SU1625879A1 - Method of producing arylarsonic acid bromoanhydrides - Google Patents

Abstract

The invention relates to organic compounds of the mouse, in particular, the preparation of aryl arsonous acid bromides with a common C6H4X-As (OR) Br, where XH, n-CH3, o-OCH3, n-Br; R-C2H6-, H30-CjH7,, tert-C4 C, which can be used in the synthesis of active substances. The goal is to create a new way of obtaining new intermediates for the specified purpose. Synthesis is prepared by reaction of the corresponding ethyl-1 arylchloroarsine in the form of C H + X-As (C2Hj.) Cl with the corresponding alcohol in the presence of triethylamine by separating the resulting triethylamine hydrochloride followed by treatment with bromine. The process is carried out in oenzol or in CC14 at 20 ° C. Yield, Lt Kip., &Amp;C;(mmHg.); gross-la: a) 95; 117-118 (1); C10H14AsBrO; b) 93; 111-113 (1); C, H, Z AsBrO; c) 96; 100-102 (1); C8H 0AsBrO; d) 94; 139-141 (1); C H AsBrO; e) 92; 165-166 (3); C | 0H, 3A5BgO; e) 96; 145.5-146 (1); C ,, h (o- AsBrOj ,,. C 8 (L

Description

The invention relates to a new method for the preparation of new mice with organic compounds, bromoanhydrides of aryl arsonous acids, which are the starting compounds for the synthesis of biologically active substances.

The purpose of the invention is to find new compounds with valuable properties.

Example 1. Bromohydrin tert.- butyloxyphenylacetic acid.

To 16 g (0.074 mol) of ethylphenylchloroarsine in 80 ml of dry benzene at room temperature is added with stirring a mixture consisting of 5.47 g (0.074 mol) of tert-butyl alcohol and 7.46 g (0.0 / 4 mol) of triethnlamine in 50 ml of benzene. Separated EtjN HC1

11.77 g (0.0 / 4 mol) of bromine in 20 ml of benzene are added dropwise to the solution with vigorous stirring. The benzene is then distilled off and the residue is distilled in vacuo. Yield 21.3 g (95%); bp 117-118 ° C ((1 mm Hg); n ™ 1.5861; d 1.5463.

PMR spectrum (SOSTS), $, ppm: 1.38 (s, CH3); /, 47 (m, C6Hff).

Mass spectrum, ra / z: Gm4 2250

Found,%: C 39.43; H 4.67; As 24.44.

Cw HHAsBrO.

Calculated,%: C 39.34; II 4.59; As 2h, 59 o

Od

1C ate

00

one

to

316

PRI mme R 2. Ethyl hydroxyhydroxy p-tolyl carboxylic acid. To 14 g (0.061 mol) of ethyl p-tolylhporarsin in 60 ml of dry CC1.4 at room temperature is added with stirring a mixture consisting of 2.79 g (0.061 mol) of ethyl alcohol and 6.13 g (0.061 g). mole) of triethylamine in 50 ml of SCC. Isolated HC1

9.71 g (0.061 mol) of bromine in 30 ml of CC1 are added dropwise to the solution with vigorous stirring. Then CC1 $ is distilled off, and the residue is distilled in vacuum. Yield 16.4 g (93%); bp 111-113 ° C (1 mm Hg); 1.5899; dЈ 1.5548.

HMR spectrum (CDC1}) L, m, d: 1.12 (t, CH3); 2.26 (s, si,); 3.70 (q, SNg); 7.24 m (S6NCH).

Mass spectrum, ra / z: m J 290; m-Br} 211-; 275.

Found,%: C 37.06; H 4.18; As 25.86. I CqH AsBrO

Calculated, As 25,77.

PRI me R 3 “Bromohydride of ethyloxyphenylcarboxylic acid.

C 37.11; H 4.1: 2;

stirring a mixture consisting of 3.6 g (0.061 mol) of isopropyl alcohol and 6.15 g (0.061 mol) of triethylamine in 40 ml of SCC. The separated EtjN "HCl" is filtered off, and in solution with vigorous stirring, 9.73 g (0.061 mol) of bromine are dripped in 30 ml of CC14. The CC1 is then distilled off and the residue is distilled in vacuo. Yield 18.3 g (94%); bp 139-141 ° C (1 mm Hg); p ™ 1.5931; 1.6102.

PMR spectrum (CDCl1), 5, ppm: 1.23 15 (d, CH3); 3.73 (s, OCH); 4.24 (q, CH); 7.25 (m, CgH).

Mass spectrum, m / z: m j 320; M-Br} 241.

Found,%: C 37.47; H 4.24; 20 as 23.24.

C, 0H14AsBr04.

Calculated,%: C 37.38; H 4.36; As 23.36.

And dim. 5. N-butyloxy-p-bromophenyl-personous acid bromohydride.

To 15 g (0.051 mol) of ethyl p-bromophenylchloroarsine in 100 ml of dry benzene at room temperature is added

To 10 g (0.046 mol) of ethylfenklchlor-30 P stirring a mixture consisting of

3.75 g (0.051 mol) of n-butyl alcohol and 5.13 g (0.051 mol) of triethylamine in 50 ml of benzene. The separated HC1 is filtered off, and 8.12 g (0.051 mol) of bromine in 30 ml of benzene are added dropwise to the solution with vigorous stirring. The benzene is then distilled off and the residue is distilled in vacuo. Yield 19.4 g (92%); bp 165-166 ° C (3 mm Hg); 1.6100; dj ° 1,8055

Arsine in 50 ml of dry benzene at room temperature is added with stirring a mixture consisting of 2.12 g (0.046 mol) of ethyl alcohol and 4.66 g (0.046 mol) of triethylamine in 30 ml of 3 benzene. The separated Et-jN-HCl is filtered off, and 39 g (0.046 mol) of bromine in 20 ml of benzene is added dropwise to the solution with vigorous stirring. Then benzene is distilled off, and the residue is distilled in vacuum. Yield 10.0 g (96%); bp 100-102 ° C (1 mm Hg);

p 1.5882; df 1.5836.

IMR spectrum (CDC1,) ,, ppm: 1.14 (t, SI3); 3.73 (q, CH2); 7.17 (m,

) -g „

Mass spectrum, m / z: (M j 276;

lI-Br 4 197.

Found,%: C 34-60; H 3.55; As 27.18.

CgH, 0 AsBrO,

Calculated,%: C 34.66; H 3.61; As 27.07.

II p and me 4 bromohydride isopropyloxy-o-anisylcarboxylic acid,

,, To 15 g (0.061 mol) of ethyl-o-anisyl-jpiopapcHHa in 100 ml of dry CC1 is added at room temperature at

four

five

five

stirring a mixture consisting of 3.6 g (0.061 mol) of isopropyl alcohol and 6.15 g (0.061 mol) of triethylamine in 40 ml of SCC. The EtjN "HC1 which is separated out is filtered off and 9.73 g (0.061 mol) of bromine in 30 ml of CC14 are added dropwise to the solution with vigorous stirring. The CC1 is then distilled off and the residue is distilled in vacuo. Yield 18.3 g (94%); bp 139-141 ° C (1 mm Hg); p ™ 1.5931; 1.6102.

PMR spectrum (CDCl1), 5, ppm: 1.23 (d, CH3); 3.73 (s, OCH); 4.24 (q, CH); 7.25 (m, CgH).

Mass spectrum, m / z: m j 320; M-Br} 241.

Found,%: C 37.47; H 4.24; As 23.24.

C, 0H14AsBr04.

Calculated,%: C 37.38; H 4.36; As 23.36.

And dim. 5. Bromoanhydride of n-butyloxy-p-bromophenylcarboxylic acid.

To 15 g (0.051 mol) of ethyl p-bromophenylchloroarsine in 100 ml of dry benzene at room temperature is added

P stirring mixture consisting of

3.75 g (0.051 mol) of n-butyl alcohol and 5.13 g (0.051 mol) of triethylamine in 50 ml of benzene. The separated HC1 is filtered off, and 8.12 g (0.051 mol) of bromine in 30 ml of benzene is added dropwise to the solution with vigorous stirring. The benzene is then distilled off and the residue is distilled in vacuo. Yield 19.4 g (92%); bp 165-166 ° C (3 mm Hg); 1.6100; dj ° 1.8055.

Mass spectrum, m / z: 382; 303; fM-BEj 2z4.

Found,%: C 31.34; H 3.50; As 19.68. С (0Н13АзВгО.

Calculated,%: C, 31.25; H 3.39; As 19.53.

PRI me R 6. Bromoanhydride n-butyl hydroxy-o-anisyl carboxylic acid.

To 20 g (0.081 mol) of ethyl-o-anisyl-chloroarsine in 150 ml of dry CC14 at room temperature is added with stirring a mixture consisting of 6.0 g (0.081 mol) of n-butyl alcohol and 8.19 g (0.081 mole) of triethylamine in 50 ml of CCl. The separated Et, N HC1 is filtered off, and 12.98 g (0.081 mol) of bromine in 50 ml are added dropwise to the solution with vigorous stirring.

CC1h Then, CC1f is distilled off, and the residue is distilled in vacuo. Yield 26.0 g (96%); -t.kip 145.5-146 ev (f mm Hg) p 1.5 / 69; df 1,5131.

Mass spectrum, m / z: M j 334; M-VgZ 22b.

Found,%: C 39.31; H 4.86; As 22.28.

C m H, 6AsBrOz.

Calculated,%: C 39.40; H 4.78; As 22.39.

When calculated on the corresponding aryl dichloroarsine, the yield is 8 / -86%.

Thus, the proposed method allows to obtain bromohydrides of aryl arsonous acids in high yields with high purity of the target products.

0

five

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Claims (1)

Invention Formula The method of obtaining bromohydrides of aryl arsonous acids of the general formula XC6H.As (OR) Br, where X is H, p-CH, o-HCFC, R -, iz-С Н ,, Н-С4.Н ,, т-С4Н ,, characterized in that ethylarylchloroarsine of the general formula XC6H4 (CrH5.) AsCl, where X - has the indicated values, is successively reacted with the corresponding alcohol in the presence of triethylamine while separating the triethylamine hydrochloride and bromine, followed by isolation of the target product, and the process is carried out in benzene or carbon tetrachloride at 20 ° C.