Decomposition of Aryldiazonium Ions in Homogenous Solutions Part II: Arylations with benzenediazonium ions and p‐nitrobenzenediazonium ions in dimethyl sulfoxide

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Abstract
When p‐nitrobenzenediazonium tetrafluoroborate is decomposed in the presence of dimethyl sulfoxide/benzene or dimethyl sulfoxide/nitrobenzene systems under nitrogen, the respective biphenyl derivatives are obtained in good yield. With benzenediazonium tetrafluoroborate in the same systems the yields are low. The influence of oxygen, iodine, iodobenzene and N, N‐diphenylhydroxylamine on the products of the reactions were determined. The by‐products, isomer distribution with nitrobenzene as a substrate, and the partial and total rate factors were also determined. From the above data it can be shown that the reaction with p‐nitrobenzenediazonium salt is a homolytic process and that with the unsubstituted benzenediazonium salt is essentially a heterolytic reaction. The problem of the mechanism of the radical forming steps (electron transfer or adduct formation) and the mechanistic relationship to other modes of arylation (aroylperoxide, classical two‐phase Gomberg‐Bachmann reaction, catalysis by transition metal ions, nitrite ions, etc. electron transfer properties of DMSO) are discussed.

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