CN115141072A - Preparation method of biphenyl and derivatives thereof - Google Patents

Preparation method of biphenyl and derivatives thereof Download PDF

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CN115141072A
CN115141072A CN202110276962.XA CN202110276962A CN115141072A CN 115141072 A CN115141072 A CN 115141072A CN 202110276962 A CN202110276962 A CN 202110276962A CN 115141072 A CN115141072 A CN 115141072A
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biphenyl
quaternary phosphonium
phosphonium salt
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曹昌盛
史延慧
喻文
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Jiangsu Normal University
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    • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
    • C07C1/324—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom the hetero-atom being a phosphorus atom
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    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C07C17/2635—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions involving a phosphorus compound, e.g. Wittig synthesis
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    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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Abstract

A preparation method of biphenyl and derivatives thereof belongs to the technical field of chemical synthesis, and comprises the following steps: using triphenyl quaternary phosphonium salt and aryl boric acid as raw material, using bis- (1, 5-cyclooctadiene) nickel (Ni (COD) 2 ) 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride salt (SIPr & HCl) is used as a ligand, cesium fluoride is used as alkali, and methylbenzene is used as a solvent for reaction, and the reaction is carried out at 110 ℃ for 20 hours to obtain biphenyl and derivatives thereof. The preparation method uses a new electrophilic coupler, and the used raw materials are cheap and easy to obtain, and have the advantages of no toxicity, no pollution and simple post-treatment.

Description

Preparation method of biphenyl and derivatives thereof
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a synthetic method of biphenyl and derivatives thereof.
Background
Due to the specific chemical and physical properties of biphenyl compounds, the biphenyl compounds are widely applied in the fields of medicines, pesticides, organic functional materials, plastics, dyes, organic synthetic intermediates and the like. The structural unit containing biphenyl is widely existed in a plurality of polymers, natural products, nano materials and medicaments with biological activity and becomes an important framework of pesticides, medicines, semiconductor materials, asymmetric catalysts and natural products.
Organometallic catalyzed cross-coupling reactions are important processes for the synthesis of biphenyl compounds, such as the Suzuki-Miyaura reaction of electrophilic couplings with organic borides, the Stille reaction of electrophilic couplings with organotin compounds, the Kumada reaction of electrophilic couplings with organomagnesium, which are all important processes for the synthesis of biphenyl compounds. For example, in 2010, discoverers of Suzuki cross-coupling, negishi cross-coupling, and Heck coupling collectively pursued the Nobel prize of chemistry of the year, which fully illustrates the importance of the Suzuki cross-coupling reaction, which is the construction of C (sp) 2 )-C(sp 2 ) One of the most effective methods of bonding.
Most of the traditional Suzuki coupling reactions use palladium to catalyze halogenated aromatic hydrocarbon to react with aryl boric acid, and most of the halogenated aromatic hydrocarbon has high price, high cost and few types; a large amount of halide is released in the reaction, and the environment is seriously polluted. How to find more electrophilic couplers capable of replacing halogenated aromatic hydrocarbon to participate in Suzuki coupling becomes one of the problems to be solved urgently. With the development of modern coordination chemistry, people gradually increase the electron donating ability of ligands (from the first generation phosphine ligands to the NHC ligands with strong electron donating ability at present) to increase the electron cloud density of central metals, and prepare a series of catalysts with high oxidative addition ability. So that some C-X bonds, such as C-O bonds, C-N bonds, C-S bonds, C-P bonds, which are otherwise inert to oxidative addition reactions, can also be cleaved and participate in the coupling reaction. Thus greatly expanding the range of the coupling reaction and promoting the development and utilization of novel electrophilic couplers; novel couplers have been developed.
The quaternary phosphonium salt has the advantages of easy obtaining, low price, various varieties, stability and easy storage, and the biphenyl aromatic hydrocarbon compound is prepared by carrying out Suzuki coupling reaction by taking the quaternary phosphonium salt as a substrate, and noble metal palladium with low abundance on the earth is not used as a catalyst in the invention; but rather more abundant nickel is used as catalyst; meanwhile, triphenyl quaternary phosphonium salt is developed to be used as an electrophilic coupler to participate in Suzuki coupling reaction, so that the application range of the compound containing carbon-phosphorus bonds as the electrophilic coupler is widened.
Disclosure of Invention
The invention aims to provide a high-efficiency preparation method of biphenyl and derivatives thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention synthesizes the quaternary phosphonium salt containing three benzene rings, and has the advantages of simple synthesis steps and convenient purification. The reaction formula is as follows:
Figure BDA0002977036860000021
the preparation method of the triphenyl methyl quaternary phosphonium salt comprises the steps of adding phosphine into a reaction vessel, wherein the amount of a solvent used is the amount of dissolved solute, and the amount of methyl trifluoromethanesulfonate is 1.1 times of that of phosphine substances; the reaction is violent, the methyl trifluoromethanesulfonate is slowly added dropwise in the reaction, and the reaction is stirred for 12 hours at normal temperature.
Post-treatment: adding excessive diethyl ether into the reaction liquid, precipitating a large amount of white solid in a container, washing the solid with diethyl ether for three times, and drying the obtained solid under a vacuum condition to obtain the clean quaternary phosphonium salt.
Preparation method of biphenyl and its derivatives from bis- (1, 5-cyclooctadiene) nickel (Ni (COD) in toluene under nitrogen protection 2 ) As a catalyst, 1, 3-bis (2, 6-diisopropylphenyl) imidazole chloride salt (SIPr & HCl) is taken as a ligand, alkali is cesium fluoride, and triphenylmethyl quaternary phosphonium salt reacts with a phenylboronic acid compound to obtain a target product. The reaction formula is as follows:
Figure BDA0002977036860000022
preferably, the catalyst is bis- (1, 5-cyclooctadiene) nickel, and the amount of the catalyst is 10% of the amount of the quaternary phosphonium salt substance.
Preferably, the ligand is 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride, and the amount of the ligand is 10% of that of the quaternary phosphonium salt.
Preferably, the base source is cesium fluoride and the amount of base used is 2 times the amount of quaternary phosphonium salt used.
Preferably, the quaternary phosphonium salt is triphenylmethylphosphonium triflate.
Preferably, the aryl boronic acid is reacted in an amount of 2 times the amount of the quaternary phosphonium salt.
Preferably, the solvent is selected from toluene, and preferably, the solvent is selected from anhydrous toluene, and the ratio of the amount of the solvent to the amount of the quaternary phosphonium salt is 5mL/1mmol.
Preferably, the temperature is 110 ℃.
Preferably, the reaction conditions are normal pressure and nitrogen protection.
Preferably, the reaction time of the reaction is 20 hours.
Preferably, the synthesis method comprises the following steps: adding triphenylmethylphosphonium triflate, arylboronic acid, 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride, cesium fluoride, bis- (1, 5-cyclooctadiene) nickel, dry toluene and toluene into a Schlenk tube under the protection of nitrogen, stirring and reacting for 20 hours at 110 ℃, and separating and purifying the obtained reaction solution to obtain the target product.
Preferably, the method further comprises the following post-treatment steps: after the reaction is finished, adding a proper amount of ethyl acetate and trifluoroacetic acid into the reaction solution for quenching; the separation and purification are carried out by adding column chromatography silica gel to the reaction solution, removing the solvent by distillation under reduced pressure, and separating the product by thin layer chromatography (petroleum ether/ethyl acetate volume ratio = 100).
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the biphenyl and the derivatives thereof takes bis- (1, 5-cyclooctadiene) nickel as a catalyst for the first time, 1, 3-bis (2, 6-diisopropylphenyl) imidazole chloride salt, triphenyl quaternary phosphonium salt and aryl boric acid as raw materials, and ultra-dry toluene as a reaction solvent; reacting for 20 hours at 110 ℃ under normal pressure to obtain aryl biphenyl and derivatives thereof;
the raw materials for preparing the triphenyl phosphonium salt are cheap and easy to obtain, and the synthesis is simple;
the phosphonium salts synthesized are stable and have not been previously developed;
the used catalyst is a nickel catalyst, so that the Suzuki coupling reaction gets rid of the dependence on the palladium catalyst in the past;
the yield of the reaction is relatively high, and the substrate universality is strong.
The specific implementation mode is as follows:
example 1
Preparation of 1,1' -biphenyl of the formula
Figure BDA0002977036860000031
Methyl triphenylmethylphosphonium trifluoromethanesulfonate (0.5 mmol), arylboronic acid (1.0 mmol), csF (151.90 mg), ni (COD) 2 (13.75mg, 0.05mmol) and SIPr. HCl (21.45mg, 0.05mmol) were added to a Schlenk tube and sealed in a glove box. Is connected withUltra dry toluene (2.5 mL) was then injected with a syringe. The mixture was heated to 110 ℃ and reacted for 20 hours. After the reaction is finished, adding a proper amount of ethyl acetate and trifluoroacetic acid into the reaction solution for quenching; the separation and purification were carried out by adding column chromatography silica gel to the reaction solution obtained, removing the solvent by distillation under reduced pressure, and separating by thin layer chromatography (petroleum ether/ethyl acetate volume ratio = 50) to obtain pure 1,1' -biphenol with a yield of 81%, and the structural characterization data are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.86–7.60(m,4H),7.48(t,J＝7.5Hz,4H),7.44–7.31(m,2H)；
13 C NMR(101MHz,CDCl 3 )δ141.3,128.8,127.3,127.2；
example 2
Preparation of 4-methoxy-1,1' -biphenyl
Figure BDA0002977036860000032
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 4-methoxyphenylboronic acid, and the procedure was otherwise the same as in example 1, and pure 4-methoxy-1,1' -biphenyl was isolated in 85% yield and the following number of structurally characterized groups:
1 H NMR(400MHz,CDCl 3 )δ7.61–7.50(m,4H),7.43(t,J＝7.6Hz,2H),7.32(t,J＝7.2Hz,1H),7.04–6.95(m,2H),3.86(s,3H)；
13 C NMR(101MHz,)δ159.26,140.94,133.88,128.84,128.27,126.85,126.78,114.32；
example 3
Preparation of 3-methoxy-1,1' -biphenyl
Figure BDA0002977036860000041
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 3-methoxyphenylboronic acid, and the procedure was otherwise the same as in example 1, and pure 3-methoxy-1,1' -biphenyl was isolated in 65% yield and the following number of structurally characterized groups:
1 H NMR(400MHz,CDCl 3 )δ7.72–7.58(m,2H),7.54–7.45(m,2H),7.46–7.32(m,2H),7.30–7.15(m,2H),6.95(ddt,J＝8.3,2.7,1.3Hz,1H),3.90(s,3H)；
13 C NMR(101MHz,CDCL3)δ160.0,142.8,141.2,129.8,128.8,127.4,127.2,119.7,113.0,112.7,55.3；
example 4
Preparation of 2-methoxy-1,1' -biphenyl
Figure BDA0002977036860000042
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 2-methoxyphenylboronic acid, and the procedure was otherwise the same as in example 1, and pure 2-methoxy-1,1' -biphenyl was isolated in 63% yield and the structural characterization numbers were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.58(d,J＝7.9Hz,2H),7.45(t,J＝7.5Hz,2H),7.37(t,J＝7.0Hz,3H),7.20–6.90(m,2H),3.85(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ156.5,138.6,131.0,130.8,129.6,128.7,128.0,127.0,120.9,111.3,55.6；
example 5
Preparation of 4-methyl-1,1' -biphenyl
Figure BDA0002977036860000043
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 4-methylphenylboronic acid, and the procedure was otherwise the same as in example 1, and pure 4-methyl-1,1' -biphenyl was isolated in 82% yield and the structural characterization numbers were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.61(dd,J＝8.2,1.0Hz,2H),7.52(t,J＝7.7Hz,2H),7.46(t,J＝7.6Hz,2H),7.39–7.33(m,1H),7.31–7.24(m,2H),2.43(d,J＝3.6Hz,3H)；
13 C NMR(101MHz,CDCl 3 )δ141.2,138.4,137.1,129.5,128.8,127.1,127.0,126.9,21.2；
example 6
Preparation of 4-fluoro-1,1' -biphenyl
Figure BDA0002977036860000051
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 4-fluorophenylboronic acid, and the procedure was otherwise the same as in example 1, and pure 4-fluoro-1,1' -biphenyl was isolated in 68% yield and the structural characterization numbers were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.57(dt,J＝9.3,2.7Hz,4H),7.46(t,J＝7.6Hz,2H),7.37(t,J＝7.3Hz,1H),7.15(t,J＝8.6Hz,2H)；
13 C NMR(101MHz,CDCl 3 )δ163.7,161.3,140.3,137.4,128.9,128.7,127.3,127.1,115.8,115.6；
19 F NMR(376MHz,CDCl3)δ-115.78；
example 7
Preparation of 4- (trifluoromethylphenyl) -1,1' -biphenol
Figure BDA0002977036860000052
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 4-trifluoromethylphenylboronic acid, and the procedure was otherwise the same as in example 1, and pure 4- (trifluoromethylphenyl) -1,1' -biphenyl was isolated in 87% yield and the structural characterization numbers were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.71(s,4H),7.65–7.58(m,2H),7.53–7.40(m,3H)；
13 C NMR(101MHz,CDCl 3 )δ144.8,139.8,129.5,129.0,128.2,127.7,127.4,125.7,123.0；
19 F NMR(376MHz,CDCl 3 )δ-62.36；
example 8
Preparation of 4- (trifluoromethyl) -1,1' -biphenyl
Figure BDA0002977036860000053
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 4-trifluoromethoxyphenylboronic acid, and the procedure was otherwise the same as in example 1, and pure 4- (trifluoromethyl) -1,1' -biphenyl was isolated in 36% yield and with the following structural characteristics:
1 H NMR(400MHz,CDCl 3 )δ7.69–7.53(m,4H),7.52–7.34(m,3H),7.34–7.27(m,2H)；
13 C NMR(101MHz,CDCl 3 )δ148.7,148.7,140.0,139.9,128.9,128.5,127.7,127.1,121.2,119.3；
19 F NMR(376MHz,CDCl 3 )δ-57.78；
example 9
Preparation of [1,1' -biphenyl ] -4-yltrimethylelanane
Figure BDA0002977036860000061
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 4-trifluoromethoxybenzeneboronic acid, and the procedure was otherwise the same as in example 1, and pure [1,1' -biphenyl ] -4-yltrimethylsilane was isolated in 42% yield and the following structural characterization numbers:
1 H NMR(400MHz,CDCl 3 )δ7.80–7.54(m,1H),7.59–7.41(m,0H),7.44–7.25(m,0H),0.33(s,2H)；
13 C NMR(101MHz,CDCl 3 )δ141.6,141.2,139.3,139.3,133.9,128.8,127.4,127.2,126.5,-1.0；
example 10
Preparation of [1,1' -biphenyl ] -4-carbonitrile of the following Structure
Figure BDA0002977036860000062
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 4-cyanophenylboronic acid, and the procedure was otherwise the same as in example 1, and pure [1,1' -biphenyl ] -4-carbonitrile was isolated in 81% yield and the following number of structurally characterized:
1 H NMR(400MHz,CDCl 3 )δ7.79–7.65(m,4H),7.63–7.57(m,2H),7.55–7.38(m,
3H)；
13 C NMR(101MHz,CDCl 3 )δ145.7,139.2,132.6,129.2,128.7,127.8,127.3,119.0,110.9；
example 11
Preparation of 4-benzyl-1, 1' -biphenyl
Figure BDA0002977036860000063
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 4-pentylphenylboronic acid, and the procedure was otherwise the same as in example 1, and pure 4-pentyl-1,1' -biphenyl was isolated in 97% yield and the structural characterization numbers were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.85–7.27(m,9H),2.72(td,J＝7.8,7.3,3.5Hz,2H),1.95–1.63(m,2H),1.44(dq,J＝7.3,3.7Hz,4H),0.99(qd,J＝6.7,2.6Hz,3H)；
13 C NMR(101MHz,CDCl 3 )δ142.2,141.8,141.3,138.6,128.9,128.8,127.1,127.0,35.7,31.7,31.3,22.7,14.1；
example 12
Preparation of 4-bromo-1,1' -biphenyl
Figure BDA0002977036860000071
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 4-bromobenzoic acid and the other steps were the same as in example 1, and pure 4-bromoo-1, 1' -biphenyl was isolated in 12% yield and the structural characterization numbers were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.67–7.59(m,4H),7.56–7.38(m,5H)；
13 C NMR(101MHz,CDCl 3 )δ140.2,140.0,132.1,131.9,128.9,128.8,127.7,127.0,121.6；
example 13
Preparing 1,1' with the structure of 4', 1' -terphenyl
Figure BDA0002977036860000072
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 4-phenylphenylboronic acid and the procedure was otherwise the same as in example 1, with the pure 1,1':4',1"-terphenyl isolated in 69% yield and the following number of structural features:
1 H NMR(400MHz,CDCl 3 )δ7.81–7.59(m,8H),7.48(t,J＝7.6Hz,4H),7.38(ddd,J＝7.4,5.5,1.1Hz,2H)；
13 C NMR(101MHz,CDCl 3 )δ140.7,140.2,128.9,127.5,127.4,127.1；
example 14
Preparation of Biphenyl derivative 5-phenylbenzole [ d ] [1,3] dioxole having the following Structure
Figure BDA0002977036860000073
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 3, 4-methylenephenylboronic acid and the procedure was otherwise the same as in example 1, and pure 5-phenylbenzozo [ d ] [1,3] dioxole was isolated in 90% yield and the following number of structurally characterized values:
1 H NMR(400MHz,CDCl 3 )δ7.71–7.48(m,2H),7.42(dd,J＝8.5,6.8Hz,2H),7.36–7.29(m,1H),7.21–7.00(m,2H),7.02–6.81(m,1H),6.01(s,2H)；
13 C NMR(101MHz,CDCl 3 )δ148.2,147.1,141.0,135.7,128.8,128.6,127.0,120.7,108.7,107.8,101.2.
example 15
Preparation of biphenyl derivative 1-phenylnaphthalene [
Figure BDA0002977036860000081
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 1-naphthalene boronic acid and the procedure was otherwise the same as in example 1, and pure 1-phenylnaphthalene was isolated in 37% yield and with the following structural characterization numbers:
1 H NMR(400MHz,CDCl 3 )δ8.11–7.71(m,3H),7.68–7.35(m,9H)；
13 C NMR(101MHz,CDCl 3 )δ140.8,140.3,133.9,131.7,130.1,128.3,127.7,127.3,127.0,126.1,126.1,125.8,125.4；
example 16
Preparation of biphenyl derivative 4- (phenoxymethyl) -1,1' -biphenyl
Figure BDA0002977036860000082
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 1-naphthoic acid, and the procedure was otherwise the same as in example 1, and pure 4- (phenoxymethyl) -1,1' -biphenol was isolated in 98% yield and having the following structural characteristics:
1 H NMR(400MHz,CDCl 3 )δ7.69–7.52(m,4H),7.52–7.40(m,6H),7.39–7.17(m,2H),7.13–7.03(m,2H)；
13 C NMR(101MHz,CDCl 3 )δ158.4,140.8,137.0,134.1,129.5,128.8,128.7,128.2,128.0,127.5,126.8,115.2,70.2；
example 17
Preparation of the Biphenyl derivative 4- (tert-butyl) -1,1' -biphenyl
Figure BDA0002977036860000083
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 4-tert-butylboronic acid and the other steps were the same as in example 1, and pure 4- (tert-butyl) -1,1' -biphenyl was isolated in 77% yield and the structural characterization numbers were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.71–7.54(m,4H),7.55–7.41(m,4H),7.37(dq,J＝7.1,2.0,1.5Hz,1H),1.70–1.18(m,9H)；
13 C NMR(101MHz,CDCl 3 )δ150.3,141.1,138.4,128.8,127.1,127.0,126.9,126.7,125.8,34.6,31.5；
example 18
Preparation of the Biphenyl derivative 1- ([ 1,1' -biphenyl ] -4-yl) ethan-1-one of the following Structure
Figure BDA0002977036860000091
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 4-acetylphenylboronic acid, and the procedure was otherwise the same as in example 1, and pure 1- ([ 1,1' -biphenyl ] -4-yl) ethan-1-one was isolated in 62% yield and the following number of structurally characterized:
1 H NMR(400MHz,CDCl 3 )δ8.19–7.93(m,2H),7.80–7.59(m,4H),7.56–7.35(m,3H),2.65(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.8,145.8,139.9,135.9,129.0,128.9,128.3,127.3,127.2,26.7；
example 19
Preparation of the biphenyl derivative tert-butyl [1,1' -biphenyl ] -4-carboxylate of the formula
Figure BDA0002977036860000092
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 4-acetylphenylboronic acid and the procedure was otherwise the same as in example 1, and the pure tert-butyl [1,1' -biphenyl ] -4-carboxylate was isolated in 85% yield and the following number of structurally characterized values:
1 H NMR(400MHz,CDCl 3 )δ8.18–7.98(m,2H),7.74–7.59(m,4H),7.54–7.34(m,3H),1.64(s,9H)；
13 C NMR(101MHz,CDCl 3 )δ165.7,145.2,140.2,130.8,130.0,128.9,128.1,127.3,126.9,81.0,28.3；
example 20
Preparation of the biphenyl derivative methyl [1,1' -biphenyl ] -4-carboxylate of the structure
Figure BDA0002977036860000101
In example 1, the phenylboronic acid used was replaced with an equimolar amount of 4-acetylphenylboronic acid and the procedure was otherwise the same as in example 1, and pure methyl [1,1' -biphenyl ] -4-carboxylate was isolated in 38% yield and having the following structural characteristics:
1 H NMR(400MHz,CDCl 3 )δ8.17–8.03(m,2H),7.76–7.57(m,4H),7.51–7.44(m,2H),7.43–7.37(m,1H),3.95(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ167.1,145.7,140.1,130.2,129.0,128.9,128.3,127.4,127.2,52.3。

Claims (6)

1. a process for the preparation of biphenyl and its derivatives, characterized in that bis- (1, 5-cyclooctadiene) nickel (Ni (COD) is used as the starting material in an organic solvent under a protective atmosphere 2 ) As a catalyst, 1, 3-bis (2, 6-diisopropylphenyl) imidazole chloride salt (SIPr & HCl) is taken as a ligand, alkali is cesium fluoride, and triphenylmethyl quaternary phosphonium salt reacts with a phenylboronic acid compound to obtain a target product.
2. The method of claim 1, wherein the catalyst is used in an amount of 10% of the amount of quaternary phosphonium salt material; the dosage of the ligand is 10% of that of the quaternary phosphonium salt; the dosage of the alkali is 2 times of that of the quaternary phosphonium salt; the quaternary phosphonium salt is triphenylmethyl phosphonium trifluoromethanesulfonate; the dosage of the aryl boric acid is 2 times of that of the quaternary phosphonium salt.
3. The method of claim 1, wherein the organic solvent is toluene.
4. The method according to claim 3, wherein the toluene is anhydrous toluene, and the ratio of the amount of the anhydrous toluene to the amount of the quaternary phosphonium salt is 5mL/1mmol.
5. The method of claim 1, wherein the reaction temperature is 110 ℃, the reaction conditions are normal pressure and nitrogen protection, and the reaction time is 20 hours.
6. The method of claim 1, further comprising a post-processing step of: after the reaction is finished, adding a proper amount of ethyl acetate and trifluoroacetic acid into the reaction solution for quenching; adding column chromatography silica gel into the obtained reaction solution, removing the solvent by reduced pressure distillation, and separating by thin layer chromatography to obtain a pure target product.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100197969A1 (en) * 2007-07-26 2010-08-05 Dynamit Nobel Gmbh Explosivstoff-Und Systemtechnik Use of phosphonium salts in coupling reactions and process for their manufacture
CN102702165A (en) * 2012-06-11 2012-10-03 江苏师范大学 Method for preparing cyclic carbonate by taking NHC/ZnBr2 system as catalyst
CN104628581A (en) * 2015-02-04 2015-05-20 北京鼎材科技有限公司 2,6,6,8-tetra-substituted-6H-benzo[cd]pyrene compound and organic electroluminescence device containing same
US20150360214A1 (en) * 2013-01-23 2015-12-17 Hokko Chemical Industry Co., Ltd. Reaction catalyst for cross-coupling and method for manufacturing aromatic compound

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100197969A1 (en) * 2007-07-26 2010-08-05 Dynamit Nobel Gmbh Explosivstoff-Und Systemtechnik Use of phosphonium salts in coupling reactions and process for their manufacture
CN102702165A (en) * 2012-06-11 2012-10-03 江苏师范大学 Method for preparing cyclic carbonate by taking NHC/ZnBr2 system as catalyst
US20150360214A1 (en) * 2013-01-23 2015-12-17 Hokko Chemical Industry Co., Ltd. Reaction catalyst for cross-coupling and method for manufacturing aromatic compound
CN104628581A (en) * 2015-02-04 2015-05-20 北京鼎材科技有限公司 2,6,6,8-tetra-substituted-6H-benzo[cd]pyrene compound and organic electroluminescence device containing same

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
，XUAN ZHANG，等: "Phosphonium Salts as Pseudohalides: Regioselective Nickel-Catalyzed Cross-Coupling of Complex Pyridines and Diazines", ANGEW. CHEM., vol. 33, no. 129, 31 December 2017 (2017-12-31), pages 9966 *
JAMES MCNULTY，等: "Suzuki cross-coupling reactions of aryl halides in phosphonium salt ionic liquid under mild conditions", C H E M . C O M M U N ., 7 August 2002 (2002-08-07), pages 1986 - 1987, XP002466821, DOI: 10.1039/b204699g *
MEIQI ZHU, 等: "Nickel-catalyzed Suzuki cross-coupling reaction of alkyl triaryl phosphonium salts", TETRAHEDRON, vol. 135, 16 February 2023 (2023-02-16), pages 1 - 11 *
孙海森: "钯催化下季鏻盐 C-P 键断裂偶联反应的研究", 中国优秀硕士学位论文全文数据库, 5 February 2021 (2021-02-05), pages 20 - 26 *
熊文芳: "化学转化二氧化碳为氨基甲酸酯研究", 中国优秀硕士学位论文全文数据库, 15 December 2018 (2018-12-15), pages 1 *
蔡正元，等: "N杂环卡宾在催化有机合成中的应用", 徐州师范大学学报（ 自然科学版 ）, vol. 29, no. 1, 31 March 2011 (2011-03-31), pages 1 - 14 *

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