CN116768842A - Method for synthesizing cyclic carbonate - Google Patents

Method for synthesizing cyclic carbonate Download PDF

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CN116768842A
CN116768842A CN202310738234.5A CN202310738234A CN116768842A CN 116768842 A CN116768842 A CN 116768842A CN 202310738234 A CN202310738234 A CN 202310738234A CN 116768842 A CN116768842 A CN 116768842A
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epoxide
formula
catalyst
cyclic carbonate
reaction
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郭凯
曹绍菊
何军
李振江
张智浩
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Nanjing Tech University
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Nanjing Tech University
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Abstract

The invention discloses a method for synthesizing cyclic carbonate, belonging to the technical field of organic catalysis. The invention adopts a brand-new organic ion pair catalyst to realize the [3+2] cycloaddition reaction of epoxide and carbon dioxide, and the cyclic carbonate is obtained with high selectivity. The catalytic reaction condition is mild (normal pressure), the application range of the substrate is wide (the cyclic carbonate contains double epoxide and internal epoxide), the obtained cyclic carbonate has no metal residue, and the cyclic carbonate has great potential for commercial application in the fields of microelectronics, polymer preparation and the like with strict control on the content of the metal residue.

Description

Method for synthesizing cyclic carbonate
Technical Field
The invention belongs to the technical field of organic catalysis, and particularly relates to a method for synthesizing five-membered cyclic carbonate and application thereof.
Background
Since the industrial revolution, the massive emission of greenhouse gases has led to serious environmental problems such as global temperature rise, melting of two-pole glaciers, frequent occurrence of unusual extreme weather, etc. The concentration of carbon dioxide in the lower atmosphere gradually rises from less than 268ppm to 420ppm, wherein the total carbon dioxide emission is 2022 in ChinaThe amount is more than 340 hundred million tons. Since the "two carbon" policy, chemical fixation of carbon dioxide has become a research hotspot. Carbon dioxide is a linear hetero-accumulation olefin with thermodynamic stability and kinetic inertia, the activation energy is 395.5kJ/mol, and the carbon dioxide has a very high energy barrier, so that the key for solving the problem is to select a high-energy substrate and design a catalyst reasonably. Epoxide is a commodity chemical and therefore inexpensive. Five-membered cyclic carbonates are a class of five-membered heterocyclic compounds containing oxygen. Cyclic carbonates are low toxicity biodegradable liquids and are mainly used as polymerization monomers for aprotic polar solvents (Curr. Opin. Green Sust. Chem.29,2021, 100457), electrolytes in secondary batteries, intermediates in fine chemical synthesis and polycarbonate-based polymers (ACS Sustin. Chem. Eng.4,2016,1032; polym. Chem.4,2013, 4545) and non-isocyanate polyurethanes (NIPU). Among them, NIPU is considered as one of the effective means for replacing the conventional petroleum-based polyurethane in the future, and is obtained by directly synthesizing a bicyclic carbonate and a diamine in one step. Compared with polyurethane prepared from traditional virulent raw materials such as phosgene, isocyanate and the like, the bio-based NIPU has biodegradability and biocompatibility, is more environment-friendly, and accords with the concept of sustainable development. From epoxides and CO 2 [3+2 of (2)]Cycloaddition (CCE) is an industrially applicable strategy for chemically fixing carbon dioxide from bulk chemicals into high value-added products.
Wherein R in the above formula represents each of fatty alkyl, aromatic alkane and glycidyl ether, wherein R 1 And R is 2 May be the same group.
Catalysts designed for this reaction are known to date and are largely divided into organic catalysts and metal catalysts. The metal catalyst has high universal activity and can catalyze CCE reaction under mild condition. However, there are some drawbacks to metal catalysts, such as the relatively high cost of rare earth metals (rare-earth metals) (ACS Sustainable chem. Eng.2016,4, 4805-4814), and the complex synthesis procedures of many metal catalysts (Dalton Trans, 2011,40,3885-3902), often requires the addition of a cocatalyst (ACS catalyst.2018, 8, 665-672), and metal residues limit further high-end applications of the product. The organic catalysts have been widely studied, including quaternary ammonium, phosphonium or imidazolium salts, but these catalysts are generally not effective in catalyzing internal epoxides (ChemSusChem 2012,5, 2032-2038) and require, for example, high temperatures, high CO 2 Severe reaction conditions (Green chem.,2016,18,4611-4615) such as pressure (ACS catalyst.2019, 9, 1895-1906), anhydrous oxygen free (ChemSusChem 2018,11,4262-426), and the like, which are phase-changed to increase cost and energy consumption, fundamentally resulting in CO 2 Is not utilized for industrial production applications.
Disclosure of Invention
The invention aims to provide a method for synthesizing five-membered cyclic carbonate and application thereof. The poor suitability of the commercial catalysts for di/polyepoxides and internal epoxides limits the further processing and use of the cyclic carbonates. The invention adopts a brand-new organic ion pair catalyst to realize the [3+2] cycloaddition reaction of epoxide and carbon dioxide, and the cyclic carbonate is obtained with high selectivity. The catalytic reaction condition is mild (normal pressure), the application range of the substrate is wide (the cyclic carbonate contains double epoxide and internal epoxide), the obtained cyclic carbonate has no metal residue, and the cyclic carbonate has great potential for commercial application in the fields of microelectronics, polymer preparation and the like with strict control on the content of the metal residue.
The invention provides for the first time that an adjustable strong Lewis acid is used as Hydrogen Bond Donor (HBD) and nucleophilic halogen anion (X) – ) The bifunctional organic catalyst of (2) catalyzes the epoxide to form cyclic carbonate with high selectivity with carbon dioxide. The target catalyst can be obtained by simply reacting commercially available pentachlorocyclopropane with easily available secondary amine, and the post-treatment is simple and easy to operate.
The present invention addresses and solves the problems found in the actual need by catalyzing the synthesis of epoxides of different substituents, including substrates of bisepoxides and internal epoxides, using a difunctional cyclopropene ion pair as a hydrogen bond donor and a nucleophilic anion. The organic molecular catalytic system is firstly applied to cycloaddition reaction of epoxide and carbon dioxide, and has mild condition and high selectivity.
The technical scheme for achieving the above-mentioned goal is as follows:
a method for synthesizing cyclic carbonate uses a catalyst shown in a formula I, and forms cyclic carbonate through epoxide shown in a formula II and carbon dioxide:
wherein the method comprises the steps of
X is selected from Cl, br, I, CH 3 COO(OAc)；
Wherein R is 1 Selected from methyl, ethyl, butyl, cyclohexyl, isopropyl. R is R 2 Selected from hydrogen, methyl, methoxy, nitro, trifluoromethyl, chlorine, bromine, iodine. E is selected from O, S;
the epoxide is selected from the structures of formula II:
R 3 、R 4 selected from hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, alkenyl having 1 to 4 carbon atoms, phenyl, halogen-or alkyl-substituted aryl, halogen-substituted alkyl, R 5 -O-CH 2 -, said R 5 Selected from phenyl, phenyl substituted with alkyl of 1 to 3 carbon atoms, allyl or straight or branched alkyl of 1 to 4 carbon atoms, allyl glyceride and bisphenol a glycerol ether.
Preferably R 1 Selected from cyclohexyl, isopropyl, R 2 Selected from hydrogen, methyl, E is selected from S
Preferably R 3 、R 4 Selected from hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, 1-butenyl, phenyl, halogen-or alkyl-substituted phenyl, chlorine-or bromine-substituted alkyl, R 5 –O–CH 2 -, said R 5 Selected from phenyl, phenyl substituted with alkyl of 1 to 3 carbon atoms, allyl glyceride and bisphenolAnd A glycerol ether.
Preferably, the catalyst of formula I is selected from the following structures:
preferably, the epoxide of formula II is selected from phenyl glycidyl ether, m-phenyl glycidyl ether, styrene oxide, 1-trifluoro-2, 3-epoxypropane, epichlorohydrin, 1, 2-epoxy-5-hexene, allyl glycidyl ether, methyl acrylate glycidyl ether, t-butyl glycidyl ether, cyclohexene oxide, 2, 3-diphenylethylene oxide.
The structure of the epoxide is shown in the following table:
the catalyst shown in the formula I is selected from the following structures:
the epoxide of formula II is selected from the following structures:
preferably, the reaction temperature of the method for synthesizing the cyclic carbonate is 25-120 ℃, the reaction time is 6-48 hours, the carbon dioxide pressure is 0.1-1 Mpa, and the molar ratio of the catalyst shown in the formula I to the epoxide shown in the formula II is 10:1 to 100:1.
preferably, the reaction temperature of the preparation method is 100 ℃, the reaction time is 6 hours, the pressure of carbon dioxide is 0.1Mpa, and the molar ratio of the catalyst shown in the formula I to the epoxide shown in the formula II is 100:1.
preferably, the specific steps of the method include:
(1) The catalyst shown in the formula I and the epoxide shown in the formula II are mixed according to the molar ratio of 100:1 into a reaction vessel;
(2) Filling 0.1Mpa carbon dioxide, and placing the reaction vessel in a heating reactor preheated in advance;
(3) Reacting for 6-12 hours, cooling, adding normal hexane into the reaction liquid, and washing to obtain the cyclic carbonate.
Advantageous effects
(1) Compared with the cyclic carbonate synthesized by using a metal catalyst in the prior art, the cyclic carbonate with high added value can be efficiently synthesized by the catalytic system, has the characteristics of high selectivity, no metal residue, mild conditions and the like, has wide substrate practicability, and is still used for double/multiple epoxy substrates. Has great potential for commercial application in the fields of biological medicine, polymer preparation and the like.
(2) The catalytic system of the invention uses strong Lewis acid as Hydrogen Bond Donor (HBD) and halogen ion (X) – ) Difunctional catalytic epoxides with carbon dioxide [3+2]]Cycloaddition to synthesize cyclic carbonates. Lewis acid as hydrogen bond donor activates epoxide and stabilizes ionic intermediate, X – The nucleophilicity is enhanced by mutual exclusion with the cyclopropenyl cation, attacking the epoxide to open it.
(3) The invention can catalyze CCE reaction under the conditions of normal pressure and low catalytic load, has short time and low temperature, and can obtain the cyclic carbonate with extremely high reaction selectivity. Compared with other conditions of high temperature, high pressure, long reaction time, high catalyst load and the like, the method for synthesizing the cyclic carbonate has the advantage of mild reaction conditions. In conclusion, compared with other existing catalytic systems, the catalyst has the obvious advantages of mildness, high efficiency, easiness in preparation, no metal residue and the like.
Drawings
Embodiments of the present invention will be described in detail with reference to the accompanying drawings, in which
FIG. 1 nuclear magnetic resonance hydrogen spectrum (400 MHz, chloroform-d) of epoxide A corresponding product
FIG. 2 Nuclear magnetic resonance carbon Spectrometry (101 MHz, chloroform-d) of the corresponding product of epoxide A
FIG. 3 nuclear magnetic resonance hydrogen spectrum of epoxide B corresponding product (400 MHz, chloroform-d)
FIG. 4 Nuclear magnetic resonance carbon Spectrometry (101 MHz, chloroform-d) for epoxide B corresponding product
FIG. 5 nuclear magnetic resonance hydrogen spectrum of epoxide C corresponding product (400 MHz, chloroform-d)
FIG. 6 Nuclear magnetic resonance carbon Spectrometry (101 MHz, chloroform-d) for epoxide C corresponding product
FIG. 7 nuclear magnetic resonance hydrogen spectrum of epoxide D corresponding product (400 MHz, chloroform-D)
FIG. 8 Nuclear magnetic resonance carbon Spectrometry (101 MHz, chloroform-D) for the corresponding product of epoxide D
FIG. 9 nuclear magnetic resonance hydrogen spectrum of epoxide E corresponding product (400 MHz, chloroform-d)
FIG. 10 nuclear magnetic resonance carbon spectrum (101 MHz, chloroform-d) of epoxide E corresponding product
FIG. 11 nuclear magnetic resonance hydrogen spectrum of epoxide F corresponding product (400 MHz, chloroform-d)
FIG. 12 nuclear magnetic resonance carbon spectrum (101 MHz, chloroform-d) of epoxide F corresponding product
FIG. 13 nuclear magnetic resonance hydrogen spectrum of epoxide G corresponding product (400 MHz, chloroform-d)
FIG. 14 nuclear magnetic resonance carbon spectrum (101 MHz, chloroform-d) of epoxide G corresponding product
FIG. 15 nuclear magnetic resonance hydrogen spectrum of epoxide H corresponding product (400 MHz, chloroform-d)
FIG. 16 Nuclear magnetic resonance carbon Spectrometry (101 MHz, chloroform-d) for epoxide H corresponding product
FIG. 17 nuclear magnetic resonance hydrogen spectrum of epoxide I corresponding product (400 MHz, chloroform-d)
FIG. 18 Nuclear magnetic resonance carbon spectrum of the corresponding product of epoxide I (101 MHz, chloroform-d)
FIG. 19 nuclear magnetic resonance hydrogen spectrum of epoxide J corresponding product (400 MHz, chloroform-d)
FIG. 20 nuclear magnetic resonance carbon spectrum of the corresponding product of epoxide J (101 MHz, chloroform-d)
FIG. 21 nuclear magnetic resonance hydrogen spectrum of epoxide K corresponding product (400 MHz, chloroform-d)
FIG. 22 Nuclear magnetic resonance carbon spectrum of epoxide K corresponding product (101 MHz, chloroform-d)
FIG. 23 nuclear magnetic resonance hydrogen spectrum of epoxide L corresponding product (400 MHz, chloroform-d)
FIG. 24 nuclear magnetic resonance carbon spectrum (101 MHz, chloroform-d) of epoxide L corresponding product
Fig. 25 to 26: nuclear magnetic resonance Hydrogen Spectrometry and carbon Spectrometry for the catalyst of example 1
Fig. 27 to 28: nuclear magnetic resonance Hydrogen Spectrometry and carbon Spectrometry for the catalyst of example 2
Fig. 29 to 30: nuclear magnetic resonance Hydrogen Spectrometry and carbon Spectrometry for the catalyst of example 3
Fig. 31: nuclear magnetic resonance Hydrogen Spectrometry for non-isocyanate polyurethane in example 17
Detailed Description
The invention will be further illustrated by the following examples, which are intended to illustrate, but not to limit, the invention. It will be understood by those of ordinary skill in the art that these examples are not limiting of the invention in any way and that appropriate modifications and data changes may be made thereto without departing from the spirit and scope of the invention.
The nuclear magnetic resonance hydrogen and carbon spectra involved in the examples were determined using a Bruker Assetnd TM-400 nuclear magnetic resonance analyzer from Bruker, inc. (Bruker), and the deuterating reagent used was deuterated chloroform (CDCl) 3 ) And deuterated dimethyl sulfoxide (DMSO-d) 6 )。
The raw materials used in the subordinate examples were all purchased from saen chemical technology (Shanghai) limited.
The catalytic system used in the examples had the following structure:
the epoxide used in the examples has the following structure:
example 1:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Catalyst 1 (2.6 mg,0.005mmol, 0.001equiv.) was added with inert gas. Epoxide A (5 mmol,1.0 equiv) was then added and carbon dioxide (0.1 MPa) was added. The reactor was reacted at 100℃for 6 hours on a heated stirrer with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and allowed to cool naturally, and was washed three times with 30 equivalents of n-hexane to give a colorless oil, which was dried to a constant weight, and the conversion rate reached 32% and the selectivity was 99%. The hydrogen spectrum of the product is shown in figure 1, and the carbon spectrum of the product is shown in figure 2. The spectrogram data are: delta 7.49-7.40 (m, 3H), 7.40-7.28 (m, 2H), 5.67 (t, j=8.0 hz, 1H), 4.79 (t, j=8.4 hz, 1H), 4.33 (dd, j=8.7, 7.8hz, 1H).
The preparation method of the catalyst 1 comprises the following steps: pentachlorocyclopropane (1 eq) was added dropwise to a dichloromethane solution of diisopropylamine (6 eq) in ice bath. The reaction was carried out at room temperature for 12 hours, and bubbling ammonia gas was carried out in an ice bath for 1 hour. After filtration, concentrated and dried, the solid was washed with 3M NaOH to give an off-white solid. Phenyl isothiocyanate (2 eq) was added and reacted for 1 hour. The reaction was washed with 3M HCl and dried to give catalyst 1. The hydrogen spectrum of the product is shown in FIG. 25, and the carbon spectrum of the product is shown in FIG. 26. The spectrogram data are: 1 δ12.02(s,1H),11.76(s,1H),7.85(d,J＝7.9Hz,2H),7.33(t,J＝7.6Hz,2H),7.15(t,J＝7.4Hz,1H),4.13(hept,J＝6.8Hz,4H),1.40(d,J＝6.8Hz,24H).
example 2:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Catalyst 1 (26 mg,0.05mmol,0.01 equiv) was added with inert gas. Epoxide A (5 mmol,1.0 equiv) was then added and carbon dioxide (0.1 MPa) was added. The reactor was reacted at 120℃for 6 hours on a heated stirrer with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, and was washed three times with 30 equivalents of n-hexane to give a colorless oil, which was dried to a constant weight, and the conversion rate reached 54% and the selectivity was 99%.
Example 3:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Catalyst 2 (28 mg,0.05mmol,0.01 equiv) was added with inert gas. Epoxide A (5 mmol,1.0 equiv) was then added and carbon dioxide (0.1 MPa) was added. The reactor was reacted at 120℃for 6 hours on a heated stirrer with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and allowed to cool naturally, and was washed three times with 30 equivalents of n-hexane to give a colorless oil, which was dried to a constant weight, and the conversion rate reached 68% and the selectivity was 99%.
The preparation method of the catalyst 2 comprises the following steps: 5mLHBr (48% aqueous solution, w/w) was added to a dichloromethane solution of catalyst 1, reacted for 24 hours, and concentrated and dried to give catalyst 2. The hydrogen spectrum of the product is shown in FIG. 27, and the carbon spectrum of the product is shown in FIG. 28. The spectrogram data are: δ10.84-10.60 (m, 2H), 7.80 (d, j=7.9 hz, 2H), 7.34 (t, j=7.7 hz, 2H), 7.17 (t, j=7.4 hz, 1H), 4.13-4.08 (m, 4H), 1.39 (d, j=6.4 hz, 24H).
Example 4:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Catalyst 3 (30 mg,0.05mmol,0.01 equiv) was added with inert gas. Epoxide A (5 mmol,1.0 equiv) was then added and carbon dioxide (0.1 MPa) was added. The reactor was reacted at 100℃for 6 hours on a heated stirrer with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, and was washed three times with 30 equivalents of n-hexane to give a colorless oil, which was dried to a constant weight, and the conversion rate reached 99% and the selectivity was 99%.
The preparation method of the catalyst 3 comprises the following steps: sodium iodide (1.2 eq.) was added to the acetone solution of catalyst 1, the solid was filtered after stirring for 2 hours, and 1.2 eq sodium iodide was added to the solution and stirring was continued for 30 minutes. After filtration, the solution was concentrated, dissolved in dichloromethane, and the solid was filtered again. Concentrating and drying the filtrate to obtain the catalyst 3. The hydrogen spectrum of the product is shown in FIG. 29, and the carbon spectrum of the product is shown in FIG. 30. The spectrogram data are: δ11.03 (s, 1H), 10.63 (s, 1H), 7.88 (d, j=7.9 hz, 2H), 7.34 (t, j=7.7 hz, 2H), 7.17 (t, j=7.4 hz, 1H), 4.10 (hept, j=6.8 hz, 4H), 1.41 (d, j=6.8 hz, 24H).
Example 5:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Catalyst 3 (30 mg,0.05mmol,0.01 equiv) was added with inert gas. Epoxide A (5 mmol,1.0 equiv) was then added and carbon dioxide (0.1 MPa) was added. The reactor was reacted at 25℃for 48 hours on a heated stirrer with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and allowed to cool naturally, and was washed three times with 30 equivalents of n-hexane to give a colorless oil, which was dried to constant weight, and the conversion rate reached 62% and the selectivity was 99%.
Example 6:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Catalyst 3 (30 mg,0.05mmol,0.01 equiv) was added with inert gas. Epoxide B (5 mmol,1.0 equiv) was then added and carbon dioxide (0.1 MPa) was charged. The reactor was reacted at 100℃for 6 hours on a heated stirrer with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, and was washed three times with 30 equivalents of n-hexane to give a colorless oil, which was dried to a constant weight, and the conversion rate reached 96% and the selectivity was 99%. The hydrogen spectrum of the product is shown in figure 3, and the carbon spectrum of the product is shown in figure 4. The spectrogram data are: δ4.98 (dq, j=9.3, 4.9,4.5hz, 1H), 4.58 (td, j=8.6, 1.4hz, 1H), 4.43-4.35 (m, 1H), 3.79 (ddd, j=12.3, 5.3,1.4hz, 1H), 3.71 (ddd, j=12.2, 3.7,1.2hz, 1H).
Example 7:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Catalyst 3 (30 mg,0.05mmol,0.01 equiv) was added with inert gas. Epoxide C (5 mmol,1.0 equiv) was then added and carbon dioxide (0.1 MPa) was added. The reactor was reacted at 100℃for 6 hours on a heated stirrer with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, and was washed three times with 30 equivalents of n-hexane to give a colorless oil, which was dried to a constant weight, and the conversion rate reached 98% and the selectivity was 99%. The hydrogen spectrum of the product is shown in fig. 5, and the carbon spectrum of the product is shown in fig. 6. The spectrogram data are: δ4.97 (dq, j=8.2, 5.3hz,1 h), 4.62 (dd, j=8.9, 8.2hz,1 h), 4.37 (dd, j=8.9, 5.9hz,1 h), 3.60 (d, j=5.2 hz,2 h).
Example 8:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Catalyst 3 (30 mg,0.05mmol,0.01 equiv) was added with inert gas. Epoxide D (5 mmol,1.0 equiv) was then added and carbon dioxide (0.1 MPa) was added. The reactor was reacted at 100℃for 6 hours on a heated stirrer with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, and was washed three times with 30 equivalents of n-hexane to give a colorless oil, which was dried to a constant weight, and the conversion rate reached 97% and the selectivity was 99%. The hydrogen spectrum of the product is shown in fig. 7, and the carbon spectrum of the product is shown in fig. 8. The spectrogram data are: delta 5.89-5.73 (m, 1H), 5.24-5.12 (m, 2H), 4.83-4.73 (m, 1H), 4.45 (t, j=8.4 hz, 1H), 4.36-4.28 (m, 1H), 4.05-3.92 (m, 2H), 3.64 (dd, j=11.2, 3.4hz, 1H), 3.54 (dd, j=11.2, 3.7hz, 1H).
Example 9:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Catalyst 3 (30 mg,0.05mmol,0.01 equiv) was added with inert gas. Epoxide E (5 mmol,1.0 equiv) was then added and carbon dioxide (0.1 MPa) was added. The reactor was reacted at 100℃for 12 hours on a heated stirrer with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, and was washed three times with 30 equivalents of n-hexane to give a colorless oil, which was dried to a constant weight, and the conversion rate reached 99% and the selectivity was 99%. The hydrogen spectrum of the product is shown in fig. 9, and the carbon spectrum of the product is shown in fig. 10. The spectrogram data are: δ4.69 (qd, j=7.5, 5.4hz, 1H), 4.55-4.47 (m, 1H), 4.05 (dd, j=8.4, 7.2hz, 1H), 1.78 (dddd, j=14.0, 10.2,7.5,4.8hz, 1H), 1.72-1.62 (m, 1H), 1.47-1.27 (m, 4H), 0.99-0.81 (m, 3H).
Example 10:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Catalyst 3 (30 mg,0.05mmol,0.01 equiv) was added with inert gas. Epoxide F (5 mmol,1.0 equiv) was then added and carbon dioxide (0.1 MPa) was added. The reactor was reacted at 100℃for 6 hours on a heated stirrer with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and allowed to cool naturally, and was washed three times with 30 equivalents of n-hexane to give a colorless oil, which was dried to a constant weight, and the conversion rate reached 84% and the selectivity was 99%. The hydrogen spectrum of the product is shown in FIG. 11, and the carbon spectrum of the product is shown in FIG. 12. The spectrogram data are: delta 7.16 (ddd, j=7.3, 4.1,2.7hz, 2H), 6.93 (td, j=7.4, 1.0hz, 1H), 6.81-6.75 (m, 1H), 5.05 (ddt, j=8.6, 5.5,3.3hz, 1H), 4.67-4.54 (m, 2H), 4.26 (dd, j=10.6, 3.6hz, 1H), 4.13 (dd, j=10.6, 3.1hz, 1H), 2.22 (s, 3H).
Example 11:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Catalyst 3 (30 mg,0.05mmol,0.01 equiv) was added with inert gas. Epoxide G (5 mmol,1.0 equiv) was then added and carbon dioxide (0.1 MPa) was added. The reactor was reacted at 100℃for 6 hours on a heated stirrer with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, and was washed three times with 30 equivalents of n-hexane to give a colorless oil, which was dried to a constant weight, and the conversion rate reached 87% and the selectivity was 99%. The hydrogen spectrum of the product is shown in fig. 13, and the carbon spectrum of the product is shown in fig. 14. The spectrogram data are: delta 7.38-7.26 (m, 2H), 7.05-6.97 (m, 1H), 6.94-6.87 (m, 2H), 5.07-4.97 (m, 1H), 4.60 (t, j=8.5 hz, 1H), 4.52 (dd, j=8.5, 5.9hz, 1H), 4.23 (dd, j=10.6, 4.0hz, 1H), 4.13 (dd, j=10.7, 3.6hz, 1H).
Example 12:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Catalyst 3 (30 mg,0.05mmol,0.01 equiv) was added with inert gas. Epoxide H (5 mmol,1.0 equiv) was then added and carbon dioxide (0.1 MPa) was added. The reactor was reacted at 100℃for 6 hours on a heated stirrer with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, and was washed three times with 30 equivalents of n-hexane to give a colorless oil, which was dried to a constant weight, and the conversion rate reached 87% and the selectivity was 99%. The hydrogen spectrum of the product is shown in fig. 15, and the carbon spectrum of the product is shown in fig. 16. The spectrogram data are: δ4.79 (ddt, j=8.4, 6.0,3.7hz, 1H), 4.47 (t, j=8.4 hz, 1H), 4.35 (dd, j=8.3, 6.0hz, 1H), 3.62 (dd, j=11.1, 3.6hz, 1H), 3.53 (dd, j=11.1, 3.8hz, 1H), 3.39 (s, 3H).
Example 13:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Catalyst 3 (30 mg,0.05mmol,0.01 equiv) was added with inert gas. Epoxide I (5 mmol,1.0 equiv) was then added and carbon dioxide (0.1 MPa) was added. The reactor was reacted at 100℃for 6 hours on a heated stirrer with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, and was washed three times with 30 equivalents of n-hexane to give a colorless oil, which was dried to a constant weight, and the conversion rate reached 94% and the selectivity was 99%. The hydrogen spectrum of the product is shown in FIG. 17, and the carbon spectrum of the product is shown in FIG. 18. The spectrogram data are: δ4.81-4.71 (m, 1H), 4.47 (t, j=8.2 hz, 1H), 4.38 (dd, j=8.3, 5.8hz, 1H), 3.61 (dd, j=10.3, 4.6hz, 1H), 3.57-3.51 (m, 1H), 1.19 (s, 9H).
Example 14:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Catalyst 3 (30 mg,0.05mmol,0.01 equiv) was added with inert gas. Epoxide J (5 mmol,1.0 equiv) was then added and carbon dioxide (0.1 MPa) was charged. The reactor was reacted at 100℃for 6 hours on a heated stirrer with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, and was washed three times with 30 equivalents of n-hexane to give a colorless oil, which was dried to a constant weight, and the conversion rate reached 88% and the selectivity was 99%. The hydrogen spectrum of the product is shown in fig. 19, and the carbon spectrum of the product is shown in fig. 20. The spectrogram data are: delta 6.14 (t, j=1.1 hz, 1H), 5.64 (p, j=1.5 hz, 1H), 4.97 (ddt, j=8.7, 5.6,3.4hz, 1H), 4.58 (t, j=8.6 hz, 1H), 4.42 (dd, j=12.6, 3.1hz, 1H), 4.36-4.28 (m, 1H), 1.94 (t, j=1.2 hz, 3H).
Example 15:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Catalyst 3 (30 mg,0.05mmol,0.01 equiv) was added with inert gas. Epoxide K (5 mmol,1.0 equiv) was then added and carbon dioxide (0.1 MPa) was charged. The reactor was reacted at 100℃for 6 hours on a heated stirrer with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, and was washed three times with 30 equivalents of n-hexane to give a colorless oil, which was dried to a constant weight, and the conversion rate reached 92% and the selectivity was 99%. The hydrogen spectrum of the product is shown in fig. 21, and the carbon spectrum of the product is shown in fig. 22. The spectrogram data are: delta 7.18-7.10 (m, 4H), 6.85-6.76 (m, 4H), 5.01 (ddt, j=8.1, 5.9,3.9hz, 2H), 4.60 (t, j=8.4 hz, 2H), 4.52 (dd, j=8.5, 5.9hz, 2H), 4.21 (dd, j=10.6, 4.3hz, 2H), 4.12 (dd, j=10.6, 3.5hz, 2H), 1.63 (s, 6H).
Example 16:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Catalyst 3 (30 mg,0.05mmol,0.01 equiv) was added with inert gas. Epoxide L (5 mmol,1.0 equiv) was then added and carbon dioxide (0.1 MPa) was added. The reactor was reacted at 100℃for 48 hours on a heated stirrer with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, and was washed three times with 30 equivalents of n-hexane to give a colorless oil, which was dried to a constant weight, and the conversion rate reached 92% and the selectivity was 99%. The hydrogen spectrum of the product is shown in fig. 23, and the carbon spectrum of the product is shown in fig. 24. The spectrogram data are: δ4.65 (t, j=4.1 hz,1 h), 1.83 (dq, j=10.0, 4.9hz,2 h), 1.54 (tt, j=8.1, 4.4hz,1 h), 1.38 (qd, j=8.7, 7.9,4.5hz,1 h).
Example 17:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. The bisphenol A cyclic carbonate (3 mmol,1 equiv) as the product of epoxide L was added under inert gas, and dissolved in 1mL of DMF as a solvent. 1, 6-hexamethylenediamine (3 mmol,1.0 equiv) and tetrabutylammonium bromide (0.03 mmol,0.01 equiv) as catalyst were further added. The reactor was reacted at 100℃for 24 hours on a stirrer with a stirring rate of 400 revolutions per minute. After the reaction is finished, the reaction tube is taken out to be naturally cooled, and the white solid is obtained by washing with water, and the conversion rate reaches 99%. The hydrogen spectrum of the product is shown in FIG. 31 (nuclear magnetic resonance hydrogen spectrum, 400MHz, CDCl) 3 )。

Claims (9)

1. A method of synthesizing a cyclic carbonate, characterized by: using a catalyst of formula i to form a cyclic carbonate with carbon dioxide via an epoxide of formula ii:
wherein the method comprises the steps of
X is selected from Cl, br, I, CH 3 COO(OAc)；
Wherein R is 1 Selected from methyl, ethyl, butyl, cyclohexyl, isopropyl, R 2 Selected from hydrogen, methyl, methoxy, nitro, trifluoromethyl, chlorine, bromine, iodine, E is selected from O, S;
the epoxide is selected from the structures of formula II:
R 3 、R 4 selected from hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, alkenyl having 1 to 4 carbon atoms, phenyl, halogen-or alkyl-substituted aryl, halogen-substituted alkyl, R 5 –O–CH 2 -, said R 5 Selected from phenyl, phenyl substituted with alkyl of 1 to 3 carbon atoms, allyl or straight or branched alkyl of 1 to 4 carbon atoms, allyl glyceride and bisphenol a glycerol ether.
2. The method of claim 1, wherein R 1 Selected from cyclohexyl, isopropyl, R 2 Selected from hydrogen, methyl, E is selected from S.
3. The method of claim 1, wherein R 3 、R 4 Selected from hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, 1-butenyl, phenyl, halogen-or alkyl-substituted phenyl, chlorine-or bromine-substituted alkyl, R 5 –O–CH 2 -, said R 5 Selected from phenyl, phenyl substituted with alkyl of 1 to 3 carbon atoms, allyl glyceride and bisphenol a glycerol ether.
4. The process of claim 1 wherein the catalyst of formula i is selected from the structures:
5. the process of claim 1 wherein the epoxide of formula ii is selected from the structures:
6. the process of claim 1 wherein the catalyst of formula i is selected from the group consisting of:
the epoxide of formula II is selected from the following structures:
7. the process according to claim 1, wherein the reaction temperature of the process for synthesizing a cyclic carbonate is 25 to 120 ℃, the reaction time is 6 to 48 hours, the carbon dioxide pressure is 0.1 to 1Mpa, and the molar ratio of the catalyst of formula i to the epoxide of formula II is 10:1 to 100:1.
8. the process of claim 7, wherein the process for synthesizing a cyclic carbonate has a reaction temperature of 100 ℃, a reaction time of 6 hours, a pressure of 0.1Mpa, and a molar ratio of the catalyst of formula i to the epoxide of formula II of 100:1.
9. the method according to claim 1, wherein the specific steps of the method include:
(1) The catalyst shown in the formula I and the epoxide shown in the formula II are mixed according to the molar ratio of 100:1 into a reaction vessel;
(2) Filling 0.1Mpa carbon dioxide, and placing the reaction vessel in a heating reactor preheated in advance;
(3) Reacting for 6-12 hours, cooling, adding normal hexane into the reaction liquid, and washing to obtain the cyclic carbonate.
CN202310738234.5A 2023-06-20 2023-06-20 Method for synthesizing cyclic carbonate Pending CN116768842A (en)

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