CN106083534B - A kind of method of the aryl boric acid phenol of visible light catalytic - Google Patents

A kind of method of the aryl boric acid phenol of visible light catalytic Download PDF

Info

Publication number
CN106083534B
CN106083534B CN201610541705.3A CN201610541705A CN106083534B CN 106083534 B CN106083534 B CN 106083534B CN 201610541705 A CN201610541705 A CN 201610541705A CN 106083534 B CN106083534 B CN 106083534B
Authority
CN
China
Prior art keywords
boric acid
visible light
mmol
ethyl acetate
phenol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201610541705.3A
Other languages
Chinese (zh)
Other versions
CN106083534A (en
Inventor
刘春�
于洪翠
戴晓枚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian University of Technology
Original Assignee
Dalian University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian University of Technology filed Critical Dalian University of Technology
Priority to CN201610541705.3A priority Critical patent/CN106083534B/en
Publication of CN106083534A publication Critical patent/CN106083534A/en
Application granted granted Critical
Publication of CN106083534B publication Critical patent/CN106083534B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles 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 to carbon atoms of the ring system

Abstract

A kind of method of the aryl boric acid phenol of visible light catalytic, belongs to technical field of organic synthesis.The preparation method is in the presence of room temperature, air and visible light and amine, and using complex of iridium or platinum complex as catalyst, aryl boric acid occurs oxidation hydroxylating and generates phenolic compound.This method has the characteristics that Atom economy is good, reaction condition is mild and easy to operate using the oxygen in air as oxidant.This method enriches the synthetic method of phenolic compound, and the synthesis of in particular big conjugation phenolic compound provides a simplicity, efficient method.

Description

A kind of method of the aryl boric acid phenol of visible light catalytic
Technical field
The present invention relates to technical field of organic synthesis, the more particularly to method of the big conjugation phenolic compound of synthesis.
Background technology
Phenolic compound is important Organic Chemicals, it can also be used as medicine, the raw material of dyestuff, preservative In production arylamine, caprolactam, alkyl phenol, the products such as aliphatic acid.In addition, it can also be widely used in oxygen heterocycle chemical combination Object synthesis (Synthetic and natural phenols, Elsevier, 1996, 52).In recent years, with phenol generalization The growth of object demand is closed, people constantly explore its synthetic method.However, the method for existing synthesis phenolic compound is still deposited centainly Deficiency, such as：High-temperature high-voltage reaction condition is needed, preparation process is complicated, and atom utilization is relatively low, strong acid and strong base etching apparatus, The more grade of by-product (The Chemistry of Phenols, John Wiley & Sons, 2004, 5;Fine chemistry industry is former Material and intermediate, 2010,5,35-41).These problems significantly limit the application of phenolic compound.
Visible light catalytic is considered as a kind of new and effective methodology of organic synthesis, is the ideal chose of green catalysis (Chem. Rev., 2013, 113, 5322-5363;Science,2014, 343, 1239176; Inorg. Chem. Front., 2014, 1, 562-576; Acc. Chem. Res., 2016, 49, 1320-1330).In recent years, metal has The fast-developing of chemical machine also brings opportunity for the research of visible light catalytic.
Invention content
The object of the present invention is to provide a kind of methods of the aryl boric acid phenol of visible light catalytic, in the item of visible light-inducing Under part, using complex of iridium or the redox characteristic of platinum complex, it converts boric acid base group in aryl boric acid to the anti-of hydroxyl It answers, to enrich the synthetic method of phenolic compound, the synthetic method of especially big conjugation phenolic compound.
The technical solution adopted by the present invention is：0.5 mmol aryl boric acids, 2 mol% complex of iridium or platinum are coordinated successively Object, 1.0 mmol amine and 4 mL solvents are added in reaction bulb.7 ~ 12 h are reacted under room temperature, air and visible light conditions, use is thin Layer chromatography tracks reaction process, after reaction, 15 mL saturated salt solutions, 15 mL ethyl acetate of reaction mixture is added Extraction 3 times, merges organic phase, and concentration uses column chromatography, obtains phenolic compound.
In above-mentioned preparation method, the aryl boric acid be selected from 1- naphthalene boronic acids, 2- naphthalene boronic acids, 3,5- diphenyl benzenes boric acid, （10- phenylanthracene -9- bases）Boric acid, 4- (diphenylamino) phenyl boric acid, 4- (9H- carbazole -9- bases) phenyl boric acids or N- phenyl -3- carbazoles Boric acid.
In above-mentioned preparation method, Ir0, Ir1 in following structures of the complex of iridium and platinum complex, Ir2, Ir3, Pt0, Pt1, Pt2 or Pt3, the synthetic method of the series compound is in Dalton Transactions 2016,45,734- 741 and Journal of Materials Chemistry C, 2015,3,2166-2174 deliver, and structure is as follows：
In above-mentioned preparation method, the amine is selected from triethylamine, diisopropylethylamine or diisopropylamine.
In above-mentioned preparation method, the solvent is selected from n,N-Dimethylformamide, acetonitrile, tetrahydrofuran, toluene or ethyl alcohol.
Serial number Aryl boric acid Catalyst Amine Solvent Yield %
1 3,5- diphenyl benzene boric acid Ir0 Triethylamine N,N-dimethylformamide 74
2 3,5- diphenyl benzene boric acid Ir0 Diisopropylethylamine N,N-dimethylformamide 70
3 3,5- diphenyl benzene boric acid Ir0 Diisopropylamine N,N-dimethylformamide 60
4 3,5- diphenyl benzene boric acid Ir0 Triethylamine Acetonitrile 65
5 3,5- diphenyl benzene boric acid Ir0 Triethylamine Tetrahydrofuran 68
6 3,5- diphenyl benzene boric acid Ir0 Triethylamine Toluene 70
7 3,5- diphenyl benzene boric acid Ir0 Triethylamine Ethyl alcohol 72
8 3,5- diphenyl benzene boric acid Ir1 Triethylamine N,N-dimethylformamide 85
9 3,5- diphenyl benzene boric acid Ir2 Triethylamine N,N-dimethylformamide 88
10 3,5- diphenyl benzene boric acid Ir3 Triethylamine N,N-dimethylformamide 82
11 3,5- diphenyl benzene boric acid Pt0 Triethylamine N,N-dimethylformamide 64
12 3,5- diphenyl benzene boric acid Pt1 Triethylamine N,N-dimethylformamide 75
13 3,5- diphenyl benzene boric acid Pt2 Triethylamine N,N-dimethylformamide 86
14 3,5- diphenyl benzene boric acid Pt3 Triethylamine N,N-dimethylformamide 72
15 （10- phenylanthracene -9- bases）Boric acid Ir2 Triethylamine N,N-dimethylformamide 80
16 （10- phenylanthracene -9- bases）Boric acid Pt2 Diisopropylethylamine N,N-dimethylformamide 76
17 4- (diphenylamino) phenyl boric acid Ir2 Triethylamine N,N-dimethylformamide 83
18 4- (diphenylamino) phenyl boric acid Pt2 Diisopropylethylamine N,N-dimethylformamide 73
19 4- (9H- carbazole -9- bases) phenyl boric acid Ir2 Triethylamine N,N-dimethylformamide 87
20 4- (9H- carbazole -9- bases) phenyl boric acid Pt2 Diisopropylethylamine N,N-dimethylformamide 88
21 N- phenyl -3- carbazole boric acid Ir2 Triethylamine N,N-dimethylformamide 95
22 N- phenyl -3- carbazole boric acid Pt2 Diisopropylethylamine N,N-dimethylformamide 85
Beneficial effects of the present invention：The preparation method is in the presence of room temperature, air and visible light and amine, with complex of iridium Or platinum complex is catalyst, aryl boric acid occurs oxidation hydroxylating and generates phenolic compound.This method is in air Oxygen is oxidant, has the characteristics that Atom economy is good, reaction condition is mild and easy to operate.This method enriches phenol generalization The synthetic method of object is closed, the synthesis of in particular big conjugation phenolic compound provides a simplicity, efficient method.
Specific implementation mode
Embodiment 1 synthesizes 3,5- diphenyl phenol
3,5- diphenyl benzene boric acid is sequentially added into reaction bulb（0.5 mmol）, triethylamine（1.0 mmol）, complex Ir0（2 mol%）With 4 mL N,N-dimethylformamides.It is reacted under room temperature, air and visible light conditions, reaction process is by thin layer Chromatography tracks.After the completion of reaction, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, Concentration, using petroleum ether and ethyl acetate as eluant, eluent, through column chromatography for separation, obtains target product 3,5- diphenyl phenol, yield 74%, product structure passes through1H NMR、13C NMR and Mass Spectrometric Identification.
Embodiment 2 synthesizes 3,5- diphenyl phenol
3,5- diphenyl benzene boric acid is sequentially added into reaction bulb（0.5 mmol）, diisopropylethylamine（1.0 mmol）、 Complex Ir0（2 mol%）With 4 mL N,N-dimethylformamides.It is reacted under room temperature, air and visible light conditions, reaction process It is tracked by thin-layered chromatography.After the completion of reaction, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges Organic phase, concentration, using petroleum ether and ethyl acetate as eluant, eluent, through column chromatography for separation, obtains target product 3,5- diphenyl benzenes Phenol, yield 70%.
Embodiment 3 synthesizes 3,5- diphenyl phenol
3,5- diphenyl benzene boric acid is sequentially added into reaction bulb（0.5 mmol）, diisopropylamine（1.0 mmol）, match Close object Ir0（2 mol%）With 4 mL N,N-dimethylformamides.Reacted under room temperature, air and visible light conditions, reaction process by Thin-layered chromatography tracks.After the completion of reaction, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction, is associated with Machine phase, concentration through column chromatography for separation, obtain target product 3 using petroleum ether and ethyl acetate as eluant, eluent, 5- diphenyl phenol, Yield 60%.
Embodiment 4 synthesizes 3,5- diphenyl phenol
3,5- diphenyl benzene boric acid is sequentially added into reaction bulb（0.5 mmol）, triethylamine（1.0 mmol）, complex Ir0（2 mol%）With 4 mL acetonitriles.It is reacted under room temperature, air and visible light conditions, reaction process is tracked by thin-layered chromatography. After the completion of reaction, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, concentration, with oil Ether and ethyl acetate are that eluant, eluent obtains target product 3,5- diphenyl phenol, yield 65% through column chromatography for separation.
Embodiment 5 synthesizes 3,5- diphenyl phenol
3,5- diphenyl benzene boric acid is sequentially added into reaction bulb（0.5 mmol）, triethylamine（1.0 mmol）, complex Ir0（2 mol%）With 4 mL tetrahydrofurans.Reacted under room temperature, air and visible light conditions, reaction process by thin-layered chromatography with Track.After the completion of reaction, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, concentrates, with Petroleum ether and ethyl acetate are that eluant, eluent obtains target product 3,5- diphenyl phenol, yield 68% through column chromatography for separation.
Embodiment 6 synthesizes 3,5- diphenyl phenol
3,5- diphenyl benzene boric acid is sequentially added into reaction bulb（0.5 mmol）, triethylamine（1.0 mmol）, complex Ir0（2 mol%）With 4 mL toluene.It is reacted under room temperature, air and visible light conditions, reaction process is tracked by thin-layered chromatography. After the completion of reaction, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, concentration, with oil Ether and ethyl acetate are that eluant, eluent obtains target product 3,5- diphenyl phenol, yield 70% through column chromatography for separation.
Embodiment 7 synthesizes 3,5- diphenyl phenol
3,5- diphenyl benzene boric acid is sequentially added into reaction bulb（0.5 mmol）, triethylamine（1.0 mmol）, complex Ir0（2 mol%）With 4 mL ethyl alcohol.It is reacted under room temperature, air and visible light conditions, reaction process is tracked by thin-layered chromatography. After the completion of reaction, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, concentration, with oil Ether and ethyl acetate are that eluant, eluent obtains target product 3,5- diphenyl phenol, yield 72% through column chromatography for separation.
Embodiment 8 synthesizes 3,5- diphenyl phenol
3,5- diphenyl benzene boric acid is sequentially added into reaction bulb（0.5 mmol）, triethylamine（1.0 mmol）, complex Ir1（2 mol%）With 4 mL N,N-dimethylformamides.It is reacted under room temperature, air and visible light conditions, reaction process is by thin layer Chromatography tracks.After the completion of reaction, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, Concentration, using petroleum ether and ethyl acetate as eluant, eluent, through column chromatography for separation, obtains target product 3,5- diphenyl phenol, yield 85%。
Embodiment 9 synthesizes 3,5- diphenyl phenol
3,5- diphenyl benzene boric acid is sequentially added into reaction bulb（0.5 mmol）, triethylamine（1.0 mmol）, complex Ir2（2 mol%）With 4 mL N,N-dimethylformamides.It is reacted under room temperature, air and visible light conditions, reaction process is by thin layer Chromatography tracks.After the completion of reaction, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, Concentration, using petroleum ether and ethyl acetate as eluant, eluent, through column chromatography for separation, obtains target product 3,5- diphenyl phenol, yield 88%。
Embodiment 10 synthesizes 3,5- diphenyl phenol
3,5- diphenyl benzene boric acid is sequentially added into reaction bulb（0.5 mmol）, triethylamine（1.0 mmol）, complex Ir3（2 mol%）With 4 mL N,N-dimethylformamides.It is reacted under room temperature, air and visible light conditions, reaction process is by thin layer Chromatography tracks.After the completion of reaction, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, Concentration, using petroleum ether and ethyl acetate as eluant, eluent, through column chromatography for separation, obtains target product 3,5- diphenyl phenol, yield 82%。
Embodiment 11 synthesizes 3,5- diphenyl phenol
3,5- diphenyl benzene boric acid is sequentially added into reaction bulb（0.5 mmol）, triethylamine（1.0 mmol）, complex Pt0（2 mol%）With 4 mL N,N-dimethylformamides.It is reacted under room temperature, air and visible light conditions, reaction process is by thin layer Chromatography tracks.After the completion of reaction, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, Concentration, using petroleum ether and ethyl acetate as eluant, eluent, through column chromatography for separation, obtains target product 3,5- diphenyl phenol, yield 64%。
Embodiment 12 synthesizes 3,5- diphenyl phenol
3,5- diphenyl benzene boric acid is sequentially added into reaction bulb（0.5 mmol）, triethylamine（1.0 mmol）, complex Pt1（2 mol%）With 4 mL N,N-dimethylformamides.It is reacted under room temperature, air and visible light conditions, reaction process is by thin layer Chromatography tracks.After the completion of reaction, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, Concentration, using petroleum ether and ethyl acetate as eluant, eluent, through column chromatography for separation, obtains target product 3,5- diphenyl phenol, yield 75%。
Embodiment 13 synthesizes 3,5- diphenyl phenol
3,5- diphenyl benzene boric acid is sequentially added into reaction bulb（0.5 mmol）, triethylamine（1.0 mmol）, complex Pt2（2 mol%）With 4 mL N,N-dimethylformamides.It is reacted under room temperature, air and visible light conditions, reaction process is by thin layer Chromatography tracks.After the completion of reaction, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, Concentration, using petroleum ether and ethyl acetate as eluant, eluent, through column chromatography for separation, obtains target product 3,5- diphenyl phenol, yield 86%。
Embodiment 14 synthesizes 3,5- diphenyl phenol
3,5- diphenyl benzene boric acid is sequentially added into reaction bulb（0.5 mmol）, triethylamine（1.0 mmol）, complex Pt3（2 mol%）With 4 mL N,N-dimethylformamides.It is reacted under room temperature, air and visible light conditions, reaction process is by thin layer Chromatography tracks.After the completion of reaction, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, Concentration, using petroleum ether and ethyl acetate as eluant, eluent, through column chromatography for separation, obtains target product 3,5- diphenyl phenol, yield 72%。
Embodiment 15 synthesizes 10- phenyl -9- anthrols
It is sequentially added into reaction bulb（10- phenylanthracene -9- bases）Boric acid（0.5 mmol）, triethylamine（1.0 mmol）, match Close object Ir2（2 mol%）With 4 mL DMF.Reacted under room temperature, air and visible light conditions, reaction process by thin-layered chromatography with Track.After the reaction was complete, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, concentrates, with Petroleum ether and ethyl acetate are that eluant, eluent obtains target product 10- phenyl -9- anthrols, yield 80%, product through column chromatography for separation Structure passes through1H NMR、13C NMR and Mass Spectrometric Identification.
Embodiment 16 synthesizes 10- phenyl -9- anthrols
It is sequentially added into reaction bulb（10- phenylanthracene -9- bases）Boric acid（0.5 mmol）, diisopropylethylamine（1.0 mmol）, complex Pt2（2 mol%）With 4 mL DMF.It is reacted under room temperature, air and visible light conditions, reaction process is by thin layer Chromatography tracks.After the reaction was complete, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, Concentration, using petroleum ether and ethyl acetate as eluant, eluent, through column chromatography for separation, obtains target product 10- phenyl -9- anthrols, yield 76%。
Embodiment 17 synthesizes 4- (diphenylamino) phenol
4- (diphenylamino) phenyl boric acid is sequentially added into reaction bulb（0.5 mmol）, triethylamine（1.0 mmol）, cooperation Object Ir2（2 mol%）With 4 mL DMF.It is reacted under room temperature, air and visible light conditions, reaction process is tracked by thin-layered chromatography. After the reaction was complete, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, concentration, with oil Ether and ethyl acetate are that eluant, eluent obtains target product 4- (diphenylamino) phenol, yield 83%, product knot through column chromatography for separation Structure passes through1H NMR、13C NMR and Mass Spectrometric Identification.
Embodiment 18 synthesizes 4- (diphenylamino) phenol
4- (diphenylamino) phenyl boric acid is sequentially added into reaction bulb（0.5 mmol）, diisopropylethylamine（1.0 mmol）, complex Pt2（2 mol%）With 4 mL DMF.It is reacted under room temperature, air and visible light conditions, reaction process is by thin layer Chromatography tracks.After the reaction was complete, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, Concentration, using petroleum ether and ethyl acetate as eluant, eluent, through column chromatography for separation, obtains target product 4- (diphenylamino) phenol, produces Rate 73%.
Embodiment 19 synthesizes 4- (9H- carbazole -9- bases) phenol
4- (9H- carbazole -9- bases) phenyl boric acid is sequentially added into reaction bulb（0.5 mmol）, triethylamine（1.0 mmol）、 Complex Ir2（2 mol%）With 4 mL DMF.It is reacted under room temperature, air and visible light conditions, reaction process is by thin-layered chromatography Tracking.After the reaction was complete, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, concentrates, Using petroleum ether and ethyl acetate as eluant, eluent, through column chromatography for separation, target product 4- (9H- carbazole -9- bases) phenol, yield are obtained 87%, product structure passes through1H NMR、13C NMR and Mass Spectrometric Identification.
Embodiment 20 synthesizes 4- (9H- carbazole -9- bases) phenol
4- (9H- carbazole -9- bases) phenyl boric acid is sequentially added into reaction bulb（0.5 mmol）, diisopropylethylamine（1.0 mmol）, complex Pt2（2 mol%）With 4 mL DMF.It is reacted under room temperature, air and visible light conditions, reaction process is by thin layer Chromatography tracks.After the reaction was complete, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, Concentration, using petroleum ether and ethyl acetate as eluant, eluent, through column chromatography for separation, obtains target product 4- (9H- carbazole -9- bases) benzene Phenol, yield 88%.
Embodiment 21 synthesizes (9- phenyl -9H- carbazole -3- bases) phenol
N- phenyl -3- carbazole boric acid is sequentially added into reaction bulb（0.5 mmol）, triethylamine（1.0 mmol）, complex Ir2（2 mol%）With 4 mL DMF.It is reacted under room temperature, air and visible light conditions, reaction process is tracked by thin-layered chromatography.Instead After answering completely, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, concentration, with petroleum ether It is eluant, eluent with ethyl acetate, through column chromatography for separation, obtains target product (9- phenyl -9H- carbazole -3- bases) phenol, yield 95%, Product structure passes through1H NMR、13C NMR and Mass Spectrometric Identification.
Embodiment 22 synthesizes (9- phenyl -9H- carbazole -3- bases) phenol
N- phenyl -3- carbazole boric acid is sequentially added into reaction bulb（0.5 mmol）, diisopropylethylamine（1.0 mmol）、 Complex Pt2（2 mol%）With 4 mL DMF.It is reacted under room temperature, air and visible light conditions, reaction process is by thin-layered chromatography Tracking.After the reaction was complete, 15 mL of saturated salt solution is added, uses ethyl acetate（3*15 mL）Extraction merges organic phase, concentrates, Using petroleum ether and ethyl acetate as eluant, eluent, through column chromatography for separation, target product (9- phenyl -9H- carbazole -3- bases) phenol is obtained, Yield 85%.
The above content is combine optimal technical scheme to the present invention do further description, and it cannot be said that the present invention Specific implementation is only limitted to these explanations.For general technical staff of the technical field of the invention, the present invention is not being departed from Design under the premise of made by changes, modifications, substitutions, combinations, simplifications, should be equivalent substitute mode, all should be considered as Protection scope of the present invention.

Claims (2)

1. a kind of method of the aryl boric acid phenol of visible light catalytic, which is characterized in that include the following steps：In reaction bulb successively N- phenyl -3- carbazoles boric acid, the triethylamine of 1.0 mmol, 2 mol% complexs Ir2 and the 4 mL DMF of 0.5 mmol are added；
The structure of the complex Ir2 is：；
It is reacted under room temperature, air and visible light conditions；After the reaction was complete, 15 mL of saturated salt solution is added, is extracted with ethyl acetate It takes, merges organic phase, concentration using petroleum ether and ethyl acetate as eluant, eluent, through column chromatography for separation, obtains target product (9- benzene Base -9H- carbazole -3- bases) phenol.
2. a kind of method of the aryl boric acid phenol of visible light catalytic, which is characterized in that include the following steps：Into reaction bulb according to The complex of secondary 4- (9H- carbazole -9- bases) phenyl boric acid that 0.5 mmol is added, the diisopropylethylamine of 1.0 mmol, 2 mol% Pt2 and 4 mL DMF；
The structure of the complex Pt2 is：；
It is reacted under room temperature, air and visible light conditions, after the reaction was complete, 15 mL of saturated salt solution is added, is extracted with ethyl acetate It takes, merges organic phase, concentration using petroleum ether and ethyl acetate as eluant, eluent, through column chromatography for separation, obtains target product 4- (9H- Carbazole -9- bases) phenol.
CN201610541705.3A 2016-07-12 2016-07-12 A kind of method of the aryl boric acid phenol of visible light catalytic Expired - Fee Related CN106083534B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610541705.3A CN106083534B (en) 2016-07-12 2016-07-12 A kind of method of the aryl boric acid phenol of visible light catalytic

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610541705.3A CN106083534B (en) 2016-07-12 2016-07-12 A kind of method of the aryl boric acid phenol of visible light catalytic

Publications (2)

Publication Number Publication Date
CN106083534A CN106083534A (en) 2016-11-09
CN106083534B true CN106083534B (en) 2018-09-04

Family

ID=57219612

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610541705.3A Expired - Fee Related CN106083534B (en) 2016-07-12 2016-07-12 A kind of method of the aryl boric acid phenol of visible light catalytic

Country Status (1)

Country Link
CN (1) CN106083534B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110668921A (en) * 2019-08-27 2020-01-10 温州大学 Method for preparing alcohol and phenol by aerobic hydroxylation reaction of boric acid derivative under condition of no photocatalyst
CN114016060B (en) * 2021-11-23 2023-05-02 南昌大学 Synthetic method of phenolic compound

Also Published As

Publication number Publication date
CN106083534A (en) 2016-11-09

Similar Documents

Publication Publication Date Title
CN105585473B (en) A kind of method for preparing propine acid compounds
Busto et al. Optically active macrocyclic hexaazapyridinophanes decorated at the periphery: synthesis and applications in the NMR enantiodiscrimination of carboxylic acids
Ibis et al. Synthesis of novel 1, 4-naphthoquinone derivatives: Antibacterial and antifungal agents
CN106083534B (en) A kind of method of the aryl boric acid phenol of visible light catalytic
US20170247352A1 (en) Method for preparing alectinib
CN105418678B (en) A kind of preparation method of Tedizolid Phosphate
CN110041222B (en) Thymoquinone derivative, intermediate, preparation method and application thereof
Kidwai et al. First time reported enzymatic synthesis of new series of quinoxalines—A green approach
Bhatra et al. Synthesis, characterization and antimicrobial activity of triorganotin (IV) derivatives of some bioactive Schiff base ligands
CN115197200B (en) Trifluoromethyl tertiary alcohol and synthetic method and application thereof
WO2023001124A1 (en) Use of chiral bisphosphonate diamine compound
Li et al. Synthesis and characterization of novel organonickel and organocobalt complexes via carbon–chlorine bond activation
CN105503864A (en) Preparing method for moxifloxacin intermediate
Sawant et al. Synthesis and characterization of transition metal complexes of novel Schiff base 8-[(z)-[3-(n-methylamino) propyl] iminomethyl]-7-hydroxy-4-methyl-2h-chromen-2-one][nmapimhmc] and their biological activities
CN112480004B (en) 5-trifluoromethyl substituted pyrazole derivative and synthesis method and application thereof
CN108358923B (en) Sophoridine pyrrole and indole derivatives, and preparation method and application thereof
Yaul et al. Synthesis, structural studies and biological activity of dioxomolybdenum (VI), dioxotungsten (VI), thorium (IV) and dioxouranium (VI) complexes with 2-hydroxy-5-methyl and 2-hydroxy-5-chloroacetophenone benzoylhydrazone
CN111675659A (en) Synthesis method of (5-fluoropyrimidine-4-yl) methanol
EP3476828B1 (en) Method for producing iron complexes and method for producing ester compounds using iron complex
CN112094237A (en) Synthesis method of fluorobenzene imidazole
CN103992280B (en) A kind of preparation method of iron catalysis microwave synthesis 4- amido quinazoline urea derivative
Kim et al. Enantiomeric recognition of d-and l-amino acid methyl ester hydrochlorides by new chiral bis-pyridino-18-crown-6 substituted with urea, and diphenyl groups
CN102675204B (en) Intermediate for synthesizing (I)-huperzine A, synthesis method and usage thereof
CN105566392B (en) A kind of preparation method of bacterio protein synthetic inhibitor
CN108003158B (en) Piperine quaternary ammonium salt derivative and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180904

Termination date: 20210712