Three-dimensional network barium complex catalyst, preparation method and application thereof

Abstract

The application belongs to the field of catalyst and its preparation technology, and particularly relates to a three-dimensional network structure barium complex catalyst and a preparation method and application thereof.The three-dimensional network structure barium complex catalyst is a monoclinic crystal.The preparation method of the three-dimensional network structure barium complex catalyst comprises the following steps: mixing 3-(3-carboxyphenyl)-isonicotinic acid, a barium source and an alkali auxiliary agent in a solvent, heating and reacting, filtering, and standing the filtrate to obtain the three-dimensional network structure barium complex catalyst.The preparation method of the three-dimensional network structure barium complex catalyst has the characteristics of low cost, low toxicity, high selectivity, good stability and green environmental protection when the prepared catalyst with a crystal structure is applied to the preparation of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalysts and its preparation technology, and particularly relates to a three-dimensional network structure barium complex catalyst and a preparation method and application thereof. BACKGROUND

[0002] At present, most of the barium complexes exhibit porous, network or layered structure, which is mainly due to the large ionic radius and flexible coordination mode of barium ions. Some barium complexes are three-dimensional network structures bridged by chlorine; some are three-dimensional framework structures based on specific organic ligands; and some are layered structures. The applications of the barium complexes reported so far are mainly concentrated on: fluorescent materials and sensing applications, adsorption and separation applications, and the potential of barium complexes as adsorbent materials, antibacterial materials, catalytic materials, photoelectric and electromagnetic materials and drug carriers is also explored. However, the in-depth study and application of barium complexes in catalytic organic synthesis are still limited.

[0003] Propargylamine is an alias of propargylamine, which is an unsaturated hydrocarbon containing carbon-carbon triple bond, a multifunctional intermediate in organic synthesis, and an important structural unit of natural products and potential drugs. Propargylamine is widely used in the synthesis of natural products and some complex molecules with certain biological activity. The traditional method is to use propargyl halide, propargyl phosphate amination reaction and nucleophilic attack of organometallic alkynylating reagent or Grignard reagent on imine or its derivative to synthesize. These methods require the synthesis of alkynylating reagents or imine derivatives with poor stability, the above reagents must be used in stoichiometric ratio, are highly sensitive to water, and require strict control of reaction conditions, and will produce an equivalent amount of by-products. However, the efficiency and feasibility of this path are highly dependent on the catalyst. At present, the mainstream catalysts are mainly based on Au, Ir, Cu, Ru, Ag and other noble metal complexes or their salts, which have certain activity, but due to the high price and scarcity of noble metals, their industrial application is seriously restricted.

[0004] In order to reduce the application of noble metals, existing research has developed different methods for the preparation of efficient and stable catalysts, such as CN103819424A discloses a method for preparing propargylamine, using ionic iron(III) complex as catalyst, prepared in anhydrous and anaerobic conditions in an inert gas atmosphere. CN102826947A discloses the use of chiral copper catalyst and base additive as cocatalyst. However, the above methods have problems such as harsh reaction conditions and low enantioselectivity of chiral catalysts. SUMMARY

[0005] The technical problem to be solved by the present application is to overcome the above-mentioned defects existing in the prior art, and provide a preparation method of a three-dimensional network structure barium complex catalyst.

[0006] The three-dimensional network structure barium complex catalyst according to the present application is monoclinic, and has a molecular formula of C 13 H 13 NO7Ba, a molecular weight of 432.58, and a cell parameter of a space group P 121 / c1, a = 12.712 (4) Å, b = 12.526 (3) Å, c = 9.182 (2) Å, β = 100.036 (11) °, and a crystal density of 1.996 g / cm 3 .

[0007] The preparation method of the three-dimensional network structure barium complex catalyst comprises the following steps: mixing 3-(3-carboxyphenyl)-isonicotinic acid, a barium source and an alkaline auxiliary agent in a solvent, heating and reacting, filtering, and slowly volatilizing the solvent at room temperature after the filtrate is placed to obtain three-dimensional network structure barium complex catalyst crystals.

[0008] The solvent is an ethanol and water mixed solvent, and the volume ratio of ethanol to water is 1:1 to 10:1.

[0009] The 3-(3-carboxyphenyl)-isonicotinic acid, the barium source and the alkaline auxiliary agent are mixed according to the following molar fraction ratio: 1 to 3 parts, 2 to 6 parts and 2 to 6 parts.

[0010] The alkaline auxiliary agent is one of sodium hydroxide, ammonia and potassium hydroxide; and the barium source is one of barium chloride, barium nitrate and barium perchlorate.

[0011] The heating and stirring reaction is performed at 50 to 85 DEG C for 1 to 6 hours.

[0012] The filtrate is placed for 10 to 20 days.

[0013] The three-dimensional network structure barium complex catalyst is used in the preparation of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine.

[0014] The catalyst, benzaldehyde, piperidine, phenylacetylene and a solvent are mixed, and then heated and reacted to prepare N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine.

[0015] The solvent is 1,4-dioxane.

[0016] The heating temperature is 80 to 130 DEG C, preferably 100 to 130 DEG C.

[0017] Specifically, the preparation method of the three-dimensional network structure barium complex catalyst includes the following steps: In an ethanol-water (volume ratio 1:1~10:1) solution, add 0.01~0.03mol (2.43~7.29g) of 3-(3-carboxyphenyl)-isonicotinic acid, 0.02~0.06mol (4.16~12.48g) of barium chloride and 0.02~0.06mol (0.7~3.36g) of an alkaline auxiliary agent (ammonia, sodium hydroxide, potassium hydroxide). After heating and stirring the mixture at 50~85℃ for 1~6h, filter the mixture and allow the filtrate to stand for 10~20 days to obtain a colorless and transparent three-dimensional network structure barium complex catalyst single crystal.

[0018] The process for preparing N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine by heating benzaldehyde, piperidine, and phenylacetylene as raw materials to carry out a three-component coupling reaction is as follows: benzaldehyde, piperidine, phenylacetylene, solvent (1,4-dioxane), and a three-dimensional network structure barium complex catalyst are added to a stainless steel reactor. The reaction mixture is then stirred at 80~130℃ for 8 hours. The conversion rate of benzaldehyde is detected by a gas chromatograph equipped with an SE-54 column (0.25μm×0.25mm×30m).

[0019] The three-dimensional network structured barium complex catalyst of the present invention has a core active site that is Ba, which has strong Lewis acidity. 2 The catalyst, through a synergistic and efficient mechanism, catalyzes a three-component coupling reaction to ultimately generate N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine: First, the three-dimensional network structure barium complex catalyst is dried under vacuum at 150°C to remove coordinated water, exposing Ba... 2+ Active site. Ba at the catalyst center. 2+ It coordinates with the carbonyl oxygen atom in the benzaldehyde molecule, significantly enhancing the polarity of the C=O bond and increasing the electrophilicity of the carbonyl carbon atom. Simultaneously, Ba... 2+ The alkynyl π-bond of phenylacetylene undergoes a weak coordination interaction, effectively activating the alkynyl bond and enhancing its reactivity. Secondly, the activated phenylacetylene undergoes nucleophilic addition to activated benzaldehyde to form Ba... 2+ A stable alkynol intermediate is formed. Piperidine undergoes a nucleophilic attack on the activated carbonyl carbon via its nitrogen atom, followed by dehydration to form an imine intermediate. Subsequently, the alkynol intermediate acts as a nucleophile, attacking the electrophilic carbon atom of the imine intermediate, resulting in C-C bond coupling. The addition product undergoes an elimination reaction, losing one molecule of piperidine, ultimately yielding the target product N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine. After the reaction is complete, the target product is derived from Ba... 2+ The active sites dissociate, the active sites of the catalyst are regenerated, and the catalytic cycle is completed.

[0020] Compared with the prior art, the present application has the beneficial effects that:

[0021] (1) The present application first designs and synthesizes a barium complex crystal with a clear structure and a three-dimensional network structure as a catalyst for catalyzing a three-component coupling reaction. Compared with the noble metal catalysts such as gold, silver, copper and ruthenium commonly used in the prior art, the catalyst takes the widely available and low-cost barium ion as the core, greatly reduces the raw material cost and environmental toxicity of the catalyst, and provides a new path for solving the problem of the scarcity and high price of noble metal resources restricting industrial application. At the same time, the crystal catalyst has a stable structure, is easy to recycle and reuse, and shows good application prospects.

[0022] (2) The preparation method of the present application is simple and has mild conditions. After heating reaction by "one-pot method", only filtration, standing of the filtrate and solvent evaporation at room temperature are needed, so that the target catalyst single crystal with high purity and regular structure can be obtained by spontaneous crystallization, avoiding complex post-treatment and purification steps, and the operation is simple, reproducible and suitable for scale-up preparation. By accurately controlling the ratio of the ligand, barium source and adjuvant and the solvent system, the stable catalytic material with the expected three-dimensional network structure and strong Lewis acidity is successfully constructed.

[0023] (3) The catalyst of the present application shows excellent catalytic performance when applied to the synthesis of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine. Compared with the prior art, the present application can efficiently catalyze the three-component reaction under relatively mild conditions (normal pressure or low pressure, ordinary stainless steel reaction kettle), avoids the preparation of unstable imine or metering metal reagent in advance, has high atom economy and less by-products. The catalytic process has high selectivity and good stability, meets the requirements of green and environmentally friendly synthesis, and provides a non-noble metal catalytic, efficient and practical new method for the synthesis of important propargyl amine intermediates. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 Crystal structure diagram of the three-dimensional network structure barium complex catalyst prepared in Example 1.

[0025] Figure 2 Powder X-ray diffraction pattern of the three-dimensional network structure barium complex catalyst prepared in Example 1 and single crystal diffraction pattern simulated from the single crystal diffraction data of the barium complex catalyst.

[0026] Figure 3 Infrared spectra of the three-dimensional network structure barium complex catalyst prepared in Example 1 and the raw material 3-(3-carboxyphenyl)-isonicotinic acid.

[0027] Figure 4 N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine prepared in Example 11 HNMR image. Detailed Implementation

[0028] The present invention will be further described below with reference to specific embodiments.

[0029] The raw materials and additives used in the following examples and comparative examples are all commercially available products.

[0030] Example 1

[0031] The preparation method of the three-dimensional network structure barium complex catalyst includes the following steps: In an ethanol-water (volume ratio 1:1) solution, 0.01 mol (2.430 g) of 3-(3-carboxyphenyl)-isonicotinic acid, 0.02 mol (4.16 g) of barium chloride, and 0.02 mol (0.8 g) of sodium hydroxide are added. After stirring and reacting at 50 °C for 1 h, the mixture is filtered, and the filtrate is allowed to stand for 20 days to obtain a colorless and transparent single crystal of the complex. The crystal structure of the barium complex is determined by X-ray single crystal diffraction, and its crystal structure diagram is shown below. Figure 1 As shown, the three-dimensional network structure barium complex catalyst is monoclinic with the following cell parameters: space group: P 121 / c1, a=12.712(4)Å, b=12.526(3)Å, c=9.182(2)Å, β= 100.036(11)°, crystal density is 1.996 g / cm³ 3 .

[0032] After grinding the three-dimensional network structured barium complex catalyst crystals obtained above into powder, X-ray diffraction experiments were performed, such as... Figure 2 As shown, it can be seen that the measured peak position (b) of the three-dimensional network structure barium complex catalyst is basically consistent with the peak position (a) simulated by the single crystal diffraction data of the barium complex catalyst. This indicates that in order to improve the catalytic efficiency, the purity and crystal form of the three-dimensional network structure barium complex catalyst used in powder form are consistent with those of the single crystal.

[0033] The infrared spectra of the above 3-(3-carboxyphenyl)-isonicotinic acid and its three-dimensional network barium complex are as follows: Figure 3 As shown, by Figure 3 It can be seen that 3-(3-carboxyphenyl)-isonicotinic acid at 1681 cm⁻¹ -1 At position (B), a stretching vibration absorption peak of the carboxyl C=O group appears, and in the three-dimensional network structure of the barium complex, at 1578 cm⁻¹, an absorption peak is observed. -1 and 1391 cm -1 At position (A), both asymmetric stretching vibration absorption peaks and symmetric stretching absorption peaks of the carboxyl radical group were observed, indicating that the carboxyl oxygen atom in the 3-(3-carboxyphenyl)-isonicotinic acid ligand coordinated with the barium ion, which is consistent with the single crystal analysis results.

[0034] The process for preparing N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine by heating to perform three-component coupling reaction with benzaldehyde, piperidine and phenylacetylene is as follows: first, the above three-dimensional network structure barium complex catalyst is dried at 150℃ under vacuum to remove coordination water, then 0.070g of the catalyst, 0.0265g of benzaldehyde, 0.0255g of piperidine, 0.0337g of phenylacetylene and 1.5g of 1,4-dioxane are added into a stainless steel reactor, and the reaction mixture is stirred at 80℃ for 8h. The conversion rate of benzaldehyde and the yield of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine are detected by a gas chromatograph equipped with SE-54 chromatographic column (0.25μm×0.25mm×30m).

[0035] The process for preparing N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine by heating to perform three-component coupling reaction with benzaldehyde, piperidine and phenylacetylene is as follows: first, the above three-dimensional network structure barium complex catalyst is dried at 150℃ under vacuum to remove coordination water, then 0.070g of the catalyst, 0.0265g of benzaldehyde, 0.0255g of piperidine, 0.0337g of phenylacetylene and 1.5g of 1,4-dioxane are added into a stainless steel reactor, and the reaction mixture is stirred at 80℃ for 8h. The conversion rate of benzaldehyde and the yield of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine are detected by a gas chromatograph equipped with SE-54 chromatographic column (0.25μm×0.25mm×30m). 1 HNMR chart, as shown in Figure 4 It can be seen from the HNMR chart that the obtained product is N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine.

[0036] Example 2

[0037] The process for preparing N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine by heating to perform three-component coupling reaction with benzaldehyde, piperidine and phenylacetylene is as follows: first, the above three-dimensional network structure barium complex catalyst is dried at 150℃ under vacuum to remove coordination water, then 0.070g of the catalyst, 0.0265g of benzaldehyde, 0.0255g of piperidine, 0.0337g of phenylacetylene and 1.5g of 1,4-dioxane are added into a stainless steel reactor, and the reaction mixture is stirred at 80℃ for 8h. The conversion rate of benzaldehyde and the yield of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine are detected by a gas chromatograph equipped with SE-54 chromatographic column (0.25μm×0.25mm×30m).

[0038] The process for preparing N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine by heating to perform three-component coupling reaction with benzaldehyde, piperidine and phenylacetylene is as follows: first, the above three-dimensional network structure barium complex catalyst is dried at 150℃ under vacuum to remove coordination water, then 0.070g of the catalyst, 0.0265g of benzaldehyde, 0.0255g of piperidine, 0.0337g of phenylacetylene and 1.5g of 1,4-dioxane are added into a stainless steel reactor, and the reaction mixture is stirred at 80℃ for 8h. The conversion rate of benzaldehyde and the yield of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine are detected by a gas chromatograph equipped with SE-54 chromatographic column (0.25μm×0.25mm×30m).

[0039] Example 3

[0040] The process for preparing N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine by heating to perform three-component coupling reaction with benzaldehyde, piperidine and phenylacetylene is as follows: first, the above three-dimensional network structure barium complex catalyst is dried at 150℃ under vacuum to remove coordination water, then 0.070g of the catalyst, 0.0265g of benzaldehyde, 0.0255g of piperidine, 0.0337g of phenylacetylene and 1.5g of 1,4-dioxane are added into a stainless steel reactor, and the reaction mixture is stirred at 80℃ for 8h. The conversion rate of benzaldehyde and the yield of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine are detected by a gas chromatograph equipped with SE-54 chromatographic column (0.25μm×0.25mm×30m).

[0041] The process for preparing N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine by heating to perform three-component coupling reaction using benzaldehyde, piperidine and phenylacetylene as raw materials is different from example 1 in that the reaction temperature in the present example is 100℃, and the rest is the same as example 1.

[0042] Example 4

[0043] The preparation method of the three-dimensional network structure barium complex catalyst comprises the following steps: in an ethanol-water (volume ratio 4:1) solution, 0.01 mol (2.430 g) of 3-(3-carboxyphenyl)-isonicotinic acid, 0.01 mol (2.082 g) of barium chloride and 0.01 mol (0.35 g) of ammonia water are added, and after stirring at 80℃ for 3h, filtration is performed, and the filtrate is placed for 20 days to obtain colorless transparent complex single crystals. The crystal structure of the three-dimensional network structure barium complex is determined by X-ray single crystal diffraction technology.

[0044] The process for preparing N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine by heating to perform three-component coupling reaction using benzaldehyde, piperidine and phenylacetylene as raw materials is different from example 1 in that the reaction temperature in the present example is 110℃, and the rest is the same as example 1.

[0045] Example 5

[0046] The preparation method of the three-dimensional network structure barium complex catalyst comprises the following steps: in an ethanol-water (volume ratio 5:1) solution, 0.01 mol (2.430 g) of 3-(3-carboxyphenyl)-isonicotinic acid, 0.02 mol (5.22 g) of barium nitrate and 0.02 mol (0.7 g) of ammonia water are added, and after stirring at 85℃ for 3h, filtration is performed, and the filtrate is placed for 20 days to obtain colorless transparent complex single crystals. The crystal structure of the three-dimensional network structure barium complex is determined by X-ray single crystal diffraction technology.

[0047] The process for preparing N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine by heating to perform three-component coupling reaction using benzaldehyde, piperidine and phenylacetylene as raw materials is different from example 1 in that the reaction temperature in the present example is 120℃, and the rest is the same as example 1.

[0048] The three-dimensional network structure barium complex catalysts used in the following examples 6 to 9 are all first filtered and washed with anhydrous ethanol to remove organic residues, and then dried at 80℃ for 12h before being reused.

[0049] Example 6

[0050] The difference between Example 5 is that in the preparation of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine, the recovered and reused three-dimensional network structure barium complex catalyst of Example 5 is added, and the rest of the preparation method and steps are the same as Example 5.

[0051] Example 7

[0052] The difference between Example 6 is that in the preparation of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine, the recovered and reused three-dimensional network structure barium complex catalyst of Example 6 is added, and the rest of the preparation method and steps are the same as Example 6.

[0053] Example 8

[0054] The difference between Example 7 is that in the preparation of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine, the recovered and reused three-dimensional network structure barium complex catalyst of Example 7 is added, and the rest of the preparation method and steps are the same as Example 7.

[0055] Example 9

[0056] The difference between Example 8 is that in the preparation of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine, the recovered and reused three-dimensional network structure barium complex catalyst of Example 8 is added, and the rest of the preparation method and steps are the same as Example 8.

[0057] Example 10

[0058] The preparation method of the three-dimensional network structure barium complex catalyst comprises the following steps: in an ethanol-water (volume ratio 10:1) solution, 0.01 mol (2.430 g) of 3-(3-carboxyphenyl)-isonicotinic acid, 0.02 mol (6.724 g) of barium perchlorate and 0.02 mol (1.12 g) of potassium hydroxide are added, heated to 85℃ and stirred for 6h, then filtered, and the filtrate is placed for 20 days to obtain colorless transparent complex single crystal. The crystal structure of the three-dimensional network structure barium complex is determined by X-ray single crystal diffraction technology.

[0059] The difference between Example 1 is that in the preparation of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine, the three-component coupling reaction is carried out by heating benzaldehyde, piperidine and phenylacetylene as raw materials, and the reaction temperature in this embodiment is 130℃, and the rest is the same as Example 1.

[0060] Comparative Example 1

[0061] Different from example 10, in the preparation of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine, no three-dimensional network structure barium complex catalyst was added, the rest was three-component coupling reaction with benzaldehyde, piperidine, phenylacetylene as raw material, and the rest of the preparation method and steps of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine were the same as example 10.

[0062] In the above examples and comparative examples, the conversion rate of benzaldehyde, the yield of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine, and the purity of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine were detected, and the results are shown in Table 1.

[0063] Table 1 Detection results

[0064]

[0065] From the data in Table 1, it can be seen that: (1) with the addition of three-dimensional network structure barium complex catalyst: in 1,4-dioxane, at a temperature of 80-120℃, the reaction was carried out for 8h, the purity of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine was 98%, but with the increase of temperature, the conversion rate of benzaldehyde and the yield of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine gradually increased, the maximum was 92.3% and 90.5% respectively. (2) Without the addition of three-dimensional network structure barium complex catalyst: the conversion rate of benzaldehyde was 3.2%, N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine was not detected, which showed that the three-dimensional network structure barium complex catalyst had strong catalytic effect. (3) The three-dimensional network structure barium complex catalyst was recycled four times, the conversion rate of benzaldehyde and the yield of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine were reduced very little, which showed that the catalytic performance of three-dimensional network structure barium complex catalyst was basically stable.

Claims

1. A three-dimensional network barium complex catalyst characterized by: The three-dimensional network barium complex catalyst is monoclinic, and the cell parameters are as follows: space group P 121 / c1, a = 12.712(4) Å, b = 12.526(3) Å, c = 9.182(2) Å, β = 100.036(11) °, and the crystal density is 1.996 g / cm 3 The crystal structure is shown as follows: .

2. A method for preparing the three-dimensional network structure barium complex catalyst according to claim 1, characterized in that: The method comprises the following steps: The 3-(3-carboxyphenyl)-isonicotinic acid, a barium source and an alkaline auxiliary agent are mixed in a solvent, heated and reacted, filtered, and the filtrate is left to stand, and the solvent is volatilized at room temperature to obtain a three-dimensional network structure barium complex catalyst crystal.

3. The process for preparing a three-dimensional network barium complex catalyst according to claim 2, characterized by: The solvent is a mixed solvent of ethanol and water, and the volume ratio of ethanol to water is 1:1-10:

1.

4. The process for preparing a three-dimensional network barium complex catalyst according to claim 2, characterized by: The alkaline auxiliary agent is one of sodium hydroxide, ammonia and potassium hydroxide; and the barium source is one of barium chloride, barium nitrate and barium perchlorate.

5. The process for preparing a three-dimensional network barium complex catalyst according to claim 2, characterized by: The reaction is heated and stirred at 50-85 DEG C for 1-6 h; and the filtrate is left to stand for 10-20 days.

6. The process for preparing a three-dimensional network barium complex catalyst according to claim 2, characterized by: The 3-(3-carboxyphenyl)-isonicotinic acid, the barium source and the alkaline auxiliary agent are mixed in a solvent, heated and reacted, filtered, and the filtrate is left to stand, and the solvent is volatilized at room temperature to obtain a three-dimensional network structure barium complex catalyst crystal.

7. Use of the three-dimensional network bar complex catalyst according to claim 1, characterized in that: The catalyst is used in the preparation of N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine.

8. Use of a three-dimensional network barium complex catalyst according to claim 7, characterized in that: The specific operation is that the catalyst, benzaldehyde, piperidine, phenylacetylene and a solvent are mixed, heated and reacted to prepare N-(1-phenyl-3-phenylprop-2-yn-1-yl)piperidine.

9. Use of a three-dimensional network barium complex catalyst according to claim 8, characterized in that: The solvent is 1,4-dioxane.

10. Use of a three-dimensional network barium complex catalyst according to claim 8, characterized in that: The heating temperature is 80-130 DEG C.

Images