2-Nitro-2-methylpropane

Nitro-2-methylpropane, 43, 89 N-Nitromorpholine, 43, 83 p-Nitroperoxybenzoic acid, 43, 96 p-Nitrophenacylamine, hydrochloride... 

Aliphatic nitro compounds with the nitro group on a tertiary carbon were reduced to amines with aluminum amalgam [146 or iron [559]. 2-Nitro-2-methylpropane afforded ferf-butylamine in 65-75% yield [146. Even some secondary nitroalkanes were hydrogenated to amines. fra s-l,4-Dinitrocy-clohexane was converted to frans-l,4-diaminocyclohexane with retention of configuration. This may be considered as an evidence that the intermediate nitroso compound is reduced directly and not after tautomerization to the isonitroso compound [560] (see Scheme 54). 

Since many aliphatic primary amines are usually prepared by methods not involving the reduction of a nitroalkane (cf. aromatic amines), their oxidation may provide a useful route to this class of compound. For amines which lead to tertiary nitroalkanes, potassium permanganate appears to be the most satisfactory reagent198 (the preparation of 2-nitro-2-methylpropane, Expt 5.191). In the case of amines which lead to primary or secondary nitroalkanes the oxidant of choice is m-chloroperbenzoic acid, and Expt 5.191 includes a general procedure for this reaction.199... 

Branched chain hydrocarbons have a greater reactivity, with the relative reactivity order being tertiary C-H > secondary C-H > primary C-H. Thus, nitration of 2-methylpropane with nitric acid in a sealed tube can lead to 2-nitro-2-methylpropane. 

In nonaqueous aprotic solvents, such as dimethoxyethane [25] or acetonitrile [26,27], the reduction product from tertiary nitroalkanes is the radical anion. Cyclic voltammetric data of 2-nitro-2-methylpropane showed that the electrochemical rate constant was rather low and depended on the size of the supporting electrolyte cation the electrochemical transfer coefficient a was found to be potential dependent [28]. The nitro-t-butyl radical anion is rather unstable (half-life of 0.66s) and decomposes into nitrite ion and t-butyl radical. Continued electrolysis results in the formatrion of di-t-alkyl nitroxide radical [25,27]. 

Contrasted with electrophilic arcmatic nitration, electrophilic aliphatic nitrations are much affected by protolytic denitrations, which particularly with tertiary and secondary nitro compounds are of major in jortance. The fact that denitration affects electrophilic aliphatic nitration can be best demonstrated in the case of 2-nitro-2-methylpropane which was found to undergo protolytic cleavage in FS03H-SbF5, HF-SbF5, and also in HF-PF solution even at -80°. The protolytic cleavage reaction yields tert-butyl cation and nitrous acid (or subsequently, nitrosonium ion). No nitronium ion is formed, as indicated by absence of any... 

Tertiary C—H bonds show the highest reactivity. However, protolytic cleavage of tertiary and secondary nitroalkanes is a major side reaction, and can lead to the formation of a variety of byproducts. Protolytic denitration was demonstrated by reacting 2-nitro-2-methylpropane with FSOjsH-SbFi, HF-SbFs, and HF-PF5 at -80 C. The protolytic clevage reaaion yields r-butyl cation and nitrous acid (or subsequently, nitrosonium ion). 

Greenblatt et al. (1987) observed the formation of OH (X H) radicals in the low-pressure gas-phase, 282 nm photolysis of nitroethane, 1- and 2-nitropropane, and 2-nitro-2-methylpropane. They did not detect OH in similar experiments with nitromethane. The mechanism is suggested to involve a 5- or 6-membered ring intermediate that leads to the OH product ... 

C4H9O3N, 2-Nitro-2-methylpropane, (CH3>3CN02 S, 1534 C5H11O2N, 1-Nitropentane, CH3CH2CH2CH2CH2NO2 OH, 952 ... 

All the.se substance. are crystalline, and dissolve readily in cold water. Tiimethylolnitrometliane melts at 165-170 0, 2-nitro-2-methylpropane-dioi-1.3 at 147-i 49 0, and 2-nitro-2-metlij lpropanol-1 at 90-95.5. The... 

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