WO2019216600A1 - Novel oxime ester compound and photoresist composition comprising same - Google Patents

Novel oxime ester compound and photoresist composition comprising same Download PDF

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WO2019216600A1
WO2019216600A1 PCT/KR2019/005284 KR2019005284W WO2019216600A1 WO 2019216600 A1 WO2019216600 A1 WO 2019216600A1 KR 2019005284 W KR2019005284 W KR 2019005284W WO 2019216600 A1 WO2019216600 A1 WO 2019216600A1
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group
unsubstituted
substituted
formula
compound
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PCT/KR2019/005284
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French (fr)
Korean (ko)
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진성민
문봉석
강지승
홍원기
하민수
이규성
진상준
박노길
이현우
변우근
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주식회사 트리엘
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/63—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the present invention relates to a novel oxime ester compound and a photoresist composition comprising the same, and more particularly, by absorbing UV and efficiently generating radicals, high transparency and high sensitivity can be realized, and outgas can be minimized.
  • the present invention relates to a novel oxime ester compound and a photoresist composition comprising the same.
  • a medium is required.
  • the medium is called a photoresist (PR).
  • Such a photoresist is a material that can selectively remove the lighted portion and the non-lighted portion during the subsequent development process by using the characteristic that the solubility in the developer is changed by receiving light of a specific wavelength.
  • photoresist removes the part selectively changed by light by using developer.
  • Positive resist is the case where the lighted area is melted well by developer, and vice versa. resist).
  • a photoresist composition is uniformly coated or coated on an insulating film or a conductive metal film formed on a substrate, and a mask having a predetermined shape is present.
  • the photoresist composition coated under the above is exposed and developed with an alkaline aqueous developer or the like to form a pattern of a desired shape.
  • the patterned photoresist film is used as a mask to dry or wet etch the metal film or the insulating film, and then the remaining photoresist film is removed to form a fine circuit on the substrate.
  • the photoresist composition is obtained by adding a photoinitiator to a polymerizable compound having an ethylenically unsaturated bond, and a photoinitiator having excellent sensitivity to a long wavelength UV light source is desired.
  • a photoinitiator having excellent sensitivity to a long wavelength UV light source is desired.
  • oxime ester compounds have been gradually used in photoresist compositions due to their relatively excellent photosensitive properties.
  • the oxime ester derivatives used in the prior arts have the advantages of excellent solubility and stability in the solvent used, but due to low photo-initiation efficiency and contamination of equipment due to outgassing during the exposure and heating processes, There is a problem of this shrinking.
  • the present invention relates to a photoresist composition which is developed with an alkaline developer used in a thin film display and is capable of forming a pattern with color resists, organic insulating films, liquid crystal alignment films, column spacers, UV overcoats, etc. of thin film display devices such as TFT-LCDs and OLEDs.
  • a photoresist composition containing a binder resin, a polyfunctional monomer having an ethylenically unsaturated bond, and a photoinitiator is preferred.
  • the sensitivity is low during the exposure process for pattern formation, so the amount of use of the photoinitiator must be increased or the exposure amount must be increased.
  • the contamination of the equipment due to the foreign matter generated after the decomposition of the photoinitiator and thereby the yield is reduced.
  • an object of the present invention is to substitute sulfide groups for fluorene, dibenzofuran, and dibenzothiophene, which have excellent solubility, to provide additional solubility due to excellent solubility in long wavelength UV light source and excellent solubility. It is possible to provide an oxime ester compound as a photoinitiator having a characteristic that can minimize the end group structure to minimize the outgas generation.
  • a second technical problem according to the present invention includes the oxime ester compound, by absorbing UV to efficiently generate radicals to provide a photoresist composition having high transparency, high sensitivity, and minimize the outgas There is a purpose.
  • the present invention provides a novel oxime ester compound represented by the following [Formula A] in order to provide a photoresist composition excellent in light sensitivity and excellent in heat resistance.
  • the substituent R ′ is hydrogen, deuterium, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted hetero atom, N, O, P, Si And C 3 -C 24 heteroaryl group having 1 to 3 atoms selected from S, substituted or unsubstituted C 1 -C 20 hydroxyalkyl group, substituted or unsubstituted C 7 -C 24 arylalkyl group And a substituted or unsubstituted C 3 -C 20 cycloalkyl group,
  • M is 0 or 1
  • N is 1 or 2, and when n is 2, each R'-S is the same or different,
  • the substituents R 1 and R 2 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 6
  • An aryl group of -C 30 a substituted or unsubstituted heteroaryl group of C 3 -C 24 having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms, a substituted or unsubstituted C Any one selected from a 1 -C 20 alkoxy group, a substituted or unsubstituted C 7 -C 24 arylalkyl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl group,
  • the substituents R 5 to R 6 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 6
  • An aryl group of -C 30 a substituted or unsubstituted heteroaryl group of C 3 -C 24 having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms, a substituted or unsubstituted C 1- C 20 alkoxy group, substituted or unsubstituted C 7 -C 24 arylalkyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl group, substituted or unsubstituted C 1 -C 20 alkylthioyl A group, a substituted or unsubstituted C 6 -C 20 arylthionyl group, a substituted or unsubsti
  • X is any one selected from CR 3 R 4 , S, O,
  • the substituents R 3 and R 4 are the same or different, and are each independently hydrogen, deuterium, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or C 3 -C 24 heteroaryl group, unsubstituted or unsubstituted C 1 -C 20 alkoxy group, unsubstituted and having 1 to 3 atoms selected from hetero atoms as N, O, P, Si, and S Or an unsubstituted C 7 -C 20 arylalkyl group or a substituted or unsubstituted C 3 -C 20 cycloalkyl group, and the substituents R 3 and R 4 are bonded to each other to form an alicyclic or aromatic group. Can form a monocyclic or polycyclic ring,
  • K is an integer selected from 0 to 4-n, and when k is 2 or more, each R 6 is the same as or different from each other,
  • L is an integer selected from 0 to 3, and when l is 2 or more, each R 5 is the same as or different from each other,
  • 'Substituted' in 'substituted or unsubstituted' in [Formula A] is deuterium, cyano group, nitro group, halogen group, hydroxy group, C 1 -C 24 alkyl group, C 3 -C 20 cycloalkyl group, alkynyl group of C 1 -C 24 halogenated alkyl group, C 2 -C 24 alkenyl, C 2 -C 24 of, C 1 - 24 heterocyclic group in the alkyl group, C 6 -C 24 aryl, C 7 -C 24 Arylalkyl group, C 3 -C 24 heteroaryl group, C 3 -C 24 heteroarylalkyl group, C 1 -C 24 alkoxy group, C 1 -C 24 alkylamino group, C 6 -C 24 arylamino group Substituted with one or more substituents selected from the group consisting of C 3 -C 24 heteroarylamino group, C 1
  • the present invention also provides a photoresist composition comprising the oxime ester compound.
  • the photoresist composition comprising the novel oxime ester compound represented by [Formula A] according to the present invention can efficiently absorb UV to provide a high sensitivity photoresist composition, and in particular, at the time of high temperature crosslinking according to the prior art. Yield decreases due to foreign substances generated after the photoinitiator is decomposed, and the problem of decreased production due to increased exposure time due to increased exposure amount can be solved, and a photoresist composition having excellent sensitivity to a long wavelength UV light source can be provided. It can be effective.
  • the present invention provides an oxime ester compound represented by the above [Formula A].
  • the substituent R ′ is hydrogen, deuterium, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted hetero atom, N, O, P, Si And a C 3 -C 24 heteroaryl group having 1 to 3 atoms selected from S, a substituted or unsubstituted C 1 -C 20 hydroxyalkyl group, a substituted or unsubstituted C 7 -C 24 arylalkyl group , And any one selected from a substituted or unsubstituted C 3 -C 20 cycloalkyl group,
  • M is 0 or 1
  • N is 1 or 2, and when n is 2, each R'-S is the same or different,
  • the substituents R 1 and R 2 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 6
  • An aryl group of -C 30 a substituted or unsubstituted heteroaryl group of C 3 -C 24 having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms, a substituted or unsubstituted C Any one selected from a 1 -C 20 alkoxy group, a substituted or unsubstituted C 7 -C 24 arylalkyl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl group,
  • the substituents R 5 to R 6 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 6
  • An aryl group of -C 30 a substituted or unsubstituted heteroaryl group of C 3 -C 24 having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms, a substituted or unsubstituted C 1- C 20 alkoxy group, substituted or unsubstituted C 7 -C 24 arylalkyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl group, substituted or unsubstituted C 1 -C 20 alkylthioyl A group, a substituted or unsubstituted C 6 -C 20 arylthionyl group, a substituted or unsubsti
  • X is any one selected from CR 3 R 4 , S, O,
  • the substituents R 3 and R 4 are the same or different, and are each independently hydrogen, deuterium, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or C 3 -C 24 heteroaryl group, unsubstituted or unsubstituted C 1 -C 20 alkoxy group, unsubstituted and having 1 to 3 atoms selected from hetero atoms as N, O, P, Si, and S Or an unsubstituted C 7 -C 20 arylalkyl group or a substituted or unsubstituted C 3 -C 20 cycloalkyl group, and the substituents R 3 and R 4 are bonded to each other to form an alicyclic or aromatic group. Can form a monocyclic or polycyclic ring,
  • K is an integer selected from 0 to 4-n, and when k is 2 or more, each R 6 is the same as or different from each other,
  • L is an integer selected from 0 to 3, and when l is 2 or more, each R 5 is the same as or different from each other,
  • the 'substituted' in 'substituted or unsubstituted' in [Formula A] is deuterium, cyano group, nitro group, halogen group, hydroxy group, C 1 -C 24 alkyl group, substituted or unsubstituted C 3 of the -C 20 cycloalkyl group, C 1 -C 24 halogenated alkyl group, C 2 -C 24 alkenyl group, C 2 -C 24 alkynyl group of, C 1 - 24 heterocyclic group, C 6 -C 24 aryl group, C 7 -C 24 arylalkyl group, C 3 -C 24 heteroaryl, C 3 -C 24 heteroaryl group, C 1 -C 24 alkoxy group, C 1 -C 24 in the alkyl group, C In the group consisting of 6 -C 24 arylamino group, C 3 -C 24 heteroarylamino group, C 1 -C 24 alkoxy group
  • a functional group including an oxime ester group is bonded to one benzene ring of fluorene, dibenzofuran or dibenzothiophene according to the kind of X in the formula (A).
  • the functional group including the oxime ester group includes substituents R 1 and R 2 , and may further have a carbonyl group at the benzene ring side.
  • oxime ester compound represented by the above [Formula A] is used as a photoresist composition, a structure in which sulfide is bonded to a terminal benzene ring in a structure having a plurality of benzene rings such as fluorene, dibenzofuran or dibenzothiophene Due to this, it is possible to provide an oxime ester compound as a photoinitiator having excellent sensitivity in a long wavelength UV light source, excellent solubility, and can minimize outgas generation.
  • the aryl group which is a substituent used in the compound of the present invention, is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and includes a single or fused ring system containing 5 to 7 members, preferably 5 or 6 members, In addition, when there is a substituent on the aryl group may be fused with a neighboring substituent (fused) with each other to further form a ring.
  • aryl group examples include a phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, naphthyl group, anthryl group, phenanthryl group, Aromatic groups such as pyrenyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl and the like, and the like.
  • Hydrogen atom is deuterium atom, halogen atom, hydroxy group, nitro group, cyano group, silyl group, amino group (-NH2, -NH (R), -N (R ') (R''),R' and R "are Independently an alkyl group of C 1 -C 10 , in this case an “alkylamino group”), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group of C 1 -C 24 , C 1 -C 24 halogenated alkyl group, C 2 -C 24 alkenyl group, C 2 -C 24 alkynyl group, C 1 -C 24 heteroalkyl group, C 6 -C 24 aryl group, C 7 -C 24 May be substituted with an arylalkyl group, a C 2 -C 24 heteroaryl group, or
  • the heteroaryl group which is a substituent used in the compound of the present invention, contains 1, 2 or 3 heteroatoms selected from N, O, P, Si, S, Ge, Se, Te, and C 2 -C wherein the remaining ring atoms are carbon.
  • a ring aromatic system of 24 wherein the rings can be fused to form a ring.
  • At least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as in the case of the aryl group.
  • alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like, and one of the alkyl groups
  • the above hydrogen atoms may be substituted with the same substituents as in the case of the aryl group.
  • the above hydrogen atoms can be substituted with the same substituents as in the case of the aryl group.
  • silyl group which is a substituent used in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl And dimethylfuryl silyl and the like, and at least one hydrogen atom in the silyl group may be substituted with the same substituent as in the case of the aryl group.
  • the substituents R 3 and R 4 may be bonded to each other to form a monocyclic or polycyclic ring of alicyclic or aromatic', and as an example, the substituents R 3 and R 4 are alkyl groups.
  • an alicyclic monocyclic ring may be formed, wherein s is preferably an integer of 0 to 5, and the carbon ring including s may further form an aliphatic or aromatic ring. It may include.
  • the substituents R 3 and R 4 when the substituents R 3 and R 4 is an aryl group, as shown in [Formula A-3], the substituents R 3 and R 4 may be bonded to each other to form an alicyclic or aromatic ring, wherein p is 0 to It is preferably an integer of 2, and the carbon ring containing p may include additional aliphatic or aromatic rings.
  • R 1 to R 4 , R ′ are as defined above, and m is 0 or 1.
  • the oxime ester compound represented by [Formula A-1] has a functional group including an oxime ester group bonded to one benzene ring of a fluorene group including R 3 and R 4, wherein the functional group is substituted with a substituent R 1 and One of the carbon atoms in the other benzene ring having an oxime ester group containing R 2 and optionally having a carbonyl group in the benzene ring of the fluorene group, and not having an oxime ester group in the fluorene group bonded thereto; It is a technical feature to have a structure in which the R'-S substituent is bonded.
  • R 1 , R 2 and R ′ are as defined above and m is 0 or 1.
  • the oxime ester compound represented by [Formula A-2] has a functional group including an oxime ester group bonded to one benzene ring of the dibenzothiophene group, and the functional group includes substituents R 1 and R 2 . It has an oxime ester group, and also has a structure containing a carbonyl group selectively in the benzene ring of the dibenzothiophene group, and one carbon atom in the other benzene ring to which the oxime ester group in the dibenzothiophene group is not bonded. It is a technical feature to have a structure in which the R'-S substituent is bonded.
  • R 1 , R 2 and R ′ are as defined above and m is 0 or 1.
  • the oxime ester compound represented by the above [Formula A-3] has a functional group including an oxime ester group bonded to one benzene ring of a dibenzofuran group, wherein the functional group includes an oxime ester containing substituents R 1 and R 2 A group having a group and optionally comprising a carbonyl group in the benzene ring of the dibenzofuran group, and also having one R'-S substituent at a carbon atom in the other benzene ring to which the oxime ester group in the dibenzofuran group is not bonded. It is characterized by having a combined structure.
  • R ' which corresponds to the sulfide substituent in [Formula A], which is a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 3 -C 20 cyclo It may be a substituent selected from an alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 7 -C 24 arylalkyl group.
  • R ' which corresponds to the sulfide substituent in [Formula A], it may be a substituent represented by (R 8 ) p -Ar-.
  • substituent R 8 is a substituted or unsubstituted C 1 -C 24 alkyl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl group, a substituted or unsubstituted C 6 -C 24 aryl group, substituted or unsubstituted hwandoen of C 7 -C 24 arylalkyl group of substituted or unsubstituted C 1 -C 24 halogenated alkyl group, a substituted or unsubstituted C 1 -C 24 alkoxy group, a substituted or unsubstituted C 1 -C 24 of Alkylsilyl group, substituted or unsubstituted C 6 -C 24 arylsilyl group, substituted or unsubstituted C 1 -C 20 alkylthioyl group, substituted or unsubstituted C 6 -C 20 arylthioyl group , A substituted or
  • the substituent R 'represented by (R 8 ) p -Ar- includes a substituted or unsubstituted C 6 -C 24 aromatic ring represented by -Ar-, and the substituent R 8 is 0 in the aromatic ring. To 3 may be substituted.
  • Ar corresponds to a substituted or unsubstituted C 6 -C 24 aryl group, and when substituted one, substituted or unsubstituted C 6 -C 24 aryl.
  • two substituents, if substituted, represent an aromatic ring in which three radicals in a substituted or unsubstituted C 6 -C 24 aromatic ring are linked to a sulfur atom or to R 8 .
  • the oxime ester compound having a substituent R 'represented by (R 8 ) p -Ar- may have an aromatic ring on one benzene ring of a fluorene group, dibenzofuran group or dibenzothiophene group depending on the type of X. Is directly bonded, the plate-like structure having a plurality of rings can be extended to provide excellent solubility characteristics, and due to this structural characteristics can further minimize the end group structure for imparting solubility to minimize outgas generation Can be.
  • R 'in [Formula A] may be a substituent represented by the following [Formula A-1].
  • the substituents R 11 to R 15 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 1 -C 24 halogenated alkyl group, substituted or unsubstituted C 6 -C 30 aryl group, substituted or unsubstituted C having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms 3 -C 24 heteroaryl group, substituted or unsubstituted C 1 -C 20 alkoxy group, substituted or unsubstituted C 7 -C 20 arylalkyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl group , Substituted or unsubstituted C 1 -C 24 alkylsilyl group, substituted or unsubstituted C 6 -C
  • a specific compound of the oxime ester compound represented by the [Formula A] in the present invention may be a compound represented by any one of the compounds 1 to 330 shown in Table 1 below, but is not limited thereto.
  • the present invention provides a photoresist composition
  • a photoresist composition comprising an oxime ester compound represented by the above [Formula A].
  • the oxime ester compound may be used as a photoinitiator material for photoresist that is included in a photoresist composition to provide radicals by light such as UV and the like, and the photoresist composition may be a column spacer, a flexible insulating film, an overcoat, a black matrix, or a color.
  • a photoresist composition may be a column spacer, a flexible insulating film, an overcoat, a black matrix, or a color.
  • the photoresist composition containing the oxime ester compound has excellent compatibility with a solvent or an acrylic monomer when used as a photoresist composition for a display or an electronic material, has excellent sensitivity to a UV light source, and efficiently uses UV. It is absorbed by, so it has high sensitivity and high transparency, so it can improve yield and performance when using.
  • the photoresist composition may be a water-based development by adding a polymerizable compound or solvent having an ethylenically unsaturated bond with the acrylic polymer, and may further include a photopolymerizable compound, an acrylic polymer or a solvent in the oxime ester compound,
  • the present invention is not limited thereto, and may further include materials used in other known photoresist compositions.
  • the photoresist composition of the present invention may include 0.1 to 20 parts by weight of the oxime ester compound and 80 to 99.9 parts by weight of the photopolymerizable compound with respect to 100 parts by weight of the photoresist composition.
  • the content of the photopolymerizable compound may include 80 to 99.9 parts by weight based on 100 parts by weight of the photoresist composition when used in only two components together with the oxime ester compound. That is, the content of the photopolymerizable compound may include 80 to 99.9 parts by weight based on 100 parts by weight of the photoresist composition when used in only two components together with the oxime ester compound.
  • the photoresist composition may further comprise an acrylic polymer or a solvent, at this time, based on 100 parts by weight of the photoresist composition, 0.1 to 20 parts by weight of the oxime ester compound, 1 to 60 parts by weight of the photopolymerizable compound, acrylic 0 to 40 parts by weight of the polymer and 10 to 90 parts by weight of the solvent.
  • the photoresist composition may further include a red, green, blue or black pigment, in this case with respect to 100 parts by weight of the photoresist composition, 0.1 to 20 parts by weight of the oxime ester compound, 1 to 60 of the photopolymerizable compound It may include parts by weight, 0 to 40 parts by weight of acrylic polymer, 1 to 50 parts by weight of red, green, blue or black pigment and 10 to 90 parts by weight of solvent.
  • a red, green, blue or black pigment in this case with respect to 100 parts by weight of the photoresist composition, 0.1 to 20 parts by weight of the oxime ester compound, 1 to 60 of the photopolymerizable compound It may include parts by weight, 0 to 40 parts by weight of acrylic polymer, 1 to 50 parts by weight of red, green, blue or black pigment and 10 to 90 parts by weight of solvent.
  • the photopolymerizable compound is a compound including one or two or more acrylic groups, methacryl groups or vinyl groups.
  • the photoinitiator according to the present invention refers to a compound in which radicals are generated by UV and crosslinked by the generated radicals.
  • the photopolymerizable compound include alkyl acrylates such as hexyl (meth) acrylate, cyclohexyl (meth) acrylate, tetradecyl (meth) acrylate and hexadecyl (meth) acrylate; Alkyl methacrylate, ethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, decanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Ta-erythritol penta (meth) acryl
  • the photoresist composition according to the present invention may selectively use an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in the side chain in order to provide thin film properties such as pattern characteristics control and heat resistance.
  • the acrylic polymer is a copolymer of monomers including the monomers described below.
  • the monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate and hexadecyl (meth) acrylate, isobonyl (meth ) Acrylate, dandanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, Acrylic acid, methacrylic acid, styrene, ace
  • the content of the acrylic polymer preferably includes 0 to 40 parts by weight based on 100 parts by weight of the photoresist composition when it contains a solvent.
  • the content of the acrylic polymer is mixed by 40 parts by weight or more, the viscosity of the solution is too high, there is a problem that the coating is difficult.
  • the photoresist composition of the present invention may be used by further adding a photoinitiator known as needed.
  • a photoinitiator known as needed.
  • ketones, ketoacetals, thioxanthones, phosphine oxides, anthraquinones, trichloromethyl triazines, oxime esters, and the like can be used.
  • photoinitiators include phenyl Biphenyl ketone, thioxanthone, isopropyl thioxanthone, diethyl thioxanthone, benzophenone, 1-benzyl-1-dimethylamino-1- (4-morpholino-benzoyl) propane, 1-hydroxy- 1-benzoylcyclohexane, 2-morpholinyl-2- (4-methylmercapto) benzoylpropane, ethylanthraquinone, 4-benzoyl-4-methyldiphenylsulfide, benzoin butyl ether, 2-hydroxy-2- Benzoylpropane, 2-hydroxy-2- (4-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, diphenyl-2,4,6-trimethylbenzoylphosphine oxide, Methyl benzoyl formate
  • the photoinitiator may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the photoresist composition in order to adjust exposure sensitivity and pattern characteristics.
  • the photoinitiator may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the photoresist composition in order to adjust exposure sensitivity and pattern characteristics.
  • the solvent is not only selectively used to dissolve the photoresist composition, but also used to obtain excellent coatability and a transparent thin film, and it is preferable to use an organic solvent as such a solvent.
  • organic solvent preferably ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate (EEP), ethyl lactate, propylene glycol Methyl ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexa Paddy, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), ⁇ -butyrolactone, diethyl ether, ethylene glycol dimethyl ether, digle Lime (DMF
  • the photoresist composition according to the present invention further comprises at least one colorant pigment selected from the group consisting of red, green, blue and black, if necessary, a photoresist composition for a color matrix or a photoresist composition for a black matrix It can be prepared as.
  • the content of the color colorant pigment to be added may be appropriately selected depending on the conditions of use of the photoresist, for example, 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the photoresist composition. have.
  • the content of the colorant pigment satisfies this range, the color purity and luminance characteristics of the color filter obtained are very excellent, and when the content of the pigment is added 50 parts by weight or more, there is a problem that the crystallization or the pattern characteristics are degraded when the pattern is formed. have.
  • the black pigment may be used a carbon black dispersion commonly used, but is not limited thereto.
  • the photoresist composition according to the present invention is a color filter, an organic light emitting element (OLED), an illumination device, a TFT-LCD, a metal sensor, a solar cell, an integrated circuit, an organic field-effect transistor (O-FET) and an organic thin film transistor It can be used in any one device selected from (O-TFT).
  • the oil obtained was solidified using 10 ml of ethyl acetate and 100 ml of methanol to obtain the target compound 1- (9,9). 9.0 g (92%) of -dimethyl-2- (phenylthio) -fluorene-7-yl) propan-1-one were obtained.
  • acryl copolymer 1 prepared in Synthesis Example 18 acryl copolymer 1 prepared in Synthesis Example 18 , PGMEA (to 100 parts by weight), a photopolymerizable compound and a photoinitiator were sequentially added according to the components and contents shown in Table 2 below at room temperature. Stirring for 12 hours to prepare a photoresist composition.
  • composition of the photoresist prepared from the above examples is shown in Table 2 below.
  • a photoresist was prepared in the same manner as in Example 1, except that the photoinitiator used 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione in place of compound 1. It was.
  • a photoresist was prepared in the same manner as in Example 2, except that the photoinitiator used 1- (o-benzoyloxime)-(dibenzo [b, d] furan-2-yl) pentanone instead of compound 15.
  • a photoresist was prepared in the same manner as in Example 3, except that the photoinitiator used 1- (o-acetyloxime)-(dibenzo [b, d] furan-2-yl) pentanone instead of compound 17.
  • the photoresist was spin-coated on a glass substrate, heated at 100 ° C. for 2 minutes in a hot plate, exposed using a step mask, and developed in a 0.04% KOH aqueous solution. Sensitivity was evaluated for the exposure amount in which the step mask pattern maintains 90% of the initial thickness.
  • the photoresist composition was applied onto the substrate using a spin coater, heated at 100 ° C. for 2 minutes, exposed to 500 mJ at 365 nm, and developed in a 0.04% KOH aqueous solution. Hard-bake was performed at 250 degreeC for 30 minutes, and the thickness ratio (%) before and after hard baking of the photoresist film was measured.
  • the photoresist composition was applied onto a substrate using a spin coater, then prebaked at 100 ° C. for 2 minutes, exposed to 500 mJ at 365 nm, and developed in a 0.04% KOH aqueous solution. After performing a hard bake at 250 ° C. for 30 minutes, the transmittance was measured at 400 nm using a UV-vis spectrophotometer.
  • Each 50mg of the prepared compound and the compound used in the comparative example were collected by heating at 230 ° C. for 30 minutes using a headspace device, and then measured by integrating the total amount of generated gas using a GC-Mass device. .
  • Example 1 65 94 98 72
  • Example 2 70 95 97 63
  • Example 3 71
  • Example 4 73
  • 94 94 63 Example 5
  • Example 6 65
  • Example 7 68
  • 96 96 55 Example 8
  • Example 9 72
  • Example 11 60 93 94 70
  • Example 12 80 91 96 81 Example 13 45 93 96 68
  • Example 14 50
  • Example 15 55
  • Example 16 83 89 96 78
  • Example 17 82 91 95 77
  • Example 18 50
  • Example 19 45 94 96 74
  • Example 20 95 97 79 Comparative Example 1 160 88 91 182 Comparative
  • the photoresist composition of the present invention has excellent physical properties such as sensitivity, residual film ratio, transmittance, and the like compared to the conventional photoresist composition, and can significantly reduce the amount of outgas generated during the process. There is an advantage.
  • This result can minimize the out-gas generated from the photoinitiator in the exposure and hard bake process during the TFT-LCD manufacturing process has the advantage of reducing the contamination and improved productivity by shortening the exposure time.

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Abstract

The present invention relates to an oxime ester group-substituted aromatic compound, a preparation method therefor, and a photoresist composition comprising same and is useful for providing a photosensitive composition, which effectively absorbs UV and exhibits high sensitivity.

Description

신규한 옥심에스테르 화합물 및 이를 포함하는 포토레지스트 조성물Novel oxime ester compound and photoresist composition comprising the same
본 발명은 신규한 옥심에스테르 화합물 및 이를 포함하는 포토레지스트 조성물에 관한 것으로, 보다 상세하게는 UV를 흡수하여 라디칼을 효율적으로 발생함으로서 고투명, 고감도의 특성을 구현할 수 있으며 아웃가스를 최소화할 수 있는, 신규한 옥심에스테르 화합물 및 이를 포함하는 포토레지스트 조성물에 관한 것이다.The present invention relates to a novel oxime ester compound and a photoresist composition comprising the same, and more particularly, by absorbing UV and efficiently generating radicals, high transparency and high sensitivity can be realized, and outgas can be minimized. The present invention relates to a novel oxime ester compound and a photoresist composition comprising the same.
TFT-LCD, OLED 등 박막 디스플레이소자와 반도체 소자에 사용되는 물질들을 노광공정을 통해 마스크 원판의 회로설계를 웨이퍼로 전사하기 위해서는 매개체가 필요한데 그 매개체를 포토레지스트(photoresist, PR)라 한다. In order to transfer the materials used in thin film display devices and semiconductor devices such as TFT-LCDs and OLEDs to the wafer through the exposure process, a medium is required. The medium is called a photoresist (PR).
이러한 포토레지스트는 특정 파장의 빛을 받아 현상액에서의 용해도가 변하는 특성을 이용해 후속 현상처리 과정 중 빛을 받은 부분과 그렇지 않은 부분을 선택적으로 제거할 수 있는 물질을 말한다.Such a photoresist is a material that can selectively remove the lighted portion and the non-lighted portion during the subsequent development process by using the characteristic that the solubility in the developer is changed by receiving light of a specific wavelength.
일반적으로 많이 사용되는 포토레지스트는 현상액을 이용하여 빛에 의하여 선택적으로 변화된 부분을 제거하게 되는데, 빛을 받은 부위가 현상액에 의해 잘 녹는 경우를 포지티브 레지스트(positive resist), 그 반대를 네가티브 레지스트(negative resist)라고 한다.Generally used photoresist removes the part selectively changed by light by using developer. Positive resist is the case where the lighted area is melted well by developer, and vice versa. resist).
포토레지스트를 이용하여 액정표시장치 또는 반도체의 집적회로와 같이 미세한 회로 패턴을 형성하기 위해서는 먼저, 기판 상에 형성된 절연막 또는 도전성 금속막에 포토레지스트 조성물을 균일하게 코팅 또는 도포하고, 소정 형상의 마스크 존재 하에서 코팅된 포토레지스트 조성물을 노광하고, 이를 알칼리성 수계 현상액 등으로 현상함으로써, 목적하는 형상의 패턴을 만든다. 이와 같이 패턴된 포토레지스트 막을 마스크로 사용하여 상기 금속막 또는 절연막을 건식 또는 습식 에칭한 다음, 남은 포토레지스트막을 제거하여 기판 상에 미세 회로를 형성하게 된다.In order to form a fine circuit pattern such as an integrated circuit of a liquid crystal display device or a semiconductor by using a photoresist, first, a photoresist composition is uniformly coated or coated on an insulating film or a conductive metal film formed on a substrate, and a mask having a predetermined shape is present. The photoresist composition coated under the above is exposed and developed with an alkaline aqueous developer or the like to form a pattern of a desired shape. The patterned photoresist film is used as a mask to dry or wet etch the metal film or the insulating film, and then the remaining photoresist film is removed to form a fine circuit on the substrate.
이때 포토레지스트 조성물은 에틸렌성 불포화결합을 가지는 중합성 화합물에 광개시제를 첨가한 것이며, 장파장의 UV광원에 뛰어난 감도를 가지는 광개시제가 요망되고 있다. 이러한 포토레지스트의 광개시제로서 최근에는, 상대적으로 탁월한 감광 특성으로 인하여 옥심 에스테르 화합물이 포토레지스트 조성물에 점차 사용되어 왔다.At this time, the photoresist composition is obtained by adding a photoinitiator to a polymerizable compound having an ethylenically unsaturated bond, and a photoinitiator having excellent sensitivity to a long wavelength UV light source is desired. As photoinitiators of such photoresists, in recent years, oxime ester compounds have been gradually used in photoresist compositions due to their relatively excellent photosensitive properties.
이와 관련한 종래 기술로서, 일본공개특허 제2001-302871호(2001.10.31), 국제특허공개공보 제2002-100903호(2002.12.19), 일본등록특허공보 제3798008호(2006.04.28) 및 일본등록특허공보 제4595374호(2010.10.01)에서 광개시제로 사용 가능한 옥심에스테르 유도체에 관한 기술이 제시되어 있다.As a related art in this regard, Japanese Patent Application Laid-Open No. 2001-302871 (2001.10.31), International Patent Publication No. 2002-100903 (2002.12.19), Japanese Patent Application Publication No. 3798008 (2006.04.28) and Japanese Registration Patent Publication No. 4595374 (October 01, 2010) discloses a technique for an oxime ester derivative which can be used as a photoinitiator.
그러나 상기 선행기술들에서 사용되는 옥심에스테르 유도체는 사용되는 용매에 대한 용해도 및 안정성이 우수한 장점을 갖고 있으나, 광개시 효율이 낮고 노광 및 가열 공정 중에 발생한 아웃가스로 인하여 장비가 오염되는 문제로 인하여 생산량이 줄어드는 문제가 있다. However, the oxime ester derivatives used in the prior arts have the advantages of excellent solubility and stability in the solvent used, but due to low photo-initiation efficiency and contamination of equipment due to outgassing during the exposure and heating processes, There is a problem of this shrinking.
따라서 상기와 같은 문제를 해결하기 위한 신규한 광개시제 재료 및 이를 포함하는 포토레지스트 조성물의 개발의 필요성은 지속적으로 요구되고 있는 실정이다.Therefore, there is a continuing need for the development of a novel photoinitiator material and a photoresist composition including the same to solve the above problems.
본 발명은 박막 디스플레이에 사용되는 알칼리 현상액으로 현상되어 TFT-LCD및 OLED와 같은 박막디스플레이 소자의 컬러레지스트, 유기 절연막, 액정 배향막, 컬럼 스페이서, UV 오버코트 등으로 패턴 형성이 가능한 포토레지스트 조성물에 관한 것으로, 이러한 패턴을 형성하기 위해서 이용되는 레지스트 조성물로는 바인더 수지, 에틸렌 불포화 결합을 갖는 다관능성 모노머 및 광개시제를 함유하는 포토레지스트 조성물이 선호되고 있다. The present invention relates to a photoresist composition which is developed with an alkaline developer used in a thin film display and is capable of forming a pattern with color resists, organic insulating films, liquid crystal alignment films, column spacers, UV overcoats, etc. of thin film display devices such as TFT-LCDs and OLEDs. As the resist composition used to form such a pattern, a photoresist composition containing a binder resin, a polyfunctional monomer having an ethylenically unsaturated bond, and a photoinitiator is preferred.
그러나, 종래의 광개시제를 이용하여 패턴을 형성하는 경우 패턴 형성을 위한 노광 공정시 감도가 낮아 광개시제의 사용량을 늘리거나 노광량을 늘려야 하고 이로 인해 노광공정 시간이 늘어나 생산량이 줄어드는 문제가 있고, 아웃가스 발생량이 많아 광개시제가 분해한 후 발생하는 이물질로 인하여 설비가 오염되고 이로 인해 수율이 저하되는 단점이 있다.However, when the pattern is formed using a conventional photoinitiator, the sensitivity is low during the exposure process for pattern formation, so the amount of use of the photoinitiator must be increased or the exposure amount must be increased. There are many disadvantages that the contamination of the equipment due to the foreign matter generated after the decomposition of the photoinitiator and thereby the yield is reduced.
따라서, 본 발명의 목적은 용해도가 우수한 구조인 플루오렌, 디벤조퓨란, 디벤조티오펜에 sulfide기를 치환시킴으로써, 장파장 UV 광원에서 뛰어난 감도를 갖고 있으며 용해도가 우수한 특성으로 인하여 추가적으로 용해도를 부여하기 위한 말단기 구조를 최소화 할 수 있어 아웃가스 발생을 최소화 할 수 있는 특성을 가지는 광개시제로서의 옥심에스테르 화합물을 제공하는 것이다. Accordingly, an object of the present invention is to substitute sulfide groups for fluorene, dibenzofuran, and dibenzothiophene, which have excellent solubility, to provide additional solubility due to excellent solubility in long wavelength UV light source and excellent solubility. It is possible to provide an oxime ester compound as a photoinitiator having a characteristic that can minimize the end group structure to minimize the outgas generation.
또한 본 발명에 따른 두 번째 기술적 과제는 상기 옥심에스테르 화합물을 포함하며, UV를 흡수하여 라디칼을 효율적으로 발생함으로서 고투명, 고감도의 특성을 가지며, 아웃가스를 최소화할 수 있는 포토레지스트 조성물을 제공하는데 그 목적이 있다. In addition, a second technical problem according to the present invention includes the oxime ester compound, by absorbing UV to efficiently generate radicals to provide a photoresist composition having high transparency, high sensitivity, and minimize the outgas There is a purpose.
상기 과제를 위해, 본 발명은 광감도 특성이 우수하고 내열성이 뛰어난 포토레지스트 조성물을 제공하기 위해, 하기 [화학식 A]로 표시되는 신규한 옥심에스테르 화합물을 제공한다.For the above problems, the present invention provides a novel oxime ester compound represented by the following [Formula A] in order to provide a photoresist composition excellent in light sensitivity and excellent in heat resistance.
[화학식 A][Formula A]
Figure PCTKR2019005284-appb-I000001
Figure PCTKR2019005284-appb-I000001
상기 [화학식 A]에서, In [Formula A],
상기 치환기 R'는 수소, 중수소, 치환 또는 비치환된 C1-C30의 알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환되고 이종 원자로 N, O, P, Si 및 S 에서 선택되는 1 내지 3의 원자를 갖는 C3-C24의 헤테로아릴기, 치환 또는 비치환된 C1-C20의 히드록시알킬기, 치환 또는 비치환된 C7-C24의 아릴알킬기 및 치환 또는 비치환된 C3-C20의 시클로알킬기 중에서 선택되는 어느 하나이며, The substituent R ′ is hydrogen, deuterium, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted hetero atom, N, O, P, Si And C 3 -C 24 heteroaryl group having 1 to 3 atoms selected from S, substituted or unsubstituted C 1 -C 20 hydroxyalkyl group, substituted or unsubstituted C 7 -C 24 arylalkyl group And a substituted or unsubstituted C 3 -C 20 cycloalkyl group,
상기 m은 0 또는 1이며,M is 0 or 1,
상기 n은 1 또는 2이며, n 이 2인 경우 각각의 R'-S 는 동일하거나 상이하며,N is 1 or 2, and when n is 2, each R'-S is the same or different,
상기 치환기 R1, R2는 각각 동일하거나 상이하며, 서로 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 치환 또는 비치환된 C1-C30의 알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환되고 이종 원자로 N, O, P, Si, 및 S 에서 선택되는 1 내지 3의 원자를 갖는 C3-C24의 헤테로아릴기, 치환 또는 비치환된 C1-C20의 알콕시기, 치환 또는 비치환된 C7-C24의 아릴알킬기, 치환 또는 비치환된 C3-C20의 시클로알킬기 중에서 선택되는 어느 하나이며,The substituents R 1 and R 2 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 6 An aryl group of -C 30 , a substituted or unsubstituted heteroaryl group of C 3 -C 24 having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms, a substituted or unsubstituted C Any one selected from a 1 -C 20 alkoxy group, a substituted or unsubstituted C 7 -C 24 arylalkyl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl group,
상기 치환기 R5 내지 R6은 각각 동일하거나 상이하며, 서로 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 치환 또는 비치환된 C1-C30의 알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환되고 이종 원자로 N, O, P, Si, 및 S 에서 선택되는 1 내지 3의 원자를 갖는 C3-C24의 헤테로아릴기, 치환 또는 비치환된 C1-C20의 알콕시기, 치환 또는 비치환된 C7-C24의 아릴알킬기, 치환 또는 비치환된 C3-C20의 시클로알킬기, 치환 또는 비치환된 C1-C20의 알킬티오닐기, 치환 또는 비치환된 C6-C20의 아릴티오닐기, 치환 또는 비치환된 C3-C20의 시클로알킬티오닐기 중에서 선택되는 어느 하나이며, The substituents R 5 to R 6 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 6 An aryl group of -C 30 , a substituted or unsubstituted heteroaryl group of C 3 -C 24 having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms, a substituted or unsubstituted C 1- C 20 alkoxy group, substituted or unsubstituted C 7 -C 24 arylalkyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl group, substituted or unsubstituted C 1 -C 20 alkylthioyl A group, a substituted or unsubstituted C 6 -C 20 arylthionyl group, a substituted or unsubstituted C 3 -C 20 cycloalkylthionyl group,
상기 X는 CR3R4, S, O 중에서 선택되는 어느 하나이며, X is any one selected from CR 3 R 4 , S, O,
상기 치환기 R3 및 R4는 각각 동일하거나 상이하며, 서로 독립적으로 수소, 중수소, 치환 또는 비치환된 C1-C30의 알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환되고 이종 원자로 N, O, P, Si, 및 S 에서 선택되는 1 내지 3의 원자를 갖는 C3-C24의 헤테로아릴기, 치환 또는 비치환된 C1-C20의 알콕시기, 치환 또는 비치환된 C7-C20의 아릴알킬기 또는 치환 또는 비치환된 C3-C20의 시클로알킬기 중에서 선택되는 어느 하나이며, 상기 치환기 R3 및 R4는 서로 결합하여 지환족 또는 방향족의 단일환 또는 다환고리를 형성할 수 있으며,The substituents R 3 and R 4 are the same or different, and are each independently hydrogen, deuterium, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or C 3 -C 24 heteroaryl group, unsubstituted or unsubstituted C 1 -C 20 alkoxy group, unsubstituted and having 1 to 3 atoms selected from hetero atoms as N, O, P, Si, and S Or an unsubstituted C 7 -C 20 arylalkyl group or a substituted or unsubstituted C 3 -C 20 cycloalkyl group, and the substituents R 3 and R 4 are bonded to each other to form an alicyclic or aromatic group. Can form a monocyclic or polycyclic ring,
상기 k는 0 내지 4-n 중에서 선택되는 하나의 정수이고, 상기 k가 2 이상인 경우에 각각의 R6는 서로 동일하거나 상이하며,K is an integer selected from 0 to 4-n, and when k is 2 or more, each R 6 is the same as or different from each other,
상기 l은 0 내지 3 중에서 선택되는 하나의 정수이며, 상기 l이 2 이상인 경우에 각각의 R5는 서로 동일하거나 상이하며,L is an integer selected from 0 to 3, and when l is 2 or more, each R 5 is the same as or different from each other,
상기 [화학식 A]에서의 ‘치환 또는 비치환된’에서의 ‘치환’은 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, C1-C24의 알킬기, C3-C20의 시클로알킬기, C1-C24의 할로겐화된 알킬기, C2-C24의 알케닐기, C2-C24의 알키닐기, C1-24의 헤테로알킬기, C6-C24의 아릴기, C7-C24의 아릴알킬기, C3-C24의 헤테로아릴기, C3-C24의 헤테로아릴알킬기, C1-C24의 알콕시기, C1-C24의 알킬아미노기, C6-C24의 아릴아미노기, C3-C24의 헤테로아릴아미노기, C1-C24의 알킬실릴기, C6-C24의 아릴실릴기, C6-C24의 아릴옥시기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환되는 것을 의미한다.'Substituted' in 'substituted or unsubstituted' in [Formula A] is deuterium, cyano group, nitro group, halogen group, hydroxy group, C 1 -C 24 alkyl group, C 3 -C 20 cycloalkyl group, alkynyl group of C 1 -C 24 halogenated alkyl group, C 2 -C 24 alkenyl, C 2 -C 24 of, C 1 - 24 heterocyclic group in the alkyl group, C 6 -C 24 aryl, C 7 -C 24 Arylalkyl group, C 3 -C 24 heteroaryl group, C 3 -C 24 heteroarylalkyl group, C 1 -C 24 alkoxy group, C 1 -C 24 alkylamino group, C 6 -C 24 arylamino group Substituted with one or more substituents selected from the group consisting of C 3 -C 24 heteroarylamino group, C 1 -C 24 alkylsilyl group, C 6 -C 24 arylsilyl group, C 6 -C 24 aryloxy group It means to be.
또한 본 발명은 상기 옥심에스테르 화합물을 포함하는 포토레지스트 조성물을 제공한다.The present invention also provides a photoresist composition comprising the oxime ester compound.
본 발명에 따른 [화학식 A]로 표시되는 신규한 옥심에스테르 화합물을 포함하는 포토레지스트 조성물은 UV를 효율적으로 흡수하여 고감도의 포토레지스트 조성물을 제공할 수 있으며, 특히, 종래 기술에 따른, 고온 가교시에 광개시제가 분해한 후 발생하는 이물질로 인해 수율이 저하되는 단점과, 노광량 증가에 따른 노광공정 시간이 늘어나 생산량이 줄어드는 문제를 해결할 수 있으며, 장파장 UV 광원에 뛰어난 감도를 갖는 포토레지스트 조성물을 제공할 수 있는 효과가 있다.The photoresist composition comprising the novel oxime ester compound represented by [Formula A] according to the present invention can efficiently absorb UV to provide a high sensitivity photoresist composition, and in particular, at the time of high temperature crosslinking according to the prior art. Yield decreases due to foreign substances generated after the photoinitiator is decomposed, and the problem of decreased production due to increased exposure time due to increased exposure amount can be solved, and a photoresist composition having excellent sensitivity to a long wavelength UV light source can be provided. It can be effective.
이하, 본 발명을 더욱 상세하게 설명한다. 다른 식으로 정의되지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 본 발명이 속하는 기술분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 가진다. 일반적으로, 본 명세서에서 사용된 명명법은 본 기술분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.Hereinafter, the present invention will be described in more detail. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.
본원 명세서 전체에서, 어떤 부분이 어떤 구성 요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있는 것을 의미한다.Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless otherwise stated.
본 발명은 상기 [화학식 A]로 표시되는 옥심에스테르 화합물을 제공한다. The present invention provides an oxime ester compound represented by the above [Formula A].
[화학식 A][Formula A]
Figure PCTKR2019005284-appb-I000002
Figure PCTKR2019005284-appb-I000002
상기 [화학식 A]에서, In [Formula A],
상기 치환기 R'는 수소, 중수소, 치환 또는 비치환된 C1-C30의 알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환되고 이종 원자로 N, O, P, Si 및 S 에서 선택되는 1 내지 3의 원자를 갖는 C3-C24의 헤테로아릴기, 치환 또는 비치환된 C1-C20의 히드록시알킬기, 치환 또는 비치환된 C7-C24의 아릴알킬기, 및 치환 또는 비치환된 C3-C20의 시클로알킬기 중에서 선택되는 어느 하나이며, The substituent R ′ is hydrogen, deuterium, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted hetero atom, N, O, P, Si And a C 3 -C 24 heteroaryl group having 1 to 3 atoms selected from S, a substituted or unsubstituted C 1 -C 20 hydroxyalkyl group, a substituted or unsubstituted C 7 -C 24 arylalkyl group , And any one selected from a substituted or unsubstituted C 3 -C 20 cycloalkyl group,
상기 m은 0 또는 1이며,M is 0 or 1,
상기 n은 1 또는 2이며, n 이 2인 경우 각각의 R'-S 는 동일하거나 상이하며,N is 1 or 2, and when n is 2, each R'-S is the same or different,
상기 치환기 R1, R2는 각각 동일하거나 상이하며, 서로 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 치환 또는 비치환된 C1-C30의 알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환되고 이종 원자로 N, O, P, Si, 및 S 에서 선택되는 1 내지 3의 원자를 갖는 C3-C24의 헤테로아릴기, 치환 또는 비치환된 C1-C20의 알콕시기, 치환 또는 비치환된 C7-C24의 아릴알킬기, 치환 또는 비치환된 C3-C20의 시클로알킬기 중에서 선택되는 어느 하나이며,The substituents R 1 and R 2 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 6 An aryl group of -C 30 , a substituted or unsubstituted heteroaryl group of C 3 -C 24 having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms, a substituted or unsubstituted C Any one selected from a 1 -C 20 alkoxy group, a substituted or unsubstituted C 7 -C 24 arylalkyl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl group,
상기 치환기 R5 내지 R6은 각각 동일하거나 상이하며, 서로 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 치환 또는 비치환된 C1-C30의 알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환되고 이종 원자로 N, O, P, Si, 및 S 에서 선택되는 1 내지 3의 원자를 갖는 C3-C24의 헤테로아릴기, 치환 또는 비치환된 C1-C20의 알콕시기, 치환 또는 비치환된 C7-C24의 아릴알킬기, 치환 또는 비치환된 C3-C20의 시클로알킬기, 치환 또는 비치환된 C1-C20의 알킬티오닐기, 치환 또는 비치환된 C6-C20의 아릴티오닐기, 치환 또는 비치환된 C3-C20의 시클로알킬티오닐기 중에서 선택되는 어느 하나이며,The substituents R 5 to R 6 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 6 An aryl group of -C 30 , a substituted or unsubstituted heteroaryl group of C 3 -C 24 having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms, a substituted or unsubstituted C 1- C 20 alkoxy group, substituted or unsubstituted C 7 -C 24 arylalkyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl group, substituted or unsubstituted C 1 -C 20 alkylthioyl A group, a substituted or unsubstituted C 6 -C 20 arylthionyl group, a substituted or unsubstituted C 3 -C 20 cycloalkylthionyl group,
상기 X는 CR3R4, S, O 중에서 선택되는 어느 하나이며, X is any one selected from CR 3 R 4 , S, O,
상기 치환기 R3 및 R4는 각각 동일하거나 상이하며, 서로 독립적으로 수소, 중수소, 치환 또는 비치환된 C1-C30의 알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환되고 이종 원자로 N, O, P, Si, 및 S 에서 선택되는 1 내지 3의 원자를 갖는 C3-C24의 헤테로아릴기, 치환 또는 비치환된 C1-C20의 알콕시기, 치환 또는 비치환된 C7-C20의 아릴알킬기 또는 치환 또는 비치환된 C3-C20의 시클로알킬기 중에서 선택되는 어느 하나이며, 상기 치환기 R3 및 R4는 서로 결합하여 지환족 또는 방향족의 단일환 또는 다환고리를 형성할 수 있으며,The substituents R 3 and R 4 are the same or different, and are each independently hydrogen, deuterium, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or C 3 -C 24 heteroaryl group, unsubstituted or unsubstituted C 1 -C 20 alkoxy group, unsubstituted and having 1 to 3 atoms selected from hetero atoms as N, O, P, Si, and S Or an unsubstituted C 7 -C 20 arylalkyl group or a substituted or unsubstituted C 3 -C 20 cycloalkyl group, and the substituents R 3 and R 4 are bonded to each other to form an alicyclic or aromatic group. Can form a monocyclic or polycyclic ring,
상기 k는 0 내지 4-n 중에서 선택되는 하나의 정수이고, 상기 k가 2 이상인 경우에 각각의 R6는 서로 동일하거나 상이하며,K is an integer selected from 0 to 4-n, and when k is 2 or more, each R 6 is the same as or different from each other,
상기 l은 0 내지 3 중에서 선택되는 하나의 정수이며, 상기 l이 2 이상인 경우에 각각의 R5는 서로 동일하거나 상이하며,L is an integer selected from 0 to 3, and when l is 2 or more, each R 5 is the same as or different from each other,
이때, 상기 [화학식 A]에서의 ‘치환 또는 비치환된’에서의 ‘치환’은 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, C1-C24의 알킬기, 치환 또는 비치환된 C3-C20의 시클로알킬기, C1-C24의 할로겐화된 알킬기, C2-C24의 알케닐기, C2-C24의 알키닐기, C1-24의 헤테로알킬기, C6-C24의 아릴기, C7-C24의 아릴알킬기, C3-C24의 헤테로아릴기, C3-C24의 헤테로아릴알킬기, C1-C24의 알콕시기, C1-C24의 알킬아미노기, C6-C24의 아릴아미노기, C3-C24의 헤테로아릴아미노기, C1-C24의 알킬실릴기, C6-C24의 아릴실릴기, C6-C24의 아릴옥시기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환되는 것을 의미한다.At this time, the 'substituted' in 'substituted or unsubstituted' in [Formula A] is deuterium, cyano group, nitro group, halogen group, hydroxy group, C 1 -C 24 alkyl group, substituted or unsubstituted C 3 of the -C 20 cycloalkyl group, C 1 -C 24 halogenated alkyl group, C 2 -C 24 alkenyl group, C 2 -C 24 alkynyl group of, C 1 - 24 heterocyclic group, C 6 -C 24 aryl group, C 7 -C 24 arylalkyl group, C 3 -C 24 heteroaryl, C 3 -C 24 heteroaryl group, C 1 -C 24 alkoxy group, C 1 -C 24 in the alkyl group, C In the group consisting of 6 -C 24 arylamino group, C 3 -C 24 heteroarylamino group, C 1 -C 24 alkylsilyl group, C 6 -C 24 arylsilyl group, C 6 -C 24 aryloxy group Substituted by one or more substituents selected.
본 발명에 따른 상기 [화학식 A]로 표시되는 옥심에스테르 화합물은 화학식 A에서, X의 종류에 따라 플루오렌, 디벤조퓨란 또는 디벤조티오펜의 한 쪽 벤젠고리에 옥심에스테르기를 포함하는 관능기가 결합하고, 상기 옥심에스테르기가 결합하지 않은 다른 쪽 벤젠고리내 1 내지 2개의 R'-S-가 결합된 구조를 기술적 특징으로 한다. In the oxime ester compound represented by the above [Formula A] according to the present invention, a functional group including an oxime ester group is bonded to one benzene ring of fluorene, dibenzofuran or dibenzothiophene according to the kind of X in the formula (A). In addition, the technical features of the structure in which one or two R'-S- in the other benzene ring to which the oxime ester group is not bonded.
이 때 상기 옥심에스테르기를 포함하는 관능기는 치환기 R1 및 R2를 포함하되, 또한 벤젠고리쪽 위치에 선택적으로 카르보닐기를 가질 수 있다.In this case, the functional group including the oxime ester group includes substituents R 1 and R 2 , and may further have a carbonyl group at the benzene ring side.
이러한 상기 [화학식 A]로 표시되는 옥심에스테르 화합물을 포토레지스트 조성물로서 사용하는 경우 플루오렌, 디벤조퓨란 또는 디벤조티오펜 등의 복수의 벤젠고리를 가지는 구조내 말단 벤젠고리에 sulfide가 결합된 구조로 인해 장파장 UV 광원에서 뛰어난 감도를 가지는 광개시제로서의 옥심에스테르 화합물을 제공할 수 있으며, 용해도가 우수하며, 아웃가스 발생을 최소화할 수 있다.When the oxime ester compound represented by the above [Formula A] is used as a photoresist composition, a structure in which sulfide is bonded to a terminal benzene ring in a structure having a plurality of benzene rings such as fluorene, dibenzofuran or dibenzothiophene Due to this, it is possible to provide an oxime ester compound as a photoinitiator having excellent sensitivity in a long wavelength UV light source, excellent solubility, and can minimize outgas generation.
한편, 본 발명에서의 상기 “치환 또는 비치환된 C1-C20의 알킬기”, “치환 또는 비치환된 C6-C20의 아릴기” 등에서의 상기 알킬기 또는 아릴기의 범위를 고려하여 보면, 상기 C1-C20의 알킬기 및 C6-C20의 아릴기의 탄소수의 범위는 각각 상기 치환기가 치환된 부분을 고려하지 않고 비치환된 것으로 보았을 때의 알킬 부분 또는 아릴 부분을 구성하는 전체 탄소수를 의미하는 것이다. 예컨대, 파라위치에 부틸기가 치환된 페닐기는 C4의 부틸기로 치환된 C6의 아릴기에 해당하는 것으로 보아야 한다. On the other hand, when considering the range of the alkyl group or the aryl group in the "substituted or unsubstituted C 1 -C 20 alkyl group", "substituted or unsubstituted C 6 -C 20 aryl group", etc. The range of carbon number of the C 1 -C 20 alkyl group and C 6 -C 20 aryl group is the total constituting the alkyl portion or the aryl portion when viewed as unsubstituted without considering the substituted portion. It means carbon number. For example, a phenyl group substituted with a butyl group in the para position should be considered to correspond to a C 6 aryl group substituted with a butyl group of C 4 .
본 발명의 화합물에서 사용되는 치환기인 아릴기는 하나의 수소 제거에 의해서 방향족 탄화수소로부터 유도된 유기 라디칼로, 5 내지 7원, 바람직하게는 5 또는 6원을 포함하는 단일 또는 융합고리계를 포함하며, 또한 상기 아릴기에 치환기가 있는 경우 이웃하는 치환기와 서로 융합 (fused)되어 고리를 추가로 형성할 수 있다.The aryl group, which is a substituent used in the compound of the present invention, is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and includes a single or fused ring system containing 5 to 7 members, preferably 5 or 6 members, In addition, when there is a substituent on the aryl group may be fused with a neighboring substituent (fused) with each other to further form a ring.
상기 아릴기의 구체적인 예로는 페닐기, o-비페닐기, m-비페닐기, p-비페닐기, o-터페닐기, m-터페닐기, p-터페닐기, 나프틸기, 안트릴기, 페난트릴기, 피레닐기, 인데닐, 플루오레닐기, 테트라히드로나프틸기, 페릴렌일, 크라이세닐, 나프타세닐,플루오란텐일등과 같은 방향족 그룹을 들 수 있고, 상기 아릴기(비방향족고리 탄소 포함) 중 하나 이상의 수소 원자는 중수소 원자, 할로겐 원자, 히드록시기, 니트로기, 시아노기, 실릴기, 아미노기 (-NH2, -NH(R), -N(R')(R''), R'과 R"은 서로 독립적으로 C1-C10의 알킬기이며, 이 경우 "알킬아미노기"라 함), 아미디노기, 히드라진기, 히드라존기, 카르복실기, 술폰산기, 인산기, C1-C24의 알킬기, C1-C24의 할로겐화된 알킬기, C2-C24의 알케닐기, C2-C24의 알키닐기, C1-C24의 헤테로알킬기, C6-C24의 아릴기, C7-C24의 아릴알킬기, C2-C24의 헤테로아릴기 또는 C2-C24의 헤테로아릴알킬기로 치환될 수 있다.Specific examples of the aryl group include a phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, naphthyl group, anthryl group, phenanthryl group, Aromatic groups such as pyrenyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl and the like, and the like. Hydrogen atom is deuterium atom, halogen atom, hydroxy group, nitro group, cyano group, silyl group, amino group (-NH2, -NH (R), -N (R ') (R''),R' and R "are Independently an alkyl group of C 1 -C 10 , in this case an “alkylamino group”), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group of C 1 -C 24 , C 1 -C 24 halogenated alkyl group, C 2 -C 24 alkenyl group, C 2 -C 24 alkynyl group, C 1 -C 24 heteroalkyl group, C 6 -C 24 aryl group, C 7 -C 24 May be substituted with an arylalkyl group, a C 2 -C 24 heteroaryl group, or a C 2 -C 24 heteroarylalkyl group.
본 발명의 화합물에서 사용되는 치환기인 헤테로아릴기는 N, O, P, Si, S, Ge, Se, Te 중에서 선택된 1, 2 또는 3개의 헤테로 원자를 포함하고, 나머지 고리 원자가 탄소인 C2-C24의 고리 방향족 시스템을 의미하며, 상기 고리들은 융합(fused)되어 고리를 형성할 수 있다. 그리고 상기 헤테로아릴기 중 하나 이상의 수소 원자는 상기 아릴기의 경우와 마찬가지의 치환기로 치환가능하다.The heteroaryl group, which is a substituent used in the compound of the present invention, contains 1, 2 or 3 heteroatoms selected from N, O, P, Si, S, Ge, Se, Te, and C 2 -C wherein the remaining ring atoms are carbon. A ring aromatic system of 24 , wherein the rings can be fused to form a ring. At least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as in the case of the aryl group.
또한 본 발명에서 사용되는 치환기인 알킬기의 구체적인 예로는 메틸, 에틸, 프로필, 이소프로필, 이소부틸, sec-부틸, tert-부틸, 펜틸, iso-아밀, 헥실 등을 들 수 있고, 상기 알킬기 중 하나 이상의 수소 원자는 원자는 상기 아릴기의 경우와 마찬가지의 치환기로 치환가능하다.In addition, specific examples of the alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like, and one of the alkyl groups The above hydrogen atoms may be substituted with the same substituents as in the case of the aryl group.
본 발명의 화합물에서 사용되는 치환기인 알콕시기의 구체적인 예로는 메톡시, 에톡시, 프로폭시, 이소부틸옥시, sec-부틸옥시, 펜틸옥시, iso-아밀옥시, 헥실옥시 등을 들 수 있고, 상기 알콕시기 중 하나 이상의 수소 원자는 상기 아릴기의 경우와 마찬가지의 치환기로 치환가능하다.Specific examples of the alkoxy group which is a substituent used in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like. At least one hydrogen atom of the alkoxy group may be substituted with the same substituent as in the case of the aryl group.
본 발명의 화합물에서 사용되는 치환기인 히드록시알킬기의 구체적인 예로는 구체적으로는 히드록시메틸, 히드록시에틸, 히드록시n-프로필, 히드록시n-부틸, 히드록시t-부틸, 히드록시n-펜틸, 히드록시i-펜틸, 히드록시i-헥실, 히드록시n-데실 등을 들 수 있고, 상기 히드록시알킬리 중 하나 이상의 수소 원자는 상기 아릴기의 경우와 마찬가지의 치환기로 치환가능하다.Specific examples of the hydroxyalkyl group which is a substituent used in the compound of the present invention are specifically hydroxymethyl, hydroxyethyl, hydroxy n -propyl, hydroxy n -butyl, hydroxy t -butyl, hydroxy n -pentyl , Hydroxy i -pentyl, hydroxy i -hexyl, hydroxy n -decyl, and the like, and at least one hydrogen atom of the hydroxyalkylli may be substituted with the same substituent as in the aryl group.
본 발명의 화합물에서 사용되는 치환기인 아릴알킬기의 구체적인 예로는 메틸페닐, 디메틸페닐, n-프로필페닐, t-부틸페닐, 메틸나프틸 등을 들 수 있고, 상기 아릴알킬기 중 하나 이상의 수소 원자는 상기 아릴기의 경우와 마찬가지의 치환기로 치환가능하다.Specific examples of the arylalkyl group which is a substituent used in the compound of the present invention include methylphenyl, dimethylphenyl, n -propylphenyl, t -butylphenyl, methylnaphthyl, and the like, and at least one hydrogen atom of the arylalkyl group is the aryl. Substituent with the same substituent as in the case of group is possible.
본 발명의 화합물에서 사용되는 치환기인 시클로알킬기의 구체적인 예로는 시클로부틸, 시클로펜틸, 시클로헥실, 메틸시클로펜틸, 메틸시클로헥실, 에틸시클로펜틸, 에틸시클로헥실 등을 들 수 있고, 상기 시클로알킬기 중 하나 이상의 수소 원자는 상기 아릴기의 경우와 마찬가지의 치환기로 치환가능 하다.Specific examples of the cycloalkyl group which is a substituent used in the compound of the present invention include cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, methylcyclohexyl, ethylcyclopentyl, ethylcyclohexyl, and the like. The above hydrogen atoms can be substituted with the same substituents as in the case of the aryl group.
본 발명의 화합물에서 사용되는 치환기인 실릴기의 구체적인 예로는 트리메틸실릴, 트리에틸실릴, 트리페닐실릴, 트리메톡시실릴, 디메톡시페닐실릴, 디페닐메틸실릴, 디페닐비닐실릴, 메틸사이클로뷰틸실릴, 디메틸퓨릴실릴 등을 들 수 있고, 상기 실릴기 중 하나 이상의 수소 원자는 상기 아릴기의 경우와 마찬가지의 치환기로 치환가능 하다.Specific examples of the silyl group which is a substituent used in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl And dimethylfuryl silyl and the like, and at least one hydrogen atom in the silyl group may be substituted with the same substituent as in the case of the aryl group.
상기 [화학식 A]에서 '상기 치환기 R3 및 R4는 서로 결합하여 지환족 또는 방향족의 단일환 또는 다환고리를 형성할 수 있으며'의 의미는 일예로서, 상기 치환기 R3 및 R4가 알킬기인 경우 [구조식A-2]에서와 같이 지환족의 단일환을 형성할 수 있으며, 이때 s는 0~5 중에서 하나의 정수인 것이 바람직하며, 상기 s를 포함하는 탄소고리는 추가의 지방족 또는 방향족 고리를 포함할 수 있다.In [Formula A], 'the substituents R 3 and R 4 may be bonded to each other to form a monocyclic or polycyclic ring of alicyclic or aromatic', and as an example, the substituents R 3 and R 4 are alkyl groups. In this case, as shown in [Formula A-2], an alicyclic monocyclic ring may be formed, wherein s is preferably an integer of 0 to 5, and the carbon ring including s may further form an aliphatic or aromatic ring. It may include.
[구조식A-2] [Formula A-2]
Figure PCTKR2019005284-appb-I000003
Figure PCTKR2019005284-appb-I000003
또한, 상기 치환기 R3 및 R4가 아릴기의 경우 [구조식A-3]과 같이 상기 치환기 R3 및 R4가 서로 결합되어 지환족 또는 방향족의 고리를 형성할 수 있으며, 이때 p는 0~2 중에서 하나의 정수인 것이 바람직하고, 상기 p를 포함하는 탄소고리는 추가의 지방족 또는 방향족 고리를 포함할 수 있다.In addition, when the substituents R 3 and R 4 is an aryl group, as shown in [Formula A-3], the substituents R 3 and R 4 may be bonded to each other to form an alicyclic or aromatic ring, wherein p is 0 to It is preferably an integer of 2, and the carbon ring containing p may include additional aliphatic or aromatic rings.
[구조식A-3] [Formula A-3]
Figure PCTKR2019005284-appb-I000004
Figure PCTKR2019005284-appb-I000004
또한, 상기 [화학식 A]로 표시되는 화합물의 바람직한 예로서, 이는 하기 [화학식 A-1]로 표시되는 화합물일 수 있다.In addition, as a preferable example of the compound represented by [Formula A], it may be a compound represented by the following [Formula A-1].
[화학식A-1][Formula A-1]
Figure PCTKR2019005284-appb-I000005
Figure PCTKR2019005284-appb-I000005
상기 치환기 R1 내지 R4, R'는 앞서 정의한 바와 같고, 상기 m은 0 또는 1이다.The substituents R 1 to R 4 , R ′ are as defined above, and m is 0 or 1.
즉, 상기 [화학식 A-1]로 표시되는 옥심에스테르 화합물은 R3 및 R4를 포함하는 플루오렌 그룹의 한 쪽 벤젠고리에 옥심에스테르기를 포함하는 관능기가 결합하고, 이 때 상기 관능기는 치환기 R1 및 R2를 포함하는 옥심에스테르기를 가지며, 또한 플루오렌 그룹의 벤젠고리에 선택적으로 카르보닐기를 포함하는 구조를 가지며, 또한 상기 플루오렌 그룹내 옥심에스테르기가 결합하지 않은 다른 쪽 벤젠고리내 탄소원자에 1 개의 R'-S 치환기가 결합된 구조를 가지는 것을 기술적 특징으로 한다. That is, the oxime ester compound represented by [Formula A-1] has a functional group including an oxime ester group bonded to one benzene ring of a fluorene group including R 3 and R 4, wherein the functional group is substituted with a substituent R 1 and One of the carbon atoms in the other benzene ring having an oxime ester group containing R 2 and optionally having a carbonyl group in the benzene ring of the fluorene group, and not having an oxime ester group in the fluorene group bonded thereto; It is a technical feature to have a structure in which the R'-S substituent is bonded.
또한, 상기 [화학식 A-1]로 표시되는 화합물의 다른 바람직한 예로서, 이는 하기 [화학식 A-4]로 표시되는 화합물일 수 있다.In addition, as another preferred example of the compound represented by [Formula A-1], it may be a compound represented by the following [Formula A-4].
[화학식A-4][Formula A-4]
Figure PCTKR2019005284-appb-I000006
Figure PCTKR2019005284-appb-I000006
상기 치환기 R1 내지 R4 , R’는 상기 [화학식A-1]에서 정의한 바와 같다.The substituents R 1 to R 4 , R ′ are as defined in the [Formula A-1].
또한, 상기 [화학식 A]로 표시되는 화합물의 다른 바람직한 예로서, 이는 하기 [화학식 A-2]로 표시되는 화합물일 수 있다.In addition, as another preferred example of the compound represented by [Formula A], it may be a compound represented by the following [Formula A-2].
[화학식A-2][Formula A-2]
Figure PCTKR2019005284-appb-I000007
Figure PCTKR2019005284-appb-I000007
상기 치환기 R1, R2 및 R'는 앞서 정의한 바와 같고, 상기 m은 0 또는 1이다.The substituents R 1 , R 2 and R ′ are as defined above and m is 0 or 1.
즉, 상기 [화학식 A-2]로 표시되는 옥심에스테르 화합물은 디벤조티오펜 그룹의 한 쪽 벤젠고리에 옥심에스테르기를 포함하는 관능기가 결합하고, 이 때 상기 관능기는 치환기 R1 및 R2를 포함하는 옥심에스테르기를 가지며, 또한 디벤조티오펜 그룹의 벤젠고리에 선택적으로 카르보닐기를 포함하는 구조를 가지며, 또한 상기 디벤조티오펜 그룹내 옥심에스테르기가 결합하지 않은 다른 쪽 벤젠고리내 탄소원자에 1 개의 R'-S 치환기가 결합된 구조를 가지는 것을 기술적 특징으로 한다. That is, the oxime ester compound represented by [Formula A-2] has a functional group including an oxime ester group bonded to one benzene ring of the dibenzothiophene group, and the functional group includes substituents R 1 and R 2 . It has an oxime ester group, and also has a structure containing a carbonyl group selectively in the benzene ring of the dibenzothiophene group, and one carbon atom in the other benzene ring to which the oxime ester group in the dibenzothiophene group is not bonded. It is a technical feature to have a structure in which the R'-S substituent is bonded.
또한, 상기 [화학식 A-2]로 표시되는 화합물의 다른 바람직한 예로서, 이는 하기 [화학식 A-5]로 표시되는 화합물일 수 있다.In addition, as another preferred example of the compound represented by [Formula A-2], it may be a compound represented by the following [Formula A-5].
[화학식A-5][Formula A-5]
Figure PCTKR2019005284-appb-I000008
Figure PCTKR2019005284-appb-I000008
상기 치환기 R1, R2 및 R’는 상기 [화학식A-2]에서 정의한 바와 같다.The substituents R 1 , R 2 and R ′ are as defined in the [Formula A-2].
또한, 상기 [화학식 A]로 표시되는 화합물의 다른 바람직한 예로서, 이는 하기 [화학식 A-3]로 표시되는 화합물일 수 있다.In addition, as another preferred example of the compound represented by [Formula A], it may be a compound represented by the following [Formula A-3].
[화학식A-3][Formula A-3]
Figure PCTKR2019005284-appb-I000009
Figure PCTKR2019005284-appb-I000009
상기 치환기 R1, R2 및 R'는 앞서 정의한 바와 같고, 상기 m은 0 또는 1이다.The substituents R 1 , R 2 and R ′ are as defined above and m is 0 or 1.
상기 [화학식 A-3]로 표시되는 옥심에스테르 화합물은 디벤조퓨란 그룹의 한 쪽 벤젠고리에 옥심에스테르기를 포함하는 관능기가 결합하고, 이 때 상기 관능기는 치환기 R1 및 R2를 포함하는 옥심에스테르기를 가지며, 또한 디벤조퓨란 그룹의 벤젠고리에 선택적으로 카르보닐기를 포함하는 구조를 가지며, 또한 상기 디벤조퓨란 그룹내 옥심에스테르기가 결합하지 않은 다른 쪽 벤젠고리내 탄소원자에 1 개의 R'-S 치환기가 결합된 구조를 가지는 것을 기술적 특징으로 한다. The oxime ester compound represented by the above [Formula A-3] has a functional group including an oxime ester group bonded to one benzene ring of a dibenzofuran group, wherein the functional group includes an oxime ester containing substituents R 1 and R 2 A group having a group and optionally comprising a carbonyl group in the benzene ring of the dibenzofuran group, and also having one R'-S substituent at a carbon atom in the other benzene ring to which the oxime ester group in the dibenzofuran group is not bonded. It is characterized by having a combined structure.
또한, 상기 [화학식 A-3]로 표시되는 화합물의 다른 바람직한 예로서, 이는 하기 [화학식 A-6]로 표시되는 화합물일 수 있다.In addition, as another preferred example of the compound represented by [Formula A-3], it may be a compound represented by the following [Formula A-6].
[화학식A-6][Formula A-6]
Figure PCTKR2019005284-appb-I000010
Figure PCTKR2019005284-appb-I000010
상기 치환기 R1, R2 및 R’는 상기 [화학식A-3]에서 정의한 바와 같다.The substituents R 1 , R 2 and R ′ are as defined in the [Formula A-3].
본 발명에 있어서 상기 [화학식 A]에서 sulfide 치환기에 해당하는, R'의 보다 바람직한 예로서, 이는 치환 또는 비치환된 C1-C30의 알킬기, 치환 또는 비치환된 C3-C20의 시클로알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환된 C7-C24의 아릴알킬기 중에서 선택되는 치환기일 수 있다.In the present invention, a more preferred example of R ', which corresponds to the sulfide substituent in [Formula A], which is a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 3 -C 20 cyclo It may be a substituent selected from an alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 7 -C 24 arylalkyl group.
한편, 상기 [화학식 A] 에서의 sulfide 치환기에 해당하는, R'의 보다 바람직한 예로서, 이는 (R8)p-Ar- 로 표시되는 치환기일 수 있다.On the other hand, a more preferred example of R ', which corresponds to the sulfide substituent in [Formula A], it may be a substituent represented by (R 8 ) p -Ar-.
이때 상기 치환기 R8은 치환 또는 비치환된 C1-C24의 알킬기, 치환 또는 비치환된 C3-C20의 시클로알킬기, 치환 또는 비치환된 C6-C24의 아릴기, 치환 또는 비치환된 C7-C24의 아릴알킬기 치환 또는 비치환된 C1-C24의 할로겐화된 알킬기, 치환 또는 비치환된 C1-C24의 알콕시기, 치환 또는 비치환된 C1-C24의 알킬실릴기, 치환 또는 비치환된 C6-C24의 아릴실릴기, 치환 또는 비치환된 C1-C20의 알킬티오닐기, 치환 또는 비치환된 C6-C20의 아릴티오닐기, 치환 또는 비치환된 C3-C20의 시클로알킬티오닐기, 시아노기, 니트로기, 할로겐기 중에서 선택되는 어느 하나이며, 상기 Ar은 치환 또는 비치환된 C6-C24의 방향족고리이고, 상기 p는 0 내지 3 중에서 하나의 정수이고, p가 2 이상인 경우에 각각의 R8은 서로 동일하거나 상이할 수 있다.Wherein the substituent R 8 is a substituted or unsubstituted C 1 -C 24 alkyl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl group, a substituted or unsubstituted C 6 -C 24 aryl group, substituted or unsubstituted hwandoen of C 7 -C 24 arylalkyl group of substituted or unsubstituted C 1 -C 24 halogenated alkyl group, a substituted or unsubstituted C 1 -C 24 alkoxy group, a substituted or unsubstituted C 1 -C 24 of Alkylsilyl group, substituted or unsubstituted C 6 -C 24 arylsilyl group, substituted or unsubstituted C 1 -C 20 alkylthioyl group, substituted or unsubstituted C 6 -C 20 arylthioyl group , A substituted or unsubstituted C 3 -C 20 cycloalkylthionyl group, cyano group, nitro group, a halogen group is selected from any one of, Ar is a substituted or unsubstituted C 6 -C 24 aromatic ring P is an integer of 0 to 3, and when p is 2 or more, each R 8 may be the same or different from each other.
즉, 상기 (R8)p-Ar- 로 표시되는 치환기 R'는 -Ar-으로 표시되는 치환 또는 비치환된 C6-C24의 방향족고리를 포함하되, 상기 방향족고리에 치환기 R8이 0 내지 3개 치환될 수 있다. That is, the substituent R 'represented by (R 8 ) p -Ar- includes a substituted or unsubstituted C 6 -C 24 aromatic ring represented by -Ar-, and the substituent R 8 is 0 in the aromatic ring. To 3 may be substituted.
예컨대, 상기 치환기 R8이 전혀 치환되지 않은 경우에는 상기 Ar 은 치환 또는 비치환된 C6-C24의 아릴기에 해당하며, 1개 치환된 경우에는 치환 또는 비치환된 C6-C24의 아릴렌기에 해당하고, 2개 치환된 경우에는 치환 또는 비치환된 C6-C24의 방향족고리내 3개의 라디칼이 황원자 또는 R8에 연결된 형태의 방향족 고리에 해당한다.For example, when the substituent R 8 is not substituted at all, Ar corresponds to a substituted or unsubstituted C 6 -C 24 aryl group, and when substituted one, substituted or unsubstituted C 6 -C 24 aryl. And two substituents, if substituted, represent an aromatic ring in which three radicals in a substituted or unsubstituted C 6 -C 24 aromatic ring are linked to a sulfur atom or to R 8 .
따라서, 상기 (R8)p-Ar- 로 표시되는 치환기 R'를 가지는 옥심에스테르 화합물은 X의 종류에 따라 플루오렌 그룹, 디벤조퓨란 그릅 또는 디벤조티오펜 그룹의 한 쪽 벤젠고리에 방향족 고리가 직접 결합되어, 복수의 고리를 가지는 판상형 구조가 확장되어 용해도가 우수한 특징을 제공할 수 있고, 이러한 구조적 특징으로 인해 추가적으로 용해도를 부여하기 위한 말단기 구조를 최소화 할 수 있어 아웃가스 발생을 최소화 할 수 있다.Accordingly, the oxime ester compound having a substituent R 'represented by (R 8 ) p -Ar- may have an aromatic ring on one benzene ring of a fluorene group, dibenzofuran group or dibenzothiophene group depending on the type of X. Is directly bonded, the plate-like structure having a plurality of rings can be extended to provide excellent solubility characteristics, and due to this structural characteristics can further minimize the end group structure for imparting solubility to minimize outgas generation Can be.
또한, 상기 [화학식 A]에서 R'는 하기 [구조식 A-1]로 표시되는 치환기일 수 있다.In addition, R 'in [Formula A] may be a substituent represented by the following [Formula A-1].
[구조식 A-1][Formula A-1]
Figure PCTKR2019005284-appb-I000011
Figure PCTKR2019005284-appb-I000011
상기 치환기 R11 내지 R15는 각각 동일하거나 상이하며, 서로 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 치환 또는 비치환된 C1-C30의 알킬기, 치환 또는 비치환된 C1-C24의 할로겐화된 알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환되고 이종 원자로 N, O, P, Si, 및 S 에서 선택되는 1 내지 3의 원자를 갖는 C3-C24의 헤테로아릴기, 치환 또는 비치환된 C1-C20의 알콕시기, 치환 또는 비치환된 C7-C20의 아릴알킬기, 치환 또는 비치환된 C3-C20의 시클로알킬기, 치환 또는 비치환된 C1-C24의 알킬실릴기, 치환 또는 비치환된 C6-C24의 아릴실릴기, 치환 또는 비치환된 C1-C20의 알킬티오닐기, 치환 또는 비치환된 C6-C20의 아릴티오닐기, 치환 또는 비치환된 C3-C20의 시클로알킬티오닐기 중에서 선택되는 어느 하나일 수 있다.The substituents R 11 to R 15 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 1 -C 24 halogenated alkyl group, substituted or unsubstituted C 6 -C 30 aryl group, substituted or unsubstituted C having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms 3 -C 24 heteroaryl group, substituted or unsubstituted C 1 -C 20 alkoxy group, substituted or unsubstituted C 7 -C 20 arylalkyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl group , Substituted or unsubstituted C 1 -C 24 alkylsilyl group, substituted or unsubstituted C 6 -C 24 arylsilyl group, substituted or unsubstituted C 1 -C 20 alkylthioyl group, substituted or unsubstituted hwandoen C 6 -C 20 is selected from any one of the aryl thionyl group, a substituted or unsubstituted cycloalkyl alkyl group of the unsubstituted C 3 -C 20 group O'Neill Can.
한편, 본 발명에서의 상기 [화학식 A]로 표시되는 옥심에스테르 화합물의 구체적인 화합물로서, 하기 표 1에 기재된 화합물 1 내지 330 중의 어느 하나로 표시되는 화합물이 될 수 있으나, 이에 제한되지 않는다. On the other hand, as a specific compound of the oxime ester compound represented by the [Formula A] in the present invention, may be a compound represented by any one of the compounds 1 to 330 shown in Table 1 below, but is not limited thereto.
[표 1]TABLE 1
Figure PCTKR2019005284-appb-I000012
Figure PCTKR2019005284-appb-I000012
Figure PCTKR2019005284-appb-I000013
Figure PCTKR2019005284-appb-I000013
Figure PCTKR2019005284-appb-I000014
Figure PCTKR2019005284-appb-I000014
Figure PCTKR2019005284-appb-I000015
Figure PCTKR2019005284-appb-I000015
Figure PCTKR2019005284-appb-I000016
Figure PCTKR2019005284-appb-I000016
Figure PCTKR2019005284-appb-I000017
Figure PCTKR2019005284-appb-I000017
Figure PCTKR2019005284-appb-I000018
Figure PCTKR2019005284-appb-I000018
Figure PCTKR2019005284-appb-I000019
Figure PCTKR2019005284-appb-I000019
Figure PCTKR2019005284-appb-I000020
Figure PCTKR2019005284-appb-I000020
Figure PCTKR2019005284-appb-I000021
Figure PCTKR2019005284-appb-I000021
Figure PCTKR2019005284-appb-I000022
Figure PCTKR2019005284-appb-I000022
Figure PCTKR2019005284-appb-I000023
Figure PCTKR2019005284-appb-I000023
Figure PCTKR2019005284-appb-I000024
Figure PCTKR2019005284-appb-I000024
Figure PCTKR2019005284-appb-I000025
Figure PCTKR2019005284-appb-I000025
Figure PCTKR2019005284-appb-I000026
Figure PCTKR2019005284-appb-I000026
Figure PCTKR2019005284-appb-I000027
Figure PCTKR2019005284-appb-I000027
Figure PCTKR2019005284-appb-I000028
Figure PCTKR2019005284-appb-I000028
Figure PCTKR2019005284-appb-I000029
Figure PCTKR2019005284-appb-I000029
Figure PCTKR2019005284-appb-I000030
Figure PCTKR2019005284-appb-I000030
Figure PCTKR2019005284-appb-I000031
Figure PCTKR2019005284-appb-I000031
Figure PCTKR2019005284-appb-I000032
Figure PCTKR2019005284-appb-I000032
Figure PCTKR2019005284-appb-I000033
Figure PCTKR2019005284-appb-I000033
한편, 본 발명은 상기 [화학식 A]로 표시되는 옥심에스테르 화합물을 포함하는 포토레지스트 조성물을 제공한다.On the other hand, the present invention provides a photoresist composition comprising an oxime ester compound represented by the above [Formula A].
한편, 상기 옥심에스테르 화합물은 포토레시스트 조성물내에 포함되어 UV 등과 같은 광에 의해 라디칼을 제공하는 포토레지스트용 광개시제 재료로서 사용될 수 있고 이러한 포토레지스트 조성물은 컬럼스페이서, 유연절연막, 오버코트, 블랙매트릭스, 컬러레지스트, 봉지재 등에 이용이 가능하다Meanwhile, the oxime ester compound may be used as a photoinitiator material for photoresist that is included in a photoresist composition to provide radicals by light such as UV and the like, and the photoresist composition may be a column spacer, a flexible insulating film, an overcoat, a black matrix, or a color. Usable for resists, encapsulants
이때, 상기 옥심에스테르 화합물을 포함하는 포토레지스트 조성물은 디스플레이용이나 전자재료용 포토레지스트 조성물로 사용하는 경우에, 용매나 아크릴 모노머와의 상용성이 우수하고 UV 광원에 뛰어난 감도를 가지고, UV를 효율적으로 흡수하여 고감도 및 고투명 특성이 우수하여 사용시 수율 및 성능을 향상시킬 수 있다.At this time, the photoresist composition containing the oxime ester compound has excellent compatibility with a solvent or an acrylic monomer when used as a photoresist composition for a display or an electronic material, has excellent sensitivity to a UV light source, and efficiently uses UV. It is absorbed by, so it has high sensitivity and high transparency, so it can improve yield and performance when using.
한편, 상기 포토레지스트 조성물은 아크릴 중합체와 에틸렌성 불포화결합을 갖는 중합성 화합물 또는 용매 등을 첨가하여 수계 현상이 가능하며, 옥심에스테르 화합물에 광중합성 화합물, 아크릴 중합체 또는 용매를 추가적으로 포함할 수 있으며, 이에 제한되지 않고 기타 공지의 포토레지스트 조성물에 사용되는 물질을 추가적으로 포함할 수 있다.On the other hand, the photoresist composition may be a water-based development by adding a polymerizable compound or solvent having an ethylenically unsaturated bond with the acrylic polymer, and may further include a photopolymerizable compound, an acrylic polymer or a solvent in the oxime ester compound, The present invention is not limited thereto, and may further include materials used in other known photoresist compositions.
본 발명의 상기 포토레지스트 조성물의 일 실시예로서, 이는 포토레지스트 조성물 100 중량부에 대해서, 상기 옥심에스테르 화합물 0.1 내지 20 중량부, 광중합성 화합물 80 내지 99.9 중량부를 포함할 수 있다.As an embodiment of the photoresist composition of the present invention, it may include 0.1 to 20 parts by weight of the oxime ester compound and 80 to 99.9 parts by weight of the photopolymerizable compound with respect to 100 parts by weight of the photoresist composition.
즉, 상기 광중합성 화합물의 함량은 옥심에스테르 화합물과 함께 2성분만으로 사용되는 경우에, 상기 포토레지스트 조성물 100 중량부를 기준으로 80 내지 99.9 중량부를 포함할 수 있다. 즉, 상기 광중합성 화합물의 함량은 옥심에스테르 화합물과 함께 2성분만으로 사용되는 경우에, 상기 포토레지스트 조성물 100 중량부를 기준으로 80 내지 99.9 중량부를 포함할 수 있다.That is, the content of the photopolymerizable compound may include 80 to 99.9 parts by weight based on 100 parts by weight of the photoresist composition when used in only two components together with the oxime ester compound. That is, the content of the photopolymerizable compound may include 80 to 99.9 parts by weight based on 100 parts by weight of the photoresist composition when used in only two components together with the oxime ester compound.
또한, 상기 포토레지스트 조성물은 아크릴 중합체 또는 용매를 추가로 포함할 수 있으며, 이 때 포토레지스트 조성물 100 중량부에 대해서, 상기 옥심에스테르 화합물 0.1 내지 20 중량부, 광중합성 화합물 1 내지 60 중량부, 아크릴 중합체 0 내지 40 중량부 및 용매 10 내지 90 중량부를 포함할 수 있다.In addition, the photoresist composition may further comprise an acrylic polymer or a solvent, at this time, based on 100 parts by weight of the photoresist composition, 0.1 to 20 parts by weight of the oxime ester compound, 1 to 60 parts by weight of the photopolymerizable compound, acrylic 0 to 40 parts by weight of the polymer and 10 to 90 parts by weight of the solvent.
또한, 상기 포토레지스트 조성물은 적색, 녹색, 청색 또는 블랙 안료를 추가로 포함할 수 있으며, 이 때 포토레지스트 조성물 100 중량부에 대해서, 상기 옥심에스테르 화합물 0.1 내지 20 중량부, 광중합성 화합물 1 내지 60 중량부, 아크릴 중합체 0 내지 40 중량부, 적색, 녹색, 청색 또는 블랙 안료 1 내지 50 중량부 및 용매 10 내지 90 중량부를 포함할 수 있다.In addition, the photoresist composition may further include a red, green, blue or black pigment, in this case with respect to 100 parts by weight of the photoresist composition, 0.1 to 20 parts by weight of the oxime ester compound, 1 to 60 of the photopolymerizable compound It may include parts by weight, 0 to 40 parts by weight of acrylic polymer, 1 to 50 parts by weight of red, green, blue or black pigment and 10 to 90 parts by weight of solvent.
상기 광중합성 화합물은 한개 혹은 두개 이상의 아크릴기, 메타아크릴기 또는 비닐기를 포함한 화합물로서, 본 발명에 따른 광개시제가 UV에 의하여 라디칼이 생성되고 생성된 라디칼에 의해 가교가 되는 화합물을 의미한다. 상기 광중합성 화합물의 예로는 헥실(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 테트라데실(메타)아크릴레이트 및 헥사데실(메타)아크릴레이트 등의 알킬아크릴레이트 또는; 알킬메타아크릴레이트, 에틸렌글리콜디(메타)아크릴레이트, 헥산디올디(메타)아크릴레이트, 데칸디올디(메타)아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 타에리스리톨펜타(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 리메틸올프로판디(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 타에리스리톨트리(메타)아크릴레이트, 아크릴산, 메타아크릴산, 글리시딜아크릴레이트, 스틸렌, 디비닐벤젠 등으로 이루어진 군으로부터 선택된 어느 하나 이상일 수 있다.The photopolymerizable compound is a compound including one or two or more acrylic groups, methacryl groups or vinyl groups. The photoinitiator according to the present invention refers to a compound in which radicals are generated by UV and crosslinked by the generated radicals. Examples of the photopolymerizable compound include alkyl acrylates such as hexyl (meth) acrylate, cyclohexyl (meth) acrylate, tetradecyl (meth) acrylate and hexadecyl (meth) acrylate; Alkyl methacrylate, ethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, decanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Ta-erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dimethylolpropanedi (meth) acrylate, trimethylolpropane tri (meth) acrylate, taerythritol tri (meth) acrylate, acrylic acid It may be at least one selected from the group consisting of methacrylic acid, glycidyl acrylate, styrene, divinylbenzene and the like.
한편, 본 발명에 따른 상기 포토레지스트 조성물은 패턴 특성 조절과 내열성 등의 박막물성을 부여하기 위하여 아크릴 중합체 또는 측쇄에 아크릴 불포화 결합을 갖는 아크릴 중합체 등을 선택적으로 사용할 수 있다. On the other hand, the photoresist composition according to the present invention may selectively use an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in the side chain in order to provide thin film properties such as pattern characteristics control and heat resistance.
상기 아크릴 중합체로는 하기에 기재된 단량체들을 포함하는 단량체들의 공중합체로서 단량체의 예로는, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트, 헥실(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 도데실(메타)아크릴레이트 및 헥사데실(메타)아크릴레이트,이소보닐(메타)아크릴레이트, 다만틸(메타)아크릴레이트, 디시클로펜타닐(메타)아크릴레이트, 벤질(메타)아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 2-에톡시에틸(메타)아크릴레이트, 아크릴산, 메타아크릴산, 스틸렌, 아세톡시스틸렌, 글리시딜아크릴레이트, 글리시딜 메타아크릴레이트, 이타코닉산, 말레익산무수물, 말레익산모노알킬 에스터, 모노알킬 퓨말레이트, 3,4-에폭시부틸(메타)아크릴레이트,2,3-에폭시시클로헥실(메타)아크릴레이트,3,4-에폭시시클로헥실메틸(메타)아크릴레이트, 3-에틸옥세탄-3-메틸(메타)아크릴레이트, 말레이미드, N-메틸말레이미드, N-부틸말레이미드, N-페닐말레이미드, (메타)아크릴아미드 등을 들 수 있으며, 이들을 각각 단독으로 또는 2종 이상을 중합하여 사용할 수 있으며, 여기서, 상기 아크릴중합체의 함량은 용매를 포함하는 경우에 상기 포토레지스트 조성물 100 중량부를 기준으로 0 내지 40 중량부를 포함하는 것이 바람직하다. 상기 아크릴 중합체의 함량을 40 중량부 이상 혼합시에는 용액의 점도가 너무 높아 코팅이 어려운 문제가 있다.The acrylic polymer is a copolymer of monomers including the monomers described below. Examples of the monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate and hexadecyl (meth) acrylate, isobonyl (meth ) Acrylate, dandanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, Acrylic acid, methacrylic acid, styrene, acetoxy styrene, glycidyl acrylate, glycidyl methacrylate, itaconic acid, maleic anhydride, maleic acid monoalkyl ester, monoalkyl fumale , 3,4-epoxybutyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-ethyloxetane-3-methyl ( Meta) acrylate, maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, (meth) acrylamide, and the like, and these may be used alone or in combination of two or more thereof. In this case, the content of the acrylic polymer preferably includes 0 to 40 parts by weight based on 100 parts by weight of the photoresist composition when it contains a solvent. When the content of the acrylic polymer is mixed by 40 parts by weight or more, the viscosity of the solution is too high, there is a problem that the coating is difficult.
또한, 본 발명의 포토레지스트 조성물은 필요에 따라서 이미 알려진 광개시제를 추가로 첨가하여 사용하는 것도 가능하다. 추가로 첨가하여 사용 가능한 광개시제로는 케톤류, 케토아세탈류, 치오잔톤류, 포스핀옥사이드류, 안트라퀴논류, 트리클로로메틸 트리아진류, 옥심에스테르류 등을 사용할 수 있으며, 이러한 광개시제의 구체적인 예로는 페닐비페닐케톤, 치오잔톤(thioxanthone), 이소프로필치오잔톤, 디에틸치오잔톤, 벤조페논, 1-벤질-1-디메틸아미노-1-(4-모폴리노-벤조일)프로판, 1-히드록시-1-벤조일시클로헥산, 2-모폴릴-2-(4-메틸머캅토) 벤조일프로판, 에틸안트라퀴논, 4-벤조일-4-메틸디페닐설파이드, 벤조인부틸에테르, 2-히드록시-2-벤조일프로판, 2-히드록시-2-(4-이소프로필)벤조일프로판, 4-부틸벤조일트리클로로메탄, 4-페녹시벤조일디클로로메탄, 디페닐-2,4,6-트리메틸벤조일포스핀옥사이드, 벤조일포름산메틸, 1,7-비스(9-아크리디닐)헵탄, 2-메틸-4,6-비스 (트리클로로메틸)-s-트리아진, 2-페닐-4,6-비스(트리클로로메틸)-s-트리아진, 2-나프틸-4,6-비스 (트리클로로메틸)-s-트리아진, 1-[9-에틸-6-(2-메틸벤조일)-9H-카바졸-3-일]-에타논-1-(O-아세틸옥심), 1-(o-아세틸옥심)-1-[9-에틸-6-(2-메틸벤조일)-9H-카르바졸-3-일]에탄온, 2-(o-벤조일옥심)-1-[4-(페닐티오)페닐]-1,2-옥탄디온 군으로부터 선택된 어느 하나 이상을 포함할 수 있다.In addition, the photoresist composition of the present invention may be used by further adding a photoinitiator known as needed. As further photoinitiators that can be added and used, ketones, ketoacetals, thioxanthones, phosphine oxides, anthraquinones, trichloromethyl triazines, oxime esters, and the like can be used. Specific examples of such photoinitiators include phenyl Biphenyl ketone, thioxanthone, isopropyl thioxanthone, diethyl thioxanthone, benzophenone, 1-benzyl-1-dimethylamino-1- (4-morpholino-benzoyl) propane, 1-hydroxy- 1-benzoylcyclohexane, 2-morpholinyl-2- (4-methylmercapto) benzoylpropane, ethylanthraquinone, 4-benzoyl-4-methyldiphenylsulfide, benzoin butyl ether, 2-hydroxy-2- Benzoylpropane, 2-hydroxy-2- (4-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, diphenyl-2,4,6-trimethylbenzoylphosphine oxide, Methyl benzoyl formate, 1,7-bis (9-acridinyl) heptane, 2-methyl-4,6-bis (trickle Rhomethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone-1- (O-acetyloxime), 1- (o-acetyloxime) -1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2- It may include any one or more selected from the group of octanedione.
이러한 광개시제는 보다 바람직하게는, 노광 감도와 패턴 특성을 조절하기 위하여 포토레지스트 조성물 100중량부를 기준으로 0.1 내지 10중량부를 사용할 수 있다. 추가로 첨가하는 광개시제를 10 중량부 이상 사용하는 경우에는 공정 중에 발생하는 아웃가스 량이 증가하여 수율이 저하되는 문제가 있다.More preferably, the photoinitiator may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the photoresist composition in order to adjust exposure sensitivity and pattern characteristics. In the case where 10 parts by weight or more of additionally added photoinitiator is used, there is a problem that the amount of outgas generated during the process increases and the yield decreases.
또한, 상기 용매는 상기 포토레지스트 조성물을 용해하는데 선택적으로 사용될 뿐만 아니라, 우수한 코팅성과 투명한 박막을 얻기 위해 사용되며, 이러한 용매로는 유기용매를 사용하는 것이 바람직하다. In addition, the solvent is not only selectively used to dissolve the photoresist composition, but also used to obtain excellent coatability and a transparent thin film, and it is preferable to use an organic solvent as such a solvent.
상기 유기용매로서, 바람직하게는 에틸아세테이트, 부틸아세테이트, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디메틸에틸에테르, 메틸메톡시프로피오네이트, 에틸에톡시프로피오네이트(EEP), 에틸락테이트, 프로필렌글리콜메틸에테르아세테이트(PGMEA), 프로필렌글리콜메틸에테르, 프로필렌글리콜프로필에테르, 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트, 디에틸렌글리콜메틸아세테이트, 디에틸렌글리콜에틸아세테이트, 아세톤, 메틸이소부틸케톤, 시클로헥사논, 디메틸포름아미드(DMF), N,N-디메틸아세트아미드(DMAc), N-메틸-2-피롤리돈(NMP), γ-부티로락톤, 디에틸에테르, 에틸렌글리콜디메틸에테르, 다이글라임(Diglyme), 테트라하이드로퓨란(THF), 메탄올, 에탄올, 프로판올, 이소-프로판올, 메틸셀로솔브, 에틸셀로솔브, 디에틸렌글리콜메틸에테르, 디에틸렌글리콜에틸에테르, 디프로필렌글리콜메틸에테르, 톨루엔, 크실렌, 헥산, 헵탄 및 옥탄 중에서 선택된 1종 이상을 사용할 수 있으며, 여기서 상기 용매의 함량은 상기 포토레지스트 조성물 100 중량부를 기준으로 10 내지 90 중량부를 포함하는 것이 바람직하다.As the organic solvent, preferably ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate (EEP), ethyl lactate, propylene glycol Methyl ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexa Paddy, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, digle Lime (Diglyme), tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl One or more selected from tere, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane and octane may be used, wherein the solvent content is 10 to 10 parts by weight based on 100 parts by weight of the photoresist composition. It is preferable to include 90 parts by weight.
또한, 본 발명에 따른 상기 포토레지스트 조성물은 필요에 따라, 적색, 녹색, 청색 및 블랙으로 이루어진 군으로부터 선택된 적어도 하나의 색재 안료를 더 포함하여, 컬러 매트릭스용 포토레지스트 조성물 또는 블랙 매트릭스용 포토레지스트 조성물로 제조될 수 있다. In addition, the photoresist composition according to the present invention further comprises at least one colorant pigment selected from the group consisting of red, green, blue and black, if necessary, a photoresist composition for a color matrix or a photoresist composition for a black matrix It can be prepared as.
이때 첨가되는 컬러 색재 안료의 함량은 포토레지스트의 사용 조건에 적절하게 선택될 수 있으며, 예를 들면 상기 포토레지스트 조성물 100 중량부를 기준으로 1 내지 50 중량부, 더 바람직하게는 5 내지 30 중량부일 수 있다. 상기 색재 안료의 함량이 이러한 범위를 만족하는 경우, 얻어지는 컬러필터의 색순도 및 휘도 특성이 매우 우수하며, 안료의 함량을 50 중량부 이상 첨가 시에는 결정화되거나 패턴 형성시에 패턴 특성이 저하되는 문제가 있다.In this case, the content of the color colorant pigment to be added may be appropriately selected depending on the conditions of use of the photoresist, for example, 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the photoresist composition. have. When the content of the colorant pigment satisfies this range, the color purity and luminance characteristics of the color filter obtained are very excellent, and when the content of the pigment is added 50 parts by weight or more, there is a problem that the crystallization or the pattern characteristics are degraded when the pattern is formed. have.
또한, 상기 블랙 안료는 통상적으로 사용되는 카본블랙 분산체를 사용할 수 있으며, 이에 제한되지 않는다.In addition, the black pigment may be used a carbon black dispersion commonly used, but is not limited thereto.
또한, 본 발명에 따른 포토레지스트 조성물은 컬러필터, 유기발광소자(OLED), 조명장치, TFT-LCD, 금속 센서, 태양전지, 집적 회로, 유기 전계-효과 트랜지스터 (O-FET) 및 유기 박막 트랜지스터 (O-TFT)에서 선택되는 어느 하나의 장치에 사용될 수 있다. In addition, the photoresist composition according to the present invention is a color filter, an organic light emitting element (OLED), an illumination device, a TFT-LCD, a metal sensor, a solar cell, an integrated circuit, an organic field-effect transistor (O-FET) and an organic thin film transistor It can be used in any one device selected from (O-TFT).
이하, 바람직한 실시예를 들어 본 발명을 더욱 상세하게 설명한다. 그러나, 이들 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 범위가 이에 의하여 제한되지 않는다는 것은 당업계의 통상의 지식을 가진 자에게 자명할 것이다. Hereinafter, the present invention will be described in more detail with reference to preferred examples. However, these examples are intended to illustrate the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited thereto.
상기 [화학식 A] 표시되는 옥심에스테르계 화합물을 합성하는 방법에 대한 구체적인 예시를 나타내면, 하기 반응식 1과 같다. Representative examples of the method for synthesizing the oxime ester compound represented by the above [Formula A] are as shown in Scheme 1 below.
[반응식 1]  Scheme 1
Figure PCTKR2019005284-appb-I000034
Figure PCTKR2019005284-appb-I000034
합성예 1 : 화합물 1의 합성Synthesis Example 1 Synthesis of Compound 1
합성예 1-(1) : 1-(2-브로모-9,9-디메틸플루오렌-7-닐)프로판-1-온(중간체 1-a)의 합성Synthesis Example 1- (1): Synthesis of 1- (2-bromo-9,9-dimethylfluorene-7-yl) propan-1-one (intermediate 1-a)
Figure PCTKR2019005284-appb-I000035
Figure PCTKR2019005284-appb-I000035
[중간체 1-a]  [Intermediate 1-a]
2-브로모-9,9-디메틸-플루오렌10.0 g (36.6mmol)을 무수 니트로벤젠 100 ml에 용해시키고 무수 염화알루미늄 5.37 g (40.3 mmol)을 가해준 다음, 반응물을 40 ~ 50 oC로 승온하여 프로피오닐클로라이드 3.73 g (40.3mmol)을 무수 니트로벤젠 30 ml에 용해시킨 용액을 30분에 걸쳐서 천천히 가해주고, 반응물을 60 ~ 70 oC로 승온하여 1시간 교반하였다. 그런 다음, 반응물을 실온으로 냉각하여 증류수 70 ml를 가해주고 30분 정도 교반 후 생성물을 여과하였다. 얻어진 고체 생성물을 50 ml의 에테르에 분산시키고 실온에서 30 분 교반 후 여과하고 건조하여 연한 노란색 1-(2-브로모-9,9-디메틸플로오렌-7-닐)프로판-1-온 9.64 g (80 %)을 얻었다.Dissolve 10.0 g (36.6 mmol) of 2-bromo-9,9-dimethyl-fluorene in 100 ml of anhydrous nitrobenzene, add 5.37 g (40.3 mmol) of anhydrous aluminum chloride, and then add the reaction to 40-50 ° C. The solution was heated slowly to add a solution of 3.73 g (40.3 mmol) of propionyl chloride in 30 ml of anhydrous nitrobenzene over 30 minutes, and the reaction was heated to 60-70 ° C. and stirred for 1 hour. Then, the reaction was cooled to room temperature, 70 ml of distilled water was added, and after stirring for about 30 minutes, the product was filtered. The resulting solid product was dispersed in 50 ml of ether, stirred at room temperature for 30 minutes, filtered and dried to provide 9.64 g of pale yellow 1- (2-bromo-9,9-dimethylflooren-7-yl) propan-1-one. (80%) was obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.18(s, 1H), 8.02~7.97(m, 2H), 7.76~7.72(m, 2H), 7.56~7.55(m, 1H), 3.55~3.54(m, 2H), 1.72(s, 6H), 1.18~1.17(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18 (s, 1H), 8.02-7.97 (m, 2H), 7.76-7.72 (m, 2H), 7.56-7.55 (m, 1H), 3.55-3.54 (m, 2H), 1.72 (s, 6H), 1.18-1.17 (m, 3H)
MS(m/e) : 328.0MS ( m / e ): 328.0
합성예 1-(2) : 1-(9,9-디메틸-2-(페닐티오)- 플루오렌-7-닐)프로판-1-온(중간체 1-b) 합성Synthesis Example 1- (2): Synthesis of 1- (9,9-dimethyl-2- (phenylthio) -fluorene-7-yl) propan-1-one (intermediate 1-b)
Figure PCTKR2019005284-appb-I000036
Figure PCTKR2019005284-appb-I000036
[중간체 1-b]                                                 [Intermediate 1-b]
1-(2-브로모-9,9-디메틸플로오렌-7-닐)프로판-1-온 9.0 g (27.3 mmol)을 디메틸포름이미드 100ml에 용해 시킨 후 벤젠티올 4.5g(41.0mmol)과 탄산칼륨 7.6g(54.7mmol)을 투입하고 130℃로 6시간 가열 교반하였다. 에틸아세테이트 100ml와 증류수 100ml를 투입하여 반응을 종료하고 물층을 제거한 뒤 유기증을 회전식증발기를 이용하여 제거하여 수득한 오일을 에틸아세테이트 10ml와 메탄올 100ml를 사용하여 고체화하여 목적화합물 1-(9,9-디메틸-2-(페닐티오)- 플루오렌-7-닐)프로판-1-온 9.0 g (92%) 을 얻었다.After dissolving 9.0 g (27.3 mmol) of 1- (2-bromo-9,9-dimethylfluoroene-7-yl) propan-1-one in 100 ml of dimethylformimide, 4.5 g (41.0 mmol) of benzenethiol and 7.6 g (54.7 mmol) of potassium carbonate was added thereto, and the mixture was heated and stirred at 130 ° C. for 6 hours. 100 ml of ethyl acetate and 100 ml of distilled water were added to terminate the reaction, the water layer was removed, and the organic oil was removed using a rotary evaporator. The oil obtained was solidified using 10 ml of ethyl acetate and 100 ml of methanol to obtain the target compound 1- (9,9). 9.0 g (92%) of -dimethyl-2- (phenylthio) -fluorene-7-yl) propan-1-one were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.18(s, 1H), 8.02~7.97(m, 2H), 7.67~7.66(m, 1H), 7.49~7.48(m, 1H), 7.42~7.41(m, 2H), 7.32~7.20(m, 4H), 3.55~3.54(m, 2H), 1.72(s, 6H), 1.18~1.17(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18 (s, 1H), 8.02-7.97 (m, 2H), 7.67-7.62 (m, 1H), 7.49-7.48 (m, 1H), 7.42-7.41 (m, 2H), 7.32-7.20 (m, 4H), 3.55-3.54 (m, 2H), 1.72 (s, 6H), 1.18-1.17 (m, 3H)
MS(m/e) : 358.1MS ( m / e ): 358.1
합성예 1-(3) : 2-(히드록시이미노)-1-(9,9-디메틸-2-(페닐티오)- 플루오렌-7-닐)프로판-1-온(중간체 1-c) 합성Synthesis Example 1- (3): 2- (hydroxyimino) -1- (9,9-dimethyl-2- (phenylthio) -fluorene-7-yl) propan-1-one (intermediate 1-c) synthesis
Figure PCTKR2019005284-appb-I000037
Figure PCTKR2019005284-appb-I000037
[중간체 1-c]                                                   [Intermediate 1-c]
1-(9,9-디메틸-2-(페닐티오)- 플루오렌-7-닐)프로판-1-온 9.0 g (25.1 mmol)을 테트라히드로퓨란 100ml에 녹인 후 0℃ 냉각하고 동당량의 이소아밀나이트리트를 투입하고, 동당량의 염산을 추가한뒤 상온에서 5시간교반하고, 증류수로 세척한 뒤 회전식증발기를 사용하여 테트라히드로퓨란을 제거한 후 헥산으로 재결정하여 연한 노란색 2-(히드록시이미노)-1-(9,9-디메틸-2-(페닐티오)- 플루오렌-7-닐)프로판-1-온 6.8 g (70 %)을 얻었다.9.0 g (25.1 mmol) of 1- (9,9-dimethyl-2- (phenylthio) -fluorene-7-yl) propan-1-one are dissolved in 100 ml of tetrahydrofuran, cooled to 0 ° C., and isopropyl equivalent. Add amyl nitrite, add equivalent hydrochloric acid, stir at room temperature for 5 hours, wash with distilled water, remove tetrahydrofuran using rotary evaporator, and recrystallize with hexane to give pale yellow 2- (hydroxyimino 6.8 g (70%) of) -1- (9,9-dimethyl-2- (phenylthio) -fluorene-7-yl) propan-1-one were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.10~8.06(m, 2H), 7.93~7.92(m, 1H), 7.67~7.66(m, 1H), 7.49~7.48(m, 1H), 7.42~7.41(m, 2H), 7.32~7.20(m, 4H), 3.11(s, 3H), 2.23(s, 1H), 1.72(s, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10 to 8.06 (m, 2H), 7.93 to 7.72 (m, 1H), 7.67 to 7.62 (m, 1H), 7.49 to 7.48 (m, 1H), 7.42 to 7.41 ( m, 2H), 7.32-7.20 (m, 4H), 3.11 (s, 3H), 2.23 (s, 1H), 1.72 (s, 6H)
MS(m/e) : 387.1MS ( m / e ): 387.1
합성예 1-(4) : 1-(9,9-디메틸-2-(페닐티오)- 플루오렌-7-닐)-2-(((3-아세틸)옥시)이미노)프로판-1-온 (화합물 1)합성Synthesis Example 1- (4): 1- (9,9-dimethyl-2- (phenylthio) -fluorene-7-yl) -2-(((3-acetyl) oxy) imino) propane-1- On (Compound 1) Synthesis
Figure PCTKR2019005284-appb-I000038
Figure PCTKR2019005284-appb-I000038
[화합물 1]                                                   [Compound 1]
2-(히드록시이미노)-1-(9,9-디메틸-2-(페닐티오)- 플루오렌-7-닐)프로판-1-온 5 g (13.9 mmol)과 아세틸클로라이드 1.22g(15.5mmol)을 디클로로메탄 40ml에 용해 시키고 0℃로 냉각시킨 뒤 트리에틸아민 1.96g(19.4mmol)을 적가하고 2시간동안 교반한다. 증류수로 세척한 뒤 유기층을 감압농축하고 헥산 및 에틸아세테이트 4: 1용매 하에서 실리카겔 컬럼으로 정제하여 흰색의 1-(9,9-디메틸-2-(페닐티오)- 플루오렌-7-닐)-2-(((3-아세틸)옥시)이미노)프로판-1-온 (화합물 1) 4.4 g (80 %)을 얻었다.5 g (13.9 mmol) of 2- (hydroxyimino) -1- (9,9-dimethyl-2- (phenylthio) -fluorene-7-yl) propan-1-one and 1.22 g (15.5 mmol) of acetyl chloride ) Is dissolved in 40 ml of dichloromethane, cooled to 0 ° C., and 1.96 g (19.4 mmol) of triethylamine is added dropwise and stirred for 2 hours. After washing with distilled water, the organic layer was concentrated under reduced pressure, and purified by silica gel column under hexane and ethyl acetate 4: 1 solvent to obtain white 1- (9,9-dimethyl-2- (phenylthio) -fluorene-7-yl)- 4.4 g (80%) of 2-(((3-acetyl) oxy) imino) propan-1-one (Compound 1) were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.10~8.06(m, 2H), 7.93~7.92(m, 1H), 7.67~7.66(m, 1H), 7.49~7.48(m, 1H), 7.42~7.41(m, 2H), 7.32~7.20(m, 4H), 3.11(s, 3H), 2.20(s, 3H), 1.72(s, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10 to 8.06 (m, 2H), 7.93 to 7.72 (m, 1H), 7.67 to 7.62 (m, 1H), 7.49 to 7.48 (m, 1H), 7.42 to 7.41 ( m, 2H), 7.32-7.20 (m, 4H), 3.11 (s, 3H), 2.20 (s, 3H), 1.72 (s, 6H)
MS(m/e) : 429.1MS ( m / e ): 429.1
합성예 2 : 화합물 15의 합성Synthesis Example 2 Synthesis of Compound 15
합성예 2-(1) : 9,9-디메틸-플루오렌-2-티올(중간체 2-a)의 합성Synthesis Example 2- (1): Synthesis of 9,9-dimethyl-fluorene-2-thiol (intermediate 2-a)
Figure PCTKR2019005284-appb-I000039
Figure PCTKR2019005284-appb-I000039
[중간체 2-a]                                            [Intermediate 2-a]
반응기에 2-브로모-9,9-디메틸플루오렌을 넣고 질소를 충진하고 THF로 교반 용해시킨 뒤 78℃로 유지하면서 2.5M 부틸리튬을 87.9ml를 적가하고 1시간동안 교반한다. 황 14.1g(439.3mmol)을 조금씩 투입하고 4시간에 걸쳐 서서히 상온으로 승온시킨다. 포화암모늄클로라이드 수용액을 투입하여 반응을 종료하고, 물층을 제거한뒤 증류수로 유기층을 여려차례 세척하여 얻어진 유기층을 무수황산마그네슘으로 건조시키고 용매를 제거하여 얻은 혼합물을 컬럼크로마토그래피(노르말헥산)하여 노란색의 목적화합물 9,9-디메틸-플루오렌-2-티올 32.7g(79%)를 수득하였다.2-bromo-9,9-dimethylfluorene was added to the reactor, charged with nitrogen, dissolved in THF, stirred and dissolved, and maintained at 78 ° C. while 87.9 ml of 2.5M butyllithium was added dropwise and stirred for 1 hour. 14.1 g (439.3 mmol) of sulfur is added little by little and gradually warmed to room temperature over 4 hours. Aqueous solution of saturated ammonium chloride was added to terminate the reaction, the water layer was removed, and the organic layer was washed several times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed. The mixture was purified by column chromatography (normal hexane) to give a yellow color. 32.7 g (79%) of the title compound 9,9-dimethyl-fluorene-2-thiol were obtained.
1H NMR (δ ppm; DMSO-d 6) : 7.87~7.86(m, 1H), 7.71~7.70(m, 1H), 7.55~7.54(m, 1H), 7.47~7.46(m, 1H), 7.38~7.28(m, 3H), 3.41(s, 1H), 1.70(s, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 7.87-7.86 (m, 1H), 7.71-7.70 (m, 1H), 7.55-7.54 (m, 1H), 7.47-7.46 (m, 1H), 7.38-7.28 ( m, 3H), 3.41 (s, 1H), 1.70 (s, 6H)
MS(m/e) : 226.1MS ( m / e ): 226.1
합성예 2-(2) : 1-(7-((9,9-디메틸-플루오렌-2-닐)티오)-9,9-디메틸-플루오렌-2-닐)프로판-1-온(중간체 2-b)의 합성Synthesis Example 2- (2): 1- (7-((9,9-dimethyl-fluorene-2-yl) thio) -9,9-dimethyl-fluoren-2-yl) propan-1-one ( Synthesis of Intermediate 2-b)
Figure PCTKR2019005284-appb-I000040
Figure PCTKR2019005284-appb-I000040
[중간체 2-b]                                                 [Intermediate 2-b]
합성예 1-(2)와 동일한 방법으로1-(7-브로모-9,9-디메틸-플루오렌-2-닐)프로판-1-온 10.0 g (30.4 mmol), 9,9-디메틸-플루오렌-2-티올 10.3g(45.6mmol)과 탄산칼륨 8.4g(60.7mmol)을 사용하여 목적화합물 1-(7-((9,9-디메틸-플루오렌-2-닐)티오)-9,9-디메틸-플루오렌-2-닐)프로판-1-온 13.4 g (93%) 을 얻었다.10.0 g (30.4 mmol) of 1- (7-bromo-9,9-dimethyl-fluoren-2-yl) propan-1-one in the same manner as in Synthesis example 1- (2), 9,9-dimethyl- Using 10.3 g (45.6 mmol) of fluorene-2-thiol and 8.4 g (60.7 mmol) of potassium carbonate, the target compound 1- (7-((9,9-dimethyl-fluorene-2-yl) thio) -9 13.4 g (93%) of, 9-dimethyl-fluoren-2-yl) propan-1-one were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.18~8.17(m, 1H), 8.01~7.87(m, 3H), 7.67~7.66(m, 2H), 7.55~7.54(m, 2H), 7.38~7.32(m, 4H), 3.54(m, 2H), 1.71(s, 6H), 1.70(s, 6H), 1.18~1.17(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18-8.17 (m, 1H), 8.01-7.87 (m, 3H), 7.67-7.62 (m, 2H), 7.55-7.54 (m, 2H), 7.38-7.32 ( m, 4H), 3.54 (m, 2H), 1.71 (s, 6H), 1.70 (s, 6H), 1.18-1.17 (m, 3H)
MS(m/e) : 474.2MS ( m / e ): 474.2
합성예 2-(3) : 1-(7-((9,9-디메틸-플루오렌-2-닐)티오)-9,9-디메틸-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온(중간체 2-c)의 합성Synthesis Example 2- (3): 1- (7-((9,9-dimethyl-fluorene-2-yl) thio) -9,9-dimethyl-fluorene-2-yl) -2- (hydroxyy Synthesis of Mino) Propan-1-one (Intermediate 2-c)
Figure PCTKR2019005284-appb-I000041
Figure PCTKR2019005284-appb-I000041
[중간체 2-c]                                                   [Intermediate 2-c]
합성예 1-(3)과 동일한 방법으로 1-(7-((9,9-디메틸-플루오렌-2-닐)티오)-9,9-디메틸-플루오렌-2-닐)프로판-1-온 10.0 g (21.1 mmol) 동당량의 이소아밀나이트리트, 염산을 사용하여 연한 노란색 1-(7-((9,9-디메틸-플루오렌-2-닐)티오)-9,9-디메틸-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 9.0 g (85 %)을 얻었다.1- (7-((9,9-dimethyl-fluorene-2-yl) thio) -9,9-dimethyl-fluorene-2-yl) propane-1 in the same manner as in Synthesis example 1- (3) 10.0 g (21.1 mmol) equivalent of isoamylnitrite, light yellow 1- (7-((9,9-dimethyl-fluoren-2-yl) thio) -9,9-dimethyl with hydrochloric acid 9.0 g (85%) of -fluorene-2-yl) -2- (hydroxyimino) propan-1-one were obtained.
1H NMR (δ ppm; DMSO-d 6): 8.10~8.06(m, 2H), 7.93~7.87(m, 2H), 7.67~7.66(m, 2H), 7.55~7.54(m, 1H), 7.49~7.48(m, 2H), 7.38~7.29(m, 4H), 3.10(s, 3H), 2.10(s, 1H), 1.71(s, 6H), 1.70(s, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10-8.06 (m, 2H), 7.93-7.87 (m, 2H), 7.67-7.62 (m, 2H), 7.55-7.54 (m, 1H), 7.49-7.48 ( m, 2H), 7.38-7.29 (m, 4H), 3.10 (s, 3H), 2.10 (s, 1H), 1.71 (s, 6H), 1.70 (s, 6H)
MS(m/e) : 503.2MS ( m / e ): 503.2
합성예 2-(4) : 2-(아세톡시이미노)-1-(7-((9,9-디메틸-플루오렌-2-닐)티오)-9,9-디메틸-플루오렌-2-닐)프로판-1-온 (화합물 15)의 합성Synthesis Example 2- (4): 2- (Acetoxyimino) -1- (7-((9,9-dimethyl-fluorene-2-yl) thio) -9,9-dimethyl-fluorene-2- Synthesis of Neyl) Propan-1-one (Compound 15)
Figure PCTKR2019005284-appb-I000042
Figure PCTKR2019005284-appb-I000042
[화합물 15]                                                  [Compound 15]
합성예 1-(4)와 동일한 방법으로1-(7-((9,9-디메틸-플루오렌-2-닐)티오)-9,9-디메틸-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 5 g (9.9 mmol), 아세틸클로라이드와 0.94g(11.9mmol) 트리에틸아민 1.51g(14.9mmol)사용하여 흰색의 2-(아세톡시이미노)-1-(7-((9,9-디메틸-플루오렌-2-닐)티오)-9,9-디메틸-플루오렌-2-닐)프로판-1-온 (화합물 15) 4.7 g (87 %)을 얻었다.1- (7-((9,9-dimethyl-fluorene-2-yl) thio) -9,9-dimethyl-fluorene-2-yl) -2- in the same manner as in Synthesis example 1- (4) 5 g (9.9 mmol) of (hydroxyimino) propan-1-one, 1.51 g (14.9 mmol) of acetyl chloride and 0.94 g (11.9 mmol) triethylamine were used as white 2- (acetoxyimino) -1- ( 4.7 g (87%) of 7-((9,9-dimethyl-fluorene-2-yl) thio) -9,9-dimethyl-fluorene-2-yl) propan-1-one (compound 15) was obtained. .
1H NMR (δ ppm; DMSO-d 6) : 8.10~8.06(m, 2H), 7.93~7.86(m, 2H), 7.67~7.66(m, 2H), 7.55~7.54(m, 1H), 7.49~7.48(m, 2H), 7.38~7.29(m, 4H), 3.10(s, 3H), 2.27(s, 3H), 1.71(s, 6H), 1.70(s, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10-8.06 (m, 2H), 7.93-7.86 (m, 2H), 7.67-7.72 (m, 2H), 7.55-7.54 (m, 1H), 7.49-7.48 ( m, 2H), 7.38-7.29 (m, 4H), 3.10 (s, 3H), 2.27 (s, 3H), 1.71 (s, 6H), 1.70 (s, 6H)
MS(m/e) : 545.2MS ( m / e ): 545.2
합성예 3 : 화합물 17의 합성Synthesis Example 3 Synthesis of Compound 17
합성예 3-(1) : 1-(7-브로모-9,9-디메틸-플루오렌-2-닐)부탄-1-온 (중간체 3-a)의 합성Synthesis Example 3- (1): Synthesis of 1- (7-bromo-9,9-dimethyl-fluoren-2-yl) butan-1-one (intermediate 3-a)
Figure PCTKR2019005284-appb-I000043
Figure PCTKR2019005284-appb-I000043
[중간체 3-a]                                                  [Intermediate 3-a]
합성예 1-(1)과 동일한 방법으로 2-브로모-9,9-디페닐플루오렌10.0 g (36.6mmol)을 무수 염화알루미늄 5.53 g (41.5 mmol) 부티릴클로라이드 4.21 g (41.5mmol)을 사용하여 흰색의 1-(7-브로모-9,9-디메틸-플루오렌-2-닐)부탄-1-온 11.43 g (91 %)을 얻었다.In the same manner as in Synthesis example 1- (1), 10.0 g (36.6 mmol) of 2-bromo-9,9-diphenylfluorene was added to 5.21 g (41.5 mmol) butyryl chloride of anhydrous aluminum chloride. To obtain 11.43 g (91%) of white 1- (7-bromo-9,9-dimethyl-fluoren-2-yl) butan-1-one.
1H NMR (δ ppm; DMSO-d 6) : 8.18(s, 1H), 8.02~7.97(m, 2H), 7.76~7.72(m, 2H), 7.56~7.55(m, 1H), 2.96~2.94(m, 2H), 1.72(s, 6H), 1.59~1.54(m,2H) .0.90~0.89(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18 (s, 1H), 8.02-7.97 (m, 2H), 7.76-7.72 (m, 2H), 7.56-7.55 (m, 1H), 2.96-2.94 (m, 2H), 1.72 (s, 6H), 1.59-1.54 (m, 2H) .0.90-0.99 (m, 3H)
(m/e) : 342.1( m / e ): 342.1
합성예 3-(2) : 1-(7-((4-메톡시페닐)티오)-9,9-디메틸-플루오렌-2-닐)부탄-1-온 (중간체 3-b)의 합성Synthesis Example 3- (2): Synthesis of 1- (7-((4-methoxyphenyl) thio) -9,9-dimethyl-fluoren-2-yl) butan-1-one (intermediate 3-b)
Figure PCTKR2019005284-appb-I000044
Figure PCTKR2019005284-appb-I000044
[중간체 3-b]                                               [Intermediate 3-b]
합성예 1-(2)와 동일한 방법으로1-(7-브로모-9,9-디메틸-플루오렌-2-닐)부탄-1-온 10.0 g (29.13 mmol), 4-메톡시벤젠티올 6.13g(43.7mmol)과 탄산칼륨 8.05g(58.3mmol)을 사용하여 목적화합물 1-(7-((4-메톡시페닐)티오)-9,9-디메틸-플루오렌-2-닐)부탄-1-온 9.4 g (80%) 을 얻었다.10.0 g (29.13 mmol) of 1- (7-bromo-9,9-dimethyl-fluoren-2-yl) butan-1-one in the same manner as in Synthesis example 1- (2), 4-methoxybenzenethiol 6.13 g (43.7 mmol) and 8.05 g (58.3 mmol) of potassium carbonate were used to target compound 1- (7-((4-methoxyphenyl) thio) -9,9-dimethyl-fluoren-2-yl) butane 9.4 g (80%) of 1-one were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.18(s, 1H), 8.01~7.95(m, 2H), 7.67~7.65(m, 1H), 7.49~7.44(m, 3H), 7.32~7.30(m, 3H), 3.83(s, 3H), 2.96~2.95(m, 2H), 1.72(s, 6H), 1.59~1.57(m, 2H), 0.90~0.89(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18 (s, 1H), 8.01-7.95 (m, 2H), 7.67-7.75 (m, 1H), 7.49-7.44 (m, 3H), 7.32-7.30 (m, 3H), 3.83 (s, 3H), 2.96-2.95 (m, 2H), 1.72 (s, 6H), 1.59-1.57 (m, 2H), 0.90-0.99 (m, 3H)
MS(m/e) : 431.2MS ( m / e ): 431.2
합성예 3-(3) : 2-(히드록시이미노)-1-(7-((4-메톡시페닐)티오)-9,9-디메틸-플루오렌-2-닐)부탄-1-온 (중간체 3-c)의 합성Synthesis Example 3- (3): 2- (hydroxyimino) -1- (7-((4-methoxyphenyl) thio) -9,9-dimethyl-fluoren-2-yl) butan-1-one Synthesis of (Intermediate 3-c)
Figure PCTKR2019005284-appb-I000045
Figure PCTKR2019005284-appb-I000045
[중간체 3-c]                                                  [Intermediate 3-c]
합성예 1-(3)과 동일한 방법으로 1-(7-((4-메톡시페닐)티오)-9,9-디메틸-플루오렌-2-닐)부탄-1-온 10.0 g (24.8 mmol) 동당량의 이소아밀나이트리트, 염산을 사용하여 연한 노란색 2-(히드록시이미노)-1-(7-((4-메톡시페닐)티오)-9,9-디메틸-플루오렌-2-닐)부탄-1-온 8.0 g (75 %)을 얻었다.10.0 g (24.8 mmol) of 1- (7-((4-methoxyphenyl) thio) -9,9-dimethyl-fluorene-2-yl) butan-1-one in the same manner as in Synthesis example 1- (3) ) Light yellow 2- (hydroxyimino) -1- (7-((4-methoxyphenyl) thio) -9,9-dimethyl-fluorene-2- using an equivalent of isoamyl nitrite and hydrochloric acid Nil) butan-1-one 8.0 g (75%) was obtained.
1H NMR (δ ppm; DMSO-d 6): 8.10~8.07(m, 2H), 7.95~7.93(m, 1H), 7.67~7.66(m, 1H), 7.49~7.44(m, 3H), 7.32~7.30(m, 3H), 3.83(s, 3H), 2.10(s, 1H), 1.72(s, 6H), 1.57~1.55(m, 2H), 1.041.03(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10-8.07 (m, 2H), 7.95-7.73 (m, 1H), 7.67-7.62 (m, 1H), 7.49-7.44 (m, 3H), 7.32-7.30 ( m, 3H), 3.83 (s, 3H), 2.10 (s, 1H), 1.72 (s, 6H), 1.57 to 1.55 (m, 2H), 1.041.03 (m, 3H)
MS(m/e) : 431.2MS ( m / e ): 431.2
합성예 3-(4) : 2-(아세톡시이미노)-1-(7-((4-메톡시페닐)티오)-9,9-디메틸-플루오렌-2-닐)부탄-1-온 (화합물 17)의 합성Synthesis Example 3- (4): 2- (acetoxyimino) -1- (7-((4-methoxyphenyl) thio) -9,9-dimethyl-fluoren-2-yl) butan-1-one Synthesis of (Compound 17)
Figure PCTKR2019005284-appb-I000046
Figure PCTKR2019005284-appb-I000046
[화합물 17]                                                  [Compound 17]
합성예 1-(4)와 동일한 방법으로2-(히드록시이미노)-1-(7-((4-메톡시페닐)티오)-9,9-디메틸-플루오렌-2-닐)부탄-1-온 5 g (11.6 mmol), 아세틸클로라이드와 1.09g(13.9mmol) 트리에틸아민 1.75g(17.4mmol)사용하여 흰색의 2-(아세톡시이미노)-1-(7-((4-메톡시페닐)티오)-9,9-디메틸-플루오렌-2-닐)부탄-1-온 (화합물 17) 4.8 g (88 %)을 얻었다.2- (hydroxyimino) -1- (7-((4-methoxyphenyl) thio) -9,9-dimethyl-fluorene-2-yl) butane- in the same manner as in Synthesis Example 1- (4)- 5 g (11.6 mmol) of 1-one, 1.75 g (17.4 mmol) of acetyl chloride and 1.09 g (13.9 mmol) of triethylamine were used as white 2- (acetoxyimino) -1- (7-((4-meth 4.8 g (88%) of methoxyphenyl) thio) -9,9-dimethyl-fluoren-2-yl) butan-1-one (Compound 17) was obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.10~8.07(m, 2H), 7.95~7.93(m, 1H), 7.67~7.66(m, 1H), 7.49~7.44(m, 3H), 7.32~7.30(m, 3H), 3.83(s, 3H), 2.28(s, 3H), 1.72(s, 6H), 1.57~1.55(m, 2H), 1.04~1.03(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10-8.07 (m, 2H), 7.95-7.73 (m, 1H), 7.67-7.62 (m, 1H), 7.49-7.44 (m, 3H), 7.32-7.30 ( m, 3H), 3.83 (s, 3H), 2.28 (s, 3H), 1.72 (s, 6H), 1.57 to 1.55 (m, 2H), 1.04 to 1.03 (m, 3H)
MS(m/e) : 473.2MS ( m / e ): 473.2
합성예 4 : 화합물 19의 합성Synthesis Example 4 Synthesis of Compound 19
합성예 4-(1) : 1-(9,9-디메틸-7-((4-니트로페닐)티오)-플루오렌-2-닐)프로판-1-온 (중간체 4-a)의 합성Synthesis Example 4- (1): Synthesis of 1- (9,9-dimethyl-7-((4-nitrophenyl) thio) -fluoren-2-yl) propan-1-one (intermediate 4-a)
Figure PCTKR2019005284-appb-I000047
Figure PCTKR2019005284-appb-I000047
[중간체 4-A]                                                [Intermediate 4-A]
합성예 1-(2)와 동일한 방법으로1-(7-브로모-9,9-디메틸-플루오렌-2-닐)프로판-1-온 10.0 g (30.4 mmol), 4-니트로벤젠티올7.1g(45.6mmol)과 탄산칼륨 8.4g(60.7mmol)을 사용하여 목적화합물 1-(9,9-디메틸-7-((4-니트로페닐)티오)-플루오렌-2-닐)프로판-1-온 8.0 g (65%) 을 얻었다.Synthesis Example 1- (2) 10.0 g (30.4 mmol) 1- (7-bromo-9,9-dimethyl-fluoren-2-yl) propan-1-one and 4-nitrobenzenethiol7.1 Compound 1- (9,9-dimethyl-7-((4-nitrophenyl) thio) -fluorene-2-yl) propane-1 using g (45.6 mmol) and 8.4 g (60.7 mmol) potassium carbonate 8.0 g (65%) of -on was obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.18(s, 1H), 8.06~7.99(m, 4H), 7.67~7.66(m, 3H), 7.49(s, 1H), 7.32~7.31(m, 1H), 3.54~3.53(m, 2H), 1.73(s, 6H), 1.18~1.17(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18 (s, 1H), 8.06 ~ 7.99 (m, 4H), 7.67 ~ 7.66 (m, 3H), 7.49 (s, 1H), 7.32 ~ 7.31 (m, 1H) , 3.54 to 3.53 (m, 2H), 1.73 (s, 6H), 1.18 to 1.17 (m, 3H)
MS(m/e) : 403.1MS ( m / e ): 403.1
합성예 4-(2) : 1-(9,9-디메틸-7-((4-니트로페닐)티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 (중간체 4-b)의 합성Synthesis Example 4- (2): 1- (9,9-dimethyl-7-((4-nitrophenyl) thio) -fluoren-2-yl) -2- (hydroxyimino) propan-1-one ( Synthesis of Intermediate 4-b)
Figure PCTKR2019005284-appb-I000048
Figure PCTKR2019005284-appb-I000048
[중간체 4-b]                                                 [Intermediate 4-b]
합성예 1-(3)과 동일한 방법으로 1-(9,9-디메틸-7-((4-니트로페닐)티오)-플루오렌-2-닐)프로판-1-온 8.0 g (19.83 mmol) 동당량의 이소아밀나이트리트, 염산을 사용하여 연한 노란색 1-(9,9-디메틸-7-((4-니트로페닐)티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 7.5 g (87 %)을 얻었다.8.0 g (19.83 mmol) of 1- (9,9-dimethyl-7-((4-nitrophenyl) thio) -fluorene-2-yl) propan-1-one in the same manner as in Synthesis example 1- (3) Light yellow 1- (9,9-dimethyl-7-((4-nitrophenyl) thio) -fluorene-2-yl) -2- (hydroxyimino) using an equivalent of isoamyl nitrite and hydrochloric acid 7.5 g (87%) of propane-1-one were obtained.
1H NMR (δ ppm; DMSO-d 6): 8.10~8.06(m, 4H), 7.93~7.92(m, 1H), 7.67~7.66(m, 3H), 7.49(s,1H), 7.32~7.31(m, 1H), 3.11(s, 3H), 3.01(s, 1H), 1.72(s, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10 to 8.06 (m, 4H), 7.93 to 7.72 (m, 1H), 7.67 to 7.62 (m, 3H), 7.49 (s, 1H), 7.32 to 7.31 (m, 1H), 3.11 (s, 3H), 3.01 (s, 1H), 1.72 (s, 6H)
MS(m/e) : 432.1MS ( m / e ): 432.1
합성예 4-(3) : 2-(아세톡시이미노)-1-(9,9-디메틸-7-((4-니트로페닐)티오)-플루오렌-2-닐)프로판-1-온 (화합물 19)의 합성Synthesis Example 4- (3): 2- (Acetoxyimino) -1- (9,9-dimethyl-7-((4-nitrophenyl) thio) -fluoren-2-yl) propan-1-one ( Synthesis of Compound 19)
Figure PCTKR2019005284-appb-I000049
Figure PCTKR2019005284-appb-I000049
[화합물 19]                                                  [Compound 19]
합성예 1-(4)와 동일한 방법으로1-(9,9-디메틸-7-((4-니트로페닐)티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 5 g (11.56 mmol), 아세틸클로라이드와 1.09g(13.9mmol) 트리에틸아민 1.75g(17.3mmol)사용하여 노란색의 2-(아세톡시이미노)-1-(9,9-디메틸-7-((4-니트로페닐)티오)-플루오렌-2-닐)프로판-1-온 (화합물 19) 4.7 g (85 %)을 얻었다.1- (9,9-dimethyl-7-((4-nitrophenyl) thio) -fluorene-2-yl) -2- (hydroxyimino) propane-1 in the same manner as in Synthesis example 1- (4) Yellow (2- (acetoxyimino) -1- (9,9-dimethyl-7-) using 5 g (11.56 mmol) acetyl chloride and 1.75 g (17.3 mmol) of 1.09 g (13.9 mmol) triethylamine 4.7 g (85%) of ((4-nitrophenyl) thio) -fluoren-2-yl) propan-1-one (Compound 19) were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.10~8.06(m, 4H), 7.93~7.92(m, 1H), 7.67~7.66(m, 3H), 7.49(s, 1H), 7.32~7.31(m, 1H), 3.11(s, 3H), 2.28(s, 3H), 1.72(s, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10 to 8.06 (m, 4H), 7.93 to 7.72 (m, 1H), 7.67 to 7.62 (m, 3H), 7.49 (s, 1H), 7.32 to 7.31 (m, 1H), 3.11 (s, 3H), 2.28 (s, 3H), 1.72 (s, 6H)
MS(m/e) : 474.1MS ( m / e ): 474.1
합성예 5 : 화합물 22의 합성Synthesis Example 5 Synthesis of Compound 22
합성예 5-(1) : 2-((벤조일옥시)이미노)-1-(9,9-디메틸-7-(페닐티오)- 플루오렌-2-닐)프로판-1-온 (화합물 22)의 합성Synthesis Example 5- (1): 2-((benzoyloxy) imino) -1- (9,9-dimethyl-7- (phenylthio) -fluoren-2-yl) propan-1-one (Compound 22 ) Synthesis
Figure PCTKR2019005284-appb-I000050
[화합물 22]
Figure PCTKR2019005284-appb-I000050
[Compound 22]
합성예 1-(4)와 동일한 방법으로 1-(9,9-디메틸-7-(페닐티오)- 플루오렌-2-닐)-2-(리드록시이미노)프로판-1-온 5 g (12.9 mmol), 벤조일클로라이드와 2.18g(15.5mmol) 트리에틸아민 1.96g(19.36mmol)사용하여 노란색의 2-(아세톡시이미노)-1-(9,9-디메틸-7-((4-니트로페닐)티오)-플루오렌-2-닐)프로판-1-온 (화합물 22) 6.34 g (85 %)을 얻었다.5 g of 1- (9,9-dimethyl-7- (phenylthio)-fluoren-2-yl) -2- (ridoxyimino) propan-1-one in the same manner as in Synthesis example 1- (4) 12.9 mmol), yellow 2- (acetoxyimino) -1- (9,9-dimethyl-7-((4-nitro) using benzoyl chloride and 1.96 g (19.36 mmol) of 2.18 g (15.5 mmol) triethylamine. Phenyl) thio) -fluoren-2-yl) propane - 1-one 6.34 g (85%) of (Compound 22) were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.21~8.20(m, 2H), 8.10~8.06(m, 2H), 7.93~7.92(m, 1H), 7.79~7.78(m, 1H), 7.67~7.66(m, 3H), 7.49~7.41(m, 3H), 7.32~7.19(m, 4H), 3.11(s, 3H), 1.72(s, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.21 to 8.20 (m, 2H), 8.10 to 8.06 (m, 2H), 7.93 to 7.82 (m, 1H), 7.79 to 7.78 (m, 1H), 7.67 to 7.62 ( m, 3H), 7.49-7.41 (m, 3H), 7.32-7.19 (m, 4H), 3.11 (s, 3H), 1.72 (s, 6H)
MS(m/e) : 491.2MS ( m / e ): 491.2
합성예 6 : 화합물 29의 합성Synthesis Example 6 Synthesis of Compound 29
합성예 6-(1) : Synthesis Example 6- (1): 1-(7-브로모-9,9-디에틸-플루오렌-2-닐)프로판-1-온 1- (7-bromo-9,9-diethyl-fluoren-2-yl) propan-1-one (중(medium
간체 6-a)의 합성Synthesis of Simplified 6-a)
Figure PCTKR2019005284-appb-I000051
Figure PCTKR2019005284-appb-I000051
[중간체 6-a]                                                  [Intermediate 6-a]
합성예 1-(1)과 동일한 방법으로 2-브로모-9,9-디에틸-플루오렌 10.0 g (49.8mmol)을 무수 염화알루미늄 5.84 g (54.8 mmol) 프로피오닐클로라이드 5.07g (54.8mmol)을 사용하여 흰색의 1-(7-브로모-9,9-디에틸-플루오렌-2-닐)프로판-1-온 17.8 g (93 %)을 얻었다.In the same manner as in Synthesis Example 1- (1), 10.0 g (49.8 mmol) of 2-bromo-9,9-diethyl-fluorene was dissolved in 5.84 g (54.8 mmol) of propionyl chloride (5.07 g, 54.8 mmol) in anhydrous aluminum chloride. To obtain 17.8 g (93%) of white 1- (7-bromo-9,9-diethyl-fluorene-2-yl) propan-1-one.
1H NMR (δ ppm; DMSO-d 6) : 8.18(s, 1H), 8.1~7.95(m, 2H), 7.76~7.72(m, 2H), 7.55~7.54(m, 1H), 3.54~3.53(m, 2H), 1.91~1.90(m, 4H), 1.18~1.17(m, 3H), 0.90~0.89(m, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18 (s, 1H), 8.1 ~ 7.95 (m, 2H), 7.76 ~ 7.72 (m, 2H), 7.55 ~ 7.54 (m, 1H), 3.54 ~ 3.53 (m, 2H), 1.91-1.90 (m, 4H), 1.18-1.17 (m, 3H), 0.90-0.99 (m, 6H)
MS(m/e) : 356.1MS ( m / e ): 356.1
합성예 6-(2) : 1-(9,9-디에틸-7-(페닐티오)-플루오렌-2-닐)프로판-1-온 (중간체 6-b)의 합성Synthesis Example 6- (2): Synthesis of 1- (9,9-diethyl-7- (phenylthio) -fluoren-2-yl) propan-1-one (intermediate 6-b)
Figure PCTKR2019005284-appb-I000052
Figure PCTKR2019005284-appb-I000052
[중간체 6-b]                                                  [Intermediate 6-b]
합성예 1-(2)와 동일한 방법으로1-(7-브로모-9,9-디에틸-플루오렌-2-닐)프로판-1-온 10.0 g (28.00 mmol), 벤젠티올 4.63g(42.00mmol)과 탄산칼륨 7.74g(56.00mmol)을 사용하여 목적화합물 1-(9,9-디에틸-7-(페닐티오)-플루오렌-2-닐)프로판-1-온 9.8 g (91%) 을 얻었다.In the same manner as in Synthesis Example 1- (2), 10.0 g (28.00 mmol) of 1- (7-bromo-9,9-diethyl-fluoren-2-yl) propan-1-one and 4.63 g of benzenethiol ( 9.8 g (91) of target compound 1- (9,9-diethyl-7- (phenylthio) -fluoren-2-yl) propan-1-one using 42.00 mmol) and 7.74 g (56.00 mmol) of potassium carbonate %) Was obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.18(s, 1H), 8.01~7.95(m, 2H), 7.67~7.66(m, 1H), 7.49~7.41(m, 3H), 7.32~7.25(m, 4H), 3.54~3.53(m, 2H), 1.91~1.90(m, 4H), 1.18~1.17(m, 3H), 0.90~0.89(m, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18 (s, 1H), 8.01-7.95 (m, 2H), 7.67-7.62 (m, 1H), 7.49-7.41 (m, 3H), 7.32-7.25 (m, 4H), 3.54-3.53 (m, 2H), 1.91-1.90 (m, 4H), 1.18-1.17 (m, 3H), 0.90-0.99 (m, 6H)
MS(m/e) : 386.17MS ( m / e ): 386.17
합성예 6-(3) : 1-(9,9-디에틸-7-(페닐티오)-플루오렌-2-닐)-2-(히드록시Synthesis Example 6- (3): 1- (9,9-Diethyl-7- (phenylthio) -fluoren-2-yl) -2- (hydroxy
이미노)프로판-1-온(중간체 6-c)의 합성Synthesis of Imino) Propan-1-one (Intermediate 6-c)
Figure PCTKR2019005284-appb-I000053
Figure PCTKR2019005284-appb-I000053
[중간체 6-c]                                                    [Intermediate 6-c]
합성예 1-(3)과 동일한 방법으로 1-(9,9-디에틸-7-(페닐티오)-플루오렌-2-닐)프로판-1-온 10.0 g (25.87 mmol) 동당량의 이소아밀나이트리트, 염산을 사용하여 연한 노란색 1-(9,9-디에틸-7-(페닐티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 9.0 g (84 %)을 얻었다.10.0 g (25.87 mmol) equivalent isoform of 1- (9,9-diethyl-7- (phenylthio) -fluoren-2-yl) propan-1-one in the same manner as in Synthesis Example 1- (3) 9.0 g of pale yellow 1- (9,9-diethyl-7- (phenylthio) -fluoren-2-yl) -2- (hydroxyimino) propan-1-one with amylnitrite, hydrochloric acid 84%).
1H NMR (δ ppm; DMSO-d 6): 8.10~8.06(m, 2H), 7.93~7.92(m, 1H), 7.67~7.66(m, 1H), 7.49~7.41(m, 3H), 7.32~7.25(m, 4H), 3.11(s, 3H), 2.0~1.90(m, 5H), 0.90~0.89(m, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10 to 8.06 (m, 2H), 7.93 to 7.72 (m, 1H), 7.67 to 7.62 (m, 1H), 7.49 to 7.41 (m, 3H), 7.32 to 7.25 ( m, 4H), 3.11 (s, 3H), 2.0-1.90 (m, 5H), 0.90-0.99 (m, 6H)
MS(m/e) : 415.2MS ( m / e ): 415.2
합성예 6-(4) : 2-(아세토이미노)-1-(9,9-디에틸-7-(페닐티오-플루오렌-2-닐)프로판-1-온 (화합물 29)의 합성Synthesis Example 6- (4): Synthesis of 2- (acetoimino) -1- (9,9-diethyl-7- (phenylthio-fluorene-2-yl) propan-1-one (Compound 29)
Figure PCTKR2019005284-appb-I000054
Figure PCTKR2019005284-appb-I000054
[화합물 29]                                                    [Compound 29]
합성예 6-(4)와 동일한 방법으로1-(9,9-디에틸-7-(페닐티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 5 g (12.03 mmol), 아세틸클로라이드와 1.13g(14.44mmol) 트리에틸아민 1.83g(18.05mmol)사용하여 흰색의 2-(아세토이미노)-1-(9,9-디에틸-7-(페닐티오-플루오렌-2-닐)프로판-1-온 (화합물 29) 4.4 g (80 %)을 얻었다.5 g of 1- (9,9-diethyl-7- (phenylthio) -fluoren-2-yl) -2- (hydroxyimino) propan-1-one in the same manner as in Synthesis example 6- (4) (12.03 mmol), white 2- (acetoimino) -1- (9,9-diethyl-7- (phenylthio-) using acetylchloride and 1.83 g (18.05 mmol) of 1.13 g (14.44 mmol) triethylamine 4.4 g (80%) of fluorene-2-yl) propan-1-one (compound 29) were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.10~8.06(m, 2H), 7.93~7.92(m, 1H), 7.67~7.66(m, 1H), 7.49~7.41(m, 3H), 7.32~7.25(m, 4H), 3.11(s, 3H), 2.28(s, H), 1.91~1.90(m, 5H), 0.90~0.89(m, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10 to 8.06 (m, 2H), 7.93 to 7.72 (m, 1H), 7.67 to 7.62 (m, 1H), 7.49 to 7.41 (m, 3H), 7.32 to 7.25 ( m, 4H), 3.11 (s, 3H), 2.28 (s, H), 1.91-1.90 (m, 5H), 0.90-0.99 (m, 6H)
MS(m/e) : 457.2MS ( m / e ): 457.2
합성예 7 : 화합물 33의 합성Synthesis Example 7 Synthesis of Compound 33
합성예 7-(1) : 1-(7-브로모-9,9-디페닐플루오렌-2-닐)프로판-1-온(중간체 7-a)의 합성Synthesis Example 7- (1): Synthesis of 1- (7-bromo-9,9-diphenylfluoren-2-yl) propan-1-one (intermediate 7-a)
Figure PCTKR2019005284-appb-I000055
Figure PCTKR2019005284-appb-I000055
[중간체 7-a]                                                   [Intermediate 7-a]
합성예 1-(1)과 동일한 방법으로 2-브로모-9,9-디페닐플루오렌15.0 g (36.6mmol)을 무수 염화알루미늄 5.53 g (41.5 mmol) 프로피오닐클로라이드 3.84 g (41.5mmol)을 사용하여 노란색 1-(7-브로모-9,9-디페닐플루오렌-2-닐)프로판-1-온 15.4 g (90 %)을 얻었다.In the same manner as in Synthesis example 1- (1), 15.0 g (36.6 mmol) of 2-bromo-9,9-diphenylfluorene was added to 5.84 g (41.5 mmol) of propionyl chloride of 5.53 g (41.5 mmol) of anhydrous aluminum chloride. 15.4 g (90%) of yellow 1- (7-bromo-9,9-diphenylfluoren-2-yl) propan-1-one was obtained.
1H NMR (δ ppm; DMSO-d 6): 8.18~8.17(m, 1H), 8.01~7.95(m, 2H), 7.76~7.75(m, 2H), 7.55~7.54(m, 1H), 7.33~7.27(m, 6H), 7.12~7.11(m, 4H), 3.54~3.53(M, 2H), 1.18~1.17(M, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18-8.17 (m, 1H), 8.01-7.95 (m, 2H), 7.76-7.75 (m, 2H), 7.55-7.54 (m, 1H), 7.33-7.27 ( m, 6H), 7.12-7.11 (m, 4H), 3.54-3.53 (M, 2H), 1.18-1.17 (M, 3H)
MS(m/e) 454.1MS ( m / e ) 454.1
합성예 7-(2) : 1-(9,9-디페닐-7-(p-톨릴티오)플루오렌-2-닐)프로판-1-온(중간체 7-b)의 합성Synthesis Example 7- (2): Synthesis of 1- (9,9-diphenyl-7- (p-tolylthio) fluoren-2-yl) propan-1-one (intermediate 7-b)
Figure PCTKR2019005284-appb-I000056
Figure PCTKR2019005284-appb-I000056
[중간체 7-b]                                                  [Intermediate 7-b]
합성예 1-(2)와 동일한 방법으로1-(7-브로모-9,9-디페닐플루오렌-2-닐)프로판-1-온 10.0 g (22.1 mmol), 4-메틸벤젠티올 4.1g(33.1mmol)과 탄산칼륨6.1g(44.1mmol)을 사용하여 목적화합물 1-(9,9-디페닐-7-(p-톨릴티오)-플루오렌-2-닐)프로판-1-온 8.8 g (80%) 을 얻었다.10.0 g (22.1 mmol) of 1- (7-bromo-9,9-diphenylfluoren-2-yl) propan-1-one in the same manner as in Synthesis Example 1- (2) 4.1 Compound 1- (9,9-diphenyl-7- (p-tolylthio) -fluoren-2-yl) propan-1-one using g (33.1 mmol) and 6.1 g (44.1 mmol) potassium carbonate 8.8 g (80%) was obtained.
1H NMR (δ ppm; DMSO-d 6): 8.18~8.17(m, 1H), 8.01~7.95(m, 2H), 7.67~7.66(m, 1H), 7.49~7.47(m, 3H), 7.33~7.27(m, 7H), 7.11~7.04(m, 6H), 3.54~3.53(m, 2H), 2.34(s, 3H), 1.18~1.17(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18-8.17 (m, 1H), 8.01-7.95 (m, 2H), 7.67-7.62 (m, 1H), 7.49-7.47 (m, 3H), 7.33-7.27 ( m, 7H), 7.11-7.04 (m, 6H), 3.54-3.53 (m, 2H), 2.34 (s, 3H), 1.18-1.17 (m, 3H)
MS(m/e) : 496.2MS ( m / e ): 496.2
합성예 7-(3) : 1-(9,9-디페닐-7-(p-톨릴티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온(중간체 3-c)의 합성Synthesis Example 7- (3): 1- (9,9-diphenyl-7- (p-tolylthio) -fluoren-2-yl) -2- (hydroxyimino) propan-1-one (intermediate 3 -c) synthesis
Figure PCTKR2019005284-appb-I000057
Figure PCTKR2019005284-appb-I000057
[중간체 7-c]                                                   [Intermediate 7-c]
합성예 1-(3)과 동일한 방법으로 1-(9,9-디페닐-7-(p-톨릴티오)플루오렌-2-닐)프로판-1-온 8.0 g (16.1 mmol) 동당량의 이소아밀나이트리트, 염산을 사용하여 연한 노란색 1-(9,9-디페닐-7-(p-톨릴티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 6.3 g (74 %)을 얻었다.8.0 g (16.1 mmol) equivalent of 1- (9,9-diphenyl-7- (p-tolylthio) fluoren-2-yl) propan-1-one in the same manner as in Synthesis Example 1- (3) Light yellow 1- (9,9-diphenyl-7- (p-tolylthio) -fluoren-2-yl) -2- (hydroxyimino) propan-1-one using isoamyl nitrite, hydrochloric acid 6.3 g (74%) was obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.10~8.07(m, 2H), 7.93~7.9(m, 1H), 7.67~7.66(m, 1H), 7.49~7.47(m, 3H), 7.33~7.27(m, 7H), 7.11~7.04(m, 6H), 3.10(s, 3H), 2.34(s, 3H), 2.10(s, 1H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10 to 8.07 (m, 2H), 7.93 to 7.9 (m, 1H), 7.67 to 7.62 (m, 1H), 7.49 to 7.47 (m, 3H), 7.33 to 7.27 ( m, 7H), 7.11-7.04 (m, 6H), 3.10 (s, 3H), 2.34 (s, 3H), 2.10 (s, 1H)
MS(m/e) : 525.2MS ( m / e ): 525.2
합성예 7-(4) : 2-(아세톡시이미노)-1-(9,9-디페닐-7-(p-톨릴티오)-플루오렌-2-닐)프로판-1-온(화합물 33)의 합성Synthesis Example 7- (4): 2- (Acetoxyimino) -1- (9,9-diphenyl-7- (p-tolylthio) -fluoren-2-yl) propan-1-one (Compound 33 ) Synthesis
Figure PCTKR2019005284-appb-I000058
Figure PCTKR2019005284-appb-I000058
[화합물 33]                                                  [Compound 33]
합성예 1-(4)와 동일한 방법으로1-(9,9-디페닐-7-(p-톨릴티오)플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 8 g (15.2 mmol), 아세틸클로라이드 1.43g(18.3mmol)과 트리에틸아민 2.31g(22.8mmol)사용하여 흰색의 : 2-(아세톡시이미노)-1-(9,9-디페닐-7-(p-톨릴티오)-플루오렌-2-닐)프로판-1-온 (화합물 33) 5.9 g (68 %)을 얻었다.1- (9,9-diphenyl-7- (p-tolylthio) fluoren-2-yl) -2- (hydroxyimino) propan-1-one 8 in the same manner as in Synthesis Example 1- (4) g (15.2 mmol), 1.43 g (18.3 mmol) of acetyl chloride and 2.31 g (22.8 mmol) of triethylamine were used as the white compound: 2- (acetoxyimino) -1- (9,9-diphenyl-7- ( 5.9 g (68%) of p-tolylthio) -fluoren-2-yl) propan-1-one (compound 33) were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.10~8.07(m, 2H), 7.93~7.92(m, 1H), 7.67~7.66(m, 1H), 7.49~7.47(m, 3H), 7.33~7.27(m, 7H), 7.11~7.04(m, 6H), 3.10(s, 3H), 2.34(s, 3H), 2.28(s, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10-8.07 (m, 2H), 7.93-7.72 (m, 1H), 7.67-7.62 (m, 1H), 7.49-7.47 (m, 3H), 7.33-7.27 ( m, 7H), 7.11-7.04 (m, 6H), 3.10 (s, 3H), 2.34 (s, 3H), 2.28 (s, 3H)
MS(m/e) : 567.2MS ( m / e ): 567.2
합성예 8 : 화합물 35의 합성Synthesis Example 8 Synthesis of Compound 35
합성예 8-(1) : 1-(2'-브로모스파이로[시클로헥산-1,9'-플루오렌]-7'-닐)프로판-1-온(중간체 4-a)의 합성Synthesis Example 8- (1): Synthesis of 1- (2'-bromospyro [cyclohexane-1,9'-fluorene] -7'-yl) propan-1-one (intermediate 4-a)
Figure PCTKR2019005284-appb-I000059
Figure PCTKR2019005284-appb-I000059
[중간체 8-a]                                              [Intermediate 8-a]
합성예 1-(1)과 동일한 방법으로 2'-브로모스파이로[시클로헥산-1,9'-플루오렌]15.0 g (47.9mmol)을 무수 염화알루미늄 7.0 g (52.7 mmol) 프로피오닐클로라이드 4.87 g (52.7mmol)을 사용하여 노란색 1-(2'-브로모스파이로[시클로헥산-1,9'-플루오렌]-7'-닐)프로판-1-온 14.9 g (84 %)을 얻었다.In the same manner as in Synthesis Example 1- (1), 15.0 g (47.9 mmol) of 2'-bromospyro [cyclohexane-1,9'-fluorene] was added to 7.0 g (52.7 mmol) propionyl chloride of anhydrous aluminum chloride. g (52.7 mmol) was used to obtain 14.9 g (84%) of yellow 1- (2'-bromospyro [cyclohexane-1,9'-fluorene] -7'-yl) propan-1-one. .
1H NMR (δ ppm; DMSO-d 6): 8.18~8.17(m, 1H), 8.017.95(m, 2H), 7.76~7.72(m, 2H), 7.55~7.54(m, 1H), 3.54~3.53(m, 2H), 2.15~1.95(m, 4H), 1.53~1.43(m, 6H), 1.18~1.17(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18-8.17 (m, 1H), 8.017.95 (m, 2H), 7.76-7.72 (m, 2H), 7.55-7.54 (m, 1H), 3.54-3.53 ( m, 2H), 2.15-1.95 (m, 4H), 1.53-1.43 (m, 6H), 1.18-1.17 (m, 3H)
MS(m/e) 368.1MS ( m / e ) 368.1
합성예 8-(2) : 1-(2'-(페닐티오)스파이로[시클로헥산-1,9'-플루오렌]-7'-닐)프로판-1-온(중간체 8-b)의 합성Synthesis Example 8- (2): of 1- (2 '-(phenylthio) spiro [cyclohexane-1,9'-fluorene] -7'-yl) propan-1-one (intermediate 8-b) synthesis
Figure PCTKR2019005284-appb-I000060
Figure PCTKR2019005284-appb-I000060
[중간체 8-b]                                               [Intermediate 8-b]
합성예 1-(2)와 동일한 방법으로1-(2'-브로모스파이로[시클로헥산-1,9'-플루오렌]-7'-닐)프로판-1-온 14.0 g (37.9 mmol), 벤젠티올 6.3g(56.9mmol)과 탄산칼륨10.5g(75.8mmol)을 사용하여 목적화합물 1-(2'-(페닐티오)스파이로[시클로헥산-1,9'-플루오렌]-7'-닐)프로판-1-온 13.1 g (87%) 을 얻었다.14.0 g (37.9 mmol) of 1- (2'-bromospyro [cyclohexane-1,9'-fluorene] -7'-yl) propan-1-one in the same manner as in Synthesis example 1- (2) , Target compound 1- (2 '-(phenylthio) spiro [cyclohexane-1,9'-fluorene] -7' using 6.3 g (56.9 mmol) of benzenethiol and 10.5 g (75.8 mmol) of potassium carbonate 13.1 g (87%) of -nil) propan-1-one was obtained.
1H NMR (δ ppm; DMSO-d 6): 8.18~8.17(m, 1H), 8.01~7.95(m, 2H), 7.76~7.75(m, 1H), 7.49~7.42(m, 3H), 7.32~7.19(m, 4H), 3.54~3.53(m, 2H), 2.15~1.95(m, 4H), 1.53~1.43(m, 6H), 1.18~1.17(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18-8.17 (m, 1H), 8.01-7.95 (m, 2H), 7.76-7.75 (m, 1H), 7.49-7.42 (m, 3H), 7.32-7.19 ( m, 4H), 3.54-3.53 (m, 2H), 2.15-1.95 (m, 4H), 1.53-1.43 (m, 6H), 1.18-1.17 (m, 3H)
MS(m/e) : 398.2MS ( m / e ): 398.2
합성예 8-(3) : 2-(히드록시이미노)-1-(2'-(페닐티오)스파이로 [시클로헥산-1,9'-플루오렌]-7'-닐)프로판-1-온(중간체 8-c)의 합성Synthesis Example 8- (3): 2- (hydroxyimino) -1- (2 '-(phenylthio) spiro [cyclohexane-1,9'-fluorene] -7'-yl) propane-1- Synthesis of On (Intermediate 8-c)
Figure PCTKR2019005284-appb-I000061
Figure PCTKR2019005284-appb-I000061
[중간체 8-c]                                                  [Intermediate 8-c]
합성예 1-(3)과 동일한 방법으로 1-(2'-(페닐티오)스파이로[시클로헥산-1,9'-플루오렌]-7'-닐)프로판-1-온 10.0 g (25.1 mmol) 동당량의 이소아밀나이트리트, 염산을 사용하여 연한 노란색 1-(9,9-디페닐-7-(p-톨릴티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 7.6 g (71 %)을 얻었다.10.0 g (25.1) of 1- (2 '-(phenylthio) spiro [cyclohexane-1,9'-fluorene] -7'-yl) propan-1-one in the same manner as in Synthesis example 1- (3) mmol) light yellow 1- (9,9-diphenyl-7- (p-tolylthio) -fluorene-2-yl) -2- (hydroxyimino) using isoamylnitrite, equivalents, hydrochloric acid 7.6 g (71%) of propane-1-one were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.10~8.07(m, 2H), 7.93~7.92(m, 1H), 7.67~7.15(m, 1H), 7.49~7.42(m, 3H), 7.32~7.19(m, 4H), 3.10(s, 3H), 2.15~1.95(m, 5H), 1.53~1.43(m, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10-8.07 (m, 2H), 7.93-7.72 (m, 1H), 7.67-7.15 (m, 1H), 7.49-7.42 (m, 3H), 7.32-7.19 ( m, 4H), 3.10 (s, 3H), 2.15-1.95 (m, 5H), 1.53-1.43 (m, 6H)
MS(m/e) : 427.2MS ( m / e ): 427.2
합성예 8-(4) : 2-((벤조옥시)이미노)-1-(2'-(페닐티오)스파이로 [시클로헥산-1,9'-플루오렌]-7'-닐)프로판-1-온(화합물 35)의 합성Synthesis Example 8- (4): 2-((benzooxy) imino) -1- (2 '-(phenylthio) spiro [cyclohexane-1,9'-fluorene] -7'-yl) propane Synthesis of -1-one (Compound 35)
Figure PCTKR2019005284-appb-I000062
Figure PCTKR2019005284-appb-I000062
[화합물 35]                                                [Compound 35]
합성예 1-(4)와 동일한 방법으로1-(9,9-디페닐-7-(p-톨릴티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 8 g (18.7 mmol), 벤조일클로라이드 3.16g(22.5mmol)과 트리에틸아민 2.84g(28.1mmol)사용하여 흰색의 : 2-(아세톡시이미노)-1-(9,9-디페닐-7-(p-톨릴티오)-플루오렌-2-닐)프로판-1-온 (화합물 35) 7.0 g (70 %)을 얻었다.1- (9,9-diphenyl-7- (p-tolylthio) -fluoren-2-yl) -2- (hydroxyimino) propan-1-one in the same manner as in Synthesis Example 1- (4) 8 g (18.7 mmol), 3.16 g (22.5 mmol) of benzoyl chloride and 2.84 g (28.1 mmol) of triethylamine were used in white: 2- (acetoxyimino) -1- (9,9-diphenyl-7- 7.0 g (70%) of (p-tolylthio) -fluoren-2-yl) propan-1-one (compound 35) were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.21~8.20(m, 2H), 8.10~8.06(m, 2H), 7.93~7.92(m, 1H), 7.79~7.78(m, 3H), 7.67~7.66(m, 3H), 7.49~7.41(m, 3H), 7.32~7.19(m, 4H), 3.10(s, 3H), 2.15~1.95(m, 4H), 1.53~1.43(m, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.21 to 8.20 (m, 2H), 8.10 to 8.06 (m, 2H), 7.93 to 7.82 (m, 1H), 7.79 to 7.78 (m, 3H), 7.67 to 7.62 ( m, 3H), 7.49-7.41 (m, 3H), 7.32-7.19 (m, 4H), 3.10 (s, 3H), 2.15-1.95 (m, 4H), 1.53-1.43 (m, 6H)
MS(m/e) : 531.2MS ( m / e ): 531.2
합성예 9 : 화합물 53의 합성Synthesis Example 9 Synthesis of Compound 53
합성예 9-(1) : 1-(2-브로모-9,9-디메틸-플루오렌-7-닐)펜탄-1-온(중간체 9-a)의 합성Synthesis Example 9- (1): Synthesis of 1- (2-bromo-9,9-dimethyl-fluorene-7-yl) pentan-1-one (intermediate 9-a)
Figure PCTKR2019005284-appb-I000063
Figure PCTKR2019005284-appb-I000063
[중간체 9-a]                                          [Intermediate 9-a]
합성예 1-(1)과 동일한 방법으로2-브로모-9,9-디메틸-플루오렌10.0 g (36.6mmol)을 무수 염화알루미늄 5.37 g (40.3 mmol) 발러릴클로라이드 4.86 g (40.3mmol)을 사용하여 노란색 1-(2-브로모-9,9-디메틸-플루오렌-7-닐)펜탄-1-온 10.6 g (81 %)을 얻었다.In the same manner as in Synthesis example 1- (1), 10.0 g (36.6 mmol) of 2-bromo-9,9-dimethyl-fluorene was added to 5.86 g (40.3 mmol) of valerian chloride of 5.37 g (40.3 mmol) of anhydrous aluminum chloride. 10.6 g (81%) of yellow 1- (2-bromo-9,9-dimethyl-fluorene-7-yl) pentan-1-one was obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.18(s, 1H), 8.02~7.97(m, 2H), 7.76~7.72(m, 2H), 7.56~7.55(m, 1H), 2.96~2.95(m, 2H), 1.72(s, 6H), 1.44~1.34(m, 4H), 0.91~0.90(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18 (s, 1H), 8.02-7.97 (m, 2H), 7.76-7.72 (m, 2H), 7.56-7.55 (m, 1H), 2.96-2.95 (m, 2H), 1.72 (s, 6H), 1.44-1.34 (m, 4H), 0.91-0.90 (m, 3H)
MS(m/e) : 356.1MS ( m / e ): 356.1
합성예 9-(2) : 1-(9,9-디메틸-2-(나프탈렌-2-닐티오) -플루오렌-7-닐)펜탄-1-온(중간체 9-b)의 합성Synthesis Example 9- (2): Synthesis of 1- (9,9-dimethyl-2- (naphthalene-2-ylthio) -fluorene-7-yl) pentan-1-one (intermediate 9-b)
Figure PCTKR2019005284-appb-I000064
Figure PCTKR2019005284-appb-I000064
[중간체 9-b]                                              [Intermediate 9-b]
합성예 1-(2)와 동일한 방법으로1-(2-브로모-9,9-디메틸플로오렌-7-닐)펜탄-1-온 9.0 g (25.2 mmol), 나프탈렌-2닐-티올 6.1g(37.8mmol)과 탄산칼륨 7.0g(50.4mmol)을 사용하여 목적화합물 1-(9,9-디메틸-2-(나프탈렌-2-닐티오) -플루오렌-7-닐)펜탄-1-온 9.2 g (84%) 을 얻었다.9.0 g (25.2 mmol) of 1- (2-bromo-9,9-dimethylfloorene-7-yl) pentan-1-one in the same manner as in Synthesis Example 1- (2), naphthalene-2yl-thiol 6.1 g (37.8 mmol) and 7.0 g (50.4 mmol) of potassium carbonate were used to prepare the desired compound 1- (9,9-dimethyl-2- (naphthalene-2-ylthio) -fluorene-7-yl) pentane-1- 9.2 g (84%) were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.18(s, 1H), 8.01~7.96(m, 4H), 7.80~7.79(m, 1H), 7.66~7.59(m, 4H), 7.49~7.48(m, 1H), 7.32~7.27(m, 2H), 2.96~2.95(m, 2H), 1.72(s, 6H), 1.44~1.34(m, 4H), 0.91~0.90(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18 (s, 1H), 8.01-7.96 (m, 4H), 7.80-7.79 (m, 1H), 7.66-7.59 (m, 4H), 7.49-7.48 (m, 1H), 7.32-7.27 (m, 2H), 2.96-2.95 (m, 2H), 1.72 (s, 6H), 1.44-1.34 (m, 4H), 0.91-0.90 (m, 3H)
MS(m/e) : 436.2MS ( m / e ): 436.2
합성예 9-(3) : 2-(히드록시이미노)-1-(9,9-메틸-2-(나프탈렌-2-닐티오)- 플루오렌-7-닐)펜탄-1-온 (중간체 9-c)의 합성Synthesis Example 9- (3): 2- (hydroxyimino) -1- (9,9-methyl-2- (naphthalene-2-ylthio) -fluorene-7-yl) pentan-1-one (intermediate) Synthesis of 9-c)
Figure PCTKR2019005284-appb-I000065
Figure PCTKR2019005284-appb-I000065
[중간체 9-c]                                                 [Intermediate 9-c]
합성예 1-(3)과 동일한 방법으로 1-(9,9-디메틸-2-(나프탈렌-2-닐티오) -플루오렌-7-닐)펜탄-1-온 9.0 g (20.6 mmol) 동당량의 이소아밀나이트리트, 염산을 사용하여 연한 노란색 2-(히드록시이미노)-1-(9,9-메틸-2-(나프탈렌-2-닐티오)- 플루오렌-7-닐)펜탄-1-온 6.8 g (71 %)을 얻었다.9.0 g (20.6 mmol) of 1- (9,9-dimethyl-2- (naphthalen-2-ylthio) -fluorene-7-yl) pentan-1-one in the same manner as in Synthesis Example 1- (3) Light yellow 2- (hydroxyimino) -1- (9,9-methyl-2- (naphthalene-2-ylthio)-fluorene-7-yl) pentane- using an equivalent of isoamyl nitrite, hydrochloric acid 6.8 g (71%) of 1-one were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.10~7.93(m, 5H), 7.80~7.79(m, 1H), 7.66~7.59(m, 4H), 7.49~7.48(m, 1H), 7.32~7.27(m, 2H), 2.21(s, 1H), 1.72(s, 6H), 1.62~1.53(m, 4H), 0.91~0.90(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10-7.73 (m, 5H), 7.80-7.79 (m, 1H), 7.66-7.59 (m, 4H), 7.49-7.48 (m, 1H), 7.32-7.27 ( m, 2H), 2.21 (s, 1H), 1.72 (s, 6H), 1.62-1.53 (m, 4H), 0.91-0.90 (m, 3H)
MS(m/e) : 465.2MS ( m / e ): 465.2
합성예 9-(4) : 1-(9,9-디메틸-2-(나프탈렌-2-닐티오)-플루오렌-7-닐)-2-(((3-아세틸)옥시)이미노)펜탄-1-온(화합물 53)의 합성Synthesis Example 9- (4): 1- (9,9-dimethyl-2- (naphthalene-2-ylthio) -fluorene-7-yl) -2-(((3-acetyl) oxy) imino) Synthesis of Pentan-1-one (Compound 53)
Figure PCTKR2019005284-appb-I000066
Figure PCTKR2019005284-appb-I000066
[화합물 53]                                                   [Compound 53]
합성예 1-(4)와 동일한 방법으로2-(히드록시이미노)-1-(9,9-메틸-2-(나프탈렌-2-닐티오)- 플루오렌-7-닐)펜탄-1-온 5 g (10.7 mmol), 아세틸클로라이드와 1.01g(12.9mmol) 트리에틸아민 1.63g(16.1mmol)사용하여 흰색의 1-(9,9-디메틸-2-(나프탈렌-2-닐티오)- 플루오렌-7-닐)-2-(((3-아세틸)옥시)이미노)펜탄-1-온 (화합물 54) 4.6 g (85 %)을 얻었다.2- (hydroxyimino) -1- (9,9-methyl-2- (naphthalene-2-ylthio) -fluorene-7-yl) pentane-1- in the same manner as in Synthesis example 1- (4) 5 g (10.7 mmol), 1- (9,9-dimethyl-2- (naphthalene-2-ylthio)--white, using acetyl chloride and 1.63 g (16.1 mmol) of 1.01 g (12.9 mmol) triethylamine. 4.6 g (85%) of fluorene-7-yl) -2-(((3-acetyl) oxy) imino) pentan-1-one (compound 54) was obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.10~7.93(m, 5H), 7.80~7.79(m, 1H), 7.66~7.59(m, 4H), 7.49~7.48(m, 1H), 7.32~7.27(m, 2H), 2.28(s, 3H), 1.72(s, 6H), 1.62~1.53(m, 4H), 0.91~0.90(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10-7.73 (m, 5H), 7.80-7.79 (m, 1H), 7.66-7.59 (m, 4H), 7.49-7.48 (m, 1H), 7.32-7.27 ( m, 2H), 2.28 (s, 3H), 1.72 (s, 6H), 1.62-1.53 (m, 4H), 0.91-0.90 (m, 3H)
MS(m/e) : 507.2MS ( m / e ): 507.2
합성예 10 : 화합물 59의 합성Synthesis Example 10 Synthesis of Compound 59
합성예 10-(1) : 1-(6,7-디브로모-9,9-디메틸-플루오렌-2-닐)프로판-1-온(중간체 10-a)의 합성Synthesis Example 10- (1): Synthesis of 1- (6,7-dibromo-9,9-dimethyl-fluoren-2-yl) propan-1-one (intermediate 10-a)
Figure PCTKR2019005284-appb-I000067
Figure PCTKR2019005284-appb-I000067
[중간체 10-a]                                             [Intermediate 10-a]
합성예 1-(1)과 동일한 방법으로2,3-디브로모-9,9-디메틸-플루오렌 15.0 g (42.6mmol)을 무수 염화알루미늄 6.25 g (46.9 mmol) 프로피오닐클로라이드 4.34 g (46.9mmol)을 사용하여 노란색 1-(6,7-디브로모-9,9-디메틸-플루오렌-2-닐)프로판-1-온 15.7 g (90 %)을 얻었다.In the same manner as in Synthesis Example 1- (1), 15.0 g (42.6 mmol) of 2,3-dibromo-9,9-dimethyl-fluorene was added to 6.34 g (46.9 mmol) propionyl chloride of anhydrous aluminum chloride. mmol) gave 15.7 g (90%) of yellow 1- (6,7-dibromo-9,9-dimethyl-fluoren-2-yl) propan-1-one.
1H NMR (δ ppm; DMSO-d 6) : 8.11~8.10(m, 1H), 8.01~7.95(m, 3H), 7.61~7.60(m, 8H), 3.54~3.55(m, 2H), 1.71(s, 6H), 1.18~1.17(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.11-8.10 (m, 1H), 8.01-7.95 (m, 3H), 7.61-7.60 (m, 8H), 3.54-3.55 (m, 2H), 1.71 (s, 6H), 1.18-1.17 (m, 3H)
MS(m/e) : 408.0MS ( m / e ): 408.0
합성예 10-(2) : 1-(9,9-디메틸-6,7-비스(페닐티오)-플루오렌-2-닐)프로판-1-온(중간체 10-b)의 합성Synthesis Example 10- (2): Synthesis of 1- (9,9-dimethyl-6,7-bis (phenylthio) -fluoren-2-yl) propan-1-one (intermediate 10-b)
Figure PCTKR2019005284-appb-I000068
Figure PCTKR2019005284-appb-I000068
[중간체 10-b]                                                 [Intermediate 10-b]
합성예 1-(2)와 동일한 방법으로 1-(6,7-디브로모-9,9-디메틸-플루오렌-2-닐)프로판-1-온 10.0 g (24.5 mmol)을 벤젠티올 8.1g(73.5mmol)과 탄산칼륨 13.5g(98.0mmol)을 사용하여 목적화합물 1-(9,9-디메틸-6,7-비스(페닐티오)-9H-플루오렌-2-닐)프로판-1-온 9.7 g (85%) 을 얻었다. In the same manner as in Synthesis example 1- (2), 10.0 g (24.5 mmol) of 1- (6,7-dibromo-9,9-dimethyl-fluoren-2-yl) propan-1-one was added to benzenethiol 8.1 Compound 1- (9,9-dimethyl-6,7-bis (phenylthio) -9H-fluorene-2-yl) propane-1 using g (73.5 mmol) and 13.5 g (98.0 mmol) of potassium carbonate 9.7 g (85%) was obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.11~8.10(m, 1H), 8.01~7.95(m, 2H), 7.58~7.57(m, 1H), 7.41~7.40(m, 4H), 7.29~7.20(m, 7H), 3.54~3.55(m, 2H), 1.71(s, 6H), 1.18~1.17(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.11-8.10 (m, 1H), 8.01-7.95 (m, 2H), 7.58-7.57 (m, 1H), 7.41-7.40 (m, 4H), 7.29-7.20 ( m, 7H), 3.54-3.55 (m, 2H), 1.71 (s, 6H), 1.18-1.17 (m, 3H)
MS(m/e) : 466.1MS ( m / e ): 466.1
합성예 10-(3) : 1-(9,9-디메틸-6,7-비스(페닐티오)-플루오렌-2-닐)-2-(하이드록시이미노)프로판-1-온 (중간체 10-c)의 합성Synthesis Example 10- (3): 1- (9,9-dimethyl-6,7-bis (phenylthio) -fluoren-2-yl) -2- (hydroxyimino) propan-1-one (intermediate 10 -c) synthesis
Figure PCTKR2019005284-appb-I000069
Figure PCTKR2019005284-appb-I000069
[중간체 10-c]                                                  [Intermediate 10-c]
합성예 1-(3)과 동일한 방법으로 1-(9,9-디메틸-6,7-비스(페닐티오)-플루오렌-2-닐)프로판-1-온 10.0 g (21.4 mmol) 동당량의 이소아밀나이트리트, 염산을 사용하여 연한 노란색 1-(9,9-디메틸-6,7-비스(페닐티오)-플루오렌-2-닐)-2-(하이드록시이미노)프로판-1-온 7.2 g (68 %)을 얻었다.10.0 g (21.4 mmol) equivalent of 1- (9,9-dimethyl-6,7-bis (phenylthio) -fluoren-2-yl) propan-1-one in the same manner as in Synthesis Example 1- (3) Isoamyl nitrite, light yellow 1- (9,9-dimethyl-6,7-bis (phenylthio) -fluorene-2-yl) -2- (hydroxyimino) propane-1- using hydrochloric acid Obtained 7.2 g (68%).
1H NMR (δ ppm; DMSO-d 6) : 8.11~8.10(m, 2H), 7.95~7.94(m, 1H), 7.58~7.57(m, 1H), 7.41~7.40(m, 4H), 7.29~7.20(m, 7H), 3.12(s, 3H), 3.01(s, 1H), 1.71(s, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.11-8.10 (m, 2H), 7.95-7.74 (m, 1H), 7.58-7.57 (m, 1H), 7.41-7.40 (m, 4H), 7.29-7.20 ( m, 7H), 3.12 (s, 3H), 3.01 (s, 1H), 1.71 (s, 6H)
MS(m/e) : 495.1MS ( m / e ): 495.1
합성예 10-(4) : 1-(((1-(9,9-디메틸-6,7-비스(페닐티오)-플루오렌-2-닐)-1-옥소프로판-2-닐리덴)아미노)옥시)부탄-1-온(화합물 59)의 합성Synthesis Example 10- (4): 1-(((1- (9,9-dimethyl-6,7-bis (phenylthio) -fluorene-2-yl) -1-oxopropane-2-ylidene) Synthesis of Amino) oxy) butan-1-one (Compound 59)
Figure PCTKR2019005284-appb-I000070
Figure PCTKR2019005284-appb-I000070
[화합물 59]                                                 [Compound 59]
합성예 1-(4)와 동일한 방법으로1-(9,9-디메틸-6,7-비스(페닐티오)-플루오렌-2-닐)-2-(하이드록시이미노)프로판-1-온 5 g (10.1 mmol), 부터릴클로라이드 1.29g(12.1mmol)과 트리에틸아민 1.53g(15.1mmol)사용하여 흰색의 1-(((1-(9,9-디메틸-6,7-비스(페닐티오)-플루오렌-2-닐)-1-옥소프로판-2-닐리덴)아미노)옥시)부탄-1-온(화합물 59) 4.7 g (82 %)을 얻었다.1- (9,9-dimethyl-6,7-bis (phenylthio) -fluoren-2-yl) -2- (hydroxyimino) propan-1-one in the same manner as in Synthesis Example 1- (4) 5 g (10.1 mmol), 1.29 g (12.1 mmol) of aryryl chloride and 1.53 g (15.1 mmol) of triethylamine were prepared using white 1-(((1- (9,9-dimethyl-6,7-bis ( 4.7 g (82%) of phenylthio) -fluorene-2-yl) -1-oxopropan-2-nilidene) amino) oxy) butan-1-one (Compound 59) were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.11~8.10(m, 2H), 7.95~7.94(m, 1H), 7.58~7.57(m, 1H), 7.41~7.40(m, 4H), 7.29~7.20(m, 7H), 3.12(s, 3H), 2.30~2.29(m, 2H), 1.17~1.68(m, 8H), 0.90~0.89(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.11-8.10 (m, 2H), 7.95-7.74 (m, 1H), 7.58-7.57 (m, 1H), 7.41-7.40 (m, 4H), 7.29-7.20 ( m, 7H), 3.12 (s, 3H), 2.30-2.29 (m, 2H), 1.17-1.68 (m, 8H), 0.90-0.99 (m, 3H)
MS(m/e) : 565.2MS ( m / e ): 565.2
합성예 11 : 화합물 61의 합성Synthesis Example 11 Synthesis of Compound 61
합성예 11-(1) : 1-(9,9-디메틸-6,7-비스(메틸티오)-플루오렌-2-닐)프로판-1-온(중간체 11-a)의 합성Synthesis Example 11- (1): Synthesis of 1- (9,9-dimethyl-6,7-bis (methylthio) -fluoren-2-yl) propan-1-one (intermediate 11-a)
Figure PCTKR2019005284-appb-I000071
Figure PCTKR2019005284-appb-I000071
[중간체 11-a]                                                    [Intermediate 11-a]
합성예 1-(2)와 동일한 방법으로 1-(6,7-디브로모-9,9-디메틸-플루오렌-2-닐)프로판-1-온 10.0 g (24.5 mmol)을 메틸티올 3.4g(98.0mmol)과 탄산칼륨 16.9g(122.5mmol)을 사용하여 목적화합물 1-(9,9-디메틸-6,7-비스(메틸티오)-플루오렌-2-닐)프로판-1-온 7.6 g (91%) 을 얻었다. In the same manner as in Synthesis Example 1- (2), 10.0 g (24.5 mmol) of 1- (6,7-dibromo-9,9-dimethyl-fluoren-2-yl) propan-1-one was dissolved in methylthiol 3.4 Compound 1- (9,9-dimethyl-6,7-bis (methylthio) -fluoren-2-yl) propan-1-one using g (98.0 mmol) and 16.9 g (122.5 mmol) of potassium carbonate 7.6 g (91%) was obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.18~8.17(m, 1H), 8.01~7.96(m, 2H), 7.66~7.65(m, 1H), 7.37~7.36(m, 1H), 3.54~3.52(m, 2H), 2.53(s, 3H), 2.52(s, 3H), 1.71(s, 6H), 1.18~1.17(s, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18-8.17 (m, 1H), 8.01-7.96 (m, 2H), 7.66-7.75 (m, 1H), 7.37-7.36 (m, 1H), 3.54-3.52 ( m, 2H), 2.53 (s, 3H), 2.52 (s, 3H), 1.71 (s, 6H), 1.18-1.17 (s, 3H)
MS(m/e) : 342.1MS ( m / e ): 342.1
합성예 11-(2) : 1-(9,9-디메틸-6,7-비스(메틸티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온(중간체 11-b)의 합성Synthesis Example 11- (2): 1- (9,9-dimethyl-6,7-bis (methylthio) -fluoren-2-yl) -2- (hydroxyimino) propan-1-one (intermediate 11 synthesis of -b)
Figure PCTKR2019005284-appb-I000072
Figure PCTKR2019005284-appb-I000072
[중간체 11-b]                                                 [Intermediate 11-b]
합성예 1-(3)과 동일한 방법으로 1-(9,9-디메틸-6,7-비스(메틸티오)-플루오렌-2-닐)프로판-1-온 10.0 g (29.2 mmol) 동당량의 이소아밀나이트리트, 염산을 사용하여 연한 노란색 1-(9,9-디메틸-6,7-비스(메틸티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 7.5 g (69 %)을 얻었다.10.0 g (29.2 mmol) equivalent of 1- (9,9-dimethyl-6,7-bis (methylthio) -fluoren-2-yl) propan-1-one in the same manner as in Synthesis Example 1- (3) Isoamyl nitrite, light yellow 1- (9,9-dimethyl-6,7-bis (methylthio) -fluoren-2-yl) -2- (hydroxyimino) propane-1- using hydrochloric acid Obtained 7.5 g (69%).
1H NMR (δ ppm; DMSO-d 6) : 8.10~8.06(m, 2H), 7.93~7.92(m, 1H), 7.66~7.65(m, 1H), 7.37~7.36(m, 1H), 3.10(s, 3H), 2.53(s, 3H), 2.52(s, 3H), 2.01(s, 1H), 1.71(s, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10-8.06 (m, 2H), 7.93-7.72 (m, 1H), 7.66-7.75 (m, 1H), 7.37-7.36 (m, 1H), 3.10 (s, 3H), 2.53 (s, 3H), 2.52 (s, 3H), 2.01 (s, 1H), 1.71 (s, 6H)
MS(m/e) : 371.1MS ( m / e ): 371.1
합성예 11-(3) : 1-(((1-(9,9-디메틸-6,7-비스(메틸티오)-플루오렌-2-닐)-1-옥소프로판-2-닐리덴)아미노)옥시)헥산-1-온(화합물 61)의 합성Synthesis Example 11- (3): 1-(((1- (9,9-dimethyl-6,7-bis (methylthio) -fluorene-2-yl) -1-oxopropane-2-nilidene) Synthesis of amino) oxy) hexan-1-one (Compound 61)
Figure PCTKR2019005284-appb-I000073
Figure PCTKR2019005284-appb-I000073
[화합물 61]                                                 Compound 61
합성예 1-(4)와 동일한 방법으로1-(9,9-디메틸-6,7-비스(메틸티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 5 g (13.5 mmol), 헥사노일클로라이드 2.17g(16.1mmol)과 트리에틸아민 2.0g(20.2mmol)사용하여 1-(((1-(9,9-디메틸-6,7-비스(메틸티오)-플루오렌-2-닐)-1-옥소프로판-2-닐리덴)아미노)옥시)헥산-1-온(화합물 61) 4.9 g (77%)을 얻었다.1- (9,9-dimethyl-6,7-bis (methylthio) -fluoren-2-yl) -2- (hydroxyimino) propan-1-one in the same manner as in Synthesis example 1- (4) 5 g (13.5 mmol), 2.17 g (16.1 mmol) of hexanoyl chloride and 2.0 g (20.2 mmol) of triethylamine were used to prepare 1-(((1- (9,9-dimethyl-6,7-bis (methylthio) 4.9 g (77%) of) -fluorene-2-yl) -1-oxopropane-2-nilidene) amino) oxy) hexan-1-one (Compound 61) was obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.10~8.06(m, 2H), 7.93~7.92(m, 1H), 7.66~7.65(m, 1H), 7.37~7.36(m, 1H), 3.10(s, 3H), 2.53(3H), 2.52(s, 3H), 2.23~2.28(m, 2H), 1.71(s, 6H), 1.52~1.51(m, 2H), 1.31~1.29(m, 4H), 0.90~0.89(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10-8.06 (m, 2H), 7.93-7.72 (m, 1H), 7.66-7.75 (m, 1H), 7.37-7.36 (m, 1H), 3.10 (s, 3H), 2.53 (3H), 2.52 (s, 3H), 2.23-2.28 (m, 2H), 1.71 (s, 6H), 1.52-1.51 (m, 2H), 1.31-1.29 (m, 4H), 0.90 ~ 0.89 (m, 3H)
MS(m/e) : 469.2MS ( m / e ): 469.2
합성예 12 : 화합물 80의 합성Synthesis Example 12 Synthesis of Compound 80
합성예 12-(1) : 1-(9,9-디메틸-7-(페닐티오)-플루오렌-2-닐)펜탄-1-온(중간체 8-a)의 합성Synthesis Example 12- (1): Synthesis of 1- (9,9-dimethyl-7- (phenylthio) -fluoren-2-yl) pentan-1-one (intermediate 8-a)
Figure PCTKR2019005284-appb-I000074
Figure PCTKR2019005284-appb-I000074
[중간체 12-a]                                                [Intermediate 12-a]
합성예 1-(2)와 동일한 방법으로1-(2-브로모-9,9-디메틸플로오렌-7-닐)펜탄-1-온 10.0 g (28.0 mmol), 벤젠티올4.6g(42.0mmol)과 탄산칼륨 7.7g(56.0mmol)을 사용하여 목적화합물 1-(9,9-디메틸-7-(페닐티오)-플루오렌-2-닐)펜탄-1-온 9.6 g (89%) 을 얻었다.In the same manner as in Synthesis Example 1- (2), 10.0 g (28.0 mmol) of 1- (2-bromo-9,9-dimethylfluoroene-7-yl) pentan-1-one and 4.6 g (42.0 mmol) of benzenethiol ) And 7.7 g (56.0 mmol) of potassium carbonate were used to prepare 9.6 g (89%) of the target compound 1- (9,9-dimethyl-7- (phenylthio) -fluorene-2-yl) pentan-1-one. Got it.
1H NMR (δ ppm; DMSO-d 6) : 8.15(s, 1H), 8.01~7.98(m, 2H), 7.45~7.41(m, 4H), 7.32~7.19(m, 4H), 2.96~2.95(m, 2H), 1.71(s, 6H), 1.47~1.43(m, 2H), 1.35~1.31(m, 2H), 0.90~0.89(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.15 (s, 1H), 8.01-7.98 (m, 2H), 7.45-7.41 (m, 4H), 7.32-7.19 (m, 4H), 2.96-2.95 (m, 2H), 1.71 (s, 6H), 1.47-1.43 (m, 2H), 1.35-1.31 (m, 2H), 0.90-0.99 (m, 3H)
MS(m/e) : 386.2MS ( m / e ): 386.2
합성예12-(2) : 1-(9,9-디메틸-7-(페닐티오)-플루오렌-2-닐)펜탄-1-온 옥심(중간체 12-b)의 합성Synthesis Example 12- (2): Synthesis of 1- (9,9-dimethyl-7- (phenylthio) -fluoren-2-yl) pentan-1-one oxime (intermediate 12-b)
Figure PCTKR2019005284-appb-I000075
Figure PCTKR2019005284-appb-I000075
[중간체 12-b]                                                 [Intermediate 12-b]
1-(9,9-디메틸-7-(페닐티오)-플루오렌-2-닐)펜탄-1-온 9g(23.3mmol)을 250ml반응기에 넣고 에탄올100ml을 넣고 강하게 교반한다. 그 후 수산화 나트륨 1.1g(27.9mmol)을 넣고 빙초산 1.7g(27.9mmol)을 넣고 교반 후 하이드록시 암모늄 클로라이드 1.9g(27.9mmol)을 넣고 3시간 교반한다. 증류수 50ml을 넣고 18시간동안 교반하여 생성된 고체를 여과 후 컬럼 분리하여 흰색의 목적화합물 1-(9,9-디메틸-7-(페닐티오)-플루오렌-2-닐)펜탄-1-온 옥심 6.2g(66%)를 얻었다.9 g (23.3 mmol) of 1- (9,9-dimethyl-7- (phenylthio) -fluoren-2-yl) pentan-1-one are placed in a 250 ml reactor, 100 ml of ethanol is added, and the mixture is stirred vigorously. Then, 1.1 g (27.9 mmol) of sodium hydroxide was added thereto, 1.7 g (27.9 mmol) of glacial acetic acid was added thereto, followed by stirring, and 1.9 g (27.9 mmol) of hydroxyammonium chloride was added thereto, followed by stirring for 3 hours. 50 ml of distilled water was added and stirred for 18 hours, and the resulting solid was filtered and separated by column to obtain white target compound 1- (9,9-dimethyl-7- (phenylthio) -fluoren-2-yl) pentan-1-one. 6.2 g (66%) of oximes were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.19~8.04(m, 3H), 7.45~7.41(m, 4H), 7.32~7.19(m, 4H), 2.72~2.71(m, 2H), 2.01(s, 1H), 1.71(s, 6H), 1.47~1.43(m, 2H), 1.35~1.31(m, 2H), 0.90~0.89(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.19-8.04 (m, 3H), 7.45-7.41 (m, 4H), 7.32-7.19 (m, 4H), 2.72-2.71 (m, 2H), 2.01 (s, 1H), 1.71 (s, 6H), 1.47-1.43 (m, 2H), 1.35-1.31 (m, 2H), 0.90-0.99 (m, 3H)
MS(m/e) : 401.2MS ( m / e ): 401.2
합성예 12-(3) : 1-(9,9-디메틸-7-(페닐티오)-플루오렌-2-닐)펜탄-1-온 O-아세틸 옥심(화합물 80)의 합성Synthesis Example 12- (3): Synthesis of 1- (9,9-dimethyl-7- (phenylthio) -fluoren-2-yl) pentan-1-one O-acetyl oxime (Compound 80)
Figure PCTKR2019005284-appb-I000076
Figure PCTKR2019005284-appb-I000076
[화합물 80]                                                   [Compound 80]
합성예 1-(4)와 동일한 방법으로1-(9,9-디메틸-7-(페닐티오)-플루오렌-2-닐)펜탄-1-온 옥심 5 g (12.5 mmol), 아세틸클로라이드와 1.17g(14.9mmol) 트리에틸아민 1.89(18.7mmol)을 사용하여 흰색의 1-(9,9-디메틸-7-(페닐티오)-플루오렌-2-닐)펜탄-1-온 O-아세틸 옥심(화합물 80) 4.2 g (75 %)을 얻었다.5 g (12.5 mmol) of 1- (9,9-dimethyl-7- (phenylthio) -fluoren-2-yl) pentan-1-one oxime in the same manner as in Synthesis example 1- (4); White 1- (9,9-dimethyl-7- (phenylthio) -fluoren-2-yl) pentan-1-one O-acetyl using 1.17 g (14.9 mmol) triethylamine 1.89 (18.7 mmol) 4.2 g (75%) of oxime (compound 80) were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.19~8.04(m, 3H), 7.45~7.41(m, 4H), 7.32~7.19(m, 4H), 2.72~2.71(m, 2H), 2.28(s, 3H), 1.71(s, 6H), 1.47~1.43(m, 2H), 1.35~1.31(m, 2H), 0.90~0.89(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.19-8.04 (m, 3H), 7.45-7.41 (m, 4H), 7.32-7.19 (m, 4H), 2.72-2.71 (m, 2H), 2.28 (s, 3H), 1.71 (s, 6H), 1.47-1.43 (m, 2H), 1.35-1.31 (m, 2H), 0.90-0.99 (m, 3H)
MS(m/e) : 443.2MS ( m / e ): 443.2
합성예 13 : 화합물 101의 합성Synthesis Example 13 Synthesis of Compound 101
합성예 13-(1) : 1-(2,7-디브로모-9,9-디메틸-플루오렌-3-닐)부탄-1-온 (중간체 13-a)의 합성Synthesis Example 13- (1): Synthesis of 1- (2,7-dibromo-9,9-dimethyl-fluoren-3-yl) butan-1-one (intermediate 13-a)
Figure PCTKR2019005284-appb-I000077
Figure PCTKR2019005284-appb-I000077
[중간체 13-a]                                                        [Intermediate 13-a]
합성예 1-(1)과 동일한 방법으로 2,7-디브로모-9,9-디메틸-플루오렌20.0 g (56.8mmol)을 무수 염화알루미늄 8.3 g (62.5 mmol) 부티릴클로라이드 6.7 g (62.5mmol)을 사용하여 노란색 1-(2,7-디브로모-9,9-디메틸-플루오렌-3-닐)부탄-1-온 17.7 g (74 %)을 얻었다.In the same manner as in Synthesis Example 1- (1), 20.0 g (56.8 mmol) of 2,7-dibromo-9,9-dimethyl-fluorene was added to 6.7 g (62.5 mmol) of butyryl chloride of anhydrous aluminum chloride. mmol) gave 17.7 g (74%) of yellow 1- (2,7-dibromo-9,9-dimethyl-fluoren-3-yl) butan-1-one.
1H NMR (δ ppm; DMSO-d 6) : 8.34(s, 1H), 7.80~7.74(m, 3H), 7.55~7.54(m, 1H), 2.96~2.95(m, 2H), 1.71(s, 6H), 1.59~1.58(m, 2H), 0.90~0.89(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.34 (s, 1H), 7.80-7.74 (m, 3H), 7.55-7.54 (m, 1H), 2.96-2.95 (m, 2H), 1.71 (s, 6H) , 1.59-1.58 (m, 2H), 0.90-0.89 (m, 3H)
MS(m/e) : 422.0MS ( m / e ): 422.0
합성예 13-(2) : 1-(9,9-디메틸-2,7-비스(페닐티오)-플루오렌-3-닐)부탄-1-온 (중간체 13-b)의 합성Synthesis Example 13- (2): Synthesis of 1- (9,9-dimethyl-2,7-bis (phenylthio) -fluoren-3-yl) butan-1-one (intermediate 13-b)
Figure PCTKR2019005284-appb-I000078
Figure PCTKR2019005284-appb-I000078
[중간체13-b]                                                   [Intermediate 13-b]
합성예1-(2)와 동일한 방법으로1-(2,7-디브로모-9,9-디메틸-플루오렌-3-닐)부탄-1-온 15.0 g (35.5mmol), 벤젠티올15.7.g(142.1mmol)과 탄산칼륨 24.6g(177.7mmol)을 사용하여 목적화합물 1-(9,9-디메틸-2,7-비스(페닐티오)-플루오렌-3-닐)부탄-1-온 14.5 g (85%) 을 얻었다.Synthesis Example 1- (2) In the same manner as 1- (2,7-dibromo-9,9-dimethyl-fluoren-3-yl) butan-1-one 15.0 g (35.5 mmol), benzenethiol 15.7 Compound 1- (9,9-dimethyl-2,7-bis (phenylthio) -fluorene-3-yl) butane-1- using .g (142.1 mmol) and 24.6 g (177.7 mmol) potassium carbonate 14.5 g (85%) were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.28(s, 1H), 7.67~7.66(M, 1H), 7.57~7.50(M, 2H), 7.41~7.40(m, 4H), 7.32~7.19(m, 7H), 2.96~2.95(m, 2H), 1.71(s, 6H), 1.59~1.58(m, 2H), 0.90~0.89(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.28 (s, 1H), 7.67 ~ 7.66 (M, 1H), 7.57 ~ 7.50 (M, 2H), 7.41 ~ 7.40 (m, 4H), 7.32 ~ 7.19 (m, 7H), 2.96-2.95 (m, 2H), 1.71 (s, 6H), 1.59-1.58 (m, 2H), 0.90-0.99 (m, 3H)
MS(m/e) : 480.2MS ( m / e ): 480.2
합성예 13-(3): 1-(9,9-디메틸-2,7-비스(페닐티오)-플루오렌-3-닐)-2-(히드록시이미노)부탄-1-온(중간체 13-c)의 합성Synthesis Example 13- (3): 1- (9,9-dimethyl-2,7-bis (phenylthio) -fluorene-3-yl) -2- (hydroxyimino) butan-1-one (intermediate 13 -c) synthesis
Figure PCTKR2019005284-appb-I000079
Figure PCTKR2019005284-appb-I000079
[중간체13-c]                                                   [Intermediate 13-c]
합성예1-(3)과 동일한 방법으로 1-(9,9-디메틸-2,7-비스(페닐티오)-플루오렌-3-닐)부탄-1-온 10.0 g (20.8mmol) 동당량의 이소아밀나이트리트, 염산을 사용하여 연한 노란색 1-(9,9-디메틸-2,7-비스(페닐티오)-플루오렌-3-닐)-2-(히드록시이미노)부탄-1-온 7.5 g (71 %)을 얻었다.10.0 g (20.8 mmol) equivalent of 1- (9,9-dimethyl-2,7-bis (phenylthio) -fluorene-3-yl) butan-1-one in the same manner as in Synthesis Example 1- (3) Light yellow 1- (9,9-dimethyl-2,7-bis (phenylthio) -fluorene-3-yl) -2- (hydroxyimino) butane-1- using isoamyl nitrite, hydrochloric acid 7.5 g (71%) was obtained.
1H NMR (δ ppm; DMSO-d 6) 8.19(s, 1H), 7.67~7.66(m, 2H), 7.49(s, 1H), 7.41~7.40(m, 4H), 7.32~7.19(m, 7H), 2.10(s, 1H), 1.71(s, 6H), 1.57~1.56(m, 2H), 1.04~1.03(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ) 8.19 (s, 1H), 7.67-77.6 (m, 2H), 7.49 (s, 1H), 7.41-7.40 (m, 4H), 7.32-7.19 (m, 7H), 2.10 (s, 1H), 1.71 (s, 6H), 1.57 ~ 1.56 (m, 2H), 1.04 ~ 1.03 (m, 3H)
MS(m/e) : 509.2MS ( m / e ): 509.2
합성예 13-(4) : 2-(아세톡시이미노)-1-(9,9-디메틸-2,7-비스(페닐티오)-플루오렌-3-닐)부탄-1-온 (화합물 101)합성Synthesis Example 13- (4): 2- (Acetoxyimino) -1- (9,9-dimethyl-2,7-bis (phenylthio) -fluoren-3-yl) butan-1-one (Compound 101 )synthesis
Figure PCTKR2019005284-appb-I000080
Figure PCTKR2019005284-appb-I000080
[화합물101]                                                     Compound 101
합성예1-(4)와 동일한 1-(9,9-디메틸-2,7-비스(페닐티오)-플루오렌-3-닐)-2-(히드록시이미노)부탄-1-온 5.0 g (9.81mmol), 아세틸클로라이드 0.92g(11.8mmol)와 트리에틸아민 1.5g(14.7mmol)사용하여 흰색의 2-(아세톡시이미노)-1-(9,9-디메틸-2,7-비스(페닐티오)-플루오렌-3-닐)부탄-1-온 (화합물 101 ) 4.1 g (75 %)을 얻었다.5.0 g of 1- (9,9-dimethyl-2,7-bis (phenylthio) -fluorene-3-yl) -2- (hydroxyimino) butan-1-one same as in Synthesis Example 1- (4) (9.81 mmol), 0.92 g (11.8 mmol) of acetyl chloride and 1.5 g (14.7 mmol) of triethylamine were used as white 2- (acetoxyimino) -1- (9,9-dimethyl-2,7-bis ( 4.1 g (75%) of phenylthio) -fluorene-3-yl) butan-1-one (Compound 101) were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.19(s, 1H), 7.68~7.67(m, 2H), 7.49~7.40(m, 5H), 7.32~7.19(m, 7H), 2.28(s, 3H), 1.71(s, 6H), 1.57~1.56(m, 2H), 1.04~1.03(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.19 (s, 1H), 7.68-7.76 (m, 2H), 7.49-7.40 (m, 5H), 7.32-7.19 (m, 7H), 2.28 (s, 3H) , 1.71 (s, 6H), 1.57 to 1.56 (m, 2H), 1.04 to 1.03 (m, 3H)
MS(m/e) : 551.2MS ( m / e ): 551.2
합성예 14 : 화합물 134의 합성Synthesis Example 14 Synthesis of Compound 134
합성예 14-(1) : 1-(8-브로모디벤조[b,d]티오펜-2-닐)프로판-1-온(중간체 14-a)의 합성Synthesis Example 14- (1): Synthesis of 1- (8-bromodibenzo [b, d] thiophen-2-yl) propan-1-one (intermediate 14-a)
Figure PCTKR2019005284-appb-I000081
Figure PCTKR2019005284-appb-I000081
[중간체 14-a]                                        [Intermediate 14-a]
합성예 1-(1)과 동일한 방법으로2-브로모디벤조[b,d]티오펜 10.0 g (38.0mmol)을 무수 염화알루미늄 5.57 g (41.8 mmol) 프로피오닐클로라이드 3.87 g (41.8mmol)을 사용하여 노란색 1-(8-브로모디벤조[b,d]티오펜-2-닐)프로판-1-온 9.7 g (80 %)을 얻었다.In the same manner as in Synthesis Example 1- (1), 10.0 g (38.0 mmol) of 2-bromodibenzo [b, d] thiophene was used with 5.87 g (41.8 mmol) of propionyl chloride (3.87 g) (41.8 mmol) 9.7 g (80%) of yellow 1- (8-bromodibenzo [b, d] thiophen-2-yl) propan-1-one was obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.46~8.45(s, 1H), 8.05~8.04(m, 1H), 7.96~7.87(m, 3H), 7.46~7.45(m, 1H), 3.55~3.54(m, 2H), 1.18~1.17(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.46-8.45 (s, 1H), 8.05-8.04 (m, 1H), 7.96-7.87 (m, 3H), 7.46-7.45 (m, 1H), 3.55-3.54 ( m, 2H), 1.18-1.17 (m, 3H)
MS(m/e) : 320.0MS ( m / e ): 320.0
합성예 14-(2) : 1-(8-(페닐티오)디벤조[b,d]티오펜-2-닐)프로판-1-온(중간체 14-b)의 합성Synthesis Example 14- (2): Synthesis of 1- (8- (phenylthio) dibenzo [b, d] thiophen-2-yl) propan-1-one (intermediate 14-b)
Figure PCTKR2019005284-appb-I000082
Figure PCTKR2019005284-appb-I000082
[중간체 14-b]                                            [Intermediate 14-b]
합성예 1-(2)와 동일한 방법으로1-(8-브로모디벤조[b,d]티오펜-2-닐)프로판-1-온 9.0 g (28.2 mmol), 벤젠티올4.7g(42.3mmol)과 탄산칼륨 7.8g(56.4mmol)을 사용하여 목적화합물 1-(8-(페닐티오)디벤조[b,d]티오펜-2-닐)프로판-1-온 9.0 g (92%) 을 얻었다.9.0 g (28.2 mmol) of 1- (8-bromodibenzo [b, d] thiophen-2-yl) propan-1-one and 4.7 g (42.3 mmol) of benzenethiol in the same manner as in Synthesis example 1- (2) ) And 9.0 g (92%) of the target compound 1- (8- (phenylthio) dibenzo [b, d] thiophen-2-yl) propan-1-one using 7.8 g (56.4 mmol) of potassium carbonate. Got it.
1H NMR (δ ppm; DMSO-d 6) : 8.46~8.45(s, 1H), 8.05~8.04(m, 1H), 7.91~7.90(m, 1H), 7.78~7.74(m, 2H), 7.41~7.40(m, 2H), 7.25~7.20(m, 4H), 3.55~3.54(m, 2H), 1.18~1.17(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.46-8.45 (s, 1H), 8.05-8.04 (m, 1H), 7.91-7.90 (m, 1H), 7.78-7.74 (m, 2H), 7.41-7.40 ( m, 2H), 7.25-7.20 (m, 4H), 3.55-3.54 (m, 2H), 1.18-1.17 (m, 3H)
MS(m/e) : 348.1MS ( m / e ): 348.1
합성예 14-(3) : 2-(히드록시이미노)-1-(8-(페닐티오)디벤조[b,d]티오펜-2-닐)프로판-1-온(중간체 14-c)의 합성Synthesis Example 14- (3): 2- (hydroxyimino) -1- (8- (phenylthio) dibenzo [b, d] thiophen-2-yl) propan-1-one (intermediate 14-c) Synthesis of
Figure PCTKR2019005284-appb-I000083
Figure PCTKR2019005284-appb-I000083
[중간체 14-c]                                               [Intermediate 14-c]
합성예 1-(3)과 동일한 방법으로 1-(8-(페닐티오)디벤조[b,d]티오펜-2-닐)프로판-1-온 9.0 g (25.8 mmol) 동당량의 이소아밀나이트리트, 염산을 사용하여 연한 노란색 2-(히드록시이미노)-1-(8-(페닐티오)디벤조[b,d]티오펜-2-닐)프로판-1-온 7.2 g (74 %)을 얻었다.9.0 g (25.8 mmol) equivalent of isoamyl of 1- (8- (phenylthio) dibenzo [b, d] thiophen-2-yl) propan-1-one in the same manner as in Synthesis Example 1- (3) 7.2 g (74%) pale yellow 2- (hydroxyimino) -1- (8- (phenylthio) dibenzo [b, d] thiophen-2-yl) propan-1-one with nitrile, hydrochloric acid )
1H NMR (δ ppm; DMSO-d 6) : 8.37(s, 1H), 8.17~8.16(m, 1H), 7.82~7.76(m, 3H), 7.41~7.40(m, 2H), 7.25~7.20(m, 4H), 3.10(s, 3H), 2.09(s, 1H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.37 (s, 1H), 8.17-8.16 (m, 1H), 7.82-7.72 (m, 3H), 7.41-7.40 (m, 2H), 7.25-7.20 (m, 4H), 3.10 (s, 3H), 2.09 (s, 1H)
MS(m/e) : 377.1MS ( m / e ): 377.1
합성예 14-(4) : 2-(아세톡시이미노)-1-(8-(페닐티오)디벤조[b,d]티오펜-2-닐)프로판-1-온(화합물 134)의 합성Synthesis Example 14- (4): Synthesis of 2- (acetoxyimino) -1- (8- (phenylthio) dibenzo [b, d] thiophen-2-yl) propan-1-one (Compound 134)
Figure PCTKR2019005284-appb-I000084
Figure PCTKR2019005284-appb-I000084
[화합물 134]                                                  [Compound 134]
합성예 1-(4)와 동일한 방법으로2-(히드록시이미노)-1-(8-(페닐티오)디벤조[b,d]티오펜-2-닐)프로판-1-온 5 g (13.2 mmol), 아세틸클로라이드와 1.25g(15.9mmol) 트리에틸아민 1.63g(19.7mmol)사용하여 흰색의 2-(아세톡시이미노)-1-(8-(페닐티오)디벤조[b,d]티오펜-2-닐)프로판-1-온 (화합물 134) 4.2 g (75 %)을 얻었다.5 g of 2- (hydroxyimino) -1- (8- (phenylthio) dibenzo [b, d] thiophen-2-yl) propan-1-one in the same manner as in Synthesis Example 1- (4) 13.2 mmol), and white 2- (acetoxyimino) -1- (8- (phenylthio) dibenzo [b, d] using acetyl chloride and 1.63 g (19.7 mmol) of 1.25 g (15.9 mmol) triethylamine. 4.2 g (75%) of thiophen-2-yl) propan-1-one (compound 134) was obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.37(s, 1H), 8.17~8.16(m, 1H), 7.82~7.76(m, 3H), 7.41~7.40(m, 2H), 7.25~7.20(m, 4H), 3.11(s, 3H), 2.27(s, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.37 (s, 1H), 8.17-8.16 (m, 1H), 7.82-7.72 (m, 3H), 7.41-7.40 (m, 2H), 7.25-7.20 (m, 4H), 3.11 (s, 3H), 2.27 (s, 3H)
MS(m/e) : 419.1MS ( m / e ): 419.1
합성예 15 : 화합물 275의 합성Synthesis Example 15 Synthesis of Compound 275
합성예 15-(1) : 1-(8-브로모디벤조[b,d]퓨란-2-닐)펜탄-1-온(중간체 15-a)의 합성Synthesis Example 15- (1): Synthesis of 1- (8-bromodibenzo [b, d] furan-2-yl) pentan-1-one (intermediate 15-a)
Figure PCTKR2019005284-appb-I000085
Figure PCTKR2019005284-appb-I000085
[중간체 15-a]                                       [Intermediate 15-a]
합성예 1-(1)과 동일한 방법으로2-브로모디벤조[b,d]퓨란 10.0 g (40.5mmol)을 무수 염화알루미늄 5.94 g (44.5 mmol) 발러릴클로라이드 5.37 g (44.5mmol)을 사용하여 노란색 1-(8-브로모디벤조[b,d]퓨란-2-닐)펜탄-1-온 10.3 g (77 %)을 얻었다.In the same manner as in Synthesis Example 1- (1), 10.0 g (40.5 mmol) of 2-bromodibenzo [b, d] furan was prepared by using 5.94 g (44.5 mmol) valeryl chloride of 5.37 g (44.5 mmol) of anhydrous aluminum chloride. 10.3 g (77%) of yellow 1- (8-bromodibenzo [b, d] furan-2-yl) pentan-1-one was obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.17~8.13(m, 3H), 7.64~7.63(m, 1H), 7.55~7.54(m, 1H), 7.36~7.35(m, 1H), 2.97~2.95(m, 2H), 1.44~1.33(m, 4H), 0.91~0.90(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.17-8.13 (m, 3H), 7.64-7.63 (m, 1H), 7.55-7.54 (m, 1H), 7.36-7.35 (m, 1H), 2.97-2.95 ( m, 2H), 1.44-1.33 (m, 4H), 0.91-0.90 (m, 3H)
MS(m/e) : 330.0MS ( m / e ): 330.0
합성예 15-(2) : 1-(8-(페닐티오)디벤조[b,d]퓨란-2-닐)펜탄-1-온(중간체 15-b) 합성Synthesis Example 15- (2): Synthesis of 1- (8- (phenylthio) dibenzo [b, d] furan-2-yl) pentan-1-one (intermediate 15-b)
Figure PCTKR2019005284-appb-I000086
Figure PCTKR2019005284-appb-I000086
[중간체 15-b]                                              [Intermediate 15-b]
합성예 1-(2)와 동일한 방법으로1-(8-브로모디벤조[b,d]퓨란-2-닐)펜탄-1-온 9.0 g (27.2 mmol), 벤젠티올4.5g(40.8mmol)과 탄산칼륨 7.5g(54.3mmol)을 사용하여 목적화합물 1-(8-(페닐티오)디벤조[b,d]퓨란-2-닐)펜탄-1-온 9.1 g (93%) 을 얻었다.9.0 g (27.2 mmol) of 1- (8-bromodibenzo [b, d] furan-2-yl) pentan-1-one in the same manner as in Synthesis example 1- (2), 4.5 g (40.8 mmol) of benzenethiol 7.5 g (54.3 mmol) of potassium carbonate were used to obtain 9.1 g (93%) of the target compound 1- (8- (phenylthio) dibenzo [b, d] furan-2-yl) pentan-1-one.
1H NMR (δ ppm; DMSO-d 6) :8.17~8.13(m, 2H), 7.64~7.63(m, 1H), 7.46~7.41(m, 4H), 7.25~7.15(m, 4H), 2.97~2.95(m, 2H), 1.44~1.33(m, 4H), 0.91~0.90(m, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.17 to 8.13 (m, 2H), 7.64 to 7.63 (m, 1H), 7.46 to 7.41 (m, 4H), 7.25 to 7.15 (m, 4H), 2.97 to 2.95 ( m, 2H), 1.44-1.33 (m, 4H), 0.91-0.90 (m, 3H)
MS(m/e) : 360.1MS ( m / e ): 360.1
합성예 15-(3) : 2-(히드록시이미노)-1-(8-(페닐티오)디벤조[b,d]퓨란-2-닐)펜탄-1-온(중간체 15-c)의 합성Synthesis Example 15- (3): of 2- (hydroxyimino) -1- (8- (phenylthio) dibenzo [b, d] furan-2-yl) pentan-1-one (intermediate 15-c) synthesis
Figure PCTKR2019005284-appb-I000087
Figure PCTKR2019005284-appb-I000087
[중간체 15-c]                                                 [Intermediate 15-c]
합성예 1-(3)과 동일한 방법으로 1-(8-(페닐티오)디벤조[b,d]퓨란-2-닐)펜탄-1-온 9.0 g (25.0 mmol) 동당량의 이소아밀나이트리트, 염산을 사용하여 연한 노란색 2-(히드록시이미노)-1-(8-(페닐티오)디벤조[b,d]퓨란-2-닐)펜탄-1-온 6.8 g (70 %)을 얻었다.9.0 g (25.0 mmol) isoamyl age of 1- (8- (phenylthio) dibenzo [b, d] furan-2-yl) pentan-1-one in the same manner as in Synthesis Example 1- (3) 6.8 g (70%) of pale yellow 2- (hydroxyimino) -1- (8- (phenylthio) dibenzo [b, d] furan-2-yl) pentan-1-one using trit, hydrochloric acid Got it.
1H NMR (δ ppm; DMSO-d 6) : 8.08~8.05(m, 2H), 7.75~7.74(m, 1H), 7.46~7.41(m, 4H), 7.25~7.15(m, 4H), 2.01(s, 1H), 1.62~1.55(m, 4H), 0.91~0.90(s, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.08 to 8.05 (m, 2H), 7.75 to 7.74 (m, 1H), 7.46 to 7.41 (m, 4H), 7.25 to 7.15 (m, 4H), 2.01 (s, 1H), 1.62-1.55 (m, 4H), 0.91-0.90 (s, 3H)
MS(m/e) : 389.1MS ( m / e ): 389.1
합성예 15-(4) : 2-(아세톡시이미노)-1-(8-(페닐티오)디벤조[b,d]퓨란-2-닐)펜탄-1-온(화합물 275)의 합성Synthesis Example 15- (4): Synthesis of 2- (acetoxyimino) -1- (8- (phenylthio) dibenzo [b, d] furan-2-yl) pentan-1-one (Compound 275)
Figure PCTKR2019005284-appb-I000088
Figure PCTKR2019005284-appb-I000088
[화합물 275]                                                  [Compound 275]
합성예 1-(4)와 동일한 방법으로2-(히드록시이미노)-1-(8-(페닐티오)디벤조[b,d]퓨란-2-닐)펜탄-1-온 5 g (12.8 mmol), 아세틸클로라이드와 1.21g(15.4mmol) 트리에틸아민 1.63g(19.3mmol)사용하여 흰색의 2-(아세톡시이미노)-1-(8-(페닐티오)디벤조[b,d]티오펜-2-닐)프로판-1-온 (화합물 275) 3.9 g (70 %)을 얻었다.5 g (12.8) of 2- (hydroxyimino) -1- (8- (phenylthio) dibenzo [b, d] furan-2-yl) pentan-1-one in the same manner as in Synthesis example 1- (4) mmol), white 2- (acetoxyimino) -1- (8- (phenylthio) dibenzo [b, d] teeth using acetyl chloride and 1.63 g (19.3 mmol) of 1.21 g (15.4 mmol) triethylamine. 3.9 g (70%) of offen-2-yl) propan-1-one (compound 275) were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.08~8.05(m, 2H), 7.75~7.74(m, 1H), 7.46~7.41(m, 4H), 7.25~7.15(m, 4H), 2.27(s, 3H), 1.62~1.55(m, 4H), 0.91~0.90(s, 3H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.08 to 8.05 (m, 2H), 7.75 to 7.74 (m, 1H), 7.46 to 7.41 (m, 4H), 7.25 to 7.15 (m, 4H), 2.27 (s, 3H), 1.62-1.55 (m, 4H), 0.91-0.90 (s, 3H)
MS(m/e) : 431.1MS ( m / e ): 431.1
합성예 16 : 화합물324의 합성Synthesis Example 16 Synthesis of Compound 324
합성예 16-(1) : 1-(7-브로모-9,9-디부틸-8-니트로-플루오렌-2-닐)프로판-1-온Synthesis Example 16- (1): 1- (7-Bromo-9,9-dibutyl-8-nitro-fluoren-2-yl) propan-1-one (중간체 16-a)의 합성Synthesis of (Intermediate 16-a)
Figure PCTKR2019005284-appb-I000089
Figure PCTKR2019005284-appb-I000089
[중간체 16-a]                                                  [Intermediate 16-a]
합성예 1-(1)과 동일한 방법으로 2-브로모-9,9-디부틸-1-니트로-플루오렌15.0 g (37.28mmol)을 무수 염화알루미늄 5.47 g (41.0 mmol) 프로피오닐클로라이드 3.79 g (41.0mmol)을 사용하여 흰색의 1-(7-브로모-9,9-디부틸-8-니트로-플루오렌-2-닐)프로판-1-온 14.52 g (85 %)을 얻었다.In the same manner as in Synthesis example 1- (1), 15.0 g (37.28 mmol) of 2-bromo-9,9-dibutyl-1-nitro-fluorene was added to 5.79 g (41.0 mmol) propionyl chloride of anhydrous aluminum chloride. White 1- (7-bromo-9,9-dibutyl-8-nitro-fluoren-2-yl) propan-1-one using (41.0 mmol) 14.52 g (85%) was obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.18~8.15(m, 2H), 8.01~7.95(m, 2H), 7.81~7.80(m, 1H), 3.54~3.53(m, 2H), 1.87~1.86(m, 4H), 1.31~1.18(m, 11H), 0.90~0.89(m, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18-8.15 (m, 2H), 8.01-7.95 (m, 2H), 7.81-7.80 (m, 1H), 3.54-3.53 (m, 2H), 1.87-1.86 ( m, 4H), 1.31-1.18 (m, 11H), 0.90-0.99 (m, 6H)
(m/e) : 457.1( m / e ): 457.1
합성예 16-(2) : 1-(9,9-디부틸-8-니트로-7-(페닐티오)-플루오렌-2-닐)프로판-1-온 (중간체 16-b)의 합성Synthesis Example 16- (2): Synthesis of 1- (9,9-dibutyl-8-nitro-7- (phenylthio) -fluoren-2-yl) propan-1-one (intermediate 16-b)
Figure PCTKR2019005284-appb-I000090
Figure PCTKR2019005284-appb-I000090
[중간체 16-b]                                                 [Intermediate 16-b]
합성예 1-(2)와 동일한 방법으로1-(7-브로모-9,9-디부틸-8-니트로-플루오렌-2-닐)프로판-1-온 14.0 g (30.54 mmol), 벤젠티올 5.05g(45.8mmol)과 탄산칼륨 8.44g(61.1mmol)을 사용하여 목적화합물 1-(9,9-디부틸-8-니트로-7-(페닐티오)-플루오렌-2-닐)프로판-1-온 11.9 g (80%) 을 얻었다.14.0 g (30.54 mmol) of 1- (7-bromo-9,9-dibutyl-8-nitro-fluoren-2-yl) propan-1-one in the same manner as in Synthesis example 1- (2), benzene Target compound 1- (9,9-dibutyl-8-nitro-7- (phenylthio) -fluoren-2-yl) propane using 5.05 g (45.8 mmol) of thiol and 8.44 g (61.1 mmol) of potassium carbonate 11.9 g (80%) of 1-one were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.18(s, 1H), 8.06~7.06(m, 3H), 7.58~7.57(m, 1H), 7.41~7.40(m, 2H), 7.25~7.19(m, 3H), 3.54~3.53(m, 2H), 1.87~1.86(m, 4H), 1.31~1.18(m, 11H), 0.90~0.89(m, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.18 (s, 1H), 8.06-7.06 (m, 3H), 7.58-7.57 (m, 1H), 7.41-7.40 (m, 2H), 7.25-7.19 (m, 3H), 3.54-3.53 (m, 2H), 1.87-1.86 (m, 4H), 1.31-1.18 (m, 11H), 0.90-0.99 (m, 6H)
MS(m/e) : 487.2MS ( m / e ): 487.2
합성예 16-(3) : 1-(9,9-디부틸-8-니트로-7-(페닐티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 (중간체 16-c)의 합성Synthesis Example 16- (3): 1- (9,9-Dibutyl-8-nitro-7- (phenylthio) -fluoren-2-yl) -2- (hydroxyimino) propan-1-one ( Synthesis of Intermediate 16-c)
Figure PCTKR2019005284-appb-I000091
Figure PCTKR2019005284-appb-I000091
[중간체 16-c]                                                   [Intermediate 16-c]
합성예 1-(3)과 동일한 방법으로 1-(9,9-디부틸-8-니트로-7-(페닐티오)-플루오렌-2-닐)프로판-1-온 10.0 g (20.51 mmol) 동당량의 이소아밀나이트리트, 염산을 사용하여 연한 노란색 1-(9,9-디부틸-8-니트로-7-(페닐티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 8.9 g (84 %)을 얻었다.10.0 g (20.51 mmol) of 1- (9,9-dibutyl-8-nitro-7- (phenylthio) -fluorene-2-yl) propan-1-one in the same manner as in Synthesis example 1- (3) Light yellow 1- (9,9-dibutyl-8-nitro-7- (phenylthio) -fluorene-2-yl) -2- (hydroxyimino) using an equivalent of isoamyl nitrite, hydrochloric acid 8.9 g (84%) of propane-1-one were obtained.
1H NMR (δ ppm; DMSO-d 6): 8.10~8.06(m, 3H), 7.93~7.92(, 1H), 7.58~7.57(m, 1H), 7.41~7.40(m, 2H), 7.25~7.19(m, 3H), 3.11(s, 3H), 2.01(s, 1H), 1.87~1.86(m, 4H), 1.31~1.29(m, 8H), 0.90~0.89(m, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10-8.06 (m, 3H), 7.93-7.72 (, 1H), 7.58-7.57 (m, 1H), 7.41-7.40 (m, 2H), 7.25-7.19 (m , 3H), 3.11 (s, 3H), 2.01 (s, 1H), 1.87-1.86 (m, 4H), 1.31-1.29 (m, 8H), 0.90-0.89 (m, 6H)
MS(m/e) : 516.2MS ( m / e ): 516.2
합성예 16-(4) : 2-(아세톡시이미노)-1-(9,9-디부틸-8-니트로-7-(페닐티오)- 플루오렌-2-닐)프로판-1-온 (화합물 324)의 합성Synthesis Example 16- (4): 2- (acetoxyimino) -1- (9,9-dibutyl-8-nitro-7- (phenylthio)-fluoren-2-yl) propan-1-one ( Synthesis of Compound 324)
Figure PCTKR2019005284-appb-I000092
Figure PCTKR2019005284-appb-I000092
[화합물 324]                                                  [Compound 324]
합성예 1-(4)와 동일한 방법으로1-(9,9-디부틸-8-니트로-7-(페닐티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 5 g (9.68 mmol), 아세틸클로라이드와 0.91g(11.6mmol) 트리에틸아민 1.47g(14.5mmol)사용하여 흰색의 2-(아세톡시이미노)-1-(9,9-디부틸-8-니트로-7-(페닐티오)- 플루오렌-2-닐)프로판-1-온 (화합물 324) 4.1 g (75 %)을 얻었다.1- (9,9-Dibutyl-8-nitro-7- (phenylthio) -fluorene-2-yl) -2- (hydroxyimino) propane-1 in the same manner as in Synthesis example 1- (4) 5 g (9.68 mmol) of -on, 1.47 g (14.5 mmol) of 0.91 g (11.6 mmol) triethylamine with acetylchloride and white 2- (acetoxyimino) -1- (9,9-dibutyl-8 4.1 g (75%) of -nitro-7- (phenylthio) -fluoren-2-yl) propan-1-one (compound 324) were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.10~8.06(m, 3H), 7.93~7.92(, 1H), 7.58~7.57(m, 1H), 7.41~7.40(m, 2H), 7.25~7.19(m, 3H), 3.11(s, 3H), 2.28(s, 3H), 1.87~1.86(m, 4H), 1.31~1.29(m, 8H), 0.90~0.89(m, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.10-8.06 (m, 3H), 7.93-7.72 (, 1H), 7.58-7.57 (m, 1H), 7.41-7.40 (m, 2H), 7.25-7.19 (m , 3H), 3.11 (s, 3H), 2.28 (s, 3H), 1.87-1.86 (m, 4H), 1.31-1.29 (m, 8H), 0.90-0.99 (m, 6H)
MS(m/e) : 558.2MS ( m / e ): 558.2
합성예 17 : 화합물330의 합성Synthesis Example 17 Synthesis of Compound 330
합성예 17-(1) : 1-(7-브로모-9,9-디에틸-3-메틸-8-페닐-플루오렌-2-닐)프로판-1-온Synthesis Example 17- (1): 1- (7-Bromo-9,9-diethyl-3-methyl-8-phenyl-fluoren-2-yl) propan-1-one (중간체 17-a)의 합성Synthesis of (Intermediate 17-a)
Figure PCTKR2019005284-appb-I000093
Figure PCTKR2019005284-appb-I000093
[중간체 17-a]                                                  [Intermediate 17-a]
합성예 1-(1)과 동일한 방법으로 2-브로모-9,9-디에틸-6-메틸-1-페닐-플루오렌 15 g (38.3mmol)을 무수 염화알루미늄 5.62 g (42.16 mmol) 프로피오닐클로라이드 3.9 g (42.2mmol)을 사용하여 흰색의 1-(7-브로모-9,9-디에틸-3-메틸-8-페닐-플루오렌-2-닐)프로판-1-온 15.1 g (88 %)을 얻었다.In the same manner as in Synthesis example 1- (1), 15 g (38.3 mmol) of 2-bromo-9,9-diethyl-6-methyl-1-phenyl-fluorene was added 5.62 g (42.16 mmol) of propane anhydrous aluminum chloride. 15.1 g of white 1- (7-bromo-9,9-diethyl-3-methyl-8-phenyl-fluoren-2-yl) propan-1-one using 3.9 g (42.2 mmol) of onyl chloride (88%) was obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.06(s, 1H), 7.72~7.71(m, 2H), 7.61~7.60(m, 1H), 7.52~7.41(m, 5H), 354~3.53(m, 2H), 2.48(s, 3H), 1.19~1.90(m, 4H), 1.18~1.17(m, 3H), 0.90~0.89(m, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.06 (s, 1H), 7.72 ~ 7.71 (m, 2H), 7.61 ~ 7.60 (m, 1H), 7.52 ~ 7.41 (m, 5H), 354 ~ 3.53 (m, 2H), 2.48 (s, 3H), 1.19-1.90 (m, 4H), 1.18-1.17 (m, 3H), 0.90-0.99 (m, 6H)
(m/e) : 446.1( m / e ): 446.1
합성예 17-(2) : 1-(9,9-디에틸-3-메틸-8-페닐-7-(페닐티오)-플루오렌-2-닐)프로판-1-온 (중간체 17-b)의 합성Synthesis Example 17- (2): 1- (9,9-diethyl-3-methyl-8-phenyl-7- (phenylthio) -fluoren-2-yl) propan-1-one (intermediate 17-b ) Synthesis
Figure PCTKR2019005284-appb-I000094
Figure PCTKR2019005284-appb-I000094
[중간체 17-b]                                                [Intermediate 17-b]
합성예 1-(2)와 동일한 방법으로1-(7-브로모-9,9-디에틸-3-메틸-8-페닐-플루오렌-2-닐)프로판-1-온 14.0 g (31.29 mmol), 벤젠티올 5.17g(46.94mmol)과 탄산칼륨 8.65g(62.6mmol)을 사용하여 목적화합물 1-(9,9-디에틸-3-메틸-8-페닐-7-(페닐티오)-플루오렌-2-닐)프로판-1-온 12.4 g (83%) 을 얻었다.14.0 g of 1- (7-bromo-9,9-diethyl-3-methyl-8-phenyl-fluoren-2-yl) propan-1-one (31.29) in the same manner as in Synthesis example 1- (2) mmol), 5.17 g (46.94 mmol) of benzenethiol and 8.65 g (62.6 mmol) of potassium carbonate were used to give the titled compound 1- (9,9-diethyl-3-methyl-8-phenyl-7- (phenylthio)- 12.4 g (83%) of fluorene-2-yl) propan-1-one were obtained.
1H NMR (δ ppm; DMSO-d 6) : 8.06(s, 1H), 7.72(s, 1H), 7.63~7.61(m, 1H), 7.52~7.38(m, 8H), 7.25~7.19(m, 3H), 3.54~3.53(m, 2H), 2.48(s, 3H), 1.19~1.90(m, 4H), 1.18~1.17(m, 3H), 0.90~0.89(m, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 8.06 (s, 1H), 7.72 (s, 1H), 7.63 ~ 7.61 (m, 1H), 7.52 ~ 7.38 (m, 8H), 7.25 ~ 7.19 (m, 3H) , 3.54 to 3.53 (m, 2H), 2.48 (s, 3H), 1.19 to 1.90 (m, 4H), 1.18 to 1.17 (m, 3H), 0.90 to 0.99 (m, 6H)
MS(m/e) : 476.2MS ( m / e ): 476.2
합성예 17-(3) : 1-(9,9-디에틸-3-메틸-8-페닐-7-(페닐티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 (중간체17-c)의 합성Synthesis Example 17- (3): 1- (9,9-Diethyl-3-methyl-8-phenyl-7- (phenylthio) -fluorene-2-yl) -2- (hydroxyimino) propane- Synthesis of 1-one (Intermediate 17-c)
Figure PCTKR2019005284-appb-I000095
Figure PCTKR2019005284-appb-I000095
[중간체 17-c]                                                  [Intermediate 17-c]
합성예 1-(3)과 동일한 방법으로 1-(9,9-디에틸-3-메틸-8-페닐-7-(페닐티오)-플루오렌-2-닐)프로판-1-온 10.0 g (21.0 mmol) 동당량의 이소아밀나이트리트, 염산을 사용하여 연한 노란색 1-(9,9-디에틸-3-메틸-8-페닐-7-(페닐티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 8.5 g (80 %)을 얻었다.10.0 g of 1- (9,9-diethyl-3-methyl-8-phenyl-7- (phenylthio) -fluoren-2-yl) propan-1-one in the same manner as in Synthesis Example 1- (3) (21.0 mmol) isoamylnitrite equivalent to light yellow 1- (9,9-diethyl-3-methyl-8-phenyl-7- (phenylthio) -fluoren-2-yl) using hydrochloric acid 8.5 g (80%) of 2- (hydroxyimino) propan-1-one were obtained.
1H NMR (δ ppm; DMSO-d 6): 7.98(s, 1H), 7.83(s, 1H), 7.63~7.61(m, 1H), 7.52~7.38(m, 8H), 7.25~7.19(m, 3H), 3.11(s, 3H), 2.48(s, 3H), 2.01~1.90(m, 5H), 0.90~0.89(m, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 7.98 (s, 1H), 7.83 (s, 1H), 7.63 ~ 7.61 (m, 1H), 7.52 ~ 7.38 (m, 8H), 7.25 ~ 7.19 (m, 3H) , 3.11 (s, 3H), 2.48 (s, 3H), 2.01-1.90 (m, 5H), 0.90-0.99 (m, 6H)
MS(m/e) : 505.2MS ( m / e ): 505.2
합성예 17-(4) : 2-(아세톡시이미노)-1-(9,9-디에틸-3-메틸-8-페닐-7-(페닐티오)- 플루오렌-2-닐)프로판-1-온 (화합물 330)의 합성Synthesis Example 17- (4): 2- (acetoxyimino) -1- (9,9-diethyl-3-methyl-8-phenyl-7- (phenylthio)-fluorene-2-yl) propane- Synthesis of 1-one (Compound 330)
Figure PCTKR2019005284-appb-I000096
Figure PCTKR2019005284-appb-I000096
[화합물 330]                                                 [Compound 330]
합성예 1-(4)와 동일한 방법으로1-(9,9-디에틸-3-메틸-8-페닐-7-(페닐티오)-플루오렌-2-닐)-2-(히드록시이미노)프로판-1-온 5 g (9.9 mmol), 아세틸클로라이드와 0.93g(11.9mmol) 트리에틸아민 1.50g(14.8mmol)사용하여 흰색의 2-(아세톡시이미노)-1-(9,9-디에틸-3-메틸-8-페닐-7-(페닐티오)- 플루오렌-2-닐)프로판-1-온 (화합물 330) 4.1 g (75 %)을 얻었다.1- (9,9-diethyl-3-methyl-8-phenyl-7- (phenylthio) -fluorene-2-yl) -2- (hydroxyimino in the same manner as in Synthesis Example 1- (4) 5 g (9.9 mmol) of propan-1-one, 1.50 g (14.8 mmol) of acetyl chloride and 0.93 g (11.9 mmol) triethylamine were used in white 2- (acetoxyimino) -1- (9,9- 4.1 g (75%) of diethyl-3-methyl-8-phenyl-7- (phenylthio) -fluoren-2-yl) propan-1-one (compound 330) were obtained.
1H NMR (δ ppm; DMSO-d 6) : 7.98(s, 1H), 7.83(s, 1H), 7.63~7.61(m, 1H), 7.52~7.38(m, 8H), 7.25~7.19(m, 3H), 3.11(s, 3H), 2.48(s, 3H), 2.028(s, 3H)1.91~1.90(m, 4H), 0.90~0.89(m, 6H) 1 H NMR (δ ppm; DMSO- d 6 ): 7.98 (s, 1H), 7.83 (s, 1H), 7.63 ~ 7.61 (m, 1H), 7.52 ~ 7.38 (m, 8H), 7.25 ~ 7.19 (m, 3H) , 3.11 (s, 3H), 2.48 (s, 3H), 2.028 (s, 3H) 1.91 ~ 1.90 (m, 4H), 0.90 ~ 0.89 (m, 6H)
MS(m/e) : 547.2MS ( m / e ): 547.2
합성예 18 : 아크릴 중합체(공중합체 1) 제조Synthesis Example 18 Preparation of Acrylic Polymer (Copolymer 1)
500mL 중합용기에 프로필렌글리콜메틸에테르아세테이트 용매 250mL 및 AIBN 2g를 첨가한 후, 아크릴산, 글리시딜메타아크릴레이트, 벤질메타아크릴레이트, 디시클로펜타닐아크릴레이트를 각각 20:30:30:20의 몰비로 아크릴 모노머의 고형분이 35 중량%로 첨가한 다음, 질소 분위기 하에서 65℃로 5시간 교반하며 중합시켜 아크릴 중합체를(공중합체 1) 합성하였다. 이와 같이 제조된 공중합체의 평균 분자량은 14,000, 분산도는 1.8로 확인되었다.250 mL of propylene glycol methyl ether acetate solvent and 2 g of AIBN were added to a 500 mL polymerization vessel, and acrylic acid, glycidyl methacrylate, benzyl methacrylate, and dicyclopentanyl acrylate were each added in a molar ratio of 20: 30: 30: 20. The solid content of the acrylic monomer was added at 35% by weight, followed by polymerization with stirring at 65 ° C. for 5 hours under a nitrogen atmosphere to synthesize an acrylic polymer (copolymer 1). The average molecular weight of the copolymer thus prepared was found to be 14,000, the degree of dispersion is 1.8.
실시예 1 ~ 20 : 포토레지스트 조성물의 제조Examples 1-20: Preparation of Photoresist Compositions
교반기가 설치되어 있는 반응기에 하기 표2에 기재된 성분과 함량에 따라 합성예18에서 제조한 아크릴 공중합체 1, 용매로서 PGMEA(to 100중량부), 광중합성 화합물 및 광개시제를 순차적으로 첨가하고 상온에서 12시간 교반하여 포토레지스트 조성물을 제조하였다. To the reactor equipped with a stirrer, acryl copolymer 1 prepared in Synthesis Example 18 , PGMEA (to 100 parts by weight), a photopolymerizable compound and a photoinitiator were sequentially added according to the components and contents shown in Table 2 below at room temperature. Stirring for 12 hours to prepare a photoresist composition.
상기의 실시예로부터 제조된 포토레지스트의 조성은 하기 표2에서 나타낸 바와 같다.The composition of the photoresist prepared from the above examples is shown in Table 2 below.
[표 2]TABLE 2
Figure PCTKR2019005284-appb-I000097
Figure PCTKR2019005284-appb-I000097
Figure PCTKR2019005284-appb-I000098
Figure PCTKR2019005284-appb-I000098
비교예 1Comparative Example 1
실시예 1에서 광개시제를 화합물 1 대신에 2-(o-벤조일옥심)-1-[4-(페닐티오)페닐]-1,2-옥탄디온을 사용한 것을 제외하고는 동일한 방법으로 포토레지스트를 제조하였다.A photoresist was prepared in the same manner as in Example 1, except that the photoinitiator used 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione in place of compound 1. It was.
비교예 2Comparative Example 2
실시예 2에서 광개시제를 화합물 15 대신에 1-(o-벤조일옥심)- (디벤조[b,d]퓨란-2-일)펜탄온을 사용한 것을 제외하고는 동일한 방법으로 포토레지스트를 제조하였다.A photoresist was prepared in the same manner as in Example 2, except that the photoinitiator used 1- (o-benzoyloxime)-(dibenzo [b, d] furan-2-yl) pentanone instead of compound 15.
비교예 3Comparative Example 3
실시예 3에서 광개시제를 화합물 17 대신에 1-(o-아세틸옥심)-(디벤조[b,d]퓨란-2-일)펜탄온을 사용한 것을 제외하고는 동일한 방법으로 포토레지스트를 제조하였다.A photoresist was prepared in the same manner as in Example 3, except that the photoinitiator used 1- (o-acetyloxime)-(dibenzo [b, d] furan-2-yl) pentanone instead of compound 17.
실험예 : 포토레지스트 평가Experimental Example: Photoresist Evaluation
1) 감도1) Sensitivity
유리 기판위에 포토레지스트를 스핀코팅 하여100℃에서 2분간 핫프레이트에서 가열한 후 스텝 마스크를 이용하여 노광 한 후 0.04% KOH 수용액에서 현상하였다. 스텝 마스크 패턴이 초기 두께 대비 90% 두께를 유지하는 노광량을 감도로 평가 하였다. The photoresist was spin-coated on a glass substrate, heated at 100 ° C. for 2 minutes in a hot plate, exposed using a step mask, and developed in a 0.04% KOH aqueous solution. Sensitivity was evaluated for the exposure amount in which the step mask pattern maintains 90% of the initial thickness.
2) 잔막율2) Residual rate
포토레지스트 조성물을 기판위에 스핀 코터를 이용하여 도포한 후, 100℃에서 2분간 가열하고, 365nm에서 500mJ노광한 후0.04% KOH 수용액에서 현상하였다. 250℃에서 30분간 하드베이크(hard-bake)를 실시하여 포토레지스트 막의 하드베이크 전 후의 두께 비율(%)을 측정하였다.The photoresist composition was applied onto the substrate using a spin coater, heated at 100 ° C. for 2 minutes, exposed to 500 mJ at 365 nm, and developed in a 0.04% KOH aqueous solution. Hard-bake was performed at 250 degreeC for 30 minutes, and the thickness ratio (%) before and after hard baking of the photoresist film was measured.
3) 투과도3) transmittance
포토레지스트 조성물을 기판위에 스핀 코터를 이용하여 도포한 후, 100℃에서 2분간 프리베이크(prebake)하고, 365nm에서 500mJ노광한 후0.04% KOH 수용액에서 현상하였다. 250℃에서 30분간 하드베이크(hard-bake)를 실시한 후 UV-vis 분광광도계로 400nm에서 투과도를 측정하였다.The photoresist composition was applied onto a substrate using a spin coater, then prebaked at 100 ° C. for 2 minutes, exposed to 500 mJ at 365 nm, and developed in a 0.04% KOH aqueous solution. After performing a hard bake at 250 ° C. for 30 minutes, the transmittance was measured at 400 nm using a UV-vis spectrophotometer.
4) 아웃가스4) Outgas
제조한 화합물 및 비교예에 사용된 화합물 각 50mg을 headspace 장비를 이용하여 230oC에서 30분간 가열하여 발생하는 가스를 포집한 후 GC-Mass 장비를 이용하여 전체 발생한 가스의 양을 적분하여 측정 하였다.Each 50mg of the prepared compound and the compound used in the comparative example were collected by heating at 230 ° C. for 30 minutes using a headspace device, and then measured by integrating the total amount of generated gas using a GC-Mass device. .
이상의 실시예 1 내지 20 및 비교예 1 내지 3에 따라 제조된 포토레지스트 조성물의 평가는 유리 기판 위에서 실시하였으며, 레지스트 조성물의 감도, 잔막율, 투과도, 내화학성 등의 성능평가를 실시하였으며, 그 결과를 하기 표 3에 표시하였다.Evaluation of the photoresist composition prepared according to the above Examples 1 to 20 and Comparative Examples 1 to 3 was performed on the glass substrate, and performance evaluation of the sensitivity, residual film ratio, transmittance, chemical resistance, etc. of the resist composition was performed. Is shown in Table 3 below.
실시예Example 감도 (mJ/cm2)Sensitivity (mJ / cm 2 ) 잔막율(%)Residual rate (%) 투과도(%)Permeability (%) 아웃가스 양(Abundance, 억)Abundance (billion)
실시예 1Example 1 6565 9494 9898 7272
실시예 2Example 2 7070 9595 9797 6363
실시예 3Example 3 7171 9595 9898 7272
실시예 4Example 4 7373 9494 9494 6363
실시예 5Example 5 6565 9494 9898 7272
실시예 6Example 6 6565 9494 9898 7373
실시예 7Example 7 6868 9696 9696 5555
실시예 8Example 8 5555 9292 9696 6363
실시예 9Example 9 7272 9494 9595 5959
실시예 10Example 10 5252 9292 9494 7878
실시예 11Example 11 6060 9393 9494 7070
실시예 12Example 12 8080 9191 9696 8181
실시예 13Example 13 4545 9393 9696 6868
실시예 14Example 14 5050 9292 9595 7878
실시예 15Example 15 5555 9292 9494 7272
실시예 16Example 16 8383 8989 9696 7878
실시예 17Example 17 8282 9191 9595 7777
실시예 18Example 18 5050 9292 9494 6969
실시예 19Example 19 4545 9494 9696 7474
실시예 20Example 20 4848 9595 9797 7979
비교예 1Comparative Example 1 160160 8888 9191 182182
비교예 2Comparative Example 2 150150 8787 9292 168168
비교예 3Comparative Example 3 150150 8787 9191 160160
상기 표 3의 결과에서 알 수 있듯이, 본 발명의 포토레지스트 조성물은 종래의 포토레지스트 조성물과 비교하여 감도, 잔막율, 투과도 및 등의 물성이 우수하고 공정중 발생하는 아웃가스양을 획기적으로 줄일 수 있는 장점이 있음을 나타내고 있다. As can be seen from the results of Table 3, the photoresist composition of the present invention has excellent physical properties such as sensitivity, residual film ratio, transmittance, and the like compared to the conventional photoresist composition, and can significantly reduce the amount of outgas generated during the process. There is an advantage.
이와 같은 결과는 TFT-LCD 제조 공정 중의 노광 및 하드베이크 공정에서 광개시제로부터 발생하는 out-gas를 최소화 할 수 있어 오염을 줄일 수 있고 노광 시간 단축으로 인하여 생산성이 개선되는 장점을 가진다.This result can minimize the out-gas generated from the photoinitiator in the exposure and hard bake process during the TFT-LCD manufacturing process has the advantage of reducing the contamination and improved productivity by shortening the exposure time.

Claims (16)

  1. 하기 [화학식 A]로 표시되는 옥심에스테르 화합물.An oxime ester compound represented by the following [Formula A].
    [화학식 A] [Formula A]
    Figure PCTKR2019005284-appb-I000099
    Figure PCTKR2019005284-appb-I000099
    상기 [화학식 A]에서, In [Formula A],
    상기 치환기 R'는 수소, 중수소, 치환 또는 비치환된 C1-C30의 알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환되고 이종 원자로 N, O, P, Si 및 S 에서 선택되는 1 내지 3의 원자를 갖는 C3-C24의 헤테로아릴기, 치환 또는 비치환된 C1-C20의 히드록시알킬기, 치환 또는 비치환된 C7-C24의 아릴알킬기, 및 치환 또는 비치환된 C3-C20의 시클로알킬기 중에서 선택되는 어느 하나이며, The substituent R ′ is hydrogen, deuterium, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted hetero atom, N, O, P, Si And C 3 -C 24 heteroaryl group having 1 to 3 atoms selected from S, substituted or unsubstituted C 1 -C 20 hydroxyalkyl group, substituted or unsubstituted C 7 -C 24 arylalkyl group , And any one selected from a substituted or unsubstituted C 3 -C 20 cycloalkyl group,
    상기 m은 0 또는 1이며,M is 0 or 1,
    상기 n은 1 또는 2이며, n 이 2인경우 각각의 R'-S 는 동일하거나 상이하며,N is 1 or 2, and when n is 2, each R'-S is the same or different.
    상기 치환기 R1, R2는 각각 동일하거나 상이하며, 서로 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 치환 또는 비치환된 C1-C30의 알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환되고 이종 원자로 N, O, P, Si, 및 S 에서 선택되는 1 내지 3의 원자를 갖는 C3-C24의 헤테로아릴기, 치환 또는 비치환된 C1-C20의 알콕시기, 치환 또는 비치환된 C7-C24의 아릴알킬기, 치환 또는 비치환된 C3-C20의 시클로알킬기 중에서 선택되는 어느 하나이며,The substituents R 1 and R 2 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 6 -C 30 aryl group, substituted or unsubstituted C 3 -C 24 heteroaryl group, substituted or unsubstituted C having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms; Any one selected from a 1 -C 20 alkoxy group, a substituted or unsubstituted C 7 -C 24 arylalkyl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl group,
    상기 치환기 R5 내지 R 6은 각각 동일하거나 상이하며, 서로 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 치환 또는 비치환된 C1-C30의 알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환되고 이종 원자로 N, O, P, Si, 및 S 에서 선택되는 1 내지 3의 원자를 갖는 C3-C24의 헤테로아릴기, 치환 또는 비치환된 C1-C20의 알콕시기, 치환 또는 비치환된 C7-C24의 아릴알킬기, 치환 또는 비치환된 C3-C20의 시클로알킬기, 치환 또는 비치환된 C1-C20의 알킬티오닐기, 치환 또는 비치환된 C6-C20의 아릴티오닐기, 치환 또는 비치환된 C3-C20의 시클로알킬티오닐기 중에서 선택되는 어느 하나이며,The substituents R 5 to R 6 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 6 -C 30 aryl group, substituted or unsubstituted C 3 -C 24 heteroaryl group, substituted or unsubstituted C having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms; 1- C 20 alkoxy group, substituted or unsubstituted C 7 -C 24 arylalkyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl group, substituted or unsubstituted C 1 -C 20 alkylthioyl A group, a substituted or unsubstituted C 6 -C 20 arylthionyl group, a substituted or unsubstituted C 3 -C 20 cycloalkylthionyl group,
    상기 X는 CR3R4, S, O 중에서 선택되는 어느 하나이며, X is any one selected from CR 3 R 4 , S, O,
    상기 치환기 R3 및 R4는 각각 동일하거나 상이하며, 서로 독립적으로 수소, 중수소, 치환 또는 비치환된 C1-C30의 알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환되고 이종 원자로 N, O, P, Si, 및 S 에서 선택되는 1 내지 3의 원자를 갖는 C3-C24의 헤테로아릴기, 치환 또는 비치환된 C1-C20의 알콕시기, 치환 또는 비치환된 C7-C20의 아릴알킬기 또는 치환 또는 비치환된 C3-C20의 시클로알킬기 중에서 선택되는 어느 하나이며, 상기 치환기 R3 및 R4는 서로 결합하여 지환족 또는 방향족의 단일환 또는 다환고리를 형성할 수 있으며,The substituents R 3 and R 4 are the same or different, and are each independently hydrogen, deuterium, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or C 3 -C 24 heteroaryl group, unsubstituted or unsubstituted C 1 -C 20 alkoxy group, unsubstituted and having 1 to 3 atoms selected from hetero atoms as N, O, P, Si, and S Or an unsubstituted C 7 -C 20 arylalkyl group or a substituted or unsubstituted C 3 -C 20 cycloalkyl group, and the substituents R 3 and R 4 are bonded to each other to form an alicyclic or aromatic group. Can form a monocyclic or polycyclic ring,
    상기 k는 0 내지 4-n 중에서 선택되는 하나의 정수이고, 상기 k가 2 이상인 경우에 각각의 R6는 서로 동일하거나 상이하며,K is an integer selected from 0 to 4-n, and when k is 2 or more, each R 6 is the same as or different from each other,
    상기 l은 0 내지 3 중에서 선택되는 하나의 정수이며, 상기 l이 2 이상인 경우에 각각의 R5는 서로 동일하거나 상이하며,L is an integer selected from 0 to 3, and when l is 2 or more, each R 5 is the same as or different from each other,
    상기 [화학식 A]에서의 ‘치환 또는 비치환된’에서의 ‘치환’은 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, C1-C24의 알킬기, 치환 또는 비치환된 C3-C20의 시클로알킬기, C1-C24의 할로겐화된 알킬기, C2-C24의 알케닐기, C2-C24의 알키닐기, C1-24의 헤테로알킬기, C6-C24의 아릴기, C7-C24의 아릴알킬기, C3-C24의 헤테로아릴기, C3-C24의 헤테로아릴알킬기, C1-C24의 알콕시기, C1-C24의 알킬아미노기, C6-C24의 아릴아미노기, C3-C24의 헤테로아릴아미노기, C1-C24의 알킬실릴기, C6-C24의 아릴실릴기, C6-C24의 아릴옥시기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환되는 것을 의미한다.'Substituted' in 'substituted or unsubstituted' in [Formula A] is deuterium, cyano group, nitro group, halogen group, hydroxy group, C 1 -C 24 alkyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl group, C 1 -C 24, of the halogenated alkyl group, C 2 -C 24 alkenyl group, C 2 -C 24 alkynyl group of, C 1 - 24 heterocyclic group, C 6 -C 24 aryl group, C 7 -C 24 arylalkyl group, C 3 -C 24 heteroaryl group, C 3 -C 24 heteroarylalkyl group, C 1 -C 24 alkoxy group, C 1 -C 24 alkylamino group, C 6- 1 selected from the group consisting of C 24 arylamino group, C 3 -C 24 heteroarylamino group, C 1 -C 24 alkylsilyl group, C 6 -C 24 arylsilyl group, C 6 -C 24 aryloxy group It means to be substituted with more than one substituent.
  2. 제1항에 있어서,The method of claim 1,
    상기 [화학식 A]로 표시되는 화합물은 하기 [화학식A-1]으로 표시되는 것을 특징으로 하는 옥심에스테르 화합물.The compound represented by the above [Formula A] is represented by the following [Formula A-1], characterized in that the oxime ester compound.
    [화학식A-1]  [Formula A-1]
    Figure PCTKR2019005284-appb-I000100
    Figure PCTKR2019005284-appb-I000100
    상기 치환기 R1 내지 R4 , R'는 상기 청구항 1에서 정의한 바와 같고,The substituents R 1 to R 4 , R ′ are as defined in claim 1,
    상기 m은 0 또는 1이다.M is 0 or 1;
  3. 제1항에 있어서,The method of claim 1,
    상기 [화학식 A]로 표시되는 화합물은 하기 [화학식A-2]으로 표시되는 것을 특징으로 하는 옥심에스테르 화합물.The compound represented by [Formula A] is represented by the following [Formula A-2], characterized in that the oxime ester compound.
    [화학식A-2] [Formula A-2]
    Figure PCTKR2019005284-appb-I000101
    Figure PCTKR2019005284-appb-I000101
    상기 치환기 R1, R2 및 R'는 상기 청구항 1에서 정의한 바와 같고,The substituents R 1 , R 2 and R ′ are as defined in claim 1,
    상기 m은 0 또는 1이다.M is 0 or 1;
  4. 제1항에 있어서,The method of claim 1,
    상기 [화학식 A]로 표시되는 화합물은 하기 [화학식A-3]으로 표시되는 것을 특징으로 하는 옥심에스테르 화합물.The compound represented by [Formula A] is represented by the following [Formula A-3], characterized in that the oxime ester compound.
    [화학식A-3]    [Formula A-3]
    Figure PCTKR2019005284-appb-I000102
    Figure PCTKR2019005284-appb-I000102
    상기 치환기 R1, R2 및 R'는 상기 청구항 1에서 정의한 바와 같고,The substituents R 1 , R 2 and R ′ are as defined in claim 1,
    상기 m은 0 또는 1이다.M is 0 or 1;
  5. 제2항에 있어서,The method of claim 2,
    상기 [화학식 A-1]로 표시되는 화합물은 하기 [화학식A-4]로 표시되는 것을 특징으로 하는 옥심에스테르 화합물.The compound represented by [Formula A-1] is represented by the following [Formula A-4].
    [화학식A-4]  [Formula A-4]
    Figure PCTKR2019005284-appb-I000103
    Figure PCTKR2019005284-appb-I000103
    상기 치환기 R1 내지 R4 , R’는 상기 청구항 1에서 정의한 바와 같다.The substituents R 1 to R 4 , R ′ are as defined in claim 1 above.
  6. 제3항에 있어서,The method of claim 3,
    상기 [화학식 A-2]로 표시되는 화합물은 하기 [화학식A-5]로 표시되는 것을 특징으로 하는 옥심에스테르 화합물.The compound represented by [Formula A-2] is represented by the following [Formula A-5].
    [화학식A-5] [Formula A-5]
    Figure PCTKR2019005284-appb-I000104
    Figure PCTKR2019005284-appb-I000104
    상기 치환기 R1, R2 및 R’는 상기 청구항 1에서 정의한 바와 같다.The substituents R 1 , R 2 and R ′ are as defined in claim 1 above.
  7. 제4항에 있어서,The method of claim 4, wherein
    상기 [화학식 A-3]으로 표시되는 화합물은 하기 [화학식A-6]으로 표시되는 것을 특징으로 하는 옥심에스테르 화합물.The compound represented by [Formula A-3] is represented by the following [Formula A-6], characterized in that the oxime ester compound.
    [화학식A-6]    [Formula A-6]
    Figure PCTKR2019005284-appb-I000105
    Figure PCTKR2019005284-appb-I000105
    상기 치환기 R1, R2 및 R’는 상기 청구항 1에서 정의한 바와 같다.The substituents R 1 , R 2 and R ′ are as defined in claim 1 above.
  8. 제1항에 있어서,The method of claim 1,
    상기 [화학식 A]에서 R’는 치환 또는 비치환된 C1-C30의 알킬기, 치환 또는 비치환된 C3-C20의 시클로알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환된 C7-C24의 아릴알킬기 중에서 선택되는 치환기인 것을 특징으로 하는 옥심에스테르 화합물.R 'in [Formula A] is a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, An oxime ester compound, which is a substituent selected from a substituted or unsubstituted C 7 -C 24 arylalkyl group.
  9. 제1항 에 있어서,The method of claim 1,
    상기 [화학식 A]에서 R'는 (R8)p-Ar- 로 표시되는 것을 특징으로 하는 옥심에스테르 화합물.R 'in the formula [A] is an oxime ester compound, characterized in that represented by (R 8 ) p -Ar-.
    상기 치환기 R8은 치환 또는 비치환된 C1-C24의 알킬기, 치환 또는 비치환된 C3-C20의 시클로알킬기, 치환 또는 비치환된 C6-C24의 아릴기, 치환 또는 비치환된 C7-C24의 아릴알킬기 치환 또는 비치환된 C1-C24의 할로겐화된 알킬기, 치환 또는 비치환된 C1-C24의 알콕시기, 치환 또는 비치환된 C1-C24의 알킬실릴기, 치환 또는 비치환된 C6-C24의 아릴실릴기, 치환 또는 비치환된 C1-C20의 알킬티오닐기, 치환 또는 비치환된 C6-C20의 아릴티오닐기, 치환 또는 비치환된 C3-C20의 시클로알킬티오닐기, 시아노기, 니트로기, 할로겐기 중에서 선택되는 어느 하나이며, The substituent R 8 is a substituted or unsubstituted C 1 -C 24 alkyl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl group, a substituted or unsubstituted C 6 -C 24 aryl group, substituted or unsubstituted a C 7 -C 24 arylalkyl group of substituted or unsubstituted C 1 -C 24 halogenated alkyl group, a substituted or unsubstituted C 1 -C 24 alkoxy group, a substituted or unsubstituted alkyl of C 1 -C 24 of Silyl group, substituted or unsubstituted C 6 -C 24 arylsilyl group, substituted or unsubstituted C 1 -C 20 alkylthioyl group, substituted or unsubstituted C 6 -C 20 arylthioyl group, It is any one selected from a substituted or unsubstituted C 3 -C 20 cycloalkylthionyl group, cyano group, nitro group, halogen group,
    상기 Ar은 치환 또는 비치환된 C6-C24의 방향족고리이고,Ar is a substituted or unsubstituted C 6 -C 24 aromatic ring,
    상기 p는 0 내지 3 중에서 하나의 정수이고, p가 2 이상인 경우에 각각의 R8은 서로 동일하거나 상이하다.P is an integer of 0 to 3, and when p is 2 or more, each R 8 is the same as or different from each other.
  10. 제1항에 있어서,The method of claim 1,
    상기 [화학식 A]에서 R'는 하기 구조식 A-1로 표시되는 것을 특징으로 하는 옥심에스테르 화합물.R 'in the formula [A] is an oxime ester compound, characterized in that represented by the following structural formula A-1.
    [구조식 A-1][Formula A-1]
    Figure PCTKR2019005284-appb-I000106
    Figure PCTKR2019005284-appb-I000106
    상기 치환기 R11 내지 R15는 각각 동일하거나 상이하며, 서로 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 치환 또는 비치환된 C1-C30의 알킬기, 치환 또는 비치환된 C1-C24의 할로겐화된 알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환되고 이종 원자로 N, O, P, Si, 및 S 에서 선택되는 1 내지 3의 원자를 갖는 C3-C24의 헤테로아릴기, 치환 또는 비치환된 C1-C20의 알콕시기, 치환 또는 비치환된 C7-C20의 아릴알킬기, 치환 또는 비치환된 C3-C20의 시클로알킬기, 치환 또는 비치환된 C1-C24의 알킬실릴기, 치환 또는 비치환된 C6-C24의 아릴실릴기, 치환 또는 비치환된 C1-C20의 알킬티오닐기, 치환 또는 비치환된 C6-C20의 아릴티오닐기, 치환 또는 비치환된 C3-C20의 시클로알킬티오닐기 중에서 선택되는 어느 하나이다.The substituents R 11 to R 15 are the same or different, and are each independently hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted C 1 -C 30 alkyl group, substituted or unsubstituted C 1 -C 24 halogenated alkyl group, substituted or unsubstituted C 6 -C 30 aryl group, substituted or unsubstituted C having 1 to 3 atoms selected from N, O, P, Si, and S as hetero atoms 3 -C 24 heteroaryl group, substituted or unsubstituted C 1 -C 20 alkoxy group, substituted or unsubstituted C 7 -C 20 arylalkyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl group , Substituted or unsubstituted C 1 -C 24 alkylsilyl group, substituted or unsubstituted C 6 -C 24 arylsilyl group, substituted or unsubstituted C 1 -C 20 alkylthioyl group, substituted or unsubstituted hwandoen C 6 -C 20 is selected from any one of the aryl thionyl group, a substituted or unsubstituted cycloalkyl alkyl group of the unsubstituted C 3 -C 20 group O'Neill The.
  11. 제1항에 있어서,The method of claim 1,
    상기 [화학식 A]로 표시되는 화합물은 하기 화합물 1 내지 화합물 330에서 선택되는 어느 하나로 표시되는 것을 특징으로 하는 옥심에스테르 화합물.The compound represented by [Formula A] is an oxime ester compound, characterized in that represented by any one selected from Compound 1 to Compound 330.
    Figure PCTKR2019005284-appb-I000107
    Figure PCTKR2019005284-appb-I000107
    Figure PCTKR2019005284-appb-I000108
    Figure PCTKR2019005284-appb-I000108
    Figure PCTKR2019005284-appb-I000109
    Figure PCTKR2019005284-appb-I000109
    Figure PCTKR2019005284-appb-I000110
    Figure PCTKR2019005284-appb-I000110
    Figure PCTKR2019005284-appb-I000111
    Figure PCTKR2019005284-appb-I000111
    Figure PCTKR2019005284-appb-I000112
    Figure PCTKR2019005284-appb-I000112
    Figure PCTKR2019005284-appb-I000113
    Figure PCTKR2019005284-appb-I000113
    Figure PCTKR2019005284-appb-I000114
    Figure PCTKR2019005284-appb-I000114
    Figure PCTKR2019005284-appb-I000115
    Figure PCTKR2019005284-appb-I000115
    Figure PCTKR2019005284-appb-I000116
    Figure PCTKR2019005284-appb-I000116
    Figure PCTKR2019005284-appb-I000117
    Figure PCTKR2019005284-appb-I000117
    Figure PCTKR2019005284-appb-I000118
    Figure PCTKR2019005284-appb-I000118
    Figure PCTKR2019005284-appb-I000119
    Figure PCTKR2019005284-appb-I000119
    Figure PCTKR2019005284-appb-I000120
    Figure PCTKR2019005284-appb-I000120
    Figure PCTKR2019005284-appb-I000121
    Figure PCTKR2019005284-appb-I000121
    Figure PCTKR2019005284-appb-I000122
    Figure PCTKR2019005284-appb-I000122
    Figure PCTKR2019005284-appb-I000123
    Figure PCTKR2019005284-appb-I000123
    Figure PCTKR2019005284-appb-I000124
    Figure PCTKR2019005284-appb-I000124
    Figure PCTKR2019005284-appb-I000125
    Figure PCTKR2019005284-appb-I000125
    Figure PCTKR2019005284-appb-I000126
    Figure PCTKR2019005284-appb-I000126
    Figure PCTKR2019005284-appb-I000127
    Figure PCTKR2019005284-appb-I000127
    Figure PCTKR2019005284-appb-I000128
    Figure PCTKR2019005284-appb-I000128
  12. 제1항 내지 제11항 중 어느 한 항에 기재된 옥심에스테르 화합물을 포함하는 포토레지스트 조성물.The photoresist composition containing the oxime ester compound in any one of Claims 1-11.
  13. 포토레지스트 조성물 100 중량부에 대해서, 제1항 내지 제11항 중 어느 한 항에 기재된 옥심에스테르 화합물 0.1 내지 20 중량부, 광중합성 화합물 80 내지 99.9 중량부를 포함하는 포토레지스트 조성물.The photoresist composition containing 0.1-20 weight part of oxime ester compounds in any one of Claims 1-11, and 80-99.9 weight part of photopolymerizable compounds with respect to 100 weight part of photoresist compositions.
  14. 포토레지스트 조성물 100 중량부에 대해서, 제1항 내지 제 11항 중 어느 한 항에 기재된 옥심에스테르 화합물 0.1 내지 20 중량부, 광중합성 화합물 1 내지 60 중량부, 아크릴 중합체 0 내지 40 중량부 및 용매 10 내지 90 중량부를 포함하는 포토레지스트 조성물.To about 100 parts by weight of the photoresist composition, 0.1 to 20 parts by weight of the oxime ester compound according to any one of claims 1 to 11, 1 to 60 parts by weight of the photopolymerizable compound, 0 to 40 parts by weight of the acrylic polymer, and a solvent 10 To 90 parts by weight of the photoresist composition.
  15. 포토레지스트 조성물 100 중량부에 대해서, 제1항 내지 제11항 중 어느 한 항에 기재된 옥심에스테르 화합물 0.1 내지 20 중량부, 광중합성 화합물 1 내지 60 중량부, 아크릴 중합체 0 내지 40 중량부, 적색, 녹색, 청색 또는 블랙 안료 1 내지 50 중량부 및 용매 10 내지 90 중량부를 포함하는 포토레지스트 조성물.With respect to 100 weight part of photoresist compositions, 0.1-20 weight part of oxime ester compounds in any one of Claims 1-11, 1-60 weight part of photopolymerizable compounds, 0-40 weight part of acrylic polymers, red, A photoresist composition comprising 1 to 50 parts by weight of a green, blue or black pigment and 10 to 90 parts by weight of a solvent.
  16. 제 12항에 있어서, The method of claim 12,
    상기 포토레지스트 조성물은 TFT-LCD, 컬러필터, 유기발광소자(OLED), 조명장치, 금속 센서, 태양전지, 집적 회로, 유기 전계-효과 트랜지스터 (O-FET) 및 유기 박막 트랜지스터 (O-TFT)에서 선택되는 어느 하나의 장치에 사용되는 것을 특징으로 하는 포토레지스트 조성물.The photoresist composition may be a TFT-LCD, a color filter, an organic light emitting diode (OLED), a lighting device, a metal sensor, a solar cell, an integrated circuit, an organic field effect transistor (O-FET), and an organic thin film transistor (O-TFT). Photoresist composition, characterized in that used in any one device selected from.
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