SU1076433A1 - Process for preparing imidamercyanino cyanic dyes - Google Patents

Abstract

METHOD OF BENEFITS , | - ethyl or phenyl; R - ethyl or allyl / X - iodine or perchlorate, characterized in that 5-acetanilinomethyl-substituted monomethine cyanine (General formula COCH5 / H. H5Ce - NC H pS,., RJ CH-VT | .f CrHy where 2 and R have the indicated meanings; C @ X-tosylate, iodine, perchlorate or eth lsulfate, is reacted with a quaternary salt of substituted 2-methylbenzimidazole of the general formula: i хЧХ 14 5 iB I: 1CsHs X where B,; R and 1H have the indicated values, in dimethyl sulfoxide at 100-105 s or boiling absolute ethanol in the presence of three ethylamine. About 4 00 WITH

Description

This invention relates to a process for the preparation of imidomericeanin cyanine dyes of the general Formula.

R

sn-hg

CiHft X

where 5G is the residue of benzoxazole, 5-phenylbenzoxaol, benzthiazole, 5-methoxybenzthiazole, 4,5-diphenylthiazole or 1-ethyl-5-trifluoromethylsulfonylbenzimidaeol; B is a carbethoxy group, trifluoromethylsulfonyl, or benzothiazolol-2; ft is ethyl or phenyl; -ethyl or allyl, - / f iodine or perchlorate.

The compounds can be used as spectral sensitizers for halogen-silver photographic emulsions used to produce black-and-white and color film photographic materials.

A known method for the preparation of merocyanin cyanine dyes, derivatives of heterocyclic nitrogen-containing bases, consists in the Eo interaction of anilinomethyl-substituted monomethine cyanine of the general formula

/ z

H C H- | -f

to the GNP

Crne X R

where R is ethyl or allyl; R is a hydrogen atom; Z is the residue of thiazole or 4,5-diphenylthiazole; X is methyl sulfate, with a quaternary salt of a methyl-substituted heterocyclic base of the general formula

&

II

CHj

Cjhj

where 2 is the residue of dihydroquinoline OR dihydropyridine; X - P-toluensulfonate, in a mixture of pyridine, acetic anhydride and triethyl on flj.

However, when using this method to obtain the imidamer cyanine dye of formula 1, the traces of the latter are formed only because of the reduced reactivity of the methyl group in the quaternary salts of the substituted 2-methylbenzimidazoles,

The purpose of the invention is to develop a process for the preparation of imidamerocyanin cyanine dyes, which allows them to be synthesized in satisfactory yields.

The goal is achieved by the fact that imidameracyaninocyanine dyes of general formula I are obtained by condensation of monomethine cyanines of general formula II, where Z is a benzoxazole residue, 5-phenylbenzoxazole, benzthiazole, 5-methoxybenzethiazole, 4,5-diphenylthiazole or 1-ethyl-5-trifluoromethylsulfanemethanemethanemethanemethanemethanemethanemethanesulfonic acid, which can be synthesized by the formula or allyl; aceto group; X is iodine, tosylate, perchlorate or ethyl sulfate, with a quaternary salt of a substituted 2-methylbenzimidazole of the general formula.

where Vir has the meanings indicated in general formula I; X is tosylate, iodine, perchlorate or ethyl sulfate, in dimethyl sulfoxide at 100-105 C or boiling absolute ethyl alcohol in the presence of triethylamine.

EXAMPLE 1. Preparation of 3, 3-diethyl-4-keto-5-methoxy-5- (1,3-diethyl-5-k, arbethoxybenzimidazolinylidene-2-ethylidene) thiazolinothiocyanine iodide (I, Z-5 - methoxybenzthiazole

X J).

В-СООС2К5.

A mixture of 0.1 g of 2-methyl-5-carbethoxyxybenzimidazole iodoethyl (0.25 mmol (IV,, B-COOCgHj-,) and 0.16 g of 3,3-di-3-methyl-4-keto-5-acetanilomethylene-5 - methoxythiazolinothiacyanin tosylate (0.25 mmol) (lla, Z-methoxybenzthiazole,.

R-COCHj, X-TOS) is dissolved at a temperature not higher than 100 ° C (in a bath) in 3 ml, 0.04 g (0.05 ml, 0.3 mol) of TEA is added and heated for 20 minutes at 100-105 C. To the hot solution was added 3 ml of 10% aqueous solution of potassium iodide, heated to 70 ° C, and left for 12-16 hours in a refrigerator. The precipitate separated is filtered off, washed on the filter successively with 7 ml of water, 1 ml of alcohol and 2 ml of ether.

Weight 0.16 g (83%), so pl. 256261 C (decomp.).

For purification, 0.16 g of the dye is recrystallized from 70 ml of alcohol. Output 0.13 g (63%), dark brown prisms with so pl. 263-265 C (decomp.).

Maximum absorption at 594 nm (in alcohol).

Found,%: C 51.48; H 5.2; N 7.17.

CjjHj JN O S2H 0. Calculated,%: C 51.2; H 5.2; N 7.47. Example 2. Preparation of 3, 3-diethyl-4-keto-5- (1, 3-diethyl-5-carbethoxibene-eimidazolinyl IJr-dden-2-ethyliden) thiazoline-thio-scieniide (I, Z-benzthiaol, I-Yo-Yc-Yc-Yc-Yc-I-Z-I-Z-I-Z-I-Z-I-Z-5- (-., XJ). It is obtained, similarly to the previous one, from 0.1 g (0.25 mmol) IVa and 0.16 g (0.25 mmol) of 3.3 diethyl-4-keto-5 acetanylinomethylene thiazoline-thiacyanine tosylate (Z - benzthiazole, R -, R-2 - COOHg,) in 1.5 ml of DMSO. After transferring to iodide, the mixture is kept for 12-16 h at 20-25 s. Weight is 0.15 g (86%), mp 250-252 0 ( decomp.). To clean, 0.15 g of the dye is recrystallized from 17 ml of alcohol. Yield 0.09 g (51%); dark green prisms with mp 259-260 ° C. Maximum absorption at 592 nm. (in alcohol). Found: C 52.73 N 5.26; N 8.26. N 4 O, S. Infusion,%: C 52.99; H 4.98; N 7.98. Example 3. Preparation of 3,3-diethyl-4-keto-5- (1,3-diethyl-5 -carbethoxybenzimidazolinylidene-2-ethylidene) thiazolinoxacyan iodide (I, Z - benzoxazole, B CoE; R; -, XJ). A mixture of 0.1 g (0.25 gmol) IVc ", 0.15 g (0.05 mmol) of 3,3-diethyl-4-keto-5-acetanylinomethylene thiazoline oxacyanitosylate (ive, Z, benzoxazole, R - C2Hj, R - COOCH) is dissolved by heating to 100 ° C in 1.5 ml of DMSO, 0.04 g (0.05 ml, 0.37 mmol) of TEA is added and heated for 20 min at 100-105 s. The solution is cooled to 20-25 ° C, 1.5 ml of alcohol is added and kept in the refrigerator for 2 hours. The precipitate is filtered off and washed on the filter with 5 ml of water, 0.5 ml of alcohol and 5 ml of ether. Weight 0.1 g (56.8%), so pl. 263-264. For purification, 0.1 g of the dye pen is crystallized from 10 ml of alcohol. Yield 0.07 g (40%), light brown shiny needles Art. square 27027lc (decomp.). Maximum absorption at 577 nm (in alcohol). Found,%: C 53.14J H 4.94) N 7.78. SH, 0. Calculated,%: C, 52.84; H 5.25 N 7.95 Example 4. Preparation of 3, 3-diethyl-4-keto-5-1-phenyl-3-ethyl-5 - (benzthiazolyl-2) benzimidazolinylidene-2-ethylidene thiazoline oxacyanide iodide (I, Z - benzoxazole, B - benzthiazolyl-2, R-, i-,). Prepared analogously to Example 2 from 0.12 g (0.25 mmol) of IVS, (R CjHj, B - benzthiazolyl-2,) and 0.15 g (0.25 mmol) of Ili. Weight 0.18 g (89%), so pl. 191-219s. For purification, 0.18 g of the product is boiled with 30 ml of alcohol, the undissolved residue is filtered and recrystallized from 90 ml of alcohol. Yield 0.05 g (25%); small green crystals with t. 266-268 with. Maximum absorption at 588 nm (in alcohol). Found,%: C 57.75; H 4.78; N8.36. Sz9 "E4. Vyisleno,%: C 57,56; H 4.42; N 8.61 Example 5. Preparation of 3,3-diethyl-4-keto-5- (jl-phenyl-3-ethyl-5- (benzthiazolyl-2) benzimidazolinylidene-2-ethylidene thiazolinothiacyanine iodide (I, Z - benzthiazole, B - benzthiazolyl-2-, R-, R-,), is obtained analogously to example 3 of 0.12 g (0.25 mmol) IV5 and 0.16 g (0.25 imol) 115. Weight 0.15 g (75 %), mp 222-230 ° C. For purification, 0.15 g of the dye is transform from 75 ml of alcohol, yield 0.08 g (39%) of dark green small prisms with mp 231232 ° С ( .). Maxim M absorptively at 602 nm (in alcohol). Found: C 56.68 H 4.52 Cjg Vm, 1: C 56.45; H 4.34 Example 6. Preparation 3, 1, 3-triethyl-4-keto-5-trifluoromethylsulfonium -5- (l, 3-diethyl-5-carbethoxybenzimndazolinylidene-2-ethylidene) thiazolino-imidiacyanine perchlorate (I, Z-1-ethyl-5-trifluoromethylsulfonylbenzimidazole, B COOC2H, R-R-CjHf, X10104)), R 0 CjHf, X 0104)), 104 4)) imidazole g (0.25 mmol) IVa, 0.17 g of 3,1,3-trihegyl-4-keto-5-acetic. anilinomethylene-5-trifluoromethylsulfonylthiazolimide cyanine perchlorate (0.25 mmol) (llr, 2-1-ethyl- 5-trifluoromethylbenzimidazole, R-CgH, R2-COCHj,) is dissolved by heating to 100 ° in 1.5 ml of DMSO, 0.04 g (0.05 ml, 0.37 mmol) of TEA is added and 30 NMH are heated at 100-105. To the hot solution was added 3 ml of a 10% aqueous solution of sodium perchlorate heated to 70 and left for 1 h at 20-25 seconds. The precipitated gummy precipitate is filtered, 30 MP of water is washed on the filter, then triturated with 5 ml of water, filtered, washed with 30 ml of water, dried, boiled with 12 ml of alcohol, the insoluble precipitate is filtered and 0.5 ml of alcohol are filtered onto the filter and 5 ml of ether. Weight 0.05 g (26%), so pl. 243-246 0 (decomp.). for cleaning 0.05 g of the dye is recrystallized from 9 ml of alcohol. Yield 0.04 g (21%) —purple brilliant needles with a m.p. 247-240 C (decomp.). Maximum absorption at S47 nm (in alcohol), Found,%: S 7.53 Cj lIjjF CINjOg Calculated,%: S 7.82 Example 7. Preparation of 3-lyl-3-ethyl-4 5-diphenyl-4-keto -5-phenyl-3-ethyl-5 - (benzthiazo-lyl-2) 6-benzimidazolinylidene-2-these-idenyl-thia-solinothiazolocyanine pyridine (I, Z-diphenyltnazol, B - benz thiazolyl-2, R,). Prepared analogously to example 1. From 0.12 (0.25 mmol) 1-phenyl-2-methyl-5- (benzthiazolyl-2 benzigchidazole (15) yodoethyl) and 0.18 g 0.25 mmol 3-allyl-3-ethyl -4-keTo -4, 5-diphenyl-5-acetanilinomethyl-thiazolinothiazolocyanine tosylate (lid; 2-4,5-diphenylthiazole, R-Cj pine,) in 1.5 ml of daso., Weight 0.21 g (91.3 %), mp 238244 C (decomp.). For purification, 0.2 g of the product is boiled with 10 ml of alcohol, hot filter s / p, residue (0.15 g, mp 255-258) a) perekristagpovyvayut from 140 ml of alcohol. Weight 0.1 g, so pl. 257-2bOs (decomp.). To obtain analytically pure sample, 0.1 g dye is recrystallized again from 120 m alcohol. Yield 0.08 g (35%) dark brown prisms with t-, pl.26 (decomp.) .. Maximum absorption at 596 nm (in alcohol). Found,%: S 10.34 Calculated,%: S 10.38 Example 8. Preparation of 3-al-lyl-3-ethyl-4-keto-45-diphenyl-5-d, 3-diethyl-5-carbethoxybenzim and azolinylidene-2-ethylidene) thiazolinothiazolocyanine iodide (I, Z-4, 5-diphenylthiazole, B-COOC H,,). Prepared analogously to example 2 of 0.1 g (0.25 mmol) IV Of and 0.18 g (0.25 mmol) lid when heated for 30 minutes. Weight 0.13 g (64%), so pl. 162-190s For purification, 0.13 g of the product is recrystallized from 8 ml of alcohol. Yield 0.04 g (20%); brownish-green with a bronze glitter Cretaceous, c.t. square 225-227 ° C (decomp.) Maximum absorption at 588 nm (in alcohol). Found,%: C 58.48, - AND 5.11, N 6.58 C4o 4-lJN Oj S2 You are 1 number,%: C 58.80; And 5.02, N 6.86. Example 9. Obtaining 3-allyl-3-ethyl-4-keto-4, 5-diphale L-, -5- (l, s-diethyl-5-trifluoromethylsulfonylbenzimidazolinylidene-2-ethylidene) thiazolinothiazolocyanine iodide (I, 2, 4.5 -diphenylthiazole, B CPgS02, R C2H5, k (,). A mixture of 0.12 g (0.25 mmol) of 1-ethyl-2-methyl-5-trifluoromethylsulfonylbenzimidazole ethyl tosylate (iVg, R C2H5, B-CFjSO, X T05) And 0.18 g (0.25 mmol) is not dissolved when heated in 1.5 ml of absolute alcohol, 0.04 g (0.05 ml, 0.37 mmol) of TEL is added, boiled for 20 minutes, added 3 ml of a 10% aqueous solution of potassium iodide heated to 1 Q ° C and left for 12-16 h at 20-25 0. The precipitate separated from Pour 10 ml of water, 1.5 ml of alcohol and 10 ml of ether on the filter, and successively wash them on the filter. Weight: 0.18 g (84%), mp 214-225 seconds (dec.). For cleaning 0.18 g The product is recrystallized from 40 ml of alcohol. Yield: 0.11 g (50%); green with a bronze luster: prisps S. mp 232-234 ° С (decomp.). Maximum in alcohol). Absorbance at 585 nm. Found,%: C 51.74, H 3.96, N 6.12 Sev bc R 40eZ3 Calculated,%: C 52.05; And 4.10; N 6.30 Example 10. Preparation of 3,3-diethyl-4-keto-5- (1, 3-diethyl-5-trifluoromethylsulfonylbnzimidazolinylidene-2-ethylidene) thiazolinothiacyanes uniodide (I, Z-benzthiazole, R). In SKZ302. It is obtained analogously to the previous one from 0.12 g (0.25 mmol) IV B and 0.16 g (0.25 mmol) 115. Weight 0.17 g (88%), so pl. 187-200 ° C (decomp.). For purification, 0.17 g of product is recrystallized from 27 ml of alcohol. Weight 0.11 g (57%), so pl. 211-214s (decomp.). To obtain an analytically pure sample, 0.11 g of the dye is re-recrystallized from 25 ml of alcohol. Yield 0.08 g (42%), brilliant bronze prisms with a m pl. 215217s (decomp.). Maximum absorption at 590 nm (in alcohol). Found,%: С 45.68; H 4.30; N 7.05. C-tsHjo J -40 Calculated,% С 45.66, - Н 3.9, Н 7.35. Example 11 Preparation of 3,3-diethyl-4-keto-5-methoxy-4-. - (1, 3-diethyl-5-trifluoromethylsulfoiylbeneimidazolinylidene-2-eti / -deden) thiazolinothiacyanine iodide (I, Z - 5-methoxybenzthiaol, B - CF, ZOL R,),

Prepared analogously to example 9 of 0.12 g (0.25 mmol) of IV6 and 0.16 g (0.25 mmol) of Na. Weight 0.14 g (70%), mp. 195-211 C.

For purification, 0.14 g of the product is recrystallized from 30 ml of alcohol. Yield 0.07 g (35%); small purple prizl "1 with t. pl. 245-247 C (decomp.). Maximum absorption at 594 times (in alcohol).

Found,%: C 44.28; H 3.93; N 6.57

zy zg Z 404b about

Selected,%: C 45,44; H 4.19; N 6.91

P-, p and m e r 12. Preparation of 3,3-diethyl-4-keto-5- (l, 3-diethyl-3-trifluoromethylsulyl benzyl 2 1 -idazolinylidene-2-ethylidene) thiazolinooxacyanine iodide (I. Z-benzoxazole, B CFjS02, R,).

Prepared analogously to Example 9, from 0.12 g (0.25) IVe and 0.15 g (0.25 mmol) IV. Weight 0.15 g (80%), so pl. 187-190s.

For purification, 0.15 g of product is recrystallized from 21 ml of alcohol.

Yield 0.1 g (54%); green with bronze glitter prism with m. 20204s (decomp.). Maximum absorption at 576 nm (in alcohol).

Found%: C 46.47 / H 4.19

 H F

Vyisleno,%: C 46.60; H 4.02

Example 13. Preparation of 3,3-diethyl-4-keto-5-phenyl-5- (1, 3-diethyl-5-trifluoromethylsulfonobenzimidazolinylidene-2-ethylidene) thiazolinooxacyanine iodide (I, Z-5-phenylbenzoxazole, 3 C7 jSO, C 2 Hff ,

Prepared analogously to Example 9 from 0.12 g (0.25 gmol) IVB and 0.16 (0.25 mmol) of 3,3-diethyl-4-keto-5-phenyl-5-acetanilino-methylenediamine-, zolinooxacyanine ethyl sulfate (lie, Z -5-phenylbenzoxazole,,,,, H5304). Weight 0.08 G (80%), so pl. 233-240C.

For purification, 0.08 g of the product is recrystallized from 20 ml of alcohol. Weight 0,05, so pl. 262-264 ° C (decomp.). To obtain an analytically pure dye, 0.05 g of product is re-recrystallized from 16 MP of alcohol. Output 0.04 g (40%) green with a bronze sheen crystals with t. Pl. 265-267 0 (decomp.). Absorption maximum at 582 nm (in

Alcohol).

Found,%: S 7.77 / J 15.38 CjjHj FjJN OjS Calculated,%: S 7.78; J 15.45 Example 14. B1l of a melted negative bromide-silver emulsion (d 1.0 μm), rVg 2.2. 3,3-diethyl-4-keto-5- (1,3-diethyl-5-carbethoxybenzyshdazolinylidene-2-ethylidene) thiazolinooxacyanide (I, Z-benzoxazole,

В-ССОС Н, R rR.,) In the amount of 32 "1 (D mol / mol AgHal (10 mg / l). Sensitized emulsion is kept in a thermostat for 20-30 min, and then watered on a plate or film. Get black White material with

  them and the boundary of the sensitization zone 640 nm.

Example 15. B1l of a molten negative bromide-silver emulsion (d 1.0. Mkm), rVg 2.2, 3,3-diethyl-4-ke-

then-5- (1, 3-diethyl-5-trifluoromethylsulfonylbenzimidazolinylidene-2-e thilideH) and azolyne-oxide sacianium neiodide (I, Z-benzoxazole R — R —C2H5, X — J) in the amount

32-10 6 yul / mol AgHal (11 mg / l). Next, do the same as the previous example. A black and white material with a D gravel of the sensitization zone of 650 nm is obtained.

Example 16. B1l of a melted negative bromide-silver emulsion (d 1.0 µm), pBg 2.2 3,3-diethyl-4-keto-5-d-phenyl-3-ethyl-5- (benzthiazolyl-2) was added benzimidazolinylidene-2-ethylideneJ - THazolinooxycyaniniodide (G, Z-benzoxazole, B-benzthiazolyl-2,, Xj) in an amount of 32-10 mol / mol AgHal (12 mg / l).

The sensitized emulsion is allowed to stand in a thermostat at 35 ° C for 20-30 clay, then a water-alkaline solution of N- (3-sulfro-6-methyl octadecylamino) -anilide-1-hydroxy-2-naphthoic acid is added in an amount of 10 g / l emulsion and after a 0.5-hour maturation, watered on the plate, or film. Get the material

.. 620 nm and the boundary of the senol zone | C

syphilization 660 nm. When conducting color processing of photographic material get a blue image. .

Example 17. B1l of a melted negative bromide-silver emulsion (d 1.0 µm), pBg i 2.2, 3-allyl-3-ethyl-4-keto-4, 5-diphenyl-5- (1,3-diethyl -5-carb toxyben zimid z oli nilide n-2-ethylidene) -thiazolinothiazolocyaniniO “

did (I, Z-diphenylthiazole, B-COC, gH, .R-C, H “. H-C3, NU, X-J) In the amount of mol / mol AgHaI (13 mg / l). The synthesized emulsion is allowed to stand in a thermostat for 20-30 minutes, then a 1-base (3-sulfo-4-phenoxyphenyl) -3-steroyl aminopyranol solution (5) is added in an amount of 10 g / l of the emulsion after 0.5 hours of standing watered on plates or film. Get stuff with

G G Not

L, f 620 nm and sensitization limit of 660 nm. When carrying out color processing of photographic material get a purple image.

Thus, the proposed method allows to obtain imidamerocyaninocyanine dyes with yields in an analytically pure state of 20-63%, which can be used for spectral sensitization of halogen-silver photographic emulsions.

Claims (1)

METHOD FOR PRODUCING IMIDAMEROCYANINOCYANINE DYES of the general formula where 2 and R have the indicated meanings; ' X- tosylate, iodine, perchlorate or ethylsulfate, is reacted with a quaternary salt of a substituted 2-methylbenzimidazole with general formula _{5 with 2N} gde1 - residue benzoxazole, 5-fenilbenzoksaeola, benetiaerla metoksibenztiazola _e-5, 4,5-difonil1 C ₂ H ₅ X '· where in ,. R and G have the indicated meanings, in dimethyl sulfoxide at 100-105 ° C or boiling absolute ethanol in the presence of triethylamine. 00 oo ί