On effectue la nitration de la dimethyl-5,5 cyclohexene-2 one et de l'isophorone qui conduit respectivement au dimethyl-5,5 nitro-2 cyclohexadiene-1,3 ol et a la trimethyl-3,5,5 nitro-2 cyclohexene-2 one. Les reactions de ces deux derniers composes sont etudiees

The Nef reaction is usually defined as the conversion of a primary or secondary nitroalkane into the corresponding carbonyl compound. This reaction was reported by the Swiss chemist J. U. Nef in 1894. Hydrochloric and sulfuric acid give the same result. The conversion of a nitro group to a carbonyl group has become an important synthetic tool because of the ease of preparation of substituted nitro compounds by condensation of nitroalkanes with aldehydes (the Henry reaction), conjugate addition of nitroalkanes to electrophilic alkenes, or carbon alkylation of the dianion of primary nitroparaffins. The Nef reaction is one of the better examples of “umpolung” reactivity in which the original nitro compound anion functions as an acyl anion equivalent.



This chapter discusses the Nef reaction and modifications of the original process that extend the variety of compounds which are useful as substrates. Each modification is considered according to general mechanistic type and is organized in a “reagent” approach. The Tabular Survey lists all known examples of both the Nef reaction and these modifications so that specific comparison of methods can be made.


Keywords:

Nef reaction;
scope;
limitations;
oxidizing agents;
reducing agents;
nitro compounds;
alkylation;
acylation;
nitroolfins;
nitroepoxides;
experimental procedures;
nitronates;
side reactions;
synthetic utility

Nitration of 2-cyclohexenone derivatives and some reactions of the products

Citations

The Nef Reaction

Partially Saturated Polynuclear Isoxazoles

Nitration of 2-cyclohexenone derivatives and some reactions of the products