JPH0651789B2 - Optically active polyamide - Google Patents

Description

The present invention relates to a novel optically active polyamide derived from an optically active transstilbendiamine.

[Structure of Invention]

That is, the present invention has a repeating unit represented by the following general formula (I) or (II) and has a reduction ratio of 0.05 to 1.0 (measured in metacresol or sulfuric acid at a concentration of 0.5 g / dl at 35 ° C.). Optically active polyamide with viscosity (Good _{C 2} a wherein R is branching _{- 2 0} alkylene _{group, C 6 - 1 0} one or more a group having an aromatic group, _{C 3 -
1 0} is a cycloaliphatic group one or more having groups of both may have an asymmetric carbon. ) Concerning.

The present invention is an optically active polyamide synthesized from an optically active transstilbendiamine and one or more dicarboxylic acids represented by the following general formula (III) HOOC-R-COOH (III).

Here, there are various methods for obtaining an optically active transstilbendiamine, but the method disclosed in Japanese Patent Application No. 59-133361, which is the invention of the present inventors, is preferable. That is, a carboxylic acid having optical activity is allowed to act on a racemic form of trans-stilbendiamine, and the produced diastereomeric salt is separated by utilizing its solubility difference,
Optically active trans-stilbendiamine can be synthesized.

The process is shown by the formula below.

That is, diastereomeric salts (A) and (B) are easily produced by mixing and heating a diamine and an optical characteristic carboxylic acid in a solvent such as ethanol. Since (A) and (B) have different solubilities, it is possible to precipitate and separate only one of them together with the formation of salt by using an appropriate solvent and conditions. For example, when (-) mandelic acid is used as the carboxylic acid, the salt with the (-) diamine is sparingly soluble in ethanol, and the salt with the (+) form is easily soluble. Also, an amino acid derivative can be used.

The salt separated and purified by an appropriate method such as recrystallization is released by a usual method. For example, a method using a dilute aqueous solution of sodium hydroxide is a preferable example. The released diamines (IV) and (V) are extracted with ether or the like.

The dicarboxylic acid represented by the general formula (III) is as follows.

R is which may have a branching _{C 2 - 2 0} alkylene group,
C _{6 - 1 0} one or more a group having an aromatic _{group, C 3 - 1 0}
The above-mentioned group has at least one alicyclic group, and each may have an asymmetric carbon.

It should be noted that any carbon of R may have a substituent such as halogen.

The dicarboxylic acid may be saturated or unsaturated.

The following are specific examples of the dicarboxylic acid represented by the general formula (III).

The aliphatic dicarboxylic acid includes the following.

The aromatic dicarboxylic acid includes the following.

The alicyclic dicarboxylic acids include the following.

Next, a method for synthesizing the polyamide of the present invention will be described. The optically active polyamide of the present invention is obtained as described above (+)
Alternatively, it can be easily obtained by reacting (−)-transstilbendiamine with the corresponding dialbonic acid or its derivative. Usually no special catalyst is required. A method of reacting equimolar amounts of both in an aprotic polar solvent is a preferred method. Preferred examples of the aprotic polar solvent include dimethylacetamide, dioxane, methylpyrrolidone, dimethylsulfoxide, and hexamethylylphosphoric triamide. For example, when a diphenyl ester is used as the dicarboxylic acid derivative, a mixture of the two is heated at 200 ° C. for 2 hours and then vacuum suction is applied to remove the phenol (phenyl ester method). When using a dicarboxylic acid chloride, there is a method (thioester method, acid chloride method) of stirring equimolar amounts of both in an aprotic polar solvent at room temperature overnight.

The original viscosity of the obtained polyamide is 0.05 to 1.0,
The measurement is 0.5 g / dl in meta-cresol or sulfuric acid.
At a temperature of 35 ° C.

The optically active polyamide of the present invention has a phenyl group protruding on both sides in the molecule, and since the optical activity is derived from this portion, it is a substance useful for optical resolution analysis and the like, and is a chromatograph for optically resolving a racemic compound. It can be used for applications such as a separating agent for E.

[Examples] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 0.4246 g (2.0 mmol) of (-) trans-stilbendiamine
And 0.5967 g (2.0 mmol) of adipic acid diphenyl ester were heated from room temperature to 200 ° C. in a nitrogen stream for 1 hour, continuously heated to 200 ° C. for 2 hours, and then vacuum sucked at 200 ° C. for 1 hour, The phenol was removed. The obtained polymer was dissolved by heating in 10 ml of N-methylpyrrolidone and then reprecipitated in a 1% potassium carbonate aqueous solution to obtain 0.5434 g of a polymer (yield: 85
%). The reduced viscosity of the polymer is 0.18 (0.
5g / dl, 35 ° C), average residue rotation [m] _D is + 127 ° (C
C.50, in metacresol).

Example 2 0.248 g (1.2 mmol) of (-) trans-stilbendiamine
And isophthalic acid di2-mercaptobenzothiazole ester (0.5575 g, 1.2 mmol) were dissolved in 5.0 ml of N-methylpyrrolidone, and stirring was continued overnight. The reaction product was reprecipitated in ethanol to obtain 0.2600 g of a polymer (yield 63%). The reduced viscosity of the polymer is 0.12 (0.54 g / dl in meta-cresol, 3
5 ° C.), and the average residue rotation was [m] _D −53 ° (C0.54 in metacresol).

Example 3 (-) Transstilbendiamine 0.2123 g (1.0 mmol)
To a solution of 0.2030 g (1.0 mmol) of terephthalic acid chloride in N-methylpyrrolidone (5.0 ml) was added 0.24 g of triethylamine, and the mixture was stirred at 80 ° C for 21 hours. The reaction product was reprecipitated in a 1% aqueous potassium carbonate solution to obtain 0.1501 g of a polymer (yield 44
%). The reduced viscosity of the polymer is 0.15 (0.
51 g / dl, 35 ° C), average residue rotation is [m] _D −160 ° (C
0.51, in meta-cresol).

Example 4 0.2123 g (1.0 mmol) of (-) trans-stilbendiamine
To a solution of 0.2030 g (1.0 mmol) of terephthalic acid chloride in dimethylacetamide (5.0 ml) was added 0.24 g of triethylamine, and stirring was continued at room temperature for 22 hours. The reaction product was reprecipitated in a 1% aqueous potassium carbonate solution to obtain 0.3084 g of a polymer (yield 9
0%). The reduced viscosity of the polymer is 0.20 (0.50 g / dl, 3 in sulfuric acid)
5 ° C.), and the average residue rotation was [m] _D −164 ° (C0.05, in sulfuric acid).

Example 5 (-) Transstilbendiamine 0.2123 g (1.0 mmol)
To 0.2030 g (1.0 mmol) of terephthalic acid chloride were added 5 ml of dimethylacetamide in which 17 mg of lithium chloride was dissolved, 0.26 g of triethylamine was further added, and stirring was continued at room temperature for 21 hours. The reaction product was reprecipitated in a 1% aqueous potassium carbonate solution to obtain 0.1652 g of a polymer (yield 51%). The reduced viscosity of the polymer is 0.11 (0.53 g / dl, 35 in meta-cresol)
C.) and the average optical rotation of the residue was [m] _D −168 ° (C0.53, in metacresol).

Example 6 (-) Transstilbendiamine 0.8493 g (4.0 mmol)
And 1.017 g of triethylamine were added to a dimethylacetamide solution (20.0 ml) of 0.8121 g (4.0 mmol) of isophthalic acid chloride and the same reaction as in Example 4 was carried out to obtain 1.0664 g of a polymer (yield 78%). . The reduced viscosity of the polymer is 0.
20 (0.50 g / dl in sulfuric acid, 35 ° C.), the average residue rotation was [m] _D −61 ° (C 0.50, in sulfuric acid).

Example 7 0.6081 g (2.9 mmol) of (-) trans-stilbendiamine
And decamethylene dicarboxylic acid chloride 0.7653 g (2.9 mmol)
0.70 g of triethylamine was added to the dimethylacetamide solution (14 ml) and the same reaction as in Example 4 was carried out to obtain 1.1409 g of a polymer (yield 98%). The reduced viscosity of the polymer is 0.12 (0.50 g / dl in meta-cresol, 35
C.) and the average optical rotation of the residue was [m] _D + 551 ° (C0.50, in metacresol).

Example 8 0.5153 g (2.4 mmol) of (-) trans-stilbendiamine
0.70 g of triethylamine was added to a dimethylacetamide solution (11 ml) of 0.4443 g (2.4 mmol) of adipic acid chloride and the same reaction as in Example 4 was carried out to obtain 0.8350 g of a polymer (yield 100%). . The reduced viscosity of the polymer is
0.11 (0.52 g / dl in meta-cresol, 35 ° C.), the average optical rotation of the residue was [m] _D + 109 ° (C 0.52 in meta-cresol).

Example 9 (−) Transstilbendiamine 0.6033 g (2.8 mmol)
And oxybisbenzoic acid chloride 0.8384 g (2.8 mmol) in dimethylacetamide (14 ml) with triethylamine 0.70
When g was added and the same reaction as in Example 4 was carried out, 1.238
3 g of polymer was obtained (yield 100%). The reduced viscosity of the polymer was 0.05 (0.52 g / dl in sulfuric acid, 35 ° C), and the average residue optical rotation was [m] _D + 64 ° (C0.52, in sulfuric acid).

Claims (1)

[Claims] 1. Reduction of 0.05 to 1.0 (measured in metacresol or sulfuric acid at a concentration of 0.5 g / dl at 35 ° C.) having a repeating unit represented by the following general formula (I) or (II): Optically active polyamide having viscosity. (Good _{C 2} a wherein R is branching _{- 2 0} alkylene _{group, C 6 - 1 0} one or more a group having an aromatic group, _{C 3 -
1 0} is a cycloaliphatic group one or more having groups of both may have an asymmetric carbon. )