The action of sulphur monochloride on 2-acyl-1,1-dimethylhydrazines; the formation of tetrazans and oxadiazolines

Abstract

The 1,3,4-oxadiazotine is not isolable, since under the conditions of the reaction it will be converted into the C.

Reactions of sulfur monochloride with some aromatic aldehyde semicarbazones and thiosemicarbazones: New syntheses of substituted 2,4‐dihydro‐1,2,4‐triazol‐3‐ones, 2,4‐dihydro‐1,2,4‐triazole‐3‐thiones and 2‐amino‐1,3,4‐oxadiazoles

“…At last, the thiosemicarbazone 13 in acetic acid at room temperature reacted immediately with sulfur monochloride to give the 2-dimethylamino-5-phenyl-l,3,4thiadiazole (14).According to previous works[5], this pathway would afford N-chlorodithio compounds. With semicarbazones or thiosemicarbazones, sulfur monochloride could give an anion which would present two contributing forms A and B when R2 is different from H and four contributing forms A, B, C and D when R2 is an hydrogen (Scheme 111).…”

“…For example, sulfur monochloride gives aminodisulfides with primary and secondary amines [ 1,2], diamidosulfides with primary amides [3], the 3,4,7,8-tetramethyl-1,2,5,6,-3,4,7,8-tetrathiatetrazocine with the 1,2-dimethylhydrazine [4] and a mixture of tetrazans and 1,3,4-oxadiazolines with 2-acyl-1,l-dimethylhydrazines [5].A proposed mechanism for these last reactions [5] involves N-(or 0)-chlorodithio compounds as intermediates which can either undergo duplication or heterocyclization, depending on the thermodynamic criteria bound to their structure. With thiosemicarbazones, the products are derivatives either of the 2-amino-1.3.4 thiadiazole or of the 2,4-dihydro-l,2,4-triazole-3-thione depending on the experimental conditions.…”

“…For example, sulfur monochloride gives aminodisulfides with primary and secondary amines [ 1,2], diamidosulfides with primary amides [3], the 3,4,7,8-tetramethyl-1,2,5,6,-3,4,7,8-tetrathiatetrazocine with the 1,2-dimethylhydrazine [4] and a mixture of tetrazans and 1,3,4-oxadiazolines with 2-acyl-1,l-dimethylhydrazines [5]. For example, sulfur monochloride gives aminodisulfides with primary and secondary amines [ 1,2], diamidosulfides with primary amides [3], the 3,4,7,8-tetramethyl-1,2,5,6,-3,4,7,8-tetrathiatetrazocine with the 1,2-dimethylhydrazine [4] and a mixture of tetrazans and 1,3,4-oxadiazolines with 2-acyl-1,l-dimethylhydrazines [5].…”

“…A proposed mechanism for these last reactions [5] involves N-(or 0)-chlorodithio compounds as intermediates which can either undergo duplication or heterocyclization, depending on the thermodynamic criteria bound to their structure.…”

“…J. Heterocyclic Chem., 23, 881 (1986).A few works on the reactions of sulfur monochloride with some nitrogen compounds have been investigated. For example, sulfur monochloride gives aminodisulfides with primary and secondary amines [ 1,2], diamidosulfides with primary amides [3], the 3,4,7,8-tetramethyl-1,2,5,6,-3,4,7,8-tetrathiatetrazocine with the 1,2-dimethylhydrazine [4] and a mixture of tetrazans and 1,3,4-oxadiazolines with 2-acyl-1,l-dimethylhydrazines [5].A proposed mechanism for these last reactions [5] involves N-(or 0)-chlorodithio compounds as intermediates which can either undergo duplication or heterocyclization, depending on the thermodynamic criteria bound to their structure.…”