CN117143067B - Metal complex in CO catalysis2Use of cyclisation for the preparation of cyclic carbonates - Google Patents

Metal complex in CO catalysis2Use of cyclisation for the preparation of cyclic carbonates Download PDF

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CN117143067B
CN117143067B CN202310997075.0A CN202310997075A CN117143067B CN 117143067 B CN117143067 B CN 117143067B CN 202310997075 A CN202310997075 A CN 202310997075A CN 117143067 B CN117143067 B CN 117143067B
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metal complex
cyclic carbonate
cyclization
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catalyst
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CN117143067A (en
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苗成霞
于宁
张丛丛
韩峰
梁淑彦
万朋
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Shandong Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to application of a metal complex in preparation of cyclic carbonate by catalyzing cyclization of CO 2. The invention takes metal complex obtained by the reaction of bipyridine diamine ligand and metal salt as catalyst, and catalyzes CO 2 to react with epoxy compound to prepare cyclic carbonate under the condition of acetonitrile as solvent or no solvent. The catalyst system for cyclizing the CO 2 has the advantages of being a single-component catalyst system, being good in economy and high in catalytic performance, and the catalyst system is adopted to catalyze the cyclizing of the CO 2, so that the yield of the cyclic carbonate is as high as 93%; in addition, the catalyst has good tolerance to substrate functional groups, and under the optimized reaction condition, the substrate with various substituents can smoothly react with CO 2 to obtain a corresponding target product, thereby being beneficial to improving the adaptability of the CO 2 cyclization process.

Description

Application of metal complex in preparation of cyclic carbonate by catalyzing cyclization of CO 2
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to application of a metal complex in preparation of cyclic carbonate by catalyzing cyclization of CO 2.
Background
In recent years, excessive consumption of fossil fuels has directly led to rapid and continuous increase in the concentration of CO 2 in the atmosphere, and in order to suppress the continuous increase in the concentration of CO 2 and also to alleviate the problem of energy shortage, utilization of CO 2 resources to convert CO 2 into high-value-added chemical products such as CO, formic acid, methanol, and cyclic carbonates has become a hot spot in research in recent years.
The cyclic carbonate substance can be used as an excellent cleaning solvent and is widely applied to the fields of extraction and separation of mixtures, processing of phenolic resin, synthesis of materials such as polycarbonate, thermosetting resin, thermosensitive recording materials and the like, high-energy-density batteries (such as lithium batteries), capacitor electrolytes and the like. In addition, the cyclic carbonate substance can be directly obtained from CO 2 and epoxide, and the reaction has 100% of atom economy and accords with the characteristic of green chemistry.
However, due to thermodynamic stability and kinetic inertia of CO 2, higher temperature and pressure are often required for cycloaddition reaction, and part of the system has the problems of complex catalytic system, difficult catalyst recycling, low catalytic efficiency and the like, so that the mass production of the catalyst is limited to a certain extent.
In addition, most of the existing catalysts for catalyzing cyclization of CO 2 to generate cyclic carbonate are metalloporphyrin, metal Salen and the like, but the problems of low yield, difficult ligand separation or difficult acquisition of purer complex and the like exist in the preparation process of the catalyst, so the catalyst with simple preparation process and high catalytic activity is provided, and has great significance for improving the conversion efficiency of CO 2 for cyclizing to synthesize the cyclic carbonate, and improving the utilization rate of CO 2.
The bipyridine diamine catalyst has an N4 structure similar to porphyrin, has higher catalytic performance, has the advantages of simple synthetic route, high yield and easy separation compared with metalloporphyrin catalysts, but is not used as a precursor of the catalyst in the preparation of cyclic carbonate by CO 2 cyclization at present, and whether the catalyst can catalyze the cyclization reaction of CO 2 is unknown.
Disclosure of Invention
In order to solve the technical problems, the invention provides application of a metal complex in preparing cyclic carbonate by catalyzing CO 2 cyclization, namely, preparing the cyclic carbonate by catalyzing CO 2 cyclization by taking the metal complex as a catalyst, wherein the metal complex is obtained by reacting bipyridine diamine ligand and metal salt;
The bipyridine diamine ligand has the following structural formula:
The structural formula of the metal salt is MX n;
wherein M is selected from any one of manganese, iron, cobalt, nickel, copper and zinc;
x is selected from any one of fluorine, chlorine, bromine, sulfonate ion and acetate ion, and n is 2, 3 or 4.
In the application, the mole ratio of the bipyridine diamine ligand to the metal salt is 1-2: 1.
Preferably, the molar ratio of bipyridine diamine ligand to metal salt is 1:1.
In the above application, the cyclic carbonate has the following structural formula:
Wherein R 1 is independently selected from propargyloxymethyl, allyloxymethyl, alkyl, alkoxymethyl, chloromethyl, phenyl, phenoxymethyl or hydrogen;
R 2 is independently selected from propargyloxymethyl, allyloxymethyl, alkyl, alkoxymethyl, chloromethyl, phenyl, phenoxymethyl or hydrogen.
In the application provided by the invention, in the process of preparing the cyclic carbonate by catalyzing CO 2 to react with the epoxy compound, the pressure of CO 2 is 1-5 MPa, and the metal complex accounts for 1-10% of the mole percentage of the epoxy compound; the structural formula of the epoxy compound is as follows:
Wherein R 1 is independently selected from propargyloxymethyl, allyloxymethyl, alkyl, alkoxymethyl, chloromethyl, phenyl, phenoxymethyl or hydrogen;
R 2 is independently selected from propargyloxymethyl, allyloxymethyl, alkyl, alkoxymethyl, chloromethyl, phenyl, phenoxymethyl or hydrogen.
In the application, the reaction solvent is acetonitrile or no reaction solvent, the reaction temperature is 60-120 ℃, and the reaction time is 2-24 h.
Preferably, the reaction temperature is 80-100 ℃ and the reaction time is 2-12 h.
Preferably, the reaction temperature is 85-95 ℃ and the reaction time is 5-10 h.
Further, in the above application provided by the present invention, the equation of the reaction process is as follows:
The invention has the beneficial effects that:
(1) The catalyst system is a single-component catalyst system, has the advantages of good economy and high catalytic performance, and can be used for catalyzing the cyclization of CO 2, and the yield of the cyclic carbonate is as high as 93%;
(2) In the raw materials adopted by the invention, the epoxide has various types, the bipyridine diamine metal catalyst has good tolerance to the substrate functional groups, and under the optimized reaction condition, the substrates with various substituents can smoothly react to obtain corresponding target products;
(3) In addition, the bipyridine diamine metal catalyst adopted by the invention has the advantages of simple synthetic route, high yield, easy separation and the like, and is mainly based on the preparation process of the catalyst, the polarity difference between the catalyst and the reaction raw materials and the like, but the preparation process of the catalyst is not the key protection of the invention, so the catalyst is not described in detail herein; the experiment proves that the catalyst provided by the invention has obviously good catalytic efficiency in the process of preparing the cyclic carbonate by the cyclization reaction of CO 2, so that the catalyst provided by the invention is a good substitute for the catalyst which has the problems of large preparation difficulty, complex process, low catalyst purity and the like in the traditional metalloporphyrin.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a product prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of the product prepared in example 1 of the present invention;
FIG. 3 is a chart showing the nuclear magnetic resonance hydrogen spectrum of the product prepared in example 2 of the present invention;
FIG. 4 is a nuclear magnetic resonance spectrum of the product prepared in example 2 of the present invention;
FIG. 5 is a chart showing the nuclear magnetic resonance hydrogen spectrum of the product prepared in example 3 of the present invention;
FIG. 6 is a nuclear magnetic resonance spectrum of the product prepared in example 3 of the present invention;
FIG. 7 is a chart showing the nuclear magnetic resonance hydrogen spectrum of the product prepared in example 4 of the present invention;
FIG. 8 is a nuclear magnetic resonance spectrum of the product prepared in example 4 of the present invention;
FIG. 9 is a chart showing the nuclear magnetic resonance hydrogen spectrum of the product prepared in example 5 of the present invention;
FIG. 10 is a nuclear magnetic resonance spectrum of the product prepared in example 5 of the present invention.
Detailed Description
The present invention will now be further described in connection with specific embodiments in order to enable those skilled in the art to better understand the invention.
The method for calculating the product yield is as follows:
Yield = actual yield/theoretical yield x 100%;
Yield calculations are referred to GB/T27417-2017.
Example 1
1Mmol of epichlorohydrin, 5% mmol of N, N '-dimethyl-N, N' -bis (phenylpyridine-2-methyl) cyclohexane-1, 2-diamine and 5% mmol of cobalt bromide are sequentially added into a reaction tube, then strong magneton and 2mL of acetonitrile are added into the reaction tube, the reaction tube is placed in a high-pressure reaction kettle, 2.5MPa CO 2 is flushed into the high-pressure reaction kettle, and then the high-pressure reaction kettle is heated and stirred at 90 ℃ for 8 hours.
After the reaction is finished, the obtained product is purified, and the specific purification operation is as follows: transferring the product into a 100mL eggplant-shaped bottle, adding silica gel (100-200 meshes), carrying out vacuum spin drying, further purifying by silica gel column chromatography (petroleum ether: ethyl acetate=5:1), and pumping the obtained product by a vacuum pump and an oil pump to obtain 118.76mg of colorless liquid product, namely 4- (chloromethyl) -1, 3-dioxolan-2-one, wherein the yield is 87%.
1H NMR(400MHz,Chloroform-d)δ5.03(dtd,J＝8.7,5.3,3.5Hz,1H),4.62(t,J＝8.6Hz,1H),4.43(dd,J＝8.9,5.7Hz,1H),3.90-3.68(m,2H).
13C NMR(101MHz,Chloroform-d)δ154.49,74.45,67.00,44.06。
Example 2
1Mmol of allyl glycidyl ether, 5% mmol of N, N '-dimethyl-N, N' -bis (phenylpyridine-2-methyl) cyclohexane-1, 2-diamine and 5% mmol of cobalt bromide are sequentially added into a reaction tube, then strong magneton and 2mL of acetonitrile are added into the reaction tube, the reaction tube is placed in a high-pressure reaction kettle, 2.5MPa CO 2 is flushed into the high-pressure reaction kettle, and the high-pressure reaction kettle is heated and stirred at 90 ℃ for 8 hours.
After the reaction was completed, the obtained product was purified by the same method as in example 1 to finally obtain 127.98mg of 4- (allyloxymethyl) -1, 3-dioxolan-2-one as a colorless liquid product in a yield of 81.75%.
1H NMR(400MHz,Chloroform-d)δ5.88(ddt,J＝16.4,10.9,5.6Hz,1H),5.26(dd,J＝25.8,13.8Hz,2H),4.85(tdd,J＝9.2,4.2,2.3Hz,1H),4.52(td,J＝8.4,1.4Hz,1H),4.42(dd,J＝8.3,6.3Hz,1H),4.15-3.99(m,2H),3.79-3.55(m,2H).
13C NMR(101MHz,Chloroform-d)δ155.06,133.67,117.94,117.92,75.12,72.55,68.81,66.28。
Example 3
1Mmol of butyl glycidyl ether, 5% mmol of N, N '-dimethyl-N, N' -bis (phenylpyridine-2-methyl) cyclohexane-1, 2-diamine and 5% mmol of cobalt bromide are sequentially added into a reaction tube, then strong magneton and 2mL of acetonitrile are added into the reaction tube, the reaction tube is placed in a high-pressure reaction kettle, 2.5MPa CO 2 is flushed into the high-pressure reaction kettle, and the high-pressure reaction kettle is heated and stirred at 90 ℃ for 8 hours.
After the reaction was completed, the product was purified by the purification method of example 1 to give 151.38mg of 4- (butoxymethyl) -1, 3-dioxolan-2-one as a product in a yield of 87.61%.
1H NMR(400MHz,Chloroform-d)δ4.82(dtd,J＝9.2,4.9,4.3,2.4Hz,1H),4.51(td,J＝8.3,1.3Hz,1H),4.40(ddd,J＝8.1,6.1,1.3Hz,1H),3.77-3.56(m,2H),3.51(t,J＝6.5Hz,2H),1.61-1.48(m,2H),1.36(h,J＝7.4Hz,2H),0.98-0.83(m,3H).
13C NMR(101MHz,Chloroform-d)δ75.14,71.86,69.59,66.31,31.50,19.15,13.87。
Example 4
1Mmol of styrene oxide, 5% mmol of N, N '-dimethyl-N, N' -bis (phenylpyridine-2-methyl) cyclohexane-1, 2-diamine and 5% mmol of cobalt bromide are sequentially added into a reaction tube, then strong magneton and 2mL of acetonitrile are added into the reaction tube, the reaction tube is placed in a high-pressure reaction kettle, 2.5MPa CO 2 is injected into the high-pressure reaction kettle, and the high-pressure reaction kettle is heated and stirred at 90 ℃ for 8 hours.
After the reaction was completed, the product was purified by the purification method of example 1 to give 152.25mg of 4-phenyl-1, 3-dioxolan-2-one as a white solid in 93% yield.
1H NMR(400MHz,Chloroform-d)δ7.51-7.29(m,5H),5.67(t,J＝8.0Hz,1H),4.79(t,J＝8.4Hz,1H),4.32(t,J＝8.2Hz,1H).
13C NMR(101MHz,Chloroform-d)δ155.03,135.87,129.75,129.25,126.01,78.10,71.26。
Example 5
1Mmol of 1, 2-epoxypropane, 5% mmol of N, N '-dimethyl-N, N' -bis (phenylpyridine-2-methyl) cyclohexane-1, 2-diamine and 5% mmol of cobalt bromide are sequentially added into a reaction tube, then strong magneton and 2mL of acetonitrile are added into the reaction tube, the reaction tube is placed in a high-pressure reaction kettle, 2.5MPa CO 2 is flushed into the high-pressure reaction kettle, and the high-pressure reaction kettle is heated and stirred at 90 ℃ for 8 hours.
After the reaction was completed, the product was purified by the purification method of example 1 to obtain 53.43mg of propylene carbonate as a colorless liquid product in 92% yield.
1H NMR(400MHz,Chloroform-d)δ4.90(tt,J＝13.4,4.7Hz,1H),4.59(t,J＝8.1Hz,1H),4.06(dd,J＝8.5,7.2Hz,1H),1.50(d,J＝6.4Hz,3H).
13C NMR(101MHz,Chloroform-d)δ155.22,73.76,70.74,19.28。
Examples 6 to 8
Unlike example 4, the following is: the amounts of the ligand and the metal salt added were adjusted, and the other matters were the same as in example 4, and the amounts of the ligand and the metal salt added and the yield of the cyclic carbonate in each example were as shown in Table 1 below.
TABLE 1 yield of cyclic carbonates at various metal complex additions
Examples Ligand (%) Metal salt (%) Yield (%)
Example 6 1 1 72
Example 7 3 3 75
Example 8 7 7 85
Examples 9 to 12
Unlike example 4, the reaction temperature settings during the cyclization reaction were varied, the specific parameter settings and the corresponding product yields are shown in Table 2 below.
TABLE 2 yields of cyclic carbonates under different reaction conditions
Examples Reaction temperature (. Degree. C.) Yield (%)
Example 9 80 91
Example 10 85 92
Example 11 95 86
Example 12 100 80

Claims (4)

1. The application of a metal complex in preparing cyclic carbonate by catalyzing CO 2 cyclization is characterized in that the metal complex is used as a catalyst to catalyze CO 2 cyclization to prepare cyclic carbonate; in the process of preparing cyclic carbonate by catalyzing CO 2 and epoxy compound to react, the pressure of CO 2 is 1-5 MPa, the metal complex accounts for 1-10% of the mole percentage of the epoxy compound, the solvent for reaction is acetonitrile, the reaction temperature is 60-120 ℃, and the reaction time is 2-24 h;
The structural formula of the epoxy compound is as follows:
wherein R 1 is independently selected from propargyloxymethyl, allyloxymethyl, alkyl, alkoxymethyl, chloromethyl, phenyl, phenoxymethyl, or hydrogen; r 2 is hydrogen;
The metal complex is obtained by reacting bipyridine diamine ligand with metal salt;
The bipyridine diamine ligand has the following structural formula:
The structural formula of the metal salt is MX n, and M is cobalt;
X is selected from any one of fluorine, chlorine and bromine, and n is 2.
2. The use of a metal complex according to claim 1 for the preparation of cyclic carbonates by catalytic CO 2 cyclization, wherein the molar ratio of bipyridine diamine ligand to metal salt is 1-2: 1.
3. The use of a metal complex according to claim 1 for the preparation of a cyclic carbonate by catalytic CO 2 cyclization, wherein the cyclic carbonate has the formula:
Wherein R 1 is independently selected from propargyloxymethyl, allyloxymethyl, alkyl, alkoxymethyl, chloromethyl, phenyl, phenoxymethyl or hydrogen; r 2 is hydrogen.
4. The use of a metal complex according to claim 1 for the preparation of cyclic carbonates by catalytic CO 2 cyclization, wherein the reaction temperature is 80-100 ℃ and the reaction time is 2-12 h.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103447091A (en) * 2013-09-05 2013-12-18 中国科学院长春应用化学研究所 Quadridentate pyridyl schiff base metal complex and preparation method thereof as well as preparation method of cyclic carbonate
JP2021138661A (en) * 2020-03-06 2021-09-16 国立研究開発法人産業技術総合研究所 Method for producing cyclic carbonates

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103447091A (en) * 2013-09-05 2013-12-18 中国科学院长春应用化学研究所 Quadridentate pyridyl schiff base metal complex and preparation method thereof as well as preparation method of cyclic carbonate
JP2021138661A (en) * 2020-03-06 2021-09-16 国立研究開発法人産業技術総合研究所 Method for producing cyclic carbonates

Non-Patent Citations (1)

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Title
Multifunctional Zn-N4 Catalysts for the Coupling of CO2 with Epoxides into Cyclic Carbonates;Wang Bingyang et al.;ACS Catal.;20230725;第13卷;第10387页图1，第10389页表1，第10390页表2，详细试验部分S4和S6页 *

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