Abstract
IRRADIATION of solutions of diphenylamine with ultraviolet light effects cyclization to carbazole in good yield1. It was of interest to determine if diphenyl sulphide would similarly afford 9-thiafluorene, some polymethyl derivatives of which were required. In the event, reaction took a different course, and benzene and diphenyl disulphide were produced. Trace amounts of diphenyl were also detected by gas-liquid chromatography but none of the desired 9-thiafluorene was found. The diphenyl disulphide (m.p. and mixed m.p. 57°–59°) was separated from unchanged sulphide by preparative gas-liquid chromatography; benzene was detected by gas-liquid chromatography but was not isolated. The following mechanism is adequate, assuming initial cleavage into free radicals as postulated in another case2. Free radical formation is energetically possible with light of wave-length less than 3900 Å taking the energy of the carbon–sulphur bond to be about 73 kcal/mole (ref. 3).
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CARRUTHERS, W. Photolysis of Organic Sulphides. Nature 209, 908 (1966). https://doi.org/10.1038/209908a0
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DOI: https://doi.org/10.1038/209908a0
