SU93374A1 - The method of obtaining thia-, selenium- and thiacelene-carbocyanine dyes - Google Patents

Description

are widely used for the sensitization of halo-silver and other emulsions.

Asymmetric carbocyanines of structure I are usually obtained by condensation of quaternary salts of nitrogenous heterocyclic bases containing the active methylene group in a- or Y-position to a nitrogen atom with quaternary salts of 2 (4) alkenyl (aralkenyl or styryl) derivatives of nitrogenous heterocyclic bases. the position of arylamino, alkyl- (or aralkyl) -thio- (or seleno) groups or a halogen atom.

Upon receipt of asymmetric carbocyanines by the condensation of quaternary salts of a- or Y-alkyl- (or

aralkyl) substituted heterocyclic bases with quaternary salts of 2 (4) -alkenyl (aralkenyl or styryl) derivatives of nitrogenous heterocyclic bases containing in the 3-position of the arylamino group, but many cases are formed, often in significant quantities, corresponding to symmetric dyes, which from the main products of the reaction is usually difficult.

The formation of symmetric carbocyanines is also observed when using acyl (or selenoacyl) derivatives of N-substituted partially hydrogenated heterocyclic bases.

The formation of asymmetric carbocyananes with the replacement of the average carbon atom of the polymethine chain occurs quite smoothly during the interaction of the quaternary salts of 2 (4) -alkenyl (aralkenyl or sterile) derivatives of nitrogenous heterocyclic bases containing alkyl (or aralkyl) in the P-position of alkyl (or aralkyl). or seleno) -groups or halogen atom. However, these compounds are relatively inaccessible.

The proposed method allows to eliminate these drawbacks. The entity concludes as follows.

It has been found that asymmetric carbocyanine dyes with substituents at the average carbon atom of the polymethine value of the general structure I are usually obtained in sufficient yields and in high purity by condensation of the quaternary 2 (4) -n-alkoxy- (or aralkoxy) -3-alkyl- ( aralkyl- or aryl) vinyl derivatives of nitrogenous heterocyclic bases with quaternary salts of nitrogenous heterocyclic bases containing the active methylic group in C1 or g-polszhesi to nitrogen nitrogen:

Y R R R YI

III Z-C C-C-- Zi

X,

R OH - f HX (or NHL

The reaction proceeds by heating the mixture of initial quaternary salts 15 of aliphatic alcohols, for example, ethyl or normal propyl alcohol, in the presence of basic substances, for example, tertiary aliphatic amines.

This method can also be used to obtain symmetric carbocyanine dyes with substituents at the middle carbon atom of the polymethine chain.

The following are examples of the preparation of thia-, selenium- and tselenenecarboiianin dyes.

Example 1. 3,3-diethyl-9-methyl - 4 5-benzothiacarbocyanine anide. 1.4 g of 3-ethyl-2-acetylmethylene-4,5-benzobenzthiazoline and 0.7 g of dimethyl sulfate are heated for 30 minutes. in an oil bath at 120-125 °. The resultant sintering mass of the quaternary salt is dissolved in 10 ml of normal propyl alcohol. 1.5 g of 2-methylbenzthiazole iodoethyl and 0.5 g of triethylamine are added to the solution and the liquid is heated for 30 minutes. in an oil bath at 120-125 °.

Ether is added to the red-violet solution after cooling. After removal of the ester, the residue is dissolved in 20 ml of ethanol and the dye iodide is precipitated by adding an equal volume of 10% aqueous potassium iodide.

The precipitated dye precipitate is filtered and washed with alcohol, water and ether.

Yield 0.9 g (32% of theory).

The dye is obtained in the form of small dark brown prisms with green tint (from ethyl alcohol) with a melting point of 242-244. Maximum absorption at (in ethyl alcohol).

Example 2 .. 3,3-dimethyl-9-ethyl4, 5-benzothiacarbocyanine iodide. 1.0 g of triethylamine and liquid are added into a solution of 3.9 g methylmethyl sulfate 2-3methoxybutenyl 4,5-benzobenzthiazole and 3.4 g methyl 2-methylbenzthiazole methyl p-toluenesulfonate in 50 ml of absolute ethyl alcohol

heated for 30 minutes. “In a boiling water bath. The dye iodide is liberated by the addition of 50 ml of a 10% aqueous solution of potassium iodide.

12 hours later the product is filtered and washed with water and alcohol.

Yield 2.0 g (36.9 from the theory).

After a single crystallization from ethyl alcohol, the dye is obtained in the form of reddish-brown prisms with a melting point of 210.

Example 3. 3,3-9-triethyl-5-methoxythiacetylenecarbocyanine aniodide. To ethyl ethyl sulfate 2-methyl-5-methoxybenzselenazole, obtained by heating for 3 hours. 2.2 g of base with 1.6 g of diethyl sulphate at 120, 3.5 g of ethylmethyl sulphate of 2-methoxybutyl benzothiazole, 40 ml of absolute ethyl alcohol and 1.0 g of triethylamine are added.

The mixture is heated 30 mip. A kin water bath and iodine dye is then released in the usual way.

Output 1.7 g (28.4% of theory).

The dye is obtained in the form of green prisms (from ethyl alcohol) with a melting point of 137-138 °. Maximum absorption at 559 / nii (in ethyl alcohol).

Example 4. 3,3-9-triethylthiacarbocyaninide. A mixture of 3.6 g of ethylmethylsulfate 2-, 3-methoxybutenylbenzthiazole and 3.5 g of ethyl-p-toluenesulfonate 2-methylbenzthiazole dissolves by heating in 60 ml of absolute ethanol. After adding 1.0 g of triethylamine, the liquid is heated for 30 minutes. A boiling water bath and dye iodide are then precipitated by the addition of 90 ml of a 10% aqueous solution of potassium iodide.

12 hours later the precipitated dye precipitate is filtered and washed with water and alcohol.

Yield 2.5 g (48% of theory).

After a single crystallization from ethyl alcohol, green prisms are obtained with a melting point of 205-206 °. Maximum absorption at 547 m (t (in ethanol).

Example 5. 3,3-diethyl-9-methyl4, o, 4,5 -dibenzothiocarbocyanine bromide. Obtained from the previous

(see Example 1), from 1.4 g of 3-ethyl-2-acetylmethyl. , 0 ml of normal propplovogo alcohol. After adding 2.0 ethyl-para-toluene sulfonate to 2-methyl-3-iaftothiazol and a solution of 0.5 urpet, 11, - | 1 l; 1 G of r, 5,0 ml to normaly propyl alcohol liquid "it is heated up 30 mnp. at 120-125 pas oil bath.

Brompd dye is excreted in the usual way. Yield 0.8 g (28.5% of theory); melting point 228-230 °.

After crystallization from methyl alcohol, the dye forms shiny blue-green needles with a melting point of 239-240 °.

Example 6. 3,3-dimethyl-9-ethyl4, 5,4,5 -dibenzothiocarbocyanine bromide. 1.4 g of 3-methyl-2-propionylmethylene-4, 5-benzobenzthiazoline p 0.7 t dimethyl sulfate are heated

30 min. at 120-125 ° in an oil bath. The resulting quaternary salt is dissolved in 7.0 ml of normal propyl alcohol. 1.9 g of methyl-para-toluenesulfonate 2-methyl-3-naphthothiazole and 0.5 s of triethylamine in 5.0 ml of porcine alcohol are added to the solution. The liquid lasts 30 minutes. at 120-125 ° m the dye bromide is excreted in the usual way.

The output of 0.6 g (22% of theory).

After crystallization from ethyl alcohol, glitter and blue-green prisms with a melting point of 230-232 ° are obtained. Maximum sweep at 575 / pi (in ethyl alcohol).

Example 7. 3,3-diethyl-9-phenylgiacarbocyanine iodide. 2.8 g of 3-ethyl-2benzoylmethylplenbepzthiazoline and 1.3 g of dimethylsulfate are heated for 1 hour in a boiling water bath. To the resulting glassy mass of the quaternary salt, 3.0 g of 2-methylbenzthiazole iodoethyl are added and the mixture is dissolved in 30 ml of absolute ethanol. After the addition of 1.0 g, the trapatilamp liquid is heated for 1.5 hours in a boiling water bath. In an intense violet colored solution, the dye is recovered in the usual way.