WO2023142460A1 - Procédé de synthèse d'arylphénol par réaction entre un halogénure d'aryle et un composé phénolique sous induction de lumière visible - Google Patents

Procédé de synthèse d'arylphénol par réaction entre un halogénure d'aryle et un composé phénolique sous induction de lumière visible Download PDF

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WO2023142460A1
WO2023142460A1 PCT/CN2022/113938 CN2022113938W WO2023142460A1 WO 2023142460 A1 WO2023142460 A1 WO 2023142460A1 CN 2022113938 W CN2022113938 W CN 2022113938W WO 2023142460 A1 WO2023142460 A1 WO 2023142460A1
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reaction
phenol
visible light
halogenated aromatic
mmol
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PCT/CN2022/113938
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English (en)
Chinese (zh)
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李红喜
朱大亮
李海燕
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苏州大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention belongs to the technical field of catalytic chemistry, and in particular relates to the application of synthesizing aryl phenol through the reaction of halogenated aromatic hydrocarbon and phenol induced by visible light.
  • diarylphenols widely exist in natural products, drug molecules, catalysts and functional materials [ J. Org. Chem. 2017 , 82 , 9367 ⁇ 9383; Org. Lett. 2018 , 20 , 4077 ⁇ 4080; ACS Catal. 2020 , 10 , 14615 ⁇ 14623; J. Am. Chem. Soc. 2015 , 137 , 15062 ⁇ 15065].
  • the arylation reaction of phenol is one of the effective methods for the synthesis of such compounds.
  • Chemists usually introduce esters, carbamates, ethers, o-pyridyls, o-pyrimidinyls, and phosphinates on the hydroxyl group of phenol as directing groups, and then use halogenated aromatics on palladium, ruthenium, or gold as directing groups.
  • the arylation reaction of phenol derivatives is completed under the condition of catalyst [ Tetrahedron 2020 , 76 , 130925; Org. Biomol. Chem. 2009 , 7 , 4853 ⁇ 4857; J. Org. Chem. 2016 , 81 , 3473 ⁇ 3478; Org . Lett.
  • the present invention provides a method of using visible light to induce the reaction of halogenated aromatic hydrocarbons and phenol under the condition of no transition metal catalyst to realize the synthesis of aryl phenolic compounds. That is to say, a series of aryl phenolic compounds were synthesized by using halogenated aromatic hydrocarbons and phenol as raw materials, dimethyl sulfoxide as solvent, and cesium carbonate as base under the irradiation of blue light strips. In addition, the present invention obtains aryl phenolic compounds with higher yield. The whole catalytic process of the invention is green, efficient and easy to operate, and is a good method for synthesizing aryl phenolic compounds.
  • the present invention adopts the following technical scheme: a method for synthesizing arylphenols by inducing the reaction of halogenated aromatic hydrocarbons and phenol compounds with visible light, comprising the following steps, using halogenated aromatic hydrocarbons and phenol compounds as raw materials, in the presence of alkali, inert gas
  • the arylphenol is prepared by the light reaction; preferably, the light reaction is carried out in an organic solvent.
  • the inert gas is selected from any one of nitrogen, helium, neon and argon, preferably nitrogen.
  • the halogenated aromatic hydrocarbon has the following chemical structural formula: ;
  • the phenolic compound has the following chemical structural formula: ; Specifically, the phenol compound has a general structural formula as shown in any one of formula (A) to formula (D): .
  • R 1 can be selected from cyano, carbonyl, ester group, trifluoromethyl, methyl, methoxy, isopropyl, tert-butyl or n-propyl;
  • R 2 can be selected from hydrogen or chlorine;
  • R 3 Can be selected from trifluoromethyl or bromine.
  • the halogenated aromatic hydrocarbon has a general structural formula as shown in any one of formula (E) to formula (H): .
  • R 4 can be selected from methyl, ethyl, n-propyl, n-butyl or phenyl;
  • R 5 can be selected from fluorine or chlorine.
  • the base is an inorganic base or an organic base, preferably, the base is selected from cesium carbonate (Cs 2 CO 3 ), potassium carbonate (K 2 CO 3 ), potassium phosphate (K 3 PO 4 ), cesium fluoride (CsF) or N-tert-butylisopropanolamine ( t -BuNH( i -Pr)).
  • cesium carbonate Cs 2 CO 3
  • potassium carbonate K 2 CO 3
  • potassium phosphate K 3 PO 4
  • CsF cesium fluoride
  • t -BuNH( i -Pr) N-tert-butylisopropanolamine
  • the solvent is selected from any one of N , N -dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile (MeCN), and chloroform (CHCl 3 ).
  • the molar ratio between the halogenated aromatic hydrocarbon, the phenol compound and the base is 1: (1.5-5): (1.5-3).
  • the light is sunlight, blue light or green light.
  • the light reaction is carried out at room temperature under the light of a blue light strip; the light reaction time is 10-50 hours, preferably 12-20 hours.
  • the present invention realizes the reaction synthesis aryl phenol compound of halogenated aromatic hydrocarbon and phenol by visible light induction, as illustration, it comprises the following steps: under the protection of inert gas, according to the molar ratio between halogenated aromatic hydrocarbon, phenol, cesium carbonate is 1: 4:2, add the above reactants into the reaction vessel equipped with a stirring device, then add 0.5 mL dimethyl sulfoxide (DMSO), under the irradiation of a blue light strip, stir and react at room temperature for 14 hours to obtain arylphenols compound.
  • the stirring device is a magnetic stirring device;
  • the reaction vessel is a sealed reaction tube.
  • the raw material 1 is a halogenated aromatic hydrocarbon, and the specific structure is as above; the raw material 2 is a phenol compound, and the specific structure is as above.
  • the invention uses halogenated aromatic hydrocarbons and phenol compounds as raw materials to prepare aryl phenols by light reaction in an organic solvent in the presence of alkali in an inert gas, without catalysts, other reagents and other conditions.
  • the present invention will be further described below in conjunction with specific embodiments. Unless otherwise specified, the reagents, materials, instruments, etc. used in the following examples can be obtained through commercial means, and the specific preparation operations involved, such as stirring, are existing conventional techniques. Unless otherwise specified, the following yields refer to separation yields.
  • Example 1 cesium carbonate is used as a base, and visible light induces the reaction between p-bromoacetophenone and phenol.
  • Example 1 On the basis of Example 1, the illumination was omitted, and the rest remained unchanged, and no product was obtained.
  • Example 1 On the basis of Example 1, the base is omitted, and the rest remain unchanged, and no product can be obtained.
  • Example 2 cesium carbonate is used as a base, and visible light induces the reaction of p-bromoacetophenone and p-cyanophenol.
  • Example 3 cesium carbonate is used as a base, and visible light induces the reaction between p-bromoacetophenone and p-acetylphenol.
  • Example 4 Cesium carbonate is used as a base, and visible light induces the reaction of p-bromoacetophenone and p-hydroxypropiophenone.
  • Example 5 Cesium carbonate is used as a base, and visible light induces the reaction between p-bromoacetophenone and methyl p-hydroxybenzoate.
  • Example 6 Cesium carbonate is used as a base, and visible light induces the reaction between p-bromoacetophenone and ethyl p-hydroxybenzoate.
  • Example 7 cesium carbonate is used as a base, and visible light induces the reaction of p-bromoacetophenone and p-trifluoromethylphenol.
  • Example 8 Using cesium carbonate as a base, visible light induces the reaction between p-bromoacetophenone and p-cresol.
  • Example 9 cesium carbonate is used as a base, and visible light induces the reaction of p-bromoacetophenone and p-methoxyphenol.
  • Example 10 Using cesium carbonate as a base, visible light induces the reaction between p-bromoacetophenone and p-isopropylphenol.
  • Example 11 cesium carbonate is used as a base, and visible light induces the reaction of p-bromoacetophenone and p-tert-butylphenol.
  • Example 12 Using cesium carbonate as a base, visible light induces the reaction between p-bromoacetophenone and p-n-propylphenol.
  • Example 13 cesium carbonate is used as a base, and visible light induces the reaction of p-bromoacetophenone and o-chlorophenol.
  • Example 14 Cesium carbonate is used as a base, and visible light induces the reaction between p-bromoacetophenone and 2,4-dichlorophenol.
  • Example 15 Cesium carbonate is used as a base, and visible light induces the reaction between p-bromoacetophenone and 3,5-bis(trifluoromethyl)phenol.
  • Example 16 cesium carbonate is used as a base, and visible light induces the reaction between p-bromoacetophenone and 3,5-dibromophenol.
  • Example 17 Using cesium carbonate as a base, visible light induces the reaction between p-bromoacetophenone and 2-naphthol.
  • Example 18 Using cesium carbonate as a base, visible light induces the reaction between p-bromopropiophenone and methyl p-hydroxybenzoate.
  • Example 19 Cesium carbonate is used as a base, and visible light induces the reaction between p-bromobutyrophenone and methyl p-hydroxybenzoate.
  • Example 20 Using cesium carbonate as a base, visible light induces the reaction between p-bromovalone and methyl p-hydroxybenzoate.
  • Example 21 Using cesium carbonate as a base, visible light induces the reaction between p-bromobenzophenone and methyl p-hydroxybenzoate.
  • Example 22 Using cesium carbonate as a base, visible light induces the reaction between 4-bromo-2-fluoroacetophenone and methyl p-hydroxybenzoate.
  • Example 23 Cesium carbonate is used as a base, and visible light induces the reaction between 4-bromo-2-chloroacetophenone and methyl p-hydroxybenzoate.
  • Example 24 Using cesium carbonate as a base, visible light induces the reaction between 3-bromo-5-trifluoromethyl-benzonitrile and p-acetylphenol.
  • Example 25 Cesium carbonate is used as a base, and visible light induces the reaction between 3-bromobenzonitrile and p-acetylphenol.
  • Example 26 Cesium carbonate is used as a base, and visible light induces the reaction of 2-bromobenzonitrile and p-acetylphenol.

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

Abstract

La présente invention concerne un procédé de synthèse d'arylphénol au moyen d'une réaction entre un halogénure d'aryle et un composé de phénol sous induction de lumière visible, lequel procédé comprend : sous la protection d'un gaz inerte, l'agitation et la réaction d'un halogénure d'aryle, d'un composé de phénol et de carbonate de césium dans du diméthylsulfoxyde (DMSO) à température ambiante sous l'irradiation de lumière visible de façon à obtenir un produit, à savoir un composé d'arylphénol. Dans la présente invention, l'ensemble du processus est écologique et efficace, et est facile à utiliser, de telle sorte que le procédé est un bon procédé de synthèse d'un composé d'arylphénol.
PCT/CN2022/113938 2022-01-26 2022-08-22 Procédé de synthèse d'arylphénol par réaction entre un halogénure d'aryle et un composé phénolique sous induction de lumière visible WO2023142460A1 (fr)

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CN114380675B (zh) * 2022-01-26 2024-06-11 苏州大学 一种可见光诱导卤代芳烃与苯酚化合物反应合成芳基酚的方法
CN115010563B (zh) * 2022-07-08 2023-03-31 大连理工大学 一种可见光促进的镍催化的卤素交换制备不同卤代芳烃的方法
CN115536498B (zh) * 2022-10-24 2023-10-20 遵义医科大学 一种丁二酮催化的取代苯酚氧化偶联的方法

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