Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
Highly sterically demanding 2,4,6-tri-t-butylphenyllithium (1) reacts with carbon disulfide to give 1,2-dibutylthio-1,2-bis(2,4,6-tri-t-butylphenylthio) ethene (3), l-butylthio-1-(2,4,6-tri-t-butylphenylthio)pent-l-ene (4), and 2-butylthio-3-(2,4,6-tri-t-butylphenylthio)-1,3-dithiole-2-thione (5) when 1 is prepared by the reaction of 1-bromo-2,4,6-tri-t-butylbenzene with n-butyllithium. When the reaction is carried out using 1 prepared from 2 and t-butyllithium and then quenched with l-iodoethane, 2-ethylthio-3-(2,4,6-tri-butylphenylthio)-1,3-dithiole-2-thione and 1,2-diethylthio-1,2-bis(2,4,6-tri-t-butylphenylthio) ethene are produced. The formation of all these products can be explained in terms of initial thiophilic attack of 1 on the sulfur of carbon disulfide and an intermediate with a dual property of carbanion and carbene (i.e., ArSC(Li)(=S) ⇌ ArSC̈SLi) is suggested. The reaction of 1 with thiophosgene affords 1,2-dichloro-1,2-bis(2,4,6-tri-t-butylphenylthio) ethene, bis(2,4,6-tri-t-butylphenylthio)acetylene, and 1-chloro 2,4,6-tri-t-butylbenzene, the first two of which are explained to be formed by thiophilic attack of 1 with thiophosgene.
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