SU740803A1 - 3,6,3',6',3",6",3''',6'''-octaoxyphthalocyanine bromoderivatives of cobalt possessing catalytic property in sodium sulfide oxidation reaction with air oxygen and their preparation method - Google Patents

Description

thieves, the starting compounds quantitatively precipitate. The products are soluble in dimethylformamide and acetic anhydride in the presence of sulfuric acid, practically insoluble in common organic solvents.

Unlike the unsubstituted 3,6,3, b, 3,6,3, b-octo-oxyphthalocyanines of divalent metals, the new compounds are dissolved in caprolactam, and the solution has a dark green color.

A compound close in structure - 4,5,4,5,4,5, 5-octachlor-3, b, 3,6,3,6, 6-octo-oxyphthalocyanine copper is obtained as follows.

The initial product of the synthesis is 3, b-dioxyphthalodinitrile 2, which is chlorinated 3 and then the resulting 4,5-dichloro-3, b-dioxyphthalodinitrile by condensation in diethylene glycol at 200 ° C in the presence of copper oxides is cyclized to 4,5,4,5 , 4, 5, 4, 5-octachlor-3, b, 3, b, 3, b, 3, b-octo-oxyphthalocyanine copper. When expanding this method to the corresponding bromo derivatives, it is not possible to obtain the target products with a bromine content of more than 2 atoms per molecule. In addition, these compounds are not soluble in aqueous solutions of alkalis, which may play a negative role in catalysis,

A process for the preparation of compounds of the formula I is described, consisting in that 3,6,3,6,3,6,3, -octa-oxy phthalocyanine cobalt, obtained mainly by condensation, by baking 3,6-dioxyphthalodinitrile 4 is subjected to bromination in a medium chlorosulfonic acid at 60 - in the presence of elemental iodine as a catalyst. The yield of the target product is 75% of the theoretical.

The dependence of the content - bromine on the synthesis temperature and maxima. The absorption of the bromo-substituted 3,6,3,6,3-, b, 3,6-octaoxyphthalocyanines of cobalt in dimethylformamide is given in the table.

6048.08 35,394,75,51

Claims (4)

8048.08 47.187.94.43 The obtained target product does not need to be purified, because the bromination is carried out in an environment of zhorosulfonic acid, followed by separation on ice, where the phthalocyanine is purified. The use of chlorosulfonic acid is due to the limited solubility of 3,6,3,6,3,6,3,6-oct oxyphthalocyanine cobalt. A change in the bromination temperature from 60-80 ° C makes it possible to obtain bromo-substituted 3,6,3,6,3,6,3,6-oct-oxyphthalocyanines of divalent metals with bromine content from b to 8 atoms per molecule. And p and meer. 0.7 g of bromine, 0.02 g of elemental iodine, and heat up to 80 ° C are added to 1.4 g 3,6,3,6, 3,6,6,6-octa-oxyphthalocyanine cobalt in 10 ml of chlorosulfonic acid and stirred at the same temperature for 8 h. Then the reaction mass is poured on ice, filtered, the precipitate is washed with water to a neutral medium and dissolved in 1% sodium hydroxide solution. The solution is filtered and acidified with hydrochloric acid. The precipitation is washed with water to a neutral medium and with acetone to a colorless filtrate, and then with methanol in a Soxhlet apparatus. The yield is 4,5,4, b, 4,5,4,5-octabrom-3, 6,3,6,3,, 3,6-octoxyphthalcyanine cobalt is 75% ..; The obtained bromo-substituted cobalt octaoxyphthalocyanines were tested for catalytic activity in the oxidation of sodium sulfide with atmospheric oxygen. For comparison, the sodium disulfophthalocyanine cobalt sodium salt is taken, which is used as an industrial catalyst in the oxidation of sulfur-containing compounds. When tested in identical conditions x disodium salt of disulfonic acid phthalocyanine cobalt showed a degree of purification of sodium sulfide solution equal to 75.61%, in contrast to 87.95% and 95.82% in the case of bromine-substituted 3,6,3 6,3,6 , 3,6-octaoxyft anodine cobalt with a content of br 35.39 and 47.18%, respectively. From a comparison of these data it blows that the proposed ones are connected by more efficient catalysts for the oxidation of sodium sulfate with oxygen in the air. Claim 1. Bromopropyl 3,6,3,6 6, 3,6-octo-oxyphthalocyanine cobalt 4 He where X is hydrogen, y is bromine; or X and Y are bromine, exhibiting a catalytic property in the oxidation of sodium sulfide by oxygen in air. 2. A method of producing compounds according to claim 1, characterized in that 3,6,3,6,3, 6, 3, 6-octa-oxyphthalocyanine cobalt is brominated in chlorosulfonic acid at 60-80 ° C in the presence of elemental iodine as a catalyst. Sources of information taken into account in expert studies 1. Dabrowski R., Witkiewicz Z. Uteenianie kumenu u obecnpsci osmio. Hydroksv - ftaPocyianiny miedzi i ej pochodnych- Tecs. nauk. fnst ciezk. ZUS.-BGD. B iachowni SCaskiei 1972, 4, No. 20, s. 87-100. 2. Methods of obtaining chemical reagents and preparations. Issue 3 VNII chemical reagents and high-purity chemicals. M., 1961, p. 66 3.MitchePe R.W.The preparation of 2,3 dycyano 5,6 dichoroginone-. Canada gournaC of Chemistry, VoK 41, 1963, p. 550. 4. Author's certificate of the USSR 192995, cl. From 09 to 47/04, 1966.