SU1199751A1 - Method of producing sodium salts of aryltetrasulfoacids - Google Patents

Abstract

METHOD FOR PRODUCING SODIUM SALTS OF ARYL TETRASULPHATE ACIDS The general formula for phenyl bridging compounds is a compound of the formula (L) where X - has the indicated meanings; Y is bromine or chlorine, which is subjected to sulfonation with 2530% oleum at a molar ratio of the compound of the formula Pi SO,. equal to 1: 4.5-13.7, and a temperature of -50160 ° C for 1-4 hours and neutralized with anhydrous sodium carbonate or an aqueous solution of sodium chloride, followed by treatment of the resulting disodium salt of the corresponding SP of the diphenyl bridging compound of the formula SOsNa X and Y have the indicated values, sodium sulfite in the presence of sulfur: o acidic copper at a molar ratio of vj equal to 1:

Description

This invention relates to an improved process for the preparation of sodium salts of aryl tetrasulfonic acids of general formula I:

N0038

SOsNa

t ozbcho

where X is .rpynriS; CO, or simple connection,

which can be used in the monomer screen for heat-resistant polymeric materials. .

The aim of the invention is to simplify the process, increase the yield and expand the range of target products.

Example 1. 20.0 g (0.08 mol of 4,4-dichlorobenzophenone, 60.0 ml (0.36 mol of St. 80) of 25% oleum is heated for 3 hours at 160 ° C. with stirring. The reaction mass is cooled to room temperature temperature and poured into 200 ml of cold water. The precipitate is filtered off, dissolved in water at BO-C and the solution is neutralized with anhydrous sodium carbonate (pH 8-9). Disodium salt of 3,3-disulfonic acid-4,4-dichlorobenzophenone is filtered washed with cold water and dried. The yield of the desired product is 29.1 g (80%).

IR spectrum: about 1650, dd 1210, 5 50/1110.

Found,%: S 14.07; CE 15.56; Na 10.28.

C HgNajO.

Calculated, S 14,00; CE 15.48; Na 10.11.

10.2 g (0.022 mol) of the disodium salt of 3,3-disulfonic acid — 4,4-dichlorobenzophenone, 10.0 g (0.079 mol) of sodium sulfite and 0.5 g (0.002 mol) of copper sulphate in 100 ml of water are heated 2, 5 hours at. The reaction mass is cooled, the precipitate is filtered off. The yield of tetrasulfuric acid of 3,4,3,4-tetrasulfonic acid benzophenone after recrystallization from water is 11.0 g (85%).

IR spectrum, 1660, so 1210,;) ebo 1110.

Found,%: S 21.50; Na 15.82.

C ,,, Na4

Calculated by; S 21.69; Na 15.59.

P p and m ep 2. 100.0 g (0.31 mol) 1,1-dichloro-2,2-5is (4-chlorophenyl) ethylene, 300 ml (1.79 mol of St. 50) 25% Oleum is heated at 50 ° C for 1 h. The reaction mass is cooled, poured into water, the precipitate of disulfonic acid is dissolved in water and neutralized with sodium carbonate as in Example 1.

The yield of the disodium salt of 1,1-dichlor2, 2- & o (4-chloro-3-sulfophenyl) ethylene is 145.7 g (90%).

IR spectrum, cm: - hr 1240;

650,1120; with

840.

SSE

Found,%: C 32.02; S 12.50; Na 8.83.

Calculated,%: C 32.18; S 12.26; Na 8.81. .

0 52.5 g (0.10 mol) of disodium salt of 1,1-dichloro-2.2-K «with (4-chloro-Ssulfofenil) ethylene, 38.0 g (0.3 mol) of sodium sulfite and 1.0 g (0.004 mol) of copper sulfate in 250 ml of water 5 is heated at 200 ° C for 4 hours. The reaction mass is cooled and the precipitate is filtered off. The target product is recrystallized from water. The yield of the tetrasodium salt of 1,1-dioxlor-2,2-Suco (3,4-disulfs) phenyl) ethylene is 53.8 g (82%).

IR spectrum, cm: eog 1200, eso 1050, 9 ° Found: C 25.32; H 1.15; S 19,34

C, 4HgNa O S4CE2

Calculated,%: C 25.57; H 0.91; S 19.48.

Froze 15.0 g (0.048 mol) of 4,4-dibromodiphenyl and 92 ml (10.66 mol of St. SOj) of 30% oleum are heated at 80 ° C for 4 hours. The reaction mass is cooled and poured into 0.5 l. 30% aqueous solution of sodium chloride. The precipitate is filtered and crystallized from water. The yield of the disodium salt of 3,3disulphonic acid-4, 4-dibromodiphenyl is 20.5 g (89%).

IR spectrum, cm-: oceo, 1200, 0.

Found,%: C 27.50; H 1.05; S 12.12.

Calculated,%: C 27.90; H 1.16; 5 S 12.40.

10.3 g (0.02 mol) of disodium salt of 3.3-disulfonic acid — 4.4-dibromodiphenyl, 8.8 g (0.07 mol) of sodium sulfate, 0.75 g (0.003 mol) of copper sulfate and 100 ml water is heated for 3 hours at 220c. The reaction mass is cooled, the precipitated precipitate is filtered and recrystallized from water. The yield of tetrasodium salt of 3,4,3,4-tetra sulfonic acid of diphenyl is 10.0 g (89%). 1130, IR spectrum, cm 55021050. Found,%: S 22.16; Na 16.78; From 25.87. C -jH Na Oi-jS Calculated,%: S 22.78; Na 16.37; From 25.62. EXAMPLE 4 20.0 g (0.08 mol of 4,4-dichlorobenzophenone, 32 ml (0.32 mol of St. SOj) of 40% oleum are heated for 0.75 h at 170 ° C. with stirring The reaction mass is cooled and poured into water. The precipitate is filtered off, dissolved in water and neutralized with sodium carbonate. The yield of disodium salt of 3.3-disulfonic acid - 4,4-dichlorobenzophenone was 23.6 g (65%). 9.2 g (0.02 mol) disodium salt of 3.3-disulfonic acid — 4.4-di chlorobenzophenone, 10.0 g (0.08 mol) of sodium sulfite and 0.99 g (0.004 mol of copper sulfate in 100 ml of water is heated 1, 5 h at 190 C. The reaction mass is cooled, the precipitate is about The yield of tetrasodium salt 3,4,3, 4-tetrasulfonic acid benzophenone after recrystallization is 88 g (75%). Example 5: 15.6 g (0.05 mol 4,4-dibromodiphenyl and 200 ml (0.75 mol of St. SO,) of 16% oleum ul f, -f is heated at 40 ° C for 5 hours. The reaction mass is cooled and drunk in 0.5 l of 30% aqueous solution of sodium chloride 51. The precipitate formed is filtered off and crystallized from water. The output of the disodium salt of 3,3-disulfonate. - 4,4-dibromodiphenyl is 15.4 g (64%). 10.3 g (0.02 mol) of disodium salt of 3.3-disulfonic acid — 4.4-dibromodiphenyl, 6.3 g (0.05 mol) of sodium sulfite, 0.1 g (0.0004 mol) of copper sulfate and 100 ml of water is heated for 5 hours at. The solution is cooled, the precipitated precipitate is filtered off and recrystallized from water. The yield of tetrasodium salt of 3,4,3,4-tetrasulfonic acid of diphenyl is 7.3 g (71%). The table shows the data justifying the proposed conditions of the process. As follows from the table, an increase in temperature and a reduction in the duration of the sulfonation and sulfide chlorination reactions leads to a decrease in the yield of the target products (experiments 1, 5, 5, 6, 9 and 10). At the same time, a decrease in temperature and a reduction in the duration of both the sulfonation process and the sulfodechlorination leads to a significant decrease in the yield of the target products (experiments 4 and 5). At optimal temperatures and processing times with an increase in the concentration of oleum during sulfonation, a decrease in the yield of the target products is observed, apparently due to the formation of polysulfonation products (experiments 3.7 and 11); At the same time, an increase in the molar ratio of the reagents during sulfonation does not lead to an increase in the yield of the target products (experiments 4.8 and 12). It also does not lead to an increase in the yield of the target products and a decrease in the concentration of oleum at the stage of sulfonation (experiments 4.8 and 12),

Table continuation

Claims (1)

METHOD FOR PRODUCING SODIUM SALTS OF ARILTETRASULFOXIDES of the general formula (I) where X is the group ^ CO, ^ C = CC? ₂ or a simple bond using sulfonation of a derivative of diphenyl bridge compounds when heated, characterized in that, in order to simplify the process, increase the yield and expand the range of target products, a compound of the formula Y - © LX - © -Y where X - has the indicated meanings; Y - bromo or chloro which is subjected to sulfonation with oleum 2530% ethyl molar ratio of the formula S0 ₃ Pi ^compound; . equal to 1: 4.5-13.7, and a temperature of -50160 C for G-4 h and neutralization with anhydrous sodium carbonate or an aqueous solution of sodium chloride, followed by treatment of the obtained g disodium salt of the corresponding diphenyl bridging compound of the formula SU. „, 1199751 where X and Y have the indicated meanings, with sodium sulfite in the presence of copper sulfate at a molar ratio of 1: (3-3.6) :( 0.04-0.15), respectively, and a temperature of 200 ~ 220 s within 2-4 hours