(1r*2s*4r*)-4-(4-aminophenyl)-cyclohexane-1,2-dicarboxylic acid

FIELD: chemistry.

SUBSTANCE: invention claims new compound, particularly (1R*2S*4R*)-4-(4-aminophenyl)-cyclohexane-1,2-dicarboxylic acid of the formula I , which can be applied in chemical industry for obtaining polyimides.

EFFECT: polyimides applied in production of liquid crystals, optical non-linear cushion layers and materials with low permittivity.

1 cl, 20 ex, 3 tbl

 

The invention relates to the field of obtaining new polyaromatics iminodicarboxylic acids, which can be used in the chemical industry for homopolymerisation and copolycondensation previously undescribed polyimides. Such polyimides are used in the manufacture of liquid crystals, nonlinear optical buffer layers, materials with low dielectric constant.

Known polyimides based dianhydride CIS - and TRANS-1,2,3,4-cyclopentanetetracarboxylic acid and aromatic diamines.

All the obtained polyimide is thermally stable at a temperature of more than 415°With (5% weight loss). Polyimide films have a module stretching 2,1-a 3.6 GPa, tensile strength 42-116 MPa, completely colorless, TRANS-polyimides have a lower glass transition temperature (Frang X. et al. Polymer. 2004. Vol.45. P.2539-2549).

A necessary condition for the formation of high molecular weight polymers with linear polymerization is equivalence reacting between a source connection.

The problem solved by the present invention is the obtaining (1R*2S*4R*)-4-(4-AMINOPHENYL)-cyclohexane-1,2-dicarboxylic acid as the monomer for polyaromatics polyimides containing in its structure the various functional g is PI, able to communicate with each other. Zwitter-ion structure of the monomer allows high-temperature polycondensation without the isolation of intermediate prepolymers, which greatly simplifies the technological scheme of production of polyimides.

States (1R*2S*4R*)-4-(4-AMINOPHENYL)-cyclohexane-1,2-dicarboxylic acid of the formula:

This compound is obtained by reaction of alkylation of benzene (1R*2S*)-4-cyclohexene-1,2-dicarboxylic acid, nitration obtained (1R*2S*4R*)-4-phenylcyclohexane-1,2-dicarboxylic acid or a mixture of (1R*2S*4R*) and (1R*2S*4S*)-4-phenylcyclohexane-1,2-dicarboxylic acid obtained after alkylation, nitric acid, followed by reduction of the resulting (1R*2S*4R)-4-(4-nitrophenyl)-cyclohexane-1,2-dicarboxylic acid according to the scheme:

Alkylation of benzene (1R*2S*)-4-cyclohexene-1,2-dicarboxylic acid is carried out in the presence of anhydrous aluminum chloride at 45-75°C. the Nitration of (1R*2S*4R*)-4-phenylcyclohexane-1,2-dicarboxylic acid or a mixture of (1R*2S*4R*) and (1R*2S*4S*)-4-phenylcyclohexane-1,2-dicarboxylic acid obtained after alkylation, is 100%nitric acid in glacial acetic acid at a temperature of 70°C. Recovery (1R*2S*4R*)-4-(4-nitrophenyl)-cyclohexane-1,2-dicarboxylic acid is carried out with hydrazine in which utilizatori Ni-Raney.

The invention is illustrated by the following examples.

Example 1. To 50 g (0.64 mol) of dry benzene is added at room temperature 17 g (0.1 mol) of (1R*2S*)-4-cyclohexene-1,2-dicarboxylic acid and 33.5 g (0.25 mol) of anhydrous aluminum chloride and heated for three hours at 45°with constant stirring. Then to the reaction mass when cooled add 50 ml of hydrochloric acid (1,098 g/cm3) and distilled benzene and water vapor. Precipitated acid is filtered and washed several times with cold water. The dried precipitate is a mixture of (1R*2S*4R*) and (1R*2S*4S*)-4-phenylcyclohexane-1,2-dicarboxylic acids, which without further purification may be used to obtain (1R*2S*4R*)-4-(4-nitrophenyl)-cyclohexane-1,2-dicarboxylic acid. To obtain pure (1R*2S*4R*)-4-phenylcyclohexane-1,2-dicarboxylic acid crystallized from a mixture of 70% aqueous acetic acid. The precipitation was filtered, washed several times with small amounts of 70% acetic acid and dried at a temperature of 70-80°C. Obtain 16.3 g (of 0.066 mol) of (1R*2S*4R*)-4-phenylcyclohexane-1,2-dicarboxylic acid. Yield 66%.

Melting point 173-176°C.

1H NMR ([2H6] DMSO) δ, J (Hz): 1,4 (1H, m); 1,7 (2H, m); 2,0 (2H, m); 2,2 (1H, m); 2,6 (1H, m); 3,1 (1H, m); 3,4 (1H, m); 7,2 (2H, t, J=8); and 7.3 (3H, d, J=8); 12,1 (2H, s).

IR, cm-1: 2648, 2575 (OH), 1710, 1698 (C=O), 1598, 1493, 1450 (Ar), 1255 (C-O), 93 (HE), 743 (Ar).

Examples 2-4. Alkylation of benzene (1R*2S*)-4-cyclohexene-1,2-dicarboxylic acid is carried out analogously to example 1. The conditions and results of the reactions are given in table 1.

Example 5. To 38 ml of glacial acetic acid was added 12 ml of nitric acid (d=1,513 g/cm3) and stirred for one minute, the mixture is heated to 40°C. Contribute 2.5 g (0.01 mol) of (1R*2S*4R*)-4-phenylcyclohexane-1,2-dicarboxylic acid, heated to 70°C and stirred for six hours. Then the reaction mass is then cooled. The precipitation is filtered and washed on the filter with 10 ml of glacial acetic acid and 100 ml of water. The precipitate is dissolved in 200 ml of 1% aqueous solution of potassium hydroxide, heated to 50°and filtered from nerastvorimogo sediment. The filtrate is heated to 90°and add 5 ml of hydrochloric acid (1,198 g/cm3). The precipitation is filtered hot (80-90°C), washed with hot water and dried at 50-60°C.

Get a 1.96 g (0,0067 mol) of (1R*2S*4R*)-4-(4-nitrophenyl)-cyclohexane-1,2-dicarboxylic acid. Yield 67%.

Melting point 203-205°C.

1H NMR ([2H6] DMSO) δ, J (Hz): 1.52m (1H; qd; J1=12,8 Hz; J2=3,66)and 1.83-2,04 (4H; m), 2,17 (1H; d; J=13,4), OF 2.54 (1H; m)to 2.67 (1H; t; J=12,2), 3,21 (1H; s), 7,52 (2H; d; J=8,54), 8,17 (2H; d; J=8,54), 12,8 (2H; br s).

IR, cm-1: 2666 (HE), 1696 (C=0), 1595 (Ar), 1516 (NO2), 1345 (NO2), 1260 (C-O), 939 (OH).

Examples 6-13 Nitration (1R*2S*4R)-4-phenylcyclohexane-1,2-dicarboxylic acid is carried out analogously to example 5. The conditions and results of the reactions are shown in table 2.

Example 14. To 39 ml of glacial acetic acid was added 11 ml of nitric acid (d=1,513 g/cm3) and stirred for one minute, the mixture is heated to 40°C. add 5 g (0.02 mol) of a mixture of (1R*2S*4R*) and (1R*2S*4S*)-4-phenylcyclohexane-1,2-dicarboxylic acid obtained after alkylation, heated to 70°C and stirred for five hours. Then the reaction mass is then cooled. The precipitation is filtered and washed on the filter with 10 ml of glacial acetic acid and 100 ml of water. The precipitate is dissolved in 150 ml of 1% aqueous solution of potassium hydroxide, heated to 50°and filtered from nerastvorimogo sediment. The filtrate is heated to 90°and add 4 ml of hydrochloric acid (1,198 g/cm3). The precipitation is filtered hot (80-90°C), washed with hot water and dried at 50-60°C. Receive 1,11 g (0,0038 mol) of (1R*2S*4R*)-4-(4-nitrophenyl)-cyclohexane-1,2-dicarboxylic acid. Yield 38%.

Examples 15-19. The nitration mixture of (1R*2S*4S*) and (1R*2S*4R*)-4-phenylcyclohexane-1,2-dicarboxylic acid carried out analogously to example 14. The conditions and results of the reactions are given in table 3.

Example 20. In 100 ml of water is dissolved 4,78 g (of 0.085 mol) of potassium hydroxide and 10 g (0,034 mol) of (1R*2S*4R*)-4-(4-nitrophenyl)-cyclohexane-1,2-dicarboxylic acid and filtered from the undissolved precipitate. The filtrate is transferred into kabui heated to 60° C. the Reaction is carried out for three hours, occasionally adding 0.5 g of the catalyst Ni-Raney and 2 ml of 70%aqueous solution of hydrazine hydrate is added. The mixture is then cooled and filtered from the catalyst. The resulting solution was acidified with 5% HCl solution up until the precipitated product will not begin to dissolve. The precipitation is quickly filtered and air-dried during the day. The obtained product is dissolved in a minimum quantity of hydrochloric acid (d=1,018 g/cm3) and filtered from the undissolved precipitate. The filtrate is alkalinized 10%solution of sodium acetate to neutralize all of hydrochloric acid. The precipitate is dried at a temperature of 50°C. Receive 7.78 g (0.03 mol) of (1R*2S*4R*)-4-(4-AMINOPHENYL)-cyclohexane-1,2-dicarboxylic acid. Yield 87%.

Melting point >300°C.

1H NMR ([2H6] DMSO) δ, J (Hz): 1,37 (1H, qd, J1=12,8; J2=4,27), was 1.69 (1H, td, J1=13,4; J2=5,49), or 1.77 (1H, d, J=12,8)and 1.83-to 1.98 (2H, m), is 2.09 (1H, d, J=12,8), to 2.29 (1H, d, J=12,2), 2,38 at 2.45 (1H, m), 3,14 (1H, s), of 6.49 (2H, d, J=7.23 percent), at 6.84 (2H, d, J=7,93).

IR, cm-1: 3378, 3303 (NH2), 2622 (OH), 1717 (C=O), 1626 (NH2), 1513 (Ar), 1191 (C-O), 933 (OH), 821 (Ar).

Table 1
Obtaining (1R*2S*4R*)-4-phenylcyclohexane-1,2-dicarboxylic acid
no experienceThe concentration of (1R*2S*)-4-cyclohexene-1,2-dicarboxylic sour is s, mol/lReaction time,The reaction temperature, °Yield, mol %
22,072005560
32,018006554
42,09007543

Table 2
Obtaining (1R*2S*4R*)-4-(4-nitrophenyl)-cyclohexane-1,2-dicarboxylic acid, (1R*2S*4R*)-4-phenylcyclohexane-1,2-dicarboxylic acid
no experienceThe concentration of (1R*2S*4R*)-4-phenylcyclohexane-1,2-dicarboxylic acid, mol/lThe concentration of nitric acid, mol/lReaction time,Yield, mol %
60,26,22160070
70,26,72160067
80,155,32160068
90,155,81800064
100,156,21800062
110,14,8 1800064
120,15,31440063
130,15,81400061

Table 3
Obtaining (1R*2S*4R*)-4-(4-nitrophenyl)-cyclohexane-1,2-dicarboxylic acid from a mixture of (1R*2S*4R*) and (1R*2S*4S*)-4-phenylcyclohexane-1,2-dicarboxylic acid obtained after alkylation
no experienceThe concentration of 4-phenylcyclohexane-1,2-dicarboxylic acid, mol/lThe concentration of nitric acid, mol/lReaction time,Yield, mol %
150,84,81080028
160,44,81080033
170,45,31080041
180,45,81080043
190,25,82160047

(1R*2S*4R)-4-(4-AMINOPHENYL)-cyclohexane-1,2-dicarboxylic acid of the formula



 

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