SU687065A1 - Disulfoacids 4,4', 4'',4'' of tetra-substituted cobalt phthalocyanine as catalyst of oxidizing thiolcompunds with molecular oxygen - Google Patents

Description

(54) Disulfonic acid 4, 4, 4, 4 - tetra-substituted phthalocyanine cobalt as catalysts for the oxidation by molecular oxygen of thiol compounds

The invention relates to the synthesis of macroheterocyclic compounds having a phthalocyanine structure, namely, the synthesis of 4, 4, 4, 4-tetramamethyl disulfonic acid cobalt phthalocyanine, which can be used as catalysts for the oxidation of thiol compounds with molecular oxygen.

This property allows us to assume the possibility of applying to the purification of sulfur-containing wastewater and gas emissions. There are 4, 4, 4, 4 -tetrazamemdenny phthalocyanine cobalt of the general formula

where R is N0, OH, and NH, which are the closest in structure to the new compounds 1. However, these compounds are insoluble in water and aqueous solutions of alkalis,

The aim of the invention is metal complexes of macroheterocyclic compounds with catalytic activity in oxidation processes.

These properties are determined by the new chemical structure of disulfonic acids of 4, 4, 4, 4-tetrasubstituted cobalt phthalocyanine, which is expressed by the following general formula:

20

25

where R is isTOg, OH or NH.

Compounds of this general formula are obtained by treating the corresponding 4, 4, 4, 4-tetrasubstituted cobalt phthalocyanine with a sulphating mixture obtained by passing nitrogen through 65% oleum heated to OOC. The process is conducted at 80-130 C.

Then, pure nitrogen is passed through for 1 hour to remove unreacted sulfuric anhydride,

The resulting product is washed with anhydrous acetone and dried under vacuum at.

Example 1. Disulfonic acid 4, 4, 4 4-tetranitrophthalocyanine cobalt. ,

3.0 g (0.0040 mol) of 4, 4, 4, 4 tetranitrophthalocyanine cobalt in a rotating flask of a modified rotary evaporator IL-1, heated before and for 3 hours, the sulphurized mixture obtained by passing nitrogen in an amount of 0.1 l is fed into the reactor / min. after 65% oleum heated to, then pure nitrogen is passed through the reactor for 1 h to remove unreacted sulfuric anhydride. The product obtained is washed with anhydrous acetone and dried under vacuum at. Dry weight 3.34 g, yield 92%.

Found,%: S 6.62; From 5.98;

With “H, j WITH.

Calculated,%: S 6.99; From 6.45.

P. m and m p 2. Disulfonic acid 4, 4, 4 tetraoxyphthalocyanine cobalt.

The preparation of disulfonic acid 4, 4, 4, 4-tetraoxy phthalocyanine cobalt is carried out under conditions similar to example 1. Sulphurisation temperature of IOS. Dry weight 3.49 g, yield 93%.

Found,%: S 7.89; From 6.96.

,

Calculated,%: S 8.01; From 7.38.

Example 3. Disulfonic acid 4, 4, 4, 4-tetraamino phthalocyanine cobalt.

Sulfonation temperature. The weight of the dry product 3,42. G, yield 91%.

Found,%: S 8.13; From 7.61.

CjiH oNw.

Calculated,%: S 8.05; From 7.42.

The resulting disulfonic acids are blue powders, A, “1xC 680, 690, 720 nm (in dimethyl sulfoxide for disulfonic acids tetranitro, tetraoxy and tetraamino phthalocyanine-cobalt, respectively).

They do not melt at 400 ° C, are readily soluble in water, aqueous alkaline solutions, dimethyl sulfoxide, and difficult to dissolve in most organic solvents.

Example 4. Determination of catalytic activity in thiol oxidation reactions.

N-propyl mercaptan (concentration 0.3 mol / l), aqueous caustic soda solution (concentration 10%), disulfonic acid 4, 4, 4, 4-tetranitrophthalocyanine cobalt (concentration 2, mol / l) are placed in a stirred reactor. The oxidation is carried out at AIA with molecular oxygen fed to the reactor through a sparger in an amount of 0.3 l / min for 15 minutes. Samples were taken during the test to determine the concentration of mercaptide. Analyzes were carried out by potentiometric titration of mercaptide with silver ammonia on a pH-340 instrument. Disulfonic acid 4, 4, 4, 4 tetranitrophthalocyanine cobalt has a high catalytic activity. Within 10 minutes, 71.1% of n-propyl mercaptan is oxidized.

Example 5. The oxidation of n-propyl mercaptan using 4, 4, 4, 4 -tetraoxyphthalocyanine cobalt as a catalyst for disulfonic acid is carried out under conditions analogous to Example 4. 89.5% of n-propyl mercaptan is oxidized in 10 minutes.

Example 6. Oxidation of n-propyl mercaptan using 4, 4-, 4, 4-tetra-amino-phthalocyanine cobalt as disulfonic acid catalyst is carried out under conditions analogous to example 4. 90.6% of n-propyl mercaptan is oxidized in 10 minutes.

Example 7. 0.05 mol of sodium diethyl dithiocarboxylate sodium three-aqueous solution is dissolved in 100 ml of water, 5-10 mol of disulfonic acid of 4, 4, 4, 4-tetranitrophthalocyanine cobalt are added and, within 3 hours, maintaining with 5% sulfuric acid acids pH 8.0-8.5 are purging; air.

The separated product (thiuram E) is filtered off, washed with water to obtain a colorless filtrate and dried at. Yield 86%, mp. 68.2-68.6С.

Example 8. Oxidation of sodium diethyldithiocarbamate using 4, 4, 4/4 -tetraoxyphthalocyanine cobalt disulfonic acid as catalyst is carried out under conditions similar to Example 7. 87% yield, m.p. 68.2-68, bs

Example9. 1.9 Sodium dimethyldithiocarbamate (MH carbamate), dissolved in 100 ml of borate buffer, solution with a pH of 8.3, is added to a bubble type glass reactor.

IjOTSlO mol of disulfonic acid is 4, 4, 4, 4-tetranitrophthalocyanine cobalt and is purged with air in an amount of 1 l / m. During the experiment, samples are taken to determine the content of carbamate MN in the reaction mixture by potentiometric titration of 0.02 n. copper sulfate solution on the device. In 1 hour, 40% of the carbamate MN is oxidized.

Example 10. The oxidation of carbamate MN using in; As a catalyst disulfonic acid 4, 4, 4, 4 -tetraoxyphthalo

cobalt cyanine is carried out under conditions analogous to example 9. In 1 hour, 41% of the carbamate of MN is oxidized.

Example. The oxidation of carbamate to MH using 4, 4, 4, 4-tetraamino phthalocyanine cyanine cobalt as disulfonic acid catalyst is carried out under conditions analogous to Example 9. 90% of the carbamate MH is oxidized.

For comparison, a proven catalyst for the oxidation of thiols — phthalocyanine cobalt disulfonic acid — is tested. The test results are carried out in table. and iz. The activity of catalysts in the oxidation reaction of n-propyl mercaptan at, Kt I 2.58-10 mol / l, NaOH 0%, RSHl 0.3 mol / l. Table 1

The activity of catalysts in the oxidation reaction of dimethylcarbg # 1ata, pH 8.3, temperature 20 С, time h, mol / l.

Cobalt phthalocyanine disulfonic acid

Disulfonic acid 4, 4, 4

4-tetranitrophthalocyanine

cobalt

Disulfonic acid 4, 4, 4,

4-tetraoxyphthalocyanine

cobalt

Disulfonic acid 4, 4, 4,

4-tetraamino phthalocyanine

cobalt

table 2

5.8 ± 0.4

7.2 ± 0.4

7.4 ± 0.3

25.3 ± 0.3

6870658

In addition, these compounds exhibit a high catalytic activity in the oxidation of sodium diethyldithiocarbexylate.

For "1 st of the invention of Disulfonic acid 4, 4, 4 4 tetra-substituted cobalt phthalocyanine of the general formula

where R is N0, OH, or NH2, as catalysts for the oxidation of thiol compounds by molecular oxygen.

Sources of information taken into account in the examination of 25 Works of the Tambov Institute

Chemical Engineering, 1969 vol. 3, s. 100.