Intrinsically safe method for preparing succinate compound through olefin oxidation double carbonylation
By using a mixed gas of palladium compound, copper compound catalyst and inert gas, the explosion risk during the oxidation of olefins is solved, and a high yield of succinate compounds is achieved, which is suitable for industrial production.
Patent Information
- Application Number
- CN202510436936.7
- 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
During the existing olefin oxidation bicarbonylation process, the explosion risks of CO/O2 and ethylene/O2 limit their industrial applications. How to develop an intrinsically safe method to reduce the risk of explosion and improve product yields.
Palladium compound and copper compound are used as bimetallic catalysts, combined with a mixed gas of CO, O2 and an inert gas, and reacted at specific temperatures and pressures. The risk of explosion is suppressed by inert gas and the oxidation of olefins is achieved to prepare succinate compounds.
It significantly reduces the explosion risk of the reaction, increases the yield of succinate compounds, and has mild reaction conditions and 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 relates to a method for preparing succinic acid esters by oxidative dicarbonylation of olefins. Background Art
[0002] Succinic acid esters are a class of C4+ diester compounds and have a wide range of uses in many fields such as biodegradable polymers, plasticizers, solvents, surfactants, organic synthesis intermediates, pharmaceutical intermediates, drug carriers, food additives, and perfume intermediates.
[0003] Traditional succinic acid esters are prepared from succinic acid derivatives, maleic acid (anhydride) and alcohols by esterification. For example, Chinese Patent CN103611546 discloses the preparation of dimethyl succinate by hydrogenation of dimethyl maleate using a supported hydrogenation catalyst, and Chinese Patent CN102863335 discloses the reaction of maleic anhydride with alcohols and further hydrogenation to obtain succinic acid esters. In addition, it can also be prepared by the oxidative carbonylation of olefins. In contrast, the oxidative dicarbonylation of ethylene is the most atom-economic and has simple raw materials, and using the same raw materials can obtain products with higher added value than reductive carbonylation. However, due to the oxidative carbonylation of olefins, olefins, 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 ethylene / air system is 3.1 - 32 vol%, which further limits the application of the oxidative dicarbonylation of olefins. Therefore, how to develop a method for the oxidative dicarbonylation of olefins with intrinsic safety is the key to realizing the industrial application of the oxidative dicarbonylation of ethylene. Summary of the Invention
[0004] The purpose of the present invention is to provide a method for preparing succinic acid esters by oxidative dicarbonylation of olefins with intrinsic safety to overcome the deficiencies of the prior art.
[0005] To this end, the present invention adopts the following technical solutions: A method for preparing succinic acid esters by oxidative dicarbonylation of olefins with intrinsic safety uses olefins and alcohols as reactants, palladium compounds and copper compounds as bimetallic catalysts, and fills a mixed gas of CO, O2 and inert gas. The reaction is carried out at 25 - 120 °C and a pressure of 0.1 - 5 MPa for 24 - 72 h to generate succinic acid esters. The reaction formula is as follows: The structural formula of the olefin is , where R1 is one of hydrogen, substituted or unsubstituted alkyl, aromatic or non-aromatic cyclic compounds containing or not containing heteroatoms.
[0006] The structural formula of the alcohol is , and R2 is a substituted or unsubstituted alkyl group.
[0007] The molar ratio of the olefin to the alcohol is 1:2 to 1:50.
[0008] The palladium compound is at least one of palladium acetate, palladium nitrate, palladium chloride, palladium acetylacetonate or palladium trifluoroacetate, and the copper compound is at least one of copper chloride, cuprous chloride, copper bromide or copper iodide.
[0009] The molar ratio of the palladium compound to the copper compound is 1:1 to 1:10.
[0010] The volume ratio of CO to O2 is 2:1 to 10:1.
[0011] 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.
[0012] The method for preparing succinate by oxidative dicarbonylation of olefins 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 succinate compounds can be obtained through oxidative carbonylation 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, high product yield, etc., is suitable for industrial production, and has a wide application prospect. Detailed implementation manners
[0013] The technical solutions of the present invention will be further explained below in conjunction with specific embodiments. All raw materials used in each embodiment are purchased from the market.
[0014] Example 1 Determination of the explosion limit of CO2 inhibiting CO / O2 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 gas was ignited by an ignition electrode to test the explosion pressure of the gas 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.
[0015] Table 1 The maximum explosion pressure of the CO2 inhibition CO / O2 explosion test Example 2 Determination of the explosion limit of N2 inhibiting CO / O2 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. The gas was ignited using an ignition electrode, and 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 effectively inhibit explosion.
[0016] Example 3 Determination of the explosion limit of Ar inhibiting CO / O2 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. The gas was ignited using an ignition electrode, and 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 effectively inhibit explosion.
[0017] Example 4 Determination of the explosion limit of CO2 inhibiting C2H4 / CO / O2 In a 20 L explosion tank, C2H4 / CO / O2 with a volume ratio of 1:2:1 was filled, and CO2 with a volume fraction of 0% - 80% was added respectively. The gas was ignited using an ignition electrode, and the explosion pressure of the gas was measured 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 C2H4 / CO / O2. When the added CO2 exceeds 50%, the explosion risk of CO / O2 can be completely inhibited, ensuring that the reaction proceeds under safe addition.
[0018] Table 2 Maximum explosion pressure of CO2 inhibiting the explosion test of C2H4 / CO / O2 Example 5 According to the results of Example 1, an intrinsically safe olefin oxidative dicarbonylation reaction was carried out. 1 mmol of styrene and 3 mL of methanol were added to a 20 mL high-pressure reaction kettle, and 11.2 mg of Pd(OAc)2 (5% mol) and 13.2 mg of CuCl2 (10% mol) were added respectively. The gas in Component 7 of Example 1 was filled at 1 MPa, and the reaction was carried out at 40 °C for 72 h. After the reaction was completed, the reaction solution was centrifuged, and the product was analyzed by gas chromatography. The yield of dimethyl 2-phenylsuccinate reached 95%, and its qualitative analysis was carried out using NMR.
[0019] The structure of the product is: .
[0020] 1 (400 MHz, Chloroform – d ) δ 7.58 – 7.13 (m, 5H), 4.09 (dd, J= 10.2, 5.2 Hz, 1H), 3.68 (s, 3H), 3.67 (s, 3H), 3.21 (dd, J = 17.0, 10.2 Hz, 1H), 2.67(dd, J = 17.0, 5.2 Hz, 1H). 13 C NMR(101 MHz, Chloroform – d ) δ 173.57, 172.13, 137.76, 129.02, 127.84, 52.51, 52.02, 47.18, 37.73. Example 6 According to the results of Example 1, an intrinsically safe oxidative dicarbonylation reaction of olefins was carried out. 1 mmol of styrene and 3 mL of methanol were added to a 20 mL high-pressure reactor, and 15.2 mg of Pd(acac)2 (5% mol) and 13.2 mg of CuCl2 (10% mol) were added respectively. 1 MPa of the gas in Component 7 of Example 1 was charged, and the reaction was carried out at 40 °C for 72 h. After the reaction was completed, the reaction solution was centrifuged, and the product was analyzed by gas chromatography. The yield of dimethyl 2-phenylsuccinate reached 94%.
[0021] Example 7 According to the results of Example 1, an intrinsically safe oxidative dicarbonylation reaction of olefins was carried out. 1 mmol of styrene and 3 mL of methanol were added to a 20 mL high-pressure reactor, and 15.2 mg of Pd(acac)2 (5% mol) and 9.8 mg of CuCl (10% mol) were added respectively. 1 MPa of the gas in Component 7 of Example 1 was charged, and the reaction was carried out at 40 °C for 72 h. After the reaction was completed, the reaction solution was centrifuged, and the product was analyzed by gas chromatography. The yield of dimethyl 2-phenylsuccinate reached 94%.
[0022] Example 8 According to the results of Example 1, an intrinsically safe oxidative dicarbonylation reaction of olefins was carried out. 1 mmol of styrene and 3 mL of methanol were added to a 20 mL high-pressure reactor, and 8.85 mg of PdCl2 (5% mol) and 13.2 mg of CuCl2 (10% mol) were added respectively. 1 MPa of the gas in Component 7 of Example 1 was charged, and the reaction was carried out at 40 °C for 72 h. After the reaction was completed, the reaction solution was centrifuged, and the product was analyzed by gas chromatography. The yield of dimethyl 2-phenylsuccinate reached 96%.
[0023] Example 9 According to the results of Example 1, an intrinsically safe oxidative dicarbonylation reaction of olefins was carried out. 1 mmol of styrene and 3 mL of methanol were added to a 20 mL high-pressure reactor, and 16.62 mg of Pd(OCCF3)2 (5% mol) and 13.2 mg of CuCl2 (10% mol) were added respectively. The gas in Component 7 of Example 1 was charged at 1 MPa, and the reaction was carried out at 40 °C for 72 h. After the reaction was completed, the reaction solution was centrifuged and the product was analyzed by gas chromatography. The yield of dimethyl 2-phenylsuccinate reached 96%.
[0024] Example 10 According to the results of Example 1, an intrinsically safe oxidative dicarbonylation reaction of olefins was carried out. 1 mmol of 4-methoxystyrene and 3 mL of methanol were added to a 20 mL high-pressure reactor, and 11.2 mg of Pd(OAc)2 (5% mol) and 13.2 mg of CuCl2 (10% mol) were added respectively. The gas in Component 7 of Example 1 was charged at 1 MPa, and the reaction was carried out at 40 °C for 72 h. After the reaction was completed, the reaction solution was centrifuged and the product was analyzed by gas chromatography. The yield of dimethyl 2-(p-methoxyphenyl)succinate reached 93%, and its qualitative analysis was carried out by NMR.
[0025] The structure of the product is as follows: 。
[0026] 1 (400 MHz, Chloroform – d ) δ 7.22 –7.15 (m, 2H), 6.88 –6.82 (m, 2H),4.06 –4.00(m, 1H), 3.78 (s, 2H), 3.67 (s, 3H), 3.66 (s, 3H), 2.21 –3.12 (m,1H), 2.69 –2.60 (m, 1H). 13 C NMR(101 MHz, Chloroform – d ) δ 173.81, 172.17, 159.16, 129.78,128.89, 114.36, 55.36, 52.44, 51.97, 46.34, 37.82. Example 11 According to the results of Example 1, an intrinsically safe olefin oxidative dicarbonylation reaction was carried out. 1 mmol of 4-fluorostyrene and 3 mL of methanol were added to a 20 mL high-pressure reactor, and 11.2 mg of Pd(OAc)2 (5% mol) and 13.2 mg of CuCl2 (10% mol) were added respectively. 1 MPa of the gas in Component 7 of Example 1 was charged, and the reaction was carried out at 40 °C for 72 h. After the reaction was completed, the reaction solution was centrifuged, and the product was analyzed by gas chromatography. The yield of dimethyl 2-(p-fluorophenyl)succinate reached 90%, and its qualitative analysis was carried out by NMR.
[0027] The structure of the product is: 。
[0028] 1 (400 MHz, Chloroform – d ) δ 7.42 – 7.13 (m, 2H), 7.10 – 6.90 (m, 2H), 4.08 (dd, J = 9.8, 5.6 Hz, 2H), 3.68 (s, 3H), 3.67 (s, 3H), 3.18 (dd, J = 16.9, 9.8 Hz, 1H), 2.66 (dd, J = 16.9, 5.6 Hz, 1H). 13 C NMR(101 MHz, Chloroform – d ) δ 173.42, 171.93, 163.58, 161.13, 133.48 (d, J = 3.0 Hz), 129.54, 129.46, 116.03, 115.81, 52.59, 52.07, 46.42, 37.75. 19 F NMR(377 MHz, Chloroform – d ) δ –114.62. Example 12 According to the results of Example 1, an intrinsically safe oxidative dicarbonylation reaction of olefins was carried out. 1 mmol of 4-chlorostyrene and 3 mL of methanol were added to a 20 mL high-pressure reactor, and 11.2 mg of Pd(OAc)2 (5% mol) and 13.2 mg of CuCl2 (10% mol) were added respectively. 1 MPa of the gas in Component 7 of Example 1 was charged, and the reaction was carried out at 40 °C for 72 h. After the reaction was completed, the reaction solution was centrifuged, and the product was analyzed by gas chromatography. The yield of dimethyl 2-(p-chlorophenyl)succinate reached 85%, and its qualitative analysis was carried out by NMR.
[0029] The structure of the product is: .
[0030] 1 (400 MHz, Chloroform – d ) δ 7.65 – 7.07 (m, 4H), 4.06 (dd, J = 9.7, 5.6Hz, 1H), 3.67 (s, 3H), 3.67 (s, 3H), 3.17 (dd, J = 17.0, 9.7 Hz, 1H), 2.65 (dd, J = 17.0, 5.6 Hz, 1H). 13 C NMR(101 MHz, Chloroform – d ) δ 173.18, 171.85, 136.20, 133.78,129.28, 52.64, 52.10, 46.56, 37.56. Example 13 According to the results of Example 1, an intrinsically safe oxidative dicarbonylation reaction of olefins was carried out. 1 mmol of 4-bromostyrene and 3 mL of methanol were added to a 20 mL high-pressure reactor, and 11.2 mg of Pd(OAc)2 (5% mol) and 13.2 mg of CuCl2 (10% mol) were added respectively. 1 MPa of the gas in Component 7 of Example 1 was charged, and the reaction was carried out at 40 °C for 72 h. After the reaction was completed, the reaction solution was centrifuged, and the product was analyzed by gas chromatography. The yield of dimethyl 2-(p-bromophenyl)succinate reached 92%, and its qualitative analysis was carried out by NMR.
[0031] The structure of the product is: .
[0032] 1 (400 MHz, Chloroform –d ) δ 7.76 – 7.36 (m, 2H), 7.25 – 7.05 (m, 2H), 4.05 (dd, J J = 9.7, 5.6 Hz, 1H), 3.67 (s, 3H), 3.66 (s, 3H), 3.17 (dd, J J = 17.0, 9.7 Hz, 1H), 2.65 (dd, J J = 17.0, 5.6 Hz, 1H). 13 C NMR (101 MHz, Chloroform – d ) δ 173.09, 171.81, 136.71, 132.14, 129.62, 121.87, 52.65, 52.11, 46.62, 37.48. Example 14 According to the results of Example 1, an intrinsically safe oxidative dicarbonylation reaction of olefins was carried out. 1 mmol of 1 - hexene and 3 mL of methanol were added to a 20 mL high - pressure reactor, and 11.2 mg of Pd(OAc)2 (5% mol) and 13.2 mg of CuCl2 (10% mol) were added respectively. The gas in Component 7 of Example 1 was charged at 1 MPa, and the reaction was carried out at 40 °C for 72 h. After the reaction was completed, the reaction solution was centrifuged, and the product was analyzed by gas chromatography. The yield of dimethyl 2 - pentylsuccinate reached 95%, and its qualitative analysis was carried out by NMR.
[0033] The structure of the product is: .
[0034] 1 1H NMR (400 MHz, Chloroform – d ) δ 3.68 (s, 3H), 3.66 (s, 3H), 2.95 – 2.64 (m, 2H), 2.47 – 2.38 (m, 1H), 1.70 – 1.40 (m, 2H), 1.26 (q, J J = 4.7, 3.8 Hz, 8H), 0.93 – 0.74 (m, 3H). 13 13C NMR (101 MHz, Chloroform – d) δ 175.67, 172.63, 51.87, 41.28, 35.93, 32.08, 31.70, 29.15, 27.00, 22.67, 14.15. Example 15 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, 11.2 mg of Pd(OAc)2 (5% mol), 13.2 mg of CuCl2 (10% mol) and 3 mL of methanol were added respectively. 1 MPa of the gas in Component 15 of Example 4 was charged, in which the gas contained about 1 mmol 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 the product was analyzed by gas chromatography. The yield of dimethyl succinate reached 75 mg, and the selectivity was greater than 95%.
[0035] Comparative Example 1 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, 11.2 mg of Pd(OAc)2 (5% mol), 13.2 mg of CuCl2 (10% mol) and 3 mL of methanol were added respectively. 0.4 MPa of the gas in Component 9 of Example 4 was charged, in which the gas contained about 1 mmol 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 the product was analyzed by gas chromatography. The yield of dimethyl succinate was 75 mg, and the selectivity was greater than 95%.
[0036] According to the results of Example 4, 15 and Comparative Example 1, it can be found that after filling a suitable inert atmosphere in the reaction system, the catalytic efficiency will not be affected. Although good reaction results can also be obtained in the comparative example, 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 an intrinsically safe oxidative dicarbonylation reaction of olefins.
[0037] In addition, the inventors of this case also carried out experiments in the manner of Examples 1-15 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.
[0038] It should be understood that the above embodiments are only used to illustrate the technical concept and characteristics of the present invention, and their purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly, and cannot be used to limit the protection scope of the present invention. All 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 succinic acid esters by oxidative dicarbonylation of olefins with intrinsic safety, characterized in that, Using olefins and alcohols as reactants, palladium compounds and copper compounds as bimetallic catalysts, filling with a mixed gas of CO, O2 and inert gas, reacting for 24 - 72 h under the conditions of 25 - 120 °C and a pressure of 0.1 - 5 MPa to produce succinic acid esters compounds.
2. The method for preparing succinic acid esters by oxidative dicarbonylation of olefins with intrinsic safety as claimed in claim 1, wherein, The structural formula of the olefin 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 succinic acid esters by oxidative dicarbonylation of olefins with intrinsic safety as claimed in claim 2, characterized in that, The olefin is one of ethylene, styrene, 4 - methoxystyrene, 4 - fluorostyrene, 4 - chlorostyrene, 4 - bromostyrene or 1 - hexene.
4. The method for preparing succinic acid esters by oxidative dicarbonylation of olefins 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.
5. The method for preparing succinic acid esters by olefin oxidative dicarbonylation with intrinsic safety as claimed in claim 3, wherein The alcohol is one of methanol, ethanol, propanol or butanol.
6. The method for preparing succinic acid esters by olefin oxidative dicarbonylation with intrinsic safety as described in claim 1, characterized in that, The molar ratio of the olefin to the alcohol is 1:2 - 1:
50.
7. The method for preparing succinic acid esters by oxidative dicarbonylation of olefins with intrinsic safety as claimed in claim 1, wherein The palladium compound is at least one of palladium acetate, palladium nitrate, palladium chloride, palladium acetylacetonate or palladium trifluoroacetate, and the copper compound is at least one of copper chloride, cuprous chloride, copper bromide or copper iodide.
8. The method for preparing succinic acid esters by oxidative dicarbonylation of olefins with intrinsic safety as claimed in claim 1, characterized in that, The molar ratio of the palladium compound to the copper compound is 1:1 - 1:
10.
9. The method for preparing succinic acid esters by oxidative dicarbonylation of olefins with intrinsic safety as described in claim 1, wherein, The volume ratio of CO to O2 is 2:1 - 10:
1.
10. The method for preparing succinic acid esters by oxidative dicarbonylation of olefins with intrinsic safety as described in claim 1, characterized in that, 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 fraction of the mixed gas.