SU93461A1 - Method for preparing quaternary salts of 2 (4) -beta-alkoxy- or aralkoxyvinyl derivatives of nitrogenous heterocyclic bases - Google Patents

Description

The subject invention is a process for preparing Nl chetvertpchnyh salts of 2 (4) -; i - alkoksn - aralkokspviniliyh or derivatives of nitrogenous heterocyclic bases, finding application in boiling noluchepii sensibiliziruyupshh type dyes symmetrical and asymmetrical karbotsianinov, dimetiimerotsianinos, dikarbotsianinov, as well as some other nolimetipovyh dyes.

A distinctive feature of the described method is. that methylene - o - aldehydes are correspondingly partly hydrogenated bases and treated with alkylating agents at a higher temperature.

The reaction is usually carried out with a brief heating of the initial veins, at temperatures of up to 1CO °.

The proposed snoz expands the possibilities of obtaining sensibilii: iruin1 dyes of various types,

Example 1. Etklmethylsulphate 2 -; i - methoxyvinylbenzthiazole

A mixture of 2.46 g of 3-ethylbepzthiazolip-2-methylene-and -aldehyde and 1.59 g of dnmethylsulfate per 45 minutes in a water bath at 50–55 °. The resulting crystalline mass of the quaternary salt, colored and raspberry-red, is triturated in several stages with dry acetone (50 ml in total), filtered and washed on the filter with cold acetone. A salary is obtained, which is 83.8% of the theoretically possible amount, based on 3-ethylbenzthiazoline-2-methylene-41-aldehyde. Pinkish crystals with a temperature of ilavle1 and.

Example 2. Ethyl methyl sulfate 2 - i - methoxyvinylbenzselenazole

A mixture of 3.02 g of 3-ethylbenzselenazolin-2-methylene-shaldehyde with 1.59 g of dimethyl sulfate is heated for 45 minutes in a water bath at a temperature of 50-55.

The crystalline mass of the quaternary salt is thoroughly triturated several times with dry acetone (only 25 ml) and, after filtration, is additionally washed on the filter with a small

kolpchsstpom cvxoio acetone. According to .i uii) T 3.24 g of salt (71. from the theory of software: 5.0) ()) iS NEED

s-and-ochlopiropeshl krnstalloi with tem1I- | 5; tu | ) oi 11la1 laziness 1-8--13 ()

11 p iiNi with p 3. Methylmethylsul). ,,,, -fat-2.-, -metho, 14-vinyl-3,3-dimetkl | 1 (|. on,

2.21 1,3,3, - TRI. | CT11LI 1DOLN11 - 2 -matilen- (- al, eguida n A6 g

.) / (dyU1e, tilsu-l-фfata nagrs1 ak) t ½ for one and a half chao) on water oaitd P6 -totchai11Y heating pinkish stegundum mass a quarter: chnoG1 of salt is treated with iipii rooms by | Temperat re dry acetone. (5 ml) and then rinse them with dry benzene (5 ml). After drying in a desiccator and rubbing it with a glass rod, the quaternary salt crystallizes. Receive; 2.98 g (82.8% of theoretically possible). Pink crystals with a melting point of 110%

Example 4. Ethyl methyl sulfate 2- 3-methoxy-vinyl-5,6-dimethylbenzthiazole

2.33 g of 3 - ethyl - 5.6, 1G of methylbenzthiazoline - 2 - methylene - w - aldehyde and 1.33 g of dimethyl sulfate are heated

in a flask with an air REFRIGERATING HOOK on a bale; 1 e water bath.

A few minutes after the start of heating, the mixture melts and then melts, without a wall, into a solid crystalline mass. Heating is carried out for one and a half hours.

After boiling with a dry apéto, Yu.1. .- (30 ml) and washing on the filter with the same solvent (6 ml) obtain 2.3 g (from theoretically possible) quarter of a salt with a melting point of 151-152 °, in the form of colorless crystals.

An additional 0.75 g of the product with a melting point of 149; - 150

The total yield of the drug is 3,05 g or 84,9 L, from the theoretically possible amount.

. PRI me R 5. Ethyl methyl sulphate 2 -; j - mstoksivinil - 4 - phenidinzola

Mixture) 0.23 g of 3-ethyl-α-phenylthiazoline-2-methylene-vo-aldehyde and 0.13 g; 1 ml of methylsul (|); g; and heat the water bath at 50 (50 for one and a half hours. Then a half : ristallichesku dark red mass and rotting with benzene (2 times 4 ml) and absolute acetone (3 times but 1.

Output O.O-i g or 11.1 from the theoretically possible. Light-colored olite crystals with an ilavleia temperature of 160--162-.

PRI me R 6. Ethyl methyl sulfate 2 - | ti -. Methoxyvinyl - 6,7-tetra 1-methylene benzthiazole

0.26 g of 3 - ethyl - G, 7 - tetra.methylenebenzethiazolip - 2 - methyles -1) -aldehyde and 0.13 g of dimethyl sulfate are heated for () d) 1 bape for one and a half hours at 50 50 65. Then a viscous dark Mass processed, 1b; (yy at boiling with dry benzene (5 times 3 ml each) and after 1% absolute acetone (9 times 1 ml).

The output of the Quaternary Sun is 0.05 g or 12 ,, from theoretically possible. Cream-colored crystals with an ilavleia temperature of 175-176.

PRI me R 7. Ethyl perchlorate 2 bottlemilk vinylbenzthiazole

A mixture of 0.21 g of 3 - ethylbenzthiazoline - 2-methylene -o-aldehyde and 0.2 g of butyl iodide bind 30 lb n: g WATER. YANO b; 1 not at 50/65. a:; athe: -l pre-fill for 30 minutes at ICO. The crystalline mass is treated, at boiling with dry benzene (10, l.n 1; rum; i6co.n () TiiiiiM acetone, OM (K) ml).

The quaternary solvent is dissolved in acetone. at. The formation of the tip during the reaction of carbocyanine (0.07 g) remains soluble.

The filtrate is evaporated in vacuo. The residue is dissolved by heating in water and chlorine acid is added to the aqueous solution:

Perchlorate 2 -; - butyl hydroxy wine or ash ash is a pink crystal with a melting point of 235-238.

PRI me R 8. Ethyl perchlorate 2 -, - butyloxykinyl - 6,7-tetramethyl leibenzthiazole

0.26 g of 3 - ethyl - 6,7 - tetramstilebeshggiazolip - 2 - methyls aldehyde and 0.2 g of butyl iodide are heated for one hour in K11n and 1, her water bath. The product of vaccine is treated with boiling powder and dry benzene (5 times 4 ml each time). The residue is dissolved by heating in water and an excess of sodium perchloric acid is added to the solution.

Ethylnerchlorate 2 - / - butyloxiviyl-6, / -tetramethyles-bepzthiazole is obtained in the form of yellowish crystals with tera turo melting 175 IBC.

Example 9. Ethyl benzene sulphonate 2 - 3 - propyloxyvinyl - 6.7 benzobenzthiazole

A mixture of 0.26 g of 3 - ethyl - 6.7 - benzobethzthiazolip - 2 - methylene α-aldehyde and 0.21 g of beisolsulfonic acid iroiyl ester is heated for one hour on a kin of water. The crystalline mass obtained is treated with boiling benzene with dry benzene and then washed nosledovatolereno hot and cold; 1m absoluted acetone. Obtain 0.23 g (from the theoretically possible) light-rich crystals with a melting point of 191 192 (with decomposition).

Example 10. Ethyl perchlorate 2-3- propyloxyvinyl - 6,7 - tetralestilene benzthiazole

A mixture of 0.26 g of 3 -ethyl-6, 7-tetramethylene benzthiazoline-2-methylene-aldehyde and 0.21 g of propyl propyl ether (rokislota heated on a boiling water bath. The resulting viscous red-brown reaction mixture was treated with iripe dry benzene and

; op: 1StavivshnG1s residue kin g s ;; ode.

Perchloric acid is added to the hot aqueous solution after filtration;:; three1 |. After cooling, the precipitates.,; 7g yellow crystals of ethyl per .-. Lormta 2 - j - propyloxivin L -6.7 tetramethylenebenzthiazole with a melting point of 125-129,

Example 11. Chloroethyl 2 - 3-benzyloxyvinylbenathiazole

A mixture of 0.41 g 3 - ethylbenzothiazoline

-2 - Methylene - w - aldehyde and 0.34 g of benzyl chloride are heated for 30 minutes in a flask with reflux condenser in an oil bath at a temperature of 110-120.

The resinous mass, which had turned dark red, was washed with absolute ether (3 times but 5 ml) and mixed with 1.5 ml of acetone. In this case, a crystalline precipitate emerges, which after one hour is filtered off and, to separate the resulting dye, is dried with dry acetone (10 ml). B1 LOW 0.07 g. Melting point 150 154.

For purification, the product is treated with dry acetone at boiling (2 times with 2 ml), filtered and washed with arieTOHOM (20 ml). Pinkish iris with melting point 160 161.

At measure 12. Iodoethyl 2 - - ethoxyvinyl - 5.6 - d-methylbenzthiazole

1.16 g of 3 - ethyl - 5.6 - dimethylbenzene, 2 - methylene -1 - aldehyde and 0.8 g of dipethyl sulfate are heated for 1 hour in a water bath. The quaternary salt obtained in the form of semi-crystalline mass is treated at the boil with dry acetone. The residue is dissolved by heating n-2-ji-ethoxyvinyl-5.6-one-methyl benzothiazole iodo-ethyl in ethyl alcohol and the mixture is compacted with a volume of 20.i-Horo of an aqueous solution of potassium nodist.

The resulting product is filtered and washed with acetone. 1.02 g of reddish crystals are obtained with a melting point of 182 - 184.

Example 13. Methyl perchlorate-etoxyvinyl-3,3 - dimethyl - 5-chloroindolenine

A mixture of 1.17 g of 1,3,3-trimethyl-5-chloroindolium-2-methylene-w-aldehyde and 0.8 g of diethyl sulfate is heated for 1 hour in a boiling water bath.

The reaction mass is then treated by boiling with dry acetone, the residue is dissolved by heating in ethyl alcohol, and methylnerchlorate 2 - |: i - ethoxyvinyl 3,3-d-methyl-5-chloroindolenine is precipitated by adding an equal volume of a 20% aqueous solution of sodium chloride.

The precipitated quaternary salt is filtered and washed with dry acetone. Reddish crystals with a melting point of 211-212 are obtained.

Subject invention

The method of obtaining quaternary salts of 2 (4) -, 3 - alkoxy - or aralkoxyvinyl derivatives of nitrogenous heterocyclic bases, characterized by the fact that methylene - o) - aldehydes derivatives of the corresponding X-substituted partially hydrogenated bases are treated with alkylating agents and enhanced temperature.