Preparation method of metal supported carbon catalyst and application thereof in synthesis of alkynylimine

Abstract

The application discloses a preparation method of a metal-loaded carbon catalyst and application of the metal-loaded carbon catalyst in synthesis of ynamines, and an expression formula of the metal-loaded carbon catalyst is M@C-T or M / L@C-T, wherein M is any one or more than one of metals Cu, Ni, Fe or Co; L is any one or more than one of bipyridine, triphenylphosphine, o-phenanthroline, tributyl phosphate or triethyl phosphite; C represents carbon; and T is temperature, and T is 300 DEG C to 800 DEG C. Through construction of the carbon catalyst and a suitable catalytic system, the application realizes preparation of ynamine derivatives by catalyzing reaction of O-acetyloxime and a terminal alkyne.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, and specifically relates to a method for preparing a metal-supported carbon catalyst and its application in the synthesis of acetylides. Background Technology

[0002] Heterocyclic compounds possess unique chemical properties and biological activities, making them widely applicable in the pharmaceutical field. For example, many anticancer drugs are heterocyclic compounds, such as paclitaxel and carboplatin, exhibiting high therapeutic efficacy and selectivity. Nitrogen-containing heterocycles have received considerable attention in terms of synthesis, reactivity, and biological evaluation. This is because nitrogen-containing heterocycles exist in a variety of compounds, holding significance not only in biology but also in industrial applications. Furthermore, nitrogen-containing heterocycles can serve as intermediates in the synthesis of other compounds. Therefore, finding simple and convenient synthetic methods is of great importance. Existing synthetic methods mainly involve metal-free and metal-catalyzed cyclization reactions of unsaturated substrates. Copper salts are among the most well-known and useful catalysts for nucleophilic hydrocarbon cyclization. However, most are used as homogeneous catalysts, which are clearly unsuitable for drug molecule synthesis. Therefore, it is necessary to develop a recyclable heterogeneous catalyst with low metal leaching.

[0003] Nitrogen-substituted alkynes possess unique nucleophilic and electrophilic centers, making them a versatile class of alkyne derivatives. However, their synthetic applications are extremely limited due to the difficulty in preparing these compounds. Current methods primarily utilize reactions of ketoximes with higher-order organic acid salts, oxidative cross-coupling reactions of imines with alkyne or alkyne-copper groups, and homogeneous metal-ligand complex catalysts. However, terminal alkynes readily dimerize in copper salts, copper acetylates, and oxygen atmospheres, forming complexes. Some imines in the starting materials are difficult to prepare and extremely unstable, capable of dimerizing into dinitrogen compounds via copper catalysis. An unprecedented [5+1] heterocyclization reaction utilizes the reactivity of imines, offering a new possibility for the efficient synthesis of medically important nitrogen-containing heterocyclic compounds. However, existing homogeneous metal-ligand complex catalysts not only require expensive ligands and cannot be recycled, but also leave metal residues, leading to a series of drug safety issues. Therefore, it is essential to design a series of heterogeneous catalysts capable of effectively catalyzing the synthesis of alkyne imines and enabling recycling. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing a metal-supported carbon catalyst and its application in the synthesis of acetylides. By constructing a metal catalyst and a suitable catalytic system, a variety of acetylides can be prepared from oxime compounds.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] The first objective of this invention is to provide a metal-supported carbon catalyst, expressed as M@CT, M / L@CT, wherein: M is any one or more of the metals Cu, Ni, Fe, or Co; L is any one or more of bipyridine, triphenylphosphine, o-phenanthroline, tributyl phosphate, or triethyl phosphite; C represents carbon; and T represents temperature, which is 300 ℃ to 800 ℃.

[0007] As an alternative implementation, the temperature T is 300 ℃, 500 ℃, 600 ℃ or 800 ℃.

[0008] As an optional implementation, for M@CT, the mass content of each component is as follows: M: 5~10%, the remainder being carbon.

[0009] As an optional implementation, for M / L@CT, the mass content of each component is as follows: M: 5-10%, L: 20-120%, and the remainder is carbon.

[0010] The second objective of this invention is to provide a method for preparing a metal-supported carbon catalyst, which is any one of methods one to two:

[0011] Method 1 includes the following steps:

[0012] Step A1: Metal salts are loaded onto carbon using an impregnation technique and then vacuum dried to obtain the catalyst precursor M@C;

[0013] Step B1: The catalyst precursor M@C is calcined in an inert gas or reducing atmosphere to obtain catalyst M@CT;

[0014] Method 2 includes the following steps:

[0015] Step A2: Using an impregnation technique, a metal salt and ligand L are co-loaded onto carbon and dried to obtain catalyst precursor M / L@C. The ligand L is any one of bipyridine, triphenylphosphine, o-phenanthroline, tributyl phosphate, or triethyl phosphite.

[0016] Step B2: The catalyst precursor M@C is calcined in an inert gas or reducing atmosphere to obtain catalyst M / L@CT.

[0017] As an optional implementation, in step B1 or B2, the calcination conditions are: calcination at 300-800 °C in an inert atmosphere for 3-5 hours.

[0018] Furthermore, as an optional implementation, in step B1 or B2, the calcination conditions are: calcination at 300–800°C in a reducing atmosphere for 5 hours.

[0019] As an optional implementation, in step B1 or B2, the inert gas is nitrogen, and the space velocity of the inert gas is in the range of 100 to 10000 mL / g catalyst / h.

[0020] As an optional implementation, in step B1 or B2, the reducing gas is a mixture of hydrogen and argon in a volume ratio of 5%:95%, and the space velocity of the reducing gas is in the range of 100 to 10000 ml / g catalyst / h.

[0021] As an optional implementation, in step A1 or A2, the metal salt is a soluble salt MX of a metal ion, wherein the metal ion M... + Including Cu 2+ Ni 2+ Fe 3+ or Co 2+ One or more of these, soluble salt X - Including OAc - NO3 - , or Cl - Any one or more of them.

[0022] As an optional implementation, in step A1, the mass ratio of the metal salt to carbon is 1:10 to 3:5.

[0023] As an optional implementation, in step A2, the mass ratio of the metal salt, ligand L, and carbon is 3:4:20 to 6:20:15.

[0024] A third objective of this invention is to provide the application of the aforementioned metal-supported carbon catalyst in the catalytic preparation of alkynylimines from oxime compounds and terminal alkyne compounds.

[0025] As an optional implementation, the oxime compound has the following structural formula:

[0026]

[0027] Wherein, R1 is selected from or .

[0028] Furthermore, as an optional embodiment, the oxime compound is 1-phenyl-1-butanone O-acetyloxime, with the following structural formula:

[0029]

[0030] As an optional implementation, the terminal alkyne compound is phenylacetylene substituted with an electron-donating group or an electron-withdrawing group, wherein the electron-donating group or electron-withdrawing group is one of methyl, tert-butyl, phenyl, cyano, or halogen (F, Cl, Br, I).

[0031] As an optional implementation, the terminal alkyne compound has the following structural formula:

[0032]

[0033] Wherein, the R2 group is an electron-donating group or an electron-withdrawing group, and the electron-donating group or electron-withdrawing group is one of methyl, tert-butyl, phenyl, cyano, or halogen (F, Cl, Br, I).

[0034] Furthermore, as an optional implementation, the R2 group is selected from any of the following structures:

[0035]

[0036] As an optional implementation, the reaction for preparing acetylinimine from oxime compounds and terminal alkynes involves mixing the oxime compounds with the terminal alkynes and reacting them in 1,2-dichloroethane, acetonitrile, tetrahydrofuran, and 1,4-dioxane reagent under the catalysis of the metal-supported carbon catalyst to obtain the acetylinimine compound.

[0037] As an optional implementation, the reaction temperature is 90-130 °C.

[0038] As an optional implementation, the molar ratio of the oxime compound and the terminal alkyne compound is 1-4:1.

[0039] As an optional implementation, the amount of the metal-supported carbon catalyst is 20 mg to 50 mg.

[0040] As an optional implementation, the amount of the 1,2-dichloroethane reagent used is 1 mL to 3 mL.

[0041] A fourth objective of this invention is to provide acetylinium prepared by any of the methods described above.

[0042] As an optional implementation, the acetylinimine compound has the following structure:

[0043]

[0044] Wherein, R1 is selected from or R2 is an electron-donating or electron-withdrawing group, wherein the electron-donating or electron-withdrawing group is one of methyl, tert-butyl, phenyl, cyano, or halogen (F, Cl, Br, I).

[0045] Furthermore, as an optional embodiment, the acetylinimine compound has any of the following structures:

[0046]

[0047] Beneficial effects: The catalyst preparation process of this invention is simple, uses inexpensive metals as catalysts, can be recycled multiple times, and can significantly reduce costs. Attached Figure Description

[0048] Figure 1 Transmission electron microscopy (TEM) images of M@CT: (a) TEM image of M@C-300 (H2) catalyst; (b) TEM image of M@C-500 (H2) catalyst; (c) TEM image of M@C-600 (H2) catalyst; (d) TEM image of M@C-800 (H2) catalyst; (e) TEM image of M@C-500 (N2) catalyst;

[0049] Figure 2 The image shows the polycrystalline X-ray diffraction (XRD) pattern of M@CT.

[0050] Figure 3 This is a schematic diagram of the catalytic reaction of the present invention;

[0051] Figure 4 This is a graph showing the cycle stability data for the M / L@CT catalyst. Detailed Implementation

[0052] The present invention will be further explained below with reference to the embodiments and accompanying drawings.

[0053] This invention discloses a method for synthesizing metal catalysts by calcination using a series of non-precious metal salts, carbon, etc. This material can catalyze the reaction of a series of oximes and their derivatives with terminal alkynes to generate alkyne imines.

[0054] Preparation example: Preparation of Cu / CT catalyst

[0055] (1) Using impregnation technology, carbon 1-1.5 g was impregnated for 12 hours with an anhydrous ethanol solution containing 150-600 mg of a soluble salt (MX) containing metal ions and 0.2-2 g of ligand L. After removing the anhydrous ethanol, the carbon was placed in an oven and vacuum dried at 80°C for 8 hours to obtain the catalyst precursor MX@C.

[0056] Optional, M is the metal Cu 2+ Ni 2+ Fe3+ or Co 2+ Any one or more of them.

[0057] Optional, soluble salt X includes OAc. - NO3 - , or Cl - Any one or more of them.

[0058] Optionally, the ligand L is any one of bipyridine, triphenylphosphine, o-phenanthroline, tributyl phosphate, or triethyl phosphite.

[0059] (2) The catalyst precursors MX@C or M / L@C prepared by impregnation method are heated to T of 300 ℃~800 ℃ respectively in a tube furnace under an inert gas N2 or a reducing H2 atmosphere, and calcined for 5 hours to obtain catalysts M / CT or M / L@CT.

[0060] Optionally, the space velocity of the inert gas can range from 100 to 10,000 mL / g catalyst / h. In the following preparation examples, an inert gas space velocity of 1200 mL / g catalyst / h is used.

[0061] Optionally, the space velocity of the reducing gas can range from 100 to 10,000 mL / g catalyst / h. In the following preparation examples, a space velocity of 1200 mL / g catalyst / h is used.

[0062] Preparation Example 1: Preparation of Catalyst Cu / C-300 (H2)

[0063] (1) Using impregnation technology, 1 g of carbon was impregnated with an anhydrous ethanol solution containing 285.9 mg of Cu ions (Cu(OAc)2) for 12 hours. After removing the anhydrous ethanol, the carbon was placed in an oven and vacuum dried at 80 °C for 8 hours to obtain the catalyst precursor Cu(OAc)2@C.

[0064] (2) The catalyst precursor Cu(OAc)2@C prepared by impregnation method was heated to T=300 ℃ in a tube furnace at a rate of 5℃ / min under a reducing H2 atmosphere and calcined for 5 hours to obtain the reduced Cu / C-300(H2) catalyst.

[0065] Preparation Example 2: Preparation of Catalyst Cu / C-500 (H2)

[0066] (1) Using impregnation technology, 1 g of carbon was impregnated with an anhydrous ethanol solution containing 285.9 mg of Cu ions (Cu(OAc)2) for 12 hours. After removing the anhydrous ethanol, the carbon was placed in an oven and vacuum dried at 80 °C for 8 hours to obtain the catalyst precursor Cu(OAc)2@C.

[0067] (2) The catalyst precursor Cu(OAc)2@C prepared by impregnation method was heated to T of 500 °C at a rate of 5 °C / min in a tube furnace under a reducing H2 atmosphere and calcined for 5 hours to obtain the reduced Cu / C-500(H2) catalyst.

[0068] Preparation Example 3: Preparation of Catalyst Cu / C-600 (H2)

[0069] (1) Using impregnation technology, 1 g of carbon was impregnated with an anhydrous ethanol solution containing 285.9 mg of Cu ions (Cu(OAc)2) for 12 hours. After removing the anhydrous ethanol, the carbon was placed in an oven and vacuum dried at 80 °C for 8 hours to obtain the catalyst precursor Cu(OAc)2@C.

[0070] (2) The catalyst precursor Cu(OAc)2@C prepared by impregnation method was heated to T of 600 °C at a rate of 5 °C / min in a tube furnace under a reducing H2 atmosphere and calcined for 5 hours to obtain the reduced Cu / C-600(H2) catalyst.

[0071] Preparation Example 4: Preparation of Catalyst Cu / C-800 (H2)

[0072] (1) Using impregnation technology, 1 g of carbon was impregnated with an anhydrous ethanol solution containing 285.9 mg of Cu ions (Cu(OAc)2) for 12 hours. After removing the anhydrous ethanol, the carbon was placed in an oven and vacuum dried at 80 °C for 8 hours to obtain the catalyst precursor Cu(OAc)2@C.

[0073] (2) The catalyst precursor Cu(OAc)2@C prepared by impregnation method was heated to T of 800 °C at a rate of 5 °C / min in a tube furnace under a reducing H2 atmosphere and calcined for 5 hours to obtain the reduced Cu / C-800(H2) catalyst.

[0074] Preparation Example 5: Preparation of Catalyst Cu / C-500 (N2)

[0075] (1) Using impregnation technology, 1 g of carbon was impregnated with an anhydrous ethanol solution containing 285.9 mg of a soluble salt of Cu ions (Cu(OAc)2) for 12 hours. After removing the anhydrous ethanol by rotary evaporation, the carbon was dried in an oven at 80 °C under vacuum for 8 hours to obtain the catalyst precursor Cu(OAc)2@C.

[0076] (2) The catalyst precursor Cu(OAc)2@C prepared by impregnation method was heated to T of 500 ℃ in a tube furnace at a rate of 5 ℃ / min under an inert N2 atmosphere and calcined for 5 hours to obtain Cu / C-500(N2) catalyst.

[0077] Preparation Example 6: Preparation of Catalyst Cu / P / C-500 (N2)

[0078] (1) Using the impregnation technique, a soluble salt containing Cu ions (Cu(OAc)2) 285.9 mg and the ligand P(OEt) 3523.1 mg were used. 1 g of carbon was impregnated with anhydrous ethanol solution for 12 hours. After removing the anhydrous ethanol, the carbon was dried under vacuum at 80 °C for 8 hours to obtain the catalyst precursor Cu(OAc)2-P(OEt)3@C.

[0079] (2) The catalyst precursor Cu(OAc)2-P(OEt)3@C prepared by impregnation method was heated to T of 500 ℃ in a tube furnace at a rate of 5 ℃ / min under an inert N2 atmosphere and calcined for 5 hours to obtain Cu / P / C-500(N2) catalyst.

[0080] The catalysts obtained in the above preparation examples were all analyzed by transmission electron microscopy (TEM), and the results are as follows: Figure 1 As shown, according to Figure 1 The results shown in (a)-(e) are as follows: (a) is M@C-300(H2) with a particle size between 20 and 50 nm; (b) is M@C-500(H2) with a particle size between 40 and 70 nm; (c) is M@C-600(H2) with a particle size between 20 and 40 nm; (d) is M@C-800(H2) with a particle size between 10 and 50 nm; and (e) is M@C-500(N2) with a particle size between 20 and 60 nm.

[0081] The catalysts obtained in the above preparation examples were all analyzed by polycrystalline X-ray diffraction (XRD), and the results are as follows: Figure 2 As shown in the figure, from top to bottom, they are M@C-300(H2), M@C-500(H2), M@C-600(H2), M@C-800(H2), and M@C-500(N2). According to... Figure 2 The results shown are from PDF card number 04-0836, with angles of 43.297, 50.433, and 74.130. The peak positions observed are the same as those of elemental copper.

[0082] Example: Evaluation of catalyst reaction performance

[0083] Metal catalysts can catalyze the preparation of acetylinimine from O-acetyloxime. The specific steps are as follows: In a Shrek reaction tube, add 20-50 mg of the catalyst prepared in the above preparation example, 20.5-82.1 mg (0.1-0.4 mmol) of 1-phenyl-1-butanone O-acetyloxime (compound 1), 16.0-64.1 mg (0.1-0.4 mmol) of terminal alkyne (compound 2), and 13.8-69.1 mg (0.1-0.5 mmol) of potassium carbonate. Add 1-3 mL of 1,2-dichloroethane (DCE), then exhaust the gas for 3 minutes. Heat to 90-130 °C under an argon atmosphere for 20 hours. Purify the product using a chromatography column to obtain the acetylinimine product (compound 3). Figure 3 As shown.

[0084] The following examples explore the optimal conditions for catalyst reaction performance through experimental investigation, and evaluate the substrate applicability of the prepared catalyst for catalytic reactions, such as... Figure 3 As shown, in the current heterogeneous reaction system, various phenylacetylenes with electron-donating or electron-withdrawing groups on the benzene ring can be converted to the corresponding products in moderate to good yields. Specific examples are as follows:

[0085] Example 1: Preparation of methyl(E)-4-(((1-phenylbutyldiene)amino)ethynyl)benzene (3a)

[0086] The specific steps are as follows: In a Shrek reaction tube, 40 mg of the catalyst (Cu / P / C-500(H2)) from Preparation Example 6, 20.5 mg (0.1 mmol) of 1-phenyl-1-butanone O-acetyl oxime, 48.1 mg (0.3 mmol) of terminal alkyne (2a), and 41.5 mg (0.3 mmol) of potassium carbonate were added. 2 mL of 1,2-dichloroethane was added, and the atmosphere was vented for 3 minutes. The mixture was heated to 110 °C for 20 hours under an argon atmosphere. The product was purified by column chromatography with a yield of 58%. Its structure was determined by NMR, confirming the product as methyl(E)-4-(((1-phenylbutyldiene)amino)ethynyl)benzene. The NMR data of the obtained product are as follows:

[0087] 1 H NMR (400 MHz, CDCl3) δ (ppm) 8.01 (d, J = 8.3 Hz, 2H), 7.97 (d, J=7.5 Hz, 2H), 7.53 - 7.42 (m, 5H), 3.93 (s, 3H), 3.15 - 3.06 (m, 2H), 1.78 (m,2H), 1.07 (t, J=7.4 Hz, 3H).

[0088] Example 2: Preparation of (E)-N-((3-fluorophenyl)ethynyl-1-phenylbutyl-1-imine (3b)

[0089] The specific steps are as follows: In a Shrek reaction tube, 40 mg of the catalyst (Cu / P / C-500(H2)) from Preparation Example 6, 20.5 mg (0.1 mmol) of 1-phenyl-1-butanone O-acetyl oxime, 36.0 mg (0.3 mmol) of terminal alkyne (2b), and 41.5 mg (0.3 mmol) of potassium carbonate were added. 2 mL of 1,2-dichloroethane was added, and the mixture was vented for 3 minutes. The mixture was heated to 110 °C and reacted for 20 hours under an argon atmosphere. The product was purified by column chromatography with a yield of 72%. Its structure was determined by NMR, confirming the product as (E)-N-((3-fluorophenyl)ethynyl-1-phenylbutyl-1-imine). The NMR data of the obtained product are as follows:

[0090] 1 H NMR (400 MHz, CDCl3) δ (ppm) 7.92 (d, J = 8.2 Hz, 2H), 7.50 (t, J =7.3 Hz, 1H), 7.41 (t, J = 7.8 Hz, 2H), 7.17 (d, J = 9.3 Hz, 2H), 7.05 (dt, J= 6.8, 4.4 Hz, 2H), 2.91 (t, J = 7.3 Hz, 2H), 1.74 (h, J = 8.9, 8.1 Hz, 2H), 0.97 (t, J = 7.4 Hz, 3H).

[0091] 13 C NMR (101 MHz, CDCl3) δ (ppm) 161.0, 132.8, 130.2, 130.1, 128.5,128.5, 128.4, 128.0, 123.3, 119.3, 119.1, 117.0, 116.8, 80.7, 74.4, 40.5,17.8, 13.9.

[0092] Example 3: Preparation of (E)-1-phenyl-N-(p-tolylethynyl)butyl-1-imine (3c)

[0093] The specific steps are as follows: In a Shrek reaction tube, 40 mg of the catalyst (Cu / P / C-500(H2)) from Preparation Example 6, 20.5 mg (0.1 mmol) of 1-phenyl-1-butanone O-acetyl oxime, 34.8 mg (0.3 mmol) of terminal alkyne (2c), and 41.5 mg (0.3 mmol) of potassium carbonate were added. 2 mL of 1,2-dichloroethane was added, and the mixture was vented for 3 minutes. The mixture was heated to 110 °C under an argon atmosphere and reacted for 20 hours. The product was purified by column chromatography with a yield of 54%. Its structure was determined by NMR, confirming the product as (E)-1-phenyl-N-(p-tolylethynyl)butyl-1-imine. The NMR data of the obtained product are as follows:

[0094] 1 H NMR (400 MHz, CDCl3 ) δ (ppm) 7.96 (d, J = 7.8 Hz, 2H), 7.45 (m,3H), 7.37 (d, J = 7.4 Hz, 2H), 7.16 (d, J = 7.7 Hz, 2H), 3.11 (t, J = 7.7 Hz,2H), 2.37 (s, 3H), 1.77 (m, 2H), 1.07 (t, J = 7.3 Hz, 3H).

[0095] 13 C NMR (101 MHz, CDCl3 ) δ (ppm) 181.5, 137.9, 136.9, 131.3, 129.2,128.6, 127.4, 121.8, 95.4, 90.3, 35.9, 29.7, 21.5, 21.1, 14.3.

[0096] Example 4: Preparation of (E)-1-phenyl-N-(thiophene-1-ethynyl)butyl-1-imine (3d)

[0097] The specific steps are as follows: In a Shrek reaction tube, 40 mg of the catalyst (Cu / P / C-500(H2)) from Preparation Example 6, 20.5 mg (0.1 mmol) of 1-phenyl-1-butanone O-acetyl oxime, 32.4 mg (0.3 mmol) of terminal alkyne (2d), and 41.5 mg (0.3 mmol) of potassium carbonate were added. 2 mL of 1,2-dichloroethane was added, and the mixture was vented for 3 minutes. The mixture was heated to 110 °C for 20 hours under an argon atmosphere. The product was purified by column chromatography with a yield of 50%. Its structure was determined by NMR, confirming the product as (E)-1-phenyl-N-(thiophene-1-ethynyl)butyl-1-imine. The NMR data of the obtained product are as follows:

[0098] 1 H NMR (400 MHz, CDCl3) δ (ppm) 7.96 (d, J = 7.4 Hz, 2H), 7.46 (m,3H), 7.32 (d, J = 4.6 Hz, 1H), 7.21 (d, J = 3.2 Hz, 1H), 7.06 – 7.01 (m, 1H), 3.09 (t, J = 7.7 Hz, 2H), 1.77 (m, 2H), 1.09 (t, J = 7.4 Hz, 3H).

[0099] 13 C NMR (101 MHz, CDCl3 ) δ (ppm) 180.8, 136.7, 134.5, 131.6, 131.3,128.7, 127.7, 127.4 (d, J = 3.6 Hz), 125.0, 94.5, 88.5, 36.2, 21.2, 14.3.

[0100] Example 5: Preparation of (E)-N-([1,1'-biphenyl]-4-ethynyl)-1-phenylbutyl-1-imine (3e)

[0101] The specific steps are as follows: In a Shrek reaction tube, 40 mg of the catalyst (Cu / P / C-500(H2)) from Preparation Example 6, 20.5 mg (0.1 mmol) of 1-phenyl-1-butanone O-acetyl oxime, 53.5 mg (0.3 mmol) of terminal alkyne (2e), and 41.5 mg (0.3 mmol) of potassium carbonate were added. 2 mL of 1,2-dichloroethane was added, and the mixture was vented for 3 minutes. The reaction was carried out at 110 °C for 20 hours under an argon atmosphere. The product was purified by column chromatography with a yield of 50%. Its structure was determined by NMR, identifying the product as (E)-N-([1,1'-biphenyl]-4-ethynyl)-1-phenylbutyl-1-imine. The NMR data of the obtained product are as follows:

[0102] 1H NMR (400 MHz, CDCl3) δ (ppm) 7.99 (d, J = 7.4 Hz, 2H), 7.61 (t, J =8.0 Hz, 4H), 7.54 (d, J = 8.2 Hz, 2H), 7.47 (m, 5H), 7.37 (t, J = 7.2 Hz,1H), 3.19 – 3.10 (m, 2H), 1.80 (m, 2H), 1.10 (t, J = 7.3 Hz, 3H).

[0103] 13 C NMR (101 MHz, CDCl3) δ (ppm) 182.0, 140.5, 136.8, 133.0, 131.7,131.6, 128.9, 128.6, 127.6, 127.4, 127.1, 127.0, 123.8, 95.0, 91.5, 36.1,21.2, 14.4.

[0104] Example 6: Preparation of (E)-1-phenyl-N-(p-tert-butylphenylethynyl)butyl-1-imine (3f)

[0105] The specific steps are as follows: In a Shrek reaction tube, 40 mg of the catalyst (Cu / P / C-500(H2)) from Preparation Example 6, 20.5 mg (0.1 mmol) of 1-phenyl-1-butanone O-acetyl oxime, 47.5 mg (0.3 mmol) of terminal alkyne (2f), and 41.5 mg (0.3 mmol) of potassium carbonate were added. 2 mL of 1,2-dichloroethane was added, and the mixture was vented for 3 minutes. The mixture was heated to 110 °C for 20 hours under an argon atmosphere. The product was purified by column chromatography with a yield of 47%. Its structure was determined by NMR, confirming the product as (E)-1-phenyl-N-(p-tert-butylphenylethynyl)butyl-1-imine. The NMR data of the obtained product are as follows:

[0106] 1 H NMR (300 MHz, CDCl3 ) δ (ppm) 7.97 (d, J = 6.7 Hz, 2H), 7.51-7.37(m, 7H), 3.16-3.06 (m, 2H), 1.82-1.72 (m, 2H), 1.34 (s, 9H), 1.07 (t, J = 7.4Hz, 3H).

[0107] 13C NMR (75 MHz, CDCl3) δ (ppm) 181.6, 151.0, 136.9, 131.5, 131.1,128.6, 127.4, 125.4, 121.8, 95.4, 90.3, 35.9, 34.8, 31.3, 21.1, 14.4.

[0108] Example 7: Preparation of (E)-4(((1-phenylbutyldiene)amino)ethynyl)cyanobenzene (3g)

[0109] The specific steps are as follows: In a Shrek reaction tube, 40 mg of the catalyst (Cu / P / C-500(H2)) from Preparation Example 6, 20.5 mg (0.1 mmol) of 1-phenyl-1-butanone O-acetyl oxime, 38.1 mg (0.3 mmol) of terminal alkyne (2 g), and 41.4 mg (0.3 mmol) of potassium carbonate were added. 2 mL of 1,2-dichloroethane was added, and the atmosphere was vented for 3 minutes. The mixture was heated to 110 °C under an argon atmosphere and reacted for 20 hours. The product was purified by column chromatography with a yield of 56%. Its structure was determined by NMR, identifying the product as (E)-4(((1-phenylbutyldiene)amino)ethynyl)cyanobenzene. The NMR data of the obtained product are as follows:

[0110] 1 H NMR (400 MHz, CDCl3) δ (ppm) 7.96 (d, J = 7.4 Hz, 2H), 7.61 (d, J =8.2 Hz, 2H), 7.49 (m, 5H), 3.09 (t, J = 7.5 Hz, 2H), 1.76 (m, 2H), 1.06 (t, J= 7.4 Hz, 3H).

[0111] 13C NMR (101 MHz, CDCl3) δ (ppm) 183.8, 136.3, 132.5, 132.1, 132.0,131.3, 130.2, 129.9, 128.7, 127.6, 118.8, 110.4, 94.4, 36.4, 21.3, 14.3.

[0112] Example 8: Preparation of methyl(Z)-4-(((2,2-dimethyl-1-phenylpropyldiene)amino)ethynyl)benzene (3h)

[0113] The specific steps are as follows: In a Shrek reaction tube, 40 mg of the catalyst (Cu / P / C-500(H2)) from Preparation Example 6, 21.9 mg (0.1 mmol) of 2,2-dimethyl-1-phenylpropanone O-acetyloxime, 48.0 mg (0.3 mmol) of terminal alkyne (2h), and 41.5 mg (0.3 mmol) of potassium carbonate were added. 2 mL of 1,2-dichloroethane was added, and the atmosphere was vented for 3 minutes. The mixture was heated to 110 °C for 20 hours under an argon atmosphere. The product was purified by column chromatography with a yield of 69%. Its structure was determined by NMR, confirming the product as methyl(Z)-4-(((2,2-dimethyl-1-phenylpropyldiene)amino)ethynyl)benzene. The NMR data of the obtained product are as follows:

[0114] 1 H NMR (400 MHz, CDCl3) δ (ppm) 7.84 (d, J = 8.3 Hz, 2H), 7.42 (m,3H), 7.18 (d, J = 7.7 Hz, 2H), 7.07 (d, J = 8.2 Hz, 2H), 3.86 (s, 3H), 1.28(s, 9H).

[0115] 13 C NMR (101 MHz, CDCl3) δ (ppm) 194.4, 166.7, 138.5, 131.1, 129.3,129.2, 128.6, 128.1, 126.3, 93.2, 88.6, 52.1, 41.1, 28.4.

[0116] Example 9: Preparation of (Z)-N-((4-fluorophenyl)ethynyl)-2,2-dimethyl-1-phenyl-1-imine (3i)

[0117] The specific steps are as follows: In a Shrek reaction tube, 40 mg of the catalyst (Cu / P / C-500(H2)) from Preparation Example 6, 21.9 mg (0.1 mmol) of 2,2-dimethyl-1-phenylpropanone O-acetyloxime, 36.0 mg (0.3 mmol) of terminal alkyne (2i), and 41.5 mg (0.3 mmol) of potassium carbonate were added. 2 mL of 1,2-dichloroethane was added, and the atmosphere was vented for 3 minutes. The mixture was heated to 110 °C for 20 hours under an argon atmosphere. The product was purified by column chromatography with a yield of 58%. Its structure was determined by NMR, identifying the product as (Z)-N-((4-fluorophenyl)ethynyl)-2,2-dimethyl-phenyl-1-imine. The NMR data of the obtained product are as follows:

[0118] 1H NMR (400 MHz, CDCl3) δ (ppm) 7.43 (m, 3H), 7.18 (d, J = 6.2 Hz,2H), 7.03 – 6.96 (m, 2H), 6.91 – 6.83 (m, 2H), 1.28 (s, 9H).

[0119] 13 C NMR (101 MHz, CDCl3) δ (ppm) 193.2, 162.1 (d, J = 248.7 Hz), 138.6, 133.3 (d, J = 8.2 Hz), 128.4, 128.0, 126.5, 120.4, 115.3 (d, J = 22.0Hz), 90.2, 88.2, 40.9, 28.4.

[0120] Results of the catalytic generation of various acetylide imine compounds using a metal-supported carbon catalyst are as follows: Figure 3 As shown.

[0121] Example 10: Repeatability Experiment of Metal-Supported Carbon Catalyst

[0122] The metal-supported carbon catalyst obtained in Preparation Example 6 was used to conduct reproducible catalytic experiments. The specific process was as follows: the catalyst was recovered by filtration using a sand core funnel, washed three times with 15 mL of ethyl acetate, then washed three times with 15 mL of deionized water, dried in a vacuum drying oven at 100 °C for 8 h, and ground to obtain a reusable catalyst.

[0123] The cycle stability data of this metal-supported carbon catalyst are as follows: Figure 4 As shown in the figure, after 6 cycles, the catalytic effect of the catalyst did not decrease significantly, and the yield error was within the normal fluctuation range.

[0124] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and extensions can be made without departing from the principle of the present invention, and these improvements and extensions should also be considered within the scope of protection of the present invention.

Claims

1. The application of metal-supported carbon catalysts in the catalytic preparation of alkynylimines from oxime compounds and terminal alkyne compounds, characterized in that: The expression for a metal-supported carbon catalyst is M / L@CT, where: M is any one or more of the metals Cu, Ni, Fe, or Co; L is any one of bipyridine, triphenylphosphine, o-phenanthroline, tributyl phosphate, or triethyl phosphite; C represents carbon; and T represents the temperature, which is 300 ℃ to 800 ℃. The preparation method of the metal-supported carbon catalyst includes the following steps: Step A2: Using an impregnation technique, a metal salt and ligand L are co-loaded onto carbon and dried to obtain catalyst precursor M / L@C. The ligand L is any one of bipyridine, triphenylphosphine, o-phenanthroline, tributyl phosphate, or triethyl phosphite. Step B2: The catalyst precursor M / L@C is calcined in an inert or reducing atmosphere at a temperature T to obtain catalyst M / L@CT.

2. The application according to claim 1, characterized in that: The oxime compound is 1-phenyl-1-butanone O-acetyloxime, and the terminal alkyne compound is phenylacetylene substituted with an electron-donating group or an electron-withdrawing group, wherein the electron-donating group or electron-withdrawing group is one of methyl, tert-butyl, phenyl, cyano, or halogen.

3. The application according to claim 1, characterized in that: The reaction for preparing alkynylimine from oxime compounds and terminal alkynes involves mixing oxime compounds, potassium carbonate, and terminal alkynes, and reacting them in a 1,2-dichloroethane reagent under the catalysis of the metal-supported carbon catalyst to obtain the alkynylimine compound.

4. The application according to claim 3, characterized in that: The reaction temperature is 90~130 ℃.

5. The application according to claim 1, characterized in that: The molar ratio of the oxime compound to the terminal alkyne is 1-4:

1.

6. The application according to claim 1, characterized in that: In step B2, the calcination conditions are: calcination at 300–800 °C in an inert or reducing atmosphere for 3–5 hours; In step B2, the inert atmosphere is nitrogen, and the space velocity of the inert atmosphere is in the range of 100 to 10000 mL / g catalyst / h; the reducing atmosphere is a mixture of hydrogen and argon in a volume ratio of 5%:95%, and the space velocity of the reducing atmosphere is in the range of 100 to 10000 mL / g catalyst / h.

7. The application according to claim 1, characterized in that: In step A2, the metal salt is a soluble salt MX of a metal ion, wherein the metal ion M + Including Cu 2+ Ni 2+ Fe 3+ or Co 2+ One or more of these, soluble salt X - Including OAc - NO 3- , or Cl - Any one or more of them.

8. The application according to claim 1, characterized in that: In step A2, the mass ratio of the metal salt, ligand L, and carbon is 3:4:20 to 6:20:15.

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