CS266753B1 - Quaternary salts of N-dimethylaminoaryl maleamic acids - Google Patents

Abstract

The solution relates to quaternary salts of N-dimethylaminoarylmaleamic acids and a method for their preparation. The essence of the solution is the quaternary salts of N-dimethylaminoarylmaleamic acids of the general formula I, in which R, Fr is hydrogen or a methyl group, RJ is a methyl, allyl or benzyl group, X- is a chloride, bromide, iodide or methylsulfate anion and the amino group is on the benzene nucleus in the 3- or 4-position. The method of preparing quaternary salts of N-dimethylaminoarylmaleamic acids of the general formula I consists in treating maleamic acids of the general formula II, in which R1, Rz have the above-mentioned meaning and the amino group is on the benzene nucleus in the 3- or 4-position, with methyl chloride, methyl bromide, methyl iodide, allyl bromide, benzyl bromide or dimethyl sulfate, usually in the presence of a solvent for one or both of the reactants.

Description

The present invention relates to quaternary salts of N-dimethylaminoarylamalic acids and to a process for their preparation. Quaternary salts of N-dimethylaminoarylmalaamic acids have not yet been prepared.

The present invention relates to quaternary salts of N-dimethylaminoethylmaleamic acids of the general formula I,

NH-CO-CH = CH-COOH

X “/ 1 /

7 wherein R, R; your group, X ^-

It is hydrogen or methyl, R 1 is methyl, allyl or benzyl, the chloride, bromide, iodide or methylsulphate anion and the amino group on the benzene ring is in the 3- or 4-position. According to the invention, it can be prepared by the action of methyl bromide, methyl chloride, methyl iodide, allyl bromide, benzyl bromide and dimethyl sulphate on N-dimethylaminoethylmaleamic acid of general formula II, h ₃ ch ₃ c

NH-CO-CH = CH-COOH / 11 /

2 in which R 1, R 2 are as defined above and the amino group is on the benzene ring

3- or 4-. The acids of the formula II can be pure or dissolved in position in suitable solvents, such as, for example, acetone, methanol, chloroform, acetic acid and N, N-dimethylformamide. The acid concentration of the formula II usually corresponds to 0.3 to 3 mol dm-3. Alkyl and aryl esters of the mineral acids RX are used in a slight molar excess relative to the maleic acid, as a rule 1.05 to 1.7 mol of RX per 1 mol of acid of the formula II. The reaction temperature can be increased to 40 to 60 ° C due to the low homopolymerization activity of maleic acids. Crystals of a quaternary salt are precipitated from the reaction mixture, which can be isolated by growth by filtration. The process for the preparation of the quaternary salts of N-dimethylaminoformalimic acids is illustrated below in the examples.

Example 1

2.34 g of N- (4-dimethylaminophenyl) maleic acid and 1.70 g of methyl iodide are weighed into 15 cm @ 3 of acetone and the red-brown suspension is left to stand for six days at room temperature. The dark red crystals are then filtered off, dried in air (2.55 g) and boiled twice with 5 cm @ 3 of water. The aqueous solution was mixed with 0.1 g of carborafin and filtered through a pad of asbestos on a glass filter. Water is distilled off from the filtrate under a water pump vacuum. The slightly yellowish solid residue of N- (4-maleamidamidophenyl) -N, N, N-trimethylammonium iodide weighs 0.75 g and melts at 170-171 ° C. Analysis of the salt of the general formula ^{ε 13 ^ 37 ^ 2 ^ 3 ^ 0 re} l ^{and a} molecular weight of 376.18: calculated 41.50% C, 4.56% H, 7.54% N; found 41.27% C, 4.56 7.56% N.

Example 2

A mixture of 2.34 g of N- (4-dimethylaminophenyl) maleic acid, 1.60 g of methyl bromide and 10 cm 3 of acetone is allowed to stand for 14 days at room temperature. The brownish precipitate is filtered off and boiled twice with 5 cm 3 of water. The aqueous solution is shaken with 0.1 g of carborafin and filtered through a layer of asbestos on a glass filter. Water is distilled off from the filtrate under a water pump vacuum and the brownish hairy residue is dried in an evacuated desiccator over anhydrous calcium chloride. The resulting brownish yellow powdery N- (4-maleimidophenyl) -N, N, N-trimethylammonium bromide weighs 1.77 g and is strongly hygroscopic. It melts in the sealed glass capillary in the range of 90 to 101 ° C. Analysis of the salt of general formula C 1 H 2 N 2 O 2 Br with a relative molecular weight of 329.19: calculated 4T, 43% C, 5.21% H, 0.51% N; found 47.00% C, 5.35% H, 0.57% N.

Example 3

1.17 g of N- (4-dimethylaminophenyl) maleic acid and 0.01 g of dimethyl sulphate are weighed into 1 cm @ 3 of acetone and the red-brown suspension is left to stand at room temperature for 24 hours. The pinkish crystalline product is filtered off and dried in an evacuated desiccator (1.50 g). It is then heated with eight cm 3 of glacial acetic acid, cooled, filtered and dried over anhydrous calcium chloride. The N- (4-malelnamidophenyl) -N, N, N-trimethylammonium methylsulfate obtained weighs 1.00 g and melts at 106-107 ° C. Analysis salts of the empirical formula ^ ^{14 ^ 20 ^ 2 ^ 7 0} 0 tive ^re l ^and a molecular weight of 360.30: calculated 46.66% C, 5.59%. H, 7.77% N; found 45.05% C, 5.42% H, 7.90% N.

Example 4

A mixture of 1.17 g of N- (4-dimethylaminophenyl) maleic acid, 0.75 g of allyl bromide and 5 cm ^{3 of} acetone is kept for 12 days at room temperature. The crystals are filtered off, washed twice with 3 cm 3 of acetone and dried in an evacuated desiccator over anhydrous calcium chloride. Dry N-allyl-N, N-dimethyl-N- (4-malelnamidophenyl) ammonium bromide weighs 1.09 g and melts between 175 and 170 ° C. Analysis of the general formula C 18 H 18 N 2 O 2 Br δ relative molecular weight 355.23: calculated 50.71% C, 5.39% H, 7.09% N; found 50.74% C, 5.32% H, 0.11% N.

Example 5

⁰ to 5 cm of acetone was weighed 1.17 g of N- / 4-dlmethylaminofenyl / maleamic acid and 1.10 benzyIbromldu and the tan suspension was allowed to stand for 17 days. at room temperature. The colorless crystals formed are then isolated and dried as in Example 4. The N-benzyl-N, N-dimethyl-N- (4-maleamidamidophenyl) ammonium bromide obtained weighs 1.75 g and melts at 154-155 ° C. Analysis salts of the empirical formula ⁰ * ^VRL and ^relative molecular mass

405.20: calculated 54.30% C, 5.22% H, 6.91% N; found 55.96% C, 5.10% H, 7.03% N.

Example 6

A solution of 1.31 g of N- (2,6-dimethyl-4-dimethylaminophenyl) maleic acid, 0.05 g of methyl iodide and 10 cm ^{3 of} acetone is allowed to stand for nine days at room temperature. The resulting colorless crystals of N- (3,5-dimethyl-4-maleimido-phenyl) -N, N, N-trimethylammonium iodide are isolated and dried as in Example 4; weighs 1.00 g and melts between 103 and 107 ° C. Analysis of the salt of the general formula ^ 5 ^ 23 ^ 2 ^ 3 ^ ⁰ relative molecular weight 404.23: calculated 44.56% C, 5.24% H, 6.93% N; found 44.41% C, 5.25% H, 6.74% N.

Example 7 A red-brown solution of 1.31 g of N- (2,6-dimethyl-4-dimethylamino-phenyl) -maleic acid and 1.30 g of methyl bromide in 6 cm @ ^{3 of} acetone is allowed to stand. 35 hours at room temperature. The green crystalline product is then diluted with 3 cm 3 of acetone, the crystals of N- (3,5-dimethyl-4-maleimido-phenyl) -N, N, N-trimethylammonium bromide are filtered off, washed twice on the filter with 3 cm ^{3 of} acetone and dried in an evacuated an desiccator over anhydrous calcium chloride; weighs 1.77 g and melts at 185-100 ° C. Analysis of the salt of the general formula C 266753 with a molecular weight of 357.25: calculated 50.43% C, 5.93% H, 7.84% N; found 49.03% C, 5.04% H, 7.32% N.

Example B

A mixture of 1.31 g of N- (2,6-dimethyl-4-dimethylaminophenyl) maleic acid, 0.70 g of methyl chloride and 5 cm ^{3 of} acetone is reacted in a sealed vial for 11 days at room temperature. Then the ampoule, cooled in a bath of solid carbon dioxide and ethanol, is opened, the colorless crystals of N- (3,5-dimethyl-4-maleamidido-phenyl) -N, N, N-trimethylammonium chloride are filtered off, washed with benzene and dried in an evacuated desiccator. over anhydrous calcium chloride; weigh 0.35 g and melt between 177 and 101 ° C. Analysis of the salt of the general formula C 18 H 18 N 2 O 2 Cl 2 with a relative molecular weight of 312.79: calculated 57.59% C, 6.77% H, 8.96% N; found 56.95% C, 6.72% H, 8.52% N. '

Example 9

A solution of 1.31 g of N- (2,6-dimethyl-4-dimethylamino-phenyl) -maleamic acid and 0.85 g of dimethyl sulfate in 5 cm ^{3 of} acetone is allowed to stand for nine days at room temperature. The off-white crystals are filtered off, dissolved in 3 cm ^{3 of} 50 ° C warm N, N-dimethylformamide and the solution is diluted with 25 cm 3 of acetone. The precipitated crystals of N- (3,5-dimethyl-4-malelnamido-phenyl) -N, N, N-trimethylammonium methylsulphate are filtered off and dried in an evacuated desiccator over anhydrous calcium chloride; weighed 1.05 g and melted at 240 DEG-245 DEG C. Analysis salts of the empirical formula ^ 15 ^ 24 ^ 2 ^ 7 ^ 0 relative molecular mass 300.37: Calculated 49.4% C, 6.23% H, 7 21% N; found 40.97% C, 6.15% H, 7.35% N.

Example 10

A mixture of 1.31 g of N- (2,6-dimethyl-4-dimethylaminophenyl) maleic acid and 1.37 g of benzyl bromide in 5 cm ^{3 of} acetone is reacted at room temperature for two days. The resulting white, above-bluish crystalline mass is filtered off, washed on the filter with 4 cm 3 of acetone and dried in an evacuated desiccator over anhydrous calcium chloride. The greenish crystals of N-benzyl-N, N-dimethyl-N- (3,5-dimethyl-4-maleamidamidophenyl) ammonium bromide weigh 2.12 g and melt at 150-153 ° C. Analysis of the salt of general formula 1¾ 1 ^ 2 5 ^^ 3 ^ ^{1 re 0 and a} molecular weight of 433.33: calculated 50.20% C, 5.02% H, 6.47% N; found 57.05% C, 5.72% H, 5.17% N. '

Example 11

A solution of 1.26 g of N- (3-dimethylamino-6-methylphenyl) maleic acid and 0.94 g of methyl bromide in 6 cm ^{3 of} acetone is reacted for four days at room temperature. The resulting colorless crystals are filtered off and washed twice with 3 cm 3 of acetone. It is then dissolved in 5 cm 3 of methanol, the solution is filtered and 30 cm 3 of benzene are added. The precipitated crystals of NZ (3-maleinamido-4-methylphenyl) -N, N, N-trimethylammonium bromide are filtered off and dried in an evacuated desiccator over anhydrous calcium chloride; weighs 1.10 and melts in a sealed capillary at 106 ° C. Analysis of the salt of the general formula C 18 H 18 N 2 O 3 Br with a relative molecular weight of 343.22: calculated 48.99% C, 5.50% H, 0.16% N; found 40.35% C, 5.66% H, 0.25% N.

The described quaternary salts of N-dimethylaminoarylamaleic acids dissolve well in water, low molecular weight alcohols, dimethylformamide, formic acid and 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 mixed polymers with hydrophilic, antibacterial and antifungal properties.

Claims (2)

Quaternary salts of N-dimethylaminoethylmaleamic acids of general formula I, wherein R \ R ^ _e j or a methyl group, R₁ is methyl, allyl or benzyl, X- is chloride, bromldový · iodide or methyIsíranový anion and the amino group on the benzene nucleus at the 3- or 4- position. 2. A process for the preparation of quaternary salts of N-dimethylaminoethylmaleamic acids of the general formula I, according to item 1, characterized in that the maleic acids of the general formula II, -W-CO-C 2 CH-COOH R ^1/11 / wherein R, R₁ are as defined above and the amino group on the benzene nucleus at the 3- or 4 acts methyIchloridem, methyIbromidem, methyljodldem, allyIbromidem, benzyIbromidem or dlmethylsulfátem solvent usually in the presence of one or both reaction components.