CN103172756A - Method for preparing side-chain amylose with different carbamates and chiral stationary phase - Google Patents
Method for preparing side-chain amylose with different carbamates and chiral stationary phase Download PDFInfo
- Publication number
- CN103172756A CN103172756A CN2013100922090A CN201310092209A CN103172756A CN 103172756 A CN103172756 A CN 103172756A CN 2013100922090 A CN2013100922090 A CN 2013100922090A CN 201310092209 A CN201310092209 A CN 201310092209A CN 103172756 A CN103172756 A CN 103172756A
- Authority
- CN
- China
- Prior art keywords
- under
- vacuum
- drying
- add
- carrying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention provides a method for preparing side-chain amylose with different carbamates and a chiral stationary phase. The method comprises the following steps of: carrying out vacuum drying on amylose, carrying out stirring reflux in anhydrous N,N-dimethyl acetamide, cooling to room temperature, then, adding lithium chloride, reheating, adding anhydrous pyridine, refluxing, then, adding superfluous triphenylchloromethane, and carrying out continuous stirring reflux; after vacuum drying, carrying out refluxing in the anhydrous pyridine, then, adding superfluous phenyl isocyanate, stopping reaction, completely washing by using methanol, and carrying out vacuum drying; dissolving into tetrahydrofuran solution containing hydrochloric acid so as to carry out hydrolysis; and fully dissolving into the anhydrous pyridine, adding superfluous cyclohexyl isocyanate, stopping reaction, adding methanol, and carrying out vacuum drying, thereby obtaining the side-chain amylose with the carbamates. According to the method, the adopted amylose is wide in source, is cheap and is easily available, and a synthesis process is simple, mature, easy to control and high in yield. The method can be applied to large-scale batch production.
Description
Technical field
The present invention relates to a kind of preparation method of amylose starch.The present invention also relates to a kind of preparation method of amylosebased chiral stationary phase.
Background technology
At present, commercial Polysaccharides Type Chiral Stationary Phases (comprising cellulose family and amylose starch class) has surpassed more than ten and has planted, but all commercialization chiral stationary phases based on material all belong to single monobasic polysaccharide derivatives, namely these derivatives all have single substituting group on its sugar unit three positions.The chiral stationary phase that has high-efficiency broad spectrum chiral recognition ability for development of new, and the range of application of expansion chiral stationary phase some have occurred the polysaccharide superpolymer have been carried out the trial that the multidigit selectivity replaces.1993, Okamoto study group application region selectivity method of substitution for the first time synthesized Mierocrystalline cellulose and the starch based derivative (Bull Chem Soc Jpn, 1993,66,2225) that sugar unit 2-, 3-position and 6-position have two kinds of phenylcarbamate groups.After this monobasic polysaccharide derivatives of such non-list is developed successively and reports, the derivative of so far developing is all to synthesize by the aromatics ester group (phenylcarbamate or benzoic ether group) of introducing respectively with different side chains on sugar unit 2-, 3-position and 6-position.Find after deliberation, there are very big-difference in the chiral recognition of multidigit substitutive derivative and fractionation ability and single substitutive derivative, wherein performance, position and the quantity of three different substituents that introduce the position of sugar unit all have larger impact for taxis and the chiral recognition ability of polysaccharide derivatives, are determined and this impact is space steric effect by benzene ring substitution group to a great extent.Therefore, the simple adduction of the not all substituting group effect of chiral recognition ability of this class multidigit selectivity substitutive derivative, but determined by the high stage structure of secondary of polysaccharide superpolymer.In addition, have chiral recognition and fractionation performance preferably with the substituent polysaccharide derivatives of aromatic ring mainly for fragrant same clan chipal compounds, and relatively poor for the chiral recognition ability of the non-aromatic compounds that does not have phenyl.In recent years, developing rapidly of chiral separation and analysis field, for the chiral recognition efficient of chiral stationary phase material and the high request of fractionation scope of application proposition, the novel chiral stationary phase with broad-spectrum high efficacy chiral recognition ability of design and development has become one of the study hotspot in this field.
Summary of the invention
The object of the present invention is to provide a kind of technique simple, be easy to control, the preparation method with different carbamate selectivity side chain amylose starchs that productive rate is high.The present invention also aims to provide a kind of preparation method with different carbamate selectivity side chain amylosebased chiral stationary phases.
The object of the present invention is achieved like this:
Preparation method with different carboxylamine ester side chain amylose starchs of the present invention is:
Step 1: amylose starch is vacuum-drying 2-8h under 80 ° of C, then stirring and refluxing 8-16h in anhydrous N,N-dimethylacetamide; Be cooled to the lithium chloride of 2 times that adds the amylose starch quality after room temperature; After continuing to stir 2-5h, again be warming up to 70 ° of C, add anhydrous pyridine, add excessive triphenylmethyl chloride after backflow 2-4h, stopped reaction after lasting stirring and refluxing 18-24h; Be cooled to room temperature, add the methyl alcohol sedimentation to filter and wash, 40-60 ° of C vacuum-drying is to constant weight;
Step 2: the step 1 products therefrom is continued vacuum-drying 2-6h under 80 ° of C, then add the excessive NCO-R that has after backflow 2-6h in anhydrous pyridine
1The phenyl isocyanate of general structure, wherein NCO-is isocyanate groups, R
1Be 3,5-3,5-dimethylphenyl, 3, a kind of in 5-dichlorophenyl or 4-chloro-phenyl-, stopped reaction after continuing backflow 12-16h under 80 ° of C fully washs and vacuum-drying with methyl alcohol;
Step 3: step 2 gained intermediate product is dissolved in the tetrahydrofuran solution that contains hydrochloric acid is hydrolyzed, the volume of hydrochloric acid is the 1-3% of tetrahydrofuran (THF), stirs the 12h stopped reaction under room temperature; Still with methanol wash and vacuum-drying;
Step 4: the step 3 products therefrom fully is dissolved in anhydrous pyridine the 2-6h that refluxes under 80 ° of C, add again excessive cyclohexyl isocyanate, continue backflow 16-30h under 60-80 ° of C, in the detection reaction system, isocyanic ester is excessive, stopped reaction, add methyl alcohol, fully washing, filter and under 40-60 ° of C vacuum-drying obtain having carboxylamine ester side chain amylose starch.
Preparation method with different carboxylamine ester side chain amylosebased chiral stationary phases of the present invention is:
To have carboxylamine ester side chain amylose starch and be dissolved in tetrahydrofuran (THF), and fully use coating process evenly to be coated in the surface of macropore aminopropyl silica gel after dissolving, and adopt homogenate method dress post, complete the preparation of chiral stationary phase.
The amylose starch wide material sources that the present invention adopts, cheap and easy to get, and amylose starch-2, the synthesis technique of 3-two (3,5-3,5-dimethylphenyl carbamate)-6-cyclohexyl carbamate is simple, ripe, be easy to control, and productive rate is high.Can be used for large-scale batch production.
The present invention is take amylose starch as initial raw material; first introduce three benzene methyls as blocking group on the sugar unit 6-position of amylose starch; then introduce respectively the phenylcarbamate group in sugar unit 2-position and 3-position; take off subsequently blocking group reduction 6-position hydroxyl in acidic solution; at 6-position introducing cyclohexyl carbamate groups, finally realize the regio-selective synthesis of straight chain starch derivative at last.On this basis, after the novel straight chain starch derivative that is synthesized is fully dissolved, use coating process that polymkeric substance evenly is coated in Silica Surface, adopt homogenate method dress post, prepare novel amylosebased chiral stationary phase.Characterize in detail with the chiral separation performance of high performance liquid chromatography to prepared chiral stationary phase.
Description of drawings
Fig. 1 is the synthetic route with different carboxylamine ester side chain straight chain starch derivatives of the present invention; Wherein: R
13,5-3,5-dimethylphenyl
, or 3,5-dichlorophenyl
, or 4-chloro-phenyl-
R
2Be cyclohexyl
Fig. 2-1 to Fig. 2-9 are the structural formula for nine kinds of racemic modifications estimating chiral stationary phase chiral separation performance of the present invention; Wherein: Fig. 2-1 is Te Luojie alkali, and Fig. 2-2 are trans 2,3-phenylbenzene oxyethane, and Fig. 2-3 are bitter almond oil camphor, and Fig. 2-4 are 2-benzyl ring hexanone, and Fig. 2-5 are 2,2,2-Trifluoromethyl-1-(9-anthryl)-ethanol, and Fig. 2-6 are triacetyl pyruvic acid cobalt,
Fig. 2-7 are flavanone, and Fig. 2-8 are 2,2-dimethyl-1-phenyl-propyl alcohol, and Fig. 2-9 are dinaphthol.
Fig. 3 be amylose starch-[2,3-two (3,5-dichlorophenyl the carbamate)-6-cyclohexyl carbamate] that become of the present invention proton nmr spectra (
1H-NMR) (500MHz, deuterated pyridine, 80 ℃).
Fig. 4 is amylose starch-2, and 3-two (3,5-3,5-dimethylphenyl carbamate)-6-cyclohexyl carbamate splits spectrogram for the chromatogram of bitter almond oil camphor enantiomorph.
Fig. 5 is that three kinds of amylosebased chiral stationary phases are for the chiral separation result of nine kinds of racemic modifications.
Embodiment
The below does more detailed description to the present invention for example:
Embodiment one:
1. get 0.2g amylose starch vacuum-drying 4h under 80 ° of C, then stirring and refluxing 12h in anhydrous N,N-dimethylacetamide; Add the 0.4g lithium chloride after being cooled to room temperature; After continuing to stir 2h, again be warming up to 70 ° of C, add anhydrous pyridine, add excessive triphenylmethyl chloride after backflow 4h, stopped reaction after lasting stirring and refluxing 24h; Be cooled to room temperature, add the methyl alcohol sedimentation to filter and wash, 60 ° of C vacuum-dryings are to constant weight, and productive rate is 88%.
2. above-mentioned intermediate product is continued vacuum-drying 4h under 80 ° of C, it is excessive 3 then to add after backflow 3h in anhydrous pyridine, the 5-dimethylphenyl isocyanate, and stopped reaction after continuing backflow 16h under 80 ° of C fully washs and vacuum-drying with methyl alcohol.
3. previous step gained intermediate product is dissolved in the tetrahydrofuran solution that contains a small amount of hydrochloric acid (volume be tetrahydrofuran (THF) 1.8%) and is hydrolyzed, stir the 12h stopped reaction under room temperature; With methanol wash and vacuum-drying, productive rate is 82%.
4. above product fully is dissolved in the 2h that refluxes under high temperature in anhydrous pyridine, then adds excessive cyclohexyl isocyanate, continue backflow 24h under 80 ° of C, in the detection reaction system, isocyanic ester is excessive, stopped reaction; Filter and vacuum-drying under 60 ° of C with methanol wash, finally obtain amylose starch-[2,3-two (3,5-3,5-dimethylphenyl)-6-cyclohexyl] carbamate, productive rate is 91%.
5. the final product 0.2g that is synthesized is dissolved in the 5mL tetrahydrofuran (THF), then use coating process polymkeric substance evenly to be coated in the surface of macropore aminopropyl silica gel (particle diameter 7 μ m, aperture 100nm), and adopt the homogenate method to fill post, complete amylose starch-[2,3-two (3,5-3,5-dimethylphenyl)-6-cyclohexyl] preparation of carbamate chirality stationary phase.
The productive rate of amylose starch that this embodiment obtains-[2,3-two (3,5-3,5-dimethylphenyl)-6-cyclohexyl] carbamate is high, and solvability is better than having same substituent cellulose derivative.
Embodiment two:
1. get 0.2g amylose starch vacuum-drying 4h under 80 ° of C, then stirring and refluxing 10h in anhydrous N,N-dimethylacetamide; Add the 0.4g lithium chloride after being cooled to room temperature; After continuing to stir 4h, again be warming up to 70 ° of C, add anhydrous pyridine, add excessive triphenylmethyl chloride after backflow 3h, stopped reaction after lasting stirring and refluxing 24h; Be cooled to room temperature, add the methyl alcohol sedimentation to filter and wash, 60 ° of C vacuum-dryings are to constant weight, and productive rate is 85%.
2. above-mentioned intermediate product is continued vacuum-drying 3h under 80 ° of C, it is excessive 3 then to add after backflow 3h in anhydrous pyridine, the 5-dichlorophenyl isocyanate, and stopped reaction after continuing backflow 12h under 80 ° of C fully washs and vacuum-drying with methyl alcohol.
3. previous step gained intermediate product is dissolved in the tetrahydrofuran solution that contains a small amount of hydrochloric acid (volume be tetrahydrofuran (THF) 1.8%) and is hydrolyzed, stir the 12h stopped reaction under room temperature; With methanol wash and vacuum-drying, productive rate is 77%.
4. above product fully is dissolved in the 4h that refluxes under high temperature in anhydrous pyridine, then adds excessive cyclohexyl isocyanate, continue backflow 25h under 80 ° of C, in the detection reaction system, isocyanic ester is excessive, stopped reaction; Filter and vacuum-drying under 60 ° of C with methanol wash, finally obtain amylose starch-[2,3-two (3,5-dichlorophenyl)-6-cyclohexyl] carbamate, productive rate is 95%.
5. the final product 0.2g that is synthesized is dissolved in the 5mL tetrahydrofuran (THF), then use coating process polymkeric substance evenly to be coated in the surface of macropore aminopropyl silica gel (particle diameter 7 μ m, aperture 100nm), and adopt the homogenate method to fill post, complete amylose starch-[2,3-two (3,5-dichlorophenyl)-6-cyclohexyl] preparation of carbamate chirality stationary phase.
The solvability of amylose starch that this embodiment obtains-[2,3-two (3,5-dichlorophenyl)-6-cyclohexyl] carbamate is better than having same substituent cellulose derivative, and has chiral recognition ability preferably.
Embodiment three:
1. get 0.2g amylose starch vacuum-drying 4h under 80 ° of C, then stirring and refluxing 10h in anhydrous N,N-dimethylacetamide; Add the 0.4g lithium chloride after being cooled to room temperature; After continuing to stir 4h, again be warming up to 70 ° of C, add anhydrous pyridine, add excessive triphenylmethyl chloride after backflow 4h, stopped reaction after lasting stirring and refluxing 23h; Be cooled to room temperature, add the methyl alcohol sedimentation to filter and wash, 60 ° of C vacuum-dryings are to constant weight, and productive rate is 90%.
2. above-mentioned intermediate product is continued vacuum-drying 3h under 80 ° of C, then add excessive 4-chloro-phenyl-isocyanic ester after backflow 4h in anhydrous pyridine, stopped reaction after continuing backflow 12h under 80 ° of C fully washs and vacuum-drying with methyl alcohol.
3. previous step gained intermediate product is dissolved in the tetrahydrofuran solution that contains a small amount of hydrochloric acid (volume be tetrahydrofuran (THF) 1.9%) and is hydrolyzed, stir the 12h stopped reaction under room temperature; With methanol wash and vacuum-drying, productive rate is 75%.
4. above product fully is dissolved in the 4h that refluxes under high temperature in anhydrous pyridine, then adds excessive cyclohexyl isocyanate, continue backflow 25h under 80 ° of C, in the detection reaction system, isocyanic ester is excessive, stopped reaction; Filter and vacuum-drying under 60 ° of C with methanol wash, finally obtain amylose starch-[2,3-two (4-chloro-phenyl-)-6-cyclohexyl] carbamate, productive rate is 92%.
5. the final product 0.2g that is synthesized is dissolved in the 6mL tetrahydrofuran (THF), then use coating process polymkeric substance evenly to be coated in the surface of macropore aminopropyl silica gel (particle diameter 7 μ m, aperture 100nm), and adopt the homogenate method to fill post, complete the preparation of amylose starch-[2,3-two (4-chloro-phenyl-)-6-cyclohexyl] carbamate chirality stationary phase.
The solvability of amylose starch that this embodiment obtains-[2,3-two (4-chloro-phenyl-)-6-cyclohexyl] carbamate is better than having same substituent cellulose derivative, and has chiral recognition ability preferably.
Fig. 3 be amylose starch-[2,3-two (3,5-dichlorophenyl the carbamate)-6-cyclohexyl carbamate] that become of the present invention proton nmr spectra (
1H-NMR) (500MHz, deuterated pyridine, 80 ℃).As can see from Figure 3, the compound with regular structure of institute's synthesis of derivatives, and meet expection composite structure target.and the chromatogram result in the table of Fig. 5 shows, this novel amylosebased chiral stationary phase demonstrates outstanding chiral separation ability to various racemic modifications, especially for Wen Zhongwu 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) and flavanone (Fig. 2-7) enantiomorph can be realized baseline separation completely, and for three kinds of enantiomorphs, be respectively Te Luojie alkali (Fig. 2-1), the separating effect of 2-benzyl ring hexanone (Fig. 2-4) and triacetyl pyruvic acid cobalt (Fig. 2-6) has surpassed in the chiral column of present commercial goods and to split excellent performance and single monobasic Chiralpak AD and another kind and have single substituent amylosebased chiral stationary phase ADCPC(amylose starch-three (3, 5-dichlorophenyl carbamate)), show that prepared novel amylosebased chiral stationary phase with selectivity side chain has larger practical value and market development potential.Wherein, novel straight chain starch derivative---amylose starch-2,3-two (3,5-dichlorophenyl carbamate)-6-cyclohexyl carbamate is shown in Fig. 4 for the chromatogram fractionation spectrogram of bitter almond oil camphor enantiomorph (Fig. 2-3), this novel chiral stationary phase has been realized baseline separation completely for the bitter almond oil camphor enantiomorph as we can see from the figure, and separating effect is considerably beyond commercialization chiral column Chiralpak AD and ADCPC.
Claims (4)
1. preparation method with different carboxylamine ester side chain amylose starchs is characterized in that:
Step 1: amylose starch is vacuum-drying 2-8h under 80 ° of C, then stirring and refluxing 8-16h in anhydrous N,N-dimethylacetamide; Be cooled to the lithium chloride of 2 times that adds the amylose starch quality after room temperature; After continuing to stir 2-5h, again be warming up to 70 ° of C, add anhydrous pyridine, add excessive triphenylmethyl chloride after backflow 2-4h, stopped reaction after lasting stirring and refluxing 18-24h; Be cooled to room temperature, add the methyl alcohol sedimentation to filter and wash, 40-60 ° of C vacuum-drying is to constant weight;
Step 2: the step 1 products therefrom is continued vacuum-drying 2-6h under 80 ° of C, then add excessive phenyl isocyanate after backflow 2-6h in anhydrous pyridine, stopped reaction after continuing backflow 12-16h under 80 ° of C fully washs and vacuum-drying with methyl alcohol;
Step 3: step 2 gained intermediate product is dissolved in the tetrahydrofuran solution that contains hydrochloric acid is hydrolyzed, stir the 12h stopped reaction under room temperature; Still with methanol wash and vacuum-drying;
Step 4: the step 3 products therefrom fully is dissolved in anhydrous pyridine the 2-6h that refluxes under 80 ° of C, add again excessive cyclohexyl isocyanate, continue backflow 16-30h under 60-80 ° of C, in the detection reaction system, isocyanic ester is excessive, stopped reaction, add methyl alcohol, fully washing, filter and under 40-60 ° of C vacuum-drying obtain having carboxylamine ester side chain amylose starch.
2. the preparation method with different carboxylamine ester side chain amylose starchs according to claim 1, it is characterized in that: described phenyl isocyanate has NCO-R
1General structure, wherein NCO-is isocyanate groups, R
1Be 3,5-3,5-dimethylphenyl, 3, a kind of in 5-dichlorophenyl or 4-chloro-phenyl-.
3. the preparation method with different carboxylamine ester side chain amylose starchs according to claim 1 and 2, it is characterized in that: the volume of hydrochloric acid is the 1-3% of tetrahydrofuran (THF).
4. preparation method with different carboxylamine ester side chain amylosebased chiral stationary phases is characterized in that:
To have carboxylamine ester side chain amylose starch and be dissolved in tetrahydrofuran (THF), and fully use coating process evenly to be coated in the surface of macropore aminopropyl silica gel after dissolving, and adopt homogenate method dress post, complete the preparation of chiral stationary phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100922090A CN103172756A (en) | 2013-03-21 | 2013-03-21 | Method for preparing side-chain amylose with different carbamates and chiral stationary phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100922090A CN103172756A (en) | 2013-03-21 | 2013-03-21 | Method for preparing side-chain amylose with different carbamates and chiral stationary phase |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103172756A true CN103172756A (en) | 2013-06-26 |
Family
ID=48632993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100922090A Pending CN103172756A (en) | 2013-03-21 | 2013-03-21 | Method for preparing side-chain amylose with different carbamates and chiral stationary phase |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103172756A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250312A (en) * | 2013-06-28 | 2014-12-31 | 株式会社大赛璐 | Chitosan carbanilate-carbamido derivative preparation method |
| CN105001344A (en) * | 2015-07-24 | 2015-10-28 | 哈尔滨工程大学 | Synthesis and application method for amylase derivatives with benzoate and phenyl carbamate substituent groups at same time |
| CN105017437A (en) * | 2015-07-24 | 2015-11-04 | 哈尔滨工程大学 | Regioselective synthesis and application methods for amylose derivatives with different carbamate side groups |
| CN105153317A (en) * | 2015-07-24 | 2015-12-16 | 哈尔滨工程大学 | Synthetic method for cellulose derivative with large volume liquid crystal unit side group |
| CN111574649A (en) * | 2020-05-20 | 2020-08-25 | 哈尔滨工程大学 | Controllable synthesis method of highly stereoregular polymethyl methacrylate |
| CN115715975A (en) * | 2022-10-28 | 2023-02-28 | 佳化化学科技发展（上海）有限公司 | Porous spherical adsorbent and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259406A (en) * | 2007-12-17 | 2008-09-10 | 南京工业大学 | Preparation method of bonding-affinity compound polysaccharide chiral stationary phase |
| CN101766995A (en) * | 2008-12-30 | 2010-07-07 | 中山海拓生物材料科技有限公司 | Bonded polysaccharide chiral separation liquid chromatography stationary phase material and synthesis method thereof |
-
2013
- 2013-03-21 CN CN2013100922090A patent/CN103172756A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259406A (en) * | 2007-12-17 | 2008-09-10 | 南京工业大学 | Preparation method of bonding-affinity compound polysaccharide chiral stationary phase |
| CN101766995A (en) * | 2008-12-30 | 2010-07-07 | 中山海拓生物材料科技有限公司 | Bonded polysaccharide chiral separation liquid chromatography stationary phase material and synthesis method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 沈军等: "多糖类氨基甲酸酯衍生物的区域选择性合成", 《高分子学报》, no. 03, 20 March 2013 (2013-03-20) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250312A (en) * | 2013-06-28 | 2014-12-31 | 株式会社大赛璐 | Chitosan carbanilate-carbamido derivative preparation method |
| CN104250312B (en) * | 2013-06-28 | 2019-03-15 | 株式会社大赛璐 | Chitosan class carbanilate-ureido derivatives preparation method |
| CN105001344A (en) * | 2015-07-24 | 2015-10-28 | 哈尔滨工程大学 | Synthesis and application method for amylase derivatives with benzoate and phenyl carbamate substituent groups at same time |
| CN105017437A (en) * | 2015-07-24 | 2015-11-04 | 哈尔滨工程大学 | Regioselective synthesis and application methods for amylose derivatives with different carbamate side groups |
| CN105153317A (en) * | 2015-07-24 | 2015-12-16 | 哈尔滨工程大学 | Synthetic method for cellulose derivative with large volume liquid crystal unit side group |
| CN111574649A (en) * | 2020-05-20 | 2020-08-25 | 哈尔滨工程大学 | Controllable synthesis method of highly stereoregular polymethyl methacrylate |
| CN115715975A (en) * | 2022-10-28 | 2023-02-28 | 佳化化学科技发展（上海）有限公司 | Porous spherical adsorbent and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103172756A (en) | Method for preparing side-chain amylose with different carbamates and chiral stationary phase | |
| CN104250312A (en) | Chitosan carbanilate-carbamido derivative preparation method | |
| CN102921193B (en) | Preparation method of capillary electro-chromatography column taking beta-cyclodextrin as bonded stationary phase and application in chiral drug separation | |
| CN105017437A (en) | Regioselective synthesis and application methods for amylose derivatives with different carbamate side groups | |
| CN102757507B (en) | Preparation method of C3- directionally-substituted carboxymethyl starch | |
| Fu et al. | Dependence of enantioseparation performance on structure of chiral selectors derived from N-cycloalkylcarbonyl chitosan | |
| CN103172755A (en) | Cellulose derivative simultaneously containing cyclohexyl carbamate and phenyl carbamate and preparation method of cellulose derivative | |
| CN103965093A (en) | 2-perfluoroalkyl indole compound as well as preparation and application thereof | |
| CN107118168B (en) | A kind of copper catalyzes and synthesizes Trifluoromethyl-1, the method for 2,4- triazineon compounds | |
| CN101519395A (en) | Preparation method of fully substituted acetylate of epigallocatechin-gallate (EGCG) | |
| CN105001344A (en) | Synthesis and application method for amylase derivatives with benzoate and phenyl carbamate substituent groups at same time | |
| CN108929215A (en) | A kind of synthetic method of the halogenated alpha, beta unsaturated ketone class compound of cis- α | |
| CN113061124B (en) | Sesquiterpene dimer compound, and preparation method, application and pharmaceutical composition thereof | |
| Zhang et al. | Asymmetric synthesis of chiral (thio) chromanes and exploration on their structure–activity relationship in macrophages | |
| CN102491888A (en) | Acyl-substituted triptycene and preparation method thereof | |
| CN105399718A (en) | Solid phase synthesis method of 2H-benzopyran compounds | |
| CN106543074B (en) | One-dimensional chirality Cu (II) chain complex of one kind and the preparation method and application thereof | |
| CN108752643A (en) | Preparation method based on cellulose derivative nano silicon dioxide hybridization material | |
| CN107973715A (en) | A kind of preparation method of polysubstituted distal end allyl ketone derivative | |
| CN114404612B (en) | Zanthoxylum oil cyclodextrin inclusion compound and preparation method thereof | |
| CN106268716A (en) | The preparation method of functionalization inorganic based on straight chain starch derivative silica-based chirality microsphere stationary phase material | |
| CN103073398B (en) | The preparation method of two (3-methylphenoxy) ethane of 1,2- | |
| Huang et al. | In (OTf) 3 catalyzed regioselective acyloin rearrangement of 1-acyl-1-indanols | |
| CN104892372A (en) | Synthetic method of micromolecule polyethylene glycol | |
| CN102675204B (en) | Intermediate for synthesizing (I)-huperzine A, synthesis method and usage thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130626 |