• Interception of the DMF adduct provides a source of the unstable 2-mercaptobenzaldehyde. Alternatively, ortho-metallated thiophenols can be formed by lithiation of the THP ether, in which coordination by oxygen favors ortho-lithiation: J. Am. Chem. Soc., 111, 658 (1989).
• Chlorination of PhSH with NCS: J. Org. Chem., 37, 1367 (1972), or SO2Cl2: Org. Synth. Coll., 8, 550 (1993), gives the useful reagent benzenesulfenyl chloride, PhSCl.
• For a detailed investigation of alkylation using, e.g. K2CO3 in acetone, see: Synth. Commun., 22, 1691 (1992). Unactivated aryl chlorides undergo nucleophilic substitution in the presence of K2CO3 in NMP to give aryl sulfides: J. Org. Chem., 56, 862 (1991).
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Dilithiation of PhSH with n-BuLi and TMEDA gives exclusive ortho-metallation: J. Am. Chem. Soc., 111, 654, 665, 2327 (1989). Subsequent treatment of the dilithio species with DMF, followed by in situ reaction with chloroacetone provides a useful route to the benzo[b]thiophene system: J. Org. Chem., 58, 1293 (1993):
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Michael additions occur readily with electron deficient alkenes. Subsequent chlorination with NCS and dehydrochlorination provides a stereoselective route to vinyl thioethers: J. Org. Chem., 46, 235 (1981):
• The Cu(I) derivative, phenylthiocopper forms complexes with alkyllithiums, which are useful alkyl transfer reagents, undergoing conjugate addition to enones, coupling with alkyl iodides to alkanes, and converting acid halides to ketones: J. Am. Chem. Soc., 95, 7788 (1973); Synthesis, 662 (1974); Org. Synth. Coll., 6, 248 (1988).
剧毒 (T+)