CN102199096A - Method for synthesizing organic ionic compounds - Google Patents
Method for synthesizing organic ionic compounds Download PDFInfo
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- CN102199096A CN102199096A CN2011100665232A CN201110066523A CN102199096A CN 102199096 A CN102199096 A CN 102199096A CN 2011100665232 A CN2011100665232 A CN 2011100665232A CN 201110066523 A CN201110066523 A CN 201110066523A CN 102199096 A CN102199096 A CN 102199096A
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Abstract
The invention discloses a method for synthesizing organic ionic compounds. The method is a two-step method comprising the steps of: first, amine or a heterocyclic compound containing N element is subject to a reaction with a matter which can provide protons, such that an amine salt or a heterocyclic onium salt is produced; second, the obtained amine salt or heterocyclic onium salt is subject to a reaction with carbonate, such that a corresponding quaternary ammonium salt or an N- substituted heterocyclic onium salt is produced. The organic ionic compound is a salt comprising one of the following anions: BF4<->, PF6<->, ClO4<->, CF3SO3<->, C4F9SO3<->, [(CF3SO2)2N] <->, [(C2F5SO2)2N] <->, [B(COOCOO)2] <->, [(CN)2N] <->, BF2(CF3)2<->, BF(CF3)3<->, PF3(C2F5)3<->, and PF3(CF3)3<->. After a reaction is carried out between an acid solution and amine or a heterocyclic compound containing N element, water is removed through heating, vaporizing or distilling, such that the ammonium salt or the heterocyclic onium salt with little water content is obtained. The first step of the method assists in controlling the acid concentration of the reaction system, such that the reaction efficiency can be improved. After the first-step reaction, water residual contents in the ammonium salt or the heterocyclic onium salt can be minimized, such that possibilities of side reactions can be reduced.
Description
Technical field
The present invention relates to a kind of synthetic method of organic ion compound, be specifically related to have the synthetic method of more low-melting organic ion compound.
Background technology
The organic ion compound is the material that a class is made of organic cation and negatively charged ion, and positively charged ion is imidazol ion, pyridinium ion, quaternary ammonium ion, tetramethyleneimine ion or piperidines ion normally, and representative molecular structure is as follows:
When negatively charged ion is BF
4 -, PF
6 -, ClO
4 -, CF
3SO
3 -, C
4F
9SO
3 -, [(CF
3SO
2)
2N]
-, [(C
2F
5SO
2)
2N]
-, [B (COOCOO)
2]
-, [(CN)
2N]
-, BF
2(CF
3)
2 -, BF (CF
3)
3 -, PF
3(C
2F
5)
3 -, PF
3(CF
3)
3 -In a kind of the time, this type of organic ion compound has lower fusing point usually, therefore, claims ionic liquid at room temperature (room temperature melting salt) again.
Low melting point organic ion compound has following characteristics usually: 1) liquid temperature wide ranges (or melting range is wide), the liquid scope of conventional solvent is all narrow, for example the liquid range temperature of water is 0 ℃～100 ℃, the liquid scope of methylcarbonate is 2 ℃～90 ℃, and most of ion liquid liquid temperature scope can reach-20 ℃～400 ℃; 2) dissolving power strong and adjustable (by adjusting positively charged ion and anionic structure) can be dissolved multiple organism and inorganics, and for example, 1-ethyl-3-methyl imidazolium tetrafluoroborate can be dissolved each other fully with propylene carbonate; 3) there is not remarkable vapour pressure, even it is not under comparatively high temps, volatile yet; 4) stability is high, and ionic liquid has thermostability and chemical stability preferably, and most of ion liquid decomposition temperatures are more than 250 ℃, chemical stability be embodied in ionic liquid under general condition with a lot of materials react with not; 5) electroconductibility is good, and general ionic liquid specific conductivity is 1～10mS/cm order of magnitude; 6) electrochemical window is wide, generally between 0～4V; 7) nonflammable or not flammable (can't light) with naked light.
Simultaneously because of the characteristic of itself, low melting point organic ion compound can provide a brand-new reaction environment for organic synthesis, can avoid because of using environmental pollution that a large amount of volatile organic solvent brings and to the mankind's harm, being green replace solvents; Be applied in the catalyzed reaction, can change the mechanism of reaction, cause new catalytic activity, improve transformation efficiency and selectivity, even itself can directly apply in the catalyzed reaction as catalyzer.
Compare conventional organic solvents, and the specific conductivity height of low melting point organic ion compound (1～10mS/cm), have better ionic conductivity, can be applicable to electrochemical field.Specific conductivity is relevant with factors such as viscosity, molecular weight, density and ionic sizes, and the influence of its medium viscosity is the most obvious, and viscosity is big more, and ionic conductivity is poor more.Can reduce viscosity, thereby increase its specific conductivity by adjustment ionic liquid positively charged ion, anionic structure.Electrochemical window electrochemical stability potential window is exactly the difference that ionic liquid begins to take place the current potential of oxidizing reaction and begins to take place the current potential of reduction reaction.The electrochemical window broad of organic ion compound, also extremely important to its application in electrochemical field, most of ion liquid electrochemical stability electrochemical window is 4V, and this compares than broad with common organic solvents, and this also is one of its advantage.
The traditional route of synthetic this type of low melting point organic ion compound is as follows:
With 1-ethyl-3-methyl imidazolium tetrafluoroborate is example.At first, N-Methylimidazole and monobromethane at organic solvent as 1,1, reaction generates 1-ethyl-3-Methylimidazole Bromide in the 1-trichloroethane, imidazoles Bromide and sodium tetrafluoroborate react in acetone or carry out anion exchange reaction with silver tetrafluoroborate in the aqueous solution then, generate 1-ethyl-3-methyl imidazolium tetrafluoroborate.Obviously, utilize the little characteristics of metal halide solubleness in organic solvent to make the halogen ion separate out the purpose that realizes ion-exchange, certainly exist reaction halfway phenomenon, i.e. residual former negatively charged ion (bromide anion) in the final product with precipitation forms.Utilize silver salt in the aqueous solution, to carry out, can react completely, but cost is too high.
Chinese patent 200710008626.7 discloses a kind of synthetic method by carbonic ether and amine salt prepared in reaction quaternary ammonium salt.In this patent application, the negatively charged ion scope of quaternary ammonium salt is confined to vitriol, hydrosulfate, nitrate, phosphoric acid salt, hydrophosphate, dihydrogen phosphate, fluoride salt, chlorate, Bromide, iodized salt, sulphide salt, carbonate, supercarbonate, oxalate, acetate and carboxylate salt.These anionic sources are corresponding acid, as sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, acetic acid etc.These acid all are more common chemical, have higher relatively thermostability and chemical stability, it is very little that the side reaction possibility takes place in the system of carbonic ether and amine salt prepared in reaction quaternary ammonium salt, disclosed embodiment has confirmed this viewpoint (yield is more than 90%, and major part reaches 99%) in the Chinese patent 200710008626.7.In addition, because these negatively charged ion (not comprising carboxylate radical) mainly show the inorganic chemistry characteristic, structure plasticity-is not strong, therefore, in the time need reaching some application purpose, mainly realize by changing cationic structure by the molecular structure of adjusting ion organic compound.
Compare acid mentioned above, following sour HBF
4, HPF
6, HClO
4, CF
3SO
3H, C
4F
9SO
3H, (CF
3SO
2)
2NH, (C
2F
5SO
2)
2NH, B (COOCOO)
2H, (CN)
2NH, BF
2(CF
3)
2H, BF (CF
3)
3H, PF
3(C
2F
5)
3H or PF
3(CF
3)
3H etc. because of its special property such as strong oxidizing property (as HClO
4) or superpower acidity (as CF
3SO
3H) may in quaterisation, show different results and cause target product yield to descend, be worth further investigation as introducing side reaction; On the other hand, contain BF
4 -, PF
6 -, ClO
4 -, CF
3SO
3 -, C
4F
9SO
3 -, [(CF
3SO
2)
2N]
-, [(C
2F
5SO
2)
2N]
-, [B (COOCOO)
2]
-, [(CN)
2N]
-, BF
2(CF
3)
2 -, BF (CF
3)
3 -, PF
3(C
2F
5)
3 -Or PF
3(CF
3)
3 -Be used widely in electrochemical field because of its special property etc. anionic low melting point organic ion compound, existing ten hundreds of documents are reported this.But as mentioned, traditional reaction scheme of synthetic this compounds is quite loaded down with trivial details, therefore, can synthesize if can find novel process to pass through simple method, and is very meaningful.
In view of this, the invention provides a kind of synthetic method of organic ion compound, by the synthetic organic ion compound of two step method, negatively charged ion is BF
4 -, PF
6 -, ClO
4 -, CF
3SO
3 -, C
4F
9SO
3 -, [(CF
3SO
2)
2N]
-, [(C
2F
5SO
2)
2N]
-, [B (COOCOO)
2]
-, [(CN)
2N]
-, BF
2(CF
3)
2 -, BF (CF
3)
3 -, PF
3(C
2F
5)
3 -Or PF
3(CF
3)
3 -
Summary of the invention
At the problems referred to above, the invention provides a kind of synthetic method of organic ion compound.To realize the synthetic of low melting point organic ion compound, can avoid because of using environmental pollution that a large amount of volatile organic solvent brings and to the mankind's harm.
To achieve these goals, solution of the present invention is as follows:
A kind of synthetic method of organic ion compound, synthesize the organic ion compound by following two step method:
The first step, amine or heterogeneous ring compound that contains the N element and the substance reaction that proton can be provided generate amine salt or heteroaryl salt; In second step, amine salt or heteroaryl salt and carbonate reaction generate corresponding quaternary ammonium salt or N-substituted heterocycle salt; Wherein, the organic ion compound is to contain to be selected from following a kind of anionic salt: BF
4 -, PF
6 -, ClO
4 -, CF
3SO
3 -, C
4F
9SO
3 -, [(CF
3SO
2)
2N]
-, [(C
2F
5SO
2)
2N]
-, [B (COOCOO)
2]
-, [(CN)
2N]
-, BF
2(CF
3)
2 -, BF (CF
3)
3 -, PF
3(C
2F
5)
3 -, or PF
3(CF
3)
3 -
Above-mentioned organic ion compound institute cation is to be selected from least a in the heterocycle ion of quaternary ammonium ion or nitrogenous element.
Wherein, positively charged ion is selected from 1-ethyl-3-Methylimidazole ion, 1-butyl-3-Methylimidazole ion 1, at least a in 2-dimethyl-3-propyl imidazole ion, picoline ion, ethylpyridine ion, dimethyl ethyl methoxyl group quaternary ammonium ion, triethyl methyl quaternary ammonium ion, methyl-propyl tetramethyleneimine ion or the methyl-propyl piperidines ion.
Above-mentioned amine or the heterogeneous ring compound that contains the N element are to be selected from least a in 1-ethyl imidazol(e), 1-butyl imidazole, 2-methyl-3-propyl imidazole, pyridine, methylethyl methoxyl group tertiary amine, triethylamine, amine, propyl pyrrole alkane or the propyl group piperidines.
Wherein, providing the material of proton can be that acid or aqueous acid (are selected from HBF
4, HPF
6, HClO
4, CF
3SO
3H, C
4F
9SO
3H, (CF
3SO
2)
2NH, (C
2F
5SO
2)
2NH, B (COOCOO)
2H, (CN)
2NH, BF
2(CF
3)
2H, BF (CF
3)
3H, PF
3(C
2F
5)
3H or PF
3(CF
3)
3At least a among the H).
Aqueous acid and amine or the heterogeneous ring compound that contains the N element react after (that is: the first step reaction), and water is removed by heating, evaporation or distillatory method, obtains moisture content amine salt or heteroaryl salt seldom.
Carbonic ether is to be selected from least a in methylcarbonate, diethyl carbonate, NSC 11801, propylene carbonate or the Methyl ethyl carbonate.
In the first step of the present invention reaction, the material (for example acid or aqueous acid) that proton can be provided be selected from following group a kind of: HBF
4, HPF
6, HClO
4, CF
3SO
3H, C
4F
9SO
3H, (CF
3SO
2)
2NH, (C
2F
5SO
2)
2NH, B (COOCOO)
2H, (CN)
2NH, BF
2(CF
3)
2H, BF (CF
3)
3H, PF
3(C
2F
5)
3H, PF
3(CF
3)
3H.When the material that proton is provided was aqueous acid, after aqueous acid and amine or the heterogeneous ring compound that contains the N element reacted, water can be removed by methods such as heating, evaporation or distillations, to obtain moisture content amine salt or heteroaryl salt seldom.Hydrolysis reaction can take place in water and carbonic ether, therefore, before carrying out the reaction of second step, preferably reduces to the moisture entrapment amount in amine salt or the heteroaryl salt minimum.In addition, in order to improve the efficient of reaction, the best first accurately concentration of Titrable acid, the heterogeneous ring compound and the acid that make amine as far as possible or contain the N element were reacted in 1: 1 in molar ratio.
In the reaction of second step, carbonic ether has molecular formula OC (OR) (OR '), wherein R and R ' contain hydrocarbon alkyl, thiazolinyl, alkynyl, phenyl, aryl or contain the wherein organic group of at least a element of aerobic, nitrogen, phosphorus, sulphur, fluorine, chlorine, bromine, iodine, R, R ' can be independent substituent groups, also can be to be unified into ring.
A kind of in the preferred methylcarbonate of carbonic ether, diethyl carbonate, NSC 11801, propylene carbonate, the Methyl ethyl carbonate.
Carried out for second when reaction step, temperature of reaction between 100～200 ℃, preferred 120～160 ℃, reaction times 1～72h, preferred 2～24h.
Be different from disclosed embodiment in the Chinese patent 200710008626.7, the most of embodiment among the present invention is by changing processing condition improve product as reduction temperature of reaction, prolongation reaction times yield.In addition, because HBF
4, HPF
6, HClO
4, CF
3SO
3H, C
4F
9SO
3H, (CF
3SO
2)
2NH, (C
2F
5SO
2)
2NH, B (COOCOO)
2H, (CN)
2NH, BF
2(CF
3)
2H, BF (CF
3)
3H, PF
3(C
2F
5)
3H, PF
3(CF
3)
3Acid such as H have severe corrosive usually, and therefore, the first step reaction and the reaction of second step are all carried out in the teflon-lined reactor is arranged in the embodiment of the invention.The reactor that is applied to the reaction of second step also must possess withstand voltage ability, at least can withstand voltage 1.6Mpa.
The invention has the beneficial effects as follows: can control the concentration of reaction system acid by the add-on of the first step reactant acid, help improving reaction efficiency.After the first step reaction, can effectively dewater, reduce to the moisture entrapment amount in amine salt or the heteroaryl salt minimum.So just can prevent that hydrolysis reaction can take place for sealing and carbonic ether, reduce the generation of side reaction.
In addition, the present invention reacts and adopts BF
4 -, PF
6 -, ClO
4 -, CF
3SO
3 -, C
4F
9SO
3 -, [(CF
3SO
2)
2N]
-, [(C
2F
5SO
2)
2N]
-, [B (COOCOO)
2]
-, [(CN)
2N]
-, BF
2(CF
3)
2 -, BF (CF
3)
3 -, PF
3(C
2F
5)
3 -, PF
3(CF
3)
3 -Etc. low melting point organic ion compound, can provide a brand-new reaction environment for organic synthesis, can avoid because of using environmental pollution that a large amount of volatile organic solvent brings and, being green replace solvents the mankind's harm; Be applied in the catalyzed reaction, can change the mechanism of reaction, produce new catalytic activity, improve transformation efficiency and selectivity.The low melting point organic ion compound that generates has melting range wide (being in a liquid state) in wide in range warm area, electrochemical window is wide (prevents the redox reaction of the electrolytic solution under state-of-charge better, can improve simultaneously the cyclical stability of battery), almost do not have advantages such as vapour pressure (no boiling point), specific conductivity height, non-inflammability, be applied to electrochemical field, have boundless use prospect.
Embodiment
A kind of synthetic method of organic ion compound is characterized in that the organic ion compound is synthetic by following two step method:
The first step, amine or heterogeneous ring compound that contains the N element and material (for example acid or the aqueous acid) reaction that proton can be provided generate amine salt or heteroaryl salt, and chemical equation is as follows:
In second step, amine salt or heteroaryl salt and carbonate reaction generate corresponding quaternary ammonium salt or N-substituted heterocycle salt, and chemical equation is as follows:
Wherein R, R ', R
1, R
2, R
3Be to contain hydrocarbon alkyl, thiazolinyl, alkynyl, phenyl, aryl or contain the wherein organic group of at least a element of aerobic, nitrogen, phosphorus, sulphur, fluorine, chlorine, bromine, iodine, R, R ', R
1, R
2, R
3Can be independent substituted radical, also can be that adjacent group is unified into ring.
Organic ion compound institute cation is that to be selected from the heterocycle ionic of quaternary ammonium ion or nitrogenous element a kind of, and structural formula is as follows, but is not limited to following structure:
Wherein R, R ', R
1, R
2, R
3, R
4, R
5Be to contain hydrocarbon alkyl, thiazolinyl, alkynyl, phenyl, aryl or contain the wherein organic group of at least a element of aerobic, nitrogen, phosphorus, sulphur, fluorine, chlorine, bromine, iodine, R, R ', R
1, R
2, R
3, R
4, R
5Can be independent substituent group, also can be that adjacent group is unified into ring.
The preferred following a kind of structure of organic ion compound institute cation: 1-ethyl-3-Methylimidazole ion, 1-butyl-3-Methylimidazole ion 1,2-dimethyl-3-propyl imidazole ion, picoline ion, ethylpyridine ion, dimethyl ethyl methoxyl group quaternary ammonium ion, triethyl methyl quaternary ammonium ion, methyl-propyl tetramethyleneimine ion, methyl-propyl piperidines ion.
In the first step reaction, amine or to contain the heterogeneous ring compound structural formula of N element as follows, but be not limited to following structure:
Wherein R, R
1, R
2, R
3, R
4, R
5Be to contain hydrocarbon alkyl, thiazolinyl, alkynyl, phenyl, aryl or contain the wherein organic group of at least a element of aerobic, nitrogen, phosphorus, sulphur, fluorine, chlorine, bromine, iodine, R, R
1, R
2, R
3, R
4, R
5Can be independent substituent group, also can be that adjacent group is unified into ring.
Amine or contain the preferred following a kind of material of heterogeneous ring compound of N element: 1-ethyl imidazol(e), 1-butyl imidazole, 2-methyl-3-propyl imidazole, pyridine, methylethyl methoxyl group tertiary amine, triethylamine, propyl pyrrole alkane, propyl group piperidines.
In the first step reaction, the material (for example acid or aqueous acid) that proton can be provided be selected from following group a kind of: HBF4, HPF
6, HClO
4, CF
3SO
3H, C
4F
9SO
3H, (CF
3SO
2)
2NH, (C
2F
5SO
2)
2NH, B (COOCOO)
2H, (CN)
2NH, BF
2(CF
3)
2H, BF (CF
3)
3H, PF
3(C
2F
5)
3H, PF
3(CF
3)
3H.When being aqueous acid, after aqueous acid and amine or the heterogeneous ring compound that contains the N element reacted, water can be removed by methods such as heating, evaporation or distillations, to obtain moisture content amine salt or heteroaryl salt seldom.Hydrolysis reaction can take place in water and carbonic ether, therefore, before carrying out the reaction of second step, preferably reduces to the moisture entrapment amount in amine salt or the heteroaryl salt minimum.In addition, when being aqueous acid, the best first accurately concentration of Titrable acid, the heterogeneous ring compound and the acid that make amine as far as possible or contain the N element were reacted in 1: 1 in molar ratio.
In the reaction of second step, carbonic ether has molecular formula OC (OR) (OR '), wherein R and R ' contain hydrocarbon alkyl, thiazolinyl, alkynyl, phenyl, aryl or contain the wherein organic group of at least a element of aerobic, nitrogen, phosphorus, sulphur, fluorine, chlorine, bromine, iodine, R, R ' can be independent substituent groups, also can be to be unified into ring.
A kind of in the preferred methylcarbonate of carbonic ether, diethyl carbonate, NSC 11801, propylene carbonate, the Methyl ethyl carbonate.
Carried out for second when reaction step, temperature of reaction between 100～200 ℃, preferred 120～160 ℃, reaction times 1～72h, preferred 2～24h.
Embodiment 1
Took by weighing a certain amount of triethylamine and tetrafluoroborate solution in 1: 1 in molar ratio, stirred at normal temperatures 2 hours, underpressure distillation removes and anhydrates then, obtains the lower triethyl Tetrafluoroboric acid amine salt (moisture content is lower than 2%) of moisture content; Take by weighing triethyl Tetrafluoroboric acid amine salt, methylcarbonate, methyl alcohol in 1: 1.1: 2 in molar ratio successively, add in the reactor, be warming up to 140 ℃, under this temperature, stirred 24 hours, be cooled to room temperature then, triethyl methyl tetrafluoroborate yield＞93%.
Embodiment 2
Took by weighing a certain amount of N-Methylimidazole and the phosphofluoric acid aqueous solution in 1: 1 in molar ratio, stirred at normal temperatures 4 hours, underpressure distillation removes and anhydrates then, obtains the lower N-Methylimidazole hexafluorophosphate (moisture content is lower than 3%) of moisture content; Took by weighing N-Methylimidazole hexafluorophosphate, methylcarbonate, methyl alcohol in 1: 1.5: 5 in molar ratio successively, add in the reactor, be warming up to 140 ℃, under this temperature, stirred 12 hours, be cooled to room temperature then, 1-ethyl-3-Methylimidazole hexafluorophosphate yield＞80%.
Embodiment 3
Took by weighing a certain amount of N-Methylimidazole and tetrafluoroborate solution in 1: 1 in molar ratio, stirred at normal temperatures 6 hours, underpressure distillation removes and anhydrates then, obtains the lower N-methyl imidazolium tetrafluoroborate (moisture content is lower than 3%) of moisture content; Take by weighing N-methyl imidazolium tetrafluoroborate, methylcarbonate in 1: 3 in molar ratio successively, add in the reactor, be warming up to 160 ℃, under this temperature, stirred 4 hours, be cooled to room temperature then, 1-ethyl-3-methyl imidazolium tetrafluoroborate yield＞82%.
Embodiment 4
Took by weighing a certain amount of N-butyl imidazole and tetrafluoroborate solution in 1: 1 in molar ratio, stirred at normal temperatures 3 hours, underpressure distillation removes and anhydrates then, obtains the lower N-butyl imidazole a tetrafluoro borate (moisture content is lower than 3%) of moisture content; Took by weighing N-butyl imidazole a tetrafluoro borate, methylcarbonate, methyl alcohol in 1: 2: 2 in molar ratio successively, add in the reactor, be warming up to 130 ℃, under this temperature, stirred 36 hours, be cooled to room temperature then, 1-butyl-3-methyl imidazolium tetrafluoroborate yield＞74%.
Embodiment 5
Took by weighing a certain amount of propyl group piperidines and trifluoromethane sulfonic acid (CF in 1: 1 in molar ratio
3SO
3H) aqueous solution stirred 2 hours at normal temperatures, and underpressure distillation removes and anhydrates then, obtains the lower propyl group piperidines trifluoromethane sulfonic acid amine salt (moisture content is lower than 2%) of moisture content; Took by weighing propyl group piperidines trifluoromethane sulfonic acid amine salt, methylcarbonate, methyl alcohol in 1: 1.1: 3 in molar ratio successively, add in the reactor, be warming up to 135 ℃, under this temperature, stirred 8 hours, be cooled to room temperature then, methyl-propyl piperidines trifluoromethyl sulfonic acid yield＞80%.
Embodiment 6
Took by weighing a certain amount of propyl pyrrole alkane and tetrafluoroborate solution in 1: 1 in molar ratio, stirred at normal temperatures 2 hours, underpressure distillation removes and anhydrates then, obtains the lower propyl pyrrole alkane Tetrafluoroboric acid amine salt (moisture content is lower than 1%) of moisture content; Took by weighing propyl pyrrole alkane Tetrafluoroboric acid amine salt, methylcarbonate, methyl alcohol in 1: 1.05: 3 in molar ratio successively, add in the reactor, be warming up to 120 ℃, under this temperature, stirred 72 hours, be cooled to room temperature then, methyl-propyl tetramethyleneimine a tetrafluoro borate yield＞70%.
Embodiment 7
Took by weighing a certain amount of Trimethylamine 99 (aqueous solution) and tetrafluoroborate solution in 1: 1 in molar ratio, stirred at normal temperatures 1 hour, underpressure distillation removes and anhydrates then, obtains the lower trimethylammonium Tetrafluoroboric acid amine salt (moisture content is lower than 1%) of moisture content; Took by weighing trimethylammonium Tetrafluoroboric acid amine salt, NSC 11801, methyl alcohol in 1: 1.2: 4 in molar ratio successively, add in the reactor, be warming up to 160 ℃, under this temperature, stirred 6 hours, be cooled to room temperature then, trimethylammonium hydroxyethyl tetrafluoroborate yield＞93%.
Embodiment 8
Took by weighing the ethyl methoxyl group amine and the phosphofluoric acid aqueous solution in 1: 1 in molar ratio, stirred at normal temperatures 2 hours, underpressure distillation removes and anhydrates then, obtains the lower ethyl methoxyl group phosphofluoric acid amine salt (moisture content is lower than 2%) of moisture content; Took by weighing ethyl methoxyl group phosphofluoric acid amine salt, methylcarbonate, methyl alcohol in 1: 2.2: 4 in molar ratio successively, add in the reactor, be warming up to 140 ℃, under this temperature, stirred 48 hours, be cooled to room temperature then, dimethyl ethyl methoxyl group phosphofluoric acid quaternary ammonium salt yield＞80%.
Embodiment 9
Took by weighing pyridine and tetrafluoroborate solution in 1: 1 in molar ratio, stirred at normal temperatures 6 hours, underpressure distillation removes and anhydrates then, obtains the lower pyridinium tetrafluoroborate salt (moisture content is lower than 5%) of moisture content; Take by weighing pyridinium tetrafluoroborate salt, methylcarbonate, methyl alcohol in 1: 2: 5 in molar ratio successively, add in the reactor, be warming up to 130 ℃, under this temperature, stirred 60 hours, be cooled to room temperature then, picoline a tetrafluoro borate yield＞68%.
Embodiment 10
Took by weighing a certain amount of Trimethylamine 99 (aqueous solution) and trifluoromethane sulfonic acid (CF in 1: 1 in molar ratio
3SO
3H) aqueous solution stirred 2 hours at normal temperatures, and underpressure distillation removes and anhydrates then, obtains the lower trimethylammonium trifluoromethane sulfonic acid amine salt (moisture content is lower than 3%) of moisture content; Took by weighing trimethylammonium trifluoromethane sulfonic acid amine salt, methylcarbonate, methyl alcohol in 1: 1.2: 4 in molar ratio successively, add in the reactor, be warming up to 140 ℃, under this temperature, stirred 4 hours, be cooled to room temperature then, tetramethyl-trifluoromethane sulfonic acid quaternary ammonium salt yield＞95%.
The variation that is appreciated that a lot of details is possible, but therefore this do not run counter to scope and spirit of the present invention, and any person of an ordinary skill in the technical field all should be considered as not breaking away from the category of patent of the present invention to its suitable variation of doing.
Claims (10)
1. the synthetic method of an organic ion compound, by the synthetic organic ion compound of following two step method:
The first step, amine or heterogeneous ring compound that contains the N element and the substance reaction that proton can be provided generate amine salt or heteroaryl salt;
In second step, amine salt or heteroaryl salt and carbonate reaction generate corresponding quaternary ammonium salt or N-substituted heterocycle salt; It is characterized in that: the organic ion compound is to contain to be selected from following a kind of anionic salt: BF
4 -, PF
6 -, ClO
4 -, CF
3SO
3 -, C
4F
9SO
3 -, [(CF
3SO
2)
2N]
-, [(C
2F
5SO
2)
2N]
-, [B (COOCOO)
2]
-, [(CN)
2N]
-, BF
2(CF
3)
2 -, BF (CF
3)
3 -, PF
3(C
2F
5)
3 -, or PF
3(CF
3)
3 -
2. the synthetic method of a kind of organic ion compound according to claim 1 is characterized in that: described organic ion compound institute cation is to be selected from least a in the heterocycle ion of quaternary ammonium ion or nitrogenous element.
3. the synthetic method of a kind of organic ion compound according to claim 2, it is characterized in that: described positively charged ion is selected from 1-ethyl-3-Methylimidazole ion, 1-butyl-3-Methylimidazole ion, 1, at least a in 2-dimethyl-3-propyl imidazole ion, picoline ion, ethylpyridine ion, dimethyl ethyl methoxyl group quaternary ammonium ion, triethyl methyl quaternary ammonium ion, methyl-propyl tetramethyleneimine ion or the methyl-propyl piperidines ion.
4. the synthetic method of a kind of organic ion compound according to claim 1 is characterized in that: described amine or the heterogeneous ring compound that contains the N element are to be selected from least a in 1-ethyl imidazol(e), 1-butyl imidazole, 2-methyl-3-propyl imidazole, pyridine, methylethyl methoxyl group tertiary amine, triethylamine, amine, propyl pyrrole alkane or the propyl group piperidines.
5. the synthetic method of a kind of organic ion compound according to claim 1 is characterized in that: the material that proton can be provided is acid or aqueous acid.
6. the synthetic method of a kind of organic ion compound according to claim 5 is characterized in that: described acid or aqueous acid are to be selected from HBF
4, HPF
6, HClO
4, CF
3SO
3H, C
4F
9SO
3H, (CF
3SO
2)
2NH, (C
2F
5SO
2)
2NH, B (COOCOO)
2H, (CN)
2NH, BF
2(CF
3)
2H, BF (CF
3)
3H, PF
3(C
2F
5)
3H or PF
3(CF
3)
3At least a among the H.
7. the synthetic method of a kind of organic ion compound according to claim 1 is characterized in that: after the first step reaction, the water in the reaction system is removed by heating, evaporation or distillatory method, obtains moisture content amine salt or heteroaryl salt seldom.
8. the synthetic method of a kind of organic ion compound according to claim 1 is characterized in that: described carbonic ether is to be selected from least a in methylcarbonate, diethyl carbonate, NSC 11801, propylene carbonate or the Methyl ethyl carbonate.
9. the synthetic method of a kind of organic ion compound according to claim 1 is characterized in that: the temperature of reaction of second step reaction is 100～200 ℃, and the reaction times is 1～72h.
10. the synthetic method of a kind of organic ion compound according to claim 9 is characterized in that: the temperature of reaction of described second step reaction is 120～160 ℃, and the reaction times is 2～24h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262224A (en) * | 2014-09-29 | 2015-01-07 | 绍兴佳华高分子材料股份有限公司 | Preparation method and industrialized production method of pyrrolidinium with tetrafluoroborate anions |
| CN107021941A (en) * | 2016-02-02 | 2017-08-08 | 微宏动力系统（湖州）有限公司 | Ionic liquid and preparation method thereof |
| CN108003033A (en) * | 2017-12-05 | 2018-05-08 | 常州大学 | A kind of preparation method of quaternary ammonium salt for super capacitor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948268A (en) * | 2005-10-10 | 2007-04-18 | 浙江师范大学 | Synthesis method of quaternary ammonium salt |
| CN101245019A (en) * | 2007-02-14 | 2008-08-20 | 邱建兴 | Novel technique for synthesizing quaternary ammonium salt |
| CN101378136A (en) * | 2007-08-28 | 2009-03-04 | 株式会社东芝 | Nonaqueous-electrolyte battery and battery pack |
-
2011
- 2011-03-15 CN CN2011100665232A patent/CN102199096A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948268A (en) * | 2005-10-10 | 2007-04-18 | 浙江师范大学 | Synthesis method of quaternary ammonium salt |
| CN101245019A (en) * | 2007-02-14 | 2008-08-20 | 邱建兴 | Novel technique for synthesizing quaternary ammonium salt |
| CN101378136A (en) * | 2007-08-28 | 2009-03-04 | 株式会社东芝 | Nonaqueous-electrolyte battery and battery pack |
Non-Patent Citations (2)
| Title |
|---|
| 《Chemistry Letters》 20101005 Wenjun Xiao et al. A Novel and Green Method for the Synthesis of Ionic Liquids Using the Corresponding Acidic Ionic Liquid Precursors and Dialkyl Carbonate 1112-1113 1-10 第39卷, 第10期 * |
| WENJUN XIAO ET AL.: "A Novel and Green Method for the Synthesis of Ionic Liquids Using the Corresponding Acidic Ionic Liquid Precursors and Dialkyl Carbonate", 《CHEMISTRY LETTERS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262224A (en) * | 2014-09-29 | 2015-01-07 | 绍兴佳华高分子材料股份有限公司 | Preparation method and industrialized production method of pyrrolidinium with tetrafluoroborate anions |
| CN107021941A (en) * | 2016-02-02 | 2017-08-08 | 微宏动力系统（湖州）有限公司 | Ionic liquid and preparation method thereof |
| US10411301B2 (en) | 2016-02-02 | 2019-09-10 | Microvast Power Systems Co., Ltd. | Ionic liquids and preparation method thereof |
| CN107021941B (en) * | 2016-02-02 | 2020-06-19 | 微宏动力系统（湖州）有限公司 | Ionic liquid and preparation method thereof |
| CN108003033A (en) * | 2017-12-05 | 2018-05-08 | 常州大学 | A kind of preparation method of quaternary ammonium salt for super capacitor |
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