阅读说明：本技术 一种双吲哚基甲烷类化合物的制备方法 (Preparation method of bis-indolyl methane compound ) 是由 刘万毅 吴志强 王刚 刘睿波 段斌 相庆雨 王旭军 陈小燕 于 2020-06-19 设计创作，主要内容包括：本发明公开了一种双吲哚基甲烷类化合物的制备方法,包括以下步骤：(1)将反应底物原料芳香醛类与吲哚类、微量的催化剂水分别加入到反应釜内；(2)在密闭状态下加热到110-180℃,保持一定的时间；(3)停止加热,使反应釜冷却到室温至80度,加入有机溶剂冲洗物料到收集槽中；(4)进行固液分离、洗涤、再结晶方法获得目标产物双吲哚基甲烷类化合物；(5)溶剂母液收集并回收产物、回收溶剂套用。本发明与现有技术相比的优点在于：成本低、环保。(The invention discloses a preparation method of a bis-indolyl methane compound, which comprises the following steps: (1) adding aromatic aldehydes, indoles and a trace amount of catalyst water serving as reaction substrate raw materials into a reaction kettle respectively; (2) heating to 110-180 ℃ in a sealed state, and keeping for a certain time; (3) stopping heating, cooling the reaction kettle to room temperature to 80 ℃, and adding an organic solvent to flush the materials into a collecting tank; (4) carrying out solid-liquid separation, washing and recrystallization to obtain a target product bis-indolyl methane compound; (5) collecting the solvent mother liquor, recovering the product, and recovering the solvent for reuse. Compared with the prior art, the invention has the advantages that: low cost and environmental protection.)

1. The preparation method of the bis-indolyl methane compound is characterized by comprising the following steps:

(1) adding aromatic aldehydes, indoles and a trace amount of catalyst water serving as reaction substrate raw materials into a reaction kettle respectively;

(2) heating to 110-180 ℃ in a sealed state, and keeping for a certain time;

(3) stopping heating, cooling the reaction kettle to room temperature to 80 ℃, and adding an organic solvent to flush the materials into a collecting tank;

(4) carrying out solid-liquid separation, washing and recrystallization to obtain a target product bis-indolyl methane compound;

(5) collecting the solvent mother liquor, recovering the product, and recovering the solvent for reuse.

2. The method for preparing bis-indolylmethane compounds according to claim 1, wherein the method comprises the following steps: the feeding proportion of the reaction substrate raw material aromatic aldehyde and the indole in the step (1) is 1:2 mol.

3. The method for preparing bis-indolylmethane compounds according to claim 1, wherein the method comprises the following steps: the catalyst used in the step (1) is water, and the using amount of the catalyst is 0.185-1.85 mol% of the reaction substrate raw material.

4. The method for preparing bis-indolylmethane compounds according to claim 1, wherein the method comprises the following steps: the reaction pressure in the step (2) is 1-10 atmospheric pressure.

5. The method for preparing bis-indolylmethane compounds according to claim 1, wherein the method comprises the following steps: the reaction time in the step (2) is 20-180 minutes.

6. The method for preparing bis-indolylmethane compounds according to claim 1, wherein the method comprises the following steps: and (3) measuring the temperature distribution of the reaction device by using an infrared measuring instrument.

7. The method for preparing bis-indolylmethane compounds according to claim 1, wherein the method comprises the following steps: the organic solvent added in the step (3) is one of polar solvents or a mixed solvent with any proportion.

Technical Field

The invention relates to the technical field of bis-indolyl methane compounds, in particular to a preparation method of a bis-indolyl methane compound.

Background

The bis-indolyl methane (BIMs) derivatives have wide application in the fields of essence, perfume, dye, medicine and agriculture, and are very important basic organic raw materials. The general synthesis method is an alkylation reaction of indole compounds and aldehydes or ketones in a solvent under the catalysis of a catalyst. Wherein the catalyst comprises acidic catalysts such as protonic acid, Lewis acid-surfactant, solid acid and the like; the solvent is dichloroethane, etc., or water and surfactant in water phase system. These processes are all carried out in open vessels, requiring stirring or milling; the catalyst is difficult to recycle and is easy to cause water pollution in general; or the catalyst preparation is complicated; or preparing organic waste liquid containing a large amount of toxic metals and surfactants due to demulsification and washing in a Lewis acid-surfactant combination (LASCs) catalyst system in an aqueous phase, and particularly generating toxic waste water containing a large amount of surfactant sodium dodecyl sulfate which is difficult to treat. Generally, the yield of various catalytic reactions is not high, the subsequent purification waste is large in production amount, and a large amount of waste liquid is generated due to the fact that a large amount of organic solvent participates in the reaction, the atom economy of the whole process is poor, the cost is high, the pollution is serious, and therefore the industrial large-scale application is difficult. Therefore, the present invention is to overcome or solve the above problems and to provide a new technical method of high efficiency, cleanness and greenness under thermal catalysis without catalyst and non-toxic solvent and trace amount of water.

Disclosure of Invention

The invention aims to overcome the technical defects and provide a preparation method of a bis-indolyl methane compound with low cost and environmental protection.

In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method of bis-indolyl methane compounds comprises the following steps:

(1) adding aromatic aldehydes, indoles and a trace amount of catalyst water serving as reaction substrate raw materials into a reaction kettle respectively;

(2) heating to 110-180 ℃ in a sealed state, and keeping for a certain time;

(3) stopping heating, cooling the reaction kettle to room temperature to 80 ℃, and adding an organic solvent to flush the materials into a collecting tank;

(4) carrying out solid-liquid separation, washing and recrystallization to obtain a target product bis-indolyl methane compound;

(5) collecting the solvent mother liquor, recovering the product, and recovering the solvent for reuse.

Compared with the prior art, the invention has the advantages that: when the preparation method of the bis-indolyl methane compound is used, other catalysts are not needed for reaction, only water is needed, the use of the catalysts in the preparation reaction process can be eliminated, a large number of resources are saved, the use cost is reduced, the pollution of a toxic solvent in the preparation reaction process can be reduced through the high-efficiency mass transfer and the self-solvent thermal catalytic effect of a reaction system, the high-efficiency and clean production of the bis-indolyl methane derivative is realized, the phenomena that the catalysts are difficult to recycle and pollute the environment are avoided, and the preparation method is more environment-friendly.

As an improvement, the feeding ratio of the aromatic aldehydes and the indoles as the reaction substrate raw materials in the step (1) is 1:2 mol.

As an improvement, the catalyst used in the step (1) is water, and the using amount of the catalyst is 0.185-1.85 mol% of the raw materials of the reaction substrates.

As an improvement, the reaction pressure in the step (2) is 1-10 atm.

As an improvement, the reaction time in the step (2) is 20 to 180 minutes.

As a modification, the temperature distribution of the reaction apparatus in (3) is measured by using an infrared measuring instrument.

As an improvement, the organic solvent added into the washing material in the step (3) is one of polar solvents or a mixed solvent with any proportion.

Detailed Description

The present invention is further described in the following by specific examples, which are illustrative only and not limiting, and should not be construed as limiting the scope of the present invention.