CN101863986B - Microcrystalline cellulose derivative and preparation method and application thereof - Google Patents
Microcrystalline cellulose derivative and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a microcrystalline cellulose derivative and a preparation method and application thereof. The general molecular formula of the microcrystalline cellulose derivative is [(XC6H4NHCO)2(C6H7O4)N3]n, wherein X is F, Cl, Br or I; n is a natural number from 15 to 375; and the structural formula of the microcrystalline cellulose derivative is shown as a formula (I). The microcrystalline cellulose derivative can be used as a chiral selective agent; and through the link effect of triazo, chemical bonds can be bonded to a silica gel carrier to form a bonded cellulose chiral stationary phase which is used for a high pressure liquid chromatograph, a gas chromatograph, a capillary electrophoresis apparatus, a supercritical fluid chromatograph and the like. The bonded cellulose chiral stationary phase prepared by the microcrystalline cellulose derivative of the invention has high chiral recognition capability and stability, and can be used for separating various different types of chiral medicaments.
Description
Technical field
The present invention relates to polysaccharides chiral stationary phase field, be specifically related to a kind of microcrystalline cellulose derivative.
Background technology
Chirality is one of human anti-natural essential attribute with existence, biomacromolecule such as protein, and nucleic acid, polysaccharide all have chirality.Carbohydrate tends to have D-form in the vital process, and amino acid almost all exists with the L-configuration, and life is built according to this D, L configuration.The solid of this biological stereoselectivity and optically active substance is synthetic, is the distinctive instinct of biosystem.Because the function of most drug is to interact through the biological substance with chirality just to manifest, and the isomer of each chiral drug might show as different pharmacological properties at aspects such as activity, the efficacy of a drug, toxicity, transporting mechanism and metabolism passages.Therefore,, reduce toxic side effect, the mechanism of action, toxicity and the drug manufacture of further investigation medicine, quality control, the problem of confirming to become a key in the medicine effect check of the identification of medicine chiral isomer and component concentration in order to improve the activity of medicine.
Chiral isomer has closely similar physicochemical property, only when interacting to polarized light and with other chiral molecules, just shows otherness.Therefore, the quantitative analysis method to the generalization compound commonly used at present is like water off a duck's back for chiral isomer.Because with HPLC separating optical isomeric body, confirm characteristics such as steric configuration has fast, makes things convenient for, cost is low.So far, up to ten thousand kinds of chiral compound enantiomers are separated, and the development with stationary phase of chiral recognition ability is the leading edge field of chiral separation technical development, also are the key and the cores of chiral chromatography stripping technique.HPLC extensively receives the attention of academia and industrial community in recent years, is considered to one of means of effective chiral separation and quantitative analysis.The present more general analytical procedure that grows up therefrom is HPLC (HPLC) or gc (GC), capillary electrophoresis (CE), the supercritical fluid chromatography (SFC) of band chiral separation post etc.
The development of CSP starts from the later stage seventies 20th century, undergoes an unusual development rapidly.A large amount of various types of CSP (as, cellulose family, cyclodextrin, protein-based is chiral crown ether class etc.) succeed in developing in succession.The CSP of part type has obtained widespread use as commodity selling in the chiral separation field.
The polysaccharides chiral stationary phase is showing huge advantage to have boundless application prospect aspect chirality Chiral Separation and the preparation.At present; Commercial polysaccharides chiral stationary phase majority is that the method that adopts physics to apply is coated in polysaccharide derivatives on the chromatography matrix; The reactive force of chiral selector and chromatography matrix is not firm, and therefore, chiral selector is easy to run off with moving phase; The selection of moving phase has received considerable restraint, thereby in chiral separation, has limitation.And chemically bonded class polysaccharide chiral stationary phase has overcome this shortcoming, has the wide advantage of moving phase range of choice.
Cellulosic molecular formula is (C
6H
10O
5)
nIt is to be that structural unit passes through 1 with β-glucose, the wire superpolymer that the 4-glycosidic link is formed by connecting, high-sequential on the space structure, type void structure in the shape of a spiral.Each structural unit has a primary hydroxyl and two secondary hydroxyls, lays respectively at C6 and C2, and on the C3 position, these hydroxyls are prone to modified and derivatize, show special chiral recognition ability.So derivatived cellulose is widely used in separating chiral compound as chiral selector.
At present, commercialization bonding type cellulose family chiral stationary phase kind also seldom, the research of bonding type cellulose chiral stationary phase is the focus in the present analysis field.
The multiple biological type of technology as chiral selector of Mierocrystalline cellulose of utilizing disclosed in the prior art.For example; U.S. Pat P 20090216006 discloses the Mierocrystalline cellulose 3 that a kind of vinyl silanes is modified; 5-3,5-dimethylphenyl carbamate chirality stationary phase, with chiral selector Mierocrystalline cellulose 3,5-3,5-dimethylphenyl carbamate is fixed on the matrix firmly through the polymerization between vinyl.U.S. Pat P 5811532 discloses with cellulose ester, and the Mierocrystalline cellulose phenylcarbamate is a chiral selector, forms chiral stationary phase with matrix through the chemical bond mould assembly.It is chiral selector that Chinese patent CN 200810225348.5 discloses with Mierocrystalline cellulose 2-phenylpropionic acid ester, is the space arm with the hexamethylene diisocyanate, with Mierocrystalline cellulose 2-phenylpropionic acid ester and silica gel bonded formation chiral stationary phase.Document (Tong Zhang et al./Analytica Chimica Acta 557 (2006) 221-228; T.Zhang et al./Journal of Pharmaceutical and Biomedical Analysis 46 (2008) 882-891) reported that respectively bonding type is with Mierocrystalline cellulose 3; 5-3,5-dimethylphenyl carbamate be stationary phase (CHIRALPAK IB) and the bonding type of chiral selector with Mierocrystalline cellulose 3,5-dichlorophenyl carbamate is the stationary phase (CHIRALPAK IC) of chiral selector.
But the shortcoming of the application type cellulose chiral stationary phase of prior art is that solvent is required height, and some organic solvent (as: trichloromethane, THF etc.) is to use as moving phase in separation.Though the bonding type cellulose chiral stationary phase of prior art has overcome some defectives of application type, separating chiral isomer limited amount has many chiral isomers to separate, even some obtains separating, but separating size is little.
Summary of the invention
The objective of the invention is to solvent required height according to what exist in the existing application type cellulose chiral stationary phase; Organic solvent can not use as moving phase in separation; The limited amount of bonding type cellulose chiral stationary phase; Defectives such as separating size is little; A kind of microcrystalline cellulose derivative is provided, and the chiral stationary phase that this verivate prepares is solvent widely applicable (water and common organic solvents all can) not only, and solved to existing bonding type cellulose chiral stationary phase can't isolating problem.
Another purpose of the present invention is to provide the preparation method of above-mentioned microcrystalline cellulose derivative.
Another purpose of the present invention is to provide the application of above-mentioned microcrystalline cellulose derivative.
Above-mentioned purpose of the present invention is achieved through following technical scheme:
A kind of microcrystalline cellulose derivative, this verivate are formed halobenzene formamyl and azido-replacement respectively through the hydrogen on the hydroxyl in the Microcrystalline Cellulose glucose structural unit, and its general molecular formula is [(XC
6H
4NHCO)
2(C
6H
7O
4) N
3]
nStructural formula is suc as formula shown in (I), and wherein, X is F, Cl, Br or I; N is the natural number between 15～375; Substituted to the halogeno-benzene formamyl is hydrogen and the hydrogen on 3 hydroxyls on 2 hydroxyls of glucose structural unit in the cellulosic molecule; Azido-is substituted to be the hydroxyl on 6 of glucose structural unit in the cellulosic molecule.
Formula (I).
The preparation method of microcrystalline cellulose derivative of the present invention comprises the steps:
(1) with Microcrystalline Cellulose, Methyl benzenesulfonyl halogen, Lithium chloride (anhydrous) be dissolved in the mixing solutions of triethylamine and DMAC N,N and react;
(2) get step (1) gained reaction product and sodiumazide and in DMSO, react, after reaction finishes reaction solution poured into and separate out deposition in the frozen water, filter;
(3) with step (2) gained resolution of precipitate in the mixed solution of pyridine and triethylamine, add the halogenophenyl isocyanic acid reacted, the reaction back adds methyl alcohol and separates out deposition, filters to collect to obtain microcrystalline cellulose derivative.
As a kind of preferred version, Microcrystalline Cellulose described in the step (1), it is 1: 10: 10 to the mol ratio of Methyl benzenesulfonyl halogen, Lithium chloride (anhydrous); The mixing solutions consumption of said triethylamine and DMAC N,N is 50～80, and the volume ratio of triethylamine and DMAC N,N is 1: 1.
As a kind of preferred version, reaction described in the step (1) is reaction under nitrogen protection, and temperature of reaction is-20～-8 ℃, and the reaction times is 24～48h.
As a kind of preferred version, the consumption of reaction product is 6～12g described in the step (2), and the consumption of sodiumazide is 0.1～0.2mol.
As a kind of preferred version, the consumption of the mixed solution of pyridine and triethylamine is 60～100ml described in the step (3), and the volume ratio of pyridine and triethylamine is 1: 1; Said consumption to the halogenophenyl isocyanic acid is 3～8g; The add-on of said methyl alcohol is 500ml.
As a kind of preferred version, temperature of reaction is 100 ℃ described in the step (3), and the reaction times is 48h.
Microcrystalline cellulose derivative of the present invention can be used as chiral selector; Method through chemically bonded is bonded to it on silica-gel carrier; Be suitable on HPLC (HPLC), gc (GC), capillary electrophoresis (CE), the supercritical fluid chromatography instruments such as (SFC) as the chiral separation stationary phase; Prepared stationary phase has very strong chiral recognition ability and good stability, can realize separating to the chiral drug of number of different types.
The structural formula of the chiral separation stationary phase that above-mentioned microcrystalline cellulose derivative prepares is suc as formula shown in (II), and wherein, R is to the halogeno-benzene formamyl; X is F, Cl, Br or I; N is the natural number between 15～375;
Formula (II).
The method of utilizing microcrystalline cellulose derivative of the present invention to prepare said chiral separation stationary phase comprises the steps:
(1) gets exsiccant ammonification silica gel, join in the THF, add microcrystalline cellulose derivative again and obtain mixture;
(2) with triphenylphosphine dissolved in THF and be added drop-wise to and react 2～10h in the said mixture, filter, product is transferred in the apparatus,Soxhlet's;
(3) use washing with acetone, remove the raw material and the reagent that do not react, vacuum-drying obtains the chiral separation stationary phase.
Compared with prior art, the present invention has following beneficial effect:
(1) microcrystalline cellulose derivative raw material sources of the present invention are extensive, and reaction conditions is gentle, and cost is low;
(2) microcrystalline cellulose derivative of the present invention is owing to be substituted with azido group on the cellulosic hydroxyl; Make this chiral selector can be connected on carrier silica gel or the silica tube inwall through the mode of chemically bonded; Thereby form stable stationary phase; Overcome that moving phase can be used on HPLC (HPLC), gc (GC), capillary electrophoresis (CE), the supercritical fluid chromatography instruments such as (SFC) the destruction of chiral selector in the application type cellulose family chiral stationary phase;
(3) microcrystalline cellulose derivative of the present invention is as chiral selector, owing on Mierocrystalline cellulose, contain π-electron-donating group promptly to halogeno-benzene formamyl (XC
6H
4NHCO-) and azido-(N
3), have a plurality of can (N H C=O), can produce certain space multistory chemical action, thereby isolating chipal compounds be widely applicable, and effect is good with the site of analyte generation interaction of hydrogen bond.
Description of drawings
Fig. 1 is cellulosic molecular structure;
Fig. 2 is cellulosic microscopic three-dimensional structural synoptic diagram.
Embodiment
Come further to explain the present invention below in conjunction with embodiment, but embodiment does not do any type of qualification to the present invention.
(1) 6-(4-Methyl benzenesulfonyl base)-cellulosic preparation:
In the 1000ml three-necked bottle of magnetic stirring apparatus and TM is housed; Add Microcrystalline Cellulose 0.04mol; Add 0.40mol Lithium chloride (anhydrous) and 0.40mol right-mixing solutions that methylbenzene semi-annular jade pendant acyl chlorides joins 50ml triethylamine and DMA is (among the v/v=1/1; Then this mixing solutions is added drop-wise in the reaction flask, nitrogen protection was-20 ℃ of following stirring reactions 24 hours; After reaction finishes, slowly be poured in the 2500ml frozen water, separate out yellow mercury oxide, filter, obtain yellow solid, use deionized water, the washing with alcohol solid, drying under vacuum overnight promptly obtains xanchromatic solid 6-(4-Methyl benzenesulfonyl base)-Mierocrystalline cellulose, about 12 grams of its output.
(2) 6-nitrine-6-deoxidation-cellulosic preparation:
In the three-necked bottle that magnetic stirring apparatus, TM and reflux condensing tube are housed; Add step (1) gained to Methyl benzenesulfonyl base Mierocrystalline cellulose 6 gram and 300ml DMSO; The back is to wherein adding the 0.1mol sodiumazide, and the oil bath control reaction temperature is 100 ℃, stirring reaction 24 hours.Cooling slowly is poured into 2500ml, separates out the grey black flocks, filters, and uses absolute ethanol washing, and 50 ℃ of vacuum-dryings promptly got purpose product A Z-Mierocrystalline cellulose in 12 hours, about 5.5 grams of its output.
(3) 6-nitrine-2,3-two (to the halogeno-benzene formamyl)-cellulosic preparation:
In the three-necked bottle that magnetic stirring apparatus and TM are housed, the product of step (2) 5 grams are dissolved in the mixed solution (v/v=1/1) of 60ml pyridine and triethylamine; After the dissolving, add 3 grams to the halogenophenyl isocyanic acid, the heating control reaction temperature is 100 ℃ of stirring reactions 48 hours; Solid after concentrating is joined in the 500ml methyl alcohol, stir, filter, obtain solid; With the cable-styled washing of methyl alcohol 24 hours, be drying to obtain chiral selector 6-nitrine of the present invention-(2,3-phenyl-dihalide formamyl)-Mierocrystalline cellulose then, about 13 grams of its output.
(4) the bonded chiral stationary phase is synthetic
Take by weighing 4.0g exsiccant ammonification silica gel; Add in the THF of 20ml, add the synthetic 6-nitrine-2 that obtains of 5 gram steps (3), 3-two (to the halogeno-benzene formamyl)-Mierocrystalline cellulose; With the 2g triphenylphosphine dissolved in the 20ml THF and be added drop-wise in the said mixture, normal temperature reaction 2 hours down.Filter, product is transferred in the apparatus,Soxhlet's, use washing with acetone, remove the raw material and the reagent that do not react.Vacuum-drying obtains product 7 grams approximately.
(1) 6-(4-Methyl benzenesulfonyl base)-cellulosic preparation:
In the 1000ml three-necked bottle of magnetic stirring apparatus and TM is housed; Add Microcrystalline Cellulose 0.06mol; Add 0.60mol Lithium chloride (anhydrous) and 0.60mol right-methylbenzene semi-annular jade pendant acyl chlorides joins in the mixing solutions (v/v=1/1) of 60ml triethylamine and DMA; Then this mixing solutions is added drop-wise in the reaction flask, nitrogen protection was-16 times stirring reactions 32 hours; After reaction finishes, slowly be poured in the 2500ml frozen water, separate out yellow mercury oxide, filter, obtain yellow solid, use deionized water, the washing with alcohol solid, drying under vacuum overnight promptly obtains xanchromatic solid 6-(4-Methyl benzenesulfonyl base)-Mierocrystalline cellulose, about 14 grams of its output.
(2) 6-nitrine-6-deoxidation-cellulosic preparation:
In the 1000ml three-necked bottle of magnetic stirring apparatus, TM and reflux condensing tube is housed; Add step (1) gained to Methyl benzenesulfonyl base Mierocrystalline cellulose 9 gram and 300ml DMSO; To wherein adding the 0.15mol sodiumazide, the oil bath control reaction temperature is 100 ℃ then, stirring reaction 24 hours.Cooling slowly is poured into 2500ml, separates out the grey black flocks, filters, and uses absolute ethanol washing, and 50 ℃ of vacuum-dryings promptly got purpose product A Z-Mierocrystalline cellulose in 12 hours, about 7.5 grams of its output.
(3) 6-nitrine-2,3-two (to the halogeno-benzene formamyl)-cellulosic preparation:
In the three-necked bottle that magnetic stirring apparatus and TM are housed, the product of step (2) 5 grams are dissolved in the mixed solution (v/v=1/1) of 80ml pyridine and triethylamine; After the dissolving, add 5 grams to the halogenophenyl isocyanic acid, the heating control reaction temperature is 100 ℃ of stirring reactions 48 hours; Solid after concentrating is joined in the 500ml methyl alcohol, stir, filter, obtain solid; With the cable-styled washing of methyl alcohol 24 hours, be drying to obtain chiral selector 6-nitrine of the present invention-(2,3-phenyl-dihalide formamyl)-Mierocrystalline cellulose then, about 16 grams of its output.
(4) chiral stationary phase is synthetic
Take by weighing 4.0g exsiccant ammonification silica gel; Add in the THF of 20ml, add the synthetic 6-nitrine-2 that obtains of 8 gram steps (3), 3-two (to the halogeno-benzene formamyl)-Mierocrystalline cellulose; With the 3g triphenylphosphine dissolved in the 20ml THF and be added drop-wise in the said mixture, normal temperature reaction 2 hours down.Filter, product is transferred in the apparatus,Soxhlet's, use washing with acetone, remove the raw material and the reagent that do not react.Vacuum-drying obtains product 6 grams approximately.
(1) 6-(4-Methyl benzenesulfonyl base)-cellulosic preparation:
In the 1000ml three-necked bottle of magnetic stirring apparatus and TM is housed; Add Microcrystalline Cellulose 0.08mol; Add 0.80mol Lithium chloride (anhydrous) and 0.80mol right-methylbenzene semi-annular jade pendant acyl chlorides joins in the mixing solutions (v/v=1/1) of 80ml triethylamine and DMA; Then this mixing solutions is added drop-wise in the reaction flask, nitrogen protection was-8 times stirring reactions 48 hours; After reaction finishes, slowly be poured in the 2500ml frozen water, separate out yellow mercury oxide, filter, obtain yellow solid, use deionized water, the washing with alcohol solid, drying under vacuum overnight promptly obtains xanchromatic solid 6-(4-Methyl benzenesulfonyl base)-Mierocrystalline cellulose, about 18 grams of its output.
(2) 6-nitrine-6-deoxidation-cellulosic preparation:
In the 1000ml three-necked bottle of magnetic stirring apparatus, TM and reflux condensing tube is housed; Add step (1) gained to Methyl benzenesulfonyl base Mierocrystalline cellulose 12 gram and 300ml DMSO; To wherein adding the 0.2mol sodiumazide, the oil bath control reaction temperature is 100 ℃ then, stirring reaction 24 hours.Cooling slowly is poured into 2500ml, separates out the grey black flocks, filters, and uses absolute ethanol washing, and 50 ℃ of vacuum-dryings promptly got purpose product A Z-Mierocrystalline cellulose in 12 hours, about 10 grams of its output.
(3) 6-nitrine-2,3-two (to the halogeno-benzene formamyl)-cellulosic preparation:
In the three-necked bottle that magnetic stirring apparatus and TM are housed, the product of step (2) 5 grams are dissolved in the mixed solution (v/v=1/1) of 100ml pyridine and triethylamine; After the dissolving, add 8 grams to the halogenophenyl isocyanic acid, the heating control reaction temperature is 100 ℃ of stirring reactions 48 hours; Solid after concentrating is joined in the 500ml methyl alcohol, stir, filter, obtain solid; With the cable-styled washing of methyl alcohol 24 hours, be drying to obtain chiral selector 6-nitrine of the present invention-(2,3-phenyl-dihalide formamyl)-Mierocrystalline cellulose then, about 18 grams of its output.
(4) chiral stationary phase is synthetic
Take by weighing 4.0g exsiccant ammonification silica gel; Add in the THF of 20ml; Add the synthetic 6-nitrine-2 that obtains of 10 gram steps (3); 3-two (to the halogeno-benzene formamyl)-Mierocrystalline cellulose, with the 4g triphenylphosphine dissolved in the 20ml THF and be added drop-wise in the said mixture, normal temperature reaction 10 hours down.Filter, product is transferred in the apparatus,Soxhlet's, use washing with acetone, remove the raw material and the reagent that do not react.Vacuum-drying obtains product 8 grams approximately.
The chiral selector 6-nitrine that embodiment 1, embodiment 2 and embodiment 3 make-(2,3-phenyl-dihalide formamyl)-cellulosic structure records through ultimate analysis, ir spectra (IR) and confirms.
Chiral selector 6-nitrine-(2,3-phenyl-dihalide formamyl)-Mierocrystalline cellulose: IR (cm
-1) 3297 (N-Hstr), 3072 (=C-H), 2108 (N
3Str), 1722 (C=O str), 1591,1560,1491 (C=C aromatic nucleus str), 1088 (sym C-O-C); Ultimate analysis is by molecular formula [(ClC
6H
4NHCO)
2(C
6H
7O
4) N
3]
nCalculated value: C48.58%, H 3.44%, and N 14.17%; Measured value: C 50.09%, H 4.68%, and N 13.83%.
Claims (5)
1. a microcrystalline cellulose derivative is characterized in that its general molecular formula is [(XC
6H
4NHCO)
2(C
6H
7O
4) N
3]
nThe structural formula of said microcrystalline cellulose derivative is suc as formula shown in (I), and wherein, X is F, Cl, Br or I; N is the natural number between 15～375; Substituted to the halogeno-benzene formamyl is hydrogen and the hydrogen on 3 hydroxyls on 2 hydroxyls of glucose structural unit in the cellulosic molecule; Azido-is substituted to be the hydroxyl on 6 of glucose structural unit in the cellulosic molecule;
Formula (I).
2. the preparation method according to the said microcrystalline cellulose derivative of claim 1 is characterized in that comprising the steps:
(1) with Microcrystalline Cellulose, Methyl benzenesulfonyl halogen, Lithium chloride (anhydrous) be dissolved in the mixing solutions of triethylamine and DMAC N,N and react;
(2) get step (1) gained reaction product and sodiumazide and in DMSO, react, after reaction finishes reaction solution poured into and separate out deposition in the frozen water, filter;
(3) with step (2) gained resolution of precipitate in the mixed solution of pyridine and triethylamine, add the halogenophenyl isocyanic acid reacted, the reaction back adds methyl alcohol and separates out deposition, filters to collect to obtain microcrystalline cellulose derivative;
Microcrystalline Cellulose described in the step (1), it is 1: 10: 10 to the mol ratio of Methyl benzenesulfonyl halogen, Lithium chloride (anhydrous); The mixing solutions consumption of said triethylamine and DMAC N,N is 50～80ml, and the volume ratio of triethylamine and DMAC N,N is 1: 1; Said reaction is reaction under nitrogen protection, and temperature of reaction is-20～-8 ℃, and the reaction times is 24～48h; The consumption of reaction product is 6～12g described in the step (2), and the consumption of sodiumazide is 0.1～0.2mol; The consumption of the mixed solution of said pyridine and triethylamine is 60～100ml, and the volume ratio of pyridine and triethylamine is 1: 1; Said consumption to the halogenophenyl isocyanic acid is 3～8g; The add-on of said methyl alcohol is 500ml; Said temperature of reaction is 100 ℃, and the reaction times is 48h.
3. application according to the said microcrystalline cellulose derivative of claim 1 is characterized in that said microcrystalline cellulose derivative as chiral selector, is used to prepare the chiral separation stationary phase.
4. chiral separation stationary phase according to claim 3, the structural formula that it is characterized in that said chiral separation stationary phase is suc as formula shown in (II), and wherein, R is to the halogeno-benzene formamyl; X is F, Cl, Br or I; N is the natural number between 15～375;
Formula (II).
5. one kind is used to prepare the method for chiral separation stationary phase according to the said microcrystalline cellulose derivative of claim 3, it is characterized in that comprising the steps:
(1) gets exsiccant ammonification silica gel, join in the THF, add microcrystalline cellulose derivative again and obtain mixture;
(2) with triphenylphosphine dissolved in THF and be added drop-wise to and react 2～10h in the said mixture, filter, product is transferred in the apparatus,Soxhlet's;
(3) use washing with acetone, remove the raw material and the reagent that do not react, vacuum-drying obtains the chiral separation stationary phase.
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