SU910700A1 - Process for producing monomethyne cyanine dyestaffs - Google Patents

Description

(B) METHOD FOR OBTAINING MONOMETINOCYANINE DYES

I

The invention relates to the field of producing polymethine dyes, in particular monomethine cyanine dyes, which are used as starting compounds for the synthesis of spectral sensitization SbH5-} TH-eH HI

where Z is 3,3-dimethylindolenin, benzox, benzthiazole, 5-methoxybenzthiazole, 5-methylthiodiazole (, +) f 1-ethyl-5-trifluoromethylsulfonylbenzimidazole or 1-ethyl-5-carbethoxybenzimidazole

and about

 to a hydrocarbon or substituted hydrocarbon residue; .

X is the acid residue (X O,

l about

 if R or R contain an acid group),

A ditch of photographic halogen-silver emulsions, including for color film photographic materials.

Methods are known for producing monometin cyanine dyes of total Lormula I

h

--1 LSN-.

7

h

X

: R

by condensation of 3 pheny-3-ethyl - (- ketothiazolinothocyanine bromide with diphenyl, 5 formamidine in ethylene glycol solution at 90-95 ° C.

The yield of the target product is 11.

A disadvantage of the known method 20 is the toxicity of the aryl or alkyl isothiocyanates used, which impairs the working conditions.

The closest to the invention is a method for preparing monometintsianinovyh dyes of general formula I. The process consists in reacting 2-.chetvertichnyh salts alkilmepkaptoproizvodnyh 5 anilinometilen- -ketotizzolina-2 and 2 () - metylzame1tsennyh heterocyclic bases in solution of anhydrous chloroform in the presence of a tertiary aliphatic amine with 10 -25C with the selection of the target product by a known technique. The yield of the target product 21.

The disadvantage of this method is the relatively low yield of the target product, the environmental pollution released by the reaction of toxic, easily volatile al il mercaptans,

The purpose of the invention is to protect the environment from pollution and increase the yield of target products.

This object is achieved in that in the preparation sposore monometintsianinovyh edges {CITEL general formula I by reaction of quaternary salts of derivatives of B-anilinometilen- -ketotiazolina2 and 2 (k) - methyl-substituted heterocyclic bases E solution of anhydrous chloroform in the presence of an aliphatic tertiary amine such as a quaternary salt derivative 5 - anilinomethylene-4-ketothiazolin 2 - a compound of the general formula y is used wherein R has the above values and the process is carried out at 25 -. Compounds ii can be readily prepared by reacting the available 3-alkyl (alkenyl) -5-anilino-methyl rhodanine with the f -propanesultone upon heating. Example 1. Preparation of 3.3 diethyl-β-keto-5-anilinomethylene-4,5-diphenypthiazoline-thiazolocyanine tosylate (1, Z-4.5-diphenyl thiazole; CnHg X-), 9 g of ethyl tosylate of 2-methyl mercapno - 5 anilino-methylenrodanine (0.02 mol) ) dissolved by heating in 35 ml of anhydrous chloroform, the solution is cooled to 20-25 ° C, a solution of 9, O g of ethyl tosylate 2 - Methyl 4,5 - dipheiyltizol (0.02 gm) in 40 ml of the same solvent is added, the mixture is stirred, cooled to 15 - iSc, add 3 g (4.2md) of triehylamine (TEA) (0.03 gm), and stir for 2 hours at room temperature (20 -), after 12-15 hours the solvent is distilled off t dryness in vacuo, the residue was triturated with 100 ml of dry acetone, filtered and washed on the filter with 50 ml of the same solvent. Obtain 7.27 g (53.4) of a green powder with m, pl, 243 - 247 ° C (with a maximum absorption at 486 and 335 nm (and ethyl alcohol). Found,%: S 14.13 Chm; Calculated , S 14.11. Example 2, Preparation of 2-sulfopropylmercapto-3-ethyl-5-anilinomethylenerodanine (|, R-C, H-), Mixture of 2.7 g of 3-ethyl-5-anilinomethylenerodanine (0.01 mol) and 1.8 g of propanesulton (0.015 mol) is heated for 5 hours at 135-140 ° C (in a bath), 15 ml of dry acetone is added, boiled for 30-40 minutes in a boiling water-bath and incubated for 12-15 h at 2025 C, The resulting solid mass is triturated, filtered and washed on the filter with 20 ml of dry acetone. Weight 3.8 g (98, P); t, mp, 193 197 ° C (with dilution,). To clean, 3.8 g of product are boiled with 15 ml of dry acetone, the hot mixture is filtered, the precipitate is the filter is washed with 5 ml of dry acetone and 3.7 g (95.5%) of a light brown powder with m, m, 194 (with diff,) are obtained. Maximum absorption at 422, 295 and 277 nm. Found, ° 4 : S 24.65, C jHiaMlHB. Calculated,%: S 24.89. EXAMPLE 3- Preparation of 2-sulfopropylmercapto-3-ellyl-5-anilinomethyleneenanine (f, R -), Mixture 2.76 g 3-l-L-5-anilinomethylenerodanine (0.01 mol) and 1.8 g-propanesulton (0.015 mol) are heated for 5 hours at 135 - (in the bath), 30 ml of dry acetic acid are added on, refluxed for 30 - 40 minutes in a boiling water bath and kept 5 12 - 15 hours at 20 25 ° C .. The resulting solid mass grow rayut, filtered and washed on .filtre 10 ml of the same oastvoritel. Weight 3.0 g (75%) -, so pl. 18H-192 ° C (with decomp.). To purify 3), 0 g of the product is boiled with 20 ml of dry acetone and the hot mixture is filtered. The precipitate was triturated with 20 ml of the same solvent, filtered, washed with 20 ml of dry acetone on a filter, and 2.70 g (67.8%) of light brown powder was obtained. 191 (with different). "Maximum absorption at 22-, 337,276 nm (in ethyl alcohol) .1 Found: S 23.89C / ibH-igO NQiSn,. Calculated: S 2,13. Example 4. Obtaining di-ethyl-A-keto-5-anilinomethylene-4,5 diphenylthiazolinothiazoanocyanine tosylate (I, Z -4,5 - diphenylthiazole; R R X -). A mixture of 0.39 g of 2-T ulfopropilmer capto-3-ethyl-5 enilinomethylenerodanine (0.001 mol) (|, R -) and 15 ml of anhydrous chloroform are heated under stirring for 10 minutes at 35 ° C (inside the mixture), added to thief 0.45 g of 2-methyl-4,5-diphenylthiazole ethyltosylate (0.001 mol) in 5 ml of the same solvent and stirred to a temperature of 15 2Q ° C; 0.15 g (0, 1 ml) of TEA (0, 0015 mol) or 0.27 g (0.35 l} of tri-n-butylamine (, 0.0015 mol) and stirred for 2 hours at room temperature. After 1215 hours, the solvent is distilled off in vacuum to dryness, and the residue is boiled with 3 to 5 ml of dry acetone. The mixture is kept for 12 - 15 while cooling () the precipitate is filtered and washed on the filter with 2.5 ml of the same solvent. Weight 0.51 (75); mp. 235 238 ° C (with decomposition). The dye is purified by boiling with 4 times the amount of ethyl alcohol and get a brown powder with p. pl. 244 - 247 C (with decomp.). Maximum absorption at 486 and 335 nm (in ethyl alcohol). Found, 1: S 14,14. With NzbMdO Yaz. Calculated,: S 14.11. Example 5. Preparation of Zethyl 3-T sulfopropyl-4-keto-5-anilinomethylene thiazolinothiacyanine betaine (I, Z-benzthiazole; R-CnH-, (CH-i) 5SO-j). 0. b It is obtained similarly to the previous one from 0.39 g (0.001 mol) (P, R i, and 0.27 g of α-sulfopropyl betaine 2-methylbenzthiazole (0.001 mol). Weight 0.38 g (76%}; mp. - (c). The dye is purified by boiling with a 5-fold amount of absolute ethanol and brown prisms are obtained with m, pl 238 (with c.). Maximum absorption at 486 and 330 nm (in ethyl alcohol). Found,% : S 19.25. S ,,. Calculated,%: S 19.17. Example 6. Preparation of 3.3 diethyl - 4-keto-5-anilinomethylene thiazolinooxacyantosylate (l, Z - benzoxazole; RR CoH5; X -). A mixture of 0.33. (1, R -) {0.001 mol) and 0, ethyl tosylate -2 - methyl benzoxazole (0.001 mol), 15 ml of anhydrous chloroform and 0.15 g (0.21 ml) of TEA (0.0015 mol) are boiled for 3 hours in a boiling water bath. After 12-15 hours, the solvent is distilled off in a dry adcum, and the residue is boiled with 5 ml of dry acetone. The mixture is kept for 12-15 hours with cooling (P-5C), the precipitate is filtered off and washed on the filter with 3 ml of the same solvent. Weight 0.37 g. (66); mp. 232-235 0 (with diff.). The dye is purified by boiling with 10 times the amount of absolute ethyl alcohol and orange prisms are obtained with a melting point of 20 ml. 250 - 253 ° C (with decomp.) "Maximum absorption at 46V and 324 nm (in ethanol). Found : S 11 .45. H (2gNj05S2 .. Calculated, I: S 11.19 P p and m.e p 7. Preparation of 3.3 diethyl-4-keto-5 -anilinomethylene -1 ethyl-5-trifluoromethylsulfonylthiazolimididianine perchlororate. (IZ - 1ethyl-5Trifluoromethylsulfonyl-chloro-chloro-hydrochloride. RR; X - C104). A mixture of 1.52 g (0.004 mol) (H,), 1.76 g of 1-ethyl-2-methyl-5-trifluoromethylsulfonylbenzimidazole iodoethyl (O, 004 mol), 80 ml of anhydrous chloroform and 0.6 (0.84 ml) TEA (0.006 gm) is boiled for 2.5 hours in a boiling water bath. After 12-15 hours, the solvent is distilled off in vacuum to dryness, the residue is dissolved by heating in 20 ml of ethanol and 60 ml of 20% aqueous solution of perchlo It is heated to 40–50 ° C. The mixture is kept for 1 hour at 20. 25 ° C, 60 ml of water are poured and kept for 12–15 hours at 0-5 ° C. The precipitate which has separated out is filtered and washed on the filter with 100 ml of water. 2.2 (g (8 / a); mp 132-135 ° C (with decomposition). For purification, the dye is recrystallized twice from ethanol because (1 g out of 12 ml) and brown prisms with half the surface are obtained. pl, 158 - 1bO ° C (with decomp.). Absorption Maximum at and nm (in ethyl alcohol):

Found,%: C1.

CQsHi, H407S (FsCl.

Calculated,%: C1 5, + 9.

Example B, Preparation of 3,3 Diethyl-4-keto-5-anilinomethylene-1-ethyl-5 - carbethoxythiazolinimidacyanine perchlorate (I, Z - 1 - etile-5 carbethoxybenzimidazole; R R CnNg; X C1 04) /

It is obtained similarly to the previous one from 0.39 g (0.001 mol) (il, R - and 0.39 g iodo ethyl 1-ethyl-2-methyl5-carbethoxybenzimidazole (0.001 mol) with 6-mass boiling. Weight 0, k2 g (70 ); mp 121-128 ° C (with decomposition). For purification, the dye is recrystallized from n-propanol (1 g from 15 ml) and light brown Prisms are obtained with mp. C (with decomposition). Absorption maximum at 138 and 408 nm (in ethyl alcohol).

Found:: C1 6.09. . .

CfiTH-i N407501.

Calculated,%: C1 6.05.

Example 9. Preparation of lil-3-ethyl-β-keto-5 anilinomethylene V, 5-diphenylthiazolinothiazolocyanine tosylate (I, Z-, 5-diphenylthiazole; R -; X -).

A mixture of 0.40 g of 2-sulfopropyl mercapto-3 allyl-5-anilino-methylenrodanine (0.001 mg) (i, R -, CiH5), 0.45 g of ethyl tosylate-2-methyl-h, 5 diphenylthiazole (0.001 mol), 20 ml of anhydrous chloroform and 0.15 g (0.21 ml) of TEA (0.0015 mol) are boiled for 3 hours in a boiling water bath. After 12-15 hours, 2 - 3,3-dimethylindolein, benzok sazol, benzthiazop, 5-etoxtoxivator are distilled off to dryness under vacuum. The residue is boiled with 5 ml of acetone, rubbed and the mixture is kept between 12 and 15 at 0-5 ° C, then the precipitate is filtered off and washed on the filter with 2.5 ml of the same solvent. Weight 0.40 g (58); m.p. 234-237С (with diff.). The dye is boiled by boiling with 4 times the amount of absolute ethyl alcohol and dark brown prisms are obtained with a melting point of 200 ml. - (with different). Maximum absorption at A83 and 338 (in ethyl alcohol). .

Found%: S 1.15. .

Calculated,%: S. Example 10 Preparation of 3 allyl-3-ethyl-β-keto-5-anilinomethylene 4, 5-diphenylthiazolinothiazolocyanine ethylsulfate (t 5 Z -, 5 - diphenylthiazole; R - X Cr H5S04)

It is obtained analogously to the previous one from 0, tO g (0.001 mol) (|, R CjH) and 0.41 ethyl ethyl sulfate 2-methyl-4, 5 diphenylthiazole (0.001 mol). Weight 0.41 g (631); That pl. 22 - (with different).

The dye is purified by boiling with a 2.5-fold amount of absolute ethyl alcohol and light-brown prisms are obtained with a melting point of 200 ml. 23b 238 ° C (with decomp.).

Absorption maximum at 484 and 338 nm (in ethyl alcohol).

Found, I: S 14.98. C ,,, H Nj05S3.

Calculated,%; S 14.84. The use of a compound of formula I as a derivative of 5 anilinomethylene-4-ketothiazolin-2 makes it possible to eliminate the formation of toxic easily volatile alkyl mercaptans and to increase the yield of the target product.

invention formula

The method of obtaining monometincyanine dyes. General formula

benzthiazole, 5 - methylthiodiazole (1 ,.), 4,5 - diphenylthiol 99107 sol, 1 - ethyl-5-trifluoromethyl-. sulfonylbenzimidazole mpi 1ethyl-5-carbethoxy6enimidazo / g hydrocarbon or substituted hydrocarbon residue; X, is the acid residue (X O, if R or R contain an acid group), by the interaction of the quaternary salts of the 5-anilino-methylene-4-keto-Yu thiazolin-2 and 2 (4) -methyl-substituted derivatives

SbN5-YN-S1H h $

where R is a hydrocarbon or substituted. a. hydrocarbon residue, and the process is carried out at 25-TOO ° C.

Sources of information taken into account in the examination

1. US patent No. 2535992, class; 269-240, pub. 1950. 5

oT SluHOjSo,

i

2. Gershtein R.A. , Sveshnikov N.N., iirova L.V. Synthesis of merocyanin cyanines from monometincyanine dyes with a residue of 5 acylarylaminoalkylidene-4-ketothiazoline-2. Scientific papers Gosniihimphotoproject, 1977, no. 25, p. 3 (prototype). 0O Heterocyclic bases in anhydrous chloroform solution in the presence of a tertiary aliphatic amine when heated; and with subsequent isolation of the target product, characterized in that, in order to increase the yield of the target product and improve environmental conditions, the compound of general formula fl is used as a quaternary salt of anilinomethylene-4-ketothiazoline-2 derivative 5

Claims (1)

•Claim A method of producing monomethincyanino ₅₀ dyes. General formula where Ζ - 3,3 - dimethylindolein, benzoxazole, benzthiazole, 5 - methoxy benzthiazole, 5 “methylthiodiazole (1,3,4), 4,5 diphenylthia9 zol, 1 - ethyl-5 - trifluoromethylsulfonylbenzimidazole or 1 .. ethyl 5-carbethoxybenzimidazo, g R ″ and R ^ is a hydrocarbon or substituted hydrocarbon residue; X-acid residue (X = O, A about ⁹ if R or R ^x contain an acid group), by the interaction of the quaternary salts of derivatives of 5 ^- anilinomethylene-4-ketothiazoline-2 and 2 (4) -methyl substituted 9Yu00 Heterocyclic bases in a solution of anhydrous chloroform in the presence of a tertiary aliphatic amine when heated, followed by isolation of the target product, characterized in that, in order to increase the yield of the target product and improve environmental conditions, as a quaternary salt of the derivative 5 ^_ anilinomethylene-4-ketothiazoline- 2 use a compound of the general formula 1'1 I with ₆ n ₅ -yan-en-t-s oAwi В ¹ where R ¹ is a hydrocarbon or substituted hydrocarbon residue, and the process is carried out at 25 “10 ° C.