SU198130A1 - METHOD OF OBTAINING POLYMETINE DYES - Google Patents

Description

A method is proposed for the preparation of polymethine dyes of the cyanine and merocyanine series, used as optical sensitizers for halogen-stimulating photographic emulsions.

Found that polymethine dyes of General structure I, II and III

OH (7 ,,,

N

IR

f g (; sn th

Z (} -en

where R is alkyl; Z - residues of thieno- (3,2 -) - quinoline-7 or -9; Zi - residues of benzthiazole, benzoxazole, benzselenazole, thieno (3,2 - {) quinoline-7 or -9; X - acid residue can be obtained by condensation of quaternary salts of 7-methylthieno (3,2 -) - quinoline or 9-methylthieno- (3,2-f) -quinoline with intermediates commonly used in the synthesis of polymethine dyes, for example, orthoformate, ethyl ether, 3-ethyl-5- {a-acetanilinomethylene) -thiazolidingione-2-on-4,2- (| 3 acetanilinovinil) -benzthiazole, l-dimethylaminobenzaldehyde.

General polymethine dyes

I, I, and III sensitize halogen-refractory photographic emulsions to the zone of 520-790 microns.

Example 1. Preparation of 6,6-diethylthieno (3b-2i-f, 3b 21-G) -Hino-9,9-carbocyanine iodide.

A mixture of 0.72 g of 9-methylthiepo- (3,2-) quinoline iodoethyl, 0.7 g of orthoformate ethyl ether and 3 l of nitrobenzene is heated for 30 minutes at 180 ° C. The reaction mixture is cooled, the dye is precipitated with ether, dissolved by heating in 3 ml of ethanol, and 3 ml of 10% aqueous solution of potassium iodide is added to the solution. The dye precipitated upon cooling is filtered off and washed

on air. Output 0.26 g, so pl. 258-259 ° C. After crystallization from ethanol - dark blue prism with m. Pl. 261-263 ° C. Maximum absorption at 729 m / s. (in ethanol). Found, s / v: N 4.49; 4.63.

C29H29IN2S2.

Calculated, o / o: N 4.72.

With the introduction of a halogen-refractory emulsion of 0.81 mg in 1 liter of the synthesized dye, photographic material is obtained that is sensitized in the zone of 720-790 m, m, k with a maximum of 760 lgj / s.

Example 2. Getting 6,6-diethylthieno (3i, 2i-f, 3i, 21 -) - hino-7,7-carbocyanine iodide.

A mixture of 0.5 g of 7-methylthieno (3.2 - {) quinoline iodoethyl, 0.4 & The orthoformate ethyl ether and 3 ml of nitrobenzene are heated at 180 ° C for 20 hours. The reaction mixture is cooled, the dye is precipitated with ether, dissolved by heating & It ml of ethanol, to the solution was added 3 ml of 20 ° / about-th solution of potassium iodide. The dye precipitated by cooling is filtered off, washed with 20 HALF water, 5 ml of 500 / ethanol, 5 ml of 96% ethanol, 20 ml of ether and dried in air. Output 0.15 g. T. pl. more than 300 ° C. After crystallization from ethanol - green nlash with t. Pl. more than 300 ° C; maximum is abundant, eni at 635 MMK (in ethanol). Found,,%; N 4.56; 4.61.

C29H25IN2S2.

Calculated, o / o: N 4.72.

With the introduction of 2.4 mg of the synthesized dye into halogen-refractory emulsion, photographic material is obtained sensitized in the zone of 560-720 mmk with a maximum at 670 mmk.

Example 3. Obtaining 3-ethyl-5- 6-ethylthieno- (3; 1,2-f) - dihydropyridyl and dan-9e t and l and d e azolidintio n-2-o-n a-4.

A mixture of 0.36 g of iodoethyl 9-methylthieno- (3,2-) quinoline, 0.3 g of 3-ethyl-5- (a-acetanilinomethylene) -thiazolidinrion-2-one-4, 5 ml of anhydrous ethanol and 0.1 g of triethylamine is heated in a boiling water bath for 30 minutes. The dye precipitated upon cooling is filtered off, washed with ethanol and dried in air. Yield 0.3 g. T. pl. 226-228 ° C. After crystallization from ethanol - green plates with m. PL. 232-234 ° C. Found, “/ o: N 6.87; 6.93.

C2Hi8N20S3.

Calculated, o / o: N 7.03. The maximum is abundant, eni at 625 MMK (in ethanol).

With the introduction of 8.96 mg of a dye-producing halogen-photographic emulsion into a liter of synthesized dye, photographic material is obtained that is sensitized in a zone up to 700 mmk with a maximum at 660 mmk.

Example 4. Obtaining 3-ethyl-5- 6-ethylthieno- (3i, 2i-f) - dihydropyridilide n-7e t and l and de e azolidintio n-2-on n a-4.

nomethylene) -thiazolidintnon-2-one-4.10 ml of anhydrous ethanol and 0.2 g of triethylamine are heated on a boiling water bath for one hour. The dye precipitated upon cooling is filtered off, washed with ethanol and dried in air. Output 0.1 g. T. pl. 238-239 ° C. After crystallization from ethanol - dark-violet needles with m. 241-243 ° C. Maximum absorption at 584 m / s (in ethanol).

With the introduction of halogen-cerebral emulsin 17.9 L1g of synthesized dye into 1 liter, photographic material is obtained that is sensitized in the zone of 530-690 m / s with a maximum at 620 m / m. Found,%: N 6.99; 7,10.

C2Hi8N20S3.

Calculated, о / д: N 7.03.

Example 5. Preparation of b-methyl-3-ethylthieno- (3i, 2i-f) - quin 0-7-t and carbocyanine diode.

A mixture of 0.46 g of iodoethyl 2- (| 3-acetanilinovinyl) -benzthiazole, 0.36 g of iodomethyl 7-methylthieno- (3,2-G) -quinoline, 5 ml of acetic anhydride / and 0.1 g of triethylamine are heated

5 nri 105-110 ° C for 20 minutes The dye which precipitated upon cooling is filtered off, washed in 10 ml of water with 5 ml of 50 ° / normal ethanol, 5 ml of 96% ethanol, 15 ml of ether and dried in air. Output 0.25 g. T. pl.

0 256-258 ° C. After crystallization from ethanol, the greenish needles with m. Pl. 261-263 ° C. Maximum absorption at 593 m / s (in ethanol). Found,%: N 5.39; 5.46.

C24H2lIN2S2.

5 Calculated o / o; N 5.31.

With the introduction of a halogen-refractory emulsion 8,22 into one liter of the synthesized dye, photographic material is obtained that is sensitized in the zone up to 680 mk with a maximum at 625 mk.

Example 6. The preparation of 6-methyl-3-, ethylthieno- (3i, 2i-f) - X and n O-7-selen acarbo ci an and n and one.

5 A mixture of 0.36 g of iodomethyl 7-methylthieno (3,2-f) -quinoline, 0.46 g of iodoethyl 2- (p-acetanilinovinil) -benzselenazole, 5 ml of acetic anhydride and 0.1 g of triethylamine are heated at 125-130 ° C for 20 min. The dye precipitated upon cooling is filtered off, washed with 10 ml of water, 5 ml of 500 / o-ethanol, 5 ml of 96% ethanol, 15 L1 L of ether and dried in air. Output 0.2 g. T. pl. 247-248 ° C. After crystallization from ethanol - dark purple needles with m. Pl. 253-254 ° C. Maximum absorption at 597 m / s (in ethanol).

Found, o /,: N 4.69; 4.87. C24H2iIN2SSe.

0 Calculated, o / o: N 4.86.

With the introduction of a halogen-refractory emulsion of 10, 7 .gr of synthesized dye into 1 liter, photographic material is obtained that is sensitized in the zone up to 680 microns with maxi. Example 7. Preparation of b-methyl-3-ethylthieno (3.1, 2i-f) - xi BUT -7-OK sa ka r bo cci an ny ny d d and d a. A mixture of 0.36 g of 7-megyltieno (3,2 -) - quinoline iodomethyl, 0.46 g of 2- (p-acetanyl iovinyl) benzoxazole iodoethyl,. 5 ml of acetic anhydride and 0.1 g of triethylamine are heated at 125-130 ° C for 20 minutes. The dye precipitated during cooling is filtered off, washed with 10 l of water, 5 ml of 50 V / o ethanol, 5 ml of 96 / o ethanol, 20 ml of ether and dried in air. Yield 0.3 g. T. pl. 246-248 ° C. After crystallization from ethanol, the greenish prisms with m. Pl. 254-256 ° C. Maximum trap. |; Eni at 559 mm, k, (in ethanol). With the introduction of 8.6 mg of the synthesizing dye into 1 liter of the halogen-refractory emulsion, photographic material sensitized in the zone up to 680 fAMK is obtained in the usual way. with a maximum at 590 MMK. Paideno, o / o: N 5.28; 5.43. C24H2lIN2SO. Calculated,%: N 5.46. Example 8. Obtaining iodomethyl and 7-p-d and methylaminosthenylthieno (3i, 2,1-f) -X and N o l and N and. A mixture of 0.36 g of iodomethyl 7-methylthieno (3,2 -) - quinoline, 0.18 g of p-dimethylaminobenzaldehyde, 2 ml of pyridine and 0.05 g of piperidine is heated at 100 ° C for one hour. The dye precipitated during cooling is filtered, washed with water, alcohol, ether and dried. Output 0.28 g. T. pl. 271-273 ° C. After crystallization from alcohol - violet prisms with m. Pl. 277-279 ° C. Maximum absorbed; enis at 528 MMK (in ethanol). Found, o / o: N 5.79; 5.83. C22H2lIN2S. Calculated, o / o: N 5.93. With the introduction of 0.97 mg dye in 1 liter of halogen-refractory emulsion, photographic material is obtained sensitized in a zone of up to 600MM.K with a maximum at 580 mmk. 6 Subject of the invention. Method of obtaining general polymethine dyes I, II, and III. s-sh He-sn- (1 Z (Z Y-en-yn-; -k (snz w in where R is alkyl; Z are thieno (3,2-G) quinoline-7 or -9 residues; Zi - residues of benzthiazole, benzoxazole, benzselenazole, thieno (3,2-) quinoline-7 or -9; X is an acidic residue that, in order to produce products suitable for optical sensitization of halogen-cerebral photographic emulsions, quaternary salts 7 -methylthieno (3,2-) -quinoline or 9-methylthieno- (3,2-G) -quinoline is condensed with intermediates commonly used in the synthesis of polymethine dyes, for example, orthramyl ethyl ethyl ether, 3-ethyl-5 - (, a-ac tanilinometilen) -tiazolidintion-2-oxazolidinone-4, 2- (p-atsetanilinovinil) -benztiazolom, p-dimethylaminobenzaldehyde.