CN106083534A - 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
CN106083534A
CN106083534A CN201610541705.3A CN201610541705A CN106083534A CN 106083534 A CN106083534 A CN 106083534A CN 201610541705 A CN201610541705 A CN 201610541705A CN 106083534 A CN106083534 A CN 106083534A
Authority
CN
China
Prior art keywords
boric acid
visible light
phenol
aryl boric
mmol
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.)
Granted
Application number
CN201610541705.3A
Other languages
Chinese (zh)
Other versions
CN106083534B (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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Indole Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The method of the aryl boric acid phenol of a kind of visible light catalytic, it belongs to technical field of organic synthesis.This preparation method is in the presence of room temperature, air and visible ray and amine, and with complex of iridium or platinum complex as catalyst, aryl boric acid occurs oxidation hydroxylating to generate phenolic compound.The method, with the oxygen in air as oxidant, has the features such as Atom economy is good, reaction condition is gentle and easy and simple to handle.The method enriches the synthetic method of phenolic compound, the especially synthesis for big conjugated phenols compounds and 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, particularly to the method synthesizing big conjugated phenols compounds.
Background technology
Phenolic compound is important Organic Chemicals, and it also can be used as medicine, dyestuff, the raw material of preservative In producing the products such as arylamine, caprolactam, alkyl phenol, fatty acid.Additionally, it also can be widely used in oxygen heterocycle chemical combination The synthesis of thing (Synthetic and natural phenols, Elsevier, 1996, 52).In recent years, along with phenol generalization The growth of compound demand, people constantly explore its synthetic method.But, the method for existing synthesis phenolic compound is still deposited necessarily Deficiency, such as: needing high-temperature high-voltage reaction condition, complicated process of preparation, 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 development of chemical machine is also that the research of visible light catalytic brings opportunity.
Summary of the invention
The method that it is an object of the invention to provide the aryl boric acid phenol of a kind of visible light catalytic, at the bar of visible light-inducing Under part, utilize the redox characteristic of complex of iridium or platinum complex, aryl boric acid mesoboric acid group is converted into the anti-of hydroxyl Should, with the synthetic method of abundant phenolic compound, the synthetic method of the biggest conjugated phenols compounds.
The technical solution used in the present invention is: 0.5 mmol aryl boric acid, 2 mol% complex of iridium or platinum are coordinated successively Thing, 1.0 mmol amine and 4 mL solvents add in reaction bulb.7 ~ 12 h are reacted, with thin under room temperature, air and visible light conditions Layer chromatography follows the tracks of reaction process, after reaction terminates, adds 15 mL saturated aqueous common salts, and reactant mixture is by 15 mL ethyl acetate Extract 3 times, merge organic facies, concentrate, use column chromatography, obtain phenolic compound.
In above-mentioned preparation method, described aryl boric acid selected from 1-naphthalene boronic acids, 2-naphthalene boronic acids, 3,5-diphenyl benzene boric acid, (10-phenylanthracene-9-base) boric acid, 4-(diphenylamino) phenylboric acid, 4-(9H-carbazole-9-base) phenylboric acid or N-phenyl-3-carbazole Boric acid.
In above-mentioned preparation method, Ir0 in following structure of described complex of iridium and platinum complex, Ir1, Ir2, Ir3, Pt0, Pt1, Pt2 or Pt3, the synthetic method of this series compound is at Dalton Transactions 2016,45,734- 741 and Journal of Materials Chemistry C, 2015,3,2166-2174 deliver, and its structure is as follows:
In above-mentioned preparation method, described amine is selected from triethylamine, diisopropylethylamine or diisopropylamine.
In above-mentioned preparation method, described solvent is selected from DMF, acetonitrile, oxolane, toluene or ethanol.
Sequence 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 Oxolane 68
6 3,5-diphenyl benzene boric acid Ir0 Triethylamine Toluene 70
7 3,5-diphenyl benzene boric acid Ir0 Triethylamine Ethanol 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-base) boric acid Ir2 Triethylamine N,N-dimethylformamide 80
16 (10-phenylanthracene-9-base) boric acid Pt2 Diisopropylethylamine N,N-dimethylformamide 76
17 4-(diphenylamino) phenylboric acid Ir2 Triethylamine N,N-dimethylformamide 83
18 4-(diphenylamino) phenylboric acid Pt2 Diisopropylethylamine N,N-dimethylformamide 73
19 4-(9H-carbazole-9-base) phenylboric acid Ir2 Triethylamine N,N-dimethylformamide 87
20 4-(9H-carbazole-9-base) phenylboric 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: this preparation method is in the presence of room temperature, air and visible ray and amine, with complex of iridium Or platinum complex is catalyst, aryl boric acid occurs oxidation hydroxylating to generate phenolic compound.The method is with in air Oxygen is oxidant, has the features such as Atom economy is good, reaction condition is gentle and easy and simple to handle.The method enriches phenol generalization The synthetic method of compound, the especially synthesis for big conjugated phenols compounds provide a simplicity, efficient method.
Detailed description of the invention
Embodiment 1 synthesizes 3,5-diphenyl phenol
3,5-diphenyl benzene boric acid (0.5 mmol), triethylamine (1.0 mmol), coordination compound Ir0(2 it is sequentially added in reaction bulb Mol%) and 4 mL N,N-dimethylformamides.Reacting under room temperature, air and visible light conditions, reaction process is by thin layer chromatography Follow the tracks of.After having reacted, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, concentrate, With petroleum ether and ethyl acetate as eluant, through column chromatography for separation, obtain target product 3,5-diphenyl phenol, productivity 74%, produce Thing structure is passed through1H NMR、13C NMR and Mass Spectrometric Identification.
Embodiment 2 synthesizes 3,5-diphenyl phenol
In reaction bulb, it is sequentially added into 3,5-diphenyl benzene boric acid (0.5 mmol), diisopropylethylamine (1.0 mmol), coordinates Thing Ir0(2 mol%) and 4 mL N,N-dimethylformamides.Reacting under room temperature, air and visible light conditions, reaction process is by thin Layer chromatography is followed the tracks of.After having reacted, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic Phase, concentrates, and with petroleum ether and ethyl acetate as eluant, through column chromatography for separation, obtains target product 3,5-diphenyl phenol, produces Rate 70%.
Embodiment 3 synthesizes 3,5-diphenyl phenol
3,5-diphenyl benzene boric acid (0.5 mmol), diisopropylamine (1.0 mmol), coordination compound it is sequentially added in reaction bulb Ir0(2 mol%) and 4 mL N,N-dimethylformamides.Reacting under room temperature, air and visible light conditions, reaction process is by thin layer Chromatography is followed the tracks of.After having reacted, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, Concentrate, with petroleum ether and ethyl acetate as eluant, through column chromatography for separation, obtain target product 3,5-diphenyl phenol, productivity 60%。
Embodiment 4 synthesizes 3,5-diphenyl phenol
3,5-diphenyl benzene boric acid (0.5 mmol), triethylamine (1.0 mmol), coordination compound Ir0(2 it is sequentially added in reaction bulb Mol%) and 4 mL acetonitriles.Reacting under room temperature, air and visible light conditions, reaction process is followed the tracks of by thin layer chromatography.React Cheng Hou, adds saturated aqueous common salt 15 mL, extracts by ethyl acetate (3*15 mL), merges organic facies, concentrates, with petroleum ether and second Acetoacetic ester is eluant, through column chromatography for separation, obtains target product 3,5-diphenyl phenol, productivity 65%.
Embodiment 5 synthesizes 3,5-diphenyl phenol
3,5-diphenyl benzene boric acid (0.5 mmol), triethylamine (1.0 mmol), coordination compound Ir0(2 it is sequentially added in reaction bulb Mol%) and 4 mL oxolanes.Reacting under room temperature, air and visible light conditions, reaction process is followed the tracks of by thin layer chromatography.Instead After should completing, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, concentrate, with petroleum ether It is eluant with ethyl acetate, through column chromatography for separation, obtains target product 3,5-diphenyl phenol, productivity 68%.
Embodiment 6 synthesizes 3,5-diphenyl phenol
3,5-diphenyl benzene boric acid (0.5 mmol), triethylamine (1.0 mmol), coordination compound Ir0(2 it is sequentially added in reaction bulb Mol%) and 4 mL toluene.Reacting under room temperature, air and visible light conditions, reaction process is followed the tracks of by thin layer chromatography.React Cheng Hou, adds saturated aqueous common salt 15 mL, extracts by ethyl acetate (3*15 mL), merges organic facies, concentrates, with petroleum ether and second Acetoacetic ester is eluant, through column chromatography for separation, obtains target product 3,5-diphenyl phenol, productivity 70%.
Embodiment 7 synthesizes 3,5-diphenyl phenol
3,5-diphenyl benzene boric acid (0.5 mmol), triethylamine (1.0 mmol), coordination compound Ir0(2 it is sequentially added in reaction bulb Mol%) and 4 mL ethanol.Reacting under room temperature, air and visible light conditions, reaction process is followed the tracks of by thin layer chromatography.React Cheng Hou, adds saturated aqueous common salt 15 mL, extracts by ethyl acetate (3*15 mL), merges organic facies, concentrates, with petroleum ether and second Acetoacetic ester is eluant, through column chromatography for separation, obtains target product 3,5-diphenyl phenol, productivity 72%.
Embodiment 8 synthesizes 3,5-diphenyl phenol
3,5-diphenyl benzene boric acid (0.5 mmol), triethylamine (1.0 mmol), coordination compound Ir1(2 it is sequentially added in reaction bulb Mol%) and 4 mL N,N-dimethylformamides.Reacting under room temperature, air and visible light conditions, reaction process is by thin layer chromatography Follow the tracks of.After having reacted, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, concentrate, With petroleum ether and ethyl acetate as eluant, through column chromatography for separation, obtain target product 3,5-diphenyl phenol, productivity 85%.
Embodiment 9 synthesizes 3,5-diphenyl phenol
3,5-diphenyl benzene boric acid (0.5 mmol), triethylamine (1.0 mmol), coordination compound Ir2(2 it is sequentially added in reaction bulb Mol%) and 4 mL N,N-dimethylformamides.Reacting under room temperature, air and visible light conditions, reaction process is by thin layer chromatography Follow the tracks of.After having reacted, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, concentrate, With petroleum ether and ethyl acetate as eluant, through column chromatography for separation, obtain target product 3,5-diphenyl phenol, productivity 88%.
Embodiment 10 synthesizes 3,5-diphenyl phenol
3,5-diphenyl benzene boric acid (0.5 mmol), triethylamine (1.0 mmol), coordination compound Ir3(2 it is sequentially added in reaction bulb Mol%) and 4 mL N,N-dimethylformamides.Reacting under room temperature, air and visible light conditions, reaction process is by thin layer chromatography Follow the tracks of.After having reacted, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, concentrate, With petroleum ether and ethyl acetate as eluant, through column chromatography for separation, obtain target product 3,5-diphenyl phenol, productivity 82%.
Embodiment 11 synthesizes 3,5-diphenyl phenol
3,5-diphenyl benzene boric acid (0.5 mmol), triethylamine (1.0 mmol), coordination compound Pt0(2 it is sequentially added in reaction bulb Mol%) and 4 mL N,N-dimethylformamides.Reacting under room temperature, air and visible light conditions, reaction process is by thin layer chromatography Follow the tracks of.After having reacted, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, concentrate, With petroleum ether and ethyl acetate as eluant, through column chromatography for separation, obtain target product 3,5-diphenyl phenol, productivity 64%.
Embodiment 12 synthesizes 3,5-diphenyl phenol
3,5-diphenyl benzene boric acid (0.5 mmol), triethylamine (1.0 mmol), coordination compound Pt1(2 it is sequentially added in reaction bulb Mol%) and 4 mL N,N-dimethylformamides.Reacting under room temperature, air and visible light conditions, reaction process is by thin layer chromatography Follow the tracks of.After having reacted, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, concentrate, With petroleum ether and ethyl acetate as eluant, through column chromatography for separation, obtain target product 3,5-diphenyl phenol, productivity 75%.
Embodiment 13 synthesizes 3,5-diphenyl phenol
3,5-diphenyl benzene boric acid (0.5 mmol), triethylamine (1.0 mmol), coordination compound Pt2(2 it is sequentially added in reaction bulb Mol%) and 4 mL N,N-dimethylformamides.Reacting under room temperature, air and visible light conditions, reaction process is by thin layer chromatography Follow the tracks of.After having reacted, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, concentrate, With petroleum ether and ethyl acetate as eluant, through column chromatography for separation, obtain target product 3,5-diphenyl phenol, productivity 86%.
Embodiment 14 synthesizes 3,5-diphenyl phenol
3,5-diphenyl benzene boric acid (0.5 mmol), triethylamine (1.0 mmol), coordination compound Pt3(2 it is sequentially added in reaction bulb Mol%) and 4 mL N,N-dimethylformamides.Reacting under room temperature, air and visible light conditions, reaction process is by thin layer chromatography Follow the tracks of.After having reacted, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, concentrate, With petroleum ether and ethyl acetate as eluant, through column chromatography for separation, obtain target product 3,5-diphenyl phenol, productivity 72%.
Embodiment 15 synthesizes 10-phenyl-9-anthrol
(10-phenylanthracene-9-base) boric acid (0.5 mmol), triethylamine (1.0 mmol), coordination compound it is sequentially added in reaction bulb Ir2(2 mol%) and 4 mL DMF.Reacting under room temperature, air and visible light conditions, reaction process is followed the tracks of by thin layer chromatography.Instead Should completely after, add saturated aqueous common salt 15 mL, with ethyl acetate (3*15 mL) extract, merge organic facies, concentrate, with petroleum ether Being eluant with ethyl acetate, through column chromatography for separation, obtain target product 10-phenyl-9-anthrol, productivity 80%, product structure leads to Cross1H NMR、13C NMR and Mass Spectrometric Identification.
Embodiment 16 synthesizes 10-phenyl-9-anthrol
Be sequentially added in reaction bulb (10-phenylanthracene-9-base) boric acid (0.5 mmol), diisopropylethylamine (1.0 mmol), Coordination compound Pt2(2 mol%) and 4 mL DMF.Reacting under room temperature, air and visible light conditions, reaction process is by thin layer chromatography Follow the tracks of.After reaction completely, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, concentrate, With petroleum ether and ethyl acetate as eluant, through column chromatography for separation, obtain target product 10-phenyl-9-anthrol, productivity 76%.
Embodiment 17 synthesizes 4-(diphenylamino) phenol
4-(diphenylamino) phenylboric acid (0.5 mmol), triethylamine (1.0 mmol), coordination compound Ir2 it is sequentially added in reaction bulb (2 mol%) and 4 mL DMF.Reacting under room temperature, air and visible light conditions, reaction process is followed the tracks of by thin layer chromatography.Reaction After Wan Quan, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, concentrate, with petroleum ether and Ethyl acetate is eluant, through column chromatography for separation, obtains target product 4-(diphenylamino) phenol, productivity 83%, and product structure leads to Cross1H NMR、13C NMR and Mass Spectrometric Identification.
Embodiment 18 synthesizes 4-(diphenylamino) phenol
In reaction bulb, it is sequentially added into 4-(diphenylamino) phenylboric acid (0.5 mmol), diisopropylethylamine (1.0 mmol), joins Compound Pt2(2 mol%) and 4 mL DMF.Under room temperature, air and visible light conditions react, reaction process by thin layer chromatography with Track.After reaction completely, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, concentrate, with Petroleum ether and ethyl acetate are eluant, through column chromatography for separation, obtain target product 4-(diphenylamino) phenol, productivity 73%.
Embodiment 19 synthesizes 4-(9H-carbazole-9-base) phenol
In reaction bulb, it is sequentially added into 4-(9H-carbazole-9-base) phenylboric acid (0.5 mmol), triethylamine (1.0 mmol), coordinates Thing Ir2(2 mol%) and 4 mL DMF.Reacting under room temperature, air and visible light conditions, reaction process is followed the tracks of by thin layer chromatography. After reaction completely, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, concentrate, with oil Ether and ethyl acetate are eluant, through column chromatography for separation, obtain target product 4-(9H-carbazole-9-base) phenol, productivity 87%, produce Thing structure is passed through1H NMR、13C NMR and Mass Spectrometric Identification.
Embodiment 20 synthesizes 4-(9H-carbazole-9-base) phenol
4-(9H-carbazole-9-base) phenylboric acid (0.5 mmol), diisopropylethylamine (1.0 it is sequentially added in reaction bulb Mmol), coordination compound Pt2(2 mol%) and 4 mL DMF.Reacting under room temperature, air and visible light conditions, reaction process is by thin layer Chromatography is followed the tracks of.After reaction completely, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, Concentrate, with petroleum ether and ethyl acetate as eluant, through column chromatography for separation, obtain target product 4-(9H-carbazole-9-base) benzene Phenol, productivity 88%.
Embodiment 21 synthesizes (9-phenyl-9H-carbazole-3-base) phenol
N-phenyl-3-carbazole boric acid (0.5 mmol), triethylamine (1.0 mmol), coordination compound Ir2 it is sequentially added in reaction bulb (2 mol%) and 4 mL DMF.Reacting under room temperature, air and visible light conditions, reaction process is followed the tracks of by thin layer chromatography.Reaction After Wan Quan, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, concentrate, with petroleum ether and Ethyl acetate is eluant, through column chromatography for separation, obtains target product (9-phenyl-9H-carbazole-3-base) phenol, productivity 95%, produces Thing structure is passed through1H NMR、13C NMR and Mass Spectrometric Identification.
Embodiment 22 synthesizes (9-phenyl-9H-carbazole-3-base) phenol
In reaction bulb, it is sequentially added into N-phenyl-3-carbazole boric acid (0.5 mmol), diisopropylethylamine (1.0 mmol), coordinates Thing Pt2(2 mol%) and 4 mL DMF.Reacting under room temperature, air and visible light conditions, reaction process is followed the tracks of by thin layer chromatography. After reaction completely, add saturated aqueous common salt 15 mL, extract by ethyl acetate (3*15 mL), merge organic facies, concentrate, with oil Ether and ethyl acetate are eluant, through column chromatography for separation, obtain target product (9-phenyl-9H-carbazole-3-base) phenol, productivity 85%。
Above content is to combine the further description that the present invention is done by optimal technical scheme, it is impossible to assert the present invention's It is embodied as being only limitted to these explanations.For general technical staff of the technical field of the invention, without departing from the present invention Design on the premise of made change, modify, substitute, combine, simplify, all should be the substitute mode of equivalence, all should be considered as Protection scope of the present invention.

Claims (3)

1. the method for the aryl boric acid phenol of a visible light catalytic, it is characterised in that comprise the following steps:
(1), under room temperature, air and visible light conditions, successively aryl boric acid, catalyst, amine and solvent are added in reaction bulb, institute Stating aryl boric acid: the amount of the material of amine is 1:2, described catalyst uses complex of iridium or platinum complex, and the consumption of catalyst is The 2mol% of aryl boric acid consumption；
(2) stirring, follows the tracks of reaction process by thin layer chromatography, after reaction terminates, adds saturated aqueous common salt, reactant mixture second Acetoacetic ester extracts, and merges organic facies, concentrates, uses column chromatography, obtain phenolic compound；
Described aryl boric acid selected from 3,5-diphenyl benzene boric acid, (10-phenylanthracene-9-base) boric acid, 4-(diphenylamino) phenylboric acid, 4-(9H-carbazole-9-base) phenylboric acid or N-phenyl-3-carbazole boric acid；
Described complex of iridium is Ir0, Ir1, Ir2 or Ir3, and described platinum complex is Pt0, Pt1, Pt2 or Pt3；
。
2. according to the method for aryl boric acid phenol of a kind of visible light catalytic described in claim 1, it is characterised in that: described amine Selected from triethylamine, diisopropylethylamine or diisopropylamine.
3. according to the method for aryl boric acid phenol of a kind of visible light catalytic described in claim 1, it is characterised in that: described molten Agent is selected from N,N-dimethylformamide, acetonitrile, oxolane, toluene or ethanol.
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 true CN106083534A (en) 2016-11-09
CN106083534B 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)

Cited By (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
CN114016060A (en) * 2021-11-23 2022-02-08 南昌大学 Synthetic method of phenolic compound

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHRISTOPHER K.PRIER ET AL.: "Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis", 《CHMICAL REVIEWS》 *
WON JOON CHOI ET AL.: "Mechanisms and applications of cyclometalated Pt(II) complexes in photoredox catalytic trifluoromethylation", 《CHEM.SCI.》 *
YOU-QUAN ZOU ET AL.: "Highly Efficient Aerobic Oxidative Hydroxylation of Arylboronic Acids:Photoredox Catalysis Using Visible Light", 《ANGEW.CHEM.》 *

Cited By (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
CN114016060A (en) * 2021-11-23 2022-02-08 南昌大学 Synthetic method of phenolic compound

Also Published As

Publication number Publication date
CN106083534B (en) 2018-09-04

Similar Documents

Publication Publication Date Title
CN104402934B (en) Preparation method and application of 2-(diphenylphosphineethyl)-(5,6,7,8-tetrahydroquinolinyl)amine ruthenium complexes
CN105254567B (en) A kind of method for preparing dexmedetomidine hydrochloride key intermediate
US20170247352A1 (en) Method for preparing alectinib
CN103694188B (en) The preparation method of Fu benzene Ni Kao oxazoline intermediate
CN105418678B (en) A kind of preparation method of Tedizolid Phosphate
CN106083534A (en) A kind of method of the aryl boric acid phenol of visible light catalytic
CN112390758A (en) Synthetic process of Laolatinib intermediate 1, 5-dimethyl-1H-pyrazole-3-ethyl formate
CN105175373B (en) Synthetic method of aryl ketone coumarin derivative
CN103864630A (en) Synthesis method of (S)-1-(4-ethyoxyl benzyl)-3-azapentane-1,5-diamine trihydrochloride
CN108794553B (en) Preparation method of baicalin aluminum complex for pig mixed feed
CN105503864A (en) Preparing method for moxifloxacin intermediate
CN105254574B (en) A kind of simple and convenient process for preparing of the cyanopyrimidine of 2 methyl of vitamin B1 key intermediate, 4 amino 5
CN107903209A (en) A kind of synthetic method of 2 amino, 5 fluorine pyridine, 3 methyl formate
CN108358923B (en) Sophoridine pyrrole and indole derivatives, and preparation method and application thereof
CN106883185B (en) Preparation method of 4-chloro-2-trifluoromethylpyrimidine
Fatullayeva et al. New cobalt (II) and nickel (II) complexes of 2-hydroxy-benzyl derivatives of 4-aminoantipyrine
CN103922934A (en) Alkylation method of active methylene compound
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
Cui et al. Synthesis and crystal structures of Schiff base oxovanadium (V) complexes [VO (Bhm)(OCH3)(CH3OH)] and [VO2 (Bpp)]
CN105198825B (en) A kind of preparation method of D seromycins
CN102603570B (en) Preparation method for 2,3,4-trimethoxy benzonitrile
CN103992280B (en) A kind of preparation method of iron catalysis microwave synthesis 4- amido quinazoline urea derivative
CN109761894A (en) A kind of preparation method of 5- bromo-2-pyridyl formic acid
CN116239529B (en) Preparation method of N-methyltetrahydroquinoline alkaloid with participation of carbon dioxide
CN109134358B (en) Synthetic method of 3, 5-dibromo-4-aminopyridine

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