CN113087590B - Synthetic method of 2,2',3,3',5,5',6,6' -octafluorobiphenyl - Google Patents
Synthetic method of 2,2',3,3',5,5',6,6' -octafluorobiphenyl Download PDFInfo
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Abstract
The invention discloses a synthetic method of 2,2',3,3',5,5',6,6' -octafluorobiphenyl, belonging to the technical field of chemical synthesis. Reacting 2,3,5, 6-tetrafluoro-1, 4-dihalobenzene with metal magnesium in an inert solvent to obtain 2,3,5, 6-tetrafluoro-4-halophenyl magnesium halide; 2,3,5, 6-tetrafluoro-4-halogenophenyl magnesium halide is subjected to self-coupling reaction in an inert solvent under the action of a copper catalyst and oxygen to obtain 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dihalobiphenyl; 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dihalobiphenyl is subjected to hydrogen hydrogenation reduction in a solvent under the action of a catalyst to obtain the 2,2',3,3',5,5',6,6' -octafluorobiphenyl. The method has the advantages of cheap and easily obtained raw materials, short reaction steps, high synthesis yield, good product quality and the like, and is suitable for industrial production and application.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a synthetic method of 2,2',3,3',5,5',6,6' -octafluorobiphenyl.
Background
2,2',3,3',5,5',6,6' -octafluorobiphenyl is a very important chemical intermediate, has wide application prospect in the field of photoelectric materials, and can be used for preparing high-end photoelectric materials such as photoelectric solid materials, organic light-emitting diodes, organic field effect transistors, solar cells and the like.
The synthesis method of 2,2',3,3',5,5',6,6' -octafluorobiphenyl mainly comprises the following three methods:
(1) decafluorobiphenyl is used as a raw material, and 2,2',3,3',5,5',6,6' -octafluorobiphenyl is obtained through reduction defluorination reaction:
the synthesis route is researched more, and a plurality of documents disclose and report that the reaction yield varies from medium to excellent by adopting different reductive defluorination schemes, such as triethylphosphine, diethylsilane, zinc powder, catalytic reductive defluorination and the like. The method has the defects that the raw material of the decafluorobiphenyl is expensive and not easy to obtain, the defluorination reaction condition is mainly researched, and the industrial application is difficult to realize.
(2) 2,3,5, 6-tetrafluorohalogenobenzene and 2,3,5, 6-tetrafluorophenylboronic acid (ester) are used as raw materials, and the raw materials are subjected to palladium-catalyzed cross-coupling reaction to obtain 2,2',3,3',5,5',6,6' -octafluorobiphenyl:
the synthesis method adopts Suzuki-Miyaura cross-coupling reaction, uses expensive palladium catalyst and phosphine ligand, has harsh reaction conditions, and the raw materials of 2,3,5, 6-tetrafluoro halogeno benzene and 2,3,5, 6-tetrafluoro phenylboronic acid (ester) are expensive and difficult to obtain, have higher synthesis cost, and are not suitable for industrial production.
(3) 2,3,5, 6-tetrafluorodihalobenzene is taken as a raw material, and the 2,2',3,3',5,5',6,6' -octafluorobiphenyl is obtained through self-coupling, reduction and dehalogenation reaction:
the synthetic method has the disadvantages that in the first step of the coupling reaction process, the excessive cuprous thiophene-2-formate is used as a coupling catalyst, so that the synthetic cost is high and the pollution is serious; in the second step, lithium aluminum hydride which is expensive and highly dangerous is used as a dehalogenation agent for reduction dehalogenation, so that the safety risk is high during industrial production; the reaction yield is low, a large amount of polymeric impurities exist, and the purification is difficult.
Disclosure of Invention
The invention aims to provide a simple and efficient synthesis method of 2,2',3,3',5,5',6,6' -octafluorobiphenyl, and lays a foundation for industrial production. The synthesis method has the advantages of cheap and easily-obtained raw materials, short reaction steps, high synthesis yield, good product quality and the like, and is suitable for industrial production and application.
The technical scheme adopted by the invention is as follows:
a synthetic method of 2,2',3,3',5,5',6,6' -octafluorobiphenyl comprises the following steps:
(1) reacting 2,3,5, 6-tetrafluoro-1, 4-dihalobenzene (I) with metal magnesium in an inert solvent to obtain 2,3,5, 6-tetrafluoro-4-halophenyl magnesium halide (II);
(2) the obtained 2,3,5, 6-tetrafluoro-4-halogenophenyl magnesium halide (II) is subjected to self-coupling reaction in an inert solvent under the action of a copper catalyst and oxygen to obtain 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dihalobiphenyl (III);
(3) and (3) hydrogenating and reducing the obtained 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dihalobiphenyl (III) in a solvent under the action of a catalyst by hydrogen to obtain the 2,2',3,3',5,5',6,6' -octafluorobiphenyl (V).
The technical route adopted by the invention can be represented by the following reaction formula:
the invention further provides that:
in the step (1):
the raw material 2,3,5, 6-tetrafluoro-1, 4-dihalobenzene is selected from one or more of the following: 2,3,5, 6-tetrafluoro-1, 4-dichlorobenzene, 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene, 2,3,5, 6-tetrafluoro-1, 4-diiodobenzene.
The inert solvent is a solvent which does not generate side reaction with raw materials, intermediates, products and the like in the reaction process. The inert solvent is selected from one or more of the following: straight-chain or branched-chain alkane solvents such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, etc.; cycloalkane-based solvents such as cyclopentane, cyclohexane, methylcyclohexane, decalin, and the like; aromatic hydrocarbon solvents such as benzene, toluene, xylene, etc.; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, etc. Preferred inert solvents are ethereal solvents, represented by the following general formula: R-O-R ', wherein R, R' is C1-C10 straight-chain, branched-chain or cyclic alkyl, C1-C10 straight-chain, branched-chain or cyclic alkoxy alkyl. Representative ether solvents are: diethyl ether, methyl propyl ether, ethyl propyl ether, methyl isopropyl ether, ethyl isopropyl ether, methyl n-butyl ether, ethyl n-butyl ether, methyl isobutyl ether, ethyl isobutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dimethoxymethane, diethoxymethane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, 1-dimethoxypropane, 1-diethoxypropane, 2-dimethoxypropane, 2-diethoxypropane, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, cyclopentyl methyl ether, cyclohexyl methyl ether, and the like. The inert solvent used can be a single solvent or a mixed solvent consisting of two or more inert solvents, and the dosage of the solvent is 1-15 times of the mass of the compound (I).
The magnesium metal is required to be dry and fresh in surface without oxides, and is processed into a form with a higher specific surface area, such as magnesium chips, magnesium powder, magnesium strips and the like, so as to ensure good reaction activity. The ratio of the amount of the metallic magnesium to the amount of the compound (I) is (1-1.5): 1, and the preferable ratio of the amount of the metallic magnesium to the amount of the compound (I) is (1-1.2): 1.
The proper reaction temperature has an important influence on the smooth progress of the reaction. The reaction initiation can be promoted by properly increasing the reaction temperature, the accumulation of raw materials in a system caused by unsuccessful initiation in the early stage of the reaction is avoided, the safety risk is increased, meanwhile, the higher reaction temperature is also beneficial to accelerating the reaction speed, shortening the reaction time and reducing the residual quantity of the raw materials after the reaction is finished, but unnecessary side reactions can be caused by the excessively high reaction temperature, so that the product content and the reaction yield are reduced. The optional reaction temperature is (-30-100) DEG C, and the preferred reaction temperature is (-20-80) DEG C.
The reaction of this step is a reaction for preparing an aryl grignard reagent by reacting an aryl halide with magnesium metal, and is required to be carried out under anhydrous conditions, so that the moisture content of raw materials, a solvent and the like needs to be strictly controlled to ensure smooth initiation and normal operation of the reaction. In addition, before the reaction starts, a proper amount of elementary iodine, 1, 2-dibromoethane, alkyl Grignard reagent such as isopropyl magnesium chloride or inert solvent solution of the prepared compound (II) can be added into the reaction system to be used as a reaction initiator to promote the successful initiation of the Grignard reaction.
In the step (2):
the inert solvent is a solvent which does not generate side reaction with raw materials, intermediates, products and the like in the reaction process. The inert solvent is selected from one or more of the following: straight-chain or branched-chain alkane solvents such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, etc.; cycloalkane-based solvents such as cyclopentane, cyclohexane, methylcyclohexane, decalin, and the like; aromatic hydrocarbon solvents such as benzene, toluene, xylene, etc.; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, etc. Preferred inert solvents are ethereal solvents, represented by the following general formula: R-O-R ', wherein R, R' is C1-C10 straight-chain, branched-chain or cyclic alkyl, C1-C10 straight-chain, branched-chain or cyclic alkoxy alkyl. Representative ether solvents are: diethyl ether, methyl propyl ether, ethyl propyl ether, methyl isopropyl ether, ethyl isopropyl ether, methyl n-butyl ether, ethyl n-butyl ether, methyl isobutyl ether, ethyl isobutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dimethoxymethane, diethoxymethane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, 1-dimethoxypropane, 1-diethoxypropane, 2-dimethoxypropane, 2-diethoxypropane, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, cyclopentyl methyl ether, cyclohexyl methyl ether, and the like. The inert solvent used may be a single solvent or a mixed solvent of two or more inert solvents, and may be the same as or different from the solvent used in step (1). The dosage of the solvent is 1-20 times of the mass of the compound (II).
The reaction in this step is a copper-catalyzed self-coupling reaction of a Grignard reagent. The copper catalyst can be inorganic copper compound, such as copper halide, cuprous halide, cupric oxide, cuprous oxide, etc., or organic copper compound, such as cupric acetate, cuprous acetate, etc., or elemental copper, such as copper powder. The preferred copper catalyst is an inorganic copper compound selected from one or more of the following: copper chloride, cuprous chloride, copper bromide, cuprous bromide, copper iodide, cuprous iodide, cupric sulfate, cuprous sulfate, cupric oxide, and cuprous oxide. The mass ratio of the copper catalyst to the compound (II) is (0.0001 to 0.5):1, and the mass ratio of the copper catalyst to the compound (II) is preferably (0.0001 to 0.3): 1.
The oxygen in the reaction is used as an oxidant, and plays a role in promoting the recycling of the copper catalyst in the reaction process, so that the using amount of the copper catalyst is reduced. If the reaction is carried out under oxygen-exclusion conditions, for example, under protection of an inert gas such as nitrogen atmosphere or argon atmosphere, the amount of the copper catalyst used is at least 0.5 equivalent or more based on the amount of the compound (II) substance, provided that the same effect is achieved. The oxygen can be pure oxygen or a mixed gas of oxygen and inert gas, and the inert gas is selected from one or more of the following: nitrogen, helium, neon, argon, krypton, and the like. Since the main components of the dry air are oxygen and inert nitrogen, wherein the oxygen accounts for about 21%, the nitrogen accounts for about 78%, and although a small amount of other gases, such as carbon dioxide, have a certain effect on the reaction, the dry air can also be used as a supply source of the oxygen for the reaction because the content of impurity gas components is small and the effect on the reaction is small. The oxygen can be provided in the form of atmosphere or in the form of bubbling, and the dosage of the oxygen does not need to be accurately controlled, and only continuous oxygen supply is ensured in the reaction process.
The reaction can be carried out at a low temperature, the optional reaction temperature is (-80-100) DEG C, and the preferred reaction temperature is (-70-80) DEG C.
In the step (3):
the solvent refers to all solvents suitable for catalytic hydrogenation and dehalogenation reaction, and the selectable solvents include alcohol solvents, ester solvents, ether solvents, alkane solvents, aromatic solvents, water and the like. Preferred solvents are alcohol solvents, ester solvents, ether solvents and water. The alcohol solvent can be monohydric alcohol solvent or polyhydric alcohol solvent, and is represented by the following general formula: r (OH)nWherein R is C1-C10 linear chain, branched chain or cyclic alkyl, C1-C10 linear chain, branched chain or cyclic alkoxy alkyl, and n is 1-3; representative alcohol solvents are methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-pentanol, n-hexanol, cyclopentanol, cyclohexanol, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-cyclohexanediol, glycerol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the like. The ester solvent is represented by the following general formula: R-CO2-R', wherein R is a linear, branched or cyclic alkyl group from C1 to C10, a linear, branched or cyclic alkoxy group from C1 to C10, a linear, branched or cyclic alkoxyalkyl group from C1 to C10; r' is C1-C10 linear chain, branched chain or cyclic alkyl, C1-C10 linear chain or branched chain alkoxy alkyl; representative ester solvents are methyl formate, ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate, cyclohexyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl methoxyacetate, ethyl methoxyacetate, and the like. The ether solvent is represented by the following general formula: R-O-R ', wherein R and R' are C1-C10 linear chain, branched chain or cyclic alkyl, C1-C10 linear chain, branched chain or cyclic alkoxy alkyl; representative ether solvents are diethyl ether, methyl propyl ether, ethyl propyl ether, methyl isopropyl ether, ethyl isopropyl ether, methyl n-butyl ether, ethyl n-butyl ether, methyl isobutyl ether, methyl ethyl isopropyl ether, methyl ethyl propyl ether, methyl isobutyl ether, methyl ethyl propyl ether, methyl ethyl butyl ether, methyl ethyl propyl ether, methyl isopropyl ether, methyl propyl ether, methyl isopropyl ether, ethyl butyl ether, methyl isobutyl ether, and the like,Ethyl isobutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dimethoxymethane, diethoxymethane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, 1-dimethoxypropane, 1-diethoxypropane, 2-dimethoxypropane, 2-diethoxypropane, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, cyclopentyl methyl ether, cyclohexyl methyl ether, and the like. The solvent is a single solvent, or a homogeneous or heterogeneous mixed solvent consisting of two or more solvents, and the dosage of the solvent is 1-20 times of the mass of the compound (III).
The catalyst is selected from one or more of the following: palladium carbon, sponge nickel, sponge cobalt. The palladium-carbon catalyst refers to an activated carbon dispersion of palladium obtained by loading metal palladium on activated carbon, and is classified into different specifications according to the effective content of palladium, whether palladium is contained in water, and the like, such as 10% dry palladium-carbon, 10% wet palladium-carbon (water content of about 50%), 5% dry palladium-carbon, 5% wet palladium-carbon (water content of about 50%), 1% dry palladium-carbon, 1% wet palladium-carbon (water content of about 50%), and the like. The spongy nickel catalyst and the spongy cobalt catalyst are also called skeleton nickel and skeleton cobalt or Raney nickel and Raney cobalt, and are prepared by treating corresponding nickel-aluminum alloy and cobalt-aluminum alloy with concentrated alkali, such as concentrated sodium hydroxide solution, concentrated potassium hydroxide solution and the like, dissolving aluminum in the corresponding nickel-aluminum alloy and cobalt-aluminum alloy, and leaving microporous metal nickel and metal cobalt which are active due to nature and can burn when exposed in air so as to be fully soaked in water for storage. The catalyst can be prepared by self or can be commercial products with different specifications. The catalyst is selected without specific limitation on the specification as long as the catalytic activity satisfies the requirements. The amount of the palladium-carbon catalyst is related to the effective content of palladium in the palladium-carbon, and the specific amount is experimentally confirmed, generally, after moisture is subtracted (i.e. dried), the amount of 10% palladium-carbon is (0.0001-0.2) times of the mass of the compound (III), and 1% palladium-carbon is used as the catalyst, after moisture is subtracted (i.e. dried), the amount of 1% palladium-carbon is (0.001-0.25) times of the mass of the compound (III). The sponge nickel catalyst and the sponge cobalt catalyst are used as an aqueous paste, wherein the effective weight of nickel and cobalt is 0.001 to 0.3 times of the mass of the compound (III).
The reaction in this step is an aromatic ring hydrogenation and dehalogenation reaction, and hydrogen halide is generated in the reaction process. Because most hydrogenation equipment used for production is stainless steel, the hydrogenation equipment cannot resist the corrosion of hydrogen halide, and in addition, catalysts, particularly sponge nickel and sponge cobalt, can react with hydrogen halide to cause the catalyst to lose efficacy. Therefore, in order to avoid the adverse effect of the generated hydrogen halide on the hydrogenation equipment and the catalyst, an appropriate amount of acid-binding agent is preferably added during the reaction process to neutralize the hydrogen halide generated by the reaction. Of course, if a reaction device with anti-corrosion capability is selected and palladium carbon is selected as a catalyst, an acid-binding agent is not needed for the reaction. The acid-binding agent can be organic amine compounds such as alkyl tertiary amine and substituted pyridine, and can also be oxides, hydroxides, carbonates, phosphates and the like of alkali metals and alkaline earth metals. The alkyl tertiary amine acid-binding agent can be represented by the following general formula: RR 'R' N, wherein R, R 'and R' are linear, branched or cyclic alkyl of C1-C10. The preferable acid-binding agent is selected from one or more of the following: lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, lithium phosphate, sodium phosphate, potassium phosphate, magnesium phosphate, calcium phosphate, dilithium hydrogenphosphate, disodium hydrogenphosphate, dipotassium hydrogenphosphate, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, dimethylethylamine, dimethyl-n-propylamine, dimethylisopropylamine, dimethyl-n-butylamine, diethylmethylamine, diethyl-n-propylamine, diethylisopropylamine, diethyl-n-butylamine, di-n-propylmethylamine, di-n-propylethylamine, di-n-propylisopropylamine, di-n-propyln-butylamine, diisopropylmethylamine, diisopropylethylamine, diisopropyln-propylamine, diisopropyln-butylamine, di-n-butylethylamine, di-butylethylamine, lithium carbonate, sodium carbonate, lithium carbonate, di-N-butyl-N-propylamine, di-N-butyl-isopropylamine, triethylene diamine, N-methylmorpholine, N-dimethylpiperazine, pyridine and 4-dimethylaminopyridine. The dosage of the acid-binding agent needs to be determined according to the acid-binding capacity of the acid-binding agent molecules, the hydrogen halide generated by the complete neutralization reaction is taken as a standard, and the preferable ratio of the acid-binding agent to the substance quantity of the compound (III) is as follows: (1:1) to (5: 1).
The reaction is carried out under a certain hydrogen pressure, usually expressed as hydrogenation pressure. The hydrogenation pressure refers to the sum of the partial pressures of various gases in the reaction kettle under certain hydrogenation conditions, such as a certain feeding ratio and reaction temperature, and includes the sum of the partial pressure of hydrogen, the partial pressure of raw material vapor, the partial pressure of solvent vapor and the like under the conditions. Under fixed conditions, the hydrogenation pressure can indirectly represent the partial pressure of hydrogen in the reaction vessel. The hydrogenation pressure has a significant influence on the hydrogenation reduction rate and the type of hydrogenation equipment. The hydrogenation pressure is low, the hydrogenation speed is slow, but the requirement on hydrogenation equipment is low; the hydrogenation pressure is high, the hydrogenation speed is high, but the requirements on hydrogenation equipment and safe operation are increased. The preferable hydrogenation pressure is (0.001 to 3.0) MPa.
The selection of the hydrogenation temperature is related to the hydrogenation system, such as the reaction solvent, the type and amount of the catalyst, the hydrogenation pressure and the like. The preferable range of the hydrogenation temperature is (0 to 100) DEG C.
Compared with the prior art, the invention has the beneficial effects that:
(1) a new route for synthesizing 2,2',3,3',5,5',6,6' -octafluorobiphenyl by taking 2,3,5, 6-tetrafluoro-1, 4-dihalobenzene as a raw material and carrying out Grignard reaction, copper catalyst/oxygen catalytic self-coupling reaction and catalytic hydrogenation dehalogenation reaction is developed.
(2) The Grignard reagent self-coupling reaction under a copper catalyst/oxygen composite catalytic system is developed, so that the recycling of the copper catalyst in the self-coupling reaction process is realized, the catalyst dosage is greatly reduced, the synthesis cost is reduced, and the reaction process is more environment-friendly.
(3) The catalytic hydrogenation dehalogenation method is adopted to replace a strong reducing agent for reduction dehalogenation, so that expensive and dangerous reducing agents such as lithium aluminum hydride and the like are avoided, the synthesis cost is reduced, the safety of the reaction process is improved, and the reaction process is really suitable for industrial production.
(4) The synthesis method has the advantages of cheap and easily-obtained raw materials, short reaction steps, high synthesis yield, good product quality and the like, and is suitable for industrial production and application.
The present invention will be further described with reference to the following embodiments. The following embodiments are only for the purpose of facilitating understanding of the present invention and do not limit the present invention. The present invention is not intended to be limited to the specific embodiments, and all the features mentioned in the description may be combined with each other to constitute a new embodiment as long as the features do not conflict with each other.
Detailed Description
Example one
Adding 2.6 g of fresh magnesium chips and 100 g of anhydrous 1, 4-dioxane into a 500 ml reaction bottle, stirring under the protection of nitrogen, heating to 70-75 ℃, dropwise adding a mixed solution of 21.9 g of 2,3,5, 6-tetrafluoro-1, 4-dichlorobenzene and 140 g of anhydrous 1, 4-dioxane, and stirring at 70-75 ℃ for reaction for 5 hours after dropwise adding to obtain a 2,3,5, 6-tetrafluoro-4-chlorophenyl magnesium chloride solution for later use.
And adding 0.7 g of cuprous sulfate and 110 g of anhydrous 1, 4-dioxane into a 500 ml reaction bottle, stirring, cooling to (0-5) DEG C, slowly blowing dry oxygen, dropwise adding the prepared 2,3,5, 6-tetrafluoro-4-chlorphenyl magnesium chloride solution, and stirring at (0-5) DEG C for reaction for 10 hours after dropwise adding. Diluting the reaction liquid into 100 g of water, stirring at room temperature, adjusting the pH value to 1-2 by using 30% sulfuric acid, removing 1, 4-dioxane by reduced pressure distillation, extracting a water phase twice by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, concentrating to remove a solvent, decoloring the residue by using activated carbon, and recrystallizing to obtain 33.1 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dichlorobiphenyl, wherein the yield is 90.2%, and the purity is 99.4%.
Adding 33.1 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dichlorobiphenyl, 200 g of methanol, 6 g of magnesium hydroxide and 1.66 g of 8% wet palladium carbon into a 500 ml high-pressure reaction kettle, sealing the high-pressure kettle, replacing gas with nitrogen for 3 times, replacing gas with hydrogen for 5 times, controlling the pressure (0.8-0.9) MPa in the kettle by using hydrogen, and stirring and hydrogenating at the temperature of (40-45) ℃ for 10 hours. Cooling the reaction system to room temperature, removing the pressure in the kettle, filtering the reaction solution, removing methanol from the filtrate under reduced pressure, washing and drying the concentrate to obtain 26.62 g of white solid, namely 2,2',3,3',5,5',6,6' -octafluorobiphenyl, wherein the yield is 99.0 percent and the purity is 99.3 percent.
Example two
Adding 2.91 g of fresh magnesium powder and 160 g of anhydrous ether into a 500 ml reaction bottle, stirring under the protection of nitrogen, cooling to (-5-0) DEG C, adding 0.5 ml of 2.0M isopropyl magnesium chloride solution through an injector, stirring for 10 minutes, dropwise adding a mixed solution of 30.79 g of 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene and 120 g of anhydrous ether, and stirring and reacting at (-5-0) DEG C for 10 hours after dropwise adding to obtain a 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution for later use.
And adding 1.98 g of cuprous chloride and 170 g of anhydrous ether into another 1L reaction bottle, starting stirring, cooling to (-50-55) DEG C, slowly blowing dry air, dropwise adding the prepared 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring at (-50-55) DEG C for reacting for 6 hours after the dropwise adding is finished. Diluting the reaction liquid into 100 g of water, stirring at room temperature, adjusting the pH value to 1-2 by using concentrated hydrochloric acid, standing to separate out an organic phase, drying by using anhydrous sodium sulfate, concentrating to remove a solvent, decoloring the residue by using activated carbon, and recrystallizing to obtain 20.93 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl, wherein the yield is 91.8%, and the purity is 99.3%.
Adding 20.93 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl, 210 g of ethanol, 130 g of water, 2.22 g of powdery magnesium oxide and 2.1 g of Raney nickel into a 500 ml high-pressure reaction kettle, sealing the high-pressure kettle, replacing gas with nitrogen for 3 times, replacing gas with hydrogen for 5 times, controlling the pressure (2.5-2.7) MPa in the kettle by hydrogen, and stirring and hydrogenating at the temperature of (50-55) ℃ for 10 hours. Cooling the reaction system to room temperature, removing the pressure in the kettle, filtering the reaction solution, removing ethanol from the filtrate under reduced pressure, filtering, washing and drying the concentrate to obtain 13.52 g of white solid, namely 2,2',3,3',5,5',6,6' -octafluorobiphenyl, wherein the yield is 98.8 percent and the purity is 99.2 percent.
EXAMPLE III
Adding 3.76 g of fresh and cut magnesium tape and 140 g of anhydrous 2-methyltetrahydrofuran into a 500 ml reaction bottle, stirring under the protection of nitrogen, heating to 50-55 ℃, slowly dropwise adding a mixed solution of 46.2 g of 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene and 180 g of anhydrous 2-methyltetrahydrofuran, stirring at 50-55 ℃ for reacting for 3 hours after dropwise adding is finished, obtaining a 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and cooling for later use.
And adding 0.11 g of cuprous bromide and 150 g of anhydrous 2-methyltetrahydrofuran into another 1-liter reaction bottle, providing an oxygen atmosphere for the reaction system by using a balloon, starting stirring, heating to the temperature of (30-35) DEG C, slowly dropwise adding the prepared 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and after dropwise adding, stirring at the temperature of (30-35) DEG C for reacting for 2 hours. Diluting the reaction liquid into 150 g of water, stirring at room temperature, adjusting the pH value to 1-2 by using 10% sulfuric acid solution, standing for layering, separating an upper organic phase, drying by using anhydrous sodium sulfate, concentrating to remove the solvent, decoloring the residue by using activated carbon, and recrystallizing to obtain 30.99 of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl, wherein the yield is 90.6%, and the purity is 99.5%.
Adding 30.99 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl, 310 g of isopropanol, 16 g of powdery potassium carbonate and 0.15 g of 10% dry palladium carbon into a 500 ml high-pressure reaction kettle, sealing the high-pressure kettle, replacing gas with nitrogen for 3 times, replacing gas with hydrogen for 5 times, controlling the internal pressure (0.02-0.03) MPa of the kettle with hydrogen, and stirring and hydrogenating at the temperature of (50-55) ℃ for 12 hours. Cooling the reaction system to room temperature, removing the pressure in the kettle, filtering the reaction solution, removing the solvent from the filtrate under reduced pressure, washing and drying the concentrate to obtain 20.1 g of white solid, namely 2,2',3,3',5,5',6,6' -octafluorobiphenyl, wherein the yield is 99.2 percent and the purity is 99.5 percent.
Example four
Adding 5.35 g of fresh magnesium chips and 60 g of anhydrous tetrahydrofuran into a 250 ml reaction bottle, stirring at room temperature under the protection of nitrogen, adding 0.2 g of dibromoethane into the reaction bottle by using a syringe, stirring for 15 minutes, slowly dropwise adding a mixed solution of 61.57 g of 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene and 60 g of anhydrous tetrahydrofuran, and after dropwise adding, stirring at room temperature for reacting for 6 hours to obtain a 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution for later use.
And adding 0.40 g of cuprous chloride and 40 g of anhydrous tetrahydrofuran into another 500 ml reaction bottle, starting stirring, providing a mixed atmosphere of 1:1 of oxygen and helium to the reaction system by using a balloon, controlling the temperature of the system to be 10-15 ℃, dropwise adding the prepared 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring and reacting at 10-15 ℃ for 3 hours after the dropwise adding is finished. Diluting the reaction liquid into 150 g of 2% hydrochloric acid solution, extracting twice by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, concentrating to remove the solvent, decoloring the residue by using activated carbon, and recrystallizing to obtain 42.17 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl, wherein the yield is 92.5%, and the purity is 99.1%.
Adding 42.17 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl, 126 g of isopropyl acetate, 37.44 g of triethylamine and 2.95 g of 5% wet palladium carbon into a 500 ml high-pressure reaction kettle, sealing the high-pressure kettle, replacing gas with nitrogen for 3 times, replacing gas with hydrogen for 5 times, controlling the pressure (0.5-0.6) MPa in the kettle by using hydrogen, and stirring and hydrogenating at the temperature of (10-15) ℃ for 8 hours. The pressure in the kettle is removed, the reaction liquid is filtered, the filtrate is decompressed to remove the solvent, and 27.41 g of white solid, namely the 2,2',3,3',5,5',6,6' -octafluorobiphenyl is obtained after the concentrate is washed and dried, the yield is 99.4 percent, and the purity is 99.6 percent.
EXAMPLE five
Adding 4.15 g of fresh and cut magnesium tape, 50 g of anhydrous 1, 4-dioxane, 0.1 g of iodine and nitrogen protection into a 250 ml reaction bottle, starting stirring, heating to (30-35) DEG C, slowly dropwise adding a mixed solution of 50 g of 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene and 100 g of anhydrous 1, 4-dioxane, and stirring and reacting at (30-35) DEG C for 5 hours after dropwise adding is finished to obtain a 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution for later use.
And adding 1.55 g of cuprous iodide and 110 g of anhydrous 1, 4-dioxane into a 500 ml reaction bottle, stirring, heating to 50-55 ℃, blowing a mixed gas of oxygen and argon in a ratio of 1:9, dropwise adding the prepared 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring at 50-55 ℃ for reaction for 1 hour after dropwise adding. Diluting the reaction liquid into 150 g of 5% sulfuric acid solution, extracting twice with ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, concentrating to remove the solvent, decoloring the residue by active carbon, and recrystallizing to obtain 33.43 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl with the yield of 90.3% and the purity of 99.4%.
Adding 33.43 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromo biphenyl, 234 g of 2-methyl tetrahydrofuran, 167 g of water, 6.45 g of sodium hydroxide and 5 g of Raney cobalt into a 500 ml high-pressure reaction kettle, sealing the high-pressure reaction kettle, replacing gas with nitrogen for 3 times, replacing gas with hydrogen for 5 times, controlling the pressure (2.0-2.1) MPa in the kettle by using hydrogen, and stirring and hydrogenating at the temperature of (60-65) ℃ for 10 hours. Cooling the reaction system to room temperature, removing the pressure in the kettle, filtering the reaction liquid, standing the filtrate to separate an organic phase, extracting a water phase by using 50 g of 2-methyltetrahydrofuran, combining the organic phases, removing the solvent under reduced pressure, washing and drying the concentrate to obtain 21.62 g of white solid, namely the 2,2',3,3',5,5',6,6' -octafluorobiphenyl, wherein the yield is 98.9 percent, and the purity is 99.3 percent.
EXAMPLE six
Adding 5.91 g of fresh magnesium powder and 210 g of anhydrous ethylene glycol dimethyl ether into a 1-liter reaction bottle, stirring under the protection of nitrogen, heating to 40-45 ℃, slowly dropwise adding a mixed solution of 70 g of 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene and 140 g of anhydrous ethylene glycol dimethyl ether, stirring and reacting at 40-45 ℃ for 4 hours after dropwise adding is finished, obtaining a 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and cooling for later use.
And adding 0.43 g of cuprous iodide and 100 g of anhydrous glycol dimethyl ether into another 1L reaction bottle, starting stirring, cooling to the temperature of (-10 to-15) DEG C, blowing dry air, dropwise adding the prepared 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring at the temperature of (-10 to-15) DEG C for reaction for 4 hours after the dropwise addition is finished. Diluting the reaction liquid into 250 g of water, adjusting the pH value to acidity by using a 20% sulfuric acid solution, extracting twice by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, concentrating to remove the solvent, decoloring the residue by using activated carbon, and recrystallizing to obtain 47.43 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl, wherein the yield is 91.5%, and the purity is 99.2%.
Adding 47.43 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl, 380 g of ethylene glycol monomethyl ether, 22.5 g of potassium phosphate and 1% of dry palladium carbon into a 1-liter high-pressure reaction kettle, sealing the high-pressure kettle, replacing gas with nitrogen for 3 times, replacing gas with hydrogen for 5 times, controlling the internal pressure (0.1-0.2) MPa of the kettle by using hydrogen, and stirring and hydrogenating at the temperature of (20-25) ℃ for 6 hours. The pressure in the kettle is removed, the reaction liquid is filtered, the filtrate is decompressed to remove the solvent, and the concentrate is washed and dried to obtain 30.8 g of white solid, namely the 2,2',3,3',5,5',6,6' -octafluorobiphenyl, wherein the yield is 99.3 percent, and the purity is 99.5 percent.
EXAMPLE seven
Adding 7.26 g of fresh magnesium chips and 160 g of anhydrous dimethoxymethane into a 500 ml reaction bottle, stirring under the protection of nitrogen, cooling to (5-10) ° C, adding 0.5 ml of newly prepared 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution by using an injector, stirring for 10 minutes, slowly dropwise adding a mixed solution of 80 g of 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene and 160 g of anhydrous dimethoxymethane, and stirring and reacting at (5-10) ° C for 8 hours after dropwise adding is finished to obtain a 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution for later use.
And adding 3.73 g of cuprous bromide and 300 g of anhydrous dimethoxymethane into another 1L reaction bottle, providing a dry air atmosphere for a reaction system by using a balloon, starting stirring, cooling to (-30 to-35) DEG C, dropwise adding the prepared 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring and reacting for 5 hours at (-30 to-35) DEG C after the dropwise adding is finished. Diluting the reaction liquid into 300 g of water, stirring at room temperature, adjusting the pH value to acidity by using a 10% hydrochloric acid solution, extracting twice by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, concentrating to remove the solvent, decoloring the residue by using activated carbon, and recrystallizing to obtain 54.08 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl, wherein the yield is 91.3%, and the purity is 99.3%.
Adding 54.08 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl, 325 g of tetrahydrofuran, 28 g of pyridine and 1.1 g of 5% dry palladium carbon into a 1-liter high-pressure reaction kettle, sealing the high-pressure kettle, replacing gas with nitrogen for 3 times, replacing gas with hydrogen for 5 times, controlling the pressure (1.5-1.6) MPa in the kettle by using hydrogen, and stirring and hydrogenating at the temperature of (40-45) ℃ for 7 hours. Cooling the reaction system to room temperature, removing the pressure in the kettle, filtering the reaction solution, removing the solvent from the filtrate under reduced pressure, washing and drying the concentrate to obtain 35.0 g of white solid, namely 2,2',3,3',5,5',6,6' -octafluorobiphenyl, wherein the yield is 99.0 percent and the purity is 99.3 percent.
Example eight
Adding 8.55 g of fresh magnesium powder, 250 g of anhydrous tetrahydrofuran and nitrogen protection into a 1L reaction bottle, stirring at room temperature, slowly dropwise adding a mixed solution of 100 g of 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene and 350 g of anhydrous tetrahydrofuran, and after dropwise adding, stirring at room temperature for reaction for 7 hours to obtain a 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution for later use.
And adding 0.1 g of cuprous iodide and 40 g of anhydrous tetrahydrofuran into another 1-liter reaction bottle, providing a mixed atmosphere of 1:1 of oxygen and helium to the reaction system by using a balloon, starting stirring, cooling to (0-5) DEG C, dropwise adding the prepared 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring at (0-5) DEG C for reaction for 3 hours after dropwise adding. Diluting the reaction liquid into 150 g of 2% hydrochloric acid solution, extracting twice by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, concentrating to remove the solvent, decoloring the residue by using activated carbon, and recrystallizing to obtain 68.49 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl, wherein the yield is 92.5%, and the purity is 99.1%.
Adding 68.49 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl, 345 g of dimethyl carbonate, 12.5 g of calcium hydroxide and 0.7 g of 5% dry palladium carbon into a 1-liter high-pressure reaction kettle, sealing the high-pressure kettle, replacing gas with nitrogen for 3 times, replacing gas with hydrogen for 5 times, controlling the pressure (1.0-1.1) MPa in the kettle by using hydrogen, and stirring and hydrogenating at the temperature of (80-85) ℃ for 5 hours. Cooling the reaction system to room temperature, removing the pressure in the kettle, filtering the reaction solution, removing the solvent from the filtrate under reduced pressure, washing and drying the concentrate to obtain 44.38 g of white solid, namely 2,2',3,3',5,5',6,6' -octafluorobiphenyl, wherein the yield is 99.1 percent and the purity is 99.4 percent.
Example nine
Adding 1.23 g of fresh magnesium powder and 20 g of anhydrous cyclohexylmethyl ether into a 250 ml reaction bottle, stirring at room temperature under the protection of nitrogen, slowly dropwise adding a mixed solution of 20 g of 2,3,5, 6-tetrafluoro-1, 4-diiodobenzene and 40 g of anhydrous cyclohexylmethyl ether, and after dropwise adding, stirring at room temperature for reacting for 4 hours to obtain a 2,3,5, 6-tetrafluoro-4-iodophenyl magnesium iodide solution for later use.
And adding 4 g of copper iodide and 30 g of anhydrous cyclohexylmethyl ether into a 250 ml reaction bottle, providing a dry air atmosphere for a reaction system by using a balloon, starting stirring, cooling to (-20 to-25) ℃, dropwise adding the prepared 2,3,5, 6-tetrafluoro-4-iodophenyl magnesium iodide solution, and stirring at (-20 to-25) ℃ for reacting for 6 hours after the dropwise adding is finished. Diluting the reaction solution into 50 g of 10% phosphoric acid solution, stirring for 15 minutes, standing to separate out an organic phase, drying by anhydrous sodium sulfate, concentrating to remove the solvent, decoloring the residue by active carbon, and recrystallizing to obtain 12.59 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -diiodobiphenyl, wherein the yield is 92.0% and the purity is 99.5%.
Adding 12.59 g of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -diiodobiphenyl, 60 g of tert-butyl acetate, 6.1 g of diisopropylethylamine and 0.45 g of 2% dry palladium carbon into a 250 ml high-pressure reaction kettle, sealing the high-pressure reaction kettle, replacing gas with nitrogen for 3 times, replacing gas with hydrogen for 5 times, controlling the pressure (0.06-0.07) MPa in the kettle by using hydrogen, and stirring and hydrogenating for 7 hours at room temperature. The pressure in the kettle is removed, the reaction liquid is filtered, the filtrate is decompressed to remove the tert-butyl acetate, and the concentrate is washed and dried to obtain 6.76 g of white solid, namely the 2,2',3,3',5,5',6,6' -octafluorobiphenyl, with the yield of 99.0 percent and the purity of 99.2 percent.
Comparative example 1
Adding 1.74 g of fresh and cut magnesium tape, 40 g of anhydrous 2-methyltetrahydrofuran and 40 g of nitrogen into a 250 ml reaction bottle, stirring, heating to 40-45 ℃, slowly dropwise adding a mixed solution of 20 g of 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene and 60 g of anhydrous 2-methyltetrahydrofuran, stirring at 40-45 ℃ for reacting for 4 hours after dropwise adding is finished, obtaining a 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and cooling for later use. And adding 0.64 g of cuprous chloride, 50 g of anhydrous 2-methyltetrahydrofuran and argon into a 250 ml reaction bottle, stirring at room temperature, slowly dropwise adding the prepared 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring at room temperature for reacting for 3 hours after dropwise adding. A sample is taken and sent to HPLC (detection wavelength of 254nm), and the content of the product 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl is 15.4 percent (area normalization method).
Adding 1.74 g of fresh and cut magnesium tape, 40 g of anhydrous 2-methyltetrahydrofuran and 40 g of nitrogen into a 250 ml reaction bottle, stirring, heating to 40-45 ℃, slowly dropwise adding a mixed solution of 20 g of 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene and 60 g of anhydrous 2-methyltetrahydrofuran, stirring at 40-45 ℃ for reacting for 4 hours after dropwise adding is finished, obtaining a 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and cooling for later use. And adding 0.64 g of cuprous chloride and 50 g of anhydrous 2-methyltetrahydrofuran into another 250 ml reaction bottle, providing an oxygen atmosphere for the reaction system by using a balloon, stirring at room temperature, slowly dropwise adding the prepared 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring at room temperature for reaction for 3 hours after dropwise adding. A sample is taken and sent to HPLC (detection wavelength of 254nm), and the content of the product 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl is 95.1 percent (area normalization method). Diluting the reaction liquid into 80 g of water, stirring at room temperature, adjusting the pH value to acidity by using 10% hydrochloric acid solution, standing for layering, separating an upper organic phase, drying by using anhydrous sodium sulfate, concentrating to remove the solvent, decoloring the residue by using activated carbon, and recrystallizing to obtain 13.46 g of white solid, namely 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl, wherein the yield is 90.9%, and the purity is 99.2%.
Comparative example 2
Adding 1.74 g of fresh and cut magnesium tape, 40 g of anhydrous 2-methyltetrahydrofuran and 40 g of nitrogen into a 250 ml reaction bottle, stirring, heating to 40-45 ℃, slowly dropwise adding a mixed solution of 20 g of 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene and 60 g of anhydrous 2-methyltetrahydrofuran, stirring at 40-45 ℃ for reacting for 4 hours after dropwise adding is finished, obtaining a 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and cooling for later use. And adding 1.86 g of cuprous bromide and 50 g of anhydrous 2-methyltetrahydrofuran into a 250 ml reaction bottle, stirring at room temperature under the protection of nitrogen, slowly dropwise adding the prepared 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring at room temperature for reacting for 3 hours after dropwise adding. A sample is taken and sent to HPLC (detection wavelength of 254nm), and the content of the product 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl is 38.2 percent (area normalization method).
Adding 1.74 g of fresh and cut magnesium tape, 40 g of anhydrous 2-methyltetrahydrofuran and 40 g of nitrogen into a 250 ml reaction bottle, stirring, heating to 40-45 ℃, slowly dropwise adding a mixed solution of 20 g of 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene and 60 g of anhydrous 2-methyltetrahydrofuran, stirring at 40-45 ℃ for reacting for 4 hours after dropwise adding is finished, obtaining a 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and cooling for later use. And adding 1.86 g of cuprous bromide and 50 g of anhydrous 2-methyltetrahydrofuran into another 250 ml reaction bottle, providing an oxygen atmosphere for the reaction system by using a balloon, stirring at room temperature, slowly dropwise adding the prepared 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring at room temperature for reacting for 3 hours after dropwise adding. A sample is taken and sent to HPLC (detection wavelength of 254nm), and the content of the product 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl is 95.8 percent (area normalization method). Diluting the reaction liquid into 80 g of water, stirring at room temperature, adjusting the pH value to acidity by using a 10% hydrochloric acid solution, standing for layering, separating an upper organic phase, drying by using anhydrous sodium sulfate, concentrating to remove the solvent, decoloring the residue by using activated carbon, and recrystallizing to obtain 13.54 g of white solid, namely 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl, wherein the yield is 91.4%, and the purity is 99.4%.
Comparative example three
Adding 1.74 g of fresh and cut magnesium tape, 40 g of anhydrous 2-methyltetrahydrofuran and 40 g of nitrogen into a 250 ml reaction bottle, stirring, heating to 40-45 ℃, slowly dropwise adding a mixed solution of 20 g of 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene and 60 g of anhydrous 2-methyltetrahydrofuran, stirring at 40-45 ℃ for reacting for 4 hours after dropwise adding is finished, obtaining a 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and cooling for later use. And adding 0.62 g of cuprous iodide and 50 g of anhydrous 2-methyltetrahydrofuran into a 250 ml reaction bottle, stirring at room temperature under the protection of nitrogen, slowly dropwise adding the prepared 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring at room temperature for reacting for 3 hours after dropwise adding. A sample is taken and sent to HPLC (detection wavelength of 254nm), and the content of the product 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl is 8.8 percent (area normalization method).
Adding 1.74 g of fresh and cut magnesium tape, 40 g of anhydrous 2-methyltetrahydrofuran and 40 g of nitrogen into a 250 ml reaction bottle, stirring, heating to 40-45 ℃, slowly dropwise adding a mixed solution of 20 g of 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene and 60 g of anhydrous 2-methyltetrahydrofuran, stirring at 40-45 ℃ for reacting for 4 hours after dropwise adding is finished, obtaining a 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and cooling for later use. And adding 0.62 g of cuprous iodide and 50 g of anhydrous 2-methyltetrahydrofuran into another 250 ml reaction bottle, providing an oxygen atmosphere for the reaction system by using a balloon, stirring at room temperature, slowly dropwise adding the prepared 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring at room temperature for reaction for 3 hours after dropwise adding. A sample is taken and sent to HPLC (detection wavelength of 254nm), and the content of the product 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl is 94.8 percent (area normalization method). Diluting the reaction liquid into 80 g of water, stirring at room temperature, adjusting the pH value to acidity by using a 10% hydrochloric acid solution, standing for layering, separating an upper organic phase, drying by using anhydrous sodium sulfate, concentrating to remove the solvent, decoloring the residue by using activated carbon, and recrystallizing to obtain 13.43 g of white solid, namely 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dibromobiphenyl, wherein the yield is 90.7%, and the purity is 99.3%.
Claims (15)
1. A synthetic method of 2,2',3,3',5,5',6,6' -octafluorobiphenyl is characterized by comprising the following steps:
(1) reacting 2,3,5, 6-tetrafluoro-1, 4-dihalobenzene with metal magnesium in an inert solvent to obtain 2,3,5, 6-tetrafluoro-4-halophenyl magnesium halide;
(2) 2,3,5, 6-tetrafluoro-4-halogenophenyl magnesium halide is subjected to self-coupling reaction in an inert solvent under the action of a copper catalyst and oxygen to obtain 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dihalobiphenyl, wherein the copper catalyst is an inorganic copper compound and is selected from one or more of the following compounds: copper chloride, cuprous chloride, copper bromide, cuprous bromide, copper iodide, cuprous iodide, copper sulfate, and cuprous sulfate;
(3) 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dihalobiphenyl is subjected to hydrogen hydrogenation reduction in a solvent under the action of a catalyst to obtain the 2,2',3,3',5,5',6,6' -octafluorobiphenyl, wherein the catalyst is selected from one or more of the following: palladium carbon, sponge nickel, sponge cobalt.
2. The method for synthesizing 2,2',3,3',5,5',6,6' -octafluorobiphenyl according to claim 1, wherein the method comprises the following steps: in the step (1), the raw material 2,3,5, 6-tetrafluoro-1, 4-dihalobenzene is selected from one or more of the following: 2,3,5, 6-tetrafluoro-1, 4-dichlorobenzene, 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene, 2,3,5, 6-tetrafluoro-1, 4-diiodobenzene.
3. The method for synthesizing 2,2',3,3',5,5',6,6' -octafluorobiphenyl according to claim 1, wherein the method comprises the following steps: in the step (1), the inert solvent is an ether solvent and is represented by the following general formula: and R-O-R ', wherein R, R' is C1-C10 linear chain, branched chain or cyclic alkyl, C1-C10 linear chain, branched chain or cyclic alkoxy alkyl, and the using amount of the solvent is 1-15 times of the mass of 2,3,5, 6-tetrafluoro-1, 4-dihalobenzene.
4. A method of synthesizing 2,2',3,3',5,5',6,6' -octafluorobiphenyl according to claim 1 or claim 3, wherein: in the step (1), the inert solvent is selected from one or more of the following: diethyl ether, methyl propyl ether, ethyl propyl ether, methyl isopropyl ether, ethyl isopropyl ether, methyl n-butyl ether, ethyl n-butyl ether, methyl isobutyl ether, ethyl isobutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dimethoxymethane, diethoxymethane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, 1-dimethoxypropane, 1-diethoxypropane, 2-dimethoxypropane, 2-diethoxypropane, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, cyclopentyl methyl ether, cyclohexyl methyl ether.
5. The method for synthesizing 2,2',3,3',5,5',6,6' -octafluorobiphenyl according to claim 1, wherein the method comprises the following steps: in the step (1), the mass ratio of the metal magnesium to the 2,3,5, 6-tetrafluoro-1, 4-dihalobenzene is (1-1.2): 1.
6. The method for synthesizing 2,2',3,3',5,5',6,6' -octafluorobiphenyl according to claim 1, wherein the method comprises the following steps: in the step (1), the reaction temperature is-20 to 80 ℃.
7. The method for synthesizing 2,2',3,3',5,5',6,6' -octafluorobiphenyl according to claim 1, wherein the method comprises the following steps: in the step (2), the inert solvent is an ether solvent and is represented by the following general formula: R-O-R ', wherein R, R' is C1-C10 linear chain, branched chain or cyclic alkyl, C1-C10 linear chain, branched chain or cyclic alkoxy alkyl, and the using amount of the solvent is 1-20 times of the mass of the 2,3,5, 6-tetrafluoro-4-halophenyl magnesium halide.
8. The method for synthesizing 2,2',3,3',5,5',6,6' -octafluorobiphenyl according to claim 1 or claim 7, wherein: in the step (2), the inert solvent is selected from one or more of the following: diethyl ether, methyl propyl ether, ethyl propyl ether, methyl isopropyl ether, ethyl isopropyl ether, methyl n-butyl ether, ethyl n-butyl ether, methyl isobutyl ether, ethyl isobutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dimethoxymethane, diethoxymethane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, 1-dimethoxypropane, 1-diethoxypropane, 2-dimethoxypropane, 2-diethoxypropane, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, cyclopentyl methyl ether, cyclohexyl methyl ether.
9. The method for synthesizing 2,2',3,3',5,5',6,6' -octafluorobiphenyl according to claim 1, wherein the method comprises the following steps: in the step (2), the mass ratio of the copper catalyst to the 2,3,5, 6-tetrafluoro-4-halophenyl magnesium halide is 0.0001-0.5: 1.
10. The method for synthesizing 2,2',3,3',5,5',6,6' -octafluorobiphenyl according to claim 1, wherein the method comprises the following steps: in the step (2), the oxygen is pure oxygen, air or a mixed gas composed of oxygen and inert gas, and the inert gas is selected from one or more of the following gases: nitrogen, helium, neon, argon, krypton.
11. The method for synthesizing 2,2',3,3',5,5',6,6' -octafluorobiphenyl according to claim 1, wherein the method comprises the following steps: in the step (2), the reaction temperature is-70-80 ℃.
12. The method for synthesizing 2,2',3,3',5,5',6,6' -octafluorobiphenyl according to claim 1, wherein the method comprises the following steps: in the step (3), the solvent is selected from one or more of the following solvents: the solvent amount is 1-20 times of the mass of 2,2',3,3',5,5',6,6' -octafluoro-4, 4' -dihalobiphenyl.
13. The method for synthesizing 2,2',3,3',5,5',6,6' -octafluorobiphenyl according to claim 1 or claim 12, wherein: in the step (3), the alcohol solvent is a monohydric alcohol solvent or a polyhydric alcohol solvent, and is represented by the following general formula: r (OH)nWherein R is C1-C10 linear chain, branched chain or cyclic alkyl, C1-C10 linear chain, branched chain or cyclic alkoxy alkyl, and n = 1-3; the selected ester solvent is represented by the following general formula: R-CO2-R ', wherein R is a linear, branched or cyclic alkyl group from C1 to C10, a linear, branched or cyclic alkoxy group from C1 to C10, a linear, branched or cyclic alkoxyalkyl group from C1 to C10, R' is a linear, branched or cyclic alkyl group from C1 to C10, a linear or branched alkoxyalkyl group from C1 to C10; the ether solvent is represented by the following general formula: R-O-R ', wherein R and R' are C1-C10 linear, branched or cyclic alkyl, and C1-C10 linear, branched or cyclic alkoxyalkyl.
14. The method for synthesizing 2,2',3,3',5,5',6,6' -octafluorobiphenyl according to claim 1, wherein the method comprises the following steps: in the step (3), the hydrogenation pressure is 0.001-3.0 MPa.
15. The method for synthesizing 2,2',3,3',5,5',6,6' -octafluorobiphenyl according to claim 1, wherein the method comprises the following steps: in the step (3), the reaction temperature is 0-100 ℃.
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