WO2012005245A1 - 多糖誘導体及びその製造方法並びに分離剤 - Google Patents
多糖誘導体及びその製造方法並びに分離剤 Download PDFInfo
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- WO2012005245A1 WO2012005245A1 PCT/JP2011/065363 JP2011065363W WO2012005245A1 WO 2012005245 A1 WO2012005245 A1 WO 2012005245A1 JP 2011065363 W JP2011065363 W JP 2011065363W WO 2012005245 A1 WO2012005245 A1 WO 2012005245A1
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- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/20—Carbocyclic rings
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
- B01J20/285—Porous sorbents based on polymers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/29—Chiral phases
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3268—Macromolecular compounds
- B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
- B01J20/3274—Proteins, nucleic acids, polysaccharides, antibodies or antigens
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B33/00—Preparation of derivatives of amylose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/14—Amylose derivatives; Amylopectin derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/8877—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample optical isomers
Definitions
- the present invention relates to a novel polysaccharide derivative, a method for producing the same, and a separating agent containing the polysaccharide derivative.
- Polysaccharide derivatives obtained by modifying hydroxyl groups and amino groups of polysaccharides with various substituents are known to have high optical resolution as chromatographic chiral stationary phases, and so far many types of polysaccharide derivatives Is synthesized.
- polysaccharide derivative useful for such a separating agent for optical isomers for example, a polysaccharide comprising a structure in which hydroxyl groups or amino groups at the 2-position and 3-position (and 6-position) of the polysaccharide are replaced with specific different substituents.
- Derivatives have been proposed (see Patent Document 1).
- the hydroxyl group or amino group of the polysaccharide is substituted with two or more different specific substituents, and particularly the 2-position and 3-position substituents.
- Polysaccharide derivatives having different substituents at the 6-position are also disclosed (see Patent Document 2).
- polysaccharide derivatives having a specific type of substituent at a specific position particularly polysaccharide derivatives having different specific substituents at the 2-position and 3-position, which are difficult to distinguish in introducing a substituent into a hexose. There is still room for further study.
- the present invention has been made in view of the above circumstances, and an object thereof is to provide a novel polysaccharide derivative that can be used as a separating agent for optical isomers, a method for producing the same, and a separating agent containing the polysaccharide derivative. .
- the present invention replaces the hydrogen atom of the 2-position hydroxyl group or amino group of the polysaccharide structural unit with a monovalent group represented by the following general formula (1), and Provided is a polysaccharide derivative including a structure in which a hydrogen atom of a 3-position hydroxyl group or amino group of a structural unit is substituted with a monovalent group represented by the following general formula (2).
- R 1 —NH—CO— (1)
- R 2 —NH—CO— (2) (In formulas (1) and (2), R 1 and R 2 represent different substituted or unsubstituted aryl groups.)
- the present invention also provides a polysaccharide derivative in which the polysaccharide is cellulose or amylose. Furthermore, the present invention provides a polysaccharide derivative wherein R 1 is a 3,5-dichlorophenyl group and R 2 is a 3,5-dimethylphenyl group.
- the hydrogen atom of the 2-position and 3-position hydroxyl group or amino group of the structural unit of the polysaccharide is the same as the following general formula (1): R 1 —NH—CO— (1)
- R 1 represents a substituted or unsubstituted aryl group.
- R 2 represents a substituted or unsubstituted aryl group different from R 1 above.
- R 2 By reacting the compound represented by the formula (1), any one of the monovalent groups represented by the above general formula (1) substituted with the hydroxyl groups at the 2nd and 3rd positions or the hydrogen atom of the amino group, Formula (2): R 2 —NH—CO— (2) (In the formula (2), R 2 has the same meaning as R 2 in the general formula (3).)
- the present invention provides a separating agent containing the polysaccharide derivative described above.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of cellulose tris (3,5-dichlorophenylcarbamate).
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of cellulose tris (3,5-dimethylphenylcarbamate).
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- FIG. 3 is a diagram showing a 1 H-NMR spectrum chart of a reaction product when producing the polysaccharide derivative of the present invention.
- the present embodiment a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary.
- the present invention is not limited to the present embodiment described below, and various modifications can be made without departing from the scope of the present invention.
- the hydrogen atom of the 2-position hydroxyl group or amino group of the polysaccharide structural unit is substituted with a monovalent group represented by the following general formula (1), and the structural unit has It includes a structure in which the hydrogen atom of the hydroxyl group or amino group at the 3-position is substituted with a monovalent group represented by the following general formula (2) (hereinafter referred to as “predetermined structure”).
- This polysaccharide derivative may be composed only of the predetermined structure, and may further include another structure.
- R 2 —NH—CO— (2)
- R 1 and R 2 represent different substituted or unsubstituted aryl groups.
- “hydrogen atom of amino group” means one of two hydrogen atoms.
- the above-mentioned polysaccharide is not particularly limited as long as it is a polysaccharide having a hydroxyl group or an amino group at least at the 2-position and 3-position.
- examples of such polysaccharides include ⁇ -1,4-glucan (cellulose), ⁇ -1,4-glucan (amylose, amylopectin), ⁇ -1,6-glucan (dextran), ⁇ -1,6- Glucan (pustulan), ⁇ -1,3-glucan (curdlan, schizophyllan), ⁇ -1,3-glucan, ⁇ -1,2-glucan (CrownGall polysaccharide), ⁇ -1,4-galactan, ⁇ -1 , 4-mannan, ⁇ -1,6-mannan, ⁇ -1,2-fructan (inulin), ⁇ -2,6-fructan (levan), ⁇ -1,4-xylan, ⁇ -1,3-xylan , ⁇ -1,4-chitosan,
- the polysaccharide is preferably cellulose and amylose, and more preferably cellulose.
- the number average degree of polymerization of the polysaccharide is preferably 5 or more, more preferably 10 or more, and there is no particular upper limit. From the viewpoint of ease, it is preferably 5 to 1000, more preferably 10 to 1000, and particularly preferably 10 to 500.
- R 1 and R 2 represent different substituted or unsubstituted aryl groups.
- the aryl group include an aryl group containing a condensed ring having 6 to 30 carbon atoms, such as a phenyl group, an indenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a pyrenyl group, a biphenyl group, And phenyl.
- a phenyl group is preferable from a viewpoint of optical resolution.
- R 1 and R 2 may have include, for example, a hydrocarbon group, a cyano group, a halogen atom, a hydroxy group, a nitro group, and an amino group, which may contain a hetero atom having 1 to 12 carbon atoms. And one or two or more substituents selected from the group consisting of a di (alkyl having 1 to 8 carbons) amino group (that is, an amino group having an alkyl group having 1 to 8 carbons as a substituent).
- a hydrocarbon group and a halogen atom which may contain a hetero atom having 1 to 12 carbon atoms are preferable.
- the hydrocarbon group which may contain a heteroatom having 1 to 12 carbon atoms is preferably an alkyl group having 1 to 2 carbon atoms
- the halogen atom is preferably a chlorine atom.
- a monovalent group represented by the above general formulas (1) and (2) (hereinafter, one substituted or unsubstituted aryl on the carbamoyl nitrogen atom as represented by the above general formulas (1) and (2));
- the substituted carbamoyl group to which the group is bonded is generally referred to as “predetermined carbamoyl group”.) Is a hydroxyl group or amino group at the corresponding position in the structural unit as long as the effect of optical resolution by these groups is obtained. May not be substituted on all of the hydrogen atoms.
- the introduction rate of a predetermined carbamoyl group into the polysaccharide derivative of the present embodiment is preferably 70 to 100%, more preferably 80 to 100%, and particularly preferably 100%.
- the introduction rate (%) is defined as follows. That is, in the polysaccharide derivative of the present embodiment, when the predetermined carbamoyl group is substituted with all of the hydrogen atoms of the hydroxyl group or amino group in the above-described structural unit, the hydroxyl group or amino group of the structural unit. Is the ratio of the total number of predetermined carbamoyl groups in the polysaccharide derivative of this embodiment to the total number of.
- the introduction rate can be determined by using a known analysis method such as NMR or elemental analysis that can identify one or both of the type and bonding position of the predetermined carbamoyl group, and can also determine the type or substituent of the predetermined carbamoyl group. It can obtain
- the introduction rate is 100 in the ratio of the number of the predetermined carbamoyl group to the total number of hydroxyl groups of the polysaccharide after the substitution. It is a numerical value multiplied by. Further, when the predetermined carbamoyl group is substituted only with the hydrogen atom of the amino group, the value is obtained by multiplying the ratio of the number of the predetermined carbamoyl group to the total number of amino groups of the polysaccharide after the substitution by 100.
- the ratio of the total number of the predetermined carbamoyl groups to the total of the total number of hydroxyl groups and the total number of amino groups of the substituted polysaccharide is set to 100. It is a value that is multiplied.
- a 2-position substituent obtained by substituting a hydrogen atom of a hydroxyl group or an amino group with a monovalent group represented by the general formula (1) (hereinafter referred to as “predetermined 2-position substituent”) is as follows. It is preferable that the hydrogen atom of the hydroxyl group is substituted with a monovalent group represented by the general formula (1).
- R 1 is preferably a substituted or unsubstituted phenyl group, more preferably a phenyl group having a substituent at the 3-position and the 5-position, and a 3,5-dichlorophenyl group or 3, A 5-dimethylphenyl group is more preferred, and a 3,5-dichlorophenyl group is particularly preferred.
- the 3-position substituent obtained by substituting the hydrogen atom of the hydroxyl group or amino group with the monovalent group represented by the general formula (2) (hereinafter referred to as “predetermined 3-position substituent”) is as follows. It is different from the predetermined substituent at the 2-position.
- the predetermined 3-position substituent is preferably a group in which a hydrogen atom of a hydroxyl group is substituted with a monovalent group represented by the general formula (2).
- R 2 is preferably a substituted or unsubstituted phenyl group, more preferably a phenyl group having a substituent at the 3-position and the 5-position, and a 3,5-dichlorophenyl group or 3, A 5-dimethylphenyl group is more preferred, and a 3,5-dimethylphenyl group is particularly preferred.
- the 6-position carbon atom may further include a substituent.
- the 6-position substituent in the structural unit is preferably a 6-position hydroxyl group or amino group hydrogen atom substituted with a predetermined carbamoyl group, and a 6-position hydroxyl group hydrogen atom substituted with a predetermined carbamoyl group. More preferably.
- the 6-position substituent is preferably the same substituent as the predetermined 2-position substituent or the predetermined 3-position substituent, and is the same substituent as the predetermined 3-position substituent. More preferably.
- the polysaccharide derivative of the present embodiment includes the above-described predetermined structure
- the above-mentioned predetermined 2-position substituent is used as at least one of the 2-position substituent and the 3-position substituent in the other structures.
- a structure having a substituent other than the predetermined 3-position substituent may include a structure in which the substituent at the 2-position and the substituent at the 3-position are different from each other in a structure other than the predetermined structure.
- any one of the substituent at the 2-position and the substituent at the 3-position, which are different from each other, is preferably such that a hydrogen atom of a hydroxyl group or an amino group is substituted with a predetermined carbamoyl group, Is more preferably substituted with a predetermined carbamoyl group.
- the polysaccharide derivative of the present embodiment may include a structure in which the substituent at the 2-position and the substituent at the 3-position are the same as each other in a structure other than the predetermined structure.
- the substituent at the 2-position and the substituent at the 3-position that are the same as each other are preferably those in which a hydrogen atom of a hydroxyl group or an amino group is substituted with a predetermined carbamoyl group, and the hydrogen atom of the hydroxyl group is replaced with a predetermined carbamoyl group. It is more preferable that it is substituted.
- the 2-position substituent and 3-position substituent that are the same as each other are preferably the same as either the 2-position or 3-position substituent in the predetermined structure.
- the polysaccharide derivative according to the present embodiment is a case where the 2-position and 3-position hydroxyl groups or amino group hydrogen atoms of the polysaccharide structural unit are substituted only with a predetermined carbamoyl group, and the predetermined carbamoyl group is
- the ratio of both carbamoyl groups at the 2-position (a: b, the same shall apply hereinafter) is preferably 80:20 to 30:70, and 50:50 to 40: More preferably, it is 60.
- the ratio of both carbamoyl groups at the 3-position is preferably 40:60 to 10:90, and more preferably 15:85 to 10:90.
- Both of the two types of carbamoyl groups are preferably a substituted or unsubstituted phenyl group as a substituted or unsubstituted aryl group, more preferably a phenyl group having a substituent at the 3-position and the 5-position, More preferred is a 5-dichlorophenyl group or a 3,5-dimethylphenyl group.
- the carbamoyl group having the ratio represented by a above has a 3,5-dichlorophenyl group as a substituted or unsubstituted aryl group, and the carbamoyl group having the ratio represented by b above It is preferable to have a 3,5-dimethylphenyl group as the group.
- the polysaccharide derivative of the present embodiment is a case where the hydrogen atom of the 2-position, 3-position and 6-position hydroxyl group or amino group of the polysaccharide structural unit is substituted only with a predetermined carbamoyl group, and
- the carbamoyl group is composed of two kinds of carbamoyl groups
- the ratio of both carbamoyl groups at the 2-position (a: b, the same shall apply hereinafter) is preferably 80:20 to 30:70, and 50:50 More preferably, it is ⁇ 40: 60.
- the ratio of both carbamoyl groups at the 3-position is preferably 40:60 to 10:90, and more preferably 15:85 to 10:90.
- the ratio of both carbamoyl groups at the 6-position in this case is preferably 0: 100.
- Both of the two types of carbamoyl groups are preferably a substituted or unsubstituted phenyl group as a substituted or unsubstituted aryl group, more preferably a phenyl group having a substituent at the 3-position and the 5-position, More preferred is a 5-dichlorophenyl group or a 3,5-dimethylphenyl group.
- the carbamoyl group having the ratio represented by a above has a 3,5-dichlorophenyl group as a substituted or unsubstituted aryl group, and the carbamoyl group having the ratio represented by b above It is preferable to have a 3,5-dimethylphenyl group as the group.
- the polysaccharide derivative of this embodiment can be produced by the following method. That is, in the method for producing a polysaccharide derivative according to the present embodiment, the hydrogen atoms of the 2-position and 3-position hydroxyl groups or amino groups of the polysaccharide constituent units are monovalent represented by the same general formula (1).
- a polysaccharide derivative (hereinafter referred to as “raw material polysaccharide derivative”) that is a raw material including a structure substituted with a group is represented by the following general formula (3): R 2 -NCO (3) Or a monovalent group represented by the above general formula (1) substituted with a hydrogen atom of the 2-position or 3-position hydroxyl group or amino group by reacting the compound represented by A step of substituting a monovalent group represented by the formula (2).
- R 2 is the same meaning as R 2 in the general formula (2).
- a raw material polysaccharide derivative is prepared.
- the raw material polysaccharide derivative may be synthesized by a known method using the polysaccharide already described in detail as a raw material, or a commercially available product may be obtained.
- a cellulose derivative and an amylose derivative are preferable, and a cellulose derivative is more preferable from the viewpoint of obtaining the target polysaccharide derivative more quickly and reliably.
- Examples of the raw material polysaccharide derivative include cellulose tris (3,5-dichlorophenyl carbamate), cellulose tris (3,5-dimethylphenyl carbamate), cellulose trisphenyl carbamate, cellulose tris (4-methylphenyl carbamate), cellulose tris (4 -Chlorophenyl carbamate).
- cellulose tris (3,5-dichlorophenyl carbamate) and cellulose tris (3,5-dimethylphenyl carbamate) are preferable, and cellulose tris (3,5-dichlorophenyl carbamate) is preferred from the viewpoint of quickly obtaining the desired polysaccharide derivative. Is more preferable.
- the compound represented by the general formula (3) (hereinafter referred to as “predetermined isocyanate”) is reacted with the raw material polysaccharide derivative.
- predetermined isocyanate any one of the monovalent groups represented by the general formula (1) substituted by the hydrogen atom of the 2-position and 3-position hydroxyl groups or amino groups is represented by the general formula (2).
- the polysaccharide derivative of this embodiment can be synthesized by substituting with a monovalent group.
- this reaction is an equilibrium reaction between the carbamate and the isocyanate, the amount of the specified isocyanate used for the monovalent group represented by the general formula (1) in the raw polysaccharide derivative, the solvent, the reaction
- the substitution amount of the monovalent group represented by the general formula (2) can be controlled.
- cellulose tris (3,5-dichlorophenylcarbamate) is used as a raw material polysaccharide derivative and 3,5-dimethylphenyl isocyanate is used as a predetermined isocyanate.
- Cellulose tris (3,5-dichlorophenylcarbamate) is dissolved in a mixed solvent of DMA / pyridine / LiCl, and 3,5-dimethylphenylisocyanate is dissolved in 3,5-dimethylphenylcarbamate in cellulose tris (3,5-dichlorophenylcarbamate).
- cellulose tris (3,5-dimethylphenylcarbamate) is used as a raw material polysaccharide derivative and 3,5-dichlorophenyl isocyanate is used as a predetermined isocyanate.
- Cellulose tris (3,5-dimethylphenylcarbamate) was dissolved in a mixed solvent of DMAc / pyridine / LiCl, and 3,5-dichlorophenyl isocyanate was dissolved therein with 3,5 in cellulose tris (3,5-dimethylphenylcarbamate). -An excessive amount is added to the dimethylphenylcarbamoyl group and reacted at, for example, 80 ° C.
- the 3,5-dimethylphenylcarbamoyl group is replaced with the 3,5-dichlorophenylcarbamoyl group.
- the substitution starts from the 3,5-dimethylphenylcarbamoyl group at the 6-position, and then the 3,5-dimethylphenylcarbamoyl group starts substitution at the 3-position and the 2-position.
- the solvent used in the above reaction is not particularly limited as long as the raw material polysaccharide derivative dissolves.
- amide solvents such as DMAc and DMF
- pyridine solvents such as pyridine and quinoline
- dimethyl sulfoxide dimethyl sulfoxide
- the solvent may contain an ionic compound that promotes dissolution of the raw material polysaccharide derivative.
- ionic compounds include lithium halides such as LiCl and LiBr.
- reaction temperature and reaction time as desired.
- the polysaccharide derivative of the present embodiment can be used by being contained in a separating agent, and can be used particularly as a separating agent for optical isomers.
- the separating agent for optical isomers may be composed only of the polysaccharide derivative of this embodiment, or may be composed of a carrier such as silica gel and the polysaccharide derivative of this embodiment supported on this carrier. , It may be in the form of an integral unit housed in the column or in the form of particles packed in the column.
- the optical isomer separating agent is produced in the same manner as the known optical isomer separating agent containing a polysaccharide derivative, except that the polysaccharide derivative of the present embodiment is used. More specifically, the polysaccharide derivative of the present embodiment is supported on a carrier, or the polysaccharide derivative itself is crushed or spherical particles are obtained by a known method (for example, a method described in JP-A-7-285889). By making it, a separating agent for optical isomers can be prepared.
- the term “support” means that a polysaccharide derivative is immobilized on a carrier.
- a known loading method can be applied to the loading method, including physical adsorption between the polysaccharide derivative and the carrier, chemical bonding between the polysaccharide derivative and the carrier, chemical bonding between the polysaccharide derivatives, polysaccharide derivatives and Methods such as a chemical bond between one or both of the carriers and the third component, light irradiation to the polysaccharide derivative, radical reaction, etc. can be applied (see, for example, JP-A-6-93002).
- the carrier examples include a porous organic carrier and a porous inorganic carrier, and a porous inorganic carrier is preferable.
- the average pore diameter of the porous carrier is preferably 1 nm to 100 ⁇ m, more preferably 5 nm to 5 ⁇ m.
- the porous organic carrier for example, a polymer substance composed of polystyrene, polyacrylamide, polyacrylate and the like is suitable, and as the porous inorganic carrier, for example, silica, alumina, zirconia, magnesia, glass, kaolin, Titanium oxide, silicate and hydroxyapatite are preferred.
- the form of the porous inorganic carrier is not limited to a particulate carrier, but is an inorganic carrier having a network shape such as an organic-inorganic composite, or JP-A-2005-17268 or JP-A-2006-150214. It may be a columnar integrated inorganic carrier that can be held in a column as described in the publication.
- a particularly preferred carrier is silica gel, and the average particle size of the silica gel is preferably 1 ⁇ m to 1 mm, more preferably 1 ⁇ m to 300 ⁇ m, still more preferably 1 ⁇ m to 100 ⁇ m.
- the carrier may be subjected to treatment for improving the affinity with the polysaccharide derivative or modifying the surface properties of the carrier itself.
- the surface treatment method there are a silanization treatment with an organosilane compound and a surface treatment method by plasma polymerization.
- the amount of the polysaccharide derivative supported on the carrier is preferably 1 to 100 parts by weight, more preferably 5 to 60 parts by weight, and particularly preferably 10 to 40 parts by weight with respect to 100 parts by weight of the optical isomer separating agent. .
- the polysaccharide derivative of the present embodiment can be used for separation of diastereomers other than the optical isomer separating agent, for example.
- Example 1 First, cellulose tris (3,5-dichlorophenylcarbamate) was synthesized according to the method described in Y. Okamoto, M. Kawashima and K. Hatada, J. Chromatogr., 363, 173 (1986). The 1 H-NMR spectrum chart (500 MHz) is shown in FIG. Next, 1.2 g (1.65 mmol) of the obtained cellulose tris (3,5-dichlorophenylcarbamate) was dried at 80 ° C. for 5 hours in a vacuum necked flask in an oil bath.
- the reaction scheme is shown below. During the reaction, in order to confirm a reaction product at each reaction time described later, a part of the solution was collected and added to methanol to cause precipitation of the cellulose derivative. Further, the content of 3,5-dimethylphenylcarbamoyl group (DMPC) in the cellulose derivative obtained through filtration, washing with methanol and drying, and 3, 2- and 3-positions of 3, 3 in the constitutional unit of the cellulose derivative. The ratio of 5-dimethylphenylcarbamoyl group (DMPC) to 3,5-dichlorophenylcarbamoyl group (DCPC) was calculated by analysis by 1 H-NMR. The results are shown in Table 1.
- Example 2 cellulose tris (3,5-dimethylphenylcarbamate) was synthesized according to the method described in Y. Okamoto, M. Kawashima and K. Hatada, J. Chromatogr., 363, 173 (1986). The 1 H-NMR spectrum chart (500 MHz) is shown in FIG. Subsequently, 1.2 g (1.99 mmol) of the obtained cellulose tris (3,5-dimethylphenylcarbamate) was dried at 80 ° C. for 5 hours in a vacuum necked flask in an oil bath.
- the reaction scheme is shown below. During the reaction, in order to confirm a reaction product at each reaction time described later, a part of the solution was collected and added to methanol to cause precipitation of the cellulose derivative. Further, the content of 3,5-dimethylphenylcarbamoyl group (DMPC) in the cellulose derivative obtained through filtration, washing with methanol and drying, and 3, 2- and 3-positions of 3, 3 in the constitutional unit of the cellulose derivative. The ratio of 5-dimethylphenylcarbamoyl group (DMPC) to 3,5-dichlorophenylcarbamoyl group (DCPC) was calculated by analysis by 1 H-NMR. The results are shown in Table 2.
- Example 3 First, 2.5 g of cellulose was dissolved in a mixed solvent of DMAc / LiCl / pyridine (mixing ratio: 7.5 mL / 0.5 g / 3.75 mL). Next, 0.53 g of 3,5-dichlorophenyl isocyanate was added thereto and reacted at 80 ° C. for 12 hours under a dry nitrogen atmosphere. Next, 2 mL (14.2 mmol) of 3,5-dimethylphenyl isocyanate was added, followed by reaction at 80 ° C. for 12 hours under a dry nitrogen atmosphere. The obtained reaction product (cellulose derivative) was precipitated in methanol, and further purified by filtration, methanol washing and drying.
- a 1 H-NMR spectrum chart (500 MHz) of the reaction product is shown in FIG.
- the ratio of DMPC to DCPC in the reaction product was 83:17 in molar ratio.
- the ratio of DCPC in 2nd position (b), 3rd position (c), and 6th position (a) is substantially the same.
- Example 4 First, 2.5 g of cellulose was dissolved in a mixed solvent of DMAc / LiCl / pyridine (mixing ratio: 7.5 mL / 0.5 g / 3.75 mL). Next, 1.35 g of 3,5-dichlorophenyl isocyanate was added thereto and reacted at 80 ° C. for 39 hours under a dry nitrogen atmosphere. Next, 2 mL (14.2 mmol) of 3,5-dimethylphenyl isocyanate was added, followed by reaction at 80 ° C. for 24 hours under a dry nitrogen atmosphere. The obtained reaction product (cellulose derivative) was precipitated in methanol, and further purified by filtration, methanol washing and drying.
- a 1 H-NMR spectrum chart (500 MHz) of the reaction product is shown in FIG.
- the ratio of DMPC to DCPC in the reaction product was 73:27 in molar ratio.
- ratio of DCPC in 2nd-position (b), 3rd-position (c), and 6th-position (a) is 36:15:49.
- the reaction scheme of Example 3 (Run 1) and Example 4 (Run 2) is shown below.
- the optical resolution of the HPLC column packed with the cellulose derivative obtained in Examples 3 and 4 was evaluated by optical resolution of racemates 1 to 7 having the following structural formulas. According to the method described in Y. Okamoto, M. Kawashima and K. Hatada, J. Chromatogr., 363, 173 (1986) The cellulose derivative was coated, and each was packed in a column (length 25 cm ⁇ inner diameter 0.20 cm) to obtain an HPLC column. From the results of TG analysis, it was found that the cellulose derivative of Example 3 was coated at 25.0% by mass and the cellulose derivative of Example 4 was coated at 23.5% by mass with respect to the silica gel. The number of HPLC column stages was about 2000.
- Acac represents acetylacetonate
- Ph represents a phenyl group
- the HPLC column according to Example 3 shows better optical resolution than the HPLC column according to Example 4.
- the HPLC column according to Example 3 shows that the racemate 2 exhibits better optical resolution than cellulose tris (3,5-dimethylphenylcarbamate) and cellulose tris (3,5-dichlorophenylcarbamate). It was.
- the polysaccharide derivative of the present invention can function as a novel separating agent for optical isomers exhibiting interesting optical resolution.
- the polysaccharide derivative of the present invention has industrial applicability to separation agents such as optical isomer separation agents.
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Abstract
Description
R1-NH-CO- (1)
R2-NH-CO- (2)
(式(1)及び(2)中、R1及びR2は、互いに異なる置換又は未置換のアリール基を示す。)
R1-NH-CO- (1)
(式(1)中、R1は置換又は未置換のアリール基を示す。)
で表される1価の基に置換した構造を含む原料である多糖誘導体に対して、下記一般式(3):
R2-NCO (3)
(式(3)中、R2は、上記R1とは異なる置換又は未置換のアリール基を示す。)
で表される化合物を反応させることにより、上記2位及び3位の水酸基又はアミノ基の水素原子に置換した上記一般式(1)で表される1価の基のいずれか一方を、下記一般式(2):
R2-NH-CO- (2)
(式(2)中、R2は、上記一般式(3)におけるR2と同義である。)
で表される1価の基に置換する工程を備える、多糖誘導体の製造方法を提供する。
R1-NH-CO- (1)
R2-NH-CO- (2)
ここで、式(1)及び(2)中、R1及びR2は、互いに異なる置換又は未置換のアリール基を示す。なお、本明細書において、「アミノ基の水素原子」は、2つあるうちの一方の水素原子を意味する。
R2-NCO (3)
で表される化合物を反応させることにより、上記2位及び3位の水酸基又はアミノ基の水素原子に置換した上記一般式(1)で表される1価の基のいずれか一方を、上記一般式(2)で表される1価の基に置換する工程を備える。ここで、式(3)中、R2は、一般式(2)におけるR2と同義である。
まず、セルローストリス(3,5-ジクロロフェニルカルバメート)を、Y. Okamoto, M. Kawashima and K. Hatada, J. Chromatogr., 363, 173 (1986)に記載の方法に従って合成した。その1H-NMRスペクトルチャート(500MHz)を図1に示す。
次いで、得られたセルローストリス(3,5-ジクロロフェニルカルバメート)1.2g(1.65mmol)を、油浴中の減圧した2口フラスコ内にて、80℃で5時間乾燥した。次に、36mLの乾燥DMAcを12時間かけて添加し、更に2.4gのLiClを添加して室温で2時間撹拌し、最後に16.8mLの乾燥ピリジンを添加して80℃で4時間撹拌した。こうして、セルローストリス(3,5-ジクロロフェニルカルバメート)をDMAc/LiCl/ピリジンの混合溶媒に均一に溶解した溶液を得た。
次いで、その溶液に3,5-ジメチルフェニルイソシアナート9.6mL(68.23mmol)を添加して、アルミ箔で遮光し、乾燥窒素雰囲気下、80℃で48時間反応させた。その反応スキームを下記に示す。反応中、後述の各反応時間での反応生成物を確認するために、溶液を一部採取してメタノール中に添加することで、セルロース誘導体の沈殿を生じさせた。更に、濾過、メタノール洗浄及び乾燥を経て得られたセルロース誘導体における3,5-ジメチルフェニルカルバモイル基(DMPC)の含有量、及び、セルロース誘導体の構成単位において2位、3位及び6位の3,5-ジメチルフェニルカルバモイル基(DMPC)と3,5-ジクロロフェニルカルバモイル基(DCPC)との比率を、1H-NMRにより分析して算出した。結果を表1に示す。また、反応中(反応開始から20分、1時間、2時間、3時間、5時間、7時間、9時間、11時間及び13時間後)における反応生成物の1H-NMRスペクトルチャート(500MHz)を、それぞれ図2~9に示す。
まず、セルローストリス(3,5-ジメチルフェニルカルバメート)を、Y. Okamoto, M. Kawashima and K. Hatada, J. Chromatogr., 363, 173 (1986)に記載の方法に従って合成した。その1H-NMRスペクトルチャート(500MHz)を図10に示す。
次いで、得られたセルローストリス(3,5-ジメチルフェニルカルバメート)1.2g(1.99mmol)を、油浴中の減圧した2口フラスコ内にて、80℃で5時間乾燥した。次に、36mLの乾燥DMAcを12時間かけて添加し、更に2.4gのLiClを添加して室温で2時間撹拌し、最後に16.8mLの乾燥ピリジンを添加して80℃で4時間撹拌した。こうして、セルローストリス(3,5-ジメチルフェニルカルバメート)をDMAc/LiCl/ピリジンの混合溶媒に均一に溶解した溶液を得た。
次いで、その溶液に3,5-ジメチルフェニルイソシアナート5.6g(26.60mmol)を添加して、アルミ箔で遮光し、乾燥窒素雰囲気下、80℃で48時間反応させた。その反応スキームを下記に示す。反応中、後述の各反応時間での反応生成物を確認するために、溶液を一部採取してメタノール中に添加することで、セルロース誘導体の沈殿を生じさせた。更に、濾過、メタノール洗浄及び乾燥を経て得られたセルロース誘導体における3,5-ジメチルフェニルカルバモイル基(DMPC)の含有量、及び、セルロース誘導体の構成単位において2位、3位及び6位の3,5-ジメチルフェニルカルバモイル基(DMPC)と3,5-ジクロロフェニルカルバモイル基(DCPC)との比率を、1H-NMRにより分析して算出した。結果を表2に示す。また、反応中(反応開始から30分、1時間、2時間、3時間、5時間、7時間、9時間、11時間及び13時間後)における反応生成物の1H-NMRスペクトルチャート(500MHz)を、それぞれ図11~18に示す。
まず、セルロース2.5gをDMAc/LiCl/ピリジンの混合溶媒(混合比:7.5mL/0.5g/3.75mL)に溶解した。次いで、そこに0.53gの3,5-ジクロロフェニルイソシアナートを添加して、乾燥窒素雰囲気下、80℃で12時間反応させた。次に、2mL(14.2mmol)の3,5-ジメチルフェニルイソシアナートを添加して、引き続き乾燥窒素雰囲気下、80℃で12時間反応させた。得られた反応生成物(セルロース誘導体)をメタノール中で沈殿させ、更に、濾過、メタノール洗浄及び乾燥を経ることにより精製した。その反応生成物の1H-NMRスペクトルチャート(500MHz)を、図19に示す。反応生成物におけるDMPCとDCPCとの比は、モル比で83:17となった。また、2位(b)、3位(c)及び6位(a)におけるDCPCの比は、ほぼ同じであることがわかった。
まず、セルロース2.5gをDMAc/LiCl/ピリジンの混合溶媒(混合比:7.5mL/0.5g/3.75mL)に溶解した。次いで、そこに1.35gの3,5-ジクロロフェニルイソシアナートを添加して、乾燥窒素雰囲気下、80℃で39時間反応させた。次に、2mL(14.2mmol)の3,5-ジメチルフェニルイソシアナートを添加して、引き続き乾燥窒素雰囲気下、80℃で24時間反応させた。得られた反応生成物(セルロース誘導体)をメタノール中で沈殿させ、更に、濾過、メタノール洗浄及び乾燥を経ることにより精製した。その反応生成物の1H-NMRスペクトルチャート(500MHz)を、図20に示す。反応生成物におけるDMPCとDCPCとの比は、モル比で73:27となった。また、2位(b)、3位(c)及び6位(a)におけるDCPCの比は、36:15:49であることがわかった。
上記実施例3(Run1)及び実施例4(Run2)の反応スキームを下記に示す。
Claims (5)
- 多糖の構成単位が有する2位の水酸基又はアミノ基の水素原子を下記一般式(1)で表される1価の基に置換し、かつ、前記構成単位が有する3位の水酸基又はアミノ基の水素原子を下記一般式(2)で表される1価の基に置換した構造を含む、多糖誘導体。
R1-NH-CO- (1)
R2-NH-CO- (2)
(式(1)及び(2)中、R1及びR2は、互いに異なる置換又は未置換のアリール基を示す。) - 前記多糖がセルロース又はアミロースである、請求項1に記載の多糖誘導体。
- 前記R1が3,5-ジクロロフェニル基であり、前記R2が3,5-ジメチルフェニル基である、請求項1又は2に記載の多糖誘導体。
- 多糖の構成単位が有する2位及び3位の水酸基又はアミノ基の水素原子を、互いに同一の下記一般式(1):
R1-NH-CO- (1)
(式(1)中、R1は置換又は未置換のアリール基を示す。)
で表される1価の基に置換した構造を含む原料である多糖誘導体に対して、下記一般式(3):
R2-NCO (3)
(式(3)中、R2は、前記R1とは異なる置換又は未置換のアリール基を示す。)
で表される化合物を反応させることにより、前記2位及び3位の水酸基又はアミノ基の水素原子に置換した前記一般式(1)で表される1価の基のいずれか一方を、下記一般式(2):
R2-NH-CO- (2)
(式(2)中、R2は、前記一般式(3)におけるR2と同義である。)
で表される1価の基に置換する工程を備える、多糖誘導体の製造方法。 - 請求項1~3のいずれか一項に記載の多糖誘導体を含む分離剤。
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US20130116418A1 (en) | 2013-05-09 |
CN102311504A (zh) | 2012-01-11 |
JP5896903B2 (ja) | 2016-03-30 |
EP2592095A4 (en) | 2013-11-27 |
EP2592095A1 (en) | 2013-05-15 |
US9458186B2 (en) | 2016-10-04 |
EP2592095B1 (en) | 2017-05-24 |
CN102311504B (zh) | 2017-05-10 |
JPWO2012005245A1 (ja) | 2013-09-02 |
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