XXIX.—The action of chlorine on organic thiocyanates. Part I. Methyl thiocyanate

Abstract

THE actlion of chlorine on methyl thiocyanate was first investigated by Cahours (Annalen, 61, 96), who found that cyanuric chloride and a heavy oil were formed ; some time later, in 1854, Riche studied the reaction more closely (Annalen, 92, 357).

Cleavage of the Carbon-Sulfur Bond in Divalent Sulfur Compounds.

“…/~SSCN + CeHiNH, heat Chlorination of methyl thiocyanate under anhydrous conditions leads to a mixture of CSC14, CSC12, CCh, and SC12 (79,222).…”

The Chemistry of Thiophosgene

“…46 A mixture of trichloromethanesulfenyl chloride and phosphorus is heated under a nitrogen atmosphere until the phosphorus melts. The slurry thus obtained is heated in Downloaded by [Carnegie Mellon University] at 16:08 02 February 2015 6 , SAlYAVAN SHARMA chlorobenzene in the presence of iodine at 130 °C to yield 91% of thiophosgene which is isolated from the crude mixture after hydrolysis.…”

“…SCHEME 12 Aliphatic and aromatic primary amino compounds containing a carbon-carbon double bond also react preferentially with thiophosgene to form the corresponding isothiocyanates. 245 -252 Thus, reaction of 3-aminomethylene-oL-camphor (42) with thiophosgene affords 3-isothiocyanatomethylene-oL-camphor (43) Reaction of 1-aminocyclohexanecarboxylic acid (44), representing a primary amine having another reactive group in its vicinity, with thiophosgene gives rise to the formation of the unstable 4-oxo-2-thioxo-3-oxa-1-azaspiro [ 4,5] decane ( 45) which, on treatment with aniline in situ, affords 1-aminocyclohexanecarboxanilide (46) and the N,N'-disubstituted thiourea (47) Japelj and coworkers 254 -256 have extended the above reaction to phenylglycine (48) and obtained 4-phenylthiazolidin-2,5-dione ( 49). Contrary to this observation, Sato 257 isolated 5-oxo-4-phenyloxazolidine-2-thione (50) when D-( + )-phenylglycine ( 48) was allowed to reflux with thiophosgene in a 1:1 mixture of dioxan and tetrahydrofuran for 3 hrs.…”

The Chemistry Of Trichloromethanesulfenyl Chloride

“…The formation of trichloromethanesulfenyl chloride has been observed during the chlorination of dimethyl sulfide (25), methyl thiocyanide (35), and carbon sulfidoselenide (12). From the preparative standpoint none of these reactions are of importance, and all methods in present use are based on Rathke's original reaction (64) in which carbon disulfide is treated with chlorine in the presence of a catalytic quantity of iodine at a temperature below 30°C.…”