CS270054B1 - Kvartem! salts of 3-dllamylaminostyrvene and a process for their preparation - Google Patents

Abstract

The solution relates to quaternary salts of 3-dimethylaminostyrene and a method for their preparation. The solution is based on quaternary salts of 3-dimethylstyrene of the general formula I, in which R is a methyl, ethyl, allyl or benzyl group and x is a chloride, bromide or methylsulfate anion. The method for producing quaternary salts of 3-dimethylaminostyrene of the general formula I consists in treating 3-dimethylaminostyrene with methyl bromide, methyl chloride, ethyl bromide, allyl bromide, allyl chloride, benzyl chloride, benzyl bromide or dimethyl sulfate.

Description

The present invention relates to quaternary salts of 3-dimethylaminostyrene and to a process for their preparation.

Of these, only Ν, Ν, Ν-trimethyl-N- (3-vinylphenyl) ammonium iodide [D.A.R. Happer, J. Chem. Soc., Perkin Trans ,, .2, 1673 (1984) | L

The invention relates to quaternary salts of 3-dimethylstyrene of the general formula I.

(I) (I) wherein R is methyl, ethyl, allyl or benzyl and X ** is chloride, bromide or methyl sulfate anlone.

According to the invention, quaternary compounds of the general formula I can be prepared by the action of methyl chloride, methyl bromide, ethyl bromide and allyl bromide. of ethyl chloride, benzyl chloride, benzyl bromide and dimethyl sulfate to 3-dimethylaminostyrene, either alone or dissolved in suitable solvents, such as benzene, acetone, tetrahydroturan, diethyl ether, acetonitrile and toluene. The concentration of 3-dimethylaminoetyrene in the reaction mixture usually corresponds to 0.5 to 3 mol / ml. Alkyl and aryl esters of the mineral acids RX, where R and X are as defined above, are used in a slight molar excess relative to 3-dimethylaminostyrene. The reaction temperature can be reduced below room temperature for rapidly interacting components and raised to 4o to 6o ° C. Due to the possibility of polymerizing 3-dimethylaminostyrene, it is expedient to add a radical polymerization inhibitor to the mixture, for example hydrochlorone, bonzochinone, 2,2-diphenyl-1-picrylhydrazyl or N-nitrosodinphenylamine, in an amount of about 0.1% by weight of 3-dimethylaminostyrene. Crystals of the quaternary salt are precipitated from the reaction mixture and can be isolated by simple filtration. The process for the preparation of quaternary salts of 3-dimethylaminostyrene salts is illustrated below in the examples.

Example 1

Solution of 2.21 g of 3-dimethylaminostyrene (n ^ ° - 1.5872), 1.71 g of methyl bromide, ο, οοί g p 3

2,2-diphenyl-1-picrylhydrazyl and ο, οοί g of hydroquinol in 3 cm of acetone are allowed to stand for 21 hours at room temperature. The crystals which precipitate are filtered off, dissolved in 8 cm @ 3 of N, N-dimethyl-3-formamide and pure Ν,. It is filtered off, washed on the filter with 1,4-dioxane and dried in an evacuated desiccator over anhydrous calcium chloride, weighed 2.72 g (74.9% by mole relative to 3-dimethylaminostyrene) and melts between 162 and 164 ° C. Analysis of the C 18 H 18 NBr salt with a relative molecular weight of 242.16: calculated 54.56% C, 6.66% H, 5.78% N | found 54.5% C, 6.72% H, 5.76% N.

Example 2

A mixture of 2.21 g of 3-dimethylaminostyrene, 0.91 g of methyl chloride, ο, οοί g of 2,2-diphenyl-1-acryhydrazyl, ο, οοί g of 1,4-benzoquinone and 3 cm 3 of acetone is reacted in a sealed glass ampoule. 7 days-at room temperature. The ampoule is then cooled in a bath of solid carbon dioxide and ethanol. The ampoule is opened, the precipitated crystals are filtered off and washed with 3 cm 3 of acetone. It is dissolved in 3 cm 3 of N, N-dimethylformamide and pure Ν, Ν, Ν-trimethyl-N- (3-vinyltenyl) ammonium chloride is precipitated from the solution with 25 cm 3 of 1,4-dioxane. After washing and drying as in Example 1, it weighs 0.24 g and melts between 172 and 175 ° C. Analysis of the salt of a molecular weight of 197.7%: calculated 66.82% C, 8.16% H, 7.19 N | found 65.47% C, 8.22% H, 7.0% N.

CS 27oo54 Bl

Example 3 2.21 g of 3-dimethylaminostyrene, 2.2 g of dimethyl sulphate, o.o. g of benzoquinone, ο, οοί g of 4-methoxyphenol are weighed into 15 cm 3 of benzene and the solution is left for 24 hours in a closed vessel at room temperature. An oily layer forms at the bottom. The solution above is decanted, the lower layer is mixed with 1 cm of 1,4-dloxane and the upper layer is decanted again after clarification. The oily residue is stirred with 1 cm of 1,4-dioxane and stored in a freezer for 2 hours. The solidified dioxane above the lower glass layer was partially thawed and the mixture was stirred. The lower layer of N, N, N-trimethyl-N- (3-vinylphenyl) ammonium methyl sulfate crystallizes. The crystals are filtered off and washed twice with 5 cm 3 of dloxane. After drying over anhydrous calcium chloride, they weigh 3.81 g and melt in the range of 60 to 64 ° C. Analysis of the salt of general formula C,. found 51.8% C, 7.8% H, 4.85% N.

Example 4

A solution of 2.21 g of 3-dimethylaminostyrene, 1.94 g of ethyl bromide and 0.005 g of hydroquinone in 3 cm 3 of benzene is left to stand in a closed vessel for 23 days at room temperature. The precipitated crystals of N, N-dimethyl-N-ethyl-N- (3-vinylphenyl) ammonium bromide are filtered off, dissolved in 3 cm @ 3 of methylformamide and 20 cm @ 3 of 1,4-dioxane are precipitated in solution. After drying over anhydrous calcium chloride, it weighs 0.44 g and melts between 168 and 170 ° C. Analysis of salt C, .H, _o NBr o rela—

X2 28 effective molecular weights 256.18: calculated 56.26% C, 7.18% H, 5.47% N; found

56.3% C, 7.17% H, 5.44% N.

Example 5

A solution of 2.21 g of 3-dimethylaminostyrene, 2.18 g of allyl bromide and 0.005 g of benzoquinone in 3 cm 3 of acetone is left for 96 hours at room temperature. The precipitated crystals of N-allyl-N, N-dimethyl--N- (3-phenylphenyl) ammonium bromide are filtered off, washed with acetone and dried in vacuo over anhydrous calcium chloride (3.14 g, 78%, m.p. 132-134). ° C. Analysis of C.H.-NBr with molecular weight 268.19 t calculated 58.22% C, 6.77% H, 5.22% N; nalo lo found 58.0% C, 6.94% Η.5.5% N.

Example 6 A mixture of 2.21 g of 3-dimethylaminostyrene, 1.38 g of allyl chloride, 8 cm 3 of water and 0.005 g of hydroquinone is stored with occasional shaking in a sealed deoxygenated glass ampoule for 3 days 34 days at room temperature. The contents of the ampoule are then shaken with 6 cm 3 of benzene, the aqueous layer is separated and shaken twice more with 6 cm 3 of benzene. The aqueous layer was then purified by adding 0.1 g of carborafin, filtered, and water was distilled off under reduced pressure. The viscous residue was dried in a vacuum desiccator over anhydrous calcium chloride. After 9 days, it is converted into crystals (1.1 g) melting in the range of 90 to 93 ° C. Analysis for C 18 H 18 NCl 2 molecular weight 223.73 s calculated 69.79% C, 8.11% H, 6.26% N; found 68.6o% C, 7.99% H, 5.82% N.

Example 7

A solution of 2.21 g of 3-dimethylaminostyrene, 3.0 g of benzyl bromide and 10 g of hydroquinone in cm ^{3 of} tetrahydrofuran is allowed to stand for 1 day at room temperature. The dried crystals were filtered off, washed with acetone and dried in vacuo over anhydrous calcium chloride 3.95 g, m.p. 98-100 ° C. Analysis of C _1? H ₂ O NBr with a molecular weight of 318.25 s calculated 64.15% C, 6.33% Η, 4.4o% N | found 63.33% C, 6.58% H, 3.82% N.

Example 8

A mixture of 2.21 g of 3-dimethylaminostyrene, 2.28 g of benzyl chloride, 2 cm of benzene and 0.55 g of hydroquinone is left for 30 days in a sealed ampoule filled with nitrogen at room temperature.

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The precipitate formed is then filtered off, washed with acetone and dried in vacuo over anhydrous calcium chloride; 0.7o g, not melting completely to 26o ° C. Dissolves in N, N-dimethylformamide. Analysis of NC1 with a molecular weight of 273.8 °: calculated 74.57% C, 7.36% H, 5.12% N;

found 73.8o% C, 7.3o% H, 5.21% N.

The described quartets of 3-dimethylaminostyrene salts dissolve well in water, low molecular weight alcohols, dimethylformamide, dimethyl sulfoxide. formic acid and less in acetic acid. They do not dissolve in aliphatic and aromatic hydrocarbons and their halogen derivatives, in ethers and ketones. They can be used to produce homopolymer and blended polymers with hydrophilic, antibacterial and antifungal properties.

Claims (2)

SUMMARY OF THE INVENTION 1. Quartets of 3-dimethylaminostyrene salts of the general formula I, (I) (I) wherein R is a methyl, ethyl, allyl or benzyl group and X - is a chloride, bromide or methyl sulfate anion. Process for the preparation of quaternary salts of 3-dimethylaminostyrene of the general formula I, characterized in that 3-dimethylaminostyrene is treated with methyl bromide, methyl chloride, ethyl bromide, allyl bromide, allyl chloride, benzyl chloride, benzyl bromide or dimethyl sulfate.