CN103641692B - Preparation of novel fluorine-containing bisphenol compound - Google Patents
Preparation of novel fluorine-containing bisphenol compound Download PDFInfo
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- CN103641692B CN103641692B CN201310616241.4A CN201310616241A CN103641692B CN 103641692 B CN103641692 B CN 103641692B CN 201310616241 A CN201310616241 A CN 201310616241A CN 103641692 B CN103641692 B CN 103641692B
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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
- C07C37/16—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 by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/02—Lithium compounds
Abstract
The invention relates to a preparation method for preparing a novel fluorine-containing bisphenol compound, namely 2, 2-bis (4-(2, 4-diaminophenoxy) phenyl) hexafluoropropane. The preparation method comprises the following steps of lithiating m-dibromobenzene to prepare m-phenyl dilithium salt; performing addition reaction on the m-phenyl dilithium salt and hexafluoroacetone to prepare 1, 3-bis (2-hydroxy-hexafluoropropylidene) benzene; and performing condensation reaction on the 1, 3-bis (2-hydroxy-hexafluoropropylidene) benzene and phenol to prepare 1, 3-bis (1-(4-hydroxyphenyl)-hexafluoropropylidene) benzene. The preparation method provided by the invention has the advantages of simplicity in operation and low cost, the purity of the obtained product is more than 99%, and the preparation method is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of synthetic method of novel fluorine bisphenol cpd 1,3-bis-(2-(4-hydroxy phenyl)-hexafluoro propylidene base) benzene, belong to technical field of fine.
Technical background
Since coming out from phase early 1930s fluorine Lyons, organic fluorine chemistry shows flourish trend always, and fluorochemicals is almost deep into the every aspect of our daily life.After 1945, along with the beginning of cold war, various defence plan is for constantly developing fluorine chemistry and utilizing fluorochemicals to provide unfailing prime mover.To 50 ~ sixties in 20th century because the more product for civilian use is as Drugs Containing Fluorine, the appearance of agricultural chemicals and fluorine material has pushed organic fluorine chemistry research to Disciplinary Frontiers, if the material being called as Kazakhstan dragon (Halon) is the brominated fluorine-containing alkane derivative of a class, it is the chemical that a class is also widely used up to now.
1938, the polytetrafluoroethylene (PTFE) that E.I.Du Pont Company Pulan Ke Te (Plunkett) invents becomes the beginning [research and development of fluorine material of fluoropolymer investigation and application, the just aobvious loose tail benevolence chief editor in [day] limit, mountain, Wen Jianxun translates, press of East China University of Science, in June, 2003 first version].At present, the application of PTFE has expanded to the every field of the national economy such as petrochemical complex, machinery, electronic apparatus, building, weaving from national defence such as initial Aeronautics and Astronautics and military projects.The fluoro-resin ethylene-tetrafluoroethylene copolymer (ETFE) of high-intensity high-tenacity is another important fluoropolymer.Olympic venue " the Water Cube " is the Typical Representative of ETFE membrane structure building.In addition to polymers, a lot of micromolecular organic fluoride also has many-sided application in the electronics industry.Some fluorine-containing organic compound gas, as: CClF
3, CHF
3and C
2f
6deng, in the plasma etch processes manufacturing microchip, be used as etching reagent.At medicinal chemistry arts, in organic molecule, introduce fluorine atom is the important directions developing new cancer therapy drug, antitumor drug, antiviral, anti-inflammation drugs etc.In Modern Agriculture Crop protection, fluorine-containing agrochemicals have been widely used as weedicide, sterilant and sterilant etc.In recent years, positron emission computerized tomography (PET) diagnosis of technique tumour and cancer is utilized to be paid close attention to widely and apply.The fluoro-deoxyglucose of [18F]-2-(FDG) is cancer diagnosis PET probe [the T.Ritter.AFluoride-Derived Electrophilic Late-Stage Fluorination Reagent for PET Imaging.Science2011 be most widely used, 334,639].
Comprehensive domestic and foreign literature, at polymeric material field, the preparation containing multi-fluorinated compounds concentrates on polyimide, propylene oxide surfactants and fluorocarbon plastic monomer.Combine close carbonization industry Gastec N.V. reported be applied to polysulfone membrane fluorochemical monomer hexafluoro-BIS-A[river on James river lucky beautiful, hexafluoro-BIS-A polysulfone membrane and the method .CN90109597.4 that is separated for fluid thereof etc. carbonization].Minnesota Mining and Manufacturing Company discloses a kind of preparation method of important chemical intermediate hexafluoro-acetone, the method preparing Perfluoroacetone from Perfluoroacetone oxime, comprise heating Perfluoroacetone oxime (or its solvent complex) and a high-concentration inorganic acid with produce Perfluoroacetone [Y Qie Bukefu. the preparation .CN95191786.2 of Perfluoroacetone and oxime thereof].Chemspec International Ltd and Yang Xiaozi Co., Ltd. then disclose the preparation method of two (2-hydroxyl hexafluoro propyl group) phenol, be that raw material is obtained by reacting brominated intermediates with C5H6Br2N2O2 in solvent and sulfuric acid with two (2-hydroxyl hexafluoro propyl group) benzene, brominated intermediates is hydrolyzed under the basic metal aqueous solution and catalysts conditions two (2-hydroxyl hexafluoro propyl group) phenol, this is the important fluorine-containing phenolic compound of a class [Yang Jianhua, etc. the preparation method .CN200510028549_2 of two (2-hydroxyl hexafluoro propyl group) phenol].
Donghua University discloses a kind of fluorine-containing organic amine 2, two [the 4-(2 of 2-, 4-diamino phenoxy) phenyl] HFC-236fa, be applied in [Yu Xin sea .2 in the fluorine-containing polymeric amide of preparation and fluorinated polyimide material, the preparation method .CN200810034956_8 of two [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fa of 2-].Fluorine-containing organic amine also can be used as the fluorine-containing solidifying agent of epoxy resin, Donghua University and Shanghai Ruitu Electronic Materials Co., Ltd. disclose a kind of 2, two [the 4-(2 of 2-, 4-diamino phenoxy) phenyl] HFC-236fa type high temperature resistant epoxy adhesive and preparation method thereof, be that the component A of 1:1-2 and B component form by mass ratio, wherein, component A is by 2, the multipolymer that two [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fa of 2-and epoxy resin react; B component is by 2, two [the 4-(2 of 2-, 4-diamino phenoxy) phenyl] solid content that reacts in strong polar non-proton organic solvent and toluene of HFC-236fa and aromatic dicarboxylic anhydride is the homogeneous phase transparent solution [Yu Xinhai of 15%-30%, Deng .2, two [4-(2,4-diamino phenoxy) phenyl] the HFC-236fa type high temperature resistant epoxy adhesive of 2-and preparation method thereof .CN201310076575_7].University Of Ji'nan then discloses a kind of 2, the preparation method of two (4-carboxyl phenyl) HFC-236fa of 2-, with 2, two (4-aminomethyl phenyl) HFC-236fa of 2-is raw material, catalytic oxidation preparation [Zhang Shuxiang is carried out at HP and transition metal salt catalyst, oxygen oxidizer, Deng. the preparation method .CN201110400454_4 of 2,2-two (4-carboxyl phenyl) HFC-236fa under new catalyst system].
Although a lot of containing the report of multi-fluorinated compounds, the report about fluorine-containing phenolic compound is less, does not also find that the patent of 1,3-bis-(2-(4-hydroxy phenyl)-hexafluoro propylidene base) benzene is openly reported.The present invention discloses a kind of synthetic method of novel fluorine bisphenol cpd 1,3-bis-(2-(4-hydroxy phenyl)-hexafluoro propylidene base) benzene, easy and simple to handle, cost is low, productive rate is high and purity is high.The present invention discloses the important source material that a kind of novel fluorine bisphenol cpd 1,3-bis-(2-(4-hydroxy phenyl)-hexafluoro propylidene base) benzene is fluoro-containing macromolecule material.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of novel fluorine bisphenol cpd 1,3-bis-(2-(4-hydroxy phenyl)-hexafluoro propylidene base) benzene.
For achieving the above object, as shown in Figure 1, its feature is to comprise three consecutive steps synthetic method provided by the invention: a) lithiumation of m-dibromobenzene, preparation isophthalic dilithium salt; B) addition reaction of isophthalic dilithium salt and Perfluoroacetone, preparation 1,3-bis-(2-hydroxyl-hexafluoro propylidene base) benzene; C) condensation reaction of 1,3-bis-(2-hydroxyl-hexafluoro propylidene base) benzene and phenol, preparation 1,3-bis-(2-(4-hydroxy phenyl)-hexafluoro propylidene base) benzene.
The lithiumation of the m-dibromobenzene in step a), carries out in the one or mixed solvent of tetrahydrofuran (THF), ether and toluene-triethylamine; The mol ratio of m-dibromobenzene and metallic lithium controls in (2 ~ 3): 1; Lithiation carries out under the anhydrous and oxygen-free condition of nitrogen protection; The temperature of lithiation 40 ~ 80 DEG C, reaction times 3-12h.By controlling above lithiumation parameter, the complete lithiumation of m-dibromobenzene can be realized.Need ben, reaction must be carried out under anhydrous and oxygen-free condition, otherwise extreme influence transformation efficiency.Solvent is through 4A molecular sieve except water treatment, if directly adopt commercially available analytical pure solvent, micro-moisture wherein affects smoothly to some extent for reaction.
Isophthalic dilithium salt in step b) and the addition reaction of Perfluoroacetone, be added drop-wise to by Perfluoroacetone in isophthalic dilithium salt solution that a) step obtains, rate of addition controls make temperature of reaction <40 DEG C, reaction times 1-10h.The addition reaction of isophthalic dilithium salt and Perfluoroacetone at room temperature can be carried out smoothly, and temperature is too high can cause side reaction on the contrary.Therefore keep reacting under natural temperature.Solvent is very large on the impact of this step, when selecting the non-polar solvents such as toluene, adds a part of tetrahydrofuran (THF) or triethylamine, is conducive to reaction and carries out smoothly.
The condensation reaction of 1,3-in step c) bis-(2-hydroxyl-hexafluoro propylidene base) benzene and phenol, solvent is one in toluene, tetrahydrofuran (THF) and ether or mixture; Reaction is carried out under an acidic catalyst effect, and an acidic catalyst is sulfuric acid, hydrochloric acid, phosphoric acid, tosic acid, the one of phospho-wolframic acid and acid polynite or mixture, and consumption is 0.5 ~ 3% of phenol quality; Setting-up point 40-100 DEG C, reaction times 3-10h.Temperature of reaction and reaction times affect very large for transformation efficiency; Consider that this reaction does not have side reaction, suggestion adopts higher temperature of reaction, such as 70-100 DEG C.Adopting the progress of thin plate chromatogram detection reaction, when reacting substantially completely, can purification be cooled.
The synthetic method of a kind of novel fluorine bisphenol cpd 1,3-bis-(2-(4-hydroxy phenyl)-hexafluoro propylidene base) benzene disclosed by the invention, has 3 features:
(1) easy and simple to handle, be easy to realize industrialization;
(2) adopt conventional inexpensive raw material and solvent, cost is low;
(3) as the raw material monomer of fluorine material, synthesis fluorine-containing epoxy resin, fluorine-containing cyanate ester resin, fluorine-containing unsaturated polyester resin and other fluoro-containing macromolecule material, be widely used.
Accompanying drawing explanation
The synthetic route chart of Figure 11,3-bis-(2-(4-hydroxy phenyl)-hexafluoro propylidene base) benzene
Embodiment
Be below embodiments of the invention, but the present invention is not limited to following examples, any preparation parameter adjustment carried out based on the method for the invention, all within the scope of the invention.
Embodiment 1
In the 500mL vial that reflux condensing tube (nitrogen protection balloon is equipped with in prolong upper end), thermometer and feed hopper are housed; add 200ml tetrahydrofuran (THF) and 2.8g (0.4mol) lithium silk; be heated to 40 DEG C; drip 11.8g (0.2mol) m-dibromobenzene under vigorous stirring; after lithiation causes, reacting liquid temperature is elevated to boiling very soon.Control drop rate and keep slight boiling condition, all drip off and about need 1h.Slight boiling condition is kept to continue reaction 2h, the completely dissolve of lithium silk.
Above reaction solution is cooled to room temperature, under agitation drips 62g (0.4mol) Perfluoroacetone, and control rate of addition and keep reacting liquid temperature not higher than 40 DEG C, Perfluoroacetone dropwises in 1h, continues natural reaction 3h and obtains cloudy suspension.With 10% hydrochloric acid neutralization, change transparent reaction liquid into.Reaction solution vacuum distilling removing fugitive constituent is obtained white solid.
After the extraction of 100ml toluene, with 4*30ml deionized water wash toluene solution, then add the agent of 15g anhydrous sodium sulfate drying, hold over night; Cross and filter siccative, obtain toluene solution.By adding 38g (0.4mol) phenol in toluene solution again, adding 0.4g tosic acid simultaneously, being heated to 70 DEG C of reaction 6h.After cool to room temperature, with 6*30ml deionized water wash toluene reaction solution.The toluene solution vacuum distilling removing toluene obtained by separatory obtains fluorine-containing bisphenol cpd 1,3-bis-(2-(4-hydroxy phenyl)-hexafluoro propylidene base) benzene 84g.Total recovery: 78%.
Ultimate analysis: C, 40.5%; H, 3.32%; F, 38.1%.IC-MS mass spectroscopy: M+(molecular weight), 538.GC:99%(purity).Fusing point (Hot stage microscope method): 136 DEG C.Solvability (good solvent): ethanol; Acetone; Tetrahydrofuran (THF).
Embodiment 2
In the 500mL vial that reflux condensing tube (nitrogen protection balloon is equipped with in prolong upper end), thermometer and feed hopper are housed; add 200ml toluene-tetrahydrofuran (THF) (mass ratio 3:1) and 2.8g (0.4mol) lithium silk; be heated to 60 DEG C; drip 11.8g (0.2mol) m-dibromobenzene under vigorous stirring; after lithiation causes, reacting liquid temperature is elevated to micro-boiling very soon.Control drop rate and keep slight boiling condition, all dripping off about needs 0.5h(to compare tetrahydrofuran (THF) medium boiling point to want high, and rate of addition just can soon).Slight boiling condition is kept to continue reaction 1h, the completely dissolve of lithium silk.
Above reaction solution is cooled to room temperature, under agitation drips 62g (0.4mol) Perfluoroacetone, and control rate of addition and keep reacting liquid temperature not higher than 40 DEG C, Perfluoroacetone dropwises in 1h, continues natural reaction 5h and obtains cloudy suspension.With 10% hydrochloric acid neutralization, change transparent reaction liquid into.Reaction solution vacuum distilling removing fugitive constituent is obtained white solid.
After the extraction of 100ml toluene, with 4*30ml deionized water wash toluene solution, then add the agent of 15g anhydrous sodium sulfate drying, hold over night; Cross and filter siccative, obtain toluene solution.By adding 38g (0.4mol) phenol in toluene solution again, adding 0.5g phosphoric acid simultaneously, being heated to 80 DEG C of reaction 4h.After cool to room temperature, with 6*30ml deionized water wash toluene reaction solution.The toluene solution vacuum distilling removing toluene obtained by separatory obtains fluorine-containing bisphenol cpd 1,3-bis-(2-(4-hydroxy phenyl)-hexafluoro propylidene base) benzene 79g.Total recovery: 73%.
Ultimate analysis: C, 40.3%; H, 3.32%; F, 37.9%.IC-MS mass spectroscopy: M+(molecular weight), 538.GC:99%(purity).Fusing point (Hot stage microscope method): 135 DEG C.Solvability (good solvent): ethanol; Acetone; Tetrahydrofuran (THF).
Claims (4)
1. the preparation method of fluorine-containing bisphenol cpd 1,3-bis-(2-(4-hydroxy phenyl)-hexafluoro propylidene base) benzene, is characterized in that, comprise three consecutive steps: a) lithiumation of m-dibromobenzene, preparation isophthalic dilithium salt; B) addition reaction of isophthalic dilithium salt and Perfluoroacetone, preparation 1,3-bis-(2-hydroxyl-hexafluoro propylidene base) benzene; C) condensation reaction of 1,3-bis-(2-hydroxyl-hexafluoro propylidene base) benzene and phenol, preparation 1,3-bis-(2-(4-hydroxy phenyl)-hexafluoro propylidene base) benzene.
2. the fluorine-containing bisphenol cpd 1 of one according to claim 1, the preparation method of 3-bis-(2-(4-hydroxy phenyl)-hexafluoro propylidene base) benzene, it is characterized in that, step a) in the lithiumation of m-dibromobenzene, carry out in the one or mixed solvent of tetrahydrofuran (THF), ether and toluene-triethylamine; The mol ratio of m-dibromobenzene and metallic lithium controls in (2 ~ 3): 1; Lithiation carries out under the anhydrous and oxygen-free condition of nitrogen protection; The temperature of lithiation 40 ~ 80 DEG C, reaction times 3-12h.
3. the fluorine-containing bisphenol cpd 1 of one according to claim 1, the preparation method of 3-bis-(2-(4-hydroxy phenyl)-hexafluoro propylidene base) benzene, it is characterized in that, step b) in isophthalic dilithium salt and the addition reaction of Perfluoroacetone, Perfluoroacetone is added drop-wise in isophthalic dilithium salt solution that a) step obtains, rate of addition controls make temperature of reaction <40 DEG C, reaction times 1-10h.
4. the fluorine-containing bisphenol cpd 1 of one according to claim 1, the preparation method of 3-bis-(2-(4-hydroxy phenyl)-hexafluoro propylidene base) benzene, it is characterized in that, step c) in 1, the condensation reaction of 3-bis-(2-hydroxyl-hexafluoro propylidene base) benzene and phenol, solvent is one in toluene, tetrahydrofuran (THF) and ether or mixture; Reaction is carried out under an acidic catalyst effect, and an acidic catalyst is sulfuric acid, hydrochloric acid, phosphoric acid, tosic acid, the one of phospho-wolframic acid and acid polynite or mixture, and consumption is 0.5 ~ 3% of phenol quality; Setting-up point 40-100 DEG C, reaction times 3-10h.
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| CN105218319A (en) * | 2015-11-10 | 2016-01-06 | 北京石油化工学院 | The preparation method of two (hexafluoro-hydroxyl sec.-propyl) benzene of a kind of 1,3- |
| CN109516929A (en) * | 2018-12-11 | 2019-03-26 | 中国航空工业集团公司济南特种结构研究所 | A kind of preparation method of fluorine-containing cyanate ester monomer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051917A (en) * | 1989-10-31 | 1991-06-05 | 联合碳化工业气体技术公司 | The hexafluoro-BIS-A polysulfone membrane of carbonization and be used for the method for fluid separation |
| CN1733674A (en) * | 2005-08-05 | 2006-02-15 | 上海康鹏化学有限公司 | Preparation method of double(2-hydroxyl hexafluopropyl) phenol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS58180531A (en) * | 1982-04-19 | 1983-10-22 | Hitachi Ltd | Fluorine-containing polyimide, polyamic acid and production thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051917A (en) * | 1989-10-31 | 1991-06-05 | 联合碳化工业气体技术公司 | The hexafluoro-BIS-A polysulfone membrane of carbonization and be used for the method for fluid separation |
| CN1733674A (en) * | 2005-08-05 | 2006-02-15 | 上海康鹏化学有限公司 | Preparation method of double(2-hydroxyl hexafluopropyl) phenol |
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