CN100569713C - A kind of preparation method of biphenyl compound - Google Patents
A kind of preparation method of biphenyl compound Download PDFInfo
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- CN100569713C CN100569713C CNB2007100113300A CN200710011330A CN100569713C CN 100569713 C CN100569713 C CN 100569713C CN B2007100113300 A CNB2007100113300 A CN B2007100113300A CN 200710011330 A CN200710011330 A CN 200710011330A CN 100569713 C CN100569713 C CN 100569713C
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Abstract
The invention provides a kind of air promoted in polyoxyethylene glycol the Suzuki cross-coupling reaction of generated in-situ nanometer palladium catalysis chlorinated aromatic hydrocarbons and aryl boric acid prepare the method for biphenyl compound.The characteristics of this method are need not add part, consisting of phase-transferring agent or promotor, do not need the protection of rare gas element, and under the catalysis of generated in-situ nanometer palladium, chlorinated aromatic hydrocarbons and aryl boric acid be efficient synthetic biphenyl compound under the reaction conditions of gentleness in polyoxyethylene glycol.Under optimal conditions, the transformation efficiency of chlorinated aromatic hydrocarbons and the separation yield of biphenyl compound reach 95～100% and 90～99% respectively.
Description
Technical field
The present invention relates to the method that in the organic synthesis aromatics a kind of Suzuki of utilization cross-coupling reaction prepares biphenyl compound.
Background technology
The Suzuki linked reaction is one of effective means of a kind of C-C of formation key, is bringing into play important effect in organic synthesis.This reaction has reaction conditions gentleness, applicable various active functional group, is subjected to the sterically hindered advantages such as little, that productive rate is high and aryl boric acid economy is easy to get that influence, at aspects such as synthesizing of natural product, medicine, agricultural chemicals, weedicide and polymer conductive material, liquid crystal material purposes (Chem.Rev.1995 is widely arranged, 95,2457-2483).
So far, most of catalyst system of bibliographical information have all been used part or promotor, and the main phosphine part that uses air and moisture-sensitive, what reaction medium had is very expensive (as ionic liquid, fluorinated solvents etc.), the toxicity that has is big (as acetonitrile, 1,4-dioxane etc.), temperature of reaction generally is higher than 80 ℃, be primarily aimed at cross-coupling reaction (Chem.Commun.2000,1249-1250, the J.Am.Chem.Soc.2000 of iodo and aryl bromide and aryl boric acid, 122,9058-9064, Angew.Chem.Int.Ed.2002,41,4176-4211, Angew.Chem.Int.Ed.2002,41,23,4500-4503, Chem.Eur.J.2004,10,1789-1797).
Over the past two years, bibliographical information be reaction medium with PEG, do not need part or promotor, temperature of reaction has obtained good catalytic activity below 60 ℃ to the cross-coupling reaction of multiple bromobenzene and aryl boric acid, even some have also been obtained catalytic effect (J.Org.Chem.2005 preferably than activatory chlorinated benzene class, 70,6122-6125, J.Org.Chem.2005,70,5409-5412, Tetrahedron 2006,62,9359-9364).But the promoted method that the Suzuki cross-coupling reaction of generated in-situ nanometer palladium catalysis chlorinated aromatic hydrocarbons and aryl boric acid prepares biphenyl compound in PEG of air is not appeared in the newspapers as yet.
The purpose of this invention is to provide a kind of air promoted in PEG the Suzuki cross-coupling reaction of generated in-situ nanometer palladium catalysis chlorinated aromatic hydrocarbons and aryl boric acid prepare the catalysis novel process of biphenyl compound.
Summary of the invention
The invention provides a kind of in the presence of solvent and catalyzer, the method for preparing biphenyl compound by the Suzuki cross-coupling reaction of chlorinated aromatic hydrocarbons and aryl boric acid, it is characterized in that this method is in air, successively with 1.0～20.0mmol solvent polyoxyethylene glycol, 0.02～0.05mmol palladium catalyst precursor, 2.0～4.0mmol alkali, 1.0mmol chlorinated aromatic hydrocarbons, 1.1 the mark n-decane adds in the 50ml round-bottomed flask in～2.0mmol aryl boric acid and the 1.0mmol, 30～60 ℃ of stirring reactions 1～5 hour, follow the tracks of with gas-chromatography in the reaction process, after reaction finishes, with 5ml * 3 time extracted with diethyl ether reaction product, merge organic phase, use anhydrous Na
2SO
4Drying is filtered, and filtrate concentrates, and uses column chromatography, and elutriant is the ethyl acetate/petroleum ether of volume ratio 1/10, obtain transformation efficiency and be 95～100% and separation yield be 90～99% biphenyl compound.
Among the above-mentioned preparation method, employed solvent is the polyoxyethylene glycol of molecular-weight average at 200～2000g/mol.
Among the above-mentioned preparation method, employed catalyst precursor is palladium or Palladous chloride.
Among the above-mentioned preparation method, the zeroth order nanometer palladium particle with catalytic activity is generated in-situ in polyoxyethylene glycol, and polyoxyethylene glycol has solvent, reductive agent and function of stabilizer concurrently.
Among the above-mentioned preparation method, employed alkali is salt of wormwood, yellow soda ash, potassium tert.-butoxide, sodium tert-butoxide, potassium ethylate, sodium ethylate, potassium hydroxide, sodium hydroxide, potassiumphosphate, Potassium monofluoride, cesium fluoride or cesium carbonate.
Among the above-mentioned preparation method, employed chlorinated aromatic hydrocarbons is a 4-methoxyl group chlorobenzene, 4-ethanoyl chlorobenzene, 4-nitro-chlorobenzene, 2-nitro-chlorobenzene, 4-hydroxyl chlorobenzene, 4-chlorobenzaldehyde, 2-chlorobenzonitrile, 2-chloro-benzoic acid or 4-trifluoromethyl chlorobenzene.
Among the above-mentioned preparation method, employed aryl boric acid is a phenylo boric acid, the 2-methylphenylboronic acid, the 3-methylphenylboronic acid, 4-methylphenylboronic acid, 2-methoxyphenylboronic acid, the 3-methoxyphenylboronic acid, 4-methoxyphenylboronic acid, 4-trifluoromethyl phenylo boric acid, the 4-fluorobenzoic boric acid, 3,4-two fluorobenzoic boric acids, 3,4,5-trifluoro-benzene boric acid or 4-chlorobenzene boric acid.
The preparation method of biphenyl compound provided by the invention does not use part, solubility promoter or promotor, does not need protection of inert gas, reaction medium environmental friendliness and can reclaim, reaction under mild conditions, be the cross-coupling reaction of catalyzer efficient catalytic chlorinated aromatic hydrocarbons and aryl boric acid with generated in-situ nanometer palladium in polyoxyethylene glycol, and its aspect such as synthetic at big right product, medicine, agricultural chemicals, weedicide and polymer conductive material, liquid crystal material has a wide range of applications.
Embodiment
Embodiment 1
The cross-coupling reaction of palladium catalytic 4-methoxyl group chlorobenzene and phenylo boric acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), salt of wormwood (2.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), phenylo boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.Reaction finishes the back with extracted with diethyl ether reaction product (5ml * 3), merges organic phase, anhydrous Na
2SO
4Drying, filtering and concentrating, column chromatography obtains biphenyl class product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (volume ratio is 1/10), and product structure passes through
1H NMR and mass spectrum are identified.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 2
The cross-coupling reaction of palladium catalytic 4-methoxyl group chlorobenzene and 2-methylphenylboronic acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), salt of wormwood (4.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 2-methylphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 3
The cross-coupling reaction of palladium catalytic 4-methoxyl group chlorobenzene and 3-methylphenylboronic acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), salt of wormwood (2.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 3-methylphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 4
The cross-coupling reaction of palladium catalytic 4-methoxyl group chlorobenzene and 4-methylphenylboronic acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), salt of wormwood (4.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 4-methylphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 5
The cross-coupling reaction of palladium catalytic 4-methoxyl group chlorobenzene and 2-methoxyphenylboronic acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), yellow soda ash (2.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 2-methoxyphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 6
The cross-coupling reaction of palladium catalytic 4-methoxyl group chlorobenzene and 3-methoxyphenylboronic acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), yellow soda ash (4.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 3-methoxyphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 7
The cross-coupling reaction of palladium catalytic 4-methoxyl group chlorobenzene and 4-methoxyphenylboronic acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), yellow soda ash (2.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 4-methoxyphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 8
The cross-coupling reaction of palladium catalytic 4-methoxyl group chlorobenzene and 4-trifluoromethyl phenylo boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), yellow soda ash (4.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 4-trifluoromethyl phenylo boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 9
The cross-coupling reaction of palladium catalytic 4-methoxyl group chlorobenzene and 4-fluorobenzoic boric acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), potassium tert.-butoxide (2.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 4-fluorobenzoic boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 10
Palladium catalytic 4-methoxyl group chlorobenzene and 3, the cross-coupling reaction of 4-two fluorobenzoic boric acids
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), potassium tert.-butoxide (4.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 3,4-two fluorobenzoic boric acids (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 11
Palladium catalytic 4-methoxyl group chlorobenzene and 3,4, the cross-coupling reaction of 5-trifluoro-benzene boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), potassium tert.-butoxide (2.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 3,4,5-trifluoro-benzene boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 12
The cross-coupling reaction of palladium catalytic 4-methoxyl group chlorobenzene and 4-chlorobenzene boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), potassium tert.-butoxide (4.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 4-chlorobenzene boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 13
The cross-coupling reaction of palladium catalytic 4-ethanoyl chlorobenzene and phenylo boric acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), sodium tert-butoxide (2.0mmol), 4-ethanoyl chlorobenzene (1.0mmol), phenylo boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 14
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of palladium and phenylo boric acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), sodium tert-butoxide (4.0mmol), 4-nitro-chlorobenzene (1.0mmol), phenylo boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 15
The cross-coupling reaction of catalytic 2-nitro-chlorobenzene of palladium and phenylo boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), sodium tert-butoxide (2.0mmol), 2-nitro-chlorobenzene (1.0mmol), phenylo boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 16
The cross-coupling reaction of palladium catalytic 4-hydroxyl chlorobenzene and phenylo boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), sodium tert-butoxide (4.0mmol), 4-hydroxyl chlorobenzene (1.0mmol), phenylo boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 17
The cross-coupling reaction of catalytic 4-chlorobenzaldehyde of palladium and phenylo boric acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), potassium ethylate (2.0mmol), 4-chlorobenzaldehyde (1.0mmol), phenylo boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 18
The cross-coupling reaction of catalytic 2-chlorobenzonitrile of palladium and phenylo boric acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), potassium ethylate (4.0mmol), 2-chlorobenzonitrile (1.0mmol), phenylo boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 19
The cross-coupling reaction of catalytic 2-chloro-benzoic acid of palladium and phenylo boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), potassium ethylate (2.0mmol), 2-chloro-benzoic acid (1.0mmol), phenylo boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 20
The cross-coupling reaction of palladium catalytic 4-trifluoromethyl chlorobenzene and phenylo boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), potassium ethylate (4.0mmol), 4-trifluoromethyl chlorobenzene (1.0mmol), phenylo boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 21
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of palladium and 2-methylphenylboronic acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), sodium ethylate (2.0mmol), 4-nitro-chlorobenzene (1.0mmol), 2-methylphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 22
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of palladium and 3-methylphenylboronic acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), sodium ethylate (4.0mmol), 4-nitro-chlorobenzene (1.0mmol), 3-methylphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 23
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of palladium and 4-methylphenylboronic acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), sodium ethylate (2.0mmol), 4-nitro-chlorobenzene (1.0mmol), 4-methylphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 24
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of palladium and 2-methoxyphenylboronic acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), sodium ethylate (4.0mmol), 4-nitro-chlorobenzene (1.0mmol), 2-methoxyphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 25
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of palladium and 3-methoxyphenylboronic acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), potassium hydroxide (2.0mmol), 4-nitro-chlorobenzene (1.0mmol), 3-methoxyphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 26
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of palladium and 4-methoxyphenylboronic acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), potassium hydroxide (4.0mmol), 4-nitro-chlorobenzene (1.0mmol), 4-methoxyphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 27
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of palladium and 4-trifluoromethyl phenylo boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), potassium hydroxide (2.0mmol), 4-nitro-chlorobenzene (1.0mmol), 4-trifluoromethyl phenylo boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 28
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of palladium and 4-fluorobenzoic boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), potassium hydroxide (4.0mmol), 4-nitro-chlorobenzene (1.0mmol), 4-fluorobenzoic boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 29
The catalytic 4-nitro-chlorobenzene of palladium and 3, the cross-coupling reaction of 4-two fluorobenzoic boric acids
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), sodium hydroxide (2.0mmol), 4-nitro-chlorobenzene (1.0mmol), 3,4-two fluorobenzoic boric acids (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 30
The catalytic 4-nitro-chlorobenzene of palladium and 3,4, the cross-coupling reaction of 5-trifluoro-benzene boric acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), sodium hydroxide (4.0mmol), 4-nitro-chlorobenzene (1.0mmol), 3,4,5-trifluoro-benzene boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 31
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of palladium and 4-chlorobenzene boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), sodium hydroxide (2.0mmol), 4-nitro-chlorobenzene (1.0mmol), 4-chlorobenzene boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 32
The cross-coupling reaction of catalytic 4-chlorobenzaldehyde of palladium and 4-methylphenylboronic acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), sodium hydroxide (4.0mmol), 4-chlorobenzaldehyde (1.0mmol), 4-methylphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 33
The cross-coupling reaction of catalytic 4-chlorobenzaldehyde of palladium and 4-methoxyphenylboronic acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), potassiumphosphate (2.0mmol), 4-chlorobenzaldehyde (1.0mmol), 4-methoxyphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 34
The cross-coupling reaction of catalytic 4-chlorobenzaldehyde of palladium and 4-trifluoromethyl phenylo boric acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), potassiumphosphate (4.0mmol), 4-chlorobenzaldehyde (1.0mmol), 4-trifluoromethyl phenylo boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 35
The cross-coupling reaction of catalytic 4-chlorobenzaldehyde of palladium and 4-fluorobenzoic boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), potassiumphosphate (2.0mmol), 4-chlorobenzaldehyde (1.0mmol), 4-fluorobenzoic boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 36
The catalytic 4-chlorobenzaldehyde of palladium and 3,4, the cross-coupling reaction of 5-trifluoro-benzene boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), potassiumphosphate (4.0mmol), 4-chlorobenzaldehyde (1.0mmol), 3,4,5-trifluoro-benzene boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 37
The cross-coupling reaction of catalytic 2-chlorobenzonitrile of palladium and 4-methylphenylboronic acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), Potassium monofluoride (2.0mmol), 2-chlorobenzonitrile (1.0mmol), 4-methylphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 38
The cross-coupling reaction of catalytic 2-chlorobenzonitrile of palladium and 4-methoxyphenylboronic acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), Potassium monofluoride (4.0mmol), 2-chlorobenzonitrile (1.0mmol), 4-methoxyphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 39
The cross-coupling reaction of catalytic 2-chlorobenzonitrile of palladium and 4-trifluoromethyl phenylo boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), Potassium monofluoride (2.0mmol), 2-chlorobenzonitrile (1.0mmol), 4-trifluoromethyl phenylo boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 40
The catalytic 2-chlorobenzonitrile of palladium and 3,4, the cross-coupling reaction of 5-trifluoro-benzene boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), Potassium monofluoride (4.0mmol), 2-chlorobenzonitrile (1.0mmol), 3,4,5-trifluoro-benzene boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 41
The cross-coupling reaction of catalytic 2-chloro-benzoic acid of palladium and 4-methylphenylboronic acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), cesium fluoride (2.0mmol), 2-chloro-benzoic acid (1.0mmol), 4-methylphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 42
The cross-coupling reaction of catalytic 2-chloro-benzoic acid of palladium and 4-methoxyphenylboronic acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), cesium fluoride (4.0mmol), 2-chloro-benzoic acid (1.0mmol), 4-methoxyphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 43
The cross-coupling reaction of catalytic 2-chloro-benzoic acid of palladium and 4-trifluoromethyl phenylo boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), cesium fluoride (2.0mmol), 2-chloro-benzoic acid (1.0mmol), 4-trifluoromethyl phenylo boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 44
The catalytic 2-chloro-benzoic acid of palladium and 3,4, the cross-coupling reaction of 5-trifluoro-benzene boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), cesium fluoride (4.0mmol), 2-chloro-benzoic acid (1.0mmol), 3,4,5-trifluoro-benzene boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 45
The cross-coupling reaction of palladium catalytic 4-trifluoromethyl chlorobenzene and 4-methylphenylboronic acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), cesium carbonate (2.0mmol), 4-trifluoromethyl chlorobenzene (1.0mmol), 4-methylphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 93% yield.
Embodiment 46
The cross-coupling reaction of palladium catalytic 4-trifluoromethyl chlorobenzene and 4-methoxyphenylboronic acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), cesium carbonate (4.0mmol), 4-trifluoromethyl chlorobenzene (1.0mmol), 4-methoxyphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 47
The cross-coupling reaction of palladium catalytic 4-trifluoromethyl chlorobenzene and 4-fluorobenzoic boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Pd (OAc)
2(0.02mmol), cesium carbonate (2.0mmol), 4-trifluoromethyl chlorobenzene (1.0mmol), 4-fluorobenzoic boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 48
Palladium catalytic 4-trifluoromethyl chlorobenzene and 3,4, the cross-coupling reaction of 5-trifluoro-benzene boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Pd (OAc)
2(0.05mmol), cesium carbonate (4.0mmol), 4-trifluoromethyl chlorobenzene (1.0mmol), 3,4,5-trifluoro-benzene boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 92% yield.
Embodiment 49
The cross-coupling reaction of Palladous chloride catalytic 4-methoxyl group chlorobenzene and phenylo boric acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Palladous chloride (0.02mmol), salt of wormwood (2.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), phenylo boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 94% yield.
Embodiment 50
The cross-coupling reaction of Palladous chloride catalytic 4-methoxyl group chlorobenzene and 2-methylphenylboronic acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Palladous chloride (0.05mmol), salt of wormwood (4.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 2-methylphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 51
The cross-coupling reaction of Palladous chloride catalytic 4-methoxyl group chlorobenzene and 3-methylphenylboronic acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Palladous chloride (0.02mmol), salt of wormwood (2.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 3-methylphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 52
The cross-coupling reaction of Palladous chloride catalytic 4-methoxyl group chlorobenzene and 4-methylphenylboronic acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Palladous chloride (0.05mmol), salt of wormwood (4.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 4-methylphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 53
The cross-coupling reaction of Palladous chloride catalytic 4-methoxyl group chlorobenzene and 2-methoxyphenylboronic acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Palladous chloride (0.02mmol), yellow soda ash (2.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 2-methoxyphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 93% yield.
Embodiment 54
The cross-coupling reaction of Palladous chloride catalytic 4-methoxyl group chlorobenzene and 3-methoxyphenylboronic acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Palladous chloride (0.05mmol), yellow soda ash (4.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 3-methoxyphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 55
The cross-coupling reaction of Palladous chloride catalytic 4-methoxyl group chlorobenzene and 4-methoxyphenylboronic acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Palladous chloride (0.02mmol), yellow soda ash (2.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 4-methoxyphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 56
The cross-coupling reaction of Palladous chloride catalytic 4-methoxyl group chlorobenzene and 4-trifluoromethyl phenylo boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Palladous chloride (0.05mmol), yellow soda ash (4.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 4-trifluoromethyl phenylo boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 57
The cross-coupling reaction of Palladous chloride catalytic 4-methoxyl group chlorobenzene and 4-fluorobenzoic boric acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Palladous chloride (0.02mmol), potassium tert.-butoxide (2.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 4-fluorobenzoic boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 58
Palladous chloride catalytic 4-methoxyl group chlorobenzene and 3, the cross-coupling reaction of 4-two fluorobenzoic boric acids
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Palladous chloride (0.05mmol), potassium tert.-butoxide (4.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 3,4-two fluorobenzoic boric acids (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 59
Palladous chloride catalytic 4-methoxyl group chlorobenzene and 3,4, the cross-coupling reaction of 5-trifluoro-benzene boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Palladous chloride (0.02mmol), potassium tert.-butoxide (2.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 3,4,5-trifluoro-benzene boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 60
The cross-coupling reaction of Palladous chloride catalytic 4-methoxyl group chlorobenzene and 4-chlorobenzene boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Palladous chloride (0.05mmol), potassium tert.-butoxide (4.0mmol), 4-methoxyl group chlorobenzene (1.0mmol), 4-chlorobenzene boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 61
The cross-coupling reaction of Palladous chloride catalytic 4-ethanoyl chlorobenzene and phenylo boric acid
In air; successively with the PEG-200 (5.0mmol) of following mol ratio; Palladous chloride (0.02mmol); sodium tert-butoxide (2.0mmol); 4-ethanoyl chlorobenzene (1.0mmol); phenylo boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 97% yield.
Embodiment 62
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of Palladous chloride and phenylo boric acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Palladous chloride (0.05mmol), sodium tert-butoxide (4.0mmol), 4-nitro-chlorobenzene (1.0mmol), phenylo boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 63
The cross-coupling reaction of catalytic 2-nitro-chlorobenzene of Palladous chloride and phenylo boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Palladous chloride (0.02mmol), sodium tert-butoxide (2.0mmol), 2-nitro-chlorobenzene (1.0mmol), phenylo boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 64
The cross-coupling reaction of Palladous chloride catalytic 4-hydroxyl chlorobenzene and phenylo boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Palladous chloride (0.05mmol), sodium tert-butoxide (4.0mmol), 4-hydroxyl chlorobenzene (1.0mmol), phenylo boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 65
The cross-coupling reaction of catalytic 4-chlorobenzaldehyde of Palladous chloride and phenylo boric acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Palladous chloride (0.02mmol), potassium ethylate (2.0mmol), 4-chlorobenzaldehyde (1.0mmol), phenylo boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 92% yield.
Embodiment 66
The cross-coupling reaction of catalytic 2-chlorobenzonitrile of Palladous chloride and phenylo boric acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Palladous chloride (0.05mmol), potassium ethylate (4.0mmol), 2-chlorobenzonitrile (1.0mmol), phenylo boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 67
The cross-coupling reaction of catalytic 2-chloro-benzoic acid of Palladous chloride and phenylo boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Palladous chloride (0.02mmol), potassium ethylate (2.0mmol), 2-chloro-benzoic acid (1.0mmol), phenylo boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 68
The cross-coupling reaction of Palladous chloride catalytic 4-trifluoromethyl chlorobenzene and phenylo boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Palladous chloride (0.05mmol), potassium ethylate (4.0mmol), 4-trifluoromethyl chlorobenzene (1.0mmol), phenylo boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 69
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of Palladous chloride and 2-methylphenylboronic acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Palladous chloride (0.02mmol), sodium ethylate (2.0mmol), 4-nitro-chlorobenzene (1.0mmol), 2-methylphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 93% yield.
Embodiment 70
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of Palladous chloride and 3-methylphenylboronic acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Palladous chloride (0.05mmol), sodium ethylate (4.0mmol), 4-nitro-chlorobenzene (1.0mmol), 3-methylphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 71
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of Palladous chloride and 4-methylphenylboronic acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Palladous chloride (0.02mmol), sodium ethylate (2.0mmol), 4-nitro-chlorobenzene (1.0mmol), 4-methylphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 72
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of Palladous chloride and 2-methoxyphenylboronic acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Palladous chloride (0.05mmol), sodium ethylate (4.0mmol), 4-nitro-chlorobenzene (1.0mmol), 2-methoxyphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 73
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of Palladous chloride and 3-methoxyphenylboronic acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Palladous chloride (0.02mmol), potassium hydroxide (2.0mmol), 4-nitro-chlorobenzene (1.0mmol), 3-methoxyphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 5 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 91% yield.
Embodiment 74
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of Palladous chloride and 4-methoxyphenylboronic acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Palladous chloride (0.05mmol), potassium hydroxide (4.0mmol), 4-nitro-chlorobenzene (1.0mmol), 4-methoxyphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 75
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of Palladous chloride and 4-trifluoromethyl phenylo boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Palladous chloride (0.02mmol), potassium hydroxide (2.0mmol), 4-nitro-chlorobenzene (1.0mmol), 4-trifluoromethyl phenylo boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 76
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of Palladous chloride and 4-fluorobenzoic boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Palladous chloride (0.05mmol), potassium hydroxide (4.0mmol), 4-nitro-chlorobenzene (1.0mmol), 4-fluorobenzoic boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 77
The catalytic 4-nitro-chlorobenzene of Palladous chloride and 3, the cross-coupling reaction of 4-two fluorobenzoic boric acids
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Palladous chloride (0.02mmol), sodium hydroxide (2.0mmol), 4-nitro-chlorobenzene (1.0mmol), 3,4-two fluorobenzoic boric acids (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, 30 ℃ of stirring reactions 5 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 78
The catalytic 4-nitro-chlorobenzene of Palladous chloride and 3,4, the cross-coupling reaction of 5-trifluoro-benzene boric acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Palladous chloride (0.05mmol), sodium hydroxide (4.0mmol), 4-nitro-chlorobenzene (1.0mmol), 3,4,5-trifluoro-benzene boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 79
The cross-coupling reaction of catalytic 4-nitro-chlorobenzene of Palladous chloride and 4-chlorobenzene boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Palladous chloride (0.02mmol), sodium hydroxide (2.0mmol), 4-nitro-chlorobenzene (1.0mmol), 4-chlorobenzene boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 5 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 92% yield.
Embodiment 80
The cross-coupling reaction of catalytic 4-chlorobenzaldehyde of Palladous chloride and 4-methylphenylboronic acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Palladous chloride (0.05mmol), sodium hydroxide (4.0mmol), 4-chlorobenzaldehyde (1.0mmol), 4-methylphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 81
The cross-coupling reaction of catalytic 4-chlorobenzaldehyde of Palladous chloride and 4-methoxyphenylboronic acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Palladous chloride (0.02mmol), potassiumphosphate (2.0mmol), 4-chlorobenzaldehyde (1.0mmol), 4-methoxyphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 93% yield.
Embodiment 82
The cross-coupling reaction of catalytic 4-chlorobenzaldehyde of Palladous chloride and 4-trifluoromethyl phenylo boric acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Palladous chloride (0.05mmol), potassiumphosphate (4.0mmol), 4-chlorobenzaldehyde (1.0mmol), 4-trifluoromethyl phenylo boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 83
The cross-coupling reaction of catalytic 4-chlorobenzaldehyde of Palladous chloride and 4-fluorobenzoic boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Palladous chloride (0.02mmol), potassiumphosphate (2.0mmol), 4-chlorobenzaldehyde (1.0mmol), 4-fluorobenzoic boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 84
The catalytic 4-chlorobenzaldehyde of Palladous chloride and 3,4, the cross-coupling reaction of 5-trifluoro-benzene boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Palladous chloride (0.05mmol), potassiumphosphate (4.0mmol), 4-chlorobenzaldehyde (1.0mmol), 3,4,5-trifluoro-benzene boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 85
The cross-coupling reaction of catalytic 2-chlorobenzonitrile of Palladous chloride and 4-methylphenylboronic acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Palladous chloride (0.02mmol), Potassium monofluoride (2.0mmol), 2-chlorobenzonitrile (1.0mmol), 4-methylphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 94% yield.
Embodiment 86
The cross-coupling reaction of catalytic 2-chlorobenzonitrile of Palladous chloride and 4-methoxyphenylboronic acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Palladous chloride (0.05mmol), Potassium monofluoride (4.0mmol), 2-chlorobenzonitrile (1.0mmol), 4-methoxyphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 1 hour, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 87
The cross-coupling reaction of catalytic 2-chlorobenzonitrile of Palladous chloride and 4-trifluoromethyl phenylo boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Palladous chloride (0.02mmol), Potassium monofluoride (2.0mmol), 2-chlorobenzonitrile (1.0mmol), 4-trifluoromethyl phenylo boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 3 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Embodiment 88
The catalytic 2-chlorobenzonitrile of Palladous chloride and 3,4, the cross-coupling reaction of 5-trifluoro-benzene boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Palladous chloride (0.05mmol), Potassium monofluoride (4.0mmol), 2-chlorobenzonitrile (1.0mmol), 3,4,5-trifluoro-benzene boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 89
The cross-coupling reaction of catalytic 2-chloro-benzoic acid of Palladous chloride and 4-methylphenylboronic acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Palladous chloride (0.02mmol), cesium fluoride (2.0mmol), 2-chloro-benzoic acid (1.0mmol), 4-methylphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 98% yield.
Embodiment 90
The cross-coupling reaction of catalytic 2-chloro-benzoic acid of Palladous chloride and 4-methoxyphenylboronic acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Palladous chloride (0.05mmol), cesium fluoride (4.0mmol), 2-chloro-benzoic acid (1.0mmol), 4-methoxyphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 91
The cross-coupling reaction of catalytic 2-chloro-benzoic acid of Palladous chloride and 4-trifluoromethyl phenylo boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Palladous chloride (0.02mmol), cesium fluoride (2.0mmol), 2-chloro-benzoic acid (1.0mmol), 4-trifluoromethyl phenylo boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 92% yield.
Embodiment 92
The catalytic 2-chloro-benzoic acid of Palladous chloride and 3,4, the cross-coupling reaction of 5-trifluoro-benzene boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Palladous chloride (0.05mmol), cesium fluoride (4.0mmol), 2-chloro-benzoic acid (1.0mmol), 3,4,5-trifluoro-benzene boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 97% yield.
Embodiment 93
The cross-coupling reaction of Palladous chloride catalytic 4-trifluoromethyl chlorobenzene and 4-methylphenylboronic acid
In air, successively with the PEG-200 (5.0mmol) of following mol ratio, Palladous chloride (0.02mmol), cesium carbonate (2.0mmol), 4-trifluoromethyl chlorobenzene (1.0mmol), 4-methylphenylboronic acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 30 ℃ of stirring reactions 5 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 94% yield.
Embodiment 94
The cross-coupling reaction of Palladous chloride catalytic 4-trifluoromethyl chlorobenzene and 4-methoxyphenylboronic acid
In air, successively with the PEG-200 (20.0mmol) of following mol ratio, Palladous chloride (0.05mmol), cesium carbonate (4.0mmol), 4-trifluoromethyl chlorobenzene (1.0mmol), 4-methoxyphenylboronic acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 92% yield.
Embodiment 95
The cross-coupling reaction of Palladous chloride catalytic 4-trifluoromethyl chlorobenzene and 4-fluorobenzoic boric acid
In air, successively with the PEG-2000 (1.0mmol) of following mol ratio, Palladous chloride (0.02mmol), cesium carbonate (2.0mmol), 4-trifluoromethyl chlorobenzene (1.0mmol), 4-fluorobenzoic boric acid (1.1mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 4 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 95% yield.
Embodiment 96
Palladous chloride catalytic 4-trifluoromethyl chlorobenzene and 3,4, the cross-coupling reaction of 5-trifluoro-benzene boric acid
In air, successively with the PEG-2000 (2.0mmol) of following mol ratio, Palladous chloride (0.05mmol), cesium carbonate (4.0mmol), 4-trifluoromethyl chlorobenzene (1.0mmol), 3,4,5-trifluoro-benzene boric acid (2.0mmol) and interior mark n-decane (1.0mmol) add the 50ml round-bottomed flask, and 60 ℃ of stirring reactions 2 hours, gas-chromatography was followed the tracks of reaction.The aftertreatment of biphenyl class product and characterizing method are with embodiment 1.The GC analytical results obtains 100% transformation efficiency and 96% yield.
Claims (6)
- One kind in the presence of solvent and catalyzer, the method for preparing biphenyl compound by the Suzuki cross-coupling reaction of chlorinated aromatic hydrocarbons and aryl boric acid, it is characterized in that this method is in air, successively with 1.0～20.0mmol solvent polyoxyethylene glycol, 0.02～0.05mmol palladium catalyst precursor, 2.0～4.0mmol alkali, 1.0mmol chlorinated aromatic hydrocarbons, 1.1 the mark n-decane adds in the 50ml round-bottomed flask in～2.0mmol aryl boric acid and the 1.0mmol, 30～60 ℃ of stirring reactions 1～5 hour, follow the tracks of with gas-chromatography in the reaction process, after reaction finishes, with 5ml * 3 time extracted with diethyl ether reaction product, merge organic phase, use anhydrous Na 2SO 4Drying is filtered, and filtrate concentrates, and uses column chromatography, and elutriant is the ethyl acetate/petroleum ether of volume ratio 1/10, obtain transformation efficiency and be 95～100% and separation yield be 90～99% biphenyl compound.
- 2. according to the preparation method of the described biphenyl compound of claim 1, it is characterized in that employed solvent is that molecular-weight average is 200～2000 polyoxyethylene glycol.
- 3. according to the preparation method of the described biphenyl compound of claim 1, it is characterized in that employed palladium catalyst precursor is palladium or Palladous chloride.
- 4. according to the preparation method of the described biphenyl compound of claim 1, it is characterized in that employed alkali is salt of wormwood, yellow soda ash, potassium tert.-butoxide, sodium tert-butoxide, potassium ethylate, sodium ethylate, potassium hydroxide, sodium hydroxide, potassiumphosphate, Potassium monofluoride, cesium fluoride or cesium carbonate.
- 5. according to the preparation method of the described biphenyl compound of claim 1, it is characterized in that employed chlorinated aromatic hydrocarbons is a 4-methoxyl group chlorobenzene, 4-ethanoyl chlorobenzene; the 4-nitro-chlorobenzene, 2-nitro-chlorobenzene, 4-hydroxyl chlorobenzene; 4-chlorobenzaldehyde, 2-chlorobenzonitrile, 2-chloro-benzoic acid or 4-trifluoromethyl chlorobenzene.
- 6. according to the preparation method of the described biphenyl compound of claim 1, it is characterized in that employed aryl boric acid is a phenylo boric acid, the 2-methylphenylboronic acid, the 3-methylphenylboronic acid, 4-methylphenylboronic acid, 2-methoxyphenylboronic acid, the 3-methoxyphenylboronic acid, 4-methoxyphenylboronic acid, 4-trifluoromethyl phenylo boric acid, the 4-fluorobenzoic boric acid, 3,4-two fluorobenzoic boric acids, 3,4,5-trifluoro-benzene boric acid or 4-chlorobenzene boric acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009156359A2 (en) | 2008-06-25 | 2009-12-30 | Basf Se | Method for producing substituted biphenyls |
| CN101434527B (en) * | 2008-12-22 | 2011-08-24 | 北京奥得赛化学股份有限公司 | Preparations of 4-formyl biphenyl, 4-hydroxymethyl biphenyl and 4-chloromethyl biphenyl |
| CN101638352B (en) * | 2009-08-14 | 2011-08-31 | 大连理工大学 | Aryl-replaced nitrogen heterocyclic compound preparation method |
| CN101857517B (en) * | 2010-06-19 | 2012-12-26 | 大连理工大学 | Method for preparing fluorobiaryl compound in pure water solution |
| CN102010280B (en) * | 2010-12-01 | 2013-06-05 | 西北师范大学 | Preparation method of biaryl compound |
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| CN102351620A (en) * | 2011-08-09 | 2012-02-15 | 太原理工大学 | Method for preparing biphenyl compound through catalyzing Suzuki coupling reaction by nanometer palladium catalyst |
| CN102491862B (en) * | 2011-12-08 | 2014-06-25 | 大连理工大学 | Method for preparing biaryl compound in pure water |
| CN102643152A (en) * | 2012-05-14 | 2012-08-22 | 黑龙江大学 | Green synthesis method for nanometer palladium catalysis biphenyl compound |
| CN105237379B (en) * | 2015-10-29 | 2017-03-22 | 河南省科学院化学研究所有限公司 | Production method for 4-bromo fluorenone |
| CN106631708A (en) * | 2016-11-23 | 2017-05-10 | 烟台海川化学制品有限公司 | Preparation method of 2,6-diphenylphenol |
| CN106831581B (en) * | 2017-02-10 | 2021-07-09 | 上海大学 | Azaspiro-bifluorene derivative and preparation method thereof |
| CN109232201A (en) * | 2018-10-25 | 2019-01-18 | 华东医药（西安）博华制药有限公司 | A kind of improved sevoflurane reaction solution post-processing approach |
| CN109761820B (en) * | 2019-01-25 | 2022-03-25 | 浙江工业大学 | Chemical synthesis method of 3',4',5 '-trifluoro- [1,1' -biphenyl ] -2-amine |
-
2007
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Non-Patent Citations (4)
| Title |
|---|
| Merrifield 树脂负载的膦钯催化剂制备及其在Suzuki 反应中的应用. 徐，宁，王全瑞*，陶凤岗.有 机 化 学，第25 卷第4期. 2005 |
| Merrifield 树脂负载的膦钯催化剂制备及其在Suzuki 反应中的应用. 徐，宁，王全瑞*，陶凤岗.有 机 化 学，第25 卷第4期. 2005 * |
| 芳基硼酸与溴代芳烃的三苯基膦钯催化偶联反应. 彭小丽3，，陈连植a，郁，通a.中国医药工业杂志，第29卷第(3)期. 1998 |
| 芳基硼酸与溴代芳烃的三苯基膦钯催化偶联反应. 彭小丽3，，陈连植a，郁，通a.中国医药工业杂志，第29卷第(3)期. 1998 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768036B (en) * | 2010-01-23 | 2013-05-08 | 大连理工大学 | Method for preparing heterocyclic aromatic compound replaced by aryl in alcohol solvent |
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