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

Abstract

The heterogeneous organic polymer catalyst has a structure that an oxidizing agent and a ligand are immobilized on an organic polymer matrix at the same time, an organic polymer is a polymerization product of a cross-linking agent monomer with at least one vinyl group on a benzene ring, the oxidizing agent is a nitroxide free radical, and the ligand is a ligand. The ligand is a nitrogen heterocyclic compound or an amine compound. The heterogeneous organic polymer catalyst disclosed by the invention is matched with copper salt, so that high-selectivity and high-yield conversion from HMF to DFF can be realized at room temperature in an oxygen atmosphere. The heterogeneous organic polymer catalyst provided by the invention not only can be recycled for multiple times, but also can realize efficient synthesis of other aldehyde and lactone compounds.

Description

Technical Field

[0001] The invention relates to the technical field of catalysts and organic synthesis, and in particular to a heterogeneous organic polymer catalyst and a preparation method thereof, and a method for synthesizing aldehyde or lactone compounds. Background Art

[0002] In recent years, biomass has received extensive attention as a renewable carbon source. The high-selectivity conversion of low-cost biomass macromolecules into organic small molecule compounds (such as high-value-added chemicals and fuels) through green and efficient methods can effectively reduce the country's dependence on fossil fuels. As an important bridge connecting biomass resources and fossil resources, 5-hydroxymethylfurfural (HMF) can be converted from renewable biomass carbohydrates by dehydration, and can be converted into high-value-added downstream products through hydrolysis, esterification, hydrogenation, oxidation-reduction and other reactions. Among them, 2,5-diformylfuran (DFF), as a high-value organic synthesis intermediate, is widely used in medicine, organic conductors, polymer materials, pesticides and other fields. Using low-cost HMF as raw material and synthesizing DFF through oxidation reaction has good economic benefits. At present, the industrial production process of HMF to DFF mainly adopts oxidation technology under high temperature and high pressure conditions. In the reaction, HMF is easily further oxidized to products such as 2,5-furandicarboxylic acid (FDCA), 5-formyl-2-furancarboxylic acid (FFCA), 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), etc. Therefore, this process usually 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-tetramethylpiperidinyl oxide (TEMPO) / N-methylimidazole (NMI) catalyst system that can oxidize primary alcohols to corresponding aldehyde compounds with high efficiency and selectivity at room temperature using oxygen as an oxidant (J.Am.Chem.Soc., 2011, 133, 16901-16910). The catalytic mechanism of this system includes two stages: (1) "catalytic oxidation", Cu I and TEMPO-H is oxidized to Cu by O2 via Cu2O2 intermediate II and TEMPO nitroxide radical; (2) “substrate oxidation”, through TEMPO nitro radical and Cu II -Reaction of alcohol oxide intermediates (J.Am.Chem.Soc., 2013, 135, 2357-2367). However, this reaction system has never been used for the conversion of HMF to DFF, and this system is a homogeneous reaction, and the added catalyst and ligand can only be used once and cannot be separated and recycled. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention aims to provide a heterogeneous organic polymer catalyst and a method for catalytically synthesizing aldehydes and lactone compounds. A heterogeneous organic polymer catalyst is prepared by immobilizing a catalytically active fragment oxidant (e.g., TEMPO) and a ligand (e.g., NMI) on an organic polymer, which can achieve high selectivity and high yield conversion of HMF to DFF at room temperature and oxygen atmosphere.

[0005] To achieve the above purpose, the specific technical solutions of the present invention are 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, wherein the organic polymer is a polymerization product of a crosslinking agent monomer having at least one vinyl group on a benzene ring, the oxidant is a nitroxide free radical, and the ligand is a nitrogen heterocyclic compound or an amine compound.

[0007] Furthermore, the cross-linking agent is one of styrene, p-divinylbenzene and mesitylene trivinylbenzene.

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

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

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

[0011] The oxidant monomer, the ligand monomer, the crosslinker monomer and the free radical initiator are dissolved in the first solvent, and the polymerization reaction is carried out at 60 to 120° C. for 6 to 24 hours to obtain polymer I;

[0012] Add polymer I and peroxide into the first solvent and react for 3 to 8 hours to obtain the heterogeneous organic polymer catalyst.

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

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

[0015] Furthermore, the peroxide is m-chloroperbenzoic acid, and the molar ratio of the peroxide to 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 aldehyde or lactone compounds provided by the present invention comprises the following steps:

[0018] The primary alcohol or diol, the heterogeneous organic polymer catalyst and the copper salt are added into the second solvent and reacted under oxygen or air atmosphere to obtain aldehyde or lactone compound.

[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 ion in the copper salt is I-valent or II-valent, and the anion is OTf-, Cl-, Br - , thiophenedicarboxylic 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 a nitrile solvent, a halogenated alkane solvent, an amide solvent, a sulfoxide solvent 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 present invention has the following beneficial effects:

[0025] The heterogeneous organic polymer catalyst provided by the present invention can simultaneously immobilize the oxidant and the ligand, can simultaneously exert the functions of the oxidant and the ligand, and can cooperate with the copper salt to achieve high selectivity and high yield conversion of HMF to DFF at room temperature and oxygen atmosphere. The heterogeneous organic polymer catalyst provided by the present invention can not only be recycled for multiple times, but also can achieve efficient synthesis of other aldehydes and lactone compounds. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

[0028] Figure 3 is an 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 NMR spectroscopy;

[0030] Figure 5 The stability test results of the heterogeneous organic polymer catalyst prepared in Example 1 are shown. DETAILED DESCRIPTION

[0031] In order to enable those skilled in the art to more clearly understand the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are further described in detail below in conjunction with the accompanying drawings and preferred embodiments. The examples cited are only used to explain the present invention and are not used 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; if not specifically specified, the technical means used are conventional means well known to those skilled in the art.

[0032] A heterogeneous organic polymer catalyst provided in an embodiment of the present invention has 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 cross-linking agent monomer having at least one vinyl group on a benzene ring, the oxidant is a nitroxide free 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, p-divinylbenzene and mesitylenetrivinylbenzene.

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

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

[0036] The method for preparing a heterogeneous organic polymer catalyst provided by an embodiment of the present invention comprises the following steps:

[0037] The oxidant monomer, the ligand monomer, the crosslinker monomer and the free radical initiator are dissolved in the first solvent, and the polymerization reaction is carried out at 60 to 120° C. for 6 to 24 hours to obtain polymer I;

[0038] Add polymer I and peroxide into the first solvent and react for 3 to 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.

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

[0042] In a preferred embodiment, the peroxide is m-chloroperbenzoic acid, and the molar ratio of the peroxide to the oxidant monomer is (0.5-2): 1. The role of the peroxide is to oxidize the NH bond in the polymer I into NO free 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 aldehyde or lactone compounds provided by the present invention comprises the following steps:

[0045] Add primary alcohol or diol, heterogeneous organic polymer catalyst and copper salt into the second solvent and react under oxygen or air atmosphere to obtain aldehyde or lactone compound. The reaction formula is as follows:

[0046]

[0047] The structural formulas of the primary alcohol and the obtained aldehyde are shown in Formula I and Formula II, and R1 is hydrogen, alkyl, cycloalkyl, olefin and alkyne groups of various chain lengths and structures, and aromatic rings of various electrical properties, 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. The electron-withdrawing or electron-donating groups can be substituted at any position, and the electron-donating groups include but are not limited to dialkylamino, alkylamino, alkoxy, hydroxyl, amide, alkyl, and phenyl groups, and the 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 obtained lactone are shown in Formula III and Formula IV, and R2 is an alkyl group, cycloalkyl group, or aromatic ring of various chain lengths and structures, wherein 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 ion in the copper salt is I-valent or II-valent, and the anion is OTf-, Cl-, Br - , thiophenedicarboxylic acid (TC - ), I - 、SO4 2- PF6 - ,OAc - 、BF4 - 、NO3 - One of them.

[0051] In a preferred embodiment, the molar ratio of the copper salt to the 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 halogenated alkane solvent, an amide solvent, a sulfoxide solvent or water. The amount thereof 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 of immobilized TEMPO and NMI, such as Figure 1 As shown, the preparation method thereof comprises the following steps:

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

[0057] 50 mL of THF solution containing 3.58 g (50 mmol) of imidazole was added dropwise to a THF suspension containing NaOH and reacted for 2 h. After the reaction solution was 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 the DMF suspension containing NaOH and stirred for 2 h. After the reaction solution dropped to 0°C, 2.3 g (15 mmol) of 4-chloromethylstyrene was added dropwise. After stirring at room temperature for 2 h, the temperature was raised 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 p-divinylbenzene monomer (B), 123 mg TEMPO monomer (C) and 25 mg azobisisobutyronitrile (ABIN) were dissolved in tetrahydrofuran (THF), and polymerization reaction occurred at 100°C. After 24 hours of reaction, the solvent was removed to obtain polymer I. Polymer I and 155 mg m-chloroperbenzoic acid (m-CPBA) were added to THF, reacted at room temperature for 6 hours, and then the solvent was removed to obtain a heterogeneous organic polymer catalyst with immobilized TEMPO and NMI.

[0061] Figure 2 This is a scanning electron microscope photograph of the heterogeneous organic polymer catalyst prepared in Example 1. It can be seen that the heterogeneous organic polymer catalyst is a block morphology with a particle size range of 1 to 5 μm.

[0062] Figure 3 This is the infrared spectrum of the heterogeneous organic polymer catalyst prepared in Example 1. -1 、1507cm -1 and 1608cm -1 The peaks correspond to the stretching vibration 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 C solid-state nuclear magnetic resonance spectrum, where 41 ppm is the peak after vinyl polymerization and 112 ppm is the peak of unpolymerized vinyl. This result indicates that the organic polymer catalyst has a high degree of polymerization.

[0064] Example 2

[0065] Compound II-1

[0066] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-1, and the method was 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 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted in an oxygen atmosphere at 25°C for 6 hours. The resulting liquid was concentrated and purified to obtain 29.5 mg of the target product of compound 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 suction filtration, washed with acetonitrile and deionized water, and vacuum dried at 60° C. to recover the used heterogeneous organic polymer catalyst. Figure 5 This is the stability test result of the heterogeneous organic polymer catalyst. It can be seen that the catalyst can be reused 8 times and its catalytic activity can be well maintained.

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

[0072] Example 3

[0073] Compound II-2

[0074] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-2, and the method was as follows:

[0075] At room temperature, 26.5 mg (0.25 mmol) of benzyl alcohol (I-2) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted in an oxygen atmosphere at 25°C for 6 hours. The resulting liquid was concentrated and purified to obtain 26.5 mg of the target product of compound 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] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-3, and the method was 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 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted in an oxygen atmosphere at 25°C for 6 hours. The resulting liquid was concentrated and purified to obtain 33.3 mg of the target product of compound 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 example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-4, and the method was 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 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours in an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 34.3 mg of the target product of compound 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] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-5, and the method was 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 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours in an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 40.8 mg of the target product of compound 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] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-6, and the method was as follows:

[0099] At room temperature, 40.1 mg (0.25 mmol) of 2-chloro-6-fluorobenzyl alcohol (I-6) and 63 mg of a heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 37.9 mg of the target product of compound 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 example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-7, and the method was 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 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 43.1 mg of the target product of compound 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 example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-8, and the method was 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 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours in an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 49 mg of the target product of compound 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] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-9, and the method was as follows:

[0117] At room temperature, 42 mg (0.25 mmol) of trityl alcohol (I-9) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours in an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 39.7 mg of the target product of compound 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] Embodiment 11

[0121] Compound II-10

[0122] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-10, and the method was as follows:

[0123] At room temperature, 40 mg (0.25 mmol) of 2-naphthalenemethanol (I-10) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours in an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 39 mg of the target product of compound 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 example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-11, and the method was as follows:

[0129] At room temperature, 18 mg (0.25 mmol) of cyclopropylmethanol (I-11) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours in an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 12.6 mg of the target product of compound 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] Embodiment 13

[0133] Compound II-12

[0134] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-12, and the method was 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 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out in an oxygen atmosphere at 25°C for 6 hours. The resulting liquid was concentrated and purified to obtain 33.5 mg of the target product of compound 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] Embodiment 14

[0139] Compound II-13

[0140] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-13, and the method was 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 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours in an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 20.8 mg of the target product of compound 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] Embodiment 15

[0145] Compound II-14

[0146] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-14, and the method was 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 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted in an oxygen atmosphere at 25°C for 6 hours. The resulting liquid was concentrated and purified to obtain 23.5 mg of the target product of compound 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] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-15, and the method was as follows:

[0153] At room temperature, 33 mg (0.25 mmol) of phenylpropargyl alcohol (I-15) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours in an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 32.5 mg of the target product of compound 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] Embodiment 17

[0157] Compound II-16

[0158] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-16, and the method was 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 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours in an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 31.8 mg of the target product of compound 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] Embodiment 18

[0163] Compound II-17

[0164] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-17, and the method was 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 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours in an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 26.7 mg of the target product of compound 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] Embodiment 19

[0169] Compound II-18

[0170] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-18, and the method was 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 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours in an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 28 mg of the target product of compound 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] Embodiment 20

[0175] Compound II-19

[0176] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-19, and the method was 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 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours in an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 34.9 mg of the target product of compound 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] Embodiment 21

[0181] Compound II-20

[0182] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-20, and the method was 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 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted in an oxygen atmosphere at 25°C for 6 hours. The resulting liquid was concentrated and purified to obtain 19.6 mg of the target product of compound 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] Embodiment 22

[0187] Compound II-21

[0188] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound II-21, and the method was as follows:

[0189] At room temperature, 38 mg (0.25 mmol) of piperonyl alcohol (I-21) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours in an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 34.5 mg of the target product of compound 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] Embodiment 23

[0193] Compound IV-1

[0194] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound IV-1, and the method was as follows:

[0195] At room temperature, 29.54 mg (0.25 mmol) of 1,6-hexanediol (III-1) and 63 mg of a heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours under an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 22.7 mg of the target product of compound 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] Embodiment 24

[0199] Compound IV-2

[0200] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound IV-2, and the method was 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, and 1.8 mg (0.0125 mmol) of CuBr was added. The reaction was carried out under oxygen atmosphere at 25°C for 6 hours, and the obtained liquid was concentrated and purified to obtain 13.5 mg of the target product of compound 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] Embodiment 25

[0205] Compound IV-3

[0206] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound IV-3, and the method was 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 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours in an oxygen atmosphere at 25°C. The resulting liquid was concentrated and purified to obtain 11.6 mg of the target product of compound 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] Embodiment 26

[0211] Compound IV-4

[0212] In this example, the heterogeneous organic polymer catalyst provided in Example 1 was used to prepare compound IV-4, and the method was as follows:

[0213] At room temperature, 34.5 mg (0.25 mmol) of o-phthalic alcohol (III-4) and 63 mg of heterogeneous organic polymer catalyst were dissolved in 2.5 mL of acetonitrile solvent, and 1.8 mg (0.0125 mmol) of CuBr was added. The mixture was reacted for 6 hours under oxygen atmosphere and 25°C. The obtained liquid was concentrated and purified to obtain 28.8 mg of the target product of compound 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 only a preferred embodiment of the present invention and does not limit the present invention in any form. Any person skilled in the art can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A heterogeneous organic polymer catalyst, characterized in that The heterogeneous organic polymer catalyst has 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 having at least one vinyl group on a benzene ring, the oxidant is a nitroxide free radical, and the ligand is a nitrogen heterocyclic compound or an amine compound.

2. The heterogeneous organic polymer catalyst according to claim 1, characterized in that The cross-linking agent is one of styrene, p-divinylbenzene and mesitylene trivinylbenzene.

3. The heterogeneous organic polymer catalyst according to claim 1, characterized in that The oxidant is one of TEMPO and its derivatives, 9-azabicyclo[3.3.1]nonane-N-oxyl free radical, and 2-azaadamantane-N-oxyl free radical; the ligand is one of NMI, 1,2-diaminocyclohexane, diamine, terpyridine, 1,10-phenanthroline, nitrogen-benzylimidazole, imidazole, nitrogen-phenylimidazole, pyrrole, pyridine, and 2-methylpyridine.

4. The method for preparing a heterogeneous organic polymer catalyst according to any one of claims 1 to 3, characterized in that: The following steps are involved: The oxidant monomer, the ligand monomer, the crosslinker monomer and the free radical initiator are dissolved in the first solvent, and the polymerization reaction is carried out at 60 to 120° C. for 6 to 24 hours to obtain polymer I; Adding polymer I and peroxide into the first solvent and reacting for 3 to 8 hours to obtain the heterogeneous organic polymer catalyst; The molar ratio of the oxidant monomer, the ligand monomer, the crosslinker monomer and the free radical initiator is 1:(0.5-2):(11-13.5):(0.2-0.55); The molar ratio of the peroxide to the oxidant monomer is (0.5-2):

1.

5. The method for preparing a heterogeneous organic polymer catalyst according to claim 4, characterized in that: The free radical initiator is an azo initiator, preferably azobisisobutyronitrile.

6. The method for preparing a heterogeneous organic polymer catalyst according to claim 4, characterized in that: The peroxide is meta-chloroperbenzoic acid.

7. The method for preparing a heterogeneous organic polymer catalyst according to claim 4, characterized in that: The first solvent is one or more of tetrahydrofuran, toluene, n-butanol or n-octanol.

8. A method for synthesizing aldehyde or lactone compounds, characterized in that: The following steps are involved: Adding a primary alcohol or a diol, the heterogeneous organic polymer catalyst according to any one of claims 1 to 3, and a copper salt into a second solvent, and reacting them under an oxygen or air atmosphere to obtain an aldehyde or a lactone compound; The mass molar ratio of the heterogeneous organic polymer catalyst to the primary alcohol or diol is 120-250 g:1 mol; The molar ratio of the copper salt to the primary alcohol or diol is (0.04-0.07):

1.

9. The method for synthesizing aldehyde or lactone compounds according to claim 8, characterized in that: The copper ion in the copper salt is I-valent or II-valent, and the anion is OTf - , Cl - Br - , thiophenedicarboxylic acid (TC - ), I - 、SO4 2- PF6 - ,OAc - 、BF4 - 、NO3 - One of them.

10. The method for synthesizing aldehyde or lactone compounds according to claim 8, characterized in that: The second solvent is at least one of a nitrile solvent, a halogenated alkane solvent, an amide solvent, a sulfoxide solvent or water; preferably, 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.

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