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47.1.4.5.3 Variation 3: Pyrolysis of Xanthates, Thiocarbamates, Thiophosphates, Arenesulfonates, Sulfamates, and Sulfuranes

DOI: 10.1055/sos-SD-047-00322

Kostikov, R. R.; Khlebnikov, A. F.; Sokolov, V. V.Science of Synthesis, (201047816.

The formation of alkenes upon the pyrolysis of xanthates, commonly called the Chugaev reaction, has been somewhat more widely used for synthetic purposes than the pyrolysis of esters, a reaction that it closely resembles. The Chugaev alkene synthesis includes the following steps (see also HoubenWeyl, Vol. 5/1b, pp 129134): (1) Reaction of an alcohol with carbon disulfide and sodium or potassium hydroxide to give the corresponding salt of an O-alkyl dithiocarbonate. (2) Alkylation of this salt with iodomethane or -ethane to give the O-alkyl S-methyl (or ethyl) xanthate. By far the most commonly used xanthate is the S-methyl derivative. (3) Thermal decomposition of the xanthate to give an alkene, carbon oxysulfide, and methane- or ethanethiol (Scheme 27).

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M-Meeeee M-Meeeee M-Meeeee M-Meeeee
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M8 M8 Meeee (%) Mee
Meee 88 Meee 88
e-Me M 88 88 [‌888‌]
MMe8Me M 88 88 [‌888‌]
e-Me Me 88 88 [‌888‌]
MMe8Me Me 88 88 [‌888‌]
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Me8 M8,M8 Meee (°M) Meeee (%) Mee
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8-eeeeeeee (MM8)8MM(e-Me)MM8 888 88 [‌888‌]
8-eeeeeeee MM(eMe)(MM8)8MMMe 88888 88 [‌888‌]
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Meeeeeee Meeeeeee Meeeeee(e) Meeeee (%) Mee
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8-eeeeeeeeeee-8-ee 8-eeeeeeeee-8-eee + 8-eeeeeeeee-8-eee 88 + 88 [‌888‌]
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Meeeeeeeeee [88, M8,M8=(MM8)8]; Meeeeee Meeeeeeee:[‌888‌]

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8-Meeeeeeeeeeeeeeeee (88); Meeeeee Meeeeeeee:[‌888‌]

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References