100244-53-9Relevant articles and documents
Synthetic routes to, transformations of, and rather surprising stabilities of (N-Methyl-N-phenylcarbamoyl)sulfenyl Chloride, ((N-Methyl-N-phenylcarbamoyl) dithio)carbonyl chloride, and related compounds
Schrader, Alex M.,Schroll, Alayne L.,Barany, George
experimental part, p. 7882 - 7892 (2011/12/14)
(Figure presented) The title compound classes, (carbamoyl)sulfenyl chlorides and ((carbamoyl)dithio)carbonyl chlorides, have been implicated previously as unstable, albeit trappable, intermediates in organosulfur chemistry. The presentwork reports for each of these functional groups: (i) several routes to prepare it in the N-methylaniline family; (ii) its direct structural characterization by several spectroscopic techniques; (iii) its rather unexpected stability and its ultimate fatewhen it decomposes; (iv) a series of further chemical transformations that give highly stable derivatives, each in turn subject to thorough characterization. Relevant kinetic and mechanistic experiments were carried out, including some with p-methyl- and 2,6-dimethyl-substituted N-methylanilines. Given that the title compounds can be isolated and are relatively stable, they may find applications in the preparation of thiolyzable and/or photolabile protecting groups for the sulfhydryl function of cysteine and for the development of new protein synthesis and modification reagents
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).
