CN103638975A - Supported gold catalyst, its preparation and its application - Google Patents
Supported gold catalyst, its preparation and its application Download PDFInfo
- Publication number
- CN103638975A CN103638975A CN201310565323.0A CN201310565323A CN103638975A CN 103638975 A CN103638975 A CN 103638975A CN 201310565323 A CN201310565323 A CN 201310565323A CN 103638975 A CN103638975 A CN 103638975A
- Authority
- CN
- China
- Prior art keywords
- load type
- reaction
- gold catalyst
- type gold
- alkynyl
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a supported gold catalyst, its preparation and its application. The invention is characterized in that the catalyst employs a phosphine ligand for complexation of a monovalent gold compound, then monovalent gold compound is supported on an ordered meso pore phenolic resins material, and then the supported gold catalyst with supporting amount of 2.4-4.0wt% is prepared. The preparation of the supported gold catalyst comprises the steps of ordered meso pore phenolic resins chloromethylation and phosphine ligand; the supported gold catalyst has strong catalytic activity for being used in an intramolecular cyclisation reaction and an intermolecular allyl alcohol amination reaction of 2-alkynyl-1,3-dicarbonyls compounds, which is equivalent to the result of a homogeneous reaction. Compared with the prior art, the preparation method has the advantages of simple process, moderate reaction condition, good activity maintenance and little precious metals consumption, the cycle utilization of the catalyst is realized, the environmental pollution is reduced, and the invention provides the effective solution approach for existed problems of the intramolecular cyclisation reaction and the allyl alcohol amination reaction by traditional homogeneous gold catalysis.
Description
Technical field
The present invention relates to chemical catalysis material and chemical applied technical field, especially a kind of load type gold catalyst for allyl alcohol aminating reaction and preparation and application.
Background technology
The mankind find and utilize golden history very remote, but because simple substance gold has good chemical stability, its catalytic performance is ignored by people for a long time.Since age end 80 year last century, the catalytic effect of gold just starts to be subject to extensive concern.The addition reaction of gold catalysis is gentle with its reaction condition, product yield advantages of higher, occupies critical role in Synthetic Organic Chemistry.The excellent properties that ionic Au (I) complex compound that the phosphine of take is part shows in the nucleophilic addition of catalytic activation alkynes class, allylic compound, thereby at aspects such as constructing of carbon-carbon bond, carbon-nitrogen bond (
angew. Chem. Int. Ed.
2006,45,7896-7936) obtain more and more and pay close attention to, wherein allyl alcohol aminating reaction and 2-alkynyl-1 of Au (I) catalysis, the intramolecular cyclization reaction of 3-dicarbapentaborane compounds is the important organic reactions of two classes.Because allylic amines compound structure is the important activity fragment being contained in a lot of natural products, it is the important organic intermediate of a class; Simultaneously, 2-alkynyl-1, the formed five-membered ring of intramolecular cyclization reaction or the six-membered ring structure of 3-dicarbapentaborane compounds are extensively present in natural products, also be important organic intermediate, the value that has a wide range of applications in the synthetic field of organic and medicine, so this two compounds synthetic is one of hot research of Synthetic Organic Chemistry.
At present, the correlated response of homogeneous phase Au (I) catalysis exists catalyst and is difficult to the shortcomings such as recovery, loss and the pollution to environment of metallic catalyst have inevitably been caused, do not meet the demand for development of Green Chemistry, especially catalyst is not recyclable, the easy residual heavy metal of product, the shortcoming such as environmental pollution is more serious, has limited it and has further developed.
Summary of the invention
A kind of load type gold catalyst and preparation and the application that for the deficiencies in the prior art, provide are provided, adopt the complexing of phosphine part to monovalence gold compound, homogeneous phase Au catalyst is carried on ordered mesoporous phenolic resin material, catalyst after load is for intermolecular allyl alcohol aminating reaction, intramolecular cyclization reaction has higher catalytic activity, not only there is reaction condition moderate, activity keeping is good, the advantage that noble metal consumption is few, and can recycle, the rate of recovery is high, environmental pollution and economic loss that metal flow is become homeless and caused have been reduced, intermolecular allyl alcohol aminating reaction and intramolecular cyclization reaction have been widened in the scope of catalyst cupport research and application, reduced the pollution to environment, promoted the development of Green Chemistry.
The concrete technical scheme that realizes the object of the invention is: a kind of load type gold catalyst, be characterized in that this catalyst adopts the complexing of phosphine part to monovalence gold compound, then be carried on ordered mesoporous phenolic resin material, make the load type gold catalyst that loading is 2.4 ~ 4.0 wt.%, its structural formula is as follows:
Wherein: R
1=Me, Et, Cy, Ph, (2-OMe) Ph, (4-OMe) Ph, (4-CF
3) Ph, OPh, Bz,
,
or
;
R
2=Et, Cy, Ph, (2-OMe) Ph, (4-OMe) Ph, (4-CF
3) Ph, OPh, Bz,
,
or
.
A preparation for load type gold catalyst, is characterized in adopting the complexing of phosphine part to monovalence gold compound, is then carried on ordered mesoporous phenolic resin material, makes the load type gold catalyst that loading is 0.42 ~ 2.62wt%, and its expression is FDU-PR
1r
2/ Au (I), concrete preparation comprises the following steps:
The chloromethylation of a, ordered mesoporous phenolic resin
Ordered mesoporous phenolic resin is mixed by 1:4.5 ~ 5.5:1 ~ 1.5 weight ratio with chloromethyl ether and aluminium chloride at 0 ℃ of temperature, then under argon shield, carry out 10 ~ 15 hours chloromethylations, the ordered mesoporous phenolic resin of preparing chloromethylation, its reaction temperature is 20 ~ 30 ℃, and described aluminium chloride is to add for 2 ~ 3 times and be 1 ~ 2 hour each interval time;
The phosphine ligand function of b, ordered mesoporous phenolic resin
By two replacement phosphonium chloride (ClPR
1r
2) by after 0.25 ~ 1.5:1 dissolving, add 2 grams of lithium stirring reactions 2 ~ 4 hours with anhydrous tetrahydro furan, then add 30 ~ 40 grams of the ordered mesoporous phenolic resins of the chloromethylation of above-mentioned preparation to continue reaction 10 ~ 14 hours, prepare the ordered mesoporous phenolic resin of phosphine ligand function;
The preparation of c, load type gold catalyst
After the ordered mesoporous phenolic resin of the phosphine ligand function of above-mentioned preparation and anhydrous tetrahydro furan are dissolved by 1:4.0 ~ 6.0, add 1 ~ 3 gram of monovalence gold compound, under normal temperature, stir 12 hours, after reaction finishes, filter to obtain load type gold catalyst.
Described monovalence gold compound is aurous chloride, dimethyl sulphide aurous chloride or sodium chloraurate.
Described two replace phosphonium chlorides be diphenyl phosphine chloride, two (2-methoxyl group) phenyl phosphonium chloride, two (4-methoxyl group) phenyl phosphonium chloride, two (4-trifluoromethyl) phenyl phosphonium chloride, two phenoxy group phosphonium chlorides, aminomethyl phenyl phosphonium chloride, dicyclohexyl phosphonium chloride, two (2-furyl) phosphonium chloride, diethyl phosphonium chloride, benzyl phenyl phosphonium chloride or
r-2,2 '-bis-(phenyl phosphonium chlorides)-1,1 '-dinaphthalene.
An application for load type gold catalyst, is characterized in that this catalyst is for 2-alkynyl-1, the intramolecular cyclization reaction of 3-dicarbapentaborane compounds and intermolecular allyl alcohol aminating reaction, and its concrete application is as follows:
A, intermolecular allyl alcohol aminating reaction
Under argon shield, after being mixed with 0.072 ~ 0.21:0.19 ~ 0.37 weight portion with aminated compounds, allyl alcohol compound adds successively silver trifluoromethanesulfonate 0.005 weight portion, load type gold catalyst (FDU-PR
1r
2/ Au (I)) 0.003 ~ 0.025 weight portion and anhydrous 1,4-dioxane 2.066 weight portions carry out intermolecular alcohol aminating reaction, adopt thin-layer chromatography TLC to follow the tracks of reaction, after reaction finishes, load type gold catalyst is leached, after concentrating filter liquor, by column chromatography chromatogram, obtaining target product is allyl amine compounds;
B, 2-alkynyl-1, the intramolecular cyclization reaction of 3-dicarbapentaborane compounds
Under argon shield; by 2-alkynyl-1; 3-dicarbapentaborane compounds mixes with the weight portion of 0.09 ~ 0.15:2.45:3.35 with isopropyl alcohol, methyl-sulfoxide, then adds successively the load type gold catalyst (FDU-PR of the silver trifluoromethanesulfonate of 0.068 weight portion, the NaOH of 0.003 weight portion and 0.017 ~ 0.11 weight portion
1r
2/ Au (I)) carry out intramolecular cyclization reaction; adopt thin-layer chromatography TLC to follow the tracks of reaction; after reaction finishes, load type gold catalyst is leached, after concentrating filter liquor, by column chromatography chromatogram, obtaining target product is 1-acyl group-2-methylene cyclopentanecarboxylic acid lipoid substance.
Described allyl alcohol compound is 1,3-diphenyl pi-allyl-1-alcohol, 1,3-bis-(4-methyl) phenyl pi-allyl-1-alcohol, 1,3-bis-(4-methoxyl group) phenyl pi-allyl-1-alcohol, 1,3-bis-(4-nitro) phenyl pi-allyl-1-alcohol, 2-thiazolinyl-n-butyl alcohol, Isosorbide-5-Nitrae-dialkylene-3-amylalcohol or 2-thiazolinyl-1-cyclohexanol.
Described aminated compounds be 4-methyl benzenesulfonamide, 4-methoxybenzenesulphoismide,
n-methyl-4-methyl benzenesulfonamide, 4-nitrobenzene sulfonamide, methylsulfonamides, 2-phenyl-acetamides, aniline, 4-chloroaniline, 4-nitroaniline or 4-aminoanisole.
Described 2-alkynyl-1, 3-dicarbapentaborane compounds is 2-benzoyl-6-alkynyl methyl heptanoate, 2-benzoyl-6-alkynyl cognac oil, 2-(4-methoxyl group) benzoyl-6-alkynyl cognac oil, 2-(3-methyl) benzoyl-6-alkynyl cognac oil, 2-(4-nitro) benzoyl-6-alkynyl cognac oil, 2-benzoyl-6-alkynyl enanthic acid isopropyl ester, 2-acetyl group-6-alkynyl methyl heptanoate, 2-acetyl group-6-alkynyl cognac oil, 2-acetyl group-6-alkynyl acid benzyl ester in heptan, 2-isopropyl bytyry-6-alkynyl cognac oil or 2-(4-pentynyl)-1-phenyl butane-1, 3-diketone.
It is simple that the present invention compared with prior art has method, easy to operate and reaction condition is gentle, good and the noble metal consumption of catalytic activity such as lacks at the advantage, and can recycle, thereby reduced the pollution of heavy metal to environment, meet Green Chemistry demand for development, made up the deficiency of traditional homogeneous catalyst on intramolecular cyclization reaction and intermolecular allyl alcohol aminating reaction, enriched the content of load type gold catalyst research field, for the intramolecular cyclization reaction of traditional homogeneous phase gold catalysis and the existing problem of allyl alcohol aminating reaction and drawback provide effective solution route.
The specific embodiment
The present invention adopts the complexing of phosphine part to monovalence gold compound, is then carried on ordered mesoporous phenolic resin material, makes the load type gold catalyst (FDU-PR of following structural formula
1r
2/ Au (I)):
Wherein: R
1=Me, Et, Cy, Ph, (2-OMe) Ph, (4-OMe) Ph, (4-CF
3) Ph, OPh, Bz,
,
or
;
R
2=Et, Cy, Ph, (2-OMe) Ph, (4-OMe) Ph, (4-CF
3) Ph, OPh, Bz,
,
or
.
By specific embodiment, preparation of the present invention and application are described in further detail below.
Embodiment 1
The chloromethylation of a, ordered mesoporous phenolic resin
20 grams of ordered mesoporous phenolic resins and 100 grams of chloromethyl ethers and 21 grams of aluminium chloride (minute add for three times and be 1 hour each interval time) are mixed at 0 ℃ of temperature; then under argon shield, carry out 12 hours chloromethylations; prepare the ordered mesoporous phenolic resin of chloromethylation, its reaction temperature is 25 ℃.
The phosphine ligand function of b, ordered mesoporous phenolic resin
48 grams of diphenyl phosphine chlorides are dissolved in 89 grams of anhydrous tetrahydro furans, add 2 grams of lithium stirring reactions 3 hours, 32 grams of ordered mesoporous phenolic resins that gained solution added to the chloromethylation of above-mentioned preparation, continue reaction 12 hours, are prepared into the ordered mesoporous phenolic resin of phosphine ligand function.
The preparation of c, load type gold catalyst
After being dissolved with 222 grams of anhydrous tetrahydro furans, 50 grams of the ordered mesoporous phenolic resins of the phosphine ligand function of above-mentioned preparation add 1.4 grams of dimethyl sulphide aurous chlorides, under normal temperature, stir 12 hours, after reaction finishes, filter and obtain 51 grams of load type gold catalyst (FDU-PPh
2/ Au (I)).
Embodiment 2
The chloromethylation of a, ordered mesoporous phenolic resin
20 grams of ordered mesoporous phenolic resins and 100 grams of chloromethyl ethers and 21 grams of aluminium chloride (minute add for three times and be 1 hour each interval time) are mixed at 0 ℃ of temperature; then under argon shield, carry out 12 hours chloromethylations; prepare the ordered mesoporous phenolic resin of chloromethylation, its reaction temperature is 25 ℃.
The phosphine ligand function of b, ordered mesoporous phenolic resin
78 gram of two (4-trifluoromethyl) phenyl phosphonium chloride is dissolved in 89 grams of anhydrous tetrahydro furans, add 2 grams of lithium stirring reactions 3 hours, 32 grams of ordered mesoporous phenolic resins that gained solution added to the chloromethylation of above-mentioned preparation, continue reaction 12 hours, be prepared into the ordered mesoporous phenolic resin of phosphine ligand function.
The preparation of c, load type gold catalyst
After being dissolved with 222 grams of anhydrous tetrahydro furans, 50 grams of the ordered mesoporous phenolic resins of the phosphine ligand function of above-mentioned preparation add 1.4 grams of dimethyl sulphide aurous chlorides, under normal temperature, stir 12 hours, after reaction finishes, filter and obtain 51 grams of load type gold catalysts (FDU-P (4-CF
3ph)
2/ Au (I)).
Embodiment 3
The chloromethylation of a, ordered mesoporous phenolic resin
20 grams of ordered mesoporous phenolic resins and 100 grams of chloromethyl ethers and 21 grams of aluminium chloride (minute add for three times and be 1 hour each interval time) are mixed at 0 ℃ of temperature; then under argon shield, carry out 12 hours chloromethylations; prepare the ordered mesoporous phenolic resin of chloromethylation, its reaction temperature is 25 ℃.
The phosphine ligand function of b, ordered mesoporous phenolic resin
62 gram of two (4-methoxyl group) phenyl phosphonium chloride is dissolved in 89 grams of anhydrous tetrahydro furans, add 2 grams of lithium stirring reactions 3 hours, 32 grams of ordered mesoporous phenolic resins that gained solution added to the chloromethylation of above-mentioned preparation, continue reaction 12 hours, prepare the ordered mesoporous phenolic resin of phosphine ligand function.
The preparation of c, load type gold catalyst
After being dissolved with 222 grams of anhydrous tetrahydro furans, 50 grams of the ordered mesoporous phenolic resins of the phosphine ligand function of above-mentioned preparation add 2.7 gram of two hydration sodium chloraurate, under normal temperature, stir 12 hours, after reaction finishes, filter and obtain 51 grams of load type gold catalysts (FDU-P (4-OMePh)
2/ Au (I)).
Embodiment 4
The chloromethylation of a, ordered mesoporous phenolic resin
20 grams of ordered mesoporous phenolic resins and 100 grams of chloromethyl ethers and 21 grams of aluminium chloride (minute add for three times and be 1 hour each interval time) are mixed at 0 ℃ of temperature; then under argon shield, carry out 12 hours chloromethylations; prepare the ordered mesoporous phenolic resin of chloromethylation, its reaction temperature is 25 ℃.
The phosphine ligand function of b, ordered mesoporous phenolic resin
62 gram of two (2-methoxyl group) phenyl phosphonium chloride is dissolved in 89 grams of anhydrous tetrahydro furans, add 2 grams of lithium stirring reactions 3 hours, 32 grams of ordered mesoporous phenolic resins that gained solution added to the chloromethylation of above-mentioned preparation, continue reaction 12 hours, be prepared into the ordered mesoporous phenolic resin of phosphine ligand function.
The preparation of c, load type gold catalyst
After being dissolved with 222 grams of anhydrous tetrahydro furans, 50 grams of the ordered mesoporous phenolic resins of the phosphine ligand function of above-mentioned preparation add 1.4 grams of dimethyl sulphide aurous chlorides, under normal temperature, stir 12 hours, after reaction finishes, filter and obtain 51 grams of load type gold catalysts (FDU-P (2-OMePh)
2/ Au (I)).
Embodiment 5
The chloromethylation of a, ordered mesoporous phenolic resin
20 grams of ordered mesoporous phenolic resins and 100 grams of chloromethyl ethers and 21 grams of aluminium chloride (minute add for three times and be 1 hour each interval time) are mixed at 0 ℃ of temperature; then under argon shield, carry out 12 hours chloromethylations; prepare the ordered mesoporous phenolic resin of chloromethylation, its reaction temperature is 25 ℃.
The phosphine ligand function of b, ordered mesoporous phenolic resin
55 gram of two phenoxy group phosphonium chloride is dissolved in 89 grams of anhydrous tetrahydro furans, add 2 grams of lithium stirring reactions 3 hours, 32 grams of ordered mesoporous phenolic resins that gained solution added to the chloromethylation of above-mentioned preparation, continue reaction 12 hours, are prepared into the ordered mesoporous phenolic resin of phosphine ligand function.
The preparation of c, load type gold catalyst
After being dissolved with 222 grams of anhydrous tetrahydro furans, 50 grams of the ordered mesoporous phenolic resins of the phosphine ligand function of above-mentioned preparation add 1.4 grams of dimethyl sulphide aurous chlorides, under normal temperature, stir 12 hours, after reaction finishes, filter and obtain 51 grams of load type gold catalysts (FDU-P (OPh)
2/ Au (I)).
Embodiment 6
The chloromethylation of a, ordered mesoporous phenolic resin
20 grams of ordered mesoporous phenolic resins and 100 grams of chloromethyl ethers and 21 grams of aluminium chloride (minute add for three times and be 1 hour each interval time) are mixed at 0 ℃ of temperature; then under argon shield, carry out 12 hours chloromethylations; prepare the ordered mesoporous phenolic resin of chloromethylation, its reaction temperature is 25 ℃.
The phosphine ligand function of b, ordered mesoporous phenolic resin
35 grams of aminomethyl phenyl phosphonium chlorides are dissolved in 89 grams of anhydrous tetrahydro furans, add 2 grams of lithium stirring reactions 3 hours, 32 grams of ordered mesoporous phenolic resins that gained solution added to the chloromethylation of above-mentioned preparation, continue reaction 12 hours, are prepared into the ordered mesoporous phenolic resin of phosphine ligand function.
The preparation of c, load type gold catalyst
After being dissolved with 222 grams of anhydrous tetrahydro furans, 50 grams of the ordered mesoporous phenolic resins of the phosphine ligand function of above-mentioned preparation add 1.4 grams of dimethyl sulphide aurous chlorides, under normal temperature, stir 12 hours, after reaction finishes, filter and obtain 51 grams of load type gold catalysts (FDU-PMePh/Au (I)).
Embodiment 7
The chloromethylation of a, ordered mesoporous phenolic resin
20 grams of ordered mesoporous phenolic resins and 100 grams of chloromethyl ethers and 21 grams of aluminium chloride (minute add for three times and be 1 hour each interval time) are mixed at 0 ℃ of temperature; then under argon shield, carry out 12 hours chloromethylations; prepare the ordered mesoporous phenolic resin of chloromethylation, its reaction temperature is 25 ℃.
The phosphine ligand function of b, ordered mesoporous phenolic resin
52 grams of dicyclohexyl phosphonium chlorides are dissolved in 89 grams of anhydrous tetrahydro furans, add 2 grams of lithium stirring reactions 3 hours, 32 grams of ordered mesoporous phenolic resins that gained solution added to the chloromethylation of above-mentioned preparation, continue reaction 12 hours, are prepared into the ordered mesoporous phenolic resin of phosphine ligand function.
The preparation of c, load type gold catalyst
After being dissolved with 222 grams of anhydrous tetrahydro furans, 50 grams of the ordered mesoporous phenolic resins of the phosphine ligand function of above-mentioned preparation add 1.4 grams of dimethyl sulphide aurous chlorides, under normal temperature, stir 12 hours, after reaction finishes, filter and obtain 51 grams of load type gold catalyst (FDU-PCy
2/ Au (I)).
Embodiment 8
The chloromethylation of a, ordered mesoporous phenolic resin
20 grams of ordered mesoporous phenolic resins and 100 grams of chloromethyl ethers and 21 grams of aluminium chloride (minute add for three times and be 1 hour each interval time) are mixed at 0 ℃ of temperature; then under argon shield, carry out 12 hours chloromethylations; prepare the ordered mesoporous phenolic resin of chloromethylation, its reaction temperature is 25 ℃.
The phosphine ligand function of b, ordered mesoporous phenolic resin
52 grams of benzyl phenyl phosphonium chlorides are dissolved in 89 grams of anhydrous tetrahydro furans, add 2 grams of lithium stirring reactions 3 hours, 32 grams of ordered mesoporous phenolic resins that gained solution added to the chloromethylation of above-mentioned preparation, continue reaction 12 hours, are prepared into the ordered mesoporous phenolic resin of phosphine ligand function.
The preparation of c, load type gold catalyst
After being dissolved with 222 grams of anhydrous tetrahydro furans, 50 grams of the ordered mesoporous phenolic resins of the phosphine ligand function of above-mentioned preparation add 1.4 grams of dimethyl sulphide aurous chlorides, under normal temperature, stir 12 hours, after reaction finishes, filter and obtain 51 grams of load type gold catalysts (FDU-PBzPh/Au (I))).
Embodiment 9
The chloromethylation of a, ordered mesoporous phenolic resin
20 grams of ordered mesoporous phenolic resins and 100 grams of chloromethyl ethers and 21 grams of aluminium chloride (minute add for three times and be 1 hour each interval time) are mixed at 0 ℃ of temperature; then under argon shield, carry out 12 hours chloromethylations; prepare the ordered mesoporous phenolic resin of chloromethylation, its reaction temperature is 25 ℃.
The phosphine ligand function of b, ordered mesoporous phenolic resin
48 grams of diphenyl phosphine chlorides are dissolved in 89 grams of anhydrous tetrahydro furans, add 2 grams of lithium stirring reactions 3 hours, 32 grams of ordered mesoporous phenolic resins that gained solution added to the chloromethylation of above-mentioned preparation, continue reaction 12 hours, are prepared into the ordered mesoporous phenolic resin of phosphine ligand function.
The preparation of c, load type gold catalyst
After being dissolved with 222 grams of anhydrous tetrahydro furans, 50 grams of the ordered mesoporous phenolic resins of the phosphine ligand function of above-mentioned preparation add 2.7 gram of two hydration sodium chloraurate, under normal temperature, stir 12 hours, after reaction finishes, filter and obtain 51 grams of load type gold catalyst (FDU-PPh
2/ Au (I)).
Embodiment 10
The chloromethylation of a, ordered mesoporous phenolic resin
20 grams of ordered mesoporous phenolic resins and 100 grams of chloromethyl ethers and 21 grams of aluminium chloride (minute add for three times and be 1 hour each interval time) are mixed at 0 ℃ of temperature; then under argon shield, carry out 12 hours chloromethylations; prepare the ordered mesoporous phenolic resin of chloromethylation, its reaction temperature is 25 ℃.
The phosphine ligand function of b, ordered mesoporous phenolic resin
48 grams of diphenyl phosphine chlorides are dissolved in 89 grams of anhydrous tetrahydro furans, add 2 grams of lithium stirring reactions 3 hours, 32 grams of ordered mesoporous phenolic resins that gained solution added to the chloromethylation of above-mentioned preparation, continue reaction 12 hours, are prepared into the ordered mesoporous phenolic resin of phosphine ligand function.
The preparation of c, load type gold catalyst
After 50 grams of the ordered mesoporous phenolic resins of the phosphine ligand function of above-mentioned preparation are dissolved with 222 grams of anhydrous tetrahydro furans, add 1.1 grams of aurous chlorides, under normal temperature, stir 12 hours, after reaction finishes, filter and obtain 51 grams of load type gold catalyst (FDU-PPh
2/ Au (I).
Embodiment 11
By load type gold catalyst (FDU-PR of the present invention
1r
2/ Au (I)) for intermolecular allyl alcohol aminating reaction, concrete operation step is as follows:
Under argon shield, after being mixed with 0.21:0.34 weight portion with 4-methyl benzenesulfonamide, 1,3-diphenyl pi-allyl-1-alcohol adds successively silver trifluoromethanesulfonate 0.005 weight portion, load type gold catalyst (FDU-PPh
2/ Au (I)) 0.007 weight portion and anhydrous 1,4-dioxane 2.066 weight portions carry out intermolecular alcohol aminating reaction, employing thin-layer chromatography TLC follows the tracks of reaction, after reaction finishes, load type gold catalyst is leached, and obtains target product be after concentrating filter liquor by column chromatography chromatogram
n-(1,3-diphenyl pi-allyl)-(4-methyl) benzsulfamide, its productive rate is 95%.The washing of the load type gold catalyst water of filtered and recycled and acetone, vacuum drying 8 hours recycles treating next time.
Embodiment 12
Under argon shield, after being mixed with 0.21:0.28 weight portion with 4-nitroaniline, 1,3-diphenyl pi-allyl-1-alcohol adds successively silver trifluoromethanesulfonate 0.005 weight portion, load type gold catalyst (FDU-PPh
2/ Au (I)) 0.007 weight portion and anhydrous 1,4-dioxane 2.066 weight portions carry out intermolecular alcohol aminating reaction, employing thin-layer chromatography TLC follows the tracks of reaction, after reaction finishes, load type gold catalyst is leached, and obtains target product be after concentrating filter liquor by column chromatography chromatogram
n-(1,3-diphenyl pi-allyl)-(4-nitro) aniline, its productive rate is 98%.The washing of the load type gold catalyst water of filtered and recycled and acetone, vacuum drying 8 hours recycles treating next time.
Embodiment 13
Under argon shield, after being mixed with 0.098:0.34 weight portion with 4-methyl benzenesulfonamide, 2-thiazolinyl-1-cyclohexanol adds successively silver trifluoromethanesulfonate 0.005 weight portion, load type gold catalyst (FDU-PPh
2/ Au (I)) 0.007 weight portion and anhydrous 1,4-dioxane 2.066 weight portions carry out intermolecular alcohol aminating reaction, employing thin-layer chromatography TLC follows the tracks of reaction, after reaction finishes, load type gold catalyst is leached, and obtains target product be after concentrating filter liquor by column chromatography chromatogram
n-(2-alkene-cyclohexyl)-(4-methyl) benzsulfamide, its productive rate is 82%.The washing of the load type gold catalyst water of filtered and recycled and acetone, vacuum drying 8 hours recycles treating next time.
Embodiment 14
Under argon shield, after being mixed with 0.21:0.34 weight portion with 4-methyl benzenesulfonamide, 1,3-diphenyl pi-allyl-1-alcohol adds successively silver trifluoromethanesulfonate 0.005 weight portion, load type gold catalyst (FDU-P (4-CF
3ph)
2/ Au (I)) 0.025 weight portion and anhydrous 1,4-dioxane 2.066 weight portions carry out intermolecular alcohol aminating reaction, employing thin-layer chromatography TLC follows the tracks of reaction, after reaction finishes, load type gold catalyst is leached, and obtains target product be after concentrating filter liquor by column chromatography chromatogram
n-(1,3-diphenyl pi-allyl)-(4-methyl) benzsulfamide, its productive rate is 98%.The washing of the load type gold catalyst water of filtered and recycled and acetone, vacuum drying 8 hours recycles treating next time.
Embodiment 15
Under argon shield, after being mixed with 0.21:0.34 weight portion with 4-methyl benzenesulfonamide, 1,3-diphenyl pi-allyl-1-alcohol adds successively silver trifluoromethanesulfonate 0.005 weight portion, load type gold catalyst (FDU-P (4-OMePh)
2/ Au (I)) 0.014 weight portion and anhydrous 1,4-dioxane 2.066 weight portions carry out intermolecular alcohol aminating reaction, employing thin-layer chromatography TLC follows the tracks of reaction, after reaction finishes, load type gold catalyst is leached, and obtains target product be after concentrating filter liquor by column chromatography chromatogram
n-(1,3-diphenyl pi-allyl)-(4-methyl) benzsulfamide, its productive rate is 93%.The washing of the load type gold catalyst water of filtered and recycled and acetone, vacuum drying 8 hours recycles treating next time.
Embodiment 16
Under argon shield, after being mixed with 0.21:0.34 weight portion with 4-methyl benzenesulfonamide, 1,3-diphenyl pi-allyl-1-alcohol adds successively silver trifluoromethanesulfonate 0.005 weight portion, load type gold catalyst (FDU-P (2-OMePh)
2/ Au (I)) 0.017 weight portion and anhydrous 1,4-dioxane 2.066 weight portions carry out intermolecular alcohol aminating reaction, employing thin-layer chromatography TLC follows the tracks of reaction, after reaction finishes, load type gold catalyst is leached, and obtains target product be after concentrating filter liquor by column chromatography chromatogram
n-(1,3-diphenyl pi-allyl)-(4-methyl) benzsulfamide, its productive rate is 90%.The washing of the load type gold catalyst water of filtered and recycled and acetone, vacuum drying 8 hours recycles treating next time.
Embodiment 17
Under argon shield, after being mixed with 0.21:0.34 weight portion with 4-methyl benzenesulfonamide, 1,3-diphenyl pi-allyl-1-alcohol adds successively silver trifluoromethanesulfonate 0.005 weight portion, load type gold catalyst (FDU-P (OPh)
2/ Au (I)) 0.15 weight portion and anhydrous 1,4-dioxane 2.066 weight portions carry out intermolecular alcohol aminating reaction, employing thin-layer chromatography TLC follows the tracks of reaction, after reaction finishes, load type gold catalyst is leached, and obtains target product be after concentrating filter liquor by column chromatography chromatogram
n-(1,3-diphenyl pi-allyl)-(4-methyl) benzsulfamide, its productive rate is 92%.The washing of the load type gold catalyst water of filtered and recycled and acetone, vacuum drying 8 hours recycles treating next time.
Embodiment 18
Under argon shield; by 1; 3-diphenyl pi-allyl-1-alcohol adds silver trifluoromethanesulfonate 0.005 weight portion, load type gold catalyst (FDU-PMePh/Au (I)) 0.097 weight portion and anhydrous 1 successively after mixing with 0.21:0.34 weight portion with 4-methyl benzenesulfonamide; 4-dioxane 2.066 weight portions carry out intermolecular alcohol aminating reaction; adopt thin-layer chromatography TLC to follow the tracks of reaction; reaction leaches load type gold catalyst after finishing, and obtains target product be after concentrating filter liquor by column chromatography chromatogram
n-(1,3-diphenyl pi-allyl)-(4-methyl) benzsulfamide, its productive rate is 89%.The washing of the load type gold catalyst water of filtered and recycled and acetone, vacuum drying 8 hours recycles treating next time.
Embodiment 19
Under argon shield, after being mixed with 0.21:0.34 weight portion with 4-methyl benzenesulfonamide, 1,3-diphenyl pi-allyl-1-alcohol adds successively silver trifluoromethanesulfonate 0.005 weight portion, load type gold catalyst (FDU-PCy
2/ Au (I)) 0.18 weight portion and anhydrous 1,4-dioxane 2.066 weight portions carry out intermolecular alcohol aminating reaction, employing thin-layer chromatography TLC follows the tracks of reaction, after reaction finishes, load type gold catalyst is leached, and obtains target product be after concentrating filter liquor by column chromatography chromatogram
n-(1,3-diphenyl pi-allyl)-(4-methyl) benzsulfamide, its productive rate is 86%.The washing of the load type gold catalyst water of filtered and recycled and acetone, vacuum drying 8 hours recycles treating next time.
Embodiment 20
Under argon shield; by 1; 3-diphenyl pi-allyl-1-alcohol adds silver trifluoromethanesulfonate 0.005 weight portion, load type gold catalyst (FDU-PBzPh/Au (I)) 0.038 weight portion and anhydrous 1 successively after mixing with 0.21:0.34 weight portion with 4-methyl benzenesulfonamide; 4-dioxane 2.066 weight portions carry out intermolecular alcohol aminating reaction; adopt thin-layer chromatography TLC to follow the tracks of reaction; reaction leaches load type gold catalyst after finishing, and obtains target product be after concentrating filter liquor by column chromatography chromatogram
n-(1,3-diphenyl pi-allyl)-(4-methyl) benzsulfamide, its productive rate is 90%.The washing of the load type gold catalyst water of filtered and recycled and acetone, vacuum drying 8 hours recycles treating next time.
Embodiment 21
By load type gold catalyst (FDU-PR of the present invention
1r
2/ Au (I)) for 2-alkynyl-1, the intramolecular cyclization reaction of 3-dicarbapentaborane compounds, concrete operations are as follows:
Under argon shield; 2-benzoyl-6-alkynyl cognac oil is mixed with the weight portion of 0.12:2.45:3.35 with isopropyl alcohol, methyl-sulfoxide, then add successively the load type gold catalyst (FDU-PPh of the silver trifluoromethanesulfonate of 0.068 weight portion, the NaOH of 0.003 weight portion and 0.035 weight portion
2/ Au (I)) carry out intramolecular cyclization reaction; adopt thin-layer chromatography TLC to follow the tracks of reaction; after reaction finishes, load type gold catalyst is leached, after concentrating filter liquor, by column chromatography chromatogram, obtaining target product is 1-benzoyl-2-methylene cyclopentanecarboxylic acid second fat, and its productive rate is 95%.The washing of the load type gold catalyst water of filtered and recycled and acetone, vacuum drying 8 hours recycles treating next time.
Embodiment 22
Under argon shield, after 1,3-diphenyl pi-allyl-1-alcohol is mixed with 0.21:0.34 weight portion with 4-methyl benzenesulfonamide, add successively silver trifluoromethanesulfonate 0.005 weight portion, use rear load type gold catalyst (the FDU-PPh reclaiming
2/ Au (I)) 0.007 weight portion and anhydrous 1,4-dioxane 2.066 weight portions carry out intermolecular alcohol aminating reaction, adopt thin-layer chromatography TLC to follow the tracks of reaction, after reaction finishes, load type gold catalyst is leached, after concentrating filter liquor, by column chromatography chromatogram, obtain target product
n-(1,3-diphenyl pi-allyl)-(4-methyl) benzsulfamide, its productive rate is 95%.The washing of the load type gold catalyst water of filtered and recycled and acetone, vacuum drying 8 hours recycles treating next time.
Embodiment 23
Under argon shield; add successively 2-benzoyl-6-alkynyl cognac oil and isopropyl alcohol, methyl-sulfoxide; weight portion with 0.12:2.45:3.35 mixes, and then adds the silver trifluoromethanesulfonate of 0.068 weight portion, load type gold catalyst (the FDU-PPh that the NaOH of 0.003 weight portion and 0.035 weight portion reclaim after using
2/ Au (I)) carry out intramolecular cyclization reaction; adopt thin-layer chromatography TLC to follow the tracks of reaction; after reaction finishes, load type gold catalyst is leached, after concentrating filter liquor, by column chromatography chromatogram, obtain target product 1-benzoyl-2-methylene cyclopentanecarboxylic acid second fat, its productive rate is 95%.The washing of the load type gold catalyst water of filtered and recycled and acetone, vacuum drying 8 hours recycles treating next time.
Just the present invention will be further described for each embodiment above, and not in order to limit patent of the present invention, all is the present invention's equivalence enforcement, within all should being contained in the claim scope of patent of the present invention.
Claims (8)
1. a load type gold catalyst, is characterized in that this catalyst adopts the complexing of phosphine part to monovalence gold compound, is then carried on ordered mesoporous phenolic resin material, makes the load type gold catalyst that loading is 2.4 ~ 4.0 wt.%, and its structural formula is as follows:
Wherein: R
1=Me, Et, Cy, Ph, (2-OMe) Ph, (4-OMe) Ph, (4-CF
3) Ph, OPh, Bz,
,
or
;
R
2=Et, Cy, Ph, (2-OMe) Ph, (4-OMe) Ph, (4-CF
3) Ph, OPh, Bz,
,
or
.
2. the preparation of load type gold catalyst described in a claim 1, it is characterized in that adopting the complexing of phosphine part to monovalence gold compound, then be carried on ordered mesoporous phenolic resin material, make the load type gold catalyst that loading is 0.42 ~ 2.62wt%, its expression is FDU-PR
1r
2/ Au (I), concrete preparation comprises the following steps:
The chloromethylation of a, ordered mesoporous phenolic resin
Ordered mesoporous phenolic resin is mixed by 1:4.5 ~ 5.5:1 ~ 1.5 weight ratio with chloromethyl ether and aluminium chloride at 0 ℃ of temperature, then under argon shield, carry out 10 ~ 15 hours chloromethylations, the ordered mesoporous phenolic resin of preparing chloromethylation, its reaction temperature is 20 ~ 30 ℃, and described aluminium chloride is to add for 2 ~ 3 times and be 1 ~ 2 hour each interval time;
The phosphine ligand function of b, ordered mesoporous phenolic resin
By two replacement phosphonium chloride (ClPR
1r
2) by after 0.25 ~ 1.5:1 dissolving, add 2 grams of lithium stirring reactions 2 ~ 4 hours with anhydrous tetrahydro furan, then add 30 ~ 40 grams of the ordered mesoporous phenolic resins of the chloromethylation of above-mentioned preparation to continue reaction 10 ~ 14 hours, prepare the ordered mesoporous phenolic resin of phosphine ligand function;
The preparation of c, load type gold catalyst
After the ordered mesoporous phenolic resin of the phosphine ligand function of above-mentioned preparation and anhydrous tetrahydro furan are dissolved by 1:4.0 ~ 6.0, add 1 ~ 3 gram of monovalence gold compound, under normal temperature, stir 12 hours, after reaction finishes, filter to obtain load type gold catalyst.
3. the preparation of load type gold catalyst according to claim 2, is characterized in that described monovalence gold compound is aurous chloride, dimethyl sulphide aurous chloride or sodium chloraurate.
4. the preparation of load type gold catalyst according to claim 2, it is characterized in that described two replace phosphonium chlorides be diphenyl phosphine chloride, two (2-methoxyl group) phenyl phosphonium chloride, two (4-methoxyl group) phenyl phosphonium chloride, two (4-trifluoromethyl) phenyl phosphonium chloride, two phenoxy group phosphonium chlorides, aminomethyl phenyl phosphonium chloride, dicyclohexyl phosphonium chloride, two (2-furyl) phosphonium chloride, diethyl phosphonium chloride, benzyl phenyl phosphonium chloride or
r-2,2 '-bis-(phenyl phosphonium chlorides)-1,1 '-dinaphthalene.
5. an application for load type gold catalyst described in claim 1, is characterized in that this catalyst is for 2-alkynyl-1, the intramolecular cyclization reaction of 3-dicarbapentaborane compounds and intermolecular allyl alcohol aminating reaction, and its concrete application is as follows:
A, intermolecular allyl alcohol aminating reaction
Under argon shield, after being mixed with 0.072 ~ 0.21:0.19 ~ 0.37 weight portion with aminated compounds, allyl alcohol compound adds successively silver trifluoromethanesulfonate 0.005 weight portion, load type gold catalyst (FDU-PR
1r
2/ Au (I)) 0.003 ~ 0.025 weight portion and anhydrous 1,4-dioxane 2.066 weight portions carry out intermolecular alcohol aminating reaction, adopt thin-layer chromatography TLC to follow the tracks of reaction, after reaction finishes, load type gold catalyst is leached, after concentrating filter liquor, by column chromatography chromatogram, obtaining target product is allyl amine compounds;
B, 2-alkynyl-1, the intramolecular cyclization reaction of 3-dicarbapentaborane compounds
Under argon shield; by 2-alkynyl-1; 3-dicarbapentaborane compounds mixes with the weight portion of 0.09 ~ 0.15:2.45:3.35 with isopropyl alcohol, methyl-sulfoxide, then adds successively the load type gold catalyst (FDU-PR of the silver trifluoromethanesulfonate of 0.068 weight portion, the NaOH of 0.003 weight portion and 0.017 ~ 0.11 weight portion
1r
2/ Au (I)) carry out intramolecular cyclization reaction; adopt thin-layer chromatography TLC to follow the tracks of reaction; after reaction finishes, load type gold catalyst is leached, after concentrating filter liquor, by column chromatography chromatogram, obtaining target product is 1-acyl group-2-methylene cyclopentanecarboxylic acid lipoid substance.
6. the application of load type gold catalyst according to claim 5, it is characterized in that described allyl alcohol compound is 1,3-diphenyl pi-allyl-1-alcohol, 1,3-bis-(4-methyl) phenyl pi-allyl-1-alcohol, 1,3-bis-(4-methoxyl group) phenyl pi-allyl-1-alcohol, 1,3-bis-(4-nitro) phenyl pi-allyl-1-alcohol, 2-thiazolinyl-n-butyl alcohol, Isosorbide-5-Nitrae-dialkylene-3-amylalcohol or 2-thiazolinyl-1-cyclohexanol.
7. the application of load type gold catalyst according to claim 5, it is characterized in that described aminated compounds be 4-methyl benzenesulfonamide, 4-methoxybenzenesulphoismide,
n-methyl-4-methyl benzenesulfonamide, 4-nitrobenzene sulfonamide, methylsulfonamides, 2-phenyl-acetamides, aniline, 4-chloroaniline, 4-nitroaniline or 4-aminoanisole.
8. the application of load type gold catalyst according to claim 5, it is characterized in that described 2-alkynyl-1, 3-dicarbapentaborane compounds is 2-benzoyl-6-alkynyl methyl heptanoate, 2-benzoyl-6-alkynyl cognac oil, 2-(4-methoxyl group) benzoyl-6-alkynyl cognac oil, 2-(3-methyl) benzoyl-6-alkynyl cognac oil, 2-(4-nitro) benzoyl-6-alkynyl cognac oil, 2-benzoyl-6-alkynyl enanthic acid isopropyl ester, 2-acetyl group-6-alkynyl methyl heptanoate, 2-acetyl group-6-alkynyl cognac oil, 2-acetyl group-6-alkynyl acid benzyl ester in heptan, 2-isopropyl bytyry-6-alkynyl cognac oil or 2-(4-pentynyl)-1-phenyl butane-1, 3-diketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310565323.0A CN103638975B (en) | 2013-11-14 | 2013-11-14 | A kind of load type gold catalyst and preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310565323.0A CN103638975B (en) | 2013-11-14 | 2013-11-14 | A kind of load type gold catalyst and preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103638975A true CN103638975A (en) | 2014-03-19 |
| CN103638975B CN103638975B (en) | 2016-05-04 |
Family
ID=50244341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310565323.0A Expired - Fee Related CN103638975B (en) | 2013-11-14 | 2013-11-14 | A kind of load type gold catalyst and preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103638975B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622374A (en) * | 2016-11-30 | 2017-05-10 | 福州大学 | Resin-based immobilized rhodium-phosphine complex catalyst as well as preparation method and application of catalyst |
| CN109046465A (en) * | 2018-07-25 | 2018-12-21 | 华东师范大学 | The preparation and application of a kind of immobilized chiral Au catalyst of mesoporous silicon material |
| CN111545247A (en) * | 2020-03-25 | 2020-08-18 | 华东师范大学 | SBA-15 loaded heterogeneous chiral phosphine gold catalyst and preparation method and application thereof |
| CN112898205A (en) * | 2021-01-12 | 2021-06-04 | 华东师范大学 | Method for synthesizing benzimidazole by using carbon dioxide and o-phenylenediamine compound |
| CN113277963A (en) * | 2021-06-02 | 2021-08-20 | 南京工业大学 | Amine compound and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101856624A (en) * | 2010-05-21 | 2010-10-13 | 华东师范大学 | Multiphase Pd catalyst and preparation method and application thereof |
| CN102139229A (en) * | 2011-01-19 | 2011-08-03 | 华东师范大学 | Method for preparing supported gold catalyst and application thereof |
-
2013
- 2013-11-14 CN CN201310565323.0A patent/CN103638975B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101856624A (en) * | 2010-05-21 | 2010-10-13 | 华东师范大学 | Multiphase Pd catalyst and preparation method and application thereof |
| CN102139229A (en) * | 2011-01-19 | 2011-08-03 | 华东师范大学 | Method for preparing supported gold catalyst and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| CHENGFU YAO，ET AL: "Mesostructured polymer-supported diphenylphosphine-palladium complex:An efficient and recyclable catalyst for Heck reactions", 《CATALYSIS COMMUNICATIONS》, vol. 10, 10 January 2009 (2009-01-10) * |
| MASAHIRO EGI，ET AL: "Reusable and Durable Immobilized-Cationic Gold(I) Catalysts for Environmentally Benign Bond-Forming Reactions", 《ADV. SYNTH. CATAL.》, vol. 353, 8 February 2011 (2011-02-08) * |
| MASARU UTSUNOMIYA, ET AL: "Direct Use of Allylic Alcohols for Platinum-Catalyzed Monoallylation of Amines", 《ORGANIC LETTERS》, vol. 9, no. 17, 21 July 2007 (2007-07-21) * |
| 于涛: ""Au（I）催化剂的负载及应用和FDU-NHC/Pd（II）在偶联反应中的应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 9, 15 September 2011 (2011-09-15) * |
| 王泳，等: "有机介孔材料负载金催化剂的制备及应用", 《第十七届全国分子筛学术大会会议论文集》, 29 August 2013 (2013-08-29) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622374A (en) * | 2016-11-30 | 2017-05-10 | 福州大学 | Resin-based immobilized rhodium-phosphine complex catalyst as well as preparation method and application of catalyst |
| CN106622374B (en) * | 2016-11-30 | 2019-02-22 | 福州大学 | A kind of resin base utilizing immobilized rhodium-and-phosphine composition catalyst and the preparation method and application thereof |
| CN109046465A (en) * | 2018-07-25 | 2018-12-21 | 华东师范大学 | The preparation and application of a kind of immobilized chiral Au catalyst of mesoporous silicon material |
| CN109046465B (en) * | 2018-07-25 | 2021-03-26 | 华东师范大学 | Preparation and application of mesoporous silicon material immobilized chiral gold catalyst |
| CN111545247A (en) * | 2020-03-25 | 2020-08-18 | 华东师范大学 | SBA-15 loaded heterogeneous chiral phosphine gold catalyst and preparation method and application thereof |
| CN112898205A (en) * | 2021-01-12 | 2021-06-04 | 华东师范大学 | Method for synthesizing benzimidazole by using carbon dioxide and o-phenylenediamine compound |
| CN112898205B (en) * | 2021-01-12 | 2022-10-04 | 华东师范大学 | Method for synthesizing benzimidazole by using carbon dioxide and o-phenylenediamine compound |
| CN113277963A (en) * | 2021-06-02 | 2021-08-20 | 南京工业大学 | Amine compound and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103638975B (en) | 2016-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103638975A (en) | Supported gold catalyst, its preparation and its application | |
| Wu et al. | Synergistic Pd/Cu catalysis in organic synthesis | |
| Borrajo-Calleja et al. | Palladium-catalyzed enantioselective intermolecular carboetherification of dihydrofurans | |
| CN102153525A (en) | Preparation method and application of novel benzothiazole salt ionic liquid | |
| CN106810517A (en) | It is a kind of that the method that 5 hydroxymethyl furfural continuously synthesizes is realized by continuous extraction | |
| CN105618139B (en) | A kind of ligocellulose degradation's method based on molybdenum multi-metal oxygen hydrochlorate | |
| CN102718826B (en) | Method for extracting and separating 24-dehydrocholesterol and cholesterol by ionic liquid | |
| CN104610256B (en) | A kind of preparation method and its obtained quiral products of 1,5 naphthyridine type compound of tetrahydro | |
| CN103553958B (en) | Column [5] aromatic derivative modified by amido podand as well as preparation method and application thereof | |
| CN104128205B (en) | The metal Ru catalyst that Ionic Liquid Modified, magnetic silica support and synthetic method thereof and application | |
| CN101940951B (en) | Load-type chiral catalyst and application thereof in catalysis preparation of Fluoxetine intermediate | |
| CN103880762A (en) | Preparation method of 1,2,3-triazole compound | |
| CN105964306A (en) | Poly(ionic liquid)-based magnetic nanoparticle and its preparation method and use in three-ingredient reaction | |
| CN103172479B (en) | Preparation method for biaryl through palladium catalysis | |
| CN102500418B (en) | Preparation method of magnetic bidentate imide palladium ligand catalyst | |
| CN102580773B (en) | Preparation method of load type chiral ketone catalyst and application thereof | |
| CN105934423B (en) | Production process of 2, 3, 6-trimethylphenol | |
| CN106349249A (en) | Method for green synthesis of norcantharidin derivative | |
| CN104402661A (en) | Economic and efficient method for asymmetric synthesis of R-configuration aromatic alcohol through copper salt catalysis | |
| CN103965057B (en) | A kind of nitrile prepares the method for primary amine | |
| CN101857517A (en) | Method for preparing fluorobiaryl compound in pure water solution | |
| CN103880675B (en) | Improved catalyzed synthesis method for 1,4-dicarbonyl compound | |
| CN109046465B (en) | Preparation and application of mesoporous silicon material immobilized chiral gold catalyst | |
| CN101879458B (en) | Preparation method of polysiloxane-loaded chiral diamine derivative catalyst | |
| CN108383755B (en) | Method for synthesizing alkene dinitrile compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160504 Termination date: 20181114 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |