CN103012125A - Method for preparing anisic acid - Google Patents
Method for preparing anisic acid Download PDFInfo
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- CN103012125A CN103012125A CN2012104414435A CN201210441443A CN103012125A CN 103012125 A CN103012125 A CN 103012125A CN 2012104414435 A CN2012104414435 A CN 2012104414435A CN 201210441443 A CN201210441443 A CN 201210441443A CN 103012125 A CN103012125 A CN 103012125A
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- anethole
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Abstract
The invention discloses an organic acid preparation and particularly discloses a method for preparing anisic acid through oxidizing anethole. According to the method for preparing the anisic acid, the anisic acid is obtained through mixing the anethole, potassium permanganate, CTAB (Cetyltrimethyl Ammonium Bromide) and water according to a weight ratio of 1: 3.33: 0.373: 37.3 and oxidizing through heating, cooling, filtering, drying and the like. The method is simple in process and low in cost; and finished products are stable in quality, mainly serve as synthesis intermediates of pharmaceuticals and other fine chemicals, and are also widely applied to the production field of spices and cosmetics.
Description
Technical field
The present invention is applicable to the organic acid preparation field, relates in particular to a kind of preparation method of anisic acid.
Background technology
Anisic acid also claims 4-anisic acid, anisic acid, 4-carboxyl methyl-phenoxide, and natural anisic acid is present in piscidia, phoenix plough piscidia, anise, eggplant and reaches in cheese, cocoa, sweet fennel, cherimoya, vanilla and the star anise.
Name of product: anisic acid;
Chemical name: 4-methoxybenzoic acid;
English name: p-Anisic acid, 4-Methoxybenzoic Acid;
CAS?NO.：100-09-4；
FEMA：3945；
EINECS：202-818-5；
JECFA：883；
Structural formula:
Quality index: 〉=99%;
Be colourless acicular crystal under the normal temperature, be dissolved in ethanol, ether, chloroform, be slightly soluble in hot water, be insoluble in cold water.
Odour characteristics: 1% solution has vanilla, cream is fragrant and sweet, powder is fragrant, apple, piperonal sample fragrance, with Radix Glycyrrhizae sample aromatic.
The concentration of sense of taste feature: 10mg/kg has cream vanilla, fragrant and sweet and powder Flavor, and with piperonal and berry sample charm.
Anisic acid is widely used in the industrial circles such as spices and essence, food, makeup, also is used as the synthetic intermediate of medicine and other fine chemicals.
As flavor of raw material, be used for cocoa and cream vanilla note, also be used for Radix Glycyrrhizae, berry and tropical fruit essence.Anisic acid plays the fixative effect simultaneously in essence.
As medicine intermediate, for the synthesis of 3-amino-4-methoxyl phenylformic acid (3-Amino-4-methoxybenzoic acid), anisoyl chloride (4-Methoxybenzoyl chloride) etc., synthesizing efficient intelligence is improved medicine aniracetam (Aniracetam) and antiarrhythmic drug SKF 33134A (Amiodarone).
As the synthetic perfume raw material, p-Methoxybenzoic acid methyl ester, ethyl anisate, pmethoxybenzyl alcohol etc.
In foodstuffs industry, anisic acid can be used as sanitas, can be used to improve the taste of non-nutritive sweetener, covers the metallic aftertaste of non-nutritive sweetener.
Also as fine chemical material for the production of spices, makeup and participate in multiple organic synthesis.
Traditionally, synthetic anisic acid method has:
(1) aubepine is made raw material and is made through oxidation, and reaction formula is:
(2) P-hydroxybenzoic acid makes through methylating under alkaline condition, and reaction formula is:
(3) take p-cresol as raw material, through methylate, oxidizing reaction makes, reaction formula is:
Natural aubepine, P-hydroxybenzoic acid are expensive, and the p-cresol price is relatively cheap, but reactions steps is many, and the alkali consumption is large, is unfavorable for cost control.
The aubepine of technical grade, P-hydroxybenzoic acid, p-cresol multi-source are in petrochemical industry, contain a large amount of poisonous and harmful impurity and heavy metal, these poisonous and harmful impurity and heavy metal may remain in the product, quality, the Application Areas of anisic acid are restricted, and this class anisic acid can not be used for food, makeup etc.
Summary of the invention
The embodiment of the invention provides that a kind of to adopt natural isoesdragol be the method that the raw material oxidation prepares anisic acid.Use the product purity of the method gained high, reach natural grade standard, be intended to solve the problem that lacks in the market the anisic acid that quality is comprehensive, technique is simple, with low cost.
Following technical scheme addresses the above problem.
1, the characteristic of property of each composition of prescription of the present invention is as follows:
(1) trans-anethole
Chemical name: trans-anethole claims again isoesdragol, trans anise camphor, 1-methoxyl group-4-(1-propenyl)-benzene;
Chemical formula: C
10H
12O;
Molecular weight: 148.2;
Storage: be kept in the encloses container, be stored in cool place, drying, ventilation, avoid assorted gas to pollute, keep fire away;
Structural formula:
Relative density (25 ℃/25 ℃): 0.983～0.988;
Refractive index (25 ℃): 1.5570～1.5620;
Solubleness (25 ℃): 1mL or 1g sample are dissolved in 3ml90% (volume fraction) ethanol entirely;
Proterties: for white with star anise sample fragrance to light yellow congealed solid or colourless to light yellow liquid.
(2) potassium permanganate
Chemical formula: KMnO
4
Molecular weight: 158.04;
Outward appearance: intense violet color has the granular or acicular crystals of metalluster rhombic system;
Density: 2.703g/cm3;
Solvability: the water-soluble amaranth solution that becomes slightly is dissolved in methyl alcohol, Glacial acetic acid, acetone and sulfuric acid;
Chemical property: ethanol, hydrogen peroxide decompose, and be heated to more than 240 ℃ and emit oxygen, be strong oxidizer.Contact easily with the vitriol oil and to blast, contact with organism, friction, collision can cause burning and emit oxygen.
(3) catalyzer: cetyl trimethylammonium bromide, another name: Cetrimonium Bromide, bromine palm fibre trimethyl ammonium, Cetrimide, whale is melted trimethylammonium bromide; CTAB; CTMAB; HTAB; CTABr; Positive soap.
English name: Hexadecyl trimethyl ammonium Bromide; Cetrimonium Bromide;
Classification: quaternary ammonium salt;
CAS?No.：57-09-0；
EINECS?No.：200-311-3；
Structural formula:
Molecular formula: C
19H
42BrN;
Molecular weight: 364.446;
Fusing point: 250-237 ℃;
Water-soluble: 13g/L (20 ℃);
Character description: white micro-crystals shape powder is a kind of quaternary ammonium salt; Water absorbability is arranged, stable in acidic solution; Be dissolved in 10 parts of water, be soluble in ethanol, be slightly soluble in acetone, be dissolved in hardly ether and benzene.
Character: be white in color or light yellow xln to Powdered, be soluble in Virahol, water soluble produces a large amount of foams during concussion, can good coordination be arranged with positively charged ion, nonionic, amphoterics.
Purposes: the present invention is mainly used in phase-transfer catalyst.
(4) stopper: 4-hydroxyl-TEMPO
Chinese: 4-hydroxyl-TEMPO, 4-hydroxy piperidine alcohol oxyradical, 4-hydroxyl-TEMPO, stopper 701;
English name: 4-Hydroxy-TEMPO, 4-Hydroxy-2,2,6,6-tetramethyl-piperidinooxy, 4-Hydroxy-2,2,6,6-tetramethyl-1-piperidin-1-yloxy;
CAS?No.：2226-96-2；
EINECS?No.：218-760-9；
Structural formula:
Molecular formula:
Molecular weight: 172.25;
Fusing point: 69～72 ℃;
Flash-point: 146 ℃ (295 °F);
4-hydroxyl-TEMPO is orange red xln, is soluble in the organic solvents such as ethanol, benzene, and is soluble in water.Be used for preventing olefinic monomer produce, separate, autohemagglutination, control and the polymerization degree of regulating olefines and derivative thereof of refining, storage or transportation.
The easy moisture absorption of 4-hydroxyl-TEMPO needs to store under the close drying condition, anti-high temperature, and what should keep packing is complete, is stored in ventilation, and clean and tidy storehouse is avoided depositing with other acidic chemical.
2, operational path of the present invention as shown in Figure 1.
3, the required main raw material of preparation process of the present invention is by weight proportion:
Trans-anethole: potassium permanganate: catalyzer: stopper: water=1: 3.33: 0.373: 0.003: 37.3.
4, the present invention prepares the technique of anisic acid and is:
By proportioning mixing water, potassium permanganate, catalyzer, stopper, in the situation that stir the proportioning trans-anethole is added in the reactor fast, continue to stir, keep 110 ℃ of reaction mass temperature to carry out back flow reaction 2h.Reaction changes back flow reaction into steam distillation after finishing, and draws not trans-anethole and other organic impurity of complete reaction.Reaction mass is cooled to 70 ℃, centrifuging, filtrate concentrating left standstill.Supernatant liquid is transferred in the souring tank, stirred lower adding concentrated hydrochloric acid solution to material pH=2.The centrifuging acidizing fluid, filtrate enters treatment tank; Filter cake is washed with water to water lotion pH=7, drying, discharging.With dry materials to moisture content less than 1.0%, through pulverize, screening, obtain the finished product anisic acid after the stdn.
Description of drawings
Fig. 1 represents the process flow sheet of the preparation anisic acid that the embodiment of the invention provides.
Embodiment
In an embodiment of the present invention, the isoesdragol oxidation prepares the ratio of main raw material of the method for anisic acid and is:
Trans-anethole: potassium permanganate: catalyzer: stopper: water=1: 3.33: 0.373: 0.003: 37.3.
Fig. 1 shows the preparation method's of the anisic acid that the embodiment of the invention provides realization flow, and details are as follows:
(1) oxidizing reaction: add entry, potassium permanganate, catalyzer, stopper respectively in enamel reaction still in proportion, add fast the proportioning trans-anethole in the situation that stir, back flow reaction (110 ℃) 2h is carried out in lasting stirring after reinforced the finishing.Reaction changes back flow reaction into steam distillation to distillate and does not contain oil content after finishing, and distillating steam does not have the trans-anethole smell.
(2) centrifuging I: reaction mass is cooled to 70 ℃, utilizes rotating speed to filter for the whizzer of 8000rpm, filtrate is to the basin standing demix, and filter cake is left utilization to be recycled concentratedly.
(3) standing demix: filtrate concentrating left standstill 24h.
(4) acidifying: the supernatant liquid behind the standing demix is transferred in the souring tank, stirred lower adding concentrated hydrochloric acid solution and be adjusted to material pH=2.
(5) centrifuging II: centrifuging acidifying material, filtrate enters treatment tank; Filter cake is washed to water lotion and is neutral (pH=7), drying, discharging.
(6) drying: material is put into 5m
3In between warm air drying, temperature is 100-130 ℃, and drying time is 24h, dries to moisture content＜1.0%.
(7) pulverize, sieve and packing.
In embodiments of the present invention, the process characteristic for preparing natural anisic acid is:
(1) adopts the steam distillation method to remove not trans-anethole and other organic impurity of complete reaction after the oxidizing reaction, alleviate subsequent handling purifying pressure, improve product purity and quality.Unreacted trans-anethole is recyclable to be recycled, and total recovery obviously improves.
(2) add stopper 4-hydroxyl-TEMPO in the oxidizing reaction, prevented the polymerization of propenyl in the reaction process trans-anethole, improved the product yield.
(3) use phase-transfer catalyst cetyl trimethylammonium bromide (CTAB) in the oxidizing reaction, make oxygenant transfer to organic phase from water fast, accelerate reaction process.Test shows, use CTAB than Catalyzed By Phase-transfer Catalyst better effects if such as traditional 4 bromide (TMAB) that uses, Tetrabutyl amonium bromide (TBAB), polyoxyethylene glycol (PEG), octyl phenyl Soxylat A 25-7s (OP), reacting balance, time shorten.
(4) through pulverizing, it is Powdered that product is, and with the xln ratio, dissolution rate is faster in the water, the convenient use.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The ratio of main raw material that isoesdragol oxidation of the present invention prepares the method for anisic acid is:
Trans-anethole: potassium permanganate: CTAB: water=1: 3.33: 0.373: 37.3.
The method that isoesdragol oxidation of the present invention prepares anisic acid mainly operates by following processing step:
(1) in the 3000L enamel still, adds entry, potassium permanganate (open to stir and add), CTAB respectively in proportion, in the header tank with trans-anethole suction reactor.In the situation that stir trans-anethole is added in the 3000L reactor, add rear continuation and stir 1h.
(2) setting the enamel still oil temperature is 118 ℃, and keeping liquid temperature is 100 ℃ of left and right sides back flow reaction.
(3) material is cooled to 80-90 ℃, filters with φ 1200 tripod pendulum type batch centrifugals, staticly settle in the filtrate suction 5000L plastics setting tank, filter cake is left concentratedly.
(4) with in the supernatant liquid suction 5000L plastics souring tank in the setting tank, stir lower adding concentrated hydrochloric acid solution to material pH=2.
(5) with the material after the φ 800 tripod pendulum type batch centrifugals filtration acidifying, filtrate enters treatment tank; Wash filter cake to filtrate pH=7, drying, discharging.
(6) material is put into 5m
3In between warm air drying, dry to moisture content＜2.0%.
(7) pulverize, weigh, pack.
Embodiment 1
Example 2
Example 3
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (3)
1. the preparation method of an anisic acid is characterized in that, described method comprises:
The formulation weight ratio is: trans-anethole 1: potassium permanganate 3.33: CTAB0.373: water 37.3;
Equipment is: 3000L enamel reaction still, 5000L plastics setting tank, 5000L plastics souring tank,
Tripod pendulum type batch centrifugal,
Tripod pendulum type batch centrifugal and 5m
3Between warm air drying;
Temperature of reaction is 100 ℃ (back flow reaction).
2. the method for claim 1 is characterized in that, the step of described method is specially:
(1) in the 3000L enamel still, adds entry, potassium permanganate (open to stir and add), CTAB respectively in proportion, in the header tank with trans-anethole suction reactor.In the situation that stir trans-anethole is added in the 3000L reactor, add rear continuation and stirred 1 hour;
(2) setting the enamel still oil temperature is 118 ℃, and keeping liquid temperature is 100 ℃ of left and right sides back flow reaction;
(3) material is cooled to 80-90 ℃, uses
Tripod pendulum type batch centrifugal filters, and staticly settles in the filtrate suction 5000L plastics setting tank, and filter cake is left concentratedly;
(4) with in the supernatant liquid suction 5000L plastics souring tank in the setting tank, stir lower adding concentrated hydrochloric acid solution to material pH=2;
(5) use
Tripod pendulum type batch centrifugal filters the material after the acidifying, and filtrate enters treatment tank; Wash filter cake to filtrate pH=7, drying, discharging;
(6) material is put into 5m
3In between warm air drying, dry to moisture content＜2.0%;
(7) pulverize, weigh and pack.
3. the method for claim 1 is characterized in that, described method prepares anisic acid by the isoesdragol oxidation, and main flow process is: oxidizing reaction-centrifuging-standing demix-acidifying-centrifuging washing-drying process-finished product.
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| CN2012104414435A CN103012125A (en) | 2012-11-08 | 2012-11-08 | Method for preparing anisic acid |
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| CN2012104414435A CN103012125A (en) | 2012-11-08 | 2012-11-08 | Method for preparing anisic acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883930A (en) * | 2017-04-13 | 2017-06-23 | 嘉兴德扬生物科技有限公司 | A kind of method extracted fennel oil from Chinese anise and prepare p-Methoxybenzoic acid methyl ester |
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|---|---|---|---|---|
| CN101423465A (en) * | 2008-12-06 | 2009-05-06 | 广西师范大学 | Method for preparing anisic aldehyde by hydrogen peroxide oxidation of anethole through microwave aided acid catalysis |
| EP2060556A1 (en) * | 2007-11-19 | 2009-05-20 | Dr. Straetmans Chemische Produkte GmbH | Method for manufacturing 4-methoxybenzoic acid from vegetable anethol and its application in cosmetic or dermatological products and foodstuffs |
| CN101792378A (en) * | 2009-12-29 | 2010-08-04 | 中国科学院广州化学研究所 | Method for preparing anisaldehyde |
| CN102336639A (en) * | 2011-07-13 | 2012-02-01 | 广西万山香料有限责任公司 | Production method of natural equivalent anisic aldehyde |
-
2012
- 2012-11-08 CN CN2012104414435A patent/CN103012125A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2060556A1 (en) * | 2007-11-19 | 2009-05-20 | Dr. Straetmans Chemische Produkte GmbH | Method for manufacturing 4-methoxybenzoic acid from vegetable anethol and its application in cosmetic or dermatological products and foodstuffs |
| CN101423465A (en) * | 2008-12-06 | 2009-05-06 | 广西师范大学 | Method for preparing anisic aldehyde by hydrogen peroxide oxidation of anethole through microwave aided acid catalysis |
| CN101792378A (en) * | 2009-12-29 | 2010-08-04 | 中国科学院广州化学研究所 | Method for preparing anisaldehyde |
| CN102336639A (en) * | 2011-07-13 | 2012-02-01 | 广西万山香料有限责任公司 | Production method of natural equivalent anisic aldehyde |
Non-Patent Citations (5)
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| 张小朋等: "合成茴香醛新工艺的研究", 《日用化学工业》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883930A (en) * | 2017-04-13 | 2017-06-23 | 嘉兴德扬生物科技有限公司 | A kind of method extracted fennel oil from Chinese anise and prepare p-Methoxybenzoic acid methyl ester |
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Application publication date: 20130403 |