阅读说明：本技术 一种戊二酰亚胺衍生物的制备方法 (Preparation method of glutarimide derivative ) 是由 许玉东 徐飞翔 于 2020-12-30 设计创作，主要内容包括：本发明公开了一种戊二酰亚胺衍生物的制备方法,所述方法包括如下步骤：在负压状态下,将乙酸酐滴加至熔融态的1,1-环己基二乙酸中,反应得到1,1-环己基二乙酸酐；将氨水加入氨化釜中,滴加1,1-环己二乙酸酐进行氨化反应,加入盐酸调节PH值,得到析出晶体即为戊烷戊酰胺酸；向反应釜中加入戊烷戊酰胺酸﹑甲苯溶剂和冰醋酸,加热搅拌反应,降温抽滤得到滤饼；将滤饼加入到氨水中浸泡搅拌,再次抽滤,用去离子水淋洗,烘干后得到戊二酰亚胺,该种戊二酰亚胺衍生物的制备方法,以乙酸酐和1,1-环己基二乙酸为原料,有效地提高了反应的效率,提高了产品的产率,有利于降低产品的生产成本,提高了生产的效益。(The invention discloses a preparation method of glutarimide derivatives, which comprises the following steps: under the negative pressure state, dripping acetic anhydride into molten 1, 1-cyclohexanediacetic acid to react to obtain 1, 1-cyclohexanediacetic anhydride; adding ammonia water into an ammoniation kettle, dropwise adding 1, 1-cyclohexanediacetic anhydride to carry out ammoniation reaction, and adding hydrochloric acid to adjust the pH value to obtain precipitated crystals, namely pentane valeramide acid; adding pentan valeryl amic acid, a toluene solvent and glacial acetic acid into a reaction kettle, heating, stirring, reacting, cooling, and filtering to obtain a filter cake; the preparation method of the glutarimide derivative takes acetic anhydride and 1, 1-cyclohexanediacetic acid as raw materials, effectively improves the reaction efficiency, improves the product yield, is beneficial to reducing the production cost of the product, and improves the production benefit.)

1. A method for preparing a glutarimide derivative, comprising the steps of:

under the negative pressure state, dripping acetic anhydride into molten 1, 1-cyclohexanediacetic acid to react to obtain 1, 1-cyclohexanediacetic anhydride;

adding ammonia water into an ammoniation kettle, dropwise adding 1, 1-cyclohexanediacetic anhydride to carry out ammoniation reaction, and adding hydrochloric acid to adjust the pH value to obtain precipitated crystals, namely pentane valeramide acid;

adding pentan valeryl amic acid, a toluene solvent and glacial acetic acid into a reaction kettle, heating, stirring, reacting, cooling, and filtering to obtain a filter cake;

and adding the filter cake into ammonia water, soaking and stirring, performing suction filtration again, leaching with deionized water, and drying to obtain the pentanediimide.

2. A method for producing a glutarimide derivative according to claim 1 wherein: the method for adding ammonia water into an ammonification kettle, dropwise adding 1, 1-cyclohexanediacetic anhydride to carry out ammonification reaction, adding hydrochloric acid to adjust the pH value, and obtaining precipitated crystals, namely pentane valeramide acid comprises the following steps:

adding 10-25 parts of ammonia water into an ammonification kettle, and dropwise adding 1, 1-cyclohexane diacetic anhydride to carry out an ammonification reaction;

adding activated carbon into the reaction solution, performing suction filtration, adding hydrochloric acid to adjust the pH value to acidity, separating out crystals, washing with deionized water, and drying to obtain pentanediamic acid;

wherein, the ammonification reaction time is 1-2 h.

3. A method for producing a glutarimide derivative according to claim 2 wherein: adding pentan valeryl amic acid, a toluene solvent and glacial acetic acid into a reaction kettle, heating, stirring, reacting, cooling, and filtering to obtain a filter cake, wherein the method comprises the following steps:

adding pentane valeryl amic acid, 20-40 parts of toluene solvent and 3-5 parts of glacial acetic acid into a reaction kettle, heating to 70-80 ℃, stirring, carrying out reflux reaction for 6-8 h, stopping heating, cooling to 10-18 ℃, and carrying out suction filtration to obtain a filter cake.

4. A method for producing a glutarimide derivative according to claim 3 wherein: the method for adding the filter cake into ammonia water for soaking and stirring, performing suction filtration again, leaching with deionized water, and drying to obtain the pentanediimide comprises the following steps:

adding the filter cake into 30-70 parts of 15% ammonia water, soaking and stirring for 3-8 hours, and performing suction filtration again;

and washing the filter cake obtained by suction filtration with deionized water, and drying at 60-85 ℃ for 1-2 h to obtain pentane glutaryl imide.

5. A method for producing a glutarimide derivative according to claim 1 wherein: the pressure of the negative pressure state is-0.15 to-0.08 MPa.

6. A method for producing a glutarimide derivative according to claim 1 wherein: the molar ratio of the 1, 1-cyclohexanediacetic acid to the acetic anhydride is 1: 1.4-2.0.

7. A method for producing a glutarimide derivative according to claim 1 wherein: the dripping time of the acetic anhydride is 0.5-3 h, and the dripping temperature is 110-130 ℃.

Technical Field

The invention relates to the technical field of compound preparation, in particular to a preparation method of a glutarimide derivative.

Background art:

in the prior art, there are many methods for synthesizing glutarimide derivatives, and for example, a great deal of disclosure is made on the relevant synthesis technology of the product in patent documents such as chinese patent CN 201880069719.7. However, because various intermediates are adopted for synthesis, the cost is high, side reactions are more, and the utilization rate of raw materials is low. The main reason why the content of the obtained product is not high and the yield is low due to incomplete anhydrization process is that 1, 1-cyclohexanediacetic acid, acetic anhydride, ammonium acetate and the like are adopted for reaction. Therefore, in order to improve the utilization rate of raw materials, increase the yield and reduce the cost, the scheme needs to be improved.

Disclosure of Invention

The invention aims to provide a preparation method of a glutarimide derivative, which aims to overcome the defect of high cost of glutarimide synthesis in the prior art.

A process for the preparation of a glutarimide derivative, said process comprising the steps of:

under the negative pressure state, dripping acetic anhydride into molten 1, 1-cyclohexanediacetic acid to react to obtain 1, 1-cyclohexanediacetic anhydride;

adding ammonia water into an ammoniation kettle, dropwise adding 1, 1-cyclohexanediacetic anhydride to carry out ammoniation reaction, and adding hydrochloric acid to adjust the pH value to obtain precipitated crystals, namely pentane valeramide acid;

adding pentan valeryl amic acid, a toluene solvent and glacial acetic acid into a reaction kettle, heating, stirring, reacting, cooling, and filtering to obtain a filter cake;

and adding the filter cake into ammonia water, soaking and stirring, performing suction filtration again, leaching with deionized water, and drying to obtain the pentanediimide.

Further, the method for adding ammonia water into an ammonification kettle, dropwise adding 1, 1-cyclohexane diacetic anhydride to carry out ammonification reaction, adding hydrochloric acid to adjust the pH value, and obtaining precipitated crystals, namely pentane valeramide acid, comprises the following steps:

adding 10-25 parts of ammonia water into an ammonification kettle, and dropwise adding 1, 1-cyclohexane diacetic anhydride to carry out an ammonification reaction;

adding activated carbon into the reaction solution, performing suction filtration, adding hydrochloric acid to adjust the pH value to acidity, separating out crystals, washing with deionized water, and drying to obtain pentanediamic acid;

wherein, the ammonification reaction time is 1-2 h.

Further, the method for adding pentane valeryl amic acid, toluene solvent and glacial acetic acid into the reaction kettle, heating, stirring, reacting, cooling and filtering to obtain the filter cake comprises the following steps:

adding pentane valeryl amic acid, 20-40 parts of toluene solvent and 3-5 parts of glacial acetic acid into a reaction kettle, heating to 70-80 ℃, stirring, carrying out reflux reaction for 6-8 h, stopping heating, cooling to 10-18 ℃, and carrying out suction filtration to obtain a filter cake.

Further, the method for preparing the pentadiimide by adding the filter cake into ammonia water for soaking and stirring, performing suction filtration again, leaching with deionized water and drying comprises the following steps:

adding the filter cake into 30-70 parts of 15% ammonia water, soaking and stirring for 3-8 hours, and performing suction filtration again;

and washing the filter cake obtained by suction filtration with deionized water, and drying at 60-85 ℃ for 1-2 h to obtain pentane glutaryl imide.

Further, the pressure of the negative pressure state is-0.15 to-0.08 MPa.

Further, the molar ratio of the 1, 1-cyclohexanediacetic acid to the acetic anhydride is 1: 1.4-2.0.

Further, the dripping time of the acetic anhydride is 0.5-3 h, and the dripping temperature is 110-130 ℃.

The invention has the advantages that: the preparation method of the glutarimide derivative takes acetic anhydride and 1, 1-cyclohexanediacetic acid as raw materials, effectively improves the reaction efficiency, improves the product yield, is beneficial to reducing the production cost of the product and improving the production benefit, and meanwhile, has wide raw material source, simple and convenient operation, convenient control of the reaction progress, low pollution, low raw material loss in production and high raw material utilization rate.

Detailed Description

In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.

A process for the preparation of a glutarimide derivative, said process comprising the steps of:

the method comprises the following steps: under the negative pressure state, dripping acetic anhydride into molten 1, 1-cyclohexanediacetic acid to react to obtain 1, 1-cyclohexanediacetic anhydride:

wherein the pressure of the negative pressure state is-0.15 to-0.08 MPa;

the molar ratio of the 1, 1-cyclohexanediacetic acid to the acetic anhydride is 1: 1.4-2.0;

the dripping time of the acetic anhydride is 0.5-3 h, and the dripping temperature is 110-130 ℃;

step two: adding ammonia water into an ammonification kettle, dropwise adding 1, 1-cyclohexane diacetic anhydride to carry out ammonification reaction, adding hydrochloric acid to adjust the pH value, and obtaining precipitated crystals, namely pentane valeramide acid:

adding 10-25 parts of ammonia water into an ammonification kettle, and dropwise adding 1, 1-cyclohexane diacetic anhydride to carry out an ammonification reaction;

adding activated carbon into the reaction solution, performing suction filtration, adding hydrochloric acid to adjust the pH value to acidity, separating out crystals, washing with deionized water, and drying to obtain pentanediamic acid;

wherein the ammoniation reaction time is 1-2 h;

step three: adding pentan valeryl amic acid, a toluene solvent and glacial acetic acid into a reaction kettle, heating, stirring, reacting, cooling, and performing suction filtration to obtain a filter cake:

adding pentane valeryl amic acid, 20-40 parts of toluene solvent and 3-5 parts of glacial acetic acid into a reaction kettle, heating to 70-80 ℃, stirring, carrying out reflux reaction for 6-8 h, stopping heating, cooling to 10-18 ℃, and carrying out suction filtration to obtain a filter cake;

step four: adding the filter cake into ammonia water, soaking and stirring, performing suction filtration again, leaching with deionized water, and drying to obtain glutarimide:

adding the filter cake into 30-70 parts of 15% ammonia water, soaking and stirring for 3-8 hours, and performing suction filtration again;

and washing the filter cake obtained by suction filtration with deionized water, and drying at 60-85 ℃ for 1-2 h to obtain glutarimide.

Example 1

Under the negative pressure state, the pressure is-0.15 MPa, 14 parts of acetic anhydride is dripped into 10 parts of molten 1, 1-cyclohexanediacetic acid to react to obtain 1, 1-cyclohexanediacetic anhydride, the dripping time is 0.5h, and the dripping temperature is 110 ℃;

adding 10 parts of ammonia water into an ammoniation kettle, dropwise adding 1, 1-cyclohexane diacetic anhydride to carry out ammoniation reaction for 1 h;

adding 5 parts of activated carbon into the reaction solution, performing suction filtration, adding 10 parts of hydrochloric acid to adjust the pH value to acidity, separating out crystals, washing with deionized water, and drying to obtain pentanediacetic amide acid;

adding pentan valeramic acid, 20 parts of toluene solvent and 3 parts of glacial acetic acid into a reaction kettle, heating to 70 ℃, stirring, carrying out reflux reaction for 6 hours, stopping heating, cooling to 10 ℃, and carrying out suction filtration to obtain a filter cake;

adding the filter cake into 30 parts of 15% ammonia water, soaking and stirring for 3 hours, and performing suction filtration again;

and washing the filter cake obtained by suction filtration with deionized water, and drying at 60 ℃ for 1h to obtain glutarimide.

Example 2

Under the negative pressure state, the pressure is-0.1 MPa, 18 parts of acetic anhydride is dripped into 10 parts of molten 1, 1-cyclohexanediacetic acid to react to obtain 1, 1-cyclohexanediacetic anhydride, the dripping time is 2h, and the dripping temperature is 120 ℃;

adding 18 parts of ammonia water into an ammonification kettle, dropwise adding 1, 1-cyclohexane diacetic anhydride to carry out ammonification reaction for 1.5 h;

adding 5 parts of activated carbon into the reaction solution, performing suction filtration, adding 10 parts of hydrochloric acid to adjust the pH value to acidity, separating out crystals, washing with deionized water, and drying to obtain pentanediacetic amide acid;

adding pentan valeramic acid, 30 parts of toluene solvent and 4 parts of glacial acetic acid into a reaction kettle, heating to 75 ℃, stirring, carrying out reflux reaction for 7 hours, stopping heating, cooling to 14 ℃, and carrying out suction filtration to obtain a filter cake;

adding the filter cake into 50 parts of ammonia water with the concentration of 15%, soaking and stirring for 5 hours, and performing suction filtration again;

and washing the filter cake obtained by suction filtration with deionized water, and drying at 75 ℃ for 1.5h to obtain glutarimide.

Example 3

Under the negative pressure state, the pressure is-0.08 MPa, 20 parts of acetic anhydride is dripped into 10 parts of molten 1, 1-cyclohexanediacetic acid to react to obtain 1, 1-cyclohexanediacetic anhydride, the dripping time is 3h, and the dripping temperature is 130 ℃;

adding 25 parts of ammonia water into an ammonification kettle, dropwise adding 1, 1-cyclohexane diacetic anhydride to carry out ammonification reaction for 2 hours;

adding 5 parts of activated carbon into the reaction solution, performing suction filtration, adding 10 parts of hydrochloric acid to adjust the pH value to acidity, separating out crystals, washing with deionized water, and drying to obtain pentanediacetic amide acid;

adding pentan valeramic acid, 40 parts of toluene solvent and 5 parts of glacial acetic acid into a reaction kettle, heating to 80 ℃, stirring, carrying out reflux reaction for 8 hours, stopping heating, cooling to 18 ℃, and carrying out suction filtration to obtain a filter cake;

adding the filter cake into 70 parts of ammonia water with the concentration of 15%, soaking and stirring for 8 hours, and performing suction filtration again;

and washing the filter cake obtained by suction filtration with deionized water, and drying at 85 ℃ for 2h to obtain glutarimide.

It will be appreciated by those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The embodiments disclosed above are therefore to be considered in all respects as illustrative and not restrictive. All changes which come within the scope of or equivalence to the invention are intended to be embraced therein.