CN110229133A - A kind of synthetic method of flavone compound - Google Patents
A kind of synthetic method of flavone compound Download PDFInfo
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- CN110229133A CN110229133A CN201910645840.6A CN201910645840A CN110229133A CN 110229133 A CN110229133 A CN 110229133A CN 201910645840 A CN201910645840 A CN 201910645840A CN 110229133 A CN110229133 A CN 110229133A
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
- C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones
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- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
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Abstract
The invention discloses a kind of synthetic method of flavone compound, the synthetic method is the following steps are included: under oxygen atmosphere, the compound that formula A the is indicated flavone compound that reacted production B is indicated in the reaction system containing catalyst Co-NC；Wherein, R1And R2It is each independently selected from the carbocyclic ring or heterocycle that aryl, the heteroaryl that carbon atom number is 3-40, the carbon atom number condensed with parent nucleus that acyl group, carbon atom number that alkynyl, carbon atom number that alkenyl, carbon atom number that alkoxy, carbon atom number that alkyl, carbon atom number that hydrogen, halogen, cyano, nitro, sulfonic group, trifluoromethyl, amino, carbon atom number are 1-12 are 1-12 are 2-12 are 2-12 are 2-12 are 6-40 are 3-40；M is selected from the integer of 1-4, and n is selected from the integer of 1-5.Synthetic method of the invention selects the catalyst Co-NC of high activity as catalyst, and oxygen realizes the one-step synthesis of flavone compound as oxidant at room temperature, reaction condition mildly, selective good, high income.
Description
Technical field
The present invention relates to technical field of organic synthesis more particularly to a kind of synthetic methods of flavone compound.
Background technique
Flavone compound (flavonoids) is that one kind is present in nature, has 2- phenyl chromone
(flavone) compound of structure.Flavone compound has extensive and important bioactivity and pharmacological action, wherein wrapping
It includes: the effects of anti-oxidant, anti-inflammatory, anticancer, anti-Mutagenesis, cardiovascular disease resistant.In recent years, to the research of flavone compound into
A new stage is entered, with the further investigation to its structure-activity relationship, it was found that the mechanism of action of Pharmacological is it
Theoretical foundation is provided in the application of medicine, field of food, accelerates the development and utilization of flavone compound.
Recently, the Study of synthesis method of flavone compound receives the extensive concern of people.In reported synthesis side
In method, it usually needs then pre-synthesis flavones precursor aoxidizes flavones precursor, also there is the precedent of one-step synthesis method, but
It is that there are the bad problems of the selectivity of five yuan and hexatomic ring for reaction.
Yu, Min et al. (Yu, Min；Liu,Guangxiang；Han,Chengyan；Zhu,Li；Yao,Xiaoquan；
Letters in Organic Chemistry；vol.15；nb.1；(2018)；P.70-77.) report using Cu NPs as urging
Agent, bipyridyl is as ligand and i-Pr2NEt synthesizes the new of flavone compound as alkali in water and toluene two-phase system
Method, but there are the selective problems of five, hexatomic ring for product made from this method, cause product separating difficulty larger.
The Chinese patent of Publication No. CN108148035A discloses a kind of preparation method of 2- aryl flavones, the preparation side
Method is using adjacent hydroxyaryl formic acid and aryl acetylenic acid as raw material, using silver salt as catalyst, K2S2O8Condition as oxidant
Under, ring closure reaction occurs in the in the mixed solvent of acetonitrile and water and generates 2- aryl flavones.It is used to urge in the preparation method
Agent silver salt is expensive, and light sensitive, and simultaneous reactions condition is not mild enough, needs using strong oxidizer, in the item of heating
It could smoothly react under part.
The Chinese patent of Publication No. CN103408525A discloses a kind of synthetic method of flavone compound, the synthesis
Method is using acetone as solvent, and under the co-catalysis of potassium carbonate and pyridine, 2- hydroxyacetophenone derivative and fragrant formyl chloride are existed
It is reacted under conditions of heating, obtains flavone compound.But in the synthetic method, fragrant formyl chloride is to water vapor sensitive, perishable
It is converted to carboxylic acid, therefore, reaction requires to carry out under the conditions of anhydrous.At the same time, reaction condition is not mild enough, and reaction needs
It carries out under heating conditions.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of new synthesis of flavone compound
Method, the good reaction selectivity of the synthetic method, reaction yield is high, and reaction condition is mild.
The purpose of the present invention is implemented with the following technical solutions:
A kind of synthetic method of flavone compound, the synthetic method is the following steps are included: under oxygen atmosphere, formula A table
The compound shown the flavone compound that reacted production B is indicated in the reaction system containing catalyst Co-NC；It is described to urge
Agent Co-NC is prepared using following methods: cobalt salt, terephthalic acid (TPA), triethylene diamine being dissolved in DMF, are added with stirring
g-C3N4, solvent is removed after reaction, solids is warming up to 850-950 DEG C of heating under an inert atmosphere, obtains catalyst after cooling
Co-NC；
Wherein, R1And R2It is each independently selected from hydrogen, halogen, cyano, nitro, sulfonic group, trifluoromethyl, amino, carbon atom
The alkynes that alkenyl that alkoxy that alkyl that number is 1-12, carbon atom number are 1-12, carbon atom number are 2-12, carbon atom number are 2-12
It is heteroaryl that aryl that acyl group that base, carbon atom number are 2-12, carbon atom number are 6-40, carbon atom number are 3-40, thick with parent nucleus
The carbon atom number of conjunction is the carbocyclic ring or heterocycle of 3-40；
M is selected from the integer of 1-4, and n is selected from the integer of 1-5.
In one embodiment, in the preparation method of the catalyst Co-NC, cobalt salt selects cabaltous nitrate hexahydrate, wherein
Cabaltous nitrate hexahydrate, terephthalic acid (TPA), triethylene diamine, g-C3N4Mass ratio be 3.89:9.07:6.4:61.8, by solids
It is warming up to 900 DEG C of heating 1h under nitrogen atmosphere, obtains catalyst Co-NC after cooling.
In one embodiment, the molar ratio of the formula A is indicated compound and catalyst Co-NC is 1:(0.5-1.5),
It is preferred that 1:1.
In one embodiment, the partial size of the catalyst Co-NC is 10nm-50nm, preferably 15nm-20nm.
In one embodiment, the reaction system further includes ether solvent and ligand, and the ether solvent is selected from tetrahydro
Furans, ether or methyl tertiary butyl ether(MTBE), preferably tetrahydrofuran, the ligand are selected from 2,2 '-bipyridyls, 4,4'-Bipyridine or 1,
10- phenanthroline, preferably 2,2 '-bipyridyls.
In one embodiment, the molar ratio of formula A is indicated compound and ligand is 1:(0.05-0.2), preferably 1:0.1.
In one embodiment, the synthetic method carries out under the conditions of illumination, oxygen atmosphere, 20-35 DEG C (room temperature).
In one embodiment, the optical wavelength of the illumination is 400nm-750nm.
In one embodiment, in the compound that formula A and formula B is indicated, R1For halogen, R2The alkane for being 1-12 for carbon atom number
Base, m and n are respectively 1 or 2.
In one embodiment, the compound that the compound and formula D that the formula C that the formula A is indicated is indicated indicate
It is reacted in the reaction system containing n-BuLi or tert-butyl lithium to obtain；The chemical combination of compound, formula D expression that formula C is indicated
The molar ratio of object and n-BuLi or tert-butyl lithium is 1:1；
Wherein, R1And R2It is each independently selected from hydrogen, halogen, cyano, nitro, sulfonic group, trifluoromethyl, amino, carbon atom
The alkynes that alkenyl that alkoxy that alkyl that number is 1-12, carbon atom number are 1-12, carbon atom number are 2-12, carbon atom number are 2-12
It is heteroaryl that aryl that acyl group that base, carbon atom number are 2-12, carbon atom number are 6-40, carbon atom number are 3-40, thick with parent nucleus
The carbon atom number of conjunction is the carbocyclic ring or heterocycle of 3-40；
M is selected from the integer of 1-4, and n is selected from the integer of 1-5.
Compared with prior art, beneficial effects of the present invention include at least: synthetic method of the invention selects high activity
Catalyst Co-NC realizes the one-step synthesis of flavone compound, reaction selectivity as oxidant as catalyst, oxygen
Good, high income, reaction condition is more mild (illumination, room temperature can be realized), and process is more convenient.
Specific embodiment
Example embodiment will be described more fully now.However, example embodiment can be implemented in a variety of forms, and
It is not understood as limited to embodiment set forth herein；On the contrary, these embodiments are provided so that the present invention more comprehensively with it is complete
It is whole, and the design of example embodiment is comprehensively communicated to those skilled in the art.
The present invention provides a kind of synthetic method of flavone compound, which selects the catalyst Co- of high activity
NC realizes efficient, the high selectivity of flavone compound as catalyst, oxygen as oxidant.
Specifically, synthetic method of the invention is shown below, and under oxygen atmosphere, the compound that formula A is indicated is containing urging
The flavone compound that reacted production B is indicated in the reaction system of agent Co-NC.Catalyst Co-NC uses following methods
Preparation: cobalt salt, terephthalic acid (TPA), triethylene diamine are dissolved in DMF (n,N-Dimethylformamide), g- is added with stirring
C3N4(graphite phase carbon nitride), removes solvent after reaction, solids is warming up to 850-950 DEG C of heating under an inert atmosphere, preferably rises
Temperature obtains catalyst Co-NC after cooling to 900 DEG C of heating 1h.g-C3N4Known formula can be used as a kind of polymer semiconductor
Method preparation.Cobalt salt can use cabaltous nitrate hexahydrate, in the synthesis of catalyst, cabaltous nitrate hexahydrate, terephthalic acid (TPA), triethylene
Diamines, g-C3N4Mass ratio be 3.89:9.07:6.4:61.8.
In the flavone compound of compound, formula B expression that formula A is indicated, R1And R2It is each independently selected from hydrogen, halogen, cyanogen
Base (- CN), nitro (- NO2), sulfonic group (- SO3H), trifluoromethyl (- CF3), amino (- NH3), carbon atom number be 1-12 alkane
Alkynyl that alkenyl that alkoxy that base, carbon atom number are 1-12, carbon atom number are 2-12, carbon atom number are 2-12, carbon atom number
For the acyl group of 2-12, carbon atom number be 6-40 aryl, carbon atom number be 3-40 heteroaryl, with parent nucleus condense carbon atom number
For the carbocyclic ring or heterocycle of 3-40.
Halogen includes fluorine (F), chlorine (Cl), bromine (Br), iodine (I), the preferred chlorine of halogen, bromine.
Carbon atom number be 1-12 alkyl include but is not limited to be methyl, ethyl, propyl, isopropyl, normal-butyl, Zhong Ding
Base, isobutyl group, tert-butyl, n-pentyl, n-hexyl, the alkyl that the preferred carbon atom number of the alkyl that carbon atom number is 1-12 is 1-6.
Carbon atom number be 1-12 alkoxy include but is not limited to be methoxyl group, ethyoxyl, propoxyl group, butoxy, penta oxygen
Base, hexyloxy, the alkoxy that the preferred carbon atom number of the alkoxy that carbon atom number is 1-12 is 1-6.
Carbon atom number be 2-12 alkenyl include but is not limited to be vinyl, 1- acrylic, 2- acrylic, 1- cyclobutenyl,
2- cyclobutenyl, the alkenyl that the preferred carbon atom number of the alkenyl that carbon atom number is 2-12 is 2-6.
Carbon atom number be 2-12 alkynyl include but is not limited to be acetenyl, 1- propinyl, 2-propynyl, 1- butynyl,
2- butynyl, the alkynyl that the preferred carbon atom number of the alkynyl that carbon atom number is 2-12 is 2-6.
Carbon atom number be 2-12 acyl group include but is not limited to be acetyl group, propiono, positive bytyry, isobutyryl, carbon
The acyl group that the preferred carbon atom number of the acyl group that atomicity is 2-12 is 2-6.
Carbon atom number is that the aryl of 6-40 can be the aryl with single ring architecture or multiring structure, is also possible to have thick
The aryl of ring structure, the preferred carbon atom number of aryl that can be 6-40 with or without substituent group, carbon atom number on aryl are
The aryl of 6-18.As an example, aryl includes but is not limited to be phenyl, naphthalene, anthryl, phenanthryl, fluorenyl, two fluorenyl of spiral shell, biphenyl
Base.
Carbon atom number is that the heteroaryl of 3-40 can have five yuan of hetero-aromatic rings or six-membered Hetero-aromatic, is also possible to have simultaneously ring
The hetero-aromatic ring of structure, hetero atom therein are selected from least one of O, N, S, can be with or without substituted on heteroaryl
Base, the heteroaryl that the preferred carbon atom number of the heteroaryl that carbon atom number is 3-40 is 3-18.As an example, heteroaryl includes but unlimited
Then furyl, pyrrole radicals, pyridyl group, thiazolyl, oxadiazoles base, pyrazinyl, carbazyl, indeno carbazyl, imidazole radicals, pyrazoles
Base, pyrimidine radicals, pyridazinyl, indyl, quinolyl.
The carbocyclic ring or heterocycle for being 3-40 with the carbon atom number that parent nucleus condenses refer to that the compound that formula A is indicated and formula B indicate
In flavone compound, R1And R2Be each independently capable of with the phenyl ring that is connected it is condensed formed carbocyclic ring that carbon atom number is 3-40 or
Heterocycle is preferably formed as the carbocyclic ring or heterocycle that are 5-15 with the carbon atom number that parent nucleus condenses.
M is selected from the integer of 1-4, such as 1,2,3 or 4, and m is preferably 1 or 2.N is selected from the integer of 1-5, such as 1,2,3,4 or 5, and m is excellent
It is selected as 1 or 2.It should be noted that when m and n is not equal to 1, in the flavone compound of compound, formula B expression that formula A is indicated,
Multiple R1Between can be identical or different, multiple R2Between can be identical or different.
Formula A indicate compound include but is not limited to be following compound:
Formula B indicate flavone compound include but is not limited to be following compound:
In the synthetic method of flavone compound of the invention, the compound that formula A is indicated is containing the anti-of catalyst Co-NC
The flavone compound that reacted production B is indicated in system is answered, the molar ratio of compound and catalyst Co-NC that formula A is indicated
Preferably 1:0.5-1.5, more preferable 1:1.The partial size of catalyst Co-NC is preferably 10nm-50nm, more preferably 15nm-20nm.
The reaction system of above-mentioned synthetic method further includes ether solvent and ligand.Wherein, ether solvent be selected from tetrahydrofuran,
Ether or methyl tertiary butyl ether(MTBE), the preferred tetrahydrofuran of ether solvent.Ligand is selected from 2,2 '-bipyridyls, 4,4 '-bipyridyls or 1,
10- phenanthroline, ligand preferably 2,2 '-bipyridyls.The molar ratio of compound and ligand that formula A is indicated is preferably 1:(0.05-
0.2), preferably 1:0.1.
The synthetic method of flavone compound of the invention preferably under the conditions of illumination, oxygen atmosphere, 20-35 DEG C (room temperature) into
Row, the optical wavelength of illumination is preferably 400nm-750nm.
In one embodiment, the compound that the compound and formula D that the formula C that formula A is indicated is indicated indicate is containing
There is reacted in the reaction system of n-BuLi or tert-butyl lithium obtain.Formula C indicate compound, formula D indicate compound with
The molar ratio of n-BuLi or tert-butyl lithium is 1:1.
Wherein, R1And R2It is each independently selected from hydrogen, halogen, cyano, nitro, sulfonic group, trifluoromethyl, amino, carbon atom
The alkynes that alkenyl that alkoxy that alkyl that number is 1-12, carbon atom number are 1-12, carbon atom number are 2-12, carbon atom number are 2-12
It is heteroaryl that aryl that acyl group that base, carbon atom number are 2-12, carbon atom number are 6-40, carbon atom number are 3-40, thick with parent nucleus
The carbon atom number of conjunction is the carbocyclic ring or heterocycle of 3-40.
M is selected from the integer of 1-4, such as 1,2,3 or 4.N is selected from the integer of 1-5, such as 1,2,3,4 or 5.It should be noted that m
When being not equal to 1 with n, in the compound of compound, formula D expression that formula C is indicated, multiple R1Between can be identical or different, multiple R2
Between can be identical or different.
The preparation example of catalyst Co-NC
Cabaltous nitrate hexahydrate 389.3mg, terephthalic acid (TPA) 906.7mg are weighed, triethylene diamine 640mg is dissolved in 50mL
In n,N-Dimethylformamide (DMF) solution, the precursor solution containing cobalt is made.Under magnetic stirring, g- is added into solution
C3N42h is stirred at room temperature in 6.18g.Evaporating solvent under reduced pressure obtains green solid powder, transfers them to and be placed in pipe in Noah's ark
In formula furnace, under nitrogen atmosphere, 900 DEG C is heated to the speed of 1.5 DEG C/min, 1h is kept the temperature, is cooled to room temperature, obtains black solid
Sample, that is, catalyst Co-NC (152mg).
Embodiment 1
Under nitrogen atmosphere, by 2.79mL (22mmol) to methyl phenylacetylene, butyl lithium hexane solution 8.4mL (2.5M) and
30mL dry tetrahydrofuran is added in Schlenk pipe, and mixed liquor is in -78 DEG C of stirring 4h.3,5-, bis- chloro-salicyloyl is added thereto
Aldehyde 1.91g (10mmol) is kept for -78 DEG C continue to stir 12h.It is cooled to room temperature to system, the ammonium chloride water of 30mL saturation is added
Reaction is quenched solution.Mixed liquor is washed with water (3 × 20mL), and gained aqueous phase solution is extracted with ether (3 × 20mL).It will be organic
Mutually merge with ether extraction liquid, adds 2g anhydrous sodium sulfate to be dried, remove organic solvent under reduced pressure.Obtained solid residue passes through
Column chromatography is separated (petroleum ether: ethyl acetate=10:1), obtains white solid (A-1) 2.46g, yield 80%.
Embodiment 2
Under oxygen atmosphere, in the tube sealing of 100mL, it is added 307.2mg substrate A -1 (1mmol), 15.6mg 2,2 '-joins pyrrole
Pyridine (10mol%), catalyst Co-NC 400mg, tetrahydrofuran 15mL, at room temperature illumination reaction 12h.To after reaction,
Catalyst is subjected to standing sedimentation, supernatant is transferred in single necked round bottom flask, the washing catalysis of 3 × 5mL methylene chloride is added
Cleaning solution is incorporated into round-bottomed flask by agent, carries out column chromatography for separation (petroleum ether: ethyl acetate=10:3) after reduced pressure,
Obtain solid (B-1) 280.8mg, reaction yield 92%.The characterize data of solid B-1 is as follows:
1H NMR(CDCl3, 300MHz): 8.08 (d, J=1.9Hz, 1H), 7.86 (d, J=8.2Hz, 2H), 7.72 (d, J
=1.9Hz, 1H), 7.34 (d, J=6.1Hz, 2H), 6.82 (s, 1H), 2.45 (s, 3H).
13C NMR(CDCl3, 75MHz): 176.5,163.7,150.5,143.0,133.7,130.8,130.0,128.1,
126.4,125.8,124.5,123.9,106.6,21.6。
Embodiment 3
Under nitrogen atmosphere, by 2.79mL (22mmol) to methyl phenylacetylene, butyl lithium hexane solution 8.4mL (2.5M) and
30mL dry tetrahydrofuran is added in Schlenk pipe, and mixed liquor is in -78 DEG C of stirring 4h.5- bromosalicylaldehyde is added thereto
2.01g (10mmol) is kept for -78 DEG C continue to stir 12h.It is cooled to room temperature to system, the ammonium chloride solution of 30mL saturation is added
Reaction is quenched liquid.Mixed liquor is washed with water (3 × 20mL), and gained aqueous phase solution is extracted with ether (3 × 20mL).By organic phase
Merge with ether extraction liquid, adds 2g anhydrous sodium sulfate to be dried, remove organic solvent under reduced pressure.Obtained solid residue passes through column
Chromatography is separated (petroleum ether: ethyl acetate=10:1), obtains white solid (A-2) 2.60g, yield 82%.
Embodiment 4
Under oxygen atmosphere, in the tube sealing of 100mL, it is added 317.2mg substrate A -2 (1mmol), 15.6mg 2,2 '-joins pyrrole
Pyridine (10mol%), catalyst Co-NC 400mg, tetrahydrofuran 15mL, at room temperature illumination reaction 12h.To after reaction,
Catalyst is subjected to standing sedimentation, supernatant is transferred in single necked round bottom flask, the washing catalysis of 3 × 5mL methylene chloride is added
Cleaning solution is incorporated into round-bottomed flask by agent, carries out column chromatography for separation (petroleum ether: ethyl acetate=10:3) after reduced pressure,
Obtain solid (B-2) 290mg, reaction yield 92%.The characterize data of solid B-2 is as follows:
1H NMR(CDCl3, 300MHz): 8.36 (d, J=1.8Hz, 1H), 7.82-7.76 (m, 3H), 7.47 (d, J=
6.7Hz, 1H), 7.34 (d, J=6.1Hz, 2H), 6.81 (s, 1H), 2.45 (s, 3H).
13C NMR(CDCl3, 75MHz): 177.1,163.9,155.0,142.6,136.6,129.9,128.6,128.4,
126.3,125.4,120.0,118.59,107.0,21.6。
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art are not departing from the principle of the present invention and objective
In the case where, it can make changes, modifications, alterations, and variations to the above described embodiments in the range of invention, all these change
Change all should belong within the scope of protection of the claims of the present invention.
Claims (10)
1. a kind of synthetic method of flavone compound, which is characterized in that the synthetic method is the following steps are included: in oxygen atmosphere
Under, the compound that formula A the is indicated flavonoid that reacted production B is indicated in the reaction system containing catalyst Co-NC
Object；The catalyst Co-NC is prepared using following methods: cobalt salt, terephthalic acid (TPA), triethylene diamine being dissolved in DMF, stirred
Mix lower addition g-C3N4, solvent is removed after reaction, solids is warming up to 850-950 DEG C of heating under an inert atmosphere, obtains after cooling
Catalyst Co-NC；
Wherein, R1And R2Being each independently selected from hydrogen, halogen, cyano, nitro, sulfonic group, trifluoromethyl, amino, carbon atom number is
Alkynyl that alkenyl that alkoxy that the alkyl of 1-12, carbon atom number are 1-12, carbon atom number are 2-12, carbon atom number are 2-12,
Heteroaryl that aryl that acyl group that carbon atom number is 2-12, carbon atom number are 6-40, carbon atom number are 3-40 is condensed with parent nucleus
Carbon atom number is the carbocyclic ring or heterocycle of 3-40；
M is selected from the integer of 1-4, and n is selected from the integer of 1-5.
2. the synthetic method of flavone compound according to claim 1, which is characterized in that the system of the catalyst Co-NC
In Preparation Method, cobalt salt selects cabaltous nitrate hexahydrate, wherein cabaltous nitrate hexahydrate, terephthalic acid (TPA), triethylene diamine, g-C3N4's
Mass ratio is 3.89:9.07:6.4:61.8, and solids is warming up to 900 DEG C of heating 1h under nitrogen atmosphere, is catalyzed after cooling
Agent Co-NC.
3. the synthetic method of flavone compound according to claim 1, which is characterized in that the compound that the formula A is indicated
Molar ratio with catalyst Co-NC is 1:(0.5-1.5).
4. the synthetic method of flavone compound according to claim 1, which is characterized in that the grain of the catalyst Co-NC
Diameter is 10nm-50nm.
5. the synthetic method of flavone compound according to claim 1, which is characterized in that the reaction system further includes ether
Class solvent and ligand, the ether solvent are selected from tetrahydrofuran, ether or methyl tertiary butyl ether(MTBE), and the ligand is selected from 2,2 '-connection
Pyridine, 4,4 '-bipyridyls or 1,10- phenanthroline.
6. the synthetic method of flavone compound according to claim 5, which is characterized in that formula A indicate compound with match
The molar ratio of body is 1:(0.05-0.2).
7. the synthetic method of flavone compound according to claim 1, which is characterized in that the synthetic method illumination,
Oxygen atmosphere carries out under the conditions of 20-35 DEG C.
8. the synthetic method of flavone compound according to claim 7, which is characterized in that the optical wavelength of the illumination is
400nm-750nm。
9. the synthetic method of flavone compound according to claim 1, which is characterized in that the compound that formula A and formula B is indicated
In, R1For halogen, R2The alkyl for being 1-12 for carbon atom number, m and n are respectively 1 or 2.
10. the synthetic method of flavone compound according to claim 1, which is characterized in that the compound that the formula A is indicated
The compound indicated by the formula C compound indicated and formula D is reacted in the reaction system containing n-BuLi or tert-butyl lithium
It obtains；The compound and n-BuLi of compound, formula D expression that formula C is indicated or the molar ratio of tert-butyl lithium are 1:1；
Wherein, R1And R2Being each independently selected from hydrogen, halogen, cyano, nitro, sulfonic group, trifluoromethyl, amino, carbon atom number is
Alkynyl that alkenyl that alkoxy that the alkyl of 1-12, carbon atom number are 1-12, carbon atom number are 2-12, carbon atom number are 2-12,
Heteroaryl that aryl that acyl group that carbon atom number is 2-12, carbon atom number are 6-40, carbon atom number are 3-40 is condensed with parent nucleus
Carbon atom number is the carbocyclic ring or heterocycle of 3-40；
M is selected from the integer of 1-4, and n is selected from the integer of 1-5.
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