89264-59-5Relevant academic research and scientific papers
Synthesis and Characterization of (Methoxy(thiocarbonyl))sulfenyl Chloride
Schroll, Alayne L.,Eastep, Steven J.,Barany, George
, p. 1475 - 1479 (2007/10/02)
(Methoxy(thiocarbonyl))sulfenyl chloride (1), a previously elusive compound, has now been generated by cleavage of methoxy(thiocarbonyl) N-methyl-N-phenylamino sulfide (7) with gaseous hydrogen chloride.The sulfenyl chloride 1 had limited stability and was characterized by trapping with O,O'-dimethyl thiocarbonate or with methanethiol to yield (methoxycarbonyl)(methoxy(thiocarbonyl))disulfane (8) or (methoxy(thiocarbonyl))methyldisulfane (9), respectively.Chlorination of acetyl methoxy(thiocarbonyl) sulfide (6) could be arrested at 1 plus acetyl chloride, and further chlorination of 1 provided (methoxydichloromethyl)disulfanyl chloride (5).
Novel Symmetrical and Mixed Carbamoyl and Amino Polysulfanes by Reactions of (Alkoxydichloromethyl)polysulfanyl Substrates with N-Methylaniline
Schroll, Alayne L.,Barany, George
, p. 1866 - 1881 (2007/10/02)
Reactions of (alkoxydichloromethyl)polysulfanes with N-methylaniline can be rationalized by a "carbamoyl" route where the alkoxydichloromethyl group behaves via loss of alkyl chloride as a "masked" acid chloride or by a "sulfenyl" route which reflects fragmentation of the (alkoxydichloromethyl)polysulfanyl functionality into the corresponding alkoxy(thiocarbonyl) and sulfenyl components (cf.Scheme I).Application of this and related chemistry to bifunctional substrates arising from partial or complete chlorination of 2Sm, R = Me, Et, i-Pr, and m = 1-4, has led to Ph(Me)N(C=O)Sn(C=O)N(Me)Ph, n = 2-12; Ph(Me)N(C=O)SnN(Me)Ph, n = 1-6; Ph(Me)NSnN(Me)Ph, n = 1-10; RO(C=S)Sn(C=O)N(Me)Ph, n = 2, 3; and RO(C=S)SnN(Me)Ph, n = 1-5.These families allowed a test of reversed-phase high-pressure liquid chromatography for evaluating homologies in polysulfane series.Treatment of bis sulfide (27c) with sulfuryl chloride in the presence of calcium carbonate conveniently gave distillable bis(chlorocarbonyl)trisulfane (14), whereas the same procedure with SO2Cl2 alone gave directly (chlorocarbonyl)disulfanyl chloride (12) (see Scheme VII).Higher Cl(C=O)SmCl, m = 3-5, were indicated but could not be isolated in the course of studies generalizing results on 14 to the preparation of higher Cl(C=O)Sn(C=O)Cl, n = 4-6.The new bis(carbamoyl) monosulfide 61 was obtained by the relatively slow triphenylphosphine or cyanide promoted desulfurization of bis(methylphenylcarbamoyl)disulfane (4) (eq. 1 and 4); cyanide treatment of the higher polysulfanes Ph(Me)N(C=O)Sn(C=O)N(Me)Ph for n > 3 rapidly gave disulfane directly (eq 5).
