CN105384603A - Synthesis method of poly-fluorinated phenol compound - Google Patents
Synthesis method of poly-fluorinated phenol compound Download PDFInfo
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- CN105384603A CN105384603A CN201510902346.5A CN201510902346A CN105384603A CN 105384603 A CN105384603 A CN 105384603A CN 201510902346 A CN201510902346 A CN 201510902346A CN 105384603 A CN105384603 A CN 105384603A
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- 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
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/02—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of halogen
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Abstract
The invention discloses a synthesis method of poly-fluorinated phenol compound. According to the synthesis method, a compound (I) carries out reactions for 6 to 12 hours in a solvent at a temperature of 100 to 180 DEG C under a pressure of 0.3 to 2.0 MPa in the presence of a catalyst. Then the reaction product is subjected to a post treatment so as to obtain a compound (II). The yield of the method can reach 80% or more and is much higher than that of conventional technologies. The product purity can reach 99.5% or more. The luster of the product is good. Moreover, the synthesis method has the advantages of mild reaction conditions, high yield, low cost, and environment-friendliness.
Description
Technical field
The invention belongs to compound technical, be specifically related to a kind of synthetic method of chemical intermediate, more specifically relate to the method for synthesis 3,4,5-trifluoromethyl phenol, 3,5-difluorophenols, 2,3,4,5,6-Pentafluorophenols.
Background technology
Phenol compound of polyfluorinated organic generation is as a kind of important field such as chemical intermediate widespread use liquid crystal, medicine, agricultural chemicals.Fluorinated liquid crystal monomer material is using fluorine atom or fluoro-containing group as terminal polar group, there is due to fluorine atom the special propertys such as electronic effect, mimic effect, stopping effect and osmotic effect, thus have that viscosity is low, resistivity is high, fast response time, specific inductivity advantages of higher, be the TFT-LCD liquid crystal material of current main flow.Wherein, the many fluoric compounds of phenol such as two fluoro, three fluoro, five fluorine band phenol are modal key intermediates in fluorinated liquid crystal monomer material.In addition, 2,3,4,5,6-Pentafluorophenol is as the key intermediate of the third liver medicine Suo Feibuwei, and cause the extensive concern of field of medicaments, its market demand significantly increases.
Phenol polyfluoro traditional at present mainly contains for compound synthesis technology: 1. diazotization hydrolysis method.Method as described in Chinese patent ZL200510049766.X, with fluoro bromobenzene for raw material, fluorophenol is obtained through ammonification, diazotization, hydrolysis three-step reaction, the limitation of this technique is that reactions steps is many, produce a large amount of contaminated wastewater serious, by product difficulty is separated, and product purity is low, and product appearance and color and luster difficulty reach requirement.2. Grignard reagent method.Method as described in Chinese patent CN102503779, CN101445431, CN100434410, with fluoro bromobenzene for raw material obtains Grignard reagent, then reacts with boric acid ester and generates fluorobenzene boric acid, then through being oxidized obtained fluorophenol.This technological reaction condition is harsh, and potential safety hazard is large, and environmental pollution is serious, and material cost is high, is not suitable for suitability for industrialized production.3. hydrolysis method.Method disclosed in patent JP10025261, CN1208398, CN102887817, CN102718635, with fluoro bromobenzene for raw material, through the obtained fluorophenol of the reactions such as lithiumation, esterification, hydrolysis, oxidation, mainly there is product quality difference, yield is low, cost is high shortcoming in these class methods, is not suitable for suitability for industrialized production equally.
Because traditional phenol polyfluoro is for the various limitation of compound synthesis technology, add industry very high for the requirement of product purity, cause its production difficulty very large, valuable product, progress is slow, there is no at present to be suitable for industrialized fluorophenol production technique and can to reach the production requirement that yield is high, purity is high, environmental pollution is little, cost is low simultaneously.
Summary of the invention
In order to overcome be that number the deficiencies in the prior art, the object of this invention is to provide the method for a kind of synthesizing phenol compound of polyfluorinated organic generation, it is to be easy to realize industrialization, and can significantly solve in the past in production process yield low, pollute the problems such as large, energy consumption is large, product quality is poor, there is reaction conditions gentleness, yield be high, cost is low and eco-friendly feature.
To achieve these goals, the technical solution used in the present invention is:
A method for synthesizing phenol compound of polyfluorinated organic generation, is characterized in that, comprise the following steps:
A () makes in solvent that formula I compound is under catalyst action, temperature of reaction 100 ~ 180 DEG C, under reaction pressure 0.3 ~ 2.0Mpa, reaction times 6 ~ 12h, substitution reaction occurs;
B the reaction mass obtained in step (a) is carried out aftertreatment and obtains formula (II) compound by ();
Reaction scheme is as follows:
。
Catalyzer in described step (a) is selected from the one in RaneyNi, Pd/C, Pt/C, Ru/C.
Formula I in described step (a) can be the one in 3,4,5-tri-fluoro-1-halogeno-benzene, 3,5-bis-fluoro-1-halogeno-benzenes, 2,3,4,5,6-five fluoro-1-halogeno-benzenes, and wherein halogenic substituent X is selected from any one in F or Cl or Br or I.
Obtained by the formula I compound that formula (II) correspondence in described step (a) is added, product is 3,4,5-trifluoromethyl phenol, 3,5-trifluoromethyl phenols, 2,3,4,5-trifluoromethyl phenols.
The aqueous solution that solvent in described step (a) is alkali and the mixed solvent that aprotic polar solvent forms, wherein alkali is selected from KOH, NaOH, Ca (OH)
2, Na
2cO
3in a kind of or several arbitrarily mixed aqueous solutions, be preferably KOH and NaOH; Aprotic polar solvent is selected from a kind of or several arbitrarily mixture in tetramethylene sulfone or methyl-sulphoxide or acetone or acetonitrile or dimethyl formamide or hexamethylphosphoramide, is preferably tetramethylene sulfone; The concentration of aqueous solution of described alkali counts 15% ~ 30% with massfraction, is preferably 18% ~ 25%; In mixed solvent, the aqueous solution of alkali and aprotic polar solvent mass ratio are 1:0.10 ~ 0.38, are preferably 1:0.16 ~ 0.31.
In described step (a), the mass ratio of formula I compound and catalyzer is 1:0.034 ~ 0.082, is preferably 1:0.045 ~ 0.064.
In described step (a), temperature of reaction is 120 ~ 160 DEG C.
In described step (a), the reaction times is 8 ~ 10h.
In described step (a), reaction pressure is for being 0.5 ~ 1.8Mpa.
Aftertreatment technology in described step (b) is: discharged from reactor by reaction mass, cools, then filters, extraction, dry, rectifying.
Compared with prior art, the invention has the beneficial effects as follows:
Adopt that technical scheme of the present invention obtains 3,4,5-trifluoromethyl phenol, 3,5-difluorophenol product quality can reach the product requirement of industrial circle intermediate, particularly can meet as fluorinated liquid crystal monomer material intermediate, 2,3,4,5,6-Pentafluorophenol product quality can meet liquid crystal intermediates, the production requirement of medicine intermediate.
Adopt technical scheme of the present invention, raw material is easy to get, and cost is low, concise in technology, and product feather weight produces yield can reach more than 80%, and far above the yield that technique in the past obtains, and suitability for industrialized is produced, and product appearance good colour purity is high.
Accompanying drawing explanation
Fig. 1 is the GC spectrogram of formula II 2,3,4,5,6-Pentafluorophenol in the present invention.
Fig. 2 is the GC spectrogram of formula II 3,4,5-trifluoromethyl phenol in the present invention.
Fig. 3 is the IR spectrogram of formula II 2,3,4,5,6-Pentafluorophenol in the present invention.
Fig. 4 is the IR spectrogram of formula II 3,4,5-trifluoromethyl phenol in the present invention.
Fig. 5 is formula II 2,3,4,5,6-Pentafluorophenol in the present invention
1h-NMR spectrogram.
Fig. 6 is formula II 3,5-difluorophenol in the present invention
1h-NMR spectrogram.
Wherein, above accompanying drawing is every detected result of 3,4,5-trifluoromethyl phenols, 3,5-difluorophenols and 2,3,4,5, the 6-Pentafluorophenol product adopting the inventive method to obtain, and does not specifically belong to certain embodiment.
Embodiment
Below in conjunction with embodiment, the present invention is described further, but the invention is not restricted to following examples.
embodiment 1
2,3,4,5,6-five fluoro-1-bromobenzene 123.5g(0.5mol is added in 1L reactor), RaneyNi catalyzer 5.5g, 25.2%(massfraction) KOH aqueous solution 267.5g, tetramethylene sulfone 60.0g, be warming up to 180 DEG C, nitrogen supercharging, to 0.8Mpa, reacts 8h.Material cools after completion of the reaction, filters, and extraction merges organic phase, and dry, rectifying, obtains 2,3,4,5,6-Pentafluorophenol product 76.5g, fusing point 34-36 DEG C, yield 83.1%, content 99.61%.
embodiment 2
With reference to method described in embodiment 1, catalyzer changes Pd/C4.8g into, and all the other conditions are constant, obtains 2,3,4,5,6-Pentafluorophenol product 75.6g, fusing point 34-36 DEG C, yield 82.2%, content 99.52%.
embodiment 3
With reference to method described in embodiment 1, raw material changes penta fluoro benzene 93.0g(0.5mol into), temperature 120 DEG C, all the other conditions are constant, obtain 2,3,4,5,6-Pentafluorophenol product 80.3g, fusing point 34-36 DEG C, yield 87.3%, content 99.84%.
embodiment 5
With reference to method described in embodiment 1, raw material changes 3,4,5-tri-fluoro-1-bromobenzene 105.5g (0.5mol) into, and RaneyNi catalyzer 5.2g, is warming up to 150 DEG C, and nitrogen supercharging, to 1.0Mpa, reacts 10h.All the other conditions are constant, obtain 3,4,5-trifluoromethyl phenol product 60.2g, fusing point 53-55 DEG C, yield 81.3%, content 99.64%.
embodiment 6
With reference to method described in embodiment 1, raw material changes 3 into, 5-bis-fluoro-1-bromobenzene 96.5g (0.5mol), RaneyNi catalyzer 5.0g, is warming up to 130 DEG C, nitrogen supercharging is constant to all the other conditions of 0.8Mpa, obtain 3,5-difluorophenol product 52.6g, fusing point 39-41 DEG C, yield 80.8%, content 99.65%.
embodiment 7
2 are added, 3,4,5 in 10L autoclave, 6-five fluoro-1-bromobenzene 1235.0g(5.0mol), RaneyNi catalyzer 55g, 21.2%(massfraction) KOH aqueous solution 3172.0g, tetramethylene sulfone 645.0g, be warming up to 160 DEG C, nitrogen supercharging, to 1.0Mpa, reacts 8h.Material cools after completion of the reaction, filters, and extraction merges organic phase, and dry, rectifying, obtains 2,3,4,5,6-Pentafluorophenol product 741.5g, yield 81.1%, content 99.53%.
embodiment 8
With reference to method described in embodiment 5, catalyzer changes Pd/C48g into, and all the other conditions are constant, obtains 2,3,4,5,6-Pentafluorophenol product 746.1g, yield 84.7%, content 99.71%.
embodiment 9
With reference to method described in embodiment 5, raw material changes phenyl-hexafluoride 930.0g(5.0mol into), temperature 120 DEG C, all the other conditions are constant, obtain 2,3,4,5,6-Pentafluorophenol product 779.2g, yield 85.2%, content 99.79%.
In sum, adopt present method synthesizing phenol compound of polyfluorinated organic generation, raw material is easy to get, and cost is low, concise in technology, and yield can reach more than 80%, and far above the yield that technique in the past obtains, product purity reaches more than 99.5%, and appearance luster is good.
Claims (10)
1. a method for synthesizing phenol compound of polyfluorinated organic generation, is characterized in that, comprise the following steps:
A () makes in solvent that formula I compound is under catalyst action, temperature of reaction 100 ~ 180 DEG C, under reaction pressure 0.3 ~ 2.0Mpa, reaction times 6 ~ 12h, substitution reaction occurs;
B the reaction mass obtained in step (a) is carried out aftertreatment and obtains formula (II) compound by ();
Reaction scheme is as follows:
。
2. the method for the many fluoric compounds of a kind of synthesizing phenol according to claim 1, it is characterized in that, described formula I can be the fluoro-1-halogeno-benzene of 3,4,5-tri-, 3, the fluoro-1-halogeno-benzene of 5-bis-, 2,3,4,5, one in the fluoro-1-halogeno-benzene of 6-five, wherein halogenic substituent X is selected from any one in F or Cl or Br or I.
3. the method for the many fluoric compounds of a kind of synthesizing phenol according to claim 1, is characterized in that, obtained by the formula I compound that described formula (II) correspondence is added, product is 3,4,5-trifluoromethyl phenol, 3,5-trifluoromethyl phenols, 2,3,4,5-trifluoromethyl phenol.
4. the method for the many fluoric compounds of a kind of synthesizing phenol according to claim 1, it is characterized in that, described catalyzer is selected from the one in RaneyNi or Pd/C or Pt/C or Ru/C.
5. the method for the many fluoric compounds of a kind of synthesizing phenol according to claim 1, is characterized in that, the aqueous solution that described solvent is alkali and the mixed solvent that aprotic polar solvent forms, and wherein alkali is selected from KOH or NaOH or Ca (OH)
2or Na
2cO
3in a kind of or several arbitrarily mixed aqueous solutions; Aprotic polar solvent is selected from a kind of or several arbitrarily mixture in tetramethylene sulfone or methyl-sulphoxide or acetone or acetonitrile or dimethyl formamide or hexamethylphosphoramide; The concentration of aqueous solution of described alkali counts 15% ~ 30% with massfraction; In mixed solvent, the aqueous solution of alkali and aprotic polar solvent mass ratio are 1:0.10 ~ 0.38.
6. the method for the many fluoric compounds of a kind of synthesizing phenol according to claim 1, is characterized in that, described formula I compound and the mass ratio of catalyzer are 1:0.034 ~ 0.082.
7. the method for the many fluoric compounds of a kind of synthesizing phenol according to claim 1, is characterized in that, described temperature of reaction is 120 ~ 160 DEG C.
8. the method for the many fluoric compounds of a kind of synthesizing phenol according to claim 1, is characterized in that, the described reaction times is 8 ~ 10h.
9. the method for the many fluoric compounds of a kind of synthesizing phenol according to claim 1, is characterized in that, described reaction pressure is for being 0.5 ~ 1.8Mpa.
10. the method for the many fluoric compounds of a kind of synthesizing phenol according to claim 1, it is characterized in that, described aftertreatment technology is: discharged from reactor by reaction mass, cools, then filters, extraction, dry, rectifying.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107353181A (en) * | 2017-05-16 | 2017-11-17 | 衢州学院 | A kind of preparation method of Pentafluorophenol |
| 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 |
| CN112608220A (en) * | 2020-11-26 | 2021-04-06 | 浙江中欣氟材股份有限公司 | Synthetic method of 3, 5-difluorophenol |
| CN116283506A (en) * | 2023-02-20 | 2023-06-23 | 上海荟银化学技术有限公司 | Method for preparing 3,4, 5-trifluorophenol based on continuous flow reaction technology |
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| CN102887817A (en) * | 2012-09-11 | 2013-01-23 | 浙江永太科技股份有限公司 | Novel method for synthesizing 2,3,4,5,6-pentafluorophenol |
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| CN1424304A (en) * | 2002-12-12 | 2003-06-18 | 厦门市先端科技有限公司 | Preparation for aniline, phenol and derivative thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107353181A (en) * | 2017-05-16 | 2017-11-17 | 衢州学院 | A kind of preparation method of Pentafluorophenol |
| CN107353181B (en) * | 2017-05-16 | 2020-04-14 | 衢州学院 | Preparation method of pentafluorophenol |
| 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 |
| CN112608220A (en) * | 2020-11-26 | 2021-04-06 | 浙江中欣氟材股份有限公司 | Synthetic method of 3, 5-difluorophenol |
| CN112608220B (en) * | 2020-11-26 | 2022-06-07 | 浙江中欣氟材股份有限公司 | Synthetic method of 3, 5-difluorophenol |
| CN116283506A (en) * | 2023-02-20 | 2023-06-23 | 上海荟银化学技术有限公司 | Method for preparing 3,4, 5-trifluorophenol based on continuous flow reaction technology |
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Application publication date: 20160309 |