CN107930695B - Metal palladium complex polymer catalyst and carbon-carbon coupling reaction method using same - Google Patents
Metal palladium complex polymer catalyst and carbon-carbon coupling reaction method using same Download PDFInfo
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Abstract
The invention discloses a metal palladium complex catalyst and a carbon-carbon coupling reaction method using the same, and the metal palladium complex catalyst mainly comprises the following steps: dissolving halogenated aromatic hydrocarbon, phenyl boric acid, alkali and metal palladium complex polymer catalyst in an alcohol, ester, aromatic hydrocarbon or ether organic solvent, reacting for 2-10 hours at 10-110 ℃, cooling, standing, performing centrifugal separation, performing column chromatography separation on supernatant liquid to obtain a pure coupling product, and using the precipitate for secondary, tertiary and more cyclic reactions. Compared with the prior art, the metal palladium coordination polymer catalyst has high catalytic activity, the cycle times are as many as ten times, the catalytic activity is not obviously reduced, the problems of difficult separation of the catalyst, product pollution and the like are well solved, and the catalyst is suitable for the requirement of commercial production.
Description
The technical field is as follows:
the invention belongs to the field of metal organic catalysts and organic synthesis, relates to a metal palladium complex polymer catalyst, and simultaneously provides a carbon-carbon coupling reaction method completed by using the catalyst.
Background art:
the carbon-carbon coupling reaction plays an important role in organic synthesis and is widely applied to the fields of pharmacy, dyes, natural polymer products, advanced materials and the like. The traditional palladium homogeneous catalyst has the advantages of good dispersibility, higher catalytic activity, good selectivity and the like, but has the problems of difficult separation of the catalyst, polluted products and the like. The palladium heterogeneous catalyst can not only solve the problems well, but also be recycled for many times, and provides possibility for industrial application.
At present, there are two main types of carriers for palladium heterogeneous catalysts: inorganic carriers and organic polymer carriers. Inorganic supports include metal oxides, silicoaluminophosphate molecular sieves, silica, activated carbon, and the like, and palladium homogeneous catalysts are generally adsorbed directly onto the supports by impregnation. The palladium heterogeneous catalyst is synthesized by taking MgO as a carrier (chemical and adhesion, 2017, 39 (2), 119-. For the organic polymer carrier, the metal palladium is supported on the carrier by coordination and the like by utilizing the special functional group on the organic polymer carrier to prepare the metal palladium organic coordination polymer catalyst (hereinafter referred to as metal palladium coordination polymer catalyst) (chemical and adhesion, 2014, 36 (4), 290-.
Based on years of research on homogeneous metal organic catalysts and heterogeneous metal organic coordination polymers, the inventor designs and synthesizes a metal palladium coordination polymer catalyst, can realize carbon-carbon coupling reaction, has high catalytic activity, has cycle times as many as ten times, has no obvious reduction of catalytic activity, well solves the problems of difficult separation of the catalyst, polluted products and the like, and is suitable for the requirement of commercial production.
Disclosure of Invention
The invention provides a metal palladium complex polymer catalyst and a carbon-carbon coupling reaction method using the same, wherein the structure of the catalyst has the following general formula:
or
（II）
Or
（III）
In the formulas (I), (II) and (III), R is hydrogen, C1-C12 alkyl, C6-C12 aryl and acenaphthenyl
Preferably hydrogen, C1-C4 alkyl, phenyl and acenaphthenyl
(ii) a In the formula (I), R1, R2, R3 and R4 can be the same or different and are respectively hydrogen, C1-C12 alkyl, halogen, nitro and C6-C12 aryl, preferably hydrogen, C1-C4 alkyl, halogen, nitro, phenyl and biphenyl; in the formula (III), R' is methylene, methylene substituted by C1-C12 alkyl, methylene substituted by C1-C12 haloalkyl, preferably methylene and methylene substituted by C1-C4 alkyl; a methylene group substituted by a C1-C4 fluoroalkyl group; x is halogen, preferably chlorine or bromine.
A preparation method of a metal palladium complex catalyst is characterized by comprising the following steps of firstly, under the protection of inert gas, dissolving an aromatic diamine compound and an α -dialdehyde or ketone compound in an organic solvent, enabling the aromatic diamine compound and α -dialdehyde or ketone to react for 0.5-48 hours at the temperature of 0-80 ℃, placing the reactant into a refrigerator for crystallization after the reaction, washing the crystal with the organic solvent after the crystal is filtered, drying in vacuum to obtain a poly α -diimine complex, and then, mixing the poly α -diimine complex with (PhCN)2PdCl2Soluble in organic solvents, poly α -diimine ligands and (PhCN)2PdCl2The molar ratio of (A) to (B) is 1-5: 1, reacting at the temperature of-10-60 ℃ for 1-72 hours, standing for layering after the reaction is finished, filtering the precipitate, and drying in vacuum to obtain the late transition metal coordination polymer. The organic solvent is one of aromatic hydrocarbon, halogenated hydrocarbon, alcohol and ether solvent.
A method for catalyzing carbon-carbon coupling reaction by using a metal palladium coordination polymer catalyst is characterized by comprising the following steps: dissolving halogenated aromatic hydrocarbon (IV), phenyl boric acid (V), alkali and metal palladium complex polymer catalyst in organic solvent of alcohols, esters, aromatic hydrocarbons or amines, reacting for 2-10 hours at 40-120 ℃, cooling, standing, performing centrifugal separation, and performing silica gel column chromatography separation (petroleum ether is used as eluent) on liquid phase to obtain pure coupled product, wherein the precipitate is used for secondary, tertiary and more cyclic reactions. The alkali is K2CO3、Na2CO3、K3PO4、Na3PO4Or CH3One of ONa; the solvent is one of monohydric alcohol of C1-C6, tetrahydrofuran, dioxane, ethyl acetate, toluene, dimethylformamide and triethylamine.
Compared with the prior art, the invention has the following obvious advantages:
the metal palladium complex polymer catalyst provided by the invention is a novel supported catalyst, has high catalytic activity, has cycle times as many as ten times, has no obvious reduction of the catalytic activity, well solves the problems of difficult separation of the catalyst, polluted products and the like, and is suitable for the requirement of commercial production.
The invention is further illustrated, but not limited, by the following examples.
Example 1
Preparation of Poly-alpha-diimine ligand L1
P-phenylenediamine (1.08 g, 10 mmol) and 70 mL of methanol were added to a 250mL reaction flask under an inert gas atmosphere, and an aqueous glyoxal solution (1.27 mL, 10 mmol) was added dropwise at 10 ℃ and the reaction was stirred for 8 hours. The reaction solution was cooled in a refrigerator for crystallization, and the precipitated crystals were filtered to give a crude product, which was washed three times with diethyl ether and dried under vacuum to give 1.18g of a product with a yield of 90.0%.
Example 2
Preparation of metallic Palladium Complex Polymer catalyst C1
Under an inert gas atmosphere, a 100mL reaction flask was charged with poly α -diimine ligand L1 (0.2 g, 1.5 mmol) prepared in example 1 and 50mL of dichloromethane, followed by addition of (PhCN)2PdCl2（0.58g，1.5 mmol) at-10 ℃ for 72 hours. After the reaction, the mixture was allowed to stand for delamination, and the precipitate was filtered, washed with anhydrous ether several times, and vacuum-dried to obtain 0.48g of brown metallic palladium complex polymer catalyst C1 with a yield of 91.6%.
Example 3
Catalysis of carbon-carbon coupling reaction by metal palladium complex polymer catalyst C1
Into a reaction flask were charged 0.43 g (2.5 mmol) of p-methylbromobenzene and 0.37 g (3mmol) of phenylboronic acid, 0.52g (3.75 mmol) of K2CO30.01 g of catalyst (C1), 6 mL of methanol is added to dissolve the catalyst, the reaction is carried out for 2 hours at 60 ℃, the cooling and the standing are carried out, the centrifugal separation is carried out, the liquid phase is separated by silica gel column chromatography (petroleum ether is used as eluent), the pure coupling product is obtained, 0.42 g is obtained, and the yield is 99%. The precipitate was used for secondary, tertiary, and more cycling reactions.
Example 4
Preparation of Poly-alpha-diimine ligand L2
2-methyl-1, 4-diaminobenzene (1.83 g, 15 mmol) and 70 mL of ethanol were added to a 250mL three-necked flask under an inert gas atmosphere, and butanedione (0.87 mL, 10 mmol) was added thereto at 80 ℃ and the reaction was stirred for 0.5 hour. The reaction solution was cooled in a refrigerator for crystallization, and the precipitated crystals were filtered to give a crude product, which was washed three times with acetone and dried under vacuum to give 1.04g of a product with a yield of 60.0%.
Example 5
Preparation of metallic Palladium Complex Polymer catalyst C2
Under an inert gas atmosphere, a 100mL reaction flask was charged with poly α -diimine ligand L2 (0.52 g, 3.0 mmol) prepared in example 3 and 50mL of dichloromethane, followed by addition of (PhCN)2PdCl2(0.58 g, 1.5 mmol) was reacted at 10 ℃ for 60 hours. Inverse directionAfter the reaction, the mixture was allowed to stand for separation, and the precipitate was filtered, washed with anhydrous ether several times, and vacuum-dried to obtain 0.53g of brown metallic palladium complex polymer catalyst C2 with a yield of 90.0%.
Example 6
Catalysis of carbon-carbon coupling reaction by metal palladium complex polymer catalyst C2
Into a reaction flask were charged 0.39 g (2.5 mmol) of bromobenzene and 0.46 g (3mmol) of p-methoxyphenylboronic acid, 0.52g (3.75 mmol) of K2CO30.01 g of catalyst (C1), 6 mL of isopropanol is added to dissolve the catalyst, the mixture reacts for 4 hours at 80 ℃, and then the mixture is cooled and stood, and then the mixture is centrifugally separated, and the liquid phase is separated by silica gel column chromatography (petroleum ether is used as eluent) to obtain pure coupling product, 0.46 g of the coupling product, and the yield is 99%. The precipitate was used for secondary, tertiary, and more cycling reactions.
Example 7
Preparation of Poly-alpha-diimine ligand L3
Under the protection of inert gas, o-nitro-p-phenylenediamine (3.06 g, 20 mmol) and 70 mL of isopropanol are added into a 250mL reaction bottle, and acenaphthenequinone (1.82 g, 10 mmol) is added at 0 ℃, and the reaction is stirred for 24 hours. The reaction solution was cooled in a refrigerator for crystallization, and the precipitated crystals were filtered to give a crude product, which was washed three times with diethyl ether and dried under vacuum to give 2.36g of a product in 79.0% yield.
Example 8
Preparation of metallic Palladium Complex Polymer catalyst C3
Under an inert gas atmosphere, a 100mL reaction flask was charged with poly α -diimine ligand L3 (1.35 g, 4.5 mmol) prepared in example 5 and 50mL of dichloromethane, followed by addition of (PhCN)2PdCl2(0.58 g, 1.5 mmol) at a temperature of 25 ℃ for 48 hours. Standing for layering after the reaction is finished, and filtering the precipitate for useWashing with anhydrous ether was conducted several times, and vacuum drying was conducted to obtain 0.67g of brown metallic palladium complex polymer catalyst C3 in a yield of 65.0%.
Example 9
Catalysis of carbon-carbon coupling reaction by metal palladium complex polymer catalyst C3
Into a reaction flask were charged 0.39 g (2.5 mmol) of p-methylbromobenzene and 0.41 g (3mmol) of p-methylbenzylboronic acid, 0.52g (3.75 mmol) of K2CO30.01 g of catalyst (C3), 6 mL of tetrahydrofuran is added to dissolve the catalyst, the reaction is carried out for 6 hours at the temperature of 40 ℃, the mixture is cooled and kept stand, centrifugal separation is carried out, and the liquid phase is separated by silica gel column chromatography (petroleum ether is used as eluent) to obtain pure coupling product, 0.45 g of the coupling product and the yield is 99%. The precipitate was used for secondary, tertiary, and more cycling reactions.
Example 10
Preparation of Poly-alpha-diimine ligand L4
2, 5-dichloro-1, 4-phenylenediamine (5.31 g, 30 mmol) and 70 mL of tert-butanol were added to a 250mL reaction flask under inert gas, 1-phenyl-1, 2-propanedione (1.48 g, 10 mmol) was added at 30 ℃ and the reaction was stirred for 24 hours. The reaction solution was cooled in a refrigerator for crystallization, and the precipitated crystals were filtered to give a crude product, which was washed three times with acetone and dried under vacuum to give 1.64g of a product in 56.7% yield.
Example 11
Preparation of metallic Palladium Complex Polymer catalyst C4
Under an inert gas atmosphere, a 100mL reaction flask was charged with poly α -diimine ligand L4 (1.19 g, 6.0 mmol) prepared in example 7 and 50mL of dichloromethane, followed by addition of (PhCN)2PdCl2(0.58 g, 1.5 mmol) at a temperature of 40 ℃ for 36 hours. Standing for layering after the reaction is finished, washing precipitates for a plurality of times by using anhydrous ether after the precipitates are filtered,drying in vacuo afforded 0.54g of brown metallic palladium complex catalyst C4 in 87.0% yield.
Example 12
Catalysis of carbon-carbon coupling reaction by metal palladium complex polymer catalyst C4
Into a reaction flask were charged 0.47 g (2.5 mmol) of p-methoxybromobenzene and 0.41 g (3mmol) of p-methylbenzylboronic acid, 0.52g (3.75 mmol) of K2CO30.01 g of catalyst (C4), 6 mL of dioxane is added, reaction is carried out for 8 hours at 100 ℃, cooling and standing are carried out, centrifugal separation is carried out, liquid phase is separated by silica gel column chromatography (petroleum ether is used as eluent), pure coupling product is obtained, 0.49 g is obtained, and the yield is 99%. The precipitate was used for secondary, tertiary, and more cycling reactions.
Example 13
Preparation of Poly-alpha-diimine ligand L5
Biphenyldiamine (9.2 g, 50 mmol) and 70 mL of methanol were added to a 250mL three-necked flask under an inert gas atmosphere, and butanedione (0.87 mL, 10 mmol) was added dropwise at 50 ℃ and the reaction was stirred for 6 hours. The reaction solution was cooled in a refrigerator for crystallization, and the precipitated crystals were filtered to give a crude product, which was washed three times with diethyl ether and dried under vacuum to give 1.38g of a product in 58.8% yield.
Example 14
Preparation of metallic Palladium Complex Polymer catalyst C5
Under an inert gas atmosphere, a 100mL reaction flask was charged with poly α -diimine ligand L5 (1.76 g, 7.5 mmol) prepared in example 9 and 50mL of dichloromethane, followed by addition of (PhCN)2PdCl2(0.58 g, 1.5 mmol) at a temperature of 50 ℃ for 6 hours. Standing for layering after the reaction is finished, filtering the precipitate, washing the precipitate for a plurality of times by using anhydrous ether, and drying the precipitate in vacuum to obtain 0.53g of brown metal palladium complex polymerReagent C5, yield 79.0%.
Example 15
Catalyzed carbon-carbon coupling with metallic palladium complex catalyst C5
Into a reaction flask were charged 0.72 g (2.5 mmol) of p-hexyliodobenzene and 0.54g (3mmol) of p-isopropoxyphenylboronic acid, 0.52g (3.75 mmol) of K2CO30.01 g of catalyst (C5), 6 mL of toluene is added, the mixture is reacted for 10 hours at 110 ℃, cooled and stood, the centrifugal separation is carried out, and the liquid phase is separated by silica gel column chromatography (petroleum ether is used as eluent) to obtain pure coupling product, 0.73 g, and the yield is 99%. The precipitate was used for secondary, tertiary, and more cycling reactions.
Example 16
Preparation of Poly-alpha-diimine ligand L6
Under the protection of inert gas, 5.65g of 2, 2-bis (4-aminophenyl) propane and 25mmol of ethanol in a 250mL three-neck flask are added, acenaphthenequinone (1.82 g and 10 mmol) is added at 60 ℃, and the reaction is stirred for 12 hours. The reaction solution was cooled in a refrigerator for crystallization, and the precipitated crystals were filtered to give a crude product, which was washed three times with acetone and dried under vacuum to give 2.541g of a product in 68.1% yield.
Example 17
Preparation of metallic Palladium Complex Polymer catalyst C6
Under an inert gas atmosphere, a 100mL reaction flask was charged with poly α -diimine ligand L6 (1.12 g, 3.0 mmol) prepared in example 5 and 50mL of dichloromethane, followed by addition of (PhCN)2PdCl2(0.58 g, 1.5 mmol) at a temperature of 60 ℃ for 1 hour. After the reaction, the mixture was allowed to stand for delamination, and the precipitate was filtered, washed with anhydrous ether several times, and vacuum-dried to obtain 0.52g of brown metallic palladium complex polymer catalyst C6 with a yield of 63.0%.
Example 18
Catalyzed carbon-carbon coupling with metallic palladium complex catalyst C6
Into a reaction flask were charged 0.39 g (2.5 mmol) of p-cyanoborobenzene and 0.49 g (3mmol) of p-propylphenylboronic acid, 0.52g (3.75 mmol) of K2CO30.01 g of catalyst (C6), 6 mL of dimethylformamide is added, reaction is carried out for 4 hours at 120 ℃, cooling and standing are carried out, centrifugal separation is carried out, and the liquid phase is separated by silica gel column chromatography (petroleum ether is used as eluent) to obtain pure coupling product, 0.55 g of coupling product, and the yield is 99%. The precipitate was used for secondary, tertiary, and more cycling reactions.
Examples 19 to 24
The reaction procedures of examples 3, 6, 9, 12, 15 and 18 were followed in various organic solvents with catalysts C1, C2, C3, C4, C5 and C6, respectively, for multiple cycles of carbon-carbon coupling reactions, and the results are shown in Table 1.
TABLE 1 results of multiple cycles of carbon-carbon coupling reactions in different catalysts and solvents
| Examples of the invention | Catalyst and process for preparing same | Solvent(s) | Number of cycles/reaction temperature (. degree. C.) | Yield (%) |
| Example 19 | C1 | Ethanol | 10 / 78 | 88.2 |
| Example 20 | C2 | Butanol | 10 / 117 | 89.1 |
| Example 21 | C3 | Isopropanol (I-propanol) | 12 / 83 | 92.5 |
| Example 22 | C4 | Ethyl acetate | 10 / 77 | 87.0 |
| Example 23 | C5 | Triethylamine | 8 / 90 | 85.3 |
| Example 24 | C6 | Toluene | 5 / 110 | 90.1 |
Claims (6)
1. A method for catalyzing carbon-carbon coupling reaction by using a metal palladium coordination polymer catalyst is characterized by comprising the following steps: halogenated aromatic hydrocarbon (IV) and phenylboronic acid (V)) Dissolving the catalyst in organic solvent of alcohol, ester, arene or amine, reacting at 40-120 deg.C for 2-10 hr, cooling, laying aside, centrifugal separation, chromatographic separation of liquid phase by silica gel column, eluting with petroleum ether to obtain pure coupled product, and using the precipitate as K alkali for secondary, tertiary and secondary cyclic reactions2CO3、Na2CO3、K3PO4、Na3PO4Or CH3ONa, wherein the organic solvent in the carbon-carbon coupling reaction is one of monohydric alcohol of C1-C6, ethyl acetate, toluene, dimethylformamide and triethylamine;
in the formula: x is Br or I; r5 and R6 are respectively selected from one of H, C1-C6 alkyl or C1-C6 alkoxy and CN;
the structure of the metal palladium coordination polymer catalyst has the following general formula:
or
（II）
Or
In the formulas (I), (II) and (III), R is hydrogen, C1-C12 alkyl, C6-C12 aryl and acenaphthenyl
(ii) a R in the formula (I)1，R2，R3And R4The same or different hydrogen, C1-C12 alkyl, halogen, nitro, C6-C12Aryl of (a); in the formula (III), R' is methylene, methylene substituted by C1-C12 alkyl, methylene substituted by C1-C12 haloalkyl; x is halogen;
the preparation method of the metal palladium complex catalyst comprises the steps of firstly, under the protection of inert gas, dissolving an aromatic diamine compound and an α -dialdehyde or ketone compound in an organic solvent, enabling the aromatic diamine compound and α -dialdehyde or ketone to react for 0.5-48 hours at the temperature of 0-80 ℃, placing the reactant into a refrigerator for crystallization after the reaction, washing the crystal with the organic solvent after the crystal is filtered, drying in vacuum to obtain a poly α -diimine complex, and then, mixing the poly α -diimine complex with (PhCN)2PdCl2Soluble in organic solvents, poly α -diimine ligands and (PhCN)2PdCl2The molar ratio of (A) to (B) is 1-5: 1, reacting at the temperature of-10-60 ℃ for 1-72 hours, standing for layering after the reaction is finished, filtering and vacuum drying precipitates to obtain the metal palladium complex polymer catalyst, wherein an organic solvent in the preparation method of the metal palladium complex polymer catalyst is one of aromatic hydrocarbon, halogenated hydrocarbon, alcohol and ether solvents.
2. The method for catalyzing carbon-carbon coupling reaction by using the metal palladium complex polymer catalyst as claimed in claim 1, wherein R in the structural formula (I), (II) and (III) of the metal palladium complex polymer catalyst is hydrogen, alkyl of C1-C4, phenyl, acenaphthylene
(ii) a R in the formula (I)1，R2，R3And R4Hydrogen, C1-C4 alkyl, halogen, nitro, phenyl and biphenyl; in the formula (III), R' is methylene, methylene substituted by C1-C4 alkyl, methylene substituted by C1-C4 fluorine-containing alkyl; x is chlorine or bromine.
3. The method for catalyzing carbon-carbon coupling reaction with a metal palladium complex catalyst according to claim 1 or 2, wherein the molar ratio of the aromatic diamine compound to the α -dialdehyde or ketone in the preparation method of the metal palladium complex catalyst is 1 to 3: 1, reacting for 3-24 hours at the temperature of 10-60 ℃.
4. The method of claim 1, wherein the palladium metal complex catalyst is prepared by reacting poly α -diimine ligand with (PhCN)2PdCl2The molar ratio of (A) to (B) is 1-3: 1, reacting for 6-48 hours at the temperature of 10-50 ℃.
5. The method of claim 1, wherein the organic solvent is one of benzene, toluene, chloroform, dichloromethane, methanol, ethanol, and diethyl ether.
6. The method of claim 1, wherein the aryl halide (IV) and the phenylboronic acid (V) have the formula R5 and R6 respectively selected from the group consisting of H, C1-C3 alkyl, C1-C3 alkoxy and CN.
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| "Synthesis of late transition nickel(Ⅱ) coordination polymer and their catalysis for olefinic polymerization";Xu Chenfei，et al;《IOP Conf. Series: Materials Science and Engineering》;20170919;第231卷;第1-5页 * |
| Xu Chenfei，et al."Synthesis of late transition nickel(Ⅱ) coordination polymer and their catalysis for olefinic polymerization".《IOP Conf. Series: Materials Science and Engineering》.2017,第231卷第1-5页. * |
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| CN107930695A (en) | 2018-04-20 |
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