CN111138396A - Method for synthesizing glutaconic anhydride compound by using carbon dioxide - Google Patents
Method for synthesizing glutaconic anhydride compound by using carbon dioxide Download PDFInfo
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Abstract
The invention belongs to the technical field of fine chemical synthesis, and relates to a method for synthesizing a glutaconic anhydride compound by using carbon dioxide. The method comprises the steps of using a 2-butenoic acid derivative as a raw material, adding an organic base and a reaction solvent, then introducing carbon dioxide, stirring and reacting for 0.5-24 hours at 0-50 ℃, standing to room temperature after the reaction is finished, slowly releasing unreacted gas, directly concentrating the reaction liquid under reduced pressure to obtain a crude product, and purifying by column chromatography or recrystallization to obtain a glutaconic anhydride product. The method uses cheap and easily-obtained 2-butenoic acid derivatives and carbon dioxide as raw materials, uses organic base as an accelerator, is safe and simple to operate, low in toxicity, environment-friendly and has potential application value in fine organic synthesis of medicines, pesticides and the like.
Description
Technical Field
The invention belongs to the technical field of fine chemical synthesis, and relates to a method for synthesizing a glutaconic anhydride compound by using carbon dioxide.
Background
The glutaconic anhydride compounds are important organic synthesis intermediates and potential alkylene oxide comonomers, and are widely used for synthesizing glutaconic acid derivatives and constructing oxygen-containing heterocyclic compounds through cycloaddition reaction.
The conventional synthesis of glutaconate anhydride compounds relies mainly on dehydration of glutaconate compounds, etc. (a) S.A. Ahmed, E.Bardshiri and T.J.Simpson, Tetrahedron Lett.,1988,29, 1595; (b) Y.Kita, K.Higuchi, Y.Yoshida, K.Iio, S.Kitagaki, K.Ueda, S.Akai and H.Fujkaio, J.Am.Chem.Soc.,2001,123,3214 c, (j.Song, Y.X.Lei and Z.Rappoport, J.Org.Chem, 2007,72, 9152; (d) C.T.Mbofana and S.J.Miller, J.Am.Chem.Soc., 2014,136,3285; (g.Zo, Whao, Wheu, Wgay, Wgay.J.2015, Wgay.J.Zhao, Wgao, 1988,29, 15980; (b) Y.Kita, Kiguchi, Y.Yoshida.Y.Y.Yoshida, K.Iio, K.Kitagki, K.K.Kitagaki, K.Iio, K.I1, K.Iigo, K. The methods need to use multi-step reaction to construct diacid precursor in advance, then use dehydrating agent to form ring, and the involved reaction steps are long, the efficiency is low, the post-treatment process is complicated, and the method is not economical and green.
Disclosure of Invention
In order to solve the problems, the invention provides a method for synthesizing the glutaconic anhydride compound by reacting the 2-butenoic acid derivative with carbon dioxide, wherein organic alkali is used as an accelerator, carbon dioxide is used as a carboxylation reagent, reaction raw materials and reagents are simple and easy to obtain, the reaction substrate type has wide universality, the post-treatment process is simple, and the yield of a target product is high.
The invention relates to a 2-butenoic acid derivative, which is characterized in that an alkenyl ketene intermediate is formed under the action of organic base, an enol ammonium intermediate is further formed under the action of base, and the enol ammonium intermediate reacts with carbon dioxide to form a carboxylic acid intermediate, and the carboxylic acid intermediate is subjected to intramolecular nucleophilic cyclization to generate an anhydride product. The method uses cheap and easily-obtained 2-butenoic acid derivatives and carbon dioxide as raw materials, uses organic base as an accelerator, is safe and simple to operate, low in toxicity, environment-friendly and has potential application value in fine organic synthesis of medicines, pesticides and the like.
The invention is realized by the following technical scheme:
a method for synthesizing a glutaconic anhydride compound by using carbon dioxide comprises the steps of adding a 2-butenoic acid derivative serving as a raw material into a reaction kettle, then adding an organic base and a reaction solvent, then introducing the carbon dioxide, stirring and reacting at 0-50 ℃ for 0.5-24 hours, standing to room temperature after the reaction is finished, slowly releasing unreacted gas, directly concentrating the reaction liquid under reduced pressure to obtain a crude product, and purifying the crude product to obtain a glutaconic anhydride product;
the above reaction is represented by the following formula:
wherein R is1Is phenyl, p-methylphenyl, p-tert-butylphenyl, p-cyclohexylphenyl, p-methoxyphenyl, p-phenylphenyl, naphthyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, 2-furyl, 2-thienyl, methyl, isohexenyl or cyclopropane;
R2is hydrogen, methyl, phenyl or benzyl; r1And R2The same or different;
x is a pentafluorophenoxy group, a difluorophenoxy group, a monofluorophenoxy group, a p-trifluoromethylphenoxy group, a 2, 4-dinitrophenoxy group, an o-nitrophenoxy group, a p-nitrophenoxy group, a phenoxy group, a hexafluoroisopropoxy group, a chlorine group, an imidazolyl group or a phthalimido group.
The reaction kettle adopts an intermittent high-pressure reaction kettle or a continuous high-pressure reaction kettle.
The pressure of the introduced carbon dioxide is 0.1-5 MPa.
The organic base is one or a mixture of more than two of 1, 8-diazabicycloundecene-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, triethylene diamine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, pyridine, p-dimethylaminopyridine, triethylamine, tri-n-butylamine and diisopropylethylamine.
The molar ratio of the added organic base to the 2-butenoic acid derivative raw material is (1-5): 1.
The solvent is one or more than two of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, toluene or acetonitrile.
And purifying the crude product by adopting column chromatography or recrystallization, wherein the eluent of the column chromatography or the recrystallization solvent is ethyl acetate or a mixed solvent of ethyl acetate and acetic acid, and the volume ratio of the ethyl acetate to the acetic acid is 100 (0-10).
The invention has the beneficial effects that: the method uses cheap and easily-obtained 2-butenoic acid derivatives and carbon dioxide as raw materials, uses organic base as an accelerator, is safe and simple to operate, low in toxicity, environment-friendly and has potential application value in fine organic synthesis of medicines, pesticides and the like.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
Adding a stirrer, 0.1 mmol of 3-phenyl-2-butenoic acid pentafluorophenyl ester, 0.3 mmol of 1, 8-diazabicycloundec-7-ene and 2 ml of acetonitrile into a 20 ml autoclave, adding 1.0MPa of carbon dioxide, stirring at 25 ℃ for 24 hours, slowly releasing unreacted carbon dioxide, decompressing reaction liquid, performing rotary evaporation to remove the acetonitrile to obtain a crude product, and performing column chromatography purification to obtain a target product. The eluent used for column chromatography is ethyl acetate and acetic acid with the volume ratio of 100: 1. The yield was 90%.
Example 2
Adding a stirrer, 0.1 mmol of 3-phenyl-2-butenoic acid pentafluorophenyl ester, 0.10 mmol of 1, 8-diazabicycloundec-7-ene and 2 ml of acetonitrile into a 20 ml autoclave, adding 1.0MPa of carbon dioxide, stirring at 25 ℃ for 24 hours, slowly releasing unreacted carbon dioxide, decompressing reaction liquid, performing rotary evaporation to remove the acetonitrile to obtain a crude product, and performing column chromatography purification to obtain a target product. The eluent used for column chromatography is ethyl acetate and acetic acid with the volume ratio of 100: 10. The yield was 64%.
Example 3
Adding a stirrer, 0.1 mmol of 3-phenyl-2-butenoic acid pentafluorophenyl ester, 0.3 mmol of 1, 8-diazabicycloundec-7-ene and 2 ml of acetonitrile into a 20 ml autoclave, adding 0.1MPa of carbon dioxide, stirring at 25 ℃ for 24 hours, slowly releasing unreacted carbon dioxide, decompressing reaction liquid, performing rotary evaporation to remove the acetonitrile to obtain a crude product, and performing column chromatography purification to obtain a target product. The eluent used for column chromatography is ethyl acetate and acetic acid with the volume ratio of 100: 1. The yield was 84%.
Example 4
Adding a stirrer, 0.1 mmol of 3-phenyl-2-butenoic acid pentafluorophenyl ester, 0.3 mmol of 1, 5-diazabicyclo [4.3.0] non-5-ene and 2 ml of acetonitrile into a 20 ml autoclave, flushing 1.0MPa carbon dioxide, stirring at 0 ℃ for 24 hours, slowly releasing unreacted carbon dioxide, decompressing reaction liquid, carrying out rotary evaporation to remove the acetonitrile to obtain a crude product, and carrying out column chromatography purification to obtain a target product. The eluent used for column chromatography is ethyl acetate and acetic acid with the volume ratio of 100: 1. The yield was 77%.
Example 5
Adding a stirrer, 0.1 mmol of 3-phenyl-2-butenoic acid pentafluorophenyl ester, 0.3 mmol of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene and 2 ml of acetonitrile into a 20 ml autoclave, flushing 5MPa carbon dioxide, stirring for 0.5 hour at 25 ℃, slowly releasing unreacted carbon dioxide, decompressing and rotary steaming reaction liquid to remove acetonitrile to obtain a crude product, and purifying by column chromatography to obtain a target product. The eluent used for column chromatography is ethyl acetate and acetic acid with the volume ratio of 100: 1. The yield was 60%.
Example 6
Adding a stirrer, 0.1 mmol of 3-phenyl-2-butenoic acid pentafluorophenyl ester, 0.3 mmol of 1, 8-diazabicycloundec-7-ene and 2 ml of toluene into a 20 ml autoclave, adding 1.0MPa of carbon dioxide, stirring at 25 ℃ for 24 hours, slowly releasing unreacted carbon dioxide, decompressing reaction liquid, performing rotary evaporation to remove the toluene to obtain a crude product, and performing column chromatography purification to obtain a target product. The eluent used for column chromatography is ethyl acetate and acetic acid with the volume ratio of 100: 1. The yield was 55%.
Example 7
Adding a stirrer, 0.1 mmol of 3-phenyl-2-butenoic acid p-fluorophenyl ester, 0.5 mmol of 1, 8-diazabicycloundec-7-ene and 2 ml of acetonitrile into a 20 ml autoclave, flushing 1.0MPa of carbon dioxide, stirring at 25 ℃ for 24 hours, slowly releasing unreacted carbon dioxide, decompressing reaction liquid, performing rotary evaporation to remove the acetonitrile to obtain a crude product, and performing column chromatography purification to obtain a target product. The eluent used for column chromatography is ethyl acetate and acetic acid with the volume ratio of 100: 1. The yield was 81%.
Example 8
Adding a stirrer, 0.1 mmol of 3-phenyl-2-butenoic acid p-trifluoromethylphenyl ester, 0.3 mmol of 1, 8-diazabicycloundec-7-ene and 2 ml of acetonitrile into a 20 ml autoclave, flushing 1.0MPa of carbon dioxide, stirring at 50 ℃ for 24 hours, slowly releasing unreacted carbon dioxide, decompressing reaction liquid, performing rotary evaporation to remove the acetonitrile to obtain a crude product, and performing column chromatography purification to obtain a target product. The eluent used for column chromatography is ethyl acetate and acetic acid with the volume ratio of 100: 1. The yield was 88%.
Example 9
Adding a stirrer, 0.1 mmol of p-nitrophenyl 3-phenyl-2-butenoate, 0.3 mmol of 1, 8-diazabicycloundec-7-ene and 2 ml of acetonitrile into a 20 ml autoclave, flushing 1.0MPa of carbon dioxide, stirring at 25 ℃ for 24 hours, slowly releasing unreacted carbon dioxide, decompressing reaction liquid, performing rotary evaporation to remove the acetonitrile to obtain a crude product, and performing column chromatography purification to obtain a target product. The eluent used for column chromatography is ethyl acetate and acetic acid with the volume ratio of 100: 1. The yield was 85%.
Example 10
Adding a stirrer, 0.1 mmol of 3-phenyl-2-butenoyl chloride, 0.3 mmol of 1, 8-diazabicycloundec-7-ene and 2 ml of acetonitrile into a 20 ml autoclave, flushing 1.0MPa of carbon dioxide, stirring at 25 ℃ for 24 hours, slowly releasing unreacted carbon dioxide, decompressing reaction liquid, performing rotary evaporation to remove acetonitrile to obtain a crude product, and performing column chromatography purification to obtain a target product. The eluent used for column chromatography is ethyl acetate and acetic acid with the volume ratio of 100: 1. The yield was 89%.
The structural characterization data of the products obtained in examples 1 to 10 are as follows:
1H NMR(400MHz,CDCl3)δ7.57–7.51(m,5H),6.62(s,1H),3.92(s,2H).13C NMR(126MHz,CDCl3)δ164.7,160.2,152.7,133.8,132.1,129.5,126.1,112.1, 33.4.IR(neatcm-1)ν2956,2922,2854,1794,1726,1466,1122,974,767.HRMS (ESI,m/z):calculated forC11H9O3[M+H]+:189.0552,found:189.0552.
the structure of the resulting product is deduced from the above data as follows:
example 11
Adding a stirrer, 0.1 mmol of 3-p-methoxyphenyl-2-butenoic acid pentafluorophenyl ester, 0.3 mmol of 1, 8-diazabicycloundec-7-ene and 2 ml of acetonitrile into a 20 ml autoclave, flushing 1.0MPa carbon dioxide, stirring at 25 ℃ for 24 hours, slowly releasing unreacted carbon dioxide, decompressing reaction liquid, carrying out rotary evaporation to remove acetonitrile to obtain a crude product, and carrying out column chromatography purification to obtain a target product. The eluent used for column chromatography is ethyl acetate and acetic acid with the volume ratio of 50: 1. The yield was 95%.
The structural characterization data for the product obtained in example 11 are as follows:
1H NMR(400MHz,CDCl3)δ7.53(d,J＝8.9Hz,2H),7.00(d,J＝8.9Hz,2H), 6.53(s,1H),3.89–3.88(m,5H).13C NMR(126MHz,CDCl3)δ165.0,162.8,160.5, 151.9,127.9,125.8,114.8,109.4,55.6,33.2.IR(neat cm-1)ν2924,2852,1791,1732, 16256,1515,1185,868,619.HRMS(ESI,m/z):calculated for C12H11O4[M+H]+: 219.0657,found:219.0652.
the structure of the resulting product is deduced from the above data as follows:
example 12
Adding a stirrer, 0.1 mmol of 3-naphthyl-2-butenoic acid pentafluorophenyl ester, 0.3 mmol of 1, 8-diazabicycloundec-7-ene and 2 ml of acetonitrile into a 20 ml autoclave, adding 1.0MPa of carbon dioxide, stirring for 16 hours at 25 ℃, slowly releasing unreacted carbon dioxide, decompressing reaction liquid, performing rotary evaporation to remove the acetonitrile to obtain a crude product, and performing column chromatography purification to obtain a target product. The eluent used for column chromatography is ethyl acetate and acetic acid with the volume ratio of 100: 1. The yield was 78%.
The structural characterization data for the product obtained in example 12 are as follows:
1H NMR(400MHz,DMSO-d6)δ8.42(s,1H),8.04–7.97(m,4H),7.62(s,2H), 6.98(s,1H),4.30(s,2H).13C NMR(101MHz,DMSO-d6)δ166.2,161.4,153.7, 134.0,132.5,131.2,129.0,128.5,128.0,127.7,127.5,126.9,123.2,111.0,33.4.IR (neat cm-1)ν2973,2929,1784,1723,1622,1384,1122,975,814,618.HRMS(ESI, m/z):calculated for C15H11O3[M+H]+:239.0708,found:239.0701.
the structure of the resulting product is deduced from the above data as follows:
example 13
Adding a stirrer, 0.1 mmol of 3-p-fluorophenyl-2-butenoic acid pentafluorophenyl ester, 0.3 mmol of 1, 8-diazabicycloundec-7-ene and 2 ml of acetonitrile into a 20 ml autoclave, flushing 1.0MPa carbon dioxide, stirring at 25 ℃ for 24 hours, slowly releasing unreacted carbon dioxide, decompressing reaction liquid, performing rotary evaporation to remove acetonitrile to obtain a crude product, and performing column chromatography purification to obtain a target product. The eluent used for column chromatography is ethyl acetate. The yield was 92%.
The structural characterization data for the product obtained in example 13 are as follows:
1H NMR(500MHz,CDCl3)δ7.57(dd,J＝8.2,5.2Hz,1H),7.20(t,J＝8.3Hz, 1H),6.57(s,1H),3.89(s,2H).13C NMR(126MHz,CDCl3)δ164.8(d,J＝255.4 Hz),164.4,160.0,151.4,129.9,128.3(d,J＝8.9Hz),116.8(d,J＝22.1Hz),111.9(d, J＝1.4Hz),33.4.IR(neat cm-1)ν2952,2854,1793,1738,1635,1416,873,836,619. HRMS(ESI,m/z):calculated for C11H8FO3[M+H]+:207.0457,found:207.0448.
the structure of the resulting product is deduced from the above data as follows:
example 14
Adding a stirrer, 0.1 mmol of 3-furyl-2-butenoic acid pentafluorophenyl ester, 0.3 mmol of 1, 8-diazabicycloundec-7-ene and 2 ml of acetonitrile into a 20 ml autoclave, flushing 1.0MPa carbon dioxide, stirring at 25 ℃ for 24 hours, slowly releasing unreacted carbon dioxide, decompressing reaction liquid, performing rotary evaporation to remove the acetonitrile to obtain a crude product, and performing column chromatography purification to obtain a target product. The eluent used for column chromatography is ethyl acetate and acetic acid with the volume ratio of 100: 1. The yield was 86%.
The structural characterization data for the product obtained in example 14 are as follows:
1H NMR(400MHz,DMSO-d6)δ8.00(s,1H),7.29(s,1H),6.74(s,1H),6.42 (s,1H),4.04(s,2H).13C NMR(126MHz,DMSO-d6)δ165.6,161.3,148.8,147.4, 142.8,116.1,113.2,105.9,31.5.IR(neat cm-1)ν2925,2854,1790,1733,1629,1562, 1004,971,841,617.HRMS(ESI,m/z):calculated for C9H7O4[M+H]+:179.0344, found:179.0339.
the structure of the resulting product is deduced from the above data as follows:
example 15
Adding a stirrer, 0.1 mmol of 3-cyclopropyl-2-butenoic acid pentafluorophenyl ester, 0.3 mmol of 1, 8-diazabicycloundec-7-ene and 2 ml of acetonitrile into a 20 ml autoclave, flushing 1.0MPa of carbon dioxide, stirring at 25 ℃ for 24 hours, slowly releasing unreacted carbon dioxide, decompressing reaction liquid, carrying out rotary evaporation to remove acetonitrile to obtain a crude product, and carrying out column chromatography purification to obtain a target product. The eluent used for column chromatography is ethyl acetate and acetic acid with the volume ratio of 100: 1. The yield was 82%.
The structural characterization data for the product obtained in example 15 are as follows:
1H NMR(400MHz,CDCl3)δ5.94(t,J＝1.5Hz,1H),3.34–3.32(m,2H), 1.69–1.62(m,1H),1.13–1.08(m,2H),0.88–0.84(m,2H).13C NMR(101MHz, CDCl3)δ164.9,162.0,159.8,110.1,33.2,16.6,9.3.IR(neat cm-1)ν2954,2918, 2852,1792,1734.HRMS(ESI,m/z):calculated for C8H9O3[M+H]+:153.0552, found:153.0546.
the structure of the resulting product is deduced from the above data as follows:
example 16
Adding a stirrer, 0.1 mmol of 3-phenyl-2-pentenoic acid pentafluorophenyl ester, 0.3 mmol of 1, 8-diazabicycloundec-7-ene and 2 ml of acetonitrile into a 20 ml autoclave, flushing 1.0MPa carbon dioxide, stirring at 25 ℃ for 24 hours, slowly releasing unreacted carbon dioxide, decompressing reaction liquid, performing rotary evaporation to remove the acetonitrile to obtain a crude product, and performing column chromatography purification to obtain a target product. The eluent used for column chromatography is ethyl acetate and acetic acid with the volume ratio of 100: 1. The yield was 70%.
The structural characterization data for the product obtained in example 16 are as follows:
1H NMR(400MHz,CDCl3)δ7.46–7.45(m,2H),7.39–7.37(m,3H),6.06(s, 1H),3.12(q,J＝7.4Hz,1H),1.08(t,J＝7.4Hz,3H).13C NMR(101MHz,CDCl3) δ171.4,164.7,140.9,129.1,128.6,127.1,116.1,24.5,13.6.IR(neat cm-1)ν2969, 2926,2871,1798,1739,1684,1616,1515,767,700.HRMS(ESI,m/z):calculated for C12H11O3[M+H]+:203.0708,found:203.0700.
the structure of the resulting product is deduced from the above data as follows:
。
Claims (10)
1. a method for synthesizing glutaconic anhydride compounds by using carbon dioxide is characterized by comprising the following steps: adding a 2-butenoic acid derivative serving as a raw material into a reaction kettle, adding an organic base and a reaction solvent, introducing carbon dioxide, stirring and reacting at 0-50 ℃ for 0.5-24 hours, standing to room temperature after the reaction is finished, slowly releasing unreacted gas, directly concentrating the reaction liquid under reduced pressure to obtain a crude product, and purifying the crude product to obtain a glutaconic anhydride product;
the above reaction is represented by the following formula:
wherein R is1Is phenyl, p-methylphenyl, p-tert-butylphenyl, p-cyclohexylphenyl, p-methoxyphenyl, p-phenylphenyl, naphthyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, 2-furyl, 2-thienyl, methyl, isohexenyl or cyclopropane;
R2is hydrogen, methyl, phenyl or benzyl; r1And R2The same or different;
x is a pentafluorophenoxy group, a difluorophenoxy group, a monofluorophenoxy group, a p-trifluoromethylphenoxy group, a 2, 4-dinitrophenoxy group, an o-nitrophenoxy group, a p-nitrophenoxy group, a phenoxy group, a hexafluoroisopropoxy group, a chlorine group, an imidazolyl group or a phthalimido group.
2. The method of claim 1, wherein the organic base is one or more selected from the group consisting of 1, 8-diazabicycloundecen-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, triethylenediamine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, pyridine, p-dimethylaminopyridine, triethylamine, tri-n-butylamine, and diisopropylethylamine.
3. The method for synthesizing glutaconic anhydride compound using carbon dioxide as claimed in claim 1 or 2, wherein the solvent is one or more of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, toluene or acetonitrile.
4. The method for synthesizing the glutaconic anhydride compound by using the carbon dioxide as claimed in claim 1 or 2, wherein the molar ratio of the added organic base to the raw material of the 2-butenoic acid derivative is (1-5: 1; the pressure of the introduced carbon dioxide is 0.1-5 MPa.
5. The method for synthesizing the glutaconic anhydride compound by using the carbon dioxide as claimed in claim 3, wherein the molar ratio of the added organic base to the raw material of the 2-butenoic acid derivative is (1-5): 1; the pressure of the introduced carbon dioxide is 0.1-5 MPa.
6. The method for synthesizing the glutaconic anhydride compound by using the carbon dioxide as claimed in claim 1, 2 or 5, wherein the crude product is purified by column chromatography or recrystallization, and the eluent of the column chromatography or the recrystallization solvent is ethyl acetate or a mixed solvent of the ethyl acetate and acetic acid, wherein the volume ratio of the ethyl acetate to the acetic acid is 100 (0-10).
7. The method for synthesizing glutaconic anhydride compounds by using carbon dioxide as claimed in claim 3, wherein the crude product is purified by column chromatography or recrystallization, and the eluent of the column chromatography or the recrystallization solvent is ethyl acetate or a mixed solvent of ethyl acetate and acetic acid, wherein the volume ratio of ethyl acetate to acetic acid is 100 (0-10).
8. The method for synthesizing glutaconic anhydride compounds by using carbon dioxide as claimed in claim 4, wherein the crude product is purified by column chromatography or recrystallization, and the eluent of the column chromatography or the recrystallization solvent is ethyl acetate or a mixed solvent of ethyl acetate and acetic acid, wherein the volume ratio of ethyl acetate to acetic acid is 100 (0-10).
9. The method for synthesizing pentenedioic anhydride compound by using carbon dioxide as claimed in claim 1, 2, 5,7 or 8, wherein said autoclave is a batch autoclave or a continuous autoclave.
10. The method for synthesizing glutaconic anhydride compound by using carbon dioxide as claimed in claim 3, wherein the reaction kettle is a batch high-pressure reaction kettle or a continuous high-pressure reaction kettle.
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| CN115073318A (en) * | 2022-06-15 | 2022-09-20 | 大连理工大学 | Carbon dioxide-promoted method for synthesizing precursors of polycondensation monomers such as glutaronitrile and the like by using acetonitrile |
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