CN102887817B - Novel method for synthesizing 2,3,4,5,6-pentafluorophenol - Google Patents
Novel method for synthesizing 2,3,4,5,6-pentafluorophenol Download PDFInfo
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- CN102887817B CN102887817B CN201210333409.6A CN201210333409A CN102887817B CN 102887817 B CN102887817 B CN 102887817B CN 201210333409 A CN201210333409 A CN 201210333409A CN 102887817 B CN102887817 B CN 102887817B
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Abstract
The invention relates to a novel method for synthesizing 2,3,4,5,6-pentafluorophenol. The method comprises the following steps of: performing hydrolysis reaction of 2,3,4,5,6-pentafluoro-1-halogenated benzene which is taken as a raw material in the presence of a catalyst and alkali, and acidizing to obtain the 2,3,4,5,6-pentafluorophenol. The invention is characterized in that the raw material is readily available, reaction conditions are mild, the product has high purity, the atom economy is high, and the like; and the product fully meets the using requirements when the product is taken as a liquid crystal intermediate and a medicinal intermediate.
Description
Technical field
The present invention relates to a kind of preparation method of TFT liquid crystal intermediates 2,3,4,5,6-Pentafluorophenol.
Background technology
As TFT liquid crystal material intermediate, 2,3,4,5,6-Pentafluorophenol is specially adapted to the preparation of polyfluoro class monomeric liquid crystal material, polyfluoro class monomeric liquid crystal material and low viscosity and high dielectric anisotropy nematic liquid crystalline material used in combination after, macromolecular dipole moment can be increased, reduce the time of response, improve the display performance of liquid crystal material, promote clearness, production high-performance liquid crystal material is had great importance.
Summary of the invention
The object of the present invention is to provide a kind of technique simple, environmental friendliness, the novel method of synthesis 2,3,4,5, the 6-Pentafluorophenol that Atom economy is high.For this reason, the present invention is by the following technical solutions:
The novel process of a kind of synthesis 2,3,4,5,6-Pentafluorophenol, be is characterized in that, realized by following reaction:
Concrete steps are:
(1) hydrolysis under the existence of catalyzer and alkali of fluoro-for 2,3,4,5,6-five 1-halogeno-benzene is obtained 2,3,4,5,6-Pentafluorophenol sodium salt;
(2) 2,3,4,5,6-Pentafluorophenol sodium is carried out acidification and obtain 2,3,4,5,6-Pentafluorophenol.Halogenic substituent X wherein in 2,3,4,5,6-five fluoro-1-halogeno-benzenes is selected from F
-, Cl
-, Br
-and I
-, be preferably Br
-, described catalyzer is selected from cupric oxide, Red copper oxide, copper powder, cupric sulfate pentahydrate, cuprous chloride and cupric chloride, is preferably Red copper oxide.
As one embodiment of the invention, in reaction, the mol ratio of 2,3,4,5,6-five fluoro-1-halogeno-benzenes and catalyzer is 1:(0.01 ~ 0.2).
As a preferred embodiment of the present invention, in reaction, the mol ratio of 2,3,4,5,6-five fluoro-1-halogeno-benzenes and catalyzer is preferably 1:(0.05 ~ 0.1).
As one embodiment of the invention, hydrolysis reaction carries out in the presence of base, and described alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide, the aqueous solution of one or more mixtures in sodium carbonate.
As a preferred embodiment of the present invention, the aqueous solution of the preferred sodium hydroxide of described alkali and sodium carbonate mixture.
As a preferred embodiment of the present invention, described sodium hydroxide and sodium carbonate total concn are that the aqueous solution form of 10 ~ 30%w/w uses, and the aqueous solution form being preferably total concn 20 ~ 25%w/w uses.
As a preferred embodiment of the present invention, in reaction, the mol ratio of 2,3,4,5,6-five fluoro-1-halogeno-benzenes and sodium hydroxide, sodium carbonate is 1:(0.5 ~ 3.0): (0.5-2.0), preferred 1:(1.0 ~ 1.8): (0.8-1.5).
As a preferred embodiment of the present invention, the temperature of reaction of step (1) hydrolysis reaction is 100 ~ 180 DEG C, preferably 130 ~ 160 DEG C.
As one embodiment of the invention, the acid used in step (2) is sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid.Experimental study according to present invention applicant finds, above-mentioned acid all can realize the present invention preferably, and surprisingly, wherein the effect of hydrochloric acid is better.
As one embodiment of the invention, the acid used in step (2) for mass concentration be the hydrochloric acid of 30%.
Owing to adopting technical scheme of the present invention, the present invention with 2,3,4, the fluoro-1-halogeno-benzene of 5,6-five is raw material, and under the existence of catalyzer and alkali, hydrolysis obtains 2,3,4,5,6-Pentafluorophenol sodium salt, 2 are obtained, 3,4 after acidified again, 5,6-Pentafluorophenol, reactions steps is few, yield is high, and product purity is high, significantly can reduce production cost.
Accompanying drawing explanation
Fig. 1 is the Pentafluorophenol nuclear magnetic resonance map of the embodiment of the present invention 1.
Embodiment
Following type reaction is used for illustrating the present invention.All belong within the technical scheme that the present invention protects inventing the simple replacement done or improvement etc. those skilled in that art.
The preparation of embodiment 1:2,3,4,5,6-Pentafluorophenol
Water 620g is added inside the autoclave of 2L, sodium hydroxide 50.6g(1.26mol), sodium carbonate 105.2g(0.99mol), Red copper oxide 11g(0.076mol), five bromofluorobenzene 222.3g(0.9mol) enclosed high pressure still, be warming up to 140 DEG C, and reaction was cooled to room temperature after 5 hours at 140 DEG C, by 2, 3, 4, 5, 6-Pentafluorophenol sodium material is poured out, filter, it is hydrochloric acid acidifying at 15-20 DEG C of 30% by filtrate 188g mass concentration, pH=4-6, after acidifying, extract with the methyl tertiary butyl ether of 250g*2, merge organic phase, distillating recovering solvent, again by tower rectifying on product, obtain 2, 3, 4, 5, 6-Pentafluorophenol 135.8g, content 99.6%, yield 82.0%.
Fig. 1 be finished product that the present embodiment rectifying is obtained through nuclear magnetic resonance spectroscopy, 1H-NMR(DMSO, 500Hz) δ: 11.37(m, 1H), display the present invention has obtained 2,3,4,5,6-Pentafluorophenols through above-mentioned steps.
The preparation of embodiment 2:2,3,4,5,6-Pentafluorophenol
By embodiment 1, replace five bromofluorobenzenes with five fluorochlorobenzenes, charging capacity is 182.3g(0.9mol), final reaction obtains 2,3,4,5,6-Pentafluorophenol 125g, content 99.3%, yield 75.5%.
The preparation of embodiment 3:2,3,4,5,6-Pentafluorophenol
By embodiment 1, change Red copper oxide into cupric oxide, charging capacity is 6.1g(0.076mol), be obtained by reacting 2,3,4,5,6-Pentafluorophenol 115g, content 99.4%, yield 69.4%.
The preparation of embodiment 4:2,3,4,5,6-Pentafluorophenol
By embodiment 1, the amount of Red copper oxide is changed and is reduced to 7.2g(0.05mol), be obtained by reacting 2,3,4,5,6-Pentafluorophenol 121g, content 99.3%, yield 73.0%.
The preparation of embodiment 5:2,3,4,5,6-Pentafluorophenol
By embodiment 1, with 90g(2.25mol) sodium hydroxide replaces the mixture of sodium carbonate and sodium hydroxide, is obtained by reacting 2,3,4,5,6-Pentafluorophenol 108g, content 95.3%, yield 65.2%.
The preparation of embodiment 6:2,3,4,5,6-Pentafluorophenol
By embodiment 1, with potassium hydroxide 70.56g(1.26mol), calcium hydroxide 73.3g(0.99mol) replace the mixture of sodium carbonate and sodium hydroxide, be obtained by reacting 2,3,4,5,6-Pentafluorophenol 112g, content 95.5%, yield 67.6%.
The preparation of embodiment 7:2,3,4,5,6-Pentafluorophenol
By embodiment 1, the charging capacity of sodium hydroxide is reduced to 40.0g(1.0mol), be obtained by reacting 2,3,4,5,6-Pentafluorophenol 126g, content 99.4%, yield 76.0%.
The preparation of embodiment 8:2,3,4,5,6-Pentafluorophenol
By embodiment 1, the charging capacity of sodium carbonate is increased to 143.1g(1.35mol), be obtained by reacting 2,3,4,5,6-Pentafluorophenol 118g, content 98.2%, yield 71.26%.
The preparation of embodiment 9:2,3,4,5,6-Pentafluorophenol
By embodiment 1, the charging capacity of water is changed into the corresponding sodium hydroxide of 818g(and sodium carbonate total concn is 16%), be obtained by reacting 2,3,4,5,6-Pentafluorophenol 129g, content 99.5%, yield 77.9%.
The preparation of embodiment 10:2,3,4,5,6-Pentafluorophenol
By embodiment 1, hydrolysising reacting temperature is increased to 170 DEG C, is obtained by reacting 2,3,4,5,6-Pentafluorophenol 115g, content 98.1%, yield 69.4%.
The preparation of embodiment 11:2,3,4,5,6-Pentafluorophenol
Replace 188g 30% hydrochloric acid by embodiment 1,77.3g 98% sulfuric acid, be obtained by reacting 2,3,4,5,6-Pentafluorophenol 128.5g, content 99.3%, yield 77.6%.
Claims (1)
1. the method for synthesis 2,3,4,5, a 6-Pentafluorophenol, is characterized in that comprising the following steps:
(1) hydrolysis under the existence of catalyzer and alkali of fluoro-for 2,3,4,5,6-five 1-halogeno-benzene is obtained 2,3,4,5,6-Pentafluorophenol sodium salt;
(2) 2,3,4,5,6-Pentafluorophenol sodium is carried out acidification and obtain 2,3,4,5,6-Pentafluorophenol.
Halogenic substituent in the fluoro-1-halogeno-benzene of 2,3,4,5,6-five is selected from Cl
-and Br
-, described catalyzer is selected from Red copper oxide, 2, 3, 4, 5, the mol ratio of the fluoro-1-halogeno-benzene of 6-five and catalyzer is 1:(0.05 ~ 0.1), the alkali used in step (1) uses sodium hydroxide and sodium carbonate mixture, sodium hydroxide and sodium carbonate use with the aqueous solution form that total concn is 20% ~ 25% w/w, in reaction 2, 3, 4, 5, the fluoro-1-halogeno-benzene of 6-five and sodium hydroxide, the mol ratio of sodium carbonate is 1:(1.0 ~ 1.8): (0.8-1.5), the temperature of the hydrolysis reaction of step (1) is 130 ~ 160 DEG C, the acid used in step (2) is hydrochloric acid, use acid for mass concentration be the hydrochloric acid of 30%.
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| CN103254039B (en) * | 2013-06-08 | 2015-07-01 | 济南卡博唐生物科技有限公司 | Preparation method of orthocresol |
| CN105593197B (en) * | 2013-10-04 | 2018-07-13 | 巴斯夫欧洲公司 | The method for hydrolyzing 1,2,4- phenyl trihalides |
| CN103787839B (en) * | 2014-01-21 | 2015-12-02 | 苏州昊帆生物科技有限公司 | The method of synthesis 2,3,4,5,6-Pentafluorophenol |
| CN104693010B (en) * | 2015-02-15 | 2016-03-30 | 浙江永太科技股份有限公司 | The method of a kind of synthesis 2,3,4,5,6-Pentafluorophenol |
| CN104761436B (en) * | 2015-04-03 | 2017-06-06 | 上海其新生物科技有限公司 | A kind of method for synthesizing Pentafluorophenol |
| CN104961629A (en) * | 2015-05-19 | 2015-10-07 | 烟台蓓丰医药科技有限公司 | Synthetic method of pentafluorophenol |
| CN105384603A (en) * | 2015-12-09 | 2016-03-09 | 陕西省石油化工研究设计院 | Synthesis method of poly-fluorinated phenol compound |
| CN106187706B (en) * | 2016-08-04 | 2019-09-10 | 陕西省石油化工研究设计院 | A kind of process for refining of high-purity Pentafluorophenol |
| CN107963974B (en) * | 2018-01-12 | 2020-09-08 | 浙江鼎龙科技有限公司 | Preparation method of 5-amino-2-methylphenol |
| CN111072455B (en) * | 2019-12-27 | 2022-06-07 | 大连奇凯医药科技有限公司 | Method for continuously preparing pentafluorophenol by microreactor |
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| CN1208398A (en) * | 1996-01-15 | 1999-02-17 | 溴化合物有限公司 | Preparation method of p-fluorophenol |
| CN100434410C (en) * | 2005-04-11 | 2008-11-19 | 临海市永太化工有限公司 | Process of producing pentafluorophenol |
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| Nucleophilic Aromatic Substitution by Hydroxide Ion under Phase-Transfer Catalysis Conditions:Fluorine Displacement in Polyfluorobenzene Derivatives;David Feldman;《J. Org. Chem.》;19911231;第56卷;第7350-7353页 * |
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