Novel pyridinium compound

Abstract

To provide a compound usable as a bleach activator and exhibiting stability in aqueous solution.SOLUTION: Provided is a novel pyridinium compound represented by the following general formula (1). In the formula, R1 is a hydrocarbon group having 2 to 24 carbon atoms; Y is a group represented below, which is bound to one of the carbon atoms at the 2-, 4-, or 6-position of the pyridine ring; R2 is a hydrocarbon group which may contain a heteroatom; and A- is an anion.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to novel pyridinium compounds, methods for producing pyridinium compounds, and compositions. [Background technology]

[0002] 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] Patent Document 1 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 the 1-position. Patent Document 2 discloses a specific novel pyridinium compound produced from a specific pyridinium compound. Furthermore, Patent Document 3 discloses a method for hardening gelatin by reacting a specific sulfonylpyridinium compound with gelatin.

[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] An oxidizing agent composition is a composition containing a compound (oxidizing agent) that has an oxidizing effect on other substances. This oxidizing effect can be recognized as a phenomenon such as decolorization, bleaching, or discoloration of colored substances. Oxidizing agent compositions are used for a variety of purposes, such as bleaching hard objects in bathrooms, toilets, and kitchens, removing mold, bleaching textile products such as clothing, decomposing stains and odor-causing substances, sterilization, pulp bleaching, and textile refining.

[0006] Various stains that occur in living environments are dealt with by cleaning, bleaching, disinfecting, and other methods for maintaining aesthetic appearance and hygiene. In particular, stains in hard-to-clean locations such as toilets, bathrooms, bath heaters, and drainage pipes are difficult to remove using detergents primarily containing surfactants, and bleach is often used. For example, dark stains on bathroom bathtubs, tile joints, door frames, window frames, controllers, and kitchen corners are caused by pigments produced by molds such as Cladosporium bacteria, and are difficult to remove using cleansers or surfactants alone. Therefore, a common method for removing these stains is the bleaching action of a sodium hypochlorite solution.

[0007] However, although mold removers using sodium hypochlorite have excellent bleaching and cleaning properties, they are highly irritating to the eyes and skin, have a distinctive chlorine-based odor, and require caution when used in small spaces such as bathrooms. Furthermore, there is also the problem that they can produce toxic gases if accidentally mixed with acidic cleaning agents.

[0008] For this reason, as an application example of an oxidizing agent composition that does not cause such problems, an agent using an oxygen-based bleaching agent has been proposed. For example, Patent Document 4 discloses a bleaching agent composition for hard surfaces that uses hydrogen peroxide, an alkali agent, and a bleaching activator in combination.

[0009] Furthermore, Patent Document 5 discloses a composition that exhibits a high bactericidal and disinfecting effect, which comprises a peroxide that dissolves in water to generate hydrogen peroxide, a chelating agent, a copper compound, and a binder compound.

[0010] Furthermore, Patent Document 6 describes a bleaching composition in which a high-viscosity composition 1 containing hydrogen peroxide, an organic thickener, an organic chelating agent, and water is mixed with a high-viscosity composition 2 containing an inorganic alkali, an organic thickener, a bleach activator, and water at the time of use. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] JP 2008-120699 [Patent Document 2] Japanese Patent Publication No. 60-112761 [Patent Document 3] Japanese Patent Publication No. 56-36645 [Patent Document 4] Japanese Patent Application Publication No. 3-220298 [Patent Document 5] Japanese Patent Application Laid-Open No. 2009-155292 [Patent Document 6] Japanese Patent Application Laid-Open No. 2002-80894 Summary of the Invention [Problem to be solved by the invention]

[0012] Thus, it has been known to use organic acid esters as bleach activators for hydrogen peroxide, an oxygen-based bleach. With this combination, the reaction that generates the bleaching active species proceeds relatively efficiently in alkaline conditions, but slows down in neutral conditions. Therefore, bleaches and oxidizing agents that use peracids such as hydrogen peroxide tend to exhibit reduced bleaching and oxidizing power in neutral conditions, limiting the flexibility of their design.

[0013] Therefore, if a new compound that can be used as a bleach activator by reacting 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 inventors have newly discovered that novel pyridinium compounds can be synthesized by a new route, leading to the present invention. That is, the present invention provides novel pyridinium compounds and novel methods for producing pyridinium compounds.

[0014] Oxygen bleaches are prepared by reacting hydrogen peroxide, an oxidizing agent, with an organic acid ester, a bleach activator, to generate active bleaching species (such as organic peracids), which oxidize and bleach the target material. In preparing oxygen bleaches, it is desirable that the bleach activator be stably supplied in the form of an aqueous solution, from the viewpoint of ease of handling. The present invention provides a composition that can be used as a bleach activator for oxygen bleaches and is stable in the form of an aqueous solution. [Means for solving the problem]

[0015] The present invention relates to a novel pyridinium compound represented by the following general formula (1) (hereinafter referred to as compound (1)).

[0016] [ka]

[0017] [In the formula, R 1 is a hydrocarbon group having 2 to 24 carbon atoms, and Y is

[0018] [ka]

[0019] Y is bonded to any one of the carbon atoms at the 2-, 4-, and 6-positions of the pyridine ring, and R 2 is a hydrocarbon group which may contain a heteroatom, and A - is an anion.

[0020] The present invention also relates to a method for producing a pyridinium compound, comprising step 1 of reacting a compound represented by the following general formula (1') with a sulfonylating agent to obtain a pyridinium compound represented by the following general formula (1):

[0021] [ka]

[0022] [In the formula, R 1 is a hydrocarbon group having 2 to 24 carbon atoms, and Y' is -O - and Y' is bonded to any one of the carbon atoms at the 2-, 4-, and 6-positions of the pyridine ring.

[0023] [ka]

[0024] [In the formula, R 1 is a hydrocarbon group having 2 to 24 carbon atoms, and Y is

[0025] [ka]

[0026] Y is bonded to any one of the carbon atoms at the 2-, 4-, and 6-positions of the pyridine ring, and R 2 is a hydrocarbon group which may contain a heteroatom, and A - is an anion.

[0027] The present invention relates to an acidic composition containing a pyridinium compound represented by the following general formula (1) [hereinafter referred to as component (A)] and water.

[0028] [ka]

[0029] [In the formula, R 1 is a hydrocarbon group having 2 to 24 carbon atoms, and Y is

[0030] [ka]

[0031] Y is bonded to any one of the carbon atoms at the 2-, 4-, and 6-positions of the pyridine ring, and R 2 is a hydrocarbon group which may contain a heteroatom, and A - is an anion.

[0032] The present invention also relates to a method for preserving a compound, which comprises preserving component (A) in acidic water.

[0033] The present invention also relates to an oxidation method in which a treatment liquid prepared from the composition of the present invention is brought into contact with an object in the presence of hydrogen peroxide.

[0034] The present invention also relates to a bleaching method in which a processing solution prepared from the composition of the present invention is brought into contact with an object in the presence of hydrogen peroxide.

[0035] The present invention also relates to use of the composition of the present invention for producing an oxidizing agent.

[0036] The present invention also relates to the use of the composition of the present invention for producing a bleaching agent. [Effects of the Invention]

[0037] According to the present invention, a novel pyridinium compound and a novel method for producing a pyridinium compound are provided. The pyridinium compounds of the present invention are expected to be useful as potentiators of oxidizing agents, for example, peracid-based oxidizing agents such as hydrogen peroxide.

[0038] Furthermore, the present invention provides a composition that can be used as a bleaching activator for oxygen bleaching agents and is stable in the form of an aqueous solution. As mentioned above, it is known that organic acid esters are used as bleach activators for oxygen-based bleaching agents such as hydrogen peroxide. With this combination, the reaction that generates bleaching active species proceeds relatively efficiently in alkaline conditions but slows down in neutral conditions. Therefore, bleaching agents and oxidizing agents that use peracids such as hydrogen peroxide tend to exhibit reduced bleaching and oxidizing power in neutral conditions. However, when the composition of the present invention is used in combination with hydrogen peroxide, the oxidizing and bleaching power of hydrogen peroxide is not reduced even in neutral conditions, and excellent effects can be achieved. DETAILED DESCRIPTION OF THE INVENTION

[0039] [Pyridinium compound (compound (1))] The compound (1) is a pyridinium compound represented by the general formula (1). In general formula (1), R 1 is a hydrocarbon group having 2 to 24 carbon atoms. 1 From the viewpoint of excellent solubility in water of compound (1), the number of carbon atoms in R may be, for example, 3 or more, further 4 or more, and 22 or less, further 20 or less, further 18 or less, further 16 or less, further 14 or less, further 12 or less, further 8 or less, or further 6 or less. 1 Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group, and an alkyl group is preferred.

[0040] In general formula (1), -R 1 Examples of the alkyl group include -CH2-(CH2) n11 -X 1 -(CH2) n12 -CH3, where X 1 is a single bond or a heteroatom, n11 and n12 are each an integer of 0 to 22, and the sum of n11 and n12 is 1 to 22. For example, the sum of n11 and n12 is 1 The total number of carbon atoms can be selected so as to be within the above range. Examples of heteroatoms include nitrogen atoms, oxygen atoms, sulfur atoms, and phosphorus atoms. 1 Regarding X, heteroatom may be meant to include groups containing heteroatoms such as SO2. 1 is preferably a single bond.

[0041] In the general formula (1), Y is the above-mentioned predetermined group, and is bonded to any one of the carbon atoms at the 2nd, 4th, and 6th positions of the pyridine ring of the compound (1), and R 2 is a hydrocarbon group which may contain a heteroatom. The positions of the pyridine ring are numbered as follows:

[0042] [ka]

[0043] In general formula (1), R 2R is a hydrocarbon group which may contain a heteroatom. 2 The number of carbon atoms in R is, for example, 1 or more and 24 or less, and from the viewpoint of excellent solubility in water of compound (1), it may be 12 or less, or even 7 or less. Examples of heteroatoms include nitrogen atoms, oxygen atoms, sulfur atoms, and phosphorus atoms. 2 Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group.

[0044] In general formula (1), -R 2 For example, -X 2 -C(Z)3, where X 2 is a hydrocarbon group having a ring structure or (C(Z)2) n21 Z is a hydrogen atom or a heteroatom, and n21 is an integer of 0 or more and 23 or less from the viewpoint of excellent solubility of compound (1) in water. X 2 The number of carbon atoms in the hydrocarbon group having a ring structure may be, for example, 6 or more and 24 or less, from the viewpoint of excellent solubility of compound (1) in water. 2 Among these, examples of hydrocarbon groups having a ring structure include groups derived from aromatic compounds, and specific examples include a phenylene group and a naphthylene group (naphthalenediyl group). 2 Among them, (C(Z)2) n21 is a single bond when n21 is 0, and is an alkylene group (alkanediyl group) when n21 is 1 or more. n21 may be 0 or more and 11 or less, or even 6 or less. Examples of heteroatoms include halogen atoms, nitrogen atoms, oxygen atoms, sulfur atoms, and phosphorus atoms.

[0045] In the general formula (1), examples of Y include a ((trifluoromethyl)sulfonyl)oxy group (TfO), a mesyloxy group (MsO), a tosyloxy group (TsO), and an orthonitrosulfonyloxy group (NsO), from the viewpoint of ease of synthesis of the compound (1).

[0046] In general formula (1), A - is an anion. -The anion in A may be either an organic anion or an inorganic anion. - Examples of anions of A include anions that are conjugate bases of acids with a pKa of 5 or less. - 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 - ) and bis(trifluoromethanesulfonic acid)imide ion ((CF3SO2)2N - ), trifluoroacetate ion (CF3COO - From the viewpoint of the excellent solubility of compound (1) in water and the ease of synthesis of compound (1), A - is preferably - OTf, - OSO3Me, - OTs, - OMs, Cl - , and Br - is an anion selected from the group consisting of:

[0047] In the compound (1), -R in the general formula (1) 2 Ga-X 2As shown in the examples below, compounds with -C(Z) can be synthesized by reacting an N-alkyl 4-pyridone compound (an N-alkyl-substituted pyridine having a carbonyl group), such as N-methyl 4-pyridone, with a sulfonylating agent, such as tosyl chloride or trifluoromethanesulfonic anhydride. N-Alkyl 4-pyridones, such as N-methyl 4-pyridone, are known to have the following resonance structure:

[0048] [ka]

[0049] A reaction solvent can be used for the synthesis of compound (1). From the viewpoint of improving the yield of compound (1), the reaction solvent is preferably a non-polar solvent, particularly an aromatic hydrocarbon solvent such as benzene or toluene. More specifically, examples of the reaction solvent include benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trifluoromethylbenzene, and nitrobenzene.

[0050] The reaction temperature during the synthesis of compound (1) is, for example, preferably −20° C. or higher, more preferably −10° C. or higher, and even more preferably 0° C. or higher, from the viewpoint of promoting a reduction in the reaction time, and is, for example, preferably 60° C. or lower, more preferably 40° C. or lower, and even more preferably 25° C. or lower, from the viewpoint of improving the yield of compound (1).

[0051] After the reaction, compound (1) can be subjected to treatments such as extraction, purification, and recovery, as necessary, and these treatments can include, for example, solid-liquid extraction, liquid-liquid extraction, column chromatography, preparative TLC, recrystallization, washing with a solvent, etc. Examples of solvents used for washing include diethyl ether, toluene, benzene, and hexane, from the viewpoints of improving the yield of compound (1) and being economical.

[0052] Compound (1) of the present invention is expected to be used directly or indirectly in a wide variety of fields, for example, as a bleaching agent, a decolorizing agent, a reactant, a cleaner, a deodorizer, an antiviral agent, a disinfectant, a sporicide, etc. Compound (1) of the present invention is expected to be used directly or indirectly in various applications, for example, in the following fields: (I) Paper and pulp industry: bleaching of various pulps, deinking and bleaching of waste paper, etc. (II) Textile industry: for bleaching natural fibers such as cotton, wool, silk, and synthetic fibers. (III) Chemical industry: raw materials for organic and inorganic peroxides, organic compounds, and epoxy compounds (IV) Electronics industry: Etching and cleaning of semiconductors and printed circuit boards (V) Pollution treatment field: Deodorization, sterilization, decolorization of sewage and industrial wastewater, soil improvement, etc. (VI) Mining industry: applications such as oxidation of metals in refining processes (VII) Food industry: sterilization of food manufacturing equipment, sterilization of containers, bleaching of food, etc. (VIII) Pharmaceutical field: Use as intermediate raw materials for pharmaceuticals (IX) Metal finishing field: Surface treatment of metals, purification of plating solutions, etc. (X) Wood industry: Wood bleaching, decorative board bleaching, etc.

[0053] [Method for producing pyridinium compounds] The present invention relates to a method for producing a pyridinium compound, which comprises step 1 of reacting a compound represented by the following general formula (1') [hereinafter referred to as compound (1')] with a sulfonylating agent to obtain a pyridinium compound represented by the following general formula (1) [compound (1)].

[0054] [ka]

[0055] [In the formula, R 1 is a hydrocarbon group having 2 to 24 carbon atoms, and Y' is -O -and Y' is bonded to any one of the carbon atoms at the 2-, 4-, and 6-positions of the pyridine ring.

[0056] [ka]

[0057] [In the formula, R 1 is a hydrocarbon group having 2 to 24 carbon atoms, and Y is

[0058] [ka]

[0059] Y is bonded to any one of the carbon atoms at the 2-, 4-, and 6-positions of the pyridine ring, and R 2 is a hydrocarbon group which may contain a heteroatom, and A - is an anion.

[0060] In general formula (1'), R 1 is a hydrocarbon group having 2 to 24 carbon atoms. 1 From the viewpoint of excellent solubility in water of the pyridinium compound of general formula (1) produced from compound (1'), the number of carbon atoms in R may be, for example, 3 or more, further 4 or more, and 22 or less, further 20 or less, further 18 or less, further 16 or less, further 14 or less, further 12 or less, further 8 or less, or further 6 or less. 1 Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group, and an alkyl group is preferred.

[0061] In general formula (1'), -R 1 Examples of the alkyl group include -CH2-(CH2) n11 -X 1 -(CH2) n12 -CH3, where X 1is a single bond or a heteroatom, n11 and n12 are each an integer of 0 to 22, and the sum of n11 and n12 is 1 to 22. For example, the sum of n11 and n12 is 1 The total number of carbon atoms can be selected so as to be within the above range. Examples of heteroatoms include nitrogen atoms, oxygen atoms, sulfur atoms, and phosphorus atoms. 1 Regarding X, heteroatom may be meant to include groups containing heteroatoms such as SO2. 1 is preferably a single bond.

[0062] In the general formula (1'), Y' is -O - and is bonded to any one of the carbon atoms at positions 2, 4, and 6 of the pyridine ring of compound (1'), and the position numbers of the pyridine ring are as described above.

[0063] As the compound (1'), from the viewpoint of ease of synthesis of the compound, for example, N-alkyl-2-pyridone, N-alkyl-4-pyridone, N-alkyl-6-pyridone, etc. are preferred, and N-alkyl-4-pyridone is more preferred.

[0064] Examples of the sulfonylating agent include sulfonyl halide compounds and sulfonic acid anhydrides. The sulfonyl halide compound is, for example, R 2 SO2X (X is a halogen. 2 is a hydrocarbon group which may contain a heteroatom. In addition, sulfonic acid anhydrides can be compounds represented by, for example, R 2 SO2OSO2R 2 (R 2 is a hydrocarbon group which may contain a hetero atom. That is, the sulfonylating agent used in the present invention is R 2 SO2X (X is a halogen. 2 is a hydrocarbon group which may contain a heteroatom. 2 SO2OSO2R 2 (R 2is a hydrocarbon group which may contain a hetero atom. R in the above formula 2 For example, -X 2 -C(Z)3, where X 2 is a hydrocarbon group having a ring structure or (C(Z)2) n21 Z is a hydrogen atom or a heteroatom, and n21 is an integer of 0 or more and 23 or less from the viewpoint of excellent solubility of compound (1) in water. X 2 The number of carbon atoms in the hydrocarbon group having a ring structure may be, for example, 6 or more and 24 or less, from the viewpoint of excellent solubility in water of the pyridinium compound produced using this sulfonylating agent. 2 Among these, examples of hydrocarbon groups having a ring structure include groups derived from aromatic compounds, and specific examples include a phenylene group and a naphthylene group (naphthalenediyl group). 2 Among them, (C(Z)2) n21 When n21 is 0, it is a single bond, and when n21 is 1 or greater, it is an alkylene group (alkanediyl group). n21 may be 0 or greater and 11 or less, or even 6 or less. Examples of heteroatoms include halogen atoms, nitrogen atoms, oxygen atoms, sulfur atoms, and phosphorus atoms. Examples of sulfonyl halide compounds and compounds of the above formula include tosyl chloride (TsCl). Examples of sulfonic acid anhydrides and compounds of the above formula include trifluoromethanesulfonic acid anhydride (TfO).

[0065] A reaction solvent can be used for the reaction of compound (1') with a sulfonylating agent. That is, in the present invention, compound (1') can be reacted with a sulfonylating agent in a reaction solvent. From the viewpoint of improving the yield of the pyridinium compound, the reaction solvent is preferably a non-polar solvent, particularly an aromatic hydrocarbon solvent such as benzene or toluene. More specifically, examples of the reaction solvent include benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trifluoromethylbenzene, and nitrobenzene.

[0066] The reaction temperature when reacting compound (1') with a sulfonylating agent is, from the viewpoint of shortening the reaction time, for example, preferably -20°C or higher, more preferably -10°C or higher, and even more preferably 0°C or higher, and from the viewpoint of improving the yield of the product, for example, preferably 60°C or lower, more preferably 40°C or lower, and even more preferably 25°C or lower.

[0067] The equivalent of compound (1') / sulfonylating agent in the reaction between compound (1') and a sulfonylating agent can be, for example, 1 or more from the viewpoint of excellent reactivity, and can be, for example, 1.25 or less, or even 1.1 or more from the viewpoint of excellent cost efficiency. Furthermore, the reaction molar ratio of compound (1') to the sulfonylating agent, compound (1') / sulfonylating agent, can be, for example, 1 or more from the viewpoint of excellent reactivity, and can be, for example, 1.25 or less, or even 1.1 or more from the viewpoint of excellent cost performance.

[0068] The reaction pressure and reaction time when reacting compound (1') with a sulfonylating agent are not particularly limited and can be set appropriately. Furthermore, the reaction of compound (1') with a sulfonylating agent is preferably carried out under stirring, for example, from the viewpoint of achieving a high yield. Stirring can be carried out at, for example, 100 rpm or more, depending on the scale of the reaction apparatus.

[0069] After the reaction of compound (1') with a sulfonylating agent, if necessary, treatments such as extraction, purification, and recovery of the target compound (pyridinium compound) can be performed, and these treatments can include, for example, solid-liquid extraction, liquid-liquid extraction, column chromatography, preparative TLC, recrystallization, washing with a solvent, etc. Examples of solvents used for washing include diethyl ether, toluene, benzene, and hexane, from the viewpoints of improving the yield of the target compound and being economical.

[0070] The method for producing a pyridinium compound of the present invention may include, before step 1, a step of reacting hydroxypyridine with an electrophilic agent to obtain compound (1′) (hereinafter referred to as the pre-step).

[0071] From the viewpoint of ease of synthesis of compound (1′), examples of hydroxypyridine include 2-hydroxypyridine, 4-hydroxypyridine, and 6-hydroxypyridine, and preferably 4-hydroxypyridine.

[0072] As the electrophile, the nitrogen atom of the hydroxypyridine is bonded to the R 1 As long as it is possible to introduce a group corresponding to R, there are no particular limitations on the electrophilic agent, and it can be appropriately selected taking into consideration factors such as cost and reactivity. Examples of electrophilic agents include electrophilic agents having a hydrocarbon group with 2 to 24 carbon atoms. This hydrocarbon group is R 1 The preferred embodiment corresponds to R 1 The electrophilic agent includes, for example, an alkylating agent, and further, an alkylating agent having a hydrocarbon group having 2 to 24 carbon atoms. Examples of the alkylating agent include alkyl halides such as alkyl bromides, and sulfonic acid esters such as alkyl tosylates and alkyl mesylates. From the viewpoint of ensuring that the pyridinium compound produced from compound (1') has excellent solubility in water, the alkylating agent may have, for example, 3 or more, further 4 or more, and 22 or less, further 20 or less, further 18 or less, further 16 or less, further 14 or less, further 12 or less, further 8 or less, or further 6 or less hydrocarbon groups. In the present invention, the term "alkylating agent" refers to a compound capable of introducing not only an alkyl group but also a hydrocarbon group into hydroxypyridine. That is, the alkylating agent may have a hydrocarbon group other than an alkyl group, such as an alkenyl group or an aryl group.

[0073] The equivalent weight in the reaction between hydroxypyridine and electrophilic agent, hydroxypyridine / electrophilic agent, can be, for example, 1 or more, further 2 or more, and 100 or less, further 10 or less, further 5 or less, from the viewpoint of excellent reactivity. The molar ratio in the reaction between hydroxypyridine and an electrophile is the ratio of hydroxypyridine to electrophile (hydroxypyridine / electrophile), and can be, for example, from the viewpoint of excellent reactivity, 1 or more, further 2 or more, and 100 or less, further 10 or less, or further 5 or less.

[0074] A reaction solvent can be used for the reaction between hydroxypyridine and an electrophile. That is, in the present invention, hydroxypyridine and an electrophile can be reacted in a reaction solvent. From the viewpoint of excellent solubility and reactivity, the reaction solvent may be a polar solvent, and preferably an aprotic polar solvent such as acetonitrile or acetone.

[0075] The reaction between hydroxypyridine and an electrophile is preferably carried out in the presence of a base. The base is preferably an inorganic base from the viewpoint of promoting the reaction between hydroxypyridine and an electrophile. Examples of inorganic bases include alkali metal carbonates such as potassium carbonate and cesium carbonate, alkaline earth metal carbonates such as calcium carbonate, phosphates such as potassium phosphate, alkali metal hydrides such as sodium hydride, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The base is preferably used in a ratio of, for example, 1 equivalent or more, more preferably 1.25 equivalents or more, and even more preferably 1.5 equivalents or more relative to the hydroxypyridine.

[0076] The reaction temperature when reacting hydroxypyridine with an electrophile is, from the viewpoint of promoting the reaction between hydroxypyridine and an electrophile, for example, preferably 40°C or higher, more preferably 50°C or higher, even more preferably 60°C or higher, and preferably 120°C or lower, more preferably 100°C or lower, even more preferably 90°C or lower.

[0077] The reaction pressure when reacting hydroxypyridine with an electrophilic agent is not particularly limited and can be set appropriately.

[0078] The reaction time for reacting hydroxypyridine with an electrophilic agent may be, for example, 8 hours or more and 24 hours or less, from the viewpoint of improving the yield of compound (1′).

[0079] The reaction of hydroxypyridine with an electrophile is preferably carried out under stirring, for example, from the viewpoint of improving the yield of compound (1'). Although it depends on the scale of the reaction apparatus, stirring can be carried out at, for example, 100 rpm or more.

[0080] After the reaction of hydroxypyridine with an electrophile, the target compound (compound (1')) can be subjected to treatments such as extraction, purification, and recovery, as necessary. For these treatments, for example, solid-liquid extraction, liquid-liquid extraction, column chromatography, preparative TLC, recrystallization, washing with a solvent, etc. Examples of solvents used for washing include diethyl ether, toluene, benzene, and hexane, from the viewpoints of improving the yield of compound (1') and being economical.

[0081] As an example of the manufacturing method of the present invention, A compound represented by the general formula (1') (compound (1')) and R 2 SO2X (X is a halogen. 2 is a hydrocarbon group which may contain a heteroatom. 2 SO2OSO2R 2 (R 2 is a hydrocarbon group which may contain a heteroatom.) to obtain a pyridinium compound represented by the general formula (1) (compound (1)).

[0082] The method for producing a pyridinium compound of the present invention is suitable as a method for producing the novel pyridinium compound of the present invention.

[0083] [Composition] The composition of the present invention is an acidic composition that contains a pyridinium compound represented by the general formula (1) [component (A)] and water. The reason why the composition of the present invention has excellent stability is not entirely clear, but it is thought that this is because active esters, which are common bleach activators, tend to be unstable under acidic conditions because the active ester group is protonated and activated, whereas component (A) of the present invention does not have an active ester group and is not activated even under acidic conditions.

[0084] Although the reason why the composition of the present invention exhibits excellent oxidizing power in a neutral state when used in combination with hydrogen peroxide is not entirely clear, it is presumed that this is because component (A) of the composition of the present invention is more reactive with hydrogen peroxide than common organic peracid precursors, and therefore sufficient active species are formed even in a neutral state. Furthermore, under acidic conditions, the reactivity of component (A) with hydrogen peroxide is extremely low, and it is presumed that component (A) can exist stably in the composition of the present invention even when hydrogen peroxide coexists. The mechanisms of the present invention are not limited to these.

[0085] The component (A) is one or more compounds selected from the compounds represented by the general formula (1), i.e., compound (1). 1 , Y, R 2 , A - Specific examples and preferred examples of the compound (1) are the same as those of the compound (1).

[0086] From the viewpoint of improving the oxidative decomposition activity, the composition of the present invention preferably contains component (A) in an amount of, for example, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, and 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0087] The composition of the present invention contains water. Examples of water include ion-exchanged water and tap water. Water can be used in an amount that makes the total composition of the composition of the present invention 100% by mass. The composition of the present invention preferably contains water in an amount of, for example, 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and more preferably 99.99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.

[0088] The composition of the present invention may contain (B) hydrogen peroxide (hereinafter referred to as component (B)). When the composition of the present invention contains component (B), the composition preferably contains component (B) in an amount of, for example, 0.01% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and more preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, from the viewpoint of excellent safety.

[0089] When the composition of the present invention contains the component (B), from the viewpoint of improving the oxidative decomposition activity, the content of the component (B) relative to 1 molar part of the content of the component (A) is, for example, preferably 1 molar part or more, more preferably 22 molar parts or more, even more preferably 33 molar parts or more, and is preferably 100 molar parts or less, more preferably 55 molar parts or less, even more preferably 44 molar parts or less.

[0090] The composition of the present invention may contain optional components in addition to component (B). Examples of such optional components include chelating agents, thickeners, surfactants, and polymers. Component (B) may also be formulated as aqueous hydrogen peroxide. When a specific component is formulated in a form containing water, such as aqueous hydrogen peroxide, the water contained in that form constitutes part or all of the water component in the liquid composition of the present invention.

[0091] The composition of the present invention is suitable for use as an oxidizing agent. That is, for example, the composition of the present invention can be used as an oxidizing agent together with hydrogen peroxide, or can be used to produce an oxidizing agent. The composition of the present invention is also suitable for use as a bleaching agent. That is, for example, the composition of the present invention can be used as a bleaching agent together with hydrogen peroxide, or can be used to produce a bleaching agent.

[0092] When the composition of the present invention is used, for example, as an oxidizing agent or bleaching agent, the concentration of component (A) is, for example, preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and is preferably 10% by mass or less, even more preferably 1% by mass or less, even more preferably 0.1% by mass or less. Furthermore, when the composition of the present invention contains component (B), the concentration of component (B) during use, for example, when used as an oxidizing agent or bleaching agent, is preferably, for example, 0.001% by mass or more, further 0.01% by mass or more, even 0.1% by mass or more, and 30% by mass or less, further 3% by mass or less, even 1% by mass or less.

[0093] The composition of the present invention may be in any form, such as a liquid composition or a gel composition. It is preferable that the composition is in a liquid form. The composition of the present invention can also be obtained, for example, by mixing a solid agent containing component (A) with water. That is, the present invention provides a kit for an acidic composition containing component (A) and water, which kit includes a solid agent containing component (A).

[0094] The composition of the present invention may have a pH at 25°C of, for example, 2 or more, preferably 3 or more, and less than 7, preferably 6 or less, and preferably 5 or less, from the viewpoint of excellent composition stability. To achieve such a pH, a pH adjuster may be contained. Examples of pH adjusters include hydrogen phosphates such as disodium hydrogen phosphate and potassium dihydrogen phosphate; organic acids such as lactic acid, succinic acid, gluconic acid, citric acid, acetic acid, and tartaric acid; inorganic acids such as phosphoric acid, boric acid, hydrochloric acid, and sulfuric acid; and sulfonic acids such as paratoluenesulfonic acid, camphorsulfonic acid, and methanesulfonic acid. The pH adjuster may be selected in combination to have buffering capacity.

[0095] The composition of the present invention can be used for various applications in which an oxidation action has a beneficial effect on an object to be treated, such as bleaching hard articles in bathrooms, toilets, kitchens, etc., mold removal, bleaching clothing, decomposition of stain- and odor-causing substances, sterilization, virucide, and pulp bleaching. The composition of the present invention can be used, if necessary, in combination with hydrogen peroxide or the like, as a bleaching agent composition, a bleaching detergent composition, a mold removal agent composition, a bleaching agent composition, a deodorizing agent composition, a disinfectant composition, a virucide composition, or the like. Of these, the composition of the present invention is preferably used for bleaching or bleach-cleaning. Furthermore, it is more preferably used for bleaching or bleach-cleaning hard articles.

[0096] The present invention provides use of the composition of the present invention for producing an oxidizing agent. The present invention also provides the use of the composition of the present invention for the production of a bleaching agent. If the composition of the present invention is suitable for oxidation or bleaching, the composition can be used as an oxidizing agent or a bleaching agent as it is. In other words, if the composition of the present invention is suitable for oxidation or bleaching, the method for producing the composition of the present invention is also a method for producing an oxidizing agent or a bleaching agent.

[0097] In the above-described use, the oxidizing agent or bleaching agent preferably contains component (A) in an amount of, for example, 0.0001% by mass or more, preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and 10% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less, from the viewpoint of improving oxidative decomposition activity. The composition may contain component (A) in this range. In the above-described use, the oxidizing agent or bleaching agent preferably contains component (B). In this case, the oxidizing agent or bleaching agent preferably contains component (B) in an amount of, for example, 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and more preferably 30% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. The composition may contain component (B) in this range.

[0098] [Oxidation method and bleaching method] The present invention provides an oxidation method in which a treatment liquid prepared from the composition of the present invention is brought into contact with a target substance, for example, a pigment such as curcumin, an environmentally hazardous substance such as dioxins, or a protein contained in a microorganism such as a bacterium or a virus, in the presence of hydrogen peroxide. The present invention also provides a bleaching method in which a treatment solution prepared from the composition of the present invention (hereinafter also referred to as the treatment solution of the present invention) is brought into contact with an object, such as clothing or a hard article, in the presence of hydrogen peroxide.

[0099] The processing solution of the present invention preferably contains component (A), component (B), and water. If the composition of the present invention is suitable for oxidation or bleaching, the composition can be used as is as the processing solution of the present invention. Alternatively, the processing solution of the present invention may be prepared by mixing a composition containing component (A) but not component (B) with a compound that serves as a source of component (B) or a composition containing component (B).

[0100] The treatment solution of the present invention can be obtained by mixing the composition of the present invention containing component (A) and water with component (B) and / or a source of component (B), such as a peroxide that generates hydrogen peroxide in water, and, if necessary, water. Peroxides that generate hydrogen peroxide in water include inorganic peroxides and hydrogen peroxide adducts, preferably one or more selected from percarbonates, tripolyphosphate-hydrogen peroxide adducts, pyrophosphate-hydrogen peroxide adducts, urea-hydrogen peroxide adducts, sulfate-hydrogen peroxide adducts, perborates, persilicates, and peroxide salts. More preferably, sodium percarbonate, sodium tripolyphosphate-hydrogen peroxide adducts, sodium pyrophosphate-hydrogen peroxide adducts, urea-hydrogen peroxide adducts, 4NaSO.2H.sub.2O.sub.2, sodium perborate monohydrate, sodium perborate tetrahydrate, sodium persilicate, sodium peroxide, calcium peroxide, etc. Alternatively, the composition of the present invention can be prepared using the kit described above, and then the composition is mixed with component (B) and / or a source of component (B), and, if necessary, water. Furthermore, as described below, depending on the intended use, a pH adjuster that also functions as a buffer, such as a phosphate buffer, may be added to adjust the pH of the processing solution to, for example, 3 or more, 5 or more, 6 or more, 12 or less, 10 or less, or 8 or less. This pH is the pH at the temperature at which the oxidation method or bleaching method of the present invention is carried out, and may be the pH at, for example, 25°C.

[0101] From the viewpoint of improving the oxidative decomposition activity, the treatment liquid of the present invention preferably contains, for example, 0.0001% by mass or more of component (A), more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and 10% by mass or less, even more preferably 1% by mass or less, even more preferably 0.1% by mass or less of component (A).

[0102] The treatment liquid of the present invention preferably contains component (B) in an amount of, for example, 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and 30% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

[0103] Examples of objects to be subjected to the oxidation method and the bleaching method include hard items such as those used in baths, toilets, and kitchens, and textile products such as clothing. In the oxidation method and the bleaching method, the composition of the present invention can be brought into contact with the object in the presence of hydrogen peroxide by immersion, application, spraying, or other methods. The contact time and contact temperature when the composition of the present invention is brought into contact with the object are not limited.

[0104] The treatment liquid of the present invention can contain any of the components described in the composition of the present invention.

[0105] From the viewpoint of improving oxidative decomposition activity, the pH of the processing solution of the present invention is, for example, preferably 3 or more, more preferably 5 or more, even more preferably 6 or more, and 12 or less, even more preferably 10 or less, even more preferably 8 or less. This pH is the pH at the temperature at which the oxidation method or bleaching method of the present invention is carried out, and may be the pH at, for example, 25°C. In the oxidation method or bleaching method of the present invention, excellent oxidizing power or bleaching power can be obtained even at a near-neutral pH in the presence of hydrogen peroxide.

[0106] [Storage method] The present invention provides a method for preserving a compound (hereinafter also referred to as the preservation method of the present invention), which comprises preserving component (A) in acidic water. The preservation method of the present invention can be appropriately applied to the matters described for the composition of the present invention. Specific examples and preferred examples of component (A) in the preservation method of the present invention are the same as those for the composition of the present invention. The preservation method of the present invention may be a method for preserving component (A) or the composition of the present invention.

[0107] In the storage method of the present invention, the content of component (A) in acidic water is, from the viewpoint of improving oxidative decomposition activity, preferably, for example, 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, and 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less.

[0108] In the preservation method of the present invention, component (A) is preserved in acidic water. The pH of the acidic water used for preservation is, for example, 2 or higher, preferably 3 or higher, and less than 7, preferably 6 or lower, and more preferably 5 or lower, from the viewpoint of excellent composition stability. To achieve such a pH, a pH adjuster can be added. Examples of pH adjusters include hydrogen phosphates such as disodium hydrogen phosphate and potassium dihydrogen phosphate; organic acids such as lactic acid, succinic acid, gluconic acid, citric acid, acetic acid, and tartaric acid; inorganic acids such as phosphoric acid, boric acid, hydrochloric acid, and sulfuric acid; and sulfonic acids such as paratoluenesulfonic acid, camphorsulfonic acid, and methanesulfonic acid. The pH adjuster may be selected in combination to have buffering capacity. Note that this pH is the pH in a state containing optional components such as component (A) and component (B).

[0109] The preservation method of the present invention can be carried out in the presence of components other than component (A). For example, the optional components described for the composition of the present invention can be added to acidic water to carry out preservation. In the present invention, it is preferable to store component (A) in acidic water in the coexistence of hydrogen peroxide as component (B). When component (B) is coexistent, in the storage method of the present invention, the content of component (B) in the acidic water is, for example, preferably 0.01% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, and 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, from the viewpoint of excellent stability and safety of the composition.

[0110] The preservation method of the present invention can be used, for example, as a method for preserving the composition of the present invention, the composition of the present invention for use as an oxidizing agent, or the composition of the present invention for use as a bleaching agent.

[0111] In the storage method of the present invention, the temperature of the acidic water is not particularly limited, but from the viewpoint of excellent stability of the composition, it is preferably, for example, 0°C or higher, more preferably 25°C or higher, and 60°C or lower, more preferably 50°C or lower.

[0112] In the storage method of the present invention, the storage period is not particularly limited, but is preferably, for example, 1 day or more, more preferably 14 days or more, and 730 days or less, more preferably 365 days or less.

[0113] In the preservation method of the present invention, for example, water, component (A), and optionally component (B) and other optional components are put into a predetermined container, and the liquidity is adjusted to be acidic, preferably to the pH within the above range, so that component (A) can be preserved. The shape, capacity, etc. of the container are not limited. The container preferably has a means for sealing the opening, such as a lid or a stopper.

Example

[0114] <NMR measurement conditions> The measurement conditions of NMR ( 1 1H NMR) performed in the synthesis examples and examples are as follows. · Apparatus: Vnmr 400MR DD2 (manufactured by Agilent) · Measurement temperature: 25 °C · Waiting time: 10 seconds · Number of integrations: 8 times · Observation range: 6410.3 Hz · Pulse: 45° · Data points: 65536

[0115] Synthesis Example 1 <Synthesis of 1-butylpyridin-4(1H)-one> The title compound was synthesized according to the following scheme.

[0116]

Chemical formula

[0117] To a 500 ml single-necked recovery flask, 10 g (72.98 mmol) of 1-bromobutane, acetone (146 ml), potassium carbonate (15.13 g, 109.47 mmol, 1.5 equivalents), and 4-hydroxypyridine (10.41 g, 109.47 mmol, 1.5 equivalents) were added and stirred overnight under reflux. After completion of the reaction, the reaction solution was cooled to room temperature (25°C) and concentrated using a rotary evaporator. After concentration, water and chloroform were added to the residue, and the aqueous layer was extracted with chloroform. The extracted organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated using a rotary evaporator. The resulting residue was purified using column chromatography (ethyl acetate:ethanol = 2:1 → 1:1) to obtain the target product (8.4 g, yield 76%). 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, CDCl3) δ : 7.27 (2H, d, J = 7.6Hz), 6.38 (1H, d, J = 7.6 Hz), 3.77 (2H, t, J = 7.2 Hz), 1.79-1.72 (2H, m),1.41-1.33 (2H, m), 0.97 (3H, t, J = 7.2 Hz) ppm.

[0118] Synthesis Example 2 <Synthesis of 1-dodecylpyridin-4(1H)-one> The title compound was synthesized according to the following scheme.

[0119] [ka]

[0120] To a 200 ml single-necked recovery flask, 5 g (20.06 mmol) of dodecyl bromide, acetonitrile (40 ml), potassium carbonate (4.16 g, 30.9 mmol, 1.5 equivalents), and 4-hydroxypyridine (3.82 g, 40.12 mmol, 2 equivalents) were added and stirred under reflux overnight. After completion of the reaction, the reaction solution was cooled to room temperature (25°C) and concentrated using a rotary evaporator. After concentration, water and chloroform were added to the residue, and the aqueous layer was extracted with chloroform. The extracted organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated using a rotary evaporator. The resulting residue was purified using column chromatography (ethyl acetate:ethanol = 4:1 → 2:1) to obtain the target product (3.2 g, yield 79%). 1 The results of 1 H NMR measurement were as follows: 1 H NMR (400MHz, CDCl3) δ : 7.27 (2H, d, J = 7.6 Hz),6.38 (1H, d, J = 7.6 Hz), 3.75 (2H, t, J = 7.2 Hz), 1.80-1.75 (2H, m), 1.41-1.22(18H, m), 0.88 (3H, t, J = 7.2 Hz) ppm.

[0121] Synthesis Example 3 <Synthesis of 1-eicocylpyridin-4(1H)-one> The title compound was synthesized according to the following scheme.

[0122] [ka]

[0123] To a 200 ml single-necked recovery flask, 10 g (27.67 mmol) of 1-bromoeicosane, acetonitrile (55.33 ml), potassium carbonate (5.74 g, 41.50 mmol, 1.5 equivalents), and 4-hydroxypyridine (3.95 g, 41.50 mmol, 1.5 equivalents) were added, and the mixture was stirred under reflux overnight. After completion of the reaction, the reaction solution was cooled to room temperature (25°C) and concentrated using a rotary evaporator. After concentration, water and chloroform were added to the residue, and the aqueous layer was extracted with chloroform. The extracted organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated using a rotary evaporator. The resulting residue was purified using column chromatography (ethyl acetate:ethanol = 4:1 → 2:1) to obtain the target product (10.4 g, yield 100%). 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, CDCl3) δ : 7.24 (2H, d, J = 7.6Hz), 6.34 (1H, d, J = 7.6 Hz), 3.74 (2H, t, J = 7.2 Hz), 1.78-1.74 (2H, m),1.41-1.33 (33H, m), 0.88 (3H, t, J = 7.2 Hz) ppm.

[0124] Example 1 <Synthesis of 1-butyl-4-(tosyloxy)pyridin-1-ium chloride> The title compound was synthesized according to the following scheme.

[0125] [ka]

[0126] To a 50 ml single-necked recovery flask, 0.5 g (3.31 mmol) of 1-butylpyridin-4(1H)-one and toluene (6.61 ml) were added and stirred at room temperature (25°C). Tosyl chloride (0.63 g, 3.31 mmol, 1 equivalent) was added and stirred at room temperature (25°C). After the reaction was completed, the reaction solution was concentrated using a rotary evaporator. The obtained crystals were washed with diethyl ether to obtain the target product (11 g, 100% yield). 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, D2O) δ : 8.74 (2H, d, J = 7.2 Hz),7.78 (2H, d, J = 8.4 Hz), 7.70 (2H, d, J = 6.8 Hz), 7.40 (2H, d, J = 8.4 Hz), 4.43(2H, t, J = 7.2 Hz), 2.34 (3H, s), 1.85-1.78 (2H, m), 1.20-1.13 (2H, m), 0.79(3H, t, J = 7.6 Hz) ppm.

[0127] Example 2 <Synthesis of 1-butyl-4-(((trifluoromethyl)sulfonyl)oxy)pyridin-1-ium trifluoromethanesulfonate> The title compound was synthesized according to the following scheme.

[0128] [ka]

[0129] To a 50 ml single-necked recovery flask, 0.5 g (3.31 mmol) of 1-butylpyridin-4(1H)-one and toluene (6.61 ml) were added and stirred at room temperature (25°C). Trifluoromethanesulfonic anhydride (0.93 g, 3.31 mmol, 1 equivalent) was added and stirred at room temperature (25°C). After completion of the reaction, the reaction solution was concentrated using a rotary evaporator. The obtained crystals were washed with diethyl ether to obtain the target product (1 g, yield 73%). 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, D2O) δ : 8.85 (2H, d, J = 7.2 Hz),7.76 (2H, d, J = 7.6 Hz), 4.49 (2H, t, J = 7.2 Hz), 1.93-1.85 (2H, m), 1.30-1.24(2H, m), 0.84 (3H, t, J = 7.6 Hz) ppm.

[0130] Example 3 <Synthesis of 1-dodecyl-4-(tosyloxy)pyridin-1-ium chloride> The title compound was synthesized according to the following scheme.

[0131] [ka]

[0132] To a 50 ml single-necked recovery flask, 1.44 g (3.8 mmol) of 1-dodecylpyridin-4(1H)-one and toluene (7.59 ml) were added and stirred at room temperature (25°C). Tosyl chloride (0.724 g, 3.8 mmol, 1 equivalent) was added and stirred at room temperature (25°C). After the reaction was completed, the reaction solution was concentrated using a rotary evaporator. The obtained crystals were washed with diethyl ether to obtain the target product (2.4 g, yield 96%). 1 The results of 1 H NMR measurement were as follows: 1H NMR(400 MHz, CDCl3) δ : 9.32 (2H, d, J = 6.8Hz), 7.88 (2H, d, J = 7.6 Hz), 7.70 (2H, d, J = 8 Hz) 7.13 (2H, J = 8 Hz), 4.75(2H, t, J = 7.6 Hz), 2.34 (3H, s), 1.87-1.81 (2H, m), 1.30-1.16 (18H, m), 0.88(3H, t, J = 7.6 Hz) ppm.

[0133] Example 4 <Synthesis of 1-dodecyl-4-(((trifluoromethyl)sulfonyl)oxy)pyridin-1-ium trifluoromethanesulfonate> The title compound was synthesized according to the following scheme.

[0134] [ka]

[0135] In a 50 ml single-necked recovery flask, 1 g (3.8 mmol) of 1-dodecylpyridin-4(1H)-one and toluene (7.59 ml) were added and stirred at room temperature (25°C). Trifluoromethanesulfonic anhydride (1.07 g, 3.8 mmol, 1 equivalent) was added and stirred at room temperature (25°C). After the reaction was completed, the reaction solution was concentrated using a rotary evaporator. The obtained crystals were washed with diethyl ether to obtain the target product (0.92 g, yield 34%). 1 The results of 1 H NMR measurement were as follows: 1H NMR(400 MHz, CDCl3) δ : 9.14 (2H, d, J = 7.2Hz), 7.93 (2H, d, J = 7.2 Hz), 4.70 (2H, t, J = 7.2 Hz), 2.0-1.98 (2H,m), 1.40-1.19 (18H, m), 0.89 (3H, t, J = 6.8 Hz) ppm.

[0136] Example 5 <Synthesis of 1-eicocyl-4-(tosyloxy)pyridin-1-ium chloride> The title compound was synthesized according to the following scheme.

[0137] [ka]

[0138] To a 50 ml single-necked recovery flask, 2 g (5.32 mmol) of 1-eicosylpyridin-4(1H)-one and toluene (10.65 ml) were added and stirred at room temperature (25°C). Tosyl chloride (1.52 g, 7.99 mmol, 1.5 equivalents) was added and stirred at room temperature (25°C). After the reaction was completed, the reaction solution was concentrated using a rotary evaporator. The obtained crystals were washed with diethyl ether to obtain the target product (3 g, yield 100%). 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, CDCl3) δ : 9.32 (2H, d, J = 7.2Hz), 7.92 (2H, d, J = 7.2 Hz), 7.74 (2H, d, J = 8 Hz) 7.15 (2H, J = 8 Hz), 4.88(2H, t, J = 7.2 Hz), 2.34 (3H, s), 1.96-1.92 (2H, m), 1.48-1.19 (34H, m), 0.89(3H, t, J = 6.8 Hz) ppm.

[0139] Example 6 <Synthesis of 1-eicocyl-4-(((trifluoromethyl)sulfonyl)oxy)pyridin-1-ium trifluoromethanesulfonate> The title compound was synthesized according to the following scheme.

[0140] [ka]

[0141] To a 50 ml single-necked recovery flask, 2 g (5.32 mmol) of 1-eicosylpyridin-4(1H)-one and toluene (10.65 ml) were added and stirred at room temperature (25°C). Trifluoromethanesulfonic anhydride (1.5 g, 5.32 mmol, 1 equivalent) was added and stirred at room temperature (25°C). After completion of the reaction, the reaction solution was concentrated using a rotary evaporator. The obtained crystals were washed with diethyl ether to obtain the target product (2.9 g, 83% yield). 1 The results of 1 H NMR measurement were as follows: 1 H NMR(400 MHz, CDCl3) δ : 9.14 (2H, d, J = 7.2Hz), 7.93 (2H, d, J = 7.2 Hz), 4.70 (2H, t, J = 7.2 Hz), 2.0-1.98 (2H,m), 1.40-1.19 (34H, m), 0.89 (3H, t, J = 6.8 Hz) ppm.

[0142] <Reagents> The reagents used in the following Examples, Comparative Examples, Reference Examples and Comparative Reference Examples 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. Sodium dihydrogen phosphate: Fujifilm Wako Pure Chemical Industries, Ltd. Sodium 3-(trimethylsilyl)-1-propane-1,1,2,2,3,3-d6-sulfonate: 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 amount in parentheses is the effective amount. The amounts shown below are effective amounts.

[0143] Example 7 and Comparative Example 7 <Evaluation of storage stability 1> A phosphate buffer solution with a pH of 2.5 (25°C) was prepared using phosphoric acid, sodium dihydrogen phosphate, and heavy water, and this was used to prepare a solution containing 26.4 mM of component (A) in Table 1-1 (the compound synthesized in Examples 1, 3, 4, and 5) and 3 mM of sodium 3-(trimethylsilyl)-1-propane-1,1,2,2,3,3-d6-sulfonate (standard substance). This solution, excluding the standard substance, corresponds to the liquid composition with the composition (% by mass) in Table 1-1. The liquid compositions of the examples in Table 1-1 can be used as raw materials for oxidizing agents or bleaching agents. Immediately after preparing the liquid composition, 1 HNMR was measured, and after the measurement, the sample was stored at room temperature (25°C). 1 H NMR was measured. 1 The H NMR measurement conditions were the same as above. The amount of reduction in the peak of the evaluation compound (component (A)) was calculated from the peak ratio of the obtained chart to that of the standard substance, and the residual rate (%) of component (A) was determined by the internal standard method to evaluate storage stability. The results are shown in Table 1-1. A higher value indicates better storage stability.

[0144] [Table 1-1]

[0145] <Evaluation of storage stability 2> A phosphate buffer solution at pH 10.5 (25°C) was prepared using sodium bicarbonate, sodium carbonate, and heavy water. This solution was used to prepare a solution containing 26.4 mM of component (A) in Table 1-2 (the compounds synthesized in Examples 1, 3, 4, and 5) and 3 mM of sodium 3-(trimethylsilyl)-1-propane-1,1,2,2,3,3-d6-sulfonate (standard substance). This solution corresponds to the liquid composition with the composition (% by mass) in Table 1-2, excluding the standard substance. Storage stability was evaluated in the same manner as in Evaluation 1 of Storage Stability, except that this liquid composition was used. The results are shown in Table 1-2. A higher value indicates better storage stability.

[0146] [Table 1-2]

[0147] Example 8 and Comparative Example 8 <Evaluation of storage stability 3> A phosphate buffer solution at pH 2.5 (25°C) was prepared using phosphoric acid, sodium dihydrogen phosphate, and heavy water. This solution was used to prepare a solution containing 3% hydrogen peroxide (component (B)), 26.4 mM of component (A) in Table 2 (compounds synthesized in Examples 1, 3, 4, and 5, and comparative compounds), and 3 mM sodium 3-(trimethylsilyl)-1-propane-1,1,2,2,3,3-d6-sulfonate (standard substance). This solution, excluding the standard substance, corresponds to the liquid composition (mass %) shown in Table 2. The liquid compositions of the examples in Table 2 can be used as oxidizing agents or bleaching agents. The storage stability was evaluated in the same manner as in Evaluation 1 of Storage Stability, except that this liquid composition was used. The results are shown in Table 2. A higher value indicates better storage stability. For convenience, compounds that do not fall under the category of component (A) are also listed in the component (A) column in Table 2.

[0148] [Table 2]

[0149] Reference Example 1 and Comparative Reference Example 1 <Evaluation of Oxidizing Power> Solutions were prepared using ion-exchanged water for a 5.29 mM solution of component (A) (Table 3) (the compounds synthesized in Examples 1, 3, 4, and 5, and comparative compounds) (referred to as solution A), ion-exchanged water and 30% hydrogen peroxide for a 1765 mM solution of component (B) (referred to as solution B), and ethanol for a 1.32 mM curcumin solution. In Table 3, compounds not corresponding to component (A) were also shown in the column for component (A) for convenience. To 18.8 mL of a phosphate buffer adjusted to pH = 7.3 (25°C) using potassium dihydrogen phosphate and disodium hydrogen phosphate, 0.1 mL of solution B and 1 mL of solution A were added, and after stirring for 10 seconds, 0.1 mL of the curcumin solution was added and stirred for 10 minutes (the final concentrations were 0.264 mM for component (A), 8.824 mM for component (B), and 0.0066 mM for curcumin). After 10 minutes, 0.5 mL was taken from the reaction solution, and 0.5 mL of a quenching solution (0.5 M phosphoric acid aqueous solution / acetonitrile = 1:1 (vol)) was added thereto to obtain a sample solution. By quantifying this by HPLC, the remaining amount of curcumin was determined. This evaluation corresponds to a test for evaluating the oxidative decomposition activity when the liquid composition in Table 2 is used under neutral conditions. As a result of quantification by HPLC, the oxidative decomposition activity (oxidizing power (%), calculated by the following formula) under neutral conditions of the liquid compositions in Table 3 was as shown in Table 3. The higher the numerical value, the better the oxidative decomposition activity. The HPLC conditions were as follows. Oxidizing power (%) = 100×[(amount of curcumin used - remaining amount of curcumin) / amount of curcumin used] <HPLC Conditions> · Apparatus 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, 150 mm × 4.6 mm, 5 μm (Chemical Substances Evaluation Institute, Incorporated Administrative Agency) Oven temperature: 40 °C, Detector: UV (430 nm), Injection volume: 10 μl, Flow rate: 1.0 mL / min, Mobile phase: A = 50 mM phosphoric acid, B = acetonitrile

[0150]

Table 3

Claims

1. A novel pyridinium compound represented by the following general formula (1). 【Chemistry 1】 [In the formula, R １ is a hydrocarbon group having 2 to 24 carbon atoms, and Y is 【Chemistry 2】 The group is represented by Y, where Y is bonded to one of the carbon atoms at positions 2, 4, and 6 of the pyridine ring, and R ２ A is a hydrocarbon group which may contain heteroatoms, － It is an anion.

2. In the general formula (1), -R １ is -CH ２ -(CH ２ ) ｎ１１ -X １ -(CH ２ ) ｎ１２ -CH ３ ; X １ is a single bond or a heteroatom; n11 and n12 are each an integer of 0 or more and 22 or less; and the sum of n11 and n12 is 1 or more and 22 or less. The compound according to claim 1.

3. In the above general formula (1), -R ２ is, -X ２ -C(Z) ３ X ２ is a hydrocarbon group having a ring structure or (C(Z) ２ ) ｎ２１ The compound according to claim 1 or 2, wherein Z is a hydrogen atom or a heteroatom, and n21 is an integer between 0 and 23.

4. A method for producing a pyridinium compound, comprising step 1 of reacting a compound represented by the following general formula (1') with a sulfonylating agent to obtain a pyridinium compound represented by the following general formula (1). 【Transformation 3】 [In the formula, R １ Y' is a hydrocarbon group having 2 to 24 carbon atoms, Y' is a group represented by -O-, and Y' is bonded to one of the carbon atoms at positions 2, 4, or 6 of the pyridine ring. 【Chemistry 4】 [In the formula, R １ is a hydrocarbon group having 2 to 24 carbon atoms, and Y is 【Transformation 5】 The group is represented by Y, where Y is bonded to one of the carbon atoms at positions 2, 4, and 6 of the pyridine ring, and R ２ A is a hydrocarbon group which may contain heteroatoms, － It is an anion.

5. The manufacturing method according to claim 4, further comprising the step of reacting hydroxypyridine with an electrophile to obtain a compound represented by the general formula (1') prior to step 1.

6. A composition containing a pyridinium compound represented by the following general formula (1) [hereinafter referred to as component (A)] and water, and which is acidic. 【Transformation 6】 [In the formula, R １ is a hydrocarbon group having 2 to 24 carbon atoms, and Y is 【Transformation 7】 The group is represented by Y, where Y is bonded to one of the carbon atoms at positions 2, 4, and 6 of the pyridine ring, and R ２ A is a hydrocarbon group which may contain heteroatoms, － It is an anion.

7. Furthermore, the composition according to claim 6, further comprising (B) hydrogen peroxide [hereinafter referred to as component (B)].

8. The composition according to claim 6 or 7, wherein the pH at 25°C is less than 7.

9. The composition according to claim 6 or 7, which is for use as an oxidizing agent.

10. The composition according to claim 6 or 7, which is for use as a bleaching agent.

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