WO2023033165A1 - アクリジン化合物 - Google Patents

アクリジン化合物 Download PDF

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WO2023033165A1
WO2023033165A1 PCT/JP2022/033207 JP2022033207W WO2023033165A1 WO 2023033165 A1 WO2023033165 A1 WO 2023033165A1 JP 2022033207 W JP2022033207 W JP 2022033207W WO 2023033165 A1 WO2023033165 A1 WO 2023033165A1
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hydrogen
halogen
compound
methyl
optionally substituted
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French (fr)
Japanese (ja)
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敬 大久保
祐介 赤尾
靖明 小泉
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Otsuka Pharmaceutical Co Ltd
University of Osaka NUC
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Osaka University NUC
Otsuka Pharmaceutical Co Ltd
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Priority to US18/689,319 priority Critical patent/US20250129029A1/en
Priority to JP2023545707A priority patent/JPWO2023033165A1/ja
Priority to KR1020247011022A priority patent/KR20240056567A/ko
Priority to CN202280060016.4A priority patent/CN117940408A/zh
Priority to EP22864747.5A priority patent/EP4400492A4/en
Publication of WO2023033165A1 publication Critical patent/WO2023033165A1/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/04—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems 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 carbon atoms of the ring system
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/58—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of molecular oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
    • C07C39/04—Phenol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/04—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems 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 carbon atoms of the ring system
    • C07D219/06—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/04—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems 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 carbon atoms of the ring system
    • C07D219/08—Nitrogen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/05—Nuclear magnetic resonance [NMR]
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to acridine compounds.
  • Phenols are important compounds that are widely used in various chemical products such as phenolic resins, various pharmaceuticals, dyes and disinfectants.
  • the cumene method is generally known as an industrial method for synthesizing phenol, which is a representative compound of phenols, but the production process is complicated.
  • a method for producing phenol by direct oxidation of benzene by light irradiation a case using a photoredox catalyst having a quinolinium skeleton has been disclosed (Patent Document 1, Non-Patent Documents 1 and 2). This method is not suitable as a production method since the production of phenol is about 50%.
  • photoredox catalysts having an acridinium skeleton for example, 9-phenyl-10-methylacridinium (Acr + -Ph) and 9-mesityl-10-methylacridinium (Acr + -Mes) are known. (Patent Documents 2 and 3).
  • JP 2011-189224 A Japanese Patent Application Laid-Open No. 2005-145853 WO2011/034071
  • Chemical formula (A) is a photoredox catalyst with high oxidizing power.
  • a high oxidizing power is required to produce phenol from benzene using a photocatalyst.
  • the present inventors have confirmed that the quinolinium derivative has a maximum absorption wavelength of about 310 nm, and that this wavelength is absorbed by the product, phenol, and the reaction stops prematurely.
  • the acridine compounds described in Patent Documents 2 and 3 have oxidizing power as photoredox catalysts, but the oxidizing power is insufficient.
  • An object of the present invention is to provide an acridine compound that has a maximum absorption wavelength at a wavelength that is not the absorption wavelength of phenol and that has remarkably high oxidizing power as a photoredox catalyst.
  • the present inventors succeeded in synthesizing a novel acridine compound represented by the following formula [I], and the compound is remarkably high as a photoredox catalyst. It was discovered that it has oxidizing power, and the present invention was completed.
  • a compound according to Item 1 [Section 3] R12 , R13 , R14 , R15 and R16 are the same or different and are hydrogen, fluorine, methyl, t-butyl, trifluoromethyl or trifluoromethoxy; R 21 and R 22 are hydrogen and R 23 is fluorine; R3 is methyl or 4-fluorophenyl, 3.
  • [Section 4] 4. The compound according to any one of items 1 to 3 selected from the following. [Section 5] 5.
  • X - is perchlorate ion (ClO 4 - ), hexafluorophosphate ion (PF 6 - ) or tetrafluoroborate ion (BF 4 - ).
  • a photoredox catalyst selected from the compounds according to any one of items 1 to 5.
  • Item 6 Use of the compound according to any one of Items 1 to 5 as a photoredox catalyst.
  • a manufacturing method comprising the step of
  • the compound of the present invention has remarkably high oxidizing power as a photoredox catalyst. Moreover, by using the compound of the present invention, phenol can be efficiently produced by direct photo-oxidation of benzene.
  • FIG. 1 is a graph showing the correlation between singlet excited state reduction potential and electron affinity.
  • FIG. 2 is a graph showing fluorescence lifetime.
  • halogen is fluorine, chlorine, bromine or iodine. Fluorine, chlorine or bromine is preferred, and fluorine or chlorine is more preferred.
  • C 1-6 alkyl examples include linear or branched alkyl having 1 to 6 carbon atoms (C 1-6 ), and specific examples thereof include methyl, ethyl, Examples include n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl and the like. “C 1-6 alkyl” also includes C 1-6 alkyl in which 1 to 7 hydrogen atoms are replaced with deuterium atoms.
  • C 1-6 alkyl optionally substituted with halogen examples include C 1-6 (C 1-6 ) optionally substituted with 1 to 4 halogens.
  • straight or branched chain alkyl groups specific examples of which are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl, fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, 2-fluoroethyl, 2-chloroethyl, 2,2, 2-trifluoroethyl, 2,2,2-trichloroethyl, 1,1,2,2-tetra
  • C 1-6 alkoxy optionally substituted with halogen examples include C 1-6 (C 1-6 ) optionally substituted with 1 to 4 halogen straight or branched chain alkoxy groups, specific examples of which are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, isopentoxy, neopentoxy; , n-hexyloxy, isohexyloxy, 3-methylpentyloxy, fluoromethoxy, chloromethoxy, bromomethoxy, iodomethoxy, difluoromethoxy, dichloromethoxy, dibromomethoxy, trifluoromethoxy, trichloromethoxy, 2-fluoroethoxy, 2 -chloroethoxy, 2,2,2-trifluoroethoxy, 2,2,2-trichloroethoxy, 1,1,2,2-te
  • sulfanyl optionally substituted with halogen examples include pentafluorosulfanyl and the like.
  • benzene optionally having substituents is benzene optionally having 1 to 5 substituents.
  • substituents include alkyl, halogen, and an alkyl group having halogen as a substituent. Specific examples include benzene, toluene, fluorobenzene, chlorobenzene, bromobenzene, o-xylene, m-xylene, p-xylene, trifluoromethylbenzene, and benzenesulfonic acid.
  • Lewis acid is an acid as defined by G. N. Lewis in 1923, and specific examples include lithium tetrafluoroborate, aluminum chloride, yttrium (III) nitrate, silicon tetrachloride, Ruthenium Chloride, Aluminum Isopropoxide, Aluminum (III) Chloride, Aluminum Bromide, Indium (III) Chloride, Copper (II) Trifluoromethanesulfonate, Lanthanum (III) Trifluoromethanesulfonate, Zinc (II) Trifluoromethanesulfonate , silver trifluoromethanesulfonate, ytterbium (III) trifluoromethanesulfonate hydrate, scandium (III) trifluoromethanesulfonate, hafnium (IV) trifluoromethanesulfonate, cerium (III) trifluoromethanesulfonate, trifluoromethanesulf
  • X - is not particularly limited as long as it is an anion, and examples thereof include fluoride ion (F - ), chloride ion (Cl - ), bromide ion ( Br ), hydroxide ion (OH - ), cyanide ion (CN - ), nitrate ion (NO 3 - ), nitrite ion (NO 2 - ), hypochlorite ion (ClO - ), chlorite ion (ClO 2 - ), chlorate ion (ClO 3 - ), perchlorate ion (ClO 4 - ), permanganate ion (MnO 4 - ), acetate ion (CH 3 COO - ), bicarbonate ion (HCO 3 - ), dihydrogen phosphate (H 2 PO 4 - ), hydrogen sulfate (HSO 4 - ), hydrogen sulfide (HS
  • perchlorate ion (ClO 4 - ), hexafluorophosphate ion (PF 6 - ) and tetrafluoroborate ion (BF - ), and more preferred is perchlorate ion (ClO 4 - ). be done.
  • the “base” is not particularly limited, but includes, for example, inorganic bases, organic bases, and the like.
  • “Inorganic bases” include alkali metal hydroxides (e.g. lithium hydroxide, sodium hydroxide, potassium hydroxide), alkaline earth metal hydroxides (e.g. magnesium hydroxide, calcium hydroxide, barium hydroxide) , alkali metal carbonates (e.g. sodium carbonate, potassium carbonate, cesium carbonate), alkaline earth metal carbonates (e.g. magnesium carbonate, calcium carbonate, barium carbonate), alkali metal hydrogen carbonates (e.g. sodium hydrogen carbonate, carbonate potassium hydrogen), alkali metal phosphates (e.g.
  • sodium phosphate, potassium phosphate, cesium phosphate alkaline earth metal phosphates (e.g. magnesium phosphate, calcium phosphate), alkali metal alkoxides (e.g. sodium methoxy sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide), alkali metal hydrides (eg, sodium hydride, potassium hydride), sodium hydride and the like.
  • alkaline earth metal phosphates e.g. magnesium phosphate, calcium phosphate
  • alkali metal alkoxides e.g. sodium methoxy sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide
  • alkali metal hydrides eg, sodium hydride, potassium hydride
  • sodium hydride and the like alkaline earth metal phosphates (e.g. magnesium phosphate, calcium phosphate)
  • alkali metal alkoxides e.g. sodium meth
  • Organic bases include trialkylamines (e.g., trimethylamine, triethylamine, N,N-diisopropylethylamine (DIPEA)), dialkylamines (e.g., diethylamine, diisopropylamine), 4-dimethylaminopyridine (DMAP), N- Methylmorpholine, picoline, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane and 1,8-diazabicyclo[5.4.0] -7-undecene (DBU) etc. One or two or more of these can be appropriately selected and mixed for use.
  • DIPEA diisopropylethylamine
  • DMAP 4-dimethylaminopyridine
  • DBU 4-dimethylaminopyridine
  • N- Methylmorpholine picoline
  • the "Bronsted base” is a base defined by Bronsted in 1923, and includes inorganic bases and organic bases. Specific examples include alkali metal hydrides (sodium hydride, potassium hydride) and alkaline earth metal hydrides (calcium hydride) as inorganic bases, and metal amides (lithium diisopropylamide, potassium hexamethyldibutylamide) as organic bases. silazide, lithium 2,2,6,6-tetramethylpiperidide).
  • palladium catalyst is not particularly limited, and examples thereof include tetravalent palladium catalysts such as sodium hexachloropalladium(IV) tetrahydrate and potassium hexachloropalladium(IV); ,1'-Bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane adduct (Pd(dppf) Cl2.CH2Cl2 ), (2-dicyclohexylphosphino- 2 ', 4 ',6'- triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate (XPhos Pd G3), [(2-dicyclohexylphosphino-3, 6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphen
  • the "leaving group” specifically includes halogen, C 1-18 alkanesulfonyl, lower alkanesulfonyloxy, arylsulfonyloxy, aralkylsulfonyloxy, perhaloalkanesulfonyloxy, sulfonio, toluenesulfoxy, and the like. is. Preferred leaving groups in this reaction include halogen.
  • halogen is fluorine, chlorine, bromine or iodine.
  • C 1-18 alkanesulfonyl examples include linear or branched alkanesulfonyl having 1 to 18 carbon atoms, and specific examples thereof include methanesulfonyl, 1-propanesulfonyl, 2-propanesulfonyl, 1-butanesulfonyl, cyclohexanesulfonyl, 1-dodecanesulfonyl, 1-octadecanesulfonyl and the like.
  • lower alkanesulfonyloxy examples include linear or branched alkanesulfonyloxy having 1 to 6 carbon atoms, and specific examples thereof include methanesulfonyloxy, ethanesulfonyloxy, 1-propanesulfonyloxy, 2-propanesulfonyloxy, 1-butanesulfonyloxy, 3-butanesulfonyloxy, 1-pentanesulfonyloxy, 1-hexanesulfonyloxy and the like.
  • arylsulfonyloxy examples include, as substituents on the phenyl ring, linear or branched alkyl having 1 to 6 carbon atoms, linear or branched alkoxy having 1 to 6 carbon atoms, nitro and Including phenylsulfonyloxy, naphthylsulfonyloxy and the like which may have 1 to 3 groups selected from the group of halogens.
  • phenylsulfonyloxy which may have a substituent include phenylsulfonyloxy, 4-methylphenylsulfonyloxy, 2-methylphenylsulfonyloxy, 4-nitrophenylsulfonyloxy, 4-methoxyphenylsulfonyloxy, 2-nitrophenylsulfonyloxy, 3-chlorophenylsulfonyloxy and the like.
  • naphthylsulfonyloxy include ⁇ -naphthylsulfonyloxy, ⁇ -naphthylsulfonyloxy and the like.
  • aralkylsulfonyloxy examples include, as substituents on the phenyl ring, linear or branched alkyl having 1 to 6 carbon atoms, linear or branched alkoxy having 1 to 6 carbon atoms, nitro and straight-chain or branched-chain alkanesulfonyloxy having 1 to 6 carbon atoms substituted with phenyl which may have 1 to 3 groups selected from the group consisting of halogen; 6 linear or branched alkyl, linear or branched alkoxy having 1 to 6 carbon atoms, naphthyl optionally having 1 to 3 groups selected from the group consisting of nitro and halogen Including straight-chain or branched-chain alkanesulfonyloxy having 1 to 6 carbon atoms.
  • phenyl-substituted alkanesulfonyloxy examples include benzylsulfonyloxy, 2-phenylethylsulfonyloxy, 4-phenylbutylsulfonyloxy, 4-methylbenzylsulfonyloxy, 2-methylbenzylsulfonyloxy, 4- nitrobenzylsulfonyloxy, 4-methoxybenzylsulfonyloxy, 3-chlorobenzylsulfonyloxy and the like.
  • naphthyl-substituted alkanesulfonyloxy examples include ⁇ -naphthylmethylsulfonyloxy, ⁇ -naphthylmethylsulfonyloxy and the like.
  • perhaloalkanesulfonyloxy examples include trifluoromethanesulfonyloxy and the like.
  • sulfonio examples include dimethylsulfonio, diethylsulfonio, dipropylsulfonio, di(2-cyanoethyl)sulfonio, di(2-nitroethyl)sulfonio, di-(aminoethyl)sulfonio, di( 2-methylaminoethyl)sulfonio, di-(2-dimethylaminoethyl)sulfonio, di-(2-hydroxyethyl)sulfonio, di-(3-hydroxypropyl)sulfonio, di-(2-methoxyethyl)sulfonio, di -(2-carbamoylethyl)sulfonio, di-(2-carbamoylethyl)sulfonio, di-(2-carboxyethyl)sulfonio, di-(2-carboxy
  • the "solvent” may be any solvent inert to the reaction, such as water, ethers (e.g., dioxane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether). , halogenated hydrocarbons (e.g. methylene chloride, chloroform, 1,2-dichloroethane, carbon tetrachloride), aromatic hydrocarbons (e.g. benzene, toluene, xylene, chlorobenzene), C1-4 alcohols (e.g.
  • ethers e.g., dioxane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether.
  • halogenated hydrocarbons e.g. methylene chloride, chloroform, 1,2-dichloroe
  • methanol, ethanol, isopropanol e.g, N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), hexamethylphosphoric acid triamide, acetonitrile.
  • polar solvents eg, N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), hexamethylphosphoric acid triamide, acetonitrile.
  • R 12 , R 13 , R 14 , R 15 and R 16 in compound [I] are the same or different and are hydrogen, halogen, C 1-6 alkyl optionally substituted with halogen or optionally substituted with halogen C 1-6 alkoxy, preferably hydrogen, fluorine, chlorine, methyl, t-butyl, trifluoromethyl or trifluoromethoxy, more preferably hydrogen, fluorine, methyl, t-butyl, trifluoromethyl or It is trifluoromethoxy.
  • R 21 , R 22 and R 23 in compound [I] are the same or different and are hydrogen, halogen, C 1-6 alkyl optionally substituted with halogen, C 1-6 alkoxy optionally substituted with halogen , optionally substituted with halogen, sulfanyl, nitro or cyano, preferably hydrogen, fluorine, chlorine, bromine, trifluoromethyl, methoxy, pentafluorosulfanyl, nitro or cyano, preferably hydrogen or fluorine be.
  • R 3 in compound [I] is C 1-6 alkyl, preferably methyl.
  • R 3 in compound [I] is and R 32 , R 33 , R 34 , R 35 and R 36 are the same or different and are hydrogen, halogen, C 1-6 alkyl optionally substituted with halogen, optionally substituted with halogen C 1-6 alkoxy, sulfanyl optionally substituted with halogen, nitro or cyano, preferably hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, pentafluorosulfanyl, nitro or cyano , more preferably 4-fluorophenyl, 2,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,3,4,5,6-pentafluorophenyl, 4-fluoro-2-methylphenyl, 4 -fluoro-2,6-dimethylphenyl, 4-trifluoromethylphenyl, 4-cyanophenyl, 4-nitrophenyl, 4-pentafluorosulfanylpheny
  • R 12 , R 13 , R 14 , R 15 , R 16 , R 21 , R 22 and R 23 are all hydrogen and R 3 is methyl or phenyl, then R 12 , R 14 , R When 16 and R 3 are all methyl and R 23 is hydrogen or fluorine, R 12 is hydrogen or methyl, R 13 is hydrogen or methyl, R 14 is hydrogen or methyl, and R 15 is hydrogen or methyl, R 16 is hydrogen or methyl, R 3 is methyl or unsubstituted phenyl, and R 23 is hydrogen, or R 12 , R 14 , R Except when all of 16 and R3 are methyl at the same time.
  • R 21 and R 22 in compound [I] are hydrogen
  • R 23 is halogen, C 1-6 alkyl optionally substituted with halogen, sulfanyl optionally substituted with halogen, nitro or cyano, preferably fluorine, chlorine, bromine, trifluoromethyl, pentafluorosulfanyl, nitro or cyano.
  • R 22 and R 23 in compound [I] are hydrogen
  • R 21 is halogen, C 1-6 alkyl optionally substituted with halogen, sulfanyl optionally substituted with halogen, nitro or cyano, preferably fluorine, chlorine, trifluoromethyl, pentafluorosulfanyl, nitro or cyano.
  • R 21 and R 23 in compound [I] are hydrogen
  • R 22 is halogen, C 1-6 alkyl optionally substituted with halogen, sulfanyl optionally substituted with halogen, nitro or cyano, preferably fluorine, chlorine, trifluoromethyl, pentafluorosulfanyl, nitro or cyano.
  • R 22 in compound [I] is hydrogen and R 21 and R 23 are fluorine.
  • each of R 23 and R 34 in compound [I] is hydrogen, halogen, alkyl optionally substituted with halogen, sulfanyl optionally substituted with halogen, cyano or nitro, preferably , hydrogen, fluorine, trifluoromethyl, pentafluorosulfanyl, cyano or nitro.
  • Preferred specific embodiments are the following compounds.
  • the anion (X ⁇ ) that forms a salt with the acridine compound is perchlorate ion (ClO 4 ⁇ ), hexafluorophosphate ion (PF 6 ⁇ ) or tetrafluoroborate ion (BF 4 ⁇ ) . ).
  • the anion (X ⁇ ) that forms a salt with the acridine compound is perchlorate ion (ClO 4 ⁇ ).
  • presentation of preferred embodiments and options for different features of the compounds, methods and compositions of the invention refers to combinations of preferred embodiments and options for such different features, so long as they are combinable and consistent. Including suggestions.
  • Compound [I] can be produced, for example, according to the production method shown below.
  • the production methods shown below are examples, and the production method of compound [I] is not limited to these.
  • reaction temperature reaction temperature, reaction time, etc.
  • reaction time reaction time
  • Compound [VI] which is an intermediate of compound [I] of the present invention, can be produced by the reaction represented by the above reaction scheme. Specifically, compound [VI] can be produced by reacting compound [IV] with compound [V] in the presence of a Bronsted base in a solvent inert to the reaction.
  • Compound [V] is a known compound or a compound that can be easily produced by a known method.
  • reaction temperature reaction temperature
  • reaction time reaction time
  • Compound [VI] which is an intermediate of compound [I] of the present invention, can be produced by the reaction represented by the above reaction scheme. Specifically, compound [VI] can be produced by reacting compound [IV] and compound [VII] in the presence of a base using a palladium catalyst in a solvent inert to the reaction.
  • Compound [VII] is a known compound or a compound that can be easily produced by a known method.
  • reaction temperature reaction temperature
  • reaction time reaction time
  • the compound [I] of the present invention can be produced by the reaction represented by the above reaction scheme. Specifically, compound [VI] and compound [VIII] are reacted in the presence of a Lewis acid in the absence of a solvent or in a solvent inert to the reaction. In addition, you may perform this process under microwave irradiation. Furthermore, the compound [I] can be produced by allowing a salt (R + ⁇ X ⁇ ) to act.
  • R is, for example, an alkali metal atom, preferably sodium.
  • Compound [VIII] is a known compound or a compound that can be easily produced by a known method.
  • reaction temperature reaction temperature
  • reaction time reaction time
  • the compound [I] of the present invention can be produced by the reaction represented by the above reaction scheme. Specifically, compound [IX] and compound [X] are reacted in a solvent inert to the reaction, and a salt (R + ⁇ X ⁇ ) is allowed to act to produce compound [I]. can be done.
  • Compound [IX] and compound [X] are either known compounds or compounds that can be easily produced by known methods. Compound [X] can also be produced from its precursor halide and magnesium and used as such in this reaction.
  • reaction temperature reaction temperature
  • reaction time reaction time
  • the product in each reaction in the above reaction scheme, can be used as a reaction solution or as a crude product in the next reaction, but it can also be isolated from the reaction mixture according to a conventional method, and can be easily separated by a conventional separation means. It can also be refined. Common separation means include, for example, recrystallization, distillation, chromatography.
  • the starting material compound, intermediate compound, target compound and compound [I] in each of the above steps include geometric isomers, stereoisomers, optical isomers and tautomers.
  • Various isomers can be separated by a general optical resolution method. It can also be produced from a suitable optically active raw material compound.
  • Compound [I] can be produced by the synthetic method shown in each of the above reaction formulas or a method equivalent thereto.
  • the raw material compound in the manufacture of compound [I] may be commercially available or manufactured according to a known method or a method equivalent thereto.
  • the starting material compounds and target compounds in each of the above steps can be used in the form of appropriate salts.
  • Examples of such salts include those similar to those exemplified below as salts of compound [I].
  • the present invention also includes various hydrates, solvates and crystal polymorphs of compound [I].
  • Compound [I] includes compounds in which one or more atoms are substituted with one or more isotopic atoms.
  • isotopic atoms include deuterium ( 2 H), tritium ( 3 H), 13 C, 15 N, 18 O, and the like.
  • the compound [I] may be a co-crystal or a co-crystal salt.
  • a co-crystal or co-crystal salt is a crystalline substance composed of two or more distinct solids at room temperature, each with different physical properties (e.g., structure, melting point, heat of fusion, etc.).
  • Co-crystals and co-crystal salts can be produced by applying known co-crystallization methods.
  • the excitation wavelength (maximum absorption wavelength) of compound [I] is visible light (360 nm to 830 nm), preferably 365 nm to 435 nm. can be done.
  • compound [I] Since compound [I] has a strong oxidizing power, it can be used as a photoredox catalyst to oxidize an aromatic compound, thereby converting the hydrogen of the aromatic compound into a hydroxyl group at a high yield.
  • compound [I] can be used as a photoredox catalyst to produce phenol from benzene in high yield.
  • Compound [I] can produce oxidative metabolites of pharmaceuticals as a photoredox catalyst.
  • compound [I] When compound [I] is used as a photoredox catalyst, 0.001 to 10 molar equivalents of compound [I] can be added to 1 mol of the substrate.
  • a method for producing phenols using the compound [I] as a photoredox catalyst is a method for producing phenols, including an oxidation step of oxidizing an aromatic compound to convert it to a phenol, wherein the oxidation step comprises: It is characterized by oxidizing an aromatic compound with a photoredox catalyst.
  • the aromatic compound that is the raw material for the phenols may have a substituent.
  • the number of the substituent is not limited as long as it has one or more conversion points to phenols. Specifically, it may have one or more substituents. When it has two or more substituents, the substituents may be the same or different. Examples of the substituent include halogen, alkyl, alkoxy, carboxy and the like.
  • the aromatic ring that forms the skeleton of the aromatic compound is not particularly limited, but examples thereof include benzene, naphthalene, anthracene, phenanthrene, pyrene, and fullerene.
  • aromatic compounds include benzene, fluorobenzene, chlorobenzene, bromobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, ethylbenzene, naphthalene, 1-chloronaphthalene, 2 -chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, 1-methylnaphthalene, 2-methylnaphthalene, anthracene, phenanthrene, pyrene and the like.
  • the photoredox catalyst of the present invention oxidizes the aromatic compound and converts it into the phenol.
  • the oxidation reaction proceeds by photoexciting the photoredox catalyst of the present invention.
  • the irradiation light in the photoreaction is also not particularly limited, but visible light is preferable from the viewpoint of further simplicity of the reaction. More specifically, it is more preferred that the photoredox catalyst of the present invention has an absorption band in the visible light region and is excitable by visible light.
  • a more preferable wavelength depends on the absorption band of the photoredox catalyst of the present invention, but for example, 300 to 450 nm is more preferable, 360 to 450 nm is more preferable, and 365 to 435 nm is more preferable. Especially preferred.
  • reaction temperature in the oxidation step is not particularly limited, it is, for example, -100 to 250°C, preferably 0 to 40°C, more preferably 0 to 30°C.
  • reaction temperature in the oxidation step is, for example, -100 to 250°C, preferably 0 to 40°C, more preferably 0 to 30°C.
  • the photoreaction can be easily carried out, for example, by using visible light contained in natural light such as sunlight.
  • natural light such as sunlight.
  • a light source such as an LED light, a xenon lamp, a halogen lamp, a fluorescent lamp, or a mercury lamp may be appropriately used.
  • a filter that cuts wavelengths other than the required wavelength may be used as appropriate.
  • Root temperature in the following examples usually means about 10°C to about 35°C.
  • the ratios shown for mixed solvents are volume ratios unless otherwise specified. % indicates % by weight unless otherwise specified.
  • 1 HNMR proto nuclear magnetic resonance spectrum
  • a compound of Reference Example 2 was produced in the same manner as in Reference Example 1 using the corresponding raw material compound.
  • Table 2 shows the structural formulas and physicochemical data of the compounds of Reference Examples 1-3.
  • Example 1 Preparation of 2,7-difluoro-10-methyl-9-(perfluorophenyl)acridin-10-ium perchlorate (1) AlCl 3 (0.608 g) was added to a solution of 4-fluoro-N-(4-fluorophenyl)-N-methylaniline (1.0 g) in DCM (20 mL), and the mixture was stirred at room temperature for 15 minutes under nitrogen atmosphere. The reaction solution was ice-cooled, a solution of Pentafluorobenzoyl chloride (0.945 mL) in DCM (3.0 mL) was added dropwise with a dropping funnel over 15 minutes, and then warmed to room temperature.
  • Example 1 Preparation of 2,7-difluoro-10-methyl-9-(perfluorophenyl)acridin-10-ium perchlorate (2) AlCl 3 (547 mg) was added to a mixture of 4-fluoro-N-(4-fluorophenyl)-N-methylaniline (1.00 g) and Pentafluorobenzoyl chloride (945 ⁇ L), and the mixture was stirred at room temperature. A 1.0 M NaClO 4 aqueous solution was added to the reaction solution and washed with Hexane. The desired product was extracted from the aqueous layer with DCM. The organic layer was separated and concentrated. The residue was crystallized with DCM/IPE and collected by filtration to obtain the desired product (0.070 g).
  • Example 5 Preparation of 2,7-difluoro-10-methyl-9-phenylacridin-10-ium perchlorate
  • 4-fluoro-N-(4-fluorophenyl)-N-methylaniline 300 mg was It was dissolved in chlorobenzene (5 mL), Benzoyl chloride (189 ⁇ L) and Tf-OH (trifluoromethanesulfonic acid) (122 ⁇ L) were added, and the mixture was stirred at 160° C. for 1 hour under microwave irradiation. The reaction was diluted with DCM and the organic layer was washed with water, 1M aqueous NaClO 4 and concentrated. The residue was dissolved in a small amount of DCM, IPE was added to precipitate crystals, IPE was further added, the crystals were collected by filtration and washed with IPE to obtain the desired product (140 mg).
  • Example 20 Preparation of 10-(4-fluorophenyl)-9-phenylacridin-10-ium perchlorate 10-(4-fluorophenyl)acridin-9(10H)-one (300 mg) was dissolved in THF (10 mL). , Phenylmagnesium bromide (691 ⁇ L) was added under ice-cooling under a nitrogen atmosphere, and the mixture was stirred at room temperature. After confirming the disappearance of the raw materials, the reaction solution was concentrated. The residue was dissolved in DCM, washed with water, 1M NaClO4 and concentrated. The residue was dissolved in a small amount of DCM, and IPE was added little by little to precipitate crystals. Crystals were collected by filtration and washed with IPE to obtain the desired product (174 mg).
  • the compounds of Examples 22 to 40 can be produced in the same manner as in Examples 1, 5 or 20 using corresponding starting compounds.
  • the structural formulas of the compounds of Examples 22-40 are shown in Tables 9-12, respectively.
  • Test results of representative compounds of the present invention are shown below, and the actions of the compounds are described, but the present invention is not limited to these test examples.
  • Test Example 1 (measurement of singlet excited state reduction potential) -Sample Preparation A sample was prepared by dissolving the compound of the present invention or a comparative compound (5 mmol/L) and TBAPF6 (100 mmol/L) shown in Table 13 below in acetonitrile (1 mL). - Cyclic voltammetry (CV) measurement A sample was injected into a cell for voltammetry, each electrode was attached in an argon atmosphere, and the measurement was performed by setting the apparatus. The one-electron reduction potential (E red ) was determined from the average value of the peak potentials.
  • Electrolyte Tetrabutylammonium hexafluorophpsphate (TBAPF6)
  • Working electrode platinum disk electrode (manufactured by BAS)
  • Counter electrode Platinum wire (manufactured by BAS)
  • Reference electrode Ag/AgNO 3 (manufactured by BAS)
  • Sweep speed 100 mV/s
  • Apparatus Electrochemical Analyzer Model 610E (manufactured by BAS) Measurement of Maximum Absorption Wavelength A sample was measured using an ultraviolet-visible spectrophotometer 8454 (manufactured by Agilent Technologies).
  • Test Example 2 Measurement of fluorescence lifetime
  • a sample was prepared by dissolving the compound of the present invention (0.1 mmol/L) in acetonitrile (3 mL), enclosing it in a 1 cm square cell, and substituting it in an argon atmosphere.
  • This sample was measured using a fluorescence lifetime photometer (DeltaFlex: manufactured by Horiba, Ltd.). The measurement results are shown in FIG.
  • Test Example 3 (DFT calculation: Electron Affinity) DFT was calculated using the following system. Hardware: High Performance Computer (manufactured by HPC Systems) Software: Gaussian09 RevD.01 Perform the following calculations 1 . Structure optimization (cation) (M06-2X/6-31++G(d)) and energy value 2. HOMO and LUMO levels 3 . Structural optimization (neutral radical) (UM06-2X/6-31++G(d)) and energy value 4. Calculation of electron affinity Figure 1 shows the results.
  • Test Example 4 production of phenol
  • the compound of the present invention (8 mol%), benzene (0.1 M), water (72 ⁇ L (arbitrary)), deuterated acetonitrile solution (2 mL) under an oxygen atmosphere, LED lamp (trade name: Aldrich (trademark) microphotochemical Reactor (manufactured by Merck) was used for irradiation at the wavelengths and irradiation times shown in Table 14.
  • LED lamp trade name: Aldrich (trademark) microphotochemical Reactor (manufactured by Merck) was used for irradiation at the wavelengths and irradiation times shown in Table 14.
  • Acr + -Mes (Comparative Example 1) was used for comparison. The results are shown in Table 14.
  • the yield indicates the phenol produced, and the residual ratio indicates the ratio of benzene used as a raw material.
  • the yield and residual rate were calculated from an NMR chart using 1,3,5-trimethoxybenzene as an internal standard reagent.

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