Method for producing diesters by oxidative carbonylation of olefins with carbon monoxide

Abstract

The present invention provides a method for producing a diester by oxidative carbonylation of an olefin with carbon monoxide. The method comprises the step of oxidatively carbonylating an olefin with carbon monoxide in an oxygen-containing atmosphere in the presence of a catalyst and a dehydrating agent to produce a 1,4-diester compound. The catalyst comprises a procatalyst containing a Pd element, a prooxidant selected from the group consisting of copper salts, iron salts, iron powder, and combinations thereof, and an acid that is a Lewis acid and / or a protonic acid. The dehydrating agent is selected from the group consisting of ketals, acetals, orthoformates, silicates, and combinations thereof. The method of the present invention provides a green, low-carbon, environmentally friendly catalyst system that has high catalytic activity, high selectivity, and high conversion, uses oxygen gas or air as an oxidant, allows catalyst reuse, is low-cost, and produces virtually no waste during the production process, making it possible to produce a 1,4-diester compound by promoting the oxidative carbonylation of an olefin with CO.

Description

[Technical Field]

[0001] [Cross reference] This application claims priority from a Chinese patent application filed with the State Intellectual Property Office of the People's Republic of China on September 26, 2022, bearing application number 202211169758.9 and entitled "Method for producing diesters by oxidative carbonylation of olefins with carbon monoxide," the entire contents of which are incorporated herein by reference.

[0002] [Technical field] The present invention belongs to the technical field of organic synthesis, and in particular to a method for producing diesters by oxidative carbonylation of olefins with carbon monoxide. [Background technology]

[0003] Oxidative carbonylation refers to the reaction of carbon monoxide with one or more nucleophiles, unsaturated hydrocarbons, etc. in the presence of an oxidant to produce compounds such as esters, carbonates, and ureas. The oxidative carbonylation of olefins with carbon monoxide to produce succinate esters typically requires Pd (usually starting from a divalent state) as a catalyst. While the reaction yields succinate esters and simultaneously releases one molecule of water, the Pd is reduced to zero. Therefore, an oxidant / pro-oxidant is required to oxidize Pd back to its divalent state and complete one catalytic cycle.

[0004] In the oxidative carbonylation reaction promoted by phosphine ligands disclosed in US Patent No. 3,530,168, the reaction rate is improved to some extent (turnover frequency (TOF) is 145 / h), but the turnover number (TON) is only 72 and the reaction selectivity is low, with the selectivity for dimethyl succinate being about 60%, and a large amount of acrylate by-products is produced during the reaction.

[0005] Conventional oxidative carbonylation reactions of olefins with CO have many problems, including low catalytic activity (requiring the use of large amounts of expensive metal catalyst Pd), low selectivity, and low conversion, or the need to use equal or excessive amounts of metal oxidants or organic oxidants (large amounts of metal and organic waste), which results in high production costs and is not environmentally friendly as a large amount of waste is generated during production. Therefore, these methods are still far from being put into practical use for production. Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a method for producing a diester by oxidative carbonylation of an olefin with carbon monoxide, which has high catalytic activity, high selectivity, high conversion, allows the catalyst to be reused, and produces substantially no waste during the production.

[0007] According to the present invention, there is provided a method for producing a diester by oxidative carbonylation of an olefin with carbon monoxide, the method comprising the steps of: That is, the method includes a step of subjecting an olefin to an oxidative carbonylation reaction with carbon monoxide in the presence of a catalyst and a dehydrating agent in an oxygen-containing atmosphere to obtain a 1,4-diester compound, the catalyst comprises a procatalyst which is a substance containing Pd element, an oxidation promoter selected from the group consisting of copper salts, iron salts, iron powder, and combinations thereof, and an acid which is a Lewis acid and / or a protonic acid; The dehydrating agent is selected from the group consisting of ketals, acetals, orthoformates, silicates, and combinations thereof.

[0008] Preferably, the pro-oxidant is a copper salt and / or an iron salt, and the molar ratio of Pd, copper salt, and iron salt in the procatalyst is 1:(0-100):(0-100).

[0009] Preferably, the Lewis acid is selected from the group consisting of boron compounds, aluminum compounds, gallium compounds, indium compounds, zinc compounds, cadmium compounds, mercury compounds, beryllium compounds, magnesium compounds, calcium compounds, strontium compounds, titanium compounds, zirconium compounds, hafnium compounds, scandium compounds, yttrium compounds, lanthanum compounds, praseodymium compounds, neodymium compounds, samarium compounds, europium compounds, gadolinium compounds, terbium compounds, dysprosium compounds, holmium compounds, erbium compounds, thulium compounds, ytterbium compounds, lutetium compounds, germanium compounds, tin compounds, antimony compounds, bismuth compounds, and combinations thereof; The protonic acid is selected from the group consisting of hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfonic acid compounds, hydrogen sulfates, selenic acid, telluric acid, nitric acid, phosphoric acid, dihydrogen phosphates, bistrifluoromethanesulfonimide, fluorosulfonimide, and combinations thereof.

[0010] Preferably, the acid is selected from the group consisting of BCl3, BBr3, AlCl3, AlBr3, SnCl2, SnCl4, Sc(OTf)3, Sc(NO3)3·H2O, ScCl3·6H2O, Sc2(SO4)3·8H2O, YCl3, YBr3, InCl3, InBr3, AuCl3, PtCl2, Ce(OTf)3, TiCl4, Ti(OR)4, ClTi(OR)3, Ti2(SO4)3, ZnCl2, ZnBr2, Zn(OTf)2, HCl, HBr, HI, sulfuric acid, nitric acid, KHSO4, and combinations thereof; The molar ratio of Pd to acid in the procatalyst is 1:(1 to 2000).

[0011] Preferably, the acid is H + is a protonic acid that provides hydroxyl groups and / or a Lewis acid containing a halide ion.

[0012] Preferably, the molar ratio of Pd to olefin in the procatalyst is 1:(700-1,000,000), The molar ratio of the dehydrating agent to the olefin is (0.5 to 8:1).

[0013] Preferably, the molar ratio of carbon monoxide to olefin is (1-5):1, and the molar ratio of oxygen to olefin in the oxygen-containing atmosphere is (0.5-3):1.

[0014] Preferably, the temperature of the oxidative carbonylation reaction is 20 to 300° C., the duration of the oxidative carbonylation reaction is 0.2 to 40 hours, and the pressure of the oxidative carbonylation reaction is 0.5 to 300 bar.

[0015] Preferably, the oxidative carbonylation reaction is carried out in an alkyl alcohol solvent, and the molar ratio of the alkyl alcohol solvent to the dehydrating agent is 10:1 to 0.1:10.

[0016] Preferably, after the oxidative carbonylation reaction is completed, the reaction product is distilled at 170°C, 200°C and 215-220°C under normal pressure, or distilled under reduced pressure, and the residue from the distillation is recovered as the catalyst.

[0017] The present invention provides a method for producing a diester by oxidative carbonylation of an olefin with carbon monoxide in an oxygen-containing atmosphere in the presence of a catalyst and a dehydrating agent to obtain a 1,4-diester compound. The catalyst comprises a procatalyst containing Pd, a prooxidant selected from the group consisting of copper salts, iron salts, iron powder, and combinations thereof, and an acid selected from the group consisting of a Lewis acid and / or a protonic acid. The dehydrating agent is selected from the group consisting of ketals, acetals, orthoformates, silicates, and combinations thereof. The process of the present invention provides high catalytic activity (TON > 50,000, TOF > 1,000 / h), high selectivity (olefin conversion selectivity > 99%), and high conversion (nearly complete olefin conversion). Furthermore, the method according to the present invention uses oxygen gas or air as an oxidant, allowing the catalyst to be reused, is low-cost, and produces virtually no waste during the production process, making it a green, low-carbon, environmentally friendly catalyst system that can promote the oxidative carbonylation reaction of olefins with CO to produce 1,4-diester compounds. DETAILED DESCRIPTION OF THE INVENTION

[0018] According to the present invention, there is provided a method for producing a diester by oxidative carbonylation of an olefin with carbon monoxide, the method comprising the steps of: That is, the method includes a step of subjecting an olefin to an oxidative carbonylation reaction with carbon monoxide in the presence of a catalyst and a dehydrating agent in an oxygen-containing atmosphere to obtain a 1,4-diester compound, the catalyst comprises a procatalyst which is a substance containing Pd element, an oxidation promoter selected from the group consisting of copper salts, iron salts, iron powder, and combinations thereof, and an acid which is a Lewis acid and / or a protonic acid; The dehydrating agent is selected from the group consisting of ketals, acetals, orthoformates, silicates, and combinations thereof.

[0019] The oxidative carbonylation reaction in the present invention is as shown in the following formula I.

[0020] [ka] In formula I, LA represents a Lewis acid, BA represents a Bronsted acid, and cat. represents a catalytic amount, and the catalytic amounts of each component may be the same or different.

[0021] The olefin in the present invention is preferably one or more selected from the group consisting of substituted or unsubstituted alkylethylenes, substituted or unsubstituted arylethylenes, and substituted or unsubstituted cycloolefins, and more preferably one or more selected from the group consisting of ethylene, propylene, butene, pentene, hexene, styrene, cyclohexene, and cyclopentene. The molar ratio of carbon monoxide to olefin is preferably (1-5):1, more preferably (2-4):1, and most preferably (2-2.2):1, e.g., 1:1, 1.5:1, 2:1, 2.2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, or 5:1, and is preferably within a range in which any of the above values ​​is the upper or lower limit.

[0022] The catalyst of the present invention preferably contains a procatalyst, an oxidation promoter, and an acid. The procatalyst is preferably a substance containing Pd element, such as one or more selected from the group consisting of simple Pd, Pd salts, Pd complexes, and supported Pd. In an embodiment of the present invention, the procatalyst may be Pd supported on activated carbon, alumina, SiO2, molecular sieves, or BaSO4, or may be one or more selected from the group consisting of palladium halide, palladium carboxylate, palladium sulfonate, Pd(dba)2, and Pd(PPh3)4. The valence state of Pd in ​​the procatalyst of the present invention may be zero or two. The molar ratio of the procatalyst to the olefin is preferably 1:(700 to 1,000,000), more preferably 1:(1,000 to 100,000), and most preferably 1:(10,000 to 20,000), for example, 1:700, 1:1,000, 1:5,000, 1:10,000, 1:20,000, 1:50,000, 1:100,000, 1:200,000, 1:500,000, or 1:1,000,000, and is preferably within a range in which any of the above values ​​is the upper or lower limit.

[0023] The prooxidant in the present invention is preferably selected from the group consisting of copper salts, iron salts, iron powder, and combinations thereof, more preferably copper salts and / or iron salts. The copper salt is preferably at least one selected from the group consisting of CuCl, CuBr, CuI, CuOAc, CuCl2, CuBr2, Cu(OAc)2, CuSO4, Cu(NO3)2, Cu(OTf)2, CuO, and basic copper carbonate. The iron salt is preferably at least one selected from the group consisting of FeCl2, FeSO4, FeCl3, and Fe(NO3)3, and may be CuCl and FeSO4 in some embodiments of the present invention. The molar ratio of Pd, copper salt, and iron salt in the procatalyst is preferably 1:(0-100):(0-100), more preferably 1:(1-10):(0.1-5), and most preferably 1:(2-8):(0.2-4).

[0024] The pro-oxidant in the present invention has the effect of promoting the oxidation of palladium from zero valence to divalent valence.

[0025] The acid in the present invention is preferably a Lewis acid and / or a protonic acid, and the Lewis acid is preferably at least one selected from the group consisting of boron compounds, aluminum compounds, gallium compounds, indium compounds, zinc compounds, cadmium compounds, mercury compounds, beryllium compounds, magnesium compounds, calcium compounds, strontium compounds, titanium compounds, zirconium compounds, hafnium compounds, scandium compounds, yttrium compounds, lanthanum compounds, praseodymium compounds, neodymium compounds, samarium compounds, europium compounds, gadolinium compounds, terbium compounds, dysprosium compounds, holmium compounds, erbium compounds, thulium compounds, ytterbium compounds, lutetium compounds, germanium compounds, tin compounds, antimony compounds, and bismuth compounds. Among these, compounds contained in Lewis acids include fluorides, chlorides, bromides, iodides, nitrates, sulfates, trifluoromethanesulfonates, bistrifluoromethanesulfonylimides, bisfluorosulfonylimides, methanesulfonates, toluenesulfonates, p-toluenesulfonates, and alkoxy salts, such as BCl3, BBr3, AlCl3, AlBr3, SnCl2, SnCl4, Sc(OTf)3, Sc(NO3)3·H2O, ScCl3·6H2O, Sc2(SO4)3·8H2O, YCl3, YBr3, InCl3, InBr3, AuCl3, PtCl2, Ce(OTf)3, TiCl4, Ti(OR)4, ClTi(OR)3, Ti2(SO4)3, ZnCl2, ZnBr2, and Zn(OTf)2. Preferably, the Lewis acid is a compound containing a halogen ion, i.e., a halide, and in the present embodiment may specifically be AlCl3.

[0026] The protonic acid (Brønsted acid) in the present invention is preferably at least one selected from the group consisting of hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfonic acid compounds, hydrogen sulfate, selenic acid, telluric acid, nitric acid, phosphoric acid, dihydrogen phosphate, bistrifluoromethanesulfonylimide, and fluorosulfonylimide, and more preferably at least one selected from the group consisting of HCl, sulfuric acid, nitric acid, and KHSO4. In the present invention, the protonic acid is generated in situ by an in situ preparation method, and hydrogen chloride or hydrogen bromide can be obtained, for example, by reacting acyl chloride or acyl bromide with methanol.

[0027] In the present invention, a Lewis acid containing a halogen and H + It is preferable to use a Lewis acid in combination with a protonic acid that provides a ketal, which can improve the reaction efficiency, especially the efficiency of the palladium catalyst recovery and recycling process. Both Lewis acids and protonic acids can promote the dehydration process in which the dehydrating agent ketal reacts with water to simultaneously produce two equivalents of methanol. The specific reaction process of the protonic acid is shown in Scheme II below, and the reaction process of the Lewis acid is similar.

[0028] [ka]

[0029] In addition to removing water, Lewis acids also promote the efficiency of the crucial carbonyl insertion reaction. Lewis acids accelerate the reaction primarily by stabilizing the transition state (e.g., the procedure shown in the box below) and by increasing the rate at which intermediates are captured by ligands such as CO or solvents in the system. The specific process is shown in Scheme III below.

[0030] [ka]

[0031] In the present invention, the molar ratio of the Lewis acid to the protonic acid is preferably 1:24 to 2:1, more preferably 1:20 to 1:1, for example, 1:24, 1:23, 1:22, 1:21, 1:20, 1:19, 1:18, 1:17, 1:16, 1:15, 1:14, 1:13, 1:12, 1:11, 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, or 2:1, and is preferably within a range in which any of the above values ​​is the upper or lower limit. The molar ratio of PD to acid in the procatalyst is preferably 1:(1 to 2000), more preferably 1:(100 to 1200), for example, 1:1, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900, 1:1000, 1:1100, 1:1200, 1:1300, 1:1400, 1:1500, 1:1600, 1:1700, 1:1800, 1:1900, or 1:2000, and is preferably within a range in which any of the above values ​​is the upper or lower limit.

[0032] In the present invention, the dehydrating agent reacts with water to produce acetone, which is recovered by distillation and then condensed with an alcohol to prepare a dehydrating agent, thereby enabling recycling of the dehydrating agent. The dehydrating agent is at least one selected from the group consisting of ketals, acetals, orthoformates, and silicates, and is preferably at least one selected from the group consisting of structures represented by the following formulas IV to VII:

[0033] [ka] However, in Formulas IV to VII, R 1 and R 2 are independently hydrogen, an alkyl group, a cycloalkyl group, or an aryl group; R 3 is an alkyl group, a cycloalkyl group, or an aryl group, and R 4is an alkyl group, a cycloalkyl group, or an aryl group. In an embodiment of the present invention, the dehydrating agent is specifically 2,2-dimethoxypropane (DMP). The molar ratio of the dehydrating agent to the olefin is preferably (0.5-8):1, more preferably (1-7):1, e.g., 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, or 8:1, and is preferably within a range in which any of the above values ​​is the upper or lower limit.

[0034] The oxidative carbonylation reaction of the present invention is preferably carried out in a reaction solvent. The reaction solvent is preferably an alcohol, more preferably at least one selected from the group consisting of alkyl alcohols, cycloalkyl alcohols, and aryl alcohols. For example, the reaction solvent may be at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, tert-butanol, cyclobutanol, n-pentanol, isopentanol, neopentyl alcohol, tert-pentanol, and cyclopentanol, and may also be a phenolic compound. For substrates with low solubility in alcohol solvents, other solvents may be added. The molar ratio of the reaction solvent to the dehydrating agent is preferably 2:1 to 1:3, more preferably 1:1 to 1:2, e.g., 2:1, 1.5:1, 1:1, 1:1.5, 1:2, 1:2.5, or 1:3, preferably within a range with any of the above values ​​as the upper or lower limit. In the present invention, the alcohol serves as both a reactant and a solvent.

[0035] The oxygen-containing atmosphere in the present invention may be oxygen gas, air, or a mixed gas obtained by diluting pure oxygen with nitrogen gas at a certain ratio. The molar ratio of oxygen gas to olefin in the oxygen-containing atmosphere is preferably (0.5-3):1, more preferably (1-2.5):1, e.g., 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, or 3:1, and is preferably within a range in which any of the above values ​​is the upper or lower limit. The concentration of oxygen gas in the oxygen-containing atmosphere in the present invention is not particularly limited as long as the ratio of the amount of oxygen gas to the amount of olefin is within the required range of the present invention.

[0036] The order of adding the raw materials in the present invention is not particularly limited, and all the raw materials may be added at a predetermined rate all at once, or may be added continuously at a constant flow rate measured by a gas flow meter. Alternatively, the olefin and carbon monoxide may be added at once first, and then oxygen may be added continuously using a gas flow meter to maintain the oxygen concentration in the reactor within an extremely safe range.

[0037] The temperature of the carbonyl oxidation reaction in the present invention is preferably 20 to 300°C, more preferably 50 to 250°C, for example, 20°C, 30°C, 50°C, 100°C, 150°C, 200°C, 250°C, or 300°C, preferably within a range with any of the above values ​​as the upper or lower limit. The duration of the carbonyl oxidation reaction is 0.2 to 40 hours, more preferably 1 to 30 hours, for example, 0.2 hours, 1 hour, 5 hours, 10 hours, 15 hours, 20 hours, 25 hours, 30 hours, 35 hours, or 40 hours, preferably within a range with any of the above values ​​as the upper or lower limit. The pressure of the carbonyl oxide reaction is 0.5 to 300 bar, more preferably 10 to 250 bar, and most preferably 50 to 200 bar, for example, 0.5 bar, 0.8 bar, 1 bar, 10 bar, 30 bar, 50 bar, 100 bar, 150 bar, 200 bar, 250 bar, or 300 bar, and is preferably within a range in which any of the above values ​​is the upper or lower limit.

[0038] The present invention provides a method for producing a diester by oxidative carbonylation of an olefin with carbon monoxide in an oxygen-containing atmosphere in the presence of a catalyst and a dehydrating agent to obtain a 1,4-diester compound. The catalyst comprises a procatalyst containing Pd, a prooxidant selected from the group consisting of copper salts, iron salts, iron powder, and combinations thereof, and an acid selected from the group consisting of a Lewis acid and / or a protonic acid. The dehydrating agent is selected from the group consisting of ketals, acetals, orthoformates, silicates, and combinations thereof. The process of the present invention provides high catalytic activity (TON > 50,000, TOF > 1,000 / h), high selectivity (olefin conversion selectivity > 99%), and high conversion (nearly complete olefin conversion). Furthermore, the method according to the present invention uses oxygen gas or air as an oxidant, allowing the catalyst to be reused, is low-cost, and produces virtually no waste during the production process, making it a green, low-carbon, environmentally friendly catalyst system that can promote the oxidative carbonylation reaction of olefins with CO to produce 1,4-diester compounds.

[0039] In order to further illustrate the present invention, the process for producing a diester by oxidative carbonylation of an olefin with carbon monoxide according to the present invention will be described in detail below with reference to examples, which should not be construed as limiting the scope of protection of the present invention.

[0040] The abbreviations used in the following examples are as follows: DMP: 2,2-dimethoxypropane; DMS: dimethyl succinate; DMO: dimethyl oxalate; DMC: dimethyl carbonate; MA: methyl acrylate. [Example 1] Effect of Pd type on reaction

[0041] Specific procedure: For the experiment using Pd / C, Pd / C (10% carbon support, 0.0125 mmol, 13.3 mg), CuCl (0.025 mmol, 2.5 mg), AlCl3 (0.10 mmol, 13.3 mg), DMP (13.5 mmol, 1660 μL), and MeOH (dry, 3.4 mL) were sequentially added to a 25 mL stainless steel autoclave. The autoclave was then tightly clamped and sequentially charged with 25 bar of air, 20 bar of CO, and 10 bar of ethylene. The autoclave was then placed in a 100 °C oil bath with a magnetic stirrer and stirred for 11 hours. Other experiments were performed in the same manner as this experiment, except that Pd / C was replaced with different palladium species.

[0042] [ka]

[0043] [Table 1]

[0044] In these experiments, a 25 mL stainless steel reaction vessel was used, the total volume of the solution was adjusted to 5 mL, and the yield was measured by nuclear magnetic resonance using mesitylene as an internal standard. The results are shown in Table 1. Table 1 shows that the form of Pd did not have a clear effect on the reaction activity. [Example 2] Effect of pro-oxidants

[0045] Specific procedure: For the experiment using Cu(acac)2, Pd / C (10% carbon support, 0.0125 mmol, 13.3 mg), Cu(acac)2 (0.025 mmol, 6.5 mg), AlCl3 (0.10 mmol, 13.3 mg), DMP (13.5 mmol, 1660 μL), and MeOH (dry, 3.4 mL) were sequentially added to a 25 mL stainless steel reaction vessel. The vessel was then tightly clamped and sequentially charged with 8 bar O2, 20 bar CO, and 10 bar ethylene. The vessel was then placed in a magnetically heated hotplate oil bath at 110 °C and stirred. Other experiments were performed in the same manner as this experiment, except that Cu(acac)2 was replaced with different copper species.

[0046] [ka]

[0047] [Table 2]

[0048] In these experiments, a 25 mL stainless steel reaction kettle was used, the total volume of the solution was adjusted to 5 mL, and the yield was measured by nuclear magnetic resonance using mesitylene as an internal standard. The results are shown in Table 2. Table 2 shows that both monovalent and divalent copper salts were able to promote the reaction.

[0049] Specific procedure: For example, in an experiment using CuCl2, AlCl3, and Fe powder, Pd / C (10% carbon support, 0.0125 mmol, 13.3 mg), CuCl2 (0.025 mmol, 3.4 mg), AlCl3 (0.10 mmol, 13.3 mg), Fe (0.30 mmol, 16.8 mg), DMP (13.5 mmol, 1660 μL), and MeOH (dry, 3.4 mL) were sequentially added to a 25 mL Hastelloy reaction vessel. The vessel was then tightly clamped and sequentially charged with 8 bar O2, 20 bar CO, and 10 bar ethylene. The vessel was then placed in a 110 °C oil bath with a magnetic stirrer and stirred. Other experiments were performed similarly to this experiment, except that CuCl2 was replaced with different copper salts, AlCl3 with different acids, and Fe powder with different iron salts.

[0050] [ka]

[0051] [Table 3]

[0052] In these experiments, a 25 mL Hastelloy reactor was used, the total volume of the solution was adjusted to 5 mL, and the yield was measured by nuclear magnetic resonance using mesitylene as an internal standard. The results are shown in Table 3. The results in Table 3 indicate that iron or iron salts have a certain promoting effect on the reaction and can be used instead of or in combination with copper salts. [Example 3] Effect of Lewis Acid

[0053] Specific procedure: For example, in the experiment using AlCl3, PdCl2 (0.0125 mmol, 2.2 mg), CuCl (0.025 mmol, 2.5 mg), AlCl3 (0.025 mmol, 3.3 mg), DMP (13.5 mmol, 1660 μL), and MeOH (dry, 3.4 mL) were sequentially added to a 25 mL stainless steel reaction vessel. The reaction vessel was then tightly clamped and sequentially filled with 25 bar of air, 20 bar of CO, and 10 bar of ethylene. The reaction vessel was then placed in a 100 °C magnetic hotplate oil bath and stirred. Other experiments were conducted in the same manner as this example, except that AlCl3 was replaced with a different Lewis acid (LA).

[0054] [ka]

[0055] [Table 4]

[0056] A 25 mL stainless steel reactor was used in these experiments. [a] indicates a reaction time of 12 hours, [b] indicates 0.05 mmol of LA, [c] indicates 0.10 mmol of LA, and [d] indicates replacing PdCl2 with Pd / C. The results are shown in Table 4. The results in Table 4 indicate that most Lewis acids promoted the reaction. [Example 4] Effect of protonic acid

[0057] Specific procedure: For the experiment using KHSO4, Pd / C (10% carbon support, 0.0125 mmol, 13.3 mg), CuCl (0.025 mmol, 2.5 mg), KHSO4 (0.30 mmol, 40.8 mg), DMP (13.5 mmol, 1660 μL), and MeOH (dry, 3.4 mL) were sequentially added to a 25 mL stainless steel reaction vessel. The vessel was then tightly clamped and sequentially charged with 8 bar of O2, 20 bar of CO, and 10 bar of ethylene. The vessel was then placed in a magnetically heated hotplate oil bath at 110 °C and stirred. Other experiments were performed in the same manner as this experiment, except that KHSO4 was replaced with different protonic acids (BAs).

[0058] [ka]

[0059] [Table 5]

[0060] In these experiments, a 25 mL stainless steel reaction vessel was used, the total volume of the solution was adjusted to 5 mL, and the yield was measured by nuclear magnetic resonance using mesitylene as an internal standard. [a] indicates that the reaction was filled with air at 25 bar, the reaction temperature was 100°C, and the reaction time was 21 hours. [b] indicates that BA was used at 0.15 mmol. [c] indicates that BA was used at 0.30 mmol. The results are shown in Table 5. The results in Table 5 indicate that most Brønsted acids had the effect of promoting the reaction. [Example 5] Effect of the ratio of catalyst components

[0061] Specific Procedure: For example, in Experiment 2 in Table 6, Pd / C (10% carbon support, 0.0125 mmol, 13.3 mg), CuCl (0.05 mmol, 5.0 mg), AlCl3 (0.10 mmol, 13.3 mg), DMP (13.5 mmol, 1660 μL), and MeOH (dry, 3.4 mL) were sequentially added to a 25 mL stainless steel reactor. The reactor was then tightly clamped and sequentially charged with 25 bar of air, 20 bar of CO, and 10 bar of ethylene. The reactor was then placed in a 100°C oil bath with a magnetic stirrer and stirred. Other experiments were conducted in the same manner as this experiment, except for the ratios of CuCl, AlCl3, and DMP.

[0062] [ka]

[0063] [Table 6]

[0064] In these experiments, a 25 mL stainless steel reaction kettle was used, the total volume of the solution was adjusted to 5 mL, and the yield was measured by nuclear magnetic resonance using mesitylene as an internal standard. [a] indicates that 0.025 mmol of FeCl3 was added. [b] indicates that 0.10 mmol of FeCl3 was added. [c] indicates that 2.8 mL of MeOH (dry) was used. The results are shown in Table 6. [Example 6] Effect of dehydrating agent

[0065] Specific procedure: For example, in an experiment using DMP, Pd / C (10% carbon support, 0.0125 mmol, 13.3 mg), CuCl (0.025 mmol, 2.5 mg), AlCl3 (0.10 mmol, 13.3 mg), DMP (13.5 mmol, 1660 μL), and MeOH (dry, 3.4 mL) were sequentially added to a 25 mL stainless steel reaction vessel. The vessel was then tightly clamped and sequentially charged with 8 bar of O2, 20 bar of CO, and 10 bar of ethylene. The vessel was then placed in a magnetically heated hotplate oil bath at 110 °C and stirred. Other experiments were performed in the same manner as this experiment, except that DMP was replaced with a different dehydrating agent [A1].

[0066] [ka]

[0067] [Table 7]

[0068] In these experiments, a 25 mL stainless steel reaction vessel was used, the total volume of the solution was approximately 5 mL, and the yield was measured by nuclear magnetic resonance using mesitylene as an internal standard. [a] indicates that the reaction time in the experiment was 6 hours. The results are shown in Table 7. Table 7 demonstrates that the organic dehydrating agent of the present invention was able to promote the reaction well. [Example 7] Effect of raw material ratio

[0069] Specific Procedure: For example, in Experiment 1 in Table 8, Pd / C (10% carbon support, 0.0125 mmol, 13.3 mg), CuCl (0.025 mmol, 2.5 mg), AlCl3 (0.10 mmol, 13.3 mg), DMP (13.5 mmol, 1660 μL), and MeOH (dry, 3.4 mL) were sequentially added to a 25 mL stainless steel reactor. The reactor was then tightly clamped and sequentially charged with 8 bar O2, 20 bar CO, and 10 bar ethylene. The reactor was then placed in a 110°C oil bath with a magnetic stirrer and stirred. Other experiments were conducted in the same manner as this experiment, except for varying the ratios of the three different gases.

[0070] [ka]

[0071] [Table 8]

[0072] In these experiments, a 25 mL stainless steel reaction kettle was used, the total volume of the solution was 5 mL, and the yield was measured by nuclear magnetic resonance using mesitylene as an internal standard. [Example 8] Effect of alcohol

[0073] Specific procedure: For example, in an experiment using ethanol, Pd / C (10% supported on carbon, 0.0125 mmol, 13.3 mg), CuCl (0.025 mmol, 2.5 mg), AlCl3 (0.10 mmol, 13.3 mg), [Al] (13.5 mmol, 2176 μL), and EtOH (dry, 2820 μL) were sequentially added to a 25 mL stainless steel reaction vessel. The vessel was then tightly clamped and sequentially charged with 8 bar O2, 20 bar CO2, and 10 bar ethylene. The vessel was then placed in a magnetically heated hotplate oil bath at 110 °C and stirred. Other experiments were conducted in the same manner as this experiment, except for the alcohol and corresponding ketal. The products were diethyl succinate (5.32 mmol), diethyl oxalate (0.1 mmol), and diethyl carbonate (0.08 mmol). [Example 9] Effect of the ratio of alcohol and dehydrating agent

[0074] Specific Procedure: For example, in Experiment 2 in Table 9, PdCl2 (0.0125 mmol, 2.2 mg), CuCl (0.025 mmol, 2.5 mg), Sc(OTf)3 (0.025 mmol, 12.4 mg), DMP (13.5 mmol, 1660 μL), and MeOH (dry, 130.21 mmol, 3.3 mL) were sequentially added to a 25 mL stainless steel reaction kettle. The reaction kettle was then tightly clamped and sequentially charged with 25 bar of air, 20 bar of CO, and 10 bar of ethylene. The reaction kettle was then placed in a 100°C oil bath with a magnetic stirrer and stirred. Other experiments were conducted in the same manner as this experiment, except for the proportions of alcohol and dehydrating agent.

[0075] [ka]

[0076] [Table 9]

[0077] In these experiments, a 25 mL stainless steel reaction kettle was used, the total volume of the solution was 5 mL, and the yield was measured by nuclear magnetic resonance using mesitylene as an internal standard. [Example 10] Effect of other solvents

[0078] Specific procedure: For example, in an experiment using toluene, Pd / C (10% carbon supported, 0.0125 mmol, 13.3 mg), CuCl (0.025 mmol, 2.5 mg), AlCl3 (0.10 mmol, 13.3 mg), DMP (13.5 mmol, 1660 μL), MeOH (dry, 2.4 mL), and toluene (dry, 1.0 mL) were sequentially added to a 25 mL stainless steel reaction vessel. The vessel was then tightly clamped and sequentially charged with 8 bar of O2, 20 bar of CO, and 10 bar of ethylene. The vessel was then placed in a magnetically heated hotplate oil bath at 110 °C and stirred. Other experiments were performed in the same manner as this experiment, except that toluene was replaced with other solvents.

[0079] [ka]

[0080] [Table 10]

[0081] In these experiments, a 25 mL stainless steel reaction kettle was used, the total volume of the solution was adjusted to 5 mL, and the yield was measured by nuclear magnetic resonance using mesitylene as an internal standard. The results are shown in Table 11. Table 11 shows that the addition of solvent did not substantially affect the reaction efficiency. [Example 11] Effect of iron powder on reaction

[0082] Specific Procedure: For example, in Experiment 2 in Table 11, Pd / C (10% carbon support, 0.0125 mmol, 13.3 mg), CuCl (0.025 mmol, 2.5 mg), AlCl3 (0.10 mmol, 13.3 mg), Fe (0.10 mmol, 5.6 mg), DMP (13.5 mmol, 1660 μL), and MeOH (dry, 3.4 mL) were sequentially added to a 25 mL Hastelloy reactor. The reactor was then tightly clamped and sequentially charged with 25 bar air, 20 bar CO, and 10 bar ethylene. The reactor was then placed in a 100°C oil bath with a magnetic stirrer and stirred. Other experiments were conducted in the same manner as this experiment, except for the amount of iron powder used.

[0083] [ka]

[0084] [Table 11]

[0085] In these experiments, a 25 mL Hastelloy reactor was used, the total volume of the solution was adjusted to 5 mL, and the yield was measured by nuclear magnetic resonance spectroscopy using mesitylene as an internal standard. Iron powder reacted in the reaction system to produce Fe salts. [Example 12] Effect of reaction parameters

[0086] Specific Procedure: For the experiment using Example 1 in Table 12, Pd / C (10% carbon support, 0.0125 mmol, 13.3 mg), CuCl (0.025 mmol, 2.5 mg), AlCl3 (0.10 mmol, 13.3 mg), Fe (0.30 mmol, 16.8 mg), DMP (13.5 mmol, 1660 μL), and MeOH (dry, 3.4 mL) were sequentially added to a 25 mL Hastelloy reaction vessel. The vessel was then tightly clamped and sequentially charged with 25 bar of air, 20 bar of CO, and 10 bar of ethylene. The reaction vessel was then placed in a 100°C oil bath with a magnetic stirrer and stirred. Other experiments were conducted in the same manner as this experiment, except for the charging air pressure, reaction temperature, and reaction time.

[0087] [ka]

[0088] [Table 12]

[0089] In these experiments, a 25 mL Hastelloy reaction vessel was used, the total volume of the solution was 5 mL, and the yield was measured by nuclear magnetic resonance using mesitylene as an internal standard. [Comparative Example]

[0090] Specific Procedure: For example, in Experiment 11 in Table 13, Pd / C (10% carbon support, 0.0125 mmol, 13.3 mg), CuCl2 (0.025 mmol, 3.4 mg), AlCl3 (0.10 mmol, 13.3 mg), Fe (0.30 mmol, 16.8 mg), DMP (13.5 mmol, 1660 μL), and MeOH (dry, 3.4 mL) were sequentially added to a 25 mL Hastelloy reactor. The reactor was then tightly clamped and sequentially charged with 8 bar O2, 20 bar CO, and 10 bar ethylene. The reactor was then placed in a 110 °C oil bath with a magnetic stirrer and stirred. Other experiments were conducted in the same manner as this experiment, except that the relevant variables were increased or decreased.

[0091] [ka]

[0092] [Table 13]

[0093] In these experiments, a 25 mL Hastelloy reaction kettle was used, the total volume of the solution was adjusted to 5 mL, and the yield was measured by nuclear magnetic resonance using mesitylene as an internal standard. [a] indicates that a 25 mL stainless steel reaction kettle was used in these experiments. [b] indicates that CuCl was replaced with CuCl2 (0.025 mmol). The results are shown in Table 13. The results in Table 13 indicate that Pd is essential, at least one of Fe and Cu is necessary, and the addition of both is efficient, and that the dehydrating agent and Lewis acid can significantly improve the reaction efficiency. Optimization Experiments

[0094] Specific procedure: For example, in Experiment 1 in Table 14, Pd / C (10% carbon support, 0.0125 mmol, 13.3 mg), CuCl (0.075 mmol, 7.4 mg), AlCl3 (0.30 mmol, 40.0 mg), DMP (100 mmol, 12296 μL), and MeOH (dry, 10.0 mL) were sequentially added to an 80 mL stainless steel reaction vessel. The reaction vessel was then tightly clamped and sequentially charged with 40 bar of CO, 20 bar of ethylene, and 15 bar of O2. The reaction vessel was then placed in a magnetically stirred hotplate oil bath at 110 °C. Other experiments were conducted in the same manner as this experiment, except for the CO and O2 ratios, the amounts of Pd / C, CuCl, and AlCl3 added, the reaction temperature (T °C), and the reaction time.

[0095] [ka]

[0096] [Table 14]

[0097] In these experiments, an 80 mL stainless steel reactor was used, and the total volume of the reaction solution was adjusted to 22 mL. The yield was measured by nuclear magnetic resonance using mesitylene as an internal standard. The results are shown in Table 14. When approximately 60 mmol of product was produced by the reaction, this indicated that the ethylene in the reactor was nearly completely reacted. Condition screening and optimization for 400mL reactor:

[0098] Specific Procedure: For Experiment 1 in Table 15, Pd / C (10% carbon support, 0.001 mmol, 1.1 mg), CuCl (0.006 mmol, 0.6 mg), FeCl2 (0.30 mmol, 38.5 mg), AlCl3 (1.00 mmol, 133.3 mg), DMP (500 mmol, 61481.8 μL), and MeOH (dry, 40.0 mL) were sequentially added to a 400 mL reaction kettle (with a polytetrafluoroethylene liner). The reaction kettle was then tightly clamped and sequentially charged with 20 bar of CO, 20 bar of ethylene, 25 bar of CO, and 20 bar of O2. The reaction kettle was then placed on a magnetic hotplate at 130 °C and stirred for 20 hours. After cooling the reaction vessel to room temperature in an ice bath, the unreacted gas was evacuated to atmospheric pressure in a draft chamber, the reaction vessel was opened, and the internal standard mesitylene (10 mmol, 1395 μL) was added and stirred for 2 minutes. Next, 0.7 mL of CDCl3 and 10 μL of the reaction solution were added to a 1.5 mL microcentrifuge tube, shaken for 30 seconds, centrifuged for 30 seconds, and the product was collected. 1 The results were measured by H NMR. The yield of each product was determined by comparing the proton integrals of these products with the internal standard mesitylene. Other experiments were performed similarly to this experiment, except that the proportions of each variable were changed, the corresponding variables were increased or decreased, different gas proportions, and reaction times were used.

[0099] [Table 15]

[0100] A 400 mL reaction kettle (polytetrafluoroethylene liner) was used in these experiments, the total volume of the solution was approximately 100 mL, and mesitylene was used as the internal standard (10 mmol). [a] indicates that the reaction temperature for the experiment was 120°C. [b] indicates that there was no FeCl2. [c] indicates that Pd / C was replaced with PdCl2. [d] indicates that 50 bar of CO was charged. [e] indicates that 600 mmol of DMP, 26 mL of MeOH, and 25 bar of O2 were used. Stepwise oxygen administration reaction to a 400mL reaction vessel (polytetrafluoroethylene liner):

[0101] Specific Procedure: For Experiment 1 in Table 16, Pd / C (10% carbon support, 0.02 mmol, 21.3 mg), CuCl (0.12 mmol, 11.9 mg), FeCl2 (0.10 mmol, 12.7 mg), AlCl3 (2.00 mmol, 266.7 mg), DMP (600 mmol, 73778.0 μL), and MeOH (dry, 26.0 mL) were sequentially added to a 400 mL reaction kettle (with a polytetrafluoroethylene liner). The reaction kettle was then tightly clamped and sequentially charged with 20 bar CO, 20 bar ethylene, 30 bar CO, and 15 bar O2. The reaction kettle was then placed on a magnetic hotplate at 130 °C and stirred for 10 hours to complete the first stage of the reaction. The reaction vessel was then cooled to room temperature in an ice bath, filled with 10 bar of O2, and placed on a hot plate with a magnetic stirrer at 130 °C for 15 hours to complete the second stage of the reaction. After cooling the reaction vessel to room temperature in an ice bath, unreacted gas was vented to atmospheric pressure in a draft chamber, the reaction vessel was opened, and internal standard mesitylene (10 mmol, 1395 μL) was added and stirred for 2 minutes. Next, 0.7 mL of CDCl3 and 10 μL of the reaction solution were added to a 1.5 mL microcentrifuge tube, shaken for 30 seconds, centrifuged for 30 seconds, and the product was collected. 1 The results were measured by H NMR. The product yields were determined by comparing the proton integrals of these products with those of the internal standard mesitylene. Other experiments were performed in the same manner as this one, except that the proportion of oxygen, the proportion of DMP and methanol, and the reaction time were changed.

[0102] [Table 16]

[0103] In these experiments, a 400 mL reaction kettle (polytetrafluoroethylene liner) was used, the total volume of the solution was approximately 100 mL, and mesitylene was used as the internal standard (10 mmol). [a] Pd / C was 0.01 mmol and CuCl was 0.06 mmol. Catalyst recovery experiment in a 400mL reactor:

[0104] Experimental procedure for the first reaction: Pd / C (10% supported on carbon, 0.02 mmol, 21.3 mg), CuCl (0.12 mmol, 11.9 mg), FeCl 2 (0.10 mmol, 12.7 mg), AlCl3 (2.00 mmol, 266.7 mg), DMP (600 mmol, 73778.0 μL), and MeOH (dry, 26.0 mL) were sequentially added to a 400 mL reaction kettle (polytetrafluoroethylene liner). The reaction kettle was then securely clamped and sequentially charged with 20 bar of CO, 20 bar of ethylene, 30 bar of CO, and 15 bar of O2. The reaction kettle was then placed on a magnetically stirred hotplate at 130 °C and stirred for 13 hours to complete the first stage of the reaction. The reaction kettle was then cooled to room temperature in an ice bath, and then charged with 10 bar of O2. The reaction kettle was then placed on a magnetically stirred hotplate at 130 °C and stirred for 26.5 hours to complete the second stage of the reaction. After cooling the reaction vessel to room temperature in an ice bath, unreacted gas was evacuated to atmospheric pressure in a draft chamber, the reaction vessel was opened, and internal standard mesitylene (10 mmol, 1395 μL) was added and stirred for 2 minutes. 0.7 mL of CDCl3 and 10 μL of the reaction solution were added to a 1.5 mL microcentrifuge tube, shaken for 30 seconds, centrifuged for 30 seconds, and then 1 The yield of each product was determined by comparing the proton integrals of these products with those of the internal standard mesitylene. The reaction solution was then transferred to a 250 mL round-bottom flask, and the initial fraction (mainly methanol, acetone, DMO, DMC, ME, ODS, etc.) was separated by evaporation at 170 and 200 °C under atmospheric pressure. The product DMS was then separated by evaporation at 215-220 °C under atmospheric pressure. Finally, the residue in the round-bottom flask was transferred to a 400 mL reaction vessel (polytetrafluoroethylene liner) to serve as the catalyst for recovery experiments.

[0105] Experimental procedure for the recovery reaction: For the second recovery reaction, the recovery catalyst (residue obtained by distilling the reaction mixture from the previous experiment), DMP (600 mmol, 73778.0 μL), MeOH (dry, 26.0 mL), and HCl (4 mol / L in MeOH, 12 mmol, 3.0 mL) were sequentially added to a 400 mL reaction vessel (polytetrafluoroethylene liner). The vessel was then tightly clamped and sequentially charged with 20 bar of CO, 20 bar of ethylene, 30 bar of CO, and 15 bar of O2. The vessel was then placed on a magnetically stirred hotplate at 130 °C and stirred for 15 hours, completing the first stage of the reaction. The vessel was then cooled to room temperature in an ice bath, charged with 10 bar of O2, and placed on a magnetically stirred hotplate at 130 °C and stirred for 7 hours, completing the second stage of the reaction. After cooling the reaction vessel to room temperature in an ice bath, unreacted gas was evacuated to atmospheric pressure in a draft chamber, the reaction vessel was opened, and the internal standard CH2Br2 (10 mmol, 700 μL) was added and stirred for 2 minutes. 0.7 mL of CDCl3 and 10 μL of the reaction solution were added to a 1.5 mL microcentrifuge tube, shaken for 30 seconds, centrifuged for 30 seconds, and then 1 The product yields were determined by H NMR. The proton integrals of these products were compared with those of the internal standard CH2Br2 to determine the yields of each product. The reaction solution was then transferred to a 250 mL round-bottom flask, and the fore-fraction (main components: methanol, acetone, DMO, DMC, ME, ODS, etc.) was separated by evaporation at 170 and 200 °C under atmospheric pressure. The product, DMS, was then separated by evaporation at 215–220 °C under atmospheric pressure. Finally, the residue in the round-bottom flask was transferred to a 400 mL reaction vessel (polytetrafluoroethylene liner) to serve as the catalyst for the next recovery experiment. Other recovery experiments were conducted in the same manner as this experiment, except that the reaction times in the first and second stages were changed and the associated variables were increased / decreased.

[0106] [Table 17] NOTE: In these experiments, a 400 mL reaction vessel was used to bring the total volume of the solution to approximately 100 mL, and dibromomethane was used as the internal standard (10 mmol). As the catalyst for the recovery experiment, the previous reaction solution was distilled to obtain a residue, which was then transferred to the reaction vessel and used as the next catalyst. [a] indicates that mesitylene was used as the internal standard (10 mmol). [b] shows that HCl was not added, 26 mL of MeOH (dry), and only 15 bar of O2 was added, and the gas pressure remained almost unchanged after 21 hours. The experiment in Entry 2 proved that the reaction required not only aluminum (AlCl3, a Lewis acid, reacted with MeOH during distillation, losing HCl to give Al(OMe)3), but also a protic acid. Substrate study

[0107] Specific procedure: For example, in an experiment using 4-methylstyrene, Pd / C (10% carbon support, 0.01 mmol, 10.6 mg), CuCl (0.02 mmol, 2.0 mg), AlCl (0.10 mmol, 13.3 mg), 4-methylstyrene (10 mmol, 1317.4 μL), DMP (20 mmol, 2459.3 μL), and MeOH (dry, 2.6 mL) were sequentially added to a 25 mL Hastelloy reaction vessel. The vessel was then tightly clamped and sequentially charged with 16 bar O and 40 bar CO. The vessel was then placed in a 120 °C oil bath with a magnetic stirrer and stirred for 24 hours. After cooling the reactor to room temperature in an ice bath, unreacted gas was evacuated to atmospheric pressure in a draft chamber, the reactor was opened, and the internal standard CH2Br2 (1 mmol, 70.0 μL) was added and stirred for 2 minutes. 0.7 mL of CDCl3 and 10 μL of the reaction solution were added to a 1.5 mL microcentrifuge tube, shaken for 30 seconds, centrifuged for 30 seconds, and then 1 The yield of each product was determined by comparing the proton integrals of these products with that of the internal standard CH2Br2.

[0108] [ka]

[0109] Experiments investigating other substrates were carried out according to the standard procedure, except that the reaction conditions were replaced with different olefins (R), different component ratios, different gas ratios, different reaction temperatures, and different reaction times.

[0110] [Table 18]

[0111] These experiments were performed using a 25 mL Hastelloy kettle with dibromomethane (1 mmol) as the internal standard. [a] PdCl2 was replaced with 0.01 mmol Pd / C, and 13 mmol DMP and 3.4 mL MeOH (dry) were added. The mixture was charged with 22 bar CO2 and 8 bar O2, and the temperature was adjusted to 110 °C. Mesitylene (1 mmol) was used as the internal standard. [b] An 80 mL stainless steel kettle was charged with 0.005 mmol Pd / C, 0.03 mmol CuCl, 0.30 mmol FeCl2, 0.25 mmol AlCl3, 100 mmol DMP, and 10.0 mL MeOH (dry) and charged with 10 bar propylene, 25 bar CO2, and 15 bar O2. [c] shows that 0.01 mmol of Pd / C, 0.06 mmol of CuCl, 0.50 mmol of AlCl, 100 mmol of DMP, 10.0 mL of MeOH (dry), and approximately 70 mmol of 3,3,3-trifluoropropene were added to an 80 mL stainless steel reaction vessel, which was then charged with 50 bar of CO and 20 bar of O, and the temperature was raised to 130°C.

[0112] The above examples demonstrate that the catalyst combination system of the present invention is highly compatible with the procatalyst Pd, and similar results can be obtained whether using elemental Pd (including supported Pd) or high-valent Pd. The catalyst system of the present invention achieves results far exceeding those reported in published patents and papers (which did not exceed 300 turnovers), with the method of the present invention achieving turnovers of over 50,000. The catalyst for the reaction can be recovered by a simple method with little change in catalytic activity, making it suitable for industrialization.

[0113] The above is only a preferred embodiment of the present invention, and those skilled in the art can make some improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be considered within the protection scope of the present invention.

Claims

1. A method for producing a diester by oxidative carbonylation of an olefin with carbon monoxide, comprising the step of subjecting an olefin to oxidative carbonylation reaction with carbon monoxide in the presence of a catalyst and a dehydrating agent in an oxygen-containing atmosphere to obtain a 1,4-diester compound, the catalyst comprises a procatalyst which is a substance containing Pd element, an oxidation promoter selected from the group consisting of copper salts, iron salts, iron powder, and combinations thereof, and an acid which is a Lewis acid and / or a protonic acid; The method, wherein the dehydrating agent is selected from the group consisting of ketals, acetals, orthoformates, silicates, and combinations thereof.

2. the pro-oxidant is a copper salt and / or an iron salt, 2. The method of claim 1, wherein the molar ratio of Pd to copper salt to iron salt in the procatalyst is 1:(0-100):(0-100).

3. the Lewis acid is selected from the group consisting of boron compounds, aluminum compounds, gallium compounds, indium compounds, zinc compounds, cadmium compounds, mercury compounds, beryllium compounds, magnesium compounds, calcium compounds, strontium compounds, titanium compounds, zirconium compounds, hafnium compounds, scandium compounds, yttrium compounds, lanthanum compounds, praseodymium compounds, neodymium compounds, samarium compounds, europium compounds, gadolinium compounds, terbium compounds, dysprosium compounds, holmium compounds, erbium compounds, thulium compounds, ytterbium compounds, lutetium compounds, germanium compounds, tin compounds, antimony compounds, bismuth compounds, and combinations thereof; 2. The method of claim 1, wherein the protonic acid is selected from the group consisting of hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfonic acid compounds, hydrogen sulfates, selenic acid, telluric acid, nitric acid, phosphoric acid, dihydrogen phosphates, bistrifluoromethanesulfonimide, fluorosulfonimide, and combinations thereof.

4. The acid is BCl ３ , BBr ３ , AlCl ３ , AlBr ３ , SnCl ２ , SnCl ４ , Sc(OTf) ３ , Sc(NO ３ ) ３ ・H ２ O, ScCl ３ ・6H ２ O, Sc ２ (SO ４ ) ３ ・8H ２ O, YCl ３ , YBr ３ , InCl ３ , InBr ３ , AuCl ３ , PtCl ２ , Ce(OTf) ３ , TiCl ４ , Ti(OR) ４ , ClTi(OR) ３ , Ti ２ (SO ４ ) ３ , ZnCl ２ , ZnBr ２ , Zn(OTf) ２ , HCl, HBr, HI, sulfuric acid, nitric acid, KHSO ４ and combinations thereof; 4. The method of claim 3, wherein the molar ratio of Pd to acid in the procatalyst is 1:(1-2000).

5. The acid is H ＋ 5. The method according to claim 4, wherein the Lewis acid is a protonic acid that provides the above-mentioned formula (I) and / or a Lewis acid that contains a halogen ion.

6. the molar ratio of Pd to olefin in the procatalyst is 1:(700-1,000,000); 2. The method of claim 1, wherein the molar ratio of the dehydrating agent to the olefin is (0.5-8):

1.

7. 2. The method of claim 1, wherein the molar ratio of carbon monoxide to olefin is (1-5):1, and the molar ratio of oxygen to olefin in the oxygen-containing atmosphere is (0.5-3):

1.

8. 2. The process of claim 1, wherein the temperature of the oxidative carbonylation reaction is from 20 to 300°C, the duration of the oxidative carbonylation reaction is from 0.2 to 40 hours, and the pressure of the oxidative carbonylation reaction is from 0.5 to 300 bar.

9. 2. The method according to claim 1, wherein the oxidative carbonylation reaction is carried out in an alkyl alcohol solvent, and the molar ratio of the alkyl alcohol solvent to the dehydrating agent is 10:1 to 0.1:

10.

10. 2. The method according to claim 1, wherein after completion of the oxidative carbonylation reaction, the reaction product is separated by distillation under atmospheric or reduced pressure, and the residue from the distillation is recovered as the catalyst.

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