Novel Symmetrical and Mixed Carbamoyl and Amino Polysulfanes by Reactions of (Alkoxydichloromethyl)polysulfanyl Substrates with N-Methylaniline

Alayne L. Schroll, George Barany, Alayne L. Schroll

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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 [RO(C—S)]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[2-propoxy(thiocarbonyl)] sulfide (27c) with sulfuryl chloride in the presence of calcium carbonate conveniently gave distillable bis(chlorocarbonyl)trisulfane (14), whereas the same procedure with SO2C12 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 4 directly (eq 5).

Original languageEnglish (US)
Pages (from-to)1866-1881
Number of pages16
JournalJournal of Organic Chemistry
Issue number10
StatePublished - Jan 1 1986


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