CN111606784A - Synthetic method of 4, 4' -dihydroxybiphenyl - Google Patents
Synthetic method of 4, 4' -dihydroxybiphenyl Download PDFInfo
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- CN111606784A CN111606784A CN202010424591.0A CN202010424591A CN111606784A CN 111606784 A CN111606784 A CN 111606784A CN 202010424591 A CN202010424591 A CN 202010424591A CN 111606784 A CN111606784 A CN 111606784A
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- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
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Abstract
The invention provides a method for synthesizing 4, 4 '-dihydroxybiphenyl, which comprises the steps of taking biphenyl as an initial raw material, obtaining 4, 4' -dicyclopentyl biphenyl or 4, 4 '-dicyclohexyl biphenyl through Friedel-crafts alkylation reaction, obtaining hydroperoxide through oxidation reaction, and then carrying out cracking reaction, thus obtaining the target product 4, 4' -dihydroxybiphenyl.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing 4, 4' -dihydroxybiphenyl.
Background
4, 4' -dihydroxy biphenyl is an important organic intermediate and has wide application in the chemical field. Can be used as antioxidant of plastics, stabilizer of dye, anti-aging agent of rubber, etc., and can also be used for preparing excellent composite material and liquid crystal polymer. In recent years, the use of bisphenol a in the production of infant-related plastic products has been increasingly prohibited globally, and 4, 4' -dihydroxybiphenyl is the best alternative to bisphenol a.
At present, the method for industrially producing the 4, 4' -dihydroxybiphenyl on a large scale mainly comprises the following steps:
1. the preparation of 4, 4' -dihydroxybiphenyl from biphenyl and its derivatives by alkali fusion by sulfonation is described in US patent 6410238,
although the method has simple synthetic route and high yield, the reaction process adopts concentrated acid and strong alkali, the three wastes are large, the serious environmental pollution is caused, and in addition, the quality of the final product is not high due to the generation of a plurality of byproducts at high reaction temperature.
2. Prepared by oxidizing and coupling a phenol compound and then removing tert-butyl, refer to Japanese patent JPH04338347A,
the method has more steps and complex route, wherein the selectivity of the first step reaction is not high, and the overall yield is influenced.
In the last two years, the invention patent proposes a one-step method for synthesizing 4, 4' -dihydroxybiphenyl:
patent CN108715574A proposes a method for preparing 4, 4' -dihydroxybiphenyl by one-step coupling reaction in ionic liquid by taking p-halophenol as a raw material and cupric salt and rare earth metal samarium as catalysts,
the catalyst of the method has higher requirement and large using amount, is difficult to recover and separate, and is not suitable for industrial production;
patent CN109896925A proposes a method for synthesizing 4, 4' -dihydroxybiphenyl in one step by using biphenyl as a raw material, hydrogen peroxide as an oxidant and a chromium-loaded HZSM-5 molecular sieve as a catalyst,
although the method has simple process and less three wastes, the preparation process of the catalyst at the early stage is complex, and the overall economic benefit is influenced.
As can be seen from the above, the high-purity 4, 4 '-dihydroxybiphenyl cannot be produced in large quantity at home at present, the use of the 4, 4' -dihydroxybiphenyl also depends on the import to the United states, and the domestic prior art has the following problems:
firstly, the reaction conditions of strong acid and strong alkali and high temperature are used, so that the energy consumption is high, the requirement on equipment is high, and a large amount of waste acid, waste water and high-temperature coking waste are generated and are difficult to treat, so that the environment is seriously polluted;
secondly, in the production process, no matter the temperature is high or the side products are more due to poor reaction selectivity, the separation and purification are difficult, the purity and the appearance of the final product are influenced, and the method is difficult to be used in high-grade manufacturing products.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a method for synthesizing 4, 4 '-dihydroxybiphenyl, which comprises the steps of taking biphenyl as an initial raw material, obtaining 4, 4' -dicyclopentyl biphenyl or 4, 4 '-dicyclohexyl biphenyl through a Friedel-crafts alkylation reaction, obtaining hydroperoxide through an oxidation reaction, and then carrying out a cracking reaction to obtain the target product 4, 4' -dihydroxybiphenyl, wherein the whole synthesis process is high in selectivity, high in yield, convenient to operate, green and environment-friendly, and suitable for industrial production.
The invention provides a method for synthesizing 4, 4' -dihydroxybiphenyl, which comprises the following steps:
(1) carrying out Friedel-crafts alkylation reaction on biphenyl to obtain 4, 4 '-dicyclopentyl biphenyl or 4, 4' -dicyclohexyl biphenyl;
(2) 4, 4 '-dicyclopentylbiphenyl or 4, 4' -dicyclohexylbiphenyl is subjected to oxidation reaction to obtain 4, 4 '-dicyclopentylbiphenyl hydroperoxide or 4, 4' -dicyclohexylbiphenyl hydroperoxide;
(3) 4, 4' -dicyclopentylbiphenyl hydroperoxide or 4, 4' -dicyclohexyl biphenyl hydroperoxide is subjected to cracking reaction to obtain 4, 4' -dihydroxybiphenyl.
Preferably, in the step (1), the biphenyl, cyclopentene, cyclohexene or halogenated cyclopentane, halogenated cyclohexane or cyclopentanol, and cyclohexanol are subjected to friedel-crafts alkylation reaction under the condition of a first catalyst to obtain 4, 4 '-dicyclopentylbiphenyl or 4, 4' -dicyclohexylbiphenyl;
the synthetic route is as follows:
in the step, biphenyl, cyclopentene, cyclohexene or halogenated cyclopentane, halogenated cyclohexane or cyclopentanol and cyclohexanol are selected to react in a Friedel-crafts alkylation reaction, the positioning effect of phenyl on the biphenyl and the large molecular structure of the phenyl and a five-membered ring or a six-membered ring are utilized, a strong steric hindrance effect can be formed, and a new substituent can only enter the para position of a benzene ring almost, so that the possibility of generating a byproduct in the reaction is greatly reduced.
Preferably, the halogenated cyclopentane is chloro-cyclopentane or bromo-cyclopentane, and the halogenated cyclohexane is chloro-cyclohexane or bromo-cyclohexane.
Preferably, the first catalyst is a lewis acid, protonic acid, or molecular sieve catalyst;
preferably, the first catalyst is aluminum trichloride AlCl3FeCl, ferric chloride3Boron trifluoride BF3Sulfuric acid H2SO4Phosphoric acid H3PO4Hydrogen fluoride HF, MCM-22 molecular sieve or a combination of more than one of the above components.
Preferably, cyclopentene, cyclohexene, halogenated cyclopentane, halogenated cyclohexane, cyclopentanol, or cyclohexanol is used in an amount of 2 to 3 times, preferably 2.2 to 2.5 times, the molar amount of biphenyl.
Preferably, the first catalyst is used in an amount of 1 to 100% by mole based on the amount of biphenyl.
Preferably, the reaction temperature of the Friedel-crafts alkylation reaction is-10-50 ℃, and the reaction solvent is dichloromethane, trichloromethane, 1, 2-dichloroethane, chlorobenzene, bromobenzene or 1, 2-dichlorobenzene.
Preferably, in the step (2), 4 '-dicyclopentylbiphenyl or 4, 4' -dicyclohexylbiphenyl is subjected to oxidation reaction with an oxidant under the conditions of a second catalyst and an initiator to obtain 4, 4 '-dicyclopentylbiphenyl hydroperoxide or 4, 4' -dicyclohexylbiphenyl hydroperoxide;
the synthetic route is as follows:
preferably, the oxidant is air or oxygen;
the second catalyst is one or the combination of more of N-hydroxyphthalimide NHPI, 4-amino-N-hydroxyphthalimide, 3-amino-N-hydroxyphthalimide, N-hydroxyphenetetrachlorophthalimide, N-hydroxytetrabromophthalimide, N-hydroxytriphenylimide, N-hydroxyphenyl-1, 2, 4-trimethylimide, pyridine-2, 3-dicarboximide, N-hydroxysuccinimide or N-hydroxy (tartrimide);
the initiator is an organic peroxy acid, preferably one or a combination of more of peroxyformic acid, peroxyacetic acid, peroxybenzoic acid, trifluoroperacetic acid or m-chloroperoxybenzoic acid.
In the step, 4 '-dicyclopentylbiphenyl or 4, 4' -dicyclohexylbiphenyl is oxidized by air or oxygen to obtain 4, 4 '-dicyclopentylbiphenyl hydroperoxide or 4, 4' -dicyclohexylbiphenyl hydroperoxide, and the oxidant in the reaction is only oxygen or oxygen in the air, so that the cost is effectively reduced.
Preferably, the second catalyst is used in an amount of 1 to 15% of the molar amount of 4, 4 '-dicyclopentylbiphenyl or 4, 4' -dicyclohexylbiphenyl; the dosage of the initiator is 1-15% of the molar weight of the 4, 4 '-dicyclopentylbiphenyl or the 4, 4' -dicyclohexylbiphenyl.
Preferably, the reaction temperature of the oxidation reaction is 0-70 ℃, the reaction time is 5-24h, and the reaction solvent is acetonitrile or propionitrile.
Preferably, in the step (3), 4' -dicyclopentylbiphenyl hydroperoxide or 4, 4' -dicyclohexylbiphenyl hydroperoxide is subjected to a cracking reaction under the condition of an acid catalyst to obtain 4, 4' -dihydroxybiphenyl;
the synthetic route is as follows:
in the step, 4' -dicyclopentylbiphenyl hydroperoxide or 4, 4' -dicyclohexylbiphenyl hydroperoxide is decomposed under the condition of an acid catalyst to obtain a target product 4, 4' -dihydroxybiphenyl, and byproducts cyclopentanone or cyclohexanone in the step are chemical raw materials which are widely applied and very important, so that the synthetic route has very high economic benefit.
Preferably, the acid catalyst is one or a combination of more of sulfuric acid, phosphoric acid or p-toluenesulfonic acid; preferably, the acid catalyst is used in an amount of 1 to 10% by mole based on the amount of 4, 4 '-dicyclopentylbiphenyl hydroperoxide or 4, 4' -dicyclohexylbiphenyl hydroperoxide.
Preferably, the reaction temperature of the cracking reaction is 0-50 ℃, and the reaction time is 1-10 h.
Compared with the traditional production method, the invention has the following advantages that:
1. the invention can almost avoid strong acid and strong alkaline substances and high temperature reaction, greatly reduces the production risk factor and the corrosion to equipment, effectively reduces three wastes, and is more environment-friendly;
2. the method can solve the problems of more byproducts and difficult separation caused by difficult directional substitution of the substituent on the benzene ring, so that the reaction selectivity is high, the product is single, and the product purity is high;
3. the raw materials of the invention are cheap and easy to obtain, only a small amount of catalyst and free radical initiator are needed in the reaction, the oxidant is oxygen or oxygen in the air, the reaction cost is low, the yield is high, and the byproduct cyclopentanone or cyclohexanone also has high economic benefit, thus being very suitable for industrial production.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 4, 4' -dihydroxybiphenyl obtained in example 1;
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A method for synthesizing 4, 4' -dihydroxybiphenyl comprises the following steps:
(1) putting anhydrous aluminum trichloride (0.4g and 0.003mol) into a dry 500mL three-neck flask, adding biphenyl (46.3g and 0.3mol) and trichloromethane (250mL), stirring to completely dissolve the biphenyl, slowly dropwise adding cyclopentene (40.9g and 0.6mol) under the stirring condition, controlling the reaction temperature at 0 ℃, stirring at room temperature for 10 hours after dropwise adding, taking a small amount of organic phase for gas chromatography analysis, wherein the biphenyl conversion rate is 98.5%, then pouring the reaction system into a separating funnel, washing 3 times with 100mL of water, carrying out reduced pressure distillation on the organic phase, recovering the solvent to obtain a crude solid product of 4, 4' -dicyclopentylbiphenyl, and the content of the product is 83.5% by a gas chromatography internal standard method;
(2) adding the crude solid product obtained in the step (1) and acetonitrile (200mL) into a 500mL three-neck flask, stirring to dissolve, then adding N-hydroxyphthalimide (0.4g, 0.00245mol) and peracetic acid (0.19g, 0.00245mol), introducing air at the temperature of below 5 ℃, stirring to react for 24 hours, measuring the conversion rate of raw materials by gas chromatography to be 99%, carrying out reduced pressure distillation to recover the acetonitrile, cooling to room temperature, adding cyclopentanone (200mL) into the residue, adding 1 wt% of sodium hydroxide solution (19.6g), stirring for 1 hour, standing and demixing to obtain an organic phase;
(3) transferring the organic phase obtained in the step (2) into a 500mL three-neck flask, adding 98 wt% concentrated sulfuric acid (0.25g, 0.00243mol), stirring and reacting at 0 ℃ for 10 hours, neutralizing the pH of the system to 6-7 with saturated sodium bicarbonate after the reaction is finished, standing and layering, distilling the organic phase to recover cyclopentanone, recrystallizing the residual white solid with ethanol, and drying to obtain white crystalline 4, 4 '-dihydroxybiphenyl with the purity of 99.0%, wherein the total amount of 40g and the total yield is 70.9%, and the nuclear magnetic hydrogen spectrum of the 4, 4' -dihydroxybiphenyl is shown in FIG. 1.
Example 2
The specific reaction process and detection method are the same as those in example 1, except that cyclopentene is changed into cyclohexene, and the obtained product, 4' -dihydroxybiphenyl, has a final yield of 71.5%.
Example 3
The specific reaction process and detection method are the same as those in example 1, except that cyclopentene is changed into chlorocyclohexane, and the obtained product, 4' -dihydroxybiphenyl, has a final yield of 71.3%.
Example 4
The specific reaction process and detection method are the same as those in example 1, except that cyclopentene is changed into cyclohexanol to obtain 4, 4' -dihydroxybiphenyl, and the final yield is 69.9%.
Example 5
A method for synthesizing 4, 4' -dihydroxybiphenyl comprises the following steps:
(1) adding biphenyl (123.4g, 0.8mol), cyclopentene (163.5g, 2.4mol) and chlorobenzene (500mL) into a high-pressure reaction kettle, uniformly stirring, cooling to-10 ℃, slowly introducing hydrogen fluoride gas (16g, 0.8mol) into the high-pressure reaction kettle for multiple times, continuously stirring at 50 ℃ for 2 hours after the reaction is finished, and taking a small amount of organic phase for gas chromatography analysis, wherein the conversion rate of the biphenyl is 99%; adding 200mL of water into the kettle, adjusting the pH value to be neutral by using sodium hydroxide, standing for layering, carrying out reduced pressure distillation on an organic phase, and recovering a solvent to obtain a solid crude product of 4, 4' -dicyclopentylbiphenyl, wherein the content of the product is 91% by using a gas chromatography internal standard method;
(2) adding the crude solid product obtained in the step (1) and acetonitrile (500mL) into a 1000mL three-neck flask, stirring to dissolve, then adding N-hydroxysuccinimide (12.4g, 0.108mol) and peroxybenzoic acid (14.9g, 0.108mol), introducing air at normal temperature, stirring to react for 18 hours, measuring the conversion rate of raw materials by gas chromatography to be 99%, carrying out reduced pressure distillation to recover acetonitrile, cooling to room temperature, adding cyclopentanone (500mL) into the residue, then adding 20 wt% of sodium hydroxide aqueous solution (43.2g), stirring for 1 hour, standing to separate layers, and obtaining an organic phase;
(3) and (3) transferring the organic phase obtained in the step (2) into a 1000mL three-neck flask, adding p-toluenesulfonic acid (12.3g, 0.0714mol), stirring and reacting at 50 ℃ for 1 hour, continuously neutralizing the pH of the system to 6-7 with saturated sodium bicarbonate at 50 ℃ after the reaction is finished, standing and layering, distilling the organic phase to recover cyclopentanone, wherein the residual off-white solid is 4, 4' -dihydroxybiphenyl, and the total yield is 80.2% after drying, and the purity is 93.4%.
Example 6
The specific reaction process and detection method are the same as those in example 5, except that cyclopentene is changed into cyclohexene, and the obtained product, 4' -dihydroxybiphenyl, is not recrystallized, the purity is 93.2%, and the final yield is 79.8%.
Example 7
The specific reaction process and detection method are the same as those in example 5, except that cyclopentene is changed into chlorocyclopentane, and the obtained product, 4' -dihydroxybiphenyl, is not recrystallized, has a purity of 93.5% and a final yield of 79.4%.
Example 8
The specific reaction process and detection method are the same as those in example 5, except that cyclopentene is changed into cyclopentanol, and the obtained product, 4' -dihydroxybiphenyl, is not recrystallized, has a purity of 92.7%, and has a final yield of 77.6%.
Example 9
(1) Adding biphenyl (123.4g, 0.8mol), cyclopentene (136.2g, 2mol) and 1, 2-dichloroethane (500mL) into a high-pressure reaction kettle, uniformly stirring, cooling to 0 ℃, slowly introducing hydrogen fluoride gas (8g, 0.4mol) and boron trifluoride gas (13.6g, 0.2mol) into the high-pressure reaction kettle for multiple times, keeping the temperature not more than 5 ℃, continuously stirring for 2 hours, taking a small amount of organic phase for gas chromatography analysis, wherein the biphenyl conversion rate is 99%; adding 200mL of water into the kettle, adjusting the pH value to be neutral by using sodium hydroxide, standing for layering, carrying out reduced pressure distillation on an organic phase, and recovering a solvent to obtain a solid crude product of 4, 4' -dicyclopentylbiphenyl, wherein the content of the product is 92% by using a gas chromatography internal standard method;
(2) adding the solid crude product obtained in the step (1) and acetonitrile (500mL) into a 1000mL three-neck flask, stirring to dissolve, adding 4-amino-N-hydroxyphthalimide (13.0g, 0.073mol) and perbenzoic acid (10.1g, 0.073mol), introducing air at normal temperature, stirring to react for 10 hours, measuring the conversion rate of raw materials by gas chromatography to be 99%, carrying out reduced pressure distillation to recover the acetonitrile, cooling to room temperature, adding cyclopentanone (500mL) into the residue, adding 20 wt% of sodium hydroxide aqueous solution (29.2g), stirring for 1 hour, standing and demixing to obtain an organic phase;
(3) transferring the organic phase obtained in the step (2) into a 1000mL three-neck flask, adding perchloric acid (7.0g, 0.07mol), stirring and reacting at 50 ℃ for 1 hour, continuously neutralizing the pH of the system to 6-7 with saturated sodium bicarbonate at 50 ℃ after the reaction is finished, standing and layering, distilling the organic phase to recover cyclopentanone, wherein the residual off-white solid is 4, 4' -dihydroxybiphenyl, and the total yield is 125g, 93.5% and 78.5% after drying.
Example 10
The specific reaction process and detection method are the same as those in example 9, except that cyclopentene is changed into cyclohexene, and the obtained product, 4' -dihydroxybiphenyl, is not recrystallized, the purity is 93.5%, and the final yield is 79.7%.
Example 11
The specific reaction process and detection method are the same as those in example 9, except that cyclopentene is changed into bromocyclohexane, and the obtained product, 4' -dihydroxybiphenyl, is not recrystallized, has a purity of 93.2% and a final yield of 79.0%.
Example 12
The specific reaction process and detection method are the same as those in example 9 except that cyclopentene is changed into cyclohexanol, and the obtained product, 4' -dihydroxybiphenyl, is not recrystallized, has a purity of 92.2% and a final yield of 77.9%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical scope of the present invention, and equivalents and modifications thereof should be included in the technical scope of the present invention.
Claims (10)
1. A method for synthesizing 4, 4' -dihydroxybiphenyl is characterized by comprising the following steps:
(1) carrying out Friedel-crafts alkylation reaction on biphenyl to obtain 4, 4 '-dicyclopentyl biphenyl or 4, 4' -dicyclohexyl biphenyl;
(2) 4, 4 '-dicyclopentylbiphenyl or 4, 4' -dicyclohexylbiphenyl is subjected to oxidation reaction to obtain 4, 4 '-dicyclopentylbiphenyl hydroperoxide or 4, 4' -dicyclohexylbiphenyl hydroperoxide;
(3) 4, 4' -dicyclopentylbiphenyl hydroperoxide or 4, 4' -dicyclohexyl biphenyl hydroperoxide is subjected to cracking reaction to obtain 4, 4' -dihydroxybiphenyl.
2. The method for synthesizing 4, 4' -dihydroxybiphenyl according to claim 1, wherein in step (1), biphenyl and cyclopentene or cyclohexene are subjected to friedel-crafts alkylation reaction under the condition of a first catalyst to obtain 4, 4' -dicyclopentylbiphenyl or 4, 4' -dicyclohexylbiphenyl;
the synthetic route is as follows:
or in the step (1), carrying out Friedel-crafts alkylation reaction on biphenyl and halogenated cyclopentane or halogenated cyclohexane under the condition of a first catalyst to obtain 4, 4 '-dicyclopentylbiphenyl or 4, 4' -dicyclohexylbiphenyl;
the synthetic route is as follows:
preferably, the halogenated cyclopentane is chloro cyclopentane or bromo cyclopentane, and the halogenated cyclohexane is chloro cyclohexane or bromo cyclohexane;
or, in the step (1), carrying out Friedel-crafts alkylation reaction on biphenyl and cyclopentanol or cyclohexanol under the condition of a first catalyst to obtain 4, 4 '-dicyclopentylbiphenyl or 4, 4' -dicyclohexylbiphenyl;
the synthetic route is as follows:
3. the method of synthesizing 4, 4' -dihydroxybiphenyl according to claim 2, wherein said first catalyst is a lewis acid, a protonic acid, or a molecular sieve catalyst; preferably, the first catalyst is aluminum trichloride AlCl3FeCl, ferric chloride3Boron trifluoride BF3Sulfuric acid H2SO4Phosphoric acid H3PO4Hydrogen fluoride HF, MCM-22 molecular sieve or a combination of more than one of the above components.
4. The method for synthesizing 4, 4' -dihydroxybiphenyl according to claim 2 or 3, wherein cyclopentene, cyclohexene, halogenated cyclopentane, halogenated cyclohexane, cyclopentanol, or cyclohexanol is used in an amount of 2 to 3 times the molar amount of biphenyl.
5. The method for synthesizing 4, 4' -dihydroxybiphenyl according to any one of claims 2-4, wherein the amount of the first catalyst is 1-100% by mole of the biphenyl.
6. The method for synthesizing 4, 4' -dihydroxybiphenyl according to any one of claims 1-5, wherein in step (2), 4' -dicyclopentylbiphenyl or 4, 4' -dicyclohexylbiphenyl is subjected to an oxidation reaction with an oxidizing agent under the conditions of a second catalyst and an initiator to obtain 4, 4' -dicyclopentylbiphenyl hydroperoxide or 4, 4' -dicyclohexylbiphenyl hydroperoxide;
the synthetic route is as follows:
7. the method of synthesizing 4, 4' -dihydroxybiphenyl according to claim 6, wherein said oxidizing agent is air or oxygen;
the second catalyst is one or the combination of more of N-hydroxyphthalimide NHPI, 4-amino-N-hydroxyphthalimide, 3-amino-N-hydroxyphthalimide, N-hydroxyphenetetrachlorophthalimide, N-hydroxytetrabromophthalimide, N-hydroxytriphenylimide, N-hydroxyphenyl-1, 2, 4-trimethylimide, pyridine-2, 3-dicarboximide, N-hydroxysuccinimide or N-hydroxy (tartrimide);
the initiator is an organic peroxy acid, preferably one or a combination of more of peroxyformic acid, peroxyacetic acid, peroxybenzoic acid, trifluoroperacetic acid or m-chloroperoxybenzoic acid.
8. The method for synthesizing 4, 4' -dihydroxybiphenyl according to claim 6 or 7, wherein the amount of the second catalyst is 1-15% of the molar amount of 4, 4' -dicyclopentylbiphenyl or 4, 4' -dicyclohexylbiphenyl; the dosage of the initiator is 1-15% of the molar weight of the 4, 4 '-dicyclopentylbiphenyl or the 4, 4' -dicyclohexylbiphenyl.
9. The method for synthesizing 4, 4 '-dihydroxybiphenyl according to any one of claims 1-8, wherein in step (3), 4' -dicyclopentylbiphenyl hydroperoxide or 4, 4 '-dicyclohexylbiphenyl hydroperoxide is subjected to a cleavage reaction under an acid catalyst to obtain 4, 4' -dihydroxybiphenyl;
the synthetic route is as follows:
10. the method for synthesizing 4, 4' -dihydroxybiphenyl according to claim 9, wherein the acid catalyst is one or more of sulfuric acid, phosphoric acid, or p-toluenesulfonic acid;
preferably, the acid catalyst is used in an amount of 1 to 10% by mole based on the amount of 4, 4 '-dicyclopentylbiphenyl hydroperoxide or 4, 4' -dicyclohexylbiphenyl hydroperoxide.
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| CN113683488A (en) * | 2021-08-09 | 2021-11-23 | 三峡大学 | Preparation method of 4,4' -dihydroxybiphenyl |
| CN115814854A (en) * | 2022-11-15 | 2023-03-21 | 中国海洋石油集团有限公司 | Catalyst for preparing 2,2' -biphenol and preparation method and application thereof |
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| CN115814854A (en) * | 2022-11-15 | 2023-03-21 | 中国海洋石油集团有限公司 | Catalyst for preparing 2,2' -biphenol and preparation method and application thereof |
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