Chemistry of sulfines. Part IV: Reaction with halogens, tetrachloro-ortho-quinone, triphenylphosphine and water†‡

The addition of chlorine and bromine to 2-methoxynaphthalene-1-thial-S-oxide (II) yields the dichloride and dibromide (IVa and b). The dichloride gives upon treatment with triethylamine 2-methoxythionaphthoyl chloride-S-oxide (V). Similarly, thiobenzaldehyde-S-oxide (prepared in situ) was converted into cis- and trans-thiobenzoyl chloride-S-oxide (scheme B). Tetrachloro-ortho-quinone reacted with xanthione-S-oxide (IX) and thiofluorenone-S-oxide (I) yielding 1:1 adducts (X and XI) in which the α-dioxo part of the quinone had acted as diene. The reduction of the sulfine I with triphenylphosphine gave initially the thioketone, which reacted further with the phosphine as outlined in scheme D. The same reaction was carried out with the thial-S-oxide II. The acid catalyzed hydrolysis of thioketone-S-oxides gave rise to the formation of the corresponding ketones (scheme E).

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