Heterogeneous organic polymer catalyst and preparation method, and method for synthesizing aldehyde or lactone compounds

Abstract

This invention discloses a heterogeneous organic polymer catalyst with a structure in which an oxidant and a ligand are simultaneously immobilized on an organic polymer matrix. The organic polymer is a polymerization product of a crosslinking agent monomer with at least one vinyl group on a benzene ring. The oxidant is a nitroxide radical, and the ligand is a nitrogen heterocyclic compound or an amine compound. When combined with a copper salt, this heterogeneous organic polymer catalyst can achieve highly selective and high-yield conversion of HMF to DFF at room temperature and in an oxygen atmosphere. This heterogeneous organic polymer catalyst can be recycled multiple times and can also achieve the efficient synthesis of other aldehydes and lactones.

Description

Technical Field

[0001] This invention relates to the fields of catalysts and organic synthesis technology, specifically to a heterogeneous organic polymer catalyst and its preparation method, as well as a method for synthesizing aldehydes or lactones. Background Technology

[0002] In recent years, biomass, as a renewable carbon source, has received widespread attention. The selective conversion of low-cost biomass macromolecules into small organic molecules (such as high-value-added chemicals and fuels) through green and efficient methods can effectively reduce a country's dependence on fossil fuels. As an important bridge connecting biomass and fossil resources, 5-hydroxymethylfurfural (HMF) can be derived from the dehydration of renewable biomass carbohydrates. Through hydrolysis, esterification, hydrogenation, and redox reactions, it can be converted into high-value-added downstream products. Among these, 2,5-dicarboxyfuran (DFF), as a high-value organic synthesis intermediate, is widely used in pharmaceuticals, organic conductors, polymer materials, and pesticides. Using low-cost HMF as a raw material to synthesize DFF through oxidation reactions offers good economic benefits. Currently, the industrial production process for converting HMF to DFF mainly employs oxidation technology under high-temperature and high-pressure conditions. During the reaction, HMF is readily oxidized to products such as 2,5-furandicarboxylic acid (FDCA), 5-formyl-2-furancarboxylic acid (FFCA), and 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). Therefore, this process typically faces challenges such as low selectivity, high energy consumption, and environmental unfriendliness.

[0003] Professor Shannon S. Stahl of the University of Wisconsin-Madison reported a homogeneous Cu / 2,2,6,6-tetramethylpiperidine oxide (TEMPO) / N-methylimidazole (NMI) catalyst system that can efficiently and selectively oxidize primary alcohols to corresponding aldehydes at room temperature using oxygen as the oxidant (J. Am. Chem. Soc., 2011, 133, 16901-16910). The catalytic mechanism of this system includes two stages: (1) “catalyst oxidation”, Cu I TEMPO-H is oxidized to Cu by O2 via Cu2O2 intermediate. II (2) Substrate oxidation, via TEMPO nitro radicals and Cu. II - The reaction of alcohol oxide intermediates was realized (J. Am. Chem. Soc., 2013, 135, 2357-2367). However, this reaction system has never been used for the conversion of HMF to DFF, and since it is a homogeneous reaction, the added catalyst and ligands can only be used once and cannot be separated and recovered. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a heterogeneous organic polymer catalyst and a method for catalytic synthesis of aldehydes and lactones. By immobilizing a catalytically active fragment oxidant (e.g., TEMPO) and a ligand (e.g., NMI) onto an organic polymer, a heterogeneous organic polymer catalyst is prepared, enabling highly selective and high-yield conversion of HMF to DFF at room temperature and in an oxygen atmosphere.

[0005] To achieve the above objectives, the specific technical solution of the present invention is as follows:

[0006] The present invention provides a heterogeneous organic polymer catalyst having a structure in which an oxidant and a ligand are simultaneously immobilized on an organic polymer matrix. The organic polymer is a polymer product of a crosslinking agent monomer with at least one vinyl group on a benzene ring, the oxidant is a nitric oxide radical, and the ligand is a nitrogen heterocyclic compound or an amine compound.

[0007] Furthermore, the crosslinking agent is one of styrene, divinylbenzene, and mesitylene.

[0008] Furthermore, the oxidant is one of TEMPO and its derivatives, 9-azabicyclo[3.3.1]nonane-N-oxygen radical (ABNO), and 2-azaadamantane-N-oxygen radical (AZADO).

[0009] Furthermore, the ligand is one of NMI, 1,2-diaminocyclohexane, diamine, terpyridine, 1,10-phenanthroline, nitrobenzylimidazole, imidazole, nitrophenylimidazole, pyrrole, pyridine, and 2-methylpyridine.

[0010] The method for preparing the heterogeneous organic polymer catalyst provided by the present invention includes the following steps:

[0011] The oxidant monomer, ligand monomer, crosslinking agent monomer and free radical initiator are dissolved in the first solvent and polymerized at 60-120℃ for 6-24 hours to obtain polymer I;

[0012] Polymer I and peroxide were added to the first solvent and reacted for 3-8 hours to obtain the heterogeneous organic polymer catalyst.

[0013] Furthermore, the free radical initiator is an azo initiator, preferably azobisisobutyronitrile (AIBN).

[0014] Furthermore, the molar ratio of the oxidant monomer, ligand monomer, crosslinking agent monomer, and free radical initiator is 1:(0.5-2):(11-13.5):(0.2-0.55).

[0015] Furthermore, the peroxide is m-chloroperoxybenzoic acid, and the molar ratio of its amount to the amount of the oxidant monomer is (0.5-2):1.

[0016] Furthermore, the first solvent is one or more of tetrahydrofuran, toluene, n-butanol, or n-octanol.

[0017] The method for synthesizing aldehydes or lactones provided by this invention includes the following steps:

[0018] Primary alcohol or diol, the above-mentioned heterogeneous organic polymer catalyst and copper salt are added to a second solvent and reacted under an oxygen or air atmosphere to obtain aldehydes or lactones.

[0019] Furthermore, the mass molar ratio of the heterogeneous organic polymer catalyst to the primary alcohol or diol is 120–250 g: 1 mol.

[0020] Furthermore, the copper ions in the copper salt are either I or II valent, and the anions are OTf-, Cl-, or Br-. - Thiophene dicarboxylic acid (TC-), I-, SO4 2- PF6 - OAc - BF4 - NO3 - One of them.

[0021] Furthermore, the molar ratio of the copper salt to the primary alcohol or diol is (0.04–0.07):1.

[0022] Furthermore, the second solvent is at least one of nitrile solvents, haloalkane solvents, amide solvents, sulfoxide solvents, or water.

[0023] Furthermore, the second solvent is selected from at least one of acetonitrile, water, dichloromethane, chloroform, 1,2-dichloroethane, N,N-dimethylformamide, N,N-dimethylacetamide, or dimethyl sulfoxide.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0025] The heterogeneous organic polymer catalyst provided by this invention simultaneously immobilizes oxidants and ligands, allowing them to function as both simultaneously. In combination with copper salts, it enables highly selective and high-yield conversion of HMF to DFF at room temperature and in an oxygen atmosphere. This heterogeneous organic polymer catalyst is not only recyclable but also enables the efficient synthesis of other aldehydes and lactones. Attached Figure Description

[0026] Figure 1This is a schematic diagram of the preparation method of the heterogeneous organic polymer catalyst in Example 1;

[0027] Figure 2 Here is a scanning electron microscope image of the heterogeneous organic polymer catalyst prepared in Example 1;

[0028] Figure 3 The infrared spectrum of the heterogeneous organic polymer catalyst prepared in Example 1;

[0029] Figure 4 The heterogeneous organic polymer catalyst prepared in Example 1 13 C solid-state nuclear magnetic resonance spectrum;

[0030] Figure 5 The results show the stability test results of the heterogeneous organic polymer catalyst prepared in Example 1. Detailed Implementation

[0031] To enable those skilled in the art to more clearly understand the technical means and effects adopted by the present invention to achieve the intended purpose, the specific embodiments, structures, features, and effects of the present invention will be further described in detail below with reference to the accompanying drawings and preferred embodiments. The examples given are only for explaining the present invention and are not intended to limit the scope of the present invention. In the embodiments of the present invention, unless otherwise specified, all raw material components are commercially available products well known to those skilled in the art; unless specifically specified, the technical means used are conventional means well known to those skilled in the art.

[0032] The present invention provides a heterogeneous organic polymer catalyst having a structure in which an oxidant and a ligand are simultaneously immobilized on an organic polymer matrix. The organic polymer is a polymerization product of a crosslinking agent monomer with at least one vinyl group on a benzene ring, the oxidant is a nitric oxide radical, and the ligand is a nitrogen heterocyclic compound or an amine compound.

[0033] In a preferred embodiment, the crosslinking agent is one of styrene, divinylbenzene, and mesitylene.

[0034] In a preferred embodiment, the oxidant is one of TEMPO and its derivatives, 9-azabicyclo[3.3.1]nonane-N-oxygen radical (ABNO), and 2-azaadamantane-N-oxygen radical (AZADO).

[0035] In a preferred embodiment, the ligand is one of NMI, 1,2-diaminocyclohexane, diamine, terpyridine, 1,10-phenanthroline, nitrobenzylimidazole, imidazole, nitrophenylimidazole, pyrrole, pyridine, and 2-methylpyridine.

[0036] The method for preparing heterogeneous organic polymer catalysts provided in this invention includes the following steps:

[0037] The oxidant monomer, ligand monomer, crosslinking agent monomer and free radical initiator are dissolved in the first solvent and polymerized at 60-120℃ for 6-24 hours to obtain polymer I;

[0038] Polymer I and peroxide were added to the first solvent and reacted for 3-8 hours to obtain the heterogeneous organic polymer catalyst.

[0039] In a preferred embodiment, the free radical initiator is an azo initiator.

[0040] In a preferred embodiment, the free radical initiator is azobisisobutyronitrile (AIBN).

[0041] In a preferred embodiment, the molar ratio of the oxidant monomer, ligand monomer, crosslinking agent monomer, and free radical initiator is 1:(0.5-2):(11-13.5):(0.2-0.55).

[0042] In a preferred embodiment, the peroxide is m-chloroperoxybenzoic acid, and its molar ratio to the oxidant monomer is (0.5–2):1. The function of the peroxide is to oxidize the NH bonds in polymer I to NO radicals.

[0043] In a preferred embodiment, the first solvent is one or more of tetrahydrofuran, toluene, n-butanol, or n-octanol.

[0044] The method for synthesizing aldehydes or lactones provided by this invention includes the following steps:

[0045] A primary alcohol or glycol, a heterogeneous organic polymer catalyst, and a copper salt are added to a second solvent and reacted under an oxygen or air atmosphere to yield an aldehyde or lactone compound. The reaction formula is as follows:

[0046]

[0047] The structural formulas of the primary alcohol and the resulting aldehyde are shown in Formulas I and II, where R1 is hydrogen, alkyl, cycloalkyl, olefinic, and alkyne groups of various chain lengths and structures, and aromatic rings of various charges, such as benzene rings, pyridine rings, furan rings, thiophene rings, pyrrole rings, pyrazine rings, oxazole rings, thiazole rings, imidazole rings, indole rings, and quinoline rings. Electron-withdrawing or electron-donating groups can be substituted at any position. Electron-donating groups include, but are not limited to, dialkylamino, alkylamino, alkoxy, hydroxyl, amide, alkyl, and phenyl groups. Electron-withdrawing groups include, but are not limited to, halogen, nitro, trifluoromethyl, cyano, carboxyl, sulfonic acid, and formyl groups.

[0048] The structural formulas of the diol and the resulting lactone are shown in Formula III and Formula IV, where R2 is an alkyl, cycloalkyl, or aromatic ring with various chain lengths and structures, and carbon atoms at different positions can be substituted.

[0049] In a preferred embodiment, the mass molar ratio of the heterogeneous organic polymer catalyst to the primary alcohol or diol is 120–250 g: 1 mol.

[0050] In a preferred embodiment, the copper ions in the copper salt are either monovalent or divalent, and the anions are OTf-, Cl-, or Br-. - Thiophene dicarboxylic acid (TC) - ), I - SO4 2- PF6 - OAc - BF4 - NO3 - One of them.

[0051] In a preferred embodiment, the molar ratio of copper salt to primary alcohol or diol is (0.04–0.07):1.

[0052] In a preferred embodiment, the second solvent is at least one of a nitrile solvent, a haloalkane solvent, an amide solvent, a sulfoxide solvent, or water. The amount used is not specifically limited, as long as it does not affect the reaction.

[0053] In a preferred embodiment, the second solvent is selected from at least one of acetonitrile, water, dichloromethane, chloroform, 1,2-dichloroethane, N,N-dimethylformamide, N,N-dimethylacetamide, or dimethyl sulfoxide.

[0054] Example 1

[0055] This embodiment provides a heterogeneous organic polymer catalyst supported on TEMPO and NMI, such as... Figure 1 As shown, its preparation method includes the following steps:

[0056] (1) Preparation of NMI monomer (A) and TEMPO monomer (C)

[0057] 50 mL of a THF solution containing 3.58 g (50 mmol) imidazole was added dropwise to a THF suspension containing NaOH and reacted for 2 h. After the reaction solution cooled to room temperature, 8.03 g (50 mmol) of 4-chloromethylstyrene was added dropwise and reacted at room temperature for 12 h to obtain 9.02 g of NMI monomer (A).

[0058] 20 mL of dimethylformamide (DMF) solution containing 2.35 g (15 mmol) of 2,2,6,6-tetramethyl-4-piperidinol was added dropwise to a DMF suspension containing NaOH and stirred for 2 h. After the reaction solution cooled to 0 °C, 2.3 g (15 mmol) of 4-chloromethylstyrene was added dropwise. The mixture was stirred at room temperature for 2 h, then heated to 60 °C and stirred for 2 h to obtain 1.25 g of TEMPO monomer (C).

[0059] (2) Preparation of heterogeneous organic polymer catalysts

[0060] 148 mg NMI monomer (A), 816 mg divinylbenzene monomer (B), 123 mg TEMPO monomer (C), and 25 mg azobisisobutyronitrile (ABIN) were dissolved in tetrahydrofuran (THF) and polymerized at 100 °C. After 24 h of reaction, the solvent was removed to obtain polymer I. Polymer I and 155 mg m-chloroperoxybenzoic acid (m-CPBA) were added to THF and reacted at room temperature for 6 hours. After removing the solvent, a heterogeneous organic polymer catalyst immobilized with TEMPO and NMI was obtained.

[0061] Figure 2 The image shown is a scanning electron microscope image of the heterogeneous organic polymer catalyst prepared in Example 1. It can be seen that the heterogeneous organic polymer catalyst has a bulk morphology and a particle size range of 1 to 5 μm.

[0062] Figure 3 The infrared spectrum of the heterogeneous organic polymer catalyst prepared in Example 1 is shown, with the spectrum located at 2918 cm⁻¹. -1 1507cm -1 and 1608cm -1 The peaks correspond to the stretching vibrations of saturated CH bonds, CN bonds, and aliphatic ether CO bonds, respectively, indicating that TEMPO and NMI have been successfully polymerized into the organic polymer.

[0063] Figure 4 The heterogeneous organic polymer catalyst prepared in Example 1 13 The solid-state nuclear magnetic resonance spectrum of C1000 shows that 41 ppm is the peak value of the polymerized vinyl group and 112 ppm is the peak value of the unpolymerized vinyl group. This result indicates that the organic polymer catalyst has a high degree of polymerization.

[0064] Example 2

[0065] Compound II-1

[0066] In this embodiment, compound II-1 was prepared using the heterogeneous organic polymer catalyst provided in Example 1, and the method is as follows:

[0067] At room temperature, 32 mg (0.25 mmol) of HMF (I-1) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 29.5 mg of the target product II-1, with a yield of 95%.

[0068] 1 H NMR (400MHz, CDCl3) δ9.87 (s, 1H), 7.35 (s, 1H).

[0069] 13 C NMR (101MHz, CDCl3) δ179.2, 154.2, 119.3.

[0070] After the reaction in Example 2 was completed, the reaction solution was separated by filtration, washed with acetonitrile and deionized water, and dried under vacuum at 60°C to recover the used heterogeneous organic polymer catalyst. Figure 5 The results of the stability test of the heterogeneous organic polymer catalyst show that the catalyst can be reused 8 times and its catalytic activity can be well maintained.

[0071] Under the reaction conditions of Example 2, the substrate was scaled up to 50 mmol. After 6 hours of reaction, the reaction was monitored by thin-layer chromatography. After the reaction, the organic phase was filtered, concentrated, and purified on a silica gel column (petroleum ether: ethyl acetate = 2:1) to obtain 5.78 g of product with a 93% separation yield. This yield is consistent with the reaction scale of 0.25 mmol substrate in Example 2, indicating that the catalyst has excellent scale-up performance. Combined with its low cost and easy separation and recovery, this catalyst shows good prospects for large-scale industrial application.

[0072] Example 3

[0073] Compound II-2

[0074] In this embodiment, compound II-2 was prepared using the heterogeneous organic polymer catalyst provided in Example 1, and the method is as follows:

[0075] At room temperature, 26.5 mg (0.25 mmol) of p-benzyl alcohol (I-2) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 26.5 mg of the target product II-2, with a yield of 99%.

[0076] 1 H NMR (400MHz, CDCl3) δ10.03 (s, 1H), 8.00–7.79 (m, 2H), 7.69–7.60 (m, 1H), 7.54 (dd, J = 8.2, 6.9Hz, 2H).

[0077] 13 C NMR (101MHz, CDCl3) δ192.43,136.42,134.49,129.77,129.02.

[0078] Example 4

[0079] Compound II-3

[0080] This embodiment uses the heterogeneous organic polymer catalyst provided in Example 1 to prepare compound II-3, and the method is as follows:

[0081] At room temperature, 34.5 mg (0.25 mmol) of p-methoxybenzyl alcohol (I-3) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out under an oxygen atmosphere at 25 °C for 6 hours. The resulting liquid was concentrated and purified to give 33.3 mg of the target product II-3, with a yield of 98%.

[0082] 1 H NMR (400MHz, CDCl3) δ9.89 (d, J = 1.7Hz, 1H), 7.91–7.75 (m, 2H), 7.01 (dd, J = 8.7, 1.7Hz, 2H), 3.89 (t, J = 1.4Hz, 3H).

[0083] 13 C NMR (101MHz, CDCl3) δ190.9,164.6,132.0,130.0,114.3,55.6.

[0084] Example 5

[0085] Compound II-4

[0086] In this embodiment, compound II-4 was prepared using the heterogeneous organic polymer catalyst provided in Example 1, and the method is as follows:

[0087] At room temperature, 35.6 mg (0.25 mmol) of p-chlorobenzyl alcohol (I-4) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out under an oxygen atmosphere at 25 °C for 6 hours. The resulting liquid was concentrated and purified to give 34.3 mg of the target product II-4, with a yield of 98%.

[0088] 1 H NMR (400MHz, CDCl3) δ9.99 (s, 1H), 7.91–7.73 (m, 2H), 7.52 (d, J = 8.2Hz, 2H).

[0089] 13 C NMR (101MHz, CDCl3) δ190.9,141.0,134.7,130.9,129.5.

[0090] Example 6

[0091] Compound II-5

[0092] This embodiment uses the heterogeneous organic polymer catalyst provided in Example 1 to prepare compound II-5, and the method is as follows:

[0093] At room temperature, 42 mg (0.25 mmol) of p-methoxybenzyl alcohol (I-5) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to give 40.8 mg of the target product II-5, with a yield of 99%.

[0094] 1 H NMR (400MHz, CDCl3) δ10.11 (s, 1H), 8.20 (d, J = 8.3Hz, 2H), 7.96 (d, J = 8.3Hz, 2H), 3.97 (s, 3H).

[0095] 13 C NMR (101MHz, CDCl3) δ191.7,166.1,139.1,135.1,130.2,129.5,52.6.

[0096] Example 7

[0097] Compound II-6

[0098] This embodiment uses the heterogeneous organic polymer catalyst provided in Example 1 to prepare compound II-6, and the method is as follows:

[0099] At room temperature, 40.1 mg (0.25 mmol) of 2-chloro-6-fluorobenzyl alcohol (I-6) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out under an oxygen atmosphere at 25 °C for 6 hours. The resulting liquid was concentrated and purified to give 37.9 mg of the target product II-6, with a yield of 96%.

[0100] 1 H NMR (400MHz, Chloroform-d) δ10.47(s,1H),7.52–7.47(m,J=8.3,5.7Hz,1H),7.29(d,J=8.1Hz,1H),7.11(t,J=8.8Hz,1H).

[0101] 13 C NMR (101MHz, CDCl3) δ187.0,187.0,164.6,162.0,135.3,135.1,126.8,126.8,115.8,115.6.

[0102] Example 8

[0103] Compound II-7

[0104] In this embodiment, compound II-7 was prepared using the heterogeneous organic polymer catalyst provided in Example 1, and the method is as follows:

[0105] At room temperature, 50.5 mg (0.25 mmol) of 2-amino-5-bromobenzyl alcohol (I-7) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out under an oxygen atmosphere at 25 °C for 6 hours. The resulting liquid was concentrated and purified to give 43.1 mg of the target product II-7, with a yield of 86%.

[0106] 1 H NMR (400MHz, Chloroform-d) δ9.78 (s, 1H), 7.57 (d, J = 2.4Hz, 1H), 7.36 (dd, J = 8.8, 2.4Hz, 1H), 6.56 (d, J = 8.8Hz, 1H), 6.16 (s, 2H).

[0107] 13C NMR (101MHz, CDCl3) δ192.8,148.7,137.9,137.4,119.9,118.0,107.2.

[0108] Example 9

[0109] Compound II-8

[0110] In this embodiment, compound II-8 was prepared using the heterogeneous organic polymer catalyst provided in Example 1, and the method is as follows:

[0111] At room temperature, 49.5 mg (0.25 mmol) of 3,5-dinitrobenzyl alcohol (I-8) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out under an oxygen atmosphere at 25 °C for 6 hours. The resulting liquid was concentrated and purified to give 49 mg of the target product II-8, with a yield of 99%.

[0112] 1 H NMR (400MHz, CDCl3) δ10.23 (d, J = 0.7Hz, 1H), 9.30 (t, J = 2.2Hz, 1H), 9.06 (d, J = 2.1Hz, 2H).

[0113] 13 C NMR (101MHz, CDCl3) δ187.2,149.3,138.5,128.7,123.3.

[0114] Example 10

[0115] Compound II-9

[0116] This embodiment uses the heterogeneous organic polymer catalyst provided in Example 1 to prepare compound II-9, and the method is as follows:

[0117] At room temperature, 42 mg (0.25 mmol) of triphenylmethanol (I-9) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out under an oxygen atmosphere at 25 °C for 6 hours. The resulting liquid was concentrated and purified to give 39.7 mg of the target product II-9, with a yield of 98%.

[0118] 1 H NMR (400MHz, CDCl3) δ10.21(s,3H),8.65(s,3H).

[0119] 13 C NMR (101MHz, CDCl3) δ189.9,137.8,134.8.

[0120] Example 11

[0121] Compound II-10

[0122] This embodiment uses the heterogeneous organic polymer catalyst provided in Example 1 to prepare compound II-10, and the method is as follows:

[0123] At room temperature, 40 mg (0.25 mmol) of 2-naphthalimethanol (I-10) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to give 39 mg of the target product II-10, with a yield of 99%.

[0124] 1 H NMR (400MHz, CDCl3) δ10.16(s,1H),8.34(d,J=1.5Hz,1H),8.12–7.80(m,5H),7.65–7.59(m,J=15.9,8.1,1.3Hz,2H).

[0125] 13 C NMR (101MHz, CDCl3) δ192.3,136.5,134.6,134.1,132.7,129.6,129.1,129.1,128.1,127.1,122.8.

[0126] Example 12

[0127] Compound II-11

[0128] In this embodiment, compound II-11 was prepared using the heterogeneous organic polymer catalyst provided in Example 1, and the method is as follows:

[0129] At room temperature, 18 mg (0.25 mmol) of cyclopropanol (I-11) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to give 12.6 mg of the target product II-11, with a yield of 72%.

[0130] 1H NMR (400MHz, CDCl3) δ8.91 (d, J=5.8Hz, 1H), 1.84 (dd, J=7.0, 5.1Hz, 1H), 1.24–0.87 (m, 4H).

[0131] 13 C NMR (101MHz, CDCl3) δ201.6, 22.7, 7.3.

[0132] Example 13

[0133] Compound II-12

[0134] This embodiment uses the heterogeneous organic polymer catalyst provided in Example 1 to prepare compound II-12, and the method is as follows:

[0135] At room temperature, 34 mg (0.25 mmol) of phenylpropanol (I-12) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 33.5 mg of the target product II-12, with a yield of 99%.

[0136] 1 H NMR (400MHz, CDCl3) δ9.82(d,J=1.5Hz,1H),7.29(d,J=7.2Hz,2H),7.23–7.15(m,3H),2.96(t,J=7.5Hz,2H),2.78(t,J=7.8,1.3Hz,2H).

[0137] 13 C NMR (101MHz, CDCl3) δ201.6,140.3,128.6,128.3,126.3,45.3,28.1.

[0138] Example 14

[0139] Compound II-13

[0140] In this embodiment, compound II-13 was prepared using the heterogeneous organic polymer catalyst provided in Example 1, and the method is as follows:

[0141] At room temperature, 32.5 mg (0.25 mmol) of n-octanol (I-13) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out under an oxygen atmosphere at 25 °C for 6 hours. The resulting liquid was concentrated and purified to give 20.8 mg of the target product II-13, with a yield of 65%.

[0142] 1 H NMR(400MHz,Chloroform-d)δ9.77(t,J=1.9Hz,1H),2.44–2.40(m,J=7.4,1.9Hz ,2H),1.70–1.57(m,3H),1.33–1.27(m,J=14.6,4.7Hz,10H),0.93–0.84(m,4H).

[0143] 13 C NMR (101MHz, CDCl3) δ203.0,43.9,31.6,29.1,29.0,22.6,22.1,14.1.

[0144] Example 15

[0145] Compound II-14

[0146] In this embodiment, compound II-14 was prepared using the heterogeneous organic polymer catalyst provided in Example 1, and the method is as follows:

[0147] At room temperature, 39 mg (0.25 mmol) of citronellol (I-14) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to give 23.5 mg of the target product II-14, with a yield of 61%.

[0148] 1 H NMR(400MHz, CDCl3)δ9.75(s,1H),5.08(t,J=7.0Hz,1H),2.35–2.45(m,1H),2.17-2.24(m,1 H),1.99(q,J=7.4Hz,2H),1.64(d,J=33.0Hz,7H),1.40–1.21(m,2H),0.97(d,J=6.7Hz,3H).

[0149] 13C NMR (101MHz, CDCl3) δ203.1,131.8,124.0,51.0,36.9,27.8,25.7,25.4,19.9,17.7.

[0150] Example 16

[0151] Compound II-15

[0152] This embodiment uses the heterogeneous organic polymer catalyst provided in Example 1 to prepare compound II-15, and the method is as follows:

[0153] At room temperature, 33 mg (0.25 mmol) of phenylpropynyl alcohol (I-15) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to give 32.5 mg of the target product II-15, with a yield of 99%.

[0154] 1 H NMR (400MHz, CDCl3) δ9.43 (s, 1H), 7.61 (d, J = 7.0Hz, 1H), 7.50 (t, J = 7.5Hz, 1H), 7.41 (t, J = 7.5Hz, 2H).

[0155] 13 C NMR (101MHz, CDCl3) δ176.8,133.3,131.3,128.8,119.4,95.2,88.4.

[0156] Example 17

[0157] Compound II-16

[0158] This embodiment uses the heterogeneous organic polymer catalyst provided in Example 1 to prepare compound II-16, and the method is as follows:

[0159] At room temperature, 38 mg (0.25 mmol) of 4-(1-hydroxyethyl)benzyl alcohol (I-16) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out under an oxygen atmosphere at 25 °C for 6 hours. The resulting liquid was concentrated and purified to give 31.8 mg of the target product II-16, with a yield of 85%.

[0160] 1H NMR (400MHz, CDCl3) δ9.98 (s, 1H), 7.86 (d, J = 8.2Hz, 2H), 7.54 (d, J = 7.9Hz, 2H), 4.99 (q, J = 6.5Hz, 1H), 1.52 (d, J = 6.5Hz, 3H).

[0161] 13 C NMR (101MHz, CDCl3) δ192.0,152.8,135.6,130.1,125.9,69.9,25.4.

[0162] Example 18

[0163] Compound II-17

[0164] This embodiment uses the heterogeneous organic polymer catalyst provided in Example 1 to prepare compound II-17, and the method is as follows:

[0165] At room temperature, 27.3 mg (0.25 mmol) of 3-pyridinemethanol (I-17) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out under an oxygen atmosphere at 25 °C for 6 hours. The resulting liquid was concentrated and purified to give 26.7 mg of the target product II-17, with a yield of 99%.

[0166] 1 H NMR (400MHz, CDCl3) δ10.14(s,1H),9.10(s,1H),8.86(dd,J=4.8,2.2Hz,1H),8.20(d,J=7.8Hz,1H),7.53–7.49(m,J=7.4,4.9,1.9Hz,1H).

[0167] 13 C NMR (101MHz, CDCl3) δ190.8,154.7,152.1,135.9,131.5,124.1.

[0168] Example 19

[0169] Compound II-18

[0170] This embodiment uses the heterogeneous organic polymer catalyst provided in Example 1 to prepare compound II-18, and the method is as follows:

[0171] At room temperature, 28.5 mg (0.25 mmol) of 2-thiophene methanol (I-18) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out under an oxygen atmosphere at 25 °C for 6 hours. The resulting liquid was concentrated and purified to give 28 mg of the target product II-18, with a yield of 99%.

[0172] 1 H NMR (400MHz, CDCl3) δ9.95 (d, J = 1.4Hz, 1H), 7.79 (m, J = 7.2, 4.3, 1.3Hz, 2H), 7.22 (dd, J = 5.0, 3.7Hz, 1H).

[0173] 13 C NMR (101MHz, CDCl3) δ183.1,144.1,136.3,135.2,128.3.

[0174] Example 20

[0175] Compound II-19

[0176] This embodiment uses the heterogeneous organic polymer catalyst provided in Example 1 to prepare compound II-19, and the method is as follows:

[0177] At room temperature, 39.8 mg (0.25 mmol) of quinoline-2-methanol (I-19) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to give 34.9 mg of the target product II-19, with a yield of 89%.

[0178] 1 H NMR (400MHz, CDCl3) δ10.24(d,J=0.9Hz,1H),8.32(d,J=8.4Hz,1H),8.26(d,J=8.5Hz,1H),8.04(d,J=8.4H z,1H),7.90(d,J=1.3Hz,1H),7.86–7.81(m,J=8.4,6.9,1.5Hz,1H),7.72–7.68(m,J=8.1,6.9,1.2Hz,1H).

[0179] 13C NMR (101MHz, CDCl3) δ193.8,152.6,148.0,137.4,130.5,130.5,130.1,129.2,127.9,117.4.

[0180] Example 21

[0181] Compound II-20

[0182] This embodiment uses the heterogeneous organic polymer catalyst provided in Example 1 to prepare compound II-20, and the method is as follows:

[0183] At room temperature, 36.8 mg (0.25 mmol) of 1H-indole-2-methanol (I-20) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out under an oxygen atmosphere at 25 °C for 6 hours. The resulting liquid was concentrated and purified to give 19.6 mg of the target product II-20, with a yield of 54%.

[0184] 1 H NMR(400MHz, CDCl3) δ9.86(s,1H),9.44(s,1H),7.75(dd,J=8.2,1.1Hz,1H),7.48(dd,J=8.4,1.1Hz,1H), 7.42–7.38(m,J=8.2,6.9,1.1Hz,1H),7.29(dd,J=2.2,0.9Hz,1H),7.20–7.16(m,J=8.0,6.8,1.0Hz,1H).

[0185] 13 C NMR (101MHz, CDCl3) δ182.3,138.2,136.0,127.4,127.3,123.5,121.3,115.0,112.6.

[0186] Example 22

[0187] Compound II-21

[0188] In this embodiment, compound II-21 was prepared using the heterogeneous organic polymer catalyst provided in Example 1, and the method is as follows:

[0189] At room temperature, 38 mg (0.25 mmol) of piperine (I-21) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to give 34.5 mg of the target product II-21, with a yield of 92%.

[0190] 1 H NMR (400MHz, Chloroform-d) δ9.81(s,1H),7.41(dd,J=8.0,1.6Hz,1H),7.33(d,J=1.6Hz,1H),6.93(d,J=7.9Hz,1H),6.08(s,2H).

[0191] 13 C NMR (101MHz, CDCl3) δ190.3,153.1,148.7,131.9,128.7,108.4,106.9,102.2.

[0192] Example 23

[0193] Compound IV-1

[0194] This embodiment uses the heterogeneous organic polymer catalyst provided in Example 1 to prepare compound IV-1, and the method is as follows:

[0195] At room temperature, 29.54 mg (0.25 mmol) of 1,6-hexanediol (III-1) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out under an oxygen atmosphere at 25 °C for 6 hours. The resulting liquid was concentrated and purified to give 22.7 mg of the target product IV-1, with a yield of 71%.

[0196] 1 H NMR (400MHz, CDCl3) δ4.27–4.19(t,2H),2.69–2.61(t,2H),1.89–1.74(m,J=39.7,10.3,6.7,4.5Hz,6H).

[0197] 13 C NMR (101MHz, CDCl3) δ176.3,69.3,34.6,29.3,29.0,22.9.

[0198] Example 24

[0199] Compound IV-2

[0200] This embodiment uses the heterogeneous organic polymer catalyst provided in Example 1 to prepare compound IV-2, and the method is as follows:

[0201] At room temperature, 26 mg (0.25 mmol) of 1,5-pentanediol (III-2) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, followed by the addition of 1.8 mg (0.0125 mmol) of CuBr. The reaction was carried out under an oxygen atmosphere at 25 °C for 6 hours. The resulting liquid was concentrated and purified to give 13.5 mg of the target product IV-2, with a yield of 54%.

[0202] 1 H NMR (400MHz, CDCl3) δ4.35(t,J=5.6Hz,1H),2.56(t,J=6.9Hz,1H),2.03–1.78(m,2H).

[0203] 13 C NMR (101MHz, CDCl3) δ171.4,69.5,29.9,22.3,19.1.

[0204] Example 25

[0205] Compound IV-3

[0206] This embodiment uses the heterogeneous organic polymer catalyst provided in Example 1 to prepare compound IV-3, and the method is as follows:

[0207] At room temperature, 22.5 mg (0.25 mmol) of 1,4-butanediol (III-3) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out under an oxygen atmosphere at 25 °C for 6 hours. The resulting liquid was concentrated and purified to give 11.6 mg of the target product IV-3, with a yield of 54%.

[0208] 1 H NMR (400MHz, CDCl3) δ4.36 (t, J = 7.1Hz, 1H), 2.58–2.39 (m, 1H), 2.33–2.23 (m, 1H).

[0209] 13 C NMR (101MHz, CDCl3) δ177.8, 68.5, 27.8, 22.2.

[0210] Example 26

[0211] Compound IV-4

[0212] This embodiment uses the heterogeneous organic polymer catalyst provided in Example 1 to prepare compound IV-4, and the method is as follows:

[0213] At room temperature, 34.5 mg (0.25 mmol) of phthalic acid (III-4) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to give 28.8 mg of the target product IV-4, with a yield of 86%.

[0214] 1 H NMR (400MHz, CDCl3) δ7.92 (d, J=7.6Hz, 1H), 7.70 (td, J=7.5, 1.1Hz, 1H), 7.58–7.50 (m, 2H).

[0215] 13 C NMR (101MHz, CDCl3) δ171.2,146.6,134.1,129.1,125.7,125.7,122.2,69.7.

[0216] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any person skilled in the art can make some modifications or alterations to the disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention, without departing from the scope of the present invention, shall still fall within the scope of the present invention.

Claims

1. A method for preparing a heterogeneous organic polymer catalyst, characterized in that, Includes the following steps: (1) Preparation of N-methylimidazolium monomer and 2,2,6,6-tetramethylpiperidine oxide monomer, 50 mL of tetrahydrofuran solution containing 3.58 g imidazole was added dropwise to a tetrahydrofuran suspension containing NaOH and reacted for 2 h. After the reaction solution was cooled to room temperature, 8.03 g of 4-chloromethylstyrene was added dropwise and reacted at room temperature for 12 h to obtain 9.02 g of N-methylimidazolium monomer. 20 mL of a dimethylformamide solution containing 2.35 g of 2,2,6,6-tetramethyl-4-piperidinol was added dropwise to a dimethylformamide suspension containing NaOH. The mixture was stirred for 2 h. After the reaction solution cooled to 0 °C, 2.3 g of 4-chloromethylstyrene was added dropwise. The mixture was stirred at room temperature for 2 h, then heated to 60 °C and stirred for 2 h to obtain 1.25 g of 2,2,6,6-tetramethylpiperidin oxide monomer. (2) Preparation of heterogeneous organic polymer catalysts, 148 mg of N-methylimidazolium monomer, 816 mg of p-divinylbenzene monomer, 123 mg of 2,2,6,6-tetramethylpiperidine oxide monomer, and 25 mg of azobisisobutyronitrile were dissolved in tetrahydrofuran and polymerized at 100 °C. After reacting for 24 h, the solvent was removed to obtain polymer I. Polymer I and 155 mg of m-chloroperoxybenzoic acid were added to tetrahydrofuran and reacted at room temperature for 6 h. After removing the solvent, a heterogeneous organic polymer catalyst immobilized with 2,2,6,6-tetramethylpiperidine oxide and N-methylimidazolium was obtained.

2. A heterogeneous organic polymer catalyst, characterized in that, It was prepared using the method for preparing a heterogeneous organic polymer catalyst as described in claim 1.

3. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, include: At room temperature, 32 mg of 5-hydroxymethylfurfural and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 29.5 mg of the target product.

4. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, include: At room temperature, 26.5 mg of p-benzyl alcohol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 26.5 mg of the target product.

5. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 34.5 mg of p-methoxybenzyl alcohol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 33.3 mg of the target product.

6. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 35.6 mg of p-chlorobenzyl alcohol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 34.3 mg of the target product.

7. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 42 mg of p-methoxybenzyl alcohol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 40.8 mg of the target product.

8. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 40.1 mg of 2-chloro-6-fluorobenzyl alcohol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 37.9 mg of the target product.

9. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 50.5 mg of 2-amino-5-bromobenzyl alcohol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 43.1 mg of the target product.

10. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 49.5 mg of 3,5-dinitrobenzyl alcohol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 49 mg of the target product.

11. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 42 mg of triphenylmethanol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 39.7 mg of the target product.

12. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 40 mg of 2-naphthalenemethanol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 39 mg of the target product.

13. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 18 mg of cyclopropane methanol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 12.6 mg of the target product.

14. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 34 mg of phenylpropanol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 33.5 mg of the target product.

15. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 32.5 mg of n-octanol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 20.8 mg of the target product.

16. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 39 mg of citronellol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 23.5 mg of the target product.

17. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 33 mg of phenylpropynyl alcohol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 32.5 mg of the target product.

18. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 38 mg of 4-(1-hydroxyethyl)benzyl alcohol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 31.8 mg of the target product.

19. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 27.3 mg of 3-pyridinemethanol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 26.7 mg of the target product.

20. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 28.5 mg of 2-thiophene methanol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 28 mg of the target product.

21. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 39.8 mg of quinoline-2-methanol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 34.9 mg of the target product.

22. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 36.8 mg of 1H-indole-2-methanol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The reaction was carried out for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 19.6 mg of the target product.

23. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 38 mg of piperine and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 34.5 mg of the target product.

24. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 29.54 mg of 1,6-hexanediol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 22.7 mg of the target product.

25. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 26 mg of 1,5-pentanediol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 13.5 mg of the target product.

26. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 22.5 mg of 1,4-butanediol and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 11.6 mg of the target product.

27. A method for applying the heterogeneous organic polymer catalyst as described in claim 2, characterized in that, At room temperature, 34.5 mg of phthalic acid and 63 mg of the heterogeneous organic polymer catalyst described in claim 2 were dissolved in 2.5 mL of acetonitrile solvent, and then 1.8 mg of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere and at 25 °C. The resulting liquid was concentrated and purified to obtain 28.8 mg of the target product.

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