Chlorination of benzylic sulfides with N-chlorosuccinimide

Chlorine-water Oxidation of Some α-Methylsulfonyl Sulfides

“…Research has been primarily directed at the chlorination of sulfides (1)(2)(3)(4)(5)(6) and sulfoxides (7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19). Our own work (20,21) has demonstrated that a-chlorodialkyl sulfides give rise to sulfonyl chlorides via sulfinyl chlorides upon chlorinatioil in dilute aqueous acetic acid.…”

“…Pummerer rearrangement of intermediate chlorosulfonium chloride salts is directed to C-3 by the a-sulfonyl group (22) thus preventing chlorination on C-5, so that the polyphenylmethyl groups retain their ability to form carbonium ions (or intimate ion pairs) as the reaction proceeds. Secondly the regular increase of the number of phenyl groups on C-5 in the series 1 + 3 increased the propensity for cleavage at progressively earlier stages during the reaction in the event that some Pummerer rearrangement preceded cleavage in the reaction of the phenylmethyl sulfide (1).…”

Synthetic approaches to the thiathromboxanes. Part 1. Preparation of functionalised dihydrothiopyrans

“…C8H,,0,S requires C, 47.5; H, 4.9%); 6,(CD3-COCD,, 80 MHz), 5.85 (2 H, m), 3.85 (0.25 H, d, J 43 Hz), 3.54(0.75H,d, J3.5Hz),3.20(1 H,m),3.19(2H,m),and2.56(2 H, d, J7.5 Hz). The acid (13) was dissolved in Ac20 and after 4 h the mixture was evaporated to give the anhydride (16) (b) If the acidified solution from hydrolysis of the triester (6) (323 mg) (previous experiment) was boiled under reflux for 20 min and then worked up as described, a mixture of the cis-and trans-dicarboxylic acids (13) (176 mg) was obtained as a yellow oil which solidified with time, G,(CDCI,, 60 MHz) 5.92 (2 H, m), 3.87 and 3.54 (d, J4.3 and 3.5 Hz respectively), 3.14 (3 H, m), and 2.58 (2 H, m). The same mixture was obtained when the acid (11) was heated at 130 "C. Dissolution of the mixture in Ac,O gave a cis-and trans-anhydride mixture.…”

Synthesis of a new thermally‐curable elastomer via regioselective chlorination of a polyimidosulfide

“…In this note, we report the successful application of eqs. (2) and (3) to the synthesis of 4 and the adaptation of eq. (3) to the preparation of a thermally crosslinkable polyimidosulfide.…”

“…Migration of the chloro group of the resulting intermediates 6 would afford a-chlorosulfides 7, poised for dehydrochlorination to oxidized specis 4 [eq. (3)]. In this note, we report the successful application of eqs.…”