Preparation method of O-3-chloro-2-allyl hydroxylamine

A technology of propenyl hydroxylamine and O-3-, which is applied in the field of preparation of O-3-chloro-2-propenyl hydroxylamine, can solve the problems of low selectivity and cumbersome operation

Pending Publication Date: 2022-04-26
杭州瑞思新材料有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The hydrolysis reaction of this method is an equilibrium reaction, and the acetone generated needs to be continuously removed to complete the reaction, and the operation is relatively cumbersome.
Another most commonly used method is the oxime method, using hydroxylamine sulfate to react with methyl acetate under alkaline conditions to generate sodium acetohydroxamic acid, protecting the hydroxylamine nitrogen, and then reacting with trans-1,3-dichloropropene Generate oxime ether, hydrolyze the nitrogen protecting group, and obtain the product chlorinated amine. This method is simple but the selectivity is not high in the reaction process, and excessive impurities are inevitably produced.
[0004] There are deficiencies in the existing methods, and industrial production urgently needs to develop more competitive preparation methods

Method used

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  • Preparation method of O-3-chloro-2-allyl hydroxylamine

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] In the first three-necked flask, 71.0 g of distilled water and 100 g of hydroxylamine sulfate were successively added, and then 162.8 g of liquid caustic soda was added dropwise to prepare 207.2 g of hydroxylamine aqueous solution. Pour the prepared hydroxylamine aqueous solution into the second three-necked flask, then add 99.6g of methyl acetate, start stirring, then add 1.5g of 4-dimethylaminopyridine catalyst, and then dropwise add 196g of 30% NaOH aqueous solution (liquid Alkali), the temperature was kept at 20°C, and the reaction was carried out for 1 h. Add 136g of trans-1,3-dichloropropene into the second three-necked flask, raise the temperature to 50°C, and react for 7h. The molar ratio of the above raw materials n(hydroxylamine):n(methyl acetate):n(4-dimethylaminopyridine):n(NaOH):n(trans-1,3-dichloropropene) is 1:1.1:0.01 :2.1:1.

[0032] Subsequently, 180 g of hydrochloric acid was added, and after stirring, it was refluxed at 60° C. for 2 h. After the s...

Embodiment 2

[0034] In the first three-necked flask, 71.0 g of distilled water and 100 g of hydroxylamine sulfate were successively added, and then 162.8 g of liquid caustic soda was added dropwise to prepare 207.2 g of hydroxylamine aqueous solution. Pour the prepared hydroxylamine aqueous solution into the second three-necked flask, then add 99.6g of methyl acetate, start stirring, then add 15.0g of 4-dimethylaminopyridine catalyst, and then dropwise add 196g of 30% NaOH aqueous solution (liquid Alkali), the temperature was kept at 20°C, and the reaction was carried out for 1 h. Add 136g of trans-1,3-dichloropropene into the second three-necked flask, raise the temperature to 70°C, and react for 5h. The molar ratio of the above raw materials n(hydroxylamine):n(methyl acetate):n(4-dimethylaminopyridine):n(NaOH):n(trans-1,3-dichloropropene) is 1:1.1:0.1 :2.1:1.

[0035] Subsequently, 180 g of hydrochloric acid was added, and after stirring, it was refluxed at 60° C. for 2 h. After the s...

Embodiment 3

[0037] In the first three-necked flask, 71.0 g of distilled water and 100 g of hydroxylamine sulfate were successively added, and then 162.8 g of liquid caustic soda was added dropwise to prepare 207.2 g of hydroxylamine aqueous solution. Pour the prepared hydroxylamine aqueous solution into the second three-necked flask, then add 99.6g of methyl acetate, start stirring, then add 7.5g of 4-dimethylaminopyridine catalyst, and then dropwise add 196g of 30% NaOH aqueous solution (liquid Alkali), the temperature was kept at 20°C, and the reaction was carried out for 1 h. Add 136g of trans-1,3-dichloropropene into the second three-necked flask, raise the temperature to 60°C, and react for 6h. The molar ratio of the above raw materials n(hydroxylamine):n(methyl acetate):n(4-dimethylaminopyridine):n(NaOH):n(trans-1,3-dichloropropene) is 1:1.1:0.05 :2.1:1.

[0038] Subsequently, 180 g of hydrochloric acid was added, and after stirring, it was refluxed at 60° C. for 2 h. After the s...

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Abstract

The invention relates to a preparation method of O-3-chloro-2-allyl hydroxylamine, which comprises the following steps: S1, adding a hydroxylamine aqueous solution and methyl acetate into a flask, completely mixing, then adding a 4-dimethylaminopyridine catalyst, and then dropwise adding liquid caustic soda into the flask for reaction; s2, adding trans-1, 3-dichloropropene into the flask again, raising the temperature, and maintaining the temperature for reaction; s3, adding hydrochloric acid, stirring, and then carrying out reflux reaction; s4, after organic matters are separated through reduced pressure distillation, liquid caustic soda is added to adjust the pH; s5, extraction is conducted at the room temperature, then reduced pressure distillation is conducted to remove the solvent, and O-3-chloro-2-allyl hydroxylamine is obtained.The method is easy to operate, high in yield and safe in reaction, impurities are effectively reduced, and the method is suitable for large-scale industrial production.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a preparation method of O-3-chloro-2-propenyl hydroxylamine. Background technique [0002] O-3-Chloro-2-propenyl hydroxylamine, also known as chlorinated amine, trans-3-chloro-2-propenyl hydroxylamine, can be used as an alkyl amination reagent, and can be used to introduce alkyl in organic synthesis and new drug production. Oxyamine groups to ketone compounds (especially steroids), can be used as intermediates in the production of medicines, as well as intermediates in the field of new medicine and new pesticide creation, and are important intermediates in the production of clethodim. [0003] At present, there are mainly the following methods for synthesizing chlorinated amines. One is the hydrolysis of acetone oxime ether method. Ketone and hydroxylamine react in an alkaline environment to generate oxime, and react with trans-1,3-dichloropropene to generate oxime ether. Hydroc...

Claims

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Application Information

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IPC IPC(8): C07C259/06C07C239/20
CPCC07C259/06C07C239/20
Inventor 张治国沈博颜吉笑王佳豪赵伟炳李彪
Owner 杭州瑞思新材料有限公司
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