Alcohol oxidation catalytic system based on combination of copper salt and bifunctional ligand and oxidation method

Abstract

The invention discloses an alcohol oxidation catalytic system based on combination of copper salt and bifunctional ligand, which is prepared by the following steps: firstly, preparing N-containing organic molecules formed by combining N, N, N-trimethyl ethylenediamine with pyridine, thiophene or benzene through amine-aldehyde condensation reaction and sodium borohydride reduction reaction; then synthesizing a bifunctional ligand containing TEMPO and the N-containing organic molecule through nucleophilic substitution reaction, and combining the bifunctional ligand with copper salt to form a catalytic system. The method is high in reaction yield and wide in substrate range, more importantly, the reaction time is short, the reaction conditions are mild, only 2 mol% of catalyst is used, the TOF can reach 50 h <-1 > at most, and the method has good application prospects.

Description

Technical Field

[0001] The present invention relates to the field of alcohol oxidation catalytic systems, and more specifically, to an alcohol oxidation catalytic system and an oxidation method based on the combination of a copper salt and a bifunctional ligand. Background Art

[0002] Aldehydes and ketones are common intermediates for many fine chemicals and pharmaceuticals. Their main production route is the selective oxidation of alcohols. Whether in the laboratory or in industrial production, the ideal way for the selective oxidation of alcohols is to achieve efficient selective oxidation of alcohols under air and room temperature conditions. In recent decades, many homogeneous and heterogeneous catalysts based on metals such as Pt, Pd, Ru, Au, Ag, Cu, and Fe have been developed and show good activity in alcohol oxidation reactions. Among them, copper-based catalysts are the most promising because they are not only cheap and easy to obtain, but also because they have efficient catalytic performance in the aerobic oxidation of alcohols.

[0003] Among the many reported copper-based catalysts, copper salts combined with nitro radicals, such as 2,2,6,6-tetramethylpiperidin-n-oxide (TEMPO), have been used for efficient alcohol selective oxidation. Generally speaking, these Cu / TEMPO systems require the addition of suitable ligands to achieve efficient alcohol oxidation processes. The most widely used catalytic system is 2,2′-bipyridine (bpy) as an auxiliary ligand and an excess of N-methylimidazole (NMI). However, these catalytic systems require many catalytic components, including copper salts, TEMPO, ligands and bases, to achieve efficient conversion of alcohols, which limits their industrial applications. There are two ways to improve the Cu / TEMPO catalytic system. One way is to reduce the catalytic components to simplify the catalytic system. According to Stahl et al., the yield of the Cu / TEMPO system with NMI as a single ligand can reach 68%. Another way is to combine the ligand and TEMPO into a bifunctional molecule. Reedijk's team made a preliminary attempt, combining TEMPO and pyrazole, pyridine or bipyridine into one molecule. These bifunctional ligands only showed good catalytic activity for the aerobic oxidation of benzyl alcohol in combination with CuBr2, but potassium tert-butoxide needed to be added additionally. Subsequently, Chen et al. used TEMPO units containing imidazole salts to react with copper powder to generate Cu-NHC-TEMPO in situ, which showed excellent catalytic activity for the aerobic oxidation of alcohols under air conditions. The disadvantage of this method is that the synthesis process of TEMPO-based imidazole salts is not easy, and the catalytic reaction can only be carried out at high temperatures. Based on the Cu(I) / TEMPO / bpy / NMI system, Gao et al. developed a catalytic system combining bifunctional ligands bpy-TEMPO or NMI-TEMPO with Cu(I) salts, and showed efficient oxidation activity for a variety of alcohols. However, these studies still require additional ligands or additives, which limits further industrial applications. Summary of the invention

[0004] In order to achieve these purposes and other advantages according to the present invention, on the one hand, a preferred embodiment of the present invention provides an alcohol oxidation catalytic system based on a combination of a copper salt and a bifunctional ligand, which is prepared by the following process:

[0005] Firstly, N,N,N-trimethylethylenediamine and N-containing organic molecules combined with pyridine, thiophene or benzene are prepared through amine-aldehyde condensation reaction and sodium borohydride reduction reaction, and then a bifunctional ligand containing TEMPO and the above-mentioned N-containing organic molecules is synthesized through a nucleophilic substitution reaction, and it is combined with a copper salt to form a catalytic system.

[0006] According to a preferred embodiment of the present invention, the N-containing organic molecule is prepared by amine-aldehyde condensation reaction of 2-pyridinecarboxaldehyde, 2-thiophenecarboxaldehyde and benzaldehyde with N,N,N-trimethylethylenediamine and sodium borohydride reduction reaction.

[0007] According to a preferred embodiment of the present invention, the bifunctional ligand is formed by combining dibromoalkanes of different carbon chain lengths with 4-OH-TEMPO and a N-containing organic molecule through a nucleophilic substitution reaction.

[0008] According to a preferred embodiment of the present invention, the bifunctional ligand contains a pyridine group, and the pyridine group is connected to a N-containing organic molecule, wherein the carbon chain length of the TEMPO group is 6.

[0009] On the other hand, according to a preferred embodiment of the present invention, there is provided an oxidation method of an alcohol oxidation catalytic system based on a combination of a copper salt and a bifunctional ligand, wherein air is used as an oxidant and the catalytic system is used as a catalyst at room temperature to catalyze the oxidation of alcohol to obtain the corresponding carbonyl compound.

[0010] According to a preferred embodiment of the present invention, the copper salt is any one or more of cuprous chloride, cuprous bromide, cuprous iodide, tetraacetonitrile copper hexafluorophosphate or cupric chloride.

[0011] According to a preferred embodiment of the present invention, during the catalytic oxidation process, the amount of the catalytic system used is 1 mol%, 2 mol%, 3 mol%, 4 mol% and 5 mol% of the substrate.

[0012] According to a preferred embodiment of the present invention, in the catalytic oxidation process, the organic solvent is selected from any one or more of DMF, DMSO, dichloromethane, acetonitrile, toluene, THF, ethanol or water.

[0013] According to a preferred embodiment of the present invention, the alcohol is any one of benzyl alcohol, allyl alcohol, heterocyclic aromatic alcohol, aliphatic primary alcohol and part of aliphatic secondary alcohol.

[0014] The present invention has at least the following beneficial effects: the present invention designs a novel bifunctional ligand containing TEMPO and an organic molecule containing N, combined with cuprous chloride to form a catalytic system, using acetonitrile as a solvent, for oxidizing various benzyl alcohols, allyl alcohols, heterocyclic aromatic alcohols and aliphatic alcohols to corresponding aldehydes or ketones under mild conditions, and improving the catalytic performance through the synergistic effect between molecules. The reaction has a high yield and a wide substrate range. More importantly, the reaction time is short and the reaction conditions are mild. Only 2 mol% of the catalyst is used, and the TOF can reach up to 50h -1 , which has good application prospects.

[0015] The specific reaction formula is as follows:

[0016]

[0017] Other advantages, objectives and features of the present invention will be embodied in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention. DETAILED DESCRIPTION

[0018] The present invention is further described in detail below in conjunction with embodiments so that those skilled in the art can implement the invention with reference to the description.

[0019] The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are only examples, and those skilled in the art can think of other obvious variations. The basic principles of the present invention defined in the following description can be applied to other embodiments, variations, improvements, equivalents, and other technical solutions that do not deviate from the spirit and scope of the present invention.

[0020] It is to be understood that the term "one" should be understood as "at least one" or "one or more", that is, in one embodiment, the number of an element may be one, while in another embodiment, the number of the element may be multiple, and the term "one" should not be understood as a limitation on the quantity.

[0021] Example 1

[0022] Add a methanol solution (40 ml) of N,N-dimethylethylenediamine (0.8815 g, 10 mmol) to a methanol solution (20 ml) of pyridine-2-carboxaldehyde (1.0711 g, 10 mmol), stir evenly, and reflux at 65°C for 20 h. Monitor the reaction with a plate until it is complete, and spin-dry the methanol to obtain 1.75 g of a brown liquid with a yield of 98.79%. 1H NMR (400MHz, CDCl3) δ8.59(s,1H),8.37(s,1H),7.93(dd,J=7.5,3.9Hz,1H),7.68(td,J=7.4,4.3Hz,1H),7.2 5(dd,J=10.1,5.5Hz,1H), 3.75(dd,J=10.9,5.9Hz,2H), 2.62(dd,J=11.3,6.8Hz,2H), 2.26(d,J=4.5Hz,6H).

[0023] Example 2

[0024] A methanol solution (60 ml) of N,N-dimethyl-1-(pyridine-2-methyl)imine (1.7713 g, 10 mmol) was cooled to 0°C in an ice bath, and a small amount of NaBH4 (0.9457 g, 25 mmol) was added to the above solution. The resulting reaction mixture was stirred at 0°C for 10 minutes, then heated to room temperature and stirred for another 5 hours. Methanol was dried by spin drying, water was added, and the mixture was extracted with ethyl acetate and dried with Na2SO4. The mixture was dried by spin drying to obtain 1.68 g of a reddish brown liquid with a yield of 94.74%. 1 H NMR(400MHz, CDCl3)δ8.49(d,J=4.8Hz,1H),7.58(td,J=7.7,1.7Hz,1H),7.30–7.22(m,1H),7.0 9(dd,J=7.3,5.0Hz,1H),3.87(s,2H),2.68(t,J=6.2Hz,2H),2.39(t,J=6.2Hz,3H),2.16(s,6H).

[0025] Example 3

[0026] Add a methanol solution (40 ml) of N,N-dimethylethylenediamine (0.8815 g, 10 mmol) to a methanol solution (20 ml) of thiophene-2-carboxaldehyde (1.1215 g, 10 mmol), stir evenly, and reflux at 65°C for 20 h. Monitor the reaction with a plate until it is complete, and spin-dry the methanol to obtain 1.80 g of a brown liquid with a yield of 98.74%. 1 H NMR (400MHz, CDCl3) δ8.37(d,J=0.7Hz,1H),7.35(d,J=5.0Hz,1H),7.26(dt,J=4.9,2.5 Hz, 1H), 7.03 (dd, J = 5.0, 3.7Hz, 1H), 3.70–3.65 (m, 2H), 2.62–2.58 (m, 2H), 2.27 (s, 6H).

[0027] Example 4

[0028] A methanol solution (60 ml) of N,N-dimethyl-1-(thiophene-2-methyl)imine (1.8230 g, 10 mmol) was cooled to 0°C in an ice bath, and a small amount of NaBH4 (0.9457 g, 25 mmol) was added to the above solution. The resulting reaction mixture was stirred at 0°C for 10 minutes, then heated to room temperature and stirred for another 5 hours. The methanol was dried by spin drying, water was added, and the mixture was extracted with ethyl acetate, dried with Na2SO4, and 1.54 g of a reddish brown liquid was obtained by spin drying, with a yield of 83.56%. 1 H NMR (400MHz, CDCl3) δ7.22–7.12(m,1H),7.00–6.85(m,2H),3.99(s,2H),2.70(t,J=6.1Hz,2H),2.40(t,J=6.1Hz,2H),2.18(s,6H).

[0029] Example 5

[0030] Add a methanol solution (40 ml) of N,N-dimethylethylenediamine (0.8815 g, 10 mmol) to a methanol solution (20 ml) of benzaldehyde (1.0612 g, 10 mmol), stir evenly, and reflux at 65°C for 20 h. Monitor the reaction with a plate until it is complete, and spin-dry the methanol to obtain 1.75 g of a light yellow liquid with a yield of 99.28%. 1 H NMR (400MHz, CDCl3) δ8.28 (s, 1H), 7.78–7.63 (m, 2H), 7.47–7.29 (m, 3H), 3.72 (t, J = 7.0Hz, 2H), 2.63 (dd, J = 10.4, 3.6Hz, 2H), 2.30 (d, J = 1.1Hz, 6H).

[0031] Example 6

[0032] A methanol solution (60 ml) of N,N-dimethyl-1-(phenyl-2-methyl)imine (1.7627 g, 10 mmol) was cooled to 0°C in an ice bath, and a small amount of NaBH4 (0.9457 g, 25 mmol) was added to the above solution. The resulting reaction mixture was stirred at 0°C for 10 minutes, then heated to room temperature and stirred for another 5 hours. The methanol was dried by spin drying, water was added, and the mixture was extracted with ethyl acetate, dried with Na2SO4, and 1.32 g of a light yellow liquid was obtained by spin drying, with a yield of 74.04%. 1 H NMR (400MHz, CDCl3) δ7.36–7.10(m,5H),3.75(s,2H),2.64(t,J=6.1Hz,2H),2.37(t,J=6.1Hz,2H),2.14(s,6H).

[0033] Example 7

[0034] 4-OH-TEMPO (1.73 g, 10 mmol) was dissolved in THF (10 ml) and added dropwise to a mixture containing Br(CH2)4-Br (6.4764 g, 30 mmol), Bu4NHSO4 (0.136 g, 4 mol%) and NaOH (50 wt%, 10 ml), and stirred at room temperature for 15 h. The reaction solution was then poured into ice water (60 ml), extracted with ethyl acetate, washed with saturated NaCl, dried over anhydrous Na2SO4, and dried with a vacuum rotary evaporator. Finally, it was purified by silica gel column chromatography to obtain 2.19 g of an orange oily liquid with a yield of 71.36%. 1 H NMR (400MHz, CDCl3, ppm): δ3.60–3.54(m,1H),3.44(dd,J=13.6,6.7Hz,4H),2.00 –1.89(m,4H),1.73–1.66(m,2H),1.54(d,J=5.9Hz,2H),1.27(s,6H),1.20(s,6H).

[0035] Example 8

[0036] A solution of 4-OH-TEMPO (1.73 g, 10 mmol) in THF (10 ml) was added dropwise to a mixture of Br(CH2)6Br (7.3191 g, 30 mmol), Bu4NHSO4 (0.136 g, 4 mol%) and an aqueous NaOH solution (50 wt%, 10 ml), and the resulting mixture was stirred overnight at room temperature. Then, the mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated NaCl, dried with anhydrous Na2SO4, and the solvent was dried by spin drying. Finally, 2.61 g of a red oily liquid was obtained by purification using silica gel column chromatography with a yield of 77.83%. 1 H NMR (400MHz, CDCl3, ppm): δ3.59–3.52(m,1H),3.40(dd,J=12.3,6.1Hz,4H),1.94(d,J=12.3Hz,2H),1.89–1.81(m,2H),1 .56(dd,J=13.8,6.5Hz,4H),1.43(dd,J=14.7,7.4Hz,2H),1.36(dd,J=14.9,7.7Hz,2H),1.29–1.24(m,6H),1.19(s,6H).

[0037] Example 9

[0038] 4-OH-TEMPO (1.73 g, 10 mmol) was dissolved in THF (10 ml) and added dropwise to a solution containing Br(CH2) 10-Br (9.0024 g, 30 mmol), Bu4NHSO4 (0.136 g, 4 mol%) and NaOH (50 wt%, 10 ml) were stirred at room temperature for 15 h. The reaction solution was then poured into ice water (60 ml), extracted with ethyl acetate, washed with saturated NaCl, dried over anhydrous Na2SO4, and dried with a vacuum rotary evaporator. Finally, it was purified by silica gel column chromatography to obtain 2.21 g of an orange oily liquid with a yield of 56.46%. 1 H NMR (400MHz, CDCl3, ppm): δ3.60–3.54(m,1H),3.39(t,J=6.8Hz,4H),2.03–1.95(m,2H),1.87–1.80(m,2H) ,1.65(s,2H),1.56–1.50(m,2H),1.39(d,J=7.3Hz,2H),1.33(d,J=19.1Hz,10H),1.25(d,J=21.4Hz,12H).

[0039] Example 10

[0040] A solution of Br(CH2)6-TEMPO (3.3531 g, 10 mmol) in THF (10 ml) was added dropwise to a mixture of N,N-dimethyl-N-(pyridine-2-methyl)ethylenediamine (3.5826 g, 20 mmol), Bu4NHSO4 (0.136 g, 4 mol%) and an aqueous NaOH solution (50 wt%, 10 ml), and the resulting mixture was stirred at room temperature for 24 h. Then, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated NaCl, dried over anhydrous Na2SO4, and the solvent was dried by spin drying. Finally, 1.64 g of an orange-red liquid (L1) was obtained by column purification with a yield of 37.84%. 1 H NMR(400MHz, CDCl3) δ8.53(d,J=1.7Hz,1H),7.66(dd,J=10.1,5.4Hz,1H),7.53–7.44(m,1 H),7.15(d,J=1.8Hz,1H),3.77(d,J=2.4Hz,2H),3.52–3.35(m,2H),3.19(d,J=1.1Hz,1H) ,2.66(d,J=7.1Hz,2H),2.54(d,J=9.7Hz,2H),2.45(d,J=3.2Hz,2H),2.34–2.15(m,6H),2 .05(d,J=3.6Hz,2H),1.90(s,2H),1.79(d,J=1.1Hz,4H),1.58–1.44(m,4H),1.26(s,12H).

[0041] Embodiment 11

[0042] A solution of THF (10 ml) containing Br(CH2)6-TEMPO (3.3531 g, 10 mmol) was added dropwise to a mixture of N,N-dimethyl-N-(thiophene-2-methyl)ethylenediamine (3.6860 g, 20 mmol), Bu4NHSO4 (0.136 g, 4 mol%) and an aqueous NaOH solution (50 wt%, 10 ml), and the resulting mixture was stirred at room temperature for 24 h. Then, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated NaCl, dried over anhydrous Na2SO4, and the solvent was dried by spin drying. Finally, 0.42 g of an orange-red liquid (L2) was obtained by column purification with a yield of 9.58%. 1 H NMR(400MHz, CDCl3) δ7.23(d,J=1.5Hz,1H),6.94(dd,J=19.0,1.9Hz,2H),3.87(s,2H),3.76–3.50(m,2H),3.44(d,J=1.0Hz,1H),2.6 4(d,J=1.4Hz,2H),2.47(d,J=7.1Hz,4H),2.27(s,6H),2.19–1.63(m,8H),1.55(d,J=5.2Hz,4H),1.28(dd,J=24.2,14.1,5.6Hz,12H).

[0043] Example 12

[0044] A solution of THF (10 ml) containing Br(CH2)6-TEMPO (3.3531 g, 10 mmol) was added dropwise to a mixture of N,N-dimethyl-N-(phenyl-2-methyl)ethylenediamine (3.5655 g, 20 mmol), Bu4NHSO4 (0.136 g, 4 mol%) and an aqueous NaOH solution (50 wt%, 10 ml), and the resulting mixture was stirred at room temperature for 24 h. Then, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated NaCl, dried with anhydrous Na2SO4, and the solvent was dried by spin drying. Finally, 1.09 g of an orange-red liquid (L3) was obtained by column purification with a yield of 25.21%. 1 H NMR (400MHz, CDCl3) δ7.35–7.20(m,5H),3.68–3.45(m,3H),3.40(d,J=6.5Hz,2H),2.56(d,J=4.3Hz ,2H),2.43(d,J=4.6Hz,4H),2.20(s,6H),2.12–1.58(m,8H),1.57–1.40(m,4H),1.36–1.12(m,12H).

[0045] Embodiment 13

[0046] A solution of THF (10 ml) containing Br(CH2)4-TEMPO (3.0725 g, 10 mmol) was added dropwise to a mixture of N,N-dimethyl-N-(pyridine-2-methyl)ethylenediamine (3.5826 g, 20 mmol), Bu4NHSO4 (0.136 g, 4 mol%) and an aqueous NaOH solution (50 wt%, 10 ml), and the resulting mixture was stirred at room temperature for 24 h. Then, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated NaCl, dried with anhydrous Na2SO4, and the solvent was dried by spin drying. Finally, 1.15 g of an orange-red liquid (L4) was obtained by column purification with a yield of 28.37%. 1 H NMR (400MHz, CDCl3) δ8.57(s,1H),7.69(d,J=0.5Hz,1H),7.54(d,J=0.6Hz,1H),7.19(d,J=2.8Hz,1H),3.81(d,J=3.9Hz,2H),3.61(d,J=6.4Hz,1H),3. 47(d,J=4.8Hz,2H),2.69(d,J=1.2Hz,2H),2.52(dd,J=29.4,2.0Hz,4H),2. 40–2.12(m,6H),2.12–1.65(m,4H),1.63–1.46(m,4H),1.34–1.20(m,12H).

[0047] Embodiment 14

[0048] Dissolve Br(CH2) 10 -TEMPO (3.9140g, 10mmol) in THF (10ml) solution was added dropwise to a mixture of N,N-dimethyl-N-(pyridine-2-methyl)ethylenediamine (3.5826g, 20mmol), Bu4NHSO4 (0.136g, 4mol%) and NaOH aqueous solution (50wt%, 10ml), and the resulting mixture was stirred at room temperature for 24h. Then, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated NaCl, dried over anhydrous Na2SO4, and the solvent was dried by spin drying. Finally, column purification was performed to obtain 1.41g of orange-red liquid (L5) with a yield of 28.79%. 1H NMR (400MHz, CDCl3) δ8.53 (d, J = 3.4Hz, 1H), 7.66 (s, 1H), 7.49 (d, J = 4.3Hz, 1H),7.32(s,1H),3.77(d,J=5.2Hz,2H),3.43(d,J=28.2Hz,2H),3.21(d,J=1 .6Hz,1H),2.65(s,2H),2.57(d,J=11.3Hz,2H),2.45(s,2H),2.25(d,J=14. 1Hz,6H),2.05(s,4H),1.86–1.51(m,12H),1.27(s,8H),1.27–1.17(m,12H).

[0049] Embodiment 15

[0050] In a 10 ml reaction tube, add cuprous chloride (9.9 mg, 0.1 mmol), L1 (43.4 mg, 0.1 mmol), benzyl alcohol (216 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 40 min. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated by the internal standard-standard curve method to be 99%.

[0051] Example 16

[0052] In a 10 ml reaction tube, add cuprous bromide (14.4 mg, 0.1 mmol), L1 (43.4 mg, 0.1 mmol), benzyl alcohol (216 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 40 min. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated by the internal standard-standard curve method to be 99%.

[0053] Embodiment 17

[0054] In a 10 ml reaction tube, add cuprous iodide (19.1 mg, 0.1 mmol), L1 (43.4 mg, 0.1 mmol), benzyl alcohol (216 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 40 min. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated to be 72% by the internal standard-standard curve method.

[0055] Embodiment 18

[0056] In a 10 ml reaction tube, add copper tetraacetonitrile hexafluorophosphate (37.3 mg, 0.1 mmol), L1 (43.4 mg, 0.1 mmol), benzyl alcohol (216 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 40 min. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated to be 42% by the internal standard-standard curve method.

[0057] Embodiment 19

[0058] In a 10 ml reaction tube, add copper chloride dihydrate (17.1 mg, 0.1 mmol), L1 (43.4 mg, 0.1 mmol), benzyl alcohol (216 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 40 min. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated to be 2% by the internal standard-standard curve method.

[0059] Embodiment 20

[0060] In a 10 ml reaction tube, add cuprous chloride (9.9 mg, 0.1 mmol), L2 (43.8 mg, 0.1 mmol), benzyl alcohol (216 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 40 min. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated to be 76% by the internal standard-standard curve method.

[0061] Embodiment 21

[0062] In a 10 ml reaction tube, add cuprous chloride (9.9 mg, 0.1 mmol), L3 (43.3 mg, 0.1 mmol), benzyl alcohol (216 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 40 min. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated by the internal standard-standard curve method to be 96%.

[0063] Embodiment 22

[0064] In a 10 ml reaction tube, add cuprous chloride (9.9 mg, 0.1 mmol), L4 (40.5 mg, 0.1 mmol), benzyl alcohol (216 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 40 min. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated to be 78% by the internal standard-standard curve method.

[0065] Embodiment 23

[0066] In a 10 ml reaction tube, add cuprous chloride (9.9 mg, 0.1 mmol), L5 (48.9 mg, 0.1 mmol), benzyl alcohol (216 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 40 min. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated by the internal standard-standard curve method to be 96%.

[0067] Embodiment 24

[0068] In a 10 ml reaction tube, add cuprous chloride (1.9 mg, 0.02 mmol), L1 (8.7 mg, 0.02 mmol), benzyl alcohol (216 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated to be 60% by the internal standard-standard curve method.

[0069] Embodiment 25

[0070] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), benzyl alcohol (216 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated by the internal standard-standard curve method to be 99%.

[0071] Embodiment 26

[0072] In a 10 ml reaction tube, add cuprous chloride (5.9 mg, 0.06 mmol), L1 (26.1 mg, 0.06 mmol), benzyl alcohol (216 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated by the internal standard-standard curve method to be 99%.

[0073] Embodiment 27

[0074] In a 10 ml reaction tube, add cuprous chloride (7.9 mg, 0.08 mmol), L1 (34.7 mg, 0.08 mmol), benzyl alcohol (216 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated by the internal standard-standard curve method to be 99%.

[0075] Embodiment 28

[0076] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), benzyl alcohol (216 mg, 2 mmol) and DMF (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated to be 37% by the internal standard-standard curve method.

[0077] Embodiment 29

[0078] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), benzyl alcohol (216 mg, 2 mmol) and DMSO (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated to be 28% by the internal standard-standard curve method.

[0079] Embodiment 30

[0080] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), benzyl alcohol (216 mg, 2 mmol) and toluene (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated to be 54% by the internal standard-standard curve method.

[0081] Embodiment 31

[0082] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), benzyl alcohol (216 mg, 2 mmol) and tetrahydrofuran (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated to be 54% by the internal standard-standard curve method.

[0083] Embodiment 32

[0084] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), benzyl alcohol (216 mg, 2 mmol) and ethanol (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated to be 53% by the internal standard-standard curve method.

[0085] Embodiment 33

[0086] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), benzyl alcohol (216 mg, 2 mmol) and dichloromethane (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated to be 58% by the internal standard-standard curve method.

[0087] Embodiment 34

[0088] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), benzyl alcohol (216 mg, 2 mmol) and water (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated to be 35% by the internal standard-standard curve method.

[0089] Embodiment 35

[0090] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (8.7 mg, 0.02 mmol), benzyl alcohol (216 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated to be 66% by the internal standard-standard curve method.

[0091] Embodiment 36

[0092] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (26.1 mg, 0.06 mmol), benzyl alcohol (216 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of benzaldehyde is calculated to be 80% by the internal standard-standard curve method.

[0093] Embodiment 37

[0094] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 2-methylbenzyl alcohol (244.3 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 20 hours. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 2-methylbenzaldehyde is calculated to be 99% by the internal standard-standard curve method.

[0095] Embodiment 38

[0096] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 3-methylbenzyl alcohol (244.3 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 3-methylbenzaldehyde is calculated to be 99% by the internal standard-standard curve method.

[0097] Embodiment 39

[0098] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 4-methylbenzyl alcohol (244.3 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 4-methylbenzaldehyde is calculated to be 99% by the internal standard-standard curve method.

[0099] Embodiment 40

[0100] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 2-methoxybenzyl alcohol (276.3 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 2-methoxybenzaldehyde is calculated to be 97% by the internal standard-standard curve method.

[0101] Embodiment 41

[0102] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 3-methoxybenzyl alcohol (276.3 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 3-methoxybenzaldehyde is calculated to be 99% by the internal standard-standard curve method.

[0103] Embodiment 42

[0104] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 4-methoxybenzyl alcohol (276.3 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 4-methoxybenzaldehyde is calculated to be 99% by the internal standard-standard curve method.

[0105] Embodiment 43

[0106] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 2-nitrobenzyl alcohol (306.3 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 20 hours. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 2-nitrobenzaldehyde is calculated to be 99% by the internal standard-standard curve method.

[0107] Embodiment 44

[0108] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 3-nitrobenzyl alcohol (306.3 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 3-nitrobenzaldehyde is calculated to be 99% by the internal standard-standard curve method.

[0109] Embodiment 45

[0110] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 4-nitrobenzyl alcohol (306.3 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 4-nitrobenzaldehyde is calculated to be 99% by the internal standard-standard curve method.

[0111] Embodiment 46

[0112] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 3-fluorobenzyl alcohol (252.1 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 3-fluorobenzaldehyde is calculated to be 99% by the internal standard-standard curve method.

[0113] Embodiment 47

[0114] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 4-fluorobenzyl alcohol (252.1 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 4-fluorobenzaldehyde is calculated to be 99% by the internal standard-standard curve method.

[0115] Embodiment 48

[0116] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 3-chlorobenzyl alcohol (285.1 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 3-chlorobenzaldehyde is calculated to be 99% by the internal standard-standard curve method.

[0117] Embodiment 49

[0118] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 4-chlorobenzyl alcohol (285.1 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 4-chlorobenzaldehyde is calculated to be 99% by the internal standard-standard curve method.

[0119] Embodiment 50

[0120] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 2-bromobenzyl alcohol (374.0 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 4 hours. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 2-bromobenzaldehyde is calculated to be 99% by the internal standard-standard curve method.

[0121] Embodiment 51

[0122] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 3-bromobenzyl alcohol (374.0 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 3-bromobenzaldehyde is calculated to be 99% by the internal standard-standard curve method.

[0123] Embodiment 52

[0124] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 4-bromobenzyl alcohol (374.0 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 4-bromobenzaldehyde is calculated to be 99% by the internal standard-standard curve method.

[0125] Embodiment 53

[0126] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), thiophene-2-methanol (228.3 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of thiophene-2-carboxaldehyde is calculated to be 97% by the internal standard-standard curve method.

[0127] Embodiment 54

[0128] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), pyridine-2-methanol (218.3 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of pyridine-2-carboxaldehyde is calculated to be 28% by the internal standard-standard curve method.

[0129] Embodiment 55

[0130] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), cinnamyl alcohol (268.4 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of cinnamaldehyde is calculated to be 93% by the internal standard-standard curve method.

[0131] Embodiment 56

[0132] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 2-butene-1-ol (144.2 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 2-butene-1-aldehyde is calculated to be 95% by the internal standard-standard curve method.

[0133] Embodiment 57

[0134] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), n-butanol (148.2 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of n-butyraldehyde is calculated to be 53% by the internal standard-standard curve method.

[0135] Embodiment 58

[0136] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), n-hexanol (204.3 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of n-hexanal is calculated to be 44% by the internal standard-standard curve method.

[0137] Embodiment 59

[0138] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), n-octanol (260.4 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of n-octanal is calculated to be 44% by the internal standard-standard curve method.

[0139] Embodiment 60

[0140] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 2-octanol (260.4 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 2-octanal is calculated to be 21% by the internal standard-standard curve method.

[0141] Embodiment 61

[0142] In a 10 ml reaction tube, add cuprous chloride (3.9 mg, 0.04 mmol), L1 (17.4 mg, 0.04 mmol), 1-phenylethanol (122.2 mg, 2 mmol) and acetonitrile (2 ml) respectively, and react at 30 ° C for 1 hour. Use biphenyl as the internal standard, draw 0.5 ml of biphenyl into a 10 ml volumetric flask with a syringe, and make up the volume with acetonitrile. Then filter with an organic microporous filter membrane, draw 0.2 μl of the solution and inject it into the gas chromatograph. The yield of 1-phenylacetaldehyde is calculated to be 31% by the internal standard-standard curve method.

[0143] The optimization process of experimental conditions is as follows:

[0144] 1. Determination of copper salt

[0145] Table 1

[0146]

[0147] Reaction conditions: benzyl alcohol (2 mmol), copper salt (0.1 mmol), L1 (0.1 mmol), acetonitrile (2 ml), 30°C, 40 min.

[0148] From the data in Table 1, it can be seen that when the copper salt is CuCl, the yield is the highest.

[0149] 2. Determination of ligand

[0150] Table 2

[0151]

[0152] Reaction conditions: benzyl alcohol (2 mmol), cuprous chloride (0.1 mmol), ligand (0.1 mmol), acetonitrile (2 ml), 30°C, 40 min.

[0153] From the data in Table 2, it can be seen that when the ligand is L1, the yield is the highest.

[0154] 3. Determination of copper salt dosage

[0155] Table 3

[0156]

[0157] Reaction conditions: benzyl alcohol (2 mmol), cuprous chloride, L1, acetonitrile (2 ml), air, 30°C, 1 h.

[0158] From the data in Table 3, it can be seen that when the molar amount of cuprous chloride is 0.04 mmol, the yield reaches 99%.

[0159] 4. Determination of solvent

[0160] Table 4

[0161]

[0162] Reaction conditions: benzyl alcohol (2 mmol), cuprous chloride (0.04 mmol), L1 (0.04 mmol), solvent (2 ml), air, 30°C, 1 h.

[0163] From the data in Table 4, it can be seen that when the solvent is acetonitrile, the yield is the highest.

[0164] 5. Determination of ligand dosage

[0165] Table 5

[0166]

[0167] Reaction conditions: benzyl alcohol (2 mmol), cuprous chloride, L1, acetonitrile (2 ml), air, 30°C, 1 h.

[0168] From the data in Table 4, it can be seen that the yield is highest when the copper chloride is 0.04 mmol and the L1 is 0.04 mmol.

[0169] Table 6

[0170]

[0171]

[0172] a Reaction conditions: substrate (2 mmol), cuprous chloride (0.04 mmol), L1 (0.04 mmol), acetonitrile (2 mL), air, 30 °C, 1 h.

[0173] b Extend the reaction time to 20 h.

[0174] c Extend the reaction time to 4 h.

[0175] The catalytic system provided by the present invention uses acetonitrile as a solvent and is used to oxidize various benzyl alcohols, allyl alcohols, heterocyclic aromatic alcohols and aliphatic alcohols to corresponding aldehydes or ketones under mild conditions, and improves the catalytic performance through the synergistic effect between molecules. The reaction has a high yield and a wide substrate range. More importantly, the reaction time is short and the reaction conditions are mild. Only 2 mol% of the catalyst is used, and the TOF can reach up to 50h -1 , which has good application prospects.

[0176] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and the embodiments shown and described herein.

Claims

1. An alcohol oxidation catalytic system based on the combination of copper salt and bifunctional ligand, characterized in that: Prepared by the following process: Firstly, N,N,N-trimethylethylenediamine and N-containing organic molecules combined with pyridine, thiophene or benzene are prepared through amine-aldehyde condensation reaction and sodium borohydride reduction reaction, and then a bifunctional ligand containing TEMPO and the above-mentioned N-containing organic molecules is synthesized through a nucleophilic substitution reaction, and it is combined with a copper salt to form a catalytic system.

2. The alcohol oxidation catalytic system based on the combination of copper salt and bifunctional ligand according to claim 1, characterized in that: The N-containing organic molecule is prepared by amine-aldehyde condensation reaction of 2-pyridinecarboxaldehyde, 2-thiophenecarboxaldehyde and benzaldehyde with N,N,N-trimethylethylenediamine and sodium borohydride reduction reaction.

3. The alcohol oxidation catalytic system based on the combination of copper salt and bifunctional ligand according to claim 2, characterized in that: The bifunctional ligand is composed of dibromoalkanes with different carbon chain lengths, 4-OH-TEMPO and a N-containing organic molecule combined together through a nucleophilic substitution reaction.

4. The alcohol oxidation catalytic system based on the combination of copper salt and bifunctional ligand according to claim 3, characterized in that: The bifunctional ligand contains a pyridine group, and the pyridine group is connected to a N-containing organic molecule, wherein the carbon chain length of the TEMPO group is 6.

5. An oxidation method according to any one of claims 1 to 4, wherein the alcohol oxidation catalytic system based on the combination of copper salt and bifunctional ligand is characterized in that: At room temperature, air is used as an oxidant and the catalytic system is used as a catalyst to catalytically oxidize alcohol to obtain the corresponding carbonyl compound.

6. The selective oxidation method of the alcohol oxidation catalytic system based on the combination of copper salt and bifunctional ligand according to claim 5, characterized in that: The copper salt is any one or more of cuprous chloride, cuprous bromide, cuprous iodide, tetraacetonitrile copper hexafluorophosphate or cupric chloride.

7. The oxidation method of the alcohol oxidation catalytic system based on the combination of copper salt and bifunctional ligand according to claim 1, characterized in that: During the catalytic oxidation process, the amount of the catalyst system used was 1 mol%, 2 mol%, 3 mol%, 4 mol% and 5 mol% of the substrate.

8. The oxidation method of the alcohol oxidation catalytic system based on the combination of copper salt and bifunctional ligand according to claim 5, characterized in that: In the catalytic oxidation process, the organic solvent is selected from any one or more of DMF, DMSO, dichloromethane, acetonitrile, toluene, THF, ethanol or water.

9. The oxidation method of the alcohol oxidation catalytic system based on the combination of copper salt and bifunctional ligand according to claim 5, characterized in that: The alcohol is any one of benzyl alcohol, allyl alcohol, heterocyclic aromatic alcohol, aliphatic primary alcohol and part of aliphatic secondary alcohol.

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