CN113754700A - Preparation method of bis (triphenylphosphine) palladium dichloride - Google Patents
Preparation method of bis (triphenylphosphine) palladium dichloride Download PDFInfo
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- CN113754700A CN113754700A CN202111222379.7A CN202111222379A CN113754700A CN 113754700 A CN113754700 A CN 113754700A CN 202111222379 A CN202111222379 A CN 202111222379A CN 113754700 A CN113754700 A CN 113754700A
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- triphenylphosphine
- palladium dichloride
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- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 74
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 37
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000047 product Substances 0.000 abstract description 35
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052763 palladium Inorganic materials 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 4
- 239000003446 ligand Substances 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- WTLOGKMDQWEFOK-UHFFFAOYSA-N oxolane;triphenylphosphane Chemical compound C1CCOC1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WTLOGKMDQWEFOK-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of palladium catalysts. The invention provides a preparation method of bis (triphenylphosphine) palladium dichloride, which comprises the following steps: mixing (1, 5-cyclooctadiene) palladium dichloride and an organic solvent to obtain a solution 1; mixing triphenylphosphine and an organic solvent to obtain a solution 2; and mixing the solution 1 and the solution 2 for reaction, and drying a reaction product in vacuum to obtain the bis (triphenylphosphine) palladium dichloride. The preparation method of the invention reduces the content of the hetero-ions in the product and the requirements of reaction conditions, the whole reaction process does not involve dangerous chemicals, the reaction conditions are mild, and the operation environment is better and safer. The preparation method has the advantages of low production cost, short synthesis period, high efficiency and simple operation steps, and the yield of the target product bis (triphenylphosphine) palladium dichloride is more than or equal to 99.2 percent, and the purity is more than or equal to 98.5 percent.
Description
Technical Field
The invention relates to the technical field of palladium catalysts, in particular to a preparation method of bis (triphenylphosphine) palladium dichloride.
Background
Bis (triphenylphosphine) palladium dichloride is an important palladium catalyst in chemical reactions and is widely applied to organic catalysis and pharmaceutical chemicals. For example, bis (triphenylphosphine) palladium dichloride is a highly effective catalyst for coupling reactions such as Sonogoshira coupling, carbonylation of halides, alkyl halides to aldehydes, carboxylic acids, amides, and the like.
Currently, the main synthesis method of bis (triphenylphosphine) palladium dichloride comprises: 1) direct reaction of palladium chloride and triphenylphosphine; 2) exchanging the complex of palladium chloride and acetonitrile (or benzonitrile) with triphenylphosphine ligand; 3) reacting tetrachloropalladate (potassium salt and sodium salt) with triphenylphosphine; 4) reacting the resultant of palladium chloride and concentrated hydrochloric acid with triphenylphosphine. The above reactions all take palladium chloride as raw material, directly react with triphenylphosphine or synthesize corresponding intermediate, and then react with triphenylphosphine to synthesize the target product bis (triphenylphosphine) palladium dichloride. The preparation process of the method is complicated, and the production cost is high. In addition, the method 1) needs more than 48 hours of reaction with long time consumption and extremely low yield; acetonitrile and benzonitrile used in the method 2) are chemicals with extremely high toxicity, and the method has long reaction time and low product purity; in the method 3), palladium chloride is reacted with sodium chloride (potassium chloride) to obtain a tetrachloropalladate solution, and then the tetrachloropalladate solution and triphenylphosphine are synthesized into bis (triphenylphosphine) palladium dichloride, although the method shortens the reaction time and improves the reaction yield, the post-treatment is more complicated, and K, Na and other impurity ions are easily introduced, so that the purity of a target product is not high; the method 4) uses palladium chloride to react with concentrated hydrochloric acid to obtain tetrachloropalladate acid solution, and then synthesizes bis (triphenylphosphine) palladium dichloride with triphenylphosphine, wherein the concentrated hydrochloric acid belongs to a controlled hazardous article, has strong acidity, has high requirement on reaction equipment, increases equipment cost, and is not suitable for industrial production.
Therefore, the research on the preparation method of the bis (triphenylphosphine) palladium dichloride with short synthesis period, simple operation steps, high synthesis efficiency, low production cost, high yield of the target product and high purity has important value and significance.
Disclosure of Invention
The invention aims to provide a preparation method of bis (triphenylphosphine) palladium dichloride aiming at the defects of the prior art, and aims to solve the problems of low yield, low purity, low synthesis efficiency and long period of bis (triphenylphosphine) palladium dichloride in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of bis (triphenylphosphine) palladium dichloride, which comprises the following steps:
1) mixing (1, 5-cyclooctadiene) palladium dichloride and an organic solvent to obtain a solution 1;
2) mixing triphenylphosphine and an organic solvent to obtain a solution 2;
3) and mixing the solution 1 and the solution 2 for reaction, and drying a reaction product in vacuum to obtain the bis (triphenylphosphine) palladium dichloride.
Preferably, the mixing temperature in the step 1) is 30-70 ℃, and the time is 15-60 min.
Preferably, the mass-to-volume ratio of the (1, 5-cyclooctadiene) palladium dichloride and the organic solvent in the step 1) is 1 g: 5-30 mL.
Preferably, the mixing temperature in the step 2) is 30-70 ℃, and the time is 15-60 min.
Preferably, the mass volume ratio of the triphenylphosphine to the organic solvent in the step 2) is 1 g: 5-20 mL; the mass ratio of the triphenylphosphine to the (1, 5-cyclooctadiene) palladium dichloride in the step 1) is 2-5: 1.
preferably, the organic solvent of step 1) and step 2) independently comprises absolute ethanol, dichloromethane or tetrahydrofuran.
Preferably, the solution 1 is dripped into the solution 2 in the mixing mode in the step 3), and the dripping speed is 20-100 mL/min; the reaction temperature is 30-70 ℃, and the reaction time is 0.5-4 h.
Preferably, the temperature of the vacuum drying in the step 3) is 50-80 ℃, the time is 3-10 h, and the vacuum degree of the vacuum drying is less than or equal to-0.04 MPa.
Preferably, before the vacuum drying in step 3), the reaction product is sequentially cooled, filtered, washed and dried to obtain a filter cake, and the filter cake is vacuum-dried.
The beneficial effects of the invention include the following:
1) according to the invention, (1, 5-cyclooctadiene) palladium dichloride is used for replacing palladium chloride or a palladium chloride complex compound, a target product is directly synthesized, the content of the impurity ions in the product and the requirements of reaction conditions are reduced, the whole reaction process does not involve dangerous chemicals, the reaction conditions are mild, and the operation environment is better and safer.
2) The preparation method has the advantages of low production cost, short synthesis period, high efficiency and simple operation steps, and the yield of the target product bis (triphenylphosphine) palladium dichloride is more than or equal to 99.2 percent, and the purity is more than or equal to 98.5 percent.
Detailed Description
The invention provides a preparation method of bis (triphenylphosphine) palladium dichloride, which comprises the following steps:
1) mixing (1, 5-cyclooctadiene) palladium dichloride and an organic solvent to obtain a solution 1;
2) mixing triphenylphosphine and an organic solvent to obtain a solution 2;
3) and mixing the solution 1 and the solution 2 for reaction, and drying a reaction product in vacuum to obtain the bis (triphenylphosphine) palladium dichloride.
The mixing temperature in the step 1) of the invention is preferably 30-70 ℃, more preferably 40-60 ℃, and more preferably 45-55 ℃; the mixing time is preferably 15-60 min, more preferably 25-50 min, and even more preferably 35-40 min; the mixing is preferably carried out under stirring.
The mass-to-volume ratio of the (1, 5-cyclooctadiene) palladium dichloride and the organic solvent in the step 1) of the invention is preferably 1 g: 5-30 mL, more preferably 1 g: 10-25 mL, more preferably 1 g: 15-20 mL.
The mixing temperature in the step 2) of the invention is preferably 30-70 ℃, more preferably 40-60 ℃, and more preferably 45-55 ℃; the mixing time is preferably 15-60 min, more preferably 25-50 min, and even more preferably 35-40 min; the mixing is preferably carried out under stirring.
The mass volume ratio of the triphenylphosphine to the organic solvent in step 2) of the invention is preferably 1 g: 5-20 mL, more preferably 1 g: 8-16 mL, more preferably 1 g: 10-13 mL; the mass ratio of the triphenylphosphine to the (1, 5-cyclooctadiene) palladium dichloride in the step 1) is preferably 2-5: 1, more preferably 3 to 4: 1.
the organic solvent in step 1) and step 2) of the present invention preferably independently comprises absolute ethanol, dichloromethane or tetrahydrofuran.
The mixing mode in the step 3) of the invention is preferably that the solution 1 is dripped into the solution 2, and the dripping speed is preferably 20-100 mL/min, more preferably 40-80 mL/min, and more preferably 50-70 mL/min; the reaction temperature is preferably 30-70 ℃, more preferably 40-60 ℃, and more preferably 45-55 ℃; the reaction time is preferably 0.5-4 h, more preferably 1-3 h, and even more preferably 2 h; the reaction is preferably carried out under stirring.
The temperature of the vacuum drying in the step 3) is preferably 50-80 ℃, more preferably 60-70 ℃, and more preferably 63-66 ℃; the vacuum drying time is preferably 3-10 h, more preferably 5-8 h, and even more preferably 6-7 h; the vacuum degree of the vacuum drying is preferably less than or equal to-0.04 MPa.
Preferably, before the vacuum drying in step 3), the reaction product is sequentially cooled, filtered, washed and dried to obtain a filter cake, and the filter cake is vacuum-dried.
The bis (triphenylphosphine) palladium dichloride obtained by the preparation method is yellow crystals.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
10.0g of (1, 5-cyclooctadiene) palladium dichloride was added to 80mL of tetrahydrofuran with stirring and dissolved at 55 ℃ for 20min to obtain a uniform tetrahydrofuran solution of (1, 5-cyclooctadiene) palladium dichloride.
25.0g of triphenylphosphine was added to 150mL of tetrahydrofuran with stirring, and dissolved at 55 ℃ for 20min to obtain a uniform tetrahydrofuran solution of triphenylphosphine.
Under the condition of rapid stirring, a tetrahydrofuran solution of (1, 5-cyclooctadiene) palladium dichloride is dropwise added into a tetrahydrofuran solution of triphenylphosphine at the speed of 30mL/min, and the reaction is stirred for 0.5h under the condition of 55 ℃. And cooling, filtering, washing and pumping the reaction product to obtain a filter cake, and performing vacuum drying on the filter cake for 3.5 hours at the temperature of 60 ℃ and the vacuum degree of-0.05 MPa to obtain the target product bis (triphenylphosphine) palladium dichloride.
The mass of bis (triphenylphosphine) palladium dichloride of example 1 was 24.53g, the product yield was 99.8%, and the product purity was 98.9%. The result of elemental analysis of bis (triphenylphosphine) palladium dichloride of example 1 was C: 61.32%, H: 4.39%, Pd: 14.99 percent; theoretical value is C: 61.60%, H: 4.32%, Pd: 15.16 percent.
Example 2
10.0g of (1, 5-cyclooctadiene) palladium dichloride was added to 100mL of dichloromethane with stirring and dissolved at 40 ℃ for 40min to obtain a uniform dichloromethane solution of (1, 5-cyclooctadiene) palladium dichloride.
30.0g of triphenylphosphine was added to 600mL of anhydrous ethanol with stirring, and dissolved at 40 ℃ for 45min to obtain a uniform ethanol solution of triphenylphosphine.
Under the condition of rapid stirring, a dichloromethane solution of (1, 5-cyclooctadiene) palladium dichloride is dropwise added into an ethanol solution of triphenylphosphine at a speed of 50mL/min, and the reaction is stirred for 3 hours at the temperature of 70 ℃. And cooling, filtering, washing and pumping the reaction product to obtain a filter cake, and performing vacuum drying on the filter cake for 5.5 hours at 70 ℃ and under the vacuum degree of-0.06 MPa to obtain the target product bis (triphenylphosphine) palladium dichloride.
The mass of bis (triphenylphosphine) palladium dichloride of example 2 was 24.46g, the product yield was 99.5%, and the product purity was 98.7%. The result of elemental analysis of bis (triphenylphosphine) palladium dichloride of example 2 was C: 61.28%, H: 4.41%, Pd: 14.96 percent; theoretical value is C: 61.60%, H: 4.32%, Pd: 15.16 percent.
Example 3
10.0g of (1, 5-cyclooctadiene) palladium dichloride was added to 300mL of anhydrous ethanol with stirring, and dissolved at 70 ℃ for 20min to obtain a uniform ethanol solution of (1, 5-cyclooctadiene) palladium dichloride.
50.0g of triphenylphosphine was added to 800mL of anhydrous ethanol with stirring, and dissolved at 70 ℃ for 20min to obtain a uniform ethanol solution of triphenylphosphine.
Under the condition of rapid stirring, the ethanol solution of (1, 5-cyclooctadiene) palladium dichloride is dropwise added into the ethanol solution of triphenylphosphine at the speed of 70mL/min, and the reaction is stirred for 3 hours under the condition of 70 ℃. And cooling, filtering, washing and pumping the reaction product to obtain a filter cake, and performing vacuum drying on the filter cake for 7.5 hours at the temperature of 75 ℃ and the vacuum degree of-0.05 MPa to obtain the target product bis (triphenylphosphine) palladium dichloride.
The mass of bis (triphenylphosphine) palladium dichloride of example 3 was 24.48g, the product yield was 99.6%, and the product purity was 98.5%. The elemental analysis of bis (triphenylphosphine) palladium dichloride of example 3 gave C: 61.36%, H: 4.40%, Pd: 14.93 percent; theoretical value is C: 61.60%, H: 4.32%, Pd: 15.16 percent.
Example 4
10.0g of (1, 5-cyclooctadiene) palladium dichloride was added to 150mL of dichloromethane with stirring and dissolved at 30 ℃ for 55min to obtain a uniform dichloromethane solution of (1, 5-cyclooctadiene) palladium dichloride.
50.0g of triphenylphosphine was added to 500mL of dichloromethane with stirring, and dissolved at 30 ℃ for 55min to obtain a uniform solution of triphenylphosphine in dichloromethane.
Under the condition of rapid stirring, a dichloromethane solution of (1, 5-cyclooctadiene) palladium dichloride is dropwise added into a dichloromethane solution of triphenylphosphine at the speed of 70mL/min, and the reaction is stirred for 4 hours under the condition of 30 ℃. And cooling, filtering, washing and pumping the reaction product to obtain a filter cake, and performing vacuum drying on the filter cake for 5 hours at the temperature of 60 ℃ and the vacuum degree of-0.06 MPa to obtain the target product bis (triphenylphosphine) palladium dichloride.
The mass of bis (triphenylphosphine) palladium dichloride of example 4 was 24.38g, the product yield was 99.2%, and the product purity was 98.5%. The elemental analysis of bis (triphenylphosphine) palladium dichloride of example 4 gave C: 61.38%, H: 4.37%, Pd: 14.93 percent; theoretical value is C: 61.60%, H: 4.32%, Pd: 15.16 percent.
Example 5
200.0g of (1, 5-cyclooctadiene) palladium dichloride was added to 1200mL of tetrahydrofuran with stirring and dissolved at 60 ℃ for 30min to obtain a uniform tetrahydrofuran solution of (1, 5-cyclooctadiene) palladium dichloride.
450.0g of triphenylphosphine was added to 3000mL of tetrahydrofuran with stirring and dissolved at 60 ℃ for 30min to obtain a uniform tetrahydrofuran solution of triphenylphosphine.
Under the condition of rapid stirring, a tetrahydrofuran solution of (1, 5-cyclooctadiene) palladium dichloride is dropwise added into a tetrahydrofuran solution of triphenylphosphine at the speed of 50mL/min, and the reaction is stirred for 1h under the condition of 60 ℃. And cooling, filtering, washing and pumping the reaction product to obtain a filter cake, and performing vacuum drying on the filter cake for 4.5 hours at the temperature of 60 ℃ and the vacuum degree of-0.05 MPa to obtain the target product bis (triphenylphosphine) palladium dichloride.
The mass of bis (triphenylphosphine) palladium dichloride of example 5 was 491.19g, the product yield was 99.9%, and the product purity was 99.3%. The elemental analysis of bis (triphenylphosphine) palladium dichloride of example 5 gave C: 61.52%, H: 4.36%, Pd: 15.05 percent; theoretical value is C: 61.60%, H: 4.32%, Pd: 15.16 percent.
Comparative example 1
The reaction temperature of the (1, 5-cyclooctadiene) palladium dichloride tetrahydrofuran solution and the triphenylphosphine tetrahydrofuran solution in example 1 was changed to 20 ℃ and the reaction time was changed to 10 hours from 0.5 hour, and the other conditions were the same as in example 1.
The bis (triphenylphosphine) palladium dichloride obtained in comparative example 1 had a mass of 23.40g, a product yield of 95.2% and a product purity of 97.5%.
From example 1 and comparative example 1, it can be seen that the reaction temperature and time have a great influence on the target product bis (triphenylphosphine) palladium dichloride, and that changing the reaction temperature and time on the basis of the present invention leads to a decrease in the yield of the target product.
Comparative example 2
The mass of triphenylphosphine in example 1 was changed to 15.0g, and the other conditions were the same as in example 1.
The bis (triphenylphosphine) palladium dichloride obtained in comparative example 2 had a mass of 19.48g, a product yield of 79.2% and a product purity of 97.8%.
From example 1 and comparative example 2, it can be seen that, on the basis of the present invention, by reducing the usage ratio of ligand triphenylphosphine and (1, 5-cyclooctadiene) palladium dichloride, the yield of the target product bis (triphenylphosphine) palladium dichloride is significantly reduced.
Comparative example 3
The mass of triphenylphosphine in example 1 was changed to 70.0g, and the other conditions were the same as in example 1.
The bis (triphenylphosphine) palladium dichloride obtained in comparative example 3 had a mass of 24.29g, a product yield of 98.8% and a product purity of 97.2%.
From example 1 and comparative example 3, it is known that increasing the amount ratio of ligand triphenylphosphine and (1, 5-cyclooctadiene) palladium dichloride based on the present invention reduces the yield of the target product bis (triphenylphosphine) palladium dichloride, and at the same time, the purity of the target product is reduced.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of bis (triphenylphosphine) palladium dichloride is characterized by comprising the following steps:
1) mixing (1, 5-cyclooctadiene) palladium dichloride and an organic solvent to obtain a solution 1;
2) mixing triphenylphosphine and an organic solvent to obtain a solution 2;
3) and mixing the solution 1 and the solution 2 for reaction, and drying a reaction product in vacuum to obtain the bis (triphenylphosphine) palladium dichloride.
2. The method according to claim 1, wherein the mixing in step 1) is carried out at 30-70 ℃ for 15-60 min.
3. The preparation method according to claim 1 or 2, wherein the mass-to-volume ratio of the (1, 5-cyclooctadiene) palladium dichloride of step 1) and the organic solvent is 1 g: 5-30 mL.
4. The preparation method according to claim 3, wherein the mixing in step 2) is carried out at 30-70 ℃ for 15-60 min.
5. The preparation method according to claim 4, wherein the mass-to-volume ratio of triphenylphosphine to organic solvent in step 2) is 1 g: 5-20 mL; the mass ratio of the triphenylphosphine to the (1, 5-cyclooctadiene) palladium dichloride in the step 1) is 2-5: 1.
6. the method according to claim 4 or 5, wherein the organic solvent of step 1) and step 2) independently comprises absolute ethanol, dichloromethane or tetrahydrofuran.
7. The preparation method according to claim 6, wherein the mixing in step 3) is performed by dropping the solution 1 into the solution 2 at a rate of 20-100 mL/min; the reaction temperature is 30-70 ℃, and the reaction time is 0.5-4 h.
8. The preparation method of claim 7, wherein the temperature of the vacuum drying in the step 3) is 50-80 ℃, the time is 3-10 h, and the vacuum degree of the vacuum drying is less than or equal to-0.04 MPa.
9. The production method according to claim 7 or 8, wherein the reaction product is sequentially cooled, filtered, washed and dried before the vacuum drying in step 3) to obtain a filter cake, and the filter cake is vacuum-dried.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Application publication date: 20211207 |