SU244887A1 - - Google Patents

Description

METHOD OF OBTAINING SYMMETRIC OR

NONYMMETRIC M 30-ALKYL SUBSTITUTED SELENA OR SILENATIACARBOCIANS, DERIVATIVES

4,5-BENZOBENZALENOZOLA

The invention relates to the method of obtaining symmetric or asymmetrical meso-alkyl substituted selenium or selenate carboarcins derived from 4,5-benzo benzselenazole, which is an effective sensitizer for halogen-silver emulsions to the orange and red parts of the spectrum.

A known method for the preparation of lazo-alkyl-substituted selenathicarbocyanines by condensation of methyl methane sulfate 2-p-naphtholelenazole with sulfoalkyl betaine 2-alkyl-mercaptoalkenyl derivatives of heterocyclic bases B in the medium of aliphatic alcohol, in a drawing a drawing bout of aliphatic alcohol, in a drawing a drawing of a mixture of alocyclic bases with aliphatic alcohol, in a drawing a drawing a drawing of a mixture of aliphatic alcohol and aliphatic alcohol.

This method is not applicable for the synthesis of 4,5,4,5 - dibenzo - 9 - alkyl selenacycarbocyanine dyes. Symmetrical 9-alkyl4, 5,45-dibenzoselenenocarbociani. They also cannot be obtained by this method.

kilosubstituted selenium- or selethiacarbocyanates (I) of the general formula

 R

P x

(one)

where Y-Se or S; B is hydrogen or a substituent group; R and Rs are alkyl; Ra is alkyl, oxy-, sulfo-, acetox-, sulfo- or carboxyalkyl; X - acid residue, consists in the condensation of the Quaternary salts of 2- | 3-chloroalkenyl-4, 5-benzobenselenazol (I) and 2-methyl-substituted nitrogen-containing heterocyclic bases (III) or the Quaternary salts of the last 2 - 3-chloroalkenyl derivatives of the last (IV) with halo allylates , alkyl alkyl sulfates or 2-methyl-3-naphthalelenazole (V) alkyl alkyl sulfonates.

 Y

H-i (-4

 Y

o-n (: - Ch

iv)

iiv;

The reaction readily proceeds in aliphatic alcohols or chloroform in the presence of tertiary aliphatic ammonia, for example, triethylamine, at room temperature or under low pressure.

Quaternary salts of 2- | 3-chloroalkenyl-4,5-beta 1-benzenselenazole can easily be obtained by exposure of phosgene to 2-acylmethyl-3-alkyl-p-naphthoselenazolines (ed. St. USSR „YO 136375). The latter can be obtained by conventional methods by acting on quaternary salts, for example, 2-methylr-naphthoselenazole iodo-acylates, carboxylic acid chlorides in pyridine (English Pat. No. 46G269) or anhydrides of the indicated acids in the presence of aliphatic tertiary amines (.HFG No. 1072765).

Example 1. Preparation of 3,3-dimethyl-9-ethyl4, 5,4,5-dibe: Nzoselencarboniyaninchloride.

A mixture of 3 g of chloromethyl 2-p-chlorobutenyl-4, 5-benzobenselenazole, 3.6 g of methyl methyl sulphate 2-methyl-p-naphthoselbnazole and 50 g of absolute ethyl alcohol are boiled for 5-7 minutes in a boiling water bath. 4 ml of tr ethylamine is added to the hot suspension and the mixture that turns blue is kept in the dark at normal temperature.

The next day, the dye is filtered off, washed with water and alcohol (weight 1.5 g, mp. 220-230 ° C), dissolved in 300 ml of ethanol when heated, and 300 M of a 10% chloride solution is added. on three . The precipitate formed is filtered off, washed with 20 ml of alcohol and 100 ml of water and dried at 40-50 ° C.

The output of 1.2 g (20% of theoretical), so pl. 185-187 ° C.

For purification, the dye is crystallized from 100 ml of ethanol and washed with alcohol and benzene.

Get large green needles; m.p. 192-193 ° C. Maximum absorption at (in ethyl alcohol); sensitization maxima at 685 and 620 nm.

Se H / -, rH r-r, H L

; i)

Calculated,%: C1 6.96.

With the same yield, the dye is formed and the reaction is carried out in chloroform.

When replacing methyl methyl sulphate 2-methyl-naphthoselenazole with the corresponding iodoethyl, 3,9-diethyl-3-methyl-4,5,4,5-dibenzoselenene, carbocyanine iodide (absorption maximum at 593 nm) are obtained. Similarly, during the condensation of chloromethyl

2- | 3-Chlorobutenyl-4,5-benzobenzselenazol with iodine- 3-hydroxyethyl 2-methyl-5-methoxybenzselenazole or Y-sulfonoiylbetaine 2,5,6trimethylbenzthiazole in absolute methanol in the presence of triethylamine heated by

the corresponding 3-methyl-3-p-hydroxyethyl - 9-ethyl-4,5-benzo-5-methoxyisethene carbocyanine iodide and 3,5,6-trimethyl-3-y-sulfopropyl - 9 - ethyl - 4,5-benzoselentatecarboxyanbetaine are formed ( yields 42 and 60% of theoretical).

For the preparation of chloromethyl 2-p-chlorobutenyl-4, 5-benzobenzenelenol to a suspension cooled to -5 ° C, 1.5 g of 2-methyl-naphthoselenazole iodomethyl in 5.5 ml of pyridine and 0.3 g of propionic acid for 20 minutes 0.74 g of propionyl chloride is added at -5-0 ° C. The mixture was placed for 3 hours at 0 ° C, after which it was heated for 1 hour in a boiling water bath. The mixture is then poured into 40 ml of water and 4 ml of hydrochloric acid (

beats. at. ,nineteen. In this case a resinous precipitate is formed, which is gradually becoming crystallized from the crystal. The precipitate is filtered off, washed with water and dried. For cleaning, the resulting 2-propionylmethylene-3-methyl-4,5-benzobenselenazoline is dissolved in benzene, the solution is chromatographed on alumina, and benzene is distilled off.

The output of 0.63 g (50% of theoretical). Yellowish needles (from alcohol) with m. Pl. 164-165 ° C.

A solution of 1.2 g of 2-propionyl1-methylene-3-methyl4, 5-benzobenselenazoline in 15 ml of dry chloroform is gradually added with stirring to a solution of 0.75 g of phosgene in Q ml of chloroform, cooled to 5 ° C.

benzselenazole is filtered off, washed with acetone and dried.

The output of 1.26 g (90% of theoretical); m.p. 119-120 ° C.

Found,%: N 3.69; 3.79.

CieHisNClsSe.

Calculated,%: N 3.77.

Example 2. Obtaining 3,3,9-trimethyl-4,5, 4,5 - dibenzoselenenocarboxyanmethyl sulfate.

A mixture of 3.6 g of chloromethyl 2- | 3-chloropropyl-4, 5-benNobenselenazole, 3 g of methyl methyl sulphate 2-methyl-:: 5-naphtholenazole and 20 ml of absolute ethanol is heated for 5 minutes in boiling water. 3 ml of triztilamine are added, an intense blue color appears, the liquid is boiled for 5 minutes, cooled and diluted with ether. The next day, the precipitate is filtered off, washed with 10 ml of alcohol, water and ether.

For purification, the dye is boiled with 300 ml of ethanol, 300 ml of water is added, and the liquid is left for 24 hours at room temperature. Selected glittering dark-green crystals are filtered, washed with alcohol, water and ether.

Yield 1.3 g (20% of theoretical); m.p. 197-198 ° C. After crystallization from ethyl alcohol, dark-blue crystals are obtained with a mp. 198-200 ° C.

Found,%: N 4.36, 4.22.

CzgHzeO NaSSe ,.

Calculated,%: N 4.27. Absorption maximum at 589 nm (in ethanol).

Similarly, during the condensation of chloromethyl 2-p-chloropropenyl-4,5-benzobenselenazole with ethyl p-toluenesulfonate 2-methyl-p-tin. Phtothiazole in ethyl alcohol in the presence of triethylamine by heating for 15 minutes followed by the addition of a 10% solution potassium bromide get 3,9-dimethyl-3-ethyl-4,5,4,5-dibenzoselenatiacarbocyanine bromide (yield 40%).

To obtain 2-p-chloropropenyl-4, 5-benzobenselenazole chloromethylate, a solution of 4.6 g of 2-acetyl: methylene-3-methyl-p-naphtholenazoline in chloroform was added to a solution of 3.8 g of phosgene in the same solvent. The next day, the liquid is diluted with ether, the precipitate is filtered off, washed with acetone and dried. Yield 5 g (93%).

2 - Acetylmethylene-3-methyl-p-naphthoselenazoline (yellowish needles from alcohol; mp. 137-139 ° C) is obtained, analogously to the 2-p-ionylmethylene derivative, by exposure to acetyl chloride on 2-methyl-p-naphthoselenazole iodomethyl in pyridine ( yield 55%).

Example 3. Obtaining 3,3,9-trimethyl-4,5, 4,5-dibvnz Oselenatiacarbocyanine iodide.

0.32 g of chloromethyl 2-p-chloropropenyl 4, 5-benzobenzthiazole and then 0.4 ml of triethylamine are used. The mixture then turns blue.

It is heated for 2-3 minutes in a boiling water bath, cooled and (30 ml of ether is added. The next day, the precipitate is filtered, washed with water and ether, dissolved by heating in 60 ml of ethanol and 30 ml of 10% is added potassium iodide solution. The separated dye is filtered off and washed with alcohol, water and ether.

The output of 0.32 g (50% of theoretical). After crystallization from 150 ml of ethyl alcohol, dark blue crystals are obtained with a melting point of 200 ml. 210-211 ° C. Maximum absorption at 580 ml (in ethyl alcohol).

Found,%: N 4.49. CasHasNoSSeJ.

Calculated,%: N 4,48.

Similarly, when replacing chloromethylate 2-chloropropenyl-4, 5-benzobenzthiazole with 2-p-chloropropenyl-5-methoxybenzthiazole chloroethylate

3,9-dimethyl-3-ethyl-4,5-benzo-5-methoxy-selenation-carbocyanine methyl sulfate is obtained.

Example 4. Obtaining 3,3-dimethyl-9-ethyl4, 5,4,5 - dibenzoselenationakarbotininoiodide. 0.8 g of methyl methyl sulphate of 2-methyl-p-naphthoselenazole and 0.68 g of chloromethyl of 2-p-chlorobutenyl-4,5-benzobenzthiazole, heated to boiling, are added to 0.8 ml of triethnlamine and 20 ml of absolute ethidyl alcohol. the dark blue liquid boils for 3 min. After cooling, the reaction mixture was diluted with ether. The next day, the precipitate is separated from the resinous mass, washed with ether last, the solution is heated in alcohol, and a 10% aqueous solution of potassium iodide is added. The precipitate formed is filtered, washed with alcohol, water and ether.

The output of 0.6 g (47% of theoretical). For 10 CLEANING, the dye is crystallized from ethyl alcohol.

Dark blue crystals are obtained with mp. 210 ° C. Absorption maximum at 587 nm (in ethanol). Maximum sensitization at 685 nm.

Found,%: N 4.40, 4.24. CagHacNaSSeJ. Calculated,%: N 4.38.

Condensation under the same conditions of 2-methyl-p-naphthoselenazole yoethyllate with 2-p-chlorobutenylbenzothiazole chlorethylate gives 3,3,9-triethyl-4,5-benzoelenatiacarbocyanine as iodide. Absorption maximum at 582 nm (in ethanol).

or selenathiacarbocyanines, 4,5-benzobenzselenazole derivatives of general formula

Se r y

Y –Sn s-1

- (one)

where Y-Se or S; B is hydrogen or a substituent group; Ri and R are alkyl; R2 is alkyl, hydroxy, sulfo, acetoxy, sulfato or carboxyalkyl; X is an acid residue by condensation in an organic solvent in the presence of a tertiary aliphatic amine at ordinary temperature or reflux, characterized in that quaternary salts are subjected to 2-chloroalkane; Nile-4,5-beisobenzselenazole with 2-methyl-substituted nitrogen-containing heterocyclic. bases or quaternary salts of 2-p-chloroalkenyl derivatives of heterocyclic bases with haloalkylates, alkyl alkyl sulphates or 2-methyl naphthalelenazole alkyl alkyl sulphonates, and as organic an aliphatic alcohol or chloroform is used for the solvent.