CS263976B1 - And N- (3-dimethylaminophenyl) methacrylamides - Google Patents

Abstract

The solution relates to N-(3-dimethylaminophenyl)methacrylamides of general formula I, in which R represents hydrogen or a methyl group. These substances are prepared by treating 3-dimethylaminoaniline of general formula II with methacryloyl chloride at a temperature not exceeding 50 °C in the presence of an organic or inorganic base, for example triethylamine or potassium carbonate.

Description

The invention relates to N- (3-dimethylaminophenyl) methacrylamides and to a process for their preparation.

These compounds are suitable for the preparation of polymers containing functional tertiary amino groups and have not been described in the literature. The present invention provides N- (3-dimethyl-aminophenyl) methacrylamides of formula (I):

CH ₃ NCH ₃ n -co-c = ch ₂

R

CH 'wherein R is hydrogen or methyl.

The process according to the invention is characterized in that the 3-dimethylaminoanilines of the formula II are

wherein R is as defined above, is treated with 2 to 3 moles of methacryloyl chloride at a temperature not exceeding 50 ^° C in the presence of an organic or inorganic base such as triethylamine or potassium carbonate.

The reaction is preferably carried out in an environment in which the methacryloyl chloride and the starting dimethylaminoaniline are well dissolved, but the neutralization products of the resulting hydrogen chloride are not dissolved by the added base. The reactants are mixed at a rate such that the heat of the mixture does not exceed 50 ° C. In order to prevent the polymerization of methacryloyl chloride and the resulting unsaturated amides during the reaction, radical polymerization inhibitors such as cuprous chloride, benzoquinone or 2,2-diphenyl-1-picrylhydrazyl are added. After standing for one day, the solid salts formed by neutralization of hydrogen chloride with added bases were collected by filtration. Residues of the base and unreacted starting components are eluted from the filtrate with water and slightly alkaline aqueous solutions. The solvent was distilled off from the dried filtrate under reduced pressure and the remaining crude product was purified by crystallization.

The process for preparing the unsaturated amides of formula I is described in the following examples.

)

Example 1

5.2 g (0.04 mole) of 3-dimethylaminoaniline and 11.1 g (0.11 mole) of triethylamine are dissolved in 90 cm @ ^{3 of} benzene and a solution of 7.4 g (0.07 mole) is added dropwise with stirring. ) of methacryloyl chloride (copper chloride stabilized) in 20 cm @ ^{3 of} benzene, cooling the water bath to maintain the temperature of 15-30 DEG C. The next day, triethylamine hydrochloride is filtered off, the filtrate is shaken four times with 50 cm @ ^{3 of} 5% aqueous acetate solution. After removal of the solvent on a vacuum evaporator, 7.8 g (100% yield) of crude N- (3-dimethylaminophenyl) methacrylamide are obtained, which, after crystallization from cyclohexane, has a melting point of 104 DEG-104 DEG C. 105 ° C.

Analysis:

C12H16N2O, mol. wt. 204.28;

Found:

% C, 70.47;% H, 8.00;% N, 13.48; Calculated:

H, 7.90; N, 13.71. Example 2

In the same manner as in Example 1, a solution of 1.5 g (0.06 mol) of methacryloyl chloride is mixed with a mixture of 4 g (0.03 mol) of 3-dimethylaminohaniline, 12.2 g (0.09 mol) of potassium carbonate (K2CO3) and 70 cm ^{3 of} benzene at room temperature. After 24 hours the solid salts are filtered off and the filtrate is extracted with 5% aqueous sodium acetate solution. 6 g (100% yield) of crude N- (3-dimethylaminophenyl) methacrylamide, which is crystallized from cyclohexane, is isolated from the filtrate after drying over sodium sulphate (Na2SO4) and removal of the solvent.

Example 3

To a mixture of 9.9 g (0.07 mol) of (3-dimethylamino-6-methyl) aniline, 19.2 g (0.19 mol) of triethylamine and 150 cm ^{3 of} benzene is added with stirring 12.8 g (0, 12 mol) of methacryloyl chloride dissolved in 40 cm ^{3 of} benzene. The precipitated triethylamine hydrochloride was filtered off the next day and the filtrate was shaken with 5% aqueous sodium acetate. After drying the benzene extract with sodium sulfate (NazSOá) and removing the solvent by rotary evaporation yielded 14.4 grams (100 yield ^1%) of crude N- (3-dimethylamino-6-methylphenyl) methacrylamide. This was purified by crystallization in benzene and precipitation with cyclohexane. Its melting point was 103-104 ° C.

Analysis:

C13H18N2O, mol. wt. 218.30;

Found:

% C, 71.43;% H, 8.22; Calculated:

H, 8.31; N, 12.83.

The prepared N-β-dimethylaminophenyl methacrylamides are white crystalline materials with a melting point of about 104 ° C. In the presence of organic or inorganic ibases (triethylamine, potassium carbonate), they are formed with quantitative yields already at room temperature and are soluble in aromatic hydrocarbons, acetone, ethanol, ethyl acetate, dimethylformamide, acetonitrile, partially dissolved in ether and acetic acid. They remain insoluble in dilute alkali and water.

By the action of radical polymerization initiators, N- (3-dimethylaminophenyl) methacrylamides homopolymerize and copolymerize with ethylenically unsaturated compounds. The presence of tertiary amino groups in units embedded in the polymer chain allows for their chemical modification and thus influence of the obtained polymers.

Claims (2)

I will invent the object N - (3-dimethylaminophenyl) methacrylamides of the formula I as claimed in claim 1, characterized in that per mole of 3-dimethylaminoaniline of the formula II, CH ₃ N-CH ₃ XLnhco-c = ch ₂ R ^CH3 wherein R is hydrogen or methyl. A process for the preparation of N- (3-dimethylaminophenyl) methacrylamides of the formula I wherein R is as defined above, reacts 2 to 3 moles of methacryloyl chloride at a temperature not exceeding 50 ° C in the presence of an organic or inorganic base such as triethylamine or potassium carbonate.