CN103086842A - Synthesis method of 3,3',4,4',5,5'-hexafluorobiphenyl - Google Patents
Synthesis method of 3,3',4,4',5,5'-hexafluorobiphenyl Download PDFInfo
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Abstract
The invention discloses a synthesis method of 3,3',4,4',5,5'-hexafluorobiphenyl. The synthesis method of 3,3',4,4',5,5'-hexafluorobiphenyl comprises the following step: performing Suzuki coupling reaction on 3,4,5-trifluorohalogenobenzene shown as Formula 1 and 3,4,5-trifluorobenzene boride shown as Formula 2 under the action of a palladium catalyst in the presence of an organic phosphine ligand, an additive and alkali in solvent, wherein X is chlorine, bromine or iodine, y is 1 or 2, OR is hydroxyl, or components shown in the specification, C2-6 represents alkylidene, and C1-6 represents alkyl; when y is 1, OR is a structure shown in the specification; when y is 2, OR is hydroxyl or a structure shown in the specification; and the additive is salt which has a general formula MnAm, wherein M is ammonium, lithium, sodium, potassium, iron or manganese, A is fluorine, chlorine, bromine, iodine, sulfate or acetate, n is 1 or 2, and m is 1, 2 or 3.
Description
Technical field
The present invention relates to 3,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl.
Background technology
Polyfluoro class liquid crystalline cpd because it has good chemical stability, wider characteristics such as operating temperature range, low-viscosity and high electric charge conservation rate, is widely used at present tft liquid crystal and shows in (TFT-LCD) technology.3,3', 4,4', 5,5'-hexafluoro biphenyl are important polyfluoro class liquid crystalline cpds, English name is 3,3', 4,4', 5,5'-Hexafluorobiphenyl, its structural formula is as follows:
In polyfluoro class liquid crystalline cpd is synthetic, construct that Fang-Fang key is even more important and difficulty, wherein the important synthesizing mean of a class is that the palladium catalysis halogenated aryl hydrocarbon of the people such as the Suzuki exploitation eighties in 20th century is constructed the biaryl compound with aryl boric acid or its boric acid derivatives coupling, and the Suzuki coupling method has been widely used in having during the synthetic or industry in the laboratory of biaryl compound of liquid crystal characteristic synthesizes at present.
Yet about 3,3', 4,4', 5,5'-hexafluoro biphenyl synthetic also reported its synthetic method without relevant disclosed documents and materials at present, and only the form with by product is in the news in a small amount of periodical or patent, and its yield is the highest less than 35%.For example, the people such as Hermann-Josef Frohn have described Pd (PPh at Journal of Fluorine Chemistry in 2002,117,115-120
3)
4Catalysis 3,4,3,4,4' is synthesized in 5-trifluorophenyl three potassium fluoborate salt and the coupling of 4-fluorophenyl diazonium a tetrafluoro borate, and 5-tetrafluoro biphenyl is wherein isolated by product 3,3', 4,4', 5,5'-hexafluoro biphenyl, yield are 34%; Equally, the people such as Hermann-Josef Frohn have described Pd (OAc) at Journal of Fluorine Chemistry in 2003,122,195-199
2Catalysis 3,4,3,4,4' is synthesized in 5-trifluorophenyl trimethoxy boric acid lithium salts and the coupling of 4-fluorine iodobenzene, and 5-tetrafluoro biphenyl is wherein isolated by product 3,3', 4,4', 5,5'-hexafluoro biphenyl, yield are only 22%; Described in patent WO2010094736 and utilized the coupling of Negishi method to synthesize the 2-aminobiphenyl compounds, in organic layer GC stratographic analysis 3,4,5-three fluoro-2'-phenylanilines: 2-bromaniline: 1,2,3-trifluoro-benzene: 3,3', 4,4', 5,5'-hexafluoro biphenyl=44:3:39:3,3,3', 4,4', 5,5'-hexafluoro biphenyl only occurs with a small amount of by-product form, has no the yield report.Described in patent WO2011023324 and utilized the coupling of Suzuki method to synthesize N-(3', 4', 5'-three fluoro-5-fluoro-biphenyl) ethanamide, HPLC stratographic analysis N-(3', 4', 5'-three fluoro-5-fluoro-biphenyl) ethanamide: 3,3', 4,4', 5,5'-hexafluoro biphenyl=96.5:3.5,3,3', 4,4', 5,5'-hexafluoro biphenyl also only occurs with a small amount of by-product form, has no the yield report.
Summary of the invention
Technical problem to be solved by this invention is in order to overcome in prior art 3,3', 4,4', 5,5'-hexafluoro biphenyl synthetic method lacks, and reaction conversion ratio is low, and Atom economy is poor, yield is low, and post-reaction treatment is loaded down with trivial details, and product purity is poor, is not suitable for the defectives such as suitability for industrialized production and provides a kind of 3,3', 4,4', 5, the synthetic method of 5'-hexafluoro biphenyl, synthetic method of the present invention, reaction conditions is gentle, and transformation efficiency is high, yield is high, and good product purity is suitable for suitability for industrialized production.
The invention provides 3,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl, it comprises the following steps: in solvent, under the condition that organophosphorus ligand, additive and alkali exist, with as shown in Equation 13,4,5-three fluoro halobenzenes with as shown in Equation 23,4,5-trifluoro-benzene boron compound carries out the Suzuki linked reaction under the effect of palladium catalyst, obtain 3,3', 4,4', 5,5'-hexafluoro biphenyl gets final product;
Wherein X is chlorine, bromine or iodine, y be 1 or 2, OR be hydroxyl,
C wherein
2-6The expression alkylidene group, C
1-6The expression alkyl; When y was 1, OR was
Namely as shown in Equation 23,4,5-trifluoro-benzene boron compound is
When y is 2, OR be hydroxyl or
Namely as shown in Equation 23,4,5-trifluoro-benzene boron compound is
Or
Described additive refers to that general formula is the salt of MnAm, and wherein M is ammonium, lithium, sodium, potassium, iron or manganese, and A is fluorine, chlorine, bromine, iodine, sulfate radical or acetate, n=1 or 2, m=1,2 or 3.
In the present invention, the preferred bromine or iodine of described X, further preferred bromine.
In the present invention, when y is 1, described
Preferably
When y is 2, described
Preferably
Or
The preferred hydroxyl of described OR.
Synthetic method of the present invention can be carried out according to the normal condition of Suzuki linked reaction in this area.In the present invention, following reaction conditions particularly preferably:
In the present invention, described solvent preferably water and/or organic solvent; One or more in the preferred ether solvent of described organic solvent, alcoholic solvent, aromatic hydrocarbon solvent and amide solvent; Described ether solvent is preferred 1, one or more in 2-glycol dimethyl ether, ether and tetrahydrofuran (THF); The preferred C of described alcoholic solvent
1-8Alcoholic solvent; Described C
1-8The preferred Virahol of alcoholic solvent; The preferred toluene of described aromatic hydrocarbon solvent and/or benzene; The preferred DMF of described amide solvent (DMF).
In the present invention, described 3,4, the preferred 0.05:1～0.25:1 of mass ratio of 5-trifluoro-benzene boron compound 2 and described solvent, further preferred 0.1:1～0.2:1.
In the present invention, described 3,4,5-three fluoro halobenzenes 1 are with described 3,4, the preferred 1:1～5:1 of mol ratio of 5-trifluoro-benzene boron compound 2.
In the present invention, the preferred Palladous chloride (PdCl of described palladium catalyst
2), palladium bromide (PdBr
2), palladium (Pd (OAc)
2), Palladous nitrate (Pd (NO
3)
2), palladium charcoal (Pd/C), four (triphenyl) phosphine palladium (Pd (PPh
3)
4), diacetonitrile closes Palladous chloride (Pd (CH
3CN)
2Cl
2), two cyanobenzenes close Palladous chloride (Pd (PhCN)
2Cl
2) and three (dibenzalacetone) two palladium (Pd
2(dba)
3) in one or more, further preferred Palladous chloride and/or palladium.
In the present invention, described palladium catalyst and described 3,4, the preferred 0.0005:1～0.10:1 of mol ratio of 5-trifluoro-benzene boron compound 2.
In the present invention, one or more in described organophosphor ligand preferred alkyl phosphine part, cycloalkyl phosphorus part and aryl phosphine part, the preferred trimethyl-phosphine part of described alkylphosphines and/or tri-butyl phosphine part; The preferred tricyclohexyl phosphine part of described cycloalkyl phosphorus part; Described aryl phosphine part is preferred 1, the two diphenyl phosphine oxide parts of 2-and/or triphenylphosphine ligand.
In the present invention, described organophosphor ligand and described 3,4, the preferred 0.005:1～0.20:1 of mol ratio of 5-trifluoro-benzene boron compound 2.
In the present invention, described general formula is that the salt of MnAm is preferably one or more in Repone K, Potassium monofluoride, sodium-chlor, sodium sulfate and ferric sulfate.
In the present invention, described additive and described 3,4, the preferred 0.001:1～0.20:1 of mol ratio of 5-trifluoro-benzene boron compound 2.
In the present invention, the oxyhydroxide of described alkali preferred as alkali, alkali-metal carbonate, alkali-metal supercarbonate, alkali-metal phosphoric acid salt, alkali-metal fluorochemical, alkali-metal acetate or alkali alcoholate, described basic metal is lithium, sodium, potassium or caesium, preferred sodium, potassium or caesium.One or more in the further preferred sodium hydroxide of described alkali, potassium hydroxide, sodium carbonate and salt of wormwood, more further preferred sodium hydroxide and/or salt of wormwood.
In the present invention, described alkali and described 3,4, the preferred 1:1～4:1 of mol ratio of 5-trifluoro-benzene boron compound 2.
In the present invention, preferred 60 ℃～160 ℃ of the temperature of described linked reaction.
In the present invention, the preferred 0～2MPa of the pressure of described linked reaction.
In the present invention, preferred 1h～24h of the time of described linked reaction.
What the synthetic method described in the present invention was better carries out under the condition that following reagent exists: tetrabutyl halogeno-amine; One or more in the preferred tetrabutyl ammonium fluoride of described tetrabutyl ammonium halide, tetrabutylammonium chloride, Tetrabutyl amonium bromide and tetrabutylammonium iodide.
In the better step of the synthetic method described in the present invention, described tetrabutyl halogeno-amine and described 3,4, the preferred 0.001:1～0.20:1 of mol ratio of 5-trifluoro-benzene boron compound 2, further preferred 0.01:1～0.1:1, more further preferred 0.05:1～0.09:1.
In the present invention, described synthetic method is better also comprises following post-processing operation step: reaction is removed reaction solvent after finishing, then extraction, and washing, organic layer cooling crystallization obtains 3,3', 4,4', 5,5'-hexafluoro biphenyl solid.
In the better post-processing step of synthetic method of the present invention, described extraction solvent used is the conventional solvent that carries out this generic operation in this area, one or more in preferred alkane solvents, aromatic hydrocarbon solvent and alcoholic solvent; The preferred C of described alkane solvents
6-8Alkane solvent, further one or more in preferred normal hexane, isohexane and hexanaphthene; One or more in the preferred benzene of described aromatic hydrocarbon solvent, toluene and dimethylbenzene; The preferred C of described alcoholic solvent
4-8Alcoholic solvent; Described C
4-8The preferred isopropylcarbinol of alcoholic solvent.
In the better post-processing step of synthetic method of the present invention, what the temperature during described extracting operation was better is 50 ℃～60 ℃.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, but arbitrary combination namely get the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available getting all.
Room temperature described in the present invention refers to 10 ℃～30 ℃.
Positive progressive effect of the present invention is: provided by the invention 3, and 3', 4,4', the synthetic method reaction conversion ratio of 5,5'-hexafluoro biphenyl is high, Atom economy good, and post-processing operation is simple, and reaction yield is high, good product purity, environmental friendliness is suitable for suitability for industrialized production.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example according to ordinary method and condition, or is selected according to catalogue.
Embodiment 13,3', 4,4', 5,5'-hexafluoro biphenyl synthetic
under room temperature, with 3, 4, 5-trifluoro-benzene boric acid 30.8g(0.175mol), 3, 4, 5-trifluorobromobenzene 38.0g(0.180mol), tetrahydrofuran (THF) 185g and water 88g drop in the 1L autoclave, then slowly add solid sodium hydroxide 9.8g(0.242mol), stirred 5 minutes, add again Palladous chloride 0.062g(0.208mmol), part triphenylphosphine 0.64g(2.44mmol), Repone K 0.12g(1.50mmol) and Potassium monofluoride 0.9g(0.015mol), nitrogen replacement three times, be warming up to 110 ℃～120 ℃, still is pressed and is maintained 0.3Mpa～0.4Mpa, insulation reaction 6h, finish reaction, be cooled to 50 ℃, underpressure distillation removes tetrahydrofuran (THF), then add the isopropylcarbinol extraction under 50 ℃～60 ℃, layering, the washing layering, organic layer slow cooling to 0 ± 2 ℃, separate out white solid product 3, 3', 4, 4', 5, 5'-hexafluoro biphenyl, HPLC content〉99%, quality 36.7g, yield 80%.
Embodiment 23,3', 4,4', 5,5'-hexafluoro biphenyl synthetic
under room temperature, with 3, 4, 5-trifluoro-benzene boric acid 30.8g(0.175mol), 3, 4, 5-trifluorobromobenzene 38.0g(0.180mol), tetrahydrofuran (THF) 185g and water 88g drop in the 1L autoclave, then slowly add solid sodium hydroxide 9.8g(0.242mol), stirred 5 minutes, add again Palladous chloride 0.062g(0.208mmol), part triphenylphosphine 0.64g(2.44mmol), Repone K 0.12g(1.50mmol) and Potassium monofluoride 0.9g(0.015mol), nitrogen replacement three times, be warming up to 85 ℃～95 ℃, still is pressed and is maintained 0.2Mpa～0.25Mpa, insulation reaction 18h, finish reaction, be cooled to 50 ℃, underpressure distillation removes tetrahydrofuran (THF), then add the isopropylcarbinol extraction under 50 ℃～60 ℃, layering, the washing layering, organic layer slow cooling to 0 ± 2 ℃, separate out white solid product 3, 3', 4, 4', 5, 5'-hexafluoro biphenyl, HPLC content〉97%, quality 28.0g, yield 61%.
Embodiment 33,3', 4,4', 5,5'-hexafluoro biphenyl synthetic
under room temperature, with 3, 4, 5-trifluoro-benzene boric acid 30.8g(0.175mol), 3, 4, 5-trifluorobromobenzene 38.0g(0.180mol), tetrahydrofuran (THF) 185g and water 88g drop in the 1L autoclave, then slowly add solid sodium hydroxide 9.8g(0.242mol), stirred 5 minutes, add again Palladous chloride 0.062g(0.208mmol), part triphenylphosphine 0.64g(2.44mmol), ferric sulfate 5.60g(0.014mol) and Potassium monofluoride 0.9g(0.015mol), nitrogen replacement three times, be warming up to 110 ℃～120 ℃, still is pressed and is maintained 0.3Mpa～0.4Mpa, insulation reaction 6h, finish reaction, be cooled to 50 ℃, underpressure distillation removes tetrahydrofuran (THF), then add the isopropylcarbinol extraction under 50 ℃～60 ℃, layering, the washing layering, organic layer slow cooling to 0 ± 2 ℃, separate out white solid product 3, 3', 4, 4', 5, 5'-hexafluoro biphenyl, HPLC content〉99%, quality 37.3g, yield 81.5%.
Embodiment 43,3', 4,4', 5,5'-hexafluoro biphenyl synthetic
under room temperature with content 16.17%(wt%) 3, 4, the tetrahydrofuran solution 220.7g of 5-trifluoro-benzene trimethyl borate (0.175mol), 3, 4, 5-trifluorobromobenzene 38.0g(0.180mol) and water 88g drop in the 1L autoclave, then slowly add solid sodium hydroxide 14g(0.350mol), stirred 5 minutes, add again Palladous chloride 0.062g(0.208mmol), part triphenylphosphine 0.64g(2.44mmol), Repone K 0.12g(1.50mmol) and Potassium monofluoride 0.9g(0.015mol), be warming up to 110 ℃～120 ℃, still is pressed and is maintained 0.3Mpa～0.4Mpa, insulation reaction 6h, finish reaction, be cooled to 50 ℃, underpressure distillation removes tetrahydrofuran (THF), then add the isopropylcarbinol extraction under 50 ℃～60 ℃, layering, the washing layering, organic layer slow cooling to 0 ± 2 ℃, separate out white solid product 3, 3', 4, 4', 5, 5'-hexafluoro biphenyl, HPLC content〉99%, quality 27.7g, yield 60.5%.
Embodiment 53,3', 4,4', 5,5'-hexafluoro biphenyl synthetic
under room temperature with 3, 4, 5-trifluoro-benzene boric acid 30.8g(0.175mol), 3, 4, 5-trifluorobromobenzene 38.0g(0.180mol), tetrahydrofuran (THF) 185g and water 88g drop in the 1L autoclave, then slowly add solid sodium hydroxide 9.8g(0.242mol), stirred 5 minutes, add again palladium 0.047g(0.208mmol), part triphenylphosphine 0.64g(2.44mmol), sodium sulfate 0.214g(1.50mmol) and Potassium monofluoride 0.9g(0.015mol), nitrogen replacement three times, be warming up to 110～120 ℃, still is pressed and is maintained 0.3Mpa～0.4Mpa, insulation reaction 6h, finish reaction, be cooled to 50 ℃, underpressure distillation removes tetrahydrofuran (THF), then add the isopropylcarbinol extraction under 50 ℃～60 ℃, layering, the washing layering, organic layer slow cooling to 0 ± 2 ℃, separate out white solid product 3, 3', 4, 4', 5, 5'-hexafluoro biphenyl, HPLC content〉99%, quality 39.5g, yield 86%.
Embodiment 63,3', 4,4', 5,5'-hexafluoro biphenyl synthetic
under room temperature with 3, 4, 5-trifluoro-benzene boric acid 30.8g(0.175mol), 3, 4, 5-trifluorobromobenzene 38.0g(0.180mol), tetrahydrofuran (THF) 185g and water 88g drop in the 1L autoclave, then slowly add solid sodium hydroxide 9.8g(0.242mol), stirred 5 minutes, add again Palladous chloride 0.062g(0.208mmol), part triphenylphosphine 0.64g(2.44mmol), sodium sulfate 0.214g(1.50mmol) and Potassium monofluoride 0.9g(0.015mol), nitrogen replacement three times, be warming up to 110 ℃～120 ℃, still is pressed and is maintained 0.3Mpa～0.4Mpa, insulation reaction 6h, finish reaction, be cooled to 50 ℃, underpressure distillation removes tetrahydrofuran (THF), then add the isopropylcarbinol extraction under 50 ℃～60 ℃, layering, the washing layering, organic layer slow cooling to 0 ± 2 ℃, separate out white solid product 3, 3', 4, 4', 5, 5'-hexafluoro biphenyl, HPLC content〉99%, quality 37.6g, yield 82%.
Embodiment 73,3', 4,4', 5,5'-hexafluoro biphenyl synthetic
under room temperature with 3, 4, 5-trifluoro-benzene boric acid 30.8g(0.175mol), 3, 4, 5-trifluorobromobenzene 38.0g(0.180mol), tetrahydrofuran (THF) 185g and water 88g drop in the 1L autoclave, then slowly add solid sodium hydroxide 9.8g(0.242mol), stirred 5 minutes, add again Palladous chloride 0.062g(0.208mmol), part triphenylphosphine 0.64g(2.44mmol), sodium sulfate 0.214g(1.50mmol) and Potassium monofluoride 0.9g(0.015mol), nitrogen replacement three times, be warming up to 110 ℃～120 ℃, still is pressed and is maintained 0.3Mpa～0.4Mpa, insulation reaction 6h, finish reaction, be cooled to 50 ℃, underpressure distillation removes tetrahydrofuran (THF), then add the isohexane extraction under 50 ℃～60 ℃, layering, the washing layering, organic layer slow cooling to 0 ± 2 ℃, separate out white solid product 3, 3', 4, 4', 5, 5'-hexafluoro biphenyl, HPLC content〉98.0%, quality 38.5g, yield 84%.
Embodiment 83,3', 4,4', 5,5'-hexafluoro biphenyl synthetic
under room temperature with 3, 4, 5-trifluoro-benzene boric acid 30.8g(0.175mol), 3, 4, 5-trifluorobromobenzene 38.0g(0.180mol), tetrahydrofuran (THF) 185g drops in the 1L autoclave, then slowly add solid sodium hydroxide 9.8g(0.242mol), stirred 5 minutes, add again Palladous chloride 0.062g(0.208mmol), part triphenylphosphine 0.64g(2.44mmol), sodium sulfate 0.214g(1.50mmol) and Potassium monofluoride 0.9g(0.015mol), nitrogen replacement three times, be warming up to 110 ℃～120 ℃, still is pressed and is maintained 0.3Mpa～0.4Mpa, insulation reaction 6h, finish reaction, be cooled to 50 ℃, underpressure distillation removes tetrahydrofuran (THF), then add the isopropylcarbinol extraction under 50 ℃～60 ℃, layering, the washing layering, organic layer slow cooling to 0 ± 2 ℃, separate out white solid product 3, 3', 4, 4', 5, 5'-hexafluoro biphenyl, HPLC content〉99%, quality 25.7g, yield 56%.
Embodiment 93,3', 4,4', 5,5'-hexafluoro biphenyl synthetic
under room temperature with 3, 4, 5-trifluoro-benzene boric acid 30.8g(0.175mol), 3, 4, 5-trifluorobromobenzene 38.0g(0.180mol), tetrahydrofuran (THF) 185g and water 88g drop in the 1L autoclave, then slowly add solid carbonic acid potassium 48.4g(0.350mol), stirred 5 minutes, add again Palladous chloride 0.062g(0.208mmol), part triphenylphosphine 0.64g(2.44mmol), sodium sulfate 0.214g(1.50mmol) and Potassium monofluoride 0.9g(0.015mol), nitrogen replacement three times, be warming up to 110 ℃～120 ℃, still is pressed and is maintained 0.3Mpa～0.4Mpa, insulation reaction 6h, finish reaction, be cooled to 50 ℃, underpressure distillation removes tetrahydrofuran (THF), then add the isopropylcarbinol extraction under 50 ℃～60 ℃, layering, the washing layering, organic layer slow cooling to 0 ± 2 ℃, separate out white solid product 3, 3', 4, 4', 5, 5'-hexafluoro biphenyl, HPLC content〉99%, quality 28.0g, yield 61%.
Embodiment 10 3,3', 4,4', 5,5'-hexafluoro biphenyl synthetic
under room temperature with 3, 4, 5-trifluoro-benzene boric acid 30.8g(0.175mol), 3, 4, 5-trifluorobromobenzene 38.0g(0.180mol), tetrahydrofuran (THF) 185g and water 88g drop in the 1L autoclave, then slowly add solid sodium hydroxide 9.8g(0.242mol), stirred 5 minutes, add again Palladous chloride 0.062g(0.208mmol), part triphenylphosphine 0.64g(2.44mmol), sodium sulfate 0.214g(1.50mmol) and tetrabutyl ammonium fluoride 3.92g(0.015mol), nitrogen replacement three times, be warming up to 110 ℃～120 ℃, still is pressed and is maintained 0.3Mpa～0.4Mpa, insulation reaction 6h, finish reaction, be cooled to 50 ℃, underpressure distillation removes tetrahydrofuran (THF), then add the isopropylcarbinol extraction under 50 ℃～60 ℃, layering, the washing layering, organic layer slow cooling to 0 ± 2 ℃, separate out white solid product 3, 3', 4, 4', 5, 5'-hexafluoro biphenyl, HPLC content〉99%, quality 39.1g, yield 85%.
Embodiment 11 3,3', 4,4', 5,5'-hexafluoro biphenyl synthetic
under room temperature with 3, 4, 5-trifluoro-benzene boric acid 30.8g(0.175mol), 3, 4, 5-trifluorobromobenzene 38.0g(0.180mol), Virahol 170g and water 88g drop in the 1L autoclave, then slowly add solid sodium hydroxide 9.8g(0.242mol), stirred 5 minutes, add again Palladous chloride 0.062g(0.208mmol), part triphenylphosphine 0.64g(2.44mmol), sodium sulfate 0.214g(1.50mmol) and Potassium monofluoride 0.9g(0.015mol), nitrogen replacement three times, be warming up to 110 ℃～120 ℃, still is pressed and is maintained 0.3Mpa～0.4Mpa, insulation reaction 6h, finish reaction, be cooled to 50 ℃, the decompression component distillation removes Virahol, then add the isopropylcarbinol extraction under 50 ℃～60 ℃, layering, the washing layering, organic layer slow cooling to 0 ± 2 ℃, separate out white solid product 3, 3', 4, 4', 5, 5'-hexafluoro biphenyl, HPLC content〉99%, quality 35.7g, yield 78%.
Claims (18)
1. one kind 3,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl is characterized in that comprising the following steps: in solvent, under the condition that organophosphorus ligand, additive and alkali exist, with as shown in Equation 13,4,5-three fluoro halobenzenes with as shown in Equation 23,4,5-trifluoro-benzene boron compound carries out the Suzuki linked reaction under the effect of palladium catalyst, obtain 3,3', 4,4', 5,5'-hexafluoro biphenyl gets final product;
Wherein X is chlorine, bromine or iodine, y be 1 or 2, OR be hydroxyl,
C wherein
2-6The expression alkylidene group, C
1-6The expression alkyl; When y was 1, OR was
When y is 2, OR be hydroxyl or
Described additive refers to that general formula is the salt of MnAm, and wherein M is ammonium, lithium, sodium, potassium, iron or manganese, and A is fluorine, chlorine, bromine, iodine, sulfate radical or acetate, n=1 or 2, m=1,2 or 3.
2. as claimed in claim 13,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl is characterized in that:
When y is 1, described
For
When y is 2, described
For
3. as claimed in claim 13,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl is characterized in that: described solvent is water and/or organic solvent; Described organic solvent is one or more in ether solvent, alcoholic solvent, aromatic hydrocarbon solvent and amide solvent.
4. as claimed in claim 33,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl is characterized in that: described ether solvent is one or more in 1,2-glycol dimethyl ether, ether and tetrahydrofuran (THF).
5. as claimed in claim 33,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl is characterized in that: described alcoholic solvent is C
1-8Alcoholic solvent.
6. as claimed in claim 53,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl is characterized in that: described C
1-8Alcoholic solvent be Virahol.
7. as claimed in claim 33,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl is characterized in that: described aromatic hydrocarbon solvent is toluene and/or benzene.
8. as claimed in claim 33,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl is characterized in that: described amide solvent is DMF.
9. as described in claim 1～8 any one 3,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl is characterized in that: described 3,4,5-three fluoro halobenzenes 1 are with described 3,4, and the mol ratio of 5-trifluoro-benzene boron compound 2 is 1:1～5:1.
10. as claimed in claim 13,3', 4,4', 5, the synthetic method of 5'-hexafluoro biphenyl is characterized in that: described palladium catalyst is that Palladous chloride, palladium bromide, palladium, Palladous nitrate, palladium charcoal, four (triphenyl) phosphine palladium, diacetonitrile close Palladous chloride, two cyanobenzenes and close one or more in Palladous chloride and three (dibenzalacetone) two palladiums; Described palladium catalyst and described 3,4, the mol ratio of 5-trifluoro-benzene boron compound 2 is 0.0005:1～0.10:1.
11. as claimed in claim 13,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl is characterized in that: described organophosphor ligand is one or more in alkylphosphines part, cycloalkyl phosphorus part and aryl phosphine part; Described organophosphor ligand and described 3,4, the mol ratio of 5-trifluoro-benzene boron compound 2 is 0.005:1～0.20:1.
12. as claimed in claim 11 3,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl is characterized in that: described alkylphosphines part is trimethyl-phosphine part and/or tri-butyl phosphine part.
13. as claimed in claim 11 3,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl is characterized in that: described cycloalkyl phosphine part is the tricyclohexyl phosphine part.
14. as claimed in claim 11 3,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl is characterized in that: described aryl phosphine part is the two diphenyl phosphine oxide parts of 1,2-and/or triphenylphosphine ligand.
15. as claimed in claim 13,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl is characterized in that: described general formula is that the salt of MnAm is one or more in Repone K, Potassium monofluoride, sodium-chlor, sodium sulfate and ferric sulfate; Described additive and described 3,4, the mol ratio of 5-trifluoro-benzene boron compound 2 is 0.001:1～0.20:1.
16. as claimed in claim 13,3', 4,4', 5, the synthetic method of 5'-hexafluoro biphenyl is characterized in that: described alkali is alkali-metal oxyhydroxide, alkali-metal carbonate, alkali-metal supercarbonate, alkali-metal phosphoric acid salt, alkali-metal fluorochemical, alkali-metal acetate or alkali alcoholate, and described basic metal is lithium, sodium, potassium or caesium; Described alkali and described 3,4, the mol ratio of 5-trifluoro-benzene boron compound 2 is 1:1～4:1.
17. as claimed in claim 16 3,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl is characterized in that: described alkali is one or more in sodium hydroxide, potassium hydroxide, sodium carbonate and salt of wormwood.
18. as claimed in claim 13,3', 4,4', the synthetic method of 5,5'-hexafluoro biphenyl is characterized in that: the temperature of described linked reaction is 60 ℃～160 ℃; The pressure of described linked reaction is 0～2MPa.
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