Thiocarbonyl compounds Subject

Historically, the first reactions involving thiocarbonyl ylides involve the preparation of thiiranes and 1,3-dithiolanes from diazomethane and thiocarbonyl compounds reported early in the last century by Staudinger and co-workers (12,13). Similar reactions have been smdied by Schonberg and co-workers (14—16) during the 1960s, but neither was the reaction mechanism understood nor have thiocarbonyl ylides been recognized as key intermediates. [For some remarks to this subject see (8) and (10) in (17).]... 

In Section III.K we have briefly summarized the major advances in the preparation of thiocarbonyl compounds stabilized by organometallics. The synthetic applications of this kind of reagents have experienced impressive growth in recent years and major contributions will be collected in this section, although the interested reader is referred to specialized Serials on this subject. 

The photochemistry of organosulfur compounds in general has been the subject both of annual reports [1,2] and of timely scattered reviews [3-5], Light-induced reactions of specific chromophores, such as sulfoxides and sulfones [6], thiocarbonyl compounds [7], and thiols [8] have been discussed in more detail, as has the photochemistry of thiophenes and certain other specific ring systems [9,10],... 

Thiocarbonyl oxides are a subject of active investigation. The natural occurrence of sulfines and related compounds in plants of the genus Allium (onion, garlic, etc.) is included in a superb and extensive review by Block [91]. Two detailed papers [92, 93] report the isolation of zwiebelanes from onions and their chemical synthesis involving intermediate sulfines produced by oxidation of di-l-propenyl disulfide, subsequent sulfoxide accelerated [3.3] sigmatropic shift and the [2+2] cycloaddition of the C=S and C=S=0 moieties. A further article [94] provides a great deal of information on the mechanism of formation of (Z)-propanethial S-oxide, the lachrymatory factor of the onion, as well as its chemical synthesis and reactions. Techniques of analysis of the volatiles of onions have been further improved [95]. 

When compounds 298, using a stoichiometric amormt of diphenylke-tene or methylphenylketene, were subjected to Aza—Wittig reactions, N-[2-alkyl(aryl)thiocarbonyl]phenyl ketenimines 299 was obtained. A/-[2-(Alkyl- or arylthio)carbonyl]phenyl keteriiniines 299 was cychzed under mild thermal conditions to give 2-alkyl(aryl)thio-3H-quinohn-4-ones... 

Poly(thiocarbonyl fluoride) and related fluorothiocarbonyl compounds have been the subject of extensive study in recent years and at least two reviews (Sharkey, 1969 1972) have been devoted to these materials. Commercial production of the material in the near future, however, seems unlikely. 

The hydrogen peroxide oxidation of N-(ethoxycarbonyl)pyrrole-2-thio-carboxamide (225) has been the subject of a recent study by Papadopoulos, who found that in basic media (225) is converted into the corresponding amide, whereas in acidic solution the sulphine (271) is formed. The thiocarbonyl group in (272) [the cyclization product obtained by heating (225) in quinoline] behaved similarly. Several examples of the formation of heterocyclic compounds, especially isothiazole derivatives, by oxidative treatment of appropriate thioamides have appeared. The... 

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