Methyl-2-nitropropane

Nitroxides are iV, iV-disubsdnited nitric oxide radicals, the unpaired electron being delocalized between the nitrogen and oxygen The reduction of 2-methyl-2-nitropropane with sodium or electrochemically yields di-r-butyl nitroxide as the final product " Such nitroxide radicals are important for the snidy of a organic ferromagnet... 

Tertiary amines have been oxidized to the corresponding nitro compounds with KMn04. For example, 2-methyl-2-nitropropane is prepared in 84% yield from t-butylamine with KMn04 (Eq. 2.55).117 In a similar fashion, 1-aminoadamantane has been oxidized to 1-nitroadamantane in 85% yield with KMn04 (see Eq. 2.63).118... 

Nitromethane reacts with t-BuNHMgBr (prepared from ethylmagnesium bromide and t-butylamine in boiling THF) to give the oxime 393 nitroethane yields the analogue 394. The action of PhN(MgBr)2 on 2-methyl-2-nitropropane (395) results in the azoxy compound 396432. 

The reactions of A-phenyl a-r-butyl nitrone (PEN) with maleimides, maleic anhydride, and diethyl maleate have been studied by EPR and two types of spin adduct detected. They arise from the reductive addition of PEN to the alkenes and the degradation product of DEN (2-methyl-2-nitropropane). The deuterium and muonium kinetic isotope effects for the addition of the hydrogen atom to a variety of alkenes have been determined experimentally and theoretically. ... 

The oxidation of Fbutylamine to 2-methyl-2-nitropropane is an example of a procedure previously illustrated in Org. Syn N-Mlutylhydroxylamine has previously been prepared by acid-catalysed hydrolysis of 2-<-butyl-3-phenyloxazirane and by oxidation of bbutylaminc. The procedure described here is based on a metliod nnuitioncd b i( lly by Smith and co-workers. 2-Methyl-2-nitrosopropane has also been ])repared directly by... 

The radical-anions of aliphatic nitrocompounds are detectable in aqueous solution as transient intermediates formed during continuous electrolysis in the cavity of the esr spectrometer [4], Decay of the species occurs by protonation and then further reactions. 2-Methyl-2-nitropropane has no acidic hydrogens so that it can be examined in aqueous alkaline solution where the radical-anion is not protonated. Over the pH range 9-11, this radical-anion decays by a first order process with k = 0.8 0.1 s at 26 C. Decay results from cleavage of the carbon-nitrogen bond to give a carbon centred radical and nitrite ion. Ultimately, the di-(ferr,-butyI)nitrone radical is formed in follow-up reactions [5],... 

The reduction of aliphatic nitrocompounds in acid solution proceeds in two steps. First the nitrosocompound is formed. A low steady state concen ation of 2-methyl-2-nitrosopropane has been detected during the reduction of 2-methyl-2-nitropropane [13]. At the cathode potential necessary to attach the first electron to a nitro group, the nitroso intermediate undergoes further reduction to the hydroxyla-mine. When the nitrocompound has one a-hydrogen substituent, tautomerism of the nitroso intermediate to an oxime is in competition with further reduction. Both temperature and proton availability affect the rate of this isomerisation. Reduction of aliphatic nitrocompounds to the hydroxylamine is usually carried out in acid solution at 0-5° C to minimise oxime formation [14, 15], The hydroxylamine is stable towards further reduction in acid solution. Oximes in acid solution are reduced... 

A. 2-Methyl-2-nitropropane. To a well-stirred suspension of 650 g. (4.11 moles) of potassium permanganate in 3 1. of water, contained in a 5-1. three-necked flask fitted with a reflux condenser, a mechanical stirrer, a thermometer, and a 250-ml. dropping funnel, is added drop wise and with stirring over a 10-minute period, 100 g. (1.37 moles) of <-butylamine (Note 1). When the addition is complete, the reaction mixture is heated to 55° over a period of approximately 2 hours, and then the reaction mixture is maintained at 55° with continuous stirring for 3 hours. The dropping funnel and reflux condenser are replaced by a stopper and a still head fitted for steam distillation and the product is steam distilled from the reaction mixture (Note 2). The liquid product is separated from the denser water layer and then diluted with 250 ml. of ether and washed successively with two 50-ml. portions of aqueous 2M hydrochloric acid and with 50 ml. of water. After the ethereal solution has been dried over anhydrous magnesium sulfate, the solution is fractionally distilled at atmospheric pressure to remove the ether. The residual crude product (Note 3) amounts to 106-128 g. and is sufficiently pure for use in the next step. In a typical run, distillation of 124 g. of the crude product afforded 110 g. (78%) of the pure 2-methyl-2-nitrobutane as a colorless liquid, b.p. 127-128°, n2 d 1.3992. The material slowly solidifies on standing to a waxy solid, m.p. 25-26° (Note 4). 

Exercise 24-21 Show how 2-methyl-2-nitropropane may be synthesized from (a) tert-butyl alcohol and (b) 2,2-dimethylpropanoic acid. (Review Sections 23-12E and 24-3B if necessary.)... 

In addition to the commercially available 2,2,6,6-tetramethylpiperidine, di-tert-alkylamines have been prepared by Rathke7 by the copper-catalyzed coupling of acetylenic amines with acetylenic chlorides in an improvement of the procedure of Hennion.8 Di-tert-butylamine has been synthesized by the reaction of 2-methyl-2-nitropropane with sodium, followed by reduction. ... 

Fig. 5.15 Comparison of experimental voltammograms for the reduction of 2-methyl-2-nitropropane at a platinum electrode (solid lines) with best fist simulations using B V (black squares) and MH (white circles) kinetics at two scan rates (a)...

MeNP, 2-methyl-2-nitropropane NPent, 1-nitropentane NPh, 3-nitrophenol COT, cycloocta-tetraene TPE, tetraphenylethylene TBAP, tetrabutylammonium perchlorate TEABr, tetraethyl-ammonium bromide TBAPIy, Tetrabutylammonium hexafluorophosphate MeCN, acetonitrile DMSO, dimethylsulfoxide DCM, dichloromethane [42]... 

Fig. 7.21 (continued) reverse scans. EE SS = —2.6V (vs. Ag), sw = 25mV, A s = 10mV. The values of the kinetic parameters and formal potential extracted in each case are given in Table 7.2. Test solution 2 mM 2-methyl-2-nitropropane, 0.1 M tetra-n-butylammonium perchlorate in acetonitrile. Reproduced from [30] with permission... 

A mixture of 2-methyl-2-nitropropane (503 g) and NH4C1 (207 g) dissolved in 6000 ml water was treated with zinc dust (648 g) while maintaining the temperature... 

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