Industrialized method for one-pot synthesis of o-chloropropene hydroxylamine

A technology of propene hydroxylamine and dichloropropene is applied in the field of industrialized synthesis of O-chloropropene hydroxylamine, which can solve the problems of increased difficulty in solvent recovery, decreased solvent recovery rate, increased cost and the like, and achieves improved reaction yield and product purity. Avoid the effect of adding and recycling separation, reducing the generation of double-joined impurities

Active Publication Date: 2019-12-13
JIANGXI HEYI CHEM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The addition of DMSO makes it more difficult to recover the solvent. Cyclohexane extracts and separates products, which easily leads to a decrease in solvent recovery rate and increased cost. Acidification and hydrolysis require rectification operations, which require high production equipment and are difficult to achieve industrialization.

Method used

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  • Industrialized method for one-pot synthesis of o-chloropropene hydroxylamine

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Experimental program
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Effect test

Embodiment 1

[0023] Embodiment 1 prepares O-chloropropene hydroxylamine with hydroxylamine salt one-pot method:

[0024] Under the environment of feeding nitrogen, drop into the reactor 650kg of ethyl acetate (molecular weight 88, 7.4kmol), hydroxylamine hydrochloride 500kg (molecular weight 69.5, 7.2kmol), 1kg hexamethylphosphoric triamide, stir for 0.5 hour, keep The temperature of the reaction solution is that dropping the mass concentration between 20-30° C. is 1000kg (7.5kmol) of 30% sodium hydroxide solution, and after the dropping is completed, the reaction is incubated for 1 hour;

[0025] After the completion of the reaction, add 1kg polyethylene glycol 800 and 1,3-dichloropropene 820kg (molecular weight 111, 7.4kmol) in the reaction solution, dropwise mass concentration is 1000kg of 30% sodium hydroxide solution, and the control reaction solution temperature is 30-40 ℃, stirring reaction for 1.5 hours;

[0026] In the reaction solution, adding mass concentration of 30% hydrochlo...

Embodiment 2

[0027] Embodiment 2 prepares O-chloropropene hydroxylamine with hydroxylamine salt one-pot method:

[0028] Under the environment of feeding nitrogen, drop into the reactor methyl acetate 810kg (molecular weight 74, 11.0kmol), hydroxylamine hydrochloride 500kg (molecular weight 69.5, 7.2kmol), 2kg DMF, stir for 0.5 hour, keep 20-30 ℃, drip The mass concentration is 1000kg (7.5kmol) of 30% sodium hydroxide solution, and after the dripping finishes, the reaction is incubated for 1 hour;

[0029] After the reaction is completed, add 2kg triethylbenzyl amine chloride and 970kg (molecular weight 111, 8.7kmol) of 1,3-dichloropropene to the reaction solution, dropwise the mass concentration of 1000kg (7.5kmol) of 30% sodium hydroxide solution. ), and the temperature of the reaction solution was controlled at 30-40 ° C, and the reaction was stirred for 1 hour;

[0030] Adding mass concentration to the reaction solution is 1000kg (8.2kmol) of hydrochloric acid of 30%, the reaction sol...

Embodiment 3

[0031] Embodiment 3 prepares O-chloropropene hydroxylamine with hydroxylamine salt one-pot method:

[0032] Under the environment of feeding nitrogen, drop into the reactor 760kg of ethyl acetate (8.6kmol), 500kg of hydroxylamine hydrochloride (molecular weight 69.5, 7.2kmol), 1.5kg DMSO, stir for 0.5 hour, keep 20-30 ° C, dropwise add mass concentration It is 1050kg (7.9kmol) of 30% sodium hydroxide solution, after the dropwise addition, the reaction is incubated for 1 hour;

[0033] After the reaction is completed, add 1.5kg 18-crown 6 and 1,3-dichloropropene 830kg (molecular weight 111, 7.5kmol) to the reaction solution, dropwise the mass concentration of 30% sodium hydroxide solution 1050kg (7.9kmol), and The temperature of the reaction solution was controlled at 30-40°C, and the reaction was stirred for 1.5 hours;

[0034] In reaction solution, adding mass concentration is 30% hydrochloric acid 1000kg (8.2kmol), be warming up to 50-60 ℃, insulation reaction 3 hours, reac...

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Abstract

The invention discloses an industrialization method for synthesizing O-chloropropene hydroxylamine by virtue of a one-pot method and a catalyst utilized in the industrialization method. The industrialization method comprises the following steps: adding acetic ester, hydroxylammonium salt and a catalyst A into a reaction kettle, adding alkali metal hydroxide, and stirring to react at 0-50 DEG C for 0-10 hours so as to generate acetohydroxamic acid; continuing to add a catalyst B and dichloropropene into reaction liquid to generate etherification reaction at 20-80 DEG C for 0-20 hours, so as to obtain N-acetyl-O-chloropropene hydroxylamine; and continuing to add protonic acid to generate acidification at 20-100 DEG C for 0-10 hours, so as to prepare O-chloropropene hydroxylammonium salt, and finally carrying out neutralization, extraction and desolvation, so as to obtain dissociative O-chloropropene hydroxylamine. The product content is higher than 99%, and the total yield is over 90%. An intermediate can be utilized for preparing high-content cyclohexenone herbicides by virtue of further reaction, is applicable to large-scale industrial production, low in cost and high in product purity and yield, and the operation is easy.

Description

technical field [0001] The invention belongs to the field of organic synthesis, in particular to an industrial synthesis method of O-chloropropene hydroxylamine. Background technique [0002] O-chloropropenylhydroxylamine is widely used in the synthesis of cyclohexenone oxime herbicides, such as clethodim, clethodim, pyrazolone, cycloxydone, saflufenone, bufendidione, etc. It is an ACCase inhibitor, a post-emergence selective herbicide, and has a good effect on most annual and perennial grass weeds. Cyclohexenone herbicides were first discovered by Japan Soda Company. In 1967, the company discovered the acaricide benzite. On the basis of this structure, the pyrone structure in coumarin was introduced, and then the pyrone compound with herbicidal activity was used as the forerunner to carry out research on it. The structure was optimized, and the oxime ether cyclohexenone herbicides with better selectivity were obtained. In 1977, the cyclohexenone herbicide researched and ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C239/20
CPCC07C239/20C07C259/06
Inventor 李有罗进超张一尘赵健
Owner JIANGXI HEYI CHEM
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