Nitroso-tert-octane

A. r>itr>o80-tert-oetane To a 1-L, three-necked flask equipped with an addition funnel, a mechanical stirrer, and a thermometer are added 120 ml of methanol, 51.7 g of tert-octylamine (0.4 mol) and 90 mL of water containing 1.2 g (0. 0028 mol) of the tetrasodium salt of ethylenediaminetetraacetic acid and 2.52 g (0. 0076 mol) of sodium tungstate dihydrate. The solution is cooled to 15°C in an ice bath and hydrogen peroxide (361 mL of a 16% solution, 1.7 mol) (Notes 1 and 2) is added over 5 hr. The blue reaction mixture is stirred for an additional 16 hr and the product is extracted with petroleum ether (3 x 50 mL). Unreacted amine is removed by washing twice with 2 N hydrochloric acid. After the blue organic layer is washed with brine, it is dried over MgS04. Petroleum ether is removed by distillation at atmospheric pressure. Continued distillation of the product affords 29.7 g of nitroso-tert-octane... 

Although it is used in excess, the amount of H202 used seems to be critical. The checkers found that the use of 2.1 mol of H202 results 1n considerable over-oxidation to nitro-tert-octane, resulting in a yield of nitroso-tert-octane of only 40%. 

Nitroso-tert-octane may also be prepared by oxidation of tert-octylamine with peracetic acid in ethyl acetate, obtained by the submitters from the Union Carbide Corporation. To a 1-L, three-necked flask equipped with a mechanical stirrer and an addition funnel are added 51.7 g of tert-octylamine (0.4 mol), 50 nL of water, and 50 nL of ethyl acetate. The flask is placed in an ice bath and the contents are stirred until the temperature reaches 0-5°C. A solution of peracetic acid in ethyl acetate (3.15 M... 

In addition to the procedure given here for the oxidation of tert-octylamine to nitroso-tert-octane,2 the oxidation may be carried out with m-chloroperoxybenzoic acid or with a solution of peroxyacetic acid in ethyl acetate.4 The lead dioxide oxidation of alkyl hydrazines to alkyl radicals appears to have general application. In addition to tert-butylhydrazine, various secondary alkylhydrazines (e.g., bornylhydrazine and menthylhydrazine) have been used to good effect. The reduction of tri-tert-alkylhydroxyl amine to the di-tert-alkylamine has also been achieved with sodium in ammonia but the insolubility of the hydrophobic substrate makes this procedure difficult. The use of sodium naphthalenide gives higher yields and is more reproducible. 

Nitroso-tert-octane Pentane, 2,2,4-trimethyl-4-nitroso- (8,9) (31044-98-1) tert-Octylamine 2-Pentanamine, 2,4,4-trimethyl- (9) (107-45-9)... 

An extension of a method developed for the preparation of butyl radicals from t-butyIhydrazine and lead dioxide, allowed synthesis of hindered chiral amines via generation of secondary radicals from bornylhydrazine and menthyIhydrazine. The radicals were trapped with nitroso-tert-octane and the resultant hydroxyl-amine mixtures reduced to give readily separable mixtures of borny1-tert-octyl amines (2),(3) and menthyl-tert-octylamines... 

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