CN110407693A - A kind of synthetic method of 4- phenoxy benzoic acid - Google Patents
A kind of synthetic method of 4- phenoxy benzoic acid Download PDFInfo
- Publication number
- CN110407693A CN110407693A CN201910641568.4A CN201910641568A CN110407693A CN 110407693 A CN110407693 A CN 110407693A CN 201910641568 A CN201910641568 A CN 201910641568A CN 110407693 A CN110407693 A CN 110407693A
- Authority
- CN
- China
- Prior art keywords
- phenol
- benzoic acid
- phenoxy benzoic
- reaction
- synthetic method
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to technical field of chemical synthesis, particularly disclose a kind of synthetic method of 4- phenoxy benzoic acid.The synthetic method of the 4- phenoxy benzoic acid, using phenol as raw material, it is characterized in that: phenol, sodium hydroxide and water Hybrid Heating are reacted, phenol sodium solution is obtained；Phenol sodium solution is slowly added dropwise into naphthane, parachlorobenzoic-acid mixture, heating is added dropwise, insulation reaction；After reaction, reaction solution is cooled down, is filtered, and obtained solid is washed, filters, and later plus clear water mixes, adjusts pH value, filtering, obtains the thick wet product of 4- phenoxy benzoic acid；Thick wet product is dissolved with ethyl alcohol, through activated carbon adsorption, filtering, cooling, filtering, obtains product.Present invention process route is simple to operation, and reaction can be completed in a step, and starting material is simple and easy to get and cheap, and the waste water of generation is few, is more suitable for industrialized production, is a completely new synthetic route.
Description
(1) technical field
The present invention relates to technical field of chemical synthesis, in particular to a kind of synthetic method of 4- phenoxy benzoic acid.
(2) background technique
4- phenoxy benzoic acid, molecular formula C13H9O3, molecular weight 213.2093 act not only as medical, pesticide
Intermediate, and be also widely used in ester liquid crystal and heat-resisting material.Slotta and Scremba is for the first time by 4-
The compound has been made through oxidation in phenoxy benzaldehyde.Litter etc. is then synthesized with postassium hypochlorite oxidation this ketone of 4- phenoxy group
4- phenoxy benzoic acid (yield 64%).
Currently, industrialized production 4- phenoxy benzoic acid, most of process route reported in the literature is to be with diphenyl ether
Starting material, through acetylation, haloform reaction, acidification and target product；Fundamental way is exactly to be taken using similar haloform method synthesis
For benzoic acid, similar report is more, and above-mentioned production line raw materials are more, generates a large amount of waste water, and the cost of raw material is high, produces
Purity, the color of product are bad.In the prior art, it is still disclosed without high income, suitable for the preferable technique of industrialized production.
(3) summary of the invention
The 4- that in order to compensate for the shortcomings of the prior art, the present invention provides a kind of steps is simple, production cost is low, product yield is high
The synthetic method of phenoxy benzoic acid.
The present invention is achieved through the following technical solutions:
A kind of synthetic method of 4- phenoxy benzoic acid includes the following steps: using phenol as raw material
(1) phenol, sodium hydroxide and water Hybrid Heating are reacted, obtains phenol sodium solution；
(2) phenol sodium solution is slowly added dropwise into naphthane, parachlorobenzoic-acid mixture, heating is added dropwise, insulation reaction；
(3) after reaction, reaction solution is cooled down, is filtered, and obtained solid is washed, filters, and later plus clear water is mixed, adjusted
PH value, filtering obtain the thick wet product of 4- phenoxy benzoic acid；
(4) thick wet product is dissolved with ethyl alcohol, through activated carbon adsorption, filtering, cooling, filtering, obtains product.
The present invention uses the phenol that cost is relatively low, is easy to get for basic raw material, passes through naphthane, parachlorobenzoic-acid and benzene
The reaction of phenol sodium, a step obtain product, and synthetic route is novel, and is more suitable for industrialized production.
More excellent technical solution of the invention are as follows:
In step (1), the molar ratio of phenol and sodium hydroxide is 1:1-3.
Phenol, sodium hydroxide and water are mixed and heated to 60 DEG C, react 2-3 hours, sample detection, until phenol converts completely
For sodium phenate, keep temperature stand-by.
In step (2), the molar ratio of naphthane and parachlorobenzoic-acid is 4-5:1.
It installs reflux water-dividing device additional on the reactor for containing naphthane, parachlorobenzoic-acid, temperature of reactor is increased to
150-160 DEG C, phenol sodium solution is slowly added dropwise, 7-9h completion of dropwise addition, insulation reaction 2h, is detected after sampling processing, with benzene later
Phenol mass concentration is reaction end less than 0.5%.
In step (3), after reaction, reactor is cooled to 30 DEG C, and filtering reacting liquid, obtained solid is added clear water and stirs
Mix, be beaten, wash after filter, then with clear water be beaten and with concentrated hydrochloric acid adjust pH value be 1-2,4- phenoxy benzoic acid is obtained by filtration
Thick wet product.
In step (4), the ethyl alcohol of mass concentration 95% is added into thick wet product, is heated to reflux, after the solid is completely dissolved,
It is cooling, active carbon is added, continues to be heated to reflux 1h, filter while hot, under stirring by obtained filtrate slow cooling to 10 DEG C hereinafter,
A large amount of white solid is precipitated, product is obtained by filtration.
Present invention process route is simple to operation, and reaction can be completed in a step, and starting material is simple and easy to get and cheap, generates
Waste water it is few, be more suitable for industrialized production, be a completely new synthetic route.
(4) specific embodiment
The present invention will be further described combined with specific embodiments below.
Embodiment 1:
A kind of new technique for synthesizing of 4- phenoxy benzoic acid, technical process are as follows:
Phenol 94.6g, sodium hydroxide 61g, water 60g are added in 250ml flask, is heated to 60 DEG C, reacts 2.5 hours, sampling
Detection is sodium phenate until phenol substantially completely reacts, keeps temperature stand-by；
600g naphthane is added in 1000ml four-hole boiling flask, 158.7g parachlorobenzoic-acid installs reflux water-dividing device additional, by system
Temperature is heated to 155 DEG C or so, and the phenol sodium solution of previous step is slowly added dropwise, can be gradually in water segregator with the progress of dropwise addition
There is water to steam, about 8h completion of dropwise addition, insulation reaction 2h after completion of dropwise addition detects after sampling processing, less than 0.5% is anti-with phenol
Answer terminal.After reaction, 30 DEG C are cooled to, filtering, obtained solid is added in 1000ml flask, and 500ml clear water is added and stirs
It is filtered after mixing mashing washing, then being beaten with 300ml water and adjusted pH with concentrated hydrochloric acid is 1.5, and 4- phenoxy benzoic acid is obtained by filtration
Thick wet product 302g.
Above-mentioned thick wet product is added in 1000ml flask, 600g95% ethyl alcohol is added, is heated to reflux, is all dissolved to solid
Afterwards, slightly cooling, 5g active carbon is added, is heated to reflux 1h, filters while hot, by obtained filtrate slow cooling to 10 DEG C under stirring
Hereinafter, a large amount of white solid is precipitated, filter, drying obtains dry product 182.6g, purity 99.6%, yield 85.3%.
Embodiment 2:
A kind of new technique for synthesizing of 4- phenoxy benzoic acid, technical process are as follows:
Phenol 94.6g, sodium hydroxide 78g, water 70g are added in 250ml flask, is heated to 60 DEG C, reacts 2 hours, sampling inspection
It surveys, is sodium phenate until phenol substantially completely reacts, keeps temperature stand-by；
530g naphthane is added in 1000ml four-hole boiling flask, 158.7g parachlorobenzoic-acid installs reflux water-dividing device additional, by system
Temperature is heated to 150 DEG C or so, and the phenol sodium solution of previous step is slowly added dropwise, can be gradually in water segregator with the progress of dropwise addition
There is water to steam, about 8h completion of dropwise addition, insulation reaction 2h after completion of dropwise addition detects after sampling processing, less than 0.5% is anti-with phenol
Answer terminal.After reaction, 30 DEG C are cooled to, filtering, obtained solid is added in 1000ml flask, and 500ml clear water is added and stirs
It is filtered after mixing mashing washing, then being beaten with 300ml water and adjusted pH with concentrated hydrochloric acid is 1, and it is thick that 4- phenoxy benzoic acid is obtained by filtration
Wet product 318g.
Above-mentioned thick wet product is added in 1000ml flask, 600g95% ethyl alcohol is added, is heated to reflux, is all dissolved to solid
Afterwards, slightly cooling, 5g active carbon is added, is heated to reflux 1h, filters while hot, by obtained filtrate slow cooling to 10 DEG C under stirring
Hereinafter, a large amount of white solid is precipitated, filter, drying obtains dry product 190.7g, purity 99.5%, yield 89.0%.
Embodiment 3:
A kind of new technique for synthesizing of 4- phenoxy benzoic acid, technical process are as follows:
Phenol 94.6g, sodium hydroxide 50g, water 60g are added in 250ml flask, is heated to 60 DEG C, reacts 3 hours, sampling inspection
It surveys, it is known that it is sodium phenate that phenol, which substantially completely reacts, keeps temperature stand-by；
650g naphthane is added in 1000ml four-hole boiling flask, 158.7g parachlorobenzoic-acid installs reflux water-dividing device additional, by system
Temperature is heated to 160 DEG C, and the phenol sodium solution of previous step is slowly added dropwise, and with the progress of dropwise addition, can gradually have water in water segregator
It steams, about 8h completion of dropwise addition, insulation reaction 2h after completion of dropwise addition, is detected after sampling processing, it is whole for reaction less than 0.5% with phenol
Point.After reaction, 30 DEG C are cooled to, filtering, obtained solid is added in 1000ml flask, and the stirring of 500ml clear water is added and beats
It is filtered after plasm scouring, then being beaten with 300ml water and adjusted pH with concentrated hydrochloric acid is 2, and the thick wet product of 4- phenoxy benzoic acid is obtained by filtration
294g。
Above-mentioned thick wet product is added in 1000ml flask, 600g95% ethyl alcohol is added, is heated to reflux, is all dissolved to solid
Afterwards, slightly cooling, 5g active carbon is added, is heated to reflux 1h, filters while hot, by obtained filtrate slow cooling to 10 DEG C under stirring
Hereinafter, a large amount of white solid is precipitated, filter, drying obtains dry product 174.6g, purity 99.7%, yield 81.6%.
Claims (7)
1. a kind of synthetic method of 4- phenoxy benzoic acid, using phenol as raw material, it is characterized in that, include the following steps: (1) by benzene
Phenol, sodium hydroxide and the reaction of water Hybrid Heating, obtain phenol sodium solution；(2) slow into naphthane, parachlorobenzoic-acid mixture
Slow that phenol sodium solution is added dropwise, heating is added dropwise, insulation reaction；(3) after reaction, reaction solution is cooled down, is filtered, obtained solid
Washed, filtering, later plus clear water mixes, adjusts pH value, filtering, obtains the thick wet product of 4- phenoxy benzoic acid；(4) by thick wet product
It is dissolved with ethyl alcohol, through activated carbon adsorption, filtering, cooling, filtering, obtains product.
2. the synthetic method of 4- phenoxy benzoic acid according to claim 1, it is characterised in that: in step (1), phenol and
The molar ratio of sodium hydroxide is 1:1-3.
3. the synthetic method of 4- phenoxy benzoic acid according to claim 1, it is characterised in that: in step (1), phenol,
Sodium hydroxide and water are mixed and heated to 60 DEG C, react 2-3 hour, sample detection, until phenol is fully converted to sodium phenate, holding
Temperature is stand-by.
4. the synthetic method of 4- phenoxy benzoic acid according to claim 1, it is characterised in that: in step (2), naphthane
Molar ratio with parachlorobenzoic-acid is 4-5:1.
5. the synthetic method of 4- phenoxy benzoic acid according to claim 1, it is characterised in that: in step (2), containing
Naphthane, parachlorobenzoic-acid reactor on install additional reflux water-dividing device, temperature of reactor is increased to 150-160 DEG C, slowly
Phenol sodium solution is added dropwise, 7-9h completion of dropwise addition, insulation reaction 2h, is detected after sampling processing, be less than with phenol quality concentration later
0.5% is reaction end.
6. the synthetic method of 4- phenoxy benzoic acid according to claim 1, it is characterised in that: in step (3), reaction knot
Shu Hou, reactor are cooled to 30 DEG C, and filtering reacting liquid, obtained solid filters after clear water stirring, mashing, washing is added, then uses
It is 1-2 that clear water, which is beaten and adjusts pH value with concentrated hydrochloric acid, and the thick wet product of 4- phenoxy benzoic acid is obtained by filtration.
7. the synthetic method of 4- phenoxy benzoic acid according to claim 1, it is characterised in that: in step (4), to thick wet
The ethyl alcohol of mass concentration 95% is added in product, is heated to reflux, it is after the solid is completely dissolved, cooling, active carbon is added, continues to heat
Flow back 1h, filters while hot, by obtained filtrate slow cooling to 10 DEG C hereinafter, a large amount of white solid is precipitated under stirring, filters
Obtain product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910641568.4A CN110407693A (en) | 2019-07-16 | 2019-07-16 | A kind of synthetic method of 4- phenoxy benzoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910641568.4A CN110407693A (en) | 2019-07-16 | 2019-07-16 | A kind of synthetic method of 4- phenoxy benzoic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110407693A true CN110407693A (en) | 2019-11-05 |
Family
ID=68361646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910641568.4A Pending CN110407693A (en) | 2019-07-16 | 2019-07-16 | A kind of synthetic method of 4- phenoxy benzoic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110407693A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114890899A (en) * | 2022-04-02 | 2022-08-12 | 南京农业大学 | Method for preparing diphenyl ether ester compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07188104A (en) * | 1993-12-28 | 1995-07-25 | Mitsui Toatsu Chem Inc | Production of phenoxybenzoic acid |
-
2019
- 2019-07-16 CN CN201910641568.4A patent/CN110407693A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07188104A (en) * | 1993-12-28 | 1995-07-25 | Mitsui Toatsu Chem Inc | Production of phenoxybenzoic acid |
Non-Patent Citations (2)
| Title |
|---|
| 王彦林等: "《精细化工单元反应与工艺》", 30 November 1996, 河南大学出版社 * |
| 顾可权: "《重要有机合成反应》", 30 June 1988, 上海科学技术出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114890899A (en) * | 2022-04-02 | 2022-08-12 | 南京农业大学 | Method for preparing diphenyl ether ester compound |
| CN114890899B (en) * | 2022-04-02 | 2023-10-03 | 南京农业大学 | Method for preparing diphenyl ether ester compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111646922B (en) | Synthetic method of 2- (4-bromo-2-cyano-6-fluorophenyl) acetic acid | |
| CN110407693A (en) | A kind of synthetic method of 4- phenoxy benzoic acid | |
| CN111004162A (en) | Method and device for preparing L-selenocysteine by using sodium triacetoxyborohydride as reducing agent | |
| CN102030669A (en) | Clean production method for glycine | |
| WO2016127890A1 (en) | Glyphosate pesticide active combination and method for preparing same | |
| CN105646324B (en) | A kind of preparation method of high-purity indoles | |
| JP5506480B2 (en) | Process for producing purified 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid | |
| CN101519360B (en) | Method for preparing iminodiacetic acid | |
| CN106748835B (en) | A kind of preparation method of stryphnonasal | |
| CN111253272B (en) | Method for preparing benzamide compound | |
| CN108203392A (en) | A kind of process for cleanly preparing of glycine in coproduction with ammonium chloride | |
| CN104163778B (en) | A kind of method preparing p-amino-benzamidine hydrochloride | |
| CN106831460A (en) | The preparation method of the aminobenzoic acid of 3 methyl 4 | |
| CN111056997A (en) | Synthetic method of benzamide compound | |
| CN109575019A (en) | A kind of preparation method of 5- bromo-7-azaindole | |
| CN108424361A (en) | A kind of preparation method of 2,4 dichlorophenoxyacetic acid | |
| CN109503339A (en) | A kind of preparation method of meta-methoxy phenol | |
| CN115124452B (en) | Preparation method of 2- (4-amino-2-ethoxyphenyl) isoindole-1, 3-dione | |
| JP2708558B2 (en) | Process for producing pyruvate or pyruvate | |
| CN114805041B (en) | Synthesis method of 2-chloro-3-fluoro-4- (trifluoromethyl) benzaldehyde | |
| CN114957202B (en) | Preparation method of DL-homocysteine thiolactone hydrochloride | |
| CN101607914A (en) | Simple method for preparing to tert-butyl benzyl amine | |
| CN110511192B (en) | Benzamide compound and synthesis method thereof | |
| CN102675232B (en) | Synthetic method of 4-(6-chlorine-quinoxaline-2-yloxy)-phenol | |
| CN101747224A (en) | One-pot method for preparing alpha-acetamidocinnamic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191105 |