CN111072519B - Preparation method of cyanoethyl ester - Google Patents
Preparation method of cyanoethyl ester Download PDFInfo
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- CN111072519B CN111072519B CN201911298047.XA CN201911298047A CN111072519B CN 111072519 B CN111072519 B CN 111072519B CN 201911298047 A CN201911298047 A CN 201911298047A CN 111072519 B CN111072519 B CN 111072519B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C261/00—Derivatives of cyanic acid
- C07C261/04—Cyanamides
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Abstract
The invention relates to a preparation method of cyanoethyl ester, which adopts isopropyl titanate as a catalyst to react methyl cyanoester with ethanol to obtain the cyanoethyl ester, and specifically comprises the following steps: s1: sequentially adding methyl cyanoester, ethanol and isopropyl titanate into a rectifying tower kettle; s2, heating to increase the temperature to enable the materials in the S1 to react, and continuously and slowly adding ethanol; s3, collecting fractions at a temperature lower than 68 ℃ in time after the cyanoethyl ester is generated in the reaction; s4, periodically taking the material in the rectifying tower kettle for gas chromatography analysis, and stopping the reaction until the content of cyanomethyl ester is less than or equal to 2%; s5, after the reaction is finished, carrying out reduced pressure distillation on the materials in the tower kettle, and recovering methanol and ethanol; s6, distilling the fraction collected in S3 under reduced pressure, and separating out low-boiling-point substances and a finished product of cyanoethyl ester. The invention has the advantages that: the cyanoethyl ester product prepared by the method has high purity, less impurity content and high molar yield, and obtains good economic benefit.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a preparation method of cyanoethyl ester.
Background
Cyanoethyl ester is a very useful fine chemical intermediate raw material, which is mainly used for synthesizing pesticides, perfumes and medicines. In the latest synthetic route of the acetamiprid in China, cyanoethyl ester is used as an important ring in the synthetic process of the acetamiprid. By improving the production process conditions, the improvement of the product quality and yield of the cyanoethyl ester plays a key role in improving the product quality of the acetamiprid and reducing the cost, and has important significance in improving the production environment and the surrounding environment.
Disclosure of Invention
The invention aims to provide a preparation method of cyanoethyl ester with high product purity, low impurity content and high molar yield.
In order to solve the technical problems, the technical scheme of the invention is as follows: the preparation method of the cyanoethyl ester has the innovation points that: the preparation method adopts isopropyl titanate as a catalyst, and enables cyanomethyl ester to react with ethanol to obtain cyanoethyl ester, and specifically comprises the following steps:
s1: sequentially adding methyl cyanoester, ethanol and isopropyl titanate into a rectifying tower kettle;
s2, heating to increase the temperature to enable the materials in the S1 to react, and continuously and slowly adding ethanol;
s3, collecting fractions at a temperature lower than 68 ℃ in time after the cyanoethyl ester is generated in the reaction;
s4, periodically taking the material in the rectifying tower kettle for gas chromatography analysis, and stopping the reaction until the content of cyanomethyl ester is less than or equal to 2%;
s5, after the reaction is finished, carrying out reduced pressure distillation on the materials in the tower kettle, and recovering methanol and ethanol;
s6, distilling the fraction collected in S3 under reduced pressure, and separating out low-boiling-point substances and a finished product of cyanoethyl ester.
In S1, the mass ratio of cyanomethyl ester to isopropyl titanate is 20-50: 1, and the molar ratio of cyanomethyl ester to ethanol is 1: 1-5.
Further, the addition of ethanol to S2 is carried out simultaneously with the reaction.
Further, the collection of the fraction in S3 was performed simultaneously with the reaction.
Further, the methanol-ethanol mixture in the column bottom after the reaction in S5 can be recycled.
The invention has the advantages that: according to the preparation method of the cyanoethyl ester, the cyanomethyl ester, the ethanol and the isopropyl titanate are adopted for reaction, and in the process of preparing the cyanoethyl ester by using the cyanomethyl ester, because the reaction is a reversible reaction, the method adopts a method of adding an ester exchange catalyst, continuously supplementing the ethanol and continuously extracting the generated cyanoethyl ester, so that the reaction tends to be carried out in the direction of generating the cyanoethyl ester, and the conversion rate of converting the cyanomethyl ester into the cyanoethyl ester is more than or equal to 98.0 percent; the methanol generated by the reaction can be recycled; the prepared cyanoethyl ester product has high purity, less impurity content and high molar yield, and obtains good economic benefit; the preparation method is safe and environment-friendly, is suitable for industrial production, and has wide application prospect.
Detailed Description
The following examples will provide those skilled in the art with a more complete understanding of the present invention, but are not intended to limit the scope of the present invention to the examples.
The preparation method of the cyanoethyl ester adopts isopropyl titanate as a catalyst, and the cyanoethyl ester is obtained by the reaction of cyanomethyl ester and ethanol, and specifically comprises the following steps:
s1: sequentially adding methyl cyanoester, ethanol and isopropyl titanate into a rectifying tower kettle;
s2, heating to increase the temperature to enable the materials in the S1 to react, and continuously and slowly adding ethanol;
s3, collecting fractions at a temperature lower than 68 ℃ in time after the cyanoethyl ester is generated in the reaction;
s4, periodically taking the material in the rectifying tower kettle for gas chromatography analysis, and stopping the reaction until the content of cyanomethyl ester is less than or equal to 2%;
s5, after the reaction is finished, carrying out reduced pressure distillation on the materials in the tower kettle, and recovering methanol and ethanol;
s6, distilling the fraction collected in S3 under reduced pressure, and separating out low-boiling-point substances and a finished product of cyanoethyl ester.
As an example, a more specific embodiment is that the mass ratio of cyanomethyl ester to isopropyl titanate in S1 is 20-50: 1, the molar ratio of cyanomethyl ester to ethanol is 1: 1-5, ethanol is added to S2 to carry out the reaction simultaneously, the fraction collected in S3 is carried out simultaneously, and the methanol-ethanol mixture in the column bottom after the reaction in S5 is finished can be recycled.
The process for producing cyanoethyl ester of the present invention will be described in detail below with reference to specific examples.
Examples
The embodiment discloses a preparation method of cyanoethyl ester, which adopts isopropyl titanate as a catalyst and comprises the following specific steps:
294g of cyanomethyl ester, 206g of ethanol and 16g of isopropyl titanate are sequentially added into a 1000ml rectifying tower kettle (anhydrous), and 208g of ethanol is added into a 250ml constant pressure dropping funnel; and (3) heating for reaction, starting to collect fractions after total reflux is carried out for 1.5h, controlling the reflux ratio to enable the temperature at the top of the tower to be less than or equal to 68 ℃, starting to slowly dropwise add ethanol for 2-3 h, and continuously collecting the fractions after dropwise addition is finished. And sampling from the rectifying tower kettle every 3 hours after the dropwise addition is finished, carrying out gas phase detection, and stopping the reaction when the gas phase detection result shows that the content of the cyanomethyl ester is less than or equal to 2%. After the reaction is finished, the materials in the rectifying tower are decompressed and distilled to recover methanol and ethanol. And the fraction collected by the rectifying tower and at the temperature of less than or equal to 68 ℃ is subjected to reduced pressure distillation to separate low-boiling-point substances and a cyanoethyl ester finished product.
In this example, the cyanoethyl ester product was analyzed by gas chromatography to obtain a cyanoethyl ester content of 99.6% and a molar yield of 97%.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A preparation method of cyanoethyl ester is characterized in that: the preparation method adopts isopropyl titanate as a catalyst, and enables cyanomethyl ester to react with ethanol to obtain cyanoethyl ester, and specifically comprises the following steps:
s1: sequentially adding methyl cyanoester, ethanol and isopropyl titanate into a rectifying tower kettle;
s2, heating to increase the temperature to enable the materials in the S1 to react, and continuously and slowly adding ethanol;
s3, collecting fractions at a temperature lower than 68 ℃ in time after the cyanoethyl ester is generated in the reaction;
s4, periodically taking the material in the rectifying tower kettle for gas chromatography analysis, and stopping the reaction until the content of cyanomethyl ester is less than or equal to 2%;
s5, after the reaction is finished, carrying out reduced pressure distillation on the materials in the tower kettle, and recovering methanol and ethanol;
s6, distilling the fraction collected in S3 under reduced pressure, and separating out low-boiling-point substances and a finished product of cyanoethyl ester.
2. The method for preparing cyanoethyl ester according to claim 1, wherein: the mass ratio of the cyanomethyl ester to the isopropyl titanate in S1 is 20-50: 1, and the molar ratio of the cyanomethyl ester to the ethanol is 1: 1-5.
3. The method for preparing cyanoethyl ester according to claim 1, wherein: the addition of ethanol to S2 was carried out simultaneously with the reaction.
4. The method for preparing cyanoethyl ester according to claim 1, wherein: the collection of fractions in S3 was performed simultaneously with the reaction.
5. The method for preparing cyanoethyl ester according to claim 1, wherein: and after the reaction in the S5 is finished, the methanol-ethanol mixed liquid in the tower kettle can be recycled.
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