JP2003277401A - Polysaccharide amino acid carbamate derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polysaccharide derivative with which an optical resolution can be performed that is considered to be difficult conventionally. <P>SOLUTION: This polysaccharide amino acid carbamate derivative capable of improving separating capability in the case of being used as a constitution material of a separation agent for a chromatography is produced by converting the whole or a part of hydroxy groups in a monosaccharide residue constituting the polysaccharide into an amino acid carbamate or its salt. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polysaccharide amino acid carbamate derivative and a method for producing the same.

[0002]

2. Description of the Related Art Separation agents using polysaccharide derivatives have excellent resolving ability for a wide variety of racemic compounds as a stationary phase for liquid chromatography, and have been conventionally used in research institutions and other places. Has been done.

[0003]

However, it is a fact that some compounds are difficult to resolve even with the use of polysaccharide derivatives that have been recognized as "excellent in separation ability".

The present invention has been made in view of the above problems, and an object of the present invention is to provide a polysaccharide derivative capable of performing optical resolution which has been difficult in the past. .

[0005]

In order to achieve the above object, in the present invention, all or part of the hydroxyl groups in the monosaccharide residues constituting the polysaccharide are substituted with amino acid carbamate or a salt thereof. The inventors have found that the use of the known polysaccharide amino acid carbamate derivative enables optical resolution that has been difficult in the past, and completed the present invention.

In the case of the main purpose of optical resolution, the amino acid residues constituting the polysaccharide amino acid carbamate derivative are amino acid residues of optically active amino acids (for example, essential amino acids other than glycine). Is preferred.

Further, the polysaccharide amino acid carbamate derivative can be obtained by adding an amino acid ester isocyanate to the hydroxyl group in the monosaccharide residue constituting the polysaccharide and then deesterifying.

[0008] Here, in the case of performing racemic resolution with a polysaccharide derivative, the higher-order structure of the polysaccharide derivative is well adapted to the structure of the racemic compound, and various adsorptive interactions between them are effective. It is considered important to work properly. INDUSTRIAL APPLICABILITY The novel polysaccharide amino acid carbamate derivative according to the present invention is used in a stationary phase for liquid chromatography for performing optical resolution because various adsorptive interactions with a racemic compound effectively work. It is useful as a raw material for a separating agent for chromatography and the like.

Further, the novel polysaccharide amino acid carbamate derivative according to the present invention is superior in biocompatibility as compared with conventional cellulose ester derivatives such as cellulose acetate, cellulose acetate butyrate and nitrocellulose, and has a high solvent content. It also has solubility. Therefore, the novel polysaccharide amino acid carbamate derivative according to the present invention is also useful as a film, paint resin, coating material, adhesive, thickener, and the like.

More specifically, the present invention provides the following.

(1) An amino acid ester isocyanate for producing a polysaccharide amino acid ester carbamate derivative represented by the general formula (I).

[0012]

[Chemical 8] (In the general formula (I), R represents a hydrogen atom, or an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms.
The aliphatic hydrocarbon or aromatic hydrocarbon is an amino group,
Hydroxyl group, carboxyl group, mercapto group, thioether group, or may be condensed with a benzene ring, 1 to
It may be substituted with a 5-membered heterocycle having 2 nitrogen atoms. R ¹ represents an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms. )

(2) A polysaccharide amino acid ester carbamate derivative represented by the general formula (II).

[0014]

[Chemical 9] (In the general formula (II), X is OR ² , NHR ² or NH.
COCH ₃ is shown, and n is an integer of 5 or more. R ² is
Each is the same or different and represents a hydrogen atom, a metal atom or a group represented by the formula (III), but in the range of n of 1 to 4, all R ^{2 s} in the general formula (II) may be H. But,
When n is 5 or more, all R ^{2 s} in the general formula (II) are H
And at least one of R ² in this case is a group represented by the formula (III). )

[0015]

[Chemical 10] (In the general formula (III), R represents a hydrogen atom, or an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms. R ¹ represents an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms. Indicates hydrogen.)

(3) A polysaccharide amino acid carbamate derivative represented by the general formula (II).

[0017]

[Chemical 11] (In the general formula (II), X is OR ² , NHR ² or NH.
COCH ₃ is shown, and n is an integer of 5 or more. R ² is
Each is the same or different and represents a hydrogen atom, a metal atom or a group represented by the formula (IV), but in the range of 1 to 4, all R ^{2 s} in the general formula (II) may be H. But,
When n is 5 or more, all R ^{2 s} in the general formula (II) are H
And at least one of R ² in this case is a group represented by the formula (IV). )

[0018]

[Chemical 12] (In the general formula (IV), R represents a hydrogen atom or an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms.
Q represents a hydrogen atom or a metal atom. )

(4) A method for producing a polysaccharide amino acid ester carbamate derivative, which comprises reacting the amino acid ester isocyanate represented by the general formula (I) with a polysaccharide.

[0020]

[Chemical 13] (In the general formula (I), R represents a hydrogen atom, or an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms.
R ¹ represents an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms. )

(5) The method according to (4), wherein the polysaccharide is cellulose, chitosan or chitin.

(6) Polysaccharide amino acid carbamate derivative for obtaining a polysaccharide amino acid carbamate derivative by deesterifying the polysaccharide amino acid ester carbamate derivative obtained by reacting the amino acid ester isocyanate represented by the general formula (I) with a polysaccharide. Manufacturing method.

[0023]

[Chemical 14] (In the general formula (I), R represents a hydrogen atom, or an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms.
R ¹ represents an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms. )

(7) The method according to (6), wherein the polysaccharide is cellulose, chitosan or chitin.

(8) The method according to claim 7, wherein the deesterification is carried out with an aqueous solution of a weakly basic alkali metal hydroxide.

In this regard, the use of an aqueous solution of a weakly basic alkali metal hydroxide is effective when the basicity is strong and the amide bond (-C of the polysaccharide amino acid ester carbamate derivative is
This is because the ONH-) part will be cut. Therefore, the term “weakly basic” means, in the present invention, basic to such an extent that the amide bond (—CONH—) of the polysaccharide amino acid ester carbamate derivative is not cut.

(9) A polysaccharide amino acid carbamate derivative in which all or part of the hydroxyl groups in the monosaccharide residues constituting the polysaccharide are replaced with amino acid carbamate or a salt thereof.

The type of amino acid corresponding to the amino acid residue of amino acid carbamate is not particularly limited. Therefore, not only the essential amino acids of the living body but also amino acid carbamates related to other amino acids can be used. When the amino acid residue is an amino acid carbamate related to glycine, α of the amino acid residue
Since carbon is not an asymmetric carbon and has no optical activity, it is better to use other materials when used as a raw material for a chromatographic separation agent used in the stationary phase of chromatography for optical resolution. There may be good cases. The "amino acid carbamate or salt thereof" referred to herein includes, for example, those represented by the general formula (IV).

(10) The amino acid carbamate is
The polysaccharide amino acid carbamate derivative according to (9), which is an amino acid carbamate containing an optically active amino acid residue.

(11) The polysaccharide amino acid carbamate derivative according to (3) or (9), which is a constituent material of a film material, a paint material, a coating material, an adhesive material, or a thickener material.

In the case of an amino acid carbamate derivative in which the amino acid of the amino acid residue is glycine, glycine can be produced at low cost because glycine is inexpensive.
It is suitable when it is a constituent material of the above-mentioned in which no inconvenience occurs because the α carbon of the amino acid residue is not an asymmetric carbon.

(12) The polysaccharide amino acid carbamate derivative according to (3), (9) or (10), which is a constituent material of a separating agent for chromatography.

(13) A method of using an amino acid ester isocyanate as an electrophile for converting a polysaccharide into a polysaccharide amino acid carbamate derivative in a stable and high yield.

(14) A method for obtaining a polysaccharide amino acid carbamate derivative by adding an amino acid ester isocyanate to a hydroxyl group in a monosaccharide residue constituting a polysaccharide and then deesterifying the same.

The production of the polysaccharide amino acid carbamate derivative according to the present invention can be understood as the inventions described in (15) to (18) below.

(15) A method for improving the solvent solubility by converting all or part of the hydroxyl groups in the monosaccharide residues constituting the polysaccharide into amino acid carbamates or salts thereof.

(16) A method for improving biocompatibility by converting all or part of the hydroxyl groups in the monosaccharide residues constituting a polysaccharide into amino acid carbamates or salts thereof.

(17) Chromatography in the case where it is used as a constituent material of a separating agent for chromatography by converting all or a part of hydroxyl groups in a monosaccharide residue constituting a polysaccharide into an amino acid carbamate or a salt thereof. How to improve resolution.

(18) Separation of optically active substances by converting all or part of the hydroxyl groups in the monosaccharide residues constituting the polysaccharide into amino acid carbamates containing optically active amino acid residues or salts thereof. A method for improving the chromatographic separation ability of an optically active substance when used as a constituent material for a chromatographic separating agent.

[0040]

The amino acid ester isocyanates used in the Detailed Description of the Invention The present invention, alanine ester isocyanate (R = _-CH 3), arginine ester isocyanate _{(R = -CH 2 CH 2 CH} 2 NHC (=
_NH) NH 2), aspartate isocyanate _(R = -CH 2 COOH), cysteine ester isocyanate (R = _-CH 2 SH), cystine ester isocyanate _(-CH 2 S), glutamate isocyanate (R = -CH ₂ CH ₂ COOH), glutamine ester isocyanate (R = -CH ₂ CH ₂ CO
NH _2), glycine ester isocyanate (R = -
H), histidine ester isocyanate (R = -CH
_{2 -C 3 H 3 N 2)} , hydroxylysine ester isocyanate _{(R = -CH 2 CH 2 CH} (OH) CH 2 NH
₂ ), hydroxyproline ester isocyanate (R
_{= -CH 2 CH (OH) CH} 2 -), isoleucine ester isocyanate _{(R = -CH (CH 3)} CH 2 CH
₃ ), leucine ester isocyanate (R = CH ₂ C
H (CH ₃ ) ₂ ), lysine ester isocyanate (R
_{= - (CH 2) 4 NH} 2), methionine ester isocyanate _{(R = -CH 2 CH 2 SCH} 3), phenylalanine ester isocyanate (R = _-CH 2 C
₆ H ₅ ), proline ester isocyanate (R = -C
_{H 2 CH 2 CH 2 -)} , serine ester isocyanate (R = _-CH 2 OH), threonine ester isocyanate _{(R = -CH (OH) CH} 3), tryptophan ester isocyanate _{(R = -CH-C 8 H} 5 NH ),
Tyrosine ester isocyanate _{(R =} -CH 2 -p-
C ₆ H ₄ -OH), valine ester isocyanate (R
= -CH _{(CH 3) 2),} and the like. However, the amino acid ester isocyanate according to the present invention,
It is not limited to these.

The amino acid ester isocyanate according to the present invention is a carbamic acid derivative produced by esterifying a portion of the carboxyl group of the amino acid using the starting material as an amino acid, then acylating the amino group, and performing the acylation. Can be obtained by dehydrating. At this time, it should be noted that if the acidic condition is increased, the possibility of racemization is increased.

When the polysaccharide to which the amino acid ester isocyanate is added is cellulose, chitosan or chitin, when the polysaccharide is cellulose, a polysaccharide amino acid carbamate derivative represented by the following general formula (V) is obtained. When the polysaccharide is chitosan, a polysaccharide amino acid carbamate derivative represented by the general formula (VI) is obtained, and when the polysaccharide is chitin, the polysaccharide amino acid carbamate derivative represented by the general formula (VII). Is obtained.

[0043]

[Chemical 15] As the dilute alkaline aqueous solution as the deesterification agent, a dilute sodium hydroxide aqueous solution or a dilute potassium hydroxide aqueous solution can be used, but it is not limited thereto and is not reducible, and nucleophilic by an anion other than a hydroxyl group is used. Any material having a low property can be preferably used. And
By carrying out deesterification using such a dilute aqueous alkaline solution, -in the functional group represented by the general formula (IV)
The COOR ¹ group is converted to a —COOH group or a salt thereof.

The novel polysaccharide amino acid carbamate derivative according to the present invention is used as a raw material for a chromatographic separating agent used in a stationary phase for liquid chromatography, as in the case of a conventional separating agent using a polysaccharide derivative. Can be used. As the manufacturing method, a conventional separating agent using a polysaccharide derivative can be adopted.

Further, the novel polysaccharide amino acid carbamate derivative according to the present invention has excellent biocompatibility and high solvent solubility in comparison with conventional cellulose ester derivatives such as cellulose acetate, cellulose acetate butyrate and nitrocellulose. It also has sex. Therefore,
The novel polysaccharide amino acid carbamate derivative according to the present invention is used as a film, a coating resin, a coating material, an adhesive, a thickener, particularly a biofilm, a biocoating material, a bioadhesive, a biothickener, etc. Is also useful. Regarding these, after dissolving the polysaccharide amino acid carbamate derivative according to the present invention in a predetermined solvent,
Conventional films, paint resins, coating materials,
Like the adhesive and the thickener, the production can be performed according to a conventional method.

[0046]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[Example 1: Synthesis of cellulose tris (L-leucine ethyl ester carbamate)]

[0048]

[Chemical 16]

Cellulose (Cellulose microcrystallin
e) 1g of (MERCK) lithium chloride {(Kanto Chemical)} /
It was added to 45 ml of a solution of {DMAc (N, N-dimethylacetamide (dehydrated)) (Kanto Kagaku)} (1/10 (w / v)), and the mixture was stirred at 100 ° C. for 24 hours. This was cooled to room temperature, 10 g of L-leucine ethyl ester isocyanate was added, and the mixture was reacted at 100 ° C. for 48 hours while stirring. After cooling, the reaction solution was poured into an excessive amount of acetone to stop the reaction. The amount of the polymer obtained was 0.75 g. Soluble in pyridine and methanol, chloroform, THF,
It was insoluble in alkanes such as pentane and hexane, aromatic compounds such as benzene and toluene, and solvents such as dimethylformamide and dimethylsulfoxide.

The degree of substitution was estimated to be about 3 from the results of elemental analysis. <Elemental analysis value = C: 45.40% H: 6.81% N: 5.01%
>

[Example 2: Synthesis of cellulose tris (L-leucine carbamate)]

[0052]

[Chemical 17]

Cellulose tris (L obtained in Example 1
-Leucine ethyl ester carbamate) to 2M Na
Aqueous OH solution was added and stirred for 24 hours. The undissolved residue was removed by filtration, the filtrate was neutralized with HCl, dialyzed with a cellulose tube for dialysis for 24 hours, and dried by freeze-drying to obtain the title compound. The obtained polymer was a white powder and was soluble in a 2M to 4M aqueous NaOH solution.

[Example 3: Synthesis of cellulose tris (L-aspartic acid diethyl ester carbamate)]

[0055]

[Chemical 18]

1 g of cellulose was added to lithium chloride / N, N-
Solution 4 of dimethylacetamide (1-10 (w / v))
It was added to 5 ml and stirred at 100 ° C. for 24 hours. This was cooled to room temperature, 10 g of L-leucine ethyl ester isocyanate was added, and the mixture was reacted at 100 ° C. for 48 hours while stirring. Then, the reaction solution was poured into an excessive amount of acetone to stop the reaction. The amount of the polymer obtained was 0.8 g. Soluble in pyridine and methanol, chloroform, T
It was insoluble in most solvents such as alkanes such as HF, pentane and hexane, aromatic compounds such as benzene and toluene, dimethylformamide and dimethylsulfoxide.

The degree of substitution was estimated to be about 3 from the results of elemental analysis. <Elemental analysis value = C: 46.27% H: 6.75% N: 4.49%
>

[Example 4: Synthesis of cellulose tris (L-aspartic acid carbamate)]

[0059]

[Chemical 19]

A 2M aqueous sodium hydroxide solution was added to cellulose tris (L-aspartic acid diethyl ester carbamate), and the mixture was stirred for 24 hours. The undissolved residue was removed by filtration, the filtrate was neutralized with HCl, dialyzed with a cellulose tube for dialysis for 24 hours, and dried by freeze-drying. The polymer obtained is a white powder, 2M
To 4M aqueous sodium hydroxide solution.

[Example 5: Synthesis of cellulose (L-phenylalanine carbamate)]

[0062]

[Chemical 20]

2 g of cellulose was added to lithium chloride / N, N-
Dimethylacetamide (1/10 (w / v)) solution 3
It was added to 0 ml and stirred at 100 ° C. for 24 hours. After cooling this to room temperature, 20 ml of pyridine and 7.02 g of L-aspartic acid diethyl ester isocyanate were added, and 10
The reaction was carried out for 48 hours with stirring at 0 ° C. Then, the reaction solution was poured into an excessive amount of methanol to stop the reaction.
This solution was filtered and then washed with 2M aqueous sodium hydroxide solution.
Stir for 4 hours. The undissolved residue was removed by filtration, the filtrate was neutralized with HCl, dialyzed with a cellulose tube for dialysis for 24 hours, and dried by freeze-drying. The amount of the polymer obtained was 1.11 g. The polymer was a white powder and was soluble in 2M to 4M aqueous sodium hydroxide solution. The degree of substitution was 0.23. <Elemental analysis value = C: 44.98% H: 5088% N: 1.48%
>

Example 6: Synthesis of chitin (L-leucine ethyl ester carbamate)

[0065]

[Chemical 21]

Chitin 0.5 g was added to lithium chloride / N, N-
Solution 4 of dimethylacetamide (1/10 (w / v))
It was added to 5 ml and stirred at 100 ° C. for 24 hours. After cooling this to room temperature, 5 g of L-leucine ethyl ester isocyanate was added, and the mixture was reacted at 100 ° C. for 48 hours while stirring. After cooling, the reaction solution was poured into an excessive amount of acetone to stop the reaction. The amount of the polymer obtained was 0.36 g. It was insoluble in most solvents such as chloroform THF. The degree of substitution was estimated to be approximately 1 from the result of elemental analysis.

[Example 7: Synthesis of chitin (L-aspartic acid diethyl ester carbamate)]

[0068]

[Chemical formula 22]

1 g of cellulose was added to lithium chloride / N, N-
Dimethylacetamide (1/10 (w / v)) solution 9
It was added to 0 ml and stirred at 100 ° C. for 24 hours. After cooling this to room temperature, 5 g of L-leucine ethyl ester isocyanate was added, and the mixture was reacted at 100 ° C. for 48 hours while stirring. Then, the reaction solution was poured into an excessive amount of acetone to stop the reaction. The amount of the polymer obtained was 0.88 g. It was insoluble in most solvents such as chloroform THF. The degree of substitution was estimated to be approximately 1 from the result of elemental analysis.

[Synthesis of Raw Material: Synthesis of Amino Acid Ester Isocyanate] In synthesizing the amino acid ester isocyanate, the following amino acids were used as raw materials. (All Kanto Chemical)

L-alanine, L-leucine, L (+)-isoleucine, L-valine, L-methionine, L (-)-phenylalanine, L-aspartic acid, L-glutamic acid, D-alanine,
D-leucine, D-isoleucine, D-valine, D-methionine, D-phenylalanine, D-aspartic acid, D-glutamic acid, DL-alanine, DL-leucine, DL-isoleucine, DL-valine, DL-methionine, DL -Phenylalanine.

[Reference Example 1: Synthesis of amino acid ester] 1.0 mol / l alcoholic hydrochloric acid (kishida) was added to the above various amino acids until all the amino acids were dissolved. After heating under reflux for 10 hours, the solution is cooled and the alcohol is distilled off under reduced pressure. The residue was dissolved in dichloromethane and extracted with a separatory funnel together with water adjusted to pH 10 with aqueous ammonia. The organic phase was extracted once again with a saturated sodium chloride solution, dried over MgSO _4, and then purified by vacuum distillation.

[Reference Example 2: Synthesis of amino acid ester isocyanate] A solution prepared by dissolving an amino acid ester in dichloromenthane was treated with DMAP (4-dimethylaminopyridine) (1.
0eq) (Wako Pure Chemical Industries) and (Boc) ₂ O (di-t-butyl dicarbonate)
(1.4 eq) (Wako Pure Chemical Industries) is added dropwise to a solution of dichloromethane. After 10 minutes, extraction was performed twice with 0.5 mol / l hydrochloric acid and ice, and the organic phase was further extracted with saturated saline. The obtained organic phase was dried over MgSO ₄ and then purified by vacuum distillation.

[Example 8: Preparation of optical resolution column] <hydrophobicization of silica gel> Silica gel (Daiso gel SP-100
(7 μm) was vacuum dried (40 ° C., 3 h), suspended in 270 ml of toluene, 53 ml of 3-aminopropyltriethoxysilane was added, and the reaction was carried out for 12 h while heating under reflux. The reaction product was filtered, thoroughly washed with methanol, washed with acetone, and dried under vacuum.

<Column packing> Hydrophobized silica gel
3.0g of the cellulose amino acid carbamate derivative (polysaccharide amino acid carbamate derivative) obtained above was dissolved in 0.75g, and the solution (solvent in which polymer was dissolved and silica gel was not dissolved) was coated. The slurry filling machine (Chemco, ECONO-
PACKER CPP-085) was used to fill a stainless steel column (1/4 x 4.6 x 250) to create an optical resolution column.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G01N 30/48 G01N 30/48 W 30/88 30/88 W // G01N 30/56 30/56 A ( 72) Inventor Tokuji Toyoji, Kita-ku, Kita-ku, Kita-ku, Article 13 West 8-chome (72) Inventor Toshifumi Sato, Kita-ku, Kita-ku, Sapporo, Kita-ku 13, Article 8 F-term (reference) 4C090 AA02 AA03 BA21 BA46 BB18 BB36 BB53 BB62 BB72 BB94 BD13 BD16 BD50 4G066 AB07A AB09A AC01A AC01B AD06B AD11A AE14B CA19 CA20 DA07 EA01 4H006 AA01 AB84

Claims (18)

[Claims] 1. An amino acid ester isocyanate for producing a polysaccharide amino acid ester carbamate derivative represented by the general formula (I). [Chemical 1] (In the general formula (I), R represents a hydrogen atom, or an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms.
The aliphatic hydrocarbon or aromatic hydrocarbon is an amino group,
Hydroxyl group, carboxyl group, mercapto group, thioether group, or may be condensed with a benzene ring, 1 to
It may be substituted with a 5-membered heterocycle having 2 nitrogen atoms. R ¹ represents an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms. ) 2. A polysaccharide amino acid ester carbamate derivative represented by the general formula (II). [Chemical 2] (In the general formula (II), X is OR ² , NHR ² or NH.
COCH ₃ is shown, and n is an integer of 5 or more. R ² is
Each is the same or different and represents a hydrogen atom, a metal atom or a group represented by the formula (III), but in the range of n of 1 to 4, all R ^{2 s} in the general formula (II) may be H. But,
When n is 5 or more, all R ^{2 s} in the general formula (II) are H
And at least one of R ² in this case is a group represented by the formula (III). ) [Chemical 3] (In the general formula (III), R represents a hydrogen atom, or an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms. R ¹ represents an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms. Indicates hydrogen.) 3. A polysaccharide amino acid carbamate derivative represented by the general formula (II). [Chemical 4] (In the general formula (II), X is OR ² , NHR ² or NH.
COCH ₃ is shown, and n is an integer of 5 or more. R ² is
Each is the same or different and represents a hydrogen atom, a metal atom or a group represented by the formula (IV), but in the range of 1 to 4, all R ^{2 s} in the general formula (II) may be H. But,
When n is 5 or more, all R ^{2 s} in the general formula (II) are H
And at least one of R ² in this case is a group represented by the formula (IV). ) [Chemical 5] (In the general formula (IV), R represents a hydrogen atom or an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms.
Q represents a hydrogen atom or a metal atom. ) 4. A method for producing a polysaccharide amino acid ester carbamate derivative, which comprises reacting the amino acid ester isocyanate represented by the general formula (I) with a polysaccharide. [Chemical 6] (In the general formula (I), R represents a hydrogen atom, or an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms.
R ¹ represents an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms. ) 5. The method according to claim 4, wherein the polysaccharide is cellulose, chitosan, or chitin. 6. A polysaccharide amino acid carbamate derivative for obtaining a polysaccharide amino acid carbamate derivative by deesterifying the polysaccharide amino acid ester carbamate derivative obtained by reacting the amino acid ester isocyanate represented by the general formula (I) with a polysaccharide. Production method. [Chemical 7] (In the general formula (I), R represents a hydrogen atom, or an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms.
R ¹ represents an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 30 carbon atoms. ) 7. The method of claim 6, wherein the polysaccharide is cellulose, chitosan or chitin. 8. The method according to claim 7, wherein the deesterification is carried out with an aqueous solution of a weakly basic alkali metal hydroxide. 9. A polysaccharide amino acid carbamate derivative in which all or part of the hydroxyl groups in the monosaccharide residues constituting the polysaccharide are replaced with amino acid carbamate or a salt thereof. 10. The polysaccharide amino acid carbamate derivative according to claim 9, wherein the amino acid carbamate is an amino acid carbamate containing an optically active amino acid residue. 11. The polysaccharide amino acid carbamate derivative according to claim 3, which is a constituent material of a film material, a paint material, a coating material, an adhesive material, or a thickener material. 12. The polysaccharide amino acid carbamate derivative according to claim 3, which is a constituent material of a separating agent for chromatography. 13. A method of using an amino acid ester isocyanate as an electrophile for converting a polysaccharide into a polysaccharide amino acid carbamate derivative in a stable and high yield. 14. A method for obtaining a polysaccharide amino acid carbamate derivative by adding an amino acid ester isocyanate to a hydroxyl group in a monosaccharide residue constituting a polysaccharide and then deesterifying the same. 15. A method for improving solvent solubility by converting all or part of hydroxyl groups in a monosaccharide residue constituting a polysaccharide into an amino acid carbamate or a salt thereof. 16. A method for improving biocompatibility by converting all or a part of hydroxyl groups in a monosaccharide residue constituting a polysaccharide into an amino acid carbamate or a salt thereof. 17. A chromatographic separation when used as a constituent material of a chromatographic separating agent by converting all or part of hydroxyl groups in a monosaccharide residue constituting a polysaccharide into an amino acid carbamate or a salt thereof. How to improve performance. 18. A chromatograph for separating optically active substances by converting all or part of hydroxyl groups in monosaccharide residues constituting a polysaccharide into amino acid carbamates containing optically active amino acid residues or salts thereof. A method for improving the chromatographic separation ability of an optically active substance when used as a constituent material of a separating agent for chromatography.