CN102887817A - Novel method for synthesizing 2,3,4,5,6-pentafluorophenol - Google Patents
Novel method for synthesizing 2,3,4,5,6-pentafluorophenol Download PDFInfo
- Publication number
- CN102887817A CN102887817A CN2012103334096A CN201210333409A CN102887817A CN 102887817 A CN102887817 A CN 102887817A CN 2012103334096 A CN2012103334096 A CN 2012103334096A CN 201210333409 A CN201210333409 A CN 201210333409A CN 102887817 A CN102887817 A CN 102887817A
- Authority
- CN
- China
- Prior art keywords
- pentafluorophenol
- novel method
- acid
- sodium hydroxide
- halogeno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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 TFT liquid crystal intermediates 2,3,4,5, the preparation method of 6-Pentafluorophenol.
Background technology
As TFT liquid crystal material intermediate, 2,3,4,5, the 6-Pentafluorophenol is specially adapted to polyfluoro class monomer liquid crystal material preparation, and polyfluoro class monomer liquid crystal material can increase macromolecular dipole moment mix use with low viscosity and high dielectric anisotropy nematic liquid crystalline material after, 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 synthetic 2,3,4,5, the 6-Pentafluorophenol that Atom economy is high.For this reason, the present invention is by the following technical solutions:
A kind of novel process of synthetic 2,3,4,5,6-Pentafluorophenol is characterized in that, realizes by following reaction:
Concrete steps are:
(1) 2,3,4,5,6-, five fluoro-1-halogeno-benzenes are hydrolyzed in the presence of catalyzer and alkali obtain 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.Wherein 2,3,4,5, the halogenic substituent X in the 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 the reaction 2,3,4,5, the mol ratio of 6-five fluoro-1-halogeno-benzenes and catalyzer is 1:(0.01~0.2).
As a preferred embodiment of the present invention, in the reaction 2,3,4,5, the mol ratio of 6-five fluoro-1-halogeno-benzenes and catalyzer is preferably 1:(0.05~0.1).
As one embodiment of the invention, hydrolysis reaction is to carry out in the presence of alkali, and described alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide, the aqueous solution of one or more mixtures in the yellow soda ash.
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 yellow soda ash total concn are that the aqueous solution form of 10~30%w/w is used, and the aqueous solution form that is preferably total concn 20~25%w/w is used.
As a preferred embodiment of the present invention, in the reaction 2,3,4,5, the mol ratio of 6-five fluoro-1-halogeno-benzenes and sodium hydroxide, yellow soda ash 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 ℃, preferred 130~160 ℃.
As one embodiment of the invention, the acid of using in the step (2) is sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid.Research finds that above-mentioned acid all can realize the present invention preferably according to the present patent application human experimentation, and beat all is that wherein the effect of hydrochloric acid is better.
As one embodiment of the invention, the acid of using in the step (2) is 30% hydrochloric acid as mass concentration.
Owing to adopt technical scheme of the present invention, the present invention is with 2,3,4,5,6-, five fluoro-1-halogeno-benzenes are raw material, and hydrolysis obtains 2,3 in the presence of catalyzer and alkali, 4,5,6-Pentafluorophenol sodium salt, obtain 2,3,4 after acidified again, 5,6-Pentafluorophenol, reactions steps is few, yield is high, and product purity is high, can the decrease production cost.
Description of drawings
Fig. 1 is the Pentafluorophenol nuclear magnetic resonance map of the embodiment of the invention 1.
Embodiment
Following type reaction is used for illustrating the present invention.The simple replacement done of invention or improvement etc. are all belonged within the technical scheme that the present invention protects those skilled in that art.
Embodiment 1:2, the preparation of 3,4,5,6-Pentafluorophenol
Autoclave the inside at 2L adds entry 620g, sodium hydroxide 50.6g(1.26mol), yellow soda ash 105.2g(0.99mol), Red copper oxide 11g(0.076mol), five bromofluorobenzene 222.3g(0.9mol) the enclosed high pressure still, be warming up to 140 ℃, and after reacting 5 hours under 140 ℃, be cooled to room temperature, with 2,3,4,5,6-Pentafluorophenol sodium material is poured out, and filters, be that 30% hydrochloric acid is 15-20 ℃ of lower acidifying with the 188g mass concentration with filtrate, pH=4-6 after the acidifying, extracts with the methyl tertiary butyl ether of 250g*2, merge organic phase, distillating recovering solvent with tower rectifying on the product, obtains 2 again, 3,4,5,6-Pentafluorophenol 135.8g, content 99.6%, yield 82.0%.
Fig. 1 for finished product that present embodiment rectifying is obtained through nuclear magnetic resonance spectroscopy, 1H-NMR(DMSO, 500Hz) δ: 11.37(m, 1H), show that the present invention has made 2,3,4,5, the 6-Pentafluorophenol through above-mentioned steps.
Embodiment 2:2, the preparation of 3,4,5,6-Pentafluorophenol
Press 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%.
Embodiment 3:2, the preparation of 3,4,5,6-Pentafluorophenol
Press embodiment 1, change Red copper oxide into cupric oxide, charging capacity is 6.1g(0.076mol), reaction obtains 2,3,4,5,6-Pentafluorophenol 115g, content 99.4%, yield 69.4%.
Embodiment 4:2, the preparation of 3,4,5,6-Pentafluorophenol
Press embodiment 1, the amount of Red copper oxide is changed be reduced to 7.2g(0.05mol), reaction obtains 2,3,4,5,6-Pentafluorophenol 121g, content 99.3%, yield 73.0%.
Embodiment 5:2, the preparation of 3,4,5,6-Pentafluorophenol
Press embodiment 1, with 90g(2.25mol) sodium hydroxide replaces the mixture of yellow soda ash and sodium hydroxide, and reaction obtains 2,3,4,5,6-Pentafluorophenol 108g, content 95.3%, yield 65.2%.
Embodiment 6:2, the preparation of 3,4,5,6-Pentafluorophenol
Press embodiment 1, with potassium hydroxide 70.56g(1.26mol), calcium hydroxide 73.3g(0.99mol) replace the mixture of yellow soda ash and sodium hydroxide, reaction obtains 2,3,4,5,6-Pentafluorophenol 112g, content 95.5%, yield 67.6%.
Embodiment 7:2, the preparation of 3,4,5,6-Pentafluorophenol
Press embodiment 1, the charging capacity of sodium hydroxide be reduced to 40.0g(1.0mol), reaction obtains 2,3,4,5,6-Pentafluorophenol 126g, content 99.4%, yield 76.0%.
Embodiment 8:2, the preparation of 3,4,5,6-Pentafluorophenol
Press embodiment 1, the charging capacity of yellow soda ash increased to 143.1g(1.35mol), reaction obtains 2,3,4,5,6-Pentafluorophenol 118g, content 98.2%, yield 71.26%.
Embodiment 9:2, the preparation of 3,4,5,6-Pentafluorophenol
Press embodiment 1, change the charging capacity of water into 818g(corresponding sodium hydroxide and the yellow soda ash total concn is 16%), reaction obtains 2,3,4,5,6-Pentafluorophenol 129g, content 99.5%, yield 77.9%.
Embodiment 10:2, the preparation of 3,4,5,6-Pentafluorophenol
Press embodiment 1, hydrolysising reacting temperature is increased to 170 ℃, reaction obtains 2,3,4,5,6-Pentafluorophenol 115g, content 98.1%, yield 69.4%.
Embodiment 11:2, the preparation of 3,4,5,6-Pentafluorophenol
Press embodiment 1,77.3g 98% sulfuric acid replaces 188g 30% hydrochloric acid, and reaction obtains 2,3,4,5,6-Pentafluorophenol 128.5g, content 99.3%, yield 77.6%.
Claims (10)
1. the novel method of synthetic 2,3,4,5, a 6-Pentafluorophenol is characterized in that may further comprise the steps:
(1) 2,3,4,5,6-, five fluoro-1-halogeno-benzenes are hydrolyzed in the presence of catalyzer and alkali obtain 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;
Wherein 2,3,4,5, the halogenic substituent in the 6-five fluoro-1-halogeno-benzenes is selected from F
-, Cl
-, Br
-And I
-, described catalyzer is selected from cupric oxide, Red copper oxide, copper powder, cupric sulfate pentahydrate, cuprous chloride and cupric chloride.
2. novel method according to claim 1 is characterized in that in the step (1) 2,3,4,5, and the mol ratio of 6-five fluoro-1-halogeno-benzenes and catalyzer is 1:(0.01 ~ 0.2), preferred 1:(0.05 ~ 0.1).
3. novel method according to claim 1 is characterized in that the alkali that uses in the step (1) as one or more the mixture in sodium hydroxide, potassium hydroxide, calcium hydroxide, the yellow soda ash, preferably uses sodium hydroxide and sodium carbonate mixture.
4. novel method according to claim 3, it is characterized in that sodium hydroxide, potassium hydroxide, calcium hydroxide, the mixture of one or more in the yellow soda ash uses with the aqueous solution form of 10% ~ 30% w/w, preferably uses with the aqueous solution form of 20% ~ 25% w/w.
5. method according to claim 3 is characterized in that the aqueous solution form use take total concn as 10% ~ 30% w/w of sodium hydroxide and yellow soda ash, and preferably the aqueous solution form take total concn as 20% ~ 25% w/w is used.
6. according to claim 3 or 5 described novel methods, it is characterized in that in the reaction 2,3,4,5, the mol ratio of 6-five fluoro-1-halogeno-benzenes and sodium hydroxide, yellow soda ash is 1:(0.5 ~ 3.0): (0.5-2.0), preferred 1:(1.0 ~ 1.8): (0.8-1.5).
7. the described novel method of any one according to claim 1-6, the temperature that it is characterized in that the hydrolysis reaction of step (1) is 100~180 ℃, preferred 130~160 ℃.
8. novel method according to claim 1 is characterized in that the acid of using in the step (2) is selected from sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, preferred hydrochloric acid.
9. novel method according to claim 1 is characterized in that the acid of using in the step (2) is 30% hydrochloric acid as mass concentration.
10. novel method according to claim 1 is characterized in that halogenic substituent is selected from Br
-Described catalyzer is Red copper oxide.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210333409.6A CN102887817B (en) | 2012-09-11 | 2012-09-11 | Novel method for synthesizing 2,3,4,5,6-pentafluorophenol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210333409.6A CN102887817B (en) | 2012-09-11 | 2012-09-11 | Novel method for synthesizing 2,3,4,5,6-pentafluorophenol |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102887817A true CN102887817A (en) | 2013-01-23 |
CN102887817B CN102887817B (en) | 2015-04-01 |
Family
ID=47531519
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201210333409.6A Active CN102887817B (en) | 2012-09-11 | 2012-09-11 | Novel method for synthesizing 2,3,4,5,6-pentafluorophenol |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102887817B (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103254039A (en) * | 2013-06-08 | 2013-08-21 | 济南卡博唐生物科技有限公司 | Preparation method of orthocresol |
CN103787839A (en) * | 2014-01-21 | 2014-05-14 | 苏州昊帆生物科技有限公司 | Method for synthesizing 2,3,4,5,6-pentafluorophenol |
CN104693010A (en) * | 2015-02-15 | 2015-06-10 | 浙江永太科技股份有限公司 | Method for synthesizing 2,3,4,5,6-pentafluorophenol |
CN104761436A (en) * | 2015-04-03 | 2015-07-08 | 上海其新生物科技有限公司 | 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 |
CN105593197A (en) * | 2013-10-04 | 2016-05-18 | 巴斯夫欧洲公司 | Process for hydrolyzing 1,2,4-trihalobenzene |
CN106187706A (en) * | 2016-08-04 | 2016-12-07 | 陕西省石油化工研究设计院 | A kind of process for refining of high-purity Pentafluorophenol |
CN107963974A (en) * | 2018-01-12 | 2018-04-27 | 浙江鼎龙科技有限公司 | The preparation method of 5- amino-2-methyl phenol |
CN111072455A (en) * | 2019-12-27 | 2020-04-28 | 大连奇凯医药科技有限公司 | Method for continuously preparing pentafluorophenol by microreactor |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1208398A (en) * | 1996-01-15 | 1999-02-17 | 溴化合物有限公司 | Preparation method of p-fluorophenol |
CN1861554A (en) * | 2005-05-09 | 2006-11-15 | 临海市永太化工有限公司 | Production tech, of 3,4,5 trifluorophenol |
CN100434410C (en) * | 2005-04-11 | 2008-11-19 | 临海市永太化工有限公司 | Process of producing pentafluorophenol |
-
2012
- 2012-09-11 CN CN201210333409.6A patent/CN102887817B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN1861554A (en) * | 2005-05-09 | 2006-11-15 | 临海市永太化工有限公司 | Production tech, of 3,4,5 trifluorophenol |
Non-Patent Citations (1)
Title |
---|
DAVID FELDMAN: "Nucleophilic Aromatic Substitution by Hydroxide Ion under Phase-Transfer Catalysis Conditions:Fluorine Displacement in Polyfluorobenzene Derivatives", 《J. ORG. CHEM.》, vol. 56, 31 December 1991 (1991-12-31), pages 7350 - 7353 * |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN103254039A (en) * | 2013-06-08 | 2013-08-21 | 济南卡博唐生物科技有限公司 | Preparation method of orthocresol |
CN105593197A (en) * | 2013-10-04 | 2016-05-18 | 巴斯夫欧洲公司 | Process for hydrolyzing 1,2,4-trihalobenzene |
CN105593197B (en) * | 2013-10-04 | 2018-07-13 | 巴斯夫欧洲公司 | The method for hydrolyzing 1,2,4- phenyl trihalides |
CN103787839A (en) * | 2014-01-21 | 2014-05-14 | 苏州昊帆生物科技有限公司 | Method for synthesizing 2,3,4,5,6-pentafluorophenol |
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 |
CN104693010A (en) * | 2015-02-15 | 2015-06-10 | 浙江永太科技股份有限公司 | Method for synthesizing 2,3,4,5,6-pentafluorophenol |
CN105418386B (en) * | 2015-02-15 | 2017-10-10 | 浙江永太科技股份有限公司 | A kind of method for synthesizing 2,3,4,5,6 Pentafluorophenols |
CN105418386A (en) * | 2015-02-15 | 2016-03-23 | 浙江永太科技股份有限公司 | Method for synthesizing 2,3,4,5,6-pentafluorophenol |
CN104761436A (en) * | 2015-04-03 | 2015-07-08 | 上海其新生物科技有限公司 | 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 |
CN106187706A (en) * | 2016-08-04 | 2016-12-07 | 陕西省石油化工研究设计院 | A kind of process for refining of high-purity Pentafluorophenol |
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 |
CN107963974A (en) * | 2018-01-12 | 2018-04-27 | 浙江鼎龙科技有限公司 | The preparation method of 5- amino-2-methyl phenol |
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 |
CN111072455A (en) * | 2019-12-27 | 2020-04-28 | 大连奇凯医药科技有限公司 | Method for continuously preparing pentafluorophenol by microreactor |
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 |
Also Published As
Publication number | Publication date |
---|---|
CN102887817B (en) | 2015-04-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102887817B (en) | Novel method for synthesizing 2,3,4,5,6-pentafluorophenol | |
CN108840854A (en) | A kind of method of one pot process 5- chlorothiophene -2- carboxylic acid | |
CN101830793B (en) | Method for preparing hydroxyl-substituted phenylacetic acid compound | |
CN103694119A (en) | Preparation method of ethyl 4,4,4-trifluoroacetoacetate | |
CN104447536A (en) | Preparation method of N-2-quinolyl aryl sulfonamide compounds | |
CN102020584A (en) | Method for synthesizing intermediate L-2-aminobutyrylamide hydrochloride of chiral drug levetiracetam | |
CN103570623B (en) | Preparation method of 3-(difluoromethyl)-1-methyl-1H-pyrazol-4-carboxylic acid | |
CN103553878B (en) | A kind of novel preparation method of cyclohexyl phenol class liquid crystal intermediates compound | |
CN107056590B (en) | Industrial method for preparing and purifying 4, 4' -dimethoxy triphenylchloromethane | |
CN107936048A (en) | A kind of preparation method of 2 fluorine, 4 methyl, 3 pyridine boronic acid | |
CN102993114B (en) | A kind of production method of 1H-TETRAZOLE-5-acetic acid | |
CN103087033B (en) | Synthesis method of poly-substituted oxacycloheptatriene-3(2H) ketone compounds | |
CN104311432B (en) | ADZ6140 important intermediate (1R, 2S)-2-(3,4-difluoro-benzene base) preparation method of cyclopropylamine | |
CN102442944A (en) | Preparation method of flunixin | |
CN101704724B (en) | Novel method for preparing high-proportion trans, trans-4-(4'-alkyl cyclohexyl) cyclohexyl alcohol liquid crystal intermediate compound | |
CN101575301B (en) | Preparation method of 2-amino-5-chlorobenzamide | |
CN103408418B (en) | Preparation and purification method of solid malonic acid | |
CN102603571A (en) | Preparation method of 2,4-dichloro-3-cyano-5-fluobenzoic acid | |
CN108947868B (en) | Preparation process of 2, 4-difluorobenzonitrile | |
CN105439969A (en) | Method for preparing 3,5-dioxo-1,2,4-triazole | |
CN105418507A (en) | Preparation method for 1-(3-methyl-1-phenyl-1H-pyrazole-5-yl)piperazine | |
CN103467280A (en) | Preparation method of 3-trifluoromethybenzoic acid | |
CN102584688B (en) | Preparing method of 2,6-dichloro-3-nitropyridine | |
CN102633646B (en) | New preparation method of 5-nitro-salicylaldehyde | |
CN103183635B (en) | New process for synthetizing 3-(pyridin-2-ylamino) ethyl propionate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |