CN110590519A - Preparation method of anisaldehyde - Google Patents
Preparation method of anisaldehyde Download PDFInfo
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- CN110590519A CN110590519A CN201910912459.1A CN201910912459A CN110590519A CN 110590519 A CN110590519 A CN 110590519A CN 201910912459 A CN201910912459 A CN 201910912459A CN 110590519 A CN110590519 A CN 110590519A
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- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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Abstract
The invention discloses a preparation method of anisaldehyde, which comprises the following steps: (1) stirring and mixing p-hydroxybenzaldehyde, sodium hydroxide and water, and carrying out a salt forming reaction in a nitrogen environment; (2) after the salt forming reaction is finished, continuously introducing preheated and gasified methyl chloride into the reaction system in the step (1) for alkylation reaction, wherein in the reaction process, when the methyl chloride is continuously introduced and the system pressure is not reduced any more, the reaction is finished, cooling and pressure relief are carried out, standing and layering are carried out under the nitrogen environment, and an organic phase is washed to be alkalescent by using a sodium sulfate solution to obtain an anisaldehyde crude product; (3) and (3) carrying out reduced pressure rectification on the anisaldehyde crude product obtained in the step (2) to obtain an anisaldehyde finished product. The invention adopts methyl chloride to replace dimethyl sulfate, greatly reduces the harm to human bodies and environment, has higher yield and lower cost, and is easier to treat wastewater.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a preparation method of anisaldehyde.
Background
Anisaldehyde, also known as anisaldehyde, p-anisaldehyde. The appearance is colorless to light yellow liquid, and the product has sweet and powdery fragranceSpicy, cream, vanilla aroma and taste. Molecular formula C8H8O2The molecular weight is 136.15, the melting point is 2.5 ℃, the boiling point is 249.5 ℃, the water-insoluble organic solvent is soluble in ethanol, ether, acetone, chloroform and other organic solvents, and the water-soluble organic solvent can volatilize along with water vapor. The method is mainly used for blending the daily essences of acacia, lilac, sunflower, sweet osmanthus, lily of the valley and the like and the edible essences of vanilla, spice, almond, cream, anise, caramel, cherry, chocolate, walnut, raspberry, strawberry, mint, nut and the like.
Currently, the industrial production mainly adopts a p-hydroxybenzaldehyde method to prepare anisaldehyde, namely, the anisaldehyde is prepared by alkylation reaction of p-hydroxybenzaldehyde and dimethyl sulfate. Compared with other methods such as anethole oxidation method, anisole chloromethylation method, paracresol synthesis method and the like, the method has the advantages of short production period, high yield (91%), low cost and the like, but dimethyl sulfate belongs to highly toxic products, has great harm to human bodies and environment, is managed and controlled in the whole process of transportation, storage, use and the like, and has high difficulty and high cost in treating waste water containing dimethyl sulfate.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of anisaldehyde, which is a method for preparing anisaldehyde by using p-hydroxybenzaldehyde as a raw material and methyl chloride as an alkylating agent.
The invention is realized by the following technical scheme:
a preparation method of anisaldehyde comprises the following preparation steps:
(1) stirring and mixing p-hydroxybenzaldehyde, sodium hydroxide and water, and carrying out a salt forming reaction in a nitrogen environment;
(2) after the salt forming reaction is finished, continuously introducing preheated and gasified methyl chloride into the reaction system in the step (1) for alkylation reaction, wherein in the reaction process, when the methyl chloride is continuously introduced and the system pressure is not reduced any more, the reaction is finished, cooling and pressure relief are carried out, standing and layering are carried out under the nitrogen environment, and an organic phase is washed to be alkalescent by using a sodium sulfate solution to obtain an anisaldehyde crude product;
(3) and (3) carrying out reduced pressure rectification on the anisaldehyde crude product obtained in the step (2) to obtain an anisaldehyde finished product.
The invention further improves the scheme as follows:
the temperature of the salt forming reaction is 70-80 ℃, and the time is 2-6 h.
The alkylation reaction temperature is 70-80 deg.C, and the pressure is 0.5-0.6 Mpa.
The molar ratio of the p-hydroxybenzaldehyde to the sodium hydroxide is 1: 1.2 ~ 1.5.5, and the mass ratio of the sodium hydroxide to the water is 1: 3 ~ 5.
The preheating gasification temperature of the chloromethane is 30-50 ℃, and the pressure is 0.5-0.6 Mpa.
The mass concentration of the sodium sulfate solution is 8% ~ 12%.
The pH of the weak base was 7.5 ~ 8.
The invention has the beneficial effects that:
the invention adopts methyl chloride to replace dimethyl sulfate, greatly reduces the harm to human bodies and environment, and the preparation method provided by the invention has higher yield which reaches about 95 percent; the preparation cost is lower, no organic solvent is used, the wastewater does not contain harmful and highly toxic substances, and the wastewater is easier to treat.
The alkylation reaction of the invention adopts the pressurization reaction, improves the reaction conversion rate, leads the yield to be higher, shortens the reaction time and lowers the production cost.
Detailed Description
Example 1
122g of p-hydroxybenzaldehyde, 48g of sodium hydroxide and 192g of water are put into a pressure kettle, the pressure kettle is sealed, the mixture is stirred, the air in the kettle is replaced by nitrogen, the temperature is controlled to be 70-80 ℃, and the salt forming reaction is carried out for 3 hours.
Preheating and gasifying chloromethane at 30-50 deg.c under 0.5-0.6 MPa.
Slowly introducing gasified and preheated chloromethane into a pressure kettle for alkylation reaction, controlling the reaction temperature to be 70-80 ℃ and the pressure to be 0.5-0.6 Mpa, stopping the reaction when the kettle pressure does not decrease any more, sampling and detecting that the content of p-hydroxybenzaldehyde is less than 0.1%, cooling, decompressing, replacing nitrogen, standing and layering in a nitrogen environment, and washing the separated organic phase with 8% of ~ 12% of sodium sulfate solution until the pH value is 7.5 ~ 8 to obtain a crude product of anisaldehyde.
The crude product is rectified under reduced pressure to obtain the finished anisaldehyde product with the effective amount of 129g and the yield of 94.85 percent.
Example 2
122g of p-hydroxybenzaldehyde, 52g of sodium hydroxide and 208g of water are put into a pressure kettle, the pressure kettle is sealed, the mixture is stirred, the air in the kettle is replaced by nitrogen, the temperature is controlled to be 70-80 ℃, and salification reaction is carried out for 2 hours.
Preheating and gasifying chloromethane at 30-50 deg.c under 0.5-0.6 MPa.
Slowly introducing gasified and preheated chloromethane into a pressure kettle for alkylation reaction, controlling the reaction temperature to be 70-80 ℃ and the pressure to be 0.5-0.6 Mpa, stopping the reaction when the kettle pressure does not decrease any more, sampling and detecting that the content of p-hydroxybenzaldehyde is less than 0.1%, cooling, decompressing, replacing nitrogen, standing and layering in a nitrogen environment, and washing the separated organic phase with 8% of ~ 12% of sodium sulfate solution until the pH value is 7.5 ~ 8 to obtain a crude product of anisaldehyde.
The crude product is rectified under reduced pressure to obtain the finished anisaldehyde product with the effective amount of 130g and the yield of 95.58 percent.
Example 3
Adding 122g of p-hydroxybenzaldehyde, 60g of sodium hydroxide and 240g of water into a pressure kettle, sealing the pressure kettle, starting stirring, replacing the air in the kettle with nitrogen, controlling the temperature to be 70-80 ℃, and carrying out salt forming reaction for 5 hours.
Preheating and gasifying chloromethane at 30-50 deg.c under 0.5-0.6 MPa.
Slowly introducing gasified and preheated chloromethane into a pressure kettle for alkylation reaction, controlling the reaction temperature to be 70-80 ℃ and the pressure to be 0.5-0.6 Mpa, stopping the reaction when the kettle pressure does not decrease any more, sampling and detecting that the content of p-hydroxybenzaldehyde is less than 0.1%, cooling, decompressing, replacing nitrogen, standing and layering in a nitrogen environment, and washing the separated organic phase with 8% of ~ 12% of sodium sulfate solution until the pH value is 7.5 ~ 8 to obtain a crude product of anisaldehyde.
The crude product is rectified under reduced pressure to obtain the finished anisaldehyde product with the effective amount of 130.5g and the yield of 95.96 percent.
Claims (7)
1. The preparation method of anisaldehyde is characterized by comprising the following preparation steps:
stirring and mixing p-hydroxybenzaldehyde, sodium hydroxide and water, and carrying out a salt forming reaction in a nitrogen environment;
after the salt forming reaction is finished, continuously introducing preheated and gasified methyl chloride into the reaction system in the step (1) for alkylation reaction, wherein in the reaction process, when the methyl chloride is continuously introduced and the system pressure is not reduced any more, the reaction is finished, cooling and pressure relief are carried out, standing and layering are carried out under the nitrogen environment, and an organic phase is washed to be alkalescent by using a sodium sulfate solution to obtain an anisaldehyde crude product;
and (3) carrying out reduced pressure rectification on the anisaldehyde crude product obtained in the step (2) to obtain an anisaldehyde finished product.
2. The method for preparing anisaldehyde according to claim 1, wherein: the temperature of the salt forming reaction is 70-80 ℃, and the time is 2-6 h.
3. The method for preparing anisaldehyde according to claim 1, wherein: the alkylation reaction temperature is 70-80 deg.C, and the pressure is 0.5-0.6 Mpa.
4. The preparation method of anisaldehyde according to claim 1, wherein the molar ratio of p-hydroxybenzaldehyde to sodium hydroxide is 1: 1.2 ~ 1.5.5, and the mass ratio of sodium hydroxide to water is 1: 3 ~ 5.
5. The method for preparing anisaldehyde according to claim 1, wherein: the preheating gasification temperature of the chloromethane is 30-50 ℃, and the pressure is 0.5-0.6 Mpa.
6. The preparation method of anisaldehyde according to claim 1, wherein the mass concentration of the sodium sulfate solution is 8% ~ 12%.
7. The method for preparing anisaldehyde according to claim 1, wherein the weakly basic pH is 7.5 ~ 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910912459.1A CN110590519A (en) | 2019-09-25 | 2019-09-25 | Preparation method of anisaldehyde |
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| CN201910912459.1A CN110590519A (en) | 2019-09-25 | 2019-09-25 | Preparation method of anisaldehyde |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863322A (en) * | 2012-10-15 | 2013-01-09 | 嘉兴市安瑞材料科技有限公司 | Method for synthesizing p-methoxylbenzaldehyde |
| CN105646167A (en) * | 2014-11-10 | 2016-06-08 | 青岛首泰农业科技有限公司 | Synthetic process for p-methoxybenzaldehyde |
| CN106187725A (en) * | 2016-07-05 | 2016-12-07 | 上海应用技术学院 | Hydroxy benzaldehyde and the etherification method of derivant thereof |
-
2019
- 2019-09-25 CN CN201910912459.1A patent/CN110590519A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863322A (en) * | 2012-10-15 | 2013-01-09 | 嘉兴市安瑞材料科技有限公司 | Method for synthesizing p-methoxylbenzaldehyde |
| CN105646167A (en) * | 2014-11-10 | 2016-06-08 | 青岛首泰农业科技有限公司 | Synthetic process for p-methoxybenzaldehyde |
| CN106187725A (en) * | 2016-07-05 | 2016-12-07 | 上海应用技术学院 | Hydroxy benzaldehyde and the etherification method of derivant thereof |
Non-Patent Citations (1)
| Title |
|---|
| 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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Application publication date: 20191220 |