Nitroparaffin sodium salts

The normal form A can pass by tautomeric change under the influence of alkali into the acidic hydroxy form B, which in turn can 3deld the sodium salt C. Nitroparaffins are therrfore pseudo-acids, and are soluble in alkaline solution. 

The nitroparaffins are named as derivatives of the corresponding hydrocarbons by usiag the prefix "nitro" to designate the NO2 group (1), eg, 1,1-dinitroethane, CH2CH(N02)2- The salts obtained from nitroparaffins and the so-called nitronic acids are identical and may be named as derivatives of either, eg, sodium salt of i7ti-nitromethane, or sodium methanenitronate [25854-38-0]. 

Data on infrared curves for many nitroparaffins and their sodium salts have been reported (10,85—89). References 87, 90 and 91 give uv spectra. Accurate analysis and positive identification of the components of a mixture of several nitroparaffins can be obtained by mass spectrometry (qv) (92). 

A new excellent method of preparing gem-dinitroparaffins was recently reported by Kaplan and Shechter [97], It consist in acting with AgN03 + NaN02 on sodium salts of nitroparaffins. 

Nitro alcohols from the condensation of aromatic aldehydes with sodium salts of nitroparaffins are oxidized to a-nitro ketones with chromic-acetic acids, as illustrated by the preparation of a-nitroacetophenone, CjHsCOCHjNOj (80%). ... 

Various procedures have been developed for the production of oximes from nitroparaffins. Direct reduction with zinc dust and acetic acid has been proposed, but the yields are poor because of the simultaneous formation of amines. A synthesis for cyclohexanone oxime has been demonstrated which involves the formation and selective hydrogenation of 1-chloro-l-nitrocyclohexane. The halogenated intermediate is prepared in quantitative yield by chlorination of the sodium salt of acz -nitrocyclo-hexane, and subsequent hydrogenation is performed in an 80% yield over palladium-on-charcoal, ... 

NUrottic esters (2). These previously little known compounds are obtained in quantitative yield by reaction with sodium salts of nitroparafFins at 0°.- Methylene... 

Henry reaction. Formation of nitroalcohols by an aldol-type condensation of nitroparaffins with aldehydes in the presence of base (Henry) or by the condensation of sodium salts of aci nitroparaffi ns with the sodium bisulfite addition products of aldehydes in the presence of a trace of alkali or weak acid (Kamlet). Widely used in sugar chemistry. 

These syntheses have resulted from application of two well-known general reactions of nitroparaffins to the sugar field. The base-catalyzed condensation of primary or secondary nitroparafiins with aldehydes gives nitro alcohols the sodium salts of these decompose in dilute mineral acid... 

With sodium azide, salts of secondary nitroparaffins rearrange to N-substituted amides (29). With SO2, primary or secondary nitroparaffins give imidodisulfonic acid salts (30). Potassium nitroform reacts quantitatively with nitryl chloride in ether to form tetranitromethane (31). 

Primary nitroparaffins react with two moles of formaldehyde and two moles of amines to yield 2-nitro-l,3-propanediamines. With excess formaldehyde, Mannich bases from primary nitroparaffins and primary amines can react further to give nitro-substituted cycHc derivatives, such as tetrahydro-l,3-oxa2iaes or hexahydropyrimidines (38,39). Pyrolysis of salts of Mannich bases, particularly of the boron trifluoride complex (40), yields nitro olefins by loss of the amine moiety. Closely related to the Mannich reaction is the formation of sodium 2-nitrobutane-1-sulfonate [76794-27-9] by warming 1-nitropropane with formaldehyde and sodium sulfite (41). 

Ttinitroparaffins can be prepared from 1,1-dinitroparaffins by electrolytic nitration, ie, electrolysis in aqueous caustic sodium nitrate solution (57). Secondary nitroparaffins dimerize on electrolytic oxidation (58) for example, 2-nitropropane yields 2,3-dimethyl-2,3-dinitrobutane, as well as some 2,2-dinitropropane. Addition of sodium nitrate to the anolyte favors formation of the former. The oxidation of salts of i7k-2-nitropropane with either cationic or anionic oxidants generally gives both 2,2-dinitropropane and acetone (59) with ammonium peroxysulfate, for example, these products are formed in 53 and 14% yields, respectively. Ozone oxidation of nitroso groups gives nitro compounds 2-nitroso-2-nitropropane [5275-46-7] (propylpseudonitrole), for example, yields 2,2-dinitropropane (60). 

The chemical properties of primary and secondary nitro compounds differ considerably from those of tertiary nitro compounds. This is due to the presence of active hydrogen atoms in the first two. The difference appears most clearly when nitro compounds are treated with alkalis. As long ago as 1872 Meyer [48,48a] observed that certain nitroparaffins were soluble in sodium hydroxide solutions. In 1888 Michael [49], and later Nef [50], suggested that the salt formed in the... 

---