5-Hydroxy-1,2,3-trithiane

The addition of H2S to an aldehyde or ketone can result in a variety of products. The most usual product is the trithiane (8). ° ot-Hydroxy thiols (5) can be prepared from polychloro and polyfluoro aldehydes and ketones.Apparently, compounds 5 are stable only when prepared from these compounds, and not even for all of them. Thioketones (6) can be prepared from certain ketones, such as diaryl ketones, by treatment with H2S and an acid catalyst, usually HCl. They are often unstable and tend to trimerize (to 8) or to react with air. Thioaldehydes are even less stable and simple ones apparently have never been isolated, though t-BuCHS has been... 

Poly(thioformaldehyde) can also be obtained by reaction of hydrogen sulfide with formaldehyde in acid media (8). Again the key intermediate is 1-hydroxy-2-oxa-4,6-dithioheptane-7-thiol. Though acid conditions favor formation of trithiane, use of a high CH20/H2S04 ratio results only in polymer formation. Credali and Russo (8) believe this to be a topochemical reaction between the dithioheptane and mercaptomethanol. 

A considerable number of electrophiles were used, and the dithiane route found great utility for the syntheses of simple monofunctional compounds as well as for polyfunctional molecules, for which the dithiane moiety affords an invaluable temporary protection of a future carbonyl group. Some experimental procedures published in Organic Syntheses — cyclobutanone [277] and 3-hydroxy-l-cyclohexene-l-carboxaldehyde [278] — are illustrative. A similar route to aldehydes [279] makes use of sym-trithiane as a formyl anion equivalent. 

Trithiane, sym- S-Trithiane 1,3,5-Trithiane (291-21-4), 65, 90 Triton B Ammonium, benzyltrimethyl-, hydroxide Benzenemethanaminium, N.N.N-trimethyl-, hydroxide (100-85-6), 68, 56 Triton X-100 Glycols, polyethylene, mono[p-(1,1,3,3,-tetramethylbutyl)-phenyl]ether Poly(oxy-1,2-ethanediyl), a-(4-(1,1,3,3-tetramethylbutyl)-phenyl]-ci)-hydroxy- (9002-93-1), 68, 56... 

A possible mechanism of this oxidative desulfurization is shown in as Fig. 6, namely, the central sulfur atom in the v-trithiane ring is oxidized to form sulfone, in which an intramolecular nucleophillic rearrangement takes place to give the 1,2-dithiolane ring and SO2. The intermediate, 5-hydroxy-l,2,3-trithiane in this reaction is a new v-trithiane compound. And, as we will mention later, it is a compound of importance as the base of insecticidal active derivatives. As there was no report on the crystal structure of v-trithiane, the stereochemical structure was investigated by X-ray analysis. ... 

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