14731-48-7

Upstream product

• 100-44-7 benzyl chloride 
• 10253-83-5 5-anilino-3H-[1,3,4]thiadiazole-2-thione 
• 79010-52-9 5-S-benzyliso-1-phenyl-2-thiohydrazodicarbonamide 
• 16437-66-4 1-phenyl-2,5-dithiobiurea 
• 10253-83-5 5-phenylamino-3H-[1,3,4]thiadiazole-2-thione 
• 10253-83-5 5-phenylamino-2-mercapto-1,3,4-thiadiazole 
• 57216-15-6 S-Benzylisothiosemicarbazide 
• 2834-31-3 1-butyl-6-phenyl-2,5-dithiobiurea 
• 61784-88-1 1-ethyl-6-phenyl-2,5-dithiobiurea 
• 125908-26-1 1-methyl-6-phenyl-2,5-dithiobiurea 
• 103-72-0 phenyl isothiocyanate 
• 125908-35-2 1-propyl-6-phenyl-2,5-dithiobiurea 

Downstream Products

• 19703-53-8 phenyl-(5-phenylmethanesulfinyl-[1,3,4]thiadiazol-2-yl)-amine 
• 16601-40-4 S-benzyl phenyl-methanethiosulfonate 

Relevant academic research and scientific papers

The route of alkylation of 5-substituted 1,3,4-thiadiazoline-2-thiones

The reaction of 5-anilino(toluidino-, morpholino)-1,3,4-thiadiazoline-2-thiones at 80°C with allyl bromide and benzyl chloride in alcohol, acetonitrile or DMF in the presence of KOH and also with phenoxymethyloxirane in alcohol in the absence of base gives the corresponding novel allyl-, benzyl-, and 2-hydroxy-3-phenoxypropyl products substituted at the exocyclic S atom. Alkylation of the indicated thiones with benzyl chloride at 150-153°C in DMF in the presence of KOH occurs similarly. Under these conditions, allyl bromide forms alkylation products at the endocyclic N(3) atom as a result of an S→N thio-Claisen rearrangement of the initially formed product which is allyl substituted at the exocyclic S atom.

Alkali catalyzed thermal cyclization of 1-substituted and 1,6-disubstituted 2,5-dithiobiureas: Formation of 1,2,4-triazolidine-3,5-dithiones and/or 1,3,4-thiadiazoline-5-thiones

Alkali catalyzed thermal cyclization of 1-alkyl and 1,6-dialkyl-2,5-dithiobiureas (I, R=alkyl, R'=H and R=R'=alkyl) results in the formation of 4-alkyl-1,2,4-triazolidine-3,5-dithiones (V) (alkyl=Me or Et) and 2-alkylamino-Δ2-1,3,4-thiadiazoline-5-thiones (VI) (alkyl=n-Pr or n-Bu).Under the same conditions, 1-alkyl-6-aryl-2,5-dithiobiureas (I, R=alkyl, R'=aryl) give 2-arylamino-Δ2-1,3,4-thiadiazoline-5-thiones (IX) (alkyl=Me, Et, n-Pr or n-Bu) and 4-alkyl-1,2,4-triazolidine-3,5-dithiones (V) also when the alkyl groups are Me or Et.

Oxidation and Eliminative Cyclisation of S-Alkylisodithiobiureas

Isothiocyanates condense with S-alkylisothiosemicarbazides to yield S-alkylisodithiobiureas.These undergo cyclisation to give 3-amino-5-mercapto-4-substituted-1,2,4-triazoles with the elimination of alkyl mercaptan on heating under neutral conditions, whereas under acidic conditions, by elimination of ammonia 5-alkylmercapto-2-substituted amino-1,3,4-thiadiazoles are formed.Condensation of isothiocyanates with thiosemicarbazides in the presence of alkali affords 1-substituted dithiobiureas.Alkylation of these dithiobiureas with alkyl halides results in the formation of 5-alkylmercapto-2-substituted-amino-1,3,4-thiadiazoles, any intermediateproduct not being isolable.On the other hand, oxidation of 1-substituted dithiobiureas with either hydrogen peroxide or iodine furnishes 2-amino-5-substituted-amino-1,3,4-thiadiazoles.