REACTION OF α-CHLOROTOLUENE WITH ELEMENTAL SULFUR IN LIQUID AMMONIA

Abstract α-Chlorotoluene (1) reacts with elemental sulfur in liquid ammonia affording dibenzyl disulfide (2), dibenzyl trisulfide (3), dibenzyl tetrasulfide (4), dibenzyl pentasulfide (5) and benzylidene benzylimide (6) at a low temperature such as 20°C. This reaction is presumed to be initiated by the nucleophilic attack of ammonium thioaminohydroxylate, “H2NS-NH4 +,” or dithioaminohydroxylate, “H2NSS-NH4,” formed upon treating elemental sulfur in liquid ammonia, on α-chlorotoluene (1). Benzylidene benzylimide (6) is presumed to be formed from benzylamine, which can be formed by treatment of α-chlorotoluene (1) with ammonia.

[1]  S. Ōae,et al.  REACTION OF 4-CHLORONITROBENZENE WITH ELEMENTAL SULFUR IN LIQUID AMMONIA , 1979 .

[2]  S. Ōae,et al.  REACTION OF AROMATIC NITRO COMPOUNDS WITH ELEMENTAL SULFUR IN LIQUID AMMONIA AND AMINES , 1979 .

[3]  S. Ōae,et al.  Reaction of 4-Nitrobenzenesulfenamide with Liquid Ammonia , 1978 .

[4]  S. Ōae.  Organic Chemistry of Sulfur , 1977 .

[5]  Y. Sasaki,et al.  Reactions of Benzylamine with Sulfur , 1971 .

[6]  J. Bunnett,et al.  Evidence for a radical mechanism of aromatic "nucleophilic" substitution , 1970 .

[7]  C. E. Farley,et al.  Organophosphorus thio esters from disulfides and primary and secondary phosphines , 1967 .

[8]  O. Gawron,et al.  pH Effects on the Kinetics of the Cystine-Cyanide Reaction , 1964 .

[9]  G. Gorin,et al.  Mercaptan—Disulfide Interchange Reactions. II. Some Equilibrium Constants1 , 1964 .

[10]  R. Hiskey,et al.  Chemistry of Aliphatic Disulfides. II.1Cyanide Cleavage of Unsymmetrical Disulfides2 , 1961 .

[11]  J. Swan,et al.  234. Syntheses of thio-oxamides and thioamides by extensions of the Kindler reaction , 1961 .

[12]  J. King,et al.  Studies on the Willgerodt reaction; a mechanism for the primary thiol oxidation. , 1948, Journal of the American Chemical Society.

[13]  C. Willgerodt.  Ueberführung von Ketonen und Aldehyden in Säuren und Säureamide mittelst gelben Schwefelammoniums , 1888 .

[14]  C. Willgerodt.  Ueber die Einwirkung von gelbem Schwefelammonium auf Ketone und Chinone , 1887 .