CN105017437A - Regioselective synthesis and application methods for amylose derivatives with different carbamate side groups - Google Patents
Regioselective synthesis and application methods for amylose derivatives with different carbamate side groups Download PDFInfo
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Abstract
The invention provides regioselective synthesis and application methods for amylose derivatives with different carbamate side groups. The synthesis method comprises taking amylose as an initial raw material, firstly introducing a tert-butyldimethylsilyl ester at 2- and 6- positions of a sugar unit of amylase as a protective group, then introducing a phenylcarbamic acid ester group at 3- position of the sugar unit, then in an alkali solution, removing the protective group and reducing hydroxyl at 2- and 6- positions, and finally introducing another kind phenylcarbamic acid ester group at 2- and 6- positions at the same time so as to finally realize regioselective synthesis of the amylose derivatives. On the basis, the synthesized novel amylose derivative is fully dissolved, the surface of silica gel is uniformly coated with the polymer through a coating process, and a column is packed by employing a homogenating process, so that a novel amylose chiral stationary phase is prepared. high performance liquid chromatography is applicable to detailed evaluation on the chiral recognition performance of the prepared chiral stationary phase.
Description
Technical field
That the present invention relates to is a kind of synthetic method of amylose starch analog derivative and the preparation method of chiral stationary phase thereof.
Background technology
Along with the development of biotechnology and life science, the demand of people to the chiral stationary phase material with new and effective chiral recognition constantly increases, the chiral recognition efficiency of chiral stationary phase and the requirement of the scope of application also more and more higher.So far, polyose (especially starch and Mierocrystalline cellulose) derivative applies the most effectively and one of chiral stationary phase material the most widely.This is because polysaccharide is Optically active polymer abundant and the most important on the earth, and on its glucose unit, the hydroxyl of three positions is easy to be substituted, and modified polysaccharide derivatives is comparatively outstanding to the chiral recognition of all kinds of optical antipode.Tradition amylose starch analog derivative introduces the identical substituting group of structure usually on sugar unit 2-﹑ 3-position with 6-position, and relatively less for introducing the substituent research of different structure on sugar unit three positions respectively, which greatly limits the development of amylose starch analog derivative and the annotation of chiral recognition mechanis thereof.For amylose starch analog derivative, have been reported and show to replace (Bull Chem Soc Jpn, 1993,66,2225) by the 6-position protection method selectivity realized between 2-, 3-position and 6-position.In addition, the selectivity that applicant successfully realizes between amylose starch sugar unit 2-position and 3-, 6-position in recent years replaces, and the while of between position, three, 2-, 3-, 6-position, selectivity introduces three kinds of different groups (J Chromatogr A, 2010,1217,1041).Research shows, the substituting group introduced of three positions all has considerable influence for the chiral recognition performance of amylose starch analog derivative.Meanwhile, such trial not only makes type and the textural association more variation of polysaccharide derivatives, and can develop the higher novel chiral stationary phase of chiral recognition performance, and can further investigate the chiral recognition mechanis of polysaccharide derivatives further.So far, be not also in the news for realizing the synthetic method that selectivity replaces between amylose starch sugar unit 2-, 6-position and 3-position.And explore that to introduce different performance and the substituent method of structure at the different positions of polysaccharide significant for the further investigation of the synthetic method and chiral recognition mechanis thereof of expanding polysaccharide derivatives, for life and biomedicine field, there is larger theory and practice value.
Summary of the invention
The object of the present invention is to provide a kind of raw material sources extensive, cheap and easy to get, synthesis technique is simple, be easy to control, the Regioselective synthesis of what productive rate was high have different carbamate sides base amylose starch analog derivative.The present invention also aims to provide a kind of application method with different carbamate sides base amylose starch analog derivative.
The Regioselective synthesis with different carbamate sides base amylose starch analog derivative of the present invention comprises:
Step one: by the amylose starch of drying at 120 DEG C ± 5 DEG C temperature, stir 2-6h in anhydrous N,N-dimethylacetamide; The lithium chloride of 1.5 ~ 2 times of amylose starch quality is added after being cooled to 100 DEG C ± 5 DEG C; Continue to stir 2-6h, add imidazo and stir, then add the tertiary hexyl chloride SiClx of excessive dimethyl, be again warming up to 100 DEG C ± 5 DEG C, Keep agitation backflow 18-24h; Be cooled to room temperature, add damping fluid sedimentation filtration, with ethanol and water washing, 40-60 DEG C of vacuum-drying, to constant weight, obtains 2-, 6-position protection intermediate product;
Step 2: by above-mentioned 2-, 6-position protection intermediate product vacuum-drying 2-4h at 80 DEG C ± 5 DEG C temperature, then reflux 4-10h in anhydrous pyridine, adds excessive phenyl isocyanate NCO-R after being warming up to 100 DEG C ± 5 DEG C
1, at 100 DEG C ± 5 DEG C, continue backflow 12-16h, fully wash and vacuum-drying with methyl alcohol;
Step 3: be dissolved in by step 2 gained intermediate product in the tetrahydrofuran solution containing tetrabutyl ammonium fluoride and be hydrolyzed, stir 24h at 50 DEG C, by methanol wash and vacuum-drying;
Step 4: step 3 products therefrom is dissolved in anhydrous pyridine the 4-10h that refluxes at 100 DEG C ± 5 DEG C, then add another kind of excessive phenyl isocyanate NCO-R
2, continue backflow 12-16h at 80-100 DEG C, in detection reaction system, isocyanic ester is excessive, stopped reaction; Add methyl alcohol, fully washing, to filter and vacuum-drying obtains having different carbamate sides base amylose starch analog derivative at 40-60 DEG C;
Wherein NCO-is isocyanate groups, R
1be 3,5-dichlorophenyl, R
2for 3-chloro-phenyl-; R
1for 4-chloro-phenyl-, R
2for 3-aminomethyl phenyl; R
1for phenyl, R
2for 3-aminomethyl phenyl.
The application method with different carbamate sides base amylose starch analog derivative of the present invention is: have different carbamate sides base amylose starch analog derivative for the preparation of chiral stationary phase, there is different carbamate sides base amylose starch analog derivative be fully dissolved in tetrahydrofuran (THF), then coating process is used evenly to be coated in the surface of macropore Aminopropyl silica gel, and adopt homogenate method to fill post, complete the preparation of chiral stationary phase, the particle diameter 7 μm of described macropore Aminopropyl silica gel, aperture 100nm.
The present invention take amylose starch as initial raw material; first on sugar unit 2-, 6-position of amylose starch, introduce the tertiary hexyl estersil of dimethyl as blocking group simultaneously; then on sugar unit 3-position, a kind of phenylcarbamate group is introduced; take off in basic solution subsequently blocking group reductase 12-, 6-position hydroxyl; finally on 2-, 6-position, introduce another kind of phenylcarbamate group simultaneously, finally realize the regio-selective synthesis of straight chain starch derivative.On this basis, after fully being dissolved by synthesized novel straight chain starch derivative, use coating process that polymer uniform is coated in Silica Surface, adopt homogenate method dress post, prepare novel Amylose Chiral Stationary Phase.Detailed assessment is carried out by the chiral recognition performance of high performance liquid chromatography to prepared chiral stationary phase.
Clear feasible, the technical maturity of above synthetic route, simple to operate and be easy to realize, can be used for large-scale batch production.The compound with regular structure of synthesized derivative, and meet expection composite structure target.
Chromatographic results in the table 1 of Fig. 7 shows, this novel straight chain starch domains selectivity substitutive derivative demonstrates outstanding chiral recognition performance to various racemic modification, especially for Wen Zhongliu kind enantiomorph, be respectively Te Luojie alkali (Fig. 2-1), trans 2, 3-phenylbenzene oxyethane (Fig. 2-2), bitter almond oil camphor (Fig. 2-3), triacetyl pyruvic acid cobalt (Fig. 2-6), flavanone (Fig. 2-7) and (+/-)-propranolol hydrochloride (Fig. 2-10), baseline separation completely can be realized, and for Te Luojie alkali (Fig. 2-1), the separating effect of bitter almond oil camphor (Fig. 2-3) and flavanone (Fig. 2-7) three kinds of enantiomorphs has exceeded effect optimum in the chiral column of current commercial goods and single monobasic ChiralcelAD post, show that prepared novel regioselectivity straight chain starch derivative chiral stationary phase has larger practical value and market development potential.Wherein, novel straight chain starch derivative---amylose starch-[2,6-bis-(3-methyl phenyl carbamate)-3-phenylcarbamate] shown in Figure 6 for the Chromatographic resolution spectrogram of flavanone (Fig. 2-7) enantiomorph, this derivative achieves baseline separation completely for flavanone enantiomorph as we can see from the figure, and separating effect is considerably beyond chirality commodity post ChiralcelAD.
Accompanying drawing explanation
Fig. 1 is the regio-selective synthesis route of straight chain starch derivative of the present invention.The substituting group that three kinds of straight chain starch derivatives synthesized in Fig. 1 are introduced is respectively: R
1it is 3,5-dichlorophenyl
r
2for 3-chloro-phenyl-
r
1for 4-chloro-phenyl-
r
2for 3-aminomethyl phenyl
r
1for phenyl
r
2for 3-aminomethyl phenyl
Fig. 2-1 to Fig. 2-10 is the structure of 10 kinds of racemic modifications for evaluating novel chiral stationary phase chiral recognition performance.Wherein, Fig. 2-1 is Te Luojie alkali, and Fig. 2-2 is trans 2; 3-phenylbenzene oxyethane, Fig. 2-3 is bitter almond oil camphor, and Fig. 2-4 is 2-phenyl hexamethylene; Fig. 2-5 is 2,2,2-Trifluoromethyl-1-(9-anthryl)-ethanol; Fig. 2-6 is triacetyl pyruvic acid cobalt; Fig. 2-7 is flavanone, and Fig. 2-8 is 2,2-dimethyl-1-phenyl-propanol; Fig. 2-9 is dinaphthol, and Fig. 2-10 is propranolol hydrochloride.
Fig. 3 be synthesized amylose starch-[2,6-bis-(3-meta-chlorocarbanilate)-3-(3,5-dichlorophenyl carbamate)] (1a) proton nmr spectra (
1h-NMR) (500MHz, deuterated pyridine, 80 DEG C).
Fig. 4 be synthesized amylose starch-[2,6-bis-(3-methyl phenyl carbamate)-3-(4-meta-chlorocarbanilate)] (1b) proton nmr spectra (
1h-NMR) (500MHz, deuterated pyridine, 80 DEG C).
Fig. 5 be synthesized amylose starch-[2,6-bis-(3-methyl phenyl carbamate)-3-phenylcarbamate] (1c) proton nmr spectra (
1h-NMR) (500MHz, deuterated pyridine, 80 DEG C).
Fig. 6 is synthesized amylose starch-[2,6-bis-(3-methyl phenyl carbamate)-3-phenylcarbamate] (1c) the Chromatographic resolution spectrogram for flavanone enantiomorph.
Fig. 7 is the chiral separation result tables of three kinds of straight chain starch derivatives for ten kinds of racemic modifications.
Embodiment
Technical scheme of the present invention mainly comprises:
1. get amylose starch vacuum-drying 2-4h under high temperature, heat up, then in anhydrous N,N-dimethylacetamide, stir 2-6h; Lithium chloride (quality is 1.5 times of amylose starch quality) is added after suitable cooling; Continue to stir 2-6h, add imidazo and stir, then add the tertiary hexyl chloride SiClx of excessive dimethyl, again heat up, stopped reaction after Keep agitation backflow 18-24h; Be cooled to room temperature, add damping fluid sedimentation filtration, with ethanol and water washing, 40-60 DEG C of vacuum-drying is to constant weight, and productive rate is 70-95%.
2. above-mentioned 2-, 6-position protection intermediate product is continued vacuum-drying 2-4h under high temperature, then reflux 4-10h in anhydrous pyridine, adds excessive phenyl isocyanate (NCO-R after intensification
1, wherein NCO-is isocyanate groups, R
1represent three kinds of different substituents respectively, as shown in Figure 1), at 100 DEG C, stopped reaction after continuation backflow 12-16h, fully washs and vacuum-drying with methyl alcohol.
3. previous step gained intermediate product is dissolved in the tetrahydrofuran solution containing tetrabutyl ammonium fluoride and is hydrolyzed, at 50 DEG C, stir 24h stopped reaction; Still by methanol wash and vacuum-drying, productive rate is 60-85%.
4. above product is fully dissolved in anhydrous pyridine the 4-10h that refluxes under high temperature, then adds another kind of excessive phenyl isocyanate (NCO-R
2, wherein NCO-is isocyanate groups, R
2represent two kinds of different substituents respectively, as shown in Figure 1), continue backflow 12-16h at 80-100 DEG C, in detection reaction system, isocyanic ester is excessive, stopped reaction; Add methyl alcohol, fully wash, filter and vacuum-drying at 40-60 DEG C, productive rate is 85-100%.
5. synthesized final product is fully dissolved in tetrahydrofuran (THF), then coating process is used polymer uniform to be coated in the surface of macropore Aminopropyl silica gel (particle diameter 7 μm, aperture 100nm), and adopt homogenate method to fill post, complete the preparation of chiral stationary phase.
Illustrate below and the present invention is described in more detail.
Embodiment one:
1. get 1g amylose starch vacuum-drying 4h at 105 DEG C, be warming up to 120 DEG C, then stirring and refluxing 4h in anhydrous N,N-dimethylacetamide; 1.5g lithium chloride is added after being cooled to 100 DEG C; Continue to stir 2h, after being cooled to room temperature, add 2.02g imidazoles; Add the tertiary hexyl chloride SiClx of excessive dimethyl after backflow 20min, be again warming up to 100 DEG C, stopped reaction after Keep agitation backflow 24h; Be cooled to room temperature, add damping fluid (adding 3.54g potassium primary phosphate and 7.14g dipotassium hydrogen phosphate in 1000ml distilled water) sedimentation filtration, with second alcohol and water (volume ratio 9:1) washing, 60 DEG C of vacuum-dryings are to constant weight, and productive rate is 80%.
2. by above-mentioned intermediate product vacuum-drying 3h at 80 DEG C, then reflux 6h in anhydrous pyridine, adds 3,5-excessive dichlorophenyl isocyanates after being warming up to 100 DEG C, and at 100 DEG C, stopped reaction after continuation backflow 12h, fully washs and vacuum-drying with methyl alcohol.
3. previous step gained intermediate product is dissolved in the tetrahydrofuran solution containing tetrabutyl ammonium fluoride (quality is 4 times for amylose starch molar equivalent) and is hydrolyzed, at 50 DEG C, stir 24h stopped reaction; By methanol wash and vacuum-drying, productive rate is 75%.
4. above product is fully dissolved in anhydrous pyridine the 6h that refluxes under high temperature, then adds excessive 3-chlorophenyl isocyanate, continue backflow 12h at 100 DEG C, in detection reaction system, isocyanic ester is excessive, stopped reaction; With the abundant washing and filtering of methyl alcohol and vacuum-drying at 60 DEG C, finally obtain amylose starch-[2,6-bis-(3-meta-chlorocarbanilate)-3-(3,5-dichlorophenyl carbamate)], productive rate is 93%.
5. synthesized final product 0.2g is dissolved in 7mL tetrahydrofuran (THF), then coating process is used polymer uniform to be coated in the surface of macropore Aminopropyl silica gel (particle diameter 7 μm, aperture 100nm), and adopt homogenate method to fill post, complete amylose starch-[2,6-bis-(3-meta-chlorocarbanilate)-3-(3,5-dichlorophenyl carbamate)] preparation of chiral stationary phase.
Amylose starch that the present invention obtains-[2,6-bis-(3-meta-chlorocarbanilate)-3-(3,5-dichlorophenyl carbamate)] productive rate high, structural regularity good (molecular structure characterization the results are shown in Figure 3), and there is outstanding chiral recognition performance.
Embodiment two:
1. get 1g amylose starch vacuum-drying 4h at 105 DEG C, be warming up to 120 DEG C, then stirring and refluxing 4h in anhydrous N,N-dimethylacetamide; 1.5g lithium chloride is added after being cooled to 100 DEG C; Continue to stir 2h, after being cooled to room temperature, add 2.02g imidazoles; Add the tertiary hexyl chloride SiClx of excessive dimethyl after backflow 20min, be again warming up to 100 DEG C, stopped reaction after Keep agitation backflow 24h; Be cooled to room temperature, add damping fluid (adding 3.54g potassium primary phosphate and 7.14g dipotassium hydrogen phosphate in 1000ml distilled water) sedimentation filtration, with second alcohol and water (volume ratio 9:1) washing, 60 DEG C of vacuum-dryings are to constant weight, and productive rate is 80%.
2. by above-mentioned intermediate product vacuum-drying 4h at 80 DEG C, then reflux 6h in anhydrous pyridine, adds excessive 4-chlorophenyl isocyanate after being warming up to 100 DEG C, and at 100 DEG C, stopped reaction after continuation backflow 14h, fully washs and vacuum-drying with methyl alcohol.
3. previous step gained intermediate product is dissolved in the tetrahydrofuran solution containing tetrabutyl ammonium fluoride (quality is 4 times for amylose starch molar equivalent) and is hydrolyzed, at 50 DEG C, stir 24h stopped reaction; By methanol wash and vacuum-drying, productive rate is 78%.
4. above product is fully dissolved in anhydrous pyridine the 7h that refluxes under high temperature, then adds excessive 3-methylphenyl isocyanate, continue backflow 12h at 100 DEG C, in detection reaction system, isocyanic ester is excessive, stopped reaction; Filter and vacuum-drying at 60 DEG C by methanol wash, finally obtain amylose starch-[2,6-bis-(3-methyl phenyl carbamate)-3-(4-meta-chlorocarbanilate)], productive rate is 90%.
5. synthesized final product 0.2g is dissolved in 6mL tetrahydrofuran (THF), then coating process is used polymer uniform to be coated in the surface of macropore Aminopropyl silica gel (particle diameter 7 μm, aperture 100nm), and adopt homogenate method to fill post, complete the preparation of amylose starch-[2,6-bis-(3-methyl phenyl carbamate)-3-(4-meta-chlorocarbanilate)] chiral stationary phase.
Amylose starch that the present invention obtains-[2,6-bis-(3-methyl phenyl carbamate)-3-(4-meta-chlorocarbanilate)] productive rate high, structural regularity good (molecular structure characterization the results are shown in Figure 4), and there is outstanding chiral recognition performance.
Embodiment three:
1. get 1g amylose starch vacuum-drying 4h at 105 DEG C, be warming up to 120 DEG C, then stirring and refluxing 4h in anhydrous N,N-dimethylacetamide; 1.5g lithium chloride is added after being cooled to 100 DEG C; Continue to stir 2h, after being cooled to room temperature, add 2.02g imidazoles; Add the tertiary hexyl chloride SiClx of excessive dimethyl after backflow 20min, be again warming up to 100 DEG C, stopped reaction after Keep agitation backflow 24h; Be cooled to room temperature, add damping fluid (adding 3.54g potassium primary phosphate and 7.14g dipotassium hydrogen phosphate in 1000ml distilled water) sedimentation filtration, with second alcohol and water (volume ratio 9:1) washing, 60 DEG C of vacuum-dryings are to constant weight, and productive rate is 80%.
2. by above-mentioned intermediate product vacuum-drying 4h at 80 DEG C, then reflux 6h in anhydrous pyridine, adds excessive phenyl isocyanate after being warming up to 100 DEG C, and at 100 DEG C, stopped reaction after continuation backflow 14h, fully washs and vacuum-drying with methyl alcohol.
3. previous step gained intermediate product is dissolved in the tetrahydrofuran solution containing tetrabutyl ammonium fluoride (quality is 4 times for amylose starch molar equivalent) and is hydrolyzed, at 50 DEG C, stir 24h stopped reaction; By methanol wash and vacuum-drying, productive rate is 76%.
4. above product is fully dissolved in anhydrous pyridine the 6h that refluxes under high temperature, then adds excessive 3-methylphenyl isocyanate, continue backflow 14h at 100 DEG C, in detection reaction system, isocyanic ester is excessive, stopped reaction; Filter and vacuum-drying at 60 DEG C by methanol wash, finally obtain amylose starch-[2,6-bis-(3-methyl phenyl carbamate)-3-phenylcarbamate], productive rate is 95%.
5. synthesized final product 0.2g is dissolved in 8mL tetrahydrofuran (THF), then coating process is used polymer uniform to be coated in the surface of macropore Aminopropyl silica gel (particle diameter 7 μm, aperture 100nm), and adopt homogenate method to fill post, complete the preparation of amylose starch-[2,6-bis-(3-methyl phenyl carbamate)-3-phenylcarbamate] chiral stationary phase.
Amylose starch that the present invention obtains-[2,6-bis-(3-methyl phenyl carbamate)-3-phenylcarbamate] productive rate high, structural regularity good (molecular structure characterization the results are shown in Figure 5), and there is outstanding chiral recognition performance.
Claims (2)
1. there is a Regioselective synthesis for different carbamate sides base amylose starch analog derivative, it is characterized in that:
Step one: by the amylose starch of drying at 120 DEG C ± 5 DEG C temperature, stir 2-6h in anhydrous N,N-dimethylacetamide; The lithium chloride of 1.5 ~ 2 times of amylose starch quality is added after being cooled to 100 DEG C ± 5 DEG C; Continue to stir 2-6h, add imidazo and stir, then add the tertiary hexyl chloride SiClx of excessive dimethyl, be again warming up to 100 DEG C ± 5 DEG C, Keep agitation backflow 18-24h; Be cooled to room temperature, add damping fluid sedimentation filtration, with ethanol and water washing, 40-60 DEG C of vacuum-drying, to constant weight, obtains 2-, 6-position protection intermediate product;
Step 2: by above-mentioned 2-, 6-position protection intermediate product vacuum-drying 2-4h at 80 DEG C ± 5 DEG C temperature, then reflux 4-10h in anhydrous pyridine, adds excessive phenyl isocyanate NCO-R after being warming up to 100 DEG C ± 5 DEG C
1, at 100 DEG C ± 5 DEG C, continue backflow 12-16h, fully wash and vacuum-drying with methyl alcohol;
Step 3: be dissolved in by step 2 gained intermediate product in the tetrahydrofuran solution containing tetrabutyl ammonium fluoride and be hydrolyzed, stir 24h at 50 DEG C, by methanol wash and vacuum-drying;
Step 4: step 3 products therefrom is dissolved in anhydrous pyridine the 4-10h that refluxes at 100 DEG C ± 5 DEG C, then add another kind of excessive phenyl isocyanate NCO-R
2, continue backflow 12-16h at 80-100 DEG C, in detection reaction system, isocyanic ester is excessive, stopped reaction; Add methyl alcohol, fully washing, to filter and vacuum-drying obtains having different carbamate sides base amylose starch analog derivative at 40-60 DEG C;
Wherein NCO-is isocyanate groups, R
1be 3,5-dichlorophenyl, R
2for 3-chloro-phenyl-; R
1for 4-chloro-phenyl-, R
2for 3-aminomethyl phenyl; R
1for phenyl, R
2for 3-aminomethyl phenyl.
2. the application method with different carbamate sides base amylose starch analog derivative prepared by a claim 1, it is characterized in that: there is different carbamate sides base amylose starch analog derivative for the preparation of chiral stationary phase, there is different carbamate sides base amylose starch analog derivative be fully dissolved in tetrahydrofuran (THF), then coating process is used evenly to be coated in the surface of macropore Aminopropyl silica gel, and adopt homogenate method to fill post, complete the preparation of chiral stationary phase, the particle diameter 7 μm of described macropore Aminopropyl silica gel, aperture 100nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105903456A (en) * | 2016-05-06 | 2016-08-31 | 哈尔滨工程大学 | Preparation method of amylose type derivative functional inorganic-silicon-based chiral micro-sphere fixed-phase material |
| CN106268716A (en) * | 2016-10-21 | 2017-01-04 | 哈尔滨工程大学 | The preparation method of functionalization inorganic based on straight chain starch derivative silica-based chirality microsphere stationary phase material |
| CN111909281A (en) * | 2020-08-31 | 2020-11-10 | 武汉工程大学 | Preparation method of amylose-2, 3-di (aryl carbamate) -6-deoxy-6-aryl urea |
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| EP0281951A1 (en) * | 1987-03-04 | 1988-09-14 | Daicel Chemical Industries, Ltd. | Alkyl-phenylcarbamate derivative of polysaccharide |
| CN102311504A (en) * | 2010-07-09 | 2012-01-11 | 株式会社大赛璐 | Polysaccharide derivates and preparation method thereof and separating agent |
| CN102633892A (en) * | 2006-09-04 | 2012-08-15 | 大赛璐化学工业株式会社 | Polysaccharide derivative and separating agent for optical isomer containing the same |
| CN102757507A (en) * | 2012-07-06 | 2012-10-31 | 华中农业大学 | Preparation method of C3- directionally-substituted carboxymethyl starch |
| CN103172756A (en) * | 2013-03-21 | 2013-06-26 | 哈尔滨工程大学 | Method for preparing side-chain amylose with different carbamates and chiral stationary phase |
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2015
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| EP0281951A1 (en) * | 1987-03-04 | 1988-09-14 | Daicel Chemical Industries, Ltd. | Alkyl-phenylcarbamate derivative of polysaccharide |
| CN102633892A (en) * | 2006-09-04 | 2012-08-15 | 大赛璐化学工业株式会社 | Polysaccharide derivative and separating agent for optical isomer containing the same |
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| CN102757507A (en) * | 2012-07-06 | 2012-10-31 | 华中农业大学 | Preparation method of C3- directionally-substituted carboxymethyl starch |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105903456A (en) * | 2016-05-06 | 2016-08-31 | 哈尔滨工程大学 | Preparation method of amylose type derivative functional inorganic-silicon-based chiral micro-sphere fixed-phase material |
| CN105903456B (en) * | 2016-05-06 | 2018-05-18 | 哈尔滨工程大学 | The preparation method of amylose analog derivative functionalization inorganic silicon substrate chirality microballoon stationary phase material |
| CN106268716A (en) * | 2016-10-21 | 2017-01-04 | 哈尔滨工程大学 | The preparation method of functionalization inorganic based on straight chain starch derivative silica-based chirality microsphere stationary phase material |
| CN111909281A (en) * | 2020-08-31 | 2020-11-10 | 武汉工程大学 | Preparation method of amylose-2, 3-di (aryl carbamate) -6-deoxy-6-aryl urea |
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