WO2008017197A1 - Procédé de préparation de p-bromofluorobenzène - Google Patents

Procédé de préparation de p-bromofluorobenzène Download PDF

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Publication number
WO2008017197A1
WO2008017197A1 PCT/CN2006/001858 CN2006001858W WO2008017197A1 WO 2008017197 A1 WO2008017197 A1 WO 2008017197A1 CN 2006001858 W CN2006001858 W CN 2006001858W WO 2008017197 A1 WO2008017197 A1 WO 2008017197A1
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reaction
bromofluorobenzene
liquid
added
bromination
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PCT/CN2006/001858
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English (en)
Chinese (zh)
Inventor
Keng Zong
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Keng Zong
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Priority to PCT/CN2006/001858 priority Critical patent/WO2008017197A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds

Definitions

  • This invention relates to a process for the preparation of a dibasic halogenated aromatic hydrocarbon in an organic compound. Background technique
  • Parabromofluorobenzene is an important intermediate for the synthesis of fine chemicals such as pharmaceuticals, pesticides and dyes, and is widely used in industrial production.
  • One method is to make fluorobenzene into p-nitrofluorobenzene after nitration reaction, and then to reduce p-nitrofluorobenzene to obtain p-fluoroaniline, p-fluoroaniline and sodium nitrite, and dilute sulfuric acid to obtain diazonium salt by low temperature, diazo
  • the salt is then reacted with cuprous bromide to produce p-bromofluorobenzene.
  • Another method is direct bromination of fluorobenzene, which uses liquid bromine to react directly with fluorobenzene to form p-bromofluorobenzene; since liquid bromine reacts with fluorobenzene, the reaction temperature is controlled from 30 ⁇ to 40 ° C, while fluorobenzene The boiling point is 84.
  • Dibromofluorobenzene because its boiling point differs greatly from the boiling point of p-bromofluorobenzene, it can be removed by distillation, but because of the addition of bromine to the material, some of the bromofluorobenzene reacts with bromine to form dibromofluoro Benzene, therefore, the yield of the method is only 75% to 80%, and the bromine consumption is large, and the production of 1 ton of p-bromofluorobenzene requires 1.2 to 1.4 tons of bromine, which is costly.
  • JP 62 221 640 and JP 62 93224 that a mixture of fluorobenzene, hydrogen bromide, oxygen and nitrogen is heated to a temperature of from 190 ° C to 200 ° C in the presence of a Cu-Y type zeolite, and the reaction is continued for 2 hours to 3 hours.
  • a method for producing p-bromofluorobenzene yielded p-bromofluorobenzene having a conversion ratio of 50% and a purity of 93 to 98%.
  • JP 63 14,742 discloses a process for producing p-bromofluorobenzene by reacting fluorobenzene with liquid bromine (molar ratio of about 1: 1.27) using iron powder as a catalyst at 5 ° C to 4 CTC.
  • the product is a mixture of 1% o-bromofluorobenzene, 0.5% m-bromofluorobenzene and 98.5% p-bromofluorobenzene, and then the isomer is separated by crystallization to obtain a purity of 99.8% of p-bromofluorobenzene; this method of making p-bromofluorobenzene has the disadvantage of being cumbersome and energy intensive.
  • No. 5,874,241 discloses a process for preparing high purity and high yield of p-bromofluorobenzene by reacting liquid bromine with fluorobenzene at minus 3 CTC to 0 °C.
  • the patented method uses a low temperature reaction method to inhibit the production of o-bromofluorobenzene, and then uses an excessive bromination method to convert o-bromofluorobenzene into a dibromide, thereby achieving the purpose of separating o-bromofluorobenzene.
  • This kind The shortcoming of the method is to maintain a very low temperature, low temperature cryogenic equipment, and high energy consumption.
  • the technical scheme for achieving the object of the present invention is: generating bromine fluorobenzene and hydrogen bromide by the bromination reaction of liquid fluorobenzene and elemental bromine as a reactant under the action of a catalyst; wherein: chlorine gas is introduced into the reaction system, The chlorine gas reacts with hydrogen bromide to form an oxidation product of hydrogen chloride and hydrogen bromide. The oxidation product of hydrogen bromide continues to bromine the fluorobenzene to form p-bromofluorobenzene, so that the bromination reaction is carried out. Chlorine gas participates in the bromination reaction; after the bromination reaction is completed, the obtained material is directly used as a finished product or the obtained material is post-treated to obtain a finished product.
  • the oxidation products formed by the oxidation reaction of chlorine gas with hydrogen bromide are elemental bromine and bromine bromide, while both elemental bromine and bromine bromide are used as brominating agents to react with fluorobenzene to form p-bromofluorobenzene.
  • the catalyst for the bromination reaction is a powdery inorganic catalyst containing iron.
  • the mass ratio of fluorobenzene to the catalyst is 500: 0.5 to 3; the reaction temperature of the bromination reaction is O'C to 40 Torr, and the bromination reaction The system is open to the atmosphere.
  • the liquid fluorobenzene and the catalyst are added to the reactor connected to the atmosphere, and the reactor is connected to the atmosphere under stirring.
  • Liquid bromine is added thereto, and chlorine gas is introduced into the liquid surface of the material until the bromination reaction is complete; the main products of the reaction are p-bromofluorobenzene and hydrogen chloride, and the by-products are o-bromofluorobenzene and p-chlorofluorobenzene.
  • the amount of chlorine in the bromination reaction is theoretically increased by adjusting the liquid bromine and chlorine gas in a molar ratio of 1. 03 ⁇ 1. 06:1; .
  • the theoretical ratio of the above chlorine gas, the theoretical amount of liquid bromine to the amount of fluorobenzene added is 1: 1:2.
  • the catalyst is selected as iron powder or powdered iron tribromide or powdered ferric chloride
  • the liquid fluorobenzene and the catalyst are added to the reactor connected to the atmosphere, and stirred into the reactor.
  • the initiation time of the bromination reaction is 5 to 15 minutes, and the amount of liquid bromine added is 3% to 6% of the theoretical amount, so that the liquid bromine is excessive in the entire bromination reaction;
  • the liquid bromine and chlorine gas are added to the material in a molar ratio of 1:1 by adjusting the rate of addition of liquid bromine and chlorine gas, and the amount of chlorine added is the theoretical amount, and the amount of liquid bromine added is also Theoretical dosage.
  • the reactor for the bromination reaction is a reactor equipped with a stirrer, a thermometer, a bromine tube, a vent tube and a reflux condenser, and the reactor is passed through a reflux condenser to the atmosphere; the reactant liquid bromine is reacted through the bromine tube. Included in the material, and the outlet of the bromine tube is located below the liquid level of the material or on the inner wall of the reactor above the liquid level of the material; chlorine gas is added to the reactor material through the vent tube, and the vent tube is The outlet is located below the level of the material.
  • the first post-treatment of the material after the bromination reaction is to wash the material with water, alkali, or alkali washing, and then the hydrogen chloride is removed by: firstly, the material after the bromination reaction is carried out. After washing with water, the organic phase obtained by liquid separation or liquid separation is the finished product, or the organic phase obtained by adding the aqueous solution of the inorganic alkali to the material after the bromination reaction for neutralization reaction, and then liquid separation and liquid separation is the finished product.
  • the aqueous solution of the inorganic base is added to the material after the bromination reaction to carry out the neutralization reaction, and then the liquid phase is separated, and the organic phase obtained by the liquid separation is washed with water, and then the liquid phase is separated again, and the organic phase obtained by the liquid separation again is For the finished product.
  • the second post-treatment of the brominated material is the sequential removal of hydrogen chloride and p-chlorofluorobenzene in the material, wherein the removal of hydrogen chloride in the material is by washing with water, causing alkali washing or washing with alkali.
  • the method comprises the following steps: firstly, the material after the bromide reaction is washed with water, then separated, and then the organic phase obtained by liquid separation is rectified, After the distillation, the finished product can be obtained, or the aqueous solution of the inorganic alkali is first added to the material after the bromination reaction to carry out the neutralization reaction, and then the liquid phase is separated, and then the organic phase obtained by the liquid separation is subjected to rectification and rectification.
  • the finished product can be obtained, or the aqueous solution of the inorganic base is added to the material after the bromination reaction to carry out the neutralization reaction, and then the liquid phase is separated, and the organic phase obtained by the liquid separation is washed with water, and then liquid separation is performed again, and the liquid separation is performed again.
  • the obtained organic phase is subjected to rectification and rectification to obtain a finished product.
  • the third post-treatment of the brominated material is to remove the o-bromofluorobenzene in the material by a sulfonation reaction by: controlling the temperature of the brominated material to 20 ⁇ to 100 ⁇ . Within the range, the sulfonating agent is added to the material under stirring, and stirring is continued for 2 to 5 hours to complete the sulfonation reaction, and the material obtained after the reaction is the finished product.
  • the sulfonation reaction in the present invention can effectively remove the o-bromofluorobenzene in the material after the bromination reaction, which is also an innovation of the present invention, although In the material after the sulfonation reaction, in addition to p-bromofluorobenzene, p-chlorofluorobenzene, hydrogen chloride, a new impurity, 3-bromo-4-fluorobenzenesulfonic acid, was introduced, but the relative bromide was removed from p-bromofluorobenzene.
  • 3-bromo-4_fluorobenzenesulfonic acid can be removed by alkali washing or water washing or alkali washing and water washing, and the operation process is simple, and the customer can purchase the material after the third post-treatment. Use it according to your own requirements or remove the relevant impurities before use.
  • the fourth post-treatment of the brominated material is the sequential removal of o-bromofluorobenzene and hydrogen chloride in the material, wherein the removal of o-bromofluorobenzene in the material is achieved by sulfonation reaction.
  • the removal of hydrogen chloride is achieved by washing with water, caustic washing, or washing with alkali and then washing with water.
  • the removal of p-chlorofluorobenzene in the material is passed through fine Distillation is achieved; the method is: firstly, the temperature of the material after the bromination reaction is controlled within a range of 2 CTC to 10 (TC), and a sulfonating agent is added to the material under stirring, and stirring is continued for 2 to 5 hours to effect a sulfonation reaction.
  • the organic phase obtained by completely and re-washing the material and then liquid separation and liquid separation is the finished product, or the temperature of the material after the bromination reaction is first controlled within a range of 20 ° (to 100 ° 0) under stirring.
  • the temperature of the material after the bromination reaction is controlled at 2 (TC to 10 (the range of TC, adding sulfonating agent to the material under stirring, stirring for 2 to 5 hours to complete the sulfonation reaction, and then the inorganic base)
  • the aqueous solution is added to the material to carry out the neutralization reaction, and then the liquid phase is separated, and the organic phase obtained by the liquid separation is washed with water and then separated again, and the organic phase obtained by the liquid separation is the finished product.
  • the fifth post-treatment of the brominated material is the sequential removal of o-bromofluorobenzene, hydrogen chloride and p-chlorofluorobenzene in the material, wherein the removal of o-bromofluorobenzene in the material is by sulfonation reaction.
  • the removal of hydrogen chloride in the material is achieved by washing with water, caustic washing, or washing with alkali and water, by: first controlling the temperature of the material after the bromination reaction within the range of 2 CTC to 100 Torr, The sulfonating agent is added to the material under stirring, stirring is continued, and the sulfonation reaction is completed for 2 to 5 hours, and then the material is washed with water, and then separated, and the organic phase obtained by liquid separation is subjected to rectification and rectification.
  • the finished product can be obtained, or the temperature of the brominated material can be controlled within 2 (TC to 100 ° C), the sulfonating agent is added to the material under stirring, and the sulfonation reaction is continued for 2 to 5 hours.
  • the aqueous solution of the inorganic base is added to the material for neutralization reaction, and then the liquid phase is separated, and the organic phase obtained by liquid separation is refined and rectified to obtain the finished product, or the bromination reaction is first carried out.
  • the sulfonating agent is added to the material under stirring, stirring is continued for 2 to 5 hours to complete the sulfonation reaction, and an aqueous solution of the inorganic alkali is added to the material for neutralization reaction.
  • the organic phase obtained by liquid separation is washed with water, and the liquid phase is separated again, and the organic phase obtained by liquid separation is refined and rectified to obtain a finished product.
  • a separate alkali is used. Washing and washing can theoretically remove the hydrogen chloride contained in the brominated material, but in industrial large production, the organic phase obtained after washing will have very little chlorinated gas dissolved, while hydrogen chloride is in rectification.
  • the above alkaline washing is directed to the aqueous solution of the alkali added to the bromination reaction, neutralizing the hydrogen chloride in the material, and separating the material after the neutralization reaction into the organic phase layer solution and the aqueous phase layer solution by standing.
  • a method of obtaining an organic phase layer solution by liquid separation; or an aqueous solution of a base added to the material after the sulfonation reaction, and the material The hydrogen chloride and 3-bromo-4-fluorobenzenesulfonic acid are neutralized, and the material after the neutralization reaction is separated into an organic phase layer solution and an aqueous phase layer solution by standing, and then the organic phase layer solution is obtained by liquid separation. method.
  • the above washing is directed to the material after the bromination reaction or the addition of water to the material after the sulfonation reaction, and the solubility of the inorganic substance such as hydrogen chloride in water is large, and the solubility of organic substances such as bromofluorobenzene in water is small, and The method of separating the mixture after the addition of water into an organic phase layer solution and an aqueous phase layer solution, and then obtaining a solution of the organic phase layer by liquid separation.
  • the neutralization solution used in the neutralization reaction carried out in the above-mentioned post-treatment is a 3% to 5% aqueous sodium carbonate solution or a 10% to 30% aqueous sodium hydroxide solution, and the neutralization reaction is carried out until the pH of the material in the reactor It is from 6 to 7.
  • the rectification carried out in the above post-treatment is atmospheric distillation or depressurization, and the number of theoretical plates is 10 to 30; when atmospheric distillation is used, the evaporator temperature is 160 ⁇ to 180 ⁇ , and the temperature at the top of the column is 13CTC to 156 ° C, the reflux ratio is (1-20): 1.
  • the sulfonating agent to be carried out in the above post-treatment is sulfur trioxide, chlorosulfonic acid or fuming sulfuric acid, and the temperature during the sulfonation reaction is controlled at 40 to 90 °C.
  • the reaction of liquid bromine with fluorobenzene is an organic reaction.
  • o-chlorofluorobenzene can be removed together with o-bromofluorobenzene; however, the formation and removal of such low-content dibromofluorobenzene, o-chlorofluorobenzene and the like do not affect the method and purpose of the present invention, so It will not be described in detail in this manual.
  • the sulfonation reaction is used to remove the o-bromofluorobenzene, and the specific method is sulfur trioxide, chlorosulfonic acid or fuming sulfuric acid as a sulfonating agent.
  • the specific method is sulfur trioxide, chlorosulfonic acid or fuming sulfuric acid as a sulfonating agent.
  • 3-bromo-4-fluorobenzenesulfonic acid which is easily reacted with a base with o-bromofluorobenzene can be separated by neutralization and liquid separation.
  • the sulfonating agent hardly reacts with p-bromofluorobenzene, but only with o-bromofluorobenzene, and the resulting 3-bromo-4-fluorobenzenesulfonic acid is easily Washed with an alkali solution; thereby reducing the content of o-bromofluorobenzene to below 0.02%, so that a relatively high purity p-bromofluorobenzene can be prepared by a simplified method.
  • chlorosulfonic acid as an example, the anti-banking is as follows (the equation is not balanced):
  • the weight content of o-bromofluorobenzene in the material to be sulfonated may be measured first.
  • the method of testing can be performed by gas chromatography, and then the theoretical amount of sulfonating agent is calculated.
  • the amount calculated by the above formula is the theoretical amount of the sulfonating agent. Since the sulfonating agent is easily hydrolyzed, in the actual production, the prepared bromide fluorobenzene containing o-bromofluorobenzene and p-chlorofluorobenzene always contains some water.
  • the actual amount of the sulfonating agent to be added is in excess of the theoretical amount, so the actual amount is from 1 to 4 times the theoretical amount, preferably 1.3 times the chamber.
  • the present invention has positive effects: (1) In the prior art, hydrogen bromide formed by the reaction of fluorobenzene with bromine cannot continue to participate in the reaction, and is volatile, thereby causing a large loss of bromine; and the method of the present invention is Chlorine gas is added, and the resulting bromide is oxidized to elemental bromine and bromine bromide. 2 Elemental bromine and chlorobromide can continue to react with fluorobenzene to form p-bromofluorobenzene.
  • the present invention can effectively inhibit the formation of by-product p-chlorofluorobenzene by slightly increasing the liquid bromine ratio in the reactor material by a theoretical excess of 1% to 6%, preferably 3% to 5%.
  • the content of p-chlorofluorobenzene is less than 1%.
  • the sulfonating agent hardly reacts with p-bromofluorobenzene, and 3-bromo-4-fluorobenzenesulfonic acid can be separated from the o-bromofluorobenzene to form an easy-to-base reaction, thereby achieving purification.
  • Purpose this can make the content of o-bromofluorobenzene from 2% to 3% It is reduced to 0.02% or less, and the method of preparing high-purity p-bromofluorobenzene can be simplified.
  • the boiling point of p-chlorofluorobenzene is 129.
  • p-bromofluorobenzene has a boiling point of 150 ° C, and the boiling points of the two are quite different, and can be separated by a rectification column having 10 to 30 theoretical plates; using the method of the invention and selecting appropriate post-treatment In the process, p-bromofluorobenzene having a purity of up to 99.9% or more can be obtained.
  • Figure 1 is a gas chromatogram of the finished product of p-bromofluorobenzene prepared in Example 9.
  • Figure 2 is a gas chromatogram of the finished product of p-bromofluorobenzene prepared in Example 21.
  • Figure 3 is a schematic view showing the structure of a batch distillation column.
  • Figure 4 is a gas chromatogram of the finished product of p-bromofluorobenzene prepared in Example 36.
  • Example 1 In a 1000 ml five-neck glass reaction flask with an electric stirrer, a thermometer, a balance funnel, a vent tube, and a reflux condenser, 500 g of liquid fluorobenzene was first added, and the balance funnel was The outlet of the vent pipe is located under the surface of the fluorobenzene; the reaction temperature is controlled by a cold water bath of 2 ⁇ 2 ° C; while stirring, 2 g of iron powder as a catalyst is added to the reaction flask, and the mixture is passed through a balance funnel to the reaction flask. Add 23 g of liquid bromine to start the reaction of the bromination reaction in the reaction flask.
  • the liquid bromine reacts with fluorobenzene to form hydrogen bromide and p-bromofluorobenzene.
  • the by-product is o-bromofluorobenzene.
  • the reaction is initiated for 15 minutes.
  • the bromination reaction in the reaction flask is started by introducing chlorine gas into the reaction system in the reaction flask through a vent pipe to become a bromination reaction in which the generated hydrogen bromide is oxidized by chlorine gas into a brominating agent (even if bromination reaction)
  • a bromination reaction with chlorine gas the same as below, add 417 g of liquid bromine to the reaction flask at a molar ratio of 1:1 for the next 8 hours, and pass 185 g of chlorine gas.
  • Example 1 The rest was the same as in Example 1, except that the iron powder as a catalyst added in the bromination reaction was 1 g, and the temperature of the bromination reaction was controlled at 15 ⁇ 2 °C. After the reaction, 868 g of a finished product was obtained, and the yield of fluorobenzene was 93%.
  • Table 1 The contents of the relevant ingredients are shown in Table 1.
  • Example 1 The rest is the same as in Example 1, except that the iron powder as a catalyst added in the bromination reaction is 0.5 g, and the reaction temperature of the bromination reaction is controlled at 25 ⁇ 2 858 after the reaction, 858 g of the finished product, The yield of fluorobenzene was 91.5%, and the contents of the relevant components are shown in Table 1.
  • Example 1 The rest was the same as in Example 1, except that the iron powder as a catalyst added in the bromination reaction was 2.5 g, and the reaction temperature of the bromination reaction was controlled at 38 ⁇ 2 °C. After the reaction, 840 g of a finished product was obtained, and the yield of fluorobenzene was 89%, and the contents of the relevant components are shown in Table 1.
  • the bromination reaction is a bromination reaction having a reaction initiation stage, and after the user purchases the finished products obtained in Examples 1 to 4, they can be directly used according to different use requirements or The impurities are removed before use.
  • Example '5 The rest was the same as in Example '5 except that the iron trichloride powder as a catalyst added in the bromination reaction was 1 g, and the temperature of the bromination reaction was controlled to 15 ⁇ 2 Torr. After the reaction, 858 g of the finished product was obtained, wherein the content by weight of the component was: 95. 0% of p-bromofluorobenzene, 2. 2% of o-bromofluorobenzene, and 0.8% of p-chlorofluorobenzene.
  • Example 5 The rest was the same as in Example 5, except that the ferric chloride powder as a catalyst was added in the bromination reaction to 0.5 g, and the temperature of the bromination reaction was controlled at 25 ⁇ 2 °C. After the reaction, 850 g of the finished product was obtained, wherein the content of the relevant components was: 96.80 % of p-bromofluorobenzene, 1.9% of o-bromofluorobenzene, and chlorofluorobenzene.
  • Example 5 The rest was the same as in Example 5 except that the ferric chloride powder as a catalyst added in the bromination reaction was 2.5 g, and the temperature of the bromination reaction was controlled at 38 ⁇ 2 °C. After the reaction, 848 g of the finished product was obtained, wherein the content of the relevant components was: 95.80 % of p-bromofluorobenzene, 2. 2% of o-bromofluorobenzene, and 0.9% of p-chlorofluorobenzene.
  • the bromination reaction is a bromination reaction without initiating a reaction stage, and after the user purchases the finished products obtained in Examples 5 to 8, it can be directly used or used according to different use requirements. The impurities are removed and used.
  • the process of the bromination reaction of this example is the same as that of Example 1. After repeating the bromination reaction of Example 1 two to three times, 1000 g of the obtained material is taken out, and the alkali treatment is followed by washing with water and then post-treatment with water washing.
  • the material is particularly s is transferred to a separatory funnel, first subjected to caustic, i.e., a suitable amount of addition of 5% aqueous sodium carbonate solution after shaking in a separatory funnel, so that the bromination reaction
  • caustic i.e., a suitable amount of addition of 5% aqueous sodium carbonate solution after shaking in a separatory funnel, so that the bromination reaction
  • the latter material is neutralized to a pH of 7 by an aqueous solution of sodium carbonate, and then allowed to stand for stratification, followed by liquid separation, and the organic phase of the lower layer is transferred to another separatory funnel; then the organic phase solution is washed with water.
  • the gas chromatogram shown in Fig. 1 was obtained by sampling and analyzing the finished product of p-bromofluorobenzene obtained in the present example, and the image data thereof is shown in Table 2.
  • the substance corresponding to each peak name in Table 2 can be obtained by infrared spectrum identification.
  • the gas chromatograph overlaps the data of the three characteristic peaks when printing the map.
  • the specific values of these three data are given in the table column with the peak numbers 4, 5 and 6 in Table 2, and their retention times are 3. 568, 3. 622 and 3. 672 minutes.
  • the instrumentation and analysis conditions used are as follows:
  • the instrument model is: GC9790 gas chromatograph manufactured by Zhejiang Wenling Fuli Analytical Instrument Co., Ltd.; the column type is SE54, diameter is 0.35 mm, length is 30 m. Chromatographic conditions: column temperature 130 ° C, vaporization chamber 250 ⁇ , detector 250 ° C.
  • the detector model is a hydrogen flame ionization detector FID; the injector is split; the column front pressure: 0. IMPa; injection volume: 0.2 microliter.
  • the procedure of the bromination reaction of this example was the same as in Example 2, and after repeating the bromination reaction of Example 2 two to three times, 1000 g of the obtained material was taken out, X!l" which was carried out in the same manner as in Example 9.
  • the post-treatment step is to remove the hydrogen chloride to obtain a purified product of p-bromofluorobenzene having a purity of 97.2%.
  • the procedure of the bromination reaction of this example was the same as that of Example 3. After repeating the bromination reaction of Example 3 two to three times, 1000 g of the obtained material was taken out, and the same procedure as in Example 9 was carried out.
  • the chlorofluorobenzene having a purity of 97.8% is obtained by a step of removing the hydrogen chloride.
  • the procedure of the bromination reaction of this example was the same as that of Example 4. After repeating the bromination reaction of Example 4 two to three times, 1000 g of the obtained material was taken out, and the same post treatment as in Example 9 was carried out. The step of removing the hydrogen chloride to obtain p-bromofluorobenzene having a purity of 97.5%. .
  • the procedure of the bromination reaction in this example was the same as in Example 1. After repeating the bromination reaction of Example 1 two to three times, 1000 g of the obtained material was taken out, and subjected to alkali washing for post-treatment to remove the bromination reaction. Hydrogen chloride, the specific method is: Move the material to the separatory funnel, add an appropriate amount of 5% aqueous sodium carbonate solution, and then oscillate to make bromine The material after the reaction is neutralized to a pH of 7 by an aqueous solution of sodium carbonate, and then left to stand for stratification, and the organic phase obtained after liquid separation is a pair containing p-chlorofluorobenzene and o-bromofluorobenzene. Finished product of bromofluorobenzene.
  • the process of the bromination reaction of this example is the same as that of Example 1. After repeating the bromination reaction of Example 1 two to three times, 1000 g of the obtained material is taken out, and subjected to post-treatment with water washing to remove the bromination reaction. Hydrogen chloride, the specific method is: the material is moved to the separatory funnel, 300 grams of water is added to the material, and then shaken, and then left to stand for stratification, liquid separation, the organic phase obtained after liquid separation is containing chlorofluoro Finished product of p-bromofluorobenzene of benzene and o-bromofluorobenzene.
  • the bromination reaction is a bromination reaction in the initiation reaction stage, and the bromination reaction is carried out after the removal of hydrogen chloride; the user purchases Examples 9 to 14. After the finished product is obtained, it can be used directly according to different use requirements or the relevant impurities can be removed before use.
  • the process for preparing p-bromofluorobenzene in this embodiment is a manufacturing process in industrial large-scale production, including a bromination reaction process and a first alkaline washing of the material after the bromination reaction, followed by water washing to remove hydrogen chloride and rectification to remove p-chlorofluorocarbon.
  • the post-treatment process of benzene is as follows: In 2Q00 liter reactor with electric stirrer, thermometer, bromine high level tank, chlorine tube, exhaust gas absorption tower, put 1500 kg of fluorobenzene, add 10 kg of trichloro Iron, 40 kg of bromine (ie, industrial liquid bromine, which contains 99.8% liquid bromine), and the reaction in the reactor begins the bromination reaction, control the reaction temperature is 10 ⁇ to 20 ° C, stirring 15 minutes; then, within 30 hours, according to the molar ratio of bromine: chlorine gas of 1:1, adding 1255 kg of bromine by adding bromine high-level tank, and introducing 555 kg of chlorine gas, so that the bromination reaction becomes Chlorine gas participates in the bromination reaction; after the chlorine gas and liquid bromine are completely added and the reaction is terminated, the material after the bromination reaction is obtained, and the reaction is kept stirring.
  • the material after the bromination reaction is then subjected to an alkali washing treatment, that is, the material after the bromination reaction is neutralized with a 5% aqueous sodium carbonate solution under stirring until the pH is 7.
  • the material is sent to the liquid-phase two-phase separation device, and after standing and layering, the organic phase solution is separated and sent to another liquid-phase two-phase separation device; then the separated organic phase solution is washed with water, that is, the separated organic
  • the phase solution was stirred with ice, and the organic phase solution was separated after standing to separate the layer, thereby obtaining the crude p-bromofluorobenzene, the weight of which was 2700 kg; at this time, the sample was subjected to gas chromatography analysis, and the content of p-bromofluorobenzene was measured.
  • the obtained crude p-bromofluorobenzene is subjected to rectification treatment: 1
  • the structure of the batch rectification column is shown in Fig. 3, and 2700 kg of crude product is added to the evaporator (also called reboiler) in the rectification column.
  • evaporator also called reboiler
  • p-Bromofluorobenzene 2 control evaporator temperature 160 ⁇ to 180 ⁇ , : top temperature 13CTC to 156 ° C; 3 refining process by controlling the reflux ratio and collecting the corresponding weight of the fraction to carry out the purification of p-bromofluorobenzene.
  • the reflux ratio was controlled to be 20:1, and the 100 kg fraction distilled was collected in a 1 # receiver, which was called No. 1 split; then the reflux ratio was controlled to 15: 1, and the distilled fraction was 160. Kilogram fraction collection In the 2# receiver, it is called the No. 2 fraction; finally, the reflux ratio is controlled to 1:10, and the remaining fractions from the rectification are collected in the 3# receiver, which is called the No. 3 fraction.
  • the No. 1 fraction, the No. 2 fraction and the No. 3 fraction were sampled and analyzed by gas chromatography, and the content of p-chlorofluorobenzene in the fraction No. 1 was about 10%, and the content of p-chlorofluorobenzene in the fraction No.
  • the rest is the same as in the first embodiment except that: after the alkali-washing treatment of the material after the bromination reaction, the organic phase obtained after the alkali washing is not washed with water, and the organic obtained directly after the alkali washing is used. After the rectification and rectification, the finished p-bromofluorobenzene containing o-bromofluorobenzene can be obtained.
  • the rest is the same as in the first embodiment except that the material after the bromination reaction is not subjected to the alkali washing treatment, and the material is directly washed with water and the organic phase obtained after the water washing is directly subjected to rectification, and after the distillation, The finished p-bromofluorobenzene containing o-bromofluorobenzene is available.
  • the bromination reaction is a bromination reaction in which a reaction phase is initiated, and the material after the bromination reaction is subjected to a post-treatment of sequentially removing hydrogen chloride and p-chlorofluorobenzene; After the finished products obtained in Examples 15 to 17 can be directly used according to different use requirements or the related impurities are removed and used.
  • the procedure of the bromination reaction of this example was the same as that of Example 2. After repeating the bromination reaction of Example 2 two to three times, 1000 g of the obtained material was taken out, and the post-treatment of the sulfonation reaction was removed.
  • the corresponding method is: sampling for gas chromatography analysis, the content of o-bromofluorobenzene in the material is 2.2%; then the material is transferred to a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser. The temperature of the material in the reactor was controlled by a cold water bath to be 22 ⁇ 2° C.
  • Example 18 The rest was the same as in Example 18 except that the sulfonating agent used in the post-bromination reaction was 200 g of 20% fuming sulfuric acid.
  • the mixture obtained after the sulfonation reaction is a finished p-bromofluorobenzene containing 3-bromo-4-fluorobenzenesulfonic acid, hydrogen chloride, p-chlorofluorobenzene, sulfuric acid.
  • the bromination reaction is a bromination reaction in the initiation reaction stage, and the bromination reaction is carried out after the removal of o-bromofluorobenzene; the user purchases Example 18 to After the finished product obtained in Example 20 can be directly used according to different use requirements or the related impurities are removed and used.
  • the procedure of the bromination reaction of this example was the same as that of Example 2. After repeating the bromination reaction of Example 2 two to three times, 1000 g of the obtained material was taken out, and the post-treatment of the sulfonation reaction was removed.
  • the o-bromofluorobenzene the specific method is: sampling for gas chromatography analysis, the content of ortho-bromofluorobenzene in the material is 2. 2%; then the material is transferred to a three-necked flask with a stirrer, thermometer and reflux condenser In the cold water bath, the temperature of the material in the reactor was controlled to be 22 ⁇ 2° C.
  • the gas chromatogram shown in Fig. 2 was obtained by sampling and analyzing the finished product of p-bromofluorobenzene obtained in this example, and the image data thereof is shown in Table 4.
  • the substances corresponding to the respective peak names in Table 4 were identified by infrared spectroscopy.
  • the gas chromatograph superimposes the data of the two characteristic 'peaks when printing the map.
  • the instrument model is: GC9790 gas chromatograph manufactured by Zhejiang Wenling Fuli Analytical Instrument Co., Ltd.; the column type is SE54, diameter is 0.35 mm, length is 30 m. Chromatographic conditions: column temperature 130 ⁇ , vaporization chamber 250 ⁇ , detector 250 ⁇ . Detector model: Hydrogen flame ionization detector FID; Injector is split; Precolumn pressure: .0. IMPa; Injection volume: 0.2 ⁇ l. (Example 22)
  • Example 21 The rest was the same as in Example 21 except that the temperature of the sulfonation reaction was controlled at 35 ⁇ 2 ° C and the reaction time was 4.5 hours.
  • the content of the relevant components in the finished product obtained after the reaction is shown in Table 3.
  • Example 21 The rest is the same as in Example 21, except that: The sample after bromination is sampled by gas chromatography to determine that the content of o-bromofluorobenzene in the material is 2.3%, and the temperature of the sulfonation reaction is controlled at 55 ⁇ 2 °C. The reaction time is 4 hours. The content of the relevant components in the finished product obtained after the reaction is shown in Table 3.
  • Example 21 The rest is the same as in Example 21, except that: The sample after bromination is sampled by gas chromatography to determine that the content of o-bromofluorobenzene in the material is 2.3%, and the temperature of the sulfonation reaction is controlled at 65 ⁇ 2 °C. , the reaction time is 3.5 hours. The content of the relevant components in the finished product obtained after the reaction is shown in Table 3.
  • Example 21 The rest is the same as in Example 21, except that: The sample after bromination is sampled by gas chromatography to determine that the content of o-bromofluorobenzene in the material is 2.3%, and the temperature of the sulfonation reaction is controlled at 75 ⁇ 2 °C. , the reaction time is 2.5 hours. The content of the relevant components in the finished product obtained after the reaction is shown in Table 3.
  • Example 21 The rest is the same as in Example 21, except that:
  • the sample after bromination is sampled by gas chromatography to determine that the content of o-bromofluorobenzene in the material is 2.2%, and the temperature of the sulfonation reaction is controlled at 98 ⁇ 2 °C.
  • the reaction time is 2 hours.
  • the content of the relevant components in the finished product obtained after the reaction is shown in Table 3.
  • the rest is the same as that of the embodiment 21, except that: after the alkali-washing treatment of the material after the sulfonation reaction, the organic phase obtained after the alkali washing is no longer washed with water, and DC and O are directly washed with the alkali.
  • the obtained organic phase is subjected to rectification, and after rectification, the finished p-bromofluorobenzene containing p-chlorofluorobenzene can be obtained.
  • Example 21 The rest was the same as in Example 21 except that the material after the sulfonation reaction was no longer subjected to an alkali washing treatment, but directly washed with water, and the organic phase obtained after washing with water was used as a finished p-bromofluorobenzene.
  • Example 21 The rest was the same as in Example 21 except that: as a sulfonating agent, 200 g of 20% fuming sulfuric acid was added in the sulfonation reaction, and the sulfonation reaction time was 3 hours.
  • the content of the relevant components in the finished product obtained after the reaction is shown in Table 5.
  • Example 21 The remainder is the same as in Example 21, except that: the difference is that the content of the material after the bromination reaction is analyzed by gas chromatography to determine the content of the o-bromofluorobenzene is 2.4%, and the sulfonation reaction is added as a sulfonating agent.
  • the content of the relevant components in the finished product obtained after the reaction is shown in Table 5.
  • Example 21 The rest is the same as in Example 21, except that: the difference is that the content of the material after the bromination reaction is analyzed by gas chromatography, and the content of the o-bromofluorobenzene is 2.3%, and the sulfonation reaction is added as a sulfonating agent.
  • the 20% fuming sulfuric acid was 190 g, the sulfonation reaction temperature was controlled to 98 ⁇ 2 ° C, and the sulfonation reaction time was 2 hours.
  • the content of the relevant components in the finished product obtained after the reaction is shown in Table 5.
  • Example 21 The rest was the same as in Example 21 except that 30 g of sulfur trioxide was added as a sulfonating agent in the sulfonation reaction, and the sulfonation reaction time was 5 hours.
  • the content of the relevant components in the finished product obtained after the reaction is shown in Table 6.
  • Example 32 The rest is the same as in Example 32, except that: The sample after the bromination reaction is subjected to gas chromatography to determine that the content of o-bromofluorobenzene is 2.1%, and the sulfonation reaction temperature is controlled to 55 ⁇ 2 ° C, sulfonation. The reaction time was 4 hours. The content of the relevant components in the finished product obtained after the reaction is shown in Table 6.
  • Example 32 The rest is the same as in Example 32, except that: the sample after the bromination reaction is sampled by gas chromatography, and the content of the o-bromofluorobenzene is 2.0%, and the sulfonation reaction temperature is controlled to 80 ⁇ 2'C. The reaction time was 3.5 hours. The content of the relevant components in the finished product obtained after the reaction is shown in Table 6.
  • Example 32 The rest was the same as in Example 32 except that the sulfonation reaction temperature was controlled to 98 ⁇ 2 ° C and the reaction time was 2 hours.
  • the content of the relevant components in the finished product obtained after the reaction is shown in Table 6.
  • the bromination reaction is a bromination reaction in which a reaction phase is initiated, and the material after the bromination reaction is subjected to a post-treatment of sequentially removing o-bromofluorobenzene and hydrogen chloride; After the finished products obtained in Examples 2i to 35 can be directly used according to different use requirements or the related impurities are removed and used.
  • Example 36
  • the process for preparing p-bromofluorobenzene in this embodiment is a manufacturing process in industrial large-scale production, including a bromination reaction process and a sulfonation reaction of a material after bromination to remove o-bromofluorobenzene, followed by washing with a base and then washing with water.
  • the post-treatment process for removing hydrogen chloride and finally using rectification to remove p-chlorofluorobenzene is as follows: In a 2000 liter reactor equipped with a electric stirrer, a thermometer, a bromine high-position tank, a chlorine tube, and a tail gas absorption tower.
  • the brominated material is first subjected to sulfonation treatment, that is, 90 kg of chlorosulfonic acid is added to the mixture obtained by the reaction under stirring, and the sulfonation reaction temperature is controlled to 2 (TC, and the reaction is terminated after 4 hours;
  • the material after the sulfonation reaction is subjected to an alkali washing treatment, that is, the material after the sulfonation reaction is neutralized with a 5% sodium carbonate aqueous solution under stirring until the pH value is 7.
  • the material is sent to the liquid night two phases.
  • Separating device after standing layering, separating the organic phase solution and transferring to another liquid-phase two-phase separation device; and then separating the separated organic phase by water washing, that is, adding the water to the separated organic phase solution, stirring After the layer, the organic phase solution was separated, and the crude p-fluorobromobenzene was obtained, and the weight was 2,650 kg. Then, the content of p-bromofluorobenzene was 98.5 %.
  • the crude bromofluorobenzene obtained by the following steps is rectified: 1
  • the structure of the batch rectification column is shown in Figure 3.
  • the fraction was collected in a 2# receiver, which was called No. 2, and after collecting 160 kg, the sample was analyzed by gas chromatography to obtain a p-chlorofluorobenzene content of about 3%. Finally, the reflux ratio was controlled to 1: 10, and the fraction was collected. 3% ⁇ The 3# receiver, referred to as the No.
  • the sample was analyzed by gas chromatography to obtain a content of p-bromofluorobenzene of about 99.9%, the content of p-chlorofluorobenzene was reduced to 0.03%;
  • the finished product of p-bromofluorobenzene has a mass of 2253 kg; 4 the bottom substrate retained in the evaporator is p-bromofluorobenzene enriched with high-boiling impurities, and the mass is 106 kg.
  • the fractions retained in the evaporator that is, the bottoms, the No. 1 fraction, and the No. 2 fraction are collected, and when they are accumulated to a certain amount, they are separately subjected to rectification, and high-purity p-bromofluorobenzene can also be obtained. .
  • the gas chromatogram shown in FIG. 4 is obtained,
  • the image data are shown in Table 7, and the substances corresponding to the respective peak names in Table 7 were identified by infrared spectroscopy.
  • the instrument and analysis conditions used are as follows - the instrument model is: GC9790 gas chromatograph manufactured by Zhejiang Wenling Fuli Analytical Instrument Co., Ltd.; the column type is 0V 1701, diameter is 0.35 mm, length is 30 m. Chromatographic conditions were column temperature 130 ° C, vaporization chamber 25 (TC, detector 250 ° C.
  • the detector model was hydrogen flame ionization detector FID; the injector was split; column pressure: 0. IMPa; Sample size: 0. 2 microliters.
  • the rest is the same as that of the embodiment 36, except that: after the alkali-washing treatment of the material after the sulfonation reaction, the water-washing treatment is not carried out, and the organic phase solution obtained after the alkali washing is directly subjected to rectification, after the distillation. 02% ⁇
  • the content of p-bromofluorobenzene is 99.9%, the content of p-chlorofluorobenzene is 0.02%.
  • the rest is the same as that of the embodiment 36, except that the material after the sulfonation reaction is no longer subjected to alkali washing, but the material after the sulfonation reaction is directly washed with water, and the organic phase obtained after washing is directly carried out.
  • the content of p-bromofluorobenzene is obtained, wherein the content of p-bromofluorobenzene is 99.9%, and the content of p-chlorofluorobenzene is 0.015%.
  • the bromination reaction is a bromination reaction in the initiation reaction stage, and the bromination reaction is carried out by sequentially removing o-bromofluorobenzene, hydrogen chloride and p-chlorofluorobenzene.
  • Post-processing After purchasing the finished products obtained in Examples 36 to 38, the user can directly use them according to the use requirements.
  • the above examples can prove that the method of the present invention is practical and has excellent effects; at the same time, it can be understood that since the control conditions are different in the actual reaction, the products obtained by the reaction and some of the entire manufacturing process are some Variations in the details of the process steps are possible without departing from the scope and spirit of the invention. Further, the data on the percentage of the relevant components in the materials mentioned in the section of the embodiment of the present invention, if no specific measurement method is mentioned, are analyzed by gas chromatography. Industrial applicability
  • the invention can be used in large-scale industrial production, and the finished product can be used to prepare a finished p-bromofluorobenzene product having a weight percentage of p-bromofluorobenzene of more than 99.9%.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé pour préparer du p-bromofluorobenzène, où une bromination est effectuée entre du fluorobenzène liquide et du brome en présence d'un catalyseur pour produire du p-bromofluorobenzène et du bromure d'hydrogène. Le procédé est caractérisé par l'introduction de chlore gazeux dans le système réactionnel pour une réaction d'oxydation avec le bromure d'hydrogène afin de produire du chlorure d'hydrogène et de l'oxyde de bromure d'hydrogène, et ensuite par la réaction de l'oxyde de bromure d'hydrogène avec du fluorobenzène pour produire du p-bromofluorobenzène. Après la bromination, le produit est utilisé en tant que produit final, ou bien il est post-traité pour éliminer au moins un élément parmi le chlorure d'hydrogène, le p-chlorofluorobenzène et m-bromofluorobenzène dans le produit, pour une pureté plus élevée du p-bromofluorobenzène.
PCT/CN2006/001858 2006-07-26 2006-07-26 Procédé de préparation de p-bromofluorobenzène WO2008017197A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115043378A (zh) * 2021-03-08 2022-09-13 北京诺维新材科技有限公司 一种回收溴的方法
CN116063145A (zh) * 2023-03-29 2023-05-05 山东新龙农化有限公司 一种高纯度高收率的4-溴氟苯合成方法
CN116283597A (zh) * 2023-03-13 2023-06-23 沈阳感光化工研究院有限公司 一种彩色相纸原料2，3，5-三氯-4-乙基硝基苯的制备方法

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Publication number Priority date Publication date Assignee Title
JPS6314742A (ja) * 1986-07-04 1988-01-21 Asahi Chem Ind Co Ltd 高純度パラブロモフルオロベンゼンの製造方法
US5847241A (en) * 1995-08-28 1998-12-08 Bromine Compounds Ltd. Process for the preparation of p-bromofluorobenzene
CN1810745A (zh) * 2005-01-26 2006-08-02 常州市派莱客化学品有限公司 对溴氟苯的制备方法

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Publication number Priority date Publication date Assignee Title
JPS6314742A (ja) * 1986-07-04 1988-01-21 Asahi Chem Ind Co Ltd 高純度パラブロモフルオロベンゼンの製造方法
US5847241A (en) * 1995-08-28 1998-12-08 Bromine Compounds Ltd. Process for the preparation of p-bromofluorobenzene
CN1810745A (zh) * 2005-01-26 2006-08-02 常州市派莱客化学品有限公司 对溴氟苯的制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115043378A (zh) * 2021-03-08 2022-09-13 北京诺维新材科技有限公司 一种回收溴的方法
CN115043378B (zh) * 2021-03-08 2024-03-01 北京诺维新材科技有限公司 一种回收溴的方法
CN116283597A (zh) * 2023-03-13 2023-06-23 沈阳感光化工研究院有限公司 一种彩色相纸原料2，3，5-三氯-4-乙基硝基苯的制备方法
CN116063145A (zh) * 2023-03-29 2023-05-05 山东新龙农化有限公司 一种高纯度高收率的4-溴氟苯合成方法

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