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2-(Diphenylphosphino)benzoic acid, isolated as the ester, was obtained by the photostimulated reaction of 2-chlorobenzoate ion with Ph2P- ions in good yield in liquid ammonia. The reaction did not occur in the dark; it was inhibited by m-dinitrobenzene and partially inhibited by a radical trap such as TEMPO. The results were consistent with the SRN1 mechanism. No evidences for aromatic nucleophilic substitution (SNAr) or benzyne mechanisms were found. [ABSTRACT FROM AUTHOR]

The synthetic scope of the reactions between benzenethiolate, 4-methoxybenzenethiolate, 2-naphthalenethiolate, and 2-pyridinethiolate anions with 1,3-dihalo-2,2-dimethylpropane was studied. These reactions render mono and disubstituted products from good to excellent yields. For all the substrates studied the monosubstituted halogenated product is the intermediate or the main product depending on the nature of the second leaving group. Aryl cyclopropyl sulfides were found as side products and their yields strongly depend on the base concentration (tert-BuOK). Finally, using neopentyl iodide as a model, the mechanism of these reactions was evaluated based on non-kinetic evidence, demonstrating that the reactions switch from SRN1 to polar SN2 according to the solvent employed. [ABSTRACT FROM AUTHOR]

The synthesis in good yields (71-85%) of di- and tristannylated benzenes from commercially available anilines, involving their conversion to the corresponding aryltrimethylammonium salts followed by the reaction with Me3SnNa 1 in liquid ammonia, is described. The results obtained clearly indicate that the stannylation reactions proceed through an SRN1 mechanism. [ABSTRACT FROM AUTHOR]