CN114656358A - Method for preparing ester compound containing olefin under catalysis of deep eutectic solvent - Google Patents
Method for preparing ester compound containing olefin under catalysis of deep eutectic solvent Download PDFInfo
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Abstract
The invention belongs to the technical field of organic synthesis, and discloses a method for preparing an ester compound containing olefin by catalysis of a deep eutectic solvent. The deep eutectic solvent selected by the invention is environment-friendly, easy to prepare, cheap in components and easy to recover, and the preparation method is simple and convenient to operate, simple to separate, free of a water-carrying agent, capable of being recycled for multiple times and high in yield.
Description
Technical Field
The invention belongs to the field of organic synthesis, and provides a novel method for preparing an ester compound containing olefin under the catalysis of a deep eutectic solvent.
Background
Ester compounds containing olefin have wide application in the fields of organic synthesis, plasticizer, pour point depressant and the like, for example, methyl methacrylate is a monomer of polymethyl methacrylate and is mainly used for manufacturing organic glass, paint, lubricating oil additive, plastic and the like [ Limin. MMA market analysis and prospect [ J ] Chinese petroleum and chemical engineering economic analysis, 2019(09):56-58 ]; neopentyl glycol dimethacrylate has the characteristics of low viscosity and high boiling point, and is applied to coatings, printing ink, fast-dissolving sol, rubber products, building materials and the like as a crosslinking monomer [ Dolomiko-neopentyl glycol dimethacrylate as a green catalytic synthesis process research [ D ] Tianjin university, 2007 ]; isooctyl methacrylate can be used as a monomer of acrylic resin [ Jontosen, Baihaixi, Qin Dynasty, Synthesis and performance research of ternary polymerization high oil absorption resin [ J ] Gansu science and technology, 2005(10): 101-; the maleic diester compound can be used as raw material of synthetic resin and paint, impregnating agent, dispersing agent, lubricating agent and pesticide for petroleum industry, fabric, plastics and paper-making industry, and can be used as plasticizer of polyvinyl chloride resin and methacrylic resin, and its copolymer can be used as internal plasticizer and adhesive, etc. (Weiqingle, used in synthesis of difenoconazole maleate, Hebei chemical industry 2006(03): 30-31).
The preparation of the ester compound containing olefin is mostly synthesized by adopting sulfuric acid catalysis at present, has the advantages of high yield and low cost, but also has the problems of serious environmental pollution, difficult recovery, serious corrosion, more side reactions and the like; in addition, the esterification reaction is catalyzed by a solid acid catalyst or a molecular sieve catalyst, which has high catalytic activity and can be recycled, but the two catalysts have poor stability, are easy to deactivate and have limited cycle times, so that the industrial application of the catalysts is limited; the ionic liquid overcomes the defect of easy inactivation, the reaction temperature is not high, the recovery is simple, the activity is still possessed after the cyclic utilization for many times, but the industrial application of the ionic liquid is limited by the limitations of higher cost, certain toxicity, poor biodegradability, relatively complex synthesis and the like [ (a) Reza Fareghi-Alamdari, MehriNadiriri, Hassan Hazarkhani. journal of Molecular Liquids,2017,227.(b) lindane.
The deep eutectic solvent is a eutectic substance which is formed by bonding two or more compounds through hydrogen bonds and is liquid at normal temperature, and the freezing point of the eutectic solvent is obviously lower than the melting point of each component pure substance. Compared with the traditional organic solvent, the deep eutectic solvent has the advantages of extremely low vapor pressure, high thermodynamic and chemical stability, extremely low toxicity and the like, and the Deep Eutectic Solvent (DESs) not only has the advantages of difficult inactivation of ionic liquid, low reaction temperature, simple recovery and good recycling effect, but also makes up the defects of high cost, high toxicity, poor degradability, complex synthesis and the like, so that the deep eutectic solvent has good application prospect in catalyzing the synthesis of the ester compound containing olefin by the deep eutectic solvent [ Xingquan, Han, Shilin, Shashang, the application of the deep eutectic solvent in green organic synthesis [ J ] organic chemistry, 2016,36(03):480-489 ].
Disclosure of Invention
The invention provides a novel method for synthesizing an ester compound containing olefin under the catalysis of a three-component deep eutectic solvent, which has the characteristics of environmental friendliness, simplicity and convenience in operation, capability of recycling the deep eutectic solvent and the like.
The technical scheme of the invention is as follows:
a process for preparing the ester compound containing olefin by deep eutectic solvent includes such steps as esterifying or ester exchange reaction in deep eutectic solvent while heating to obtain ester compound containing olefin, which can be used as solvent, catalyst and polymerization inhibitor. The synthetic route is as follows:
Synthetic route two
Synthetic route III
In the formula: n is greater than or equal to 0; r1Is alkyl, alkenyl or phenyl; r2、R3、R5And R6Is H or alkyl, the same or different; r4Is alkyl or haloalkyl;
the reaction temperature is 70-130 ℃, and the reaction time is 4-12 hours;
after the reaction is finished, the deep eutectic solvent and the ester layer are directly layered, the ester layer is purified to obtain a product, and the deep eutectic solvent layer is recycled.
Further, in the present invention,
the deep eutectic solvent is mainly prepared from quaternary ammonium salt, organic acid and phenolic compounds according to a molar ratio of 1: 0.5-3: 0.1 to 2 percent of the raw materials are mixed and heated to 50 to 100 ℃ until the system becomes a clear and transparent eutectic substance.
Further, in the present invention,
the molar ratio of the monoacid acid (ester) to the monohydric alcohol compound in the first synthetic route is 1: 2-3: 1;
the molar ratio of the dibasic acid to the monohydric alcohol compound in the second synthetic route is 2: 5;
in the third synthetic route, the molar ratio of the monocarboxylic acid (ester) to the dihydric alcohol compound is 5: 1-5: 2.
Further, in the present invention, it is preferable that,
in the first synthetic route, in the reaction of the monoacid acid and the monohydric alcohol, the molar ratio of the deep eutectic solvent to the monohydric alcohol is 1: 1-1: 30;
in the second synthetic route, in the reaction of the dibasic acid and the monohydric alcohol, the molar ratio of the deep eutectic solvent to the monohydric alcohol is 1: 1-1: 30;
in the third synthetic route, in the reaction of monocarboxylic acid (ester) and dihydric alcohol, the molar ratio of the deep eutectic solvent to the olefine acid is 1: 1-1: 30.
Further, the ammonium salt is tetrabutylammonium bromide, tetrabutylammonium chloride, choline chloride, tetraethylammonium bromide or tetraethylammonium chloride.
Further, the phenolic compound is bisphenol A, 3, 5-di (tert-butyl) catechol, 2, 6-di-tert-butyl-p-methylphenol, hydroquinone monomethyl ether, p-tert-butyl catechol or di (tert-butyl) p-cresol.
Further, the organic acid is trichloroacetic acid, monochloroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, oxalic acid, citric acid, malonic acid, tartaric acid or succinic acid.
The invention has the beneficial effects that: the invention selects and utilizes quaternary ammonium salt-organic acid-phenol compound ternary systems to form hydrogen bonds and molecular interlocking to form a stable deep eutectic solvent which can be simultaneously used as a solvent, a catalyst and a polymerization inhibitor, has good catalytic efficiency on the complete esterification of olefine acid, and can stratify a product ester and the deep eutectic solvent in the reaction process so as to remove a reaction system when the carbon number of fatty alcohol is more than 3, promote the forward esterification reaction and be easy to separate and recycle; when using methyl enoate as substrate, the product ester can still be separated from the deep eutectic solvent, and the lower boiling point of the methanol accompanying the product ester can be easily separated during the preparation process. When the deep eutectic solvent is used as a catalyst, a water-carrying agent is not needed in the reaction, so that a large amount of organic solvent is avoided, the deep eutectic solvent can be directly layered with an ester layer after the reaction is finished, the ester layer can be subjected to simple treatment to obtain a product ester, the deep eutectic solvent can be applied to the next cycle, the catalytic effect is still ideal after ten cycles of monitoring, and compared with the traditional catalytic mode, the deep eutectic solvent is more environment-friendly. In addition, by comparing the binary deep eutectic solvent formed by the p-toluenesulfonic acid and the choline chloride and the ternary deep eutectic solvent formed by the p-toluenesulfonic acid, the choline chloride and the hydroquinone in the invention respectively used for catalyzing the reaction of the methacrylic acid and the lauryl alcohol under the same condition, the yield of the binary deep eutectic solvent is 89%, the yield of the ternary deep eutectic solvent is 95%, and the ternary deep eutectic solvent has better catalytic effect and higher yield obviously.
Drawings
FIG. 1 is a drawing showing the preparation of lauryl sorbate in example 11H nuclear magnetic spectrum.
FIG. 2 is a drawing showing the preparation of lauryl sorbate in example 113C nuclear magnetic spectrum.
FIG. 3 is a photograph of lauryl cinnamate of example 21H nuclear magnetic spectrum.
FIG. 4 is a photograph of lauryl cinnamate of example 213C nuclear magnetic spectrum.
FIG. 5 is a drawing of dilauryl maleate in example 31H nuclear magnetic spectrum.
FIG. 6 is a representation of dilauryl maleate in example 313C nuclear magnetic spectrum.
FIG. 7 is a graph of lauryl 4-pentenoate in example 41H nuclear magnetic spectrum.
FIG. 8 is a graph of lauryl 4-pentenoate in example 413C nuclear magnetic spectrum.
FIG. 9 is a drawing showing the preparation of cyclohexanol methacrylate in example 51H nuclear magnetic spectrum.
FIG. 10 is a drawing showing the preparation of cyclohexanol methacrylate in example 513C nuclear magnetic spectrum.
FIG. 11 is a drawing showing the preparation of sec-butyl methacrylate in example 61H nuclear magnetic spectrum.
FIG. 12 is a drawing showing the preparation of sec-butyl methacrylate in example 613C nuclear magnetic spectrum.
FIG. 13 is a drawing of lauryl methacrylate from example 71H nuclear magnetic spectrum.
FIG. 14 is a drawing of lauryl methacrylate from example 713C nuclear magnetic spectrum.
FIG. 15 is a drawing of lauryl acrylate of example 81H nuclear magnetic spectrum.
FIG. 16 is a drawing of lauryl acrylate of example 813C nuclear magnetic spectrum.
FIG. 17 is a drawing showing the preparation of 6-methyl-1-heptanol methacrylate in example 91H nuclear magnetic spectrum.
FIG. 18 is a drawing showing the preparation of 6-methyl-1-heptanol methacrylate in example 913C nuclear magnetic spectrum.
FIG. 19 is a schematic representation of neopentyl glycol dimethacrylate as in example 101H nuclear magnetic spectrum.
FIG. 20 is a schematic representation of neopentyl glycol dimethacrylate as in example 1013C nuclear magnetic spectrum.
FIG. 21 is a drawing showing the preparation of 1, 5-pentanediol dimethacrylate in example 111H nuclear magnetic spectrum.
FIG. 22 is a drawing showing the preparation of 1, 5-pentanediol dimethacrylate in example 1113C nuclear magnetic spectrum.
FIG. 23 is a photograph of glycidyl methacrylate in example 121H nuclear magnetic spectrum.
FIG. 24 is a schematic representation of the glycidyl methacrylate ester of example 1213C nuclear magnetic spectrum.
FIG. 25 is a photograph of benzyl methacrylate in example 131H nuclear magnetic spectrum.
FIG. 26 is a photograph of benzyl methacrylate in example 1313C nuclear magnetic spectrum.
FIG. 27 is the 3-chloro-1-propanol methacrylate of example 141H nuclear magnetic spectrum.
FIG. 28 is a 3-chloro-1-propanol methacrylate example 1413C nuclear magnetic spectrum.
Detailed Description
The preparation method for preparing the ester compound containing the olefin under the catalysis of the three-component deep eutectic solvent has the advantages of low raw material price, environmental friendliness, no need of a water-carrying agent, convenience in operation, recyclability of the deep eutectic solvent and the like.
The invention will be further illustrated with reference to the following specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. The simple replacement or improvement of the present invention by those skilled in the art is within the technical scheme of the present invention.
Example 1: synthesis of lauryl sorbate
A100 mL single-neck flask was charged with oxalic acid (7.2g, 0.08mol), tetraethylammonium chloride (13.3g, 0.08mol), and p-tert-butylcatechol (0.14g, 1%) and stirred at 80 ℃ for 30min until the system became a colorless and transparent liquid to give a deep eutectic solvent, and then added with sorbic acid (10.76g, 0.096mol) and lauryl alcohol (18.2mL, 0.08mol) and reacted at 90 ℃ for 8h, after completion of the reaction, the layers were separated, cooled, and the organic layer was taken as lauryl sorbate, yielding 83%. Adding new raw materials into the residual deep eutectic solvent layer, and repeating the above process, wherein the yield of the deep eutectic solvent is still over 80% after the deep eutectic solvent is recycled for 10 times.
A colorless liquid;1H NMR(400MHz,Chloroform-d)δ7.25(dd,J＝15.4,10.1Hz,1H),6.23–6.09(m,2H),5.78(d,J＝15.4Hz,1H),4.13(t,J＝6.7Hz,2H),1.85(d,J＝5.8Hz,3H),1.69–1.62(m,2H),1.38–1.27(m,18H),0.92–0.85(t,J＝6.5Hz 3H)；13C NMR(101MHz,Chloroform-d)δ167.4,144.9,139.1,129.8,119.1,64.4,31.9,29.7,29.7,29.6,29.5,29.4,29.3,28.7,26.0,22.7,18.6,14.1.
example 2: synthesis of lauryl cinnamate
In a 100mL single-neck flask, citric acid (15.4g, 0.08mol), choline chloride (5.6g, 0.08mol) and 3, 5-di (tert-butyl) catechol (0.18g, 1%) are added, stirred at 80 ℃ for 30min until the system becomes colorless and transparent liquid to obtain a deep eutectic solvent, cinnamic acid (14.2g, 0.096mol) and lauryl alcohol (18.2mL, 0.08mol) are added, the reaction is carried out at 90 ℃ for 8h, layering is carried out after the reaction is finished, the organic layer which is lauryl cinnamate is taken out after cooling, the yield is 98%, new raw materials are added into the residual deep eutectic solvent layer, the process is repeated, and the yield is still over 90% after the deep eutectic solvent is recycled for 10 times.
A colorless liquid;1H NMR(400MHz,Chloroform-d)δ7.71(d,J＝16.0Hz,1H),7.56–7.53(m,2H),7.42–7.38(m,3H),6.47(d,J＝16.0Hz,1H),4.23(t,J＝6.7Hz,2H),1.76–1.69(m,2H),1.34–1.29(m,18H),0.97–0.88(t,J＝6.5Hz,3H)；13C NMR(101MHz,Chloroform-d)δ167.1,144.6,134.5,130.2,128.9,128.1,118.3,64.7,32.0,29.7,29.7,29.6,29.6,29.4,29.3,28.8,26.0,22.7,14.2.
example 3: synthesis of dilauryl maleate
Adding trichloroacetic acid (13.1g, 0.08mol), tetrabutylammonium chloride (11.1g, 0.04mol) and bisphenol A (0.1g, 1%) into a 100mL single-neck flask, stirring at 50 ℃ for 30min until the system becomes colorless and transparent liquid to obtain a deep eutectic solvent, adding maleic acid (4.65g, 0.04mol) and lauryl alcohol (22.7mL, 0.1mol), reacting at 90 ℃ for 8h, layering after the reaction is finished, distilling the lauryl alcohol from the upper organic layer under reduced pressure (-100KPa) at 110 ℃ to obtain a product of dilauryl maleate with yield of 92%, putting the distilled lauryl alcohol into the deep eutectic solvent for continuous reaction, adding new raw materials, and repeating the above process, wherein the yield of the deep eutectic solvent is still more than 80% after 10 times of cyclic use.
A colorless liquid;1H NMR(400MHz,Chloroform-d)δ6.25(s,2H),4.19(t,J＝6.8Hz,4H),1.70–1.64(m,4H),1.38–1.23(m,36H),0.96–0.87(t,J＝6.6Hz,6H)；13C NMR(101MHz,Chloroform-d)δ165.1,133.6,65.5,31.9,29.6,29.6,29.6,29.5,29.3,29.2,28.5,25.9,22.7,14.1.
example 4: synthesis of 4-pentenoic acid lauryl ester
Adding p-chloroacetic acid (7.6g, 0.08mol), choline chloride (2.8g, 0.04mol) and di (tert-butyl) p-cresol (0.18g, 1%) into a 100mL single-neck flask, stirring at 50 ℃ for 30min until the system becomes colorless transparent liquid to obtain a deep eutectic solvent, adding 4-pentenoic acid (9.8mL, 0.096mol) and lauryl alcohol (18.2mL, 0.08mol), reacting at 100 ℃ for 6h, layering after the reaction is finished, distilling an upper organic layer under reduced pressure (-100KPa) at 70 ℃ to evaporate 4-pentenoic acid and recover to obtain a product of 4-pentenoic acid lauryl ester, putting the evaporated 4-pentenoic acid into the deep eutectic solvent for continuous reaction, adding new raw materials, repeating the above processes, wherein the yield of the deep eutectic solvent is still over 90% after 10 times of cyclic use.
A colorless liquid;1H NMR(400MHz,Chloroform-d)δ5.85–5.75(m,1H),5.06–4.96(m,2H),4.07(t,J＝6.7Hz,2H),2.41–2.32(m,4H),1.63–1.56(m,2H),1.34–1.20(m,18H),0.88(t,J＝6.7Hz,3H)；13C NMR(101MHz,Chloroform-d)δ173.1,136.7,115.4,64.5,33.6,31.9,29.6,29.6,29.6,29.5,29.4,29.2,28.9,28.6,25.9,22.7.
example 5: synthesis of cyclohexyl methacrylate
Adding p-toluenesulfonic acid (15.2g, 0.08mol), choline chloride (5.6g, 0.08mol) and hydroquinone (0.09g, 1%) into a 100mL single-neck flask, stirring for 30min at 70 ℃ until the system becomes colorless transparent liquid to obtain a deep eutectic solvent, adding methacrylic acid (8.2mL, 0.096mol) and cyclohexanol (8.3mL, 0.08mol), reacting for 6h at 100 ℃, layering after the reaction is finished, distilling the methacrylic acid at 40 ℃ by reduced pressure (-100KPa) in an upper organic layer, recovering to obtain a cyclohexyl methacrylate yield of 83%, adding a new raw material, repeating the above process, and recycling the deep eutectic solvent for 10 times, wherein the yield is still over 70%.
A colorless liquid;1H NMR(400MHz,Chloroform-d)δ6.09(s,1H),5.53(s,1H),4.87–4.81(m,1H),1.94(s,3H),1.89–1.82(m,2H),1.76–1.70(m,2H),1.56–1.26(m,6H)；13C NMR(101MHz,Chloroform-d)δ166.9,137.0,124.8,72.6,31.5,25.5,23.6,18.3.
example 6: synthesis of sec-butyl methacrylate
Adding trifluoromethanesulfonic acid (2.4mL, 0.03mol), tetrabutylammonium bromide (3.2g, 0.01mol) and di (tert-butyl) p-cresol (1.32g, 2%) into a 200mL single-neck flask, stirring at 50 ℃ for 30min until the system becomes colorless transparent liquid to obtain a deep eutectic solvent, adding methacrylic acid (25.4mL, 0.3mol) and sec-butyl alcohol (55.6mL, 0.6mol), heating and refluxing at 100 ℃ for 6h to finish the reaction, layering after the reaction is finished, distilling under reduced pressure (-100KPa) in an upper organic layer at 15 ℃ to evaporate and recover sec-butyl alcohol, obtaining the product sec-butyl methacrylate with the yield of 73%, adding new raw materials into the remaining deep eutectic solvent layer, and repeating the above process, wherein the yield of the deep eutectic solvent is still more than 60% after the deep eutectic solvent is recycled for 10 times.
A colorless liquid;1H NMR(400MHz,Chloroform-d)δ6.08(s,1H),5.52(s,1H),4.94–4.86(m,1H),1.94(s,3H),1.69–1.54(m,2H),1.24(d,J＝6.3Hz,3H),0.92(t,J＝7.5Hz,3H)；13C NMR(101MHz,Chloroform-d)δ167.1,136.9,124.8,72.4,28.8,19.4,18.3,9.6.
example 7: synthesis of lauryl methacrylate
The method comprises the following steps:
adding p-toluenesulfonic acid (15.2g, 0.08mol), choline chloride (5.6g, 0.08mol) and hydroquinone (0.09g, 1%) into a 100mL single-neck flask, stirring for 30min at 70 ℃ until the system becomes colorless transparent liquid to obtain a deep eutectic solvent, adding methacrylic acid (8.2mL, 0.096mol) and lauryl alcohol (18.2mL, 0.08mol), reacting for 6h at 100 ℃, layering after the reaction is finished, distilling the methacrylic acid at 40 ℃ by reduced pressure (-100KPa) in an upper organic layer, recovering to obtain a product lauryl alcohol methacrylate yield of 94%, putting the distilled methacrylic acid into the deep eutectic solvent for continuous reaction, adding new raw materials, and repeating the above process, wherein the yield of the deep eutectic solvent is still over 90% after 13 times of recycling.
The method 2 comprises the following steps:
adding p-toluenesulfonic acid (15.2g, 0.08mol), choline chloride (5.6g, 0.08mol) and hydroquinone (0.09g, 2%) into a 100mL single-neck flask, stirring for 30min at 70 ℃ until the system becomes colorless transparent liquid to obtain a deep eutectic solvent, adding methyl methacrylate (12.8mL, 0.12mol) and lauryl alcohol (18.2mL, 0.08mol), heating and refluxing at 100 ℃ for 6h, absorbing methanol in the reaction process by water through a water separator, layering after the reaction is finished, distilling an upper organic layer under reduced pressure (-100KPa) to evaporate methyl methacrylate at 15 ℃ and recovering to obtain a product lauryl methacrylate yield of 86%, adding a new raw material, and repeating the post-treatment process, wherein the yield of the deep eutectic solvent is still over 70% after 10 times of cyclic use.
A colorless liquid;1H NMR(400MHz,Chloroform-d)δ6.05(s,1H),5.48(s,1H),4.09(t,J＝6.7Hz,2H),1.89(s,3H),1.68–1.61(m,2H),1.35–1.24(m,18H),0.83(t,J＝6.7Hz,3H)；13C NMR(101MHz,Chloroform-d)δ167.4,136.5,125.0,64.7,31.9,29.6,29.6,29.6,29.5,29.3,29.2,28.6,26.0,22.7,18.2,14.0.
example 8: synthesis of lauryl acrylate
Adding p-toluenesulfonic acid (15.2g, 0.08mol), choline chloride (5.6g, 0.08mol) and hydroquinone (0.09g, 1%) into a 100mL single-neck flask, stirring for 30min at 70 ℃ until the system becomes colorless transparent liquid to obtain a deep eutectic solvent, adding acrylic acid (6.6mL, 0.096mol) and lauryl alcohol (18.2mL, 0.08mol), reacting for 6h at 100 ℃, layering after the reaction is finished, distilling acrylic acid from an upper organic layer at 15 ℃ by reduced pressure distillation (-100KPa) to recover, so as to obtain a product lauryl alcohol acrylate yield of 92%, adding a new raw material into the deep eutectic solvent layer, repeating the post-treatment process, and recycling the deep eutectic solvent for 10 times, wherein the yield is still more than 80%.
A colorless liquid;1H NMR(400MHz,Chloroform-d)δ6.41(dd,J＝17.4Hz,1.5Hz,1H),6.13(dd,J＝17.3Hz,10.4Hz,1H),5.82(dd,J＝10.4Hz,1.5Hz,1H),4.16(t,J＝6.7Hz,2H),1.72–1.64(m,2H),1.40–1.25(m,18H),0.89(t,J＝6.6Hz,3H)；13C NMR(101MHz,Chloroform-d)δ166.3,130.4,128.7,64.7,31.9,29.6,29.6,29.5,29.4,29.3,29.3,28.6,25.9,22.7,14.1.
example 9: synthesis of methacrylic acid 6-methyl-1-heptanol ester
Adding p-toluenesulfonic acid (15.2g, 0.08mol), choline chloride (5.6g, 0.08mol) and hydroquinone (0.09g, 1%) into a 100mL single-neck flask, stirring at 70 ℃ for 30min until the system becomes colorless and transparent liquid to obtain a deep eutectic solvent, adding methacrylic acid (8.2mL, 0.096mol) and 6-methyl-1-heptanol (12.7mL, 0.08mol), reacting at 100 ℃ for 6h, demixing after the reaction is finished, distilling an upper organic layer under reduced pressure (-100KPa) at 40 ℃ to evaporate and recover the methacrylic acid to obtain a product of 6-methyl-1-heptanol ester yield of methacrylic acid of 94%, adding a new raw material, repeating the above process, wherein the yield of the deep eutectic solvent is still over 90% after 10 times of recycling.
A colorless liquid;1H NMR(400MHz,Chloroform-d)δ6.01(s,1H),5.44(s,1H),4.02–3.93(t,J＝5.7Hz,2H),1.85(s,3H),1.57–1.51(m,1H),1.34–1.18(m,8H),0.82(d,J＝7.4Hz,6H)；13C NMR(101MHz,Chloroform-d)δ167.2,136.5,124.8,66.8,38.7,30.5,28.9,23.9,22.9,18.1,13.8,10.9.
example 10: synthesis of neopentyl glycol dimethacrylate
Adding p-toluenesulfonic acid (15.2g, 0.08mol), choline chloride (5.6g, 0.08mol) and hydroquinone (0.09g, 2%) into a 100mL single-neck flask, stirring at 70 ℃ for 30min until the system becomes colorless transparent liquid to obtain a deep eutectic solvent, adding methacrylic acid (8.5mL, 0.1mol) and neopentyl glycol (4mL, 0.04mol), reacting at 100 ℃ for 6h, layering after the reaction is finished, distilling the methacrylic acid in an upper organic layer under reduced pressure (-100KPa) at 40 ℃ to recover, so as to obtain a neopentyl glycol dimethacrylate yield of 91%, adding a new raw material into the deep eutectic solvent, repeating the above process, and obtaining a yield of more than 80% after the deep eutectic solvent is recycled for 10 times.
A colorless liquid;1H NMR(400MHz,Chloroform-d)δ6.05(s,2H),5.51(s,2H),3.93(s,4H),1.89(s,6H),0.98(s,6H)；13C NMR(101MHz,Chloroform-d)δ167.0,136.2,125.5,69.3,34.9,21.8,18.2.
example 11: synthesis of 1, 5-dimethyl acrylic acid pentanediol ester
Into a 100mL single-neck flask, malonic acid (1.04g, 0.01mol), choline chloride (0.7g, 0.01mol), and 2, 6-di-tert-butyl-p-methylphenol (0.07g, 0.5%) were added, and stirred at 100 ℃ for 30min until the system became a colorless and transparent liquid to obtain a deep eutectic solvent, methacrylic acid (25.5mL, 0.3mol) and 1, 5-pentanediol (6.45mL, 0.06mol) were added, and the mixture was reacted at 90 ℃ for 10h, after the reaction was completed, the layers were separated, and the upper organic layer was distilled under reduced pressure (-100KPa) at 40 ℃ to distill off methacrylic acid and recover the product, i.e., 1, 5-pentanediol dimethacrylate, yielding 93%. Adding new raw materials into the deep eutectic solvent, and repeating the above process, wherein the yield of the deep eutectic solvent is still more than 70% after the deep eutectic solvent is recycled for 10 times.
A colorless liquid;1H NMR(400MHz,Chloroform-d)δ6.02(s,2H),5.47(s,2H),4.09(t,J＝6.5Hz,4H),1.82(s,6H),1.69–1.62(m,4H),1.46–1.38(m,2H)；13C NMR(101MHz,Chloroform-d)δ167.5,136.4,125.3,64.4,28.2,22.6,18.3.
example 12: synthesis of glycidyl methacrylate
Adding p-toluenesulfonic acid (3.8g, 0.02mol), choline chloride (1.4g, 0.02mol) and hydroquinone (0.09g, 1%) into a 100mL single-neck flask, stirring at 70 ℃ for 30min until the system becomes colorless and transparent liquid to obtain a deep eutectic solvent, adding methacrylic acid (20.4mL, 0.24mol) and glycidol (5.2mL, 0.08mol), reacting at 70 ℃ for 12h, extracting with dichloromethane after the reaction is finished, removing dichloromethane from a lower organic layer at normal pressure, distilling under reduced pressure (-100KPa) at 40 ℃ to evaporate methacrylic acid and recovering to obtain a product glycidyl methacrylate yield of 87%, adding a new raw material into the deep eutectic solvent, repeating the above process, and obtaining the yield of over 60% after the deep eutectic solvent is recycled for 10 times.
A colorless liquid;1H NMR(400MHz,Chloroform-d)δ6.16(s,1H),5.61(s,1H),4.48(d,J＝12.5Hz,1H),4.00(d,J＝12.3Hz,1H),3.28–3.23(m,1H),2.85(d,J＝4.6Hz,1H),2.67(d,J＝2.6Hz,1H),1.96(s,3H)；13C NMR(101MHz,Chloroform-d)δ167.0,135.9,126.2,65.1,49.4,44.6,18.2.
example 13: synthesis of benzyl methacrylate
In a 100mL single-neck flask, tartaric acid (1.5g, 0.01mol), choline chloride (1.4g, 0.02mol) and hydroquinone (0.11g, 0.1%) are added and stirred at 90 ℃ for 30min until the system becomes colorless and transparent liquid to obtain a deep eutectic solvent, methacrylic acid (47.5mL, 0.6mol) and benzyl alcohol (10.4mL, 0.1mol) are added and reacted at 130 ℃ for 4h, after the reaction is finished, dichloromethane is used for extraction and layering, dichloromethane is distilled out at normal pressure from a lower organic layer, methacrylic acid is distilled out at 40 ℃ under reduced pressure (-100KPa) and recovered, the yield of benzyl methacrylate product is 88%, new raw materials are added into the deep eutectic solvent, the process is repeated, and the yield of the deep eutectic solvent is still over 60% after 10 times of recycling.
A colorless liquid;1H NMR(400MHz,Chloroform-d)δ7.41–7.33(m,5H),6.17(s,1H),5.59(s,1H),5.20(s,2H),1.98(s,3H)；13C NMR(101MHz,Chloroform-d)δ167.3,136.3,136.2,128.6,128.2,128.0,125.8,66.4,18.4.
example 14: synthesis of 3-chloro-1-propanol methacrylate
Adding succinic acid (3.6g, 0.03mol), tetraethylammonium bromide (2.1g, 0.01mol) and hydroquinone monomethyl ether (0.25g, 1%) into a 100mL single-neck flask, stirring at 80 ℃ for 30min until the system becomes colorless and transparent liquid to obtain a deep eutectic solvent, adding methacrylic acid (33.9mL, 0.4mol) and 3-chloro-1-propanol (16.7mL, 0.2mol), reacting at 120 ℃ for 4h, extracting with dichloromethane after the reaction is finished, distilling dichloromethane from an upper dichloromethane layer at normal pressure, distilling methacrylic acid at 40 ℃ by reduced pressure distillation (-100KPa) and recovering to obtain a product of 3-chloro-1-propanol methacrylate with a yield of 72%, adding a new raw material into the deep eutectic solvent, repeating the above process, wherein the yield of the deep eutectic solvent is still over 70% after 10 times of recycling.
A colorless liquid;1H NMR(400MHz,Chloroform-d)δ6.19–6.09(s,1H),5.60(s,1H),4.32(t,J＝6.0Hz,2H),3.66(t,J＝6.4Hz,2H),2.17(p,J＝6.3Hz,2H),1.97(s,3H)；13C NMR(101MHz,Chloroform-d)δ167.3,136.2,125.7,61.4,41.3,31.7,18.3.
Claims (9)
1. a method for preparing ester compound containing olefin by catalysis of deep eutectic solvent is characterized in that carboxylic acid containing olefin or carboxylic ester containing olefin and alcohol compound are used as raw materials, esterification or ester exchange reaction is carried out in the deep eutectic solvent under the heating condition to generate the ester compound containing olefin, and the deep eutectic solvent can be used as solvent, catalyst and polymerization inhibitor at the same time. The synthetic route is as follows:
synthetic route 1
Synthetic route two
Synthetic route III
In the formula: n is greater than or equal to 0; r1Is alkyl, alkenyl or phenyl; r2、R3、R5And R6Is H or alkyl, the same or different; r4Is alkyl or haloalkyl;
the reaction temperature is 70-130 ℃, and the reaction time is 4-12 hours;
after the reaction is finished, the deep eutectic solvent and the ester layer are directly layered, the ester layer is purified to obtain a product, and the deep eutectic solvent layer is recycled.
2. The method as claimed in claim 1, wherein the deep eutectic solvent consists essentially of a quaternary ammonium salt, an organic acid and a phenolic compound in a molar ratio of 1: 0.5-3: 0.1 to 2 percent of the components are mixed and heated to 50 to 100 ℃ until the system becomes a clear and transparent eutectic.
3. The method according to claim 1 or 2,
in the first synthesis route, the molar ratio of the monoacid acid/ester to the monohydric alcohol compound is 1: 2-3: 1;
in the second synthetic route, the molar ratio of the dibasic acid to the monohydric alcohol compound is 2: 5;
in the third synthetic route, the molar ratio of the monoacid acid/ester to the dihydric alcohol compound is 5: 1-5: 2.
4. The method of synthesis according to claim 3,
in the first synthetic route, in the reaction of the monoacid olefine acid/ester and the monohydric alcohol, the molar ratio of the deep eutectic solvent to the monohydric alcohol is 1: 1-1: 30;
in the second synthetic route, in the reaction of the dibasic acid and the monohydric alcohol, the molar ratio of the deep eutectic solvent to the monohydric alcohol is 1: 1-1: 30;
in the third synthetic route, in the reaction of monocarboxylic acid/ester and dihydric alcohol, the molar ratio of the deep eutectic solvent to olefine acid is 1: 1-1: 30.
5. A synthesis method according to claim 2 or 4, characterized in that the ammonium salt is tetrabutylammonium bromide, tetrabutylammonium chloride, choline chloride, tetraethylammonium bromide or tetraethylammonium chloride.
6. A method of synthesis according to claim 3, characterized in that the ammonium salt is tetrabutylammonium bromide, tetrabutylammonium chloride, choline chloride, tetraethylammonium bromide or tetraethylammonium chloride.
7. The method of claim 5, wherein the phenolic compound is bisphenol A, 3, 5-di (tert-butyl) catechol, 2, 6-di-tert-butyl-p-methylphenol, hydroquinone monomethyl ether, p-tert-butyl catechol, or di (tert-butyl) p-cresol.
8. The method of claim 6, wherein the phenolic compound is bisphenol A, 3, 5-di (tert-butyl) catechol, 2, 6-di-tert-butyl-p-methylphenol, hydroquinone monomethyl ether, p-tert-butyl catechol, or di (tert-butyl) p-cresol.
9. The method of claim 7 or 8, wherein the organic acid is trichloroacetic acid, monochloroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, oxalic acid, citric acid, malonic acid, tartaric acid, or succinic acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023249130A3 (en) * | 2022-11-18 | 2024-03-14 | 株式会社日本触媒 | (meth)acrylic acid ester production method |
| WO2023249129A3 (en) * | 2022-11-18 | 2024-03-21 | 株式会社日本触媒 | (meth)acrylic acid ester production method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160122676A1 (en) * | 2014-11-03 | 2016-05-05 | Exxonmobil Research And Engineering Company | Low transition temperature mixtures or deep eutectic solvents and processes for preparation thereof |
| CN108484405A (en) * | 2018-04-24 | 2018-09-04 | 六盘水师范学院 | A kind of carboxylic acid aryl esters compounds process for production thereof based on alkenyl carboxylate's ester exchange reaction |
| CN111269115A (en) * | 2020-02-26 | 2020-06-12 | 陕西科技大学 | Preparation method of cinnamate in eutectic solvent |
| CN112552172A (en) * | 2021-01-25 | 2021-03-26 | 华东理工大学 | Method for synthesizing methyl cinnamate based on eutectic solvent catalyst |
| CN112679346A (en) * | 2021-01-22 | 2021-04-20 | 华东理工大学 | Method for catalytically synthesizing p-tert-butyl methyl benzoate based on eutectic solvent |
| CN112812008A (en) * | 2021-01-11 | 2021-05-18 | 大连理工大学 | Method for preparing diacid diester compound under catalysis of deep eutectic solvent |
| CN114105769A (en) * | 2021-12-10 | 2022-03-01 | 华东理工大学 | Method for catalytically synthesizing n-propyl cinnamate based on choline chloride eutectic solvent |
-
2022
- 2022-03-28 CN CN202210309393.9A patent/CN114656358B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160122676A1 (en) * | 2014-11-03 | 2016-05-05 | Exxonmobil Research And Engineering Company | Low transition temperature mixtures or deep eutectic solvents and processes for preparation thereof |
| CN108484405A (en) * | 2018-04-24 | 2018-09-04 | 六盘水师范学院 | A kind of carboxylic acid aryl esters compounds process for production thereof based on alkenyl carboxylate's ester exchange reaction |
| CN111269115A (en) * | 2020-02-26 | 2020-06-12 | 陕西科技大学 | Preparation method of cinnamate in eutectic solvent |
| CN112812008A (en) * | 2021-01-11 | 2021-05-18 | 大连理工大学 | Method for preparing diacid diester compound under catalysis of deep eutectic solvent |
| CN112679346A (en) * | 2021-01-22 | 2021-04-20 | 华东理工大学 | Method for catalytically synthesizing p-tert-butyl methyl benzoate based on eutectic solvent |
| CN112552172A (en) * | 2021-01-25 | 2021-03-26 | 华东理工大学 | Method for synthesizing methyl cinnamate based on eutectic solvent catalyst |
| CN114105769A (en) * | 2021-12-10 | 2022-03-01 | 华东理工大学 | Method for catalytically synthesizing n-propyl cinnamate based on choline chloride eutectic solvent |
Non-Patent Citations (5)
| Title |
|---|
| CHEN SHEN ET AL.: "A green one-pot method for simultaneous extraction and transesterification of seed oil catalyzed by a p-toluenesulfonic acid based deep eutectic solvent", 《INDUSTRIAL CROPS & PRODUCTS》 * |
| V.FISCHER ET AL.: "Eco-friendly onepotsynthesisofcaffeicacidphenethylester(CAPE) via anin-situformeddeepeutecticsolvent", 《SUSTAINABLECHEMISTRYANDPHARMACY》 * |
| WEI LIU ET AL.: "p-Toluenesulfonic Acid-based Deep Eutectic Solvent as Transesterification Catalyst for Biodiesel Production", 《JOURNAL OF OLEO SCIENCE》 * |
| 岳旭东等: "低共熔溶剂在有机合成和萃取分离中的应用进展", 《化工进展》 * |
| 蒋宇佳等: "深共融溶剂催化制备二酯类化合物", 《精细化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023249130A3 (en) * | 2022-11-18 | 2024-03-14 | 株式会社日本触媒 | (meth)acrylic acid ester production method |
| WO2023249129A3 (en) * | 2022-11-18 | 2024-03-21 | 株式会社日本触媒 | (meth)acrylic acid ester production method |
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