CN101417241B - Preparation method of macromolecule loaded quinine type compound - Google Patents
Preparation method of macromolecule loaded quinine type compound Download PDFInfo
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- CN101417241B CN101417241B CN2008102035480A CN200810203548A CN101417241B CN 101417241 B CN101417241 B CN 101417241B CN 2008102035480 A CN2008102035480 A CN 2008102035480A CN 200810203548 A CN200810203548 A CN 200810203548A CN 101417241 B CN101417241 B CN 101417241B
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- cinchona alkaloid
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Abstract
The invention provides a preparation method used for preparing compounds such as cinchona alkaloid loaded by polymer, comprising the steps as follows: with the existence of organic solvent and inorganic alkali or organic alkali, the compounds such as the cinchona alkaloid reacts with chloromethylated porous polystyrene resin for 10-60 at the temperature ranging from 20 DEG C to a reflux temperature; subsequently, the resin is filtrated; and the molar ratio of chloromethyl and alkali in the porous polystyrene resin of the compounds such as the cinchona alkaloid is 0.6-2.5:1:1.0-3.0. The compounds such as the cinchona alkaloid loaded by polymer prepared by the method is used as the catalyst, has simple operation, can be circularly used, is friendly to the environment, and can be more widelyapplied to the preparation of chiral compounds.
Description
Technical field
The present invention relates to the preparation method of the chiral catalyst of a family macromolecule load, be specifically related to the preparation method of the cinchona alkaloid compound of macromolecule loading.
Background technology
Though chipal compounds has identical molecular composition, be mutually mirror image between its enantiomer, can not be overlapping.Many identical physicochemical properties are arranged between the enantiomer of chipal compounds, as fusing point, solubility etc., but some physicochemical property differences are arranged also, as optical activity, smell etc., these differences show especially with the closely-related biochemical reaction of organism in, as the pharmacological properties of chipal compounds.Studies show that the enantiomer pharmacological properties that has is close, an enantiomer has the effect of curing the disease in the chipal compounds that has, another does not then have disease cure function, enantiomer has opposite pharmacological properties in the chipal compounds that has, and promptly an enantiomer is a good medicine, and another then is a poison.Present many countries stipulate that all the medicine producer must study enantiomter contained in medicine pharmacological action, toxicity and clinical effectiveness separately, thereby rejects poisonous enantiomter.Worldwide caused the upsurge of chipal compounds research and development thus.At present, chiral drug has accounted for sells the over half of medicine, and this trend is also rising.
Except chiral drug, other chipal compounds such as chiral amino acid, chiral alcohol, chiral epoxy compound, chiral sulphide, Chiral Amine etc. have in fields such as perfume industry, agricultural chemicals, biomedicine and special materials widely to be used.Chipal compounds has become the research focus of each big drugmaker of the whole world and research institution.
The preparation method of chipal compounds mainly contains fractionation, asymmetric syntheses and biosynthesis etc., along with kind and the quantity of fields such as medical industry, agricultural chemicals, life science and material to chipal compounds constantly increases, the preparation method of traditional chipal compounds has been difficult to satisfy the demands, excites people constantly to seek to develop the technology of synthesizing chiral compound.The asymmetric syntheses technology has become present research focus, the especially asymmetric syntheses of chiral catalyst catalysis.
Chiral catalyst mostly is metal complex greatly, catalytic efficiency height, but the central ion of chiral catalyst heavy metal or noble metal often, in course of reaction, may decompose and pollution products, simultaneously the cost of catalyst own is higher, and is difficult to shortcoming such as recovery, is difficult to extensive use.Quinine is a kind of alkaloid, is present in the bark of Peruvian bark tree, and the quaternary ammonium salt of quinine can be used for chiral catalyst.For the metal species chiral catalyst, the quinine stable performance, bought easily, relatively cheap, can be recycled and easily modification etc. a bit be subjected to paying close attention to widely.
The quinine that macromolecule is immobilized or its quaternary ammonium salt have easy separation, can be recycled, advantage such as environmentally friendly.Publication number CN 101168134A has reported with the mesoporous material to be carrier, synthetic a kind of heterogeneous quinine bionic catalyst.The patent report of publication number CN 1523024A immobilized cinchonine Alkaloid part and the synthetic method of macromolecule.Publication number CN 1524835A has reported the preparation method of the dicinchonine Alkaloid part that macromolecule is immobilized.
In patent and other documents, the macromolecule carrier that is used for load quinine or its quaternary ammonium salt mainly contains the Merrifield of linear polystyrene, polyethylene glycol and gel-type
TMResin etc.The shortcoming of these carrier maximums shows: on the one hand, need add when catalytic reaction that specific solvent dissolves or these solid-carrying type chiral catalysts of swelling, different carriers need dissolve or swelling in different solvents, needing to add specific precipitating reagent after reaction is finished again separates out carrier, so not only increased the use amount of solvent greatly, and Application of Catalyst also is subjected to the restriction of solvent species, thus the range of application of limiting catalyst; On the other hand, when reclaiming catalyst, cause the loss of catalyst easily.Excessive use solvent also causes the increase of cost and the burden of environment.We are faced with serious environmental now and pollute, and the pollution of volatile solvent is the main source of environmental pollution, develops the trend that environment amenable green catalyst is a current social development.
Therefore, this area press for exploitation separate easily, simple to operate, can be recycled, the preparation method and the chiral catalyst thereof of environment amenable chiral catalyst.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of cinchona alkaloid compound of macromolecule loading.
Another object of the present invention provides a kind of cinchona alkaloid compound of macromolecule loading.
A further object of the present invention provides a kind of quinine quaternary ammonium salt that contains the macromolecule loading of different anions.
This paper " cinchona alkaloid compound " refers to quinine, its isomers, and quaternary ammonium salt.Include but not limited to cinchonine (CN), cinchonidine (CD), N-9-anthracene methylene cinchonine salt or N-9-anthracene methylene cinchonidine etc.Described " quinine " comprises quinine (QN), chinidine (QD), cinchonine (CN), cinchonidine (CD).
" porous crosslinked polystyrene " described herein or " macroporous cross-linked polystyrene " are used interchangeably.Recommending to use the degree of cross linking is 6%～50%, and granularity is 20～100 orders, the porous crosslinked polystyrene of aperture 20～200 nanometers.Better, the granularity of porous crosslinked polystyrene is 30～60 orders, the aperture is 50～150 nanometers.
Many (greatly) hole crosslinked polystyrene carrier of the at first synthetic different degrees of cross linking of inventor, by series reaction the quinine of chirality or its quaternary ammonium salt mode with chemical bond (ehter bond) is connected on the carrier then, thereby has synthesized the quinine and the quaternary ammonium salt solid-phase catalyst thereof of the crosslinked macromolecule loading in many (greatly) hole.
A first aspect of the present invention provides a kind of preparation method of cinchona alkaloid compound of macromolecule loading, promptly in organic solvent and inorganic base or organic base in the presence of, the expanded polystyrene resin of cinchona alkaloid compound and chloromethylation reacted 10～60 hours to reflux temperature at 20 ℃, leached resin then; The mol ratio of chloromethyl and alkali is 0.6～3.0:1:1.0～5.0 in described cinchona alkaloid compound, the expanded polystyrene resin.
Above-mentioned cinchona alkaloid compound is for having compound in structural formula I, its isomers and quaternary ammonium salt thereof:
Wherein R is H or CH
3O.
Above-mentioned cinchona alkaloid compound is quinine, chinidine, cinchonine, cinchonidine, N-9-anthracene methylene quinine salt, N-9-anthracene methylene chinidine, N-9-anthracene methylene cinchonine salt or N-9-anthracene methylene cinchonidine.
The degree of cross linking of above-mentioned porous crosslinked polystyrene resin is 6%～50%, and granularity is 20～100 orders, aperture 20～200 nanometers.The granularity of preferred porous crosslinked polystyrene resin is 20～100 orders, aperture 20～200 nanometers.
Above-mentioned organic solvent is toluene, dimethylbenzene, N, N-dimethyl formamide, methyl-sulfoxide or other aprotic solvent.Reflux temperature of the present invention is the reflux temperature of above-mentioned organic solvent.
Above-mentioned alkali is selected from NaOH, KOH, NaH, NaNH
2, C
4H
9A kind of among the Li.Above-mentioned alkali can be the mixture of a kind of organic base and a kind of inorganic base.Above-mentioned alkali is selected from NaOH, KOH, NaH, NaNH
2, C
4H
9Any two kinds are mixed use among the Li.Preferable, described alkali is NaH.
The mol ratio of chloromethyl and alkali is 1.0～1.5:1:1.5～3.3 in above-mentioned cinchona alkaloid compound, the expanded polystyrene resin.
A second aspect of the present invention provides a kind of cinchona alkaloid compound of macromolecule loading of method for preparing, and the cinchona alkaloid compound of described macromolecule loading is compound, its isomers and the quaternary ammonium salt thereof with structural formula II:
Wherein
Be porous crosslinked polystyrene; R is H or CH
3O.The degree of cross linking of described porous crosslinked polystyrene is 6%～50%, and granularity is 20～100 orders, aperture 20～200 nanometers.The granularity of preferred porous crosslinked polystyrene is 30～60 orders, and the aperture is 50～150 nanometers.
The quaternary ammonium salt of the compound of said structure formula II is compound or its isomers with molecule formula III:
Wherein zero is porous crosslinked polystyrene; R is H or CH
3O; X
-Be F
-, Cl
-, Br
-, I
-, SO
4 2-, CF
3COO
-, CF
3SO
3 -, (CF
3SO
2) N
-Or (CF
3CO)
2N
-Preferred X
-Be Cl
-Or CF
3SO
3 -
The degree of cross linking of above-mentioned porous crosslinked polystyrene is 6%～50%, and granularity is 20～100 orders, aperture 20～200 nanometers.The granularity of preferred porous crosslinked polystyrene is 30～60 orders, and the aperture is 50～150 nanometers.
The cinchona alkaloid compound of the macromolecule loading of method for preparing is the quaternary ammonium salt of the quinine of the quinine of macromolecule loading or macromolecule loading.
The quinine of the macromolecule loading of method for preparing is:
Or
Or
The quaternary ammonium salt of the quinine of above-mentioned macromolecule loading is:
Wherein
Represent many (greatly) hole crosslinked polystyrene, X
-Be F
-, Cl
-, Br
-, I
-, SO
4 2-, CF
3COO
-, CF
3SO
3 -, (CF
3SO
2) N
-Or (CF
3CO)
2N
-Preferred X
-Be Cl
-
Product of the present invention is a kind of chiral catalyst of excellent performance, especially is fit to be applied to the asymmetric syntheses of chipal compounds.
The reusable quinine of many (greatly) of the present invention hole cross-linked polymer load or the synthetic method of quinine quaternary ammonium salt can be expressed as follows:
Concrete synthetic method is many (greatly) hole polystyrene with different degrees of cross linking of earlier synthetic chloromethylation: be crosslinking agent and many (greatly) the hole polystyrene carrier (5) of BPO (dibenzoyl peroxide) for the synthetic different degrees of cross linking of initator with the divinylbenzene, obtain the macroporous cross-linked polystyrene (6) of chloromethylation then with the chloromethyl ether reaction.
Synthesizing of the 9-anthracene methylene quaternary ammonium salt of quinine (cinchonine CN and cinchonidine CD): cinchonine CN (1) or cinchonidine CD (3) are dissolved in the toluene, add 9-chloromethyl anthracene (9-chloromethylanthracene) again, refluxing to obtain the 9-anthracene methylene quaternary ammonium salt (2) of cinchonine CN and the 9-anthracene methylene quaternary ammonium salt (4) of cinchonidine CD in 4～5 hours.
PS-CN-3 of the present invention synthetic is to be raw material with quinine CN (1), in organic solvent and inorganic base or organic base in the presence of, quinine CN (1) reacted under 20～reflux temperature 10～60 hours with many (greatly) the hole polystyrene resin (6) of chloromethylation, leached resin then.The molar ratio of chloromethyl and alkali is 0.6～3.0:1:1.0～5.0 in described quinine CN (1), many (greatly) hole polystyrene resin, and the recommendation ratio is 1.0～1.5:1:1.5～3.3.
PS-CD-4 of the present invention synthetic is to be raw material with quinine CD (3), in organic solvent and inorganic base or organic base in the presence of, quinine CD (3) reacted under 20～reflux temperature 10～60 hours with many (greatly) the hole polystyrene resin (6) of chloromethylation, leached resin then.The molar ratio of chloromethyl and alkali is 0.6～3.0:1:1.0～5.0 in described quinine CD (3), many (greatly) hole polystyrene resin, and the recommendation ratio is 1.0～1.5:1:1.5～3.3.
PS-CN-7 of the present invention synthetic is that the 9-anthracene methylene quaternary ammonium salt (2) with quinine CN is a raw material, in organic solvent and inorganic base or organic base in the presence of, the 9-anthracene methylene quaternary ammonium salt (2) of quinine CN reacted under 20～reflux temperature 10～60 hours with many (greatly) the hole polystyrene resin (6) of chloromethylation, leached resin then.The molar ratio of chloromethyl and alkali is 0.6～3.0:1:1.0～5.0 in the 9-anthracene methylene quaternary ammonium salt (2) of described quinine CN, many (greatly) hole polystyrene resin, and the recommendation ratio is 1.0～1.5:1:1.5～3.3.
PS-CD-8 of the present invention synthetic is that the 9-anthracene methylene quaternary ammonium salt (4) with quinine CD is a raw material, in organic solvent and inorganic base or organic base in the presence of, the 9-anthracene methylene quaternary ammonium salt (4) of quinine CD reacted under 20～reflux temperature 10～60 hours with many (greatly) the hole polystyrene resin (6) of chloromethylation, leached resin then.The molar ratio of chloromethyl and alkali is 0.6～3.0:1:1.0～5.0 in the 9-anthracene methylene quaternary ammonium salt (4) of described quinine CD, many (greatly) hole polystyrene resin, and the recommendation ratio is 1.0～1.5:1:1.5～3.3.
Anion in the 9-anthracene methylene quaternary ammonium salt of the quinine of macromolecule loading of the present invention is except Cl
-Can also be F outward,
-, Br
-, I
-, SO
4 2-, CF
3COO
-, CF
3SO
3 -, (CF
3SO
2) N
-Or (CF
3CO)
2N
-Deng anion, its synthetic method is by containing Cl
-The quinine 9-anthracene methylene quaternary ammonium salt of the macromolecule loading of ion and NaF, NaBr, NaI, Na
2SO
4, NaCF
3COO, NaCF
3SO
3, Na (CF
3SO
2) N, Na (CF
3CO)
2N prepares by ion-exchange.
The degree of cross linking of many (greatly) of the present invention hole cross-linked polystyrene resin is 6%～50%, and granularity is 20～100 orders, and recommending granularity is 30～60 orders, aperture 20～200 nanometers, and recommending the aperture is 50～150 nanometers.
Organic solvent of the present invention is meant toluene, dimethylbenzene, N, N-dimethyl formamide, methyl-sulfoxide or other aprotic solvent.
Organic base of the present invention or inorganic base are meant NaOH, KOH, NaH, NaNH
2, C
4H
9Li etc. can be the mixture of one or both organic bases or inorganic base in actual use.
The cinchona alkaloid compound that utilizes macromolecule loading of the present invention is when catalytic reaction, do not need specific dissolution with solvents or swelling, not only reduce the use amount of solvent, environmentally friendly, and be not subjected to the influence of solvent species, catalytic reaction can carried out in the solvent scope widely.
Others of the present invention are because disclosing of the technology of this paper is conspicuous to those skilled in the art.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only are used to illustrate the present invention, limit the scope of the invention and be not used in.
Embodiment 1 degree of cross linking is the synthetic of 10% macroporous cross-linked polystyrene carrier
In the there-necked flask of the 250mL that mechanical agitation and condenser pipe are housed, add gelatin 0.3g, distilled water 150mL, heating and stirring make the gelatin dissolving, add normal heptane 20mL then, styrene 18g, divinylbenzene 2g, BPO0.2g (being added in the styrene).Start mechanical agitation and control mixing speed, drop is controlled in the suitable scope.Progressively be warming up to 70oC, be incubated 2 hours, be warming up to 85oC again, be incubated and rise to 95oC after 4 hours, be incubated after 1 hour, filter, with hot wash for several times, with drying for standby after the acetone extracting.Promptly obtain the degree of cross linking and be 10% macroporous cross-linked polystyrene resin.
Embodiment 2 degrees of cross linking are the synthetic of 6% macroporous cross-linked polystyrene carrier
In the there-necked flask of the 250mL that mechanical agitation and condenser pipe are housed, add gelatin 0.3g, distilled water 150mL, heating and stirring make the gelatin dissolving, add normal heptane 20mL then, styrene 18.8g, divinylbenzene 1.2g, BPO0.2g (being added in the styrene).Start mechanical agitation and control mixing speed, drop is controlled in the suitable scope.Progressively be warming up to 70 ℃, be incubated 2 hours, be warming up to 85 ℃ again, be incubated and rise to 95 ℃ after 4 hours, be incubated after 1 hour, filter, with hot wash for several times, with drying for standby after the acetone extracting.Promptly obtain the degree of cross linking and be 6% macroporous cross-linked polystyrene resin.
Embodiment 3 degrees of cross linking are the synthetic of 50% macroporous cross-linked polystyrene carrier
In the there-necked flask of the 250mL that mechanical agitation and condenser pipe are housed, add gelatin 0.3g, distilled water 150mL, heating and stirring make the gelatin dissolving, add normal heptane 20mL then, styrene 10g, divinylbenzene 10g, BPO 0.2g (being added in the styrene).Start mechanical agitation and control mixing speed, drop is controlled in the suitable scope.Progressively be warming up to 70 ℃, be incubated 2 hours, be warming up to 85 ℃ again, be incubated and rise to 95 ℃ after 4 hours, be incubated after 1 hour, filter, with hot wash for several times, with drying for standby after the acetone extracting.Promptly obtain the degree of cross linking and be 50% macroporous cross-linked polystyrene resin.
Embodiment 4 degrees of cross linking are the chloromethylation of 10% macropore polystyrene resin (ps)
In the there-necked flask of 150mL, add 10% crosslinked macropore polystyrene resin (ps) 5g and chloromethyl ether 20mL of embodiment 1 preparation and place and spend the night, add 10mL nitrobenzene, the 7g anhydrous zinc chloride, be warming up to 95 ℃ gradually, react and finish reaction after 10 hours, leach resin, respectively with ethanol and deionized water washing, drying for standby.
The Cholromethylation method of many (greatly) hole polystyrene resin of other degrees of cross linking is the same.
Synthesizing of embodiment 5 N-9-anthracene methylene cinchonine salts (2)
Filling adding 10 gram cinchonine CN (1) in the 250mL round-bottomed flask of 125mL toluene, 9-chloromethyl anthracene 10 grams, under agitation added hot reflux 3 hours, after the cooling reactant liquor is poured in the ether of 450mL, filtration obtains the thick product of solid N-9-anthracene methylene cinchonine salt, with mixed solvent carrene/ether recrystallization purifying, obtain pure product.
Synthesizing of embodiment 6 N-9-anthracene methylene cinchonidine salt (4)
Filling adding 10.7 gram cinchonidine CD (3) in the 250mL round-bottomed flask of 125mL toluene, 9-chloromethyl anthracene 10 grams, under agitation added hot reflux 3 hours, after the cooling reactant liquor is poured in the ether of 450mL, filtration obtains the thick product of solid N-9-anthracene methylene cinchonidine salt, with mixed solvent carrene/ether recrystallization purifying, obtain pure product.
Embodiment 7 PS-CN-3's is synthetic
Add 2.3g (7.82mmol) cinchonine CN (1) in the 50mL round-bottomed flask of 25mL toluene filling, stirring makes its dissolving, add 0.21g (8.7mmol) sodium hydride then, stirring at room adds 1.45g embodiment 4 preparation after 5 hours the degree of cross linking is 10% chloromethylation macroreticular resin (6), stirred 15～20 hours down at 35 ℃, filter, respectively for several times with ethanol, toluene and acetone washing, drying.
Embodiment 8 PS-CN-3's is synthetic
Add 2.9g (9.86mmol) cinchonine CN (1) in the 50mL round-bottomed flask of 25mL toluene filling, stirring makes its dissolving, add 0.31g (12.9mmol) sodium hydride then, stirring at room adds 1.45g after 5 hours be 20% chloromethylation macroreticular resin (6) according to the degree of cross linking of embodiment 4 methods preparations, stirred 15～20 hours down at 35 ℃, filter, respectively for several times with ethanol, toluene and acetone washing, drying.
Embodiment 9 PS-CD-4's is synthetic
Add 2.3g (7.82mmol) cinchonidine CD (3) in the 50mL round-bottomed flask of 25mL toluene filling, stirring makes its dissolving, add 0.21g (8.7mmol) sodium hydride then, stirring at room adds 1.45g after 5 hours be 50% chloromethylation macroreticular resin (6) according to the degree of cross linking of the method for embodiment 4 preparation, stirred 15～20 hours down at 35 ℃, filter, respectively for several times with ethanol, toluene and acetone washing, drying.
Embodiment 10 PS-CN-4's is synthetic
Filling the quaternary ammonium salt (2) that adds 3.36g (6.46mmol) cinchonine CN in the 50mL round-bottomed flask of 25mL toluene, stirring makes its dissolving, add 0.171g (7.12mmol) sodium hydride then, stirring at room adds 1.20g after 6 hours be 30% chloromethylation macroreticular resin (6) according to the degree of cross linking of embodiment 4 methods preparations, stirred 17 hours down at 35 ℃, filter, respectively for several times with ethanol, toluene and acetone washing, drying.
Embodiment 11 PS-CN-7's is synthetic
Filling the quaternary ammonium salt (2) that adds 3.93g (7.55mmol) cinchonine CN in the 50mL round-bottomed flask of 25mL toluene, stirring makes its dissolving, add 0.24g (10mmol) sodium hydride then, stirring at room adds 1.20g after 6 hours be 25% chloromethylation macroreticular resin (6) according to the degree of cross linking of embodiment 4 methods preparations, stirred 17 hours down at 35 ℃, filter, respectively for several times with ethanol, toluene and acetone washing, drying.
Embodiment 12 PS-CD-8's is synthetic
Filling the quaternary ammonium salt (4) that adds 3.36g (6.46mmol) cinchonidine CD in the 50mL round-bottomed flask of 25mL toluene, stirring makes its dissolving, add 0.171g (7.12mmol) sodium hydride then, stirring at room adds 2.0g after 6 hours be 6% chloromethylation macroreticular resin (6) according to the degree of cross linking of the method for embodiment 4 preparation, stirred 17 hours down at 35 ℃, filter, respectively for several times with ethanol, toluene and acetone washing, drying.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned instruction content of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (4)
1. the preparation method of the cinchona alkaloid compound of a macromolecule loading, it is characterized in that, in organic solvent and inorganic base or organic base in the presence of, the expanded polystyrene resin of cinchona alkaloid compound and chloromethylation reacted 10～60 hours to reflux temperature at 20 ℃, leached resin then; The mol ratio of chloromethyl and alkali is 0.6～3.0 in described cinchona alkaloid compound, the expanded polystyrene resin: 1: 1.0～5.0;
Described cinchona alkaloid compound is for having compound in structural formula I, its isomers and N-9-anthracene methylene quaternary ammonium salt thereof:
Wherein R is H or CH
3O;
Described expanded polystyrene cross-linkage of resin is 6%～50%, and granularity is 20～100 orders, aperture 20～200 nanometers.
2. the preparation method of the cinchona alkaloid compound of the described macromolecule loading of claim 1, it is characterized in that described cinchona alkaloid compound is quinine, chinidine, cinchonine, cinchonidine, N-9-anthracene methylene cinchonine salt, N-9-anthracene methylene cinchonidine, N-9-anthracene methylene quinine salt and N-9-anthracene methylene chinidine.
3. the preparation method of the cinchona alkaloid compound of claim 1 or 2 described macromolecule loadings is characterized in that, described organic solvent is toluene, dimethylbenzene, N, dinethylformamide or methyl-sulfoxide.
4. the preparation method of the cinchona alkaloid compound of the described macromolecule loading of claim 1 is characterized in that, the mol ratio of chloromethyl and alkali is 1.0～1.5 in described cinchona alkaloid compound, the expanded polystyrene resin: 1: 1.5～3.3.
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| CN101735368B (en) * | 2009-12-15 | 2011-11-16 | 上海第二工业大学 | Sulfonated porous crosslinked polystyrene resin loaded cinchona alkaloid compound and preparation method thereof |
| CN101733153B (en) * | 2009-12-15 | 2011-12-21 | 上海第二工业大学 | Porous crosslinked polystyrene sulfonic acid resin loaded quinine quaternary ammonium salt and preparation method thereof |
| CN103551191B (en) * | 2013-10-30 | 2015-06-24 | 新乡学院 | Application of chiral amphiphilic block copolymer in chiral synthesis |
| CN105688983B (en) * | 2014-09-04 | 2018-04-24 | 中国药科大学 | A kind of preparation method and purposes of ring-type quinine quarternary ammonium salt compound |
| CN105348428B (en) * | 2015-10-20 | 2017-07-25 | 华东师范大学 | A kind of preparation method and applications of cross-linking type polymerization catalyst |
| CN111116333B (en) * | 2019-12-27 | 2023-10-20 | 泛亚（武汉）食品科技有限公司 | High-molecular-load oxidant containing iodine with high valence, preparation method and application |
| CN115672400B (en) * | 2022-10-31 | 2024-06-11 | 西南大学 | Anchoring heterogeneous organic catalyst and preparation method and application thereof |
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| CN1523024A (en) * | 2003-09-12 | 2004-08-25 | 中国科学院上海有机化学研究所 | Macromolecule immobilized cinchonine alkaloid ligand, synthesis method and use thereof |
Non-Patent Citations (1)
| Title |
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| Baptiste Thierry et al.Cinchona alkaloid-based polymer-bound phase-transfer catalysts: Efficient enantioselective alkylation of benzophenone imine of glycine esters.《Molecular Diversity》.2005,第9卷第281页Scheme 7,第280页左栏第4段至第282页左栏Figure 5下第1段,第287页左栏第5段至右栏第2段. * |
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