CN114456210A - Synthesis method of tetrakis (triphenylphosphine) palladium (0) catalyst - Google Patents
Synthesis method of tetrakis (triphenylphosphine) palladium (0) catalyst Download PDFInfo
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- CN114456210A CN114456210A CN202111555707.5A CN202111555707A CN114456210A CN 114456210 A CN114456210 A CN 114456210A CN 202111555707 A CN202111555707 A CN 202111555707A CN 114456210 A CN114456210 A CN 114456210A
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
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- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- C—CHEMISTRY; METALLURGY
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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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
Abstract
The invention relates to the technical field of catalyst synthesis, and discloses a synthesis method of a tetrakis (triphenylphosphine) palladium (0) catalyst, which comprises the following steps: heating a divalent palladium precursor and triphenylphosphine in an organic solvent to react to obtain a bis (triphenylphosphine) palladium (II) complex, reducing the complex at a certain temperature, and coordinating the complex with excessive triphenylphosphine to obtain tetrakis (triphenylphosphine) palladium (0); and cooling, crystallizing, filtering, washing and drying to obtain the target product. The divalent palladium precursor selected by the invention is an easily synthesized high-purity palladium complex, can dissociate out alkali in the reaction process to neutralize the generated acid, and the reaction solvent is a sulfur-free environment-friendly polar solvent with high boiling point and high stability. The process has high yield, and the prepared tetrakis (triphenylphosphine) palladium (0) has high purity, good stability and no sulfur impurity residue, and is suitable for the pharmaceutical industry.
Description
Technical Field
The invention relates to the technical field of catalyst synthesis, in particular to a synthesis method of a tetrakis (triphenylphosphine) palladium (0) catalyst.
Background
The coupling reaction refers to a process of obtaining one organic molecule by performing a certain chemical reaction on two organic chemical molecules, and includes Heck reaction, Suzuki reaction, Negishi coupling, Stille coupling, Sonogashira coupling and the like, and the coupling reaction is widely applied to organic synthesis. Tetrakis (triphenylphosphine) palladium (0) is used as an important coupling reaction catalyst, is mainly used for constructing carbon-carbon bonds or carbon-heteroatom bonds, is successfully used for synthesizing medicaments, pesticides and organic functional molecules at present, and has the characteristics of mild catalytic conditions and high efficiency, and can catalyze a plurality of reactions which are difficult to occur under the action of similar catalysts.
The molecular formula of the tetrakis (triphenylphosphine) palladium (0) is Pd [ P (C)6H5)3]4Often abbreviated as Pd (PPh)3)4It is a bright yellow crystal, and can be slowly oxidized to brown when exposed to air, and the decomposition of tetrakis (triphenylphosphine) palladium (0) can be promoted by temperature or light, so that it is necessary to keep the crystal in a dark place in an inert gas atmosphere. The literature reports various methods for synthesizing tetrakis (triphenylphosphine) palladium (0), and the following methods are mainly used:
(1) palladium chloride and triphenylphosphine are dissolved in DMSO or DMF solvent under heating and then reduced with hydrazine hydrate (Inorganic Synthesis 1972, 121-. Similarly, bis (triphenylphosphine) palladium dichloride was mixed with triphenylphosphine and hydrazine hydrate was added as a reducing agent (PCT 2004028535; PCT int.appl., 2004093803); the yield is 90-99%.
(2) The method comprises the following steps of putting palladium chloride and triphenylphosphine in a mixed solvent of toluene and methanol, and taking a potassium hydroxide methanol solution as a reducing agent, (PCT2010128316) yield is 75-93%.
(3)From Pd (DBA)2Or Pd2(DBA)3With PPh3The reaction is prepared by ligand exchange (J.organomet.chem.1974, 73, 401; Tetrahedron Letters, 29(38), 4851-4, 1988).
(4) Palladium chloride and triphenylphosphine were reduced with ascorbic acid or formic acid in DMSO in the presence of a base (US10875881) in about 97% yield.
In addition, some methods obtain the tetrakis (triphenylphosphine) palladium (0) by reducing different palladium precursors with different reducing agents, but the yield is not improved, and the application range of the process is limited.
In summary, the palladium precursor is typically a divalent palladium chloride PdCl2The (II) is the main one, but the difference of the synthesis process causes the actually used palladium chloride to have a certain purity deviation, such as different acidity or doping with a small amount of palladium with different forms, and the factors have great influence on the quality and stability of the tetrakis (triphenylphosphine) palladium (0). In addition, dimethyl sulfoxide (DMSO) is often used as a reaction solvent in the prior art, and the solvent is partially decomposed into methyl sulfide (boiling point 38 ℃), dimethyl disulfide (boiling point 109 ℃) and methyl mercaptan (boiling point 123 ℃) under heating, especially when palladium chloride has certain acidity, and the odor is unpleasant, and residual organic sulfur compounds can promote the decomposition of tetrakis (triphenylphosphine) palladium to form dark patches. Even if DMF is used as a reaction solvent, DMF can be decomposed into dimethylamine and formic acid under acidic conditions, and the quality of the product is influenced. The ligand exchange method needs to synthesize the raw material Pd (DBA) in advance2Or Pd2(DBA)3The yield is not as high as that of direct reaction of palladium chloride and triphenylphosphine, and the exchanged DBA ligand is not easy to remove.
The high quality pure product of the tetrakis (triphenylphosphine) palladium (0) presents beautiful golden yellow, while the low quality or deteriorated product usually presents brown or brown color or even dark green color, even though the catalytic performance of the products produced by different batches of the same reagent company can have large difference. To overcome the above disadvantages, the new process requires stable palladium precursors, suitable reaction solvents and reducing agents, with comparable yields.
Disclosure of Invention
In order to solve the technical problem, the invention provides a synthesis method of a tetrakis (triphenylphosphine) palladium (0) catalyst. The invention selects a specific divalent palladium compound as a precursor, reacts with triphenylphosphine in a specific polar solvent, and finally obtains the product of the tetrakis (triphenylphosphine) palladium (0) through reduction. The product of the invention has high yield, purity and stability, and the used solvent does not contain sulfur, thus being beneficial to the recycling of noble metal palladium in the later period.
The specific technical scheme of the invention is as follows: a method for synthesizing a tetrakis (triphenylphosphine) palladium (0) catalyst has a reaction equation:
l: a ligand; n is 0-4; x: cl, Br, acac or AcO; MX: an inorganic salt.
The method specifically comprises the following steps: under the atmosphere of inert gas, mixing a divalent palladium precursor and triphenylphosphine in a reaction vessel, heating and dissolving in an organic solvent, reacting at 130-150 ℃ for 0.5-1 h to obtain an intermediate bis (triphenylphosphine) palladium (II) complex, then cooling the obtained reaction liquid to 95-110 ℃, adding a reducing agent under full stirring to reduce Pd (II) into Pd (0), and then coordinating Pd (0) with excessive triphenylphosphine to obtain tetrakis (triphenylphosphine) palladium (0); after cooling, crystallization, filtration, washing and drying, the tetrakis (triphenylphosphine) palladium (0) catalyst is obtained as yellow crystals.
The divalent palladium precursor is palladium bromide, dichlorodiammine palladium, dichlorotetraammine palladium, bis (acetylacetone) palladium, tetraammine palladium tetrachloropalladate ([ Pd (NH)3)4][PdCl4]) And sodium tetrachloropalladate.
The organic solvent is one or more of N, N-Dimethylacetamide (DMAC), N-Diethylformamide (DEF), d-pyrrolidone, N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP) and diethylene glycol dimethyl ether.
The invention selects a specific divalent palladium compound as a precursor, reacts with triphenylphosphine in a specific polar solvent, and finally obtains the product of the tetrakis (triphenylphosphine) palladium (0) through reduction. The product of the invention has high yield, purity and stability; and the used solvent does not contain sulfur, thereby being beneficial to the recycling of noble metal palladium in the later period. Specifically, the method comprises the following steps:
(1) selection of palladium precursor: in the prior art, palladium chloride is generally used as a raw material, and the preparation process determines that the palladium chloride may have high acidity or be doped with palladium with different valence states, which affects the purity and stability of tetrakis (triphenylphosphine) palladium (0). If taking palladium dichlorodiammine as an example, the reaction substrate is easy to synthesize, does not dope acidic impurities and has the characteristic of high purity, and the ammonia molecules and chloride ions form ammonium chloride after reduction, so the pH value of the reaction system can be stabilized without adding extra alkaline substances, and the yield and the purity of the tetrakis (triphenylphosphine) palladium (0) are improved.
(2) Selection of the reducing agent: in the prior art, hydrazine hydrate is mainly used as a reducing agent, so that a relatively ideal reduction effect can be achieved, but in the research process, the reaction is very violent, the hydrazine hydrate is oxidized to generate a large amount of nitrogen, and certain risk exists for large-scale production. In the research process, the team of the invention finds that the sodium formate is used as a reducing agent, the reduction reaction of the sodium formate is mild, the sodium formate is oxidized into alkaline sodium salt, and hydrogen ions generated by the reaction are neutralized at the same time, so that the effect of stabilizing the pH value of a system is achieved, and the effect of the reducing agent and the effect of alkali are achieved.
(3) Selection of reaction solvent: dimethyl sulfoxide (DMSO) has been used as a solvent in many cases in the prior art, and this solvent is partially decomposed into sulfur-containing organic substances such as methyl sulfide, dimethyl disulfide and methyl mercaptan under heating conditions, particularly under acidic conditions, and an organic sulfur compound which is unpleasant in odor and remains may promote decomposition of tetrakis (triphenylphosphine) palladium (0). If DMF is used as a reaction solvent, the boiling point of DMF is 153 ℃, and the acidic condition can promote the DMF to be decomposed into dimethylamine and formic acid at the temperature close to the boiling point, the product quality is influenced, the solubility of the reaction intermediate in DMF is not very high, and the corresponding solvent dosage is increased. In the research process of the invention, the team discovers that the high-boiling-point sulfur-free organic solvent is taken as a reaction solvent, and N, N-Diethylformamide (DEF) and N-methyl-2-pyrrolidone (NMP) are taken as examples, so that the boiling point and the stability are improved, the decomposition is avoided even under a certain acidity condition, the residue of sulfur-containing substances is avoided, and the quality of the final product tetrakis (triphenylphosphine) palladium (0) is ensured. In addition, the method does not discharge sulfur dioxide in the process of recovering palladium in the mother solution, and is an environment-friendly polar solvent.
The tetrakis (triphenylphosphine) palladium (0) has certain stability in air, can be weighed conventionally and then packaged by filling nitrogen for refrigeration storage, and has a little difference in crystallinity and purity of the tetrakis (triphenylphosphine) palladium (0) according to differences of palladium precursors and differences of reaction conditions, so that the stability is different. The high-purity crystallized tetrakis (triphenylphosphine) palladium (0) is golden yellow, can be exposed in dry air for 24 hours at the room temperature of 10-15 ℃ without discoloring, and the powder or the tetrakis (triphenylphosphine) palladium (0) with trace impurities slowly loses luster in the air and finally becomes brown yellow powder. The product obtained by the invention is bright yellow crystal powder and has better stability.
Preferably, the divalent palladium precursor is palladium bis (acetylacetonate) and/or palladium dichlorodiammine.
In view of the ease of synthesis of the palladium precursor and the reaction yield, bis (acetylacetonato) palladium and dichlorodiamidopalladium are preferable as the palladium precursor. Wherein, the anion of the bis (acetylacetone) palladium is weak acid, and the acetylacetone generated after reduction is easy to dissolve in a reaction solvent and is easy to separate from a product. The dichlorodiammine palladium is an intermediate for recovering palladium in the waste catalyst, can be directly used for synthesizing the tetrakis (triphenylphosphine) palladium (0), and greatly improves the recycling efficiency of the noble metal.
Preferably, the organic solvent is N, N-Diethylformamide (DEF) and/or N-methyl-2-pyrrolidone (NMP).
The polar solvent with high boiling point and high stability is selected as the reaction solvent, the solvent has better solubility to reaction substrates at higher temperature, and the solvent has smaller solubility to the tetrakis (triphenylphosphine) palladium (0) at room temperature, so that the product is easy to precipitate and separate.
Preferably, the molar ratio of the divalent palladium precursor to triphenylphosphine is 1: 4-1: 6, and the amount of the organic solvent is 7-12L per mole of the divalent palladium precursor; the molar ratio of the divalent palladium precursor to the reducing agent is 1: 0.5-1: 3.
Preferably, the reducing agent is 75-85wt% hydrazine hydrate, hydrazine hydrochloride, formic acid or sodium formate.
Preferably, the reducing agent is 75-85wt% hydrazine hydrate or sodium formate.
Preferably, the pH of the system changes before and after the reduction reaction, and in the reaction using palladium bromide or sodium tetrachloropalladate as a divalent palladium precursor, an alkaline substance is added to neutralize hydrogen ions generated during the reduction process, and dichlorodiamminepalladium, dichlorotetraaminepalladium, and tetraaminepalladium tetrachloropalladate ([ Pd (NH) is used3)4][PdCl4]) When the compound coordinated by ammonia is a divalent palladium precursor, no alkaline substance is needed to be added in the reaction process, and when the bis (acetylacetone) palladium is used as the divalent palladium precursor for the reaction, the acetylacetonato radical after the reaction of the bis (acetylacetone) palladium can be combined with hydrogen ions to form acetylacetone, so that no alkaline substance is needed to be added. Preferably, the basic substance is an inorganic base or organic ammonia; the inorganic alkali is sodium bicarbonate and sodium carbonate; the organic ammonia is triethylamine and diisopropylamine.
Preferably, the basic substance is organic ammonia.
Preferably, the cooling, crystallizing, filtering, washing and drying are specifically: cooling the reaction system to 20-40 ℃ for crystallization, performing filter pressing under nitrogen, washing the product with deoxidized deionized water, ethanol and anhydrous ether respectively for 2-3 times, finally performing vacuum drying for 1-2 h under the conditions that the temperature is 35-40 ℃ and the vacuum degree is less than or equal to-0.09 MPa, cooling to room temperature, filling nitrogen, and refrigerating for storage.
Compared with the prior art, the invention has the following technical effects: the invention selects a specific divalent palladium compound as a precursor, reacts with triphenylphosphine in a specific polar solvent, and finally obtains the product of the tetrakis (triphenylphosphine) palladium (0) through reduction. The product of the invention has high yield, purity and stability, and the used solvent does not contain sulfur, thus being beneficial to the recycling of noble metal palladium in the later period.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A method for synthesizing a tetrakis (triphenylphosphine) palladium (0) catalyst comprises the following steps: under the inert gas atmosphere, mixing a divalent palladium precursor and triphenylphosphine in a reaction container according to the molar ratio of 1: 4-1: 6; adding 7-12L of organic solvent into each mole of divalent palladium precursor, heating for dissolving, reacting for 0.5-1 h at 130-150 ℃ to obtain an intermediate bis (triphenylphosphine) palladium (II) complex, cooling the obtained reaction liquid to 95-110 ℃, adding a reducing agent with 0.5-3 times of the molar weight of the divalent palladium precursor under sufficient stirring to reduce Pd (II) into Pd (0), and coordinating Pd (0) with excessive triphenylphosphine to obtain tetrakis (triphenylphosphine) palladium (0); cooling the reaction system to 20-40 ℃ for crystallization, performing filter pressing under nitrogen, washing the product with deoxidized deionized water, ethanol and anhydrous ether respectively for 2-3 times, finally performing vacuum drying for 1-2 h under the conditions that the temperature is 35-40 ℃ and the vacuum degree is less than or equal to-0.09 MPa, cooling to room temperature, filling nitrogen, refrigerating and storing to obtain the yellow crystalline tetrakis (triphenylphosphine) palladium (0) catalyst, wherein the purity of the product can be obtained by dividing the actual palladium content by the theoretical palladium content.
The divalent palladium precursor is palladium bromide, dichlorodiammine palladium, dichlorotetraammine palladium, bis (acetylacetone) palladium, (1, 5-cyclooctadiene) palladium dichloride, tetraammine palladium tetrachloropalladate ([ Pd (NH)3)4][PdCl4]) One or more of sodium tetrachloropalladate, bis (acetonitrile) palladium chloride and palladium acetate; further preferred is palladium bis (acetylacetonate) and/or palladium dichlorodiammine.
The organic solvent is one or more of N, N-Dimethylacetamide (DMAC), N-Diethylformamide (DEF), alpha-pyrrolidone, N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP) and diethylene glycol dimethyl ether; further preferred is N, N-Diethylformamide (DEF) and/or N-methyl-2-pyrrolidone (NMP). The reducing agent is 75-85wt% of hydrazine hydrate, hydrazine hydrochloride, formic acid or sodium formate; further preferably 75 to 85% by weight of hydrazine hydrate or sodium formate.
Wherein, the pH value of the system can change before and after the reduction reaction, and for the palladium precursor without ammonia coordination, alkaline substances are added for the reaction to neutralize the hydrogen ions generated in the reduction process. The alkaline substance is inorganic alkali or organic ammonia; the inorganic alkali is sodium bicarbonate and sodium carbonate; the organic ammonia is triethylamine and diisopropylamine. Further preferred is organic ammonia.
Example 1
Adding 15.2g (50mmol) of palladium bis (acetylacetonate) and 59.0g (225mmol) of triphenylphosphine into a 1L reaction kettle, adding 600mL of N, N-Diethylformamide (DEF) under stirring, vacuumizing to the vacuum degree of less than or equal to-0.08 MPa, introducing nitrogen to replace air, repeating for three times, heating the reaction system to 140 +/-2 ℃ through an oil bath, slowly dissolving the raw materials, obtaining a brownish red transparent solution after all solids are dissolved, removing the oil bath, cooling to about 100 ℃, adding 3.1g (about 50mmol) of 80% hydrazine hydrate under rapid stirring to reduce, and controlling the adding speed of the hydrazine hydrate to prevent a large amount of generated gas from causing spray. After the reaction is finished, cooling in a water bath, precipitating a large amount of yellow crystals, starting filtering when the reaction system is cooled to below 30 ℃, carrying out pressure filtration under the protection of nitrogen, washing the product by using deoxidized deionized water 2x100mL, ethanol 3x80mL and anhydrous ether 2x80mL respectively, finally carrying out vacuum drying for 1.5h under the conditions that the temperature is 40 +/-2 ℃ and the vacuum degree is less than or equal to-0.09 MPa, cooling to room temperature, filling nitrogen, refrigerating and storing in a dark place to obtain 57.2g of tetrakis (triphenylphosphine) palladium (0) bright yellow crystal powder, wherein the yield is 99.0%.
The detected Pd content is 9.12 percent, and the theoretical content is 9.21 percent. The CHN elemental analysis value is: c, 74.33%; h, 5.33%; n: less than 0.1%, the theoretical value is: c, 74.84%; h, 5.23%; n: 0 percent.
Example 2
15.2g (50mmol) of palladium bis (acetylacetonate) and 65.6g (250mmol) of triphenylphosphine were charged into a 1L reactor, 600mL of DEF was added with stirring, vacuum was applied until the vacuum degree was not more than-0.08 MPa, then air was replaced with nitrogen gas, and the reaction system was heated to 140. + -. 2 ℃ by an oil bath, and after the raw materials were dissolved, the temperature was lowered to about 105 ℃ and 6.8g (about 100mmol) of a solution of sodium formate in 15mL of water was added, and the post-treatment was the same as in example 1, whereby 57.0g of tetrakis (triphenylphosphine) palladium (0) was obtained as bright yellow crystal powder with a yield of 98.6%.
The detected Pd content is 9.07 percent, and the CHN element analysis value is as follows: c, 74.49%; h, 5.26%; n: is less than 0.1 percent.
Example 3
A1L reactor was charged with 15.2g (50mmol) of palladium bis (acetylacetonate) and 65.6g (250mmol) of triphenylphosphine, and 500mL of NMP was added with stirring and with a reducing agent of 3.1g (about 50mmol) of 80% hydrazine hydrate under the same conditions as in example 1 to obtain 56.7g of tetrakis (triphenylphosphine) palladium (0) as bright yellow crystals in 98.1% yield.
The detected Pd content is 9.11%, and the CHN element analysis value is as follows: c, 74.51%; h, 5.38%; n: is less than 0.1 percent.
Example 4
A1L reactor was charged with 10.5g (50mmol) of dichlorodiammine palladium and 65.6g (250mmol) of triphenylphosphine as a reducing agent of 3.1g (about 50mmol) of 80% hydrazine hydrate under the same conditions as in example 1 to obtain 56.8g of tetrakis (triphenylphosphine) palladium (0) as a bright yellow crystalline powder with a yield of 98.3%.
The detected Pd content is 9.10%, and the CHN element analysis value is as follows: c, 74.47%; h, 5.36%; n: is less than 0.1 percent.
Example 5
A1L reactor was charged with 10.5g (50mmol) of dichlorodiamminepalladium and 59.0g (225mmol) of triphenylphosphine in a solution of 5.2g (50mmol) of hydrazine hydrochloride in 15mL of deionized water at a reducing temperature of 110 ℃ under the same conditions as in example 1 to obtain 56.3g of tetrakis (triphenylphosphine) palladium (0) as bright yellow crystals in 97.5% yield.
The detected Pd content is 9.05 percent, and the CHN element analysis value is as follows: c, 74.14%; h, 5.31%; n: is less than 0.1 percent.
The reaction conditions for examples 6-9 are shown in the following table, the unlabeled conditions and operations were performed as described in example 1, and the results are shown below.
Comparative examples 1 to 5
The team of the present invention makes further comparisons with respect to the prior art, with the reaction conditions as shown in the following table, the unlabeled conditions and operations as described in example 1, and the results as shown below.
As can be seen from the data in the table above, the yield of each proportion is 95-98%, the yield is reduced compared with the examples, and the stability comparison test in air shows that the product obtained by using the sulfur-containing solvent DMSO as the reaction solvent is poor in stability.
The stability of the tetrakis (triphenylphosphine) palladium (0) can be judged according to color change, and stability test comparison is carried out on products synthesized by different palladium precursors and solvent cases under the same conditions, wherein the test conditions are as follows: the product is exposed in the air, the temperature is controlled to be 28-30 ℃, and the humidity is controlled to be 30-70% RH.
Note: a is bright yellow, b is yellow, c is dark yellow, d is brown, and e is dark brown, as can be seen from the comparison of the data in the above table, different palladium precursors and reaction solvents have a large influence on the stability of the product. For example, examples 1, 3 and 4 use palladium bis (acetylacetonate) or palladium dichlorodiammine as the palladium precursor, as compared to comparative examples 1, 3 and 5 using palladium chloride or Pd (CH)3CN)2Cl2Is a palladium precursor, the stability of the obtained product is greatly improved. And, although the product obtained in comparative example 5 has a high palladium content (9.10%), it uses DMSO as a solvent, and the sulfide is somewhat left, which promotes the decomposition of the product, resulting in poor product stability.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for synthesizing a tetrakis (triphenylphosphine) palladium (0) catalyst is characterized by comprising the following steps: under the atmosphere of inert gas, mixing a divalent palladium precursor and triphenylphosphine in a reaction vessel, heating and dissolving in an organic solvent, reacting at 130-150 ℃ for 0.5-1 h to obtain an intermediate bis (triphenylphosphine) palladium (II) complex, then cooling the obtained reaction liquid to 95-110 ℃, adding a reducing agent under full stirring to reduce Pd (II) into Pd (0), and then coordinating Pd (0) with excessive triphenylphosphine to obtain tetrakis (triphenylphosphine) palladium (0); cooling, crystallizing, filtering, washing and drying to obtain a yellow crystalline tetrakis (triphenylphosphine) palladium (0) catalyst;
the divalent palladium precursor is palladium bromide, dichlorodiammine palladium, dichlorotetraammine palladium, bis (acetylacetone) palladium, tetraammine palladium tetrachloropalladate ([ Pd (NH)3)4][PdCl4]) And sodium tetrachloropalladate;
the organic solvent is one or more of N, N-dimethylacetamide, N-diethylformamide, alpha-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and diethylene glycol dimethyl ether.
2. The method of synthesis of claim 1, wherein: the divalent palladium precursor is palladium bis (acetylacetonate) and/or palladium dichlorodiammine.
3. The method of synthesis of claim 1, wherein: the organic solvent is N, N-diethylformamide and/or N-methyl-2-pyrrolidone.
4. A method of synthesis according to any one of claims 1 to 3, characterized in that: the molar ratio of the divalent palladium precursor to triphenylphosphine is 1: 4-1: 6, and the amount of the organic solvent is 7-12L per mole of the divalent palladium precursor; the molar ratio of the divalent palladium precursor to the reducing agent is 1: 0.5-1: 3.
5. A method of synthesis according to any one of claims 1 to 3, characterized in that: the reducing agent is 75-85wt% of hydrazine hydrate, hydrazine hydrochloride, formic acid or sodium formate.
6. The method of synthesis of claim 5, wherein: the reducing agent is 75-85wt% of hydrazine hydrate or sodium formate.
7. The method of synthesis of claim 1, wherein: for divalent palladium precursors that do not contain ammonia coordination, a basic substance is added during the reduction reaction to neutralize the hydrogen ions generated during the reduction.
8. The method of synthesis of claim 7, wherein: the alkaline substance is inorganic alkali or organic ammonia; the inorganic alkali is sodium bicarbonate and sodium carbonate; the organic ammonia is triethylamine and diisopropylamine.
9. The method of synthesis of claim 8, wherein: the alkaline substance is organic ammonia.
10. A method of synthesis according to any one of claims 1 to 3, characterised in that: the cooling, crystallizing, filtering, washing and drying are specifically as follows: cooling the reaction system to 20-40 ℃ for crystallization, performing filter pressing under nitrogen, washing the product with deoxidized deionized water, ethanol and anhydrous ether respectively for 2-3 times, finally performing vacuum drying for 1-2 h under the conditions that the temperature is 35-40 ℃ and the vacuum degree is less than or equal to-0.09 MPa, cooling to room temperature, filling nitrogen, and refrigerating for storage.
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