Method of producing metal complexes phthalocyaninato acids

 

(57) Abstract:

Method for obtaining metal complexes phthalocyaninato acids, which can be used as oxidation catalysts and pharmaceuticals. The process involves a new way of synthesis of telogen - 3,4-dicarboxyphenoxy acid. In contrast to the previously described multi-stage synthesis, the new method allows to obtain the product over a short path. By this method dimethylphthalate phosphorylate diethylphosphate in the presence of di-tert-butylperoxide formed ester hydrolyzing to 3.4-dicarboxyphenoxy acid, and potassium salt of this acid is heated with urea and a salt of the metal in the presence of high-boiling organic solvent and a catalytic amount of ammonium molybdate.

The invention relates to the field of organic chemistry, namely, to the synthesis of phthalocyanines, which can be used as oxidation catalysts, optical and medical supplies.

Given the wide applicability of the dyes of this class is of great importance to find new ways of synthesis of derivatives of phthalocyanine (Pc), which has a solubility in on what triphosphorylation copper, dye capable of dissolving in an aqueous-alkaline solution. According to this method, by heating in an autoclave of o-xylene with P2ABOUT5at 275oC receive 3,4-dimethylphenylphosphine acid, which is then transferred to the acid chloride; acid chloride 3,4-dimethylphosphinic acid glorious under irradiation of UV light; the resulting acid chloride 3,4-bischlorethylnitrosourea acid hydrolyzing to 3.4-delegitimisation acid; the resulting dialdehyde oxidize KMnO4to 3,4-dicarboxyphenoxy acid; translated synthesized acid in her Moncalieri salt; specinen potassium salt of 3,4-dicarboxyphenoxy acid with copper chloride and urea in the presence of molybdate of ammonium and chloride of zirconium get copper complex phthalocyaninato acid. (When playing a stage production of the metallic complex phthalocyanine of the potassium salt of 3,4-dicarboxyphenoxy acid prototype received output not exceeding 32%). The described method is complex and time-consuming.

The task of the invention was to develop a simpler method of obtaining the desired products. To solve this problem is proposed synthesis, including obtaining 3,4-d is pet-butylperoxide, acid hydrolysis of the resulting product and translation of the resulting acid Moncalieri salt followed by heating the potassium salt of 3,4-dicarboxyphenoxy acid metal salt and urea in the presence of ammonium molybdate and high-boiling organic solvent.

The process proceeds according to the following scheme:

< / BR>
where

MX - salt of the metal, Rwith- the rest of the phthalocyanine (C32H12N8)

Phosphorylation of dimethylphthalate (not previously described) is held at the boiling temperature of di-tert-butylperoxide. The product obtained at this stage, without isolation in individual form, is subjected to acid hydrolysis; after treatment of the reaction mass CON secrete soluble Moncalieri salt of 3,4-di-carboxyvinyltransferase acid. At the stage of synthesis of the phthalocyanine to improve product yield applied high-boiling organic solvent.

The invention is illustrated in the following examples.

Example 1.

A mixture of 9.7 g ( 0.05 m) dimethylphthalate, 3.7 g of di-tert-butylperoxide and 5.5 g of dimethylphosphite heated at boiling for 30 hours. Then add in the mass of 1.8 g of di-tert-butylperoxide and 2.8 g of dimethylphosphite and continue (in the form of a thick recrystallizes mass) hydrolyzing when heated with 15 ml of hydrochloric acid for 5 hours. A small residue of phthalic acid is separated by filtration, the mother liquor evaporated in vacuum and dissolved in acetone or ethyl acetate. Then the mixture is poured a solution of KOH as long as the environment does not become weak acid and the mass leave for a few hours. The precipitation was separated, washed with water, methanol, acetone and dried. Yield analytically pure montalieu salt of 3,4-dicarboxyphenoxy acid, 3.1 g (22%). Found %: C - 34,19; H, 2.51, 2.63. Calculated%: C - 33,8; H - 2,16. The connection structure is confirmed by IR and PMR spectra.

A mixture of 0.3 g (0,00165 mol) of montalieu salt of 3,4-dicarboxyphenoxy acid 0.07 g of cobalt acetate, 0.5 g of urea, 0.005 g of ammonium molybdate and 1 ml of nitrobenzene are heated at a temperature of 170owithin 3 hours the Mixture is treated with hydrochloric acid and dried. Exit-phthalocyaninato acid, calculated on the original salt of 3,4-dicarboxyphenoxy acid (0,19) - 81%. Previously this product was not described.

The absorption of an aqueous solution of the product at pH>7 is a characteristic phtalocyanine dyes, molecules which are not aggregated: two narrow stripsmax(H2O) 676 nm and 618 nm with intensities ratios of 4.5:1, respectively.

Sola take trichlorobenzene. The yield of 76.7 percent.

Example 3 (comparative).

Synthesis of Co-phthalocyaninato acid is carried out by sintering 3,4-dicarboxyphenoxy acid with cobalt acetate, urea and additives according to the method of the prototype. The yield of 27.8%.

Example 3.

The process is conducted according to example 1, using copper chloride instead of cobalt acetate. Output Cu-phthalocyaninatoaluminum acid 69%.max(H2O) 681 nm and 613 nm (the ratio of the intensities of 4.4:1, respectively).

Example 4.

Synthesis of Cu-phthalocyaninato acid is carried out according to the method of the prototype. Yield of 32%.

Example 5.

The synthesis was carried out according to the method of example 1 using instead of cobalt acetate aluminum chloride and the solvent is sulfolane. Al-ftalotsianinatov acid is obtained with a yield of 6.7 %. In the absorption spectrum of an aqueous solution (pH>7) absorption bandmax683 nm and 615 nm with a ratio of intensities of 3.8:1, respectively. Previously, the product was not received.

Thus, the proposed method allows to obtain metal complexes phthalocyaninato acid (including previously unknown.

Method of producing metal complexes phthalocyaninato acids, including the interaction of 3,4-dicarboxyphenoxy acid with potassium hydroxide, followed by the interaction of the obtained potassium salt of 3,4-dicarboxyphenoxy acid with urea and the corresponding metal salt in the presence of a catalyst of ammonium molybdate by heating, characterized in that the use of 3,4-dicarboxyphenoxy acid obtained by the phosphorylation of dimethylphthalate dimethylphosphite in the presence of dicret. butylperoxide, with subsequent acid hydrolysis of the resulting ester and the interaction of the obtained potassium salt of 3,4-dicarboxyphenoxy acid with urea and a salt of the respective metal lead in the environment of high-boiling organic solvent.

 

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