CN105367557B - A kind of preparation method of epoxy quinoline - Google Patents
A kind of preparation method of epoxy quinoline Download PDFInfo
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- CN105367557B CN105367557B CN201510822792.5A CN201510822792A CN105367557B CN 105367557 B CN105367557 B CN 105367557B CN 201510822792 A CN201510822792 A CN 201510822792A CN 105367557 B CN105367557 B CN 105367557B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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Abstract
The present invention discloses a kind of preparation method of epoxy quinoline, belongs to insecticide preparing technical field.This method is first under nitrogen protection; N nitro imido imidazolyl alkanes and organic solvent are added in reactor, sodium hydride is then added portionwise, is heated to 50~60 DEG C of temperature; epoxychloropropane is slowly added dropwise into reactor; after the cooling of question response product, chloroform is added, is filtered with diatomite; re-evaporation crystallization separates out; filtrate decompression after processing is distilled to obtain faint yellow thick shape solid, is then extracted with the chloroform of heat, finally obtains epoxy quinoline with the ethanol or acetone recrystallization of heat：The sterling of 1 (2,3 glycidyl) N Nitroimidazolines, 2 base amine, yield is about 83%.The method of the present invention reaction time is shorter, yield higher and environmentally protective, more suitable for large-scale industrial production.
Description
Technical field
The invention belongs to insecticide preparing technical field, and in particular to and 1- (2,3- glycidyl)-N- Nitroimidazolines-
The preparation method of 2- bases amine, that is, epoxy quinoline.
Background technology
Epoxy quinoline is to be based on Computeraided drug design (CADD) method, that is, utilizes COMFA analog results, synthesis
4 kinds of anabasine compounds in the best one kind of insecticidal effect, its insecticidal activity and the most salable desinsection in world market
The insecticidal activity of agent --- imidacloprid is suitable.But widely using for imidacloprid has made pest generate certain resistance to the action of a drug, and
The raw materials used pyridine of imidacloprid synthesis is not only of high cost, and produces substantial amounts of pollutant in process of production.And epoxy quinoline is not
It is only capable of efficiently against disadvantage mentioned above, and there is preferable insecticidal effect as imidacloprid, and toxicity is lower, as one kind
Noval chemical compound, has the characteristics that high selectivity, security are good, and production cost is also only 1/3rd of imidacloprid, has more
Wide application prospect.2009, Chinese patent CN 101503406A disclosed 1- (2,3- glycidyl)-N- nitros Asia miaow
Two kinds of synthetic routes of oxazolidine -2- base amine, path 1 use two-step synthesis method, epoxy are added dropwise into ethylenediamine while stirring first
Chloropropane, is 45 DEG C or so in temperature, and vacuum distillation removing solvent obtains intermediate glycidyl ethylenediamine after reacting 2~3h,
Then it is intermediate and nitroguanidine is soluble in water, dilute hydrochloric acid is added dropwise while stirring, reacts 2~3h postcoolings in 85 DEG C or so, uses
Dichloromethane extracts, and vacuum distillation removes solvent, is recrystallized with butanone, two-step reaction, reaction temperature is higher, and last handling process
It need to be extracted using substantial amounts of dichloromethane equal solvent, therefore Product industrialization value is little.Route 2 is first by N- nitros Asia miaow
Oxazolidine, potassium carbonate and organic solvent are added in reaction bulb, and epoxy chlorine is added dropwise thereto after being heated to 80 DEG C of question response thing dissolvings
Propane, reaction terminates after heating 4h, and after being cooled to room temperature, filtering, filtrate is evaporated, and gained residue adds water, then uses dichloromethane
Extraction, vacuum distillation removes solvent, then is recrystallized with butanone, its aftertreatment technology is relatively complicated, and yield is relatively low, limits
Its industrialized production application.
The content of the invention
The present invention is directed to above-mentioned technical problem existing in the prior art, there is provided a kind of preparation method of epoxy quinoline.The present invention
N- nitro imido imidazolyl alkanes and epoxychloropropane is used to prepare epoxy quinoline for raw material：1- (1,2- glycidyl)-N- nitros are sub-
Imidazolidine -2- base amine.
A kind of preparation method of epoxy quinoline provided by the present invention comprises the following steps that：
(1) under nitrogen protection, N- nitro imido imidazolyl alkanes and organic solvent are added in reactor, then in batches
Sodium hydride is added, is heated to 50~60 DEG C of temperature, after the dissolving of N- nitroiminos Asia imidazolidine, is slowly added dropwise into reactor
Epoxychloropropane, is added dropwise, and continues heating 1~1.5h of reaction and terminates to reaction, reaction process is monitored with TLC or HPLC.
The molar ratio of the epoxychloropropane, N- nitro imido imidazolyl alkanes and sodium hydride is：Epoxychloropropane: N- nitros
Imido imidazolyl alkane: sodium hydride=1：1.1-1.5：1.1-1.5；The organic solvent is N, N'- dimethylformamides or N, N'-
The mixed solvent of dimethylformamide and toluene；The purity of the sodium hydride is 60wt%.
(2) after the cooling of step (1) reaction product, the chloroform of 0.5 times of volume of reaction product is added thereto, into one
Step separates out the sodium chloride byproduct of dissolving from organic solvent, is filtered with diatomite, removes sodium chloride salinity in filtrate, and pass through
To isolate sodium chloride, re-evaporation crystallization separates out washing diatomite.
(3) most of organic solvent is distilled off in the filtrate decompression after step (2) processing, obtains faint yellow thick shape
Solid, then uses the chloroform of heat to extract, then obtains faint yellow solid product after removing solvent, and epoxy quinoline is obtained after dry：1- (2,3- rings
Oxygen propyl group)-N- Nitroimidazoline -2- base amine crude product, vacuum distillation temperature be 40 DEG C, pressure 0.3Kpa.
(4) the epoxy quinoline finally obtained with the ethanol or acetone of heat to step (3)：1- (2,3- glycidyl)-N- nitros
Sub- imidazolidine -2- bases amine crude product is recrystallized, and the epoxy quinoline is finally made：1- (2,3- glycidyl)-N- nitros Asia miaow
The sterling of oxazolidine -2- base amine, yield is about 83%.
Wherein：Sodium hydride is added portionwise, because substantial amounts of hydrogen can be produced by adding sodium hydride；During suction filtration, diatomite is used
Or carclazyte more thorough desalination and can isolate salinity byproduct.
The reaction equation of the above process is as follows：
The present invention has following technical characterstic：
1st, can be effectively complete by the weaker hydrogen of resonant middle acidity in N- nitro imido imidazolyl alkanes using sodium hydride
Dissociate and switch to sodium salt, and other organic by-products will not be produced.
2nd, the use of polarity and the stronger N of dissolubility, N'- dimethylformamides is reaction dissolvent, solvent can be greatly reduced
Usage amount, and the N being evaporated under reduced pressure out, N'- dimethylformamide can be with recycleds, more economical environmental protection.
3rd, reaction temperature is 50~60 DEG C, and heat condition is gentleer, and energy consumption is less.
4th, byproduct sodium chloride can be efficiently separated out in product separation process, to reduce the generation of solid waste.
5th, chloroform continues can also be recycled in processing procedure after the reaction, reduces cost.
6th, compared with prior art, the method for the present invention reaction time is shorter, yield higher, and aftertreatment technology is also relatively simple
It is single.
In short, the method for the present invention is to prepare a kind of more environmentally protective process of epoxy quinoline, there is the reality of higher
With value, more suitable for large-scale industrial production.
Brief description of the drawings
Fig. 1 is the process flow chart that the present invention prepares epoxy quinoline.
Embodiment
Embodiment 1：By 97.5g (0.75mol) N- nitro imido imidazolyl alkanes, 18g (0.75mol) sodium hydrides and 125mL
N, N'- dimethylformamide and 75mL toluene solvants are added in reaction bulb, are heated to 65 DEG C, after imidazolidine dissolves substantially,
46.3g (0.5mol) epoxychloropropane is added dropwise thereto, the reaction was continued 1.5h after being added dropwise, and supervised with TLC or HPLC tracking
Reaction process is surveyed until reaction terminates.After reaction, question response thing cools down, and adds 100mL chloroforms, is crossed and filtered out by diatomite
Filtered after salt, then most of solvent is distilled off in filtrate decompression, obtain thick shape solid, extracted with the chloroform of heat, collect extraction
Liquid, removes chloroform and obtains faint yellow solid product, and dry crude product, is recrystallized with the ethanol solution of heat, luridly dry
1- (2,3- glycidyl)-N- Nitroimidazoline -2- base amine solid product 77.3g, yield 83.2%, fusing point：87~90 DEG C.
Embodiment 2：By 97.5g (0.75mol) N- nitro imido imidazolyl alkanes, 18g (0.75mol) sodium hydrides and 175mL
N, N'- solvent dimethylformamide are added in reaction bulb, are heated to 60 DEG C, treat that N- nitro imido imidazolyl alkanes dissolve substantially
Afterwards, 46.3g (0.5mol) epoxychloropropane is added dropwise thereto, after being added dropwise the reaction was continued 2h, TLC or HPLC monitoring react into
Journey.After reaction, after the cooling of question response thing, filtering, carries out vacuum distillation by filtrate and removes major part N, N'- dimethyl formyl
Amine, obtains thick solid, and add diethyl ether multiple washing, filtering, obtains light yellow solid, the acetone recrystallization of crude product reusable heat, does
It is dry to obtain lurid 1- (2,3- glycidyl)-N- Nitroimidazolines -2- base amine solid 78g, yield 83.9%, fusing point：87
~90 DEG C.
Claims (1)
1. a kind of preparation method of epoxy quinoline, it is characterised in that the preparation method comprises the following steps that：
(1) under nitrogen protection, N- nitro imido imidazolyl alkanes and organic solvent are added in reactor, are then added portionwise
Sodium hydride, is heated to 50~60 DEG C of temperature, and after the dissolving of N- nitroiminos Asia imidazolidine, epoxy is slowly added dropwise into reactor
Chloropropane, is added dropwise, and continues heating 1~1.5h of reaction and terminates to reaction, reaction process is monitored with TLC or HPLC；The ring
The molar ratio of oxygen chloropropane, N- nitro imido imidazolyl alkanes and sodium hydride is：Epoxychloropropane: N- nitro imido imidazolyl alkanes:
Sodium hydride=1：1.1-1.5：1.1-1.5；The organic solvent is N, N'- dimethylformamides or N, N'- dimethylformamide
With the mixed solvent of toluene；The purity of the sodium hydride is 60wt%；
(2) after the cooling of step (1) reaction product, add the chloroform of 0.5 times of volume of reaction product thereto, further from
The sodium chloride byproduct of dissolving is separated out in organic solvent, is filtered with diatomite, removes sodium chloride salinity in filtrate, and pass through washing
To isolate sodium chloride, re-evaporation crystallization separates out diatomite；
(3) most of organic solvent is distilled off in the filtrate decompression after step (2) processing, obtains faint yellow thick shape and consolidate
Body, then uses the chloroform of heat to extract, then obtains faint yellow solid product after removing solvent, and epoxy quinoline is obtained after dry：1- (2,3- epoxies
Propyl group)-N- Nitroimidazoline -2- base amine crude product, vacuum distillation temperature be 40 DEG C, pressure 0.3KPa；
(4) the epoxy quinoline finally obtained with the ethanol or acetone of heat to step (3)：1- (2,3- glycidyl)-N- nitros Asia miaow
Oxazolidine -2- base amine crude products are recrystallized, and the epoxy quinoline is finally made：1- (2,3- glycidyl)-N- Nitroimidazolines-
The sterling of 2- base amine.
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