CN116903538A

CN116903538A - Imidazole ionic compound containing fluorosulfonate radical and synthesis and application thereof

Info

Publication number: CN116903538A
Application number: CN202310513338.6A
Authority: CN
Inventors: 林江滨; 肖吉昌; 林锦鸿
Original assignee: Hangzhou Baoming New Material Technology Co ltd; Shanghai Institute of Organic Chemistry of CAS; University of Shanghai for Science and Technology
Current assignee: Hangzhou Baoming New Material Technology Co ltd; Shanghai Institute of Organic Chemistry of CAS; University of Shanghai for Science and Technology
Priority date: 2023-05-09
Filing date: 2023-05-09
Publication date: 2023-10-20

Abstract

The invention relates to an imidazole ion compound containing fluorine sulfonate, and synthesis and application thereof. The synthesis method of the invention comprises a brand new imidazole ionic compound of polyfluoro or perfluorosulfonate, and the density of the ionic compound is more than or equal to 1.5g/cm ³ The glass transition temperature is less than or equal to-40 ℃ and the decomposition temperature is 294-442 ℃. In addition, the ions of the inventionThe liquid synthesis method is simple, the reaction condition is mild, the raw materials are cheap and easy to obtain, the yield is high, and the product purity is good. The ions have higher density and have certain application potential in the fields of aerospace gyro oil materials and pesticides.

Description

Imidazole ionic compound containing fluorosulfonate radical and synthesis and application thereof

Technical Field

The invention relates to the field of organic synthesis, in particular to synthesis and application of fluoroalkyl sulfonate ionic liquid.

Background

Ionic liquids are salts composed of an organic cation and an organic or inorganic anion that are liquid at or near room temperature. It is very different from conventional high temperature molten ionic salts. Conventional ionic salts can only become liquid at high temperatures, whereas ionic liquids are liquid over a wide temperature range around room temperature.

The development of ionic liquids dates back to more than one hundred years but has not received attention at that time (s.sugden et al, j.chem. Soc.,1929, 1291-1298). In 1948, hurley and Wier used ionic liquids in the electrochemical field, but the study of ionic liquids has not attracted the academic attention (F.H.Hurley, U.S.Patent 2,446,331,1948). The ionic liquid has been newly applied in the middle of the 80 s of the last century, and Seddon et al have found that an ionic liquid with chloroaluminate as an anion can be used as a reaction medium (t.b. scheffler et al, inorg. Chem.1983,22, 2099-2100). However, ionic liquids composed of these halogenated metal salts are very sensitive to water and air and are difficult to be widely used. In 1992, wilkes et al synthesized the first ionic liquid [ emim ] stable to both water and air][BF ₄ ](J.S. Wilkes et al J.Chem.Soc., chem.Commun.,1992, 965-967); shortly thereafter, [ emim ]][PF ₆ ]Also known (J. Fuller et al, J.Chem.Soc., chem.Commun.,1994, 299-300). [ BF ] ₄ ^- ]And [ PF ] ₆ ^- ]The ionic liquid which is anions is stable to water and has good practicability. Thereafter, ionic liquids have evolved vigorously. By the year 2000, pyridines (d.zhao et al, j.am.chem.soc.2004,126, 15876-15882), pyrroles (a. -v.musing et al, angelw). Ionic liquids in which chem.int.ed.2005,44, 5485-5488), quaternary phosphonium species (j.mcnulty et al, chem.eur.j.2006,12, 9314-9322), polyamines (s.i.lall et al, chem.Commun.,2000, 2413-2414), even bisimidazoles (k.ito et al, electrochimica Acta,2000,45,1295-1298) and the like are cationic are reported successively. The anion species are also numerous, and the rapidly developing ionic liquid species lay the foundation for the large-scale development of the foundation and application research of ionic liquids (d.zhao et al., cat. Today 2002,74,157-189).

Ionic liquids have many unique properties (R.Sheodon, chem.Commum.2001,2399-2407): the vapor pressure is low and the volatile matter is not easy to volatilize; the chemical stability is high; can dissolve a plurality of organic, inorganic and metal organic compounds; gases such as hydrogen, oxygen, carbon monoxide, and the like can be dissolved; are immiscible with certain organic solvents, such as alkanes, and thus can be used in two-phase systems; similarly, lipophilic ionic liquids can be used in water-ionic liquid two-phase systems; the polarity and hydrophilicity, and lipophilicity can be changed by adjusting the collocation of anions and cations; the coordination ability of anions is weak, so that the ionic liquid can be used as a high-polarity low-coordination solvent.

The ionic liquid [ emim ]][BF ₄ ]And [ emim ]][PF ₆ ]Are all fluorine-containing ionic liquids. Compared to non-fluorine containing ionic liquids, fluorine containing ionic liquids have many advantageous properties: has strong hydrophobicity, good stability, difficult oxidation and strong acid and alkali resistance. These advantages have led to the development of new fluorine-containing ionic liquids. The fluorine-containing ionic liquid can be divided into two types according to the difference of fluorine-containing substituent positions, wherein one type is cationic fluorine-containing ionic liquid, and the other type is anionic fluorine-containing ionic liquid. Along with the continuous synthesis of various novel fluorine-containing ionic liquids, the application fields of the novel fluorine-containing ionic liquids are also continuously expanded. However, in general, studies on fluorine-containing ionic liquids have been carried out. Therefore, on one hand, the design synthesis of the novel fluorine-containing ionic liquid needs to be developed, and a novel synthesis method of the fluorine-containing ionic liquid is developed through the development of novel fluorine-containing anions and the synthesis of fluorine-containing cations; meanwhile, the structure and the performance of the fluorine-containing ionic liquid are further explored through testing and characterizing the physicochemical properties of the fluorine-containing ionic liquidRelationship between them.

High density fluids have a wide range of applications such as peg-top oil slivers for aerospace technology. Polyhalogenated compounds have relatively high densities, but they have the common disadvantage of being highly volatile and toxic, which limits their use in a temperature range around room temperature. In view of the characteristics of the ionic liquid, the ionic liquid with higher density and lower melting point can be synthesized (density >1.5g/cm ^-3 High density fluids are generally considered to be relatively dense and fluids having a melting point below room temperature are generally considered to be relatively low), and should be able to remedy this deficiency.

The greater the volume of anions, the greater the density of the ionic liquid in general. For the same cations, the general order in which the density of ionic liquids gradually increases from anion to anion is (C.Ye, J.M.Shreeve, J.Org.Chem.2004,69, 6511-6513): [ CH ] ₃ SO ₃ ]-≈[BF ₄ ] ^- <[CF ₃ COO] ^- <[CF ₃ SO ₃ ] ^- <[PF ₆ ]-<[NTf ₂ ]-. The larger the volume of the cation, the smaller the density of the ionic liquid is, and the small change of the cation structure can adjust the density of the ionic liquid to different degrees.

After the hydrogen in the organic compound is replaced by fluorine, the fluorine-containing compound generally has a higher density because of the larger atomic weight of fluorine than hydrogen, and the fluorine-containing ionic liquid should have a higher density than the corresponding fluorine-free ionic liquid. The research on the influence of the introduction of fluorine element into ionic liquid on the density is lacking at present. Therefore, we explore the synthesis of a series of high density fluorine-containing ionic liquids.

Disclosure of Invention

The invention aims to solve the technical problems of synthesis of novel fluoroalkyl sulfonate ionic liquid and find application of the ionic liquid in the research fields of high-density materials and pesticides.

In one aspect, the invention provides an imidazole ionic compound containing fluorosulfonate, wherein the density of the ionic compound is more than or equal to 1.5g/cm ³ 。

In a preferred embodiment, the ionic compound has a glass transition temperature of less than or equal to-38℃and a decomposition temperature of 294-442 ℃.

On the other hand, the invention also provides an imidazole ionic compound containing fluorine sulfonate, wherein the ionic compound has the following structural formula:

wherein:

R ¹ 、R ³ is C ₁ -C ₄ Alkyl, C ₁ -C ₄ Fluoroalkyl or aryl;

R ² 、R ⁴ 、R ⁵ is hydrogen or C ₁ -C ₄ Alkyl, C ₁ -C ₄ Alkoxy or aryl;

x is hydrogen, fluorine, chlorine or iodine;

n is an integer of 1 to 3.

In a preferred embodiment, the present invention provides an ionic compound wherein the aryl group isR ⁶ 、R ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ Is C ₁ -C ₄ Alkyl or C ₁ -C ₄ An alkoxy group.

In a preferred embodiment, the present invention provides an ionic compound wherein the aryl group is preferably phenyl or naphthyl.

The C is ₁ -C ₄ The alkyl is selected from at least one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl.

In a preferred embodiment, the present invention provides an ionic compound, said C ₁ -C ₄ The alkoxy group is selected from at least one of methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy.

In a preferred embodiment, the present invention provides an ionic compound, said C ₁ -C ₄ Fluoroalkyl is selected from fluorogensAt least one of a child-substituted methyl group, a fluorine-atom-substituted ethyl group, a fluorine-atom-substituted propyl group, a fluorine-atom-substituted isopropyl group, a fluorine-atom-substituted butyl group, a fluorine-atom-substituted isobutyl group, or a fluorine-atom-substituted tert-butyl group.

In a preferred embodiment, the present invention provides an ionic compound,

the methyl substituted by fluorine atoms is monofluoromethyl;

the fluorine atom substituted ethyl is monofluoroethyl;

the fluorine atom-substituted propyl group is a monofluoropropyl group;

the fluorine atom-substituted isopropyl is monofluoroisopropyl;

the fluorine atom-substituted butyl is monofluorobutyl;

the fluorine atom-substituted isobutyl is monofluoroisobutyl;

the fluorine atom-substituted tert-butyl group is monofluorine tert-butyl group.

In a preferred embodiment, the present invention provides an ionic compound having any one of the following structures:

in a preferred embodiment, the present invention provides an ionic compound having a density of 1.5g/cm or more ³ 。

In a preferred embodiment, the present invention provides an ionic compound having a glass transition temperature of at most-38deg.C and a decomposition temperature of 294-442 deg.C.

In yet another aspect, the present invention also provides a process for preparing an ionic compound as defined in the claims, comprising: ion exchange reaction of ionic salts with sulfonates in solvents, wherein:

the ionic salt is

The sulfonate is X (CF) ₂ CF ₂ )nOCF ₂ CF ₂ SO ₃ M，

R ¹ 、R ³ Is C ₁ -C ₄ Alkyl, C ₁ -C ₄ Fluoroalkyl or aryl;

y is halogen, preferably chlorine, bromine or iodine;

x is hydrogen, fluorine, chlorine or iodine;

m is tetraalkylammonium, sodium or potassium;

n is an integer of 1 to 3.

In a preferred embodiment, the present invention also provides a process for preparing the ionic compound as described in the claims, wherein the solvent is selected from one or more of water, an alcoholic solvent, a mixed solvent of water and an alcoholic solvent, an amide-based solvent, a sulfoxide-based solvent and a nitrile-based solvent.

In a preferred embodiment, the present invention also provides a process for preparing the ionic compounds as described in the claims, the amide solvent preferably being N, N-dimethylformamide; the alcohol solvent is preferably ethanol, tertiary butanol or tertiary amyl alcohol; the nitrile solvent is preferably acetonitrile; the sulfoxide solvent is preferably dimethyl sulfoxide.

In a preferred embodiment, the present invention also provides a process for preparing an ionic compound as defined in the claims, wherein the aryl group is R ⁶ 、R ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ Is C ₁ -C ₄ Alkyl or C ₁ -C ₄ An alkoxy group.

In a preferred embodiment, the present invention also provides a process for preparing an ionic compound as described in the claims, said C ₁ -C ₄ The alkyl is selected from at least one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl.

In a preferred embodiment, the present invention also provides a process for preparing an ionic compound as described in the claims, said C ₁ -C ₄ The alkoxy group is selected from at least one of methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy.

In a preferred embodiment, the present invention also provides a process for preparing an ionic compound as described in the claims, said C ₁ -C ₄ The fluoroalkyl group is at least one selected from a fluorine atom-substituted methyl group, a fluorine atom-substituted ethyl group, a fluorine atom-substituted propyl group, a fluorine atom-substituted isopropyl group, a fluorine atom-substituted butyl group, a fluorine atom-substituted isobutyl group, and a fluorine atom-substituted tert-butyl group.

In a preferred embodiment, the present invention also provides a process for preparing an ionic compound as described in the claims,

the methyl substituted by fluorine atoms is monofluoromethyl;

the fluorine atom substituted ethyl is monofluoroethyl;

the fluorine atom-substituted propyl group is a monofluoropropyl group;

the fluorine atom-substituted isopropyl is monofluoroisopropyl;

the fluorine atom-substituted butyl is monofluorobutyl;

the fluorine atom-substituted isobutyl is monofluoroisobutyl;

In a preferred embodiment, the present invention also provides a process for preparing the ionic compounds as described in the claims, the reaction temperature of the ion exchange reaction being from 0 to 120 ℃.

In a preferred embodiment, the present invention also provides a process for preparing an ionic compound as described in the claims, wherein the time of the ion exchange reaction is from 0.5 to 24 hours.

In a preferred embodiment, the present invention also provides a process for preparing an ionic compound as described in the claims, the sulfonate being prepared by the steps of:

a) At 80 ℃, C _4-8 1, 4-dioxane solution of iodide;

b) Dripping into 1, 4-dioxane solution of zinc powder until the zinc powder amount is no longer reduced, cooling to room temperature, and transferring into 0-5deg.C ice water bath;

c) Adding HCl solution until zinc powder is not reduced, filtering, adding water into filtrate, shaking, standing to upper layer, and layering lower layer;

d) Extracting the aqueous layer with dichloromethane, mixing the dichloromethane extract and the oil layer, washing with water, drying, and distilling to obtain C _4-8 A hydride;

e) C is C _4-8 Dissolving the hydride in ethanol, adding aqueous solution of sodium hydroxide, and heating to 110deg.C

Then, refluxing and stirring at 80 ℃ until the reaction is stopped, concentrating under reduced pressure to remove ethanol, heating with ethyl acetate until the mixture is refluxed and dissolved, filtering, concentrating under reduced pressure to obtain white solid;

wherein, the liquid crystal display device comprises a liquid crystal display device,

the C in step a) _4-8 The mass ratio of iodide to zinc powder in step c) was 3.28:1, a step of;

step e) said C _4-8 The mass ratio of the hydride to the sodium hydroxide is 3.75:1.

c is C _4-8 Dissolving iodide in ethanolAdding sodium hydroxide aqueous solution, heating to 110deg.C, refluxing at 80deg.C, stirring to stop reaction, concentrating under reduced pressure to remove ethanol, heating with ethyl acetate to reflux, dissolving, filtering, concentrating under reduced pressure to obtain white solid;

the C is _4-8 The mass ratio of iodide to sodium hydroxide is 3.75:1.

in a preferred embodiment, the present invention also provides a process for preparing an ionic compound as described in the claims, said C _4-8 The iodide is selected from: ICF (information and communication function) ₂ CF ₂ OCF ₂ CF ₂ SO ₂ F、I(CF ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₂ F、I(CF ₂ CF ₂ ) ₃ OCF ₂ CF ₂ SO ₂ F。

In a preferred embodiment, the present invention also provides a process for preparing an ionic compound as described in the claims, said ionic salt being prepared by the steps of: freezing 1-methylimidazole liquid nitrogen to-190 deg.C, adding C _1-3 The iodate is recovered to normal temperature, and the reaction is carried out at 50-120 ℃ under vacuum until the reaction is stopped, and the product is obtained after the product is washed by diethyl ether, wherein the 1-methylimidazole and the C _1-3 The mass ratio of the iodoalkane is 0.53:1.

In a preferred embodiment, the present invention also provides a process for preparing an ionic compound as described in the claims, said C _1-3 The iodoalkane is selected from: methyl iodide, ethyl iodide, and propyl iodide.

In yet another aspect, the present invention also provides an application of an ionic compound in the field of high density materials.

In a preferred embodiment, the invention also provides the use of an ionic compound in the field of pesticides.

The fields of pesticides of the present invention include, but are not limited to, the fields of herbicidal, bactericidal and insecticidal activity.

The above preferred conditions can be arbitrarily combined on the basis of not deviating from the common knowledge in the art, and thus, each preferred embodiment of the present invention can be obtained.

The invention has the positive progress effects that: the synthesis method has the advantages of simple method, mild reaction condition, low-cost and easily-obtained raw materials, high yield and good product purity; the fluoroalkyl sulfonate ionic liquid has high density and important application value in the field of high density; but also has herbicidal, bactericidal and insecticidal activities and has important application value in pesticide research.

Drawings

FIG. 1 is a fluorine nuclear magnetic resonance (F-NMR) spectrum of an ionic liquid 7ab reddish brown liquid prepared in example 17;

FIG. 2 is a hydrogen nuclear magnetic resonance (H-NMR) spectrum of an ionic liquid 7ab reddish brown liquid prepared in example 17;

FIG. 3 is a fluorine nuclear magnetic resonance (F-NMR) spectrum of an ionic liquid 7ac reddish brown liquid prepared in example 18;

FIG. 4 is a hydrogen nuclear magnetic resonance (H-NMR) spectrum of an ionic liquid 7ac reddish brown liquid prepared in example 18;

FIG. 5 is a fluorine nuclear magnetic resonance (F-NMR) spectrum of an ionic liquid 7ad reddish brown liquid prepared in example 19;

FIG. 6 is a hydrogen nuclear magnetic resonance (H-NMR) spectrum of an ionic liquid 7ad reddish brown liquid prepared in example 19;

FIG. 7 is a fluorine nuclear magnetic resonance (F-NMR) spectrum of an ionic liquid 7bb reddish brown liquid prepared in example 20;

FIG. 8 is a hydrogen nuclear magnetic resonance (H-NMR) spectrum of an ionic liquid 7bb reddish brown liquid prepared in example 20;

FIG. 9 is a fluorine nuclear magnetic resonance (F-NMR) spectrum of a reddish brown liquid of the ionic liquid 7bc prepared in example 21;

FIG. 10 is a hydrogen nuclear magnetic resonance (H-NMR) spectrum of a reddish brown liquid of the ionic liquid 7bc prepared in example 21;

FIG. 11 is a fluorine nuclear magnetic resonance (F-NMR) spectrum of an ionic liquid 7bd reddish brown liquid prepared in example 22;

FIG. 12 is a hydrogen nuclear magnetic resonance (H-NMR) spectrum of a 7bd reddish brown liquid of the ionic liquid prepared in example 22;

FIG. 13 is a fluorine nuclear magnetic resonance (F-NMR) spectrum of an ionic liquid 7ca reddish brown liquid prepared in example 23;

FIG. 14 is a hydrogen nuclear magnetic resonance (H-NMR) spectrum of an ionic liquid 7ca reddish brown liquid prepared in example 23;

FIG. 15 is a fluorine nuclear magnetic resonance (F-NMR) spectrum of an ionic liquid 7cb reddish brown liquid prepared in example 24;

FIG. 16 is a hydrogen nuclear magnetic resonance (H-NMR) spectrum of an ionic liquid 7cb reddish brown liquid prepared in example 24;

FIG. 17 is a fluorine nuclear magnetic resonance (F-NMR) spectrum of 7cc of reddish brown liquid of the ionic liquid prepared in example 25;

FIG. 18 is a hydrogen nuclear magnetic resonance (H-NMR) spectrum of 7cc of reddish brown liquid of the ionic liquid prepared in example 25;

FIG. 19 is a fluorine nuclear magnetic resonance (F-NMR) spectrum of an ionic liquid 7cd, reddish brown liquid prepared in example 26;

FIG. 20 is a hydrogen nuclear magnetic resonance (H-NMR) spectrum of an ionic liquid 7cd, reddish brown liquid prepared in example 26;

FIG. 21 is a fluorine nuclear magnetic resonance (F-NMR) spectrum of a 7db reddish brown liquid of the ionic liquid prepared in example 27;

FIG. 22 is a hydrogen nuclear magnetic resonance (H-NMR) spectrum of a 7db reddish brown liquid of the ionic liquid prepared in example 27;

FIG. 23 is a fluorine nuclear magnetic resonance (F-NMR) spectrum of an ionic liquid 7dc reddish brown liquid prepared in example 28;

FIG. 24 is a hydrogen nuclear magnetic resonance (H-NMR) spectrum of an ionic liquid 7dc reddish brown liquid prepared in example 28;

FIG. 25 is a fluorine nuclear magnetic resonance (F-NMR) spectrum of an ionic liquid 7dd reddish brown liquid prepared in example 29;

FIG. 26 is a hydrogen nuclear magnetic resonance (H-NMR) spectrum of an ionic liquid 7dd reddish brown liquid prepared in example 29;

FIG. 27 is a fluorine nuclear magnetic resonance (F-NMR) spectrum of an ionic liquid 7ec reddish brown liquid prepared in example 30;

FIG. 28 is a hydrogen nuclear magnetic resonance (H-NMR) spectrum of an ionic liquid 7ec reddish brown liquid prepared in example 30;

Detailed Description

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described herein. For the purposes of the present invention, the following terms are defined below.

Alkoxy group

Alkoxy in the present invention means an alkyl group linked through an oxygen bridge; the alkyl group means a saturated straight or branched monovalent hydrocarbon group having one to twelve carbon atoms.

Alkoxy groups according to the invention are preferably C ₁ -C ₄ An alkoxy group.

The invention is described as C ₁ -C ₄ The alkoxy group is selected from at least one of methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy.

Alkyl group

The alkyl group according to the present invention means a saturated straight or branched monovalent hydrocarbon group having one to twelve carbon atoms.

The alkyl groups of the invention are preferably C ₁ -C ₄ Alkyl, said C ₁ -C ₄ The alkyl is at least one selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl.

Aryl group

Aryl as used herein refers to any stable mono-or bicyclic carbocycle of up to 10 atoms in each ring, wherein both are aromatic.

The aryl group isR ⁶ 、R ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ Is C ₁ -C ₄ Alkyl or C ₁ -C ₄ An alkoxy group.

The aryl group is selected from phenyl or naphthyl.

Fluoroalkyl group

Fluoroalkyl in the context of the present invention means a compound containing at least one fluorinated carbon atom. The fluoroalkyl groups according to the invention are preferably C ₁ -C ₄ A fluoroalkyl group.

The invention is described as C ₁ -C ₄ The fluoroalkyl group is at least one selected from a fluorine atom-substituted methyl group, a fluorine atom-substituted ethyl group, a fluorine atom-substituted propyl group, a fluorine atom-substituted isopropyl group, a fluorine atom-substituted butyl group, a fluorine atom-substituted isobutyl group, and a fluorine atom-substituted tert-butyl group.

The methyl substituted by fluorine atoms is monofluoromethyl;

the fluorine atom substituted ethyl is monofluoroethyl;

the fluorine atom-substituted propyl group is a monofluoropropyl group;

the fluorine atom-substituted isopropyl is monofluoroisopropyl;

the fluorine atom-substituted butyl is monofluorobutyl;

the fluorine atom-substituted isobutyl is monofluoroisobutyl;

Imidazole ion compound containing fluorosulfonate

The imidazole ionic compound containing the fluoro sulfonate can also be called imidazole ionic liquid containing the fluoro sulfonate or imidazole ionic salt containing the fluoro sulfonate.

Wherein the fluorine-containing sulfonate refers to sulfonate ions conforming to the following structural characteristics: x (CF) ₂ CF ₂ ) _n OCF ₂ CF ₂ SO ₃ ^- 。

The imidazole ion compound containing the fluorine sulfonate has any one of the following structures:

compound 1a

The invention relates to the compoundObject 1a is ICF ₂ CF ₂ OCF ₂ CF ₂ SO ₂ F chinese name: 2- (2-iodotetrafluoroethoxy) tetrafluoroethylsulfonyl fluoride, english name:

1, 2-tetrafluoroo-2- (1, 2-tetrafluoroo-2-iodoethoxy) ethane-1-sulfonyl fluoride, CAS No.:66137-74-4 molecular formula: c (C) ₄ F ₉ IO ₃ S molecular weight: 425.9961.

compound 2a

The compound 2a of the invention is HCF ₂ CF ₂ OCF ₂ CF ₂ SO ₂ F english name: 1, 2-tetrafluoro-2- (1, 2-tetrafluoro-ethoxy) ethane-1-sulfonyl fluoride.

Compound 3a

The compound 3a of the invention is HCF ₂ CF ₂ OCF ₂ CF ₂ SO ₃ Na english name: sodium1, 2-tetrafluoro-2- (1, 2-tetrafluoro-ethoxy) ethane-1-sulfonate.

Compound 1b

The compound 1b of the invention is I (CF) ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₂ F english name: 1, 2-tetrafluoro-2- (1, 2,3, 4-) Otafluoro-4-iodobutoxy) ethane-1-sulfonyl fluoride.

Compound 2b

The compound 2b of the invention is H (CF) ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₂ F English name 1, 2-tetrafluoro-2- (1, 2,3, 4) -octafluoroxy) ethane-1-sulfofluoroide.

Compound 3b

Compound 3b of the present invention is ICF ₂ CF ₂ OCF ₂ CF ₂ SO ₃ Na english name: sodium1, 2-tetrafluoro-2- (1, 2-tetrafluoro-2-iodoethoxy) ethane-1-sulfonate.

Compound 1c

The compound 1c of the present invention is I (CF) ₂ CF ₂ ) ₃ OCF ₂ CF ₂ SO ₂ F english name: 2- ((1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-6-iodoxyoxy) -1, 2-tetrafluoroethane-1-sulfonyl fluoride).

Compound 2c

The compound 2c of the present invention is H (CF) ₂ CF ₂ ) ₃ OCF ₂ CF ₂ SO ₂ F english name: 2- ((1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl) oxy) -1, 2-tetrafluoroethane-1-sulfonyl fluoride.

Compound 3c

The compound 3c of the present invention is H (CF) ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₃ Na english name: the liquid crystal material of the silicon substrate is 1,1, 2-tetrafluoro-2- (1, 2,3, 4-octafluoroxy) ethane-1-sulfonate.

Compound 3d

The compound 3d of the invention is I (CF) ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₃ Na english name: the liquid crystal material of the silicon substrate is 1,1, 2-tetrafluoro-2- (1, 2,3, 4-octafluoro-4-iodobutoxy) ethane-1-sulfonate.

Compound 3e

The compound 3e of the invention is H (CF) ₂ CF ₂ ) ₃ OCF ₂ CF ₂ SO ₃ Na english name: sodium2- ((1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl) oxy) -1, 2-tetrafluoroethane-1-sulfonate.

Compound 4a

The compound 4a of the invention, english name: 1, 3-dimethyl-1H-imidozol-3-ium iodide with structural formula

Compound 4b

Compound 4b, english name: 3-methyl-1H-imidozol-3-ium iodide with structural formula

Compound 4c

Compound 4c, english name: 1-methyl-3-propyl-1H-imidozol-3-ium iodate with structural formula

Compound 4d

Compound 4d, english name: 3-butyl-1-methyl-1H-imidozol-3-ium iodate with structural formula

Compound 4e

The compound 4e provided by the invention has the following English name: 3- (4-chloro-3, 4-tetrafluoroyl) -1, 2-dimethyl-1H-iminozol-3-iumiodide with structural formula

Compound 4f

The compound 4f of the invention, english name: 1- (2-bromoo-1, 2-tetrafluoroethyl) -3-methyl-1H-iminozol-3-iumiodide with structural formula

Compound 5

Compound 5 of the invention, english name: 1-chloro-1, 2-tetrafluoro-4-iodobutane.

Compound 6

Compound 6 of the present invention, english name: 1- (2-bromoethyl) -1H-imidozole with structural formula of 1, 2-tetrafluoro-1

Ionic liquid 7ab

The compound 7ab of the invention has the following English name: 1, 3-dimethyl-1H-imidozol-3-ium 1, 2-tetrafluoro-2- (1, 2-tetrafluoro-2-iodothoxy) ethane-1-sulfonate of the formula

Ionic liquid 7ac

The compound 7ac provided by the invention has the following English name: 1, 3-dimethyl-1H-imidozol-3-ium 1,1, 2-tetrafluoro-2- (1, 2,3, 4-octafluoroxy) ethane-1-sulfonate with structural formula

Ionic liquid 7ad

The invention relates to a compound 7ad, english name: 1, 3-dimethyl-1H-imidozol-3-ium 1,1, 2-tetrafluoro-2- (1, 2,3, 4-octafluoro-4-iodobutoxy) ethane-1-sulfonate with structural formula

Ionic liquid 7bb

Compound 7bb, english name: 3-methyl-1H-imidozol-3-ium 1, 2-tetrafluoro-2- (1, 2-tetrafluoro-2-iodomethoxy) ethane-1-sulfonate of the formula

Ionic liquid 7bc

Compound 7bc, english name: 3-methyl-1H-imidozol-3-ium 1,1, 2-tetrafluoro-2- (1, 2,3, 4-octafluoroxy) ethane-1-sulfonate with structural formula

Ionic liquid 7bd

Compound 7bd of the present invention, english name: 3-methyl-1H-imidozol-3-ium 1,1, 2-tetrafluoro-2- (1, 2,3, 4-octafluoro-4-iodobutoxy) ethane-1-sulfonate with structural formula

Ionic liquid 7ca

Compound 7ca, english name: 1-methyl-3-propyl-1H-imidozol-3-ium 1, 2-tetrafluoro-2- (1, 2-tetrafl uoroethoxy) ethane-1-sulfonate with structural formula

Ionic liquid 7cb

Compound 7cb of the invention, english name: 1-methyl-3-propyl-1H-imidozol-3-ium 1, 2-tetrafluoro-2- (1, 2-tetrafluoro-2-iodomethoxy) ethane-1-sulfonate of the formula

7cc of ionic liquid

Compound 7cc, english name: 1-methyl-3-propyl-1H-imidozol-3-ium 1,1, 2-tetrafluoro-2- (1, 2,3, 4-octafluoroxy) ethane-1-sulfonate with structural formula

Ionic liquid 7cd

The compound 7cd of the invention, english name: 1-methyl-3-propyl-1H-imidozol-3-ium 1,1, 2-tetrafluoro-2- (1, 2,3, 4-octafluoro-4-iodobutoxy) ethane-1-sulfonate with structural formula

7db of ionic liquid

The compound 7db of the invention has the following English name: 3-butyl-1-methyl-1H-imidozol-3-ium 1, 2-tetrafluoro-2- (1, 2-tetrafluoro-2-iodomethoxy) ethane-1-sulfonate of the formula

Ionic liquid 7dc

Compound 7dc, english name: 3-butyl-1-methyl-1H-imidozol-3-ium 1,1, 2-tetrafluoro-2- (1, 2,3, 4-octafluoroxy) ethane-1-sulfonate with structural formula

Ionic liquid 7dd

Compound 7dd of the invention, english name: 3-butyl-1-methyl-1H-imidozol-3-ium 1,1, 2-tetrafluoro-2- (1, 2,3, 4-octafluoro-4-iodobutoxy) ethane-1-sulfonate with structural formula

Ionic liquid 7ec

The compound 7ec of the invention, english name: 1- (4-chloro-3, 4-tetrafluoroyl) -2, 3-dimethyl-1H-imidozol-3-ium 1,1, 2-tetrafluoro-2- (1, 2,3, 4-octafluoroxy) ethane-1-sulfonate with structural formula

The term "about" as used herein refers to an amount, level, value, dimension, size, or use that may differ by up to 30%, 20%, or 10% from the amount, level, value, dimension, size, or use of a reference. The percentages used herein are by weight unless otherwise indicated.

Throughout the specification and claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

Experimental materials:

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the invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.

Example 1: compound HCF ₂ CF ₂ OCF ₂ CF ₂ SO ₂ Preparation of F (2 a)

ICF ₂ CF ₂ OCF ₂ CF ₂ SO ₂ F (0.1 mol,42.6 g) was dissolved in 30mL 1, 4-dioxane, slowly added dropwise to a 250mL three-necked flask containing zinc powder (0.2 mol,13 g) and 50mL 1, 4-dioxane at 80℃and 30mL of ICF ₂ CF ₂ OCF ₂ CF ₂ SO ₂ F, dropwise adding the solution at a constant speed within 3h, continuing to react for 10 hours until the zinc powder amount is not reduced, namely finishing the first step of reaction, and transferring into an ice water bath after cooling to room temperature.

Under ice water bath (0-5 ℃), adding 40mL of 3mol/L HCl solution, reacting for 1h, filtering after the zinc powder is no longer reduced, adding 100mL of water into the filtrate, shaking, standing to an upper water layer, and layering a lower oil layer. The lower oil layer was separated and the aqueous layer was extracted 3 times with 100mL of methylene chloride. The dichloromethane extract and the oil layer were combined, washed 3 times with 100mL of water, dried over anhydrous sodium sulfate, and dried without caking after further addition of anhydrous sodium sulfate. Then distilled at 90℃to give a clear liquid (9.9 g,33% yield) of compound 2a for use.

Test example 1: nuclear magnetic resonance

Test sample: HCF prepared in example 1 ₂ CF ₂ OCF ₂ CF ₂ SO ₂ Transparent liquid of F (Compound 2 a).

¹ H NMR was measured on a Bruker AM 300 (300 MHz) NMR at room temperature; chemical shift (δ) is expressed in ppm with tetramethylsilicon as an internal standard; the order of the hydrogen numbers is reported in terms of peak types (broad peak for br, single peak for s, double peak for d, triple peak for t, quadruple peak for q, multiple peak for m, heptadouble peak for sept, coupling constant Hz).

¹ H NMR(CDCl ₃ ,300MHz)δ6.03(tt,J＝51.7Hz,4.9Hz,1H). ¹⁹ F NMR(CDCl ₃ ,282MHz)δ45.20(s,1F),-82.26～-82.43(m,2F),-88.30～-88.46(m,2F),-112.67(m,2F),-137.88(dt,J＝51.7Hz,4.9Hz,2F).

Example 2: compound H (CF) ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₂ F) (2 b) preparation

I(CF ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₂ F (0.1 mol,42.6 g) was dissolved in 30mL 1, 4-dioxane, slowly added dropwise to a 250mL three-necked flask containing zinc powder (0.2 mol,13 g) and 50mL 1, 4-dioxane at 80℃and the reaction was continued for 10 hours after 3 hours dropwise addition until the amount of zinc powder was no longer reduced, i.e., the first reaction step was completed, and after cooling to room temperature was transferred to an ice-water bath.

Under ice water bath (0-5 ℃), adding 40mL of 3mol/L HCl solution, reacting for 1h, filtering after the zinc powder is no longer reduced, adding 100mL of water into the filtrate, shaking, standing to an upper water layer, and layering a lower oil layer. The lower oil layer was separated and the aqueous layer was extracted 3 times with 100mL of methylene chloride. The dichloromethane extract and the oil layer were combined, washed 3 times with 100mL of water, dried over anhydrous sodium sulfate, and dried without caking after further addition of anhydrous sodium sulfate. Then distilled at 90℃to give a clear liquid of Compound 2b for use (16.8 g,42% yield).

Test example 2: nuclear magnetic resonance

Test sample: h (CF) prepared in example 2 ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₂ Transparent liquid of F (Compound 2 b).

¹ H NMR was measured on a Bruker AM 300 (300 MHz) NMR at room temperature; chemical shift (δ) is expressed in ppm with tetramethylsilicon as an internal standard; according to the peak type (broad peak is expressed as br, single peak is expressed as s, double peak is expressed as d, triple peak is expressed as t, and quadruple peak is expressed asq, multiple peaks expressed as m, seven peaks as sept, coupling constant Hz), the order of the hydrogen numbers.

¹ H NMR(CDCl ₃ ,300MHz)δ6.04(tt,J＝52.0Hz,5.0Hz,1H). ¹⁹ F NMR(CDCl ₃ ,282MHz)δ45.38(s,1F),-82.48～-82.67(m,2F),-83.65～-83.86(m,2F),-112.92(s,2F),-127.29(m,2F),-130.13(m,2F),-137.74～-138.06(m,2F).

Example 3: compound H (CF) ₂ CF ₂ ) ₃ OCF ₂ CF ₂ SO ₂ F) (2 c) preparation

I(CF ₂ CF ₂ ) ₃ OCF ₂ CF ₂ SO ₂ F (0.1 mol,42.6 g) was dissolved in 30mL 1, 4-dioxane, slowly added dropwise to a 250mL three-necked flask containing zinc powder (0.2 mol,13 g) and 50mL 1, 4-dioxane at 80℃and the reaction was continued for 10 hours after 3 hours dropwise addition until the Zn powder amount was no longer reduced, i.e., the first reaction step was completed and the reaction was transferred to an ice-water bath after cooling to room temperature.

40ml of 3mol/L HCl solution was added under an ice water bath (0-5 ℃ C.) and 40ml of 3mol/L HCl solution was added to react for 1 hour until the amount of Zn powder was no longer reduced. Filtering, adding 100mL of water into the filtrate, shaking, standing to an upper water layer, and layering a lower oil layer. The lower oil layer was separated and the aqueous layer was extracted 3 times with 100mL of methylene chloride. The dichloromethane extract and the oil layer were combined, washed 3 times with 100mL of water, dried over anhydrous sodium sulfate, and dried without caking after further addition of anhydrous sodium sulfate. Then distilled at 90℃to give a clear liquid of Compound 2c for use (27.5 g,55% yield).

Test example 3: nuclear magnetic resonance

Test sample: h (CF) prepared in example 3 ₂ CF ₂ ) ₃ OCF ₂ CF ₂ SO ₂ Transparent liquid of F (Compound 2 c).

¹ H NMR was performed on a Bruker AM 300 (300 MHz) NMR apparatus at room temperatureSetting; chemical shift (δ) is expressed in ppm with tetramethylsilicon as an internal standard; g according to the peak type (broad peak is denoted as br, single peak is denoted as s, double peak is denoted as d, triple peak is denoted as t, quadruple peak is denoted as q, multiple peak is denoted as m, heptad peak is denoted as sept, coupling constant Hz).

¹ H NMR(CDCl ₃ ,300MHz)δ6.06(tt,J＝52.4Hz,5.1Hz,1H). ¹⁹ FNMR(CDCl ₃ ,282MHz)δ45.48(s,1F),82.26～-82.44(m,2F),-83.11～-83.32(m,2F),-112.72(s,2F),-112.90(s,2F),-123.98(s,2F),-125.83(s,2F),-129.654～-129.85(m,2F),-137.35～-137.68(m,2F).

Example 4: compound HCF ₂ CF ₂ OCF ₂ CF ₂ SO ₃ Preparation of Na (3 a)

Weighing the compound HCF prepared in example 1 ₂ CF ₂ OCF ₂ CF ₂ SO ₂ F (0.1 mol,30 g) was dissolved in 30mL of ethanol, and a 20mL aqueous solution of sodium hydroxide (0.2 mol,8 g) was injected into the ethanol solution using a syringe. Heated to 110 ℃, refluxed and stirred for 2 hours at 80 ℃ with a stirring rate of 500r/min. The reaction was stopped, the solvent ethanol was removed by concentration under reduced pressure, the crude product was added to ethyl acetate, heated to reflux, dissolved, filtered while hot, and the filtrate collected was concentrated under reduced pressure to give compound 3a as a white solid for use (25.6 g,95% yield).

Test example 4: nuclear magnetic resonance

Test sample: HCF prepared in example 4 ₂ CF ₂ OCF ₂ CF ₂ SO ₃ White solid of Na (compound 3 a).

¹ H NMR was measured on a Bruker AM 300 (300 MHz) NMR at room temperature; chemical shift (δ) is expressed in ppm with tetramethylsilicon as an internal standard; according to the peak type (broad peak is expressed as br, single peak is expressed as s, double peak is expressed as d, triple peak is expressed as t, quadruple peak is expressed as q, multiple peak is expressed as m, heptad peak is sept, coupling constant Hz), the number of hydrogen is calculated Is reported in the order of (2).

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ6.47(tt,J＝52.0Hz,3.7Hz,1H). ¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-83.07～-83.19(m,2F),-90.15～

-90.33(m,2F),-119.17(s,2F),-139.66～-139.89(m,2F).

Example 5: compound ICF ₂ CF ₂ OCF ₂ CF ₂ SO ₃ Preparation of Na (3 b)

Weighing Compound ICF ₂ CF ₂ OCF ₂ CF ₂ SO ₂ F (0.1 mol,30 g) was dissolved in 30mL of ethanol, and a 20mL aqueous solution of sodium hydroxide (0.2 mol,8 g) was injected into the ethanol solution using a syringe. Heated to 110 ℃, refluxed and stirred for 2 hours at 80 ℃ with a stirring rate of 500r/min. The reaction was stopped, the solvent ethanol was removed by concentration under reduced pressure, the crude product was added to ethyl acetate, heated to reflux, dissolved, filtered while hot, and the filtrate collected was concentrated under reduced pressure to give compound 3b as a white solid for use (40.2 g,91% yield).

Test example 5: nuclear magnetic resonance

Test sample: ICF prepared in example 5 ₂ CF ₂ OCF ₂ CF ₂ SO ₃ White solid of Na (compound 3 b).

¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-68.68～-68.89(m,2F),-82.49～-82.57(m,2F),-86.07～-86.29(m,2F),-118.47(s,2F).

Example 6: chemical treatmentCompound H (CF) ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₃ Preparation of Na (3C)

Compound H (CF) prepared in example 2 was weighed ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₂ F (0.1 mol,30 g) was dissolved in 30mL of ethanol, and a 20mL aqueous solution of sodium hydroxide (0.2 mol,8 g) was injected into the ethanol solution using a syringe. Heated to 110 ℃, refluxed and stirred for 2 hours at 80 ℃ with a stirring rate of 500r/min. The reaction was stopped, the solvent ethanol was removed by concentration under reduced pressure, the crude product was added to ethyl acetate, heated to reflux, dissolved, filtered while hot, and the filtrate was dried by spinning to give compound 3c as a white solid for use (38.8 g,97% yield).

Test example 6: nuclear magnetic resonance

Test sample: h (CF) prepared in example 6 ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₃ White solid of Na (compound 3 c).

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ7.09(tt,J＝50.2Hz,6.0Hz,1H). ¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-82.34～-82.51(m,2F),-84.08～-84.31(m,2F),-118.60(s,2F),-128.43(m,2F),-131.48(m,2F),-138.82～-139.16(m,2F).

Example 7: compound I (CF) ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₃ Preparation of Na (3 d)

Weigh Compound I (CF) ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₂ F (0.1 mol,30 g) was dissolved in 30mL of ethanol, and a 20mL aqueous solution of sodium hydroxide (0.2 mol,8 g) was injected into the ethanol solution using a syringe. Heated to 110 ℃, refluxed and stirred for 2 hours at 80 ℃ with a stirring rate of 500r/min. The reaction was stopped, the solvent ethanol was removed by concentration under reduced pressure, the crude product was added to ethyl acetate, heated to reflux, dissolved, filtered while hot, and the filtrate was dried by spinning to give compound 3d as a white solid for use (51.9 g,95% yield).

Test example 7: nuclear magnetic resonance

Test sample: example 7 preparation of I (CF ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₃ White solid of Na (compound 3 d).

¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-65.16～-65.48(m,2F),-82.04～-82.33(m,2F),-83.47～-83.79(m,2F),-114.09(m,2F),-118.31(s,2F),-124.77(m,2F).

Example 8: compound H (CF) ₂ CF ₂ ) ₃ OCF ₂ CF ₂ SO ₃ Preparation of Na (3 e):

compound H (CF) prepared in example 3 was weighed ₂ CF ₂ ) ₃ OCF ₂ CF ₂ SO ₂ F (0.1 mol,30 g) was dissolved in 30mL of ethanol, and 20mL of sodium hydroxide (0.2 mol,8 g) was dissolved in waterThe solution was injected into the ethanol solution with a syringe. Heated to 110 ℃, refluxed and stirred for 2 hours at 80 ℃ with a stirring rate of 500r/min. The reaction was stopped, the solvent ethanol was removed by concentration under reduced pressure, the crude product was added to ethyl acetate, heated to reflux, dissolved, filtered while hot, and the filtrate was dried by spinning to give compound 3e as a white solid for use (47.8 g,92% yield).

Test example 8: nuclear magnetic resonance

Test sample: h (CF) prepared in example 8 ₂ CF ₂ ) ₃ OCF ₂ CF ₂ SO ₃ White solid of Na (compound 3 e).

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ6.91(tt,J＝49Hz,5.2Hz,1H)； ¹⁹ F NMR(CDCl ₃ ,282MHz)δ-86.82～-87.09(m,2F),-87.94～-88.22(m,2F),-123.20～-123.35(m,2F),-127.23～-127.51(m,2F),-128.45～-128.70(m,2F),-130.53～-1230.83(m,2F),-134.65～-134.90(m,2F),-143.49～-143.83(m,2F).

Example 9: preparation of Compound 4a

1-methylimidazole (0.1 mol,8.2 g) was added to a 50 mL-sealed tube, frozen in liquid nitrogen, the system temperature was brought to-190℃and after methyl iodide (0.11 mol,15.6 g) was added, the low-temperature apparatus was removed, the reaction was resumed at room temperature for 12 hours, the reaction was stopped, and the crude residue was continuously washed 3 times with 15mL of diethyl ether to give a crude residue, which was recrystallized from ethanol and diethyl ether to give a white solid compound 4a (20.1 g,90% yield) for use.

Test example 9: nuclear magnetic resonance

Test sample: compound 4a prepared in example 9 as a white solid.

¹ H NMR(D ₂ O,300MHz)δ3.77(s,6H),7.30(s,2H),8.54(s,1H).

Example 10: preparation of Compound 4b

1-methylimidazole (0.1 mol,8.2 g) was added to a 50 mL-sealed tube, frozen in liquid nitrogen, the system temperature was brought to-190℃and after the addition of iodoethane (0.11 mol,15.6 g), the low-temperature apparatus was removed, the reaction was stopped at 50℃under vacuum for 12 hours, and the reaction was continuously washed 3 times with 15mL of diethyl ether to give a crude residue, which was recrystallized from ethanol and diethyl ether to give a white solid compound 4b, ready for use (20.1 g,85% yield).

Test example 10: nuclear magnetic resonance

Test sample: compound 4b prepared in example 10 as a white solid.

¹ H NMR(D ₂ O,300MHz)δ1.38(t,J＝7.3Hz,3H),3.77(s,3H),4.11(q,J＝7.3Hz,2H),7.30(d,J＝1.5Hz,1H),7.37(d,J＝1.5Hz,1H),8.61(s,1H).

Example 11: preparation of Compound 4c

1-methylimidazole (0.1 mol,8.2 g) was added to a 50 mL-sealed tube, frozen in liquid nitrogen, the system temperature was brought to-190℃and after iodopropane (0.11 mol,15.6 g) was added, the low-temperature apparatus was removed, the reaction was stopped at 120℃under vacuum for 12 hours, and the reaction was continuously washed 3 times with 15mL of diethyl ether to give a crude residue, which was dried under vacuum to give pale yellow liquid compound 4c for use.

Test example 11: nuclear magnetic resonance

Test sample: a pale yellow liquid of the compound 4c prepared in example 11.

¹ H NMR was measured on a Bruker AM 300 (300 MHz) NMR at room temperature; chemical shift (δ) is expressed in ppm with tetramethylsilicon as an internal standard; the order of the hydrogen numbers is reported in terms of peak type (broad peak for br, single peak for s, double peak for d, triple peak for t, quadruple peak for q, multiple peak for m, heptadouble peak for sept, coupling constant Hz).

¹ H NMR(D ₂ O,300MHz)δ0.80(t,J＝7.4Hz,3H),1.72～1.84(m,2H),3.79(s,3H),4.06(t,J＝7.2Hz,2H),7.34(d,J＝2.2Hz,1H),7.39(d,J＝2.2Hz,1H).

Example 12: preparation of Compound 4d

1-methylimidazole (0.1 mol,8.2 g) was added to a 50 mL-sealed tube, the system was frozen with liquid nitrogen to a temperature of-190℃and after iodopropane (0.11 mol,15.6 g) was added, the low-temperature apparatus was removed, the reaction was stopped at 120℃for 12 hours under vacuum, and the reaction was continuously washed 3 times with 30mL of diethyl ether to give a crude residue, which was dried in vacuo to give a pale yellow liquid compound 4d for use.

Test example 12: nuclear magnetic resonance

Test sample: pale yellow liquid of compound 4d prepared in example 12.

¹ H NMR on a Bruker AM 300 (300 MHz) Nuclear magnetic resonance apparatusMeasuring at room temperature; chemical shift (δ) is expressed in ppm with tetramethylsilicon as an internal standard; the order of the hydrogen numbers is reported in terms of peak type (broad peak for br, single peak for s, double peak for d, triple peak for t, quadruple peak for q, multiple peak for m, heptadouble peak for sept, coupling constant Hz).

¹ H NMR(D ₂ O,300MHz)δ0.80(t,J＝7.4Hz,3H),1.14～1.27(m,2H),1.69～1.79(m,2H),3.78(s,3H),4.09(t,J＝7.1Hz,2H),7.32(d,J＝2.2Hz,1H),7.38(d,J＝2.2Hz,1H),8.63(s,1H).

Example 13: preparation of Compound 5

1-chloro-2-iodotetrafluoroethane (0.22 mol,57.53 g) and BPO (dibenzoyl peroxide) (2.91 mmol,0.7 g) were weighed into a reaction vessel, and reacted at 80℃for 6 hours under 15atm of ethylene gas. The reaction was stopped and distilled at 53℃under normal pressure to give a clear liquid 5 (19 g,30% yield) for use.

Test example 13: nuclear magnetic resonance

Test sample: transparent liquid of compound 5 prepared in example 13.

¹ H NMR(CDCl ₃ ,300MHz)δ2.63～2.80(m,2H),3.25(t,J＝8.2Hz,2H). ¹⁹ F NMR(CDCl ₃ ,282MHz)δ-71.67(s,2F),-115.23(t,J＝16.5Hz,2F).

Example 14: preparation of Compound 4e

The compound 5 (100 mmol,29 g) prepared in example 13 and 1, 2-dimethylimidazole (40 mmol,3.88 g) were weighed into a sealed tube and heated to 150 ℃ under vacuum to react for 48 hours until the starting material had been completely consumed. The reaction was stopped and washed 5 times with 10mL of diethyl ether. Then, the solution was clarified by heating with 5mL of ethanol, cooled to room temperature, and then slowly added with 25mL of diethyl ether and allowed to stand overnight to gradually precipitate a large amount of solid, to give 4e as a white solid for use (3.90 g,25% yield).

Test example 14: nuclear magnetic resonance

Test sample: compound 4e prepared in example 14 as a white solid.

¹ H NMR(D ₂ O,300MHz)δ2.45(s,3H),2.57～2.74(m,2H),3.59(s,3H),4.34(t,J＝7.1Hz,2H),7.18(d,J＝2.1Hz,1H),7.27(d,J＝2.1Hz,1H). ¹⁹ F NMR(D ₂ O,282MHz)δ-72.85(s,2F),-114.58(t,J＝18.2Hz,2F).

Example 15: preparation of Compound 6

NaH (44 mol,1.76 g) was added to a 100mL egg-shaped bottle, and after three times of nitrogen purging, a solution of imidazole (40 mmol,2.72 g) in DMF (N, N-dimethylformamide) (15 mL) was poured in an ice bath (0-5 ℃ C.) and stirred at room temperature for 40min. Tetrabutylammonium iodide (0.54 mmol,0.2 g) in DMF (15 mL) was added, and after stirring for 5min, a homogeneous system solution was obtained, and 1, 2-dibromotetrafluoroethane (80 mmol,20.8 g) was added until all was dissolved in the system, and stirred at room temperature overnight to obtain a homogeneous reaction solution.

The reaction solution was poured into 100mL of water, the organic layer was extracted 4 times with 100mL of n-pentane, the 4 extracted organic layers were combined, and the organic layer was washed 2 times with 200mL of water. After washing with water, the organic layer was dried over anhydrous magnesium sulfate, n-pentane was distilled off under normal pressure, and the product was distilled under reduced pressure to give a transparent liquid compound 6 (6.12 g,62% yield) for use.

Test example 15: nuclear magnetic resonance

Test sample: a transparent liquid of compound 6 prepared in example 15.

¹ H NMR(CDCl ₃ ,300MHz)δ7.19(s,1H),7.20(s,1H),7.84(s,1H). ¹⁹ F NMR(CDCl ₃ ,282MHz)δ-68.40(t,J＝4.2Hz,2F),-95.03(t,J＝4.2Hz,2F).

Example 16: preparation of Compound 4f

Compound 6 (19.38 mmol,4.79 g) prepared in example 15 was weighed into a sealed tube, frozen in liquid nitrogen, methyl iodide (21.3 mmol,3.03 g) was added and heated to 120℃under vacuum to react overnight to give a solid product. After washing the solid product 2 times with 10mL of diethyl ether, it was dissolved by heating with 15mL of ethanol, cooled to room temperature, and 50mL of diethyl ether was slowly added. Standing for 10h until the upper layer is liquid, and the lower layer is layering of solid sediment. Filtering to obtain a lower solid precipitate, and vacuum drying to obtain a pink solid product 4f for later use. (7.23 g,96% yield).

Test example 16: nuclear magnetic resonance

Test sample: the compound 4f prepared in example 16 was a pink solid (whether modified to a white powder solid is more suitable here).

¹ H NMR was measured on a Bruker AM 300 (300 MHz) NMR at room temperature; chemical shift (δ) is expressed in ppm with tetramethylsilicon as an internal standard; according to the peak type (broad peak is denoted as br, single peak is denoted as s, double peak is denoted as d, triple peak is denoted as t, quadruple peak is denoted as q, multiple peak is denoted as m, heptad peak is denoted as sept, coupling constant Hz).

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ4.34(s,3H),8.31(s,1H),8.35(s,1H),10.57(s,1H). ¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-75.66(s,2F),

-100.79(s,2F).

Example 17: synthesis of ionic liquid 7ab

An aqueous solution (8 mL) of the compound 4a (11 mmol,2.09 g) prepared in example 9 was weighed and added dropwise to the compound ICF prepared in example 5 ₂ CF ₂ OCF ₂ CF ₂ SO ₃ A solution of Na (3 b) (10 mmol,4.46 g) in methanol (8 mL) was stirred overnight at room temperature. Concentrating under reduced pressure to remove methanol, extracting with 15mL of dichloromethane for 3 times, mixing the 3 dichloromethane extract layers, drying with anhydrous magnesium sulfate, concentrating under reduced pressure, heating to 80deg.C, and vacuum drying to obtain reddish brown liquid 7ab (3.46 g,70% yield).

Test example 17: nuclear magnetic resonance

Test sample: a reddish brown liquid of ionic liquid 7ab prepared in example 17.

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ4.02(s,3H),7.69(m,2H),9.00(s,1H). ¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-70.16(t,J＝5.6Hz,2F),

-83.41(t,J＝13.3Hz,2F),-86.90～-87.06(m,2F),-119.13(s,2F).IR(film)(cm ^-1 ):3164,3125,1578,1336,1293,1261,1176,1147,1054,975,759.MS(ESI):422.7[anion] ^- .Anal.Cacld for C ₉ H ₉ F ₈ IN ₂ O ₄ S:C,20.78；H,1.74；N,5.39.Found:C,20.67；H,1.66；N,5.36.

Example 18: synthesis of ionic liquid 7ac

An aqueous solution (8 mL) of the compound 4a (11 mmol,2.09 g) prepared in example 9 was weighed and added dropwise to the compound H (CF) prepared in example 6 ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₃ A solution of Na (3C) (10 mmol,4.46 g) in methanol (8 mL) was stirred overnight at room temperature. Methanol was removed by concentrating under reduced pressure, extracting successively 3 times with 15mL of dichloromethane, combining the 3 dichloromethane extracts, drying over anhydrous magnesium sulfate, concentrating under reduced pressure, heating to 80 ℃ and drying under vacuum to give 7ac as a reddish brown liquid, ready for use (3.4 g,70% yield).

Test example 18: nuclear magnetic resonance

Test sample: the ionic liquid 7ac prepared in example 18 was a reddish brown liquid.

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ4.06(s,6H),7.09(tt,J＝50.5Hz,6.2Hz,1H),7.71(m,2H),9.04(s,1H). ¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-83.48～-83.62(m,2F),-85.15～-85.36(m,2F),-120.12(s,2F),-129.46～-129.59(m,2F),-132.36～-132.53(m,2F),-139.91～-140.22(m,2F).IR(film)(cm ^-1 ):3166,3126,1579,1350,1316,1265,1195,1146,1054,975,811,760.MS(ESI):396.7[anion]-.Anal.Cacld for C ₁₁ H ₁₀ F ₁₂ N ₂ O ₄ S.H ₂ O:C,25.79；H,2.36；N,5.47.Found:C,26.15；H,1.97；N,5.37.

Example 19: synthesis of ionic liquid 7ad

An aqueous solution (8 mL) of the compound 4a (11 mmol,2.09 g) prepared in example 9 was weighed and added dropwise to the compound I (CF) prepared in example 7 ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₃ A solution of Na (3 d) (10 mmol,4.46 g) in methanol (8 mL) was stirred overnight at room temperature. Concentrating under reduced pressure to remove methanol, extracting with 15mL dichloromethane for 3 times, mixing the 3 dichloromethane extract layers, drying with anhydrous magnesium sulfate, concentrating under reduced pressure, heating to 80deg.C, and vacuum drying to obtain reddish brown liquid 7ad (3.9 g,64% yield)

Test example 19: nuclear magnetic resonance

Test sample: the ionic liquid 7ad prepared in example 19 was a reddish brown liquid.

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ4.03(s,6H),7.69(s,2H),9.02(s,1H). ¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-65.64(t,J＝14.4Hz,2F),-82.93～-83.05(m,2F),-84.26～-84.49(m,2F),-114.68～-114.86(m,2F),

-119.23(s,2F),-125.50～-125.74(m,2F).IR(film)(cm ^-1 ):3163,3123,1578,1351,1315,1265,1199,1148,1087,1054,971,757.MS(ESI):522.8[anion]-.Anal.Cacld for C ₁₁ H ₉ F ₁₂ IN ₂ O ₄ S:C,21.30；H,1.46；N,4.52.Found:C,21.30；H,1.38；N,4.49.

Example 20: synthesis of ionic liquid 7bb

An aqueous solution (8 mL) of the compound 4b (11 mmol,2.09 g) prepared in example 10 was weighed and added dropwise to the compound ICF prepared in example 5 ₂ CF ₂ OCF ₂ CF ₂ SO ₃ A solution of Na (3 b) (10 mmol,4.46 g) in methanol (8 mL) was stirred overnight at room temperature. Methanol was removed by concentrating under reduced pressure, extracting with 15mL dichloromethane for 3 times successively, combining the 3 dichloromethane extracts, drying over anhydrous magnesium sulfate, concentrating under reduced pressure, heating to 80deg.C, and vacuum drying to give 7bb as a reddish brown liquid (3.3 g,62% yield).

Test example 20: nuclear magnetic resonance

Test sample: a reddish brown liquid of ionic liquid 7bb prepared in example 20.

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ1.54(t,J＝7.5Hz,3H),4.03(s,3H),4.38(q,J＝7.5Hz,2H),7.71(m,1H),7.79(m,1H),9.10(s,1H). ¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-70.00(t,J＝5.6Hz,2F),-83.33～-83.45(m,2F),-86.92～-87.06(m,2F),-119.13(s,2F).IR(film)(cm ^-1 ):3157,3119,2992,1574,1471,1456,1432,1393,1336,1293,1261,1218,1148,1054,976,916,759.MS(ESI):111.2[cation] ⁺ ,422.7[anion] ^- .Anal.Cacld for C ₁₀ H ₁₁ F ₈ IN ₂ O ₄ S.H ₂ O:C,21.75；H,2.37；N,5.07.Found:C,21.58；H,2.02；N,4.83.

Example 21: synthesis of ionic liquid 7bc

An aqueous solution (8 mL) of the compound 4b (11 mmol,2.09 g) prepared in example 10 was weighed and added dropwise to the compound H (CF) prepared in example 6 ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₃ A solution of Na (3C) (10 mmol,4.46 g) in methanol (8 mL) was stirred overnight at room temperature. Methanol was removed by concentrating under reduced pressure, extracting with 15mL of dichloromethane for 3 times successively, combining the 3 dichloromethane extracts, drying over anhydrous magnesium sulfate, concentrating under reduced pressure, heating to 80deg.C, and vacuum drying to give a reddish brown liquid 7bc (3.3 g,66% yield) for use.

Test example 21: nuclear magnetic resonance

Test sample: the ionic liquid 7bc prepared in example 21 was a reddish brown liquid.

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ1.54(t,J＝7.5Hz,3H),4.03(s,3H),4.39(q,7.5Hz,2H),7.06(tt,J＝50.5Hz,6.2Hz,1H),7.71(m,1H),7.79(m,1H),9.10(s,1H). ¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-83.51(t,J＝13.1Hz,2F),-85.15～-85.36(m,2F),-119.75(s,2F),-129.36～-129.49(m,2F),-132.36～-132.53(m,2F),-139.91～-140.22(m,2F).IR(film)

(cm ^-1 ):3157,3119,1575,1351,1315,1267,1193,1146,1054,975,915,811,760.MS(ESI):111.2[cation] ⁺ ,396.7[anion] ^- .Anal.Cacld for C ₁₂ H ₁₂ F ₁₂ N ₂ O ₄ S:C,28.36；H,2.38；N,5.51.Found:C,28.32；H,2.67；N,5.38.

Example 22: synthesis of ionic liquid 7bd

An aqueous solution (8 mL) of the compound 4b (11 mmol,2.09 g) prepared in example 10 was weighed and added dropwise to the compound I (CF) prepared in example 7 ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₃ A solution of Na (3 d) (10 mmol,4.46 g) in methanol (8 mL) was stirred overnight at room temperature. Methanol was removed by concentrating under reduced pressure, extracting with 15mL of dichloromethane for 3 times successively, combining the 3 dichloromethane extracts, drying over anhydrous magnesium sulfate, concentrating under reduced pressure, heating to 80deg.C, and vacuum drying to give 7bd as a reddish brown liquid (4.0 g,63% yield).

Test example 22: nuclear magnetic resonance

Test sample: the ionic liquid 7bd prepared in example 22 was a reddish brown liquid.

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ1.55(t,J＝7.5Hz,3H),4.04(s,3H),4.39(q,J＝7.5Hz,2H),7.72(m,1H),7.79(m,1H),9.11(s,1H). ¹⁹ FNMR(CD ₃ OCD ₃ ,282MHz)δ-65.39(t,J＝13.7Hz,2F),-82.87～-83.00(m,2F),-84.26～-84.49(m,2F),-114.68～-114.86(m,2F),-119.23(s,2F),-125.48～-125.69(m,2F).IR(film)(cm ^-1 ):3156,3119,1575,1351,1315,1265,1199,1147,1087,1054,971,915,719.MS(ESI):111.2

[cation] ⁺ ,522.8[anion]-.Anal.Cacld for C ₁₂ H ₁₁ F ₁₂ IN ₂ O ₄ S:C,22.73；H,1.75；N,4.42.Found:C,22.78；H,1.65；N,4.52.

Example 23: synthesis of ionic liquid 7ca

An aqueous solution (8 mL) of the compound 4c (11 mmol,2.09 g) prepared in example 11 was weighed and added dropwise to the compound HCF prepared in example 4 ₂ CF ₂ OCF ₂ CF ₂ SO ₃ A solution of Na (3 a) (10 mmol,4.46 g) in methanol (8 mL) was stirred overnight at room temperature. Methanol was removed by concentrating under reduced pressure, extracting with 15mL of dichloromethane for 3 times successively, combining the 3 dichloromethane extracts, drying over anhydrous magnesium sulfate, concentrating under reduced pressure, heating to 80deg.C, and vacuum drying to give a reddish brown liquid, 7ca, ready for use (1.7 g,40% yield).

Test example 23: nuclear magnetic resonance

Test sample: the ionic liquid 7ca prepared in example 23 was a reddish brown liquid.

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ0.94(t,J＝7.8Hz,3H),1.88～2.00(m,2H),4.04(s,3H),4.31(t,J＝7.8Hz,2H),6.50(tt,J＝52.3Hz,3.4Hz,1H),7.73(m,1H),7.78(m,1H),9.13(s,1H). ¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-83.05～-83.14(m,2F),-89.94～-90.09(m,2F),-119.26(s,2F),-139.74(dt,J＝52.3Hz,4.8Hz,2F).IR(film)(cm ^-1 ):3156,3119,1575,1330,1277,1262,1209,1146,1054,973,854,749.MS(ESI):125.2[cation] ⁺ ,296.7[anion] ^- .Anal.Cacld for C ₁₁ H ₁₄ F ₈ N ₂ O ₄ S ^. H ₂ O:C,30.01；H,3.66；N,6.36.Found:C,29.78；H,3.40；N,5.94.

Example 24: synthesis of Ionic liquid 7cb

An aqueous solution (8 mL) of the compound 4c (11 mmol,2.09 g) prepared in example 11 was weighed and added dropwise to the compound ICF prepared in example 5 ₂ CF ₂ OCF ₂ CF ₂ SO ₃ A solution of Na (3 b) (10 mmol,4.46 g) in methanol (8 mL) was stirred overnight at room temperature. The methanol was removed by concentration, extraction was continued 3 times with 15mL of dichloromethane, the 3 dichloromethane extracts were combined, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, heated to 80 ℃ and dried under vacuum to give 7cb as a reddish brown liquid for use (3.9 g,72% yield).

Test example 24: nuclear magnetic resonance

Test sample: the ionic liquid 7cb prepared in example 24 was a reddish brown liquid.

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ0.94(t,J＝7.9Hz,3H),1.88～2.01(m,2H),4.04(s,3H),4.31(q,J＝7.9Hz,2H),7.72(m,1H),7.78(m,1H),9.11(s,1H). ¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-70.16(t,J＝5.7Hz,2F),-83.30～-83.43(m,2F),-86.87～-87.02(m,2F),-119.13(s,2F)；IR(film)(cm ^-1 ):3155,3119,2974,1575,1336,1293,1260,1218,1147,1053,975,916,759.MS(ESI):125.2[cation] ⁺ ,422.7[anion]-.Anal.Cacld for C ₁₁ H ₁₃ F ₈ IN ₂ O ₄ S:C,24.10；H,2.39；N,5.11.Found:C,23.90；H,2.43；N,5.16.

Example 25: synthesis of ionic liquid 7cc

An aqueous solution (8 mL) of the compound 4c (11 mmol,2.09 g) prepared in example 11 was weighed and added dropwise to the compound H (CF) prepared in example 6 ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₃ A solution of Na (3C) (10 mmol,4.46 g) in methanol (8 mL) was stirred overnight at room temperature. Methanol was removed by concentrating under reduced pressure, extracting successively 3 times with 15mL of dichloromethane, combining the 3 dichloromethane extracts, drying over anhydrous magnesium sulfate, concentrating under reduced pressure, heating to 80 ℃ and drying under vacuum to obtain 7cc of reddish brown liquid for use (3.8 g,72% yield).

Test example 25: nuclear magnetic resonance

Test sample: 7cc of the ionic liquid prepared in example 25 was a reddish brown liquid.

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ0.94(t,J＝7.9Hz,3H),1.88～2.01(m,2H),4.03(s,3H),4.30(q,J＝7.9Hz,2H),7.01(tt,J＝49.5Hz,5.9Hz,1H),7.72(m,1H),7.78(m,1H),9.11(s,1H). ¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-83.51(t,J＝13.0Hz,2F),-85.15～-85.36(m,2F),-119.75(s,2F),-129.23～129.35(m,2F),-132.36～-132.53(m,2F),-139.91～-140.22(m,2F).IR(film)(cm ^-1 ):3150,3120,2974,1575,1350,1315,1264,1194,1146,1054,975,811,760.MS(ESI):125.3[cation] ⁺ ,396.7[anion]-.Anal.Cacld for C ₁₃ H ₁₄ F ₁₂ N ₂ O ₄ S.H ₂ O:C,28.90；H,2.98；N,5.18.Found:C,28.97；H,2.59；N,4.90.

Example 26: synthesis of ionic liquid 7cd

An aqueous solution (8 mL) of the compound 4c (11 mmol,2.09 g) prepared in example 11 was weighed and added dropwise to the compound I (CF) prepared in example 7 ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₃ A solution of Na (3 d) (10 mmol,4.46 g) in methanol (8 mL) was stirred overnight at room temperature. The methanol was removed by concentrating under reduced pressure, extracting with 15mL of dichloromethane for 3 times successively, combining the 3 dichloromethane extracts, drying over anhydrous magnesium sulfate, concentrating under reduced pressure, heating to 80 ℃ and drying under vacuum to obtain a reddish brown liquid 7cd, 3.8g for use, 59% yield).

Test example 26: nuclear magnetic resonance

Test sample: the ionic liquid 7cd prepared in example 26 was a reddish brown liquid.

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ0.94(t,J＝7.9Hz,3H),1.88～2.01(m,2H),4.04(s,3H),4.31(q,J＝7.9Hz,2H),7.72(m,1H),7.78(m,1H),9.11(s,1H). ¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-65.20(t,J＝13.9Hz,2F),-82.88～-83.12(m,2F),-84.26～-84.49(m,2F),-114.68～-114.86(m,2F),-119.23(s,2F),-125.58(m,2F).IR(film)(cm ^-1 ):3155,3120,1575,1350,1315,1260,1198,1146,1087,1053,969,756,719.MS(ESI):125.3[cation] ⁺ ,522.8[anion] ^- .Anal.Cacld for C ₁₃ H ₁₄ F ₁₂ N ₂ O ₄ S:C,24.09；H,2.02；N,4.32.Found:C,23.91；H,1.94；N,4.26.

Example 27: synthesis of ionic liquid 7db

An aqueous solution (8 mL) of the compound 4d (11 mmol,2.09 g) prepared in example 12 was weighed and added dropwise to the compound ICF prepared in example 5 ₂ CF ₂ OCF ₂ CF ₂ SO ₃ A solution of Na (3 b) (10 mmol,4.46 g) in methanol (8 mL) was stirred overnight at room temperature. Methanol was removed by concentrating under reduced pressure, extracting with 15mL of dichloromethane for 3 times successively, combining the 3 dichloromethane extracts, drying over anhydrous magnesium sulfate, concentrating under reduced pressure, heating to 80deg.C, and vacuum drying to give 7db of reddish brown liquid (3.6 g,64% yield) for use.

Test example 27: nuclear magnetic resonance

Test sample: the ionic liquid prepared in example 27 was a 7db reddish brown liquid.

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ0.91(t,J＝7.2Hz,3H),1.26～1.38(m,2H),1.76～1.87(m,2H),3.93(s,3H),4.16(t,J＝7.4Hz,2H),7.37(m,1H),7.41(m,1H),9.06(s,1H). ¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-63.89～-64.02(m,2F),-80.46(t,J＝13.0Hz,2F),-83.55～-83.75(m,2F),-119.13(s,2F).IR(film)(cm ^-1 ):3155,3114,2968,2880,1575,1336,1292,1260,1146,1053,975,915,759.MS(ESI):139.3[cation] ⁺ ,422.7[anion] ^- .Anal.Cacld for C ₁₃ H ₁₄ F ₁₂ N ₂ O ₄ S:C,25.64；H,2.69；N,4.98.Found:C,25.73；H,2.81；N,4.81.T _g <-64℃.

Example 28: synthesis of ionic liquid 7dc

An aqueous solution (8 mL) of the compound 4d (11 mmol,2.09 g) prepared in example 12 was weighed and added dropwise to the compound H (CF) prepared in example 6 ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₃ A solution of Na (3C) (10 mmol,4.46 g) in methanol (8 mL) was stirred overnight at room temperature. The methanol was removed by concentrating under reduced pressure, extracting successively 3 times with 15mL of dichloromethane, combining the 3 dichloromethane extracts, drying over anhydrous magnesium sulfate, concentrating under reduced pressure, heating to 80 ℃ and drying under vacuum to give a reddish brown liquid 7dc (3.4 g,63% yield) for use.

Test example 28: nuclear magnetic resonance

Test sample: the ionic liquid 7dc prepared in example 28 was a reddish brown liquid.

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ0.93(t,J＝7.2Hz,3H),1.31～1.43(m,2H),1.86～1.96(m,2H),4.04(s,3H),4.35(t,J＝7.4Hz,2H),7.04(tt,J＝50.3Hz,6.1Hz,1H),7.72(m,1H),7.78(m,1H),9.09(s,1H).

¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-83.49(t,J＝13.3Hz,2F),-85.15～-85.36(m,2F),-119.75(s,2F),-129.37(s,2F),-132.36～-132.53(m,2F),-139.91～-140.22(m,2F).IR(film)(cm ^-1 ):3156,3119,2971,2883,1575,1471,1350,1315,1264,1193,1146,1054,975,811,760.MS(ESI):139.3[cation] ⁺ ,396.7[anion] ^- .Anal.Cacld for C ₁₄ H ₁₆ F ₁₂ N ₂ O ₄ S ^. H ₂ O:C,30.33；H,3.27；N,5.05.Found:C,30.66；H,2.96；N,4.73.

Example 29: synthesis of Ionic liquid 7dd

An aqueous solution (8 mL) of the compound 4d (11 mmol,2.09 g) prepared in example 12 was weighed and added dropwise to the compound I (CF) prepared in example 7 ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₃ A solution of Na (3 d) (10 mmol,4.46 g) in methanol (8 mL) was stirred overnight at room temperature. Methanol was removed by concentrating under reduced pressure, extracting successively 3 times with 15mL of dichloromethane, combining the 3 dichloromethane extracts, drying over anhydrous magnesium sulfate, concentrating under reduced pressure, heating to 80 ℃ and drying under vacuum to give a reddish brown liquid 7dd (3.9 g,59% yield) for use.

Test example 29: nuclear magnetic resonance

Test sample: the ionic liquid 7dd prepared in example 29 was a reddish brown liquid.

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ0.93(t,J＝7.2Hz,3H),1.31～1.43(m,2H),1.86～1.95(m,2H),4.03(s,3H),4.34(t,J＝7.4Hz,2H),7.72(m,1H),7.78(m,1H),9.11(s,1H). ¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-65.55(t,J＝13.4Hz,2F),-82.95(m,2F),-84.26～-84.49(m,2F),-114.68～-114.86(m,2F),-119.23(s,2F),-125.49～-129.69(m,2F).IR(film)(cm ^-1 ):3155,3117,2969,2881,1575,1468,1350,1315,1263,1199,1147,1087,1054,970,757,719.MS(ESI):139.3[cation] ⁺ ,522.8[anion] ^- .Anal.Cacld for C ₁₄ H ₁₅ F ₁₂ IN ₂ O ₄ S:C,25.39；H,2.28；N,4.23.Found:C,25.39；H,2.31；N,4.13.

Example 30: synthesis of ionic liquid 7ec

An aqueous solution (8 mL) of the compound 4e (11 mmol,2.09 g) prepared in example 14 was weighed and added dropwise to the compound H (CF) prepared in example 6 ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₃ A solution of Na (3C) (10 mmol,4.46 g) in methanol (8 mL) was stirred overnight at room temperature. The methanol was removed by concentrating under reduced pressure, extracting with 15mL of dichloromethane for 3 times successively, combining the 3 dichloromethane extracts, drying over anhydrous magnesium sulfate, concentrating under reduced pressure, heating to 80 ℃ and drying under vacuum to obtain a reddish brown liquid, 7ec, ready for use (4.6 g,70% yield).

Test example 30: nuclear magnetic resonance

Test sample: the ionic liquid prepared in example 30 was 7ec of a reddish brown liquid.

¹ H NMR(CD ₃ OCD ₃ ,300MHz)δ2.86(s,3H),2.92～3.09(m,2H),3.99(s,3H),4.74(t,J＝7.4Hz,2H),7.10(tt,J＝50.8Hz,6.5Hz,1H),7.68(d,J＝2.3Hz,1H),7.81(d,J＝2.3Hz,1H). ¹⁹ F NMR(CD ₃ OCD ₃ ,282MHz)δ-77.10(s,2F),-87.70～-87.86(m,2F),-89.54(s,2F),

-119.06(t,J＝18.7Hz,2F),-123.98(s,2F),-133.76(s,2F),-136.70～

136.89(m,2F),-144.15～-144.47(m,2F).IR(film)(cm ^-1 ):3147,1595,1542,1350,1315,1266,1196,1147,1098,1054,975,939,811,760,640.MS(ESI):259.1[cation] ⁺ ,397.0[anion]-.Anal.Cacld for C ₁₅ H ₁₃ ClF ₁₆ N ₂ O ₄ S:C,27.43；H,2.00；N,4.27.Found:C,27.63；H,2.06；N,4.30.

Test example 31: determination of glass transition temperature and decomposition temperature of ionic liquid

Test sample: the ionic liquids prepared in examples 17-30.

Parameters: TGA/DSC 3+, RT to 1100 ℃,0.02to 250K/min, manufacturer: meltretolidol technology.

The steps are as follows: before using, starting up, opening balance protection gas, regulating flow, opening host power supply, self-checking, starting computer, editing experiment method, lofting, closing furnace body, starting test, after the test is finished, taking out sample, processing data, closing instrument and reaction gas and power supply.

The glass transition temperature (Tg) and decomposition temperature (Td) of the ionic liquid were measured by DSC-TGA:

glass transition temperature and decomposition temperature of ionic liquids

In practice, ionic liquids must have a high density in order to provide sufficient buoyancy to the instrument components, and also require a relatively high viscosity to obtain good damping characteristics. While most highly halogenated aryl materials are volatile and have a strong toxicity, this can be a major problem for use in the environment or at high temperatures. To circumvent this problem, nonvolatile ionic liquids may be the first liquid, and methylimidazolium, pyridinium and pyridinium salts have densities that are easily quaternized due to the variety of structures, so imidazole analogs are selected as the primary candidates for developing high-density ionic liquids, the key of which is the introduction of bromine or iodine halogens into the cation.

As can be seen from comparing the data in the tables, when the anion of the ionic liquid is iodide:

The cations of example 17 and example 19 are both H and CH ₃ The anions are ionic liquids of iodide, the glass transition temperature (Tg) of example 17 > the glass transition temperature (Tg) of example 19, while the decomposition temperature (Td) of example 17 < the decomposition temperature (Td) of example 19;

the cations of example 20 and example 22 are both H and C ₂ H ₅ The anions are ionic liquids of iodide, the glass transition temperature (Tg) of example 20 > the glass transition temperature (Tg) of example 22, while the decomposition temperature (Td) of example 20 < the decomposition temperature (Td) of example 22;

the cations of example 24 and example 26 are both H and n-C ₃ H ₇ Ionic liquid with iodide as anion, glass transition temperature (Tg) of example 24>Glass transition temperature (Tg) of example 26, while decomposition temperature (Td) of example 24 < decomposition temperature (Td) of example 26;

examples 27 and 29 both have the same cations H and n-C ₄ H ₉ Ionic liquid with iodide as anion, glass transition temperature (Tg) of example 27<Glass transition temperature (Tg) of example 29, while decomposition temperature (Td) of example 27 < decomposition temperature (Td) of example 29;

As can be seen from comparing the data in the tables, the cations in the ionic liquid are H and C _1-4 When alkyl is:

the cations of example 17 and example 18 are both H and CH ₃ The anion of example 17 was an ionic liquid of iodide and the anion of example 18 was an ionic liquid of hydride. Glass transition temperature (Tg) of example 17 > glass transition temperature (Tg) of example 18, while decomposition temperature (Td) of example 17 < decomposition temperature (Td) of example 18;

the cations of example 21 and example 22 are the sameIs H and C ₂ H ₅ The anion of example 21 was the hydride ionic liquid and the anion of example 22 was the iodide ionic liquid. Glass transition temperature (Tg) of example 21>Glass transition temperature (Tg) of example 22, while decomposition temperature (Td) of example 21 > decomposition temperature (Td) of example 22;

the cations of both example 23 and example 24 are the same as H and n-C ₃ H ₇ The anion of example 23 was the hydride ionic liquid and the anion of example 24 was the iodide ionic liquid. Glass transition temperature (Tg) of example 23<The glass transition temperature (Tg) of example 24, while the decomposition temperature (Td) of example 23 > the decomposition temperature (Td of example 24;

Examples 28 and 29 both have the same cations H and n-C ₄ H ₉ The anion of example 28 was the hydride ionic liquid and the anion of example 29 was the iodide ionic liquid. Glass transition temperature (Tg) of example 28<Glass transition temperature (Tg) of example 29, while decomposition temperature (Td) of example 28 > decomposition temperature (Td) of example 29.

Thus, it can be seen that the thermal stability of ionic liquids in which the anion is iodide increases slightly with increasing anion chain length for the same cation. But not as good as the corresponding hydride.

For the same anions, the thermal stability of the ionic liquid decreases with the increase of the alkyl chain on the imidazole ring; but when the anion is H (CF) ₂ ) ₄ O(CF ₂ ) ₂ SO ₃ ^- When the ionic liquid is used, the thermal stability of the ionic liquid is very similar, the ionic liquid is not greatly related to cations, and the decomposition temperatures of the ionic liquid and the cation are very high.

Specifically, the anions of example 17, example 20, example 24 and example 27 are the same as I (CF) ₂ ) ₂ O(CF ₂ ) ₂ SO ₃ The cation being C _1-4 An alkyl group and H. Glass transition temperature (Tg) of example 20 > glass transition temperature (Tg) of example 17 > glass transition temperature (Tg) of example 24 > glass transition temperature (Tg) of example 27 Temperature (Tg) was varied while decomposition temperature (Td) of example 20 < decomposition temperature (Td) of example 17 > decomposition temperature (Td) of example 24 > decomposition temperature (Td) of example 27.

The anions of examples 18, 21, 25, 28 and 30 are all H (CF) ₂ ) ₄ O(CF ₂ ) ₂ SO ₃ The cation being C _1-4 Alkyl, H and Cl (CF) ₂ ) ₂ (CH ₂ ) ₂ Is an ionic liquid of (a). The glass transition temperature (Tg) of example 18 < the glass transition temperature (Tg) of example 30 < the glass transition temperature (Tg) of example 21 < the glass transition temperatures (Tg) of example 25 and example 28, while the decomposition temperatures (Td) of example 25 and example 30 < the decomposition temperatures (Td) of example 18 and example 28 < the decomposition temperature (Td) of example 21.

The anions of example 19, example 22, example 26 and example 29 are all identical I (CF ₂ ) ₄ O(CF ₂ ) ₂ SO ₃ The cation being C _1-4 An alkyl group and H. The glass transition temperatures (Tg) of example 19, example 22 and example 29 are slightly greater than the glass transition temperature (Tg) of example 26, while the decomposition temperature (Td) of example 29 < the decomposition temperature (Td) of example 26 > the decomposition temperature (Td) of example 22 > the decomposition temperature (Td) of example 19.

Surprisingly, all ionic salts, in particular cations, formed from these sulfonates are [ mmim ] ⁺ 、[emim] ⁺ The glass transition temperature is very low. Other commonly used anions reported in the literature at present [ BF ₄ ]-、[PF ₆ ] ^- 、[Tf ₂ N] ^- It is difficult to achieve this effect. Therefore, these 3-oxapolyfluoroalkyl sulfonates are expected to be novel fluorine-containing anions.

Test example 32: ion liquid density determination

Test sample: the ionic liquids prepared in examples 17-30.

Name: G-DenPyc X900 manufacturer: the national instrument quantum science and technology steps: starting an analyzer, checking machine airflow, placing a sample, inputting necessary parameters, measuring by the instrument, and recording the result. The density was determined at 25 ℃.

The measured ionic liquid densities are shown in the following table:

density of ionic liquid

/>

The larger the volume of the cation, the smaller the density of the ionic liquid is, and the small change of the cation structure can adjust the density of the ionic liquid to different degrees.

After the hydrogen in the organic compound is replaced by fluorine, the fluorine-containing compound generally has a higher density because of the larger atomic weight of fluorine than hydrogen, and the fluorine-containing ionic liquid should have a higher density than the corresponding fluorine-free ionic liquid. The research on the influence of the introduction of fluorine element into ionic liquid on the density is lacking at present. Therefore, we explore the synthesis of a series of high density fluorine-containing ionic liquids. "

The ionic liquid has a density which follows a general rule, and the ionic liquid with iodide as the anion is denser than the corresponding hydride ionic liquid due to the presence of heavy elemental iodine. For the same anions, the density of the ionic liquid decreases as the alkyl chain on the cation grows, since an increase in the volume of the cation decreases the density of the ionic liquid.

For ionic liquids whose cations do not contain fluorine, the density is not too high. Therefore, we have designed to synthesize fluorine-containing cations. In the synthesized ionic liquid, the density of the ionic liquid of example 17 is as high as 2.23g/cm ³ . Where the cation volume is relatively highThe small pair also plays a certain role in improving the density.

The ionic liquids of comparative example 28 and example 30, both of which have the same anion H (CF ₂ ) ₄ O(CF ₂ ) ₂ SO ₃ Example 30 cation of ionic liquid (CH ₃ And Cl (CF) ₂ ) ₂ (CH ₂ ) ₂ ) The volume ratio of cations (H and n-C) of the ionic liquid of example 28 ₄ H ₉ ) The ionic liquid of example 30 should be smaller in density from a volumetric point of view, but in contrast, the ionic liquid of example 30 has a density > that of the ionic liquid of example 28, whereby it can be seen that the introduction of fluorine into the cation does help to increase the ionic liquid density.

The ionic liquid prepared by the invention is applied to the fields of high-density materials and pesticides as follows.

Application example 1: high density material

On the other hand, the ionic liquid has good application prospect as a new material, including new medium for preparing micro or nano materials, aerosol or gel, gas absorbent, carbon dioxide capture reagent, lubricant and the like, and the ionic liquid is widely applied in the field of material preparation, and the research scope comprises synthesis of polymers in the ionic liquid, preparation of inorganic nano materials, processing of natural polymers and the like.

Application example 2: pesticide

The ionic liquid can be used as a solvent to dissolve cellulose, and is used as a catalyst for efficiently assisting plant components to extract and provide stable green for converting biodiesel.

Claims

1. An imidazole ionic compound containing fluorosulfonate, which is characterized in that the density of the ionic compound is more than or equal to 1.5g/cm ³ 。

2. The ionic compound of claim 1, wherein: the glass transition temperature of the ionic compound is less than or equal to-38 ℃ and the decomposition temperature is 294-442 ℃.

3. An imidazole ion compound containing fluorosulfonate, wherein the ion compound has the following structural formula: Wherein:

R ¹ 、R ³ is C ₁ -C ₄ Alkyl, C ₁ -C ₄ Fluoroalkyl or aryl;

x is hydrogen, fluorine, chlorine or iodine;

n is an integer of 1 to 3.

4. The ionic compound of claim 3, wherein: the aryl group isR ⁶ 、R ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ Is C ₁ -C ₄ Alkyl or C ₁ -C ₄ An alkoxy group.

5. The ionic compound of claim 4, wherein: the aryl group is preferably phenyl or naphthyl.

6. The ionic compound of any one of claims 3 or 4, wherein: the C is ₁ -C ₄ The alkyl is selected from at least one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl.

7. The ionic compound of any one of claims 3 or 4, wherein: the C is ₁ -C ₄ The alkoxy group is selected from at least one of methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy.

8. The ionic compound of claim 3, wherein: the C is ₁ -C ₄ The fluoroalkyl group is at least one selected from a fluorine atom-substituted methyl group, a fluorine atom-substituted ethyl group, a fluorine atom-substituted propyl group, a fluorine atom-substituted isopropyl group, a fluorine atom-substituted butyl group, a fluorine atom-substituted isobutyl group, and a fluorine atom-substituted tert-butyl group.

9. The ionic compound of claim 8, wherein:

the methyl substituted by fluorine atoms is monofluoromethyl;

the fluorine atom substituted ethyl is monofluoroethyl;

the fluorine atom-substituted propyl group is a monofluoropropyl group;

the fluorine atom-substituted isopropyl is monofluoroisopropyl;

the fluorine atom-substituted butyl is monofluorobutyl;

the fluorine atom-substituted isobutyl is monofluoroisobutyl;

10. The ionic compound of claim 3, wherein the ionic compound has any one of the following structures:

11. the ionic compound of claim 3, wherein: the density of the ionic compound is more than or equal to 1.5g/cm ³ 。

12. The ionic compound of claim 11, wherein: the glass transition temperature of the ionic compound is less than or equal to-38 ℃ and the decomposition temperature is 294-442 ℃.

13. A process for preparing the ionic compound of any one of claims 1 or 3, which comprises: ion exchange reaction of ionic salts with sulfonates in solvents, wherein:

the ionic salt is

The sulfonate is X (CF) ₂ CF ₂ ) _n OCF ₂ CF ₂ SO ₃ M，

R ¹ 、R ³ Is C ₁ -C ₄ Alkyl, C ₁ -C ₄ Fluoroalkyl or aryl;

y is halogen, preferably chlorine, bromine or iodine;

x is hydrogen, fluorine, chlorine or iodine;

m is tetraalkylammonium, sodium or potassium;

n is an integer of 1 to 3.

14. The method of claim 13, wherein the solvent is selected from one or more of water, an alcoholic solvent, a mixed solvent of water and an alcoholic solvent, an amide-based solvent, a sulfoxide-based solvent, and a nitrile-based solvent.

15. The method according to claim 14, wherein the amide-based solvent is preferably N, N-dimethylformamide; the alcohol solvent is preferably ethanol, tertiary butanol or tertiary amyl alcohol; the nitrile solvent is preferably acetonitrile; the sulfoxide solvent is preferably dimethyl sulfoxide.

16. The method of claim 13, wherein the aryl group isR ⁶ 、R ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ Is C ₁ -C ₄ Alkyl or C ₁ -C ₄ An alkoxy group.

17. The method of claim 16, wherein the C ₁ -C ₄ The alkyl is selected from at least one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl.

18. The method of claim 16, wherein the C ₁ -C ₄ The alkoxy group is selected from at least one of methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy.

19. The method of claim 13, wherein: the C is ₁ -C ₄ The alkyl is selected from at least one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl.

20. The method of claim 13, wherein: the C is ₁ -C ₄ The alkoxy group is selected from at least one of methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy.

21. The method of claim 13, wherein: the C is ₁ -C ₄ The fluoroalkyl group is at least one selected from a fluorine atom-substituted methyl group, a fluorine atom-substituted ethyl group, a fluorine atom-substituted propyl group, a fluorine atom-substituted isopropyl group, a fluorine atom-substituted butyl group, a fluorine atom-substituted isobutyl group, and a fluorine atom-substituted tert-butyl group.

22. The method of claim 21, wherein:

the methyl substituted by fluorine atoms is monofluoromethyl;

the fluorine atom substituted ethyl is monofluoroethyl;

the fluorine atom-substituted propyl group is a monofluoropropyl group;

the fluorine atom-substituted isopropyl is monofluoroisopropyl;

the fluorine atom-substituted butyl is monofluorobutyl;

the fluorine atom-substituted isobutyl is monofluoroisobutyl;

23. The method of claim 13, wherein: the reaction temperature of the ion exchange reaction is 0-120 ℃.

24. The method of claim 13, wherein: the time of the ion exchange reaction is 0.5-24 hours.

25. The method of claim 13, wherein: the sulfonate is prepared by the following steps:

a) At 80 ℃, C _4-8 1, 4-dioxane solution of iodide;

e) C is C _4-8 Dissolving hydride in ethanol, adding aqueous solution of sodium hydroxide, heating to 110deg.C, refluxing at 80deg.C, stirring to stop reaction, concentrating under reduced pressure to remove ethanol, heating with ethyl acetate to reflux, dissolving, filtering, concentrating under reduced pressure to obtain white solid;

26. the method of claim 13, wherein: the sulfonate is prepared by the following steps:

c is C _4-8 Dissolving iodide in ethanol, adding aqueous solution of sodium hydroxide, heating to 110deg.C, refluxing at 80deg.C, stirring to stop reaction, concentrating under reduced pressure to remove ethanol, heating with ethyl acetate to reflux, dissolving, filtering, concentrating under reduced pressure to obtain white solid;

the C is _4-8 The mass ratio of iodide to sodium hydroxide is 3.75:1.

27. the method of any one of claims 25 or 26, wherein: the C is _4-8 The iodide is selected from: ICF (information and communication function) ₂ CF ₂ OCF ₂ CF ₂ SO ₂ F、I(CF ₂ CF ₂ ) ₂ OCF ₂ CF ₂ SO ₂ F、I(CF ₂ CF ₂ ) ₃ OCF ₂ CF ₂ SO ₂ F。

28. The method of claim 13, wherein: the ionic salt is prepared by the following steps: freezing 1-methylimidazole liquid nitrogen to-190 deg.C, adding C _1-3 The iodate is recovered to normal temperature, and the reaction is carried out at 50-120 ℃ under vacuum until the reaction is stopped, and the product is obtained after the product is washed by diethyl ether, wherein the 1-methylimidazole and the C _1-3 The mass ratio of the iodoalkane is 0.53:1.

29. The method as recited in claim 28, wherein: the C is _1-3 The iodoalkane is selected from: methyl iodide, ethyl iodide, and propyl iodide.

30. Use of an ionic compound according to any one of claims 1 or 3 in the field of high density materials.

31. Use of an ionic compound according to any one of claims 1 or 3 in the field of pesticides.