Novel fluoroalkane derivatives and gelling agents using them

Abstract

The present invention addresses the problem of providing novel fluoroalkane derivatives that are of a low-molecular-weight type having no hydrogen-bonding functional groups in the molecule, are capable of gelling a wide range of organic solvents in a low concentration, and can form gelling agents that obtain a gel of adequate thermal stability and strength.　Fluoroalkane derivatives represented by formula (1) are used as gelling agents.　In formula (1), R1 represents an alkyl group in which 60% or more of the hydrogen atoms have been substituted by fluorine atoms or a C1-30 hydrocarbon group having an alkyl group in which 60% or more of the hydrogen atoms have been substituted by fluorine atoms, Ar1 represents a substituted or unsubstituted C3-20 divalent aromatic group, R represents a substituted or unsubstituted C1-30 hydrocarbon group or a group represented by formula (2) (in formula (2), Y1 represents a cyano group, a nitro group, a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C1-20 alkoxy group, a substituted or unsubstituted C1-20 alkylsulfanyl group, a substituted or unsubstituted C1-20 alkylsulfinyl group, or a substituted or unsubstituted C1-20 alkylsulfonyl group, Ar2 represents a substituted or unsubstituted C3-20 divalent aromatic group, and L represents a divalent linking group.), and n represents 1 or 2.

Description

Technical Field

[0001] The present invention relates to a novel fluoroalkane derivative capable of gelling various organic solvents, a gelling agent containing the derivative, and a gel composition containing the derivative and an organic solvent.

Background Art

[0002] In various industrial fields (for example, paints, cosmetics, pharmaceuticals and medical care, oil spill treatment, electronics and optics fields, environmental fields, etc.), gelling agents are used for the purpose of solidifying liquid substances, that is, hardening them into a jelly-like state or thickening them.

[0003] These gelling agents can be roughly classified into a high molecular weight type and a low molecular weight type. Among the low molecular weight type gelling agents, gelling agents having no hydrogen bonding functional group in the molecule are expected to construct a next-generation organic gel electrolyte with both high ionic conductivity and mechanical strength because the formed organic gel electrolyte can maintain high electrochemical stability. As such low molecular weight type gelling agents having no hydrogen bonding functional group in the molecule, compounds represented by the following formulas (I) to (III) are known (see Patent Documents 1 and 2).

[0004]

Chemical Formula

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] Conventionally known low molecular weight gelling agents have not always had satisfactory performance, such as low ability to gel fluorinated solvents or hydrophobic ionic liquids, or insufficient thermal stability and strength of the gels formed. An object of the present invention is to provide a novel fluoroalkane derivative that can be a gelling agent which is a low molecular weight type having no hydrogen-bonding functional group in the molecule, can gel a wide range of organic solvents at low concentrations, and can obtain gels with sufficient thermal stability and strength.

Means for Solving the Problems

[0007] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using an alkyl group-substituted aromatic hydrocarbon (substituted with a sulfoxide group or a sulfonyl group having a fluoroalkyl chain) or a benzoic acid derivative (substituted with a sulfoxide group or a sulfonyl group having a fluoroalkyl chain) as a gelling agent, and have completed the present invention.

[0008] That is, the present invention is as follows, specified by the following matters. [1] A fluoroalkane derivative represented by the following formula (1).

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0009] By using the fluoroalkyl derivative of the present invention, it is possible to gel fluorinated solvents and hydrophobic ionic liquids that were difficult to gel conventionally. In addition, various organic solvents can be gelled at low concentrations, and the sol-gel phase transition temperature of the resulting gel can be set to 150 °C or higher, which has not been achievable conventionally, thereby enhancing the thermal stability of the gel. [Brief Description of the Drawings]

[0010]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Embodiments for Carrying Out the Invention

[0011] The fluoroalkane derivative of the present invention is represented by the formula (1). In the present invention, the term "unsubstituted" means only the group that serves as the parent nucleus. When described only by the name of the group that serves as the parent nucleus, it means "unsubstituted" unless otherwise specified. On the one hand, the term "substituted" means that any hydrogen atom of the parent nucleus is substituted by a group having the same or different structure from the parent nucleus. Therefore, a "substituent" is another group bonded to the parent nucleus. There may be one substituent or two or more substituents. Two or more substituents may be the same or different, and two or more substituents may be bonded to the same atom or different atoms.

[0012] The "substituent" is chemically acceptable and is not particularly limited as long as it has the effects of the present invention. Specific examples of the group that can be a "substituent" include the following groups.

[0013] C1-C6 alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group; C2-C6 alkenyl groups such as vinyl group, 1-propenyl group, 2-propenyl group (allyl group), propen-2-yl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group; C2-C6 alkynyl groups such as ethynyl group, 1-propynyl group, 2-propynyl group (propargyl group), 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group;

[0014] C3-C8 cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cubanyl group; C6-C10 aryl groups such as phenyl group, naphthyl group; C6-C10 aryl C1-C6 alkyl groups such as benzyl group, phenethyl group; 3-6 membered heterocyclyl group; 3-6 membered heterocyclyl C1-C6 alkyl group;

[0015] Oxo group; Hydroxyl group; C1-6 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group; C2-6 alkenyloxy groups such as vinyloxy group, allyloxy group, 1-propenyloxy group, propen-2-yloxy group, 3-butenyloxy group, 2-butenyloxy group; C2-6 alkynyloxy groups such as ethynyloxy group, propargyloxy group; C6-10 aryloxy groups such as phenoxy group, naphthoxy group; C6-10 aryl C1-6 alkoxy groups such as benzyloxy group, phenethyloxy group; 5-6 membered heteroaryloxy groups such as thiazolyloxy group, pyridyloxy group; 5-6 membered heteroaryl C1-6 alkyloxy groups such as thiazolylmethyloxy group, pyridylmethyloxy group;

[0016] Formyl group; C1-6 alkylcarbonyl groups such as acetyl group, propionyl group; Formyloxy group; C1-6 alkylcarbonyloxy groups such as acetyloxy group, propionyloxy group; C6-10 arylcarbonyl groups such as benzoyl group; Carboxy group; C1-6 alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group; C1-6 alkoxycarbonyloxy groups such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group;

[0017] Halo groups such as fluoro group, chloro group, bromo group, iodo group; C1-C6 haloalkyl groups such as 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; C2-C6 haloalkenyl groups such as 2-chloro-1-propenyl group, 2-fluoro-1-butenyl group; C2-C6 haloalkynyl groups such as 4,4-dichloro-1-butynyl group, 4-fluoro-1-pentynyl group, 5-bromo-2-pentynyl group; C1-C6 haloalkoxy groups such as trifluoromethoxy group, 2-chloro-n-propoxy group, 2,3-dichlorobutoxy group; C2-C6 haloalkenyloxy groups such as 2-chloropropenyloxy group, 3-bromobutenyloxy group; C1-C6 haloalkylcarbonyl groups such as chloroacetyl group, trifluoroacetyl group, trichloroacetyl group;

[0018] amino group; mono-C1-C6 alkyl-substituted amino groups or di-C1-C6 alkyl-substituted amino groups (in the latter case, the C1-C6 alkyls may be the same or different) such as methylamino group, dimethylamino group, diethylamino group; C6-C10 arylamino groups such as anilino group, naphthylamino group; C6-C10 aryl-C1-C6 alkylamino groups such as benzylamino group, phenethylamino group; formylamino group; C1-6 alkylcarbonylamino groups such as acetylamino group, propanoylamino group, butyrylamino group, i-propylcarbonylamino group; C1-6 alkoxycarbonylamino groups such as methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, i-propoxycarbonylamino group; C1-6 alkylsulfoximino groups such as S,S-dimethylsulfoximino group; Unsubstituted or substituted aminocarbonyl groups such as aminocarbonyl group, dimethylaminocarbonyl group, phenylaminocarbonyl group, N-phenyl-N-methylaminocarbonyl group; Imino C1-6 alkyl groups such as iminomethyl group, 1-iminoethyl group, 1-imino-n-propyl group; Substituted or unsubstituted N-hydroxyimino C1-6 alkyl groups such as N-hydroxy-iminomethyl group, 1-(N-hydroxyimino)ethyl group, 1-(N-hydroxyimino)propyl group, N-methoxyiminomethyl group, 1-(N-methoxyimino)ethyl group; Hydroxyimino group; C1-6 alkoxyimino groups such as methoxyimino group, ethoxyimino group, n-propoxyimino group, i-propoxyimino group, n-butoxyimino group; Aminocarbonyloxy group; Mono C1-6 alkyl-substituted aminocarbonyloxy groups or di C1-6 alkyl-substituted aminocarbonyloxy groups (in the latter case, the C1-6 alkyls may be the same or different) such as ethylaminocarbonyloxy group, dimethylaminocarbonyloxy group;

[0019] Thioxo group; Thiol (mercapto) group; C1-6 alkylthio groups such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group; C1-6 haloalkylthio groups such as trifluoromethylthio group, 2,2,2-trifluoroethylthio group; C6-10 arylthio groups such as phenylthio group and naphthylthio group; 5-6 membered heteroarylthio groups such as thiazolylthio group and pyridylthio group;

[0020] C1-6 alkylsulfinyl groups such as methylsulfinyl group, ethylsulfinyl group and t-butylsulfinyl group; C1-6 haloalkylsulfinyl groups such as trifluoromethylsulfinyl group and 2,2,2-trifluoroethylsulfinyl group; C6-10 arylsulfinyl groups such as phenylsulfinyl group; 5-6 membered heteroarylsulfinyl groups such as thiazolylsulfinyl group and pyridylsulfinyl group;

[0021] C1-6 alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group and t-butylsulfonyl group; C1-6 haloalkylsulfonyl groups such as trifluoromethylsulfonyl group and 2,2,2-trifluoroethylsulfonyl group; C6-10 arylsulfonyl groups such as phenylsulfonyl group; 5-6 membered heteroarylsulfonyl groups such as thiazolylsulfonyl group and pyridylsulfonyl group; Sulfonic group; C1-6 alkylsulfonyloxy groups such as methylsulfonyloxy group, ethylsulfonyloxy group and t-butylsulfonyloxy group; C1-6 haloalkylsulfonyloxy groups such as trifluoromethylsulfonyloxy group and 2,2,2-trifluoroethylsulfonyloxy group;

[0022] Tri-C1-6 alkyl-substituted silyl groups such as trimethylsilyl group, triethylsilyl group and t-butyldimethylsilyl group; Tri-C6-10 aryl-substituted silyl groups such as triphenylsilyl group; C2-C6 alkenyl C1-C6 dialkyl-substituted silyl groups such as allyldimethylsilyl group and vinyldimethylsilyl group; C1-C6 alkyl such as t-butyldiphenylsilyl group and diphenylmethylsilyl group Di-C6-C10 aryl-substituted silyl group; Di-C1-C6 alkyl-C6-C10 aryl-substituted silyl group such as dimethylphenylsilyl group; (C6-C10 phenyl-C1-C6 alkyl)di-C1-C6 alkylsilyl group such as benzyldimethylsilyl group and 3-phenylpropyldimethylsilyl group; C1-C6 alkyl-C6-C10 aryl-C2-C6 alkenylsilyl group such as methylphenylvinylsilyl group, Tri-C1-C6 alkoxy-substituted silyl group such as trimethoxysilyl group and triethoxysilyl group; Di-C1-C6 alkyl-substituted silyl group such as dimethylsilyl group and diethylsilyl group; Di-C1-C6 alkoxy-substituted silyl group such as dimethoxysilyl group and diethoxysilyl group; C1-C6 alkoxydi-C1-C6 alkyl-substituted silyl group such as methoxydimethylsilyl group; C1-C6 alkoxydi-C6-C10 aryl-substituted silyl group such as t-butoxydiphenylsilyl group; C1-C6 alkyldi-C1-C6 alkoxy-substituted silyl group such as methyldimethoxysilyl group; Cyano group; Nitro group.

[0023] In addition, the above-mentioned "3- to 6-membered heterocyclic group" means a group containing 1 to 4 heteroatoms selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom as ring-constituting atoms. The heterocyclic group may be either a monocyclic or polycyclic group. In the polycyclic heterocyclic group, as long as at least one ring is a heterocyclic ring, the remaining rings may be any of saturated alicyclic, unsaturated alicyclic or aromatic hydrocarbon rings. Examples of the "3- to 6-membered heterocyclic group" include 3- to 6-membered saturated heterocyclic groups, 5- to 6-membered heteroaryl groups, 5- to 6-membered partially unsaturated heterocyclic groups, and the like.

[0024] Examples of the 3- to 6-membered saturated heterocyclyl group include an aziridinyl group, an epoxy group, a pyrrolidinyl group, a tetrahydrofuryl group, a thiazolidinyl group, a piperidyl group, a piperazinyl group, a morpholinyl group, a dioxolanyl group, and a dioxanyl group.

[0025] Examples of the 5-membered heteroaryl group include a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a triazolyl group, an oxadiazolyl group, a thiadiazolyl group, a tetrazolyl group, an indolyl group, an isoindolinyl group, an indolizinyl group, a benzimidazolyl group, and a carbazolyl group. Examples of the 6-membered heteroaryl group include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, a cinnolinyl group, a quinazolinyl group, a phthalazinyl group, an acridinyl group, a naphthyridinyl group, and a phenazinyl group. Examples of the 5- to 6-membered partially unsaturated heterocyclyl group include an isoxazolinyl group and a pyrazolinyl group. Examples of the 3- to 6-membered heterocyclyl 1- to 6-alkyl group include a glycidyl group, a 2-tetrahydrofurylmethyl group, a 2-pyrrolylmethyl group, a 2-imidazolylmethyl group, a 3-isoxazolylmethyl group, a 5-isoxazolylmethyl group, a 2-pyridylmethyl group, a 4-pyridylmethyl group, and a 3-isoxazolinylmethyl group.

[0026] Terms such as "C1-6" indicate that the number of carbon atoms in the parent nucleus group is 1 to 6, etc. This number of carbon atoms does not include the number of carbon atoms in the substituents. For example, an ethoxybutyl group is classified as a C2 alkoxy C4 alkyl group because the parent nucleus group is a butyl group and the substituent is an ethoxy group. However, when using the terms "C1-6 alkylcarbonyl" and "C6-10 arylcarbonyl", the carbon of the carbonyl group is not included in the number of carbon atoms.

[0027] Any of these "substituents" may have any hydrogen atom in the substituent replaced by a group of a different structure.

[0028] In formula (1), R 1 represents an alkyl group in which 60% or more of the hydrogen atoms are replaced by fluorine atoms or a C1-30 hydrocarbon group having an alkyl group in which 60% or more of the hydrogen atoms are replaced by fluorine atoms. Examples of the alkyl group in the "alkyl group in which 60% or more of the hydrogen atoms are replaced by fluorine atoms" may be linear or branched, and include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group, i-butyl group, s-butyl group, t-butyl group, i-pentyl group, neopentyl group, 2-methyl-n-butyl group, i-hexyl group, n-pentyl group, n-octyl group, n-decyl group, n-tetradecyl group, n-octadecyl group, n-eicosanyl group, etc.

[0029] The substitution rate of fluorine atoms is not particularly limited as long as it is 60% or more of the total number of hydrogen atoms contained in the alkyl group, and 70% or more, 80% or more, 90% or more are preferable, and it is even more preferable that it is 100% (corresponding to a perfluoroalkyl group). Specific examples of the alkyl group in which 60% or more of the hydrogen atoms are substituted with fluorine atoms include a trifluoromethyl group, a pentafluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, a 1H,1H-perfluoro-n-propyl group, a 1,1,1,3,3,3-hexafluoro-propan-2-yl group, a 2,2,3,3,3-pentafluoro-n-propyl group, a perfluoro-n-propyl group, a perfluoroisopropyl group, a 2,2,3,3,4,4,4-heptafluoro-n-butyl group, a perfluoro-n-butyl group, a 1H,1H-perfluoro-n-butyl group, a 1H,1H,3H-perfluoro-n-butyl group, a perfluoro-n-pentyl group, a 1H,1H,5H-perfluoro-n-pentyl group, a 1H,1H,2H,2H-perfluoro-n-hexyl group, a perfluoro-n-hexyl group, a 1H,1H,2H,2H,3H,3H-perfluoro-n-heptyl group, a 1H,1H,2H,2H-perfluoro-n-octyl group, a 1H,1H,2H,2H-perfluoro-n-nonyl group, a 1H,1H,2H,2H,3H,3H-perfluoro-n-nonyl group, a 1H,1H,2H,2H,3H,3H-perfluoro-n-decyl group, a 3,3,4,4,5,5,6,6,7,7,8,8,9,10,10,10-hexadecafluoro-9-trifluoromethyl-n-decyl group, a 1H,1H,2H,2H-perfluoro-n-decyl group, and the like.

[0030] The C1-C30 hydrocarbon group of the "C1-C30 hydrocarbon group having an alkyl group in which 60% or more of the hydrogen atoms are substituted with fluorine atoms" represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aromatic hydrocarbon group, a combination thereof, and the like. Examples of the alkyl group include the same ones as those exemplified for the above alkyl group. Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group (allyl group), a propen-2-yl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl-2-propenyl group, a 2-methyl-2-propenyl group, and the like. Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group (propargyl group), 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group and the like.

[0031] Examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cubanyl group and the like. Examples of the cycloalkenyl group include cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group and the like. The aromatic hydrocarbon group may be either monocyclic or polycyclic. In the case of the polycyclic aromatic hydrocarbon group, as long as at least one ring is an aromatic ring, the remaining rings may be any of saturated alicyclic rings, unsaturated alicyclic rings or aromatic rings. Specifically, examples thereof include phenyl group, naphthyl group, anthracenyl group, phenanthryl group, azulenyl group, pyrenyl group, fluorenyl group, indenyl group, indanyl group, tetralinyl group and the like.

[0032] These combinations refer to groups formed by combining two or more selected from the group consisting of alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups and aromatic hydrocarbon groups. Specifically, examples thereof include combinations of an alkyl group and a cycloalkyl group such as cyclopropylmethyl group and cyclohexylethyl group, and combinations of an alkyl group and an aromatic hydrocarbon group such as benzyl group, phenethyl group and naphthylmethyl group.

[0033] "Having an alkyl group in which 60% or more of the hydrogen atoms are substituted with fluorine atoms" means not only the case where the hydrogen atoms on a C1-30 hydrocarbon group are substituted with an alkyl group in which 60% or more of the hydrogen atoms are substituted with fluorine atoms, but also the case where the alkyl group is bonded via a divalent linking group chemically acceptable on the C1-30 hydrocarbon group. Examples of the chemically acceptable divalent linking group include alkylene group, alkenylene group, alkynylene group, arylene group, heteroarylene group, -O-, -S-, -S(O)-, -SO2-, -C(=O)-, -NR 10 -, -C(=NR 11)-(R 10 and R 11 each independently represent a hydrogen atom, an alkyl group or an aryl group), and combinations of these groups and the like can be mentioned. The combination of these groups refers to a group formed by combining two or more of the groups exemplified as the divalent linking group, and specifically, a biphenylene group, -O-alkylene-, -C(=O)-O- and the like can be mentioned.

[0034] Examples of the C1-C30 hydrocarbon group having an alkyl group in which 60% or more of the hydrogen atoms are substituted with fluorine atoms include a 4-(1H,1H,2H,2H-perfluorohexyl)phenyl group, a 4-(1H,1H,2H,2H-perfluorohexyloxy)phenyl group, a 2-(1H,1H,2H,2H-perfluorohexyloxy)ethyl group, a 1H,1H,2H,3H-perfluoro-3-decenyl group and the like.

[0035] R 1 Among them, the group represented by formula (4) is particularly preferred. In formula (4), m represents any integer from 1 to 20, k represents any integer from 1 to 6, and l represents 0 or 1. m and k can be arbitrarily selected within the range satisfying the above conditions, but m is preferably 4 or more, more preferably 6 or more, 8 or more, 10 or more, and preferably 12 or less. m, k, and l are not particularly limited as long as they are within the range satisfying the above conditions, but preferably have the relationship shown in the following formula. (2m + 1) / [(2m + 1)+2k×l]≧0.6

[0036] Examples of the group represented by formula (4) include a 1H,1H,2H,2H-perfluoro-n-hexyl group, a 1H,1H,2H,2H,3H,3H-perfluoro-n-octyl group, a 1H,1H,2H,2H-perfluoro-n-decyl group and the like. In formula (1), n represents 1 or 2.

[0037] In formula (1), Ar 1represents a substituted or unsubstituted divalent aromatic group having 3 to 20 carbon atoms. Here, "C3~20" represents the carbon atoms constituting the aromatic group, and in order to satisfy aromaticity, it may contain atoms other than carbon (for example, oxygen atom, sulfur atom, etc.) to form a divalent aromatic group. Specifically, examples include cases where a divalent aromatic group is formed from four carbon atoms and an oxygen atom or a sulfur atom, such as a furanylene group, a thienylene group, etc. The aromatic group may be either monocyclic or polycyclic. For a polycyclic aromatic group, as long as at least one ring is an aromatic ring, the remaining rings may be either saturated alicyclic or unsaturated alicyclic. The aromatic group includes an aromatic hydrocarbon group and an aromatic heterocyclic group. Specifically, divalent aromatic hydrocarbon groups such as a phenylene group, a naphthylene group, an anthranylene group, a phenanthrylene group, an azulylene group, a pyrenylene group, a chrysenylene group, a fluorenylene group, a fluoranthenylene group, an indenylene group, an indanylene group, a tetralinylene group, etc., divalent 5-membered ring aromatic heterocyclic groups such as a pyrrolylene group, a furylene group, a thienylene group, an imidazolylene group, a pyrazolylene group, an oxazolylene group, an isoxazolylene group, a thiazolylene group, an isothiazolylene group, an indolylene group, an isoindolinylene group, an indolizinylene group, a benzimidazolylene group, a carbazolylene group, etc., divalent 6-membered ring aromatic heterocyclic groups such as a pyridylene group, a pyrazinylene group, a pyrimidylene group, a pyridazinylene group, a triazinylene group, a quinolyylene group, an isoquinolyylene group, a quinoxalylene group, a cinnolylene group, a quinazolinylene group, a phthalazylene group, an acridylene group, a naphthylene group, a phenylene group, etc. are included.

[0038] In addition, the polycyclic aromatic group includes, in addition to the group in which aromatic rings are condensed as described above, a group in which aromatic rings are directly bonded like a biphenylene group, and a group in which aromatic rings are bonded via a chemically acceptable divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a heteroarylene group, -O-, -S-, -S(O)-, -SO2-, -C(=O)-, -NR 10 -, -C(=NR 11 )-(R 10 , R 11(each independently represents a hydrogen atom, an alkyl group, or an aryl group), and combinations of these groups, etc. can be mentioned. The combination of these groups refers to a group formed by combining two or more of the groups exemplified as the divalent linking group, and specifically includes a biphenylene group, -O-alkylene-, -C(=O)-O-, etc. Specific examples of the group in which aromatic rings are directly bonded and the group in which aromatic rings are bonded via a chemically acceptable divalent linking group include the groups shown below.

[0039] [Chemical formula]

[0040] In formula (1), R represents an unsubstituted or substituted C1-30 hydrocarbon group or a group represented by formula (2). Examples of the C1-30 hydrocarbon group of the "unsubstituted or substituted C1-30 hydrocarbon group" are the same as those exemplified by R 1 above.

[0041] In formula (2), Y 1 represents a cyano group, a nitro group, an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted C1-20 alkoxy group, an unsubstituted or substituted C1-20 alkylsulfanyl group, an unsubstituted or substituted C1-20 alkylsulfinyl group, or an unsubstituted or substituted C1-20 alkylsulfonyl group.

[0042] Examples of the C1-20 alkyl group may be linear or branched, and include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an i-propyl group, an i-butyl group, an s-butyl group, a t-butyl group, an i-pentyl group, a neopentyl group, a 2-methyl-n-butyl group, an i-hexyl group, an n-octyl group, an n-decyl group, an n-tetradecyl group, an n-octadecyl group, an n-eicosanyl group, etc.

[0043] As the C1-20 alkoxy group, it may be linear or branched, and examples thereof include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentenoxy group, n-hexyloxy group, i-propoxy group, i-butoxy group, s-butoxy group, t-butoxy group, i-pentenoxy group, neopentenyloxy group, 2-methyl-n-butoxy group, i-hexyloxy group, n-octyloxy group, n-decyloxy group, n-tetradecyloxy group, n-octadecyloxy group, n-eicosanyloxy group and the like.

[0044] As the C1-20 alkylsulfanyl group, it may be linear or branched, and examples thereof include methylsulfanyl group, ethylsulfanyl group, n-propylsulfanyl group, n-butylsulfanyl group, n-pentylsulfanyl group, n-hexylsulfanyl group, i-propylsulfanyl group, i-butylsulfanyl group, s-butylsulfanyl group, t-butylsulfanyl group, i-pentylsulfanyl group, neopentylsulfanyl group, 2-methyl-n-butylsulfanyl group, i-hexylsulfanyl group, n-octylsulfanyl group, n-decylsulfanyl group, n-tetradecylsulfanyl group, n-octadecylsulfanyl group, n-eicosanyl sulfanyl group and the like. As the C1-20 alkylsulfinyl group, it may be linear or branched, and examples thereof include methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group, n-butylsulfinyl group, n-pentylsulfinyl group, n-hexylsulfinyl group, i-propylsulfinyl group, i-butylsulfinyl group, s-butylsulfinyl group, t-butylsulfinyl group, i-pentylsulfinyl group, neopentylsulfinyl group, 2-methyl-n-butylsulfinyl group, i-hexylsulfinyl group, n-octylsulfinyl group, n-decylsulfinyl group, n-tetradecylsulfinyl group, n-octadecylsulfinyl group, n-eicosanyl sulfinyl group and the like.

[0045] Examples of the C1-20 alkylsulfonyl group include linear or branched ones such as methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, n-butylsulfonyl group, n-pentylsulfonyl group, n-hexylsulfonyl group, i-propylsulfonyl group, i-butylsulfonyl group, s-butylsulfonyl group, t-butylsulfonyl group, i-pentylsulfonyl group, neopentylsulfonyl group, 2-methyl-n-butylsulfonyl group, i-hexylsulfonyl group, n-octylsulfonyl group, n-decylsulfonyl group, n-tetradecylsulfonyl group, n-octadecylsulfonyl group, n-eicosanyl sulfonyl group, and the like.

[0046] Y in formula (2) 1 Examples of the substituents of "unsubstituted or substituted C1-20 alkyl group, unsubstituted or substituted C1-20 alkoxy group, unsubstituted or substituted C1-20 alkylsulfanyl group, unsubstituted or substituted C1-20 alkylsulfinyl group, or unsubstituted or substituted C1-20 alkylsulfonyl group" in include those exemplified as the above substituents. Among them, halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom are preferably mentioned, and among them, fluorine atom is preferably mentioned.

[0047] Examples of the fluorine atom-substituted group include 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, 1H,1H,2H,2H-perfluorooctyl group, 1H,1H,2H,2H-perfluorohexyl group, fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, pentafluoroethoxy group, 3,3,3-trifluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, perfluoropropoxy group, 2,2,2-trifluoro-1-trifluoromethylethoxy group, perfluoroisopropoxy group, 4-fluorobutoxy group, 2,2,3,3,4,4,4-heptafluorobutoxy group, perfluorobutoxy group, perfluoropentyloxy group, perfluorohexyloxy group, 1H,1H,2H,2H-perfluorooctyloxy group, 1H,1H,2H,2H-perfluorohexyloxy group, fluoromethylsulfanyl group, difluoromethylsulfanyl group, trifluoromethylsulfanyl group, 2,2,2-trifluoroethylsulfanyl group, pentafluoroethylsulfanyl group, 3,3,3-trifluoropropylsulfanyl group, 2,2,3,3,3-pentafluoropropylsulfanyl group, perfluoropropylsulfanyl group, 2,2,2-trifluoro-1-trifluoromethylethylsulfanyl group, perfluoroisopropylsulfanyl group, 4-fluorobutylsulfanyl group, 2,2,3,3,4,4,4-heptafluorobutylsulfanyl group, perfluorobutylsulfanyl group, perfluoropentylsulfanyl group, perfluorohexylsulfanyl group, 1H,1H,2H,2H-perfluorooctylsulfanyl group, 1H,1H,2H,2H-perfluorohexylsulfanyl group, fluoromethylsulfonyl group, difluoromethylsulfonyl group, trifluoromethylsulfonyl group, 2,2,2-trifluoroethylsulfonyl group, pentafluoroethylsulfonyl group, 3,3,3-trifluoropropylsulfonyl group, 2,2,3,3,3-pentafluoropropylsulfonyl group, perfluoropropylsulfonyl group, 2,2,2-trifluoro-1-trifluoromethylethylsulfonyl group, perfluoroisopropylsulfonyl group, 4-fluorobutylsulfonyl group, 2,2,3,3,4,4,4-heptafluorobutylsulfonyl group, perfluorobutylsulfonyl group, perfluoropentylsulfonyl group, perfluorohexylsulfonyl group, 1H,1H,2H,2H-perfluorooctylsulfonyl group, 1H,1H,2H,2H-perfluorohexylsulfonyl group, and the like can be mentioned.,

[0048] In formula (2), Ar 2 represents an unsubstituted or substituted divalent aromatic group having 3 to 20 carbon atoms. As the divalent aromatic group having 3 to 20 carbon atoms, it has the same meaning as the divalent aromatic group having 3 to 20 carbon atoms in Ar 1 in formula (1), and specifically, those similar to those exemplified by Ar 1 can be mentioned. Among them, a phenylene group, a biphenylene group or a naphthalene group is preferable, and a 1,4-phenylene group, a 4,4'-biphenylene group, a 2,6-naphthalene group are particularly preferably mentioned.

[0049] In formula (2), L represents a divalent linking group, and is not particularly limited as long as it is a chemically acceptable divalent group. Specifically, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a heteroarylene group, -O-, -S-, -S(O)-, -SO2-, -C(=O)-, -NR 10 -, -C(=NR 11 )(R 10 , R 11 each independently represents a hydrogen atom, an alkyl group or an aryl group), combinations of these groups, and the like can be mentioned. These combinations of groups refer to groups formed by combining two or more of the groups exemplified as divalent linking groups. Specifically, examples include a biphenylene group, -O-alkylene-, -C(=O)-O-, etc.

[0050] Among them, as L, an oxygen atom or a linking group represented by the formula (3) is preferable. In the formula (3), as X, an oxygen atom, a sulfur atom, NR 2 represents, and R 2 represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, etc. R 2 Among them, as the alkyl group and the aryl group, those similar to those exemplified by R 1 can be mentioned, and as the aralkyl group, a benzyl group, a phenethyl group, etc. can be mentioned. In the formula (3), L 2 represents a divalent linking group. Specifically, those similar to those exemplified by L can be mentioned. Among them, the groups represented by the formula (5a), (5b) or (5c) are preferably mentioned.

[0051] In the formula (3), L 1 represents an unsubstituted or substituted C2-20 divalent hydrocarbon group which may have an oxygen atom or a sulfur atom in the chain. The divalent hydrocarbon group represents a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a divalent group combining these. Examples of the divalent aliphatic hydrocarbon group can include an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkenylene group, combinations of these groups, etc. Examples of the alkylene group include an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 1,4-butylene group, a 1,3-butylene group, etc. Examples of the alkenylene group include an ethenylene group, a 1,3-propenylene group, a 1,2-propynylene group, a 1-butene-1,4-ylene group, a 1-butene-1,3-ylene group, a 1,3-butadiene-1,4-ylene group, etc. Examples of the alkynylene group include an ethynylene group, a propynylene group, a 1-butyne-1,4-ylene group, a 1-butyne-1,3-ylene group, etc. Examples of the cycloalkylene group include a cyclopropylene group, a 1,3-cyclobutylene group, a 1,4-cyclohexylene group, and the like. Examples of the cycloalkenylene group include a cyclopropenylene group, a 1,3-cyclobutenylene group, a 2-cyclohexene-1,4-diyl group, and the like.

[0052] The divalent aromatic hydrocarbon group has the same meaning as the divalent aromatic hydrocarbon group of Ar in formula (1), and specifically, examples thereof are the same as those exemplified for the divalent aromatic hydrocarbon group of Ar. 1 1

[0053] The divalent group formed by combining these represents a divalent group formed by combining two or more divalent groups selected from the group consisting of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group. Specific examples include the groups shown below.

[0054]

Chemical formula

[0055] Examples of the C2-20 divalent hydrocarbon group which may have an oxygen atom or a sulfur atom in the chain in the "unsubstituted or substituted C2-20 divalent hydrocarbon group which may have an oxygen atom or a sulfur atom in the chain" include an alkyleneoxyalkylene group, an alkylenethioalkylene group, an aryleneoxyarylene group, an arylenethioarylene group, an aryleneoxyalkylene group, an arylenethioalkylene group, an aryleneoxyalkyleneoxyarylene group, etc. Among them, the group represented by the following formula (6) is preferably mentioned.

[0056]

Chemical formula

[0057] In formula (6), R 4 and R 5represents an alkylene group or an arylene group of C2 to C20 respectively, t represents an integer of 1 to 5, and when t is 2 or more, R 4 may be the same or different. Examples of the group represented by formula (6) include the following groups.

[0058] [Chemical formula]

[0059] Specific examples of the fluoroalkane derivative represented by formula (1) (hereinafter sometimes referred to as "compound (1)") include the following compounds. In Tables 1 to 3, nC4H9O-: n-butoxy group, nC5H 11 O-: n-pentyloxy group, nC6H 13 O-: n-hexyloxy group, nC7H 15 O-: n-heptyloxy group, nC8H 17 O-: n-octyloxy group, nC9H 19 O-: n-nonyloxy group, nC 10 H 21 O-: n-decyloxy group, -Ph-: 1,4-phenylene group, -BiPh-: 4,4'-biphenylene group, -NaPh-: 2,6-naphthylene group, -Ph-Py-: 1,4-phenylene-3,6-pyridylene group.

[0060] [Table 1]

[0061] [Table 2]

[0062] [Table 3]

[0063] [Table 4]

[0064]

Table 5

[0065]

Table 6

[0066]

Table 7

[0067] The method for producing the fluoroalkane derivative represented by the formula (1) is not particularly limited, and for example, it can be synthesized by the following scheme or a scheme similar thereto. More specifically, it can be synthesized by the method described in the examples. In addition, among the symbols in each formula, the same symbol as that in the above formula (1) has the same meaning as that in the formula (1), and when there are the same symbols between different formulas, those symbols have the same meaning as each other. R 20 represents a protecting group for a carboxy group.

[0068]

Chemical formula

[0069] The compound (1) of the present invention can be used as a gelling agent for gelling an organic solvent. The compound (1) of the present invention is advantageous in that it can gel or solidify various organic solvents by adding a small amount. Further, the gel composition of the present invention contains one or more compounds (1) and an organic solvent.

[0070] 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 an organic solvent that is liquid at room temperature is preferably mentioned.

[0071] 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, and 3-pentanone; hydrocarbons which may have fluorine atoms such as pentane, hexane, octane, cyclohexane, perfluorodecalin, benzene, toluene, xylene, fluorobenzene, and hexafluorobenzene; ethers such as diethyl ether, 1,2-dimethoxyethane, 1,4-dioxane, crown ethers, glymes, tetrahydrofuran, and fluoroalkyl ethers; amides such as N,N-dimethylacetamide, N,N-dimethylformamide, and N,N-diethylformamide; amines which may have fluorine atoms such as ethylenediamine, pyridine, and perfluorotributylamine; carbonates such as propylene carbonate, ethylene carbonate, vinylene carbonate, fluoroethylene carbonate, diethyl carbonate, and ethyl methyl carbonate; nitriles such as acetonitrile, propionitrile, adiponitrile, and methoxyacetonitrile; lactams such as N-methylpyrrolidone (NMP); sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide; industrial oils such as silicone oil and petroleum; and edible oils.

[0072] In addition, ionic liquids can also be used as organic solvents. Ionic liquids refer to molten salts, and more specifically, ionic salts that become liquid near room temperature. Ionic liquids are liquids composed only of ions, and the cations constituting the ionic liquids are not limited to specific cations. Examples of such cations include those with nitrogen as the ionic center, those with phosphorus as the ionic center, those with sulfur as the ionic center, and those with nitrogen and sulfur as the ionic center.

[0073] Examples of cations with nitrogen as the ion center include imidazolium cation, ammonium cation, pyridinium cation, quinolinium cation, pyrrolidinium cation, piperazinium cation, morpholinium cation, pyridazinium cation, pyrimidinium cation, pyrazinium cation, pyrazolium cation, thiazolium cation, oxazolium cation, triazolium cation, guanidinium cation, 4-aza-1-azonia-bicyclo-[2,2,2]octanium, etc. These cations may have substituents represented by an alkyl group at any position, and the number of substituents may be plural.

[0074] Examples of imidazolium cations include 1-methylimidazolium, 1-ethylimidazolium, 1-propylimidazolium, 1-butylimidazolium, 1-butyl-3-methylimidazolium [BMIM], 1-ethyl-3-methylimidazolium [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-dimethyl-3-propylimidazolium and other 1,2,3-trialkylimidazoliums, 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]imidazolium, etc.

[0075] Examples of ammonium cations include tetramethylammonium, tetraethylammonium, tetrabutylammonium, 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-N-(2-phenoxyethyl)-1-dodecylammonium, and the like.

[0076] Examples of pyridinium cations include 1-ethylpyridinium, 1-butylpyridinium, 1-(3-hydroxypropyl)pyridinium, 1-ethyl-3-methylpyridinium , 1-butyl-3-methylpyridinium, 1-butyl-4-methylpyridinium, 1-(3-cyanopropyl)pyridinium, and the like.

[0077] Examples of pyrrolidinium cations include 1-methyl-1-propylpyrrolidinium [P13], 1-butyl-1-methylpyrrolidinium, 1-(2-hydroxyethyl)-1-methylpyrrolidinium, 1-ethyl-1-methylpyrrolidinium, and the like.

[0078] Examples of piperidinium cations include 1-methyl-1-propylpiperidinium, 1-butyl-1-methylpiperidinium, 1-(2-hydroxyethyl)-1-methylpiperidinium, 1-ethyl-1-methylpiperidinium, and the like.

[0079] Cations with phosphorus as the ionic center are generally called phosphonium cations, and specifically include tetrabutylphosphonium, tetrahexylphosphonium, trihexyltetradecylphosphonium, triphenylmethylphosphonium, (2-cyanoethyl)triethylphosphonium, (3-chloropropyl)trioctylphosphonium, tributyl(4-vinylbenzyl)phosphonium, triisobutylmethylphosphonium, triethylmethylphosphonium, tributylmethylphosphonium, tributylhexadecylphosphonium, 3-(triphenylphosphonio)propane-1-sulfonic acid, etc.

[0080] Cations with sulfur as the ionic center are generally called sulfonium cations, and specifically include triethylsulfonium, tributylsulfonium, 1-ethyltetrahydrothiophenium, 1-butyltetrahydrothiophenium, etc.

[0081] As anions that pair with cations, there are fluoride, chloride, bromide, iodide, dicyanamide, bis(fluorosulfonyl)amide [FSA], bis(trifluoromethylsulfonyl)amide [TFSA], bis(trifluoroethylsulfonyl)amide, bis(pentafluoroethylsulfonyl)amide, bis(nonafluorobutylsulfonyl)amide, tetrafluoroborate [BF4], 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, perfluorooctanesulfonate, heptadecafluorooctanesulfonate, 3-sulfopropyl methacrylate, 3-sulfopropyl acrylate, methyl sulfate, ethyl sulfate, octyl sulfate, diethylene glycol monomethyl ether sulfate, hydrogen sulfate, hexafluorophosphate [PF6], tris(trifluoromethyl)trifluorophosphate, tris(pentafluoroethyl)trifluorophosphate, dihydrogen phosphate, dibutyl phosphate, diethyl phosphate, dimethyl phosphate, bis(2,4,(4-trimethylpentyl)phosphinate, methyl phosphonate, methyl methyl phosphonate, 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, acesulfame, saccharinate, pyrazolate, imidazolate, thiazolate, triazolate, tetrazolate, indazolate, benzothiazolate, hexafluoroastatinate, hexafluoroantimonate, thiocyanate, tetrachloroaluminate, tetrachlorophenylate [FeCl4], carbonate, methyl carbonate, carbamate, etc. can be mentioned., These organic solvents are used alone or in combination of two or more kinds.,

[0082] The gel-like composition of the present invention preferably contains 0.05 to 10.0% by mass of the compound (1) based on the total amount, more preferably 0.1 to 8.0% by mass, and even more preferably 0.3 to 5.0% by mass. When the content is at least the above lower limit, the compound (1) tends to function more sufficiently as a gelling agent. When the content is at most the above upper limit, the economy and handleability tend to be further improved, the gelling agent is further suppressed from becoming an impurity, and the deterioration of the performance of the organic solvent can be further prevented. From the same viewpoint, the gel-like composition of the present invention preferably contains 90 to 99.95% by mass of the organic solvent based on the total amount, more preferably 92 to 99.9% by mass, and even more preferably 95 to 99.7% by mass.,

[0083] In addition to the compound (1) and the organic solvent, the gel composition of the present invention may contain other components as long as the function of the compound (1) as a gelling agent is not inhibited. Such components include, for example, gelling agents other than the compound (1), coagulants, thickeners, stabilizers, antioxidants, emulsifiers, lubricants, and safety improvers. When used as a gel electrolyte for a lithium-ion secondary battery, examples of the lithium salt to be added include LiPF6, LiBF4, LiClO4, LiSiF6, LiOSO2C k F 2k+1 、LiN(SO2C k F 2k+1 )2、LiPF n (C k F 2k+1 ) 4-n 、LiB(C2O2)2,Li BF2(C2O2)、LiPF3(C2O2), etc.

[0084] The method for preparing the gel composition of the present invention is not particularly limited. For example, it can be prepared by mixing an organic solvent, the compound (1), and other additives while heating to form a uniform mixture and then cooling the mixture. The mixing order of each component is not particularly limited, but a method of preparing a solution composed of an organic solvent and additives in advance and then mixing the gelling agent is preferred because it more easily forms a uniform mixture.

[0085] Hereinafter, the present invention will be described in more detail with reference to examples, but the technical scope of the present invention is not limited thereto. Table 4 summarizes the specific embodiments of the fluoroalkyl derivative of the present invention.

[0086]

Table 8

Examples

[0087] [Synthesis of Compound (1a-2)]

Chemical formula

[0088] 1H,1H,2H,2H-Perfluorooctyl iodide (10.08 g, 21.3 mmol), 4-methylbenzenethiol (2.64 g, 21.3 mmol), potassium carbonate (2.94 g, 21.3 mmol), and 100 ml of 3-pentanone were placed in a 300 ml eggplant flask, equipped with a calcium chloride tube, and refluxed at 110 °C for 3 days. After the reaction, the reaction solution was cooled to room temperature, water was added to dissolve the insoluble matter in the 300 ml eggplant flask. Then, it was transferred to a separatory funnel, chloroform was added thereto, and the mixture was separated into an organic layer and an aqueous layer. Anhydrous magnesium sulfate was added to the obtained organic layer, and the mixture was allowed to stand for 30 minutes. Then, the organic layer was filtered through a pleated filter paper, and the filtrate was concentrated with an evaporator. The obtained liquid was purified by silica gel column chromatography using chloroform as a developing solvent to obtain compound 1a’ as a pale yellow liquid (yield: 6.24 g, yield: 62.4%).

[0089] After dissolving 1a’ (1.87 g, 3.98 mmol) and 70% meta-chloroperbenzoic acid (1.96 g, 16.2 mmol) in chloroform respectively, they were placed in a 300 ml eggplant flask, equipped with a calcium chloride tube, and refluxed at 80 °C for 24 hours. After the reaction, it was allowed to cool to room temperature. Then, the reaction solution was transferred to a separatory funnel, sodium bisulfite dissolved in 50 ml of water was added, and further 50 ml of saturated aqueous sodium hydrogen carbonate solution and water were added to separate the mixture into an organic layer and an aqueous layer. Anhydrous magnesium sulfate was added to the obtained organic layer, and the mixture was allowed to stand for 30 minutes. Then, the organic layer was filtered through a pleated filter paper, and the filtrate was concentrated with an evaporator. The obtained solid was dissolved in methanol and recrystallized to obtain compound 1a-1 as a white solid (yield: 1.10 g, yield: 55.0%).

Example

[0090] [Synthesis of Compound (1b-2)] Compound 1b-2 was obtained in the same manner as in Example 1, except that 4-ethylbenzenethiol was used instead of 4-methylbenzenethiol.

Example

[0091] [Synthesis of Compounds (1c-1) and (1c-2)] [Chemical Formula]

[0092] 1H,1H,2H,2H-Perfluorodecyl iodide (7.39 g, 12.9 mmol), 4-methylbenzenethiol (1.60 g, 12.9 mmol), potassium carbonate (1.78 g, 12.9 mmol), and 100 ml of 3-pentanone were placed in a 300-ml eggplant flask equipped with a calcium chloride tube and refluxed at 110 °C for 3 days. After the reaction, the reaction solution was cooled to room temperature, water was added to dissolve the insoluble matter in the 300-ml eggplant flask. Then, it was transferred to a separatory funnel, chloroform was added, and the mixture was separated into an organic layer and an aqueous layer. Anhydrous magnesium sulfate was added to the obtained organic layer, and the mixture was allowed to stand for 30 minutes. Then, the organic layer was filtered through a pleated filter paper, and the filtrate was concentrated using an evaporator. Subsequently, the obtained solid was recrystallized from chloroform and methanol to obtain Compound 1c' as a white solid (yield: 4.10 g, yield rate: 55.8%).

[0093] Compound 1c' (1.46 g, 2.56 mmol) dissolved in chloroform was placed in a 300-ml eggplant flask and cooled in an ice bath for 10 minutes. To this, 70% meta-chloroperbenzoic acid (0.631 g, 5.22 mmol) dissolved in chloroform was added, and the mixture was stirred in an ice bath for 30 minutes. After the reaction, it was transferred to a separatory funnel, sodium bisulfite (1.00 g, 9.61 mmol) dissolved in 100 ml of water was added, and further, 50 ml of saturated aqueous sodium hydrogen carbonate solution and water were added to separate the mixture into an organic layer and an aqueous layer. Anhydrous magnesium sulfate was added to the obtained organic layer, and the mixture was allowed to stand for 30 minutes. Then, the organic layer was filtered through a pleated filter paper, and the filtrate was concentrated using an evaporator. Subsequently, the obtained solid was dissolved in methanol and recrystallized to obtain Compound 1c-1 as a white solid (yield: 1.30 g, yield rate: 86.7%).

[0094] Instead of 1H,1H,2H,2H-perfluorooctyl iodide, the procedure of Example 1 was repeated except that 1H,1H,2H,2H-perfluorodecyl iodide was used to obtain Compound (1c-2).

Example

[0095] [Synthesis of Compounds (1d-1) and (1d-2)] The procedure of Example 4 was repeated except that 4-ethylbenzenethiol was used instead of 4-methylbenzenethiol to obtain Compound (1d-1) and Compound (1d-2).

Example

[0096] [Synthesis of Compound (1e-2)] The procedure of Example 1 was repeated except that 1H,1H,2H,2H-perfluorododecyl iodide was used instead of 1H,1H,2H,2H-perfluorooctyl iodide to obtain Compound 1e-2.

Example

[0097] [Synthesis of Compound (1f-2)] The procedure of Example 5 was repeated except that 4-ethylbenzenethiol was used instead of 4-methylbenzenethiol to obtain Compound 1f-2. The physical property values of the compounds prepared in Examples 1 to 6 are summarized in Table 5 below.

[0098]

Table 9

[0099] Specific examples of another aspect of the compounds of the present invention are shown below (Table 6).

[0100]

Table 10

Example

[0101] [Synthesis of Compound (2a-1)] [Chemical formula]

[0102] To a 1000 ml eggplant flask, 4-mercaptobenzoic acid (10 g, 0.0644 mol) and 200 ml of methanol were added. After adding 5 ml of concentrated sulfuric acid, a calcium chloride tube was attached and refluxed for 1 day. Then, it was allowed to cool to room temperature, transferred to a separatory funnel, and cyclopentyl methyl ether, water, and saturated brine were added for washing. Magnesium sulfate was added to the organic layer obtained by liquid separation, and after standing for 30 minutes, it was filtered through a pleated filter paper. The solvent was distilled off under reduced pressure, and the obtained solid was recrystallized from methanol to obtain methyl 4-mercaptobenzoate (yield: 9.73 g, yield rate: 89%) as a yellow solid.

[0103] Methyl 4-mercaptobenzoate (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 iodide (21.54 g, 0.0575 mol) were added, a calcium chloride tube was attached, and refluxed for 2 days. Then, it was allowed to cool to room temperature, and the solution was filtered through a pleated filter paper. The filtrate was concentrated with an evaporator, allowed to cool to room temperature, and the obtained solid was recrystallized from methanol to obtain methyl 4-(2-(perfluorobutyl)ethylthio)benzoate (yield: 16.86 g, yield rate: 78.3%) as a brown solid.

[0104] Compound methyl 4-(2-(perfluorobutyl)ethylthio)benzoate (25 g, 0.0601 mol) 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, under ice-cooling, 12N HCl aqueous solution was added to make it acidic, and the obtained solid was recrystallized using methanol to obtain 4-(2-(perfluorobutyl)ethylthio)benzoic acid (yield: 17.43 g, yield rate: 72%) as a yellow solid.

[0105] In a 50 ml eggplant flask, 2.0 g (4.99 mmol) of 4-(2-(perfluorobutyl)ethylthio)benzoic acid and 8 ml of thionyl chloride solution were stirred on a water bath (80 °C) for 40 minutes. The solvent was distilled off under reduced pressure on a water bath (80 °C), and 8 ml of anhydrous toluene was added to the residue. An 8 ml solution of 0.97 g of p-hexyloxyphenol in anhydrous pyridine was slowly added dropwise. After stirring on an oil bath (80 °C) for 4 hours, the solvent was distilled off under reduced pressure, and the residue was washed with ethanol to obtain 2a’ as a colorless powder (yield: 0.81 g, yield rate: 37.4%). was obtained.

[0106] The compound 2a’ (0.81 g, 1.39 mmol) dissolved in chloroform was put into a 200 ml eggplant flask and cooled in an ice bath. To this, 0.239 g of 70% meta-chloroperbenzoic acid dissolved in chloroform was added, and the mixture was stirred in an ice bath for 30 minutes. After the reaction, it was transferred to a separatory funnel, 1.0 g of sodium bisulfite dissolved in 100 ml of chloroform and water was added, and liquid separation was performed to take out the organic layer. Further, a sodium hydrogen carbonate solution was added to the organic layer to separate the organic layer and the aqueous layer. Anhydrous magnesium sulfate was added to the obtained organic layer and allowed to stand for 30 minutes, then the organic layer was filtered through a pleated filter paper, the solvent was distilled off under reduced pressure, and the obtained solid was recrystallized from methanol. Further, purification was carried out by silica gel column chromatography using chloroform as the developing solution to obtain compound 2a-1 as a colorless powder (yield: 0.33 g, yield rate: 40.1%).

Example

[0107] [Synthesis of compound (2b-1)] Compound (2b-1) was obtained in the same manner as in Example 7, except that p-octyloxyphenol was used instead of p-hexyloxyphenol.

Example

[0108] [Synthesis of compound (2d-1)] Compound (2d-1) was obtained in the same manner as in Example 7, except that p-dodecyloxyphenol was used instead of p-hexyloxyphenol.

Example

[0109] [Synthesis of Compound 2a-2] [Chemical formula]

[0110] 10.00 g of 4-(2-(perfluorobutyl)ethylthio)benzoic acid, 200 ml of acetic acid, and 11.38 g of 30 wt% H2O2 were placed in a 300 ml eggplant flask and refluxed for three days. After allowing to cool to room temperature, 60 ml of a 20 wt% aqueous sodium sulfite solution was added to the reaction solution, followed by filtration and washing with water to obtain 4-(2-(perfluorobutyl)ethylsulfonyl)benzoic acid as a colorless powder (yield: 10.57 g, yield rate: 99.3%).

[0111] In a 50 ml eggplant flask, 4-(2-(perfluorobutyl)ethylsulfonyl)benzoic acid (0.90 g, 2.08 mmol), 0.4 g of phosphorus pentachloride, and 8 ml of thionyl chloride solution were stirred on an oil bath (80 °C) for 30 minutes. The solvent was distilled off under reduced pressure on an oil bath (80 °C), and 8 ml of anhydrous toluene was added to the residue. A solution of 0.4 g of p-hexyloxyphenol in 8 ml of anhydrous pyridine was slowly added dropwise thereto. After stirring on an oil bath (80 °C) for 4 hours, the solvent was distilled off under reduced pressure, and the residue was washed with ethanol to obtain 2a-2 as a colorless powder (yield: 0.29 g, yield rate: 23.0%). [Examples]

[0112] [Synthesis of Compounds (2b-2), (2c-2) and (2d-2)] Compounds (2b-2), (2c-2) and (2d-2) were obtained in the same manner as in Example 10, except that p-octyloxyphenol, p-decyloxyphenol, and p-dodecyloxyphenol were used instead of p-hexyloxyphenol, respectively. [Examples]

[0113] [Synthesis of Compound (2e-2)] [Chemical formula]

[0114] Dissolve 16.06 g of methyl 4-mercaptobenzoate in 400 ml of 3-pentanone in a 1000 ml eggplant flask, add 15.00 g of K2CO3 and 50 g of 2-(perfluorohexyl)ethyl iodide, attach a calcium chloride tube, and reflux for 2 days. Then, allow to cool to room temperature and filter. After concentrating the obtained filtrate, allow to cool to room temperature to obtain methyl 4-(2-(perfluorohexyl)ethylthio)benzoate as a yellow solid (yield: 42.39 g, yield rate: 86.27%). Dissolve 15.02 g of methyl 4-(2-(perfluorohexyl)ethylthio)benzoate in 500 ml of methanol in a 1000 ml eggplant flask, add 60 ml of 10N NaOH thereto, and reflux for 2 hours. After the reaction, add 12N HCl aqueous solution under ice cooling to make it acidic, and recrystallize the obtained solid using methanol to obtain 4-(2-(perfluorohexyl)ethylthio)benzoic acid as a white needle-like solid (yield: 10.36 g, yield rate: 70.91%).

[0115]

[0116] Place 10.00 g of 4-(2-(perfluorohexyl)ethylthio)benzoic acid, 11.38 g of 30 wt% H2O2, and 200 ml of acetic acid in a 300 ml eggplant flask, attach a calcium chloride tube, and reflux for three days. Allow to cool to room temperature, add 60 ml of 20 wt% sodium sulfite aqueous solution to the reaction solution, filter the precipitated solid, wash with water, and obtain 4-(2-(perfluorohexyl)ethylsulfonyl)benzoic acid as a colorless solid (yield: 10.57 g, yield rate: 99.3%).

[0117] Add 2.00 g of 4-(2-(perfluorohexyl)ethylsulfonyl)benzoic acid, 0.80 g of phosphorus pentachloride, and 20 ml of thionyl chloride to a 50 ml eggplant flask, attach a calcium chloride tube, and heat and stir in an oil bath (80 °C) for 1 hour. After stirring, distill off under reduced pressure until it becomes a solid to obtain 4-(2-(perfluorohexyl)ethylsulfonyl)benzoyl chloride. This was used in the next reaction without separation and purification. 0.63 g of p-butoxyphenol and 10 ml of pyridine were added to a 100 ml eggplant flask to dissolve the p-butoxyphenol. 4-(2-(Perfluorohexyl)ethylsulfonyl)benzoic acid chloride was dissolved in 30 ml of toluene, added to a 100 ml eggplant flask, equipped with a calcium chloride tube, and heated with stirring in an oil bath (80 °C) for 4 hours. The solvent was removed by distillation under reduced pressure, washed with ethanol, and 2e-2 (yield: 2.30 g, yield rate: 89.9%) was obtained as a colorless solid.

Example

[0118] [Synthesis of Compounds (2f-2), (2g-2), (2h-2) and (2i-2)] Compound (2f-2), (2g-2), (2h-2) and (2i-2) were obtained in the same manner as in Example 12, except that p-hexyloxyphenol, p-octyloxyphenol, p-decyloxyphenol, and p-dodecyloxyphenol were used instead of p-butoxyphenol, respectively.

Example

[0119] [Synthesis of Compounds (2j-2), (2k-2), (2l-2) and (2m-2)] Compound (2j-2), (2k-2), (2l-2) and (2m-2) were obtained in the same manner as in Example 12, except that 4-butoxy-4'-hydroxybiphenyl, 4-hexyloxy-4'-hydroxybiphenyl, 4-octyloxy-4'-hydroxybiphenyl, and p-dodecyloxy-4'-hydroxybiphenyl were used instead of p-butoxyphenol, respectively. The physical property values of the compounds produced in Examples 7 to 14 below are summarized in Table 7.

[0120]

Table 11

[0121] Specific examples of the compounds of another aspect of the present invention are shown below (Table 8).

[0122]

Table 12

Example

[0123] [Synthesis of Compound (3a-2)]

Chemical formula

[0124] In a 1 L eggplant flask, 25.0 g (0.164 mol) of methyl 4-hydroxybenzoate and 29.25 g (0.171 mol) of benzyl bromide were added to a solution of 3-pentanone (500 ml), and 22.6 g (0.164 mol) of potassium carbonate was added. The mixture was refluxed for 30 hours. After completion of the reaction, the mixture was cooled to room temperature, and the precipitate was filtered off by suction filtration. The solvent was distilled off under reduced pressure. The residue was recrystallized from toluene to obtain methyl 4-benzyloxybenzoate (yield: 24.69 g, yield rate: 62.1%) as a colorless solid.

[0125] In a 1 L eggplant flask, a mixed solvent of 15.06 g (62.6 mmol) of methyl 4-benzyloxybenzoate in 2N aqueous sodium hydroxide solution (150 ml) and ethanol (600 ml) was refluxed for three hours. After completion of the reaction, the mixture was cooled and acidified to pH = 1 with concentrated hydrochloric acid, and the resulting crystals were filtered off by suction filtration. Recrystallization from methanol gave 4-benzyloxybenzoic acid (yield: 10.49 g, yield rate: 68.4%) as colorless needle crystals.

[0126] In a 50 ml eggplant flask, a solution of 5.0 g (0.0219 mol) of 4-benzyloxybenzoic acid and 4.56 g (0.0219 mol) of phosphorus pentachloride in thionyl chloride (10 ml) was stirred on a water bath (80 °C) for 40 minutes. The solvent was distilled off under reduced pressure on a water bath (80 °C), and anhydrous toluene (20 ml) was added to the residue. A solution of 3.64 g (0.0219 mol) of 4-butoxyphenol in anhydrous pyridine (20 ml) was slowly added dropwise thereto. After stirring on an oil bath (80 °C) for 4 hours, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography using a chloroform developing solution. Thereafter, recrystallization was performed with a chloroform-ethanol mixed solvent to obtain 4-butoxyphenyl 4-benzyloxybenzoate (yield: 7.36 g, yield rate: 89.2%) as a colorless powder.

[0127] Under a hydrogen atmosphere, in a 1 L hydrogenation flask, 3.00 g (7.97 mmol) of 4-butoxyphenyl 4-benzyloxybenzoate, 0.50 g of palladium-carbon (Pd 10%), ethanol (400 ml), and toluene (200 ml) were vigorously stirred until hydrogen absorption ceased. After filtering off the precipitate and distilling off the solution under reduced pressure, the residue was purified by silica gel column chromatography using a chloroform developing solution and recrystallized with ethanol to obtain 4-butoxyphenyl 4-hydroxybenzoate (yield: 2.34 g, yield rate: 73.24%) as colorless needle crystals.

[0128] In a 50 ml eggplant flask, a solution of 1.75 g (3.49 mmol) of 4-(2-(perfluorohexyl)ethylthio)benzoic acid and 0.73 g (3.49 mmol) of phosphorus pentachloride in thionyl chloride (7 ml) was stirred on a water bath (80 °C) for 40 minutes. The solvent was distilled off under reduced pressure on a water bath (80 °C), and anhydrous toluene (10 ml) was added to the residue. A solution of 1.00 g (3.49 mmol) of 4-butoxyphenyl 4-hydroxybenzoate in anhydrous pyridine (10 ml) was slowly added dropwise thereto. After stirring on an oil bath (80 °C) for 4 hours, the solvent was distilled off under reduced pressure, and the residue was washed with ethanol to obtain 3a' (yield: 2.32 g, yield rate: 90.3%) as a colorless powder.

[0129] Weighed 0.8 g of compound 3a' into a 50 ml eggplant flask, added 0.8 g of 35% aqueous hydrogen peroxide and 40 ml of acetic acid, and refluxed at 120 °C for 3 days. After allowing to cool to room temperature, 5 ml of 20 wt% aqueous sodium sulfite solution and 40 ml of water were added. The precipitate was collected by suction filtration and dried to obtain 3a-2 as a colorless powder (yield: 0.77 g, yield rate: 94.3%).

Example

[0130] [Synthesis of Compounds (3b-2), (3c-2), (3d-2) and (3e-2)] Compounds (3b-2), (3c-2), (3d-2) and (3e-2) were obtained in the same manner as in Example 15, except that 4-hexyloxyphenyl 4-hydroxybenzoate, 4-octyloxyphenyl 4-hydroxybenzoate, 4-butoxy-4'-biphenyl 4-hydroxybenzoate and 4-hexyloxy-4'-biphenyl 4-hydroxybenzoate were used instead of 4-butoxyphenyl 4-hydroxybenzoate, respectively.

Example

[0131] [Synthesis of Compound (3f-2)] Methyl 4-hydroxybenzoate (50.1 g, 0.330 mol), acetone (200 ml), potassium carbonate (57.1, 0.413 mol), and 1-bromohexane (60.6 g, 0.368 mol) were added in this order to a 1 L eggplant flask and refluxed in an oil bath at 110 °C for two days. After the reaction, suction filtration was performed using an aspirator, and after filtering off the precipitate, the filtrate was distilled off under reduced pressure using an evaporator, allowed to cool to room temperature, and methyl 4-hexyloxybenzoate was obtained as a colorless transparent solid (yield: 47.5 g, yield rate: 61.1%).

[0132] To a 1 L eggplant flask, add methyl 4 - hexyloxybenzoate (37.1 g, 0.157 mol), 10 N aqueous sodium hydroxide solution (100 ml), and methanol (400 ml). Reflux at 100 °C in an oil bath for 3 hours. After the reaction, while cooling with ice, add hydrochloric acid until the pH reaches 1 to precipitate. Use an aspirator for suction filtration, filter off the precipitate, and then recrystallize the precipitate from ethanol to obtain 4 - hexyloxybenzoic acid as a colorless powder (yield: 22.4 g, yield rate: 64.2%).

[0133] To a 100 ml eggplant flask, add 4 - hexyloxybenzoic acid (8.04 g, 36.2 mmol) and thionyl chloride (15 ml). Heat and stir at 80 °C in an oil bath for 1 hour and 30 minutes. After the reaction, use an evaporator to distill off thionyl chloride under reduced pressure to obtain 4 - hexyloxybenzoyl chloride. To a 100 ml eggplant flask, add 4 - benzyloxyphenol (7.27, 36.2 mmol) and pyridine (15 ml), and then add 4 - hexyloxybenzoyl chloride (8.70 g, 36.2 mmol) dissolved in toluene (40 ml). Heat and stir at 80 °C in an oil bath for one day. After the reaction, use an evaporator to distill off the solvent under reduced pressure, dissolve the pyridine hydrochloride with ethanol and separate the layers, and then use an evaporator to distill off the toluene layer under reduced pressure. Recrystallize the residue from toluene to obtain 4 - hexyloxybenzoic acid 4 - benzyloxyphenyl as a colorless powder (yield: 13.7 g, yield rate: 93.4%).

[0134] To a 1 L Erlenmeyer flask with a cork, add 4 - hexyloxybenzoic acid 4 - benzyloxyphenyl (5.00 g, 12.9 mmol), ethanol (400 ml), toluene (200 ml), and 5% palladium on carbon (0.500 g). Stir vigorously for 4 days under a hydrogen atmosphere. After the reaction, filter off the 5% palladium on carbon, and then use an evaporator to distill off the solvent under reduced pressure to obtain 4 - hexyloxybenzoic acid 4 - hydroxyphenyl as a colorless powder (yield 3.72 g, yield rate 91.8%).

[0135] To a 100 ml eggplant flask, 4-(2-(perfluorohexyl)ethylsulfonyl)benzoic acid (1.00 g, 1.90 mmol) and thionyl chloride (15 ml) were added, and the mixture was heated with stirring at 80 °C in an oil bath for 1 hour and 30 minutes. After the reaction, thionyl chloride was distilled off under reduced pressure using an evaporator to obtain 4-(2-(perfluorohexyl)ethylsulfonyl)benzoyl chloride was obtained.

[0136] To a 100 ml eggplant flask, 4-hexyloxybenzoic acid 4-hydroxyphenyl (0.590 g, 1.90 mmol) and pyridine (15 ml) were added, and then 4-(2-(perfluorohexyl)ethylsulfonyl)benzoyl chloride dissolved in toluene (40 ml) was added. The mixture was heated with stirring at 80 °C in an oil bath for one day. After the reaction, the solvent was distilled off under reduced pressure using an evaporator, pyridine hydrochloride was dissolved with ethanol and separated by liquid extraction. After the toluene layer was distilled off under reduced pressure using an evaporator, the residue was recrystallized from toluene to obtain 3f-2 as a colorless powder (yield: 1.30 g, yield rate: 83.5%).

Example

[0137] [Synthesis of compound (3g-2)] Compound (3g-2) was obtained in the same manner as in Example 17, except that 1-bromooctane was used instead of 1-bromohexane.

Example

[0138] [Synthesis of compound (3i-2)]

Chemical formula

[0139] To a 100 ml eggplant flask, 4-(2-(perfluorohexyl)ethylthio)benzoic acid (1.50 g, 3.0 mmol) and thionyl chloride (15 ml) were added, and the mixture was heated with stirring at 80 °C in an oil bath for 1 hour and 30 minutes. After the reaction, thionyl chloride was distilled off under reduced pressure using an evaporator to obtain 4-(2-(perfluorohexyl)ethylthio)benzoyl chloride. 100 ml eggplant flask was charged with hydroquinone (0.170 g, 1.5 mmol) and pyridine (10 ml), then dissolved in toluene (40 ml), and 4-(2-(perfluorohexyl)ethylthio)benzoic acid chloride was added. The mixture was heated with stirring at 80 °C in an oil bath for 4 hours. After the reaction, the solvent was distilled off under reduced pressure using an evaporator. Pyridine hydrochloride was dissolved with ethanol, and after suction filtration, the filtrate was recrystallized with toluene to obtain 3i’ as a colorless powder (yield: 2.23 g, yield rate: 69.2%).

[0140] 0.50 g of 3i’ was placed in a 200 ml eggplant flask, 80 ml of acetic acid and 1.60 g of 30 wt% hydrogen peroxide were refluxed in an oil bath (120 °C) for 2 days. After cooling to room temperature, 100 ml of 20 wt% aqueous sodium sulfite solution was added to the reaction solution, followed by washing with water. The precipitate was suction filtered to obtain 3i-2 as a white solid (yield: 0.34 g, yield rate: 68%).

Example

[0141] [Synthesis of Compounds (3h-2), (3j-2), (3k-2), (3l-2) and (3m-2)] Compound (3h-2) was obtained in the same manner as in Example 19, except that 4-(2-(perfluorobutyl)ethylthio)benzoic acid was used instead of 4-(2-(perfluorohexyl)ethylthio)benzoic acid. Compounds (3j-2), (3k-2), (3l-2) and (3m-2) were obtained in the same manner as in Example 19, except that 1,4-butylene glycol, 1,6-hexylene glycol, 1,8-octylene glycol and 1,10-decylene glycol were used instead of hydroquinone, respectively. The physical property values of the compounds synthesized in Examples 15 to 20 are summarized in Table 9.

[0142]

Table 13

Example

[0143] [Measurement of Gelation Ability (Minimum Gelation Concentration, Sol-Gel Transition Temperature)] Approximately 3.5 mg of the gelling agent was weighed into a microtube (manufactured by Maruemu Co., Ltd., 11 mm in diameter). An appropriate amount of the solvent was added thereto, the sample tube was heated, and it was vigorously stirred using a vortex mixer. After allowing it to cool, the state of the solution was visually confirmed. At this time, when the sample tube was inverted, if it was in a solid state, it was regarded as "gel", and if it was in a liquid state, it was regarded as "sol". When it was judged to be a gel, the solvent was further added to determine the minimum gelation concentration. In addition, the temperature at the time of phase transition from the gel state to the sol state was measured and this was defined as the "sol-gel transition temperature". Regarding the minimum gelation concentration, it is summarized and shown in Tables 10 to 12, and regarding the sol-gel transition temperature, it is summarized and shown in Tables 13 to 15. In the tables, "-" indicates non-measurement. Also,

[0144] [Table 14] *1: PC: Propylene carbonate *2: GBL: γ-Butyrolactone *3: Registered trademark

[0145] [Table 15] *1: Registered trademark *2: At a concentration of 5% by mass, it indicates a state in which the compound is not completely or partially dissolved and is not gelled.

[0146] [Table 16] *1: At a concentration of 5% by mass, it indicates a state in which the compound is not completely or partially dissolved and is not gelled.

[0147] [Table 17]

[0148] [Table 18] *1: Concentration of compound 3% by mass *2: Concentration of compound 4% by mass *3: Concentration of compound 2% by mass

[0149]

Table 19

Examples

[0150] [Evaluation as an electrolyte solution] 1. Evaluation of gelation ability 1 EC and EMC were mixed so that the mass ratio was 1:2, and LiPF6 was added to the mixed solution to a concentration of 1 mol / L to prepare an ungelled electrolyte solution (A). To the total amount of the electrolyte solution (A) and the mixed solution (B) of EC and EMC with a mass ratio of 1:2, the compound No(2e-2) as a perfluoro group-containing compound as a gelling agent was added at a predetermined concentration, heated to 95°C and uniformly mixed, and then cooled to 25°C to obtain a gel electrolyte (a1) and a gel (b1). The obtained gel electrolyte (a1) and gel (b1) were heated to determine the phase transition temperature to a sol. The results are shown in Figure 1. Here, gel (b1) means a gel composed only of a mixed solution of EC and EMC not containing LiPF6 and the compound No(2e-2) as a gelling agent. 2. Evaluation of gelation ability 2 The phase transition temperature to a sol was determined in the same manner as in the case of the LiPF6 / EC-EMC example in (1) above, except that LiClO4 was added to PC to a concentration of 3 mol / L to prepare an ungelled electrolyte solution (A). The results are shown in Figure 2. As a comparative example, the results of using the compound (comparative compound θ) represented by the following formula as a gelling agent are shown.

Chemical formula

[0151] 3. Gel Strength Measurement EC and EMC were mixed so that the mass ratio was 1:2, and LiPF6 was added to the mixed solution to a concentration of 1 mol / L to prepare an ungelled electrolyte (A). To the total amount of the electrolyte (A), compound No(2e - 2) as a perfluoro group-containing compound which is a gelling agent was added at a concentration of 5% by mass, heated to 95°C and uniformly mixed, then filled into a sample bottle, and cooled to 25°C to create a gel with a height of 1 cm. At room temperature (about 20°C), using a rheometer (CR - 500DX - SII, manufactured by Sun Scientific Co., Ltd.; adapter diameter 10 mm), the adapter was inserted 5 mm into the gel, and the gel strength (g / cm 2 ) was calculated from the maximum load (g). As a result, the strength of the gel was 342.5 kg / cm 2 .

[0152] 4. Measurement of Ionic Conductivity 1 EC and EMC were mixed so that the mass ratio was 1:2, and LiPF6 was added to the mixed solution to a concentration of 1 mol / L to prepare an ungelled electrolyte (A). To the total amount of the electrolyte (A), compound No(2e - 2) as a perfluoro group-containing compound which is a gelling agent was added at concentrations of 1% by mass and 5% by mass, heated to 95°C and uniformly mixed, then in a glove box, before gelling, it was impregnated into glass fiber filter paper, and gelled in that state to obtain a gel electrolyte (a2) with a concentration of 1% by mass and a gel electrolyte (a3) with a concentration of 5% by mass. Pt was used for the working electrode and the counter electrode, and the obtained gel electrolytes (a2) and (a3) were used as separators to assemble a two - electrode cell. The two - electrode cell was placed in a thermostatic bath, and in the temperature range from - 20°C to 50°C at 10°C intervals, using an electrochemical measurement system (1280Z, manufactured by Solartron Analytical, UK), the impedance was measured under the following measurement conditions. The ionic conductivity was calculated from the impedance obtained by the measurement. The results are shown in Figure 3. [Measurement Conditions] Frequency range: 20000 - 5 Hz Applied voltage (AC amplitude): 5 mVp - p (p - p: between peak and peak) DC voltage: 0 mV Temperature: - 20~50°C

[0153] 5. Measurement of Ionic Conductivity 2 EC, PC, DMC, and EMC were mixed at a mass ratio of 15:10:65:10, and LiPF6 was added to the mixed solution to a concentration of 1 mol / L to prepare an ungelled electrolyte (C). To the total amount of the electrolyte (C), compound No(2f-2) as a perfluoro group-containing compound as a gelling agent was added at a concentration of 1% by mass, heated to 95 °C and uniformly mixed, and then in a glove box, before gelling, it was impregnated into glass fiber filter paper and gelled in that state to obtain a 1% by mass concentration gel electrolyte (a4). Pt was used for the working electrode and the counter electrode, and a two-electrode cell was assembled using the obtained gel electrolyte (a4) as a separator. The two-electrode cell was placed in a thermostat, and impedance was measured under the following measurement conditions using an electrochemical measurement system (1280Z, manufactured by Solartron, UK) in a temperature range of 0 °C to 60 °C in 10 °C increments. The ionic conductivity was calculated from the impedance obtained by the measurement. The results are shown in Figure 4. [Measurement Conditions] Frequency range: 20000 - 5 Hz Applied voltage (AC amplitude): 5 mVp-p (p-p: between peak and peak) DC voltage: 0 mV Temperature: 0 - 60 °C

[0154] 6. Measurement of Ionic Conductivity 3 Instead of the mixed solution obtained by mixing EC and EMC at a mass ratio of 1:2, [BMIM][TFSA], an ionic liquid, was used, and the measurement was performed in the same manner as in the measurement of ionic conductivity 1 except that the obtained gel electrolyte (a5) was used as a separator. The results are shown in Figure 5.

[0155] 7. Measurement of Potential Window 1 EC, PC, DMC, and EMC were mixed at a mass ratio of 15:10:65:10, and LiPF6 was added to the mixed solution to a concentration of 1 mol / L to prepare an ungelled electrolyte (C). To the total amount of the electrolyte (C), compound No(2f-2) as a perfluoro group-containing compound as a gelling agent was added at a concentration of 1% by mass, heated to 95 °C and uniformly mixed, and then impregnated into glass fiber filter paper in a glove box before gelling, and gelled in that state to obtain a 1% by mass concentration gel electrolyte (a6). Pt was used for the working electrode and the counter electrode, and Ag was used for the reference electrode. The obtained gel electrolyte (a6) was used as a separator to assemble a three-electrode cell. The three-electrode cell was placed in a thermostatic bath and set to 25 °C. Using an electrochemical measurement system (HZ5000(HAG3001), manufactured by Hokuto Denko Corporation), LSV measurement was performed with a potential scanning rate of 1.0 mV / s between the natural potential: +4V and the natural potential: -4V. The potential window was observed from the range where the reaction current did not show a large value. The results are shown in Figure 6.

[0156] 8. Measurement of potential window 2 Instead of the mixed solution of EC, PC, DMC, and EMC mixed at a mass ratio of 15:10:65:10, [BMIM][TFSA] was used, and 2e-2 and 2j-2 were used as gelling agents. Gel electrolytes (a7) and (a8) obtained with a gelling agent concentration of 5% by mass were used as separators, and the measurement was performed in the same manner as in the measurement of the potential window 1 except that the potential scanning range was set to 0.3 - 4.0V. The results are shown in Figure 7.

[0157] 9. Measurement of potential window 3 Among the conditions of the measurement of the potential window 1, the mixed solution was replaced with a solution of EC and EMC at a mass ratio of 1:2, and the measurement was performed in the same manner as in the measurement of the potential window 1 except that the gelling agent was replaced with compound No(2e-2) which is a perfluoro group-containing compound. The results are shown in Figure 8.

Example

[0158] [Evaluation of dynamic viscoelasticity] Gels were formed by blending propylene carbonate with the compounds 1a-2, 1b-2, 1c-2, 1d-2, 1e-2, and 1f-2, which are the compounds of the present invention, to a concentration of 3% by mass (gels (b2) for compound (1a-2), gel (b3) for compound (1b-2), gel (b4) for compound (1c-2), gel (b5) for compound (1d-2), gel (b6) for compound (1e-2), and gel (b7) for compound (1f-2), respectively).). For the obtained gels, a dynamic viscoelasticity measuring device (Rheosol-G1000-YM, manufactured by UBM Co., Ltd.) was used to measure in the frequency range of 0.01 to 5 Hz, and the storage modulus (G’) and the loss modulus (G’’) were determined, and tanδ (G’’ / G’) was determined based on the obtained values G’, G’’. The results are summarized and shown in Fig. 9. From Fig. 9, tanδ is 1 or more regardless of which gelling agent of the present invention is used, and the gel using the gelling agent of the present invention is a highly viscous gel and can be said to have liquid-like properties.

Industrial Applicability

[0159] There are many requirements for gelation in both water and organic solvents, and various gelling agents are used depending on the purpose and application. Therefore, the gelling agent of the present invention can be used in industrial fields such as cosmetics, pharmaceuticals and medical care, foods, paints, adhesives, and sludge treatment. By using the fluoroalkane derivative of the present invention, it was possible to form an ionic liquid gel that maintained a gel state up to a temperature of about 180°C, which was difficult in the prior art. Since the organic gelling agent does not have a hydrogen-bonding functional group, there is no electrochemical instability or decomposition due to pH changes. Furthermore, the ionic conductivity of the formed ionic liquid gel is almost the same as that in the liquid state. Therefore, the gelling agent of the present invention has the potential to construct a next-generation organic gel electrolyte that combines high ionic conductivity and mechanical strength, and its application to all-solid-state lithium-ion batteries can be expected. Furthermore, the ionic liquid gel produced by the gelling agent of the present invention is expected to be applied to a carbon dioxide separation membrane, and can be applied as an innovative CO2 separation material that can remove acidic gases and water for the ultimate purpose of CO2 reuse.

Claims

1. A fluoroalkane derivative represented by the following formula (1). 【Chemical 1】 {In formula (1), R １ is represented by the following formula (4) 【Chemical Formula 2】 (In formula (4), m represents any integer from 1 to 20, k represents any integer from 1 to 6, and l represents 1.) represents a group represented by, Ar １ represents an unsubstituted 1,4-phenylene group, R represents a group represented by the following formula (2). [Chemical Formula 3] [In formula (2), Y １ represents an unsubstituted C1-20 alkoxy group or an unsubstituted or fluorine atom-substituted C1-20 alkylsulfonyl group, Ar ２ represents an unsubstituted 1,4-phenylene group or an unsubstituted 4,4'-biphenylene group, L represents an oxygen atom or a divalent linking group represented by the following formula (3). 【Chemical Formula 4】 (In formula (3), X represents an oxygen atom, L １ represents an unsubstituted alkylene group having 2 to 20 carbon atoms or an unsubstituted 1,4-phenylene group, L ２ represents a group represented by the following formula (5a) or (5b). [Chemical Formula 5] (In Formulas (5a) and (5b), *1 represents the position of attachment to L １ and *2 represents the position of attachment to Ar ２ .))] n represents 2.}

2. A gelling agent containing the fluoroalkane derivative according to Claim 1.

3. A gel composition containing the fluoroalkane derivative according to Claim 1 or 2 and an organic solvent.

4. The gel composition according to Claim 3, wherein the organic solvent is an ionic liquid.

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