Intrinsically safe method for preparing fumarate and maleate compounds through alkyne oxidation double carbonylation
By using palladium salt catalyst and iodized salt additive in the alkyne oxidation bicarbonylation reaction, combined with inert gas inhibitors, the explosion risk of alkyne oxidation bicarbonylation is solved, and the efficient preparation of fumarate and maleate compounds is achieved, which is suitable for industrial production.
Patent Information
- Application Number
- CN202510437068.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-09
- Publication Date
- 2025-07-08
AI Technical Summary
The existing alkyne oxidation bicarbonylation methods have the risk of explosion, limiting their industrial applications.
Palladium salt is used as a catalyst and iodized salt is used as an auxiliary agent, and a mixed gas of CO, O2 and inert gas are used to react under specific conditions. The risk of explosion is reduced by using inert gas as a chemical explosion inhibitor.
The preparation of fumarate and maleate compounds with high yields has been achieved, with mild reaction conditions and high atomic utilization rate, which is suitable for industrial production.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing fumarate and maleate compounds by oxidative dicarbonylation of alkynes. Background Art
[0002] Fumarate and maleate compounds are a class of unsaturated dicarboxylate derivatives, which have various chemical and biological activities and are widely used in the fields of medicine, food, industry, etc. In addition, fumarate and maleate compounds can be further used to prepare succinate compounds, and succinates are also a class of dicarboxylate derivatives with wide applications.
[0003] Traditional fumarate and maleate compounds are prepared by esterifying succinic acid derivatives, maleic anhydride with alcohols; for example, Chinese patents CN115322092 and CN101475477 respectively disclose the use of organic sulfonic acid catalysts to achieve the reaction of maleic anhydride with methanol to prepare dimethyl maleate and dimethyl fumarate; Chinese patent CN103848739 discloses the use of sulfuric acid catalyst to achieve the reaction of fumaric acid with alcohol to prepare dimethyl fumarate. The above-mentioned maleic anhydride and fumaric acid raw materials are all prepared by oxidizing butane under high temperature conditions, which requires a large amount of energy. In addition, it can also be prepared by acetylene oxidative carbonylation method. In contrast, ethylene oxidative dicarbonylation is the most atom-economical and simple raw material process, and acetylene is cheaper than butane. However, due to acetylene oxidative carbonylation, acetylene (C2H2), carbon monoxide (CO) and air (O2) need to be added simultaneously. The mixing of these gases poses a potential explosion risk. For example, the explosion limit of the CO / air mixture is 12.5 - 74 vol%, and the acetylene / air system is 2.5 - 81 vol%, which further limits the application of alkynes oxidative dicarbonylation. Therefore, how to develop an intrinsically safe method for alkynes oxidative dicarbonylation is the key to realizing the industrial application of alkynes oxidative dicarbonylation. Summary of the Invention
[0004] The purpose of the present invention is to provide an intrinsically safe method for preparing fumarate and maleate compounds by oxidative dicarbonylation of alkynes to overcome the deficiencies of the prior art.
[0005] For this purpose, the present invention adopts the following technical solutions: An intrinsically safe method for preparing fumarate and maleate compounds by oxidative dicarbonylation of alkynes, using alkynes and alcohols as reactants, palladium salt as a catalyst, iodide salt as an auxiliary agent, filling a mixed gas of CO, O2 and inert gas, and reacting at 25 - 120 °C and a pressure of 0.1 - 5 MPa for 24 - 48 h to generate fumarate and maleate compounds. The reaction formula is as follows: The structural formula of the alkyne is , where R1 is one of hydrogen, substituted or unsubstituted alkyl, aromatic or non-aromatic cyclic compounds with or without heteroatoms. Specifically, it is acetylene.
[0006] The structural formula of the alcohol is , where R2 is substituted or unsubstituted alkyl. Specifically, it is methanol.
[0007] The molar ratio of the alkyne to the alcohol is 1:2 to 1:50.
[0008] The palladium salt is one or more of palladium iodide, palladium acetate, palladium nitrate, palladium chloride, palladium acetylacetonate, and palladium trifluoroacetate.
[0009] The iodine salt is one or more of potassium iodide, sodium iodide, quaternary ammonium iodide, and imidazole iodide.
[0010] The molar ratio of the palladium salt to the iodine salt is 1:1 to 1:10.
[0011] The volume ratio of CO to O2 is 2:1 to 10:1.
[0012] The inert gas is at least one of carbon dioxide, nitrogen, argon, or helium, and the addition amount accounts for 60% - 90% of the total volume of the mixed gas.
[0013] The method for preparing fumarate and maleate compounds by oxidative dicarbonylation of alkynes with inherent safety provided by the present invention uses an inert gas as a chemical explosion inhibitor, reducing the potential explosion risk of the reaction. High-yield target fumarate and maleate compounds can be obtained through oxidative dicarbonylation reaction, and the reaction has a high atom utilization rate with the by-product being H2O. The present invention has the advantages of inherent safety, mild reaction conditions, and high product yield, is suitable for industrial production, and has a wide application prospect. Specific Embodiments
[0014] The following further explains the technical solutions of the present invention in combination with specific embodiments. Most of the raw materials used in each embodiment are commercially available.
[0015] Example 1 Determination of the CO2 Inhibition of the CO / O2 Explosion Limit In a 20L explosion tank, CO / O2 with a volume ratio of 2:1 was filled, and CO2 with a volume fraction of 0% - 80% was added respectively. The ignition electrode was used to ignite the gas, and the explosion pressure of the gas was tested to determine the safety of the reaction. The results are shown in Table 1. It can be seen that adding CO2 can significantly reduce the explosion risk of CO / O2. When the added CO2 exceeds 65%, the explosion risk of CO / O2 can be completely inhibited.
[0016] Table 1 Maximum explosion pressure of CO2 inhibiting CO / O2 explosion test 。
[0017] Example 2 Determination of N2 inhibiting CO / O2 explosion limit In a 20 L explosion tank, CO / O2 with a volume ratio of 2:1 was filled, and N2 with a volume fraction of 65% was added respectively. Using an ignition electrode to ignite the gas, it was found that the CO / O2 mixed gas could not be ignited and detonated. It can be seen that adding a certain amount of N2 can also effectively inhibit the explosion.
[0018] Example 3 Determination of Ar inhibiting CO / O2 explosion limit In a 20 L explosion tank, CO / O2 with a volume ratio of 2:1 was filled, and Ar with a volume fraction of 70% was added respectively. Using an ignition electrode to ignite the gas, it was found that the CO / O2 mixed gas could not be ignited and detonated. It can be seen that adding a certain amount of Ar can also effectively inhibit the explosion.
[0019] Example 4 Determination of CO2 inhibiting C2H2 / CO / O2 explosion limit In a 20 L explosion tank, C2H2 / CO / O2 with a volume ratio of 1:2:1 was filled, and CO2 with a volume fraction of 0% - 80% was added respectively. Using an ignition electrode to ignite the gas, the explosion pressure of the gas was tested to determine the safety of the reaction. The results are shown in Table 2. It can be seen that adding CO2 can significantly reduce the explosion risk of C2H2 / CO / O2. When the added CO2 exceeds 60%, the explosion risk of CO / O2 can be completely inhibited, ensuring that the reaction proceeds under safe addition.
[0020] Table 2 Maximum explosion pressure of CO2 inhibiting C2H4 / CO / O2 explosion test 。
[0021] Example 5 According to the results of Example 4, an intrinsically safe olefin oxidative dicarbonylation reaction was carried out. In a 20 mL high-pressure reaction kettle, 3.6 mg of PdI2, 16 mg of KI and 3 mL of methanol were added respectively. 1 MPa of the gas in Component 16 of Example 4 was filled, in which the gas contained about 26 mg of acetylene gas. The reaction was carried out at 40 °C for 24 h. After the reaction was completed, the reaction solution was centrifuged and analyzed by gas chromatography. The overall yield of dimethyl fumarate and dimethyl maleate reached 100 mg, the selectivity was greater than 98%, and the ratio of dimethyl fumarate to dimethyl maleate was 13:12.
[0022] Example 6 According to the results of Example 4, a intrinsically safe oxidative dicarbonylation reaction of olefins was carried out. In a 20 mL high-pressure reactor, 3.6 mg of PdI2, 16 mg of KI and 3 mL of methanol were added respectively. 1 MPa of the gas in Component 16 of Example 4 was charged, in which the gas contained about 26 mg of acetylene gas. The reaction was carried out at 40 °C for 48 h. After the reaction was completed, the reaction solution was centrifuged and the products were analyzed by gas chromatography. The overall yield of dimethyl fumarate and dimethyl maleate reached 132 mg, the selectivity was greater than 98%, and the ratio of dimethyl fumarate to dimethyl maleate was 13:12.
[0023] Example 7 According to the results of Example 4, a intrinsically safe oxidative dicarbonylation reaction of olefins was carried out. In a 20 mL high-pressure reactor, 3.6 mg of PdI2, 15 mg of NaI and 3 mL of methanol were added respectively. 1 MPa of the gas in Component 16 of Example 4 was charged, in which the gas contained about 26 mg of acetylene gas. The reaction was carried out at 40 °C for 24 h. After the reaction was completed, the reaction solution was centrifuged and the products were analyzed by gas chromatography. The overall yield of dimethyl fumarate and dimethyl maleate reached 98 mg, the selectivity was greater than 98%, and the ratio of dimethyl fumarate to dimethyl maleate was close to 1:1.
[0024] Example 8 According to the results of Example 4, a intrinsically safe oxidative dicarbonylation reaction of olefins was carried out. In a 20 mL high-pressure reactor, 3.6 mg of PdI2, 37 mg of tetrabutylammonium iodide and 3 mL of methanol were added respectively. 1 MPa of the gas in Component 16 of Example 4 was charged, in which the gas contained about 26 mg of acetylene gas. The reaction was carried out at 40 °C for 24 h. After the reaction was completed, the reaction solution was centrifuged and the products were analyzed by gas chromatography. The overall yield of dimethyl fumarate and dimethyl maleate reached 99 mg, the selectivity was greater than 98%, and the ratio of dimethyl fumarate to dimethyl maleate was close to 1:1.
[0025] Example 9 According to the results of Example 4, an intrinsically safe oxidative dicarbonylation reaction of olefins was carried out. In a 20 mL high-pressure reactor, 2.2 mg of Pd(OAc)2, 16 mg of KI and 3 mL of methanol were added respectively. 1 MPa of the gas in Component 16 of Example 4 was charged, in which the gas contained about 26 mg of acetylene gas. The reaction was carried out at 40 °C for 24 h. After the reaction was completed, the reaction solution was centrifuged and the products were analyzed by gas chromatography. The total yield of dimethyl fumarate and dimethyl maleate reached 96 mg, the selectivity was greater than 98%, and the ratio of dimethyl fumarate to dimethyl maleate was close to 1:1.
[0026] Example 10 According to the results of Example 4, an intrinsically safe oxidative dicarbonylation reaction of olefins was carried out. In a 20 mL high-pressure reactor, 3 mg of Pd(acac)2, 16 mg of KI and 3 mL of methanol were added respectively. 1 MPa of the gas in Component 16 of Example 4 was charged, in which the gas contained about 26 mg of acetylene gas. The reaction was carried out at 40 °C for 24 h. After the reaction was completed, the reaction solution was centrifuged and the products were analyzed by gas chromatography. The total yield of dimethyl fumarate and dimethyl maleate reached 104 mg, the selectivity was greater than 98%, and the ratio of dimethyl fumarate to dimethyl maleate was close to 1:1.
[0027] Example 11 According to the results of Example 4, an intrinsically safe oxidative dicarbonylation reaction of olefins was carried out. In a 20 mL high-pressure reactor, 1.8 mg of PdCl2, 16 mg of KI and 3 mL of methanol were added respectively. 1 MPa of the gas in Component 16 of Example 4 was charged, in which the gas contained about 26 mg of acetylene gas. The reaction was carried out at 40 °C for 24 h. After the reaction was completed, the reaction solution was centrifuged and the products were analyzed by gas chromatography. The total yield of dimethyl fumarate and dimethyl maleate reached 92 mg, the selectivity was greater than 98%, and the ratio of dimethyl fumarate to dimethyl maleate was close to 1:1.
[0028] Example 12 According to the results of Example 4, an intrinsically safe oxidative dicarbonylation reaction of olefins was carried out. In a 300 mL high-pressure reactor, 18 mg of PdI2, 80 mg of KI and 50 mL of methanol were added respectively. 2.5 MPa of the gas in Component 16 of Example 4 was charged, in which the gas contained about 0.9 g of acetylene gas. The reaction was carried out at 40 °C for 48 h. After the reaction was completed, the reaction solution was centrifuged and the products were analyzed by gas chromatography. The total yield of dimethyl fumarate and dimethyl maleate reached 4.8 g, the selectivity was greater than 98%, and the ratio of dimethyl fumarate to dimethyl maleate was close to 1:1.
[0029] Example 13 Based on the results of Example 4, a intrinsically safe oxidative dicarbonylation reaction of olefins was carried out. In a 20 mL high-pressure reactor, 3.6 mg of PdI2, 16 mg of KI and 3 mL of ethanol were added respectively. 1 MPa of the gas in Component 16 of Example 4 was charged, in which the gas contained about 26 mg of acetylene gas. The reaction was carried out at 40 °C for 24 h. After the reaction was completed, the reaction solution was centrifuged and separated, and the products were analyzed by gas chromatography. The overall yield of dimethyl fumarate and dimethyl maleate reached 131 mg, the selectivity was greater than 98%, and the ratio of diethyl fumarate to diethyl maleate was close to 1:1.
[0030] Comparative Example 1 In a 20 mL high-pressure reactor, 3.6 mg of PdI2, 16 mg of KI and 3 mL of methanol were added respectively. 0.4 MPa of the gas in Component 10 of Example 4 was charged, in which the gas contained about 26 mg of ethylene gas. The reaction was carried out at 40 °C for 24 h. After the reaction was completed, the reaction solution was centrifuged and separated, and the products were analyzed by gas chromatography. The yield of dimethyl fumarate and dimethyl maleate was 99 mg, and the selectivity was greater than 98%.
[0031] Comparative Example 2 This comparative example is from the literature Journal of Catalysis 413 (2022) 762–768. The reaction conditions were as follows: A Pd catalyst (0.3 g, 1 wt% Pd), CH3OH (10.0 g) were added into the reaction kettle, and then acetylene (8.0 mmol), CO 2.6 MPa, air 2.5 MPa were charged. The reaction was carried out at 80 °C for 10 h. The best conversion rate reached 78%, and the overall selectivity of dimethyl fumarate and dimethyl maleate was greater than 98%.
[0032] According to the results of the examples and Comparative Examples 1 and 2 provided by the present invention, it can be found that after charging an appropriate proportion of inert gas into the reaction system, the catalytic efficiency will not be affected. Although good reaction results can also be obtained in the comparative examples, once an explosion occurs, extremely serious consequences will be caused. Therefore, the technical solution provided by the present invention can significantly reduce the explosion risk of the reaction system and realize the intrinsically safe oxidative dicarbonylation reaction of olefins.
[0033] In addition, the inventors of this case also carried out experiments in the manner of Examples 1-13 with other raw materials and conditions listed in this specification, and corresponding effects can also be achieved. The synthesis method has a high yield, is suitable for industrial production, and has a wide application prospect.
[0034] It should be understood that the above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly, and it cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit and essence of the present invention should be covered within the protection scope of the present invention.
Claims
1. A method for preparing fumarate and maleate compounds by oxidative dicarbonylation of alkynes with intrinsic safety, characterized in that: Using alkynes and alcohols as reactants, palladium salts as catalysts, and iodide salts as promoters, a mixed gas of CO, O2, and inert gas is charged, and the reaction is carried out at 25~120 °C and a pressure of 0.1~5 MPa for 24~48 h to produce fumarate and maleate compounds.
2. The method for preparing fumarate and maleate compounds by oxidative dicarbonylation of alkynes with intrinsic safety as described in claim 1, characterized in that, The structural formula of the alkyne is , where R1 is one of hydrogen, a substituted or unsubstituted alkyl group, an aromatic or non-aromatic cyclic compound with or without heteroatoms.
3. The method for preparing fumarate and maleate compounds by oxidative dicarbonylation of alkynes with intrinsic safety as claimed in claim 1, wherein, The structural formula of the alcohol is , and R2 is a substituted or unsubstituted alkyl group.
4. The method for preparing fumarate and maleate compounds by oxidative dicarbonylation of alkynes with intrinsic safety as claimed in claim 1, wherein The molar ratio of the alkyne to the alcohol is 1:2~1:
50.
5. The method for preparing fumarate and maleate compounds by oxidative dicarbonylation of alkynes with intrinsic safety as claimed in claim 1, wherein The palladium salt is one or more of palladium iodide, palladium acetate, palladium nitrate, palladium chloride, palladium acetylacetonate, and palladium trifluoroacetate.
6. The method for preparing fumarate and maleate compounds by oxidative dicarbonylation of alkynes with intrinsic safety as claimed in claim 1, wherein, The iodide salt is one or more of potassium iodide, sodium iodide, quaternary ammonium iodide, and imidazole iodide.
7. The method for preparing fumarate and maleate compounds by oxidative dicarbonylation of alkynes with intrinsic safety as described in claim 1, characterized in that, The molar ratio of the palladium salt to the iodide salt is 1:1~1:
10.
8. The method for preparing fumarate and maleate compounds by oxidative dicarbonylation of alkynes with intrinsic safety as described in claim 1, characterized in that, The volume ratio of CO to O2 is 2:1~10:
1.
9. The method for preparing fumarate and maleate compounds by oxidative dicarbonylation of alkynes with intrinsic safety as claimed in claim 1, wherein, The inert gas is at least one of carbon dioxide, nitrogen, argon, or helium, and the addition amount accounts for 60%~90% of the total volume of the mixed gas.