CN106008262A - Preparation method of 4,5-dicyan base-2-trifluoro-methylimidazole and prepared intermediate and salt thereof - Google Patents
Preparation method of 4,5-dicyan base-2-trifluoro-methylimidazole and prepared intermediate and salt thereof Download PDFInfo
- Publication number
- CN106008262A CN106008262A CN201610412624.3A CN201610412624A CN106008262A CN 106008262 A CN106008262 A CN 106008262A CN 201610412624 A CN201610412624 A CN 201610412624A CN 106008262 A CN106008262 A CN 106008262A
- Authority
- CN
- China
- Prior art keywords
- dicyano
- solvent
- trifluoro
- preparation
- trifluoromethyl imidazoles
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/30—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same unsaturated acyclic carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members 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
- C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
Abstract
The invention belongs to the technical field of chemical synthesis and particularly relates to a preparation method of 4,5-dicyan base-2-trifluoro-methylimidazole and a prepared intermediate and salt thereof. Diaminoaleo dinitrile and trifluoroacetic acid ester are subjected to aminolysis of ester with solvent or without solvent, amide is obtained, the amide is then subjected to intramolecular dehydration, a crude product of the 4,5-dicyan base-2-trifluoro-methylimidazole is obtained, after the crude product is purified, high-purity dehydrate of the 4,5-dicyan base-2-trifluoro-methylimidazole is obtained, then the high-purity dehydrate is mixed with water phase suspension liquid of salt of metal elements and stirred for a reaction, after the reaction is ended, filtering is conducted to remove an undissolved substance, filtrate is evaporated to be dry in a rotary evaporation mode, after dissolution with solvent is conducted again, filtering, rotary evaporation and vacuum drying are conducted, and the high-purity 4,5-dicyan base-2-trifluoro-methylimidazole salt is obtained. The condition of the whole technological process is safer and milder compared with those of other processes for producing the 4,5-dicyan base-2-trifluoro-methylimidazole, and the preparation method meets the requirement for scaled production.
Description
Technical field
The invention belongs to chemosynthesis technical field, be specifically related to a kind of 4,5-dicyano-2-trifluoromethyl imidazoles, its prepare the preparation method of intermediate and salt thereof.
Background technology
In recent years, the compact electronic devices such as mobile charging treasured, mobile phone, flat board have been widely used in a variety of applications in life, and the Large Electric instruments such as electric motor car are also under the promotion of national policy etc. in fast development, therefore the demand of the following secondary cell for excellent performance is by increasing.
At present, utilize lithium reaction most commonly seen as the lithium secondary battery of discharge and recharge reaction, be with a wide range of applications, and in the lithium ion battery of industrialized production, LiPF6Use still account for leading position.But in actual use, LiPF6Having exposed under facile hydrolysis, high temperature the situations such as fast decoupled, this not only easily causes safety problem also can significantly reduce the life-span of battery, hides some dangers for, constrain the development of a series of relevant industries in following lithium electricity application and development.
Therefore, series of new lithium salts is synthesized and is applied to lithium ion battery electrolyte to solving the problems referred to above.Wherein 4,5-dicyano-2-trifluoromethyl imidazoles lithium contain less fluorine atom and compared with the phosphorus-fluorine bond of LiPF6 carbon-fluorine bond higher, therefore this salt has good electric conductivity and has extraordinary dissociation between imidazole anion and lithium cation.This material heat decomposition temperature is high, can exceed that 250 DEG C, and electrochemical oxidation voltage is higher, the highest to the corrosion potential of current collector aluminum foil, additionally has higher lithium ion transference number and can meet the use requirement of the lower positive electrode of actual application.Therefore, when futurity industry metaplasia is produced and applies, 4,5-dicyano-2-trifluoromethyl imidazoles lithiums are expected to substitute now widely used LiPF6Become a kind of Novel lithium-ion battery electrolyte.
It is currently known 4, 5-dicyano-2-trifluoromethyl imidazoles and salt thereof obtain synthetic route and are mostly diaminomaleonitrile and fluorinated, acid anhydride reactant, but fluorination anhydride boiling point is low, volatile, zest is strong, tear-gas, to water sensitive, there is chance water and can be decomposed into poisonous fluoride gas, burning produces the features such as poisonous fluoride smog, safety is poor, additionally due to this matter-pole is volatile also can cause the use inconvenience caused in large-scale production such as measurement deviation etc., if this material can cause higher two aminoacylates made on diaminomaleonitrile of local concentration to generate by-products adding fashionable stirring not in time in production, yield is caused to reduce, Impurity removal difficulty, degradation adverse consequences under product quality.Therefore, it is within the contemplation of the invention that by avoiding use fluorination anhydride to make production process safer, adjust the purity of final products, raising productivity, the kind controlling by-product and quantity by the change of raw material and flow process simultaneously.
Summary of the invention
For solving the deficiencies in the prior art, the invention provides a kind of 4,5-dicyano-2-trifluoromethyl imidazoles, its prepare the preparation method of intermediate and salt thereof.
A kind of 4,5-dicyano-2-trifluoromethyl imidazoles prepare intermediate, for having the amide of formula:
Present invention also offers a kind of 4, the preparation method of 5-dicyano-2-trifluoromethyl imidazoles, including procedure below: diaminomaleonitrile and trifluoro-acetate add solvent or without solvent under conditions of carry out the amine solution of ester, obtain amide provided by the present invention, amide provided by the present invention intramolecular dehydration again, obtain 4,5-dicyano-2-trifluoromethyl imidazoles.
Concrete, the formula of trifluoro-acetate is CF3COOR, wherein R is alkyl, preferably the alkyl of 1～10 carbon.
Concrete, diaminomaleonitrile is 1:0.5～5 with the inventory of trifluoroacetic acid in molar ratio.
Concrete, the response time is 0.25～12h.
Concrete, react under dry argon gas is protected.
Further, the boiling point of trifluoro-acetate is Tb, as 75 DEG C≤TbWhen≤140 DEG C, diaminomaleonitrile and trifluoro-acetate carry out the amine solution of ester under conditions of without solvent, and course of reaction includes the first temperature stage T1With the second temperature stage T2, wherein, T1＜ T2, 30 DEG C≤T2＜ Tb。
Preferably, 75 DEG C≤T2＜ Tb。
Further, the boiling point of trifluoro-acetate is Tb, as 75 DEG C≤TbWhen≤140 DEG C, diaminomaleonitrile and trifluoro-acetate carry out the amine solution of ester under conditions of adding solvent, and the boiling point of solvent is Ta, course of reaction includes the first temperature stage T1With the second temperature stage T2, wherein, T1＜ T2, 30 DEG C≤T2＜ Ta。
Preferably, 75 DEG C≤T2＜ Tb
Further, the boiling point of trifluoro-acetate is Tb, work as Tb＜ 75 DEG C or TbDuring ＞ 140 DEG C, diaminomaleonitrile and trifluoro-acetate carry out the amine solution of ester under conditions of adding solvent, and the boiling point of solvent is Ta, course of reaction includes the first temperature stage T1With the second temperature stage T2, wherein, T1＜ T2, 30 DEG C≤T2＜ Ta。
Preferably, 75 DEG C≤T2＜ Ta, and, T2≤140℃。
Due to trifluoro-acetate, to melt boiling point too high or too low, is unfavorable for the carrying out of reaction, needs to select suitable solvent.When boiling point is too high when, need to add solvent and reduce the concentration of reactant, it is to avoid react the most violent.
Concrete, solvent is selected from any one or a few the mixing in ethanol, acetonitrile, diethylene glycol dimethyl ether, oxolane, dioxane, glycol dimethyl ether or diethylene glycol dimethyl ether, and the consumption of solvent is the 50～90wt% of total inventory.
Provided by the present invention 4, on the basis of the preparation method of 5-dicyano-2-trifluoromethyl imidazoles, can be further purified and obtain 4, the dihydrate of 5-dicyano-2-trifluoromethyl imidazoles, step includes:
The stage of reaction
Carrying out the reaction of 0.25～12h, reaction terminates the evaporated unnecessary trifluoro-acetate of final vacuum and solvent, obtains crude product 4,5-dicyano-2-trifluoromethyl imidazoles；
Purification phase
Crude product except the purification step such as color, filtration, repeatedly recrystallization, finally gives the purest 4, the dihydrate of 5-dicyano-2-trifluoromethyl imidazoles through dissolving, activated carbon.
In purification phase, available water dissolves crude product, with activated carbon except color, the temperature keeping certain filters to remove activated carbon and insoluble impurities, and filtrate crystallisation by cooling filters, then for solvent, light color crystalline solid repeatedly recrystallization i.e. be can get highly purified dihydrochloride dihydrate crystal with water.
Present invention also offers a kind of safety and highly purified 4, the preparation method of 5-dicyano-2-trifluoromethyl imidazoles salt, comprise the steps: 4, the dihydrate solvent of 5-dicyano-2-trifluoromethyl imidazoles dissolve after with the aqueous phase suspension mix and blend of the salt of metallic element to react, reaction is filtered to remove insoluble matter after terminating, rotation steaming is evaporated filtrate, through filtering, revolve steaming and vacuum drying after again dissolving with solvent, obtain high-purity 4,5-dicyano-2-trifluoromethyl imidazoles salt.
Concrete, metallic element is selected from any one in lithium, sodium, potassium, magnesium or calcium, to prepare a series of 4,5-dicyano-2-trifluoromethyl imidazoles salt.
Concrete, salt is selected from any one in carbonate, villaumite or hydride, hydroxide.
Concrete, solvent is selected from any one in acetonitrile, acetone, dioxane, and it is miscible with water and can dissolve 4,5-dicyano-2-trifluoromethyl imidazoles and the organic solvent of lithium salts thereof.
Concrete, the temperature that rotation is steamed is 100～120 DEG C, and revolves the temperature boiling point more than solvent of steaming.
Concrete, vacuum drying temperature is 100～120 DEG C, and vacuum drying temperature is more than the boiling point of solvent, and the vacuum drying time is 1～5h.
Synthetic route
With 4, as a example by the preparation of 5-dicyano-2-trifluoromethyl imidazoles lithium, synthetic route is as follows:
Principle and the advantage of the present invention are as follows:
The present invention uses diaminomaleonitrile to react under optimum conditions with trifluoro-acetate, 4 that reaction is generated, 5-dicyano-2-trifluoromethyl imidazoles crude product is purified, highly purified product can be obtained, product also can be prepared corresponding 4 further with metal carbonate reactant salt, 5-dicyano-2-trifluoromethyl imidazoles salt.
Diaminomaleonitrile and trifluoroacetic acid Lipase absobed 4 in the present invention, 5-dicyano-2-trifluoromethyl imidazoles crude product is considered as two stages, first stage is the amine solution of two kinds of raw material generation esters, obtain amide substance, second stage is, this amide substance is dehydrated formation imidazoles at a suitable temperature.Owing to the temperature of second stage is best with 75～140 DEG C of effects, at 30 DEG C, reaction is difficult to carry out, therefore under conditions of necessity (as the lowest in the trifluoro-acetate boiling point as raw material), heating also can be divided into two sections, first react a period of time at a lower temperature, then be warming up to 75～140 DEG C.
The present invention can avoid using the trifluoroacetic anhydride of one of reactant conventional in existing method, due to trifluoroacetic anhydride, to have zest strong, tear-gas, to water sensitive, meet water and can be decomposed into poisonous fluoride gas, burning produces poisonous fluoride smog, boiling point is low, lightning is low, the feature such as volatile, thus and inflammable and danger of combustion is the biggest, make to need sound instrument facility with the link such as raw material shipping storage in process of production, emergency mechanism and establishment officer has been set up periodically to drill emergency trouble shooting measures etc. in theory, these all will strengthen production cost, but, even if measure is perfect, buy from raw material sell finished product during still can there is various unavoidable potential safety hazard, at any time may be to company and resident around, environment etc. damage.In modern production, the proportion of production safety is more and more important, thus wish to find a kind of more suitable, safer raw material to synthesize required 4 with replacement trifluoroacetic anhydride, 5-dicyano-2-trifluoromethyl imidazoles and the salt of correspondence thereof, and trifluoro-acetate boiling point, flash-point selected by the present invention is generally high than trifluoroacetic anhydride, safety is also higher than trifluoroacetic anhydride.
Raw material of the present invention is diaminomaleonitrile, various trifluoro-acetate (such as Trifluoroacetic Acid Ethyl Ester etc.), metal carbonate, suitable solvent etc., these raw materials have the industrialized process for preparing of maturation and large batch of stable supply, in addition to diaminomaleonitrile, many raw materials all list alternative product, raw material and some technical parameter can be adjusted flexibly, it is ensured that produce and the stablizing of price when portion of material price fluctuation is bigger.
The present invention is 4, the producing process of 5-dicyano-2-trifluoromethyl imidazoles dihydrate has been carried out purification, it is possible not only to directly sell highly purified 4,5-dicyano-2-trifluoromethyl imidazoles, also can be with highly purified 4, the reaction of 5-dicyano-2-trifluoromethyl imidazoles prepares corresponding salt, and owing to the imidazoles purity as raw material is the highest, the salt of generation is easier to separate with foreign pigment.The most not only widen the kind that can sell product, and the problem greatly simplifiing subsequent reactions magazins' layout, it is easier to obtain highly purified product.
Purification of the present invention and the follow-up process producing salt are relatively easy, and power consumption is few, and imidazoles dihydrate purification phase can not use that organic solvent, environmental pollution be little, aqueous solution therefore cost little than organic solvent processing load reduces the most accordingly.
The whole technological process condition that the present invention is previously mentioned relatively before other produce 4; the flow process of 5-dicyano-2-trifluoromethyl imidazoles is safer and gentle, be suitable for the requirement of large-scale production; required relevant process matched therewith flow process is simple (such as sewage disposal), thus the equipment investment of this project entirety is relatively low.
Detailed description of the invention
Principle and feature to the present invention are described below, and example is served only for explaining the present invention, is not intended to limit the scope of the present invention.
Embodiment 1
With motor stirrer, reflux condensing tube, thermometer, tetra-mouthfuls of round-bottomed flasks of 1L of airway; in glove box, diaminomaleonitrile 43.24g (0.4mol) is added under room temperature; trifluoro-acetate 51.22g (0.4mol); 1; 4-dioxane 500mL; the good device of frame, opens aeration equipment and ensures that whole process has dry argon shield with reaction.Stirring 2h at 25 DEG C makes two kinds of reactants fully react generation amide, then heat to 1, the boiling point (101 DEG C) of 4-dioxane refluxes with guarantee system, at a temperature of Gai, dehydration of amide forms imidazoles, stop reacting by heating after backflow 2h to terminate, obtain containing 4, the mixed solution of 5-dicyano-2-trifluoromethyl imidazoles.
Evaporative removal solvent and remaining trifluoro-acetate under dry argon gas is protected, add water in system 600ml, add 24g activated carbon except color, before filtration, heat makes system temperature to be filtered be 25～35 DEG C to carry out filter operation more a little, remove activated carbon and other materials water-fast, filtrate is concentrated into 200ml, crystallisation by cooling, it is filtrated to get crystal and washs with frozen water 100ml, gained crystal 200ml water recrystallization, again repeat frozen water washing process, the purest 4 are obtained after repeatedly recrystallization, 5-dicyano-2-trifluoromethyl imidazoles, filtrate in recrystallization process is reusable repeatedly with cleaning mixture,
By 4,5-dicyano-2-trifluoromethyl imidazoles acetonitrile dissolves, and adds the aqueous phase suspension of lithium carbonate in this acetonitrile solution, it is ensured that the stirring of reaction system limit makes the uniform limit of system at the uniform velocity drip aqueous phase suspension, stops when being 7 to pH.The heating of gained solution maintains 25～35 DEG C, filter to remove insoluble matter (mostly being unreacted lithium carbonate), at filtrate 110 DEG C, evacuation rotation is evaporated off water, again add acetonitrile to dissolve 4 be dried in bottle, 5-dicyano-2-trifluoromethyl imidazoles lithium, after being filtered to remove impurity, at 82 DEG C, air-distillation is evaporated off major part acetonitrile, after more moist solid matter is proceeded in vacuum drying oven, 3h it is vacuum dried at 110 DEG C, obtain being dried lithium salts 64.95g, productivity 84.65%, purity 99.97%g.
Embodiment 2
With motor stirrer, reflux condensing tube, thermometer, tetra-mouthfuls of round-bottomed flasks of 250mL of airway; in glove box, diaminomaleonitrile 43.24g (0.4mol) is added under room temperature; TAB 68.05g (0.4mol); the good device of frame, opens aeration equipment and ensures that whole process has dry argon shield with reaction.The boiling point 100 DEG C being heated to TAB is easy to make system reflux, two kinds of reactants first generate amide at such a temperature, rear dehydration of amide cyclization forms imidazoles, this reaction 3h altogether, reaction stops heating question response system cooling and i.e. can obtain containing 4 after terminating, the mixed solution of 5-dicyano-2-trifluoromethyl imidazoles.
Will be containing 4, the mixed solution of 5-dicyano-2-trifluoromethyl imidazoles proceeds in 1L flask, add water 600ml, add 24g activated carbon except color, before filtration, heat makes system temperature to be filtered be 25～35 DEG C to carry out filter operation more a little, remove activated carbon and non-water soluble impurity, filtrate is concentrated into 200ml, crystallisation by cooling, it is filtrated to get crystal and washs with frozen water 100ml, gained crystal 200ml water recrystallization, again repeat frozen water washing process, the purest 4 are obtained after repeatedly recrystallization, 5-dicyano-2-trifluoromethyl imidazoles, filtrate in recrystallization process is reusable repeatedly with cleaning mixture,
By 4,5-dicyano-2-trifluoromethyl imidazoles ethanol dissolves, and adds the aqueous phase suspension of lithium carbonate in this ethanol solution, it is ensured that the stirring of reaction system limit makes the uniform limit of system at the uniform velocity drip aqueous phase suspension, stops when being 7 to pH.The heating of gained solution maintains 25～35 DEG C, filter to remove insoluble matter (mostly being unreacted lithium carbonate), at filtrate 110 DEG C, evacuation rotation is evaporated off water, again add ethanol to dissolve 4 be dried in bottle, 5-dicyano-2-trifluoromethyl imidazoles lithium, after being filtered to remove impurity, at 82 DEG C, air-distillation is evaporated off major part ethanol, after more moist solid matter is proceeded in vacuum drying oven, 3h it is vacuum dried at 110 DEG C, obtain being dried lithium salts 63.02g, productivity 82.05%, purity 99.93%g.
Embodiment 3
With motor stirrer, reflux condensing tube, thermometer, tetra-mouthfuls of round-bottomed flasks of 1L of airway; in glove box, diaminomaleonitrile 43.24g (0.4mol) is added under room temperature; Trifluoroacetic Acid Ethyl Ester 142.08g (1mol); 1; 4-dioxane 500mL; the good device of frame, opens aeration equipment and ensures that whole process has dry argon shield with reaction.Stirring 2h at 50 DEG C makes two kinds of reactants fully react generation amide, then heat to 1, the boiling point (101 DEG C) of 4-dioxane refluxes with guarantee system, at a temperature of Gai, dehydration of amide forms imidazoles, stop reacting by heating after backflow 2h to terminate, obtain containing 4, the mixed solution of 5-dicyano-2-trifluoromethyl imidazoles.
Evaporative removal solvent and remaining Trifluoroacetic Acid Ethyl Ester under dry argon gas is protected, add water in system 600ml, add 24g activated carbon except color, before filtration, heat makes system temperature to be filtered be 25～35 DEG C to carry out filter operation more a little, remove activated carbon and other materials water-fast, filtrate is concentrated into 200ml, crystallisation by cooling, it is filtrated to get crystal and washs with frozen water 100ml, gained crystal 200ml water recrystallization, again repeat frozen water washing process, the purest 4 are obtained after repeatedly recrystallization, 5-dicyano-2-trifluoromethyl imidazoles, filtrate in recrystallization process is reusable repeatedly with cleaning mixture,
By 4,5-dicyano-2-trifluoromethyl imidazoles acetonitrile dissolves, and adds the aqueous phase suspension of sodium carbonate in this acetonitrile solution, it is ensured that the stirring of reaction system limit makes the uniform limit of system at the uniform velocity drip aqueous phase suspension, stops when being 7 to pH.The heating of gained solution filters to remove insoluble matter (mostly being unreacted sodium carbonate) at a temperature of maintaining 25-35 DEG C, filtrate evacuation rotation at 110 DEG C is evaporated off water, again add acetonitrile to dissolve 4 be dried in bottle, 5-dicyano-2-trifluoromethyl imidazoles sodium, after being filtered to remove impurity, at 82 DEG C, air-distillation is evaporated off major part acetonitrile, after more moist solid matter is proceeded in vacuum drying oven, 3h it is vacuum dried at 110 DEG C, obtain being dried sodium salt 79.54g, productivity 95.59%, purity 99.92%.
Embodiment 4
With motor stirrer, reflux condensing tube, thermometer, tetra-mouthfuls of round-bottomed flasks of 1L of airway; in glove box, diaminomaleonitrile 43.24g (0.4mol) is added under room temperature; trifluoroacetic acid hexamethylene alcohol ester 392.33g (2mol); 1; 4-dioxane 500mL; the good device of frame, opens aeration equipment and ensures that whole process has dry argon shield with reaction.Stirring 2h at 50 DEG C makes two kinds of reactants fully react generation amide, then heat to 1, the boiling point (101 DEG C) of 4-dioxane refluxes with guarantee system, at a temperature of Gai, dehydration of amide forms imidazoles, stop reacting by heating after backflow 2h to terminate, obtain containing 4, the mixed solution of 5-dicyano-2-trifluoromethyl imidazoles.
Evaporative removal solvent under dry argon gas is protected, add water in system 600ml, add 24g activated carbon except color, before filtration, heat makes system temperature to be filtered be 25-35 DEG C to carry out filter operation more a little, remove activated carbon and other materials water-fast, filtrate is concentrated into 200ml, crystallisation by cooling, it is filtrated to get crystal and washs with frozen water 100ml, gained crystal 200ml water recrystallization, again repeat frozen water washing process, the purest 4 are obtained after repeatedly recrystallization, 5-dicyano-2-trifluoromethyl imidazoles, filtrate in recrystallization process is reusable repeatedly with cleaning mixture,
By 4,5-dicyano-2-trifluoromethyl imidazoles acetonitrile dissolves, and adds the aqueous phase suspension of lithium carbonate in this acetonitrile solution, it is ensured that the stirring of reaction system limit makes the uniform limit of system at the uniform velocity drip aqueous phase suspension, stops when being 7 to pH.The heating of gained solution filters to remove insoluble matter (mostly being unreacted lithium carbonate) at a temperature of maintaining 25-35 DEG C, filtrate evacuation rotation at 110 DEG C is evaporated off water, again add acetonitrile to dissolve 4 be dried in bottle, 5-dicyano-2-trifluoromethyl imidazoles sodium, after being filtered to remove impurity, at 82 DEG C, air-distillation is evaporated off major part acetonitrile, after more moist solid matter is proceeded in vacuum drying oven, 3h it is vacuum dried at 110 DEG C, obtain being dried lithium salts 69.64g, productivity 90.70%, purity 99.90%.
The foregoing is only the better embodiment of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (10)
1. one kind 4,5-dicyano-2-trifluoromethyl imidazoles prepare intermediate, it is characterised in that for having
The amide of formula:
2. one kind 4, the preparation method of 5-dicyano-2-trifluoromethyl imidazoles, it is characterised in that include following
Step: diaminomaleonitrile and trifluoro-acetate add solvent or without solvent under conditions of enter
The amine solution of row ester, obtains the amide described in claim 1, the intramolecular again of the amide described in claim 1
Dehydration, obtains 4,5-dicyano-2-trifluoromethyl imidazoles.
The preparation method of the most according to claim 24,5-dicyano-2-trifluoromethyl imidazoles, it is special
Levying and be, the boiling point of trifluoro-acetate is Tb, as 75 DEG C≤TbWhen≤140 DEG C, diaminourea maleic two
Nitrile and trifluoro-acetate carry out the amine solution of ester under conditions of without solvent, and course of reaction includes the first temperature
Spend stage T1With the second temperature stage T2, wherein, T1＜ T2, 30 DEG C≤T2＜ Tb。
The preparation method of the most according to claim 24,5-dicyano-2-trifluoromethyl imidazoles, it is special
Levying and be, the boiling point of trifluoro-acetate is Tb, as 75 DEG C≤TbWhen≤140 DEG C, diaminourea maleic two
Nitrile and trifluoro-acetate carry out the amine solution of ester under conditions of adding solvent, and the boiling point of solvent is Ta, reaction
Process includes the first temperature stage T1With the second temperature stage T2, wherein, T1＜ T2, 30 DEG C≤T2＜
Ta。
5. according to 4 described in claim 3 or 4, the preparation method of 5-dicyano-2-trifluoromethyl imidazoles,
It is characterized in that: 75 DEG C≤T2＜ Tb。
The preparation method of the most according to claim 24,5-dicyano-2-trifluoromethyl imidazoles, it is special
Levy and be: the boiling point of trifluoro-acetate is Tb, work as Tb＜ 75 DEG C or TbDuring ＞ 140 DEG C, diaminourea is along fourth
Alkene dintrile and trifluoro-acetate carry out the amine solution of ester under conditions of adding solvent, and the boiling point of solvent is Ta,
Course of reaction includes the first temperature stage T1With the second temperature stage T2, wherein, T1＜ T2, 30 DEG C≤
T2＜ Ta。
The preparation method of the most according to claim 64,5-dicyano-2-trifluoromethyl imidazoles, it is special
Levy and be: 75 DEG C≤T2＜ Ta, and, T2≤140℃。
8. one kind 4, the preparation method of 5-dicyano-2-trifluoromethyl imidazoles salt, it is characterised in that include with
Lower step: with metallic element after the dihydrate solvent of 4,5-dicyano-2-trifluoromethyl imidazoles is dissolved
The aqueous phase suspension mix and blend of salt to react, reaction is filtered to remove insoluble matter after terminating, rotation is steamed
It is evaporated filtrate, through filtering, revolve steaming and vacuum drying after again dissolving with solvent, obtains high-purity 4,5-bis-
Cyano group-2-trifluoromethyl imidazoles salt.
The preparation method of the most according to claim 84,5-dicyano-2-trifluoromethyl imidazoles salt, its
It is characterised by:
Metallic element is selected from any one in lithium, sodium, potassium, magnesium or calcium；
Salt is selected from any one in carbonate, villaumite or hydride, hydroxide；
Solvent is selected from any one in acetonitrile, acetone, dioxane.
The preparation method of the most according to claim 84,5-dicyano-2-trifluoromethyl imidazoles salt,
It is characterized in that:
The temperature that rotation is steamed is 100～120 DEG C, and revolves the temperature boiling point more than solvent of steaming；
Vacuum drying temperature is 100～120 DEG C, and vacuum drying temperature is more than the boiling point of solvent,
The vacuum drying time is 1～5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610412624.3A CN106008262B (en) | 2016-06-13 | 2016-06-13 | 4,5- dicyano -2- trifluoromethyl imidazoles, its prepare the preparation method of intermediate and its salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610412624.3A CN106008262B (en) | 2016-06-13 | 2016-06-13 | 4,5- dicyano -2- trifluoromethyl imidazoles, its prepare the preparation method of intermediate and its salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106008262A true CN106008262A (en) | 2016-10-12 |
| CN106008262B CN106008262B (en) | 2018-05-08 |
Family
ID=57087402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610412624.3A Active CN106008262B (en) | 2016-06-13 | 2016-06-13 | 4,5- dicyano -2- trifluoromethyl imidazoles, its prepare the preparation method of intermediate and its salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106008262B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109659615A (en) * | 2018-12-20 | 2019-04-19 | 河南电池研究院有限公司 | Match the lithium-ion battery electrolytes of silicon-carbon cathode material and its battery of preparation |
| CN112774569A (en) * | 2021-01-11 | 2021-05-11 | 江门市华熊新材料有限公司 | Fluorine-containing imidazole surfactant and preparation method and application thereof |
| CN114341115A (en) * | 2019-09-06 | 2022-04-12 | 阿科玛法国公司 | Process for purifying 2- (fluoroalkyl or fluoroalkoxy) -4, 5-dicyanoimidazole |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102264926A (en) * | 2008-08-29 | 2011-11-30 | 国立科学研究中心 | Pentacyclic anion salt and use thereof as an electrolyte |
| CN103930405A (en) * | 2011-11-14 | 2014-07-16 | 阿克马法国公司 | Method for preparing pentacyclic anion salt |
| CN104447564A (en) * | 2014-11-24 | 2015-03-25 | 广州天赐高新材料股份有限公司 | Preparation method of high-purity 4,5-dicyano-2-trifluoromethylimidazole and salts thereof |
| CN105518916A (en) * | 2013-09-05 | 2016-04-20 | 阿科玛法国公司 | Additives for improving the ionic conductivity of lithium-ion battery electrodes |
-
2016
- 2016-06-13 CN CN201610412624.3A patent/CN106008262B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102264926A (en) * | 2008-08-29 | 2011-11-30 | 国立科学研究中心 | Pentacyclic anion salt and use thereof as an electrolyte |
| CN103930405A (en) * | 2011-11-14 | 2014-07-16 | 阿克马法国公司 | Method for preparing pentacyclic anion salt |
| CN105518916A (en) * | 2013-09-05 | 2016-04-20 | 阿科玛法国公司 | Additives for improving the ionic conductivity of lithium-ion battery electrodes |
| CN104447564A (en) * | 2014-11-24 | 2015-03-25 | 广州天赐高新材料股份有限公司 | Preparation method of high-purity 4,5-dicyano-2-trifluoromethylimidazole and salts thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109659615A (en) * | 2018-12-20 | 2019-04-19 | 河南电池研究院有限公司 | Match the lithium-ion battery electrolytes of silicon-carbon cathode material and its battery of preparation |
| CN114341115A (en) * | 2019-09-06 | 2022-04-12 | 阿科玛法国公司 | Process for purifying 2- (fluoroalkyl or fluoroalkoxy) -4, 5-dicyanoimidazole |
| CN112774569A (en) * | 2021-01-11 | 2021-05-11 | 江门市华熊新材料有限公司 | Fluorine-containing imidazole surfactant and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106008262B (en) | 2018-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3381923B1 (en) | Novel method for preparing lithium bis(fluorosulfonyl)imide | |
| CN106044728B (en) | A kind of preparation method of imidodisulfuryl fluoride lithium salt | |
| JP5396239B2 (en) | Solid electrolyte manufacturing apparatus and manufacturing method | |
| CN113800485B (en) | Preparation method of lithium bis (fluorosulfonyl) imide | |
| WO2022262175A1 (en) | Lithium bis(fluorosulfonyl)imide, preparation method therefor and application thereof | |
| EP3617139B1 (en) | Method of preparing high-purity lithium difluorophosphate crystal and non-aqueous electrolyte solution for secondary battery including the crystal | |
| JP2018188359A (en) | Granule or powder of disulfonyl amide salt | |
| CN106008262A (en) | Preparation method of 4,5-dicyan base-2-trifluoro-methylimidazole and prepared intermediate and salt thereof | |
| CN109734734A (en) | A kind of preparation method of dioxalic acid lithium borate | |
| CN109134273A (en) | A kind of method of purification of quaternary ammonium salt | |
| CN109721037B (en) | Novel process of bis (fluorosulfonyl) imide salt | |
| CN111533094A (en) | Method for simply preparing high-purity lithium bis (fluorosulfonyl) imide | |
| CN114524422A (en) | Preparation method of lithium bis (fluorosulfonyl) imide | |
| CN103342372B (en) | Method for preparing lithium tetrafluoroborate | |
| JP2009269917A (en) | Method for producing tetrafluoroboric acid quaternary ammonium salt | |
| WO2024002386A1 (en) | Preparation method for lithium difluorophosphate and product obtained therefrom | |
| CN109678898A (en) | A kind of preparation method of difluorine oxalic acid boracic acid lithium | |
| CN112661791A (en) | Preparation method of lithium difluorobis (oxalate) phosphate | |
| CN108912156B (en) | Preparation method of lithium bis (oxalato) borate | |
| CA2339593C (en) | Method for producing highly pure libf4 | |
| CN115557980A (en) | Synthesis and purification process of sodium bisoxalato | |
| CN110003277A (en) | A kind of tetrafluoro oxalic acid lithium phosphate and preparation method thereof | |
| JPH1087574A (en) | Production of quaternary alkylammonium salt | |
| CN103985866A (en) | Process for manufacturing lithium polysulfide needed by lithium sulfur battery | |
| KR20220156229A (en) | Mass Production Method of Metal bis(fluorosulfonyl)imide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |