JP2022136032A - Novel fluorinated aromatic ester compound and gelator containing the same - Google Patents

Abstract

To provide a novel compound able to serve as a gelator that is of a low-molecular-weight type not having a hydrogen-bondable functional group in each molecule, and can gelate a wide range of organic solvents at low concentration.SOLUTION: A compound according to one embodiment of the present invention is a fluorinated aromatic ester compound represented by the following formula (I) (where Ar is a substituted or unsubstituted divalent aromatic group, y is 0, 1 or 2, m and n independently represent an integer of 1-20, p and q independently represent an integer of 0-6, and r represents an integer of 1-3).SELECTED DRAWING: None

Description

There is an application for application of Article 30, Paragraph 2 of the Patent Act. "Gel Physical Properties and Electrochemical Properties of Li-Ion Liquid Gel Electrolytes Formed with Fluorine-Containing Low-Molecular-Weight Gelling Agents" and "Evaluation of Physical Properties of Gels Using Biphenyl Derivatives Having Perfluoroalkyl Groups" in Kochi Conference Abstracts (2) On November 13, 2021, at the 2021 Chugoku-Shikoku Branch Meeting of the Chemical Society of Japan in Kochi, a poster presentation of the online holding method, "Li-ion liquid gel electrolyte formed with fluorine-containing low-molecular-weight gelling agent "Physical Properties and Electrochemical Properties of Gels" and "Evaluation of Physical Properties of Gels Using Biphenyl Derivatives Having Perfluoroalkyl Groups"

TECHNICAL FIELD The present invention relates to a novel fluorine-containing aromatic ester compound, particularly an aromatic ester compound having a perfluoroalkyl group and a gelling agent containing the same.

In various industrial fields (e.g., paints, cosmetics, pharmaceuticals and medical care, oil spill treatment, electronic/optical fields, environmental fields, etc.), the purpose of solidifying organic liquid substances, that is, solidifying them into jelly or increasing their viscosity. gelling agents are used in

Conventionally, low-molecular-weight or high-molecular-weight organic gelling agents have been used to immobilize organic liquids. Many of these organic gelators are known to be low-molecular-weight compounds with hydrogen-bonding functional groups (e.g., amino groups, amide groups, urea, etc.) or high-molecular-weight compounds with a three-dimensional network structure. It is Although the development of the former is relatively slow compared to the latter, dialkyl urea derivatives (Patent Document 1) and perfluoroalkyl derivatives [Non-Patent Document 1, Patent Document 2] are known. However, these compounds have problems such as limited types of gelling solvents, difficulty in compound stability, and gelation of organic electrolytes containing high-concentration supporting electrolytes. On the other hand, although Patent Document 3 is known as a compound having a molecular structure similar to that of the present invention, these compounds only have physical properties as nonlinear optical materials, and there is no description of gelation.
The present inventors have advanced the development of gelling agents capable of gelling various organic solvents at low concentrations, and have particularly proposed fluoroalkane derivatives.
Patent Documents 4 to 7 describe the following fluoroalkane derivatives.
(Patent Document 4)
CmF2m+1-(CH2)y-CHX-CnH2n-O-Ar-OR
(Wherein, X is a hydrogen atom or a halogen atom, y is 0 when X is a hydrogen atom, and y is 0 or 1 when X is a halogen atom. Ar is a substituted or unsubstituted C5 ~30 divalent aromatic group, R is a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms, m is a natural number of 6 to 12, and n is a natural number of 1 to 4.)
(Patent document 5)
R2-L1-Ar1-X1-R1
(In the formula (1), Ar represents a substituted or unsubstituted divalent aromatic group having 6 to 30 nuclear atoms, and R represents a saturated or unsaturated C 2 to 22 aromatic group having a perfluoroalkyl group. represents a monovalent hydrocarbon group, X represents an oxygen atom, a sulfur atom or a group represented by -SO2-, R2 represents a specific monovalent group, L1 is -COO- depending on the type of R2; represents a group represented by or -OCO-.)
(Patent document 6)
RX-Ar1-O-R1-O-Ar2-Y
(In the formula, Ar1 and Ar2 each independently represent a substituted or unsubstituted divalent aromatic group having 6 to 30 nuclear atoms, and R1 may have an oxygen atom or a sulfur atom in the chain. represents a good saturated or unsaturated divalent hydrocarbon group having 1 to 20 carbon atoms, R represents a saturated or unsaturated monovalent hydrocarbon group having 2 to 22 carbon atoms having a perfluoroalkyl group, and X represents a group represented by -S- or -SO2-, and Y represents a cyano group, a nitro group, a saturated or unsaturated monovalent alkoxyl group having 2 to 20 carbon atoms, or a fluorine atom.)
(Patent Document 7)
CmF2m+1R1-SO2-ZO-R2-O-Z-SO2-R3CnF2n+1
(Wherein, each of a plurality of Z independently represents a substituted or unsubstituted divalent aromatic hydrocarbon group having 5 to 30 nuclear atoms, and each of R1 and R3 independently represents a single bond or a saturated or unsaturated represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R is two or more substituted or unsubstituted divalent hydrocarbon groups having 2 to 18 carbon atoms and one or more oxygen and/or sulfur atoms. and m and n each independently represent a natural number of 2 to 18.)

JP-A-8-231942 JP-A-2007-191626 WO1991/008198 pamphlet JP 2019-081836 A JP 2016-175873 A JP 2016-064990 A JP 2011-246422 A

J. Fluorine Chem. 111, 47-58 (2001)

The present invention provides a novel compound that is a low-molecular-weight type that does not have a hydrogen-bonding functional group in the molecule and that can be a gelling agent capable of gelling a wide range of organic solvents including organic electrolytes and ionic liquids at low concentrations. The task is to provide

As a result of intensive studies aimed at solving the above problems, the present inventors have found that an aromatic ester compound having a perfluoroalkyl chain can solve the above problems, and have completed the present invention.

That is, the present invention includes the aspects shown below.
[1] A fluorine-containing aromatic ester compound represented by the following formula (1).

(In the formula,
Ar represents a substituted or unsubstituted divalent aromatic group,
y represents 0, 1 or 2,
m and n are each independently an integer from 1 to 20,
p and q each independently represent any integer from 0 to 6,
r represents any integer from 1 to 3)
[2] The fluorine-containing aromatic ester compound according to [1], wherein Ar in formula (I) is a substituted or unsubstituted phenylene group, naphthylene group or biphenylene group.
[3] A gelling agent containing the fluorine-containing aromatic ester compound according to [1] or [2]. [4] A gel composition containing the gelling agent according to [3] and an organic solvent.
[5] The gel composition according to [4], wherein the organic solvent is an ionic liquid.

The fluorine-containing aromatic ester compound of the present invention can gel various organic solvents such as protic organic solvents (alcoholic solvents) having active hydrogen (protons) and aprotic organic solvents.
Furthermore, basic organic solvents (N,N-diethylaniline) and ionic liquids can be gelled. In particular, protic ionic liquids, which have been difficult to gel with conventional techniques, can be gelled.

Gels (● and ■) of the compound (2-6-6) of the present invention and solvents (PC and [EMIM][FSA]), and compound (2-6-6) of the present invention and solvents and supporting electrolytes ( 1M LiClO_Four/pc and 1molkg^-1LiFSA/ [EMIM][FSA]) and gels (○ and □) show the relationship between the phase transition temperature to sol and the compound concentration. FIG. 2 is a diagram showing the relationship between the phase transition temperature to sol and the compound concentration for gels of compounds (1-6-6 and 2-6-6) of the present invention and 1-octanol. For gels of the compounds (2-6-6, 3-6-6, 4-6-6 and 5-6-6) of the present invention and propylene carbonate, the relationship between the phase transition temperature to sol and the compound concentration was determined. FIG. 4 is a diagram showing; Numbers in the figure indicate compound numbers. For gels of compounds of the present invention (1-6-6, 2-6-6, 3-6-6, 4-6-6 and 5-6-6) and ionic liquids [BMIM] [TFSA], sol It is a figure which shows the relationship between the phase transition temperature to and compound density|concentration. Numbers in the figure indicate compound numbers. For gels of the compounds of the present invention (2-6-6, 3-6-6 and 4-6-6) and 1M LiFSA / EC:PC:DEC, the relationship between the phase transition temperature to sol and the compound concentration was examined. FIG. 4 is a diagram showing; Numbers in the figure indicate compound numbers. FIG. 2 is a graph showing the relationship between shear rate and viscosity for compound (3-6-6) of the present invention and comparative example (compound K-8). The right figure is the compound (3-6-6) of the present invention, and the left figure is a comparative example (compound K-8).

(Fluorine-containing aromatic ester compound)
The fluorine-containing aromatic ester compound of the present invention is a compound represented by the following formula (1).

In the above formula,
Ar represents a substituted or unsubstituted divalent aromatic group,
y represents 0, 1 or 2,
m and n are each independently an integer from 1 to 20,
p and q each independently represent any integer from 0 to 6,
r represents an integer of 1 to 3;

The "divalent aromatic group" of the "substituted or unsubstituted divalent aromatic group" of Ar specifically represents a "C3-10 aromatic group". Here, "C3-10" represents the number of carbon atoms constituting the aromatic group, and in order to satisfy the aromaticity, a divalent aromatic group containing atoms other than carbon such as oxygen atoms, nitrogen atoms, sulfur atoms may form a family group. The aromatic group may be either monocyclic or polycyclic, and the polycyclic aromatic group has at least one aromatic ring and the remaining rings are saturated or unsaturated alicyclics. Either can be used. Aromatic groups include aromatic hydrocarbon groups and aromatic heterocyclic groups. Specifically, bivalent aromatic hydrocarbons such as phenylene group, naphthylene group, anthranylene group, phenanthrylene group, azulenylene group, pyrenylene group, chrysenylene group, fluorenylene group, fluorantenylene group, indenylene group, indanylene group, and tetralinylene group. pyrrolylene group, furylene group, thienylene group, imidazolene group, pyrazolene group, oxazolene group, isoxazolene group, thiazolene group, isothiazolene group, indolylene group, isoindolinylene group, indolizinylene group, benzimidazolene group, carbazolene group, etc. A divalent five-membered aromatic heterocyclic group, a pyridylene group, a pyrazinylene group, a pyrimidylene group, a pyridazylene group, a triazylene group, a quinolylene group, an isoquinolylene group, a quinoxalylen group, a cinolylene group, a quinazolylene group, a phthalazylene group, an acridylene group, and a naphthalylene group. , a bivalent 6-membered aromatic heterocyclic group such as a phenadylene group.
The polycyclic aromatic group also includes a group in which the aromatic rings are directly bonded together, such as a biphenylene group, in addition to the groups in which the aromatic rings are condensed as described above.
An aromatic hydrocarbon group is preferred, a phenylene group, a naphthylene group or a biphenylene group is more preferred, and a phenylene group is particularly preferred.

The substituent of the divalent aromatic group is not particularly limited as long as the effects of the present invention are achieved. Specific examples of groups that can be "substituents" include the following groups.

C1-6 alkyl groups such as a methyl group and an ethyl group;
C2-6 alkenyl groups such as a vinyl group and a 1-propenyl group;
C2-6 alkynyl groups such as an ethynyl group and a 1-propynyl group;
C3-8 cycloalkyl groups such as cyclopropyl group and cyclobutyl group;
C6-10 aryl group such as phenyl group and naphthyl group;
Halogeno groups such as fluoro, chloro, bromo and iodo groups;
fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3- pentafluoropropyl group, perfluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, perfluoroisopropyl group, 4-fluorobutyl group, 2,2,3,3,4,4, 4-heptafluorobutyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, chloromethyl group, bromomethyl group, dichloromethyl group, dibromomethyl group, trichloromethyl group, tribromomethyl group, 1-chloroethyl group , 2,2,2-trichloroethyl group, 4-chlorobutyl group, perchlorohexyl group, 2,4,6-trichlorohexyl group and other C1-6 haloalkyl groups.

m and n in C _m F _2m+1 (CH ₂ ) _p and (CH ₂ ) _q C _n F _2n+1 in formula (I) each independently represent an integer of 1 to 20, p and q each independently represents an integer of 0 to 6.

Specific examples of groups represented by C _m F _2m+1 (CH ₂ ) _p and (CH ₂ ) _q C _n F _2n+1 include a perfluoromethyl group, a perfluoroethyl group, a perfluoro-n-propyl group, perfluoro-n-butyl group, 1H,1H-perfluoro-n-butyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, 1H,1H,-perfluoro-n-pentyl group, 1H , 1H,2H,2H-perfluoro-n-hexyl group, 1H,1H,2H,2H,3H,3H-perfluoro-n-heptyl group, 1H,1H,2H,2H-perfluoro-n-octyl group , 1H,1H,2H,2H-perfluoro-n-nonyl group, 1H,1H,2H,2H,3H,3H-perfluoro-n-nonyl group, 1H,1H,2H,2H-perfluoro-n- decyl group, 1H, 1H, 2H, 2H, 3H, 3H-perfluoro-n-dodecyl group, and the like.

Examples of fluorine-containing aromatic ester compounds represented by formula (I) include compounds shown below when Ar is an aromatic hydrocarbon group.
In Table 1, each symbol represents the following.
Ph: 1,4-phenylene group,
BiPh: 4,4'-biphenylene group,
NaPh: 2,6-naphthylene group

(Method for Producing Fluorine-Containing Aromatic Ester Compound Represented by Formula (I))
The method for producing the fluorine-containing aromatic ester compound represented by formula (I) is not particularly limited.

In the above reaction formula, Ar, m, n, p, q, r and y are defined as in formula (I).
R represents an alkyl group such as a methyl group or an ethyl group, and X represents a halogeno group such as an iodine atom.
In step 1, first, thiolcarboxylic acid compound (1) is reacted with alcohol such as methanol in the presence of an acid catalyst such as sulfuric acid to obtain thiolcarboxylic acid ester compound (2). Then, the thiol carboxylic acid ester compound (2) is reacted with C _n F _2n+1 (CH ₂ ) in the presence of an alkali metal compound such as K ₂ CO ₃ in a solvent such as a ketone solvent such as acetone, 3-pentanone, or cyclohexanone. _q After thioetherification by reacting with a fluoroalkyl halide represented by X, the ester group is converted in a solvent such as an alcoholic solvent such as methanol or ethanol in the presence of an alkali metal hydroxide such as sodium hydroxide. Hydrolysis gives the thiophenyl compound (3).
Furthermore, it is oxidized with an oxidizing agent such as hydrogen peroxide in the presence of a catalyst such as acetic acid to obtain a sulfinyl compound (4-1) or a sulfonyl compound (4-2).

In step 2, the thiophenyl compound (3), sulfinyl compound (4-1) or sulfonyl compound (4-2) obtained in step 1 (collectively referred to as compound (5)) is first treated with thionyl chloride, etc. and then reacted with a fluoroalkyl alcohol represented by C _m F _2m+1 (CH ₂ ) _p OH in a solvent such as anhydrous pyridine or toluene to esterify the target compound. A certain fluorine-containing aromatic ester compound (6) is obtained.

(Gelling agent and gel composition)
The compound represented by formula (I) of the present invention can be used as a gelling agent for gelling an organic solvent. Compound (I) of the present invention is advantageous in that it can be gelled or solidified by adding a small amount of various organic solvents. Moreover, the gel composition of the present invention contains one or more compounds (I) and an organic solvent.
The gel composition of the present invention also includes gel electrolytes as electrolytes for lithium ion secondary batteries and electrolytes for fuel cells.

The organic solvent contained in the gel composition of the present invention is not particularly limited as long as it is an organic solvent, and organic solvents that are liquid at room temperature are preferred.

(organic solvent)
Examples of such organic solvents include
alcohols such as methanol, ethanol, isopropanol, butanol and octanol; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, γ-butyrolactone, γ-valerolactone and ε-caprolactone;
Ketones such as acetone, diethyl ketone, methyl ethyl ketone, 3-pentanone;
Hydrocarbons optionally having a fluorine atom such as pentane, hexane, octane, cyclohexane, perfluorodecalin, benzene, toluene, xylene, fluorobenzene, hexafluorobenzene;
diethyl ether, 1,2-dimethoxyethane, 1,4-dioxane, crown ethers; glymes;
Ethers such as tetrahydrofuran and fluoroalkyl ether;
Amides such as N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide;
amines optionally having a fluorine atom such as ethylenediamine, N,N-diethylaniline, pyridine, perfluorotributylamine;
Carbonates such as propylene carbonate, ethylene carbonate, vinylene carbonate, fluoroethylene carbonate, diethyl carbonate, ethylmethyl carbonate;
Nitriles such as acetonitrile, propionitrile, adiponitrile, methoxyacetonitrile;
Lactams such as N-methylpyrrolidone (NMP);
sulfones such as sulfolane;
Sulfoxides such as dimethylsulfoxide;
Silicon oil, industrial oils such as petroleum, and edible oils.

(ionic liquid)
Moreover, an ionic liquid can also be used as an organic solvent. An ionic liquid refers to a molten salt, and more specifically refers to an ionic salt that becomes liquid near room temperature. An ionic liquid is a liquid composed only of ions, and the cations that constitute the ionic liquid are not limited to specific cations. Examples of the cation include those with nitrogen as the ion center, those with phosphorus as the ion center, those with sulfur as the ion center, and those with nitrogen and sulfur as the ion center.

Examples of cations centered on nitrogen include imidazolium cations, ammonium cations, pyridinium cations, quinolinium cations, pyrrolidinium cations, piperazinium cations, piperazinium cations, morpholinium cations, and pyridazinium cations. , pyrimidinium cation, pyrazinium cation, pyrazolium cation, thiazolium cation, oxazolium cation, triazolium cation, guanidinium cation, 4-aza-1-azonia-bicyclo-[2,2 , 2] octanium and the like, and these cations may have a substituent represented by an alkyl group at any position, and the number of substituents may be plural.

The imidazolium cations include 1-methylimidazolium, 1-ethylimidazolium, 1-propylimidazolium, 1-butylimidazolium, 1-butyl-3-methylimidazolium [BMIM], 1-ethyl-3-methylimidazolium. lithium [EMIM], 1-allyl-3-methylimidazolium, 1,3-diallylimidazolium, 1-benzyl-3-methylimidazolium, 1-methyl-3-octylimidazolium, 1-ethyl-2,3 -dimethylimidazolium 1-butyl-2,3-dimethylimidazolium, 1,2,3-trialkylimidazolium such as 1,2-dimethyl-3-propylimidazolium, 1-cyanopropyl-3-methylimidazolium , 1,3-biscyanomethylimidazolium, 1,3-bis(3-cyanopropyl)imidazolium, 1-(2-hydroxyethyl)-3-methylimidazolium, 1-methoxyethyl-3-methylimidazolium , 1-[2-(2-methoxyethoxy)-ethyl]-3-methylimidazolium, 1,3-diethoxyimidazolium, 1,3-dimethoxyimidazolium, 1,3-dihydroxyimidazolium, 1-methyl -3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylimidazolium, 1-methyl-3-[(triethoxysilyl)propyl ] and imidazolium.

Ammonium cations include tetramethylammonium, tetraethylammonium, tetrabutylammonium, diethylmethylammonium [dema], tetrahexylammonium, trihexyltetradecylammonium, (2-hydroxyethyl)trimethylammonium, N,N-diethyl-N -(2-methoxyethyl)-N-methylammonium [DEME], tris(2-hydroxyethyl)methylammonium, N,N-trimethyl-N-propylammonium [TMPA], trimethyl (1H,1H,2H,2H- heptadecafluorodecyl)ammonium, trimethyl-(4-vinylbenzyl)ammonium, tributyl-(4-vinylbenzyl)ammonium, 2-(methacryloyloxy)ethyltrimethylammonium, benzyldimethyl(octyl)ammonium, N,N-dimethyl- and N-(2-phenoxyethyl)-1-dodecylammonium.

Pyridinium cations include 1-ethylpyridinium, 1-butylpyridinium, 1-(3-hydroxypropyl)pyridinium, 1-ethyl-3-methylpyridinium, 1-butyl-3-methylpyridinium, 1-butyl-4-methyl pyridinium, 1-(3-cyanopropyl)pyridinium and the like.

Examples of pyrrolidinium cations include 1-methyl-1-propylpyrrolidinium [P13], 1-butyl-1-methylpyrrolidinium, 1-(2-hydroxyethyl)-1-methylpyrrolidinium, 1- and ethyl-1-methylpyrrolidinium.

Piperidinium cations include 1-methyl-1-propylpiperidinium, 1-butyl-1-methylpiperidinium, 1-(2-hydroxyethyl)-1-methylpiperidinium, 1-ethyl-1- methyl piperidinium and the like.

Cations having phosphorus as an ion center are generally called phosphonium cations, and specific examples include tetrabutylphosphonium, tetrahexylphosphonium, trihexyltetradecylphosphonium, triphenylmethylphosphonium, (2-cyanoethyl)triethylphosphonium, (3-chloropropyl)trioctylphosphonium, tributyl(4-vinylbenzyl)phosphonium, triisobutylmethylphosphonium, triethylmethylphosphonium, tributylmethylphosphonium, tributylhexadecylphosphonium, 3-(triphenylphosphonio)propane-1-sulfone acids and the like.

A cation having sulfur as an ion center is generally called a sulfonium cation, and specific examples thereof include triethylsulfonium, tributylsulfonium, 1-ethyltetrahydrothiophenium, and 1-butyltetrahydrothiophenium.

Examples of anions that serve as pairs of cations include fluoride, chloride, bromide, iodide, dicyanamide, bis(fluorosulfonyl)amide [FSA], bis(trifluoromethylsulfonyl)amide [TFSA], bis(trifluoroethylsulfonyl)amide, bis(pentafluoroethylsulfonyl)amide, bis(nonafluorobutylsulfonyl)amide, tetrafluoroborate [BF ₄ ], bis(trifluoromethyl)difluoroborate, (trifluoromethyl)trifluoroborate, tetrakis[3,5- Bis(trifluoromethyl)phenyl]borate, methanesulfonate, butylsulfonate, trifluoromethanesulfonate, tetrafluoroethanesulfonate, nonafluorobutanesulfonate, benzenesulfonate, p-toluenesulfonate, 2,4,6-trimethylbenzenesulfonate, styrenesulfonate , perfluorooctane sulfonate, heptadecafluorooctane sulfonate, 3-sulfopropyl methacrylate, 3-sulfopropyl acrylate, methyl sulfate, ethyl sulfate, octyl sulfate, diethylene glycol monomethyl ether sulfate, hydrogen sulfate, hexafluorophosphate [PF ₆ ], tris(trifluoromethyl)trifluorophosphate, tris(pentafluoroethyl)trifluorophosphate, dihydrogenphosphate, dibutylphosphate, diethylphosphate, dimethylphosphate, bis(2,4,4-trimethylpentyl) Phosphinate, methylphosphonate, methylmethylphosphonate, formate, acetate, propionate, butyrate, trifluoroacetate, hydroxyacetate, perfluorononanoate, decanoate, mandelate, thiosalicylate, benzoate, salicylate, fluorohydrogenate, lactate, glycinate, alaninate, Leucinate, Valinate, Trifluoromethanesulfonyl Leucinate, Trifluoromethanesulfonyl Valinate, Nitrate, Perchlorate, Phenoxide, Thiocyanate, Tris(trifluoromethanesulfonyl)methide, Acesulfamate, Saccharinate, Pyrazolate, Imidazolate, Thiazolate, Triazolate, Tetrazole indazolate, benzothiazolate, hexafluoroastatinate, hexafluoroantimonate, thiocyanate, tetrachloroaluminate, tetrachloroferrate [FeCl ₄ ], carbonate, methyl carbonate, carbamate and the like.
These organic solvents are used singly or in combination of two or more.

Ionic liquids are classified into protic ionic liquids and aprotic ionic liquids. A protic ionic liquid is an ionic liquid formed from an acid and a base, in which protons migrate from the acid to the base to form a conjugate base and a conjugate acid. Aprotic ionic liquids refer to liquids that are not classified as protic ionic liquids.
Examples of aprotic ionic liquids include, for example, [BMIM] [TFSA] (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide), [EMIM] [FSA] (1-ethyl-3 methylimidazolium bis(fluorosulfonyl)amide), etc. Examples of protic ionic liquids include [dema][TfO] (diethylmethylammonium trifluoromethanesulfonate), [dema][TFSA] (diethylmethylammonium bis (trifluoromethylsulfonyl)amide), [N,N-diethylaniline] [TFSA] and the like.

(gel electrolyte)
The gelling agent of the present invention can gel high dielectric constant solvents suitable for organic electrolytes, such as propylene carbonate. A gel produced by gelling a high dielectric constant solvent with the gelling agent of the present invention can be used as a gel electrolyte. This gel electrolyte can be used in lithium ion batteries. It can also be used as a gel electrolyte for dye-sensitized solar cells and fuel cells.
The electrolyte is one that is used as a normal non-aqueous electrolyte in the electrolytic solution, but when it is used in a lithium ion secondary battery, a lithium salt is used as a supporting electrolyte. Specific examples of the lithium salt include, but are not limited to, LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , Li ₂ SiF ₆ , LiOSO ₂ C _k F _2k+1 [k is an integer of 1 to 8], LiN (SO ₂ C _k F _2k+1 ) ₂ [k is an integer of 1 to 8], LiPFn(C _k F _2k+1 ) _6-n [n is an integer of 1 to 5, k is an integer of 1 to 8], LiBF _n ( (C _k F _2k+1 ) _4-n [n is an integer of 1 to 3, k is an integer of 1 to 8], lithium bis(oxalate)borate represented by LiB(C ₂ O ₄ ) ₂ , LiBF ₂ (C ₂ O ₄ ), lithium tetrafluoro(oxalate) phosphate represented by LiPF ₄ (C ₂ O ₄ ), LiPO ₂ F ₂ and Li ₂ PO ₃ F.
These lithium salts are used individually by 1 type or in combination of 2 or more types.

(Preparation of gel composition)
The gel composition of the present invention preferably contains 0.05 to 10.0% by mass, more preferably 0.1 to 8.0% by mass, of the compound represented by formula (I) with respect to the total amount. , more preferably 0.3 to 5.0% by mass. When the content is at least the above lower limit, the compound represented by the formula (I) tends to function more adequately as a gelling agent, and when it is at most the above upper limit, economy and handling are improved. tends to be further improved, the gelling agent can be further suppressed from becoming an impurity, and the deterioration of the performance of the organic solvent can be further prevented. From the same point of view, the gel composition of the present invention preferably contains 90 to 99.95% by mass of an organic solvent, more preferably 92 to 99.9% by mass, and more preferably 95 to 99.7% by mass of the total amount of the organic solvent. It is more preferable to contain it in mass %.

The gel composition of the present invention contains, in addition to the compound represented by formula (I) and an organic solvent, other components as long as they do not inhibit the function of the compound represented by formula (I) as a gelling agent. may contain. Examples of such components include gelling agents, coagulants, thickeners, stabilizers, antioxidants, emulsifiers, lubricants, and safety-enhancing additives other than the compound represented by formula (I). mentioned.

The method for preparing the gel composition of the present invention is not particularly limited. It can be prepared by lowering the temperature of the mixture. The order in which the components are mixed is not particularly limited, but it is preferable to prepare a solution of an organic solvent and an additive in advance and then mix the solution with the gelling agent, because a uniform mixed solution can be obtained more easily.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the technical scope of the present invention is not limited to these. Measurements in the examples were as follows.
(Nuclear magnetic resonance (NMR) spectrum measurement)
¹ H-NMR spectrum measurement was performed using JNM-ECA500 manufactured by JEOL Ltd. Measurements were performed at room temperature, CDCl ₃ or DMSO-d ₆ was used as the measurement solvent, and TMS (tetramethyl silane) or DMSO-H (2.49 ppm) was used as the internal standard. Denshi Co., Ltd.) was used.
(Infrared absorption (IR) spectrum measurement)
Infrared absorption spectrum measurement is performed using a Fourier transform infrared spectrophotometer (SHIMADZU IRprestage-21) manufactured by Shimadzu Corporation. was attached and measured by the total reflection measurement (ATR) method. IR Solution and Lab Solution IR were used for measurement and analysis.
(Melting point measurement)
The melting points of the compounds were measured using a micro melting point analyzer (RFS-10 special type) manufactured by J Science Co., Ltd.
(purity measurement)
The purity of the gelling agent was measured using a high-performance liquid chromatograph manufactured by Shimadzu Corporation (HPLC, UV-visible spectrophotometer detector SPD-20A, system controller CBM-20A, column oven CTO-20A, column ODS-H, liquid unit LC-20AT) was used. 99.7% methanol was used as a developing solvent, the measurement wavelength was 290 nm, the measurement temperature was 42° C., and the liquid feeding rate was 1.0 mL/min.
(Silica gel column chromatograph)
For silica gel column chromatography, distilled chloroform was used as a developing solvent, and a normal phase silica gel column chromatograph was used with porous fractured silica gel (Daiso Co., Ltd. IR-60-15173) as a carrier.

[Synthesis of compound (1-6-6)]
(1) Esterification

In a 1 L eggplant flask, 20.2 g (131 mmol) of compound (a), 360 mL of methanol, and 9 mL of sulfuric acid as a catalyst were added and refluxed for 3 days. Cyclopentyl methyl ether and water were added thereto for extraction. A saturated NaCl aqueous solution was added to the obtained organic layer to extract again. Anhydrous magnesium sulfate was added to the obtained organic layer to dry it, and the solid was separated by folding filtration. The obtained filtrate was concentrated under reduced pressure and then recrystallized with methanol to obtain 16.3 g of compound (b) (yield: 74%, melting point: 49-52°C, ¹ H-NMR (500 MHz, CDCl ₃ ): δ = 3.55 (1H, s), 3.84 (1H, s), 7.23 (2H, d, J=7.9 Hz), 7.83 (2H, d, J=8.5 Hz) ppm, IR (KBr disc): ν _(CO) = 1274 cm ^-1 , ν _(C=C) = 1580 cm ^-1 , ν _(C=O) = 1720 cm ^-1 , ν _(CH) = 2940 cm ^-1 )

(2) Thioetherification

In a 1 L eggplant flask, 16.1 g (95.7 mmol) of the compound (b) obtained in (1) above and 50 g (133 mmol) of 2-(perfluorohexyl)ethyl iodide were dissolved in 400 mL of 3-pentanone, 15 g of potassium carbonate was added thereto and refluxed for 2 days. After confirming the disappearance of the starting materials by high-performance liquid chromatography, the mixture was allowed to cool to room temperature, potassium carbonate was removed using fold filtration, and the resulting solution was concentrated under reduced pressure to obtain 42.4 g of compound (c). (Yield: 86%, melting point: 60-62°C, ¹ H-NMR (500 MHz, CDCl ₃ ): δ = 2.36 (2H, q, J = 7.3 Hz), 3.13-3.16 (2H, m), 3.85 (3H, s), 7.26 (2H, d, J=8.5 Hz), 7.91 (2H, d, J=8.5 Hz) ppm, IR (KBr disc): ν _(CF) = 1090-1284 cm ^-1 , ν _(CO) = 1283 cm ^-1 , ν _(C=C) = 1600 cm ^-1 , ν _(C=O) = 1720 cm ^-1 , ν _(CH) = 2950 cm ^-1 )

(3) Hydrolysis

15.0 g of the compound (c) obtained in the above (2) was transferred to a 1 L eggplant flask, 500 mL of methanol and 60 mL of a 10N aqueous sodium hydroxide solution were added, and the mixture was refluxed for 2 hours. After completion of the reaction, the reaction vessel was cooled in an ice bath, 12N hydrochloric acid was added thereto to acidify the mixture, and the mixture was stirred in the ice bath for 1 hour. The precipitated solid was collected by suction filtration, washed with water, dried, and recrystallized with methanol to obtain 10.4 g of compound (aS). (Yield: 71%, Melting point: 161-162°C, ¹ H-NMR (500 MHz, DMSO-d ₆ ): δ = 2.56 (2H, q, J = 7.3 Hz), 3.34 (2H, m), 7.45 (2H, d, J=8.5 Hz), 7.81 (2H, d, J=8.5 Hz), 12.96 (1H, s) ppm, IR (KBr disc): ν _(CF) = 1090 - 1284 cm ^-1 , ν _(CO) = 1283 cm ^-1 , ν _(C=C) = 1600 cm ^-1 , ν _(C=O) = 1720 cm ^-1 , ν _(CH) = 2950 cm ^-1 , ν _(OH) = 3160 cm ^{-1 1} )

(4) Esterification

2.00 g (4.00 mmol) of the compound (aS) obtained in (3) above and an excess amount of thionyl chloride were added to a 1 L eggplant flask, stirred at 80° C. for 45 minutes, and then chlorinated with a water-jet aspirator. Thionyl was removed. The reaction residue was dissolved in 8 mL of anhydrous toluene. To this solution, 1.46 g (4.00 mmol) of C ₆ F ₁₃ C ₂ H ₄ OH dissolved in 8 mL of anhydrous pyridine was added and reacted with stirring at 80° C. for 4 hours. After the reaction, the solvent was removed with an evaporator, ethanol was added to the resulting residue to remove pyridine hydrochloride as a by-product, suction filtration was performed, and the target compound (1-6 -6) 2.32 g was obtained (yield: 68%, melting point: 74-75°C, ¹ H-NMR (500 MHz, CDCl ₃ ): δ = 2.39-2.49 (2H, m), 2.55-2.65 ( 2H, m), 3.20-3.23 (2H, m), 4.62 (2H, t, J=6.3Hz), 7.33 (2H, d, J=8.6Hz), 7.97 (2H, dd, J=6.3, 1.7Hz ) ppm, IR (ATR-IR): ν _(CF) = 1080-1230 cm ^-1 , ν _(CO) = 1261-1366 cm ^-1 , ν _(CH) = 1599 cm ^-1 , ν _(C=O) = 1716 cm ^-1 )

[Synthesis of compound (2-6-6)]
Using compound (aS) obtained in the hydrolysis step of Example 1, compound (2-6-6) was obtained in the following steps.

(1) Oxidation

10.0 g (20.0 mmol) of the compound (aS) obtained in (3) of Example 1 above, 11.38 g of 35% by mass hydrogen peroxide, and 200 mL of acetic acid were placed in a 300 mL eggplant flask and refluxed for 3 days. gone. After completion of the reaction, the mixture was allowed to stand still to room temperature, and 60 mL of a 20% by mass aqueous solution of sodium hydrogen sulfite was added thereto, followed by suction filtration to obtain 10.6 g of compound (a-SO ₂ ) (yield: 99%, melting point: 268). -269°C, ¹ H-NMR (500 MHz, CDCl ₃ ): δ = 2.48-2.73 (2H, m), 3.34(2H, s), 8.03 (2H, d, J=8.6 Hz), 8.28 (2H, d, J=8.6 Hz) ppm, IR (KBr disc): ν _(CF) = 1090-1284 cm ^-1 , ν _(S=O) = 1120-1363 cm ^-1 , ν _(CO) = 1283 cm ^-1 , ν _(C=C) = 1600 cm ^-1 , ν _(C=O) = 1720 cm ^-1 , ν _(CH) = 2950 cm ^-1 , ν _(OH) = 3340 cm ^-1 )

(2) Esterification

In a 50 mL eggplant flask, 1.00 g (2.00 mmol) of the compound (a-SO ₂ ) obtained in (1) above and an excess amount of thionyl chloride were added, stirred at 80° C. for 90 minutes, and then Thionyl chloride was removed with an aspirator. The reaction residue was dissolved in 8 mL of anhydrous toluene. To this solution, 1.46 g (2.00 mmol) of C ₆ F ₁₃ C ₂ H ₄ OH dissolved in 8 mL of anhydrous pyridine was added and reacted with stirring at 80° C. for 4 hours. After the reaction, the solvent is removed with an evaporator, ethanol is added to the resulting residue to remove pyridine hydrochloride as a by-product, suction filtration is performed, and the target compound (2-6 -6) 2.80 g was obtained (yield: 79%, melting point: 135-137°C, ¹ H-NMR (500 MHz, CDCl ₃ ): δ = 2.49-2.63 (4H, m), 3.27-3.30 ( 2H, m), 4.63 (2H, t, J=6.3 Hz), 7.98 (2H, dd, J=6.6, 2.0 Hz), 8.21 (2H, dd, J=6.3, 1.7 Hz) ppm, IR (ATR- IR): ν _(CF) =1085-1228 cm ^-1 , ν _(S=O) = 1107-1217 cm ^-1 , ν _(CO) = 1263-1329 cm ^-1 , ν _(C=O) = 1720 cm ^-1 )

[Synthesis of compound (1-8-6)]

(1) Esterification

4-mercaptobenzoic acid (20.2 g, 131 mmol), 360 mL of methanol and 9 mL of concentrated sulfuric acid were added to a 1 L eggplant flask and refluxed for 3 days. After completion of the reaction, the mixture was allowed to cool to room temperature, the reaction solution was transferred to a separatory funnel, and cyclopentyl methyl ether and water were added thereto for extraction. A saturated NaCl aqueous solution was added to the obtained organic layer, and extracted again. Anhydrous MgSO ₄ was added to the resulting organic layer to dry it, and the solids were separated by pleated filtration. The resulting filtrate was concentrated under reduced pressure and then recrystallized with methanol to obtain 16.3 g of compound (A). (Yield: 74%, melting point: 49-52°C, ¹ H-NMR (500 MHz, CDCl ₃ ): δ = 3.55 (1H, s), 3.84 (1H, s), 7.23 (2H, d, J= 7.9 Hz), 7.83 (2H, d, J=8.5 Hz) ppm, IR (KBr disc): v _(CO) = 1274 cm ^-1 , v _(C=C) = 1580 cm ^-1 , v _{(C=O )} = 1720 cm ^-1 , ν _(CH) = 2940 cm ^-1 )

(2) Thioetherification

Compound A (16.1 g, 95.7 mmol), 2-(perfluorohexyl)ethyl iodide (50 g, 133 mmol), K ₂ CO ₃ 15 g, and 3-pentanone 400 mL were added to a 1 L eggplant flask and refluxed for 2 days. Thereafter, the mixture was allowed to cool to room temperature, solids were removed by fold filtration, and the filtrate was concentrated under reduced pressure to obtain 42.4 g of compound (B-6). (Yield: 86%, melting point: 60 - 62°C, ¹ H-NMR (500 MHz, CDCl ₃ ): δ = 2.36 (2H, q, J = 7.3 Hz), 3.13-3.16 (2H, m), 3.85 (3H, s), 7.26 (2H, d, J=8.5 Hz), 7.91 (2H, d, J=8.5 Hz) ppm, IR (KBr disc): v _(CF) = 1090 - 1284 cm ^-1 , v _(CO) = 1283 cm ^-1 , v _(C=C) = 1600 cm ^-1 , v _(C=O) = 1720 cm ^-1 , ν _(CH) = 2950 cm ^-1 )

(3) Hydrolysis

Compound (B-6) (15.0 g, 29.2 mmol), 500 mL of methanol, and 60 mL of 10N NaOH aqueous solution were added to a 1 L eggplant flask and refluxed for 2 hours. After completion of the reaction, the reaction solution was transferred to a 2 L Erlenmeyer flask, 3 pieces of ice were added, and the reaction solution was sufficiently cooled in an ice bath. The resulting solid was suction filtered and recrystallized with methanol to obtain 10.4 g of compound (C-6). (Yield: 71 %, melting point: 161 - 163°C, ¹ H-NMR (500 MHz, DMSO-d ₆ ): δ = 2.56 (2H, q, J = 7.3 Hz), 3.34 (2H, m), 7.45 (2H, d, J=8.5 Hz), 7.81 (2H, d, J=8.5 Hz), 12.96 (1H, s) ppm, IR (KBr disc): v _(CF) = 1090 - 1284 cm ^-1 , v _(CO) = 1283 cm ^-1 , v _(C=C) = 1600 cm ^-1 , v _(C=O) = 1720 cm ^-1 , ν _(CH) = 2950 cm ^-1 , v _(OH) = 3160 cm ^{- 1} )

(4) Esterification

Compound (c-6) (1.0 g, 2.0 mmol), 1H, 1H, 2H, 2H-perfluoro-1-decanol (1.0 g, 2.0 mmol), 1-(3-Dimethylaminopropyl) were placed in a 50 mL eggplant flask. -3-ethylcarbodiimide Hydrochloride (EDC.HCl, 0.63 g, 3.3 mmol), 4-dimethylaminopyridine (DMAP; 0.1 g, 0.81 mmol), and 20 mL of dimethylformamide (DMF) were added and stirred overnight at room temperature. Toluene and water were added to extract the organic layer, and then the organic layer was washed with saturated brine. The resulting organic layer was dried over anhydrous _MgSO4 and the solids separated by pleated filtration. The resulting filtrate was concentrated under reduced pressure and then recrystallized from a chloroform-ethanol mixed solvent to obtain 1.4 g of the target compound (1-8-6). (Yield: 73%. Melting point: 83 - 84°C, ¹ H-NMR (500 MHz, CDCl ₃ ): δ = 2.39-2.49 (2H, m), 2.55-2.65 (2H, m), 3.20-3.23 ( 2H, m), 4.62 (2H, t, J=6.3 Hz), 7.33 (2H, d, J=8.6 Hz), 7.97 (2H, d, J=8.6 Hz) ppm, IR (ATR-IR): ν _(CF) = 1080-1230 cm ^-1 , ν _(CO) = 1261-1366 cm ^-1 , ν _(CH) = 1599 cm ^-1 , ν _(C=O) = 1716 cm ^-1 )

[Synthesis of compound (2-6-4)]
Using compound (A) obtained in (1) of Example 3, compound (2-6-4) was obtained in the following steps.

(1) Thioetherification

Compound (A) (9.74 g, 0.0576 mol) was added to a 1000 mL eggplant flask and dissolved in 200 mL of 3-Pentanone. Further, 10 g of potassium carbonate and 2-(perfluorobutyl)ethyl ionide (21.54 g, 0.0575 mol) were added and refluxed for 2 days. After that, the mixture was allowed to cool to room temperature, and the solution was filtered through a folded filter paper. The filtrate was concentrated by an evaporator and allowed to cool to room temperature to obtain a brown solid. The obtained solid was recrystallized with methanol to obtain 16.86 g of compound (B-4). (Yield: 78%, melting point: 45-46°C, ¹ HNMR (500 MHz, CDCl ₃ ) δ = 1.06 (2H, t, J=7.2 Hz), 3.21 (2H, t, J=8.2 Hz), 3.91 ( 3H, s), 7.33 (2H, d, J=8.5 Hz), 7.98 (2H, d, J=8.5 Hz) ppm, IR (KBr disc)ν _(CS) =1190 cm ⁻¹ ,ν _(CF) =1209 cm ⁻¹ , ν _(CO) =1296cm ⁻¹ , ν _(CH) =1337cm ⁻¹ , ν _(C=O) =1712cm ⁻¹ )

(2) Hydrolysis

Compound (B-4) (25 g, 60.1 mmol) was added to a 1000 mL eggplant flask and dissolved in 500 mL of methanol. 60 mL of 10N NaOH aqueous solution was added thereto and refluxed for 2 hours. After the reaction, the reactant after refluxing was transferred to a 2000 mL Erlenmeyer flask and acidified by adding 12N HCl aqueous solution and 8 pieces of ice. Since heat of neutralization was generated at this time, the mixture was stirred in an ice bath for 1 hour. The resulting solid was suction filtered and recrystallized using methanol to obtain 17.43 g of compound (C-4). (Yield: 72%, melting point: 140 - 141°C, ¹ HNMR (500 MHz, DMSO-d ₆ ) δ = 2.45 (2H, t, J = 8.5 Hz), 3.22 (2H, t, J = 8.2 Hz), 7.34 (2H, d, J=8.0 Hz), 8.03 (2H, d, J=8.5 Hz) ppm, IR (KBr disc) ν _(CF) =1223 cm ⁻¹ , ν _(C=O) =1676 cm ⁻¹ , ν _(OH) =2979 cm ^-1 )

(3) Oxidation

10.00 g of compound (C-4), 200 mL of acetic acid, 30 wt% H₂O.₂11.38 g was added and refluxed for 3 days. After allowing to cool to room temperature, 60 mL of a 20 wt % sodium sulfite aqueous solution was added to the reaction solution, followed by washing with water. The precipitate was suction filtered to obtain 10.57 g of compound (D-4). (Yield: 99%, Melting point: 164-167°C,¹H-NMR (500 MHz, DMSO-d₆) δ = 2.54-2.65 (2H, m), 3.77 (2H, t, J=8.0 Hz), 8.06 (2H, d, J=8.6 Hz), 8.17 (2H, d, J=8.6 Hz) ppm, IR (KBr disc): ν_(CF) = 1270-1190cm^-1, ν_(CO) = 1740 cm^-1, ν_(CH)= 2900cm^-1)

(4) Esterification

Compound (D-4) (0.51 g, 1.18 mmol), 1H,1H,2H,2H-perfluor-1-octanol (0.43 g, 1.18 mmol), (1-(3-Dimethylaminopropyl )-3-ethylcarbodiimide Hydrochloride, EDC.HCl, 0.34 g, 1.77 mmol), 4-dimethylaminopyridine (DMAP; 0.5 g, 4.46 mmol), and 20 mL of dimethylformamide (DMF) were added and stirred overnight at room temperature. Toluene and water were added to extract the organic layer, and then the organic layer was washed with saturated brine. The resulting organic layer was dried over anhydrous _MgSO4 and the solids separated by pleated filtration. The resulting filtrate was concentrated under reduced pressure and then recrystallized from a chloroform-ethanol mixed solvent to obtain 0.63 g of the target compound (2-6-4). (Yield: 69%, Melting point: 128-129°C, ¹ H-NMR (500 MHz, CDCl ₃ ) δ = 2.49-2.63 (4H, m), 3.27-3.30 (2H, m), 4.64 (2H, t , J=6.3 Hz), 7.98 (2H, d, J=8.6 Hz), 8.21 (2H, d, J=8.6 Hz) ppm, IR (ATR-IR): ν _(CF) = 1085-1230 cm ^-1 , ν _(S=O) = 1110-1220 cm ^-1 , ν _(CO) = 1260-1330 cm ^-1 , ν _(C=O) = 1720 cm ^-1 )

300mLナスフラスコにMethyl 4-hydroxybenzoate (10g, 66 mmol)、Benzyl bromide (11g, 66mmol)、K₂CO₃30 g、3-pentanone 200 mLを加えて30時間還流した。反応終了後、ひだ折り濾過により固体を取り除き、減圧濃縮して得られた固体をメタノールで再結晶して化合物E 8.0 gを得た。（収率： 73%、融点：108 - 110℃、¹H-NMR (500 MHz, CDCl₃) δ = 3.80 (3H, s), 5.03 (2H, s), 6.91 (2H, d, J=8.6 Hz), 7.25-7.36 (5H, m), 7.91 (2H, d, J=8.6 Hz) ppm、IR (ATR-IR): v_(Me-O)= 1008 - 1242 cm^-1, v_(Ph-O) = 1028 - 1317 cm^-1, v_(C=O) = 1709 cm^-1, v_{(C-H of Me)} = 2848 cm^-1, v_{(C-H of Ph)} = 2954 cm^-1）
[Synthesis of compound 3-6-6]
(1) Benzyl etherification

Methyl 4-hydroxybenzoate (10g, 66 mmol), Benzyl bromide (11g, 66mmol), K₂CO₃30 g of 3-pentanone and 200 mL of 3-pentanone were added and refluxed for 30 hours. After completion of the reaction, the solid was removed by pleat filtration, and the solid obtained by concentration under reduced pressure was recrystallized with methanol to obtain 8.0 g of Compound E. (Yield: 73%, Melting point: 108 - 110°C,¹H-NMR (500 MHz, CDCl₃) δ = 3.80 (3H, s), 5.03 (2H, s), 6.91 (2H, d, J=8.6 Hz), 7.25-7.36 (5H, m), 7.91 (2H, d, J=8.6 Hz) ppm , IR (ATR-IR): v_(Me-O)= 1008 - 1242 cm^-1, v_(Ph-O) = 1028 - 1317 cm^-1, v_(C=O)= 1709 cm^-1, v_{(CH of Me)} = 2848 cm^-1, v_{(CH of Ph)} = 2954 cm^-1)

300mLナスフラスコに化合物E (6.0g, 15mmol)、メタノール150 mL、6N NaOH水溶液50mLを加えて2時間還流した。反応終了後、反応溶液を2L三角フラスコに移し、そこに氷３個加えて氷浴中で反応溶液を十分に冷却した後、12N HCl水溶液150 mLを加えて氷浴中で1時間攪拌した。得られた固体を吸引ろ過した後に水洗して化合物F4.1 gを得た。（収率：72%、融点：193 - 195℃、¹H-NMR (500 MHz, DMSO-d₆) δ = 5.16 (2H, s), 7.08 (2H, d, J=8.6 Hz), 7.32-7.45 (5H, m), 7.87 (2H, d, J=8.6 Hz) ppm、IR (ATR-IR): ν_(C-O) =1273 cm^-1, ν_(C-H) = 1337 cm^-1, ν_(C=O) = 1720 cm^-1, ν_(C=C)= 1597 cm^-1, ν_(O-H) = 2979 cm^-1） (2) Hydrolysis

Compound E (6.0 g, 15 mmol), 150 mL of methanol, and 50 mL of 6N NaOH aqueous solution were added to a 300 mL eggplant flask and refluxed for 2 hours. After completion of the reaction, the reaction solution was transferred to a 2 L Erlenmeyer flask, 3 pieces of ice were added, and the reaction solution was sufficiently cooled in an ice bath. The resulting solid was suction filtered and then washed with water to obtain 4.1 g of compound F. (Yield: 72%, Melting point: 193-195 ° C., ¹ H-NMR (500 MHz, DMSO-d ₆ ) δ = 5.16 (2H, s), 7.08 (2H, d, J = 8.6 Hz), 7.32- 7.45 (5H, m), 7.87 (2H, d, J=8.6 Hz) ppm, IR (ATR-IR): ν _(CO) =1273 cm ^-1 , ν _(CH) = 1337 cm ^-1 , ν _{(C =O)} = 1720 cm ^-1 , ν _(C=C) = 1597 cm ^-1 , ν _(OH) = 2979 cm ^-1 )

50 mLナスフラスコに化合物F (2.5g, 11mmol)、2-(perfluorohexyl)ethanol (4.0 g, 11 mmol)、1-ethyl-3-(3-dimethylaminopropyl)carbodiimide-hydrochloride (EDC・HCl, 2.2 g, 11 mmol), dimethylaminopyridine (DMAP, 0.5 g)、N,N-dimethylformamide (DMF, 20 mL)を加えて室温で一晩攪拌した。得られた反応混合物を、トルエンで2回抽出し、有機層を飽和食塩水で洗浄した。得られた有機層をエバポレーターで減圧濃縮して得られた固体をクロロホルム?エタノール混合溶媒で再結晶を行って化合物G 2.8 gを得た。（収率：44%、融点：60 - 61℃、¹H-NMR (500 MHz, CDCl₃) δ = 2.47-2.57 (2H, m), 4.53 (2H, t, J=6.3 Hz), 5.06 (2H, s), 6.93 (2H, d, J=8.6 Hz), 7.28-7.39 (5H, m), 7.92 (2H, d, J=9.2 Hz) ppm、IR (ATR-IR): ν_(C-F) = 1018 - 1282 cm^-1, ν_(C-O)=1230 cm^-1, ν_(C-H) = 1319 cm^-1, ν_(C=C)= 1579 cm^-1,ν_(C=O) = 1714 cm^-1） (3) Esterification

Compound F (2.5 g, 11 mmol), 2-(perfluorohexyl)ethanol (4.0 g, 11 mmol), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide-hydrochloride (EDC・HCl, 2.2 g, 11 mmol), dimethylaminopyridine (DMAP, 0.5 g) and N,N-dimethylformamide (DMF, 20 mL) were added and stirred overnight at room temperature. The resulting reaction mixture was extracted twice with toluene, and the organic layer was washed with saturated brine. The solid obtained by concentrating the obtained organic layer under reduced pressure with an evaporator was recrystallized with a chloroform-ethanol mixed solvent to obtain 2.8 g of compound G. (Yield: 44%, Melting point: 60-61°C, ¹ H-NMR (500 MHz, CDCl ₃ ) δ = 2.47-2.57 (2H, m), 4.53 (2H, t, J=6.3 Hz), 5.06 ( 2H, s), 6.93 (2H, d, J=8.6 Hz), 7.28-7.39 (5H, m), 7.92 (2H, d, J=9.2 Hz) ppm, IR (ATR-IR): ν _(CF) = 1018 - 1282 cm ^-1 , ν _(CO) =1230 cm ^-1 , ν _(CH) = 1319 cm ^-1 , ν _(C=C) = 1579 cm ^-1 , ν _(C=O) = 1714 cm ^{- 1} )

1 L水添瓶に化合物G (2.0g, 3.5mmol)、エタノール400mL、トルエン200mLを加え化合物を溶解させた後に5%パラジウム炭素(0.5 g)を加え、反応容器を脱気してH₂を注入し激しく撹拌した。H₂が反応容器に注入できなくなったら、反応容器を大気開放してパラジウム炭素を濾別し、反応溶液をエバポレーターで減圧濃縮して得られた固体をトルエンで再結晶を行って化合物H 1.3 gを得た。（収率：77%、融点：109 - 110℃、¹H-NMR: CDCl₃、DMSO-d₆ともに不溶のため測定不可、IR (KBr disc.): ν_(C-F) = 1010 - 1280 cm^-1, ν_(C-O) =1230 cm^-1, ν_(C-H) = 1315 cm^-1, ν_(C=C) = 1589 cm^-1,ν_(C=O)= 1678 cm^-1,ν_(O-H) = 3269 cm^-1） (4) Debenzylation

Compound G (2.0 g, 3.5 mmol), 400 mL of ethanol, and 200 mL of toluene were added to a ₁ L hydrogenation bottle to dissolve the compound. Pour in and stir vigorously. When H ₂ could not be injected into the reaction vessel, the reaction vessel was opened to the atmosphere, palladium carbon was filtered off, the reaction solution was concentrated under reduced pressure using an evaporator, and the obtained solid was recrystallized with toluene to obtain 1.3 g of compound H. got (Yield: 77%, melting point: 109 - 110°C, ¹ H-NMR: both CDCl ₃ and DMSO-d ₆ are insoluble and cannot be measured, IR (KBr disc.): ν _(CF) = 1010 - 1280 cm ^{- 1} , ν _(CO) =1230 cm ^-1 , ν _(CH) = 1315 cm ^-1 , ν _(C=C) = 1589 cm ^-1 , ν _(C=O) = 1678 cm ^-1 , ν _(OH) = 3269 cm ^-1 )

50mLナスフラスコに化合物C-6 (0.52g, 1.0mmol)、化合物H (0.50g, 1.0mmol)、EDC・HCl (0.30g, 1.5mmol)、DMAP (0.5g)、DMF (25mL)を加え、塩化カルシウム管を取り付けて室温で一晩撹拌した。得られた反応混合物を、トルエンで2回抽出し、有機層を飽和食塩水で洗浄した。得られた有機層をエバポレーターで減圧濃縮し、展開溶媒をクロロホルムとしたシリカゲルカラムクロマトグラフィーで精製して化合物（3-6-6）0.65 gを得た。（収率：67%、融点：127 - 128℃、¹H-NMR (500 MHz, CDCl₃): δ = 2.36-2.47 (2H, m), 2.51-2.61 (2H, m), 3.19 (2H, t, J=8.3 Hz), 4.58 (2H, t, J=6.3 Hz), 7.25 (2H, d, J=8.6 Hz), 7.33 (2H, d, J=8.6 Hz), 8.06 (4H, dd, J=8.3, 7.2 Hz) ppm、IR (ATR-IR): ν_(C-F) = 1078 - 1230 cm^-1, ν_(C-O) = 1280 - 1367 cm^-1, ν_(C-H) = 1608 cm^-1） (5) Esterification

Compound C-6 (0.52g, 1.0mmol), compound H (0.50g, 1.0mmol), EDC-HCl (0.30g, 1.5mmol), DMAP (0.5g) and DMF (25mL) were added to a 50mL eggplant flask. A calcium chloride tube was attached and stirred overnight at room temperature. The resulting reaction mixture was extracted twice with toluene, and the organic layer was washed with saturated brine. The resulting organic layer was concentrated under reduced pressure using an evaporator and purified by silica gel column chromatography using chloroform as a developing solvent to obtain 0.65 g of compound (3-6-6). (Yield: 67%, melting point: 127 - 128°C, ¹ H-NMR (500 MHz, CDCl ₃ ): δ = 2.36-2.47 (2H, m), 2.51-2.61 (2H, m), 3.19 (2H, t, J=8.3 Hz), 4.58 (2H, t, J=6.3 Hz), 7.25 (2H, d, J=8.6 Hz), 7.33 (2H, d, J=8.6 Hz), 8.06 (4H, dd, J=8.3, 7.2 Hz) ppm, IR (ATR-IR): ν _(CF) = 1078 - 1230 cm ^-1 , ν _(CO) = 1280 - 1367 cm ^-1 , ν _(CH) = 1608 cm ^-1 )

50 mLナスフラスコに化合物D-6 (0.65 g, 1.2 mmol)、塩化チオニル10 mLを加えて80℃で90分間加熱撹拌して酸クロリド化した。反応終了後、減圧除去を行い、そこにトルエン8 mLと化合物H(0.59 g, 1.2 mmol)の無水ピリジン(8 mL)溶液を加えて80℃で4時間加熱攪拌した。その後、エバポレーターを用いて減圧濃縮を行い、残渣にエタノールを加えて副生成物であるピリジン塩酸塩を除去し、吸引濾過した後、展開溶媒をクロロホルムとしたシリカゲルカラムクロマトグラフィーで精製して化合物（4-6-6）0.69 gを得た。（収率：58%、融点：168 - 169℃、¹H-NMR (500 MHz, CDCl₃): δ = 2.57-2.68 (4H, m), 3.36-3.40 (2H, m), 4.65 (2H, t, J=6.4 Hz), 7.34 (2H, d, J=8.6 Hz), 8.11 (2H, d, J=8.6 Hz), 8.15 (2H, d, J=8.6 Hz), 8.44 (2H, d, J=6.9 Hz) ppm、IR (ATR-IR): ν_(C-F) = 1087 - 1232 cm^-1, ν_(C-O) = 1267-1366 cm^-1, ν_(C-H)= 1599 cm^-1） [Synthesis of compound 4-6-6]
Using the compound (a-SO ₂ ; referred to as D-6 here) obtained in the oxidation step of Example 2, compound (4-6-6) was obtained in the following steps.

Compound D-6 (0.65 g, 1.2 mmol) and 10 mL of thionyl chloride were added to a 50 mL eggplant flask, and the mixture was heated and stirred at 80° C. for 90 minutes for acid chloride formation. After completion of the reaction, the mixture was removed under reduced pressure, 8 mL of toluene and a solution of compound H (0.59 g, 1.2 mmol) in anhydrous pyridine (8 mL) were added thereto, and the mixture was heated and stirred at 80° C. for 4 hours. Thereafter, concentration under reduced pressure is performed using an evaporator, ethanol is added to the residue to remove the by-product pyridine hydrochloride, and after suction filtration, purification is performed by silica gel column chromatography using chloroform as a developing solvent to obtain the compound ( 4-6-6) 0.69 g was obtained. (Yield: 58%, Melting point: 168 - 169°C, ¹ H-NMR (500 MHz, CDCl ₃ ): δ = 2.57-2.68 (4H, m), 3.36-3.40 (2H, m), 4.65 (2H, t, J = 6.4 Hz), 7.34 (2H, d, J = 8.6 Hz), 8.11 (2H, d, J = 8.6 Hz), 8.15 (2H, d, J = 8.6 Hz), 8.44 (2H, d, J=6.9 Hz) ppm, IR (ATR-IR): ν _(CF) = 1087 - 1232 cm ^-1 , ν _(CO) = 1267-1366 cm ^-1 , ν _(CH) = 1599 cm ^-1 )

By the same method as in Example 1, the following compound (5-6-6) was synthesized. (Yield: 21%, melting point: 145-148°C)

[Gelling ability (minimum gelling concentration, sol-gel transition temperature) measurement]
About 3.5 mg of the gelling agent was weighed into a microtube (manufactured by Maruem Co., Ltd., 11 mmφ). A mixed sample in which an appropriate amount of solvent was added to the gelling agent was heated together with the microtube to dissolve, and vigorously stirred using a vortex mixer. After standing to cool, the state of the solution was visually confirmed. At this time, when the sample tube was turned upside down, if it was in a solid state, it was called "gel", and if it was in a liquid state, it was called "sol". When gel was determined, additional solvent was added to determine the minimum gelling concentration. Also, the temperature at which the phase transition from the gel state to the sol state was measured, and this was defined as the "sol-gel transition temperature".
The minimum gelling concentrations are shown in Table 2, and the sol-gel transition temperatures are shown in Figures 1-5. In the table, "-" represents unmeasured.
In Table 2, G indicates gel and I indicates insoluble. The numbers in parentheses indicate the minimum gelling concentration (wt%). Further, in Table 2, the top numbers 1-6-6, 2-6-4, 2-6-6, 3-6-6, 4-6-6 and 5-6-6 are the above synthesis examples The number of the compound synthesized in is shown.

Table 2 shows the evaluation results of the minimum gelling concentration for each compound.

DMSO：dimethyl sulfoxide (高誘電性溶媒)
PC : propylene carbonate (高誘電性溶媒)
1M LiClO₄/PC ：支持電解質（LiClO₄）を含有する高誘電性溶媒
1M LiFSA/EC:PC:DEC：支持電解質（LiFSA）を含有する高誘電性溶媒（EC:PC:DEC=2:1:7 (体積比)）
EC = ethylene carbonate
PC = propylene carbonate
DEC = diethyl carbonate
N,N-dimethylaniline: 塩基性有機溶媒
[EMIM][FSA] ：１－エチル－３メチルイミダゾリウムビス（フルオロスルホニル）アミド（イオン液体）
1 mol kg^-1 LiFSA/[EMIM][FSA] ：支持電解質（LiFSA）を含有するイオン液体
[dema][TfO] ：ジエチルメチルアンモニウムトリフルオロメタンスルホナート（プロトン性イオン液体）
[N,N-dimethylaniline][TFSA]：プロトン性イオン液体
[BMIM][TFSA] : （１－ブチル－３－メチルイミダゾリウムビス（トリフルオロメチルスルホニル）アミド）（イオン液体）
[BMIM][FeCl₄] ：（１－ブチル－３－メチルイミダゾリウムテトラクロロフェレート（イオン液体）

DMSO: dimethyl sulfoxide (high dielectric solvent)
PC : propylene carbonate (high dielectric solvent)
1M LiClO ₄ /PC : High dielectric solvent containing supporting electrolyte (LiClO ₄ )
1M LiFSA/EC:PC:DEC: high dielectric solvent containing supporting electrolyte (LiFSA) (EC:PC:DEC=2:1:7 (volume ratio))
EC = ethylene carbonate
PC = propylene carbonate
DEC = diethyl carbonate
N,N-dimethylaniline: basic organic solvent
[EMIM][FSA] : 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)amide (ionic liquid)
1 mol kg ^-1 LiFSA/[EMIM][FSA] : Ionic liquid containing supporting electrolyte (LiFSA)
[dema][TfO] : Diethylmethylammonium trifluoromethanesulfonate (protic ionic liquid)
[N,N-dimethylaniline][TFSA]: protic ionic liquid
[BMIM][TFSA] : (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide) (ionic liquid)
[BMIM][FeCl ₄ ] : (1-butyl-3-methylimidazolium tetrachloroferrate (ionic liquid)

FIG. 1 shows a gel of the compound (2-6-6) of the present invention and a solvent (PC and [EMIM] [FSA]), and a solvent and a supporting electrolyte (1M LiClO_Four/PC and 1 mol kg^-1LiFSA/ [EMIM][FSA]) shows the relationship between the phase transition temperature to sol and the compound concentration.
FIG. 2 shows the relationship between the phase transition temperature to sol and the compound concentration for gels of the compounds of the present invention (1-6-6 and 2-6-6) and 1-octanol.
FIG. 3 shows the phase transition temperature to sol and the compound concentration for gels of the compounds of the present invention (2-6-6, 3-6-6, 4-6-6 and 5-6-6) and propylene carbonate. indicates a relationship with
FIG. 4 shows gels of compounds of the present invention (1-6-6, 2-6-6, 3-6-6, 4-6-6 and 5-6-6) and [BMIM][TFSA]. , shows the relationship between the phase transition temperature to sol and the compound concentration.
FIG. 5 shows the phase transition temperature to sol and the compound concentration for gels of the compounds of the present invention (2-6-6, 3-6-6 and 4-6-6) and 1M LiFSA / EC:PC:DEC indicates a relationship with

[Measurement of Durability of Gel Electrolyte]
A non-gelled electrolyte was prepared by adding the supporting electrolyte LiFSA to 1 M to a high dielectric mixed solvent (EC/PC/DEC (2:1:7). After adding and mixing the invention compound (3-6-6), the mixture was gelled in a glove box under an argon atmosphere to obtain a gel electrolyte with a concentration of 5% by weight.
As a comparative example, instead of the compound of the present invention (3-6-6), compound K-8 (the chemical formula is shown in FIG. 6) was used to similarly obtain a gel electrolyte with a concentration of 5% by weight. .
The relationship between viscosity and shear rate was evaluated by steady flow viscosity measurement using Rheosol-G1000 manufactured by UBM Co., Ltd.
<Measurement conditions>
Measurement mode Shear rate dependence: 2.76×10 ^-2 ~ 143 sec ^-1
chuck cone plate
Cone diameter 40mm
Cone angle 2.0°
The results are shown in FIG. The gels of the comparative examples showed a large decrease in viscosity upon shearing, whereas the gels of the present invention exhibited a small decrease in viscosity upon shearing.

[Measurement of ionic conductivity]
1 Electrolyte using ionic liquid [EMIM][FSA] Add supporting electrolyte LiFSA to ionic liquid [EMIM][FSA] so that it becomes 1 mol kg ^-1 to make a non-gelled electrolyte. made. To the electrolytic solution, the compound (2-6-6) of the present invention was added at a concentration of 3% by weight with respect to the total amount of the electrolytic solution, heated to 95° C. and uniformly mixed, then in a glove box, Before gelling, it was impregnated into a glass fiber filter paper and gelled in that state to obtain a gel electrolyte with a concentration of 3% by weight. A bipolar cell was assembled by using Pt for the working and counter electrodes and inserting a glass fiber filter paper impregnated with a gel electrolyte. The bipolar cell was placed in a constant temperature bath, and the impedance was measured in the temperature range from -20°C to 60°C in increments of 10°C using an electrochemical measurement system under the following measurement conditions. The ionic conductivity was calculated from the impedance obtained by the measurement. Table 3 shows the results.
[Measurement condition]
・Equipment Solartron analytical 1280C
・Measurement method Constant potential AC impedance measurement > Frequency range: 20000 - 0.1 Hz
> Applied voltage (AC amplitude): 10 mVp-p
> DC voltage: 0V
・Measurement temperature -20 - 60℃ (ESPEC SU-241)
・Cell: Hosen Co., Ltd. HS Flat Cell ・Working electrode: Platinum, Counter electrode: Platinum ・Separator: Glass fiber filter paper (Toyo Roshi Kaisha, Ltd. GB-100R)

2. In the case of protic ionic liquids Compounds of the present invention (2-6-6 and 3-6-6) for protic ionic liquids ([dema][TfO] and [N,N-diethylaniline][TFSA]) was added at a concentration of 5% by weight with respect to the total amount of protic ionic liquid, heated to 95 ° C. and mixed uniformly, and then impregnated into a glass fiber filter paper before gelation in a glove box. The mixture was gelled in this state to obtain a gel with a concentration of 5% by weight. A bipolar cell was assembled by using Pt for the working and counter electrodes and inserting a glass fiber filter paper impregnated with a gel electrolyte. The bipolar cell was placed in a constant temperature bath, and the impedance was measured in the temperature range of 0° C. to 80° C. in increments of 20° C. using an electrochemical measurement system under the same measurement conditions as in 1 above. The ionic conductivity was calculated from the impedance obtained by the measurement. The results are shown in Tables 4 and 5.

As a comparative example, the following formula, which is a known gelling agent,

Tomohiro Yasuda, Masayoshi Watanabe, Japan It is described in Journal of Ion Exchange Society, 22, 58 (2011).
Here, a graph of the results of measuring the ionic conductivity of a gel obtained by adding SPI-6 to [dema][TfO] in an amount of 20 wt% to 50 wt% is shown. As shown in Table 6, the ionic conductivity of the gel obtained by adding 5% of the gelling agent of the present invention to the protic ionic liquid was 1.0% higher than that of the gel obtained by adding 20% of the known gelling agent to the protic ionic liquid. 5 to 5 times higher.

[Synthesis of protic ionic liquid ([N,N-diethylaniline] [TFSA])]
N,N-diethylaniline (6.9 g, 46.5 mmol) was added to a 100 mL eggplant flask and sufficiently cooled in an ice bath. 5 mmol) was added, and the mixture was stirred in an ice bath for 30 minutes, and then stirred at room temperature for 7 hours. After completion of the reaction, the pressure was reduced overnight using a Kugelrohr to obtain 17.5 g of [N,N-diethylaniline][TFSA] (yield 87%, mp 268-269°C) ¹ H-NMR (500 MHz, CDCl ₃ ): δ = 1.11 (6H, t, J=6.0 Hz), 3.64 (4H, q, J=6.9 Hz), 7.11 (1H, s), 7.44-7.57 (5H, m) ppm, IR (ATR- IR) : ν _(S=O) = 1132-1178 cm ^-1 ν _(C=C) = 1600 cm ^-1 , ν _(NH) = 3125 cm ^-1

The fluorine-containing aromatic ester compound of the present invention can be used not only as a gelling agent in industrial fields such as cosmetics, pharmaceuticals, foods, paints, adhesives, and sludge treatment, but also in ionic liquids including protic ionic liquids. can be gelled.
Furthermore, it has excellent electrochemical stability and is free from decomposition due to pH changes. In addition, the ionic conductivity of the formed ionic liquid gel is almost the same as in the liquid state. Therefore, it is possible to construct a next-generation organic gel electrolyte that has both high ionic conductivity and mechanical strength, and it is expected to be applied to all-solid-state lithium-ion batteries and fuel cells.
In addition, the ionic liquid gel produced by the gelling agent of the present invention selectively absorbs carbon dioxide, and since it is a hydrophobic ionic liquid gel, it is easy to separate from water. Applications are expected, and innovative CO ₂ separation materials and applications that can remove acid gases and water with the ultimate goal of CO ₂ reuse are possible.

Claims (5)

A fluorine-containing aromatic ester compound represented by formula (I).

(In the formula,
Ar represents a substituted or unsubstituted divalent aromatic group,
y represents 0, 1 or 2,
m and n are each independently an integer from 1 to 20,
p and q each independently represent any integer from 0 to 6,
r represents any integer from 1 to 3) 2. The fluorine-containing aromatic ester compound according to claim 1, wherein Ar in formula (I) is a substituted or unsubstituted phenylene group, naphthylene group or biphenylene group. A gelling agent containing the fluorine-containing aromatic ester compound according to claim 1 or 2. A gel composition containing the gelling agent according to claim 3 and an organic solvent. 5. The gel composition according to claim 4, wherein the organic solvent is an ionic liquid.

Images