CN113072517A - Synthetic method of five-membered oxygen heterocyclic compound - Google Patents

Synthetic method of five-membered oxygen heterocyclic compound Download PDF

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CN113072517A
CN113072517A CN202110371662.XA CN202110371662A CN113072517A CN 113072517 A CN113072517 A CN 113072517A CN 202110371662 A CN202110371662 A CN 202110371662A CN 113072517 A CN113072517 A CN 113072517A
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isocyanate
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CN113072517B (en
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郭凯
陈恺
李振江
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Nanjing Tech University
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    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
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Abstract

The invention discloses a synthesis method of a five-membered oxygen-containing heterocyclic compound, which adopts epoxide and hetero-accumulated diene as raw materials and adopts the catalyst of the formula I provided by the invention to react to obtain the five-membered oxygen-containing heterocyclic compound. The method has the advantages of cheap and easily-obtained reagents, capability of synthesizing the product by a one-step method, mild conditions, no metal residue in the whole reaction system, no byproduct generation and high selectivity for obtaining a single product.

Description

Synthetic method of five-membered oxygen heterocyclic compound
Technical Field
The invention belongs to the technical field of organic catalysis, and particularly relates to a method for producing a five-membered oxygen-containing heterocyclic compound by using a [3+2] cyclization reaction of an epoxide and carbon disulfide or isocyanate.
Background
The ternary heterocyclic compounds have important significance in organic synthesis due to high ring strain force. The ring expansion reaction of these heterocyclic compounds, especially the [3+2] cyclization reaction of epoxides with heterocumulative dienes, is considered to be an efficient method for synthesizing polysubstituted five-membered oxygen-containing heterocyclic compounds. Carbon disulfide, isocyanate and other hetero-accumulative dienes are important reagents in organic synthesis, and carbon atoms in the hetero-accumulative dienes have high electrophilicity, so that the hetero-accumulative dienes are easy to attack by nucleophilicity, and the hetero-accumulative dienes are beneficial to a [3+2] cycloaddition reaction with epoxide.
Figure BDA0003009525550000011
The products of cyclization reaction of epoxide and hetero-accumulated diene through [3+2], five-membered oxygen heterocyclic compounds, are widely used for medicine and organic synthesis. Aryl substituted oxazolidinones are reported to have antibacterial as well as antipsychotic and antidepressant activity, and thiocarbonate cyclic ester has radioprotective activity, which are widely used. Until now, a large number of metal ion catalysts and metal complex catalysts have been reported, but the problem of metal ion residues is difficult to avoid, which limits their application in biology and medicine. Compared to metal catalysis, organic catalysis has been rarely reported in this [3+2] cyclization reaction. In the last decade, non-covalent catalysis, especially hydrogen bonding catalysis, has been receiving increasing attention and has been reported to catalyze the [3+2] cyclization reaction.
Halogen bonds are hydrophobic hydrogen bond analogs defined as the non-covalent catalytic interaction formed between an electrophilic center of a halogen atom and a lewis base, the molecule providing the halogen atom being referred to as the "halogen bond donor" and the lewis base as the "halogen bond acceptor". Due to the anisotropy of the electrostatic energy distribution on the surface of the halogen substituent, the electron density perpendicular to the R-X bond is high, so that a positive charge region called 'sigma-hole' exists in the extension direction of the R-X bond, and compared with a hydrogen bond, the halogen bond has the characteristics of directionality, hydrophobicity, controllability and the like, so that the application of the halogen bond in organic catalysis is always the focus of attention of researchers, and a great deal of successful reports are made.
Figure BDA0003009525550000021
North et al have separately reported the use of metal complex catalysts to efficiently catalyze the [3+2] cyclization reaction of epoxides with isocyanates or carbon disulfide, while overcoming the high temperature and high loading of previous metal ion catalysts, but have not avoided the addition of toxic metals. (J.org.chem.2010,75, 6201-6207) Toda et al reported the synthesis of oxazolidinones using tetraarylphosphonium salts to catalyze epoxides with isocyanates, which opened up a new field of organocatalytic cyclization of epoxides with heterocumulative diene [3+2 ]. (org.Lett.2017,19, 5786-Asa 5789) Rostami subsequently reported that squaramide double hydrogen bond catalyzed [3+2] cyclization reactions in 2020, which was the first case reported to be non-covalently catalyzed. Meanwhile, the group of people firstly proposes the assumption of synthesizing cyclic carbonate by catalyzing epoxide and carbon dioxide through nitrogen-halogen bond based on the similarity of halogen bond and hydrogen bond, and has achieved (Chemussem 2021,14(2),738-744), but the electropositivity of nitrogen-halogen bond exists on nitrogen atom, which is a stronger halogen bond, and according to the discovery, we propose the application of relatively weaker carbon-halogen bond in the [3+2] cyclization reaction.
The [3+2] cyclization reaction of epoxides with heterocumulative dienes is different from the CCE reaction with carbon dioxide. CCE reaction of epoxide with carbon dioxide because the product cyclic carbonate is centrosymmetric in structure
Figure BDA0003009525550000022
This results in the formation of only one cyclic carbonate. However, the hetero-cumulated dienes of isocyanate and carbon disulfide produce a variety of products due to asymmetry of the parent nucleus. By the 3+2 cyclization reaction of epoxides with isocyanates
Figure BDA0003009525550000031
The attack of the epoxide by the nucleophilic anion at different sites leads to two different oxazolidinones, however, the [3+2] cyclization of the epoxide with carbon disulfide is very complex and produces a very large number of by-products
Figure BDA0003009525550000032
Since the reaction intermediate is a dithiocarbonate, this intermediate is a highly reactive free radical intermediate RAFT reagent which results in the exchange of sulfur with oxygen, thus yielding 5 or more of the above products. Although the [3+2] cyclization reaction of epoxide and hetero-accumulative diene is the most efficient method for synthesizing the five-membered oxygen-containing heterocyclic compound, selectivity always becomes the greatest challenge of the method, and how to efficiently target and synthesize a single five-membered oxygen-containing heterocyclic compound is always the focus of attention of researchers.
The invention firstly proposes to use a halogen bond donor catalyst, namely 2-halogenated imidazolium salt to catalyze the [3+2] cyclization reaction of epoxide and hetero-accumulated diene. There are a number of reports on the preparation of 2-haloimidazolium salts by reacting imidazolium salts with N-iodosuccinimide in dichloromethane solvent at 40 ℃ for 2 hours, with simple procedure, yield close to 100% and no purification (chem. Eur. J.2018,24, 3464-.
Based on practical application, the invention utilizes 2-halogenated imidazolium salt which is a carbon-halogen bond donor to catalyze and synthesize a series of five-membered oxygen-containing heterocyclic compounds according to the experience of catalyzing epoxide and CCE of carbon dioxide by nitrogen-halogen bond, the system is firstly proposed and applied to the [3+2] cyclization reaction of epoxide and hetero-accumulated diene, and the targeted synthesis of specific five-membered oxygen-containing heterocyclic compounds is realized.
Disclosure of Invention
The invention aims to provide a method for producing five-membered oxygen-containing heterocyclic compounds by catalyzing an epoxide and carbon disulfide or isocyanate to perform a [3+2] cyclization reaction based on a carbon-halogen bond. The method can accurately prepare the five-membered oxygen heterocyclic compound.
A method for synthesizing five-membered oxygen-containing heterocyclic compound under catalysis of carbon-halogen bond, epoxide and carbon disulfide or isocyanate are used as substrates, and five-membered oxygen-containing heterocyclic compound and derivatives thereof are obtained under catalysis of aryl-substituted 2-halogenated imidazolium salt, wherein the structure of the 2-halogenated imidazolium salt is shown as formula (I):
Figure BDA0003009525550000041
O＝C＝N-R4
(III)
r in formula I1、R2Is selected from 2, 4, 6-substituted phenyl and 2, 6-substituted phenyl, and the substituent is methyl, ethyl and isopropyl;
x in the formula I is selected from chlorine and bromine.
R3Selected from one of chloromethyl, phenoxymethyl and phenyl.
R4One selected from p-tolyl, 3, 5-bistrifluoromethylphenyl and m-tolyl.
The structure of the 2-halogenated imidazolium salt is as follows:
Figure BDA0003009525550000042
Figure BDA0003009525550000051
the epoxide is epichlorohydrin, phenyl glycidyl ether and styrene oxide.
The isocyanate is p-tolyl isocyanate, 3, 5-bis (trifluoromethyl) phenyl isocyanate or m-tolyl isocyanate.
Preferably, the epoxide of formula (II) is phenyl glycidyl ether, the isocyanate of formula (III) is 3, 5-bis-trifluoromethylphenyl isocyanate, and the catalyst of formula (I) is a catalyst of formula 4.
Preferably, the epoxide represented by the formula (II) is epichlorohydrin, the isocyanate represented by the formula (III) is p-tolyl isocyanate, and the catalyst represented by the formula (I) is the catalyst represented by the formula 5.
Figure BDA0003009525550000052
The preparation method of the catalyst shown in the formula (I) comprises the steps of carrying out substitution reaction on imidazolium chloride shown in the formula (IV) and N-iodosuccinimide to generate iodoimidazolium chloride shown in the formula (V);
the iodoimidazole chloride shown in the formula (V) is subjected to ion exchange to obtain the bromoimidazole iodide shown in the formula (VII).
Dissolving the substrate of the reaction in dichloromethane, stirring for 1-4h at 30-60 ℃, and washing to obtain a white solid.
The molar ratio of the epoxy substrate represented by the formula (II) to the catalyst represented by the formula (I) is 20: 1.
The synthesis method comprises the specific steps of reacting epoxide shown in a formula (II), hetero-accumulated diene and catalyst shown in a formula (I) in an organic solvent at 70-80 ℃ to obtain a product, namely the five-membered oxygen-containing heterocyclic compound.
Preferably, the organic solvent is chlorobenzene, DMF, toluene or dioxane.
Preferably, the reaction is carried out for 24 hours at the temperature of 80 ℃, and the reaction liquid is subjected to column chromatography to obtain the product, namely the five-membered oxygen heterocyclic compound.
The molar ratio of the epoxy substrate to the catalyst is 20: 1.
The method for synthesizing the five-membered oxygen heterocyclic compound by the epoxide and the carbon disulfide or the isocyanate comprises the specific steps of reacting the epoxide, the carbon disulfide or the isocyanate and the 2-halogenated imidazolium salt at 70-80 ℃ under the condition of a solvent. The five-membered oxygen heterocyclic compound is obtained by column chromatography.
Has the advantages that:
(1) the invention can efficiently synthesize oxazolidinone and thio-cyclic carbonate with diversity through the catalytic system, and has the characteristics of high yield, no metal residue, wide application and the like compared with the method of utilizing a metal catalyst or a metal composite catalyst in the prior art. Has great commercial application potential in biomedicine and fields.
(2) The catalytic system of the invention catalyzes the cyclization reaction of epoxide and carbon disulfide or isocyanate by the action of halogen bond in 2-halogenated imidazolium salt. There are currently only a few reported non-covalent catalyzed [3+2] cyclization reactions and are limited to hydrogen bond catalysis, carbon halogen bond catalysis being first reported in this work. The non-covalent catalytic temperature reported at present is generally higher than 100 ℃, but is reduced to 80 ℃ for the first time in the invention, and the applicability is wide. Compared with the previous report, the carbon halogen bond catalysis overcomes a large amount of byproducts generated in the preparation of the thio-cyclic carbonate and the oxazolidinone, and the target product is synthesized in a targeted mode.
(3) The catalytic system used in the invention has the characteristics of easy preparation, high catalytic efficiency, high conversion rate and high efficiency.
Compared with other existing catalytic systems, the catalyst has the obvious advantages of being mild, efficient, easy to prepare, free of metal and the like.
Drawings
Embodiments of the present invention are described in detail below with reference to the attached drawing figures, wherein
FIG. 1: example 1 hydrogen spectrum of product catalyst 1
FIG. 2: example 1 carbon spectrum of product catalyst 1
FIG. 3: example 2 hydrogen spectrum of product catalyst 2
FIG. 4: example 2 carbon spectrum of product catalyst 2
FIG. 5: example 3 hydrogen spectrum of product catalyst 3
FIG. 6: example 3 carbon spectra of product catalyst 3
FIG. 7: example 4 hydrogen spectrum of product catalyst 4
FIG. 8: example 4 carbon spectrum of product catalyst 4
FIG. 9: example 5 hydrogen spectrum of product catalyst 5
FIG. 10: example 5 carbon spectra of product catalyst 5
FIG. 11: example 6 hydrogen spectrum of product catalyst 6
FIG. 12: example 6 carbon spectra of product catalyst 6
FIG. 13: examples 7-10 product Hydrogen Spectroscopy
FIG. 14: carbon spectra of products of examples 7-10
FIG. 15: example 11 product Hydrogen Spectrum
FIG. 16: example 11 product carbon Spectrum
FIG. 17: example 12 product Hydrogen Spectrum
FIG. 18: example 12 carbon spectrum of product
FIG. 19: example 13 product Hydrogen Spectrum
FIG. 20: example 13 carbon spectrum of product
FIG. 21: example 14 product Hydrogen Spectrum
FIG. 22: example 14 carbon spectrum of product
FIG. 23: example 15 product Hydrogen Spectrum
FIG. 24: example 15 carbon spectrum of product
Detailed Description
The invention is further illustrated by the following examples, which are intended to be illustrative and not limiting. It will be understood by those of ordinary skill in the art that these examples are not intended to limit the present invention in any way and that suitable modifications and data transformations may be made without departing from the spirit of the invention and from the scope of the invention.
The structure of the catalytic system used in the examples is as follows:
Figure BDA0003009525550000081
example 1:
a250 mL reaction flask was thoroughly dried and purged with inert gas. 1, 3- (2, 6-diisopropylphenyl) imidazolium chloride (4.25g,10mmol,1.0equiv.) was added and dissolved with 100mL of anhydrous dichloromethane, followed by addition of N-iodosuccinimide (2.36g,10.5mmol,1.05equiv.) and after stirring at 40 ℃ for 2 hours, the reaction solution was washed with deionized water 50X 3, the organic phases were combined, dried, and the solvent was removed under reduced pressure to give catalyst 1 as a pale yellow powder in a yield of 98%.1H NMR(400MHz,DMSO-d6)δ8.63(s,2H),7.69(t,J＝7.8Hz,2H),7.55(d,J＝7.8Hz,4H),2.24(p,J＝6.7Hz,6H),1.23(dd,J＝19.3,6.8Hz,12H).13C NMR(101MHz,DMSO-d6)δ144.83,132.24,131.98,127.57,125.00,120.16,39.60,28.98,24.19,22.91.
Example 2:
catalyst 1(0.55g,1.0mmol,1.0equiv.) was dissolved in anhydrous dichloromethane, sodium tetrafluoroborate (0.12g,1.1mmol,1.1equiv.) was added to form a suspension, which was stirred at room temperature for 2 hours, filtered, and the filtrate was spin-dried to obtain the tetrafluoroborate salt of catalyst 1. To the tetrafluoroborate salt (0.6g,1.0mmol,1.0equiv.) of the dried catalyst 1 was added ethyl acetate to form a suspension. Preparing acetone saturated solution (0.6g,4mmol,4.0equiv.) of sodium iodide, dropwise adding the saturated solution into the suspension, stirring the mixed reaction solution at room temperature for 12 hours, filtering, washing the filter residue with ethyl acetate and trace acetone, and drying the filter residue to obtain catalyst 2 which is white powder.1H NMR(400MHz,DMSO-d6)δ8.65(s,2H),7.69(t,J＝7.8Hz,2H),7.56(d,J＝7.8Hz,4H),2.24(p,J＝6.7Hz,6H),1.24(dd,J＝18.3,6.8Hz,12H).13C NMR(101MHz,DMSO-d6)δ144.81,132.15,132.04,127.65,125.03,119.50,28.98,24.17,22.92.
Example 3:
a250 mL reaction flask was thoroughly dried and purged with inert gas. 1, 3- (2, 6-diisopropylphenyl) -4, 5-methylimidazolium chloride (4.53g,10mmol,1.0equiv.) was added and dissolved with 100mL of anhydrous dichloromethane, followed by addition of N-iodosuccinimide (2.36g,10.5mmol,1.05equiv.) and, after stirring at 40 ℃ for 2 hours, the reaction solution was washed with deionized water (50X 3), the organic phases were combined, dried, and the solvent was removed under reduced pressure to give catalyst 3 as a pale yellow powder in a yield of 96%.1H NMR(400MHz,DMSO-d6)δ7.89–7.68(m,2H),7.60(d,J＝7.8Hz,4H),2.24(p,J＝6.8Hz,4H),2.17(s,6H),1.23(dd,J＝6.8,2.9Hz,24H).13C NMR(101MHz,DMSO-d6)δ145.02,132.45,131.71,129.84,125.57,107.02,28.66,23.60(d,J＝19.9Hz),10.06.
Example 4:
a250 mL reaction flask was thoroughly dried and purged with inert gas. 1, 3- (2, 6-diethylphenyl) imidazolium chloride (3.68g,10mmol, 1) was added.0equiv.) and dissolved by adding 100mL of anhydrous dichloromethane, followed by addition of N-iodosuccinimide (2.36g,10.5mmol,1.05equiv.) and after stirring at 40 ℃ for 2 hours, the reaction solution was washed with deionized water 50 × 3, the organic phases were combined, dried, and the solvent was removed under reduced pressure to give catalyst 4 as a pale yellow powder with a yield of 96%.1H NMR(400MHz,DMSO-d6)δ7.64(s,2H),7.41(t,J＝7.7Hz,2H),7.19(d,J＝7.7Hz,4H),2.21(dp,J＝25.1,7.6Hz,8H),1.10(t,J＝7.6Hz,12H).13C NMR(101MHz,DMSO-d6)δ140.20,133.73,131.64,127.69,127.63,114.91,29.85,23.78,14.39.
Example 5:
a250 mL reaction flask was thoroughly dried and purged with inert gas. 1, 3- (2, 6-dimethylphenyl) imidazolium chloride (3.12g,10mmol,1.0equiv.) was added and dissolved with 100mL of anhydrous dichloromethane, followed by addition of N-iodosuccinimide (2.36g,10.5mmol,1.05equiv.) and, after stirring at 40 ℃ for 2 hours, the reaction solution was washed with deionized water 50X 3, the organic phases were combined, dried, and the solvent was removed under reduced pressure to give catalyst 5 as a pale yellow powder in 93% yield.1H NMR(400MHz,DMSO-d6)δ8.40(s,2H),7.59–7.48(m,2H),7.44(d,J＝7.6Hz,4H),2.07(s,12H).13C NMR(101MHz,DMSO-d6)δ135.18,134.88,131.16,129.2,126.50,116.34,39.60,17.26.
Example 6:
a250 mL reaction flask was thoroughly dried and purged with inert gas. 1, 3- (2, 4, 6-trimethylphenyl) imidazolium chloride (3.40g,10mmol,1.0equiv.) was added and dissolved by adding 100mL of anhydrous dichloromethane, followed by addition of N-iodosuccinimide (2.36g,10.5mmol,1.05equiv.) and, after stirring at 40 ℃ for 2 hours, the reaction solution was washed with deionized water 50X 3, the organic phases were combined, dried, and the solvent was removed under reduced pressure to give catalyst 6 as a pale yellow powder with a yield of 99%.1H NMR(400MHz,Chloroform-d)δ7.53(s,2H),6.98(s,4H),2.32(s,6H),1.95(s,12H).13C NMR(101MHz,Chloroform-d)δ141.39,134.09,132.16,129.86,125.46,116.51,21.07,17.44.
Example 7:
performing three times on a pressure-resistant pipeThe drying and oxygen removal operations were repeated, and inert gas was bubbled through for protection, catalyst 1(27.5mg, 0.05mmol, 0.05equiv) and phenyl glycidyl ether (0.135mL, 1mmol, 1.0equiv) were added, chlorobenzene solvent (0.5mL) was added, and finally p-tolyl isocyanate (0.138mL, 1.1mmol,1.1 equiv) was added. The lid was screwed down and placed in an oil bath pan at 70 ℃ to react for 24 hours. After the reaction is finished, cooling, purifying by column chromatography (petroleum ether: ethyl acetate: 5:1), and spin-drying on a rotary evaporator to obtain white powder, and drying to constant weight with the yield of 65%.1H NMR(400MHz,Chloroform-d)δ7.51–7.41(m,2H),7.34–7.27(m,2H),7.23–7.14(m,2H),7.00(tt,J＝7.4,1.1Hz,1H),6.93–6.88(m,2H),4.97(dtd,J＝8.8,5.6,4.3Hz,1H),4.24–4.14(m,3H),4.04(dd,J＝8.9,5.9Hz,1H),2.34(s,3H).13C NMR(101MHz,Chloroform-d)δ158.03,154.52,135.61,133.95,129.67,121.76,118.44,114.61,70.33,67.92,47.61,20.78.
Example 8:
the pressure tube was dried and deoxygenated repeatedly three times, inert gas was bubbled through to protect, catalyst 1(27.5mg, 0.05mmol, 0.05equiv) and phenyl glycidyl ether (0.135mL, 1mmol, 1.0equiv) were added, chlorobenzene solvent (0.5mL) was added, and p-tolyl isocyanate (0.138mL, 1.1mmol,1.1 equiv) was added last. The lid was screwed down and placed in an oil bath pan at 80 ℃ for 24 hours. After the reaction, it was cooled, purified by column chromatography (petroleum ether: ethyl acetate: 5:1), and then spin-dried on a rotary evaporator to obtain a white powder, which was dried to a constant weight, with a yield of 87%.1H NMR(400MHz,Chloroform-d)δ7.51–7.41(m,2H),7.34–7.27(m,2H),7.23–7.14(m,2H),7.00(tt,J＝7.4,1.1Hz,1H),6.93–6.88(m,2H),4.97(dtd,J＝8.8,5.6,4.3Hz,1H),4.24–4.14(m,3H),4.04(dd,J＝8.9,5.9Hz,1H),2.34(s,3H).13C NMR(101MHz,Chloroform-d)δ158.03,154.52,135.61,133.95,129.67,121.76,118.44,114.61,70.33,67.92,47.61,20.78.
Example 9:
the drying and oxygen removal operations were repeated three times for the pressure tube, and inert gas was introduced to protect it, catalyst 2(29.8mg, 0.05mmol, 0.05equiv) and phenyl glycidyl ether (0.135mL, 1mmol, 1.0equiv) were added, DMF was added and dissolvedAgent (0.5mL), and finally p-tolyl isocyanate (0.138mL, 1.1mmol,1.1 equiv) was added. The lid was screwed down and placed in an oil bath pan at 80 ℃ for 24 hours. After the reaction is finished, cooling, purifying by column chromatography (petroleum ether: ethyl acetate: 5:1), and spin-drying on a rotary evaporator to obtain white powder which is dried to constant weight, wherein the yield is 78%.1H NMR(400MHz,Chloroform-d)δ7.51–7.41(m,2H),7.34–7.27(m,2H),7.23–7.14(m,2H),7.00(tt,J＝7.4,1.1Hz,1H),6.93–6.88(m,2H),4.97(dtd,J＝8.8,5.6,4.3Hz,1H),4.24–4.14(m,3H),4.04(dd,J＝8.9,5.9Hz,1H),2.34(s,3H).13C NMR(101MHz,Chloroform-d)δ158.03,154.52,135.61,133.95,129.67,121.76,118.44,114.61,70.33,67.92,47.61,20.78.
Example 10:
the pressure tube was dried and deoxygenated repeatedly three times, inert gas was bubbled through to protect, catalyst 3(3.09mg, 0.05mmol, 0.05equiv) and phenyl glycidyl ether (0.135mL, 1mmol, 1.0equiv) were added, chlorobenzene solvent (0.5mL) was added, and p-tolyl isocyanate (0.138mL, 1.1mmol,1.1 equiv) was added last. The lid was screwed down and placed in an oil bath pan at 80 ℃ for 24 hours. After the reaction, it was cooled, purified by column chromatography (petroleum ether: ethyl acetate: 5:1), and then spin-dried on a rotary evaporator to obtain a white powder, which was dried to a constant weight, with a yield of 89%.1H NMR(400MHz,Chloroform-d)δ7.51–7.41(m,2H),7.34–7.27(m,2H),7.23–7.14(m,2H),7.00(tt,J＝7.4,1.1Hz,1H),6.93–6.88(m,2H),4.97(dtd,J＝8.8,5.6,4.3Hz,1H),4.24–4.14(m,3H),4.04(dd,J＝8.9,5.9Hz,1H),2.34(s,3H).13C NMR(101MHz,Chloroform-d)δ158.03,154.52,135.61,133.95,129.67,121.76,118.44,114.61,70.33,67.92,47.61,20.78.
Example 11:
the pressure tube was subjected to three repetitions of drying and oxygen removal operations, and inert gas was introduced for protection, catalyst 4(24.7mg, 0.05mmol, 0.05equiv) and phenyl glycidyl ether (0.135mL, 1mmol, 1.0equiv) were added, chlorobenzene solvent (0.5mL) was added, and finally 3, 5-bistrifluoromethylphenyl isocyanate (0.19mL, 1.1mmol,1.1 equiv) was added. The lid was screwed down and placed in an oil bath pan at 80 ℃ for 24 hours. After the reaction is finished, coolingAnd purifying by column chromatography (petroleum ether: ethyl acetate: 5:1), and spin-drying on a rotary evaporator to obtain white powder, and drying to constant weight with a yield of 91%.1H NMR(400MHz,Chloroform-d)δ8.08(d,J＝1.6Hz,2H),7.68–7.63(m,1H),7.36–7.26(m,2H),7.06–6.98(m,1H),6.94–6.87(m,2H),5.12–5.01(m,1H),4.33–4.17(m,3H),4.17(dd,J＝8.7,5.9Hz,1H).13C NMR(101MHz,Chloroform-d)δ157.66,152.68,139.98,132.94,132.59,129.88,122.20,117.73,117.01,114.77,70.87,67.69,47.11.
Example 12:
the pressure tube was subjected to three repetitions of drying and oxygen removal operations, and inert gas was introduced for protection, catalyst 5(21.9mg, 0.05mmol, 0.05equiv) and epichlorohydrin (0.08mL, 1mmol, 1.0equiv) were added, chlorobenzene solvent (0.5mL) was added, and finally m-tolyl isocyanate (0.138mL, 1.1mmol,1.1 equiv) was added. The lid was screwed down and placed in an oil bath pan at 80 ℃ for 24 hours. After the reaction was completed, it was cooled, purified by column chromatography (petroleum ether: ethyl acetate: 5:1), and then spin-dried on a rotary evaporator to obtain a white powder, which was dried to a constant weight, with a yield of 93%.1H NMR(400MHz,Chloroform-d)δ7.39(d,J＝2.0Hz,1H),7.35–7.22(m,3H),6.98(d,J＝7.3Hz,1H),4.86(dddd,J＝8.7,6.8,5.6,4.0Hz,1H),4.16(t,J＝9.0Hz,1H),3.77(qd,J＝11.6,5.4Hz,2H),2.38(s,3H).13C NMR(101MHz,Chloroform-d)δ154.07,139.31,137.88,129.43,119.18,115.65,70.96,48.48,44.65,21.77.
Example 13:
the pressure tube was subjected to three repetitions of drying and oxygen removal operations, and inert gas was introduced for protection, and catalyst (6) (23.3mg, 0.05mmol, 0.05equiv) and styrene oxide (0.12mL, 1mmol, 1.0equiv) were added, chlorobenzene solvent (0.5mL) was added, and p-tolylisocyanate (0.138mL, 1.1mmol,1.1 equiv) was added. The lid was screwed down and placed in an oil bath pan at 80 ℃ for 24 hours. After the reaction, the reaction mixture was cooled, purified by column chromatography (petroleum ether: ethyl acetate: 5:1), and spin-dried on a rotary evaporator to obtain a white powder, which was dried to a constant weight, with a yield of 82%.1H NMR(400MHz,Chloroform-d)δ7.46–7.35(m,7H),7.18(d,J＝8.3Hz,2H),5.63(t,J＝8.1Hz,1H),4.36(t,J＝8.8Hz,1H),3.94(dd,J＝8.9,7.6Hz,1H),2.33(s,3H).13C NMR(101MHz,Chloroform-d)δ154.94,138.36,135.76,134.03,129.76,129.21,129.16,125.82,118.54,77.36,74.14,52.99,20.89.
Example 14:
the pressure tube was subjected to three repetitions of drying and oxygen removal operations, and inert gas was introduced for protection, and catalyst (2) (29.8mg, 0.05mmol, 0.05equiv) and epichlorohydrin (0.08mL, 1mmol, 1.0equiv) were added, chlorobenzene solvent (0.5mL) was added, and p-tolylisocyanate (0.138mL, 1.1mmol,1.1 equiv) was added. The lid was screwed down and placed in an oil bath pan at 80 ℃ for 24 hours. After the reaction is finished, cooling, purifying by column chromatography (petroleum ether: ethyl acetate: 5:1), and spin-drying on a rotary evaporator to obtain white powder, and drying to constant weight with the yield of 94%.1H NMR(400MHz,Chloroform-d)δ7.47–7.32(m,2H),7.22–7.11(m,2H),4.85(dddd,J＝8.7,6.6,5.7,4.1Hz,1H),4.14(t,J＝9.0Hz,1H),3.93(dd,J＝9.2,5.7Hz,1H),3.85–3.70(m,2H),2.33(s,3H).13CNMR(101MHz,Chloroform-d)δ154.18,135.41,134.31,129.81,118.65,70.97,48.48,44.68,20.88.
Example 15:
the pressure tube was dried and deoxygenated repeatedly three times, inert gas was bubbled through to protect, catalyst (2) (29.8mg, 0.05mmol, 0.05equiv) and phenyl glycidyl ether (0.135mL, 1mmol, 1.0equiv) were added, and carbon disulfide (1.0mL) was added. The lid was screwed down and placed in an oil bath pan at 80 ℃ for 24 hours. After the reaction is finished, cooling, purifying by column chromatography (petroleum ether: ethyl acetate ═ 5:1), and spin-drying on a rotary evaporator to obtain a light yellow oily substance which is dried to constant weight and the yield is 84%.1H NMR(400MHz,Chloroform-d)δ7.36–7.28(m,2H),7.02(td,J＝7.3,1.1Hz,1H),6.96–6.89(m,2H),5.50–5.39(m,1H),4.32(h,J＝5.6Hz,2H),3.78(qd,J＝11.2,7.5Hz,2H).13C NMR(101MHz,Chloroform-d)δ211.45,157.84,129.84,122.05,114.67,66.35,36.45.

Claims (10)

1. A synthetic method of a five-membered oxygen heterocyclic compound is characterized in that an epoxide shown as a formula (II) and carbon disulfide or isocyanate shown as a formula (III) are used as raw materials, and a catalyst shown as a formula (I) is adopted to react to obtain the five-membered heterocyclic compound
Figure FDA0003009525540000011
Wherein R is1、R2Is selected from 2, 4, 6-substituted phenyl and 2, 6-substituted phenyl, and the substituent is methyl, ethyl and isopropyl;
x is selected from chlorine and bromine,
R3selected from the group consisting of monochloromethyl, phenoxymethyl, phenyl,
R4selected from p-tolyl, 3, 5-bistrifluoromethylphenyl, m-tolyl.
2. The synthesis process according to claim 1, characterized in that the catalyst of formula (I) is selected from the following structures:
Figure FDA0003009525540000021
3. the method of synthesis according to claim 2, characterized in that: the epoxide shown in the formula (II) is phenyl glycidyl ether, the isocyanate shown in the formula (III) is 3, 5-bis (trifluoromethyl) phenyl isocyanate, and the catalyst shown in the formula (I) is a catalyst shown in a formula 4.
4. The method of synthesis according to claim 2, characterized in that: the epoxide shown in the formula (II) is epichlorohydrin, the isocyanate shown in the formula (III) is p-tolyl isocyanate, and the catalyst shown in the formula (I) is a catalyst shown in a formula 5.
5. The method of synthesis according to claim 1, characterized in that:
Figure FDA0003009525540000022
Figure FDA0003009525540000031
the preparation method of the catalyst shown in the formula (I) comprises the steps of carrying out substitution reaction on imidazolium chloride shown in the formula (IV) and N-iodosuccinimide to generate iodoimidazolium chloride shown in the formula (V);
the iodoimidazole chloride shown in the formula (V) is subjected to ion exchange to obtain the bromoimidazole iodide shown in the formula (VII).
6. The method of synthesis according to claim 5, characterized in that: dissolving the substrate of the reaction in dichloromethane, stirring for 1-4h at 30-60 ℃, and washing to obtain a white solid.
7. A synthesis method according to any one of claims 1 to 3, characterized in that: the molar ratio of the epoxy substrate represented by the formula (III) to the catalyst represented by the formula (I) is 20: 1.
8. A synthesis method according to any one of claims 1 to 3, characterized in that: the synthesis method comprises the specific steps of reacting epoxide shown in a formula (II), hetero-accumulated diene and catalyst shown in a formula (I) in an organic solvent at 70-80 ℃ to obtain a product, namely the five-membered oxygen-containing heterocyclic compound.
9. The method of synthesis according to claim 8, characterized in that: the organic solvent is chlorobenzene, DMF, toluene or dioxane.
10. The method of synthesis according to claim 8, characterized in that: the reaction is carried out for 24 hours at the temperature of 80 ℃, and the reaction liquid is subjected to column chromatography to obtain the product five-membered oxygen heterocyclic compound.
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