SU1544767A1 - Method of producing halogen-glioxyms - Google Patents

Abstract

The invention relates to substituted oximes, in particular the preparation of bromo- or chloro-halogenoximes of the total fi r-C (= N-OH) -C (= N-OH) -X, where X = CL, BR

diamidr = BR, CN, C (O) NH ₂

C (O) NH-C ₆ H ₄ -4-SdiAMidL, for the synthesis furazans, furoxanes and isoxazoles. The goal is to expand the range of target oximes and simplify the process. The latter lead nitrosirovaniem oxime f-ly R ₁ -CH ₂ -C (= N-OH) -NH ₂ , where R ₁ = CN

C (O) NH ₂

C (O) NH-C ₆ H ₄ -4-CL

C (NH ₂ ) = N-OH

C (O) -NH-OH, using sodium nitrite in a solution of HCL-or HBR-acid. These conditions simplify the process by using available raw materials.

Description

This invention relates to the chemistry of glyoximes, and specifically to a process for the preparation of halogen-glyoximes of the general Formula

I

R-c

-s

NOH NOH

where R is CN, Br, CONH ,; CONHCtH f-b-Cl;

X - Cl, Br,

which are used to produce glyoximes with different functional groups, as well as to produce furasans, furoxans and isoxazoles.

The aim of the invention is to simplify the process and expand the range of products obtained.

Example 1. Chlorocyanoglyoxime.

1.98 g (0.02 mol) of cytoacid acid amidoxime is dissolved in 20 ml of concentrated hydrochloric acid and a solution of 4.14 g (0.06 mol) of sodium nitrite in a minimum amount of water is added dropwise at 0-5 ° C. Stand 3 hours

the product is then filtered or extracted with ethyl acetate. Obtain 1.77 g (60%) of the desired substance, so pl. 209-210 ° C.

HMR spectrum: 10.96 s (OH); 11.07 s (OH).

IR spectrum, cm 1: 3150-3320 (OH); 1600 (); 2270 (CaN); 929 and 1023 (N-0); 436 (C-C1).

PRI mme R 2. Bromcyanoglyoxime.

Out of 1.98 g (0.02 mol) of amidoxime of cyanoacetic acid, 20 ml of concentrated hydrobromic acid and 4.14 g (0.06 mol) of sodium nitrite, 2.15 g (56%) of the desired substance is obtained, mp. 191 C.

PMR spectrum, ppm: 11.07 s (OH); 11.94 s (OH).

IR Spectrum, 3150-3300 (OH); 2265 (C-N); 1600 (); 905 and 1020 (N-0); 639 (C-Br).

PRI me R 3. (i-Ulor-o /, /} - Ditchg - nitrozopropioamid.

(L

with

ate

4 vj

O5 4

From 2.30 g (0.02 mol) of carbamoyl acetamidoxime, 20 ml of concentrated acid, and 4.14 g (0.06 mol) of sodium nitrite, 1.62 g (49%) of the desired substance is obtained, m.p. 180-182 ° C.

PMR spectrum, ppm: 7.0 s (NH7); 11.82 s (OH); 12.13 with (OH).

Mass spectrum, m / e: 165 (M4); 129 (M-HC1); 99 (M-HC1-CONH g); 69 (M-HC1- -NO-0).

PC spectrum: 3410 and 3390 (NH,) 3200 (OH); 1675 (); 1638 (); 930 and 1010 (N-0).

Example 7 p-Chloro-o, i-diisonitropionamide.

Out of 2.64 g (0.02 mol) of maloneamid sima, 20 ml of concentrated hydrochloric acid and 4.14 g (0.06 mol) of sodium nitrite give 1.82 g (56%) of a certain substance.

The spectral and physicochemical characteristics are similar to the product obtained from carbamoyl acetamidoxa.

EXAMPLE 5 4-Chloranilide- (3-chloro-c), p-di-nitrosopropionic acid.

Out of 4.55 g (0.02 mol) of p-chlorophenyl carbamoyl acetamidoxime, 20 ml of concentrated hydrochloric acid, 4.14 g (0.06 mol) of sodium nitrite, 6.13 g (61%) of the desired substance is obtained, t .pl. 180-182 ° C.

PMR spectrum, ppm: 7.33, d, 1 9.0 Hz (o-CtH4); 7.64, d, 0 Hz (M-CtF4); 8.89 with (OH); 10.91 s (OH); 11.04 s (NH).

IR spectrum, cm: 3270 (N4); 3110-3200 (OH); 1,690 (); 1610 (); 970 and 1014 (N-0).

0

five

0

II p and me R 6. Dibromglyoxime.

Out of 2.66 g (0.02 mol) of 1-amino-3-ox-1,3-diisonitrosopropane, 20 ml of concentrated hydrobromic acid and 4.14 g (0.06 mol) of sodium nitrite, 1.47 g are obtained (30%) of the desired substance, so pl. 215-217 ° C (lit. 217 ° C).

Thus, the method allows to obtain a wide range of previously inaccessible and inaccessible halo-iglioximes in a technologically convenient way using more readily available raw materials — various corresponding amidoximes.

Claims (1)

Invention Formula The method of obtaining halogen-glyoxomas of the common formula "-S -s NOH NOH where R is Br, CN, CONHg, CONHC H „-4-C1; X - Cl, Br, from oxime derivatives, characterized in that, in order to simplify the process and expand the range of products obtained, amidooxime of the total Lormula NgCH2-C-Shg NOH where R, - CN, SOMNg, CONH-4-C1-C6H4; , CONH-OH, nitrosate with sodium nitrite in a solution of hydrochloric or hydrobromic acid.