Thiolcarbonates

Thiolcarbonic Acid, HS.CO.OH, yields carbon oxysulphide, COS, by decomposition its esters yield alcohols or mereaptans when saponified, according to whether the alkyl group is attached to oxygen or to sulphur by this means the constitutions of the thiocarbonic acids are established. 

Aqueous solutions of the caustic alkalis act only slowly with the oxysulphide to form thiolcarbonates, which, however, soon decompose into carbonate and hydrosulphide ... 

Thiolcarbonic aoid, 266, 268. Thiolthionearbamic acid, 274. Thiolthioncarbonic acid, 266. 

Quantitative relationships have been reported between the global electrophilicity index and the experimental rate coefficients for the reactions of thiolcarbonates and dithio-carbonates with piperidine. The validated scale of electrophilicity was then used to rationalize the reaction mechanisms of these systems. This scale also makes it possible to predict both rate coefficients and Hammett substituent constants for a series of systems that have not been experimentally evaluated to date.48... 

The utility of the [3,3]-sigmatropic rearrangement of eight-membered thionocarbon-ates for the highly stereo-controlled synthesis of Z- or -double bonds in 10-membered thiolcarbonates has been reviewed.5,5-Disubstituted thiotetronic acids (139) have been synthesized using an allylic xanthate (137) to dithiocarbonate (138) rearrangement which has permitted the introduction of a sulfur at a tertiary centre with concomitant deconjugation of the double bond (see Scheme 39). 

The Shonberg rearrangement consists of the thermal rearrangement of diaryl thioncarbonates to diaryl thiolcarbonates,... 

A solution of 1.2 g (1.2 mmol) of 2-methyl-l-penten-3-ol in 10mL of pyridine is cooled to — 20 °C, and 2.2 g (1.28 mmol) of phenyl chlorothionoformate are added with stirring. After 1 h the product is poured into H20, and the organic material is extracted with Et20. The ethereal layers are washed with 2 N NaOH, H20, 3 N HC1, and H20 again. The combined ethereal layers are dried over anhyd Na2S04, and the solvent is evaporated. The residue is distilled to obtain the thiolcarbonate as a pale yellow oil vield 1.77 g (67%) bp 110°C/1 Torr. 

Formation of Thionecarbonates, Thiolcarbonates, Xanthates, Chlorothione-formates, and Carbamates... 

Aromatic thiolcarbonates, e.g. benzo- or naphtho[d]oxathiol-2-ones, behave like aromatic thiol esters on irradiation in undergoing S-acyl bond cleavage followed by CO elimination. If a phenolic OH group is located in para position to the C-O bond, a tautomeric equilibrium hydroxy-keto-thione / 2-mercapto-p-quinone is established [82]. This mercaptoquinone can be trapped with alkenes... 

Full details on the synthesis of 5-thio-D-glucose based on the radical promoted rearrangement of cyclic thionocarbonate 38 to 5,6-S,0-thiolcarbonate 39 have... 

Tetraethylammonium fluoride Thioethers from thiolcarbonic acid esters... 

A soln. of O-methyl S-phenyl thiolcarbonate in acetonitrile containing tetraethylammonium fluoride kept 64hrs. at 35° methyl phenyl sulfide. Y 97%. F. e., catalysts such as trioctylphosphine, and solvents s. F. N. Jones, J. Org. Chem. 33, 4290 (1968). 

Thiocarbonic acid esters s.a. Mono-thiolcarbonic acid esters Trithio-carbonic - -Thiocarbonyl compds. 

S-Acoxysulfides Acyl sulfenates 20 Monothiolcarbonic acid esters Monothiocarbonate esters 40 Thiolcarbonic acid esters 20 Monothioorthocarboxylic -Monothioorthoformic — Sulfenes... 

Thiol-binding centres 645-647 Thiolcarbonates, diaryl, from... 

Carbazic from thiolcarbonic acid esters OGOSR OGONHNH2... 

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