CN110229133B - Synthetic method of flavonoid compound - Google Patents
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- CN110229133B CN110229133B CN201910645840.6A CN201910645840A CN110229133B CN 110229133 B CN110229133 B CN 110229133B CN 201910645840 A CN201910645840 A CN 201910645840A CN 110229133 B CN110229133 B CN 110229133B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- 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
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—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
- 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
- C07D405/04—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 directly linked by a ring-member-to-ring-member bond
Abstract
The invention discloses a method for synthesizing a flavonoid compound, which comprises the following steps: under the oxygen atmosphere, reacting the compound shown in the formula A in a reaction system containing a catalyst Co-NC to generate a flavonoid compound shown in the formula B;
wherein R is1And R2Each independently selected from the group consisting of hydrogen, halogen, cyano, nitro, sulfonic acid, trifluoromethyl, amino, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkynyl having 2 to 12 carbon atoms, acyl having 2 to 12 carbon atoms, aryl having 6 to 40 carbon atoms, heteroaryl having 3 to 40 carbon atoms, carbocyclic ring or heterocyclic ring having 3 to 40 carbon atoms fused to the parent nucleus; m is an integer from 1 to 4, and n is an integer from 1 to 5. The synthesis method provided by the invention adopts a high-activity catalyst Co-NC as a catalyst, oxygen as an oxidant, realizes one-step synthesis of the flavonoid compound at room temperature, and has the advantages of mild reaction conditions, good selectivity and high yield.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing a flavonoid compound.
Background
Flavonoids (flavanones) are a class of compounds that occur in nature and have the structure of 2-phenyl chromones (flavanones). Flavonoids have a wide range of important biological and pharmacological actions, including: antioxidant, antiinflammatory, anticancer, gene mutagenesis resisting, and cardiovascular disease resisting effects. In recent years, research on flavonoids has entered a new stage, and with the intensive research on structure-activity relationship, an action mechanism of partial pharmacological action is discovered, which provides a theoretical basis for the application of flavonoids in the fields of medicine and food, and accelerates the development and utilization of flavonoids.
Recently, research on synthetic methods of flavonoids has received much attention. In the reported synthesis method, a flavone precursor is usually synthesized in advance and then oxidized, and a one-step synthesis method is also a precedent, but the reaction has the problem of poor selectivity of five-membered ring and six-membered ring.
Yu, Min et al (Yu, Min; Liu, Guangxiang; Han, Chengyan; Zhu, Li; Yao, Xiaooaquan; Letters in Organic Chemistry; vol.15; nb.1; (2018); p.70-77.) report Cu NPs as catalyst, bipyridine as ligand and i-Pr2NEt is used as alkali to synthesize flavone compounds in a water and toluene two-phase system, but the product prepared by the method has the selectivity problem of five-membered ring and six-membered ring, so that the separation difficulty of the product is higher.
Chinese patent with publication number CN108148035A discloses a preparation method of 2-aryl flavone, which takes ortho-hydroxyl aryl formyl formic acid and aryl alkynoic acid as raw materials, silver salt as catalyst, K2S2O8Under the condition of being used as an oxidant, the 2-aryl flavone is generated by ring closing reaction in a mixed solvent of acetonitrile and water. In the preparation method, the used catalyst silver salt is expensive and sensitive to light, and meanwhile, the reaction condition is not mild enough, and a strong oxidant is needed to be used for smooth reaction under the heating condition.
Chinese patent publication No. CN103408525A discloses a method for synthesizing flavonoids, which comprises reacting 2-hydroxyacetophenone derivatives with aroyl chloride under heating in the presence of potassium carbonate and pyridine under the catalysis of acetone as solvent to obtain flavonoids. However, in this synthesis, the aroyl chloride is sensitive to moisture and is easily transformed into carboxylic acid, and therefore, the reaction is required to be carried out under anhydrous conditions. Meanwhile, the reaction conditions are not mild enough, and the reaction needs to be carried out under heating conditions.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a novel synthesis method of flavonoid compounds, which has the advantages of good reaction selectivity, high reaction yield and mild reaction conditions.
The purpose of the invention is realized by adopting the following technical scheme:
a synthetic method of a flavonoid compound, comprising the following steps: under the oxygen atmosphere, reacting the compound shown in the formula A in a reaction system containing a catalyst Co-NC to generate a flavonoid compound shown in the formula B; the catalyst Co-NC is prepared by adopting the following method: dissolving cobalt salt, terephthalic acid and triethylene diamine in DMF, adding g-C under stirring3N4Removing the solvent after the reaction, heating the solid to 850-950 ℃ in an inert atmosphere, and cooling to obtain a catalyst Co-NC;
wherein R is1And R2Each independently selected from the group consisting of hydrogen, halogen, cyano, nitro, sulfonic acid, trifluoromethyl, amino, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkynyl having 2 to 12 carbon atoms, acyl having 2 to 12 carbon atoms, aryl having 6 to 40 carbon atoms, heteroaryl having 3 to 40 carbon atoms, carbocyclic ring or heterocyclic ring having 3 to 40 carbon atoms fused to the parent nucleus;
m is an integer from 1 to 4, and n is an integer from 1 to 5.
In one embodiment, the catalystIn the preparation method of the reagent Co-NC, cobalt nitrate hexahydrate is selected as the cobalt salt, wherein the cobalt nitrate hexahydrate, terephthalic acid, triethylene diamine and g-C3N4The mass ratio of (A) to (B) is 3.89: 9.07: 6.4: 61.8, heating the solid to 900 ℃ in nitrogen atmosphere, heating for 1h, and cooling to obtain the catalyst Co-NC.
In one embodiment, the molar ratio of the compound represented by formula a to the catalyst Co — NC is 1: (0.5-1.5), preferably 1: 1.
in one embodiment, the catalyst Co-NC has a particle size of 10nm to 50nm, preferably 15nm to 20 nm.
In one embodiment, the reaction system further comprises an ethereal solvent selected from tetrahydrofuran, diethyl ether or methyl tert-butyl ether, preferably tetrahydrofuran, and a ligand selected from 2,2 ' -bipyridine, 4 ' -bipyridine or 1, 10-phenanthroline, preferably 2,2 ' -bipyridine.
In one embodiment, the molar ratio of compound represented by formula a to ligand is 1: (0.05-0.2), preferably 1: 0.1.
in one embodiment, the synthesis process is carried out under light, oxygen atmosphere, 20-35 ℃ (room temperature).
In one embodiment, the light has a wavelength of 400nm to 750 nm.
In one embodiment, in the compounds represented by formula A and formula B, R1Is halogen, R2Is alkyl with 1-12 carbon atoms, and m and n are respectively 1 or 2.
In one embodiment, the compound represented by the formula a is obtained by reacting a compound represented by the formula C with a compound represented by the formula D in a reaction system containing n-butyllithium or t-butyllithium; the molar ratio of the compound represented by the formula C to the compound represented by the formula D to n-butyllithium or t-butyllithium is 1: 1;
wherein R is1And R2Each independently selected from hydrogen, halogen, cyano, nitro, sulfonic acid, and trifluoromethylA group, an amino group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a carbocyclic ring or heterocyclic ring having 3 to 40 carbon atoms condensed with a mother nucleus;
m is an integer from 1 to 4, and n is an integer from 1 to 5.
Compared with the prior art, the invention has the beneficial effects that at least: the synthesis method provided by the invention adopts a high-activity catalyst Co-NC as a catalyst, oxygen as an oxidant to realize one-step synthesis of the flavonoid compound, and has the advantages of good reaction selectivity, high yield, milder reaction conditions (realized under illumination and room temperature), and more convenient and faster working procedures.
Detailed Description
Example embodiments will now be described more fully. Example embodiments may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of example embodiments to those skilled in the art.
The invention provides a method for synthesizing a flavonoid compound, which adopts a high-activity catalyst Co-NC as a catalyst and oxygen as an oxidant to realize the high-efficiency and high-selectivity synthesis of the flavonoid compound.
Specifically, the synthesis method disclosed by the invention is as shown in the following formula, wherein the compound represented by the formula A is reacted in a reaction system containing a catalyst Co-NC under an oxygen atmosphere to generate the flavonoid compound represented by the formula B. The catalyst Co-NC is prepared by adopting the following method: dissolving cobalt salt, terephthalic acid and triethylene diamine in DMF (N, N-dimethylformamide), and adding g-C under stirring3N4(graphite phase carbon nitride), removing the solvent after reaction, heating the solid to 850-950 ℃ in an inert atmosphere, preferably to 900 ℃ for 1h, and cooling to obtain the catalyst Co-NC. g-C3N4The polymer semiconductor can be produced by a known method. The cobalt salt can be cobalt nitrate hexahydrateIn the synthesis of the catalyst, cobalt nitrate hexahydrate, terephthalic acid, triethylene diamine and g-C3N4The mass ratio of (A) to (B) is 3.89: 9.07: 6.4: 61.8.
in the compound represented by the formula A and the flavonoid compound represented by the formula B, R1And R2Each independently selected from hydrogen, halogen, cyano (-CN), nitro (-NO)2) Sulfonic acid group (-SO)3H) Trifluoromethyl (-CF)3) Amino (-NH-)3) An alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a carbocyclic ring or heterocyclic ring having 3 to 40 carbon atoms which is fused with the mother nucleus.
The halogen includes fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), and the halogen is preferably chlorine or bromine.
The alkyl group having 1 to 12 carbon atoms includes, but is not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl and n-hexyl, and the alkyl group having 1 to 12 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms.
The alkoxy group having 1 to 12 carbon atoms includes, but is not limited to, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the alkoxy group having 1 to 12 carbon atoms is preferably an alkoxy group having 1 to 6 carbon atoms.
The alkenyl group having 2 to 12 carbon atoms includes, but is not limited to, ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, and the alkenyl group having 2 to 12 carbon atoms is preferably an alkenyl group having 2 to 6 carbon atoms.
The alkynyl group having 2 to 12 carbon atoms includes, but is not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl and 2-butynyl, and the alkynyl group having 2 to 12 carbon atoms is preferably an alkynyl group having 2 to 6 carbon atoms.
The acyl group having 2 to 12 carbon atoms includes, but is not limited to, acetyl, propionyl, n-butyryl, isobutyryl, and the acyl group having 2 to 12 carbon atoms is preferably an acyl group having 2 to 6 carbon atoms.
The aryl group having 6 to 40 carbon atoms may be an aryl group having a monocyclic structure or a polycyclic structure or an aryl group having a condensed ring structure, and the aryl group may have a substituent or not, and the aryl group having 6 to 40 carbon atoms is preferably an aryl group having 6 to 18 carbon atoms. By way of example, aryl groups include, but are not limited to, phenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, spirobifluorenyl, biphenyl.
The heteroaryl group having 3 to 40 carbon atoms may have a five-membered heteroaryl ring or a six-membered heteroaryl ring, or may have a fused ring structure, wherein the heteroatom is at least one selected from the group consisting of O, N, S, the heteroaryl group may or may not have a substituent, and the heteroaryl group having 3 to 40 carbon atoms is preferably a heteroaryl group having 3 to 18 carbon atoms. As an example, heteroaryl includes, but is not limited to, furyl, pyrrolyl, pyridyl, thiazolyl, oxadiazolyl, pyrazinyl, carbazolyl, indenocarbazolyl, imidazolyl, pyrazolyl, pyrimidinyl, pyridazinyl, indolyl, quinolinyl.
The carbocyclic ring or heterocyclic ring having 3-40 carbon atoms condensed with the mother nucleus refers to the compound represented by formula A and the flavonoid compound represented by formula B, wherein R is1And R2Each independently being capable of fusing with the attached benzene ring to form a carbocyclic or heterocyclic ring of 3 to 40 carbon atoms, preferably 5 to 15 carbon atoms fused to the parent nucleus.
m is selected from an integer from 1 to 4, such as 1, 2, 3 or 4, m is preferably 1 or 2. n is selected from an integer from 1 to 5, such as 1, 2, 3, 4 or 5, m is preferably 1 or 2. When m and n are not equal to 1, a plurality of R in the compound represented by the formula A and the flavonoid compound represented by the formula B1May be the same or different from each other, a plurality of R2May be the same or different.
Compounds represented by formula a include, but are not limited to, the following:
flavonoids represented by formula B include, but are not limited to, the following:
in the method for synthesizing the flavonoid compound, the compound represented by the formula A is reacted in a reaction system containing a catalyst Co-NC to generate the flavonoid compound represented by the formula B, and the molar ratio of the compound represented by the formula A to the catalyst Co-NC is preferably 1: 0.5-1.5, more preferably 1: 1. the particle size of the catalyst Co-NC is preferably 10nm-50nm, more preferably 15nm-20 nm.
The reaction system of the synthesis method also comprises an ether solvent and a ligand. Wherein the ether solvent is selected from tetrahydrofuran, diethyl ether or methyl tert-butyl ether, and the ether solvent is preferably tetrahydrofuran. The ligand is selected from 2,2 ' -dipyridyl, 4 ' -dipyridyl or 1, 10-phenanthroline, and the ligand is preferably 2,2 ' -dipyridyl. The molar ratio of the compound represented by formula a to the ligand is preferably 1: (0.05-0.2), preferably 1: 0.1.
the synthesis method of the flavonoid compound is preferably carried out under the conditions of illumination, oxygen atmosphere and 20-35 ℃ (room temperature), and the wavelength of light waves of the illumination is preferably 400nm-750 nm.
In one embodiment, the compound represented by formula a is obtained by reacting a compound represented by formula C with a compound represented by formula D in a reaction system containing n-butyllithium or t-butyllithium. The molar ratio of the compound represented by the formula C to the compound represented by the formula D to n-butyllithium or t-butyllithium is 1: 1.
wherein R is1And R2Each independently selected from the group consisting of hydrogen, halogen, cyano, nitro, sulfonic acid, trifluoromethyl, amino, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkynyl having 2 to 12 carbon atoms, acyl having 2 to 12 carbon atoms, aryl having 6 to 40 carbon atoms, heteroaryl having 3 to 40 carbon atoms, and aryl having 3 to 40 carbon atoms fused to the parent nucleusCarbocyclic or heterocyclic.
m is selected from an integer from 1 to 4, such as 1, 2, 3 or 4. n is selected from an integer of 1 to 5, such as 1, 2, 3, 4 or 5. When m and n are not equal to 1, a plurality of R in the compound represented by the formula C or the compound represented by the formula D1May be the same or different from each other, a plurality of R2May be the same or different.
Preparation example of catalyst Co-NC
389.3mg of cobalt nitrate hexahydrate, 906.7mg of terephthalic acid and 640mg of triethylene diamine are weighed and dissolved in 50mLN, N-Dimethylformamide (DMF) solution to prepare a precursor solution containing cobalt. Adding g-C to the solution under magnetic stirring3N46.18g, stirred at room temperature for 2 h. And (3) evaporating the solvent under reduced pressure to obtain green solid powder, transferring the green solid powder into a canoe, placing the canoe into a tube furnace, heating the green solid powder to 900 ℃ at the speed of 1.5 ℃/min under nitrogen atmosphere, preserving the temperature for 1h, and cooling the green solid powder to room temperature to obtain a black solid sample, namely a catalyst Co-NC (152 mg).
Example 1
Under nitrogen, 2.79mL (22mmol) of p-methylphenylacetylene, 8.4mL (2.5M) of butyllithium n-hexane solution and 30mL of dried tetrahydrofuran were added to a Schlenk tube, and the mixture was stirred at-78 ℃ for 4 h. 1.91g (10mmol) of 3, 5-dichlorosalicylaldehyde was added thereto, and stirring was continued at-78 ℃ for 12 h. After the system was cooled to room temperature, the reaction was quenched by the addition of 30mL of saturated aqueous ammonium chloride. The mixture was washed with water (3X 20mL), and the resulting aqueous solution was extracted with diethyl ether (3X 20 mL). The organic phase was combined with the ether extract, dried over 2g of anhydrous sodium sulfate and evaporated under reduced pressure to remove the organic solvent. The obtained solid residue was separated by column chromatography (petroleum ether: ethyl acetate: 10:1) to obtain 2.46g of a white solid (a-1) in 80% yield.
Example 2
307.2mg of the substrate A-1(1mmol), 15.6mg of 2, 2' -bipyridine (10 mol%), a catalyst Co-NC 400mg, and 15mL of tetrahydrofuran were charged in a 100mL sealed tube under an oxygen atmosphere, and the mixture was reacted with light at room temperature for 12 hours. After the reaction was completed, the catalyst was allowed to stand and settle, the supernatant was transferred to a single-neck round-bottom flask, 3 × 5mL of dichloromethane was added to wash the catalyst, the washing solution was combined into the round-bottom flask, and after concentration under reduced pressure, column chromatography separation was performed (petroleum ether: ethyl acetate ═ 10:3) to obtain 280.8mg of solid (B-1) with a reaction yield of 92%. Characterization data for solid B-1 are 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。
example 3
Under nitrogen, 2.79mL (22mmol) of p-methylphenylacetylene, 8.4mL (2.5M) of butyllithium n-hexane solution and 30mL of dried tetrahydrofuran were added to a Schlenk tube, and the mixture was stirred at-78 ℃ for 4 h. 2.01g (10mmol) of 5-bromosalicylaldehyde is added into the solution, and the solution is kept at-78 ℃ and stirred for 12 hours. After the system was cooled to room temperature, the reaction was quenched by the addition of 30mL of saturated aqueous ammonium chloride. The mixture was washed with water (3X 20mL), and the resulting aqueous solution was extracted with diethyl ether (3X 20 mL). The organic phase was combined with the ether extract, dried over 2g of anhydrous sodium sulfate and evaporated under reduced pressure to remove the organic solvent. The obtained solid residue was separated by column chromatography (petroleum ether: ethyl acetate: 10:1) to obtain 2.60g of a white solid (a-2) in 82% yield.
Example 4
317.2mg of the substrate A-2(1mmol), 15.6mg of 2, 2' -bipyridine (10 mol%), 400mg of the catalyst Co-NC, and 15mL of tetrahydrofuran were charged in a 100mL sealed tube under an oxygen atmosphere, and the mixture was reacted with light at room temperature for 12 hours. After the reaction was completed, the catalyst was allowed to stand and settle, the supernatant was transferred to a single-neck round-bottom flask, 3 × 5mL of dichloromethane was added to wash the catalyst, the washing solution was combined into the round-bottom flask, and after concentration under reduced pressure, column chromatography separation was performed (petroleum ether: ethyl acetate: 10:3) to obtain 290mg of solid (B-2) with a reaction yield of 92%. Characterization data for solid B-2 are 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 embodiments of the present invention have been shown and described, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that those skilled in the art may make changes, modifications, substitutions and alterations to the above embodiments without departing from the spirit and scope of the present invention, all such changes being within the scope of the appended claims.
Claims (7)
1. A synthetic method of a flavonoid compound is characterized by comprising the following steps: under the oxygen atmosphere, reacting the compound shown in the formula A in a reaction system containing a catalyst Co-NC to generate a flavonoid compound shown in the formula B; the synthesis method is carried out under the conditions of illumination, oxygen atmosphere and 20-35 ℃, the wavelength of light wave of the illumination is 400nm-750nm, the reaction system further comprises an ether solvent and a ligand, the ether solvent is selected from tetrahydrofuran, diethyl ether or methyl tert-butyl ether, the ligand is selected from 2,2 '-bipyridyl, 4' -bipyridyl or 1, 10-phenanthroline, and the catalyst Co-NC is prepared by adopting the following method: dissolving cobalt salt, terephthalic acid and triethylene diamine in DMF, adding g-C under stirring3N4Reaction ofThen removing the solvent, heating the solid to 850-950 ℃ in an inert atmosphere, and cooling to obtain a catalyst Co-NC;
wherein R is1And R2Each independently selected from the group consisting of hydrogen, halogen, cyano, nitro, sulfonic acid, trifluoromethyl, amino, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkynyl having 2 to 12 carbon atoms, acyl having 2 to 12 carbon atoms, aryl having 6 to 40 carbon atoms, heteroaryl having 3 to 40 carbon atoms, carbocyclic ring or heterocyclic ring having 3 to 40 carbon atoms fused to the parent nucleus;
m is an integer from 1 to 4, and n is an integer from 1 to 5.
2. The method for synthesizing flavonoids compounds according to claim 1, wherein in the preparation method of the catalyst Co-NC, cobalt salt is selected from cobalt nitrate hexahydrate, wherein the cobalt nitrate hexahydrate, terephthalic acid, triethylene diamine, and g-C3N4The mass ratio of (A) to (B) is 3.89: 9.07: 6.4: 61.8, heating the solid to 900 ℃ in nitrogen atmosphere, heating for 1h, and cooling to obtain the catalyst Co-NC.
3. The method for synthesizing flavonoids according to claim 1, wherein the molar ratio of the compound represented by formula a to the catalyst Co — NC is 1: (0.5-1.5).
4. The method for synthesizing flavonoids compounds according to claim 1, wherein the particle size of the catalyst Co-NC is 10nm to 50 nm.
5. The method for synthesizing a flavonoid compound according to claim 1, wherein the molar ratio of the compound represented by formula a to the ligand is 1: (0.05-0.2).
6. According to claimA process for synthesizing a flavonoid compound according to claim 1, wherein R in the compounds represented by the formulae A and B1Is halogen, R2Is alkyl with 1-12 carbon atoms, and m and n are respectively 1 or 2.
7. The method for synthesizing flavonoids according to claim 1, wherein the compound represented by formula a is obtained by reacting a compound represented by formula C with a compound represented by formula D in a reaction system containing n-butyllithium or tert-butyllithium;
wherein R is1And R2Each independently selected from the group consisting of hydrogen, halogen, cyano, nitro, sulfonic acid, trifluoromethyl, amino, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkynyl having 2 to 12 carbon atoms, acyl having 2 to 12 carbon atoms, aryl having 6 to 40 carbon atoms, heteroaryl having 3 to 40 carbon atoms, carbocyclic ring or heterocyclic ring having 3 to 40 carbon atoms fused to the parent nucleus;
m is an integer from 1 to 4, and n is an integer from 1 to 5.
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Non-Patent Citations (3)
| Title |
|---|
| One Pot Synthesis of g-Benzopyranones via Iron-Catalyzed Aerobic Oxidation and Subsequent 4-Dimethylaminopyridine Catalyzed 6-endo Cyclization;Di Zhai，等;《Adv. Synth. Catal.》;20171117;第360卷;153-160 * |
| One-pot synthesis of aurones through oxidation-cyclization tandem reaction catalyzed by copper nanoparticles catalyst;Min Yu，等;《Letters in organic chemistry》;20181231;第15卷;70-77 * |
| Synthesis of Chromones through LiOtBu/Air-Mediated Oxidation and Regioselective Cyclization of o-Hydroxyphenyl Propargyl Carbinols;Shuai Zhang，等;《Eur. J. Org. Chem.》;20130228;2080–2083 * |
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