The method of obtaining aluminum and gallium complexes phthalocyaninato acids

 

(57) Abstract:

The invention relates to the synthesis of aluminum and gallium complexes phthalocyaninato acids, which can be used as dyes, catalysts of oxidation reactions of various substrates, and products for optical and electronic products and medicine. In accordance with the proposed method, aluminum and gallium complexes phthalocyaninato acids are obtained by heating the source of the metal complex of phthalocyanine with a mixture of organic peroxide and dialkylphosphate at boiling, and formed alkylphosphonate phthalocyanine is subjected to acid hydrolysis. The method allows to obtain aluminum and gallium complexes phthalocyaninato acids with satisfactory yield and simplified technology, eliminating the synthesis of phosphorus-containing palagano.

The invention relates to the field of organic chemistry, namely the synthesis of water-soluble phthalocyanines which can be used as dyes, catalysts of oxidation reactions of various substrates, and products for optical and electronic products and medicine.

A method of obtaining m is obtained by postliminium dimethylphthalate dimethylphosphite with subsequent acid hydrolysis of the resulting ester and translated into the potassium salt, bake with a suitable metal salt in the presence of urea in the environment of high-boiling organic solvent (patent RF 2103291, 09 At 47/04, 1998). However, this method, which allowed to obtain a satisfactory yield of copper and cobalt complexes phthalocyaninato acids in the case of aluminum and gallium complexes was not as successful Aluminum complex phthalocyaninato acid obtained with the yield of 6.7%, and the corresponding gallium complex only in trace amounts.

The task of the invention is to develop a more efficient method for the synthesis of aluminum and gallium complexes phthalocyaninato acids.

To solve this problem, a method is proposed, which consists in the fact that the original metal complex of phthalocyanine is heated with a mixture of organic peroxide and dialkylphosphate at boiling, and formed alkylphosphonate phthalocyanine is subjected to acid hydrolysis.

The process proceeds according to the following scheme:

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where R=t-C4H9; R1=CH3C2H5C3H7; n=1-4; M=Al, Ga; Pc is a phthalocyanine.

Vospominanie carried out by heating phthalocyanines in excess of dialkylphosphate and t is or NVG.

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where M=Al, Ga; R=H, PO(OH)2.

As our investigations have shown that the method leads to the production of mainly mono-, di-, tri - and tetrafluorothiophenol acids. According to elemental analysis, the obtained acid contain about 6 molecules of water of crystallization. The dried product at a temperature of 100oWith the above leads to the loss of water of crystallization and dehydration process involving phosphonate groups. In the absorption spectrum of such a "dried" product (unlike the original) strip substantially broadened and distorted. After hydrolysis of the cross-linked product of the absorption spectrum is restored.

Example 1. To 0.5 g (0,8710-3M) ll add 4 ml of dimethylphosphite (410-2M) and 4 ml (2,110-2M) di(tert-butyl)peroxide. The mixture is heated under stirring and boiling peroxide for 17 hours Volatile products are distilled off in vacuum, the residue is washed with hexane, and then heated with 3 ml conc. Nug at a temperature of about 100oC for 3 hours the Precipitate was separated, washed with water, alcohol, periostat from aqueous alkali solution and dried at 50oC. Not dissolved in the alkali solution, the dye is a clean source phthalocyanine. The yield of the target products is 42,48, N of 3.53, N KZT 12.39; P 10,27 Found, %: C 42,70, 42,40; H 2,95, 3,10, N 11,63, 11,81; P 10,26, 9,95; VG - UTS. PMR (D2O+NaOD, M. D.: becomes 9.97 (m, 1H), 9,9 (d, 1H), and 9.6 (m, 4H), to 9.15 (t, 1H), 8,8 (m, 1H), 8,67 (t, 1H), 8,35 (m, 3H), 7,5 (m, 1H).

The signals in the spectrum of TMR somewhat broadened, which is associated with a tendency phthalocyanine aggregation at high concentrations of

max(H2O+NaOH)675 nm, =1,78105l/malism.

Example 2. The synthesis was carried out analogously to the above, but instead of dimethylphosphite used diethylphosphate, and heating was continued for 10 hours, the Yield of 41.5%, taking into account the conversion range of the PMR is the same as in example 1.

Example 3. A mixture of 0.2 g (3,210-4M) lG, 2 ml of diethylphosphate (2,0410-2M), 1 ml (7,210-3M) di(tert-butyl)peroxide is heated for 6 hours under stirring at a bath temperature of 120-130oC. the Dye is then precipitated with hexane, washed with water, and then heated with 2 ml conc. Nug g for 2 hours the Precipitate was separated, washed with water, alcohol and periostat from aqueous alkali solution. The product yield 0,094 g (44.7 per cent, taking into account the conversion). Molecular weight 847,3.

Calculated for HOGaPc[P= O(OH)2]36N2O %: R - 9,80. Found %: P 9,34, to 9.32 PMR (DMCOd6), M. D. : 9,75 (2N), 9,45 (2N), OF 8.95 (3H), OF 8.25 (3H), 7,7-7,4 (3H).max(H2O+NaOH)690 nm, =1,27105l/malism.

Example 5. Synthesis is carried out analogously to example 3, but the time postlarvae is 2-3 hours. Receive a product with a degree of substitution=1.

Example 6. Synthesis is carried out analogously to example 3, but the time postlarvae is 10 o'clock Receive the product with a degree of substitution of n=4.

When using other dialkylphosphites get similar technical results.

Thus, the proposed method allows to obtain aluminum and gallium complexes phthalocyaninato acids, bypassing the synthesis of phosphorus-containing palagano, with a satisfactory yield.

The method of obtaining aluminum and gallium complexes phthalocyaninato acids of General formula

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where M = Al, Ga; R = H, PO(OH)2, characterized in that the corresponding chlorine substituted metal phthalocyanine complex is heated with a mixture of dicret-butylperoxide and dialkylphosphate at boiling, and formed alkylphosphonate phthalocyanine is subjected to acid hydrolysis.

 

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