CN107602424B - Ionic liquid, preparation method and application - Google Patents

Ionic liquid, preparation method and application Download PDF

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CN107602424B
CN107602424B CN201710796543.2A CN201710796543A CN107602424B CN 107602424 B CN107602424 B CN 107602424B CN 201710796543 A CN201710796543 A CN 201710796543A CN 107602424 B CN107602424 B CN 107602424B
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ionic liquid
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anion
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CN107602424A (en
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赵国英
万亚萌
张锁江
王傲运
张振华
徐子晨
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Institute of Process Engineering of CAS
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    • C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
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    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
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    • C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
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Abstract

The invention relates to an ionic liquid, wherein the cation of the ionic liquid contains hexafluoroisopropylsulfonic acid groups. According to the ionic liquid provided by the invention, hexafluoroisopropylsulfonic acid groups are introduced into the cation part of the ionic liquid to endow the ionic liquid with a super-strong acid center, and the anion type is modulated to obtain the ionic liquid with the acidity higher than that of concentrated sulfuric acid with the acidity of more than 98%, and the Hamlet acidity (H) in the obtained ionic liquid0) Up to-14.13.

Description

Ionic liquid, preparation method and application
Technical Field
The invention belongs to the field of ionic liquid preparation, relates to an ionic liquid, a preparation method and application, and particularly relates to an ionic liquid containing hexafluoroisopropylsulfonic acid groups, and a preparation method and application thereof.
Background
The ionic liquid consists of organic cations and inorganic anions and is liquid at room temperature or use temperature. Compared with the traditional organic solvent, the ionic liquid has excellent characteristics: 1) the structure function has ion designability; 2) good solubility, good solubility to organic/inorganic substances; 3) almost has no vapor pressure, is not volatile and is not explosive, so the pollution is low; 4) the melting point is low, and the chemical and thermodynamic properties are stable; 5) the post-treatment is simple and can be recycled; 6) the ionic liquid can be used as a reaction catalyst, and has obvious advantages in the aspects of improving the reaction rate, improving the product selectivity and recycling the catalyst; 7) has a relatively wide electrochemical window. In recent years, the ionic liquid as a novel green reaction solvent and catalyst plays a unique role in oxidation reaction, catalytic hydrogenation reaction, Friedel-Crafts reaction, Diels-Alder reaction, Beckman rearrangement reaction, fuel oil desulfurization, cellulose dissolution and the like; in addition, ionic liquids also have comparable advantages in solid electrolytes. The strong acid ionic liquid is loaded or polymerized to prepare the solid electrolyte material, so that the defect of short service life caused by leakage and volatilization of the liquid electrolyte in the using process is overcome, and meanwhile, the quasi-ionic liquid solid electrolyte material has the advantages of plasticity which cannot be achieved by inorganic solid electrolyte materials, small volume and light weight. Ionic liquid electrolyte batteries are particularly useful in computers, memory-backed power supplies, self-powered large-scale integrated circuits, portable devices, electric vehicles, and the like. In the present day that energy is increasingly tense, the research and development of the ionic liquid solid electrolyte which is environment-friendly and can continuously discharge has important significance.
By utilizing the advantage of structural/functional designability of the acidic ionic liquid, a series of functionalized ionic liquids with special properties can be obtained by properly modulating and modifying anions and cations according to the characteristics of target products and the catalytic process, and the universality and the application range of the ionic liquids can be greatly enhanced by the functionalized ionic liquids. The acidic ionic liquid is used as a type of functionalized ionic liquid and plays the roles of a catalyst and a reaction solvent simultaneously in the reaction.The research in the field of catalysis is earlier that Lewis acid type ionic liquid has the advantages of adjustable acidity and good catalytic performance, but the Lewis acid type ionic liquid is sensitive to water and limits the further application of the Lewis acid type ionic liquid. And many are
Figure BDA0001400449800000011
The acid ionic liquid has the advantage of stability to water/air, and has wide application prospect.
Common to all
Figure BDA0001400449800000012
Acid ionic liquids can be divided into two categories according to structural classification: one kind is that basic heterocyclic compounds such as imidazole, pyridine, etc. are protonated or protonated quaternary ammonium salt, quaternary phosphonium salt are taken as cation, corresponding acid radical ion is taken as ionic liquid anion, the ionic liquid is obtained by one-step reaction of strong acid and weak base, so the acidity of the ionic liquid depends on the acidity of the raw material mother acid; the other type is that acidic groups are directly introduced into heterocyclic rings such as imidazole, pyridine, piperidine and the like in a covalent bond form to form acid-functionalized cations, and then the acidic groups are acidified to obtain the acidic ionic liquid, wherein the acidity generally depends on the number of the acidic groups, the acidity of the acidic groups, the volume size of the ionic liquid and the like.
Hexafluoroisopropylsulfonic acid is a novel fluorosulfonic acid, and the results of gas phase acidity and nuclear magnetic detection acidity coefficient are shown in the following table:
name (R) H0 GA
Hexafluoroisopropylsulfonic acid -13.46 1217KJ/mol
Trifluoromethanesulfonic acid -14 1237KJ/mol
Concentrated sulfuric acid -10.37 1265±10KJ/mol
As can be seen from the above table, H of hexafluoroisopropylsulfonic acid0The GAs phase acidity GA of the three shows that the GAs phase acidity of hexafluoroisopropylsulfonic acid is greater than that of trifluoromethanesulfonic acid (the lower GA, the greater the GAs phase acidity). The super strong acidity is attributed to a super strong acidity hexafluoroisopropylsulfonic acid group contained in the cation, the strong electron withdrawing effect of the perfluoroalkyl group, and the weak coordination property of hexafluoroisopropylsulfonic acid.
In the prior art, hexafluoro-isopropyl sulfonic acid reacts with imidazole or quaternary ammonium salt to obtain a series of novel acidic ionic liquids, but hexafluoro-isopropyl sulfonate is used as the acidity of the ionic liquid of anions, and the acidity of the ionic liquid is far lower than that of hexafluoro-isopropyl sulfonic acid, so that the advantage of strong acidity of hexafluoro-isopropyl sulfonic acid on the catalytic performance cannot be reflected.
There is a need in the art to develop an ionic liquid which is highly acidic and is less affected by the use environment during use, and which can provide better catalytic effect.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide an ionic liquid having a cation comprising hexafluoroisopropanol sulfonic acid functional group.
The hexafluoro-isopropylsulfonic acid group is introduced into the cation of the ionic liquid, and the super-strong acidity is attributed to the super-strong acidity hexafluoro-isopropylsulfonic acid group contained in the cation, the strong electron withdrawing effect of perfluoroalkyl and the weak coordination of hexafluoro-isopropylsulfonic acid, and the cooperativity of anions is modulated, so that the cationic ionic liquid with the hexafluoro-isopropylsulfonic acid group has super-strong acidity and is excellent in catalytic performance.
Preferably, the cation of the ionic liquid of the present invention has the structure of formula (I):
Figure BDA0001400449800000021
in the formula (I), Y is selected from
Figure BDA0001400449800000022
A combination of any 1 or at least 2 of
Wherein R is1Selected from alkylene groups;
wherein R is2、R3、R4、R5、R7Each independently selected from the group consisting of a hydrogen atom, an unsubstituted hydrocarbyl group, a hydrocarbyl group having an acidic group, -SO3Any 1 or a combination of at least 2 of H;
wherein R is6Selected from any 1 of hydrocarbyl, hydroxyl, carboxyl, alkoxy.
In the structure of formula (I), a hexafluoroisopropylsulfonic acid group is bonded to an amino group, an imidazole group, and a pyridine group via an alkylene group, and a hexafluoroisopropylsulfonic acid group is introduced into a cation to impart strong acidity to an ionic liquid.
The alkylene group in the present invention means an alkane group in which two hydrogen atoms are removed, that is, an alkyl group capable of connecting to other groups through two bonds. Exemplary alkylene groups include alkylene groups, phenylene groups, and the like.
The alkyl is exemplified by saturated or unsaturated alkyl with 1-20 carbon atoms; the hydroxyl is a saturated or unsaturated hydroxyl with 1-20 carbon atoms; the carboxyl is a saturated or unsaturated carboxyl with 1-20 carbon atoms; the alkoxy is a saturated or unsaturated alkoxy having 1-20 carbon atoms.
Preferably, said R is1Selected from alkylene radicalsAny 1 of the groups, preferably from- (CH)2)nAny 1 of phenylene groups, wherein n is a positive integer of not less than 0, such as 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 17, 19, and the like.
Preferably, in the hydrocarbon group having an acidic group, the acidic group includes-SO3H、-COOH、
Figure BDA0001400449800000031
Any 1 of them.
Illustratively, the hydrocarbyl group having an acidic group is- (CH)2)3-SO3H、-(CH2)4-SO3H、-CH2-COOH、-(CH2)5-COOH、
Figure BDA0001400449800000032
Any 1 of them.
The present invention is not particularly limited to the anion of the ionic liquid of the present invention, and any anion that can be used for the ionic liquid can be used for the present invention.
Preferably, the anion of the ionic liquid comprises ClSO3 -、CF3SO3 -、CF3COO-、HSO4 -、NO3 -、SO4 2-、H2PO4 -、BF4 -、PF6 -、SbF6 -、(CF3)2PF4 -、(CF3)2CSO4 -、(NTF2)-、p-MeC6H4SO3 -、PW12O40 3-、SiW12O40 4-、AlCl4 -、Al2Cl7 -、FeCl4 -、ZnCl3 -Or a halogen anion X-Any 1 of (1).
When the anion of the ionic liquid is a perfluorate anion, e.g. CF3SO3 -、BF4-、PF6 -、SbF6、(NTF2)-And the obtained ionic liquid has stronger acidity.
Preferably, the cation of the ionic liquid comprises any 1 of the following structures:
Figure BDA0001400449800000041
in the formula (i-a), the formula (i-b), the formula (i-c), the formula (i-d), the formula (i-e), R1Selected from alkylene groups; r2、R3、R4、R5、R7Each independently selected from the group consisting of a hydrogen atom, an unsubstituted hydrocarbyl group, a hydrocarbyl group containing an acidic group, -SO3Any 1 or a combination of at least 2 of H; r6Selected from any 1 of hydrocarbyl, hydroxyl, carboxyl, alkoxy.
The second purpose of the invention is to provide a preparation method of the ionic liquid, which comprises the following steps:
(1) synthesizing a compound containing a hexafluoroisopropanol group;
(2) quaternizing the compound containing the hexafluoroisopropanol group obtained in the step (1) to obtain a quaternary ammonium salt grafted with the hexafluoroisopropanol group;
(3) and (3) performing chlorosulfonation reaction on the quaternary ammonium salt grafted with the hexafluoroisopropanol group obtained in the step (2) to obtain the ionic liquid of which the cation contains the hexafluoroisopropanol sulfonic acid group.
Optionally, step (3) is followed by step (4) of reacting the ionic liquid of step (3) with a compound containing an anion M-The acid or inorganic salt is subjected to anion exchange reaction to obtain ionic liquid with other anions.
The method for synthesizing the hexafluoroisopropanol group-containing compound of the present invention is not particularly limited, and any method capable of synthesizing a hexafluoroisopropanol group-containing compound can be used in the present invention.
Preferably, the acid/salt containing the target anion comprises HClSO3、HCF3SO3、CF3COOH、H2SO4、HNO3、H3PO4、KBF4、NaPF6、NaSbF6、H(CF3)2PF4、(CF3)2CCSO4H、Li(NTF2、p-MeC6H4SO3H、H3PW12O40、H4SiW12O40、AlCl3、FeCl3、ZnCl2And a combination of any 1 or at least 2 of the halogen acids;
preferably, the hydrohalic acid comprises any 1 or a combination of at least 2 of HF, HBr, HCl.
Alternatively, when the cation-containing compound has the structural formula of formula (i-a), the preparation method comprises the steps of:
(1a) will be provided with
Figure BDA0001400449800000051
By N-alkylation to give
Figure BDA0001400449800000052
(2a) Subjecting the obtained product to
Figure BDA0001400449800000053
Quaternization to give
Figure BDA0001400449800000054
(3a) To pair
Figure BDA0001400449800000055
Chlorosulfonation to give
Figure BDA0001400449800000056
(4a) Subjecting the obtained product to
Figure BDA0001400449800000057
With a compound containing an anion M-Acid or inorganic salt ofCarrying out anion exchange reaction to obtain the ionic liquid of corresponding anions
Figure BDA0001400449800000058
Wherein the quaternizing agent of step (2a) comprises a halogenated hydrocarbon R4X; x is a halogen element, preferably any 1 or combination of at least 2 of chlorine, bromine and iodine.
Wherein R is1Selected from alkylene groups; r2、R3、R4Each independently selected from the group consisting of a hydrogen atom, an unsubstituted hydrocarbyl group, a hydrocarbyl group having an acidic group, -SO3Any 1 or a combination of at least 2 of H;
wherein M is-Is ClSO3 -、CF3SO3 -、CF3COO-、HSO4 -、NO3 -、SO4 2-、H2PO4 -、BF4-、PF6 -、SbF6 -、(CF3)2PF4 -、(CF3)2CSO4 -、(NTf2)-、p-MeC6H4SO3 -、PW12O40 3-、SiW12O40 4-、AlCl4 -、Al2Cl7 -、FeCl4 -、ZnCl3 -Or a halogen anion X-Any 1 of (1).
The halogen comprises any 1 of fluorine, chlorine, bromine and iodine or any 1 of combination of at least 2 of fluorine, chlorine, bromine and iodine.
Exemplarily, the following steps are carried out:
the conditions for the N-alkylation described in step (1a) (in the case of methylation) are: will be provided with
Figure BDA0001400449800000061
Placing in a three-neck flask, adding isopropanol solvent, stirring and heatingSlowly dripping formic acid into the mixture when the temperature is 35 ℃, then continuously heating the mixture to 50 ℃, and slowly dripping formaldehyde into the mixture under strong stirring; finally, heating the mixture to 80 ℃, and carrying out reflux reaction for 21 h; cooling, alkalizing with NaOH solution until pH is 13, layering, extracting the upper layer with n-hexane, evaporating solvent with rotary evaporator at maximum rotary evaporation temperature of 70 deg.C to obtain crude product. Mixing the crude product with a certain amount of acetic anhydride in 30mL of diethyl ether, and refluxing for 2 h; adding 30mL of 10% hydrochloric acid, stirring for 2h, cooling, and transferring to a separating funnel; basifying with NaOH solution to pH 13, extracting the upper layer with n-hexane, and distilling off the solvent. The product was dried under vacuum for 24 h.
The conditions for quaternization (in the case of bromobutane) in step (2a) are: taking the product
Figure BDA0001400449800000062
Dissolving in isopropanol, heating to 45 deg.C, and adding (after 45min of dropwise addition) bromobutane with the same molar weight; refluxing for 28h, cooling and evaporating the solvent; recrystallizing the white solid product in an ethanol-ethyl acetate mixed solution; dissolving the product in an ethanol-ethyl acetate mixed solution during recrystallization, heating to 74-76 ℃, filtering while the solution is hot, repeating the process for three times, standing and cooling the filtrate, and standing for 24 hours until crystals are generated; vacuum drying the filtered solid to constant weight to obtain the product
Figure BDA0001400449800000071
Preferably, the chlorosulfonation conditions of step (3a) are: slowly dropwise adding chlorosulfonic acid to the reactant at-15 deg.C
Figure BDA0001400449800000072
Stirring, heating at about 50 deg.C after dripping, and adding N2Removing HCl gas generated in the reaction, draining HCl, washing with dichloromethane to obtain the product
Figure BDA0001400449800000073
Optionally, step (4a) an anion exchange step (with CF)3SO3H is example) reaction of CF at ambient temperature3SO3H is slowly dripped to an equimolar amount
Figure BDA0001400449800000074
Stirring for 12h, washing the reaction product with dichloromethane, and rotary evaporating to dryness to obtain anionic ionic liquid
Figure BDA0001400449800000075
Alternatively, when the cation-containing compound has the structural formula of formula (i-a), the preparation method comprises the steps of:
(1 a') mixing
Figure BDA0001400449800000076
Chlorosulfonation to give
Figure BDA0001400449800000077
(2 a') subjecting the resultant to
Figure BDA0001400449800000081
Performing acid-base neutralization reaction with acid HM containing anions to obtain ionic liquid of corresponding anions
Figure BDA0001400449800000082
Exemplarily, the following steps are carried out:
step (1 a') step of Chlorosulfonation referring to step (3a) the Chlorosulfonation step, only the reactants were replaced with
Figure BDA0001400449800000083
Step (2 a') is to
Figure BDA0001400449800000084
Reacting with acid HM containing anions to obtain ionic liquid of corresponding anions
Figure BDA0001400449800000085
When the cation-containing compound has the structural formula of formula (i-b), the preparation method comprises the steps of:
(1b) will be provided with
Figure BDA0001400449800000086
By P-alkylation to give
Figure BDA0001400449800000087
(2b) Subjecting the obtained product to
Figure BDA0001400449800000088
Quaternization to obtain
Figure BDA0001400449800000089
(3b) To pair
Figure BDA0001400449800000091
Chlorosulfonation to give
Figure BDA0001400449800000092
(4b) Subjecting the obtained product to
Figure BDA0001400449800000093
With a compound containing an anion M-Reacting the acid or inorganic salt to obtain the ionic liquid of corresponding anion
Figure BDA0001400449800000094
Wherein the quaternary ammonium agent of the quaternary phosphonium salt in the step (2b) comprises a halogenated hydrocarbon R4X; x is a halogen element, preferably any 1 or combination of at least 2 of chlorine, bromine and iodine.
Wherein R is1Selected from alkylene groups; r2、R3、R4Each independently selected from the group consisting of a hydrogen atom, an unsubstituted hydrocarbyl group, a hydrocarbyl group having an acidic group, -SO3Any 1 or a combination of at least 2 of H;
wherein M is-Is ClSO3 -、CF3SO3 -、CF3COO-、HSO4 -、NO3 -、SO4 2-、H2PO4 -、BF4-、PF6 -、SbF6 -、(CF3)2PF4 -、(CF3)2CSO4 -、(NTF2)-、p-MeC6H4SO3 -、PW12O40 3-、SiW12O40 4-、AlCl4 -、Al2Cl7 -、FeCl4 -、ZnCl3 -Or a halogen anion X-Any 1 of (1).
The halogen comprises any 1 of fluorine, chlorine, bromine and iodine or any 1 of combination of at least 2 of fluorine, chlorine, bromine and iodine.
Exemplarily, the following steps are carried out:
the conditions for the P-alkylation in step (1b) (the starting material is n-butene for example) are: will be provided with
Figure BDA0001400449800000095
And (3) placing the mixture into a reaction kettle, fully replacing the nitrogen, adding n-butene and an initiator, heating and stirring the mixture at the temperature of 80 ℃, reacting for 2 hours at the reaction pressure of 5-8 MPa. Opening the kettle when the temperature is reduced to below 50 ℃, rectifying the reacted liquid, and collecting 150 ℃ distillate with the pressure of 5mbar
Figure BDA0001400449800000101
The conditions for the quaternary phosphating (in the case of n-butyl chloride) of step (2b) are: mixing equimolar amounts of
Figure BDA0001400449800000102
Mixing with n-butyl chloride, heating at 140 deg.C under nitrogen protection, stirring for 12 hr, reacting, distilling under reduced pressure to remove volatile substances to obtain the final product
Figure BDA0001400449800000103
Preferably, the chlorosulfonation step of step (3b) is referenced to the chlorosulfonation step of step (3a) except that the raw materials are replaced with
Figure BDA0001400449800000104
Alternatively, step (4b) the anion exchange step refers to the anion exchange step of step (4a) except that the starting material is replaced with
Figure BDA0001400449800000105
Or the preparation method comprises the following steps:
(1 b') mixing
Figure BDA0001400449800000106
Chlorosulfonation to give
Figure BDA0001400449800000107
(2 b') subjecting the resultant to
Figure BDA0001400449800000111
With a compound containing an anion M-Reacting the acid or salt to obtain the ionic liquid of corresponding anion
Figure BDA0001400449800000112
Figure BDA0001400449800000113
The specific synthetic steps can be referred to
Figure BDA0001400449800000114
And (3) a synthesis step.
Wherein M is-Is ClSO3 -、CF3SO3 -、CF3COO-、HSO4 -、NO3 -、SO4 2-、H2PO4 -、BF4 -、PF6 -、SbF6 -、(CF3)2PF4 -、(CF3)2CSO4 -、(NTf2)-、p-MeC6H4SO3 -、PW12O40 3-、SiW12O40 4-、AlCl4 -、Al2Cl7 -、FeCl4 -、ZnCl3 -Or a halogen anion X-Any 1 of (1).
As another alternative, when the cation-containing compound has the structural formula of formula (i-c), the preparation method comprises the steps of:
(1c) will be provided with
Figure BDA0001400449800000115
Cyclization of imidazole to give
Figure BDA0001400449800000116
(2c) To pair
Figure BDA0001400449800000117
Chlorosulfonation to give
Figure BDA0001400449800000118
(3c) Subjecting the obtained product to
Figure BDA0001400449800000119
With an anion M-The acid or salt of the acid or salt reacts to carry out anion exchange, and the ionic liquid of corresponding anions can be obtained
Figure BDA0001400449800000121
Exemplarily, the following steps are carried out:
the conditions for cyclization of imidazole in step (1c) are that nucleophilic addition of ammonia and aldehyde is utilized, and ammonium acetate is used as ammoniaThe source of (A) is subjected to affinity reaction with glyoxal and formaldehyde, and specifically comprises the following steps: will be provided with
Figure BDA0001400449800000122
Placing in a single-mouth bottle, then adding glyoxal, formaldehyde and ammonium acetate, and taking acetic acid as a catalyst; stirring and heating for 3h at 70 ℃, and then removing water and acetic acid by rotary evaporation to obtain a product
Figure BDA0001400449800000123
Exemplary, conditions for chlorosulfonation in step (2 c): slowly adding chlorosulfonic acid dropwise to the reaction mass at-15 deg.C
Figure BDA0001400449800000124
Stirring, heating at about 50 deg.C after dripping, and adding N2Removing HCl gas generated in the reaction, draining HCl, washing with dichloromethane to obtain the product
Figure BDA0001400449800000125
Illustratively, the step (3c) reaction step refers to the anion exchange step of step (4a), except that the starting material is replaced with
Figure BDA0001400449800000126
As a further alternative, when the cation-containing compound has the formula (i-c), the preparation method comprises the steps of:
(1 c') mixing
Figure BDA0001400449800000131
Cyclization of imidazole to give
Figure BDA0001400449800000132
(2 c') subjecting the obtained
Figure BDA0001400449800000133
Quaternization to give
Figure BDA0001400449800000134
(3 c') pair
Figure BDA0001400449800000135
Chlorosulfonation to give
Figure BDA0001400449800000136
(4 c') subjecting the obtained
Figure BDA0001400449800000137
With a compound containing an anion M-To obtain the ionic liquid of corresponding anion
Figure BDA0001400449800000138
Illustratively, the conditions for imidazole cyclization in step (1 c') are referenced to the step for imidazole cyclization in step (1 c).
Illustratively, the step of quaternizing in step (2 c') refers to the step of step (2a), except that the starting material is replaced with
Figure BDA0001400449800000139
Illustratively, the conditions for chlorosulfonation in step (3 c') are referenced to those in step (3a), except that the starting materials are replaced with
Figure BDA0001400449800000141
Wherein R is1Selected from alkylene groups; r6Selected from hydrogen atoms, unsubstituted hydrocarbon radicals, hydrocarbon radicals having acidic groups, -SO3Any 1 or a combination of at least 2 of H; the quaternized quaternizing agent comprises a halogenated hydrocarbon R5X; x is a halogen element, preferably any 1 or combination of at least 2 of chlorine, bromine and iodine;
wherein M is-Is ClSO3 -、CF3SO3 -、CF3COO-、HSO4 -、NO3 -、SO4 2-、H2PO4 -、BF4-、PF6 -、SbF6 -、(CF3)2PF4 -、(CF3)2CSO4 -、(NTF2)-、p-MeC6H4SO3 -、PW12O40 3-、SiW12O40 4-、AlCl4 -、Al2Cl7 -、FeCl4 -、ZnCl3 -Or a halogen anion X-Any 1 of (1).
As a further alternative, when the cation-containing compound has the formula (i-d), the preparation method comprises the steps of:
(1d) will be provided with
Figure BDA0001400449800000142
Carrying out bigeminylation to obtain
Figure BDA0001400449800000143
(2d) Subjecting the obtained product to
Figure BDA0001400449800000144
Chlorosulfonation to give
Figure BDA0001400449800000145
(3d) Subjecting the obtained product to
Figure BDA0001400449800000151
With a compound containing an anion M-The acid or salt anion exchange reaction of (a) to obtain the ionic liquid of the corresponding anion
Figure BDA0001400449800000152
Exemplarily, the following steps are carried out:
the conditions of the biimidazole in the step (1d) are that nucleophilic addition of ammonia and aldehyde is utilized, ammonium acetate is used as a source of ammonia, and the reaction is subjected to affinity reaction with glyoxal, and specifically the conditions are as follows: will be provided with
Figure BDA0001400449800000153
Dissolving in a solution with the volume ratio of acetic acid to water being 3:1, and then adding glyoxal; stirring and heating at 60 deg.C for 0.5h, treating with hydrochloric acid water solution, and drying to obtain product
Figure BDA0001400449800000154
The conditions for chlorosulfonation in step (2d) are the same as those for chlorosulfonation in step (3a), except that the starting materials are replaced with
Figure BDA0001400449800000155
Step (3d) method of anion exchange referring to step (4a) anion exchange step, the only difference is that the starting material is replaced with
Figure BDA0001400449800000161
Wherein R is1Selected from alkylene groups; r6Selected from hydrogen atoms, unsubstituted hydrocarbon radicals, hydrocarbon radicals having acidic groups, -SO3Any 1 or a combination of at least 2 of H; the quaternized quaternizing agent comprises a halogenated hydrocarbon R5X; x is a halogen element, preferably any 1 or combination of at least 2 of chlorine, bromine and iodine;
wherein M is-Is ClSO3 -、CF3SO3 -、CF3COO-、HSO4 -、NO3 -、SO4 2-、H2PO4 -、BF4-、PF6 -、SbF6 -、(CF3)2PF4 -、(CF3)2CSO4 -、(NTF2)-、p-MeC6H4SO3、PW12O40 3-、SiW12O40 4-、AlCl4 -、Al2Cl7 -、FeCl4 -、ZnCl3 -Or a halogen anion X-Any 1 of (1).
As a further alternative, when the cation-containing compound has the formula (i-d), the preparation method comprises the steps of:
(1 d') mixing
Figure BDA0001400449800000162
Carrying out bigeminylation to obtain
Figure BDA0001400449800000163
(2 d') subjecting the mixture to
Figure BDA0001400449800000164
Quaternization to give
Figure BDA0001400449800000165
Figure BDA0001400449800000166
(3 d') subjecting the resultant to
Figure BDA0001400449800000171
Chlorosulfonation is carried out to obtain the corresponding
Figure BDA0001400449800000172
(4 d'): subjecting the obtained product to
Figure BDA0001400449800000173
With a compound containing an anion M-Reacting the acid or salt to obtain the ionic liquid of corresponding anion
Figure BDA0001400449800000174
Figure BDA0001400449800000175
Exemplarily, the following steps are carried out:
the step of biimidation in step (1 d') refers to the step of biimidation in step (1 d).
The quaternization conditions in step (2 d') are (the quaternizing agent is n-butyl iodide for example): reacting the reactants
Figure BDA0001400449800000176
Placing neutral and n-butyl iodide in a sealed tube, reacting for 12h at about 90 ℃ under the protection of nitrogen, and generating when the molar ratio of reactants to the n-butyl iodide is 1:1
Figure BDA0001400449800000181
When the molar ratio of reactant to n-butyl iodide is 1:2
Figure BDA0001400449800000182
Step (4 d') the method of anion exchange is as described with reference to step (4a) with the only difference that the starting material is replaced by
Figure BDA0001400449800000183
As a further alternative, when the cation-containing compound has the formula (i-e), the preparation method comprises the steps of:
(1e) will be provided with
Figure BDA0001400449800000184
Dehydrating under the action of concentrated sulfuric acid to obtain hexafluoroacetone
Figure BDA0001400449800000185
A gas;
(2e) hexafluoroacetone is reacted with
Figure BDA0001400449800000186
Gas synthesis of 2-hexafluoroisopropanol pyridine compounds
Figure BDA0001400449800000187
(3e) To pair
Figure BDA0001400449800000188
Quaternization of N on pyridine ring
Figure BDA0001400449800000189
(4e) To pair
Figure BDA00014004498000001810
Chlorosulfonation to yield the product
Figure BDA00014004498000001811
Optionally, step (4e) is followed by step (5e) will
Figure BDA0001400449800000191
Ion liquid which is exchanged and reacted with acid or salt anion containing anion M-to obtain corresponding anion
Figure BDA0001400449800000192
Exemplarily, the following steps are carried out:
the synthesis conditions of the hexafluoroacetone gas in the step (1e) are as follows: and slowly dripping hexafluoroacetone trihydrate into concentrated sulfuric acid by using a constant-pressure dropping funnel, and slowly introducing the generated hexafluoroacetone gas into a Schlenk bottle through a double needle for synthesizing the 2-hexafluoroisopropanol-based pyridine.
Step (2e) Synthesis conditions of alkyl-2-aminohexafluoroisopropanol pyridine Compound are: using a needle tube to transfer a certain amount of 2-bromopyridine to a cooled repainfan bottle, then using a long needle to add anhydrous tetrahydrofuran, stirring, erecting the device, reducing the temperature of the system to-78 ℃, slowly adding a certain amount of n-butyllithium 2.5M hexane solution to the bottle, and stirring for 1.5h at-78 ℃ for synthesizing 2-lithium pyridine; and (3) slowly introducing hexafluoroacetone gas into a Schlenk bottle for reaction, stirring for 4 hours, absorbing tail gas by using carbon tetrachloride, and slowly heating the reaction to room temperature. The reacted solution was rotary evaporated to remove the solvent, an excess of ethyl acetate was added to the residue after rotary evaporation, the solution was adjusted to PH 4 with diluted HCl, and after washing three times with deionized water, the organic phase was dried over anhydrous magnesium sulfate, and the organic phase after drying was rotary evaporated to remove the solvent. The substrate was distilled under reduced pressure at 40 ℃ at 300mtorr to give 2-hexafluoroisopropanol pyridine as a colorless liquid.
The quaternization conditions of step (3e) are as for the quaternization step of step (2a), except that the starting material is replaced by
Figure BDA0001400449800000193
The chlorosulfonation condition in the step (4e) is as follows: slowly adding 1-butyl-2 hexafluoroisopropanol pyridine bromide into chlorosulfonic acid at-15 ℃, and slowly heating to 35 ℃ and preserving heat for 5 hours after the addition is finished. Washing the product with dichloromethane, and then drying in vacuum to obtain the target product 1-butyl-2 hexafluoroisopropylsulfonic acid pyridine chlorosulfonate.
The anion exchange step of step (5e) is the anion exchange step of step (4a) except that the starting material is replaced with
Figure BDA0001400449800000201
Preferably, the quaternising agent of step (3e) comprises a halogenated hydrocarbon R7X; x is a halogen element, preferably any 1 or combination of at least 2 of chlorine, bromine and iodine;
wherein R is1Selected from alkylene groups; r7Selected from hydrogen atoms, unsubstituted hydrocarbon radicals, hydrocarbon radicals having acidic groups, -SO3Any 1 or a combination of at least 2 of H; r6Each independently selected from any 1 of hydrocarbyl, hydroxyl, carboxyl and alkoxy.
Wherein M is-Is ClSO3 -、CF3SO3 -、CF3COO-、HSO4 -、NO3 -、SO4 2-、H2PO4 -、BF4-、PF6 -、SbF6 -、(CF3)2PF4 -、(CF3)2CSO4 -、(NTF2)-、p-MeC6H4SO3 -、PW12O40 3-、SiW12O40 4-、AlCl4 -、Al2Cl7 -、FeCl4 -、ZnCl3 -Or a halogen anion X-Any 1 of (1).
As a further alternative, when the cation-containing compound has the formula (i-e), the preparation method comprises the steps of:
(1 e') subjecting
Figure BDA0001400449800000202
Dehydrating under the action of concentrated sulfuric acid to obtain hexafluoroacetone
Figure BDA0001400449800000203
A gas; (2 e') reacting hexafluoroacetone
Figure BDA0001400449800000204
Gas synthesis of 2-hexafluoroisopropanol pyridine compounds
Figure BDA0001400449800000205
(3 e') pairs
Figure BDA0001400449800000206
Chlorosulfonation to yield the product
Figure BDA0001400449800000207
Optionally, step (3e ') is followed by step (4 e') which is
Figure BDA0001400449800000208
With a compound containing an anion M-Reacting the acid or salt to obtain the ionic liquid of corresponding anion
Figure BDA0001400449800000209
Exemplarily, the following steps are carried out:
the synthesis conditions of the hexafluoroacetone gas in the step (1 e') refer to the synthesis conditions of the hexafluoroacetone gas in the step (1 e);
the 2-hexafluoroisopropanoxy pyridine compound of the step (2 e') refers to the synthesis conditions of the 2-hexafluoroisopropanoxy pyridine compound of the step (2 e);
the step of chlorosulfonation in step (3 e') refers to the step of chlorosulfonation in step (4e), except that the raw materials are replaced with
Figure BDA0001400449800000211
The anion replacement step of step (4 e') is carried out with reference to the anion replacement step of step (4a), except that the starting material is replaced with
Figure BDA0001400449800000212
It is a further object of the present invention to provide the use of an ionic liquid according to one of the objects for alkylation, Diels Alder reaction, esterification, aldolization, dimerization, Michael addition, isomerization reactions.
Preferably, the ionic liquid is used as a reaction medium and/or a reaction catalyst.
In the alkylation reaction, Diels Alder reaction, esterification reaction, acetal reaction, dimerization reaction, Michael addition, isomerization reaction, when the ionic liquid is used only as a catalyst, the amount added is exemplarily 1.5 times or less, preferably 1 time or less, and more preferably 0.1 time or less of the reactants; when the ionic liquid is used as both the reaction medium and the catalyst, the addition ratio is not limited to the above, and those skilled in the art can add the ionic liquid according to the reaction requirement.
Compared with the prior art, the invention has the following beneficial effects:
according to the ionic liquid provided by the invention, hexafluoroisopropylsulfonic acid groups are introduced into the cation part of the ionic liquid to endow the ionic liquid with a super-strong acid center, and the anion type is modulated to obtain the ionic liquid with the acidity higher than that of concentrated sulfuric acid with the acidity of more than 98%, and the Hamlet acidity (H) in the obtained ionic liquid0) Up to-14.13.
Drawings
FIG. 1 is a total ion flow diagram of gas chromatography-mass spectrometry in application example 2.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1 preparation of N, N, N-dimethylbutyl hexafluoroisopropylsulfonate ammonium chlorosulfonate (Ionic liquid # 1)
The synthetic route is as follows:
Figure BDA0001400449800000221
the method comprises the following specific steps:
(1) synthesis of N, N-dimethylhexafluoroisopropanol amine: 0.1mol of aminohexafluoroisopropanol was taken in a three-necked flask, 100mL of isopropanol was added, and the mixture was heated to 35 ℃ with stirring. Then slowly dripping 0.5mol of formic acid by using a constant pressure dropping funnel (dripping is finished in 40 min), and heating the mixture to 50 ℃; 0.2mol of formaldehyde is taken and added by a constant pressure dropping funnel under strong stirring (the dropping is finished within 4.5 hours); the mixture was heated to 80 ℃ and maintained at reflux for 21 h. Cooling, alkalizing with NaOH solution until pH is 13, layering, extracting the upper layer with n-hexane, evaporating solvent with rotary evaporator at maximum rotary evaporation temperature of 70 deg.C to obtain crude product. Mixing the crude product with 0.1mol of acetic anhydride in 30mL of ether, and refluxing for 2 h; adding 30mL of 10% hydrochloric acid, stirring for 2h, cooling, and transferring to a separating funnel; alkalizing with NaOH solution until pH is 13, extracting the upper layer with n-hexane, and distilling off solvent; the product was dried in vacuo for 24 h.
(2) Synthesis of N, N-dimethylbutyl hexafluoroisopropanolammonium bromide: dissolving the product obtained in the step (1) in 115mL of isopropanol, heating to 45 ℃, and adding (after 45min of dropwise addition) bromobutane with the same molar weight; refluxing for 28h, cooling, evaporating the solvent to obtain a product, and recrystallizing in an ethanol-ethyl acetate mixed solution; and during recrystallization, dissolving the product in an ethanol-ethyl acetate mixed solution, heating to 74-76 ℃, filtering while hot, repeating the operation for three times, standing and cooling the filtrate, and standing for 24 hours until crystals are generated. The filtered solid was dried under vacuum to constant weight.
(3) Synthesis of N, N, N-dimethylbutyl hexafluoroisopropylsulfonate ammonium chlorosulfonate: slowly adding 0.07mol of the product into 0.154mol of chlorosulfonic acid at minus 15 ℃, and slowly heating to 35 ℃ for 5 hours after the addition is finished. The product was washed with dichloromethane and dried in vacuo.
And (3) characterization:
1H NMR(300MHz,[D6]DMSO,25℃):δ＝0.89(t,3H,N(CH2)3CH3),1.3(m,2H,N(CH2)2CH2CH3),1.71(m,2H,NCH2CH2CH2CH3),3.3(s,6H,N(CH3)2),3.22(t,2H,NCH2(CH2)2CH3),4.2(s,1H,OH).ESI/MS:m/z(+)348.07,m/z(－)115.9。
and (3) testing acidity:
the detection method comprises the steps of taking the isopropylidene acetone (α -unsaturated ketone) as an inducer, taking the tetramethylsilane as an internal standard, respectively mixing the isopropylidene acetone (α -unsaturated ketone) and the tetramethylsilane with the ionic liquid, carrying out 13C nuclear magnetic analysis (300K, Bruker Avance III 600MHz spectrometer), and calculating the acidity coefficient H of the ionic liquid by the internal standard method0。
The test shows that the acidity of the 1# ionic liquid is H0＝-9.21。
Example 2 preparation of N, N, N-dimethylbutyl hexafluoroisopropylsulfonate ammonium triflate (# 2 ionic liquid)
After the step (3) of example 1, the step (4) was performed, and the N, N-dimethylbutyl ammonium hexafluoroisopropylsulfonate chlorosulfonate obtained in the step (3) was subjected to anion exchange with trifluoromethanesulfonic acid at normal temperature for 24 hours with stirring to obtain N, N-dimethylbutyl ammonium hexafluoroisopropylsulfonate trifluoromethanesulfonate.
And (3) characterization:
1H NMR(300MHz,[D6]DMSO,25℃):δ＝0.89(t,3H,N(CH2)3CH3),1.3(m,2H,N(CH2)2CH2CH3),1.71(m,2H,NCH2CH2CH2CH3),3.3(s,6H,N(CH3)2),3.22(t,2H,NCH2(CH2)2CH3),4.2(s,1H,OH).ESI/MS:m/z(+)348.07,m/z(－)149。
the acidity of the 2# ionic liquid is tested to be H0＝-9.401。
Example 3 preparation of hexafluoroisopropylsulfonate-disulfonate ammonium triflate (3# ionic liquid)
The synthetic route is as follows:
Figure BDA0001400449800000231
the method comprises the following specific steps:
slowly dripping 0.1mol (18.3g) of 2-amino hexafluoroisopropanol into 0.4mol of chlorosulfonic acid at the temperature of minus 15 ℃, stirring while dripping, slowly heating to the temperature of minus 5 ℃ after dripping is finished, stirring for 5h, heating to the temperature of 35 ℃, stirring for 5h, washing a substrate after reaction by using dichloromethane, then performing vacuum drying, slowly dripping one time of molar weight of trifluoromethanesulfonic acid into the dried substrate at normal temperature, stirring while dripping, reacting for 24h, performing rotary evaporation on a product after reaction, and performing vacuum drying to obtain a target product.
And (3) characterization:
1H NMR(300MHz,[D6]DMSO,25℃):δ＝4.2(s,1H,SO4H),7.2(s,1H,NH),8.5(s,2H,2SO3H),3.3(s,6H,N(CH3)2),3.22(t,2H,NCH2(CH2)2CH3),4.2(s,1H,OH).ESI/MS:m/z(+)423.9,m/z(－)149。
the purity of the product was determined to be 93% by high performance liquid chromatography.
The test shows that the acidity of the 3# ionic liquid is H0＝-14.13。
EXAMPLE 42 preparation of hexafluoroisopropylidene sulfoimidazole chlorosulfate (4# ionic liquid)
The synthetic route is as follows:
Figure BDA0001400449800000241
the method comprises the following specific steps:
adding 0.1mol (18.3g) of 2-aminohexafluoroisopropanol into a 250mL single-neck flask, adding 36.6mL of glacial acetic acid, stirring, sequentially adding 0.2mol of formaldehyde, 0.2mol of glyoxal and 0.1mol of ammonium acetate, heating to 70 ℃ under the protection of nitrogen, keeping the temperature for about 2.5 hours, washing, extracting and carrying out rotary evaporation to obtain brown liquid 2-imidazole hexafluoroisopropanol. Under the protection of nitrogen atmosphere, 2-imidazole hexafluoroisopropanol and chlorosulfonic acid are uniformly stirred and mixed at the temperature of-15 ℃ according to the molar ratio of 1:3, the temperature is gradually increased to 35 ℃ until no bubbles are generated in the system, and a substrate is subjected to rotary evaporation at the temperature of 60 ℃ to obtain the target product, namely 2-hexafluoroisopropylsulfonic acid imidazole chlorosulfonate.
And (3) characterization: h NMR (600MHz,) δ 8.00(dd, J ═ 17.8,8.6Hz,19H),7.91(dd, J ═ 25.0,10.2Hz,6H), 7.88-7.71 (m,25H), 2.23-1.98 (m,59H), 1.86-1.78 (m,1H), 1.64-1.59 (m,1H),1.32(d, J ═ 51.4Hz,1H), ESI/MS: m/z (+)470.97, m/z (-) 115.9.
The acidity of the 4# ionic liquid is tested to be H0＝-9.21。
EXAMPLE 52 preparation of hexafluoroisopropylsulfonate imidazole trifluoromethanesulfonate (5# Ionic liquid)
2-hexafluoroisopropylsulfonate imidazole trifluoromethanesulfonate is prepared by performing ion exchange on the 2-hexafluoroisopropylsulfonate imidazole chlorosulfonate obtained in example 4 and trifluoromethanesulfonic acid at room temperature for 12h and then performing rotary evaporation.
And (3) characterization: h NMR (600MHz,) δ 8.00(dd, J ═ 17.8,8.6Hz,19H),7.91(dd, J ═ 25.0,10.2Hz,6H), 7.88-7.71 (m,25H), 2.23-1.98 (m,59H), 1.86-1.78 (m,1H), 1.64-1.59 (m,1H),1.32(d, J ═ 51.4Hz,1H), ESI/MS: m/z (+)470.97, m/z (-) 149.
The test shows that the 5# ionic liquid has the acidity of H0＝-9.42。
EXAMPLE 61 preparation of 1,1 ' -Dihexafluoroisopropylsulfonate-3, 3 ' -sulfonic acid-2, 2 ' -biimidazolium bischlorosulfonate (No. 6 Ionic liquid)
The synthetic route is as follows:
Figure BDA0001400449800000242
the method comprises the following specific steps:
dissolving 0.1mol (18.3g) of 2-aminohexafluoroisopropanol in 80mL of glacial acetic acid/water volume ratio of 3:1 in a 250mL single-neck flask, stirring, adding 0.2mol of formaldehyde aqueous solution (mass fraction 37%), adding 0.2mol of glyoxal aqueous solution, keeping the temperature of the mixture at 60 ℃, heating for about 0.5h, adding 20mL of hydrochloric acid aqueous solution (3M) after the reaction is finished, adding water to dilute to obtain a crude product 1,1 '-dihexafluoroisopropanoxy-2, 2' -biimidazole, and drying the crude product in air; and then, stirring and mixing 1,1 ' -dihexafluoroisopropanolate-2, 2 ' -biimidazole and 0.6mol of chlorosulfonic acid uniformly at the temperature of-15 ℃ under the protection of nitrogen atmosphere, gradually heating to 115 ℃ until no bubbles are generated in the system, and carrying out rotary evaporation on the reaction liquid at 60 ℃ to obtain the target product 1,1 ' -dihexafluoroisopropanolate-3, 3 ' -sulfo-2, 2 ' -biimidazole dichlorosulfonate.
And (3) characterization:
1H NMR(300MHz,[D6]DMSO,25℃):δ＝4.2(s,2H,2SO4H),1.3(m,2H,2SNH),7.92(m,2H,2NH),8.5(s,2H,2SO3H).ESI/MS:m/z(+)788,m/z(－)115。
the test shows that the acidity of the 6# ionic liquid is H0＝-8.75。
Example 71 preparation of, 1 ' -Dihexafluoroisopropylsulfonate-3, 3 ' -sulfonic acid-2, 2 ' -bigeminylimidazole bistrifluoromethane sulfonate (7# Ionic liquid)
The 1,1 '-dihexafluoroisopropylsulfonate-3, 3' -sulfonic-2, 2 '-biimidazole bis-chloride sulfonate prepared in example 6 and trifluoromethanesulfonic acid are subjected to ion exchange for 24h at normal temperature and then subjected to rotary evaporation to obtain 1, 1' -dihexafluoroisopropylsulfonate-3, 3 '-sulfonic-2, 2' -biimidazole bis-triflate.
And (3) characterization:1H NMR(300MHz,[D6]DMSO,25℃):δ＝4.2(s,2H,2SO4H),1.3(m,2H,2SNH),7.92(m,2H,2NH),8.5(s,2H,2SO3H).ESI/MS:m/z(+)788,m/z(－)149。
the acidity of the 7# ionic liquid is tested to be H0＝-8.89。
EXAMPLE 81 preparation of butyl-2-hexafluoroisopropylsulfonato pyridine chlorosulfonate (# 8 Ionic liquid)
The synthetic route is as follows:
Figure BDA0001400449800000251
the method comprises the following specific steps:
(1) synthesis of 2-hexafluoroisopropanoylpyridine: using a needle tube to transfer 3.2mL of 2-bromopyridine to inject into the cooled repairaben bottle, then using a long needle to add 100mL of anhydrous tetrahydrofuran, stirring, erecting the device, pouring acetone into a Dewar flask, adding liquid nitrogen, and cooling to-78 ℃; 19.7mL of a 2.5M hexane solution of n-butyllithium was slowly added to the flask, and stirred at-78 ℃ for 1.5 hours to synthesize 2-lithiopyridine; dripping 8.14g of a constant-pressure dropping funnel of hexafluoroacetone trihydrate into concentrated sulfuric acid, slowly introducing generated hexafluoroacetone gas into a repainfan bottle through a double needle head, stirring for 4 hours at-78 ℃, absorbing tail gas by using carbon tetrachloride, and slowly heating to room temperature during reaction; removing the solvent from the reacted solution by rotary evaporation, adding excessive ethyl acetate into residues after the rotary evaporation, adjusting the pH of the solution to 4 by using diluted HCl, washing the solution with deionized water for three times, drying the organic phase by using anhydrous magnesium sulfate, and removing the solvent from the dried organic phase by rotary evaporation; the substrate was distilled under reduced pressure at 40 ℃ at 300mtorr to give 2-hexafluoroisopropanol pyridine as a colorless liquid.
(2) Synthesis of 1-butyl-2 hexafluoroisopropanol pyridine bromide salt: the product of the previous step was dissolved in 115mL of isopropanol, heated to 45 ℃ and the same molar amount of bromobutane was added (45min after addition). Refluxing for 28h, cooling, evaporating the solvent to obtain a product, and recrystallizing in ethanol-ethyl acetate mixed solution. And during recrystallization, dissolving the product in an ethanol-ethyl acetate mixed solution, heating to 74-76 ℃, filtering while the solution is hot, repeating the operation for three times, standing and cooling the filtrate, and standing for 24 hours until crystals are generated. The filtered solid was dried under vacuum to constant weight. The product of the previous step was dissolved in 115mL of isopropanol, heated to 45 ℃ and the same molar amount of bromobutane was added (45min after addition). Refluxing for 28h, cooling, evaporating the solvent to obtain a product, and recrystallizing in ethanol-ethyl acetate mixed solution. And during recrystallization, dissolving the product in an ethanol-ethyl acetate mixed solution, heating to 74-76 ℃, filtering while the solution is hot, repeating the operation for three times, standing and cooling the filtrate, and standing for 24 hours until crystals are generated. The filtered solid was dried under vacuum to constant weight.
(3) Synthesis of 1-butyl-2 hexafluoroisopropylsulfonic pyridine chlorosulfonate: slowly adding 0.1mol of the product into 0.22mol of chlorosulfonic acid at-15 ℃, and slowly heating to 35 ℃ for 5 hours after the addition is finished. Washing the product with dichloromethane, and then drying in vacuum to obtain the target product 1-butyl-2 hexafluoroisopropylsulfonic acid pyridine chlorosulfonate.
And (3) characterization:
1H NMR(300MHz,[D6]DMSO,25℃):δ＝0.89(m,3H,(CH2)3CH3),1.3(m,2H,N(CH2)2CH2CH3),2.01(m,2H,N(CH2)CH2(CH2CH3)),4.2(m,1H,SO4H),5.01(m,2H,NCH2CH2CH2CH3),8.09(m,1H,N(CH)CH(CHCHC)),8.31(m,1H,N(CHCHCH)CHC)),8.56(m,1H,N(CHCH)CH(CHC)),8.92(d,1H,NCH(CHCHCH)C)).ESI/MS:m/z(+)382,m/z(－)114.9。
the test shows that the acidity of the 8# ionic liquid is H0＝-8.241。
EXAMPLE 91 preparation of butyl-2-hexafluoroisopropylsulfonate pyridine triflate (# 9 Ionic liquid)
The 1-butyl-2 hexafluoroisopropylsulfonate pyridine chlorosulfonate prepared in example 8 and trifluoromethanesulfonic acid are subjected to ion exchange at normal temperature for 24h and then subjected to rotary evaporation to obtain 1-butyl-2 hexafluoroisopropylsulfonate pyridine trifluoromethanesulfonate.
And (3) characterization:
1H NMR(300MHz,[D6]DMSO,25℃):δ＝0.89(m,3H,(CH2)3CH3),1.3(m,2H,N(CH2)2CH2CH3),2.01(m,2H,N(CH2)CH2(CH2CH3)),4.2(m,1H,SO4H),5.01(m,2H,NCH2CH2CH2CH3),8.09(m,1H,N(CH)CH(CHCHC)),8.31(m,1H,N(CHCHCH)CHC)),8.56(m,1H,N(CHCH)CH(CHC)),8.92(d,1H,NCH(CHCHCH)C)).ESI/MS:m/z(+)382,m/z(－)149。
the acidity of the 9# ionic liquid is tested to be H0＝-8.27。
Comparative example 1 preparation of Methylimidazolium hexafluoroisopropylsulfonate
Figure BDA0001400449800000271
In a 100mL single-neck flask, 0.1mol of methylimidazole (8.2g) was dissolved in 16.4mL of anhydrous ether, and 0.1mol of hexafluoroisopropylsulfonic acid (24.8g) was placed in an isobaric dropping funnel under nitrogen protection. When the temperature of the system is reduced to 0 ℃, slowly dripping hexafluoro-isopropylsulfonic acid into the ether solution of the methylimidazole, continuously stirring and reacting for 2 hours after the dripping of the hexafluoro-isopropylsulfonic acid is finished, stopping cooling, heating the system to room temperature, washing the crude product for 3 times by using anhydrous ether, and performing rotary evaporation to obtain the methylimidazole hexafluoro-isopropylsulfonate which is marked as No. 10 ionic liquid.
And (3) characterization:1H NMR(300MHz,[D6]DMSO,25℃):δ＝3.72(s,3H,CH3),7.75(t,1H,(CH)CH(NH)),7.92(d,1H,NCH),8.92(d,1H,(NH)CHN),9.0(m,1H,CH(CF3)2),11.12(s,1H,NH).ESI/MS:m/z(+)83.06,m/z(－)246.95。
the acidity of the ionic liquid prepared in the comparative example was tested to be H0＝-5.45。
Comparative example 2 preparation of Ionic liquid of Methylimidazolium triflate
Figure BDA0001400449800000272
In a 100mL single-neck flask, 0.1mol of methylimidazole (8.2g) was dissolved in 16.4mL of water, and 0.1mol of trifluoromethanesulfonic acid (15.01g) was placed in a constant-pressure dropping funnel under nitrogen. When the temperature of the system is reduced to 0 ℃, slowly dripping hexafluoro-isopropylsulfonic acid into the ether solution of the methylimidazole, continuously stirring and reacting for 2 hours after the dripping of the hexafluoro-isopropylsulfonic acid is finished, stopping cooling, heating the system to room temperature, and performing rotary evaporation to obtain methylimidazole hexafluoro-isopropylsulfonate, which is marked as 11# ionic liquid.
And (3) characterization:1H NMR(300MHz,[D6]DMSO,25℃):δ＝3.72(s,3H,CH3),7.75(t,1H,(CH)CH(NH)),7.92(d,1H,NCH),8.92(d,1H,(NH)CHN),9.0(m,1H,CH(CF3)2),11.12(s,1H,NH).ESI/MS:m/z(+)83.06,m/z(－)246.95。
the acidity of the ionic liquid prepared in the comparative example was tested to be H0＝-5.51。
Comparative example preparation of 31, 3-dimethyl-2-imidazolidinone hexafluoroisopropylsulfonate
Figure BDA0001400449800000273
In a 100mL single-neck flask, 0.1mol of 1, 3-dimethyl-2-imidazolidinone (11.4g) was dissolved in 22.8mL of anhydrous ether, and 0.1mol of hexafluoroisopropylsulfonic acid (24.8g) was placed in a constant pressure dropping funnel under nitrogen. When the temperature of the system is reduced to 0 ℃, slowly dripping hexafluoro-isopropylsulfonic acid into the ether solution of the methylimidazole, continuously stirring and reacting for 2 hours after the dripping of the hexafluoro-isopropylsulfonic acid is finished, stopping cooling, heating the system to room temperature, washing the crude product for 3 times by using anhydrous ether, and performing rotary evaporation to obtain 1, 3-dimethyl-2-imidazolidinone hexafluoro-isopropylsulfonate which is marked as # 12 ionic liquid.
And (3) characterization:1HNMR(300MHz,[D6]DMSO,25℃):δ＝2.90(s,3H,(NH)CH3),3.27(s,3H,NCH3),3.59(m,2H,(NH)CH2),3.70(m,2H,NCH3),7.2(s,1H,NH),8.3(m,1H,CH(CF3)2).ESI/MS:m/z(+)115.09,m/z(－)246.95。
the acidity of the ionic liquid prepared in the comparative example was tested to be H0＝-5.27。
Synthesis of n-butyl acetate
Application example 1:
the hexafluoroisopropylsulfonate-disulfonic acid ammonium trifluoromethanesulfonate ionic liquid (3# ionic liquid) is used for synthesizing the catalyst of n-butyl acetate, and the specific steps are as follows: adding 0.12mol of acetic acid into a three-neck flask, then adding 0.1mol of n-butyl alcohol, adding 0.001mol of ionic liquid, heating at 90 ℃, reacting for 2h, separating a product by using a separating funnel to obtain n-butyl acetate, and analyzing by gas mass spectrometry to obtain the yield of over 99 percent.
Comparative application example 1-1: the method is characterized in that methylimidazole hexafluoroisopropylsulfonate ionic liquid (10# ionic liquid) is used for synthesizing the catalyst of n-butyl acetate, and the method comprises the following specific steps: adding 0.12mol of acetic acid into a three-neck bottle, then adding 0.1mol of n-butyl alcohol, adding 0.001mol of ionic liquid, heating at 90 ℃, reacting for 2h, and failing to perform esterification reaction.
Comparative application examples 1-2: the method is characterized in that 1, 3-dimethyl-2-imidazolidinone hexafluoro-isopropyl sulfonate ionic liquid (No. 12 ionic liquid) is used for synthesizing the catalyst of n-butyl acetate, and comprises the following specific steps: adding 0.12mol of acetic acid into a three-neck bottle, then adding 0.1mol of n-butyl alcohol, adding 0.001mol of ionic liquid, heating at 90 ℃, reacting for 2h, and failing to perform esterification reaction.
Synthesis of methyl tetrahydrophthalic anhydride
Application example 2
The hexafluoroisopropylsulfonate-disulfonic acid ammonium trifluoromethanesulfonate ionic liquid (3# ionic liquid) is used for synthesizing the catalyst of the methyl tetrahydrophthalic anhydride, and the specific steps are as follows: adding 0.12mol of isoprene into a three-neck flask, then adding 0.1mol of maleic anhydride, adding 0.001mol of ionic liquid, heating at 50 ℃, reacting for 2.5h, and dissolving the product in acetone for gas mass spectrometry detection. The GC-MS spectrum is shown in FIG. 1, from left to right, as the solvents acetone (retention time 0.7), isoprene (retention time 2.5) and methyl tetrahydrophthalic anhydride (retention time 32.5). The conversion rate of maleic anhydride is more than 99 percent, and the yield is 99 percent.
Comparative application example 2-1:
the method is characterized in that methylimidazole hexafluoroisopropylsulfonate ionic liquid (10# ionic liquid) is used for synthesizing the catalyst of methyl tetrahydrophthalic anhydride, and the method comprises the following specific steps: adding 0.12mol of isoprene into a three-neck flask, then adding 0.1mol of maleic anhydride, adding 0.001mol of ionic liquid, heating at 50 ℃, reacting for 2.5h, and dissolving the reaction product in acetone for gas mass spectrometry detection. The proportion of the polymerization reaction product is more than 50 percent, and the specific gravity of the methyl tetrahydrophthalic anhydride is lower than 20 percent.
Synthesis of benzoic acid
Application example 3
The synthesis of the benzoic acid catalyst by using hexafluoroisopropylsulfonate-disulfonate ammonium hexafluoroisopropylsulfonate ionic liquid (13# ionic liquid) comprises the following specific steps: adding 0.69mol of acrylic acid into a three-necked bottle, then adding 0.01mol of furan, adding 0.001mol of ionic liquid, heating at 100 ℃, reacting for 2 hours, diluting with dimethyl sulfoxide, then carrying out gas phase detection, and comparing with a standard sample to prove that the product benzoic acid is obtained.
Comparative application example 3-1: the method is characterized in that methylimidazole hexafluoroisopropylsulfonate ionic liquid (10# ionic liquid) is used for synthesizing benzoic acid catalyst, and the method comprises the following specific steps: 0.69mol of acrylic acid, 0.01mol of furan and 0.001mol of ionic liquid are added into a three-necked flask, the mixture is heated at 100 ℃ for 2 hours to react, and after the mixture is diluted by dimethyl sulfoxide, gas phase detection is carried out, and no benzoic acid is generated.
Comparative application example 3-2: the 1, 3-dimethyl-2-imidazolidinone hexafluoro-isopropyl sulfonate ionic liquid is used as a catalyst for synthesizing benzoic acid, and the method specifically comprises the following steps: 0.69mol of acrylic acid, 0.01mol of furan and 0.001mol of ionic liquid are added into a three-necked flask, the mixture is heated at 100 ℃ for 2 hours to react, and after the mixture is diluted by dimethyl sulfoxide, gas phase detection is carried out, and no benzoic acid is generated.
Synthesis of para-xylene
Application example 4
The method is characterized in that hexafluoroisopropylsulfonate-disulfonate ammonium hexafluoroisopropylsulfonate ionic liquid (3# ionic liquid) is used for synthesizing a catalyst for paraxylene, and comprises the following specific steps: adding 0.69mol of acrylic acid into a three-neck flask, then adding 0.01mol of dimethyl furan, adding 0.001mol of ionic liquid, heating at 30 ℃, reacting for 2 hours, diluting with acetone, and then carrying out gas mass spectrometry for detecting the content of a main product, namely the paraxylene, by 20%.
Application example 4-1: the method is characterized in that methylimidazole hexafluoroisopropylsulfonate ionic liquid (10# ionic liquid) is used as a catalyst for synthesizing paraxylene, and comprises the following specific steps: adding 0.69mol of acrylic acid into a three-neck flask, then adding 0.01mol of dimethyl furan, adding 0.001mol of ionic liquid, heating at 30 ℃, reacting for 2h, diluting with acetone, and then carrying out gas phase mass spectrometry detection, wherein the generation of p-xylene or 2, 5-dimethyl benzoic acid is not detected.
Application example 4-2: the acidity of methylimidazole hexafluoroisopropylsulfonate (10# ionic liquid) is increased to obtain methylimidazole: the acidic ionic liquid of hexafluoro-isopropylsulfonic acid ═ 1:1.2 is used as a catalyst for synthesizing paraxylene, and the specific steps are as follows: adding 0.69mol of acrylic acid into a three-neck flask, then adding 0.01mol of dimethyl furan, adding 0.001mol of ionic liquid, heating at 30 ℃, reacting for 2h, diluting with acetone, and then carrying out gas-phase mass spectrometry detection, wherein the main product is p-xylene, and the yield is 23%.
The applicant states that the present invention is illustrated by the above examples of the process of the present invention, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (7)

1. An ionic liquid, wherein a cation of the ionic liquid contains a hexafluoroisopropylsulfonic acid group, and the cation has any one of the following structures:
Figure FDA0002409568970000011
2. the method of claim 1An ionic liquid, characterized in that the anion of the ionic liquid comprises ClSO3 -、CF3SO3 -、CF3COO-、HSO4 -、NO3 -、SO4 2-、H2PO4 -、BF4 -、PF6 -、SbF6 -、(CF3)2PF4 -、(CF3)2CSO4 -、NTf2 -、p-MeC6H4SO3 -、PW12O40 3-、SiW12O40 4-、AlCl4 -、Al2Cl7 -、FeCl4 -、ZnCl3 -Or a halogen anion X-Any 1 of (1).
3. A process for the preparation of an ionic liquid according to claim 1 or 2, comprising the steps of:
(1) synthesizing a compound containing a hexafluoroisopropanol group;
(2) quaternizing the compound containing the hexafluoroisopropanol group obtained in the step (1) to obtain a halogenated quaternary ammonium salt containing the hexafluoroisopropanol group;
(3) and (3) performing chlorosulfonation reaction on the quaternary ammonium salt containing the hexafluoroisopropanol group obtained in the step (2) to obtain the ionic liquid of which the cation contains the hexafluoroisopropanol sulfonic acid group.
4. The production method according to claim 3, wherein step (3) is followed by step (4): and (4) carrying out neutralization reaction on the ionic liquid in the step (3) and acid containing target anions or double decomposition reaction on inorganic salt containing the target anions, and replacing the anions to obtain the ionic liquid of the target anions.
5. The method of claim 4, wherein the target-containing anions are selected from the group consisting ofThe acid/salt of seed comprises HClSO3、HCF3SO3、CF3COOH、H2SO4、HNO3、H3PO4、KBF4、NaPF6、NaSbF6、H(CF3)2PF4、(CF3)2CSO4H、LiNTf2、p-MeC6H4SO3H、H3PW12O40、H4SiW12O40、AlCl3、FeCl3、ZnCl2And a combination of any 1 or at least 2 of the halogen acids.
6. The method of claim 5, wherein the hydrohalic acid comprises any 1 or a combination of at least 2 of HF, HBr, HCl.
7. Use of an ionic liquid according to claim 1 or 2 as a reaction medium and/or acid catalyst for alkylation reactions, Diels Alder reactions, esterification reactions, aldolisation reactions, dimerization reactions, Michael additions, isomerization reactions.
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