CN113087592B - Synthetic method of 4,4' -dibromo octafluoro biphenyl - Google Patents
Synthetic method of 4,4' -dibromo octafluoro biphenyl Download PDFInfo
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Abstract
The invention discloses a synthesis method of 4,4' -dibromo octafluoro biphenyl, belonging to the technical field of chemical synthesis. 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene reacts with metal magnesium in an inert solvent to obtain 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide, and then the self-coupling reaction is carried out in the inert solvent under the action of a copper catalyst and oxygen to obtain the 4,4' -dibromo 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 synthesis method of 4,4' -octafluoro dibromo biphenyl.
Background
The 4,4' -dibromo 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 4,4 '-dibromo octafluoro biphenyl is rarely reported, and a compound with a similar structure, such as 2, 2' -dibromo octafluoro biphenyl, can be referred to, and the synthesis method is as follows:
the synthesis method has harsh reaction conditions, needs n-butyllithium which is expensive and has higher safety risk as a reaction reagent besides the reaction at the low temperature of minus 78 ℃, also needs titanium tetrachloride with more than molar equivalent as a coupling reagent, has higher synthesis cost, and is not suitable for industrial production.
Disclosure of Invention
The invention aims to provide a simple, convenient and efficient synthesis method of 4,4' -dibromo 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 method for synthesizing 4,4' -dibromo octafluorobiphenyl comprises the following steps:
(1) reacting 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene (I) with metal magnesium in an inert solvent to obtain 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide (II);
(2) and carrying out self-coupling reaction on the obtained 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide (II) in an inert solvent under the action of a copper catalyst and oxygen to obtain the 4,4' -dibromo octafluorobiphenyl (III).
The technical route adopted by the invention can be shown as the following reaction formula:
the invention further provides that:
in the step (1):
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 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, fresh in surface and free of oxides, and is processed into a form with a high specific surface area, such as magnesium chips, magnesium powder, magnesium strips and the like, so as to ensure good reactivity. The mass ratio of the metal magnesium to the compound (I) is (1-1.5): 1, and the preferred mass ratio of the metal magnesium to 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 favorable for 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, and the product content and the reaction yield are reduced. The optional reaction temperature is-30 to 100 ℃, and the preferred reaction temperature is-20 to 80 ℃.
The reaction of the step is a reaction for preparing the aryl Grignard reagent by reacting the aryl bromide with the metal magnesium, and is required to be carried out under anhydrous conditions, so that the moisture content of raw materials, solvents and the like needs to be strictly controlled, and smooth initiation and normal running of the reaction are ensured. In addition, before the reaction starts, a proper amount of elemental iodine, 1, 2-dibromoethane and an alkyl Grignard reagent such as isopropyl magnesium chloride or an inert solvent solution of 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide prepared in advance can be added into the reaction system to serve 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 undergo side reactions 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 amount 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, cupric bromide, cuprous bromide, cupric iodide, cuprous iodide, cupric sulfate, cuprous sulfate, cupric oxide, cuprous oxide. The mass ratio of the copper catalyst to the compound (II) is (0.0001-0.5): 1, and the preferred mass ratio of the copper catalyst to the compound (II) is (0.0001-0.3): 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 the exclusion of oxygen, for example, under the protection of an inert gas such as nitrogen atmosphere or argon atmosphere, the amount of the copper catalyst is at least 0.5 equivalent or more based on the amount of the compound (II) substance, on the premise that the same reaction 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.
Compared with the prior art, the invention has the beneficial effects that:
(1) a new route for synthesizing 4,4' -dibromo octafluoro biphenyl by taking 2,3,5, 6-tetrafluoro-1, 4-dibromo-benzene as a raw material through a Grignard reaction and a copper catalyst/oxygen catalytic self-coupling 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 synthesis process is more environment-friendly.
(3) 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. It should be noted that the following embodiments are only for assisting 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 specification may be combined with each other to constitute a new embodiment as long as the features do not conflict with each other.
The specific implementation mode is as follows:
example one
Adding 2.88 g of fresh magnesium powder, 160 g of anhydrous ether and 160 g of nitrogen into a 500 ml reaction bottle, starting stirring, cooling to the temperature of (-5-0) DEG C by using a low-temperature bath, 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 the temperature of (-5-0) DEG C for 10 hours after dropwise adding is finished to obtain a 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution for later use.
And adding 1.98 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, stirring at (-50-55) DEG C for reacting for 6 hours after the dropwise adding is finished, and stopping the reaction. 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 for layering, separating out an upper 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 a white solid, namely the 4,4' -dibromo octafluorobiphenyl, wherein the yield is 91.8%, and the purity is 99.3%.
Example two
Adding 3.76 g of fresh and sheared magnesium tape, 140 g of anhydrous 2-methyltetrahydrofuran and 140 g of nitrogen into a 500 ml reaction bottle, starting stirring, 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 reaction 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 1L reaction bottle, providing an oxygen atmosphere for a reaction system by using a balloon, starting stirring, heating to (30-35) DEG C, slowly dropwise adding the prepared 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring at (30-35) DEG C for reacting for 2 hours after dropwise adding. 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 g of white solid, namely the 4,4' -dibromo octafluorobiphenyl, wherein the yield is 90.6%, and the purity is 99.5%.
EXAMPLE III
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 a 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 dropwise adding. Diluting the reaction liquid into 150 g of 2% hydrochloric 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, recrystallizing to obtain 42.17 g of white solid, namely the 4,4' -dibromo octafluorobiphenyl, wherein the yield is 92.5%, and the purity is 99.1%.
Example four
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 another 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, recrystallizing to obtain 33.43 g of white solid, namely the 4,4' -dibromo octafluorobiphenyl, wherein the yield is 90.3%, and the purity is 99.4%.
EXAMPLE five
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 (-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 (-10 to-15) DEG C for reaction for 4 hours after the dropwise adding is finished. Diluting the reaction liquid into 250 g of water, adjusting the pH value to acidity by using 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, recrystallizing to obtain 47.43 g of white solid, namely the 4,4' -dibromo octafluorobiphenyl, wherein the yield is 91.5%, and the purity is 99.2%.
EXAMPLE six
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 at (-30 to-35) DEG C for reaction for 5 hours after 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 white solid, namely the 4,4' -dibromo octafluorobiphenyl, wherein the yield is 91.3%, and the purity is 99.3%.
EXAMPLE seven
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 stirring at room temperature for reaction for 7 hours after dropwise adding is finished 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 1L reaction bottle, providing a mixed atmosphere of 1:1 of oxygen and helium gas for 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 12% hydrochloric 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 68.49 g of white solid, namely the 4,4' -dibromo octafluorobiphenyl, wherein the yield is 92.5%, and the purity is 99.1%.
Comparative example 1
Adding 1.74 g of fresh and sheared magnesium tape and 40 g of anhydrous 2-methyltetrahydrofuran into a 250 ml reaction bottle, stirring under nitrogen protection, 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. The sample is sent to HPLC for detection (the detection wavelength is 254nm), and the content of the product 4,4' -dibromo octafluoro biphenyl is 15.4% (area normalization method).
Adding 1.74 g of fresh and sheared magnesium tape and 40 g of anhydrous 2-methyltetrahydrofuran into a 250 ml reaction bottle, stirring under nitrogen protection, 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 is finished. A sample is taken and sent to HPLC (detection wavelength of 254nm), and the content of the product 4,4' -dibromo octafluoro biphenyl is 95.1 percent (area normalization method). Diluting the reaction solution 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 13.46 g of a white solid, namely the 4,4' -dibromo octafluorobiphenyl, wherein the yield is 90.9%, and the purity is 99.2%.
Comparative example 2
Adding 1.74 g of fresh and sheared magnesium tape and 40 g of anhydrous 2-methyltetrahydrofuran into a 250 ml reaction bottle, stirring under nitrogen protection, 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 4,4' -dibromo octafluoro biphenyl 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. The sample is sent to HPLC for detection (the detection wavelength is 254nm), and the content of the product 4,4' -dibromo octafluoro biphenyl is 95.8% (area normalization method). Diluting the reaction solution 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 a white solid, namely the 4,4' -dibromo octafluorobiphenyl, wherein the yield is 91.4%, and the purity is 99.4%.
Comparative example III
Adding 1.74 g of fresh and sheared magnesium tape and 40 g of anhydrous 2-methyltetrahydrofuran into a 250 ml reaction bottle, stirring under nitrogen protection, 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, 50 g of anhydrous 2-methyltetrahydrofuran and nitrogen 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 reaction for 3 hours after dropwise adding. The sample is sent to HPLC for detection (the detection wavelength is 254nm), and the content of the product 4,4' -dibromo octafluoro biphenyl is 8.8% (area normalization method).
Adding 1.74 g of fresh and sheared magnesium tape and 40 g of anhydrous 2-methyltetrahydrofuran into a 250 ml reaction bottle, stirring under nitrogen protection, 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 is finished. A sample is taken and sent to HPLC (detection wavelength of 254nm), and the content of the product 4,4' -dibromo octafluoro biphenyl is 94.8 percent (area normalization method). Diluting the reaction solution 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 a white solid, namely the 4,4' -dibromo octafluorobiphenyl, wherein the yield is 90.7%, and the purity is 99.3%.
Claims (7)
1. A method for synthesizing 4,4' -dibromo octafluoro biphenyl is characterized by comprising the following steps:
(1)2, 3,5, 6-tetrafluoro-1, 4-dibromobenzene and magnesium metal in an inert solvent at the temperature of-20 to 80 DEG C o Reacting under the condition of C to obtain 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide, wherein the mass ratio of the metal magnesium to the 2,3,5, 6-tetrafluoro-1, 4-dibromobenzene is 1-1.2: 1;
(2) 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide is added into an inert solvent under the action of a copper catalyst and oxygen at the temperature of-70 to 80 DEG C o C self-coupling reaction to obtain 4,4' -dibromo octafluorobiphenyl,
the copper catalyst is any one of cuprous chloride, cuprous bromide and cuprous iodide.
2. The synthesis method of 4,4' -dibromo octafluorobiphenyl according to claim 1, wherein the synthesis 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-dibromobenzene.
3. The method for synthesizing 4,4' -dibromooctafluorobiphenyl according to claim 1 or claim 2, 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.
4. The method for synthesizing 4,4' -dibromooctafluorobiphenyl 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: 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 1-20 times of the mass of 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide.
5. The method for synthesizing 4,4' -dibromooctafluorobiphenyl according to claim 1 or claim 4, wherein: in the step (2), the inert solvent is selected from one or more of the following solvents: 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.
6. The method for synthesizing 4,4' -dibromooctafluorobiphenyl according to claim 1 or claim 1, wherein: in the step (2), the mass ratio of the copper catalyst to the 2,3,5, 6-tetrafluoro-4-bromophenyl magnesium bromide is 0.0001-0.5: 1.
7. The synthesis method of 4,4' -dibromo octafluorobiphenyl according to claim 1, wherein the synthesis 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.
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