CN109529937B - Preparation method of trifluoroethyl-coordinated nickel-based procatalyst - Google Patents

Preparation method of trifluoroethyl-coordinated nickel-based procatalyst Download PDF

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CN109529937B
CN109529937B CN201811532080.XA CN201811532080A CN109529937B CN 109529937 B CN109529937 B CN 109529937B CN 201811532080 A CN201811532080 A CN 201811532080A CN 109529937 B CN109529937 B CN 109529937B
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trifluoroethyl
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杨义
蔡俊杰
罗根
童霞
冯健
杨桃
董宇婷
欧青滕
舒雨玫
周雪梅
李静宇
袁香
郑玉彬
陆文杰
赵延川
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Sichuan University of Science and Engineering
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    • 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
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
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    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
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    • 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
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Abstract

The invention belongs to the technical field of organic metal catalyst preparation, and particularly relates to a preparation method of a trifluoroethyl-coordinated nickel-based procatalyst. The method comprises the following steps: under the atmosphere of reaction solution and nitrogen, taking 2, 2' -bipyridyl ligand, a zero-valent nickel catalyst and trifluoroiodoethane as raw materials, stirring at room temperature until the reaction end point is reached, and then performing separation and purification steps such as draining, filtering and washing to obtain the trifluoroethyl-coordinated nickel-based procatalyst. The method has the advantages of mild catalyst preparation conditions, simple and easy-to-operate steps, easy-to-amplify preparation scale, and general applicability to catalysis of arylboronic acid and sp3Suzuki-type coupling reactions of hybrid halogenated hydrocarbons.

Description

Preparation method of trifluoroethyl-coordinated nickel-based procatalyst
Technical Field
The invention belongs to the technical field of organic metal catalyst preparation, and particularly relates to a preparation method of a trifluoroethyl-coordinated nickel-based procatalyst.
Technical Field
Since the generation of catalytic concepts, transition metal complex catalysts have made great progress in industrial applications, especially in the production of organic synthesis fields such as some chemical products, fine chemicals and high molecular materials. In these fields, the construction of carbon-carbon bonds using transition metal catalysts to catalyze the reaction is a powerful approach. However, the conventional inorganic salt type transition metal catalyst, such as nickel fluoride, has the disadvantages of poor solubility in organic solvents and the like, which are not favorable for the catalytic reaction. Some transition metal complex catalysts, such as bis- (1, 5-cyclooctadiene) nickel, are sensitive to air and moisture, are easy to oxidize and difficult to store, and are not suitable for industrial production. Meanwhile, the development of novel catalysts and novel preparation technologies plays a vital role in environmental protection and optimal utilization of energy resources. Therefore, the method for simply, conveniently and quickly preparing the high-efficiency catalyst has great practical significance.
At present, most transition metal complex procatalysts on the market are noble metal palladium complexes, while nickel-based complex procatalysts are not common, and more rarely and less fluoro-alkyl-coordinated nickel-based procatalysts. The existing preparation method has the defects that the preparation efficiency is reduced due to the need of step-by-step preparation, the Grignard reagent needs to be used at low temperature and the like, and the process is relatively complex and is not beneficial to large-scale production. The specific preparation route is as follows:
(1)
Figure BDA0001905925410000021
(2)
Figure BDA0001905925410000022
in conclusion, the existing synthetic routes have certain defects, and a preparation route meeting the industrial production needs is urgently needed to be searched, and the application of the fluoroalkyl-coordinated nickel-based procatalyst in the catalytic coupling reaction is explored.
Disclosure of Invention
The invention aims to overcome the defects and provide a preparation method of the trifluoroethyl-coordinated nickel-based procatalyst, which has the advantages of low cost, simple and convenient process, easy operation and safe production.
In order to achieve the above object, the technical solution of the present application is:
a method for preparing a trifluoroethyl-complexed nickel-based procatalyst comprising the steps of:
under the atmosphere of reaction solution and nitrogen, 2' -bipyridyl ligand, zero-valent nickel catalyst and trifluoroiodoethane are used as raw materials, and after the raw materials are stirred at room temperature and reach the reaction end point, the trifluoroethyl-coordinated nickel-based procatalyst is obtained through the steps of pumping, filtering, washing and other separation and purification steps.
The preparation method comprises the following steps:
1) adding 2, 2' -bipyridine ligand, a zero-valent nickel catalyst and a reaction solvent into a round-bottom flask in a nitrogen atmosphere, and stirring at room temperature for 12 hours to obtain a reaction solution I;
2) adding trifluoroiodoethane into a reaction solvent, and uniformly mixing;
3) adding the mixed solution obtained in the step 2) into the reaction solution I in the step 1), and stirring at room temperature for 12 hours to obtain a reaction solution II;
4) separating and purifying the reaction liquid II in the step 3) to obtain the trifluoroethyl coordination nickel-based procatalyst.
Preferably, the ratio of the amount of the zero-valent nickel catalyst to the amount of the 2, 2' -bipyridine ligand species is 1:1 to 1.5; the quantity ratio of the zero-valent nickel catalyst to the trifluoroiodoethane substance is 1: 1-2.0; the volume ratio of the zero-valent nickel catalyst to the reaction solvent is 1:1-20 mol.L < -1 >.
Preferably, the zero-valent nickel catalyst is one of bis- (1, 5-cyclooctadiene) nickel, bis (triphenylphosphine) dicarbonyl nickel and tetrakis (triphenylphosphine) nickel; more preferred is bis- (1, 5-cyclooctadiene) nickel.
Preferably, the reaction solvent is any one of tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide; still more preferred is tetrahydrofuran.
Preferably, the reaction temperature is controlled to be 20-40 ℃, and the reaction time is 12-24 h.
Preferably, the separation and purification steps are as follows: and after 24 hours of reaction, draining the reaction solvent, extracting the residual solid matters for multiple times by using an organic extraction solvent benzene or toluene until the extracting solution is colorless, collecting the extracting solution, removing the organic extraction solvent, washing the residual solid with an organic washing solvent, and drying in vacuum to obtain the trifluoroethyl coordination nickel-based procatalyst.
The organic washing solvent is any one of diethyl ether, n-pentane and n-hexane.
Compared with the prior art, the invention has the following advantages:
compared with the existing procatalyst, the trifluoroethyl-coordinated nickel-based procatalyst prepared by the invention has more stable property and is insensitive to air and moisture.
The invention uses cheap and easily obtained 2, 2' -bipyridyl ligand, trifluoroiodoethane and commercially available bis- (1, 5-cyclooctadiene) nickel as raw materials, and the raw materials are stirred in tetrahydrofuran to react to generate the trifluoroethyl coordination nickel-based procatalyst.
And (III) the preparation method belongs to a one-pot method, and does not need to be carried out step by step like the traditional method for preparing the procatalyst. The preparation condition is mild, heating or low-temperature operation is not needed, the extraction and separation process is simple and convenient, the reaction scale is easy to expand, acid-base waste liquid and waste gas are not generated, and the method is favorable for industrial production.
(IV) the trifluoroethyl coordinated nickel-based procatalyst prepared by the method can effectively catalyze arylboronic acid and sp3Suzuki-type coupling reaction of hybridized halogenated hydrocarbon to obtain satisfactory yield.
Drawings
FIG. 1 is a compound trifluoroethyl-coordinated nickel-based procatalyst (bipy) Ni (CH)2CF3)2X-ray diffraction crystal structure diagram of (1);
FIG. 2 is a compound trifluoroethyl-coordinated nickel-based procatalyst (bipy) Ni (CH)2CF3)2The nuclear magnetic resonance hydrogen spectrum of (a);
FIG. 3 is a compound trifluoroethyl-coordinated nickel-based procatalyst (bipy) Ni (CH)2CF3)2Nuclear magnetic resonance carbon spectrum of (a);
FIG. 4 is a compound trifluoroethyl-coordinated nickel-based procatalyst (bipy) Ni (CH)2CF3)2Nuclear magnetic resonance fluorine spectrum of (a).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples. It should be understood that the specific examples described herein are intended to be illustrative only and are not intended to be limiting.
The preparation method of a trifluoroethyl-coordinated nickel-based procatalyst according to the present invention is described in detail below with reference to specific principles and preparation procedures.
The reaction equation for preparing the trifluoroethyl-coordinated nickel-based procatalyst of the present invention is as follows:
Figure BDA0001905925410000041
the preparation method of the trifluoroethyl-coordinated nickel-based procatalyst comprises the steps of stirring bipyridine ligands, zero-valent nickel catalysts and trifluoroiodoethane serving as raw materials in tetrahydrofuran at room temperature for 24 hours in a nitrogen atmosphere, and then performing separation and purification steps such as draining, filtering, washing and the like to obtain the trifluoroethyl-coordinated nickel-based procatalyst.
In the preparation method, nitrogen is inert gas, does not react with a reaction substrate and a catalyst, and can effectively prevent the oxidation and inactivation of transition metal species under the protection of the inert gas. The reaction solvent has the functions of providing a favorable reaction environment and performing dilution and dispersion functions to avoid side reactions caused by overhigh local concentration.
The preparation method and practical application of the trifluoroethyl-coordinated nickel-based procatalyst of the present invention are specifically described below with reference to specific examples.
Example 1: preparation of nickel-based procatalyst with trifluoroethyl coordination compound
This example prepared the chemical reaction formula for the compound trifluoroethyl-coordinated nickel-based procatalyst as follows:
Figure BDA0001905925410000051
the preparation process comprises the following steps:
to a round-bottom flask, 2' -bipyridine (abbreviated as bipy, 3.1236g, 20.0mmol), bis (triphenylphosphine) nickel dicarbonyl (12.7856g, 20.0mmol), and tetrahydrofuran (40mL) as a solvent were added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 12 hours. A solution of trifluoroiodoethane (4.1998g, 20.0mmol) in tetrahydrofuran (10mL) was then added to the reaction system, and the reaction was stirred at room temperature for 12 hours. The reaction was stopped, after removing the solvent tetrahydrofuran using an oil pump, 20mL of benzene was added to the flask, filtered through a sand-core funnel, and the trifluoroethyl-coordinated nickel-based procatalyst was extracted from the remaining solid with benzene (20mL x 3), the extract was collected, and the solvent benzene was recovered using oil pump-cold hydrazine-liquid nitrogen. Finally, the trifluoroethyl-coordinated nickel-based procatalyst was washed with n-pentane (10mL x 3) and dried under vacuum to give 0.99g of product in 13% yield.
The structural data for the product prepared in this example are characterized as follows:
1H NMR(500MHz,THF-d8):δ8.69(d,J＝7.8Hz,2H),8.23(d,J＝7.8Hz,2H),8.09(dt,J＝7.8Hz,1.3Hz,2H),7.59(m,2H),1.06(q,J＝16.2Hz,4H)；19F NMR(470MHz,CDCl3):δ-47.98(t,J＝16.2Hz,6F)；13C NMR(125MHz,CDCl3):δ156.22,150.56,139.39,135.38(q,J＝273.8Hz),127.16,122.24,6.11(q,J＝23.6Hz).
example 2: preparation of nickel-based procatalyst with trifluoroethyl coordination compound
This example prepared the chemical reaction formula for the compound trifluoroethyl-coordinated nickel-based procatalyst as follows:
Figure BDA0001905925410000061
the preparation process comprises the following steps:
2, 2' -bipyridine (3.1236g, 20.0mmol), bis- (1, 5-cyclooctadiene) nickel (5.5012g, 20.0mmol), and solvent dioxane (40mL) were added to a round-bottom flask under a nitrogen atmosphere, and stirred at room temperature for 12 hours. A solution of trifluoroiodoethane (4.1998g, 20.0mmol) in dioxane (10mL) was then added to the reaction system, and the reaction was stirred at room temperature for 12 hours. The reaction was stopped, the solvent dioxane was removed using an oil pump, 20mL of solvent benzene was added to the bottle, filtered through a sand-core funnel, and the trifluoroethyl-coordinated nickel-based procatalyst was extracted from the remaining solid with solvent benzene (20mL x 3), the extract was collected, and the solvent benzene was recovered using an oil pump-cold hydrazine-liquid nitrogen. Finally, the trifluoroethyl-coordinated nickel-based procatalyst was washed with n-pentane (10mL x 3) and dried under vacuum to give 3.05g of product in 40% yield.
Example 3: preparation of nickel-based procatalyst with trifluoroethyl coordination compound
This example prepared the chemical reaction formula for the compound trifluoroethyl-coordinated nickel-based procatalyst as follows:
Figure BDA0001905925410000062
the preparation process comprises the following steps:
to a round-bottomed flask were added 2, 2' -bipyridine (3.1236g, 20.0mmol), bis- (1, 5-cyclooctadiene) nickel (5.5012g, 20.0mmol), and a solvent ethylene glycol dimethyl ether (abbreviated as: DME, 40mL) under a nitrogen atmosphere, and the mixture was stirred at room temperature for 12 hours. Then, a solution of trifluoroiodoethane (4.1998g, 20.0mmol) in ethylene glycol dimethyl ether (10mL) was added to the reaction system, and the reaction was stirred at room temperature for 12 hours. The reaction was stopped, the solvent ethylene glycol dimethyl ether was removed using an oil pump, 20mL of benzene solvent was added to the bottle, filtered through a sand-core funnel, the trifluoroethyl-coordinated nickel-based procatalyst was extracted from the remaining solid with benzene solvent (20mL x 3), the extract was collected, and the solvent benzene was recovered using oil pump-cold hydrazine-liquid nitrogen. Finally, the trifluoroethyl-coordinated nickel-based procatalyst was washed with n-pentane (10mL x 3) and dried under vacuum to give 3.12g of product in 41% yield.
Example 4: preparation of nickel-based procatalyst with trifluoroethyl coordination compound
This example prepared the chemical reaction formula for the compound trifluoroethyl-coordinated nickel-based procatalyst as follows:
Figure BDA0001905925410000071
the preparation process comprises the following steps:
2, 2' -bipyridine (3.1236g, 20.0mmol), bis- (1, 5-cyclooctadiene) nickel (5.5012g, 20.0mmol), and dimethyl sulfoxide (abbreviated as DMSO, 40mL) were added to a round-bottom flask under a nitrogen atmosphere, and stirred at room temperature for 12 hours. Then, iodotrifluoroethane (4.1998g, 20.0mmol) in dimethylsulfoxide (10mL) was added to the reaction system, and the reaction was stirred at room temperature for 12 hours. The reaction was stopped, the solvent dimethyl sulfoxide was removed using an oil pump, 20mL of benzene solvent was added to the bottle, filtered through a sand-core funnel, and the trifluoroethyl-coordinated nickel-based procatalyst was extracted from the remaining solid with benzene solvent (20mL x 3), the extract was collected, and the solvent benzene was recovered using oil pump-cold hydrazine-liquid nitrogen. Finally, the trifluoroethyl complex nickel-based procatalyst was washed with n-pentane (10mL x 3) and dried under vacuum to give 0.38g of product in 5% yield.
Example 5: preparation of nickel-based procatalyst with trifluoroethyl coordination compound
This example prepared the chemical reaction formula for the compound trifluoroethyl-coordinated nickel-based procatalyst as follows:
Figure BDA0001905925410000072
the preparation process comprises the following steps:
2, 2' -bipyridine (3.1236g, 20.0mmol), bis- (1, 5-cyclooctadiene) nickel (5.5012g, 20.0mmol) and solvent N, N-dimethylformamide (40mL) were added to a round-bottom flask under a nitrogen atmosphere, and stirred at room temperature for 12 hours. Then, trifluoroiodoethane (4.1998g, 20.0mmol) and N, N-dimethylformamide (10mL) were added to the reaction system, and the reaction was stirred at room temperature for 12 hours. The reaction was stopped, the solvent N, N-dimethylformamide was removed using an oil pump, 20mL of benzene solvent was added to the flask, filtered through a sand-core funnel, and the trifluoroethyl-coordinated nickel-based procatalyst was extracted from the remaining solid with benzene solvent (20mL x 3), the extract was collected, and the benzene solvent was recovered using oil pump-cold hydrazine-liquid nitrogen. Finally, the trifluoroethyl-coordinated nickel-based procatalyst was washed with n-pentane (10mL x 3) and dried under vacuum to give 1.14g of product in 15% yield.
Example 6: preparation of nickel-based procatalyst with trifluoroethyl coordination compound
This example prepared the chemical reaction formula for the compound trifluoroethyl-coordinated nickel-based procatalyst as follows:
Figure BDA0001905925410000081
the preparation process comprises the following steps:
2, 2' -bipyridine (3.1236g, 20.0mmol), bis- (1, 5-cyclooctadiene) nickel (5.5012g, 20.0mmol), and tetrahydrofuran (40mL) as a solvent were added to a round-bottom flask under a nitrogen atmosphere, and the mixture was stirred at room temperature for 12 hours. Trifluoroiodoethane (4.1998g, 20.0mmol) in tetrahydrofuran (10mL) was then added to the reaction system, and the reaction was stirred at room temperature for 12 hours. The reaction was stopped, the solvent tetrahydrofuran was removed using an oil pump, 20mL of benzene was added to the flask, filtered through a sand-core funnel, and the trifluoroethyl-coordinated nickel-based procatalyst was extracted from the remaining solids with benzene (20mL x 3), the extract collected, and the solvent benzene was recovered using an oil pump-cold hydrazine-liquid nitrogen. Finally, the trifluoroethyl complex nickel-based procatalyst was washed with n-pentane (10mL x 3) and dried under vacuum to give 3.66g with 48% yield.
Example 7: preparation of nickel-based procatalyst with trifluoroethyl coordination compound
This example prepared the chemical reaction formula for the compound trifluoroethyl-coordinated nickel-based procatalyst as follows:
Figure BDA0001905925410000082
the preparation process comprises the following steps:
2, 2' -bipyridine (3.1236g, 20.0mmol), bis- (1, 5-cyclooctadiene) nickel (5.5012g, 20.0mmol) and tetrahydrofuran (40mL) as a solvent were added to a round-bottom flask under a nitrogen atmosphere, and the mixture was stirred at 60 ℃ for 12 hours. Trifluoroiodoethane (4.1998g, 20.0mmol) in tetrahydrofuran (10mL) was then added to the reaction system, and the reaction was stirred at 60 ℃ for 12 hours. After the reaction solution was cooled, the solvent tetrahydrofuran was removed using an oil pump, 20mL of benzene solvent was added to the flask, filtered through a sand-core funnel, and the trifluoroethyl-coordinated nickel-based procatalyst was extracted from the remaining solid with benzene solvent (20mL x 3), and the extract was collected, and the benzene solvent was recovered using oil pump-cold hydrazine-liquid nitrogen. Finally, the trifluoroethyl complex nickel-based procatalyst was washed with n-pentane (10mL x 3) and dried under vacuum to give 1.68g of product in 22% yield.
Example 8: preparation of nickel-based procatalyst with trifluoroethyl coordination compound
This example prepared the chemical reaction formula for the compound trifluoroethyl-coordinated nickel-based procatalyst as follows:
Figure BDA0001905925410000091
the preparation process comprises the following steps:
2, 2' -bipyridine (4.6854g, 30.0mmol), bis- (1, 5-cyclooctadiene) nickel (5.5012g, 20.0mmol), and tetrahydrofuran (50mL) as a solvent were added to a round-bottom flask under a nitrogen atmosphere, and the mixture was stirred at room temperature for 12 hours. Trifluoroiodoethane (5.0386g, 24.0mmol) in tetrahydrofuran (10mL) was then added to the reaction system, and the reaction was stirred at room temperature for 12 hours. The reaction was stopped, the solvent tetrahydrofuran was removed using an oil pump, 20mL of benzene was added to the flask, filtered through a sand-core funnel, and the trifluoroethyl-coordinated nickel-based procatalyst was extracted from the remaining solids with benzene (20mL x 3), the extract collected, and the solvent benzene was recovered using an oil pump-cold hydrazine-liquid nitrogen. Finally, the trifluoroethyl complex nickel-based procatalyst was washed with n-pentane (10mL x 3) and dried under vacuum to give 3.43g of product in 45% yield.
Example 9: preparation of nickel-based procatalyst with trifluoroethyl coordination compound
This example prepared the chemical reaction formula for the compound trifluoroethyl-coordinated nickel-based procatalyst as follows:
Figure BDA0001905925410000092
the preparation process comprises the following steps:
2, 2' -bipyridine (6.2472g, 40.0mmol), bis- (1, 5-cyclooctadiene) nickel (5.5012g, 20.0mmol), and tetrahydrofuran (60mL) as a solvent were added to a round-bottom flask under a nitrogen atmosphere, and the mixture was stirred at room temperature for 12 hours. Trifluoroiodoethane (6.2982g, 30.0mmol) in tetrahydrofuran (10mL) was then added to the reaction system, and the reaction was stirred at room temperature for 12 hours. The reaction was stopped, the solvent tetrahydrofuran was removed using an oil pump, 20mL of benzene was added to the flask, filtered through a sand-core funnel, and the trifluoroethyl-coordinated nickel-based procatalyst was extracted from the remaining solids with benzene (20mL x 3), the extract collected, and the solvent benzene was recovered using an oil pump-cold hydrazine-liquid nitrogen. Finally, the trifluoroethyl-coordinated nickel-based procatalyst was washed with n-pentane (10mL x 3) and dried under vacuum to give 3.05g of product in 40% yield.
Example 10: preparation of nickel-based procatalyst with trifluoroethyl coordination compound
This example prepared the chemical reaction formula for the compound trifluoroethyl-coordinated nickel-based procatalyst as follows:
Figure BDA0001905925410000101
the preparation process comprises the following steps:
2, 2' -bipyridine (3.1236g, 20.0mmol), bis- (1, 5-cyclooctadiene) nickel (5.5012g, 20.0mmol), and tetrahydrofuran (40mL) as a solvent were added to a round-bottom flask under a nitrogen atmosphere, and the mixture was stirred at room temperature for 12 hours. Trifluoroiodoethane (8.3976g, 40.0mmol) in tetrahydrofuran (20mL) was then added to the reaction system, and the reaction was stirred at room temperature for 12 hours. The reaction was stopped, the solvent tetrahydrofuran was removed using an oil pump, 20mL of benzene was added to the flask, filtered through a sand-core funnel, and the trifluoroethyl-coordinated nickel-based procatalyst was extracted from the remaining solids with benzene (20mL x 3), the extract collected, and the solvent benzene was recovered using an oil pump-cold hydrazine-liquid nitrogen. Finally, the trifluoroethyl complex nickel-based procatalyst was washed with n-pentane (10mL x 3) and dried under vacuum to give 2.74g of product in 36% yield.
Example 11: application of nickel-based procatalyst coordinated by compound trifluoroethyl in coupling reaction
The chemical reaction formula for this exemplary trifluoroethyl-coordinated nickel-based procatalyst in the coupling reaction is as follows:
Figure BDA0001905925410000111
the preparation process comprises the following steps:
adding 4-biphenylboronic acid (2.9705g, 15mmol) and potassium phosphate (6.3681g, 30mmol) into a sealed tube under a nitrogen atmosphere, then adding a glycol dimethyl ether solution (10mL) of trifluoroiodoethane (2.0994g, 10mmol), finally adding a glycol dimethyl ether solution (5mL) of a nickel-based procatalyst (190.47mg, 0.5mmol) coordinated with trifluoroethyl, stirring and reacting in an oil bath at 80 ℃ for 24 hours after sealing, cooling the reaction liquid to room temperature, monitoring the reaction end point by using GC-MS, then filtering insoluble substances in the reaction liquid by using a diatomite sand core funnel, washing with a small amount of diethyl ether, and collecting filtrate. To the filtrate was added 20mL of water, the aqueous phase was extracted three times (20mL x 3) with ether, the organic phases were combined, the organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, the solvent was recovered by rotary evaporation, and the residue was separated by silica gel column chromatography to give 2.1498g of the product in 91% yield.
The product structure data obtained in this example are characterized as follows:
1H NMR(600MHz,CDCl3)δ7.58(d,J＝7.7Hz,4H),7.44(t,J＝7.6Hz,2H),7.35(t,J＝8.5Hz,3H),3.40(q,J＝10.8Hz,2H)；19F NMR(470MHz,CDCl3)δ-65.85(t,J＝10.8Hz,3F)；13C NMR(151MHz,CDCl3)δ141.12(s),140.53(s),130.60(s),129.14(q,J＝2.9Hz),128.86(s),127.54(s),127.44(s),127.14(s),125.84(q,J＝276.8Hz),39.92(q,J＝29.8Hz).
example 12: application of nickel-based procatalyst coordinated by compound trifluoroethyl in coupling reaction
The chemical reaction formula for this exemplary trifluoroethyl-coordinated nickel-based procatalyst in the coupling reaction is as follows:
Figure BDA0001905925410000112
the preparation process comprises the following steps:
under nitrogen atmosphere, 4-tert-butyl boric acid (2.6706g, 15mmol) and potassium phosphate (6.3681g, 30mmol) are added into a sealed tube, then ethylene glycol dimethyl ether solution (10mL) of trifluoroiodoethane (2.0994g, 10mmol) is added, finally ethylene glycol dimethyl ether solution (5mL) of trifluoroethyl-coordinated nickel-based procatalyst (190.47mg, 0.5mmol) is added, after sealing, the reaction is stirred in an oil bath at 80 ℃ for 24 hours, the reaction solution is cooled to room temperature, the reaction endpoint is monitored by GC-MS, insoluble substances in the reaction solution are filtered by a diatomite sand core funnel, a small amount of ether is washed, and the filtrate is collected. To the filtrate was added 20mL of water, the aqueous phase was extracted three times (20mL x 3) with ether, the organic phases were combined, the organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, the solvent was recovered by rotary evaporation, and the residue was separated by silica gel column chromatography to give 1.7084g of the product in 79% yield.
The product structure data obtained in this example are characterized as follows:
1HNMR(500MHz,CDCl3):δ7.38(d,J＝8.4Hz,2H),7.23(d,J＝8.1Hz,2H),3.33(q,J＝10.9Hz,2H),1.33(s,9H)；19F NMR(470MHz,CDCl3):δ-65.97(t,J＝10.9Hz,3F)；13C NMR(125MHz,CDCl3):δ151.27,130.06,127.35(q,J＝2.7Hz),126.14(q,J＝276.6Hz),125.83,39.93(q,J＝29.6Hz),34.75,31.50.
example 13: application of nickel-based procatalyst coordinated by compound trifluoroethyl in coupling reaction
The chemical reaction formula for this exemplary trifluoroethyl-coordinated nickel-based procatalyst in the coupling reaction is as follows:
Figure BDA0001905925410000121
the preparation process comprises the following steps:
under nitrogen atmosphere, 4-methoxycarbonylphenylboronic acid (2.700g, 15mmol) and potassium phosphate (6.3681g, 30mmol) are added into a sealed tube, then ethylene glycol dimethyl ether solution (10mL) of ethyl bromoacetate (1.6700g, 10mmol) is added, finally ethylene glycol dimethyl ether solution (5mL) of trifluoroethyl-coordinated nickel-based procatalyst (190.47mg, 0.5mmol) is added, after sealing, the reaction is stirred in an oil bath at 80 ℃ for 24 hours, the reaction solution is cooled to room temperature, the reaction endpoint is monitored by GC-MS, insoluble substances in the reaction solution are filtered by a diatomite sand core funnel, a small amount of ethyl ether is washed, and the filtrate is collected. To the filtrate was added 20mL of water, the aqueous phase was extracted three times (20mL x 3) with ether, the organic phases were combined, the organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, the solvent was recovered by rotary evaporation, and the residue was separated by silica gel column chromatography to give 1.600g of the product in 72% yield.
The product structure data obtained in this example are characterized as follows:
1H NMR(600MHz,CDCl3)δ8.00(d,J＝8.3Hz,2H),7.36(d,J＝8.2Hz,2H),4.16(q,J＝7.1Hz,2H),3.91(s,3H),3.67(s,2H),1.25(t,J＝7.1Hz,3H).13C NMR(151MHz,CDCl3)δ170.86,166.8,139.29,129.85,129.35,129.01,61.10,52.10,41.38,14.15.
example 14: application of nickel-based procatalyst coordinated by compound trifluoroethyl in coupling reaction
The chemical reaction formula for this exemplary trifluoroethyl-coordinated nickel-based procatalyst in the coupling reaction is as follows:
Figure BDA0001905925410000131
the preparation process comprises the following steps:
under nitrogen atmosphere, 4-methoxycarbonylphenylboronic acid (2.700g, 15mmol) and potassium phosphate (6.3681g, 30mmol) are added into a sealed tube, then an ethylene glycol dimethyl ether solution (10mL) of allyl bromide (1.2098g, 10mmol) is added, finally an ethylene glycol dimethyl ether solution (5mL) of a trifluoroethyl-coordinated nickel-based procatalyst (190.47mg, 0.5mmol) is added, after sealing, the mixture is stirred and reacted in an oil bath at 80 ℃ for 24 hours, the reaction solution is cooled to room temperature, the reaction endpoint is monitored by GC-MS, insoluble substances in the reaction solution are filtered by a diatomite sand core funnel, a small amount of ethyl ether is washed, and the filtrate is collected. To the filtrate was added 20mL of water, the aqueous phase was extracted three times (20mL x 3) with ether, the organic phases were combined, the organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, the solvent was recovered by rotary evaporation, and the residue was separated by silica gel column chromatography to give 1.2512g of the product in 71% yield.
The product structure data obtained in this example are characterized as follows:
1H NMR(600MHz,CDCl3)δ7.97(d,J＝8.2Hz,2H),7.26(d,J＝8.0Hz,2H),5.95(ddt,J＝16.9,10.2,6.7Hz,1H),5.13–5.06(m,2H),3.90(s,3H),3.44(d,J＝6.7Hz,2H).13C NMR(151MHz,CDCl3)δ167.12,145.51,136.41,129.78,128.63,128.10,116.60,52.01,40.16.
example 15: application of nickel-based procatalyst coordinated by compound trifluoroethyl in coupling reaction
The chemical reaction formula for this exemplary trifluoroethyl-coordinated nickel-based procatalyst in the coupling reaction is as follows:
Figure BDA0001905925410000141
the preparation process comprises the following steps:
4-tert-butylboronic acid (2.6706g, 15mmol) and potassium phosphate (6.3681g, 30mmol) were added to a sealed tube under nitrogen, followed by the addition of a solution of 3-iodooxetane (1.8398g, 10mmol) in ethylene glycol dimethyl ether (10mL), and finally the addition of a solution of trifluoroethyl-coordinated nickel-based procatalyst (190.47mg, 0.5mmol) in ethylene glycol dimethyl ether (5mL), followed by sealing and stirring in an oil bath at 80 ℃ for reaction for 24 hours, the reaction solution was cooled to room temperature, the end of the reaction was monitored by GC-MS, and then the insoluble matter in the reaction solution was filtered off with a celite core funnel, rinsed with a small amount of diethyl ether, and the filtrate was collected. To the filtrate was added 20mL of water, the aqueous phase was extracted three times (20mL x 3) with ether, the organic phases were combined, the organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, the solvent was recovered by rotary evaporation, and the residue was separated by silica gel column chromatography to give 1.5413g of the product in 81% yield.
The product structure data obtained in this example are characterized as follows:
1H NMR(600MHz,CDCl3)δ7.59(d,J＝7.0Hz,2H),7.57(d,J＝7.0Hz,2H),7.50–7.41(m,4H),7.35(t,J＝7.4Hz,1H),5.10(dd,J＝8.4,6.1Hz,2H),4.81(t,J＝6.4Hz,2H),4.31–4.22(m,1H)；13C NMR(151MHz,CDCl3)δ140.76,140.61,140.07,128.83,127.50,127.34,127.28,127.06,78.92,40.09.
the above description is only exemplary of the present invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (5)

1. A preparation method of a trifluoroethyl-coordinated nickel-based procatalyst is characterized by comprising the following steps: under the atmosphere of reaction solution and nitrogen, taking 2, 2' -bipyridyl ligand, zero-valent nickel catalyst and trifluoroiodoethane as raw materials, stirring at room temperature until the reaction end point is reached, and separating and purifying to obtain a trifluoroethyl coordination nickel-based procatalyst; the quantity ratio of the zero-valent nickel catalyst to the 2, 2' -bipyridyl ligand substance is 1: 1-2.0; the quantity ratio of the zero-valent nickel catalyst to the trifluoroiodoethane substance is 1: 1-4.0; the volume ratio of the zero-valent nickel catalyst to the reaction solvent is 1:1-20 mol.L-1(ii) a The zero-valent nickel catalyst is any one of bis- (1, 5-cyclooctadiene) nickel and bis (triphenylphosphine) dicarbonyl nickel; the reaction solvent is any one of tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
2. A process for preparing a trifluoroethyl complex nickel-based procatalyst as set forth in claim 1 wherein: the reaction temperature is 20-40 ℃, and the reaction time is 12-24 h.
3. The method for preparing the trifluoroethyl-coordinated nickel-based procatalyst according to claim 1, wherein the steps of separating and purifying are as follows: and after the reaction, pumping out the reaction solvent, extracting the residual solid matters for multiple times by using an organic extraction solvent, collecting the extracting solution, removing the solvent, washing the residual solid matters by using an organic washing solvent, and drying in vacuum to obtain the trifluoroethyl coordination nickel-based procatalyst.
4. A process for preparing a trifluoroethyl complex nickel-based procatalyst as set forth in claim 3 wherein: the organic extraction solvent is benzene or toluene.
5. A process for preparing a trifluoroethyl complex nickel-based procatalyst as set forth in claim 3 wherein: the organic washing solvent is any one of diethyl ether, n-pentane and n-hexane.
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