SE126488C1 - - Google Patents

Description

Inventor: A. W. Anish.

Priority was given on January 19, 1945 (United States of America).

The present invention relates to a process for producing three-core iminol cyanines. The cyanine dyes, which contain several or two kernels, are already known. The dyes of this kind are described, for example, in U.S. Pat. No. 2,276,554 and British Pat. No. 489,335. heterocyclic character of the kind known as rodanin nuclei. In these dyes, however, the central, heterocyclic nucleus is connected to the spirits of two different resonance systems.

The present invention relates to a process for the preparation of trivalent iminol cyanines, which is characterized in that a methylenediazole is reacted with a compound of the following formula: COCH 3 ■ C61-1N - (CH). - CC = 0 where Z represents the atoms required to form a fern- or six-membered heterocyclic ring, and n Sr is equal to 1, 3 or 5.

The dyes produced in this way have certain important properties which the known dyes lack. For example, the dyes are not only marked sensitizers for silver halide emulsions but form Sven stable silver salts with silver ions. These properties Ora dyes are valuable not only as the sensitizing dyes but Sven as the filter and light protection dyes for silver halide emulsions.

The invention will be described in more detail in the following with the aid of some illustrative embodiments.

The tri-core iminol cyanine dyes prepared according to the invention have the following general formula: X C-C-C Y N-N / (CH).

! Z RO - C-1 where X and Y are the same or different and represent the atoms which are necessary for the completion of a heteroeyclic ring system of the type common in the eyanin dye, e.g. substituted or unsubstituted indolenines, lepidines, oxazoles, oxazolines, selenazoles, selenazolines, pyridine, quinoline, thiazoles, thiazolines; diazoles and quinazolines and the corresponding substituted or unsubstituted polycyclic compounds, such as benzthiazoles, benzelenazoles, naphthothiazoles, naphthoselenazoles, diazines and the like, Z represent the atoms required to form a five-membered or ex-membered ring, heterocycle. a substituted or unsubstituted barbituric acid, thiobarbituric acid, rhodanin, oxazoldione, thiazolone, pyrazolone, imidazolone, imidazole dione and so on, n Sr equal to 1, 3 or 5 and H Sr either vale or a pair of tongs e.g. silver, lead, mercury and the like.

In the preparation of the above-mentioned tri-nucleic iminol cyanines, an alcoholic solution of a methylenediazole with a five-membered or six-membered heterocyclicuranan product obtained from barbituric acid, thiobutyric acid, thiouricuric acid (glycolylthiourea name), oxazoldione, thiazolone or pyrazolone having a reactive acetanilido group, as Sr attached to a ring carbon atom closest to a keto group in such an intermediate. The acid metric methylenediazoles used in the preparation of the dyes according to the invention are described in Journal of the Chemical Society, 121, p. 464, 1922, and the asymmetric methylene cliazoles are described in U.S. Pat. No. 2,323,503.

The five-membered heterocyclic intermediates obtained from rodanin, thiazolone, hydantoin, oxazoldione and pyrazolone are described in U.S. Pat. No. 2,186,608 and are represented by the general formula: COCH, C, H, N - (CH) have the same value as stated above. More specifically, this general formula represents such compounds as: 4- (γ-acetanilidoallylidene) -1-benzothiazolyl-3-methyl-5-pyrazolone, 4- (γ-acetanilidoallylidene) -3-methyl-1-phenyl-5- pyrazolone, 5-acetanilidomethylene-3-allylrodanine, 5-acetanilidopropaclienylidene-3-allylrodanine, 5-acetanilidomethylene-3-phenylrodanine, XC - CH, - CY 3-ethyl-2-thio-2,4 (3,5) -oxazoldione, 5- (γ-acetanilidoallylidene) -2-diphenylamino-4 (5) -thiazolone, 5- (γ-acetanilidoallylidene) -3-ethyl- 2-thio-2,4 (3,5) -oxazoldione, 5- (γ-acetanilidoallylidene) -3-ethyl-1-phenyl-2-thiohydantoin, 5- (5-acetanilido-P24-pentadienylidene) -3-ethylrodanine .

As condensing agents in the preparation of the dyes according to the invention, they can be used incorrectly. Heterocyclic, nitrogen-containing bases, such as pyridine, diraethylpyridine, ethylpyridine, ethylmethylpyridine, trimethylpyridine, quinoline and the like using basic catalysts, such as triethylamine, tributylamine, sodium or potassium carbonate, or acidic condensing acid or hydrasic acid. In general, the amount of condensing agent used can vary within wide limits, e.g. frail 1-25 moles. Concentrations between 1 and 15 moles are preferred.

When 1 mol of a methylenediazole is condensed with 1 moi of a five-membered or six-membered, heterocyclic intermediate in the presence of a condensing agent, e.g. pyridine, a reaction can take place which can be written as follows: COCH, -Z- C, H, N - (CH) n - CC / N / \ \ / NH COCH3 XC — C — CY \ N1 II \ Nf (CH ).

C .., ii OH The following examples describe in detail how to produce certain special dyes according to the invention, but they are of course included only for the purpose of clarifying the invention and may not be construed as limiting the scope of the invention.

Example 1. 2-Diphenylamino-4-hydroxy-540), a) -dibenzothiazolylbutadienyl- (1,3) 1-thiazoline HO - CC - N (C6H3) 2 g (1 mol) of 5- (2i-acetanilidoallylidene) -2-diphenylamino-4 (5) -thiazolone was mixed in 20 cm 3 of taint pyridine, containing 1 cm 3 of triethylamine. The mixture was boiled under reflux for 11 .mu.m, cooled and then diluted with 5 cm @ 3 of water. The mixture was stirred vigorously for a few minutes and then diluted with another 10 cm 3 of water. D. the mixture was allowed to stand, separated from an oil which sank to the bottom from the liquid liquid on top. The oil was separated by decantation and dissolved in the smallest possible amount of methanol and diluted with 5% superchloric acid solution. The dye which separated was boiled twice with 95% ethyl alcohol and dried. - Example 3 2-thio-3-ethyl-4-hydroxy-5- [α,--dibenzothiazolylbutaclienyl- (1,3)] - 2,3, -dihydroxazole / C - C - C CH 2 / CH CH C - O III HO - CC = S 3-Ethyl-2-thio-2,4, (3,5) -oxazolidione was mixed with 20 cm 3 of dry pyridine, containing 1 cm 3 of triethylamine. The mixture was boiled under reflux for 11/2 hours, cooled and then diluted with 5 cm 3 of water. The mixture was stirred vigorously for a few minutes, then diluted with another 10 cm 3 of water. When the mixture was allowed to stand, an oil separated, which sank to the bottom from the liquid liquid on top. The oil was separated by decantation and dissolved in the least possible amount of methanol and diluted with 5% hydrochloric acid solution. The dye which separated was boiled twice with 95% ethyl alcohol and dried.

Example 3. 1-Phenyl-2-thio-3-ethyl-4-hydroxy-5- {co-co-dibenzoxazolyibutadienyl- (1,3)} - 2,3-dihydrimidazole C - C - C - C, HI HO - GC = S 2-Thiohydantoin was mixed with 20 cm 3 of dry pyridine, containing 1 cm 3 of triethylamine. The mixture was boiled under reflux for 11/2 hours, cooled and then spit out. 5 cm 'of water. The mixture was stirred vigorously for a few minutes and then diluted with a further 10 cm of water. DA the mixture lick sta oriird, sink an oil to the bottom, from the top liquid liquid. This oil was separated by decantation and dissolved in the smallest possible amount of methanol and diluted with 5% superchloric acid. The colored soul was separated, boiled twice with 95% ethyl alcohol and dried.

Example 4. 1-Phenyl-3-methyl-5-hydroxy-4- [,, co-benzoxabenstiazolylbutadienyl- (1,3) 1-pyrazolyl] -C-C N / CH CH CH C - CH - CH3 III HO - CN -3-Methyl-1-phenyl-5-pyrazolone was mixed with 20 cm 3 of dry quinoline, containing 1 cm 3 of triethylamine. The mixture was boiled under Aterfilide for 1112 hours, cooled and then diluted with. 5 cm 'of water. The mixture was stirred vigorously for a few minutes and diluted with a further 10 cm 3 of water. When the mixture was stirred, pour an oil to the bottom of the liquid liquid on top. This oil was separated by decantation and dissolved in the smallest possible amount of methanol and diluted with 5% superchloric acid solution. The dye which separated was boiled twice with 95% ethyl alcohol and dried d5rpA.

Example 5. 2-Thio-3-ethyl-4-hydroxy-5-k, o-dibenzothiazolylhexatrienyl- (1,3,5) 1-2,3-dihydrotiazole -, CC = S \ W. 2.8 g (1 mol) of methylenedibenzothiazole and 3.6 g (1 mol) of 5- (5-acetanilido-Q2,4-pentadienylidene) -3-ethylrodanine were mixed in 20 cm 3 of dry ethylpyridine, containing 1 cm 3 of tributylamine. The mixture was boiled under reflux for 11/2 hours, cooled and then diluted with 5 cm 3 of water. The mixture was stirred vigorously for a few minutes and diluted with a further 10 cm 3 of water. DA blanclningen lick sta. words, a oil sank to the bottom Iran the above liquid liquid. This oil was separated by decantation and dissolved in the smallest possible amount of methanol and diluted with 5% superchloric acid solution. The dye, which was separated, was boiled twice with 95% ethyl alcohol and dried.

Example 6. 1.4 g of methylenedibenzothiazole and 1.6 g of 3-allyl-acetanilidomethylenrodanine were read in 15 cm 3 of dry pyridine containing 1 cm 3 of triethylamine. The mixture was refluxed for 11/3 hours, cooled and then diluted with 5 cm 3 of water. The mixture was stirred vigorously and then further diluted with 10 cm 3 of water. The oil which separated thickened rapidly, and the liquid part was decanted. The oil was dissolved in the least possible amount of methanol and diluted generously with 5% superchloric acid solution. The dye which was separated was boiled twice with ethyl alcohol.

Example 7. (d-dibenzoxazolyltenyl) -2,3-dihydrotiazole [C] -C = S C31-1, 5 g of methylenedibenzoxazole and 6.4 g of 3-allyl-5-acetanilidomethylenrodanine were dissolved in 30 cm 3 of dry pyridine, and g of anhydrous sodium acetate were added. The mixture was refluxed for 3 hours and cooled. Water was added to precipitate the dye as an oil. The cooled mixture lick sta. orord Overnight, and the solidified oil was filtered off and washed. with water. The crude dye was redissolved in 60 cm3 of pyridine and carefully diluted with water. The discharge became cloudy. The diluted pyridine solution was cooled for 4-5 hours and the unreacted material was filtered off. The filtrate was treated with% superchloric acid flake until thorough. DA filtrate lick sta orort, utfalides fargamnes crystals. The mixture was washed with water and dried.

Example 8. Benzoxazolylbenzthiazolylmethane and 3.2 g of 3-allyl-5-acetanilidomethylenodanine were used as starting materials.

Example 9. 2-Thio-3-allyl-4-hydroxy-5- [,, co-dibenzothiazolylbutadienyl- (1,3)] - 2,3-dihydrotiazole S 5-Acetanilido-allylidene-1,3-rhodanine and 3.2 g of methylenedihenestiazole were dissolved in 30 cm 3 of dry pyridine, and 0.5 cm 3 of triethylamine were added. The mixture was heated on an steam bath for 30 minutes. The reaction mixture was diluted with an equal volume of water. When the mixture was stirred, an oil sank to the bottom of the liquid liquid on top, and this oil was separated by decantation. The oil was dissolved in the least possible amount of methanol and diluted with 5% superchloric acid solution. The dye which was separated was boiled twice with 95% ethyl alcohol.

Example 10. C-NH 2.8 g (1 mol) of methylenedibenzothiazole and 2.8 g (1 mol) of 5- (γ-acetanilidoallylidene) -2,4,6-triketohexahydropyrimidine were mixed in 20 cm 3 of dry pyridine, containing 1 cm 3 of triethylamine. The mixture was boiled under Aterflode for 11/2 hours, cooled and then diluted with 5 ml of water. The mixture was stirred vigorously for a few minutes and then further diluted with 10 cm 3 of water. This oil was separated by decantation and thawed in the least possible amount of methanol and diluted with 5% superchloric acid solution, the dye separated was boiled twice with 95% ethyl alcohol and then dried.

Example 11. 2-Thio-4-oxo-6-hydroxy-5- [,, co-benzoxabenstiazolyl-butadienyl- (1,3) 1-1,2,3,4-tetrahydropyrimidine] 2.7 g (1 mol) of 2,2'-benzoxazolylbenzthiazolylmethane and 2.9 g (1 mol) of 5- (γ-acetanilidoallylidene) - 2 - thio-4,6-diketohexahydropyrimine was mixed with 20 cm 3 of dry pyridine containing 1.0 cm 3 of triethylamine. The mixture was boiled under Aterflade for 1 hour, cooled, and then diluted with 5 cm 3 of water. The mixture was stirred vigorously for a few minutes and then diluted with an additional 10 cm 3 of water. When the mixture was stirred, an oil sank to the bottom from the liquid liquid on top. This oil was separated by decantation and dissolved in the smallest possible amount of methanol and diluted with 5% superchloric acid solution. The dye which separated was boiled twice with 95% ethyl alcohol and then dried.

Although the invention has been described in detail with reference to certain preferred methods and materials, it is clear that the invention is limited thereto without many modifications being made. For example, the dyes which contain a merocyanine nucleus, e.g. oxazoldione, hydantoin (glycolylurinarone) and rodanin nuclei, as set forth in Examples 2, 3 and further treated with a quaternizing compound, such as methyl iodide. The quaternized compound is clarified under reflux with a cyclic ammonium base or salt, e.g. N-methyl-2-methylbenstiazole, which has a reactive methyl group in the alpha position in relation to the nitrogen atom, in the presence of such a condensing agent as pyridine, quinoline or the like. In the first reaction (alkylation), the triuclear iminol cyanine is modified in the male or all of the nitrogen atom in the 3-position of the oxazoldione, hydantoin or rhodanine ring. - 126'88 - is tarized and the sulfur atom in the 2-position is converted to a ten-ether group. In the second reaction (condensation), the alkylated, tri-nucleic iminocyanin is condensed with a cyclic ammonium base or salt, whereby new compounds, as well as valuable sensitizers, filter and light-shielding agents, are formed and have the following general purposes: XC-C CY (CH).

CQ II RO - C C = CH - C „RL \ NZ and X C — C — C Y (CH).

CQ RO - CC = CH - C R 2 X 'where R, X and Y and n have the same value as in the general formula given above, R 1 represents an alkyl, alkylene or aryl radical, R 2 represents an alkyl radical, X' represents an acid radical of the type common in cyanine dyes and Q represents either nitrogen, oxygen or sulfur. All such modifications and variations are intended to be within the scope of the present invention.

Claims (6)

Patent claim: 1. Set to produce tri-nucleic iminol cyanines, characterized in that a methylenediazole is reacted with a compound of the following form: COCH 2 - - -1 C 6 HN - (CH) r = CC = O where Z represents the atoms required to form a fern- or six-membered, heterocyclic ring, and ri fir equal to 1, 3 or 5. 2. A claim according to claim 1, characterized in that in molar respects equal amounts of methylenedibenzoxazole and 3-allyl-5-acetanilido-methylenrodanine are reacted with each other. 3. A claim according to claim 1, characterized in that in molar respects equal amounts of methyleneclibenestiazole and 3-allyl-5-acetanilido-allylidene-rodanine are reacted with each other. 4. A kit according to claim 1, characterized in that in molar respects equal amounts of 2,2'-benzoxazolylbenzthiazolylmethane and 3-allyl-5-acetanilidomethylenrodanine are reacted with each other. 5. according to claim 1, characterized in that the reaction takes place in the presence of heterocyclic, nitrogen-containing base, containing one tertiary amine. 6. A claim according to claim 2, characterized in that the reaction takes place in the presence of pyridine, containing triethylamine. Stockholm 1949. Kungl. Boktr. P. 'A. Norstedt & SiMer 490059