From thioketones

The preparation of thiiranes is most conveniently performed in solution. However, there are also protocols reported for reaction in the gas and solid phase. By using diazo and thiocarbonyl compounds in ether as solvent, both alkyl and aryl substituted thiiranes are accessible. As indicated earlier, aryl substituents destabilize the initially formed 2,5-dihydro-1,3,4-thiadiazole ring and, in general, thiiranes are readily obtained at low temperature (13,15,35). On the other hand, alkyl substituents, especially bulky ones, enhance the stability of the initial cycloadduct, and the formation of thiiranes requires elevated temperatures (36 1,88). Some examples of sterically crowded thiiranes prepared from thioketones and a macro-cyclic diazo compound have been published by Atzmiiller and Vbgtle (106). Diphenyldiazomethane reacts with (arylsulfonyl)isothiocyanates and this is followed by spontaneous N2 elimination to give thiirane-2-imines (60) (107,108). Under similar conditions, acyl-substituted isothiocyanates afforded 2 1-adducts 61 (109) (Scheme 5.23). It seems likely that the formation of 61 involves a thiirane intermediate analogous to 60, which subsequently reacts with a second equivalent... 

When enamines are employed as sulfene traps, thiete 1,1-dioxides (e.g. 142) can be prepared by subsequent Hofmann elimination of amine. An alternative route to thiete 1,1-dioxides involves trapping sulfenes with ynamines, as illustrated by preparation of (144) (73S534). Certain thietes such as (145) (80LA873, 78TL3617, 78TL4839) are available directly from thioketones by 2 + 2 photocycloaddition with alkynes. 

It must be noted that this selective synthesis of enethiols from thioketones is restricted to cases for which regio- and stereoselective deprotonation occurs, as was achieved above with the symmetrical thiones (2a)-(2d). 

Germylenes can be generated either thermally or photochemically438 and, apart from thioketones, they have been reacted with thioketenes to afford initially... 

Cyclocondensations. The cyclopropanation of conjugated sulfones with dimethyl-sulfoxonium methylide generated under PTC conditions is higher yielding than employing the r-BuOK-DMSO system. Related to the the well-known dichlorocyclo-propanation is the formation of 2,2-dichloroepisulfides from thioketones. ... 

Peroxyacetic acid s. under H20 /0HgCOOH Peroxyphthalic acid Sulfines from thioketones... 

Hydrogen peroxide acetic acid HiOjCHgCOOH Sulfines from thioketones C S C S O with peroxyphthalic acid cf. 21, 130 with aq. in acetic acid, f. reactions of thioketones, s. A. Ohno et al., Chem. Lett. 1975, 983 ... 

A degassed soln. of 2,2-dimethyl-l-p-tolylpentane-l-thione in benzene irradiated 26 hrs. with a 450 w. medium-pressure Hg-arc in an evacuated Pyrex tube, the solvent-free intermediate (conversion ca. 95%) dissolved in glacial acetic acid, treated with mercuric acetate, and stirred 0.5 hr. at room temp. 5,5-dimethyl-1-p-tolylcyclopentene. Y 65%. F. de Mayo and R. Suau, Soc. Perkin I 7974, 2559 cyclopropanethiols from thioketones s. A. Couture, M. Hoshino, and P. de Mayo, Chem. Commun. 1976, 131. 

Synthesis of ethylene derivatives from thioketones and diazo compounds via sulfido compounds... 

Irradiation oxygen Ketones from thioketones by singlet oxygen... 

N-Sulfonylthion S-imides from thioketones N-Sulfonyldithiocarboxylic acid ester S4mides from dithiocarboxylic acid esters... 

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