CN107793295A - A kind of preparation method of 3,5 difluorophenol - Google Patents
A kind of preparation method of 3,5 difluorophenol Download PDFInfo
- Publication number
- CN107793295A CN107793295A CN201610772273.7A CN201610772273A CN107793295A CN 107793295 A CN107793295 A CN 107793295A CN 201610772273 A CN201610772273 A CN 201610772273A CN 107793295 A CN107793295 A CN 107793295A
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- added dropwise
- preparation
- difluorophenols
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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
- C07C37/01—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
- C07C37/045—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 a group bound to the ring by nitrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/20—Diazonium compounds
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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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
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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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
-
- 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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
Abstract
The invention discloses a kind of preparation method of 3,5 difluorophenols, including comprise the following steps that：(a) raw material prepares；(b) preparation of diazol：3,4,5 trifluoromethyl anilines are added drop-wise to mass fraction as in 50% sulfuric acid solution；(c) react；(d) hydrolysis of diazol：50% hypophosphorous acid solution, then add catalyst, diazonium salt solution is added dropwise and is stirred；(e) separating-purifying：Extracting rectifying, obtain target compound.The technique that the present invention designs this synthetic route is relatively simple, and raw material is easy to get, and cost is relatively low, and mild condition, yield is higher, is ideal synthetic method, and target compound is widely used, is adapted to industrialized production.
Description
【Technical field】
The present invention relates to medicine, agricultural chemicals, liquid crystal material intermediate technical field, particularly one kind 3,5- difluorophenols
The technical field of preparation method.
【Background technology】
The chemical stability and physiologically active of organofluorine compound possess stronger fat apparently higher than other compound
Dissolubility and hydrophobicity, empirical tests show that fluorine-containing medicines compare in performance that other product toxicities are lower, drug effect is higher, generation with agricultural chemicals
Thank that ability is stronger, therefore be widely used in the fields such as the manufacture of medicine and agricultural chemicals.In addition, in some other necks
It can also be seen in domain, such as fluoride dye of synthesis, fluorine-containing surfactant, and the development and application of fabric finishing agent, coating etc.
To market prospects.
3,5- difluorophenols are pale white crystals body, 51~55 DEG C of fusing point, are used for synthesizing liquid crystal material, antimycotic agent
Deng being additionally operable to synthetic dyestuffs, plastics and rubber additive, be important medicine, agricultural chemicals, liquid crystal material intermediate, market has and needed
Ask, but the country has no synthesis report, and foreign countries are now with several synthetic methods：
1) by H that 3,5- difluoros phenyl boric acid and mass fraction are 10%2O2Reacted in diethyl ether solution, obtain 3,5- difluoros
Phenol；
2) the fluoro- 6- alkoxyl anilines of 2,4- bis- are raw material, deaminizating and alkyl, obtain 3,5- difluorophenols；
3) with 1,3- difluorobenzenes for raw material, hydrogen is pulled out by LDA, hydrolysis, then by H2O2Reaction, obtains target chemical combination
Thing 3,5- difluorophenols；
4) 3,4,5- trifluoromethyl anilines, with natrium nitrosum diazotising, then hydrolyze to obtain 3,5- difluorophenols in sulfuric acid.
【The content of the invention】
The purpose of the present invention is exactly to solve the problems of the prior art, proposes the preparation method of one kind 3,5- difluorophenols,
To achieve the above object, the present invention proposes the preparation method of one kind 3,5- difluorophenols, including specific steps are such as
Under：
(a) raw material prepares：3,4,5- trifluoromethyl aniline mass fractions are 99%, and concentrated sulfuric acid mass fraction is 98%, hypophosphorous acid
Mass fraction is 50% aqueous solution, equal industrial goods, natrium nitrosum and dichloromethane, and chemistry is pure；
(b) preparation of diazol：It is 50% sulfuric acid solution that 3,4,5- trifluoromethyl anilines, which are added drop-wise to equipped with appropriate mass fraction,
Reaction bulb A in, while be added dropwise while be stirred, controlling reaction temperature, when 3,4,5- trifluoromethyl anilines be added dropwise exceed half amount when, water
Bath heating, accelerates rate of addition；
(c) react：Cooled down after being added dropwise, then the sodium nitrite solution that mass fraction is 30% be added dropwise into reaction bulb A,
Rate of addition is controlled, keeps reaction temperature, reaction end is determined with starch potassium iodide paper, stops being added dropwise, it is molten to obtain diazol
Liquid；
(d) hydrolysis of diazol：Under conditions of 45~50 DEG C, diazonium salt solution is stirred, cooled and filtered obtains
To orange-yellow clear solution, the hypophosphorous acid solution that appropriate mass fraction is 50% is poured into reaction bulb B, adds appropriate catalysis
Agent, stirring heating, is added dropwise diazonium salt solution, controls rate of addition and ensures reaction temperature, room temperature is cooled to after being added dropwise, after
Continuous stirring, obtains mixed liquor；
(e) separating-purifying：Mixed liquor is extracted 3 times with q. s. methylene chloride, combining extraction liquid, normal pressure steams dichloromethane
Afterwards, rectification under vacuum is carried out, obtains 3,5- difluorophenol solids.
Preferably, in the step (a), natrium nitrosum and dichloromethane are as catalyst.
Preferably, in the step (b), reaction bulb A is polythene material, and controlling reaction temperature is less than 30 DEG C, water-bath
The temperature of heating is 55 DEG C.
Preferably, in the step (c), the temperature of cooling is less than 20 DEG C, and reaction temperature is maintained at less than 20 DEG C.
Preferably, in the step (d), diazonium salt solution is stirred 2h, and stirring is warming up to 50 DEG C, and reaction temperature is
50~55 DEG C, continue to stir 0.5h.
Beneficial effects of the present invention：The technique that the present invention designs this synthetic route is relatively simple, and the raw material cost that is easy to get is relatively low,
Mild condition, yield is higher, is ideal synthetic method, and target compound is widely used, is adapted to industrialized production.
The feature and advantage of the present invention will be described in detail by embodiment.
【Embodiment】
The preparation method of one kind 3,5- difluorophenols of the invention, including comprise the following steps that：
(a) raw material prepares：3,4,5- trifluoromethyl aniline mass fractions are 99%, and concentrated sulfuric acid mass fraction is 98%, hypophosphorous acid
Mass fraction is 50% aqueous solution, equal industrial goods, natrium nitrosum and dichloromethane, and chemistry is pure；Natrium nitrosum and dichloromethane
Alkane is as catalyst.
(b) preparation of diazol：It is 50% sulfuric acid solution that 3,4,5- trifluoromethyl anilines, which are added drop-wise to equipped with appropriate mass fraction,
Reaction bulb A in, while be added dropwise while be stirred, controlling reaction temperature be less than 30 DEG C, when 3,4,5- trifluoromethyl anilines be added dropwise more than one
During half amount, warming-in-water temperature is 55 DEG C, accelerates rate of addition；Reaction bulb A is polythene material.
(c) react：Less than 20 DEG C are cooled to after being added dropwise, then the Asia that mass fraction is 30% is added dropwise into reaction bulb A
Sodium nitrate solution, rate of addition is controlled, keep reaction temperature, reaction end is determined with starch potassium iodide paper, stopped being added dropwise, obtain
To diazonium salt solution；Reaction temperature is maintained at less than 20 DEG C.
(d) hydrolysis of diazol：Under conditions of 45~50 DEG C, diazonium salt solution is stirred 2h, cooled and filtered
Orange-yellow clear solution is obtained, the hypophosphorous acid solution that appropriate mass fraction is 50% is poured into reaction bulb B, adds and urges in right amount
Agent, stirring are warming up to 50 DEG C, and diazonium salt solution is added dropwise, and control rate of addition and ensure that reaction temperature is 50~55 DEG C, are added dropwise
After be cooled to room temperature, continue stir 0.5h, obtain mixed liquor；Reaction bulb B is polythene material.
(e) separating-purifying：Mixed liquor is extracted 3 times with q. s. methylene chloride, combining extraction liquid, normal pressure steams dichloromethane
Afterwards, rectification under vacuum is carried out, obtains 3,5- difluorophenol solids.
Obtained 3,5- difluorophenol solids, purity can reach more than 98%, yield more than 68%.
The present invention, it is relatively simple to design the technique of this synthetic route, and the raw material cost that is easy to get is relatively low, mild condition, yield compared with
Height, it is ideal synthetic method, target compound is widely used, is adapted to industrialized production.
Above-described embodiment is the description of the invention, is not limitation of the invention, it is any to simple transformation of the present invention after
Scheme belong to protection scope of the present invention.
Claims (5)
1. one kind 3, the preparation method of 5- difluorophenols, including comprise the following steps that：
(a) raw material prepares：3,4,5- trifluoromethyl aniline mass fractions are 99%, and concentrated sulfuric acid mass fraction is 98%, hypophosphorous acid quality
Fraction is 50% aqueous solution, equal industrial goods, natrium nitrosum and dichloromethane, and chemistry is pure；
(b) preparation of diazol：It is the anti-of 50% sulfuric acid solution that 3,4,5- trifluoromethyl anilines, which are added drop-wise to equipped with appropriate mass fraction,
Answer in bottle A, be stirred when being added dropwise, controlling reaction temperature, when 3,4,5- trifluoromethyl anilines, which are added dropwise, exceedes half amount, water-bath liter
Temperature, accelerate rate of addition；
(c) react：Cooled down after being added dropwise, then the sodium nitrite solution that mass fraction is 30%, control are added dropwise into reaction bulb A
Rate of addition, reaction temperature is kept, reaction end is determined with starch potassium iodide paper, stopped being added dropwise, obtain diazonium salt solution；
(d) hydrolysis of diazol：Under conditions of 45~50 DEG C, diazonium salt solution is stirred, cooled and filtered obtains orange
Yellow transparent solution, the hypophosphorous acid solution that appropriate mass fraction is 50% is poured into reaction bulb B, adds proper catalyst,
Stirring heating, is added dropwise diazonium salt solution, controls rate of addition and ensures reaction temperature, room temperature is cooled to after being added dropwise, continues
Stirring, obtains mixed liquor；
(e) separating-purifying：Mixed liquor is extracted 3 times with q. s. methylene chloride, combining extraction liquid, after normal pressure steams dichloromethane,
Rectification under vacuum is carried out, obtains 3,5- difluorophenol solids.
2. the preparation method of one kind 3,5- difluorophenols as claimed in claim 1, it is characterised in that：It is sub- in the step (a)
Sodium nitrate and dichloromethane are as catalyst.
3. the preparation method of one kind 3,5- difluorophenols as claimed in claim 1, it is characterised in that：In the step (b), instead
It is polythene material to answer bottle A, and controlling reaction temperature is less than 30 DEG C, and the temperature of warming-in-water is 55 DEG C.
4. the preparation method of one kind 3,5- difluorophenols as claimed in claim 1, it is characterised in that：It is cold in the step (c)
But temperature is less than 20 DEG C, and reaction temperature is maintained at less than 20 DEG C.
5. the preparation method of one kind 3,5- difluorophenols as claimed in claim 1, it is characterised in that：In the step (d), weight
Nitrogen salt solution is stirred 2h, and stirring is warming up to 50 DEG C, and reaction temperature is 50~55 DEG C, continues to stir 0.5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610772273.7A CN107793295A (en) | 2016-08-30 | 2016-08-30 | A kind of preparation method of 3,5 difluorophenol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610772273.7A CN107793295A (en) | 2016-08-30 | 2016-08-30 | A kind of preparation method of 3,5 difluorophenol |
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| CN107793295A true CN107793295A (en) | 2018-03-13 |
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| CN201610772273.7A Pending CN107793295A (en) | 2016-08-30 | 2016-08-30 | A kind of preparation method of 3,5 difluorophenol |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110937979A (en) * | 2019-12-13 | 2020-03-31 | 盐城工学院 | Method for separating and purifying fluorobenzene by extractive distillation |
| CN111978159A (en) * | 2020-07-15 | 2020-11-24 | 宁夏东吴农化股份有限公司 | Method for synthesizing para-fluorophenol by tubular reactor |
| CN115108891A (en) * | 2022-07-18 | 2022-09-27 | 烟台盛华液晶材料有限公司 | Preparation method of 3, 5-difluorophenol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1149715A (en) * | 1997-07-31 | 1999-02-23 | Kanto Denka Kogyo Co Ltd | Production of difluorophenols |
-
2016
- 2016-08-30 CN CN201610772273.7A patent/CN107793295A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1149715A (en) * | 1997-07-31 | 1999-02-23 | Kanto Denka Kogyo Co Ltd | Production of difluorophenols |
Non-Patent Citations (2)
| Title |
|---|
| A. S. MATHARU，等: "Laterally fluorinated liquid crystals containing the 2,2′‐bithiophene moiety", 《LIQUID CRYSTALS》 * |
| 李娜，等: "2，3-二氟苯酚的合成", 《化工生产与技术》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110937979A (en) * | 2019-12-13 | 2020-03-31 | 盐城工学院 | Method for separating and purifying fluorobenzene by extractive distillation |
| CN110937979B (en) * | 2019-12-13 | 2022-09-06 | 盐城工学院 | Method for separating and purifying fluorobenzene by extractive distillation |
| CN111978159A (en) * | 2020-07-15 | 2020-11-24 | 宁夏东吴农化股份有限公司 | Method for synthesizing para-fluorophenol by tubular reactor |
| CN115108891A (en) * | 2022-07-18 | 2022-09-27 | 烟台盛华液晶材料有限公司 | Preparation method of 3, 5-difluorophenol |
| CN115108891B (en) * | 2022-07-18 | 2024-04-23 | 烟台盛华液晶材料有限公司 | Preparation method of 3, 5-difluorophenol |
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Application publication date: 20180313 |