CN111217769B - Method for synthesizing epoxy compound by catalyzing olefin epoxy by using nano alumina - Google Patents

Method for synthesizing epoxy compound by catalyzing olefin epoxy by using nano alumina Download PDF

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CN111217769B
CN111217769B CN202010133019.9A CN202010133019A CN111217769B CN 111217769 B CN111217769 B CN 111217769B CN 202010133019 A CN202010133019 A CN 202010133019A CN 111217769 B CN111217769 B CN 111217769B
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epoxy
olefin
nano alumina
epoxy compound
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CN111217769A (en
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胡建强
周璇
戚朝荣
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B01J35/23—
    • B01J35/40—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • C07D303/06—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms in which the oxirane rings are condensed with a carbocyclic ring system having three or more relevant rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals

Abstract

The invention belongs to the field of organic synthesis and catalysis, and discloses a method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina. The method comprises the following steps: adding solvent, olefin, nano alumina and fatty aldehyde into a reactor to obtain a mixed solution, wherein the olefin in the mixed solution is used as a raw material, the nano alumina is used as a catalyst, the fatty aldehyde is used as a reducing agent, vacuumizing a reaction container, introducing oxygen, heating and stirring for reaction, obtaining a reaction solution after the reaction is finished, and separating and purifying the reaction solution to obtain the epoxy compound. The catalyst used in the method is cheap and easy to obtain, the reaction condition is mild, the applicability to the substrate is wide, the operation is safe and simple, and the method has potential industrial application prospect.

Description

Method for synthesizing epoxy compound by catalyzing olefin epoxy by using nano alumina
Technical Field
The invention belongs to the field of organic synthesis and catalysis, and in particular relates to a method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina.
Background
The epoxidation of olefins is a very important oxidation reaction, since the epoxy compounds obtained by the reaction have wide application in the production of chemicals such as epoxy resins, paints and surfactants. In addition, epoxy compounds are also an important class of organic synthesis intermediates, for example, a series of functional molecules can be obtained through nucleophilic ring-opening reaction of epoxy compounds, and chemicals such as medical molecules, pesticides, fragrances and the like can be further synthesized. Thus, the development of efficient catalysts for the selective epoxidation of olefins is of great importance (Q.H.Xia, H.Q.Ge, C.P.Ye, Z.M.Liu, K.X.Su, chem.Rev.2005,105,1603-1662; O.A.Wong, Y.Shi, chem.Rev.2008,108,3958-3987; K.P.Bryiakov, chem.Rev.2017,117,11406-11459;W.Yan,G.Zhang,H.Yan,Y.Liu,X.Chen,X.Feng,X.Jin,C.Yang,ACS Sustainable Chem.Eng.2018,6,4423-4452; Y.Zhu, Q.Wang, R.G.Cornwall, Y.Shi, chem.Rev.2014,114, 8199-8256).
Oxidants currently reported for the epoxidation of olefins include peroxyacids (A.J.Jensen, K.Luthman, tetrahedron Lett.1998,39, 3213-3214), iodosobenzenes (S.Mukerjee, A.Stassinopoulos, J.P.Caradonna, J.Am.Chem.Soc.1997,119,8097-8098; Y.Murakami, K.Konishi, J.am.chem.Soc.129, 14401-14407), hydrogen peroxide (B.S.Lane, K.Burgess, chem.Rev.2003,103,2457-2473; O.Cuss, X.Ribas, J.Lloret-Fillol, M.Costas, angew.Chem.Int.Ed.2015,54,2729-2733; Y.Nakagawa, K.Kamata, M.Kotani, K.Yamaguchi, N.Mizuno, angew.chem.Int.Ed.2005,44,5136-5141; N.Mizuno, S.Uchida, K.Kamata, R.Ishimoto, S.Nojima, K.Yonehara, Y.Sumida, angew.chem.Int.Id.2010, 49, 9972-9976), t-butyl hydroperoxide (D.Banerjee, R.V.Jagadeesh, K.Junge, M. -M.Pohl, J.Radnik, A.Br ckner, M.Beller, angew.Chem.Int.Ed.2014,53,4359-4363; M.Shokuhimehr, Y.Piao, J.Kim, Y.Jang, T.Hyeon, angew.chem.Int.Ed.2007,46, 7039-7043) and oxygen (T.Mukaiyama, T.Yamada, bull.Chem.Soc.Jpn.1995,68,13-35). Oxygen is becoming a growing concern to chemists and industry due to its inexpensive and readily available, easy to handle, and non-toxic nature. Over the past several decades, many transition metal catalysts have included manganese (L.Hadian-Dehkordi, H.Hosseini-Monfared, P.Aleshkevych, inorg.Chim.Acta 2017,462,142-151; S.Mohebbi, F.Nikpour, S.Raiati, J.mol. Catalyst. A2006,256, 265-268), cobalt (N.V.Maksimchuk, M.S.Melgunov, Y.A.Chesalov, J).
Figure BDA0002396303590000021
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Figure BDA0002396303590000022
O.A.Kholdeeva, J.Catal.2007,246,241-248), copper (Y.Qi, Y.Luan, J.Yu, X.Peng, G.Wang, chem.Eur.J.2015,21,1589-1597; G.Yang, H.Du, J.Liu, Z.Zhou, X.Hu, Z.Zhang, green chem.,2017,19,675-681), palladium (X.He, L.Chen, X.Zhou, H.Ji, catal.Commun.2016,83,78-81), ruthenium (P.Mekrattanachai, J.Liu, Z.Li, C.Cao, W.Song, chem.Commun.2018,54, 1433-1436), and the like are reported for the oxygen epoxidation of olefins. In order to facilitate separation of the catalyst from the product and recovery and reuse of the catalyst, it is particularly important to develop efficient heterogeneous catalysts. For example, wang et al found that epoxidation of olefins could be achieved under mild conditions using copper metal organic framework materials as heterogeneous catalysts, which remained active for 15 cycles (Y.Qi, Y.Luan, J.Yu, X.Peng, G.Wang, chem.Eur.J.2015,21, 1589-1597). Hosseini-Monfared et al report the synthesis of chiral epoxy compounds by catalytic asymmetric epoxidation of olefins using magnetic nano ferroferric oxide stabilized with chiral tartaric acid at room temperature, with 5 activities remaining unchanged for catalyst recovery (L.Hadian-Dehkordi, H.Hosseini-Monfared, green chem.2016,18, 497-507). Pereira et al use a nano ferroferric oxide supported manganese porphyrin complex to catalyze the epoxidation of olefins (L.D.Dias, R.M.B.Carrilho, C.A.Henriques, M.J.F.Calvete, A.M.Masdeu-Bultj, C.Claver, L.M.Rossi, M.M.Pereira, chemCatChem 2018,10,2792-2803).
Although the development of olefin epoxidation catalysts has been greatly progressed at present, many catalysts have the problems of low catalytic activity, high price, difficult synthesis, environmental friendliness and the like. Therefore, the development of a catalyst system which is cheap and easily available, environment-friendly, recyclable, and high in activity and selectivity is still of great importance.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina.
The invention provides a method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina. The method is characterized in that olefin is used as a raw material, and epoxidation reaction is carried out in one step under the conditions that nano aluminum oxide is used as a catalyst, aliphatic aldehyde is used as a reducing agent and oxygen is used as an oxidant to obtain the epoxy compound.
The object of the invention is achieved by at least one of the following technical solutions.
According to the method provided by the invention, a solvent, olefin, nano aluminum oxide and fatty aldehyde are added into a reactor to obtain a mixed solution, the olefin in the mixed solution is used as a raw material, the nano aluminum oxide is used as a catalyst, the fatty aldehyde is used as a reducing agent, the reaction vessel is vacuumized and then oxygen is introduced, the reaction is heated and stirred for reaction, the reaction solution is obtained after the reaction is finished, and the reaction solution is separated and purified to obtain the epoxy compound.
The invention provides a method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following chemical reaction equation:
Figure BDA0002396303590000031
in the method, in the process of the invention,
Figure BDA0002396303590000032
is 1-phenyl-1-cyclohexene, 1-octene, n-decene, tetracyclododecene, cyclododecene, styrene, cis-1-phenylpropene, trans-1-phenylpropene, 1-allyl-2-toluene, 4-phenyl-1-butene, 3-bromostyrene, 3-chlorostyrene, 4-bromoOne of styrene, 4-chlorostyrene, trans-1, 2-stilbene, 1-acetyl-1-cyclohexene, trans-4-phenyl-3-buten-2-one, allyl phenylacetate, trans-chalcone, 2-benzylidene cyclohexanone, trans-3-hexenoic acid ethyl ester, methyl cinnamate, cinnamate acetate, cinnamate propionate, cinnamate butyrate, cinnamate isobutyrate, 1, 4-epoxy-1, 4-dihydronaphthalene;
in the method, in the process of the invention,
Figure BDA0002396303590000033
1-phenyl-7-oxa-bicyclo [4.1.0]Heptane, 1, 2-epoxyoctane, 1, 2-epoxysunflower-alkylene, 2R,2aR,3S,6R,6aS, 7S) -decahydro-2:, 7:3, 6-dimethyloctahydronaphthalene, tetracyclo [2,3-b ]]Ethylene oxide, 1, 3-oxabicyclo [10.1.0 ]]Tridecane, phenyloxirane, cis-2-methyl-3-phenyloxirane, trans-2-methyl-3-phenyloxirane, 2-methyl-1, 2-phenylpropanolene, 1, 2-epoxy-4-phenyl-butane, 3-bromophenyloxirane, 3-chlorophenyl oxirane, 4-bromophenyloxirane, 4-chlorophenyl oxirane, trans-1, 2-diphenyloxirane, 1- (7-oxabicyclo [4.1.0 ]]Hept-1-yl) ethanone, 1- (3-phenyloxiranyl) -ethanone, (oxiranylmethyl) phenylacetate, (3-phenyloxiranyl) phenylmethanone, 2-phenyl-1-oxaspiro [2.5 ]]Octane-4-one, ethyl 2- (3-ethyloxiranyl) acetate, methyl 2-phenyloxirane-1-carboxylate, 3-phenyloxiranylmethyl acetate, 3-phenyloxiranylmethyl propionate, 3-phenyloxiranylmethyl butyrate, 3-phenyloxiranylmethyl isobutyrate, 3-phenyloxiranylmethyl cinnamate, 1a,2,7 a-tetrahydro-2, 7-epoxynaphtho [2,3-b ]]One of ethylene oxide.
The invention provides a method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
(1) Adding an organic solvent, olefin, nano alumina and fatty aldehyde into a reaction container, uniformly mixing to obtain a mixed solution, vacuumizing the reaction container, introducing oxygen, heating, stirring for reaction, and cooling to room temperature to obtain a reaction solution;
(2) And (3) separating and purifying the reaction liquid in the step (1) to obtain the epoxy compound.
Further, the organic solvent in the step (1) is one of acetonitrile and ethyl acetate.
Further, the olefin in the step (1) is 1-phenyl-1-cyclohexene, 1-octene, n-sunflower, tetracyclododecene, cyclododecene, styrene, cis-1-phenylpropene, trans-1-phenylpropene, 1-allyl-2-toluene, 4-phenyl-1-butene, 3-bromostyrene, 3-chlorostyrene, 4-bromostyrene, 4-chlorostyrene, trans-1, 2-stilbene, 1-acetyl-1-cyclohexene, trans-4-phenyl-3-butene-2-one, allyl phenylacetate, trans-chalcone, 2-benzylidene cyclohexanone, trans-3-hexenoate, methyl cinnamate, cinnamyl acetate, cinnamyl propionate, cinnamyl butyrate, cinnamyl isobutyrate, and 1, 4-epoxy-1, 4-dihydronaphthalene.
Further, the particle size of the nano alumina in the step (1) is 20-100 nanometers; the molar ratio of the nano alumina to the olefin is (0.05-0.15): 1.
further, the fatty aldehyde in the step (1) is butyraldehyde, isobutyraldehyde, isovaleraldehyde, valeraldehyde, nonanal, 3, 5-trimethylhexanal, cyclohexanal, benzaldehyde or 3-methylbenzaldehyde; the mole ratio of the fatty aldehyde to the olefin is (2-3): 1.
further, the molar volume ratio of the olefin to the organic solvent in the step (1) is 0.1-0.5mmol/mL.
Further, after the oxygen is introduced in the step (1), the gas pressure of the reaction vessel is 1-2 atmospheres.
Further, the heating temperature in the step (1) is 50-60 ℃, and the stirring speed of the stirring reaction is 400-800rpm; the stirring reaction time is 12-36h.
Further, the separation and purification of the step (2) comprises:
filtering and concentrating the reaction liquid obtained in the step (1) under reduced pressure to obtain a crude product, and purifying the crude product by column chromatography to obtain an epoxy compound; the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is (10-50): 1.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the method for synthesizing the epoxy compound by catalyzing olefin epoxy by using nano alumina is different from the traditional epoxy compound synthesis method, has the advantages of cheap and easily available catalyst, mild reaction condition, wide applicability to substrates, safe and simple operation and potential industrial application prospect.
Drawings
FIGS. 1 and 2 are respectively a hydrogen spectrum and a carbon spectrum of the target products obtained in examples 1 to 12;
FIGS. 3 and 4 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 13;
FIGS. 5 and 6 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 14;
FIGS. 7 and 8 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 15;
FIGS. 9 and 10 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 16;
FIGS. 11 and 12 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 17;
FIGS. 13 and 14 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 18;
FIGS. 15 and 16 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 19;
FIGS. 17 and 18 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 20;
fig. 19 and 20 are a hydrogen spectrum and a carbon spectrum, respectively, of the target product obtained in example 21.
Detailed Description
Specific implementations of the invention are further described below with reference to the drawings and examples, but the implementation and protection of the invention are not limited thereto. It should be noted that the following processes, if not specifically described in detail, can be realized or understood by those skilled in the art with reference to the prior art. The reagents or apparatus used were not manufacturer-specific and were considered conventional products commercially available.
Example 1
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of 1-phenyl-1-cyclohexene, 3 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 20 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction is stirred for 24 hours at 60 ℃, the stirring speed is 700rpm, heating and stirring are stopped, cooling to room temperature, the reaction solution is filtered, decompressed and concentrated, and then the target product is obtained by separating and purifying by column chromatography, wherein the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1.
Example 2
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of 1-phenyl-1-cyclohexene, 3 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction is stirred for 24 hours at 60 ℃, the stirring speed is 700rpm, heating and stirring are stopped, cooling to room temperature, the reaction solution is filtered, decompressed and concentrated, and then the target product is obtained by separating and purifying by column chromatography, wherein the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1.
Example 3
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of 1-phenyl-1-cyclohexene, 3 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 100 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction is stirred for 24 hours at 60 ℃, the stirring speed is 700rpm, heating and stirring are stopped, cooling to room temperature, the reaction solution is filtered, decompressed and concentrated, and then the target product is obtained by separating and purifying by column chromatography, wherein the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1.
Example 4
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of 1-phenyl-1-cyclohexene, 3 mmol of 3, 5-trimethylhexanal and 0.05 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction is stirred for 24 hours at 60 ℃, the stirring speed is 700rpm, heating and stirring are stopped, cooling to room temperature, the reaction solution is filtered, decompressed and concentrated, and then the target product is obtained by separating and purifying by column chromatography, wherein the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1.
Example 5
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of 1-phenyl-1-cyclohexene, 3 mmol of 3, 5-trimethylhexanal and 0.15 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction is stirred for 24 hours at 60 ℃, the stirring speed is 700rpm, heating and stirring are stopped, cooling to room temperature, the reaction solution is filtered, decompressed and concentrated, and then the target product is obtained by separating and purifying by column chromatography, wherein the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1.
Example 6
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of 1-phenyl-1-cyclohexene, 3 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction is stirred for 24 hours at 50 ℃, the stirring speed is 700rpm, heating and stirring are stopped, cooling to room temperature, the reaction solution is filtered, decompressed and concentrated, and then the target product is obtained by separating and purifying by column chromatography, wherein the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1.
Example 7
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of 1-phenyl-1-cyclohexene, 3 mmol of isobutyraldehyde and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction tube is stirred at 60 ℃ for 24 hours, the stirring speed is 700rpm, heating and stirring are stopped, the reaction tube is cooled to room temperature, the reaction liquid is filtered, decompressed and concentrated, and then separated and purified by column chromatography, wherein the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1, and the target product is obtained with the yield of 54%.
Example 8
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
2 ml of acetonitrile, 1mmol of 1-phenyl-1-cyclohexene, 3 mmol of butyraldehyde and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction tube is stirred at 60 ℃ for 24 hours, the stirring speed is 700rpm, heating and stirring are stopped, the reaction tube is cooled to room temperature, the reaction liquid is filtered, the reduced pressure concentration is carried out, the separation and the purification are carried out through column chromatography, the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1, and the target product is obtained with the yield of 24%.
Example 9
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
10 ml of acetonitrile, 1mmol of 1-phenyl-1-cyclohexene, 3 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction is stirred for 24 hours at 60 ℃, the stirring speed is 700rpm, heating and stirring are stopped, cooling to room temperature, the reaction solution is filtered, decompressed and concentrated, and then the target product is obtained by separating and purifying by column chromatography, wherein the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1.
Example 10
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of ethyl acetate, 1mmol of 1-phenyl-1-cyclohexene, 3 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction tube is stirred for 24 hours at 60 ℃, the stirring speed is 700rpm, heating and stirring are stopped, the reaction liquid is cooled to room temperature, the reaction liquid is filtered, decompressed and concentrated, and then the target product is obtained by separating and purifying through column chromatography, wherein the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1.
Example 11
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of 1-phenyl-1-cyclohexene, 2 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction is stirred for 24 hours at 60 ℃, the stirring speed is 700rpm, heating and stirring are stopped, cooling to room temperature, the reaction solution is filtered, decompressed and concentrated, and then the target product is obtained by separating and purifying by column chromatography, wherein the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1.
Example 12
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of 1-phenyl-1-cyclohexene, 3 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 2 atmospheres, the reaction is stirred for 12 hours at 60 ℃, the stirring speed is 400rpm, heating and stirring are stopped, cooling to room temperature, the reaction solution is filtered, decompressed and concentrated, and then the target product is obtained by separating and purifying by column chromatography, wherein the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1.
The hydrogen and carbon spectra of the products obtained in examples 1 to 12 are shown in fig. 1 and 2, respectively, and the structural characterization data are shown as follows:
1 H NMR(500MHz,CDCl 3 ):δ＝7.27–7.11(m,5H),2.95(d,J＝3.5Hz,1H),2.19–2.13(m,1H),2.02-1.97(m,1H),1.92–1.81(m,2H),1.53–1.47(m,2H),1.38-1.31(m,1H),1.24-1.15(m,1H)；
13 C NMR(126MHz,CDCl 3 ):δ＝142.6,128.3,127.2,125.3,77.4,77.1,76.9,61.9,60.2,28.9,24.8,20.2,19.8；
IR(KBr):3060,2933,1450,966,859,749,543cm -1 。
the structure of the target product is deduced from the above data as follows:
Figure BDA0002396303590000081
example 13
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of 1-octene, 3 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction tube is stirred at 60 ℃ for 12 hours, the stirring speed is 800rpm, heating and stirring are stopped, cooling to room temperature, the reaction liquid is filtered, decompressed and concentrated, separation and purification are carried out through column chromatography, and the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1, so that the target product is obtained, and the yield is 63%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 3 and 4, and the structural characterization data are shown as follows:
1 H NMR(400MHz,CDCl 3 ):δ＝2.82–2.77(m,1H),2.64–2.62(m,1H),2.36–2.34(m,1H),1.46–1.21(m,10H),0.80(t,J＝6.8Hz,3H)；
13 C NMR(100MHz,CDCl 3 ):δ＝77.4,77.1,76.8,52.2,46.8,32.4,31.7,29.0,25.9,22.5,13.9；
IR(KBr):2934,1462,836cm -1 。
the structure of the target product is deduced from the above data as follows:
Figure BDA0002396303590000082
example 14
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of n-decene, 3 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction tube is stirred at 60 ℃ for 24 hours, the stirring speed is 700rpm, heating and stirring are stopped, cooling to room temperature, the reaction liquid is filtered, reduced pressure concentration is carried out, separation and purification are carried out through column chromatography, and the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1, thus obtaining the target product with the yield of 75%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 5 and 6, and the structural characterization data are shown as follows:
1 H NMR(500MHz,CDCl 3 ):δ＝2.88(s,1H),2.73-2.71(m,1H),2.44–2.43(m,1H),1.53–1.26(m,14H),0.86(t,J＝6.5Hz,3H)；
13 C NMR(126MHz,CDCl 3 ):δ＝77.3,77.0,76.8,52.4,47.1,32.5,31.8,29.5,29.4,29.2,26.0,22.6,14.0；
IR(KBr):2932,1461,836cm -1 。
the structure of the target product is deduced from the above data as follows:
Figure BDA0002396303590000091
example 15
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of tetracyclododecene, 3 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction tube is stirred at 60 ℃ for 24 hours, the stirring speed is 700rpm, heating and stirring are stopped, cooling to room temperature, the reaction liquid is filtered, decompressed and concentrated, separation and purification are carried out through column chromatography, and the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1, so that the target product is obtained, and the yield is 90%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 7 and 8, and the structural characterization data are shown as follows:
1 H NMR(500MHz,CDCl 3 ):δ＝3.07(s,2H),2.53(s,2H),2.21(s,2H),1.80(d,J＝11.0Hz,1H),1.75(t,J＝9.5Hz,2H),1.42(d,J＝7.5Hz,2H),1.32(d,J＝9.5Hz,1H),0.97–0.93(m,2H),0.89(d,J＝11.0Hz,1H),0.55(d,J＝9.5Hz,1H)；
13 C NMR(126MHz,CDCl 3 ):δ＝77.4,77.1,76.9,51.4,50.0,41.5,36.9,36.6,31.1,28.2；
IR(KBr):2908,1469,851cm -1 ；
HRMS(ESI)Calcd for C 12 H 16 O[M+H] + :199.1093,Found 199.1089。
the structure of the target product is deduced from the above data as follows:
Figure BDA0002396303590000092
example 16
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of styrene, 3 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction tube is stirred at 60 ℃ for 36 hours, the stirring speed is 700rpm, heating and stirring are stopped, cooling to room temperature, the reaction liquid is filtered, reduced pressure concentration is carried out, separation and purification are carried out through column chromatography, the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1, and the target product is obtained, and the yield is 69%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 9 and 10, and the structural characterization data are shown as follows:
1 H NMR(500MHz,CDCl 3 ):δ＝7.31–7.22(m,5H),3.78(t,J＝3.0Hz,1H),3.05(t,J＝5.0Hz,1H),2.72(dd,J＝5.5Hz,2.5Hz,1H)；
13 C NMR(126MHz,CDCl 3 ):δ＝137.8,128.6,128.2,125.6,77.5,77.3,77.0,52.4,51.2；
IR(KBr):3676,3042,1708,1582,1480,1385,984,877,757,692,540cm -1 。
the structure of the target product is deduced from the above data as follows:
Figure BDA0002396303590000101
example 17
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of trans-1, 2-stilbene, 3 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction is stirred for 24 hours at 60 ℃, the stirring speed is 700rpm, heating and stirring are stopped, the reaction liquid is cooled to room temperature, the reaction liquid is filtered, decompressed and concentrated, and then the target product is obtained by separating and purifying through column chromatography, wherein the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 50:1.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 11 and 12, and the structural characterization data are shown as follows:
1 H NMR(400MHz,CDCl 3 ):δ＝7.51–7.42(m,10H),3.98(s,2H)；
13 C NMR(100MHz,CDCl 3 ):δ＝137.3,128.7,128.5,125.7,77.6,77.3,76.9,63.0；
IR(KBr):3692,3029,1724,1578,1485,1289,1004,863,704cm -1 。
the structure of the target product is deduced from the above data as follows:
Figure BDA0002396303590000102
example 18
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of cinnamyl acetate, 3 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction tube is stirred at 60 ℃ for 24 hours, the stirring speed is 700rpm, heating and stirring are stopped, cooling to room temperature, the reaction liquid is filtered, reduced pressure concentration is carried out, separation and purification are carried out through column chromatography, and the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 20:1, thus obtaining the target product with the yield of 76%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 13 and 14, and the structural characterization data are shown as follows:
1 H NMR(500MHz,CDCl 3 ):δ＝7.34–7.21(m,5H),4.42(dd,J＝12.5Hz,3.0Hz,1H),4.05–4.01(m,1H),3.75(s,1H),3.21–3.20(m,1H),2.06–2.05(m,3H)；
13 C NMR(126MHz,CDCl 3 ):δ＝170.7,136.3,128.6,128.5,125.7,77.5,77.3,77.0,64.2,59.3,56.4,20.7；
IR(KBr):3694,3483,3144,1729,1572,987cm -1 。
the structure of the target product is deduced from the above data as follows:
Figure BDA0002396303590000111
example 19
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of cinnamyl propionate, 3 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction tube is stirred at 60 ℃ for 24 hours, the stirring speed is 700rpm, heating and stirring are stopped, cooling to room temperature, the reaction liquid is filtered, reduced pressure concentration is carried out, separation and purification are carried out through column chromatography, and the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 20:1, thus obtaining the target product with the yield of 86%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 15 and fig. 16, and the structural characterization data are shown as follows:
1 H NMR(500MHz,CDCl 3 ):δ＝7.28–7.18(m,5H),4.40(dd,J＝12.5Hz,3.5Hz,1H),4.01(dd,J＝12.5Hz,6.0Hz,1H),3.72(d,J＝2.0Hz,1H),3.19-3.16(m,1H),2.31(q,J＝7.5Hz,2H),1.08(t,J＝7.5Hz,3H)；
13 C NMR(126MHz,CDCl 3 ):δ＝174.1,136.3,128.6,128.5,125.7,77.5,77.2,77.0,64.1,59.3,56.4,27.3,9.0；
IR(KBr):3665,3495,3282,3130,2975,1722,1583cm -1 ；
HRMS(ESI)Calcd for C 12 H 14 O 3 [M+H] + :229.0835,Found 229.0840。
the structure of the target product is deduced from the above data as follows:
Figure BDA0002396303590000121
example 20
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of cinnamyl butyrate, 3 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction tube is stirred at 60 ℃ for 24 hours, the stirring speed is 700rpm, heating and stirring are stopped, cooling to room temperature, the reaction liquid is filtered, reduced pressure concentration is carried out, separation and purification are carried out through column chromatography, and the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 20:1, thus obtaining the target product with the yield of 82%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 17 and 18, and the structural characterization data are shown as follows:
1 H NMR(500MHz,CDCl 3 ):δ＝7.28–7.18(m,5H),4.40(dd,J＝12.5,3.5,1H),4.02(dd,J＝12.5Hz,6.0Hz,1H),3.71(d,J＝2.0Hz,1H),3.18–3.16(m,1H),2.27(t,J＝7.5Hz,2H),1.64-1.56(m,2H),0.88(t,J＝7.5Hz,3H)；
13 C NMR(126MHz,CDCl 3 ):δ＝173.3,136.3,128.6,128.5,125.7,77.4,77.1,76.8,63.9,59.4,56.4,35.9,18.4,13.7；
IR(KBr):3680,3477,2959,1735,1583,1460,1175,993,880,690cm -1 ；
HRMS(ESI)Calcd for C 13 H 16 O 3 [M+H] + :243.0992,Found 243.0996。
the structure of the target product is deduced from the above data as follows:
Figure BDA0002396303590000122
example 21
A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina, which comprises the following steps:
5 ml of acetonitrile, 1mmol of cinnamyl isobutyrate, 3 mmol of 3, 5-trimethylhexanal and 0.1 mmol of nano alumina (particle size of 50 nm) are added into a reaction tube, the reaction tube is vacuumized, then oxygen is filled, the gas pressure of the reaction tube after the oxygen is filled is 1 atmosphere, the reaction tube is stirred at 60 ℃ for 24 hours, the stirring speed is 700rpm, heating and stirring are stopped, cooling to room temperature, the reaction liquid is filtered, decompressed and concentrated, separation and purification are carried out through column chromatography, and the used column chromatography developing agent is petroleum ether and ethyl acetate mixed solvent with the volume ratio of 20:1, so that the target product is obtained, and the yield is 88%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 19 and 20, and the structural characterization data are shown as follows:
1 H NMR(500MHz,CDCl 3 ):δ＝7.32–7.21(m,5H),4.44(dd,J＝12.0Hz,3.0Hz,1H),4.05(dd,J＝12.5Hz,6.0Hz,1H),3.75(d,J＝2.0Hz,1H),3.22-3.20(m,1H),2.62-2.53(m,1H),1.16(d,J＝7.5Hz,6H)；
13 C NMR(126MHz,CDCl 3 ):δ＝176.8,136.3,128.6,128.5,125.7,77.4,77.1,76.9,64.0,59.4,56.3,33.9,19.0；
IR(KBr):3680,2961,1737,1589,1463,1373,1163,990,881,758,695cm -1 ；
HRMS(ESI)Calcd for C 13 H 16 O 3 [M+H] + :243.0992,Found 243.0996。
the structure of the target product is deduced from the above data as follows:
Figure BDA0002396303590000131
the above examples are only preferred embodiments of the present invention, and are merely for illustrating the present invention, not for limiting the present invention, and those skilled in the art should not be able to make any changes, substitutions, modifications and the like without departing from the spirit of the present invention.

Claims (5)

1. A method for synthesizing an epoxy compound by catalyzing olefin epoxy by using nano alumina is characterized in that a chemical reaction equation is that
Figure FDA0004049299990000011
In the method, in the process of the invention,
Figure FDA0004049299990000012
is one of 1-phenyl-1-cyclohexene, 1-octene, n-decene, tetracyclododecene, cyclododecene, styrene, cis-1-phenylpropene, trans-1-phenylpropene, 1-allyl-2-toluene, 4-phenyl-1-butene, 3-bromostyrene, 3-chlorostyrene, 4-bromostyrene, 4-chlorostyrene, trans-1, 2-stilbene, 1-acetyl-1-cyclohexene, trans-4-phenyl-3-buten-2-one, allyl phenylacetate, trans-chalcone, 2-benzylidene cyclohexanone, trans-3-hexenoate ethyl ester, methyl cinnamate, cinnamyl acetate, cinnamyl propionate, cinnamyl butyrate, cinnamyl isobutyrate, 1, 4-epoxy-1, 4-dihydronaphthalene;
in the middle of，
Figure FDA0004049299990000013
1-phenyl-7-oxa-bicyclo [4.1.0]Heptane, 1, 2-epoxyoctane, 1, 2-epoxysunflower-alkylene, tetracyclo [6.2.1.1 ] 3,6 .0 2,7 ]Twelve-4, 5-epoxy alkane, 1, 3-oxabicyclo [10.1.0 ]]Tridecane, phenyloxirane, cis-2-methyl-3-phenyloxirane, trans-2-methyl-3-phenyloxirane, 2-methyl-1, 2-phenylpropanolene, 1, 2-epoxy-4-phenyl-butane, 3-bromophenyloxirane, 3-chlorophenyl oxirane, 4-bromophenyloxirane, 4-chlorophenyl oxirane, trans-1, 2-diphenyloxirane, 1- (7-oxabicyclo [4.1.0 ]]Hept-1-yl) ethanone, 1- (3-phenyloxiranyl) -ethanone, (oxiranylmethyl) phenylacetate, (3-phenyloxiranyl) phenylmethanone, 2-phenyl-1-oxaspiro [2.5 ]]Octane-4-one, ethyl 2- (3-ethyloxiranyl) acetate, methyl 2-phenyloxirane-1-carboxylate, 3-phenyloxiranylmethyl acetate, 3-phenyloxiranylmethyl propionate, 3-phenyloxiranylmethyl butyrate, 3-phenyloxiranylmethyl isobutyrate, 3-phenyloxiranylmethyl cinnamate, 1a,2,7 a-tetrahydro-2, 7-epoxynaphtho [2,3-b ]]One of ethylene oxide;
the method for synthesizing the epoxy compound by catalyzing olefin epoxy by using nano alumina comprises the following steps:
(1) Adding an organic solvent, olefin, nano aluminum oxide and fatty aldehyde into a reaction vessel, uniformly mixing to obtain a mixed solution, vacuumizing the reaction vessel, introducing oxygen, heating, stirring for reaction, and cooling to obtain a reaction solution, wherein the particle size of the nano aluminum oxide is 20-100 nanometers, and the molar ratio of the nano aluminum oxide to the olefin is (0.05-0.15): 1, the organic solvent is one of acetonitrile and ethyl acetate, the fatty aldehyde is 3, 5-trimethyl hexanal, the gas pressure of the reaction vessel after oxygen is introduced is 1-2 atmospheres, and the heating temperature is 50-60 ℃;
(2) And (3) separating and purifying the reaction liquid in the step (1) to obtain the epoxy compound.
2. The method for synthesizing an epoxy compound by catalyzing olefin epoxidation with nano alumina according to claim 1, wherein the molar volume ratio of the olefin to the organic solvent in the step (1) is 0.1-0.5:1mmol/mL.
3. The method for synthesizing an epoxy compound by catalyzing the epoxidation of an olefin with nano alumina according to claim 1, wherein the molar ratio of the fatty aldehyde to the olefin in the step (1) is (2-3): 1.
4. the method for synthesizing an epoxy compound by catalyzing an olefin epoxidation with nano alumina according to claim 1, wherein in the step (1), the stirring rate of the stirring reaction is 400 to 800rpm; the stirring reaction time is 12-36h.
5. The method for synthesizing an epoxy compound by catalyzing an olefin epoxidation with nano alumina according to claim 1, wherein said separating and purifying in the step (2) comprises:
filtering and concentrating the reaction liquid obtained in the step (1) under reduced pressure to obtain a crude product, and purifying the crude product by column chromatography to obtain an epoxy compound; the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is (10-50): 1.
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