37545-44-1

Upstream product

• 937-31-5 (4-Nitrophenyl)acetylene 
• 6111-94-0 1-Tosyl-5-p-nitrophenyl-1,2,3-triazole 
• 6111-97-3 5-(4-nitrophenyl)-1H-1,2,3-triazole 
• 14181-73-8 α-bromomethyl p-nitrophenyl ketoxime 

Relevant academic research and scientific papers

Conversion of enamines, enamides and triazoles by trithiazyl trichloride into 1,2,5-thiadiazoles

Trithiazyl trichloride 1 converts primary and secondary enamines, enamides and 1,2,3-triazoles into 1,2,5-thiadiazoles. These mild reactions provide one-pot routes to various alkyl, aryl, functional and quaternary 1,2,5-thiadiazoles, in moderate to good yields. The trimer 1 reacts as a 1,2-bis-electrophile adding an N-S unit across C=C-N. For primary enamines 15N-labelling reveals an additional, minor pathway in which N-S-N is added across C=C, with elimination of the enamine nitrogen. With N-alkylated enamines the alkyl group is retained in a quaternised thiadiazole, but this can be dealkylated in situ. Enamides react similarly but with spontaneous N-deacylation. 1,2,3-Triazoles with electron withdrawing groups to stabilise their acyclic diazoimine tautomers also give 1,2,5-thiadiazoles, with loss of dinitrogen. Mechanisms are proposed for these new reactions.

Reaction of trithiazyl trichloride with alkenes and alkynes

Alkenes and alkynes react readily with trithiazyl trichloride 1 to give 1,2,5-thiadiazoles 2 in one step. Thus 3-amino-1,2,5-thiadiazole 5 is now readily available from N-vinylphthalimide and 1 in two steps. Cyclic alkenes react similarly to give fused thiadiazoles (7, 12) and phenanthrene gives the phenanthrothiadiazole 16. Tetra-substituted alkenes such as 13 appear to give the analogous 3,4-dihydrothiadiazoles (e.g. 14) which spontaneously ring open to give readily hydrolysed bis(methyleneamino) sulfides (e.g. 15). A simple set of mechanisms is proposed for all of these reactions.

Reactions of Monohalomethyl Aryl Ketoximes with Tetrasulfur Tetranitride: Much Improved Synthesis of 3-Aryl-1,2,5-thiadiazoles

Reactions of chloromethyl aryl ketoximes (1, X = Cl) with tetrasulfur tetranitride in p-dioxane at reflux for 4 h afforded 3-aryl-1,2,5-thiadiazoles (2) in 37-92percent yields, whereas those of bromo analogs under the same conditions gave 2 and 3-aryl-4-bromo-1,2,5-thiadiazoles 3 in 48-81percent and 17-31percent yields, respectively.However, the compounds (3) were not formed in the presence of pyridine. α-Nitrosostyrene and its ring-substituted derivatives (4) are proposed as intermediates for the formations of 2.