JPS60223803A - Polysaccharide derivative - Google Patents

Abstract

PURPOSE:The titled derivative soluble in organic solvents and useful as an adsorbent, enzyme carrier, chromatographic carrier, liquid crystal substance, or the like, prepared by substituting specified groups for more than half of the hydroxyl groups of a polysaccharide molecule. CONSTITUTION:A highly active polysaccharide obtained by dissolving a polysaccharide (e.g., beta-1,4-glucan including cellulose) in a solvent such as water or formic acid, precipitating it from a different solvent and drying the precipitate is esterified with a carboxylic acid anhydride or halide containing a group of formula I -V (e.g., benzoquinonecarboxylic acid halide) in the presence of a catalyst such as sulfuric acid to obtain a polysaccharide derivative in which at least 50% hydroxyl groups are replaced by the groups of formulas I -V (e.g., benzoquinonecarboxylic acid ester of a polysaccharide).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel polysaccharide derivatives, and more particularly to polysaccharide esters of benzoquinone carboxylic acid, naphthoquinone carboxylic acid, and anthraquinone carboxylic acid.

Although various compounds are known as carboxylic acid esters of polysaccharides, cases where the carboxylic acid has a carboxyl group directly bonded to benzoquinone, naphthoquinone, or anthraquinone are hardly known.

Benzoquinone carboxylic acid esters, naphthoquinone carboxylic acid esters, and anthraquinone carboxylic acid esters of polysaccharides are generally soluble in organic solvents, especially when they are highly substituted esters in which 50% or more of the hydroxyl groups in the polysaccharide molecules are various. There is a high possibility that it can be used as an adsorbent, an enzyme carrier, a chromatographic additive, an optical isomer separating agent, a liquid crystal substance, etc.

That is, the present invention relates to a polysaccharide derivative in which the hydroxyl group in the polysaccharide molecule is substituted with one of the groups represented by the following formula.

Polysaccharides that have various monosaccharides as constituent units can be used, but those that have a linear molecular structure, or those that have a relatively small degree of branching even if they have branches, are useful. be. In addition, relatively simple structures with at most two or less types of monosaccharides as constituent units and their bonding forms are particularly useful. Examples of these are β-1,4-glucan containing cellulose; Amylose, pullulan Kanakuramu α-1,4-/)I/lJ 7, α-1,6-glucan containing dextran, cardsin, pachyman,
lentinan k containing trβ-1,3-glucan, β-2,1-fructan containing inulin, β-2 containing levan,
6-fructan, galactan including agar, polyunaloid including alginic acid, glucomannan including chitin, chitosan, and heteroglycan including mannan, xycin and glucomannan, galactomannan, arabic/galactan.

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 (the reaction catalyst may be sulfuric acid,
Brønsted acids such as perchloric acid, Lewis acids such as zinc chloride, bases such as pyridine, triethylamine, and 4-dimethylaminopyridine can be used as appropriate.

In the synthesis of the polysaccharide@derivatives of the present invention, the raw material polysaccharide is one that has been dissolved in a solvent such as water or formic acid and then precipitated in a different type of solvent and dried, one that has been directly freeze-dried from an aqueous solution, or one that has been directly freeze-dried from an aqueous solution, or an acetate ester. If the raw material is obtained by hydrolyzing a polysaccharide ester such as ester, it can be advantageously used because it has a large reaction activity.

Although the reactivity varies depending on the type of polysaccharide and the degree of polymerization, the degree of substitution of the 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, the degree of polymerization is relatively high.For example, 6
A value of 0 or more is preferable in terms of the physical strength of the molded product. Further, 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.

Among the polysaccharide derivatives of the present invention, those with a higher degree of substitution, for example, those in which 50 or more of the hydroxyl groups in the molecule are converted to carboxylic acid esters, are more soluble in organic solvents.

and a tendency to be superior in various functions.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 Cellulose acetate was saponified with hydrazine, washed, replaced with a7tone, and dried to obtain cellulose. Add 70 M of dehydrated pyridine, 5.1 side of dehydrated triethylamine, and 50~ of dimethylaminopyridine to this cellulose 11,
While stirring, anthraquinone β-carbonyl chloride 15I was added, and the mixture was stirred and reacted at 100 C for 5 hours. The product was precipitated by adding 400 tnl of ethanol and washed thoroughly with ethanol. Thereafter, it was thoroughly washed with dihydrofuran and then with N,N-dimethylacetamide.

After further washing with ethanol, the liquid was removed and vacuum dried. The purified yield of product was 3.7 g.

The infrared spectrum obtained by the KBr tablet method is shown in Figure 1, and the characteristic absorption bands are as follows.

3070cm-' Aromatic 0-H stretching vibration 17400f
'cm of carboxylic acid ester.

Stretching vibration 1680crn C=O stretching vibration of quinone 1600, 1
490.1420. In the anthraquinone ring, skeletal vibration due to stretching of carbon and carbon 15 o 0.1240 cm - Planar bending vibration of cu bond in ring 1270 crn C-O stretching vibration of ester 1040
~1170 cm-' 0-0-00 stretching vibration of cellulose 700-880 crIr1 The characteristic absorption of the proton NMR spectrum measured in OF and 0OOD and the out-of-plane bending vibration of the O-H bond of the ring is as follows. be.

7.2-8, 6ppm Proton of anthraquinone ring 3-6ppm Cellulose ring and methylene 7' at position 6
The ratio of roton ant 2 quinone ring protons to cellulose moiety protons was 5:1. When the degree of esterification was measured by the saponification method, it was found to be approximately trisubstituted.

From the above, the product is cellulose with a degree of conversion of approximately 3.0)
It can be identified as 9-quinone β-carboxylic acid ester.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum of the polysaccharide conductor of the present invention obtained in an interwoven example. -Applicant's agent Kaoru Furuya

Claims (1)

[Scope of Claims] 1. A polysaccharide derivative in which the hydroxyl group in the polysaccharide molecule is substituted with one of the groups represented by the following formula 12. -α-1,4-glucan containing pullulan, α-1,6-glucan containing dextrin, β-1,3-glucan containing curdlan, bakiman, and lentinan, and β containing inulin.
-2,1-fructan, trβ-2,6-fructan containing levan, galactan containing agar, polyunaroid containing alginic acid, chitin. The polysaccharide derivative according to claim M1, which is selected from the group of compounds consisting of gelcosabanan including chitosan, and mannan, xylan, and heteroglycan including glucomannan, galactomannan, and arabinogalactan. 3. The polysaccharide derivative according to claim 1 or 2, wherein 50% or more of the hydroxyl groups in the polysaccharide molecule are substituted.