Benzopyran type flavonoid compound, preparation method and application thereof, and pharmaceutical preparation

Abstract

The invention provides a benzopyran type flavonoid compound, a preparation method and application thereof and a medicinal preparation, and belongs to the technical field of medicinal chemistry. The benzopyran type flavonoid compound provided by the invention has a structure as shown in a formula I or a formula II. The benzopyran type flavonoid compound provided by the invention takes a SWEET protein family member of a plant as a target spot, can selectively inhibit the sugar transport activity of the SWEET protein of the plant, and has broad-spectrum antibacterial activity, and the two effects are superposed to enhance the broad-spectrum disease resistance of the plant. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of pharmaceutical chemistry, and specifically relates to a benzopyran-type flavonoid compound, a preparation method and application thereof, and a pharmaceutical preparation. Background Art

[0002] Many microorganisms, including fungi, bacteria, viruses, and mycoplasm, can parasitize in plants and cause harmful effects on plants, which are called diseases. Microorganisms that cause plant diseases are called pathogens. Existing studies have shown that the losses caused to plants by diseases are considerable every year. Rice sheath blight and soybean sclerotinia often bring major or even devastating disasters to production. Therefore, how to improve the disease resistance of crops is almost a key factor in determining agricultural production.

[0003] In the competitive interaction between pathogens and host plants, nutritional competition is the main factor, in which the distribution ratio of sugars between pathogens and host plants directly affects the virulence of pathogens and the disease resistance of host plants. When pathogens invade host plants, bidirectional sugar transporters SWEETs (Sugars will eventually be exportedtransporters), also known as sugar efflux proteins, are targeted and activated by pathogens as susceptibility factors, thereby promoting the leakage of sugars in the plant into the apoplast for absorption and utilization by pathogens. In addition, the sugar efflux function of SWEETs and the characteristics of being targeted by pathogens are relatively conservative in different crop-pathogen interaction systems. It can be seen that it is expected to achieve disease control by inhibiting the sugar transport function of SWEETs. However, there are few studies on this module in this field. How to obtain compounds that can effectively inhibit the sugar transport function of SWEETs is a problem that current researchers urgently need to solve. Summary of the invention

[0004] The object of the present invention is to provide a benzopyran flavonoid compound and its preparation method and application, and a pharmaceutical preparation. The benzopyran flavonoid compound provided by the present invention targets members of the SWEETs protein family of plants, can selectively inhibit the sugar transport activity of the SWEET protein of plants, and has good broad-spectrum antibacterial activity.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a benzopyran flavonoid compound or a pharmaceutically acceptable salt thereof, wherein the benzopyran flavonoid compound has a structure shown in Formula I or Formula II:

[0007]

[0008] In Formula I and Formula II, the R1 is selected from substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, and the substitution means that one or more hydrogen atoms in the group are replaced by alkyl, alkoxy, halogen, hydroxyl, nitro, haloalkyl, aralkyl, alkylamino or heterocyclic amino;

[0009] The R2 is selected from -H or alkyl;

[0010] The R3 is selected from -H, hydroxyl or alkoxy.

[0011] Preferably, the aryl group in the substituted or unsubstituted aryl group is phenyl; the heteroaryl group in the substituted or unsubstituted heteroaryl group is indolyl or N-methylindolyl;

[0012] In the R1, the number of carbon atoms in the alkyl group is 1 to 5, the number of carbon atoms in the alkoxy group is 1 to 5, the number of carbon atoms in the haloalkyl group is 1 to 5, the number of carbon atoms in the aralkyl group is 6 to 8, the number of carbon atoms in the alkylamino group is 2 to 6, the number of carbon atoms in the heterocyclic amino group is 4 to 8, the halogen atom in the haloalkyl group is chlorine or bromine, and the number of halogen atoms in the haloalkyl group is 1 to 3;

[0013] In said R2, said alkyl group is methyl or ethyl;

[0014] In the R3, the alkoxy group is a methoxy group or an ethoxy group.

[0015] Preferably, the haloalkyl group is trifluoromethyl, the aralkyl group is benzyl, the alkylamino group is dimethylamino or diethylamino, and the heterocyclic amino group is morpholinyl, 4-methylpiperazin-1-yl, 4-ethylpiperazin-1-yl, piperidin-1-yl or pyrrolidin-1-yl.

[0016] Preferably, the R1 is selected from any of the following groups:

[0017]

[0018]

[0019] Preferably, the benzopyran-type flavonoid compound is any one of the following compounds:

[0020]

[0021]

[0022]

[0023] The present invention provides a method for preparing the benzopyran-type flavonoid compound described in the above technical solution, comprising the following steps:

[0024] (1) The method for preparing a benzopyran-type flavonoid compound having a structure shown in Formula I comprises the following steps:

[0025] Compound F is mixed with an aromatic aldehyde compound and ethanol, and subjected to a condensation reaction under alkaline conditions to obtain a benzopyran-type flavonoid compound having a structure shown in Formula I;

[0026] (2) The method for preparing a benzopyran-type flavonoid compound having a structure shown in Formula II comprises the following steps:

[0027] The benzopyran flavonoid compound having a structure shown in Formula I when R2 is -H is mixed with iodine and dimethyl sulfoxide to perform a ring-forming reaction to obtain a benzopyran flavonoid compound having a structure shown in Formula II;

[0028] The structural formula of the aromatic aldehyde compound is R1-CHO; the structural formula of the compound F is shown in Formula F:

[0029]

[0030] The R1, R2 and R3 are as defined in Formula I or Formula II.

[0031] The present invention provides the use of the benzopyran flavonoid compound described in the above technical solution in the preparation of a broad-spectrum antibacterial drug.

[0032] The present invention provides the use of the benzopyranose flavonoid compound described in the above technical solution in the preparation of a plant sugar transporter inhibitor.

[0033] The present invention provides a pharmaceutical preparation, comprising an active ingredient and a pharmaceutical excipient; the active ingredient is the benzopyran-type flavonoid compound described in the above technical solution.

[0034] Preferably, the dosage form of the pharmaceutical preparation includes wettable powder, suspension, aqueous solution, granule, spray, tablet, capsule, aerosol or nano preparation.

[0035] The present invention provides a benzopyran flavonoid compound having a structure shown in Formula I or Formula II. The benzopyran flavonoid compound provided by the present invention targets members of the SWEET protein family of plants and can selectively inhibit the sugar transport activity of the SWEET protein of plants; at the same time, the benzopyran flavonoid compound has a broad-spectrum antibacterial activity, and the two effects are superimposed to enhance the broad-spectrum disease resistance of plants.

[0036] Furthermore, the present invention prepares novel benzopyran-type flavonoid compounds based on the xanthohumol C structural skeleton. The antibacterial activity test results of the embodiments show that the benzopyran flavonoid compound ZQQ26 prepared by the present invention has a significant inhibitory effect on the mycelial growth of pathogenic fungi such as rice blast, corn leaf blight, corn ear rot and tobacco brown spot, and can effectively inhibit the growth rate of pathogenic bacteria such as Chinese cabbage soft rot, tobacco wildfire and tobacco bacterial wilt; the benzopyran flavonoid compound ZQQ35 has a significant inhibitory effect on the mycelial growth of pathogenic fungi such as corn leaf blight, corn ear rot, soybean sclerotinia and grape canker, and can effectively inhibit the growth rate of pathogenic bacteria such as rice white leaf blight, tobacco angular spot and tobacco bacterial wilt; ZQQ41 has a significant inhibitory effect on the mycelial growth of rice blast, corn leaf blight, rice sheath blight and soybean sclerotinia, and can effectively inhibit the growth rate of pathogenic bacteria such as Chinese cabbage soft rot, tobacco angular spot and tobacco bacterial wilt. Therefore, the benzopyran-type flavonoid compounds provided by the present invention have good potential to become broad-spectrum antibacterial agents and can be used to treat a variety of diseases including corn ear rot, corn leaf blight, grape canker, tobacco angular spot, tobacco bacterial wilt, rice sheath blight, rice blast and rice white leaf blight. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0038] Figure 1 It is a schematic diagram of the structural formula of benzopyran flavonoid compounds;

[0039] Figure 2 The figure is the result of the biological activity test of benzopyran flavonoid compounds ZQQ2, ZQQ3 and ZQQ4;

[0040] Figure 3 The figure is the result of the biological activity test of benzopyran flavonoid compounds ZQQ5, ZQQ6 and ZQQ7;

[0041] Figure 4 The figure is the result of the biological activity test of benzopyran flavonoid compounds ZQQ8, ZQQ9 and ZQQ10;

[0042] Figure 5 The figure shows the results of biological activity tests of benzopyran flavonoid compounds ZQQ11, ZQQ12 and ZQQ13;

[0043] Figure 6 The figure is the result of the biological activity test of benzopyran flavonoid compounds ZQQ14, ZQQ15 and ZQQ16;

[0044] Figure 7 The figure shows the results of biological activity tests of benzopyran flavonoid compounds ZQQ17, ZQQ18 and ZQQ19;

[0045] Figure 8 The figure is the result of the biological activity test of benzopyran flavonoid compounds ZQQ21, ZQQ22 and ZQQ23;

[0046] Fig. 9 The figure is the result of the biological activity test of benzopyran flavonoid compounds ZQQ25, ZQQ26 and ZQQ27;

[0047] Fig.10 The figure is a biological activity test result diagram of benzopyran flavonoid compounds ZQQ28, ZQQ29 and ZQQ30;

[0048] Fig.11 The figure is a biological activity test result diagram of benzopyran flavonoid compounds ZQQ31, ZQQ32 and ZQQ33;

[0049] Fig.12 The figure is the result of the biological activity test of benzopyran flavonoid compounds ZQQ34, ZQQ35 and ZQQ36;

[0050] Fig.13 The figure is a graph showing the biological activity test results of benzopyran flavonoid compounds ZQQ37, ZQQ41 and ZQQ42;

[0051] Fig.14 The figure is the result of biological activity test of benzopyran flavonoid compounds ZQQ43, ZQQ44 and ZQQ45;

[0052] Fig.15 The figure is the result of biological activity test of benzopyran flavonoid compounds ZQQ46, ZQQ47 and ZQQ48;

[0053] Fig.16 The figure is the result of biological activity test of benzopyran flavonoid compounds ZQQ49, ZQQ50 and ZQQ51;

[0054] Fig.17 The figure is a biological activity test result diagram of benzopyran flavonoid compounds ZQQ54, ZQQ56 and ZQQ57;

[0055] Fig.18The figure is the result of the biological activity test of benzopyran flavonoid compounds ZQQ58, ZQQ59 and ZQQ60;

[0056] Fig.19 The figure is a biological activity test result diagram of benzopyran flavonoid compounds ZQQ61, ZQQ62 and ZQQ63;

[0057] Fig. 20 The figure is a biological activity test result diagram of benzopyran flavonoid compounds ZQQ64, ZQQ65 and ZQQ66;

[0058] Fig.21 The figure is a graph showing the biological activity test results of benzopyran flavonoid compounds ZQQ70, ZQQ71 and ZQQ75;

[0059] Fig. 22 The results of the hyphae growth test and colony diameter test with the addition of the benzopyran flavonoid compound ZQQ26 are shown in Figure 1.

[0060] Fig.23 The results of the hyphae growth test and colony diameter after adding the benzopyran flavonoid compound ZQQ35 are shown;

[0061] Fig.24 The results of the hyphae growth test and colony diameter test with the addition of the benzopyran flavonoid compound ZQQ41 are shown;

[0062] Fig.25 This is a graph showing the results of a bacterial growth rate test with the addition of benzopyran-type flavonoid compound ZQQ26;

[0063] Fig.26 This is a graph showing the results of a bacterial growth rate test with the addition of benzopyran-type flavonoid compound ZQQ35;

[0064] Fig. 27 This is a graph showing the results of a bacterial growth rate test with the addition of the benzopyran flavonoid compound ZQQ41. DETAILED DESCRIPTION

[0065] The present invention provides a benzopyran flavonoid compound or a pharmaceutically acceptable salt thereof, wherein the benzopyran flavonoid compound has a structure shown in Formula I or Formula II:

[0066]

[0067] In Formula I and Formula II, the R1 is selected from substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, and the substitution means that one or more hydrogen atoms in the group are replaced by alkyl, alkoxy, halogen, hydroxyl, nitro, haloalkyl, aralkyl, alkylamino or heterocyclic amino;

[0068] The R2 is selected from -H or alkyl;

[0069] The R3 is selected from -H, hydroxyl or alkoxy.

[0070] In the present invention, the aryl group in the substituted or unsubstituted aryl group may be a phenyl group; the heteroaryl group in the substituted or unsubstituted heteroaryl group may be an indolyl group or an N-methylindolyl group.

[0071] In the R1 of the present invention, the number of carbon atoms in the alkyl group may be 1 to 5; in a specific embodiment, the number of carbon atoms in the alkyl group may be 1, 2, 3, 4 or 5. In the R1 of the present invention, the number of carbon atoms in the alkoxy group may be 1 to 5; in a specific embodiment, the number of carbon atoms in the alkoxy group may be 1, 2, 3, 4 or 5. In the R1 of the present invention, the number of carbon atoms in the haloalkyl group may be 1 to 5, specifically 1, 2, 3, 4 or 5; the halogen atom in the haloalkyl group may be chlorine or bromine; the number of halogen atoms in the haloalkyl group may be 1 to 3, specifically 1, 2 or 3; in a specific embodiment of the present invention, the haloalkyl group may be a trifluoromethyl group. In the R1 of the present invention, the number of carbon atoms in the aralkyl group may be 6 to 8, specifically 6, 7 or 8; in a specific embodiment, the aralkyl group may be a benzyl group. In R1 of the present invention, the number of carbon atoms in the alkylamino group may be 2 to 6, specifically 2, 4 or 6; in a specific embodiment, the alkylamino group may be a dimethylamino group or a diethylamino group. In R1 of the present invention, the number of carbon atoms in the heterocyclic amino group may be 4 to 8, specifically 4, 5, 6, 7 or 8; in a specific embodiment, the heterocyclic amino group may be a morpholinyl group, a 4-methylpiperazin-1-yl group, a 4-ethylpiperazin-1-yl group, a piperidin-1-yl group or a pyrrolidin-1-yl group.

[0072] In the benzopyran-type flavonoid compound of the present invention, the R1 can be selected from any of the following groups:

[0073]

[0074]

[0075] In R2 of the present invention, the alkyl group may be a methyl group or an ethyl group.

[0076] In R3 of the present invention, the alkoxy group may be a methoxy group or an ethoxy group.

[0077] The benzopyran-type flavonoid compound of the present invention may be any one of the following compounds:

[0078]

[0079]

[0080]

[0081] In the present invention, the benzopyranose flavonoid compound targets the members of the SWEET protein family of plants, can selectively inhibit the sugar transport activity of the SWEET protein of plants, and has a broad-spectrum antibacterial activity. The combination of the two effects enhances the broad-spectrum disease resistance of plants.

[0082] The present invention also provides a method for preparing the benzopyran-type flavonoid compound described in the above technical solution, comprising the following steps:

[0083] (1) The method for preparing a benzopyran-type flavonoid compound having a structure shown in Formula I comprises the following steps:

[0084] Compound F is mixed with an aromatic aldehyde compound and ethanol, and subjected to a condensation reaction under alkaline conditions to obtain a benzopyran-type flavonoid compound having a structure shown in Formula I;

[0085] (2) The method for preparing a benzopyran-type flavonoid compound having a structure shown in Formula II comprises the following steps:

[0086] The benzopyran flavonoid compound having a structure shown in Formula I when R2 is -H is mixed with iodine and dimethyl sulfoxide to perform a ring-forming reaction to obtain a benzopyran flavonoid compound having a structure shown in Formula II;

[0087] The structural formula of the aromatic aldehyde compound is R1-CHO; the structural formula of the compound F is shown in Formula F:

[0088]

[0089] The R1, R2 and R3 are as defined in Formula I or Formula II.

[0090] In the present invention, unless otherwise specified, the raw materials used are commercially available products well known to those skilled in the art or are prepared by methods well known to those skilled in the art.

[0091] In the compound F of the present invention, the R2 may be -H or an alkyl group; in the embodiment of the present invention, the R2 may specifically be -H or -CH3.

[0092] In a specific embodiment of the present invention, the preparation method of the benzopyran flavonoid compound having the structure shown in Formula I comprises the following steps:

[0093] (1) When R2 is -H, the method for preparing a benzopyranose flavonoid compound having a structure shown in Formula I comprises the following steps:

[0094] Compound F1 is mixed with an aromatic aldehyde compound and ethanol, and subjected to a first condensation reaction under alkaline conditions to obtain a benzopyran-type flavonoid compound having a structure shown in Formula I;

[0095] (2) When R2 is -CH3, the preparation method of the benzopyran-type flavonoid compound having the structure shown in Formula I comprises the following steps:

[0096] Compound F1 is mixed with tetrabutylammonium bromide, dimethyl sulfate, dichloromethane and water, and subjected to a methylation reaction under alkaline conditions to obtain compound F2;

[0097] The compound F2 is mixed with an aromatic aldehyde compound and ethanol, and a second condensation reaction is carried out under alkaline conditions to obtain a benzopyran-type flavonoid compound having a structure shown in Formula I.

[0098] In the present invention, the structural formulas of the compound F1 and the compound F2 are shown in Formula F1 and Formula F2 respectively:

[0099]

[0100] In the present invention, the preparation method of the compound F1 may include the following steps:

[0101] Mixing compound A, an organic ether compound and a first solvent, and performing a substitution reaction under alkaline conditions to obtain compound B;

[0102] The compound B, tetrabutylammonium bromide, dimethyl sulfate and a second solvent are mixed, and a methylation reaction is carried out under alkaline conditions to obtain a compound C;

[0103] The compound C, the acidic reagent and the third solvent are mixed to perform a hydrolysis reaction to obtain a compound D;

[0104] The compound D, 3-methyl-2-butenal and the fourth solvent are mixed and subjected to a condensation reaction under alkaline conditions to obtain compound F1.

[0105] The structural formulas of compound A, compound B, compound C and compound D are shown in formula A, formula B, formula C and formula D respectively:

[0106]

[0107] Said R4 is selected from hydrogen or hydroxyl;

[0108] The R5 is selected from hydrogen or alkoxy.

[0109] The present invention mixes compound A, an organic ether compound and a first solvent, and performs a substitution reaction under alkaline conditions to obtain compound B. In the present invention, the organic ether compound may be chloromethyl methyl ether or bromomethyl methyl ether. In the present invention, the molar ratio of compound A to the organic ether compound may be 3.28:6.56-9.84; in a specific embodiment, the molar ratio of compound A to the organic ether compound is 3.28:8.20. The first solvent of the present invention may be acetone. In a specific embodiment of the present invention, compound A is 2,4,6-trihydroxyacetophenone, and the organic ether compound is chloromethyl methyl ether, and the compound B prepared thereby is 2-hydroxy-4,6-di(methoxymethoxy)acetophenone. In a specific embodiment of the present invention, 2,4,6-trihydroxyacetophenone is mixed with potassium carbonate, and acetone is added thereto for pretreatment to obtain a pretreated mixed liquid; then chloromethyl methyl ether is added to the pretreated mixed liquid to perform a substitution reaction. In a specific embodiment of the present invention, the molar ratio of the 2,4,6-trihydroxyacetophenone and potassium carbonate can be 3.28:13.13. In a specific embodiment of the present invention, the temperature of the pretreatment can be 60°C and the time can be 30min. In the present invention, the temperature of the substitution reaction can be 50-80°C and the time can be 2-5h; in a specific embodiment, the temperature of the substitution reaction can be 50°C, 60°C, 70°C or 80°C, and the time can be 3h or 4h. The substitution reaction of the present invention can be carried out under reflux conditions. The present invention can track the progress of the substitution reaction by thin layer chromatography (TLC). After the substitution reaction is completed, the present invention can cool the obtained reaction liquid to room temperature, filter, collect the liquid material and remove the solvent in the liquid material to obtain a concentrated solution; and then the concentrated solution is subjected to silica gel column chromatography to obtain compound B. The present invention can remove the solvent in the liquid material by reduced pressure distillation. In the present invention, the eluent used for the silica gel column chromatography may be a petroleum ether-ethyl acetate mixed reagent (PE-EA mixed reagent), and the volume ratio of petroleum ether (PE) to ethyl acetate (EA) in the PE-EA mixed reagent may be 15:1.

[0110] After obtaining compound B, the present invention mixes the compound B, tetrabutylammonium bromide, dimethyl sulfate and a second solvent, and performs a methylation reaction under alkaline conditions to obtain compound C. In the present invention, the molar ratio of compound B, tetrabutylammonium bromide and dimethyl sulfate can be 1.81:0.09-0.45:1.81-5.43; in a specific embodiment, the molar ratio of compound B, tetrabutylammonium bromide and dimethyl sulfate can be 1.81:0.18:3.98. The second solvent of the present invention can be a mixed solvent composed of dichloromethane and water, and the volume ratio of dichloromethane and water can be 3:2. In the specific implementation of the present invention, In the example, the compound B is 2-hydroxy-4,6-di(methoxymethoxy)acetophenone, and the compound C prepared therefrom is 2-methoxy-4,6-di( Crude product of methoxymethoxy)acetophenone. In a specific embodiment of the present invention, 2-hydroxy-4,6-bis(methoxymethoxy)acetophenone is dissolved in a mixed solvent consisting of dichloromethane and water, solid sodium hydroxide and tetrabutylammonium bromide are added thereto, and dimethyl sulfate is added dropwise to the obtained mixture under stirring to carry out a methylation reaction. In a specific embodiment of the present invention, the molar ratio of the 2-hydroxy-4,6-bis(methoxymethoxy)acetophenone to the solid sodium hydroxide can be 1.81:2.71. In the present invention, the temperature of the methylation reaction can be 20 to 35°C, and the time can be 1.5 to 12h; in a specific embodiment, the temperature of the methylation reaction can be 20°C, 25°C, 30°C or 35°C; the time can be 2h, 5h, 7h or 10h. The present invention can track the progress of the methylation reaction by TLC. After the methylation reaction is completed, the present invention can heat the obtained reaction liquid at 60° C. for 30 minutes to destroy the remaining dimethyl sulfate; then cool the obtained reaction liquid to room temperature, add sodium hydroxide aqueous solution thereto to adjust the pH value to neutral, extract with dichloromethane as an extractant, dry the organic layer obtained after extraction, collect the organic layer by filtration, and remove the solvent in the organic layer to obtain compound C. In the present invention, the concentration of the sodium hydroxide aqueous solution can be 1 mol / L. The present invention can remove the solvent in the organic layer by reduced pressure distillation, and can use anhydrous magnesium sulfate for drying.

[0111] After obtaining compound C, the present invention mixes the compound C, an acidic reagent and a third solvent to perform a hydrolysis reaction to obtain compound D. In the present invention, the acidic reagent may be hydrochloric acid, and the concentration of the hydrochloric acid may be 2-4 mol / L; in a specific embodiment, the concentration of the hydrochloric acid may be 3 mol / L. The third solvent of the present invention may be anhydrous ethanol. In a specific embodiment of the present invention, the compound C is 2-methoxy-4,6-di(methoxymethoxy)acetophenone, and the compound D prepared thereby is 2,4-dihydroxy-6-methoxyacetophenone. In the present invention, the temperature of the hydrolysis reaction may be 25-60°C, and the time may be 2-12h; in a specific embodiment, the temperature of the hydrolysis reaction may be 30°C, 40°C or 50°C, and the time may be 3h, 6h, 9h or 12h. The present invention may track the progress of the hydrolysis reaction by TLC. After the hydrolysis reaction is completed, the present invention can adjust the pH value of the obtained reaction liquid to neutral, then extract with dichloromethane as an extractant, dry the organic layer obtained after extraction, collect the organic layer by filtration, and remove the solvent in the organic layer to obtain a concentrated solution; the concentrated solution is subjected to silica gel column chromatography to obtain compound D. The present invention can remove the solvent in the organic layer by reduced pressure distillation, and can be dried with anhydrous magnesium sulfate. In the present invention, the eluent used for the silica gel column chromatography can be a PE-EA mixed reagent, and the volume ratio of PE and EA in the PE-EA mixed reagent can be 5:1.

[0112] After obtaining compound D, the present invention mixes the compound D, 3-methyl-2-butenal and a fourth solvent, and performs a condensation reaction under alkaline conditions to obtain compound F1. In the present invention, the molar ratio of compound D to 3-methyl-2-butenal can be 0.57:0.57-1.71; in a specific embodiment, the molar ratio of compound D to 3-methyl-2-butenal can be 0.57:1.15. The fourth solvent of the present invention can be anhydrous ethanol. In a specific embodiment of the present invention, the compound D is 2,4-dihydroxy-6-methoxyacetophenone, and the compound F1 prepared thereby is 1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)ethanone. In a specific embodiment of the present invention, 1-(2,4-dihydroxy-6-methoxyphenyl)ethanone, 3-methyl-2-butenal, anhydrous ethanol, calcium chloride and triethylamine are mixed and subjected to a condensation reaction. In a specific embodiment of the present invention, the molar ratio of 1-(2,4-dihydroxy-6-methoxyphenyl)ethanone, calcium chloride and triethylamine can be 0.57:0.57:1.73. In the present invention, the temperature of the condensation reaction can be 60-100°C, and the time can be 0.5-3h; in a specific embodiment, the temperature of the condensation reaction can be 70°C, 80°C or 90°C, and the time can be 1h, 2h or 2.5h. The present invention can track the progress of the condensation reaction by TLC. After the condensation reaction is completed, the present invention can cool the obtained reaction liquid to room temperature, remove the solvent in the reaction liquid, and obtain a concentrated solution; and then perform silica gel column chromatography on the concentrated solution to obtain compound F1. The present invention can remove the solvent in the reaction liquid by reduced pressure distillation. In the present invention, the eluent used for the silica gel column chromatography can be a PE-EA mixed reagent, and the volume ratio of PE and EA in the PE-EA mixed reagent can be 50:1.

[0113] After obtaining compound F1, the present invention mixes compound F1 with an aromatic aldehyde compound and ethanol, and performs a first condensation reaction under alkaline conditions to obtain a benzopyran-type flavonoid compound having a structure shown in formula I when R2 is -H. In the present invention, the molar ratio of compound F1 to the aromatic aldehyde compound can be 0.83:0.42-1.0; in a specific embodiment, the molar ratio of compound F1 to the aromatic aldehyde compound can be 0.83:0.55. The ethanol of the present invention can be anhydrous ethanol. In the present invention, the benzopyran-type flavonoid compound having a structure shown in formula I when R2 is -H is selected from ZQQ2-25, ZQQ27 or ZQQ30-37. In a specific embodiment of the present invention, the compound F1 is 1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)ethanone, the aromatic aldehyde compound is 4-(methoxymethoxy)benzaldehyde, and the benzopyran-type flavonoid compound prepared thereby is ZQQ2. In a specific embodiment of the present invention, 1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)ethanone, 4-(methoxymethoxy)benzaldehyde, anhydrous ethanol and sodium hydroxide aqueous solution are mixed to carry out a first condensation reaction. In a specific embodiment of the present invention, the mass fraction of the sodium hydroxide aqueous solution can be 40%; the volume ratio of the sodium hydroxide aqueous solution to anhydrous ethanol can be 3:20. In the present invention, the temperature of the first condensation reaction can be 20-35°C, and the time can be 24-96h; in a specific embodiment, the temperature of the first condensation reaction can be 20°C, 25°C, 30°C or 35°C; the time can be 24h, 48h, 72h or 96h. In the present invention, the first condensation reaction can be carried out under stirring. The present invention can track the progress of the first condensation reaction by TLC. After the first condensation reaction is completed, the present invention can extract the obtained reaction liquid with dichloromethane as an extractant, and dry the organic layer obtained after the extraction, and then collect the organic layer by filtration, and remove the solvent in the organic layer to obtain a concentrated solution; then the concentrated solution is subjected to a first silica gel column chromatography to obtain an intermediate. The present invention can remove the solvent in the organic layer by reduced pressure distillation, and can be dried with anhydrous magnesium sulfate. In the present invention, the eluent used for the silica gel column chromatography can be a PE-EA mixed reagent, and the volume ratio of PE and EA in the PE-EA mixed reagent can be 6:1. After obtaining the intermediate, the present invention can spin-dry the intermediate and mix it with an acidic reagent and anhydrous ethanol to perform a hydrolysis reaction to obtain a benzopyran-type flavonoid compound having a structure shown in Formula I when R2 is -H. In the present invention, the acidic reagent can be hydrochloric acid, and the concentration of the hydrochloric acid can be 2 to 4 mol / L; in a specific embodiment, the concentration of the hydrochloric acid can be 3 mol / L, and the volume ratio of the hydrochloric acid to the anhydrous ethanol can be 0.5:20.In the present invention, the temperature of the hydrolysis reaction can be 25-60°C, and the time can be 2-12h; in a specific embodiment, the temperature of the hydrolysis reaction can be 30°C, 40°C or 50°C, and the time can be 3h, 6h, 9h or 12h. The present invention can track the progress of the hydrolysis reaction by TLC. After the hydrolysis reaction is completed, the present invention can adjust the pH value of the obtained reaction liquid to neutral, then extract it with dichloromethane as an extractant, and dry the organic layer obtained after extraction, and then collect the organic layer by filtration, and remove the solvent in the organic layer to obtain a concentrated solution; the concentrated solution is subjected to a second silica gel column chromatography, and the benzopyran-type flavonoid compound having a structure shown in formula I when R2 is -H. The present invention can remove the solvent in the organic layer by reduced pressure distillation, and can be dried with anhydrous magnesium sulfate. In the present invention, the eluent used for the second silica gel column chromatography can be a PE-EA mixed reagent, and the volume ratio of PE and EA in the PE-EA mixed reagent can be 6:1.

[0114] After obtaining compound F1, the present invention mixes compound F1 with tetrabutylammonium bromide, dimethyl sulfate, dichloromethane and water, and performs methylation reaction under alkaline conditions to obtain compound F2. In the present invention, the molar ratio of compound F1, tetrabutylammonium bromide and dimethyl sulfate can be 0.51:0.03-0.1:0.51-1.5; in a specific embodiment, the molar ratio of compound F1, tetrabutylammonium bromide and dimethyl sulfate can be 0.51:0.05:1.07. The volume ratio of dichloromethane and water in the present invention can be 3:2. In a specific embodiment of the present invention, the compound F1 is 1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)ethanone, and the compound F2 prepared thereby is 1-(5,7-dimethoxy-2,2-dimethyl-2H-benzopyran-6-yl)ethanone. In a specific embodiment of the present invention, 1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)ethanone is dissolved in a mixed solvent consisting of dichloromethane and water, solid sodium hydroxide and tetrabutylammonium bromide are added thereto, and dimethyl sulfate is added dropwise to the resulting mixture under stirring to carry out a methylation reaction. In a specific embodiment of the present invention, the molar ratio of the 1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)ethanone to the solid sodium hydroxide can be 0.51:0.76. In the present invention, the temperature of the methylation reaction can be 20-35°C, and the time can be 1.5-12h; in a specific embodiment, the temperature of the methylation reaction can be 20°C, 25°C, 30°C or 35°C; the time can be 3h, 6h, 9h or 12h. The present invention can track the progress of the methylation reaction by TLC. After the methylation reaction is completed, the present invention can heat the obtained reaction liquid at 60°C for 30 minutes to destroy the remaining dimethyl sulfate; then cool the obtained reaction liquid to room temperature, add sodium hydroxide aqueous solution to adjust the pH value to neutral, extract with dichloromethane as the extractant, dry the organic layer obtained after extraction, collect the organic layer by filtration, and remove the solvent in the organic layer to obtain a concentrated solution; the concentrated solution is subjected to silica gel column chromatography to obtain compound F2. In the present invention, the concentration of the sodium hydroxide aqueous solution can be 1 mol / L. The present invention can remove the solvent in the organic layer by reduced pressure distillation, and can be dried with anhydrous magnesium sulfate. In the present invention, the eluent used for the silica gel column chromatography can be a PE-EA mixed reagent, and the volume ratio of PE and EA in the PE-EA mixed reagent can be 80:1.

[0115] After obtaining compound F2, the present invention mixes the compound F2 with an aromatic aldehyde compound and ethanol, and performs a second condensation reaction under alkaline conditions to obtain a benzopyran-type flavonoid compound having a structure shown in formula I when R2 is -CH3. In the present invention, the molar ratio of the compound F2 to the aromatic aldehyde compound can be 0.83:0.42-1.0; in a specific embodiment, the molar ratio of the compound F2 to the aromatic aldehyde compound can be 0.83:0.55. The ethanol of the present invention can be anhydrous ethanol. In the present invention, the benzopyran-type flavonoid compound having a structure shown in formula I when R2 is -CH3 is selected from ZQQ26, ZQQ28 or ZQQ29. In a specific embodiment of the present invention, the compound F2 is 1-(5,7-dimethoxy-2,2-dimethyl-2H-benzopyran-6-yl)ethanone, the aromatic aldehyde compound is 4-(methoxymethoxy)benzaldehyde, and the benzopyran-type flavonoid compound prepared thereby is ZQQ26. In a specific embodiment of the present invention, 1-(5,7-dimethoxy-2,2-dimethyl-2H-benzopyran-6-yl)ethanone, 4-(methoxymethoxy)benzaldehyde, anhydrous ethanol and sodium hydroxide aqueous solution are mixed to carry out a second condensation reaction. In a specific embodiment of the present invention, the mass fraction of the sodium hydroxide aqueous solution can be 40%; the volume ratio of the sodium hydroxide aqueous solution to anhydrous ethanol can be 3:20. In the present invention, the temperature of the second condensation reaction can be 20-35°C, and the time can be 24-96h; in a specific embodiment, the temperature of the second condensation reaction can be 20°C, 25°C, 30°C or 35°C; the time can be 24h, 48h, 72h or 96. In the present invention, the second condensation reaction can be carried out under stirring. The present invention can track the progress of the second condensation reaction by TLC. After the second condensation reaction is completed, the present invention can extract the obtained reaction liquid with dichloromethane as an extractant, and dry the organic layer obtained after extraction, and then collect the organic layer by filtration, and remove the solvent in the organic layer to obtain a concentrated solution; then the concentrated solution is subjected to a first silica gel column chromatography to obtain an intermediate. In the present invention, the present invention can remove the solvent in the organic layer by reduced pressure distillation, and anhydrous magnesium sulfate can be used for drying. In the present invention, the eluent used for the silica gel column chromatography can be a PE-EA mixed reagent, and the volume ratio of PE and EA in the PE-EA mixed reagent can be 6:1. After obtaining the intermediate, the present invention can spin-dry the intermediate and mix it with an acidic reagent and anhydrous ethanol to perform a hydrolysis reaction to obtain a benzopyran-type flavonoid compound having a structure shown in formula I when R2 is -CH3.In the present invention, the acidic reagent may be hydrochloric acid, and the concentration of the hydrochloric acid may be 2-4 mol / L; in a specific embodiment, the concentration of the hydrochloric acid may be 3 mol / L, and the volume ratio of the hydrochloric acid to anhydrous ethanol may be 0.5:20. In the present invention, the temperature of the hydrolysis reaction may be 25-60°C, and the time may be 2-12h; in a specific embodiment, the temperature of the hydrolysis reaction may be 30°C, 40°C or 50°C, and the time may be 3h, 6h, 9h or 12h. The present invention may track the progress of the hydrolysis reaction by TLC. After the hydrolysis reaction is completed, the present invention may adjust the pH value of the obtained reaction liquid to neutral, and then extract with dichloromethane as an extractant, and dry the organic layer obtained after the extraction, and then collect the organic layer by filtration, and remove the solvent in the organic layer to obtain a concentrated solution; the concentrated solution is subjected to a second silica gel column chromatography to obtain any one of the benzopyran-type flavonoid compounds ZQQ26, ZQQ28 or ZQQ29. The present invention can remove the solvent in the organic layer by reduced pressure distillation, and can be dried using anhydrous magnesium sulfate. In the present invention, the eluent used for the second silica gel column chromatography can be a PE-EA mixed reagent, and the volume ratio of PE to EA in the PE-EA mixed reagent can be 6:1.

[0116] When obtaining a benzopyran flavonoid compound having a structure shown in Formula I when R2 is -H, the present invention mixes the benzopyran flavonoid compound having a structure shown in Formula I when R2 is -H with iodine and dimethyl sulfoxide, and performs a ring-forming reaction to obtain a benzopyran flavonoid compound having a structure shown in Formula II. In the present invention, the molar ratio of the benzopyran flavonoid compound having a structure shown in Formula I when R2 is -H to iodine can be 1:0.02-0.1. In a specific embodiment, the molar ratio of the benzopyran flavonoid compound having a structure shown in Formula I when R2 is -H to iodine can be 20:1. The sixth solvent of the present invention can be dimethyl sulfoxide. In the present invention, the benzopyran flavonoid compound having a structure shown in Formula II is selected from any one of ZQQ41-76. In a specific embodiment of the present invention, a benzopyran flavonoid compound ZQQ6 is used to synthesize a benzopyran flavonoid compound ZQQ69, wherein the benzopyran flavonoid compound ZQQ6 is (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one. In the present invention, the temperature of the cyclization reaction can be 100 to 150°C, and the time can be 1 to 4 hours; in a specific embodiment, the temperature of the cyclization reaction can be 110°C, 120°C or 140°C, and the time can be 1.5 hours, 2 hours or 3 hours. After the cyclization reaction is completed, the present invention can mix the obtained reaction liquid with a saturated sodium thiosulfate solution, extract the obtained mixed liquid multiple times with ethyl acetate as an extractant, combine the obtained organic layers, dry and concentrate them in sequence, and obtain a concentrated solution; the concentrated solution is subjected to a first silica gel column chromatography to obtain an intermediate. In the present invention, the extraction times of ethyl acetate can be 3 times; anhydrous magnesium sulfate can be used for drying; and the concentration can be vacuum concentration. In the present invention, the eluent used for the silica gel column chromatography can be a dichloromethane-methanol mixed solvent, and the volume ratio of dichloromethane to methanol in the dichloromethane-methanol mixed solvent can be 20:1. After the cyclization reaction, the present invention mixes the obtained cyclization product with boron tribromide and dichloromethane to carry out a nucleophilic substitution reaction to obtain a benzopyran-type flavonoid compound having a structure shown in formula II. In a specific embodiment of the present invention, the cyclization product is ZQQ43, and the benzopyran-type flavonoid compound having a structure shown in formula II synthesized therefrom is ZQQ69. In the present invention, the molar ratio of the cyclization product to boron tribromide can be 1:1-3; in a specific embodiment, the molar ratio of the cyclization product to boron tribromide can be 1:1.5. In the present invention, the temperature of the nucleophilic substitution reaction can be -40 to -20°C, and the time can be 0.25 to 1h; in a specific embodiment, the temperature of the nucleophilic substitution reaction can be -40°C, -30°C or -20°C, and the time can be 15min, 30min, 15min or 60min.The present invention can track the progress of the nucleophilic substitution reaction by TLC. After the nucleophilic substitution reaction is completed, the present invention can add anhydrous methanol to quench the reaction, and the obtained reaction liquid is subjected to a second silica gel column chromatography to obtain a benzopyran-type flavonoid compound having a structure shown in Formula II. In the present invention, the eluent used for the second silica gel column layer can be a dichloromethane-methanol mixed reagent, and the volume ratio of dichloromethane to methanol in the dichloromethane-methanol mixed reagent can be 50:1.

[0117] In a specific embodiment of the present invention, ZQQ6 can be used as a raw material to prepare ZQQ43; ZQQ43 can be used as a raw material to prepare ZQQ69; ZQQ27 can be used as a raw material to prepare ZQQ55; ZQQ76 can be prepared using ZQQ55 as a raw material; ZQQ20 can be used as a raw material to prepare ZQQ47; ZQQ2 can be used as a raw material to prepare ZQQ70; ZQQ70 can be used as a raw material to prepare ZQQ73; ZQQ23 can be used as a raw material to prepare ZQQ46; ZQQ9 can be used as a raw material to prepare ZQQ53; ZQQ49 can be used as a raw material to prepare ZQQ75; ZQQ15 can be used as a raw material to prepare ZQQ48; ZQQ11 can be used as a raw material to prepare ZQQ50; ZQQ36 can be used as a raw material to prepare ZQQ54; and ZQQ52 can be used as a raw material to prepare ZQQ74.

[0118] The present invention also provides the use of the benzopyran flavonoid compound described in the above technical solution in the preparation of a broad-spectrum antibacterial drug.

[0119] The present invention also provides the use of the benzopyranose flavonoid compound described in the above technical solution in the preparation of a plant sugar transporter inhibitor. In the present invention, the benzopyranose flavonoid compound targets members of the SWEET protein family of plants.

[0120] The present invention also provides a pharmaceutical preparation, comprising an active ingredient and a pharmaceutical excipient; the active ingredient is the benzopyran flavonoid compound described in the above technical solution. In the present invention, the dosage form of the pharmaceutical preparation may include wettable powder, suspension, aqueous solution, granules, spray, tablet, capsule, aerosol or nano preparation.

[0121] The invention prepares novel benzopyran flavonoid compounds based on the xanthohumol C structural skeleton. The novel benzopyran flavonoid compounds take members of the SWEET protein family of plants as targets, selectively inhibit the sugar transport activity of the SWEET proteins of plants, have broad-spectrum antibacterial activity, and significantly inhibit the hyphae growth of pathogenic fungi such as rice blast pathogen, corn leaf blight pathogen, corn ear rot pathogen, rice sheath blight pathogen, tobacco brown spot pathogen, soybean sclerotinia pathogen, grape canker pathogen, and the like. Meanwhile, the novel benzopyran flavonoid compounds can effectively inhibit the growth rate of pathogenic bacteria such as Chinese cabbage soft rot pathogen, tobacco wildfire pathogen, rice white leaf blight pathogen, tobacco angular leaf spot pathogen, tobacco bacterial wilt pathogen, and the like.

[0122] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0123] The "room temperature" mentioned in the examples is 25°C.

[0124] Preparation Example 1

[0125] (1) Acetone (40 mL) was added to a reaction flask containing 2,4,6-trihydroxyacetophenone (compound A, 552 mg, 3.28 mmol) and potassium carbonate (1.82 g, 13.13 mmol), and the mixture was reacted at 60°C for 30 min; then chloromethyl methyl ether (622 μL, 8.20 mmol) was added dropwise thereto, and the reaction was refluxed at 60°C for 3 h starting from the completion of the addition of chloromethyl methyl ether. The reaction progress was monitored by TLC during the reaction. After the reaction was completed, the reaction liquid was cooled to room temperature, filtered, and the liquid material was collected; the solvent in the liquid material was removed by vacuum distillation to obtain a concentrated solution; the concentrated solution was subjected to silica gel column chromatography using a PE-EA mixed reagent (wherein the volume ratio of PE to EA was 15:1) as an eluent, and 2-hydroxy-4,6-di(methoxymethoxy)acetophenone (i.e., compound B, colorless oil, 463 mg, yield 60%) was obtained.

[0126] The characterization data of compound B are as follows: 1 H NMR (400MHz, CDCl3): δ13.71(s,1H),6.29-6.21(m,2H),5.25(s,2H),5.17(s,2H),3.51(s,3H),3.47(s,3H),2.65(s,3H).

[0127] (2) Compound B (463 mg, 1.81 mmol) obtained in step (1) was dissolved in a dichloromethane-water mixed solvent (25 mL, wherein the volume ratio of dichloromethane to water was 3:2), and sodium hydroxide (108 mg, 2.71 mmol) and tetrabutylammonium bromide (58 mg, 0.18 mmol) were added thereto, and dimethyl sulfate (386 μL, 3.98 mmol) was added dropwise while stirring. The timing was started from the completion of the addition of dimethyl sulfate. The resulting mixture was stirred at room temperature for 2 h, and the reaction progress was monitored by TLC during the reaction. After the reaction is completed, the obtained reaction liquid is heated at 60° C. for 30 min to destroy the remaining dimethyl sulfate, and then the obtained reaction liquid is cooled to room temperature, and a sodium hydroxide aqueous solution (**mol / L) is added to adjust the pH value to 7, and then the obtained liquid is extracted with dichloromethane as an extractant; the organic layer obtained after the extraction is dried with anhydrous magnesium sulfate, filtered, and an organic layer is obtained. The solvent in the organic layer is removed by reduced pressure distillation to obtain 2-methoxy-4,6-di(methoxymethoxy)acetophenone (compound C), and compound C is directly used for the next step reaction.

[0128] (3) Compound C obtained in step (2) was completely dissolved in anhydrous ethanol (20 mL), and 3 mol / L hydrochloric acid (0.5 mL) was added, and the mixture was reacted at 50° C. for 3 h. The reaction progress was monitored by TLC. After the reaction was completed, 3 mol / L sodium bicarbonate aqueous solution was added to the reaction solution to adjust the pH value to 7, and the solution was extracted with dichloromethane as an extractant. The organic layer obtained after the extraction was dried with anhydrous magnesium sulfate, filtered, and the organic layer was obtained. The solvent in the organic layer was removed by vacuum distillation to obtain a concentrated solution; the concentrated solution was subjected to silica gel column chromatography using a PE-EA mixed reagent (wherein the volume ratio of PE to EA was 5:1) as an eluent, and 1-(2,4-dihydroxy-6-methoxyphenyl)ethanone (i.e., compound D, white solid, 229 mg, yield 75%) was obtained after the reaction.

[0129] The characterization data of compound D are as follows: 1 H NMR (400MHz, DMSO-d6): δ13.81(s,1H),10.63(s,1H), δ5.97(s,1H),5.87(s,1H),3.82(s,3H),2.51(s,3H).

[0130] (4) Anhydrous ethanol (20 mL) was added to a reaction bottle containing compound D (105 mg, 0.57 mmol) obtained in step (3) and 3-methyl-2-butenal (111 μL, 1.15 mmol), and calcium chloride (64 mg, 0.57 mmol) and triethylamine (240 μL, 1.73 mmol), and the mixture was reacted at 80° C. for 1 h. The reaction progress was monitored by TLC during the reaction. After the reaction, the reaction solution was cooled to room temperature, and the solvent in the reaction solution was removed by vacuum distillation to obtain a concentrated solution; the concentrated solution was subjected to silica gel column chromatography using a PE-EA mixed reagent (wherein the volume ratio of PE to EA was 50:1) as an eluent, and 1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)ethanone (i.e., compound F1, orange-yellow solid, 86 mg, yield 65%) was obtained.

[0131] The characterization data of compound F1 are as follows: 1 H NMR (400MHz, CDCl3): δ14.27(s,1H),6.64(d,J=9.9Hz,1H),5.88(s,1H),5.44(d,J=10.0Hz,1H),3.85(s,3H),2.59(s,3H),1.44(s,6H).

[0132] Preparation Example 2

[0133] The compound F1 (126 mg, 0.51 mmol) obtained in Preparation Example 1 was dissolved in a dichloromethane-water mixed solvent (25 mL, wherein the volume ratio of dichloromethane to water was 3:2), and sodium hydroxide (30 mg, 0.76 mmol) and tetrabutylammonium bromide (16 mg, 0.05 mmol) were added thereto, and dimethyl sulfate (104 μL, 1.07 mmol) was added dropwise while stirring. The timing was started from the completion of the addition of dimethyl sulfate. The resulting mixture was stirred at room temperature for 3 h, and the reaction progress was monitored by TLC during the reaction. After the reaction, the obtained reaction liquid was heated at 60° C. for 30 min to destroy the remaining dimethyl sulfate, and then the obtained reaction liquid was cooled to room temperature, and an aqueous sodium hydroxide solution (**mol / L) was added to adjust the pH value to 7, and then extracted with dichloromethane as an extractant, and the organic layer obtained after the extraction was dried with anhydrous magnesium sulfate, filtered to obtain an organic layer, and the solvent in the organic layer was removed by reduced pressure distillation to obtain a concentrated solution; the concentrated solution was subjected to silica gel column chromatography using a PE-EA mixed reagent (wherein the volume ratio of PE to EA is 80:1) as an eluent, and 1-(5,7-dimethoxy-2,2-dimethyl-2H-benzopyran-6-yl)ethanone (compound F2, yellow solid, 106 mg, yield 80%) was obtained.

[0134] The characterization data of compound F2 are as follows: 1 H NMR (400MHz, CDCl3) δ6.47(d,J=9.9Hz,1H),6.19(s,1H),5.52(d,J=9.9Hz,1H),3.77(s,3H),3.75(s,3H),2.48(s,3H),1.42(s,6H).

[0135] Example 1

[0136] Anhydrous ethanol (20 mL) and 40 wt% sodium hydroxide aqueous solution (3 mL) were added to a reaction bottle containing compound F1 (205 mg, 0.83 mmol) obtained in Preparation Example 1 and 4-(methoxymethoxy)benzaldehyde (91 mg, 0.55 mmol), and the mixture was stirred at room temperature for 48 h. The reaction progress was monitored by TLC during the reaction. After the reaction, the obtained feed liquid was extracted with dichloromethane as an extractant, and the organic layer obtained after the extraction was dried with anhydrous magnesium sulfate, filtered, and an organic layer was obtained. The solvent in the organic layer was removed by reduced pressure distillation to obtain a concentrated solution; the concentrated solution was subjected to silica gel column chromatography with a PE-EA mixed reagent (wherein the volume ratio of PE and EA can be 6:1) as an eluent, and intermediate 2 (orange oil, 142 mg) was obtained after the reaction.

[0137] The intermediate 2 was dried and dissolved in anhydrous ethanol (20 mL), 3 mol / L hydrochloric acid (0.5 mL) was added, and then reacted at 50°C for 3 h. The reaction progress was monitored by TLC. After the reaction, 3 mol / L sodium bicarbonate aqueous solution was added to adjust the pH value to 7, and then the obtained feed liquid was extracted with dichloromethane as an extractant, and the organic layer obtained after extraction was dried with anhydrous magnesium sulfate, filtered, and the organic layer was obtained. The solvent in the organic layer was removed by reduced pressure distillation to obtain a concentrated solution; the concentrated solution was subjected to silica gel column chromatography using a PE-EA mixed reagent (wherein the volume ratio of PE and EA was 6:1) as an eluent, and after the end, a benzopyran-type flavonoid compound ZQQ2 (orange solid particles, 85 mg, yield 44%) was obtained.

[0138] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ2 are as follows:

[0139] (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(4-hydroxyphenyl)prop-2-en-1-one;

[0140]

[0141] 1 H NMR (400MHz, CDCl3) δ14.62(s,1H),7.76(s,2H),7.50(d,J=8.6Hz,2H),6.86(d,J=8.4Hz,2 H),6.68(d,J=10.0Hz,1H),5.92(s,1H),5.46(d,J=10.0Hz,1H),3.91(s,3H),1.46(s,6H). 13 C NMR (101MHz, CDCl3) δ192.83,162.66,162.57,160.26,157.83,142.49,130.39,128.38,125.45 ,125.21,116.15,115.99,106.14,103.10,91.62,78.30,55.94,28.43.ESI-MS:m / z=353.2[M+H] +

[0142] Example 2

[0143] The benzopyran flavonoid compound ZQQ3 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 3-methoxy-4-(methoxymethoxy)benzaldehyde.

[0144] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ3 are as follows:

[0145] (E)-3-(4-hydroxy-3-methoxyphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0146]

[0147] Orange solid; yield 36%; 1 H NMR (400MHz, CDCl3) δ7.75 (s, 2H), 7.20 (dd, J = 8.3, 1.9Hz, 1H), 7.08 (d, J = 1.9Hz, 1H), 6.94 (d, J = 8.2Hz, 1H),6.69(d,J=10.0Hz,1H),5.92(s,1H),5.46(d,J=10.0Hz,1H),3.94(s,3H),3.91(s,3H),1.45(s,6H). 13C NMR (101MHz, CDCl3) δ192.62,162.61,162.58,160.20,147.91,146.75,142.77,128.31,125.43,125.36,12 2.69,116.19,114.93,110.58,106.14,103.14,91.59,78.26,55.96,55.91,28.44.ESI-MS: m / z=383.2[M+H] + .

[0148] Example 3

[0149] The benzopyran flavonoid compound ZQQ4 was prepared in the manner of Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by benzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0150] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ4 are as follows:

[0151] (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-phenylprop-2-en-1-one;

[0152]

[0153] Yellow solid; yield 48%; 1 H NMR (400MHz, CDCl3) δ14.52 (s, 1H), 7.92-7.73 (m, 2H), 7.63-7.58 (m, 2H), 7.40 (d, J = 6.7Hz, 3H),6.69(d,J=10.0Hz,1H),5.93(s,1H),5.47(d,J=10.0Hz,1H),3.92(s,3H),1.46(s,6H). 13 C NMR (101MHz, CDCl3) δ192.79,162.70,162.62,160.43,142.24,135.68,130.08,128.94,128.41 ,127.74,125.46,116.13,106.15,103.09,91.62,78.33,55.95,28.46.ESI-MS: m / z=337.2[M+H] + .

[0154] Example 4

[0155] The benzopyran flavonoid compound ZQQ5 was prepared in the manner of Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 4-isopropylbenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0156] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ5 are as follows:

[0157] (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(4-isopropylphenyl)prop-2-en-1-one;

[0158]

[0159] Yellow solid; yield 45%; 1 H NMR (400MHz, CDCl3) δ7.75 (s, 2H), 7.20 (d, J = 10.1Hz, 1H), 7.07 (s, 1H), 6.93 (s, 1H), 6.69 (d ,J=10.0Hz,1H),5.92(s,1H),5.46(d,J=10.0Hz,1H),3.94(s,3H),3.91(s,3H),1.45(s,6H). 13 C NMR (101MHz, CDCl3) δ192.85,162.68,162.61,160.30,151.46,142.45,133.33,128.56,127.07,126.7 9,125.41,116.18,106.18,103.09,91.59,78.28,55.91,34.17,28.44,23.86.ESI-MS: m / z=379.2[M+H] + .

[0160] Example 5

[0161] The benzopyran flavonoid compound ZQQ6 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 4-chlorobenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0162] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ6 are as follows:

[0163] (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0164]

[0165] Yellow solid; yield 46%; 1 H NMR (400MHz, CDCl3) δ14.46(s,1H),7.83(d,J=15.6Hz,1H),7.70(d,J=15.6Hz,1H),7.52(d,J=8.5Hz,2H),7 .37(d,J=8.5Hz,2H),6.68(d,J=10.0Hz,1H),5.92(s,1H),5.47(d,J=10.0Hz,1H),3.91(s,3H),1.46(s,6H). 13 C NMR (101MHz, CDCl3) δ192.46,162.65,162.63,160.57,140.68,135.88,134.19,129.51,129.20 ,128.23,125.52,116.06,106.09,103.10,91.65,78.41,55.98,28.47.ESI-MS:m / z=371.1[M+H] + .

[0166] Example 6

[0167] The benzopyran flavonoid compound ZQQ7 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 2-(methoxymethoxy)benzaldehyde.

[0168] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ7 are as follows:

[0169] (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(2-hydroxyphenyl)prop-2-en-1-one;

[0170]

[0171] Orange oil; yield 33%; 1H NMR (400MHz, CDCl3) δ14.54(s,1H),8.15-7.89(m,2H),7.53(d,J=7.7Hz,1H),7.25-7.19(m,1H),6.93(t,J=7.6Hz, 1H), 6.87 (d, J = 8.1Hz, 1H), 6.69 (d, J = 10.0Hz, 1H), 5.92 (s, 1H), 5.47 (d, J = 10.0Hz, 1H), 3.89 (s, 3H), 1.46 (s, 6H). 13 CNMR(101MHz, CDCl3)δ193.41,162.82,162.53,160.48,155.58,137.90,131.37,129.01,128.25,125.47 ,122.92,120.84,116.67,116.12,106.23,103.05,91.71,78.35,55.94,28.45.ESI-MS: m / z=353.2[M+H] + .

[0172] Example 7

[0173] The benzopyran flavonoid compound ZQQ8 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 3,5-dimethyl-4-(methoxymethoxy)benzaldehyde.

[0174] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ8 are as follows:

[0175] (E)-3-(4-hydroxy-3,5-dimethoxyphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0176]

[0177] Orange solid; yield: 29%; 1 H NMR (400MHz, CDCl3) δ7.79-7.67(m,2H),6.85(s,2H),6.68(d,J=10.0Hz,1H) ,5.92(s,1H),5.46(d,J=10.0Hz,1H),3.94(s,6H),3.90(s,3H),1.45(s,6H). 13C NMR (101MHz, CDCl3) δ192.46,162.60,162.53,160.24,147.27,142.92,137.20,127.23,125.66,12 5.47,116.15,106.12,105.49,103.16,91.62,78.29,56.37,55.89,28.43.ESI-MS:m / z=413.2[M+H] + .

[0178] Example 8

[0179] The benzopyran flavonoid compound ZQQ9 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 4-methoxy-3-(methoxymethoxy)benzaldehyde.

[0180] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ9 are as follows:

[0181] (E)-3-(3-hydroxy-4-methoxyphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0182]

[0183] Orange solid; yield 33%; 1 H NMR (400MHz, CDCl3) δ14.62(s,1H),7.73(d,J=3.8Hz,2H),7.23(d,J=2.1Hz,1H),7.09(dd,J=8.3,2.1Hz,1H),6.86(d,J=8. 3Hz,1H),6.68(d,J=10.0Hz,1H),5.92(s,1H),5.70(s,1H),5.46(d,J=10.0Hz,1H),3.93(s,3H),3.91(s,3H),1.45(s,6H). 13 C NMR (101MHz, CDCl3) δ192.72,162.67,162.61,160.23,148.54,145.87,142.47,129.33,125.85,125.39,12 2.86,116.19,112.82,110.59,106.15,103.07,91.56,78.26,56.08,55.96,28.44.ESI-MS: m / z=383.2[M+H]+ .

[0184] Example 9

[0185] The benzopyran flavonoid compound ZQQ10 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 2-methoxy-4-(methoxymethoxy)benzaldehyde.

[0186] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ10 are as follows:

[0187] (E)-3-(4-hydroxy-2-methoxyphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0188]

[0189] Orange oil; yield 33%; 1 H NMR (400MHz, DMSO-d6) δ14.81(s,1H),10.24(s,1H),7.96(dd,J=15.6,4.5Hz,1H),7.83(dd,J=15.6,7.1Hz,1H),7.54(d,J=8.3Hz,1 H),6.54(d,J=10.0Hz,1H),6.47(d,J=9.8Hz,2H),6.09(d,J=4.5Hz,1H),5.62-5.55(m,1H),3.91(s,3H),3.85(s,3H),1.40(s,6H). 13 C NMR(101MHz,DMSO-d6)δ192.87,162.86,162.43,161.90,160.91,160.04,139.48,131.57,126.44,123.75,1 15.83,115.19,108.98,105.96,102.53,99.71,92.35,78.52,56.74,56.04,28.50.ESI-MS: m / z=383.2[M+H] + .

[0190] Example 10

[0191] The benzopyran flavonoid compound ZQQ11 was prepared in the manner of Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 3,4,5-trimethylbenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0192] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ11 are as follows:

[0193] (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(3,4,5-trimethoxyphenyl)prop-2-en-1-one;

[0194]

[0195] Yellow solid; yield 44%; 1 H NMR (400MHz, CDCl3) δ14.53 (s, 1H), 7.81-7.64 (m, 2H), 6.83 (s, 2H), 6.68 (d, J = 10.0 Hz,1H),5.92(s,1H),5.46(d,J=10.0Hz,1H),3.90(s,9H),3.89(s,3H),1.45(s,6H). 13 C NMR (101MHz, CDCl3) δ192.47,162.61,162.57,160.38,153.46,142.32,140.11,131.24,127.12,125.5 0,116.10,106.11,105.60,103.13,91.64,78.34,61.06,56.18,55.89,28.44.ESI-MS: m / z=427.2[M+H] + .

[0196] Embodiment 11

[0197] The benzopyran flavonoid compound ZQQ12 was prepared in the manner of Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 3,5-dimethylbenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0198] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ12 are as follows:

[0199] (E)-3-(3,5-dimethoxyphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0200]

[0201] Yellow solid; yield 48%;1 H NMR (400MHz, CDCl3) δ7.90-7.60(m,2H),6.75(d,J=2.2Hz,2H),6.68(d,J=10.0Hz,1H),6.50( t,J=2.3Hz,1H),5.92(s,1H),5.47(d,J=10.0Hz,1H),3.91(s,3H),3.83(s,6H),1.46(s,6H). 13 C NMR (101MHz, CDCl3) δ192.71,162.60,161.04,160.48,142.11,137.62,128.34,125.49,116.10 ,106.40,106.23,106.14,102.13,91.63,78.36,55.96,55.47,28.45.ESI-MS: m / z=397.2[M+H] + .

[0202] Example 12

[0203] The benzopyran flavonoid compound ZQQ13 was prepared in the manner of Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 2,3-dimethylbenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0204] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ13 are as follows:

[0205] (E)-3-(2,3-dimethoxyphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0206]

[0207] Yellow solid; yield 42%; 1 H NMR (400MHz, CDCl3) δ8.10-7.90(m,2H),7.22(d,J=7.9Hz,1H),7.08(t,J=8.0Hz,1H),6.94(d,J=8.0Hz, 1H),6.69(d,J=10.0Hz,1H),5.92(s,1H),5.46(d,J=10.0Hz,1H),3.90(s,3H),3.89(s,6H),1.45(s,6H). 13C NMR (101MHz, CDCl3) δ193.05,162.71,162.63,160.35,153.29,148.88,137.07,129.85,129.14,125.41,124.2 0,119.82,116.17,113.74,106.23,103.07,91.58,78.29,61.37,55.95,55.92,28.45.ESI-MS: m / z=397.2[M+H] + .

[0208] Embodiment 13

[0209] The benzopyran flavonoid compound ZQQ14 was prepared in the manner of Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 2,3,4-trimethylbenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0210] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ14 are as follows:

[0211] (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(2,3,4-trimethoxyphenyl)prop-2-en-1-one;

[0212]

[0213] Yellow solid; yield 40%; 1 H NMR(400MHz, CDCl3)δ8.03-7.85(m,2H),7.34(d,J=10.0Hz,1H),6.74-6.66(m,2H) ,5.92(s,1H),5.45(d,J=11.4Hz,1H),3.95(s,3H),3.91-3.88(m,9H),1.44(s,6H). 13 C NMR (101MHz, CDCl3) δ193.01,162.63,160.11,155.52,153.77,142.54,137.78,126.72,125.37,123.80,122.7 5,116.24,107.68,106.24,103.10,91.54,78.22,61.49,60.99,56.14,55.89,28.43.ESI-MS: m / z=427.2[M+H] + .

[0214] Embodiment 14

[0215] The benzopyran flavonoid compound ZQQ15 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 3-methylbenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0216] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ15 are as follows:

[0217] (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(3-methoxyphenyl)prop-2-en-1-one;

[0218]

[0219] Yellow solid; yield 48%; 1 H NMR (400MHz, CDCl3) δ7.91-7.65(m,2H),7.32(t,J=7.9Hz,1H),7.21(d,J=7.6Hz,1H),7.12(s,1H),6.94(d,J= 8.1Hz,1H),6.69(d,J=10.0Hz,1H),5.93(s,1H),5.47(d,J=9.9Hz,1H),3.92(s,3H),3.85(s,3H),1.46(s,6H). 13 CNMR(101MHz, CDCl3)δ192.74,162.69,162.61,160.46,159.93,142.09,137.09,129.91,128.09,125.47,12 0.98,116.12,115.64,113.69,106.15,103.08,91.62,78.35,55.95,55.35,28.46.ESI-MS: m / z=367.2[M+H] + .

[0220] Embodiment 15

[0221] The benzopyran flavonoid compound ZQQ16 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 3-methylbenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0222] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ16 are as follows:

[0223] (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(3-methoxyphenyl)prop-2-en-1-one;

[0224]

[0225] Yellow solid; yield 48%; 1 H NMR (400MHz, CDCl3) δ7.91-7.65(m,2H),7.32(t,J=7.9Hz,1H),7.21(d,J=7.6Hz,1H),7.12(s,1H),6.94(d,J= 8.1Hz,1H),6.69(d,J=10.0Hz,1H),5.93(s,1H),5.47(d,J=9.9Hz,1H),3.92(s,3H),3.85(s,3H),1.46(s,6H). 13 CNMR(101MHz, CDCl3)δ192.74,162.69,162.61,160.46,159.93,142.09,137.09,129.91,128.09,125.47,12 0.98,116.12,115.64,113.69,106.15,103.08,91.62,78.35,55.95,55.35,28.46.ESI-MS: m / z=367.2[M+H] + .

[0226] Example 16

[0227] The benzopyran flavonoid compound ZQQ17 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 5-bromo-2-ethoxybenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0228] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ17 are as follows:

[0229] (E)-3-(5-bromo-2-ethoxyphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0230]

[0231] Yellow solid; yield: 38.34%; 1H NMR (400MHz, CDCl3) δ8.07-7.79(m,2H),7.68(d,J=2.5Hz,1H),7.43-7.36(m,1H),6.78(d,J=8.9Hz,1H),6.68 (d,J=10.0Hz,1H),5.92(s,1H),5.46(d,J=10.0Hz,1H),4.09(q,J=6.9Hz,2H),3.91(s,3H),1.51-1.44(m,9H). 13 CNMR(101MHz, CDCl3)δ192.87,162.68,162.53,160.41,156.95,135.86,133.55,130.88,129.05,126.86,125.4 4,116.14,113.90,112.87,106.24,103.05,91.60,78.32,64.46,56.04,28.46,14.80.ESI-MS:m / z=459.2[M+H] + .

[0232] Embodiment 17

[0233] The benzopyran flavonoid compound ZQQ18 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 3-benzyloxybenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0234] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ18 are as follows:

[0235] (E)-3-(3-(benzyloxy)phenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0236]

[0237] Yellow solid; yield 38%; 1 H NMR (400MHz, CDCl3) δ7.88-7.68(m,2H),7.47-7.38(m,4H),7.37-7.29(m,2H),7.24-7.17(m,2H),7.01(dd,J=8.1 ,2.5Hz,1H),6.69(d,J=10.0Hz,1H),5.92(s,1H),5.47(d,J=10.0Hz,1H),5.11(s,2H),3.89(s,3H),1.46(s,6H).13 C NMR (101MHz, CDCl3) δ192.73,162.69,162.59,160.47,159.17,142.05,137.13,136.80,129.95,128.74,128.17,128.10,12 7.55,125.47,121.30,116.59,116.12,114.61,106.15,103.07,91.62,78.35,70.18,55.98,28.46.ESI-MS: m / z=443.3[M+H] + .

[0238] Embodiment 18

[0239] The benzopyran flavonoid compound ZQQ19 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 3-bromobenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0240] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ19 are as follows:

[0241] (E)-3-(3-bromophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0242]

[0243] Yellow solid; yield 47%; 1 H NMR (400MHz, CDCl3) δ14.40(s,1H),7.83(d,J=15.6Hz,1H),7.72(s,1H),7.65(d,J=15.6Hz,1H),7.49(dd,J=7.9,1.8 Hz,2H),7.27(t,J=7.9Hz,1H),6.68(d,J=10.0Hz,1H),5.93(s,1H),5.47(d,J=10.0Hz,1H),3.92(s,3H),1.46(s,6H). 13C NMR (101MHz, CDCl3) δ192.35,162.68,162.62,160.67,140.23,137.88,132.74,130.90,130.43,129.12 ,127.06,125.53,123.05,116.04,106.09,103.08,91.68,78.43,56.04,28.48.ESI-MS: m / z=415.1[M+H] + .

[0244] Embodiment 19

[0245] The benzopyran flavonoid compound ZQQ20 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 4-trifluoromethylbenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0246] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ20 are as follows:

[0247] (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-one;

[0248]

[0249] Yellow solid; yield 42%; 1 H NMR (400MHz, CDCl3) δ14.36(s,1H),7.91(d,J=15.6Hz,1H),7.73(d,J=15.7Hz,1H),7.70-7.63 (m,4H),6.68(d,J=10.0Hz,1H),5.93(s,1H),5.48(d,J=10.0Hz,1H),3.92(s,3H),1.46(s,6H). 13 C NMR (101MHz, CDCl3) δ192.36,162.66,160.62,140.29,135.73,133.57,130.88,130.42,127.93,127 .67,125.90,125.49,116.09,106.11,103.09,91.63,78.41,55.98,28.47.ESI-MS:m / z=405.2[M+H] + .

[0250] Embodiment 20

[0251] The benzopyran flavonoid compound ZQQ21 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 3-tert-butylbenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0252] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ21 are as follows:

[0253] (E)-3-(4-(tert-butyl)phenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0254]

[0255] Yellow solid; yield 46%; 1 H NMR (400MHz, CDCl3) δ7.93-7.75(m,2H),7.62(s,1H),7.44(t,J=7.6Hz,2H),7.34(t,J=7.7Hz,1H), 6.69(d,J=10.0Hz,1H),5.93(s,1H),5.47(d,J=9.9Hz,1H),3.92(s,3H),1.46(s,6H),1.36(s,9H). 13 C NMR (101MHz, CDCl3) δ192.84,162.68,162.65,160.37,151.79,142.91,135.35,128.68,127.43,127.35,125.9 0,125.45,125.19,116.15,106.14,103.10,91.61,78.31,55.87,34.75,31.31,28.45.ESI-MS: m / z=393.3[M+H] + .

[0256] Embodiment 21

[0257] The benzopyran flavonoid compound ZQQ22 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 2-bromobenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0258] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ22 are as follows:

[0259] (E)-3-(2-bromophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0260]

[0261] Yellow solid; yield 43%; 1 H NMR (400MHz, CDCl3) δ8.09(d,J=15.6Hz,1H),7.79(d,J=15.5Hz,1H),7.69-7.65(m,1H),7.64-7.61(m,1H),7.34(t,J= 7.6Hz,1H),7.24-7.19(m,1H),6.69(d,J=10.0Hz,1H),5.92(s,1H),5.47(d,J=10.0Hz,1H),3.90(s,3H),1.46(s,6H). 13 C NMR (101MHz, CDCl3) δ192.39,162.63,162.60,160.45,153.84,140.49,132.15,130.05,129.42,126.70 ,125.49,116.55,116.10,110.86,106.09,103.10,91.64,78.36,56.01,28.46.ESI-MS: m / z=415.1[M+H] + .

[0262] Embodiment 22

[0263] The benzopyran flavonoid compound ZQQ23 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 4-bromobenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0264] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ23 are as follows:

[0265] (E)-3-(4-bromophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0266]

[0267] Yellow solid; yield 48%; 1H NMR (400MHz, CDCl3) δ14.44(s,1H),7.84(d,J=15.6Hz,1H),7.68(d,J=15.6Hz,1H),7.52(d,J=8.5Hz,2H),7 .44(d,J=8.5Hz,2H),6.68(d,J=10.0Hz,1H),5.92(s,1H),5.47(d,J=10.0Hz,1H),3.91(s,3H),1.46(s,6H). 13 C NMR (101MHz, CDCl3) δ192.43,162.64,160.59,140.71,134.61,132.16,129.73,128.34,125 .51,124.22,116.05,106.08,103.09,91.64,78.41,55.98,28.47.ESI-MS:m / z=415.1[M+H] + .

[0268] Embodiment 23

[0269] The benzopyran flavonoid compound ZQQ24 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 3-bromo-4-hydroxybenzaldehyde.

[0270] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ24 are as follows:

[0271] (E)-3-(3-bromo-4-hydroxyphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0272]

[0273] Orange solid; yield 26%; 1 H NMR (400MHz, CDCl3) δ14.50(s,1H),7.74(d,J=15.4Hz,1H),7.71(s,1H),7.65(d,J=15.7Hz,1H),7.48(d,J=8.4Hz, 1H),7.04(d,J=8.4Hz,1H),6.68(d,J=10.0Hz,1H),5.92(s,1H),5.47(d,J=10.0Hz,1H),3.92(s,3H),1.46(s,6H). 13CNMR(101MHz, CDCl3)δ179.92,163.37,162.96,159.68,149.91,147.32,139.30,131.34,127.9 5,124.05,114.07,107.37,104.43,99.60,95.36,79.37,56.51,28.54.ESI-MS: m / z=431.2[M+H] + .

[0274] Embodiment 24

[0275] The benzopyran flavonoid compound ZQQ25 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 4-nitrobenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0276] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ25 are as follows:

[0277] (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(4-nitrophenyl)prop-2-en-1-one;

[0278]

[0279] Yellow solid; yield 39%; 1 H NMR (400MHz, CDCl3) δ8.28(d,J=8.8Hz,2H),7.97(d,J=8.8Hz,2H),6.75(s,1H),6. 63(d,J=9.9Hz,1H),6.11(s,1H),5.67(d,J=9.9Hz,1H),3.96(s,3H),1.52(s,6H). 13 C NMR (101MHz, CDCl3) δ195.19,158.79,158.09,156.01,154.65,146.08,130.63,127.84,127.0 3,126.23,116.59,116.08,108.03,96.31,76.94,63.38,55.96,27.97.ESI-MS: m / z=380.1[MH] + .

[0280] Embodiment 25

[0281] The benzopyran flavonoid compound ZQQ26 was prepared in the same manner as in Example 1, except that compound F1 was replaced by compound F2.

[0282] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ26 are as follows:

[0283] (E)-1-(5,7-dimethoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(4-hydroxyphenyl)prop-2-en-1-one;

[0284]

[0285] Yellow solid; yield 42%; 1 H NMR (400MHz, CDCl3) δ7.39(d,J=8.6Hz,2H),7.34(d,J=16.0Hz,1H),6.86(d,J=15.9Hz,1H),6.83(d,J=8.6 Hz,2H),6.50(d,J=10.0Hz,1H),6.24(s,1H),5.54(d,J=9.9Hz,1H),3.73(s,3H),3.71(s,3H),1.45(s,6H). 13 C NMR (101MHz, CDCl3) δ192.29,162.68,162.64,160.80,139.91,139.14,128.38,125.89,125.85 ,125.59,115.98,106.08,103.10,91.70,78.49,56.00,55.62,28.48.ESI-MS: m / z=367.2[M+H] + .

[0286] Embodiment 26

[0287] The benzopyran flavonoid compound ZQQ27 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 4-(4-methylpiperazinyl)benzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0288] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ27 are as follows:

[0289] (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(4-(4-methyl piperazin-1-yl)phenyl)prop-2-en-1-one;

[0290]

[0291] Orange oil; yield 41.39%; 1 H NMR (400MHz, CDCl3) δ14.75(s,1H),7.76(d,J=2.6Hz,2H),7.51(d,J=8.8Hz,2H),6.89(d,J=8.8Hz,2H),6.68(d,J=10.0Hz, 1H),5.91(s,1H),5.45(d,J=10.0Hz,1H),3.90(s,3H),3.37-3.30(m,4H),2.59(t,J=5.1Hz,4H),2.37(s,3H),1.45(s,6H). 13 C NMR (101MHz, CDCl3) δ192.66,162.62,162.58,159.96,152.45,143.03,130.11,126.16,125.33,123.89,1 16.28,114.97,106.19,103.10,91.51,78.16,55.88,54.85,47.83,46.15,28.42.ESI-MS: m / z=435.3[M+H] + .

[0292] Embodiment 27

[0293] The benzopyran flavonoid compound ZQQ28 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by benzaldehyde, and compound F1 was replaced by compound F2, and the hydrochloric acid hydrolysis step was not required.

[0294] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ28 are as follows:

[0295] (E)-1-(5,7-dimethoxy-2,2-dimethyl-2H-chromen-6-yl)-3-phenylprop-2-en-1-one;

[0296]

[0297] Yellow solid; yield 59%;1 H NMR (400MHz, CDCl3) δ7.53(dd,J=6.7,3.0Hz,2H),7.41(d,J=16.0Hz,1H),7.38-7.33(m,3H),7.01(d,J=16. 0Hz,1H),6.52(d,J=9.9Hz,1H),6.25(s,1H),5.54(d,J=9.9Hz,1H),3.74(s,3H),3.74(s,3H),1.46(s,6H). 13 C NMR (101MHz, CDCl3) δ194.23,158.21,156.09,154.88,144.80,134.90,130.43,128.90,128.80,12 8.55,127.80,116.63,116.33,108.08,96.25,76.92,63.40,55.97,27.98.ESI-MS:m / z=351.2[M+H] + .

[0298] Embodiment 28

[0299] The benzopyran flavonoid compound ZQQ29 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 4-chlorobenzaldehyde, and compound F1 was replaced by compound F2, and the hydrochloric acid hydrolysis step was not required.

[0300] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ29 are as follows:

[0301] (E)-3-(4-chlorophenyl)-1-(5,7-dimethoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0302]

[0303] Yellow solid; yield 57%; 1 H NMR (400MHz,CDCl3) 1 H NMR(400MHz, CDCl3) δ7.46(d,J=8.6Hz,2H),7.41-7.30(m,3H),6.97(d,J=16.1Hz,1H),6.51 (d,J=9.9Hz,1H),6.25(s,1H),5.55(d,J=9.9Hz,1H),3.75(s,3H),3.74(s,3H),1.46(s,6H). 13C NMR (101MHz, CDCl3) δ193.79,158.23,156.23,154.93,143.00,136.25,133.43,129.67,129.17 ,127.88,116.55,116.23,108.10,96.29,76.97,63.48,55.99,27.98.ESI-MS: m / z=385.2[M+H] + .

[0304] Embodiment 29

[0305] The benzopyran flavonoid compound ZQQ30 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 5-indolecarboxaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0306] The English name, structure and characterization data of the benzopyran-type flavonoid compound ZQQ30 are as follows: (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(1H-indol-5-yl)prop-2-en-1-one;

[0307]

[0308] Orange solid; yield: 21%; 1 H NMR (400MHz, DMSO-d6) δ14.72(s,1H),11.39(s,1H),7.91(d,J=9.7Hz,2H),7.85(d,J=15.5Hz,1H),7 .55-7.40(m,3H),6.59-6.51(m,2H),6.12(s,1H),5.60(d,J=10.0Hz,1H),3.95(s,3H),1.42(s,6H). 13 C NMR(101MHz,DMSO-d6)δ192.64,162.92,161.81,160.15,146.22,137.98,128.57,127.30,126.49,123.74,12 3.62,121.50,115.81,112.80,105.99,102.79,102.54,92.42,78.57,56.90,28.52.ESI-MS:m / z=376.2[M+H] + .

[0309] Embodiment 30

[0310] The benzopyran flavonoid compound ZQQ31 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 4-piperidin-1-ylbenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0311] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ21 are as follows:

[0312] (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(4-(piperidin-1-yl)phenyl)prop-2-en-1-one;

[0313]

[0314] Yellow solid; yield 43%; 1 H NMR (400MHz, CDCl3) δ14.81(s,1H),7.76(d,J=6.2Hz,2H),7.50(d,J=8.6Hz,2H),6.96-6.84(m,2H),6.69(d,J= 10.0Hz,1H),5.92(s,1H),5.45(d,J=10.0Hz,1H),3.90(s,3H),3.30(t,J=5.3Hz,4H),1.70(s,3H),1.45(s,6H). 13 C NMR (101MHz, CDCl3) δ192.64,162.62,162.57,159.89,143.26,132.06,130.21,125.30,123.44,116.30,115. 15,113.35,106.20,103.10,91.49,78.14,55.87,49.42,48.46,28.41,25.43,24.30.ESI-MS:m / z=420.3[M+H] + .

[0315] Embodiment 31

[0316] The benzopyran flavonoid compound ZQQ32 was prepared in the manner of Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by N,N-dimethyl-4-aminobenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0317] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ32 are as follows:

[0318] (E)-3-(4-(dimethylamino)phenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0319]

[0320] Yellow solid; yield 44%; 1 H NMR (400MHz, CDCl3) δ14.89(s,1H),7.82(d,J=15.4Hz,1H),7.73(d,J=15.4Hz,1H),7.51(d,J=8.7Hz ,2H),6.74-6.65(m,3H),5.92(s,1H),5.45(d,J=10.0Hz,1H),3.91(s,3H),3.04(s,6H),1.45(s,6H). 13 C NMR (101MHz, CDCl3) δ192.61,162.64,162.54,159.74,151.87,143.92,130.41,128.91,125.26,123.48 ,122.26,116.36,111.95,106.22,103.12,91.46,78.08,55.86,40.22,28.41.ESI-MS:m / z=380.3[M+H] + .

[0321] Embodiment 32

[0322] The benzopyran flavonoid compound ZQQ33 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 4-(1-pyrrolidinyl)benzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0323] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ33 are as follows:

[0324] (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(4-(pyrrolidin-1-yl)phenyl)prop-2-en-1-one;

[0325]

[0326] Yellow solid; yield 44%; 1H NMR (400MHz, CDCl3) δ15.00(s,1H),7.93-7.70(m,2H),7.54(d,J=8.8Hz,2H),6.77-6.70(m,1H),6.59(d,J=8.4Hz,2H ),5.95(s,1H),5.49(d,J=10.0Hz,1H),3.94(d,J=8.0Hz,3H),3.39(t,J=6.6Hz,4H),2.10-2.05(m,4H),1.49(s,6H). 13 C NMR (101MHz, CDCl3) δ192.54,162.64,162.51,159.63,149.47,144.41,130.66,125.22,122.83,121.4 8,116.40,111.80,106.24,103.13,91.43,78.04,55.85,47.64,28.40,25.52.ESI-MS: m / z=406.2[M+H] + .

[0327] Embodiment 33

[0328] The benzopyran flavonoid compound ZQQ34 was prepared in the manner of Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by N,N-diethyl-4-aminobenzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0329] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ34 are as follows:

[0330] (E)-3-(4-(diethylamino)phenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)prop-2-en-1-one;

[0331]

[0332] Yellow solid; yield 41%; 1 H NMR (400MHz, CDCl3) δ14.99 (s, 1H), 7.91-7.69 (m, 2H), 7.53 (d, J = 8.5Hz, 2H), 6.76-6.66 (m, 3H), 5.95 ( s,1H),5.49(d,J=10.0Hz,1H),3.94(s,3H),3.45(q,J=7.1Hz,4H),1.49(s,6H),1.24(t,J=7.0Hz,6H). 13C NMR (101MHz, CDCl3) δ192.56,162.64,162.52,159.64,149.51,144.11,130.77,125.24,122.62,121.5 7,116.38,111.35,106.24,103.13,91.43,78.05,55.83,44.58,28.39,12.67.ESI-MS:m / z=408.3[M+H] + .

[0333] Embodiment 34

[0334] The benzopyran flavonoid compound ZQQ35 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 2-(4-methylpiperazinyl)benzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0335] The English name, structure and characterization data of the benzopyran-type flavonoid compound ZQQ35 are as follows: (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(2-(4-methyl piperazin-1-yl)phenyl)prop-2-en-1-one;

[0336]

[0337] Orange oil; yield 33%; 1 H NMR (400MHz, CDCl3) δ14.62(s,1H),8.16(d,J=15.7Hz,1H),7.82(d,J=15.7Hz,1H),7.61(d,J=7.7Hz,1H),7.35(t,J=7.3Hz,1H),7.07(dd,J=8.0 ,4.6Hz,2H),6.70(d,J=10.0Hz,1H),5.92(s,1H),5.46(d,J=10.0Hz,1H) ,3.90(s,3H),3.07-3.00(m,4H),2.67(s,4H),2.40(s,3H),1.46(s,6H). 13C NMR (101MHz, CDCl3) δ193.10,162.65,162.62,160.21,152.93,139.88,130.76,129.82,128.01,127.30,125.38,1 22.84,118.89,116.22,106.19,103.09,91.53,78.24,55.92,55.32,52.76,46.08,28.43.ESI-MS:m / z=435.3[M+H] + .

[0338] Embodiment 35

[0339] The benzopyran flavonoid compound ZQQ36 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by 3-(4-methylpiperazinyl)benzaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0340] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ36 are as follows:

[0341] (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(3-(4-methyl piperazin-1-yl)phenyl)prop-2-en-1-one;

[0342]

[0343] Orange oil; yield 42%; 1 H NMR (400MHz, CDCl3) δ14.53(s,1H),7.84(d,J=15.5Hz,1H),7.73(d,J=15.5Hz,1H),7.28(t,J=7.8Hz,1H),7.16-7.07(m,2H),6.96(dd,J=8.2,2.5Hz ,1H),6.68(d,J=10.0Hz,1H),5.92(s,1H),5.46(d,J=10.0Hz,1H),3.90(s ,3H),3.29-3.22(m,4H),2.61(t,J=5.0Hz,4H),2.37(s,3H),1.45(s,6H). 13C NMR (101MHz, CDCl3) δ192.81,162.67,162.60,160.38,151.67,142.88,136.53,129.59,127.69,125.45,119.33,1 17.99,116.40,116.14,106.15,103.08,91.61,78.31,55.92,55.05,48.98,46.12,28.45.ESI-MS: m / z=435.3[M+H] + .

[0344] Embodiment 36

[0345] The benzopyran flavonoid compound ZQQ37 was prepared in the same manner as in Example 1, except that 4-(methoxymethoxy)benzaldehyde was replaced by N-methyl-3-indolecarboxaldehyde, and the hydrochloric acid hydrolysis step was not required.

[0346] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ37 are as follows:

[0347] (E)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)-3-(1-methyl-1H-indol-3-yl)prop-2-en-1-one;

[0348]

[0349] Yellow solid; yield 33%; 1 H NMR (400MHz, CDCl3) δ8.14-7.98(m,3H),7.40(s,1H),7.39-7.32(m,2H),7.32-7.27(m,1H),6.7 2(d,J=9.9Hz,1H),5.96(s,1H),5.46(d,J=10.0Hz,1H),3.98(s,3H),3.82(s,3H),1.47(s,6H). 13 C NMR(101MHz,DMSO-d6)δ192.16,162.73,162.24,161.51,159.76,138.73,137.70,126.37,125.91,123.42,122.24,1 20.80,120.45,115.95,112.74,111.64,105.73,102.68,92.33,78.44,56.90,33.55,28.51.ESI-MS: m / z=390.2[M+H] + .

[0350] Embodiment 37

[0351] 1.00 mmol of benzopyran flavonoid compound ZQQ6 ((E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one) was added to dimethyl sulfoxide (DMSO), and then 0.05 mmol of I2 was added, and the reaction was stirred at 120° C. for 1.5 hours. After the reaction, the obtained feed liquid was poured into a saturated sodium thiosulfate solution, extracted with ethyl acetate as an extractant, and the organic phase was collected; the extraction operation was repeated three times, the obtained organic phases were combined and dried with anhydrous magnesium sulfate, and then vacuum concentrated to obtain a concentrated solution; the concentrated solution was subjected to silica gel column chromatography with a dichloromethane-methanol mixed solvent as an eluent, and the benzopyran flavonoid compound ZQQ43 (light yellow solid, yield 77%) was obtained after the reaction.

[0352] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ43 are as follows:

[0353] 2-(4-chlorophenyl)-5-methoxy-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0354]

[0355] Yellow solid; yield 77%; 1 H NMR (400MHz, CDCl3) δ7.77(d,J=8.6Hz,2H),7.46(d,J=8.6Hz,2H),6.79(d,J=10.0H z,1H),6.61(s,1H),6.32(s,1H),5.62(d,J=10.0Hz,1H),3.94(s,3H),1.49(s,6H). 13 C NMR (101MHz, CDCl3) δ177.56,160.73,159.30,158.23,153.92,137.52,130.20,129 .40,127.79,127.22,115.17,108.96,108.74,102.69,78.27,96.86,56.55,28.29.

[0356] Embodiment 38

[0357] 1mmol of benzopyran flavonoid compound ZQQ43 was dissolved in CH2Cl2, and 1.5mmol of BBr3 was added at -70℃, and the reaction was continued for 30min at -20℃. The reaction progress was monitored by TLC. After the reaction was completed, anhydrous methanol was added to quench the reaction; then the obtained reaction liquid was subjected to silica gel column chromatography using a dichloromethane-methanol mixed reagent (the volume ratio of dichloromethane to methanol was 50:1) as an eluent, and the benzopyran flavonoid compound ZQQ69 (yellow solid, yield 34%) was obtained after the reaction.

[0358] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ69 are as follows:

[0359] 2-(4-chlorophenyl)-5-hydroxy-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0360]

[0361] Yellow solid; yield 34%; 1 H NMR (400MHz, CDCl3) δ12.70(s,1H),7.81(d,J=8.2Hz,2H),7.51(d,J=8.8Hz,2H),6.76 (d,J=10.0Hz,1H),6.62(s,1H),6.29(s,1H),5.63(dd,J=9.9,1.0Hz,1H),1.49(s,6H). 13 C NMR (101MHz, CDCl3) δ182.41,162.37,161.85,159.86,151.93,138.22,130. 01,129.57,127.81,127.49,114.73,106.11,101.39,100.60,78.20,28.26.

[0362] Embodiment 39

[0363] The benzopyran-type flavonoid compound ZQQ41 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(2-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0364] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ41 are as follows:

[0365] 2-(2-chlorophenyl)-5-methoxy-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0366]

[0367] Yellow solid; yield 37%; 1 H NMR (400MHz, CDCl3) δ7.61(d,J=8.0Hz,1H),7.53(d,J=7.9Hz,1H),7.42(dt,J=19.9,7.2Hz,2H),6.76 (d,J=11.8Hz,1H),6.57(s,1H),6.35(s,1H),5.56(dd,J=10.0,1.9Hz,1H),3.95(s,3H),1.49(s,6H). 13 C NMR (101MHz, CDCl3) δ177.72,160.74,160.13,158.29,154.39,132.95,131.73,131.61,130.95 ,130.78,127.52,127.19,115.25,113.98,108.67,102.77,96.82,78.32,77.40,56.51,28.37.

[0368] Embodiment 40

[0369] The benzopyran-type flavonoid compound ZQQ42 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(3-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0370] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ42 are as follows:

[0371] 2-(3-chlorophenyl)-5-methoxy-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0372]

[0373] Yellow solid; yield 65%; 1 H NMR (400MHz, CDCl3) δ7.83(s,1H),7.73(d,J=7.5Hz,1H),7.46(dt,J=15.9,8.2Hz,2H),6.82( d,J=10.0Hz,1H),6.71(s,1H),6.34(s,1H),5.65(d,J=10.0Hz,1H),3.95(s,3H),1.51(s,6H). 13 C NMR (101MHz, CDCl3) δ177.51,160.76,158.99,158.37,153.94,135.27,133.55,131.29,130.39 ,127.87,126.05,124.15,115.14,109.41,108.74,102.72,96.94,96.80,78.34,56.57,28.31.

[0374] Embodiment 41

[0375] The benzopyran-type flavonoid compound ZQQ44 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(2,4-dichlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0376] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ44 are as follows:

[0377] 2-(2,4-dichlorophenyl)-5-methoxy-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0378]

[0379] Yellow solid; yield 21%; 1 H NMR (400MHz, CDCl3) δ7.55 (d, J=8.4Hz, 2H), 7.38 (dd, J=8.4, 2.1Hz, 1H), 6.71 (d, J=10 .0Hz,1H),6.54(s,1H),6.34(s,1H),5.56(d,J=10.1Hz,1H),3.95(s,3H),1.48(s,6H). 13C NMR (101MHz, CDCl3) δ177.26,160.79,159.02,158.43,154.29,137.34,133.79,131.51 ,130.88,130.10,127.66,115.07,113.99,108.55,102.70,96.95,78.40,56.58,28.38.

[0380] Embodiment 42

[0381] The benzopyran-type flavonoid compound ZQQ45 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(3,4-dichlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0382] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ45 are as follows:

[0383] 2-(3,4-dichlorophenyl)-5-methoxy-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0384]

[0385] Yellow solid; yield 33%; 1 H NMR (400MHz, CDCl3) δ7.93(d,J=2.0Hz,1H),7.67(d,J=10.5Hz,1H),7.62-7.56(m,1H),6.78( d,J=10.0Hz,1H),6.70(s,1H),6.34(s,1H),5.66(d,J=10.0Hz,1H),3.95(s,3H),1.51(s,6H). 13 C NMR (101MHz, CDCl3) δ177.30,160.75,158.42,158.03,153.84,135.63,133.68,131.69,131 .17,127.98,127.75,125.05,115.04,109.54,108.72,102.67,97.02,78.36,56.60,28.32.

[0386] Embodiment 43

[0387] The benzopyran-type flavonoid compound ZQQ46 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(4-bromophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0388] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ46 are as follows:

[0389] 2-(4-bromophenol)-5-methoxy-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0390]

[0391] Yellow solid; yield 79%; 1 H NMR (400MHz, CDCl3) δ7.72(d,J=8.7Hz,2H),7.64(d,J=8.7Hz,2H),6.81(d,J=10.0H z,1H),6.68(s,1H),6.34(s,1H),5.63(d,J=10.0Hz,1H),3.95(s,3H),1.50(s,6H). 13 C NMR (101MHz, CDCl3) δ177.54,160.77,159.40,158.26,153.95,132.38,130.72,127 .80,127.41,125.92,115.16,109.02,108.79,102.70,96.89,78.27,56.54,28.30.

[0392] Embodiment 44

[0393] The benzopyran-type flavonoid compound ZQQ47 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(4-trifluoromethylphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0394] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ47 are as follows:

[0395] 5-methoxy-8,8-dimethyl-2-(4-(trifluoromethyl)phenyl)-4H,8H-pyrano[2,3-f]chromen-4-one;

[0396]

[0397] Yellow solid; yield 70%; 1 H NMR (400MHz, CDCl3) δ7.96(d,J=8.1Hz,2H),7.76(d,J=8.2Hz,2H),6.81(d,J=10.0H z,1H),6.72(s,1H),6.34(s,1H),5.64(d,J=10.0Hz,1H),3.95(s,3H),1.50(s,6H). 13 C NMR (101MHz, CDCl3) δ177.38,160.77,158.71,158.41,153.94,135.18,133.03,127.91 ,126.32,126.09,126.06,115.06,110.05,108.80,102.70,96.98,78.35,56.57,28.30.

[0398] Embodiment 45

[0399] The benzopyran-type flavonoid compound ZQQ48 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(3-methoxyphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0400] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ48 are as follows:

[0401] 5-methoxy-2-(3-methoxyphenyl)-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0402]

[0403] Yellow solid; yield 55%; 1H NMR (400MHz, CDCl3) δ7.47-7.38(m,2H),7.36(s,1H),7.04(d,J=9.2Hz,1H),6.84(d,J=10.0Hz ,1H),6.66(s,1H),6.33(s,1H),5.62(d,J=10.0Hz,1H),3.95(s,3H),3.88(s,3H),1.50(s,6H). 13 C NMR (101MHz, CDCl3) δ177.83,160.72,160.41,160.03,158.25,154.05,133.01,130.19,127.71 ,118.49,116.98,115.25,111.50,108.88,108.71,102.76,96.81,78.28,56.57,55.53,28.31.

[0404] Embodiment 46

[0405] The benzopyran-type flavonoid compound ZQQ49 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(3,4-dimethoxyphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0406] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ49 are as follows:

[0407] 2-(3,4-dimethoxyphenyl)-5-methoxy-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0408]

[0409] Yellow solid; yield 34%; 1 H NMR (400MHz, CDCl3) δ7.48 (d, J = 6.5 Hz, 1H), 7.44 (s, 1H), 7.29 (s, 1H), 7.00 (d, J = 8. 6Hz,1H),6.65(s,1H),6.31(s,1H),3.97(s,3H),3.95(d,J=3.9Hz,6H),1.62(s,6H). 13C NMR (101MHz, CDCl3) δ177.52,161.19,160.57,157.20,152.67,152.03,149.36,127.45,123.76,1 19.62,111.30,108.68,108.51,107.56,104.44,96.83,96.61,82.02,56.66,56.17,56.03,28.25.

[0410] Embodiment 47

[0411] The benzopyran-type flavonoid compound ZQQ50 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(3,4,5-trimethylphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0412] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ50 are as follows:

[0413] 5-methoxy-8,8-dimethyl-2-(3,4,5-trimethoxyphenyl)-4H,8H-pyrano[2,3-f]chromen-4-one;

[0414]

[0415] Yellow solid; yield 25%; 1 H NMR (400MHz, CDCl3) δ7.07 (s, 2H), 6.77 (d, J = 10.0Hz, 1H), 6.64 (s, 1H), 6.33 (s, 1H), 5.63 (d, J = 10.0Hz, 1H), 3.95 (s, 3H), 3.94 (s, 6H), 3.91 (s, 3H), 1.50 (s, 6H). 13 C NMR (101MHz, CDCl3) δ177.76,160.71,160.27,158.15,153.98,153.61,140.97,127.86,126.9 5,115.04,108.70,108.55,103.46,103.26,102.64,96.78,78.20,61.10,56.55,56.39,28.30.

[0416] Embodiment 48

[0417] The benzopyran-type flavonoid compound ZQQ51 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(4-methoxyphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0418] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ51 are as follows:

[0419] 5-methoxy-2-(4-methoxyphenyl)-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0420]

[0421] Yellow solid; yield 64%; 1 H NMR (400MHz, CDCl3) δ7.80(d,J=8.9Hz,2H),7.00(d,J=8.9Hz,2H),6.83(d,J=10.0Hz,1H),6.61( s,1H),6.32(s,1H),5.62(d,J=10.0Hz,1H),5.29(s,1H),3.94(s,3H),3.87(s,3H),1.50(s,6H). 13 C NMR (101MHz, CDCl3) δ177.85,162.15,160.68,160.44,157.92,153.98,127.64,127.57 ,124.02,115.40,114.50,108.75,107.45,102.74,96.64,78.13,56.52,55.55,28.28.

[0422] Embodiment 49

[0423] The benzopyran-type flavonoid compound ZQQ52 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(2-methoxyphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0424] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ52 are as follows:

[0425] 5-methoxy-2-(2-methoxyphenyl)-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0426]

[0427] Yellow solid; yield 34%; 1 H NMR (400MHz, CDCl3) δ7.83(dd,J=7.8,1.8Hz,1H),7.49-7.38(m,1H),7.08(t,J=8.1Hz,1H),7.02(d,J=9.4Hz,1H) ,6.98(s,1H),6.80(d,J=10.0Hz,1H),6.31(s,1H),5.58(d,J=10.0Hz,1H),3.94(s,3H),3.92(s,3H),1.49(s,6H). 13 C NMR (101MHz, CDCl3) δ178.26,160.66,158.02,157.83,157.80,154.28,132.07,128.88,127.32 ,120.76,120.73,115.54,113.91,111.79,108.85,102.69,96.43,78.05,56.49,55.69,28.28.

[0428] Embodiment 50

[0429] The benzopyran-type flavonoid compound ZQQ53 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(3-hydroxy-4-methoxyphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0430] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ53 are as follows:

[0431] 2-(3-hydroxy-4-methoxyphenyl)-5-methoxy-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0432]

[0433] Yellow solid; yield 21%; 1 H NMR (400MHz, CDCl3) δ7.47(s,1H),7.39(d,J=8.6Hz,1H),6.93(d,J=8.6Hz,1H),6.84(d,J=10.0Hz,1H ),6.65(s,1H),6.31(s,1H),5.59(d,J=10.0Hz,1H),3.94(d,J=8.9Hz,6H),2.62(s,3H),1.48(s,6H). 13 C NMR (101MHz, CDCl3) δ177.98,160.61,160.32,157.88,153.95,149.41,146.16,127.53,124.78,11 8.63,115.45,112.25,110.89,108.77,107.77,102.76,96.58,78.14,56.49,56.14,40.97,28.26.

[0434] Embodiment 51

[0435] The benzopyran-type flavonoid compound ZQQ54 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(3-(4-methylpiperazinyl)phenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0436] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ54 are as follows:

[0437] 5-methoxy-8,8-dimethyl-2-(3-(4-methylpiperazin-1-yl)phenyl)-4H,8H-pyrano[2,3-f]chromen-4-one;

[0438]

[0439] Yellow solid; yield: 28%; 1H NMR (400MHz, CDCl3) δ7.37(dd,J=16.0,8.2Hz,3H),7.07(d,J=7.6Hz,1H),6.81(d,J=10.0Hz,1H),6.64(s,1H),6.32 (s,1H),5.61(d,J=10.0Hz,1H),3.95(s,3H),3.29(t,J=4.9Hz,4H),2.63(t,J=4.9Hz,4H),2.38(s,3H),1.50(s,6H). 13 C NMR (101MHz, CDCl3) δ177.92,160.82,160.66,157.96,154.07,151.67,132.65,129.80,127.62,119.0 1,117.27,115.32,113.11,109.03,108.94,102.76,96.64,78.16,56.55,54.98,48.89,46.13,28.30.

[0440] Embodiment 52

[0441] The benzopyran-type flavonoid compound ZQQ55 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(4-(4-methylpiperazinyl)phenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0442] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ55 are as follows:

[0443] 5-methoxy-8,8-dimethyl-2-(4-(4-methylpiperazin-1-yl)phenyl)-4H,8H-pyrano[2,3-f]chromen-4-one;

[0444]

[0445] Yellow solid; yield 30%; 1H NMR (400MHz, CDCl3) δ7.78(d,J=8.5Hz,2H),6.99(d,J=8.6Hz,2H),6.88(d,J=10.0Hz,1H),6.58(s,1H),6.34(s, 1H),5.64(d,J=10.0Hz,1H),3.98(s,3H),3.40(t,J=5.0Hz,4H),2.64(t,J=5.0Hz,4H),2.41(s,3H),1.53(s,6H). 13 CNMR (101MHz, CDCl3) δ177.96,160.66,160.62,157.69,153.96,152.93,127.44,127.26,121.37,115.51 ,114.81,108.86,106.70,102.74,96.47,78.04,77.43,77.11,76.79,56.51,54.74,47.60,46.10,28.27.

[0446] Embodiment 53

[0447] The benzopyran-type flavonoid compound ZQQ56 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(4-(4-ethylpiperazinyl)phenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0448] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ56 are as follows:

[0449] 2-(4-(4-ethylpiperazin-1-yl)phenyl)-5-methoxy-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0450]

[0451] Yellow solid; yield 16%; 1H NMR (400MHz, CDCl3) δ7.75(s,2H),6.95(d,J=9.0Hz,2H),6.84(d,J=10.0Hz,1H),6.54(s,1H),6.30(s,1H),5.60(d,J=10.0H z,1H),3.93(s,3H),3.37(t,J=5.0Hz,4H),2.64(t,J=5.0Hz,4H),2.51(q,J=7.2Hz,2H),1.49(s,6H),1.15(t,J=7.2Hz,3H). 13 C NMR (101MHz, CDCl3) δ177.87,160.64,160.59,157.68,153.97,152.85,127.43,127.26,121.54,1 15.51,114.86,108.90,106.79,102.75,96.49,78.02,56.51,52.41,52.38,47.48,28.27,11.71.

[0452] Embodiment 54

[0453] The benzopyran-type flavonoid compound ZQQ57 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(3-morpholinylphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0454] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ57 are as follows:

[0455] 5-methoxy-8,8-dimethyl-2-(3-morpholinophenyl)-4H,8H-pyrano[2,3-f]chromen-4-one;

[0456]

[0457] Yellow solid; yield 48%; 1H NMR (400MHz, CDCl3) δ7.39(d,J=7.0Hz,2H),7.33(s,1H),7.06(dt,J=7.3,2.3Hz,1H),6.82(d,J=10.0Hz,1H),6.6 4(s,1H),6.33(s,1H),5.63(d,J=10.0Hz,1H),3.95(s,3H),3.90(t,J=4.8Hz,4H),3.26-3.20(m,4H),1.50(s,6H). 13 CNMR(101MHz, CDCl3)δ177.89,160.70,160.68,157.99,154.06,151.70,132.75,129.89,127.67,1 18.65,117.64,115.29,112.77,109.09,108.94,102.74,96.67,78.17,66.85,56.56,49.18,28.30.

[0458] Embodiment 55

[0459] The benzopyran-type flavonoid compound ZQQ58 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(4-morpholinylphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0460] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ58 are as follows:

[0461] 5-methoxy-8,8-dimethyl-2-(4-morpholinophenyl)-4H,8H-pyrano[2,3-f]chromen-4-one

[0462]

[0463] Yellow solid; yield 51%; 1H NMR (400MHz, CDCl3) δ7.76(d,J=8.6Hz,2H),6.95(d,J=8.6Hz,2H),6.84(d,J=10.0Hz,1H),6.56(s,1H),6. 31(s,1H),5.61(d,J=10.0Hz,1H),3.94(s,3H),3.87(t,J=4.8Hz,4H),3.28(t,J=4.9Hz,4H),1.50(s,6H). 13 C NMR (101MHz, CDCl3) δ177.90,160.64,160.52,157.71,153.96,153.09,127.46,127.27,12 1.88,115.50,114.57,108.88,106.88,102.74,96.50,78.05,66.68,56.53,47.94,28.27.

[0464] Embodiment 56

[0465] The benzopyran-type flavonoid compound ZQQ59 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(4-chlorophenyl)-1-(5-hydroxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0466] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ59 are as follows:

[0467] 2-(4-chlorophenyl)-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0468]

[0469] Yellow solid; yield 78%; 1 H NMR (400MHz, CDCl3) δ7.99(d,J=8.7Hz,1H),7.83(d,J=8.7Hz,2H),7.51(d,J=8.6 Hz,2H),6.89(t,J=9.7Hz,2H),6.77(s,1H),5.77(d,J=10.0Hz,1H),1.52(s,6H). 13C NMR (101MHz, CDCl3) δ177.78,161.59,157.79,152.33,137.79,130.67,130.58, 129.49,127.44,126.16,117.70,115.43,115.07,109.46,107.57,77.87,28.21.

[0470] Embodiment 57

[0471] The benzopyran-type flavonoid compound ZQQ60 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(3-chlorophenyl)-1-(5-hydroxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0472] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ60 are as follows:

[0473] 2-(3-chlorophenyl)-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0474]

[0475] Yellow solid; yield 67%; 1 H NMR (400MHz, CDCl3) δ7.98(d,J=8.7Hz,1H),7.86(s,1H),7.75(d,J=7.6Hz,1H),7.48(dt,J=15 .6,8.1Hz,2H),6.88(dd,J=14.4,9.4Hz,2H),6.73(s,1H),5.78(d,J=10.0Hz,1H),1.52(s,6H). 13 C NMR (101MHz, CDCl3) δ177.73,161.11,157.81,152.32,135.33,133.94,131.43,130.72, 130.44,126.22,126.15,124.31,117.77,115.47,115.08,109.50,108.10,77.90,28.21.

[0476] Embodiment 58

[0477] The benzopyran-type flavonoid compound ZQQ61 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(2-chlorophenyl)-1-(5-hydroxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0478] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ61 are as follows:

[0479] 2-(2-chlorophenyl)-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0480]

[0481] Yellow solid; yield 41%; 1 H NMR (400MHz, CDCl3) δ8.01(d,J=8.7Hz,1H),7.62(d,J=7.4Hz,1H),7.54(d,J=7.9Hz,1H),7.43(dt, J=20.1,7.5Hz,2H),6.85(dd,J=13.2,9.4Hz,2H),6.59(s,1H),5.69(d,J=10.0Hz,1H),1.50(s,6H). 13 C NMR (101MHz, CDCl3) δ177.71,162.14,157.70,152.77,132.98,132.06,131.79,130.97, 130.82,130.39,127.22,126.11,117.66,115.38,115.17,112.66,109.56,77.88,28.27.

[0482] Embodiment 59

[0483] The benzopyran-type flavonoid compound ZQQ62 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(2,4-dimethoxyphenyl)-1-(5-hydroxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0484] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ62 are as follows:

[0485] 2-(2,4-dimethoxyphenyl)-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0486]

[0487] Yellow solid; yield 30%; 1 H NMR (400MHz, CDCl3) δ7.97(d,J=8.7Hz,1H),7.82(d,J=8.8Hz,1H),7.05(s,1H),6.87(d,J=10.0Hz,1H),6.82(d,J=8.7Hz ,1H),6.63(dd,J=8.8,2.3Hz,1H),6.55(d,J=2.3Hz,1H),5.71(d,J=10.0Hz,1H),3.91(s,3H),3.88(s,3H),1.50(s,6H). 13 C NMR (101MHz, CDCl3) δ178.51,163.19,160.25,159.66,157.29,152.51,130.21,130.18,126.00 ,117.63,115.45,114.78,113.86,110.96,109.36,105.40,98.99,77.62,55.73,55.63,28.18.

[0488] Embodiment 60

[0489] The benzopyran-type flavonoid compound ZQQ63 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(4-methoxyphenyl)-1-(5-hydroxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0490] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ63 are as follows:

[0491] 2-(4-methoxyphenyl)-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0492]

[0493] Yellow solid; yield 66%;1 H NMR (400MHz, CDCl3) δ7.98(d,J=8.7Hz,1H),7.84(d,J=8.9Hz,2H),7.02(d,J=8.9Hz,2H),6.91(d,J =10.0Hz,1H),6.84(d,J=8.7Hz,1H),6.69(s,1H),5.75(d,J=10.0Hz,1H),3.88(s,3H),1.51(s,6H). 13 C NMR (101MHz, CDCl3) δ177.98,162.76,162.35,157.50,152.31,130.48,127.87,126 .06,124.32,117.71,115.27,115.09,114.57,109.46,105.95,77.74,55.58,28.19.

[0494] Embodiment 61

[0495] The benzopyran-type flavonoid compound ZQQ64 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(3-methoxyphenyl)-1-(5-hydroxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0496] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ64 are as follows:

[0497] 2-(3-methoxyphenyl)-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0498]

[0499] Yellow solid; yield 57%; 1 H NMR (400MHz, CDCl3) δ7.98 (d, J = 8.7Hz, 1H), 7.46 (dd, J = 15.8, 7.6Hz, 2H), 7.40 (s, 1H), 7.07 (d, J = 8.0 Hz,1H),6.88(dd,J=21.9,9.3Hz,2H),6.77(s,1H),5.75(d,J=10.0Hz,1H),3.89(s,3H),1.51(s,6H). 13C NMR (101MHz, CDCl3) δ178.02,162.52,160.06,157.67,152.39,133.43,130.55,130.24,126 .09,118.63,117.79,116.87,115.28,115.18,111.85,109.51,107.63,77.82,55.53,28.21.

[0500] Embodiment 62

[0501] The benzopyran-type flavonoid compound ZQQ65 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(2,3-dimethoxyphenyl)-1-(5-hydroxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0502] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ65 are as follows:

[0503] 2-(2,3-dimethoxyphenyl)-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0504]

[0505] Yellow solid; yield 29%; 1 H NMR (400MHz, CDCl3) δ8.00(d,J=8.8Hz,1H),7.34(d,J=9.5Hz,1H),7.18(t,J=8.1Hz,1H),7.07(d,J=9.8 Hz,1H),6.95(s,1H),6.89-6.81(m,2H),5.70(d,J=10.0Hz,1H),3.92(s,3H),3.86(s,3H),1.49(s,6H). 13 C NMR (101MHz, CDCl3) δ178.26,160.88,157.52,153.49,152.72,148.13,130.31,126.70,126.08 ,124.34,120.67,117.73,115.35,115.13,114.90,112.07,109.47,77.75,61.05,56.13,28.21.

[0506] Embodiment 63

[0507] The benzopyran-type flavonoid compound ZQQ66 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(2,3,4-trimethoxyphenyl)-1-(5-hydroxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0508] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ66 are as follows:

[0509] 8,8-dimethyl-2-(2,3,4-trimethoxyphenyl)-4H,8H-pyrano[2,3-f]chromen-4-one;

[0510]

[0511] Yellow solid; yield 18%; 1 H NMR (400MHz, CDCl3) δ7.98 (d, J = 8.7Hz, 1H), 7.10 (s, 2H), 6.86 (d, J = 9.7Hz, 2H),6.72(s,1H),5.80-5.73(m,1H),3.96(s,6H),3.93(s,3H),1.51(s,6H). 13 C NMR (101MHz, CDCl3) δ177.90,162.57,157.67,153.65,152.33,141.16,130.73,127.34 ,126.12,117.69,115.28,114.96,109.39,107.19,103.71,77.79,61.12,56.41,28.21.

[0512] Embodiment 64

[0513] The benzopyran-type flavonoid compound ZQQ67 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(3,4-dimethoxyphenyl)-1-(5-hydroxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0514] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ67 are as follows:

[0515] 2-(3,4-dimethoxyphenyl)-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0516]

[0517] Yellow solid; yield 42%; 1 H NMR (400MHz, CDCl3) δ7.96(d,J=8.7Hz,1H),7.52(dd,J=8.5,2.1Hz,1H),7.33(d,J=2.1Hz,1H),6.97(d,J=8.5Hz ,1H),6.86(dd,J=17.2,9.4Hz,2H),6.69(s,1H),5.75(d,J=10.0Hz,1H),3.97(s,3H),3.95(s,3H),1.50(s,6H). 13 CNMR(101MHz,CDCl3)δ177.90,162.66,157.53,152.29,152.03,149.34,130.57,126.05,12 4.52,119.81,117.68,115.12,111.25,109.41,108.78,106.21,77.73,56.14,56.11,28.18.

[0518] Embodiment 65

[0519] The benzopyran-type flavonoid compound ZQQ68 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(2-methoxyphenyl)-1-(5-hydroxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0520] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ68 are as follows:

[0521] 2-(2-methoxyphenyl)-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0522]

[0523] Yellow solid; yield 35%; 1H NMR(400MHz, CDCl3) δ7.98(d,J=8.7Hz,1H),7.85(dd,J=7.8,1.8Hz,1H),7.51-7.42(m,1H),7.09(d,J=1 1.2Hz,2H),7.04(d,J=8.4Hz,1H),6.92-6.80(m,2H),5.71(d,J=10.0Hz,1H),3.93(s,3H),1.50(s,6H). 13 C NMR (101MHz, CDCl3) δ178.43,160.23,158.03,157.44,152.65,132.34,130.27,129.09,126 .04,121.08,120.81,117.66,115.38,114.98,112.33,111.88,109.43,77.70,55.73,28.20.

[0524] Embodiment 66

[0525] The benzopyran-type flavonoid compound ZQQ70 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(4-hydroxyphenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0526] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ70 are as follows:

[0527] 2-(4-hydroxyphenyl)-5-hydroxy-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one

[0528]

[0529] Yellow solid; yield 21%; 1 H NMR (400MHz, DMSO-d6) δ10.23(s,1H),7.87(d,J=8.7Hz,2H),6.90(dd,J=12.6,9.3H z,3H),6.58(s,1H),6.44(s,1H),5.78(d,J=10.0Hz,1H),3.81(s,3H),1.45(s,6H). 13C NMR(101MHz,DMSO-d6)δ176.15,161.06,160.56,160.25,157.59,153.59,128.58,128.41,12 8.34,121.94,116.53,116.48,115.32,108.59,106.58,102.60,97.15,78.43,56.65,28.31.

[0530] Embodiment 67

[0531] The benzopyran-type flavonoid compound ZQQ71 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(4-(4-methylpiperazinyl)phenyl)-1-(5-hydroxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0532] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ71 are as follows:

[0533] 8,8-dimethyl-2-(4-(4-methylpiperazin-1-yl)phenyl)-4H,8H-pyrano[2,3-f]chromen-4-one;

[0534]

[0535] Yellow solid; yield 31%; 1 H NMR (400MHz, CDCl3) δ7.96 (d, J = 8.7Hz, 1H), 7.77 (t, J = 9.3Hz, 2H), 6.99-6.90 (m, 3H), 6.83 (t, J = 9.2Hz, 1H) ,6.63(d,J=4.1Hz,1H),5.78-5.71(m,1H),3.41-3.34(m,4H),2.65-2.57(m,4H),2.38(s,3H),1.53(s,6H). 13 C NMR (101MHz, CDCl3) δ177.94,162.97,157.30,153.01,134.91,131.04,130.33,127.49,126.01 ,121.70,117.87,115.36,114.80,114.73,109.43,105.15,77.61,54.65,47.46,45.96,28.17.

[0536] Embodiment 68

[0537] The benzopyran-type flavonoid compound ZQQ72 was prepared in the same manner as in Example 37, except that (E)-3-(4-chlorophenyl)-1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one was replaced by (E)-3-(4-hydroxyphenyl)-1-(5-hydroxy-2,2-dimethyl-2H-benzopyran-6-yl)prop-2-en-1-one.

[0538] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ72 are as follows:

[0539] 2-(4-hydroxyphenyl)-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0540]

[0541] Yellow solid; yield 33%; 1 H NMR (400MHz, DMSO-d6) δ10.27(s,1H),7.94(d,J=8.8Hz,2H),7.77(d,J=8.7Hz,1H),7.00(d,J=10.0Hz ,1H),6.93(d,J=8.8Hz,2H),6.88(d,J=8.7Hz,1H),6.77(s,1H),5.96(d,J=10.0Hz,1H),1.46(s,6H). 13 C NMR(101MHz,DMSO)δ176.74,162.88,161.36,157.10,151.95,131.77,128.70,1 25.75,122.20,117.83,116.52,115.14,115.05,109.79,105.01,78.23,28.18.

[0542] Embodiment 69

[0543] The benzopyran flavonoid compound ZQQ73 was prepared in the same manner as in Example 38, except that ZQQ43 was replaced by ZQQ70.

[0544] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ73 are as follows:

[0545] 5-hydroxy-2-(4-hydroxyphenyl)-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0546]

[0547] Yellow solid; yield 14%; 1 H NMR (400MHz, DMSO-d6) δ13.10 (s, 1H), 10.38 (s, 1H), 7.97 (d, J = 8.7Hz, 2H), 6.94 (d, J=8.8Hz,2H),6.90-6.84(m,2H),6.22(s,1H),5.80(d,J=10.0Hz,1H),1.45(s,6H). 13 C NMR (101MHz, DMSO) δ182.56,164.31,161.89,161.45,159.22,151.78,129.13, 128.63,121.58,116.60,114.89,105.11,103.51,101.57,99.84,78.67,28.28.

[0548] Embodiment 70

[0549] The benzopyran flavonoid compound ZQQ74 was prepared in the same manner as in Example 38, except that ZQQ43 was replaced by ZQQ52.

[0550] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ74 are as follows:

[0551] 5-hydroxy-2-(2-methoxyphenyl)-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0552]

[0553] Yellow solid; yield 21%; 1 H NMR (400MHz, CDCl3) δ7.85(d,J=7.8Hz,1H),7.49(t,J=8.7Hz,1H),7.11(t,J=7.6Hz,1H),7.05(d,J=8.4H z,1H),7.01(s,1H),6.75(d,J=10.0Hz,1H),6.27(s,1H),5.58(d,J=9.9Hz,1H),3.94(s,3H),1.48(s,6H).13 C NMR (101MHz, CDCl3) δ183.03,161.80,160.98,159.54,158.16,152.29,132.71,129.08,127 .32,120.89,120.50,115.05,111.93,110.90,105.51,101.28,100.09,78.03,55.75,28.25.

[0554] Embodiment 71

[0555] The benzopyran flavonoid compound ZQQ75 was prepared in the same manner as in Example 38, except that ZQQ43 was replaced by ZQQ49.

[0556] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ75 are as follows:

[0557] 2-(3,4-dimethoxyphenyl)-5-hydroxy-8,8-dimethyl-4H,8H-pyrano[2,3-f]chromen-4-one;

[0558]

[0559] Yellow solid; yield 18%; 1 H NMR (400MHz, CDCl3) δ12.89(s,1H),7.52(d,J=8.2Hz,1H),7.38(s,1H),7.31(s,1H),7.26( s,1H),7.02(d,J=8.5Hz,1H),6.58(s,1H),6.27(s,1H),3.98(d,J=5.2Hz,6H),1.61(s,6H). 13 C NMR (101MHz, CDCl3) δ182.38,163.62,162.37,158.54,152.56,150.67,149.49,127.05,123.65 ,120.11,111.39,108.79,105.45,104.81,103.13,100.39,96.64,81.86,56.20,56.09,28.21.

[0560] Embodiment 72

[0561] The benzopyran flavonoid compound ZQQ76 was prepared in the same manner as in Example 38, except that ZQQ43 was replaced by ZQQ55.

[0562] The English name, structure and characterization data of the benzopyran flavonoid compound ZQQ76 are as follows:

[0563] 5-hydroxy-8,8-dimethyl-2-(4-(4-methylpiperazin-1-yl)phenyl)-4H,8H-pyrano[2,3-f]chromen-4-one;

[0564]

[0565] Yellow solid; yield 10%; 1 H NMR (400MHz, CDCl3) δ12.96(s,1H),7.75(d,J=8.9Hz,2H),6.94(d,J=8.7Hz,2H),6.78(d,J=9.9Hz,1H),6.51(s, 1H), 6.25 (s, 1H), 5.60 (d, J = 10.0Hz, 1H), 3.38 (t, J = 5.1Hz, 4H), 2.60 (t, J = 5.0Hz, 4H), 2.38 (s, 3H), 1.48 (s, 6H). 13 CNMR (101MHz, CDCl3) δ182.50,163.95,161.81,159.34,153.30,151.93,127.83,127.67,127.3 9,120.75,115.04,114.58,105.38,103.32,101.31,100.16,77.96,54.67,47.34,46.03,28.23.

[0566] Test Example 1

[0567] Effects of benzopyran flavonoids on the glucose transport function of plant SWEETs proteins

[0568] The biological activity of benzopyran flavonoids was tested by yeast growth assay. The specific method is as follows:

[0569] (1) Construction of SWEETs sugar transporter expression vector

[0570] The cDNA of rice variety ZH11 (from Oryza sativa Japonica Group) 48 hours after inoculation with rice blast fungus was used as a template, and the OsSWEET4 nucleotide sequence was amplified by conventional PCR procedure. The PCR reaction system was: cDNA 1μL, forward primer (10μmol / L) 2μL, reverse primer (10μmol / L) 2μL, Phanta high-fidelity DNA polymerase (P501-d2) 1μL, 5×SF buffer (with 10mmol / LMgSO4) 10μL, dNTP mixture (10mM each) 1μL, ultrapure water 33μL. The PCR amplification procedure was: 95℃ pre-denaturation for 3min; 95℃ 15s, 59℃ 15s, 72℃ 1min, 33 cycles; 72℃ final extension for 10min. After agarose gel electrophoresis, the gel was cut and the fragment was recovered. The amplified fragment size was 777bp.

[0571] The recovered fragments were homologously recombined with the pDONR221 vector (Kanamycin) by the Gateway method to obtain the pDONR221-OsSWEET4 ligation product. After selecting the positive clones and sequencing verification, the ligation product pDRf-eGFP-GW was homologously recombined with the Gateway method to obtain the pDRf-OsSWEET4. After selecting the positive clones and sequencing verification, the correct yeast expression vector was obtained.

[0572] (2) Transfer of recombinant vector into EBY4000

[0573] A: Reagent preparation:

[0574] PEG4000: Add 10 g PEG4000 to 20 mL with ultrapure water and sterilize;

[0575] LIAc: 3.2995 g LIAc powder plus 50 mL ultrapure water to make up to 50 mL, sterilize;

[0576] 10XTE buffer: 100 ml 1 mol / L Tris-Hcl, 20 mL 500 mmol / L ETA, add 800 mL ultrapure water to 1 L, adjust the pH to 6.5-7.5, and sterilize.

[0577] B: Yeast strain activation

[0578] Take the -80℃ frozen strain (EBY4000), streak it on the YPM plate, and culture it at 28-30℃ until colonies are produced; pick a single colony and culture it in YPM (YP+maltose) liquid culture for about 24 hours. After the culture is completed, the culture medium becomes turbid.

[0579] C: Yeast transformation

[0580] Add the bacterial solution obtained in step B to a 2 mL centrifuge tube, centrifuge at 10,000 rpm for 1 min, and discard the culture medium; add 1 mL of ultrapure water to resuspend, and centrifuge at 10,000 rpm for 1 min; repeat once, resuspend the bacteria with 300 μL ultrapure water (as Yeast) and carry out subsequent experiments.

[0581] The system used in the yeast growth test consisted of the following:

[0582] PEG4000: 70 μL;

[0583] LiAc: 8 μL;

[0584] 10XTE buffer: 8 μL;

[0585] Yeast: 10 μL;

[0586] Carrier DNA: 2 μL;

[0587] Plasmid DNA: 5 μL (Plasmid DNA includes pDRf-OsSWEET4, pDRf-TaSWEET2a, pDRf-ZmSWEET4a, pDR196-AtSWEET1 and pDRf-eGFP-GW (blank control)).

[0588] After the system used for the yeast growth test was formed according to the above ratio, the resulting system was set to perform a yeast transformation reaction in a PCR gene amplification instrument, and the reaction program was 28°C for 30 minutes, then 42°C for 13 minutes, and finally 28°C for 1-2 minutes. The resulting liquid was centrifuged for 1 minute, the supernatant was discarded, and the bacteria were resuspended with 50 μL of ultrapure water, spread on the corresponding selective SD / -Ura medium (added with maltose), and cultured at 28°C until positive yeast colonies grew on the medium plate.

[0589] (3) Effects of benzopyranose flavonoids on the sugar transport activity of SWEETs

[0590] First, prepare YP+1% Maltose medium and YP+1% Glucose medium, the specific compositions are as follows:

[0591] Yeast extract: 1g powder;

[0592] Agar powder: 2g powder;

[0593] Peptone: 2 g powder, dilute to volume with 90 mL ultrapure water, sterilize;

[0594] Maltose or glucose: 2 g, add 10 mL ultrapure water to make up to volume, and sterilize.

[0595] Then, the following components were added to the YP+1% Maltose medium or the YP+1% Glucose medium to prepare medium groups A, B, C and D:

[0596] Group A culture medium (control group): 120 μL DMSO was added to YP+1% Maltose culture medium and YP+1% Glucose culture medium respectively; (referred to as Mock);

[0597] Group B culture medium (control group): 120 μL of 50 mmol / L curcumin (final concentration 60 μmol / L, referred to as C-60 μmol / L) was added to YP+1% Maltose medium and YP+1% Glucose medium, respectively;

[0598] Group C culture medium (experimental group): 80 μL of 50 mmol / L benzopyran-type flavonoids (final concentration of 40 μmol / L, referred to as ZQQXX) were added to YP+1% Maltose medium and YP+1% Glucose medium, respectively;

[0599] Culture medium of group D (experimental group): 120 μL of 50 mmol / L benzopyran flavonoids (final concentration of 60 μmol / L, referred to as ZQQXX) were added to YP+1% Maltose culture medium and YP+1% Glucose culture medium, respectively.

[0600] Yeast drop plate: Pick a single colony of the yeast transformation product and add 2mL YPM (YP+Maltose) liquid to culture for about 24 hours (turbid); then centrifuge at 10000rpm for 1min to collect the bacteria and discard the supernatant; then wash the yeast twice with 1mL ultrapure water in the clean bench; after determination, prepare the bacterial suspension to an OD value of 0.5 and press 10 -1 , 10 -2 , 10 -3 and 10 -4 Dilute the yeast suspension in four concentration gradients. Take 4 μL of yeast suspension and drip it onto the culture medium of groups A, B, C and D in order. After the droplets dripped on the culture medium are completely dried, seal the culture medium and culture it at 28-30℃ for about 2 days until colonies grow. Observe the trend and take photos to record. Figures 2 to 21 shown.

[0601] The results showed that compared with the control group, adding 40 μmol / L or 60 μmol / L of compounds ZQQ26, ZQQ35 or ZQQ41 to YPM medium did not affect the growth of yeast, while adding 40 μmol / L or 60 μmol / L of compounds ZQQ26, ZQQ35 or ZQQ41 to YPD weakened the yeast growth compared with the Mock, and the inhibitory effect of compounds ZQQ26, ZQQ35 or ZQQ41 added at 60 μmol / L on yeast growth was stronger than that added at 40 μmol / L, indicating that benzopyran flavonoid compounds ZQQ26, ZQQ35 and ZQQ41 have significant inhibitory activity on the sugar transport activity of SWEETs at 60 μmol / L.

[0602] Test Example 2

[0603] The antibacterial activity of benzopyran flavonoid compounds ZQQ26, ZQQ35 and ZQQ41 was tested by mycelium growth test. The specific method is as follows:

[0604] Types of pathogenic fungi: Pathogenic fungi include Magnaporthe oryzae, Exserohilum turcicum, Fusarium graminearum, Alteraria alternata, Botryosphaeri dothidea, Rhizoctonia solani and Sclerotinia sclerotiorum.

[0605] (1) Preparation of culture medium: The test compound was dissolved in DMSO to prepare a stock solution with a concentration of 50 mmol / L, and then added to the PDA culture medium and diluted to prepare a PDA culture medium plate containing the test sample, so that the final concentration of the test compound was 60 μmol / L. PDA culture medium containing an equal volume of DMSO was used as a mock control, and PDA culture medium containing the fungicide pyraclostrobin was used as a positive control.

[0606] (2) Pathogenic fungal mycelium growth test: The activated pathogenic fungi were inoculated into prepared medium containing DMSO, 60 μmol / L curcumin, 60 μmol / L C 22 H 20 O5 (compound ZQQ26), 60 μmol / L C 26 H 30 O4N2 (compound ZQQ35) and 60 μmol / LC21 H 16 O4Cl (compound ZQQ41) on PDA medium, and cultured in a 28°C incubator; the activated soybean sclerotinia fungus was also inoculated on the above medium, placed in a 24°C light-shielded incubator, and the hyphae growth of the pathogenic fungus was observed and recorded. The results are as follows Figures 22-24 shown.

[0607] The results showed that compared with the CK (Mock) control, compound ZQQ26 had a significant inhibitory effect on the mycelial growth of pathogenic fungi such as rice blast, corn leaf blight, corn ear rot and tobacco brown spot pathogen; compound ZQQ35 had a significant inhibitory effect on the mycelial growth of pathogenic fungi such as corn leaf blight, corn ear rot, soybean sclerotinia and grape canker; compound ZQQ41 had a significant inhibitory effect on the mycelial growth of pathogenic fungi such as rice blast, corn leaf blight, rice sheath blight and soybean sclerotinia. Although the inhibitory effects of benzopyran flavonoids ZQQ26, ZQQ35 and ZQQ41 on fungi were weaker than those of the positive control, the benzopyran flavonoids provided by the present invention still have good potential to become broad-spectrum antibacterial agents.

[0608] Test Example 3

[0609] The antibacterial activity of benzopyran flavonoid compounds ZQQ26, ZQQ35 and ZQQ41 was tested by bacterial growth rate test. The specific method is as follows:

[0610] Bacterial species: Pectobacterium carotovorum subsp. carotovorum (Pcc), Pseudomonas syringaepv. tabaci (Pst), Ralstonia solanacearum, Xanthomonas oryzaeepv. Oryzae (Xoo), and Pseudomonas syringaepv. angula (Psa)

[0611] (1) Preparation of liquid culture medium: The test compound was dissolved in DMSO to prepare a 50 mmol / L stock solution, which was then added to LB culture medium to prepare a culture medium with a final concentration of the test compound of 60 μmol / L. Kanamycin sulfate and curcumin at the same concentration were used as control culture medium, and DMSO containing the same volume as the test compound was used as mock culture medium.

[0612] (2) Pathogenic bacteria growth rate test: Pick newly activated bacteria in 2 mL of LB culture medium, shake and culture at 30°C and 220 rpm for 12 hours; then take 10 μL of bacterial suspension and mix with 2 mL of LB culture medium containing the test compound, antibiotics, curcumin and DMSO in step (1); then divide the mixed liquid into two parts, take 1 mL of liquid to measure the OD600 before culture and record it, marked as OD1; take another 1 mL of liquid and shake and culture at 30°C and 220 rpm for 16 hours, measure the OD600 after culture and record it, marked as OD2; the inhibitory effect of the test compound on pathogenic bacteria is determined by calculating the growth rate of the OD of pathogenic bacteria in different treatment groups before and after culture. The calculation formula is as follows:

[0613] Growth rate calculation formula: (OD2-OD1) / OD1*100%.

[0614] The bacterial growth rate test results of benzopyran flavonoid compounds ZQQ26, ZQQ35 and ZQQ41 are as follows Figures 25-27 The results showed that compared with the CK (Mock) control, compound ZQQ26 could effectively inhibit the growth rate of Chinese cabbage soft rot pathogen, tobacco wildfire pathogen and tobacco bacterial wilt pathogen. Compared with the antibiotic treatment, compound ZQQ26 had similar inhibitory effects on the above three bacteria, which were significantly higher than the CK control; compound ZQQ35 could effectively inhibit the growth rate of rice bacterial blight pathogen, tobacco angular spot pathogen and tobacco bacterial wilt pathogen. Compared with the antibiotic treatment, compound ZQQ35 had similar inhibitory effects on the above three bacteria, which were significantly higher than the CK control; compound ZQQ41 could effectively inhibit the growth rate of Chinese cabbage soft rot pathogen, tobacco angular spot pathogen and tobacco bacterial wilt pathogen. Compared with the antibiotic treatment, compound ZQQ41 had similar inhibitory effects on the above three bacteria, which were significantly higher than the CK control.

[0615] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A benzopyran flavonoid compound or a pharmaceutically acceptable salt thereof, characterized in that: The benzopyran flavonoid compound has a structure shown in Formula I or Formula II: In Formula I and Formula II, the R1 is selected from substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, and the substitution means that one or more hydrogen atoms in the group are replaced by alkyl, alkoxy, halogen, hydroxyl, nitro, haloalkyl, aralkyl, alkylamino or heterocyclic amino; The R2 is selected from -H or alkyl; The R3 is selected from -H, hydroxyl or alkoxy.

2. The benzopyran-type flavonoid compound according to claim 1, characterized in that: The aryl group in the substituted or unsubstituted aryl group is phenyl; the heteroaryl group in the substituted or unsubstituted heteroaryl group is indolyl or N-methylindolyl; In the R1, the number of carbon atoms in the alkyl group is 1 to 5, the number of carbon atoms in the alkoxy group is 1 to 5, the number of carbon atoms in the haloalkyl group is 1 to 5, the number of carbon atoms in the aralkyl group is 6 to 8, the number of carbon atoms in the alkylamino group is 2 to 6, the number of carbon atoms in the heterocyclic amino group is 4 to 8, the halogen atom in the haloalkyl group is chlorine or bromine, and the number of halogen atoms in the haloalkyl group is 1 to 3; In said R2, said alkyl group is methyl or ethyl; In the R3, the alkoxy group is a methoxy group or an ethoxy group.

3. The benzopyran-type flavonoid compound according to claim 2, characterized in that: The haloalkyl group is trifluoromethyl, the aralkyl group is benzyl, the alkylamino group is dimethylamino or diethylamino, and the heterocyclic amino group is morpholinyl, 4-methylpiperazin-1-yl, 4-ethylpiperazin-1-yl, piperidin-1-yl or pyrrolidin-1-yl.

4. The benzopyranose flavonoid compound according to any one of claims 1 to 3, characterized in that: The R1 is selected from any of the following groups:

5. The benzopyran-type flavonoid compound according to claim 1, characterized in that: The benzopyran-type flavonoid compound is any one of the following compounds:

6. The method for preparing the benzopyranose flavonoid compound according to any one of claims 1 to 5, comprising the following steps: (1) The method for preparing a benzopyran-type flavonoid compound having a structure shown in Formula I comprises the following steps: Compound F is mixed with an aromatic aldehyde compound and ethanol, and subjected to a condensation reaction under alkaline conditions to obtain a benzopyran-type flavonoid compound having a structure shown in Formula I; (2) The method for preparing a benzopyran-type flavonoid compound having a structure shown in Formula II comprises the following steps: The benzopyran flavonoid compound having a structure shown in Formula I when R2 is -H is mixed with iodine and dimethyl sulfoxide to perform a ring-forming reaction to obtain a benzopyran flavonoid compound having a structure shown in Formula II; The structural formula of the aromatic aldehyde compound is R1-CHO; the structural formula of the compound F is shown in Formula F: The R1, R2 and R3 are as defined in Formula I or Formula II.

7. Use of the benzopyranose flavonoid compound according to any one of claims 1 to 5 in the preparation of broad-spectrum antibacterial drugs.

8. Use of the benzopyranose flavonoid compound according to any one of claims 1 to 5 in the preparation of a plant sugar transporter inhibitor.

9. A pharmaceutical preparation comprising an active ingredient and a pharmaceutical excipient; the active ingredient is the benzopyranose flavonoid compound according to any one of claims 1 to 5.

10. The pharmaceutical preparation according to claim 9, characterized in that The dosage form of the pharmaceutical preparation includes wettable powder, suspension, aqueous solution, granule, spray, tablet, capsule, aerosol or nano preparation.

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