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Quarternary phosphonium salts are formed during the γ-irradiation of mixtures of triphenylphosphine (TPP) or tributylphosphine with aryl halides. The rate of conversion is markedly increased upon dilution of the mixtures with hydrocarbon solvents such as benzene, cyclohexane and cyclohexene. An ionic mechanism is discussed in which a positive charge transfer from the solvent to TPP and dissociative electron capture by the aryl halide are involved. Several phosphonium salts were synthesized. Arsonium salts are produced from triphenylarsin-arylhalide-mixtures with G-values about ten times lower than in the corresponding TPP reactions. The yield of stibonium salts is still lower. Trialkylamines react with aryl halides to give trialkyl or dialkyl ammonium salts. The rate of conversion can also be drastically increased by the addition of benzene.

Präparative und kinetische Aspekte der γ-strahlenchemischen Bildung von Phosphonium- und anderen Oniumsalzen