CN103804105A - Synthesis method for biphenyl compounds - Google Patents

Synthesis method for biphenyl compounds Download PDF

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CN103804105A
CN103804105A CN201410053408.5A CN201410053408A CN103804105A CN 103804105 A CN103804105 A CN 103804105A CN 201410053408 A CN201410053408 A CN 201410053408A CN 103804105 A CN103804105 A CN 103804105A
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biphenyl compound
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冯高峰
刘福建
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University of Shaoxing
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Abstract

The invention relates to the field of organic synthesis, and discloses a synthesis method for biphenyl compounds. The method comprises the following steps: in the presence of an inorganic base, in a mixed solvent of ethanol and water, adding arylboronic acid, aryl halide and a heterogeneous catalyst ZrO2-Pd(OAc)2; reacting 30-180 min while the temperature is controlled at 60-120 DEG C; after reaction liquid is cooled to room temperature, filtering the reaction liquid, washing, and recovering the catalyst; adding a NaOH aqueous solution into filtrate, and carrying out extraction, drying and concentration on the obtained product so as to obtain a high-purity biphenyl compound. According to the invention, the heterogeneous catalyst ZrO2-Pd(OAc)2 which is high in catalytic activity and reusable is used for the first time, the quick coupling of aryl halide and arylboronic acid is realized by taking green and non-toxic ethanol and water as solvents under mild conditions, and then excessive arylboronic acid is removed by using the NaOH aqueous solution, so that the high-purity biphenyl compound is obtained. The method is good in catalytic effect, simple in operation, and environment-friendly.

Description

A kind of synthetic method of biphenyl compound
Technical field
The present invention relates to organic synthesis field, related in particular to a kind of synthetic method of biphenyl compound.
Background technology
Biphenyl compound is the very important compound of a class, is widely used in the fields such as medicine, dyestuff, advanced functional materials, and developing its green, low cost and synthetic method simple to operate is the study hotspot of organic synthesis.The halogenated aryl hydrocarbon of Pd catalysis and the linked reaction of aryl boric acid---Suzuki reaction is one of effective ways of synthetic biphenyl compound.Classical Suzuki reacts take palladium as catalyzer, and under the existence of part and alkali, halogenated aryl hydrocarbon and aryl boric acid carry out coupling and obtain aryl-linking compound in homogeneous system.Although homogeneous phase Suzuki reaction has the advantages such as the high and good reaction selectivity of catalytic activity, exists catalyzer can not separate with product, catalyzer is not easy to be recycled and product is caused to the shortcomings such as metallic pollution.Meanwhile, the common complex structure of part that the homogeneous phase Suzuki of Pd catalysis reacts used, expensive, to water and air sensitivity, solvent used is generally the polar solvent that toxicity is larger, conventionally needs protection of inert gas in reaction process.These limitation have restricted to a great extent homogeneous phase Suzuki and have reacted in industrial application.
Summary of the invention
There is the unsettled part that needs to use costliness in the halogenated aryl hydrocarbon and the aryl boric acid homogeneous phase linked reaction that the present invention is directed to palladium catalysis in prior art, Pd can not recycle and use in a large number the shortcomings such as the organic solvent that toxicity is larger, a kind of synthetic method of biphenyl compound is provided, and present method is to utilize high catalytic activity reusable heterogeneous catalyst ZrO 2-Pd (OAc) 2and under gentle condition, halogenated aryl hydrocarbon and aryl boric acid are carried out to quick coupling take the second alcohol and water of green non-poisonous property as solvent, carry out simple process with the NaOH aqueous solution and get final product to obtain high purity biphenyl compound afterwards.Present method excellent catalytic effect, simple to operate, environmentally friendly.
In order to solve the problems of the technologies described above, the present invention is solved by following technical proposals:
A synthetic method for biphenyl compound as shown in the formula (I), method is as follows:
Under mineral alkali existence condition, in the mixed solvent of second alcohol and water, add aryl boric acid, halogenated aryl hydrocarbon, heterogeneous catalyst ZrO 2-Pd (OAc) 2, control temperature is 60-120, ℃ reaction 30-180min, and reaction solution is cooled to after room temperature through filtering, washing and recycling catalyzer, adds the NaOH aqueous solution to filtrate, obtains high purity biphenyl compound through extraction, after dry, concentrated; Its reaction formula is as follows:
Wherein, X=I or Br, R 1=H, F, C 2h 5or CHO, R 2=CH 3, C 2h 5, COCH 3, OCH 3, CN or CHO.
As preferably, described ZrO 2-Pd (OAc) 2the preparation method of catalyzer is as follows: by mesoporous ZrO 2be scattered in tetrahydrofuran (THF), add a certain amount of Pd (OAc) 2, under room temperature, stir after 3 hours, use Rotary Evaporators concentrating under reduced pressure, at the temperature of 50 ℃, vacuum-drying obtain catalyst Z rO 2-Pd (OAc) 2.Catalyst Z rO 2-Pd (OAc) 2pd (OAc) in use 2quality percentage composition is with Pd (OAc) 2theoretical percentage composition calculate.
As preferably, described Pd (OAc) 2with mesoporous ZrO 2mass ratio be 1:(40-100).Pd (OAc) 2be dispersed in mesopore metal oxide ZrO 2in, the reunion of Pd in reaction process can be prevented, thereby its catalytic activity can be kept.
As preferably, Pd (OAc) in the described catalyzer adding 2molar mass be the 0.1-1% of halogenated aryl hydrocarbon molar mass.The inventive method is that the building-up process of biphenyl compound participates in without part, without protection of inert gas.Catalyst Z rO 2-Pd (OAc) 2catalytic activity is high, reclaims simply, reusable and do not reduce its catalytic activity, effectively saves synthetic cost.
As preferably, in described mixed solvent, the volume ratio of ethanol and water is 3:(1-3).The solvent using is the second alcohol and water of green non-poisonous property, environmentally friendly.
As preferably, described mineral alkali is K 2cO 3.
As preferably, described reclaims after catalyzer after filtration through cooled reaction solution, adds the NaOH aqueous solution to process to filtrate, and with organic solvent extraction, organic layer is used saturated NaCl solution washing, anhydrous Na successively 2sO 4be dried, after concentrating under reduced pressure, obtain highly purified biphenyl compound.Remove the remaining aryl boric acid of reaction with the NaOH aqueous solution, method is simple and effect is very good.
As preferably, described halogenated aryl hydrocarbon be to toluene iodide, paraiodoanisole, to iodobenzene formonitrile HCN, adjacent iodanisol, para-bromo toluene, m-bromotoluene, Meta Bromo Anisole, a bromoacetophenone, to methiodide benzene, in methiodide benzene any.
The present invention, owing to having adopted above technical scheme, has significant technique effect:
1, Pd (OAc) 2be dispersed in mesopore metal oxide ZrO 2in, the reunion of Pd in reaction process can be prevented, thereby its catalytic activity can be kept.
2, the building-up process of biphenyl compound participates in without part, without protection of inert gas.Catalyst Z rO 2-Pd (OAc) 2catalytic activity high (molar mass of Pd be low to moderate halogenated aryl hydrocarbon molar mass 0.1%), reclaims simply, reusable and do not reduce its catalytic activity, effectively saves synthetic cost.
3, the inventive method subsequent processes is removed the remaining aryl boric acid of reaction with the NaOH aqueous solution, and this treatment process is simple, cost is low, effective.
4, the solvent that the inventive method is used is the second alcohol and water of green non-poisonous property, environmentally friendly.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail:
Embodiment 1
In the withstand voltage reaction tubes of 100mL, add successively magneton, to toluene iodide (5mmol), phenylo boric acid (7.5mmol), ZrO 2-Pd (OAc) 2catalyzer (280mg contains 2.8mg palladium, 0.25mol%), K 2cO 3(10mmol), water (5mL) and ethanol (15mL).Reaction tubes with after silicone rubber pad sealing the oil bath heating of 100 ℃ 0.5 hour, react completely through vapor detection, and by the method for filtration by catalyst recovery.Water (4mL × 2), ethyl acetate (100mL × 2) washing successively for catalyzer.After being merged, filtrate adds the NaOH aqueous solution branch vibration layer.Organic layer is used saturated NaCl solution washing, anhydrous Na successively 2sO 4dry, warp after concentrating under reduced pressure 1h-NMR detects and is defined as highly purified coupled product, and productive rate is 97%, and structure is as follows:
Figure BDA0000466372720000031
Embodiment 2-5
In the withstand voltage reaction tubes of 100mL, add successively magneton, in toluene iodide (5mmol), phenylo boric acid (7.5mmol), embodiment 1 reclaim whole ZrO 2-Pd (OAc) 2catalyzer, K 2cO 3(10mmol), water (5mL) and ethanol (15mL).Reaction tubes with after silicone rubber pad sealing the oil bath heating of 100 ℃ 0.5 hour, react completely through vapor detection, and by the method for filtration by catalyst recovery.Water (4mL × 2), ethyl acetate (100mL × 2) washing successively for catalyzer.After being merged, filtrate adds the NaOH aqueous solution branch vibration layer.Organic layer is used saturated NaCl solution washing, anhydrous Na successively 2sO 4dry, warp after concentrating under reduced pressure 1h-NMR detects and is defined as highly purified coupled product.The catalyzer that reclaims gained is repeated to experiment, the results are shown in Table one.
Table one: ZrO 2-Pd (OAc) 2catalyzer recycle experiment
Figure BDA0000466372720000032
Embodiment 6
In the withstand voltage reaction tubes of 10mL, add successively magneton, paraiodoanisole (1mmol), phenylo boric acid (1.5mmol), ZrO 2-Pd (OAc) 2catalyzer (56mg contains 0.56mg palladium, 0.25mol%), K 2cO 3(2mmol), water (1mL) and ethanol (3mL).Reaction tubes with after silicone rubber pad sealing the oil bath heating of 100 ℃ 0.5 hour, react completely through vapor detection, and by the method for filtration by catalyst recovery.Water (2mL × 2), ethyl acetate (50mL × 2) washing successively for catalyzer.After being merged, filtrate adds the NaOH aqueous solution branch vibration layer.Organic layer is used saturated NaCl solution washing, anhydrous Na successively 2sO 4dry, after concentrating under reduced pressure, obtain highly purified coupled product, productive rate is 97%, warp 1h-NMR detects, and structure is as follows:
Embodiment 7
In the withstand voltage reaction tubes of 10mL, add successively magneton, to iodobenzene formonitrile HCN (1mmol), phenylo boric acid (1.5mmol), ZrO 2-Pd (OAc) 2catalyzer (56mg contains 0.56mg palladium, 0.25mol%), K 2cO 3(2mmol), water (1mL) and ethanol (3mL).After reaction tubes sealing, the oil bath heating of 100 ℃ 0.5 hour, react completely through vapor detection, and by the method for filtration by catalyst recovery.Water (2mL × 2), ethyl acetate (50mL × 2) washing successively for catalyzer.After being merged, filtrate adds the NaOH aqueous solution branch vibration layer.Organic layer is used saturated NaCl solution washing, anhydrous Na successively 2sO 4dry, after concentrating under reduced pressure, obtain highly purified coupled product, productive rate is 99%, warp 1h-NMR detects, and structure is as follows:
Figure BDA0000466372720000041
Embodiment 8
In the withstand voltage reaction tubes of 10mL, add successively magneton, adjacent iodanisol (1mmol), phenylo boric acid (1.5mmol), ZrO 2-Pd (OAc) 2catalyzer (56mg contains 0.56mg palladium, 0.25mol%), K 2cO 3(2mmol), water (1mL) and ethanol (3mL).After reaction tubes sealing, the oil bath heating of 100 ℃ 1 hour, react completely through vapor detection, and by the method for filtration by catalyst recovery.Water (2mL × 2), ethyl acetate (50mL × 2) washing successively for catalyzer.After being merged, filtrate adds the NaOH aqueous solution branch vibration layer.Organic layer is used saturated NaCl solution washing, anhydrous Na successively 2sO 4dry, after concentrating under reduced pressure, obtain highly purified coupled product, productive rate is 98%, warp 1h-NMR detects, and structure is as follows:
Figure BDA0000466372720000042
Embodiment 9
In the withstand voltage reaction tubes of 10mL, add successively magneton, para-bromo toluene (1mmol), phenylo boric acid (1.5mmol), ZrO 2-Pd (OAc) 2catalyzer (56mg contains 0.56mg palladium, 0.25mol%), K 2cO 3(2mmol), water (1mL) and ethanol (3mL).After reaction tubes sealing, the oil bath heating of 100 ℃ 3 hours, react completely through vapor detection, and by the method for filtration by catalyst recovery.Water (2mL × 2), ethyl acetate (50mL × 2) washing successively for catalyzer.After being merged, filtrate adds the NaOH aqueous solution branch vibration layer.Organic layer is used saturated NaCl solution washing, anhydrous Na successively 2sO 4dry, after concentrating under reduced pressure, obtain highly purified coupled product, productive rate is 97%, warp 1h-NMR detects, and structure is as follows:
Figure BDA0000466372720000043
Embodiment 10
In the withstand voltage reaction tubes of 10mL, add successively magneton, m-bromotoluene (1mmol), phenylo boric acid (1.5mmol), ZrO 2-Pd (OAc) 2catalyzer (56mg contains 0.56mg palladium, 0.25mol%), K 2cO 3(2mmol), water (1mL) and ethanol (3mL).After reaction tubes sealing, the oil bath heating of 100 ℃ 3 hours, react completely through vapor detection, and by the method for filtration by catalyst recovery.Water (2mL × 2), ethyl acetate (50mL × 2) washing successively for catalyzer.After being merged, filtrate adds the NaOH aqueous solution branch vibration layer.Organic layer is used saturated NaCl solution washing, anhydrous Na successively 2sO 4dry, after concentrating under reduced pressure, obtain highly purified coupled product, productive rate is 91%, warp 1h-NMR detects, and structure is as follows:
Figure BDA0000466372720000051
Embodiment 11
In the withstand voltage reaction tubes of 10mL, add successively magneton, Meta Bromo Anisole (1mmol), phenylo boric acid (1.5mmol), ZrO 2-Pd (OAc) 2catalyzer (56mg contains 0.56mg palladium, 0.25mol%), K 2cO 3(2mmol), water (1mL) and ethanol (3mL).After reaction tubes sealing, the oil bath heating of 100 ℃ 3 hours, react completely through vapor detection, and by the method for filtration by catalyst recovery.Water (2mL × 2), ethyl acetate (50mL × 2) washing successively for catalyzer.After being merged, filtrate adds the NaOH aqueous solution branch vibration layer.Organic layer is used saturated NaCl solution washing, anhydrous Na successively 2sO 4dry, after concentrating under reduced pressure, obtain highly purified coupled product, productive rate is 98%, warp 1h-NMR detects, and structure is as follows:
Figure BDA0000466372720000052
Embodiment 12
In the withstand voltage reaction tubes of 10mL, add successively magneton, a bromoacetophenone (1mmol), phenylo boric acid (1.5mmol), ZrO 2-Pd (OAc) 2catalyzer (56mg contains 0.56mg palladium, 0.25mol%), K 2cO 3(2mmol), water (1mL) and ethanol (3mL).After reaction tubes sealing, the oil bath heating of 100 ℃ 3 hours, react completely through vapor detection, and by the method for filtration by catalyst recovery.Water (2mL × 2), ethyl acetate (50mL × 2) washing successively for catalyzer.After being merged, filtrate adds the NaOH aqueous solution branch vibration layer.Organic layer is used saturated NaCl solution washing, anhydrous Na successively 2sO 4dry, after concentrating under reduced pressure, obtain highly purified coupled product, productive rate is 97%, detects through 1H-NMR, structure is as follows:
Embodiment 13
In the withstand voltage reaction tubes of 10mL, add successively magneton, to methiodide benzene (1mmol), 4-fluorobenzoic boric acid (1.5mmol), ZrO 2-Pd (OAc) 2catalyzer (56mg contains 0.56mg palladium, 0.25mol%), K 2cO 3(2mmol), water (1mL) and ethanol (3mL).After reaction tubes sealing, the oil bath heating of 100 ℃ 0.5 hour, react completely through vapor detection, and by the method for filtration by catalyst recovery.Water (2mL × 2), ethyl acetate (50mL × 2) washing successively for catalyzer.After being merged, filtrate adds the NaOH aqueous solution branch vibration layer.Organic layer is used saturated NaCl solution washing, anhydrous Na successively 2sO 4dry, after concentrating under reduced pressure, obtain highly purified coupled product, productive rate is 99%, warp 1h-NMR detects, and structure is as follows:
Figure BDA0000466372720000061
Embodiment 14
In the withstand voltage reaction tubes of 10mL, add successively magneton, to methiodide benzene (1mmol), 4-formylphenylboronic acid (1.5mmol), ZrO 2-Pd (OAc) 2catalyzer (56mg contains 0.56mg palladium, 0.25mol%), K 2cO 3(2mmol), water (1mL) and ethanol (3mL).After reaction tubes sealing, the oil bath heating of 100 ℃ 40 minutes, react completely through vapor detection, and by the method for filtration by catalyst recovery.Water (2mL × 2), ethyl acetate (50mL × 2) washing successively for catalyzer.After being merged, filtrate adds the NaOH aqueous solution branch vibration layer.Organic layer is used saturated NaCl solution washing, anhydrous Na successively 2sO 4dry, after concentrating under reduced pressure, obtain highly purified coupled product, productive rate is 91%, warp 1h-NMR detects, and structure is as follows:
Figure BDA0000466372720000062
Embodiment 15
In the withstand voltage reaction tubes of 10mL, add successively magneton, to methiodide benzene (1mmol), 4-ethylbenzene boric acid (1.5mmol), ZrO 2-Pd (OAc) 2catalyzer (56mg contains 0.56mg palladium, 0.25mol%), K 2cO 3(2mmol), water (1mL) and ethanol (3mL).After reaction tubes sealing, the oil bath heating of 100 ℃ 0.5 hour, react completely through vapor detection, and by the method for filtration by catalyst recovery.Water (2mL × 2), ethyl acetate (50mL × 2) washing successively for catalyzer.After being merged, filtrate adds the NaOH aqueous solution branch vibration layer.Organic layer is used saturated NaCl solution washing, anhydrous Na successively 2sO 4dry, after concentrating under reduced pressure, obtain highly purified coupled product, productive rate is 99%, warp 1h-NMR detects, and structure is as follows:
Figure BDA0000466372720000063
In a word, the foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to the covering scope of patent of the present invention.

Claims (8)

1. a synthetic method for biphenyl compound as shown in the formula (I), is characterized in that, method is as follows:
Under mineral alkali existence condition, in the mixed solvent of second alcohol and water, add aryl boric acid, halogenated aryl hydrocarbon, heterogeneous catalyst ZrO 2-Pd (OAc) 2, control temperature is 60-120, ℃ reaction 30-180min, and reaction solution is cooled to after room temperature through filtering, washing and recycling catalyzer, adds the NaOH aqueous solution to filtrate, obtains high purity biphenyl compound through extraction, after dry, concentrated; Its reaction formula is as follows:
Figure FDA0000466372710000011
Wherein, X=I or Br, R 1=H, F, C 2h 5or CHO, R 2=CH 3, C 2h 5, COCH 3, OCH 3, CN or CHO.
2. the synthetic method of biphenyl compound according to claim 1, is characterized in that: described ZrO 2-Pd (OAc) 2the preparation method of catalyzer is as follows: by mesoporous ZrO 2be scattered in tetrahydrofuran (THF), add Pd (OAc) 2, under room temperature, stir after 3 hours, use Rotary Evaporators concentrating under reduced pressure, at the temperature of 50 ℃, vacuum-drying obtain catalyst Z rO 2-Pd (OAc) 2.
3. the synthetic method of biphenyl compound according to claim 2, is characterized in that: described Pd (OAc) 2with mesoporous ZrO 2mass ratio be 1:(40-100).
4. the synthetic method of biphenyl compound according to claim 1, is characterized in that: described in Pd (OAc) in the catalyzer that adds 2molar mass be the 0.1-1% of halogenated aryl hydrocarbon molar mass.
5. the synthetic method of biphenyl compound according to claim 1, is characterized in that: in described mixed solvent, the volume ratio of ethanol and water is 3:(1-3).
6. the synthetic method of biphenyl compound according to claim 1, is characterized in that: described mineral alkali is K 2cO 3.
7. the synthetic method of biphenyl compound according to claim 1, it is characterized in that: describedly reclaim after filtration after catalyzer through cooled reaction solution, add the NaOH aqueous solution to process to filtrate, and with organic solvent extraction, organic layer is used saturated NaCl solution washing, anhydrous Na successively 2sO 4after dry, obtain product after concentrating under reduced pressure.
8. the synthetic method of biphenyl compound according to claim 1, is characterized in that: described halogenated aryl hydrocarbon for to toluene iodide, paraiodoanisole, to iodobenzene formonitrile HCN, adjacent iodanisol, para-bromo toluene, m-bromotoluene, Meta Bromo Anisole, a bromoacetophenone, to methiodide benzene, in methiodide benzene any.
CN201410053408.5A 2014-02-17 2014-02-17 Synthesis method for biphenyl compounds Pending CN103804105A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104058909A (en) * 2014-07-02 2014-09-24 魏建华 Catalyzed synthesis method for drug intermediate diaryl-class compounds
WO2016019588A1 (en) * 2014-08-08 2016-02-11 The Broad Institute, Inc. Oxacazone compounds to treat clostridium difficile
CN106610397A (en) * 2015-10-27 2017-05-03 济南大学 Method for electrochemical detection of dopamine by using biphenyl organic mesoporous material-doped carbon paste electrode
CN108484372A (en) * 2018-04-04 2018-09-04 绍兴文理学院 A method of preparing biaryl by aryl hydrazines and aryl bromide

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4241747A1 (en) * 1992-12-11 1994-06-16 Merck Patent Gmbh Cross coupling reaction between aryl:boronic acid and aryl halide - in presence of catalyst and large excess of base to minimise coupling between boronic acid molecules
CN1745049A (en) * 2002-12-09 2006-03-08 麻省理工学院 Ligands for metals and improved metal-catalyzed processes based thereon
CN101029098A (en) * 2006-02-27 2007-09-05 三菱瓦斯化学株式会社 Preparation method for hydrogenated polymer
CN101225056A (en) * 2008-01-21 2008-07-23 浙江大学 Alpha-biphenyl-N-alkyl nitrone compound and synthetic method thereof
JP2009028645A (en) * 2007-07-27 2009-02-12 Nof Corp Palladium heterogeneous catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4241747A1 (en) * 1992-12-11 1994-06-16 Merck Patent Gmbh Cross coupling reaction between aryl:boronic acid and aryl halide - in presence of catalyst and large excess of base to minimise coupling between boronic acid molecules
CN1745049A (en) * 2002-12-09 2006-03-08 麻省理工学院 Ligands for metals and improved metal-catalyzed processes based thereon
CN101029098A (en) * 2006-02-27 2007-09-05 三菱瓦斯化学株式会社 Preparation method for hydrogenated polymer
JP2009028645A (en) * 2007-07-27 2009-02-12 Nof Corp Palladium heterogeneous catalyst
CN101225056A (en) * 2008-01-21 2008-07-23 浙江大学 Alpha-biphenyl-N-alkyl nitrone compound and synthetic method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ANTONIO MONOPOLI等: "Palladium/Zirconium Oxide Nanocomposite as a Highly Recyclable Catalyst for C-C Coupling Reactions in Water", 《MOLECULES》 *
AZIZ FIHRI等: "Nanocatalysts for Suzuki cross-coupling reactions", 《CHEM. SOC. REV.》 *
GAOFENG FENG等: "Crystalline mesoporous γ-Al2O3 supported palladium: Novel and efficient catalyst for Suzuki–Miyaura reaction under controlled microwave heating", 《CATALYSIS COMMUNICATIONS》 *
林梦依等: "Pd(OAc)2负载的Al2O3在Suzuki反应中的应用研究", 《绍兴文理学院学报》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104058909A (en) * 2014-07-02 2014-09-24 魏建华 Catalyzed synthesis method for drug intermediate diaryl-class compounds
WO2016019588A1 (en) * 2014-08-08 2016-02-11 The Broad Institute, Inc. Oxacazone compounds to treat clostridium difficile
CN106610397A (en) * 2015-10-27 2017-05-03 济南大学 Method for electrochemical detection of dopamine by using biphenyl organic mesoporous material-doped carbon paste electrode
CN108484372A (en) * 2018-04-04 2018-09-04 绍兴文理学院 A method of preparing biaryl by aryl hydrazines and aryl bromide
CN108484372B (en) * 2018-04-04 2021-07-02 绍兴文理学院 Method for preparing biaryl from aryl hydrazine and brominated aromatic hydrocarbon

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Application publication date: 20140521