Victor Meyer reaction

In the examples, a nitro group is substituted for a hydrogen atom, and water is a by-product. Nitro groups may, however, be substituted for other atoms or groups of atoms. In Victor Meyer reactions which use silver nitrite, the nitro group replaces a hahde atom, eg, I or Br. In a modification of this method, sodium nitrite dissolved in dimethyl formamide or other suitable solvent is used instead of silver nitrite (1). Nitro compounds can also be produced by addition reactions, eg, the reaction of nitric acid or nitrogen dioxide with unsaturated compounds such as olefins or acetylenes. 

Historical. NMe was First prepd by Victor Meyer who treated Me iodide with Ag nitrite and obtained a 90% yield (Ref 2). This proc came to be known as the Victor Meyer reaction (Ref 50). It has also been prepd by the action of Me sulfate on K nitrite (Ref 3). In the Victor Meyer reaction the ratio of NMe to Me nitrite obtained was found to be dependent upon solv, temp, and the reagents used (Ref 5)... 

In exptl work, indirect methods of introducing nitro groups find wide application as, for example, the replacement of a halogen (iodine or bromine in an alkyl iodide or bromide) by the nitro group, by means of silver nitrite (the Victor Meyer reaction)... 

The reaction of alkyl halides with metal nitrites is one of the most important methods for the preparation of nitroalkanes. As a metal nitrite, silver nitrite (Victor-Meyer reaction), potassium nitrite, or sodium nitrite (Kornblum reaction) have been frequently used. The products are usually a mixture of nitroalkanes and alkyl nitrites, which are readily separated by distillation (Eq. 2.47). The synthesis of nitro compounds by this process is well documented in the reviews, and some typical cases are listed in Table 2.3.92a Primary and secondary alkyl iodides and bromides as well as sulfonate esters give the corresponding nitro compounds in 50-70% yields on treatment with NaN02 in DMF or DMSO. Some of them are described precisely in vol 4 of Organic Synthesis. For example, 1,4-dinitrobutane is prepared in 41 -46% yield by the reaction of 1,4-diiodobutane with silver nitrite in diethyl ether.92b 1-Nitrooctane is prepared by the reaction with silver nitrite in 75-80% yield. The reaction of silver nitrite with secondary halides gives yields of nitroalkanes of about 15%, whereas with tertiary halides the yields are 0-5%.92c Ethyl a-nitrobutyrate is prepared by the reaction of ethyl a-bromobutyrate in 68-75% yield with sodium nitrite in DMF.92d Sodium nitrite is considerably more soluble in DMSO than in DMF as a consequence, with DMSO, much more concentrated solutions can be employed and this makes shorter reaction times possible.926... 

Primary alkyl iodides and bromides are excellent substrates for the Victor Meyer reaction, providing a route to both substituted and unsubstituted nitroalkanes (Table i. i).63,65,70,7i formation of the corresponding nitrite ester is a side-reaction and so the nitroalkane is usually isolated by distillation when possible. The reaction of primary alkyl chlorides with silver nitrite is too slow to be synthetically useful. Secondary alkyl halides and substrates with branching on... 

The synthesis of aliphatic nitro compounds from the reaction of alkyl halides with alkali metal nitrites was discovered by Kornblum and co-workers and is known as the modified Victor Meyer reaction or the Kornblum modification. The choice of solvent in these reactions is crucial when sodium nitrite is used as the nitrite soiuce. Both alkyl halide and nitrite anion must be in solution to react, and the higher the concentration of nitrite anion, the faster the reaction. For this reason, both DMF and DMSO are widely used as solvents, with both able to dissolve appreciable amounts of sodium nitrite. Although sodium nitrite is more soluble in DMSO than DMF the former can react with some halide substrates.Urea is occasionally added to DMF solutions of sodium nitrite to increase the solubility of this salt and hence increase reaction rates. Other alkali metal nitrites can be used in these reactions, like lithium nitrite,which is more soluble in DMF than sodium nitrite but is also less widely available. 

A modification of the Victor Meyer reaction for long chain hydrocarbons (over Cjt) was given by Kornblum (Vol. I. p. 127) [127] and reviewed by the same author. Another modification of the V. Meyer reaction was given as early as 1870 by ter Meer [128). It applies to 1-nitro-1-haloalkanes. By acting with... 

The Importance ( ) of the salts of a,a -d1n1trocyclanones Is Indicated by their facile conversion In high yield to a,w-d1n1tro-alkanes (eq 5). The method Is superior to the well known Victor Meyer reaction In which halogen compounds are treated with silver nitrite. When the ring opening reaction Is performed In reflux-... 

The reaction of alkyl halides with silver nitrite (Victor Meyer reaction) is of value in the preparation of primary nitroalkanes. In the case of secondary nitroalkanes, reactions are slow and yields are low. The reaction is of little value for the preparation of tertiary nitroalkanes. 

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