S.","degree_level":"masters","degree_discipline":"Chemistry","degree_department":"Chemistry","school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1975,"date_issued":"1975","date_published":"1975","updated_at":"2026-07-22T22:18:58Z","subjects":[],"languages":["en"],"rights":["In Copyright"],"rights_urls":["http://rightsstatements.org/vocab/InC/1.0/"],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/10919/114394","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.department","label":"Department","values":["Chemistry"]},{"key":"dc:creator","label":"Author","values":["Kahley, Richard Allan"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2023-04-07T05:16:53Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2023-04-07T05:16:53Z"]},{"key":"dc:date.issued","label":"Date","values":["1975"]},{"key":"dc:publisher","label":"Institution","values":["Virginia Polytechnic Institute and State University"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.dcmitype","label":"Dc Type Dcmitype","values":["Text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["masters"]},{"key":"thesis:degree_name","label":"Degree Name","values":["M.S."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Virginia Polytechnic Institute and State University"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["In Copyright"]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://rightsstatements.org/vocab/InC/1.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/10919/114394"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["N,N'-Dimethyldiaminodiphenylmethanes and N,N'-dialkyldiaminobenzophenones were successfully prepared from the respective primary amines via alkylation of their methanesulfonamide derivatives. Initially N,N'-diaminodiphenylmethanes and N,N'-diaminobenzophenones were treated 0 with 2.2 equivalents of methanesulfonyl chloride in pyridine at 80° to afford the corresponding bis methanesulfonamide derivatives in 79-91% yields. Alkylation was accomplished by reacting the sulfonamides with 2.2 equivalents of dry potassium hydroxide in hexamethylphosphoramide at 75°, followed by addition of 2.2 equivalents of alkylating agent (methyl iodide, ethyl iodide, and benzyl chloride) to afford 70-84% of the alkylated sulfonamides. Subsequently the N,N'-dialkylsulfonamides were cleanly cleaved using a mixture of concentrated sulfuric/acetic acids (40-60%, vol/vol) to afford N,N'-dimethyldiaminodiphenylmethanes and N,N'-dialkyldiaminobenzophenones in 68-87% and 64-85% yields, respectively. β-Hydroxy sulfonamides were prepared by treating N-methyl methanesulfonanilide with a 10% excess of n-butyllithium in tetrahydrofuran at -78°, followed by addition of benzophenone or acetone to afford the corresponding β-hydroxy sulfonanilides in 76% yield. Upon heating the sulfonanilide-benzophenone adduct in refluxing toluene, water was eliminated to form the corresponding unsaturated sulfonanilide in 89% yield. The attempted preparation of β-hydroxy sulfinamides involved initially the synthesis of N-methanesulfin-p-toluidide following the procedure of Corey and Durst. This compound was subsequently alkylated with sodium hydride and methyl iodide in 1.2-dimethoxyethane in 76% yield. Treatment of the resulting methylated sulfinamide with lithium 0 diisopropylamide at - 78° followed by addition of water, resulted in elimination of the methanesulfine group to afford N-methyl-p-toluidine as the major product."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["M.S."]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Preparation of N,N'-Dialkyl bis(diamino) diphenylmethanes and N,N'-Dialkyl bis(diamino) benzophenones: preparation of B-hydroxy sulfonamides and B-hydroxy sulfinamides"]}]}],"canonical_facts":{"dc:contributor.department":["Chemistry"],"dc:creator":["Kahley, Richard Allan"],"dc:date.accessioned":["2023-04-07T05:16:53Z"],"dc:date.available":["2023-04-07T05:16:53Z"],"dc:date.issued":["1975"],"dc:description.abstract":["N,N'-Dimethyldiaminodiphenylmethanes and N,N'-dialkyldiaminobenzophenones were successfully prepared from the respective primary amines via alkylation of their methanesulfonamide derivatives. Initially N,N'-diaminodiphenylmethanes and N,N'-diaminobenzophenones were treated 0 with 2.2 equivalents of methanesulfonyl chloride in pyridine at 80° to afford the corresponding bis methanesulfonamide derivatives in 79-91% yields. Alkylation was accomplished by reacting the sulfonamides with 2.2 equivalents of dry potassium hydroxide in hexamethylphosphoramide at 75°, followed by addition of 2.2 equivalents of alkylating agent (methyl iodide, ethyl iodide, and benzyl chloride) to afford 70-84% of the alkylated sulfonamides. Subsequently the N,N'-dialkylsulfonamides were cleanly cleaved using a mixture of concentrated sulfuric/acetic acids (40-60%, vol/vol) to afford N,N'-dimethyldiaminodiphenylmethanes and N,N'-dialkyldiaminobenzophenones in 68-87% and 64-85% yields, respectively. β-Hydroxy sulfonamides were prepared by treating N-methyl methanesulfonanilide with a 10% excess of n-butyllithium in tetrahydrofuran at -78°, followed by addition of benzophenone or acetone to afford the corresponding β-hydroxy sulfonanilides in 76% yield. Upon heating the sulfonanilide-benzophenone adduct in refluxing toluene, water was eliminated to form the corresponding unsaturated sulfonanilide in 89% yield. The attempted preparation of β-hydroxy sulfinamides involved initially the synthesis of N-methanesulfin-p-toluidide following the procedure of Corey and Durst. This compound was subsequently alkylated with sodium hydride and methyl iodide in 1.2-dimethoxyethane in 76% yield. Treatment of the resulting methylated sulfinamide with lithium 0 diisopropylamide at - 78° followed by addition of water, resulted in elimination of the methanesulfine group to afford N-methyl-p-toluidine as the major product."],"dc:description.degree":["M.S."],"dc:format.mimetype":["application/pdf"],"dc:identifier.uri":["http://hdl.handle.net/10919/114394"],"dc:language.iso":["en"],"dc:publisher":["Virginia Polytechnic Institute and State University"],"dc:rights":["In Copyright"],"dc:rights.uri":["http://rightsstatements.org/vocab/InC/1.0/"],"dc:title":["Preparation of N,N'-Dialkyl bis(diamino) diphenylmethanes and N,N'-Dialkyl bis(diamino) benzophenones: preparation of B-hydroxy sulfonamides and B-hydroxy sulfinamides"],"dc:type":["Thesis"],"dc:type.dcmitype":["Text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["masters"],"thesis:degree_name":["M.S."],"thesis:institution_name":["Virginia Polytechnic Institute and State University"]},"updated_at":"2026-07-22T22:18:58Z"}