Tert-Nitrobutane

Fig. 56. Location of the half-wave potential of a quasi-reversible electrode reaction according to Eq. (102). 1 and 1 forward and backward linear sweep voltammogram of 1.5 mM tert-nitrobutane in DMF, sweep rate 18mVs" 2 and 2 convoluted (vs. time) current transients potential is transferred vs. Ag/AgI electrode. Adapted according to [121].

The oxidation of some aliphatic amines is a good route to aliphatic nitro compounds. tert-Butylamine is oxidized in 83% yield to 2-methyl-2-nitropropane by potassium permanganate in water at 45 °C for 8 h and at 55 °C for 8 h [738, 892], Under similar conditions, 4-amino-2,2,4-tri-methylpentane is converted into 4-nitro-2,2,4-trimethylpentane in 69-82% yields [859]. Refluxing 3a-acetoxy-20a-amino-5p-pregnane with a chloroform solution of m-chloroperoxybenzoic acid for 40 min furnishes 3a-acetoxy-20a-nitro-5p-pregnane in 66% yield [379]. 2-Aminobutane is converted into 2-nitrobutane by peroxyacetic acid [253] or dimeth yldioxirane [277] (equation 498). 

A mixture containing valeroyl nitrate, prepared at ca. 20° from excess valeroyl anhydride and 90%-HNOg, dropped through a glass tube packed with glass helices and heated to ca. 290° 1-nitrobutane. Y 56.5%. Prim., sec., tert., as well as ar. nitro compds. can be prepared by this method without isomerization. This makes decarboxylative nitration the most broadly applicable and for many nitroalkanes the best of the known syntheses. F. e. s. G. B. Bachman and T. F. Biermann, J. Org. Chem. 55, 4229 (1970). 

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