SU608797A1 - Nona- or undecametine combinations as intermediate combination for synthesis of polymethine dyes - Google Patents

Description

followed by treating the reaction products with salts of aromatic amines in an acidic medium 2. These pentamethine compounds are intermediates in the synthesis of tricarbocyanine dyes, absorbing in the IR-Private spectrum.

However, such tricarbocyanine dyes cannot be used to sensitize halogo-silver emulsions to the more distant IR part of the spectrum, and also as a component of passive gates of optical quantum generators in a certain long-wavelength band of the spectrum.

The compounds of general formula (I) and their properties are not described in the literature.

The purpose of the invention is the synthesis of compounds of general formula (I) used as intermediates for the synthesis of polymethine dyes with valuable properties.

Starting from nona- and undecametin compounds of the general formula (I), polymethine dyes are obtained, which absorb in a much more distant IR region than the known dyes and are suitable for sensing halogen-cerebral emulsions and as components of passive gates of optical quantum generators in the long-wavelength region of the spectrum .

The proposed compounds of general formula (I) are obtained by reacting alkoxon acetals containing cyclic fragments in a hydrocarbon chain of general formula

ORSC: -. JR

(RO) (:: HCltiCH CHCH - (,, - CH-))

Chg

P

where R is methyl or ethyl;

t, p-O or 1, with amine salts in an acidic medium at room temperature or at a lower temperature, followed by separation of the target product by known methods.

Example 1. Chloride 9- (L-phenylamino) 2, 4 - dimethylenenone - 2,4,6,8-tetraenylidene phenylammonium.

To a mixture of 0.3 g (0.001 mol) 1,1,5,9,9-pentametoxy-2, 4-dimethylene-2,6-nonadiene and 0.39 g (0.003 mol) of aniline hydrochloride, cooled to 0 ° C, add 1 ml of dilute hydrochloric acid (1:10) and leave for 1 hour at 0 ° C. The mixture is then diluted with ice water, the crystalline precipitate is filtered off, washed with cold water, repeatedly with benzene, ether, and dissolved in a vacuum desiccator. Obtain 0.25 g (69%) of the target substance in the form of small dark blue crystals with so pl. 130 ° C (sintered), Yamako at 742 times (in alcohol), S 88000.

Found,%: C 72.33, 72.38; H 6.82, 6.51; N 7.23, 7.41; C1 8.86, 8.73.

СгзНазМгСЬНгО.

Calculated,%: C 72.51; H 6.63; N 7.35; C1 9.30.

Example 2. Chloride 9- (L-phenylamino) 2, 4 - trimethylenenone - 2,4,6,8-tetraenylidene phenylammonium.

To a mixture of 0.33 g (0.001 mol), 1,5,9,9-tetramethoxy-1-ethoxy-2, 4 - trimethylene-2,6-nonadiene and 0.19 g (0.002 mol) of aniline with careful placement and cooling to 0 ° C

1 ml of diluted (1: 1) hydrochloric acid is added. The mixture is left for 2 hours at room temperature. The crystalline precipitate is filtered off, washed thoroughly with ether, benzene, and more ether, and dried in

vacuum desiccator. 0.19 g (50%) of the desired product is obtained in the form of dark blue crystals, does not melt to 260 ° C (polymerized by heating), Lmax. at 700 nm (in alcohol), 8 97000.

Found,%: N 7.21, 7.13; C1 9.16, 9.23.

C24H25N2C1.

Calculated,%: N 7.43; C1 9.40. Example 3. Chloride 11- (N-methylanilino) -4,6-trimethylene-dekade - 2,4,6,8,10-pentaenylidene-Y-methylaniline.

To a mixture of 0.75 g (0.002 mol) of 1,3,7,11,11-hexamethoxy-1-ethoxy-4, 6-trimethylene discadien-4, 8 and 2.15 g (0.015 mol) of N-methylaniline hydrochloride are added 3 ml of diluted (1: 10) hydrochloric acid. The mixture is moved at room temperature until the appearance of green crystals (2-3 minutes) and incubated for 4 hours at 0 ° C. The precipitate is filtered off, washed thoroughly with cold water, ether, benzene and it is present in a vacuum desiccator. Obtain 0.26 g (30%) of the target substance in the form of green crystals with so pl. 76-78 ° C (decomp.), Amaks. 780 nm (in alcohol), e 109,000.

Found,%: C 75.23, 75.31; H 7.21, 7.30; C1 7.75, 7.62.

C28H3lClN2-H20.

Calculated,%: C 75.05; H 7.43; C1 7.70. Example 4. Chloride 11- (S-tetrahydroquinolino) -4,6-trimethylene-dedec - 2,4,6,8,10-pentaenylidene-tetrahydroquinolini.

To a carefully moved mixture of 0.4 g

(0.001 mol) 1,1-diethoxy-3,7,11,11-tetramethoxy-4, 6-trimethylendecadien-4,8,0,27 g

(0.002 mol) of tetrahydroquinoline and 1 ml of methylene chloride at O-4 ° C are added 1 ml

diluted hydrochloric acid (1: 1). Mixture

carefully moved and left at

room temperature for 2 hours.

the crystals are filtered out repeatedly

washed with ether, benzene, then again

dry ether is dried in a vacuum desiccator.

Obtain 0.35 g (73%) of the target substance in

a form of dark green crystals with m. pl. 106 ° C

(decomp.), Hmaks at 825 nm (in alcohol), e 135000.

Found,%: N 5.78, 5.73; C1 7.35, 7.41.

CgaHasNaCl.

Claims (2)

Calculated,%: iN 5.80; C1 7.34. Example 5. Obtaining polymethine dye-3,3-diethyl-12,14- (trimethylene) -thi-hexacarbocyanine tosylate. To a mixture of 0.18 g (0.0004 mol) of chloride 11- (L-methylanilino) 4,6 - trimethyleneendec2, 4,6,8,10 - pentadienylidene-N - methylaniline, 0.44 g (0.0012 mol) 1-ethyl-2methylbenzthiazole tosylate and b ml of acetic anhydride are added dropwise while cooling with ice 1.2 ml of a 1 M solution of triethylamine in acetic anhydride. The mixture was stirred, left at room temperature for 10 minutes, and then kept at 0 ° C for 1.5 hours. JQ The precipitate was filtered, washed with 2 ml of acetic anhydride, ether, water, again ether, and dried in a vacuum desiccator. For purification, the dye is mixed with 3 ml of a mixture of benzene-methylene chloride (5: 1), filtered and washed with 2 ml of the same solvent. The operation was repeated sequentially with mixtures of benzene and methylene chloride in ratios of 3: 2 and 1: 1, each time taking 3 ml of the mixture of solvents. 20% yield 0.09 g (32%) of the desired colorant in the form of dark brown crystals, so pl. 177-179 ° C (decomp.). Found,%: C 69.31, 69.49; H 6.94, 5.96; N 3.72, 3.69.25 C41H42Y2O33. Calculated,%: C 69.64; H 5.98; N 3.96. 6 Claims of the invention are on- or undecamethine compounds of formula e, and RI is hydrogen or methyl; R2 is phenyl or RiR2N is a tetrahydroquinoline residue; pit - O or 1; X is chlorine. as intermediates for the synthesis of polymethine dyes. Sources of information taken into account during the examination 1. USSR author's certificate № 299503,. C 07 C 47/38, 12.23.69. 2. USSR author's certificate No. 457692,. From 07C 87/48, 12.06.73.