CN101671368A - Method for preparing coumaphos by aqueous phase method - Google Patents
Method for preparing coumaphos by aqueous phase method Download PDFInfo
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- CN101671368A CN101671368A CN200910010046A CN200910010046A CN101671368A CN 101671368 A CN101671368 A CN 101671368A CN 200910010046 A CN200910010046 A CN 200910010046A CN 200910010046 A CN200910010046 A CN 200910010046A CN 101671368 A CN101671368 A CN 101671368A
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Abstract
The invention relates to a method for preparing coumaphos by an aqueous phase method, belonging to the field of chemical vermifuge synthesis technologies. The method comprises the following steps: (A)feeding materials: feeding water into a reaction kettle, starting a stirrer, then feeding an acid-binding agent, 3-chlorin-4-methyl-7 hydroxy coumarin and a phase transfer catalyst, and adding ethylchloride; (B) controlling temperature: reacting at room temperature after feeding the materials, increasing the temperature to 50-80 DEG C and then reacting for 20-150 minutes, and discharging the materials; (C) discharging, washing and drying the materials: placing the materials into a vacuum filter to filter out waste water, then washing the coumaphos as a target product to be neutral by clear water, and then delivering the coumaphos as the target product into a drying chamber for controlling the temperature and drying. The invention has low reaction temperature, short reaction time and highyield, prevents a large quantity of organic solvents from being used, eliminates flammable and explosive hidden troubles and is outstanding in environmental protection effect.
Description
Technical field
The invention belongs to pest control with insecticide medicament synthesis technique field, relate in particular to the method that a kind of water legal system is equipped with Coumaphos.
Background technology
Coumaphos is O, and O-diethyl-O-(3-chloro-4-methylcoumarin-7) phosphorothionate is mainly used in control tussah decorations abdomen tachinid, acarine disease, domestic animal epizootic disease and pet medication etc.Because its unique chemical structure, pharmacology and toxicity characteristics, this medicine is compared with other pest control with insecticide miticides, efficient, low residue, nuisanceless, and application is all safer in livestock product and in the bee product.
3-chloro-4-methyl-7 Hydroxycoumarin and diethylaluminum monochloride obtain Coumaphos through condensation reaction, just relevant its synthetic data searching as can be known, its condensation process is synthetic still to be rested on acetone or butanone and does that (current paper is referring to Jan Kochansky.Synthesis of (Diethyl-d10) Coumaphosand Related Compounds on the solvent levels, J.Agric.Food Chem.2000,48,2826-2828).Use butanone to be solvent in a large number, methyl alcohol is for separating out carrier, the temperature of reaction height, the time is long, finish after the reaction through repeatedly separating out, recrystallization, post-processing steps such as solvent recuperation, production security is poor, pollute high, the cost height.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art part and provides a kind of temperature of reaction low, and the reaction times is short, and the yield height avoids a large amount of organic solvents to use, and eliminates inflammable and explosive hidden danger, and the significant water legal system of environmental protection efficacy is equipped with the Coumaphos method.
For achieving the above object, the present invention is achieved in that
The water legal system is equipped with the method for Coumaphos, carries out successively as follows:
(A) feed intake: in reactor, drop into water, start agitator, drop into acid binding agent, 3-chloro-4-methyl-7 Hydroxycoumarin and phase-transfer catalyst again, add diethylaluminum monochloride;
(B) temperature control: after feeding intake, at room temperature reaction when being warmed up to 50～80 ℃ again, was reacted discharging 20～150 minutes;
(C) discharging, washing and drying: blowing is gone into vacuum filter, behind the filtering waste water, send kiln temperature control, drying after with clear water target product Coumaphos being washed till neutrality.
As a kind of preferred version scheme, the acid binding agent in the step of the present invention (A) can be salt of wormwood.
As another kind of preferred version scheme, phase-transfer catalyst of the present invention is triethylamine or 1,4-Dimethylamino pyridine.
In addition, diethylaluminum monochloride of the present invention is O, the O-o,o-diethylthiophosphoryl chloride.
Secondly, the mol ratio of 3-chloro-4-methyl-umbelliferone of the present invention, diethylaluminum monochloride and phase-transfer catalyst is followed successively by: 1: 1: (0.1～0.2).
Once more, 3-chloro-4-methyl-umbelliferone of the present invention, O, the mol ratio of O-o,o-diethylthiophosphoryl chloride and triethylamine is followed successively by: 1: 1: 0.15; Described 3-chloro-4-methyl-umbelliferone, O, the mol ratio of O-o,o-diethylthiophosphoryl chloride and 1,4-Dimethylamino pyridine is followed successively by: 1: 1: 0.08.
It is that solvent substitutes the organic solvent butanone in the former route that the present invention adopts water, and after the adding phase-transfer catalyst, temperature of reaction reduces, and the reaction times shortens, and Coumaphos can obtain product through separating out, filter, washing, and is simple to operate.The present invention can realize energy-saving and emission-reduction, and safety and environmental protection significantly reduces production costs, and the further market expansion that helps Coumaphos is used.
Description of drawings
Below in conjunction with the drawings and specific embodiments the present invention is further described.Protection scope of the present invention will not only be confined to the statement of following content.
Fig. 1 is a process flow sheet of the present invention.
Embodiment
The present invention is with 3-chlorine 4-methyl-7 Hydroxycoumarin and O, O-o,o-diethylthiophosphoryl chloride (hereinafter to be referred as diethylaluminum monochloride) is a raw material, through water method synthesizing coumaphos by use, selecting triethylamine or 1,4-Dimethylamino pyridine is phase-transfer catalyst, the mol ratio of 3-chlorine 4-methyl-umbelliferone and diethylaluminum monochloride is 1: 1, the pH value is controlled at 11～13, and temperature of reaction is 60 ℃, 2 hours reaction times.
Concrete operations scheme of the present invention is: 3-chloro-4-methyl-7 Hydroxycoumarin, water, acid binding agent salt of wormwood, phase-transfer catalyst triethylamine or 1,4-Dimethylamino pyridine are joined in the reactor that agitator, thermometer are housed, slowly be warmed up to certain temperature, drip diethylaluminum monochloride reaction 2～3 hours, after reaction finishes, be discharged to vacuum filter while hot, take out filtrate and obtain Powdered Coumaphos, through washing, oven dry, packing warehouse-in.
The molar ratio of material of above-mentioned raw materials thing: 3-chloro-4-methyl-7 Hydroxycoumarin: O, the O-o,o-diethylthiophosphoryl chloride: triethylamine is 1: 1: 0.15; 3-chloro-4-methyl-7 Hydroxycoumarin: O, the O-o,o-diethylthiophosphoryl chloride: 1, the 4-Dimethylamino pyridine is 1: 1: 0.08.
Embodiment 1:
(1) feed intake: in 500 liters of reactors, drop into 300 kilograms in water earlier, start agitator, throw 36 kilograms in salt of wormwood again, 45 kilograms of 3-chloro-4-methyl-7 Hydroxycoumarins, 2 kilograms of phase-transfer catalyst 1,4-Dimethylamino pyridines add 40～45 kilograms of diethylaluminum monochlorides.
(2) temperature control: the back timing that feeds intake was at room temperature reacted 1 hour.When being warmed up to 60 ℃ again, reacted discharging 30 minutes.
(3), discharging, washing and drying: blowing is gone into vacuum filter, behind the filtering waste water, send the kiln temperature control to carry out drying at 75 ~ 80 ℃ after with clear water Coumaphos being washed till neutrality.
Embodiment 2:
(1) feeds intake: 300 kg of water are squeezed into reactor, add 36 kilograms of salt of wormwood after starting agitator, treat that salt of wormwood dissolving back (about 5 ~ 10 minutes) adds 45 kilograms of 3-chloro-4-methyl-7 Hydroxycoumarins again, open reactor heating valve, add 3 kilograms of triethylamines when treating liquid temperature rise to 40 in the still ~ 45 ℃, 40～45 kilograms of diethylaluminum monochlorides that then will weigh up and squeeze into test tank are in advance put into reactor.
(2) temperature control: after muriate adds, when treating jar interior liquid temperature rise to 70 ℃, pick up counting and temperature control 70 ~ 73 ℃ of reactions 2 hours, open the cooling water valve cooling then, when treating jar interior liquid temperature drop to the 55 ℃ left and right sides, react end, discharging.
(3) discharging, washing and drying: blowing is gone into vacuum filter, behind the filtering waste water, send the kiln temperature control to carry out drying at 75 ~ 80 ℃ after with clear water Coumaphos being washed till neutrality.
Claims (6)
1, the water legal system is equipped with the method for Coumaphos, it is characterized in that, carries out successively as follows:
(A) feed intake: in reactor, drop into water, start agitator, drop into acid binding agent, 3-chloro-4-methyl-7 Hydroxycoumarin and phase-transfer catalyst again, add diethylaluminum monochloride;
(B) temperature control: after feeding intake, at room temperature reaction when being warmed up to 50～80 ℃ again, was reacted discharging 20～150 minutes;
(C) discharging, washing and drying: blowing is gone into vacuum filter, behind the filtering waste water, send kiln temperature control, drying after with clear water target product Coumaphos being washed till neutrality.
2, water legal system as claimed in claim 1 is equipped with the method for Coumaphos, it is characterized in that: the acid binding agent in the described step (A) is a salt of wormwood.
3, water legal system as claimed in claim 1 or 2 is equipped with the method for Coumaphos, it is characterized in that: described phase-transfer catalyst is triethylamine or 1,4-Dimethylamino pyridine.
4, water legal system as claimed in claim 3 is equipped with the method for Coumaphos, it is characterized in that: described diethylaluminum monochloride is 0, the 0-o,o-diethylthiophosphoryl chloride.
5, water legal system as claimed in claim 1 is equipped with the method for Coumaphos, it is characterized in that: the mol ratio of described 3-chloro-4-methyl-7 Hydroxycoumarin, diethylaluminum monochloride and phase-transfer catalyst is followed successively by: 1: 1: (0.1～0.2).
6, water legal system as claimed in claim 4 is equipped with the method for Coumaphos, it is characterized in that: described 3-chloro-4-methyl-7 Hydroxycoumarin, 0, and the mol ratio of 0-o,o-diethylthiophosphoryl chloride and triethylamine is followed successively by: 1: 1: 0.15; Described 3-chloro-4-methyl-7 Hydroxycoumarin, 0, the mol ratio of 0-o,o-diethylthiophosphoryl chloride and 1,4-Dimethylamino pyridine is followed successively by: 1: 1: 0.08.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100100460A CN101671368B (en) | 2009-01-09 | 2009-01-09 | Method for preparing coumaphos by aqueous phase method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100100460A CN101671368B (en) | 2009-01-09 | 2009-01-09 | Method for preparing coumaphos by aqueous phase method |
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| CN101671368A true CN101671368A (en) | 2010-03-17 |
| CN101671368B CN101671368B (en) | 2012-06-06 |
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| CN2009100100460A Active CN101671368B (en) | 2009-01-09 | 2009-01-09 | Method for preparing coumaphos by aqueous phase method |
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Inventor after: Zhang Huichun Inventor after: Wang Lishi Inventor after: Niu Xionglei Inventor after: Yang Jinchen Inventor before: Zhang Huichun Inventor before: Wang Lishi Inventor before: Niu Xionglei Inventor before: Yang Jinchen |
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