CN102731370B - Preparation method of ionic liquid and synthesizing method of biphenyl compounds by applying palladium carbon catalysis in ionic liquid - Google Patents

Preparation method of ionic liquid and synthesizing method of biphenyl compounds by applying palladium carbon catalysis in ionic liquid Download PDF

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CN102731370B
CN102731370B CN201210243523XA CN201210243523A CN102731370B CN 102731370 B CN102731370 B CN 102731370B CN 201210243523X A CN201210243523X A CN 201210243523XA CN 201210243523 A CN201210243523 A CN 201210243523A CN 102731370 B CN102731370 B CN 102731370B
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ionic liquid
palladium carbon
boric acid
methyl
biphenyl compound
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CN102731370A (en
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初文毅
孙志忠
王熳
李新民
任力敏
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Heilongjiang University
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Abstract

The invention provides a preparation method of ionic liquid and synthesizing method of biphenyl compounds by applying palladium carbon catalysis in the ionic liquid, relates to an ionic liquid and a synthesizing method of the biphenyl compounds, and aims to solve the technical problems of complicated synthesis steps, difficult availability and high price of organic ligand required by a conventional biphenyl compound synthesizing method. The ionic liquid is prepared from 4-methylpyridine, 2-chloroethyl methyl ether, methyl cyanide and activated carbon. The preparation method of the biphenyl compounds comprises the following steps: adding aryl halide, arylboronic acid, palladium carbon and potassium carbonate into the aqueous solution of the ionic solution; stirring in magnetic force, adding saturated NaCl solution, and extracting with ethyl acetate; drying and filtering with anhydrous sodium sulfate, and concentrating in vacuum; performing chromatography with a silicagel column; and eluting to obtain the biphenyl compounds. The ionic liquid participates in promoting palladium carbon catalysis to synthesize the biphenyl compounds along with high yield and easy separation; and the catalyst can be recycled, so that cost can be saved, and operation is simple.

Description

The preparation method of ionic liquid and application ionic liquid palladium carbon catalyze and synthesize the method for biphenyl compound
Technical field
The present invention relates to the method for a kind of ionic liquid and synthetic biphenyl compound.
Background technology
Biphenyl structural extensively is present in the natural product, such as terpene (terpenes), and lignanoid (lignans), flavonoid compound (flavonoids) is in peptide (petides) and the alkaloid (alkaloids).Many biphenyl compounds have certain biological activity, if significantly reduce serum glutamic pyruvic transminase, alleviate the hepatic pathology damage and strengthen liver detoxification function etc.Biphenyl structural also is the common structure unit such as agricultural chemicals and dyestuff simultaneously, and wherein polyaromatic is because its special physics and characteristic electron have been used as organic conductor, semi-conductor and liquid crystal material.Because biphenyl compound has these functions and paid close attention to more and more widely, therefore adopt new synthetic method can synthesize efficiently, fast and cheaply the work problem that biphenyl compound has become many researchers.
The formation of C-C is one of most basic organic chemical reactions process, is the committed step that forms complicated molecule from simple precursor.The Suzuki linked reaction of the famous scientist's Suzuki Zhang Faming of Japan is one of important method of preparation biphenyl compound, this reaction has realized that carrying out cross-coupling by halogenated aryl hydrocarbon and aryl boric acid forms new C-C and synthesize biphenyl compound, this catalyzed reaction not only reaction conditions is gentle, and have highly chemistry, three-dimensional and the selectivity zone, in organic synthesis, be widely used, but also have following problems:
(1) the common organic ligand that needs to use large steric hindrance, electron rich, the numerous and diverse difficult acquisition of the synthesis step of these organic ligands, price is high;
(2) use volatile, poisonous in a large number organic solvent and cause environmental pollution.
Summary of the invention
The objective of the invention is numerous and diverse, the difficult acquisition and the high technical problem of price of organic ligand synthesis step for the method needs that solve existing synthetic biphenyl compound, a kind of preparation method of ionic liquid is provided and has used the method that ionic liquid palladium carbon catalyzes and synthesizes biphenyl compound.
The preparation method of ionic liquid carries out according to following steps:
In the single port bottle, add successively 9.3g 4-picoline and 10.4g 2-chloroethyl methyl ether, then at 70 ℃ of stirring reaction 48h, cool to room temperature adds the 100ml acetonitrile, the 3g gac is at 70 ℃ of reaction 24h, be cooled to 0 ℃, filter, then the solid that obtains is washed three times with ether, drain, vacuum-drying 24h obtains 1-ethyl-methyl ether-4-picoline villaumite, and structural formula is:
Figure BDA00001885480100011
R in the formula 1It is methyl; R 2It is methyl.
The preparation method of ionic liquid carries out according to following steps:
In the single port bottle, add 10g 1-ethyl-methyl ether-4-picoline villaumite and 16.83g bis trifluoromethyl sulfimide lithium, add again the 20ml deionized water, stirring at room 24h, static be divided into two-layer, wash layer with deionized water, vacuum-drying 24h obtains 1-ethyl-methyl ether-4 picoline bis trifluoromethyl sulfimide salt.
The method that application ionic liquid palladium carbon catalyzes and synthesizes biphenyl compound is as follows:
Halogenated aryl hydrocarbon, aryl boric acid, palladium carbon and salt of wormwood are joined in the ionic liquid aqueous solution, at 80 ℃ of magnetic agitation 1h, add saturated NaCl solution, use again ethyl acetate extraction 4 times, then use anhydrous sodium sulfate drying, filter, vacuum concentration, the recycle silicon plastic column chromatography, the mixed solution wash-out with sherwood oil and ethyl acetate namely gets biphenyl compound;
The mol ratio of described halogenated aryl hydrocarbon and aryl boric acid is 0.8-4: 1;
The addition of described palladium carbon is the 0.1-15% of halogenated aryl hydrocarbon molar weight;
The add-on of described salt of wormwood is 1-5 times of halogenated aryl hydrocarbon molar weight;
The mass ratio of described ionic liquid aqueous solution intermediate ion liquid and water is 1: 0.1-10;
The mixed solution PetroChina Company Limited. ether of described sherwood oil and ethyl acetate and the volume ratio of ethyl acetate are 1-10: 1;
Described halogenated aryl hydrocarbon is 3,4-dimethoxy bromobenzene, para-bromoanisole, p-bromobenzaldehyde, 4-methoxyl group bromobenzene or p-Nitrobromobenzene;
Described aryl boric acid is 4-trifluoromethyl phenylo boric acid, 3,4-dimethoxy phenylo boric acid, 2,5-dimethylphenyl boronic acid, 2,6-dimethylphenyl boronic acid, naphthalene phenylo boric acid or phenylo boric acid;
Described ionic liquid is 1-ethyl-methyl ether-4-picoline villaumite or 1-ethyl-methyl ether-4 picoline bis trifluoromethyl sulfimide salt.
Using ionic liquid palladium carbon, to catalyze and synthesize the reaction expression of biphenyl compound as follows:
Figure BDA00001885480100021
R wherein 3Hydrogen, methoxyl group, oxyethyl group, propoxy-, alkyl, chloro alkyl, fluoro-alkyl, 4-trifluoromethyl, 2,5-dimethyl, 2,6-dimethyl or 3,4-dimethoxy; R is hydrogen, 4-nitro, 4-aldehyde radical, 4-methoxyl group, 4-cyano group or 3,4-dimethoxy.
Method of the present invention is utilized the Suzuki linked reaction, in the aqueous solution of green solvent ionic liquid, to have realized cross-coupling reaction between aryl boric acid and the halogenated aryl hydrocarbon without the palladium carbon of part as catalyzer, can synthesize efficiently biphenyl compound, that the method has is simple to operate, cost is low, catalyzer can be recycled and reaction is easy to the advantages such as lock out operation.
The present invention includes following advantage:
(1) ionic liquid of the present invention participates in promoting that palladium carbon catalyzes and synthesizes biphenyl compound, and yield is high, and is easily separated;
(2) synthetic method of the present invention has accomplished that catalyzer can be recycled, and saves cost, and is simple to operate.
Description of drawings
Fig. 1 is the 1-ethyl-methyl ether-4-picoline villaumite nucleus magnetic hydrogen spectrum figure of embodiment one preparation;
Fig. 2 is the 1-ethyl-methyl ether-4-picoline villaumite nuclear-magnetism carbon spectrogram of embodiment one preparation;
Fig. 3 is the 1-ethyl-methyl ether-4 picoline bis trifluoromethyl sulfimide salt nuclear-magnetism hydrogen spectrogram of embodiment two preparations;
Fig. 4 is the 1-ethyl-methyl ether-4 picoline bis trifluoromethyl sulfimide salt nuclear-magnetism carbon spectrogram of embodiment two preparations;
Fig. 5 is 3 of experiment one preparation, the 4-dimethoxy-4 ' '-the nucleus magnetic hydrogen spectrum figure of trifluoromethyl-biphenyl;
Fig. 6 is 3 of experiment one preparation, the 4-dimethoxy-4 ' '-the nuclear-magnetism carbon spectrogram of trifluoromethyl-biphenyl;
Fig. 7 is the nucleus magnetic hydrogen spectrum figure that tests the two 4-methoxyl group-4 ' for preparing-trifluoromethyl-biphenyls;
Fig. 8 is the 4-formyl radical-3 ' of experiment three preparations, the hydrogen spectrogram of 4 '-dimethoxy-biphenyl;
Fig. 9 is 3,4 dimethoxy-4 's of experiment four preparations ' the nucleus magnetic hydrogen spectrum figure of methoxyl biphenyl;
Figure 10 is the 4-nitro-3 ' of experiment five preparations, the nucleus magnetic hydrogen spectrum figure of 4 ' dimethoxy-biphenyl;
Figure 11 is the 4-nitro-2 ' of experiment six preparations, the nucleus magnetic hydrogen spectrum figure of 5 '-dimethyl diphenyl;
Figure 12 is the 4-nitro-2 ' of experiment seven preparations, the nucleus magnetic hydrogen spectrum figure of 6 '-dimethyl diphenyl;
Figure 13 is 3 of experiment eight preparations, 4-dimethoxy-2 ', the nucleus magnetic hydrogen spectrum figure of 5 '-dimethyl diphenyl;
Figure 14 is 3 of experiment eight preparations, 4-dimethoxy-2 ', the nuclear-magnetism carbon spectrogram of 5 '-dimethyl diphenyl;
Figure 15 is the hydrogen spectrogram of testing the nine 1-naphthalene for preparing-4-oil of mirbane;
Figure 16 tests the hydrogen spectrogram of the 4-formyl biphenyl of ten preparations.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of present embodiment ionic liquid carries out according to following steps:
In the single port bottle, add successively 9.3g 4-picoline and 10.4g 2-chloroethyl methyl ether, then at 70 ℃ of stirring reaction 48h, cool to room temperature adds the 100ml acetonitrile, and the 3g gac is at 70 ℃ of reaction 24h, be cooled to 0 ℃, filter, then the solid that obtains is washed three times (at every turn using ether 30mL) with ether, drain, vacuum-drying 24h obtains 1-ethyl-methyl ether-4-picoline villaumite (incarnadine).
1-ethyl-methyl ether-4-picoline villaumite nmr analysis data and high resolution mass spectrum data:
1H?NMR(400MHz，D2O)δ8.65(d，J＝6.7Hz，1H)，7.90(d，J＝6.4Hz，1H)，4.82-4.70(m，2H)，4.01-3.92(m，1H)，3.37(s，1H)，2.67(s，2H)。
13C?NMR(101MHz，CDCl3)δ158.45(s，1H)，144.67(s，2H)，128.16(s，2H)，77.48(s，8H)，77.16(s，9H)，76.84(s，8H)，70.66(s，1H)，60.42(s，1H)，58.63(s，1H)，21.98(s，1H)。
HRMS(EI)calcd?for?C 9H 14ClNO(M-)：187.08.Found：187.07。
Embodiment two: the preparation method of present embodiment ionic liquid carries out according to following steps:
In the single port bottle, add 10g 1-ethyl-methyl ether-4-picoline villaumite and 16.83g bis trifluoromethyl sulfimide lithium, add again the 20ml deionized water, stirring at room 24h, static be divided into two-layer, wash layer with deionized water, vacuum-drying 24h obtains 1-ethyl-methyl ether-4 picoline bis trifluoromethyl sulfimide salt.
1-ethyl-methyl ether-4 picoline bis trifluoromethyl sulfimide salt nmr analysis data and high resolution mass spectrum data:
1H?NMR(400MHz，CDCl3)δ8.59(d，J＝5.9Hz，2H)，7.79(d，J＝5.6Hz，2H)，4.74-4.59(m，2H)，3.87-3.74(m，2H)，3.32(s，3H)，2.67(s，3H)。
13C?NMR(101MHz，CDCl3)δ160.20(s，5H)，143.96(s，20H)，128.78(s，20H)，124.69(s，1H)，121.49(s，3H)，118.30(s，3H)，115.11(s，1H)，77.67(s，12H)，77.35(s，12H)，77.03(s，12H)，70.11(s，12H)，61.01(s，11H)，58.94(s，10H)，22.08(s，9H)。
HRMS(EI)calcd?for?C 11H 14ClN 2O 5F 6S 2(M-)：432.36.Found：432.34。
Embodiment three: the method that present embodiment application ionic liquid palladium carbon catalyzes and synthesizes biphenyl compound is as follows:
Halogenated aryl hydrocarbon, aryl boric acid, palladium carbon and salt of wormwood are joined in the ionic liquid aqueous solution, at 80 ℃ of magnetic agitation 1h, add saturated NaCl solution, use again ethyl acetate extraction 4 times, then use anhydrous sodium sulfate drying, filter, vacuum concentration, the recycle silicon plastic column chromatography, the mixed solution wash-out with sherwood oil and ethyl acetate namely gets biphenyl compound;
The mol ratio of described halogenated aryl hydrocarbon and aryl boric acid is 0.8-4: 1;
The addition of described palladium carbon is the 0.1-15% of halogenated aryl hydrocarbon molar weight;
The add-on of described salt of wormwood is 1-5 times of halogenated aryl hydrocarbon molar weight;
The mass ratio of described ionic liquid aqueous solution intermediate ion liquid and water is 1: 0.1-10;
The mixed solution PetroChina Company Limited. ether of described sherwood oil and ethyl acetate and the volume ratio of ethyl acetate are 1-10: 1;
Described halogenated aryl hydrocarbon is 3,4-dimethoxy bromobenzene, para-bromoanisole, p-bromobenzaldehyde, 4-methoxyl group bromobenzene or p-Nitrobromobenzene;
Described aryl boric acid is 4-trifluoromethyl phenylo boric acid, 3,4-dimethoxy phenylo boric acid, 2,5-dimethylphenyl boronic acid, 2,6-dimethylphenyl boronic acid, naphthalene phenylo boric acid or phenylo boric acid;
Described ionic liquid is 1-ethyl-methyl ether-4-picoline villaumite or 1-ethyl-methyl ether-4 picoline bis trifluoromethyl sulfimide salt.
Embodiment four: present embodiment and embodiment three are different is that the mol ratio of described halogenated aryl hydrocarbon and aryl boric acid is 1-3: 1.Other is identical with embodiment three.
Embodiment five: present embodiment and embodiment three are different is that the mol ratio of described halogenated aryl hydrocarbon and aryl boric acid is 2: 1.Other is identical with embodiment three.
Embodiment six: present embodiment and embodiment three are different is that the addition of described palladium carbon is the 1-13% of halogenated aryl hydrocarbon molar weight.Other is identical with embodiment three.
Embodiment seven: present embodiment and embodiment three are different is that the addition of described palladium carbon is 10% of halogenated aryl hydrocarbon molar weight.Other is identical with embodiment three.
Embodiment eight: present embodiment and embodiment three are different is that the add-on of described salt of wormwood is 3 times of halogenated aryl hydrocarbon molar weight.Other is identical with embodiment three.
Embodiment nine: present embodiment and embodiment three are different is that the mass ratio of described ionic liquid aqueous solution intermediate ion liquid and water is 1: 1-9.Other is identical with embodiment three.
Embodiment ten: present embodiment and embodiment three are different is that the mass ratio of described ionic liquid aqueous solution intermediate ion liquid and water is 1: 5.Other is identical with embodiment three.
Adopt following experimental verification effect of the present invention:
Experiment one:
In the single port bottle, add successively 0.5mmol 3,4-dimethoxy bromobenzene (109mg), 0.6mmol4-trifluoromethyl phenylo boric acid (114mg), 1.75mmolK 2CO 3(242mg), 0.0125mmol palladium carbon (30mg), 1.5g ionic liquid 1-ethyl-methyl ether-4-picoline villaumite and 3mL distilled water, at 80 ℃ of magnetic agitation 1h, after reaction finishes, add the saturated NaCl solution of 15mL, and with ethyl acetate (each 15mL) extraction 4 times, then with behind the anhydrous sodium sulfate drying, filter, vacuum concentration, the recycle silicon plastic column chromatography, mixed solution (volume ratio of sherwood oil and ethyl acetate is 1: the 1) wash-out of use sherwood oil and ethyl acetate obtains 3, the 4-dimethoxy-4 ' '-trifluoromethyl-biphenyl 140mg (white solid), yield 99.2%.
3,4-dimethoxy-4 ' '-nucleus magnetic hydrogen spectrum nmr analysis data and the high resolution mass spectrum data of trifluoromethyl-biphenyl:
1H?NMR(400MHz，CDCl 3)δ7.72-7.61(m，4H)，7.17(dd，J＝8.3，2.1Hz，1H)，7.10(d，J＝2.1Hz，1H)，6.97(d，J＝8.3Hz，1H)，3.96(s，3H)，3.94(s，3H)。
13C?NMR(100MHz，CDCl3)δ149.49，149.41，144.55，132.68，127.06，125.71，125.67，1，121.44，119.77，111.61，110.48，56.04，29.71。
HRMS(EI)calcd?for?C 15H 13F 2O 2(M-)：282.0957.Found：242.0948。
Experiment two:
In the single port bottle, add successively 0.5mmol para-bromoanisole (95mg), 0.6mmol4-trifluoromethyl phenylo boric acid (114mg), 1.75mmolK 2CO 3(242mg), 0.0125mmol palladium carbon (30mg), 1.5g ionic liquid and 3mL distilled water, at 80 ℃ of magnetic agitation 1h, after reaction finishes, add the saturated NaCl solution of 15mL, and with ethyl acetate extraction 4 times (each 15mL), use anhydrous sodium sulfate drying, filter, vacuum concentration, the recycle silicon plastic column chromatography, use mixed solution (volume ratio of sherwood oil and ethyl acetate is 1: the 1) wash-out of sherwood oil and ethyl acetate, get 4-methoxyl group-4 '-trifluoromethyl-biphenyl (white solid) 124mg, yield 98.6%.
4-methoxyl group-4 '-trifluoromethyl-biphenyl nucleus magnetic hydrogen spectrum nmr analysis data:
1H?NMR(400MHz，CDCl 3)δ7.54(t，J＝8.3Hz，4H)，7.42(d，J＝7.5Hz，1H)，7.40(d，J＝7.8Hz，1H)，7.30(t，J＝7.4Hz，1H)，6.98(d，J＝8.7Hz，2H)，3.85(s，3H)。
Experiment three:
In the single port bottle, add successively 0.5mmol p-bromobenzaldehyde (92mg), 0.6mmol4-trifluoromethyl phenylo boric acid (114mg), 1.75mmol K 2CO 3(242mg), 0.0125mmol palladium carbon (30mg), 1.5g ionic liquid and 3mL distilled water; at 80 ℃ of magnetic agitation 1h; after reaction finishes; add the saturated NaCl solution of 15mL; and with ethyl acetate extraction 4 times (each 15mL); use anhydrous sodium sulfate drying; filter; vacuum concentration; the recycle silicon plastic column chromatography, mixed solution (volume ratio of sherwood oil and ethyl acetate is 1: the 1) wash-out of use sherwood oil and ethyl acetate obtains 4-formyl radical-3 '; 4 '-dimethoxy-biphenyl (white solid) 115mg, yield 95.0%.
4-formyl radical-3 ', 4 '-dimethoxy-biphenyl nucleus magnetic hydrogen spectrum nmr analysis data:
1H?NMR(400MHz，CDCl3)δ10.04(s，1H)，7.93(d，J＝8.3Hz，2H)，7.72(d，J＝8.2Hz，2H)，7.22(dd，J＝8.3，2.1Hz，1H)，7.15(d，J＝2.0Hz，1H)，6.98(d，J＝8.3Hz，1H)，3.97(s，3H)，3.94(s，3H)。
Experiment four:
In the single port bottle, add successively 0.5mmol4-methoxyl group bromobenzene (93mg), 0.6mmol3,4-dimethoxy phenylo boric acid (109mg), 1.75mmol K 2CO 3(242mg), 0.0125mmol palladium carbon (30mg), ionic liquid 1.5g distilled water 3mL.At 80 ℃ of magnetic agitation 1h.After reaction finishes, add the saturated NaCl solution of 15mL, and with ethyl acetate extraction 4 times (each 15mL), use anhydrous sodium sulfate drying, filter, vacuum concentration, the recycle silicon plastic column chromatography, mixed solution (volume ratio of sherwood oil and ethyl acetate is 1: the 1) wash-out of use sherwood oil and ethyl acetate obtains 3,4 dimethoxy-4 's ' methoxyl biphenyl (white solid) 119mg, yield 97.6%.
3,4 dimethoxy-4 's ' methoxyl biphenyl nucleus magnetic hydrogen spectrum nmr analysis data:
1H?NMR(400MHz，CDCl3)δ7.53-7.43(m，2H)，7.09(dd，J＝8.2，2.1Hz，1H)，7.06(d，J＝2.0Hz，1H)，6.99-6.94(m，2H)，6.93(d，J＝8.2Hz，1H)，3.94(s，3H)，3.91(s，3H)，3.85(s，3H)。
Experiment five:
In the single port bottle, add successively 0.5mmol p-Nitrobromobenzene (101mg), 0.6mmol3,4-dimethoxy phenylo boric acid (109mg), 1.75mmolK 2CO 3(242mg), 0.0125mmol palladium carbon (30mg), 1.5g ionic liquid and 3mL distilled water, at 80 ℃ of magnetic agitation 1h, after reaction finishes, add the saturated NaCl solution of 15mL, and with ethyl acetate extraction 4 times (each 15mL), use anhydrous sodium sulfate drying, filter, vacuum concentration, the recycle silicon plastic column chromatography, mixed solution (volume ratio of sherwood oil and ethyl acetate is 1: the 1) wash-out of use sherwood oil and ethyl acetate obtains 4-nitro-3 ', 4 '-dimethoxy-biphenyl (white solid) 125mg, yield 96.5%.
4-nitro-3 ', 4 '-dimethoxy-biphenyl nucleus magnetic hydrogen spectrum nmr analysis data:
1H?NMR(400MHz，CDCl3)δ8.34-8.23(m，2H)，7.77-7.66(m，2H)，7.21(dd，J＝8.3，2.2Hz，1H)，7.13(d，J＝2.1Hz，1H)，6.99(d，J＝8.4Hz，1H)，3.97(s，3H)，3.95(s，3H)。
Experiment six:
In the single port bottle, add successively 0.5mmol p-Nitrobromobenzene (101mg), 0.6mmol2 successively, 5-dimethylphenyl boronic acid (90mg), 1.75mmol K 2CO 3(242mg), 0.0125mmol palladium carbon (30mg), 1.5g ionic liquid and 3mL distilled water, at 80 ℃ of magnetic agitation 1h.After reaction finishes, add the saturated NaCl solution of 15mL, and with ethyl acetate extraction 4 times (each 15mL), use anhydrous sodium sulfate drying, filter, vacuum concentration, the recycle silicon plastic column chromatography, mixed solution (volume ratio of sherwood oil and ethyl acetate is 1: the 1) wash-out of use sherwood oil and ethyl acetate obtains white solid 4-nitro-2 ', 5 '-dimethyl diphenyl 115mg, yield 92.4%.
4-nitro-2 ', 5 '-dimethyl diphenyl nucleus magnetic hydrogen spectrum nmr analysis data:
1H?NMR(500MHz，CDCl 3)δ8.27(d，J＝8.0Hz，2H)，7.49(d，J＝7.9Hz，2H)，7.20(d，J＝7.7Hz，1H)，7.14(d，J＝7.8Hz，1H)，7.04(s，1H)，2.37(s，3H)，2.23(s，3H)。
Experiment seven:
In the single port bottle, add successively 0.5mmol p-Nitrobromobenzene (101mg), 0.6mmol 2,6-dimethylphenyl boronic acid (90mg), 1.75mmolK 2CO 3(242mg), 0.0125mmol palladium carbon (30mg), 1.5g ionic liquid and 3mL distilled water, at 80 ℃ of magnetic agitation 1h, after reaction finishes, add the saturated NaCl solution of 15mL, and with ethyl acetate extraction 4 times (each 15mL), use anhydrous sodium sulfate drying, filter, vacuum concentration, the recycle silicon plastic column chromatography, mixed solution (volume ratio of sherwood oil and ethyl acetate is 1: the 1) wash-out of use sherwood oil and ethyl acetate obtains white solid 4-nitro-2 ', 5 '-dimethyl diphenyl 95mg, yield 77.9%.
4-nitro-2 ', 5 '-dimethyl diphenyl nucleus magnetic hydrogen spectrum nmr analysis data:
1H?NMR(400MHz，CDCl 3)δ8.31(d，J＝8.6Hz，2H)，7.34(d，J＝8.7Hz，2H)，7.21(d，J＝6.9Hz，1H)，7.13(d，J＝7.5Hz，2H)，2.01(s，6H)。
Experiment eight:
In the single port bottle, add successively 0.5mmol3,4-dimethoxy bromobenzene (109mg), 0.6mmol2,5-dimethylphenyl boronic acid (90mg), 1.75mmolK 2CO 3(242mg), 0.0125mmol palladium carbon (30mg), 1.5g ionic liquid and 3mL distilled water, at 80 ℃ of magnetic agitation 1h, after reaction finishes, add the saturated NaCl solution of 15mL, and with ethyl acetate extraction 4 times (each 15mL), use anhydrous sodium sulfate drying, filter, vacuum concentration, recycle silicon plastic column chromatography, mixed solution (volume ratio of sherwood oil and ethyl acetate is 1: the 1) wash-out of use sherwood oil and ethyl acetate, obtain 3,4-dimethoxy-2 ', 5 '-dimethyl diphenyl (white solid) 118mg, yield 98.5%.
3,4-dimethoxy-2 ', 5 '-dimethyl diphenyl nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon spectrum nmr analysis data:
1H?NMR(400MHz，CDCl 3)δ7.13(d，J＝7.5Hz，1H)，7.04(d，J＝9.8Hz，2H)，6.91-6.87(m，1H)，6.84(dd，J＝5.8，1.7Hz，2H)，3.88(s，3H)，3.85(d，J＝5.8Hz，3H)，2.33(s，3H)，2.23(s，3H).
13C?NMR(100MHz，CDCl3)δ148.53，147.96，141.62，135.17，134.96，132.32，130.58，130.31127.84，121.40，112.72，110.94，55.92，20.95，20.08.
HRMS(EI)calcd?for?C 16H 8O 2(M-)：242.1365.Found：242.1376。
Experiment nine:
In the single port bottle, add successively 0.5mmol p-Nitrobromobenzene (101mg), 0.6mmol naphthalene phenylo boric acid (103mg), 1.75mmolK 2CO 3(242mg), 0.0125mmol palladium carbon (30mg), 1.5g ionic liquid and 3mL distilled water, at 80 ℃ of magnetic agitation 1h, after reaction finishes, add the saturated NaCl solution of 15mL, and with ethyl acetate extraction 4 times (each 15mL), use anhydrous sodium sulfate drying, filter vacuum concentration, the recycle silicon plastic column chromatography, use mixed solution (volume ratio of sherwood oil and ethyl acetate is 1: the 1) wash-out of sherwood oil and ethyl acetate, obtain white solid 1-naphthalene-4-oil of mirbane 75mg, yield 60.0%.
The nucleus magnetic hydrogen spectrum nmr analysis data of 1-naphthalene-4-oil of mirbane:
1H?NMR(400MHz，CDCl 3)δ8.34(d，J＝8.1Hz，2H)，8.10(s，1H)，8.03-7.80(m，5H)，7.74(d，J＝8.1Hz，1H)，7.55(s，2H)。
Experiment ten:
In the single port bottle, add successively 0.5mmol p-bromobenzaldehyde (92mg), 0.6mmol phenylo boric acid (73mg), 1.75mmolK 2CO 3(242mg); 0.0125mmol palladium carbon (30mg); 1.5g ionic liquid and 3mL distilled water; at 80 ℃ of magnetic agitation 1h; after reaction finishes; add the saturated NaCl solution of 15mL; and with ethyl acetate extraction 4 times (each 15mL); use anhydrous sodium sulfate drying, filter vacuum concentration; the recycle silicon plastic column chromatography; use mixed solution (volume ratio of sherwood oil and ethyl acetate is 1: the 1) wash-out of sherwood oil and ethyl acetate, obtain white solid 4-formyl biphenyl 90mg, yield 99.0%.
The nucleus magnetic hydrogen spectrum nmr analysis data of 4-formyl biphenyl:
1H?NMR(400MHz，CDCl 3)δ10.06(s，1H)，7.95(d，J＝8.4Hz，2H)，7.75(d，J＝8.2Hz，2H)，7.66-7.61(m，2H)，7.48(t，J＝7.3Hz，2H)，7.45-7.39(m，1H).

Claims (10)

1. the preparation method of ionic liquid is characterized in that the preparation method of ionic liquid carries out according to following steps:
In the single port bottle, add successively 9.3g4-picoline and 10.4g2-chloroethyl methyl ether, then at 70 ℃ of stirring reaction 48h, cool to room temperature adds the 100ml acetonitrile, and the 3g gac is at 70 ℃ of reaction 24h, be cooled to 0 ℃, filter, then the solid that obtains is washed three times with ether, drain, vacuum-drying 24h obtains R in the formula 1Methyl, R 2Methyl, Y -It is chlorion.
2. the preparation method of ionic liquid is characterized in that the preparation method of ionic liquid carries out according to following steps:
Add that 10g claim 1 obtains in the single port bottle
Figure FDA00003457814700012
R in the formula 1Methyl, R 2Methyl, Y -Be chlorion, and 16.83g bis trifluoromethyl sulfimide lithium, add the 20ml deionized water again, stirring at room 24h staticly is divided into two-layerly, washes layer with deionized water, and vacuum-drying 24h obtains
Figure FDA00003457814700013
R in the formula 1Methyl, R 2Methyl, Y -It is bis trifluoromethyl sulfimide ion.
3. use the method that ionic liquid palladium carbon catalyzes and synthesizes biphenyl compound, it is characterized in that using ionic liquid palladium carbon, to catalyze and synthesize the method for biphenyl compound as follows:
Halogenated aryl hydrocarbon, aryl boric acid, palladium carbon and salt of wormwood are joined in the ionic liquid aqueous solution, at 80 ℃ of magnetic agitation 1h, add saturated NaCl solution, use again ethyl acetate extraction 4 times, then use anhydrous sodium sulfate drying, filter, vacuum concentration, the recycle silicon plastic column chromatography, the mixed solution wash-out with sherwood oil and ethyl acetate namely gets biphenyl compound;
The mol ratio of described halogenated aryl hydrocarbon and aryl boric acid is 0.8-4: 1;
The addition of described palladium carbon is the 0.1-15% of halogenated aryl hydrocarbon molar weight;
The add-on of described salt of wormwood is 1-5 times of halogenated aryl hydrocarbon molar weight;
The mass ratio of described ionic liquid aqueous solution intermediate ion liquid and water is 1: 0.1-10;
The mixed solution PetroChina Company Limited. ether of described sherwood oil and ethyl acetate and the volume ratio of ethyl acetate are 1-10: 1;
Described halogenated aryl hydrocarbon is 3,4-dimethoxy bromobenzene, para-bromoanisole, p-bromobenzaldehyde, 4-methoxyl group bromobenzene or p-Nitrobromobenzene;
Described aryl boric acid is 4-trifluoromethyl phenylo boric acid, 3,4-dimethoxy phenylo boric acid, 2,5-dimethylphenyl boronic acid, 2,6-dimethylphenyl boronic acid or phenylo boric acid;
Described ionic liquid is
Figure FDA00003457814700014
R in the formula 1Methyl, R 2Methyl, Y -Chlorion or bis trifluoromethyl sulfimide ion.
4. described application ionic liquid palladium carbon catalyzes and synthesizes the method for biphenyl compound according to claim 3, and the mol ratio that it is characterized in that described halogenated aryl hydrocarbon and aryl boric acid is 1-3: 1.
5. described application ionic liquid palladium carbon catalyzes and synthesizes the method for biphenyl compound according to claim 3, and the mol ratio that it is characterized in that described halogenated aryl hydrocarbon and aryl boric acid is 2: 1.
6. described application ionic liquid palladium carbon catalyzes and synthesizes the method for biphenyl compound according to claim 3, and the addition that it is characterized in that described palladium carbon is the 1-13% of halogenated aryl hydrocarbon molar weight.
7. described application ionic liquid palladium carbon catalyzes and synthesizes the method for biphenyl compound according to claim 3, and the addition that it is characterized in that described palladium carbon is 10% of halogenated aryl hydrocarbon molar weight.
8. described application ionic liquid palladium carbon catalyzes and synthesizes the method for biphenyl compound according to claim 3, and the add-on that it is characterized in that described salt of wormwood is 3 times of halogenated aryl hydrocarbon molar weight.
9. described application ionic liquid palladium carbon catalyzes and synthesizes the method for biphenyl compound according to claim 3, and the mass ratio that it is characterized in that described ionic liquid aqueous solution intermediate ion liquid and water is 1: 1-9.
10. described application ionic liquid palladium carbon catalyzes and synthesizes the method for biphenyl compound according to claim 3, and the mass ratio that it is characterized in that described ionic liquid aqueous solution intermediate ion liquid and water is 1: 5.
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钯/碳催化交叉偶联反应制备联苯类化合物;初文毅 等;《中国化学会第28届学术年会第6分会场摘要集》;20120413;第81页 *

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