Method for preparing zinc phthalocyanine

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for synthesis of zinc phthalocyanine of high purity degree that can be used as a photosensitizing agent for photodynamic therapy. Method is carried out by interaction of phthalonitrile with zinc salt at heating in the presence of a tertiary amine - N,N-dialkylaniline, N,N-dialkylethanolamine or trialkylamine in an aprotonic dipolar solvent medium, for example, dimethylformamide. Method provides preparing the end product with 97-99% content of the basic substance. Method shows the technological effectiveness as it suggests using inexpensive reagents, small amount of solvent and it doesn't require the complex purifying procedures.

EFFECT: improved method of synthesis.

2 cl, 4 ex

 

The invention relates to the field of organic chemistry, namely the synthesis of phthalocyanine zinc (PcZn) of high purity, which can be used in particular as a photosensitizer for photodynamic therapy or liposomal composition [Igele U., Schieweck K., Kessler, R., van Hoogevest, P., Capraro H.G. J.Pharm.Sci., 1995, vol.84, R], or as starting material to obtain its hydrophilic derivatives (Patent RF № 2.181.736 (2002); IPC 7 09 At 47.24, bull. 2002, № 12).

Described in the literature methods for the synthesis of PcZn not workable and not allow to obtain high-purity product. So, in synthesis, passing by heating phthalonitrile with zinc dust at 260-270° [Barlett P.A., C.E. Dent, R.P. Linstead, J.Chem.Soc., 1936, R], is formed PcZn, containing, according to certain us molar extinction coefficient (ε=2.25×105l/(mol×cm); literature data ε=2.85×105l/(mol×cm) in pyridine [A.B.P. Lever, Adv.Inorg.Chem.Radiochem., 1965, vol.7, p.27-114]), about 80% of the basic substance. After the featured authors purification by resultant deposition rates of the sulfuric acid content of the basic substance is increased to 90% (ε=2.54×105l/(mol×cm)), which is insufficient for its use in medical practice.

Know of any other way of getting PcZn using phthalonitrile, zinc salts and hexamethyldisilazane [Uchida M., Tanaka N., loshiyama H., Reddy P.Y., Nakamura Sh., Tory T. Synltt, 2002, No. 10, R]. Obtained by this method PcZn has a molar extinction coefficient ε=2.45×105l/mol×cm, which corresponds to the content of the basic substance of 87%. Featured authors purification by extraction device socket not adaptable to production.

The closest technical solution (prototype) of the present invention is a method of obtaining PcZn interaction phthalonitrile with salts of zinc in aliphatic alcohols in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) [Tomada H., Saito, S., Ogawa S. Chem.Lett., 1980, p.1277]. Because alcohols are poor solvents used in this method, reagents, it is necessary to use a large number (˜40 ml per 1 g of the product), which is associated with the use of bulky equipment and regeneration of large quantities of solvents. In addition, the use of DBU and DBN significantly increases the price of the product.

Thus, the disadvantages of the described method are its low-tech and economiccost.

The task of the invention is to find ways of getting PcZn, which would ensure a product of high purity while manufacturability and efficiency of the process.

To solve this problem is proposed a method of obtaining PcZn, consisting in nahrawan the zinc salts with phthalonitrile in dipolar aprotic solvents in the presence of N,N-dialkylanilines, N,N-dialkylacrylamide or trialkylamine (for example, tributylamine) as tertiary amines. As salts preferably used acetate or zinc chloride. As dipolar aprotic solvents can be used, for example, dimethylformamide, dimethyl sulfoxide or N-organic.

The process is carried out by heating a mixture of the above reagents at 115-130°C for 4-6 hours, the precipitate is filtered off, washed with methanol and/or diluted hydrochloric acid, water and dried. Ready PcZn receive in the form of a crystalline powder with a bronze lustre; the molar extinction coefficient in pyridine ε=(2.77-2.82)×105l/(mol×cm) (which corresponds to the content of the basic substance 97-98%).

A high degree of purity PcZn is achieved, probably due to our proposed joint use of these tertiary amines with dipolar aprotic solvents, in which the solution is held by-products and the conditions obtain pure crystals of the product, with which surface is easily washed away impurities.

The invention is illustrated by the following examples.

Example 1

A mixture of 2.9 g (0.0226 mol) of phthalonitrile, 1 g (0.0045 mol) of zinc acetate dihydrate, 3.9 ml of N,N-dimethylaminoethanol and 3 ml of dimethyl sulfoxide is heated at a temperature 115122° C for 5 hours. The mass is filtered, the precipitate washed with methanol and dried, yielding 1.83 g PcZn (69.5% relative to zinc acetate or 56.1% relative phthalonitrile). The electronic absorption spectrum in pyridine, λmaxnm (ε, l/(mol×cm)): 672 (2.80×105).

Example 2

A mixture of 0.97 g (0.00757 mol) of phthalonitrile, 0.30 g (0.00136 mol) of zinc acetate dihydrate, 1.5 ml of N,N-diethylaniline and 1 ml of dimethylformamide is heated at a temperature of 120-125°C for 5 hours. The mass is filtered, the precipitate washed with methanol, 10%hydrochloric acid, water, dried, yielding 0.53 g PcZn (48.6%). The electronic absorption spectrum in pyridine, λmax; nmε, l/(mol×cm)): 672 (2.82×105).

Example 3

A mixture of 0.97 g (0.00757 mol) of phthalonitrile, 0.34 g (0.00155 mol) of zinc acetate dihydrate, 1.5 ml tributylamine and 1.5 ml of dimethyl sulfoxide is heated at a temperature 120-122°C for 4 hours. The mass is filtered, the precipitate washed with methanol and dried, yielding 0.54 g PcZn (49,5%). The electronic absorption spectrum in pyridine, λmaxnm (ε, l/(mol×cm)): 672 (2.80×105).

Example 4

A mixture of 0.97 g (0.00757 mol) of phthalonitrile, 0.34 g (0.00155 mol) of zinc acetate dihydrate, 1.5 ml of N,N-dimethylaminoethanol and 1.5 ml of N-methylpyrrolidone heated at a temperature of 115-120°C for 5 hours. The mass is filtered, the precipitate washed with methanol and dried, yielding 0.73 g PcZn (67.2 per cent). The electron is first absorption spectrum in pyridine, λmaxnm (ε, l/(mol×cm)): 672 (2.80×105).

Thus, it is proposed technological method for the synthesis of PcZn, which allows to obtain a product with the content of the basic substance 97-99% using cheap reagents at low expenditure ratios of solvents and without the use of complex methods of treatment.

The method of producing phthalocyanine zinc interaction of phthalonitrile with zinc salts in an organic solvent under heating in the presence of tertiary amines, characterized in that the solvent used aprotic dipolar solvents, and as a tertiary amine - N,N-dialkylanilines, N,N-dialkylacrylamide, trialkylamine.



 

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