CN111825532A - Preparation method of 4-hydroxybiphenyl - Google Patents
Preparation method of 4-hydroxybiphenyl Download PDFInfo
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- CN111825532A CN111825532A CN202010749312.8A CN202010749312A CN111825532A CN 111825532 A CN111825532 A CN 111825532A CN 202010749312 A CN202010749312 A CN 202010749312A CN 111825532 A CN111825532 A CN 111825532A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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Abstract
The invention claims a preparation method of 4-hydroxybiphenyl, belonging to the field of chemical intermediate preparation. The preparation method takes biphenyl as an initial raw material, and 4-hydroxybiphenyl can be obtained through acylation reaction and oxidation reaction, and comprises the following steps: (1) adding biphenyl into a solvent, adding a catalyst, then dropwise adding an acylating agent, sampling and detecting, after the reaction is finished, washing with water, concentrating and crystallizing. (2) And (3) adding a solvent into the product for dissolving, adding an oxidant, sampling and detecting, washing and filtering after the reaction is finished, and crystallizing, drying and distilling the product to obtain the product with the content of more than 99.5%. The method has the advantages of low production cost, environment-friendly process and high yield, and is suitable for industrial production.
Description
Technical Field
The invention relates to a preparation method of 4-hydroxybiphenyl, belonging to the field of chemical intermediate preparation.
Background
4-hydroxy biphenyl is an intermediate which can be used for liquid crystal materials, pesticides, dyes, resins and rubber, and a red light sensitizing fuel and a green light sensitizing fuel which are further synthesized by the intermediate are one of the main raw materials of color films; it can also be used as analytical reagent, inhibitor for colorimetric determination of acetaldehyde and lactic acid, quantitative determination of muramic acid and deoxyribonuclease, and solubilizer for dye, resin, rubber intermediate, bactericide, and water-soluble paint.
At present, various preparation methods are applied to production, and the following preparation processes are widely applied to known production.
The method comprises the following steps: the biphenyl-4-sodium sulfonate is subjected to high-temperature alkali dissolution reaction in an alkali melting kettle, then the process has the problems of large strong alkali, strong acid waste liquid and high energy consumption through acidification, centrifugal filtration and recrystallization, and a sulfonation alkali dissolution method is already listed in various obsolete processes, and the old process is gradually shut down for production.
The second method comprises the following steps: under the protection of inert gas, THF is used as a solvent, and 4-methoxy bromobenzene reacts with magnesium chips to obtain a Grignard reagent; reacting the Grignard reagent with bromobenzene under the catalysis of a catalyst, washing, drying, concentrating and crystallizing to obtain 4-methoxybiphenyl, heating and refluxing with hydrobromic acid to remove methyl, washing, drying, concentrating, and recrystallizing with toluene to obtain 4-hydroxybiphenyl. The process uses a format reagent method, a catalyst is expensive and has multiple steps, and self-coupling products exist in the product and are difficult to remove, so that the quality of the product is influenced.
The third method comprises the following steps: the 4-hydroxybiphenyl is synthesized by utilizing a Suzuki coupling reaction and palladium-catalyzed cross coupling reactions of organic aromatic borides (4-hydroxyphenylboronic acid or phenylboronic acid) and halogenated aromatic benzene (bromobenzene or 3-bromophenol) under the action of alkali (potassium carbonate, potassium phosphate and sodium hydroxide), wherein the organic aromatic borides (4-hydroxyphenylpalladium and bis (triphenylphosphine) palladium chloride) are synthesized by using palladium, but the synthesis method has the problems of complicated post-treatment and high product purification difficulty, and most importantly, an expensive metal palladium catalyst is used, so that the cost is high, and the synthesis method is not suitable for industrial production.
In conclusion, the existing preparation method of 4-hydroxybiphenyl has the technical defects of high preparation price, difficulty in removing impurities in the product and high energy consumption, and a novel environment-friendly and low-cost method is found to meet the urgent demand of the market on the product, so that the method becomes the requirement of the industry.
Chinese patent CN1171389 discloses a process for preparing 4-hydroxybiphenyl, which comprises heating a reaction mixture containing 4-hydroxybiphenyl obtained by basic hydrolysis of biphenyl-4-sulfonic acid under high pressure at a temperature higher than 115 ℃ and a pH of 0 to less than 6.5. The method adopts the first method for production, and the process is gradually eliminated due to harsh reaction conditions and low energy consumption and high energy consumption.
Chinese patent application CN109651091A discloses a separation and purification device is used in processing of 4-hydroxybiphenyl, including reaction equipment and crystallization equipment, reaction equipment includes upper strata reacting chamber and lower floor's layering room the internally mounted of upper strata reacting chamber has horizontal (mixing) shaft and vertical (mixing) shaft the internally mounted of lower floor's layering room has the vibrting spear, the inside of lower floor's layering room has been placed and has been floated reaction equipment's lower extreme intercommunication is connected with the purifying box one end surface mounting of purifying box has the suction pump, crystallization equipment fixed connection is in reaction equipment's right side, crystallization equipment includes cooling chamber and cooling drum crystallization equipment's right side lower extreme intercommunication is connected with ejection of compact pipeline a side surface mounting of ejection of compact pipeline has the PLC controller. The separation and purification device for processing the 4-hydroxybiphenyl realizes the separation and purification of the 4-hydroxybiphenyl through reaction equipment and crystallization equipment, and has higher use value. Which protects objects differently from the present invention.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an industrial production method which is low in cost, high in yield, green, environment-friendly and recyclable. The invention provides a preparation method of 4-hydroxybiphenyl, which takes biphenyl as a starting raw material, and can obtain the 4-hydroxybiphenyl through acylation reaction and oxidation reaction.
The invention realizes the technical effects through the following technical scheme:
a preparation method of 4-hydroxybiphenyl takes biphenyl as a starting raw material, and 4-hydroxybiphenyl can be obtained through acylation reaction and oxidation reaction, and the preparation method specifically comprises the following steps:
step 1): adding biphenyl into a solvent, stirring for dissolving, adding a catalyst and an acylating agent at a certain temperature for reaction, and hydrolyzing to obtain an acylated product;
the chemical reaction formula is as follows;
step 2): the acylation product is dissolved in a solvent, an oxidant is added for reaction, and the 4-hydroxybiphenyl with the content of 99.8 percent is obtained after filtration, washing, drying, distillation and crystallization.
The chemical reaction formula is as follows:
the 4-hydroxybiphenyl prepared by the preparation method has pure quality, white color and luster, the content of 99.8 percent and the total yield of 86 percent based on the biphenyl.
Preferably: in the step 1), the solvent is selected from one of dichloromethane, toluene, dichloroethane, chloroform and carbon tetrachloride.
Preferably: in the step 1), the catalyst is one or more of aluminum trichloride, ferric trichloride and zinc chloride.
Preferably: in the step 1), the reaction temperature is between-20 and 40 ℃.
Preferably: the step 1) is carried out, wherein the molar ratio of the materials is biphenyl: catalyst: the acylating agent is 1: (1.05-1.4): (1.1-1.3).
Preferably: in the step 1), the acylating agent is one or two of acyl chloride and anhydride.
Preferably: in the step 2), the solvent is one or two of dioxane, tetrahydrofuran, isopropyl acid, dichloroethane, benzene, acetic acid and water.
Preferably: in the step 2), the oxidant is one or more of potassium persulfate, ammonium persulfate, sodium perchlorate, hydrogen peroxide, peroxyacetic acid and potassium permanganate;
preferably: in the step 2), the temperature of the oxidation reaction is between 0 and 50 ℃.
Preferably: in the step 2), the crystallization solvent is one or two of toluene, methanol, ethanol, methyl isobutyl ketone and water.
Preferably: in the step 2), the distillation operation condition is that 120-126/3mmHg fraction is distilled under reduced pressure;
preferably: the invention designs an acylation process and an oxidation process, and the production can be completed by two steps.
Compared with the prior art, the synthesis method of the 4-hydroxybiphenyl has the advantages of environmental protection, low cost, circular economy and sustainable development, and simultaneously, the problem of three wastes is properly solved. The beneficial effects are as follows:
1. the invention adopts biphenyl as the main raw material, the auxiliary materials (acylating agent and oxidant) are all industrialized products, the raw materials are cheap and easy to obtain, and the related reaction conditions are mild, the operation is convenient, the reaction is easy to control, the reaction equipment is simple, and the whole process is very suitable for industrialized mass production; the 4-hydroxybiphenyl prepared by the preparation process has pure quality, white color and luster, the content of 99.8 percent and the total yield of 86 percent based on the biphenyl.
2. The solvent of the acylation procedure can be recycled through simple dewatering operation, and the acylation waste water can be used for preparing a by-product flocculant solution and can be used for a flocculation process in sewage treatment, so that the reaction cost is low, the waste water treatment cost is saved, and the method has higher economic value.
3. The solvent recovered in the oxidation procedure can be recycled after liquid separation and distillation, so that the reaction cost is reduced; the filtered filtrate of the wastewater generated in the oxidation process can be used as a biochemical oxidant of a sewage treatment station after being extracted, can degrade macromolecules into micromolecules, reduces the material cost of sewage treatment, and has higher economic value.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the teachings of the present invention, and such equivalents also fall within the scope of the appended claims.
The chemical equation of the synthetic process of the invention is as follows:
example 1:
the embodiment provides a process method for synthesizing 4-hydroxybiphenyl, which comprises the following specific synthesis steps:
1400kg of chloroform and 182 kg of aluminum trichloride are added into a 2000L enamel reaction kettle, the temperature is reduced to-10 ℃ by cold bath stirring, 300kg of biphenyl is added, the temperature is reduced to-15 ℃ continuously, 102kg of anhydride is added dropwise, the temperature is kept for 3 hours after dropping for about 1 hour, 1500kg of water is added under stirring, hydrolysis is completed, liquid separation is carried out, water is washed to be neutral, water is purified, desolventization is carried out at normal pressure, the temperature is kept for standby application, 366 kg of aluminum trichloride with the content of more than 97.3 percent is produced, and the yield is 96 percent.
Adding acylated biphenyl and 1170kg of benzene into a 3000L kettle, cooling to 10 ℃, dropwise adding 380kg of 50% hydrogen peroxide, keeping the temperature at 20 ℃ for 9 hours, filtering after the reaction is finished, leaching to obtain a crude product, extracting the filtrate with toluene, barreling (for sewage biochemical treatment), drying the crude product, distilling under reduced pressure, and recrystallizing with ethanol to obtain a white product with the content of 99.8% and the yield of 87%.
Example 2:
1350Kg of dichloromethane and 405 Kg of ferric trichloride are added into a 2000L reaction kettle, the temperature is reduced to-10 ℃ by cold bath stirring, 300Kg of biphenyl is added, the temperature is further reduced to-15 ℃, 180Kg of acetyl chloride is added dropwise, the dropwise addition is completed within about 1 hour, the temperature is kept for 3 hours, 1600Kg of water is added under stirring, after the hydrolysis, liquid separation and washing are performed to neutrality, water is separated and purified, the solution is desolventized under normal pressure, the solution is cooled to 110 ℃, and after the solution is cooled slightly, the solution is transferred into a stainless steel kettle while the solution is hot, 354Kg is produced, the content is more than 98.4%, and.
Adding acylated biphenyl and 1230kg of acetic acid into a 3000L kettle, dissolving, cooling to 10 ℃, dropwise adding 238kg of peroxyacetic acid, keeping the temperature at 20 ℃ for 8 hours, filtering after the reaction is finished, leaching to obtain a crude product, extracting the filtrate with toluene, barreling (for sewage biochemical treatment), drying the crude product, distilling under reduced pressure, and recrystallizing with toluene to obtain a white product with the content of 99.9 percent and the yield of 84 percent.
Example 3:
1210Kg of dichloroethane and 365Kg of zinc chloride are added into a 2000L reaction kettle, the temperature is reduced to-10 ℃ by cold bath stirring, 300Kg of biphenyl is added, the temperature is further reduced to-15 ℃, 110Kg of anhydride is added dropwise, the dropwise addition is completed within about 1 hour, 1600Kg of water is added under stirring when the temperature is kept for 4 hours, the hydrolysis is completed, liquid separation is carried out, the water is washed to be neutral, the purified water is separated, the desolventization is carried out under normal pressure to 110 ℃, the mixture is transferred into a stainless steel kettle when the mixture is hot after being slightly cooled, 288Kg of water with the content of more than 98.6 percent is produced, and the yield.
In a 3000L kettle, adding acylated biphenyl, 1026kg of dioxane and 623kg of potassium persulfate, cooling to 10 ℃, dropwise adding 480kg of 60% sulfuric acid, keeping the temperature at 20 ℃ for 12 hours, filtering after the reaction is finished, leaching to obtain a crude product, extracting the filtrate with toluene, barreling (for sewage biochemical treatment), drying the crude product, distilling under reduced pressure, and recrystallizing with ethanol to obtain a white product with the content of 99.8% and the yield of 86%.
Claims (8)
1. A preparation method of 4-hydroxybiphenyl takes biphenyl as a starting raw material, and 4-hydroxybiphenyl can be obtained through acylation reaction and oxidation reaction, and the preparation method specifically comprises the following steps:
step 1): adding biphenyl into a solvent, stirring for dissolving, adding a catalyst and an acylating agent at a certain temperature for reaction, and hydrolyzing to obtain an acylated product;
the chemical reaction formula is as follows;
step 2): dissolving the acylation product in a solvent, adding an oxidant for reaction, filtering, washing with water, drying, distilling and crystallizing to obtain 4-hydroxybiphenyl;
the chemical reaction formula is as follows:
2. the method for preparing 4-hydroxybiphenyl according to claim 1, wherein the solvent in step 1) is selected from one of dichloromethane, toluene, dichloroethane, chloroform, carbon tetrachloride; the catalyst is one or more of aluminum trichloride, ferric trichloride and zinc chloride; the acylating agent is one or two of acyl chloride and anhydride.
3. The method for producing 4-hydroxybiphenyl according to claim 1, wherein in the step 1), the reaction temperature is between-20 ℃ and 40 ℃; the molar ratio of the materials is biphenyl: catalyst: the acylating agent is 1: (1.05-1.4): (1.1-1.3).
4. The method for preparing 4-hydroxybiphenyl according to claim 1, wherein the solvent in step 2) is one or two of dioxane, tetrahydrofuran, isopropyl acid, dichloroethane, benzene, acetic acid, and water; the oxidant is one or more of potassium persulfate, ammonium persulfate, sodium perchlorate, hydrogen peroxide, peroxyacetic acid and potassium permanganate.
5. The method for producing 4-hydroxybiphenyl according to claim 1, wherein the oxidation reaction temperature in the step 2) is between 0 and 50 ℃.
6. The method for preparing 4-hydroxybiphenyl according to claim 1, wherein the crystallization solvent in step 2) is one or two of toluene, methanol, ethanol, methyl isobutyl ketone and water.
7. The process for producing 4-hydroxybiphenyl according to claim 1, wherein the distillation conditions in the step 2) are distillation under reduced pressure of 120 to 126/3 mmHg.
8. The process for the preparation of 4-hydroxybiphenyl according to claim 1, characterized in that it comprises the following steps:
(1) adding biphenyl into a solvent with the mass of 1-5 times that of the biphenyl at the temperature of-20-30 ℃ under the stirring condition, then adding a certain amount of catalyst into the solvent, wherein the catalyst is aluminum trichloride, ferric trichloride and zinc chloride, adding an acylating agent, the acylating agent is acid anhydride and acyl chloride, reacting for 1-4 hours, and after monitoring the reaction, hydrolyzing and washing, concentrating the solvent to obtain an acylated product;
(2) adding the product of the previous step under stirring at 10-50 ℃, adding a mixed solvent of one of dichloroethane, dioxane, tetrahydrofuran, acetic acid and isopropyl acid and water, adding an oxidant which is potassium persulfate, ammonium persulfate, sodium perchlorate, hydrogen peroxide, peroxyacetic acid and potassium permanganate, reacting for 1-12 hours, filtering, washing with water, centrifuging, drying and distilling to obtain the product after the reaction is finished.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112374970A (en) * | 2020-12-02 | 2021-02-19 | 黑龙江中医药大学 | Synthesis of biphenols |
| CN114835560A (en) * | 2022-06-13 | 2022-08-02 | 连云港市三联化工有限公司 | Preparation method of 4-hydroxybiphenyl |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171389A (en) * | 1996-06-18 | 1998-01-28 | 拜尔公司 | Process for preparation of 4-hydroxybiphenyl |
| CN108147946A (en) * | 2017-12-04 | 2018-06-12 | 华南农业大学 | A kind of method for preparing 4- phenylphenols |
-
2020
- 2020-07-30 CN CN202010749312.8A patent/CN111825532A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171389A (en) * | 1996-06-18 | 1998-01-28 | 拜尔公司 | Process for preparation of 4-hydroxybiphenyl |
| CN108147946A (en) * | 2017-12-04 | 2018-06-12 | 华南农业大学 | A kind of method for preparing 4- phenylphenols |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112374970A (en) * | 2020-12-02 | 2021-02-19 | 黑龙江中医药大学 | Synthesis of biphenols |
| CN112374970B (en) * | 2020-12-02 | 2023-11-24 | 黑龙江中医药大学 | Synthesis of biphenol |
| CN114835560A (en) * | 2022-06-13 | 2022-08-02 | 连云港市三联化工有限公司 | Preparation method of 4-hydroxybiphenyl |
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