Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
  • C07D213/79—Acids; Esters
  • C07D213/80—Acids; Esters in position 3
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/61—Halogen atoms or nitro radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
  • C07D213/81—Amides; Imides
  • C07D213/82—Amides; Imides in position 3
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/542—Dye sensitized solar cells

Definitions

• the present invention relates to a novel pyridinium compound.
• Pyridinium compounds are compounds containing cations derived from pyridine, and are chemically modified as necessary for various uses such as bleaching, agricultural chemicals, medicines, sterilization, synthesis reagents, and catalysts. It is used.
• JP-A No. 2008-120699 discloses a drug 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.
• JP-A-60-112761 discloses certain new pyridinium compounds prepared from certain pyridinium compounds.
• oxidizing agents such as hydrogen peroxide are used as so-called oxygen bleaching agents, but bleach activators are sometimes used in combination to enhance the bleaching power.
• bleach activators compounds that react with hydrogen peroxide to generate organic peracids (active species) are known.
• the present invention relates to a novel pyridinium compound represented by the following general formula (1), (2) or (3).
• 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.
• X 11 is a halogen atom
• X 11 is bonded to the carbon atom at the 2-position, 4-position, or 6-position of the pyridine ring
• R 11 is a carbon atom that may contain a hetero atom It is an alkylene group having a number of 1 or more and 24 or less.
• X 21 is a halogen atom
• X 21 is bonded to the carbon atom at the 2nd, 4th or 6th position of the pyridine ring
• Z 21 is -COO-R 22 , -CONH- A group selected from R 23 and -CON(R 24 ) (R 25 )
• 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 hetero It is an alkyl group having 3 or more carbon atoms and 24 or less carbon atoms which may contain an atom
• R 22 , R 23 , R 24 and R 25 are each an alkyl group having 3 or more carbon atoms which may contain a hetero atom.
• a 21- is an anion.
• X 31 is a halogen atom
• X 31 is bonded to the carbon atom at the 2-position, 4-position, or 6-position of the pyridine ring
• R 31 is a carbon atom that may contain a hetero atom It is a branched alkyl group having a number of 10 or more and 24 or less
• a 31- is an anion.
• a novel pyridinium compound is provided.
• the pyridinium compound of the present invention can be expected to be used as an oxidizing agent, for example, an efficacy enhancer of peracid oxidizing agents such as hydrogen peroxide.
• Compound (1) is a pyridinium compound represented by the above general formula (1).
• X 11 is a halogen atom, and X 11 is bonded to the carbon atom at the 2-position, 4-position or 6-position of the pyridine ring.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred. Note that the position numbers of the pyridine ring are as follows.
• R 11 is an alkylene group having 1 to 24 carbon atoms and which may contain a hetero atom.
• the number of carbon atoms in R 11 is, for example, 2 or more, 3 or more, 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, and 4 or less.
• the heteroatom include a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.
• R 11 is an alkylene group containing a hetero atom
• the number of carbon atoms in R 11 may be the total number of carbon atoms in the carbon chain excluding the hetero atom.
• R 11 may be an alkylene group having 1 or more and 24 or less carbon atoms that does not contain a hetero atom.
• -R 11 -SO 3 includes, for example, -CH 2 -(CH 2 ) n11 -Y 1 -(CH 2 ) n12 -SO 3 .
• Y 1 is a single bond or a heteroatom
• n11 and n12 are each an integer of 0 to 23
• the sum of n11 and n12 is 0 to 23.
• Compound (1) can be synthesized, for example, by reacting a halogenated pyridine with a sultone. As shown in Examples below, compound (1) can be synthesized, for example, by reacting 2-chloropyridine and 1,3-propanesultone.
• the synthesis of compound (1) can be performed without a solvent or in the presence of a reaction solvent.
• the reaction solvent include 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, nitrobenzene, etc. can be used.
• 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 is below 60°C.
• processes such as extraction, purification, and recovery of compound (1) can be performed as necessary, and these processes include, for example, column chromatography, preparative TLC, recrystallization, and the use of solvents. cleaning, etc. can be used.
• Compound (2) is a pyridinium compound represented by the general formula (2).
• X 21 is a halogen atom, and X 21 is bonded to the carbon atom at the 2-position, 4-position or 6-position of the pyridine ring.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred.
• Z 21 is a group selected from -COO-R 22 , -CONH-R 23 and -CON(R 24 )(R 25 ), and Z 21 is the carbon to which X 21 is bonded. It is bonded to a different carbon atom in the pyridine ring.
• R 22 , R 23 , R 24 and R 25 are each an alkyl group having 3 or more carbon atoms and which may contain a hetero atom.
• the number of carbon atoms in R 22 , R 23 , R 24 and R 25 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.
• heteroatom examples include a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.
• R 22 , R 23 , R 24 and R 25 are alkyl groups containing a hetero atom
• the number of carbon atoms in R 22 , R 23 , R 24 and R 25 is the total number of carbon atoms in the carbon chain excluding the hetero atom. It's good.
• R 22 , R 23 , R 24 and R 25 may be an alkyl group having the above carbon number and not containing a hetero atom.
• Z 21 is preferably a group selected from -COO-R 22 and -CONH-R 23 .
• R 21 is an alkyl group having 3 to 24 carbon atoms and which may contain a hetero atom.
• the carbon number of R 21 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.
• the heteroatom include a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.
• R 21 is an alkyl group containing a hetero atom
• the number of carbon atoms in R 21 may be the total number of carbon atoms in the carbon chain excluding the hetero atom.
• R 21 may be an alkyl group having 3 or more and 24 or less carbon atoms that does not contain a hetero atom.
• -R 21 includes, for example, -CH 2 -(CH 2 ) n21 -Y 2 -(CH 2 ) n22 -CH 3 .
• Y 2 is a single bond or a heteroatom
• n21 and n22 are each an integer of 0 or more and 22 or less
• the sum of n21 and n22 is 1 or more and 22 or less.
• a 21- is an anion.
• the anion of A 21- may be either an organic anion or an inorganic anion.
• Examples of the anion of A 21- include anions that are conjugate bases of acids with a pKa of 5 or less.
• anion of A21- examples include sulfonic acid ions such as trifluoromethanesulfonate ion ( -OTf ), para-toluenesulfonate ion ( -OTs ), methanesulfonate ion ( -OMs ), and methyl sulfate ion ( - Alkyl sulfate ions such as OSO 3 Me), halide ions such as chloride ions (Cl ⁇ ), bromide ions (Br ⁇ ), and iodide ions (I ⁇ ), and tetrafluoroborate ions (BF 4 ⁇ ), etc.
• sulfonic acid ions such as trifluoromethanesulfonate ion ( -OTf ), para-toluenesulfonate ion ( -OTs ), methanesulfonate ion ( -OMs ), and methyl sulf
• Fluoroborate ion fluorophosphate ion such as hexafluorophosphate ion (PF 6 - ), imide ion such as bis(trifluoromethanesulfonic acid) imide ion ((CF 3 SO 2 ) 2 N - ), trifluoroacetate ion (CF Examples include fluoroacetate ions such as 3COO- ) .
• a 21- is preferably an anion selected from - OTf, - OSO 3 Me, - OTs, - OMs, Cl - and Br - .
• compounds in which Z 21 in general formula (2) is -COO-R 22 include, for example, 2chloronicotinic acid chloride, 1-butanol, and dodecanol, as shown in the examples below. , by quaternizing an ester compound obtained by reacting with an alcohol such as 2-decyl-1-tetradecanol using a quaternizing agent such as butyl trifluoromethanesulfonate or dodecyl trifluoromethanesulfonate. Can be synthesized.
• compounds in which Z 21 in general formula (2) is -CONH-R 23 include, for example, dichloronicotinic acid chloride and butylamine, as shown in the examples below.
• It can be synthesized by quaternizing an amide compound obtained by reacting with an alkylamine using a quaternizing agent such as butyl trifluoromethanesulfonate or dodecyl trifluoromethanesulfonate.
• a quaternizing agent such as butyl trifluoromethanesulfonate or dodecyl trifluoromethanesulfonate.
• a reaction solvent can be used in the synthesis of compound (2).
• the reaction solvent include 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, nitrobenzene, etc. can be used.
• 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 is below 60°C.
• processes such as extraction, purification, and recovery of compound (2) can be performed as necessary, and these processes include, for example, column chromatography, preparative TLC, recrystallization, and use of a solvent. cleaning, etc. can be used.
• Compound (3) is a pyridinium compound represented by the general formula (3).
• X 31 is a halogen atom, and X 31 is bonded to the carbon atom at the 2-position, 4-position or 6-position of the pyridine ring.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred.
• R 31 is a branched alkyl group having 10 to 24 carbon atoms and which may contain a hetero atom.
• the carbon number of R 31 is, for example, 12 or more, further 16 or more, further 20 or more, and 28 or less, further 24 or less, and further 22 or less.
• the heteroatom include a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.
• R 31 is an alkyl group containing a hetero atom
• the number of carbon atoms in R 31 may be the total number of carbon atoms in the carbon chain excluding the hetero atom.
• R 31 may be a branched alkyl group having 10 to 24 carbon atoms and not containing a hetero atom. From the viewpoint of availability, R 31 is preferably a branched alkyl group having a methyl branch, and more preferably a branched alkyl group having a plurality of methyl branches.
• examples of -R 31 include -CH 2 -R 311 -Y 3 -R 312 -CH 3 .
• Y 3 is a single bond or a hetero atom
• R 311 and R 312 are each a single bond or an alkylene group
• the total number of carbon atoms of R 311 and R 312 is 8 or more and 22 or less
• R 311 and at least one of R 312 is a branched alkylene group.
• a 31- is an anion.
• the anion of A 31- may be either an organic anion or an inorganic anion.
• Examples of the anion of A 31- include anions that are conjugate bases of acids with a pKa of 5 or less.
• anion of A 31- examples include sulfonic acid ions such as trifluoromethanesulfonate ion ( -OTf ), para-toluenesulfonate ion ( -OTs ), methanesulfonate ion ( -OMs ), and methyl sulfate ion ( - Alkyl sulfate ions such as OSO 3 Me), halide ions such as chloride ions (Cl ⁇ ), bromide ions (Br ⁇ ), and iodide ions (I ⁇ ), and tetrafluoroborate ions (BF 4 ⁇ ), etc.
• sulfonic acid ions such as trifluoromethanesulfonate ion ( -OTf ), para-toluenesulfonate ion ( -OTs ), methanesulfonate ion ( -OMs ), and methyl sulf
• Fluoroborate ion fluorophosphate ion such as hexafluorophosphate ion (PF 6 - ), imide ion such as bis(trifluoromethanesulfonic acid) imide ion ((CF 3 SO 2 ) 2 N - ), trifluoroacetate ion (CF Examples include fluoroacetate ions such as 3COO- ) .
• a 31- is preferably an anion selected from - OTf, - OSO 3 Me, - OTs, - OMs, Cl - , and Br - .
• Compound (3) is produced by combining an alcohol such as 3,7-dimethyloctanol or 3,7,11,15-tetramethylhexadecanol with trifluoromethanesulfonic anhydride, as shown in the examples below. It can be synthesized by reacting the resulting sulfonic acid ester with 2-chloropyridine.
• a reaction solvent can be used in the synthesis of compound (3).
• the reaction solvent include 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, nitrobenzene, etc. can be used.
• 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 is below 60°C.
• processes such as extraction, purification, and recovery of compound (3) can be carried out as necessary, and these processes include, for example, column chromatography, preparative TLC, recrystallization, and the use of solvents. cleaning, etc. can be used.
• the compounds (1) to (3) of the present invention can be used directly or indirectly in a wide variety of fields, such as bleaching, decolorization, reactive agents, cleaning, deodorizing, antiviral, sterilizing, sporicidal, etc. You can expect it to be used.
• Compounds (1) to (3) of the present invention are, for example, (I) In the paper and pulp industry, it is used for bleaching various pulps, removing ink from waste paper, etc. (II) In the textile industry, for purposes such as bleaching natural fibers such as cotton, wool, and silk, as well as synthetic fibers, etc. (III) In the chemical industry, for use as raw materials for organic and inorganic peroxides, raw materials for organic compounds, raw materials for epoxy compounds, etc.
• the present invention provides oxidative decomposition of a novel pyridinium compound represented by the general formula (1), a novel pyridinium compound represented by the general formula (2), or a novel pyridinium compound represented by the general formula (3). Provides use as an activator.
• the present invention provides a novel pyridinium compound represented by the general formula (1), a novel pyridinium compound represented by the general formula (2), or a novel pyridinium compound represented by the general formula (3) in the production of an oxidative decomposition activator. Provided are uses of novel pyridinium compounds.
• the present invention provides a novel pyridinium compound represented by the general formula (1), a novel pyridinium compound represented by the general formula (2), or a novel pyridinium compound represented by the general formula (3) in the production of an oxidizing agent. Uses of pyridinium compounds are provided.
• the present invention further comprises a novel pyridinium compound represented by the general formula (1), a novel pyridinium compound represented by the general formula (2), or a novel pyridinium compound represented by the general formula (3). Provides an oxidative decomposition activator.
• the present invention also provides a novel pyridinium compound represented by the general formula (1), a novel pyridinium compound represented by the general formula (2), or a novel pyridinium compound represented by the general formula (3).
• a novel pyridinium compound represented by the general formula (1) a novel pyridinium compound represented by the general formula (2), or a novel pyridinium compound represented by the general formula (3) in the production of a bleach activator.
• the present invention provides a novel pyridinium compound represented by the general formula (1), a novel pyridinium compound represented by the general formula (2), or a novel pyridinium compound represented by the general formula (3) in the production of bleach. Uses of pyridinium compounds are provided.
• the present invention further comprises a novel pyridinium compound represented by the general formula (1), a novel pyridinium compound represented by the general formula (2), or a novel pyridinium compound represented by the general formula (3).
• Provide bleach activator for these uses, oxidative decomposition activators, and bleach activators, the matters described for compounds (1) to (3) of the present invention can be applied as appropriate.
• X 11 is a halogen atom
• X 11 is bonded to the carbon atom at the 2-position, 4-position, or 6-position of the pyridine ring
• R 11 is a carbon atom that may contain a hetero atom It is an alkylene group having a number of 1 or more and 24 or less.
• X 21 is a halogen atom
• X 21 is bonded to the carbon atom at the 2nd, 4th or 6th position of the pyridine ring
• Z 21 is -COO-R 22 , -CONH- A group selected from R 23 and -CON(R 24 ) (R 25 )
• 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 hetero It is an alkyl group having 3 or more carbon atoms and 24 or less carbon atoms which may contain an atom
• R 22 , R 23 , R 24 and R 25 are each an alkyl group having 3 or more carbon atoms which may contain a hetero atom.
• a 21- is an anion.
• X 31 is a halogen atom
• X 31 is bonded to the carbon atom at the 2-position, 4-position, or 6-position of the pyridine ring
• R 31 is a carbon atom that may contain a hetero atom It is a branched alkyl group having a number of 10 or more and 24 or less
• a 31- is an anion.
• X 11 is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and further is a chlorine atom.
• the carbon number of R 11 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, and further 8 or less. , further 6 or less, further 4 or less, the compound described in ⁇ 1> or ⁇ 2>.
• the heteroatom of R 11 is at least one selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, as described in any of ⁇ 1> to ⁇ 3>.
• R 11 is an alkylene group having 1 to 24 carbon atoms and not containing a hetero atom.
• -R 11 -SO 3 is -CH 2 -(CH 2 ) n11 -Y 1 -(CH 2 ) n12 -SO 3
• Y 1 is a single bond or a hetero atom.
• n11 and n12 are each an integer of 0 to 23, and the sum of n11 and n12 is 0 to 23, the compound described in any one of ⁇ 1> to ⁇ 5>.
• X 11 is a chlorine atom
• X 11 is bonded to the 2- or 6-position carbon atom of the pyridine ring
• R 11 is an alkylene group having 3 carbon atoms.
• X 21 is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and further is a chlorine atom, according to any one of ⁇ 1> to ⁇ 7>. compound.
• the number of carbon atoms in R 22 , R 23 , R 24 and R 25 is 4 or more, further 8 or more, further 12 or more, and 24 or less, further 20 or less, and further 18 or less.
• each of the heteroatoms R 22 , R 23 , R 24 and R 25 is at least one selected from a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, ⁇ 1> A compound described in any of ⁇ 9>.
• R 22 , R 23 , R 24 and R 25 are an alkyl group having the above number of carbon atoms and not containing a hetero atom, as described in any one of ⁇ 1> to ⁇ 10>.
• Z 21 is a group selected from -COO-R 22 and -CONH-R 23 , the compound described in any one of ⁇ 1> to ⁇ 11>.
• the number of carbon atoms in R 21 is any one of ⁇ 1> to ⁇ 12>, which is 4 or more, further 8 or more, further 12 or more, and 24 or less, further 20 or less, and further 18 or less.
• the heteroatom of R 21 is at least one selected from nitrogen atom, oxygen atom, sulfur atom, and phosphorus atom, and is described in any one of ⁇ 1> to ⁇ 13>.
• R 21 is an alkyl group having 3 to 24 carbon atoms and not containing a hetero atom, the compound described in any one of ⁇ 1> to ⁇ 13>.
• -R21 is -CH2- ( CH2 ) n21 - Y2- ( CH2 ) n22 - CH3 , Y2 is a single bond or a heteroatom, and n21 and The compound according to any one of ⁇ 1> to ⁇ 14>, wherein each n22 is an integer of 0 to 22, and the sum of n21 and n22 is 1 to 22.
• a 21- is an anion selected from an organic anion and an inorganic anion, the compound described in any one of ⁇ 1> to ⁇ 16>.
• a 21- is an anion that is a conjugate base of an acid having a pKa of 5 or less, the compound described in any one of ⁇ 1> to ⁇ 17>.
• a 21- is an anion selected from a sulfonate ion, an alkyl sulfate ion, a halide ion, a fluoroborate ion, a fluorophosphate ion, an imide ion, and a fluoroacetate ion, and further, Trifluoromethanesulfonate ion ( -OTf ), paratoluenesulfonate ion ( -OTs ), methanesulfonate ion ( -OMs ), methyl sulfate ion ( -OSO3Me ), chloride ion ( Cl- ) , bromide ion ( Br ⁇ ), iodide ion (I ⁇ ), tetrafluoroborate ion (BF 4 ⁇ ), hexafluorophosphate ion (PF 6 ⁇ ), bis(trifluorfluoronate ion (
• a 21- is any of ⁇ 1> to ⁇ 19>, which is an anion selected from - OTf, - OSO 3 Me, - OTs, - OMs, Cl - , and Br - .
• X 21 is a chlorine atom
• X 21 is bonded to the carbon atom at the 2-position of the pyridine ring
• Z 21 is -COO-R 22 and -CONH-R 23
• 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 a group selected from a butyl group, a dodecyl group, and a tetracosyl group.
• a 21 is - OTf, the compound described in any one of ⁇ 1> to ⁇ 20>.
• X 21 is a chlorine atom
• X 21 is bonded to the carbon atom at the 2-position of the pyridine ring
• Z 21 is -COO-R 22
• Z 21 is , 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 butyl
• a 21 is -OTf .
• X 21 is a chlorine atom
• X 21 is bonded to the carbon atom at the 2-position of the pyridine ring
• Z 21 is -COO-R 22
• R 22 is , is a butyl group
• Z 21 is bonded to the 3rd carbon atom of the pyridine ring
• R 21 is a dodecyl group
• a 21 is -OTf , ⁇ 1> to ⁇ 22>
• X 21 is a chlorine atom
• X 21 is bonded to the carbon atom at the 2-position of the pyridine ring
• Z 21 is -COO-R 22
• R 22 is , is a dodecyl group
• Z 21 is bonded to the 3rd carbon atom of the pyridine ring
• R 21 is a dodecyl group
• a 21 is -OTf , ⁇ 1> to ⁇ 22>
• X 21 is a chlorine atom
• X 21 is bonded to the carbon atom at the 2-position of the pyridine ring
• Z 21 is -COO-R 22
• R 22 is , is a 2-decyltetradecyl group
• Z 21 is bonded to the 3-position carbon atom of the pyridine ring
• R 21 is a dodecyl group
• a 21 is -OTf, ⁇ 1> ⁇
• X 21 is a chlorine atom
• X 21 is bonded to the carbon atom at the 2-position of the pyridine ring
• Z 21 is -COO-R 22
• R 22 is , is a dodecyl group
• Z 21 is bonded to the 3rd carbon atom of the pyridine ring
• R 21 is a butyl group
• a 21 is -OTf , ⁇ 1> to ⁇ 22>
• X 21 is a chlorine atom
• X 21 is bonded to the carbon atom at the 2-position of the pyridine ring
• Z 21 is -COO-R 22
• R 22 is , is a dodecyl group
• Z 21 is bonded to the 3-position carbon atom of the pyridine ring
• R 21 is a tetracosyl group
• a 21 is -OTf Any of ⁇ 1> to ⁇ 22> A compound described in
• X 21 is a chlorine atom
• X 21 is bonded to the carbon atom at the 2-position of the pyridine ring
• Z 21 is -CONH-R 23
• Z 21 is ,
• X 21 is bonded to a different carbon atom of the pyridine ring than the carbon atom to which R 23 is a butyl group
• R 21 is a group selected from a butyl group and a dodecyl group
• a 21 is a group selected from a butyl group and a dodecyl group.
• - The compound described in any of ⁇ 1> to ⁇ 21>, which is OTf.
• X 21 is a chlorine atom
• X 21 is bonded to the carbon atom at the 2-position of the pyridine ring
• Z 21 is -CONH-R 23
• R 23 is , is a butyl group
• Z 21 is bonded to the 3rd carbon atom of the pyridine ring
• R 21 is a butyl group
• a 21 is -OTf , ⁇ 1> to ⁇ 21>
• X 21 is a chlorine atom
• X 21 is bonded to the carbon atom at the 2-position of the pyridine ring
• Z 21 is -CONH-R 23
• R 23 is , is a butyl group
• Z 21 is bonded to the 3rd carbon atom of the pyridine ring
• R 21 is a dodecyl group
• a 21 is -OTf , any of ⁇ 1> to ⁇ 21>
• X 31 is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and further is a chlorine atom, as described in any one of ⁇ 1> to ⁇ 30> compound.
• the number of carbon atoms in R 31 is any one of ⁇ 1> to ⁇ 31>, which is 12 or more, further 16 or more, further 20 or more, and 28 or less, further 24 or less, and further 22 or less.
• the heteroatom of R 31 is at least one selected from nitrogen atom, oxygen atom, sulfur atom, and phosphorus atom, and is described in any one of ⁇ 1> to ⁇ 32>.
• R 31 is a branched alkyl group having 10 to 24 carbon atoms and containing no heteroatoms, and further a branched alkyl group having 10 to 24 carbon atoms and having a methyl branch. Furthermore, the compound described in any one of ⁇ 1> to ⁇ 33> is a branched alkyl group having 10 to 24 carbon atoms and having multiple methyl branches.
• -R 31 is -CH 2 -R 311 -Y 3 -R 312 -CH 3
• Y 3 is a single bond or a hetero atom
• R 311 and R 312 are each , a single bond or an alkylene group
• the total carbon number of R 311 and R 312 is 8 or more and 22 or less
• at least one of R 311 and R 312 is a branched alkylene group, ⁇ 1> to ⁇ 34>
• a 31- is an anion selected from an organic anion and an inorganic anion, the compound described in any one of ⁇ 1> to ⁇ 35>.
• a 31- is an anion that is a conjugate base of an acid having a pKa of 5 or less, the compound described in any one of ⁇ 1> to ⁇ 36>.
• a 31- is an anion selected from a sulfonate ion, an alkyl sulfate ion, a halide ion, a fluoroborate ion, a fluorophosphate ion, an imide ion, and a fluoroacetate ion, and further, Trifluoromethanesulfonate ion ( -OTf ), paratoluenesulfonate ion ( -OTs ), methanesulfonate ion ( -OMs ), methyl sulfate ion ( -OSO3Me ), chloride ion ( Cl- ) , bromide ion ( Br ⁇ ), iodide ion (I ⁇ ), tetrafluoroborate ion (BF 4 ⁇ ), hexafluorophosphate ion (PF 6 ⁇ ), bis(trifluorfluoronate ion (
• X 31 is a chlorine atom
• X 31 is bonded to the 2- or 6-position carbon atom of the pyridine ring
• R 31 is a 3,7-dimethyloctyl group.
• X 31 is a chlorine atom
• X 31 is bonded to the 2- or 6-position carbon atom of the pyridine ring
• R 31 is 3,7,11,15-
• Example ⁇ NMR measurement conditions The measurement conditions for NMR ( 1 H NMR) performed in the synthesis examples and examples are as follows. ⁇ Equipment: Vnmr 400MR DD2 (manufactured by Agilent) ⁇ Measurement temperature: 25°C ⁇ Waiting time: 10 seconds ⁇ Number of integration: 8 times ⁇ Observation range: 6410.3Hz ⁇ Pulse: 45° ⁇ Data points: 65536
• the obtained organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated using a rotary evaporator to obtain a crude product.
• the 1 H NMR measurement results of the compound were as follows.
• the obtained organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated using a rotary evaporator to obtain a crude product.
• the 1 H NMR measurement results of the compound were as follows.
• 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 performed using a 100 mL one-necked eggplant flask.
• 1,3-propanesultone (4.04g, 33.03mmol, 0.75 eq.) was added to 2-chloropyridine (5g, 44.03mmol), and the mixture was stirred at 60°C for 5 hours. Acetone was added to the final solution, and the resulting crystals were collected by filtration and dried under reduced pressure to obtain 4.98 g of the title compound (21.14 mmol, yield 64%).
• the 1 H NMR measurement results of the compound were as follows.
• 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 performed using a 100 mL one-necked eggplant flask.
• 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 performed using a 100 mL one-necked eggplant flask.
• Example 4 ⁇ 3-(2-decyltetradecyloxycarbonyl)-2-chloro-1-dodecylpyridin-1-ium trifluoromethanesulfonic acid (3-(2-decyltetradecyloxycarbonyl)-2-chloro-1-dodecylpyridin-1 Synthesis of -ium trifluoromethanesulfonate> The title compound was synthesized according to the following scheme. The synthesis was performed using a 100 mL one-necked eggplant flask.
• Example 5 ⁇ 1-butyl-2-chloro-3-((dodecyloxy)carbonyl)pyridin-1-ium trifluoromethanesulfonate (1-butyl-2-chloro-3-((dodecyloxy)carbonyl)pyridin-1 Synthesis of -ium trifluoromethanesulfonate> The title compound was synthesized according to the following scheme. The synthesis was performed using a 200 mL one-necked eggplant flask.
• Example 6 ⁇ 1-tetracosyl-2-chloro-3-((dodecyloxy)carbonyl)pyridin-1-ium trifluoromethanesulfonate (1-tetracosyl-2-chloro-3-((dodecyloxy)carbonyl)pyridin-1 Synthesis of -ium trifluoromethanesulfonate> The title compound was synthesized according to the following scheme. The synthesis was performed using a 200 mL one-necked eggplant flask.
• 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 performed using a 100 mL one-necked eggplant flask.
• 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 performed using a 100 mL one-necked eggplant flask.
• Example 9 ⁇ 2-chloro-1-(3,7-dimethyloctyl)pyridin-1-ium trifluoromethanesulfonate (2-chloro-1-(3,7-dimethyloctyl)pyridin-1-ium trifluoromethanesulfonate) synthesis>
• the title compound was synthesized according to the following scheme. The synthesis was performed using a 100 mL one-necked eggplant flask.
• Example 10 ⁇ 2-chloro-1-(3,7,11,15-tetramethylhexadecyl)pyridin-1-ium trifluoromethanesulfonate (2-chloro-1-(3,7,11,15- Synthesis of (tetramethylhexadecyl)pyridin-1-ium trifluoromethanesulfonate>
• the title compound was synthesized according to the following scheme. The synthesis was performed using a 50 mL one-necked eggplant flask.
• solution A A solution of 5.29mM of the pyridinium compound of Example 1 using ion-exchanged water (referred to as solution A), a 1765mM hydrogen peroxide solution (referred to as solution B) using ion-exchanged water and 30% hydrogen peroxide, A 1.32mM curcumin solution was prepared using ethanol.
• solution B a 1765mM hydrogen peroxide solution
• solution B a 1765mM hydrogen peroxide solution
• curcumin solution A 1.32mM curcumin solution was prepared using ethanol.
• the HPLC conditions were as follows. Note that when the same evaluation is performed using the compounds of Examples 2 to 10 instead of the pyridinium compound of Example 1, the same oxidative decomposition activity as that of the pyridinium compound of Example 1 can be obtained.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Pyridine Compounds (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=88329835

Family Applications (1)

Country Status (5)

Citations (8)

• 2023
  • 2023-04-12 WO PCT/JP2023/014845 patent/WO2023199938A1/ja not_active Ceased
  • 2023-04-12 US US18/856,458 patent/US20250263379A1/en active Pending
  • 2023-04-12 JP JP2024514981A patent/JPWO2023199938A1/ja active Pending
  • 2023-04-12 CN CN202380033923.4A patent/CN119013258A/zh active Pending
  • 2023-04-12 EP EP23788356.6A patent/EP4509495A1/en active Pending

Patent Citations (8)

Non-Patent Citations (4)

Also Published As

Similar Documents

Legal Events