CN106366127A - One-pot method for synthesizing chlorpyrifos - Google Patents
One-pot method for synthesizing chlorpyrifos Download PDFInfo
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- CN106366127A CN106366127A CN201610742186.7A CN201610742186A CN106366127A CN 106366127 A CN106366127 A CN 106366127A CN 201610742186 A CN201610742186 A CN 201610742186A CN 106366127 A CN106366127 A CN 106366127A
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Abstract
The invention provides a one-pot method for synthesizing chlorpyrifos. The one-pot method comprises the following steps: (1) performing an addition reaction: adding a first catalyst into a reactive raw material consisting of acrylonitrile, dichlorobenzene and trichloroacetyl chloride, reflowing and heating to 120 DEG C, and after completion of the reaction, cooling and filtering out the first catalyst; (2) performing a cyclization reaction: adding a second catalyst aluminum trichloride, heating to 64-66 DEG C, and cyclizing to obtain 3, 3, 5, 6-tetrachloro-4, 4-dihydropyridine-2-one; (3) synthesizing the chlorpyrifos by the one-pot method: filtering to obtain a 3, 3, 5, 6-tetrachloro-4, 4-dihydropyridine-2-one solid, adding water into the solid, adding a third catalyst, and dropwise adding ethyl chloride to obtain crude chlorpyrifos; (4) rinsing by using sodium hypochlorite. By the one-pot method provided by the invention, economic benefits of an enterprise are greatly increased, the labor is saved, material loss is reduced and the equipment investment is reduced.
Description
Technical field
The invention belongs to organic compound field is and in particular to a kind of method of synthesis chlopyrifos.
Background technology
Chlopyrifos, chemical name is o, o- diethyl-o- (3,5,6 one trichloro-2-pyridyl) thiophosphate, is a kind of
Efficiently, wide spectrum, low-residual and low drug-fast organophosphorus pesticide.Chlopyrifos has stomach toxicity, tags, fumigates triple role, to many
Plant chewing type and sucking pest is respectively provided with favorable effect.Its mixed compatibility is good, and toxicity is low compared with conventional pesticide, kills
Worm spectrum is wide, no systemic action, and the safety that can preferably ensure agricultural product, consumer is it is adaptable to the life of pollution-free high-quality agricultural product
Produce.
Chlopyrifos is domestic the dosage forms such as cream, granule, microemulsion at present.Wherein with 40.7% cream (same suitable, happy this
This) content highest；Most of is 40% cream (aeontium basis, Xin Nongbao, Bole), and in use with cream at most, effect is good；5%
Granule (Jia Siben) be mainly used in vegetable, the preventing and treating of melon subterranean pest-insect, be replace high-toxic pesticide 3% carbofuran Granules
Improved seeds；30% microemulsion is progressively promoted.
In current industrial, synthesis chlopyrifos mainly adopts dry product trichloro pyridyl sodium alcoholate to close with diethylaluminum monochloride " Aqueous phase "
Become chlopyrifos, but the major defect of the method is to synthesize, and dry product trichloro pyridyl sodium alcoholate high energy consumption, wastewater flow rate be big, wet product sodium alkoxide system
Become that during dry product sodium alkoxide work situation is poor, material loss is many.About 7.5 tons of Aqueous Phase Synthesis of Chlorpyrifos output per ton waste water, wherein pyrrole
Pyridine ketone alkaline hydrolysis needs to be cooled to 0～5 DEG C of filtration after becoming sodium alkoxide, need artificial, material loss, the energy loss more.
Content of the invention
It is an object of the invention to overcoming the weak point of the presence of prior art, proposing a kind of " one kettle way " synthesis and poisoning with poison
The method of Tickss.
Realizing above-mentioned purpose technical scheme of the present invention is:
The method that a kind of " one kettle way " synthesizes chlopyrifos, comprises the following steps:
(1) additive reaction: add in acrylonitrile, dichloro-benzenes (1,2- dichloro-benzenes), the reaction raw materials of trichloro-acetic chloride composition
Enter the first catalyst, flow back temperature reaction, terminates to 120 DEG C of reactions of temperature, then cooling filters out the first catalyst, and distillation is anti-
Answer mixed liquor to tribromo-acetyl chlorinity≤0.5% in residual liquid；Described catalyst is tetrabutyl ammonium bromide, copper powder, Cu-lyt.
One or more of；
(2) ring-closure reaction: add the second catalyst aluminum chloride in the substrate after distillation, be warming up to 64～66 DEG C, ring
Conjunction obtains 3,3,5,6- tetra- chloro- 4,4- dihydropyridine -2- ketone (hereinafter referred to as pyridone)；
(3) " one kettle way " synthesis chlopyrifos: be filtrated to get 3,3,5,6- tetra- chloro- 4,4- dihydropyridine -2- ketone (pyridone)
Solid, adds water in solid, adds the 3rd catalyst, and Deca diethylaluminum monochloride obtains chlopyrifos crude product；
(4) rinse through sodium hypochlorite, add water washing, dehydrate obtains chlopyrifos finished product.
Preferably, in reaction raw materials, acrylonitrile, trichloro-acetic chloride, the mass ratio of dichloro-benzenes are 80～120:200～400:
600, the quality of the first catalyst accounts for 5～the 10 ‰ of reaction raw materials gross mass.
Start 100 DEG C about of the temperature flowing back in step (1), in course of reaction, temperature gradually rises, stop to when 120 DEG C
Reaction, the time of reaction can be empirically 24～28h.
Wherein, described first catalyst is 2～4 parts of the tetrabutyl ammonium bromide of mass parts, 1～3 part of copper powder, Cu-lyt. 2
～4 parts of compositions.
Wherein, in described step (2), carry out at 64～66 DEG C ring-closure reaction to reactant liquor in 2,2,4- tri- chloro- 4- cyanogen
Base butyryl chlorinity≤0.1%.
Wherein, in described step (2), the ratio according to dichloro-benzenes 600 mass parts adds 1～2 mass parts aluminum chloride.
Wherein, in described step (3), the ratio of 3,3,5,6- tetra- chloro- 4,4- dihydropyridine -2- ketone solids and water is 100
～200:500, controlling ph value by Deca liquid caustic soda is 11～12.
Described liquid caustic soda is sodium hydroxide solution, and mass fraction is 32～45%.
Wherein, in described step (3), described 3rd catalyst is tri-n-octyl methyl ammonium chloride, tetrabutyl ammonium bromide, benzyl
In tributyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetramethyl ammonium chloride, Polyethylene Glycol, DMAP one
Plant or several；The addition of the 3rd catalyst accounts for 1～the 2 ‰ of the quality of water.
Preferably, in described step (3), described 3rd catalyst be DMAP, tetrabutyl ammonium bromide, 12
Alkyl trimethyl ammonium chloride, the mass ratio of three is 3:5～8:5～8.
Wherein, in described step (4), the temperature of sodium hypochlorite rinsing is 30～70 DEG C.15 are stirred after adding sodium hypochlorite
Minute, add water, be warming up to 65 DEG C and stir 30 minutes, separate oil reservoir with separatory funnel, take out oil reservoir and be warming up to 90 DEG C and protect
Temperature 1 hour, vacuum distillation obtains brown yellow oil liquid and is product.
The beneficial effects of the present invention is:
Method proposed by the present invention, substantially increases the economic benefit of enterprise, comprising:
Wastewater flow rate: by calculating, chlopyrifos per ton can reduce 3.5 tons of waste water according to new technology；
Energy consumption and artificial: a, pyridone alkaline hydrolysis are no longer cooled to 0～5 DEG C of filtration after becoming sodium alkoxide, can be directly on 45 DEG C of left sides
Right synthesis chlopyrifos, 240 degree of equivalent chlopyrifos using electricity wisely per ton；B, sodium alkoxide are no longer lowered the temperature, and cooling agitator operating needs
Energy consumption, 100 degree of equivalent chlopyrifos using electricity wisely per ton；The sodium alkoxide that c, alkaline hydrolysis obtain, as individually taken out, needs manual cleaning, needs
Want flash dryer to dry, need artificial discharging again, environment is poor, and has material loss (about 5%).
Using method proposed by the present invention, add up to 340 degree of chlopyrifos using electricity wisely per ton, save artificial, reduce material and damage
Lose, decrease the input of equipment (filter press, flash dryer).
Brief description
Fig. 1 is standard chlopyrifos sample liquid chromatogram.
Fig. 2 is the chlopyrifos sample liquid chromatogram that embodiment 1 is obtained.
Specific embodiment
Below by most preferred embodiment, the present invention to be described.Those skilled in the art institute it should be understood that, embodiment is only used for
Illustrate rather than for limiting the scope of the present invention.
In embodiment, if no special instructions, means used are the conventional means in this area.
Embodiment 1
Equipped with agitator, the 1000ml there-necked flask of thermometer, adding 90g acrylonitrile, 300g trichloro-acetic chloride,
600g dichloro-benzenes, 3g Cu-lyt., 2g tetrabutyl ammonium bromide, 2g copper powder, flow back temperature reaction, to 120 DEG C, is reaction end
(time is 26 hours, and temperature has reached 120 DEG C)；
It is cooled to 60 DEG C about beginning vacuum distillations, stop after tribromo-acetyl chlorinity≤0.5% in detection distillation substrate
Distillation, adds 1.8g aluminum chloride to the substrate after distillation, is warming up to 65 DEG C and is incubated 4 hours, 2,2,4- tri- in detection reactant liquor
Chloro- 4- cyano group butyryl chlorinity≤0.1%, that is, think that reaction reaches terminal, be filtrated to get pyridone solid；
Equipped with agitator, the 1000ml there-necked flask of thermometer, add 500g water, 120g pyridone, control temperature
Less than 45 DEG C of Deca 120g liquid caustic soda, detect ph=11～12, such as ph not, then add appropriate liquid caustic soda (mass fraction 32%
Sodium hydroxide solution, similarly hereinafter), 45 ± 3 DEG C are incubated 1 hour, add 0.3g4- dimethylamino naphthyridine, 0.6g tetra- fourth at this temperature
Base ammonium bromide, 0.6g Dodecyl trimethyl ammonium chloride, start stream plus 86g diethylaluminum monochloride, are incubated 2 hours after stream plus end；
Material in reaction bulb is poured in the separatory funnel of prior preheating (temperature of preheating is 60 DEG C about, similarly hereinafter),
Standing 30 minutes about, filtered while hot, in the clean there-necked flask of the 500ml equipped with agitator, thermometer, adds 15g hypochlorous acid
Sodium stirs 15 minutes, adds 150g water, is warming up to 65 DEG C and stirs 30 minutes；
Material in reaction bulb is poured in the separatory funnel of prior preheating, stands 30 minutes about, separate oil reservoir in dress
Have in the there-necked flask of 500ml cleaning of agitator, thermometer, be warming up to 90 DEG C and be incubated 1 hour under -0.09mpa, decompression is steamed
Evaporate and obtain as clear as crystal brown yellow oil liquid, after cooling, obtain faint yellow solid chlopyrifos, content is 97.15%, yield is
98.1%.
Measure embodiment 1 and chlopyrifos and standard chlopyrifos sample (Shenyang Chemical Engineering Inst are obtained under same experimental conditions
System) liquid chromatogram, as shown in figure 1, the chlopyrifos (as shown in Fig. 2 and Biao 2) that the present invention is obtained and standard chlopyrifos sample
(as shown in figure 1 and table 1) chromatographic peak retention time is consistent, verifies that the present invention is obtained chlopyrifos and meets national standard.
Table 1: Fig. 1 goes out peak data
| Peak number | Time delay | Area | Peak height | Area compares % |
| 1 | 10.949 | 41525468 | 2815757 | 100 |
| Amount to | 41525468 | 2815757 | 100 |
Table 2: Fig. 2 goes out peak data
| Peak number | Time delay | Area | Peak height | Area compares % |
| 1 | 10944 | 47515009 | 2962947 | 100 |
| Amount to | 47515009 | 2962947 | 100 |
Embodiment 2:
Equipped with agitator, the 1000ml there-necked flask of thermometer, adding 110g acrylonitrile, 300g trichloro-acetic chloride,
600g dichloro-benzenes, 3g Cu-lyt., 2g tetrabutyl ammonium bromide, 2g copper powder, flow back temperature reaction 25h, is that reaction is whole to 120 DEG C
Point；
It is cooled to 60 DEG C about beginning vacuum distillations, stop steaming after detection distillation substrate tribromo-acetyl chlorinity≤0.5%
Evaporate, add 1.8g aluminum chloride, be warming up to 65 DEG C and be incubated 4 hours, in detection reactant liquor, 2,2,4- tri- chloro- 4- cyano group butyl chlorides contain
Amount≤0.1%, that is, think that reaction reaches terminal, be filtrated to get pyridone solid；
Equipped with agitator, the 1000ml there-necked flask of thermometer, add 500g water, 120g pyridone, control temperature
Less than 45 DEG C of Deca 120g liquid caustic soda, detect ph=11 12, such as ph not, then add appropriate liquid caustic soda, 45 ± 3 DEG C of insulations 1 are little
When, add 0.3g4- dimethylamino naphthyridine, 0.6g tetrabutyl ammonium bromide, 0.6g trimethyl chlorination at this temperature
Ammonium, starts stream plus 86g diethylaluminum monochloride, is incubated 2 hours after stream plus end；
Material in reaction bulb is poured in the separatory funnel of prior preheating, stands 30 minutes about, filtered while hot is to dress
Have in the there-necked flask of 500ml cleaning of agitator, thermometer, add 15g sodium hypochlorite to stir 15 minutes, add 150g water, rise
Temperature stirs 30 minutes to 65 DEG C；
Material in reaction bulb is poured in the separatory funnel of prior preheating, stands 30 minutes about, separate oil reservoir in dress
Have in the there-necked flask of 500ml cleaning of agitator, thermometer, be warming up to 90 DEG C and be incubated 1 hour under -0.09mpa, decompression is steamed
Evaporate and obtain as clear as crystal brown yellow oil liquid, after cooling, obtain faint yellow solid chlopyrifos, content is 97.19%, yield is
97.5%.
Embodiment 3:
Equipped with agitator, the 1000ml there-necked flask of thermometer, adding 110g acrylonitrile, 300g trichloro-acetic chloride,
600g dichloro-benzenes, 2g Cu-lyt., 2g tetrabutyl ammonium bromide, 1g copper powder, flow back temperature reaction 27h, to 120 DEG C of reaction ends；
It is cooled to 60 DEG C about beginning vacuum distillations, stop steaming after detection distillation substrate tribromo-acetyl chlorinity≤0.5%
Evaporate, add 1.8g aluminum chloride, be warming up to 65 DEG C and be incubated 4 hours, in detection reactant liquor, 2,2,4- tri- chloro- 4- cyano group butyl chlorides contain
Amount≤0.1%, that is, think that reaction reaches terminal, be filtrated to get pyridone solid；
Equipped with agitator, the 1000ml there-necked flask of thermometer, add 500g water, 120g pyridone, control temperature
Less than 45 DEG C of Deca 120g liquid caustic soda, detect ph=11 12, such as ph not, then add appropriate liquid caustic soda, 45 ± 3 DEG C of insulations 1 are little
When, add 0.3g4- dimethylamino naphthyridine, 0.6g tetrabutyl ammonium bromide, 0.6g trimethyl chlorination at this temperature
Ammonium, starts stream plus 86g diethylaluminum monochloride, is incubated 2 hours after stream plus end；
Material in reaction bulb is poured in the separatory funnel of prior preheating, stands 30 minutes about, filtered while hot is to dress
Have in the there-necked flask of 500ml cleaning of agitator, thermometer, add 15g sodium hypochlorite to stir 15 minutes, add 150g water, rise
Temperature stirs 30 minutes to 65 DEG C；
Material in reaction bulb is poured in the separatory funnel of prior preheating, stands 30 minutes about, separate oil reservoir in dress
Have in the there-necked flask of 500ml cleaning of agitator, thermometer, be warming up to 90 DEG C and be incubated 1 hour under -0.09mpa, decompression is steamed
Evaporate and obtain as clear as crystal brown yellow oil liquid, after cooling, obtain faint yellow solid chlopyrifos, content is 97.09%, yield is
96.5%.
Embodiment 4:
Equipped with agitator, the 1000ml there-necked flask of thermometer, adding 100g acrylonitrile, 310g trichloro-acetic chloride,
600g dichloro-benzenes, 3g Cu-lyt., 2g tetrabutyl ammonium bromide, 2g copper powder, flow back temperature reaction 26h, to 120 DEG C of reaction ends；
It is cooled to 60 DEG C about beginning vacuum distillations, stop steaming after detection distillation substrate tribromo-acetyl chlorinity≤0.5%
Evaporate, add 1.8g aluminum chloride, be warming up to 65 DEG C and be incubated 4 hours, in detection reactant liquor, 2,2,4- tri- chloro- 4- cyano group butyl chlorides contain
Amount≤0.1%, that is, think that reaction reaches terminal, be filtrated to get pyridone solid；
Equipped with agitator, the 1000ml there-necked flask of thermometer, add 500g water, 120g pyridone, control temperature
Less than 45 DEG C of Deca 120g liquid caustic soda, detect ph=11 12, such as ph not, then add appropriate liquid caustic soda, 45 ± 3 DEG C of insulations 1 are little
When, add 0.3g4- dimethylamino naphthyridine, 0.6g tetrabutyl ammonium bromide, 0.6g trimethyl chlorination at this temperature
Ammonium, starts stream plus 86g diethylaluminum monochloride, is incubated 2 hours after stream plus end；
Material in reaction bulb is poured in the separatory funnel of prior preheating, stands 30 minutes about, filtered while hot is to dress
Have in the there-necked flask of 500ml cleaning of agitator, thermometer, add 15g sodium hypochlorite to stir 15 minutes, add 150g water, rise
Temperature stirs 30 minutes to 65 DEG C；
Material in reaction bulb is poured in the separatory funnel of prior preheating, stands 30 minutes about, separate oil reservoir in dress
Have in the there-necked flask of 500ml cleaning of agitator, thermometer, be warming up to 90 DEG C and be incubated 1 hour under -0.09mpa, decompression is steamed
Evaporate and obtain as clear as crystal brown yellow oil liquid, after cooling, obtain faint yellow solid chlopyrifos, content is 97.16%, yield is
98.3%.
Embodiment 5:
Equipped with agitator, the 1000ml there-necked flask of thermometer, adding 90g acrylonitrile, 300g trichloro-acetic chloride,
600g dichloro-benzenes, 3g Cu-lyt., 2g tetrabutyl ammonium bromide, 2g copper powder, backflow temperature reaction, to 120 DEG C, is reaction end；
It is cooled to 60 DEG C about beginning vacuum distillations, stop steaming after detection distillation substrate tribromo-acetyl chlorinity≤0.5%
Evaporate, add 1.8g aluminum chloride, be warming up to 65 DEG C and be incubated 4 hours, in detection reactant liquor, 2,2,4- tri- chloro- 4- cyano group butyl chlorides contain
Amount≤0.1%, that is, think that reaction reaches terminal, be filtrated to get pyridone solid；
Equipped with agitator, the 1000ml there-necked flask of thermometer, add 500g water, 120g pyridone, control temperature
Less than 45 DEG C of Deca 120g liquid caustic soda, detect ph=11 12, such as ph not, then add appropriate liquid caustic soda, 45 ± 3 DEG C of insulations 1 are little
When, add 0.3g4- dimethylamino naphthyridine, 0.6g tetrabutyl ammonium bromide, 0.6g trimethyl chlorination at this temperature
Ammonium, starts stream plus 86g diethylaluminum monochloride, is incubated 2 hours after stream plus end；
Material in reaction bulb is poured in the separatory funnel of prior preheating, stands 30 minutes about, filtered while hot is to dress
Have in the there-necked flask of 500ml cleaning of agitator, thermometer, add 25g sodium hypochlorite to stir 15 minutes, add 150g water, rise
Temperature stirs 30 minutes to 65 DEG C；
Material in reaction bulb is poured in the separatory funnel of prior preheating, stands 30 minutes about, separate oil reservoir in dress
Have in the there-necked flask of 500ml cleaning of agitator, thermometer, be warming up to 90 DEG C and be incubated 1 hour under -0.09mpa, decompression is steamed
Evaporate and obtain as clear as crystal brown yellow oil liquid, after cooling, obtain faint yellow solid chlopyrifos, content is 97.55%, yield is
98.2%.
Embodiment 6:
Equipped with agitator, the 1000ml there-necked flask of thermometer, adding 100g acrylonitrile, 300g trichloro-acetic chloride,
500g dichloro-benzenes, 3g Cu-lyt., 2g tetrabutyl ammonium bromide, 2g copper powder, backflow temperature reaction to temperature reaches 120 DEG C, for reaction
Terminal；
It is cooled to 60 DEG C about beginning vacuum distillations, stop steaming after detection distillation substrate tribromo-acetyl chlorinity≤0.5%
Evaporate, add 1.8g aluminum chloride, be warming up to 65 DEG C and be incubated 4 hours, in detection reactant liquor, 2,2,4- tri- chloro- 4- cyano group butyl chlorides contain
Amount≤0.1%, that is, think that reaction reaches terminal, be filtrated to get pyridone solid；
Equipped with agitator, the 1000ml there-necked flask of thermometer, add 500g water, 120g pyridone, control temperature
Less than 45 DEG C of Deca 120g liquid caustic soda, detect ph=11 12, such as ph not, then add appropriate liquid caustic soda, 45 ± 3 DEG C of insulations 1 are little
When, add 0.3g4- dimethylamino naphthyridine, 0.6g tetrabutyl ammonium bromide, 0.6g trimethyl chlorination at this temperature
Ammonium, starts stream plus 86g diethylaluminum monochloride, is incubated 2 hours after stream plus end；
Material in reaction bulb is poured in the separatory funnel of prior preheating, stands 30 minutes about, filtered while hot is to dress
Have in the there-necked flask of 500ml cleaning of agitator, thermometer, add 25g sodium hypochlorite to stir 15 minutes, add 150g water, rise
Temperature stirs 30 minutes to 65 DEG C；
Material in reaction bulb is poured in the separatory funnel of prior preheating, stands 30 minutes about, separate oil reservoir in dress
Have in the there-necked flask of 500ml cleaning of agitator, thermometer, be warming up to 90 DEG C and be incubated 1 hour under -0.09mpa, decompression is steamed
Evaporate and obtain as clear as crystal brown yellow oil liquid, after cooling, obtain faint yellow solid chlopyrifos, content is 97.35%, yield is
97.9%.
Embodiment 7:
Equipped with agitator, the 1000ml there-necked flask of thermometer, adding 100g acrylonitrile, 300g trichloro-acetic chloride,
500g dichloro-benzenes, 2g Cu-lyt., 2g tetrabutyl ammonium bromide, 1g copper powder, backflow temperature reaction, to 120 DEG C, is reaction end；
It is cooled to 60 DEG C about beginning vacuum distillations, stop steaming after detection distillation substrate tribromo-acetyl chlorinity≤0.5%
Evaporate, add 1.8g aluminum chloride, be warming up to 65 DEG C and be incubated 4 hours, in detection reactant liquor, 2,2,4- tri- chloro- 4- cyano group butyl chlorides contain
Amount≤0.1%, that is, think that reaction reaches terminal, be filtrated to get pyridone solid；
Equipped with agitator, the 1000ml there-necked flask of thermometer, add 500g water, 120g pyridone, control temperature
Less than 45 DEG C of Deca 120g liquid caustic soda, detect ph=11 12, such as ph not, then add appropriate liquid caustic soda, 45 ± 3 DEG C of insulations 1 are little
When, add 0.3g4- dimethylamino naphthyridine, 0.6g tetrabutyl ammonium bromide, 0.6g trimethyl chlorination at this temperature
Ammonium, starts stream plus 86g diethylaluminum monochloride, is incubated 2 hours after stream plus end；
Material in reaction bulb is poured in the separatory funnel of prior preheating, stands 30 minutes about, filtered while hot is to dress
Have in the there-necked flask of 500ml cleaning of agitator, thermometer, add 25g sodium hypochlorite to stir 15 minutes, add 150g water, rise
Temperature stirs 30 minutes to 65 DEG C；
Material in reaction bulb is poured in the separatory funnel of prior preheating, stands 30 minutes about, separate oil reservoir in dress
Have in the there-necked flask of 500ml cleaning of agitator, thermometer, be warming up to 90 DEG C and be incubated 1 hour under -0.09mpa, decompression is steamed
Evaporate and obtain as clear as crystal brown yellow oil liquid, after cooling, obtain faint yellow solid chlopyrifos, content is 97.42%, yield is
96.2%.
Above embodiment is only that the preferred embodiment of the present invention is described, and not the scope of the present invention is entered
Row limits, on the premise of without departing from design spirit of the present invention, the technical side to the present invention for this area ordinary skill technical staff
Various modifications and improvement that case is made, all should fall in the protection domain of claims of the present invention determination.
Claims (9)
1. a kind of method of " one kettle way " synthesis chlopyrifos is it is characterised in that comprise the following steps:
(1) additive reaction: add the first catalyst in acrylonitrile, dichloro-benzenes, the reaction raw materials of trichloro-acetic chloride composition, backflow
Heat up, reach 120 DEG C of reactions to temperature and terminate, then cooling filters out the first catalyst, three in distillation reaction mixed liquor to residual liquid
Chloracetyl chloride content≤0.5%；Described catalyst is one or more of tetrabutyl ammonium bromide, copper powder, Cu-lyt.；
(2) ring-closure reaction: add the second catalyst aluminum chloride to the substrate after distillation, be warming up to 64～66 DEG C, cyclization obtains
3,3,5,6- tetra- chloro- 4,4- dihydropyridine -2- ketone；
(3) " one kettle way " synthesis chlopyrifos: be filtrated to get 3,3,5,6- tetra- chloro- 4,4- dihydropyridine -2- ketone solids, in solid
Add water, add the 3rd catalyst, Deca diethylaluminum monochloride obtains chlopyrifos crude product；
(4) rinse through sodium hypochlorite, add water washing, dehydrate obtains chlopyrifos finished product.
2. method according to claim 1 is it is characterised in that acrylonitrile in reaction raw materials, trichloro-acetic chloride, dichloro-benzenes
Mass ratio is 80～120:200～400:600, and the quality of the first catalyst accounts for 5～the 10 ‰ of reaction raw materials gross mass.
3. method according to claim 1 is it is characterised in that described first catalyst is the tetrabutyl ammonium bromide of mass parts
2～4 parts, 1～3 part of copper powder, 2～4 parts of Cu-lyt. composition.
4. method according to claim 1 is it is characterised in that in described step (2), carry out cyclization anti-at 64～66 DEG C
Should to reactant liquor 2,2,4- tri- chloro- 4- cyano group butyryl chlorinity≤0.1%.
5. method according to claim 1 is it is characterised in that in described step (2), according to dichloro-benzenes 600 mass parts
Ratio adds 1～2 mass parts aluminum chloride.
6. method according to claim 1 is it is characterised in that in described step (3), 3,3,5,6- tetra- chloro- 4,4- dihydros
The ratio of pyridin-2-ones solid and water is 100～200:500, and controlling ph value by Deca liquid caustic soda is 11～12.
7. method according to claim 1 is it is characterised in that in described step (3), described 3rd catalyst is trioctylphosphine
Ammonio methacrylate, tetrabutyl ammonium bromide, benzyl tributyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetramethyl ammonium chloride, poly-
One or more of ethylene glycol, DMAP；The addition of the 3rd catalyst accounts for 1～the 2 ‰ of the quality of water.
8. method according to claim 1 is it is characterised in that in described step (3), described 3rd catalyst is 4- diformazan
Aminopyridine, tetrabutyl ammonium bromide, Dodecyl trimethyl ammonium chloride, the mass ratio of three is 3:5～8:5～8.
9. method according to claim 1 is it is characterised in that in described step (4), the temperature of sodium hypochlorite rinsing is 30
～70 DEG C.
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