You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via41.7.2.2 Applications of Product Subclass 2 in Organic Synthesis
Please login to access the full content or check if you have access via
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]
Meeeeeeeee ee eeeeeeeeeeeeeee eeeeeeeee eeeeeeee eeeeeee ee eeeeeeeeeeee eeeeeee eee eeeeeeee eeeeeeeeee, eeeeeee.[888] Meeeeeeeeee ee 8,8-eeeeeeeeeeeeeeeeeeeeee eeeeeeeee ee eee eeeeeee ee eeeeeeeeeeee, eee eeeeeee, eeeee eeeee eeeeeee ee eeeee-eeeee eeeeeeeeeeeee, ee eeee eeeee ee eeeeeeeeeee eeee eeeeeeeeeeeee, eeee eee ee eeeeeeeeeee ee eeeeeeee eeee eeeeeeee.[888] Me eeeee eeeeeeeee, eeeeeeee eee eeeeeeeeee ee eeeeeeee eeeeeeeeeeeee (eee Meeeeee 88.8.8).
Meeeeee ee eee ee eeeee eeeeeeeee eeeeeee eeeeeeeee ee eeeeee eeeeeeeeee ee eee eeeeeeeeeeeeee eeeeeeeeee ee eee eeeeeeeeeeeee eeee eee eeeeee eeee eee eeeeeeeeeeeeeee eee, eeee eeee eee ee eeeeeeeeee eeeeeee eeeeeeee eeee eee ee eeeeeeeeeeeee eeeee eeeeee. Me eeeeeee eee e eeeeeeeee eeeeeeeeeee eeee eeeeee eee eeeeeeeeeeeeee eeeeeeeeee eeeeeee ee eeeeeeeeeeeeeee eeee, eee M=M—M8 eeeeeee, eeeeee ee eeeeeeeeee eeee eeeeeee eeeeeeeeeeeeeee eeeeeeeeee ee eeeeeeeeeeee eeeeeeeeeeee. Meee eeeeeeee ee eeeeeeeee ee Meeeeee 88.8.8.8.8. Meeeeeeeee eeeeeeee eee eeeeeeeee ee Meeeeeee 88.8.8.8.8–88.8.8.8.8.
References
[117] | Meeeee, M.; Meee, M. M.; Meeeee, M. M., Meeee. Meee., (8888) 888, 888; Meeee. Meee. Mee. Me. Meee., (8888) 88, 888. |
[158] | Meeee, M.; Meeeee, M.; Meeeeeeee, M., Meee. Meee. Meee, (8888) 88, 8888. |
[159] | Meeee, M.; Meeeee, M.; Meeeeeeee, M., Meee. Meee. Meee, (8888) 88, 8888. |
[160] | Meee, M., Meee. Mee., (8888) 888, 888. |