M-benzene bridged alkynyl pyrazole pyridine derivative as well as preparation method and application thereof

Abstract

The invention discloses an m-benzene bridged alkynyl pyrazole pyridine derivative as well as a preparation method and application thereof, and belongs to the technical field of pyrazole pyridine derivatives. The preparation method of the m-benzene bridged alkynyl pyrazole pyridine derivative comprises the following steps: dissolving pyrazole halide, an ethynyl aromatic compound and a catalyst in a solvent, carrying out heating reflux in an N2 atmosphere, and carrying out filtering, spin-drying and chromatographic evaporation to obtain a solid product; and adding the solid product into a mixed solvent prepared from methanol and dichloromethane according to a volume ratio of 1: 1, adding HCl into the mixed solvent to remove a protecting group, adding NaHCO3 to adjust the pH value of the mixed solvent to 7, filtering to obtain a solid, and washing, filtering and vacuum drying the solid to obtain the derivative. By adopting the m-benzene bridged alkynyl pyrazole pyridine derivative as well as the preparation method and the application thereof, the problems that a single pyridine pyrazole ligand adopted in the prior art is simple in coordination form and an obtained complex is single in structure and function can be solved.

Description

Technical Field

[0001] The invention relates to the technical field of pyrazole and pyridine derivatives, and in particular to an isophenyl bridged alkynyl pyrazole and pyridine derivative and a preparation method and application thereof. Background Art

[0002] Pyrazole ligands are a relatively complex class of multifunctional organic bridging ligands, and their supramolecular assemblies have good application value in catalysis, magnetism, molecular recognition, ion sensing, photophysical properties, etc. At the same time, supramolecular self-assembly driven by transition metal-directed coordination of pyridine system has become a research hotspot in recent years due to its good guidance and suitable chemical bond energy.

[0003] The existing technology usually uses a single pyrazole or pyridine ligand, most of which are one-step reactions, have relatively simple products, and cannot be controlled. Therefore, it is particularly important to design pyrazole and pyridine ligands with different functions into the same ligand and adopt a programmed hierarchical self-assembly strategy. At the same time, the weak π interaction between the alkynyl group and the metal cation provides favorable conditions for the formation of novel supramolecular structures. This strategy can obtain a more novel structure and adjustable function supramolecular system by controlling the selection of different secondary assembly metal centers. Summary of the invention

[0004] The purpose of the present invention is to provide an isophenyl bridged alkynyl pyrazole pyridine derivative and a preparation method and application thereof, so as to solve the problems that the coordination form of the single pyridine pyrazole ligand used in the prior art is simple and the structure and function of the obtained complex are single.

[0005] To achieve the above object, the present invention provides an isophenyl bridged alkynyl pyrazole pyridine derivative, the chemical structure of which is:

[0006]

[0007] R 1 For -H or

[0008] R 2 for

[0009] The preparation method of the above-mentioned m-phenyl bridged alkynyl pyrazole pyridine derivative comprises the following steps:

[0010] S1. Dissolve the pyrazole halide, ethynyl aromatic compound and catalyst in a solvent and 2 The mixture was heated to reflux under an atmosphere, and a solid product was obtained after filtration, spin drying, and chromatography evaporation;

[0011] S2. Add the solid product to a mixed solvent of methanol and dichloromethane in a volume ratio of 1:1, add HCl to the mixed solvent to remove the protecting group, and add NaHCO 3 The pH of the mixed solvent is adjusted to 7, and a solid is obtained after filtration. The solid is washed, filtered, and vacuum dried to obtain a derivative.

[0012] Preferably, in S1, the pyrazole halide is 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, the ethynyl aromatic compound is 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, the catalyst is tetrakistriphenylphosphine palladium and cuprous iodide, and the solvent is triethylamine and toluene;

[0013] 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, tetrakistriphenylphosphine palladium, cuprous iodide, and 1 MOL / L tetrabutylammonium fluoride tetrahydrofuran solution were dissolved in triethylamine and toluene. 2 Heat to reflux at 50°C-80°C under atmosphere for 8 hours-15 hours, filter, spin-dry at 40°C-60°C, chromatograph, and rotary evaporate to obtain a solid product;

[0014] The molar ratio of 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole to 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is 1:1.0-1.2, the molar ratio of 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine to 1MOL / L tetrabutylammonium fluoride tetrahydrofuran solution is 1:1.0-1.5, and the eluent during chromatography is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 2-5:1;

[0015] The S2 is obtained by R 1 For -H, R 2 for Derivatives of.

[0016] Preferably, in S1, the pyrazole halide is 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole, the ethynyl aromatic compound is 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, the catalyst is tetrakistriphenylphosphine palladium and cuprous iodide, and the solvent is triethylamine and toluene;

[0017] 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole, 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, tetrakistriphenylphosphine palladium, cuprous iodide, and 1 MOL / L tetrabutylammonium fluoride tetrahydrofuran solution were dissolved in triethylamine and toluene. 2Heat to reflux at 50°C-80°C under atmosphere for 8 hours-15 hours, filter, spin-dry at 40°C-60°C, chromatograph, and rotary evaporate to obtain a solid product;

[0018] The molar ratio of 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole and 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is 1:1.0-1.2, the molar ratio of 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine and 1MOL / L tetrabutylammonium fluoride tetrahydrofuran solution is 1:1.0-1.5, and the eluent during chromatography is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 2-5:1;

[0019] The S2 is obtained by R 1 for R 2 for Derivatives of.

[0020] Preferably, the preparation method of the 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is:

[0021] Dissolve (3-bromophenylethynyl)trimethylsilane, 3-ethynylpyridine, tetrakistriphenylphosphine palladium, and cuprous iodide in triethylamine and toluene. 2 The mixture was stirred at 60° C.-90° C. for 12 to 18 hours under an atmosphere, filtered through diatomaceous earth, dried by rotation, chromatographed, and rotary evaporated to obtain 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine; the molar ratio of (3-bromophenylethynyl)trimethylsilane to 3-ethynylpyridine was 1:1.0-1.2; and the eluent during chromatography was pure dichloromethane.

[0022] Preferably, the preparation method of the 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole is:

[0023] Dissolve 4-ethyl-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole, 1,3-dibromo-5-iodobenzene, bistriphenylphosphine palladium dichloride, and cuprous iodide in triethylamine. 2 The mixture was heated to reflux at 35°C-45°C under an atmosphere for 8 hours to 15 hours, filtered through diatomaceous earth, dried by rotation at 40°C-60°C, chromatographed, and rotary evaporated to obtain 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole;

[0024] The molar ratio of 1,3-dibromo-5-iodobenzene and 4-ethyl-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole is 1:1.0-1.2, and the eluent during chromatography is a mixture of petroleum ether and ethyl acetate in a volume ratio of 8-15:1.

[0025] Preferably, in S1, the pyrazole halide is 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, the ethynyl aromatic compound is 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, the catalyst is tetrakistriphenylphosphine palladium and cuprous iodide, and the solvent is triethylamine and toluene;

[0026] 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, tetrakistriphenylphosphine palladium, cuprous iodide, and 1 MOL / L tetrabutylammonium fluoride tetrahydrofuran solution were dissolved in triethylamine and toluene. 2 Heat to reflux at 50°C-80°C under atmosphere for 8 hours-15 hours, filter, spin-dry at 40°C-60°C, chromatograph, and rotary evaporate to obtain a solid product;

[0027] The molar ratio of 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole to 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is 1:1.0-1.2, the molar ratio of 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine to 1MOL / L tetrabutylammonium fluoride tetrahydrofuran solution is 1:1.0-1.5, and the eluent during chromatography is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 2-5:1;

[0028] The S2 is obtained by R 1 For -H, R 2 for Derivatives of.

[0029] Preferably, the preparation method of 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is:

[0030] Dissolve (3-bromophenylethynyl)trimethylsilane, 4-ethynylpyridine, tetrakistriphenylphosphine palladium, and cuprous iodide in triethylamine and toluene. 2 The mixture was stirred at 60° C.-90° C. under an atmosphere for 12 to 18 hours, filtered through diatomaceous earth, dried by rotation, chromatographed, and rotary evaporated to obtain 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine; the molar ratio of (3-bromophenylethynyl)trimethylsilane to 4-ethynylpyridine was 1:1.0-1.2; and the eluent during chromatography was pure dichloromethane.

[0031] Preferably, in S1, the pyrazole halide is 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, the ethynyl aromatic compound is m-diethynylbenzene, the catalyst is tetrakistriphenylphosphine palladium and cuprous iodide, and the solvent is triethylamine;

[0032] Dissolve 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, m-diethynylbenzene, tetrakistriphenylphosphine palladium, and cuprous iodide in triethylamine. 2 Heat under reflux at 40°C-50°C for 6 hours-10 hours under atmosphere, filter, spin-dry at 40°C-60°C, chromatograph, and rotary evaporate to obtain a solid product;

[0033] The molar ratio of 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole to m-diethynylbenzene is 1:2.21, and the eluent during chromatography is a mixture of dichloromethane and ethyl acetate in a volume ratio of 40:1;

[0034] The S2 is obtained by R 1 For -H, R 2 for Derivatives of.

[0035] The above-mentioned m-phenyl bridged alkynyl pyrazole pyridine derivatives are used in coordination chemistry, heavy metal ion detection, catalysis, and molecular machines.

[0036] The m-phenyl-bridged alkynyl pyrazole and pyridine derivatives at different positions have different coordination angles. By designing compounds that can coordinate with different metal ions to form compounds with different angles, shapes, and coordination numbers, materials with novel structures and good catalytic and sensing properties are obtained.

[0037] Pyrazole ligands are a class of organic ligands with bidentate coordination functions, which can form three coordination forms in supramolecular self-assembly: monodentate coordination, bidentate bridging and bidentate chelation. Compared with some monodentate ligands, the self-assembled molecules constructed by pyrazole ligands have more novel structures and richer functional properties. At the same time, the supramolecular self-assembly driven by transition metal-guided coordination of pyridine system is applied to many synthetic fields due to its good guidance, suitable chemical bond energy and other advantages. The present invention designs pyrazole and pyridine into the same ligand, adopts programmed hierarchical self-assembly, and prepares a novel and functionally adjustable supramolecular structure by controlling and selecting different secondary assembly metal centers. At the same time, by introducing alkynyl groups to produce π weak interactions with metal cations, the assembly structure can be made more novel, and the pyrazole and pyridine functional groups in the ligand can realize the selective recognition of metal cations through the metal-organic coordination of metal ions.

[0038] The advantages and positive effects of the isophenyl bridged alkynyl pyrazole pyridine derivatives and their preparation methods and applications are as follows:

[0039] 1. The present invention designs pyrazole and pyridine into the same ligand with different coordination angles. By designing compounds that can coordinate with different metal ions to form different angles, shapes, and coordination numbers, a material with novel structure and good catalytic and sensing properties is obtained. At the same time, by introducing an alkynyl group to generate a π weak interaction with a metal cation, the assembly structure can be made more novel. The pyrazole and pyridine functional groups in the ligand can realize the selective recognition of metal cations through the metal-organic coordination of metal ions.

[0040] 2. The preparation method of the present invention is simple to operate and involves only common organic synthesis steps; the production cost is low, and the raw materials are cheap and easily available; the yield is above 70%; the post-processing and purification are simple, and it is suitable for the industrial production of isophenyl-bridged alkynylpyrazole and pyridine derivatives.

[0041] 3. The m-phenyl bridged alkynyl pyrazole pyridine derivatives of the present invention can be applied to the fields of coordination chemistry, heavy metal ion sensing, catalysis, molecular machines, etc., and have a wide range of applications.

[0042] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 The synthetic route diagram of Example 1 to Example 4 of the present invention;

[0044] Figure 2 From the a-axis direction, the complex Ag-[(bpy)Pd] 2 (L) 2 (NO 3 ) 2 -Crystal structure diagram of OTf;

[0045] Figure 3 From the a-axis direction, the complex Ag-[(bpy)Pd] 2 (L) 2 (NO 3 ) 2 Crystal stacking structure diagram;

[0046] Figure 4 From the b-axis direction, the complex Ag-[(bpy)Pd] 2 (L) 2 (NO 3 ) 2 Crystal stacking structure diagram;

[0047] Figure 5 From the c-axis direction, the complex Ag-[(bpy)Pd] 2 (L) 2 (NO 3 ) 2Crystal stacking structure diagram;

[0048] Figure 6 For the complex [(bpy)Pd] 2 (L) 2 (NO 3 ) 2 UV-visible absorption spectra of mixed solutions with different cation additions;

[0049] Figure 7 For the complex [(bpy)Pd] 2 (L) 2 (NO 3 ) 2 Hg was added to the solution 2+ and Hg 2+ UV-visible absorption spectra of other cations. DETAILED DESCRIPTION

[0050] The embodiments of the present invention are described in detail below in conjunction with the accompanying drawings.

[0051] Embodiment 1

[0052] R in a metaphenyl bridged alkynylpyrazole pyridine derivative 1 For -H, R 2 for The structural formula of the derivative is:

[0053]

[0054] Synthetic circuits such as Figure 1 As shown, the specific steps are as follows:

[0055] S2. Dissolve 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole (1.65 g; 5.99 mmol), 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine (1.66 g; 5.97 mmol), tetrakistriphenylphosphine palladium (0.023 eq; 160 mg, 0.138 mmol), cuprous iodide (0.048 eq; 54 mg, 0.284 mmol), and tetrabutylammonium fluoride (1 MOL / L tetrahydrofuran solution, 6.1 mL) in triethylamine (20 mL) and toluene (10 mL). 2 The mixture was heated to reflux at 60°C for 10 hours under ambient temperature, filtered through celite, dried by rotation at 50°C, chromatographed (petroleum ether: ethyl acetate = 3:1), and rotary evaporated to obtain a solid product.

[0056] The preparation method of 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is:

[0057] (3-Bromophenylethynyl)trimethylsilane (7.02 mmol; 1.77 g), 3-ethynylpyridine (7.09 mmol; 730.97 mg), tetrakistriphenylphosphine palladium (0.025 eq; 0.176 mmol; 202.80 mg), and cuprous iodide (0.026 eq; 0.183 mmol; 34.76 mg) were dissolved in triethylamine (20 mL) and toluene (10 mL). 2 The mixture was stirred at 80°C overnight under an atmosphere, filtered through celite, dried at 50°C, chromatographed (dichloromethane), and rotary evaporated to obtain 1.66 g of 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine. The yield of 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine was 85%.

[0058] S2, use 20mL methanol and 20mL dichloromethane to prepare a mixed solvent, dissolve the solid product in the mixed solvent, add 1ml HCl to remove the protecting group, add NaHCO 3 The pH was adjusted to 7, and a solid was obtained by filtration. A small amount of methanol was added to the solid for washing, and the solid was filtered and dried in vacuo to obtain 1.14 g of compound I. The yield of compound I was 71%.

[0059] Embodiment 2

[0060] An isophenyl bridged alkynyl pyrazole pyridine derivative R 1 For -H, R 2 for The structural formula of the derivative is:

[0061]

[0062] Synthetic circuits such as Figure 1 As shown, the specific synthesis steps are the same as those in Example 1, except that:

[0063] In step S1, 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine.

[0064] In the preparation process of 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, 3-ethynylpyridine is 4-ethynylpyridine.

[0065] The yield of compound II was 82%.

[0066] Embodiment 3

[0067] R in a metaphenyl bridged alkynylpyrazole pyridine derivative 1 for R 2 for The structural formula of the derivative is:

[0068]

[0069] Synthetic circuits such as Figure 1 As shown, the specific steps are as follows:

[0070] S1. Dissolve 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine (1.37 g; 4.98 mmol), 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole (1.00 g; 2.45 mmol), tetrakistriphenylphosphine palladium (0.026 eq; 147.22 mg, 0.127 mmol), cuprous iodide (0.025 eq; 37.71 mg, 0.198 mmol), and tetrabutylammonium fluoride (1 MOL / L tetrahydrofuran solution, 5.2 mL) in triethylamine (20 mL) and toluene (10 mL). 2 The mixture was heated to reflux at 60°C overnight under ambient temperature, filtered through celite, dried by rotation at 50°C, chromatographed (petroleum ether: ethyl acetate = 3:1), and rotary evaporated to obtain a solid product.

[0071] The preparation method of 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole is as follows:

[0072] 4-Ethyl-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole (1.15 g; 6.53 mmol), 1,3-dibromo-5-iodobenzene (2.28 g; 6.34 mmol), bistriphenylphosphine palladium dichloride (0.025 eq; 111.25 mg, 0.159 mmol), and cuprous iodide (0.026 eq; 31.39 mg, 0.165 mmol) were dissolved in triethylamine (30 mL) and N 2 The mixture was heated to reflux at 40°C for 9 hours under an atmosphere, filtered through diatomaceous earth, dried at 50°C, chromatographed (petroleum ether: ethyl acetate = 10: 1), and rotary evaporated to obtain 2.25 mg of the intermediate product 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole. The yield of 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole was 87%.

[0073] S2, use 20mL methanol and 20mL dichloromethane to prepare a mixed solvent, dissolve the solid product in the mixed solvent, add 1ml HCl to remove the protecting group, add NaHCO 3 The pH was adjusted to 7, and a solid was obtained by filtration. A small amount of dichloromethane and a large amount of petroleum ether were added to the solid for recrystallization. After filtration and vacuum drying, 985.67 mg of compound III was obtained. The yield of compound III was 70.5%.

[0074] Embodiment 4

[0075] R in a metaphenyl bridged alkynylpyrazole pyridine derivative 1 For -H, R 2 for The structural formula of the derivative is:

[0076]

[0077] Synthetic circuits such as Figure 1 As shown, the specific steps are as follows:

[0078] 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole (2.43 g; 8.74 mmol), m-diethynylbenzene (500 mg; 5.97 mmol), tetrakistriphenylphosphine palladium (0.012 eq; 109.82 mg, 0.095 mmol), and cuprous iodide (0.025 eq; 37.71 mg, 0.198 mmol) were dissolved in triethylamine (15 mL). 2 The mixture was heated to reflux at 45°C for 8 hours under ambient temperature, and then dried at 50°C. The solid product was obtained by chromatography (dichloromethane: ethyl acetate = 40:1) and rotary evaporation.

[0079] Use 20 mL of methanol and 20 mL of dichloromethane to prepare a mixed solvent, dissolve the solid product in the mixed solvent, add 1 ml of HCl to remove the protecting group, and add NaHCO 3 The pH was adjusted to 7, and a solid was obtained by filtration. A small amount of methanol was added to the solid for washing, and the solid was filtered and dried in vacuo to obtain 716 mg of compound IV. The yield of compound IV was 70%.

[0080] Experimental Testing

[0081] (1) The nuclear magnetic resonance analysis results of the m-phenyl bridged alkynyl pyrazole pyridine derivatives prepared in Examples 1 to 4 are as follows:

[0082] Example 1 Compound Ⅰ:

[0083] 1 H NMR (400 MHz, DMSO-d 6 ,ppm)=13.24(br,1H),8.78(s,1H),8.62(d,J=4.0Hz,1H),8.17(s,1H),8.01(d ,J=8.0Hz,1H),7.77(s,1H),7.69(s,1H),7.60-7.54(m,2H),7.50-7.46(m,2H).

[0084] Example 2 Compound II:

[0085] 1 H NMR (400 MHz, DMSO-d 6 ,ppm)=13.26(s,1H),8.65(dd,J=4.4,1.6Hz,2H),8.18(s,1H),7.77(s,1H),7.71(t,J=1.4Hz,1H),7.63–7.54(m,4H),7.50(t,J=7.7Hz,1H).

[0086] Example 3 Compound III:

[0087] 1 H NMR (400 MHz, DMSO-d 6 ,ppm)=13.28(s,1H),8.80(s,2H),8.62(d,J=4.8Hz,2H),8.01(t,J=7.5Hz,4H),7.84(s,2H),7.7 8(s,1H),7.73(s,2H),7.67(d,J=7.7Hz,4H),7.55(t,J=7.7Hz,2H),7.50(dd,J=7.8,5.0Hz,2H).

[0088] Example 4 Compound IV:

[0089] 1 H NMR (400 MHz, DMSO-d 6 ,ppm)=13.23(s,2H),8.16(s,2H),7.76(s,2H),7.54(s,1H),7.49–7.45(m,2H),7.42(dd,J=9.1,5.9Hz,1H).

[0090] The nitrogen on the pyrazole and the nitrogen on the pyridine in the pyrazole-pyridine ligands have good coordination ability with metals, so a supramolecular structure is obtained by coordination with metals, as shown in (2) to (3) below:

[0091] (2) Compound I obtained in Example 1 was firstly reacted with bpyPd(NO 3 ) 2 The primary assembly is obtained by assembling and positioning, and then assembled with silver nitrate and silver trifluoromethanesulfonate to obtain different topological structures. The specific operation includes the following steps:

[0092] a. The compound obtained in Example 1 and bpyPd(NO 3 ) 2 Assemble the position, the specific operations are as follows:

[0093] Compound (11.4 mg, 0.02 mmol) and bpyPd(NO3 ) 2 (19.3 mg, 0.05 mmol) dissolved in 1.0 mL DMSO-d 6 The assembly was carried out at 40 °C and the assembly was monitored by H NMR tracking.

[0094] Complex [(bpy)Pd] 2 (L) 2 (NO 3 ) 2 The results of the NMR analysis are:

[0095] 1 H NMR (400MHz, DMSO, ppm) = 8.80 (d, J = 1.8Hz, 1H), 8.65 (dd, J = 4.8, 1.2Hz, 1H), 8.46 (s, 2H), 8.41 (s, 2H), 8.38 (s, 2H), 8.20 (d, J = 5. 0Hz,2H),8.04–8.00(m,1H),7.82(t,J=6.8Hz,2H),7.54(dd,J=7.7,5.0Hz,1H),7.42(d,J=27.0Hz,2H),7.19(s,1H),7.04(s,1H).

[0096] b. The primary assembly [(bpy)Pd] 2 (L) 2 (NO 3 ) 2 (14.82 mg, 0.125 mmol) and AgOTf (3.21 mg, 0.0125 mmol) were dissolved in 1.0 mL DMSO-d 6 The mixture was stirred at room temperature for 30 min and at 40 °C for 1 h, and ethyl acetate was diffused into the above solution. Block crystals were obtained after 5 days. The assembly was monitored by hydrogen spectrum nuclear magnetic resonance.

[0097] Complex Ag-[(bpy)Pd] 2 (L) 2 (NO 3 ) 2 The results of NMR analysis of -OTf are:

[0098] 1 H NMR (400 MHz, DMSO-d 6,ppm)=8.80(s,4H),8.65(d,J=4.6Hz,5H),8.54–8.31(m,22H),8.20(d,J=5.2Hz,7H),8.03(d,J=7.9 Hz,4H),7.82(t,J=6.5Hz,7H),7.59–7.51(m,5H),7.40(d,J=20.0Hz,7H),7.17(s,4H),7.02(s,3H).

[0099] Complex Ag-[(bpy)Pd] 2 (L) 2 (NO 3 ) 2 The crystal structure of -OTf is as follows Figure 2 shown.

[0100] c. The primary assembly [(bpy)Pd] 2 (L) 2 (NO 3 ) 2 (23.72 mg, 0.02 mmol) and AgNO 3 (3.40 mg, 0.02 mmol) dissolved in 1.0 mL DMSO-d 6 The mixture was stirred at room temperature for 30 min and at 40 °C for 1 h. Ethyl acetate was added to precipitate the solid, which was centrifuged and dried. The solid was dissolved in a 1:1 mixture of acetonitrile and methanol. Isopropyl ether, a poor solvent, was diffused into the above solution. Block crystals were obtained after 2 days. The assembly was monitored by hydrogen spectrum nuclear magnetic resonance tracking.

[0101] Complex Ag-[(bpy)Pd] 2 (L) 2 (NO 3 ) 2 -NO 3 The results of the NMR analysis are:

[0102] 1 H NMR (400 MHz, DMSO-d 6 ,ppm)=8.88(s,6H),8.72(s,9H),8.41(s,28H),8.19(s,15H),7.80(s,10H),7.66(s,10H),7.41(s,10H),7.07(d,J=74.3Hz,7H).

[0103] Complex Ag-[(bpy)Pd] 2 (L) 2 (NO 3 ) 2 -NO 3 The crystal structure of Figure 3 , Figure 4 , Figure 5 shown.

[0104] Example 3 Compound II obtained by reacting bpyPd(NO 3 ) 2 Assembly

[0105] (3) Compound II obtained in Example 3 and bpyPd(NO 3 ) 2 Assemble the position, the specific operations are as follows:

[0106] Compound II (11.4 mg, 0.02 mmol) and bpyPd(NO 3 ) 2 (7.73 mg, 0.02 mmol) was dissolved in 0.7 mL DMSO-d 6 The assembly was carried out at 40 °C and the assembly was monitored by H NMR tracking.

[0107] The results of NMR analysis of complex II are as follows:

[0108] 1 H NMR (400MHz, DMSO, ppm) = 9.48 (d, J = 39.4Hz, 3H), 9.33 (s, 3H), 9.10 (s, 3H), 8.81 (s, 9H), 8.69 (s, 4H), 8.63 (s, 7H), 8.47 (d, J = 34.1Hz, 29H), 8.25 (d ,J=27.9Hz,19H),8.02(d,J=7.1Hz,8H),7.84(s,26H),7.71(dd,J=23.2, 5.5Hz,26H),7.65–7.57(m,11H),7.49(s,12H),7.33(s,7H),7.21(s,2H).

[0109] (4) For the complex [(bpy)Pd] 2 (L) 2 (NO 3 ) 2 Conduct UV test.

[0110] The complex [(bpy)Pd] 2 (L) 2 (NO 3 ) 2 Dissolved to a concentration of 10 μM. Take 2 mL of the mixed solution and add 5 μL of cation (Cd 2+ 、Co 2+ , Hg 2+ , K + , Li+ Mg 2+ , Mn 2+ 、Na + 、Ni 2+ 、Zn 2+ ) were tested in parallel, with a cation solution concentration of 0.1 M. Hg 2+ It was found that Hg can still be detected in the presence of other ions. 2+ . Figure 6 For the complex [(bpy)Pd] 2 (L) 2 (NO 3 ) 2 UV-visible absorption spectra of mixed solutions with different cation additions; Figure 7 For the complex [(bpy)Pd] 2 (L) 2 (NO 3 ) 2 With Hg 2+ The UV-visible absorption spectrum of other cations added to the mixed solution. Figure 6 , Figure 7 As shown, only the addition of Hg 2+ It shows obvious UV absorption enhancement, indicating that the structure can single recognize Hg 2+ .

[0111] Therefore, the present invention adopts the above-mentioned meta-phenyl bridged alkynylpyrazole pyridine derivative and its preparation method and application. The preparation method has few steps, simple operation, and only involves common organic synthesis steps; the production cost is low, and the raw materials are cheap and easy to obtain; the yield is more than 70%; the post-treatment and purification are simple, and it is suitable for industrial production of meta-phenyl bridged alkynylpyrazole pyridine derivatives. The meta-phenyl bridged alkynylpyrazole pyridine derivatives of the present invention can solve the problems of simple coordination form of the single pyridine pyrazole ligand used in the prior art and single structure and function of the obtained complex.

[0112] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. An isophenyl bridged alkynylpyrazole pyridine derivative, characterized in that: Its chemical structure is: R1 is -H or R2 is 2. The method for preparing an isophenyl bridged alkynylpyrazole pyridine derivative according to claim 1, characterized in that: The following steps are involved: S1, dissolving the pyrazole halide, the ethynyl aromatic compound and the catalyst in a solvent, heating under reflux in a N2 atmosphere, filtering, spin drying, and chromatographic evaporation to obtain a solid product; S2. Add the solid product to a mixed solvent of methanol and dichloromethane in a volume ratio of 1:1, add HCl to the mixed solvent to deprotect the protecting group, add NaHCO3 to adjust the pH of the mixed solvent to 7, filter to obtain a solid, wash, filter and vacuum dry the solid to obtain a derivative.

3. The method for preparing an isophenyl bridged alkynylpyrazole pyridine derivative according to claim 2, characterized in that: In S1, the pyrazole halide is 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, the ethynyl aromatic compound is 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, the catalyst is tetrakistriphenylphosphine palladium and cuprous iodide, and the solvent is triethylamine and toluene; Dissolve 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, tetrakistriphenylphosphine palladium, cuprous iodide, and 1MOL / L tetrabutylammonium fluoride tetrahydrofuran solution in triethylamine and toluene, heat under reflux at 50° C.-80° C. for 8 hours-15 hours under N2 atmosphere, filter, spin-dry at 40° C.-60° C., chromatograph, and rotary evaporate to obtain a solid product; The molar ratio of 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole to 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is 1:1.0-1.2, the molar ratio of 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine to 1MOL / L tetrabutylammonium fluoride tetrahydrofuran solution is 1:1.0-1.5, and the eluent during chromatography is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 2-5:1; In the S2, R1 is -H, and R2 is Derivatives of.

4. The method for preparing an isophenyl bridged alkynylpyrazole pyridine derivative according to claim 2, characterized in that: In S1, the pyrazole halide is 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole, the ethynyl aromatic compound is 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, the catalyst is tetrakistriphenylphosphine palladium and cuprous iodide, and the solvent is triethylamine and toluene; Dissolve 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole, 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, tetrakistriphenylphosphine palladium, cuprous iodide, and 1MOL / L tetrabutylammonium fluoride tetrahydrofuran solution in triethylamine and toluene, heat under reflux at 50° C.-80° C. for 8 hours-15 hours under N2 atmosphere, filter, spin-dry at 40° C.-60° C., chromatograph, and rotary evaporate to obtain a solid product; The molar ratio of 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole and 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is 1:1.0-1.2, the molar ratio of 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine and 1MOL / L tetrabutylammonium fluoride tetrahydrofuran solution is 1:1.0-1.5, and the eluent during chromatography is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 2-5:1; The S2 obtained in R1 is R2 is Derivatives of.

5. The method for preparing an isophenyl bridged alkynylpyrazole pyridine derivative according to claim 3 or 4, characterized in that: The preparation method of the 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is: (3-bromophenylethynyl)trimethylsilane, 3-ethynylpyridine, tetrakistriphenylphosphine palladium and cuprous iodide are dissolved in triethylamine and toluene, stirred at 60°C-90°C for 12-18 hours under N2 atmosphere, filtered through diatomaceous earth, spin dried, chromatographed and rotary evaporated to obtain 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine; the molar ratio of (3-bromophenylethynyl)trimethylsilane to 3-ethynylpyridine is 1:1.0-1.2; the eluent during chromatography is pure dichloromethane.

6. The method for preparing an isophenyl bridged alkynylpyrazole pyridine derivative according to claim 4, characterized in that: The preparation method of the 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole is: Dissolve 4-ethyl-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole, 1,3-dibromo-5-iodobenzene, bistriphenylphosphine palladium dichloride, and cuprous iodide in triethylamine, heat and reflux at 35°C-45°C under N2 atmosphere for 8 hours-15 hours, filter with diatomaceous earth, spin dry at 40°C-60°C, chromatograph, and rotary evaporate to obtain 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole; The molar ratio of 1,3-dibromo-5-iodobenzene and 4-ethyl-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole is 1:1.0-1.2, and the eluent during chromatography is a mixture of petroleum ether and ethyl acetate in a volume ratio of 8-15:

1.

7. The method for preparing an isophenyl bridged alkynylpyrazole pyridine derivative according to claim 2, characterized in that: In S1, the pyrazole halide is 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, the ethynyl aromatic compound is 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, the catalyst is tetrakistriphenylphosphine palladium and cuprous iodide, and the solvent is triethylamine and toluene; Dissolve 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, tetrakistriphenylphosphine palladium, cuprous iodide, and 1MOL / L tetrabutylammonium fluoride tetrahydrofuran solution in triethylamine and toluene, heat under reflux at 50° C.-80° C. for 8 hours-15 hours under N2 atmosphere, filter, spin-dry at 40° C.-60° C., chromatograph, and rotary evaporate to obtain a solid product; The molar ratio of 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole to 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is 1:1.0-1.2, the molar ratio of 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine to 1MOL / L tetrabutylammonium fluoride tetrahydrofuran solution is 1:1.0-1.5, and the eluent during chromatography is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 2-5:1; In the S2, R1 is -H, and R2 is Derivatives of.

8. The method for preparing an isophenyl bridged alkynylpyrazole pyridine derivative according to claim 7, characterized in that: The preparation method of the 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is: (3-bromophenylethynyl)trimethylsilane, 4-ethynylpyridine, tetrakistriphenylphosphine palladium, and cuprous iodide are dissolved in triethylamine and toluene, stirred at 60°C-90°C for 12-18 hours under a N2 atmosphere, filtered through diatomaceous earth, dried by rotation, chromatographed, and rotary evaporated to obtain 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine; the molar ratio of (3-bromophenylethynyl)trimethylsilane to 4-ethynylpyridine is 1:1.0-1.2; and the eluent during chromatography is pure dichloromethane.

9. The method for preparing an isophenyl bridged alkynylpyrazole pyridine derivative according to claim 2, characterized in that: In S1, the pyrazole halide is 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, the ethynyl aromatic compound is m-diethynylbenzene, the catalyst is tetrakistriphenylphosphine palladium and cuprous iodide, and the solvent is triethylamine; Dissolve 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, m-diethynylbenzene, tetrakistriphenylphosphine palladium and cuprous iodide in triethylamine, heat under reflux at 40°C-50°C for 6 hours-10 hours under N2 atmosphere, filter, spin-dry at 40°C-60°C, chromatograph and rotary evaporate to obtain a solid product; The molar ratio of 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole to m-diethynylbenzene is 1:2.21, and the eluent during chromatography is a mixture of dichloromethane and ethyl acetate in a volume ratio of 40:1; In the S2, R1 is -H, and R2 is Derivatives of.

10. Use of the m-phenyl bridged alkynyl pyrazole pyridine derivative as claimed in claim 1 in coordination chemistry, heavy metal ion detection, catalysis, and molecular machinery.

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