SU391137A1 - METHOD OF OBTAINING NITROXYL RADICALS - Google Patents

Description

one

The invention relates to the synthesis of nitrogen-containing derivatives, and to the process for the production of myroyl radicals.

A known method is to obtain iproxyl radicals in the putu of treating secondary aluminums with a priest of hydrogen in the presence of tungstic acid salts in an aqueous IDA water-alcohol medium as a catalyst. It is possible to obtain nitracoyl radicals with HIGH yields, however, the reaction is long (about 10 days).

In order to reduce the process time and the possibility of production (reaction in non-polar media, secondary amines are proposed to be oxidized with hydrogen oxide in acetonitrile at a pH of 8-10, followed by separation of the products with known npHeMaiM.

Example 1. To a solution of 1.68 g of 2,2,5,5-tetramethyl-3-; carbamidyrroline in 16 ml of methanol was added 0.5 g of sodium hydrogen carbonate, 1.55 tons of acetonyl and 3, 6 ml of OZ of hydrogen peroxide. The mixture was left at room temperature for two days and at room temperature, the bicarbonate was filtered off with sodium | p1 and the filtrate was evaporated in vacuo. After evaporation, 10 ml of water, 1 ml of 5/0 solution of hydrochloric acid are added to the solid residue, and after stirring, 1.39 g of crystalline 2,2,5,5-tetramethyl-3-urea-pyrroline-2-oxyl are sucked off. Additional 0.10 g of radical is additionally obtained from chloroform from the mother gum. Total yield of the iminoxy is 1.49 g (), mp 196-198 ° C (by liter of titanium and 203 ° C).

Example 2. To a solution of 1.70 g of 2,2,6,6-tetramethylpiperidine in 19 ml of metaiol was added 0.6 g of bi1carbo sodium ata, 1.86 ml of aceto nitrile and 4.3 ml of D30 / o hydrogen peroxide. The mixture is heated for 2 hours at 60 ° C, then it is processed as indicated in Example 1. 1.15 g (62Vo) 2.2,6,6-tetramethyl-hyperidium-oxyl, t. (Pl. 36- 37 ° С (according to literary data 37.8-38.1 ° С).

Example 3. To a solution of 1.69 g of diphenylamine in 16 ml of ether was added 0.5 g of sodium bicarbonate, 3.10 ml of acetone-nitrile and 3.6 ml of DL of o-hydrogen peroxide. The mixture was left at room temperature for two days, then the ether layer was separated and washed three times with water. The content of diphenylazotoxide, determined iodometrically, is IBVo from the theoretical value.

Prev Invention

A method of producing nitroxyl radicals by treating secondary amines with pers30 hydrogen at 15-60 ° C, 3 characterized in that, in order to reduce the reaction time, the reaction is carried out in acetanitrol at 4 pH 8-10 and the products are isolated with known nipneiMaMiH.