Preparation method and application of amphiphilic phosphine-containing porous organic copolymer supported palladium metal catalyst
By developing an amphiphilic porous organic copolymer-supported palladium metal catalyst, the problems of catalyst deactivation and contaminants in heterogeneous catalytic alkyne hydrogen carboxylation reaction are solved, and efficient and recyclable catalytic effect is achieved.
Patent Information
- Application Number
- CN202510216679.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-26
- Publication Date
- 2025-05-30
AI Technical Summary
There are problems of catalyst deactivation and contaminants in heterogeneous catalytic alkyne hydrogen carboxylation reaction, and few studies on porous organic polymer-supported metal catalysts are studied.
A class of amphiphilic porous organic copolymer-supported palladium metal catalysts were developed, and the catalyst was prepared by polymerization and applied in alkyne hydrogen carboxylation reaction.
This catalyst exhibits high activity, good yield and recyclability in alkyne hydrogen carboxylation reaction, solving the problems of catalyst deactivation and contaminants.
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Figure CN120059050A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a preparation method and application of a class of amphiphilic phosphine-containing porous organic copolymer supported palladium metal catalysts. Specifically, it relates to a class of porous polymers containing polyphosphine ligands and a preparation method thereof. The polymer supported palladium metal catalyst can efficiently catalyze the hydrocarboxylation reaction of alkynes, belonging to the technical field of organic chemistry. Technical Background
[0002] The hydrocarboxylation reaction of alkynes refers to the process in which alkynes use water as a carbonyl source and react in the presence of CO to form α,β-unsaturated fatty acids. As an important organic synthesis intermediate, α,β-unsaturated fatty acids have important medicinal values, especially important applications in the construction of heterocyclic compounds, and can also be used for the synthesis of ligands. Using water as the carbonyl source and in the presence of CO, the palladium metal-catalyzed hydrocarboxylation reaction of alkynes provides a class of green synthesis methods for the synthesis of α,β-unsaturated fatty acids. Compared with the hydrocarboxylation reaction of homogeneous catalytic systems, the hydrocarboxylation reaction of heterogeneous catalytic systems has greater research value. However, in the hydrocarboxylation reaction of heterogeneous catalytic systems, there are relatively few studies on the synthesis of porous organic polymers as ligands and the loading of metals in porous organic polymers to catalyze the hydrocarboxylation reaction of alkynes. As an organic ligand carrier, porous organic polymer supported metal catalysts have the advantages of porosity, high specific surface area, stable chemical properties and easy recovery. Developed to date, there are still many difficulties to overcome in the heterogeneous catalytic hydrocarboxylation reaction: First, most heterogeneous reaction systems have the problem of catalyst deactivation during the recycling process; Second, a large number of metal organic reagents produce a large amount of pollutants. Therefore, based on the above problems, this patent has successfully developed a class of heterogeneous catalysts constructed by amphiphilic phosphine-containing porous organic copolymer supported palladium metal catalysts, which show high activity, good yield and recyclability in the hydrocarboxylation reaction of alkynes and have practical value. Summary of the Invention
[0003] The purpose of the present invention is to provide a preparation method and application of a class of amphiphilic phosphine-containing porous organic copolymer supported palladium metal catalysts, adding a new class of catalysts for the heterogeneous catalytic hydrocarboxylation reaction of alkynes.
[0004] A class of amphiphilic phosphine-containing porous organic copolymer supported palladium metal catalysts described in the present invention has the following general structural formula I:
[0005]
[0006] In the above general formula: R 1 、R 2 、R 3 、R 4 、R 5 、R 6, R 7 , R 8 , R 9 are each independently selected from hydrogen, sulfonic acid group, halogen, nitrile group, C 1 -C 12 alkyl group, C 1 -C 10 alkanoyl group, C 1 -C 10 ester group, C 1 -C 10 sulfonic acid ester group;
[0007] The l:n:m ratio is 1:1:1 to 1:20:100.
[0008] The above-mentioned amphiphilic phosphine-containing porous organic copolymer is characterized in that: Polymer I is obtained by the polymerization reaction of Compound 1, Compound 2 and Compound 3, and the reaction general formula (1) is as follows:
[0009]
[0010] In the general formula (1), Compound 1 is obtained by reacting Compound 4 with p-vinylbenzyl chloride The reaction is as follows: The reaction general formula (2) is as follows:
[0011]
[0012] R in the above general formula 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 has the same meaning as that described in Claim 1.
[0013] The amphiphilic phosphine-containing porous organic copolymer-supported palladium metal catalyst described in the present invention is an application for catalyzing the hydrocarboxylation reaction of alkynes.
[0014] As a further preferred embodiment, the preparation of the above catalyst includes the following steps: Under an inert gas, the porous organic polymer containing the amphiphilic phosphine ligand and the transition metal salt are added to an organic solvent, and stirred and reacted at 0-100 °C for 0.1-24 hours, and the solvent is removed to obtain an amphiphilic phosphine-containing porous organic copolymer / palladium metal salt catalyst.
[0015] As an even more preferred embodiment, the mass ratio of the amphiphilic phosphine-containing porous organic copolymer to the metal salt is 1:1 to 500:1 respectively.
[0016] As a further preferred embodiment, the palladium salt is Pd(OAc) 2 , PdCl 2 , PdBr 2 , PdI 2 .
[0017] As a further preferred embodiment, the inert atmosphere is an argon atmosphere or a nitrogen atmosphere; the organic solvent is selected from benzene, toluene, xylene, mesitylene, ether, tetrahydrofuran, N,N-dimethylformamide, N-methylpyrrolidone, methyl tert-butyl ether, ethylene glycol dimethyl ether, chloroform, dichloromethane.
[0018] As a further preferred embodiment, an alkyne substrate and CO are added to a reaction kettle containing a catalyst, and a hydrocarboxylation reaction is carried out under the condition of 0 to 200 °C; the alkyne substrate is diphenylacetylene and its derivatives with other functional groups; the molar ratio of the alkyne substrate to Pd in the catalyst is 2:1 to 200:1; the CO pressure is 1 to 10 atmospheres.
[0019] Compared with the prior art, the present invention has the following remarkable effects:
[0020] 1. The amphiphilic phosphine-containing porous organic copolymer supported palladium metal catalyst provided by the present invention has high catalytic activity and recyclability for the hydrocarboxylation reaction of alkynes.
[0021] 2. The preparation method of the amphiphilic phosphine-containing porous organic copolymer supported palladium metal catalyst provided by the present invention is simple, the reaction conditions are mild, the yield is high, it is suitable for large-scale production, and has practical value. Specific Embodiments
[0022] The present invention will be further described in detail and completely below in conjunction with embodiments.
[0023] Example 1
[0024] Synthesis of Compound 1: Under an ice-water bath, compound (110 mg) and DMF (10 mL) were added to a Schlenk tube, and finally NaH (30 mg) was added in batches, and the reaction was carried out at 70 °C for 1.5 h. After cooling to room temperature, 4-vinylbenzyl chloride was added to the reaction The reaction was carried out at 60 °C for 18 h. The product was washed 3 times with petroleum ether and air-dried to obtain a green solid (115 mg).
[0025] Example 2
[0026] Synthesis of the amphiphilic phosphine-containing porous organic copolymer 1 supported palladium metal catalyst I / Pd.
[0027] Under nitrogen protection, 100 mL of Schlenk tube was respectively added with compound 1 (35 mg), trivinyltriphenylphosphine (89 mg), sodium p-toluenesulfonate (11 mg), AIBN (5 mg), and THF (10 mL). It was heated to 100 °C and reacted for 24 hours. After the reaction was completed, the white solid product polymer I was obtained by centrifugation.
[0028] Under nitrogen atmosphere, 100 mL of Schlenk tube was respectively added with polymer 1 (100 mg), Pd(OAc) 2 (8 mg), and tetrahydrofuran (5 mL). It was reacted at 100 °C for 24 h, and the reaction product was washed with petroleum ether and then centrifuged. Such centrifugation and washing were carried out 3 times. Finally, the petroleum ether was removed by rotary evaporation under reduced pressure, and then pumped with an oil pump for 3 h to obtain catalyst I / Pd (105 mg).
[0029] Example 3
[0030] Hydrocarboxylation reaction of diphenylacetylene catalyzed by catalyst I / Pd (substrate: catalyst = 50)
[0031] Under nitrogen atmosphere, catalyst I / Pd (14.6 mg), H 2 O (2 mL), and diphenylacetylene (89 mg) were added to the reaction kettle. Then, CO was charged to replace the nitrogen in the Schlenk tube three times, and then CO (1 atm) was charged. The reaction was stirred at 110 °C in an oil bath for 24 h. After the reaction was completed, the product was collected by column chromatography purification, and the yield was 96%. The characterization data of 1H NMR spectrum: 1 1H NMR (CDCl 3 , 500 MHz): δ 7.88 (s, 1H), 7.31 - 7.29 (m, 3H), 7.18 - 7.15 (m, 3H), 7.11 - 7.08 (m, 2H), 7.01 - 6.99 (m, 2H) ppm.
[0032] Example 4
[0033] Hydrocarboxylation reaction of 1,2-bis(3-methylphenyl)acetylene catalyzed by catalyst I / Pd (substrate: catalyst = 50)
[0034] Under nitrogen atmosphere, catalyst I / Pd (14.6 mg), H 2 O (2 mL), and 1,2-bis(3-methylphenyl)acetylene (103 mg) were added to the reaction kettle. Then, CO was charged to replace the nitrogen in the Schlenk tube three times, and then CO (1 atm) was charged. The reaction was stirred at 110 °C in an oil bath for 24 h. After the reaction was completed, the product was collected by column chromatography purification, and the yield was 92%.
[0035] Example 5
[0036] Hydrocarboxylation reaction of 1,2-bis(4-methoxyphenyl)acetylene catalyzed by Catalyst I / Pd (substrate:catalyst = 50)
[0037] Under a nitrogen atmosphere, Catalyst I / Pd (14.6 mg), H 2 O (2 mL), and 1,2-bis(4-methoxyphenyl)acetylene (119 mg) were added to the reaction kettle. Then, CO was introduced to displace the nitrogen in the Schlenk tube three times, and then CO (1 atm) was introduced. The reaction was stirred at 110 °C in an oil bath for 24 h. After the reaction was completed, the product was collected by column chromatography purification, and the yield was 85%.
[0038] Example 6
[0039] Hydrocarboxylation reaction of 1,2-bis(3-formylphenyl)acetylene catalyzed by Catalyst I / Pd (substrate:catalyst = 50)
[0040] Under a nitrogen atmosphere, Catalyst I / Pd (14.6 mg), H 2 O (2 mL), and 1,2-bis(3-formylphenyl)acetylene (117 mg) were added to the reaction kettle. Then, CO was introduced to displace the nitrogen in the Schlenk tube three times, and then CO (1 atm) was introduced. The reaction was stirred at 110 °C in an oil bath for 24 h. After the reaction was completed, the product was collected by column chromatography purification, and the yield was 80%.
[0041] Example 7
[0042] Hydrocarboxylation reaction of 1,2-bis(2-furyl)acetylene catalyzed by Catalyst I / Pd (substrate:catalyst = 50)
[0043] Under a nitrogen atmosphere, Catalyst I / Pd (14.6 mg), H 2 O (2 mL), and 1,2-bis(furyl)acetylene (79 mg) were added to the reaction kettle. Then, CO was introduced to displace the nitrogen in the Schlenk tube three times, and then CO (1 atm) was introduced. The reaction was stirred at 110 °C in an oil bath for 24 h. After the reaction was completed, the product was collected by column chromatography purification, and the yield was 94%.
[0044] Example 8
[0045] Hydrocarboxylation reaction of 1,2-bis(2-thienyl)acetylene catalyzed by Catalyst I / Pd (substrate:catalyst = 50)
[0046] Under a nitrogen atmosphere, Catalyst I / Pd (14.6 mg), H 2 O (2 mL), and 1,2-bis(2-thienyl)acetylene (95 mg) were added to the reaction kettle. Then, CO was introduced to displace the nitrogen in the Schlenk tube three times, and then CO (1 atm) was introduced. The reaction was stirred at 110 °C in an oil bath for 24 h. After the reaction was completed, the product was collected by column chromatography purification, and the yield was 93%.
[0047] Example 9
[0048] Hydrocarboxylation of 2-phenylethynylnaphthalene (substrate: catalyst = 50) catalyzed by Catalyst I / Pd
[0049] Under a nitrogen atmosphere, add Catalyst I / Pd (14.6 mg), H 2 O (2 mL), and 2-phenylethynylnaphthalene (114 mg) to the reaction kettle. Then fill with CO to displace the nitrogen in the Schlenk tube three times, and then fill with CO (1 atm). Stir and react at 110 °C in an oil bath for 24 h. After the reaction is completed, purify the product by column chromatography and collect the product, with a yield of 87%.
[0050] Example 10
[0051] Hydrocarboxylation of 1-methyl-3-phenylethynylbenzene (substrate: catalyst = 50) catalyzed by Catalyst I / Pd
[0052] Under a nitrogen atmosphere, add Catalyst I / Pd (14.6 mg), H 2 O (2 mL), and 1-methyl-3-phenylethynylbenzene (96 mg) to the reaction kettle. Then fill with CO to displace the nitrogen in the Schlenk tube three times, and then fill with CO (1 atm). Stir and react at 110 °C in an oil bath for 24 h. After the reaction is completed, purify the product by column chromatography and collect the product, with a yield of 88%.
[0053] Example 11
[0054] Hydrocarboxylation of 1-methyl-2-phenylethynylbenzene (substrate: catalyst = 50) catalyzed by Catalyst I / Pd
[0055] Under a nitrogen atmosphere, add Catalyst I / Pd (14.6 mg), H 2 O (2 mL), and 1-methyl-2-phenylethynylbenzene (96 mg) to the reaction kettle. Then fill with CO to displace the nitrogen in the Schlenk tube three times, and then fill with CO (1 atm). Stir and react at 110 °C in an oil bath for 24 h. After the reaction is completed, purify the product by column chromatography and collect the product, with a yield of 83%.
[0056] Example 12
[0057] Hydrocarboxylation of 1-phenyl-1-propyne (substrate: catalyst = 50) catalyzed by Catalyst I / Pd
[0058] Under a nitrogen atmosphere, add Catalyst I / Pd (14.6 mg), H 2O (2 mL), 1-phenyl-1-propyne (58 mg). Then, nitrogen in the Schlenk tube was replaced with CO three times, and then CO (1 atm) was charged. The reaction was stirred at 110 °C in an oil bath for 24 h. After the reaction was completed, the product was collected by column chromatography purification, and the yield was 93%.
[0059] Example 13
[0060] Hydrocarboxylation reaction of 1-phenyl-1-butyne catalyzed by catalyst I / Pd (substrate:catalyst = 50)
[0061] Under a nitrogen atmosphere, catalyst I / Pd (14.6 mg), H 2 O (2 mL), 1-phenyl-1-butyne (65 mg) were added to the reaction kettle. Then, nitrogen in the Schlenk tube was replaced with CO three times, and then CO (1 atm) was charged. The reaction was stirred at 110 °C in an oil bath for 24 h. After the reaction was completed, the product was collected by column chromatography purification, and the yield was 95%.
[0062] Example 14
[0063] Hydrocarboxylation reaction of phenylacetylene catalyzed by catalyst I / Pd (substrate:catalyst = 50)
[0064] Under a nitrogen atmosphere, catalyst I / Pd (14.6 mg), H 2 O (2 mL), phenylacetylene (51 mg) were added to the reaction kettle. Then, nitrogen in the Schlenk tube was replaced with CO three times, and then CO (1 atm) was charged. The reaction was stirred at 110 °C in an oil bath for 24 h. After the reaction was completed, the product was collected by column chromatography purification, and the yield was 76%.
[0065] Example 15
[0066] Hydrocarboxylation reaction of 2-pentyne catalyzed by catalyst I / Pd (substrate:catalyst = 50)
[0067] Under a nitrogen atmosphere, catalyst I / Pd (14.6 mg), H 2 O (2 mL), 2-pentyne (34 mg) were added to the reaction kettle. Then, nitrogen in the Schlenk tube was replaced with CO three times, and then CO (1 atm) was charged. The reaction was stirred at 110 °C in an oil bath for 24 h. After the reaction was completed, the product was collected by column chromatography purification, and the yield was 86%.
[0068] Example 16
[0069] Hydrocarboxylation reaction of diphenylacetylene catalyzed by catalyst I / Pd (substrate:catalyst = 50)
[0070] Under a nitrogen atmosphere, catalyst I / Pd (14.6 mg), H 2O (2 mL), diphenylacetylene (89 mg). Then, the Schlenk tube was purged with CO three times to displace the nitrogen inside, and then filled with CO (1 atm), and stirred at 110 °C in an oil bath for 24 h. After the reaction was completed, the catalyst was recycled, and the product was purified and collected by column chromatography, and the yield was calculated. The catalyst was washed 3 times with petroleum ether, the solvent was dried by evaporation and vacuum dried, and then recycled 6 times under the same reaction conditions. The specific test data are as follows:
[0071]
[0072] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, for those of ordinary skill in the art, it is still possible to modify the technical solutions described in the foregoing embodiments, or to equivalently replace some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions required to be protected by the present invention.
Claims
1. A type of amphiphilic phosphine-containing porous organic copolymer having the following structural formula I: In the above general formula: R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are independently selected from hydrogen, sulfonic acid, halogen, nitrile, C1-C 12 Alkyl, C1~C 10 Alkanoyl, C1~C 10 Ester group, C1~C 10 Sulfonate group; The ratio of l:n:m is 1:1:1 to 1:20:
100.
2. The amphiphilic phosphine-containing porous organic copolymer according to claim 1, characterized in that: Polymer I is obtained by polymerization reaction of compound 1, compound 2 and compound 3, and the general reaction formula (1) is as follows: The compound 1 in the general formula (1) is prepared by reacting compound 4 with p-vinylbenzyl chloride The reaction is carried out to obtain; the general reaction formula (2) is shown as follows: In the above general formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 The meanings are the same as those in claim 1.
3. An application of the amphiphilic phosphine-containing porous organic copolymer according to claim 1, characterized in that: Used to catalyze the hydrocarboxylation of alkynes.
4. The use according to claim 3, characterized in that: A class of amphiphilic phosphine-containing copolymers are combined with transition metal salts to form I / Pd catalysts, which are then used to catalyze the hydrocarboxylation of alkynes.
5. The use according to claim 4, characterized in that: The preparation of I / Pd catalyst includes the following steps: under inert gas, a class of amphiphilic phosphine-containing porous organic copolymers and Pd(OAc)2 metal salts are added to tetrahydrofuran in a mass ratio of 1:1 to 500:1, stirred and reacted at 0 to 100°C for 0.1 to 20 hours, and the solvent is removed to obtain the I / Pd catalyst.
6. The use according to claim 4, characterized in that: The operation of using I / Pd catalyst to catalyze the hydrocarboxylation reaction of alkynes is as follows: under an inert atmosphere, add alkyne substrate and CO into a reaction kettle containing the catalyst, and react at 0-300°C.