2- nitropropane, sodium compounds

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). 

Nitro compounds in alkaline medium are used for rather specific oxidations. 2-Nitropropane in the form of its sodium salt converts benzylic halides into aromatic aldehydes under fairly mild conditions [987. Nitrobenzene transforms isoeugenol [95S] and similar aromatic compounds with side chains that contain double bonds conjugated with the aromatic rings into aldehydes [988, 989], In the Skraup synthesis, nitrobenzene dehydrogenates the dihydroquinoline intermediate to quinoline. 

A) ci-Form of Nitro Compounds. Place in three tubes five drops of 1-nitropropane, 2-nitropropane, and nitrobenzene, respectively. To each add 2 ml of dilute sodium hydroxide. Shake, and note whether the compoxmd dissolves. 

B) Reduction of Nitro Compounds to Amines. Place 0.5 ml of nitromethane or 1-nitropropane in a test tube immersed in cold water add 2 ml of concentrated hydrochloric acid and then a piece of granulated tin. When the reduction is complete, add with cooling 5 ml of 6 N sodium hydroxide solution. Note the strong odor of alkylamine. Devise a test for confirmation. 

The reaction of FITS compounds with the sodium salt of 2-methylcyclohexan-l,3-dione led to the 0-perfluoroalkylated and the C-perfluoroalkylated products. The ratio 0-derivatives C-derivatives was strongly dependent upon the reaction temperature, the C-perfluoroalkylated product predominating at lower temperature. Similar results were obtained with ethyl 2-methylacetoacetate. In the case of the sodium salt of diethyl 2-methylmalonate and of 2-nitropropane, only the C-perfluoroalkylated products were isolated. ... 

A general procedure for conversion of substituted benzyl halides into aldehydes consists in their reaction with the sodium salts of aliphatic nitro compounds, particularly those of 2-nitropropane and nitrocyclohexane which afford unstable ester-like intermediates with benzyl halides the intermediates decompose to oxime and aldehyde ... 

The formation of these products was rationalized in terms of the initial formation of (83). The diene (83), which is a stable, isolable compound tautomeric with (84), reacted with 2-nitropropane anion to give the above-mentioned products, and with sodium p-toluenesulphinate to give (85). The analogous compounds (86 ... 

This reaction was initially reported by Hass and Bender in 1949. It is the synthesis of aromatic aldehydes by treatment of substituted benzyl halides with sodium nitropropane salt (also called sodium propane-nitronate ). Therefore, this reaction is called the Hass-Bender reaction or Hass-Bender oxidation. This reaction also takes place on aromatic polycyclic compounds. ... 

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