Fluorine-containing alkylammonium borate compound and method for producing the same

Abstract

A purpose of the present invention is to provide a compound useful as a co-catalyst to be used in polymerization reactions of olefins, dienes, and acetylenes. According to the present invention, a fluorine-containing alkyl ammonium borate compound represented by formula (1) (Definitions of symbols in the formula are as described in the specification.) that is useful and has high activity as a co-catalyst to be used in polymerization reactions of olefins, dienes, and acetylenes, a composition that contains the same, and methods for producing these can be provided.

Description

[Technical Field]

[0001] The present invention relates to a fluorine-containing alkylammonium borate compound useful as a cocatalyst for the polymerization of olefins, dienes, and acetylenes, a composition containing the same, and a method for producing the same. [Background technology]

[0002] There have been many reports of the use of non-metallocene metal complex catalysts such as metallocene compounds, diimine complexes, and phenoxy complexes as catalysts for the polymerization of olefins, dienes, and acetylenes. As co-catalysts used to stabilize the cationic active species of these metal complex catalysts, alkylaluminums, aluminoxanes such as methylaluminoxane (MAO), Bronsted acid salts such as ammonium borate, and Lewis acid salts such as triphenylcarbenium borate have been used (Non-Patent Document 1).

[0003] In the catalytic activation reaction by the Bronsted acid salt, the leaving group on the metal complex catalyst is protonated and eliminated from the metal complex catalyst, generating a cationic active species of the metal complex catalyst, and the non-coordinating anion derived from the Bronsted acid salt stabilizes the active species. As the Bronsted base constituting the Bronsted acid salt, various borate compounds such as tetrakis(pentafluorophenyl)borate, which is a non-coordinating anion, have been reported (Non-Patent Document 1), and as the Bronsted acid, a Bronsted acid containing nitrogen, phosphorus, oxygen, and / or sulfur is known (Patent Document 1).

[0004] Known examples of the Bronsted acid salt include nitrogen-containing Bronsted acid salts (ammonium borates), such as dimethylanilinium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, and methylpyrrolidinium tetrakis(pentafluorophenyl)borate (Patent Document 2). In the catalytic activation reaction using these ammonium borates, a neutral amine compound is produced by losing a proton during the protonation step. Such neutral amine compounds may interact with the cationic active species of the metal complex catalyst, which may adversely affect the polymerization reaction.

[0005] In order to reduce the basicity of the neutral amine compound produced in the catalytic activation reaction, N-(pentafluorophenyl)pyrrolidinium tetrakis(pentafluorophenyl)borate and the like have been proposed as cocatalysts (Patent Document 3). [Prior art documents] [Non-patent literature]

[0006] [Non-Patent Document 1] Chem.Rev.2000,100,1391-1434 [Patent documents]

[0007] [Patent Document 1] U.S. Patent No. 5,132,380 [Patent Document 2] International Publication No. 2010 / 014344 [Patent Document 3] International Publication No. 2001 / 042249 Summary of the Invention [Problem to be solved by the invention]

[0008] In view of these conventional techniques, the present inventors have an object to provide a fluorine-containing alkylammonium borate compound which exhibits higher polymerization activity as a co-catalyst for use in the polymerization reaction of olefins, dienes and acetylenes with a metal complex catalyst, as compared with the prior art, a composition containing the same, and an industrial process for producing the same. [Means for solving the problem]

[0009] As a result of extensive investigation, the present inventors have found that the compound represented by the following formula (1):

[0010] [ka]

[0011] [In the formula, R 1 , R 2 , R 3 and R 4 are each independently one or more fluorine atoms or one or more fluoro C 1-4 C substituted with alkyl groups 6-14 represents an aryl group, R 5 is a C substituted with one or more fluorine atoms 6-14 C substituted with one or more substituents selected from the group consisting of aryl groups and fluorine atoms 1-30 represents an alkyl group, R 6 and R 7 each independently represents an optionally substituted C 1-30 alkyl group, optionally substituted C 3-15 cycloalkyl group or optionally substituted C 6-14 represents an aryl group, or R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are attached form an optionally substituted cyclic group, n represents 1, and m represents 1 or 2. The present inventors have found for the first time that a compound represented by the formula (hereinafter also referred to as "the compound of the present invention") exhibits high metal complex catalyst activation ability in the polymerization reaction of olefins, dienes, and acetylenes, and is useful as a co-catalyst, thereby completing the present invention.

[0012] That is, the present invention is as follows. [1] Formula (1):

[0013] [ka]

[0014] [In the formula, R 1 , R 2 , R 3 and R 4 are each independently one or more fluorine atoms or one or more fluoro C 1-4 C substituted with alkyl groups 6-14 represents an aryl group, R 5 is a C substituted with one or more fluorine atoms 6-14 C substituted with one or more substituents selected from the group consisting of aryl groups and fluorine atoms 1-30 represents an alkyl group, R 6 and R 7 each independently represents an optionally substituted C 1-30 alkyl group, optionally substituted C 3-15 cycloalkyl group or optionally substituted C 6-14 represents an aryl group, or R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are attached form an optionally substituted cyclic group, n represents 1, and m represents 1 or 2. A compound represented by the formula: [2]R 1 , R 2 , R 3 and R 4each independently represents one or more fluorine atoms or one or more fluoro C 1-4 The compound according to [1] above, which is a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenylyl group, a 3-biphenylyl group, a 4-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 9-phenanthryl group, or a 3-phenanthryl group, each of which is substituted with an alkyl group. [3]R 1 , R 2 , R 3 and R 4 are all pentafluorophenyl groups, 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl) groups, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl groups, or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl groups. [4]R 5 is substituted with a phenyl group or a naphthyl group, each of which is substituted with one or more fluorine atoms 1-6 Alkyl group or fluoro C 1-6 The compound according to any one of the above [1] to [3], which is an alkyl group. [5]R 6 and R 7 However, each independently, (1) C optionally substituted with a halogen atom 6-14 aryl groups, (2) Halogen atoms and (3) C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 1-30 an alkyl group; or (1) a halogen atom, (2) C 1-30 alkyl groups, (3) C 1-30 alkoxy groups, (4) Haro C 1-30 Alkyl groups and (5) Haro C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 3-8cycloalkyl group The compound according to any one of [1] to [4] above, [6]R 6 and R 7 are bonded to each other and, together with the nitrogen atom to which they are bonded, form a cyclic group derived from an optionally substituted 3- to 8-membered monocyclic nitrogen-containing non-aromatic heterocyclic group. [7]R 5 But Fluoro C 1-6 is an alkyl group, and R 6 and R 7 However, each independently, (1) C optionally substituted with a halogen atom 6-14 aryl groups, (2) Halogen atoms and (3) C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 1-30 Alkyl group The compound according to any one of [1] to [4] above, [8] The compound according to any one of the above [1] to [7], wherein n and m are both 1. [9]R 5 , R 6 and R 7 The compound according to any one of [1] to [8] above, wherein the total number of carbon atoms is 25 or more.

[10] The compound according to any one of the above [1] to [9], and the compound according to the following formula (2):

[0015] [ka]

[0016] [In the formula, R and R′ are each independently an optionally substituted C 1-30 alkyl group, optionally substituted C 3-15 cycloalkyl group or optionally substituted C 6-14 represents an aryl group.] A composition containing a compound represented by the formula (hereinafter also referred to as "the composition of the present invention").

[11] R and R' are each independently an optionally substituted C 1-30 The composition according to

[10] above, wherein the group is an alkyl group.

[12] The composition according to

[10] or

[11] , wherein the content of the compound represented by formula (2) is in the range of 0.01 to 10 moles per mole of the compound represented by formula (1).

[13] The composition according to

[10] or

[11] , wherein the content of the compound represented by formula (2) is in the range of 0.1 to 3 moles per mole of the compound represented by formula (1).

[14] The compound according to any one of the above [1] to [9], and the compound according to the following formula (3):

[0017] [ka]

[0018] [R in the formula 5 , R 6 and R 7 has the same meaning as above.] A compound represented by (In the composition, the compound represented by formula (3) is an amine compound obtained by deprotonating the cation constituting formula (1) described in [1] above.)

[15] The composition according to

[14] , wherein the content of the compound represented by formula (3) is in the range of 0.01 to 10 moles per mole of the compound represented by formula (1).

[16] The composition according to

[14] , wherein the content of the compound represented by formula (3) is in the range of 0.5 to 3 moles per mole of the compound represented by formula (1).

[17] Furthermore, the following formula (2):

[0019] [ka]

[0020] [In the formula, R and R′ are each independently an optionally substituted C 1-30 alkyl group, optionally substituted C 3-15 cycloalkyl group or optionally substituted C 6-14 represents an aryl group.] A compound represented by The composition according to any one of

[14] to

[16] above, comprising:

[18] A co-catalyst for polymerization of at least one monomer selected from the group consisting of olefins, dienes, and acetylenes, comprising the compound according to any one of [1] to [9] above or the composition according to any one of

[10] to

[17] above.

[19] A method for producing a polymer, comprising polymerizing at least one monomer selected from the group consisting of olefins, dienes, and acetylenes using the compound according to any one of [1] to [9] above or the composition according to any one of

[10] to

[17] above as a co-catalyst.

[20] Formula (1):

[0021] [ka]

[0022] [In the formula, R 1 , R 2 , R 3 and R 4 are each independently one or more fluorine atoms or one or more fluoro C 1-4 C substituted with alkyl groups 6-14 represents an aryl group, R 5 teeth, (1) C substituted with one or more fluorine atoms 6-14 aryl groups and (2) Fluorine atom C substituted with one or more substituents selected from the group consisting of 1-30 Alkyl group represents R 6 and R 7 each independently represents an optionally substituted C1-30 alkyl group, optionally substituted C 3-15 cycloalkyl group or optionally substituted C 6-14 represents an aryl group, or R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are attached form an optionally substituted cyclic group, n represents 1, and m represents 1 or 2. A method for producing a compound represented by the following formula (4):

[0023] [ka]

[0024] [In the formula, R 1 , R 2 , R 3 and R 4 has the same meaning as above, M p+ represents an alkali metal ion or an alkaline earth metal ion, and p represents 1 or 2. In the presence of a protonic acid, a compound represented by the following formula (3):

[0025] [ka]

[0026] [R in the formula 5 , R 6 and R 7 has the same meaning as above.] A production method comprising the step of reacting a compound represented by the formula (I) with a compound represented by the formula (I). [Effects of the Invention]

[0027] According to the present invention, there are provided a fluorine-containing alkylammonium borate compound which exhibits high metal complex catalyst activation ability and is useful as a cocatalyst in the polymerization reactions of olefins, dienes, and acetylenes, a composition containing the same, and an industrial process for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0028] The definitions of the terms and symbols used in this specification are explained below.

[0029] In this specification, the term "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0030] In this specification, the term "alkyl (group)" refers to a straight-chain or branched-chain alkyl group having one or more carbon atoms.

[0031] In this specification, "C 1-30 The term "alkyl (group)" refers to a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, nonadecyl, eicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl.

[0032] In this specification, "C 1-18The term "alkyl (group)" refers to a straight-chain or branched-chain alkyl group having 1 to 18 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, and octadecyl.

[0033] In this specification, "C 1-6 The term "alkyl (group)" refers to a linear or branched alkyl group having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, and 2-ethylbutyl. Among these, C 1-4 Alkyl groups are preferred.

[0034] As used herein, "halo C" 1-30 The "C alkyl (group)" is defined as 1-30 It means a group in which one or more hydrogen atoms in the "alkyl" group are substituted with a halogen atom. Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, 2,2-difluoropropyl, 1,1,2,2-tetrafluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 4,4,4-trifluorobutyl, 2,2-difluoropentyl, 5,5,5-trifluoropentyl, 2,2-difluorohexyl, and 6,6,6-trifluorohexyl. Among these, the above-mentioned "halo C" is particularly preferred. 1-30The halogen atom in the alkyl (group) is a fluorine atom, and C is substituted with one or more fluorine atoms. 1-30 The alkyl group "fluoro C 1-30 Alkyl (group) is preferred.

[0035] As used herein, "halo C" 1-6 The "C alkyl (group)" is 1-6 It means a group in which one or more hydrogen atoms in the "alkyl" group are substituted with a halogen atom. Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, 2,2-difluoropropyl, 1,1,2,2-tetrafluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 4,4,4-trifluorobutyl, 2,2-difluoropentyl, 5,5,5-trifluoropentyl, 2,2-difluorohexyl, and 6,6,6-trifluorohexyl. Among these, the above-mentioned "halo C" is particularly preferred. 1-6 "Fluoro C" where the halogen atom in the "alkyl" group is a fluorine atom 1-6 Alkyl (group) is preferred.

[0036] "Fluoro C 1-6 Specific examples of the alkyl (group) include fluoromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, 2,2-difluoropropyl, 1,1,2,2-tetrafluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 4,4,4-trifluorobutyl, 2,2-difluoropentyl, 5,5,5-trifluoropentyl, 2,2-difluorohexyl, and 6,6,6-trifluorohexyl. Among these, R 5Fluoro-C in the definition 1-6 Specific examples of the alkyl (group) include fluoro C groups having fluorine atoms at the β- and / or γ-positions, such as 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, and 2,2-difluorohexyl. 1-6 Alkyl (group) is preferred, and fluoro C having a fluorine atom at the β-position such as 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, and 2,2-difluorobutyl. 1-4 Alkyl (group) is more preferred, and fluoro C having a fluorine atom at the β-position and three or more fluorine atoms, such as 2,2,2-trifluoroethyl and 2,2,3,3,3-pentafluoropropyl, is preferred. 2-4 Alkyl groups are more preferred.

[0037] R 1 , R 2 , R 3 and R 4 C in 6-14 Substituents of aryl groups, or R 6 and R 7 "Fluoro C" as a substituent of a cyclic group formed by bonding together with the nitrogen atom to which they are attached 1-4Specific examples of the alkyl (group) include fluoromethyl, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, 1,1,2,2-tetrafluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1-difluoropropyl, 2,2-difluoropropyl, nonafluorobutyl, 1,1,2,2-tetrafluorobutyl, 2,2-difluorobutyl, 1,1-difluorobutyl, and 4,4,4-trifluorobutyl. Among these, trifluoromethyl, 1,1-difluoroethyl, pentafluoroethyl, 1,1-difluoropropyl, heptafluoropropyl, 1,1-difluorobutyl, and nonafluorobutyl are preferred, and trifluoromethyl, 1,1-difluoroethyl, and pentafluoroethyl are more preferred.

[0038] In the present specification, the term "cycloalkyl (group)" refers to a cyclic alkyl group, and when there is no particular limitation on the range of the number of carbon atoms, it is preferably C 3-15 is a cycloalkyl group, more preferably C 3-8 It is a cycloalkyl group.

[0039] In this specification, "C 3-15 The term "cycloalkyl (group)" refers to a cyclic alkyl group having 3 to 15 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclotetradecyl, and cyclopentadecyl. 3-8 The term "cycloalkyl (group)" refers to a cyclic alkyl group having 3 to 8 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. 3-6 Cycloalkyl groups are preferred.

[0040] As used herein, the term "alkoxy (group)" refers to a group in which a straight-chain or branched-chain alkyl group is bonded to an oxygen atom.

[0041] In this specification, "C 1-30 The term "alkoxy (group)" refers to a straight-chain or branched-chain alkoxy group having 1 to 30 carbon atoms, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, isohexyloxy, 1,1-dimethylbutoxy, 2,2-dimethylbutoxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy, eicosyloxy, docosyloxy, tricosyloxy, tetracosyloxy, pentacosyloxy, hexacosyloxy, heptacosyloxy, octacosyloxy, nonacosyloxy, and triacontyloxy.

[0042] In this specification, "C 1-6 The term "alkoxy (group)" refers to a straight-chain or branched-chain alkoxy group having 1 to 6 carbon atoms, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, and hexyloxy. 1-4 Alkoxy groups are preferred.

[0043] As used herein, "halo C" 1-30 The "alkoxy (group)" is defined as "C 1-30"Alkoxy" refers to a group in which one or more hydrogen atoms have been replaced with halogen atoms. Specific examples include difluoromethoxy, trifluoromethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, heptafluoropropoxy, 2,2-difluoropropoxy, 1,1,2,2-tetrafluoropropoxy, 2,2,3,3-tetrafluoropropoxy, 3,3,3-trifluoropropoxy, 2,2,3,3,3-pentafluoropropoxy, 2,2-difluorobutoxy, 2,2,3,3,3-pentafluoropropoxy, 4,4,4-trifluorobutoxy, 2,2-difluoropentyloxy, 5,5,5-trifluoropentyloxy, 2,2-difluorohexyloxy, and 6,6,6-trifluorohexyloxy. 1-6 "HaloC" in which one or more hydrogen atoms in the "alkoxy" group are replaced with halogen atoms 1-6 Alkoxy is preferred.

[0044] As used herein, "fluoro C 1-6 The term "alkoxy (group)" refers to the same as the above "halo C 1-6"alkoxy" means a group in which the halogen atom in the group is a fluorine atom. Specific examples include difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, heptafluoropropoxy, 2,2-difluoropropoxy, 1,1,2,2-tetrafluoropropoxy, 2,2,3,3-tetrafluoropropoxy, 3,3,3-trifluoropropoxy, 2,2,3,3,3-pentafluoropropoxy, 2,2-difluorobutoxy, 2,2,3,3,3-pentafluoropropoxy, 4,4,4-trifluorobutoxy, 2,2-difluoropentyloxy, 5,5,5-trifluoropentyloxy, 2,2-difluorohexyloxy, and 6,6,6-trifluorohexyloxy. Among them, "fluoro C" such as difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, pentafluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 3,3,3-trifluoropropoxy, and 4,4,4-trifluorobutoxy are preferred. 1-4 Alkoxy (group) is preferred, with difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy or pentafluoroethoxy being more preferred, and trifluoromethoxy being particularly preferred.

[0045] In the present specification, the term "aryl (group)" refers to a monocyclic or polycyclic (fused) hydrocarbon group exhibiting aromaticity, and specifically includes, for example, C aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 3-phenanthryl, and 9-phenanthryl. 6-14 Among them, phenyl, 4-biphenylyl, 1-naphthyl, and 2-naphthyl are preferred.

[0046] As used herein, "one or more fluorine atoms or one or more fluoro C 1-4 C substituted with alkyl groups 6-14 The term "aryl (group)" refers to the C 6-14One or more hydrogen atoms in the aryl group are replaced with a fluorine atom or a fluoroC 1-4 It means a group substituted with an alkyl group, and specific examples thereof include a pentafluorophenyl group, a 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl) group, a 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group, a 1,3,4,5,6,7,8-heptafluoro-2-naphthyl group, a 4-trifluoromethylphenyl group, a 3,4-bis(trifluoromethyl)phenyl group, etc. Among these, a pentafluorophenyl group, a 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl) group, a 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group, and a 1,3,4,5,6,7,8-heptafluoro-2-naphthyl group are preferred.

[0047] As used herein, "C substituted with one or more fluorine atoms" refers to 6-14 C substituted with aryl groups 1-30 The term "alkyl (group)" refers to the C 6-14 C in which one or more hydrogen atoms in the aryl group are replaced by a group substituted with a fluorine atom 1-30 alkyl group, preferably C substituted with phenyl or naphthyl groups, each of which is substituted with one or more fluorine atoms. 1-6 It is an alkyl group. Specific examples thereof include a pentafluorophenylmethyl group, a 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl)methyl group, a 2,3,4,5,6,7,8-heptafluoro-1-naphthylmethyl group, and a 1,3,4,5,6,7,8-heptafluoro-2-naphthylmethyl group, among which a pentafluorophenylmethyl group, a 2,3,4,5,6,7,8-heptafluoro-1-naphthylmethyl group, or a 1,3,4,5,6,7,8-heptafluoro-2-naphthylmethyl group is preferred, and a pentafluorophenylmethyl group is more preferred.

[0048] In this specification, R 6 and R 7The "cyclic group" formed by bonding together with the nitrogen atom to which they are bonded means a cyclic ammonio group derived from a saturated nitrogen-containing non-aromatic heterocyclic group (in the case of the compound of the present invention (compound (1))) or a saturated nitrogen-containing non-aromatic heterocycle (in the case of compound (3) described below). Here, the "cyclic ammonio group derived from a saturated nitrogen-containing non-aromatic heterocyclic group" refers to a group represented by R 6 and R 7are bonded to each other and a hydrogen atom is bonded to the nitrogen atom to which they are bonded. Such a "cyclic group" may have a heteroatom selected from an oxygen atom, a sulfur atom, and a nitrogen atom in addition to carbon atoms as ring-constituting atoms other than the nitrogen atom of the amino group, and examples of such a "cyclic group" include cyclic ammonio groups derived from a 3- to 8-membered (preferably 4- to 6-membered) monocyclic nitrogen-containing non-aromatic heterocyclic group. Specific examples of the "cyclic group" include cyclic ammonio groups derived from 3- to 8-membered monocyclic nitrogen-containing non-aromatic heterocyclic groups such as an aziridinyl group, azetidinyl group, pyrrolidinyl group, pyrrolinyl group, piperidyl group, azepanyl group, morpholinyl group, thiomorpholinyl group, piperazinyl group, oxazolidinyl group, thiazolidinyl group, imidazolidinyl group, oxazolinyl group, thiazolinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, tetrahydropyridyl group, tetrahydropyrimidinyl group, and tetrahydrotriazolyl group. Among these, cyclic ammonio groups derived from an azetidinyl group, pyrrolidinyl group, piperidyl group, piperazinyl group, or morpholinyl group are preferred, and cyclic ammonio groups derived from a piperidyl group or piperazinyl group are more preferred. The "saturated nitrogen-containing non-aromatic heterocycle" includes a 3- to 8-membered (preferably 4- to 6-membered) monocyclic nitrogen-containing non-aromatic heterocycle, which may have a heteroatom selected from oxygen, sulfur, and nitrogen atoms as a ring-constituting atom other than carbon atoms in addition to the nitrogen atom of the amino group. Specific examples of such a "saturated nitrogen-containing non-aromatic heterocycle" include 3- to 8-membered monocyclic nitrogen-containing non-aromatic heterocycles such as aziridine, azetidine, pyrrolidine, pyrroline, piperidine, azepane, morpholine, thiomorpholine, piperazine, oxazolidine, thiazolidine, imidazolidine, oxazoline, thiazoline, imidazoline, pyrazolidine, pyrazoline, tetrahydropyridine, tetrahydropyrimidine, and tetrahydrotriazoline. Among these, azetidine, pyrrolidine, piperidine, piperazine, and morpholine are preferred, and piperidine and piperazine are more preferred.

[0049] In the present specification, the term "optionally substituted" means unsubstituted or having one or more substituents, and unless otherwise specified, the "substituents" include (1) a halogen atom, (2) a nitro group, (3) a cyano group, (4) a C 1-30 Alkyl group, (5) halo C 1-30 Alkyl group, (6) C 3-8 Cycloalkyl groups, (7) C 1-30 Alkoxy group, (8) haloC 1-30 Alkoxy group, (9)C 6-14 Among them, halogen atoms, cyano groups, C 1-6 Alkyl group, halo C 1-6 Alkyl group, C 1-6 Alkoxy group, haloC 1-6 An alkoxy group or a phenyl group is preferred, a halogen atom (e.g., a fluorine atom), C 1-4 Alkyl groups (e.g., methyl, ethyl), C 1-4 Alkoxy groups (e.g., methoxy, ethoxy), haloC 1-4 Alkyl groups (e.g., trifluoromethyl, 2,2,2-trifluoroethyl, etc.) 1-4 alkyl group) or halo C 1-4 Alkoxy groups (e.g., fluoro C such as trifluoromethoxy and 2,2,2-trifluoroethoxy) 1-4 An alkoxy group is more preferred. When a plurality of substituents are present, the substituents may be the same or different. The above substituents may further each be one or more of C 1-6 Alkyl group, C 1-6 It may be substituted with an alkoxy group, a halogen atom, a phenyl group, or the like.

[0050] In the present specification, specific examples of the "alkali metal ion" include lithium ion, potassium ion, sodium ion, cesium ion, and the like.

[0051] In the present specification, specific examples of the "alkaline earth metal ion" include magnesium ion, calcium ion, and the like.

[0052] In this specification, the term "hydrocarbon solvent" refers to solvents including aromatic hydrocarbon solvents and / or aliphatic hydrocarbon solvents. Among these, aliphatic hydrocarbon solvents are preferred in terms of odor and toxicity.

[0053] In the present specification, examples of the "aromatic hydrocarbon solvent" include benzene, toluene, xylene, etc.

[0054] In the present specification, examples of the "aliphatic hydrocarbon solvent" include n-hexane, isohexane, n-heptane, n-octane, cyclohexane, methylcyclohexane, and mixed solvents thereof.

[0055] As used herein, "soluble in a hydrocarbon solvent (or an aliphatic hydrocarbon solvent)" means that, in a solution of the compound (or composition) of the present invention and a hydrocarbon solvent (or an aliphatic hydrocarbon solvent) at 25°C, the compound (or composition) of the present invention dissolves at a concentration of 5% by weight or more to form a transparent, homogeneous solution. Also, "easily soluble in a hydrocarbon solvent (or an aliphatic hydrocarbon solvent)" means that, in a solution of the compound (or composition) of the present invention and a hydrocarbon solvent (or an aliphatic hydrocarbon solvent) at 25°C, the compound (or composition) of the present invention dissolves at a concentration of 20% by weight or more (preferably, 30% by weight or more) to form a transparent, homogeneous solution.

[0056] (Compounds of the present invention) The compounds of the present invention will be described below.

[0057] The compound of the present invention is represented by the following formula (1):

[0058] [ka]

[0059] [In the formula, R 1 , R 2 , R 3 and R 4 are each independently one or more fluorine atoms or one or more fluoro C 1-4C substituted with alkyl groups 6-14 represents an aryl group, R 5 is a C substituted with one or more fluorine atoms 6-14 C substituted with one or more substituents selected from the group consisting of aryl groups and fluorine atoms 1-30 represents an alkyl group, R 6 and R 7 each independently represents an optionally substituted C 1-30 alkyl group, optionally substituted C 3-15 cycloalkyl group or optionally substituted C 6-14 represents an aryl group, or R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are attached form an optionally substituted cyclic group, n represents 1, and m represents 1 or 2. It is a compound represented by the formula:

[0060] A preferred embodiment of the compound represented by formula (1) (hereinafter also referred to as "compound (1)") will be explained below.

[0061] Each group in compound (1) will be explained below.

[0062] R 1 , R 2 , R 3 and R 4 are preferably each independently one or more fluorine atoms or one or more fluoro C 1-4R is a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 3-phenanthryl group, or 9-phenanthryl group substituted with an alkyl group (e.g., trifluoromethyl group), more preferably a phenyl group, 1-naphthyl group, 2-naphthyl group, or 4-biphenylyl group each independently substituted with one or more fluorine atoms or one or more trifluoromethyl groups, and particularly preferably 1 , R 2 , R 3 and R 4 are all the same, a pentafluorophenyl group, a 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl) group, a 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group, or a 1,3,4,5,6,7,8-heptafluoro-2-naphthyl group.

[0063] R 5 is preferably a C substituted with a phenyl or naphthyl group, each of which is substituted with one or more fluorine atoms. 1-6 Alkyl group or fluoro C 1-6 alkyl group, more preferably a phenylmethyl group substituted with one or more fluorine atoms (e.g., a pentafluorophenylmethyl group) or a fluoroC 1-6 alkyl group, more preferably fluoro C 1-6 Fluoro C alkyl groups having fluorine atoms at the β- and / or γ-positions, such as 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, and 2,2-difluorohexyl 1-6 alkyl group), and particularly preferably fluoro C 1-4Fluoro C alkyl groups having a fluorine atom at the β-position, such as 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, and 2,2-difluorobutyl. 1-4 alkyl group).

[0064] R 6 and R 7 are preferably each independently (1) C optionally substituted with a halogen atom 6-14 aryl groups, (2) Halogen atoms and (3) C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 1-30 an alkyl group; or (1) a halogen atom, (2) C 1-30 alkyl groups, (3) C 1-30 alkoxy groups, (4) Haro C 1-30 Alkyl groups and (5) Haro C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 3-8 cycloalkyl group and more preferably, each independently: (1) C optionally substituted with a halogen atom (e.g., a fluorine atom) 6-14 aryl groups, (2) Halogen atoms and (3) C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 1-30 Alkyl group is.

[0065] R 6 and R 7 In another embodiment, preferably, R 6 and R7 are bonded to each other together with the nitrogen atom to which they are bonded to form a cyclic group derived from an optionally substituted 3- to 8-membered monocyclic nitrogen-containing non-aromatic heterocyclic group, and more preferably, R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are bonded, (1) a halogen atom (e.g., a fluorine atom), (2) C 1-4 alkyl groups (e.g., methyl, ethyl); (3) C 1-4 Alkoxy groups (e.g., methoxy, ethoxy), (4) Haro C 1-4 Alkyl groups (e.g., trifluoromethyl, 2,2,2-trifluoroethyl, etc.) 1-4 alkyl group) and (5) Haro C 1-4 alkoxy group and forming a cyclic group derived from an azetidinyl group, a pyrrolidinyl group, a piperidyl group, a piperazinyl group, or a morpholinyl group, which may be substituted with a substituent selected from the group consisting of 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are bonded, form a halogen atom (e.g., a fluorine atom), C 1-4 Alkyl groups (e.g., methyl, ethyl), C 1-4 Alkoxy groups (e.g., methoxy, ethoxy), haloC 1-4 Alkyl groups (e.g., trifluoromethyl, 2,2,2-trifluoroethyl, etc.) 1-4 alkyl group) or halo C 1-4 A cyclic group derived from a piperidyl group or a piperazinyl group, which may be substituted with an alkoxy group, is formed.

[0066] R 5 , R 6 and R 7 The total number of carbon atoms is preferably 25 or more, and more preferably 35 or more.

[0067] n is preferably 1.

[0068] m is preferably 1 or 2, and more preferably 1.

[0069] Suitable compounds (1) include the following compounds:

[0070] [Compound (1-1)] In the formula (1), R 1 , R 2 , R 3 and R 4 each independently represents one or more fluorine atoms or one or more fluoro C 1-4 a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenylyl group, a 3-biphenylyl group, a 4-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 3-phenanthryl group, or a 9-phenanthryl group, each of which is substituted by an alkyl group (e.g., a trifluoromethyl group), R 5 is substituted with a phenyl group or a naphthyl group, each of which is substituted with one or more fluorine atoms 1-6 Alkyl group or fluoro C 1-6 an alkyl group (preferably a fluoro C group having a fluorine atom at the β-position and three or more fluorine atoms, such as 2,2,2-trifluoroethyl or 2,2,3,3,3-pentafluoropropyl); 2-4 is an alkyl group; R 6 and R 7 However, each independently, (1) C optionally substituted with a halogen atom 6-14 aryl groups, (2) Halogen atoms and (3) C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 1-30 an alkyl group; or (1) a halogen atom, (2) C 1-30 alkyl groups, (3) C 1-30 alkoxy groups, (4) Haro C1-30 Alkyl groups and (5) Haro C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 3-8 is a cycloalkyl group, n is 1, and Compound (1), wherein m is 1.

[0071] [Compound (1-2)] In the formula (1), R 1 , R 2 , R 3 and R 4 are each independently a phenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 4-biphenylyl group substituted with one or more fluorine atoms or one or more trifluoromethyl groups, R 5 is a phenylmethyl group substituted with one or more fluorine atoms (e.g., a pentafluorophenylmethyl group) or a fluoroC 1-6 alkyl group, more preferably fluoro C 1-6 Fluoro C alkyl groups having fluorine atoms at the β- and / or γ-positions, such as 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, and 2,2-difluorohexyl 1-6 alkyl group), and particularly preferred are fluoro C groups having a fluorine atom at the β-position and three or more fluorine atoms, such as 2,2,2-trifluoroethyl and 2,2,3,3,3-pentafluoropropyl. 2-4 is an alkyl group, R 6 and R 7 However, each independently, (1) C optionally substituted with a halogen atom (e.g., a fluorine atom) 6-14 aryl groups, (2) Halogen atoms and (3) C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 1-30 is an alkyl group, n is 1, and Compound (1), wherein m is 1.

[0072] [Compound (1-3)] In the formula (1), R 1 , R 2 , R 3 and R 4 are all identical pentafluorophenyl groups, 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl) groups, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl groups, or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl groups, R 5 But Fluoro C 1-6 Fluoro C alkyl groups having fluorine atoms at the β- and / or γ-positions, such as 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, and 2,2-difluorohexyl 1-6 alkyl group), R 6 and R 7 However, each independently, (1) C optionally substituted with a halogen atom (e.g., a fluorine atom) 6-14 aryl groups, (2) Halogen atoms and (3) C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 1-30 Alkyl group and n is 1, and Compound (1), wherein m is 1.

[0073] [Compound (1-4)] In the formula (1), R 1 , R 2 , R 3 and R 4 are all identical pentafluorophenyl groups, 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl) groups, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl groups, or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl groups, R 5 But Fluoro C 1-4 Alkyl groups (e.g., 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, etc.) having a fluorine atom at the β-position 1-4 Among them, fluoro C alkyl groups having a fluorine atom at the β-position and three or more fluorine atoms, such as 2,2,2-trifluoroethyl and 2,2,3,3,3-pentafluoropropyl, are preferred. 2-4 An alkyl group is preferred. R 6 and R 7 However, each independently, (1) C optionally substituted with a halogen atom (e.g., a fluorine atom) 6-14 aryl groups, (2) Halogen atoms and (3) C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 1-30 is an alkyl group, n is 1, and Compound (1), wherein m is 1.

[0074] [Compound (1-5)] In the formula (1), R 1 , R 2 , R 3and R 4 each independently represents one or more fluorine atoms or one or more fluoro C 1-4 a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenylyl group, a 3-biphenylyl group, a 4-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 3-phenanthryl group, or a 9-phenanthryl group substituted by an alkyl group (e.g., a trifluoromethyl group), R 5 is substituted with a phenyl group or a naphthyl group, each of which is substituted with one or more fluorine atoms 1-6 Alkyl group or fluoro C 1-6 an alkyl group (preferably a fluoro C group having a fluorine atom at the β-position and three or more fluorine atoms, such as 2,2,2-trifluoroethyl or 2,2,3,3,3-pentafluoropropyl); 2-4 is an alkyl group; R 6 and R 7 are bonded to each other and, together with the nitrogen atom to which they are bonded, form a cyclic group derived from an optionally substituted 3- to 8-membered monocyclic nitrogen-containing non-aromatic heterocyclic group, n is 1, and Compound (1), wherein m is 1 or 2.

[0075] [Compound (1-6)] In the formula (1), R 1 , R 2 , R 3 and R 4 are each independently a phenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 4-biphenylyl group substituted with one or more fluorine atoms or one or more trifluoromethyl groups, R 5 is a phenylmethyl group substituted with one or more fluorine atoms (e.g., a pentafluorophenylmethyl group) or a fluoroC 1-6 alkyl group, more preferably fluoro C 1-6alkyl groups (e.g., 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, and the like) 1-6 Among them, fluoro C alkyl groups having a fluorine atom at the β-position and three or more fluorine atoms, such as 2,2,2-trifluoroethyl and 2,2,3,3,3-pentafluoropropyl, are preferred. 2-4 An alkyl group is preferred. R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are bonded, (1) a halogen atom (e.g., a fluorine atom), (2) C 1-4 alkyl groups (e.g., methyl, ethyl); (3) C 1-4 Alkoxy groups (e.g., methoxy, ethoxy), (4) Haro C 1-4 Alkyl groups (e.g., trifluoromethyl, 2,2,2-trifluoroethyl, etc.) 1-4 alkyl group) and (5) Haro C 1-4 alkoxy group forming a cyclic group derived from an azetidinyl group, a pyrrolidinyl group, a piperidyl group, a piperazinyl group or a morpholinyl group, which may be substituted with a substituent selected from the group consisting of n is 1, and Compound (1), wherein m is 1 or 2.

[0076] [Compound (1-7)] In the formula (1), R 1 , R 2 , R 3 and R 4are all identical pentafluorophenyl groups, 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl) groups, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl groups, or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl groups, R 5 But Fluoro C 1-6 alkyl groups (e.g., 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, and the like) 1-6 Among them, fluoro C alkyl groups having a fluorine atom at the β-position and three or more fluorine atoms, such as 2,2,2-trifluoroethyl and 2,2,3,3,3-pentafluoropropyl, are preferred. 2-4 An alkyl group is preferred. R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are bonded, (1) a halogen atom (e.g., a fluorine atom), (2) C 1-4 alkyl groups (e.g., methyl, ethyl); (3) C 1-4 Alkoxy groups (e.g., methoxy, ethoxy), (4) Haro C 1-4 Alkyl groups (e.g., trifluoromethyl, 2,2,2-trifluoroethyl, etc.) 1-4 alkyl group) and (5) Haro C 1-4 alkoxy group forming a cyclic group derived from a piperidyl group or a piperazinyl group, which may be substituted with a substituent selected from the group consisting of n is 1, and Compound (1), wherein m is 1 or 2.

[0077] [Compound (1-8)] In the formula (1), R 1 , R 2 , R 3 and R 4 are all identical pentafluorophenyl groups, 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl) groups, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl groups, or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl groups, R 5 But Fluoro C 1-4 Alkyl groups (e.g., 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, etc.) having a fluorine atom at the β-position 1-4 Among them, fluoro C alkyl groups having a fluorine atom at the β-position and three or more fluorine atoms, such as 2,2,2-trifluoroethyl and 2,2,3,3,3-pentafluoropropyl, are preferred. 2-4 An alkyl group is preferred. R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are bonded, (1) a halogen atom (e.g., a fluorine atom), (2) C 1-4 alkyl groups (e.g., methyl, ethyl); (3) C 1-4 Alkoxy groups (e.g., methoxy, ethoxy), (4) Haro C 1-4 Alkyl groups (e.g., trifluoromethyl, 2,2,2-trifluoroethyl, etc.) 1-4 alkyl group) and (5) Haro C 1-4 alkoxy group forming a cyclic group derived from a piperidyl group, which may be substituted with a substituent selected from the group consisting of n is 1, and Compound (1), wherein m is 1.

[0078] Preferred specific examples of compound (1) include the compounds of Examples 1, 4 to 21, 23, and 25 described below.

[0079] (Composition of the present invention) The composition of the present invention will now be described.

[0080] The composition of the present invention comprises the compound (1) (the compound of the present invention) and a compound of the following formula (2):

[0081] [ka]

[0082] [In the formula, R and R′ are each independently an optionally substituted C 1-30 alkyl group, optionally substituted C 3-15 cycloalkyl group or optionally substituted C 6-14 represents an aryl group.] The composition contains a compound represented by the formula (hereinafter also referred to as "compound (2)").

[0083] The composition containing compound (1) and compound (2) is not particularly limited as long as it contains both compounds, and may contain a compound in which compound (2) is coordinated with compound (1) to form a complex. The composition of the present invention is preferably a composition containing a complex formed by compound (1) and compound (2).

[0084] A preferred embodiment of compound (2) will be explained below. Each group in compound (2) will be explained below.

[0085] R and R′ are each independently an optionally substituted C 1-30 alkyl group, optionally substituted C 3-15 cycloalkyl group or optionally substituted C 6-14are each independently an aryl group, and preferably (1) a halogen atom, (2) C 1-30 Alkoxy groups and (3) Haro C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 1-30 alkyl groups; (1) a halogen atom, (2) C 1-30 alkyl groups, (3) C 1-30 alkoxy groups, (4) Haro C 1-30 Alkyl groups and (5) Haro C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 3-15 a cycloalkyl group; or (1) a halogen atom, (2) C 1-30 alkyl groups, (3) C 1-30 alkoxy groups, (4) Haro C 1-30 Alkyl groups and (5) Haro C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 6-14 aryl group, more preferably each independently C 1-30 Alkyl group; C 3-8 cycloalkyl groups (e.g., cyclopentyl, cyclohexyl, etc.); or (1) a halogen atom, (2) C 1-6 alkyl groups, (3) C 1-6 alkoxy groups, (4) Haro C 1-6 Alkyl groups and (5) Haro C 1-6 alkoxy group and more preferably, each independently represents a phenyl group optionally substituted with a substituent selected from the group consisting of 1-30Alkyl groups (preferably C groups such as methyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl) 1-18 alkyl group).

[0086] Preferred examples of compound (2) include dibutyl ether, dihexyl ether, dioctyl ether, didecyl ether, didodecyl ether, ditetradecyl ether, dihexadecyl ether, dioctadecyl ether, cyclopentyl methyl ether, diphenyl ether, and phenyloctadecyl ether.

[0087] In the composition of the present invention, the content of compound (2) relative to 1 mole of compound (1) is preferably in the range of 0.01 to 10 moles, more preferably in the range of 0.1 to 3 moles.

[0088] Specific preferred examples of the composition of the present invention include the compositions of Examples 2, 3, 24, and 26 to 34 described below.

[0089] Another embodiment of the composition of the present invention is a composition comprising the compound (1) (the compound of the present invention) and a compound of the following formula (3):

[0090] [ka]

[0091] [R in the formula 5 , R 6 and R 7 has the same meaning as above.] A compound represented by the formula (hereinafter also referred to as "compound (3)") (In the composition, compound (3) is an amine compound obtained by deprotonating the cation constituting compound (1)).

[0092] A preferred embodiment of compound (3) is R 6 and R 7are deprotonated when they are bonded to each other and together with the nitrogen atom to which they are attached form a cyclic group. 5 , R 6 and R 7 ) is the same as the preferred embodiment.

[0093] Suitable compounds (3) include the following compounds:

[0094] [Compound (3-1)] In the formula (3), R 5 is substituted with a phenyl group or a naphthyl group, each of which is substituted with one or more fluorine atoms 1-6 Alkyl group or fluoro C 1-6 an alkyl group (preferably a fluoro C group having a fluorine atom at the β-position and three or more fluorine atoms, such as 2,2,2-trifluoroethyl or 2,2,3,3,3-pentafluoropropyl); 2-4 is an alkyl group; and R 6 and R 7 However, each independently, (1) C optionally substituted with a halogen atom 6-14 aryl groups, (2) Halogen atoms and (3) C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 1-30 an alkyl group; or (1) a halogen atom, (2) C 1-30 alkyl groups, (3) C 1-30 alkoxy groups, (4) Haro C 1-30 Alkyl groups and (5) Haro C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 3-8 Compound (3), which is a cycloalkyl group.

[0095] [Compound (3-2)] In the formula (3), R 5 is a phenylmethyl group substituted with one or more fluorine atoms (e.g., a pentafluorophenylmethyl group) or a fluoroC 1-6 alkyl group, more preferably fluoro C 1-6 alkyl groups (e.g., 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, and the like) 1-6 Among them, fluoro C alkyl groups having a fluorine atom at the β-position and three or more fluorine atoms, such as 2,2,2-trifluoroethyl and 2,2,3,3,3-pentafluoropropyl, are preferred. 2-4 An alkyl group is preferred. R 6 and R 7 However, each independently, (1) C optionally substituted with a halogen atom (e.g., a fluorine atom) 6-14 aryl groups, (2) Halogen atoms and (3) C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 1-30 Compound (3), which is an alkyl group.

[0096] [Compound (3-3)] In the formula (3), R 5 But Fluoro C 1-6alkyl groups (e.g., 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, and the like) 1-6 Among them, fluoro C alkyl groups having a fluorine atom at the β-position and three or more fluorine atoms, such as 2,2,2-trifluoroethyl and 2,2,3,3,3-pentafluoropropyl, are preferred. 2-4 An alkyl group is preferred. R 6 and R 7 However, each independently, (1) C optionally substituted with a halogen atom (e.g., a fluorine atom) 6-14 aryl groups, (2) Halogen atoms and (3) C 1-30 alkoxy group C optionally substituted with a substituent selected from the group consisting of 1-30 Compound (3), which is an alkyl group.

[0097] [Compound (3-4)] In the formula (3), R 5 But Fluoro C 1-4 Alkyl groups (e.g., 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, etc.) having a fluorine atom at the β-position 1-4 Among them, fluoro C alkyl groups having a fluorine atom at the β-position and three or more fluorine atoms, such as 2,2,2-trifluoroethyl and 2,2,3,3,3-pentafluoropropyl, are preferred. 2-4 An alkyl group is preferred. R 6 and R7 are each independently optionally substituted with a halogen atom (e.g., a fluorine atom), 6-14 Aryl groups, halogen atoms and C 1-30 C optionally substituted with a substituent selected from the group consisting of alkoxy groups 1-30 Compound (3), which is an alkyl group.

[0098] [Compound (3-5)] In the formula (3), R 5 is substituted with a phenyl group or a naphthyl group, each of which is substituted with one or more fluorine atoms 1-6 Alkyl group or fluoro C 1-6 an alkyl group (preferably a fluoro C group having a fluorine atom at the β-position and three or more fluorine atoms, such as 2,2,2-trifluoroethyl or 2,2,3,3,3-pentafluoropropyl); 2-4 is an alkyl group; and R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are attached form an optionally substituted 3- to 8-membered monocyclic nitrogen-containing non-aromatic heterocycle.

[0099] [Compound (3-6)] In the formula (3), R 5 is a phenylmethyl group substituted with one or more fluorine atoms (e.g., a pentafluorophenylmethyl group) or a fluoroC 1-6 alkyl group, more preferably fluoro C 1-6 alkyl groups (e.g., 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, and the like) 1-6Among them, fluoro C alkyl groups having a fluorine atom at the β-position and three or more fluorine atoms, such as 2,2,2-trifluoroethyl and 2,2,3,3,3-pentafluoropropyl, are preferred. 2-4 An alkyl group is preferred. R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are bonded, (1) a halogen atom (e.g., a fluorine atom), (2) C 1-4 alkyl groups (e.g., methyl, ethyl); (3) C 1-4 Alkoxy groups (e.g., methoxy, ethoxy), (4) Haro C 1-4 Alkyl groups (e.g., trifluoromethyl, 2,2,2-trifluoroethyl, etc.) 1-4 alkyl group) and (5) Haro C 1-4 alkoxy group Compound (3) which forms azetidine, pyrrolidine, piperidine, piperazine or morpholine, optionally substituted with a substituent selected from the group consisting of:

[0100] [Compound (3-7)] In the formula (3), R 5 But Fluoro C 1-6 alkyl groups (e.g., 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, and the like) 1-6 Among them, fluoro C alkyl groups having a fluorine atom at the β-position and three or more fluorine atoms, such as 2,2,2-trifluoroethyl and 2,2,3,3,3-pentafluoropropyl, are preferred. 2-4 An alkyl group is preferred. R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are bonded, (1) a halogen atom (e.g., a fluorine atom), (2) C 1-4 alkyl groups (e.g., methyl, ethyl); (3) C 1-4 Alkoxy groups (e.g., methoxy, ethoxy), (4) Haro C 1-4 Alkyl groups (e.g., trifluoromethyl, 2,2,2-trifluoroethyl, etc.) 1-4 alkyl group) and (5) Haro C 1-4 alkoxy group Compound (3), which forms a piperidine or piperazine, optionally substituted with a substituent selected from the group consisting of:

[0101] [Compound (3-8)] In the formula (3), R 5 But Fluoro C 1-4 Alkyl groups (e.g., 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, etc.) having a fluorine atom at the β-position 1-4 Among them, fluoro C alkyl groups having a fluorine atom at the β-position and three or more fluorine atoms, such as 2,2,2-trifluoroethyl and 2,2,3,3,3-pentafluoropropyl, are preferred. 2-4 An alkyl group is preferred. R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are bonded, (1) a halogen atom (e.g., a fluorine atom), (2) C 1-4 alkyl groups (e.g., methyl, ethyl); (3) C 1-4 Alkoxy groups (e.g., methoxy, ethoxy), (4) Haro C 1-4 Alkyl groups (e.g., trifluoromethyl, 2,2,2-trifluoroethyl, etc.) 1-4 alkyl group) and (5) Haro C 1-4 alkoxy group Compound (3), which forms a piperidine, optionally substituted with a substituent selected from the group consisting of:

[0102] Preferred specific examples of compound (3) include the fluorine-containing alkylamines and fluorine-containing alkyl cyclic amines used in the synthesis of the compounds of Examples 1 and 4 to 21 described below.

[0103] In the composition of the present invention containing compound (1) and compound (3), the content of compound (3) relative to 1 mole of compound (1) is preferably in the range of 0.01 to 10 moles, more preferably in the range of 0.5 to 3 moles.

[0104] A specific preferred example of the composition of the present invention containing compound (1) and compound (3) is the composition of Example 22 described below.

[0105] The composition of the present invention containing the compound (1) and the compound (3) may further contain the compound (2) in addition to the compound (1) and the compound (3).

[0106] The preferred embodiments of the compound (2) that may be further contained are the same as the preferred embodiments and preferred specific examples of each group (R and R') in the compound (2). In addition, in the composition of the present invention containing the compound (1), the compound (2), and the compound (3), the contents of the compound (2) and the compound (3) per mole of the compound (1) are the same as those described above.

[0107] Among the compounds or compositions of the present invention, R 5 , R 6 and R 7When the total carbon number of the borate compound is 25 or more, it is soluble in an aliphatic hydrocarbon solvent at room temperature (15 to 30°C). In contrast, conventionally known borate compounds (e.g., hydrogenated tetrakis(pentafluorophenyl)borate, hydrogenated tetrakis(pentafluorophenyl)borate diethyl ether complex, lithium tetrakis(pentafluorophenyl)borate, etc.) are insoluble in aliphatic hydrocarbon solvents such as n-hexane. Therefore, known borate compounds are usually used in polymerization reactions as a solution in an aromatic hydrocarbon solvent. As a result, the aromatic hydrocarbon solvent must be removed, which increases the number of steps and results in significant commercial costs. In addition, they may be used in polymerization reactions as a suspension in an aliphatic hydrocarbon solvent. However, this suspension presents problems such as poor operability and the need for excessive amounts. Therefore, the compound or composition of the present invention, which is soluble in an aliphatic hydrocarbon solvent, is particularly useful as a cocatalyst for homogeneous polymerization reactions of olefins, dienes, and acetylenes using hydrocarbon solvents (especially aliphatic hydrocarbon solvents).

[0108] (Method for producing the compound of the present invention) The method for producing the compound (or composition) of the present invention (hereinafter also referred to as "the production method of the present invention") will be described below.

[0109] The method for producing the compound (or composition) of the present invention is not particularly limited, and it can be produced, for example, according to the following Production Methods 1 to 3, or the methods described in the Production Examples or Examples below. In particular, by producing a fluorine-containing alkylamine by the following production method, it is possible to obtain the compound (or composition) of the present invention by simpler operations, at lower cost, and in higher yield than conventional methods, and therefore it can be used as an industrial production method.

[0110] (Method 1) Production method 1 includes the steps of: (1) reacting dialkylamine compound (5) with fluoroalkylcarboxylic acid anhydride (6) in the presence of a base in a solvent that does not influence the reaction to obtain compound (7); (2) reducing compound (7) with a reducing agent in a solvent that does not influence the reaction to convert it into compound (3a); and (3) reacting compound (3a) with compound (4) in the presence of an acid in a solvent that does not influence the reaction to obtain compound (1a) (the compound of the present invention).

[0111] [ka]

[0112] (In the formula, R 8 is a C substituted with one or more fluorine atoms 6-14 C substituted with one or more substituents selected from the group consisting of aryl groups and fluorine atoms 1-29 represents an alkyl group, and the definitions of the other symbols are the same as those defined above.

[0113] (Process 1) Examples of the solvent used in this step include hydrocarbon solvents such as toluene, n-hexane, isohexane, n-heptane, n-octane, cyclohexane, and methylcyclohexane; ethers such as diethyl ether and tetrahydrofuran; halogenated solvents such as chloroform and dichloromethane; and mixed solvents thereof, and among these, a toluene-tetrahydrofuran mixed solvent is preferred.

[0114] The amount of compound (6) used is usually 1 to 3 moles, preferably 1 to 2 moles, more preferably 1.2 moles, per mole of compound (5).

[0115] Examples of the base used in this step include organic bases such as triethylamine, N,N-diisopropylethylamine, pyridine, and 2,6-lutidine, and among these, triethylamine is preferred. The amount of the base used is usually 1 to 3 moles, preferably 1 to 2 moles, and more preferably 1.2 moles, per mole of compound (5).

[0116] The reaction temperature is usually 0°C to 40°C, preferably 10°C to 35°C, more preferably room temperature (15°C to 30°C), and the reaction time is usually about 10 minutes to 10 hours, preferably about 30 minutes to 2 hours.

[0117] In Production Method 1, the compound (7) prepared as above can be used in Step 2 as is.

[0118] (Process 2) The solvent used in this step is not particularly limited, but examples thereof include ethers such as triglyme, tetrahydrofuran, tetrahydropyran, and dioxane, and among these, tetrahydrofuran is preferred.

[0119] The reducing agent used in this step includes boron-based hydrides, aluminum-based hydrides, etc. Specific examples of the reducing agent include, but are not limited to, sodium borohydride, lithium borohydride, lithium aluminum hydride, borane-tetrahydrofuran complex, borane-dimethyl sulfide complex, sodium borohydride / iodine, sodium borohydride / trifluoroacetic acid, etc. Among these, boron-based hydrides such as borane-tetrahydrofuran complex, borane-dimethyl sulfide complex, sodium borohydride / iodine, and sodium borohydride / trifluoroacetic acid are preferred. The amount of the reducing agent used, such as borane-tetrahydrofuran complex, borane-dimethyl sulfide complex, sodium borohydride / iodine, or sodium borohydride / trifluoroacetic acid, is usually 2 to 10 moles, and preferably 2 to 3 moles, per mole of compound (7).

[0120] The reaction temperature is the reflux temperature of the solvent usually used, preferably 40°C to 80°C. The reaction time is usually about 30 minutes to 10 hours, preferably about 1 to 4 hours.

[0121] (Step 3) The solvent used in this step is not particularly limited, but examples include halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, carbon tetrachloride, and trichloroethylene, and hydrocarbon solvents such as toluene, n-hexane, isohexane, n-heptane, n-octane, cyclohexane, and methylcyclohexane. Of these, dichloromethane, chloroform, n-hexane, isohexane, n-heptane, cyclohexane, and methylcyclohexane are preferred, and dichloroethane, chloroform, n-hexane, isohexane, n-heptane, and methylcyclohexane are particularly preferred.

[0122] Examples of the acid used in this step include protic acids such as hydrogen bromide, hydrogen chloride, and hydrogen iodide, among which hydrogen chloride is preferred. As hydrogen chloride, commercially available products (1.0 M hydrogen chloride-diethyl ether solution or hydrochloric acid) can be used as they are. The amount of the acid used is usually 1 to 5 moles, and preferably 1 to 2 moles, per mole of compound (3a).

[0123] The compound (4) used in this step is not particularly limited, and may be a commercially available product or a purified product, or may be prepared by a method known per se. Specific examples of compound (4) include lithium tetrakis(pentafluorophenyl)borate, potassium tetrakis(pentafluorophenyl)borate, lithium tetrakis(heptafluoronaphthyl)borate, potassium tetrakis(heptafluoronaphthyl)borate, chloromagnesium tetrakis(pentafluorophenyl)borate, chloromagnesium tetrakis(heptafluoronaphthyl)borate, bromomagnesium tetrakis(pentafluorophenyl)borate, bromomagnesium tetrakis(heptafluoronaphthyl)borate, lithium tetrakis(nonafluorobiphenyl)borate, potassium tetrakis(nonafluorobiphenyl)borate, chloromagnesium tetrakis(nonafluorobiphenylyl)borate, bromomagnesium tetrakis(nonafluorobiphenyl)borate, a tri-diethyl ether complex of lithium tetrakis(pentafluorophenyl)borate, and a mono-diethyl ether complex of lithium tetrakis(pentafluorophenyl)borate. The amount of compound (4) used is usually 1 to 1.5 moles, preferably 1 mole, per mole of compound (3a).

[0124] The reaction temperature is usually 0° C. to 80° C., preferably 15° C. to 60° C., and the reaction time is usually about 10 minutes to 10 hours, preferably about 1 to 3 hours.

[0125] (Method 2) In the production method 2, the reaction in step 3 of the production method 1 is carried out in accordance with the formula (2):

[0126] [ka]

[0127] [The definitions of each symbol in the formula are the same as those defined above.] This method is a method for obtaining a composition containing compound (1a) and compound (2) (the composition of the present invention) by carrying out the reaction in the presence of a compound (compound (2)) represented by the following formula:

[0033] Except for adding compound (2), the method can be carried out in the same manner as in step 3 of the above-mentioned Production Method 1.

[0128] The amount of compound (2) used is usually 0.01 to 10 mol, preferably 0.1 to 3 mol, per 1 mol of compound (4).

[0129] (Method 3) Production Method 3 is a method for obtaining a composition containing compound (1a) and compound (3a) (the composition of the present invention) by using an excess amount of compound (3a) in the reaction of step 3 of Production Method 1. Except for using an excess amount of compound (3a), Production Method 3 can be carried out in the same manner as step 3 of Production Method 1.

[0130] The amount of compound (3a) used is usually 1.01 to 11 mol, preferably 1.1 to 4 mol, per 1 mol of compound (4).

[0131] The compound (compound (1)) or composition of the present invention is a compound or composition derived from a fluorine-containing alkylamine, and therefore does not substantially contain compounds that can act as catalyst poisons, such as highly basic and nucleophilic amine compounds. Therefore, it is useful as a cocatalyst for the polymerization of olefins, dienes, and acetylenes.

[0132] The present invention encompasses a method for producing a polymer, which comprises polymerizing at least one monomer selected from the group consisting of olefins, dienes, and acetylenes using the compound of the present invention (compound (1)) or the composition of the present invention as a co-catalyst.

[0133] Specifically, the production of a polymer using the compound (compound (1)) (or composition) of the present invention as a co-catalyst can be carried out, for example, in accordance with the method described in the Test Examples below. [Example]

[0134] The present invention will be specifically explained below with reference to Examples, Production Examples, and Test Examples, but the present invention is not limited to these Examples, etc. % indicates mol / mol% for yield, and % by weight for other values unless otherwise specified. Furthermore, room temperature indicates a temperature of 15°C to 30°C unless otherwise specified.

[0135] Unless otherwise specified, solvents and reagents used in the following examples were purchased from distributors such as Sigma-Aldrich, Tokyo Chemical Industry Co., Ltd., Fujifilm Wako Pure Chemical Industries, Ltd., Junsei Chemical Co., Ltd., Kanto Chemical Co., Ltd., and Combi-Blocks. Deuterated solvents used in NMR measurements were purchased from Cambridge Isotope Laboratory. The following instruments were used for the analysis: 1 H-NMR and 19 F-NMR: 400YH manufactured by JEOL Ltd. (JEOL)

[0136] [Manufacturing Example 1] Synthesis of N,N-dioctadecyl-2,2,2-trifluoroacetamide N,N-Dioctadecylamine (2.0 g, 3.8 mmol) and triethylamine (0.5 g, 5.0 mmol) were dissolved in tetrahydrofuran (10 mL), and trifluoroacetic anhydride (1.0 g, 4.8 mmol) was added at room temperature. The mixture was stirred at room temperature for 1 hour, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with 1 M hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to give the title compound (1.87 g, 79%). 1 H NMR (CDCl3) δ: 0.89 (6H, t), 1.26-1.43 (60H, m), 1.56-1.59 (4H, m), 3.30-3.37 (4H, m); 19 F NMR (CDCl3) δ: -70.1 (3F, s).

[0137] [Manufacturing Example 2] Synthesis of N,N-dioctadecyl-2,2,2-trifluoroethylamine N,N-Dioctadecyl-2,2,2-trifluoroacetamide (1.0 g, 1.6 mmol) obtained in Preparation Example 1 was dissolved in tetrahydrofuran (10 mL), and a 1 M solution of borane-tetrahydrofuran complex in tetrahydrofuran (5 mL) was added, followed by refluxing for 3 hours. After ice-cooling the mixture, water was carefully added dropwise, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give the title compound (0.87 g, 88%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.25-1.40 (60H, m), 1.42-1.44 (4H, m), 2.56 (4H, t), 3.00 (2H, q); 19 F NMR (CDCl3) δ: -71.3 (3F, t).

[0138] [Manufacturing Example 3] Synthesis of N,N-dioctadecyl-2,2,2-trifluoroethylamine hydrochloride N,N-Dioctadecyl-2,2,2-trifluoroethylamine (1.0 g, 1.7 mmol) obtained in Preparation Example 2 was dissolved in n-hexane (10 mL), and 1.0 M hydrogen chloride-diethyl ether solution (10 mL) was added, followed by stirring at room temperature for 3 hours. The resulting precipitate was collected by filtration, washed with n-hexane, and dried under reduced pressure to obtain the title compound (0.987 g, 93%). 1 H NMR (CDCl3) δ: 0.88 (6H, t),1.19-1.40 (60H, m), 1.93 (4H, br s), 3.15 (4H, br s), 3.77 (2H, q); 19 F NMR (CDCl3) δ: -63.4 (3F, t).

[0139] [Example 1] Synthesis of N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate N,N-Dioctadecyl-2,2,2-trifluoroethylamine hydrochloride (0.32 g, 0.5 mmol) obtained in Preparation Example 3 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (0.45 g, 0.5 mmol) was added. The mixture was stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to obtain the title compound (0.62 g, 97%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.19-1.40 (60H, m), 1.94 (4H, br s), 3.15 (4H, br s), 3.77 (2H, q); 19 F NMR (CDCl3) δ: -66.7 (3F, t), -134.1(8H, m), -163.2 (4H, m), -1675.5 (8H, m).

[0140] [Example 2] Synthesis of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and ditetradecyl ether The title composition was obtained by mixing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (0.30 g, 0.22 mmol) obtained in Example 1 and ditetradecyl ether (0.09 g, 0.22 mmol). 1 H NMR (CDCl3) δ: 0.85-0.90 (12H, m), 1.20-1.33 (104H, m), 1.52-1.68 (8H, m), 3.14-3.18 (4H, m), 3.40 (4H, t), 3.62 (2H, q); 19F NMR (CDCl3) δ: -66.8 (3F, br s), -134.0 (8F, m), -163.2 (4F, t), -167.5 (8F, m).

[0141] N-hexane was added to the composition obtained in Example 2 to prepare a 20 wt % n-hexane solution, which was confirmed to be a homogeneous solution.

[0142] Isohexane was added to the composition obtained in Example 2 to prepare a 20 wt % isohexane solution, which was confirmed to be a homogeneous solution.

[0143] N-heptane was added to the composition obtained in Example 2 to prepare a 20 wt % n-heptane solution, which was confirmed to be a homogeneous solution.

[0144] ISOPAR E (registered trademark) was added to the composition obtained in Example 2 to prepare a 20 wt % ISOPAR E (registered trademark) solution, and it was confirmed that the solution was homogeneous.

[0145] Cyclohexane was added to the composition obtained in Example 2 to prepare a 20 wt % cyclohexane solution, which was confirmed to be a homogeneous solution.

[0146] Methylcyclohexane was added to the composition obtained in Example 2 to prepare a 20 wt % methylcyclohexane solution, which was confirmed to be a homogeneous solution.

[0147] [Example 3] Synthesis of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and dibutyl ether The title composition was obtained by mixing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (300 mg, 0.23 mmol) obtained in Example 1 and dibutyl ether (62 mg, 0.46 mmol). 1H NMR (CDCl3) δ: 0.87 (6H, t), 0.92 (12H, t), 1.20-1.68 (78H, m), 3.14-3.18 (4H, m), 3.41 (8H, t), 3.62 (2H, q); 19 F NMR (CDCl3) δ: -66.7 (3F, s), -134.0 (8F, s), -163.3 (4F, t), -167.5 (8H, m).

[0148] It was confirmed that the composition obtained in Example 3 was soluble in n-hexane at 30% by weight.

[0149] [Example 4] Synthesis of N,N-dioctadecyl-N-(2,2,2-trifluoroethyl)ammonium tetrakis(2-heptafluoronaphthyl)borate A diethyl ether solution (46.9 wt%) (1.0 g, 0.46 mmol) of lithium tetrakis(2-heptafluoronaphthyl)borate prepared by a method known per se (see, for example, International Publication No. 2007 / 070770) and dioctadecyl-N-(2,2,2-trifluoroethyl)ammonium hydrochloride (0.292 g, 0.46 mmol) were added to 10 mL of dichloromethane and stirred at room temperature. Water was then added to separate the organic layer. Anhydrous sodium sulfate was added to dry the organic layer, and the organic layer was concentrated to obtain the title compound (0.78 g) as a yellow solid. 1 H NMR (CDCl3) δ: 0.87 (6H, t), 1.24 (60H, m), 1.62 (4H, m), 3.20 (4H, t), 3.69 (2H, q); 19 F NMR (CDCl3) δ: -63.3 (3F, t), -106.7 (4F, m), -123.4 (4F, m), -143.3 (4F, m), -146.8 (4F, m), -152.5 (4F, m), -155.8 (4F, m), -157.3 (4F, m).

[0150] [Manufacturing Example 4] Synthesis of N-benzyl-N-methyl-2,2,2-trifluoroethylamine N-Methylbenzylamine (Kanto Chemical Co., Inc.) (1.1 g, 9.1 mmol) and triethylamine (1.5 g, 15 mmol) were mixed, and 2,2,2-trifluoroethyl trifluoromethanesulfonate (2.2 g, 9.5 mmol) was added at room temperature. The mixture was stirred overnight, then 1 M hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (n-hexane / ethyl acetate = 98 / 2 to 90 / 10) to give the title compound (1.65 g, 86%). 1 H NMR (CDCl3) δ: 2.43 (3H, s), 3.03 (2H, q), 3.71 (2H, s), 7.25-7.34 (5H, m); 19 F NMR (CDCl3) δ: -69.9 (3F, t).

[0151] [Manufacturing Example 5] Synthesis of N-benzyl-N-methyl-2,2,2-trifluoroethylamine hydrochloride A 1 M hydrogen chloride-diethyl ether solution (20 mL) was added to N-benzyl-N-methyl-2,2,2-trifluoroethylamine (1.65 g, 8.1 mmol) obtained in Production Example 4. The mixture was stirred at room temperature for 1 hour, and the solvent was evaporated under reduced pressure to obtain the title compound (1.97 g, 100%). 1 H NMR (CDCl3) δ: 2.96 (3H, s), 3.70-3.81 (2H, m), 4.46 (2H, s), 7.41-7.52 (3H, m), 7.59-7.67 (2H, m); 19 F NMR (CDCl3) δ: -63.2 (3F, br s).

[0152] [Example 5] Synthesis of N-benzyl-N-methyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate N-benzyl-N-methyl-2,2,2-trifluoroethylamine hydrochloride (0.30 g, 1.25 mmol) obtained in Preparation Example 5 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (1.10 g, 1.21 mol) was added and stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to obtain the title compound (1.07 g, 93%). 1 H NMR (CDCl3) δ: 2.97 (3H, s), 3.60 (2H, q), 4.33 (2H, s), 7.41-7.57 (5H, m); 19 F NMR (CDCl3) δ: -65.3 (3F, t), -134.0 (8H, m), -163.4 (4F, t), -167.6 (8F, m).

[0153] [Manufacturing Example 6] Synthesis of N,N-bis(pentafluorophenylmethyl)-1-butylamine Pentafluorobenzaldehyde (3.0 g, 15.3 mmol), 1-butylamine (0.50 g, 7.0 mmol), and acetic acid (0.40 g) were dissolved in tetrahydrofuran (30 mL), and sodium triacetoxyborohydride (3.50 g, 17.0 mmol) was added. The mixture was stirred at room temperature for 15 hours. The reaction mixture was made basic with saturated aqueous sodium bicarbonate and extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0 to 90 / 10) to give the title compound (2.65 g, 90%). 1H NMR (CDCl3) δ: 0.81 (3H, t), 1.17-1.23 (2H, m), 1.43-1.48 (2H, m), 2.40 (2H, t), 3.71 (4H, s). 19 F NMR (CDCl3) δ: -143.8 (4F, dd), -156.1 (2H, t), -163.4 (4F, m).

[0154] [Manufacturing Example 7] Synthesis of N,N-bis(pentafluorophenylmethyl)-1-butylamine hydrochloride N,N-bis(pentafluorophenylmethyl)-1-butylamine (2.30 g, 5.1 mmol) obtained in Production Example 6 was dissolved in n-hexane (30 mL), and 1 M hydrogen chloride-diethyl ether (20 mL) was added. The mixture was stirred at room temperature for 1 hour, and the solvent was evaporated under reduced pressure to give the title compound (1.98 g, 80%). 1 H NMR (CDCl3) δ: 0.99 (3H, t), 1.38-1.43 (2H, m), 2.03-2.11 (2H, m), 2.99-3.03 (2H, m), 4.36 (4H, m); 19 F NMR (CDCl3) δ: -136.8 (4F, d), -147.9 (2F, t), -159.5 (4H, m).

[0155] [Example 6] Synthesis of N,N-bis(pentafluorophenylmethyl)-1-butylammonium tetrakis(pentafluorophenyl)borate N,N-bis(pentafluorophenylmethyl)-1-butylamine hydrochloride (0.93 g, 1.02 mmol) obtained in Preparation Example 7 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (0.50 g, 1.03 mol) was added. After stirring at room temperature for 1 hour, the insoluble material was filtered off. The insoluble material was dissolved in water and dichloromethane, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain the title compound (0.65 g, 65%). 1 H NMR (DMSO-d6) δ: 0.77 (3H, t), 1.13-1.22 (2H, m), 1.42-1.48 (2H, m), 2.43-2.50 (2H, m), 4.62 (2H, br s); 19 F NMR (DMSO-d6) δ: -132.7 (8F, m), -143.0 (4F, br s), -156.3 (2F, br s), -161.7 (4F, t), -163.3 (4F, br s), -166.2 (8F, m).

[0156] [Manufacturing Example 8] Synthesis of N,N-dioctadecyl-(2,3,4,5,6-pentafluorophenyl)methyl-1-amine Pentafluorobenzaldehyde (0.50 g, 2.60 mmol) and N,N-dioctadecylamine (1.50 g, 2.87 mmol) were dissolved in tetrahydrofuran (30 mL), sodium triacetoxyborohydride (1.00 g, 4.72 mmol) was added, and the mixture was stirred at room temperature for 15 hours. The reaction mixture was made basic with saturated aqueous sodium bicarbonate and extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to give the title compound (1.05 g, 52%). 1H NMR (CDCl3) δ: 0.88 (6H, t), 1.20-1.30 (64H, m), 2.38 (4H, t), 3.69 (2H, s); 19 F NMR (CDCl3) δ: -143.0 (8F, m), -157.1 (4F, m), -163.8 (8F, m).

[0157] [Manufacturing Example 9] Synthesis of N,N-dioctadecyl-(2,3,4,5,6-pentafluorophenyl)methyl-1-amine hydrochloride N,N-Dioctadecyl-(2,3,4,5,6-pentafluorophenyl)methyl-1-amine (2.95 g, 4.2 mmol) obtained in Preparation Example 8 was dissolved in n-hexane (30 mL), and 1 M hydrogen chloride-diethyl ether (20 mL) was added. The reaction mixture was stirred at room temperature for 1 hour, and the solvent was evaporated under reduced pressure to give the title compound (3.05 g, 98%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.21-1.35 (60H, m), 1.88-1.93 (4H, m), 2.92-3.02 (4H, m), 4.32 (2H, s); 19 F NMR (CDCl3) δ: -137.4 (1F, d), -148.6 (2F, t), -159.6 (2F, m).

[0158] [Example 7] Synthesis of N,N-dioctadecyl-(2,3,4,5,6-pentafluorophenyl)methyl-1-ammonium tetrakis(pentafluorophenyl)borate N,N-Dioctadecyl-(2,3,4,5,6-pentafluorophenyl)methyl-1-amine hydrochloride (0.50 g, 0.68 mmol) obtained in Preparation Example 9 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (0.58 g, 0.60 mol) was added and stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure at 45°C to give the title compound (0.83 g, 98%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.21-1.30 (60H, m), 1.73 (4H, br s), 3.05 (4H, br s), 4.27 (2H, s); 19 F NMR (CDCl3) δ: -134.1 (8H, br s), -139.8 (2H, br s), -146.0 (1H, br s), -158.5 (2H, br s), -163.6 (4H, t), -167.8 (8H, t).

[0159] Methylcyclohexane was added to the compound of Example 7 to prepare a 10 wt % methylcyclohexane solution, which was confirmed to be a homogeneous solution.

[0160] [Manufacturing Example 10] Synthesis of N,N-dicyclohexyl-2,2,2-trifluoroacetamide Dicyclohexylamine (2.0 g, 11 mmol) and triethylamine (1.2 g, 12 mmol) were dissolved in tetrahydrofuran (50 mL), and trifluoroacetic anhydride (2.3 g, 11 mmol) was added dropwise at room temperature. After stirring at room temperature for 1 hour, 1 M hydrochloric acid was added. The mixture was extracted with n-hexane, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0 to 90 / 10) to obtain the title compound (2.65 g, 87%). 1H NMR (CDCl3) δ: 1.08-1.84 (14H, m), 2.38-2.48 (4H, m), 3.01-3.08 (2H, m), 3.65-3.68 (2H, m); 19 F NMR (CDCl3) δ: -70.3 (3F, s).

[0161] [Manufacturing Example 11] Synthesis of N,N-dicyclohexyl-2,2,2-trifluoroethylamine N,N-Dicyclohexyl-2,2,2-trifluoroacetamide (2.65 g, 9.56 mmol) obtained in Preparation Example 10 was dissolved in tetrahydrofuran (30 mL) and a 1.0 M borane-tetrahydrofuran complex solution (20 mL) in tetrahydrofuran was added at room temperature. The reaction mixture was stirred at 60°C for 5 hours. The mixture was allowed to cool to room temperature, and water (30 mL) was carefully added dropwise under ice cooling. The mixture was extracted with n-hexane, washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to give the title compound (2.35 g, 93%). 1 H NMR (CDCl3) δ: 0.87-1.25 (10H, m), 1.56-1.78 (10H, m), 2.51-2.57 (2H, m), 3.11 (2H, q); 19 F NMR (CDCl3) δ: -72.9 (3F, t).

[0162] [Manufacturing Example 12] Synthesis of N,N-dicyclohexyl-2,2,2-trifluoroethylamine hydrochloride N,N-Dicyclohexyl-2,2,2-trifluoroethylamine (2.35 g, 8.9 mmol) obtained in Preparation 11 was dissolved in n-hexane (30 mL), and 1.0 M hydrogen chloride-diethyl ether solution (20 mL) was added thereto, followed by stirring for 1 hour. The reaction mixture was concentrated under reduced pressure to give the title compound (2.65 g, 99%). 1 H NMR (CDCl3) δ: 1.18-1.40 (6H, m), 1.69-1.81 (6H, m), 1.95-2.07 (4H, m), 2.19 (4H, br s), 3.44-3.52 (2H, m), 3.76 (2H, q); 19 F NMR (CDCl3) δ: -59.7 (3F, t).

[0163] [Example 8] Synthesis of N,N-dicyclohexyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate N,N-Dicyclohexyl-2,2,2-trifluoroethylamine hydrochloride (0.33 g, 1.1 mmol) obtained in Preparation Example 12 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (1.0 g, 1.1 mmol) was added. The mixture was stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to obtain the title compound (0.98 g, 94%). 1 H NMR (CDCl3) δ: 1.13-2.06 (20H, m), 3.42-3.48 (2H, m), 3.66 (2H, q); 19 F NMR (CDCl3) δ: -66.0 (3F, s), -134.0 (8H, m), -163.8 (4F, m), -167.8 (8F, m).

[0164] [Manufacturing Example 13] Synthesis of N,N-dihexyl-2,2-difluoroethylamine 1-Hexanal (2.5 g, 25 mmol) and 2,2-difluoroethylamine (1 g, 12 mmol) were dissolved in tetrahydrofuran (30 mL), sodium triacetoxyborohydride (6 g, 28 mmol) was added, and the mixture was stirred at room temperature for 15 hours. The reaction mixture was made basic with saturated aqueous sodium bicarbonate and extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to give the title compound (2.98 g, 97%). 1 H NMR (CDCl3) δ: 0.87 (6H, t), 1.21-1.44 (16H, m), 2.46-2.50 (4H, m), 2.76 (2H, dt), 5.74 (1H, tt); 19 F NMR (CDCl3) δ: -120.4 (2F, dt).

[0165] [Manufacturing Example 14] Synthesis of N,N-dihexyl-2,2-difluoroethylamine hydrochloride N,N-Dihexyl-2,2-difluoroethylamine (2.95 g, 11.8 mmol) obtained in Production Example 13 was dissolved in n-hexane (30 mL), and 1.0 M hydrogen chloride-diethyl ether solution (20 mL) was added thereto, followed by stirring for 1 hour. The reaction mixture was concentrated under reduced pressure to give the title compound (3.05 g, 90%). 1 H NMR (CDCl3) δ: 0.90 (6H, t), 1.30-1.41 (12H, m), 1.78-1.86 (4H, m), 3.07-3.17 (4H, m), 3.36-3.45 (2H, m), 6.78 (1H, tt); 19 F NMR (CDCl3) δ: -118.3 (2H, dt).

[0166] [Example 9] Synthesis of N,N-dihexyl-2,2-difluoroethylammonium tetrakis(pentafluorophenyl)borate N,N-Dihexyl-2,2-difluoroethylamine hydrochloride (0.40 g, 1.4 mmol) obtained in Preparation Example 14 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (1.25 g, 1.38 mmol) was added and stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to obtain the title compound (1.04 g, 81%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.24-1.36 (12H, m), 1.64-1.72 (4H, m), 3.16-3.21 (4H, m), 3.40-3.48 (2H, m), 6.18 (1H, t); 19 F NMR (CDCl3) δ: -65.3 (2F, dt), -134.1 (8H, m), -163.4 (4F, t), -167.6 (8F, m).

[0167] [Manufacturing Example 15] Synthesis of N,N-dihexyl-3,3,3-trifluoropropylamine 1-Hexanal (1 g, 10 mmol), 2,2-difluoroethylamine (0.5 g, 4.0 mmol), and acetic acid (0.3 mL) were dissolved in tetrahydrofuran (30 mL), and sodium triacetoxyborohydride (2.5 g, 12 mmol) was added. The mixture was stirred at room temperature for 15 hours. The mixture was made basic with saturated aqueous sodium bicarbonate and extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to give the title compound (1.35 g, 100%). 1H NMR (CDCl3) δ: 0.87-0.92 (6H, m), 1.25-1.45 (16H, m), 2.16-2.29 (2H, m), 2.36-2.41 (4H, m), 2.67-2.71 (2H, m); 19 F NMR (CDCl3) δ: -66.5 (3F, t).

[0168] [Manufacturing Example 16] Synthesis of N,N-dihexyl-3,3,3-trifluoropropylamine hydrochloride N,N-Dihexyl-3,3,3-trifluoropropylamine (1.0 g, 3.55 mmol) obtained in Production Example 15 was dissolved in n-hexane (30 mL), and 1.0 M hydrogen chloride-diethyl ether solution (20 mL) was added thereto, followed by stirring for 1 hour. The reaction mixture was concentrated under reduced pressure to give the title compound (1.1 g, 97%). 1 H NMR (CDCl3) δ: 0.90 (6H, t), 1.31-1.39 (12H, m), 1.77-1.84 (4H, m), 2.87-2,99 (1H, m), 3.00-3.05 (3H, m), 3.18 (1H, m); 19 F NMR (CDCl3) δ: -66.6 (3F, t)

[0169] [Example 10] Synthesis of N,N-dihexyl-3,3,3-trifluoropropylammonium tetrakis(pentafluorophenyl)borate N,N-Dihexyl-3,3,3-trifluoropropylamine hydrochloride (0.30 g, 0.94 mmol) obtained in Preparation Example 16 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (0.85 g, 0.94 mmol) was added. The mixture was stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to obtain the title compound (0.90 g, 100%). 1H NMR (CDCl3) δ: 0.87 (6H, t), 1.21-1.35 (12H, m), 1.63-1.69 (4H, m), 2.56-2.61 (2H, m), 3.07 (4H, m), 3.30-3.35 (2H, m); 19 F NMR (CDCl3) δ: -66.4 (3F, t), -134.1 (8F, br s), -163.4 (4F, t), -167.7 (8F, m).

[0170] [Manufacturing Example 17] Synthesis of N,N-dioctadecyl-2,2,3,3,3-pentafluoropropylamine 1-Octadecanal (1.5 g, 5.59 mmol), 2,2,3,3,3-pentafluoropropylamine (0.40 g, 2.7 mmol), and acetic acid (0.3 mL) were dissolved in tetrahydrofuran (30 mL), and sodium triacetoxyborohydride (1.2 g, 5.7 mmol) was added and stirred at room temperature for 15 hours. The mixture was made basic with saturated aqueous sodium bicarbonate and extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to give the title compound (1.65 g, 100%). 1 H NMR (CDCl3) δ:0.88 (6H, t), 1.25-1.43 (64H, m), 2.56 (4H, br s), 2.95-3.10 (2H, m); 19 F NMR (CDCl3) δ: -85.2 (3F, br s), -121.2 (2F, br s).

[0171] [Manufacturing Example 18] Synthesis of N,N-dioctadecyl-2,2,3,3,3-pentafluoropropylamine hydrochloride N,N-Dioctadecyl-2,2,3,3,3-pentafluoropropylamine (1.5 g, 2.29 mmol) obtained in Preparation Example 17 was dissolved in n-hexane (30 mL), and 1.0 M hydrogen chloride-diethyl ether solution (20 mL) was added thereto, followed by stirring for 1 hour. The reaction mixture was concentrated under reduced pressure to give the title compound (1.45 g, 92%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.19-1.40 (64H, m), 1.94 (4H, br s), 3.22 (4H, t), 3.77 (2H, t); 19 F NMR (CDCl3) δ: -86.3 (3F, br s), -117.8 (2H, t).

[0172] [Example 11] Synthesis of N,N-dioctadecyl-2,2,3,3,3-pentafluoropropylammonium tetrakis(pentafluorophenyl)borate N,N-Dioctadecyl-2,2,3,3,3-pentafluoropropylamine hydrochloride (0.50 g, 0.72 mmol) obtained in Preparation Example 18 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (0.65 g, 0.72 mmol) was added. The mixture was stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to give the title compound (0.89 g, 93%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.18-1.31 (64H, m), 1.72 (4H, br s), 3.21-3.23 (4H, m), 3.67 (2H, t); 19 F NMR (CDCl3) δ: -85.9 (3F, t), -118.6 (2F, m), -134.0 (8F, br s), -163.4 (4F, t), -167.6 (8F, m).

[0173] Methylcyclohexane was added to the compound of Example 11 to prepare a 10 wt % methylcyclohexane solution, which was confirmed to be a homogeneous solution.

[0174] [Manufacturing Example 19] Synthesis of N,N-dioctyl-2,2,2-trifluoroethylamine 1-Octanal (5.5 g, 43 mmol), 2,2,2-trifluoroethylamine (2.0 g, 20 mmol), and acetic acid (0.5 mL) were dissolved in tetrahydrofuran (50 mL), and sodium triacetoxyborohydride (10 g, 47 mmol) was added. The mixture was stirred at room temperature for 15 hours. The reaction mixture was made basic with saturated aqueous sodium bicarbonate and extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to give the title compound (5.56 g, 85%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.27-1.43 (24H, m), 2.56 (4H, t), 3.00 (2H, q); 19 F NMR (CDCl3) δ: -71.3 (3F, s).

[0175] [Manufacturing Example 20] Synthesis of N,N-dioctyl-2,2,2-trifluoroethylamine hydrochloride N,N-Dioctyl-2,2,2-trifluoroethylamine (1.5 g, 4.64 mmol) obtained in Preparation 19 was dissolved in n-hexane (30 mL), and 1.0 M hydrogen chloride-diethyl ether solution (20 mL) was added thereto and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure to give the title compound (1.45 g, 87%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.26-1.34 (20H, m), 1.94 (4H, br s), 3.15 (4H, br s), 3.78 (2H, q); 19 F NMR (CDCl3) δ: -63.4 (3F, t).

[0176] [Example 12] Synthesis of N,N-dioctyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate N,N-Dioctyl-2,2,2-trifluoroethylamine hydrochloride (0.50 g, 1.39 mmol) obtained in Preparation Example 20 was dissolved in chloroform (10 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (1.25 g, 1.38 mmol) was added and stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to obtain the title compound (1.25 g, 87%). 1 H NMR (CDCl3) δ: 0.86 (6H, t), 1.19-1.29 (20H, m), 1.67-1.73 (4H, m), 3.18-3.22 (4H, m), 3.62-3.67 (2H, m); 19 F NMR (CDCl3) δ: -66.0 (3F, t), -134.1 (8F, br s), -163.4 (4F, t), -167.6 (8F, m).

[0177] [Manufacturing Example 21] Synthesis of N,N-didodecyl-2,2,2-trifluoroethylamine 1-Dodecanal (5.5 g, 30 mmol), 2,2,2-trifluoroethylamine (1.5 g, 15 mmol), and acetic acid (0.5 mL) were dissolved in tetrahydrofuran (50 mL), and sodium triacetoxyborohydride (7 g, 33 mmol) was added. The mixture was stirred at room temperature for 15 hours. The reaction mixture was made basic with saturated aqueous sodium bicarbonate and extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to give the title compound (6.5 g, 99%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.26-1.43 (40H, m), 2.56 (4H, t), 3.00 (2H, q); 19 F NMR (CDCl3) δ: -71.3 (3F, t).

[0178] [Manufacturing Example 22] Synthesis of N,N-didodecyl-2,2,2-trifluoroethylamine hydrochloride N,N-didodecyl-2,2,2-trifluoroethylamine (0.5 g, 1.06 mmol) obtained in Preparation 21 was dissolved in n-hexane (30 mL), and 1.0 M hydrogen chloride-diethyl ether solution (20 mL) was added and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure to give the title compound (2.09 g, 96%). 1 H NMR (CDCl3) δ: 0.87 (6H, t), 1.26-1.34 (36H, m), 1.93 (4H, br s), 3.15 (4H, br s), 3.78 (2H, q); 19 F NMR (CDCl3) δ: -63.4 (3F, t).

[0179] [Example 13] Synthesis of N,N-didodecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate N,N-didodecyl-2,2,2-trifluoroethylamine hydrochloride (0.50 g, 1.06 mmol) obtained in Preparation Example 22 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (0.96 g, 1.06 mmol) was added. The mixture was stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to give the title compound (1.19 g, 100%). 1 H NMR (CDCl3) δ: 0.87 (6H, t), 1.19-1.29 (36H, m), 1.65-1.71 (4H, m), 3.15-3.22 (4H, m), 3.65 (2H, q); 19 F NMR (CDCl3) δ: -66.4 (3F, br s), -134.0 (8F, m), -163.4 (4F, t), -167.6 (8F, m).

[0180] Methylcyclohexane was added to the compound of Example 13 to prepare a 10 wt % methylcyclohexane solution, which was confirmed to be a homogeneous solution.

[0181] [Manufacturing Example 23] Synthesis of N,N-dioctadecyl-2,2-difluoroethylamine 1-Octadecanal (3.0 g, 11 mmol), 2,2-difluoroethylamine (0.45 g, 5.6 mmol), and acetic acid (0.3 mL) were dissolved in tetrahydrofuran (30 mL), and sodium triacetoxyborohydride (2.50 g, 12 mmol) was added. The mixture was stirred at room temperature for 15 hours. The reaction mixture was made basic with saturated aqueous sodium bicarbonate and extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to give the title compound (2.9 g, 89%). 1H NMR (CDCl3) δ: 0.89(6H, t), 1.17-1.47 (64H, m), 2.49 (4H, t), 2.77 (2H, dt), 5.75 (1H, t); 19 F NMR (CDCl3) δ: -120.4 (2H, dt).

[0182] [Manufacturing Example 24] Synthesis of N,N-dioctadecyl-2,2-difluoroethylamine hydrochloride N,N-Dioctadecyl-2,2-difluoroethylamine (2.0 g, 3.41 mmol) obtained in Preparation Example 23 was dissolved in n-hexane (30 mL), and 1.0 M hydrogen chloride-diethyl ether solution (20 mL) was added and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure to give the title compound (2.09 g, 98%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.18-1.41 (58H, m), 1.79-1.83 (4H, m), 3.07-3.11 (4H, m), 3.32-3.38 (4H,m), 6.78(1H, t); 19 F NMR (CDCl3) δ: -118.2 (2F, dt).

[0183] [Example 14] Synthesis of N,N-dioctadecyl-2,2-difluoroethylammonium tetrakis(pentafluorophenyl)borate N,N-Dioctadecyl-2,2-difluoroethylamine hydrochloride (0.50 g, 0.80 mmol) obtained in Preparation Example 24 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (0.72 g, 0.79 mmol) was added. The mixture was stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to give the title compound (0.97 g, 97%). 1H NMR (CDCl3) δ: 0.86 (3H, t), 1.17-1.43 (58H, m), 1.71 (4H, br s), 3.16 (4H, br s), 3.42 (2H, t), 6.25 (1H, t); 19 F NMR (CDCl3) δ: -121.3 (2F, d), -134.0 (8F, d), -163.4 (8F, t), -167.6 (8F, t).

[0184] Methylcyclohexane was added to the compound of Example 14 to prepare a 10 wt % methylcyclohexane solution, which was confirmed to be a homogeneous solution.

[0185] [Manufacturing Example 25] Synthesis of 1-(2,2,2-trifluoroethyl)piperidine hydrochloride 1-(2,2,2-Trifluoroethyl)piperidine (1.5 g, 8.97 mmol) was dissolved in n-hexane (30 mL), and 1.0 M hydrogen chloride-diethyl ether solution (20 mL) was added and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure to give the title compound (1.85 g, 100%). 1 H NMR (CDCl3) δ: 1.43-1.94 (4H, m), 2.37 (2H, br s), 3.10 (2H, br s), 3.56 (2H, br s), 3.77 (2H, t); 19 F NMR (CDCl3) δ: -63.0 (3F, t).

[0186] [Example 15] Synthesis of 1-(2,2,2-trifluoroethyl)piperidinium tetrakis(pentafluorophenyl)borate 1-(2,2,2-Trifluoroethyl)piperidine hydrochloride (0.30 g, 1.47 mmol) obtained in Preparation Example 25 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (1.33 g, 1.46 mmol) was added. The mixture was stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to obtain the title compound (1.19 g, 96%). 1 H NMR (CDCl3) δ: 1.47-1.62 (2H, m), 1.92-1.99 (2H, m), 2.10-2.20 (2H, m), 3.01 (2H, br s), 3.57-3.63 (4H, m); 19 F NMR (CDCl3) δ: -63.2 (3F, t), -134.0 (8F, br s), -163.8 (4F, t), -167.9 (8F, m).

[0187] [Manufacturing Example 26] Synthesis of N,N-dioctadecyl-3,3,3-trifluoropropylamine 1-Octadecanal (2.4 g, 8.94 mmol), 3,3,3-trifluoropropylamine (0.50 g, 4.42 mmol), and acetic acid (0.3 mL) were dissolved in tetrahydrofuran (30 mL), and sodium triacetoxyborohydride (2.10 g, 9.9 mmol) was added and stirred at room temperature for 15 hours. The reaction mixture was made basic with saturated aqueous sodium bicarbonate and extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to give the title compound (2.4 g, 88%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.18-1.43 (64H, m), 2.23-2.27 (2H, m), 2.38-2.44 (4H, m), 2.70 (2H, t); 19 F NMR (CDCl3) δ: -66.5 (3F, t).

[0188] [Manufacturing Example 27] Synthesis of N,N-dioctadecyl-3,3,3-trifluoropropylamine hydrochloride N,N-Dioctadecyl-3,3,3-trifluoropropylamine (1.5 g, 2.43 mmol) obtained in Preparation Example 26 was dissolved in n-hexane (10 mL), and 1.0 M hydrogen chloride-diethyl ether solution (10 mL) was added and stirred for 3 hours. The resulting precipitate was collected by filtration, washed with n-hexane, and dried under reduced pressure to obtain the title compound (1.45 g, 91%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.19-1.40 (60H, m), 1.70-1.81 (4H, m), 2.86-3.03 (6H, m), 3.17-3.22 (2H, m); 19 F NMR (CDCl3) δ: -66.6 (3F, t).

[0189] [Example 16] Synthesis of N,N-dioctadecyl-3,3,3-trifluoropropylammonium tetrakis(pentafluorophenyl)borate N,N-Dioctadecyl-3,3,3-trifluoropropylamine hydrochloride (0.50 g, 0.764 mmol) obtained in Preparation Example 27 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (0.65 g, 0.72 mmol) was added. The mixture was stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried at 70 °C under reduced pressure to obtain the title compound (0.89 g, 96%). 1H NMR (CDCl3) δ: 0.88 (6H, t), 1.18-1.38 (60H, m), 1.65-1.72 (4H, m), 2.60-2.67 (2H, m), 3.04-3.07 (4H, m), 3.27-3.32 (2H, m); 19 F NMR (CDCl3) δ: -64.4 (3F, t), -131.8 (8F, m), -161.4 (4F, m), -165.6 (8F, m).

[0190] Methylcyclohexane was added to the compound of Example 16 to prepare a 10 wt % methylcyclohexane solution, which was confirmed to be a homogeneous solution.

[0191] [Manufacturing Example 28] Synthesis of N,N-dioctadecyl-2-fluoroethylamine 1-Octadecanal (3.0 g, 11 mmol), a tert-butanol solution of 2-fluoroethylamine (10 wt %, 3.3 g, 5.2 mmol), and acetic acid (0.3 mL) were dissolved in tetrahydrofuran (30 mL), and sodium triacetoxyborohydride (2.50 g, 12 mmol) was added and stirred at room temperature for 15 hours. The reaction mixture was made basic with saturated aqueous sodium bicarbonate and extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0 to 90 / 10) to give the title compound (2.02 g, 32%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.18-1.64 (65H, m), 2.44-2.51 (4H, m), 2.77 (2H, dt), 4.50 (1H, dt); 19 F NMR (CDCl3) δ: -2220.6 (1F, br s).

[0192] [Manufacturing Example 29] Synthesis of N,N-dioctadecyl-2-fluoroethylamine hydrochloride N,N-Dioctadecyl-2-fluoroethylamine (1.50 g, 2.64 mmol) obtained in Preparation Example 28 was dissolved in n-hexane (30 mL), and 1.0 M hydrogen chloride-diethyl ether solution (20 mL) was added and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure to give the title compound (1.45 g, 91%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.19-1.40 (60H, m), 1.78-1.82 (4H, m), 3.04-3,11 (4H, m), 3.32-3.40 (2H, m), 5.02 (2H, dt); 19 F NMR (CDCl3) δ: -223.5 (1F, m).

[0193] [Example 17] Synthesis of N,N-dioctadecyl-2-fluoroethylammonium tetrakis(pentafluorophenyl)borate N,N-Dioctadecyl-2-fluoroethylamine hydrochloride (0.50 g, 0.83 mmol) obtained in Preparation Example 29 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (0.75 g, 0.83 mmol) was added. The mixture was stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried at 70 °C under reduced pressure to obtain the title compound (0.89 g, 86%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.18-1.31 (60H, m), 1.65-1.73 (4H, m), 3.11-3.13 (4H, m), 3.34-3.43 (2H, m), 4.76 (2H, dt); 19 F NMR (CDCl3) δ: -133.9 (8F, br s), -163.3 (4F, t), -167.5 (8F, m), -223.4 (1H, br s).

[0194] Methylcyclohexane was added to the compound of Example 17 to prepare a 10 wt % methylcyclohexane solution, which was confirmed to be a homogeneous solution.

[0195] [Manufacturing Example 30] Synthesis of 1,4-bis(2,2,2-trifluoroethyl)piperazine A 1M solution of borane-tetrahydrofuran complex (40 mL, 40 mmol) in tetrahydrofuran (30 mL) was added to 1,4-bis(trifluoroacetyl)piperazine (3.5 g, 13 mmol) at room temperature, followed by stirring at 60°C for 3 hours. The mixture was cooled on ice, and water was carefully added. The mixture was then extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 95 / 5-80 / 20) to give the title compound (2.08 g, 66%). 1 H NMR (CDCl3) δ: 2.71 (8H, s), 2.96 (4H, q); 19 F NMR (CDCl3) δ: -70.2 (6F, t).

[0196] [Manufacturing Example 31] Synthesis of 1,4-bis(2,2,2-trifluoroethyl)piperazine dihydrochloride 1,4-Bis(2,2,2-trifluoroethyl)piperazine (1.50 g, 6.0 mmol) obtained in Preparation Example 30 was dissolved in n-hexane (30 mL), and 1.0 M hydrogen chloride-diethyl ether solution (20 mL) was added thereto, followed by stirring for 1 hour. The mixture was concentrated under reduced pressure to give the title compound (1.85 g, 96%). 1 H NMR (DMSO-d6) δ: 3.03 (8H, br s), 3.67 (4H, br s); 19 F NMR (DMSO-d6) δ: -65.8 (6F, br s).

[0197] [Example 18] Synthesis of 1,4-bis(2,2,2-trifluoroethyl)piperazinium bis[tetrakis(pentafluorophenyl)borate] 1,4-Bis(2,2,2-trifluoroethyl)piperazine dihydrochloride (0.50 g, 1.55 mmol) obtained in Preparation Example 31 was dissolved in dichloromethane (50 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (2.81 g, 3.09 mmol) was added and stirred at room temperature for 3 hours. Insoluble matter was collected by filtration and dissolved in water and dichloromethane, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain the title compound (0.87 g, 35%). 1 H NMR (DMSO-d6) δ: 2.78 (8H, br s), 3.93 (4H, br s); 19 F NMR (DMSO-d6) δ: -67.6 (6F, br s), -132.7 (16F, br s), -161.6 (8F, t), -166.2 (16F, t).

[0198] [Manufacturing Example 32] Synthesis of N,N-didocosyl-2,2,2-trifluoroethylamine 1-Docosanal (4.0 g, 12.3 mmol), 2,2,2-trifluoroethylamine (0.50 g, 5.0 mmol), and acetic acid (0.05 mL) were dissolved in tetrahydrofuran (50 mL), and sodium triacetoxyborohydride (2.80 g, 13 mmol) was added. The mixture was stirred at room temperature for 15 hours. The reaction mixture was made basic with saturated aqueous sodium bicarbonate and extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to give the title compound (1.38 g, 40%). 1H NMR (CDCl3) δ: 0.88 (6H, t), 1.25-1.30 (76H, m), 1.40-1.43 (4H, m), 2.56 (4H, t), 3.00 (2H, q); 19 F NMR (CDCl3) δ: -71.3 (3F, t).

[0199] [Manufacturing Example 33] Synthesis of N,N-didocosyl-2,2,2-trifluoroethylamine hydrochloride N,N-Didocosyl-2,2,2-trifluoroethylamine (1.30 g, 1.82 mmol) obtained in Production Example 32 was dissolved in n-hexane (30 mL), and 1.0 M hydrogen chloride-diethyl ether solution (10 mL) was added and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure to give the title compound (1.34 g, 98%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.25-1.40 (76H, m), 1.85-2.00 (4H, m), 3.14 (4H, t), 3.75 (2H, q); 19 F NMR (CDCl3) δ: -63.5 (3F, t).

[0200] [Example 19] Synthesis of N,N-didocosyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate N,N-Didocosyl-2,2,2-trifluoroethylamine hydrochloride (0.40 g, 0.53 mmol) obtained in Preparation Example 33, lithium tetrakis(pentafluorophenyl)borate-diethyl ether complex (0.41 g, 0.53 mmol), and methylcyclohexane (20 mL) were mixed and stirred at room temperature for 3 hours. The reaction mixture was washed with water, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure at 45° C. to obtain the title compound (0.65 g, 88%). 1H NMR (CDCl3) δ: 0.87 (6H, t), 1.25-1.29 (76H, m), 1.60-1.65 (4H, m), 3.12-3.16 (4H, m). 3.60 (2H, q); 19 F NMR (CDCl3) δ: -65.9 (3F, t), -132.8 (8F, t), -162.3 (4F, m), -166.2 (8F, m).

[0201] Methylcyclohexane was added to the compound of Example 19 to prepare a 10 wt % methylcyclohexane solution, which was confirmed to be a homogeneous solution.

[0202] [Manufacturing Example 34] Synthesis of N,N-(3,7,11,15-tetramethylhexadecyl)-2,2,2-trifluoroethylamine 3,7,11,15-Tetramethylhexadecanal (2.3 g, 7.8 mmol), 2,2,2-trifluoroethylamine (0.20 g, 2.0 mmol), and acetic acid (0.3 mL) were dissolved in tetrahydrofuran (30 mL), and sodium triacetoxyborohydride (1.5 g, 7.8 mmol) was added and stirred at room temperature for 15 hours. The reaction mixture was made basic with saturated aqueous sodium bicarbonate and extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to give the title compound (1.13 g, 85%). 1 H NMR (CDCl3) δ: 0.84-0.88 (30H, m), 1.07-1.56 (48H, m), 2.57-2.61 (4H, m), 3.00 (2H, q); 19 F NMR (CDCl3) δ: -70.9 (3F, t).

[0203] [Manufacturing Example 35] Synthesis of N,N-(3,7,11,15-tetramethylhexadecyl)-2,2,2-trifluoroethylamine hydrochloride N,N-(3,7,11,15-tetramethylhexadecyl)-2,2,2-trifluoroethylamine (2.35 g, 3.56 mmol) obtained in Production Example 34 was dissolved in n-hexane (20 mL), and 1.0 M hydrogen chloride-diethyl ether solution (10 mL) was added and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure to give the title compound (2.48 g, 100%). 1 H NMR (CDCl3) δ: 0.84-0.95 (30H, m), 1.13-1.57 (48H, m), 3.13-3.25 (4H, m), 3.76 (2H, q); 19 F NMR (CDCl3) δ: -63.4 (3F, t).

[0204] [Example 20] Synthesis of N,N-(3,7,11,15-tetramethylhexadecyl)-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate N,N-(3,7,11,15-tetramethylhexadecyl)-2,2,2-trifluoroethylamine hydrochloride (0.50 g, 0.72 mmol) obtained in Preparation Example 35, lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (0.66 g, 0.72 mmol), and methylcyclohexane (15 mL) were mixed and stirred at room temperature for 3 hours. The mixture was washed with water, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure at 45° C. to give the title compound (0.96 g, 68%). 1 H NMR (CDCl3) δ: 0.82-0.89 (30H, m), 1.13-1.57 (48H, m), 3.15-3.25 (4H, m), 3.60 (2H, q); 19F NMR (CDCl3) δ: -67.1 (3F, t), -133.9 (8F, d), -164.4 (4F, t), -167.5 (8F, t).

[0205] Methylcyclohexane was added to the compound of Example 20 to prepare a 10 wt % methylcyclohexane solution, which was confirmed to be a homogeneous solution.

[0206] [Manufacturing Example 36] Synthesis of N,N-(3,7,11-trimethyldodecyl)-2,2,2-trifluoroethylamine 3,7,11-Trimethyldodecanal (1.2 g, 5.3 mmol), 2,2,2-trifluoroethylamine (0.20 g, 2.0 mmol), and acetic acid (0.3 mL) were dissolved in tetrahydrofuran (30 mL), and sodium triacetoxyborohydride (1.5 g, 7.8 mmol) was added and stirred at room temperature for 15 hours. The reaction mixture was made basic with saturated aqueous sodium bicarbonate and extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to give the title compound (0.95 g, 91%). 1 H NMR (CDCl3) δ: 0.83-0.88 (24H, m), 1.00-1.57 (34H, m), 2.58-2.60 (4H, m), 3.00 (2H, q); 19 F NMR (CDCl3) δ: -71.1 (3F, t).

[0207] [Example 21] Synthesis of N,N-(3,7,11-trimethyldodecyl)-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate N,N-(3,7,11-trimethyldodecyl)-2,2,2-trifluoroethylamine (0.56 g, 1 mmol) obtained in Preparation Example 36 was dissolved in methylcyclohexane (20 mL), 1.0 M hydrogen chloride-diethyl ether solution (1 mL) was added, and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (0.91 g, 1 mmol) was added. The reaction mixture was stirred at room temperature for 1 hour. After washing the mixture with water, the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure at 45 °C to give the title compound (1.20 g, 74%). 1 H NMR (CDCl3) δ: 0.81-0.89 (24H, m), 1.03-1.51 (34H, m), 2.95-3.00 (4H, m), 3.41 (2H, q); 19 F NMR (CDCl3) δ: -68.2 (3F, t), -133.9 (8F, d), -164.4 (4F, t), -167.5 (8F, t).

[0208] Methylcyclohexane was added to the compound of Example 21 to prepare a 10 wt % methylcyclohexane solution, which was confirmed to be a homogeneous solution.

[0209] [Example 22] Preparation of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and N,N-dioctadecyl-2,2,2-trifluoroethylamine N,N-Dioctadecyl-2,2,2-trifluoroethylamine (0.90 g, 1.49 mmol) obtained in Preparation Example 2 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (0.91 g, 1.00 mmol) and 1.0 M hydrogen chloride-diethyl ether solution were added, followed by stirring at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 70 °C to obtain the title composition (1.51 g). 1H NMR (CDCl3) δ: 0.86 (6H, t), 1.23-1.30 (60H, m), 1.68-1.76 (4H, m), 3.12-3.16 (4H, m), 3.61 (2H, q); 19 F NMR (CDCl3) δ: -65.3 (4.8F, t), -133.9 (8F, m), -163.8 (4F, t), -167.8 (8F, t).

[0210] N-hexane was added to the composition of Example 22 to prepare a 20 wt % n-hexane solution, which was confirmed to be a homogeneous solution.

[0211] Isohexane was added to the composition of Example 22 to prepare a 20 wt % isohexane solution, which was confirmed to be a homogeneous solution.

[0212] N-heptane was added to the composition of Example 22 to prepare a 20 wt % n-heptane solution, which was confirmed to be a homogeneous solution.

[0213] ISOPAR E (registered trademark) was added to the composition of Example 22 to prepare a 20 wt % ISOPAR E (registered trademark) solution, and it was confirmed that the solution was homogeneous.

[0214] Cyclohexane was added to the composition of Example 22 to prepare a 20 wt % cyclohexane solution, which was confirmed to be a homogeneous solution.

[0215] Methylcyclohexane was added to the composition of Example 22 to prepare a 20 wt % methylcyclohexane solution, which was confirmed to be a homogeneous solution.

[0216] [Manufacturing Example 37] Synthesis of N,N-ditetradecyl-2,2,2-trifluoroethylamine 1-Tetradecanal (4.0 g, 18.8 mmol), 2,2,2-trifluoroethylamine (0.90 g, 9.1 mmol), and acetic acid (0.3 mL) were dissolved in tetrahydrofuran (30 mL), and sodium triacetoxyborohydride (4.0 g, 18.9 mmol) was added. The mixture was stirred at room temperature for 15 hours. The reaction mixture was made basic with saturated aqueous sodium bicarbonate and extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to give the title compound (4.0 g, 89%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.26-1.43 (48H, m), 2.55 (4H, t), 3.00 (2H, q); 19 F NMR (CDCl3) δ: -71.3 (3F, t).

[0217] [Manufacturing Example 38] Synthesis of N,N-ditetradecyl-2,2,2-trifluoroethylamine hydrochloride N,N-Ditetradecyl-2,2,2-trifluoroethylamine (1.50 g, 3.05 mmol) obtained in Preparation Example 37 was dissolved in n-hexane (30 mL), and 1.0 M hydrogen chloride-diethyl ether solution (20 mL) was added and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure to give the title compound (1.45 g, 90%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.20-1.40 (44H, m), 1.96 (4H, br s), 3.15 (4H, br s), 3.78 (2H, q); 19 F NMR (CDCl3) δ: -63.4 (3F, t).

[0218] [Example 23] Synthesis of N,N-ditetradecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate N,N-ditetradecyl-2,2,2-trifluoroethylamine (0.60 g, 1.14 mmol) obtained in Preparation Example 38 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (1.04 g, 1.14 mmol) was added. The mixture was stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried at 70 °C under reduced pressure to obtain the title compound (1.34 g, 100%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.19-1.36 (44H, m), 1.65-1.70 (4H, m), 3.14-3.18 (4H, m), 3.62 (2H, q); 19 F NMR (CDCl3) δ: -66.4 (3F, t), -134.0 (8F, m), -163.4 (4F, t), -167.6 (8F, t).

[0219] Cyclohexane was added to Example 23 to prepare a 20 wt % cyclohexane solution, which was confirmed to be a homogeneous solution.

[0220] [Example 24] Preparation of a composition containing N,N-ditetradecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and didodecyl ether N,N-ditetradecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (58 mg, 0.05 mmol) obtained in Example 23 and didodecyl ether (40 mg, 0.10 mmol) were added and mixed to obtain the title composition. 1H NMR (CDCl3) δ: 0.85-0.88 (18H, m), 1.24-1.35 (116H, m), 1.51-1.58 (8H, m), 1.64-1.70 (4H, m), 3.11-3.15 (4H, m), 3.38 (8H, t), 3.60 (2H, q); 19 F NMR (CDCl3) δ: -66.6 (3F, s), -134.0 (8F, s), -163.5 (4F, t), -167.6 (8F, t).

[0221] N-hexane was added to the composition of Example 24 to prepare a 20 wt % n-hexane solution, which was confirmed to be a homogeneous solution.

[0222] [Manufacturing Example 39] Synthesis of N,N-dihexadecyl-2,2,2-trifluoroethylamine 1-Hexadecanal (4.0 g, 16.6 mmol), 2,2,2-trifluoroethylamine (0.84 g, 8.5 mmol), and acetic acid (0.5 mL) were dissolved in tetrahydrofuran (50 mL), and sodium triacetoxyborohydride (4.0 g, 18.9 mmol) was added and stirred at room temperature for 15 hours. The reaction mixture was made basic with saturated aqueous sodium bicarbonate and extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to give the title compound (4.56 g, 98%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.26-1.43 (56H, m), 2.56 (4H, t), 3.00 (2H, q); 19 F NMR (CDCl3) δ: -71.3 (3F, t).

[0223] [Manufacturing Example 40] Synthesis of N,N-dihexadecyl-2,2,2-trifluoroethylamine hydrochloride N,N-Dihexadecyl-2,2,2-trifluoroethylamine (1.50 g, 2.74 mmol) obtained in Preparation Example 39 was dissolved in n-hexane (30 mL), and 1.0 M hydrogen chloride-diethyl ether solution (20 mL) was added thereto, followed by stirring for 1 hour. The reaction mixture was concentrated under reduced pressure to give the title compound (1.55 g, 97%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.19-1.40 (52H, m), 1.93 (4H, br s), 3.15 (4H, br s), 3.77 (2H, q); 19 F NMR (CDCl3) δ: -63.4 (3F, t).

[0224] [Example 25] Synthesis of N,N-dihexadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate N,N-Dihexadecyl-2,2,2-trifluoroethylamine (0.60 g, 1.03 mmol) obtained in Preparation Example 40 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (0.95 g, 1.05 mmol) was added. The mixture was stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried at 70 °C under reduced pressure to obtain the title compound (1.51 g). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.19-1.36 (54H, m), 1.65-1.70 (4H, m), 3.14-3.18 (4H, m), 3.62 (2H, q); 19 F NMR (CDCl3) δ: -66.4 (3F, t), -134.0 (8F, m), -163.4 (4F, t), -167.6 (8F, t).

[0225] Cyclohexane was added to the compound of Example 25 to prepare a 20 wt % cyclohexane solution, which was confirmed to be a homogeneous solution.

[0226] [Example 26] Preparation of a composition containing N,N-dihexadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and dihexadecyl ether N,N-dihexadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (60 mg, 0.05 mmol) obtained in Example 25 and dihexadecyl ether (23 mg, 0.05 mmol) were added and mixed to obtain the title composition. 1 H NMR (CDCl3) δ: 0.86-0.90 (12H, m), 1.20-1.36 (104H, m), 1.52-1.58 (4H, m), 1.63-1.70 (4H, m), 3.15-3.19 (4H, m), 3.39 (4H, t), 3.64 (2H, q); 19 F NMR (CDCl3) δ: -66.7(3F, s), -134.1 (8F, s), -163.5 (4F, t), -167.6 (8F, t).

[0227] N-hexane was added to the composition of Example 26 to prepare a 20 wt % n-hexane solution, which was confirmed to be a homogeneous solution.

[0228] [Example 27] Preparation of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and dioctyl ether The title composition was obtained by adding and mixing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (64 mg, 0.05 mmol) obtained in Example 1 and dioctyl ether (12 mg, 0.05 mmol). 1 H NMR (CDCl3) δ: 0.88 (12H, t), 1.20-1.37 (80H, m), 1.52-1.58 (4H, m), 1.65-1.70 (4H, m), 3.14-3.19 (4H, m), 3.39 (4H, t), 3.63 (2H, q); 19 F NMR (CDCl3) δ: -66.6 (3F, br s), -134.0 (8F, br s), -163.4 (4F, t), -167.6 (8F, t).

[0229] N-hexane was added to the composition of Example 27 to prepare a 20 wt % n-hexane solution, which was confirmed to be a homogeneous solution.

[0230] [Example 28] Preparation of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and didodecyl ether The N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (64 mg, 0.05 mmol) obtained in Example 1 and didodecyl ether (15 mg, 0.05 mmol) were added and mixed to obtain the title composition. 1 H NMR (CDCl3) δ: 0.86-0.90 (12H, m), 1.20-1.38 (96H, m), 1.53-1.60 (4H, m), 1.65-1.72 (4H, m), 3.15-3.20 (4H, m), 3.39 (4H, t), 3.65 (2H, q); 19 F NMR (CDCl3) δ: -66.4 (3F, br s), -134.0 (8F, br s), -163.4 (4F, t), -167.5 (8F, m).

[0231] N-hexane was added to the composition of Example 28 to prepare a 20 wt % n-hexane solution, which was confirmed to be a homogeneous solution.

[0232] [Example 29] Preparation of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and dihexadecyl ether The N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (64 mg, 0.05 mmol) obtained in Example 1 and dihexadecyl ether (23 mg, 0.05 mmol) were added and mixed to obtain the title composition. 1 H NMR (CDCl3) δ: 0.86-0.98, (12H, m), 1.20-1.35 (112H, m), 1.52-1.75 (8H, m), 3.15-3.20 (4H, m), 3.39 (4H, t), 3.65 (2H, q); 19 F NMR (CDCl3) δ: -66.5 (3F, br s), -134.2 (8F, br s), -163.6 (4F, t), -167.7 (8F, m).

[0233] N-hexane was added to the composition of Example 29 to prepare a 20 wt % n-hexane solution, which was confirmed to be a homogeneous solution.

[0234] [Example 30] Preparation of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and diphenyl ether The title composition was obtained by adding and mixing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (64 mg, 0.05 mmol) obtained in Example 1 and diphenyl ether (8.5 mg, 0.05 mmol). 1H NMR (CDCl3) δ: 0.86-0.90, (6H, m), 1.20-1.40 (58H, m), 1.62-1.68 (4H, m), 3.12-3.16 (4H, m), 3.61 (4H, q), 6.99-7.03 (4H, m), 7.08-7.12 (2H, m), 7.31-7.36 (4H, m); 19 F NMR (CDCl3) δ: -66.9 (3F, br s), -134.1 (8F, br s), -163.4 (4F, t), -167.6 (8F, m).

[0235] N-hexane was added to the composition of Example 30 to prepare a 20 wt % n-hexane solution, which was confirmed to be a homogeneous solution.

[0236] [Example 31] Preparation of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and octadecyl phenyl ether The title composition was obtained by adding and mixing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (64 mg, 0.05 mmol) obtained in Example 1 and octadecyl phenyl ether (18 mg, 0.05 mmol). 1 H NMR (CDCl3) δ: 0.84-0.98 (12H, m), 1.20-1.44 (85H, m), 1.62-1.81 (6H, m), 3.13-3.18 (4H, m), 3.61 (4H,q), 3.95 (2H, t),6.88-6.94 (2H, m), 7.25-7.30 (3H, m); 19 F NMR (CDCl3) δ: -66.8 (3F, br s), -134.1 (8F, br s), -163.4 (4F, t), -167.6 (8F, m).

[0237] N-hexane was added to the composition of Example 31 to prepare a 20 wt % n-hexane solution, which was confirmed to be a homogeneous solution.

[0238] [Example 32] Preparation of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and cyclopentyl methyl ether The title composition was obtained by adding N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (64 mg, 0.05 mmol) obtained in Example 1 and cyclopentyl methyl ether (10 mg, 0.10 mmol) to the mixture and mixing. 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.20-1.35 (60H, m), 1.53-1.56 (4H, m), 1.61-1.76 (16H, m), 3.12-3.17 (4H, m), 3.28 (6H,s), 3.61 (2H, q), 3.79-3.83 (2H, m); 19 F NMR (CDCl3) δ: -66.6 (3F, br s), -133.9 (8F, br s), -163.5 (4F, t), -167.6 (8F, m).

[0239] N-hexane was added to the composition of Example 32 to prepare a 20 wt % n-hexane solution, which was confirmed to be a homogeneous solution.

[0240] [Example 33] Preparation of a composition containing N,N-dihexadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and ditetradecyl ether N,N-Dihexadecyl-2,2,2-trifluoroethylamine hydrochloride (8.10 g, 13.9 mmol) obtained in Preparation Example 40 was dissolved in dichloromethane (80 mL), and ditetradecyl ether (8.10 g, 13.9 mmol) and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (14.2 g, 13.7 mmol) were added. The mixture was stirred at room temperature for 1 hour. Water was added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. The aqueous layer was separated, and the organic layer was washed with water. The organic layer was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was dried at 80°C under reduced pressure to obtain the title composition (22.5 g). 1 H NMR (CDCl3) δ: 0.87-0.89 (12H, m), 1.20-1.80 (104H, m), 3.21-3.24 (4H, m), 3.38-3.41 (4H, m), 3.69 (2H, q); 19 F NMR (CDCl3) δ: -66.7 (3F, br s), -134.0 (8F, m), -163.4 (4F, t), -167.5 (8F, t).

[0241] N-hexane was added to the composition obtained in Example 33 to prepare a 20 wt % n-hexane solution, which was confirmed to be a homogeneous solution.

[0242] [Example 34] Preparation of a composition containing N,N-dihexadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and didodecyl ether N,N-dihexadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (439.2 mg, 0.36 mmol) obtained in Example 25 and didodecyl ether (254 mg, 0.72 mmol) were mixed, and n-hexane (1.756 g) was added to prepare a homogeneous hexane solution of the title composition. The solution was confirmed to be homogeneous. This solution was concentrated under reduced pressure and analyzed by NMR. 1 H NMR (CDCl3) δ: 0.87-0.91 (12H, m), 1.20-1.42 (100H, m), 1.53-1.69 (12H, m), 3.20-3.24 (4H, m), 3.40 (8H, t), 3.67 (2H, q); 19 F NMR (CDCl3) δ: -66.9 (3F, t), -134.0 (8F, m), -163.8 (4F, t), -167.4 (8F, t).

[0243] [Comparative Example 1] Attempts were made to prepare a 10 wt % solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate in methylcyclohexane or n-hexane, but no homogeneous solution was obtained. In the test examples described below, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate was used as the co-catalyst in Comparative Example 1.

[0244] Comparative Example 2 An attempt was made to prepare a 10 wt% n-hexane solution of N,N-dioctadecyl-methylammonium tetrakis(pentafluorophenyl)borate, but a homogeneous solution was not obtained. In the test examples described below, N,N-dioctadecyl-methylammonium tetrakis(pentafluorophenyl)borate was used as the co-catalyst in Comparative Example 2.

[0245] [Test Example] (Polymerization Performance Evaluation) A typical polymerization method using the compound or composition of the present invention as a cocatalyst is shown below.

[0246] In a glove box, a 100 mL autoclave was charged with 1-octene, triisobutylaluminum (TIBA, 0.55 M hexane solution), and solvent (methylcyclohexane (MCH) or toluene) to prepare a comonomer solution. The polymerization catalyst dimethylsilylene(tert-butylamido)-(tetramethylcyclopentadienyl)-titanium(IV)-dichloride (CGC), triisobutylaluminum (0.55 M hexane solution), and solvent were added to prepare a catalyst solution of a predetermined concentration, which was then transferred to a Schlenk flask. The cocatalyst was dissolved in the solvent to prepare a cocatalyst solution of a predetermined concentration, which was then transferred to a Schlenk flask. After mixing the comonomer solution, catalyst solution, and cocatalyst solution, the total amount of solvent and triisobutylaluminum was kept constant during the reaction. After purging the autoclave with ethylene, the catalyst solution and cocatalyst solution were added to the autoclave in sequence. Immediately after this, the ethylene pressure was adjusted to a predetermined pressure and the mixture was stirred at a predetermined temperature (25°C or 100°C) for a predetermined time. After cooling the reaction mixture with ice and venting the ethylene gas, the mixture was poured into methanol (100mL) containing 3mL of hydrochloric acid and stirred at room temperature for 30 minutes. The precipitate was collected by filtration and dried under reduced pressure at 60°C to obtain an ethylene-octene copolymer.

[0247] [Melting point measurement] Differential scanning calorimetry (DSC) measurements were carried out using a DSC6220 instrument (Seiko Instruments Inc.), and the sample (polymer) was heated from 40° C. to 150° C. at a rate of 10° C. / min to measure the melting point.

[0248] The results of the polymerization reaction at 25°C and 100°C are shown in Tables 1 and 2 below, respectively.

[0249] [Table 1]

[0250] [Table 2]

[0251] Tables 1 and 2 confirm that, regardless of the polymerization temperature or the type of solvent used, the fluorine-containing ammonium borate compounds of Examples 1, 2, 4, 7, 11, and 22 exhibit higher polymerization activity than the fluorine-atom-free compounds of Comparative Examples 1 and 2. Furthermore, as shown in Table 1, the compositions (or complexes) of the present invention (Examples 1, 2, 4, and 22) can give polymers with lower melting points than the comparative examples, depending on the polymerization conditions, and it is believed that the amount of comonomer incorporated is increased. [Industrial Applicability]

[0252] The compound or composition of the present invention exhibits high metal complex catalyst activation ability in the polymerization reaction of olefins, dienes, and acetylenes, and is useful as a cocatalyst. Furthermore, the present invention can also provide an industrial process for producing the compound or composition of the present invention.

[0253] This application is based on patent application No. 2020-144177 filed in Japan on August 28, 2020, patent application No. 2020-196704 filed on November 27, 2020, and patent application No. 2021-037078 filed on March 9, 2021, the contents of which are incorporated in their entirety herein.

Claims

1. The following formula (1): 【Chemical 1】 [In the formula, R １ , R ２ , R ３ and R ４ are each independently one or more fluorine atoms or one or more fluoro C １－４ C substituted with an alkyl group ６－１４ represents an aryl group, R ５ represents a fluoro C1-6 alkyl group, R ６ and R ７ are each independently (1) a halogen atom, and (2) C 1-30 alkoxy group a C 1-30 alkyl group optionally substituted with a substituent selected from the group consisting of: (1) a halogen atom, (2) a C 1-30 alkyl group, (3) a C 1-30 alkoxy group, (4) haloC 1-30 alkyl groups and (5) haloC 1-30 alkoxy group represents a C 3-8 cycloalkyl group optionally substituted by a substituent selected from the group consisting of: n represents 1; m represents 1 or 2, and The total number of carbon atoms of R 5 , R 6 and R 7 is 25 or more.] A compound represented by the formula:

2. R １ , R ２ , R ３ and R ４ each independently represents one or more fluorine atoms or one or more fluoro C １－４ The compound according to claim 1, which is a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenylyl group, a 3-biphenylyl group, a 4-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 9-phenanthryl group, or a 3-phenanthryl group, each of which is substituted with an alkyl group.

3. R １ , R ２ , R ３ and R ４ are all pentafluorophenyl groups, 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl) groups, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl groups, or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl groups.

4. The compound according to any one of claims 1 to 3, wherein n and m are both 1.

5. The compound according to any one of claims 1 to 4, and a compound represented by the following formula (3): 【Chemistry 2】 [In the formula, R 5 represents a fluoroC 1-6 alkyl group; R 6 and R 7 are each independently (1) a halogen atom, and (2) C 1-30 alkoxy group a C 1-30 alkyl group optionally substituted with a substituent selected from the group consisting of: (1) a halogen atom, (2) a C 1-30 alkyl group, (3) a C 1-30 alkoxy group, (4) haloC 1-30 alkyl groups and (5) haloC 1-30 alkoxy group represents a C 3-8 cycloalkyl group optionally substituted by a substituent selected from the group consisting of: The total number of carbon atoms of R 5 , R 6 and R 7 is 25 or more.] A compound represented by (In the composition, the compound represented by formula (3) is an amine compound obtained by deprotonating a cation constituting formula (1) described in claim 1.)

6. 6. The composition according to claim 5, wherein the content of the compound represented by formula (3) is in the range of 0.01 to 10 moles relative to 1 mole of the compound represented by formula (1).

7. 6. The composition according to claim 5, wherein the content of the compound represented by formula (3) is in the range of 0.5 to 3 moles per mole of the compound represented by formula (1).

8. Furthermore, the following formula (2): 【Chemistry 3】 [In the formula, R and R′ are each independently an optionally substituted C １－３０ alkyl group, optionally substituted C ３－１５ a cycloalkyl group or an optionally substituted C ６－１４ represents an aryl group.] The composition according to any one of claims 5 to 7, comprising a compound represented by the formula:

9. A co-catalyst for polymerizing at least one monomer selected from the group consisting of olefins, dienes, and acetylenes, comprising the compound according to any one of claims 1 to 4 or the composition according to any one of claims 5 to 8.

10. A method for producing a polymer, comprising polymerizing at least one monomer selected from the group consisting of olefins, dienes, and acetylenes, using the compound according to any one of claims 1 to 4 or the composition according to any one of claims 5 to 8 as a co-catalyst.

11. The following formula (1): 【Chemistry 4】 [In the formula, R １ , R ２ , R ３ and R ４ are each independently one or more fluorine atoms or one or more fluoro C １－４ C substituted with alkyl group ６－１４ represents an aryl group, R ５ teeth, represents a fluoro C 1-6 alkyl group; R 6 and R 7 are each independently (1) a halogen atom, and (2) C 1-30 alkoxy group a C 1-30 alkyl group optionally substituted with a substituent selected from the group consisting of: (1) a halogen atom, (2) a C 1-30 alkyl group, (3) a C 1-30 alkoxy group, (4) haloC 1-30 alkyl groups and (5) haloC 1-30 alkoxy group represents a C 3-8 cycloalkyl group optionally substituted by a substituent selected from the group consisting of: n represents 1; m represents 1 or 2, and The total number of carbon atoms of R 5 , R 6 and R 7 is 25 or more.] The present invention relates to a method for producing a compound represented by the following formula (4): 【Chemistry 5】 [In the formula, R １ , R ２ , R ３ and R ４ represents the same definition as each group in formula (1) above, M ｐ＋ represents an alkali metal ion or an alkaline earth metal ion, and p represents 1 or 2. In the presence of a protonic acid, a compound represented by the following formula (3): 【Chemistry 6】 [wherein R ５ , R ６ and R ７ represents the same definition as each group in formula (1). A production method comprising the step of reacting a compound represented by the formula (I) with a compound represented by the formula (I).

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