CN1995049A - Manganese catalyst of 8-hydroxy quinoline derivative and its uses in olefin epoxidation - Google Patents
Manganese catalyst of 8-hydroxy quinoline derivative and its uses in olefin epoxidation Download PDFInfo
- Publication number
- CN1995049A CN1995049A CNA2006101369894A CN200610136989A CN1995049A CN 1995049 A CN1995049 A CN 1995049A CN A2006101369894 A CNA2006101369894 A CN A2006101369894A CN 200610136989 A CN200610136989 A CN 200610136989A CN 1995049 A CN1995049 A CN 1995049A
- Authority
- CN
- China
- Prior art keywords
- general formula
- catalyst
- iii
- alkene
- hydrogen peroxide
- 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.)
- Granted
Links
Abstract
The invention discloses a manganese catalyst of 8-hydroxy quinoline derivant and application in the olefin epoxidised course, which is characterized by the following: the 8-hydroxy quinoline derivant of general formula (I) of catalyst is complex compound of ligand and magnesium ion, which forms general formula (II) or (III); the catalyst is reacted by olefin and hydrogen peroxide as oxidant in the solvent; the molar rate of catalyst is 0.5-5% corresponding to the molar rate of olefin.
Description
Technical field
The present invention relates to a kind of Mn catalyst of oxine derivative and the application in alkene epoxidation thereof.
Background technology
Manganese is with its cheapness, low toxicity and high reactivity and highly selective and be widely used in catalyzer in the organic synthesis, and be applied to the epoxidation of hydrogen peroxide as the alkene of oxygenant, but mn ion has very strong capacity of decomposition to hydrogen peroxide, causes the utilization ratio of hydrogen peroxide in reaction process very low.People attempt using various part and manganese coordination improving the utilization ratio of hydrogen peroxide, but the result is not really desirable.For example the many Salen type manganese complexs of report are the very effective catalyzer (a.E.N.Jacobsen of alkene epoxidation both at home and abroad, W.Zhang, A.R.Muci, J.R.Ecker, and L.Deng, J.Am.Chem.Soc., 1991,113,7063.b.Y.N.Ito and T.Katsuki, Bull.Chem.Soc.Jpn., 1999,72,603), but when using hydrogen peroxide as oxidant, it is bigger not only to exist catalyst levels, easy inactivation, and the hydrogen peroxide utilization ratio is low, therefore generally will use metachloroperbenzoic acid, it is just more effective that PhIO or clorox are made oxygenant.External report (a.Lane, the B.S. that once attempts doing olefin epoxidation catalysts with inexpensive manganese salt; Burgess, K.J.Am.Chem.Soc.2001,123,2933.b.Lane, B.S.; Vogt, M.; DeRose, V.J.; Burgess, K.J.Am.Chem.Soc.2002,124,11946.), but use this catalyzer alkene to be transformed fully with excessive greatly hydrogen peroxide (being approximately 10 times of amounts of substrate).People such as Banfi report the Manganese Porphyrin of using band chlorobenzene ring to modify and make catalyzer, drop to about 2 times (Banfi, S of substrate adding the consumption that can make hydrogen peroxide when imidazoles or imidazoles and carboxylic acid are made auxiliary agent; Legramandi, F.; Montanari, F.; Pozzi, G.; Quici, S.J.Chem.Soc., Chem.Commun.1991,1285.), this is our the highest catalysis epoxidation system of hydrogen peroxide utilization ratio of seeing up to now.But because the part of this catalyzer is difficult to synthesize, recovery difficult is big, and uses higher relatively methylene dichloride or the acetonitrile of toxicity to make solvent, so practical value is not high.
Summary of the invention
The object of the present invention is to provide the Mn catalyst of a kind of oxine and derivative thereof and the application in alkene epoxidation thereof.Realizing that Preparation of Catalyst is simple, cheap, reusable, chemo-selective height, hydrogen peroxide utilization ratio height during with hydrogen peroxide as oxidant, epoxidation efficient height, good stability, the used nontoxic or low toxicity of solvent, reaction conditions gentleness.
Technical scheme of the present invention is: catalyzer is that the oxine derivative by general formula general formula (I) is the complex compound that part and mn ion form general formula (II) or general formula (III);
Substituent R in the general formula (I) on the aromatic ring
4, R
5, R
6, R
7, R
8, R
9Each hydrogen naturally independently of one another, halogen, alkyl, alkoxyl group, hydroxyl, nitro, amido, glycosyl replaces glycosyl and cyclodextrin; General formula (II), (III) metal ion in is Mn; Dentate X in the general formula (III) can be a halogen, PF
6 -, methyl ethyl diketone, acetate moiety and other carboxylate radical negative ion.
The synthetic method of the catalyzer of general formula (II) may further comprise the steps:
(1) part with 10mmol general molecular formula (II) is dissolved in the organic solvent;
(2) under agitation dropwise add the ethanolic soln of the manganous salt of 5mmol;
(3) continue to stir at normal temperatures 10 to 20 minutes,
(4) suction filtration is used washing with alcohol, and drying gets catalyzer.
The synthetic method of the catalyzer of general formula (III) may further comprise the steps:
(1) part with 10mmol general molecular formula (II) is dissolved in the organic solvent;
(2) under agitation dropwise add the ethanolic soln of the manganous salt of 5mmol;
(3) splash into the 2-3mmol hydrogen peroxide, splash into ammoniacal liquor again the pH value of solution value is transferred between the 6-7, or splash into 4ml and contain 10mmolNH
4The aqueous solution of OAc;
(4) continue to stir at normal temperatures or refluxed 1 to 2 hour;
(5) suction filtration is used washing with alcohol, drying, the solid catalyst (X=Cl or OAc) of general formula (III).
Described organic solvent is methyl alcohol, ethanol, acetone, methylene dichloride, tetrahydrofuran (THF) etc.
Above-mentioned catalyzer prepares application on the epoxide at catalyzing expoxidation of olefines, is in the presence of catalyzer, and alkene and oxidants hydrogen peroxide are reacted in solvent, and its catalyst consumption is the 0.5-5% of alkene molar weight.
Above-mentioned catalyzer used additives or not in the catalyzing expoxidation of olefines process with carboxylate salt, carboxylic acid, carbonate, imidazoles or nitrogen-containing heterocycle compound are auxiliary agent, the preferred mol ratio of catalyzer and auxiliary agent is 1: 1-20.
Described solvent is one or more the mixed solvent in water, ketone, alcohol, hydrochloric ether, aromatic hydrocarbons, DMF, ether or the ester.The mixed solvent of water and acetone preferably; The volume ratio of water and acetone is 1: 2-5.
Described alkene is general formula (IV), preferably cyclenes, fragrant alkene, alkene, terpenes, enol class.
In the general formula (IV), R, R
1, R
2And R
3, each hydrogen naturally independently of one another, alkyl, aryl, arylalkyl, thiazolinyl, alkynyl, hydroxyl, ether, epoxy group(ing), halogeno-group, aldehyde radical, ketone group, carbonyl, ester group, amide group, cyanate ester based, isocyanate group, thiocyanate groups, amido, diazo, nitro, itrile group, nitroso-group, sulfenyl, sulfoxide group, sulfuryl, thiol group, ortho acid ester group, at least a in imido grpup and the urea groups.
Olefin epoxidation method may further comprise the steps: the general formula (II) of the 0.5-5% of alkene molar weight or oxine derivative Mn catalyst (III) are dissolved in the reaction solvent, add raw material olefin again, after stirring, under 0-25 ℃ of temperature, dropwise add the 1-3 oxidant hydrogen peroxide doubly of alkene molar weight, reacted 1-24 hour.
Advantage of the present invention is: Preparation of Catalyst is simple, cheap, reusable, chemo-selective height, when being applied to the reaction in solvent of alkene and oxidants hydrogen peroxide, hydrogen peroxide utilization ratio height, epoxidation efficient height, good stability, the used nontoxic or low toxicity of solvent, the reaction conditions gentleness.
Embodiment
Embodiment 1: general formula (II) catalyzer synthetic:
The part of 10mmol general molecular formula (I) is dissolved in 30-100ml ethanol or the methylene dichloride, under agitation dropwise adds 20ml and contain 5mmol Mn (OAc)
2Ethanolic soln.Continue to stir at normal temperatures 10 to 20 minutes.Suction filtration is used washing with alcohol, and drying gets the catalyzer that solid is general formula (II).Product yield is about 90%.
Embodiment 2: general formula (III) catalyzer synthetic:
The part of 10mmol general molecular formula (I) is dissolved in 30-50ml
In the tetrahydrofuran (THF), under agitation dropwise add 20ml and contain 5mmol MnCl
2Ethanolic soln.And then splash into the 2-3mmol hydrogen peroxide, splash into ammoniacal liquor again and transfer to the pH value of solution value between the 6-7 or splash into 4ml and contain 10mmolNH
4The aqueous solution of OAc.Continue to stir at normal temperatures or refluxed 1 to 2 hour.Suction filtration is used washing with alcohol, drying, the catalyzer (X=Cl) of general formula (III).Product yield is about 90%.
Embodiment 3: general formula (III) catalyzer synthetic:
The part of 10mmol general molecular formula (I) is dissolved in the 30-50ml tetrahydrofuran (THF), under agitation dropwise adds 20ml and contain 5mmol Mn (OAc)
2Ethanolic soln.And then splash into the 2-3mmol hydrogen peroxide; Continue to stir at normal temperatures or refluxed 1 to 2 hour; Suction filtration is used washing with alcohol, and drying gets solid and is required catalyzer (X=OAc); Product yield is about 90%.
Embodiment 4: cinnamic epoxidation
The catalyzer (M=Mn, the R that in reactor, add 0.03mmol general formula (II)
4=R
5=R
6=R
8=H, R
7=Cl, R
9=I), and then add 2.25ml acetone, and add vinylbenzene 1mmol.Under agitation add and contain 0.2mmol NH
4The aqueous solution 0.75ml of OAc and 0.1mmol HOAc, after stirring, under 0 ℃ of condition, the hydrogen peroxide solution that will contain 1.5mmol concentration and be 10% (w/w) dropwise adds this mixture, adds through 2 hours, and total reaction time is 3 hours.The styrene conversion rate is 100%, and the Styryl oxide productive rate is 99%.
Embodiment 5: the epoxidation of indenes
Catalyzer (M=Mn, R with 0.03mmol general molecular formula (III)
4=R
5=R
5=R
8=H, R
7=Cl, R
9=I X=Cl) adds in the reactor, and then adds 2.25ml acetone, and adds indenes 1mmol.Under agitation add and contain 0.2mmol ammonium benzoate and the benzoic aqueous solution 0.75ml of 0.1mmol, after stirring, under 10 ℃ of conditions, the hydrogen peroxide solution that will contain 1.5mmol concentration and be 10% (w/w) dropwise adds this mixture, add through 1 hour, total reaction time is 2 hours.The transformation efficiency of indenes is 100%, and the productive rate of its epoxide is 100%.
Embodiment 6: the epoxidation of beta-pinene
Catalyzer (M=Mn, R with 0.03mmol general molecular formula (III)
4=R
5=R
6=R
8=H, R
7=Cl, R
9=I X=Cl) adds in the reactor, and then adds 2.25ml acetone, and adds alkene 1mmol.Under agitation add the aqueous solution 0.75ml that contains the 0.2mmol ammonium tartrate, after stirring, under 10 ℃ of conditions, the hydrogen peroxide solution that will contain 1.5mmol concentration and be 10% (w/w) dropwise adds this mixture, add through 1 hour, total reaction time is 2 hours.The transformation efficiency of beta-pinene is 100%, and the productive rate of epoxypinane is 100%.
The epoxidation of embodiment 7:1-benzyl ring hexene
Catalyzer (M=Mn, R with 0.03mmol general molecular formula (III)
4=R
5=R
6=R
8=H, R
7=Cl, R
9=I X=Cl) adds in the reactor, and then adds 2.25ml acetone, and adds 1-benzyl ring hexene 1mmol.Under agitation add and contain 0.2mmol NH
4The aqueous solution 0.75ml of OAc and 0.1mmol HOAc, after stirring, under 10 ℃ of conditions, the hydrogen peroxide that will contain 1.5mmol concentration and be 10% (w/w) dropwise adds this mixture, adds through 1 hour.Total reaction time is 2 hours.The transformation efficiency of 1-benzyl ring hexene is 90%, 1, and the productive rate of 2-epoxy-1-Santosol 360 is 86%.
Embodiment 8: the epoxidation of tetrahydrobenzene
Catalyzer (M=Mn, R with 0.03mmol general molecular formula (III)
4=R
5=R
6=R
8=H, R
7=Cl, R
9=I X=Cl) adds in the reactor, and then adds 2.25ml acetone, and adds tetrahydrobenzene 1mmol.Under agitation add and contain 0.05mmol NH
4The aqueous solution 0.75ml of OAc and 0.05mmol HOAc, after stirring, under 10 ℃ of conditions, the hydrogen peroxide solution that will contain 1.5mmol concentration and be 10% (w/w) is through adding this mixture in 2 hours.Total reaction time is 3.5 hours.The transformation efficiency of tetrahydrobenzene is 93%, 1, and the productive rate of 2-epoxy cyclohexane is 81%.
Embodiment 9: the recycling of catalyzer
Post reaction mixture among the embodiment 8 is centrifugal, abandon its clear liquid, precipitate and separate is come out, test by the operation steps among the embodiment 8 once more after the drying.The transformation efficiency of tetrahydrobenzene is 92%, and the productive rate of its epoxide is 79%.As seen, after catalyst recovery was utilized, descending did not appear in activity.
Embodiment 10: the epoxidation of alpha-methyl styrene
Catalyzer (M=Mn, R with 0.05mmol general molecular formula (III)
4=R
5=R
6=R
8=H, R
7=Cl, R
9=I X=Cl) adds in the reactor, and then adds 2.25ml acetone, and adds alpha-methyl styrene 1mmol.Under agitation add and contain 0.2mmol NH
4The aqueous solution 0.75ml of OAc and 0.1mmol HOAc, after stirring, under 10 ℃ of conditions, the hydrogen peroxide solution that will contain 1.5mmol concentration and be 10% (w/w) is through adding this mixture in 2 hours.Total reaction time is 3.5 hours.The transformation efficiency of alpha-methyl styrene is 100%, and the productive rate of 2-methyl-2-phenyl ethylene oxide is 98%.
Embodiment 11: the epoxidation of styryl carbinol
Catalyzer (M=Mn, R with 0.05mmol general molecular formula (III)
4=R
5=R
6=R
8=H, R
7=Cl, R
9=I X=Cl) adds in the reactor, and then adds 2.25ml acetone, and adds styryl carbinol 1mmol.Under agitation add and contain 0.2mmol NH
4The aqueous solution 0.75ml of OAc and 0.1mmol HOAc, after stirring, under 10 ℃ of conditions, the hydrogen peroxide solution that will contain 1.5mmol concentration and be 10% (w/w) is through adding this mixture in 2 hours.Total reaction time is 3 hours.The transformation efficiency of styryl carbinol is 95%, and the productive rate of trans-2-hydroxymethyl-3-phenyl ethylene oxide is 83%.
The epoxidation of embodiment 12:2-hexen-1-ol
Catalyzer (M=Mn, R with 0.03mmol general molecular formula (III)
4=R
5=R
6=R
8=H, R
7=Cl, R
9=I X=Cl) adds in the reactor, and then adds 2.25ml acetone, and adds 2-hexen-1-ol 1mmol.Under agitation add and contain 0.2mmol NH
4The aqueous solution 0.75ml of OAc and 0.1mmol HOAc, after stirring, under 10 ℃ of conditions, the hydrogen peroxide solution that will contain 1.5mmol concentration and be 10% (w/w) is through adding this mixture in 2 hours.Total reaction time is 3.5 hours.The transformation efficiency of trans-2-hexen-1-ol is 72%, 2, and the productive rate of 3-epoxy-1-hexanol is 56%.
The epoxidation of embodiment 13:1-octene
Catalyzer (M=Mn, R with 0.03mmol general molecular formula (III)
4=R
5=R
6=R
8=H, R
7=Cl, R
9=I X=Cl) adds in the reactor, and then adds 2.4ml acetone, and adds 1-octene 1mmol.Under agitation add and contain 0.05mmol NH
4The aqueous solution 0.6ml of OAc and 0.05mmol HOAc, after stirring, under 10 ℃ of conditions, this mixture in the hydrogen peroxide solution that will contain 3mmol concentration and be 25% (w/w) added through 6 hours.Total reaction time is 24 hours.The transformation efficiency of 1-octene is 95%, 1, and the productive rate of 2-octylene oxide is 93%.
Embodiment 14: the epoxidation of trans toluylene
Catalyzer (M=Mn, R with 0.01mmol general molecular formula (III)
4=R
5=R
6=R
8=H, R
7=Cl, R
9=I X=Cl) adds in the reactor, and then adds 3ml acetone, and adds alkene 1mmol.After stirring, under 10 ℃ of conditions, this mixture in the hydrogen peroxide solution that will contain 1.5mmol concentration and be 25% (w/w) added through 6 hours.Total reaction time is 24 hours.The transformation efficiency of trans toluylene is 98%, and the productive rate of trans phenylbenzene oxyethane is 81%.
Claims (10)
1. the Mn catalyst of an oxine derivative is characterized in that, is that the oxine derivative by general formula (I) is the complex compound that part and mn ion form general formula (II) or general formula (III);
Substituent R in the general formula (I) on the aromatic ring
4, R
5, R
6, R
7, R
8, R
9Each hydrogen naturally independently of one another, halogen, alkyl, alkoxyl group, hydroxyl, nitro, amido, glycosyl replaces glycosyl and cyclodextrin; General formula (II), (III) metal ion in is Mn; Dentate X in the general formula (III) can be a halogen, PF
6 -, methyl ethyl diketone, acetate moiety and other carboxylate radical negative ion.
2. the preparation method of the Mn catalyst of the oxine derivative of general formula (II) described in the claim 1 is characterized in that, may further comprise the steps:
(1) part with 10mmol general molecular formula (I) is dissolved in the organic solvent;
(2) under agitation dropwise add the ethanolic soln of the manganous salt of 5mmol;
(3) continue to stir at normal temperatures 10 to 20 minutes,
(4) suction filtration is used washing with alcohol, drying, the solid catalyst finished product of general formula (II).
3. the synthetic method of the catalyzer of general formula (III) described in the claim 1 may further comprise the steps:
(1) part with 10mmol general molecular formula (I) is dissolved in the organic solvent;
(2) under agitation dropwise add the ethanolic soln of the manganous salt of 5mmol;
(3) splash into the 2-3mmol hydrogen peroxide, splash into ammoniacal liquor again the pH value of solution value is transferred between the 6-7, or splash into the aqueous solution that 4ml contains the 10mmol ammonium acetate;
(4) continue to stir at normal temperatures or refluxed 1 to 2 hour;
(5) suction filtration is used washing with alcohol, drying, the solid catalyst (X=Cl or OAc) of general formula (III).
4. the described Application of Catalyst of claim 1 is characterized in that, is used for alkene and oxidants hydrogen peroxide is reacted at solvent, and its catalyst consumption is the 0.5-5% of alkene molar weight.
5. application according to claim 4 is characterized in that containing in the described catalyzer carboxylate salt, carboxylic acid, carbonate or imidazoles nitrogen-containing heterocycle compound as auxiliary agent, and the mol ratio of catalyzer and auxiliary agent is 1: 1-20.
6. application according to claim 4 is characterized in that described oxidants hydrogen peroxide is the aqueous solution, and its concentration is 10 ~ 30%.
7. application according to claim 4 is characterized in that described solvent is water, ketone, alcohol, hydrochloric ether, aromatic hydrocarbons, N, a kind of in N-two-methylformamide, ether or the ester or their mixture.
8. application according to claim 4 is characterized in that described solvent is the mixed solvent of water and acetone, and the volume ratio of water and acetone is 1: 2-5.
9. application according to claim 4 is characterized in that described alkene is cyclenes, fragrant alkene, alkene, terpenes, enol class.
10. application according to claim 4, it is characterized in that, may further comprise the steps: the general formula (II) of the 0.5-5% of alkene molar weight or oxine derivative Mn catalyst (III) are dissolved in the reaction solvent, add raw material olefin again, after stirring, under 0-25 ℃ of temperature, dropwise add the 1-3 oxidant hydrogen peroxide doubly of alkene molar weight, reacted 1-24 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101369894A CN100545167C (en) | 2006-12-29 | 2006-12-29 | The Mn catalyst of oxine derivative and the application in alkene epoxidation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101369894A CN100545167C (en) | 2006-12-29 | 2006-12-29 | The Mn catalyst of oxine derivative and the application in alkene epoxidation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1995049A true CN1995049A (en) | 2007-07-11 |
| CN100545167C CN100545167C (en) | 2009-09-30 |
Family
ID=38250265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101369894A Expired - Fee Related CN100545167C (en) | 2006-12-29 | 2006-12-29 | The Mn catalyst of oxine derivative and the application in alkene epoxidation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100545167C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658203A (en) * | 2012-04-26 | 2012-09-12 | 河南化工职业学院 | Novel epoxidation catalyst, preparation method and applications |
| CN103936723A (en) * | 2013-01-23 | 2014-07-23 | 中国中化股份有限公司 | Method of preparing epoxiconazole by catalyzing epoxidation of triazole olefin |
| CN103934028A (en) * | 2013-01-23 | 2014-07-23 | 中国中化股份有限公司 | Manganese catalyst of 2-pyridinecarboxylic acid derivatives, synthetic method of the manganese catalyst and applications of the manganese catalyst |
| CN105642349A (en) * | 2016-02-17 | 2016-06-08 | 上海电力学院 | Preparation method of manganese-based MOF (metal-organic framework) magnetic material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2149569A1 (en) | 2008-08-01 | 2010-02-03 | Hexion Specialty Chemicals Research Belgium S.A. | Process for the manufacture of a 1,2-Epoxide |
-
2006
- 2006-12-29 CN CNB2006101369894A patent/CN100545167C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658203A (en) * | 2012-04-26 | 2012-09-12 | 河南化工职业学院 | Novel epoxidation catalyst, preparation method and applications |
| CN103936723A (en) * | 2013-01-23 | 2014-07-23 | 中国中化股份有限公司 | Method of preparing epoxiconazole by catalyzing epoxidation of triazole olefin |
| CN103934028A (en) * | 2013-01-23 | 2014-07-23 | 中国中化股份有限公司 | Manganese catalyst of 2-pyridinecarboxylic acid derivatives, synthetic method of the manganese catalyst and applications of the manganese catalyst |
| CN103936723B (en) * | 2013-01-23 | 2016-06-29 | 沈阳中化农药化工研发有限公司 | A kind of method that catalysis triazole alkene epoxidation prepares epoxiconazole |
| CN103934028B (en) * | 2013-01-23 | 2016-09-14 | 沈阳中化农药化工研发有限公司 | The Mn catalyst of pyridine-2-formic acid derivates and synthetic method thereof and application |
| CN105642349A (en) * | 2016-02-17 | 2016-06-08 | 上海电力学院 | Preparation method of manganese-based MOF (metal-organic framework) magnetic material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100545167C (en) | 2009-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100545167C (en) | The Mn catalyst of oxine derivative and the application in alkene epoxidation thereof | |
| CN102336736B (en) | Method for catalyzing and preparing annular carbonic ester by supported ionic liquid | |
| CN101508631B (en) | Method for oxidizing ethanol into corresponding aldehyde in catalyst action | |
| CN107442177A (en) | The method that 5 hydroxymethylfurfural selective hydrogenations synthesize 2,5 furyl dimethyl carbinols | |
| CN110105321A (en) | A kind of method of eutectic ionic liquid catalysis carbon dioxide synthesizing annular carbonate | |
| CN106279094B (en) | A kind of method of Thiourea preparing cyclic carbonate by catalyzing with ionic liquid | |
| CN103447091A (en) | Quadridentate pyridyl schiff base metal complex and preparation method thereof as well as preparation method of cyclic carbonate | |
| CN111423326A (en) | Method for preparing dimethyl carbonate by alkaline ionic liquid catalysis one-step method | |
| CN101130170A (en) | Manganese or iron catalyzer of 8- hydroxyquinoline derivant of hexa-tooth coordination structure and uses of the same | |
| CN101613424A (en) | A kind of method for preparing polybutadiene epoxy resin | |
| CN102336735B (en) | Method for preparing cyclic carbonate by catalyzing with ionic liquid | |
| CN104588049A (en) | Solid acid catalyst as well as preparation method and application of solid acid catalyst | |
| CN101906045B (en) | Method for directly synthesizing aniline from benzene and ammonia by one step | |
| CN100425585C (en) | Styrene catalytic oxidation method | |
| CN111889141A (en) | Ionic liquid functionalized bipyridine porous polymer catalyst for catalyzing cycloaddition reaction of carbon dioxide and epoxide | |
| CN102167686B (en) | Method for preparing 2,2'-dibenzothiazyl disulfide by catalyzing oxidation through molecular oxygen | |
| Benaglia et al. | Synthesis of poly (ethylene glycol)-supported manganese porphyrins: efficient, recoverable and recyclable catalysts for epoxidation of alkenes | |
| CN105593220A (en) | Process for the production of furanic compounds comprising at least one amine function | |
| CN107233921B (en) | Method for preparing catalyst by using modified cellulose loaded SalenMX and application | |
| CN103788023A (en) | Method for preparing styrene oxide through epoxidation of styrene | |
| CN103145630B (en) | Method for catalytically synthesizing quinoxaline compound | |
| CN101182288A (en) | Method for oxo isophorone by heterogeneous oxidization | |
| Jehbez et al. | A novel catalytic one-pot three-component reaction of aldehydes, o-phenylenediamine derivatives and isocyanides for synthesis of 3, 4-dihydroquinoxalin-2-amine derivatives in the presence of zirconium tetrachloride | |
| CN101565341B (en) | Method for synthesizing (E)-Alpha, Beta-unsaturated carbonyl compounds | |
| CN115340475B (en) | Preparation method of 1-diphenyl diazene oxide or derivative 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090930 Termination date: 20111229 |