CN112374970B - Synthesis of biphenol - Google Patents

Synthesis of biphenol Download PDF

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CN112374970B
CN112374970B CN202011394759.4A CN202011394759A CN112374970B CN 112374970 B CN112374970 B CN 112374970B CN 202011394759 A CN202011394759 A CN 202011394759A CN 112374970 B CN112374970 B CN 112374970B
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reaction
felbinac
treatment
catalyst
diacetone
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CN112374970A (en
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黄楠楠
徐永海
姚林山
牛立中
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Fuyu County Agricultural Technology Extension Center
Heilongjiang University
Heilongjiang University of Chinese Medicine
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Fuyu County Agricultural Technology Extension Center
Heilongjiang University
Heilongjiang University of Chinese Medicine
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
    • C07C37/0555—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group being esterified hydroxy groups
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters

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

Abstract

The invention discloses a green process route of diphenol. The biphenyl is subjected to Friedel-crafts acylation reaction to prepare the biphenyl, wherein the waste water containing aluminum trichloride, which is generated by Friedel-crafts acylation hydrolysis, can be treated to obtain polyaluminium chloride, and is widely used for sewage treatment. The diphenyl acetic ester is obtained by the oxidation rearrangement reaction of the obtained diacetone through the Baeyer-Villiger, the oxidant used by the oxidation rearrangement reaction of the Baeyer-Villiger is a maleic anhydride/hydrogen peroxide system, and maleic anhydride can be obtained again by dehydration treatment of the reaction byproduct maleic acid, so that the reuse of the oxidant is realized. Finally, the biphenol is obtained by alkaline hydrolysis of the felbinac. The synthesis process designed by the invention is a safe, green and environment-friendly process route, has mild reaction and controllable reaction process, and has high industrial value.

Description

Synthesis of biphenol
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a synthetic process of diphenol.
Background
Biphenol is also called p-phenylphenol, and has a molecular formula of C 6 H 5 C 6 H 4 OH, its structural formula is:
biphenol is an almost white crystal, insoluble in water, in ethanol, caustic soda solution and various organic solvents. Biphenol is an important novel fine chemical intermediate, and the red light sensitization dye and the green light sensitization dye synthesized by the biphenol are one of main raw materials of a color film and can be used as an analysis reagent; can also be used for preparing oil-soluble resin and emulsifying agent, and can be used as a component of corrosion-resistant paint, a carrier for printing and dyeing, and the like. In a comprehensive view, the diphenol is widely applied to the fields of dyes, pesticides, preservatives, coatings, printing and dyeing assistants, photosensitive materials and the like.
In view of the potential application of biphenol, the demand of China for biphenol is increased year by year, and at present, a plurality of defects exist in the synthesis, and in the aspect of a typical method of industrialized synthesis, for example:
the cyclohexanone phenol method is used for preparing biphenol. Specifically, firstly, phenol and cyclohexanone are condensed to generate 1, 1-bis- (4-hydroxyphenyl) cyclohexane, the 1, 1-bis- (4-hydroxyphenyl) cyclohexane is separated from a reaction system and then heated under the action of a hydrogen transfer catalyst to generate a cracking dehydrogenation reaction, and the superfluous phenol in the first reaction can be used as a hydrogen absorbent in the second reaction. The method is simple and economical, and has the defects that the activity of the Pd/C catalyst used has great influence on the reaction and the reaction time is long, and the method is gradually replaced by a biphenyl sulfonated alkali fusion method.
The biphenyl sulfonated alkali fusion method for producing p-phenylphenol has been industrialized for many years abroad, such as Bayer company in Germany, japanese three photochemical company, etc., and the technology is relatively mature. The method comprises the steps of sulfonating biphenyl by sulfuric acid, diluting a sulfonation mixture by water, partially neutralizing by sodium hydroxide solution, and then filtering and drying to obtain sodium salt of sulfonic acid; the sodium sulfonate is then reacted with the alkali melt at elevated temperature (at least 350 ℃) for a prolonged period of time, the post-reaction treatment being pouring the reaction solution into hot water. The method is not ideal in both purity and yield. The adoption of high temperature and post-treatment in the reaction process is difficult to the production environment in the operation process, and the safety is poor. The salt produced in the sulfonation process of biphenyl contains sodium sulfate, sodium sulfite and sodium bisulfite, and the salt of the sodium sulfate, sodium sulfite and sodium bisulfite has reducibility, which brings great difficulty to the treatment of the salt.
For the above reasons, there is a need to provide a safe, environment-friendly and green synthesis method of biphenol.
Disclosure of Invention
In order to overcome the above problems, the present inventors have made intensive studies to develop a green process route for biphenol. The biphenyl is subjected to Friedel-crafts acylation reaction to prepare the biphenyl, wherein the waste water containing aluminum trichloride, which is generated by Friedel-crafts acylation hydrolysis, can be treated to obtain polyaluminium chloride, and is widely used for sewage treatment. The diphenyl acetic ester is obtained by the oxidation rearrangement reaction of the obtained diacetone through the Baeyer-Villiger, the oxidant used by the oxidation rearrangement reaction of the Baeyer-Villiger is a maleic anhydride/hydrogen peroxide system, and maleic anhydride can be obtained again by dehydration treatment of the reaction byproduct maleic acid, so that the reuse of the oxidant is realized. Finally, the biphenol is obtained by alkaline hydrolysis of the felbinac. The synthesis process designed by the invention is a safe, green and environment-friendly process route, has mild reaction and controllable reaction process, and has high industrial value.
An aspect of the present invention is to provide a process for synthesizing diphenol, which comprises the steps of:
step 1, preparing diacetone;
step 2, oxidizing and rearranging the diacetone to obtain felbinac;
and 3, carrying out hydrolysis reaction on felbinac to obtain biphenol.
Wherein, step 1 comprises the following steps:
step 1-1, adding biphenyl, acetyl chloride, a catalyst and an organic solvent into a reactor for reaction;
and step 1-2, after the reaction is finished, carrying out post-treatment to obtain the diacetone.
Wherein, in the step 1-1,
the organic solvent is preferably an aprotic organic solvent, more preferably dichloroethane, as an inert solvent;
the catalyst is preferably any one or more of ferric oxide, potassium bromide, aluminum trichloride and ferric trichloride, and more preferably aluminum trichloride.
Wherein, in step 1-2, the post-processing comprises: stirring, standing, separating and washing.
Wherein, step 2 includes:
step 2-1, adding diacetone, an oxidant and an organic solvent into a reactor for reaction;
step 2-2, after the reaction is finished, carrying out post-treatment to obtain felbinac;
optionally, the felbinac obtained in the step 2-2 is subjected to secondary oxidation rearrangement.
Wherein, in the step 2-1,
the organic solvent is an aprotic organic solvent, more preferably the same organic solvent as used in the synthesis of biacetophenone.
The oxidizing agent includes acid anhydride, peracid, inorganic strong acid, peroxide, preferably acid anhydride and hydrogen peroxide as the oxidation reaction system, more preferably maleic anhydride and hydrogen peroxide.
Wherein, in step 2-2, the post-processing includes: filtering, standing and separating.
Wherein, step 3 includes the following steps:
step 3-1, feeding materials into a reactor to react;
step 3-2, acidifying the solution obtained in the step 3-1, and adjusting the pH;
and 3-3, performing post-treatment to obtain the diphenol.
Wherein, in step 3-1, the feed to the reactor comprises felbinac, a hydrocarbon derivative, a base, and a solvent.
Another aspect of the present invention is to provide a diphenol prepared by the synthesis process according to the first aspect of the present invention.
The invention has the beneficial effects that:
1. when the invention synthesizes biphenol, biphenyl is adopted at the front end to prepare the diacetone through Friedel-crafts acylation reaction, wherein aluminum trichloride generated by Friedel-crafts acylation hydrolysis can be treated to obtain polyaluminium chloride, and the polyaluminium chloride is widely used for sewage treatment and reduces the generation of three wastes from the source.
2. In the reaction process, the felbinac is prepared through Baeyer-Villiger oxidation rearrangement reaction, the oxidant used in the oxidation rearrangement reaction is a maleic anhydride/hydrogen peroxide system, maleic anhydride can be obtained again through dehydration treatment of the by-product maleic acid of the reaction, and the recycling of the oxidant is realized.
3. The catalyst used in the invention can be used for sewage treatment after treatment, and the generation of waste water and waste residue is reduced.
4. The invention has simple post-treatment process after the reaction is finished when synthesizing biphenol, and fundamentally solves the problems of more three wastes and serious environmental pollution of the traditional process.
5. The method for synthesizing the biphenol is simple, mild in condition, easy to control and safe in intermediate reaction process, and has high industrial value.
Drawings
FIG. 1 shows the nuclear magnetic resonance spectrum of biphenol obtained in example 1 of the present invention.
Detailed Description
The invention is further described in detail below by means of the figures and examples. The features and advantages of the present invention will become more apparent from the description.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
According to the present invention, there is provided a process for synthesizing biphenol, the process comprising the steps of:
step 1, preparing the diacetone.
In a further preferred embodiment, step 1 comprises the steps of:
step 1-1, adding biphenyl, acetyl chloride and an organic solvent into a reactor for reaction.
In step 1-1, the organic solvent is used as an inert solvent to provide a reaction system for the reaction, preferably the organic solvent is an aprotic organic solvent, for example: dichloromethane, dichloroethane, nitrobenzene, nitromethane, petroleum ether, carbon tetrachloride, etc., more preferably dichloroethane.
In the step 1-1, the inventor researches and discovers that the raw material biphenyl has better solubility in dichloroethane, and the dichloroethane is used as a reaction system solvent, so that the reaction is simpler and safer no matter the reaction condition or the process, and meanwhile, the reaction process is more stable, and the dichloroethane is used as the reaction system solvent and does not participate in the reaction, thereby being beneficial to the reaction.
In step 1-1, optionally, a catalyst is also added to the reactor. The catalyst is preferably any one or more of ferric oxide, potassium bromide, aluminum trichloride and ferric trichloride, and more preferably aluminum trichloride.
In the invention, aluminum trichloride is preferably used as a reaction catalyst, so that the reaction process can be accelerated, the recovery is convenient after the diacetone required by the reaction is obtained, the polyaluminum chloride can be obtained after further treatment, and the polyaluminum chloride is used for sewage treatment, so that the generation of three wastes is reduced from the source, and is very environment-friendly.
In a further preferred embodiment, the catalyst is added in batches, and a great amount of practices prove that the catalyst can be effectively prevented from being added in batches at one time, so that the defect of too fast and uncontrollable reaction is avoided, the small temperature change of the system is ensured, and the generation of byproducts is properly reduced.
In a further preferred embodiment, the catalyst is added under ice bath conditions at a temperature of less than 18 ℃, preferably less than 12 ℃, more preferably 0-10 ℃, the ice bath conditions being sufficient to ensure that the reaction proceeds, so that the reaction is milder, while the production of by-products may be further reduced.
In step 1-1, the molar ratio of biphenyl, acetyl chloride and catalyst is 0.5-2:0.5-3:0.1-2, preferably 0.8-1.5:0.8-2:0.5-1.5, more preferably 1:1:1.05, wherein the molar amount of biphenyl is calculated on the molar amount of the molecule, the molar amount of acetyl chloride is calculated on the molar amount of the molecule, and the catalyst is calculated on the molar amount of the molecule.
In the invention, along with the increase of the adding amount of the catalyst, the reaction rate is effectively accelerated, the selectivity of the diacetone is improved, but the excessive catalyst has little influence on the reaction, and the workload of post-treatment is increased.
In step 1-1, the catalyst addition is completed, preferably the reaction is continued at room temperature, the reaction time is less than 3 hours, preferably less than 2 hours, more preferably 30 minutes, the reaction process is simple, the time is short, and the product is easy to obtain.
In step 1-1, the reactor is not limited to any vessel in which the reaction can be performed, preferably the reactor is a flask, more preferably the reactor is a four-necked flask, so that the reactants can be added at any time during the reaction.
In a preferred embodiment, biphenyl is subjected to Friedel-crafts acylation to obtain biacetophenone, wherein the reaction in step 1-1 is shown as a formula (1):
and step 1-2, after the reaction is finished, carrying out post-treatment to obtain the diacetone.
In step 1-2, the post-processing comprises: stirring, standing, separating and washing.
In the step 1-2, standing for layering, wherein the supernatant contains the catalyst, and the catalyst is further treated to be recycled; the lower liquid is further washed and is used for the subsequent reaction for preparing the target product diphenol.
In the step 1, the diacetone obtained by the reaction contains the organic solvents such as dichloroethane and the like, but no further treatment is needed, because the solvents are added into the diacetone in the subsequent reaction, and practical researches prove that the residual liquid obtained in the step 1 is directly used for synthesizing the target product diphenol in the subsequent reaction, so that the quality of the diphenol is not influenced, the production and quality requirements of the diphenol are completely met, the used catalyst can be recycled, the generation of three wastes is reduced from the source, and the energy consumption is reduced.
And 2, oxidizing and rearranging the diacetone to obtain the felbinac.
In a further preferred embodiment, step 2 comprises:
and 2-1, adding the diacetone, the oxidant and the organic solvent into a reactor for reaction.
In step 2-1, the organic solvent is an aprotic organic solvent, such as: dichloromethane, dichloroethane, nitrobenzene, nitromethane, petroleum ether, carbon tetrachloride, etc., more preferably the same organic solvent as used in the synthesis of diacetone, avoiding the introduction of other impurities.
In step 2-1, the oxidizing agent comprises an anhydride, a peracid, a strong mineral acid, a peroxide, for example: peroxosulfuric acid, peroxoacetic acid, peroxotrifluoroacetic acid, maleic anhydride, hydrogen peroxide, etc., which cause Baeyer-Villiger oxidative rearrangement of the diacetone, anhydride and hydrogen peroxide are preferred as the oxidation reaction system, and maleic anhydride and hydrogen peroxide are more preferred.
In step 2-1, maleic anhydride and hydrogen peroxide are preferable as the oxidation reaction system. In the process of synthesizing the ester, in order to improve the yield of the ester, the reaction is required to move rightwards, the maleic anhydride is taken as an oxidant, the reaction is mild, water generated by the reaction can be properly removed by the maleic anhydride, the reaction balance is broken, the reaction is promoted to move rightwards, and the reaction yield is improved. In the reaction process, maleic anhydride can be obtained by dehydration treatment only after the reaction is finished, and the maleic anhydride can be directly applied to the reaction process of the next batch, so that zero emission of three wastes is realized, and the method has great significance for industrialized industry.
In the step 2-1, hydrogen peroxide is used as an oxidant, so that unnecessary side reactions in chemical synthesis can be effectively reduced and avoided, the method has the advantage of no corrosion to a reaction container, little environmental pollution is caused, when the oxidation capacity of the method is consumed, only water is generated, and the expensive cost of wastewater treatment can be reduced.
In step 2-1, the molar amount ratio of the oxidizing agent maleic anhydride to hydrogen peroxide is 0.1-2:0.3-3, preferably 0.5-1.2:0.8-2, more preferably 1:1, wherein maleic anhydride is based on the molar amount of its molecules and hydrogen peroxide is based on the molar amount of its molecules.
In the present invention, the inventors have found that the conversion of the diacetone is highest when the molar ratio of maleic anhydride to hydrogen peroxide is 0.1 to 2:0.3 to 3, especially when the molar ratio is 1:1, and that too much maleic anhydride or hydrogen peroxide causes an increase in byproducts and is disadvantageous for the post-reaction treatment.
In a further preferred embodiment, the diacetone, maleic anhydride, organic solvent produced in the reaction of step 1 are added to a reaction vessel, and hydrogen peroxide is added at low temperature. Wherein the low temperature is not more than 20 ℃, preferably less than 15 ℃, more preferably less than 10 ℃. Hydrogen peroxide is extremely easily decomposed, and for effective control of the reaction rate, it is preferable to add hydrogen peroxide dropwise to the reactor at a low temperature.
In step 2-1, it is preferable that the catalyst is added thereto after the above-mentioned liquids are uniformly mixed and the reaction is continued for 5 to 24 hours, preferably 8 to 16 hours, more preferably 9 to 13 hours, for example 12 hours, and the longer the reaction time, the more sufficient the reaction, but the longer the reaction time is, the less practical it is.
Wherein the catalyst is preferably one or more of zinc powder, zinc chloride, ferric chloride and stannous chloride, and more preferably zinc powder.
In the present invention, the inventors have found that zinc powder is preferable as a catalyst for oxidation reaction, and not only can the reaction progress be effectively accelerated, but also, more importantly, the reaction can be made more thorough.
In a further preferred embodiment, the biacetophenone undergoes a Baeyer-Villiger oxidative rearrangement to give felbinac, and the reaction occurring in step 2-1 is as shown in formula (2):
and 2-2, after the reaction is finished, carrying out post-treatment to obtain felbinac.
In step 2-2, the post-processing includes: filtering, standing and separating.
In the step 2-2, the filter cake obtained by filtration is collected and recycled; and standing the filtrate to obtain a lower layer solution which is the reaction liquid felbinac required by the subsequent reaction.
In a preferred embodiment, the felbinac obtained in step 2-2 is subjected to a secondary oxidative rearrangement.
In step 2, the present inventors have studied and found that after the completion of the primary oxidation rearrangement reaction, part of the diacetone remains unreacted, and in order to improve the conversion rate of the diacetone and the selectivity and yield of felbinac, it is preferable to perform the secondary oxidation of the felbinac obtained as described above.
Further, the step 2-1 is repeated by adding an oxidizing agent and a catalyst to the reaction solution felbinac, preferably, the oxidizing agent and the catalyst are selected from the same types of oxidizing agents and catalysts used in the step 2-1 in order to reduce side reactions and avoid introducing new impurities.
Wherein the oxidizing agent is preferably a maleic anhydride to hydrogen peroxide system, the molar ratio of maleic anhydride to hydrogen peroxide being from 0.1 to 2:0.3 to 3, preferably from 0.5 to 1.2:0.8 to 2, more preferably 1:1, wherein the maleic anhydride is in terms of moles of its molecules and the hydrogen peroxide is in terms of moles of its molecules.
Further, after the reaction is finished, separating and purifying to obtain an organic solvent and felbinac, wherein the felbinac participates in the subsequent reaction process, and the organic solvent is directly sleeved for the next batch reaction.
And 3, carrying out hydrolysis reaction on felbinac to obtain biphenol.
In a further preferred embodiment, step 3 comprises the steps of:
step 3-1, feeding materials into a reactor to perform reaction.
In step 3-1, the feed to the reactor comprises felbinac, a hydrocarbon derivative, a base, and a solvent.
Among them, the hydrocarbon derivatives are preferably alcohols including methanol, butanol, isopropanol, ethylene glycol, more preferably methanol. The methanol is cheap and easy to obtain and recycle, and the felbinac has good solubility in the methanol and does not influence the reaction.
Wherein, the felbinac is subjected to hydrolysis reaction in an alkaline environment to generate the creosote. The base is a strong base including potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium carbonate, preferably a strong base metal hydroxide, more preferably sodium hydroxide.
In step 3-1, sodium hydroxide is used as an alkali dissolution solvent, so that higher-quality creosote can be obtained.
Wherein, the solvent is water or deionized water, preferably water, and the source is wide.
In step 3-1, the base and solvent provide an alkali-soluble environment for the felbinac.
In step 3-1, the above raw materials are added into a reactor and reacted under reflux.
Step 3-2, acidifying the solution obtained in step 3-1, and adjusting pH.
In step 3-2, an acidic solution is selected for acidification, said acidic solution being a strong acid, preferably an inorganic strong acid, more preferably hydrochloric acid.
In the invention, the inventor researches and discovers that the pH of the system is regulated to 3-4 by hydrochloric acid, which is helpful for improving the quality and yield of the finished bisphenol product.
In a further preferred embodiment, the felbinac undergoes a hydrolysis reaction in an alkali-soluble environment to give a biphenol salt, and after acidification, the biphenol salt undergoes a reaction represented by formula (3):
and 3-3, performing post-treatment to obtain the diphenol.
In step 3-3, the post-processing includes: stirring, filtering, washing with water, drying, and recrystallizing.
Among them, the solvent used for the recrystallization is preferably an alcohol such as isopropyl alcohol.
According to a second aspect of the present invention there is provided a biphenol prepared by a synthesis process according to the first aspect of the present invention.
The synthesis process of biphenol provided by the invention realizes the recycling of the catalyst and the oxidant, the reaction process does not involve high-temperature reaction, and compared with the existing large-scale biphenyl sulfonated alkali fusion method for preparing biphenol, the synthesis process of biphenol has the advantages of less pollution, mild reaction, controllable reaction process and simple equipment, and has high industrial value.
Examples
Example 1
150ml of dichloroethane, 30.8g of biphenyl and 15.7g of acetyl chloride are added into a 500ml four-necked flask, 28.8g of aluminum trichloride is added in portions under ice bath cooling, and the temperature is controlled between 0 ℃ and 10 ℃. Stirring is continued for 0.5 hour after the addition, the ice bath is removed, the temperature is naturally raised to room temperature, stirring is continued for 0.5 hour, and liquid phase monitoring is carried out. After the reaction, the obtained solution was poured into 150ml of ice water, stirred for 20min, and allowed to stand for delamination. The lower layer was washed with water, the organic layer was distilled off about 1/3, and the remaining residual liquid was directly used for the next reaction.
Adding the solution after the reaction treatment in the previous step, 40g of maleic anhydride and 100ml of dichloroethane into a 500ml four-mouth bottle, cooling to below 10 ℃, dropwise adding 27.2g of hydrogen peroxide with the concentration of 50%, controlling the temperature between 0 and 10 ℃, continuously stirring for 2.0h after the addition, and adding 0.5g of zinc powder. Stirring at room temperature for 12.0 hours, filtering the obtained solution, standing the filtrate, and removing a water layer to obtain a reaction liquid of the next reaction, refluxing and separating the filter cake maleic acid by dimethylbenzene to obtain maleic anhydride, directly using the maleic anhydride in the reaction process of secondary oxidation, and directly using the redundant maleic anhydride in the next reaction batch.
And adding 20g of maleic anhydride obtained by the reaction treatment in the previous step into the obtained reaction liquid, dropwise adding 13.6g of hydrogen peroxide with the concentration of 50%, adding 0.2g of zinc powder, repeating the first dropwise adding and reacting process, and after the reaction is finished, evaporating dichloroethane at normal pressure and then evaporating the solvent under reduced pressure to obtain a light yellow solid, wherein the distilled dichloroethane is directly added into the next batch for reaction.
To a 500ml reaction flask, the pale yellow solid, 100ml of methanol, 24g of sodium hydroxide and 100ml of water were added, and the mixture was refluxed for 1.0 hour, followed by monitoring the reaction in a liquid phase. After the reaction conversion is finished, the temperature is reduced below 20 ℃, 60ml of hydrochloric acid with the concentration of 35 percent is dripped, the PH value is regulated to be 3-4, the mixture is stirred for 0.5 hour, and the crude product of biphenol is obtained by filtering, washing and drying about 28.0g.
The crude biphenol product is further subjected to recrystallization treatment: the slurry was treated with isopropanol and the white powdered solid bisphenol was filtered to dryness at about 25.0g.
The obtained biphenol is characterized, the nuclear magnetic hydrogen spectrum of the biphenol is shown in figure 1, and the structure of the final product is further proved to be obtained.
The invention has been described in detail with reference to preferred embodiments and illustrative examples. It should be noted, however, that these embodiments are merely illustrative of the present invention and do not limit the scope of the present invention in any way. Various improvements, equivalent substitutions or modifications can be made to the technical content of the present invention and its embodiments without departing from the spirit and scope of the present invention, which all fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (3)

1. The process for synthesizing the diphenol is characterized by comprising the following steps of:
step 1, preparing the biacetophenone, which specifically comprises the following steps:
step 1-1, adding biphenyl, acetyl chloride, a catalyst and an organic solvent dichloroethane into a reactor for reaction, wherein the catalyst is aluminum trichloride, the catalyst is added under the ice bath condition, the ice bath temperature is between 0 and 10 ℃,
step 1-2, after the reaction is finished, carrying out post-treatment to obtain the diacetone;
step 2, oxidizing and rearranging the diacetone to obtain felbinac, wherein the step 2 comprises the following steps:
step 2-1, adding diacetone, oxidant and organic solvent dichloroethane into a reactor to react, wherein the oxidant is maleic anhydride and hydrogen peroxide, dropping 50% hydrogen peroxide at a temperature below 10 ℃ and controlling the temperature between 0 and 10 ℃,
adding a catalyst which is zinc powder,
step 2-2, after the reaction is finished, carrying out post-treatment to obtain felbinac,
carrying out secondary oxidation rearrangement on the felbinac obtained in the step 2-2;
step 3, carrying out hydrolysis reaction on felbinac to obtain biphenol, wherein step 3 comprises the following steps:
step 3-1, adding materials including felbinac, methanol, sodium hydroxide and water into a reactor to react,
step 3-2, acidifying the solution obtained in the step 3-1, regulating the pH value to be 3-4,
and 3-3, performing post-treatment to obtain the diphenol.
2. The process according to claim 1, wherein in step 1-2, the post-treatment comprises: stirring, standing, separating and washing.
3. The process according to claim 1, wherein in step 2-2, the post-treatment comprises: filtering, standing and separating.
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