CN111057037B - Ultraviolet light-promoted synthesis method of xanthone compound - Google Patents
Ultraviolet light-promoted synthesis method of xanthone compound Download PDFInfo
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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
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
- C07D311/84—Xanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D311/86—Oxygen atoms, e.g. xanthones
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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
Abstract
The invention discloses an ultraviolet light-promoted synthesis method of xanthone compounds, which comprises the steps of taking the xanthone compounds as reaction substrates, taking oxygen in the air as an oxidant, reacting the reaction substrates in an organic solvent at normal temperature under the irradiation condition of 380-385 nm ultraviolet light, and separating after the reaction is finished to obtain the xanthone compounds. The synthesis method of the invention replaces the traditional heating reaction with the illumination reaction, thus saving energy; no catalyst is used.
Description
Technical Field
The invention relates to an ultraviolet light-promoted synthesis method of xanthone compounds.
Background
Xanthone compounds are important organic molecules and are widely applied to the fields of medicines and advanced materials. The xanthone compound is a natural product which is firstly separated from plants and microorganisms, and researches show that the xanthone compound has biological activities of resisting hypertension, thrombus, tumor and the like.
In view of the important role of xanthones, the search for synthetic methods is also ongoing. With Pd (OAc)2As a catalyst, K2S2O8As an oxidant, the diphenyl ether is subjected to an insertion carbonyl reaction by CO gas to synthesize a xanthone compound (Angewandte Chemie International Edition,2012,51: 5204); the palladium chloride of the bis-triphenylphosphine is used as a catalyst, and the o-dibromobenzene and the salicylaldehyde react to synthesize the xanthone compound (Chemical Communications,2009,42: 6469); the xanthone compound can also be synthesized by taking cesium fluoride as a catalyst and 2- (trimethylsilyl) phenyl trifluoromethanesulfonate and o-fluorobenzoic acid as raw materials (Organic Letters,2010,12: 3117).
Furthermore, xanthones can also be prepared by direct oxidation of xanthenes, which are directly oxidized to xanthones using stoichiometric amounts of potassium permanganate as the oxidant (Synthetic Communications,1999,29: 2405); the literature (Journal of the American Chemical Society,2002,124:4198) uses (n-C)4H9N+)3[PMo12O40]3-Oxidizing xanthene into xanthone by a PMSO catalytic oxidation system; literature (Tetrahedron,2004,60:11415) reports KMnO4/MnO2The mixture is an oxidant, and under the action of ultrasonic waves, xanthene is quickly oxidized into xanthone; literature (Advanced Synthesis)&Catalysis,2007,349:861) reported FeCl3A reaction of xanthene to xanthone in a TBHP catalytic oxidation system; literature (Green Chemistry,2011,13:2161) in polyethylene glycol solvent, with palladium complex as catalyst, molecular oxygen O2As a terminal oxidant, xanthene is oxidized to xanthone; literature (Advanced Synthesis)&Catalysis,2011,353:401) the KI/TBHP non-metallic catalytic oxidation system was used for the oxidation of xanthenes to xanthones; literature (Tetrahedron Letters,2015,56:2517) use of a fe (taml) Li/TBHP catalytic oxidation system for the oxidation of xanthenes to xanthones; the document (Applied Organometallic Chemistry 2015,29:456) reports the reaction of AuNPs @3D- (N) GFs catalytic system with air as terminal oxidant to oxidize xanthene to xanthone; co (ClO) is reported in the literature (Tetrahedron Letters,2016,57:5278)4)2Reaction of xanthene to xanthone with Oxone catalytic oxidation system; the document (ChemCatchem,2016,8:1825) reports the reaction of an oxygenated xanthene to a xanthone catalyzed by an Au-pDA-rGO/NHPI catalytic system; the literature (Synlett,2019,30:218) reports visible light-promoted DDQ/TBN/AcOH/O2Reaction of the system to oxidize xanthene to xanthone.
Disclosure of Invention
The invention aims to provide a method for preparing xanthone compounds by directly promoting oxidation reaction by ultraviolet light under the condition of no catalyst by using the xanthone compounds as raw materials.
In order to achieve the purpose, the invention adopts the following technical scheme: a xanthene compound is used as a reaction substrate, oxygen in the air is used as an oxidant, the reaction substrate is reacted in an organic solvent at normal temperature under the irradiation condition of 380-385 nm ultraviolet light, and the xanthene compound is obtained through separation treatment after the reaction is finished.
The structural formula of the xanthene compound is shown as a formula (II), and the structural formula of the corresponding obtained product xanthene ketone compound is shown as a formula (I);
in formula (I) or formula (II), Ar1And Ar2Each is phenyl, substituted phenyl, naphthyl or substituted naphthyl; the substituted phenyl or substituted naphthyl refers to that hydrogen on a benzene ring or a naphthalene ring is substituted by one or more substituents, and each substituent is independently selected from one of the following groups: C1-C8 alkyl, C1-C2 alkoxy, F, Cl, Br, NO2、CN、COOCH3Or CF3Preferably methyl, t-butyl, methoxy, F, Cl, Br, COOCH3Or NO2。
In the invention, the solvent is 1, 2-dichloroethane or dimethyl sulfoxide; the mass usage of the solvent is recommended to be 25-75 times of that of the reaction substrate.
In the invention, the reaction time is 16-30 h.
The post-treatment method of the reaction liquid comprises the following steps: after the reaction is finished, adding water into the reaction system, extracting with ethyl acetate, decompressing the extract liquor, evaporating to remove the solvent, and then carrying out column chromatography separation, wherein the volume ratio of ethyl acetate to petroleum ether is 1: 50 as eluent, collecting the eluent containing the target compound, and evaporating the solvent to obtain the xanthone compound.
The invention specifically recommends that the method for synthesizing the xanthone compound by using the xanthone compound as a reaction substrate is carried out according to the following steps: adding a xanthene compound into a 1, 2-dichloroethane solvent or dimethyl sulfoxide, reacting for 16-30 h under the irradiation of a 380-385 nm ultraviolet lamp at normal temperature in an air atmosphere, adding water into a reaction system, extracting with ethyl acetate, evaporating an extract under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of ethyl acetate to petroleum ether is 1: 50 as eluent, collecting the eluent containing the target compound, and evaporating the solvent to obtain the xanthone compound.
The synthesis method has the beneficial effects that:
(A) the illumination reaction replaces the traditional heating reaction, and the energy can be saved.
(B) No catalyst is used.
It is worth noting that visible light has been reported in the prior art to promote the relevant reaction, but under visible light conditions, a catalyst must be used to carry out the reaction. From the mechanism analysis, the visible light actually excites the activity of the catalyst and promotes the reaction; the ultraviolet light used in the present invention acts directly on the reactants, so that no catalyst may be used.
Detailed Description
The invention is further illustrated by the following specific examples, without limiting the scope of the invention thereto.
The following examples used xanthene compounds having the structural formulas shown in formulas (1-1) to (1-23), respectively:
the structural formulas of the xanthone compounds correspondingly prepared from the xanthone compounds of (1-1) to (1-23) are respectively shown in formulas (2-1) to (2-23):
example 1: preparation of xanthone (formula (2-1))
Adding 0.2mmol of xanthene (formula (1-1)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped with a magnetic stirrer, reacting at room temperature for 24 hours under the irradiation of a 380-385 nm ultraviolet lamp, adding water into a reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of ethyl acetate to petroleum ether is 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product xanthone, wherein the separation yield is 91%.
Example 2: preparation of xanthone (formula (2-1))
The reaction procedure was as in example 1, except that the solvent was changed to 1, 2-dichloroethane and the isolation yield of xanthone was 85%.
Example 3: preparation of 2-t-butylxanthone (formula (2-2))
Adding 0.2mmol of 2-tert-butyl xanthene (formula (1-2)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped with a magnetic stirrer, reacting at room temperature for 21h under the irradiation of a 380-385 nm ultraviolet lamp, adding water into a reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation according to the volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 2-tert-butyl xanthone, wherein the separation yield is 82%.
Example 4: preparation of 2-methylxanthone (formula (2-3))
Adding 0.2mmol of 2-methylxanthene (formula (1-3)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped with a magnetic stirrer, reacting at room temperature for 21h under the irradiation of a 380-385 nm ultraviolet lamp, adding water into a reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation at a volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 2-methyl xanthone, wherein the separation yield is 98%.
Example 5: preparation of 3-methylxanthone (formula (2-4))
Adding 0.2mmol of 3-methylxanthene (formula (1-4)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped with a magnetic stirrer, reacting at room temperature for 21h under the irradiation of a 380-385 nm ultraviolet lamp, adding water into a reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation at a volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 3-methyl xanthone, wherein the separation yield is 82%.
Example 6: preparation of 2-methoxyxanthone (formula (2-5))
Adding 0.2mmol of 2-methoxy xanthene (formula (1-5)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped with a magnetic stirrer, reacting at room temperature for 18h under the irradiation of a 380-385 nm ultraviolet lamp, adding water into a reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of ethyl acetate to petroleum ether is 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 2-methoxy xanthone, wherein the separation yield is 84%.
Example 7: preparation of 4-methoxy xanthone (formula (2-6))
Adding 0.2mmol of 4-methoxy xanthene (formula (1-6)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped with a magnetic stirrer, reacting at room temperature for 18h under the irradiation of a 380-385 nm ultraviolet lamp, adding water into a reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation at a volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 4-methoxy xanthone, wherein the separation yield is 80%.
Example 8: preparation of 7H-benzo [ c ] xanthen-7-one (formula (2-7))
Adding 0.2mmol of 7H-benzo [ c ] xanthene (formula (1-7)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped magnetic stirrer, reacting at room temperature for 18H under the irradiation of a 380-385 nm ultraviolet lamp, adding water into the reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation according to the volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 7H-benzo [ c ] xanthene-7-ketone, wherein the separation yield is 95%.
Example 9: preparation of 12H-benzo [ a ] xanthen-12-one (formula (2-8))
Adding 0.2mmol of 12H-benzo [ a ] xanthene (formula (1-8)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped magnetic stirrer, reacting at room temperature for 18H under the irradiation of a 380-385 nm ultraviolet lamp, adding water into the reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation according to the volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 12H-benzo [ a ] xanthene-12-ketone, wherein the separation yield is 94%.
Example 10: preparation of 2-fluoroxanthone (formula (2-9))
Adding 0.2mmol of 2-fluoroxanthene (formula (1-9)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped with a magnetic stirrer, reacting at room temperature for 21h under the irradiation of a 380-385 nm ultraviolet lamp, adding water into a reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation at a volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 2-fluoro xanthone, wherein the separation yield is 90%.
Example 11: preparation of 2-chlorooxanthrone of formula (2-10)
Adding 0.2mmol of 2-chloroxanthene (formula (1-10)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open assembly of a magnetic stirrer, reacting at room temperature for 24 hours under the irradiation of a 380-385 nm ultraviolet lamp, adding water into a reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of ethyl acetate to petroleum ether is 1: 50 as eluent, collecting eluent containing target compound, evaporating solvent to obtain product 2-chlorooxaanthone, with separation yield of 99%.
Example 12: preparation of 2-bromooxa-anthrone (formula (2-11))
Adding 0.2mmol of 2-bromoxanthene (formula (1-11)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped with a magnetic stirrer, reacting at room temperature for 24 hours under the irradiation of a 380-385 nm ultraviolet lamp, adding water into a reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of ethyl acetate to petroleum ether is 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 2-bromine oxygen heterocyclic anthrone, wherein the separation yield is 98%.
Example 13: preparation of 2-nitroxanthone (formula (2-12))
Adding 0.2mmol of 2-nitro xanthene (formula (1-12)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped with a magnetic stirrer, reacting at room temperature for 24 hours under the irradiation of a 380-385 nm ultraviolet lamp, adding water into a reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of ethyl acetate to petroleum ether is 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 2-nitro xanthone, wherein the separation yield is 41%.
Example 14: preparation of methyl xanthone-2-carboxylate (formula (2-13))
Adding 0.2mmol of xanthene-2-carboxylic acid methyl ester (formula (1-13)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped with a magnetic stirrer, reacting at room temperature for 26h under the irradiation of a 380-385 nm ultraviolet lamp, adding water into a reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation according to the volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product methyl xanthone-2-carboxylate with the separation yield of 90%.
Example 15: preparation of 2-methoxy-6-methylxanthone (formula (2-14))
Adding 0.2mmol of 2-methoxy-6-methylxanthene (formula (1-14)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped magnetic stirrer, reacting at room temperature for 30h under the irradiation of a 380-385 nm ultraviolet lamp, adding water into the reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation according to the volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 2-methoxy-6-methyl xanthone, wherein the separation yield is 48%.
Example 16: preparation of 2-chloro-6-methylxanthone (formula (2-15))
Adding 0.2mmol of 2-chloro-6-methylxanthene (formula (1-15)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped magnetic stirrer, reacting at room temperature for 24h under the irradiation of a 380-385 nm ultraviolet lamp, adding water into the reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation according to the volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 2-chloro-6-methyl xanthone, wherein the separation yield is 88%.
Example 17: preparation of 9-methyl-7H-benzo [ c ] xanthen-7-one (formula (2-16))
Adding 0.2mmol of 9-methyl-7H-benzo [ c ] xanthene (formula (1-16)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped with a magnetic stirrer, reacting at room temperature for 18H under the irradiation of a 380-385 nm ultraviolet lamp, adding water into the reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation according to the volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 9-methyl-7H-benzo [ c ] xanthene-7-ketone, wherein the separation yield is 99%.
Example 18: preparation of 10-methyl-7H-benzo [ c ] xanthen-7-one (formula (2-17))
Adding 0.2mmol of 10-methyl-7H-benzo [ c ] xanthene (formula (1-17)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped with a magnetic stirrer, reacting at room temperature for 24H under the irradiation of a 380-385 nm ultraviolet lamp, adding water into the reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation according to the volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 10-methyl-7H-benzo [ c ] xanthene-7-ketone with the separation yield of 79%.
Example 19: preparation of 9-methoxy-7H-benzo [ c ] xanthen-7-one (formula (2-18))
Adding 0.2mmol of 9-methoxy-7H-benzo [ c ] xanthene (formula (1-18)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open magnetic stirrer, reacting at room temperature for 18H under the irradiation of a 380-385 nm ultraviolet lamp, adding water into the reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation according to the volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 9-methoxy-7H-benzo [ c ] xanthene-7-ketone, wherein the separation yield is 76%.
Example 20: preparation of 11-methoxy-7H-benzo [ c ] xanthen-7-one (formula (2-19))
Adding 0.2mmol of 11-methoxy-7H-benzo [ c ] xanthene (formula (1-19)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open magnetic stirrer, reacting at room temperature for 18H under the irradiation of a 380-385 nm ultraviolet lamp, adding water into the reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation according to the volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 11-methoxy-7H-benzo [ c ] xanthene-7-ketone with the separation yield of 86%.
Example 21: preparation of 9-chloro-7H-benzo [ c ] xanthen-7-one (formula (2-20))
Adding 0.2mmol of 9-chloro-7H-benzo [ c ] xanthene (formula (1-20)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped with a magnetic stirrer, reacting at room temperature for 18H under the irradiation of a 380-385 nm ultraviolet lamp, adding water into the reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation according to the volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 9-chloro-7H-benzo [ c ] xanthene-7-ketone with the separation yield of 80%.
Example 22: preparation of 2-bromo-7H-benzo [ c ] xanthen-7-one (formula (2-21))
Adding 0.2mmol of 2-bromo-7H-benzo [ c ] xanthene (formula (1-21)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped with a magnetic stirrer, reacting at room temperature for 24H under the irradiation of a 380-385 nm ultraviolet lamp, adding water into the reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation according to the volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product 2-bromo-7H-benzo [ c ] xanthene-7-ketone with the separation yield of 75%.
Example 23: preparation of 14H-dibenzo [ a, H ] xanthen-14-one (formula (2-22))
Adding 0.2mmol of 14H-dibenzo [ a, H ] xanthene (formula (1-22)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with an open equipped with a magnetic stirrer, reacting at room temperature for 18H under the irradiation of a 380-385 nm ultraviolet lamp, adding water into the reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation at a volume ratio of ethyl acetate/petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the 14H-dibenzo [ a, H ] xanthene-14-ketone product, wherein the separation yield is 62%.
Example 24: preparation of 14H-dibenzo [ a, j ] xanthen-14-one (formula (2-23))
Adding 0.2mmol of 14H-dibenzo [ a, j ] xanthene (formula (1-23)) and 2mL of dimethyl sulfoxide into a 15mL reaction tube with a magnetic stirrer, reacting at room temperature for 24H under the irradiation of a 380-385 nm ultraviolet lamp, adding water into the reaction system, extracting with ethyl acetate, evaporating the extract under reduced pressure to remove the solvent, and performing column chromatography separation at a volume ratio of ethyl acetate to petroleum ether of 1: 50 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the 14H-dibenzo [ a, j ] xanthene-14-ketone product, wherein the separation yield is 68%.
Claims (5)
1. An ultraviolet light-promoted synthesis method of xanthone compounds is characterized in that: taking a xanthene compound as a reaction substrate, taking oxygen in the air as an oxidant, reacting the reaction substrate in an organic solvent at normal temperature under the irradiation condition of 380-385 nm ultraviolet light, and separating after the reaction is finished to obtain the xanthene ketone compound;
the structural formula of the xanthene compound is shown as a formula (II), and the structural formula of the corresponding obtained product xanthene ketone compound is shown as a formula (I);
in formula (I) or formula (II), Ar1And Ar2Each is phenyl, substituted phenyl, naphthyl or substituted naphthyl; the substituted phenyl or substituted naphthyl refers to that hydrogen on a benzene ring or a naphthalene ring is substituted by one or more substituents, and each substituent is independently selected from one of the following groups: C1-C8 alkyl, C1-C2 alkoxy, F, Cl, Br, NO2、CN、COOCH3Or CF3。
2. The method of claim 1, wherein: the substituent is preferably methyl, tert-butyl, methoxy, F, Cl, Br, COOCH3Or NO2。
3. The method of claim 2, wherein: the organic solvent is 1, 2-dichloroethane or dimethyl sulfoxide; the mass consumption of the solvent is 25-75 times of that of the reaction substrate.
4. The method of claim 2, wherein: the reaction time is 16-30 h.
5. The method of claim 2, wherein: the post-treatment method of the reaction liquid comprises the following steps: after the reaction is finished, adding water into the reaction system, extracting with ethyl acetate, decompressing the extract liquor, evaporating to remove the solvent, and then carrying out column chromatography separation, wherein the volume ratio of ethyl acetate to petroleum ether is 1: 50 as eluent, collecting the eluent containing the target compound, and evaporating the solvent to obtain the xanthone compound.
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