CN110683925A - Synthetic method of biphenyl compound - Google Patents

Synthetic method of biphenyl compound Download PDF

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CN110683925A
CN110683925A CN201911009292.4A CN201911009292A CN110683925A CN 110683925 A CN110683925 A CN 110683925A CN 201911009292 A CN201911009292 A CN 201911009292A CN 110683925 A CN110683925 A CN 110683925A
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ethyl acetate
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CN110683925B (en
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毛泽伟
高慧
李敏欣
唐燕玲
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Yunnan University of Traditional Chinese Medicine TCM
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • 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
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • 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

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Abstract

The invention discloses a synthesis method of biphenyl compounds, which comprises the steps of taking aromatic boric acid as a reaction substrate, taking palladium as a catalyst, adding a catalytic amount of phase transfer catalyst, reacting for 1-5 hours at 50 ℃ in sodium hypochlorite aqueous solution, carrying out self-oxidative coupling, and carrying out post-reaction treatment to obtain a target product biphenyl compound. The method has the characteristics of mild reaction conditions, simple operation and purification, wide application range of the substrate, high yield, high reaction speed and the like, and has practicability.

Description

Synthetic method of biphenyl compound
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthetic method of biphenyl compounds.
Background
Biphenyl compounds not only exist widely in a plurality of natural products with physiological activity, but also are a very important high molecular material and ligand organic compound, and the synthesis research of biphenyl compounds is receiving more and more attention at present. The method is commonly used at present, and the aryl halide is obtained by coupling reaction of halogenated aromatic hydrocarbon and reagents such as aromatic boric acid, aromatic Grignard reagent or aromatic hydrazine under the catalysis of transition metal (palladium, copper, silver, nickel, ruthenium, rhodium and the like). The currently reported method has the defects of high cost, slow reaction, complex operation, low yield, difficult purification and the like. Therefore, the research on how to synthesize the symmetrical biphenyl compounds with high efficiency is very important.
Disclosure of Invention
The invention aims to provide a synthetic method of a biphenyl compound.
The invention aims to realize the purpose, the aromatic boric acid, the palladium catalyst and the quaternary ammonium salt phase transfer catalyst are dispersed in the sodium hypochlorite aqueous solution and stirred for 1 to 5 hours at the temperature of 50 ℃; after the reaction is finished, ether or ethyl acetate is used for extraction, an organic phase is dried and then concentrated, and the biphenyl compound is obtained, wherein the reaction equation in the synthesis method is as follows:
Figure 593823DEST_PATH_IMAGE001
wherein R is hydrogen, fluorine, chlorine, bromine, iodine, alkyl, alkoxy, phenyl, phenoxy, acetyl, cyano, nitro or trifluoromethyl.
The method takes cheap and easily-obtained aromatic boric acid as a reaction substrate, takes palladium as a catalyst (palladium chloride, palladium acetate, palladium trifluoroacetate or the like), adds a catalytic amount of quaternary ammonium salt (benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride or the like) as a phase transfer catalyst, and reacts for 1-5 hours at 50 ℃ in a sodium hypochlorite aqueous solution (with the mass concentration of 10-13%). After the reaction is finished, ether or ethyl acetate is used for extraction, and the organic phase is dried and then concentrated to obtain the biphenyl compound without further purification. The method has the advantages of no addition of ligand and alkali, reaction in aqueous solution, high yield and simple and convenient post-treatment.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to be limiting in any way, and any modifications or alterations based on the teachings of the present invention are intended to fall within the scope of the present invention.
The invention relates to a synthesis method of biphenyl compounds, which comprises the following steps: dispersing aromatic boric acid, a palladium catalyst and a quaternary ammonium salt phase transfer catalyst in a sodium hypochlorite aqueous solution, and stirring for 1-5 hours at 50 ℃; after the reaction is finished, ether or ethyl acetate is used for extraction, an organic phase is dried and then concentrated, and the biphenyl compound is obtained, wherein the reaction equation in the synthesis method is as follows:
wherein R is hydrogen, fluorine, chlorine, bromine, iodine, alkyl, alkoxy, phenyl, phenoxy, acetyl, cyano, nitro or trifluoromethyl.
The palladium catalyst is palladium chloride, palladium acetate or palladium trifluoroacetate.
The quaternary ammonium salt phase transfer catalyst is benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride.
The mass concentration of the sodium hypochlorite aqueous solution is 10-13%.
The mass-volume ratio of the aromatic boric acid to the sodium hypochlorite aqueous solution is 1mmol:3 ~ 10 mL.
The invention is further illustrated by the following specific examples:
example 1
Figure 448646DEST_PATH_IMAGE003
A10 mL reaction tube was charged with 1a (1mmol,122mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (68mg, 88%). The characterization data for this compound are as follows:1H NMR(400MHz, CDCl3)δ: 7.64-7.67(m, 4H), 7.47-7.51(m,4H), 7.38-7.42(m, 2H);13C NMR(100MHz, CDCl3)δ: 141.39, 128.89, 127.38,127.30.
1a (1mmol,122mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (69mg, 90%).
A10 mL reaction tube was charged with 1a (1mmol,122mg), Pd (CF)3COO)2(0.03mmol,10mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). Sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to roomAnd (4) warming. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (66mg, 86%).
A10 mL reaction tube was charged with 1a (1mmol,122mg), Pd (OAc)2(0.03mmol,6.7mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (68mg, 88%).
1a (1mmol,122mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (69mg, 90%).
A10 mL reaction tube was charged with 1a (1mmol,122mg), Pd (CF)3COO)2(0.03mmol,10mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (66mg, 86%).
A10 mL reaction tube was charged with 1a (1mmol,122mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (68mg, 88%).
1a (1mmol,122mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (69mg, 90%).
A10 mL reaction tube was charged with 1a (1mmol,122mg), Pd (CF)3COO)2(0.03mmol,10mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (66mg, 86%).
A10 mL reaction tube was charged with 1a (1mmol,122mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (68mg, 88%).
1a (1mmol,122mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (69mg, 90%).
A10 mL reaction tube was charged with 1a (1mmol,122mg), Pd (CF)3COO)2(0.03mmol,10mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqouso soProposal). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (66mg, 86%).
A10 mL reaction tube was charged with 1a (1mmol,122mg), Pd (OAc)2(0.03mmol,6.7mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (68mg, 88%).
1a (1mmol,122mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (69mg, 90%).
A10 mL reaction tube was charged with 1a (1mmol,122mg), Pd (CF)3COO)2(0.03mmol,10mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (66mg, 86%).
A10 mL reaction tube was charged with 1a (1mmol,122mg), Pd (OAc)2(0.03mmol,6.7mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extracting with diethyl ether or ethyl acetate (5 mL. times.3), sequentially adding water and saturated food to the organic phaseWashed twice with brine, dried over anhydrous sodium sulfate and filtered, and the filtrate concentrated in vacuo to give the desired product 2a (68mg, 88%).
1a (1mmol,122mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (69mg, 90%).
A10 mL reaction tube was charged with 1a (1mmol,122mg), Pd (CF)3COO)2(0.03mmol,10mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2a (66mg, 86%).
Example 2
Figure DEST_PATH_IMAGE004
A10 mL reaction tube was charged with 1b (1mmol,136mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2b (77mg, 85%).
1b (1mmol,136mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with Ether or Ethyl acetate (5 mL. times.3), organic phaseWashed twice with water and saturated brine in this order, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2b (80mg, 88%).
1b (1mmol,136mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2b (79mg, 87%).
A10 mL reaction tube was charged with 1b (1mmol,136mg), Pd (OAc)2(0.03mmol,6.7mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2b (81mg, 89%).
1b (1mmol,136mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2b (82mg, 90%).
1b (1mmol,136mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2b (77mg, 85%).
At 10Into a mL reaction tube were added 1b (1mmol,136mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2b (84mg, 92%).
1b (1mmol,136mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2b (82mg, 90%).
1b (1mmol,136mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2b (75mg, 82%).
A10 mL reaction tube was charged with 1b (1mmol,136mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2b (76mg, 84%).
1b (1mmol,136mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). The reaction tube is sealed and then placed in an oil bath at 50 ℃ to be stirredAnd cooling to room temperature for 1 h. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2b (82mg, 90%).
1b (1mmol,136mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2b (80mg, 88%).
A10 mL reaction tube was charged with 1b (1mmol,136mg), Pd (OAc)2(0.03mmol,6.7mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2b (79mg, 87%).
1b (1mmol,136mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2b (79mg, 87%).
1b (1mmol,136mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with diethyl ether or ethyl acetate (5 mL. times.3), washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate, filtration and filtrationThe solution was concentrated in vacuo to give the desired product 2b (76mg, 84%).
A10 mL reaction tube was charged with 1b (1mmol,136mg), Pd (OAc)2(0.03mmol,6.7mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2b (80mg, 88%).
1b (1mmol,136mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2b (77mg, 85%).
1b (1mmol,136mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2b (74mg, 81%).
Example 3
Figure 916799DEST_PATH_IMAGE005
A10 mL reaction tube was charged with 1c (1mmol,152mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with diethyl ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in successionAgain, after drying over anhydrous sodium sulfate, filtration and concentration of the filtrate in vacuo, the desired product 2c (93mg, 87%) was obtained. The characterization data for this compound are as follows:1H NMR(400MHz, CDCl3)δ: 7.49(d, J=8.8Hz, 4H), 6.97(d, J=8.8Hz, 4H), 3.84(s, 6H);13C NMR(100MHz, CDCl3)δ: 158.87, 133.66, 127.89,114.33, 55.50.
1c (1mmol,152mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate concentrated in vacuo to give the desired product 2c (90mg, 84%).
1c (1mmol,152mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2c (93mg, 87%).
A10 mL reaction tube was charged with 1c (1mmol,152mg), Pd (OAc)2(0.03mmol,6.7mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2c (74mg, 88%).
1c (1mmol,152mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with diethyl ether or ethyl acetate (5 mL. times.3) and the organic phase was taken in turn with waterAnd saturated brine, dried over anhydrous sodium sulfate and filtered, and the filtrate concentrated in vacuo to give the desired product 2c (93mg, 87%).
1c (1mmol,152mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2c (89mg, 83%).
A10 mL reaction tube was charged with 1c (1mmol,152mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2c (95mg, 89%).
1c (1mmol,152mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2c (96mg, 90%).
1c (1mmol,152mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2c (92mg, 86%).
1c was added to a 10mL reaction tube(1mmol,152mg)、Pd(OAc)2(0.03mmol,6.7mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2c (89mg, 83%).
1c (1mmol,152mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate concentrated in vacuo to give the desired product 2c (90mg, 84%).
1c (1mmol,152mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2c (88mg, 82%).
A10 mL reaction tube was charged with 1c (1mmol,152mg), Pd (OAc)2(0.03mmol,6.7mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2c (94mg, 88%).
1c (1mmol,152mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). The reaction tube is sealed and then placed in an oil bath at 50 ℃ to be stirredThe reaction was carried out for 1h, and cooled to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2c (97mg, 91%).
1c (1mmol,152mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate concentrated in vacuo to give the desired product 2c (90mg, 84%).
A10 mL reaction tube was charged with 1c (1mmol,152mg), Pd (OAc)2(0.03mmol,6.7mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2c (92mg, 86%).
1c (1mmol,152mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2c (94mg, 88%).
1c (1mmol,152mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with diethyl ether or ethyl acetate (5 mL. times.3), washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate andfiltration and concentration of the filtrate in vacuo gave the title product 2c (93mg, 87%).
Example 4
Figure DEST_PATH_IMAGE006
A10 mL reaction tube was charged with 1d (1mmol,182mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2d (122mg, 89%). The characterization data for this compound are as follows:1H NMR(400MHz, CDCl3)δ: 7.11(d, J=2.1Hz, 1H), 7.08(d,J=2.1Hz, 1H), 7.06(d, J=2.1Hz, 2H), 6.94(s, 1H), 6.92(s, 1H), 3.95(s, 6H),3.91(s, 6H);13C NMR(100MHz, CDCl3)δ:149.28, 148.50, 134.38, 119.26, 111.69,110.61, 56.13.
1d (1mmol,182mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2d (115mg, 84%).
A10 mL reaction tube was charged with 1d (1mmol,182mg), Pd (CF)3COO)2(0.03mmol,10mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2d (118mg, 86%).
A10 mL reaction tube was charged with 1d (1mmol,182mg), Pd (OAc)2(0.03mmol,6.7mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate concentrated in vacuo to give the desired product 2d (116mg, 85%).
1d (1mmol,182mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2d (122mg, 89%).
A10 mL reaction tube was charged with 1d (1mmol,182mg), Pd (CF)3COO)2(0.03mmol,10mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2d (110mg, 80%).
A10 mL reaction tube was charged with 1d (1mmol,182mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2d (121mg, 88%).
1d (1mmol,182mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. With diethyl ether orExtraction with ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine twice in succession, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2d (125mg, 91%).
A10 mL reaction tube was charged with 1d (1mmol,182mg), Pd (CF)3COO)2(0.03mmol,10mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2d (112mg, 82%).
A10 mL reaction tube was charged with 1d (1mmol,182mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2d (110mg, 80%).
1d (1mmol,182mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate concentrated in vacuo to give the desired product 2d (116mg, 85%).
A10 mL reaction tube was charged with 1d (1mmol,182mg), Pd (CF)3COO)2(0.03mmol,10mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2d (118mg, 86%).
A10 mL reaction tube was charged with 1d (1mmol,182mg), Pd (OAc)2(0.03mmol,6.7mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2d (111mg, 81%).
1d (1mmol,182mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2d (114mg, 83%).
A10 mL reaction tube was charged with 1d (1mmol,182mg), Pd (CF)3COO)2(0.03mmol,10mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2d (107mg, 78%).
A10 mL reaction tube was charged with 1d (1mmol,182mg), Pd (OAc)2(0.03mmol,6.7mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2d (111mg, 81%).
1d (1mmol,182mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg) and hypochlorous acidSodium (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2d (121mg, 88%).
A10 mL reaction tube was charged with 1d (1mmol,182mg), Pd (CF)3COO)2(0.03mmol,10mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2d (114mg, 83%).
Example 5
Figure 515270DEST_PATH_IMAGE007
A10 mL reaction tube was charged with 1e (1mmol,178mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the title product 2e (117mg, 88%). The characterization data for this compound are as follows:1H NMR(400MHz, CDCl3)δ: 7.56(d, J=8.4Hz, 4H), 7.48(d,J=8.4Hz, 4H), 1.38(s, 18H);13C NMR(100MHz, CDCl3)δ:150.06, 138.35, 126.81,125.78, 34.65, 31.54.
1e (1mmol,178mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with diethyl ether or ethyl acetate (5 mL. times.3) and washing of the organic phase twice with water and saturated brine in succession withoutAfter drying over sodium sulfate, filtration and concentration of the filtrate in vacuo, the desired product 2e was obtained (110mg, 83%).
1e (1mmol,178mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the title product 2e (115mg, 87%).
A10 mL reaction tube was charged with 1e (1mmol,178mg), Pd (OAc)2(0.03mmol,6.7mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2e (108mg, 81%).
1e (1mmol,178mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2e (120mg, 90%).
1e (1mmol,178mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2e (109mg, 82%).
A10 mL reaction tube was charged with 1e (1mmol,178mg), Pd (g)OAc)2(0.03mmol,6.7mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2e (108mg, 81%).
1e (1mmol,178mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the title product 2e (116mg, 87%).
1e (1mmol,178mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the title product 2e (114mg, 86%).
A10 mL reaction tube was charged with 1e (1mmol,178mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the title product 2e (117mg, 88%).
1e (1mmol,178mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. With diethyl ether orExtraction with ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine twice in succession, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2e (104mg, 78%).
1e (1mmol,178mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2e (109mg, 82%).
A10 mL reaction tube was charged with 1e (1mmol,178mg), Pd (OAc)2(0.03mmol,6.7mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2e (108mg, 81%).
1e (1mmol,178mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2e (109mg, 82%).
1e (1mmol,178mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extracting with diethyl ether or ethyl acetate (5 mL. times.3), washing the organic phase with water and saturated brine twice in sequence, drying over anhydrous sodium sulfate, filtering, and vacuum concentrating the filtrate to obtain the desired productProduct 2e (108mg, 81%).
A10 mL reaction tube was charged with 1e (1mmol,178mg), Pd (OAc)2(0.03mmol,6.7mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the title product 2e (116mg, 87%).
1e (1mmol,178mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2e (110mg, 83%).
1e (1mmol,178mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 1h, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the title product 2e (106mg, 80%).
Example 6
Figure DEST_PATH_IMAGE008
A10 mL reaction tube was charged with 1f (1mmol,140mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with diethyl ether or ethyl acetate (5 mL. times.3), washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtrationThe filtrate was concentrated in vacuo to give the desired product 2f (79mg, 83%).
1f (1mmol,140mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine twice in succession followed by drying over anhydrous sodium sulfate and filtration gave the title product 2f (80mg, 84%) which was concentrated in vacuo.
1f (1mmol,140mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2f (82mg, 87%).
A10 mL reaction tube was charged with 1f (1mmol,140mg), Pd (OAc)2(0.03mmol,6.7mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2f (82mg, 86%).
1f (1mmol,140mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine twice in succession followed by drying over anhydrous sodium sulfate and filtration gave the title product 2f (76mg, 80%) which was concentrated in vacuo.
1f (1mmol,140mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), benzylTriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine twice in succession followed by drying over anhydrous sodium sulfate and filtration gave the title product 2f (75mg, 79%) which was concentrated in vacuo.
A10 mL reaction tube was charged with 1f (1mmol,140mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2f (82mg, 86%).
1f (1mmol,140mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2f (77mg, 81%).
1f (1mmol,140mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2f (70mg, 74%).
A10 mL reaction tube was charged with 1f (1mmol,140mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with diethyl ether or ethyl acetate (5 mL. times.3), organic phase dependentWashed twice with water and saturated brine, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2f (74mg, 78%).
1f (1mmol,140mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2f (82mg, 86%).
1f (1mmol,140mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2f (78mg, 82%).
A10 mL reaction tube was charged with 1f (1mmol,140mg), Pd (OAc)2(0.03mmol,6.7mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine twice in succession followed by drying over anhydrous sodium sulfate and filtration gave the title product 2f (76mg, 80%) which was concentrated in vacuo.
1f (1mmol,140mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine twice in succession followed by drying over anhydrous sodium sulfate and filtration gave the title product 2f (80mg, 84%) which was concentrated in vacuo.
Reaction at 10mL1f (1mmol,140mg), Pd (CF) were added to the tube3COO)2(0.03mmol,10mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2f (77mg, 81%).
A10 mL reaction tube was charged with 1f (1mmol,140mg), Pd (OAc)2(0.03mmol,6.7mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine twice in succession followed by drying over anhydrous sodium sulfate and filtration gave the title product 2f (76mg, 80%) which was concentrated in vacuo.
1f (1mmol,140mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine twice in succession followed by drying over anhydrous sodium sulfate and filtration gave the title product 2f (75mg, 79%) which was concentrated in vacuo.
1f (1mmol,140mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2f (77mg, 81%).
Example 7
Figure 516593DEST_PATH_IMAGE009
A10 mL reaction tube was charged with 1g (1mmol,156mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2g (89mg, 80%).
A10 mL reaction tube was charged with 1g (1mmol,156mg) of PdCl2(0.03mmol,5.3mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded 2g (92mg, 83%) of the desired product.
A10 mL reaction tube was charged with 1g (1mmol,156mg) of Pd (CF)3COO)2(0.03mmol,10mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded 2g (87mg, 78%) of the desired product.
A10 mL reaction tube was charged with 1g (1mmol,156mg), Pd (OAc)2(0.03mmol,6.7mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded 2g (94mg, 85%) of the title product.
A10 mL reaction tube was charged with 1g (1mmol,156mg) of PdCl2(0.03mmol,5.3mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aq)The ueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded 2g (86mg, 78%) of the desired product.
A10 mL reaction tube was charged with 1g (1mmol,156mg) of Pd (CF)3COO)2(0.03mmol,10mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded 2g (93mg, 84%) of the desired product.
A10 mL reaction tube was charged with 1g (1mmol,156mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2g (89mg, 80%).
A10 mL reaction tube was charged with 1g (1mmol,156mg) of PdCl2(0.03mmol,5.3mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded 2g (91mg, 82%) of the desired product.
A10 mL reaction tube was charged with 1g (1mmol,156mg) of Pd (CF)3COO)2(0.03mmol,10mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3), washing the organic phase twice with water and saturated brine in succession,after drying over anhydrous sodium sulfate, filtration and concentration of the filtrate in vacuo, 2g (88mg, 79%) of the desired product were obtained.
A10 mL reaction tube was charged with 1g (1mmol,156mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded 2g (96mg, 87%) of the desired product.
A10 mL reaction tube was charged with 1g (1mmol,156mg) of PdCl2(0.03mmol,5.3mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2g (90mg, 81%).
A10 mL reaction tube was charged with 1g (1mmol,156mg) of Pd (CF)3COO)2(0.03mmol,10mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded 2g (91mg, 82%) of the desired product.
A10 mL reaction tube was charged with 1g (1mmol,156mg), Pd (OAc)2(0.03mmol,6.7mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded 2g (95mg, 86%) of the desired product.
A10 mL reaction tube was charged with 1g (1mmol,156mg) of PdCl2(0.03mmol,5.3mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2g (89mg, 80%).
A10 mL reaction tube was charged with 1g (1mmol,156mg) of Pd (CF)3COO)2(0.03mmol,10mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded 2g (91mg, 82%) of the desired product.
A10 mL reaction tube was charged with 1g (1mmol,156mg), Pd (OAc)2(0.03mmol,6.7mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded 2g (92mg, 83%) of the desired product.
A10 mL reaction tube was charged with 1g (1mmol,156mg) of PdCl2(0.03mmol,5.3mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2g (99mg, 89%).
A10 mL reaction tube was charged with 1g (1mmol,156mg) of Pd (CF)3COO)2(0.03mmol,10mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). The reaction tube is sealed and then put in a 50 ℃ oil bathThe reaction is stirred for 2h and cooled to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded 2g (85mg, 77%) of the desired product.
Example 8
Figure DEST_PATH_IMAGE010
A10 mL reaction tube was charged with 1h (1mmol,190mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2h (107mg, 74%).
A10 mL reaction tube was charged with 1h (1mmol,190mg) of PdCl2(0.03mmol,5.3mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2h (101mg, 70%).
A10 mL reaction tube was charged with 1h (1mmol,190mg), Pd (CF)3COO)2(0.03mmol,10mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2h (113mg, 78%).
A10 mL reaction tube was charged with 1h (1mmol,190mg), Pd (OAc)2(0.03mmol,6.7mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). The reaction tube is sealed and then placed at 50The mixture is stirred and reacted for 5 hours in an oil bath at the temperature of between, and cooled to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2h (94mg, 65%).
A10 mL reaction tube was charged with 1h (1mmol,190mg) of PdCl2(0.03mmol,5.3mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2h (104mg, 72%).
A10 mL reaction tube was charged with 1h (1mmol,190mg), Pd (CF)3COO)2(0.03mmol,10mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2h (116mg, 80%).
A10 mL reaction tube was charged with 1h (1mmol,190mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2h (106mg, 73%).
A10 mL reaction tube was charged with 1h (1mmol,190mg) of PdCl2(0.03mmol,5.3mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3), washing of the organic phase with water and saturated brine twice in succession, drying over anhydrous sodium sulfate, filtration, concentration of the filtrate in vacuo,the expected product was obtained in 2h (103mg, 71%).
A10 mL reaction tube was charged with 1h (1mmol,190mg), Pd (CF)3COO)2(0.03mmol,10mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the title product 2h (112mg, 77%).
A10 mL reaction tube was charged with 1h (1mmol,190mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2h (103mg, 70%).
A10 mL reaction tube was charged with 1h (1mmol,190mg) of PdCl2(0.03mmol,5.3mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2h (104mg, 72%).
A10 mL reaction tube was charged with 1h (1mmol,190mg), Pd (CF)3COO)2(0.03mmol,10mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2h (104mg, 72%).
A10 mL reaction tube was charged with 1h (1mmol,190mg), Pd (OAc)2(0.03mmol,6.7mg), dodecyl trimethyl ChlorinationAmmonium (0.1mmol, 26mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2h (100mg, 69%).
A10 mL reaction tube was charged with 1h (1mmol,190mg) of PdCl2(0.03mmol,5.3mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2h (103mg, 70%).
A10 mL reaction tube was charged with 1h (1mmol,190mg), Pd (CF)3COO)2(0.03mmol,10mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2h (104mg, 72%).
A10 mL reaction tube was charged with 1h (1mmol,190mg), Pd (OAc)2(0.03mmol,6.7mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2h (106mg, 73%).
A10 mL reaction tube was charged with 1h (1mmol,190mg) of PdCl2(0.03mmol,5.3mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. With diethyl ether or ethyl acetateExtraction (5 mL. times.3), washing of the organic phase with water and saturated brine in turn twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2h (109mg, 75%).
A10 mL reaction tube was charged with 1h (1mmol,190mg), Pd (CF)3COO)2(0.03mmol,10mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2h (103mg, 71%).
Example 9
Figure 276739DEST_PATH_IMAGE011
A10 mL reaction tube was charged with 1i (1mmol,147mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2i (80mg, 78%).
1i (1mmol,147mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2i (76mg, 75%).
1i (1mmol,147mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). Sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring and reacting for 5 hours, and coolingAnd (4) cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2i (80mg, 78%).
A10 mL reaction tube was charged with 1i (1mmol,147mg), Pd (OAc)2(0.03mmol,6.7mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2i (80mg, 78%).
1i (1mmol,147mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2i (84mg, 82%).
1i (1mmol,147mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2i (83mg, 81%).
A10 mL reaction tube was charged with 1i (1mmol,147mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3), washing of the organic phase twice with water and saturated brine in succession, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2i (80mg, 78)％)。
1i (1mmol,147mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2i (76mg, 75%).
1i (1mmol,147mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2i (82mg, 80%).
A10 mL reaction tube was charged with 1i (1mmol,147mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2i (76mg, 75%).
1i (1mmol,147mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine twice in succession followed by drying over anhydrous sodium sulfate and filtration gave the title product 2i (81mg, 79%) which was concentrated in vacuo.
1i (1mmol,147mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqu)eous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2i (71mg, 70%).
A10 mL reaction tube was charged with 1i (1mmol,147mg), Pd (OAc)2(0.03mmol,6.7mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine twice in succession followed by drying over anhydrous sodium sulfate and filtration gave the title product 2i (81mg, 79%) which was concentrated in vacuo.
1i (1mmol,147mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2i (72mg, 71%).
1i (1mmol,147mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2i (80mg, 78%).
A10 mL reaction tube was charged with 1i (1mmol,147mg), Pd (OAc)2(0.03mmol,6.7mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with diethyl ether or ethyl acetate (5 mL. times.3), successive application of water to the organic phase and saturation of the organic phaseAnd brine twice, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the objective product 2i (83mg, 81%).
1i (1mmol,147mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2i (75mg, 74%).
1i (1mmol,147mg), Pd (CF) were put into a 10mL reaction tube3COO)2(0.03mmol,10mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, the filtrate was concentrated in vacuo to give the desired product 2i (77mg, 76%).
Example 10
Figure DEST_PATH_IMAGE012
A10 mL reaction tube was charged with 1j (1mmol,167mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2j (83mg, 68%).
1j (1mmol,167mg) PdCl was added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extracted with diethyl ether or ethyl acetate (5 mL. times.3) withThe organic phase was washed twice with water and saturated brine in this order, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2j (79mg, 65%).
1j (1mmol,167mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the title product 2j (76mg, 62%).
A10 mL reaction tube was charged with 1j (1mmol,167mg), Pd (OAc)2(0.03mmol,6.7mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the title product 2j (76mg, 62%).
1j (1mmol,167mg) PdCl was added to a 10mL reaction tube2(0.03mmol,5.3mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the title product 2j (79mg, 65%).
1j (1mmol,167mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2j (74mg, 61%).
A10 mL reaction tube was charged with 1j (1mmol,167mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2j (73mg, 60%).
1j (1mmol,167mg) PdCl was added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the title product 2j (79mg, 65%).
1j (1mmol,167mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2j (71mg, 58%).
A10 mL reaction tube was charged with 1j (1mmol,167mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2j (84mg, 69%).
1j (1mmol,167mg) PdCl was added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). The reaction tube is sealed and then placed in an oil bath at 50 DEG CThe reaction was stirred for 5h and cooled to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2j (81mg, 66%).
1j (1mmol,167mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2j (82mg, 67%).
A10 mL reaction tube was charged with 1j (1mmol,167mg), Pd (OAc)2(0.03mmol,6.7mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2j (74mg, 61%).
1j (1mmol,167mg) PdCl was added to a 10mL reaction tube2(0.03mmol,5.3mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2j (73mg, 60%).
1j (1mmol,167mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with diethyl ether or ethyl acetate (5 mL. times.3), washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfateFiltration and concentration of the filtrate in vacuo gave the desired product 2j (73mg, 60%).
A10 mL reaction tube was charged with 1j (1mmol,167mg), Pd (OAc)2(0.03mmol,6.7mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2j (74mg, 61%).
1j (1mmol,167mg) PdCl was added to a 10mL reaction tube2(0.03mmol,5.3mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2j (78mg, 64%).
1j (1mmol,167mg), Pd (CF) were added to a 10mL reaction tube3COO)2(0.03mmol,10mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase was washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the title product 2j (77mg, 63%).
Example 11
Figure 229258DEST_PATH_IMAGE013
A10 mL reaction tube was charged with 1k (1mmol,180mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with diethyl ether or ethyl acetate (5 mL. times.3), successive application of water and saturated brine to the organic phaseWashed twice, dried over anhydrous sodium sulfate and filtered, and the filtrate concentrated in vacuo to give the desired product 2k (94mg, 70%). The characterization data for this compound are as follows:1H NMR(400MHz, CDCl3)δ:8.14(d, J=8.6Hz, 4H), 7.70(d, J=8.6Hz, 4H), 3.95(s, 6H);13C NMR(100MHz, CDCl3)δ:158.67, 144.53, 130.37,127.41, 52.36.
1k (1mmol,180mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate concentrated in vacuo to give the desired product 2k (97mg, 72%).
A10 mL reaction tube was charged with 1k (1mmol,180mg) and Pd (CF)3COO)2(0.03mmol,10mg), tetrabutylammonium bromide (0.1mmol,33mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate concentrated in vacuo to give the desired product 2k (82mg, 61%).
A10 mL reaction tube was charged with 1k (1mmol,180mg), Pd (OAc)2(0.03mmol,6.7mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2k (92mg, 68%).
1k (1mmol,180mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with diethyl ether or ethyl acetate (5 mL. times.3) and successive organic phasesWashed twice with water and saturated brine, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated in vacuo to give the desired product 2k (84mg, 62%).
A10 mL reaction tube was charged with 1k (1mmol,180mg) and Pd (CF)3COO)2(0.03mmol,10mg), benzyltriethylammonium chloride (0.1mmol, 23mg) and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2k (89mg, 66%).
A10 mL reaction tube was charged with 1k (1mmol,180mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2k (94mg, 70%).
1k (1mmol,180mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2k (93mg, 69%).
A10 mL reaction tube was charged with 1k (1mmol,180mg) and Pd (CF)3COO)2(0.03mmol,10mg), tetrabutylammonium chloride (0.1mmol, 28mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2k (81mg, 60%).
Adding into a 10mL reaction tube1k (1mmol,180mg), Pd (OAc)2(0.03mmol,6.7mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and the organic phase washed twice with water and saturated brine in succession, dried over anhydrous sodium sulfate and filtered, and the filtrate concentrated in vacuo to give the desired product 2k (97mg, 72%).
1k (1mmol,180mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2k (90mg, 67%).
A10 mL reaction tube was charged with 1k (1mmol,180mg) and Pd (CF)3COO)2(0.03mmol,10mg), tetrabutylammonium hydrogen sulfate (0.1mmol, 34mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2k (94mg, 70%).
A10 mL reaction tube was charged with 1k (1mmol,180mg), Pd (OAc)2(0.03mmol,6.7mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2k (90mg, 67%).
1k (1mmol,180mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). The reaction tube is sealed and then placed in an oil bath at 50 DEG CThe reaction was stirred for 5h and cooled to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2k (81mg, 60%).
A10 mL reaction tube was charged with 1k (1mmol,180mg) and Pd (CF)3COO)2(0.03mmol,10mg), dodecyltrimethylammonium chloride (0.1mmol, 26mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2k (88mg, 65%).
A10 mL reaction tube was charged with 1k (1mmol,180mg), Pd (OAc)2(0.03mmol,6.7mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2k (96mg, 71%).
1k (1mmol,180mg), PdCl were added to a 10mL reaction tube2(0.03mmol,5.3mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with ether or ethyl acetate (5 mL. times.3) and washing of the organic phase with water and saturated brine in succession twice, drying over anhydrous sodium sulfate and filtration, and concentration of the filtrate in vacuo afforded the desired product 2k (92mg, 68%).
A10 mL reaction tube was charged with 1k (1mmol,180mg) and Pd (CF)3COO)2(0.03mmol,10mg), tetradecyltrimethylammonium chloride (0.1mmol, 29mg), and sodium hypochlorite (3mL, 10% aqueous solution). And sealing the reaction tube, placing the reaction tube in an oil bath at 50 ℃, stirring for reaction for 5 hours, and cooling to room temperature. Extraction with diethyl ether or ethyl acetate (5 mL. times.3), washing of the organic phase twice with water and saturated brine in succession, drying over anhydrous sodium sulfateAfter drying, filtration and concentration of the filtrate in vacuo, the desired product 2k (86mg, 64%) was obtained.

Claims (5)

1. A synthetic method of biphenyl compounds is characterized by comprising the following specific steps: dispersing aromatic boric acid, a palladium catalyst and a quaternary ammonium salt phase transfer catalyst in a sodium hypochlorite aqueous solution, and stirring for 1-5 hours at 50 ℃; after the reaction is finished, ether or ethyl acetate is used for extraction, an organic phase is dried and then concentrated, and the biphenyl compound is obtained, wherein the reaction equation in the synthesis method is as follows:
wherein R is hydrogen, fluorine, chlorine, bromine, iodine, alkyl, alkoxy, phenyl, phenoxy, acetyl, cyano, nitro or trifluoromethyl.
2. The method for synthesizing biphenyl compounds according to claim 1, wherein the palladium catalyst is palladium chloride, palladium acetate or palladium trifluoroacetate.
3. The method for synthesizing biphenyl compounds according to claim 1, wherein the quaternary ammonium salt phase transfer catalyst is benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride.
4. The method for synthesizing biphenyl compounds according to claim 1, wherein the mass concentration of the sodium hypochlorite aqueous solution is 10-13%.
5. The method for synthesizing biphenyl compounds according to claim 1, wherein the mass-to-volume ratio of the aromatic boric acid to the aqueous solution of sodium hypochlorite is 1mmol:3 ~ 10 mL.
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