CN105017067B - Synthetic method of one kind 2 chlorine N (2,4 dichlorophenyl) imines for chloroacetic chloride - Google Patents
Synthetic method of one kind 2 chlorine N (2,4 dichlorophenyl) imines for chloroacetic chloride Download PDFInfo
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- CN105017067B CN105017067B CN201410164338.0A CN201410164338A CN105017067B CN 105017067 B CN105017067 B CN 105017067B CN 201410164338 A CN201410164338 A CN 201410164338A CN 105017067 B CN105017067 B CN 105017067B
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- dichlorophenyl
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Abstract
Synthetic method the invention discloses one kind 2 chlorine N (2,4 dichlorophenyl) imines for chloroacetic chloride.With 2 chlorine N (2,4 dichlorophenyls) acetamide and phosphorus pentachloride be raw material, reacted in toluene, reaction temperature is 25~30 DEG C, reaction depressurizes precipitation after terminating, accessory substance is eliminated by repeatedly adding toluene to be evaporated under reduced pressure again, crude product obtains target product by high vacuum distillation again, cools down preservation.Detected through GC, the conversion ratio of 2 chlorine N (2,4 dichlorophenyl) acetamide can reach more than 99.8%.
Description
Technical field
The invention belongs to organic chemicals to synthesize field, is related to the synthetic methods of haloimines, more particularly to a kind of 2- chloro-
Synthetic method of N- (2,4- the dichlorophenyl)-imines for chloroacetic chloride.
Background technology
Phosphorus chloride be it is a kind of apply very extensive chlorination reagent in organic synthesis, one of which application is exactly and α-carbon
On not amide structure hydrogeneous and hydrogeneous on nitrogen (including ketone form structure in azacyclo-) reaction generate corresponding chlorimide：
The chloro- N- of 2- (2,4- dichlorophenyl)-imines as a kind of pesticide intermediate, has a wide range of applications for chloroacetic chloride,
There is presently no the report of related methods of synthesis.Its structural formula is as follows：
The content of the invention
Synthetic method it is an object of the invention to provide a kind of chloro- N- of 2- (2,4- dichlorophenyl)-imines for chloroacetic chloride.
The technical solution for realizing the object of the invention is：
With the chloro- N- of 2- (2,4- dichlorophenyl)-acetamides and phosphorus pentachloride for raw material, reacted in toluene, reaction temperature
For 25~30 DEG C, precipitation is depressurized in reaction after terminating, then eliminates accessory substance by repeatedly adding toluene to be evaporated under reduced pressure, and crude product is again through too high
Vacuum distillation obtains target product, cools down preservation.
Reaction equation：
Wherein, phosphorus pentachloride is pharmaceutical grade, and content >=99.5%, the dosage of phosphorus pentachloride is 2- chloro- N- (2,4- dichloro-benzenes
Base)-acetamide 0.95 times (W/W), solvent toluene is technical grade, moisture ＜ 0.1%, and dosage is 3 times (W/W) of phosphorus pentachloride
Reaction time is higher than 4 hours.
The feed way of the chloro- N- of 2- (2,4- dichlorophenyl)-acetamide is by the way of vacuum is repeatedly pumped into, charge temperature
Between 10~15 DEG C, 2~2.5 hours time.
Depressurize the precipitation stage, vacuum -0.095Mpa, highest liquid temperature is no more than 100 DEG C.
The accessory substance is phosphorus trichloride and hydrogen chloride, and toluene is evaporated under reduced pressure and eliminates phosphorus trichloride and hydrogen chloride process, very
Sky -0.095Mpa, highest liquid temperature are no more than 100 DEG C, at least distill 3 times.
The high vacuum distillation of crude product, vacuum -0.097Mpa, liquid temperature are no more than 130 DEG C, collect 118~120 DEG C of cuts.
Preservation is cooled down, chilling temperature is less than 40 DEG C.
Reaction mechanism discussion：
The present invention is based on above-mentioned reaction mechanism, and reasoning is with phosphorus pentachloride with the chloro- N- of 2- (2,4- dichlorophenyl)-acetamide
Raw material, synthesize target product.Course of reaction find, 1, the control of reaction temperature play a key effect in the reaction, reason be by
In when reaction temperature is too high, Cl can substitute the H on R1, R2 to produce by-product impurities, for the chloro- N- of 2- (2,4- bis-
Chlorphenyl) for-acetamide this raw material, 2,2-, bis- chloro- N- (2,4- dichlorophenyl)-acetamides can be generated and 2,2- bis- is chloro-
Both accessory substances of N- (2,4,6- trichlorophenyls)-acetamides.By many experiments demonstration draw reaction temperature control 25~
30 DEG C optimal.2nd, because moisture can cause greatly to negatively affect to the reaction, therefore feed way is used and repeatedly taken out using vacuum
The mode entered, in order to the moisture completely cut off in air, while charging is also allowed for temperature control at 10~15 DEG C several times,
Reduce the generation of accessory substance.3rd, the accessory substance phosphorus trichloride and hydrogen chloride, a large amount of residuals can cause product quality to decline, influence
Product uses, it is therefore necessary to eliminates accessory substance, the present invention is evaporated under reduced pressure by solvent toluene and eliminates phosphorus trichloride and hydrogen chloride mistake
Journey, vacuum -0.095Mpa, highest liquid temperature are no more than 100 DEG C, at least distill 3 times, and three are free of in the product after experiment test distillation
Phosphorus chloride and hydrogen chloride.
Compared with prior art, its remarkable advantage is the present invention：
1. feed stock conversion is high.During phosphorus pentachloride reaction generation target product, 2- chloro- N- (2,4- dichloro-benzenes
Base) conversion ratio of-acetamide can reach more than 99.8%；
2. good product quality.Bis- chloro- N- of bis- chloro- N- of accessory substance 2,2- (2,4 dichloro benzene base)-acetamides and 2,2- (2,4,
6- trichlorophenyls)-acetyl amine content be less than 8%.Final products make accessory substance trichlorine oxygen by repeatedly distillation and high vacuum rectification
Phosphorus residual can reach less than 0.1%.The main content of product can also reach more than 92%, and outward appearance is faint yellow clear oil
Shape；
3. it is fairly simple that toluene applies mechanically required processing, reduce solvent cost.
Embodiment
The present invention is described in further detail with reference to embodiment.
Embodiment 1
Step 1, the preparation of the chloro- N- of 2- (2,4- dichlorophenyl)-acetamide
1000mL four-hole boiling flasks connect tail gas water absorption plant, and 638g toluene, 100.31g2,4- dichloro-benzenes are put into bottle
Amine, 63 DEG C are heated to, start that 71.82g chloracetyl chlorides are added dropwise, control dropping temperature is cooled down between 60~65 DEG C with ordinary water.Drop
With water bath with thermostatic control, temperature keeps reaction 3 hours or so in 65 DEG C after complete.During insulation prepares in another 2000mL four-hole bottles
Aqueous sodium carbonate (8.36g sodium carbonate+200g water), is preheated to 35 DEG C, standby.Material is cooled to 51 after completion of the reaction
DEG C, it is poured slowly into prefabricated aqueous sodium carbonate, 42 DEG C of temperature after mixing, is thoroughly stirred 30 minutes between 40~45 DEG C.
Standing branch vibration layer after 30 minutes, organic phase are stirred 30 minutes with 200g ordinary waters wash again, are layered after standing 30 minutes and are removed water.Will
Divide in the organic phase input 1000mL four-hole bottles after water, connect condenser pipe, water knockout drum, be heated to the azeotropic that flows back, originate azeotropic temperature
87 DEG C, steaming thing is discarded.Evaporation capacity is reduced after 92 DEG C, starts reflux water-dividing.It is basicly stable after 115 DEG C of boiling point, continue to keep
Reflux water-dividing 5 hours.Divide after the completion of water, slowly cool to 40~50 DEG C of insulations, four-hole bottle is sealed standby.The above-mentioned chloro- N- of 2-
(2,4 dichloro benzene base)-acetamide Ye Ke cities reach.
Step 2, preparation of the chloro- N- of 2- (2,4- the dichlorophenyl)-imines for chloroacetic chloride
452g toluene is put into dry 2000mL four-hole bottles, lower addition phosphorus pentachloride 144.87g is stirred, with ethanol system
Cooling system is cooled to less than 10 DEG C.It is with vacuum that the obtained insulation acid amides of step 1, the toluene of point multiple batches of suction phosphorus pentachloride is molten
In liquid, control temperature is no more than 15 DEG C.Charging in about 2 hours finishes, 13 DEG C of temperature.Reaction solution is warming up to 28 with water bath with thermostatic control
DEG C, insulation reaction 4 hours.After completion of the reaction, four-hole bottle is connect to the vacuum system for breaking once with alkali filter in front end, by material-
0.095Mpa, lower distillation removing toluene, 96 DEG C of highest vapo(u)rizing temperature.250mL fresh toluenes are added, are steamed again in conditions above
Evaporate and take hydrogen chloride and POCl3 out of, so in triplicate, maximum temperature is no more than 100 DEG C, obtains light brown crude product 166.24g.
Four-hole bottle is connect into sliding vane rotary vacuum pump, under vacuum -0.097Mpa, heating is evaporated under reduced pressure, and is collected 118~120 DEG C of cuts, is obtained shallow
Yellow clear oil finished product 133.17g, G/C content 92.72%, POCl3 noresidue.
Embodiment 2
Preparation of the chloro- N- of 2- (2,4- the dichlorophenyl)-imines for chloroacetic chloride
457g toluene is put into dry 2000mL four-hole bottles, lower addition 145.11g phosphorus pentachlorides is stirred, is cooled to 10
Below DEG C.With vacuum, by the chloro- N- of 152.64g2- (2,4- dichlorophenyl)-acetamides and the mixed liquor of 600g toluene, several times
It is pumped into the toluene solution of phosphorus pentachloride, control temperature is no more than 15 DEG C.Charging in about 2 hours finishes, 12 DEG C of temperature.Material is used
Water bath with thermostatic control is warming up to 27 DEG C, insulation reaction 4 hours.After completion of the reaction, four-hole bottle is connect to the vacuum system for breaking once with alkali filter in front end
System, by material in -0.095Mpa, lower distillation removing toluene, 94 DEG C of highest vapo(u)rizing temperature.Add 250mL fresh toluenes, in
Upper condition is distilled again takes hydrogen chloride and POCl3 out of, and so in triplicate, maximum temperature is no more than 100 DEG C, obtains light brown
Crude product 170.38g.Four-hole bottle is connect into sliding vane rotary vacuum pump, under vacuum -0.097Mpa, heating is evaporated under reduced pressure, and collects 118~120
DEG C cut, obtains light yellow clear oil finished product 134.19g, G/C content 92.33%, POCl3 noresidue.
Embodiment 3
Preparation of the chloro- N- of 2- (2,4- the dichlorophenyl)-imines for chloroacetic chloride
454g toluene is put into dry 2000mL four-hole bottles, lower addition 145.68g phosphorus pentachlorides is stirred, is cooled to 10
Below DEG C.With vacuum, by the chloro- N- of 153.17g2- (2,4- dichlorophenyl)-acetamides and the mixed liquor of 600g toluene, several times
It is pumped into the toluene solution of phosphorus pentachloride, control temperature is no more than 15 DEG C.Charging in about 2 hours finishes, 14 DEG C of temperature.Material is used
Water bath with thermostatic control is warming up to 28 DEG C, insulation reaction 4 hours.After completion of the reaction, four-hole bottle is connect to the vacuum system for breaking once with alkali filter in front end
System, by material in -0.095Mpa, lower distillation removing toluene, 96 DEG C of highest vapo(u)rizing temperature.Add 250mL fresh toluenes, in
Upper condition is distilled again takes hydrogen chloride and POCl3 out of, and so in triplicate, maximum temperature is no more than 100 DEG C, obtains light brown
Crude product 168.21g.Four-hole bottle is connect into sliding vane rotary vacuum pump, under vacuum -0.097Mpa, heating is evaporated under reduced pressure, and collects 118~120
DEG C cut, obtains light yellow clear oil finished product 134.54g, G/C content 92.84%, POCl3 noresidue.
Claims (3)
1. a kind of chloro- N- of 2- (2,4- dichlorophenyl)-imines is for the synthetic method of chloroacetic chloride, it is characterised in that：With the chloro- N- of 2-
(2,4- dichlorophenyl)-acetamide and phosphorus pentachloride are raw material, are reacted in toluene, and reaction temperature is 25~30 DEG C, reaction knot
Precipitation is depressurized after beam, then accessory substance is eliminated by repeatedly adding toluene to be evaporated under reduced pressure, crude product obtains target by high vacuum distillation again
Product, preservation is cooled down, wherein, the dosage of phosphorus pentachloride is 0.95 times (W/W) of the chloro- N- of 2- (2,4- dichlorophenyl)-acetamide,
Reaction time is higher than 4 hours；The feed way of the chloro- N- of 2- (2,4 dichloro benzene base)-acetamide uses the side that vacuum is repeatedly pumped into
Formula, charge temperature is between 10~15 DEG C, 2~2.5 hours time；Depressurize precipitation stage, vacuum -0.095Mpa, highest liquid
Temperature is no more than 100 DEG C；The accessory substance is POCl3 and hydrogen chloride, adds toluene to be evaporated under reduced pressure and eliminates POCl3 and hydrogen chloride
Process, vacuum -0.095Mpa, highest liquid temperature are no more than 100 DEG C, at least distill 3 times.
2. for the synthetic method of chloroacetic chloride, its feature exists the chloro- N- of 2- (2,4- dichlorophenyl)-imines according to claim 1
In：The high vacuum distillation of crude product, vacuum -0.097Mpa, liquid temperature are no more than 130 DEG C, collect 118~120 DEG C of cuts.
3. for the synthetic method of chloroacetic chloride, its feature exists the chloro- N- of 2- (2,4- dichlorophenyl)-imines according to claim 1
In：Preservation is cooled down, chilling temperature is less than 40 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410164338.0A CN105017067B (en) | 2014-04-22 | 2014-04-22 | Synthetic method of one kind 2 chlorine N (2,4 dichlorophenyl) imines for chloroacetic chloride |
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| CN201410164338.0A CN105017067B (en) | 2014-04-22 | 2014-04-22 | Synthetic method of one kind 2 chlorine N (2,4 dichlorophenyl) imines for chloroacetic chloride |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0018943A1 (en) * | 1979-04-20 | 1980-11-12 | Ciba-Geigy Ag | 1-Triazolo-N-(phenyl)-azomethine derivatives, process for their preparation, compositions containing them and their use as pesticides |
| EP0496900A1 (en) * | 1990-08-22 | 1992-08-05 | Central Glass Company, Limited | N-acyl-n-phenyltetrahydrophthalamic acid derivative, production thereof, and herbicide containing the same as active ingredient |
-
2014
- 2014-04-22 CN CN201410164338.0A patent/CN105017067B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0018943A1 (en) * | 1979-04-20 | 1980-11-12 | Ciba-Geigy Ag | 1-Triazolo-N-(phenyl)-azomethine derivatives, process for their preparation, compositions containing them and their use as pesticides |
| EP0496900A1 (en) * | 1990-08-22 | 1992-08-05 | Central Glass Company, Limited | N-acyl-n-phenyltetrahydrophthalamic acid derivative, production thereof, and herbicide containing the same as active ingredient |
Non-Patent Citations (1)
| Title |
|---|
| N-Arylamidines and N-Arylimidates of Substituted Acetic Acids and Their Insecticidal and Acaricidal Properties;Gerhard Salbeck et al;《Pestic. Sci.》;19821231;第13卷;647-652 * |
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