CN113121516A - Compound and method for preparing compound by catalyzing 5-chloromethyl furfural with carbene - Google Patents
Compound and method for preparing compound by catalyzing 5-chloromethyl furfural with carbene Download PDFInfo
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- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
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- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention relates to a compound and a method for preparing the compound by catalyzing 5-chloromethyl furfural with carbene. A compound having the formula:
the synthetic route of the compound is as follows:
. The method has the advantages of one-step reaction, mild reaction conditions, low cost and no pollution to the environment, and provides convenience for high-value utilization of the 5-chloromethyl furfural.
Description
Technical Field
The invention belongs to the field of biomass catalytic conversion, and particularly relates to a compound and a method for preparing the compound by catalyzing 5-chloromethyl furfural with carbene.
Background
With the gradual depletion of fossil energy resources, human beings face huge social crisis. The utilization of renewable resources is urgently needed to be developed, and the sustainable development of the society is realized. The conversion and utilization of the biomass provide a green sustainable development way for people. Professor Mark massal, davis university, california, 2008, developed a process for the efficient preparation of 5-chloromethyl furfural from biomass-derived cellulose (angew. However, the further transformation of 5-chloromethylfurfural is slow, and a method for further transformation into high value-added chemicals is lacked.
Disclosure of Invention
The first purpose of the invention is to provide a compound, which is used as a conversion product of 5-chloromethyl furfural, has high additional value, can be used as an intermediate for preparing polyolefin, pesticides, antitumor drugs and the like, and has wide application.
The second purpose of the invention is to provide a preparation method of the compound, the preparation method takes 5-chloromethyl furfural as a raw material, only has one-step reaction, has mild reaction conditions, low cost and no pollution to the environment, and provides convenience for the high-value utilization of the 5-chloromethyl furfural.
In order to achieve the above purpose, the invention provides the following technical scheme:
a compound having the formula:
wherein R is1，R2Independently selected from one of hydrogen, cyano, nitro, ester group, C1-C50 alkyl, halogenated C1-C50 alkyl, substituted and unsubstituted C6-C10 aryl and substituted and unsubstituted heteroaryl, or R1、R2And carbon connected with the two forms substituted and unsubstituted six-membered ring hydrocarbon or substituted and unsubstituted nitrogen-containing heterocycle;
R3，R4，R5independently selected from one of hydrogen, cyano, nitro, ester group, C1-C50 alkyl, halogenated C1-C50 alkyl, substituted and unsubstituted C6-C10 aryl and substituted and unsubstituted heteroaryl; or R3，R4，R5Wherein one is hydrogen and the other two carbons to which it is attached form a cycloalkyl or substituted cycloalkyl group;
X1is selected from any one of O, NR, S, P, CR and halogen, R is selected fromFrom hydrogen, aryl or C1-C50 alkyl;
Y1any one selected from N, C, O.
In the present invention, the C6-C10 aryl group means the total number of carbon atoms contained in the aromatic ring, the number of carbon atoms not including a substituent, and the aryl group may be a phenyl group, a naphthyl group or the like.
The halogenated C1-C50 alkyl in the invention can be fluorine substituted, chlorine substituted, bromine substituted or iodine substituted, the number of the substitution is not limited, and the carbon chain length can be methyl, ethyl, propyl, isopropyl, butyl and isomers thereof, pentyl and the like.
Substituted C6-C10 aryls described herein include, but are not limited to, p-bromophenyl, o-bromophenyl, m-bromophenyl, p-chlorophenyl, o-chlorophenyl, m-chlorophenyl, p-nitrophenyl, p-methoxyphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, 3, 4-dimethylphenyl, 3, 4-dimethoxyphenyl, 3, 5-dimethylphenyl, or 3, 5-dimethoxyphenyl.
Heteroaryl groups described herein include, but are not limited to, 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 4-pyridyl, 3-pyridyl, or 2-pyridyl.
Substituted heteroaryl groups described herein include, but are not limited to, 5-methyl-2-furyl, 3-methyl-2-thienyl, 4-methyl-2-thienyl, or 5-methyl-2-thienyl.
R1、R2And the carbons to which they are attached constitute a substituted, unsubstituted six-membered ring hydrocarbon, or a substituted, unsubstituted nitrogen-containing heterocycle, including but not limited to the following types:
In some embodiments, the substituted C6-C10 aryl is a halogen, trichloromethyl, tribromomethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl, cyano, nitro, alkoxy, or alkyl substituted C6-C10 aryl;
in some embodiments, the substituted heteroaryl is halogen, trichloromethyl, tribromomethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl, cyano, nitro, C1-C50 alkoxy, or C1-C50 alkyl substituted heteroaryl.
In some embodiments, the R is1，R2Independently selected from hydrogen, cyano, nitro, ester, trichloromethyl, tribromomethyl, perfluoro C1-C50 alkyl, difluoromethyl or difluorochloromethyl, preferably independently selected from hydrogen, cyano, nitro, ester, trichloromethyl, tribromomethyl, trifluoromethyl, difluoromethyl or difluorochloromethyl, or R1、R2And carbon connected with the two forms substituted six-membered cyclic hydrocarbon or substituted nitrogen-containing heterocycle;
in some embodiments, R3，R4，R5Independently selected from hydrogen, cyano, nitro, ester, trichloromethyl, tribromomethyl, perfluoro C1-C50 alkyl, difluoromethyl or difluorochloromethyl, preferably independently selected from hydrogen, cyano, nitro, ester, trichloromethyl, tribromomethyl, trifluoromethyl, difluoromethyl or difluorochloromethyl.
In some embodiments, the compounds are as follows:
the compound is used as a downstream product of 5-chloromethyl furfural, has wide application, can be used as an intermediate for preparing polyolefin, pesticides, antitumor drugs and the like, and has higher additional value.
These compounds can be synthesized using the following route:
wherein the carbene catalyst is a compound of formula III:
R1，R2independently selected from one of hydrogen, cyano, nitro, ester group, C1-C50 alkyl, halogenated C1-C50 alkyl, substituted and unsubstituted C6-C10 aryl and substituted and unsubstituted heteroaryl, or R1、R2And carbon connected with the two forms substituted and unsubstituted six-membered ring hydrocarbon or substituted and unsubstituted nitrogen-containing heterocycle;
R3，R4，R5，R6，R7，R8，R9independently selected from one of hydrogen, cyano, nitro, ester group, C1-C50 alkyl, halogenated C1-C50 alkyl, substituted and unsubstituted C6-C10 aryl and substituted and unsubstituted heteroaryl; or R3，R4，R5Wherein one is hydrogen and the other two carbons to which it is attached form a cycloalkyl or substituted cycloalkyl group;
X1、X2、X3independently selected from any one of O, NR, S, P, CR and halogen, R is selected from hydrogen, aryl or C1-C50 alkyl;
Y1any one selected from N, C, O, preferably O;
Y2any one selected from N, C; and Y is2When N is equal to 1; y is2When the carbon atom is C, n is a positive integer;
z is selected from any one of N and C.
The preparation method takes 5-chloromethyl furfural as a raw material, and carbene III as a catalyst to react with an electrophilic reagent (I) and a nucleophilic reagent (II) in a solvent, only one step is needed, the process is simple and convenient, the yield is high, and the preparation method can be used for kilogram-level preparation and has important application value.
In the specific reaction process, the adding sequence of the raw materials is arbitrary, preferably, the carbene catalyst shown in the formula III and the alkali are dissolved in the solvent, and then the electrophilic reagent shown in the formula CMF and I and the nucleophilic reagent shown in the formula II are uniformly mixed for reaction.
In some embodiments, the base is selected from at least one of 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 4-diazabicyclo [2.2.2] octane (DABCO), Triethylamine (TEA), diethylamine, N-Diisopropylethylamine (DIPEA), potassium phosphate, potassium acetate, cesium carbonate, potassium carbonate, sodium hydroxide, sodium methoxide. The function of the alkali is as follows: generating carbene in situ and neutralizing hydrogen chloride generated by the reaction.
In some embodiments, the solvent is selected from at least one of toluene, xylene, chlorobenzene, benzene, dioxane, Tetrahydrofuran (THF), diethyl ether, chloroform, Dichloromethane (DCM), 1, 2-Dichloroethane (DCE), ethyl acetate (EtOAc), acetone, acetonitrile, and N, N-Dimethylformamide (DMF).
In some embodiments, the carbene catalyst catalyzes the reaction for a time of 2 hours or more.
In some embodiments, the temperature of the carbene-based catalyst is 20-30 ℃, i.e., the carbene-based catalyst is generally carried out at room temperature
In some embodiments, the molar ratio of the carbene catalyst to the base, CMF, compound I, compound II is from 0.001 to 1: 1-50: 1-50: 1-20: 1-100, preferably 0.01-0.5: 2-10: 2-10: 1: 1-50, more preferably 0.01: 1: 1: 1: 1.
in summary, compared with the prior art, the invention achieves the following technical effects:
(1) provides a compound with high added value, and provides a new intermediate for the synthesis of polyolefin, pesticide, antitumor drugs and the like;
(2) the preparation method is simple, the conditions are mild, the yield is high, and the speed is high.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings.
FIG. 1 shows the preparation of the compound of formula IV-1 obtained in example 11H NMR spectrum;
FIG. 2 shows the preparation of the compound of formula IV-2 obtained in example 21H NMR spectrum;
FIG. 3 shows the preparation of the compound of formula IV-3 obtained in example 31H NMR spectrum;
FIG. 4 shows the preparation of the compound of formula IV-4 obtained in example 41H NMR spectrum;
FIG. 5 shows the preparation of the compound of formula IV-5 obtained in example 51H NMR spectrum;
FIG. 6 shows preparation of compound of formula IV-6 from example 61H NMR spectrum;
FIG. 7 shows preparation of compound of formula IV-7 from example 71H NMR spectrum;
FIG. 8 shows preparation of compound represented by formula IV-8 in example 81H NMR spectrum;
FIG. 9 shows preparation of compound of formula IV-9 from example 91H NMR spectrum.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The synthetic route of all the following examples of the invention is as follows:
wherein the substituents have the meanings given above, and the carbene catalysts used are
However, it will be appreciated by those skilled in the art that only catalysts of the type suitable for this reaction are suitable.
Example 1
The carbene catalyst of the formula III (0.002mmol) was added to a 5mL reaction flask in the presence of 1, 2-dichloroethane (2.0mL), K2CO3(0.2mmol), trifluoromethyl-2-thiopheneacetone shown in formula I (0.2mmol), MeOH shown in formula II (0.2mmol) and 0.2mmol CMF are added into the system and stirred for 2 hours at room temperature, after TLC detection reaction is completed, the compound shown in formula IV-1 is obtained after concentration column chromatography separation.
1H NMR(500MHz,CDCl3)δ7.32(dd,J＝5.1,1.3Hz,1H),7.13(d,J＝3.6Hz,1H),7.01(dd,J＝4.7,3.6Hz,2H),6.06(d,J＝3.3Hz,1H),3.85(s,3H),3.60(d,J＝2.9Hz,1H),3.58–3.40(m,2H).
The nuclear magnetic spectrum and mass spectrum identify the product as the structure, which is the compound shown in the formula IV-1, and the calculated yield is about 83.21%.
Example 2
Preparation of the Compound of formula IV-2
The carbene catalyst of the formula III (0.002mmol) was added to a 5mL reaction flask in the presence of 1, 2-dichloroethane (2.0mL), K2CO3(0.2mmol), (E) -4- (4-chlorophenyl) -2-oxo-3-butenoic acid ethyl ester represented by the formula I (0.2mmol) and 6-hydroxy-2-azaspiro [3.3 ] represented by the formula II]Adding tert-butyl heptane-2-carboxylate (0.2mmol) and CMF (0.2mmol) into the system, stirring at room temperature for 2 hr, detecting by TLC, and separating by concentration column chromatography to obtain compound shown in formula IV-2.
1H NMR(400MHz,CDCl3)δ7.39–7.26(m,4H),7.09(d,J＝3.4Hz,1H),6.85(d,J＝15.8Hz,1H),6.37(d,J＝15.8Hz,1H),6.33(d,J＝3.5Hz,1H),5.08(p,J＝7.2Hz,1H),4.38(dq,J＝10.5,7.2Hz,1H),4.28(dq,J＝10.3,7.1Hz,1H),3.98(s,2H),3.93(s,2H),3.66(s,1H),3.37(s,1H),3.15(d,J＝15.0Hz,1H),2.80–2.63(m,2H),2.33(ddd,J＝10.3,7.2,3.4Hz,2H),1.45(s,9H),1.36(t,J＝7.2Hz,3H).
The nuclear magnetic spectrum and mass spectrum identify the product as the structure, which is the compound shown in the formula IV-2, and the calculated yield is about 84.58%.
Example 3
Preparation of the Compound of formula IV-3
The carbene catalyst of the formula III (0.002mmol) was added to a 5mL reaction flask in the presence of 1, 2-dichloroethane (2.0mL), K2CO3(0.2mmol), ethyl 4- (phenyl) -2-oxo-3-butynoate of formula I (0.2mmol), methanol of formula II (0.2mmol), and CMF (0.2mmol) were added to the system and stirred at room temperature for 2 hours, after completion of the TLC detection reaction, the compound of formula IV-3 was obtained by concentration column chromatography.
1H NMR(500MHz,CDCl3)δ7.45(dt,J＝6.7,1.7Hz,2H),7.39–7.29(m,3H),7.11(d,J＝3.4Hz,1H),6.40(d,J＝3.5Hz,1H),3.94(s,3H),3.86(s,4H),3.70(s,1H),3.49(d,J＝3.7Hz,2H).
The nuclear magnetic spectrum and mass spectrum identify the product as the structure, which is the compound shown in the formula IV-3, and the calculated yield is about 83.21%.
Example 4
Preparation of the Compound of formula IV-4
The carbene catalyst of the formula III (0.002mmol) was added to a 5mL reaction flask in the presence of 1, 2-dichloroethane (2.0mL), K2CO3(0.2mmol), 1,1, 1-trifluoro-4-phenylbut-3-en-2-one (0.2mmol) shown in formula I, methanol (0.2mmol) shown in formula II and 0.2mmol of CMF are added into the system, stirred for 2 hours at room temperature, and after the TLC detection reaction is completed, the compound shown in formula IV-4 is obtained after concentration column chromatography separation.
1H NMR(500MHz,CDCl3)δ7.41–7.24(m,5H),7.08(d,J＝3.4Hz,1H),6.76(d,J＝16.0Hz,1H),6.32(d,J＝3.4Hz,1H),6.23(d,J＝16.0Hz,1H),3.83(s,3H),3.34(d,J＝15.1Hz,1H),3.26(d,J＝15.1Hz,1H),2.96(s,1H).
The nuclear magnetic spectrum and mass spectrum identify the product as the structure, which is the compound shown in the formula IV-4, and the calculated yield is about 81.54 percent.
Example 5
Preparation of the Compound of formula IV-5
The carbene catalyst of the formula III (0.002mmol) was added to a 5mL reaction flask in the presence of 1, 2-dichloroethane (2.0mL), K2CO3(0.2mmol), phenanthrenequinone of formula I (0.2mmol), methanol of formula II (0.2mmol), and CMF 0.2mmol, were added to the system and stirred at room temperature for 2 hours, after TLC detection reaction was complete, the compound of formula IV-5 was obtained by concentration column chromatography.
1H NMR(500MHz,CDCl3)δ7.96(dd,J＝7.6,1.5Hz,1H),7.91(d,J＝7.9Hz,1H),7.85(dd,J＝7.4,1.6Hz,1H),7.70(td,J＝7.7,1.7Hz,2H),7.52–7.33(m,3H),7.00(d,J＝3.4Hz,1H),6.06(d,J＝3.4Hz,1H),4.22(s,1H),3.85(s,3H),3.28–3.04(m,2H).
The nuclear magnetic spectrum and mass spectrum identify the product as the structure, which is the compound shown in the formula IV-5, and the calculated yield is about 89.76%.
Example 6
Preparation of the Compound of formula IV-6
The carbene catalyst of the formula III (0.002mmol) was added to a 5mL reaction flask in the presence of 1, 2-dichloroethane (2.0mL), K2CO3(0.2mmol), methyl trifluoropyruvate of formula I (0.2mmol) and methanol of formula II (0.2mmol),and 0.2mmol CMF, adding into the system, stirring at room temperature for 2 hours, detecting by TLC, and separating by concentration column chromatography to obtain the compound shown in formula IV-6.
The nuclear magnetic spectrum and mass spectrum identify the product as the structure, which is the compound shown in the formula IV-6, and the calculated yield is about 85.32%.
Example 7
Preparation of the Compound of formula IV-7
The carbene catalyst of the formula III (0.002mmol) was added to a 5mL reaction flask in the presence of 1, 2-dichloroethane (2.0mL), K2CO3(0.2mmol), 1-benzyl-1H-indole-2, 3-dione (0.2mmol) shown in formula I, methanol (0.2mmol) shown in formula II and 0.2mmol CMF are added into the system, stirred for 2 hours at room temperature, and after TLC detection reaction is completed, the compound shown in formula IV-7 is obtained after concentration column chromatography separation.
1H NMR(500MHz,CDCl3)δ7.30–7.21(m,4H),7.25–7.16(m,2H),7.15–7.06(m,2H),7.08–6.86(m,2H),6.66(d,J＝7.8Hz,1H),6.13(d,J＝3.4Hz,1H),4.97(d,J＝15.7Hz,1H),4.70(d,J＝15.7Hz,1H),3.81(s,3H),3.70(d,J＝2.1Hz,1H),3.49(d,J＝14.7Hz,1H),3.34(d,J＝14.7Hz,1H).
The nuclear magnetic spectrum and mass spectrum identify the product as the structure, which is the compound shown in the formula IV-7, and the calculated yield is about 90.21%.
Example 8
Preparation of the Compound of formula IV-8
The carbene catalyst of the formula III (0.002mmol) was added to a 5mL reaction flask in the presence of 1, 2-dichloroethane (2.0mL), K2CO3(0.2mmol), ethyl 4-bromophenyl glyoxylate of formula I (0.2mmol) and methanol of formula II (0.2mmol), and 0.2mmol of CMF were added to the system and stirred at room temperatureAfter the TLC detection reaction is completed for 2 hours, the compound shown as the formula IV-8 is obtained after the concentration column chromatographic separation.
1H NMR(500MHz,CDCl3)δ7.54(d,J＝8.7Hz,2H),7.50(d,J＝8.7Hz,2H),7.07(d,J＝3.5Hz,1H),6.26(d,J＝3.4Hz,1H),4.33(dq,J＝10.7,7.1Hz,1H),4.23(dq,J＝10.7,7.1Hz,1H),3.93(s,1H),3.86(s,3H),3.65(d,J＝15.2Hz,1H),3.30(d,J＝15.1Hz,1H),1.30(t,J＝7.1Hz,3H).
The nuclear magnetic spectrum and mass spectrum identify the product as the structure, which is the compound shown in the formula IV-8, and the calculated yield is about 84.33%.
Example 9
Preparation of the Compound of formula IV-9
The carbene catalyst of the formula III (0.002mmol) was added to a 5mL reaction flask in the presence of 1, 2-dichloroethane (2.0mL), K2CO3(0.2mmol), (E, E) -4- (phenyl) -2-oxo-3, 5-hexadienoic acid methyl ester of formula I (0.2mmol) and methanol of formula II (0.2mmol), and (0.2mmol) CMF were added to the system and stirred at room temperature for 2 hours, after completion of the TLC detection reaction, the compound of formula IV-9 was obtained by concentration column chromatography.
1H NMR(400MHz,CDCl3)δ7.45–7.37(m,2H),7.37–7.28(m,2H),7.28–7.24(m,1H),7.09(d,J＝3.4Hz,1H),6.87–6.72(m,1H),6.72–6.54(m,2H),6.30(d,J＝3.5Hz,1H),5.97(d,J＝14.8Hz,1H),3.87(s,3H),3.86(s,3H),3.53(s,1H),3.35(d,J＝14.9Hz,1H),3.10(d,J＝15.0Hz,1H).
The nuclear magnetic spectrum and mass spectrum identify the product as the structure, which is the compound shown in the formula IV-9, and the calculated yield is about 88.45%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A compound of the formula:
wherein R is1，R2Independently selected from one of hydrogen, cyano, nitro, ester group, C1-C50 alkyl, halogenated C1-C50 alkyl, substituted and unsubstituted C6-C10 aryl and substituted and unsubstituted heteroaryl, or R1、R2And carbon connected with the two forms substituted and unsubstituted six-membered ring hydrocarbon or substituted and unsubstituted nitrogen-containing heterocycle;
R3，R4，R5independently selected from one of hydrogen, cyano, nitro, ester group, C1-C50 alkyl, halogenated C1-C50 alkyl, substituted and unsubstituted C6-C10 aryl and substituted and unsubstituted heteroaryl; or R3，R4，R5Wherein one is hydrogen and the other two carbons to which it is attached form a cycloalkyl or substituted cycloalkyl group; x1Is selected from any one of O, NR, S, P, CR and halogen, R is selected from hydrogen, aryl or C1-C50 alkyl;
Y1any one selected from N, C, O, preferably O.
2. The compound of claim 1, wherein the substituted C6-C10 aryl is halogen, trichloromethyl, tribromomethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl, cyano, nitro, alkoxy, or alkyl substituted C6-C10 aryl;
the substituted heteroaryl is halogen, trichloromethyl, tribromomethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl, cyano, nitro, C1-C50 alkoxy or C1-C50 alkyl substituted heteroaryl.
3. A compound of claim 1, wherein R is1，R2Independently selected from hydrogen, cyano, nitro, ester, trichloromethyl, tribromomethyl, perfluoro C1-C50 alkyl, difluoromethyl or difluorochloromethyl, preferably independently selected from hydrogen, cyano, nitro, ester, trichloromethyl, tribromomethyl, trifluoromethyl, difluoromethyl or difluorochloromethyl, or R1、R2And carbon connected with the two forms substituted six-membered cyclic hydrocarbon or substituted nitrogen-containing heterocycle;
R3，R4，R5independently selected from hydrogen, cyano, nitro, ester, trichloromethyl, tribromomethyl, perfluoro C1-C50 alkyl, difluoromethyl or difluorochloromethyl, preferably independently selected from hydrogen, cyano, nitro, ester, trichloromethyl, tribromomethyl, trifluoromethyl, difluoromethyl or difluorochloromethyl.
4. The compound of claim 1, being of one of the following formulae:
5. method for preparing a compound according to any one of claims 1 to 4 by carbene-catalyzed 5-chloromethylfurfural, characterized in that the synthesis is carried out by the following route:
wherein the carbene catalyst is a compound of formula III:
R1，R2independently selected from one of hydrogen, cyano, nitro, ester group, C1-C50 alkyl, halogenated C1-C50 alkyl, substituted and unsubstituted C6-C10 aryl and substituted and unsubstituted heteroaryl, or R1、R2And carbon connected with the two forms substituted and unsubstituted six-membered ring hydrocarbon or substituted and unsubstituted nitrogen-containing heterocycle;
R3，R4，R5，R6，R7，R8，R9independently selected from one of hydrogen, cyano, nitro, ester group, C1-C50 alkyl, halogenated C1-C50 alkyl, substituted and unsubstituted C6-C10 aryl and substituted and unsubstituted heteroaryl; or R3，R4，R5Wherein one is hydrogen and the other two carbons to which it is attached form a cycloalkyl or substituted cycloalkyl group;
X1、X2、X3independently selected from any one of O, NR, S, P, CR and halogen, R is selected from hydrogen, aryl or C1-C50 alkyl;
Y1any one selected from N, C, O, preferably O;
Y2any one selected from N, C; and Y is2When N is equal to 1; y is2When the carbon atom is C, n is a positive integer;
z is selected from any one of N and C.
6. The method according to claim 5, wherein the base is selected from at least one of 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 4-diazabicyclo [2.2.2] octane, triethylamine, diethylamine, N, N-diisopropylethylamine, potassium phosphate, potassium acetate, cesium carbonate, potassium carbonate, sodium hydroxide, and sodium methoxide.
7. The method according to claim 5, wherein the solvent is at least one selected from the group consisting of toluene, xylene, chlorobenzene, benzene, dioxane, tetrahydrofuran, diethyl ether, chloroform, dichloromethane, 1, 2-dichloroethane, ethyl acetate, acetone, acetonitrile, and N, N-dimethylformamide.
8. The method of claim 5, wherein the carbene catalyst catalyzes the reaction for 2 hours or more.
9. The method according to claim 5, wherein the temperature of the carbene catalyst for catalyzing the reaction is 20-30 ℃.
10. The method of claim 5, wherein the molar ratio of carbene catalyst to base, CMF, Compound I, Compound II is from 0.001 to 1: 1-50: 1-50: 1-20: 1-100, preferably 0.01-0.5: 2-10: 2-10: 1: 1-50, more preferably 0.01: 1: 1: 1: 1.
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