CN110156591A - A method of high-purity parafluorobenzoic acid is prepared using 4-Fluorobenzaldehyde by-product crude acid - Google Patents
A method of high-purity parafluorobenzoic acid is prepared using 4-Fluorobenzaldehyde by-product crude acid Download PDFInfo
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- CN110156591A CN110156591A CN201910457316.6A CN201910457316A CN110156591A CN 110156591 A CN110156591 A CN 110156591A CN 201910457316 A CN201910457316 A CN 201910457316A CN 110156591 A CN110156591 A CN 110156591A
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- C07—ORGANIC CHEMISTRY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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Abstract
The invention discloses a kind of methods using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid.4-Fluorobenzaldehyde by-product crude acid and water are mixed first, adjust the pH value of mixed system using liquid alkaline under stiring, until mixed system dissolution clarification；Then organic solvent and oxidant is added, carries out extraction reaction under constant stirring；Standing split-phase is carried out after extraction reaction, divides and goes organic phase, active carbon is added in gained water phase and is stirred adsorption bleaching, is filtered after decoloration；Gained filtrate is adjusted into its pH value using hydrochloric acid, crystallization, filtering, washing and drying is then successively stirred, high-purity parafluorobenzoic acid product is obtained after drying.Using technical solution of the present invention, the purity of the by-product parafluorobenzoic acid of 4-Fluorobenzaldehyde can be increased to 99.5% or more by 90% or so, to meet the needs of downstream client is to 99.5% or more high-purity parafluorobenzoic acid.
Description
One, technical field:
The present invention relates to a kind of preparation methods of chemical intermediate, utilize 4-Fluorobenzaldehyde by-product more particularly, to a kind of
The method of crude acid preparation high-purity parafluorobenzoic acid.
Two, background technique:
4-Fluorobenzaldehyde (abbreviation PFDA) is a kind of very important organic synthesis intermediate, can be used for medicine, pesticide and
The synthesis of dyestuff etc. also can be used as cosmetic additive agent, plastic additive and its plant protection product, fungicide, deodorant etc., it
Can be used to synthesize drug haloperidol, droperidol and the blood lipid-lowering medicine Rosuvastain fourth for the treatment of the nervous system disease, stand it is general
Peace etc..In addition, 4-Fluorobenzaldehyde, which can also be used in synthesis actasal, anticarcinogen and muscle, broadcasts medicine etc..
Currently, the main method of synthesis 4-Fluorobenzaldehyde has: p-chlorobenzaldehyde fluoride process, fluorobenzoyl method, to fluorine first
Benzene indirect electrochemical oxidation method, p-fluorotoluene side chain halogen process and p-fluorotoluene chlorinolysis.When 4-Fluorobenzaldehyde use pair
Toluene fluoride is raw material, when with the preparation of chlorinated hydrolysis route, can generate by-product parafluorobenzoic acid crude product, but in this by-product acid crude
Often containing 4-Fluorobenzaldehyde, to the impurity such as three benzyl chloride of fluorine, the chloro- 4- fluobenzoic acid of 2-, the chloro- 4- fluobenzoic acid of 3-, product purity
Only 90% or so, it cannot meet customer need.
Three, summary of the invention:
The technical problem to be solved by the present invention is preparing 4-Fluorobenzaldehyde process according to current p-fluorotoluene chlorinolysis
Middle by-product parafluorobenzoic acid crude product purity is not able to satisfy the technical problem of customer requirement, and the present invention provides a kind of using to fluorobenzene
The method of formaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid.
To solve the above-mentioned problems, the technical solution adopted by the present invention is that:
The present invention provides a kind of method using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid, described
Preparation method the following steps are included:
A, 4-Fluorobenzaldehyde by-product crude acid, that is, parafluorobenzoic acid crude product and water are mixed, is used under constant stirring
Liquid alkaline adjusts the pH value of mixed system, until mixed system dissolution clarification；
B, organic solvent and oxidant are then added into reaction system obtained by step a, is extracted under constant stirring
Reaction；
C, standing split-phase is carried out after extraction reaction, divides and goes organic phase, active carbon is added in gained water phase and is stirred absorption
Decoloration, is filtered after decoloration；
D, gained filtrate is adjusted into its pH value using hydrochloric acid, is then successively stirred crystallization, filtering, washing and drying,
High-purity parafluorobenzoic acid product is obtained after drying.
According to the above-mentioned method using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid, in step a
When the parafluorobenzoic acid crude product and water are mixed, mixing mass ratio between the two is 1:5~20.
According to the above-mentioned method using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid, in step a
The pH value of mixed system is adjusted to 8~12 using liquid alkaline；The liquid alkaline is the sodium hydrate aqueous solution of mass percentage concentration 30%.
According to the above-mentioned method using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid, in step b
The organic solvent is at least one of methylene chloride, dichloroethanes, ethyl acetate, methyl tertiary butyl ether(MTBE) and toluene；It is described
Oxidant is hydrogen peroxide, sodium hypochlorite or sodium peroxide.
According to the above-mentioned method using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid, in step b
Mass ratio between the parafluorobenzoic acid crude product and organic solvent is 1:1~10, the parafluorobenzoic acid crude product and oxidant
Between mass ratio be 1:0.05~0.2.
According to the above-mentioned method using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid, in step c
Mass ratio between the additional amount and parafluorobenzoic acid crude product of the active carbon is 0.02~0.3:1.
According to the above-mentioned method using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid, in step d
Gained filtrate adjusts its pH value to 1~5 using hydrochloric acid.
According to the above-mentioned method using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid, in step d
It is that product is dried to water in products under the conditions of temperature is 100 DEG C to divide mass percentage < 0.5% when the drying.
Positive beneficial effect of the invention:
It, can be by the purity of the by-product parafluorobenzoic acid of 4-Fluorobenzaldehyde by 90% or so using technical solution of the present invention
It is increased to 99.5% or more, to meet the needs of downstream client is to 99.5% or more high-purity parafluorobenzoic acid.Therefore, this hair
It is bright to produce significant economic benefit.
Four, Detailed description of the invention:
Liquid chromatogram before the processing of Fig. 1 4-Fluorobenzaldehyde by-product crude acid；
The liquid chromatogram of 1 products obtained therefrom high-purity parafluorobenzoic acid of Fig. 2 embodiment of the present invention；
The liquid chromatogram of 2 products obtained therefrom high-purity parafluorobenzoic acid of Fig. 3 embodiment of the present invention；
The liquid chromatogram of 3 products obtained therefrom high-purity parafluorobenzoic acid of Fig. 4 embodiment of the present invention.
Five, specific embodiment:
The present invention is further explained with reference to embodiments, but is not intended to limit the range of technical solution of the present invention protection.
Embodiment 1:
The method that the present invention prepares high-purity parafluorobenzoic acid using 4-Fluorobenzaldehyde by-product crude acid, the preparation method
Detailed step is as follows:
A, 4-Fluorobenzaldehyde by-product crude acid, that is, parafluorobenzoic acid crude product 200kg and 1600kg water is mixed, not
Using the pH value of the sodium hydrate aqueous solution adjusting mixed system of mass percentage concentration 30% to 10, stirring to mixing under disconnected stirring
System dissolution clarification；
B, dichloroethanes 1200kg and hydrogen peroxide 20kg is then added into reaction system obtained by step a, is being stirred continuously
Under carry out extraction reaction；
C, standing split-phase is carried out after extraction reaction, divides and goes organic phase, active carbon 10kg is added in gained water phase and is stirred
Adsorption bleaching is filtered after decoloration；
D, gained filtrate is adjusted into its pH value to 4 using hydrochloric acid, is then successively stirred crystallization, filtering, washing, then
Water in products is dried under the conditions of temperature is 100 DEG C and divides mass percentage < 0.5%, obtains the production of high-purity parafluorobenzoic acid
Product.
The purity of high-purity parafluorobenzoic acid product obtained by the present embodiment is 99.81%, is detailed in attached drawing 2.
Embodiment 2:
The method that the present invention prepares high-purity parafluorobenzoic acid using 4-Fluorobenzaldehyde by-product crude acid, the preparation method
Detailed step is as follows:
A, 4-Fluorobenzaldehyde by-product crude acid, that is, parafluorobenzoic acid crude product 200kg and 2200kg water is mixed, not
Using the pH value of the sodium hydrate aqueous solution adjusting mixed system of mass percentage concentration 30% to 9, stirring to mixing under disconnected stirring
System dissolution clarification；
B, methyl tertiary butyl ether(MTBE) 1000kg and sodium peroxide 16kg is then added into reaction system obtained by step a, not
Extraction reaction is carried out under disconnected stirring；
C, standing split-phase is carried out after extraction reaction, divides and goes organic phase, active carbon 15kg is added in gained water phase and is stirred
Adsorption bleaching is filtered after decoloration；
D, gained filtrate is adjusted into its pH value to 3 using hydrochloric acid, is then successively stirred crystallization, filtering, washing, then
Water in products is dried under the conditions of temperature is 100 DEG C and divides mass percentage < 0.5%, obtains the production of high-purity parafluorobenzoic acid
Product.
The purity of high-purity parafluorobenzoic acid product obtained by the present embodiment is 99.96%, is detailed in attached drawing 3.
Embodiment 3:
The method that the present invention prepares high-purity parafluorobenzoic acid using 4-Fluorobenzaldehyde by-product crude acid, the preparation method
Detailed step is as follows:
A, 4-Fluorobenzaldehyde by-product crude acid, that is, parafluorobenzoic acid crude product 200kg and 3000kg water is mixed, not
Using the pH value of the sodium hydrate aqueous solution adjusting mixed system of mass percentage concentration 30% to 11, stirring to mixing under disconnected stirring
System dissolution clarification；
B, ethyl acetate 1600kg and sodium hypochlorite 10kg is then added into reaction system obtained by step a, is constantly stirring
Extraction reaction is carried out under mixing；
C, standing split-phase is carried out after extraction reaction, divides and goes organic phase, active carbon 16kg is added in gained water phase and is stirred
Adsorption bleaching is filtered after decoloration；
D, gained filtrate is adjusted into its pH value to 2 using hydrochloric acid, is then successively stirred crystallization, filtering, washing, then
Water in products is dried under the conditions of temperature is 100 DEG C and divides mass percentage < 0.5%, obtains the production of high-purity parafluorobenzoic acid
Product.
The purity of high-purity parafluorobenzoic acid product obtained by the present embodiment is 99.88%, is detailed in attached drawing 4.
Embodiment 4:
The method that the present invention prepares high-purity parafluorobenzoic acid using 4-Fluorobenzaldehyde by-product crude acid, the preparation method
Detailed step is as follows:
A, 4-Fluorobenzaldehyde by-product crude acid, that is, parafluorobenzoic acid crude product 200kg and 3600kg water is mixed, not
Using the pH value of the sodium hydrate aqueous solution adjusting mixed system of mass percentage concentration 30% to 10, stirring to mixing under disconnected stirring
System dissolution clarification；
B, dichloroethanes 1600kg and hydrogen peroxide 25kg is then added into reaction system obtained by step a, is being stirred continuously
Under carry out extraction reaction；
C, standing split-phase is carried out after extraction reaction, divides and goes organic phase, active carbon 20kg is added in gained water phase and is stirred
Adsorption bleaching is filtered after decoloration；
D, gained filtrate is adjusted into its pH value to 3 using hydrochloric acid, is then successively stirred crystallization, filtering, washing, then
Water in products is dried under the conditions of temperature is 100 DEG C and divides mass percentage < 0.5%, obtains high-purity parafluorobenzoic acid product.
Claims (8)
1. a kind of method using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid, which is characterized in that described
Preparation method the following steps are included:
A, 4-Fluorobenzaldehyde by-product crude acid, that is, parafluorobenzoic acid crude product and water are mixed, uses liquid alkaline under constant stirring
The pH value of mixed system is adjusted, until mixed system dissolution clarification；
B, organic solvent and oxidant are then added into reaction system obtained by step a, carries out extraction reaction under constant stirring；
C, standing split-phase is carried out after extraction reaction, divides and goes organic phase, active carbon is added in gained water phase and is stirred adsorption bleaching,
It is filtered after decoloration；
D, gained filtrate is adjusted into its pH value using hydrochloric acid, is then successively stirred crystallization, filtering, washing and drying, dried
After obtain high-purity parafluorobenzoic acid product.
2. the method according to claim 1 using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid,
It is characterized by: mixing mass ratio between the two is 1:5 when parafluorobenzoic acid crude product and water described in step a are mixed
~20.
3. the method according to claim 1 using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid,
It is characterized by: using the pH value of liquid alkaline adjusting mixed system to 8~12 in step a；The liquid alkaline is mass percentage concentration
30% sodium hydrate aqueous solution.
4. the method according to claim 1 using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid,
It is characterized by: organic solvent described in step b is methylene chloride, dichloroethanes, ethyl acetate, methyl tertiary butyl ether(MTBE) and toluene
At least one of；The oxidant is hydrogen peroxide, sodium hypochlorite or sodium peroxide.
5. the method according to claim 1 using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid,
It is characterized by: the mass ratio between parafluorobenzoic acid crude product and organic solvent described in step b is 1:1~10, it is described to fluorine
Mass ratio between benzoic acid crude product and oxidant is 1:0.05~0.2.
6. the method according to claim 1 using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid,
It is characterized by: the mass ratio between the additional amount and parafluorobenzoic acid crude product of active carbon described in step c is 0.02~0.3:
1。
7. the method according to claim 1 using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid,
It is characterized by: gained filtrate uses hydrochloric acid to adjust its pH value to 1~5 in step d.
8. the method according to claim 1 using 4-Fluorobenzaldehyde by-product crude acid preparation high-purity parafluorobenzoic acid,
It is characterized by: being that product is dried to water in products sub-prime amount under the conditions of temperature is 100 DEG C when being dried described in step d
Percentage composition < 0.5%.
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| CN201910457316.6A CN110156591A (en) | 2019-05-29 | 2019-05-29 | A method of high-purity parafluorobenzoic acid is prepared using 4-Fluorobenzaldehyde by-product crude acid |
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| CN201910457316.6A CN110156591A (en) | 2019-05-29 | 2019-05-29 | A method of high-purity parafluorobenzoic acid is prepared using 4-Fluorobenzaldehyde by-product crude acid |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3950431A (en) * | 1972-11-21 | 1976-04-13 | Sumitomo Chemical Company, Limited | Process for removing impurities in an oxidation mixture |
| CN104192802A (en) * | 2014-08-29 | 2014-12-10 | 浙江大洋生物科技集团股份有限公司 | Purification method of coproduct hydrochloric acid of 2-chloro-6-fluorobenzaldehyde or analogs |
| CN109020801A (en) * | 2018-09-04 | 2018-12-18 | 江苏超跃化学有限公司 | The recovery method of by-product parachlorobenzoic-acid in a kind of p-chlorobenzaldehyde production process |
-
2019
- 2019-05-29 CN CN201910457316.6A patent/CN110156591A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3950431A (en) * | 1972-11-21 | 1976-04-13 | Sumitomo Chemical Company, Limited | Process for removing impurities in an oxidation mixture |
| CN104192802A (en) * | 2014-08-29 | 2014-12-10 | 浙江大洋生物科技集团股份有限公司 | Purification method of coproduct hydrochloric acid of 2-chloro-6-fluorobenzaldehyde or analogs |
| CN109020801A (en) * | 2018-09-04 | 2018-12-18 | 江苏超跃化学有限公司 | The recovery method of by-product parachlorobenzoic-acid in a kind of p-chlorobenzaldehyde production process |
Non-Patent Citations (2)
| Title |
|---|
| 董成国等: "对氟苯甲醛的合成研究", 《染料工业》 * |
| 陈红飙等: "邻氟苯甲醛的合成研究", 《有机氟工业》 * |
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Application publication date: 20190823 |