CN109651344A - A kind of benzofuran triarylmethane class compound and its green catalysis synthetic method - Google Patents
A kind of benzofuran triarylmethane class compound and its green catalysis synthetic method Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- 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
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- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract
Present invention discloses a kind of benzofuran triarylmethane class compound and its green catalysis synthetic methods, this method is using benzofuranone and its derivative and heteroaromatic compound as primary raw material, using cuprous bromide as catalyst, it is solvent in acetonitrile, potassium peroxydisulfate is oxidant, potassium dihydrogen phosphate is under conditions of alkali, higher yields obtains triaryl quaternary carbon class compound.This method has the advantages that cost is relatively low, and yield is high, easy to operate, pollution-free, has potential prospects for commercial application.This method provides cheap, green a approach for the preparation of triaryl quaternary carbon compound.
Description
[technical field]
The invention belongs to be catalyzed organic synthesis field, relate in particular in the case where cuprous bromide is as catalysts conditions, benzene
And Furanones compound is closed with heteroaromatic compound (quinoline, indoles, carbazole or thiophene) by intersecting dehydrogenation coupling reaction
At the new method of triarylmethane class compound.This method is based on benzofuranone and its derivative and heteroaromatic compound
Raw material is wanted, is solvent in acetonitrile, potassium peroxydisulfate is oxidant, and potassium dihydrogen phosphate is the condition of alkali using cuprous bromide as catalyst
Under, higher yields obtain triarylmethane class compound.
[background technique]
In recent years, copper catalysed cross dehydrogenation coupling (CDC) reaction has become the high-efficiency synthesis method of building carbon-carbon bond.
And triarylmethane class compound structure, it is widely present in material science and pharmaceutical chemistry.In terms of material science, triphenyl first
Radical derivative represents a kind of important dyestuff, these dyestuffs are with its brilliant colouring intensity and low resistance on many substrates
Photosensitiveness and it is well-known.The trityl group compound that stable quinoid can be generated occupies important position in organic dyestuff chemistry
It sets, frequently as dyestuff and fluorogen.These compounds provide usually in the form of functional derivatives, suitable for biomolecule
Covalent fluorescent marker.Triarylmethane (TAMs) also causes the concern of many scientists in field of medicaments, and multifunctionality exists
It is apparent in daily use.Simple triarylmethane has the work of inhibitory activity to intestines worm, filaria, trichmonad and trypanosome
With, and the phenol derivatives of known TAM shows anti-oxidation characteristics, anti-tumor activity etc..For example, following several triaryl first
Alkyl compound has become the pharmaceutical preparation for being hopeful treating cancer, bacterium infection and diabetes, and structural formula is as follows:
Some carbonyl Benzazole compounds with triarylmethane class compound structure have been identified as cancer cell increasing
The effective inhibitor grown, structural formula are as follows:
Due to practicability of the triaryl class compound in material science and pharmaceutical chemistry, the exploitation of high-efficiency synthesis method
It is a vital task of organic chemistry.The especially research of the chiral asymmetric triarylmethane method of catalysis asymmetric syntheses,
The extensive concern of people is caused in recent years.In the past decade, the highly selective and efficient functionalization of c h bond causes science
The great attention on boundary and industrialization educational circles.From the perspective of Green Chemistry, c h bond activation and the formation of C-C key are preferably to close
At one of method.And cross-coupling reaction is to form one of most important method of C-C key.Intersect dehydrogenation coupling reaction, is straight
It connects using the c h bond in differential responses substrate, under oxidative conditions, carries out dehydrogenation coupling reaction and form C-C key.In general, in order to
The cross-coupling products to succeed, it usually needs one or two kinds of pre- functionalized reactants.With conventional construction asymmetry C-C
The reaction of key is compared, and combines the CDC for forming new C-C key to react two c h bonds, has more in terms of efficiency and cost-effectiveness
More advantages.It avoids the needs for preparing pre- functionalization material, and keeps organic synthesis simpler and more effective, realizes shorter
Synthetic route and higher atom utilization efficiency are not only directly to carry out efficient complicated organic synthesis using simple raw material
Task provides a new thinking and means, and more green chemical synthesis has made major contribution.It is reported from Li Chaojun et al.
First example of the CDC reaction of copper catalysis is forming C-C, is having been achieved for many impressive progresses in terms of C-N and C-P key.
This process represents Green Chemistry in very various major progress: simple organic substrates can effectively be coupled without
Want pre- functionalization；Amount of waste significantly reduces；Reaction provides most direct and effective method for the formation of C-C and C-X key.To current
Until, there is also the methods of many building quaternary carbon structural units in organic chemistry filed, they develop quite mature mostly,
But building triarylmethane class compound method report is few, and does not report to react using copper catalysis by CDC and construct
The method of triarylmethane class compound, therefore for deficiency present in current synthetic method, we use with cuprous bromide
It is solvent in acetonitrile, potassium peroxydisulfate is oxidant, and potassium dihydrogen phosphate is Benzopyranone kind under conditions of alkali for catalyst
It closes object and synthesizes triarylmethane by intersecting dehydrogenation coupling reaction with heteroaromatic compound (quinoline, indoles, carbazole or thiophene)
Class compound, and obtained triarylmethane class compound is all noval chemical compound, and the method is not necessarily to special equipment requirement,
Yield is high, no pollution to the environment, meets the theory of the Ecological Civilization Construction of country's proposition.Currently, both at home and abroad not yet about copper
Catalysis prepares open source literature and the patent application of triarylmethane class compound by CDC reaction.
[summary of the invention]
The purpose of the present invention is to provide a kind of triarylmethane class compound and preparation method thereof, the catalysis synthesis process with
Cuprous bromide is catalyst, is solvent in acetonitrile, potassium peroxydisulfate is oxidant, and potassium dihydrogen phosphate is three virtue of preparation under conditions of alkali
The method of methylmethane class compound.Benzofuranone and its derivative are under the action of cuprous bromide is as catalyst, with heterocycle
Class aromatic compound (quinoline, indoles, carbazole or thiophene) occur intersect dehydrogenation coupling reaction, reaction under the conditions of acetonitrile solvent into
Row, can obtain preferable reaction effect.This method has the advantages that cost is relatively low, and yield is high, easy to operate, pollution-free, for
Realize that its industrialized production has certain feasibility.To achieve the above object of the invention, the present invention proposes technical solution below:
In above-mentioned preparation method, it is characterised in that: using cuprous bromide as catalyst, potassium peroxydisulfate is oxidant, di(2-ethylhexyl)phosphate
Hydrogen potassium is alkali, is with benzofuranone and its derivative I and quinoline amides II or indoles III or carbazole IV or thiophene V
Reaction raw materials, in acetonitrile solvent, 80 DEG C of effecting reactions can respectively obtain benzofuran triarylmethane within the time of 12h
Class compound A-D；Wherein benzofuranone and its derivative I, quinoline amides II, indoles III, carbazole IV, thiophene V, Yi Jisuo
The product structure formula of corresponding triarylmethane class compound A-D is as follows:
Wherein R1-R2It is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, methoxyl group, benzene
Base, fluorine, chlorine, bromine；R3It is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, vinyl, phenyl, benzyl
Base, furyl, thienyl, cyclopenta, cyclohexyl, trifluoromethyl, perfluorophenyl；R4It is selected from methyl, methoxyl group, phenyl, ester
Base, amino, cyano, fluorine, chlorine, bromine；R5It is selected from hydrogen, bromine, aldehyde radical；R6It is selected from hydrogen, ethyl, pyridyl group；R7Be selected from methyl,
Phenyl；
In above-mentioned preparation method, which is characterized in that the solvent is acetonitrile, and oxidant is potassium peroxydisulfate, and alkali is di(2-ethylhexyl)phosphate
Hydrogen potassium.
In above-mentioned preparation method, which is characterized in that the dosage of the catalyst is 10mol%, and the reaction time is
12h, reaction temperature are 80 DEG C.
Method provided by the present invention opens a new economy for the preparation of novel triarylmethane class compound
" green " approach, the advantage is that: cost of material is low, green catalyst, yield is higher, and experimental implementation is easy, without harmful by-product
Object generates, environmentally protective.
[Detailed description of the invention]
It is the route map provided by the present invention for preparing novel triarylmethane class compound shown in attached drawing.
[specific embodiment]
The synthesis road provided by the present invention that novel triarylmethane class compound is prepared using cuprous bromide as catalyst
Line refers to attached drawing 1: by benzofuranone and its derivative 0.24mmol, heterocyclic aromatic compounds (quinoline, indoles, carbazole or
Thiophene) 0.2mmol be added 10mL reaction tube in, the cuprous bromide of 10mol%, the potassium peroxydisulfate of 0.4mmol, 0.4mmol is added
Potassium dihydrogen phosphate and 2mL acetonitrile, effecting reaction 12h in the environment of 80 DEG C obtains target compound triarylmethane class
Compound.
Below with reference to specific preparation example, the present invention will be further described:
Preparation example 1
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=tert-butyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=tert-butyl), obtain white solid, yield 75%.
Preparation example 2
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=isopropyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=isopropyl), obtain white solid, yield 46%.
Preparation example 3
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=methyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and second
Nitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- methyl, R2
=H, R3=methyl), obtain white solid, yield 66%.
Preparation example 4
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=n-pentyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=n-pentyl), obtain white solid, yield 62%.
Preparation example 5
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=n-hexyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=n-hexyl), obtain white solid, yield 69%.
Preparation example 6
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=cyclopenta) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=cyclopenta), obtain white solid, yield 77%.
Preparation example 7
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=cyclohexyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=cyclohexyl), obtain white solid, yield 66%.
Preparation example 8
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=trifluoromethyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=trifluoromethyl), obtain white solid, yield 71%.
Preparation example 9
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=phenyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and second
Nitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- methyl, R2
=H, R3=phenyl), obtain white solid, yield 42%.
Preparation example 10
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=p-methylphenyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=p-methylphenyl), obtain white solid, yield 49%.
Preparation example 11
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=tolyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=tolyl), obtain white solid, yield 60%.
Preparation example 12
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=o-tolyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=o-tolyl), obtain white solid, yield 50%.
Preparation example 13
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=p-fluorophenyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=p-fluorophenyl), obtain white solid, yield 49%.
Preparation example 14
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=rubigan) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=rubigan), obtain white solid, yield 62%.
Preparation example 15
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=p-bromophenyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=p-bromophenyl), obtain white solid, yield 66%.
Preparation example 16
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=perfluorophenyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=perfluorophenyl), obtain white solid, yield 58%.
Preparation example 17
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=benzyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and second
Nitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- methyl, R2
=H, R3=benzyl), obtain white solid, yield 59%.
Preparation example 18
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=allyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=allyl), obtain white solid, yield 32%.
Preparation example 19
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=thienyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=thienyl), obtain white solid, yield 63%.
Preparation example 20
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=furyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R3=furyl), obtain white solid, yield 50%.
Preparation example 21
Benzofuranone analog derivative (R is added in 10mL reaction tube1=H, R2=H) 0.24mmol and quinoline
(R3=tert-butyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and acetonitrile
2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=H, R2=H, R3
=tert-butyl), obtain white solid, yield 30%.
Preparation example 22
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methoxyl group, R2=H) 0.24mmol and quinoline
Derivative (R3=tert-butyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- first
Oxygroup, R2=H, R3=tert-butyl), obtain white solid, yield 52%.
Preparation example 23
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- ethyl, R2=H) 0.24mmol and quinoline spread out
Biology (R3=tert-butyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- second
Base, R2=H, R3=tert-butyl), obtain white solid, yield 70%.
Preparation example 24
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- isopropyl, R2=H) 0.24mmol and quinoline
Derivative (R3=tert-butyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4- is different
Propyl, R2=H, R3=tert-butyl), obtain white solid, yield 46%.
Preparation example 25
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=4-Br) 0.24mmol and quinoline
Quinoline derivant (R3=tert-butyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4-
Methyl, R2=4-Br, R3=tert-butyl), obtain white solid, yield 47%.
Preparation example 26
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=4-Cl) 0.24mmol and quinoline
Quinoline derivant (R3=tert-butyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound A (R is obtained through column chromatography for separation1=4-
Methyl, R2=4-Cl, R3=tert-butyl), obtain white solid, yield 56%.
Preparation example 27
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=5- methyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R4=5- methyl), obtain white solid, yield 65%.
Preparation example 28
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=6- methyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R4=6- methyl), obtain white solid, yield 55%.
Preparation example 29
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=7- methyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R4=7- methyl), obtain white solid, yield 26%.
Preparation example 30
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=2,5- dimethyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4-
Methyl, R2=H, R4=2,5- dimethyl), obtain white solid, yield 73%.
Preparation example 31
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=2- phenyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R4=2- phenyl), obtain white solid, yield 68%.
Preparation example 32
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=2- methyl formate base) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate
0.4mmol and acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B is obtained through column chromatography for separation
(R1=4- methyl, R2=H, R4=2- methyl formate base), obtain white solid, yield 41%.
Preparation example 33
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=5- methyl formate base) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate
0.4mmol and acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B is obtained through column chromatography for separation
(R1=4- methyl, R2=H, R4=5- methyl formate base), obtain white solid, yield 68%.
Preparation example 34
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=2- group-4 ethyl formate) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate
0.4mmol and acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B is obtained through column chromatography for separation
(R1=4- methyl, R2=H, R4=2- group-4 ethyl formate), obtain white solid, yield 56%.
Preparation example 35
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=5- methoxyl group) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R4=5- methoxyl group), obtain white solid, yield 39%.
Preparation example 36
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=5- amino) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R4=5- amino), obtain white solid, yield 58%.
Preparation example 37
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=5- cyano) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R4=5- cyano), obtain white solid, yield 58%.
Preparation example 38
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=5-F) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and second
Nitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4- methyl, R2
=H, R4=5-F), obtain white solid, yield 64%.
Preparation example 39
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=6-Cl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and second
Nitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4- methyl, R2
=H, R4=6-Cl), obtain white solid, yield 68%.
Preparation example 40
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=5-Br) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and second
Nitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4- methyl, R2
=H, R4=6-Br), obtain white solid, yield 68%.
Preparation example 41
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=3- aldehyde radical) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R4=3- aldehyde radical), obtain white solid, yield 34%.
Preparation example 42
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- ethyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=5- amino) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4- second
Base, R2=H, R4=5- amino), obtain white solid, yield 79%.
Preparation example 43
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- isopropyl, R2=H) 0.24mmol and indoles
Derivative (R4=5- amino) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4- is different
Propyl, R2=H, R4=5- amino), obtain white solid, yield 69%.
Preparation example 44
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- phenyl, R2=H) 0.24mmol and indoles spread out
Biology (R4=5- amino) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4- benzene
Base, R2=H, R4=5- amino), obtain white solid, yield 91%.
Preparation example 45
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4-F, R2=H) 0.24mmol and indoles be derivative
Object (R4=5- amino) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and second
Nitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4-F, R2=
H, R4=5- amino), obtain white solid, yield 85%.
Preparation example 46
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4-Cl, R2=H) 0.24mmol and indoles be derivative
Object (R4=5-Br) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and acetonitrile
2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4-Cl, R2=H,
R4=5-Br), obtain white solid, yield 83%.
Preparation example 47
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=4-Cl) 0.24mmol and Yin
Diindyl derivative (R4=5- amino) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4-
Methyl, R2=4-Cl, R4=5- amino), obtain white solid, yield 65%.
Preparation example 48
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=4-Br) 0.24mmol and Yin
Diindyl derivative (R4=5- amino) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=4-
Methyl, R2=4-Br, R4=5- amino), obtain white solid, yield 77%.
Preparation example 49
Benzofuranone analog derivative (R is added in 10mL reaction tube1=2- tert-butyl, R2=H) 0.24mmol and indoles
Derivative (R4=5- amino) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound B (R is obtained through column chromatography for separation1=uncle 2-
Butyl, R2=H, R4=5- amino), obtain white solid, yield 75%.
Preparation example 50
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and carbazole spread out
Biology (R5=H, R6=H) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound C (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R5=H, R6=H), obtain white solid, yield 33%.
Preparation example 51
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and carbazole spread out
Biology (R5=3-Br, R6=H) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound C (R is obtained through column chromatography for separation1=4-
Methyl, R2=H, R5=3-Br, R6=H), obtain white solid, yield 53%.
Preparation example 52
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and carbazole spread out
Biology (R5=H, R6=ethyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound C (R is obtained through column chromatography for separation1=4-
Methyl, R2=H, R5=H, R6=ethyl), obtain white solid, yield 37%.
Preparation example 53
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and carbazole spread out
Biology (R5=H, R6=pyridyl group) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate
0.4mmol and acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound C is obtained through column chromatography for separation
(R1=4- methyl, R2=H, R5=H, R6=pyridyl group), obtain white solid, yield 40%.
Preparation example 54
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and carbazole spread out
Biology (R5=2- aldehyde radical, R6=ethyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate
0.4mmol and acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound C is obtained through column chromatography for separation
(R1=4- methyl, R2=H, R5=2- aldehyde radical, R6=ethyl), obtain white solid, yield 35%.
Preparation example 55
Benzofuranone analog derivative (R is added in 10mL reaction tube1=H, R2=H) 0.24mmol and carbazole derivates
(R5=H, R6=H) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and acetonitrile
2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound C (R is obtained through column chromatography for separation1=H, R2=H, R5
=H, R6=H), obtain white solid, yield 24%.
Preparation example 56
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4-Cl, R2=H) 0.24mmol and carbazole be derivative
Object (R5=H, R6=H) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and second
Nitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound C (R is obtained through column chromatography for separation1=4-Cl, R2=
H, R5=H, R6=H), obtain white solid, yield 27%.
Preparation example 57
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- ethyl, R2=H) 0.24mmol and carbazole spread out
Biology (R5=H, R6=H) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound C (R is obtained through column chromatography for separation1=4- second
Base, R2=H, R5=H, R6=H), obtain white solid, yield 50%.
Preparation example 58
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methoxyl group, R2=H) 0.24mmol and carbazole
Derivative (R5=H, R6=H) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound C (R is obtained through column chromatography for separation1=4- first
Oxygroup, R2=H, R5=H, R6=H), obtain white solid, yield 59%.
Preparation example 59
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- phenyl, R2=H) 0.24mmol and carbazole spread out
Biology (R5=H, R6=H) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound C (R is obtained through column chromatography for separation1=4- benzene
Base, R2=H, R5=H, R6=H), obtain white solid, yield 59%.
Preparation example 60
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- isopropyl, R2=H) 0.24mmol and carbazole
Derivative (R5=H, R6=H) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound C (R is obtained through column chromatography for separation1=4- is different
Propyl, R2=H, R5=H, R6=H), obtain white solid, yield 54%.
Preparation example 61
Benzofuranone analog derivative (R is added in 10mL reaction tube1=2- tert-butyl, R2=H) 0.24mmol and carbazole
Derivative (R5=H, R6=H) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound C (R is obtained through column chromatography for separation1=uncle 2-
Butyl, R2=H, R5=H, R6=H), obtain white solid, yield 24%.
Preparation example 62
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=4-Cl) 0.24mmol and click
Zole derivatives (R5=H, R6=H) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound C (R is obtained through column chromatography for separation1=4-
Methyl, R2=4-Cl, R5=H, R6=H), obtain white solid, yield 48%.
Preparation example 63
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=4-Br) 0.24mmol and click
Zole derivatives (R5=H, R6=H) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound C (R is obtained through column chromatography for separation1=4-
Methyl, R2=4-Br, R5=H, R6=H), obtain white solid, yield 45%.
Preparation example 64
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and thiophene spread out
Biology (R7=2- methyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound D (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R7=2- methyl), obtain white solid, yield 73%.
Preparation example 65
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=H) 0.24mmol and thiophene spread out
Biology (R7=2- phenyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound D (R is obtained through column chromatography for separation1=4- first
Base, R2=H, R7=2- phenyl), obtain white solid, yield 64%.
Preparation example 66
Benzofuranone analog derivative (R is added in 10mL reaction tube1=H, R2=H) 0.24mmol and thiophene derivant
(R7=2- methyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and acetonitrile
2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound D (R is obtained through column chromatography for separation1=H, R2=H, R7
=2- methyl), obtain white solid, yield 30%.
Preparation example 67
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- ethyl, R2=H) 0.24mmol and thiophene spread out
Biology (R7=2- methyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound D (R is obtained through column chromatography for separation1=4- second
Base, R2=H, R7=2- methyl), obtain white solid, yield 60%.
Preparation example 68
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- isopropyl, R2=H) 0.24mmol and thiophene
Derivative (R7=2- methyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol with
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound D (R is obtained through column chromatography for separation1=4- is different
Propyl, R2=H, R7=2- methyl), obtain white solid, yield 67%.
Preparation example 69
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- phenyl, R2=H) 0.24mmol and thiophene spread out
Biology (R7=2- methyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol and
Acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound D (R is obtained through column chromatography for separation1=4- benzene
Base, R2=H, R7=2- methyl), obtain white solid, yield 61%.
Preparation example 70
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=4-Cl) 0.24mmol and thiophene
Pheno derivative (R7=2- methyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound D (R is obtained through column chromatography for separation1=4-
Methyl, R2=4-Cl, R7=2- methyl), obtain white solid, yield 66%.
Preparation example 71
Benzofuranone analog derivative (R is added in 10mL reaction tube1=4- methyl, R2=4-Br) 0.24mmol and thiophene
Pheno derivative (R7=2- methyl) 0.2mmol, cuprous bromide 10mol%, potassium peroxydisulfate 0.4mmol, potassium dihydrogen phosphate 0.4mmol
And acetonitrile 2mL, reaction carry out 12h at 80 DEG C.After reaction, target compound D (R is obtained through column chromatography for separation1=4-
Methyl, R2=4-Br, R7=2- methyl), obtain white solid, yield 39%.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (3)
1. one kind benzofuran triarylmethane class compound A-D and its synthetic method, wherein compound A-D structural formula is as follows:
The wherein R1-R2It is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, methoxyl group, benzene
Base, fluorine, chlorine, bromine；R3It is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, vinyl, phenyl, benzyl
Base, furyl, thienyl, cyclopenta, cyclohexyl, trifluoromethyl, perfluorophenyl；R4 is selected from methyl, methoxyl group, phenyl, ester
Base, amino, cyano, fluorine, chlorine, bromine；R5It is selected from hydrogen, bromine, aldehyde radical；R6It is selected from hydrogen, ethyl, pyridyl group；R7Be selected from methyl,
Phenyl；
The wherein green catalysis synthetic method of compound A-D, which is characterized in that using cuprous bromide as catalyst, potassium peroxydisulfate is oxygen
Agent, potassium dihydrogen phosphate are alkali, with benzofuranone and its derivative I and quinoline amides II or indoles III or carbazole IV
Or thiophene V is reaction raw materials, in acetonitrile solvent, 80 DEG C of effecting reactions can respectively obtain higher yields within the time of 12h
Benzofuran triarylmethane class compound A-D.
2. synthetic method according to claim 1, wherein benzofuranone and its derivative I, quinoline amides II, indoles
III, carbazole IV, thiophene V structure formula are as follows:
The wherein R1-R2It is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, methoxyl group, benzene
Base, fluorine, chlorine, bromine；R3It is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, vinyl, phenyl, benzyl
Base, furyl, thienyl；R4 is selected from methyl, methoxyl group, phenyl, ester group, amino, cyano, fluorine, chlorine, bromine；R5Be selected from hydrogen,
Bromine, aldehyde radical；R6It is selected from hydrogen, ethyl, pyridyl group；R7It is selected from methyl, phenyl.
3. synthetic method according to claim 1, which is characterized in that raw materials used benzofuranone and its derivative I and
The ratio of heterocyclic aromatic compounds II-V is 1.2:1；The dosage of catalyst is 10mol%；Oxidizer is 2 equivalents, and alkali is used
Amount is 2 equivalents, and the organic solvent is acetonitrile；The reaction time is 12h, and reaction temperature is 80 DEG C.
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