CN105330662A - Preparation of imidazole type ionic liquid derived by cinchona alkaloid - Google Patents
Preparation of imidazole type ionic liquid derived by cinchona alkaloid Download PDFInfo
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- CN105330662A CN105330662A CN201510854748.2A CN201510854748A CN105330662A CN 105330662 A CN105330662 A CN 105330662A CN 201510854748 A CN201510854748 A CN 201510854748A CN 105330662 A CN105330662 A CN 105330662A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D453/00—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids
- C07D453/02—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids containing not further condensed quinuclidine ring systems
- C07D453/04—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids containing not further condensed quinuclidine ring systems having a quinolyl-4, a substituted quinolyl-4 or a alkylenedioxy-quinolyl-4 radical linked through only one carbon atom, attached in position 2, e.g. quinine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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Abstract
The invention discloses the preparation of imidazole type ionic liquid derived by cinchona alkaloid. The preparation is characterized by adopting quinine or cinchonine to modify 9-hydroxyl of the cinchona alkaloid; carrying out a replacement reaction on chloride salt of obtained imidazole type ionic liquid and inorganic metal salt; preparing imidazole type ionic liquid catalysts of different anions. Compared with the prior art, the preparation disclosed by the invention has the advantages that the catalytic activity is high, the catalysts are easily separated and recycled and can be reused again, the preparation is simple, post-processing is easy, the stability of the catalysts is greatly increased, the application range of the catalysts in a micromolecular organic asymmetric reaction is expanded, reaction conditions are optimized, reaction requirements are reduced, the catalytic activity and the enantioselectivity of a chiral imidazole type ionic liquid catalyst in an asymmetric reaction are further increased, and great significance is obtained for researching medicinal chemistry and medical intermediate compounds.
Description
Technical field
The present invention relates to organic catalyst technical field, the preparation of the imidazole type ion liquid that especially a kind of quinine be used in asymmetric reaction derives.
Background technology
At present, for the catalyzer of asymmetric reaction as noble metal complexes, natural enzyme etc., although better catalytic activity, catalyst levels is large, and can not recycle again, easily cause the irrational utilization of resource, wastage of material is serious.In recent years, the application of small molecules organic catalyst in asymmetric reaction gets more and more people's extensive concerning, and especially quinine and derivative thereof show good catalytic activity and enantioselectivity is also more and more subject to people's attention in the reactions such as asymmetric Michael Reaction, asymmetric Friedel-Crafts react.Although this type of micromolecule catalyst preparation technology is simple, raw material cheap, the later stage modifies easily, and reaction environment is gentle, catalytic activity is good, pollutes the advantages such as little, but does not have the Stability Analysis of Structures of imidazole type ion liquid, dissolving power is strong, steam forces down, and viscosity is suitable, the good characteristic that electroconductibility is high, and with the functionalized ion liquid of chirality in organic reaction as reaction medium or catalyzer, can change reaction mechanism, make the activity of catalyzer, stability better, selectivity, transformation efficiency are higher.So how the natural chiral center of quinine is combined with imidazole ion liquid, form the quinine imidazole type ion liquid catalyzer that a class is novel, in small molecules organic catalysis, there is considerable Research Significance and application prospect.
Summary of the invention
The preparation of the imidazole type ion liquid that a kind of quinine that the object of the invention is to provide for the deficiencies in the prior art derives, adopt the modification to quinine 9-position hydroxyl, build the imidazole type ion liquid that quinine is derivative with N-Methylimidazole quaterisation after constructing benzyl alkyl chloride, make the natural chiral center of quinine and imidazole ion liquid in conjunction with the novel quinine imidazole type ion liquid catalyzer of formation one class, to expand the range of application of catalyzer in the organic asymmetric reaction of small molecules, Optimal reaction conditions, reduce reaction requirement, the catalytic activity of further raising chiral imidazole type ionic-liquid catalyst in asymmetric reaction, the utilization ratio of enantioselectivity and raw material.
The concrete technical scheme realizing the object of the invention is: the preparation of the imidazole type ion liquid that a kind of quinine derives, be characterized in adopting quinine or cinchonine to the modification of quinine 9-position hydroxyl, then the villaumite of the imidazole ion liquid obtained and inorganic metal salt are carried out replacement(metathesis)reaction, the imidazole type ion liquid catalyzer of preparation different anions, concrete preparation is undertaken by following reaction structure formula and operation steps:
Wherein: Cl
–may be exchanged for NO
3 –, PF
6 –, BF
4 –, NTf
2 –, OAc
–or OTf
–.
The first step: by quinine (Quinine), Quinidine (Quinidine), cinchonine (Cinchonine) or cinchonine fourth (Cinchonidine) and triethylamine and tetrahydrofuran (THF), acetonitrile or dimethyl formamide (DMF) are placed in 0 DEG C of ice-water bath by 1:1.1 ~ 1.8:10 ~ 200 mixed in molar ratio, drip solution chloromethyl benzoic acid chlorides and methylene dichloride or tetrahydrofuran (THF) being pressed to 1:10 ~ 50 mixed in molar ratio, at normal temperature after dropping, synthesis under normal pressure 5 ~ 24 hours, be spin-dried for solvent after reaction terminates and carry out separatory with isopyknic methylene dichloride and water, the isopyknic methylene dichloride of aqueous phase extracts at twice, extract with saturated aqueous common salt after merging organic phase, extraction liquid drying, filter, the compound that concentrated and silica gel column chromatography obtains quinine 9-position hydroxyl modified is benzyl alkyl chloride (QN-Cl, QD-Cl, CN-Cl or CD-Cl), described 1:10 ~ 50 mixed in molar ratio is pressed to chloromethyl benzoic acid chlorides and methylene dichloride.
Second step: above-mentioned benzyl alkyl chloride (QN-Cl, QD-Cl, CN-Cl or CD-Cl) and N-Methylimidazole and acetonitrile are pressed 1:1.0 ~ 2.0:50 ~ 100 mixed in molar ratio, 5 ~ 48 hours quaterisations are carried out under 25 ~ 45 DEG C of temperature, normal pressure, be spin-dried for solvent after reaction terminates, obtaining target product through silica gel column chromatography is the imidazole type ion liquid (QN-IL, QD-IL, CN-IL or CD-IL) that quinine derives.
3rd step: above-mentioned imidazole type ion liquid (QN-IL, QD-IL, CN-IL or CD-IL) and Silver Nitrate, Silver monoacetate or silver trifluoromethanesulfonate are pressed 1:1.0 ~ 1.2 mixed in molar ratio, under normal temperature, normal pressure, carry out the replacement(metathesis)reaction of 12 ~ 48 hours, thus obtain the imidazole type ion liquid catalyzer of different anions.
It is high that the present invention compared with prior art has catalytic activity, the easily separated recovery of catalyzer and again recycling, preparation is simple, processing ease, synthetic route is short, aftertreatment is easy, raw material availability is high, substantially increase the stability of catalyzer, to expand the range of application of catalyzer in the organic asymmetric reaction of small molecules, Optimal reaction conditions, reduce reaction requirement, the catalytic activity of further raising chiral imidazole type ionic-liquid catalyst in asymmetric reaction, the utilization ratio of enantioselectivity and raw material, especially the research of pharmaceutical chemistry and pharmaceutical intermediate compound is had important practical significance.
Embodiment
By following specific embodiment, the present invention is described in further detail.
Embodiment 1
The first step: take 8.68g quinine (Quinine) and 2.98g triethylamine is dissolved in 40ml tetrahydrofuran (THF), 5.02g is dissolved in 5ml tetrahydrofuran (THF) to chloromethyl benzoic acid chlorides, at 0 DEG C of temperature, the tetrahydrofuran solution of acyl chlorides is slowly dropwise instilled in the tetrahydrofuran solution of quinine triethylamine, after dropwising, at normal temperature, react 12 hours under normal pressure, TLC monitors after reaction terminates and is spin-dried for solvent, with 20ml methylene dichloride and water equal-volume hybrid extraction, aqueous phase extracts at twice with 40ml methylene dichloride again, once appropriate anhydrous Na is added afterwards with the extraction of 30ml saturated NaCl solution after merging organic phase
2sO
4dry, then filtration, concentrated filtrate and silica gel column chromatography (EA:PE=1:5) obtain the compound of quinine 9-position hydroxyl modified is benzyl alkyl chloride (QN-Cl) (3-(4-(((R)-(6-methoxyquinolin-4-yl) ((1S, 2S, 4S, 5R)-5-vinylquinuclidin-2-yl) methoxy) carbonyl) benzyl)-1-methyl-1H-imidazol-3-iumchloride), its productive rate is 90%.
Second step: take above-mentioned benzyl alkyl chloride (QN-Cl) compound 4.76g and be dissolved in 5ml acetonitrile, and add 0.98gN-Methylimidazole, and at 40 DEG C of temperature, synthesis under normal pressure 12 hours, solvent is spin-dried for, through silica gel column chromatography (EA:CH after reaction terminates
3oH=1:1) obtaining target product is the imidazole type ion liquid (QN-IL) that quinine derives, and its productive rate is 65%.
3rd step: take 2.0g imidazole type ion liquid (QN-IL) and the replacement(metathesis)reaction of carrying out 24 hours containing the inorganic salt of different anions under normal temperature, normal pressure, if inorganic salt are Silver Nitrate, then add-on is 0.61g, and its productive rate is 70%; If inorganic salt are Silver monoacetate, then add-on is 0.60g, and its productive rate is 76%; If inorganic salt are silver trifluoromethanesulfonate, then add-on is 0.92g, and its productive rate is 83%, thus obtains the quinine imidazole type ion liquid catalyzer of different anions.
Embodiment 2
The first step: take 4.15g Quinidine (Quinidine) and 1.53g triethylamine is dissolved in the acetonitrile of 20ml, 2.46g is dissolved in 3ml tetrahydrofuran (THF) to chloromethyl benzoic acid chlorides, at 0 DEG C of temperature, just the tetrahydrofuran solution of acyl chlorides slowly dropwise instills in the acetonitrile solution of Quinidine triethylamine, after dropwising, at normal temperature, synthesis under normal pressure 16 hours, TLC monitors after reaction terminates and is spin-dried for solvent, with 20ml methylene dichloride and water equal-volume hybrid extraction, aqueous phase extracts at twice with 40ml methylene dichloride again, once appropriate anhydrous Na is added afterwards with the extraction of 30ml saturated NaCl solution after merging organic phase
2sO
4dry, then filtration, concentrated filtrate and silica gel column chromatography (EA:PE=1:3) obtain compound is benzyl alkyl chloride (QD-Cl) (3-(4-(((S)-(6-methoxyquinolin-4-yl) ((1S, 2S, 4S, 5R)-5-vinylquinuclidin-2-yl) methoxy) carbonyl) benzyl)-1-methyl-1H-imidazol-3-iumchloride), its productive rate is 82%.
Second step: take above-mentioned benzyl alkyl chloride (QD-Cl) compound 5.40g and be dissolved in 5ml acetonitrile, and add 1.86gN-Methylimidazole, and at 40 DEG C of temperature, synthesis under normal pressure 14 hours, solvent is spin-dried for, through silica gel column chromatography (EA:CH after reaction terminates
3oH=1:2) obtaining target product is the imidazole type ion liquid (QD-IL) that Quinidine derives, and its productive rate is 61%.
3rd step: take 1.0g imidazole type ion liquid (QD-IL) and the replacement(metathesis)reaction of carrying out 24 hours containing the inorganic salt of different anions under normal temperature, normal pressure, if inorganic salt are Silver Nitrate, then add-on is 0.32g, and its productive rate is 75%; If inorganic salt are Silver monoacetates, then add-on is 0.32g, and its productive rate is 82%; If inorganic salt are silver trifluoromethanesulfonates, then add-on is 0.49g, and its productive rate is 83%.Thus obtain the Quinidine imidazole type ion liquid catalyzer of different anions.
Embodiment 3
The first step: take 8.59g cinchonine (Cinchonine) and 3.24g triethylamine is dissolved in the dimethyl formamide (DMF) of 50ml, 5.46g is dissolved in 3ml tetrahydrofuran (THF) to chloromethyl benzoic acid chlorides, at 0 DEG C of temperature, the tetrahydrofuran solution of acyl chlorides is slowly dropwise instilled in the DMF solution of Quinidine triethylamine, after dropwising, at normal temperature, synthesis under normal pressure 16 hours, TLC monitors after reaction terminates and is spin-dried for solvent, add 20ml ethyl acetate, 200ml distilled water diluting, the white solid that collecting by filtration is separated out, filtrate is separatory again, aqueous phase extracts at twice by 40ml ethyl acetate again, once appropriate anhydrous Na is added afterwards with the extraction of 20ml saturated NaCl solution after merging organic phase
2sO
4dry, then filtration, concentrated filtrate and silica gel column chromatography (EA:PE=1:5) obtain compound is benzyl alkyl chloride (CN-Cl) (1-methyl-3-(4-(((S)-quinolin-4-yl ((1S, 2S, 4S, 5R)-5-vinylquinuclidin-2-yl) methoxy) c-arbonyl) benzyl)-1H-imidazol-3-iumchloride), its productive rate is 90%.
Second step: take above-mentioned benzyl alkyl chloride (CN-Cl) compound 3.38g and be dissolved in 5ml acetonitrile, and add 0.62gN-Methylimidazole, and at 40 DEG C of temperature, synthesis under normal pressure 14 hours, solvent is spin-dried for, through silica gel column chromatography (EA:CH after reaction terminates
3oH=1:2) obtaining target product is the imidazole type ion liquid (CN-IL) that cinchonine derives, and its productive rate is 70%.
3rd step: take 0.80g imidazole type ion liquid (CN-Cl) and the replacement(metathesis)reaction of carrying out 36 hours containing the inorganic salt of different anions under normal temperature, normal pressure, if inorganic salt are Silver Nitrate, then add-on is 0.26g, and its productive rate is 76%; If inorganic salt are Silver monoacetate, then add-on is 0.25g, and its productive rate is 86%; If inorganic salt are silver trifluoromethanesulfonate, then add-on is 0.39g, and its productive rate is 73%, thus obtains the cinchonine imidazole type ion liquid catalyzer of different anions.
Embodiment 4
The first step: take 4.36g cinchonine fourth (Cinchonidine) and 1.67g triethylamine is dissolved in the acetonitrile of 20ml, 2.90g4-chloromethyl benzoic acid chlorides is dissolved in 2ml tetrahydrofuran (THF), at 0 DEG C of temperature, the tetrahydrofuran solution of acyl chlorides is slowly dropwise instilled in the acetonitrile solution of cinchonine fourth triethylamine, then after dropwising, at normal temperature, synthesis under normal pressure 8 hours, TLC monitors after reaction terminates and is spin-dried for solvent, with 20ml methylene dichloride and water equal-volume hybrid extraction, aqueous phase extracts at twice with 40ml methylene dichloride again, once appropriate anhydrous Na is added afterwards with the extraction of 30ml saturated NaCl solution after merging organic phase
2sO
4dry, then filtration, concentrated filtrate and silica gel column chromatography (EA:PE=1:2) obtain compound is benzyl alkyl chloride (CD-Cl) (1-methyl-3-(4-(((R)-quinolin-4-yl ((1S, 2S, 4S, 5R)-5-vinylquinuclidin-2-yl) methoxy)-carbonyl) benzyl)-1H-imidazol-3-iumchloride), its productive rate is 82%.
Second step: take above-mentioned benzyl alkyl chloride (CD-Cl) compound 1.52g and be dissolved in 5ml acetonitrile, and add 0.28gN-Methylimidazole, and at 40 DEG C of temperature, synthesis under normal pressure 14 hours, solvent is spin-dried for, through silica gel column chromatography (EA:CH after reaction terminates
3oH=1:3) obtaining target product is the imidazole type ion liquid (CD-IL) that Cinchonidune derives, and its productive rate is 57%.
3rd step: take 0.80g imidazole type ion liquid (CD-IL) and the replacement(metathesis)reaction of carrying out 36 hours containing the inorganic salt of different anions under normal temperature, normal pressure, if inorganic salt are Silver Nitrate, then add-on is 0.18g, and its productive rate is 74%; If inorganic salt are Silver monoacetate, then add-on is 0.18g, and its productive rate is 80%; If inorganic salt are silver trifluoromethanesulfonate, then add-on is 0.27g, and its productive rate is 78%, thus obtains the cinchonine Butamisole type ionic-liquid catalyst of different anions.
Just the present invention will be further described for each embodiment above, and be not used to limit patent of the present invention, allly implements for the present invention's equivalence, within the right that all should be contained in patent of the present invention.
Claims (1)
1. the preparation of imidazole type ion liquid that derives of a quinine, it is characterized in that adopting quinine or cinchonine to the modification of quinine 9-position hydroxyl, then the villaumite of the imidazole ion liquid obtained and inorganic metal salt are carried out replacement(metathesis)reaction, the imidazole type ion liquid catalyzer of preparation different anions, concrete preparation is undertaken by following reaction structure formula and operation steps:
Wherein: Cl
–may be exchanged for NO
3 –, PF
6 –, BF
4 –, NTf
2 –, OAc
–or OTf
–;
The first step: by quinine (Quinine), Quinidine (Quinidine), cinchonine (Cinchonine) or cinchonine fourth (Cinchonidine) and triethylamine and tetrahydrofuran (THF), acetonitrile or dimethyl formamide (DMF) are placed in 0 DEG C of ice-water bath by 1:1.1 ~ 1.8:10 ~ 200 mixed in molar ratio, drip solution chloromethyl benzoic acid chlorides and methylene dichloride or tetrahydrofuran (THF) being pressed to 1:10 ~ 50 mixed in molar ratio, at normal temperature after dropping, synthesis under normal pressure 5 ~ 24 hours, be spin-dried for solvent after reaction terminates and carry out separatory with isopyknic methylene dichloride and water, the isopyknic methylene dichloride of aqueous phase extracts at twice, extract with saturated aqueous common salt after merging organic phase, extraction liquid drying, filter, the compound that concentrated and silica gel column chromatography obtains quinine 9-position hydroxyl modified is benzyl alkyl chloride (QN-Cl, QD-Cl, CN-Cl or CD-Cl), described 1:10 ~ 50 mixed in molar ratio is pressed to chloromethyl benzoic acid chlorides and methylene dichloride.
Second step: above-mentioned benzyl alkyl chloride (QN-Cl, QD-Cl, CN-Cl or CD-Cl) and N-Methylimidazole and acetonitrile are pressed 1:1.0 ~ 2.0:50 ~ 100 mixed in molar ratio, the quaterisation of 5 ~ 48 hours is carried out under 25 ~ 45 DEG C of temperature, normal pressure, be spin-dried for solvent after reaction terminates, obtaining target product through silica gel column chromatography is the imidazole type ion liquid (QN-IL, QD-IL, CN-IL or CD-IL) that quinine derives.
3rd step: above-mentioned imidazole type ion liquid (QN-IL, QD-IL, CN-IL or CD-IL) and Silver Nitrate, Silver monoacetate or silver trifluoromethanesulfonate are pressed 1:1.0 ~ 1.2 mixed in molar ratio, under normal temperature, normal pressure, carry out the replacement(metathesis)reaction of 12 ~ 48 hours, thus obtain the imidazole type ion liquid catalyzer of different anions.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105732387A (en) * | 2016-04-14 | 2016-07-06 | 大连理工大学 | Novel method for asymmetric alpha-hydroxylation of photo-oxygenation beta-dicarbonyl compound based on C-2' phase transfer catalyst |
| CN105777742A (en) * | 2016-04-29 | 2016-07-20 | 大连理工大学 | Chiral ionic liquid |
| CN105903457A (en) * | 2016-06-12 | 2016-08-31 | 中国科学院青岛生物能源与过程研究所 | Imidazole ionic liquid chiral stationary phase and preparation method and application |
| CN107899611A (en) * | 2017-11-03 | 2018-04-13 | 大连理工大学 | One kind has the organic catalyst of visible light catalytic asymmetry photocatalysis hydroxylating performance, preparation method and applications |
| CN110511217A (en) * | 2019-09-25 | 2019-11-29 | 京博农化科技有限公司 | It is a kind of to be catalyzed the catalyst and its application that indoxacarb key intermediate synthesizes |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732387A (en) * | 2016-04-14 | 2016-07-06 | 大连理工大学 | Novel method for asymmetric alpha-hydroxylation of photo-oxygenation beta-dicarbonyl compound based on C-2' phase transfer catalyst |
| CN105732387B (en) * | 2016-04-14 | 2019-03-05 | 大连理工大学 | The method of novel C -2` phase transfer catalyst photooxidation beta-dicarbonyl compound asymmetry 'alpha '-hydroxylation |
| CN105777742A (en) * | 2016-04-29 | 2016-07-20 | 大连理工大学 | Chiral ionic liquid |
| CN105903457A (en) * | 2016-06-12 | 2016-08-31 | 中国科学院青岛生物能源与过程研究所 | Imidazole ionic liquid chiral stationary phase and preparation method and application |
| CN107899611A (en) * | 2017-11-03 | 2018-04-13 | 大连理工大学 | One kind has the organic catalyst of visible light catalytic asymmetry photocatalysis hydroxylating performance, preparation method and applications |
| CN107899611B (en) * | 2017-11-03 | 2020-04-07 | 大连理工大学 | Organic catalyst with visible light catalytic asymmetric photocatalytic hydroxylation performance, preparation method and application thereof |
| CN110511217A (en) * | 2019-09-25 | 2019-11-29 | 京博农化科技有限公司 | It is a kind of to be catalyzed the catalyst and its application that indoxacarb key intermediate synthesizes |
| CN110511217B (en) * | 2019-09-25 | 2022-01-28 | 京博农化科技有限公司 | Catalyst for catalyzing synthesis of indoxacarb key intermediate and application thereof |
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| CN105330662B (en) | 2017-05-24 |
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