Novel symmetrical and mixed carbamoyl and aminopolysulfanes by reactions of (alkoxydichloromethyl)polysulfanyl substrates with N-methylaniline

Crystal structures of (N-methyl-N-phenylamino)(N-methyl-N-phenylcarbamoyl)sulfide and the corresponding disulfane

“…As part of a multifaceted program in synthetic and mechanistic organosulfur chemistry (Barany et al, 1983;Barany & Mott, 1984;Schroll & Barany, 1986;Schrader et al, 2011, and references cited therein), we frequently encounter challenging-to-characterize compounds with one or more reactive acid chloride and/or sulfenyl chloride moieties. These are converted to the corresponding stable carbamoyl and/or sulfenamide derivatives, which are often crystalline, through their reliable, rapid, and high-yield reactions with N-methylaniline.…”

“…The title compounds are derived respectively from (chlorocarbonyl)sulfenyl chloride and (chlorocarbonyl)disulfanyl chloride, which are noxious, distillable liquids. They are the first two members of a general family of compounds with the structure Ph(Me)N(C O)S n N(Me)Ph, in which the higher members (n = 3-6) were found, but not isolated in crystalline form, as components in the reactions of in situ generated (2-propoxydichloromethyl)(chlorocarbonyl)polysulfanes with N-methylaniline (Schroll & Barany, 1986).…”

“…To prepare compound (II), a solution of (chlorocarbonyl)-disulfanyl chloride (Schroll & Barany, 1986) (814 mg, 5.0 mmol) in CH 2 Cl 2 (15 mL) was added over 10 min to a stirred solution of N-methylaniline (2.2 mL, 20 mmol) in CH 2 Cl 2 (11 mL) at 273 K. The homogeneous reaction mixture was allowed to warm to 298 K, stirred an additional 30 min, and standard extractive workup [compare to procedure above for (I)] gave the product as a brown oil (1.44 g, 94% crude yield). The crude product was purified by flash column chromatography, eluting with hexane-ethyl acetate (8:1), to provide a yellow oil (1.37 g), which after storing under hexanes at 253 K overnight produced the title product as an offwhite solid (757 mg, 2.5 mmol, 50%), m.p.…”

Experimental and theoretical studies on bis(chlorocarbonyl)trisulfane, ClC(O)SSSC(O)Cl

“…ClC(O)SSSC(O)Cl was prepared as reported previously [12], with a slight modification: in this work 10 mmol of (CH 3 ) 2 CHOC(S)SC-(S)OCH(CH 3 ) 2 were dissolved in 10 mL of hexane instead of petroleum ether, used in Ref. [12].…”

“…Attempts to isolate this compound by short-path distillation at high vacuum were unsuccessful. In a later work ClC(O)SSSC(O)Cl was isolated by chlorination in petroleum ether of bis[2-propoxy(thiocarbonyl)] sulphide in the presence of catalytic calcium carbonate, being the only characterization presented for this compound the 13 C NMR signal at d = 163.0 ppm [12]. In this work ClC(O)-SSSC(O)Cl have been synthesized, and extensively studied by vibrational spectroscopy including matrix isolation photochemistry and mass spectra complemented by quantum chemical calculations.…”