CN102250041A - Pyrrolidine ionic compounds containing phenoxy substituents, and preparation method thereof - Google Patents

Pyrrolidine ionic compounds containing phenoxy substituents, and preparation method thereof Download PDF

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CN102250041A
CN102250041A CN2010101851794A CN201010185179A CN102250041A CN 102250041 A CN102250041 A CN 102250041A CN 2010101851794 A CN2010101851794 A CN 2010101851794A CN 201010185179 A CN201010185179 A CN 201010185179A CN 102250041 A CN102250041 A CN 102250041A
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ionic compound
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pyrrolidines ionic
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CN102250041B (en
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刘正平
窦军彦
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Beijing Normal University
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Beijing Normal University
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Abstract

The invention relates to pyrrolidine ionic compounds A<+>B<->. A<+> is represented by a formula (I), wherein R1 is hydrocarbonyl containing 1 to 6 carbon atoms. R2 has a structure represented by a formula (II), wherein n is an integer from 1 to 6, and Y is H, C1 to C6 alkyl or nitro. * represents a connection between the structure of the formula (II) and a nitrogen atom in the formula (I). B<-> is Cl<->, Br<->, I<->, NO3<->, SO4<->, PO4<->, BF4<->, PF6<->, [(CF3SO2)2N] <->, Ac<->, [CH3C6H4SO3]<-> or [CF3SO3]<->. The invention also relates to a preparation method of A<+>B<-> pyrrolidine ionic compounds. The method comprises the steps that: compounds represented by a formula (III) are subject to compounds represented by a formula (IV), such that halide pyrrolidine ionic compounds A<+>B<->, in which B<-> is Cl<->, Br<-> or I<->, are obtained. Pyrrolidine ionic compounds containing other anions can be obtained through ion replacements upon the halide pyrrolidine ionic compounds. The halide pyrrolidine ionic compounds provided by the invention can be used as solvents or catalysts used in fields of organic synthesis, high-molecular synthesis, high-molecular processing, and the like.

Description

Contain pyrrolidines ionic compound of benzene alkyl substituent and preparation method thereof
Technical field
The present invention relates to a kind of pyrrolidines ionic compound, relate in particular to a kind of pyrrolidines ionic compound that contains the benzene alkyl substituent, this compound can be used as ionic liquid.The invention still further relates to the preparation method of aforementioned tetramethyleneimine ionic compound.
Background technology
Ionic liquid is meant by relative less inorganic or the organic melting salt that organic anion constitutes with volume of the relatively large asymmetric organic cation of specific volume.Ionic liquid is compared with traditional fluent meterial (molecular solvent), and it is an ionic compound.Thereby ionic liquid often shows unique character and functions peculiar, is novel " soft " functional materials or the medium that a class has application potential.
When as solvent, with respect to conventional solvent, ionic liquid has following advantage: almost do not have vapour pressure, nonflammable, have high thermostability,, can realize the Modulatory character of ionic liquid physicochemical property etc. by modifying or regulating YIN and YANG ionic structure or kind.
Because the physicochemical property of ionic liquid uniqueness make it obtain extensive studies and application in fields such as organic synthesis, Polymer Synthesizing and processing, separating and extracting, functional materials and life sciences.
At present, reported various N, the glyoxaline ion liquid that N '-dialkyl replaces has especially been reported to introduce on the imidazoles azonia to contain a C 1～C 6Alkylidene group substituting group and a C 1～C 6The N of the di-substituted-phenyl of alkyl, nitro or halogenic substituent, the glyoxaline ion liquid that N '-dialkyl replaces, but do not find on the tetramethyleneimine positively charged ion, to introduce the report of benzene alkyl substituent.The inventor finds that the pyrrolidines ionic compound that contains the benzene alkyl substituent can be used as ionic liquid, and as the solvent of synthetic PET, having of wherein said benzene alkyl substituent is beneficial to the dissolving of PET in the tetramethyleneimine ionic compound.
Summary of the invention
The object of the present invention is to provide a kind of pyrrolidines ionic compound that contains the benzene alkyl substituent.
Another object of the present invention is to provide the preparation method of above-mentioned pyrrolidines ionic compound.
According to a first aspect of the invention, the invention provides a kind of pyrrolidines ionic compound that contains the benzene alkyl substituent, this compound has general formula A +B -, wherein
Described A +Shown in (I)
In the formula (I): R 1For containing the saturated or undersaturated straight or branched alkyl of 1～6 carbon atom, and R 2Have following general formula (II) structure:
In the formula (II),
N is 1～6 integer;
Y is H, C 1～C 6Alkyl or nitro; With
*The tie point of nitrogen heteroatom in expression (II) structure and the formula (I),
And
Described B -For being selected from down the negatively charged ion of group: chlorion, bromide anion, iodide ion, nitrate radical, sulfate radical, phosphate radical, tetrafluoroborate, hexafluoro-phosphate radical, bis trifluoromethyl sulfimide root, acetate moiety, tosic acid root and trifluoromethanesulfonic acid root.
In pyrrolidines ionic compound of the present invention, R 1For containing the saturated or undersaturated straight or branched alkyl of 1～6 carbon atom, thereby, R 1Can be for containing the straight or branched alkyl of 1～6 carbon atom, contain the straight or branched thiazolinyl of 2～6 carbon atoms and, two or more pairs key, perhaps contain the straight or branched alkynyl of 2～6 carbon atoms and, two or more three keys.As the straight or branched alkyl that contains 1～6 carbon atom, can mention methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 2,3-dimethylbutyl and 2, the 2-dimethylbutyl.As the straight or branched thiazolinyl that contains 2～6 carbon atoms and two keys, can mention vinyl, the 1-methyl ethylene, allyl group, propenyl, the 1-butylene base, crotyl, the 3-butenyl, 1-methyl isophthalic acid-propenyl, 2-methyl isophthalic acid-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, the 1-pentenyl, pentenyl, the 2-methyl-1-butene thiazolinyl, the 3-methyl-1-butene base, 3-methyl-2-butene base, 2-methyl-2-butene base, the 1-hexene, the 2-hexene, the 3-hexene, 2-methyl-1-pentene thiazolinyl, 2-methyl-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4-pentenyl, 3-methyl-1-pentene thiazolinyl, 3-methyl-pentenyl, 2-ethyl-1-butylene base, 3,3-dimethyl-1-butylene base, 2,3-dimethyl-1-butylene base and 2,3-dimethyl-crotyl.As the straight or branched alkynyl that contains 2～6 carbon atoms and one three key, can mention ethynyl, 1-proyl, 2-propynyl, ethyl acetylene base, 2-butyne base, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, valerylene base, 2-methyl-1-butene alkynyl, 3-methyl isophthalic acid-butynyl, 2-methyl-2-butyne base, 3-methyl-2-butyne base, 1-hexin base, 2-hexin base, 3-hexin base, 3-methyl-1-pentene alkynyl, 4-methyl-1-pentene alkynyl, 4-methyl-valerylene base and 3,3-dimethyl-ethyl acetylene base.1-alkyl substituted pyrrolidin so R owing to be easy to get on the market 1Be preferably C 1～C 4The straight or branched alkyl, first-selected methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or isobutyl-, more preferably methyl, normal-butyl or isobutyl-; In addition, as R 1, also preferred C 2～C 4Straight or branched thiazolinyl or C 2～C 4Straight or branched alkynyl, for example allyl group or propargyl.
In pyrrolidines ionic compound of the present invention, R 2Have general formula (II) structure, in the formula, n is 1～6 integer, is 1,2,3,4,5 or 6, is preferably 1 or 2; Y is H, C 1～C 6Alkyl or nitro.For this C 1～C 6Alkyl, it can be any straight or branched alkyl, for example can mention methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 2,3-dimethylbutyl and 2, the 2-dimethylbutyl.Equally, consider that for raw material sources Y is preferably H, C 1～C 4Alkyl, as methyl, or nitro.In addition, Y group can be separately located in 2,3 or 4 of phenyl ring shown in the formula (II).
In a particularly preferred embodiment of the present invention, pyrrolidines ionic compound of the present invention is:
N-(2-nitrobenzyl)-N-crassitude bromide;
N-(3-nitrobenzyl)-N-crassitude bromide;
N-(4-nitrobenzyl)-N-crassitude bromide;
N-(4-nitrobenzyl)-N-crassitude a tetrafluoro borate;
N-(4-nitrobenzyl)-N-crassitude hexafluorophosphate;
N-(2-nitrobenzyl)-N-crassitude bis trifluoromethyl sulfimide salt;
N-(3-nitrobenzyl)-N-crassitude bis trifluoromethyl sulfimide salt;
N-(4-nitrobenzyl)-N-crassitude bis trifluoromethyl sulfimide salt;
N-(4-methyl-benzyl)-N-crassitude bromide;
N-(4-methyl-benzyl)-N-crassitude bis trifluoromethyl sulfimide salt;
N-(4-nitrobenzyl)-N-n-butylpyrrolioine bromide;
N-(4-nitrobenzyl)-N-n-butylpyrrolioine bis trifluoromethyl sulfimide salt;
N-(4-nitrobenzyl)-N-isobutyl-tetramethyleneimine bromide;
N-(4-nitrobenzyl)-N-isobutyl-tetramethyleneimine bis trifluoromethyl sulfimide salt;
N-(4-nitrobenzyl)-N-crassitude acetate;
N-(4-nitrobenzyl)-N-crassitude tosilate;
N-(4-nitrobenzyl)-N-allyl group tetramethyleneimine bromide;
N-(4-nitrobenzyl)-N-propargyl tetramethyleneimine bromide;
N-(4-nitrobenzyl)-N-allyl group tetramethyleneimine bis trifluoromethyl sulfimide salt;
N-(4-nitrobenzyl)-N-propargyl tetramethyleneimine bis trifluoromethyl sulfimide salt;
N-styroyl-N-crassitude bromide;
N-styroyl-N-crassitude hexafluorophosphate; Or
N-styroyl-N-crassitude bis trifluoromethyl sulfimide salt.
Pyrrolidines ionic compound of the present invention can be used as ionic liquid, and it has lower melt temperature, and wherein the overwhelming majority can be used as ionic liquid at room temperature.The negatively charged ion of specifically enumerating during the preceding paragraph falls is the solvent that the tetramethyleneimine ionic compound of bis trifluoromethyl sulfimide especially can be used as synthesizing polyester (as PET), can anti-200 ℃ even higher temperature; And the pyrrolidines ionic compound that the preceding paragraph is specifically enumerated in falling is all stable to water.Therefore, pyrrolidines ionic compound of the present invention can be used as solvent, catalyzer etc. and is applied in fields such as organic synthesis, Polymer Synthesizing, Process Technologies of Polymer.
According to chemical structure, those skilled in the art will envision that, as will be as R 1Methyl C 2～C 6Straight chained alkyl substitutes, and/or will be as R 2The benzyl that replaces of nitro meet R of the present invention with other 2The benzene alkyl of definition substitutes, and the character of the pyrrolidines ionic compound of the present invention of gained obvious change can not take place, and still can bring into play as ion liquid function, for example as the solvent of synthesis of aromatic polyester.
According to a further aspect in the invention, provide a kind of method for preparing pyrrolidines ionic compound of the present invention.The preparation of pyrrolidines ionic compound of the present invention is according to its negatively charged ion B -Different and adopt different preparation methods.In preparation method of the present invention, according to the negatively charged ion difference, pyrrolidines ionic compound of the present invention can be divided into halogenide class and non-halide class.
Therefore, the invention provides wherein B of a kind of preparation -Be Cl -, Br -Or I -The method of halogenide pyrrolidines ionic compound, this method comprises:
Make following formula (III) compound:
Figure GSA00000121923000051
Wherein n and Y define for formula (II) as mentioned, and X ' is chlorine, bromine or iodine,
With the reaction of following formula (IV) compound,
Figure GSA00000121923000052
R wherein 1Define for formula (I) as mentioned,
Obtain general formula A of the present invention +B -The pyrrolidines ionic compound, B wherein -Be Cl -, Br -Or I -, and A +General formula A as mentioned +B -The middle definition.
Reaction among the above-mentioned preparation method is conventional to those skilled in the art.
Method produced according to the present invention advantageously before formula (III) compound and formula (IV) compound are reacted, need be carried out purification process with them and solvent.Formula (III) compound can use with equimolar amount or molar excess with respect to formula (IV) compound, preferably uses with molar excess, and for example the mole dosage ratio of the former with the latter can be 1.0: 1～1.5: 1.
The reaction of formula (III) compound and formula (IV) compound is carried out in the presence of solvent usually.This solvent is included in any solvent that does not participate in this chemical reaction under the reaction conditions of formula (III) compound and formula (IV) compound and be liquid form, can mention ethyl acetate, toluene, tetrahydrofuran (THF) etc. to this, preferably use the solvent of ethyl acetate as this reaction.These solvents can singlely use, and also can compoundly use.The consumption of solvent is conventional, as long as formula (III) compound and formula (IV) compound are successfully reacted; Usually, the consumption of solvent (especially ethyl acetate) should make: the ratio of the integral molar quantity of the molar weight of this solvent and reactant (that is, formula (III) compound and formula (IV) compound) is 5: 1～10: 1; Advantageously, the consumption of solvent (especially ethyl acetate) should make: the ratio of the molar weight of the integral molar quantity of this solvent and formula (IV) compound is 10: 1～20: 1.
In above-mentioned preparation method of the present invention, interpolation or hybrid mode for solvent and reactant, both can be in advance formula (III) compound and formula (IV) compound be dissolved in respectively and formed solution in the solvent, and then the solution of formula (III) compound dropwise splashed in the solution of formula (IV) compound, perhaps the solution with formula (IV) compound dropwise splashes in the solution of formula (III) compound, a kind of being dissolved in formula (III) compound and formula (IV) compound can also be formed solution in the solvent, then this solution is mixed with another kind in formula (III) compound and formula (IV) compound, for example formula (III) compound dissolution is formed solution in solvent, then formula (IV) compound slowly is added drop-wise in the solution of formula (III) compound for preparing or the drips of solution of formula (III) compound for preparing is added in formula (IV) compound.
In a preferred embodiment of the inventive method, with formula (III) compound and formula (IV) compound is to be dissolved in this solvent in 1: 5～1: 10 with the mol ratio with solvent respectively, form the solution of formula (III) compound and the solution of formula (IV) compound respectively, the solution with formula (III) compound dropwise splashes in the solution of formula (IV) compound then.
The temperature of reaction and the reaction pressure of the reaction between formula (III) compound that relates among the above-mentioned preparation method of the present invention and formula (IV) compound are conventional.Usually, this reaction can be carried out under 20～50 ℃, and reaction pressure is preferably autogenous pressure.The time of this reaction is depended on multiple factor, for example productive rate and temperature of reaction, and for economic aim, this reaction was carried out 1～24 hour usually.This reaction can also under agitation be carried out, and any agitator that is suitable for this purpose can use, and comprises paddle stirrer, magnetic stirring apparatus etc.
According to the present invention advantageously, the active degree of the concrete hybrid mode of reactant and solvent and solvent (especially ethyl acetate) add-on visual response thing and deciding.
For example, be formula (III) compound of chlorine during when adopting X ' as reactant because the reactive behavior of this compound is low, therefore, can adopt a small amount of solvent (especially ethyl acetate) to dilute, and with disposable the joining in the reactor of formula (IV) compound.In this case advantageously, reaction mixture is heated to little back flow reaction of boiling after feeding intake.
When adopting n wherein is 1 formula (III) compound during as reactant, its reactive behavior height, and the exothermic heat of reaction amount is big, can strengthen the consumption of solvent (for example ethyl acetate) or diluting reaction thing or mix in the mode that drips in advance.For example, all be dissolved in the solvent respectively formula (III) compound and formula (IV) compound, form two kinds of solution, and then with these two kinds of solution mixing, perhaps formula (IV) compound dissolution is formed solution in solvent, then with the disposable adding of formula (III) compound or slowly be added drop-wise in the gained solution.In this case advantageously, suitably adopt temperature in the ice-water bath controlling reactor, to prevent to react very exothermic and side reaction generation.
After reaction is finished, from reaction mixture, separate and remove employed solvent, for example by decant or suction filtration, to remove most of solvent,, then products therefrom is vacuumized as ethyl acetate, removing volatile component remaining in the pyrrolidines ionic compound, thereby obtain wherein B -Be Cl -, Br -Or I -Anionic pyrrolidines ionic compound of the present invention.
Making wherein B -On the basis for the pyrrolidines ionic compound of the present invention of halide anion, can make other type pyrrolidines ionic compound of the present invention by ion exchange.
Therefore, as the negatively charged ion B of pyrrolidines ionic compound of the present invention -During for non-halide anion, the method for preparing pyrrolidines ionic compound of the present invention comprises:
(a) according to above-mentioned preparation B wherein -Method for the pyrrolidines ionic compound of the present invention of halide anion makes B -Halogenide pyrrolidines ionic compound for halide anion; And
(b1) make halogenide pyrrolidines ionic compound and the silver nitrate aqueous solution reaction that obtains in the step (a), make the halogen ion generate precipitation, thereby obtain wherein B -Pyrrolidines ionic compound of the present invention for nitrate radical; Perhaps
(b2) the halogenide pyrrolidines ionic compound that obtains in the step (a) and Tetrafluoroboric acid or its an alkali metal salt are reacted in the presence of dehydrated alcohol, obtain wherein B -Pyrrolidines ionic compound of the present invention for tetrafluoroborate; Perhaps
(b3) make the halogenide pyrrolidines ionic compound that obtains in the step (a) and the reactant aqueous solution of phosphofluoric acid or its an alkali metal salt, obtain wherein B -Pyrrolidines ionic compound of the present invention for hexafluoro-phosphate radical; Perhaps
(b4) make the reactant aqueous solution of lithium, sodium or the sylvite of the halogenide pyrrolidines ionic compound that obtains in the step (a) and bis trifluoromethyl sulfimide, obtain wherein B -Pyrrolidines ionic compound of the present invention for bis trifluoromethyl sulfimide root; Perhaps
(b5) make the halogenide pyrrolidines ionic compound that obtains in the step (a) and the reactant aqueous solution of lead acetate or silver acetate, make the halogen ion generate precipitation, obtain wherein B -Pyrrolidines ionic compound of the present invention for acetate moiety; Perhaps
(b6) make the halogenide pyrrolidines ionic compound that obtains in the step (a) and the reactant aqueous solution of tosic acid or trifluoromethanesulfonic acid, make the halogen ion generate haloid acid, obtain wherein B -Be respectively the pyrrolidines ionic compound of the present invention of tosic acid root or trifluoromethanesulfonic acid root; Perhaps
(b7) make halogenide pyrrolidines ionic compound and the aqueous solution of phosphoric acid or its aqueous solution or phosphoric acid alkali metal salt or the reactant aqueous solution of the vitriol oil or its aqueous solution or sulfuric acid an alkali metal salt that obtains in the step (a), make the halogen ion generate haloid acid or alkali metal halide, obtain wherein B -Be respectively the pyrrolidines ionic compound of the present invention of phosphate radical or sulfate radical.
In above-mentioned preparation method's step (b1), advantageously, with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, afterwards again with the aqueous solution of Silver Nitrate.With respect to halogenide pyrrolidines ionic compound, Silver Nitrate preferably uses with equimolar amount.The temperature of the reaction in the step (b1) has no particular limits, and advantageously at room temperature carries out, and reaction pressure is preferably autogenous pressure.The time of this reaction is depended on multiple factor, for example productive rate and temperature of reaction, and for economic aim, this reaction was carried out 1～24 hour usually.This reaction can also under agitation be carried out, and any agitator that is suitable for this purpose can use, and comprises paddle stirrer, magnetic stirring apparatus etc.Reaction in the step (b1) makes the halogen ion (comprise Cl -, Br -And I -Negatively charged ion) form with silver halide precipitates.After reaction is finished, filter, and, preferably revolve steaming, promptly obtain B the filtrate evaporation -Pyrrolidines ionic compound of the present invention for nitrate radical.
In an especially preferred embodiment, in step (b1), with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, mix with the Silver Nitrate of the equimolar amount that is aqueous solution form more afterwards, at room temperature reaction, make halide anion generate silver halide precipitation, filter, and with the filtrate evaporation, thereby wherein B obtained -Pyrrolidines ionic compound of the present invention for nitrate radical.
In above-mentioned preparation method's step (b2), advantageously, with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the dehydrated alcohol, mix with Tetrafluoroboric acid or its an alkali metal salt more afterwards.With respect to Tetrafluoroboric acid or its an alkali metal salt, this halogenide pyrrolidines ionic compound can use or excessive use with equimolar amount, and preferably the two uses with equimolar amount.The temperature of the reaction in the step (b2) has no particular limits, and advantageously at room temperature carries out, and reaction pressure is preferably autogenous pressure.The time of this reaction is depended on multiple factor, for example productive rate and temperature of reaction, and for economic aim, this reaction was carried out 1～24 hour usually.This reaction can also under agitation be carried out, and any agitator that is suitable for this purpose can use, and comprises paddle stirrer, magnetic stirring apparatus etc.After reaction is finished, under the situation of using Tetrafluoroboric acid, filtrate is evaporated, preferably revolve steaming, and under the situation of using the Tetrafluoroboric acid an alkali metal salt, isolate lower floor's solid, filtrate is revolved steaming to remove a large amount of dehydrated alcohols, to revolve the mixture suction filtration that obtains after steaming to remove residual inorganic salt, promptly obtain wherein B -Pyrrolidines ionic compound of the present invention for tetrafluoroborate.
For the present invention, an alkali metal salt of above-mentioned Tetrafluoroboric acid refers to the lithium of Tetrafluoroboric acid, sodium, potassium, rubidium and cesium salt, preferably its lithium, sodium and sylvite.
In an especially preferred embodiment, in step (b2), with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the dehydrated alcohol, mix with Tetrafluoroboric acid or its an alkali metal salt of equimolar amount more afterwards, at room temperature stirring reaction is 1～24 hour, after reaction is finished, under the situation of using Tetrafluoroboric acid, filtrate is evaporated, preferably revolve steaming, and under the situation of using the Tetrafluoroboric acid an alkali metal salt, filter to isolate lower floor's solid, filtrate is revolved steaming to remove a large amount of dehydrated alcohols, will revolve the mixture suction filtration that obtains after steaming, promptly obtain wherein B to remove residual inorganic salt -Pyrrolidines ionic compound of the present invention for tetrafluoroborate.
In above-mentioned preparation method's step (b3), advantageously, with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, afterwards again with the aqueous solution of phosphofluoric acid or its an alkali metal salt.With respect to phosphofluoric acid or its an alkali metal salt, this halogenide pyrrolidines ionic compound can use or excessive use with equimolar amount, and preferably the two uses with equimolar amount.The temperature of the reaction in the step (b3) has no particular limits, and advantageously at room temperature carries out, and reaction pressure is preferably autogenous pressure.The time of this reaction is depended on multiple factor, for example productive rate and temperature of reaction, and for economic aim, this reaction was carried out 1～24 hour usually.This reaction can also under agitation be carried out, and any agitator that is suitable for this purpose can use, and comprises paddle stirrer, magnetic stirring apparatus etc.Reaction is isolated lower floor's oil phase or solid after finishing, and uses the deionized water repetitive scrubbing, and the halogen negatively charged ion (comprises Cl in washings -, Br -And I -Negatively charged ion) (this can check by Silver Nitrate and verify,, silver nitrate aqueous solution is splashed into whether observation has precipitation to judge in the washings that is) promptly obtains wherein B till -Pyrrolidines ionic compound of the present invention for hexafluoro-phosphate radical.
For the present invention, an alkali metal salt of above-mentioned phosphofluoric acid refers to the lithium of phosphofluoric acid, sodium, potassium, rubidium and cesium salt, preferably its lithium, sodium and sylvite.
In an especially preferred embodiment, in step (b3), with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, mix with phosphofluoric acid or its an alkali metal salt of the equimolar amount that is aqueous solution form more afterwards, at room temperature stirring reaction is 1～24 hour, isolate lower floor's oil phase or solid, use the deionized water repetitive scrubbing, in washings till the halogen negatively charged ion, thereby obtain wherein B -Pyrrolidines ionic compound of the present invention for hexafluoro-phosphate radical.
In above-mentioned preparation method's step (b4), advantageously, with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, afterwards again with the aqueous solution of lithium, sodium or the sylvite of bis trifluoromethyl sulfimide.With respect to lithium, sodium or the sylvite of bis trifluoromethyl sulfimide, this halogenide pyrrolidines ionic compound can use or excessive use with equimolar amount, and preferably the two uses with equimolar amount.Temperature of reaction in the step (b4) has no particular limits, and advantageously at room temperature carries out, and reaction pressure is preferably autogenous pressure.The time of this reaction is depended on multiple factor, for example productive rate and temperature of reaction, and for economic aim, this reaction was carried out 1～24 hour usually.This reaction can also under agitation be carried out, and any agitator that is suitable for this purpose can use, and comprises paddle stirrer, magnetic stirring apparatus etc.Reaction is isolated lower floor's oil phase or solid after finishing, and uses the deionized water repetitive scrubbing, and the halogen negatively charged ion (comprises Cl in washings -, Br -And I -Negatively charged ion) (this can check by Silver Nitrate and verify,, silver nitrate aqueous solution is splashed into whether observation has precipitation to judge in the washings that is) promptly obtains wherein B till -Pyrrolidines ionic compound of the present invention for bis trifluoromethyl sulfimide root.
In an especially preferred embodiment, in step (b4), with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, mix with lithium, sodium or the sylvite of the bis trifluoromethyl sulfimide of the equimolar amount that is aqueous solution form more afterwards, at room temperature stirring reaction is 1～24 hour, isolate lower floor's oil phase or solid, use the deionized water repetitive scrubbing, in washings till the halogen negatively charged ion, thereby obtain wherein B -Pyrrolidines ionic compound of the present invention for bis trifluoromethyl sulfimide root.
In above-mentioned preparation method's step (b5), advantageously, with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, afterwards again with the aqueous solution of lead acetate or silver acetate.With respect to lead acetate or silver acetate, this halogenide pyrrolidines ionic compound preferably uses with stoichiometric quantity.Temperature of reaction in the step (b5) has no particular limits, and advantageously at room temperature carries out, and reaction pressure is preferably autogenous pressure.The time of this reaction is depended on multiple factor, for example productive rate and temperature of reaction, and for economic aim, this reaction was carried out 1～24 hour usually.This reaction can also under agitation be carried out, and is applicable to that any agitator of this purpose can use, and comprises paddle stirrer, magnetic stirring apparatus etc.Reaction in the step (b5) makes the halogen ion (comprise Cl -, Br -And I -Negatively charged ion) form with lead halide or silver halide precipitates.After reaction is finished, filter,, promptly obtain B the filtrate evaporation -Pyrrolidines ionic compound of the present invention for acetate moiety.
In an especially preferred embodiment, in step (b5), with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, mix with the lead acetate or the silver acetate of the stoichiometric quantity that is aqueous solution form more afterwards, reaction at room temperature, make halide anion generate lead halide or silver halide precipitation, filter, with the filtrate evaporation, thereby obtain wherein B -Pyrrolidines ionic compound of the present invention for acetate moiety.
In above-mentioned preparation method's step (b6), advantageously, with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, afterwards again with the aqueous solution of tosic acid or trifluoromethanesulfonic acid.With respect to tosic acid or trifluoromethanesulfonic acid, halogenide pyrrolidines ionic compound preferably uses with equimolar amount.Temperature of reaction in the step (b6) has no particular limits, and advantageously at room temperature carries out, and reaction pressure is preferably autogenous pressure.The time of this reaction is depended on multiple factor, for example productive rate and temperature of reaction, and for economic aim, this reaction was carried out 1～24 hour usually.This reaction can also under agitation be carried out, and is applicable to that any agitator of this purpose can use, and comprises paddle stirrer, magnetic stirring apparatus etc.Reaction in the step (b6) makes the halogen ion (comprise Cl -, Br -And I -Negatively charged ion) generates haloid acid, from reaction system, discharge with the form of hydrogen halide.After reaction is finished,, preferably revolve steaming, promptly obtain B the filtrate evaporation -Be respectively the pyrrolidines ionic compound of the present invention of tosic acid root or trifluoromethanesulfonic acid root.
In an especially preferred embodiment, in step (b6), with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, mix with the tosic acid or the trifluoromethanesulfonic acid of the equimolar amount that is aqueous solution form more afterwards, under room temperature and autogenous pressure, react, make halide anion generate haloid acid, with the filtrate evaporation, thereby obtain wherein B -Be respectively the pyrrolidines ionic compound of the present invention of tosic acid root or trifluoromethanesulfonic acid root.
In above-mentioned preparation method's step (b7), advantageously, with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, again the aqueous solution of phosphoric acid or its aqueous solution or phosphoric acid alkali metal salt or the aqueous solution of the vitriol oil or its aqueous solution or sulfuric acid an alkali metal salt are added dropwise to wherein afterwards.With respect to halogenide pyrrolidines ionic compound, the aqueous solution of the aqueous solution of phosphoric acid or its aqueous solution or phosphoric acid alkali metal salt or the vitriol oil or its aqueous solution or sulfuric acid an alkali metal salt preferably uses with stoichiometric quantity.Temperature of reaction in the step (b7) is not particularly limited, and advantageously carries out under-10～0 ℃, and reaction pressure is preferably autogenous pressure.The time of this reaction is depended on multiple factor, for example productive rate and temperature of reaction, and for economic aim, this reaction was carried out 1～24 hour usually.This reaction can also under agitation be carried out, and is applicable to that any agitator of this purpose can use, and comprises paddle stirrer, magnetic stirring apparatus etc.Reaction in the step (b7) makes the halogen ion (comprise Cl -, Br -And I -Negatively charged ion) generates haloid acid or alkali metal halide.After reaction is finished, under the situation of using phosphoric acid or its aqueous solution or the vitriol oil or its aqueous solution, filtrate is evaporated, preferably revolve steaming, and under the situation of the aqueous solution that uses phosphoric acid alkali metal salt or sulfuric acid an alkali metal salt, alkali metal halide is separated out the filtrate cooling, again filtrate is evaporated after the filtration, preferably revolve steaming, promptly obtain B -Be respectively the pyrrolidines ionic compound of the present invention of phosphate radical or sulfate radical.
For the present invention, above-mentioned phosphoric acid alkali metal salt and sulfuric acid an alkali metal salt refer to phosphoric acid and sulfuric acid lithium, sodium, potassium, rubidium and cesium salt separately, preferably their lithium, sodium and sylvite separately.
In an especially preferred embodiment, in step (b7), with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, again the aqueous solution of phosphoric acid or its aqueous solution or phosphoric acid alkali metal salt or the aqueous solution of the vitriol oil or its aqueous solution or sulfuric acid an alkali metal salt are added dropwise to wherein afterwards, under-10～0 ℃ and autogenous pressure, react, make halide anion generate haloid acid or alkali metal halide, under the situation of using phosphoric acid or its aqueous solution or the vitriol oil or its aqueous solution, filtrate is evaporated, and cooling filtrate is separated out alkali metal halide under the situation of the aqueous solution that uses phosphoric acid alkali metal salt or sulfuric acid an alkali metal salt, again filtrate is evaporated after the filtration, thereby obtain wherein B -Be respectively the pyrrolidines ionic compound of the present invention of phosphate radical or sulfate radical.
Embodiment
Following examples are used to illustrate pyrrolidines ionic compound of the present invention and preparation method thereof, but these embodiment do not constitute limitation of the scope of the invention.
Embodiment 1: N-(2-nitrobenzyl)-N-crassitude bromide synthetic
Figure GSA00000121923000131
Take by weighing 2-nitrobenzyl bromine 10.80g (50mmol) and N-crassitude 4.26g (50mmol) and be dissolved in wiring solution-forming in 50mL (0.50mol) ethyl acetate respectively.Under agitation condition, the ethyl acetate solution of 2-nitrobenzyl bromine slowly is added drop-wise in the ethyl acetate solution of N-crassitude, stirring reaction is 8 hours under the room temperature.Filter to isolate solid product, and wash solid product 8 times with new distillatory ethyl acetate, each consumption 20mL, volatile component is taken off in vacuum-drying then, obtains the pale solid powder.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 98%.FTIR(cm -1)：3465，3391，3032，3015，1605，1575，1527，1480，1457，1348，1007，935，915，860，792，753，711。 1H?NMR(D 2O)：δ＝8.14-8.16(m，1H)，7.68-7.78(m，3H)，4.94(s，2H)，3.47-3.49(m，4H)，2.90(s，3H)，2.13-2.15(t，4H)ppm。Fusing point: 110 ℃; Heat decomposition temperature: 190 ℃.
Embodiment 2: N-(3-nitrobenzyl)-N-crassitude bromide synthetic
Figure GSA00000121923000132
Take by weighing 3-nitrobenzyl bromine 10.80g (50mmol) and be dissolved in wiring solution-forming in 25mL (0.25mol) ethyl acetate, take by weighing N-crassitude 4.26g (50mmol) and be dissolved in wiring solution-forming in 70mL (0.70mol) ethyl acetate.Under agitation condition, the ethyl acetate solution of 3-nitrobenzyl bromine slowly is added drop-wise in the ethyl acetate solution of N-crassitude, stirring reaction is 8 hours under the room temperature.Filter to isolate solid product, and wash solid product 8 times with new distillatory ethyl acetate, each consumption 20mL, volatile component is taken off in vacuum-drying then, obtains the pale solid powder.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 93%.FTIR(cm -1)：3069，3003，2960，2892，1532，1474，1459，1351，1090，878，902，819，808，747，723，699，675。 1H?NMR(D 2O)：δ＝8.33-8.36(m，2H)，7.87-7.89(d，1H)，7.67-7.71(t，1H)，4.58(s，2H)，3.57-3.59(m，2H)，3.39-3.43(m，2H)，2.91(s，3H)，2.15-2.21(m，4H)ppm。Fusing point: 150 ℃; Heat decomposition temperature: 230 ℃.
Embodiment 3: N-(4-nitrobenzyl)-N-crassitude bromide synthetic
Figure GSA00000121923000141
Take by weighing 4-nitrobenzyl bromine 10.80g (50mmol), be dissolved in wiring solution-forming in 30mL (0.30mol) ethyl acetate, take by weighing N-crassitude 4.26g (50mmol) and be dissolved in wiring solution-forming in 50mL (0.50mol) ethyl acetate.Under agitation condition, the ethyl acetate solution of 4-nitrobenzyl bromine slowly is added drop-wise in the ethyl acetate solution of N-crassitude, stirring reaction is 8 hours under the room temperature.Filter to isolate solid product, and wash solid product 8 times with new distillatory ethyl acetate, each consumption 20mL, volatile component is taken off in vacuum-drying then, obtains the light yellow solid powder.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 95%.FTIR(cm -1)：3038，3007，2963，2886，1605，1527，1461，1346，1105，1076，1013，881，857，838，722，703。 1H?NMR(D 2O)：δ＝8.29-8.31(m，2H)，7.73-7.76(m，2H)，4.60(s，2H)，3.59-3.62(m，2H)，3.42-3.47(m，2H)，2.94(s，3H)，2.18-2.23(m，4H)ppm。Fusing point: 160 ℃; Heat decomposition temperature: 220 ℃.
Embodiment 4: N-(4-nitrobenzyl)-N-crassitude a tetrafluoro borate synthetic
Figure GSA00000121923000142
Take by weighing N-(4-nitrobenzyl)-N-crassitude bromide 3.01g (10mmol) and be dissolved in the 30mL dehydrated alcohol, take by weighing sodium tetrafluoroborate 1.10g (10mmol), join in the above-mentioned solution, stirring reaction is 24 hours under room temperature.Filter to isolate lower floor's solid, filtrate is revolved to steam afterwards and remove dehydrated alcohol, will revolve the mixture suction filtration that obtains after steaming to remove residual inorganic salt.The filtrate vacuum-drying that will so obtain afterwards 24 hours obtains light yellow liquid.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 50%.FTIR(cm -1)：3112，2970，1608，1525，1475，1352，1214，1187，1062，973，918，874，857，832，758，705。 1H?NMR(D 2O)：δ＝8.25-8.27(d，2H)，7.69-7.71(d，2H)，4.55(s，2H)，3.53-3.58(m，2H)，3.37-3.42(m，2H)，2.89(s，3H)，2.14-2.19(m，4H)ppm。Heat decomposition temperature: 280 ℃.
Embodiment 5: N-(4-nitrobenzyl)-N-crassitude hexafluorophosphate synthetic
Figure GSA00000121923000151
Take by weighing N-(4-nitrobenzyl)-N-crassitude bromide 3.01g (10mmol) and be dissolved in the 30mL deionized water, take by weighing Potassium Hexafluorophosphate 1.84g (10mmol) and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed, and stirring reaction is 24 hours under room temperature.The gained system is filtered isolating solid product, and till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying afterwards 24 hours obtains white powdery solid with deionized water repetitive scrubbing solid product.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 81%.FTIR(cm -1)：3119，3080，3024，2987，2957，2908，2866，1601，1530，1479，1467，1358，1212，1192，848，557。 1H?NMR(d-DMSO)：δ＝8.16-8.18(d，2H)，7.67-7.69(d，2H)，4.52(s，2H)，3.39-3.41(m，2H)，3.23-3.27(m，2H)，2.73(s，3H)，1.94-1.96(m，4H)ppm。Fusing point: 150 ℃; Heat decomposition temperature: 290 ℃.
Embodiment 6: N-(2-nitrobenzyl)-N-crassitude bis trifluoromethyl sulfimide salt synthetic
Figure GSA00000121923000152
Take by weighing N-(2-nitrobenzyl)-N-crassitude bromide 3.01g (10mmol) and be dissolved in the 30mL deionized water, take by weighing bis trifluoromethyl sulfimide lithium 2.87g (10mmol) and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed under agitation condition, and stirring reaction is 24 hours under room temperature.The gained system is filtered isolating solid product, and till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying afterwards 24 hours obtains pale solid with deionized water repetitive scrubbing solid product.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 92%.FTIR(cm -1)：3119，3064，3034，2981，2923，1610，1580，1537，1477，1455，1357，1204，1142，1059，929，907，861，833，798，762，741，705，622，611，569，514。 1H?NMR(d-DMSO)：δ＝8.14-8.16(m，1H)，7.82-7.88(m，3H)，4.93(s，2H)，3.50(b，4H)，2.85(s，3H)，2.09(b，4H)ppm。Fusing point: 60 ℃; Heat decomposition temperature: 300 ℃.
Embodiment 7: N-(3-nitrobenzyl)-N-crassitude bis trifluoromethyl sulfimide salt synthetic
Figure GSA00000121923000161
Take by weighing N-(3-nitrobenzyl)-N-crassitude bromide 3.01g (10mmol) and be dissolved in the 30mL deionized water, take by weighing bis trifluoromethyl sulfimide lithium 2.87g (10mmol) and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed under agitation condition, and stirring reaction is 24 hours under room temperature.The gained system is filtered isolating solid product, and till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying afterwards obtained white solid after 24 hours with deionized water repetitive scrubbing solid product.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 85%.FTIR(cm -1)：3097，3080，3045，2996，2899，1619，1544，1480，1464，1358，1198，1139，1049，810，791，741，703，675，615，570，514。 1H?NMR(d-DMSO)：δ＝8.48(s，1H)，8.38-8.40(d，1H)，8.01-8.03(d，1H)，7.79-7.83(t，1H)，4.72(s，2H)，3.57-3.59(m，2H)，3.40-3.44(m，2H)，2.92(s，3H)，2.13-2.14(m，4H)ppm。Fusing point: 60 ℃; Heat decomposition temperature: 325 ℃.
Embodiment 8: N-(4-nitrobenzyl)-N-crassitude bis trifluoromethyl sulfimide salt synthetic
Figure GSA00000121923000162
Take by weighing N-(4-nitrobenzyl)-N-crassitude bromide 3.01g (10mmol) and be dissolved in the 30mL deionized water, take by weighing bis trifluoromethyl sulfimide lithium 2.87g (10mmol) and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed under agitation condition, and stirring reaction is 24 hours under room temperature.Outwell the upper strata water, till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying afterwards 24 hours obtains yellow liquid with deionized water repetitive scrubbing lower floor oil phase.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 76%.FTIR(cm -1)：3119，3085，2983，1610，1529，1477，1464，1352，1194，1138，1056，856，830，789，704，653。 1H?NMR(d-DMSO)：δ＝8.32-8.34(m，2H)，7.84-7.86(m，2H)，4.69(s，2H)，3.56-3.59(m，2H)，3.40-3.44(m，2H)，2.90(s，3H)，2.12-2.13(m，4H)ppm。Heat decomposition temperature: 310 ℃.
Embodiment 9: N-(4-methyl-benzyl)-N-crassitude bromide synthetic
Figure GSA00000121923000171
Take by weighing 4-methyl-benzyl bromine 9.25g (50mmol) and N-crassitude 4.26g (50mmol) and be dissolved in wiring solution-forming in 50mL (0.50mol) ethyl acetate respectively.Under agitation condition, the ethyl acetate solution of 4-methyl-benzyl bromine slowly is added drop-wise in the ethyl acetate solution of N-crassitude, stirring reaction is 8 hours under the room temperature.Filter to isolate solid product, and wash solid product 8 times with new distillatory ethyl acetate, each consumption 20mL, volatile component is taken off in vacuum-drying then, obtains the white solid powder.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 88%.FTIR(cm -1)：3014，2958，2891，1623，1517，1456，1424，1404，1381，934，921，811，759，634，585，485。 1H?NMR(D 2O)：δ＝7.27-7.36(m，4H)，4.37(s，2H)，3.50-3.53(m，2H)，3.30-3.33(m，2H)，2.86(s，3H)，2.29(s，3H)，2.13-2.14(d，4H)ppm。Fusing point: 70 ℃; Heat decomposition temperature: 240 ℃.
Embodiment 10: N-(4-methyl-benzyl)-N-crassitude bis trifluoromethyl sulfimide salt synthetic
Figure GSA00000121923000172
Take by weighing N-(4-methyl-benzyl)-N-crassitude bromide 2.70g (10mmol) and be dissolved in the 30mL deionized water, take by weighing 2.87g (10mmol) bis trifluoromethyl sulfimide lithium and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed under agitation condition, and stirring reaction is 24 hours under room temperature.Outwell the upper strata water, till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying afterwards 24 hours obtains colourless liquid with deionized water repetitive scrubbing lower floor oil phase.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 74%.FTIR(cm -1)：3033，2982，2927，1615，1517，1477，1464，1429，1352，1197，1138，1056，930，816，789，761，740，654，617，570。 1H?NMR(d-DMSO)：δ＝7.29-7.44(m，4H)，4.47(s，2H)，3.50-3.53(t，2H)，3.32-3.36(t，2H)，2.85(s，3H)，2.34(s，3H)，2.09-2.10(m，4H)ppm。Heat decomposition temperature: 350 ℃.
Embodiment 11: N-(4-nitrobenzyl)-N-n-butylpyrrolioine bromide synthetic
Figure GSA00000121923000181
Take by weighing 4-nitrobenzyl bromine 10.80g (50mmol) and N-n-butylpyrrolioine 6.35g (50mmol), be dissolved in wiring solution-forming in 50mL (0.50mol) ethyl acetate respectively.Under agitation condition, the ethyl acetate solution of 4-nitrobenzyl bromine slowly is added drop-wise in the ethyl acetate solution of N-n-butylpyrrolioine, stirring reaction is 5 hours under the room temperature.Filter to isolate solid product, and wash solid product 8 times with new distillatory ethyl acetate, each consumption 20mL, volatile component is taken off in vacuum-drying then, obtains the white solid powder.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 87%.FTIR(cm -1)：3415，3043，2999，2958，2876，1608，1520，1457，1399，1348，1219，1189，1106，1004，938，871，858，828，721，705，604，511。 1H?NMR(D 2O)：δ＝8.26-8.28(d，2H)，7.68-7.70(d，2H)，4.53(s，2H)，3.51-3.54(m，2H)，3.42-3.45(m，2H)，3.05-3.09(t，2H)，2.12-2.13(m，4H)，1.77-1.85(m，2H)，1.23-1.33(m，2H)，0.84-0.88(t，3H)ppm。Fusing point: 80 ℃; Heat decomposition temperature: 220 ℃.
Embodiment 12: N-(4-nitrobenzyl)-N-n-butylpyrrolioine bis trifluoromethyl sulfimide salt synthetic
Take by weighing N-(4-nitrobenzyl)-N-n-butylpyrrolioine bromide 3.43g (10mmol) and be dissolved in the 30mL deionized water, take by weighing 2.87g (10mmol) bis trifluoromethyl sulfimide lithium and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed under agitation condition, and stirring reaction is 24 hours under room temperature.The gained system is filtered isolating solid product, and till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying afterwards 24 hours obtains white powdery solid with deionized water repetitive scrubbing solid product.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 92%.FTIR(cm -1)：3111，3072，2971，2881，1605，1526，1471，1456，1350，1324，1194，1143，1132，1055，923，893，877，860，821，797，754，740，707，612，569，513，408。 1H?NMR(d-DMSO)：δ＝8.34-8.37(d，2H)，7.84-7.86(d，2H)，4.67(d，2H)，3.46-3.54(m，4H)，3.06(t，2H)，2.06-2.08(m，4H)，1.78-1.86(m，2H)，1.26-1.33(m，2H)，0.94-0.96(t，3H)ppm。Fusing point: 50 ℃; Heat decomposition temperature: 310 ℃.
Embodiment 13: N-(4-nitrobenzyl)-N-isobutyl-tetramethyleneimine bromide synthetic
Take by weighing 4-nitrobenzyl bromine 10.80g (50mmol) and N-isobutyl-tetramethyleneimine 6.35g (50mmol), be dissolved in wiring solution-forming in 50mL (0.50mol) ethyl acetate respectively.Under agitation condition, the ethyl acetate solution of 4-nitrobenzyl bromine slowly is added drop-wise in the ethyl acetate solution of N-isobutyl-tetramethyleneimine, stirring reaction is 24 hours under the room temperature.Filter to isolate solid product, and wash solid product 8 times with new distillatory ethyl acetate, each consumption 20mL, volatile component is taken off in vacuum-drying then, obtains the white solid powder.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 52%.FTIR(cm -1)：3448，3390，3100，3067，2968，2934，1623，1605，1523，1468，1347，1217，1107，1068，1030，917，875，857，834，724，698，616，541。 1H?NMR(D 2O)：δ＝8.26-8.28(d，2H)，7.68-7.70(d，2H)，4.57(s，2H)，3.51-3.56(m，2H)，3.44-3.49(m，2H)，3.05-3.06(d，2H)，2.33-2.39(m，1H)，2.10-2.13(m，4H)，1.02-1.03(d，6H)ppm。Fusing point: 70 ℃; Heat decomposition temperature: 220 ℃.
Embodiment 14: N-(4-nitrobenzyl)-N-isobutyl-tetramethyleneimine bis trifluoromethyl sulfimide salt synthetic
Figure GSA00000121923000201
Take by weighing N-(4-nitrobenzyl)-N-isobutyl-tetramethyleneimine bromide 3.43g (10mmol) and be dissolved in the 30mL deionized water, take by weighing 2.87g (10mmol) bis trifluoromethyl sulfimide lithium and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed under agitation condition, and stirring reaction is 12 hours under room temperature.The gained system is filtered isolating solid product, and till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying afterwards 24 hours obtains white powdery solid with deionized water repetitive scrubbing solid product.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 91%.FTIR(cm -1)：3112，3033，2982，2945，2879，1608，1527，1473，1342，1324，1182，1133，1055，971，920，895，871，858，788，741，705，655，595，570，509。 1H?NMR(d-DMSO)：δ＝8.35-8.37(d，2H)，7.84-7.86(d，2H)，4.70(s，2H)，3.48-3.53(m，4H)，3.08-3.10(d，2H)，2.32-2.33(m，1H)，2.02-2.04(m，4H)，1.05-1.06(d，6H)ppm。Fusing point: 40 ℃; Heat decomposition temperature: 310 ℃.
Embodiment 15: N-(4-nitrobenzyl)-N-crassitude acetate synthetic
Figure GSA00000121923000202
Take by weighing N-(4-nitrobenzyl)-N-crassitude bromide 3.01g (10mmol) and be dissolved in the 30mL deionized water, take by weighing 1.62g (5mmol) lead acetate and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed, and stirring reaction is 24 hours under room temperature.Remove by filter insolubles, filtrate is revolved steaming to remove big water gaging, vacuum-drying afterwards obtained yellow thick liquid to remove residuary water and volatile constituent in 24 hours.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 70%.FITR(cm -1)：3115，2963，1573，1521，1474，1402，1350，1214，1187，1110，1013，937，918，874，857，832，757，705。 1HNMR(D 2O)：δ＝8.23-8.25(d，2H)，7.69-7.71(d，2H)，4.55(s，2H)，3.53-3.57(m，2H)，3.38-3.42(m，2H)，2.89(s，3H)，2.14-2.19(m，4H)，1.79(s，3H)ppm。Heat decomposition temperature: 280 ℃.
Embodiment 16: N-(4-nitrobenzyl)-N-crassitude tosilate synthetic
Figure GSA00000121923000211
Take by weighing N-(4-nitrobenzyl)-N-crassitude bromide 3.01g (10mmol) and be dissolved in the 30mL deionized water, take by weighing 1.72g (10mmol) tosic acid and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed, and stirring reaction is 24 hours under room temperature.Revolve to steam and remove big water gaging, vacuum-drying afterwards obtained yellow liquid to remove residuary water and volatile constituent in 24 hours.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 80%.FITR(cm -1)：3113，2970，1693，1608，1525，1495，1462，1397，1350，1215，1123，1032，1007，936，916，873，856，819，757，704，681，564。 1HNMR(D 2O)：δ＝8.19-8.21(d，2H)，7.63-7.66(d，2H)，7.51-7.53(d，2H)，7.19-7.21(d，2H)，4.49(d，2H)，3.48-3.52(m，2H)，3.33-3.37(m，2H)，2.84(s，3H)，2.23(s，3H)，2.10-2.11(m，4H)ppm。Heat decomposition temperature: 270 ℃.
Embodiment 17: N-(4-nitrobenzyl)-N-allyl group tetramethyleneimine bromide synthetic
Figure GSA00000121923000212
Take by weighing 4-nitrobenzyl bromine 10.80g (50mmol) and N-allyl group tetramethyleneimine 5.55g (50mmol), be dissolved in wiring solution-forming in 50mL (0.50mol) ethyl acetate respectively.Under agitation condition, the ethyl acetate solution of 4-nitrobenzyl bromine slowly is added drop-wise in the ethyl acetate solution of N-allyl group tetramethyleneimine, stirring reaction is 24 hours under the room temperature.Filter to isolate solid product, and wash solid product 8 times with new distillatory ethyl acetate, each consumption 20mL, volatile component is taken off in vacuum-drying then, obtains the white solid powder.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 80%.FTIR(cm -1)：3421，3042，3006，2958，1605，1525，1462，1448，1428，1409，1351，1211，1108，1044，1005，982，963，906，871，857，736，704，601。 1H?NMR(D 2O)：δ＝8.23-8.26(d，2H)，7.68-7.71(d，2H)，5.99-6.09(m，1H)，5.63-5.66(d，1H)，5.56-5.60(d，1H)，4.52(s，2H)，3.75-3.77(d，2H)，3.45-3.47(m，4H)，2.08-2.10(m，4H)ppm。Fusing point: 80 ℃; Heat decomposition temperature: 210 ℃.
Embodiment 18: N-(4-nitrobenzyl)-N-propargyl tetramethyleneimine bromide synthetic
Take by weighing 4-nitrobenzyl bromine 10.80g (50mmol) and N-propargyl tetramethyleneimine 5.45g (50mmol), be dissolved in wiring solution-forming in 50mL (0.50mol) ethyl acetate respectively.Under agitation condition, the ethyl acetate solution of 4-nitrobenzyl bromine slowly is added drop-wise in the ethyl acetate solution of N-propargyl tetramethyleneimine, stirring reaction is 24 hours under the room temperature.Filter to isolate solid product, and wash solid product 8 times with new distillatory ethyl acetate, each consumption 20mL, volatile component is taken off in vacuum-drying then, obtains the light yellow solid powder.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 90%.FTIR(cm -1)：3171，3064，2964，2945，2917，2861，2117，1728，1607，1525，1468，1450，1352，1239，1042，885，870，858，832，719，702。 1H?NMR(D 2O)：δ＝8.24-8.26(d，2H)，7.77-7.79(d，2H)，4.02-4.04(m，1H)，3.94(s，2H)，3.59-3.62(m，4H)，2.11-2.20(m，4H)，1.95(s，1H)，1.11-1.14(t，1H)ppm。Fusing point: 70 ℃; Heat decomposition temperature: 220 ℃.
Embodiment 19: N-(4-nitrobenzyl)-N-allyl group tetramethyleneimine bis trifluoromethyl sulfimide salt synthetic
Figure GSA00000121923000222
Take by weighing N-(4-nitrobenzyl)-N-allyl group tetramethyleneimine bromide 3.27g (10mmol) and be dissolved in the 30mL deionized water, take by weighing 2.87g (10mmol) bis trifluoromethyl sulfimide lithium and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed under agitation condition, and stirring reaction is 12 hours under room temperature.The gained system is filtered isolating solid product, and till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying afterwards 24 hours obtains light yellow solid with deionized water repetitive scrubbing solid product.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 83%.FTIR(cm -1)：3125，3079，2979，2893，2863，2361，1610，1524，1461，1351，1191，1136，1107，1057，993，955，910，867，856，790，759，740，704，613，568，513。 1H?NMR(d-DMSO)：δ＝8.34-8.36(d，2H)，7.87-7.89(d，2H)，6.16-6.26(m，1H)，5.68-5.71(d，1H)，5.66-5.67(d，2H)，4.68(s，2H)，3.83-3.85(d，2H)，3.49(m，4H)，2.07-2.08(m，4H)ppm。Fusing point: 70 ℃; Heat decomposition temperature: 310 ℃.
Embodiment 20: N-(4-nitrobenzyl)-N-propargyl tetramethyleneimine bis trifluoromethyl sulfimide salt synthetic
Figure GSA00000121923000231
Take by weighing N-(4-nitrobenzyl)-N-propargyl tetramethyleneimine bromide 3.25g (10mmol) and be dissolved in the 30mL deionized water, take by weighing 2.87g (10mmol) bis trifluoromethyl sulfimide lithium and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed under agitation condition, and stirring reaction is 12 hours under room temperature.The gained system is filtered isolating solid product, and till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying afterwards 24 hours obtains light yellow powdery solid with deionized water repetitive scrubbing solid product.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 83%.FTIR(cm -1)：3282，3128，2987，2966，2136，1611，1524，1472，1457，1351，1327，1190，1136，1056，1005，931，912，869，856，792，761，741，703，611，569，514。 1H?NMR(d-DMSO)：δ＝8.36-8.38(d，2H)，7.87-7.89(d，2H)，4.76(s，2H)，4.17(s，2H)，4.16(m，1H)，3.53-3.67(m，4H)，2.12-2.17(m，4H)ppm。Fusing point: 90 ℃; Heat decomposition temperature: 310 ℃.
Embodiment 21: N-styroyl-N-crassitude bromide synthetic
Figure GSA00000121923000241
Take by weighing 2-phenyl-bromide ethane 9.25g (50mmol) and N-crassitude 4.26g (50mmol), be dissolved in wiring solution-forming in 50mL (0.50mol) ethyl acetate respectively.Under agitation condition, the ethyl acetate solution of 2-phenyl-bromide ethane is added drop-wise in the ethyl acetate solution of N-crassitude, stirring reaction is 24 hours under the room temperature.Filter to isolate solid product, and wash solid product 8 times with new distillatory ethyl acetate, each consumption 20mL, volatile component is taken off in vacuum-drying then, obtains light yellow solid.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 80%.FTIR(cm -1)：3058，3021，3000，2969，2954，2887，1601，1583，1456，1181，1088，1045，1015，993，966，932，759，702，552，509。 1HNMR(D 2O)：δ＝7.37-7.39(m，2H)，7.32-7.33(m，3H)，3.55-3.58(t，2H)，3.52-3.54(m，4H)，3.12-3.16(t，2H)，3.10(s，3H)，2.19(b，4H)ppm。Fusing point: 110 ℃; Heat decomposition temperature: 250 ℃.
Embodiment 22: N-styroyl-N-crassitude hexafluorophosphate synthetic
Figure GSA00000121923000242
Take by weighing N-styroyl-N-crassitude bromide 2.70g (10mmol) and be dissolved in the 30mL deionized water, take by weighing Potassium Hexafluorophosphate 1.84g (10mmol) and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed, and stirring reaction is 24 hours under room temperature.The gained system is filtered isolating solid product, and till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying afterwards 24 hours obtains white solid with deionized water repetitive scrubbing solid product.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 62%.FTIR(cm -1)：3076，3033，2983，2941，1605，1468，1431，1403，837，755，701，557。 1H?NMR(d-DMSO)：δ＝7.02-7.13(m，5H)，3.31(m，2H)，3.27(m，4H)，2.84(s，3H)，2.80-2.82(m，2H)，1.86(b，4H)ppm。Fusing point: 200 ℃; Heat decomposition temperature: 320 ℃.
Embodiment 23: N-styroyl-N-crassitude bis trifluoromethyl sulfimide salt synthetic
Figure GSA00000121923000251
Take by weighing N-styroyl-N-crassitude bromide 2.70g (10mmol) and be dissolved in the 30mL deionized water, take by weighing 2.87g (10mmol) bis trifluoromethyl sulfimide lithium and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed under agitation condition, and stirring reaction is 12 hours under room temperature.The gained system is filtered isolating solid product, and till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying afterwards 24 hours obtains white solid with deionized water repetitive scrubbing solid product.Products therefrom is confirmed to be the compound that shrinks in the title through infrared spectra and nmr analysis, and productive rate is 85%.FTIR(cm -1)：3094，3070，3039，2980，2939，2896，1605，1529，1464，1436，1344，1185，1136，1061，788，739，700，653，599，570，507。 1HNMR(d-DMSO)：δ＝7.26-7，34(m，5H)，3.55(m，2H)，3.51(m，4H)，3.08(s，3H)，3.03-3.05(m，2H)，2.10(b，4H)。Fusing point: 50 ℃; Heat decomposition temperature: 410 ℃.
Embodiment 24: the polycondensation of synthetic PET experiment in ionic liquid
This compound experiment comprised for two steps in general: the first step is that transesterification reaction obtains condensation monomers B HET (bis-), and second step was the polycondensation of condensation monomers B HET in the presence of pyrrolidines ionic compound of the present invention.
Synthetic BHET.In the four-hole boiling flask that mechanical stirrer, thermometer, still head, prolong, tail adapter and receiving bottle are housed, add dimethyl terephthalate (DMT) (DMT) (29.14g, 0.15mol), the oil bath type of heating is preheating to 110 ℃ with it, adds ethylene glycol (1,2 ethylene glycol, EG) (19.22g, 0.31mol), continuing stirring with 95 rev/mins of stirring velocitys and be warming up to 135 ℃, DMT begins a large amount of fusings.Under agitation continue to heat up, when temperature rises to 190 ℃, add manganous acetate (0.006g) and magnesium acetate (0.005g) as catalyzer, maintenance is 30 minutes under this temperature, distillates methyl alcohol afterwards, keeps this stopped reaction after temperature-resistant 6 hours.Products therefrom is a colourless transparent liquid, leave standstill cooling after, condense into the oyster white block, this product is BHET.
Take by weighing BHET condensation monomer and pyrrolidines ionic compound of the present invention respectively according to following the amount of Table 1, with they add simultaneously agitator is housed and be furnished with prolong and the there-necked flask of receiving bottle in, add antimony glycol (0.0015g) or antimonous oxide (0.0015g) or antimony acetate (0.0015g) afterwards as catalyzer.With the flask sealing, be evacuated to 200Pa, logical nitrogen, this operates three times with the oxygen in the metathesis reactor repeatedly.Afterwards, oil bath heats up, and under agitation, reaction mixture is reacted 0.5 hour down with normal pressure in 200 ℃, is warming up to 230 ℃ then, is decompressed to 1.0 * 10 under this temperature 3Pa reaction 1.5 hours is kept this and temperature-resistant system pressure is transferred to 0.5 * 10 3Pa reaction 1.5 hours is warming up to 240 ℃ of reactions 0.5 hour then again under this pressure.It is normal pressure that stopped reaction, inflated with nitrogen make the flask internal pressure, reduces to room temperature then naturally, obtains solid product.This solid product is pulverized, and is solvent with ethanol, adopts the Soxhlet method for extracting that product is carried out purifies and separates, obtains polymerisate PET.The weight-average molecular weight Mw of each PET product and polydispersity index Mw/Mn see Table 1.
Molecular weight of polyesters characterizes: take by weighing each PET sample of 3.0mg respectively in 10mL tool plug test tube, add the 0.3mL ortho chloro phenol, place 95～105 ℃ baking oven to place 15 minutes in tool plug test tube, the PET sample is dissolved in the ortho chloro phenol fully, treat to dilute with chloroform after the sample dissolution, carry out gpc analysis after the filtration, wherein with polystyrene as standard specimen.Used instrument is gel permeation chromatograph (PL-GPC50 Gel Permeation Chromatograph, a Britain Polymer laboratories company).
Table 1
Figure GSA00000121923000261

Claims (11)

1. pyrrolidines ionic compound, this compound has general formula A +B -, wherein
Described A +Shown in (I):
Figure FSA00000121922900011
In the formula (I): R 1For containing the saturated or undersaturated straight or branched alkyl of 1～6 carbon atom, and
R 2Have following general formula (II) structure:
Figure FSA00000121922900012
In the formula (II),
N is 1～6 integer, is preferably 1 or 2;
Y is H, C 1～C 6Alkyl or nitro; With
*The tie point of nitrogen heteroatom in expression (II) structure and the formula (I),
And
Described B -For being selected from down the negatively charged ion of group: chlorion, bromide anion, iodide ion, nitrate radical, sulfate radical, phosphate radical, tetrafluoroborate, hexafluoro-phosphate radical, bis trifluoromethyl sulfimide root, acetate moiety, tosic acid root and trifluoromethanesulfonic acid root.
2. pyrrolidines ionic compound as claimed in claim 1 is characterized in that, Y is H, C 1～C 4Straight or branched alkyl, or nitro.
3. pyrrolidines ionic compound as claimed in claim 1 or 2 is characterized in that R 1Be C 1～C 4Straight or branched alkyl, C 2～C 4Straight or branched thiazolinyl or C 2～C 4The straight or branched alkynyl, preferable methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, allyl group or propargyl.
4. pyrrolidines ionic compound as claimed in claim 1 is characterized in that, this pyrrolidines ionic compound is:
N-(2-nitrobenzyl)-N-crassitude bromide;
N-(3-nitrobenzyl)-N-crassitude bromide;
N-(4-nitrobenzyl)-N-crassitude bromide;
N-(4-nitrobenzyl)-N-crassitude a tetrafluoro borate;
N-(4-nitrobenzyl)-N-crassitude hexafluorophosphate;
N-(2-nitrobenzyl)-N-crassitude bis trifluoromethyl sulfimide salt;
N-(3-nitrobenzyl)-N-crassitude bis trifluoromethyl sulfimide salt;
N-(4-nitrobenzyl)-N-crassitude bis trifluoromethyl sulfimide salt;
N-(4-methyl-benzyl)-N-crassitude bromide;
N-(4-methyl-benzyl)-N-crassitude bis trifluoromethyl sulfimide salt;
N-(4-nitrobenzyl)-N-n-butylpyrrolioine bromide;
N-(4-nitrobenzyl)-N-n-butylpyrrolioine bis trifluoromethyl sulfimide salt;
N-(4-nitrobenzyl)-N-isobutyl-tetramethyleneimine bromide;
N-(4-nitrobenzyl)-N-isobutyl-tetramethyleneimine bis trifluoromethyl sulfimide salt;
N-(4-nitrobenzyl)-N-crassitude acetate;
N-(4-nitrobenzyl)-N-crassitude tosilate;
N-(4-nitrobenzyl)-N-allyl group tetramethyleneimine bromide;
N-(4-nitrobenzyl)-N-propargyl tetramethyleneimine bromide;
N-(4-nitrobenzyl)-N-allyl group tetramethyleneimine bis trifluoromethyl sulfimide salt;
N-(4-nitrobenzyl)-N-propargyl tetramethyleneimine bis trifluoromethyl sulfimide salt;
N-styroyl-N-crassitude bromide;
N-styroyl-N-crassitude hexafluorophosphate; Or
N-styroyl-N-crassitude bis trifluoromethyl sulfimide salt.
5. one kind prepares as each desired wherein B in the claim 1～4 -Be Cl -, Br -Or I -Anionic halogenide pyrrolidines ionic compound A +B -Method, this method comprises:
Make following formula (III) compound:
Figure FSA00000121922900021
Wherein n and Y in the claim 1～4 each for formula (II) definition, and X ' is chlorine, bromine or iodine,
With the reaction of following formula (IV) compound,
Figure FSA00000121922900031
R wherein 1Such as in the claim 1～4 each for formula (I) definition,
Obtain pyrrolidines ionic compound A +B -, B wherein -Be Cl -, Br -Or I -Negatively charged ion, and A +As each mutual-through type A in the claim 1～4 +B -Define.
6. method as claimed in claim 5 is characterized in that, formula (III) compound uses with equimolar amount or molar excess with respect to formula (IV) compound, and the mole dosage ratio of preferred the former with the latter is 1.0: 1～1.5: 1.
7. as claim 5 or 6 described methods, it is characterized in that be reflected at solvent-especially ethyl acetate, toluene, tetrahydrofuran (THF) or its any mixture-existence of formula (III) compound and formula (IV) compound were carried out 1～24 hour down under 20～50 ℃.
8. method as claimed in claim 7, it is characterized in that, formula (III) compound and formula (IV) compound be dissolved in respectively form solution in the solvent, and then the solution of formula (III) compound dropwise splashed in the solution of formula (IV) compound, vice versa, is 1: 5～1: 10 with the mol ratio of solvent respectively to this preferred formula (III) compound and formula (IV) compound; Perhaps a kind of being dissolved in formula (III) compound and formula (IV) compound formed solution in the solvent, then this solution is mixed with another kind in formula (III) compound and formula (IV) compound.
9. one kind prepares as each desired wherein B in the claim 1～4 -Pyrrolidines ionic compound A for nitrate radical, tetrafluoroborate, hexafluoro-phosphate radical, bis trifluoromethyl sulfimide root, acetate moiety, tosic acid root, trifluoromethanesulfonic acid root, phosphate radical or sulfate radical +B -Method, this method comprises:
(a) prepare as each desired wherein B in the claim 1～4 according to each method in the claim 5～8 -Be Cl -, Br -Or I -Anionic halogenide pyrrolidines ionic compound A +B -, A wherein +As each mutual-through type A in the claim 1～4 +B -Define; And
(b1) make halogenide pyrrolidines ionic compound and the silver nitrate aqueous solution reaction that obtains in the step (a), make the halogen ion generate precipitation, thereby obtain pyrrolidines ionic compound A +B -, B wherein -Be nitrate radical, and A +As each mutual-through type A in the claim 1～4 +B -Define; Perhaps
(b2) the halogenide pyrrolidines ionic compound that obtains in the step (a) and Tetrafluoroboric acid or its an alkali metal salt are reacted in the presence of dehydrated alcohol, obtain pyrrolidines ionic compound A +B -, B wherein -Be tetrafluoroborate, and A +As each mutual-through type A in the claim 1～4 +B -Define; Perhaps
(b3) make the halogenide pyrrolidines ionic compound that obtains in the step (a) and the reactant aqueous solution of phosphofluoric acid or its an alkali metal salt, obtain pyrrolidines ionic compound A +B -, B wherein -Be hexafluoro-phosphate radical, and A +As each mutual-through type A in the claim 1～4 +B -Define; Perhaps
(b4) make the reactant aqueous solution of lithium, sodium or the sylvite of the halogenide pyrrolidines ionic compound that obtains in the step (a) and bis trifluoromethyl sulfimide, obtain pyrrolidines ionic compound A +B -, B wherein -Be bis trifluoromethyl sulfimide root, and A +As each mutual-through type A in the claim 1～4 +B -Define; Perhaps
(b5) make the halogenide pyrrolidines ionic compound that obtains in the step (a) and the reactant aqueous solution of lead acetate or silver acetate, make the halogen ion generate precipitation, thereby obtain pyrrolidines ionic compound A +B -, B wherein -Be acetate moiety, and A +As each mutual-through type A in the claim 1～4 +B -Define; Perhaps
(b6) make the halogenide pyrrolidines ionic compound that obtains in the step (a) and the reactant aqueous solution of tosic acid or trifluoromethanesulfonic acid, make the halogen ion generate haloid acid, thereby obtain pyrrolidines ionic compound A +B -, B wherein -Be respectively tosic acid root or trifluoromethanesulfonic acid root, and A +As each mutual-through type A in the claim 1～4 +B -Define; Perhaps
(b7) make halogenide pyrrolidines ionic compound and the aqueous solution of phosphoric acid or its aqueous solution or phosphoric acid alkali metal salt or the reactant aqueous solution of the vitriol oil or its aqueous solution or sulfuric acid an alkali metal salt that obtains in the step (a), make the halogen ion generate haloid acid or alkali metal halide, thereby obtain pyrrolidines ionic compound A +B -, B wherein -Be respectively phosphate radical or sulfate radical, and A +As each mutual-through type A in the claim 1～4 +B -Define.
10. method as claimed in claim 9 is characterized in that,
In step (b1), with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, mix with the Silver Nitrate of the equimolar amount that is aqueous solution form more afterwards, at room temperature reaction, make halide anion generate silver halide precipitation, filter afterwards, and with the filtrate evaporation, thereby wherein B obtained -Pyrrolidines ionic compound A for nitrate radical +B -Perhaps
In step (b2), with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the dehydrated alcohol, mix with Tetrafluoroboric acid or its an alkali metal salt more afterwards, at room temperature stirring reaction is 1～24 hour, under the situation of using Tetrafluoroboric acid, with the filtrate evaporation, and under the situation of using the Tetrafluoroboric acid an alkali metal salt, isolate lower floor's solid, filtrate is revolved steaming to remove a large amount of dehydrated alcohols, will revolve the mixture suction filtration that obtains after steaming removing residual inorganic salt, thereby obtain wherein B -Be respectively the pyrrolidines ionic compound A of tetrafluoroborate +B -Perhaps
In step (b3), with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, mix with phosphofluoric acid or its an alkali metal salt of the equimolar amount that is aqueous solution form more afterwards, at room temperature stirring reaction is 1～24 hour, isolate lower floor's oil phase or solid, use the deionized water repetitive scrubbing, in washings till the halogen negatively charged ion, thereby obtain wherein B -Be respectively the pyrrolidines ionic compound A of hexafluoro-phosphate radical +B -Perhaps
In step (b4), with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, mix with lithium, sodium or the sylvite of the bis trifluoromethyl sulfimide of the equimolar amount that is aqueous solution form more afterwards, at room temperature stirring reaction is 1～24 hour, isolate lower floor's oil phase or solid, use the deionized water repetitive scrubbing, in washings till the halogen negatively charged ion, thereby obtain wherein B -Pyrrolidines ionic compound A for bis trifluoromethyl sulfimide root +B -Perhaps
In step (b5), with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, mix with the lead acetate or the silver acetate of the stoichiometric quantity that is aqueous solution form more afterwards, reaction at room temperature, make halide anion generate lead halide or silver halide precipitation, filter afterwards, with the filtrate evaporation, thereby obtain wherein B -Pyrrolidines ionic compound A for acetate moiety +B -Perhaps
In step (b6), with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, mix with the tosic acid or the trifluoromethanesulfonic acid of the equimolar amount that is aqueous solution form more afterwards, under room temperature and autogenous pressure, react, make halide anion generate haloid acid, with the filtrate evaporation, thereby obtain wherein B -Be respectively the pyrrolidines ionic compound A of tosic acid root or trifluoromethanesulfonic acid root +B -Perhaps
In step (b7), with the B that obtains in the step (a) -For the halogenide pyrrolidines ionic compound of halide anion is dissolved in the deionized water, again the aqueous solution of phosphoric acid or its aqueous solution or phosphoric acid alkali metal salt or the aqueous solution of the vitriol oil or its aqueous solution or sulfuric acid an alkali metal salt are added dropwise to wherein afterwards, under-10～0 ℃ and autogenous pressure, react, make halide anion generate haloid acid or alkali metal halide, under the situation of using phosphoric acid or its aqueous solution or the vitriol oil or its aqueous solution, filtrate is evaporated, and cooling filtrate is separated out alkali metal halide under the situation of the aqueous solution that uses phosphoric acid alkali metal salt or sulfuric acid an alkali metal salt, again filtrate is evaporated after the filtration, thereby obtain B -Be respectively the pyrrolidines ionic compound A of phosphate radical or sulfate radical +B -
11. as claim 9 or 10 described methods, it is characterized in that Tetrafluoroboric acid an alkali metal salt, phosphofluoric acid an alkali metal salt, phosphoric acid alkali metal salt and sulfuric acid an alkali metal salt are Tetrafluoroboric acid, phosphofluoric acid, phosphoric acid and sulfuric acid lithium, sodium, potassium, rubidium or cesium salt separately.
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