SU1348341A1 - Method of producing salts of 3,5-dialkylpyrocatecholphosphoric acid - Google Patents

Description

The invention relates to the chemistry of organophosphorus compounds, namely to a method for the preparation of salts of 3.5 dialkylpyrocatechiphosphoric acid of the general formula

HE

1С%) (0) (ОУ) 2

R

where r y

methyl or t-butyl;

alkali metal cation or

triethylammonium,

O-blending antioxidant with your own-- CTBaNra, soluble in water

can be used in biology, medicine, food industry and agriculture, as well as in organisms,

The purpose of the invention is to develop a simple and affordable method for the preparation of salts 3 :, 5-dialkylpyro-catechin phosphoric acid of formula I,

Example 1, Preparation of 3,5-d. I -t-butylpyrocatechol phosphate of lithium, K 1.54 g (O ,, 01 mol) phosphorus oxychlorides of dissolved in 20 ml of absolute benzene, with a switch: licking, a solution of 2.22 is added simultaneously g (0.01 mol) 3 H-di-tert-butyl pyrocatechols-h in 20 mp of absolute benzene and a solution of 15.01 g three times in absolute, Mixture is sewn for 1 h at time, triethylamine hydro: sg10rid, K the resulting solution of the phosphorylating product in benzene with vigorous stirring and 20 ° C is added during 1 h g (0.04 mol) of crushed hydroxide and stirring was continued for another 4 hours "FILTER O-extracting the resulting mixture of salts, the filter cake washed with chloroform. The chloroform extracts are evaporated in vacuo; 5 the residue is washed with acetone and dried.

3,5-di-tert-butyl pyroca-technical lithium phosphate is obtained; yield 1 g (32%) ;.

sublimation temperature 220 ° C; +1.66 m, d

Found, I C 53.49; H 6.70; O 25.44; P 9.91; Li 4., 46.

31

„I4 ,. Calculated.,%: C 53.53;

H

6.69; O 25.45; R 9.88; Li 4.45.

Soluble in water (0.02 mol / l), methanol, ethanol, chloroform, oryme problems in benzene, ether, acetone.

reaction1-g but relative to in h

Electron velocity K ,, 3 10 m.

PRI mme R 2. Obtaining 3.5-di-tert-butylpyrocotane 1. lithium hinfosfat.

To 2 g (0.013 mol) of 4c oxychloride sphora, dissolved 1-south n 20 ml of absolute 6eH3o.nas IIH stirring, the solution is simultaneously boiled

; 2.22 g (0.01 mol) of 3,5-di-tert-butyl-pyrocatechin in 20 ml of absolute betazol and a solution of 1.01 g (0.01 mol) of triethylamine in abscess benzene. The mixture is stirred for 1 h at 20 ° C, triztilamine hydrochloride, O, is obtained from fs.

.. Packed over for 1 hour. About „96 g

 J -;

(0.04 mol) of crushed; watered hydroxide ;; tsti and pro; -, they are left to be diluted: h, Filtered: (this mixture of salts formed is precipitated; chlorine is evaporated. The chloroform extracts are evaporated in an Akum. Residue It is washed with acetone, Po.-3 35 D-di-ter-butylpirsshatechin phosphate lithium is taken in. Yield 1 g (: 2%) i -I- 1.66 m, d, sublimation temperature.,

Found,% :: C 53,50; H 6.71; About 25, D2, R 9 ,. 90: Li 4.47,

five

6.69; 3.5 di

9

, Li2 (XP

Calculated 5%; C 33.53; B: 25.45; R 9.88; Li 4.45. PRI me R 3. Getting

 tri-butyl pyrocatechol phosphate tri-3: 1 ammonium.

K 1.54 g (0.01 mol) oxychloride

0 phosphorus; dissolved in 20 ml of absolute beiso.l, while stirring, a solution of 2–22 g (, 0–01 mol) of 3 5 5-di-tert-butyl-pyrocatechiga a in 20 ppm of absolute ben5 ash and a solution of 1 g (0.01 mol) of tri-ethipamine in absolute .. benzene. The mixture is stirred for 1 h with a gri of 20 ° C, filtering triethylamine hydrochloride is released, the solution is evaporated in a vacuum,

0 The resulting Pro duct of phosphorylation of 3,5-di-tert-butylpyrocatechol is dissolved in 20 ml of absolute 1,4-cyoxane and, under vigorous stirring at 20 ° C, at the same time, drip: gf, add a solution of 0.36 g (0, 02 mol) of water in 10 ml of absolute 1., 4-dioxane and a solution of 4.04 g (0.04 units of triethylamine-) w in 10 ml of absolute 1.4-dioxane. Stirring the product. Efu.e 4 h.

313A83414

The calculated amount (0.04 mol) of crushed triethylamine hydrochloride hydroxide is filtered off.

The solution of the hydrolysis product in 1,4-dioxane is evaporated in vacuo, the residue is washed with acetone and dried to obtain 3,5-di-tert-butylpyrocatechol triethylammonium 5 yield 2.3 g (56%), so pl. 110-111 C, +1.9 ppm

Calculated,%: C 61.90, H 10.52; O 15.87, P 6.15, N 5.55.

.

Found,%: C 61.81; H 10.55; About 15.80; P 6.21; N 5.61.

PRI me R 4. Obtaining 5-methyl -3-tert-butylpyrocatechinphosphate lithium.

 To the benzene solution of the phosphorylation product 1.8 g (0.01 mol) of 5-methyl-3-tert-butylpyrocatechin; po10

15

20

sodium, stirring is carried out for another 4 hours. The mixture of salts is filtered off and the precipitate is washed with chloroform to separate the alkali metal chloride. The chloroform extracts are evaporated in vacuo, the residue is washed with acetone and dried. 3,5-di-tert-butyl pyrocatechol phosphate sodium is obtained; yield 1.5 g (43%), t, pl. 340-342 C, +1.51 ppm

Calculated,%: C 48.55; H 6.07; O 23, 12; P 8.96; Na 13.29.

C h iNaaOsP

Found,%: C 48.50; H 6.11, O 23 J 1 1; P 8.98; Na 13.30.

PRI me R 6. Getting 3 5-di-tert-butylpyrocatechol potassium phosphate.

To 1.54 g (O., 01 mol) of phosphorus oxychloride dissolved in 20 ml of abs. benzene, while stirring, a solution of 2, .22 g (0.01 mol) of 355-di-tert-butyl pyroca-techin in 20 ml of abs. benzene and a solution of 0.79 g (0.01 mol) of pyridine in 20 ml of abs “benzene. The mixture is stirred for 1.5 hours at 20 ° C, filtered off with pyridine hydrochloride. To the obtained solution of the phosphorylation product in benzene with vigorous stirring, 2.24 g (0.04 mol) of crushed potassium hydroxide are added over 1 hour. Stirring is carried out more than 4 hours. The resulting mixture of salts is filtered off and the filter cake is washed with methanol to separate the silk metal chloride. The alcoholic extracts are evaporated in vacuo, the residue is washed with acetone, and dried.

luchennoto similar to examples

with vigorous stirring at 20 ° C, 0.95 g (0.04 mol) of ground lithium hydroxide was added over 1 hour. Stirring is continued; e 4 h. The resulting salt mixture is filtered and the precipitate is washed with chloroform. The chloroform extracts are evaporated in vacuo, the residue is washed with acetone, and dried.

Get 5-methyl-3-tert-butylpyrcium lithium catechol phosphate.

Output 1.1 g (40.4%), sublimation temperature - 220 ° C, 8 p + 1.7 m, d.

Found,%: C 48.53; H 5.51; O 29.41-, P 11.40, Li 5.15 „

C ,, H ,, Li,

Calculated,%: C 48.45; H 5.62;

029.45; P 1 1.34; Li 5.14.

Example 5: Preparation of 3,5-di-tert-butyl pyrocatechol sodium phosphate

To 1.54 g (0.01 mol) of phosphorus oxychloride dissolved in 20 ml of absolute benzene, a solution of 2.22 g (0.01 mol) of 3,5-di-tert-butylpyrocatechin in 20 ml is added dropwise with stirring absolute benzene and a solution of 1.01 g (0.01 mol) of triethylamine in 20 ml of absolute benzene. The mixture is stirred for

1 h at 20 ° C, triethylamine hydrochloride is filtered off. To the resulting solution of the phosphorylation product in benzene with vigorous stirring and 20 ° C, 1.6 g are added over 1 hour.

VNIIPI Order 5163/24

Random polygons pr-tie, Uzhgorod, st. Project, 4

c- (0.04 mol) crushed hydroxide

-

ten

15

20

thirty

35

;) 5 e-

 ,

45

sodium, stirring is carried out for another 4 hours. The mixture of salts is filtered off and the precipitate is washed with chloroform to separate the alkali metal chloride. The chloroform extracts are evaporated in vacuo, the residue is washed with acetone and dried. 3,5-di-tert-butyl pyrocatechol phosphate sodium is obtained; yield 1.5 g (43%), t, pl. 340-342 C, +1.51 ppm

Calculated,%: C 48.55; H 6.07; O 23, 12; P 8.96; Na 13.29.

C h iNaaOsP

Found,%: C 48.50; H 6.11, O 23 J 1 1; P 8.98; Na 13.30.

PRI me R 6. Getting 3 5-di-tert-butylpyrocatechol potassium phosphate.

To 1.54 g (O., 01 mol) of phosphorus oxychloride dissolved in 20 ml of abs. benzene, while stirring, a solution of 2, .22 g (0.01 mol) of 355-di-tert-butyl pyroca-techin in 20 ml of abs. benzene and a solution of 0.79 g (0.01 mol) of pyridine in 20 ml of abs “benzene. The mixture is stirred for 1.5 hours at 20 ° C, filtered off with pyridine hydrochloride. To the obtained solution of the phosphorylation product in benzene with vigorous stirring, 2.24 g (0.04 mol) of crushed potassium hydroxide are added over 1 hour. Stirring is carried out more than 4 hours. The resulting salt mixture is filtered off and the filter cake is washed with methanol to separate the silk silk chloride. The alcoholic extracts are evaporated in vacuo, the residue is washed with acetone, and dried.

3,5-di-tert-butyl pyroca-technical potassium phosphate is obtained, yield 1.3 g (34%), m.p. 450 ° C, +1.59 ppm

Calculated,%: C 44.44, - H 5.56, O 21, 16; P 8.20; To 20.64 ..

C ,, H, KjOsP.

Found,%: C 44.40; H 5.58, O 21.19; P 8, 18; To 20.65.

Thus, the proposed method allows to obtain water-soluble salts of 3,5-dialkyl pyrocatechol phosphoric acid in an accessible way with a relatively good yield by selecting the appropriate conditions (temperature, solvent, molar ratio) for each stage of the process.

Circulation 347

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Claims (1)

METHOD FOR PRODUCING 3,5-DIAL KILPIR SALTS ABOUT CATHEINPHOSPHORIC ACID of general formula OH R where R is methyl or tert-butyl J Y is an alkali metal or triethylammonium cation, which consists in the fact that 3-alkyl-5-tert-butylpyrocatechol is reacted with phosphorus oxychloride (5+) in a molar ratio of 1.0: 1.0-1.3, in the presence of pyridine or triethylamine in dry benzene at room temperature in an inert gas atmosphere, followed by separation of the resulting 3-alkyl-5-tert-butyl pyrocatechindichlorophosphate, its hydrolysis by the gradual addition of a stoichiometric amount of finely ground alkali metal hydroxide _e in benzene and whether S of an aqueous solution of triethylamine in 1,4-dioxane at room temperature and vigorous stirring for 3.5-4.0 hours, and washing the target product with acetone. I48341