SU109457A1 - The method of obtaining symmetric and asymmetric tricarbocyanine dyes - Google Patents

Description

The essence of the proposed method for the preparation of these dyes consists in carrying out the condensation reaction of alkoxy-substituted tetramethymecyanine dye derivatives of benzthiazole or benzenelenazole, as well as their acetylation products (general structure II) with p-quaternary salts of p-alkoxypropenylbenzthiazole or p-alkoxypropene-skene-sphalene-sphalenecane-sphalene-skazlezelazole or p-alkoxypropene-benzthalene-sphalene-azole-d-alkoxy. pyridine in the presence of bases, for example triethylamine, at temperatures up to 100 °.

The method of obtaining the starting compounds, General structure II and III:

OR,

R,

CH C-CH CH-N-Ar

where: R, R I, R ri, R III - identical or different alkyl residues; Riv is hydrogen or acyl group;

B |, BO, BZ, B4-hydrogen, alkyl, alkoxy, halogen atom, or other substituents, or

BI and B2 or VB and B4 are together a benzo group; Y, Y-S or Se;

X-acid residue; Ag-aryl residue, described respectively in ed. St. No. 107123 and in ed. St. No. 95503.

The dyes obtained by the proposed method, in most cases with good yields and a sufficient degree of purity, are effective sensitizers for gallion-silver emulsions and can be used in the film and photo industry.

Example 1. 3,3-diethyl-9,13-dimethoxytricarbocyanine perchlorate.

To a mixture of 0.5 g of iodoethyl 2- | (3-methoxy-d-anilino-butadienylbenzthiazole, 0.4 g of ethylmethylsulfate 2-p-methoxypropenylbenzothiazole, 1.5 ml of acetic anhydride and 0.75 ml of pyridine was added 0.15 g of triethylamine. After heating the mixture for 3 minutes on a boil, with a water bath, the mass is diluted with ether, the precipitate separated is washed with eh, e several times with ether, dissolved in 20 ml of ethyl alcohol and 20 ml of 15% is added to the solution. an aqueous solution of sodium perchloric acid.

The precipitated dye is filtered off and washed with water, ethyl alcohol (until a clear blue color appears) and ether. Yield 0.42 g (72.9%). Melting point 160-161 °. Small dark green prisms (of ethanol) with a melting point of 181-182 °. Maximum absorption at 682m | j- (B ethyl alcohol).

2-3-methoxy-b-anilino-butadienylbenzthiazole iodoethyl can be replaced by the corresponding 2-p-methoxy-6a and 2-p-methoxy-6a iodo-ethyl; eganiline-butadienylbenzthiazole.

Example 2. 3,3-diethyl-9,13-diethoxytricarbocyanine perchlorate.

Into a mixture of 0.5 g of iodoethyl 2- | 3-ethoxy-b-anilinobutadienylbenzthiazole, 0.4 g of ethylmethylsulfate 2-p-ethoxypropenylbenzothiazole, 1.5 ml of acetic anhydride and 0.75 ml of pyridine are added 0.15 ml of triethylamine. In this case, an intense green color appears. After heating the mixture for 2 minutes. in a boiling water bath, the mass is diluted with ether, the precipitated crystalline precipitate is washed several times with ether, dissolved by heating in 10 ml of ethyl alcohol, and 5 ml of a 15% aqueous solution of sodium chloride are added to the solution. The crystalline precipitated glitter is filtered and washed on the filter in several stages with 10 ml of ethyl alcohol and ether. You 0.5 g (83%). Melting point 180-182 °.

After a single crystalzin of 300 parts of ethyl ozoxy alcohol, shiny bronze-colored needles are obtained. Melting point 184-185 °.

Maximum absorption at C82p ;; - (in ethyl alcohol).

Similarly, 3,3-diethyl-5,6,5,6-tetramethyl-9,13-dPethoxythiricarbocyanine iodide and 3,3-dimethyl-5,5-dimethoxy-9,13-dPethoxythiotricarbocyanine perchlorate are obtained.

Example 3. 3,3-diethyl-9.13-dimethoxy-6,7, 6,7-dibepzothiatricarbocyanine aniodide.

To a mixture of 0.5 g of iodoethyl 2-p-methoxy-b-apylinobutadie-6,7-benzobenzothiazole, 0.4 g of ethyl methyl sulphate 2- | 3-methoxypropane P1l-6,7-beisobenzthiazole, 1.5 ml acetic anhydride and 0.75. ml of pyridine add 0.15 liters of triethylamine; at the same time, an intense green color appears immediately. After heating for 3 minutes. in a boiling water bath, the mass is diluted with ether. The isolated precipitate is washed several times with ether, dissolved by heating in 10 ml of ethyl alcohol and 10 ml of a 10% aqueous solution of potassium iodide is added to the solution.

The precipitated dye is filtered off and washed with water, ethyl alcohol (until a clear blue color appears) and ether. The output of 0.35 g (50%).

The dye is washed several times with boiling methyl alcohol for cleaning.

Get prism with a golden sheen. Melting point 164-166 °. Maximum absorption at 712m; i (in ethyl alcohol).

Similarly, 3,3-diethyl-9,13-dimethoxy-4,5,4,5-dibenzothiatricarbocyanine-iodide-3, 3-diethyl-5.5-dichloro-9.13-diethoxythiocarbo-ianino-iodide and 3,3, 6,6-tetramethyl-9 are obtained , 13-dimethoxytricarbociapiipiperperlorate.

Example 4. 3,3-Diethyl-9,13-dimethoxane-acetylene-tricarbociaine perchlorate.

The dye is obtained analogously to examples 1-3.

A mixture of 0.5 g of 2-p-methoxy-b-aialine-butadienylbenzthiazole iodoethyl, 0.4 g of ethylmethylsulfate 2- | 3-methoxypropenylbenzselenazole, 1.5.yl acetic anhydride, 0.75 ml of pyridine and 0.15 ml of triethylamine are heated for two minutes in a boiling water bath. The mass is diluted with ether, the precipitate separated is washed several times with ether, dissolved by heating in 15% of ethyl alcohol and 15 ml of 15 / aqueous sodium perchloric acid solution are added to the solution. The separated dye is filtered off and washed on the filter with water, alcohol and ether. Yield 0.3 g (48.4%).

For purification, the dye is sequentially washed several times with boiling benzene and ethyl alcohol, and then chromatographed in chloroform solution on active alumina.

Dark green prisms are obtained with a golden sheen.

Melting point 172-173 ° (decomposed).

Maximum absorption at 688 mi (ethyl alcohol).

Similarly, 3-ethyl-3, 7-dimethyl-5, 9, 13-trimethoxythi-citrate-carbocyanine aniodide is obtained.

Example 5. 3,3-diethyl-9,13-dimethoxysilane carboxyaniline perchlorate.

A mixture of 0.5 g of iodoethyl 2- | 3-methoxy-A-anilinobutadienylbenzselenazol, 0.4 g, ethylmethylsulfate 2- | 3-methoxypropenylbenzselenazole, 1.5 jMA acetic anhydride, 0.75 ml of pyridine and 0.15 ml of triethylamine is heated 2 missions. in a boiling water bath. Further operations are the same as indicated in examples 1-3.

No. 109457

Yield 0.25 g (37.3%). Melting point 165-166 °.

For purification, the dye is washed several times with boiling benzene and then with absolute ethyl alcohol.

Dark green prisms are obtained. Melting point 167-168 °.

Maximum absorption at 629tr. (in ethanol).

EXAMPLE 6 3,3-Diethyl-9-methoxy-13-ethoxy-tricarbocyanine nerhlorate.

A mixture of 0.5 g of iodoethyl 2-p-methoxy-b-anilinobutadienylbenzthiazole, 0.4 g of ethyl ethyl sulfate 2- | 3-ethoxypropylbenzothiazole, 1.5 ml of acetic anhydride, 0.75 ly of pyridine and 0.15. -Vj.z triethylamine heating for 3 min. in a boiling water bath. Further operations are the same as in examples 1-3.

Yield 0.40 g (67.5%). Melting point 148-149 °.

After crystallization from 250 parts of ethyl alcohol, brown needles are obtained with a melting point of 165-166 °. Maximum absorption at 682 m p. (in ethanol).

Example 7. 3,3-diethyl-9-methoxy-13-ethoxythiene selenotricarbocyanine perchlorate.

A mixture of 0.5 g of 2- (3-methoxy-b-anilino-butadienyl benzselenazole iodoethyl), 1.5 ml of acetic anhydride, 0.75 ml of pyridine, and 0.15 ml of triethylamine is heated for 3 minutes in a boiling water bath. are the same as in examples 1-3.

Yield 0.23 g (37.1%).

The dye is purified by crystallization from ethyl alcohol.

Melting point 175-176 °. Maximum absorption at 682t i (in ethyl alcohol).

Subject invention

The method of obtaining symmetric and asymmetric tricarboxylic dyes containing polymethanes in the | 3, | 3-positions

Bit I n knvir T-T-rmrnrTiLT Lggt t

8 alkoxy groups of general structure I.

C-Sn-Sn-Sn-Sgde: R, Ri Rn, Rm are the same or different alkyl residues; BIBJ, BZ, B4-hydrogen, alkyl, alkoxy, halogen atom:

or other substituents, or B. and Ba or Bz and B4-together benzogroup; Y, Y-S or Se; X-acid residue;

It is characterized by the fact that: 3-alkoxy-substituted tetramethimidecyanine dyes or their acetylation products of general structure II are condensed with quaternary salts of β-alkoxypropenyl derivatives of benzthiazole or benzenelenazole of general structure III.

tY OR, R

CH C-CH CH-N-Ar X