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Preparation method of trans-3-chloro-2-propenyl hydroxylamine

A technology of propenyl hydroxylamine and dichloropropene, which is applied in the field of preparation of trans-3-chloro-2-propenyl hydroxylamine, can solve the problems of high cost, difficulty in industrialization, and inconvenient operation, and achieve high yield and easy operation. The effect of simplicity and easy purchase of raw materials

Active Publication Date: 2021-02-12
UNIV OF SCI & TECH BEIJING
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Problems solved by technology

[0003] The existing common method for synthesizing trans-3-chloro-2-propenylhydroxylamine is to introduce a large amount of hydrogen chloride gas into the toluene solution of acetonitrile and absolute ethanol, stir for 22 hours, then drop Add hydroxylamine hydrochloride aqueous solution, stir until the organic layer is separated to form the compound ethyl hydroxamate, and then use tetrabutylammonium bromide as a phase transfer catalyst to react with trans-1,3-dichloropropene to obtain trans-3 -Chloro-2-propenyl hydroxylamine, this method uses a large amount of hydrogen chloride gas, pollution and corrosion are all very serious, and more expensive phase transfer catalysts are used, which is not conducive to industrialization in terms of cost and environmental protection
In addition, there is also a common method of alkylating N-hydroxyphthalamide and 1,3-dichloropropene with dimethyl sulfoxide as a solvent at room temperature to obtain the product 2-((3-chloroalkene Propyl)oxy)isoindoline-1,3-dione, then 2-((3-chloroallyl)oxy)isoindoline-1,3-dione and anhydrous hydrazine in Reaction in ethanol solution to obtain trans-3-chloro-2-propenyl hydroxylamine, the anhydrous hydrazine used in this method is highly poisonous, very inconvenient to operate, and also causes great pollution to the environment, the price of anhydrous hydrazine is very high Expensive, no domestic production, high cost, difficult to industrialize

Method used

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  • Preparation method of trans-3-chloro-2-propenyl hydroxylamine

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[0024] Such as figure 1 Shown, a kind of preparation method of trans-3-chloro-2-propenyl hydroxylamine of the present invention, described preparation method specifically comprises the following steps:

[0025] S1): using trans-1,3-dichloropropene as raw material, first hydrolyzing trans-1,3-dichloropropene to obtain 3-chloropropenol;

[0026] S2): 3-chloropropenol obtained in S1 and hydroxylamine salt are catalyzed by an acidic catalyst to generate trans-3-chloro-2-propenylhydroxylamine.

[0027] The specific steps of said S1) are:

[0028] S1.1) Now mix trans-1,3-dichloropropene and alkali metal carbonate evenly in proportion;

[0029] S1.2) The homogeneously mixed material of S1.1) is subjected to a hydrolysis reaction at a temperature of 98-100° C., and the reaction time is 8-12 hours;

[0030] S1.3) After the completion of the hydrolysis reaction, let it stand for 25-35 minutes, take the upper layer and extract it with ethyl acetate for 3 to 5 times, then distill under...

Embodiment 1

[0042] Put trans-1,3-dichloropropene and potassium carbonate into the reaction flask, raise the temperature to 80°C, and react for 8 hours to obtain an aqueous solution of 3-chloropropenol, then let it stand for 30 minutes, and extract the upper layer with ethyl acetate for 3-5 After that, distill under reduced pressure at 50°C, distill the fraction at 28°C to obtain 3-chloropropenol; put 3-chloropropenol and hydroxylamine sulfate into the reaction flask, then add sulfonic acid resin for alcohol dehydration reaction, and heat up to 80°C, React for 8 hours, then let stand for 30 minutes, extract and distill to obtain trans-3-chloro-2-propenyl hydroxylamine; the molar ratio of trans-1,3-dichloropropene and potassium carbonate is 1:0.7; the 3- The molar ratio of chloropropenol to hydroxylamine sulfate is 1:1.2.

[0043] The yield of trans-3-chloro-2-propenyl hydroxylamine obtained in this example was 81%, and the purity was 89%.

Embodiment 2

[0045] Put trans-1,3-dichloropropene and sodium carbonate into the reaction flask, raise the temperature to 90°C, and react for 10 hours to obtain an aqueous solution of 3-chloropropenol, then let it stand for 30 minutes, and extract the upper layer with ethyl acetate for 3-5 After that, distill under reduced pressure at 50°C, and distill the fraction at 28°C to obtain 3-chloropropenol; put 3-chloropropenol and hydroxylamine hydrochloride into the reaction flask, then add sulfonic acid resin for alcohol dehydration reaction, and heat up to 90°C. Reacted for 10 hours, then stood still for 30 minutes, and extracted and distilled to obtain trans-3-chloro-2-propenyl hydroxylamine; the molar ratio of the trans-1,3 dichloropropene and potassium carbonate was 1:0.9; the 3-chloro The molar ratio of allyl alcohol to hydroxylamine sulfate is 1:1.5.

[0046] The yield of trans-3-chloro-2-propenyl hydroxylamine obtained in this example was 85%, and the purity was 99.2%.

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Abstract

The invention belongs to the technical field of organic synthesis, and relates to a preparation method of trans-3-chloro-2-propenyl hydroxylamine for producing clethodim technical intermediates and other pesticide important intermediates, which specifically comprises the following steps: hydrolyzing trans-1, 3-dichloropropene serving as a raw material to obtain 3-chloropropenol; and reacting the obtained 3-chloropropenol with hydroxylamine salt under the catalysis of an acidic catalyst to generate the trans-3-chloro-2-propenyl hydroxylamine. By adopting the technical scheme, the preparation method disclosed by the invention has the beneficial effects that the raw materials are easy to purchase, the operation is simple and convenient, the yield is high, no pollution is caused, and industrial production is easy.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and relates to a preparation method of trans-3-chloro-2-propenyl hydroxylamine used for producing clethodim technical intermediates and other important pesticide intermediates. Background technique [0002] At present, trans-3-chloro-2-propenyl hydroxylamine, chloroamine (O-3-chloro-2-propenyl hydroxylamine), is an important pesticide and pharmaceutical intermediate, widely used in cyclohexenone Synthesis of herbicides, which are acetyl-coA carboxylase (ACCsae) inhibitors, have the characteristics of high efficiency, safety, and high selectivity, and can inhibit the biosynthesis of fatty acids and ultimately lead to crop death. It can be used to prevent and control a variety of grass weeds including annual and perennial grass weeds, and is safe for dicotyledonous crops; it has good systemic properties, and the active ingredients are absorbed within 1 to 3 hours after application. Rainf...

Claims

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Application Information

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IPC IPC(8): C07C239/08C07C29/124C07C33/42
CPCC07B2200/09C07C29/124C07C239/08C07C33/423
Inventor 杨运旭杜晓雨
Owner UNIV OF SCI & TECH BEIJING
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