CN106008434B - A kind of synthetic method of 3- benzoyls coumarin kind compound - Google Patents
A kind of synthetic method of 3- benzoyls coumarin kind compound Download PDFInfo
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- CN106008434B CN106008434B CN201610428012.3A CN201610428012A CN106008434B CN 106008434 B CN106008434 B CN 106008434B CN 201610428012 A CN201610428012 A CN 201610428012A CN 106008434 B CN106008434 B CN 106008434B
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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
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/12—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 3 and unsubstituted in position 7
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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
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/14—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 6 and unsubstituted in position 7
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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
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
Abstract
The present invention provides a kind of synthetic methods of 3 benzoyl coumarin kind compound; belong to organic synthesis field; can be 3 benzoyl coumarin kind compound of Material synthesis directly using coumarin kind compound and aldehyde compound; this method is simple; synthetic product yield is high; and participated in without metal, it is environmental-friendly.The synthetic method includes the following steps：Coumarin kind compound, aldehyde compound and di-tert-butyl peroxide are separately added into reaction bulb, and is reacted 10 24 hours at a temperature of 100 200 DEG C；It treats after reaction, to be extracted using organic solvent, merges organic phase；After being dried to the organic phase, chromatographic isolation is carried out, obtains 3 benzoyl coumarin kind compounds.The present invention can be used in being synthetically prepared of 3 benzoyl coumarin kind compounds.
Description
Technical field
The present invention relates to organic synthesis field more particularly to a kind of synthesis sides of 3- benzoyls coumarin kind compound
Method.
Background technology
At present, the method for existing synthesizing coumarin class compound needs the ginseng of metallic catalyst and organic solvent mostly
With, such as：Reporting within 2015 cumarin can synthesizing coumarin class chemical combination under the action of silver nitrate with 2- carbonyl -2- phenylacetic acids
Object, yield were 24% (referring to Tetrahedron (tetrahedron), 630-636 pages of 4 phases of volume 71 in 2015).In addition, in 2015 also
It proposed using 3- benzyls frerrous chloride is catalyst, chlorobenzene is synthesizing coumarin class compound under conditions of solvent, production
Rate was 54% (referring to RSC Adv. (Royal Society of Chemistry), 88258-88265 pages of 107 phases of volume 5 in 2015).
But when using above method synthesizing coumarin class compound, used reaction system is complex, not only
Reaction time is longer, and low yield, at the same time, due to needing the participation of metal in reaction system, is also faced with environment
Unfriendly problem.
Invention content
The purpose of the present invention is to provide a kind of synthetic methods of 3- benzoyls coumarin kind compound, can be directly sharp
It is Material synthesis 3- benzoyl coumarin kind compounds with coumarin kind compound and aldehyde compound, this method is simple, closes
It is participated in into products collection efficiency height, and without metal, it is environmental-friendly.
An aspect of of the present present invention provides a kind of synthetic method of 3- benzoyls coumarin kind compound, including walking as follows
Suddenly：
It is separately added into coumarin kind compound, aldehyde compound and di-tert-butyl peroxide into reaction bulb, and
It is reacted 10-24 hours at a temperature of 100-200 DEG C；
It treats after reaction, to be extracted using organic solvent, merges organic phase；
After being dried to the organic phase, chromatographic isolation is carried out, obtains 3- benzoyl coumarin kind compounds.
MM ratio of the coumarin kind compound, aldehyde compound and di-tert-butyl peroxide is 1:1-2:1-3.
MM ratio of the coumarin kind compound, aldehyde compound and di-tert-butyl peroxide is 1:2:2.
The coumarin kind compound has shown formula (A) structure：Wherein,
R1Selected from-H ,-CH3、-NO2、-CH3O, any one of-OH；
R2Selected from-H or-CH3。
The aldehyde compound has shown formula (B) structure：Wherein,
R3Selected from-CH3O, any one of-H ,-Br ,-Cl.
The chromatographic column used in the chromatographic isolation is silicagel column, and the eluant, eluent used is the mixed of ethyl acetate and petroleum ether
Bonding solvent, volume ratio 1:3-2:1.
The organic phase is dried using anhydrous sodium sulfate.
The organic solvent is selected from dichloromethane or ethyl acetate.
Another aspect provides a kind of 3- benzoyl cumarins as described in any of the above-described technical solution
The 3- benzoyl coumarin kind compounds that the synthetic method of class compound synthesizes have shown formula (C) structure：
Wherein, R1Selected from-CH3、-NO2、-CH3O, any one of-OH；R2Selected from-H or-CH3；R3Selected from-CH3O、-H、-
Any one of Br ,-Cl.
Formula (C) structure specifically includes following compounds：
The present invention provides a kind of synthetic method of 3- benzoyls coumarin kind compound, compared with the prior art and
Speech, synthetic method provided by the present invention can be Material synthesis 3- benzene directly using coumarin kind compound and aldehyde compound
Formoxyl coumarin kind compound.Not only method is simple for this method, mild condition, and the yield of synthetic product is high, can
Reach more than 80%, also, in the method also without the participation of metal, it is environmental-friendly, it can be provided for those skilled in the art
A kind of new method for synthesizing 3- benzoyl coumarin kind compounds.
Specific embodiment
The technical solution in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's all other embodiments obtained without making creative work belong to the model that the present invention protects
It encloses.
The embodiment of one aspect of the present invention provides a kind of synthetic method of 3- benzoyls coumarin kind compound, including
Following steps：
S1：It is separately added into coumarin kind compound, aldehyde compound and di-tert-butyl peroxide into reaction bulb, and
It is reacted 10-24 hours at a temperature of 100-200 DEG C.
In this step, 3- benzene is synthesized using coumarin kind compound, aldehyde compound and di-tert-butyl peroxide
Formoxyl coumarin kind compound, in this step, di-tert-butyl peroxide are generated by the way that homolysis occurs in a heated condition
Tert-butoxy free radical carrys out initiation reaction, and in this step, the participation without metal.It is understood that for the step
Set temperature and reaction time in rapid, those skilled in the art can be selected according to real reaction situation, as long as really
Protect reaction raw materials reaction fully, thoroughly.
S2：It treats after reaction, to be extracted using organic solvent, merges organic phase.
In this step, the reactant obtained in S1 is extracted using organic solvent, can extracted repeatedly, by gained
The coumarin kind compound arrived extracts more complete.
S3：After being dried to the organic phase, chromatographic isolation is carried out, obtains 3- benzoyl coumarin kind compounds.
In this step, dry organic phase, removes the moisture included, then carries out chromatographic isolation, by gradient elution with
Obtain 3- benzoyl coumarin kind compounds.
The present invention provides a kind of synthetic method of 3- benzoyls coumarin kind compound, compared with the prior art and
Speech, synthetic method provided by the present invention can be Material synthesis 3- benzene directly using coumarin kind compound and aldehyde compound
Formoxyl coumarin kind compound.Not only method is simple for this method, mild condition, and the yield of synthetic product is high, also,
It is environmental-friendly also without the participation of metal in this method, a kind of synthesis 3- benzoyl basic notes can be provided for those skilled in the art
The new method of beans chlorins compound.
In one embodiment of this invention, the coumarin kind compound, aldehyde compound and di-tert-butyl peroxide
MM ratio be 1:1-2:1-3.In the present embodiment, the addition of above-mentioned three kinds of raw materials, i.e. a mM ratio are set as 1:1-
2:1-3, wherein, di-tert-butyl peroxide can be excessive addition with respect to both remaining, can ensure that coumarin kind compound in this way
The reaction was complete with aldehyde compound；In a preferred embodiment, the coumarin kind compound, aldehyde compound and di-t-butyl
MM ratio of peroxide is 1:2:2, under the ratio, it can not only ensure the abundant reaction of each reaction raw materials, it can also be effective
The addition of each raw material is controlled, so as to reduce reaction cost.
In one embodiment of this invention, the coumarin kind compound has shown formula (A) structure：Wherein, R1Selected from-H ,-CH3、-NO2、-CH3O, any one of-OH；R2Selected from-H or-
CH3.In the present embodiment, the concrete structure formula of coumarin kind compound used in specifically defining, it is to be understood that this
Coumarin kind compound defined in embodiment is the compound being derived based on cumarin, and structure is relatively simple,
But it is not precluded in the present embodiment and prepares the 3- benzene that the application finally obtains by the more complicated coumarin derivatives of structure
Formoxyl coumarin kind compound.
In one embodiment of this invention, the aldehyde compound has shown formula (B) structure：Wherein, R3Selected from-CH3O, any one of-H ,-Br ,-Cl.In the present embodiment, specifically
The concrete structure formula of aldehyde compound used in defining, it is to be understood that the aldehydes chemical combination defined in the present embodiment
Object is the compound being derived based on benzaldehyde, and structure is relatively simple, but be not precluded in the present embodiment by structure compared with
The 3- benzoyl coumarin kind compounds that the application finally obtains are prepared for complicated Benzaldehyde derivatives.
In one embodiment of this invention, the chromatographic column used in the chromatographic isolation be silicagel column, the eluant, eluent used
For ethyl acetate and the mixed solvent of petroleum ether, volume ratio 1:3-2:1.In the present embodiment, to subsequently from organic phase
The ingredient being obtained by extraction recycles silicagel column to carry out gradient elution, so as to isolated expected synthetic product.It is mixed according to similar
Principle and in view of the polarity size of synthetic product, it is 1 that volume ratio is selected in the present embodiment:3-2:1 ethyl acetate and oil
The mixed solvent of ether carries out gradient elution, and in the range, those skilled in the art can be adjusted according to actual conditions.
In one embodiment of this invention, the organic phase is dried using anhydrous sodium sulfate.In the present embodiment, it utilizes
Anhydrous sodium sulfate removes the moisture in organic phase, it is to be understood that also can be selected familiar to those skilled in the art other
Organic phase is dried in substance or method.
In one embodiment of this invention, the organic solvent is selected from dichloromethane or ethyl acetate.In the present embodiment,
In view of the polarity size of expected synthetic product, organic solvent is defined to dichloromethane or ethyl acetate, from effect of extracting, into
Present aspect consider, the two preferably as the organic solvent in the present embodiment, but it is understood that, the selectable model of organic solvent
Enclose and be not limited to above-mentioned cited solvent, can also be polarity it is similar be applicable to extract the other of expected synthetic product
Solvent.
The embodiment of another aspect of the present invention provides a kind of 3- benzoyl basic notes as described in any of the above-described embodiment
The 3- benzoyl coumarin kind compounds that the synthetic method of beans chlorins compound synthesizes have shown formula (C) structure：
Wherein, R1Selected from-CH3、-NO2、-CH3O, any one of-OH；R2Selected from-H or-CH3；R3Selected from-CH3O、-H、-
Any one of Br ,-Cl.
In one embodiment of this invention, formula (C) structure specifically includes following compounds：
In order to become apparent from introducing the conjunction of 3- benzoyl coumarin kind compounds that the embodiment of the present invention is provided in detail
Into method, illustrated below with reference to specific embodiment.
Embodiment 1
Cumarin, benzaldehyde and di-tert-butyl peroxide are separately added into reaction bulb, and anti-at a temperature of 100 DEG C
It answers 10 hours；It treats after reaction, to be extracted using ethyl acetate, combined ethyl acetate phase；It treats to dry ethyl acetate phase
Afterwards, chromatographic isolation is carried out, obtains clear crystal, i.e. 3- benzoyls -2H- chromen-2-ones (1)：
Magnetic resonance spectroscopy analysis is carried out to above-mentioned clear crystal powder, data are as follows：
1H NMR(400MHz,CDCl3)δ:8.08 (s, 1H), 7.90 (d, 7.4Hz, 2H), 7.85 (td, J=8.7Hz, J=
1.5Hz, 1H), 7.64 (dd, J=7.9Hz, J=1.5Hz, 1H), 7.49 (d, J=7.9Hz, 2H), 7.38 (t, J=8.3Hz,
1H), 7.39 (td, J=7.9Hz, J=0.7Hz, 1H)；
13C NMR(100MHz,CDCl3)d:191.7,158.4,154.7,145.4,136.2,133.8,133.7,
129.6,129.2,128.6,125.0,118.2,116.9；
After identified, spectral data is corresponding with structural formula, it was demonstrated that synthesis is 3- benzoyl -2H- chromen-2-ones, production
Rate is 85%.
Embodiment 2
Cumarin, 4- hydroxy benzaldehydes and di-tert-butyl peroxide are separately added into reaction bulb, and in 120 DEG C of temperature
The lower reaction of degree 12 hours；It treats after reaction, to be extracted using ethyl acetate, combined ethyl acetate phase；It treats to ethyl acetate
Mutually after drying, chromatographic isolation is carried out, obtains white solid, i.e. 3- (4- methoxybenzoyls) -2H- chromen-2-ones (2)：
Magnetic resonance spectroscopy analysis is carried out to above-mentioned white solid powder, data are as follows：
1H NMR(400MHz,CDCl3)δ:8.02 (s, 1H), 7.89 (d, J=8.7Hz, 2H), 7.68 (td, J=8.7Hz,
J=1.4Hz, 1H), 7.63 (dd, J=7.7Hz, J=1.1Hz, 1H), 7.42 (d, J=8.1Hz, 1H), 7.35 (t, J=
7.3Hz, 1H), 6.96 (d, J=8.9Hz, 1H), 3.89 (s, 3H)；
13C NMR(100MHz,CDCl3)d:190.5,164.6,158.9,154.6,144.8,133.1,132.2,
129.2,129.0,127.6,124.8,118.2,116.9,113.9,55.9；
After identified, spectral data is corresponding with structural formula, it was demonstrated that synthesis is 3- (4- methoxybenzoyls) -2H- colors
Alkene -2- ketone, yield 81%.
Embodiment 3
It is separately added into 6-Methylcoumarin, 4-methoxybenzaldehyde and di-tert-butyl peroxide into reaction bulb, and
It is reacted 14 hours at a temperature of 140 DEG C；It treats after reaction, to be extracted using dichloromethane, combined dichloromethane phase；It treats pair
After dichloromethane is mutually dried, chromatographic isolation is carried out, obtains white solid, i.e. 3- (4- methoxybenzoyls) -6- methyl -2H- colors
Alkene -2- ketone (3)：
Magnetic resonance spectroscopy analysis is carried out to above-mentioned white solid powder, data are as follows：
1HNMR(400MHz,CDCl3):δ：7.98 (s, 1H), 7.88 (d, J=8.4Hz, 2H), 7.46-7.42 (m, 1H),
7.38 (s, 1H), 7.32 (d, J=8.4Hz, 1H), 6.98 (d, J=8.0Hz, 2H), 3.90 (s, 3H), 2.45 (s, 3H)；
13C NMR(100MHz,CDCl3):δ=190.3,164.4,158.9,152.8,144.8,134.5,134.3,
132.2,129.2,128.5,127.3,118.2,116.8,113.7,55.8,20.9；
After identified, spectral data is corresponding with structural formula, it was demonstrated that synthesis is 3- (4- methoxybenzoyls) -6- first
Base -2H- chromen-2-ones, yield 93%.
Embodiment 4
It is separately added into 6- nitros cumarin, 4-methoxybenzaldehyde and di-tert-butyl peroxide into reaction bulb, and
It is reacted 16 hours at a temperature of 160 DEG C；It treats after reaction, to be extracted using dichloromethane, combined dichloromethane phase；It treats pair
After dichloromethane is mutually dried, chromatographic isolation is carried out, obtains light yellow solid, i.e. 3- (4- methoxybenzoyls) -6- nitros -2H-
Chromen-2-one (4)：
Magnetic resonance spectroscopy analysis is carried out to above-mentioned light yellow solid powder, data are as follows：
1H NMR(400MHz,DMSO)δ:8.84 (d, J=2.6Hz, 1H), 8.53 (dd, J=9.1Hz, J=2.8Hz,
1H), 8.47 (s, 1H), 7.99 (dd, J=7.1Hz, J=2.2Hz, 2H), 7.75 (d, J=9.1Hz, 1H), 7.06 (dd, J=
7.2Hz, J=2.1Hz, 2H), 3.86 (s, 3H)；
13C NMR(100MHz,DMSO)d:189.9,164.7,158.1,157.9,144.1,143.7,132.5,129.0,
128.5,128.0,125.6,119.2,118.1,114.7,56.1；
After identified, spectral data is corresponding with structural formula, it was demonstrated that synthesis is 3- (4- methoxybenzoyls) -6- nitre
Base -2H- chromen-2-ones, yield 95%.
Embodiment 5
It is separately added into umbelliferone, 4-methoxybenzaldehyde and di-tert-butyl peroxide into reaction bulb, and
It is reacted 18 hours at a temperature of 180 DEG C；It treats after reaction, to be extracted using dichloromethane, combined dichloromethane phase；It treats pair
After dichloromethane is mutually dried, chromatographic isolation is carried out, obtains light yellow solid, i.e. 7- hydroxyls -3- (4- methoxybenzoyls) -2H-
Chromen-2-one (5)：
Magnetic resonance spectroscopy analysis is carried out to above-mentioned light yellow solid powder, data are as follows：
1H NMR(400MHz,DMSO)δ:10.96 (s, 1H), 8.24 (s, 1H), 7.86 (dd, J=6.8Hz, J=
2.0Hz, 2H), 7.69 (d, J=8.5Hz, 1H), 7.06 (dd, J=6.8Hz, J=2.0Hz, 2H), 6.89 (dd, J=8.5Hz,
J=2.2Hz, 1H), 6.82 (d, J=2.2Hz, 1H), 3.83 (s, 3H)；
13C NMR(100MHz,DMSO)d:190.8,164.2,163.4,158.7,156.8,146.4,132.2,131.6,
129.6,122.1,114.1,114.0,111.1,102.6,56.1；
After identified, spectral data is corresponding with structural formula, it was demonstrated that synthesis is 7- hydroxyls -3- (4- methoxybenzene first
Acyl) -2H- chromen-2-ones, yield 80%.
Embodiment 6
6- methoxy coumarins, 4- bromobenzaldehydes and di-tert-butyl peroxide are separately added into reaction bulb, and 200
It is reacted 20 hours at a temperature of DEG C；It treats after reaction, to be extracted using ethyl acetate, combined ethyl acetate phase；It treats to second
After acetoacetic ester is mutually dried, carry out chromatographic isolation, obtain light yellow solid, i.e. 3- (4- Bromophenacyls) -6- methoxyl group -2H- chromenes -
2- ketone (6)：
Magnetic resonance spectroscopy analysis is carried out to above-mentioned light yellow solid powder, data are as follows：
1H NMR(400MHz,CDCl3):δ：8.11 (s, 1H), 7.78 (d, J=8.6Hz, 2H), 7.66 (d, J=8.3Hz,
2H), 7.36 (d, J=9.2Hz, 1H), 7.24 (dd, J=9.2,2.8Hz, 1H), 7.04 (d, J=2.8Hz, 1H), 3.89 (s,
1H)；
13C NMR(100MHz,CDCl3):δ：190.8,158.4,156.2,149.6,145.8,135.2,131.9,
131.2,129.0,126.8,122.2,118.4,118.1,110.6,55.7；
After identified, spectral data is corresponding with structural formula, it was demonstrated that synthesis be 3- (4- Bromophenacyls) -6- methoxyl groups -
2H- chromen-2-ones, yield 89%.
Embodiment 7
It is separately added into Hymecromone, benzaldehyde and di-tert-butyl peroxide into reaction bulb, and
It is reacted 22 hours at a temperature of 130 DEG C；It treats after reaction, to be extracted using ethyl acetate, combined ethyl acetate phase；It treats pair
After ethyl acetate phase drying, chromatographic isolation is carried out, obtains white solid, i.e. 3- benzoyls -7- hydroxy-4-methyls-chromen-2-one
(7)：
Magnetic resonance spectroscopy analysis is carried out to above-mentioned white solid powder, data are as follows：
1HNMR (400MHz, acetone-d6):δ：8.00-7.98 (m, 2H), 7.78-7.76 (dd, J=8.8,1.2Hz,
1H), 7.72-7.66 (td, J=8.0,1.2Hz, 1H), 7.57-7.52 (t, J=7.6Hz, 2H), 6.96-6.93 (dd, J=
8.8,2.4Hz, 1H), 6.84-6.82 (d, J=2.4Hz, 1H), 3.00 (s, 1H), 2.33 (s, 3H)；
13C NMR (100MHz, acetone-d6):δ：194.2,162.4,159.3,156.0,151.4,137.9,134.7,
130.1,129.8,128.4,123.3,114.2,113.1,103.1,15.8；
After identified, spectral data is corresponding with structural formula, it was demonstrated that synthesis is 3- benzoyls -7- hydroxy-4-methyls-color
Alkene -2- ketone, yield 85%.
Embodiment 8
Cumarin, 2- chlorobenzaldehydes and di-tert-butyl peroxide are separately added into reaction bulb, and in 150 DEG C of temperature
Lower reaction 24 hours；It treats after reaction, to be extracted using dichloromethane, combined dichloromethane phase；It treats to dichloromethane phase
After drying, chromatographic isolation is carried out, obtains light yellow solid, i.e. 3- (2- chlorobenzoyls) -2H- chromen-2-ones (8)：
Magnetic resonance spectroscopy analysis is carried out to above-mentioned light yellow solid powder, data are as follows：
1H NMR(400MHz,CDCl3)δ：8.39 (s, 1H), 7.68-7.64 (m, 2H), 7.57 (d, J=7.5Hz, 1H),
7.45 (d, J=6.2Hz, 1H), 7.47-7.32 (m, 4H)；
13C NMR(100MHz,CDCl3)δ：191.4,158.2,155.3,147.2,138.2,134.5,132.1,
131.6,129.7,129.6,127.3,126.2,124.9,118.5,116.9；
After identified, spectral data is corresponding with structural formula, it was demonstrated that synthesis is 3- (2- chlorobenzoyls) -2H- chromenes -2-
Ketone, yield 95%.
Claims (6)
1. a kind of synthetic method of 3- benzoyls coumarin kind compound, which is characterized in that include the following steps：
Coumarin kind compound, aldehyde compound and di-tert-butyl peroxide are separately added into reaction bulb, and in 100-200
It is reacted 10-24 hours at a temperature of DEG C；
It treats after reaction, to be extracted using organic solvent, merges organic phase；
After being dried to the organic phase, chromatographic isolation is carried out, obtains 3- benzoyl coumarin kind compounds；
The coumarin kind compound has shown formula (A) structure：Wherein,
R1Selected from-H ,-CH3、-NO2、-CH3O, any one of-OH；R2Selected from-H or-CH3；
The aldehyde compound has shown formula (B) structure：Wherein,
R3Selected from-CH3O, any one of-H ,-Br ,-Cl；
Obtained 3- benzoyl coumarin kind compounds have shown formula (C) structure：
Wherein, R1Selected from-CH3、-NO2、-CH3O, any one of-OH；R2Selected from-H or-CH3；R3Selected from-CH3O、-H、-Br、-
Any one of Cl.
2. synthetic method according to claim 1, which is characterized in that the coumarin kind compound, aldehyde compound and
MM ratio of di-tert-butyl peroxide is 1:1-2:1-3.
3. synthetic method according to claim 2, which is characterized in that the coumarin kind compound, aldehyde compound and
MM ratio of di-tert-butyl peroxide is 1:2:2.
4. synthetic method according to claim 1, which is characterized in that the chromatographic column used in the chromatographic isolation is silica gel
Column, mixed solvent of the eluant, eluent used for ethyl acetate and petroleum ether, volume ratio 1:3-2:1.
5. synthetic method according to claim 1, which is characterized in that dried using anhydrous sodium sulfate to the organic phase.
6. synthetic method according to claim 1, which is characterized in that the organic solvent is selected from dichloromethane or acetic acid second
Ester.
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