Organic Esters of Bivalent Sulfur. I. Dialkoxy Disulfides

Sulfur monochloride in organic synthesis

“…36,37 Scheme 23 c. Dialkoxy disulfides Dialkoxy disulfides have been known for more than 100 years; however, interest in these compounds is unabated owing to their diverse reactivity. Modern strategy of synthesis of dialkoxy disulfides is based on the method described by Thompson et al 38 These synthetically important compounds are often introduced into further transformations without isolation from the reaction mixture.…”

Reactivity Pattern of Bis(propargyloxy) Disulfides: Tandem Rearrangements and Cyclizations

“…9, 131.8, 128.7, 128.6, 128.4, 128.3, and 122.4 (Ar for four isomers), 88.14 and 88.09 (≡C-each), 88.0 (≡C-for two isomers); 86.9 (≡C-for two isomers), 86.7 and 86.6 (≡C-each); 72.0 (-CH-for two isomers), 70.12 and 70.08 22.7,22.62,22.55, 85.3,85.0,81.8,, 81.0 and 80.9 (≡C-each), 80.6 (≡C-for two isomers); 76. 6,76.3,75.7,and 75.6 (≡CH each),36.3,36.2,36.0, Rearrangement of a-Alkyl-Substituted Bis(propargyloxy) Disulfides; General Procedure Unless otherwise specified, a CHCl 3 soln of the appropriate bis(propargyloxy) disulfide was stirred at r.t. for 21.5 h. 14 This reaction was characterized by the soln turning dark brown in color. The solvent was evaporated under reduced pressure and the residue was purified by chromatography (silica gel).…”

“…It was further reported that the product from propargyl alcohol decomposed below room temperature and that during attempted distillation diallyloxy disulfide disproportionated to acrolein, allyl alcohol, and elemental sulfur. 6 We recently reported in preliminary communications the successful preparation of both diallyloxy 7a,b and bis(propargyloxy) disulfides 7a,c,d in good to excellent yields. This success was putatively attributed to the modified preparative procedure (diethyl ether as solvent, reaction temperature of 0°C, and low-temperature workup), in the course of which the chloride ion produced is precipitated as triethylamine hydrochloride (Scheme 1).…”

“…More recently, the reaction of sulfur monochloride with alcohols in dichloromethane solution in the presence of triethylamine was reported to yield primary and secondary saturated dialkoxy disulfides. 6 However, no pure dialkoxy disulfides of tertiary saturated alcohols were obtained. It was further reported that the product from propargyl alcohol decomposed below room temperature and that during attempted distillation diallyloxy disulfide disproportionated to acrolein, allyl alcohol, and elemental sulfur.…”

A Practical Synthesis of Mixed Allyl and Allenesulfinates

“…4 More recently, this cyclization has also been used as a model for the design of a new class of DNA cleaving molecules which could mimic the biological activity of the naturally occurring enediynes. 5,6 Notwithstanding the previously reported unsuccessful attempts to prepare allylic and propargylic dialkoxy disulfides, 7 we have recently succeeded in the preparation of a variety of such esters in good to high yields. 8,9 Testing the reactivity of allylic dialkoxy disulfides 1a-f we have found that on heating in refluxing acetonitrile solution, these esters readily undergo a double [2,3]-sigmatropic rearrangement to the expected vic-disulfoxides 3a-f, which rearrange further to the corresponding thiosulfonates 4af due to their well known instability (Scheme 2).…”