JPS60217201A - Polysaccharide derivative - Google Patents

Abstract

PURPOSE:A novel polysaccharide derivative soluble in organic solvents, obtained by linking a COOH-containing compound consisting substantially of only one of a pair of optical antipodes which exist to a polysaccharide by ester bond. CONSTITUTION:(A) A COOH-containing compound consisting substantially of only one of a pair of optical antipodes which exist, except amino acid (e.g., one of optical antipodes such as chrysanthemumic acid, l-menthoxyacetic acid, d- tocopheroxyacetic acid, etc.) is esterified with (B) a polysaccharide (e.g., beta-1,4- glucan including cellulose, alpha-2,6-fructan including levan, galactan including agar, etc.), to give a novel derivative (preferably >=50wt% OH in a polysaccharide molecule is replaced with the compound A) wherein the compounds A and B are linked by ester bond. USE:Useful as a carrier for chromatography, a liquid crystal substance, a resolving reagent for optically active substance.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel polysaccharide derivatives, and more particularly to polysaccharide esters of optically active carboxylic acids.

Various compounds are known as carboxylic acid esters of polysaccharides, but most of them are not known, except for polysaccharide carboxylic acid esters where the carboxylic acid is optically active, and cases where the carboxylic acid is an acid. do not have.

Polysaccharide esters with optically active carboxylic acids
Especially if it is a highly substituted ester in which 50% or more of the hydroxyl groups in the polysaccharide molecule have been substituted, it is generally acidic to organic solvents and has a high possibility of being used as a chromatography frame, liquid crystal material, etc. However, it is considered to be particularly useful as a separating agent for optically active substances.

The optically active carboxylic acid used in the synthesis of the polysaccharide derivative of the present invention is one that has a pair of optical antipodes and consists essentially of only one of them, and derivatives thereof.

For example, (1) one of the optical antipodes of carboxylic acids such as dilute acids and camphor acid, (2) menthol,
An optically active carboxylic acid obtained by reacting one of the optical antipodes of a compound having a hydroxyl group such as tocopherols, horneol, and binaphthol with an α-halocarboxylic acid;
That is,! -menthoxyacetic acid, d-menthoxyacetic acid,! −
Menthoxypropionic acid, d-menthoxyacetic acid,! -bornyloxy vinegar 1 (1-polkyloxy vinegar 11.7-
) Coferoxyacetic acid, d-tocopheroxyacetic acid, etc.

Polysaccharides can be those with a variety of monosaccharide constituent units, but those with a linear molecular structure, or those with a relatively small degree of branching even if they have branches, are useful. It is. Moreover, those with a relatively simple structure, in which the types of monosaccharides that are the constituent units and the bonding forms thereof are at most two types or less, are particularly useful. Examples of these include β-1,4-glucan containing cellulose, amylose, and α-1,4-glucan containing pullulan.

α-1,6-glucan containing dextran, β-1,3-glucan containing kartran, pachyman, and lentinan;
β-2,1-fructan containing inulin, β-2,6-fructan containing lebanon, galactan containing agar, polyunaloid containing alginic acid, chitin, glucomannan containing chitosan, mannan, xylan and glucomannan, galacti These include heteroglycans, including arabinogalactin and arabinogalactin.

The reaction reagent for esterifying the above polysaccharide to lead to the derivative of the present invention may be the corresponding carboxylic acid anhydride or carboxylic acid halide, and the reaction catalyst may be sulfuric acid,
Bress/Stead acids such as perchloric acid, Lewis acids such as zinc chloride, bases such as pyridine, triethylamine, and 4-dimethylaminopyridine can be used as appropriate.

For the synthesis of the polysaccharide derivatives of the present invention, raw material polysaccharides include those that have been dissolved in a solvent such as water or formic acid and then precipitated in a different type of solvent and dried, and those that have been dried directly from an aqueous solution. When using raw materials such as polysaccharide esters, or those obtained by hydrolyzing polysaccharide esters such as acetate esters,
It has great reaction activity and can be used advantageously.

Although the reactivity varies depending on the type of polysaccharide and the degree of polymerization, the degree of substitution of the polysaccharide derivative can be adjusted by selecting reaction conditions.

The polysaccharide derivatives of the present invention can be used in various forms. For example, it is used after being molded into a film, fiber, or particulate form. In this case, 1 has a relatively high degree of polymerization, for example 6.
0 or more.

This is preferable in terms of the physical strength of the molded product.

In addition, when used as supported on microscopic silica gel, those having a relatively low degree of polymerization, for example, about 10 to 80, are more advantageous in terms of coating properties.

The polysaccharide derivative of the present invention has a high degree of substitution.

For example, compounds in which 50% or more of the hydroxyl groups in the molecule are converted to carboxylic acid esters tend to have better organic solvent solubility and various functions.

The present invention will be explained below with reference to Examples.

The present invention is not limited to this.

Example 1 Cellulose triacetate was saponified with hydrazine to obtain cellulose, which was thoroughly washed with water, replaced with acetone, and dried in vacuum.

Thus obtained cellulose 1.5f, pyridine 70m
,) Put 7.7 mg of ethyl aquine and 50 sy of dimethylaminopyridine into a three-bottle flask equipped with a stirring bar and a cooling condenser, add 18.2 F of L-menthoxyacetyl chloride at room temperature, and stir at 100°C for 5 hours. did.

The obtained reaction product was added to 500-mL ethanol with stirring. A precipitate was obtained, which was filtered through a glass filter.
and washed with ethanol. The obtained solid was dried, then dissolved in methylene chloride, reprecipitated in ethanol, filtered, washed with ethanol, sieved, and dried under vacuum.

Dissolve in methylene chloride and apply to a 1-salt cell.

The infrared absorption spectrum obtained after drying is as shown in FIG. 1, and the characteristic absorption band is as shown in the following diagram.

2850-2930 Sono-1 methyl group, methylene group 0-H
Stretching vibration 1750-17701) ml" O=0 stretching vibration of carboxylic acid ester 1450-1470 Sono-1 Methyl group 0-H Antisymmetric bending vibration Methylene group Scissor vibration 11300 II-1 Menthoxy group o-o-o stretching vibration Based on the OR of the o-o-o stretching vibration of cellulose 920iyi-1gam-dimethyl group 0-H bending vibration of 1040-1200 sei-1 cellulose (almost no absorption near 54 fSQs-'' was observed, TAIL'! This shows that it is a substituted product.The characteristic absorption of the proton NMR spectrum measured in 0DOJ is as follows.

3.8~4.4ppm Methylene proton of carboxymethyl group 0.2~! ! , 5 ppm Contained in menthoxy group ~
6 ppm Proton of cellulose ring and methylene at position 6 From these results, the product is recognized to be cellulose-L-menthoxyacetic acid ester with a degree of substitution of about 3.0.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing an infrared absorption spectrum of the polysaccharide derivative of Example 1. Applicant's agent Kaoru Furuya

Claims (1)

[Claims] A novel compound in which a carboxyl group consisting of only one pair of optical antipodes (excluding amino acids) and a polysaccharide form an ester bond. Polysaccharide molecule 2 β-1,4 where polysaccharide contains cellulose
- α-1,4- containing glucan, amylose, pullulan
α-1,6-glucan containing glucan, dex)9,
β-1,5- including curdlan, pachyman, lentinan
β-2,1-fructan containing glucan and inulin, β-2,6-fructan containing lebanon, and galactan containing agar. Polyunaroids containing alginic acid, chitin, glucomannans containing chitosan, and compounds selected from the group consisting of mannan, xylan, glucomannan, galactomannan, arabinogalactan t-containing tr-hetep-glycan Polysaccharide derivative according to item 1. 5 Claim 1 in which 50% or more of the hydroxyl groups in the polysaccharide molecule are substituted with a compound having a carboxyl group
The polysaccharide derivative according to item 1 or 2.