SU721412A1 - Pernitrous acid derivatives and their preparation method - Google Patents

Description

(54) DERIVATIVES OF PERAZOTIC ACID AND METHOD FOR THEIR PRODUCTION

one

The invention relates to the field of synthesis of new chemical compounds,

Perazoti acid HOONO in the most unknown form. It is a low stable, intermediate compound. Its existence has been proven only in acidified aqueous solutions of hydrogen peroxide and sodium nitrite, which are used for effective hydroxylation and nitration of aromatic compounds at room temperature,

The formation of a peraspotonic acid and its role as a nitrating and hydroxylating agent are confirmed experimentally

Derivative acid derivatives, their properties and method of preparation are unknown,

The aim of the invention is to synthesize peraspidic acid esters (alkyl peroxynitrites) of the general formula R-0-O-NO, which can be used as alkoxylation, nitrating, nitrosating agents of aromatic compounds in the synthesis of physiologically active preparations.

Derivatives of the acid of this general formula are nit

organic hydroperers; acidic nitrous acid and its derivatives in an aqueous medium or in an indifferent solvent at a temperature of about. As organic hydroperoxides, alkyl or arylalkyl hydroperoxides containing ethyl, tert-butyl cumyl, etc. radicals are used.

Nitrosation is carried out with nitrous anhydride, nitrosyl chloride, alkyl nitrites, nitrous acid. The most convenient and affordable is nitrosation with nitrous acid, which is formed at the time of separation from sodium nitrite during acidification with hydrochloric acid with a slight excess of nitrous acid to hydroperoxide (1.1: 1 molar ratio).

In cases when nitrosation is carried out with hydroperoxides more sensitive to acid-catalytic decomposition, for example cumyl hydroperoxide, non-aqueous solutions or inert solvents such as ether, dioxane, etc. are used for a better yield of the target products.

Claims (2)

Preparation of perazoic acid derivatives is carried out at lower temperatures. The optimum temperature when using aqueous solutions is about 0 ° C. Example. Tert-butyl peroxy nitrite. To the mixture, freshly prepared by distillation, containing 9 g of tert-butyl hydroperoxide, 7.6 g of sodium nitrite, in 14 ml of water with vigorous stirring and slowly added 9 ml of concentrated hydrochloric acid, without increasing the temperature by more than 5 ° (cooled with ice and salt). Then 40 ml of water are added to the reaction mixture and stirred for another 10 minutes at 0.5 ° C. The organic layer is decanted, washed with 2.3% -Hfc 4 soda solution, water, and dried over calcium chloride or magnesium sulfate. The output is slightly yellow, 10.4 g (80% of theory) With According 1.4014,, 0504. After the first race, the tert-butyl peroxynitrite is T70, a colorless oil with m, kip. 44 ° C / 53-55 mm ppm; , 4006, 0633, mol. Weight 125 (in benzene), calculated 129. M RQ: 29.44, calculated 29.00 ... Found,%: C 36.89; H 6.54; N 10.49. C HgNOj. Calculated,% C 37.20; H 6.97; N 1 sg, 85. PRI me R. 2. Cumyl peroxynitrite 16.0 g of technical cumene hydroperoxide are mixed with a 90% basic substance content in 15 ml of diethyl ether with 7.6 g of sodium nitrite in 14 ml of water, cooled to -3 ° C, and slowly with vigorous stirring, 9 ml of concentrated hydrochloric acid, do not allow the temperature to rise BNiue. 40 ml of water are added and the erne is stirred for 20 minutes at a temperature of about 0 ° C. The organic layer is decanted, washed with dilution with cold soda solution and dried over calcium chloride. After removal of the ether under vacuum, 12.6 g are obtained (calculated on 100% hydroperoxide). Cumyl peroxynitrite at the time of separation from the reaction mixture is a yellowish oil with d 1.1420 with a yield of 60% (without ether). Mol. Weight 174 (in benzene), WELCH, 181. Found:%: N 8.46. Calculated,%: N 8,83. The physiological effect of alkyl peroxynitrite is manifested in the expansion of peripheral blood vessels and an increase in the rate of pulse inhaling their vapors. Claims of the invention 1. Derivatives of pyramid acids of the general formula R — O — O — NO, where R is cumyl, tert-butyl. 2. A process for the preparation of compounds according to claim 1, comprising nitrosating the alkyl or aryl alkyl hydroperoxides with an excess of sodium nitrota in an acidic medium or derivatives of nitrous acid in an aqueous medium, or in the presence of an inert solvent at. Sources of information taken into account in the examination, Organic Chemistry, 1968, W 5, p.84b.