CN103497094A - Preparation method of anisic aldehyde - Google Patents
Preparation method of anisic aldehyde Download PDFInfo
- Publication number
- CN103497094A CN103497094A CN201310428640.8A CN201310428640A CN103497094A CN 103497094 A CN103497094 A CN 103497094A CN 201310428640 A CN201310428640 A CN 201310428640A CN 103497094 A CN103497094 A CN 103497094A
- Authority
- CN
- China
- Prior art keywords
- estragole
- isomery
- anisyl aldehyde
- anethole
- pot
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/32—Preparation of ethers by isomerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of anisic aldehyde and aims to provide a novel preparation method of anisic aldehyde in order to reduce the production cost of the anisic aldehyde and the environment pollution. The method comprises the following steps: isomerizing; carrying out refrigerated centrifugation; oxidizing; centrifuging; washing; and neutralizing. Estragole is subjected to steps such as isomerization, centrifugation and oxidization in the presence of a catalyst so that electrons in estragole molecules are rearranged, and foreign matters generate required anethole. The anethole is subjected to oxidization reaction under an acidic condition of manganese dioxide and transformed from ketone to aldehyde so that anisic aldehyde is obtained finally. According to the invention, the estragole is used as the raw material, the purification content of the estragole for preparing the anisic aldehyde can be up to over 97% and is about 13% higher than that of the traditional process. The preparation method is capable of remarkably increasing the yield of the anisic aldehyde and meeting the requirement for large-scale industrial production, easier to purify as well as little in equipment corrosion and environment pollution.
Description
Technical field
The present invention relates to the production of flavor field, especially a kind of preparation method of anisyl aldehyde.
Background technology
The chemical name of anisyl aldehyde is aubepine, and it has application comparatively widely.It has lasting hawthorn fragrance, and fragrance is tempting, thereby is widely used in preparing the multiple essence such as sweet floral type, hawthorn odor type and cloves odor type, and the preparation of food, carbohydrate and beverage class essence; Aspect medical, it is the important intermediate of the medicine (as medicines such as hydroxybenzyl mould rope, Porphyrin-Based Sensitizer) of the anti-thing of supporting one's family of preparation; In electroplating industry, it can be used as the good brightening agent of non-cyanogen galvanization DE additive; At agriculture field, anisyl aldehyde can be used as sterilant, sterilant additive, biological growth inhibitor etc.Because anisyl aldehyde has excellent performance, thereby be widely used.
At present, the method for domestic synthetic anisyl aldehyde mainly contains three kinds.First method is the isoesdragol oxidation style, and the method is owing to being limited by natural resource, and cost value is higher, now seldom adopts.The second is to take the oxidation style (being the Sommelet reaction method) that methyl-phenoxide (sodium dichromate) is raw material, and the method can produce a large amount of acid waste water, and equipment is caused to seriously corroded.The third is the cresols synthesis method, and the method exists three-waste pollution serious, the problem that yield is not high.
Therefore, at present, in the urgent need to a kind of preparation method of new anisyl aldehyde, to reduce the production cost of anisyl aldehyde, reduce the pollution to environment.
Summary of the invention
Goal of the invention of the present invention is: for the problem of above-mentioned existence, provide a kind of preparation method of anisyl aldehyde.The present invention be take estragole as raw material, by a kind of new technical process is provided, successfully prepares anisyl aldehyde.The present invention can significantly improve the production yield of anisyl aldehyde, and simplification of flowsheet shortens the production cycle, reduces production costs.The present invention is little to the corrosion of equipment, thereby work-ing life that can extension device, is conducive to industrialization, the scale operation of anisyl aldehyde.
To achieve these goals, the present invention adopts following technical scheme:
A kind of preparation method of anisyl aldehyde, comprise the steps:
(1) isomery: estragole is put into to the isomery pot, then add potassium hydroxide in the isomery pot, the temperature of controlling in the isomery pot is 175-185 ℃, reaction 3-5h, and reaction stops the isomery pot is heated after finishing, and obtains trans-anethole;
(2) frozen centrifugation: the trans-anethole that step 1 is obtained carries out freezingly subzero below 20 ℃, under freezing conditions simultaneously, trans-anethole is carried out centrifugal, obtains the high purity trans-anethole;
(3) oxidation: the high purity trans-anethole that step 2 is obtained is put into reactor, and adds dilute sulphuric acid, MnO in reactor
2, the temperature of controlling in reactor is 80-110 ℃, reaction 2-6h, obtain the anisyl aldehyde crude product;
(4) centrifugal, washing: the anisyl aldehyde crude product is put into to whizzer and carry out centrifugation, washed with salt solution again after centrifugation;
(5) neutralization: the anisyl aldehyde crude product after washing is carried out to the secondary washing with sodium bicarbonate water, make the pH value of anisyl aldehyde crude product be alkalescence, obtain product.
In described step 1, the 3%-10% that the quality of the potassium hydroxide added is the estragole quality;
In described step 3, add the ratio of weight and number of component as follows: 1000 parts of high purity trans-anetholes, 100-300 part dilute sulphuric acid, 200-500 part MnO
2catalyzer;
In described step 4, salt solution is mixed by muriate and water, and muriate accounts for the 2%-10% of brine quality, and muriate is a kind of in sodium-chlor, Repone K;
In described step 5, in sodium bicarbonate water, the mass percent of solute is 2-20%.
In described step 1, raw material natural grass estragole is dropped in rectifying tower, purified, the tower reactor temperature of rectifying tower is 150-170 ℃, and the temperature of tower top is 110-130 ℃, the estragole after being purified;
Estragole after purifying is put into to the isomery pot, then add potassium hydroxide in the isomery pot, the temperature of controlling in the isomery pot is 175-185 ℃, reaction 3-5h, and reaction stops the isomery pot is heated after finishing, and obtains trans-anethole.
In described step 1, raw material natural grass estragole is dropped in rectifying tower, purified, the tower reactor temperature of rectifying tower is 155-165 ℃, and the temperature of tower top is 115-125 ℃, the estragole after being purified.
In described step 1, the quality of the potassium hydroxide added is 5% of estragole quality.
In described step 1, estragole is put into to the isomery pot, then add potassium hydroxide in the isomery pot, the temperature of controlling in the isomery pot is 180 ℃, reaction 4h, and reaction stops the isomery pot is heated after finishing, and obtains trans-anethole.
In described step 2, the brain that returns that step 1 is obtained carries out freezingly at subzero 20 ℃, under freezing conditions, to returning brain, carry out centrifugally simultaneously, and centrifugation time is 10-60min, obtains the high purity trans-anethole.
In described step 3, the high purity trans-anethole that step 2 is obtained is put into reactor, and adds dilute sulphuric acid, MnO in reactor
2, the temperature of controlling in reactor is 100 ℃, reaction 4h, obtain the anisyl aldehyde crude product;
Add the ratio of weight and number of component as follows: 1000 parts of high purity trans-anetholes, 200 parts of dilute sulphuric acids, 300 parts of MnO2 catalyzer.
In described step 5, the anisyl aldehyde crude product after washing is carried out to the secondary washing with sodium bicarbonate water, the pH value that makes the anisyl aldehyde crude product is 7.5-8.5.
In described step 5, the anisyl aldehyde crude product after washing is carried out to the secondary washing with sodium bicarbonate water, the pH value that makes the anisyl aldehyde crude product is 8.
In described step 5, in sodium bicarbonate water, the mass percent of solute is 5%.
In described step 5, anisyl aldehyde crude product after washing is carried out to the secondary washing with sodium bicarbonate water, make the pH value of anisyl aldehyde crude product be alkalescence, obtain product, again product is sent in rectifying tower and purified, the tower reactor temperature of rectifying tower is 155 ℃-165 ℃, and tower top temperature is 115 ℃-125 ℃, purifies and obtains high purity product.
The molecular structural formula of estragole is as follows:
Preparation method of the present invention comprises the steps such as isomery, frozen centrifugation, oxidation, centrifugal, washing, neutralization.Due to the estragole purity in the place of production, usually in 50% left and right, therefore can first to raw material natural grass estragole, be purified.The condition that estragole is purified is comparatively harsh, and the present invention drops into raw material natural grass estragole in rectifying tower, is purified, and the tower reactor temperature of rectifying tower is 150-170 ℃, and the temperature of tower top is 110-130 ℃, the estragole after being purified.Through purifying, the purity of the 50% raw material natural grass estragole that can make purity be is largely increased, and is up to 98%.
Then estragole is carried out to the isomery processing, the selection of being depended on fast smoothly catalyzer and reaction conditions of isomerization reaction, for the present invention, the catalyzer adopted during isomery, temperature of reaction, the reaction times material impact that had to isomerization reaction.This step can make the estragole chain rupture become trans-anethole, and after measured: adopt the present invention, the transformation efficiency of isomery reaches more than 98%, after stopped reaction, can access approximately 95% trans-anethole.
Again trans-anethole is carried out to frozen centrifugation, by carrying out freezingly below-20 ℃ by trans-anethole, and under freezing conditions, trans-anethole is carried out centrifugal, can obtain the high purity trans-anethole.Further, by trans-anethole, at-20 ℃, carry out freezing.Aubepine belongs to thermo-sensitivity spices, if neutralization reaction or polyreaction can occur in excess Temperature, thereby must strict control condition.The present invention carries out frozen centrifugation to trans-anethole, can obtain 99.9% trans-anethole.
Again the high purity trans-anethole is carried out to oxide treatment, obtain the anisyl aldehyde crude product.Oxidation is reaction types of a class uniqueness to the reaction of the two key oxidation scissions of organic compound, and its product depends on the structure of matter, solvent species and temperature of reaction.In the present invention, the catalyzer used in oxidizing reaction, solvent, temperature of reaction, time have material impact to final product, and it directly determines the conversion of trans-anethole to anisyl aldehyde.
And then to the anisyl aldehyde crude product carry out centrifugal, the washing and the neutralization.Anisyl aldehyde crude product after washing is carried out to the secondary washing with sodium bicarbonate water, make the pH value of anisyl aldehyde crude product be alkalescence, obtain product.Further, making the pH value of anisyl aldehyde crude product is 7.5-8.5; Further again, the pH value that makes the anisyl aldehyde crude product is 8.The applicant is through the research discovery, and under alkaline condition, anisyl aldehyde is difficult for polymerization reaction take place, thereby selects sodium bicarbonate water to carry out the secondary washing.Further, the product obtained is sent in rectifying tower and purified, the tower reactor temperature of rectifying tower is 155 ℃-165 ℃, and tower top temperature is 115 ℃-125 ℃, and purifying and obtaining purity is the product more than 99%.
Dilute sulphuric acid refers to the sulfuric acid of concentration below 70%, the sulfuric acid that wherein the massfraction of solute is less than 70%.In the present invention, the concentration of the dilute sulphuric acid of employing can be 3%-70%.In sodium bicarbonate water, the mass percent of solute is 5% to refer to, in sodium bicarbonate water, sodium bicarbonate accounts for 5% of sodium bicarbonate water total mass.In step 1, raw material natural grass estragole is dropped in rectifying tower, purified, estragole after being purified, the tower reactor temperature of rectifying tower is 150-170 ℃, the temperature of tower top is 110-130 ℃, rectifying tower is with adopting thermal oil to be heated, and the temperature of thermal oil is 180 ℃-200 ℃.
In the present invention, only produce a small amount of waste water, effectively reduce the quantity discharged of waste water, only need to be precipitated waste water, neutralizing treatment, after reaching emission standard, can discharge, effectively reduce the intractability of waste water.
The applicant by with the other unit cooperation, obtained the present invention.The present invention, by steps such as estragole isomerization under catalyzer potassium hydroxide existence condition, centrifugal, oxidations, resets the electronics in the estragole molecule, and foreign matter generates the trans-anethole needed.Trans-anethole carries out oxidizing reaction under the acidic conditions of Manganse Dioxide, by ketone, is converted into aldehyde, finally obtains anisyl aldehyde.The present invention is usingd estragole as raw material, and the purification content for preparing estragole can reach more than 97%, than the purification content of traditional technology, exceeds 13% left and right.The present invention can significantly improve the yield of anisyl aldehyde, more easily purifies, and can meet large-scale industrialization production, and little to the corrosion of equipment, few to the pollution of environment.The price of anisyl aldehyde is more than 2 times of trans-anethole, thereby adopts the present invention can significantly improve value-added content of product.
Embodiment
Disclosed all features in this specification sheets, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Disclosed arbitrary feature in this specification sheets, unless special narration all can be replaced by other equivalences or the alternative features with similar purpose.That is,, unless special narration, each feature is an example in a series of equivalences or similar characteristics.
Embodiment 1
The raw material natural grass estragole that is 50% by purity drops in rectifying tower, is purified, and the tower reactor temperature of rectifying tower is 160 ℃, and the temperature of tower top is 120 ℃, the estragole after being purified, and its purity is 98% left and right.
Estragole after purifying is put into to the isomery pot, then add catalyzer potassium hydroxide in the isomery pot, the temperature of controlling in the isomery pot is 180 ℃, reaction 4h, and reaction stops the isomery pot is heated after finishing, and obtains trans-anethole.5% of the quality that the quality of the potassium hydroxide wherein, added is the estragole after purifying.
Carry out freezingly by trans-anethole below 20 ℃ subzero, under freezing conditions simultaneously, trans-anethole is carried out centrifugal, centrifugation time is 20min, obtains the high purity trans-anethole.
1000kg high purity trans-anethole is put into to reactor, and add 200kg dilute sulphuric acid, 300kgMnO in reactor
2, the temperature of controlling in reactor is 100 ℃, reaction 4h, obtain the anisyl aldehyde crude product.The concentration of dilute sulphuric acid is 20%.
The anisyl aldehyde crude product is put into to whizzer and carry out centrifugation, washed with salt solution again after centrifugation.Wherein, salt solution is the sodium chloride solution that mass percent is 5%.
The sodium bicarbonate water that is 5% by the solute mass percent by the anisyl aldehyde crude product after washing carries out the secondary washing, and making the pH value of anisyl aldehyde crude product is 8.0, obtains product.
Again product is sent in rectifying tower and purified, the tower reactor temperature of rectifying tower is 160 ℃, and tower top temperature is 120 ℃, purifies and obtains the high purity product that purity is 98-99%.
Embodiment 2
Raw material natural grass estragole is dropped in rectifying tower, purified, the tower reactor temperature of rectifying tower is 150 ℃, and the temperature of tower top is 110 ℃, the estragole after being purified.
Estragole after purifying is put into to the isomery pot, then add potassium hydroxide in the isomery pot, the temperature of controlling in the isomery pot is 185 ℃, reaction 3h, and reaction stops the isomery pot is heated after finishing, and obtains trans-anethole.3% of the quality that the quality of the potassium hydroxide wherein, added is the estragole after purifying.
Carrying out freezingly below-20 ℃ by trans-anethole, under freezing conditions simultaneously, trans-anethole is being carried out centrifugal, centrifugation time is 50min, obtains the high purity trans-anethole.
1000kg high purity trans-anethole is put into to reactor, and add 100kg dilute sulphuric acid, 400kgMnO in reactor
2, the temperature of controlling in reactor is 100 ℃, and reaction 4h, obtain the anisyl aldehyde crude product, and wherein, the concentration of dilute sulphuric acid is 35%.
The anisyl aldehyde crude product is put into to whizzer and carry out centrifugation, washed with salt solution again after centrifugation.Wherein, salt solution is the sodium chloride solution that mass percent is 3%.
The sodium bicarbonate water that is 6% by the solute mass percent by the anisyl aldehyde crude product after washing carries out the secondary washing, makes the pH value of anisyl aldehyde crude product be alkalescence, obtains product.
Again product is sent in rectifying tower and purified, the tower reactor temperature of rectifying tower is 155 ℃, and tower top temperature is 115 ℃, purifies and obtains high purity product.
Embodiment 3
Raw material natural grass estragole is dropped in rectifying tower, purified, the tower reactor temperature of rectifying tower is 155 ℃, and the temperature of tower top is 115 ℃, the estragole after being purified.
Estragole after purifying is put into to the isomery pot, then add potassium hydroxide in the isomery pot, the temperature of controlling in the isomery pot is 175 ℃, reaction 5h, and reaction stops the isomery pot is heated after finishing, and obtains trans-anethole.8% of the quality that the quality of the potassium hydroxide wherein, added is the estragole after purifying.
Carrying out freezingly below-25 ℃ by trans-anethole, under freezing conditions simultaneously, trans-anethole is being carried out centrifugal, centrifugation time is 15min, obtains the high purity trans-anethole.
1000kg high purity trans-anethole is put into to reactor, and add 300kg dilute sulphuric acid, 250kgMnO in reactor
2, the temperature of controlling in reactor is 105 ℃, reaction 3h, obtain the anisyl aldehyde crude product.
The anisyl aldehyde crude product is put into to whizzer and carry out centrifugation, washed with salt solution again after centrifugation.Wherein, salt solution is the sodium chloride solution that mass percent is 7%.
Anisyl aldehyde crude product after washing is carried out to the secondary washing with sodium bicarbonate water, make the pH value of anisyl aldehyde crude product be alkalescence, obtain product.In sodium bicarbonate water, the mass percent of sodium bicarbonate is 10%.
Again product is sent in rectifying tower and purified, the tower reactor temperature of rectifying tower is 160 ℃, and tower top temperature is 120 ℃, purifies and obtains the high purity product that purity is 98-99%.
Embodiment 4
Raw material natural grass estragole is dropped in rectifying tower, purified, the tower reactor temperature of rectifying tower is 165 ℃, and the temperature of tower top is 125 ℃, the estragole after being purified.
Estragole after purifying is put into to the isomery pot, then add potassium hydroxide in the isomery pot, the temperature of controlling in the isomery pot is 180 ℃, reaction 4.5h, and reaction stops the isomery pot is heated after finishing, and obtains trans-anethole.7% of the quality that the quality of the potassium hydroxide wherein, added is the estragole after purifying.
Carrying out freezingly below-22 ℃ by trans-anethole, under freezing conditions simultaneously, trans-anethole is being carried out centrifugal, centrifugation time is 20min, obtains the high purity trans-anethole.
1000kg high purity trans-anethole is put into to reactor, and add 200kg dilute sulphuric acid, 200kgMnO in reactor
2, the temperature of controlling in reactor is 100 ℃, reaction 5h, obtain the anisyl aldehyde crude product.
The anisyl aldehyde crude product is put into to whizzer and carry out centrifugation, washed with salt solution again after centrifugation.Wherein, salt solution is the Klorvess Liquid that mass percent is 5%.
The sodium bicarbonate water that is 15% by the solute mass percent by the anisyl aldehyde crude product after washing carries out the secondary washing, makes the pH value of anisyl aldehyde crude product be alkalescence, obtains product.
Again product is sent in rectifying tower and purified, the tower reactor temperature of rectifying tower is 165 ℃, and tower top temperature is 125 ℃, purifies and obtains high purity product.
Embodiment 5
Raw material natural grass estragole is dropped in rectifying tower, purified, the tower reactor temperature of rectifying tower is 160 ℃, and the temperature of tower top is 120 ℃, the estragole after being purified.
Estragole after purifying is put into to the isomery pot, then add potassium hydroxide in the isomery pot, the temperature of controlling in the isomery pot is 180 ℃, reaction 4h, and reaction stops the isomery pot is heated after finishing, and obtains trans-anethole.6% of the quality that the quality of the potassium hydroxide wherein, added is the estragole after purifying.
Carrying out freezingly below-20 ℃ by trans-anethole, under freezing conditions simultaneously, trans-anethole is being carried out centrifugal, centrifugation time is 40min, obtains the high purity trans-anethole.
1000kg high purity trans-anethole is put into to reactor, and add 250kg dilute sulphuric acid, 350kgMnO in reactor
2, the temperature of controlling in reactor is 105 ℃, reaction 4.5h, obtain the anisyl aldehyde crude product.
The anisyl aldehyde crude product is put into to whizzer and carry out centrifugation, washed with salt solution again after centrifugation.Wherein, salt solution is the Klorvess Liquid that mass percent is 3%.
The sodium bicarbonate water that is 3% by the solute mass percent by the anisyl aldehyde crude product after washing carries out the secondary washing, makes the pH value of anisyl aldehyde crude product be alkalescence, obtains product.
Again product is sent in rectifying tower and purified, the tower reactor temperature of rectifying tower is 160 ℃, and tower top temperature is 120 ℃, purifies and obtains high purity product.
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature or any new combination disclosed in this manual, and the arbitrary new method disclosed or step or any new combination of process.
Claims (10)
1. the preparation method of an anisyl aldehyde, is characterized in that, comprises the steps:
(1) isomery: estragole is put into to the isomery pot, then add potassium hydroxide in the isomery pot, the temperature of controlling in the isomery pot is 175-185 ℃, reaction 3-5h, and reaction stops the isomery pot is heated after finishing, and obtains trans-anethole;
(2) frozen centrifugation: the trans-anethole that step 1 is obtained carries out freezingly subzero below 20 ℃, under freezing conditions simultaneously, trans-anethole is carried out centrifugal, obtains the high purity trans-anethole;
(3) oxidation: the high purity trans-anethole that step 2 is obtained is put into reactor, and adds dilute sulphuric acid, MnO in reactor
2, the temperature of controlling in reactor is 80-110 ℃, reaction 2-6h, obtain the anisyl aldehyde crude product;
(4) centrifugal, washing: the anisyl aldehyde crude product is put into to whizzer and carry out centrifugation, washed with salt solution again after centrifugation;
(5) neutralization: the anisyl aldehyde crude product after washing is carried out to the secondary washing with sodium bicarbonate water, make the pH value of anisyl aldehyde crude product be alkalescence, obtain product;
In described step 1, the 3%-10% that the quality of the potassium hydroxide added is the estragole quality;
In described step 3, add the ratio of weight and number of component as follows: 1000 parts of high purity trans-anetholes, 100-300 part dilute sulphuric acid, 200-500 part MnO
2catalyzer;
In described step 4, salt solution is mixed by muriate and water, and muriate accounts for the 2%-10% of brine quality, and muriate is a kind of in sodium-chlor, Repone K;
In described step 5, in sodium bicarbonate water, the mass percent of solute is 2-20%.
2. the preparation method of anisyl aldehyde according to claim 1, is characterized in that, in described step 1, raw material natural grass estragole is dropped in rectifying tower, purified, the tower reactor temperature of rectifying tower is 150-170 ℃, the temperature of tower top is 110-130 ℃, the estragole after being purified;
Estragole after purifying is put into to the isomery pot, then add potassium hydroxide in the isomery pot, the temperature of controlling in the isomery pot is 175-185 ℃, reaction 3-5h, and reaction stops the isomery pot is heated after finishing, and obtains trans-anethole.
3. the preparation method of anisyl aldehyde according to claim 2, is characterized in that, in described step 1, raw material natural grass estragole is dropped in rectifying tower, purified, the tower reactor temperature of rectifying tower is 155-165 ℃, the temperature of tower top is 115-125 ℃, the estragole after being purified.
4. the preparation method of anisyl aldehyde according to claim 1, is characterized in that, in described step 1, the quality of the potassium hydroxide added is 5% of estragole quality.
5. the preparation method of anisyl aldehyde according to claim 1, it is characterized in that, in described step 1, estragole is put into to the isomery pot, then add potassium hydroxide in the isomery pot, the temperature of controlling in the isomery pot is 180 ℃, reaction 4h, reaction stops the isomery pot is heated after finishing, and obtains trans-anethole.
6. the preparation method of anisyl aldehyde according to claim 1, is characterized in that, in described step 2, time brain that step 1 is obtained carries out freezing at subzero 20 ℃, under freezing conditions, to returning brain, carry out centrifugal simultaneously, centrifugation time is 10-60min, obtains the high purity trans-anethole.
7. according to the preparation method of the described anisyl aldehyde of claim 1-6 any one, it is characterized in that, in described step 3, the high purity trans-anethole that step 2 is obtained is put into reactor, and adds dilute sulphuric acid, MnO in reactor
2, the temperature of controlling in reactor is 100 ℃, reaction 4h, obtain the anisyl aldehyde crude product;
Add the ratio of weight and number of component as follows: 1000 parts of high purity trans-anetholes, 200 parts of dilute sulphuric acids, 300 parts of MnO
2catalyzer.
8. the preparation method of anisyl aldehyde according to claim 1, is characterized in that, in described step 5, the anisyl aldehyde crude product after washing carried out to the secondary washing with sodium bicarbonate water, and the pH value that makes the anisyl aldehyde crude product is 7.5-8.5.
9. the preparation method of anisyl aldehyde according to claim 8, is characterized in that, in described step 5, the anisyl aldehyde crude product after washing carried out to the secondary washing with sodium bicarbonate water, and the pH value that makes the anisyl aldehyde crude product is 8.
10. according to the preparation method of claim 1-6,8, the described anisyl aldehyde of 9 any one, it is characterized in that, in described step 5, anisyl aldehyde crude product after washing is carried out to the secondary washing with sodium bicarbonate water, make the pH value of anisyl aldehyde crude product be alkalescence, obtain product, again product is sent in rectifying tower and purified, the tower reactor temperature of rectifying tower is 155 ℃-165 ℃, and tower top temperature is 115 ℃-125 ℃, purifies and obtains high purity product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310428640.8A CN103497094B (en) | 2013-09-18 | 2013-09-18 | A kind of preparation method of anisic aldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310428640.8A CN103497094B (en) | 2013-09-18 | 2013-09-18 | A kind of preparation method of anisic aldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103497094A true CN103497094A (en) | 2014-01-08 |
| CN103497094B CN103497094B (en) | 2016-08-17 |
Family
ID=49862384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310428640.8A Active CN103497094B (en) | 2013-09-18 | 2013-09-18 | A kind of preparation method of anisic aldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103497094B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152877A (en) * | 2015-09-08 | 2015-12-16 | 广西中烟工业有限责任公司 | Preparation method for estragole and application of estragole |
| CN106220483A (en) * | 2016-07-26 | 2016-12-14 | 四川惠泉生物科技有限公司 | A kind of method that hexanal is prepared in sodium dichromate oxidation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201737863U (en) * | 2010-07-07 | 2011-02-09 | 广西万山香料有限责任公司 | Anisic aldehyde production line |
| 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 |
| CN102491884A (en) * | 2011-11-29 | 2012-06-13 | 广西壮族自治区林业科学研究院 | Isolation method for high purity anethole |
| CN102503788A (en) * | 2011-11-21 | 2012-06-20 | 湖南大学 | Application of 4-(2-methylallyl)-1,2-dihydroxybenzene in preparation of perfume |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU455087A1 (en) * | 1973-03-23 | 1974-12-30 | Всесоюзный научно-исследовательский институт синтетических и натуральных душистых веществ | The method of obtaining trans-anethole |
-
2013
- 2013-09-18 CN CN201310428640.8A patent/CN103497094B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201737863U (en) * | 2010-07-07 | 2011-02-09 | 广西万山香料有限责任公司 | Anisic aldehyde production line |
| 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 |
| CN102503788A (en) * | 2011-11-21 | 2012-06-20 | 湖南大学 | Application of 4-(2-methylallyl)-1,2-dihydroxybenzene in preparation of perfume |
| CN102491884A (en) * | 2011-11-29 | 2012-06-13 | 广西壮族自治区林业科学研究院 | Isolation method for high purity anethole |
Non-Patent Citations (4)
| Title |
|---|
| THI XUAN THI LUU等: "Fast and Green Microwave-Assisted Conversion of Essential Oil Allylbenzenes into the Corresponding Aldehydes via Alkene Isomerization and Subsequent Potassium Permanganate Promoted Oxidative Alkene Group Cleavage", 《MOLECULES》, vol. 14, 3 September 2009 (2009-09-03) * |
| 何春茂: "茴脑的性质及生产、利用", 《林产化工通讯》, vol. 38, no. 01, 31 December 2004 (2004-12-31), pages 31 - 35 * |
| 曹婷婷等: "1-烯丙基-4-甲氧基苯碱性异构研究", 《现代化工》, vol. 31, 30 June 2011 (2011-06-30), pages 329 - 331 * |
| 李正球等: "二氧化锰氧化茴脑制备茴香醛的工艺研究", 《林产化学与工业》, vol. 29, no. 04, 15 August 2009 (2009-08-15), pages 59 - 62 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152877A (en) * | 2015-09-08 | 2015-12-16 | 广西中烟工业有限责任公司 | Preparation method for estragole and application of estragole |
| CN106220483A (en) * | 2016-07-26 | 2016-12-14 | 四川惠泉生物科技有限公司 | A kind of method that hexanal is prepared in sodium dichromate oxidation |
| CN106220483B (en) * | 2016-07-26 | 2019-03-19 | 四川惠泉生物科技有限公司 | A kind of method that sodium dichromate oxidation prepares hexanal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103497094B (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106928253A (en) | A kind of preparation method of pinoxaden | |
| CN102617385B (en) | Methylene method for producing acetochlor | |
| CN103497094A (en) | Preparation method of anisic aldehyde | |
| CN107892640B (en) | Preparation method for preparing camphene by alpha-pinene isomerization | |
| CN106748752B (en) | A kind of preparation method of 2,3- naphthalenedicarboxylic acid | |
| CN103951546B (en) | Novel synthetic process of thymol | |
| CN106380383A (en) | Synthesis method of 2-hexenal | |
| CN104311405A (en) | Preparation method of benzaldehyde | |
| CN107337576B (en) | Normal temperature catalytic synthesis of 2-bromo-5-fluorobenzotrifluoride | |
| CN113563168B (en) | Method for reducing waste water in production of pseudo ionone | |
| CN105601533B (en) | Industrial method for synthesizing O-chloropropene hydroxylamine by one-pot method | |
| CN103601405A (en) | Aliphatic high-efficiency water reducing agent and preparation method thereof | |
| CN111187146B (en) | Process for producing 2-methyl-3-buten-2-ol | |
| CN104072361A (en) | Preparing method of o-hydroxyphenylacetic acid | |
| CN109535106B (en) | Preparation method of benzofuranone | |
| CN104292197A (en) | Synthesis method of spirodiclofen | |
| CN103130630A (en) | Cyclopentanol green synthetic method | |
| CN103524565A (en) | Preparation method of acetyl acetone dicarbonyl rhodium | |
| CN113563193A (en) | New preparation method of fenisobromolate | |
| CN102766235A (en) | Synthesis technology of hydrolytic polymaleic anhydride | |
| CN108080027B (en) | Resin catalyst treatment process for preparing caprolactam through liquid phase Beckmann rearrangement | |
| CN101628861A (en) | Method for synthesizing 2, 5-dichloro-phthaldialdehyde | |
| CN107176904A (en) | The preparation method of high ortho position Bisphenol F | |
| CN111807991A (en) | Method for synthesizing 2-amino-2, 3-dimethylbutyronitrile by using microchannel reactor | |
| CN105503789A (en) | Method for catalytic conversion of xylose into furfural by use of montmorillonite-supported metal ion solid acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 622150, six village, Qinglong village, Wenchang Town, Zitong County, Sichuan, Mianyang Applicant after: Sichuan Huiquan Biological Technology Co., Ltd. Address before: 622150, six village, Qinglong village, Wenchang Town, Zitong County, Sichuan, Mianyang Applicant before: Zitong County favour spring spices chemical industry company limited |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |