SU93582A1 - The method of obtaining symmetric and asymmetric dicarbocyanine dyes - Google Patents

Description

The subject of the invention is a method for producing symmetric and asymmetric dicarbocyanine dyes with an alkoxy group in the polyloxyl chain position. These dyes are used as optical sensitizers for halo-silver emulsions.

The described method for the preparation of symmetric and asymmetric dicarbocyanine dyes allows for additional synthesis of these compounds.

The peculiarity of this method is that the quaternary salts of 2- alkoxypropenyl derivatives of heterocyclic

benzthiazole, benzenelenol or their substituted bases are condensed with quaternary salts of 2- alkoxyvinyl derivatives of the same or other heterocyclic bases when heated in an ethanol environment in the presence of triethylamine.

Example 1. 3,3-, diethyl-E-methoxythiadicarbocyanine aniodide

A mixture of 1.7 g of 2-3-methoxypropenylbenzthiazole ethyl methyl sulfate and 1.7-½ g of ethyl methyl vinyl sulfate 1.7 g of ethyl methyl sulfate is dissolved by heating in 25% absolute ethyl alcohol. 0.5 g of triethylamine is added to the solution in 5 ml of absolute alcohol, and an intense blue-violet color immediately appears.

The liquid is heated for 15 minutes in a boiling water bath and the dye iodide is precipitated by adding an equal volume of 10% aqueous solution of potassium iodide.

After cooling, the colored dye is filtered and washed with water and alcohol.

Yield 1.5 g (about 55.5% of theoretical). Pace. square 133-134 °.

After two crystallizations from ethyl alcohol (1 g from 150 ml), green rectangular prisms are obtained with a temp. square 138-140 °. Maximum absorption at 620 (in ethanol). Maximum sensitization

660 fflJA.

PRI mme R 2. 3,3-diegil-9-methoxyselenadicarbodianiniodide

In a solution of 2.0 g of ethylmethylsulphate, 2- 3-methoxypropenylbenzselenazole and 1.9 g of ethylmethylsulphate of 2- methoxyiviylbenzselenazole in 20 ml of absolute ethyl alcohol are added 0.5 g of triethylamine in 5 ml of absolute alcohol, and immediately .

The liquid is heated for 15 minutes in a boiling water bath and the dye iodide is precipitated by adding an equal volume of 10% aqueous solution of potassium iodide. After 12 hours, the precipitated crystalline dye precipitate is filtered and washed with water and alcohol.

Yield 2.0 g (62.5% of theoretical). Pace. square 156-157 °.

After two-time crystallization from ethyl alcohol (1 g from 75 ml receive small V-violet needles with a temp. Pl. 158-159 °. Maximum absorption at 630 tons (in ethyl alcohol). Maximum sensitization 680 / rzjj

Example 3. 3, E-diethyl-9-methoxy6, 7 6 7 -dibenzothiadicarbociipipbromide

3.6 g of ethylmethylsulfate 2-3-methoxypropenyl-6, 7-benzobenzthiazole and 3.4 g of ethylmethylsulfate 2-3-methoxy-vinyl 6, 7-benzobenzethiazole are dissolved by heating in 30 ml of absolute ethanol. In addition, 0.9 g of triethylamine and a liquid that instantly becomes intensely visible in color is heated for 15 minutes on a boiling water bath, after which the dye bromide is precipitated by adding an equal volume of a 10% aqueous solution of potassium bromide.

The precipitated crystalline precipitate is filtered and washed on the filter with alcohol and water. Yield 1.3 g (about 24% of theoretical). Pace. square 140-144 °.

After three times crystallization from absolute ethyl alcohol, thin blue needles are obtained with a temp. square 179-181 °.

Maximum absorption at 650 tons (in ethanol).

Maximum sensitization 690 OTJJ.

Example 4. 3,3-diethyl-9-ethoxythiadicarbocyanine iodide

3.7 g of ethyl ethyl sulfate, 2-p-ethoxypropenyl benzethiazole and 3.3 g of ethyl methyl sulfate 2- methoxy-vinyl benzthiazole are dissolved by heating in 30 ml of absolute ethanol. 1.0 g of triethylamine is added to the solution, and an intense blue-violet color immediately appears. After heating for 15 minutes in a boiling water bath, the dye iodide is precipitated by adding 30 ml of a 10% aqueous potassium iodide solution. After cooling, the precipitated precipitate is filtered and the MHBatoT is filtered on the filter with water and a small amount of alcohol. Output 3.6 C (64.3% of theoretical). Pace. silt 146-148 °.

To remove the carbocyanine impurity, the dye is treated several times with 3.5% hydrochloric acid with shaking (4 times 25 ml). The acidic solution is neutralized with aqueous ammonia, the liberated dicarbocyanine is filtered off and washed with water.

After two-time crystallization from absolute ethyl alcohol, brilliant green prisms with a temp. square 158-160 °. Maximum absorption with neg. (in ethanol).

EXAMPLE 5 3,3-Diethyl-9-methoxy6, 7-benzothiaselenadicarboxyananone and neiodide.

A mixture of 4.0 g of ethylmethylsulphate, 2-p-methoxypropenyl-6,7-benzobenzthiazole and 3.8 g of ethylmethylsulphate, 2-p-methoxyvin and lane, is dissolved in solution and dissolved by heating in 30 ml of absolute ethanol. After adding 1.0 g of triethylamine. The liquid is heated for 15 minutes in a boiling water bath. From the intense blue-colored solution, the dye iodide is precipitated by adding 30 ml of 10% potassium iodide solution. The precipitated crystalline precipitate is filtered and washed on the filter with water and ether.

Yield 1.1 g (17.0% of theoretical). Pace. square 138-144 °.

After double crystallization from absolute ethyl alcohol