Preparation of Some Polyfunctional Indenes and Indanones: The Reaction of Mercapto-Substituted Cyclopropenium Salts with Alcohols and Thiols.

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The reaction of 1-methylthio-, 1-(4-methylphenylthio)-, or 1-t-butylthio-2,3-diphenylcyclopropenium salts with alcohols, phenols, and thiols in the presence of triethylamine at around 80°C gave 1H-indene-1-thiol derivatives in fair to moderate yields. In contrast, the same reactions at room temperature afforded 1-alkylthio- or arylthio-1-cyclopropene derivatives together with a small amount of the 3-isomer. Some 1-isomers were separated as pure crystals and produced the corresponding indenes in quantitative yields when heated. Kinetic studies of the ring-opening of cyclopropenes suggested a vinylcarbene intermediate based on the small effects of solvent polarities and phenoxyl substituents on the reaction rates. The reaction of diphenylcyclopropenone with thiol in the presence of trifluoroacetic acid yielded 1H-indene-1,3-dithiol detivatives via a 1,3-bis(alkylthio)-or (arylthio)-1-cyclopropene intermediate. On acidic hydrolysis of 3-alkoxyindenes and on heating of 3-allyloxy- and 3-(2-propynyloxy)indenes, polyfunctionally-substituted indanones were obtained in good yields.
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