CN104402806A - Nitenpyram preparation method - Google Patents
Nitenpyram preparation method Download PDFInfo
- Publication number
- CN104402806A CN104402806A CN201410609272.1A CN201410609272A CN104402806A CN 104402806 A CN104402806 A CN 104402806A CN 201410609272 A CN201410609272 A CN 201410609272A CN 104402806 A CN104402806 A CN 104402806A
- Authority
- CN
- China
- Prior art keywords
- still
- layering
- drip
- precipitation
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
Abstract
The invention discloses a nitenpyram preparation method which is as follows: 1, two intermediates are synthesized, to be more specific, an ethylamine intermediate is obtained by reaction of 2-chloro-5-chloro methyl pyridine and triethylamine; 2, 1,1,1-trichloro-2-nitroethane is obtained by reaction of 1, 1-dichloroethylene and hydrochloric acid and nitric acid mixed acid, the 1,1,1-trichloro-2-nitroethane is reacted with a liquid alkali for elimination reaction of a molecule of hydrogen chloride to produce 1, 1-dichloro-2-nitro ethylene intermediate; and 3, the ethylamine intermediate is reacted with the 1, 1-dichloro-2-nitro ethylene intermediate and monomethylamine to produce final products nitenpyram, the 2-chloro-5-chloro methyl pyridine is used as a main raw material, is produced in large scale in China, and is easy to purchase, and the preparation method is simple and easy to operate, in no need of special equipment and no need of high temperature, high pressure conditions, and is high in yield.
Description
Technical field
The invention belongs to organic synthesis field, particularly relate to a kind of preparation method of Ti304.
Background technology
Ti304 is the new variety in the important nicotinic insecticide of a class, has the features such as efficient, wide spectrum, low toxicity, resistance, worldwide obtains the application of wide model.It is the excellent control medication of the multiple insect pests such as important food crop, cash crop.Domestic existing sterilant is difficult to some insect pests, particularly aphid, leafhopper, Ji book, Hemipteran pest, water rice hopper etc. of preventing and kill off, show remarkable activity, and expenses for prevention and control is cheap.Its low toxicity and the specific action of target insect pest is also widely applied in veterinary drug.At present worldwide (comprise China) and obtain the application of wide model, prospect is very wide.Its synthetic route is: 1, ethylaminely operate at normal temperatures and pressures, CCMP and ethamine react and generate N-(6-chloro-3-pyridyl ylmethyl)-N-ethamine intermediate, reaction conditions is gentle, easy to control, will reclaim excessive monoethylamine after reaction terminates.2, this reaction needed chilled brine of nitration is lowered the temperature, 1,1-Ethylene Dichloride and hydrochloric acid, nitric acid reaction generate 1,1, the chloro-2-nitroethane of 1-tri-, need after end to add buck neutralization, eliminate a part hydrogenchloride, generation 1,1-dichloro 2-nitroethylene intermediate.3, synthesize ethylamine reaction generate intermediate N (6-chloro-3-pyridyl ylmethyl)-N-ethamine and nitration reaction generate 1,1-dichloro 2-nitroethylene intermediate reaction, last reaction with Monomethylamine again generates the finished product Ti304 product, the synthesis of this step needs chilled brine to drop to room temperature reaction, drip Monomethylamine speed not easily too fast, recycling design temperature can not be high.
Ti304 is the new variety in the important nicotinic insecticide of a class, there is the features such as efficient, wide spectrum, low toxicity, resistance, worldwide obtaining the application of wide model, be the excellent control medication of the multiple insect pests such as important food crop, cash crop, and expenses for prevention and control is cheap.Its low toxicity and the specific action of target insect pest is also widely applied in veterinary drug.
Summary of the invention
The object of this invention is to provide a kind of preparation method of Ti304.
The present invention adopts following technical scheme to achieve these goals:
A preparation method for Ti304, is characterized in that, comprises the following steps:
A, ethylamine
Quantitative toluene solvant is dropped in enamel reaction still, drop to less than 10 DEG C, drop into the CCMP that melting is good, ethamine is dripped in 0-10 DEG C, control temperature well, drip and finish, 5-6 hour is incubated at 20-25 DEG C, when CCMP reacts completely, in proceeding to and still, add liquid caustic soda neutralization, layering, lower aqueous layer toluene recovery extracting twice, water layer extraction oil reservoir and still in oil reservoir merge, washing once, divide sub-cloud water layer, oil reservoir carries out negative pressure recycling design, the recycling design later stage adds a small amount of water, steam residual solvent, obtain ethylamine intermediate,
B, nitration
Quantitative hydrochloric acid and nitric acid are dropped in enamel reaction still, drops to less than 10 DEG C, drip 1,1-Ethylene Dichloride, control temperature is at 20-25 DEG C, and be incubated 4 hours, Intermediate nitro ethane is washed to obtain in layering, nitroethane is dropped in enamel still, control temperature, at 0-5 DEG C, drips 15% liquid caustic soda, drips Bi Baowen 1 hour, leave standstill 2 little layereds, obtain nitroethylene intermediate;
C, synthesis
Suitable quantity of water is dropped in enamel reaction still, drop into dichloroethane solvent, add salt of wormwood under stirring, suction nitroethylene intermediate, drip ethylamine intermediate in 4-6 DEG C, dripping finishes in this temperature 4 hours, at this temperature, drip Monomethylamine again, be incubated 4 hours, be warming up to 30 DEG C of insulations 1 hour, reaction terminates, and layering, suction filtration, extraction, precipitation, crystallization, centrifugally obtains product.
The preparation method of described a kind of Ti304, is characterized in that: preparation method comprises the following steps:
A, ethylamine
﹙ 1 ﹚, in enamel reaction still, drop into 500kg toluene, open and stir, frozen cooling, is cooled to less than 10 DEG C, then drops into the CCMP of 250kg of the good content of melting 92%;
﹙ 2 ﹚, start the ethamine of the 300kg dripping content 70% still temperature 0 ~ 10 DEG C, drip and finish, at 20-25 DEG C of insulation 5-6 hour, until CCMP content≤0.5%, reaction terminates;
During material proceeds to after terminating by ﹙ 3 ﹚, reaction and still, the liquid caustic soda 260kg adding content 30% neutralizes, and stirs 30 minutes, standing layering in 30 minutes;
﹙ 4 ﹚, point lower aqueous layer are to layering basin, and upper toluene turns material to precipitation still;
﹙ 5 ﹚, by water layer suction and still, to extract with toluene 180kg, extraction secondary;
﹙ 6 ﹚, combining methylbenzene layer go to precipitation still, and add 150kg water in still, and once, stratification, divides sub-cloud water layer to washing toluene layer;
﹙ 7 ﹚, hot water heat up, negative pressure-0.095MPa piptonychia benzene, and temperature controls within 100 DEG C, and when toluene flux reduces, suitably after cooling, then to suction 50kg water in still, azeotropic deviates from residual toluene;
After ﹙ 8 ﹚, distillation terminate, open below cooling water temperature to 40 DEG C, release material barrelling in precipitation still, obtain ethylamine intermediate;
B, nitrated
﹙ 1 ﹚, dropped in enamel reaction still to open by hydrochloric acid 800 ㎏ of content 30% and stir, frozen cooling, is cooled to less than 10 DEG C, opens device for absorbing tail gas;
﹙ 2 ﹚, in enamel reaction still, slowly add the 650kg nitric acid of content 65%, be configured to nitration mixture;
﹙ 3 ﹚, drip in enamel reaction still 500kg 1,1-Ethylene Dichloride, control temperature at 20-25 DEG C, drip terminate, 20 ~ 25 DEG C insulation 4 hours;
﹙ 4 ﹚, standing layering in 20 minutes, lower floor is transferred to washing layering still, and upper strata spent acid is directly discharged into spent acid pond;
﹙ 5 ﹚, washing layering still add water 200kg, stir 20 minutes, standing layering in 20 minutes, obtain 1,1,1-tri-chloro-2-nitroethane intermediate;
﹙ 6 ﹚, by 1,1, in 1-tri-chloro-2-nitroethane intermediate 736kg suction reactor, drip the liquid caustic soda 1028kg of content 15% at 0-5 DEG C, carry out eliminative reaction, drip and finish in 0-5 DEG C of insulation 1 hour, leave standstill 2 little layereds, obtain 1,1-dichloro 2-nitroethylene intermediate;
C, synthesis
﹙ 1 ﹚, the water of 700 ㎏ is added in enamel reaction still, open and stir, drop into 98% salt of wormwood 180 ㎏, be made into about 20% aqueous solution; The ethylene dichloride of suction 800kg, below frozen cooling to 0 DEG C;
﹙ 2 ﹚, in enamel reaction still, add 1,1-dichloro 2-nitroethylene intermediate 160kg, temperature may not exceed 3 DEG C;
﹙ 3 ﹚, drip 147kg ethylamine intermediates at 4 ~ 6 DEG C, dropwise, in 4 ~ 6 DEG C of insulations 4 hours;
﹙ 4 ﹚, drip 350kg Monomethylamines at 4 ~ 6 DEG C again, dropwise in 5 ~ 7 DEG C of insulations 4 hours, be warming up to 20 ~ 25 DEG C and turn still to layering still, be warming up to 30 DEG C of insulations 1 hour;
﹙ 5 ﹚, be incubated complete, leave standstill after 30 minutes layering suction filtration to precipitation still;
﹙ 6 ﹚, extract 2 times with ethylene dichloride again, each 125kg, rear layering suction filtration is to precipitation still precipitation;
﹙ 7 ﹚, precipitation still precipitation adopt and are warming up to 65-70 DEG C, heat up with circulating hot water;
﹙ 8 ﹚, precipitation are complete, add 300kg ethyl acetate, turn material to crystallization kettle crystallization, centrifugal, dry and get final product.
The synthesis of this product first will synthesize two intermediates, and two intermediate reactions react with Monomethylamine and generate Ti304 the finished product.
1 is ethylamine:
2 nitrations:
Cl
2C＝CH
2+HCl+HNO
3→Cl
3C—CH
2NO
2
The chloro-2-nitroethane of vinylidene chloride acid of hydrochloric acid and nitric acid 1,1,1-tri-
Cl
3CCH
2NO
2+NaOH→Cl
2CCHNO
2
The chloro-2-nitroethylene of 1,1,1-tri-chloro-2-nitroethane liquid caustic soda 1,1-bis-
3 synthesis:
Beneficial effect of the present invention:
The present invention is in CCMP, ethylamine intermediate yield reaches 95%, in vinylidene chloride, 1,1, the yield of the chloro-2-nitroethane of 1-tri-68% and 1,1-bis-chloro-2-nitroethylene yield 55%, with ethylamine intermediate, Ti304 yield is 63% total recovery is that this technological operation condition of 52.25%. is wide, reaction conditions is gentle, easy to control, yield is higher, unit cost is low, is successful production technology.
Embodiment
Embodiment 1,
1, ethylamine
﹙ 1 ﹚, in enamel reaction still, drop into 500kg toluene, open and stir, frozen cooling, is cooled to less than 10 DEG C, then drops into the CCMP of 250kg of the good content of melting 92%;
﹙ 2 ﹚, start the ethamine of the 300kg dripping content 70% still temperature 0 ~ 10 DEG C, drip and finish, at 20-25 DEG C of insulation 5-6 hour, until CCMP content≤0.5%, reaction terminates;
During material proceeds to after terminating by ﹙ 3 ﹚, reaction and still, the liquid caustic soda 260kg adding content 30% neutralizes, and stirs 30 minutes, standing layering in 30 minutes;
﹙ 4 ﹚, point lower aqueous layer are to layering basin, and upper toluene turns material to precipitation still;
﹙ 5 ﹚, by water layer suction and still, to extract with toluene 180kg, extraction secondary;
﹙ 6 ﹚, combining methylbenzene layer go to precipitation still, and add 150kg water in still, and once, stratification, divides sub-cloud water layer to washing toluene layer;
﹙ 7 ﹚, hot water heat up, and negative pressure-0.095MPa piptonychia benzene, temperature controls within 100 DEG C.When toluene flux reduces, suitably after cooling, then to suction 50kg water in still, azeotropic deviates from residual toluene;
﹙ 8 ﹚, open below cooling water temperature to 40 DEG C, release material barrelling in precipitation still, obtain the ethylamine intermediate of content 92% weight 250.1kg, yield 95%.
2, nitrated
﹙ 1 ﹚, dropped in enamel reaction still to open by hydrochloric acid 800 ㎏ of content 30% and stir, frozen cooling, is cooled to less than 10 DEG C, opens device for absorbing tail gas;
﹙ 2 ﹚, in enamel reaction still, slowly add the 650kg nitric acid of content 65%, be configured to nitration mixture;
﹙ 3 ﹚, drip in enamel reaction still 500kg 1,1-Ethylene Dichloride, control temperature at 20-25 DEG C, note temperature in the kettle change, drip terminate, 20 ~ 25 DEG C insulation 4 hours;
﹙ 4 ﹚, standing layering in 20 minutes, lower floor is transferred to washing layering still, and upper strata spent acid is directly discharged into spent acid pond;
﹙ 5 ﹚, washing layering still add water 200gkg, stir 20 minutes, standing layering in 20 minutes, obtain 1 of content 85%, 1,1-tri-chloro-2-nitroethane intermediate 736kg, yield 68%;
﹙ 6 ﹚, by 1,1, in 1-tri-chloro-2-nitroethane intermediate 736kg suction reactor, the liquid caustic soda 1028kg of content 15% is dripped at 0-5 DEG C, carry out eliminative reaction, drip and finish in 0-5 DEG C of insulation 1 hour, leave standstill 2 little layereds, content 80% 1,1-dichloro 2-nitroethylene intermediate 498kg, yield 80%.
3, synthesize
﹙ 1 ﹚, the water of 700 ㎏ is added in enamel reaction still, open and stir, drop into 98% salt of wormwood 180 ㎏, be made into about 20% aqueous solution; The ethylene dichloride of suction 800kg, below frozen cooling to 0 DEG C;
﹙ 2 ﹚, in enamel reaction still, add 1,1-dichloro 2-nitroethylene intermediate 160kg, temperature may not exceed 3 DEG C;
﹙ 3 ﹚, drip 147kg ethylamine intermediates at 4 ~ 6 DEG C, dropwise, in 4 ~ 6 DEG C of insulations 4 hours;
﹙ 4 ﹚, drip 350kg Monomethylamines at 4 ~ 6 DEG C, control to drip flow, prevent temperature from rising too high, dropwise in 5 ~ 7 DEG C of insulations 4 hours, be warming up to 20 ~ 25 DEG C and turn still to layering still, be warming up to 30 DEG C of insulations 1 hour;
﹙ 5 ﹚, be incubated complete, leave standstill after 30 minutes layering suction filtration to precipitation still;
﹙ 6 ﹚, extract 2 times with ethylene dichloride, each 125kg, layering suction filtration is to precipitation still precipitation;
﹙ 7 ﹚, precipitation still adopt and are warming up to 65-70 DEG C, heat up with circulating hot water;
﹙ 8 ﹚, precipitation are complete, add 300kg ethyl acetate, turn material to crystallization kettle crystallization, centrifugal, dry to obtain the Ti304 product 140kg of content 95%.
Test-results shows, in CCMP, ethylamine yield reaches 95%; In vinylidene chloride, 1,1, the chloro-2-nitroethylene yield of yield 68%, 1,1-bis-of 1-tri-chloro-2-nitroethane is 55%; With ethylamine intermediate, Ti304 yield 63%, three step total recovery is that this technological operation condition of 52.25%. is wide, reaction conditions is gentle, easy to control, and yield is higher, unit cost is low, is successful production technology.
Embodiment 2,
A preparation method for Ti304, comprises the following steps:
A, ethylamine
Quantitative toluene solvant is dropped in enamel reaction still, drop to less than 10 DEG C, drop into the CCMP that melting is good, drip ethamine in 5 DEG C, control temperature well, drip and finish, 5 hours are incubated, when CCMP reacts completely, in proceeding to and still at 25 DEG C, add liquid caustic soda neutralization, layering, lower aqueous layer toluene recovery extracting twice, water layer extraction oil reservoir and still in oil reservoir merge, washing once, divide sub-cloud water layer, oil reservoir carries out negative pressure recycling design, and the recycling design later stage adds a small amount of water, steam residual solvent, obtain ethylamine intermediate;
B, nitration
Quantitative hydrochloric acid and nitric acid are dropped in enamel reaction still, drops to less than 10 DEG C, drip 1,1-Ethylene Dichloride, control temperature is at 20-25 DEG C, and be incubated 4 hours, Intermediate nitro ethane is washed to obtain in layering, nitroethane is dropped in enamel still, control temperature, at 0-5 DEG C, drips 15% liquid caustic soda, drips Bi Baowen 1 hour, leave standstill 2 little layereds, obtain nitroethylene intermediate;
C, synthesis
Suitable quantity of water is dropped in enamel reaction still, drop into dichloroethane solvent, add salt of wormwood under stirring, suction nitroethylene intermediate, drip ethylamine intermediate in 4-6 DEG C, dripping finishes in this temperature 4 hours, at this temperature, drip Monomethylamine again, be incubated 4 hours, be warming up to 30 DEG C of insulations 1 hour, reaction terminates, and layering, suction filtration, extraction, precipitation, crystallization, centrifugally obtains product.
Test-results shows, in CCMP, ethylamine yield reaches 97%.
Embodiment 3,
The preparation method of described a kind of Ti304, preparation method comprises the following steps:
A, ethylamine
﹙ 1 ﹚, in enamel reaction still, drop into 500kg toluene, open and stir, frozen cooling, is cooled to less than 10 DEG C, then drops into the CCMP of 250kg of the good content of melting 92%;
﹙ 2 ﹚, start the ethamine of the 300kg dripping content 70% still temperature 10 DEG C, drip and finish, at 20-25 DEG C of insulation 5-6 hour, until CCMP content≤0.5%, reaction terminates;
During material proceeds to after terminating by ﹙ 3 ﹚, reaction and still, the liquid caustic soda 260kg adding content 30% neutralizes, and stirs 30 minutes, standing layering in 30 minutes;
﹙ 4 ﹚, point lower aqueous layer are to layering basin, and upper toluene turns material to precipitation still;
﹙ 5 ﹚, by water layer suction and still, to extract with toluene 180kg, extraction secondary;
﹙ 6 ﹚, combining methylbenzene layer go to precipitation still, and add 150kg water in still, and once, stratification, divides sub-cloud water layer to washing toluene layer;
﹙ 7 ﹚, hot water heat up, negative pressure-0.095MPa piptonychia benzene, and temperature controls within 100 DEG C, and when toluene flux reduces, suitably after cooling, then to suction 50kg water in still, azeotropic deviates from residual toluene;
After ﹙ 8 ﹚, distillation terminate, open below cooling water temperature to 40 DEG C, release material barrelling in precipitation still, obtain ethylamine intermediate;
B, nitrated
﹙ 1 ﹚, dropped in enamel reaction still to open by hydrochloric acid 800 ㎏ of content 30% and stir, frozen cooling, is cooled to less than 10 DEG C, opens device for absorbing tail gas;
﹙ 2 ﹚, in enamel reaction still, slowly add the 650kg nitric acid of content 65%, be configured to nitration mixture;
﹙ 3 ﹚, drip in enamel reaction still 500kg 1,1-Ethylene Dichloride, control temperature at 25 DEG C, drip terminate, 25 DEG C insulation 4 hours;
﹙ 4 ﹚, standing layering in 20 minutes, lower floor is transferred to washing layering still, and upper strata spent acid is directly discharged into spent acid pond;
﹙ 5 ﹚, washing layering still add water 200kg, stir 20 minutes, standing layering in 20 minutes, obtain 1,1,1-tri-chloro-2-nitroethane intermediate;
﹙ 6 ﹚, by 1,1, in 1-tri-chloro-2-nitroethane intermediate 736kg suction reactor, drip the liquid caustic soda 1028kg of content 15% at 5 DEG C, carry out eliminative reaction, drip and finish in 0-5 DEG C of insulation 1 hour, leave standstill 2 little layereds, obtain 1,1-dichloro 2-nitroethylene intermediate;
C, synthesis
﹙ 1 ﹚, the water of 700 ㎏ is added in enamel reaction still, open and stir, drop into 98% salt of wormwood 180 ㎏, be made into about 20% aqueous solution; The ethylene dichloride of suction 800kg, below frozen cooling to 0 DEG C;
﹙ 2 ﹚, in enamel reaction still, add 1,1-dichloro 2-nitroethylene intermediate 160kg, temperature may not exceed 3 DEG C;
﹙ 3 ﹚, drip 147kg ethylamine intermediates at 6 DEG C, dropwise, in 6 DEG C of insulations 4 hours;
﹙ 4 ﹚, drip 350kg Monomethylamines at 4 DEG C again, dropwise in 7 DEG C of insulations 4 hours, be warming up to 20 DEG C and turn still to layering still, be warming up to 30 DEG C of insulations 1 hour;
﹙ 5 ﹚, be incubated complete, leave standstill after 30 minutes layering suction filtration to precipitation still;
﹙ 6 ﹚, extract 2 times with ethylene dichloride again, each 125kg, rear layering suction filtration is to precipitation still precipitation;
﹙ 7 ﹚, precipitation still precipitation adopt and are warming up to 70 DEG C, heat up with circulating hot water;
﹙ 8 ﹚, precipitation are complete, add 300kg ethyl acetate, turn material to crystallization kettle crystallization, centrifugal, dry the Ti304 product 140kg of content 95%.
Claims (2)
1. a preparation method for Ti304, is characterized in that, comprises the following steps:
A, ethylamine
Quantitative toluene solvant is dropped in enamel reaction still, drop to less than 10 DEG C, drop into the CCMP that melting is good, ethamine is dripped in 0-10 DEG C, control temperature well, drip and finish, 5-6 hour is incubated at 20-25 DEG C, when CCMP reacts completely, in proceeding to and still, add liquid caustic soda neutralization, layering, lower aqueous layer toluene recovery extracting twice, water layer extraction oil reservoir and still in oil reservoir merge, washing once, divide sub-cloud water layer, oil reservoir carries out negative pressure recycling design, the recycling design later stage adds a small amount of water, steam residual solvent, obtain ethylamine intermediate,
B, nitration
Quantitative hydrochloric acid and nitric acid are dropped in enamel reaction still, drops to less than 10 DEG C, drip 1,1-Ethylene Dichloride, control temperature is at 20-25 DEG C, and be incubated 4 hours, Intermediate nitro ethane is washed to obtain in layering, nitroethane is dropped in enamel still, control temperature, at 0-5 DEG C, drips 15% liquid caustic soda, drips Bi Baowen 1 hour, leave standstill 2 little layereds, obtain nitroethylene intermediate;
C, synthesis
Suitable quantity of water is dropped in enamel reaction still, drop into dichloroethane solvent, add salt of wormwood under stirring, suction nitroethylene intermediate, drip ethylamine intermediate in 4-6 DEG C, dripping finishes in this temperature 4 hours, at this temperature, drip Monomethylamine again, be incubated 4 hours, be warming up to 30 DEG C of insulations 1 hour, reaction terminates, and layering, suction filtration, extraction, precipitation, crystallization, centrifugally obtains product.
2. the preparation method of a kind of Ti304 according to claim 1, is characterized in that: preparation method comprises the following steps:
A, ethylamine
﹙ 1 ﹚, in enamel reaction still, drop into 500kg toluene, open and stir, frozen cooling, is cooled to less than 10 DEG C, then drops into the CCMP of 250kg of the good content of melting 92%;
﹙ 2 ﹚, start the ethamine of the 300kg dripping content 70% still temperature 0 ~ 10 DEG C, drip and finish, at 20-25 DEG C of insulation 5-6 hour, until CCMP content≤0.5%, reaction terminates;
During material proceeds to after terminating by ﹙ 3 ﹚, reaction and still, the liquid caustic soda 260kg adding content 30% neutralizes, and stirs 30 minutes, standing layering in 30 minutes;
﹙ 4 ﹚, point lower aqueous layer are to layering basin, and upper toluene turns material to precipitation still;
﹙ 5 ﹚, by water layer suction and still, to extract with toluene 180kg, extraction secondary;
﹙ 6 ﹚, combining methylbenzene layer go to precipitation still, and add 150kg water in still, and once, stratification, divides sub-cloud water layer to washing toluene layer;
﹙ 7 ﹚, hot water heat up, negative pressure-0.095MPa piptonychia benzene, and temperature controls within 100 DEG C, and when toluene flux reduces, suitably after cooling, then to suction 50kg water in still, azeotropic deviates from residual toluene;
After ﹙ 8 ﹚, distillation terminate, open below cooling water temperature to 40 DEG C, release material barrelling in precipitation still, obtain ethylamine intermediate;
B, nitrated
﹙ 1 ﹚, dropped in enamel reaction still to open by hydrochloric acid 800 ㎏ of content 30% and stir, frozen cooling, is cooled to less than 10 DEG C, opens device for absorbing tail gas;
﹙ 2 ﹚, in enamel reaction still, slowly add the 650kg nitric acid of content 65%, be configured to nitration mixture;
﹙ 3 ﹚, drip in enamel reaction still 500kg 1,1-Ethylene Dichloride, control temperature at 20-25 DEG C, drip terminate, 20 ~ 25 DEG C insulation 4 hours;
﹙ 4 ﹚, standing layering in 20 minutes, lower floor is transferred to washing layering still, and upper strata spent acid is directly discharged into spent acid pond;
﹙ 5 ﹚, washing layering still add water 200kg, stir 20 minutes, standing layering in 20 minutes, obtain 1,1,1-tri-chloro-2-nitroethane intermediate;
﹙ 6 ﹚, by 1,1, in 1-tri-chloro-2-nitroethane intermediate 736kg suction reactor, drip the liquid caustic soda 1028kg of content 15% at 0-5 DEG C, carry out eliminative reaction, drip and finish in 0-5 DEG C of insulation 1 hour, leave standstill 2 little layereds, obtain 1,1-dichloro 2-nitroethylene intermediate;
C, synthesis
﹙ 1 ﹚, the water of 700 ㎏ is added in enamel reaction still, open and stir, drop into 98% salt of wormwood 180 ㎏, be made into about 20% aqueous solution; The ethylene dichloride of suction 800kg, below frozen cooling to 0 DEG C;
﹙ 2 ﹚, in enamel reaction still, add 1,1-dichloro 2-nitroethylene intermediate 160kg, temperature may not exceed 3 DEG C;
﹙ 3 ﹚, drip 147kg ethylamine intermediates at 4 ~ 6 DEG C, dropwise, in 4 ~ 6 DEG C of insulations 4 hours;
﹙ 4 ﹚, drip 350kg Monomethylamines at 4 ~ 6 DEG C again, dropwise in 5 ~ 7 DEG C of insulations 4 hours, be warming up to 20 ~ 25 DEG C and turn still to layering still, be warming up to 30 DEG C of insulations 1 hour;
﹙ 5 ﹚, be incubated complete, leave standstill after 30 minutes layering suction filtration to precipitation still;
﹙ 6 ﹚, extract 2 times with ethylene dichloride again, each 125kg, rear layering suction filtration is to precipitation still precipitation;
﹙ 7 ﹚, precipitation still precipitation adopt and are warming up to 65-70 DEG C, heat up with circulating hot water;
﹙ 8 ﹚, precipitation are complete, add 300kg ethyl acetate, turn material to crystallization kettle crystallization, centrifugal, dry and get final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410609272.1A CN104402806A (en) | 2014-10-31 | 2014-10-31 | Nitenpyram preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410609272.1A CN104402806A (en) | 2014-10-31 | 2014-10-31 | Nitenpyram preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104402806A true CN104402806A (en) | 2015-03-11 |
Family
ID=52640488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410609272.1A Pending CN104402806A (en) | 2014-10-31 | 2014-10-31 | Nitenpyram preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104402806A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330593A (en) * | 2015-11-23 | 2016-02-17 | 上海晋景化学有限公司 | Improved preparation method of nitenpyram |
| CN106841489A (en) * | 2017-03-09 | 2017-06-13 | 江苏泰洁检测技术有限公司 | A kind of Gas Chromatographic Determination of the pyridine methylene ethylamine of 6 chlorine 3 |
| CN107382736A (en) * | 2017-08-09 | 2017-11-24 | 江苏克胜集团股份有限公司 | The synthetic method of the nitroethylene of 1,1 dichloro 2 and Nitenpyram |
| CN109851505A (en) * | 2019-02-15 | 2019-06-07 | 台州学院 | A kind of preparation method of (Z)-beta-aromatic-β-Nitroenamine |
| CN113121422A (en) * | 2021-04-16 | 2021-07-16 | 武威联硕生物科技有限公司 | Preparation method of nitenpyram |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031079A (en) * | 1987-08-01 | 1989-02-15 | 武田药品工业株式会社 | α-unsaturated amine, its production method and application thereof |
| GB2228003A (en) * | 1989-02-13 | 1990-08-15 | Shell Int Research | Pesticidal nitroethene compounds |
| US5364989A (en) * | 1989-01-31 | 1994-11-15 | Takeda Chemical Industries, Ltd. | 1,1,1-trichloro-2-nitroethane production |
| JP3932791B2 (en) * | 2000-09-25 | 2007-06-20 | 東亞合成株式会社 | Method for producing vinylidene chloride |
| CN102816112A (en) * | 2012-09-13 | 2012-12-12 | 浙江禾本科技有限公司 | Method for preparing pesticide nitenpyram |
-
2014
- 2014-10-31 CN CN201410609272.1A patent/CN104402806A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031079A (en) * | 1987-08-01 | 1989-02-15 | 武田药品工业株式会社 | α-unsaturated amine, its production method and application thereof |
| US5364989A (en) * | 1989-01-31 | 1994-11-15 | Takeda Chemical Industries, Ltd. | 1,1,1-trichloro-2-nitroethane production |
| GB2228003A (en) * | 1989-02-13 | 1990-08-15 | Shell Int Research | Pesticidal nitroethene compounds |
| JP3932791B2 (en) * | 2000-09-25 | 2007-06-20 | 東亞合成株式会社 | Method for producing vinylidene chloride |
| CN102816112A (en) * | 2012-09-13 | 2012-12-12 | 浙江禾本科技有限公司 | Method for preparing pesticide nitenpyram |
Non-Patent Citations (4)
| Title |
|---|
| 李建，等: "新烟碱类杀虫剂-Nitenpyram", 《河南化工》 * |
| 李敏，等: "新烟碱类杀虫剂烯啶虫胺述评", 《农药研究与应用》 * |
| 王党生: "烯啶虫胺的合成路线", 《农药》 * |
| 陶玉成，等: "烯啶虫胺合成方法的研究", 《现代农药》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330593A (en) * | 2015-11-23 | 2016-02-17 | 上海晋景化学有限公司 | Improved preparation method of nitenpyram |
| CN106841489A (en) * | 2017-03-09 | 2017-06-13 | 江苏泰洁检测技术有限公司 | A kind of Gas Chromatographic Determination of the pyridine methylene ethylamine of 6 chlorine 3 |
| CN107382736A (en) * | 2017-08-09 | 2017-11-24 | 江苏克胜集团股份有限公司 | The synthetic method of the nitroethylene of 1,1 dichloro 2 and Nitenpyram |
| CN107382736B (en) * | 2017-08-09 | 2019-09-03 | 江苏克胜集团股份有限公司 | The synthetic method of the chloro- 2- nitroethylene of 1,1- bis- and Nitenpyram |
| CN109851505A (en) * | 2019-02-15 | 2019-06-07 | 台州学院 | A kind of preparation method of (Z)-beta-aromatic-β-Nitroenamine |
| CN113121422A (en) * | 2021-04-16 | 2021-07-16 | 武威联硕生物科技有限公司 | Preparation method of nitenpyram |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104402806A (en) | Nitenpyram preparation method | |
| CN102795993B (en) | Preparation method of 2-bromo-6-fluorobenzoic acid | |
| CN105153149B (en) | A kind of selective kinase inhibitors Palbociclib preparation method | |
| CN105175329B (en) | A kind of shellfish reaches the synthetic route and method of quinoline raceme | |
| CN105418612B (en) | Preparation method of doxofylline | |
| CN107235970B (en) | Synthesis method of imidaclothiz | |
| CN102153459B (en) | Method for preparing 5-chloro-valeryl chloride and adipoyl chloride simultaneously by one-pot method | |
| CN102816112A (en) | Method for preparing pesticide nitenpyram | |
| CN105859589B (en) | A method of preparing bambuterol impurity C | |
| CN101372497A (en) | Preparation of O,O-diethyl-O-(3,5,6- trichloro-2-pyridinyl)thiophosphate | |
| CN104163786A (en) | Method for preparing 5-methyl-3-bromomethylpyridine hydrobromide | |
| CN104478974A (en) | Synthesis method of 20,23-dipiperidino-5-O-mycaminose-tylosin lactone | |
| CN104693025A (en) | Feeding manner for preparing L-monomenthyl glutarate | |
| CN104892349B (en) | A kind of HBCD preparation method | |
| CN109867637A (en) | The preparation method of fumidil amido alcohol | |
| CN109867639A (en) | The method for preparing fumidil amido alcohol | |
| CN107573238B (en) | Preparation method of (DL) -mandelic acid | |
| CN102391157A (en) | Preparation method of creatine nitrate | |
| CN103626657A (en) | Synthesis of plodia interpunctella sex pheromone 9Z, 12E-tetradecadiene-1-acetate | |
| CN102911123A (en) | Preparation method of 2-chloro trifluoromethyl pyrimidine compound | |
| CN112079772A (en) | Method for ammoniation reaction in 4-trifluoromethyl nicotinic acid | |
| CN105601640B (en) | A kind of N- tertbutyloxycarbonyls -7-（Amine methyl）The synthetic method of -6- oxa- -2- spiral shells [4.5] decane | |
| CN105481740A (en) | Method for preparing isothiocyano methyl formate | |
| CN105367391B (en) | A kind of preparation method of the trimethoxy-ethane of 2 chlorine 1,1,1 | |
| CN104059022B (en) | One prepares the method for 2,4,5-trinitro-imidazoles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150311 |
|
| RJ01 | Rejection of invention patent application after publication |