阅读说明：本技术 一种4-甲基-7-二乙氨基香豆素的制备方法及其应用 (Preparation method and application of 4-methyl-7-diethylamino coumarin ) 是由 包泉兴 成家钢 于 2020-06-08 设计创作，主要内容包括：本发明属于香豆素染料合成技术领域,尤其涉及一种4-甲基-7-二乙氨基香豆素的制备方法及其应用。技术方案主要包括：间羟基-N,N-二乙基苯胺与乙酰乙酸乙酯反应,二者的摩尔比为1：1.5-2.2,一部分乙酰乙酸乙酯作溶剂,边反应边蒸出反应生成的乙醇和水,之后在高温段保温一段时间,提高收率。反应好后加入冰醋酸和水,搅拌冷却至0℃,甩干得粗品,之后用甲醇精制得成品4-甲基-7-二乙氨基香豆素。本发明制备的4-甲基-7-二乙氨基香豆素,含量可达到99.5％,收率高达95％,产品品质高,能够克服传统制备方法纯度低,收率低的缺陷。且本制备方法简单,易进行工业化生产。(The invention belongs to the technical field of coumarin dye synthesis, and particularly relates to a preparation method and application of 4-methyl-7-diethylamino coumarin. The technical scheme mainly comprises the following steps: reacting m-hydroxy-N, N-diethylaniline with ethyl acetoacetate in a molar ratio of 1: 1.5-2.2, taking a part of ethyl acetoacetate as a solvent, evaporating ethanol and water generated in the reaction while reacting, and then preserving the temperature for a period of time at a high temperature section to improve the yield. After the reaction, glacial acetic acid and water are added, the mixture is stirred and cooled to 0 ℃, a crude product is obtained by drying, and then the finished product of 4-methyl-7-diethylamino coumarin is prepared by methanol refining. The content of the 4-methyl-7-diethylamino coumarin prepared by the method can reach 99.5%, the yield can reach 95%, the product quality is high, and the defects of low purity and low yield of the traditional preparation method can be overcome. And the preparation method is simple and easy for industrial production.)

1. A preparation method of 4-methyl-7-diethylamino coumarin is characterized by comprising the following steps:

reacting m-hydroxy-N, N-diethylaniline with ethyl acetoacetate at a high temperature, wherein the molar ratio of the m-hydroxy-N, N-diethylaniline to the ethyl acetoacetate is 1: 1.5-2.2; evaporating ethanol and water generated by the reaction while reacting, and carrying out heat preservation reaction; after the reaction, glacial acetic acid and water are added, stirred, cooled and dried to obtain a crude product, and then methanol is used for refining to obtain the finished product of the 4-methyl-7-diethylamino coumarin.

2. The method for preparing 4-methyl-7-diethylaminocoumarin according to claim 1, wherein: the high-temperature reaction temperature is 120-145 ℃.

3. The method for preparing 4-methyl-7-diethylaminocoumarin according to claim 1, wherein: the reaction was carried out under nitrogen.

4. The method for preparing 4-methyl-7-diethylaminocoumarin according to claim 1, wherein: adding zinc powder, ammonium chloride and acetic anhydride into the reaction system.

5. The method for preparing 4-methyl-7-diethylaminocoumarin according to claim 1, wherein: the reaction time is kept for 3-5 h.

6. The method for preparing 4-methyl-7-diethylaminocoumarin according to claim 1, wherein: the temperature of stirring and cooling was 0 ℃.

7. The method for preparing 4-methyl-7-diethylaminocoumarin according to claim 1, wherein: the amount of the methanol is 2 to 3 times of the mass of the m-hydroxy-N, N-diethylaniline.

8. The method for preparing 4-methyl-7-diethylaminocoumarin according to claim 1, wherein: refining with methanol, decolorizing with active carbon, filtering, cooling, and oven drying to obtain 4-methyl-7-diethylamino coumarin.

9. The method for preparing 4-methyl-7-diethylaminocoumarin according to claim 8, wherein: mixing the crude product with methanol and active carbon, heating, refluxing and decolorizing for 0.5-2 h. Preferably 1 h.

10. Use of a process for the preparation of 4-methyl-7-diethylaminocoumarin according to any one of claims 1 to 9 for the preparation of 4-methyl-7-diethylaminocoumarin.

Technical Field

The invention belongs to the technical field of coumarin dye synthesis, and particularly relates to a preparation method and application of 4-methyl-7-diethylamino coumarin.

Background

4-methyl-7-diethylamino coumarin is a white sheet-shaped object, belongs to one of coumarin compounds, has been used in the laser field and has been successfully expanded to the field of fluorescent whitening agents. With the deep popularization of the product application, the fluorescent dye can be widely applied to various organic light-emitting devices, and the application of the fluorescent dye can be further expanded by combining the fluorescent dye with a solid medium. In clinical medicine, the coumarin drugs have the effects of resisting bacteria, relieving spasm, dilating coronary artery, resisting cancer, dispelling wind-damp and the like, and a plurality of documents research the interaction between the coumarin drugs and protein. The 4-methyl-7-diethylamino coumarin is also used as a fluorescent whitening agent for whitening textiles such as chinlon, terylene, aramid fiber and the like, and for whitening paper products and the like, and has obvious effect. Therefore, the development and research of the products have important practical significance.

The most common synthetic route currently used for the synthesis of 4-methyl-7-diethylaminocoumarin is: and (2) cyclizing and condensing m-hydroxy-N, N-diethylaniline and beta-ethyl ketobutyrate under the condition of a catalyst to prepare the 4-methyl-7-diethylamino coumarin. However, this synthetic route has a long reaction time, a low product yield and a low product purity, and is not effective when used as a dye.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a preparation method and application of 4-methyl-7-diethylamino coumarin, and aims to solve part of problems in the prior art or at least alleviate part of problems in the prior art.

The invention is realized in such a way that the preparation method of the 4-methyl-7-diethylamino coumarin comprises the following steps:

reacting m-hydroxy-N, N-diethylaniline with ethyl acetoacetate at a high temperature, wherein the molar ratio of the m-hydroxy-N, N-diethylaniline to the ethyl acetoacetate is 1: 1.5-2.2, preferably 1: 1.5; evaporating ethanol and water generated by the reaction while reacting, and carrying out heat preservation reaction; after the reaction, glacial acetic acid and water are added, stirred, cooled and dried to obtain a crude product, and then methanol is used for refining to obtain the finished product of the 4-methyl-7-diethylamino coumarin. The synthetic route is shown in figure 1.

Further, the high temperature reaction temperature is 120-145 ℃. Preferably 127-135 deg.C, more preferably 130 deg.C.

Further, the reaction was carried out under nitrogen protection.

Furthermore, zinc powder, ammonium chloride and acetic anhydride are added into the reaction system. The mass ratio of the m-hydroxy-N, N-diethylaniline to the m-hydroxy-N, N-diethylaniline is 140: 1: 1: 1.

further, the reaction time is kept for 3-5 h. Preferably 4 hours.

Further, the stirring cooling temperature was 0 ℃ to completely precipitate the product.

Furthermore, the using amount of the methanol is 2 to 3 times of the mass of the m-hydroxy-N, N-diethylaniline.

Further, refining by using methanol, decoloring by using activated carbon, filtering, cooling and drying to obtain the finished product of the 4-methyl-7-diethylamino coumarin.

Further, mixing the crude product with methanol and active carbon, and heating up, refluxing and decoloring for 0.5-2 h. Preferably 1 h.

The preparation method of the 4-methyl-7-diethylamino coumarin is applied to preparation of the 4-methyl-7-diethylamino coumarin.

In summary, the advantages and positive effects of the invention are:

the application provides a novel preparation method of 4-methyl-7-diethylamino coumarin, which comprises the steps of reacting m-hydroxy-N, N-diethylaniline with ethyl acetoacetate in a nitrogen atmosphere under the action of a catalyst while distilling out by-products of ethanol and water to promote the reaction, and refining with methanol to finally obtain the 4-methyl-7-diethylamino coumarin with high purity and high yield.

The 4-methyl-7-diethylamino coumarin prepared by the technical scheme of the invention has the content of 99.5%, the yield of 95% and high product quality, and can overcome the defects of low purity and low yield of the traditional preparation method. And the preparation method is simple and easy for industrial production.

Drawings

FIG. 1 is a technical scheme of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. The specific embodiments described herein are merely illustrative of the invention and are not intended to be limiting.

The invention discloses a preparation method and application of 4-methyl-7-diethylamino coumarin, and the technical scheme mainly comprises the following steps: reacting m-hydroxy-N, N-diethylaniline with ethyl acetoacetate in a molar ratio of 1: 1.5-2.2, taking a part of ethyl acetoacetate as a solvent, evaporating ethanol and water generated in the reaction while reacting, and then preserving the temperature for a period of time at a high temperature section to improve the yield. After the reaction, glacial acetic acid and water are added, the mixture is stirred and cooled to 0 ℃, a crude product is obtained by drying, and then the finished product of 4-methyl-7-diethylamino coumarin is prepared by methanol refining. The reaction principle is shown in FIG. 1, and the specific embodiment is shown in the following examples.