CN108283936A - A kind of preparation method and applications of the recyclable palladium catalyst of water soluble polymer load - Google Patents
A kind of preparation method and applications of the recyclable palladium catalyst of water soluble polymer load Download PDFInfo
- Publication number
- CN108283936A CN108283936A CN201810026071.7A CN201810026071A CN108283936A CN 108283936 A CN108283936 A CN 108283936A CN 201810026071 A CN201810026071 A CN 201810026071A CN 108283936 A CN108283936 A CN 108283936A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- water
- soluble polymer
- water soluble
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
- B01J2231/4227—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group with Y= Cl
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of the recyclable palladium catalyst of water soluble polymer load and its applications in Suzuki coupling reactions, include the following steps：Water, water soluble polymer and chlorine palladium acid sodium is added and is stirred until homogeneous；Reducing agent is added, continues to stir, obtains black or dark brown aqueous solution；Centrifugal treating is carried out to obtained aqueous solution, supernatant is obtained, then remove the water in supernatant by the way of freeze-drying, obtains catalyst；Obtained catalyst is put into protective gas, 150 DEG C of 1 1.5h of roasting, then disperses in aqueous solution, to form catalyst water storing liquid again.Catalyst after use can be detached the complete substrate of unreacted, product and catalyst by simple liquid separation made from step using the present invention, enormously simplify operation element amount；Aqueous phase catalyst after separation can store, and can continue to carry out next step catalytic cycle, facilitate industrial production, improve efficiency.
Description
Technical field
It is loaded the present invention relates to organic synthesis palladium catalyst manufacturing technology field more particularly to a kind of water soluble polymer
The preparation method of recyclable palladium catalyst and its application in Suzuki coupling reactions.
Background technology
Transition metal-catalyzed homogeneous reaction has very high efficiency and selectivity, but apparent disadvantage there are two them,
First is that noble metal catalyst is difficult to recycle after the reaction, and second is that heavy metal has minimal residue in the product, this
Have led to the loss of noble metal and the pollution to product.Therefore, the catalyst of support type has obtained extensively in Chemical Manufacture
Attention and application.Immobilized one of the common method of palladium is that palladium is fixed in a manner of physical absorption on carrier, and carrier is main
Including activated carbon, zeolite molecular sieve, metal oxide, clay, alkalies and alkaline earth salt and organic polymer.It is another normal
It is to graft ligand on carrier with method, complex compound, such as sulfydryl, phosphine, Cabbeen, imines and polyethylene glycol is formed with palladium.
The palladium heterogeneous catalysis that either prepared by which kind of method, the means detached from reaction system are all centrifugation, mistake
Filter, or magnet concentration and separation is utilized to magnetic carrier.For a large amount of reactant and heterogeneous catalysis in chemical industry
Agent, separation process are all time-consuming and laborious, are not conducive to improve production efficiency.Powder carrier is difficult to and easily there is also filtering
The problems such as being polluted by reactant.
Application No. is a kind of nano Pd catalyst and its preparation are described in 200510040669.4 Chinese patent literature
Method is prepared in water soluble polymer and low-carbon alcohols using water soluble polymer as carrier by water-soluble inorganic palladium salt
Polymer-supported nano Pd catalyst.Process parameter control is more coarse in its preparation process, after the reaction not to product
It is handled, causes the catalyst purity generated and quality relatively low, and the separating-purifying in later stage is more complicated, leads to organic efficiency
It is low.
Invention content
Technical problem to be solved by the present invention lies in provide a kind of being coupled for Suzuki for water soluble polymer load
Reaction recyclable palladium catalyst preparation method, which solve traditional preparation methods prepare palladium catalyst catalyst purity and
Quality is relatively low, and caused separating-purifying is complicated for operation, the low problem of organic efficiency.
The technical problems to be solved by the invention are realized using following technical scheme：
A kind of preparation method of the recyclable palladium catalyst of water soluble polymer load, includes the following steps：
A, water soluble polymer and chlorine palladium acid sodium are added to the water, are stirred until homogeneous；
B, reducing agent is added, continues to stir, obtains black or dark brown aqueous solution；
C, centrifugal treating is carried out to obtained aqueous solution, obtains supernatant, it will be in supernatant by the way of freeze-drying
Water remove, obtain catalyst；
D, obtained catalyst is placed in protective gas, 150 DEG C of roasting 1-1.5h, then be re-dispersed into water, formed
Catalyst water storing liquid.
Further improvement lies in that per in 100ml water, the dosage of the water soluble polymer is 5g, the dosage of chlorine palladium acid sodium
Dosage for 0.7g, reducing agent is 0.1-0.25g.
Further improvement lies in that 100ml water is often added in step a, the dosage of water described in step d is 100ml.
Further improvement lies in that water soluble polymer described in step a be bovine serum albumin, it is egg white lyase, water-soluble
It is one or more in property starch, polyacrylamide.
Further improvement lies in that stirring described in step a is carried out under the conditions of 50 DEG C.
Further improvement lies in that reducing agent described in step b is one in sodium borohydride, potassium borohydride, tert-butylamine borine
Kind.
Further improvement lies in that the time stirred described in step b is 1-2h.
Further improvement lies in that the condition of centrifugal treating described in step c is rotating speed 10000rpm, time 10min.
The present invention also provides application of the above-mentioned water soluble polymer supported catalyst in Suzuki coupling reactions, packets
The load capacity for measuring catalyst in advance is included, certain catalyst/substrate ratios is then pressed, launches boric acid substrate, hydrocarbonization on demand
Close object substrate, alkaline substrate and above-mentioned catalyst water storing liquid, reaction system is vacuumized and under protective gas protection into
Row reaction, waits for after reaction standing reaction solution, then carries out water-oil separating, direct to the aqueous phase catalyst obtained after separation
Recycling carries out separating-purifying into next step catalysis reaction to oil-phase product.
Further improvement lies in that the boric acid substrate is aryl boric acid, ene boric acid or borate, the hydrocarbon
Substrate is aromatic hydrocarbon or alkene, and the alkalinity substrate is carbonate or fluoride salt.
The beneficial effects of the invention are as follows：The catalyst prepared using the above method is completed in catalysis Suzuki coupling reactions
Later, substrate and product are all dissolved in organic phase, and catalyst is also in water, can will not by simple liquid separation after standing
Reacted substrate, product and catalyst separation, enormously simplify operation element amount.Aqueous phase catalyst after separation can store up
It deposits, can continue to carry out next step catalytic cycle, facilitate industrial production, improve efficiency.
Specific implementation mode
It elaborates below to the embodiment of the present invention, the present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
200ml water is added in container bottle, the bovine serum albumin and 1.4g chlorine palladium acid sodium of 10g stir under the conditions of 50 DEG C；
0.2g sodium borohydride reduction agent is added, continues to stir 1h, obtains black or dark brown aqueous solution.10000rpm centrifuges 10min,
Unsupported palladium particle centrifugation is fallen, supernatant is removed water by the way of freeze-drying, catalyst is obtained, then in nitrogen
It under atmosphere, after catalyst is roasted 1h at 150 DEG C, is dispersed in again in 200ml aqueous solutions, forms catalyst water storing liquid simultaneously
It is saved backup in 4 DEG C.
Embodiment 2
The addition 200ml water in container bottle, the water soluble polymer egg white lyase and 1.4g chlorine palladium acid sodium of 10g,
It is stirred under the conditions of 50 DEG C.0.3g potassium borohydride reduction agent is added, continues to stir 1.5h, obtains black or dark brown aqueous solution.
10000rpm centrifuges 10min, unsupported palladium particle centrifugation is fallen, supernatant is removed water by the way of freeze-drying, so
Afterwards and then under nitrogen atmosphere, it after catalyst being roasted 1.2h at 150 DEG C, is dispersed in again in 200ml aqueous solutions, formation is urged
Agent water storing liquid is simultaneously saved backup in 4 DEG C.
Embodiment 3
200ml water, the water soluble polymer water soluble starch and 1.4g chlorine palladium acid sodium of 10g, 50 are added in container bottle
It is stirred under the conditions of DEG C.0.4g potassium borohydride reduction agent is added, continues to stir 1.5h, obtains black or dark brown aqueous solution.
10000rpm centrifuges 10min, unsupported palladium particle centrifugation is fallen, supernatant is removed water by the way of freeze-drying, so
Afterwards and then under nitrogen atmosphere, it after catalyst being roasted 1.2h at 150 DEG C, is dispersed in again in 200ml aqueous solutions, formation is urged
Agent water storing liquid is simultaneously saved backup in 4 DEG C.
Embodiment 4
200ml water, the water soluble polymer polyacrylamide and 1.4g chlorine palladium acid sodium of 10g, 50 are added in container bottle
It is stirred under the conditions of DEG C.0.5g tert-butylamine borane reduction agent is added, continues to stir 2h, obtains black or dark brown aqueous solution.
10000rpm centrifuges 10min, unsupported palladium particle centrifugation is fallen, supernatant is removed water by the way of freeze-drying, so
Afterwards and then under nitrogen atmosphere, it after catalyst being roasted 1.5h at 150 DEG C, is dispersed in again in 200ml aqueous solutions, formation is urged
Agent water storing liquid is simultaneously saved backup in 4 DEG C.
It chooses phenyl boric acid and bromobenzene etc. and carries out Suzuki coupling reactions (suzuki reaction), above-mentioned preparation is added in reaction process
Catalyst.
It is tested by taking palladium catalyst made from embodiment 2 as an example, passes through ICP AES (inductively coupled plasma atoms
Emission spectrometry) to measure the load capacity of this catalyst be 1.3%wt (weight ratio), concentration of the catalyst in water phase storing liquid is
5g/100ml, specific catalysis operation are as follows：
0.122g phenyl boric acids and 0.105ml bromobenzenes is taken to be scattered in 20ml toluene, catalyst water storing liquid 3.27ml, bottom
Object/Pd molar ratios are 100/2 and 2.5equiv K2CO3(0.345g) is placed in a reaction flask.Reaction system is taken out with biexhaust pipe
Nitrogen protection is carried out after vacuum, and 1.5h is vigorously stirred under the conditions of 50 DEG C.After reaction, reaction solution is stood, then uses and divides
Liquid funnel carries out water-oil separating operation, aqueous phase catalyst recycling, into next step catalysis reaction；Separation is carried out to oil-phase product to carry
It is pure.
Using classical commercialization palladium/carbon (Pd/C) catalyst as comparative example, ingredient proportion is consistent with above-mentioned catalyst, because
Pd load capacity is 10% in palladium/carbon, therefore the Pd/C mass being added is 21 μ g.
Experiment obtains catalyst activity correction data, sees following table：
It can be seen that from the experimental data of table and using water-soluble heterogeneous catalysis produced by the present invention be catalyzed instead
The yield answered is equally higher, has been approached the recovery levels of commercialized palladium/carbon (Pd/C) catalyst.But the present invention is returning
Work of bringing drill to an end is upper need to can only to be detached the complete substrate of unreacted, product and catalyst by simple liquid separation, and behaviour is enormously simplified
Make workload, and the aqueous phase catalyst after separation can store, can continue to carry out next step catalytic cycle, facilitate industrial life
Production improves efficiency.
It is a kind of detailed embodiment and specific operating process of the present invention above, is before being with technical solution of the present invention
It puts and is implemented, but protection scope of the present invention is not limited to the above embodiments.
Claims (10)
1. a kind of preparation method of the recyclable palladium catalyst of water soluble polymer load, which is characterized in that include the following steps：
A, water soluble polymer and chlorine palladium acid sodium are added to the water, are stirred until homogeneous；
B, reducing agent is added, continues to stir, obtains black or dark brown aqueous solution；
C, centrifugal treating is carried out to obtained aqueous solution, supernatant is obtained, by the water in supernatant by the way of freeze-drying
It removes, obtains catalyst；
D, obtained catalyst is placed in protective gas, 150 DEG C of roasting 1-1.5h, then be re-dispersed into water, form catalysis
Agent water storing liquid.
2. a kind of preparation method of the recyclable palladium catalyst of water soluble polymer load according to claim 1, special
Sign is that, per in 100ml water, the dosage of the water soluble polymer is 5g, and the dosage of chlorine palladium acid sodium is 0.7g, the use of reducing agent
Amount is 0.1-0.25g.
3. a kind of preparation method of the recyclable palladium catalyst of water soluble polymer load according to claim 1, special
Sign is, 100ml water is often added in step a, and the dosage of water described in step d is 100ml.
4. a kind of preparation method of the recyclable palladium catalyst of water soluble polymer load according to claim 1, special
Sign is that water soluble polymer described in step a is bovine serum albumin, egg white lyase, water soluble starch, polyacrylamide
In it is one or more.
5. a kind of preparation method of the recyclable palladium catalyst of water soluble polymer load according to claim 1, special
Sign is that stirring is carried out under the conditions of 50 DEG C described in step a.
6. a kind of preparation method of the recyclable palladium catalyst of water soluble polymer load according to claim 1, special
Sign is that reducing agent described in step b is one kind in sodium borohydride, potassium borohydride, tert-butylamine borine.
7. a kind of preparation method of the recyclable palladium catalyst of water soluble polymer load according to claim 1, special
Sign is that the time stirred described in step b is 1-2h.
8. a kind of preparation method of the recyclable palladium catalyst of water soluble polymer load according to claim 1, special
Sign is that the condition of centrifugal treating described in step c is rotating speed 10000rpm, time 10min.
9. a kind of application of the water soluble polymer supported catalyst in Suzuki coupling reactions as described in claim 1-9,
It is characterised in that it includes：The load capacity of catalyst is measured in advance, is then pressed certain catalyst/substrate ratios, is launched boron on demand
Sour substrate, hydrocarbon substrate, alkaline substrate and above-mentioned catalyst water storing liquid, vacuumize reaction system and are protecting
It is reacted under gas shield, waits for after reaction standing reaction solution, then carry out water-oil separating, to the water obtained after separation
Phase catalyst directly recycles, and into next step catalysis reaction, separating-purifying is carried out to oil-phase product.
10. a kind of application of the water soluble polymer supported catalyst according to claim 9 in Suzuki coupling reactions,
It is characterized in that, the boric acid substrate is aryl boric acid, ene boric acid or borate, the hydrocarbon substrate is aromatic hydrocarbon
Or alkene, the alkalinity substrate is carbonate or fluoride salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810026071.7A CN108283936A (en) | 2018-01-11 | 2018-01-11 | A kind of preparation method and applications of the recyclable palladium catalyst of water soluble polymer load |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810026071.7A CN108283936A (en) | 2018-01-11 | 2018-01-11 | A kind of preparation method and applications of the recyclable palladium catalyst of water soluble polymer load |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108283936A true CN108283936A (en) | 2018-07-17 |
Family
ID=62834982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810026071.7A Pending CN108283936A (en) | 2018-01-11 | 2018-01-11 | A kind of preparation method and applications of the recyclable palladium catalyst of water soluble polymer load |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108283936A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6074979A (en) * | 1997-05-23 | 2000-06-13 | Celanese Gmbh | Polybetaine-stabilized, palladium-containing nanoparticles, a process for preparing them and also catalysts prepared from them for producing vinyl acetate |
| US6462095B1 (en) * | 1997-10-17 | 2002-10-08 | Axiva Gmbh | Polymer-stabilized metal colloid solutions, method for producing said solutions and use of the same as catalysts for fuel cell |
| CN1994631A (en) * | 2005-12-28 | 2007-07-11 | 中国科学院理化技术研究所 | Method for preparing re-dispersible silver nanoparticles by silver halide pre-crystallization reduction method |
| CN101219397A (en) * | 2008-01-22 | 2008-07-16 | 江南大学 | Process for producing platinum metal nano-particle for catalysis with polymer microsphere as carrier |
| CN103433071A (en) * | 2013-09-17 | 2013-12-11 | 绍兴文理学院 | IPN (interpenetrating polymer network)-loaded palladium nano catalyst as well as preparation method and applications thereof |
| CN106187783A (en) * | 2016-07-01 | 2016-12-07 | 中南大学 | The application in the hydrogenation of aromatic nitro compound of the polyamic acid supported palladium nanocatalyst |
| CN106607015A (en) * | 2016-12-07 | 2017-05-03 | 广州市逸都环保科技有限公司 | Nano titanium dioxide photocatalyst with double-particle size distribution and preparation method thereof |
-
2018
- 2018-01-11 CN CN201810026071.7A patent/CN108283936A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6074979A (en) * | 1997-05-23 | 2000-06-13 | Celanese Gmbh | Polybetaine-stabilized, palladium-containing nanoparticles, a process for preparing them and also catalysts prepared from them for producing vinyl acetate |
| US6462095B1 (en) * | 1997-10-17 | 2002-10-08 | Axiva Gmbh | Polymer-stabilized metal colloid solutions, method for producing said solutions and use of the same as catalysts for fuel cell |
| CN1994631A (en) * | 2005-12-28 | 2007-07-11 | 中国科学院理化技术研究所 | Method for preparing re-dispersible silver nanoparticles by silver halide pre-crystallization reduction method |
| CN101219397A (en) * | 2008-01-22 | 2008-07-16 | 江南大学 | Process for producing platinum metal nano-particle for catalysis with polymer microsphere as carrier |
| CN103433071A (en) * | 2013-09-17 | 2013-12-11 | 绍兴文理学院 | IPN (interpenetrating polymer network)-loaded palladium nano catalyst as well as preparation method and applications thereof |
| CN106187783A (en) * | 2016-07-01 | 2016-12-07 | 中南大学 | The application in the hydrogenation of aromatic nitro compound of the polyamic acid supported palladium nanocatalyst |
| CN106607015A (en) * | 2016-12-07 | 2017-05-03 | 广州市逸都环保科技有限公司 | Nano titanium dioxide photocatalyst with double-particle size distribution and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| FEYYAZ DURAP等: ""New route to synthesis of PVP-stabilized palladium(0) nanoclusters and their enhanced catalytic activity in Heck and Suzuki cross-coupling reactions"", 《APPL. ORGANOMETAL. CHEM.》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110270348B (en) | Noble metal monatomic catalyst and preparation and application thereof | |
| Bergbreiter et al. | Microwave promoted Heck reactions using an oligo (ethylene glycol)-bound SCS palladacycle under thermomorphic conditions | |
| CN100349832C (en) | Method for the telomerisation of non-cyclic olefins | |
| Yuan et al. | N‐Heterocyclic Carbene–Ytterbium Amide as a Recyclable Homogeneous Precatalyst for Hydrophosphination of Alkenes and Alkynes | |
| CN102020307B (en) | Disposal method of organic silicon copper-containing waste catalyst | |
| CN1852882A (en) | Process for reduction of carbon dioxide with organometallic complex | |
| CN1899972A (en) | Process for the preparation of a nickel/phosphorus ligand catalyst for olefin hydrocyanation | |
| CN108262072A (en) | It is a kind of for catalyzed by ruthenium complexes agent of acetylene hydrochlorination and its preparation method and application | |
| Shi et al. | Silica-assisted Suzuki–Miyaura reactions of heteroaryl bromides in aqueous media | |
| CN104069882A (en) | Method for preparing carbon-nitrogen material loaded nano metal catalyst | |
| CN101011669A (en) | Method for preparing chitose magnetic microsphere metal palladium complex catalyst | |
| CN110975924B (en) | Catalyst for preparing cyclohexanone by catalytic oxidation of cyclohexene, preparation method and application thereof | |
| Zhao et al. | Merging manganese and iminium catalysis: selective hydroalkenylation of unsaturated aldehydes and ketones | |
| CN108283936A (en) | A kind of preparation method and applications of the recyclable palladium catalyst of water soluble polymer load | |
| CN1966476A (en) | Iron-catalysed allylic alkylation | |
| CN107602369A (en) | A kind of preparation method of acrylic acid or acrylate | |
| CN102500418B (en) | Preparation method of magnetic bidentate imide palladium ligand catalyst | |
| CN106316866B (en) | A kind of preparation method of N- methyl aminated compounds | |
| CN101514188A (en) | Method for preparing 8-hydroxyquinoline metal compounds | |
| CN101444753A (en) | Method for preparing aldehyde by utilizing immobilized rhodium-and-phosphine composition catalyst | |
| CN112920227B (en) | Indenoindole structure-containing metallocene compound, preparation method and application thereof, and preparation method of alpha-olefin | |
| CA2555790A1 (en) | Extraction of metals with diquaternary ammonium salts | |
| CN103739543A (en) | Preparation method of tetrachlorpyridine | |
| Tsvelikhovsky et al. | On the involvement of palladium nanoparticles in the Heck and Suzuki reactions | |
| Amini et al. | Palladium nanoparticles immobilized on multifunctional hyperbranched polyglycerol-grafted magnetic nanoparticles as a sustainable and efficient catalyst for CC coupling reactions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180717 |