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Please login to access the full content or check if you have access via 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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Meeee Meeee Meeeeeeee Meee (°M) Meeee (%) ee Mee-8-eee Meeee (%) ee Mee-8-eee Mee
M-Meeeee M-Meeeee M-Meeeee M-Meeeee
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Meeee 88 Meeeeeeee ee Meeeeee eeee e Meeeeeee Meeee Meeee ee eee Meeeee Meee[‌888‌]

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]
e-Me Me 88 88 [‌888‌]

Mee eeeeeeeee ee ee eeeeeeeeeee eeeeee eeee ee 8-eeeeeeeee-8,8-eeeeeeeeeeee-8-eee (88) ee eeeeeeeeeeee eeeeeeee eeee 8-eeeeeeeee-8,8-eeeeeeeeeeeeee-8-ee (88) eeeeeee eeeeeeeee ee eee eeeeeeeeeeeee M-eeeee eeeeeeee 88 eee eee eeeeeeeeee eeeeeeeee (Meeeee 88).[‌888‌]

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Meeeee 88 Meeeee Meeeeeeee eeee M-Meeee Meeeeeeeeeeeeeeeeeeeee[‌888‌]

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Meeee 88 Meeeeeeee ee Meeeeeeeeeee ee Meeeeeeee ee Meeeeeeeee Meeeeeeeeeeeeee[‌888‌]

Me8 M8,M8 Meee (°M) Meeee (%) Mee
8-eeeeeeee (MM8)8 888 88 [‌888‌]
8-eeeeeeee (MM8)8MM(e-Me)MM8 888 88 [‌888‌]
8-eeeeeeee MM(eMe)(MM8)8MMMe 88888 88 [‌888‌]
8-eeeeeee (MM8)8 888 88 [‌888‌]
8-eeeeeee (MM8)8MM(e-Me)MM8 888 88 [‌888‌]
8-eeeeeee (MM8)8MM(e-Me)MM8 888 888 [‌888‌]
8-MeMMM8M8 (MM8)8 888888 88 [‌888‌]
8-MeMMM8M8 (MM8)8 888888 88 [‌888‌]

(Meeeeeeeeeeeeeee)eeeeeeeeeeeeeeee eeeeeeeee (eeeee eeee) eeeeee eeeee (88) eeeeee eeee e eeeee eeeeeeee ee eeeeeeee ee eeeeeee eeeee M-(eeeeeeeeeeeeeee)eeeeeeeee eeeeee 88. Meeee eeeeeeeee eeeeee eeeeeee eeeeeeeeeee eee eeeeeeeeeee ee eeee eeeeeee (Meeeee 88).[‌888‌] Me eeee eee, eeeeeeee eee eeeeeeeee eeeeeeee eee eeeeeeeee eeee eeeee eeee: 8,8-eeeeeeeeeeeeee-8-ee eeeee 8-eeeeeeeee-8-eee (88%), 8-eeeeeeeeeeeeeeeee-8-ee eeeeeeee 8-eeeeeeeeeeeeeeeeee (88; 88%), eeeee-8-ee eeeee e eeeeeee ee eee-8-eee (88%) eee eee-8-eee (88%), 8-eeee-eeeee-8,8,8-eeeeeeeeeeeeeee-8-ee eeeee ee 8-eeee-eeeee-8,8,8-eeeeeeeeeeeee-8-eee (88%), eee 8,8-eeeeeeeeeeeeeee eeeeeeeee (M)-eeeeeeee (88%).

Meeeee 88 Meeeeeeeeee ee Meeeeeee eee Meeeeeeeeeee Meeeeeeee Meeeee[‌888‌]

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Meeeee 88 Meeeee Meeeeeeee eeee Meeeeeee eee e Meeeeeeee[‌888‌]

Meeee 88 Meeeee Meeeeeeee eeee Meeeeeee eee e Meeeeeeee[‌888‌]

Meeeeeee Meeeeeee Meeeeee(e) Meeeee (%) Mee
eeeee-8-ee eee-8-eee + (M)- eee (M)-eee-8-eeee 88 + 88 [‌888‌]
eeee-eeeee eeeeeee eeeeeeeee 888 [‌888‌]
8-eeeeeeeeeee-8-ee 8-eeeeeeeee-8-eee + 8-eeeeeeeee-8-eee 88 + 88 [‌888‌]
eeeeeeeeeeee eeeeeeeeeee 888 [‌888‌]
8-eeeeeeeeeeeeeeeee-8-ee 8-eeeeeeeeeeeeeeeeee 888 [‌888‌]
8-eeeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeeeeee + 8-eeeeeeeeeeeeeeeee 88 + 88 [‌888‌]
eee-8-eeeeeeeeeeeeeeeeee 8-eeeeeeeeeeeeeeeee + 8-eeeeeeeeeeeeeeeee 88 + 88 [‌888‌]
eeeee-8-eeeeeeeeeeeeeeeeee 8-eeeeeeeeeeeeeeeee 888 [‌888‌]
eeeeeeeeeeeeeeeeeeeeee (eeeeeeeeeeeeeeeeeeeeee)eeeeeeeeeeee 88e [‌888‌]
eee- eee eeeee-8-eeee-eeeeeeeeeeeeeeeeee (88:88) 8-eeee-eeeeeeeeeeeeeeee 888 [‌888‌]

e Me eeee eeeeeeeeeee ee eeeeeeeeeeeeeeeee.

e Meee MMM eeeeeeee: 88% (eeeeeeeeeeeeeeeeeeeeee)eeeeeeeeeeee eee 88% 8-eeeeee-8,8-eeeeeeeeeeeeeeee-8-eee.

Meeeeeeeeeee Meeeeeeee

Meeeeeeeeee [88, M8,M8=(MM8)8]; Meeeeee Meeeeeeee:[‌888‌]

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

Meee 8-eeeeeeeeeeeeeeeee-8-ee (8.88e, 8.888eee) eee eeeee ee (eeeeeeeeeeeeeeee)eeeeeeeeeeeeeeee eeeeeeeee eeeeee eeeee (8.88e, 8.888eee) ee e 88-eM eeeee-eeeeeeee eeeee eeeeeeeee ee e eeeeeeeeeee eeeeeeeee ee ee eeeee e eeeeee ee eee M8. Meeee 88eee, ee eeeeeeeeee eeeeeeee eeeeee, eee eeeeeee eeeeee eeeeeeeeeee, eee e eeeee, eeeeeeeee eeeeee eeeeeeeee eeee eee eeee eeee. MMM eee MMM eeeeeeee ee eee eeeeeeeeee eeeeee eee eeeeeee eeeeeee ee eee eeee eeeeeeeee; eeeee: 8.88e (88%); 8M MMM (MMMe8, δ): 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (eeeeeee e, 8M), 8.88 (e, 8M).