SU1395646A1 - Method of producing ammonium salt of tetrasulfophthalocyanine metallocomplexes - Google Patents

Abstract

The invention relates to metal-organic complexes, in particular the preparation of the ammonium salt of tetrasulfophosphate-cobalt (iron or copper) complexes, used as a catalyst for redox processes or as dyes. The process is carried out by sulfonating phthalic anhydride with oleum, followed by sequential treatment of the sulfomass with the main component — an aqueous solution of NH and the corresponding metal chloride, taken in an amount of (0.3–0.5) moles per 1 mol of the reaction sulfomass. These conditions simplify the process of synthesis and purification of the target product by eliminating the step of separating the intermediate product and obtaining the target substances in one apparatus with a yield of up to 90-94% while reducing the process time from 7-8 to 1.5-2 hours (L

Description

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The invention relates to an improved process for the preparation of the ammonium salt of tetrasulfophthalocyanine metal complexes of the general formula

SOslt H

BN40zzZ

HAZARD

which are widely used as catalysts for redox processes, as well as dyes.

The purpose of the invention is to increase the yield of the target product, simplifying the process.

Example 1. Obtaining sulfonic mass. In a two-neck flask supplied

I with a stirrer and placed in the melt of Wood,

I load 50 g of phthalic anhydride and melt at 140 ° C, then 40 ml of 25% oleum is poured and the temperature is raised to 200 ° C. Within 4 hours, 4.5 ml of 60% oleum is poured with stirring. Then the mixture you-.

Hold for 2 more hours and heat off. Upon cooling, a sulfomass is obtained, containing a solution of 4-sulfophthalic anhydride in sulfuric acid.

Example 2, 10 ml of sulfomass containing 10 g of sulfophthalic anhydride and 7 g of sulfuric acid are neutralized while cooling 12.2-12.5 ml of a 35% aqueous solution of ammonia to a neutral environment. Then, 3.6 g is added to the resulting solution, which corresponds to 0.4 mol per 1 mol of the ammonium salt of 4-sulfophthalic acid and kept at 220 ° C for 2 hours. The resulting melt is crushed. The content of ammonium salt of tetra-sulfophthalocyanine cobalt in terms of 82%. Yield 11.19 g (94%). The resulting substance is readily soluble in water, DMSO, DMF, sulfuric acid, insoluble in acetone, ethanol. Spectrum

Example 8. In a manner analogous to Example 2, the sulfomass is neutralized, then 3.7 g is added and held at 2 hours. Content target

absorption has absorption bands

with maxima, in DMF-348, 645, 675 nm of the substance in the melt 77%. Yield 11.67 g

(92%). The resulting substance is readily soluble in water, DMF, DMSO, sulfuric acid, has absorption maxima.

N 16.71. In DMF at 340, 640, 674 nm.

in water 290, 325, 630, 665 nm. Found,%: C 39.93; H 3.09;

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Calculated,%: C 40.04; H 2.92; N 17.05.

Example 3. Analogously to example 2, the sulfas mass is neutralized, then 2.7 g of cobalt chloride is added, which corresponds to 0.3 mol per 1 mol of 4-SPC ammonium salt and is maintained at 2 hours. The content of the target substance in the melt is 78%, the yield is 11.26 g (90%).

Example 4. Analogously to example 2, the sulfas mass is neutralized, then 4.5 g of cobalt chloride is added, which corresponds to 0.5 mol per 1 mol of 4-SPC ammonium salt and kept at 220 ° C for 2 hours. The content of the substance in the water is 72%, yield 12.74 g (94%).

Example 5. The synthesis is carried out analogously to example 2, but at 240 ° C for 1.5 hours. The content of the substance in the melt is 82%. Yield 11.19 g (94%).

Example 6. The synthesis is carried out analogously to example 2, but at 270 ° C for 1.5 hours. The content of the target substance in the melt is 74%. Yield 12.00 g (91%). The decrease in the content of the target substance in the melt and its release is explained by the course of the desulfu process. and formation of cobalt in phthalocyanine in this case.

Example 7. Analogously to example 2, the sulphatic mass is neutralized, then 3.6 g is added, which corresponds to 0.4 mol per 1 mol of ammonium salt of 4-SFC and is maintained for 2 hours. The content of the target substance in the melt is 72%. Yield 12.03 g (89%).

Calculated,%: C 40.17; H 2.93; N 17.57.

Found,%: C 39.15; H 2.98; N 17.83.

The spectrum of the compound obtained in DMF has absorption maxima at 350, 640, -676 nm. The compound obtained is readily soluble in water, DMF, DMSO,. Sulfuric acid.

Example 8. In a manner analogous to Example 2, the sulfomass is neutralized, then 3.7 g is added and held at 2 hours. Content target

Calculated,%: C 40.02; H 2.92; N 17.5.

Found,%: C 40.56; H 3.07; N 16.9.

Claims (1)

Thus, the present invention allows to increase the content of the target substance in the melt from 15 to 72-82% with a yield of 90-94%, exclude urea and ammonium molybdate from the process, reduce the duration of the process from 7-8 hours to 1.5- 2 h, reduce the consumption of metal salt to values close to stoichiometric. All this greatly simplifies the process of obtaining NIN and purification of the target product, leads to a decrease in the energy intensity of the process. The proposed method can be used by the industry to obtain the ammonium salt of tetrasulfonic phthalocyanine metal complexes in one apparatus and without the separation of intermediate products. Invention Formula The method of obtaining the ammonium salt of tetrasulfophthalocyaninone metal complexes of the general formula W4.0ZZ-X W /. -k Mch  .N / n  N $ Oz1Sh4 where M is Co, Fe, Cu, sulphurization of phthalic anhydride with oleum, followed by successive neutralization of the reaction sultfossa with the main component and treatment with the corresponding metal chloride, characterized in that, in order to increase the yield of the target product and simplify the process sulfomass using water solution of ammonia, while the metal chloride is taken in the ratio of 0.3: 0.5 mol per 1 mol of the reaction sulfomass.