A benzopyran-type flavonoid compound, its preparation method and application, and a pharmaceutical preparation

Abstract

The present invention provides a benzopyran-type flavonoid compound, its preparation method and application, and a pharmaceutical preparation, belonging to the field of pharmaceutical chemistry technology. The present invention provides a benzopyran-type flavonoid compound having a structure represented by Formula I or Formula II. The benzopyran-type flavonoid compound provided by the present invention targets members of the SWEET protein family in plants, selectively inhibiting the sugar transport activity of plant SWEET proteins while also exhibiting broad-spectrum antibacterial activity. These combined effects enhance the broad-spectrum disease resistance of plants. #imgabs0#

Description

Technical Field

[0001] The present invention belongs to the technical field of pharmaceutical chemistry, and in particular 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 plants, causing harmful effects known as diseases. Microorganisms that cause plant disease are called pathogens. Existing research shows that diseases cause significant losses to plants each year. Diseases such as rice sheath blight and soybean sclerotinia often cause significant, even devastating, damage to production. Therefore, improving crop disease resistance is a critical 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 exported transporters), 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 ability to be targeted by pathogens are relatively conserved in different crop-pathogen interaction systems. Therefore, it is expected that disease control can be achieved 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 an urgent problem that current researchers need to solve. Summary of the Invention

[0004] The present invention aims to provide a benzopyran-type flavonoid compound, its preparation method and application, and a pharmaceutical preparation. The benzopyran-type flavonoid compound provided by the present invention targets members of the plant SWEETs protein family and can selectively inhibit the sugar transport activity of plant SWEET proteins while exhibiting 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-type flavonoid compound or a pharmaceutically acceptable salt thereof, wherein the benzopyran-type flavonoid compound has a structure shown in Formula I or Formula II:

[0007]

[0008] In Formula I and Formula II, 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, hydroxy, nitro, haloalkyl, aralkyl, alkylamino or heterocyclic amino groups;

[0009] Said 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 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 the R2, the alkyl group is a methyl group or an ethyl group;

[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 one 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 preparation method of the benzopyran-type flavonoid compound having the structure shown in Formula I comprises the following steps:

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

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

[0027] The benzopyran-type flavonoid compound having the structure shown in Formula I, wherein R2 is -H, is mixed with iodine and dimethyl sulfoxide to undergo a ring-forming reaction to obtain a benzopyran-type flavonoid compound having the 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-type 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 benzopyran-type 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 pharmaceutical excipients; 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-type flavonoid compound having a structure represented by Formula I or Formula II. The benzopyran-type flavonoid compound provided by the present invention targets members of the SWEET protein family in plants and can selectively inhibit the sugar transport activity of plant SWEET proteins. Furthermore, the benzopyran-type flavonoid compound exhibits broad-spectrum antibacterial activity, and these two effects, combined, 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 examples 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 fungus, corn leaf blight fungus, corn ear rot fungus and tobacco brown spot fungus, and can effectively inhibit the growth rate of pathogenic bacteria such as Chinese cabbage soft rot fungus, tobacco wildfire fungus and tobacco wilt fungus; the benzopyran flavonoid compound ZQQ35 has a significant inhibitory effect on the mycelial growth of pathogenic fungi such as corn leaf blight fungus, corn ear rot fungus, soybean sclerotinia fungus and grape ulcer fungus, and can effectively inhibit the growth rate of pathogenic bacteria such as rice white leaf blight fungus, tobacco angular spot fungus and tobacco wilt fungus; ZQQ41 has a significant inhibitory effect on the mycelial growth of rice blast fungus, corn leaf blight fungus, rice sheath blight fungus and soybean sclerotinia fungus, and can effectively inhibit the growth rate of pathogenic bacteria such as Chinese cabbage soft rot fungus, tobacco angular spot fungus and tobacco wilt fungus. 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 leaf spot, tobacco bacterial wilt, rice sheath blight, rice blast and rice bacterial 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 following briefly introduces the drawings required for use in the embodiments. 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 any creative work.

[0038] Figure 1 Schematic diagram of the structural formula of benzopyran flavonoids;

[0039] Figure 2 The figure shows the results of biological activity tests of benzopyran flavonoid compounds ZQQ2, ZQQ3 and ZQQ4;

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

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

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

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

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

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

[0046] Figure 9 The figure shows the results of biological activity tests of benzopyran flavonoid compounds ZQQ25, ZQQ26 and ZQQ27;

[0047] Figure 10 The figure shows the biological activity test results of benzopyran flavonoid compounds ZQQ28, ZQQ29 and ZQQ30;

[0048] Figure 11 The figure shows the biological activity test results of benzopyran flavonoid compounds ZQQ31, ZQQ32 and ZQQ33;

[0049] Figure 12 The figure shows the biological activity test results of benzopyran flavonoid compounds ZQQ34, ZQQ35 and ZQQ36;

[0050] Figure 13 The figure shows the biological activity test results of benzopyran flavonoid compounds ZQQ37, ZQQ41 and ZQQ42;

[0051] Figure 14 The figure shows the biological activity test results of benzopyran flavonoid compounds ZQQ43, ZQQ44 and ZQQ45;

[0052] Figure 15 The figure shows the biological activity test results of benzopyran flavonoid compounds ZQQ46, ZQQ47 and ZQQ48;

[0053] Figure 16 The figure shows the biological activity test results of benzopyran flavonoid compounds ZQQ49, ZQQ50 and ZQQ51;

[0054] Figure 17 The figure shows the biological activity test results of benzopyran flavonoid compounds ZQQ54, ZQQ56 and ZQQ57;

[0055] Figure 18The figure shows the biological activity test results of benzopyran flavonoid compounds ZQQ58, ZQQ59 and ZQQ60;

[0056] Figure 19 The figure shows the results of biological activity tests of benzopyran flavonoid compounds ZQQ61, ZQQ62 and ZQQ63;

[0057] Figure 20 The figure shows the biological activity test results of benzopyran flavonoid compounds ZQQ64, ZQQ65 and ZQQ66;

[0058] Figure 21 The figure shows the results of biological activity tests of benzopyran flavonoid compounds ZQQ70, ZQQ71 and ZQQ75;

[0059] Figure 22 The results of the hyphae growth test and colony diameter after adding the benzopyran flavonoid compound ZQQ26 are shown;

[0060] Figure 23 The graphs show the results of the mycelial growth test and colony diameter after adding the benzopyran flavonoid compound ZQQ35;

[0061] Figure 24 The graphs show the results of mycelial growth and colony diameter tests with the addition of the benzopyran flavonoid compound ZQQ41.

[0062] Figure 25 This is the result of the bacterial growth rate test after adding the benzopyran flavonoid compound ZQQ26;

[0063] Figure 26 This is the result of the bacterial growth rate test after adding the benzopyran flavonoid compound ZQQ35;

[0064] Figure 27 This is the result of the bacterial growth rate test with the addition of the benzopyran flavonoid compound ZQQ41. DETAILED DESCRIPTION

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

[0066]

[0067] In Formula I and Formula II, 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, hydroxy, nitro, haloalkyl, aralkyl, alkylamino or heterocyclic amino groups;

[0068] Said 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 R1 described in the present invention, the number of carbon atoms in the alkyl group may be 1 to 5; in specific embodiments, the number of carbon atoms in the alkyl group may be 1, 2, 3, 4, or 5. In R1 described in the present invention, the number of carbon atoms in the alkoxy group may be 1 to 5; in specific embodiments, the number of carbon atoms in the alkoxy group may be 1, 2, 3, 4, or 5. In R1 described in 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 specific embodiments, the haloalkyl group may be a trifluoromethyl group. In R1 described in the present invention, the number of carbon atoms in the aralkyl group may be 6 to 8, specifically 6, 7, or 8; in specific embodiments, 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 specific embodiments, 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 specific embodiments, 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 benzopyran-type flavonoid compound targets members of the plant SWEET protein family and can selectively inhibit the sugar transport activity of the plant SWEET protein while having a broad-spectrum antibacterial activity. The combination of these two effects enhances the broad-spectrum disease resistance of the plant.

[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 preparation method of the benzopyran-type flavonoid compound having the structure shown in Formula I comprises the following steps:

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

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

[0086] The benzopyran-type flavonoid compound having the structure shown in Formula I, wherein R2 is -H, is mixed with iodine and dimethyl sulfoxide to undergo a ring-forming reaction to obtain a benzopyran-type flavonoid compound having the 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 using 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 an 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-type flavonoid compound having the structure shown in Formula I comprises the following steps:

[0093] (1) When R2 is -H, the preparation method of the benzopyran-type flavonoid compound having the 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 represented by 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 compound F2 are shown in Formula F1 and Formula F2, respectively:

[0099]

[0100] In the present invention, the preparation method of 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] Mixing the compound B, tetrabutylammonium bromide, dimethyl sulfate and a second solvent, and performing a methylation reaction under alkaline conditions to obtain compound C;

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

[0104] The compound D, 3-methyl-2-butenal and a 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] In the present invention, compound A, an organic ether compound, and a first solvent are mixed and subjected to 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 may be acetone. In a specific embodiment, compound A is 2,4,6-trihydroxyacetophenone, and the organic ether compound is chloromethyl methyl ether. Compound B prepared thereby is 2-hydroxy-4,6-bis(methoxymethoxy)acetophenone. In a specific embodiment, 2,4,6-trihydroxyacetophenone is mixed with potassium carbonate, and acetone is added thereto for pretreatment to obtain a pretreated mixed liquid. Chloromethyl methyl ether is then added to the pretreated mixed liquid to carry out the substitution reaction. In a specific embodiment of the present invention, the molar ratio of 2,4,6-trihydroxyacetophenone to potassium carbonate can be 3.28:13.13. In a specific embodiment of the present invention, the pretreatment temperature can be 60°C and the duration can be 30 minutes. In the present invention, the substitution reaction temperature can be 50-80°C and the duration can be 2-5 hours. In specific embodiments, the substitution reaction temperature can be 50°C, 60°C, 70°C, or 80°C, and the duration can be 3 hours or 4 hours. The substitution reaction of the present invention can be carried out under reflux conditions. The progress of the substitution reaction can be tracked by thin-layer chromatography (TLC). After the substitution reaction is completed, the reaction mixture can be cooled to room temperature, filtered, and the liquid material can be collected and the solvent removed to obtain a concentrated solution. The concentrated solution can then be subjected to silica gel column chromatography to obtain Compound B. The solvent in the liquid material can be removed by vacuum 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 embodiment of the present invention, In this example, the compound B is 2-hydroxy-4,6-bis(methoxymethoxy)acetophenone, and the compound C prepared therefrom is 2-methoxy-4,6-di( Crude 2-hydroxy-4,6-bis(methoxymethoxy)acetophenone. In a specific embodiment of the present invention, 2-hydroxy-4,6-bis(methoxymethoxy)acetophenone is dissolved in a mixed solvent of dichloromethane and water, solid sodium hydroxide and tetrabutylammonium bromide are added, 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 2-hydroxy-4,6-bis(methoxymethoxy)acetophenone to solid sodium hydroxide can be 1.81:2.71. In the present invention, the methylation reaction temperature can be 20-35°C and the reaction time can be 1.5-12 hours. In specific embodiments, the methylation reaction temperature can be 20°C, 25°C, 30°C, or 35°C, and the reaction time can be 2 hours, 5 hours, 7 hours, or 10 hours. The progress of the methylation reaction can be tracked by TLC. After the methylation reaction is completed, the present invention can heat the resulting reaction liquid at 60° C. for 30 minutes to destroy the remaining dimethyl sulfate; then cool the resulting reaction liquid to room temperature, add a sodium hydroxide aqueous solution to adjust the pH to neutral, extract with dichloromethane as an extractant, dry the resulting organic layer, collect the organic layer by filtration, and remove the solvent from 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 from the organic layer by distillation under reduced pressure, and can be dried using anhydrous magnesium sulfate.

[0111] After obtaining compound C, the present invention mixes 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, compound C is 2-methoxy-4,6-bis(methoxymethoxy)acetophenone, and the compound D prepared thereby is 2,4-dihydroxy-6-methoxyacetophenone. In the present invention, the hydrolysis reaction temperature may be 25-60°C, and the reaction time may be 2-12 hours; in a specific embodiment, the hydrolysis reaction temperature may be 30°C, 40°C, or 50°C, and the reaction time may be 3 hours, 6 hours, 9 hours, or 12 hours. The progress of the hydrolysis reaction can be tracked by TLC. After the hydrolysis reaction is completed, the pH of the resulting reaction solution can be adjusted to neutral, and then extraction can be performed using dichloromethane as an extractant. The organic layer obtained after extraction can be dried, and the organic layer can be collected by filtration, and the solvent in the organic layer can be removed to obtain a concentrated solution. The concentrated solution can be subjected to silica gel column chromatography to obtain compound D. The solvent in the organic layer can be removed by vacuum distillation, and drying can be performed using 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 to EA in the PE-EA mixed reagent can be 5:1.

[0112] After obtaining Compound D, the present invention mixes Compound D, 3-methyl-2-butenal, and a fourth solvent and conducts 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 to 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, Compound D is 2,4-dihydroxy-6-methoxyacetophenone, and the compound F1 prepared thereby is 1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-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 condensation reaction temperature can be 60-100°C, and the reaction time can be 0.5-3 hours. In specific embodiments, the reaction temperature can be 70°C, 80°C, or 90°C, and the reaction time can be 1 hour, 2 hours, or 2.5 hours. The progress of the condensation reaction can be tracked by TLC. After the condensation reaction, the reaction solution can be cooled to room temperature, and the solvent can be removed to obtain a concentrated solution. The concentrated solution can then be subjected to silica gel column chromatography to obtain Compound F1. The solvent can be removed from the reaction solution by vacuum distillation. In the present invention, the eluent used for 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 50:1.

[0113] After obtaining compound F1, the present invention mixes compound F1 with an aromatic aldehyde compound and ethanol, and conducts a first condensation reaction under alkaline conditions to obtain a benzopyran-type flavonoid compound having the structure represented by Formula I, where 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 specific embodiments, the molar ratio of compound F1 to the aromatic aldehyde compound can be 0.83:0.55. The ethanol described in the present invention can be anhydrous ethanol. In the present invention, the benzopyran-type flavonoid compound having the structure represented by Formula I, where 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-chromen-6-yl)ethanone, the aromatic aldehyde compound is 4-(methoxymethoxy)benzaldehyde, and the benzopyran-type flavonoid compound prepared thereby is ZQQ2. In this specific embodiment of the present invention, 1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)ethanone, 4-(methoxymethoxy)benzaldehyde, anhydrous ethanol, and an aqueous sodium hydroxide solution are mixed to perform a first condensation reaction. In this specific embodiment of the present invention, the mass fraction of the aqueous sodium hydroxide solution may be 40%, and the volume ratio of the aqueous sodium hydroxide solution to anhydrous ethanol may be 3:20. In the present invention, the temperature of the first condensation reaction can be 20-35°C, and the duration can be 24-96 hours. In specific embodiments, the temperature of the first condensation reaction can be 20°C, 25°C, 30°C, or 35°C, and the duration can be 24 hours, 48 ​​hours, 72 hours, or 96 hours. In the present invention, the first condensation reaction can be carried out under stirring. The progress of the first condensation reaction can be tracked by TLC. After the first condensation reaction, the reaction liquid can be extracted with dichloromethane as the extractant, and the resulting organic layer can be dried. The organic layer can then be collected by filtration and the solvent removed from the organic layer to obtain a concentrated solution. The concentrated solution can then be subjected to a first silica gel column chromatography to obtain the intermediate. The solvent in the organic layer can be removed by vacuum distillation, and drying can be performed using anhydrous magnesium sulfate. In the present invention, the eluent used for the silica gel column chromatography can be a PE-EA mixture, where the volume ratio of PE to EA in the PE-EA mixture can be 6:1. After obtaining the intermediate, the present invention can spin-dry the intermediate and then mix it with an acidic reagent and anhydrous ethanol to perform a hydrolysis reaction to obtain a benzopyran-type flavonoid compound having the 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 anhydrous ethanol can be 0.5:20.In the present invention, the hydrolysis reaction temperature can be 25-60°C, and the reaction time can be 2-12 hours. In specific embodiments, the hydrolysis reaction temperature can be 30°C, 40°C, or 50°C, and the reaction time can be 3 hours, 6 hours, 9 hours, or 12 hours. The progress of the hydrolysis reaction can be tracked by TLC. After the hydrolysis reaction, the pH of the resulting reaction solution can be adjusted to neutral, followed by extraction with dichloromethane. The resulting organic layer can be dried, collected by filtration, and the solvent removed from the organic layer to obtain a concentrated solution. The concentrated solution can be subjected to a second silica gel column chromatography to obtain the benzopyran-type flavonoid compound having the structure of Formula I when R2 is -H. The solvent in the organic layer can be removed by vacuum distillation, and drying can be performed using anhydrous magnesium sulfate. In the present invention, the eluent used for the second silica gel column chromatography can be a PE-EA mixture, where the volume ratio of PE to EA can be 6:1.

[0114] After obtaining Compound F1, the present invention mixes Compound F1 with tetrabutylammonium bromide, dimethyl sulfate, dichloromethane, and water, and conducts a 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 to water can be 3:2. In a specific embodiment of the present invention, Compound F1 is 1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)ethanone, and the compound F2 prepared thereby is 1-(5,7-dimethoxy-2,2-dimethyl-2H-chromen-6-yl)ethanone. In a specific embodiment of the present invention, 1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)ethanone is dissolved in a mixed solvent of dichloromethane and water, solid sodium hydroxide and tetrabutylammonium bromide are added, 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 1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)ethanone to solid sodium hydroxide can be 0.51:0.76. In the present invention, the methylation reaction temperature can be 20-35°C, and the reaction time can be 1.5-12 hours. In specific embodiments, the methylation reaction temperature can be 20°C, 25°C, 30°C, or 35°C, and the reaction time can be 3 hours, 6 hours, 9 hours, or 12 hours. The progress of the methylation reaction can be monitored by TLC. After the methylation reaction is completed, the present invention can heat the resulting reaction solution at 60°C for 30 minutes to destroy the remaining dimethyl sulfate. The reaction solution is then cooled to room temperature, and an aqueous sodium hydroxide solution is added to adjust the pH to neutral. Extraction is then performed using dichloromethane as the extractant. The resulting organic layer is dried and filtered to remove the solvent from the organic layer to obtain a concentrated solution. The concentrated solution is then subjected to silica gel column chromatography to obtain compound F2. In the present invention, the concentration of the aqueous sodium hydroxide solution can be 1 mol / L. The solvent in the organic layer can be removed by vacuum distillation, and drying can be performed using anhydrous magnesium sulfate. In the present invention, the eluent used for the silica gel column chromatography can be a PE-EA mixture, where the volume ratio of PE to EA can be 80:1.

[0115] After obtaining compound F2, the present invention mixes compound F2 with an aromatic aldehyde compound and ethanol, and conducts a second condensation reaction under alkaline conditions to obtain a benzopyran-type flavonoid compound having the structure represented by Formula I, where R2 is -CH3. In the present invention, the molar ratio of compound F2 to the aromatic aldehyde compound can be 0.83:0.42-1.0; in specific embodiments, the molar ratio of compound F2 to the aromatic aldehyde compound can be 0.83:0.55. The ethanol described in the present invention can be anhydrous ethanol. In the present invention, the benzopyran-type flavonoid compound having the structure represented by Formula I, where 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, and the aromatic aldehyde compound is 4-(methoxymethoxy)benzaldehyde. The benzopyran-type flavonoid compound prepared thereby is ZQQ26. In this specific embodiment of the present invention, 1-(5,7-dimethoxy-2,2-dimethyl-2H-benzopyran-6-yl)ethanone, 4-(methoxymethoxy)benzaldehyde, anhydrous ethanol, and an aqueous sodium hydroxide solution are mixed to perform a second condensation reaction. In this specific embodiment of the present invention, the mass fraction of the aqueous sodium hydroxide solution may be 40%, and the volume ratio of the aqueous sodium hydroxide solution to anhydrous ethanol may be 3:20. In the present invention, the temperature of the second condensation reaction can be 20-35°C, and the duration can be 24-96 hours. In specific embodiments, the temperature of the second condensation reaction can be 20°C, 25°C, 30°C, or 35°C, and the duration can be 24 hours, 48 ​​hours, 72 hours, or 96 hours. In the present invention, the second condensation reaction can be carried out under stirring. The progress of the second condensation reaction can be monitored by TLC. After the second condensation reaction, the reaction liquid can be extracted with dichloromethane as the extractant, and the resulting organic layer can be dried. The organic layer can then be collected by filtration and the solvent removed from the organic layer to obtain a concentrated solution. The concentrated solution can then be subjected to a first silica gel column chromatography to obtain the intermediate. In the present invention, the solvent in the organic layer can be removed by vacuum distillation, and drying can be performed using anhydrous magnesium sulfate. In the present invention, the eluent used for the silica gel column chromatography can be a PE-EA mixture, where the volume ratio of PE to EA in the PE-EA mixture 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 2-12 hours. In a specific embodiment, the temperature of the hydrolysis reaction may be 30°C, 40°C, or 50°C, and the time may be 3 hours, 6 hours, 9 hours, or 12 hours. The progress of the hydrolysis reaction can be tracked by TLC. After the hydrolysis reaction, the pH of the resulting reaction solution can be adjusted to neutral, and then extraction can be performed using dichloromethane as an extractant. The resulting organic layer is dried, and the organic layer is collected by filtration. The solvent in the organic layer is removed 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 vacuum 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-type flavonoid compound having a structure shown in Formula I when R2 is -H, the present invention mixes the benzopyran-type flavonoid compound having a structure shown in Formula I when R2 is -H with iodine and dimethyl sulfoxide, and performs a cyclization reaction to obtain a benzopyran-type flavonoid compound having a structure shown in Formula II. In the present invention, the molar ratio of the benzopyran-type 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-type 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-type 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-type flavonoid compound ZQQ6 is used to synthesize a benzopyran-type flavonoid compound ZQQ69, wherein the benzopyran-type 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 100-150°C and the time can be 1-4 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 mixture multiple times with ethyl acetate as an extractant, combine the obtained organic layers, dry and concentrate them in sequence to 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 with ethyl acetate can be performed three times; drying can be performed using anhydrous magnesium sulfate; and the concentration can be performed under vacuum. In the present invention, the eluent used for silica gel column chromatography can be a dichloromethane-methanol mixed solvent, wherein 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 resulting cyclized product with boron tribromide and dichloromethane to undergo a nucleophilic substitution reaction to obtain a benzopyran-type flavonoid compound having the structure represented by Formula II. In a specific embodiment of the present invention, the cyclized product is ZQQ43, and the benzopyran-type flavonoid compound having the structure represented by Formula II synthesized thereby is ZQQ69. In the present invention, the molar ratio of the cyclized product to boron tribromide can be 1:1-3; in a specific embodiment, the molar ratio of the cyclized 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 1 hour; 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 15 minutes, 30 minutes, 15 minutes or 60 minutes.The present invention can track the progress of the nucleophilic substitution reaction using TLC. After the nucleophilic substitution reaction is completed, the present invention can add anhydrous methanol to quench the reaction, and the resulting reaction liquid can be subjected to a second silica gel column chromatography to obtain a benzopyran-type flavonoid compound having the structure represented by Formula II. In the present invention, the eluent used for the second silica gel column chromatography can be a dichloromethane-methanol mixture, and the volume ratio of dichloromethane to methanol in the dichloromethane-methanol mixture 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; ZQQ55 can be used as a raw material to prepare ZQQ76; 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-type flavonoid compound described in the above technical solution in the preparation of broad-spectrum antibacterial drugs.

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

[0120] The present invention also provides a pharmaceutical preparation comprising an active ingredient and pharmaceutical excipients; the active ingredient is the benzopyran-type flavonoid compound described in the above technical solution. In the present invention, the pharmaceutical preparation can be in the form of a wettable powder, a suspension, an aqueous solution, a granule, a spray, a tablet, a capsule, an aerosol, or a nanoformulation.

[0121] The present invention prepares novel benzopyran-type flavonoid compounds based on the xanthohumol C structural skeleton. These novel benzopyran-type flavonoid compounds target members of the plant SWEET protein family, selectively inhibit the sugar transport activity of the plant SWEET protein, and have broad-spectrum antibacterial activity. They 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, and grape canker pathogen. At the same time, they can effectively inhibit the growth rate of pathogenic bacteria such as Chinese cabbage soft rot pathogen, tobacco wildfire pathogen, rice bacterial blight pathogen, tobacco angular leaf spot pathogen, and tobacco bacterial wilt pathogen.

[0122] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some 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 making creative efforts 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. Chloromethyl methyl ether (622 μL, 8.20 mmol) was then added dropwise. The mixture 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. After the reaction, the reaction solution 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 to obtain 2-hydroxy-4,6-bis(methoxymethoxy)acetophenone (i.e., Compound B, colorless oil, 463 mg, yield 60%).

[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). 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 time was started from the completion of the addition of dimethyl sulfate. The resulting mixture was stirred at room temperature for 2 h. The reaction progress was monitored by TLC during the reaction. After the reaction is completed, the resulting reaction solution is heated at 60° C. for 30 minutes to destroy the remaining dimethyl sulfate, and then the resulting reaction solution is cooled to room temperature, an aqueous sodium hydroxide solution (**mol / L) is added to adjust the pH value to 7, and then the resulting solution is extracted with dichloromethane as an extractant; the organic layer obtained after extraction is dried with anhydrous magnesium sulfate and filtered to obtain an organic layer, and the solvent in the organic layer is removed by reduced pressure distillation to obtain 2-methoxy-4,6-bis(methoxymethoxy)acetophenone (Compound C), which is directly used in the next 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. The mixture was reacted at 50° C. for 3 h, and the reaction progress was monitored by TLC. After the reaction, 3 mol / L sodium bicarbonate aqueous solution was added to the reaction solution to adjust the pH to 7. The solution was then extracted with dichloromethane as an extractant. The organic layer obtained after extraction was dried with anhydrous magnesium sulfate and filtered to obtain an organic layer. 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 to obtain 1-(2,4-dihydroxy-6-methoxyphenyl)ethanone (i.e., compound D, white solid, 229 mg, yield 75%).

[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 flask 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). The mixture was reacted at 80°C for 1 h. The reaction progress was monitored by TLC. 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 to obtain 1-(5-hydroxy-7-methoxy-2,2-dimethyl-2H-benzopyran-6-yl)ethanone (i.e., compound F1, an orange-yellow solid, 86 mg, yield 65%).

[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] 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). 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 with stirring. The reaction 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 solution was heated at 60° C. for 30 min to destroy the remaining dimethyl sulfate, and then the obtained reaction solution 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. The organic layer obtained after extraction was dried with anhydrous magnesium sulfate and filtered to obtain an organic layer. 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 80:1) as an eluent to obtain 1-(5,7-dimethoxy-2,2-dimethyl-2H-benzopyran-6-yl)ethanone (compound F2, yellow solid, 106 mg, yield 80%).

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

[0137] The intermediate 2 was dried and dissolved in anhydrous ethanol (20 mL). 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, a 3 mol / L aqueous sodium bicarbonate solution was added to adjust the pH to 7. The resulting solution was extracted with dichloromethane. The organic layer obtained after extraction was dried with anhydrous magnesium sulfate and filtered to obtain an organic layer. 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 6:1) as an eluent to obtain the benzopyran-type flavonoid compound ZQQ2 (orange solid particles, 85 mg, yield 44%).

[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-type 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-type flavonoid compound ZQQ4 was prepared in the same manner as in 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-type 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-type flavonoid compound ZQQ5 was prepared in the same manner as in 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-type 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-type 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-type 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-type 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-type 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-type 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-type flavonoid compound ZQQ11 was prepared in the same manner as in 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] Example 11

[0197] The benzopyran-type flavonoid compound ZQQ12 was prepared in the same manner as in 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-type flavonoid compound ZQQ13 was prepared in the same manner as in 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] Example 13

[0209] The benzopyran-type flavonoid compound ZQQ14 was prepared in the same manner as in 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-type 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] Example 14

[0215] The benzopyran-type 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] Example 15

[0221] The benzopyran-type 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-type 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] Example 17

[0233] The benzopyran-type 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] Example 18

[0239] The benzopyran-type 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] Example 19

[0245] The benzopyran-type 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] Example 20

[0251] The benzopyran-type 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-type 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] Example 21

[0257] The benzopyran-type 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-type 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] Example 22

[0263] The benzopyran-type 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-type 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] Example 23

[0269] The benzopyran-type 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] Example 24

[0275] The benzopyran-type 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] Example 25

[0281] The benzopyran-type 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-type 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] Example 26

[0287] The benzopyran-type 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] Example 27

[0293] The benzopyran-type 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] Example 28

[0299] The benzopyran-type 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-type 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 (400 MHz, 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] Example 29

[0305] The benzopyran-type 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] Example 30

[0310] The benzopyran-type 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-type 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] Example 31

[0316] The benzopyran-type flavonoid compound ZQQ32 was prepared in the same manner as in 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-type 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] Example 32

[0322] The benzopyran-type 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-type 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] Example 33

[0328] The benzopyran-type flavonoid compound ZQQ34 was prepared in the same manner as in 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-type 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] Example 34

[0334] The benzopyran-type 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] Example 35

[0339] The benzopyran-type 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] Example 36

[0345] The benzopyran-type 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-type 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] Example 37

[0351] 1.00 mmol of a benzopyran-type 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), followed by the addition of 0.05 mmol of I2. The reaction was stirred at 120° C. for 1.5 h. After the reaction, the resulting solution was poured into a saturated sodium thiosulfate solution and extracted with ethyl acetate as an extractant, and the organic phase was collected. The extraction operation was repeated three times, and the resulting organic phases were combined and dried over anhydrous magnesium sulfate, and then concentrated in vacuo to obtain a concentrated solution. The concentrated solution was subjected to silica gel column chromatography using a dichloromethane-methanol mixed solvent as an eluent to obtain a benzopyran-type flavonoid compound ZQQ43 (pale yellow solid, yield 77%).

[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] Example 38

[0357] 1 mmol of the benzopyran-type flavonoid ZQQ43 was dissolved in CH2Cl2. 1.5 mmol of BBr3 was added at -70°C and the reaction was allowed to proceed at -20°C for 30 minutes. The reaction progress was monitored by TLC. After completion, the reaction was quenched by the addition of anhydrous methanol. The resulting solution was then eluted with a dichloromethane-methanol mixture (dichloromethane:methanol, 50:1 volume ratio) and subjected to silica gel column chromatography to obtain the benzopyran-type flavonoid ZQQ69 (yellow solid, 34% yield).

[0358] The English name, structure and characterization data of the benzopyran-type 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] Example 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] Example 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 with (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] Example 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 with (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] Example 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 with (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] Example 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 with (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] Example 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] Example 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-type 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] Example 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-type 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] Example 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 with (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] Example 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] Example 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-type 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] Example 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-type 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] Example 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-type 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] Example 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] Example 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] Example 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-type 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] Example 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 with (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-type 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] Example 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 with (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] Example 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 with (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] Example 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] Example 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-type 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] Example 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-type 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] Example 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 with (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-type 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] Example 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] Example 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-type 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] Example 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] Example 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 with (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] Example 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 with (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] Example 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] Example 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 with (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-type 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] Example 69

[0543] The benzopyran-type 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-type 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] Example 70

[0549] The benzopyran-type 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-type 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] Example 71

[0555] The benzopyran-type 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-type 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] Example 72

[0561] The benzopyran-type 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-type 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-type 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 OsSWEET4 nucleotide sequence was amplified using conventional PCR using cDNA from the rice variety ZH11 (Oryza sativa Japonica Group) 48 hours after inoculation with rice blast fungus. The PCR reaction system consisted of 1 μL of cDNA, 2 μL of 10 μmol / L forward primer, 2 μL of 10 μmol / L reverse primer, 1 μL of Phanta High-Fidelity DNA Polymerase (P501-d2), 10 μL of 5× SF buffer (with 10 mmol / L MgSO₄), 1 μL of 10 mM dNTP mix, and 33 μL of ultrapure water. The PCR amplification protocol was as follows: initial denaturation at 95°C for 3 minutes, followed by 33 cycles of 95°C for 15 seconds, 59°C for 15 seconds, and 72°C for 1 minute, followed by a final extension at 72°C for 10 minutes. The fragment was recovered by agarose gel electrophoresis and excision, yielding a 777-bp amplified fragment.

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

[0572] (2) Transformation of the recombinant vector into EBY4000

[0573] A: Reagent preparation:

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

[0575] LIAc: Add 3.2995 g LIAc powder to 50 mL of ultrapure water and make up to 50 mL. Sterilize.

[0576] 10XTE buffer: 100 ml 1 mol / L Tris-HCl, 20 mL 500 mmol / L E-TTA, 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) and streak it on a YPM plate. 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; resuspend in 1 mL of ultrapure water and centrifuge at 10,000 rpm for 1 min; repeat this process once, and resuspend the bacteria in 300 μL of ultrapure water (as yeast) for subsequent experiments.

[0581] The system used in the yeast growth test consists 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 preparing the yeast growth assay system using the above ratios, perform the yeast transformation reaction on a PCR amplifier programmed to maintain a temperature of 28°C for 30 minutes, followed by 42°C for 13 minutes, and finally 28°C for 1-2 minutes. The resulting solution was centrifuged for 1 minute, the supernatant discarded, and the cells resuspended in 50 μL of ultrapure water. The cells were then plated on the corresponding selective SD / -Ura medium (supplemented with maltose) and incubated at 28°C until positive yeast colonies appeared on the culture plates.

[0589] (3) Effects of benzopyran-type 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, and sterilize.

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

[0595] Then, the following components were added to YP+1% Maltose medium or 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 medium and YP+1% Glucose medium, respectively (referred to as Mock);

[0597] Group B culture medium (control group): 120 μL of 50 mmol / L curcumin (final concentration of 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 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-type 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 1 minute to collect the bacteria and discard the supernatant; then wash the yeast twice with 1mL ultrapure water in a 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 Four concentration gradients were used to dilute the yeast suspension. 4 μL of yeast suspension was added dropwise to the culture media of groups A, B, C, and D in order. After the droplets on the culture media were completely dried, the culture media was sealed and cultured at 28-30°C for about 2 days until colonies grew. The trend was observed and photographed. The results were as follows: Figures 2 to 21 shown.

[0601] The results showed that compared with the control group, the addition of 40 μmol / L or 60 μmol / L of compounds ZQQ26, ZQQ35 or ZQQ41 to YPM medium did not affect the growth of yeast, while the addition of 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 on yeast growth was stronger when added at a concentration of 60 μmol / L than when added at a concentration of 40 μmol / L, indicating that the 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 flavonoids ZQQ26, ZQQ35, and ZQQ41 was tested by mycelial growth assay. 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) Culture medium preparation: The test compound was dissolved in DMSO to prepare a 50 mmol / L stock solution. The solution was then added to PDA culture medium and diluted to prepare a PDA culture medium plate containing the test sample. The final concentration of the test compound was 60 μmol / L. PDA culture medium containing an equal volume of DMSO served as a mock control, and PDA culture medium containing the fungicide pyraclostrobin served as a positive control.

[0606] (2) Pathogenic fungal mycelial growth test: The activated pathogenic fungi were inoculated into the prepared C 22 H 20 O5 (compound ZQQ26), 60 μmol / L C 26 H 30 O4N2 (compound ZQQ35) and 60 μmol / LC21 H 16 The activated soybean sclerotinia pathogen was also inoculated on the above culture medium and cultured in a 24°C light-shielded incubator. The mycelial growth of the pathogenic fungus was observed and recorded. Figures 22-24 shown.

[0607] The results showed that compared to the CK (Mock) control, compound ZQQ26 significantly inhibited the mycelial growth of the pathogenic fungi Magnaporthe grisea, U. maydis leaf blight, Corn ear rot, and Tobacco brown spot pathogen; compound ZQQ35 also significantly inhibited the mycelial growth of the pathogenic fungi U. maydis leaf blight, Corn ear rot, Soybean sclerotinia, and Grape canker; and compound ZQQ41 significantly inhibited the mycelial growth of the pathogenic fungi Magnaporthe grisea, U. maydis leaf blight, Rice sheath blight, and Soybean sclerotinia. Although the inhibitory effects of the benzopyran-type flavonoids ZQQ26, ZQQ35, and ZQQ41 on fungi were weaker than those of the positive control, the benzopyran-type flavonoids provided by the present invention still have good potential as broad-spectrum antifungal agents.

[0608] Test Example 3

[0609] The antibacterial activity of benzopyran flavonoids 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: Dissolve the test compound in DMSO to prepare a 50 mmol / L stock solution. Then, add the test compound to LB culture medium to prepare a culture medium with a final concentration of 60 μmol / L of the test compound. Use the same concentrations of kanamycin sulfate and curcumin as control culture medium, and use DMSO containing the same volume as the test compound as the mock culture medium.

[0612] (2) Pathogenic bacteria growth rate test: Pick newly activated bacteria and place them in 2 mL of LB culture medium, shake and culture them at 30°C and 220 rpm for 12 hours; then take 10 μL of bacterial suspension and mix them with 2 mL of LB culture medium containing the test compound, antibiotic, 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 place it at 30°C and shake and culture it at 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] The growth rate calculation formula is: (OD2-OD1) / OD1*100%.

[0614] The bacterial growth rate test results of benzopyran flavonoids 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 pyrophosphate pathogen, and tobacco bacterial wilt pathogen. Compared with the antibiotic treatment, the inhibitory effect of compound ZQQ26 on the above three bacteria was similar and significantly higher than that of the CK control. Compound ZQQ35 could effectively inhibit the growth rate of rice bacterial blight pathogen, tobacco angular leaf spot pathogen, and tobacco bacterial wilt pathogen. Compared with the antibiotic treatment, the inhibitory effect of compound ZQQ35 on the above three bacteria was similar and significantly higher than that of the CK control. Compound ZQQ41 could effectively inhibit the growth rate of Chinese cabbage soft rot pathogen, tobacco angular leaf spot pathogen, and tobacco bacterial wilt pathogen. Compared with the antibiotic treatment, the inhibitory effect of compound ZQQ41 on the above three bacteria was similar and significantly higher than that of the CK control.

[0615] Although the above embodiment provides a detailed description of the present invention, 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 scope of protection of the present invention.

Claims

1. A use of a benzopyran-type flavonoid compound in the preparation of a plant sugar transporter inhibitor, characterized in that: The plant sugar transporters are SWEETs; The benzopyran-type flavonoid compound has a structure shown in Formula I or Formula II: In Formula I and Formula II, 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, hydroxy, nitro, haloalkyl, aralkyl, alkylamino or heterocyclic amino groups; 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 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 Said R2 is selected from one of -H, methyl and ethyl; The R3 is selected from one of -H, hydroxyl, methoxy and ethoxy.

2. The use according to claim 1, 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.

3. The use according to claim 1, characterized in that The R1 is selected from any of the following groups:

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

5. The use according to claim 1, comprising the following steps: (1) The preparation method of the benzopyran-type flavonoid compound having the structure shown in Formula I comprises the following steps: Compound F is mixed with an aromatic aldehyde compound and ethanol, and a condensation reaction is carried out under alkaline conditions to obtain a benzopyran-type flavonoid compound having a structure represented by Formula I; (2) The preparation method of the benzopyran-type flavonoid compound having the structure shown in Formula II comprises the following steps: The benzopyran-type flavonoid compound having the structure shown in Formula I, wherein R2 is -H, is mixed with iodine and dimethyl sulfoxide to undergo a ring-forming reaction to obtain a benzopyran-type flavonoid compound having the 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.

6. The use of claim 1 for preparing a pharmaceutical preparation comprising an active ingredient and pharmaceutical excipients; characterized in that: The active ingredient is a benzopyran-type flavonoid compound.

7. The use according to claim 6, 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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