2- Methyl-2-nitrobutane

A. 2-Methyl-2-nitropro]f)ane. 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 dropwise and with stirring over a 10-minute period, 100 g. (1.37 moles) of i-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°, d 1.3992. The material slowly solidifies on standing to a waxy solid, m.p. 25-26° (Note 4). 

With aliphatic nitro alcohols, such as 2-methyl-2-nitropropan-l-ol, 2-nitrobutan-l-ol and 3-nitrobutan-2-ol, the reaction with 2 similarly yields only the corresponding 2,3.3,3-tetrafluoro-... 

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). 

Methyl-l-nitrobutane, A"33.8 Valine, A4.19, A"15 Norvaline, A10.15, A"8 2-Amino-2-methylbutyric acid, A40.9 4-Amino-2-methylbutyric acid, A34.5 4-Amino-3-methylbutyric acid, A27.16 4-Aminopentanoic acid, A 14.14, A"6, A"8 [4- C]Valine, D 3.10... 

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