A heterogeneous catalyst which can be used for the synthesis of benzyl phenylpropynoate compounds

Abstract

The application relates to the technical field of chemical synthesis, in particular to a heterogeneous catalyst which can be used for synthesizing benzyl phenylpropynoate compounds. x Ni y M z , M is at least one of Pt, Pd, Rh, Ru and Ir, x, y and z represent molar numbers, x+y+z=10, z is 1-2, and x:y is 1-8:1; and the carrier is a metal oxide or a molecular sieve. The heterogeneous catalyst can be used for synthesizing benzyl phenylpropynoate compounds by adopting a one-pot method, has high catalyst activity, good substrate universality, good stability, can be repeatedly used for more than 5 times, and can be separated by adopting a filtering mode, so that the separation method is simple. Moreover, a product post-treatment method is simple, and the target product has high yield.

Description

Technical Field

[0001] This invention relates to the field of chemical synthesis technology, and in particular to a heterogeneous catalyst that can be used to synthesize benzyl phenylpropynate compounds. Background Technology

[0002] With the continuous improvement of living standards, human demand for production materials and requirements for the living environment are constantly increasing. On the one hand, there is a strong desire to improve the environment upon which we depend for survival; on the other hand, there is a search for new resources to replace existing ones. CO2, as a major representative of the greenhouse effect, threatens human survival, but it is also a widely available carbon dioxide resource in nature, possessing advantages such as low cost, easy availability, and non-toxicity. Therefore, how to convert carbon dioxide into high-value-added chemicals has dual significance. Carbon dioxide is chemically stable; therefore, capturing, fixing, and converting CO2 into high-value-added chemicals presents a significant challenge. Currently, research on carbon dioxide is not yet mature, with only a small amount of research results translated into industrial production. However, this is still a drop in the ocean compared to the enormous emissions. Furthermore, the chemical products synthesized using carbon dioxide have a relatively simple structure and significant limitations.

[0003] Acrylates and their derivatives are an important class of compounds, widely found in bioactive molecules, and are highly valuable intermediates in the chemical and pharmaceutical industries. However, there are relatively few synthetic methods for acetylates, and the reported methods involve harsh reaction conditions and complex post-reaction processing, which means they are still some distance from industrialization.

[0004] Researchers have conducted extensive studies on transition metal-catalyzed C / C coupling, and this technology is also applicable to the carboxylation of CH bonds between CO2 and terminal alkynes. Silver (copper)-catalyzed carboxylation of terminal alkynes with CO2 has been widely reported; this catalyst system exhibits high catalytic activity and good stability, as well as good substrate applicability and strong compatibility with functional groups. However, these reported catalysts are not easily recycled, leading to excessively high reaction costs. Summary of the Invention

[0005] First, the present invention provides a multiphase catalyst, comprising: an alloy and a support;

[0006] The alloy is Ag. x Ni y M z M is at least one of Pt, Pd, Rh, Ru and Ir, x, y and z represent the number of moles, x+y+z=10, z is 1~2, x:y is 1~8:1;

[0007] The carrier is a metal oxide or a molecular sieve.

[0008] In the heterogeneous catalyst of this invention, the alloy composed of silver, nickel, and M exhibits strong interactions with the support, significantly promoting the adsorption of phenyl-terminated alkynes, benzyl halides, and carbon dioxide on its surface, thereby increasing the reaction rate and demonstrating high catalytic activity and good substrate universality. Simultaneously, the catalyst of this invention exhibits good stability and is easily recyclable; after washing and drying, it can be reused more than five times, greatly reducing reaction costs while ensuring a high yield of the target product.

[0009] In a preferred embodiment of the present invention, M is Pd.

[0010] In a preferred embodiment of the present invention, the metal oxide is at least one selected from SiO2, Al2O3, TiO2, and ZrO2;

[0011] And / or, the molecular sieve is a Y-type, β-type, ZSM-5, or MCM-41 molecular sieve, preferably a ZSM-5 molecular sieve.

[0012] When ZSM-5 molecular sieve is selected as the support, it can generate a stronger interaction with the above alloy, which further improves the catalytic efficiency.

[0013] In a preferred embodiment of the present invention, the weight ratio of the alloy to the carrier is 1:1 to 50; preferably 1:2 to 9.

[0014] Furthermore, the present invention also provides a method for preparing a heterogeneous catalyst in any of the above embodiments, comprising:

[0015] (1) Silver salt, nickel salt, M metal salt, organic base, solvent and anhydrous sodium sulfate are mixed and ground to obtain a mixture;

[0016] The volume ratio of organic base to solvent is 1:1 to 10; the molar ratio of all metal salts to organic base is 1:1 to 3.

[0017] (2) The mixture is calcined at 200-500°C to obtain a solid powder, and then the solid powder is mixed with a 0.01-0.5 mol / L hydrazine hydrate solution and filtered to obtain the alloy;

[0018] (3) The alloy is mixed with the support and then subjected to a reduction reaction at 200-300°C under a hydrogen atmosphere to obtain the multiphase catalyst.

[0019] In the specific implementation process, in step (1), the silver salt, nickel salt, M metal salt can be mixed with organic base and solvent and stirred first, and then mixed with anhydrous sodium sulfate and stirred a second time; the preferred stirring time is 0.5 to 2 hours.

[0020] Preferably, in step (2), the roasting time is 0.5h to 3h.

[0021] Preferably, in step (2), the filtering is performed at least 3 times.

[0022] Preferably, in step (2), the alloy is dried after filtration.

[0023] In the specific implementation process, drying is included, but is not limited to, drying in a vacuum drying oven.

[0024] Preferably, in step (3), the alloy is mixed with the carrier and then ground, preferably for 25 to 35 minutes, more preferably for 30 minutes.

[0025] Preferably, in step (3), the hydrogen space velocity is 1000–40000 h⁻¹. -1 Preferably 5000-20000h -1 .

[0026] Preferably, in step (3), the reduction reaction takes 1 to 2 hours.

[0027] In specific implementation, the reduction reaction may include, but is not limited to, being carried out in a fixed-bed reactor.

[0028] In the specific implementation process, this includes, but is not limited to, grinding in an agate mortar.

[0029] In the specific implementation process, the metal salt is an inorganic metal salt or an organic metal salt;

[0030] The silver salt is preferably AgNO3, and the nickel salt is preferably Ni(NO3)2.

[0031] In a preferred embodiment of the present invention, the organic base in the preparation method is at least one selected from methylamine, urea, ethylamine, ethanolamine, ethylenediamine, dimethylamine, trimethylamine, triethylamine, propylamine, isopropylamine, 1,3-propanediamine, 1,2-propanediamine, tripropylamine, triethanolamine, butylamine, isobutylamine, tert-butylamine, hexylamine, octylamine, aniline, benzylamine, cyclohexylamine, o-toluidine, m-toluidine, p-toluidine, diphenylamine, and benzidine, preferably n-hexylamine;

[0032] And / or, the solvent is at least one selected from benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dichloromethane, methanol, ethanol, isopropanol, acetonitrile, pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide, preferably xylene.

[0033] Furthermore, the present invention also provides a method for synthesizing benzyl phenylpropynate compounds, comprising:

[0034] In an anhydrous inert gas environment, benzyl phenylpropynate compounds are prepared by reacting phenyl-terminated alkyne compounds, benzyl halides, bases, organic solvents, and carbon dioxide as raw materials under the catalysis of a heterogeneous catalyst in any of the above embodiments.

[0035] Preferably, benzyl phenylpropynate compounds are synthesized in an anhydrous and oxygen-free argon atmosphere.

[0036] Preferably, the reaction time is 12 to 48 hours, more preferably 12 to 24 hours.

[0037] In specific implementation processes, the synthesis methods for benzyl phenylpropynate compounds include:

[0038] In an anhydrous inert gas environment, phenyl-terminated alkynes, benzyl halides, bases, organic solvents, and the aforementioned heterogeneous catalyst are mixed, and then carbon dioxide (1 atm) is introduced to carry out the reaction, yielding benzyl phenylpropynate compounds. The reaction route is as follows:

[0039]

[0040] In a preferred embodiment of the present invention, the concentration of the heterogeneous catalyst in the liquid-phase reaction system during the synthesis method is 1-10 g / L, preferably 2-5 g / L.

[0041] In a preferred embodiment of the present invention, the structural formula of the phenyl-terminated alkyne compound in the synthesis method is as follows:

[0042]

[0043] The structural formula of the benzyl halide is:

[0044]

[0045] Wherein, R is selected from hydrogen, alkyl, alkoxy, phenyl, aldehyde, nitro, cyano, ester, trifluoromethyl, or halogen; X is selected from F, Cl, Br, or I;

[0046] And / or, the base is at least one of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, tert-butylpotassium, and tert-butylsodium, more preferably cesium carbonate or tert-butylpotassium;

[0047] And / or, the organic solvent is at least one of dichloromethane, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, and dimethyl sulfoxide, preferably N,N-dimethylformamide.

[0048] In a preferred embodiment of the present invention, the molar ratio of the base to the phenyl-terminated alkyne compound in the synthesis method is 0.5 to 3:1, preferably 1 to 2:1;

[0049] And / or, the molar ratio of the phenyl-terminated alkyne compound to the benzyl halide is 1:1 to 2, preferably 1:1 to 1.3.

[0050] In a preferred embodiment of the present invention, the reaction temperature in the synthesis method is 20–40°C, preferably 25–40°C.

[0051] This invention uses supported Ag-Ni-M alloy powder as a catalyst, adheres to the principle of "green chemistry," aims for energy conservation and high efficiency, and takes into account "atom economy." Under mild conditions, it catalyzes the carboxylation coupling reaction of terminal alkynes, carbon dioxide, and benzyl halides in a "one-pot" process, efficiently converting CO2 into benzyl acetylate products, which has significant research value.

[0052] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0053] This invention provides a heterogeneous catalyst for the synthesis of benzyl phenylpropynate compounds, enabling a one-pot synthesis of these compounds. The catalyst exhibits high activity, good substrate versatility, and good stability, allowing for reuse more than five times. The catalyst can be easily separated by filtration, making the separation method simple. Furthermore, the product post-processing method is simple, and the yield of the target product is high.

[0054] Furthermore, this invention uses carbon dioxide as a reaction substrate to synthesize benzyl phenylpropynate compounds, providing a direction for the chemical utilization of greenhouse gases and energy conservation and emission reduction. Detailed Implementation

[0055] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0056] Unless otherwise specified, all methods used in the examples were conventional or performed according to techniques or conditions described in the literature in this field, or in accordance with the product instructions. Reagents and instruments used without specified manufacturers were all conventional products that could be purchased from legitimate channels.

[0057] Example 1: Preparation of catalyst Ag6Ni2Pd2 / ZSM-5

[0058] 2 mL of n-hexylamine and 10 mL of xylene were measured into round-bottom flasks, respectively. 6 mmol (1.0194 g) of AgNO3, 2 mmol (0.3654 g) of Ni(NO3)2, and 2 mmol (0.449 g) of Pd(CH3COO)2 were added, and the mixture was stirred for 30 min. Then, 80 g of anhydrous sodium sulfate was added to the mixture, and stirring was continued for another 30 min. The mixture was placed in a tube furnace and reacted at 300 °C for 1 h. After cooling to room temperature, the resulting solid powder was dissolved in a 0.1 mol / L hydrazine hydrate solution, washed, filtered, and repeated at least three times. Finally, the powder was dried in a vacuum drying oven at 80 °C for 12 h to obtain nano-Ag6Ni2Pd2 alloy powder catalyst.

[0059] The prepared 0.3g Ag6Ni2Pd2 nano-alloy and 3.0g ZSM-5 molecular sieve support were thoroughly ground in an agate mortar for 30 min. Then, the solid powder was loaded into a fixed-bed reactor and reduced at 200℃ for 2 h under a hydrogen atmosphere with a hydrogen space velocity of 10000 h⁻¹. -1 A supported nano-Ag6Ni2Pd2 / ZSM-5 alloy powder catalyst was prepared.

[0060] Example 2: Preparation of catalyst Ag4Ni4Pt2 / MCM-41

[0061] 1.8 mL of ethylenediamine and 18 mL of xylene were measured into round-bottom flasks, respectively. 4 mmol (0.6796 g) of AgNO3, 4 mmol (0.7308 g) of Ni(NO3)2, and 2 mmol (0.8878 g) of (NH4)2PtCl6 were added, and the mixture was stirred for 30 min. Then, 80 g of anhydrous sodium sulfate was added to the mixture, and stirring was continued for another 30 min. The mixture was placed in a tube furnace and reacted at 200 °C for 2 h. After cooling to room temperature, the resulting solid powder was dissolved in a 0.1 mol / L hydrazine hydrate solution, washed, filtered, and repeated at least three times. Finally, the powder was dried in a vacuum drying oven at 80 °C for 12 h to obtain nano-Ag4Ni4Pt2 alloy powder catalyst.

[0062] The prepared 0.3g Ag4Ni4Pd2 nano-alloy and 2.7g ZSM-5 molecular sieve support were thoroughly ground in an agate mortar for 30 min. Then, the solid powder was loaded into a fixed-bed reactor and reduced at 200℃ for 2 h under a hydrogen atmosphere with a hydrogen space velocity of 5000 h⁻¹. -1 A supported nano-Ag4Ni4Pt2 / MCM-41 alloy powder catalyst was prepared.

[0063] Example 3: Preparation of catalyst Ag5Ni3Ru2 / USY

[0064] 2 mL of o-toluidine and 2 mL of toluene were measured into round-bottom flasks, respectively. 5 mmol (0.8495 g) of AgNO3, 3 mmol (0.5481 g) of Ni(NO3)2, and 2 mmol (0.4185 g) of RhCl3 were added, and the mixture was stirred for 30 min. Then, 80 g of anhydrous sodium sulfate was added to the mixture, and stirring was continued for another 30 min. The mixture was placed in a tube furnace and reacted at 400 °C for 1 h. After cooling to room temperature, the resulting solid powder was dissolved in a 0.1 mol / L hydrazine hydrate solution, washed, filtered, and repeated at least three times. Finally, the powder was dried in a vacuum drying oven at 80 °C for 12 h to obtain nano-Ag5Ni3Ru1 alloy powder catalyst.

[0065] The prepared 0.3g Ag5Ni3Ru2 nanoalloy and 1.7g USY molecular sieve support were thoroughly ground in an agate mortar for 30 min. Then, the solid powder was loaded into a fixed-bed reactor and reduced at 200℃ for 2 h under a hydrogen atmosphere with a hydrogen space velocity of 15000 h⁻¹. -1 A supported nano-Ag5Ni3Ru2 / USY alloy powder catalyst was prepared.

[0066] Example 4: Preparation of catalyst Ag8Ni1Rh1 / SiO2

[0067] 1.5 mL of triethanolamine and 6 mL of ethanol were measured into round-bottom flasks, respectively. 6 mmol (1.3592 g) of AgNO3, 1 mmol (0.1827 g) of Ni(NO3)2, and 1 mmol (0.2093 g) of RhCl3 were added, and the mixture was stirred for 30 min. Then, 80 g of anhydrous sodium sulfate was added to the mixture, and stirring was continued for another 30 min. The mixture was placed in a tube furnace and reacted at 400 °C for 1 h. After cooling to room temperature, the resulting solid powder was dissolved in a 0.1 mol / L hydrazine hydrate solution, washed, filtered, and repeated at least three times. Finally, the powder was dried in a vacuum drying oven at 80 °C for 12 h to obtain the nano-Ag8Ni1Rh1 alloy powder catalyst.

[0068] The prepared 0.3g Ag8Ni1Rh1 nanoalloy and 1.2g SiO2 support were thoroughly ground in an agate mortar for 30 min. Then, the solid powder was loaded into a fixed-bed reactor and reduced at 200℃ for 2 h under a hydrogen atmosphere with a hydrogen space velocity of 20000 h⁻¹. -1 A supported nano-Ag8Ni1Rh1 / SiO2 alloy powder catalyst was prepared.

[0069] Example 5: Preparation of catalyst Ag6Ni2Pt2 / Al2O3

[0070] 2 mL of n-hexylamine and 4 mL of xylene were measured into round-bottom flasks, respectively. 6 mmol (1.0194 g) of AgNO3, 2 mmol (0.3654 g) of Ni(NO3)2, and 2 mmol (0.8878 g) of (NH4)2PtCl6 were added, and the mixture was stirred for 30 min. Then, 80 g of anhydrous sodium sulfate was added to the mixture, and stirring was continued for another 30 min. The mixture was placed in a tube furnace and reacted at 500 °C for 0.5 h. After cooling to room temperature, the resulting solid powder was dissolved in a 0.1 mol / L hydrazine hydrate solution, washed, filtered, and repeated at least three times. Finally, the powder was dried in a vacuum drying oven at 80 °C for 12 h to obtain nano-Ag6Ni2Pt2 alloy powder catalyst.

[0071] The prepared 0.3g Ag6Ni2Pt2 nanoalloy and 0.7g Al2O3 support were thoroughly ground in an agate mortar for 30 min. Then, the solid powder was loaded into a fixed-bed reactor and reduced at 300℃ for 1 h under a hydrogen atmosphere with a hydrogen space velocity of 10000 h⁻¹. -1 A supported nano-Ag6Ni2Pt2 / Al2O3 alloy powder catalyst was prepared.

[0072] Example 6: Preparation of the catalyst Ag6Ni2Rh2 / TiO2

[0073] 2 mL of n-hexylamine and 12 mL of xylene were measured into round-bottom flasks, respectively. 6 mmol (1.0194 g) of AgNO3, 2 mmol (0.3654 g) of Ni(NO3)2, and 2 mmol (0.4185 g) of RhCl3 were added, and the mixture was stirred for 30 min. Then, 80 g of anhydrous sodium sulfate was added to the mixture, and stirring was continued for another 30 min. The mixture was placed in a tube furnace and reacted at 200 °C for 2 h. After cooling to room temperature, the resulting solid powder was dissolved in a 0.1 mol / L hydrazine hydrate solution, washed, filtered, and repeated at least three times. Finally, the powder was dried in a vacuum drying oven at 80 °C for 12 h to obtain nano-Ag6Ni2Rh2 alloy powder catalyst.

[0074] The prepared 0.3g Ag6Ni2Rh2 nanoalloy and 0.3g TiO2 support were thoroughly ground in an agate mortar for 30 min. Then, the solid powder was loaded into a fixed-bed reactor and reduced at 300℃ for 1 h under a hydrogen atmosphere with a hydrogen space velocity of 15000 h⁻¹. -1 A supported nano-Ag6Ni2Rh2 / TiO2 alloy powder catalyst was prepared.

[0075] Example 7: Preparation of the catalyst Ag6Ni2Ru2 / ZrO2

[0076] 2 mL of n-hexylamine and 16 mL of xylene were measured into round-bottom flasks, respectively. 6 mmol (1.0194 g) of AgNO3, 2 mmol (0.3654 g) of Ni(NO3)2, and 2 mmol (0.5230 g) of RuCl3·3H2O were added and the mixture was stirred for 30 min. Then, 80 g of anhydrous sodium sulfate was added to the mixture and stirring was continued for another 30 min. The mixture was placed in a tube furnace and reacted at 400 °C for 1 h. After cooling to room temperature, the resulting solid powder was dissolved in a 0.1 mol / L hydrazine hydrate solution, washed, filtered, and repeated at least three times. Finally, the powder was dried in a vacuum drying oven at 80 °C for 12 h to obtain nano-Ag6Ni2Ru2 alloy powder catalyst.

[0077] The prepared 0.3g Ag6Ni2Ru2 nanoalloy and 14.7g ZrO2 molecular sieve support were thoroughly ground in an agate mortar for 30 min. Then, the solid powder was loaded into a fixed-bed reactor and reduced at 200℃ for 2 h under a hydrogen atmosphere with a hydrogen space velocity of 20000 h⁻¹. -1 A supported nano-Ag6Ni2Ru2 / ZrO2 alloy powder catalyst was prepared.

[0078] The preparation conditions of the catalysts in Examples 1 to 7 are compared as shown in Table 1.

[0079] Table 1 Catalyst preparation conditions

[0080]

[0081] Example 8: Synthesis of 3-cyanobenzyl phenylpropynate catalyzed by Ag6Ni2Pd2 / ZSM-5. The structural formula of 3-cyanobenzyl phenylpropynate is shown below:

[0082]

[0083] Under an anhydrous and oxygen-free argon atmosphere, 2.0 mmol of phenylacetylene, 2.2 mmol of 3-cyanobenzyl bromide, 60 mg of Ag6Ni2Pd2 / ZSM-5, 3.0 mmol of cesium carbonate, and 15 mL of DMF were added to a 50 mL Schlenk flask. CO2 (1 atm) was introduced, and the reaction was carried out at 40 °C for 12 h. After the reaction was completed, the reaction solution was transferred to a K2CO3 solution (2N, 10 mL), stirred at room temperature for 30 min, and the mixture was extracted with dichloromethane (3 × 5 mL). The aqueous layer was acidified with hydrochloric acid to pH = 1, and then extracted with diethyl ether (3 × 5 mL). The organic layer was dried with anhydrous Na2SO4 for 12 h, filtered, and the solvent was removed by vacuum to obtain the target product with a yield of 95%.

[0084] Examples 9-14: Reusability of Ag6Ni2Pd2 / ZSM-5

[0085] The catalyst separated in Example 8 can be reused after washing and drying with diethyl ether. The yields of the product after five uses were 95%, 95%, 93%, 92%, and 92%, respectively.

[0086] Example 15 Synthesis of 4-methylphenylpropynic acid-3-cyanobenzyl ester catalyzed by Ag4Ni4Pt2 / MCM-41 The structural formula of 4-methylphenylpropynic acid-3-cyanobenzyl ester is shown below:

[0087]

[0088] Under an anhydrous and oxygen-free argon atmosphere, catalyst Ag4Ni4Pt2 / MCM-41 (100 mg), potassium tert-butyl (6.0 mmol, 577 mg), 4-methylphenylacetylene (2.0 mmol, 234 mg), 3-cyanobenzyl bromide (2.2 mmol, 464 mg), and acetonitrile (15 mL) were added to a 50 mL Schlenk flask. CO2 (1 atm) was then introduced, and the reaction was carried out at 30 °C for 16 hours. After the reaction was completed, the reaction solution was transferred to a K2CO3 solution (2N, 10 mL), stirred at room temperature for 30 min, and the mixture was extracted with dichloromethane (3 × 5 mL). The aqueous layer was acidified with hydrochloric acid to pH 1, and then extracted with diethyl ether (3 × 5 mL). The organic layer was dried with anhydrous Na2SO4 for 12 hours, filtered, and the solvent was removed by vacuum to obtain the target product with a separation yield of 83%.

[0089] Example 16 Synthesis of 4-n-propylphenylpropynic acid-3-cyanobenzyl ester catalyzed by Ag5Ni3Ru2 / USY The structural formula of 4-n-propylphenylpropynic acid-3-cyanobenzyl ester is shown below:

[0090]

[0091] Under an anhydrous and oxygen-free argon atmosphere, the catalyst Ag5Ni3Ru2 / USY (15 mg), rubidium carbonate (1.0 mmol, 331 mg), 4-n-propylphenylacetylene (2.0 mmol, 286 mg), 3-cyanobenzyl bromide (3.0 mmol, 633 mg), and dimethyl sulfoxide (15 mL) were added to a 50 mL Schlenk flask. CO2 (1 atm) was then introduced, and the reaction was carried out at 35 °C for 16 hours. After the reaction was completed, the reaction solution was transferred to a K2CO3 solution (2N, 10 mL), stirred at room temperature for 30 min, and the mixture was extracted with dichloromethane (3 × 5 mL). The aqueous layer was acidified with hydrochloric acid to pH 1, and then extracted with diethyl ether (3 × 5 mL). The organic layer was dried with anhydrous Na2SO4 for 12 hours, filtered, and the solvent was removed by vacuum to obtain the target product with a separation yield of 77%.

[0092] Example 17: Synthesis of 4-phenylphenylpropynic acid-3-cyanobenzyl ester catalyzed by Ag8Ni1Rh1 / SiO2. The structural formula of 4-phenylphenylpropynic acid-3-cyanobenzyl ester is shown below:

[0093]

[0094] Under an anhydrous and oxygen-free argon atmosphere, the catalyst Ag8Ni1Rh1 / SiO2 (60 mg), lithium carbonate (3.0 mmol, 222 mg), 4-phenylphenylacetylene (2.0 mmol, 358 mg), 3-cyanobenzyl bromide (2.2 mmol, 464 mg), and tetrahydrofuran (15 mL) were added to a 50 mL Schlenk flask. CO2 (1 atm) was then introduced, and the reaction was carried out at 40 °C for 12 hours. After the reaction was completed, the reaction solution was transferred to a K2CO3 solution (2 N, 10 mL), stirred at room temperature for 30 min, and the mixture was extracted with dichloromethane (3 × 5 mL). The aqueous layer was acidified with hydrochloric acid to pH 1, and then extracted with diethyl ether (3 × 5 mL). The organic layer was dried with anhydrous Na2SO4 for 12 hours, filtered, and the solvent was removed by vacuum to obtain the target product with a separation yield of 82%.

[0095] Example 18 Synthesis of 4-methoxyphenylpropynic acid-3-cyanobenzyl ester catalyzed by Ag6Ni2Pt2 / Al2O3 The structural formula of 4-methoxyphenylpropynic acid-3-cyanobenzyl ester is shown below:

[0096]

[0097] Under an anhydrous and oxygen-free argon atmosphere, the catalyst Ag6Ni2Pt2 / Al2O3 (60 mg), sodium carbonate (3.0 mmol, 318 mg), 4-methoxyphenylacetylene (2.0 mmol, 270 mg), 3-cyanobenzyl bromide (2.0 mmol, 422 mg), and dichloromethane (15 mL) were added to a 50 mL Schlenk flask. CO2 (1 atm) was then introduced, and the reaction was carried out at 25 °C for 30 hours. After the reaction was completed, the reaction solution was transferred to a K2CO3 solution (2N, 10 mL), stirred at room temperature for 30 min, and the mixture was extracted with dichloromethane (3 × 5 mL). The aqueous layer was acidified with hydrochloric acid to pH 1, and then extracted with diethyl ether (3 × 5 mL). The organic layer was dried with anhydrous Na2SO4 for 12 hours, filtered, and the solvent was removed by vacuum to obtain the target product with a separation yield of 75%.

[0098] Example 19: Synthesis of 4-fluorophenylpropynic acid-3-cyanobenzyl ester catalyzed by Ag6Ni2Rh2 / TiO2. The structural formula of 4-fluorophenylpropynic acid-3-cyanobenzyl ester is shown below:

[0099]

[0100] Under an anhydrous and oxygen-free argon atmosphere, the catalyst Ag6Ni2Rh2 / TiO2 (60 mg), cesium carbonate (3.0 mmol, 977 mg), 4-fluorophenylacetylene (2.0 mmol, 242 mg), 3-cyanobenzyl bromide (2.2 mmol, 464 mg), and DMF (15 mL) were added to a 50 mL Schlenk flask. CO2 (1 atm) was then introduced, and the reaction was carried out at 25 °C for 48 hours. After the reaction was completed, the reaction solution was transferred to a K2CO3 solution (2N, 10 mL), stirred at room temperature for 30 min, and the mixture was extracted with dichloromethane (3 × 5 mL). The aqueous layer was acidified with hydrochloric acid to pH = 1, and then extracted with diethyl ether (3 × 5 mL). The organic layer was dried with anhydrous Na2SO4 for 12 hours, filtered, and the solvent was removed by vacuum to obtain the target product with a separation yield of 87%.

[0101] Example 20: Synthesis of 3-fluorophenylpropynic acid-3-cyanobenzyl ester catalyzed by Ag6Ni2Ru2 / ZrO2. The structural formula of 3-fluorophenylpropynic acid-3-cyanobenzyl ester is shown below:

[0102]

[0103] Under an anhydrous and oxygen-free argon atmosphere, the catalyst Ag6Ni2Ru2 / ZrO2 (60 mg), cesium carbonate (3.0 mmol, 977 mg), 3-fluorophenylacetylene (2.0 mmol, 242 mg), 3-cyanobenzyl bromide (2.2 mmol, 464 mg), and DMF (15 mL) were added to a 50 mL Schlenk flask. CO2 (1 atm) was then introduced, and the reaction was carried out at 25 °C for 16 hours. After the reaction was completed, the reaction solution was transferred to a K2CO3 solution (2 N, 10 mL), stirred at room temperature for 30 min, and the mixture was extracted with dichloromethane (3 × 5 mL). The aqueous layer was acidified with hydrochloric acid to pH = 1, and then extracted with diethyl ether (3 × 5 mL). The organic layer was dried with anhydrous Na2SO4 for 12 hours, filtered, and the solvent was removed by vacuum to obtain the target product with a separation yield of 82%.

[0104] Example 21 Synthesis of 4-chlorophenylpropynic acid-3-cyanobenzyl ester catalyzed by Ag6Ni2Pd2 / ZSM-5 The structural formula of 4-chlorophenylpropynic acid-3-cyanobenzyl ester is shown below:

[0105]

[0106] Under an anhydrous and oxygen-free argon atmosphere, the catalyst Ag6Ni2Pd2 / ZSM-5 (60 mg), cesium carbonate (3.0 mmol, 977 mg), 4-chlorophenylacetylene (2.0 mmol, 275 mg), 3-cyanobenzyl bromide (2.2 mmol, 464 mg), and DMF (15 mL) were added to a 50 mL Schlenk flask. CO2 (1 atm) was then introduced, and the reaction was carried out at 25 °C for 16 hours. After the reaction was completed, the reaction solution was transferred to a K2CO3 solution (2N, 10 mL), stirred at room temperature for 30 min, and the mixture was extracted with dichloromethane (3 × 5 mL). The aqueous layer was acidified with hydrochloric acid to pH 1, and then extracted with diethyl ether (3 × 5 mL). The organic layer was dried with anhydrous Na2SO4 for 12 hours, filtered, and the solvent was removed by vacuum to obtain the target product with a separation yield of 75%.

[0107] Example 22 Synthesis of 4-cyanophenylpropynic acid-3-cyanobenzyl ester catalyzed by Ag6Ni2Pd2 / ZSM-5 The structural formula of 4-cyanophenylpropynic acid-3-cyanobenzyl ester is shown below:

[0108]

[0109] Under an anhydrous and oxygen-free argon atmosphere, the catalyst Ag6Ni2Pd2 / ZSM-5 (60 mg), cesium carbonate (3.0 mmol, 977 mg), 4-cyanophenylacetylene (2.0 mmol, 256 mg), 3-cyanobenzyl bromide (2.2 mmol, 464 mg), and DMF (15 mL) were added to a 50 mL Schlenk flask. CO2 (1 atm) was then introduced, and the reaction was carried out at 25 °C for 16 hours. After the reaction was completed, the reaction solution was transferred to a K2CO3 solution (2N, 10 mL), stirred at room temperature for 30 min, and the mixture was extracted with dichloromethane (3 × 5 mL). The aqueous layer was acidified with hydrochloric acid to pH 1, and then extracted with diethyl ether (3 × 5 mL). The organic layer was dried with anhydrous Na2SO4 for 12 hours, filtered, and the solvent was removed by vacuum to obtain the target product with a separation yield of 58%.

[0110] Example 23: Synthesis of 4-nitrophenylpropynic acid-3-cyanobenzyl ester catalyzed by Ag6Ni2Pd2 / ZSM-5. The structural formula of 4-nitrophenylpropynic acid-3-cyanobenzyl ester is shown below:

[0111]

[0112] Under an anhydrous and oxygen-free argon atmosphere, the catalyst Ag6Ni2Pd2 / ZSM-5 (60 mg), cesium carbonate (3.0 mmol, 977 mg), 4-nitrophenylacetylene (2.0 mmol, 296 mg), 3-cyanobenzyl bromide (2.2 mmol, 464 mg), and DMF (15 mL) were added to a 50 mL Schlenk flask. CO2 (1 atm) was then introduced, and the reaction was carried out at 25 °C for 16 hours. After the reaction was completed, the reaction solution was transferred to a K2CO3 solution (2 N, 10 mL), stirred at room temperature for 30 min, and the mixture was extracted with dichloromethane (3 × 5 mL). The aqueous layer was acidified with hydrochloric acid to pH 1, and then extracted with diethyl ether (3 × 5 mL). The organic layer was dried with anhydrous Na2SO4 for 12 hours, filtered, and the solvent was removed by vacuum to obtain the target product with a separation yield of 45%.

[0113] Example 24: Synthesis of benzyl phenylpropynate with increased Ag6Ni2Pd2 nano-alloy catalyst

[0114] Under an anhydrous and oxygen-free argon atmosphere, Ag₆Ni₂Pd₂ (120 mg), cesium carbonate (3.0 mmol, 977 mg), phenylacetylene (2.0 mmol, 204 mg), 3-cyanobenzyl bromide (2.2 mmol, 464 mg), and DMF (15 mL) were added to a 50 mL Schlenk flask. CO₂ (1 atm) was then introduced, and the reaction was carried out at 25 °C for 16 hours. After the reaction was completed, the reaction solution was transferred to a K₂CO₃ solution (2 N, 10 mL), stirred at room temperature for 30 min, and the mixture was extracted with dichloromethane (3 × 5 mL). The aqueous layer was acidified with hydrochloric acid to pH = 1, and then extracted with diethyl ether (3 × 5 mL). The organic layer was dried with anhydrous Na₂SO₄ for 12 hours, filtered, and the solvent was removed by vacuum to obtain the target product with a separation yield of 92%.

[0115] Comparative Example 1: Synthesis of benzyl phenylpropynate without catalyst

[0116] In an anhydrous and oxygen-free argon atmosphere, cesium carbonate (3.0 mmol, 977 mg), phenylacetylene (2.0 mmol, 204 mg), 3-cyanobenzyl bromide (2.2 mmol, 464 mg), and DMF (15 mL) were added to a 50 mL Schlenk flask. CO2 (1 atm) was introduced, and the reaction was carried out at 25 °C for 16 hours. After the reaction, the reaction solution was transferred to a K2CO3 solution (2N, 10 mL), stirred at room temperature for 30 min, and the mixture was extracted with dichloromethane (3 × 5 mL). The aqueous layer was acidified with hydrochloric acid to pH 1, then extracted with diethyl ether (3 × 5 mL). The organic layer was dried with anhydrous Na2SO4 for 12 hours, filtered, and the solvent was removed by vacuum to obtain the target product with a separation yield of 23%. Comparative Example 2: Synthesis of benzyl phenylpropynate catalyzed by ZSM-5 molecular sieve.

[0117] Under an anhydrous and oxygen-free argon atmosphere, ZSM-5 molecular sieve (60 mg), cesium carbonate (3.0 mmol, 977 mg), 3-cyanobenzyl bromide (2.2 mmol, 464 mg), phenylacetylene (2.0 mmol, 204 mg), and DMF (15 mL) were added to a 50 mL Schlenk flask. CO2 (1 atm) was then introduced, and the reaction was carried out at 25 °C for 16 hours. After the reaction was completed, the reaction solution was transferred to a K2CO3 solution (2 N, 10 mL), stirred at room temperature for 30 min, and the mixture was extracted with dichloromethane (3 × 5 mL). The aqueous layer was acidified with hydrochloric acid to pH 1, and then extracted with diethyl ether (3 × 5 mL). The organic layer was dried with anhydrous Na2SO4 for 12 hours, filtered, and the solvent was removed by vacuum to obtain the target product with a separation yield of 30%.

[0118] Comparative example: Synthesis of benzyl phenylpropynate catalyzed by 3Ag6Ni2Pd2 nanoalloys

[0119] Under an anhydrous and oxygen-free argon atmosphere, Ag6Ni2Pd2 (60 mg), cesium carbonate (3.0 mmol, 977 mg), phenylacetylene (2.0 mmol, 204 mg), 3-cyanobenzyl bromide (2.2 mmol, 464 mg), and DMF (15 mL) were added to a 50 mL Schlenk flask. CO2 (1 atm) was then introduced, and the reaction was carried out at 25 °C for 16 hours. After the reaction was completed, the reaction solution was transferred to a K2CO3 solution (2N, 10 mL), stirred at room temperature for 30 min, and the mixture was extracted with dichloromethane (3 × 5 mL). The aqueous layer was acidified with hydrochloric acid to pH = 1, and then extracted with diethyl ether (3 × 5 mL). The organic layer was dried with anhydrous Na2SO4 for 12 hours, filtered, and the solvent was removed by vacuum to obtain the target product with a separation yield of 87%.

[0120] The above results demonstrate that the preparation of benzyl phenylpropynate using the catalyst of this invention can convert CO2 into high-value-added chemicals. This reaction can be carried out under normal temperature and pressure conditions, with mild reaction conditions, high product yield, and good substrate versatility. The supported catalyst is easily recovered and reused during the reaction, and the reaction process is simple and easy to operate. This invention provides a new process route for the high-value utilization of carbon dioxide.

[0121] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for synthesizing benzyl phenylpropynate compounds, characterized in that, include: Benzyl phenylpropynate compounds were prepared by reacting phenyl-terminated alkynes, benzyl halides, bases, organic solvents and carbon dioxide as raw materials under the catalysis of a heterogeneous catalyst in an anhydrous inert gas environment. The multiphase catalyst comprises: an alloy and a support; The alloy is Ag. x Ni y M z M is at least one of Pt, Pd, Rh, Ru and Ir, x, y and z represent the number of moles, x+y+z=10, z is 1~2, x:y is (1~8):1; The carrier is a metal oxide or a molecular sieve.

2. The synthesis method according to claim 1, characterized in that, The metal oxide is at least one of SiO2, Al2O3, TiO2, and ZrO2; and / or the molecular sieve is a Y-type, β-type, ZSM-5, or MCM-41 molecular sieve.

3. The synthesis method according to claim 1 or 2, characterized in that, The weight ratio of the alloy to the carrier is 1:(1~50).

4. The synthesis method according to claim 3, characterized in that, The weight ratio of the alloy to the carrier is 1:(2~9).

5. The synthesis method according to claim 1 or 2, characterized in that, The preparation method of the heterogeneous catalyst includes: (1) Silver salt, nickel salt, M metal salt, organic base, solvent and anhydrous sodium sulfate are mixed and ground to obtain a mixture; The volume ratio of organic base to solvent is 1:(1~10); the molar ratio of all metal salts to organic bases is 1:(1~3). (2) The mixture is calcined at 200℃~500℃ to obtain solid powder, and then the solid powder is mixed with 0.01~0.5 mol / L hydrazine hydrate solution, and the alloy is obtained after filtration; (3) The alloy is mixed with the support and then a reduction reaction is carried out at 200℃~300℃ in a hydrogen atmosphere to obtain the multiphase catalyst.

6. The synthesis method according to claim 5, characterized in that, The organic base is at least one selected from methylamine, urea, ethylamine, ethanolamine, ethylenediamine, dimethylamine, trimethylamine, triethylamine, propylamine, isopropylamine, 1,3-propanediamine, 1,2-propanediamine, tripropylamine, triethanolamine, butylamine, isobutylamine, tert-butylamine, hexylamine, octylamine, aniline, benzylamine, cyclohexylamine, o-toluidine, m-toluidine, p-toluidine, diphenylamine, and benzidine. And / or, the solvent is at least one selected from benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dichloromethane, methanol, ethanol, isopropanol, acetonitrile, pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

7. The synthesis method according to claim 1, characterized in that, The concentration of the heterogeneous catalyst in the liquid-phase reaction system is 1~10 g / L.

8. The synthesis method according to claim 7, characterized in that, The concentration of the heterogeneous catalyst in the liquid-phase reaction system is 2~5 g / L.

9. The synthesis method according to claim 1 or 2, characterized in that, The structural formula of the phenyl-terminated alkyne compound is: ； The structural formula of the benzyl halide is: ； Wherein, R is selected from hydrogen, alkyl, alkoxy, phenyl, aldehyde, nitro, cyano, ester, trifluoromethyl, or halogen; X is selected from F, Cl, Br, or I; And / or, the base is at least one selected from lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, tert-butylpotassium, and tert-butylsodium; And / or, the organic solvent is at least one selected from dichloromethane, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, and dimethyl sulfoxide.

10. The synthesis method according to claim 1 or 2, characterized in that, The molar ratio of the base to the phenyl-terminated alkyne compound is (0.5~3):1; And / or, the molar ratio of the phenyl-terminated alkyne compound to the benzyl halide is 1:1 to 2.

11. The synthesis method according to claim 10, characterized in that, The molar ratio of the base to the phenyl-terminated alkyne compound is (1~2):1; the molar ratio of the phenyl-terminated alkyne compound to the benzyl halide is 1:(1~1.3).

12. The synthesis method according to claim 1 or 2, characterized in that, The reaction temperature is 20℃~40℃.

13. The synthesis method according to claim 12, characterized in that, The reaction temperature is 25℃~40℃.

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