CN103588811B - A kind of preparation method of Profenofos intermediate three ester - Google Patents
A kind of preparation method of Profenofos intermediate three ester Download PDFInfo
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- CN103588811B CN103588811B CN201310585869.2A CN201310585869A CN103588811B CN 103588811 B CN103588811 B CN 103588811B CN 201310585869 A CN201310585869 A CN 201310585869A CN 103588811 B CN103588811 B CN 103588811B
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- bromophenol
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Abstract
The present invention relates to a kind of preparation method of Profenofos intermediate three ester, comprise the steps: (1) 2 ,-chloro-4-bromophenol and potassium hydroxide react and generate sylvite; (2) 2-chloro-4-bromophenol potassium and O, O-o,o-diethylthiophosphoryl chloride generate three esters under the effect of Trimethylamine 99 phase-transfer catalyst.Adopt the method for the invention that the yield of product can be made to bring up to more than 98% by 96%, content brings up to 99.0% by 98.0%, it is a kind of method that high-level efficiency prepares high-purity Profenofos intermediate three ester, waste water becomes potassium chloride salt from past sodium chloride salt simultaneously, as potash fertilizer raw material, be convenient to wastewater treatment.
Description
Technical field
The present invention relates to a kind of preparation method of Profenofos intermediate three ester, particularly relate to a kind of method preparing high yield, high purity Profenofos intermediate three ester.
Background technology
The existing production technique of preparation method of Profenofos intermediate three ester does Fu's acid agent by sodium hydroxide, the chloro-4-bromophenol of 2-, with O, the condensation of O-o,o-diethylthiophosphoryl chloride generates three esters (full name: O, O-diethyl O-(2-chlorine 4-bromophenyl) thiophosphatephosphorothioate), yield 96%, content 98%, trade effluent is 15%-20% salts solution.Three esters have a lot of effect in the industrial production.Three ester industrial goods are transparent liquid.Longer storage duration, color can turn yellow gradually, and direct sunlight, air are stored, and color change is fast, can be temporarily muddy after commoving, and naturally clarifies, have amine taste, be dissolved in the organic solvents such as ethanol, ether, chloroform, benzene after a few hours.Mainly for the production of Profenofos.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of a kind of high yield, high purity Profenofos intermediate three ester.
A preparation method for Profenofos intermediate three ester, comprises the steps:
(1) 2 ,-chloro-4-bromophenol and potassium hydroxide react and generate sylvite;
(2) 2-chloro-4-bromophenol potassium and O, O-o,o-diethylthiophosphoryl chloride generate three esters under quaternary ammonium salt phase transfer catalyst effect.
The preparation method of Profenofos intermediate three ester of the present invention, the mol ratio of the chloro-4-bromophenol of 2-and potassium hydroxide is 1:1.0 ~ 1.2 in step (1), 2 ,-chloro-4-bromophenol and potassium hydroxide were 50-80 DEG C of salify 2 hours.
The preparation method of Profenofos intermediate three ester of the present invention, in step (2), 2-chloro-4-bromophenol potassium and O, O-o,o-diethylthiophosphoryl chloride generates three esters under quaternary ammonium salt phase transfer catalyst effect, mol ratio is 2-chloro-4-bromophenol potassium: O, O-o,o-diethylthiophosphoryl chloride: quaternary ammonium salt=1:1.02 ~ 1.10:0.02, condensation 5-6 hour under temperature is 35-50 DEG C of condition.
Profenofos intermediate three ester preparation method difference from prior art of the present invention is: in the present invention, Fu's acid agent is that potassium hydroxide substitutes sodium hydroxide, during condensation, ph value of reaction is gentleer than sodium hydroxide, pH value change is inviolent, institute is few with reaction side reaction, carry out thoroughly, the yield of product brings up to more than 98% by 96%, content brings up to 99.0% by 98.0%, it is a kind of method that high-level efficiency prepares high-purity Profenofos intermediate three ester, waste water becomes potassium chloride salt from past sodium chloride salt simultaneously, as potash fertilizer raw material, be convenient to wastewater treatment.
Embodiment
For further illustrating the present invention, illustrate with the following Examples:
Embodiment 1
(1) 2-chloro-4-bromophenol 1000Kg(96.5%), potassium hydroxide 1.1 i.e. 289Kg(99%), 50 DEG C are reacted 2 hours, proceed to condensation;
(2) 2-chloro-4-bromophenol potassium solution is a collection of, O, O-o,o-diethylthiophosphoryl chloride 1.02 i.e. 887Kg (99.5%), the Trimethylamine 99 18Kg(30% aqueous solution), 35 DEG C are reacted 5 hours, and layering obtains three ester 1654Kg, content 99.1%, yield 98.1%.
Embodiment 2
(1) 2-chloro-4-bromophenol 1000Kg(96.5%), potassium hydroxide 1.15 i.e. 302Kg(99%), 70 DEG C are reacted 2 hours, proceed to condensation;
(2) 2-chloro-4-bromophenol potassium solution is a collection of, O, O-o,o-diethylthiophosphoryl chloride 1.05 i.e. 913Kg (99.5%), the Trimethylamine 99 18Kg(30% aqueous solution), 40 DEG C are reacted 5 hours, and layering obtains three ester 1651Kg, content 99.4%, yield 98.2%.
Embodiment 3
(1) 2-chloro-4-bromophenol 1000Kg(96.5%), potassium hydroxide 1.2 i.e. 315Kg(99%), 70 DEG C are reacted 2 hours, proceed to condensation;
(2) 2-chloro-4-bromophenol potassium solution is a collection of, O, O-o,o-diethylthiophosphoryl chloride 1.1 i.e. 956Kg (99.5%), the Trimethylamine 99 18Kg(30% aqueous solution), 50 DEG C are reacted 6 hours, and layering obtains three ester 1657Kg, content 99.0%, yield 98.2%.
Embodiment 4
(1) 2-chloro-4-bromophenol 1000Kg(96.5%), potassium hydroxide 1.15 i.e. 302Kg(99%), 80 DEG C are reacted 2 hours, proceed to condensation;
(2) 2-chloro-4-bromophenol potassium solution is a collection of, O, O-o,o-diethylthiophosphoryl chloride 1.05 i.e. 913Kg (99.5%), the Trimethylamine 99 18Kg(30% aqueous solution), 50 DEG C are reacted 6 hours, and layering obtains three ester 1656Kg, content 99.4%, yield 98.5%.
Above-described embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that the common engineering technical personnel in this area make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.
Claims (1)
1. a preparation method for Profenofos intermediate three ester, is characterized in that: comprise the steps:
(1) 2-chloro-4-bromophenol and potassium hydroxide react and generate sylvite: the mol ratio of the chloro-4-bromophenol of 2-and potassium hydroxide is 1:1.0 ~ 1.2, and the chloro-4-bromophenol of 2-and potassium hydroxide are at 50-80 DEG C of salify 2-3 hour;
(2) 2-chloro-4-bromophenol potassium and O, O-o,o-diethylthiophosphoryl chloride generates three esters under the effect of Trimethylamine 99 phase-transfer catalyst, described Trimethylamine 99 to be concentration be 30% the aqueous solution, mol ratio is 2-chloro-4-bromophenol potassium: O, O-o,o-diethylthiophosphoryl chloride: Trimethylamine 99=1:1.02 ~ 1.10:0.02, condensation 5-7 hour under temperature is 35-50 DEG C of condition.
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| CN110922425A (en) * | 2019-11-07 | 2020-03-27 | 山东亿盛实业股份有限公司 | Continuous countercurrent extraction synthesis method of profenofos intermediate triester |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100241A (en) * | 1985-04-01 | 1986-07-09 | 武汉大学 | Synthesis of methyl 1605 by phase transition catalysis method |
| CN1101646A (en) * | 1994-07-23 | 1995-04-19 | 南开大学 | Synthesizing method for propyl-bromo-phopshorous of organic phosphorous insecticide |
| CN102617636A (en) * | 2012-02-24 | 2012-08-01 | 山东科源化工有限公司 | Preparation method of high-purity profenofos |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100241A (en) * | 1985-04-01 | 1986-07-09 | 武汉大学 | Synthesis of methyl 1605 by phase transition catalysis method |
| CN1101646A (en) * | 1994-07-23 | 1995-04-19 | 南开大学 | Synthesizing method for propyl-bromo-phopshorous of organic phosphorous insecticide |
| CN102617636A (en) * | 2012-02-24 | 2012-08-01 | 山东科源化工有限公司 | Preparation method of high-purity profenofos |
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Denomination of invention: A preparation method of propyl bromophosphorus intermediate triester Effective date of registration: 20211124 Granted publication date: 20160330 Pledgee: Hainan Runyu economic and Trade Co.,Ltd. Pledgor: SHANDONG KEYUAN CHEMICAL Co.,Ltd. Registration number: Y2021980013078 |
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