Science of Synthesis

Kubik, S., Science of Synthesis, (2010) 41, 534.

Alkenediazonium compounds lose nitrogen much less readily than alkanediazonium compounds do. However, alkenediazonium compounds are still highly reactive and stable only in the absence of nucleophiles. A systematic investigation of the reactions of 2,2-diethoxyethenediazonium hexachloroantimonate with various nucleophiles reveals that this compound behaves like an alkylating agent toward ethers, alcohols, and water forming ethyl diazoacetate, which reacts further with excess of the nucleophile.[‌158‌] The products of the reaction with a secondary amine such as diethylamine derive from the nucleophilic addition of the amine at the 2-position. Thermal decomposition in inert solvents leads to the alkylation of the counterion, i.e. formation of chloroethane, and in anisole, alkylation and chlorination of the solvent also take place. With 2-naphtholate, no azo-coupling reaction is observed. Thus, none of the reactions of 2,2-diethoxyethenediazonium hexachloroantimonate are explained by the intervention of vinyl cations formed by cleavage of the C—N bond and it is therefore suggested that the reactivity of this alkenediazonium compound is better represented by the mesomeric structures ‌14B‌–D in ‌Scheme 15‌ (Section ‌41.7.2‌).[‌158‌] A crystal structure supports this assumption.[‌117‌]

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