SU574443A1 - Stable nitroxyl radicals of 4-cyano-2,2,5,5 tetramethyl-d3-imidazoline-1-oxyls and method of preparing thereof - Google Patents

Description

at 3-15 ° C in water or water-alcohol solution, followed by alkali treatment

XO

 .

R-NH, 0, X

NH OSOjH

-alkyl

No. I O

(Oah, 5)

with high yields.

Source 4-gret-butylimine-2,2,5,5 tetramethyl-D-imidazolin-1-oxyl and 4-cyclohexylaminomethyl-2,2,5,5-tetramethyl-D imidazolin-3-oxide-1-oxyl is prepared by known methods 3, 4.

Example 1. Preparation of 4-cyano-2,2,5,5-tetramethyl-D-imidazolin-1-oxyl (1a).

To a suspension of 0.448 g (2.0 mmol) of 4-greg-butylimino-methyl-2, 2,5,5-tetramethyl-D-imidazolin-1-oxyl in 5 ml of water, with ice cooling, 0.256 g (2, 26 mmol) oxylamine-O-sulfonic acids so that the temperature does not rise above 15 ° C. The aqueous solution is washed with ether, the ether extracts are discarded. 10 ml of ether are added to the aqueous solution and 1 n is added dropwise with stirring. caustic soda solution. After adding 0.5 ml of aqueous alkali, the colored ethereal solution is drained, the aqueous solution is treated with 10 ml of ether and 0.5 ml of aqueous alkali is added. The operation is repeated until 5 ml of 1N is added. caustic soda solution. The combined ether extracts are dried over magnesium sulphate, filtered and evaporated. The residue is crystallized upon cooling. The yield of the target product 0,272 g (82%), so pl. 32-33 ° C (sublimation, 1 mm / 25 ° C).

Found,%: C 57.83; P 7.32; N 25.40

CgniaNaO

Calculated,%: C 57.83; H 7.23; N 25.30

1610, 1190,

(SCC; 5%): 2250,

IR PTSM-Igs 3.171;

(alcohol): 240 nm, UV spectrum 208 nm, Ige 3,584.

Example 2. Getting 4-cyan-2,2,5,5-tetramethyl-D - imidazoline - 3 - oxide-1-oxyl

(sixteen).

To a suspension of 0.91 g (3.4 mmol) of 4-cyclohexyliminomethyl-2,2,5,5-tetramethyl-D imidazolin-3-oxide-1-oxyl in a mixture of 3 ml of methyl alcohol and 7 ml of water under ice cooling with 3 ° C and 0.58 g (5.1 mol) oxylamine-0-sulfonic acid are added with stirring. The temperature should not exceed. The aqueous solution is washed with ether, the ether extracts are discarded. To the aqueous solution was added 10 ml of ether and with stirring, dropwise 1 n. caustic solution

salts of imine-solution of alkyl alkyl ammonium sulfonic acids according to the scheme:

.0

№С

TO

W№

F OH

,

1 1 About

isr

I

about

(Y.B)

soda. After adding 1 ml of aqueous alkali, the colored ethereal solution is drained, the aqueous solution is again treated with 10 ml of ether and 1 ml of aqueous alkali is added. The operation is repeated until 10 ml of 1N is added. caustic soda solution. The combined ether extracts are dried over magnesium sulphate, filtered and evaporated. The residue is crystallized upon cooling. The yield of the target product 0,462 g (74,3%), so pl. 70-71.5 ° С (sublimation, 5 mm / 80 ° С).

Paydeno,%: C 53.05; P 6.57; N 23.04

CgHisNsOs

Calculated,%: C 52.75; P 6.59; N 23.08.

IR spectrum (KBG; 0.25%): 2220, 1560, 1180, 1100 cm-1

UV-spectrum (alcohol): 268 nm, Igs 4.004.

Claims (4)

Invention Formula . Stable nitroxyl radicals 4-cyan-2,2,5,5-tetramethyl - A-imidazoline - 1oxyl formula 1a — at position 3, the nitrogen atom (N-, without oxygen atom) is located; 16 - in position 3 is the N-oxide group (). Ia, 5) 1 2. A method of producing a compound according to claim 1, wherein tl and h and y and n with the fact that 4-alkylimino-methyl-2, 2,5,5 - tetramethyl - D - imidazolin-1oxyl formula l  -j %) J (1. o (iia, 6) where R is alkyl, N Yu has the specified value, interact with an excess of oxylamine-0-sulfonic acid at 3-15 ° C in water or in a water-alcohol solution, followed by treatment with alkali and the selection of the target product. 5 Sources of information in view of the examination 1. Rozantsev EG. Free iminoxoxyl radicals. Ed. “Chemistry, 1970. 2.Fiset S., Streith I. Hydroxylamin o-sulfo-5 nic acid .-“ Tetrahedron Lett, 1974, p. 3187. 3. Grigoriev I. A., Volodarsky L. B. b Interaction of 4-bromomethyl and 4-dibromomethyl derivatives. - “Journal of organic himmine, 1974, № 10. 4. Grigoriev, I. A., Volodarsky, L. B. On the intramolecular oxidation of a 4-aminoalkyl group. - “Journal of Organic Chemistry, 1975, №11.