87463-01-2Relevant academic research and scientific papers
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).
A General Strategy for Elaboration of the Dithiocarbonyl Functionality, -(C=O)SS-: Application to the Synthesis of Bis(chlorocarbonyl)disulfane and Related Derivatives of Thiocarbonic Acids
Barany, George,Schroll, Alayne L.,Mott, Andrew W.,Halsrud, David A.
, p. 4750 - 4761 (2007/10/02)
A variety of sulfenyl chlorides have been reacted with a variety of alkoxythiocarbonyl compounds to give adducts which then lose (spontaneously, or upon thermolysis, or in the presence of Lewis acid catalyst) the alkyl chloride to provide an assortment of dithiocarbonyl compounds in good to excellent yields.The preparations of bis(chlorocarbonyl)disulfane (1), ((trichloromethyl)dithio)carbonyl chloride (2), ((alkoxycarbonyl)dithio)carbonyl chlorides (3 and 4), and (((alkylthio)carbonyl)dithio)carbonyl chlorides (5 and 6) by this methodology were optimized; some of the (alkoxydichloromethyl)disulfanyl adducts, e.g., ROCCl2SS(C=O)Cl (10) and ROCCl2SS(C=O)OR'(54), were reasonable stable and could be isolated.All new compounds were characterized by analytical data, 1H and 13C NMR, IR, UV, and mass spectrometry, and high-yield derivatizations with alcohols or N-methylaniline.The reaction with N-methylaniline was also adapted to a rapid, convenient, and precise analytical-scale assay of mixtures of compounds containing acid chloride and/or sulfenyl chloride functionalities.The kinetics, mechanism, and stereochemistry of the dithiocarbonyl synthesis are discussed.
