阅读说明：本技术 一种2-(2,4,6-三氯苯氧基)乙基丙胺的合成方法 (Synthetic method of 2- (2,4, 6-trichlorophenoxy) ethylpropylamine ) 是由 李宝才 潘光荣 于 2020-05-27 设计创作，主要内容包括：本发明公开了一种2-(2,4,6-三氯苯氧基)乙基丙胺的合成方法,包括如下步骤：2,4,6-三氯苯酚在三氟化硼乙醚催化下,与环乙胺反应后,再与盐酸成盐,得到化合物A；化合物A在氢氧化铯一水合物催化下,以碳酸钠为缚酸剂,与1-溴丙烷反应得到2-(2,4,6-三氯苯氧基)乙基丙胺。本发明操作步骤简单,所用反应原料廉价易得、总摩尔收率为94.18％,生产出来的2-(2,4,6-三氯苯氧基)乙基丙胺纯度为98.0％以上,产品的质量较好,适合于工业化生产。(The invention discloses a method for synthesizing 2- (2,4, 6-trichlorophenoxy) ethylpropylamine, which comprises the following steps: reacting 2,4, 6-trichlorophenol with ethylamine under the catalysis of boron trifluoride diethyl etherate, and then salifying with hydrochloric acid to obtain a compound A; and reacting the compound A with 1-bromopropane under the catalysis of cesium hydroxide monohydrate by taking sodium carbonate as an acid-binding agent to obtain the 2- (2,4, 6-trichlorophenoxy) ethylpropylamine. The method has simple operation steps, cheap and easily-obtained reaction raw materials, 94.18% of total molar yield, more than 98.0% of purity of the produced 2- (2,4, 6-trichlorophenoxy) ethylpropylamine and better product quality, and is suitable for industrial production.)

1. The synthesis method of the 2- (2,4, 6-trichlorophenoxy) ethylpropylamine is characterized by sequentially comprising the following steps of:

step (a): reacting 2,4, 6-trichlorophenol with ethylamine under the catalysis of boron trifluoride diethyl etherate, and then salifying with hydrochloric acid to obtain a compound A; the reaction formula is as follows:

step (b): under the catalysis of cesium hydroxide monohydrate, sodium carbonate is used as an acid-binding agent to react with 1-bromopropane to obtain 2- (2,4, 6-trichlorophenoxy) ethylpropylamine, and the reaction formula is as follows:

2. the method for synthesizing 2- (2,4, 6-trichlorophenoxy) ethylpropylamine according to claim 1, wherein in the synthesis of the compound A in the step (a), the reaction solvent is toluene, and the weight of the reaction solvent is 4-8 times that of 2,4, 6-trichlorophenol.

3. The method for synthesizing 2- (2,4, 6-trichlorophenoxy) ethylpropylamine according to claim 1, wherein in the synthesis of the compound A in the step (a), the molar ratio of 2,4, 6-trichlorophenol to ethylamine is 1: 1.0-1.1.

4. The method for synthesizing 2- (2,4, 6-trichlorophenoxy) ethylpropylamine according to claim 1, wherein in the synthesis of compound A in step (a), the weight of boron trifluoride diethyl etherate is 4-6% of that of 2,4, 6-trichlorophenol.

5. The method for synthesizing 2- (2,4, 6-trichlorophenoxy) ethylpropylamine according to claim 1, wherein in the synthesis of the compound A in the step (a), the reaction temperature is 50-55 ℃, the time for dripping the ethylamine is 0.5-1.5 h, and the heat preservation time is 2-3 h after dripping.

6. The method for synthesizing 2- (2,4, 6-trichlorophenoxy) ethylpropylamine according to claim 1, wherein in the step (b) for synthesizing 2- (2,4, 6-trichlorophenoxy) ethylpropylamine, the reaction solvent is N, N-dimethylformamide, and the weight of the reaction solvent is 8-12 times that of 2,4, 6-trichlorophenol.

7. The method for synthesizing 2- (2,4, 6-trichlorophenoxy) ethylpropylamine according to claim 1, wherein in the synthesis of 2- (2,4, 6-trichlorophenoxy) ethylpropylamine in step (b), the molar ratio of compound A to 1-bromopropane and sodium carbonate is 1: 1.0-1.1: 2.0-2.2.

8. The method for synthesizing 2- (2,4, 6-trichlorophenoxy) ethylpropylamine according to claim 1, wherein in the step (b) for synthesizing 2- (2,4, 6-trichlorophenoxy) ethylpropylamine, the weight of cesium hydroxide monohydrate is 4-6% of that of compound A.

9. The method for synthesizing 2- (2,4, 6-trichlorophenoxy) ethylpropylamine according to claim 1, wherein in the synthesis of 2- (2,4, 6-trichlorophenoxy) ethylpropylamine in step (b), the reaction temperature is 30-35 ℃, the time for dripping 1-bromopropane is 0.5-1.5 h, and the heat preservation time is 4-6 h after dripping.

Technical Field

The invention belongs to the technical field of synthesis of pesticide intermediates, and particularly relates to a synthesis method of 2- (2,4, 6-trichlorophenoxy) ethylpropylamine.

Background

2- (2,4, 6-trichlorophenoxy) ethyl propylamine is an important fine chemical intermediate and a key intermediate for synthesizing pesticide prochloraz.

The synthesis of 2- (2,4, 6-trichlorophenoxy) ethylpropylamine mainly comprises the following two routes:

(1) chinese patent (CN101402608) reports that 2,4, 6-trichlorophenol is used as a substrate, and reacts with dichloroethane and liquid alkali to obtain an etherate, and then reacts with n-propylamine to obtain 2- (2,4, 6-trichlorophenoxy) ethylpropylamine, wherein the reaction is as follows:

in the first step of the method, in the presence of liquid alkali, the obtained etherate is easy to have elimination reaction, and in addition, the reaction with n-propylamine requires high temperature and high pressure, the reaction conditions are harsh, the reaction is not easy to control, the requirement on equipment is high, and the investment is large.

(2) Wenxianxia et al (N-N-propyl-N-2- (2,4, 6-trichlorophenoxy) ethylamine, Shanxi chemical, 1999) reported that starting from 2-phenoxyethanol, 2- (2,4, 6-trichlorophenoxy) ethanol was first obtained by reaction with chlorine, then 2- (2,4, 6-trichlorophenoxy) ethyl chloride was obtained by reaction with thionyl chloride, and then 2- (2,4, 6-trichlorophenoxy) ethyl propylamine was obtained by reaction with N-propylamine under high pressure. The method also avoids the disadvantages of harsh reaction conditions, difficult reaction control, high requirements on reaction equipment and large investment, and the reaction is as follows:

in summary, the existing synthesis method of 2- (2,4, 6-trichlorophenoxy) ethylpropylamine generally has the defects of harsh reaction conditions, difficult control of reaction, high requirement on equipment and large investment, and no satisfactory result is obtained in domestic research on synthesis of 2- (2,4, 6-trichlorophenoxy) ethylpropylamine at present. Therefore, the development of a synthetic route of the 2- (2,4, 6-trichlorophenoxy) ethylpropylamine which has mild reaction conditions and safe operation and is suitable for industrial production is significant.

Disclosure of Invention

The invention aims to provide a synthesis method of 2- (2,4, 6-trichlorophenoxy) ethylpropylamine, which has mild reaction conditions, safe operation and high yield and is suitable for industrial production, so as to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme:

a synthetic method of 2- (2,4, 6-trichlorophenoxy) ethylpropylamine sequentially comprises the following steps:

step (a): reacting 2,4, 6-trichlorophenol with ethylamine under the catalysis of boron trifluoride diethyl etherate, and then salifying with hydrochloric acid to obtain a compound A, wherein the reaction formula is as follows:

step (b): reacting the compound A with 1-bromopropane under the catalysis of cesium hydroxide monohydrate by taking sodium carbonate as an acid-binding agent to obtain 2- (2,4, 6-trichlorophenoxy) ethylpropylamine; the reaction formula is as follows:

as a further scheme of the invention: in the synthesis of the compound A in the step (a), the reaction solvent is toluene, and the weight of the reaction solvent is 4-8 times that of 2,4, 6-trichlorophenol.

As a further scheme of the invention: in the synthesis of the compound A in the step (a), the molar ratio of 2,4, 6-trichlorophenol to the cyclic ethylamine is 1: 1.0-1.1.

As a further scheme of the invention: in the synthesis of the compound A in the step (a), the weight of boron trifluoride ethyl ether is 4-6% of that of 2,4, 6-trichlorophenol.

As a further scheme of the invention: in the synthesis of the compound A in the step (a), the reaction temperature is 50-55 ℃, the time for dripping the cyclic ethylamine is 0.5-1.5 h, and the heat preservation time is 2-3 h after dripping.

As a further scheme of the invention: in the step (b), in the synthesis of the 2- (2,4, 6-trichlorophenoxy) ethylpropylamine, the reaction solvent is N, N-dimethylformamide, and the weight of the N, N-dimethylformamide is 8-12 times that of the 2,4, 6-trichlorophenol.

As a further scheme of the invention: in the step (b), in the synthesis of the 2- (2,4, 6-trichlorophenoxy) ethylpropylamine, the molar ratio of the compound A to the 1-bromopropane to the sodium carbonate is 1: 1.0-1.1: 2.0-2.2.

As a further scheme of the invention: in the step (b), in the synthesis of 2- (2,4, 6-trichlorophenoxy) ethylpropylamine, the weight of cesium hydroxide monohydrate is 4-6% of that of compound A.

As a further scheme of the invention: in the step (b), in the synthesis of the 2- (2,4, 6-trichlorophenoxy) ethylpropylamine, the reaction temperature is 30-35 ℃, the time for dripping 1-bromopropane is 0.5-1.5 h, and the heat preservation time is 4-6 h after dripping is finished.

Compared with the prior art, the invention has the beneficial effects that: the reaction conditions of the 2- (2,4, 6-trichlorophenoxy) ethyl propylamine prepared by the invention are mild, the operation is safe, and the method is suitable for industrial production.

Detailed Description

The technical solution of the present patent will be described in further detail with reference to the following embodiments.