CN1036454C - Preparation method of anisole - Google Patents
Preparation method of anisoleInfo
- Publication number
- CN1036454C CN1036454C CN 94101265 CN94101265A CN1036454C CN 1036454 C CN1036454 C CN 1036454C CN 94101265 CN94101265 CN 94101265 CN 94101265 A CN94101265 A CN 94101265A CN 1036454 C CN1036454 C CN 1036454C
- Authority
- CN
- China
- Prior art keywords
- anisole
- hour
- reaction
- dimethyl sulfate
- sodium hydroxide
- 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.)
- Expired - Fee Related
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a preparation method of anisole, which belongs to preparation methods of ethers. The present invention is characterized in that excessive dimethyl sulphate and sodium phenolate are adopted and converted into anisole through a thorough reaction. Not only is production cost reduced, but also excessive dimethyl sulphate is converted into sodium sulfate by sodium hydroxide, and thus, the problem of environmental protection is conveniently solved. Anisole is an intermediate body for organic synthesis and can be widely used for synthesizing pesticides, perfumes, medicines, etc. The present invention has obvious use value.
Description
The invention relates to a preparation method of ether, in particular to a preparation method of anisole.
Anisole is an intermediate in organic synthesis and can be used for synthesizing pesticides, perfumes, medicines and the like. In the preparation method of anisole, one synthetic route is to react sodium phenate with dimethyl sulfate to prepare anisole. In carrying out this synthetic route, an excess of sodium phenolate may be employed to effect a complete reaction of the dimethyl sulfate (U.S. Pat. No. 5, 2,490,842). According to the national conditions, the price of phenol is higher than that of dimethyl sulfate, and the excessive sodium phenolate causes the difficulty of wastewater treatment.
The invention aims to provide a preparation method of anisole, which fully utilizes phenol, reduces the synthesis cost and reduces the phenol content in reaction residues.
The preparation method of the anisole provided by the invention is carried out according to the following reaction principle,
the method is characterized by comprising the following steps:
firstly, 10 to 30 percent of excessive dimethyl sulfate and sodium phenolate solution (prepared by 20 percent of sodium hydroxide solution and phenol according to equimolar) react for 1 hour at 10 to 30 ℃, react for half an hour at 40 ℃, and react for half an hour at reflux temperature;
(II) distilling anisole by azeotropic distillation, and returning the distilled water part to the reactor in the distillation process:
and thirdly, when the anisole obtained by azeotropic distillation is close to 90 percent of the theoretical yield, supplementing a sodium hydroxide solution with the concentration of 20 percent (weight) into the reactor, continuing the reaction, distilling for half an hour to 1 hour to ensure that the generated anisole is completely distilled out, and then drying and redistilling the anisole product.
The dosage of the dimethyl sulfate in the step (I) is calculated according to the molar ratio of a reaction equation, and the optimal excess is 20-25 percent; the amount of sodium hydroxide supplemented in the step (three) is limited to the total amount of sodium hydroxide and dimethyl sulfate which are equimolar.
The materials used in the reaction (by weight) were: 94 parts of phenol (sodium phenolate solution prepared from 40 parts of sodium hydroxide and 160 parts of water) and 69-82 parts of dimethyl sulfate.
The specific reaction process is as follows: firstly, adding dimethyl sulfate into a reaction bottle, cooling to 10 ℃, dropwise adding the prepared sodium phenolate solution within 1 hour, raising the reaction temperature to 30 ℃, gradually raising the temperature to 40 ℃, maintaining for 30 minutes, and then raising the temperature and refluxing for 30 minutes. Then the product is distilled off by azeotropy (the distillation temperature is 92-98 ℃), and in the distillation process, the distilled water is returned to the reaction bottle in 150 parts in three times. Adding 4-12 parts by weight of sodium hydroxide (prepared into a 20% solution) into a reaction bottle when the azeotropic distilled anisole reaches 100 parts, continuing the reaction, distilling for half an hour to 1 hour, and stopping the reaction. Separating the anisole distilled off by azeotropy from water. Drying anisole with anhydrous calcium chloride or anhydrous sodium sulfate, and distilling to obtain anisole with yield of over 90% and reaction residue of sodium sulfate.
Example 1
75.5 g of dimethyl sulfate (20% excess) are placed in a reaction flask equipped with a fractionating column, a stirrer and a dropping funnel, cooled to 10 ℃, and a prepared sodium phenolate solution (40 g of sodium hydroxide is dissolved in 160 g of water, 94 g of phenol is added, and the solution is stirred uniformly) is added dropwise. The reaction temperature was maintained at 10-30 ℃ and the sodium phenolate solution was added dropwise over a period of 1 hour. Then raising the temperature to 40 ℃ for half an hour, and raising the temperature and refluxing for half an hour. Then azeotropic distillation is carried out to distill out anisole and water (the gas phase temperature is 92-98 ℃). In the azeotropic distillation process, 150ml of distilled water is returned to the reaction flask for three times; when the amount of anisole distilled off by azeotropy is about 100 g, 40 g of 20% sodium hydroxide solution is added into a reaction bottle, the reaction is continued, and the distillation is carried out for half an hour to 1 hour. The reaction was then stopped. Separating the distilled anisole from water. The crude anisole was dried with anhydrous calcium chloride and distilled to give 103 g anisole with a yield of 95%.
Example 2
The dimethyl sulfate is used in an excess of 10% (the total amount of sodium hydroxide is equal to the molar amount of dimethyl sulfate), the other conditions are the same as in example 1, and the yield of anisole is 90-92%.
Example 3
The dimethyl sulfate was used in an excess of 25% (the total amount of sodium hydroxide was equimolar to the dimethyl sulfate), and the other conditions were the same as in example 1, giving an anisole yield of 97%.
Example 4
The dimethyl sulfate is used in an excess of 30% (the total amount of sodium hydroxide is equal to the molar amount of dimethyl sulfate), the other conditions are the same as in example 1, and the yield of anisole is 98%.
Compared with the prior art, the invention uses the excessive dimethyl sulfate to ensure that the sodium phenate is fully reacted and converted into the anisole, thereby not only reducing the production cost, but also conveniently solving the environmental protection problem because the excessive dimethyl sulfate is converted into the sodium sulfate by using the sodium hydroxide. The invention has obvious practical value.
Claims (3)
1. A method for preparing anisole by the reaction of dimethyl sulfate and sodium phenate is characterized in that: 10-30% of excessive dimethyl sulfate and sodium phenate solution prepared by 20% (weight) of sodium hydroxide and phenol according to equal mole are reacted at 10-30 ℃ for 1 hour, reacted at 40 ℃ for half an hour, and after the reaction is carried out for half an hour at reflux temperature, anisole is azeotropically distilled out, the distilled water part is returned to a reactor in the distillation process, when the anisole obtained by azeotropic distillation is close to 90% of theoretical yield, 20% (weight) of sodium hydroxide solution is supplemented in the reactor, the reaction is continued, the distillation is carried out for half an hour to 1 hour, the generated anisole is completely distilled out, and then the crude anisole product is dried and steamed again.
2. The method for preparing anisole according to claim 1, wherein the dimethyl sulfate is used in an excess of 20 to 25% in terms of molar ratio based on the reaction equation.
3. The method for preparing anisole according to claim 1, characterized in that the amountof supplemental sodium hydroxide is limited to the total amount of sodium hydroxide equimolar to dimethyl sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94101265 CN1036454C (en) | 1994-01-30 | 1994-01-30 | Preparation method of anisole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94101265 CN1036454C (en) | 1994-01-30 | 1994-01-30 | Preparation method of anisole |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1105974A CN1105974A (en) | 1995-08-02 |
| CN1036454C true CN1036454C (en) | 1997-11-19 |
Family
ID=5030081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94101265 Expired - Fee Related CN1036454C (en) | 1994-01-30 | 1994-01-30 | Preparation method of anisole |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1036454C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588625B (en) * | 2013-11-21 | 2015-04-15 | 浙江大洋生物科技集团股份有限公司 | Method for synthesizing anisol by utilizing methyl sodium sulfate waste residue |
| CN103922965B (en) * | 2014-04-28 | 2016-08-24 | 西安瑞联新材料股份有限公司 | A kind of synthetic method of 4-methoxyl group-2-methylbenzeneacetonitrile |
| CN107573220A (en) * | 2017-07-31 | 2018-01-12 | 常州市卜诺赛机电技术有限公司 | A kind of production method of methyl phenyl ethers anisole |
| CN107628931B (en) * | 2017-08-31 | 2020-05-29 | 清华大学 | Micro-reaction system and method for synthesizing anisole and derivatives thereof |
| CN107686441B (en) * | 2017-08-31 | 2021-03-02 | 清华大学 | Method for synthesizing aryl alkyl ether |
| CN110054549A (en) * | 2019-04-12 | 2019-07-26 | 新昌县泰如科技有限公司 | A kind of preparation method of p-methyl anisole |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2490842A (en) * | 1947-01-27 | 1949-12-13 | Du Pont | Anisole manufacture |
| US4192949A (en) * | 1977-06-28 | 1980-03-11 | Basf Aktiengesellschaft | Preparation of aralkyl phenyl ethers and alkyl phenyl ethers |
-
1994
- 1994-01-30 CN CN 94101265 patent/CN1036454C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2490842A (en) * | 1947-01-27 | 1949-12-13 | Du Pont | Anisole manufacture |
| US4192949A (en) * | 1977-06-28 | 1980-03-11 | Basf Aktiengesellschaft | Preparation of aralkyl phenyl ethers and alkyl phenyl ethers |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1105974A (en) | 1995-08-02 |
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