RU2277556C1 - 5,15-bis-(4'-allyloxyphenyl)-3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporphyine and 5,15-bis-(3'-allyloxyphenyl)-3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporphyne - Google Patents

Abstract

FIELD: organic chemistry.

SUBSTANCE: invention relates to new chemical compounds of porphyne class, in particular, to 5,15-bis-(4'-allyloxypehnyl)-3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporphyne of the formula (I):and 5,15-bis-(3'-allyloxyphenyl)-3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporphyne of the formula (II):

that can be used as a dyeing substance in the development of optical filters.

EFFECT: valuable properties of compounds.

Description

The invention relates to the chemical industry, namely to tetrapyrrole macroheterocycles - diphenyloctaalkylporphins, i.e. porphins substituted at two meso positions with phenyl rings that contain allyloxy substituents and at β positions with eight alkyl substituents, specifically to the new chemical compounds 5.15-bis (4′-allyloxyphenyl) -3,7, -13,17 -tetramethyl-2,8,12,18-tetrabutylporfin and 5,15-bis (3′-allyloxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin, which can be used in as a coloring matter of optical filters.

State of the art

Tetrapyrrole macroheterocycles play an important role in wildlife and technology, entering the structure of respiratory pigments, enzymes, vitamins, catalysts, sensors, etc. and, having a narrow, intense absorption band in the visible region, can be used as a dye optical filters.

Of interest are tetraphenylporphins having a maximum of light absorption in the range of 620-630 nm in order to use them for photodynamic therapy and create optical filters.

Optical filters are most often colored organic glasses and can be obtained from the so-called "color polymers", i.e. polymers containing macromolecules elementary units containing chromophores. Such polymers are prepared by copolymerization of vinyl monomers, for example, methacrylic acid derivatives with dyes containing a vinyl group.

Known for 5.15-bis (4′-hydroxyphenyl) -3,7,13,17-tetramethyl-2,8,12, -18-tetrabutylporfin (Syrbu S.A., Semeykin A.S. J. organic chemistry , 1999, vol. 35, No. 8, P.1264), having a maximum absorption in organic solvents in the region of 625 nm and which is a structural analogue of the claimed compounds.

However, it cannot be used as a coloring substance in optical filters based on “color polymers”, because It does not contain the necessary functional groups.

SUMMARY OF THE INVENTION

The objective of the invention is to find a new compound suitable for producing a "color polymer" in order to use the latter as an optical filter.

The problem was solved by 5.15-bis (4′-allyloxyphenyl) -3,7, -13,17-tetramethyl-2,8,12,18-tetrabutylporfin (I) and 5.15-bis (3′-allyloxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin (II).

The individuality and structure of the claimed compounds was established by analogy of the spectral characteristics in the visible spectrum of their solutions in chloroform with those of their closest structural analogue, ¹ H NMR and IR spectra.

Electronic absorption spectra of solutions of the claimed compounds and their structural analogue in chloroform were recorded on a Perkin Elmer Lambda 20 spectrophotometer in quartz rectangular cuvettes 10 mm thick, the concentration of solutions was ~ 10 ^-5 M. The positions of the long-wavelength absorption bands of these spectra are given below.

The high analogy of the visible parts of the electronic absorption spectra convincingly indicates that the claimed compounds belong to the class of diphenylctaalkylporfins, namely, disubstituted 5.15-bisphenyl-3,7,13,17-tetramethyl-2,8,12, -18-tetrabutylporfins .

Allyloxy groups act as substituents. The number, position and nature of the substituents clearly follows from the structure of the synthones 5.15-bis (4′-hydroxyphenyl) -3,7,13,17-tetramethyl-2,8,12, -18-tetrabutylporfin used to obtain the claimed compounds and 5.15-bis (3′-hydroxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin and absorption bands in the PC spectra. For compound I, bands were identified in the region of 1241 cm ^-1 and 1021 cm ^-1 related to asymmetric and symmetric stretching vibrations of the С-О-С group, respectively, and in the region of 814 cm ^-1 , related to deformation vibrations of NH - porphyrin groups; for compound II: in the region of 1292 cm ^-1 and 1027 cm ^-1 related to asymmetric and symmetric stretching vibrations of the С-О-С group, respectively, and in the region of 776 cm ^-1 , related to deformation vibrations of NH - porphyrin groups.

¹ H NMR spectra of the claimed compounds were recorded on a Bruker AS-200 NMR spectrometer, CDCl ₃ solvent, TMS internal standard. The spectral parameters of the claimed compounds (in ppm) with the assignment of signals given below fully confirm the structure attributed to them:

5.15-bis (4′-allyloxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin 7.83d (oH Ph);
7.28d (mH Ph);
6.10m (CH);
5.48m (CH ₂ );
4.82d (OCH ₂ );
2.56 s (CH ₂ );
3.97t (CH ₂ Bu);
2.16p (CH ₂ Bu);
1.78m (CH ₂ Bu);
1.08 (CH ₃ Bu);
10.20s (ms-H);
-2.40bs (NH) 5.15-bis (3′-allyloxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin 7.62m (H Ph);
7.37m (H Ph);
6.13m (CH);
5.50m (CH ₂ );
4.68d (OCH ₂ );
2.56 s (CH ₃ );
3.98 t (CH ₂ Bu);
2.16p (CH ₂ Bu);
1.76m (CH ₂ Bu);
1.08 (CH ₃ Bu);
10.23s (ms-H);
-2.44bs (NH)

Thus, the set of spectral data uniquely determines the structure of the claimed compounds as 5.15-bis (4′-allyloxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin and 5,15-bis (3′-allyloxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin.

These compounds are brownish-violet crystalline substances with a metallic luster, not fusible to 400 ° C, soluble in chloroform, pyridine, dimethylformamide and dimethyl sulfoxide to form intensely colored solutions and can be used to obtain “colored polymers” with the aim of using the latter as optical filters.

Information confirming the possibility of carrying out the invention

To obtain the claimed compounds use the following substances:

- 5.15-bis (4′-hydroxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin and 5.15-bis (3′-hydroxyphenyl) -3,7,13 , 17-tetramethyl-2,8,12,18-tetrabutylporfin, which were obtained by saponification of the corresponding methoxy derivatives according to the method (Syrbu S.A., Semeykin A.S. org. Chemistry, 1999, v. 35, No. 8, C .1264);

- allyl bromide - TU 6-09-456-75;

- potassium carbonate - GOST 4221;

- dimethylformamide - GOST 20289-74;

- aluminum oxide for chromatography of the III degree of activity according to Brockman - TU 6-09-3916 (GOST 8136);

- methylene chloride - GOST 9968-86;

- ethanol - GOST 5962-67.

The inventive compound can be obtained, for example, as follows.

115.8 mg (0.142 mmol) 5.15-bis (4′-hydroxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin or 5.15-bis (3′-hydroxyphenyl ) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin, 0.25 ml (2.89 mmol) of allyl bromide, 0.4 g (2.89 mmol) of potassium carbonate and 20 ml dimethylformamide is stirred on a magnetic stirrer at room temperature for one day. Then the solution is poured into 200 ml of water and incubated for 3 hours. The precipitate formed is filtered off, washed with water and dried at 80′C. For purification, the precipitate is dissolved in 30 ml of methylene chloride and chromatographed on a column with Brockmann grade III alumina, eluting with methylene chloride. The eluate is evaporated to 3-5 ml and the product is precipitated by adding 50 ml of ethanol.

99.3 mg (0.116 mmol) of 5.15-bis (4′-allyloxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin or 68 mg (0,079 mmol) of 5.15 are obtained bis (3′-allyloxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin. The yield is ~ 81.8% and 56% of theory, respectively.

To determine the possibility of using 5.15-bis (4′-allyloxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin or 5.15-bis (3′-allyloxyphenyl) -3, 7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin as a dye of optical filters received samples of colored organic glass.

For this, a solution of this compound in 50 ml of methyl methacrylate with a concentration of ~ 10 ^-5 M was prepared, 60 g of PN-1 unsaturated polyester were dissolved in the resulting solution, 1.5 g of isopropylbenzene hydroperoxide were added, and 4 g of an 8% solution of cobalt naphthenate in styrene. The reaction mixture was poured into collapsible glass molds and cured at 60 ° C. for 1 hour. Then, the obtained samples of colored organic glass were removed from the molds and the wavelength of the long-wavelength absorption maximum was determined.

For optical filters based on 5.15-bis (4′-allyloxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin, it is 624 nm, and for optical filters based on 5.15 bis (3′-allyloxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin it is 626 nm. The achieved optical density also depends on the amount of 5.15-bis (4′-allyloxyphenyl) -3,7,13,17-tetramethyl-2,8,12, -18-tetrabutylporfin or 5,15-bis (3′-allyloxyphenyl ) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin included in the copolymer and the filter thickness.

Thus, having a maximum absorption at 624 nm, the proposed 5.15-bis (4′-allyloxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin and 5,15-bis ( 3′-allyloxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin can be used as a coloring material to create optical filters.

Claims (1)

5.15-bis (4'-allyloxyphenyl) -3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporfin (I) and 5.15-bis (3'-allyloxyphenyl) -3,7 , 13,17-tetramethyl-2,8,12,18-tetrabutylporfin (II)

as a coloring matter of optical filters.