CN113680379B - A kind of preparation method and application of microporous material supported copper catalyst - Google Patents

Abstract

The invention relates to a preparation method and application of a microporous material loaded copper catalyst, which comprises the steps of firstly, uniformly mixing DY-32 zeolite, sodium hydroxide, a template agent, water and seed crystals in an agate mortar, carrying out crystal transformation in an oven, washing and calcining a product to obtain Na-type SSZ-39 zeolite, and carrying out ion exchange to obtain H-type SSZ-39 zeolite; and carrying out incipient wetness impregnation on the H-SSZ-39 zeolite by using a copper salt solution, naturally drying in the shade, then drying in vacuum, and then roasting to obtain the microporous material loaded copper catalyst Cu/H-SSZ-39, wherein the microporous material loaded copper catalyst can be applied to catalytic decarboxylation coupling reaction. The catalyst has the advantages of high activity, easy separation, good stability, high activity, long service life, less metal residue, simple operation and simple equipment requirement; the catalyst has high activity after being recycled for many times, and has the advantages of economy, high efficiency, environmental protection and the like.

Description

A kind of preparation method and application of microporous material supported copper catalyst

technical field

The invention belongs to the technical field of organometallic catalysis, and in particular relates to a preparation method of a microporous material-loaded copper catalyst and its application in catalytic decarboxylation coupling reactions.

Background technique

Decarboxylation cross-coupling is a very important method for the flexible construction of C-C bond compounds in modern organic chemical synthesis. α-Acylated ethers are important molecular fragments that can be used in the preparation of various bioactive products and pharmaceutical intermediates. Previously reported synthesis methods mainly use homogeneous noble metals as catalysts, and their high price and difficult recycling of toxic ligands limit their industrial applications. Therefore, heterogeneous transition metal-supported catalysts have attracted much attention.

In recent years, the development of transition metal-catalyzed organic synthesis just caters to the needs of this era, and the preparation of cheap, efficient, and non-toxic supported metal catalysts is the focus and difficulty of promoting the development of this field. As a kind of cheap, easy-to-obtain and non-toxic porous materials, zeolite compounds are ideal raw materials for the synthesis of organometallic catalyst supports. Heterogeneous reactions have many advantages over homogeneous reactions. For example, after the reaction is complete, the separation of the catalyst and the product is simple, it can be recycled, the cost is greatly reduced, and the stereoselectivity of the reaction can be better controlled during the reaction. After seeing these huge advantages, scientific researchers have devoted themselves to the design and synthesis of various catalyst supports, and loaded homogeneous catalysts on various supports. Common carriers include silica, biomass, magnetic materials and polymers, etc. Zeolite is a kind of green and environmentally friendly porous material. s concern.

Contents of the invention

The object of the present invention is to provide a preparation method of microporous material supported copper catalyst and its application in catalytic decarboxylation coupling reaction. The catalyst of the present invention can be used for highly selective decarboxylation to prepare Csp ² -Csp ³ coupling compound.

A preparation method of microporous material supported copper catalyst, comprising the steps of:

(1) In an agate mortar, mix DY-32 zeolite, sodium hydroxide, template agent, water and seed crystals evenly and turn crystallization (crystallization) in an oven. The product is washed and calcined to obtain Na-type SSZ-39 zeolite. Exchange to obtain H-type SSZ-39 zeolite;

(2) The H-SSZ-39 zeolite was impregnated with a copper salt solution, dried in the shade, vacuum-dried, and calcined to obtain a microporous material supported copper catalyst Cu/H-SSZ-39.

Preferably, the template agent is N,N-dimethyl-3,5-dimethylpiperidine hydroxide solution, and the seed crystal is H-SSZ-39 seed crystal.

Preferably, the mass ratio of DY-32 zeolite, sodium hydroxide and template agent is 1:0.115-0.135:0.85-1.05. More preferably, the mass ratio of DY-32 zeolite, sodium hydroxide and template agent is 1:0.125:0.95.

Preferably, the crystal transformation temperature in step (1) is 120-160°C, and the crystal transformation time is 2-4 days; the vacuum drying temperature in step (2) is 60-120°C, the drying time is 8-16 hours, and the roasting temperature is 300～600℃. More preferably, the vacuum drying temperature is 100°C, the drying time is 12 hours, and the calcination temperature is 450°C.

As preferably, the copper salt is one of copper acetate, copper sulfate, copper nitrate, copper chloride; more preferably, the copper salt is copper nitrate; the copper salt solution is copper salt solution, copper salt solution ethanol solution, or copper salt methanol solution.

As preferably, the preparation method of the microporous material supported copper catalyst comprises the following steps:

(1) Add 1g DY-32 zeolite to an agate mortar, add 0.95g N,N-dimethyl-3,5-dimethylpiperidine hydroxide solution, and grind evenly; add 0.05g to the mixture to Ionized water, grind evenly; add 0.125g granular sodium hydroxide to the mixture, grind evenly; add 0.02g H-SSZ-39 zeolite seed crystals to the mixture, grind evenly; transfer the mixture to a hydrothermal kettle, crystallize at 150℃ 3 days; the product was calcined at 550°C for 4 hours; the obtained product was ion-exchanged twice at 80°C in 1M ammonium nitrate solution to obtain the H-type product H-SSZ-39-0.95 zeolite;

(2) Add H-SSZ-39-0.95 zeolite into the beaker, slowly add copper nitrate solution dropwise until the zeolite is completely wet, and dry in the shade; transfer to a vacuum oven at 100°C for 12 hours; crush the catalyst solid and put it in a porcelain boat , heated at 5°C per minute, and fired at 450°C for 3 hours to obtain Cu/H-SSZ-39.

The preparation route of the microporous material-supported copper catalyst (Cu/H-SSZ-39) of the present invention is shown in FIG. 1 .

The present invention also provides the application of the microporous material supported copper catalyst in catalyzing decarboxylation coupling reaction.

As preferably, the application of the above-mentioned microporous material-loaded copper catalyst in the catalytic decarboxylation coupling reaction adopts the following method: add benzoylformic acid, microporous material-loaded copper catalyst, ether compounds and tert-butyl peroxide to the reactor. Hydrogen oxide, after vacuuming, nitrogen gas, decarboxylation coupling reaction under heating conditions for 1.5 to 3 hours; after the reaction, the reaction solution was cooled to room temperature, filtered, and the solvent was evaporated to obtain the decarboxylation coupling product.

In the invention, benzoylformic acid is used as a raw material, the microporous material is loaded with a copper catalyst, and a liquid ether compound is used as a solvent, and the benzoylmethine ether compound is synthesized through Csp ² -Csp ³ decarboxylation coupling at reflux temperature.

Preferably, the molar ratio of benzoylformic acid to the microporous material-supported copper catalyst is 100:5-25. More preferably, the molar ratio of the benzoylformic acid and the copper catalyst supported by the microporous material is 100:10.

Preferably, the amount/volume ratio of benzoylformic acid and ether compounds is 1:1-4; more preferably 1:3, for example, 1 mmol:3 mL.

Preferably, the decarboxylation coupling reaction temperature is 80-170°C. A more preferred reaction temperature is 120°C.

The route of Cu/H-SSZ-39 catalytic decarboxylation coupling of the present invention to synthesize benzoyl methine ether compound is as follows:

Compared with the prior art, the beneficial effects of the present invention are:

The catalyst of the present invention has high activity, easy separation, good stability, high activity, long service life, less metal residue, simple operation, and simple equipment requirements; and the catalyst of the present invention has high activity for repeated use, and is economical, efficient, and environmentally friendly. advantage.

Description of drawings

Fig. 1 is the preparation roadmap of zeolite supported copper catalyst (Cu/H-SSZ-39) of the present invention;

Fig. 2 is the ¹ H NMR spectrogram of the product 2-(1,4-dioxane) benzophenone prepared by the present invention;

Fig. 3 is the ¹³ C NMR spectrogram of the product 2-(1,4-dioxane) benzophenone prepared by the present invention;

Fig. 4 is the ¹ H NMR spectrogram of the product 2,3-dimethoxyphenylacetone prepared by the present invention;

Fig. 5 is a catalytic effect diagram after the catalyst of the present invention is recycled for 5 times.

Detailed ways

The invention will be further described below in conjunction with specific embodiments, but the protection scope of the invention is not limited thereto. Those skilled in the art can and should know that any simple changes or substitutions based on the essence and spirit of the present invention shall fall within the scope of protection required by the present invention.

Example 1

Synthesis of H-SSZ-39

Add and grind 1g DY-32, 0.95g DMDMPOH, 0.05g deionized water, 0.125g granular sodium hydroxide, and 0.02g H-SSZ-39 seed crystals in an agate mortar in sequence. The mixture was placed in a hydrothermal kettle and crystallized at 140°C for 3 days. After the product was washed and dried, it was calcined at 550°C to obtain Na-SSZ-39. The obtained product was ion-exchanged twice at 80°C in 1M ammonium nitrate solution to obtain the hydrogen form product H-SSZ-39.

Preparation of Cu/H-SSZ-39-300(400, 450, 500)-A

Add H-SSZ-39 zeolite into the beaker, slowly add copper nitrate salt aqueous solution dropwise until the zeolite is completely wet, then dry it in the shade naturally, and transfer it to a vacuum oven at 100°C for 12 hours. Grind the catalyst solid into a porcelain boat, raise the temperature at 5°C per minute, and bake at 300°C, 400°C, 450°C, and 500°C for 3 hours to obtain catalysts Cu/H-SSZ-39-300-A, Cu/H - SSZ-39-400-A, Cu/H-SSZ-39-450-A, Cu/H-SSZ-39-500-A.

Example 2

Preparation of Cu/H-SSZ-39-400-E

Add H-SSZ-39 zeolite into a beaker, slowly add copper nitrate ethanol solution dropwise until the zeolite is completely wet, then dry it in the shade naturally, and transfer it to a vacuum oven at 100°C for 12 hours. Grind the catalyst solid into a porcelain boat, raise the temperature at 5°C per minute, and bake at 400°C for 3 hours to obtain the catalyst Cu/H-SSZ-39-400-E.

Example 3

Add benzoylformic acid (25mmol, 3.753g), Cu/H-SSZ-39-450-A (10mol%, 0.3g), 1,4-dioxane (75mL) in a 150mL round bottom flask, and use After ultrasonic mixing, tert-butyl hydroperoxide (37.5 mmol, 3.380 g) was added. Install a thorn-shaped fractionating column and a three-way pipe, and heat to reflux at 120° C. for 3 hours under the protection of nitrogen. After the reaction control is completed, cool the reaction liquid to room temperature, filter the catalyst, add excess lye to neutralize benzoylformic acid in the filtrate, extract the mixed liquid with ethyl acetate, take the organic phase, and remove the organic solvent with a rotary evaporator , to obtain the product 2-(1,4-dioxane)benzophenone, the yield is 98%, and ^{the 1} H NMR spectrum of the product 2-(1,4-dioxane)benzophenone is shown in Figure 2 As shown, the ¹³ C NMR spectrum is shown in FIG. 3 .

¹ H NMR (400MHz,DMSO-d ₆ )δ8.05–8.01(m,2H),7.72–7.67(m,1H),7.56(t,J＝7.7Hz,2H),6.03(s,1H), 4.05(ddd, J＝3.2, 10.3, 11.6Hz, 1H), 3.78(dt, J＝2.3, 19.0Hz, 3H), 3.74–3.68(m, 1H), 3.63(dt, J＝2.4, 11.7Hz, 1H).

¹³ C NMR (101 MHz, DMSO-d ₆ ) δ 164.44, 133.69, 129.44, 129.34, 128.85, 89.59, 67.06, 65.37.

Example 4

Add benzoylformic acid (25mmol, 3.753g), Cu/H-SSZ-39-400-A (10mol%, 0.3g), 1,4-dioxane (75mL) in a 150mL round bottom flask, and use After ultrasonic mixing, tert-butyl hydroperoxide (37.5 mmol, 3.380 g) was added. Install a thorn-shaped fractionating column and a three-way pipe, and heat to reflux at 120° C. for 3 hours under the protection of nitrogen. After the reaction control is completed, cool the reaction liquid to room temperature, filter the catalyst, add excess lye to neutralize benzoylformic acid in the filtrate, extract the mixed liquid with ethyl acetate, take the organic phase, and remove the organic solvent with a rotary evaporator , the product 2-(1,4-dioxane)benzophenone was obtained with a yield of 95%.

Example 5

In a 150mL round bottom flask, add benzoylformic acid (25mmol, 3.753g), Cu/H-SSZ-39-500-A (10mol%, 0.3g), 1,4-dioxane (75mL), and use After ultrasonic mixing, tert-butyl hydroperoxide (37.5 mmol, 3.380 g) was added. Install a thorn-shaped fractionating column and a three-way pipe, and heat to reflux at 120° C. for 3 hours under the protection of nitrogen. After the reaction control is completed, cool the reaction liquid to room temperature, filter the catalyst, add excess lye to neutralize benzoylformic acid in the filtrate, extract the mixed liquid with ethyl acetate, take the organic phase, and remove the organic solvent with a rotary evaporator , the product 2-(1,4-dioxane)benzophenone was obtained with a yield of 92%.

Example 6

In a 150mL round bottom flask, add benzoylformic acid (25mmol, 3.753g), Cu/H-SSZ-39-400-E (10mol%, 0.3g), 1,4-dioxane (75mL), and use After ultrasonic mixing, tert-butyl hydroperoxide (37.5 mmol, 3.380 g) was added. Install a thorn-shaped fractionating column and a three-way pipe, and heat to reflux for 3 hours under nitrogen protection. After the reaction control is completed, cool the reaction solution to room temperature, filter the catalyst, add excess lye to neutralize benzoylformic acid in the filtrate, extract the mixed solution with ethyl acetate, take the organic phase, and remove the organic solvent with a rotary evaporator , the product 2-(1,4-dioxane)benzophenone was obtained with a yield of 90%.

Example 7

Add benzoylformic acid (25mmol, 3.753g), Cu/H-SSZ-39-450-A (10mol%, 0.3g), ethylene glycol dimethyl ether (75mL) into a 150mL round bottom flask, and mix by ultrasonic After homogenization, tert-butyl hydroperoxide (37.5 mmol, 3.380 g) was added. Install a thorn-shaped fractionating column and a three-way pipe, and heat to reflux at 100° C. for 3 hours under the protection of nitrogen. After the reaction control is completed, cool the reaction liquid to room temperature, filter the catalyst, add excess lye to neutralize benzoylformic acid in the filtrate, extract the mixed liquid with ethyl acetate, take the organic phase, and remove the organic solvent with a rotary evaporator , the product 2,3-dimethoxyphenylacetone was obtained with a yield of 90%. ^{The 1} H NMR spectrum of the product 2,3-dimethoxyphenylacetone is shown in FIG. 4 .

¹ H NMR (400MHz, CDCl ₃ ) δ8.10 (t, J = 8.0Hz, 2H), 7.59 (t, J = 7.8Hz, 1H), 7.47 (q, J = 7.3, 7.7Hz, 2H), 6.14 (t, J=4.9Hz, 1H), 3.64(t, J=4.5Hz, 2H), 3.55(s, 3H), 3.44(s, 3H).

Example 8

Cu/H-SSZ-39-450-A recycling

Add benzoylformic acid (25mmol, 3.753g), Cu/H-SSZ-39-450-A (10mol%, 0.3g), 1,4-dioxane (75mL) in a 150mL round bottom flask, and use After ultrasonic mixing, tert-butyl hydroperoxide (37.5 mmol, 3.380 g) was added. Install a thorn-shaped fractionating column and a three-way pipe, and heat to reflux at 120° C. for 3 hours under the protection of nitrogen. After the reaction control is completed, cool the reaction solution to room temperature, centrifuge to recover the catalyst, add excess lye to the filtrate to neutralize benzoylformic acid, extract the mixed solution with ethyl acetate, take the organic phase, and remove the organic solvent with a rotary evaporator , the product 2-(1,4-dioxane)benzophenone was obtained, and the dried catalyst was used under the same catalytic conditions, and the catalytic effect after recycling 5 times was shown in Figure 5, and the results showed that the catalyst was recycled after 5 cycles. The catalytic effect did not decrease significantly after that.

The present invention has been described in detail above in conjunction with the examples, but the content is only the specific implementation of the present invention, but it should not be construed as limiting the patent scope of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, any modifications and improvements made according to the scope of the application of the present invention should still belong to the scope of the patent of the present invention. within range.

Claims (8)

1. an application of a microporous material-supported copper catalyst, characterized in that said microporous material-supported copper catalyst comprises the steps: (1) In an agate mortar, mix DY-32 zeolite, sodium hydroxide, template agent, water and seed crystals evenly and transfer crystals in an oven. The product is washed and calcined to obtain Na-type SSZ-39 zeolite, and ion-exchanged to obtain H-type SSZ-39 zeolite; (2) H-SSZ-39 zeolite is impregnated with copper salt solution for incipient wetness, after natural drying in the shade, vacuum-dried, then after roasting, obtain microporous material supported copper catalyst Cu/H-SSZ-39; The microporous material-supported copper catalyst is applied to the catalytic decarboxylation coupling reaction: add benzoylformic acid, microporous material-supported copper catalyst, ether compounds and tert-butyl hydroperoxide to the reactor, and then introduce Nitrogen, decarboxylation coupling reaction under heating conditions for 1.5 to 3 hours; after the reaction, the reaction liquid is cooled to room temperature, filtered, and the solvent is evaporated to obtain the decarboxylation coupling product. 2. according to the application of the microporous material supported copper catalyst of claim 1, it is characterized in that: the template agent is N, N-dimethyl-3,5-dimethylpiperidine hydroxide solution, the The seed crystal is H-SSZ-39 seed crystal. 3. The application of microporous material-supported copper catalyst according to claim 1, characterized in that the mass ratio of DY-32 zeolite, sodium hydroxide and template agent is 1:0.115-0.135:0.85-1.05. 4. The application of the microporous material-supported copper catalyst according to claim 1, characterized in that: in the step (1), the crystal transformation temperature is 120 to 160° C., and the crystal transformation time is 2 to 4 days; in the step (2), vacuum drying The temperature is 60-120°C, the drying time is 8-16 hours, and the calcination temperature is 300-600°C. 5. according to the application of the described microporous material supported copper catalyst of claim 1, it is characterized in that: described copper salt is the one in copper acetate, copper sulfate, copper nitrate, cupric chloride; Described copper salt solution is copper Saline solution, copper salt ethanol solution, or copper salt methanol solution. 6. according to the application of the described microporous material supported copper catalyst of claim 1, it is characterized in that comprising the steps: (1) Add 1g of DY-32 zeolite to an agate mortar, add 0.95g of N,N-dimethyl-3,5-dimethylpiperidine hydroxide solution, grind evenly; add 0.05g to the mixture Ionized water, grind evenly; add 0.125g granular sodium hydroxide to the mixture, grind evenly; add 0.02g H-SSZ-39 zeolite seed crystals to the mixture, grind evenly; 3 days; the product was calcined at 550°C for 4 hours; the obtained product was ion-exchanged twice at 80°C in 1M ammonium nitrate solution to obtain the H-type product H-SSZ-39-0.95 zeolite; (2) Add H-SSZ-39-0.95 zeolite into the beaker, slowly add copper nitrate solution dropwise until the zeolite is completely wet, and dry in the shade; transfer to a vacuum oven at 100°C for 12 hours; crush the catalyst solid and put it in a porcelain boat , heated at 5°C per minute, and fired at 450°C for 3 hours to obtain Cu/H-SSZ-39. 7 . The application of the microporous material-supported copper catalyst according to claim 1 , characterized in that: the molar ratio of benzoylformic acid to the microporous material-supported copper catalyst is 100:5-25. 8. The application of the microporous material-supported copper catalyst according to claim 1, characterized in that: the decarboxylation coupling reaction temperature is 80-170°C.

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