CN113004144B - Synthesis method of perfluorobisphenol A - Google Patents
Synthesis method of perfluorobisphenol A Download PDFInfo
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- CN113004144B CN113004144B CN202110254026.9A CN202110254026A CN113004144B CN 113004144 B CN113004144 B CN 113004144B CN 202110254026 A CN202110254026 A CN 202110254026A CN 113004144 B CN113004144 B CN 113004144B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
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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
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
Abstract
The invention discloses a synthesis method of perfluorobisphenol A, belonging to the technical field of organic synthesis and comprising the following steps: s1, 2,3,5, 6-tetrafluoro-4- (1,1,1,3,3, 3-hexafluoro-2-hydroxypropane-2-yl) phenol, and synthesizing a compound of formula (II) through esterification reaction; s2 coupling the compound of formula (II) with tetrafluorophenol under the action of acid catalysis to synthesize a compound of formula (III), namely perfluorobisphenol A; the method has the advantages of short route, simple post-treatment, easily obtained raw materials, mild reaction conditions, easy control, high purity of the obtained product, high yield and batch production and application.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of perfluorobisphenol A.
Background
Bisphenol A is an important organic chemical raw material, is an important derivative of phenol and acetone, and is mainly used for producing various high polymer materials such as polycarbonate, epoxy resin, polysulfone resin, polyphenyl ether resin and the like. Can also be used in fine chemical products such as plasticizers, flame retardants, antioxidants, heat stabilizers, rubber antioxidants, pesticides, coatings and the like. Bisphenol a is used in the manufacture of plastic (milk) bottles, drinking cups for toddlers, and can internal coatings for food and beverage (milk powder). However, bisphenol a can also cause endocrine disorders, threatening the health of the fetus and children. Cancer and obesity caused by metabolic disorders are also considered to be associated therewith. The perfluorinated bisphenol A is used for replacing bisphenol A to synthesize a material, has more excellent thermal stability, solubility, flame resistance, oxidation resistance, light transmittance, wear resistance, oil resistance and low temperature resistance, can reduce dielectric constant, crystallinity and water absorption, can be widely applied to the fields of medicines, pesticides, synthetic materials, microelectronics, optics, aerospace and the like, and particularly has profound significance as a raw material for synthesizing a high polymer material in a special field.
However, the conventional synthesis method of perfluorobisphenol a is still immature, the common method is to catalyze the reaction of hexafluoroacetone and phenol by strong acid, the common acid is hydrogen fluoride and trifluoromethanesulfonic acid, the high temperature and high pressure have high requirements on equipment, and the success rate of synthesizing perfluorobisphenol a is low, so that a preparation method of perfluorobisphenol a is needed.
Disclosure of Invention
In order to solve the problems, the invention provides a synthesis method of perfluorobisphenol A, which has the advantages of simple synthesis route and high yield and is suitable for batch production and application.
A method for synthesizing perfluorobisphenol A comprises the following steps:
s1, carrying out esterification reaction on the compound of the formula (I) and trifluoromethanesulfonic anhydride or trifluoroacetyl chloride under the action of base catalysis to synthesize a compound of the formula (II);
s2, under the atmosphere of inert gas, coupling the compound of the formula (II) prepared by the S1 with tetrafluorophenol under the action of acid catalysis to synthesize a compound of a formula (III), namely perfluorobisphenol A;
the synthetic route is as follows:
wherein R is trifluoromethanesulfonyl or trifluoroacetyl.
Preferably, in S1, the base is triethylamine, N-dimethylaniline or pyridine.
Preferably, in S1, the compound of formula (i): trifluoromethanesulfonic anhydride or trifluoroacetyl chloride: the mass ratio of the alkali is 2.8-4.4: 1.2-2.7: 1.
Preferably, in S1, the reaction temperature is 40-60 ℃ and the reaction time is 5-6 h.
Preferably, in S1, after the reaction is completed, the reaction solution is washed with water to neutrality and concentrated to obtain the compound of formula (ii).
Preferably, in S2, the acid is one or more of sulfuric acid, phosphoric acid, chlorosulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, aluminum trichloride, titanium tetrachloride and boron tribromide.
Preferably, in S2, the compound of formula (ii): tetrafluorophenol: the mass ratio of the acid is 2.5-2.8: 1: 1.5-1.9.
Preferably, in S2, the reaction temperature is 80-180 ℃ and the reaction time is 20-30 h.
Preferably, in S2, the solvent is dichloromethane, dichloroethane, dibromoethane or dichlorobenzene.
Preferably, in S2, after the reaction is finished, washing with water to be neutral, and concentrating to obtain the perfluorobisphenol A.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a method for synthesizing perfluorobisphenol A, which takes 2,3,5, 6-tetrafluoro-4- (1,1,1,3,3, 3-hexafluoro-2-hydroxypropane-2-yl) phenol as a raw material, converts the phenol into active ester, and then couples with tetrafluorophenol under the catalysis of acid to successfully synthesize perfluorobisphenol A;
(2) the method has the advantages of short route, simple post-treatment, easily obtained raw materials, mild reaction conditions, easy control, high purity (99.0144%) of the obtained product, high yield (72%), and batch production and application.
Drawings
FIG. 1 is a gas chromatogram of perfluorobisphenol A obtained in example 1;
FIG. 2 is a gas mass spectrum of perfluorobisphenol A obtained in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described below with reference to the following specific embodiments and the accompanying drawings, but the embodiments are not meant to limit the present invention. The following detection methods, unless otherwise specified, are all conventional methods; the raw materials and reagents, unless otherwise specified, are conventional materials and are commercially available.
The invention provides a synthesis method of perfluorobisphenol A, which comprises the following steps:
s1, carrying out esterification reaction on the compound of the formula (I) and trifluoromethanesulfonic anhydride or trifluoroacetyl chloride under the action of base catalysis to synthesize a compound of the formula (II);
s2, under the atmosphere of inert gas, coupling the compound of the formula (II) prepared by the S1 with tetrafluorophenol under the action of acid catalysis to synthesize a compound of a formula (III), namely perfluorobisphenol A;
the synthetic route is as follows:
wherein R is trifluoromethanesulfonyl or trifluoroacetyl.
The general synthesis method of the compound shown in the formula (I), namely 2,3,5, 6-tetrafluoro-4- (1,1,1,3,3, 3-hexafluoro-2-hydroxypropane-2-yl) phenol, specifically comprises the following steps:
synthesis of 2,3,5, 6-tetrafluoro-anisole: under the protection of nitrogen, 24g of sodium hydride is added into 120ml of tetrahydrofuran, tetrahydrofuran solution of 2,3,5, 6-tetrafluoro-phenol (166.07 g of 2,3,5, 6-tetrafluoro-phenol and 1660ml of tetrahydrofuran) is dripped, the temperature is controlled to be 25-30 ℃, stirring reaction is carried out for 2h, 141.9g of methyl iodide is dripped, the temperature is controlled to be 35-40 ℃, stirring reaction is carried out for 10h, the reaction solution is slowly added into 5000ml of water, 1660ml of dichloromethane is added for extraction, water washing is carried out until the solution is neutral, anhydrous magnesium sulfate is dried, and 175g of liquid product is obtained after concentration.
Synthesis of 2,3,5, 6-tetrafluoro-4- (1,1,1,3,3, 3-hexafluoro-2-hydroxypropan-2-yl) phenol: under the protection of nitrogen, adding 60g of the obtained 2,3,5, 6-tetrafluoro-anisole into 600ml of tetrahydrofuran, cooling liquid nitrogen to-78 ℃, dropwise adding 199ml of butyl lithium (concentration is 2mol/L), after dropwise adding, keeping the temperature for reaction for 2h, introducing 82.9g of hexafluoroacetone, keeping the temperature for reaction for 2h, heating the reaction liquid to room temperature, pouring the reaction liquid into 2L of water, adding 500ml of dichloromethane for extraction, washing the mixture to be neutral, drying anhydrous magnesium sulfate, and concentrating to obtain 110g of liquid product.
The method for synthesizing perfluorobisphenol A according to the present invention is specifically described below with reference to examples 1 to 3.
Example 1
A method for synthesizing perfluorobisphenol A comprises the following steps:
the first step is as follows: adding 173ml of tetrahydrofuran into 34.6g of 2,3,5, 6-tetrafluoro-4- (1,1,1,3,3, 3-hexafluoro-2-hydroxypropane-2-yl) phenol, adding 10.1g of triethylamine, dropwise adding 28.2g of trifluoromethanesulfonic anhydride while stirring and controlling the temperature at 40 ℃, reacting for 5 hours, pouring the reaction solution into water, adding 200ml of dichloromethane, washing with water to be neutral, and concentrating to obtain 46.4g of a liquid product;
the second step is that: under the protection of nitrogen, adding 200ml of dichloroethane and 20ml of trifluoroacetic acid into the obtained intermediate (46.4g) and 16.6g of tetrafluorophenol, stirring, heating to reflux, reacting for 20 hours, pouring the reaction solution into water, washing with water to be neutral, and concentrating to obtain 44.6g of perfluorobisphenol A, and recrystallizing with toluene to obtain 31.2g of refined product with the content of 99.2% and the yield of 70%.
Example 2
A method for synthesizing perfluorobisphenol A comprises the following steps:
the first step is as follows: adding 173ml of tetrahydrofuran into 34.6g of 2,3,5, 6-tetrafluoro-4- (1,1,1,3,3, 3-hexafluoro-2-hydroxypropane-2-yl) phenol, adding 12.1g of N, N-dimethylaniline, stirring, controlling the temperature at 60 ℃, dropwise adding 13.2g of trifluoroacetyl chloride, reacting for 6h, pouring the reaction solution into water, adding 200ml of dichloromethane, washing with water to be neutral, and concentrating to obtain 42.8g of a liquid product;
the second step is that: under the protection of nitrogen, 200ml of dichlorobenzene and 15ml of titanium tetrachloride are added into the obtained intermediate (42.8g) and 16.6g of tetrafluorophenol under the protection of nitrogen, the temperature is raised to 170 ℃, the reaction is carried out for 30 hours, the reaction liquid is poured into water, the water washing is neutral, the concentration is carried out, 44.6g of perfluorobisphenol A is obtained, and the fine product 30.3g, the content is 99.0 percent and the yield is 68 percent are obtained through the recrystallization of toluene.
Example 3
A method for synthesizing perfluorobisphenol A comprises the following steps:
the first step is as follows: adding 173ml of tetrahydrofuran into 34.6g of 2,3,5, 6-tetrafluoro-4- (1,1,1,3,3, 3-hexafluoro-2-hydroxypropane-2-yl) phenol, adding 7.9g of pyridine, dropwise adding 13.2g of trifluoroacetyl chloride while stirring and controlling the temperature to be 50 ℃, reacting for 6 hours, pouring the reaction solution into water, adding 200ml of dichloromethane, washing with water to be neutral, and concentrating to obtain 42.8g of a liquid product;
the second step is that: under the protection of nitrogen, 200ml of dibromoethane, 5ml of titanium tetrachloride and 10ml of chlorosulfonic acid are added into the obtained intermediate (42.8g) and 16.6g of tetrafluorophenol, the obtained intermediate and the tetrafluorophenol are stirred, the temperature is raised to 130 ℃, the reaction is carried out for 30 hours, the reaction solution is poured into water, the water washing is carried out for neutrality, and the concentration is carried out, so that 44.6g of perfluorobisphenol A is obtained, and the refined product 32.3g, the content of which is 99.0%, and the yield of which is 72% are obtained through the recrystallization of toluene.
The performances of the perfluorobisphenol a prepared in the examples 1 to 3 are similar, and the prepared perfluorobisphenol a is characterized by only taking the example 1 as the following, wherein fig. 1 is a perfluorobisphenol a gas chromatography analysis chart, as shown in fig. 1, the purity of the perfluorobisphenol a is 99.0144%, and fig. 2 is a perfluorobisphenol a gas mass spectrum, which shows that the molecular weight of the perfluorobisphenol a is 480 and is consistent with that of the target product. It can be shown that perfluorobisphenol a is successfully prepared by the present invention, and the route is simple, requiring only two steps: the method takes 2,3,5, 6-tetrafluoro-4- (1,1,1,3,3, 3-hexafluoro-2-hydroxypropane-2-yl) phenol as a raw material, firstly converts the phenol into active ester, then couples the active ester with tetrafluorophenol under the catalysis of acid, has simple post-treatment, easily obtained raw materials, mild reaction conditions and easy control, and obtains the product with high purity (99.0144%) and high yield (72%), which can be produced and applied in batches.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the appended claims and their equivalents.
Claims (8)
1. A method for synthesizing perfluorobisphenol A is characterized by comprising the following steps:
s1, carrying out esterification reaction on the compound of the formula (I) and trifluoromethanesulfonic anhydride or trifluoroacetyl chloride under the action of base catalysis to synthesize a compound of the formula (II);
the alkali is triethylamine, N-dimethylaniline or pyridine;
s2, under the atmosphere of inert gas, coupling the compound of the formula (II) prepared by the S1 with tetrafluorophenol under the action of acid catalysis to synthesize a compound of a formula (III), namely perfluorobisphenol A;
the acid is one or a mixture of chlorosulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, aluminum trichloride, titanium tetrachloride and boron tribromide;
the synthetic route is as follows:
wherein R is trifluoromethanesulfonyl or trifluoroacetyl.
2. The method for synthesizing perfluorobisphenol a according to claim 1, wherein in S1, the compound of formula (i): trifluoromethanesulfonic anhydride or trifluoroacetyl chloride: the mass ratio of the alkali is 2.8-4.4: 1.2-2.7: 1.
3. The method for synthesizing perfluorobisphenol A according to claim 1, wherein the reaction temperature in S1 is 40 to 60 ℃ and the reaction time is 5 to 6 hours.
4. The method for synthesizing perfluorobisphenol A according to claim 1, wherein the compound of formula (II) is obtained by washing the reaction mixture with water to neutrality and concentrating after the completion of the reaction in S1.
5. The method for synthesizing perfluorobisphenol a according to claim 1, wherein in S2, the compound of formula (ii): tetrafluorophenol: the mass ratio of the acid is 2.5-2.8: 1: 1.5-1.9.
6. The method for synthesizing perfluorobisphenol A according to claim 1, wherein the reaction temperature in S2 is 80 to 180 ℃ and the reaction time is 20 to 30 hours.
7. The method for synthesizing perfluorobisphenol A according to claim 1, wherein the solvent used in S2 is dichloromethane, dichloroethane, dibromoethane, or dichlorobenzene.
8. The method for synthesizing perfluorobisphenol A according to claim 1, wherein the perfluorobisphenol A is obtained by washing S2 with water to neutrality and concentrating after completion of the reaction.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05229976A (en) * | 1992-02-18 | 1993-09-07 | Ukichi Akiyama | Production of tetrafluorobisphenol a |
| CN111574334A (en) * | 2020-04-16 | 2020-08-25 | 江汉大学 | Novel phenolic compound and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3299571B2 (en) * | 1992-10-27 | 2002-07-08 | 本州化学工業株式会社 | Novel fluorinated bisphenols and production method thereof |
| US5763674A (en) * | 1996-12-09 | 1998-06-09 | General Electric Company | High molecular weight dibenzoylresorcinol UV absorbers |
| US5990362A (en) * | 1998-08-31 | 1999-11-23 | General Electric Company | Method for preparing bisphenol A |
| JP4152655B2 (en) * | 2002-03-29 | 2008-09-17 | 出光興産株式会社 | Method for producing bisphenol A |
| JP3981334B2 (en) * | 2002-09-04 | 2007-09-26 | 出光興産株式会社 | Method for producing bisphenol A |
| WO2005051898A2 (en) * | 2003-11-20 | 2005-06-09 | Eli Lilly And Company | Vitamin d receptor modulators |
| CN101747154B (en) * | 2008-12-12 | 2013-06-05 | 南京理工大学 | Method for preparing bisphenol AF |
| CN110950740B (en) * | 2019-12-20 | 2022-07-26 | 湖南有色郴州氟化学有限公司 | Synthesis method of hexafluorobisphenol A |
| CN112409125B (en) * | 2020-11-30 | 2024-02-02 | 山东华夏神舟新材料有限公司 | Method for continuously preparing diaryl hexafluoropropane |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05229976A (en) * | 1992-02-18 | 1993-09-07 | Ukichi Akiyama | Production of tetrafluorobisphenol a |
| CN111574334A (en) * | 2020-04-16 | 2020-08-25 | 江汉大学 | Novel phenolic compound and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Enantioselective Phenolic α-Oxidation Using H2O2 via an Unusual Double Dearomatization Mechanism;Michael F. McLaughlin 等;《J.Am.Chem.Soc.》;20190130;第141卷;第2645-2651页 * |
| Some reactions of 3,5-di-tert-butyl-4-hydroxybenzyl acetate;Mukmeneva,N.A.等;《Zhurnal Obshchei Khimii》;19961231;第66卷(第10期);第1725-1727页 * |
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