Thiirane tetra-

Chloroethyldisulfides are obtained by electrophilic attack on the sulfur atom of thiiranes by sulfenyl halides (Scheme 39). Sulfur dichloride and disulfur dichloride react similarly to give more sulfur-rich derivatives di- and tri-sulfenyl halides, and tri- and tetra-sulfides (Scheme 42). A 1 1 ratio of sulfur halide to thiirane gives the di- or tri-sulfenyl halide a 2 1 ratio the tri- or tetra-sulfide. Thiirane 1-oxides are cleaved by sulfenyl halides to thiolsulfinates (Scheme 43) (74JAP7440461). 

Some of the more important monomers whose ring opening polymerisations have been induced by stable cation salts include, 1,4-epoxides, notably tetra-hydrofuran (20,112,113), 1,2-epoxides (114), 1,3-episulphides (thietans) (33,53), 1,2-episulphides (thiiranes) (53), azetidines (115,116), aziridines (117), the cyclic formals, 1,3-dioxolan (23,54, 118-120), and 1,3-dioxepan (118,119), trioxane (121,122) and more recently lactones (123). Aldehydes (124) may also be included since these molecules can be regarded as the smallest possible oxygen hetero-... 

Reaction of 3-(4-methoxyphenyl)-2-(W-methyl)benzylamino-5-phenyl-l,3-thiazolium-4-olate 382 with benzalde-hyde or 4-nitrobenzaldehyde in dichloromethane at room temperature gave corresponding thiiranes in 63% and 15% yields (Scheme 111). Reaction of 383 with tetra-O-acetyl-D-arabinose in refluxing benzene for 1 h gave a mixture of thiiranes 384 in 45-50% yield (Scheme 112) <2001TA2265, 2003JOC6338>. 

In one example the process involves loss of nitrogen and a sulfur atom. Thus cyclohexanone is treated with hydrazine and hydrogen sulfide to give the tetra-hydrothiadiazole (1) in quantitative yield. This is then oxidized with lead tetraacetate at 0° to give the azo sulfide (2) in 95% yield. When (2) is heated with triphenylphosphine (1.1 moles) at 100° for one hour, biscyclohexylidene (4) is obtained in 77% yield. The thiirane (3) is an intermediate it has been obtained by pyrolysis of (2).6... 

Although the highly strained bis-thiiran (14) was not obtained on irradiation of 2,5-diphenyl-1,4-dithiin, photolysis of tetra(trifluoromethyl)thio-phen (15) gave the thiiran (16). A previous structure for the product was... 

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