CN112774731A - Para-methoxy substituted palladium catalyst and application thereof in Heck reaction - Google Patents
Para-methoxy substituted palladium catalyst and application thereof in Heck reaction Download PDFInfo
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- CN112774731A CN112774731A CN202110086332.6A CN202110086332A CN112774731A CN 112774731 A CN112774731 A CN 112774731A CN 202110086332 A CN202110086332 A CN 202110086332A CN 112774731 A CN112774731 A CN 112774731A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 44
- 150000002940 palladium Chemical class 0.000 title claims abstract description 33
- 238000007341 Heck reaction Methods 0.000 title claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 14
- 229910000071 diazene Inorganic materials 0.000 claims abstract description 13
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000005594 diketone group Chemical group 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- TWBPWBPGNQWFSJ-UHFFFAOYSA-N 2-phenylaniline Chemical compound NC1=CC=CC=C1C1=CC=CC=C1 TWBPWBPGNQWFSJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract description 4
- 229910002666 PdCl2 Inorganic materials 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 6
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000019502 Orange oil Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010502 orange oil Substances 0.000 description 2
- -1 phosphine compound Chemical class 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- VFJRKWVRBRAQIU-UHFFFAOYSA-L disodium;toluene;carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O.CC1=CC=CC=C1 VFJRKWVRBRAQIU-UHFFFAOYSA-L 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 238000010651 palladium-catalyzed cross coupling reaction Methods 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
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Abstract
The invention discloses a para methoxy substituted palladium catalyst and application thereof in Heck reaction; the p-methoxy substituted palladium catalyst is prepared by reacting aniline and diketone to obtain diimine ligand, and reacting the diimine ligand with PdCl2Carrying out coordination to obtain a para-methoxy substituted palladium catalyst; methoxy is introduced into the para position of the ligand of the para methoxy substituted palladium catalyst, phenyl is introduced into the ortho position, the steric hindrance of the palladium metal catalyst is further increased on the framework, and the catalytic efficiency is higher when the palladium catalyst catalyzes Heck reaction.
Description
Technical Field
The invention belongs to the field of catalytic chemistry, and particularly relates to a para-methoxy substituted palladium catalyst and application thereof in Heck reaction.
Background
The transition metal catalyzed C-C bond coupling reaction is a very effective organic synthesis means by which the formation of C-C bonds at specific positions can be achieved under relatively mild conditions; therefore, the method can be used for synthesizing various natural products, pharmaceutical intermediates and organic materials, and has important significance in academic research and industrial development. And the transition metal palladium catalyzed cross-coupling reaction among them developed particularly rapidly.
Conventionally, Heck reaction using a palladium compound and an organic phosphine compound as a catalyst has been carried out in a relatively large number, but since phosphine ligands are unstable and toxic, their application is limited, and in recent years, sp is used3the-N-bidentate Pd complex is subjected to stability and good catalytic performanceMore and more attention is paid to the method, and based on the method, the para-methoxy substituted palladium catalyst is prepared.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention provides the para-methoxy substituted palladium catalyst, wherein methoxy is introduced into the para position of the ligand of the para-methoxy substituted palladium catalyst, phenyl is introduced into the ortho position, the steric hindrance of the palladium metal catalyst is further increased on the framework, and the catalytic efficiency is higher when the palladium catalyst catalyzes Heck reaction.
The invention aims to provide a para-methoxy substituted palladium catalyst.
Another object of the present invention is to provide a process for producing the above para-methoxy substituted palladium catalyst.
The invention further aims to provide the application of the para-methoxy substituted palladium catalyst in the Heck reaction.
The above purpose of the invention is realized by the following technical scheme:
a p-methoxy substituted palladium catalyst, the structural formula of which is shown as the following formula (I):
a preparation method of a para-methoxy substituted palladium catalyst comprises the following steps:
(1) under the conditions of nitrogen atmosphere and room temperature, sequentially adding 4-methoxy-2, 6-phenylaniline and a solvent into a 100mL bottle with a mouth, then slowly adding trimethylaluminum by using an injector, raising the reaction temperature to 110 ℃, reducing the reaction temperature to room temperature after reacting for 2 hours, then adding diketone, continuing to react for 6 hours at the temperature of 110 ℃, reducing the temperature to 0 ℃, stopping the reaction system by using 5% sodium hydroxide ice water solution, extracting an organic phase by using ethyl acetate, and then using anhydrous MgSO4Drying, evaporating the solvent to dryness under reduced pressure to obtain an orange oil, and recrystallizing or separating with ethanol to obtain an orange diimine ligand.
Further, the diketones have the following structural formula:
furthermore, the molar ratio of the diketone to the 4-methoxy-2, 6-phenylaniline to the trimethylaluminum is 1: 2-2.5.
Further, the solvent used in the reaction is one of toluene, tetrahydrofuran and dioxane.
(2) Adding diimine, palladium chloride and solvent into a bottle with a branch mouth, N2Stirring and reacting for 16h at 60 ℃ under protection, cooling to room temperature, passing through a column, collecting filtrate, recrystallizing dichloromethane/n-hexane, washing the obtained solid with n-hexane, performing suction filtration, and repeatedly washing for three times to obtain the orange-red palladium catalyst.
Further, the structural formula of the diimine ligand is as follows:
further, the solvent is one of methanol, dichloromethane, toluene and tetrahydrofuran.
Further, the molar ratio of the diimine to the palladium chloride is 1-1.5: 1.
The invention also provides application of the para-methoxy substituted palladium catalyst in a Heck reaction.
The Heck reaction can be seen in the following reaction equation:
the p-methoxy substituted palladium catalyst is used as a Heck reaction catalyst, the reaction time is 12-24 h, the reaction temperature is 110-150 ℃, the reaction solvent is any one or more of N, N-dimethyl acetyl, N-dimethyl formamide and toluene, and the alkali used in the reaction is Na2CO3，K2CO3And NaOAc under any one or more conditionsThe intermediate of the stilbene dye is prepared.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the para-methoxy substituted palladium catalyst obtained by the invention has low toxicity when being applied to a Heck reaction for preparing a dye intermediate, and the traditional Heck reaction is generally carried out in PdCl2Or Pd (OAc)2The method is carried out under the action of a homogeneous catalyst, but the palladium catalyst has poor thermal stability in the reaction process, palladium ions are easy to reduce to generate palladium black to inactivate the catalyst, the occurrence of the palladium catalyst of an organophosphorus ligand greatly improves the service life and efficiency of the catalyst, and the organophosphorus ligand is generally sensitive to air, complicated to operate, high in toxicity and not friendly to the environment and high in price, so that the para-methoxy substituted palladium catalyst prepared by the method is applied to the Heck reaction.
Drawings
FIG. 1 is a single crystal structural view of a diimine ligand prepared in the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
The method for calculating the conversion rate of all substrates is used for calculating through gas chromatography tests, and the conversion rate of bromobenzene is obtained through checking the integral area of peaks and then calculating.
Example 1
Under the conditions of nitrogen atmosphere and room temperature, 4-methoxy-2, 6-phenylaniline (12mmol) and 20mL of toluene are sequentially added into a 100mL opening bottle, then 12mL (1.0M and 12mmol) of trimethylaluminum is slowly added by a syringe, the reaction temperature is raised to 110 ℃ for reaction, methane gas is discharged at the moment, after the reaction is carried out for 2 hours, the reaction temperature is reduced to the room temperature, and then diketone (5mmol) is added, at the moment, the reaction system is changed from colorless to deep red, and a large amount of heat is released. Continuing to react for 6h at 110 ℃, then cooling to 0 ℃, stopping the reaction system by using 5% sodium hydroxide ice water solution, and extracting the organic phase by using ethyl acetateTaking, and then using anhydrous MgSO4Drying, evaporating the solvent to dryness under reduced pressure to give an orange oil, and recrystallizing or column-separating with ethanol to give an orange diimine ligand with a yield of 83.6%.
Example 2
The diimine ligand (1mmol), palladium chloride (1.1mmol) and 8mL of methanol were added to a vial, N2Stirring and reacting for 16h at 60 ℃ under protection, cooling to room temperature, carrying out dry-process column chromatography by using dichloromethane as an eluent, collecting filtrate, dissolving the filtrate by using a small amount of dichloromethane after spin-drying, slowly dropwise adding the solution into a n-hexane solution in a stirring state, immediately precipitating a large amount of yellow solid powder, carrying out suction filtration and repeated washing for three times to obtain the orange-red p-methoxy substituted palladium catalyst, wherein the yield is 85.6%.
Example 3
The prepared para-methoxy substituted palladium catalyst catalyzes Heck reaction under different reaction conditions.
Firstly, 4 mu mol of para-methoxy substituted palladium catalyst is dissolved in 5mL of reaction solvent to prepare the palladium catalyst with the concentration of 8 multiplied by 10- 4Adding 2.0mmol of bromobenzene, 2.4mmol of styrene, 2.2mmol of alkali and 4mL of reaction solvent into a dry Schlenk tube with 50mL in sequence under the protection of nitrogen, finally taking out 50 μ L of solution from the prepared palladium catalyst solution with the substitution of the para-methoxy group by using a clean injector (with the range of 50 μ L), injecting the solution into the Schlenk tube, sealing, placing the reaction solution into methyl silicone oil, stirring the reaction solution at the reaction temperature of 150 ℃, taking out 25 μ L of solution from the reaction solution by using a clean injector (with the range of 50 μ L) after the reaction time is stopped, diluting the taken-out reaction solution by using the reaction solvent by 3-4 times, injecting 1-2 μ L of diluent into a gas chromatography, and calculating the conversion rate of the bromobenzene by checking the integral area. Simultaneously, cooling the reaction solution to room temperature, extracting with ethyl acetate (3 × 40mL) and deionized water (50mL) for three times after cooling to room temperature, taking an organic phase, washing with saturated saline solution for three times, drying with anhydrous magnesium sulfate to remove a small amount of water remained in the organic phase, filtering to remove magnesium sulfate, performing rotary evaporation concentration, separating by silica gel column chromatography, removing the solvent by rotary evaporation, and performing vacuum distillationThe dried product was dried in an air drying oven for 24 hours to obtain a pure white flaky solid (1, 2-stilbene).
TABLE 1 results of Heck reaction catalyzed by para-methoxy substituted palladium catalyst
| Serial number | Alkali | Solvent(s) | Temperature (. degree.C.) | Time (h) | Conversion (%) |
| 1 | Na2CO3 | DMA | 130 | 12 | 31 |
| 2 | Na2CO3 | DMA | 150 | 12 | 93 |
| 3 | Na2CO3 | DMA | 150 | 24 | 97 |
| 4 | NaOAc | DMA | 150 | 12 | 81 |
| 5 | K2CO3 | DMA | 150 | 12 | 43 |
| 6 | Na2CO3 | DMF | 150 | 12 | 65 |
| 7 | Na2CO3 | Toluene | 110 | 12 | trance |
From the data in table 1, we can see that the para-methoxy substituted palladium catalyst prepared by the invention can efficiently catalyze Heck to prepare the dye intermediate 1, 2-stilbene.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A para-methoxy substituted palladium catalyst, wherein the para-methoxy substituted palladium catalyst has the structure of formula (I):
2. the method for preparing a p-methoxy substituted palladium catalyst as claimed in claim 1, comprising the steps of:
(1) under the conditions of nitrogen atmosphere and room temperature, sequentially adding 4-methoxy-2, 6-phenylaniline and a solvent into a 100mL bottle with a mouth, then slowly adding trimethylaluminum by using an injector, raising the reaction temperature to 110 ℃, reducing the reaction temperature to room temperature after reacting for 2 hours, then adding diketone, continuing to react for 6 hours at the temperature of 110 ℃, reducing the temperature to 0 ℃, stopping the reaction system by using 5% sodium hydroxide ice water solution, extracting an organic phase by using ethyl acetate, and then using anhydrous MgSO4Drying, evaporating the solvent to dryness under reduced pressure to obtain orange oily substance, and recrystallizing with ethanol or separating with column chromatography to obtain orange diimine ligand;
(2) adding diimine, palladium chloride and solvent into a bottle with a branch mouth, N2Stirring and reacting for 16h at 60 ℃ under protection, cooling to room temperature, passing through a column, collecting filtrate, recrystallizing dichloromethane/n-hexane, washing the obtained solid with n-hexane, performing suction filtration, and repeatedly washing for three times to obtain the orange-red palladium catalyst.
3. The method for preparing a p-methoxy-substituted palladium catalyst as claimed in claim 2, wherein the molar ratio of the diketone to the 4-methoxy-2, 6-phenylaniline to the trimethylaluminum in step (1) is 1:2 to 2.5.
4. The method for preparing a p-methoxy substituted palladium catalyst as claimed in claim 2, wherein the diketone has the following structural formula in step (1):
5. the method for preparing a p-methoxy substituted palladium catalyst as claimed in claim 2, wherein the solvent used in the reaction in step (1) is one of toluene, tetrahydrofuran and dioxane.
6. The method of claim 2, wherein in step (1), the diimine ligand has the formula:
7. the method for preparing a p-methoxy substituted palladium catalyst as claimed in claim 2, wherein the solvent in step (2) is one of methanol, dichloromethane, toluene and tetrahydrofuran.
8. The method for preparing a p-methoxy substituted palladium catalyst as claimed in claim 2, wherein the molar ratio of diimine to palladium chloride in step (2) is 1 to 1.5: 1.
9. The application of the para-methoxy substituted palladium catalyst in the Heck reaction according to claim 1, wherein the reaction time is 12-24 h, the reaction temperature is 110-150 ℃, and the reaction solventIs one or more of N, N-dimethyl acetyl, N-dimethyl formamide and toluene, and the alkali used in the reaction is Na2CO3，K2CO3And NaOAc.
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