CN107930695A - A kind of Metal Palladium is with polymers catalyst and uses its carbon carbon coupling reaction method - Google Patents
A kind of Metal Palladium is with polymers catalyst and uses its carbon carbon coupling reaction method Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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Abstract
A kind of Metal Palladium is with polymers catalyst and matches somebody with somebody polymers catalyst using its carbon carbon coupling reaction method the invention discloses a kind of Metal Palladium and uses its carbon carbon coupling reaction method, it is mainly comprised the following steps：Halogenated aryl hydrocarbon, phenylboric acid, alkali and Metal Palladium are matched somebody with somebody into polymers catalyst, it is dissolved in alcohols, esters, aromatic hydrocarbons or ether organic solvent, in 10 DEG C 110 DEG C, react 2 10 it is small when, cooling, stands, is centrifuged, supernatant liquor obtains pure coupled product through column chromatography for separation, and sediment is used for secondary, three times and more times circular response.Compared with prior art, Metal Palladium of the invention is high with polymers catalyst activity, and cycle-index, up to more than ten time, catalytic activity is not decreased obviously, and solves the problems such as catalyst is difficult to separate, product is contaminated well, is adapted to the requirement commercially produced.
Description
Technical field：
The invention belongs to orgnometallic catalyst and organic synthesis field, is related to a kind of Metal Palladium and matches somebody with somebody polymers catalyst, carries at the same time
The C-C coupling reaction method completed for this kind of catalyst.
Background technology：
C-C coupling reaction occupies an important position in organic synthesis, is widely used in pharmacy, dyestuff, natural polymer
The field such as product and advanced material.Traditional palladium homogeneous catalyst is higher with good dispersion, catalytic activity, selectively good etc. excellent
Point, but there is catalyst be difficult to separate, the problems such as product is contaminated.And palladium heterogeneous catalysis can not only solve this well
A little problems, but also can recycled for multiple times, provide possibility for industrial applications.
At present, the carrier of palladium heterogeneous catalysis mainly has two classes：Inorganic carrier and organic polymer carrier.Inorganic carrier
In have metal oxide, silicoaluminophosphamolecular molecular sieve, silica, activated carbon etc., usually by infusion process by palladium homogeneous catalysis
Agent is directly adsorbed on carrier.Liang Xiliang etc. is using MgO as carrier（Chemistry and bonding, 2017,39（2）, 119-223）, Zou Bing etc.
Using multi-walled carbon nanotube as carrier（Wuhan University of Technology's journal, 2009,28（1）, 9-12）, grade then uses single to Wang Zhi forever
Pipe is as carrier（Acta PhySico-Chimica Sinica, 2009,25（5）, 825-828）Deng synthesis palladium heterogeneous catalysis, and applied to catalysis
Suzuki coupling reactions obtain higher yield.For organic polymer carrier, then using special on organic polymer carrier
Functional group, Metal Palladium is loaded on carrier, Metal Palladium organic coordination polymer catalyst is prepared by coordination etc.（Below
Abbreviation Metal Palladium matches somebody with somebody polymers catalyst）（Chemistry and bonding, 2014,36（4）, 290-294）.
Inventor based on the research to homogeneous orgnometallic catalyst and heterogeneous metal organic coordination polymer for many years,
Design, synthesized a kind of Metal Palladium and match somebody with somebody polymers catalyst, it is possible to achieve to C-C coupling reaction, catalytic activity is high, and circulates time
Up to more than ten times, catalytic activity is not decreased obviously number, solves the problems such as catalyst is difficult to separate, product is contaminated well,
It is adapted to the requirement commercially produced.
The content of the invention
The present invention provides a kind of Metal Palladium to match somebody with somebody polymers catalyst, and uses its C-C coupling reaction method, it is tied
Structure has below general formula：
(I)
Or（II）
Or（III）
Formula（I）、（II）、（III）Middle R is hydrogen, C1 ~ C12 alkyl, the aryl of C6 ~ C12, acenaphthenyl, be preferably hydrogen, C1 ~
Alkyl, phenyl, the acenaphthenyl of C4；Formula（I）Middle R1, R2, R3 and R4 can be identical or different, are respectively hydrogen, C1 ~ C12 alkane
Base, halogen, nitro, the aryl of C6 ~ C12, are preferably hydrogen, the alkyl of C1 ~ C4, halogen, nitro, phenyl, xenyl；Formula（III）
The methylene that middle R ' is methylene, the alkyl-substituted methylene of C1 ~ C12, C1 ~ C12 haloalkyls substitute, preferably methylene,
The alkyl-substituted methylene of C1 ~ C4；The fluorine-containing alkyl-substituted methylene of C1 ~ C4；X is halogen, is preferably chlorine, bromine.
A kind of Metal Palladium matches somebody with somebody the preparation method of polymers catalyst, it is characterised in that as follows including step：First, in indifferent gas
Under body protection, aromatic diamine compound and α-dialdehyde or ketone compound are dissolved in organic solvent, aromatic diamine compound and α-
The molar ratio of two aldehydes or ketones is 1 ~ 5：1, when reaction 0.5 ~ 48 is small at 0 ~ 80 DEG C of temperature, reactant is put into refrigerator after reaction
Crystallization, crystal use organic solvent washing after filtering, are dried in vacuo, obtain poly- alpha-diimine ligand；Then, by poly- alpha-diimine
Ligand with（PhCN）2PdCl2Be dissolved in organic solvent, poly- alpha-diimine ligand with（PhCN）2PdCl2Molar ratio be 1 ~ 5：1, in
When temperature -10 ~ 60 DEG C reaction 1-72 is small, stratification after reaction, sediment is filtered, and vacuum drying, obtains rear transition
Metal matches somebody with somebody polymers.The organic solvent is one of aromatic hydrocarbon, halogenated hydrocarbons, alcohols, ether solvent.
Match somebody with somebody the method for polymers catalyst C-C coupling reaction with Metal Palladium, it is characterised in that as follows including step：Will
Halogenated aryl hydrocarbon（IV）, phenylboric acid（V）, alkali and Metal Palladium match somebody with somebody polymers catalyst, be dissolved in alcohols, esters, aromatic hydrocarbons or amine etc.
In organic solvent, in 40 DEG C -120 DEG C, when reaction 2-10 is small, cool down, stand, be centrifuged, liquid phase is through silica gel column chromatography point
From（Petroleum ether is eluent）, obtain pure coupled product, sediment is used for secondary, three times and more times circular response.It is described
Alkali be K2CO3、Na2CO3、K3PO4、Na3PO4Or CH3One of ONa；The solvent be the monohydric alcohol of C1-C6, tetrahydrofuran,
One of dioxane, ethyl acetate, toluene, dimethylformamide, triethylamine.
The present invention has following obvious advantages compared with prior art：
Metal Palladium provided by the invention is a kind of novel supported catalyst with polymers catalyst, has catalytic activity height, and follow
Often up to more than ten times, catalytic activity is not decreased obviously ring, is solved that catalyst is difficult to separate, product is contaminated well etc. and is asked
Topic, is adapted to the requirement commercially produced.
The present invention, however, the present invention is not limited thereto are further illustrated below by embodiment.
Example 1
The preparation of poly- alpha-diimine ligand L 1
（L1）
Under inert gas shielding, p-phenylenediamine is added in the reaction bulb of 250mL（1.08g, 10 mmol）With 70 mL methanol,
Glyoxal water solution is added dropwise at 10 DEG C（1.27mL, 10 mmol）, when stirring reaction 8 is small.Reaction solution is put into refrigerator cooling
Crystallization, the crystal of precipitation is filtered to obtain crude product, is washed three times with ether, and vacuum drying, obtains product 1.18g, yield
90.0%。
Example 2
Metal Palladium matches somebody with somebody the preparation of polymers catalyst C1
（C1）
Under inert gas shielding, the poly- alpha-diimine ligand L 1 for preparing is added in embodiment 1 in the reaction bulb of 100ml
（0.2g, 1.5mmol）With 50 mL dichloromethane, add (PhCN)2PdCl2（0.58g, 1.5mmol）, at -10 DEG C of temperature
React 72 it is small when.Stratification after reaction, sediment are washed for several times with anhydrous ether after filtering, and vacuum drying, obtains
0.48g browns Metal Palladium matches somebody with somebody polymers catalyst C1, yield 91.6%.
Example 3
With Metal Palladium with polymers catalyst C1 catalysis C-C coupling reactions
0.43 g (2.5 mmol) is added in reaction bulb to methyl bromobenzene and 0.37 g (3 mmol) phenyl boric acid, 0.52 g
(3.75 mmol) K2CO3, catalyst（C1）0.01 g, adds the dissolving of 6 mL methanol, and at 60 DEG C, when reaction 2 is small, cooling is quiet
Put, be centrifuged, liquid phase is separated through silica gel column chromatography（Petroleum ether is eluent）, pure coupled product is obtained, 0.42 g, is received
Rate is 99%.Sediment is used for secondary, three times and more times circular response.
Example 4
The preparation of poly- alpha-diimine ligand L 2
（L2）
Under inert gas shielding, 2- methyl isophthalic acids, bis- amido benzene of 4- are added in 250ml three-necked flasks（1.83g, 15 mmol）
With 70 mL ethanol, diacetyl is added at 80 DEG C（0.87mL, 10 mmol）, when stirring reaction 0.5 is small.Reaction solution is put into
Refrigerator crystallisation by cooling, the crystal of precipitation is filtered to obtain crude product, is washed three times with acetone, and vacuum drying, obtains product
1.04g, yield 60.0%.
Example 5
Metal Palladium matches somebody with somebody the preparation of polymers catalyst C2
（C2）
Under inert gas shielding, the poly- alpha-diimine ligand L 2 for preparing is added in embodiment 3 in the reaction bulb of 100ml
（0.52g, 3.0 mmol）With 50 mL dichloromethane, add (PhCN)2PdCl2（0.58g, 1.5mmol）, at 10 DEG C of temperature
React 60 it is small when.Stratification after reaction, sediment are washed for several times with anhydrous ether after filtering, and vacuum drying, obtains
0.53g browns Metal Palladium matches somebody with somebody polymers catalyst C2, yield 90.0%.
Example 6
With Metal Palladium with polymers catalyst C2 catalysis C-C coupling reactions
Add 0.39 g (2.5 mmol) bromobenzenes and 0.46 g (3 mmol) p-methoxyphenyl boric acid in reaction bulb, 0.52
g (3.75 mmol) K2CO3, catalyst（C1）0.01 g, adds the dissolving of 6 mL isopropanols, cold when reaction 4 is small at 80 DEG C
But, stand, be centrifuged, liquid phase is separated through silica gel column chromatography（Petroleum ether is eluent）, obtain pure coupled product, 0.46
G, yield 99%.Sediment is used for secondary, three times and more times circular response.
Example 7
The preparation of poly- alpha-diimine ligand L 3
（L3）
Under inert gas shielding, adjacent nitro p-phenylenediamine is added in the reaction bulb of 250mL（3.06g, 20 mmol）With 70
ML isopropanols, acenaphthenequinone is added at 0 DEG C（1.82g, 10 mmol）, when stirring reaction 24 is small.Reaction solution is put into refrigerator cooling
Crystallization, the crystal of precipitation is filtered to obtain crude product, is washed three times with ether, and vacuum drying, obtains product 2.36g, yield
79.0%。
Example 8
Metal Palladium matches somebody with somebody the preparation of polymers catalyst C3
(C3)
Under inert gas shielding, the poly- alpha-diimine ligand L 3 for preparing is added in embodiment 5 in the reaction bulb of 100ml
（1.35g, 4.5 mmol）With 50 mL dichloromethane, add (PhCN)2PdCl2（0.58g, 1.5mmol）, in 25 DEG C of temperature
It is lower reaction 48 it is small when.Stratification after reaction, sediment are washed for several times with anhydrous ether after filtering, and vacuum drying, obtains
Match somebody with somebody polymers catalyst C3, yield 65.0% to 0.67g browns Metal Palladium.
Example 9
With Metal Palladium with polymers catalyst C3 catalysis C-C coupling reactions
0.39 g (2.5 mmol) is added in reaction bulb to methyl bromobenzene and 0.41 g (3 mmol) to methylphenylboronic acid,
0.52 g (3.75 mmol) K2CO3, catalyst（C3）0.01 g, adds the dissolving of 6 mL tetrahydrofurans, at 40 DEG C, reaction 6
Hour, cool down, stand, be centrifuged, liquid phase is separated through silica gel column chromatography（Petroleum ether is eluent）, obtain pure coupling production
Thing, 0.45 g, yield 99%.Sediment is used for secondary, three times and more times circular response.
Example 10
The preparation of poly- alpha-diimine ligand L 4
(L4)
Under inert gas shielding, 2,5- bis--chloro- Isosorbide-5-Nitrae-phenylenediamine is added in the reaction bulb of 250mL（5.31 g, 30
mmol）With the 70 mL tert-butyl alcohols, 1- phenyl -1,2- propanedione is added at 30 DEG C（1.48g, 10 mmol）, it is small that stirring reacts 24
When.Reaction solution is put into refrigerator crystallisation by cooling, the crystal of precipitation is filtered to obtain crude product, is washed three times with acetone, vacuum is done
It is dry, obtain product 1.64g, yield 56.7%.
Example 11
Metal Palladium matches somebody with somebody the preparation of polymers catalyst C4
(C4)
Under inert gas shielding, the poly- alpha-diimine ligand L 4 for preparing is added in embodiment 7 in the reaction bulb of 100ml
（1.19g, 6.0 mmol）With 50 mL dichloromethane, add (PhCN)2PdCl2（0.58g, 1.5mmol）, in 40 DEG C of temperature
It is lower reaction 36 it is small when.Stratification after reaction, sediment are washed for several times with anhydrous ether after filtering, and vacuum drying, obtains
Match somebody with somebody polymers catalyst C4, yield 87.0% to 0.54g browns Metal Palladium.
Example 12
With Metal Palladium with polymers catalyst C4 catalysis C-C coupling reactions
0.47 g (2.5 mmol) is added in reaction bulb to methoxybromobenzene and 0.41 g (3 mmol) to methylbenzene boron
Acid, 0.52 g (3.75 mmol) K2CO3, catalyst（C4）0.01 g, adds 6 mL dioxane, at 100 DEG C, reaction 8
Hour, cool down, stand, be centrifuged, liquid phase is separated through silica gel column chromatography（Petroleum ether is eluent）, obtain pure coupling production
Thing, 0.49 g, yield 99%.Sediment is used for secondary, three times and more times circular response.
Example 13
The preparation of poly- alpha-diimine ligand L 5
(L5)
Under inert gas shielding, benzidine is added in 250mL three-necked flasks（9.2g, 50 mmol）With 70 mL methanol,
Diacetyl is added dropwise at 50 DEG C（0.87mL, 10 mmol）, when stirring reaction 6 is small.Reaction solution is put into refrigerator crystallisation by cooling, is analysed
The crystal that goes out is filtered to obtain crude product, is washed three times with ether, and vacuum drying, obtains product 1.38g, yield 58.8%.
Example 14
Metal Palladium matches somebody with somebody the preparation of polymers catalyst C5
（C5）
Under inert gas shielding, the poly- alpha-diimine ligand L 5 for preparing is added in embodiment 9 in the reaction bulb of 100ml
（1.76g, 7.5 mmol）With 50 mL dichloromethane, add (PhCN)2PdCl2（0.58g, 1.5mmol）, in temperature 50 C
It is lower reaction 6 it is small when.Stratification after reaction, sediment are washed for several times with anhydrous ether after filtering, and vacuum drying, obtains
0.53g browns Metal Palladium matches somebody with somebody polymers catalyst C5, yield 79.0%.
Example 15
Match somebody with somebody the catalysis C-C coupling reaction of polymers catalyst C5 with Metal Palladium
0.72 g (2.5 mmol) is added in reaction bulb to hexyl iodobenzene and 0.54 g (3mmol) to isopropoxy benzene boron
Acid, 0.52 g (3.75 mmol) K2CO3, catalyst（C5）0.01 g, adds 6 mL toluene, and at 110 DEG C, reaction 10 is small
When, cool down, stand, be centrifuged, liquid phase is separated through silica gel column chromatography（Petroleum ether is eluent）, obtain pure coupling production
Thing, 0.73 g, yield 99%.Sediment is used for secondary, three times and more times circular response.
Example 16
The preparation of poly- alpha-diimine ligand L 6
(L6)
Under inert gas shielding, double (4- aminophenyls) the propane 5.65g, 25 mmol of 2,2- are added in 250mL three-necked flasks）
With 70 mL ethanol, acenaphthenequinone is added at 60 DEG C（1.82g, 10 mmol）, when stirring reaction 12 is small.Reaction solution is put into refrigerator
Crystallisation by cooling, the crystal of precipitation is filtered to obtain crude product, is washed three times with acetone, and vacuum drying, obtains product 2.541g, produces
Rate 68.1%.
Example 17
Metal Palladium matches somebody with somebody the preparation of polymers catalyst C6
（C6）
Under inert gas shielding, the poly- alpha-diimine ligand L 6 for preparing is added in embodiment 5 in the reaction bulb of 100ml
（1.12g, 3.0 mmol）With 50 mL dichloromethane, add (PhCN)2PdCl2（0.58g, 1.5mmol）, in temperature 60 C
It is lower reaction 1 it is small when.Stratification after reaction, sediment are washed for several times with anhydrous ether after filtering, and vacuum drying, obtains
0.52g browns Metal Palladium matches somebody with somebody polymers catalyst C6, yield 63.0%.
Example 18
Match somebody with somebody the catalysis C-C coupling reaction of polymers catalyst C6 with Metal Palladium
0.39 g (2.5 mmol) is added in reaction bulb to cyano group bromobenzene and 0.49 g (3 mmol) to propyl group phenyl boric acid,
0.52 g (3.75 mmol) K2CO3, catalyst（C6）0.01 g, adds 6 mL dimethylformamides, at 120 DEG C, reaction 4
Hour, cool down, stand, be centrifuged, liquid phase is separated through silica gel column chromatography（Petroleum ether is eluent）, obtain pure coupling production
Thing, 0.55 g, yield 99%.Sediment is used for secondary, three times and more times circular response.
Example 19-24
With C1, C2, C3, C4, C5 and C6 catalyst, respectively in different organic solvents, according to embodiment 3,6,9,12,15
With the reactions steps in 18, the multiple circulation of C-C coupling reaction is carried out, acquired results are shown in Table 1.
Table 1 carries out the multiple circulation result of C-C coupling reaction in different catalysts and solvent
| Example | Catalyst | Solvent | Cycle-index/reaction temperature（℃） | Yield（%） |
| Example 19 | C1 | Ethanol | 10 / 78 | 88.2 |
| Example 20 | C2 | Butanol | 10 / 117 | 89.1 |
| Example 21 | C3 | Isopropanol | 12 / 83 | 92.5 |
| Example 22 | C4 | Ethyl acetate | 10 / 77 | 87.0 |
| Example 23 | C5 | Triethylamine | 8 / 90 | 85.3 |
| Example 24 | C6 | Toluene | 5 / 110 | 90.1 |
Claims (10)
1. a kind of Metal Palladium matches somebody with somebody polymers catalyst, it is characterised in that its structure has below general formula：
(I)
Or（II）
Or（III）
Formula（I）、（II）、（III）Middle R is hydrogen, C1 ~ C12 alkyl, the aryl of C6 ~ C12, acenaphthenyl；Formula（I）Middle R1, R2,
R3And R4Can be identical or different, it is respectively hydrogen, C1 ~ C12 alkyl, halogen, nitro, the aryl of C6 ~ C12；Formula（III）Middle R ' is
The alkyl-substituted methylene of methylene, C1 ~ C12, the methylene of C1 ~ C12 haloalkyls substitution；X is halogen.
2. Metal Palladium according to claim 1 matches somebody with somebody polymers catalyst, it is characterised in that formula（I）、（II）、（III）Middle R is preferred
For hydrogen, the alkyl of C1 ~ C4, phenyl, acenaphthenyl；Formula（I）Middle R1, R2, R3 and R4 are preferably hydrogen, the alkyl of C1 ~ C4, halogen
Element, nitro, phenyl, xenyl；Formula（III）Middle R ' is preferably methylene, the alkyl-substituted methylene of C1 ~ C4；C1 ~ C4 contains fluothane
The methylene of base substitution；X is preferably chlorine, bromine.
3. a kind of Metal Palladium according to claim 1 matches somebody with somebody the preparation method of polymers catalyst, it is characterised in that including step
It is as follows：First, under inert gas shielding, aromatic diamine compound and α-dialdehyde or ketone compound are dissolved in organic solvent,
The molar ratio of aromatic diamine compound and α-two aldehydes or ketones is 1 ~ 5：1, when reaction 0.5 ~ 48 is small at 0 ~ 80 DEG C of temperature, reaction
Reactant is put into refrigerator crystallization afterwards, crystal uses organic solvent washing after filtering, is dried in vacuo, obtains poly- alpha-diimine and match somebody with somebody
Body；Then, by poly- alpha-diimine ligand with（PhCN）2PdCl2Be dissolved in organic solvent, poly- alpha-diimine ligand with（PhCN）2PdCl2Molar ratio be 1 ~ 5：1, when temperature -10 ~ 60 DEG C reaction 1-72 is small, stratification, sediment pass through after reaction
Filtering, vacuum drying, obtains late transition metal and matches somebody with somebody polymers, and the organic solvent is that aromatic hydrocarbon, halogenated hydrocarbons, alcohols, ethers are molten
One of agent.
4. preparation method according to claim 3, it is characterised in that α-dialdehyde or ketone compound and aromatic diamine compound
Molar ratio be 1 ~ 3：1, when reaction 3 ~ 24 is small at 10 ~ 60 DEG C of temperature.
5. preparation method according to claim 3, it is characterised in that poly- alpha-diimine ligand with（PhCN）2PdCl2Mole
Than for 1 ~ 3：1, reacted at 10 ~ 50 DEG C of temperature 6-48 it is small when.
6. preparation method according to claim 3, it is characterised in that the organic solvent for benzene, toluene, chloroform,
One of dichloromethane, methanol, ethanol, ether.
7. match somebody with somebody the method for polymers catalyst C-C coupling reaction with Metal Palladium, it is characterised in that as follows including step：By halogen
For aromatic hydrocarbons（IV）, phenyl boric acid（V）, alkali and Metal Palladium match somebody with somebody polymers catalyst, it is organic to be dissolved in alcohols, esters, aromatic hydrocarbons or amine etc.
In solvent, in 40 DEG C -120 DEG C, when reaction 2-10 is small, cool down, stand, be centrifuged, liquid phase is separated through silica gel column chromatography（Stone
Oily ether is eluent）, obtain pure coupled product, sediment is used for secondary, three times and more times circular response, the alkali
For K2CO3、Na2CO3、K3PO4、Na3PO4Or CH3One of ONa, the solvent are monohydric alcohol, tetrahydrofuran, the dioxy of C1-C6
One of six rings, ethyl acetate, toluene, dimethylformamide, triethylamine；
In formula：X is Br or I；R5, R6 are respectively selected from one of the alkyl of H, C1-C6 or the alkoxy of C1-C6 and CN.
8. the method for C-C coupling reaction according to claim 7, it is characterised in that wherein R5, R6 are respectively selected from H, C1
One kind in the alkyl of-C3, the alkoxy and CN of C1-C3.
9. the method for C-C coupling reaction according to claim 7, it is characterised in that wherein solvent is the unitary of C1-C4
Alcohol, dioxane or toluene.
10. the method for C-C coupling reaction according to claim 7, it is characterised in that wherein described solvent is first
Alcohol, ethanol or isopropanol.
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| CN112121859A (en) * | 2020-09-25 | 2020-12-25 | 万华化学集团股份有限公司 | Catalyst and preparation method thereof, and preparation method of 1,1,4, 4-tetramethoxy-2-butene |
| CN112892595A (en) * | 2021-01-22 | 2021-06-04 | 邹育英 | Para-nitro-substituted palladium catalyst and application thereof in Heck reaction |
| CN112958161A (en) * | 2021-02-22 | 2021-06-15 | 江南大学 | Palladium catalyst and application thereof in catalyzing aryl ethanol compound deoxidation coupling reaction |
| CN116239784A (en) * | 2023-02-24 | 2023-06-09 | 兰州大学 | Photosensitive MOF and preparation method and application thereof |
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| CN112121859A (en) * | 2020-09-25 | 2020-12-25 | 万华化学集团股份有限公司 | Catalyst and preparation method thereof, and preparation method of 1,1,4, 4-tetramethoxy-2-butene |
| CN112121859B (en) * | 2020-09-25 | 2022-07-12 | 万华化学集团股份有限公司 | Catalyst and preparation method thereof, and preparation method of 1,1,4, 4-tetramethoxy-2-butene |
| CN112892595A (en) * | 2021-01-22 | 2021-06-04 | 邹育英 | Para-nitro-substituted palladium catalyst and application thereof in Heck reaction |
| CN112958161A (en) * | 2021-02-22 | 2021-06-15 | 江南大学 | Palladium catalyst and application thereof in catalyzing aryl ethanol compound deoxidation coupling reaction |
| CN116239784A (en) * | 2023-02-24 | 2023-06-09 | 兰州大学 | Photosensitive MOF and preparation method and application thereof |
| CN116239784B (en) * | 2023-02-24 | 2024-05-03 | 兰州大学 | Photosensitive MOF and preparation method and application thereof |
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