A method for preparing gamma-oxoesters and / or amides

Abstract

The present invention relates to a method for preparing γ-oxoesters / amides. Specifically, under the catalytic conditions of nickel and nitrogen ligands, ethers are carbonylated with phenols, alcohols, or amines to prepare the γ-oxoesters / amides. The method uses ether compounds widely found in nature, including cyclic ethers, linear ethers, phenols, alcohols, and amines, as raw materials. Using CO gas as a C1 source and ethylene gas as a C2 source, in the presence of a catalytic amount of an inexpensive nickel catalyst, the ether γ-carbonylation product is obtained with high atomic utilization and high yield.

Description

Technical Field

[0001] The present invention relates to a method for synthesizing gamma-oxoesters and / or amides. Background Art

[0002] Ethers are biologically active chemical fragments, widely found in biomass energy sources and pharmaceuticals. The functionalization of ether compounds is of great significance for energy regeneration drug discovery and other applications. γ-Oxoesters / amides are a key group of these fragments, found in many pharmaceutical molecules. Ethylene gas is an important C2 source and a fundamental chemical raw material for synthetic fibers, synthetic rubber, synthetic plastics, and synthetic ethanol. It is also used in the manufacture of vinyl chloride, styrene, ethylene oxide, acetic acid, acetaldehyde, and explosives. Ethylene is one of the world's most produced chemical products. The ethylene industry is at the core of the petrochemical industry, accounting for over 75% of petrochemical production and playing a crucial role in the national economy. Ethylene production is now considered a key indicator of a country's petrochemical development. The introduction of simple small ethylene molecules into molecules is of great significance for scientific development. In recent years, transition-metal-catalyzed carbonylation, esterification, and amination reactions have emerged as a promising method for preparing amides and esters with various functional groups. However, these reported reactions also have some disadvantages, such as the need to use expensive palladium-phosphine catalysts; the use of activated substrates; the narrow applicability of substrates, etc.

[0003] Compared to previous methods for synthesizing γ-oxoesters / amides, we have developed a novel carbonylation reaction catalyzed by inexpensive nickel. Using readily available phenols, alcohols, and amines, ethers widely found in various useful natural products, inexpensive peroxides, and the industrial raw material ethylene, we can synthesize γ-oxoesters / amides in a CO atmosphere with high yield, excellent selectivity, and a broad substrate range.

[0004] In summary, this paper describes a nickel-catalyzed carbonylation esterification method for the preparation of γ-oxoesters / amides. Summary of the Invention

[0005] The object of the present invention is to provide a method for synthesizing gamma-oxoester / amide.

[0006]

[0007] Reaction Equation 1: γ-Oxoester / amide

[0008] The specific operation steps are as follows (reaction equation 1):

[0009] The reaction is carried out in a 300 ml autoclave. The catalyst, catalyst promoter, and hydroxyl- or amine-containing compound 3 are weighed. Peroxide and ether are injected under a nitrogen atmosphere. The reaction is then placed in an atmosphere of carbon monoxide and ethylene at 70-150°C, preferably 110-130°C. The reaction time is 10-36 hours, preferably 18-24 hours. After completion of the reaction, the γ-oxoester / amide derivative 4 is isolated.

[0010] The catalyst is nickel di(acetylacetonate), nickel acetate, nickel chloride, or nickel iodide, preferably nickel di(acetylacetonate). The catalyst promoter is 6,6'-dimethyl-2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, or 2,2'-bipyridine, preferably 4,4'-dimethyl-2,2'-bipyridine.

[0011] The molar ratio of phenol, alcohol or amine to nickel di(acetylacetonate) and 6,6'-dimethyl-2,2'-bipyridine is 100:1:1-100:20:20, preferably 100:5:5-100:10:10.

[0012] The gas pressure of carbon monoxide is 1 to 30 atmospheres, preferably 1 to 10 atmospheres.

[0013] The gas pressure of carbon monoxide is 1 to 30 atmospheres, preferably 1 to 10 atmospheres.

[0014] The present invention has the following advantages:

[0015] First, the carbonylation synthesis of γ-oxoesters / amides eliminates the need for expensive transition metal catalysis, significantly reducing costs. Second, the system can be used with a wide variety of phenols, alcohols, and amines, broadening the applicability of the reaction. Third, the use of inexpensive and readily available CO as a carbonyl source significantly reduces costs. Fourth, the use of ethylene gas as a C2 source opens up new possibilities for large-scale production and ethylene conversion.

[0016] The present invention uses gaseous CO as a carbonyl source and ethylene gas as a C2 source, and under the action of a catalytic amount of a cheap metal nickel catalyst, obtains γ-oxoester / amide products with high atom utilization, high yield, and wide substrate applicability. DETAILED DESCRIPTION

[0017] In order to better understand the present invention, the following examples are provided for illustration. The reaction materials and results of Examples 1-13 are shown in Table 1.

[0018] Table 1 Reaction results of different substituted phenols or alcohols, ethers and amines

[0019]

[0020]

[0021]

[0022] The product structure is as follows:

[0023]

[0024] Example 1

[0025] The reaction was carried out in a 300 ml autoclave. First, a hydroxyl or amino compound 3 (0.3 mmol), nickel di(acetylacetonate) (0.015 mmol), and 4,4'-dimethyl-2,2'-bipyridine (0.015 mmol) were added to a 4 ml glass vial and mixed. Under a nitrogen atmosphere, 1.5 ml of ether 1 was added as a solvent, reactant, and solvent, and di-tert-butyl peroxide (0.75 mmol) was injected to obtain a mixture. The vial was tightly capped with a rubber cap, and one end of a syringe needle was inserted through the vial. The vial was inserted into the vial through the bottle cap, and the vial was connected to the outside world through the needle. The reaction vial was then placed in a high-pressure reactor, and the carbon monoxide in the high-pressure reactor was replaced by 1 atmosphere of carbon monoxide, 1 atmosphere of ethylene gas, and 8 atmospheres of nitrogen. At this time, the carbon monoxide in the autoclave was connected to the interior of the vial through the needle. The reaction was then carried out at 120° C. for 22.0 hours. After the reaction, the γ-oxoester / amide compound 4a was obtained by column chromatography separation in a yield of 88%. The compound was structurally identified by nuclear magnetic resonance (H and C spectra) and high-resolution mass spectrometry.

[0026] The test data is as follows:

[0027] 4a: 1 H NMR (700MHz, CDCl3) δ7.37(t,J=7.9Hz,2H),7.21(t,J=7.4Hz,1H),7.08(d,J=8.0Hz,2H),3.99–3.90(m,1H),3.90–3.85( m,1H),3.81–3.72(m,1H),2.75–2.68(m,1H),2.67–2.61(m,1H),2.10–2.00(m,1H),2.00–1.84(m,4H),1.58–1.49(m,1H).

[0028] 13 C NMR (176MHz, CDCl3) δ172.1,150.7,129.3,125.6,121.5,78.0,67.7,31.2,31.2,30.6,25.7.

[0029] HRMS(ESI-TOF)m / z:[M+Na]+Calcd for C 13H 16 O3Na 243.0992; Found:243.0999.

[0030] Example 2

[0031] The operation process and conditions were the same as those in Example 1, except that the starting materials contained hydroxyl or amino compounds 3 and / or ethers 1 as shown in Table 1. The yield of 4b was 89%, and the structure of the compound was identified by nuclear magnetic resonance (H and C) and high-resolution mass spectrometry.

[0032] 4b: 1 H NMR (700MHz, CDCl3) δ7.80–7.58(m,2H),7.23(d,J=8.5Hz,2H),3.99–3.89(m,1H),3.89–3.83(m,1H),3.79– 3.70(m,1H),2.86–2.62(m,2H),2.12–2.01(m,1H),1.99–1.94(m,1H),1.94–1.84(m,3H),1.58–1.47(m,1H).

[0033] 13 C NMR (176MHz, CDCl3) δ171.3,154.1,133.6,122.7,118.3,109.6,77.9,67.8,31.3,31.2,30.5,25.7.

[0034] HRMS(ESI-TOF)m / z:[M+Na]+Calcd for C 14 H 15 O3N Na 268.0944; Found:268.0944.

[0035] Example 3

[0036] The operation process and conditions were the same as those in Example 1, except that the starting materials contained hydroxyl or amino compounds 3 and / or ethers 1 as shown in Table 1. The yield of 4c was 88%, and the structure of the compound was identified by H-NMR and C-NMR and high-resolution mass spectrometry.

[0037] 4c: 1H NMR (700MHz, CDCl3) δ4.80–4.70(m,1H),3.87–3.76(m,2H),3.73–3.65(m,1H),2.50–2.37(m,1H),2.37–2.30(m,1H),2.07–1.93(m,1H),1.92– 1.84(m,2H),1.81(dq,J=7.9,6.4,5.8Hz,4H),1.73–1.65(m,2H),1.58 –1.50(m,1H),1.48–1.44(m,1H),1.41–1.31(m,4H),1.29–1.19(m,1H).

[0038] 13 C NMR (176MHz, CDCl3) δ173.0,78.2,72.4,67.6,31.6,31.6,31.5,31.1,30.8,28.1,25.7,25.4,23.7.

[0039] HRMS(ESI-TOF)m / z:[M+Na]+Calcd for C 13 H 22 O3Na 249.1461; Found:249.1462.

[0040] Example 4

[0041] The operation process and conditions were the same as those in Example 1, except that the raw materials contained hydroxyl or amino compounds 3 and / or ether 1 as shown in Table 1. The yield of 4d was 68%, and the structure of the compound was identified by nuclear magnetic resonance (H and C spectra) and high-resolution mass spectrometry.

[0042] 4d: 1 H NMR(700MHz, CDCl3)δ11.22(br,1H),3.93–3.77(m,2H),3.77–3.65(m,1H),2.53–2.43(m,1H), 2.43–2.35(m,1H),2.10–1.94(m,1H),1.92–1.83(m,2H),1.83–1.73(m,2H),1.57–1.32(m,1H).

[0043] 13 C NMR(176MHz, CDCl3)δ178.9,78.1,67.6,31.1,30.9,30.2,25.6.HRMS(ESI-TOF)m / z:[M+Na]+Calcd for C7H 12 O3Na 167.0679; Found:167.0680.

[0044] Example 5

[0045] The operation process and conditions were the same as those in Example 1, except that the raw materials contained hydroxyl or amino compounds 3 and / or ethers 1 as shown in Table 1. The yield of 4e was 75%, and the structure of the compound was identified by nuclear magnetic resonance (H and C) and high-resolution mass spectrometry.

[0046] 4e: 1 H NMR (700MHz, CDCl3) δ8.12(s,1H),7.51(d,J=8.0Hz,2H),7.30(t,J=7.8Hz,2H),7.08(t,J=7.4Hz,1H),3.93–3.85(m,2H ),3.77(q,J=7.5Hz,1H),2.59–2.41(m,2H),2.11–1.97(m,2H),1.96–1.86(m,2H),1.86–1.75(m,1H),1.65–1.43(m,1H).

[0047] 13 C NMR (176MHz, CDCl3) δ171.3,138.2,128.9,123.9,119.6,78.7,67.8,34.8,31.3,31.0,25.7.

[0048] HRMS(ESI-TOF)m / z:[M+Na]+Calcd for C 13 H 17 NO2Na 242.1151; Found:242.1151.

[0049] Example 6

[0050] The operation process and conditions were the same as those in Example 1, except that the raw materials contained hydroxyl or amino compounds 3 and / or ether 1 as shown in Table 1. The yield of 4f was 82%, and the structure of the compound was identified by nuclear magnetic resonance (H and C spectra) and high-resolution mass spectrometry.

[0051] 4f: 1 H NMR (700MHz, CDCl3) δ7.12(s,1H),5.04(q,J=6.9Hz,1H),4.91(t,J=7.1Hz,2H),4.50(t,J=6.5Hz,2H),4.00–3.80(m,2H ),3.74(q,J=7.5Hz,1H),2.43–2.24(m,2H),2.14–1.96(m,1H),1.96–1.79(m,3H),1.80–1.65(m,1H),1.62–1.45(m,1H).

[0052] 13 C NMR (176MHz, CDCl3) δ172.7,78.4,78.4,78.4,67.6,44.5,33.2,31.2,31.0,25.5.

[0053] HRMS(ESI-TOF)m / z:[M+Na]+Calcd for C 10 H 17 NO2Na 206.1151; Found:206.1151.

[0054] Example 7

[0055] The operation process and conditions were the same as those in Example 1, except that the raw materials contained hydroxyl or amino compounds 3 and / or ether 1 as shown in Table 1, and the yield of 4 g was 61%. The structure of the compound was identified by nuclear magnetic resonance (H and C spectra) and high-resolution mass spectrometry.

[0056] 4g: 1 H NMR (400MHz, CDCl3) δ3.99–3.74(m,2H),3.72–3.57(m,1H),3.46–3.09(m,4H),2.51–2.26(m,2H),2. 13–1.77(m,4H),1.76–1.63(m,1H),1.60–1.40(m,1H),1.12(t,J=7.2Hz,3H),1.05(t,J=7.1Hz,3H).

[0057] 13 C NMR (100MHz, CDCl3) δ171.8,78.5,67.5,41.8,40.0,31.3,31.1,29.7,25.5,14.2,12.9.

[0058] HRMS(ESI-TOF)m / z:[M+Na]+Calcd for C 11 H 21 O2NNa 222.1465; Found:222.1470.

[0059] Example 8

[0060] The operation process and conditions were the same as those in Example 1, except that the raw materials contained hydroxyl or amino compounds 3 and / or ether 1 as shown in Table 1. The yield was 81% in 4 hours, and the structure of the compound was identified by nuclear magnetic resonance (H and C spectra) and high-resolution mass spectrometry.

[0061] 4h: 1H NMR (700MHz, CDCl3) δ7.37(t,J=7.9Hz,2H),7.22(t,J=7.4Hz,1H),7.07(d,J=8.0Hz,2H),3.83–3.77(m,1H),3. 78–3.69(m,3H),3.67–3.57(m,2H),3.42–3.22(m,1H),2.77–2.69(m,1H),2.69–2.62(m,1H),1.84–1.77(m,2H).

[0062] 13 C NMR (176MHz, CDCl3) δ171.8,150.6,129.4,125.7,121.5,74.2,71.0,66.7,66.5,30.0,26.5.

[0063] HRMS(ESI-TOF)m / z:[M+Na]+Calcd for C 13 H 16 O4Na 259.0941; Found:259.0947.

[0064] Example 9

[0065] The operation process and conditions were the same as those in Example 1, except that the starting materials contained hydroxyl or amino compounds 3 and / or ether 1 as shown in Table 1. The yield of 4i was 77%, and the structure of the compound was identified by nuclear magnetic resonance (H and C) and high-resolution mass spectrometry.

[0066] 4i: 1 H NMR (700MHz, CDCl3) δ7.40–7.34(m,2H),7.22(t,J=7.4Hz,1H),7.08(d,J=7.6Hz,2H),3.64–3.54(m, 1H),3.55–3.47(m,1H),3.47–3.35(m,1H),2.69–2.55(m,2H),2.02–1.77(m,2H),1.28–1.17(m,6H).

[0067] 13 C NMR (176MHz, CDCl3) δ172.3,150.8,129.4,125.7,121.5,73.9,63.8,31.6,30.5,19.7,15.6.

[0068] HRMS(ESI-TOF)m / z:[M+H]+Calcd for C 13 H 18O3Na 245.1142; Found:245.1138.

[0069] Example 10

[0070] The operation process and conditions were the same as those in Example 1, except that the raw materials contained hydroxyl or amino compounds 3 and / or ethers 1 as shown in Table 1. The yield of 4j was 68%, and the structure of the compound was identified by nuclear magnetic resonance (H and C spectra) and high-resolution mass spectrometry.

[0071] 4j: 1 H NMR (700MHz, CDCl3) δ7.37(t,J=7.8Hz,2H),7.22(t,J=7.4Hz,1H),7.08(d,J=8.0Hz,2H),3.53–3.45(m,1H),3.46–3.38(m,1H),3. 38–3.24(m,1H),2.71–2.46(m,2H),2.08–1.91(m,1H),1.90–1.80(m,1H),1.64–1.48(m,3H),1.45–1.31(m,5H),1.04–0.85(m,6H).

[0072] 13 C NMR (176MHz, CDCl3) δ172.4,150.8,129.3,125.7,121.5,78.0,68.9,36.1,32.3,30.3,29.0,19.4,18.6,14.2,13.9.

[0073] HRMS(ESI-TOF)m / z:[M+H]+Calcd for C 17 H 27 O3 279.1955; Found:279.1951.

[0074] Example 11

[0075] The operation process and conditions were the same as those in Example 1, except that the raw materials contained hydroxyl or amino compounds 3 and / or ether 1 as shown in Table 1. The yield of 4k was 52%, and the structure of the compound was identified by nuclear magnetic resonance (H and C spectra) and high-resolution mass spectrometry.

[0076] 4k: 1H NMR (700MHz, CDCl3) δ7.37(t,J=7.8Hz,2H),7.22(t,J=7.4Hz,1H),7.09(d,J=7.5Hz,2H),3.17(s,3H),2.67– 2.51(m,2H),2.20–1.99(m,2H),1.94–1.84(m,2H),1.81–1.69(m,2H),1.68–1.58(m,2H),1.54–1.39(m,2H).

[0077] 13 C NMR (176MHz, CDCl3) δ172.6,150.8,129.4,125.7,121.5,85.9,49.4,35.6,30.5,29.7,23.7,23.7.

[0078] HRMS(ESI-TOF)m / z:[M+H]+Calcd for C 15 H 21 O3 249.1485; Found:249.1490.

[0079] Example 12

[0080] The operation process and conditions were the same as those in Example 1, except that the raw materials contained hydroxyl or amino compounds 3 and / or ethers 1 as shown in Table 1, and the yield of 41 was 62%. The structure of the compound was identified by nuclear magnetic resonance (H and C spectra) and high-resolution mass spectrometry.

[0081] 4l: 1 H NMR (700MHz, CDCl3) δ7.37(t,J=7.8Hz,2H),7.29(t,J=7.8Hz,2H),7.22(t,J=7.5Hz,1H),7.08(d,J=8.0Hz,2H) ,6.95(t,J=7.3Hz,1H),6.92(d,J=8.2Hz,2H),4.08(t,J=6.0Hz,2H),2.79(t,J=7.3Hz,2H),2.39–2.09(m,2H).

[0082] 13 C NMR (176MHz, CDCl3) δ171.8,158.8,150.6,129.5,129.4,125.8,121.5,120.8,114.5,66.4,31.0,24.6.

[0083] HRMS(ESI-TOF)m / z:[M+H]+Calcd for C 16 H 17O3 257.1172; Found:257.1178.

[0084] Example 14

[0085] Keeping the other reaction conditions described in Example 1 unchanged (i.e., the operating process and conditions are the same as in Example 1), the difference is that the catalytic co-agent of the reaction is changed to bipyridine, and the yield of the target product γ-ether amide / ester compound is reduced to 74%, at which time the raw material is fully converted.

[0086] Example 15

[0087] Keeping the other reaction conditions described in Example 1 unchanged (ie, the operating process and conditions are the same as in Example 1), except that the reaction temperature is lowered to 100 degrees Celsius, the yield of the target product γ-ether amide / ester compound is reduced to 56%.

[0088] Example 16

[0089] Keeping the other reaction conditions described in Example 1 unchanged (i.e., the operating procedures and conditions are the same as in Example 1), the difference is that the amount of di-tert-butyl peroxide used in the reaction is reduced to 1 equivalent, and the yield of the target product γ-ether amide / ester compound is reduced to 41%.

[0090] Example 17

[0091] Keeping the other reaction conditions described in Example 1 unchanged (i.e., the operating procedures and conditions are the same as in Example 1), except that the pressures of carbon monoxide and ethylene in the reaction were raised to 10 bar, respectively, the yield of the target product γ-ether amide / ester compound was reduced to 78%.

[0092] Example 18

[0093] Keeping the other reaction conditions described in Example 1 unchanged (i.e., the operating procedures and conditions are the same as in Example 1), the difference is that the catalyst of the reaction is changed to nickel chloride, and the yield of the target product γ-ether amide / ester compound is reduced to 68%.

[0094] Example 18

[0095] Keeping the other reaction conditions described in Example 1 unchanged (i.e., the operating process and conditions are the same as in Example 1), the difference is that the amount of catalyst used in the reaction is changed to 10 mol%, and the yield of the target product γ-ether amide / ester compound is reduced to 77%.

[0096] Comparative Example 1

[0097] Keeping the other reaction conditions described in Example 1 unchanged (i.e., the operating procedures and conditions are the same as in Example 1), the difference is that the reaction temperature is reduced to 60 degrees Celsius, the yield of the target product γ-ether amide / ester compound is reduced to 0%, and a large amount of raw materials remain.

[0098] Comparative Example 2

[0099] Keeping the other reaction conditions described in Example 1 unchanged (i.e., the operating procedures and conditions are the same as in Example 1), except that the catalyst of the reaction is changed to nickel iodide, the yield of the target product γ-ether amide / ester compound is reduced to 29%, and the raw material is not fully converted.

[0100] Comparative Example 3

[0101] Keeping the other reaction conditions described in Example 1 unchanged (i.e., the operating process and conditions are the same as in Example 1), the difference is that the peroxide in the reaction is selected as hydrogen peroxide, the yield of the target product γ-ether amide / ester compound is reduced to 0%, and the raw material portion remains.

[0102] Comparative Example 4

[0103] The other reaction conditions described in Example 1 were kept unchanged (i.e., the operating procedures and conditions were the same as in Example 1), except that the co-catalyst was changed to 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene. The yield of the target product γ-ether amide / ester compound was reduced to 2%.

[0104] Comparative Example 5

[0105] Keeping the other reaction conditions described in Example 1 unchanged (i.e., the operating process and conditions are the same as in Example 1), the difference is that the catalyst of the reaction is removed, the yield of the target product γ-ether amide / ester compound is reduced to 0%, and a large amount of raw materials remain.

[0106] Comparative Example 6

[0107] Keeping the other reaction conditions described in Example 1 unchanged (i.e., the operating process and conditions are the same as in Example 1), the difference is that the catalyst is removed, the yield of the target product γ-ether amide / ester compound is reduced by 18%, and the raw material is fully converted.

[0108] Comparative Example 7

[0109] Keeping the other reaction conditions described in Example 1 unchanged (i.e., the operating process and conditions are the same as in Example 1), the difference is that the peroxide in the reaction is removed, the yield of the target product γ-ether amide / ester compound is reduced to 0%, and a large amount of raw materials remain.

[0110] Comparative Example 8

[0111] Keeping the other reaction conditions described in Example 1 unchanged (i.e., the operating process and conditions are the same as in Example 1), the difference is that the catalyst of the reaction is changed to palladium chloride, the yield of the target product γ-ether amide / ester compound is reduced to 0%, and a large amount of raw materials remain.

[0112] Comparative Example 9

[0113] Keeping the other reaction conditions described in Example 1 unchanged (i.e., the operating process and conditions are the same as in Example 1), the difference is that the reaction time is reduced to 10 hours, the yield of the target product γ-ether amide / ester compound is reduced by 41%, and the raw materials are fully converted.

Claims

1. A γ -A method for preparing oxoesters / amides, characterized in that: Prepared from ether, ethylene, carbon monoxide and phenol, alcohol, amine or water γ - one of the oxoester / or amide derivatives, produced by using the following formula as raw materials: ether 1, one of the hydroxyl-containing or amino compounds 3, namely phenol, alcohol, amine or water, carbon monoxide and ethylene gas. γ- One of the oxoester / amide ether 4, the reaction formula is as follows: The structure of ether 1 in the reaction formula represents that ether 1 is one of cyclic ether and linear ether; The cyclic ether is one of tetrahydrofuran and 1,4-dioxane; in the general formula of ether 1, R 1 is one of methyl, n-propyl, and tert-butyl; in the general formula of ether 1, R 2 is one of hydrogen, ethyl, and phenyl; In addition, the hydroxyl or amino compound 3 is one of phenol, alcohol, water or amine; in the general formula, R 3 is one of hydrogen, phenyl, 4-cyanophenyl, and cyclohexyl; R 4 is one of phenyl, cyclopropyl and ethyl; R 5 For one of hydrogen and ethyl; The specific steps are as follows: The reaction is carried out in a high-pressure reactor. The catalyst, the catalyst promoter, and the hydroxyl- or amino-containing compound 3 are weighed and mixed to obtain a mixture. Peroxide and ether are injected into the mixture under an inert gas atmosphere to obtain a mixed material. The mixed material is placed in a reactor or the mixed material is mixed or prepared directly in the reactor. The gas atmosphere in the reactor is replaced with carbon monoxide gas and ethylene gas. The reaction is carried out at 70-150°C for 10-36 hours. After the reaction is completed, the obtained product is separated. γ - one of the oxoesters / amides 4; the peroxide is one or more of hydrogen peroxide, cumene hydroperoxide, tert-butyl perbenzoate, and di-tert-butyl peroxide; The catalyst is one or more of nickel di(acetylacetonate), nickel acetate, nickel chloride, and nickel iodide; The catalyst auxiliary agent is one or more of 6,6'-dimethyl-2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine and 2,2'-bipyridine.

2. The preparation method according to claim 1, characterized in that: The reaction temperature is 110-130°C; the reaction time is 18-24 hours.

3. The preparation method according to claim 1, characterized in that: The molar ratio of the hydroxyl- or amino-containing compound 3 to the catalyst and the catalyst auxiliary is 100:1:1-100:20:

20.

4. The preparation method according to claim 3, characterized in that: The molar ratio of the hydroxyl- or amino-containing compound 3 to the catalyst and the catalyst auxiliary is 100:5:5-100:10:

10.

5. The preparation method according to claim 1, characterized in that: The molar ratio of the hydroxyl- or amino-containing compound 3 to the peroxide is 1:2-1:

5.

6. The preparation method according to claim 5, characterized in that: The molar ratio of the hydroxyl- or amino-containing compound 3 to the peroxide is 1:2-1:

4.

7. The preparation method according to claim 1, characterized in that: The atmospheric pressure of carbon monoxide is 1-30 atmospheres; The gas pressure of ethylene gas is 1-30 atmospheres; The total volume of the reaction substrate, catalyst, co-catalyst and peroxide shall not exceed 50% of the volume of the high-pressure reactor.

8. The preparation method according to claim 7, characterized in that: The atmospheric pressure of carbon monoxide is 1-10 atmospheres; The pressure of ethylene gas is 1-10 atmospheres.

9. The preparation method according to claim 1, characterized in that: The above ethers serve as both solvent and reaction substrate in this reaction; the amount of ether 1 used is 0.1-2.0 ml per 0.3 mmol of hydroxyl- or amino-containing compound 3.

10. The preparation method according to claim 9, characterized in that: The above ethers serve as both solvent and reaction substrate in this reaction; the amount of ether 1 used is 0.5-1.5 ml per 0.3 mmol of hydroxyl- or amino-containing compound 3.

Images