SU740802A1 - Phthalocyanineocta-4,5-carboxylic acid dialkylamides for producing optical filters absorbing in red part of spectrum - Google Patents

Description

where M C, Co, VO, R,,

SDI

allowing the use of these compounds of DPP optical filters.

The proposed compounds, in contrast to the known phthalocyanines, have good solubility in organic solvents, for example benzene, chloroform, dimethylformamide, and also dissolve well in ethyl alcohol

A distinctive feature of the proposed compounds is their ability to form true molecular solutions, which allows them to be used to obtain optical filters.

The absorption spectra of copper complexes of tetra-tre / chbutylphthalocyanine 2 and octa-4,5-dibutylcarbamoylphthalocyanine in a film of polymethyl methacrylate (PMMA) were measured at their identical concentration (1 IQ3 Mol / L). The spectrum of the proposed compound in a 30 μm thick PMMA film has a narrow intense long-wave maximum characteristic of a true solution, with a clear vibrational structure, while a 200 μm thick tetra-r butyl-Fc copper film has a spectrum characteristic of an aggregated substance — a wide band with two maxima. .

The compounds obtained have good compatibility with polymethyl methacrylate and therefore can be used as an absorbing component of optical filters and colored polymer glasses.

Example 1. Octa-4,5-diethylcarbamoyl phthalocyanine copper 1.

A mixture of 2.17 g of 4,5-dibromophthalic acid bisdiethylamide and 1.35 g of CuCN in 4 ml of dimethylformamide is boiled (bp 152-153 ° C) with stirring. Research institutes 5 hours. The cooled reaction mass is poured onto water, the precipitate is washed with water and dried. The product is extracted with chloroform, then purified by chromatography on alumina (eluent is chloroform). Obtain 0.51 g (yield 30%) octa-4,5-diethylcarbamoyl phthalocyanine copper, so pl. .

Found,%: C 62.91; 63.05;

. H 6.75; 6.76; N 16.37 16.15.

Cv HgaCuN.eOg

Calculated,%: C, 63.25; H 6.37; N 16.39.

 max (in ethanol): 671, 640; 604, 344 (;; nm).

When quinoline is used instead of dimethylformamide (i.e., bale), while maintaining the remaining conditions (example 1), 0.88 g of product is obtained (yield 52%).

Preparation of 4,5-dibromophthalic acid bisdiethylamide intermediate.

A mixture of 6.1 g of 4,5-dibromophthalic anhydride (T. pl. 213 214 ° C) and 4.4 g

The phosphorus pentachloride is heated under reflux for 10 hours at 150-160 ° C in an oil bath. Raise the bath temperature to 250 ° C, remove the POCVj. To the benzene solution of the 4,5-dibromophthalic acid dichloride formed is added with stirring a solution of 7.3 g of diethylamine in 30 ml of benzene, stirred at 50 ° C for 1 h and left overnight. The benzene solution is washed successively with 5% hydrochloric acid, water, 5% soda, and again with water. The product is purified by chromatography on alumina, eluting with benzene. This gives 6.74 g (78%) of 4,5-dibromophthalic acid bisdiztilamide, m.p. 62-63 ° C (from heptane).

Example 2. Octa-4,5-dibutylcarbamoyl phthalocyanine copper.

A mixture of 2.73 g of bisdibutylamide, 4,5-dibromophthalic acid (mp. 4950 ° C) and 1.35 g of CuCN a. 5.5 ml of dimethylformamide are boiled (so bp. 152-153 0 with stirring for 5 hours. After purification with alumina (eluent chloroform), 0.57 g (25% yield) of octa-4,5-dibutylcarbamoyl phthalocyanine are obtained copper, mp 200-202 ° C.

Found,%: C 68.45, 68.56;

And 8.25, 8.17; N 12.21, 12.28.

C o4H-t52CuN ,, Oa Calculated,%: C 68.89; H 8.37;

N 12.34.

 MoiKc (in ethanol): 671, 642, 605, 347 (nm).

Example 3. Octa-4,5-diethylcarbamoyl phthalocyanine cobalt.

A mixture of 0.2 g of dinitrile 4,5-bis (yes. Ethylcarbamoyl) phthalic acid and 0.04 g of cobalt acetic acid in 0.5 ml of trichlorobenzene is boiled for 2-3 hours. After purification by chromatography on alumina (eluant - chloroform) T-0.056 g of octa-4,5-diethylcarbamoyl phthalocyanine cobalt (10% yield). Found,%: N 16.04, 16.12. .g Og. Calculated,%: N 16.44. MQKc (in ethanol): 658, 598, 330 (nm).

Claims (2)

Dinitrile 4,5-bis (diethylcarbamoyl) phthalic acid is obtained according to the following procedure: a mixture of 1.3 g of bis-N, N-diethylamide of 4,5-dibrrMphthalic acid, 0.81 g of CuCN, 0.05 g of iodine and 0.5 ml of aa. detonitrile in 26 ml of dimethylformamide is stirred at 150 ° C for 5 hours. The cooled reaction mass is added to a solution of ferric chloride in 30 ml of 5% hydrochloric acid, stirred for 15 minutes at 40c, extracted with ether. 0.24 g (25% yield) of dinitrile was isolated by chromatography on alumina (eluent: chloroform), m.p. 191-192s 5 (from heptane). Example 4. Octa-4,5-diethylcarbamoylphthalociaiine Vanadyl. A mixture of 0.2 g of dinitrile 4,5-bis (diethylcarbamoyl) phthalic acid and 0.06 g of vanadyl acetylacetonate in 0.5 ml of quinoline is heated for 2 hours at 230 235 ° C. The cooled reaction mass is mixed with 10 ml of 5% hydrochloric acid; the product is extracted with chloroform. After purification by xp by chromatography on alumina (eluent chloroform), 0.04 g (2% yield) of octa-4,5-diethylcarbamoyl phthalocyanine vanadyl is obtained. Found,%: N 15.91, 15.98. C iHasNieOg Calculated,%: N 16.34; MOikc (in ethanol): 685, 650, 618, 350 (them). The invention claims Phylesalkylamides of phthalocyaninoct-4, 5-carboxylic acids of the general formula do® K 8 COBBj for producing optical filters with absorption in the red region of the spectrum. Sources of information taken into account in the examination 1. German patent number 2006663, cl. 22a 47/08, published, 1974. 2. The patent of France No. 1580683, cl. From 09 To d D 06 p, published. 1969.