CN111253207B - Preparation method of visible light catalyzed double-chlorine addition product of aromatic olefin - Google Patents
Preparation method of visible light catalyzed double-chlorine addition product of aromatic olefin Download PDFInfo
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Abstract
The invention relates to a preparation method of a visible light catalyzed double-chlorine addition product of aromatic olefin, which comprises the following steps: taking aromatic olefin as a substrate, taking copper chloride with visible light absorption capacity as a chlorine source, reacting in an organic solvent under the irradiation of visible light, carrying out the reaction in an inert atmosphere, and obtaining a double-chlorine addition product of the aromatic olefin after the reaction is completed; aromatic olefins include carbon-carbon double bonds and aromatic groups covalently bonded to the carbon-carbon double bond. The method utilizes visible light to provide energy required by reaction, utilizes copper chloride with visible light absorption capacity and a reaction substrate to carry out photoinduced chlorine atom transfer to initiate addition reaction, and obtains a dichloride addition product.
Description
Technical Field
The invention relates to the technical field of synthesis of a bischloro addition product, in particular to a preparation method of a visible light catalyzed bischloro addition product of aromatic olefin.
Background
More than 2000 natural products containing the double chlorine structure exist, and the natural products are often used as chiral catalysts, pharmaceutical intermediates and organic synthesis intermediates. The introduction of chlorine atoms will significantly change the physical and chemical properties of compounds, which are often used in the fields of medicine, pesticides, material science, etc. Therefore, the synthesis of the bischloro-containing compound is particularly important. Through literature investigation, the existing methods for synthesizing the dichlorine compound have some defects, such as harsh reaction conditions, low yield, narrow substrate range, need of toxic and harmful heavy-pollution chlorine sources and the like. For example:
(1) BabakBorhan et al reported the use of chiral catalysts (DHQD)2PHAL and DCDMH (1, 3-dichloro-5, 5-dimethylhydantoin) are added to olefin to obtain the dichloro compound. However, the method needs to use expensive catalyst, a large amount of inorganic salt and has a limited reaction substrate, and the method focuses on allyl amide compounds and is not suitable for common aliphatic olefins and aromatic olefins (see: Babak Borhan; J.am.chem.Soc.2017,139, 2132-2135);
(2) rendy Kartika et al reported the use of potassium peroxymonosulfonate and ammonium chloride to generate a chlorine positive ion that in turn undergoes a chloride onium ion addition to styrene. The process requires a large amount of dangerous inorganic salt oxidant, which brings safety hazard and causes serious environmental pollution (see: Nama Narender, synthesis, 2014,46, 251-257);
(3) james b.hendrickson et al reported the use of an epoxy compound, triphosgene and pyridine to produce a similar chloronium ion intermediate to give a bischloro compound. The synthesis of the epoxy compound as the raw material is complicated, the substrate is relatively limited, and the reaction conditions are relatively dangerous (see James B.Hendrickson; J.org.chem.2018,83, 3367-one 3377);
(4) song Lin et al reported that the formation of double-chlorinated products by the radical addition of chlorine radicals with olefins in an electrocatalytic mode using transition metal manganese as a catalyst and magnesium chloride as a chlorine source. The system is novel, but dangerous strong oxidant lithium perchlorate is adopted as electrolyte, and the reaction system is complicated. (see: Song Lin; J.am.chem.Soc.2017,139, 15548-15553).
(5) CN 103304355A, CN 103304367A, CN 103382144A and CN106831314A disclose a halogenation method of alkane, cycloalkane, alkylaromatic hydrocarbon, alkene or alkene derivative by using visible light to provide energy required for reaction or double bond addition halogenation method, using halogen acid or halogen acid salt as halogenating agent, reacting substrate under the catalysis of nano noble metal/semiconductor surface plasma composite material to obtain final product. The catalyst used in the above reaction is a noble metal catalyst, which is expensive. And the electrons of the halogen anions need to be transferred by the semiconductor gaps in the photocatalyst, and the process causes partial loss of the light energy absorbed by the catalyst. In addition, the reaction system is nano heterogeneous catalysis and has the defect of poor repeatability.
In summary, the methods for synthesizing the bischloro compounds reported at present are complicated in reaction process, adopt a chlorine source with high toxicity, and have the disadvantages of harsh reaction conditions, low yield and single reaction mode (most of the methods are thermal reactions). Therefore, it is important to develop a green, mild, efficient, energy-saving and environment-friendly visible light catalytic chlorination method with abundant raw material sources.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of a double-chlorine addition product of aromatic olefin catalyzed by visible light.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention relates to a preparation method of a visible light catalyzed double-chlorine addition product of aromatic olefin, which comprises the following steps:
taking aromatic olefin as a substrate, taking copper chloride with visible light absorption capacity as a chlorine source, reacting in an organic solvent under the irradiation of visible light, carrying out the reaction in an inert atmosphere, and obtaining a double-chlorine addition product of the aromatic olefin after the reaction is completed; the aromatic olefin comprises a carbon-carbon double bond and a C6-C15 aryl group covalently bonded to the carbon-carbon double bond.
Further, the aromatic olefin has the structural formula
The structural formula of the double-chlorine addition product of the aromatic olefin is shown as
Wherein one of R1 and R2 is selected from substituted or unsubstituted C6-C10 aryl; another is selected from hydrogen or a substituted or unsubstituted C6-C10 aryl group; the substituent on the aryl is selected from one or more of C1-C4 alkyl, C1-C4 alkoxy, nitro, phenyl, halogen, trifluoromethyl, acetoxyl, cyano and carboxyl.
Preferably, R1And R2Is selected from substituted or unsubstituted C6-C10 aryl; the other is selected from hydrogen.
Further, aryl is phenyl, naphthyl, biphenyl, or benzoyl.
Furthermore, the substituent on the aryl is selected from one or more of nitro, phenyl, halogen, trifluoromethyl, acetoxyl, cyano and carboxyl.
Preferably, R1And R2One of which is hydrogen and the other is selected from phenyl, naphthyl, biphenyl and mono-substituted phenyl, wherein the substituent on the mono-substituted phenyl is halogen, acetoxy or nitro.
Further, halogen is fluorine, chlorine, bromine or iodine.
Preferably, R1And R2Are all phenyl; or R1And R2One of them is phenyl and the other is benzoyl.
Further, the reaction temperature is 23-25 ℃; the reaction time is 36-72 hours. Preferably, the reaction time is 72 hours.
Further, the organic solvent is one or more of petroleum ether, 1, 2-dichloroethane, 1,1, 1-trichloroethane, 1,1, 2-trichloroethane, nitromethane, acetonitrile, ethyl acetate and acetone. Preferably, the organic solvent is acetonitrile.
Further, the inert atmosphere is a nitrogen atmosphere. For the aromatic olefin, an inert atmosphere is used as the reaction condition, considering that the substrate is relatively active and chlorocarbonyl type compounds are easily produced.
Further, the chlorine source is 4 times the molar amount of the aromatic olefin.
Further, the light source of the visible light is an LED lamp. The LED lamp can be a white lamp, a green lamp or a blue lamp; the power is 18W-38W.
Preferably, the source of visible light is a white LED lamp with a power of 38W.
Further, the reaction is completed, and the purification steps of drying the product with anhydrous sodium sulfate, removing the solvent with a rotary evaporator and performing column chromatography are included.
The 'light' in the light reaction is a special reagent which can participate in the reaction, and a metal complex, an organic dye or a semiconductor with visible light absorption is used as a photosensitizer, so that the photosensitizer and a reaction substrate generate photoinduced electron transfer to generate a positive ion free radical or a negative ion free radical of the substrate, and the subsequent reaction is initiated. Compared with the classical thermochemical reaction, the photochemical reaction has the following characteristics: (1) thermochemical reaction needs larger activation energy and can be carried out only by heating to a certain temperature; the photochemical reaction does not need activation energy or needs very small activation energy, so that the photochemical reaction does not need heating generally and can be rapidly carried out at room temperature; (2) complex molecules often contain multiple reactive groups. In the thermochemical reaction, other groups need to be protected to react with one group; the photochemical reaction can select light with a specific wavelength to excite a certain group according to different positions of the group in a molecule and different wavelengths of absorbed light to initiate the reaction; (3) in most cases, the thermochemical reaction is different from the photochemical reaction, and thus a product which cannot be synthesized by the thermochemical reaction can be synthesized by the photochemical reaction.
The invention adopts a green, environment-friendly, mild, high-efficiency and energy-saving visible light catalysis strategy to synthesize the dichlorine compound, wherein a light source is visible light, and the copper chloride is a commercial product and can be directly purchased and obtained.
The reaction mechanism of the invention is as follows: the invention takes copper chloride as a chlorine source, generates chlorine free radicals in an LMCT (ligand metal charge transfer) process after absorbing visible light, and further generates an addition reaction with an olefin substrate to obtain a target product.
By the scheme, the invention at least has the following advantages:
1. the invention adopts visible light catalysis mode to prepare the dichloride, and compared with the prior technology for synthesizing the dichloride, the method has the advantages of cleanness, mild reaction condition, energy conservation, saving and the like;
2. the technology of the invention does not need to pretreat the chlorine source, and can directly utilize commercial copper chloride to participate in the reaction, thereby avoiding the problem of complicated operation;
3. compared with the prior art, the method has the advantages that the olefin substrate is used as the reaction raw material, the epoxy compound is not used as the reaction raw material, and the operation is simple and convenient.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a preferred embodiment of the present invention and is described in detail below.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the present invention, the substrate olefin can be prepared from carboxylic acid or alcohols, amines, phenols, etc. as starting materials, respectively, depending on the structure.
Example one
3a (0.2mmol,30.8mg), CuCl was added in one portion to a gas shield tube2(0.8mmol,107.6mg), acetonitrile MeCN (5 mL). Then, after the system was stirred under nitrogen atmosphere at room temperature with a 38W white LED for 72 hours, the reaction system was quenched with a saturated sodium sulfite solution, extracted 3 times with ethyl acetate, and the organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, adsorbed on silica gel and purified by simple column chromatography to give the product 4a in 75% yield. The main test data of the prepared product are as follows, and through analysis,the actual synthesis product was consistent with theoretical analysis.
1H NMR(400MHz,CDCl3)δ7.89-7.83(m,4H),7.52–7.50(m,3H),5.18-5.14(m,1H),4.10–3.99(m,2H).13C NMR(100MHz,CDCl3)δ135.1,133.5,132.9,128.9,128.1,127.7,127.2,126.8,126.6,124.1,62.0,48.1；MS(EI)calculatedfor[C12H10Cl2]:224.02,found 224.00；IR(neat,cm-1):υ3057,2954,2831,1598,1506,1422,832,784,751,716,673,640.
Example two
3b (0.2mmol,36.0mg), CuCl was added in one portion to a gas shield tube2(0.8mmol,107.6mg), acetonitrile MeCN (5 mL). Then, after the system was stirred under nitrogen atmosphere at room temperature with a 38W white LED for 72 hours, the reaction system was quenched with a saturated sodium sulfite solution, extracted 3 times with ethyl acetate, and the organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, adsorbed on silica gel and purified by simple column chromatography to give 4b in 85% yield. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.61-7.57(m,4H),7.48-7.42(m,4H),7.37-7.34(m,1H),5.06-5.02(t,J＝7.2Hz,1H),4.04-3.93(m,2H).13C NMR(100MHz,CDCl3)δ142.1,140.2,136.9,128.8,127.8,127.7,127.5,127.1,61.5,48.2；MS(EI)calculatedfor[C14H12Cl2]:250.03,found 250.05；IR(neat,cm-1):υ3035,2970,1487,1435,1409,841,773,747,723,700,690.
EXAMPLE III
Adding 3c into the gas protection tube at one time(0.2mmol,24.4mg)，CuCl2(0.8mmol,107.6mg), acetonitrile MeCN (5 mL). Then, after the system was stirred under nitrogen atmosphere at room temperature with a 38W white LED for 72 hours, the reaction system was quenched with a saturated sodium sulfite solution, extracted 3 times with ethyl acetate, and the organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, adsorbed on silica gel and purified by simple column chromatography to give 4c in 64% yield. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.40-7.35(m,2H),7.09-7.03(m,2H),4.99-4.95(m,1H),3.99-3.94(m,1H),3.89-3.84(m,1H).113C NMR(100MHz,CDCl3)δ162.8(d,J＝248.6Hz),133.8(d,J＝3.3Hz),129.2(d,J＝8.5Hz),115.7(d,J＝21.9Hz),60.8,48.2；MS(EI)calculatedfor[C8H7Cl2F]:191.99,found 192.00；IR(neat,cm-1):υ2956,2926,1605,1510,1442,1424,837,792.
Example four
3d (0.2mmol,27.6mg), CuCl was added in one portion to a gas shield tube2(0.8mmol,107.6mg), acetonitrile MeCN (5 mL). Then, after the system was stirred under nitrogen atmosphere at room temperature with a 38W white LED for 72 hours, the reaction system was quenched with a saturated sodium sulfite solution, extracted 3 times with ethyl acetate, and the organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, adsorbed on silica gel and purified by simple column chromatography to give 4d in 63% yield. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.36-7.30(m,4H),4.96-4.93(m,1H),3.97-3.83(m,2H).13C NMR(100MHz,CDCl3)δ136.4,134.9,128.9,128.7,60.6,48.0；MS(EI)calculatedfor[C14H12Cl2]:207.96,found 207.95；IR(neat,cm-1):υ2953,1597,1493,1441,1410,829.
EXAMPLE five
3e (0.2mmol,36.4mg), CuCl was added in one portion to a gas shield tube2(0.8mmol,107.6mg), acetonitrile MeCN (5 mL). Then, after the system was stirred under nitrogen atmosphere at room temperature with a 38W white LED for 72 hours, the reaction system was quenched with a saturated sodium sulfite solution, extracted 3 times with ethyl acetate, and the organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporator, adsorbed on silica gel and the product 4e was obtained by simple column chromatography with a yield of 73%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.54-7.50(m,2H),7.30-7.26(m,2H),4.96-4.93(m,1H),3.99-395(m,1H),3.89-3.84(m,1H).13C NMR(100MHz,CDCl3)δ137.0,132.0,129.1,123.2,60.7,47.9；MS(EI)calculatedfor[C8H7BrCl2]:251.91,found 251.85；IR(neat,cm-1):υ2969,2953,1592,1489,1406,825,688.
EXAMPLE six
3f (0.2mmol,32.4mg), CuCl was added in one portion to a gas shield tube2(0.8mmol,107.6mg), acetonitrile MeCN (5 mL). Then the system is irradiated and stirred by a 38W white light LED for 72 hours at room temperature in the nitrogen atmosphere, the reaction system is quenched by saturated sodium sulfite solution, extracted for 3 times by ethyl acetate, organic layers are combined, dried by anhydrous sodium sulfate, a solvent is removed by a rotary evaporator, silica gel is adsorbed, and a product 4f is obtained by simple column chromatography, wherein the yield is 80%. The main test data of the products obtained are as follows, which can be found by analysisThe products of the interpositional synthesis were consistent with theoretical analysis.
1H NMR(400MHz,CDCl3)δ7.44-7.40(m,2H),7.14-7.10(m,2H),5.01-4.98(m,1H),3.99-3.95(m,1H),3.91-3.87(m,1H),3.20(s,3H).13C NMR(100MHz,CDCl3)δ169.1,151.0,135.5,128.6,121.9,61.1,48.3,21.1；HRMS(ESI-TOF):Anal Calcd.For.C10H10 35Cl2O2+Na+:254.9950,C10H10 35Cl37ClO2+Na+:256.9921,C10H10 37Cl2O2+Na+:258.9891,Found:254.9958,256.9916,258.9921；IR(neat,cm-1):υ2920,2850,1742,1608,1513,1448,1427,1200,854.
EXAMPLE seven
3g (0.2mmol,36.4mg) of CuCl were added in one portion to a gas-shielded tube2(0.8mmol,107.6mg), acetonitrile MeCN (5 mL). Then the system is irradiated and stirred by a 38W white light LED for 72 hours at room temperature in the nitrogen atmosphere, the reaction system is quenched by saturated sodium sulfite solution, extracted for 3 times by ethyl acetate, organic layers are combined, dried by anhydrous sodium sulfate, a rotary evaporator is used for removing a solvent and silica gel adsorption, and the product 4g can be obtained by simple column chromatography, wherein the yield is 76%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.56-7.55(m,1H),7.49-7.47(m,1H),7.34-7.31(m,1H),7.24-7.22(m,1H),4.94-4.90(m,1H),3.98-3.84(m,2H).13C NMR(100MHz,CDCl3)δ140.0,132.2,130.2,130.25,126.1,122.7,60.5,48.0；MS(EI)calculatedfor[C8H7BrCl2]:251.91,found252.00；IR(neat,cm-1):υ3062,2951,2924,2852,1572,1476,880,757.
Example eight
Add 3h (0.2mmol,27.6mg) of CuCl in one portion to a gas shield tube2(0.8mmol,107.6mg), acetonitrile MeCN (5 mL). Then the system is irradiated and stirred by a 38W white light LED for 72 hours at room temperature in the nitrogen atmosphere, the reaction system is quenched by saturated sodium sulfite solution, extracted for 3 times by ethyl acetate, organic layers are combined, dried by anhydrous sodium sulfate, a solvent is removed by a rotary evaporator, silica gel is adsorbed, and a product is obtained by simple column chromatography for 4 hours, wherein the yield is 76%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.60-7.58(m,1H),7.42-7.39(m,1H),7.37-7.27(m,2H),5.63-5.99(t,J＝6.9Hz,1H),4.03-3.94(m,2H).13C NMR(100MHz,CDCl3)δ135.3,133.3,130.1,129.8,128.6,127.4,57.4,47.5；MS(EI)calculatedfor[C8H7Cl3]:207.96,found 208.00；IR(neat,cm-1):υ2952,1597,1492,1440,1409,829,790,723.
Example nine
3i (0.2mmol,29.8mg), CuCl was added in one portion to a gas shield tube2(0.8mmol,107.6mg), acetonitrile MeCN (5 mL). Then the system is irradiated and stirred by a 38W white light LED for 72 hours at room temperature in the nitrogen atmosphere, the reaction system is quenched by saturated sodium sulfite solution, extracted for 3 times by ethyl acetate, organic layers are combined, dried by anhydrous sodium sulfate, a solvent is removed by a rotary evaporator, silica gel is adsorbed, and a product 4i can be obtained by simple column chromatography, wherein the yield is 96%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ8.27-8.25(m,2H),7.63-7.60(m,2H),5.10-5.07(m,1H),4.07-4.02(m,1H),3.95-3.90(m,1H).13C NMR(100MHz,CDCl3)δ148.1,144.7,128.6,123.9,59.6,47.5；MS(EI)calculatedfor[C8H7Cl2NO2]:218.99,found 219.00；IR(neat,cm-1):υ3106,3077,3013,2921,2855,1517,1348,828.
Example ten
3j (0.2mmol,36.0mg), CuCl was added in one portion to a gas shield tube2(0.8mmol,107.6mg), acetonitrile MeCN (5 mL). Then the system is irradiated and stirred by a 38W white light LED for 72 hours at room temperature in the nitrogen atmosphere, the reaction system is quenched by saturated sodium sulfite solution, extracted for 3 times by ethyl acetate, organic layers are combined, dried by anhydrous sodium sulfate, a solvent is removed by a rotary evaporator, silica gel is adsorbed, and a product 4j can be obtained by simple column chromatography, wherein the yield is 70%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.44-7.34(m,10H),5.21(s,2H).13C NMR(100MHz,CDCl3)δ138.3,129.0,128.5,128.0,65.7；MS(EI)calculatedfor[C14H12Cl2]:250.03,found 250.05；IR(neat,cm-1):υ3066,3031,2956,2918,2850,772,691.
EXAMPLE eleven
3k (0.2mmol,41.6mg), CuCl was added in one portion to a gas shield tube2(0.8mmol,107.6mg), acetonitrile MeCN (5 mL). Then, after the system was stirred under nitrogen atmosphere at room temperature with a 38W white LED for 72 hours, the reaction system was quenched with a saturated sodium sulfite solution, extracted 3 times with ethyl acetate, and the organic layers were combined and dried over anhydrous sodium sulfate. ,the solvent was removed by a rotary evaporator, adsorbed on silica gel and purified by simple column chromatography to give 4k with a yield of 70%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ8.10-8.08(m,2H),7.68-7.63(m,1H),7.56-7.51(m,4H),7.46-7.37(m,3H),5.53-5.47(m,2H).13C NMR(100MHz,CDCl3)δ191.3,137.0,134.6,134.3,129.3,129.0,129.0,128.8,128.3,60.0,57.0；HRMS(ESI-TOF):Anal Calcd.For.C15H12 35Cl2O2+Na+:301.0157,Found:301.0175.C15H12 35Cl37ClO2+Na+:303.0128,Found:303.0148.C15H12 37Cl2O2+Na+:305.0098,Found:305.014；IR(neat,cm-1):υ3064,2981,2851,1685,1594,1579,1499,1449,1277,746,684.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a visible light catalyzed double-chlorine addition product of aromatic olefin is characterized by comprising the following steps:
taking aromatic olefin as a substrate, taking copper chloride with visible light absorption capacity as a chlorine source, reacting in an organic solvent under the irradiation of visible light, carrying out the reaction in an inert atmosphere, and obtaining a double-chlorine addition product of the aromatic olefin after the reaction is completed; the aromatic alkene comprises a carbon-carbon double bond and a C6-C15 aryl group which is connected with the carbon-carbon double bond through a covalent bond.
2. The method of claim 1, wherein: the structural formula of the aromatic olefin is shown as
The structural formula of the double-chlorine addition product of the aromatic olefin is shown as
Wherein R is1And R2Is selected from substituted or unsubstituted C6-C10 aryl; another is selected from hydrogen or a substituted or unsubstituted C6-C10 aryl group; the substituent on the aryl is selected from one or more of C1-C4 alkyl, C1-C4 alkoxy, nitro, phenyl, halogen, trifluoromethyl, acetoxyl, cyano and carboxyl.
3. The method of claim 2, wherein: r1And R2Is selected from substituted or unsubstituted C6-C10 aryl; the other is selected from hydrogen.
4. The production method according to claim 2 or 3, characterized in that: the aryl group is phenyl, naphthyl, biphenyl or benzoyl.
5. The production method according to claim 2 or 3, characterized in that: the substituent on the aryl is selected from one or more of nitro, phenyl, halogen, trifluoromethyl, acetoxyl, cyano and carboxyl.
6. The production method according to any one of claims 1 to 3, characterized in that: the reaction temperature is 23-25 ℃; the reaction time is 36-72 hours.
7. The production method according to any one of claims 1 to 3, characterized in that: the organic solvent is one or more of petroleum ether, 1, 2-dichloroethane, 1,1, 1-trichloroethane, 1,1, 2-trichloroethane, nitromethane, acetonitrile, ethyl acetate and acetone.
8. The production method according to any one of claims 1 to 3, characterized in that: the inert atmosphere is a nitrogen atmosphere.
9. The production method according to any one of claims 1 to 3, characterized in that: the chlorine source is 4 times of the molar amount of the aromatic olefin.
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