Novel pyridinium compound

Abstract

The present invention provides a novel pyridinium compound which is represented by general formula (1), (2) or (3). (In the formulae, each of X11, X21 and X31 represents a halogen atom, and each of X11, X21 and X31 is bonded to a carbon atom in the 2-position, the 4-position or the 6-position of a pyridine ring; R11 represents an alkylene group which may contain a heteroatom, while having 1 to 24 carbon atoms; Z21 represents a group that is selected from among -COO-R22, -CONH-R23 and -CON(R24)(R25), and Z21 is bonded to a carbon atom of the pyridine ring, the carbon atom being different from the carbon atom to which X21 is bonded; R21 represents an alkyl group which may contain a heteroatom, while having 3 to 24 carbon atoms; each of R22, R23, R24 and R25 represents an alkyl group which may contain a heteroatom, while having 3 or more carbon atoms; R31 represents a branched alkyl group which may contain a heteroatom, while having 10 to 24 carbon atoms; and each of A21- and A31- represents a negative ion.)

Description

Novel pyridinium compounds

[0001] The present invention relates to novel pyridinium compounds.

[0002] BACKGROUND ART Pyridinium compounds are compounds containing a cation derived from pyridine, and are used in a variety of applications, including bleaching, pesticides, medicines, disinfectants, synthetic reagents, and catalysts, after being chemically modified as necessary.

[0003] Japanese Patent Laid-Open No. 2008-120699 discloses a medicine containing a specific pyridinium derivative formed by bonding a naphthalene ring to a pyridinium ring having an aryl group or the like bonded to position 1. Japanese Patent Laid-Open No. 60-112761 discloses a specific novel pyridinium compound produced from a specific pyridinium compound.

[0004] On the other hand, oxidizing agents such as hydrogen peroxide are used as so-called oxygen bleaches, but bleach activators are sometimes used in combination to reinforce the bleaching power. Known bleach activators are compounds that react with hydrogen peroxide to produce organic peracids (active species).

[0005] SUMMARY OF THE INVENTION If a new compound that can be used as a bleach activator, such as one that reacts with hydrogen peroxide to generate an organic peracid (active species), could be provided, it would be possible to realize a more desirable situation in terms of design freedom, etc. The present invention provides a novel pyridinium compound.

[0006] The present invention relates to novel pyridinium compounds represented by the following general formula (1), (2), or (3): Hereinafter, the novel pyridinium compounds represented by the following general formulas (1), (2), and (3) will be referred to as compound (1), compound (2), and compound (3), respectively.

[0007]

[0008] [In the formula, X １１ is a halogen atom, and X １１ is bonded to the 2-, 4- or 6-position carbon atom of the pyridine ring, and R １１ is an alkylene group having 1 to 24 carbon atoms which may contain a heteroatom.

[0009]

[0010] [In the formula, X ２１ is a halogen atom, and X ２１ is bonded to the carbon atom at the 2-, 4- or 6-position of the pyridine ring, and Z ２１ is -COO-R ２２ , -CONH-R ２３ and -CON(R ２４ ) (R ２５ ) and Z ２１ is X ２１ is bonded to a carbon atom of the pyridine ring different from the carbon atom to which R is bonded, ２１ is an alkyl group having 3 to 24 carbon atoms which may contain a heteroatom, and R ２２ , R ２３ , R ２４ and R ２５ are each an alkyl group having 3 or more carbon atoms which may contain a heteroatom, and A ２１－ is an anion.

[0011]

[0012] [In the formula, X ３１ is a halogen atom, and X ３１ is bonded to the 2-, 4- or 6-position carbon atom of the pyridine ring, and R ３１ is a branched alkyl group having 10 to 24 carbon atoms which may contain a heteroatom, and A ３１－ is an anion.

[0013] According to the present invention, a novel pyridinium compound is provided. The pyridinium compound of the present invention is expected to be useful as an efficacy enhancer for oxidizing agents, for example, peracid-based oxidizing agents such as hydrogen peroxide.

[0014] Mode for Carrying Out the Invention <Compound (1)> Compound (1) is a pyridinium compound represented by the general formula (1). In the general formula (1), X １１ is a halogen atom, and X １１is bonded to the carbon atom at the 2nd, 4th or 6th position of the pyridine ring. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a chlorine atom being preferred. The position numbers of the pyridine ring are as follows:

[0015]

[0016] In general formula (1), R １１ R is an alkylene group having 1 to 24 carbon atoms which may contain a heteroatom. １１ The number of carbon atoms in R is, for example, 2 or more, further 3 or more, and 20 or less, further 18 or less, further 16 or less, further 14 or less, further 12 or less, further 10 or less, further 8 or less, further 6 or less, and further 4 or less. Examples of heteroatoms include nitrogen atoms, oxygen atoms, sulfur atoms, and phosphorus atoms. １１ When R is an alkylene group containing a heteroatom, １１ The carbon number of R may be the total number of carbon atoms in the carbon chain excluding heteroatoms. １１ may be an alkylene group containing no heteroatoms and having 1 to 24 carbon atoms.

[0017] In general formula (1), -R １１ -SO ３ Examples of the group include -CH ２ - (CH ２ ) ｎ１１ -Y １ - (CH ２ ) ｎ１２ -SO ３ Here, Y １ represents a single bond or a heteroatom; n11 and n12 each represent an integer of 0 or more and 23 or less; and the sum of n11 and n12 is 0 or more and 23 or less.

[0018] Compound (1) can be synthesized, for example, by reacting a halogenated pyridine with a sultone. As shown in the examples below, compound (1) can be synthesized, for example, by reacting 2-chloropyridine with 1,3-propane sultone.

[0019] The synthesis of compound (1) can be carried out in the absence of a solvent or in the presence of a reaction solvent, such as dichloromethane, dichloroethane, chloroform, diethyl ether, tetrahydrofuran, dioxane, diglyme, dimethoxyethane, cyclopentyl methyl ether, dibutyl ether, cyclohexane, acetone, acetonitrile, methyl ethyl ketone, ethyl acetate, dimethylformamide, benzene, toluene, xylene, trifluoromethylbenzene, or nitrobenzene.

[0020] The reaction temperature during the synthesis of compound (1) is preferably 0°C or higher, more preferably 25°C or higher, and preferably 100°C or lower, more preferably 60°C or lower, from the viewpoint of improving the yield of the product.

[0021] After the reaction, compound (1) can be subjected to treatments such as extraction, purification, and recovery, as necessary. For such treatments, for example, column chromatography, preparative TLC, recrystallization, washing with a solvent, and the like can be used.

[0022] <Compound (2)> Compound (2) is a pyridinium compound represented by the general formula (2). ２１ is a halogen atom, and X ２１ is bonded to the carbon atom at position 2, 4 or 6 of the pyridine ring. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferred.

[0023] In general formula (2), Z ２１ is -COO-R ２２ , -CONH-R ２３ and -CON(R ２４ ) (R ２５ ) and Z ２１ is X ２１ is bonded to a carbon atom of the pyridine ring different from the carbon atom to which R is bonded. ２２ , R ２３ , R ２４ and R ２５ R is an alkyl group having 3 or more carbon atoms which may contain a heteroatom.２２ , R ２３ , R ２４ and R ２５ The number of carbon atoms in each of R is, for example, 4 or more, further 8 or more, further 12 or more, and 24 or less, further 20 or less, and further 18 or less. Examples of heteroatoms include nitrogen atoms, oxygen atoms, sulfur atoms, and phosphorus atoms. ２２ , R ２３ , R ２４ and R ２５ When R is an alkyl group containing a heteroatom, ２２ , R ２３ , R ２４ and R ２５ The carbon number of R may be the total number of carbon atoms in the carbon chain excluding heteroatoms. ２２ , R ２３ , R ２４ and R ２５ may be an alkyl group having the above carbon number and not containing a heteroatom. ２１ is -COO-R ２２ and -CONH-R ２３ A group selected from the following is preferred.

[0024] In general formula (2), R ２１ R is an alkyl group having 3 to 24 carbon atoms which may contain a heteroatom. ２１ The number of carbon atoms in R is, for example, 4 or more, further 8 or more, further 12 or more, and 24 or less, further 20 or less, further 18 or less. Examples of heteroatoms include nitrogen atoms, oxygen atoms, sulfur atoms, and phosphorus atoms. ２１ When R is an alkyl group containing a heteroatom, ２１ The carbon number of R may be the total number of carbon atoms in the carbon chain excluding heteroatoms. ２１ may be an alkyl group having 3 to 24 carbon atoms and containing no heteroatoms.

[0025] In general formula (2), -R ２１ Examples of the group include -CH ２ - (CH ２ ) ｎ２１ -Y ２ - (CH ２ ) ｎ２２ -CH ３ Here, Y ２represents a single bond or a heteroatom; n21 and n22 each represent an integer of 0 or more and 22 or less; and the sum of n21 and n22 is 1 or more and 22 or less.

[0026] In general formula (2), A ２１－ is an anion. ２１－ The anion may be either an organic anion or an inorganic anion. ２１－ Examples of the anion include anions that are conjugate bases of acids with a pKa of 5 or less. ２１－ As an anion, for example, trifluoromethanesulfonate ion ( － OTf), paratoluenesulfonate ion ( － OTs), methanesulfonate ion ( － OMs), sulfonate ions, methyl sulfate ions ( － Alkyl sulfate ions such as OSO3Me, chloride ions (Cl － ), bromide ion (Br － ), iodide ion (I － ), tetrafluoroborate ion (BF4 － ) and hexafluorophosphate ions (PF6 - fluorophosphate ions such as bis(trifluoromethanesulfonyl)imide ions ((CF3SO2)2N － ), imide ions such as trifluoroacetate ions (CF3COO － Fluoroacetate ions such as fluoroacetate ions. ２１－ is preferably － OTf, － OSO3Me, － OTs, － OMs, Cl － , and Br － is an anion selected from the group consisting of:

[0027] Among compounds (2), Z in general formula (2) ２１ Ga-COO-R ２２As shown in the examples below, the compound represented by the formula (2) can be synthesized by, for example, reacting 2-chloronicotinic acid chloride with an alcohol such as 1-butanol, dodecanol, or 2-decyl-1-tetradecanol to obtain an ester compound, and then quaternizing the ester compound with a quaternizing agent such as butyl trifluoromethanesulfonate or dodecyl trifluoromethanesulfonate. ２１ Ga-CONH-R ２３ As shown in the Examples below, the compound represented by the formula (I) can be synthesized by, for example, reacting 2-chloronicotinic acid chloride with an alkylamine such as butylamine to obtain an amide compound, and then quaternizing the amide compound with a quaternizing agent such as butyl trifluoromethanesulfonate or dodecyl trifluoromethanesulfonate.

[0028] A reaction solvent can be used for the synthesis of compound (2), such as dichloromethane, dichloroethane, chloroform, diethyl ether, tetrahydrofuran, dioxane, diglyme, dimethoxyethane, cyclopentyl methyl ether, dibutyl ether, cyclohexane, acetone, acetonitrile, methyl ethyl ketone, ethyl acetate, dimethylformamide, benzene, toluene, xylene, trifluoromethylbenzene, or nitrobenzene.

[0029] The reaction temperature during the synthesis of compound (2) is preferably 0°C or higher, more preferably 25°C or higher, and preferably 100°C or lower, more preferably 60°C or lower, from the viewpoint of improving the yield of the product.

[0030] After the reaction, compound (2) can be subjected to treatments such as extraction, purification, and recovery, as necessary. For such treatments, for example, column chromatography, preparative TLC, recrystallization, washing with a solvent, and the like can be used.

[0031] <Compound (3)> Compound (3) is a pyridinium compound represented by the general formula (3). ３１ is a halogen atom, and X ３１is bonded to the carbon atom at position 2, 4 or 6 of the pyridine ring. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferred.

[0032] In general formula (3), R ３１ R is a branched alkyl group having 10 to 24 carbon atoms which may contain a heteroatom. ３１ The number of carbon atoms in R is, for example, 12 or more, further 16 or more, further 20 or more, and 28 or less, further 24 or less, further 22 or less. Examples of heteroatoms include nitrogen atoms, oxygen atoms, sulfur atoms, and phosphorus atoms. ３１ When R is an alkyl group containing a heteroatom, ３１ The carbon number of R may be the total number of carbon atoms in the carbon chain excluding heteroatoms. ３１ R may be a branched alkyl group containing 10 to 24 carbon atoms and containing no heteroatoms. ３１ From the viewpoint of availability, a branched chain alkyl group having a methyl branch is preferred, and a branched chain alkyl group having a plurality of methyl branches is more preferred.

[0033] In general formula (3), -R ３１ For example, -R ３１ is -CH ２ -R ３１１ -Y ３ -R ３１２ -CH ３ Here, Y ３ is a single bond or a heteroatom, and R ３１１ and R ３１２ are each a single bond or an alkylene group, and R ３１１ and R ３１２ The total number of carbon atoms in R is 8 to 22, ３１１ and R ３１２ At least one of them is a branched alkylene group.

[0034] In general formula (3), A ３１－ is an anion. ３１－ The anion may be either an organic anion or an inorganic anion. ３１－ Examples of the anion include anions that are conjugate bases of acids with a pKa of 5 or less. ３１－As an anion, for example, trifluoromethanesulfonate ion ( － OTf), paratoluenesulfonate ion ( － OTs), methanesulfonate ion ( － OMs), sulfonate ions, methyl sulfate ions ( － Alkyl sulfate ions such as OSO3Me, chloride ions (Cl － ), bromide ion (Br － ), iodide ion (I － ), tetrafluoroborate ion (BF4 － ) and hexafluorophosphate ions (PF6 - fluorophosphate ions such as bis(trifluoromethanesulfonyl)imide ions ((CF3SO2)2N － ), imide ions such as trifluoroacetate ions (CF3COO － Fluoroacetate ions such as fluoroacetate ions. ３１－ is preferably － OTf, － OSO3Me, － OTs, － OMs, Cl － , and Br － is an anion selected from the group consisting of:

[0035] As shown in the Examples below, compound (3) can be synthesized by reacting an alcohol such as 3,7-dimethyloctanol or 3,7,11,15-tetramethylhexadecanol with trifluoromethanesulfonic anhydride to obtain a sulfonate ester, and then reacting the sulfonate ester with 2-chloropyridine.

[0036] A reaction solvent can be used for the synthesis of compound (3), such as dichloromethane, dichloroethane, chloroform, diethyl ether, tetrahydrofuran, dioxane, diglyme, dimethoxyethane, cyclopentyl methyl ether, dibutyl ether, cyclohexane, acetone, acetonitrile, methyl ethyl ketone, ethyl acetate, dimethylformamide, benzene, toluene, xylene, trifluoromethylbenzene, or nitrobenzene.

[0037] The reaction temperature during the synthesis of compound (3) is preferably 0°C or higher, more preferably 25°C or higher, and preferably 100°C or lower, more preferably 60°C or lower, from the viewpoint of improving the yield of the product.

[0038] After the reaction, compound (3) can be subjected to treatments such as extraction, purification, and recovery, as necessary. For such treatments, for example, column chromatography, preparative TLC, recrystallization, washing with a solvent, and the like can be used.

[0039] The compounds (1) to (3) of the present invention are expected to be used directly or indirectly in a wide variety of fields, for example, as bleaching agents, decolorizing agents, reactants, cleaners, deodorizers, antiviral agents, sterilizers, sporicides, and the like. The compounds (1) to (3) of the present invention are useful in, for example, (I) in the paper and pulp industry for bleaching of various pulps, deinking and bleaching of waste paper, etc.; (II) in the textile industry for bleaching of natural fibers such as cotton, wool, silk, and synthetic fibers, etc.; (III) in the chemical industry for raw materials for organic and inorganic peroxides, raw materials for organic compounds, raw materials for epoxy compounds, etc.; (IV) in the electronics industry for etching and cleaning of semiconductors and printed circuit boards, etc.; (V) in the pollution treatment field for deodorization, sterilization, decolorization treatment of sewage and industrial wastewater, soil improvement, etc.; (VI) in the mining field for oxidation of metals in refining processes, etc.; (VII) in the food field for sterilization of initial product manufacturing equipment, sterilization of containers, food bleaching, etc.; (VIII) in the pharmaceutical field for intermediate raw materials for pharmaceuticals, etc.; (IX) in the metal finishing field for surface treatment of metals, purification of plating solutions, etc.; (X) In the wood industry, it is expected to be used directly and indirectly for purposes such as bleaching wood and decorative panels.

[0040] The present invention provides use of the novel pyridinium compound represented by general formula (1), the novel pyridinium compound represented by general formula (2), or the novel pyridinium compound represented by general formula (3) as an oxidative decomposition activator. The present invention provides use of the novel pyridinium compound represented by general formula (1), the novel pyridinium compound represented by general formula (2), or the novel pyridinium compound represented by general formula (3) in the production of an oxidative decomposition activator. The present invention also provides use of the novel pyridinium compound represented by general formula (1), the novel pyridinium compound represented by general formula (2), or the novel pyridinium compound represented by general formula (3) in the production of an oxidizing agent. The present invention further provides an oxidative decomposition activator comprising the novel pyridinium compound represented by general formula (1), the novel pyridinium compound represented by general formula (2), or the novel pyridinium compound represented by general formula (3). The present invention also provides use of the novel pyridinium compound represented by general formula (1), the novel pyridinium compound represented by general formula (2), or the novel pyridinium compound represented by general formula (3) as a bleach activator. The present invention also provides use of the novel pyridinium compound represented by general formula (1), the novel pyridinium compound represented by general formula (2), or the novel pyridinium compound represented by general formula (3) in the production of a bleach activator. The present invention also provides use of the novel pyridinium compound represented by general formula (1), the novel pyridinium compound represented by general formula (2), or the novel pyridinium compound represented by general formula (3) in the production of a bleach. The present invention further provides a bleach activator comprising the novel pyridinium compound represented by general formula (1), the novel pyridinium compound represented by general formula (2), or the novel pyridinium compound represented by general formula (3). The matters described for compounds (1) to (3) of the present invention can be appropriately applied to these uses, oxidative decomposition activators, and bleach activators.

[0041] In addition to the above-described embodiments, the present invention discloses the following aspects: <1> A novel pyridinium compound represented by the following general formula (1), (2) or (3).

[0042]

[0043] [In the formula, X １１ is a halogen atom, and X １１ is bonded to the 2-, 4- or 6-position carbon atom of the pyridine ring, and R １１ is an alkylene group having 1 to 24 carbon atoms which may contain a heteroatom.

[0044]

[0045] [In the formula, X ２１ is a halogen atom, and X ２１ is bonded to the carbon atom at the 2-, 4- or 6-position of the pyridine ring, and Z ２１ is -COO-R ２２ , -CONH-R ２３ and -CON(R ２４ ) (R ２５ ) and Z ２１ is X ２１ is bonded to a carbon atom of the pyridine ring different from the carbon atom to which R ２１ is an alkyl group having 3 to 24 carbon atoms which may contain a heteroatom, and R ２２ , R ２３ , R ２４ and R ２５ are each an alkyl group having 3 or more carbon atoms which may contain a heteroatom, and A ２１－ is an anion.

[0046]

[0047] [In the formula, X ３１ is a halogen atom, and X ３１ is bonded to the 2-, 4- or 6-position carbon atom of the pyridine ring, and R ３１ is a branched alkyl group having 10 to 24 carbon atoms which may contain a heteroatom, and A ３１－ is an anion.

[0048] <2> In the general formula (1), X １１ is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and is preferably a chlorine atom.

[0049] <3> In the general formula (1), R １１ The compound according to <1> or <2>, wherein the number of carbon atoms is 2 or more, further 3 or more, and 20 or less, further 18 or less, further 16 or less, further 14 or less, further 12 or less, further 10 or less, further 8 or less, further 6 or less, or further 4 or less.

[0050] <4> In the general formula (1), R １１ The compound according to any one of <1> to <3>, wherein the heteroatom is at least one selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.

[0051] <5> In the general formula (1), R １１ <4> The compound according to any one of <1> to <4>, wherein is an alkylene group containing no heteroatom and having 1 to 24 carbon atoms.

[0052] <6> In the general formula (1), —R １１ -SO ３ is -CH ２ - (CH ２ ) ｎ１１ -Y １ - (CH ２ ) ｎ１２ -SO ３ and Y １ represents a single bond or a heteroatom, n11 and n12 each represent an integer of 0 to 23, and the sum of n11 and n12 is 0 to 23.

[0053] <7> In the general formula (1), X １１ is a chlorine atom, and X １１ is bonded to the 2- or 6-position carbon atom of the pyridine ring, and R １１ <6> The compound according to any one of <1> to <6>, wherein is an alkylene group having 3 carbon atoms.

[0054] <8> In the general formula (2), X ２１ <7> The compound according to any one of <1> to <7>, wherein is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and is preferably a chlorine atom.

[0055] <9> In the general formula (2), R ２２ , R ２３ , R ２４ and R ２５ The compound according to any one of <1> to <8>, wherein the number of carbon atoms in each of the above is 4 or more, further 8 or more, further 12 or more, and 24 or less, further 20 or less, or further 18 or less.

[0056] <10> In the general formula (2), R ２２ , R ２３ , R ２４ and R ２５ The compound according to any one of <1> to <9>, wherein each hetero atom is at least one selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.

[0057] <11> In the general formula (2), the R ２２ , R ２３ , R ２４ and R ２５ <10> The compound according to any one of <1> to <10>, wherein is an alkyl group having the above carbon number and not containing a heteroatom.

[0058] <12> In the general formula (2), Z ２１ is -COO-R ２２ and -CONH-R ２３ The compound according to any one of <1> to <11>, wherein the compound is a group selected from the group consisting of:

[0059] <13> In the general formula (2), R ２１ The compound according to any one of <1> to <12>, wherein the number of carbon atoms is 4 or more, further 8 or more, further 12 or more, and 24 or less, further 20 or less, further 18 or less.

[0060] <14> In the general formula (2), R ２１ The compound according to any one of <1> to <13>, wherein the heteroatom is at least one selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.

[0061] <15> In the general formula (2), R ２１<14> The compound according to any one of <1> to <13>, wherein is an alkyl group having 3 to 24 carbon atoms and containing no heteroatom.

[0062] <16> In the general formula (2), —R ２１ is -CH ２ - (CH ２ ) ｎ２１ -Y ２ - (CH ２ ) ｎ２２ -CH ３ and Y ２ represents a single bond or a heteroatom, n21 and n22 each represent an integer of 0 to 22, and the sum of n21 and n22 is 1 to 22.

[0063] <17> In the general formula (2), A ２１－ <17> The compound according to any one of <1> to <16>, wherein is an anion selected from organic anions and inorganic anions.

[0064] <18> In the general formula (2), A ２１－ <17> The compound according to any one of <1> to <17>, wherein the anion is a conjugate base of an acid having a pKa of 5 or less.

[0065] <19> In the general formula (2), A ２１－ is an anion selected from sulfonate ion, alkyl sulfate ion, halide ion, fluoroborate ion, fluorophosphate ion, imide ion, and fluoroacetate ion, and further, trifluoromethanesulfonate ion ( － OTf), paratoluenesulfonate ion ( － OTs), methanesulfonate ion ( － OMs), methyl sulfate ions ( － OSO3Me), chloride ions (Cl － ), bromide ion (Br － ), iodide ion (I － ), tetrafluoroborate ion (BF4 － ), hexafluorophosphate ion (PF6 - ), bis(trifluoromethanesulfonic acid)imide ion ((CF3SO2)2N－ ), and trifluoroacetate ion (CFCOO － The compound according to any one of <1> to <18>, wherein the anion is selected from the group consisting of:

[0066] <20> In the general formula (2), A ２１－ teeth, － OTf, － OSO3Me, － OTs, － OMs, Cl － , and Br － The compound according to any one of <1> to <19>, wherein the anion is selected from the group consisting of:

[0067] <21> In the general formula (2), X ２１ is a chlorine atom, and X ２１ is bonded to the carbon atom at the 2nd position of the pyridine ring, and Z ２１ is -COO-R ２２ and -CONH-R ２３ is a group selected from ２１ is X ２１ is bonded to a carbon atom of the pyridine ring different from the carbon atom to which R is bonded, ２１ is a group selected from a butyl group, a dodecyl group, and a tetracosyl group, and A ２１ teeth, － The compound according to any one of <1> to <20>, which is OTf.

[0068] <22> In the general formula (2), X ２１ is a chlorine atom, and X ２１ is bonded to the carbon atom at the 2nd position of the pyridine ring, and Z ２１ is -COO-R ２２ and Z ２１ is X ２１ is bonded to a carbon atom of the pyridine ring different from the carbon atom to which R is bonded, ２２ is a group selected from a butyl group, a dodecyl group, and a 2-decyltetradecyl group, and R ２１ is a group selected from a butyl group, a dodecyl group, and a tetracosyl group, and A ２１ teeth, － The compound according to any one of <1> to <21>, which is OTf.

[0069] <23> In the general formula (2), X ２１ is a chlorine atom, and X ２１ is bonded to the carbon atom at the 2nd position of the pyridine ring, and Z ２１ is -COO-R ２２ and R ２２ is a butyl group, and Z ２１ is bonded to the carbon atom at the 3-position of the pyridine ring, and R ２１ is a dodecyl group, and A ２１ teeth, － The compound according to any one of <1> to <22>, which is OTf.

[0070] <24> In the general formula (2), X ２１ is a chlorine atom, and X ２１ is bonded to the carbon atom at the 2nd position of the pyridine ring, and Z ２１ is -COO-R ２２ and R ２２ is a dodecyl group, and Z ２１ is bonded to the carbon atom at the 3-position of the pyridine ring, and R ２１ is a dodecyl group, and A ２１ teeth, － The compound according to any one of <1> to <22>, which is OTf.

[0071] <25> In the general formula (2), X ２１ is a chlorine atom, and X ２１ is bonded to the carbon atom at the 2nd position of the pyridine ring, and Z ２１ is -COO-R ２２ and R ２２ is a 2-decyltetradecyl group, and Z ２１ is bonded to the carbon atom at the 3-position of the pyridine ring, and R ２１ is a dodecyl group, and A ２１ The compound according to any one of <1> to <22>, wherein is -OTf.

[0072] <26> In the general formula (2), X ２１ is a chlorine atom, and X ２１ is bonded to the carbon atom at the 2nd position of the pyridine ring, and Z ２１ is -COO-R ２２ and R２２ is a dodecyl group, and Z ２１ is bonded to the carbon atom at the 3-position of the pyridine ring, and R ２１ is a butyl group, and A ２１ teeth, － The compound according to any one of <1> to <22>, which is OTf.

[0073] <27> In the general formula (2), X ２１ is a chlorine atom, and X ２１ is bonded to the carbon atom at the 2nd position of the pyridine ring, and Z ２１ is -COO-R ２２ and R ２２ is a dodecyl group, and Z ２１ is bonded to the carbon atom at the 3-position of the pyridine ring, and R ２１ is a tetracosyl group, and A ２１ teeth, － The compound according to any one of <1> to <22>, which is OTf.

[0074] <28> In the general formula (2), X ２１ is a chlorine atom, and X ２１ is bonded to the carbon atom at the 2nd position of the pyridine ring, and Z ２１ is -CONH-R ２３ and Z ２１ is X ２１ is bonded to a carbon atom of the pyridine ring different from the carbon atom to which R is bonded, ２３ is a butyl group, and R ２１ is a group selected from a butyl group and a dodecyl group, and A ２１ teeth, － The compound according to any one of <1> to <21>, which is OTf.

[0075] <29> In the general formula (2), X ２１ is a chlorine atom, and X ２１ is bonded to the carbon atom at the 2nd position of the pyridine ring, and Z ２１ is -CONH-R ２３ and R ２３ is a butyl group, and Z ２１ is bonded to the carbon atom at the 3-position of the pyridine ring, and R ２１ is a butyl group, and A２１ teeth, － The compound according to any one of <1> to <21>, which is OTf.

[0076] <30> In the general formula (2), X ２１ is a chlorine atom, and X ２１ is bonded to the carbon atom at the 2nd position of the pyridine ring, and Z ２１ is -CONH-R ２３ and R ２３ is a butyl group, and Z ２１ is bonded to the carbon atom at the 3-position of the pyridine ring, and R ２１ is a dodecyl group, and A ２１ teeth － The compound according to any one of <1> to <21>, which is OTf.

[0077] <31> In the general formula (3), X ３１ <30> The compound according to any one of <1> to <30>, wherein is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and is preferably a chlorine atom.

[0078] <32> In the general formula (3), R ３１ The compound according to any one of <1> to <31>, wherein the number of carbon atoms is 12 or more, further 16 or more, further 20 or more, and 28 or less, further 24 or less, further 22 or less.

[0079] <33> In the general formula (3), R ３１ The compound according to any one of <1> to <32>, wherein the heteroatom is at least one selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.

[0080] <34> In the general formula (3), R ３１ is a branched-chain alkyl group having 10 to 24 carbon atoms and containing no heteroatom, a branched-chain alkyl group having 10 to 24 carbon atoms and further having a methyl branch, or a branched-chain alkyl group having 10 to 24 carbon atoms and further having a plurality of methyl branches.

[0081] <35> In the general formula (3), —R ３１ is -CH２ -R ３１１ -Y ３ -R ３１２ -CH ３ and Y ３ is a single bond or a heteroatom, and R ３１１ and R ３１２ are each a single bond or an alkylene group, and R ３１１ and R ３１２ The total number of carbon atoms in R is 8 to 22, ３１１ and R ３１２ The compound according to any one of <1> to <34>, wherein at least one of the groups is a branched alkylene group.

[0082] <36> In the general formula (3), A ３１－ <35> The compound according to any one of <1> to <35>, wherein is an anion selected from organic anions and inorganic anions.

[0083] <37> In the general formula (3), A ３１－ <36> The compound according to any one of <1> to <36>, wherein the anion is a conjugate base of an acid having a pKa of 5 or less.

[0084] <38> In the general formula (3), A ３１－ is an anion selected from sulfonate ion, alkyl sulfate ion, halide ion, fluoroborate ion, fluorophosphate ion, imide ion, and fluoroacetate ion, and further, trifluoromethanesulfonate ion ( － OTf), paratoluenesulfonate ion ( － OTs), methanesulfonate ion ( － OMs), methyl sulfate ions ( － OSO3Me), chloride ions (Cl － ), bromide ion (Br － ), iodide ion (I － ), tetrafluoroborate ion (BF4 － ), hexafluorophosphate ion (PF6 - ), bis(trifluoromethanesulfonic acid)imide ion ((CF3SO2)2N － ), and trifluoroacetate ion (CFCOO －) an anion selected from － OTf, － OSO3Me, － OTs, － OMs, Cl － , and Br － The compound according to any one of <1> to <37>, wherein the anion is selected from the group consisting of:

[0085] <39> In the general formula (3), X ３１ is a chlorine atom, and X ３１ is bonded to the 2- or 6-position carbon atom of the pyridine ring, and R ３１ is a 3,7-dimethyloctyl group, and A ３１ teeth, － The compound according to any one of <1> to <38>, which is OTf.

[0086] <40> In the general formula (3), X ３１ is a chlorine atom, and X ３１ is bonded to the 2- or 6-position carbon atom of the pyridine ring, and R ３１ is a 3,7,11,15-tetramethylhexadecyl group, and A ３１ teeth, － The compound according to any one of <1> to <38>, which is OTf.

[0087] Examples <NMR measurement conditions> NMR ( 1 The measurement conditions for 1 H NMR were as follows: Apparatus: Vnmr 400MR DD2 (Agilent) Measurement temperature: 25°C Waiting time: 10 seconds Number of accumulations: 8 Observation range: 6410.3 Hz Pulse: 45° Data points: 65536

[0088] Synthesis Example 1 <Synthesis of butyl 2-chloronicotinate> The title compound (intermediate 1) was synthesized according to the following scheme: The synthesis was carried out using a 200 ml three-necked recovery flask.

[0089]

[0090] To a solution obtained from 5 g (28.41 mmol) of 2-chloronicotinic acid chloride and dichloromethane (56.82 ml), 2.32 g (31.25 mmol, 1.1 eq.) of 1-butanol was added and cooled to 0°C. 4.31 g of triethylamine (42.62 mol, 1.5 eq.) was added dropwise, and the mixture was stirred at room temperature (25°C) for 1 hour. After completion of the reaction, the reaction solution was quenched by adding saturated aqueous ammonium chloride solution, and extracted with dichloromethane. The resulting organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated on a rotary evaporator to obtain a crude product. The resulting crude product was purified using silica gel column chromatography (hexane:ethyl acetate = 4:1 → 1:1) to obtain 5.95 g (27.85 mmol, 98% yield) of the title compound (Intermediate 1). The compound 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, CDCl3) δ: 8.5(1H, d, J= 4.8 Hz), 8.2 (1H, d, J = 8 Hz), 7.3 (1H, dd, J = 4.8, 8 Hz), 4.4(2H, t, J =6.4 Hz), 1.8-1.7 (2H, m), 1.5-1.4 (2H, m), 1.0 (3H, t, J = 7.6 Hz)ppm.

[0091] Synthesis Example 2 <Synthesis of dodecyl 2-chloronicotinate> The title compound (intermediate 2) was synthesized according to the following scheme: The synthesis was carried out using a 200 mL three-necked recovery flask.

[0092]

[0093] To a solution obtained from 3 g (19.04 mmol) of 2-chloronicotinic acid and dichloromethane (38.08 ml), 3.55 g (19.04 mmol, 1.0 eq.) of dodecanol was added and the mixture was cooled to 0°C. 0.12 g (0.95 mmol, 0.05 eq.) of 4-dimethylaminopyridine (DMAP) was added, followed by 4.38 g (22.85 mmol, 1.2 eq.) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCl), and the mixture was stirred overnight at room temperature (25°C). After completion of the reaction, the reaction solution was quenched by adding saturated aqueous ammonium chloride and extracted with dichloromethane. The resulting organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated on a rotary evaporator to obtain the crude product. The obtained crude product was purified using silica gel column chromatography (hexane:ethyl acetate=4:1→1:1) to obtain 6.1 g (18.71 mmol, yield 98%) of the title compound (intermediate 2). 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, CDCl3) δ: 9.5(1H, d, J= 6.4 Hz), 8.9 (1H, dd, J = 1.6, 8 Hz),8.2 (1H, dd, J = 6, 7.6 Hz),5.0 (2H,t, J = 7.6 Hz), 4.4 (2H, t, 6.8 Hz), 2.04-1.97 (2H, m), 1.87-1.77 (2H, m),1.49-1.25 (11H, m), 0.90-0.86 (6H, m)ppm.

[0094] Synthesis Example 3 Synthesis of 2-decyltetradecyl 2-chloronicotinate The title compound (Intermediate 3) was synthesized according to the following scheme: The synthesis was carried out using a 200 mL three-necked recovery flask.

[0095]

[0096] To a solution obtained from 5 g (28.41 mmol) of 2-chloronicotinic acid chloride and dichloromethane (56.82 ml), 11.08 g (31.25 mmol, 1.1 eq.) of 2-decyl-1-tetradecanol was added, and the mixture was cooled to 0°C. 4.31 g of triethylamine (42.62 mol, 1.5 eq.) was added dropwise, and the mixture was stirred at room temperature (25°C) for 1 hour. After completion of the reaction, the reaction solution was quenched by adding saturated aqueous ammonium chloride solution, and extracted with dichloromethane. The resulting organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated on a rotary evaporator to obtain a crude product. The resulting crude product was purified using silica gel column chromatography (hexane:ethyl acetate = 4:1 → 1:1) to obtain 13.8 g (27.85 mmol, 98% yield) of the title compound (Intermediate 3). The compound 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, CDCl3) δ: 8.51(1H, dd,J = 2.4, 4.8 Hz), 8.12 (1H, dd, J = 2, 7.6 Hz), 7.33 (1H, dd, J = 4.4,7.6 Hz),4.28 (2H, d, 5.2 Hz), 1.79-1.76 (1H, m), 1.45-1.26 (40H, m), 0.88 (6H,t, J =6.4 Hz) ppm.

[0097] Synthesis Example 4 Synthesis of N-butyl-2-chloronicotinamide The title compound (intermediate 4) was synthesized according to the following scheme: The synthesis was carried out using a 100 mL three-necked recovery flask.

[0098]

[0099] A solution of 2-chloronicotinic acid chloride (5 g, 28.41 mmol) in dichloromethane (56.82 ml) was cooled to 0°C, and 2.18 g of butylamine (29.83 mmol, 1.05 eq.) was added dropwise thereto, followed by 4.31 g of triethylamine (42.62 mol, 1.5 eq.). The mixture was stirred at room temperature (25°C) for 1 hour. After completion of the reaction, saturated aqueous ammonium chloride solution was added to the reaction solution to terminate the reaction, and the mixture was extracted with dichloromethane. The resulting organic layer was washed with water and saturated aqueous sodium chloride solution and then dried over anhydrous sodium sulfate. The organic layer was concentrated using a rotary evaporator and purified by column chromatography (hexane:ethyl acetate = 10:1 → 3:1) to obtain 5.74 g (2.70 mmol, 95% yield) of the title compound (Intermediate 4). The compound 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, CDCl3) δ: 8.5(1H, d, J= 4.8 Hz), 8.1 (1H, d, J = 8 Hz), 7.4 (1H, dd, J = 4.8, 8 Hz), 6.5(1H, s), 3.5(2H, q, J = 5.6, 7.2 Hz), 1.7-1.7 (2H, m), 1.6-1.4 (2H, m), 1.0(3H, t, J = 7.6Hz) ppm.

[0100] Synthesis Example 5 <Synthesis of butyl trifluoromethanesulfonate> The title compound (intermediate 5) was synthesized according to the following scheme: The synthesis was carried out using a 100 mL three-necked recovery flask.

[0101]

[0102] A recovery flask was charged with 1 g (13.5 mmol) of butanol and 27 ml of dichloromethane, and the mixture was cooled to 0°C. Subsequently, trifluoromethanesulfonic anhydride (5.71 g, 20.25 mmol, 1.5 eq.) and pyridine (1.17 g, 14.9 mmol, 1.1 eq.) were added dropwise, and the mixture was stirred at 0°C for 1 hour. After the reaction was completed, hexane was added to the reaction mixture, and the resulting crystals were removed by filtration. The filtrate was concentrated using an evaporator, and hexane was added to the residue. The organic layer was washed with water and saturated brine. The organic layer was dried over anhydrous sodium sulfate and then concentrated using an evaporator. The resulting residue (containing the title compound) was used in the reaction without further purification.

[0103] Synthesis Example 6 Synthesis of dodecyl trifluoromethanesulfonate The title compound (intermediate 6) was synthesized according to the following scheme: The synthesis was carried out using a 100 mL three-necked recovery flask.

[0104]

[0105] A recovery flask was charged with 1 g (5.36 mmol) of dodecanol and 10.7 ml of dichloromethane, and the mixture was cooled to 0°C. Trifluoromethanesulfonic anhydride (2.27 g, 8.04 mmol, 1.5 eq.) and pyridine (0.47 g, 5.9 mmol, 1.1 eq.) were then added dropwise, followed by stirring at 0°C for 1 hour. After the reaction was complete, hexane was added to the reaction mixture, and the resulting crystals were filtered off. The filtrate was concentrated using an evaporator, and hexane was added to the residue. The organic layer was washed with water and saturated brine. The organic layer was dried over anhydrous sodium sulfate and then concentrated using an evaporator. The resulting residue (containing the title compound) was used in the reaction without further purification.

[0106] Synthesis Example 7 Synthesis of 3,7-dimethyloctyl trifluoromethanesulfonate The title compound (Intermediate 7) was synthesized according to the following scheme: The synthesis was carried out using a 100 mL three-necked recovery flask.

[0107]

[0108] A recovery flask was charged with 1 g (6.32 mmol) of 3,7-dimethyloctanol and 12.6 ml of dichloromethane, and the mixture was cooled to 0°C. Trifluoromethanesulfonic anhydride (2.67 g, 9.48 mmol, 1.5 eq.) and pyridine (0.55 g, 6.95 mmol, 1.1 eq.) were then added dropwise, followed by stirring at 0°C for 1 hour. After completion of the reaction, hexane was added to the reaction mixture, and the resulting crystals were filtered off. The resulting filtrate was concentrated using an evaporator, and hexane was added to the residue. The organic layer was washed with water and saturated brine. The organic layer was dried over anhydrous sodium sulfate and then concentrated using an evaporator. The resulting residue (containing the title compound) was used in the reaction without further purification.

[0109] Synthesis Example 8 Synthesis of 3,7,11,15-tetramethylhexadecyl trifluoromethanesulfonate The title compound (Intermediate 8) was synthesized according to the following scheme: The synthesis was carried out using a 50 mL three-necked recovery flask.

[0110]

[0111] A recovery flask was charged with 1 g (3.35 mmol) of 3,7,11,15-tetramethylhexadecanol and dichloromethane (6.7 ml) and cooled to 0°C. Then, trifluoromethanesulfonic anhydride (1.42 g, 50.3 mmol, 1.5 eq.) and pyridine (0.29 g, 3.67 mmol, 1.1 eq.) were added dropwise, and the mixture was stirred at 0°C for 1 hour. After the reaction was complete, hexane was added to the reaction mixture, and the resulting crystals were filtered off. The filtrate was concentrated using an evaporator, and hexane was added to the residue. The organic layer was washed with water and saturated brine. The organic layer was dried over anhydrous sodium sulfate and then concentrated using an evaporator. The resulting residue (containing the title compound) was used in the reaction without further purification.

[0112] Synthesis Example 9 Synthesis of tetracosyl trifluoromethanesulfonate The title compound (Intermediate 9) was synthesized according to the following scheme: The synthesis was carried out using a 50 mL three-necked recovery flask.

[0113]

[0114] A recovery flask was charged with 1 g (2.82 mmol) of tetracosanol and dichloromethane (5.64 ml) and cooled to 0°C. Then, trifluoromethanesulfonic anhydride (1.19 g, 4.23 mmol, 1.5 eq.) and pyridine (0.25 g, 3.1 mmol, 1.1 eq.) were added dropwise, and the mixture was stirred at 0°C for 1 hour. After the reaction was completed, hexane was added to the reaction mixture, and the resulting crystals were removed by filtration. The filtrate was concentrated using an evaporator, and hexane was added to the residue. The organic layer was washed with water and saturated brine. The organic layer was dried over anhydrous sodium sulfate and then concentrated using an evaporator. The resulting residue (containing the title compound) was used in the reaction without further purification.

[0115] Example 1 Synthesis of 3-(2-chloropyridin-1-ium-1-yl)propane-1-sulfonate The title compound was synthesized according to the following scheme: The synthesis was carried out using a 100 mL single-necked recovery flask.

[0116]

[0117] 1,3-propanesultone (4.04g, 33.03mmol, 0.75 eq.) was added to 2-chloropyridine (5g, 44.03mmol) and stirred at 60°C for 5 hours. Acetone was added to the reaction mixture, and the resulting crystals were collected by filtration and dried under reduced pressure to give 4.98g of the title compound (21.14mmol, 64% yield). 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, D2O) δ: 9.0 (1H, d, J = 6.4 Hz), 8.5 (1H, t, J = 6.4 Hz), 8.2 (1H, d, J =8.4 Hz), 8.0 (1H, t, J= 8.4 Hz), 5.0 (2H, t, J = 8 Hz), 3.1 (2H, t, J = 7.2Hz), 2.5 (2H, m) ppm.

[0118] Example 2 Synthesis of 3-(butoxycarbonyl)-2-chloro-1-dodecylpyridin-1-ium trifluoromethanesulfonate The title compound was synthesized according to the following scheme: The synthesis was carried out using a 100 mL single-necked recovery flask.

[0119]

[0120] To the intermediate 6 (dodecyl trifluoromethanesulfonate) obtained in the previous reaction, dichloromethane (10.7 ml) and 1.03 g (4.82 mmol, 0.9 eq.) of the previously synthesized intermediate 1 (butyl 2-chloronicotinate) were added, and the mixture was stirred under reflux at 45°C (water bath temperature) for 24 hours. After the reaction was completed, the reaction mixture was concentrated using an evaporator. Hexane was added to the resulting residue, and the resulting crystals were collected. The resulting crystals were washed with diethyl ether to obtain 2.13 g (4.0 mmol, 83% yield) of the title compound. 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, CDCl3) δ: 9.45(1H, dd,J = 1.6, 6 Hz), 8.88 (1H, dd, J = 1.6, 8 Hz), 8.24 (1H, dd, J = 6, 8Hz), 4.90(2H, t, J = 8 Hz), 4.44 (2H, t, 6.8 Hz), 2.03-1.95 (2H, m), 1.82-1.75(2H, m),1.52-1.26 (20H, m), 0.98 (3H, t, J = 7.2 Hz), 0.88 (3H, t, J = 6.8Hz)ppm.

[0121] Example 3 Synthesis of 3-(dodecyloxycarbonyl)-2-chloro-1-dodecylpyridin-1-ium trifluoromethanesulfonate The title compound was synthesized according to the following scheme: The synthesis was carried out using a 100 mL single-necked recovery flask.

[0122]

[0123] To the intermediate 6 (dodecyl trifluoromethanesulfonate) obtained in the previous reaction, dichloromethane (10.7 ml) and 1.57 g (4.82 mmol, 0.9 eq.) of the previously synthesized intermediate 2 (dodecyl 2-chloronicotinate) were added, and the mixture was stirred under reflux at 45°C (water bath temperature) for 24 hours. After the reaction was completed, the reaction mixture was concentrated using an evaporator. Hexane was added to the resulting residue, and the resulting crystals were collected. The resulting crystals were washed with diethyl ether to obtain 1.93 g (3.0 mmol, 62% yield) of the title compound. 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, CDCl3) δ: 9.59(1H, dd,J = 1.6, 6.4 Hz), 8.83 (1H, dd, J = 1.6, 8 Hz), 8.20 (1H, dd, J = 6, 8Hz),4.97 (2H, t, J = 8 Hz), 4.45 (2H, t, 6.8 Hz), 2.05-1.97 (2H, m), 1.84-1.77(2H,m), 1.47-1.21 (36H, m), 0.88 (6H, t, J = 6.8 Hz) ppm.

[0124] Example 4 Synthesis of 3-(2-decyltetradecyloxycarbonyl)-2-chloro-1-dodecylpyridin-1-ium trifluoromethanesulfonate The title compound was synthesized according to the following scheme: The synthesis was carried out using a 100 mL single-necked eggplant flask.

[0125]

[0126] To the intermediate 6 (dodecyl trifluoromethanesulfonate) obtained in the previous reaction, dichloromethane (10.7 ml) and 2.4 g (4.82 mmol, 0.9 eq.) of the previously synthesized intermediate 3 (2-chloronicotinic acid (2-decyltetradecyl)) were added, and the mixture was stirred under reflux at 45°C (water bath temperature) for 24 hours. After the reaction was completed, the reaction mixture was concentrated using an evaporator. Hexane was added to the resulting residue, and the resulting crystals were collected. The resulting crystals were washed with diethyl ether to obtain 2.0 g (2.46 mmol, 51% yield) of the title compound. 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, CDCl3) δ: 9.56(1H, dd,J = 1.6, 6.4 Hz), 8.83 (1H, dd, J = 1.6, 8 Hz), 8.25 (1H, dd, J = 6.4,8.4 Hz),4.95 (2H, t, J = 7.6 Hz), 4.36 (2H, d, J= 5.6 Hz), 2.02-1.97 (2H, m), 1.81-1.78 (1H, m), 1.48-1.22 (61H, m), 0.90-0.86 (6H, m) ppm.

[0127] Example 5 Synthesis of 1-butyl-2-chloro-3-((dodecyloxy)carbonyl)pyridin-1-ium trifluoromethanesulfonate The title compound was synthesized according to the following scheme: The synthesis was carried out using a 200 mL single-necked recovery flask.

[0128]

[0129] To the intermediate 5 (butyl trifluoromethanesulfonate) obtained in the previous reaction, dichloromethane (26.97 ml) and 3.95 g (12.14 mmol, 0.9 eq.) of the previously synthesized intermediate 2 (2-chloronicotinic acid dodecyl) were added, and the mixture was stirred under reflux at 45°C (water bath temperature) for 24 hours. After the reaction was completed, the reaction mixture was concentrated using an evaporator. Hexane was added to the resulting residue, and the resulting crystals were collected. The resulting crystals were washed with diethyl ether to obtain 3.25 g (6.1 mmol, 50% yield) of the title compound. 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, CDCl3) δ: 9.50(1H, dd,J = 1.6, 6 Hz), 8.82 (1H, dd, J = 1.6, 8 Hz), 8.24 (1H, dd, J = 6, 7.6Hz),4.94 (2H, t, J = 8 Hz), 4.43 (2H, t, 6.8 Hz), 2.03-1.95 (2H, m), 1.83-1.76(2H,m), 1.53-1.21 (20H, m), 1.01 (3H, t, J = 7.2 Hz), 0.88 (3H, t, J = 6.4 Hz)ppm.

[0130] Example 6 Synthesis of 1-tetracosyl-2-chloro-3-((dodecyloxy)carbonyl)pyridin-1-ium trifluoromethanesulfonate The title compound was synthesized according to the following scheme. The synthesis was carried out using a 200 mL single-necked recovery flask.

[0131]

[0132] To the intermediate 9 (tetracosyl trifluoromethanesulfonate) obtained in the previous reaction, dichloromethane (26.97 ml) and 3.95 g (12.14 mmol, 0.9 eq.) of the previously synthesized intermediate 2 (2-chloronicotinic acid dodecyl) were added, and the mixture was stirred under reflux at 45°C (water bath temperature) for 24 hours. After the reaction was completed, the reaction mixture was concentrated using an evaporator. Hexane was added to the resulting residue, and the resulting crystals were collected. The resulting crystals were washed with diethyl ether to obtain 7.3 g (9.0 mmol, 74% yield) of the title compound. 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, CDCl3) δ: 9.55(1H, d,J = 6.4 Hz), 8.85 (1H, dd, J = 1.6, 8 Hz), 8.22 (1H, dd, J = 6, 7.6 Hz),4.95(2H, t, J = 7.6 Hz), 4.44 (2H, t, 6.8 Hz), 2.04-1.97 (2H, m), 1.87-1.77(2H,m), 1.50-1.21 (60H, m), 0.88 (6H, t, J = 6.4 Hz) ppm.

[0133] Example 7 Synthesis of 1-butyl-3-(butylcarbamoyl)-2-chloropyridin-1-ium trifluoromethanesulfonate The title compound was synthesized according to the following scheme: The synthesis was carried out using a 100 mL single-necked recovery flask.

[0134]

[0135] To the intermediate 5 (butyl trifluoromethanesulfonate) obtained in the previous reaction, dichloromethane (10.7 ml) and 1.03 g (4.82 mmol, 0.9 eq.) of the previously synthesized intermediate 4 (N-butyl-2-chloronicotinamide) were added, and the mixture was stirred under reflux at 45°C (water bath temperature) for 24 hours. After the reaction was completed, the reaction mixture was concentrated using an evaporator. Hexane was added to the resulting residue, and the resulting crystals were collected. The resulting crystals were washed with diethyl ether to obtain 0.79 g (1.88 mmol, 39% yield) of the title compound. 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, CDCl3) δ: 9.00(1H, dd,J = 1.2, 6.4 Hz), 8.38 (1H, dd, J = 1.2, 7.6 Hz), 8.02 (1H, t, J = 5.6Hz),7.96 (1H, td, J = 6.4, 7.6 Hz), 4.72 (2H, t,J = 7.6 Hz), 3.42 (2H, dd, J=6.8, 12.8 Hz), 1.99-1.91 (2H, m), 1.64-1.57 (2H, m), 1.51-1.37 (4H,m),1.01-0.93 (6H, m) ppm.

[0136] Example 8 Synthesis of 3-(butylcarbamoyl)-2-chloro-1-dodecylpyridin-1-ium trifluoromethanesulfonate The title compound was synthesized according to the following scheme: The synthesis was carried out using a 100 mL single-necked recovery flask.

[0137]

[0138] To the intermediate 6 (dodecyl trifluoromethanesulfonate) obtained in the previous reaction, dichloromethane (10.7 ml) and 1.03 g (4.82 mmol, 0.9 eq.) of the previously synthesized intermediate 4 (N-butyl-2-chloronicotinamide) were added, and the mixture was stirred under reflux at 45°C (water bath temperature) for 24 hours. After the reaction was completed, the reaction mixture was concentrated using an evaporator. Hexane was added to the resulting residue, and the resulting crystals were collected. The resulting crystals were washed with diethyl ether to obtain 0.91 g (1.71 mmol, 35% yield) of the title compound. 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, CDCl3) δ: 8.99(1H, dd,J = 1.2, 6 Hz), 8.37 (1H, dd, J = 1.2, 7.6 Hz), 8.04 (1H, t, J = 5.6Hz), 7.95(1H, dd, J = 6.4, 8 Hz), 4.71 (2H, t, J =8 Hz), 3.42 (2H, dd, J = 6.8,12.8Hz), 2.03-1.92 (2H, m), 1.65-1.57 (2H, m), 1.46-1.24 (20H, m), 0.97-0.88(6H,m) ppm.

[0139] Example 9 Synthesis of 2-chloro-1-(3,7-dimethyloctyl)pyridin-1-ium trifluoromethanesulfonate The title compound was synthesized according to the following scheme: The synthesis was carried out using a 100 mL single-necked recovery flask.

[0140]

[0141] To 1.22 g (4.2 mmol, 1.1 eq.) of the intermediate 7 (3,7-dimethyloctyl trifluoromethanesulfonate) obtained in the previous reaction, dichloromethane (7.62 ml) and 2-chloropyridine (0.6 g, 3.81 mmol) were added and stirred at 45°C for 24 hours. After the reaction was completed, the reaction solution was concentrated using an evaporator to obtain 1.5 g (3.71 mmol, 97% yield) of the title compound. 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, CDCl3) δ: 9.1(1H, d, J = 6 Hz), 8.5 (1H, t, J = 6.4 Hz), 8.1 (2H, m),4.8 (2H, m), 1.9(1H, m), 1.8 (1H, m), 1.6 (1H, m), 1.5 (1H, m), 1.4-1.2(6H, m),1.0 (3H, t, J =6.8 Hz), 0.9 (6H, m) ppm.

[0142] Example 10 Synthesis of 2-chloro-1-(3,7,11,15-tetramethylhexadecyl)pyridin-1-ium trifluoromethanesulfonate The title compound was synthesized according to the following scheme: The synthesis was carried out using a 50 mL single-necked recovery flask.

[0143]

[0144] To 1.44 g (1.1 eq.) of the intermediate 8 (3,7,11,15-tetramethylhexadecyl trifluoromethanesulfonate) obtained in the previous reaction, dichloromethane (6.7 ml) and 2-chloropyridine (0.35 g, 3.05 mmol) were added, and the mixture was stirred under reflux at 45°C (water bath temperature) for 24 hours. After the reaction was completed, the reaction mixture was concentrated using an evaporator. The resulting residue was purified using preparative TLC to obtain 0.38 g (0.7 mmol, 23% yield) of the title compound. 1 The results of 1 H NMR measurement were as follows: 1H NMR(400 MHz, CDCl3) δ: 9.24(1H, dd,J = 1.6, 6 Hz), 8.52 (1H, dt, J = 1.6, 8.4 Hz), 8.1 (1H, t, J = 6, Hz),8.04(1H, dd, J = 1.2, 8 Hz), 4.82 (2H, m), 2.00-1.92 (1H, m), 1.84-1.74 (1H,m),1.69-1.64 (1H, m), 1.57-1.47 (1H, m), 1.40-1.02(20H, m), 0.90-0.84 (15H,m)ppm.

[0145] <Test Example 1> (1) Reagents The reagents used in Test Example 1 are as follows: Phosphoric acid (85%): FUJIFILM Wako Pure Chemical Industries, Ltd. Disodium hydrogen phosphate: FUJIFILM Wako Pure Chemical Industries, Ltd. Potassium dihydrogen phosphate: FUJIFILM Wako Pure Chemical Industries, Ltd. Ethanol (99.5%): FUJIFILM Wako Pure Chemical Industries, Ltd. Curcumin: FUJIFILM Wako Pure Chemical Industries, Ltd. Acetonitrile: FUJIFILM Wako Pure Chemical Industries, Ltd. Hydrogen peroxide (30%): FUJIFILM Wako Pure Chemical Industries, Ltd. The amounts in parentheses are effective amounts. The amounts shown below are effective amounts.

[0146] (2) Evaluation of oxidative decomposition activity 3-(2-chloropyridin-1-ium-1-yl)propane-1-sulfonate of Example 1 (hereinafter referred to as the pyridinium compound of Example 1) was used to evaluate oxidative decomposition activity.

[0147] A 5.29 mM solution of the pyridinium compound of Example 1 (Solution A) was prepared using ion-exchanged water, a 1765 mM hydrogen peroxide solution (Solution B) was prepared using ion-exchanged water and 30% hydrogen peroxide, and a 1.32 mM curcumin solution was prepared using ethanol. To 18.8 ml of phosphate buffer adjusted to pH 7.3, 0.1 ml of Solution B and 1 ml of Solution A were added and stirred for 10 seconds. After stirring for 10 minutes, 0.1 ml of the curcumin solution was added and stirred (final concentrations were 0.264 mM of the pyridinium compound of Example 1, 8.824 mM hydrogen peroxide, and 0.0066 mM curcumin). The pH 7.3 phosphate buffer was prepared from disodium hydrogen phosphate and potassium dihydrogen phosphate. After 10 minutes, 0.5 ml of the reaction mixture was sampled and 0.5 ml of a quenching solution (0.5 M aqueous phosphoric acid solution / acetonitrile = 1:1 (vol)) was added to prepare the sample solution. The remaining amount of curcumin was determined by HPLC quantification. The HPLC quantification results showed that the oxidative decomposition activity of the pyridinium compound of Example 1 under neutral conditions was 100%. The HPLC conditions were as follows. Note that, when a similar evaluation was performed using the compounds of Examples 2 to 10 instead of the pyridinium compound of Example 1, oxidative decomposition activity equivalent to that of the pyridinium compound of Example 1 was obtained.

[0148] <HPLC conditions> ・Equipment SHIMAZU CBM-20A Pump:LC-20A, UV-Vis detector:SPD-20A, PDA detector:SPD-M20A, Column oven:CTO-20A, Auto sampler:SIL-20A ・Analysis conditions Column:L-column ODS,150mm×4.6mm, 5μm(Japan Chemical Substances Evaluation Agency) Oven temperature:40℃, Detector:UV(430nm), Injection volume:10μl, Flow rate:1.0mL / min, Mobile phase:A=50mM phosphoric acid,B=acetonitrile

Claims

1. A novel pyridinium compound represented by the following general formula (2) or (3). 【Chemistry 1】 [wherein, X ２１ is a halogen atom, X ２１ is bonded to the carbon atom at the 2-position, 4-position or 6-position of the pyridine ring, Z ２１ is -COO-R ２２ , -CONH-R ２３ and -CON(R ２４ )(R ２５ ) and is a group selected therefrom, Z ２１ is bonded to a carbon atom of a pyridine ring different from the carbon atom to which X ２１ is bonded, R ２１ is an alkyl group having 3 to 24 carbon atoms which may contain a hetero atom, R ２２ , R ２４ and R ２５ are each an alkyl group having 8 to 24 carbon atoms which may contain a hetero atom, R 23 is an alkyl group having 3 or more carbon atoms which may contain a hetero atom, A ２１－ is an anion.] 【Chemistry 2】 [In the formula, X ３１ X is a halogen atom, ３１ It is bonded to the carbon atom at position 2, 4, or 6 of the pyridine ring, R ３１ A is a branched alkyl group having 10 to 24 carbon atoms, which may contain heteroatoms. ３１－ It is an anion.

2. In the above general formula (2), -R ２１ is, -CH ２ - (CH ２ ) ｎ２１ -Y ２ - (CH ２ ) ｎ２２ -CH ３ Y ２ The compound according to claim 1, wherein n21 is a single bond or a heteroatom, n21 and n22 are each integers between 0 and 22, and the sum of n21 and n22 is between 1 and 22.

3. In the above general formula (3), -R ３１ is, -CH ２ -R ３１１ -Y ３ -R ３１２ -CH ３ Y ３ R is a single bond or a heteroatom, ３１１ and R ３１２ Each of these is either a single bond or an alkylene group, R ３１１ and R ３１２ The total number of carbon atoms is 8 or more and 22 or less, R ３１１ and R ３１２ The compound according to claim 1 or 2, wherein at least one of the groups is a branched alkylene group.

4. In the above general formula (2), R ２１ The compound according to claim 1 or 2, wherein is an alkyl group having 3 to 24 carbon atoms and not containing a heteroatom.

5. In the above general formula (2), Z ２１ is, -COO-R ２２ and -CONH-R ２３ A compound according to claim 1 or 2, wherein the group is selected from the above.

6. The compound according to claim 1 or 2, wherein in the general formula (2), X 21 is a chlorine atom, X 21 is bonded to the carbon atom at position 2 of the pyridine ring, Z 21 is a group selected from -COO-R 22 and -CONH-R 23, Z 21 is bonded to a carbon atom of the pyridine ring different from the carbon atom to which X 21 is bonded, R 21 is a group selected from a butyl group, a dodecyl group and a tetracosyl group, and A 21 is a trifluoromethanesulfonate ion.

7. The compound according to claim 1 or 2, wherein in the general formula (2), X 21 is a chlorine atom, X 21 is bonded to the carbon atom at position 2 of the pyridine ring, Z 21 is -COO-R 22, Z 21 is bonded to a carbon atom of the pyridine ring different from the carbon atom to which X 21 is bonded, R 22 is a group selected from a butyl group, a dodecyl group and a 2-decyltetradecyl group, R 21 is a group selected from a butyl group, a dodecyl group and a tetracosyl group, and A 21 is a trifluoromethanesulfonate ion.

8. The compound according to claim 1 or 2, wherein in the general formula (2), X 21 is a chlorine atom, X 21 is bonded to the carbon atom at position 2 of the pyridine ring, Z 21 is -CONH-R 23, Z 21 is bonded to a carbon atom of the pyridine ring different from the carbon atom to which X 21 is bonded, R 23 is a butyl group, R 21 is a group selected from a butyl group and a dodecyl group, and A 21 is a trifluoromethanesulfonate ion.

9. In the above general formula (3), R ３１ The compound according to claim 1 or 2, wherein is a branched alkyl group having 10 to 24 carbon atoms and no heteroatoms.

10. The compound according to claim 1 or 2, wherein in the general formula (3), X 31 is a chlorine atom, X 31 is bonded to the carbon atom at position 2 or 6 of the pyridine ring, R 31 is a 3,7-dimethyloctyl group, and A 31 is a trifluoromethanesulfonate ion.

11. The compound according to claim 1 or 2, wherein in the general formula (3), X 31 is a chlorine atom, X 31 is bonded to the carbon atom at position 2 or 6 of the pyridine ring, R 31 is a 3,7,11,15-tetramethylhexadecyl group, and A 31 is a trifluoromethanesulfonate ion.

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