CN111087333A - Method for preparing clethodim technical through low-temperature condensation - Google Patents
Method for preparing clethodim technical through low-temperature condensation Download PDFInfo
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- CN111087333A CN111087333A CN201911341288.8A CN201911341288A CN111087333A CN 111087333 A CN111087333 A CN 111087333A CN 201911341288 A CN201911341288 A CN 201911341288A CN 111087333 A CN111087333 A CN 111087333A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing clethodim technical material by low-temperature condensation, which is characterized in that petroleum ether is used as a solvent, trione and allyloxyamine are subjected to condensation reaction to prepare clethodim, and a stabilizer ketone complex is added during the condensation reaction; firstly, putting petroleum ether into a reaction container, then adding the trione and ketone complex, adding allyloxy amine under full stirring, and keeping the temperature in the reaction container at 18-25 ℃ for condensation reaction; washing with water, and desolventizing at 60-70 ℃ to obtain clethodim; in the condensation reaction: a forced circulation stirring structure is introduced. The invention introduces a forced stirring device, improves the condensation efficiency and effect, and obtains good effect through actual detection.
Description
Technical Field
The present invention relates to a synthetic process of agricultural herbicide clethodim, namely (+/-) -2- [ (E) -3-chloroallyloxyimino ] propyl-5- [2- (ethylthio) propyl ] -3-hydroxycyclohex-2-enone.
Background
(±) -2- [ (E) -3-chloroallyloxyimino ] propyl-5- [2- (ethylthio) propyl ] -3-hydroxy cyclohexyl-2-ketene is a common name of agricultural herbicide clethodim, the existing method for preparing the clethodim by condensation reaction of trione and allyloxyamine by taking petroleum ether as a solvent has the problems of high reaction temperature, high energy consumption in the production process, only about 86% of yield, only 90% of content and inconvenience for economical industrial production, and the produced clethodim is extremely unstable at high temperature.
Disclosure of Invention
The invention aims to provide a method for preparing clethodim technical material by low-temperature condensation, which improves the reaction yield, the content of reactants and the stability at high temperature.
The technical scheme adopted by the invention is as follows: a method for preparing clethodim technical material by low-temperature condensation comprises the steps of taking petroleum ether as a solvent, carrying out condensation reaction on propanetrione and allyloxyamine to prepare clethodim, and adding a stabilizer ketone complex during the condensation reaction;
firstly, putting petroleum ether into a reaction container, then adding the trione and ketone complex, adding allyloxy amine under full stirring, and keeping the temperature in the reaction container at 18-25 ℃ for condensation reaction; washing with water, and desolventizing at 60-70 ℃ to obtain clethodim;
in the condensation reaction: a forced circulation stirring structure is introduced.
Further, the forced circulation stirring structure is: the reactor comprises two reactors, wherein the two reactors are provided with conveying pipelines for conveying materials, and the materials are forced to circulate in the two conveying pipelines.
Furthermore, one of the two reactors is marked as a first reactor, and the other is marked as a second reactor, wherein the height of the first reactor is higher than that of the second reactor;
recording the direction from the first reactor to the second reactor, wherein the conveying pipeline is a first conveying pipeline, and the first conveying pipeline is obliquely and downwards arranged from the first reactor to the second reactor;
and in the direction from the second reactor to the first reactor, the conveying pipeline is a second conveying pipeline, and a conveying pump is arranged on the path of the second conveying pipeline.
Furthermore, heating devices are arranged on the paths of the first reactor, the second reactor, the first conveying pipeline and the second conveying pipeline.
The weight ratio of the ketone complex to the glycerol trione is 3-5: 100. The proper addition amount of the stabilizer not only can not increase the production cost, but also can achieve the design purpose.
The ketone complex is nitrogen methyl pyrrolidone.
The invention introduces a forced stirring device, improves the condensation efficiency and effect, and obtains good effect through actual detection.
Detailed Description
Example one:
the following reactions are carried out in a forced circulation stirring structure with a first reactor, a second reactor, a first conveying pipeline and a second conveying pipeline:
600 g of petroleum ether, 50 g of tricaprylin and 1.5 g of azomethyl pyrrolidone are put into a 1000ml three-neck flask, stirred for thirty minutes, kept at the temperature of 20 ℃ by a water bath, 20 g of allyloxy amine is added, kept at the temperature of 20 ℃ and reacted for 2.5 hours, the content of the allyloxy amine is detected to be less than 0.5 percent, the reaction is finished, then washed by acid water, and distilled under negative pressure at the temperature of 70 ℃ to remove a water-containing solvent, so that the clethodim is obtained, the yield is 98.2 percent and the content is 96 percent.
Example two:
the following reactions are carried out in a forced circulation stirring structure with a first reactor, a second reactor, a first conveying pipeline and a second conveying pipeline:
600 g of petroleum ether, 50 g of tricarbone and 2.5 g of azomethine are put into a 1000ml three-neck flask, stirred for thirty minutes, kept at 18 ℃ by a water bath, 20 g of allyloxy amine is added, kept at 22 ℃ and reacted for 2.5 hours, the content of the allyloxy amine is detected to be less than 0.5 percent, the reaction is finished, then washed by acid water, and distilled under negative pressure at 70 ℃ to remove the water-containing solvent, so that the clethodim is obtained, the yield is about 97.2 percent and the content is 95.2 percent.
Example three (comparative experiment):
600 g of petroleum ether and 50 g of alanyl trione are put into a 1000ml three-neck flask, stirred for three ten minutes, the temperature is kept at 20 ℃, 20 g of allylamine is added, the temperature is kept at 18 ℃, the reaction is carried out for 4 hours, the content of the allylamine is detected to be less than 0.5%, the reaction is finished, then the reaction is washed by acid water, and the water-containing solvent is removed by negative pressure distillation at 80 ℃ to obtain the clethodim, wherein the yield is about 96% and the content is 95%.
Claims (4)
1. A method for preparing clethodim technical material by low-temperature condensation is characterized in that petroleum ether is used as a solvent, trione and allyloxyamine are subjected to condensation reaction to prepare clethodim, and a stabilizer ketone complex is added during the condensation reaction;
firstly, putting petroleum ether into a reaction container, then adding the trione and ketone complex, adding allyloxy amine under full stirring, and keeping the temperature in the reaction container at 18-25 ℃ for condensation reaction; washing with water, and desolventizing at 60-70 ℃ to obtain clethodim;
in the condensation reaction: a forced circulation stirring structure is introduced.
2. The method for preparing clethodim technical material by low-temperature condensation according to claim 1, wherein the forced circulation stirring structure is that: the reactor comprises two reactors, wherein the two reactors are provided with conveying pipelines for conveying materials, and the materials are forced to circulate in the two conveying pipelines.
3. The method for preparing clethodim technical material by low-temperature condensation according to claim 2, wherein two reactors are provided, one is a first reactor, the other is a second reactor, and the height of the first reactor is higher than that of the second reactor;
recording the direction from the first reactor to the second reactor, wherein the conveying pipeline is a first conveying pipeline, and the first conveying pipeline is obliquely and downwards arranged from the first reactor to the second reactor;
and in the direction from the second reactor to the first reactor, the conveying pipeline is a second conveying pipeline, and a conveying pump is arranged on the path of the second conveying pipeline.
4. The method for preparing clethodim technical product by low-temperature condensation according to claim 3, wherein heating devices are arranged on the first reactor, the second reactor, the first conveying pipeline and the second conveying pipeline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911341288.8A CN111087333A (en) | 2019-12-24 | 2019-12-24 | Method for preparing clethodim technical through low-temperature condensation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911341288.8A CN111087333A (en) | 2019-12-24 | 2019-12-24 | Method for preparing clethodim technical through low-temperature condensation |
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| CN111087333A true CN111087333A (en) | 2020-05-01 |
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| CN201911341288.8A Pending CN111087333A (en) | 2019-12-24 | 2019-12-24 | Method for preparing clethodim technical through low-temperature condensation |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978220A (en) * | 2020-08-10 | 2020-11-24 | 宁夏一帆生物科技有限公司 | Method for synthesizing clethodim crude drug |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1994540A (en) * | 2006-11-15 | 2007-07-11 | 陈罘杲 | A novel liquid circulated stirring device |
| CN101575307A (en) * | 2009-06-11 | 2009-11-11 | 江苏长青农化股份有限公司 | Method for synthesizing clethodim |
| CN202983606U (en) * | 2012-12-24 | 2013-06-12 | 唐山拓普生物科技有限公司 | Forced circulation stirring device |
-
2019
- 2019-12-24 CN CN201911341288.8A patent/CN111087333A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1994540A (en) * | 2006-11-15 | 2007-07-11 | 陈罘杲 | A novel liquid circulated stirring device |
| CN101575307A (en) * | 2009-06-11 | 2009-11-11 | 江苏长青农化股份有限公司 | Method for synthesizing clethodim |
| CN202983606U (en) * | 2012-12-24 | 2013-06-12 | 唐山拓普生物科技有限公司 | Forced circulation stirring device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978220A (en) * | 2020-08-10 | 2020-11-24 | 宁夏一帆生物科技有限公司 | Method for synthesizing clethodim crude drug |
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Application publication date: 20200501 |
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