Nothing Special   »   [go: up one dir, main page]

WO2016122160A1 - Novel dioximester compound, and photopolymerization initiator and photoresist composition containing same - Google Patents

Novel dioximester compound, and photopolymerization initiator and photoresist composition containing same Download PDF

Info

Publication number
WO2016122160A1
WO2016122160A1 PCT/KR2016/000635 KR2016000635W WO2016122160A1 WO 2016122160 A1 WO2016122160 A1 WO 2016122160A1 KR 2016000635 W KR2016000635 W KR 2016000635W WO 2016122160 A1 WO2016122160 A1 WO 2016122160A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
mol
added
biphenyl
minutes
Prior art date
Application number
PCT/KR2016/000635
Other languages
French (fr)
Korean (ko)
Inventor
오천림
이득락
이민선
이원중
이재훈
조용일
Original Assignee
주식회사 삼양사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 삼양사 filed Critical 주식회사 삼양사
Publication of WO2016122160A1 publication Critical patent/WO2016122160A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/68—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with at least one of the esterifying carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • 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
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Definitions

  • the present invention relates to a novel dioxime ester compound and a photopolymerization initiator and photoresist composition comprising the same.
  • the photopolymerization initiator used in the photoresist composition various kinds such as acetophenone derivatives, benzophenone derivatives, triazine derivatives, biimidazole derivatives, acylphosphine oxide derivatives and oxime ester derivatives are known. It absorbs ultraviolet rays, exhibits little color, has high radical generation efficiency, and has excellent compatibility and stability with photoresist composition materials.
  • the earlier developed oxime derivative compounds have a low photoinitiation efficiency, in particular, a low sensitivity in the pattern exposure process, so the exposure should be increased, resulting in a decrease in production.
  • the oxime ester compound is capable of polymerizing and curing a polymerizable compound having an unsaturated bond by irradiating the photoresist composition with light of 365-435 nm, which is used for a black matrix, color filter, column spacer, flexible insulating film, photoresist composition for overcoat, and the like. It is becoming.
  • the photoinitiator has high sensitivity to long wavelength light sources such as 365-435 nm, has good photopolymerization reactivity, easy to manufacture, high thermal stability and storage stability, and easy to handle, and it is easy to handle (PGMEA; propylene glycol monomethyl ether acetate).
  • PGMEA propylene glycol monomethyl ether acetate
  • photoresist compositions used in thin film displays such as liquid crystal display devices and OLEDs
  • alkaline developer to form organic insulating films, column spacers, UV overcoats, R.G.B.
  • a lot of research is being conducted on the photoresist composition containing a high-sensitivity photopolymerization initiator capable of pattern formation with a color resist, a black matrix, or the like.
  • the photoresist composition containing a binder resin, the polyfunctional monomer which has an ethylenically unsaturated bond, and a photoinitiator is preferable.
  • the sensitivity is low during the exposure process for pattern formation, so the amount of use of the photopolymerization initiator must be increased or the exposure amount must be increased, thereby contaminating the mask in the exposure process, and the photopolymerization initiator at high temperature crosslinking.
  • the yield is reduced as a by-product generated after decomposition, there is a problem that the production process is reduced by increasing the exposure process time according to the increase in the exposure amount, efforts are being made to solve this problem.
  • Patent Document 1 JP 2001-302871 A (2001.10.31)
  • Patent Document 2 JP 2006-160634 A (2006.06.22)
  • Patent Document 3 JP 2005-025169 A (2005.01.27)
  • Patent Document 4 JP 2005-242279 A (2005.09.08)
  • Patent Document 5 WO 02/100903 (2002.12.19)
  • Patent Document 6 WO 07/071497 (2007.06.28)
  • Patent Document 7 WO 08/138733 (2008.11.20)
  • Patent Document 8 WO 08/078686 (2008.07.03)
  • Patent Document 9 WO 09/081483 (2009.07.02)
  • an object of the present invention is to provide a novel dioxime ester compound, a photopolymerization initiator containing the same, and a photoresist composition comprising the dioxime ester compound.
  • Another object of the present invention is to provide a molded article comprising a cured product of a photoresist composition containing a novel dioxime ester compound.
  • Another object of the present invention is to provide a display device including the molding of the present invention.
  • the present invention provides a dioxime ester compound represented by the following formula (1), a photopolymerization initiator and a photoresist composition comprising the same.
  • R 1 to R 3 are each independently hydrogen, halogen, (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl, (C 1 -C 20 ) alkoxy, (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl, hydroxy (C 1 -C 20 ) alkyl, hydroxy (C 1 -C 20 ) alkoxy (C 1 -C 20 ) alkyl, (C 3 -C 20 ) cycloalkyl or (C 3 -C 20 ) cycloalkyl (C 1 -C 20 ) alkyl;
  • A is hydrogen, halogen, (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl, (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl, amino, nitro, cyano or hydroxy ego;
  • n is an integer of 0-2.
  • halo or halogen in the present invention means fluorine, chlorine, bromine or iodine atoms.
  • alkyl refers to a monovalent straight-chain or pulverized saturated hydrocarbon radical consisting solely of carbon and hydrogen atoms, e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl , Octyl, nonyl, and the like.
  • aryl in the present invention refers to an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, in which a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, suitably in each ring It includes a system, including a form in which a plurality of aryl is connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, and the like.
  • alkoxy refers to an -O-alkyl radical, which may be exemplified by methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy and the like.
  • arylalkyl of the present invention is an alkyl group substituted with aryl as defined above, and may be exemplified by benzyl and the like.
  • hydroxyalkyl of the present invention is an hydroxy substituted alkyl group, which may be exemplified by hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, and the like.
  • hydroxyalkoxyalkyl of the present invention is an alkyl group substituted with hydroxyalkoxy, which is hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, Hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl, hydroxyethoxyhexyl and the like.
  • cycloalkyl as used herein means a monocyclic alkyl group having 3 to 7 carbon atoms as well as a polycyclic alkyl group in which two or more monocyclic alkyls are fused. Specific examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
  • cycloalkylalkyl refers to an alkyl group substituted with a cycloalkyl as defined above, and may be exemplified by cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclopropylethyl and the like.
  • the '(C 1 -C 20 ) alkyl' group described in the present invention is preferably (C 1 -C 10 ) alkyl, more preferably (C 1 -C 6 ) alkyl.
  • the '(C 6 -C 20 ) aryl' group is preferably (C 6 -C 18 ) aryl.
  • the '(C 1 -C 20 ) alkoxy' group is preferably (C 1 -C 10 ) alkoxy, more preferably (C1-C4) alkoxy.
  • the '(C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl' group is preferably (C 6 -C 18 ) aryl (C 1 -C 10 ) alkyl, more preferably (C 6 -C 18) ) Aryl (C 1 -C 6 ) alkyl.
  • the 'hydroxy (C 1 -C 20 ) alkyl' group is preferably hydroxy (C 1 -C 10 ) alkyl, more preferably hydroxy (C 1 -C 6 ) alkyl.
  • the 'hydroxy (C 1 -C 20 ) alkoxy (C 1 -C 20 ) alkyl' group is preferably hydroxy (C 1 -C 10 ) alkoxy (C 1 -C 10 ) alkyl, more preferably hydroxy (C 1 -C 4 ) alkoxy (C 1 -C 6 )) alkyl.
  • the '(C 3 -C 20 ) cycloalkyl' group is preferably (C 3 -C 10 ) cycloalkyl.
  • the '(C 3 -C 20 ) cycloalkyl (C 1 -C 20 ) alkyl' group is preferably (C 3 -C 10 ) cycloalkyl (C 1 -C 10 ) alkyl, more preferably (C 3- C 10 ) cycloalkyl (C 1 -C 6 ) alkyl.
  • each R 1 may be the same or different from each other.
  • R 1 to R 3 are each independently hydrogen, bromo, chloro, iodo, methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, t -butyl, n -pentyl , i -pentyl, n -hexyl, i -hexyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy, n -propyloxy, i -propyloxy, n -Butoxy, i -butoxy, t -butoxy, benzyl, hydroxymethyl, hydroxyethyl, hydroxy n -propyl, hydroxy n -butyl, hydroxy i -butyl, hydroxy n -pentyl, methyl,
  • A is hydrogen, bromo, chloro, methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, t -butyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, Phenanthryl, benzyl, amino, nitro, cyano or hydroxy, but is not limited thereto.
  • R 1 is hydrogen, (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl, hydroxy (C 1 -C 20 ) alkyl, hydride Oxy (C 1 -C 20 ) alkoxy (C 1 -C 20 ) alkyl, (C 3 -C 20 ) cycloalkyl or (C 3 -C 20 ) cycloalkyl (C 1 -C 20 ) alkyl;
  • R 2 and R 3 are each independently (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl, (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl, hydroxy (C 1- C 20 ) alkyl, hydroxy (C 1 -C 20 ) alkoxy (C 1 -C 20 ) alkyl, (C 3 -C 20 ) cycloalkyl or (
  • R 1 is hydrogen, (C 1 -C 20 ) alkyl, (C 3 -C 20 ) cycloalkyl or (C 3 -C 20 ) cycloalkyl (C 1 -C 20 ) alkyl ;
  • R 2 and R 3 are each independently (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl or (C 3 -C 20 ) cycloalkyl;
  • A can be hydrogen, halogen, (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl, nitro or cyano.
  • the dioxime ester compound according to the present invention may include the following compounds, but the following compounds are not intended to limit the present invention.
  • the dioxime ester compound represented by Formula 1 according to the present invention may be prepared as shown in Scheme 1 below.
  • the present invention provides a photopolymerization initiator comprising a dioxime ester compound represented by the formula (1).
  • the present invention provides a photoresist composition
  • a photoresist composition comprising a dioxime ester compound represented by the formula (1).
  • the dioxime ester compound represented by Chemical Formula 1 may be included in the photoresist composition as a photopolymerization initiator.
  • the photoresist composition of the present invention includes a dioxime ester compound represented by Chemical Formula 1, a binder resin, a polymerizable compound having an ethylenically unsaturated bond, a solvent, and the like, and has thin film properties such as pattern property control and heat resistance and chemical resistance. outstanding.
  • the photoresist composition of the present invention is a thioxanthone compound, acetophenone compound, biimidazole compound, triazine compound, thiol compound and O-acyl oxime compound in addition to the dioxime ester compound represented by the formula (1) It may further comprise one or two or more known photopolymerization initiators selected from the group consisting of.
  • thioxanthone-based compound examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-dichlorothioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- diisopropyl thioxanthone, etc., These can be used individually or in mixture of 2 or more types, respectively.
  • acetophenone compounds examples include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholine Nophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like; It can mix and use species.
  • biimidazole-based compound 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis ( 2,4-dichlorolophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4 , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, and the like, and these may be used alone or in combination of two or more thereof.
  • triazine-based compound examples include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- ( 5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [ 2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl ) -s
  • an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in the side chain may be used, and thin film properties such as pattern property control and heat resistance and chemical resistance may be used. It is preferable to use 3 to 50% by weight with respect to 100% by weight of the photoresist composition, polystyrene reduced weight average molecular weight by gel permeation chromatography (GPC) of the acrylic polymer is 2,000 to 30,000,000, dispersion degree is It is preferable to use what is 1.0-10.0, and it is more preferable to use what is a weight average molecular weight 4,000-100000,00.
  • GPC gel permeation chromatography
  • the acrylic polymer is a copolymer of monomers including the following monomers.
  • the monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth).
  • An acrylic polymer having an acrylic unsaturated bond in the side chain is a copolymer obtained by adding an epoxy resin to an acrylic copolymer containing a carboxylic acid, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and maleic acid monoalkyl ester.
  • a carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and maleic acid monoalkyl ester.
  • an acrylic polymer having an acrylic unsaturated bond in the side chain is a copolymer in which a carboxylic acid is added to an acrylic copolymer containing an epoxy group, and glycidyl acrylate, glycidyl methacrylate, and 3,4-epoxy.
  • Acrylic monomer containing methyl groups such as butyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, methyl (meth) acrylate, hexyl Alkyl (meth) acrylates, such as (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclo Pentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, styrene, ⁇ -methylstyrene, acetoxystyrene, N ⁇ Me Maleimide, N - e
  • the polymerizable compound having an ethylenically unsaturated bond serves to form a pattern by crosslinking by photoreaction at the time of pattern formation and crosslinking at high temperature to impart chemical resistance and heat resistance.
  • the polymerizable compound having an ethylenically unsaturated bond preferably uses 0.001 to 40% by weight based on 100% by weight of the photoresist composition.
  • the polymerizable compound having an ethylenically unsaturated bond is specifically methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acryl Alkyl ester of (meth) acrylic acid, such as the rate, glycidyl (meth) acrylate, polyethyleneglycol mono (meth) acrylate whose number of ethylene oxide groups is 2-14, ethylene glycol di (meth) acrylate, ethylene oxide group Polyethylene glycol di (meth) acrylate having a number of from 2 to 14, propylene glycol di (meth) acrylate having a number of from 2 to 14 of propylene oxide group, trimethylolpropanedi (meth) acrylate, bisphenol A diglycidyl ether Acrylic acid adduct, phthalic acid diester of ⁇ -hydroxyethyl
  • the amount of the dioxime ester compound of Chemical Formula 1 used as a photopolymerization initiator in the photoresist composition of the present invention is 0.01 to 10% by weight with respect to 100% by weight of the photoresist composition, preferably to increase transparency and minimize exposure. It is more effective to use 0.1 to 5% by weight.
  • the photoresist composition of the present invention may further include a silicone-based compound having an epoxy group or an amine group as an adhesion aid as necessary.
  • the silicon-based compound may improve adhesion between the ITO electrode and the photoresist composition and may increase heat resistance after curing.
  • a silicone type compound which has the said epoxy group or an amine group (3-glycidoxy propyl) trimethoxysilane, (3-glycidoxy propyl) triethoxy silane, (3-glycidoxy propyl) methyl dimethoxy silane Phosphorus, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyl Trimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane,
  • the photoresist composition of the present invention may further include a compatible additive such as a photosensitizer, a thermal polymerization inhibitor, an antifoaming agent, a leveling agent and the like as necessary.
  • a compatible additive such as a photosensitizer, a thermal polymerization inhibitor, an antifoaming agent, a leveling agent and the like as necessary.
  • the photoresist composition of the present invention is spin-coated onto a substrate by adding a solvent, and then forms a pattern through a method of developing with an alkali developer by irradiating ultraviolet rays using a mask, wherein the photoresist composition is 10 to 95% by weight based on 100% by weight of the photoresist composition. It is preferred to add% solvent to adjust the viscosity to be in the range of 1 to 50 cps.
  • the solvent may be ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate in consideration of compatibility with binder resins, photoinitiators and other compounds.
  • EEP ethyl lactate
  • PMEA propylene glycol monomethyl ether acetate
  • PMEP propylene glycol methyl ether propionate
  • EEP ethyl lactate
  • PMEA propylene glycol monomethyl ether acetate
  • PMEP propylene glycol methyl ether propyl ether
  • methyl cellosolve acetate ethyl cellosolve acetate
  • Diethylene glycol methyl acetate diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N , N -dimethylacetamide (DMAc), N -methyl-2-pyrroli Don (NMP), ⁇ -butylolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofue Column (THF), methanol, ethanol, propanol,
  • Photoresist composition according to an embodiment of the present invention is a known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, immersion, soda glass, quartz glass, semiconductor substrate, metal, It can be applied to a supporting substrate such as paper or plastic. Moreover, it can transfer to another support base body after performing it once on support bases, such as a film, and there is no restriction
  • a photoresist composition according to an embodiment of the present invention is a color filter in a liquid crystal display device of a color display such as a photocurable paint or varnish, a photocurable adhesive, a printed board, or a color television, a PC monitor, a portable information terminal, a digital camera, or the like.
  • Electrode material for plasma display panel powder coating, printing ink, printing plate, adhesive, dental composition, gel coating, photoresist for electronic engineering, electroplating resist, etching resist, solder resist for both liquid and dry film, various marking Compositions for manufacturing color matrices for use or for forming structures in plasma display panels, electroluminescent displays, and LCDs, compositions for encapsulating electrical and electronic components, magnetic recording materials, micromechanical components Waveguides, Optical Switches, Plating Masks, Etch Masks, Color Test Systems, Fiberglass Cables Coating, stencils for screen printing, materials for manufacturing three-dimensional objects by stereo lithography, materials for holographic recording, image recording materials, microelectronic circuits, color decoloring materials, color decoloring materials for image recording materials, image recording materials using microcapsules It can be used for various applications such as discoloration material for photoresist, photoresist material for printed wiring board, photoresist material for UV and visible laser direct imaging system, photoresist material for forming
  • the present invention provides a photoresist composition comprising a coloring material in the photoresist composition comprising a dioxime ester compound represented by the formula (1).
  • the photoresist composition may be added to the coloring material according to the use to prepare a colored photoresist composition, the coloring material may be used a variety of coloring materials, such as black, red, yellow, green, blue. In order to manufacture a black matrix, a black coloring material is added, and in order to manufacture a color filter, various coloring materials which show R.G.B.color etc. can be used.
  • a coloring material contained in order to apply it to molded object formation resists such as a color filter and a black matrix
  • cyan, magenta, yellow, and black pigment of a red, green, blue, and dark blue mixed system are mentioned.
  • pigments CI Pigment Yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 166, 168 , CI Pigment Orange 36, 43, 51, 55, 59, 61, CI Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226 , 227, 228, 240, CI Pigment Violet 19, 23, 29, 30, 37, 40, 50, CI Pigment Blue 15, 15: 1, 15: 4, 15: 6, 22, 60, 64, CI Pigment Green 7, 36, CI Pigment brown 23, 25, 26, CI pigment black 7, titanium
  • the present invention also provides a molded article comprising the cured product of the photoresist composition.
  • the molding of the present invention is characterized in that the array planarization film, the insulating film, the column spacer, the black column spacer, the black matrix or the color filter.
  • the present invention provides a display device including the molding.
  • the dioxime ester compound of the present invention When used as a photoinitiator of the photoresist composition, the dioxime ester compound of the present invention has excellent sensitivity even when used in a small amount, and has excellent physical properties such as residual film ratio, pattern stability, chemical resistance, and ductility. And it is possible to minimize the outgassing from the photopolymerization initiator in the post-baking process can reduce the contamination and there is an advantage that can minimize the defects that can be caused by this.
  • reaction solution was cooled to room temperature, 30 mL of H 2 O was added thereto, followed by stirring for about 30 minutes, and 40 mL of 1% HCl aqueous solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • n -hexane 1: 4) to obtain 8.54 g (92.0%) of 1- (biphenyl-4-yl) butane-1,3-dione O, O-dicyclohexanecarbonyl dioxime ( 6 ) Got it.
  • reaction solution was cooled to room temperature, 30 mL of H 2 O was added thereto, followed by stirring for about 30 minutes, and 40 mL of 1% HCl aqueous solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • n -hexane 1: 4
  • n -hexane 1: 4
  • Biphenyl ( 14 ) Dissolve 10.0 g (0.065 mol) in 100 mL of dichloromethane, cool the reaction to -5 ° C, slowly add 10.40 g (0.78 mol) of aluminum chloride, and 5 mL of dichloromethane, taking care not to raise the temperature of the reaction. 12.53 g (0.078 mol) of 2-cyclohexylacetyl chloride diluted in was slowly added over 2 hours, and the reaction was stirred at -5 ° C for 1 hour.
  • reaction solution was cooled to room temperature, 30 mL of H 2 O was added, followed by stirring for about 30 minutes, and 30 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • n - hexane 1: 4) to give 1- (biphenyl-4-yl) -2-cyclohexyl-butane-1,3-dione O, O- di-acetyl-di-oxime (18) 5.49 g (90.3% )
  • Biphenyl ( 14 ) Dissolve 10.0 g (0.065 mol) in 100 mL of dichloromethane, cool the reaction to -5 ° C, slowly add 10.40 g (0.78 mol) of aluminum chloride, and 5 mL of dichloromethane, taking care not to raise the temperature of the reaction. 12.53 g (0.078 mol) of 3-cyclopentylpropionyl chloride diluted in was slowly added over 2 hours, and the reaction was stirred at -5 ° C for 1 hour.
  • reaction solution was cooled to room temperature, 30 mL of H 2 O was added, followed by stirring for about 30 minutes, and 30 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • reaction solution was cooled to room temperature, 30 mL of H 2 O was added thereto, followed by stirring for about 30 minutes, and 40 mL of 1% HCl aqueous solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • n -hexane 1: 4) to obtain 5.84 g (90.3%) of 1- (biphenyl-4-yl) hexane-1,3-dione O, O-diacetyl dioxime ( 25 ).
  • reaction solution was cooled to room temperature, 30 mL of H 2 O was added thereto, followed by stirring for about 30 minutes, and 80 mL of an aqueous 1% HCl solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained solid product was dispersed in 500 mL of distilled water, stirred at room temperature for about 30 minutes, filtered, washed sufficiently with distilled water, and dried to light gray 1- (4'-nitro-biphenyl-4-yl) ethanone ( 31 ). 17.8 g (67.2%) was obtained.
  • reaction solution was cooled to room temperature, 30 mL of H 2 O was added thereto, followed by stirring for about 30 minutes, and 80 mL of an aqueous 1% HCl solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • reaction solution was cooled to room temperature, 30 mL of H 2 O was added thereto, followed by stirring for about 30 minutes, and 80 mL of an aqueous 1% HCl solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • Biphenyl ( 14 ) Dissolve 10.0 g (0.065 mol) in 100 mL of dichloromethane, cool the reaction to -5 ° C, slowly add 10.40 g (0.78 mol) of aluminum chloride, and 5 mL of dichloromethane, taking care not to raise the temperature of the reaction. 11.59 g (0.078 mol) of heptanoyl chloride diluted in was slowly added over 2 hours, and the reaction was stirred at -5 ° C for 1 hour.
  • reaction solution was cooled to room temperature, 30 mL of H 2 O was added, followed by stirring for about 30 minutes, and 30 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • reaction solution was cooled to room temperature, 30 mL of H 2 O was added, followed by stirring for about 30 minutes, and 30 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • reaction solution was cooled to room temperature, 30 mL of H 2 O was added, followed by stirring for about 30 minutes, and 30 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • reaction solution was cooled to room temperature, 30 mL of H 2 O was added thereto, stirred for about 30 minutes, and then slowly added dropwise 50 mL of an aqueous 1% HCl solution to neutralize the reactant to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • reaction solution was cooled to room temperature, 30 mL of H 2 O was added thereto, followed by stirring for about 30 minutes, and 40 mL of 1% HCl aqueous solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • methacrylic acid, styrene, methylmethacrylic acid, and cyclohexyl methacrylic acid were added in a molar ratio of 40: 20: 20: 20, respectively.
  • a binder of acrylic polymer having an acrylic unsaturated bond in the side chain was added by adding 20 molar ratios of glycidylmethacrylic acid to 0.3 g of N, N -dimethylaniline and 100 moles of solids of all monomers in the reactor.
  • Resin 2 was prepared.
  • the weight average molecular weight of polystyrene reduced by gel permeation chromatography (GPC) of the copolymer thus prepared was 20, 000 and the degree of dispersion was 2.0.
  • glycidylmethacrylic acid, styrene, methylmethacrylic acid and cyclohexylmethacrylic acid were each acrylic in a molar ratio of 40: 20: 20: 20.
  • a solid content of the monomer was added at 40% by weight, and then polymerized by stirring with stirring at 70 ° C. for 5 hours under a nitrogen atmosphere.
  • 0.3 g of N, N -dimethylaniline and 20 molar ratios of acrylic acid were added to 100 moles of solids of the entire monomer, followed by stirring at 100 ° C.
  • binder resin 3 an acrylic polymer having an acrylic unsaturated bond in the side chain. It was.
  • the weight average molecular weight of polystyrene reduced by gel permeation chromatography (GPC) of the copolymer thus prepared was 18,000, and the degree of dispersion was found to be 1.8.
  • Binder resins 1 to 3 according to the components and contents shown in Table 1 below in the reaction mixing tank equipped with the ultraviolet shielding film and the stirrer; Photoreactive compounds; Photopolymerization initiator of the present invention; And FC-430 (a 3M leveling agent) were added sequentially, stirred at room temperature, and PGMEA was added to the solvent so that the composition totaled 100% by weight to prepare a photoresist composition.
  • a red photoresist composition was prepared in the same manner except that 50 wt% of Pigment Red 177 (PR 177) dispersion having a solid content of 25 wt% was used instead of carbon black in Example 44. .
  • a photoresist composition was prepared in the same manner as in Example 27, except that Compound 4 was used instead of Compound 4 as a photopolymerization initiator.
  • the photoresist was spin coated on a glass substrate, dried on a hot plate at 100 ° C. for 1 minute, exposed using a step mask, and then developed in a 0.04% KOH aqueous solution. Sensitivity was evaluated for the exposure amount in which the step mask pattern maintains 80% of the initial thickness.
  • the photoresist composition was applied onto the substrate using a spin coater, then prebaked at 100 ° C. for 1 minute, exposed at 365 nm, and post-baked at 230 ° C. for 20 minutes to form a resist film.
  • the thickness ratio (%) before and after the postbaking was measured.
  • the silicon wafer in which the photoresist pattern was formed was cut
  • the pattern side wall was erected at an angle of 55 degrees or more with respect to the substrate, the film was not reduced, and it was determined as 'good', and the reduction of the film was judged as 'film'.
  • the resist film formed through a process such as prebake and postbake was immersed in a stripper solution for 10 minutes at 40 ° C., and then The change in transmittance and thickness was examined. When the change in transmittance and thickness is 2% or less, it is set as 'good', and when the change in transmittance and thickness is 2% or more, it is determined as 'poor'.
  • the photoresist composition was prebaked at 100 ° C. for 1 minute, exposed to the sensitivity of the photoresist, and then developed with a KOH aqueous solution to form a pattern of 20 um x 20 um. .
  • the formed pattern was crosslinked by postbake at 230 ° C. for 20 minutes, and the ductility was measured using a nano indentor. The measurement of the nanoindenter was determined to be 'good' if the total variation was more than 500 nm with 5 g.f loading, and 'bad' if it was less than 500 nm.
  • Example Sensitivity (mJ / cm 2 ) Residual rate (%) Pattern stability Chemical resistance ductility 27 45 91 Good Good Good 28 50 92 Good Good Good 29 45 91 Good Good Good 30 35 93 Good Good Good 31 45 93 Good Good 32 40 91 Good Good Good 33 40 91 Good Good Good 34 45 90 Good Good Good 35 50 92 Good Good Good 36 50 90 Good Good Good 37 50 89 Good Good Good 38 30 93 Good Good 39 45 91 Good Good Good 40 45 90 Good Good Good Good 41 40 93 Good Good Good Good 42 35 90 Good Good Good Good 43 40 90 Good Good Good Good 44 35 92 Good Good Good 45 40 91 Good Good Good Good Comparative Example 1 200 87 Film Bad Good Comparative Example 2 250 80 Film Bad Bad Bad
  • Dioxime ester compound according to the present invention from Table 2 is excellent in sensitivity even when using a small amount when used as a photopolymerization initiator of the photoresist composition, excellent properties such as residual film ratio, pattern stability, chemical resistance and ductility TFT- It was confirmed that the outgassing generated from the photopolymerization initiator can be minimized in the exposure and post-baking processes during the LCD manufacturing process, thereby reducing contamination and minimizing the defects that may occur.
  • the dioxime ester compound of the present invention When used as a photoinitiator of the photoresist composition, the dioxime ester compound of the present invention has excellent sensitivity even when used in a small amount, and has excellent physical properties such as residual film ratio, pattern stability, chemical resistance, and ductility. And it is possible to minimize the outgassing from the photopolymerization initiator in the post-baking process can reduce the contamination and there is an advantage that can minimize the defects that can be caused by this.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a novel dioximester compound, and a photopolymerization initiator and photoresist composition containing the same.

Description

신규한 디옥심에스테르 화합물 및 이를 포함하는 광중합 개시제 및 포토레지스트 조성물Novel dioxime ester compound and photopolymerization initiator and photoresist composition comprising same
본 발명은 신규한 디옥심에스테르 화합물 및 이를 포함하는 광중합 개시제 및 포토레지스트 조성물에 관한 것이다.The present invention relates to a novel dioxime ester compound and a photopolymerization initiator and photoresist composition comprising the same.
포토레지스트 조성물에 사용되는 광중합 개시제의 일반적인 예는 아세토페논 유도체, 벤조페논 유도체, 트리아진 유도체, 비이미다졸 유도체, 아실포스핀 옥사이드 유도체 및 옥심에스테르 유도체 등 여러 종류가 알려져 있으며, 이중 옥심에스테르 유도체는 자외선을 흡수하여 색을 거의 나타내지 않고, 라디칼 발생 효율이 높으며, 포토레지스트 조성물 재료들과의 상용성 및 안정성이 우수한 장점을 갖고 있다. 그러나 초기에 개발된 옥심 유도체 화합물은 광개시 효율이 낮으며, 특히 패턴 노광 공정 시 감도가 낮아 노광량을 늘려야 하고 이로 인해 생산량이 줄어드는 문제가 있다.As a general example of the photopolymerization initiator used in the photoresist composition, various kinds such as acetophenone derivatives, benzophenone derivatives, triazine derivatives, biimidazole derivatives, acylphosphine oxide derivatives and oxime ester derivatives are known. It absorbs ultraviolet rays, exhibits little color, has high radical generation efficiency, and has excellent compatibility and stability with photoresist composition materials. However, the earlier developed oxime derivative compounds have a low photoinitiation efficiency, in particular, a low sensitivity in the pattern exposure process, so the exposure should be increased, resulting in a decrease in production.
그러므로 광 감도가 우수한 광중합 개시제의 개발은 적은 양으로 충분한 감도를 구현 할 수 있어 원가 절감 효과 및 우수한 감도로 인해 노광량을 낮출 수 있어 생산량을 높일 수 있다. Therefore, the development of a photopolymerization initiator having excellent light sensitivity can realize sufficient sensitivity in a small amount, thereby reducing the exposure amount due to the cost reduction effect and the excellent sensitivity, thereby increasing the yield.
포토레지스트 조성물에 광중합 개시제로 사용 가능한 하기 화학식 A로 표시되는 다양한 옥심에스테르 화합물 유도체는 이미 공지되어 있다.Various oxime ester compound derivatives represented by the following formula (A) which can be used as photopolymerization initiators in photoresist compositions are already known.
[화학식 A] [Formula A]
Figure PCTKR2016000635-appb-I000001
Figure PCTKR2016000635-appb-I000001
옥심에스테르기를 갖는 광중합 개시제의 경우 화합물의 R, R', R"에 적절한 치환기를 도입하여 광중합 개시제의 흡수영역이 조절 가능한 다양한 광중합 개시제의 합성이 용이하다.In the case of the photoinitiator which has an oxime ester group, it is easy to synthesize | combine the various photoinitiator which can adjust the absorption region of a photoinitiator by introduce | transducing a suitable substituent to R, R ', and R "of a compound.
옥심에스테르 화합물은 포토레지스트 조성물에 365-435 nm의 빛을 조사함으로서 불포화 결합을 갖는 중합성 화합물을 중합 및 경화시킬 수 있어서 블랙매트릭스, 컬러필터, 컬럼 스페이서, 유연 절연막, 오버코트용 포토레지스트 조성물 등에 이용되고 있다.The oxime ester compound is capable of polymerizing and curing a polymerizable compound having an unsaturated bond by irradiating the photoresist composition with light of 365-435 nm, which is used for a black matrix, color filter, column spacer, flexible insulating film, photoresist composition for overcoat, and the like. It is becoming.
따라서 광개시제는 365-435 nm 등 장파장 광원에 높은 감도를 가지며, 광중합 반응성이 좋고, 제조가 용이하며, 열안정성 및 저장안정성이 높아 취급이 용이하며 용제(PGMEA; 프로필렌 글리콜 모노메틸 에테르 아세테이트)에 대한 만족할 만한 용해도 등 산업 현장의 요구를 충족시킬 수 있는 다양한 용도에 적합한 새로운 광개시제가 지속적으로 요구되고 있다.Therefore, the photoinitiator has high sensitivity to long wavelength light sources such as 365-435 nm, has good photopolymerization reactivity, easy to manufacture, high thermal stability and storage stability, and easy to handle, and it is easy to handle (PGMEA; propylene glycol monomethyl ether acetate). There is a continuing need for new photoinitiators suitable for a variety of applications that can meet the needs of industrial sites, such as satisfactory solubility.
최근에는 액정표시소자 및 OLED 등 박막 디스플레이에 사용되는 포토레지스트 조성물에 관하여, 보다 상세하게는 알칼리 현상액으로 현상되어 TFT-LCD와 같은 액정표시소자의 유기 절연막, 컬럼 스페이서, UV 오버코트, R.G.B. 컬러 레지스트 및 Black Matrix 등으로 패턴 형성이 가능한 고감도 광중합 개시제를 함유하는 포토레지스트 조성물에 관한 연구가 많이 진행되고 있다.Recently, photoresist compositions used in thin film displays, such as liquid crystal display devices and OLEDs, have been developed in more detail with alkaline developer to form organic insulating films, column spacers, UV overcoats, R.G.B. A lot of research is being conducted on the photoresist composition containing a high-sensitivity photopolymerization initiator capable of pattern formation with a color resist, a black matrix, or the like.
일반적으로 패턴을 형성하기 위해서 이용되는 레지스트 조성물로는 바인더 수지, 에틸렌 불포화 결합을 갖는 다관능성 모노머 및 광중합 개시제를 함유하는 포토레지스트 조성물이 선호되고 있다. Generally, as a resist composition used for forming a pattern, the photoresist composition containing a binder resin, the polyfunctional monomer which has an ethylenically unsaturated bond, and a photoinitiator is preferable.
그러나 종래의 광중합 개시제를 이용하여 패턴을 형성하는 경우 패턴 형성을 위한 노광 공정 시 감도가 낮아 광중합 개시제의 사용량을 늘리거나 노광량을 늘려야 하고 이로 인해 노광 공정에서 마스크를 오염시키고, 고온 가교 시에 광중합 개시제가 분해한 후 발생하는 부산물로 수율이 저하되는 단점이 있고, 노광량 증가에 따른 노광공정 시간이 늘어나 생산량이 줄어드는 문제점 등이 있어 이를 해결하기 위한 노력이 진행되고 있다.However, when the pattern is formed using a conventional photopolymerization initiator, the sensitivity is low during the exposure process for pattern formation, so the amount of use of the photopolymerization initiator must be increased or the exposure amount must be increased, thereby contaminating the mask in the exposure process, and the photopolymerization initiator at high temperature crosslinking. There is a disadvantage in that the yield is reduced as a by-product generated after decomposition, there is a problem that the production process is reduced by increasing the exposure process time according to the increase in the exposure amount, efforts are being made to solve this problem.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
[특허문헌 1] JP 2001-302871 A (2001.10.31)[Patent Document 1] JP 2001-302871 A (2001.10.31)
[특허문헌 2] JP 2006-160634 A (2006.06.22)[Patent Document 2] JP 2006-160634 A (2006.06.22)
[특허문헌 3] JP 2005-025169 A (2005.01.27)[Patent Document 3] JP 2005-025169 A (2005.01.27)
[특허문헌 4] JP 2005-242279 A (2005.09.08)[Patent Document 4] JP 2005-242279 A (2005.09.08)
[특허문헌 5] WO 02/100903 (2002.12.19)[Patent Document 5] WO 02/100903 (2002.12.19)
[특허문헌 6] WO 07/071497 (2007.06.28)[Patent Document 6] WO 07/071497 (2007.06.28)
[특허문헌 7] WO 08/138733 (2008.11.20)[Patent Document 7] WO 08/138733 (2008.11.20)
[특허문헌 8] WO 08/078686 (2008.07.03)[Patent Document 8] WO 08/078686 (2008.07.03)
[특허문헌 9] WO 09/081483 (2009.07.02)[Patent Document 9] WO 09/081483 (2009.07.02)
[특허문헌 10] KR 2013-0124215 A (2013.05.03)[Patent Document 10] KR 2013-0124215 A (2013.05.03)
[특허문헌 11] KR 2013-0115272 A (2013. 10.21)[Patent Document 11] KR 2013-0115272 A (2013. 10.21)
따라서 본 발명은 신규의 디옥심에스테르 화합물 및 이를 함유하는 광중합 개시제 및 상기 디옥심에스테르 화합물을 포함하는 포토레지스트 조성물을 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a novel dioxime ester compound, a photopolymerization initiator containing the same, and a photoresist composition comprising the dioxime ester compound.
또한, 본 발명은 신규의 디옥심에스테르 화합물을 포함하는 포토레지스트 조성물의 경화물을 포함하는 성형물을 제공하는데 또 다른 목적이 있다. Another object of the present invention is to provide a molded article comprising a cured product of a photoresist composition containing a novel dioxime ester compound.
또한, 본 발명은 본 발명의 성형물을 포함하는 디스플레이 장치를 제공하는데 또 다른 목적이 있다.Another object of the present invention is to provide a display device including the molding of the present invention.
상기의 목적을 달성하기 위하여 본 발명은 하기 화학식 1로 표시되는 디옥심에스테르 화합물 및 이를 포함하는 광중합 개시제 및 포토레지스트 조성물을 제공한다.In order to achieve the above object, the present invention provides a dioxime ester compound represented by the following formula (1), a photopolymerization initiator and a photoresist composition comprising the same.
[화학식 1][Formula 1]
Figure PCTKR2016000635-appb-I000002
Figure PCTKR2016000635-appb-I000002
상기 화학식 1에서, In Chemical Formula 1,
R1 내지 R3은 각각 독립적으로 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, (C1-C20)알콕시, (C6-C20)아릴(C1-C20)알킬, 히드록시(C1-C20)알킬, 히드록시(C1-C20)알콕시(C1-C20)알킬, (C3-C20)사이클로알킬 또는 (C3-C20)사이클로알킬(C1-C20)알킬이고; R 1 to R 3 are each independently hydrogen, halogen, (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl, (C 1 -C 20 ) alkoxy, (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl, hydroxy (C 1 -C 20 ) alkyl, hydroxy (C 1 -C 20 ) alkoxy (C 1 -C 20 ) alkyl, (C 3 -C 20 ) cycloalkyl or (C 3 -C 20 ) cycloalkyl (C 1 -C 20 ) alkyl;
A는 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, (C6-C20)아릴(C1-C20)알킬, 아미노, 니트로, 시아노 또는 히드록시이고;A is hydrogen, halogen, (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl, (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl, amino, nitro, cyano or hydroxy ego;
n은 0 내지 2의 정수이다.n is an integer of 0-2.
본 발명의 용어 "할로" 또는 "할로겐"은 불소, 염소, 브롬 또는 요오드 원자를 의미한다. The term "halo" or "halogen" in the present invention means fluorine, chlorine, bromine or iodine atoms.
본 발명의 용어 "알킬"은 탄소 및 수소 원자만으로 구성된 1가의 직쇄 또는 분쇄 포화 탄화수소 라디칼을 의미하는 것으로, 구체적인 예로 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, t-부틸, 펜틸, 헥실, 옥틸, 노닐 등을 포함하지만 이에 한정되지는 않는다.As used herein, the term "alkyl" refers to a monovalent straight-chain or pulverized saturated hydrocarbon radical consisting solely of carbon and hydrogen atoms, e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl , Octyl, nonyl, and the like.
본 발명의 용어 "아릴"은 하나의 수소 제거에 의해서 방향족 탄화수소로부터 유도된 유기 라디칼로, 각 고리에 적절하게는 4 내지 7개, 바람직하게는 5 또는 6개의 고리원자를 포함하는 단일 또는 융합고리계를 포함하며, 다수개의 아릴이 단일결합으로 연결되어 있는 형태까지 포함한다. 구체적인 예로 페닐, 나프틸, 바이페닐, 터페닐, 안트릴, 인데닐(indenyl), 플루오레닐, 페난트릴 등을 포함하지만, 이에 한정되지는 않는다. The term "aryl" in the present invention refers to an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, in which a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, suitably in each ring It includes a system, including a form in which a plurality of aryl is connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, and the like.
본 발명의 용어 "알콕시"는 -O-알킬 라디칼을 의미하는 것으로, 메톡시, 에톡시, 이소프로폭시, 부톡시, 이소부톡시, t-부톡시 등으로 예시될 수 있다.As used herein, the term "alkoxy" refers to an -O-alkyl radical, which may be exemplified by methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy and the like.
본 발명의 용어 "아릴알킬"는 상기 정의한 아릴이 치환된 알킬 기로, 벤질 등으로 예시될 수 있다.The term "arylalkyl" of the present invention is an alkyl group substituted with aryl as defined above, and may be exemplified by benzyl and the like.
본 발명의 용어 "히드록시알킬"은 히드록시가 치환된 알킬기로, 히드록시메틸, 히드록시에틸, 히드록시프로필, 히드록시부틸, 히드록시펜틸, 히드록시헥실 등으로 예시될 수 있다.The term "hydroxyalkyl" of the present invention is an hydroxy substituted alkyl group, which may be exemplified by hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, and the like.
본 발명의 용어 "히드록시알콕시알킬"은 히드록시알콕시로 치환된 알킬 기로, 히드록시메톡시메틸, 히드록시메톡시에틸, 히드록시메톡시프로필, 히드록시메톡시부틸, 히드록시에톡시메틸, 히드록시에톡시에틸, 히드록시에톡시프로필, 히드록시에톡시부틸, 히드록시에톡시펜틸, 히드록시에톡시헥실 등으로 예시될 수 있다.The term "hydroxyalkoxyalkyl" of the present invention is an alkyl group substituted with hydroxyalkoxy, which is hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, Hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl, hydroxyethoxyhexyl and the like.
본 발명의 용어 "시클로알킬"은 탄소 고리원수 3 내지 7의 단환상 알킬 기 뿐만 아니라 두 개 이상의 단환상 알킬이 융합된 다환상 알킬 기를 의미한다. 구체적인 예로는 시클로프로필, 시클로부틸, 시클로펜틸, 시클로헥실 등을 들 수 있으나, 이에 한정되지는 않는다.The term "cycloalkyl" as used herein means a monocyclic alkyl group having 3 to 7 carbon atoms as well as a polycyclic alkyl group in which two or more monocyclic alkyls are fused. Specific examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
본 발명의 용어 "시클로알킬알킬"은 상기 정의한 시클로알킬이 치환된 알킬기를 의미하는 것으로, 시클로프로필메틸, 시클로부틸메틸, 시클로펜틸메틸, 시클로프로필에틸 등으로 예시될 수 있다.The term "cycloalkylalkyl" as used herein refers to an alkyl group substituted with a cycloalkyl as defined above, and may be exemplified by cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclopropylethyl and the like.
또한, 본 발명에 기재되어 있는 '(C1-C20)알킬'기는 바람직하게는 (C1-C10)알킬이고, 더 바람직하게는 (C1-C6)알킬이다. '(C6-C20)아릴'기는 바람직하게는 (C6-C18)아릴이다. '(C1-C20)알콕시'기는 바람직하게는 (C1-C10)알콕시이고, 더 바람직하게는 (C1-C4)알콕시이다. '(C6-C20)아릴(C1-C20)알킬'기는 바람직하게는 (C6-C18)아릴(C1-C10)알킬이고, 더 바람직하게는 (C6-C18)아릴(C1-C6)알킬이다. '히드록시(C1-C20)알킬'기는 바람직하게는 히드록시(C1-C10)알킬이고, 더 바람직하게는 히드록시(C1-C6)알킬이다. '히드록시(C1-C20)알콕시(C1-C20)알킬'기는 바람직하게는 히드록시(C1-C10)알콕시(C1-C10)알킬이고, 더 바람직하게는 히드록시(C1-C4)알콕시(C1-C6))알킬이다. '(C3-C20)사이클로알킬'기는 바람직하게는 (C3-C10)사이클로알킬이다. '(C3-C20)사이클로알킬(C1-C20)알킬'기는 바람직하게는 (C3-C10)사이클로알킬(C1-C10)알킬이고, 더 바람직하게는 (C3-C10)사이클로알킬(C1-C6)알킬이다. In addition, the '(C 1 -C 20 ) alkyl' group described in the present invention is preferably (C 1 -C 10 ) alkyl, more preferably (C 1 -C 6 ) alkyl. The '(C 6 -C 20 ) aryl' group is preferably (C 6 -C 18 ) aryl. The '(C 1 -C 20 ) alkoxy' group is preferably (C 1 -C 10 ) alkoxy, more preferably (C1-C4) alkoxy. The '(C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl' group is preferably (C 6 -C 18 ) aryl (C 1 -C 10 ) alkyl, more preferably (C 6 -C 18) ) Aryl (C 1 -C 6 ) alkyl. The 'hydroxy (C 1 -C 20 ) alkyl' group is preferably hydroxy (C 1 -C 10 ) alkyl, more preferably hydroxy (C 1 -C 6 ) alkyl. The 'hydroxy (C 1 -C 20 ) alkoxy (C 1 -C 20 ) alkyl' group is preferably hydroxy (C 1 -C 10 ) alkoxy (C 1 -C 10 ) alkyl, more preferably hydroxy (C 1 -C 4 ) alkoxy (C 1 -C 6 )) alkyl. The '(C 3 -C 20 ) cycloalkyl' group is preferably (C 3 -C 10 ) cycloalkyl. The '(C 3 -C 20 ) cycloalkyl (C 1 -C 20 ) alkyl' group is preferably (C 3 -C 10 ) cycloalkyl (C 1 -C 10 ) alkyl, more preferably (C 3- C 10 ) cycloalkyl (C 1 -C 6 ) alkyl.
상기 화학식 1에서, n이 2인 경우 각각의 R1은 서로 동일하거나 상이할 수 있다. In Formula 1, when n is 2, each R 1 may be the same or different from each other.
보다 구체적으로 상기 R1 내지 R3는 각각 독립적으로 수소, 브로모, 클로로, 아이오도, 메틸, 에틸, n-프로필, i-프로필, n-부틸, i-부틸, t-부틸, n-펜틸, i-펜틸, n-헥실, i-헥실, 페닐, 나프틸, 바이페닐, 터페닐, 안트릴, 인데닐, 페난트릴, 메톡시, 에톡시, n-프로필옥시, i-프로필옥시, n-부톡시, i-부톡시, t-부톡시, 벤질, 히드록시메틸, 히드록시에틸, 히드록시n-프로필, 히드록시n-부틸, 히드록시i-부틸, 히드록시n-펜틸, 히드록시i-펜틸, 히드록시n-헥실, 히드록시i-헥실, 히드록시메톡시메틸, 히드록시메톡시에틸, 히드록시메톡시프로필, 히드록시메톡시부틸, 히드록시에톡시메틸, 히드록시에톡시에틸, 히드록시에톡시프로필, 히드록시에톡시부틸, 히드록시에톡시펜틸, 히드록시에톡시헥실, 사이클로프로필, 사이클로펜틸, 사이클로헥실, 사이클로프로필메틸, 사이클로펜틸메틸 또는 사이클로헥실메틸이고;More specifically, R 1 to R 3 are each independently hydrogen, bromo, chloro, iodo, methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, t -butyl, n -pentyl , i -pentyl, n -hexyl, i -hexyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy, n -propyloxy, i -propyloxy, n -Butoxy, i -butoxy, t -butoxy, benzyl, hydroxymethyl, hydroxyethyl, hydroxy n -propyl, hydroxy n -butyl, hydroxy i -butyl, hydroxy n -pentyl, hydroxy i -pentyl, hydroxy n -hexyl, hydroxy i -hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxy Ethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl, hydroxyethoxyhexyl, cyclopropyl, cyclopentyl, cyclohexyl, A cycle methyl, cyclopentyl-methyl or cyclohexyl-methyl;
A는 수소, 브로모, 클로로, 메틸, 에틸, n-프로필, i-프로필, n-부틸, i-부틸, t-부틸, 페닐, 나프틸, 바이페닐, 터페닐, 안트릴, 인데닐, 페난트릴, 벤질, 아미노, 니트로, 시아노 또는 히드록시일 수 있으며, 이에 한정되지는 않는다.A is hydrogen, bromo, chloro, methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, t -butyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, Phenanthryl, benzyl, amino, nitro, cyano or hydroxy, but is not limited thereto.
바람직하게, 상기 화학식 1에서 R1은 수소, (C1-C20)알킬, (C6-C20)아릴(C1-C20)알킬, 히드록시(C1-C20)알킬, 히드록시(C1-C20)알콕시(C1-C20)알킬, (C3-C20)사이클로알킬 또는 (C3-C20)사이클로알킬(C1-C20)알킬이고; R2 및 R3은 각각 독립적으로 (C1-C20)알킬, (C6-C20)아릴, (C6-C20)아릴(C1-C20)알킬, 히드록시(C1-C20)알킬, 히드록시(C1-C20)알콕시(C1-C20)알킬, (C3-C20)사이클로알킬 또는 (C3-C20)사이클로알킬(C1-C20)알킬이고; A는 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, (C6-C20)아릴(C1-C20)알킬, 니트로 또는 시아노일 수 있다.Preferably, in Formula 1, R 1 is hydrogen, (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl, hydroxy (C 1 -C 20 ) alkyl, hydride Oxy (C 1 -C 20 ) alkoxy (C 1 -C 20 ) alkyl, (C 3 -C 20 ) cycloalkyl or (C 3 -C 20 ) cycloalkyl (C 1 -C 20 ) alkyl; R 2 and R 3 are each independently (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl, (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl, hydroxy (C 1- C 20 ) alkyl, hydroxy (C 1 -C 20 ) alkoxy (C 1 -C 20 ) alkyl, (C 3 -C 20 ) cycloalkyl or (C 3 -C 20 ) cycloalkyl (C 1 -C 20 ) Alkyl; A can be hydrogen, halogen, (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl, (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl, nitro or cyano.
보다 바람직하게, 상기 화학식 1에서 R1은 수소, (C1-C20)알킬, (C3-C20)사이클로알킬 또는 (C3-C20)사이클로알킬(C1-C20)알킬이고; R2 및 R3은 각각 독립적으로 (C1-C20)알킬, (C6-C20)아릴 또는 (C3-C20)사이클로알킬이고; A는 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, 니트로 또는 시아노일 수 있다.More preferably, in Formula 1, R 1 is hydrogen, (C 1 -C 20 ) alkyl, (C 3 -C 20 ) cycloalkyl or (C 3 -C 20 ) cycloalkyl (C 1 -C 20 ) alkyl ; R 2 and R 3 are each independently (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl or (C 3 -C 20 ) cycloalkyl; A can be hydrogen, halogen, (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl, nitro or cyano.
본 발명에 따른 디옥심에스테르 화합물로는 대표적으로 하기의 화합물을 들 수 있으나, 하기 화합물이 본 발명을 한정하는 것은 아니다.The dioxime ester compound according to the present invention may include the following compounds, but the following compounds are not intended to limit the present invention.
Figure PCTKR2016000635-appb-I000003
Figure PCTKR2016000635-appb-I000003
Figure PCTKR2016000635-appb-I000004
Figure PCTKR2016000635-appb-I000004
Figure PCTKR2016000635-appb-I000005
Figure PCTKR2016000635-appb-I000005
Figure PCTKR2016000635-appb-I000006
Figure PCTKR2016000635-appb-I000006
Figure PCTKR2016000635-appb-I000007
Figure PCTKR2016000635-appb-I000007
Figure PCTKR2016000635-appb-I000008
Figure PCTKR2016000635-appb-I000008
Figure PCTKR2016000635-appb-I000009
Figure PCTKR2016000635-appb-I000009
Figure PCTKR2016000635-appb-I000010
Figure PCTKR2016000635-appb-I000010
본 발명에 따른 상기 화학식 1로 표시되는 디옥심에스테르 화합물은 일례로 하기 반응식 1에 나타난 바와 같이 제조될 수 있다.The dioxime ester compound represented by Formula 1 according to the present invention may be prepared as shown in Scheme 1 below.
[반응식 1] Scheme 1
Figure PCTKR2016000635-appb-I000011
Figure PCTKR2016000635-appb-I000011
[상기 반응식 1에서 A, R1 내지 R3 및 n은 화학식 1에서의 정의와 동일하고, X1 및 X2는 각각 독립적으로 할로겐이다.][In Scheme 1, A, R 1 to R 3 and n are the same as defined in Formula 1, and X 1 and X 2 are each independently halogen.]
또한, 본 발명은 상기 화학식 1로 표시되는 디옥심에스테르 화합물을 포함하는 광중합 개시제를 제공한다.In addition, the present invention provides a photopolymerization initiator comprising a dioxime ester compound represented by the formula (1).
또한, 본 발명은 상기 화학식 1로 표시되는 디옥심에스테르 화합물을 포함하는 포토레지스트 조성물을 제공한다.In another aspect, the present invention provides a photoresist composition comprising a dioxime ester compound represented by the formula (1).
본 발명에서 상기 화학식 1로 표시되는 디옥심에스테르 화합물은 광중합 개시제로써 포토레지스트 조성물에 포함될 수 있다.In the present invention, the dioxime ester compound represented by Chemical Formula 1 may be included in the photoresist composition as a photopolymerization initiator.
본 발명의 포토레지스트 조성물은 상기 화학식 1로 표시되는 디옥심에스테르 화합물, 바인더 수지, 에틸렌성 불포화결합을 갖는 중합성 화합물 및 용매 등을 포함하며, 패턴 특성 조절과 내열성 및 내화학성 등의 박막 물성이 뛰어나다.The photoresist composition of the present invention includes a dioxime ester compound represented by Chemical Formula 1, a binder resin, a polymerizable compound having an ethylenically unsaturated bond, a solvent, and the like, and has thin film properties such as pattern property control and heat resistance and chemical resistance. outstanding.
또한, 본 발명의 포토레지스트 조성물은 상기 화학식 1로 표시되는 디옥심에스테르 화합물 이외에 티옥산톤계 화합물, 아세토페논계 화합물, 비이미다졸계 화합물, 트리아진계 화합물, 티올계 화합물 및 O-아실옥심계 화합물로 이루어지는 군으로부터 선택되는 1종 또는 2종 이상의 공지의 광중합 개시제를 더 포함할 수 있다.In addition, the photoresist composition of the present invention is a thioxanthone compound, acetophenone compound, biimidazole compound, triazine compound, thiol compound and O-acyl oxime compound in addition to the dioxime ester compound represented by the formula (1) It may further comprise one or two or more known photopolymerization initiators selected from the group consisting of.
상기 티옥산톤계 화합물로는 티옥산톤, 2-클로로티옥산톤, 2-메틸티옥산톤, 2-이소프로필티옥산톤, 4-이소프로필티옥산톤, 2,4-디클로로티옥산톤, 2,4-디메틸티옥산톤, 2,4-디에틸티옥산톤, 2,4-디이소프로필티옥산톤 등이 있으며, 이들을 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 상기 아세토페논계 화합물로는 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)부탄-1-온, 2-(4-메틸벤질)-2-(디메틸아미노)-1-(4-모르폴리노페닐)부탄-1-온 등이 있으며, 이들을 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 상기 비이미다졸계 화합물로는 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라페닐-1,2'-비이미다졸, 2,2'-비스(2,4-디클로로로페닐)-4,4',5,5'-테트라페닐-1,2'-비이미다졸, 2,2'-비스(2,4,6-트리클로로페닐)-4,4',5,5'-테트라페닐-1,2'-비이미다졸 등이 있으며, 이들을 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 상기 트리아진계 화합물로는 2,4,6-트리스(트리클로로메틸)-s-트리아진, 2-메틸-4,6-비스(트리클로로메틸)-s-트리아진, 2-[2-(5-메틸푸란-2-일)에테닐]-4,6-비스(트리클로로메틸)-s-트리아진, 2-[2-(푸란-2-일)에테닐]-4,6-비스(트리클로로메틸)-s-트리아진, 2-[2-(4-디에틸아미노-2-메틸페닐)에테닐]-4,6-비스(트리클로로메틸)-s-트리아진, 2-[2-(3,4-디메톡시페닐)에테닐]-4,6-비스(트리클로로메틸)-s-트리아진, 2-(4-메톡시페닐)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(4-에톡시스티릴)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(4-n-부톡시페닐)-4,6-비스(트리클로로메틸)-s-트리아진 등이 있으며, 이들을 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 상기 O-아실옥심계 화합물로서는, 예를 들면, 1,2-옥탄디온-1-[4-(페닐티오)페닐]-2-(O-벤조일옥심), 에탄온-1-[9-에틸-6-(2-메틸벤조일)-9H-카르바졸-3-일]-1-(O-아세틸옥심), 에탄온-1-[9-에틸-6-(2-메틸-4-테트라하이드로푸라닐메톡시벤조일)-9H-카르바졸-3-일]-1-(O-아세틸옥심), 에탄온-1-[9-에틸-6-(2-메틸-4-(2,2-디메틸-1,3-디옥소라닐)메톡시벤조일 r-9H-카르바졸-3-일]-1-(O-아세틸옥심) 등이 있으며, 이들을 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 상기 공지의 광중합 개시제는 박막 패턴 형성을 보다 유연하게 하기 위한 특성을 부여하기 위하여 포토레지스트 조성물 100 중량%에 대하여 0.1 내지 5.0 중량%를 사용할 수 있다.Examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-dichlorothioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- diisopropyl thioxanthone, etc., These can be used individually or in mixture of 2 or more types, respectively. Examples of the acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholine Nophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like; It can mix and use species. As the biimidazole-based compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis ( 2,4-dichlorolophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4 , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, and the like, and these may be used alone or in combination of two or more thereof. Examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- ( 5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [ 2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl ) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6- Bis (trichloromethyl) -s-triazine and the like, and these may be used alone or in combination of two or more thereof. As said O-acyl oxime type compound, the 1, 2- octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyl oxime), ethanone-1- [9-ethyl, for example] -6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydro Furanylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4- (2,2-dimethyl -1,3-dioxoranyl) methoxybenzoyl r-9H-carbazol-3-yl] -1- (O-acetyloxime), and the like, and these may be used alone or in combination of two or more thereof. The known photopolymerization initiator may be used in an amount of 0.1 to 5.0% by weight based on 100% by weight of the photoresist composition in order to impart properties for more flexible thin film pattern formation.
본 발명의 일 구체예에 따르면, 상기 포토레지스트 조성물에 사용되는 바인더 수지로는 아크릴 중합체 또는 측쇄에 아크릴 불포화 결합을 갖는 아크릴 중합체를 사용할 수 있으며, 패턴 특성 조절과 내열성 및 내화학성 등의 박막 물성을 부여하기 위하여 포토레지스트 조성물 100 중량%에 대하여 3 내지 50 중량%를 사용하는 것이 바람직하며, 아크릴 중합체의 겔 투과 크로마토그래피(GPC)에 의한 폴리스티렌 환산 중량 평균 분자량은 2,000 내지 30O,O00, 분산도는 1.0 내지 10.0 인 것을 사용하는 것이 바람직하며, 중량 평균 분자량 4,000 내지 10O,O00 인 것을 사용하는 것이 더욱 바람직하다.According to one embodiment of the present invention, as the binder resin used in the photoresist composition, an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in the side chain may be used, and thin film properties such as pattern property control and heat resistance and chemical resistance may be used. It is preferable to use 3 to 50% by weight with respect to 100% by weight of the photoresist composition, polystyrene reduced weight average molecular weight by gel permeation chromatography (GPC) of the acrylic polymer is 2,000 to 30,000,000, dispersion degree is It is preferable to use what is 1.0-10.0, and it is more preferable to use what is a weight average molecular weight 4,000-100000,00.
상기 아크릴 중합체는 하기 단량체들을 포함하는 단량체들의 공중합체로서 단량체의 예로는 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트, 펜틸(메타)아크릴레이트, 헥실(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 헵틸(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 노닐(메타)아크릴레이트, 데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 도데실(메타)아크릴레이트, 테트라데실(메타)아크릴레이트, 헥사데실(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 아다만틸(메타)아크릴레이트, 디시클로펜타닐(메타)아크릴레이트, 디시클로펜테닐(메타)아크릴레이트, 벤질(메타)아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 2-에톡시에틸(메타)아크릴레이트, 아크릴산, 메타아크릴산, 이타코닉산, 말레익산, 말레익산무수물, 말레익산모노알킬에스터, 모노알킬 이타코네이트, 모노알킬 퓨말레이트, 글리시딜아크릴레이트, 글리시딜메타아크릴레이트, 3,4-에폭시부틸(메타)아크릴레이트, 2,3-에폭시시클로헥실(메타)아크릴레이트, 3,4-에폭시시클로헥실메틸(메타)아크릴레이트, 3-메틸옥세탄-3-메틸(메타)아크릴레이트, 3-에틸옥세탄-3-메틸(메타)아크릴레이트, 스틸렌, α-메틸스틸렌, 아세톡시스틸렌, N-메틸말레이미드, N-에틸말레이미드, N-프로필말레이미드, N-부틸말레이미드, N-시클로헥실말레이미드, (메타)아크릴아미드, N-메틸(메타)아크릴아미드 등을 들 수 있으며, 이들을 각각 단독으로 또는 2종 이상 함께 사용할 수 있다.The acrylic polymer is a copolymer of monomers including the following monomers. Examples of the monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth). Acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) ) Acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) ) Acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, acrylic acid, methacryl , Itaconic acid, maleic acid, maleic acid anhydride, maleic acid monoalkyl ester, monoalkyl itaconate, monoalkyl fumaleate, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth ) Acrylate, 2,3-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-methyloxetane-3-methyl (meth) acrylate, 3-ethyl jade Cetane-3-methyl (meth) acrylate, styrene, α-methylstyrene, acetoxystyrene, N -methylmaleimide, N -ethylmaleimide, N -propylmaleimide, N -butylmaleimide, N -cyclohexyl Maleimide, (meth) acrylamide, N -methyl (meth) acrylamide, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.
측쇄에 아크릴 불포화 결합을 갖는 아크릴 중합체는 카르복실 산을 함유한 아크릴 공중합체에 에폭시 수지를 부가반응한 공중합체로서 아크릴산, 메타아크릴산, 이타코닉산, 말레익산, 말레익산모노알킬에스터 등의 카르복실산을 함유한 아크릴 모노머와 메틸(메타)아크릴레이트, 헥실(메타)아크릴레이트 등의 알킬(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 아다만틸(메타)아크릴레이트, 디시클로펜타닐(메타)아크릴레이트, 디시클로펜테닐(메타)아크릴레이트, 벤질(메타)아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 2-에톡시에틸(메타)아크릴레이트, 스틸렌, α-메틸스틸렌, 아세톡시스틸렌, N-메틸말레이미드, N-에틸말레이미드, N-프로필말레이미드, N-부틸말레이미드, N-시클로헥실말레이미드, (메타)아크릴 아미드, N-메틸(메타)아크릴아미드 등의 모노머 2종 이상을 공중합 하여 얻은 카르복실산을 함유한 아크릴 공중합체에 글리시딜아크릴레이트, 글리시딜메타아크릴레이트, 3,4-에폭시부틸(메타)아크릴레이트, 2,3-에폭시시클로헥실(메타)아크릴레이트, 3,4-에폭시시클로헥실메틸(메타)아크릴레이트 등의 에폭시 수지를 40 내지 180 ℃의 온도에서 부가 반응하여 얻어진 바인더 수지를 사용할 수 있다.An acrylic polymer having an acrylic unsaturated bond in the side chain is a copolymer obtained by adding an epoxy resin to an acrylic copolymer containing a carboxylic acid, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and maleic acid monoalkyl ester. Acrylic monomer containing acid, alkyl (meth) acrylates, such as methyl (meth) acrylate and hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) ) Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylic acrylate, styrene, α- methyl styrene, acetoxy-styrene, N - methyl maleimide, N - ethyl maleimide, N - propyl maleimide, N - butyl maleimide, N - cyclohexyl maleimide, Oh (meth) Reel amide, N - methyl (meth) glycidyl acrylate in the copolymer containing a carboxylic acid obtained by copolymerizing monomers of two or more thereof, such as acrylamide, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxy-butyl Binder resin obtained by addition reaction of epoxy resins, such as (meth) acrylate, 2, 3- epoxycyclohexyl (meth) acrylate, and 3, 4- epoxycyclohexyl methyl (meth) acrylate, at the temperature of 40-180 degreeC Can be used.
측쇄에 아크릴 불포화 결합을 갖는 아크릴 중합체의 또 다른 예로는 에폭시기를 함유한 아크릴 공중합체에 카르복실산을 부가반응한 공중합체로 글리시딜아크릴레이트, 글리시딜메타아크릴레이트, 3,4-에폭시부틸(메타)아크릴레이트, 2,3-에폭시시클로헥실(메타)아크릴레이트, 3,4-에폭시시클로헥실 메틸(메타)아크릴레이트 등의 에폭시기를 함유한 아크릴 모노머와 메틸(메타)아크릴레이트, 헥실(메타)아크릴레이트 등의 알킬(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 아다만틸(메타)아크릴레이트, 디시클로펜타닐(메타)아크릴레이트, 디시클로펜테닐(메타)아크릴레이트, 벤질(메타)아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 2-에톡시에틸(메타)아크릴레이트, 스틸렌, α-메틸스틸렌, 아세톡시스틸렌, N-메틸말레이미드, N-에틸말레이미드, N-프로필말레이미드, N-부틸말레이미드, N-시클로헥실말레이미드, (메타)아크릴아미드, N-메틸(메타)아크릴아미드 등의 모노머 2종 또는 2종 이상을 공중합 하여 얻은 에폭시기를 함유한 아크릴 공중합체에 아크릴산, 메타아크릴산, 이타코닉산, 말레익산, 말레익산모노알킬 에스터 등의 카르복실산을 함유한 아크릴 모노머와 40 내지 180 ℃의 온도에서 부가 반응하여 얻어진 바인더 수지를 사용할 수 있다.Another example of an acrylic polymer having an acrylic unsaturated bond in the side chain is a copolymer in which a carboxylic acid is added to an acrylic copolymer containing an epoxy group, and glycidyl acrylate, glycidyl methacrylate, and 3,4-epoxy. Acrylic monomer containing methyl groups such as butyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, methyl (meth) acrylate, hexyl Alkyl (meth) acrylates, such as (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclo Pentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, styrene, α-methylstyrene, acetoxystyrene, N − Me Maleimide, N - ethyl maleimide, N - propyl maleimide, N - butyl maleimide, N - cyclohexyl maleimide, (meth) acrylamide, N - methyl (meth) 2 alone or in combination of two monomers such as acrylamide The addition reaction at the temperature of 40-180 degreeC with the acryl monomer containing the carboxylic acid, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and monoalkyl ester, to the acrylic copolymer containing the epoxy group obtained by copolymerizing the above The binder resin obtained by the use can be used.
본 발명의 포토레지스트 조성물에 있어서 에틸렌성 불포화결합을 갖는 중합성 화합물은 패턴 형성 시 광반응에 의하여 가교되어 패턴을 형성하는 역할을 하며 고온 가열시 가교되어 내화학성 및 내열성을 부여한다. 상기 에틸렌성 불포화결합을 갖는 중합성 화합물은 포토레지스트 조성물 100 중량%에 대하여 0.001 내지 40 중량%를 사용하는 것이 바람직하다. 에틸렌성 불포화결합을 갖는 중합성 화합물이 과량 첨가되면 가교도가 지나치게 높아져 패턴의 연성이 저하되는 단점이 발생할 수 있다.In the photoresist composition of the present invention, the polymerizable compound having an ethylenically unsaturated bond serves to form a pattern by crosslinking by photoreaction at the time of pattern formation and crosslinking at high temperature to impart chemical resistance and heat resistance. The polymerizable compound having an ethylenically unsaturated bond preferably uses 0.001 to 40% by weight based on 100% by weight of the photoresist composition. When an excessive amount of the polymerizable compound having an ethylenically unsaturated bond is added, a crosslinking degree may be excessively high, which may cause a disadvantage in that the ductility of the pattern is lowered.
상기 에틸렌성 불포화결합을 갖는 중합성 화합물은 구체적으로 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 라우릴(메타)아크릴레이트 등의 (메타)아크릴산의 알킬에스테르, 글리시딜(메타)아크릴레이트, 에틸렌옥사이드기의 수가 2 내지 14인 폴리에틸렌 글리콜모노(메타)아크릴레이트, 에틸렌글리콜디(메타)아크릴레이트, 에틸렌 옥사이드기의 수가 2 내지 14인 폴리에틸렌 글리콜디(메타)아크릴레이트, 프로필렌옥사이드기의 수가 2 내지 14인 프로필렌글리콜디(메타)아크릴레이트, 트리메틸올프로판디(메타)아크릴레이트, 비스페놀 A 디글리시딜에테르아크릴산 부가물, β-히드록시 에틸(메타)아크릴레이트의 프탈산디에스테르, β-히드록시에틸(메타)아크릴레이트의 톨루엔 디이소시아네이트 부가물, 트리메틸올프로판트리(메타)아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 디펜타에리스리톨트리(메타)아크릴레이트와 같이 다가 알코올과 α,β-불포화 카르복시산을 에스테르화하여 얻어지는 화합물, 트리메틸올프로판트리글리시딜에테르아크릴산 부가물과 같이 다가 글리시딜 화합물의 아크릴산 부가물 등을 들 수 있으며, 이들을 각각 단독으로 또는 2종 이상 함께 사용할 수 있다. The polymerizable compound having an ethylenically unsaturated bond is specifically methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acryl Alkyl ester of (meth) acrylic acid, such as the rate, glycidyl (meth) acrylate, polyethyleneglycol mono (meth) acrylate whose number of ethylene oxide groups is 2-14, ethylene glycol di (meth) acrylate, ethylene oxide group Polyethylene glycol di (meth) acrylate having a number of from 2 to 14, propylene glycol di (meth) acrylate having a number of from 2 to 14 of propylene oxide group, trimethylolpropanedi (meth) acrylate, bisphenol A diglycidyl ether Acrylic acid adduct, phthalic acid diester of β-hydroxyethyl (meth) acrylate, toluene diisocyanate of β-hydroxyethyl (meth) acrylate Yite adduct, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylic A compound obtained by esterifying a polyhydric alcohol and an α, β-unsaturated carboxylic acid, such as a latent and dipentaerythritol tri (meth) acrylate, and an acrylic acid adduct of a polyvalent glycidyl compound, such as a trimethylolpropanetriglycidyl ether acrylic acid adduct. These etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.
또한, 본 발명의 포토레지스트 조성물에서 광중합 개시제로 사용되는 상기 화학식 1의 디옥심에스테르 화합물의 첨가량은 투명성을 높이며 노광량을 최소화하기 위한 함량으로서 포토레지스트 조성물 100 중량%에 대하여 0.01 내지 10 중량%, 바람직하게는 0.1 내지 5 중량%를 사용하는 것이 보다 효과적이다.In addition, the amount of the dioxime ester compound of Chemical Formula 1 used as a photopolymerization initiator in the photoresist composition of the present invention is 0.01 to 10% by weight with respect to 100% by weight of the photoresist composition, preferably to increase transparency and minimize exposure. It is more effective to use 0.1 to 5% by weight.
또한, 본 발명의 포토레지스트 조성물은 필요에 따라 접착보조제로 에폭시기 또는 아민기를 갖는 실리콘계 화합물을 더 포함할 수 있다.In addition, the photoresist composition of the present invention may further include a silicone-based compound having an epoxy group or an amine group as an adhesion aid as necessary.
본 발명의 포토레지스트 조성물에서 실리콘계 화합물은 ITO 전극과 포토레지스트 조성물과의 접착력을 향상시키며, 경화 후 내열 특성을 증대시킬 수 있다. 상기 에폭시기 또는 아민기를 갖는 실리콘계 화합물로는 (3-글리시드옥시프로필)트리메톡시실레인, (3-글리시드옥시프로필)트리에톡시실레인, (3-글리시드옥시프로필)메틸디메톡시실레인, (3-글리시드옥시프로필)메틸디에톡시실레인, (3-글리시드옥시프로필)디메틸메톡시실레인, (3-글리시드옥시프로필)디메틸에톡시실레인, 3,4-에폭시부틸트리메톡시실레인, 3,4-에폭시부틸트리에톡시실레인, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실레인, 2-(3,4-에폭시시클로헥실)에틸트리에톡시실레인 및 아미노프로필트리메톡시실레인 등이 있으며, 이들을 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 상기 에폭시기 또는 아민기를 갖는 실리콘계 화합물은 포토레지스트 조성물 100 중량%에 대하여 0.0001 내지 3 중량%이다.In the photoresist composition of the present invention, the silicon-based compound may improve adhesion between the ITO electrode and the photoresist composition and may increase heat resistance after curing. As a silicone type compound which has the said epoxy group or an amine group, (3-glycidoxy propyl) trimethoxysilane, (3-glycidoxy propyl) triethoxy silane, (3-glycidoxy propyl) methyl dimethoxy silane Phosphorus, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyl Trimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrie Methoxysilane, aminopropyltrimethoxysilane, and the like, and these may be used alone or in combination of two or more thereof. The silicone compound having the epoxy group or the amine group is 0.0001 to 3% by weight based on 100% by weight of the photoresist composition.
또한, 본 발명의 포토레지스트 조성물은 필요에 따라 광증감제, 열중합 금지제, 소포제, 레벨링제 등의 상용성이 있는 첨가제를 더 포함할 수 있다.In addition, the photoresist composition of the present invention may further include a compatible additive such as a photosensitizer, a thermal polymerization inhibitor, an antifoaming agent, a leveling agent and the like as necessary.
본 발명의 포토레지스트 조성물은 용매를 가하여 기판 위에 스핀코팅한 후 마스크를 이용하여 자외선을 조사하여 알칼리 현상액으로 현상하는 방법을 통하여 패턴을 형성하게 되는데, 포토레지스트 조성물 100 중량%에 대하여 10 내지 95 중량%의 용매를 첨가하여 점도를 1 내지 50 cps 범위가 되도록 조절하는 것이 바람직하다. The photoresist composition of the present invention is spin-coated onto a substrate by adding a solvent, and then forms a pattern through a method of developing with an alkali developer by irradiating ultraviolet rays using a mask, wherein the photoresist composition is 10 to 95% by weight based on 100% by weight of the photoresist composition. It is preferred to add% solvent to adjust the viscosity to be in the range of 1 to 50 cps.
상기 용매로는 바인더 수지, 광개시제 및 기타 화합물과의 상용성을 고려하여 에틸아세테이트, 부틸아세테이트, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜 디메틸에틸에테르, 메틸메톡시프로피오네이트, 에틸에톡시프로피오네이트(EEP), 에틸락테이트, 프로필렌글리콜모노메틸에테르아세테이트(PGMEA), 프로필렌글리콜메틸에테르프로피오네이트(PGMEP), 프로필렌글리콜메틸에테르, 프로필렌글리콜프로필에테르, 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트, 디에틸렌글리콜메틸아세테이트, 디에틸렌글리콜에틸아세테이트, 아세톤, 메틸이소부틸케톤, 시클로헥사논, 디메틸포름아미드(DMF), N,N-디메틸아세트아미드(DMAc), N-메틸-2-피롤리돈(NMP), γ-부틸로락톤, 디에틸에테르, 에틸렌글리콜 디메틸 에테르, 다이글라임(Diglyme), 테트라하이드로퓨란(THF), 메탄올, 에탄올, 프로판올, 이소-프로판올, 메틸셀로솔브, 에틸셀로솔브, 디에틸렌글리콜메틸에테르, 디에틸렌글리콜에틸에테르, 디프로필렌글리콜메틸에테르, 톨루엔, 크실렌, 헥산, 헵탄, 옥탄 등의 용매를 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다.The solvent may be ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate in consideration of compatibility with binder resins, photoinitiators and other compounds. (EEP), ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether propionate (PGMEP), 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, cyclohexanone, dimethylformamide (DMF), N , N -dimethylacetamide (DMAc), N -methyl-2-pyrroli Don (NMP), γ-butylolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofue Column (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane And octane can be used alone or in combination of two or more thereof.
본 발명의 일 실시예에 따른 포토레지스트 조성물은 스핀코터, 롤코터, 바코터, 다이코터, 커튼코터, 각종의 인쇄, 침지 등의 공지의 수단으로, 소다 유리, 석영 유리, 반도체 기판, 금속, 종이, 플라스틱 등의 지지 기체상에 적용할 수 있다. 또한 일단 필름 등의 지지 기체상에 실시한 후 다른 지지 기체상에 전사할 수 있고, 그 적용방법에 제한은 없다.Photoresist composition according to an embodiment of the present invention is a known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, immersion, soda glass, quartz glass, semiconductor substrate, metal, It can be applied to a supporting substrate such as paper or plastic. Moreover, it can transfer to another support base body after performing it once on support bases, such as a film, and there is no restriction | limiting in the application method.
본 발명의 일 실시예에 따른 포토레지스트 조성물은 광경화성 도료 혹은 바니시, 광경화성 접착제, 프린트기판, 또는 컬러 텔레비전, PC 모니터, 휴대 정보 단말, 디지털 카메라 등의 컬러 표시의 액정 표시 소자에서의 컬러 필터, 플라즈마 표시 패널용의 전극재료, 분말 코팅, 인쇄 잉크, 인쇄판, 접착제, 치과용 조성물, 겔코팅, 전자 공학용의 포토레지스트, 전기 도금 레지스트, 에칭 레지스트, 액상 및 건조막의 쌍방용 솔더 레지스트, 다양한 표시 용도용의 컬러 매트릭스를 제조하기 위한 혹은 플라즈마 표시 패널, 전기 발광 표시장치, 및 LCD의 제조공정에 있어서 구조를 형성하기 위한 레지스트, 전기 및 전자부품을 봉입하기 위한 조성물, 자기기록재료, 미세 기계부품, 도파로, 광 스위치, 도금용 마스크, 에칭 마스크, 컬러 시험계, 유리 섬유 케이블 코팅, 스크린 인쇄용 스텐실, 스테레오 리소그래피에 의해 삼차원 물체를 제조하기 위한 재료, 홀로그래피 기록용 재료, 화상기록재료, 미세전자회로, 탈색재료, 화상기록재료를 위한 탈색재료, 마이크로 캡슐을 사용하는 화상기록재료용의 탈색재료, 인쇄 배선판용 포토레지스트 재료, UV 및 가시 레이저 직접 화상계용의 포토레지스트 재료, 프린트 회로기판의 순차 적층에서의 유전체층 형성에 사용하는 포토레지스트 재료 또는 보호막 등의 각종의 용도에 사용할 수 있고, 그 용도에 특별히 제한은 없다.A photoresist composition according to an embodiment of the present invention is a color filter in a liquid crystal display device of a color display such as a photocurable paint or varnish, a photocurable adhesive, a printed board, or a color television, a PC monitor, a portable information terminal, a digital camera, or the like. , Electrode material for plasma display panel, powder coating, printing ink, printing plate, adhesive, dental composition, gel coating, photoresist for electronic engineering, electroplating resist, etching resist, solder resist for both liquid and dry film, various marking Compositions for manufacturing color matrices for use or for forming structures in plasma display panels, electroluminescent displays, and LCDs, compositions for encapsulating electrical and electronic components, magnetic recording materials, micromechanical components Waveguides, Optical Switches, Plating Masks, Etch Masks, Color Test Systems, Fiberglass Cables Coating, stencils for screen printing, materials for manufacturing three-dimensional objects by stereo lithography, materials for holographic recording, image recording materials, microelectronic circuits, color decoloring materials, color decoloring materials for image recording materials, image recording materials using microcapsules It can be used for various applications such as discoloration material for photoresist, photoresist material for printed wiring board, photoresist material for UV and visible laser direct imaging system, photoresist material for forming dielectric layer in sequential lamination of printed circuit board or protective film. There is no restriction | limiting in particular in the use.
또한, 본 발명은 상기 화학식 1로 표시되는 디옥심에스테르 화합물을 포함하는 포토레지스트 조성물에 착색재를 포함하는 포토레지스트 조성물을 제공한다. In addition, the present invention provides a photoresist composition comprising a coloring material in the photoresist composition comprising a dioxime ester compound represented by the formula (1).
상기 포토레지스트 조성물은 용도에 따라서 착색재를 첨가하여 착색 포토레지스트 조성물을 제조할 수 있으며, 착색재는 블랙, 레드, 엘로우, 그린, 블루 등 다양한 착색재를 사용할 수 있다. 블랙 매트릭스를 제조하기 위해서는 블랙 착색재를 첨가하고, 컬러 필터를 제조하기 위해서는 R.G.B.색등을 나타내는 다양한 착색재를 사용할 수 있다.The photoresist composition may be added to the coloring material according to the use to prepare a colored photoresist composition, the coloring material may be used a variety of coloring materials, such as black, red, yellow, green, blue. In order to manufacture a black matrix, a black coloring material is added, and in order to manufacture a color filter, various coloring materials which show R.G.B.color etc. can be used.
컬러 필터나 블랙 매트릭스 등의 성형물 형성용 레지스트로 적용하기 위해 포함되는 착색재로는 레드, 그린, 블루와 감색 혼합계의 시안, 마젠다, 옐로우, 블랙 안료를 들 수 있다. 안료로는 C.I.피그먼트 옐로우 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 166, 168, C.I. 피그먼트 오렌지 36, 43, 51, 55, 59, 61, C.I.피그먼트 레드 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. 피그먼트바이올렛 19, 23, 29, 30, 37, 40, 50, C.I.피그먼트 블루 15, 15:1, 15:4, 15:6, 22, 60, 64, C.I.피그먼트 그린 7, 36, C.I.피그먼트 브라운 23, 25, 26, C.I.피그먼트 블랙 7, 티탄 블랙 및 카본블랙 등을 들 수 있다.As a coloring material contained in order to apply it to molded object formation resists, such as a color filter and a black matrix, cyan, magenta, yellow, and black pigment of a red, green, blue, and dark blue mixed system are mentioned. As pigments CI Pigment Yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 166, 168 , CI Pigment Orange 36, 43, 51, 55, 59, 61, CI Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226 , 227, 228, 240, CI Pigment Violet 19, 23, 29, 30, 37, 40, 50, CI Pigment Blue 15, 15: 1, 15: 4, 15: 6, 22, 60, 64, CI Pigment Green 7, 36, CI Pigment brown 23, 25, 26, CI pigment black 7, titanium black, carbon black, etc. are mentioned.
또한, 본 발명은 상기 포토레지스트 조성물의 경화물을 포함하는 성형물을 제공한다.The present invention also provides a molded article comprising the cured product of the photoresist composition.
나아가, 본 발명의 상기 성형물이 어레이 평탄화막, 절연막, 컬럼 스페이서, 블랙 컬럼 스페이서, 블랙 매트릭스 또는 컬러필터인 것을 특징으로 한다.Furthermore, the molding of the present invention is characterized in that the array planarization film, the insulating film, the column spacer, the black column spacer, the black matrix or the color filter.
뿐만 아니라, 본 발명은 상기 성형물을 포함하는 디스플레이 장치를 제공한다.In addition, the present invention provides a display device including the molding.
본 발명의 디옥심에스테르 화합물은 포토레지스트 조성물의 광중합 개시제로 사용될 때 소량을 사용하여도 감도가 월등히 우수하며, 잔막율, 패턴안정성, 내화학성 및 연성 등의 물성이 뛰어나 TFT-LCD 제조 공정 중의 노광 및 포스트베이크 공정에서 광중합 개시제로부터 발생하는 아웃개싱을 최소화할 수 있어 오염을 줄일 수 있고 이로 인해 발생할 수 있는 불량을 최소화할 수 있는 장점이 있다.When used as a photoinitiator of the photoresist composition, the dioxime ester compound of the present invention has excellent sensitivity even when used in a small amount, and has excellent physical properties such as residual film ratio, pattern stability, chemical resistance, and ductility. And it is possible to minimize the outgassing from the photopolymerization initiator in the post-baking process can reduce the contamination and there is an advantage that can minimize the defects that can be caused by this.
이하에서, 본 발명의 상세한 이해를 위하여 본 발명의 대표 화합물을 실시예 및 비교예를 들어 상세하게 설명하겠는바, 본 발명에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석 되어져서는 안된다. 본 발명의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되는 것이다.Hereinafter, for the detailed understanding of the present invention, the exemplary compounds of the present invention will be described in detail with reference to Examples and Comparative Examples. Examples according to the present invention may be modified in various other forms, and the scope of the present invention. Should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
[[ 실시예Example 1] 1-(비페닐-4-일)부탄-1,3- 1] 1- (biphenyl-4-yl) butane-1,3- 디온Dion O,OO, O -- 디아세틸Diacetyl 디옥심(4)의Dioxim (4) 제조 Produce
반응 1. 1-(비페닐-4-일)부탄-1,3-디온(2) 합성 Reaction 1. Synthesis of 1- (biphenyl-4-yl) butane-1,3-dione ( 2 )
Figure PCTKR2016000635-appb-I000012
Figure PCTKR2016000635-appb-I000012
질소분위기 하에서 무수 초산 에틸 50 mL를 5℃로 유지한 다음 수소화나트륨 3.08 g (60% in mineral oil, 0.077 mol)을 가한 후 30분 동안 교반하였다. 초산 에틸 50 mL에 용해한 4-아세틸비페닐(1) 10.0 g (0.051 mol)을 가한 후 1시간 동안 교반한 후 반응 용액을 서서히 승온하여 60℃에서 5 시간 동안 교반하여 반응을 완결하였다. 반응용액을 실온으로 냉각시키고 H2O 30 mL을 가해준 다음 30분 정도 교반 후, 1% HCl 수용액 40 mL을 천천히 적가하여 반응물의 pH가 6~7이 되도록 중화하였다. 반응용액에 초산 에틸 100 mL을 가하여주고 30분 동안 교반하여 유기층을 분리한 후 H2O로 충분히 씻어준 다음, 회수한 유기층을 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)부탄-1,3-디온(2) 7.2g (62.0 %)을 얻었다. 50 mL of anhydrous ethyl acetate was maintained at 5 ° C. under a nitrogen atmosphere, and then 3.08 g (60% in mineral oil, 0.077 mol) of sodium hydride was added thereto, followed by stirring for 30 minutes. After adding 10.0 g (0.051 mol) of 4-acetylbiphenyl ( 1 ) dissolved in 50 mL of ethyl acetate, the mixture was stirred for 1 hour, and then the reaction solution was gradually heated up and stirred at 60 ° C. for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, 30 mL of H 2 O was added thereto, followed by stirring for about 30 minutes, and 40 mL of 1% HCl aqueous solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Purification by chromatography (developing solvent; ethyl acetate: n -hexane = 1: 4) yielded 7.2 g (62.0%) of 1- (biphenyl-4-yl) butane-1,3-dione ( 2 ).
1H NMR(δ ppm; CDCl3) : 2.09 (3H, s), 3.68 (2H, s), 7.36-7.37(3H, m), 7.74-7.76 (4H, m), 7.87-7.89(2H, m) 1 H NMR (δ ppm; CDCl 3 ): 2.09 (3H, s), 3.68 (2H, s), 7.36-7.37 (3H, m), 7.74-7.76 (4H, m), 7.87-7.89 (2H, m )
MS(m/e):238MS ( m / e ): 238
반응 2. 1-(비페닐-4-일)부탄-1,3-디온 디옥심(3)의 합성Reaction 2. Synthesis of 1- (biphenyl-4-yl) butane-1,3-dione dioxime ( 3 )
Figure PCTKR2016000635-appb-I000013
Figure PCTKR2016000635-appb-I000013
1-(비페닐-4-일)부탄-1,3-디온(2) 5.0 g (0.021 mol)을 에탄올 100 mL에 분산시키고 염산히드록실아민 4.38 g (0.063 mol)과 초산나트륨 5.17 g(0.063 mol)을 가해준 다음, 반응용액을 서서히 승온하여 1 시간 동안 환류 반응하였다. 반응물을 실온으로 냉각하고 증류수 100 mL와 초산 에틸 200 mL를 가해준 다음, 30분 정도 교반하여 유기층을 분리한 후 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)부탄-1,3-디온 디옥심(3) 5.23 g (92.9 %)을 얻었다. 5.0 g (0.021 mol) of 1- (biphenyl-4-yl) butane-1,3-dione ( 2 ) is dispersed in 100 mL of ethanol, 4.38 g (0.063 mol) of hydroxylamine hydrochloride and 5.17 g (0.063) of sodium acetate mol) was added, and the reaction solution was gradually heated to reflux for 1 hour. The reaction was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, the mixture was stirred for about 30 minutes, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethyl acetate: n -hexane = 1: 4) to give 5.23 g (92.9%) of 1- (biphenyl-4-yl) butane-1,3-dione dioxime ( 3 ).
1H NMR(δ ppm; CDCl3) : 1.86 (3H, s), 2.89 (2H, s), 7.34-7.38(3H, m), 7.80-7.86 (4H, m), 8.01-8.12 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.86 (3H, s), 2.89 (2H, s), 7.34-7.38 (3H, m), 7.80-7.86 (4H, m), 8.01-8.12 (2H, m )
MS(m/e):268MS ( m / e ): 268
반응 3. 1-(비페닐-4-일)부탄-1,3-디온 O,O-디아세틸 디옥심(4)의 합성Reaction 3. Synthesis of 1- (biphenyl-4-yl) butane-1,3-dione O, O-diacetyl dioxime ( 4 )
Figure PCTKR2016000635-appb-I000014
Figure PCTKR2016000635-appb-I000014
1-(비페닐-4-일)부탄-1,3-디온 디옥심(3) 5.0 g (0.019 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 4.25 g (0.042 mol)을 가해주고 반응용액을 30분 동안 교반한 후 염화아세틸 3.30g (0.042 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)부탄-1,3-디온 O,O-디아세틸 디옥심(4) 5.82 g (92.3 %)을 얻었다.5.0 g (0.019 mol) of 1- (biphenyl-4-yl) butane-1,3-dione dioxime ( 3 ) was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction was kept at -5 ° C, and then 4.25 g (0.042 mol) of ethylamine was added thereto, the reaction solution was stirred for 30 minutes, and then 3.30 g (0.042 mol) of acetyl chloride was added slowly, and the reaction solution was stirred for 30 minutes while being careful not to raise the reaction temperature. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. : n -hexane = 1: 4) to give 5.82 g (92.3%) of 1- (biphenyl-4-yl) butane-1,3-dione O, O-diacetyl dioxime ( 4 ).
1H NMR(δ ppm; CDCl3) : 0.96(6H, s), 1.88 (3H, s), 2.89 (2H, s), 7.34-7.38(3H, m), 7.80-7.86 (4H, m), 8.01-8.12 (3H, m) 1 H NMR (δ ppm; CDCl 3 ): 0.96 (6H, s), 1.88 (3H, s), 2.89 (2H, s), 7.34-7.38 (3H, m), 7.80-7.86 (4H, m), 8.01-8.12 (3H, m)
MS(m/e):352MS ( m / e ): 352
[[ 실시예Example 2] 1-(비페닐-4-일)부탄-1,3- 2] 1- (biphenyl-4-yl) butane-1,3- 디온Dion O,OO, O -- 디프로피오닐Dipropionyl 디옥심(5)의Dioxim (5) 제조 Produce
Figure PCTKR2016000635-appb-I000015
Figure PCTKR2016000635-appb-I000015
1-(비페닐-4-일)부탄-1,3-디온 디옥심(3) 5.0 g (0.019 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 4.25 g (0.042 mol)을 가해주고 반응용액을 30분 동안 교반한 후 프로피오닐 클로라이드 3.88 g (0.042 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)부탄-1,3-디온 O,O-디프로피오닐 디옥심(5) 6.65 g (92.0 %)을 얻었다.5.0 g (0.019 mol) of 1- (biphenyl-4-yl) butane-1,3-dione dioxime ( 3 ) was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction was kept at -5 ° C, and then 4.25 g (0.042 mol) of ethylamine was added and the reaction solution was stirred for 30 minutes, and then 3.88 g (0.042 mol) of propionyl chloride was added slowly, and the mixture was stirred for 30 minutes while being careful not to raise the reaction temperature. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. : n -hexane = 1: 4) to give 6.65 g (92.0%) of 1- (biphenyl-4-yl) butane-1,3-dione O, O-dipropionyl dioxime ( 5 ).
1H NMR(δ ppm; CDCl3) : 0.96(6H, t), 1.88 (3H, s), 2.27 (4H, q), 2.69 (2H, s), 7.35-7.38(3H, m), 7.78-7.82 (4H, m), 8.01-8.05 (3H, m) 1 H NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.88 (3H, s), 2.27 (4H, q), 2.69 (2H, s), 7.35-7.38 (3H, m), 7.78- 7.82 (4H, m), 8.01-8.05 (3H, m)
MS(m/e):380MS ( m / e ): 380
[[ 실시예Example 3] 1-(비페닐-4-일)부탄-1,3- 3] 1- (biphenyl-4-yl) butane-1,3- 디온Dion O,OO, O -- 디시클로헥산카보닐Dicyclohexanecarbonyl 디옥심(6)의Dioxim (6) 제조 Produce
Figure PCTKR2016000635-appb-I000016
Figure PCTKR2016000635-appb-I000016
1-(비페닐-4-일)부탄-1,3-디온 디옥심(3) 5.0 g (0.019 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 4.25 g (0.042 mol)을 가해주고 반응용액을 30분 동안 교반한 후 시클로헥산카보닐 클로라이드 6.16 g (0.042 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)부탄-1,3-디온 O,O-디시클로헥산카보닐 디옥심(6) 8.54 g (92.0 %)을 얻었다.5.0 g (0.019 mol) of 1- (biphenyl-4-yl) butane-1,3-dione dioxime ( 3 ) was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction was kept at -5 ° C, and then 4.25 g (0.042 mol) of ethylamine was added and the reaction solution was stirred for 30 minutes, and then 6.16 g (0.042 mol) of cyclohexanecarbonyl chloride was added slowly, and the mixture was stirred for 30 minutes while being careful not to raise the reaction temperature. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. : n -hexane = 1: 4) to obtain 8.54 g (92.0%) of 1- (biphenyl-4-yl) butane-1,3-dione O, O-dicyclohexanecarbonyl dioxime ( 6 ) Got it.
1H NMR(δ ppm; CDCl3) : 1.12-1.15(10H, m), 1.60-1.66 (12H, m), 1.88 (3H, s), 2.69 (2H, s), 7.35-7.38(3H, m), 7.78-7.82 (4H, m), 8.01-8.05 (3H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.12-1.15 (10H, m), 1.60-1.66 (12H, m), 1.88 (3H, s), 2.69 (2H, s), 7.35-7.38 (3H, m ), 7.78-7.82 (4H, m), 8.01-8.05 (3H, m)
MS(m/e):487MS ( m / e ): 487
[[ 실시예Example 4] 1-(비페닐-4-일)부탄-1,3- 4] 1- (biphenyl-4-yl) butane-1,3- 디온Dion O,OO, O -- 디벤조일Dibenzoyl 디옥심(7)의Dioxim (7) 제조 Produce
Figure PCTKR2016000635-appb-I000017
Figure PCTKR2016000635-appb-I000017
1-(비페닐-4-일)부탄-1,3-디온 디옥심(3) 5.0 g (0.019 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 4.25 g (0.042 mol)을 가해주고 반응용액을 30분 동안 교반한 후 벤조일 클로라이드 5.90 g (0.042 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)부탄-1,3-디온 O,O-디벤조일 디옥심(7) 8.26 g (91.2 %)을 얻었다.5.0 g (0.019 mol) of 1- (biphenyl-4-yl) butane-1,3-dione dioxime ( 3 ) was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction was kept at -5 ° C, and then 4.25 g (0.042 mol) of ethylamine was added and the reaction solution was stirred for 30 minutes, and then 5.90 g (0.042 mol) of benzoyl chloride was added slowly, and the mixture was stirred for 30 minutes while being careful not to raise the reaction temperature. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. : n -hexane = 1: 4) to obtain 8.26 g (91.2%) of 1- (biphenyl-4-yl) butane-1,3-dione O, O-dibenzoyl dioxime ( 7 ).
1H NMR(δ ppm; CDCl3) : 1.85 (3H, s), 2.65 (2H, s), 7.35-7.38(3H, m), 7.55-7.58 (6H, m) 7.78-7.82 (4H, m), 8.01-8.05 (3H, m), 8.18-8.20 (4H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.85 (3H, s), 2.65 (2H, s), 7.35-7.38 (3H, m), 7.55-7.58 (6H, m) 7.78-7.82 (4H, m) , 8.01-8.05 (3H, m), 8.18-8.20 (4H, m)
MS(m/e):477MS ( m / e ): 477
[[ 실시예Example 5] 1-(비페닐-4-일)-2- 5] 1- (biphenyl-4-yl) -2- 메틸부탄Methylbutane -1,3--1,3- 디온Dion O,OO, O -- 디아세틸Diacetyl 디옥심(11)의Dioxim (11) 제조 Produce
반응 1. 1-(비페닐-4-일)-2-메틸부탄-1,3-디온(9) 합성 Reaction 1. 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione ( 9 ) synthesis
Figure PCTKR2016000635-appb-I000018
Figure PCTKR2016000635-appb-I000018
질소분위기 하에서 무수 초산 에틸 50 mL를 5℃로 유지한 다음 수소화나트륨 2.88 g (60% in mineral oil, 0.072 mol)을 가한 후 30분 동안 교반하였다. 초산 에틸 50 mL에 용해한 4-프로피오닐 비페닐(8) 10.0 g (0.048 mol)을 가한 후 1시간 동안 교반한 후 반응 용액을 서서히 승온하여 60℃에서 5 시간 동안 교반하여 반응을 완결하였다. 반응용액을 실온으로 냉각시키고 H2O 30 mL을 가해준 다음 30분 정도 교반 후, 1% HCl 수용액 40 mL을 천천히 적가하여 반응물의 pH가 6~7이 되도록 중화하였다. 반응용액에 초산 에틸 100 mL을 가하여주고 30분 동안 교반하여 유기층을 분리한 후 H2O로 충분히 씻어준 다음, 회수한 유기층을 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)-2-메틸부탄-1,3-디온(9) 7.07g (58.2 %)을 얻었다. 50 mL of anhydrous ethyl acetate was maintained at 5 ° C. under a nitrogen atmosphere, and then 2.88 g of sodium hydride (60% in mineral oil, 0.072 mol) was added thereto, followed by stirring for 30 minutes. After adding 10.0 g (0.048 mol) of 4-propionyl biphenyl ( 8 ) dissolved in 50 mL of ethyl acetate, the mixture was stirred for 1 hour, and the reaction solution was gradually warmed up and stirred at 60 ° C. for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, 30 mL of H 2 O was added thereto, followed by stirring for about 30 minutes, and 40 mL of 1% HCl aqueous solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 7.07 g (58.2%) of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione ( 9 ) was purified by chromatography (developing solvent; ethyl acetate: n -hexane = 1: 4). Got it.
1H NMR(δ ppm; CDCl3) : 1.39 (3H, d), 2.09 (3H, s), 4.00 (1H, m), 7.35-7.37(3H, m), 7.75-7.76 (4H, m), 7.86-7.89(2H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.39 (3H, d), 2.09 (3H, s), 4.00 (1H, m), 7.35-7.37 (3H, m), 7.75-7.76 (4H, m), 7.86-7.89 (2H, m)
MS(m/e):252MS ( m / e ): 252
반응 2. 1-(비페닐-4-일)-2-메틸부탄-1,3-디온 디옥심(10)의 합성Reaction 2. Synthesis of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione dioxime ( 10 )
Figure PCTKR2016000635-appb-I000019
Figure PCTKR2016000635-appb-I000019
1-(비페닐-4-일)-2-메틸부탄-1,3-디온(9) 5.0 g (0.020 mol)을 에탄올 100 mL에 분산시키고 염산히드록실아민 4.18 g (0.060 mol)과 초산나트륨 4.92 g(0.060 mol)을 가해준 다음, 반응용액을 서서히 승온하여 1 시간 동안 환류 반응하였다. 반응물을 실온으로 냉각하고 증류수 100 mL와 초산 에틸 200 mL를 가해준 다음, 30분 정도 교반하여 유기층을 분리한 후 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)-2-메틸부탄-1,3-디온 디옥심(10) 5.02 g (88.9 %)을 얻었다. 5.0 g (0.020 mol) of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione ( 9 ) is dispersed in 100 mL of ethanol, and 4.18 g (0.060 mol) of hydroxylamine hydrochloride and sodium acetate 4.92 g (0.060 mol) was added thereto, and the reaction solution was gradually heated to reflux for 1 hour. The reaction was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, the mixture was stirred for about 30 minutes, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethyl acetate: n -hexane = 1: 4) to give 5.02 g (88.9%) of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione dioxime ( 10 ).
1H NMR(δ ppm; CDCl3) : 1.35 (3H, d), 1.87 (3H, s), 3.98 (1H, m), 7.34-7.38(3H, m), 7.80-7.86 (4H, m), 8.01-8.12 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.35 (3H, d), 1.87 (3H, s), 3.98 (1H, m), 7.34-7.38 (3H, m), 7.80-7.86 (4H, m), 8.01-8.12 (2H, m)
MS(m/e):282MS ( m / e ): 282
반응 3. 1-(비페닐-4-일)-2-메틸부탄-1,3-디온 O,O-디아세틸 디옥심(11)의 합성Reaction 3. Synthesis of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione O, O-diacetyl dioxime ( 11 )
Figure PCTKR2016000635-appb-I000020
Figure PCTKR2016000635-appb-I000020
1-(비페닐-4-일)-2-메틸부탄-1,3-디온 디옥심(10) 5.0 g (0.018 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 4.05 g (0.040 mol)을 가해주고 반응용액을 30분 동안 교반한 후 염화아세틸 3.14g (0.040 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)-2-메틸부탄-1,3-디온 O,O-디아세틸 디옥심(11) 5.94 g (90.1 %)을 얻었다.5.0 g (0.018 mol) of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione dioxime ( 10 ) is dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction is kept at -5 ° C. Then, 4.05 g (0.040 mol) of triethylamine was added thereto, the reaction solution was stirred for 30 minutes, and then 3.14 g (0.040 mol) of acetyl chloride was slowly added thereto, and the mixture was stirred for 30 minutes while being careful not to raise the reaction temperature. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. : n -hexane = 1: 4), purified by 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione O, O-diacetyl dioxime ( 11 ) 5.94 g (90.1%) Got.
1H NMR(δ ppm; CDCl3) : 0.96(6H, s), 1.32 (3H, d), 1.88 (3H, s), 3.89 (1H, m), 7.34-7.38(3H, m), 7.80-7.86 (4H, m), 8.01-8.12 (3H, m) 1 H NMR (δ ppm; CDCl 3 ): 0.96 (6H, s), 1.32 (3H, d), 1.88 (3H, s), 3.89 (1H, m), 7.34-7.38 (3H, m), 7.80- 7.86 (4H, m), 8.01-8.12 (3H, m)
MS(m/e):366MS ( m / e ): 366
[[ 실시예Example 6] 1-(비페닐-4-일)-2- 6] 1- (biphenyl-4-yl) -2- 메틸부탄Methylbutane -1,3--1,3- 디온Dion O,OO, O -- 디시클로헥산카보닐Dicyclohexanecarbonyl 디옥심(12)의 제조 Preparation of Dioxime 12
Figure PCTKR2016000635-appb-I000021
Figure PCTKR2016000635-appb-I000021
1-(비페닐-4-일)-2-메틸부탄-1,3-디온 디옥심(10) 5.0 g (0.018 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 4.05 g (0.040 mol)을 가해주고 반응용액을 30분 동안 교반한 후 시클로헥산카보닐 클로라이드 5.86g (0.040 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)-2-메틸부탄-1,3-디온 O,O-디시클로헥산카보닐 디옥심(12) 8.48 g (88.8 %)을 얻었다.5.0 g (0.018 mol) of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione dioxime ( 10 ) is dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction is kept at -5 ° C. Then add 4.05 g (0.040 mol) of triethylamine, stir the reaction solution for 30 minutes, and slowly add 5.86 g (0.040 mol) of cyclohexanecarbonyl chloride for 30 minutes, taking care not to raise the reaction temperature. Stirred. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 8.48 g of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione O, O-dicyclohexanecarbonyl dioxime ( 12 ) purified by n -hexane = 1: 4) 88.8%).
1H NMR(δ ppm; CDCl3) : 1.12-1.14(10H, m), 1.30 (3H, d), 1.62-1.66 (12H, m), 1.90 (3H, s), 3.85 (1H, m), 7.36-7.38(3H, m), 7.82-7.86 (4H, m), 8.01-8.08 (3H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.12-1.14 (10H, m), 1.30 (3H, d), 1.62-1.66 (12H, m), 1.90 (3H, s), 3.85 (1H, m), 7.36-7.38 (3H, m), 7.82-7.86 (4H, m), 8.01-8.08 (3H, m)
MS(m/e):503MS ( m / e ): 503
[[ 실시예Example 7] 1-(비페닐-4-일)-2- 7] 1- (biphenyl-4-yl) -2- 메틸부탄Methylbutane -1,3--1,3- 디온Dion O,OO, O -- 디벤조일Dibenzoyl 디옥심(13)의Dioxim (13) 제조 Produce
Figure PCTKR2016000635-appb-I000022
Figure PCTKR2016000635-appb-I000022
1-(비페닐-4-일)-2-메틸부탄-1,3-디온 디옥심(10) 5.0 g (0.018 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 4.05 g (0.040 mol)을 가해주고 반응용액을 30분 동안 교반한 후 벤조일 클로라이드 5.62g (0.040 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)-2-메틸부탄-1,3-디온 O,O-디벤조일 디옥심(13) 8.22 g (88.2 %)을 얻었다.5.0 g (0.018 mol) of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione dioxime ( 10 ) is dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction is kept at -5 ° C. Then, 4.05 g (0.040 mol) of triethylamine was added and the reaction solution was stirred for 30 minutes, and then 5.62 g (0.040 mol) of benzoyl chloride was added slowly, and the reaction solution was stirred for 30 minutes while being careful not to raise the reaction temperature. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. : n -hexane = 1: 4), purified by 1- (biphenyl-4-yl) -2-methylbutan-1,3-dione O, O-dibenzoyl dioxim ( 13 ) 8.22 g (88.2%) Got.
1H NMR(δ ppm; CDCl3) : 1.30 (3H, d), 1.85 (3H, s), 3.85 (1H, m), 7.36-7.38(3H, m), 7.55-7.58 (6H, m) 7.80-7.82 (4H, m), 8.01-8.04 (3H, m), 8.18-8.20 (4H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.30 (3H, d), 1.85 (3H, s), 3.85 (1H, m), 7.36-7.38 (3H, m), 7.55-7.58 (6H, m) 7.80 -7.82 (4H, m), 8.01-8.04 (3H, m), 8.18-8.20 (4H, m)
MS(m/e):491MS ( m / e ): 491
[[ 실시예Example 8] 1-(비페닐-4-일)-2- 8] 1- (biphenyl-4-yl) -2- 시클로헥실부탄Cyclohexylbutane -1,3--1,3- 디온Dion O,OO, O -- 디아세틸Diacetyl 디옥심(18)의Dioxim (18) 제조 Produce
반응 1. 1-(비페닐-4-일)-2-시클로헥실에타온 (15)의 합성Reaction 1. Synthesis of 1- (biphenyl-4-yl) -2-cyclohexylethanone ( 15 )
Figure PCTKR2016000635-appb-I000023
Figure PCTKR2016000635-appb-I000023
비페닐(14) 10.0 g (0.065 mol)을 디클로로메탄 100 mL에 용해시키고 반응물을 -5 ℃로 냉각한 후, 염화알루미늄 10.40 g (0.78 mol)을 천천히 가해준 다음 반응물의 온도가 승온되지 않도록 주의 하면서 디클로로메탄 5 mL에 희석시킨 염화 2-시클로헥실아세틸 12.53 g (0.078 mol)을 2시간에 걸쳐서 천천히 가해주고 -5 ℃에서 1시간 동안 반응물을 교반하였다. 그런 다음 반응물을 얼음물 1 L에 천천히 붓고 30분 동안 교반하여 유기층을 분리한 후, 증류수 500 mL로 씻어주고 회수한 유기층을 감압 증류하여 얻은 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)-2-시클로헥실에타온 (15) 11.07g (61.2 %)을 얻었다. Biphenyl ( 14 ) Dissolve 10.0 g (0.065 mol) in 100 mL of dichloromethane, cool the reaction to -5 ° C, slowly add 10.40 g (0.78 mol) of aluminum chloride, and 5 mL of dichloromethane, taking care not to raise the temperature of the reaction. 12.53 g (0.078 mol) of 2-cyclohexylacetyl chloride diluted in was slowly added over 2 hours, and the reaction was stirred at -5 ° C for 1 hour. Then, the reaction mixture was slowly poured into 1 L of ice water and stirred for 30 minutes to separate the organic layer, and then washed with 500 mL of distilled water, and the recovered organic layer was distilled under reduced pressure (developing solvent; ethyl acetate: n -hexane = 1: 4) to give 11.07 g (61.2%) of 1- (biphenyl-4-yl) -2-cyclohexylethanone ( 15 ).
1H NMR(δ ppm; CDCl3) : 1.12-1.14(10H, m), 1.62-1.66 (12H, m), 2.51 (2H, d), 7.36-7.38(3H, m), 7.82-7.86 (4H, m), 8.01-8.08 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.12-1.14 (10H, m), 1.62-1.66 (12H, m), 2.51 (2H, d), 7.36-7.38 (3H, m), 7.82-7.86 (4H , m), 8.01-8.08 (2H, m)
MS(m/e):278MS ( m / e ): 278
반응 2. 1-(비페닐-4-일)-2-시클로헥실부탄-1,3-디온(16)의 합성Reaction 2. Synthesis of 1- (biphenyl-4-yl) -2-cyclohexylbutane-1,3-dione ( 16 )
Figure PCTKR2016000635-appb-I000024
Figure PCTKR2016000635-appb-I000024
질소분위기 하에서 무수 초산 에틸 50 mL를 5℃로 유지한 다음 수소화나트륨 2.16 g (60% in mineral oil, 0.054 mol)을 가한 후 30분 동안 교반하였다. 초산 에틸 50 mL에 용해한 1-(비페닐-4-일)-2-시클로헥실에타온 (15) 10.0 g (0.036 mol)을 가한 후 1시간 동안 교반한 후 반응 용액을 서서히 승온하여 60℃에서 5 시간 동안 교반하여 반응을 완결하였다. 반응용액을 실온으로 냉각시키고 H2O 30 mL을 가해준 다음 30분 정도 교반 후, 1% HCl 수용액 30 mL을 천천히 적가하여 반응물의 pH가 6~7이 되도록 중화하였다. 반응용액에 초산 에틸 100 mL을 가하여주고 30분 동안 교반하여 유기층을 분리한 후 H2O로 충분히 씻어준 다음, 회수한 유기층을 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)-2-시클로헥실부탄-1,3-디온(16) 6.37 g (55.2 %)을 얻었다. 50 mL of anhydrous ethyl acetate was maintained at 5 ° C. under a nitrogen atmosphere, and then 2.16 g of sodium hydride (60% in mineral oil, 0.054 mol) was added thereto, followed by stirring for 30 minutes. 10.0 g (0.036 mol) of 1- (biphenyl-4-yl) -2-cyclohexylethanone ( 15 ) dissolved in 50 mL of ethyl acetate was added thereto, stirred for 1 hour, and the reaction solution was gradually heated to 60 ° C. Stir for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, 30 mL of H 2 O was added, followed by stirring for about 30 minutes, and 30 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 6.37 g (55.2%) of 1- (biphenyl-4-yl) -2-cyclohexylbutane-1,3-dione ( 16 ) by purification by chromatography (developing solvent; ethyl acetate: n -hexane = 1: 4). Got.
1H NMR(δ ppm; CDCl3) : 1.12-1.14(10H, m), 1.62-1.66 (12H, m), 2.10 (3H, s), 3.51 (1H, d), 7.36-7.38(3H, m), 7.82-7.86 (4H, m), 8.01-8.08 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.12-1.14 (10H, m), 1.62-1.66 (12H, m), 2.10 (3H, s), 3.51 (1H, d), 7.36-7.38 (3H, m ), 7.82-7.86 (4H, m), 8.01-8.08 (2H, m)
MS(m/e):320MS ( m / e ): 320
반응 3. 1-(비페닐-4-일)-2-시클로헥실부탄-1,3-디온 디옥심(17)의 합성Reaction 3. Synthesis of 1- (biphenyl-4-yl) -2-cyclohexylbutane-1,3-dione dioxime ( 17 )
Figure PCTKR2016000635-appb-I000025
Figure PCTKR2016000635-appb-I000025
1-(비페닐-4-일)-2-시클로헥실부탄-1,3-디온(16) 5.0 g (0.016 mol)을 에탄올 100 mL에 분산시키고 염산히드록실아민 3.34 g (0.048 mol)과 초산나트륨 3.94 g(0.048 mol)을 가해준 다음, 반응용액을 서서히 승온하여 1 시간 동안 환류 반응하였다. 반응물을 실온으로 냉각하고 증류수 100 mL와 초산 에틸 200 mL를 가해준 다음, 30분 정도 교반하여 유기층을 분리한 후 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)-2-시클로헥실부탄-1,3-디온 디옥심(17) 4.87 g (86.9 %)을 얻었다. 5.0 g (0.016 mol) of 1- (biphenyl-4-yl) -2-cyclohexylbutane-1,3-dione ( 16 ) is dispersed in 100 mL of ethanol, and 3.34 g (0.048 mol) of hydroxylamine hydrochloride and acetic acid 3.94 g (0.048 mol) of sodium was added thereto, and the reaction solution was gradually heated to reflux for 1 hour. The reaction was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, the mixture was stirred for about 30 minutes, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethyl acetate: n -hexane = 1: 4) to obtain 4.87 g (86.9%) of 1- (biphenyl-4-yl) -2-cyclohexylbutane-1,3-dione dioxime ( 17 ); .
1H NMR(δ ppm; CDCl3) : 1.10-1.12(10H, m), 1.60-1.64 (12H, m), 2.08 (3H, s), 3.45 (1H, d), 7.33-7.35(3H, m), 7.80-7.82 (4H, m), 8.01-8.06 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.10-1.12 (10H, m), 1.60-1.64 (12H, m), 2.08 (3H, s), 3.45 (1H, d), 7.33-7.35 (3H, m ), 7.80-7.82 (4H, m), 8.01-8.06 (2H, m)
MS(m/e):350MS ( m / e ): 350
반응 4. 1-(비페닐-4-일)-2-시클로헥실부탄-1,3-디온 O,O-디아세틸 디옥심(18)의 합성Reaction 4. Synthesis of 1- (biphenyl-4-yl) -2-cyclohexylbutane-1,3-dione O, O-diacetyl dioxime ( 18 )
Figure PCTKR2016000635-appb-I000026
Figure PCTKR2016000635-appb-I000026
1-(비페닐-4-일)-2-시클로헥실부탄-1,3-디온 디옥심(17) 5.0 g (0.014 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 3.24 g (0.032 mol)을 가해주고 반응용액을 30분 동안 교반한 후 염화아세틸 2.51g (0.032 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)-2-시클로헥실부탄-1,3-디온 O,O-디아세틸 디옥심(18) 5.49 g (90.3 %)을 얻었다.5.0 g (0.014 mol) of 1- (biphenyl-4-yl) -2-cyclohexylbutane-1,3-dione dioxime ( 17 ) is dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction is brought to -5 ° C. After that, 3.24 g (0.032 mol) of triethylamine was added thereto, the reaction solution was stirred for 30 minutes, and then 2.51 g (0.032 mol) of acetyl chloride was slowly added thereto, and the mixture was stirred for 30 minutes while being careful not to raise the reaction temperature. . Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. : n - hexane = 1: 4) to give 1- (biphenyl-4-yl) -2-cyclohexyl-butane-1,3-dione O, O- di-acetyl-di-oxime (18) 5.49 g (90.3% )
1H NMR(δ ppm; CDCl3) : 0.96(6H, s), 1.10-1.12(10H, m), 1.58-1.60 (12H, m), 2.05 (3H, s), 3.48 (1H, d), 7.33-7.35(3H, m), 7.80-7.82 (4H, m), 8.01-8.06 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 0.96 (6H, s), 1.10-1.12 (10H, m), 1.58-1.60 (12H, m), 2.05 (3H, s), 3.48 (1H, d), 7.33-7.35 (3H, m), 7.80-7.82 (4H, m), 8.01-8.06 (2H, m)
MS(m/e):435MS ( m / e ): 435
[[ 실시예Example 9] 1-(비페닐-4-일)-2-( 9] 1- (biphenyl-4-yl) -2- ( 시클로펜틸메틸Cyclopentylmethyl )부탄-1,3-Butane-1,3- 디온Dion O,OO, O -- 디아세틸Diacetyl 디옥심(22)의 제조 Preparation of Dioxime (22)
반응 1. 1-(비페닐-4-일)-3-시클로펜틸프로판-1-온 (19)의 합성Reaction 1. Synthesis of 1- (biphenyl-4-yl) -3-cyclopentylpropan-1-one (19)
Figure PCTKR2016000635-appb-I000027
Figure PCTKR2016000635-appb-I000027
비페닐(14) 10.0 g (0.065 mol)을 디클로로메탄 100 mL에 용해시키고 반응물을 -5 ℃로 냉각한 후, 염화알루미늄 10.40 g (0.78 mol)을 천천히 가해준 다음 반응물의 온도가 승온되지 않도록 주의 하면서 디클로로메탄 5 mL에 희석시킨 3-시클로펜틸프로피오닐 클로라이드 12.53 g (0.078 mol)을 2시간에 걸쳐서 천천히 가해주고 -5 ℃에서 1시간 동안 반응물을 교반하였다. 그런 다음 반응물을 얼음물 1 L에 천천히 붓고 30분 동안 교반하여 유기층을 분리한 후, 증류수 500 mL로 씻어주고 회수한 유기층을 감압 증류하여 얻은 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)-3-시클로펜틸프로판-1-온 (19) 10.64 g (58.8 %)을 얻었다. Biphenyl ( 14 ) Dissolve 10.0 g (0.065 mol) in 100 mL of dichloromethane, cool the reaction to -5 ° C, slowly add 10.40 g (0.78 mol) of aluminum chloride, and 5 mL of dichloromethane, taking care not to raise the temperature of the reaction. 12.53 g (0.078 mol) of 3-cyclopentylpropionyl chloride diluted in was slowly added over 2 hours, and the reaction was stirred at -5 ° C for 1 hour. Then, the reaction mixture was slowly poured into 1 L of ice water and stirred for 30 minutes to separate the organic layer, and then washed with 500 mL of distilled water, and the recovered organic layer was distilled under reduced pressure (developing solvent; ethyl acetate: n -hexane = 1: 4) to give 10.64 g (58.8%) of 1- (biphenyl-4-yl) -3-cyclopentylpropan-1-one ( 19 ).
1H NMR(δ ppm; CDCl3) : 1.35-1.60(9H, m), 1.45 (2H, m), 2.51 (2H, t), 7.36-7.38(3H, m), 7.82-7.86 (4H, m), 8.01-8.08 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.35-1.60 (9H, m), 1.45 (2H, m), 2.51 (2H, t), 7.36-7.38 (3H, m), 7.82-7.86 (4H, m ), 8.01-8.08 (2H, m)
MS(m/e):278MS ( m / e ): 278
반응 2. 1-(비페닐-4-일)-2-(시클로펜틸메틸)부탄-1,3-디온(20)의 합성Reaction 2. Synthesis of 1- (biphenyl-4-yl) -2- (cyclopentylmethyl) butane-1,3-dione ( 20 )
Figure PCTKR2016000635-appb-I000028
Figure PCTKR2016000635-appb-I000028
질소분위기 하에서 무수 초산 에틸 50 mL를 5℃로 유지한 다음 수소화 나트륨 2.16 g (60% in mineral oil, 0.054 mol)을 가한 후 30분 동안 교반하였다. 초산 에틸 50 mL에 용해한 1-(비페닐-4-일)-3-시클로펜틸프로판-1-온 (19) 10.0 g (0.036 mol)을 가한 후 1시간 동안 교반한 후 반응 용액을 서서히 승온하여 60℃에서 5 시간 동안 교반하여 반응을 완결하였다. 반응용액을 실온으로 냉각시키고 H2O 30 mL을 가해준 다음 30분 정도 교반 후, 1% HCl 수용액 30 mL을 천천히 적가하여 반응물의 pH가 6~7이 되도록 중화하였다. 반응용액에 초산 에틸 100 mL을 가하여주고 30분 동안 교반하여 유기층을 분리한 후 H2O로 충분히 씻어준 다음, 회수한 유기층을 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)-2-(시클로펜틸메틸)부탄-1,3-디온(20) 6.37 g (55.2 %)을 얻었다. 50 mL of anhydrous ethyl acetate was kept at 5 ° C. under a nitrogen atmosphere, and then 2.16 g of sodium hydride (60% in mineral oil, 0.054 mol) was added thereto, followed by stirring for 30 minutes. 10.0 g (0.036 mol) of 1- (biphenyl-4-yl) -3-cyclopentylpropan-1-one ( 19 ) dissolved in 50 mL of ethyl acetate was added thereto, stirred for 1 hour, and the reaction solution was gradually warmed up. The reaction was completed by stirring at 60 ° C. for 5 hours. The reaction solution was cooled to room temperature, 30 mL of H 2 O was added, followed by stirring for about 30 minutes, and 30 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 6.37 g of 1- (biphenyl-4-yl) -2- (cyclopentylmethyl) butane-1,3-dione ( 20 ), purified by chromatography (developing solvent; ethyl acetate: n -hexane = 1: 4). 55.2%).
1H NMR(δ ppm; CDCl3) : 1.35-1.60(9H, m), 1.48 (2H, m), 2.05 (3H, s), 2.45 (2H, t), 7.36-7.38(3H, m), 7.82-7.86 (4H, m), 8.01-8.08 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.35-1.60 (9H, m), 1.48 (2H, m), 2.05 (3H, s), 2.45 (2H, t), 7.36-7.38 (3H, m), 7.82-7.86 (4H, m), 8.01-8.08 (2H, m)
MS(m/e):320MS ( m / e ): 320
반응 3. 1-(비페닐-4-일)-2-(시클로펜틸메틸)부탄-1,3-디온 디옥심(21)의 합성Reaction 3. Synthesis of 1- (biphenyl-4-yl) -2- (cyclopentylmethyl) butane-1,3-dione dioxime ( 21 )
Figure PCTKR2016000635-appb-I000029
Figure PCTKR2016000635-appb-I000029
1-(비페닐-4-일)-2-(시클로펜틸메틸)부탄-1,3-디온(20) 5.0 g (0.016 mol)을 에탄올 100 mL에 분산시키고 염산히드록실아민 3.34 g (0.048 mol)과 초산나트륨 3.94 g(0.048 mol)을 가해준 다음, 반응용액을 서서히 승온하여 1 시간 동안 환류 반응하였다. 반응물을 실온으로 냉각하고 증류수 100 mL와 초산 에틸 200 mL를 가해준 다음, 30분 정도 교반하여 유기층을 분리한 후 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)-2-(시클로펜틸메틸)부탄-1,3-디온 디옥심(21) 4.94 g (88.1 %)을 얻었다. 5.0 g (0.016 mol) of 1- (biphenyl-4-yl) -2- (cyclopentylmethyl) butane-1,3-dione ( 20 ) is dispersed in 100 mL of ethanol and 3.34 g (0.048 mol) of hydroxylamine hydrochloride ) And sodium acetate 3.94 g (0.048 mol) were added, and the reaction solution was gradually heated to reflux for 1 hour. The reaction was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, the mixture was stirred for about 30 minutes, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 4.94 g (88.1%) of 1- (biphenyl-4-yl) -2- (cyclopentylmethyl) butane-1,3-dione dioxime ( 21 ) purified by ethyl acetate: n -hexane = 1: 4) )
1H NMR(δ ppm; CDCl3) : 1.35-1.60(9H, m), 1.48 (2H, m), 2.08 (3H, s), 2.45 (2H, t), 7.33-7.35(3H, m), 7.80-7.82 (4H, m), 8.01-8.06 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.35-1.60 (9H, m), 1.48 (2H, m), 2.08 (3H, s), 2.45 (2H, t), 7.33-7.35 (3H, m), 7.80-7.82 (4H, m), 8.01-8.06 (2H, m)
MS(m/e):350MS ( m / e ): 350
반응 4. 1-(비페닐-4-일)-2-(시클로펜틸메틸)부탄-1,3-디온 O,O-디아세틸 디옥심(22)의 합성Reaction 4. Synthesis of 1- (biphenyl-4-yl) -2- (cyclopentylmethyl) butane-1,3-dione O, O-diacetyl dioxime ( 22 )
Figure PCTKR2016000635-appb-I000030
Figure PCTKR2016000635-appb-I000030
1-(비페닐-4-일)-2-(시클로펜틸메틸)부탄-1,3-디온 디옥심(21) 5.0 g (0.014 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 3.24 g (0.032 mol)을 가해주고 반응용액을 30분 동안 교반한 후 염화아세틸 2.51g (0.032 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)-2-(시클로펜틸메틸)부탄-1,3-디온 O,O-디아세틸 디옥심(22) 5.49 g (90.3 %)을 얻었다.5.0 g (0.014 mol) of 1- (biphenyl-4-yl) -2- (cyclopentylmethyl) butane-1,3-dione dioxime ( 21 ) are dissolved in 50 mL of ethyl acetate under a nitrogen atmosphere and the reaction is- After the temperature was maintained at 5 ° C., 3.24 g (0.032 mol) of triethylamine was added thereto, the reaction solution was stirred for 30 minutes, and then 2.51 g (0.032 mol) of acetyl chloride was slowly added thereto. Was stirred. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 5.49 g of 1- (biphenyl-4-yl) -2- (cyclopentylmethyl) butane-1,3-dione O, O-diacetyl dioxime ( 22 ) purified by n -hexane = 1: 4) (90.3%).
1H NMR(δ ppm; CDCl3) : 0.96(6H, s), 1.35-1.60(9H, m), 1.48 (2H, m), 2.05 (3H, s), 2.42 (2H, t), 7.33-7.35(3H, m), 7.80-7.82 (4H, m), 8.01-8.06 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 0.96 (6H, s), 1.35-1.60 (9H, m), 1.48 (2H, m), 2.05 (3H, s), 2.42 (2H, t), 7.33- 7.35 (3H, m), 7.80-7.82 (4H, m), 8.01-8.06 (2H, m)
MS(m/e):435MS ( m / e ): 435
[[ 실시예Example 10] 1-(비페닐-4-일) 10] 1- (biphenyl-4-yl) 헥산Hexane -1,3--1,3- 디온Dion O,OO, O -- 디아세틸Diacetyl 디옥심(25)의Dioxim (25) 제조 Produce
반응 1. 1-(비페닐-4-일)헥산-1,3-디온(23)합성 Reaction 1. 1- (biphenyl-4-yl) hexane-1,3-dione ( 23 ) synthesis
Figure PCTKR2016000635-appb-I000031
Figure PCTKR2016000635-appb-I000031
질소분위기 하에서 무수 에틸 부틸레이트 50 mL를 5℃로 유지한 다음 수소화 나트륨 3.08 g (60% in mineral oil, 0.077 mol)을 가한 후 30분 동안 교반하였다. 에틸 부틸레이트 50 mL에 용해한 4-아세틸비페닐(1) 10.0 g (0.051 mol)을 가한 후 1시간 동안 교반한 후 반응 용액을 서서히 승온하여 60℃에서 5 시간 동안 교반하여 반응을 완결하였다. 반응용액을 실온으로 냉각시키고 H2O 30 mL을 가해준 다음 30분 정도 교반 후, 1% HCl 수용액 40 mL을 천천히 적가하여 반응물의 pH가 6~7이 되도록 중화하였다. 반응용액에 초산 에틸 100 mL을 가하여주고 30분 동안 교반하여 유기층을 분리한 후 H2O로 충분히 씻어준 다음, 회수한 유기층을 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)헥산-1,3-디온(23) 8.01g (59.0 %)을 얻었다. 50 mL of anhydrous ethyl butyrate was maintained at 5 ° C. under a nitrogen atmosphere, and then 3.08 g of sodium hydride (60% in mineral oil, 0.077 mol) was added thereto, followed by stirring for 30 minutes. After adding 10.0 g (0.051 mol) of 4-acetylbiphenyl ( 1 ) dissolved in 50 mL of ethyl butyrate, the mixture was stirred for 1 hour, and then the reaction solution was gradually heated up and stirred at 60 ° C. for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, 30 mL of H 2 O was added thereto, followed by stirring for about 30 minutes, and 40 mL of 1% HCl aqueous solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Purification by chromatography (developing solvent; ethyl acetate: n -hexane = 1: 4) afforded 8.01 g (59.0%) of 1- (biphenyl-4-yl) hexane-1,3-dione ( 23 ).
1H NMR(δ ppm; CDCl3) : 0.96 (3H, t), 1.59 (2H, q), 2.09 (3H, s), 3.68 (2H, s), 7.36-7.37(3H, m), 7.74-7.76 (4H, m), 7.87-7.89(2H, m) 1 H NMR (δ ppm; CDCl 3 ): 0.96 (3H, t), 1.59 (2H, q), 2.09 (3H, s), 3.68 (2H, s), 7.36-7.37 (3H, m), 7.74- 7.76 (4H, m), 7.87-7.89 (2H, m)
MS(m/e):266MS ( m / e ): 266
반응 2. 1-(비페닐-4-일)헥산-1,3-디온 디옥심(24)의 합성Reaction 2. Synthesis of 1- (biphenyl-4-yl) hexane-1,3-dione dioxime ( 24 )
Figure PCTKR2016000635-appb-I000032
Figure PCTKR2016000635-appb-I000032
1-(비페닐-4-일)헥산-1,3-디온(23) 5.0 g (0.019 mol)을 에탄올 100 mL에 분산시키고 염산히드록실아민 3.97 g (0.057 mol)과 초산나트륨 4.68 g(0.057 mol)을 가해준 다음, 반응용액을 서서히 승온하여 1 시간 동안 환류 반응하였다. 반응물을 실온으로 냉각하고 증류수 100 mL와 초산 에틸 200 mL를 가해준 다음, 30분 정도 교반하여 유기층을 분리한 후 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)헥산-1,3-디온 디옥심(24) 5.01 g (88.9 %)을 얻었다. 5.0 g (0.019 mol) of 1- (biphenyl-4-yl) hexane-1,3-dione ( 23 ) is dispersed in 100 mL of ethanol, 3.97 g (0.057 mol) of hydroxylamine hydrochloride and 4.68 g (0.057) of sodium acetate mol) was added, and the reaction solution was gradually heated to reflux for 1 hour. The reaction was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, the mixture was stirred for about 30 minutes, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethyl acetate: n -hexane = 1: 4) to give 5.01 g (88.9%) of 1- (biphenyl-4-yl) hexane-1,3-dione dioxime ( 24 ).
1H NMR(δ ppm; CDCl3) : 0.95 (3H, t), 1.61 (2H, q), 1.86 (3H, s), 2.89 (2H, s), 7.34-7.38(3H, m), 7.80-7.86 (4H, m), 8.01-8.12 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 0.95 (3H, t), 1.61 (2H, q), 1.86 (3H, s), 2.89 (2H, s), 7.34-7.38 (3H, m), 7.80- 7.86 (4H, m), 8.01-8.12 (2H, m)
MS(m/e):296MS ( m / e ): 296
반응 3. 1-(비페닐-4-일)헥산-1,3-디온 O,O-디아세틸 디옥심(25)의 합성Reaction 3. Synthesis of 1- (biphenyl-4-yl) hexane-1,3-dione O, O-diacetyl dioxime ( 25 )
Figure PCTKR2016000635-appb-I000033
Figure PCTKR2016000635-appb-I000033
1-(비페닐-4-일)헥산-1,3-디온 디옥심(24) 5.0 g (0.017 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 3.74 g (0.037 mol)을 가해주고 반응용액을 30분 동안 교반한 후 염화아세틸 2.90g (0.037 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)헥산-1,3-디온 O,O-디아세틸 디옥심(25) 5.84 g (90.3 %)을 얻었다.5.0 g (0.017 mol) of 1- (biphenyl-4-yl) hexane-1,3-dione dioxime ( 24 ) was dissolved in 50 mL of ethyl acetate under a nitrogen atmosphere, and the reaction was kept at -5 ° C, and then 3.74 g (0.037 mol) of ethylamine was added thereto, the reaction solution was stirred for 30 minutes, and then 2.90 g (0.037 mol) of acetyl chloride was added slowly, and the reaction mixture was stirred for 30 minutes while being careful not to raise the reaction temperature. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. : n -hexane = 1: 4) to obtain 5.84 g (90.3%) of 1- (biphenyl-4-yl) hexane-1,3-dione O, O-diacetyl dioxime ( 25 ).
1H NMR(δ ppm; CDCl3) : 0.94 (3H, t), 0.96 (6H, s), 1.61 (2H, q), 1.88 (3H, s), 2.89 (2H, s), 7.34-7.38(3H, m), 7.80-7.86 (4H, m), 8.01-8.12 (3H, m) 1 H NMR (δ ppm; CDCl 3 ): 0.94 (3H, t), 0.96 (6H, s), 1.61 (2H, q), 1.88 (3H, s), 2.89 (2H, s), 7.34-7.38 ( 3H, m), 7.80-7.86 (4H, m), 8.01-8.12 (3H, m)
MS(m/e):380MS ( m / e ): 380
[[ 실시예Example 11] 1-(비페닐-4-일)펜탄-1,4- 11] 1- (biphenyl-4-yl) pentane-1,4- 디온Dion O,OO, O -- 디아세틸Diacetyl 디옥심(28)의Dioxim (28) 제조 Produce
반응 1. 1-(비페닐-4-일)펜탄-1,4-디온(26)의 합성 Reaction 1. Synthesis of 1- (biphenyl-4-yl) pentane-1,4-dione (26)
Figure PCTKR2016000635-appb-I000034
Figure PCTKR2016000635-appb-I000034
질소분위기 하에서 무수 초산 에틸 50 mL를 5℃로 유지한 다음 수소화 나트륨 5.96 g (60% in mineral oil, 0.144 mol)을 가한 후 30분 동안 교반하였다. 초산 에틸 50 mL에 용해한 4-프로피오닐 비페닐(8) 20.0 g (0.096 mol)을 가한 후 1시간 동안 교반한 후 반응 용액을 서서히 승온하여 60℃에서 5 시간 동안 교반하여 반응을 완결하였다. 반응 용액을 실온으로 냉각시키고 H2O 30 mL을 가해준 다음 30분 정도 교반 후, 1% HCl 수용액 80 mL을 천천히 적가하여 반응물의 pH가 6~7이 되도록 중화하였다. 반응용액에 초산 에틸 100 mL을 가하여주고 30분 동안 교반하여 유기층을 분리한 후 H2O로 충분히 씻어준 다음, 회수한 유기층을 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)펜탄-1,4-디온(26) 6.35g (26.2 %)을 얻었다. 50 mL of anhydrous ethyl acetate was maintained at 5 ° C. under a nitrogen atmosphere, and then 5.96 g of sodium hydride (60% in mineral oil, 0.144 mol) was added thereto, followed by stirring for 30 minutes. After adding 20.0 g (0.096 mol) of 4-propionyl biphenyl ( 8 ) dissolved in 50 mL of ethyl acetate, the mixture was stirred for 1 hour, and the reaction solution was gradually warmed up and stirred at 60 ° C. for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, 30 mL of H 2 O was added thereto, followed by stirring for about 30 minutes, and 80 mL of an aqueous 1% HCl solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Purification by chromatography (developing solvent; ethyl acetate: n -hexane = 1: 4) yielded 6.35 g (26.2%) of 1- (biphenyl-4-yl) pentane-1,4-dione ( 26 ).
1H NMR(δ ppm; CDCl3) : 1.87 (3H, s), 2.44 (2H, t), 2.98 (2H, t), 7.35-7.37(3H, m), 7.75-7.76 (4H, m), 7.86-7.89(2H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.87 (3H, s), 2.44 (2H, t), 2.98 (2H, t), 7.35-7.37 (3H, m), 7.75-7.76 (4H, m), 7.86-7.89 (2H, m)
MS(m/e):252MS ( m / e ): 252
반응 2. 1-(비페닐-4-일)펜탄-1,4-디온 디옥심(27)의 합성Reaction 2. Synthesis of 1- (biphenyl-4-yl) pentane-1,4-dione dioxime ( 27 )
Figure PCTKR2016000635-appb-I000035
Figure PCTKR2016000635-appb-I000035
1-(비페닐-4-일)펜탄-1,4-디온(26) 5.0 g (0.020 mol)을 에탄올 100 mL에 분산시키고 염산히드록실아민 4.18 g (0.060 mol)과 초산나트륨 4.92 g(0.060 mol)을 가해준 다음, 반응용액을 서서히 승온하여 1 시간 동안 환류 반응하였다. 반응물을 실온으로 냉각하고 증류수 100 mL와 초산 에틸 200 mL를 가해준 다음, 30분 정도 교반하여 유기층을 분리한 후 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)펜탄-1,4-디온 디옥심(27) 4.98 g (88.2 %)을 얻었다. 5.0 g (0.020 mol) of 1- (biphenyl-4-yl) pentane-1,4-dione ( 26 ) is dispersed in 100 mL of ethanol, 4.18 g (0.060 mol) of hydroxylamine hydrochloride and 4.92 g (0.060) of sodium acetate mol) was added, and the reaction solution was gradually heated to reflux for 1 hour. The reaction was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, the mixture was stirred for about 30 minutes, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethyl acetate: n -hexane = 1: 4) to obtain 4.98 g (88.2%) of 1- (biphenyl-4-yl) pentane-1,4-dione dioxime ( 27 ).
1H NMR(δ ppm; CDCl3) : 1.90 (3H, s), 2.45 (2H, t), 2.96 (2H, t), 7.34-7.38(3H, m), 7.80-7.86 (4H, m), 8.01-8.12 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.90 (3H, s), 2.45 (2H, t), 2.96 (2H, t), 7.34-7.38 (3H, m), 7.80-7.86 (4H, m), 8.01-8.12 (2H, m)
MS(m/e):282MS ( m / e ): 282
반응 3. 1-(비페닐-4-일)펜탄-1,4-디온 O,O-디아세틸 디옥심(28)의 합성Reaction 3. Synthesis of 1- (biphenyl-4-yl) pentane-1,4-dione O, O-diacetyl dioxime ( 28 )
Figure PCTKR2016000635-appb-I000036
Figure PCTKR2016000635-appb-I000036
1-(비페닐-4-일)펜탄-1,4-디온 디옥심(27) 5.0 g (0.018 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 4.05 g (0.040 mol)을 가해주고 반응용액을 30분 동안 교반한 후 염화아세틸 3.14g (0.040 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)펜탄-1,4-디온 O,O-디아세틸 디옥심(28) 5.88 g (89.1 %)을 얻었다.5.0 g (0.018 mol) of 1- (biphenyl-4-yl) pentane-1,4-dione dioxime ( 27 ) was dissolved in 50 mL of ethyl acetate under a nitrogen atmosphere, and the reaction was kept at -5 ° C, and then 4.05 g (0.040 mol) of ethylamine was added thereto, the reaction solution was stirred for 30 minutes, and then 3.14 g (0.040 mol) of acetyl chloride was added slowly, and the reaction mixture was stirred for 30 minutes while being careful not to raise the reaction temperature. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product obtained was subjected to silica gel column chromatography (developing solvent; ethyl acetate). : n -hexane = 1: 4) to give 5.88 g (89.1%) of 1- (biphenyl-4-yl) pentane-1,4-dione O, O-diacetyl dioxime ( 28 ).
1H NMR(δ ppm; CDCl3) : 0.96(6H, s), 1.90 (3H, s), 2.45 (2H, t), 2.96 (2H, t), 7.34-7.38(3H, m), 7.80-7.86 (4H, m), 8.01-8.12 (3H, m) 1 H NMR (δ ppm; CDCl 3 ): 0.96 (6H, s), 1.90 (3H, s), 2.45 (2H, t), 2.96 (2H, t), 7.34-7.38 (3H, m), 7.80- 7.86 (4H, m), 8.01-8.12 (3H, m)
MS(m/e):366MS ( m / e ): 366
[[ 실시예Example 12] 1-(비페닐-4-일)펜탄-1,4- 12] 1- (biphenyl-4-yl) pentane-1,4- 디온Dion O,OO, O -- 디시클로헥산카보닐Dicyclohexanecarbonyl 디옥심(29)의Dioxim (29) 제조 Produce
Figure PCTKR2016000635-appb-I000037
Figure PCTKR2016000635-appb-I000037
1-(비페닐-4-일)펜탄-1,4-디온 디옥심(27) 5.0 g (0.018 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 4.05 g (0.040 mol)을 가해주고 반응용액을 30분 동안 교반한 후 시클로헥산카보닐 클로라이드 5.86g (0.040 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)펜탄-1,4-디온 O,O-디시클로헥산카보닐 디옥심(29) 18.00g (89.5 %)을 얻었다.5.0 g (0.018 mol) of 1- (biphenyl-4-yl) pentane-1,4-dione dioxime ( 27 ) was dissolved in 50 mL of ethyl acetate under a nitrogen atmosphere, and the reaction was kept at -5 ° C, and then 4.05 g (0.040 mol) of ethylamine was added thereto, the reaction solution was stirred for 30 minutes, and then 5.86 g (0.040 mol) of cyclohexanecarbonyl chloride was added slowly, and the reaction mixture was stirred for 30 minutes while being careful not to raise the reaction temperature. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product obtained was purified by silica gel column chromatography (developing solvent; ethyl acetate 1- (biphenyl-4-yl) pentane-1,4-dione O, O-dicyclohexanecarbonyl dioxime ( 29 ) was purified by n -hexane = 1: 4) to obtain 18.00 g (89.5%) of 1- (biphenyl-4-yl) pentane-1,4-dione. Got it.
1H NMR(δ ppm; CDCl3) : 1.12-1.15(10H, m), 1.60-1.66 (12H, m), 1.90 (3H, s), 2.45 (2H, t), 2.96 (2H, t), 7.34-7.38(3H, m), 7.80-7.86 (4H, m), 8.01-8.12 (3H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.12-1.15 (10H, m), 1.60-1.66 (12H, m), 1.90 (3H, s), 2.45 (2H, t), 2.96 (2H, t), 7.34-7.38 (3H, m), 7.80-7.86 (4H, m), 8.01-8.12 (3H, m)
MS(m/e):503MS ( m / e ): 503
[[ 실시예Example 13] 1-(비페닐-4-일)펜탄-1,4- 13] 1- (biphenyl-4-yl) pentane-1,4- 디온Dion O,OO, O -- 디벤조일Dibenzoyl 디옥심(30)의Dioxime (30) 제조 Produce
Figure PCTKR2016000635-appb-I000038
Figure PCTKR2016000635-appb-I000038
1-(비페닐-4-일)펜탄-1,4-디온 디옥심(27) 5.0 g (0.018 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 4.05 g (0.040 mol)을 가해주고 반응용액을 30분 동안 교반한 후 벤조일 클로라이드 5.62g (0.040 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)펜탄-1,4-디온 O,O-디벤조일 디옥심(30) 17.36g (88.5 %)을 얻었다.5.0 g (0.018 mol) of 1- (biphenyl-4-yl) pentane-1,4-dione dioxime ( 27 ) was dissolved in 50 mL of ethyl acetate under a nitrogen atmosphere, and the reaction was kept at -5 ° C, and then 4.05 g (0.040 mol) of ethylamine was added thereto, the reaction solution was stirred for 30 minutes, and then 5.62 g (0.040 mol) of benzoyl chloride was added slowly, and the reaction mixture was stirred for 30 minutes while being careful not to raise the reaction temperature. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product obtained was purified by silica gel column chromatography (developing solvent; ethyl acetate : n -hexane = 1: 4) to give 17.36 g (88.5%) of 1- (biphenyl-4-yl) pentane-1,4-dione O, O-dibenzoyl dioxime ( 30 ).
1H NMR(δ ppm; CDCl3) : 1.91 (3H, s), 2.42 (2H, t), 2.95 (2H, t), 7.36-7.38(3H, m), 7.55-7.58 (6H, m), 7.80-7.82 (4H, m), 8.01-8.04 (3H, m), 8.18-8.20 (4H, m) 1 H NMR (δ ppm; CDCl 3 ): 1.91 (3H, s), 2.42 (2H, t), 2.95 (2H, t), 7.36-7.38 (3H, m), 7.55-7.58 (6H, m), 7.80-7.82 (4H, m), 8.01-8.04 (3H, m), 8.18-8.20 (4H, m)
MS(m/e):491MS ( m / e ): 491
[[ 실시예Example 14] 1-(4'- 14] 1- (4'- 니트로비페닐Nitrobiphenyl -4-일)부탄-1,3--4-yl) butane-1,3- 디온Dion O,OO, O -- 디아세틸Diacetyl 디옥심(34)의Dioxim (34) 제조 Produce
반응 1. 1-(4'-니트로-비페닐-4-일)에탄온(31) 합성 Reaction 1. 1- (4'-nitro-biphenyl-4-yl) ethanone ( 31 ) synthesis
Figure PCTKR2016000635-appb-I000039
Figure PCTKR2016000635-appb-I000039
4-아세틸비페닐(1) 21.6 g(0.11 mol)을 진한 황산 150 mL에 용해시키고 반응물을 -10℃로 유지한 다음, 질산칼륨 12.1g(0.12 mol)을 3시간에 걸쳐서 천천히 가해주고, 반응물을 -10℃에서 30분 동안 교반하였다. 그런 다음 에탄올 400mL를 반응물의 온도가 0℃를 넘지 않도록 주의하면서 가해주고 1시간 정도 교반 후 생성물을 여과하였다. 얻어진 고체 생성물을 500mL의 증류수에 분산시키고 실온에서 30분 정도 교반 후 여과하고 증류수로 충분히 씻어준 다음 건조하여 연회색의 1-(4'-니트로-비페닐-4-일)에탄온(31) 17.8 g(67.2 %)을 얻었다. 21.6 g (0.11 mol) of 4-acetylbiphenyl (1) was dissolved in 150 mL of concentrated sulfuric acid and the reaction was maintained at -10 ° C. Then, 12.1 g (0.12 mol) of potassium nitrate was slowly added over 3 hours. Was stirred at −10 ° C. for 30 minutes. Then, 400 mL of ethanol was added while being careful not to exceed the temperature of the reactant, and the product was filtered after stirring for about 1 hour. The obtained solid product was dispersed in 500 mL of distilled water, stirred at room temperature for about 30 minutes, filtered, washed sufficiently with distilled water, and dried to light gray 1- (4'-nitro-biphenyl-4-yl) ethanone ( 31 ). 17.8 g (67.2%) was obtained.
1H-NMR(δ ppm; CDCl3) : 2.66(3H, s), 7.71-7.80(4H, m), 8.05(2H, d), 8.31(2H, d) 1 H-NMR (δ ppm; CDCl 3 ): 2.66 (3H, s), 7.71-7.80 (4H, m), 8.05 (2H, d), 8.31 (2H, d)
MS(m/e) : 241MS ( m / e ): 241
반응 2. 1-(4'-니트로-비페닐-4-일)부탄-1,3-디온(32)의 합성 Reaction 2. Synthesis of 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione ( 32 )
Figure PCTKR2016000635-appb-I000040
Figure PCTKR2016000635-appb-I000040
질소분위기 하에서 무수 초산 에틸 50 mL를 5℃로 유지한 다음 수소화 나트륨 5.00 g (60% in mineral oil, 0.125 mol)을 가한 후 30분 동안 교반하였다. 초산 에틸 50 mL에 용해한 1-(4'-니트로-비페닐-4-일)에탄온(31) 20.0 g (0.083 mol)을 가한 후 1시간 동안 교반한 후 반응 용액을 서서히 승온하여 60℃에서 5 시간 동안 교반하여 반응을 완결하였다. 반응 용액을 실온으로 냉각시키고 H2O 30 mL을 가해준 다음 30분 정도 교반 후, 1% HCl 수용액 80 mL을 천천히 적가하여 반응물의 pH가 6~7이 되도록 중화하였다. 반응용액에 초산 에틸 100 mL을 가하여주고 30분 동안 교반하여 유기층을 분리한 후 H2O로 충분히 씻어준 다음, 회수한 유기층을 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-니트로-비페닐-4-일)부탄-1,4-디온(32) 13.59 g (57.8 %)을 얻었다. 50 mL of anhydrous ethyl acetate was maintained at 5 ° C. under a nitrogen atmosphere, and then 5.00 g (60% in mineral oil, 0.125 mol) of sodium hydride were added thereto, followed by stirring for 30 minutes. 20.0 g (0.083 mol) of 1- (4'-nitro-biphenyl-4-yl) ethanone ( 31 ) dissolved in 50 mL of ethyl acetate was added thereto, stirred for 1 hour, and the reaction solution was gradually heated to 60 ° C. Stir for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, 30 mL of H 2 O was added thereto, followed by stirring for about 30 minutes, and 80 mL of an aqueous 1% HCl solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 13.59 g (57.8%) of 1- (4'-nitro-biphenyl-4-yl) butane-1,4-dione ( 32 ), purified by chromatography (developing solvent; ethyl acetate: n -hexane = 1: 4). Got.
1H NMR(δ ppm; CDCl3) : 1.87 (3H, s), 2.44 (2H, s), 7.70-7.78(4H, m), 8.02(2H, d), 8.26(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 1.87 (3H, s), 2.44 (2H, s), 7.70-7.78 (4H, m), 8.02 (2H, d), 8.26 (2H, d)
MS(m/e):283MS ( m / e ): 283
반응 3. 1-(4'-니트로-비페닐-4-일)부탄-1,3-디온 디옥심(33)의 합성Reaction 3. Synthesis of 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione dioxime ( 33 )
Figure PCTKR2016000635-appb-I000041
Figure PCTKR2016000635-appb-I000041
1-(4'-니트로-비페닐-4-일)부탄-1,4-디온(32) 5.0 g (0.018 mol)을 에탄올 100 mL에 분산시키고 염산히드록실아민 3.76 g (0.054 mol)과 초산나트륨 4.43 g (0.054 mol)을 가해준 다음, 반응용액을 서서히 승온하여 1 시간 동안 환류 반응하였다. 반응물을 실온으로 냉각하고 증류수 100 mL와 초산 에틸 200 mL를 가해준 다음, 30분 정도 교반하여 유기층을 분리한 후 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-니트로-비페닐-4-일)부탄-1,3-디온 디옥심(33) 4.97 g (88.2 %)을 얻었다. 5.0 g (0.018 mol) of 1- (4'-nitro-biphenyl-4-yl) butane-1,4-dione ( 32 ) is dispersed in 100 mL of ethanol, and 3.76 g (0.054 mol) of hydroxylamine hydrochloride and acetic acid 4.43 g (0.054 mol) of sodium was added thereto, and the reaction solution was gradually heated to reflux for 1 hour. The reaction was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, the mixture was stirred for about 30 minutes, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethyl acetate: n -hexane = 1: 4) to obtain 4.97 g (88.2%) of 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione dioxime ( 33 ); .
1H NMR(δ ppm; CDCl3) : 1.90 (3H, s), 2.45 (2H, s), 7.70-7.76(4H, m), 8.00(2H, d), 8.25(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 1.90 (3H, s), 2.45 (2H, s), 7.70-7.76 (4H, m), 8.00 (2H, d), 8.25 (2H, d)
MS(m/e):313MS ( m / e ): 313
반응 4. 1-(4'-니트로-비페닐-4-일)부탄-1,3-디온 O,O-디아세틸 디옥심(34)의 합성Reaction 4. Synthesis of 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione O, O-diacetyl dioxime ( 34 )
Figure PCTKR2016000635-appb-I000042
Figure PCTKR2016000635-appb-I000042
1-(4'-니트로-비페닐-4-일)부탄-1,3-디온 디옥심(33) 5.0 g (0.016 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 3.56 g (0.035 mol)을 가해주고 반응용액을 30분 동안 교반한 후 염화아세틸 2.75 g (0.035 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-니트로-비페닐-4-일)부탄-1,3-디온 O,O-디아세틸 디옥심(34) 5.67 g (89.1 %)을 얻었다.5.0 g (0.016 mol) of 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione dioxime ( 33 ) are dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction is brought to -5 ° C. After that, 3.56 g (0.035 mol) of triethylamine was added thereto, the reaction solution was stirred for 30 minutes, and then 2.75 g (0.035 mol) of acetyl chloride was slowly added thereto, and the mixture was stirred for 30 minutes while being careful not to raise the reaction temperature. . Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product obtained was purified by silica gel column chromatography (developing solvent; ethyl acetate 5.67 g (89.1%) of 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione O, O-diacetyl dioxime ( 34 ) by purification with n -hexane = 1: 4) )
1H NMR(δ ppm; CDCl3) : 0.96(6H, s), 1.90 (3H, s), 2.45 (2H, s), 7.70-7.76(4H, m), 8.00(2H, d), 8.25(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 0.96 (6H, s), 1.90 (3H, s), 2.45 (2H, s), 7.70-7.76 (4H, m), 8.00 (2H, d), 8.25 ( 2H, d)
MS(m/e):397MS ( m / e ): 397
[[ 실시예Example 15] 1-(4'- 15] 1- (4'- 니트로비페닐Nitrobiphenyl -4-일)부탄-1,3--4-yl) butane-1,3- 디온Dion O,OO, O -- 디시클로헥산카보닐Dicyclohexanecarbonyl 디옥심(35)의Dioxim (35) 제조 Produce
Figure PCTKR2016000635-appb-I000043
Figure PCTKR2016000635-appb-I000043
1-(4'-니트로-비페닐-4-일)부탄-1,3-디온 디옥심(33) 5.0 g (0.016 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 3.56 g (0.035 mol)을 가해주고 반응용액을 30분 동안 교반한 후 시클로헥산카보닐 클로라이드 5.13 g (0.035 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-니트로-비페닐-4-일)부탄-1,3-디온 O,O-디시클로헥산카보닐 디옥심(35) 7.35 g (86.1 %)을 얻었다.5.0 g (0.016 mol) of 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione dioxime ( 33 ) are dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction is brought to -5 ° C. Then, add 3.56 g (0.035 mol) of triethylamine and stir the reaction solution for 30 minutes, and then slowly add 5.13 g (0.035 mol) of cyclohexanecarbonyl chloride, taking 30 minutes, taking care not to raise the reaction temperature. Was stirred. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product obtained was subjected to silica gel column chromatography (developing solvent; ethyl acetate). 7.35 g of 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione O, O-dicyclohexanecarbonyl dioxime ( 35 ) purified by n -hexane = 1: 4) (86.1%) was obtained.
1H NMR(δ ppm; CDCl3) : 1.12-1.15(10H, m), 1.60-1.66 (12H, m), 1.92 (3H, s), 2.48 (2H, s), 7.70-7.75(4H, m), 8.01(2H, d), 8.24(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 1.12-1.15 (10H, m), 1.60-1.66 (12H, m), 1.92 (3H, s), 2.48 (2H, s), 7.70-7.75 (4H, m ), 8.01 (2H, d), 8.24 (2H, d)
MS(m/e):534MS ( m / e ): 534
[[ 실시예Example 16] 1-(4'- 16] 1- (4'- 니트로비페닐Nitrobiphenyl -4-일)부탄-1,3--4-yl) butane-1,3- 디온Dion O,OO, O -- 디벤조일Dibenzoyl 디옥심(36)의Dioxim (36) 제조 Produce
Figure PCTKR2016000635-appb-I000044
Figure PCTKR2016000635-appb-I000044
1-(4'-니트로-비페닐-4-일)부탄-1,3-디온 디옥심(33) 5.0 g (0.016 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 3.56 g (0.035 mol)을 가해주고 반응용액을 30분 동안 교반한 후 벤조일 클로라이드 4.92 g (0.035 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-니트로-비페닐-4-일)부탄-1,3-디온 O,O-디벤조일 디옥심(36) 7.19 g (86.2 %)을 얻었다.5.0 g (0.016 mol) of 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione dioxime ( 33 ) are dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction is brought to -5 ° C. After that, 3.56 g (0.035 mol) of triethylamine was added and the reaction solution was stirred for 30 minutes, and then 4.92 g (0.035 mol) of benzoyl chloride was added slowly, and the reaction mixture was stirred for 30 minutes while being careful not to raise the reaction temperature. . Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product obtained was purified by silica gel column chromatography (developing solvent; ethyl acetate : n-hexane = 1: 4) to give 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione O, O- dibenzoyl-D-oxime (36) 7.19 g (86.2% )
1H NMR(δ ppm; CDCl3) : 1.92 (3H, s), 2.48 (2H, s), 7.55-7.58 (6H, m), 7.70-7.75(4H, m), 7.80-7.82 (4H, m), 8.01(2H, d), 8.24(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 1.92 (3H, s), 2.48 (2H, s), 7.55-7.58 (6H, m), 7.70-7.75 (4H, m), 7.80-7.82 (4H, m ), 8.01 (2H, d), 8.24 (2H, d)
MS(m/e):522MS ( m / e ): 522
[[ 실시예Example 17] 1- 17] 1- 시클로헥실Cyclohexyl -3-(4'--3- (4'- 니트로비페닐Nitrobiphenyl -4-일)프로판-1,3--4-yl) propane-1,3- 디온Dion O,OO, O -- 디아세틸Diacetyl 디옥심(39)의Dioxim (39) 제조 Produce
반응 1. 1-시클로헥실-3-(4'-니트로비페닐-4-일)프로판-1,3-디온(37)의 합성 Reaction 1. Synthesis of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) propane-1,3-dione ( 37 )
Figure PCTKR2016000635-appb-I000045
Figure PCTKR2016000635-appb-I000045
질소분위기 하에서 무수 에틸시클로헥산카르복실레이트 50 mL를 5℃로 유지한 다음 수소화 나트륨 5.00 g (60% in mineral oil, 0.125 mol)을 가한 후 30분 동안 교반하였다. 에틸시클로헥산카르복실레이트 50 mL에 용해한 1-(4'-니트로-비페닐-4-일)에탄온(31) 20.0 g (0.083 mol)을 가한 후 1시간 동안 교반한 후 반응 용액을 서서히 승온하여 60℃에서 5 시간 동안 교반하여 반응을 완결하였다. 반응 용액을 실온으로 냉각시키고 H2O 30 mL을 가해준 다음 30분 정도 교반 후, 1% HCl 수용액 80 mL을 천천히 적가하여 반응물의 pH가 6~7이 되도록 중화하였다. 반응용액에 초산 에틸 100 mL을 가하여주고 30분 동안 교반하여 유기층을 분리한 후 H2O로 충분히 씻어준 다음, 회수한 유기층을 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-시클로헥실-3-(4'-니트로비페닐-4-일)프로판-1,3-디온(37) 15.11 g (51.8 %)을 얻었다. 50 mL of anhydrous ethylcyclohexanecarboxylate was maintained at 5 ° C. under a nitrogen atmosphere, and then 5.00 g (60% in mineral oil, 0.125 mol) of sodium hydride were added thereto, followed by stirring for 30 minutes. 20.0 g (0.083 mol) of 1- (4'-nitro-biphenyl-4-yl) ethanone ( 31 ) dissolved in 50 mL of ethylcyclohexanecarboxylate was added thereto, stirred for 1 hour, and the reaction solution was gradually warmed up. The mixture was stirred at 60 ° C. for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, 30 mL of H 2 O was added thereto, followed by stirring for about 30 minutes, and 80 mL of an aqueous 1% HCl solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 15.11 g of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) propane-1,3-dione ( 37 ) purified by chromatography (developing solvent; ethyl acetate: n -hexane = 1: 4) (51.8%) was obtained.
1H NMR(δ ppm; CDCl3) : 1.11-1.15(10H, m), 1.58-1.66 (12H, m), 2.42 (2H, s), 7.71-7.77(4H, m), 8.01(2H, d), 8.20(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 1.11-1.15 (10H, m), 1.58-1.66 (12H, m), 2.42 (2H, s), 7.71-7.77 (4H, m), 8.01 (2H, d ), 8.20 (2H, d)
MS(m/e):351MS ( m / e ): 351
반응 2. 1-시클로헥실-3-(4'-니트로비페닐-4-일)프로판-1,3-디온 디옥심(38)의 합성Reaction 2. Synthesis of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) propane-1,3-dione dioxime ( 38 )
Figure PCTKR2016000635-appb-I000046
Figure PCTKR2016000635-appb-I000046
1-시클로헥실-3-(4'-니트로비페닐-4-일)프로판-1,3-디온(37) 10.0 g (0.028 mol)을 에탄올 100 mL에 분산시키고 염산히드록실아민 5.85 g (0.084 mol)과 초산나트륨 6.89 g (0.054 mol)을 가해준 다음, 반응용액을 서서히 승온하여 1 시간 동안 환류 반응하였다. 반응물을 실온으로 냉각하고 증류수 100 mL와 초산 에틸 200 mL를 가해준 다음, 30분 정도 교반하여 유기층을 분리한 후 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-시클로헥실-3-(4'-니트로비페닐-4-일)프로판-1,3-디온 디옥심(38) 8.99 g (84.2 %)을 얻었다. 10.0 g (0.028 mol) of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) propane-1,3-dione ( 37 ) was dispersed in 100 mL of ethanol and 5.85 g (0.084) of hydroxylamine hydrochloride mol) and 6.89 g (0.054 mol) of sodium acetate were added, and the reaction solution was gradually heated to reflux for 1 hour. The reaction was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, the mixture was stirred for about 30 minutes, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 8.99 g (84.2) of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) propane-1,3-dione dioxime ( 38 ) purified by ethyl acetate: n -hexane = 1: 4) %) Was obtained.
1H NMR(δ ppm; CDCl3) : 1.11-1.14 (10H, m), 1.58-1.67 (12H, m), 2.43 (2H, s), 7.71-7.76(4H, m), 8.01(2H, d), 8.25(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 1.11-1.14 (10H, m), 1.58-1.67 (12H, m), 2.43 (2H, s), 7.71-7.76 (4H, m), 8.01 (2H, d ), 8.25 (2H, d)
MS(m/e):381MS ( m / e ): 381
반응 3. 1-시클로헥실-3-(4'-니트로비페닐-4-일)프로판-1,3-디온 O,O-디아세틸 디옥심(39)의 합성Reaction 3. Synthesis of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) propane-1,3-dione O, O-diacetyl dioxime ( 39 )
Figure PCTKR2016000635-appb-I000047
Figure PCTKR2016000635-appb-I000047
1-시클로헥실-3-(4'-니트로비페닐-4-일)프로판-1,3-디온 디옥심(38) 5.0 g (0.013 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 2.93 g (0.029 mol)을 가해주고 반응용액을 30분 동안 교반한 후 염화아세틸 2.28 g (0.029 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-시클로헥실-3-(4'-니트로비페닐-4-일)프로판-1,3-디온 O,O-디아세틸 디옥심(39) 4.97 g (82.1 %)을 얻었다.5.0 g (0.013 mol) of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) propane-1,3-dione dioxime ( 38 ) are dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction is carried out. After maintaining at -5 ° C, 2.93 g (0.029 mol) of triethylamine was added, the reaction solution was stirred for 30 minutes, and then slowly added 2.28 g (0.029 mol) of acetyl chloride, taking care not to raise the reaction temperature. Stir for minutes. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product obtained was purified by silica gel column chromatography (developing solvent; ethyl acetate : n - hexane = 1: 4) to provide 1-cyclohexyl-3- (4'-knit lobby-4-yl) propane-1,3-dione O, O- di-acetyl-di-oxime (39) 4.97 g (82.1%) was obtained.
1H NMR(δ ppm; CDCl3) : 0.95 (6H, s), 1.10-1.14 (10H, m), 1.57-1.65 (12H, m), 2.43 (2H, s), 7.70-7.76(4H, m), 8.00(2H, d), 8.25(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 0.95 (6H, s), 1.10-1.14 (10H, m), 1.57-1.65 (12H, m), 2.43 (2H, s), 7.70-7.76 (4H, m ), 8.00 (2H, d), 8.25 (2H, d)
MS(m/e):466MS ( m / e ): 466
[[ 실시예Example 18] 1-(4'- 18] 1- (4'- 니트로비페닐Nitrobiphenyl -4-일)-2--4-yl) -2- 펜틸부탄Pentylbutane -1,3--1,3- 디온Dion O,OO, O -- 디아세틸Diacetyl 디옥심(44)의 제조 Preparation of Dioxime 44
반응 1. 1-(비페닐-4-일)헵탄-1-온(40)의 합성Reaction 1. Synthesis of 1- (biphenyl-4-yl) heptan-1-one ( 40 )
Figure PCTKR2016000635-appb-I000048
Figure PCTKR2016000635-appb-I000048
비페닐(14) 10.0 g (0.065 mol)을 디클로로메탄 100 mL에 용해시키고 반응물을 -5 ℃로 냉각한 후, 염화알루미늄 10.40 g (0.78 mol)을 천천히 가해준 다음 반응물의 온도가 승온되지 않도록 주의 하면서 디클로로메탄 5 mL에 희석시킨 헵타노일클로라이드 11.59 g (0.078 mol)을 2시간에 걸쳐서 천천히 가해주고 -5 ℃에서 1시간 동안 반응물을 교반하였다. 그런 다음 반응물을 얼음물 1 L에 천천히 붓고 30분 동안 교반하여 유기층을 분리한 후, 증류수 500 mL로 씻어주고 회수한 유기층을 감압 증류하여 얻은 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)헵탄-1-온(40) 10.56 g (61.0 %)을 얻었다. Biphenyl ( 14 ) Dissolve 10.0 g (0.065 mol) in 100 mL of dichloromethane, cool the reaction to -5 ° C, slowly add 10.40 g (0.78 mol) of aluminum chloride, and 5 mL of dichloromethane, taking care not to raise the temperature of the reaction. 11.59 g (0.078 mol) of heptanoyl chloride diluted in was slowly added over 2 hours, and the reaction was stirred at -5 ° C for 1 hour. Then, the reaction mixture was slowly poured into 1 L of ice water and stirred for 30 minutes to separate the organic layer, and then washed with 500 mL of distilled water, and the recovered organic layer was distilled under reduced pressure (developing solvent; ethyl acetate: n -hexane = 1: 4) to give 10.56 g (61.0%) of 1- (biphenyl-4-yl) heptan-1-one ( 40 ).
1H NMR(δ ppm; CDCl3) : 0.85(3H, t), 1.25(8H, m), 1.70(2H, m), 7.35-7.38(3H, m), 7.82-7.86 (4H, m), 8.01-8.08 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 0.85 (3H, t), 1.25 (8H, m), 1.70 (2H, m), 7.35-7.38 (3H, m), 7.82-7.86 (4H, m), 8.01-8.08 (2H, m)
MS(m/e): 266MS ( m / e ): 266
반응 2. 1-(4'-니트로-비페닐-4-일)헵탄-1-온(41)의 합성 Reaction 2. Synthesis of 1- (4'-nitro-biphenyl-4-yl) heptan-1-one ( 41 )
Figure PCTKR2016000635-appb-I000049
Figure PCTKR2016000635-appb-I000049
1-(비페닐-4-일)헵탄-1-온(40) 10.0 g(0.038 mol)을 진한 황산 100 mL에 용해시키고 반응물을 -10℃로 유지한 다음, 질산칼륨 4.65 g(0.046 mol)을 3시간에 걸쳐서 천천히 가해주고, 반응물을 -10℃에서 30분 동안 교반하였다. 그런 다음 에탄올 400 mL를 반응물의 온도가 0℃를 넘지 않도록 주의하면서 가해주고 1시간 정도 교반 후 생성물을 여과하였다. 얻어진 고체 생성물을 500 mL의 증류수에 분산시키고 실온에서 30분 정도 교반 후 여과하고 증류수로 충분히 씻어준 다음 건조하여 연회색의 1-(4'-니트로-비페닐-4-일)헵탄-1-온(41) 7.36 g(62.2 %)을 얻었다. 10.0 g (0.038 mol) of 1- (biphenyl-4-yl) heptan-1-one ( 40 ) is dissolved in 100 mL of concentrated sulfuric acid and the reaction is kept at -10 ° C., followed by 4.65 g (0.046 mol) of potassium nitrate. Was added slowly over 3 hours and the reaction was stirred at -10 ° C for 30 minutes. Then, 400 mL of ethanol was added while being careful not to exceed the temperature of the reactant, and the product was filtered after stirring for about 1 hour. The obtained solid product was dispersed in 500 mL of distilled water, stirred at room temperature for 30 minutes, filtered, washed sufficiently with distilled water, and dried to light gray 1- (4'-nitro-biphenyl-4-yl) heptan-1-one. (41) was obtained 7.36 g (62.2%).
1H-NMR(δ ppm; CDCl3) : 0.87(3H, t), 1.28(8H, m), 1.72(2H, m), 7.71-7.78(4H, m), 8.05(2H, d), 8.31(2H, d) 1 H-NMR (δ ppm; CDCl 3 ): 0.87 (3H, t), 1.28 (8H, m), 1.72 (2H, m), 7.71-7.78 (4H, m), 8.05 (2H, d), 8.31 (2H, d)
MS(m/e) : 311MS ( m / e ): 311
반응 3. 1-(4'-니트로-비페닐-4-일)-2-펜틸부탄-1,3-디온(42)의 합성Reaction 3. Synthesis of 1- (4'-nitro-biphenyl-4-yl) -2-pentylbutane-1,3-dione ( 42 )
Figure PCTKR2016000635-appb-I000050
Figure PCTKR2016000635-appb-I000050
질소분위기 하에서 무수 초산 에틸 50 mL를 5℃로 유지한 다음 수소화 나트륨 1.92 g (60% in mineral oil, 0.048 mol)을 가한 후 30분 동안 교반하였다. 초산 에틸 50 mL에 용해한 1-(4'-니트로-비페닐-4-일)헵탄-1-온(41) 10.0 g (0.032 mol)을 가한 후 1시간 동안 교반한 후 반응 용액을 서서히 승온하여 60℃에서 5 시간 동안 교반하여 반응을 완결하였다. 반응용액을 실온으로 냉각시키고 H2O 30 mL을 가해준 다음 30분 정도 교반 후, 1% HCl 수용액 30 mL을 천천히 적가하여 반응물의 pH가 6~7이 되도록 중화하였다. 반응용액에 초산 에틸 100 mL을 가하여주고 30분 동안 교반하여 유기층을 분리한 후 H2O로 충분히 씻어준 다음, 회수한 유기층을 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-니트로-비페닐-4-일)-2-펜틸부탄-1,3-디온(42) 5.89 g (52.1 %)을 얻었다. 50 mL of anhydrous ethyl acetate was maintained at 5 ° C. under a nitrogen atmosphere, and then 1.92 g (60% in mineral oil, 0.048 mol) of sodium hydride was added thereto, followed by stirring for 30 minutes. 10.0 g (0.032 mol) of 1- (4'-nitro-biphenyl-4-yl) heptan-1-one ( 41 ) dissolved in 50 mL of ethyl acetate was added thereto, stirred for 1 hour, and the reaction solution was gradually warmed up. The reaction was completed by stirring at 60 ° C. for 5 hours. The reaction solution was cooled to room temperature, 30 mL of H 2 O was added, followed by stirring for about 30 minutes, and 30 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 5.89 g of 1- (4'-nitro-biphenyl-4-yl) -2-pentylbutane-1,3-dione ( 42 ) purified by chromatography (developing solvent; ethyl acetate: n -hexane = 1: 4). (52.1%) was obtained.
1H NMR(δ ppm; CDCl3) : 0.87(3H, t), 1.28(8H, m), 1.72(1H, t), 2.10 (3H, s), 7.32-7.36 (3H, m), 7.80-7.84 (4H, m), 8.01-8.06 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 0.87 (3H, t), 1.28 (8H, m), 1.72 (1H, t), 2.10 (3H, s), 7.32-7.36 (3H, m), 7.80- 7.84 (4H, m), 8.01-8.06 (2H, m)
MS(m/e): 353MS ( m / e ): 353
반응 4. 1-(4'-니트로-비페닐-4-일)-2-펜틸부탄-1,3-디온 디옥심(43)의 합성Reaction 4. Synthesis of 1- (4'-nitro-biphenyl-4-yl) -2-pentylbutane-1,3-dione dioxime ( 43 )
Figure PCTKR2016000635-appb-I000051
Figure PCTKR2016000635-appb-I000051
1-(4'-니트로-비페닐-4-일)-2-펜틸부탄-1,3-디온(42) 5.0 g (0.014 mol)을 에탄올 100 mL에 분산시키고 염산히드록실아민 2.92 g (0.042 mol)과 초산나트륨 3.45 g(0.042 mol)을 가해준 다음, 반응용액을 서서히 승온하여 1 시간 동안 환류 반응하였다. 반응물을 실온으로 냉각하고 증류수 100 mL와 초산 에틸 200 mL를 가해준 다음, 30분 정도 교반하여 유기층을 분리한 후 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-니트로-비페닐-4-일)-2-펜틸부탄-1,3-디온 디옥심(43) 4.45 g (82.9 %)을 얻었다. 5.0 g (0.014 mol) of 1- (4'-nitro-biphenyl-4-yl) -2-pentylbutane-1,3-dione ( 42 ) are dispersed in 100 mL of ethanol and 2.92 g (0.042) of hydroxylamine hydrochloride mol) and sodium acetate 3.45 g (0.042 mol) were added, and the reaction solution was gradually heated to reflux for 1 hour. The reaction was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, the mixture was stirred for about 30 minutes, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 4.45 g (82.9) of 1- (4'-nitro-biphenyl-4-yl) -2-pentylbutane-1,3-dione dioxime ( 43 ), purified by ethyl acetate: n -hexane = 1: 4); %) Was obtained.
1H NMR(δ ppm; CDCl3) : 0.88(3H, t), 1.29(8H, m), 1.72(1H, t), 2.09 (3H, s), 3.44 (1H, d), 7.32-7.34(3H, m), 7.80-7.82 (4H, m), 8.01-8.06 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 0.88 (3H, t), 1.29 (8H, m), 1.72 (1H, t), 2.09 (3H, s), 3.44 (1H, d), 7.32-7.34 ( 3H, m), 7.80-7.82 (4H, m), 8.01-8.06 (2H, m)
MS(m/e): 383MS ( m / e ): 383
반응 5. 1-(4'-니트로-비페닐-4-일)-2-펜틸부탄-1,3-디온 O,O-디아세틸 디옥심(44)의 합성Reaction 5. Synthesis of 1- (4'-nitro-biphenyl-4-yl) -2-pentylbutane-1,3-dione O, O-diacetyl dioxime ( 44 )
Figure PCTKR2016000635-appb-I000052
Figure PCTKR2016000635-appb-I000052
1-(4'-니트로-비페닐-4-일)-2-펜틸부탄-1,3-디온 디옥심(43) 5.0 g (0.013 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 2.93 g (0.029 mol)을 가해주고 반응용액을 30분 동안 교반한 후 염화아세틸 2.28g (0.029 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-니트로-비페닐-4-일)-2-펜틸부탄-1,3-디온 O,O-디아세틸 디옥심(44) 5.55 g (91.3 %)을 얻었다.5.0 g (0.013 mol) of 1- (4'-nitro-biphenyl-4-yl) -2-pentylbutane-1,3-dione dioxime ( 43 ) are dissolved in 50 mL of ethyl acetate under a nitrogen atmosphere and the reaction is carried out. After maintaining at -5 ° C, 2.93 g (0.029 mol) of triethylamine was added, the reaction solution was stirred for 30 minutes, and then slowly added 2.28 g (0.029 mol) of acetyl chloride, taking care not to raise the reaction temperature. Stir for minutes. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product obtained was purified by silica gel column chromatography (developing solvent; ethyl acetate : 1- (4'-nitro-biphenyl-4-yl) -2-pentylbutane-1,3-dione O, O-diacetyl dioxime ( 44 ) by purification with n -hexane = 1: 4) 5.55 g (91.3%) was obtained.
1H NMR(δ ppm; CDCl3) : 0.86(3H, t), 0.96(6H, s), 1.28(8H, m), 1.72(1H, t), 7.33-7.35(3H, m), 7.80-7.82 (4H, m), 8.01-8.06 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 0.86 (3H, t), 0.96 (6H, s), 1.28 (8H, m), 1.72 (1H, t), 7.33-7.35 (3H, m), 7.80- 7.82 (4H, m), 8.01-8.06 (2H, m)
MS(m/e): 468MS ( m / e ): 468
[[ 실시예Example 19] 1-(4'- 19] 1- (4'- 니트로비페닐Nitrobiphenyl -4-일)-2--4-yl) -2- 펜틸부탄Pentylbutane -1,3--1,3- 디온Dion O,OO, O -- 디벤조일Dibenzoyl 디옥심(45)의 제조 Preparation of Dioxime 45
Figure PCTKR2016000635-appb-I000053
Figure PCTKR2016000635-appb-I000053
1-(4'-니트로-비페닐-4-일)-2-펜틸부탄-1,3-디온 디옥심(43) 5.0 g (0.013 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 2.93 g (0.029 mol)을 가해주고 반응용액을 30분 동안 교반한 후 벤조일 클로라이드 4.07 g (0.029 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-니트로비페닐-4-일)-2-펜틸부탄-1,3-디온 O,O-디벤조일 디옥심(45) 6.87 g (89.3 %)을 얻었다.5.0 g (0.013 mol) of 1- (4'-nitro-biphenyl-4-yl) -2-pentylbutane-1,3-dione dioxime ( 43 ) are dissolved in 50 mL of ethyl acetate under a nitrogen atmosphere and the reaction is carried out. After maintaining at -5 ° C, 2.93 g (0.029 mol) of triethylamine was added, the reaction solution was stirred for 30 minutes, and then slowly added 4.07 g (0.029 mol) of benzoyl chloride, taking care not to raise the reaction temperature. Stir for minutes. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product obtained was purified by silica gel column chromatography (developing solvent; ethyl acetate 6.87 g of 1- (4'-nitrobiphenyl-4-yl) -2-pentylbutan-1,3-dione O, O-dibenzoyl dioxime ( 45 ) purified by n -hexane = 1: 4) (89.3%) was obtained.
1H NMR(δ ppm; CDCl3) : 0.88(3H, t), 1.28(8H, m), 1.74(1H, t), 7.56-7.58 (6H, m), 7.71-7.75(4H, m), 7.80-7.82 (4H, m), 8.03(2H, d), 8.24(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 0.88 (3H, t), 1.28 (8H, m), 1.74 (1H, t), 7.56-7.58 (6H, m), 7.71-7.75 (4H, m), 7.80-7.82 (4H, m), 8.03 (2H, d), 8.24 (2H, d)
MS(m/e): 592MS ( m / e ): 592
[[ 실시예Example 20] 1- 20] 1- 시클로헥실Cyclohexyl -3-(4'--3- (4'- 니트로비페닐Nitrobiphenyl -4-일)-2--4-yl) -2- 펜틸프로판Pentylpropane -1,3--1,3- 디온Dion O,O-디아세틸  O, O-diacetyl 디옥심(48)의Dioxim (48) 제조 Produce
반응 1. 1-시클로헥실-3-(4'-니트로비페닐-4-일)-2-펜틸프로판-1,3-디온(46)의 합성Reaction 1. Synthesis of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) -2-pentylpropane-1,3-dione ( 46 )
Figure PCTKR2016000635-appb-I000054
Figure PCTKR2016000635-appb-I000054
질소분위기 하에서 무수 에틸시클로헥산카르복실레이트 50 mL를 5℃로 유지한 다음 수소화 나트륨 2.16 g (60% in mineral oil, 0.054 mol)을 가한 후 30분 동안 교반하였다. 에틸시클로헥산카르복실레이트 50 mL에 용해한 1-(4'-니트로-비페닐-4-일)헵탄-1-온(41) 10.0 g (0.032 mol)을 가한 후 1시간 동안 교반한 후 반응 용액을 서서히 승온하여 60℃에서 5 시간 동안 교반하여 반응을 완결하였다. 반응용액을 실온으로 냉각시키고 H2O 30 mL을 가해준 다음 30분 정도 교반 후, 1% HCl 수용액 30 mL을 천천히 적가하여 반응물의 pH가 6~7이 되도록 중화하였다. 반응용액에 초산 에틸 100 mL을 가하여주고 30분 동안 교반하여 유기층을 분리한 후 H2O로 충분히 씻어준 다음, 회수한 유기층을 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-시클로헥실-3-(4'-니트로비페닐-4-일)-2-펜틸프로판-1,3-디온(46) 6.76 g (50.1 %)을 얻었다. 50 mL of anhydrous ethylcyclohexanecarboxylate was maintained at 5 ° C. under a nitrogen atmosphere, and then 2.16 g of sodium hydride (60% in mineral oil, 0.054 mol) was added thereto, followed by stirring for 30 minutes. 10.0 g (0.032 mol) of 1- (4'-nitro-biphenyl-4-yl) heptan-1-one ( 41 ) dissolved in 50 mL of ethylcyclohexanecarboxylate was added thereto, followed by stirring for 1 hour. The reaction mixture was slowly warmed up and stirred at 60 ° C. for 5 hours. The reaction solution was cooled to room temperature, 30 mL of H 2 O was added, followed by stirring for about 30 minutes, and 30 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Purification by chromatography (developing solvent; ethyl acetate: n -hexane = 1: 4) yielded 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) -2-pentylpropane-1,3-dione ( 46 ) 6.76 g (50.1%) was obtained.
1H NMR(δ ppm; CDCl3) : 0.87 (3H, t), 1.10-1.14 (10H, m), 1.28 (8H, m), 1.58-1.64 (12H, m), 1.72(1H, t), 2.10 (3H, s), 7.32-7.36 (3H, m), 7.80-7.84 (4H, m), 8.01-8.06 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 0.87 (3H, t), 1.10-1.14 (10H, m), 1.28 (8H, m), 1.58-1.64 (12H, m), 1.72 (1H, t), 2.10 (3H, s), 7.32-7.36 (3H, m), 7.80-7.84 (4H, m), 8.01-8.06 (2H, m)
MS(m/e): 422MS ( m / e ): 422
반응 2. 1-시클로헥실-3-(4'-니트로비페닐-4-일)-2-펜틸프로판-1,3-디온 디옥심(47)의 합성Reaction 2. Synthesis of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) -2-pentylpropane-1,3-dione dioxime ( 47 )
Figure PCTKR2016000635-appb-I000055
Figure PCTKR2016000635-appb-I000055
1-시클로헥실-3-(4'-니트로비페닐-4-일)-2-펜틸프로판-1,3-디온(46) 5.0 g (0.012 mol)을 에탄올 100 mL에 분산시키고 염산히드록실아민 2.50 g (0.036 mol)과 초산나트륨 2.95 g(0.036 mol)을 가해준 다음, 반응용액을 서서히 승온하여 1 시간 동안 환류 반응하였다. 반응물을 실온으로 냉각하고 증류수 100 mL와 초산 에틸 200 mL를 가해준 다음, 30분 정도 교반하여 유기층을 분리한 후 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-시클로헥실-3-(4'-니트로비페닐-4-일)-2-펜틸프로판-1,3-디온 디옥심(47) 4.38 g (80.9 %)을 얻었다. 5.0 g (0.012 mol) of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) -2-pentylpropane-1,3-dione ( 46 ) is dispersed in 100 mL of ethanol and hydroxylamine hydrochloride 2.50 g (0.036 mol) and sodium acetate 2.95 g (0.036 mol) were added thereto, and the reaction solution was gradually heated to reflux for 1 hour. The reaction was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, the mixture was stirred for about 30 minutes, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethyl acetate: n -hexane = 1: 4), and purified by 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) -2-pentylpropane-1,3-dione dioxime ( 47 ). 4.38 g (80.9%) were obtained.
1H NMR(δ ppm; CDCl3) : 0.87(3H, t), 1.10-1.14 (10H, m), 1.28(8H, m), 1.58-1.64 (12H, m), 1.72(1H, t), 2.10 (3H, s), 7.32-7.34(3H, m), 7.80-7.82 (4H, m), 8.01-8.06 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 0.87 (3H, t), 1.10-1.14 (10H, m), 1.28 (8H, m), 1.58-1.64 (12H, m), 1.72 (1H, t), 2.10 (3H, s), 7.32-7.34 (3H, m), 7.80-7.82 (4H, m), 8.01-8.06 (2H, m)
MS(m/e): 452MS ( m / e ): 452
반응 3. 1-시클로헥실-3-(4'-니트로비페닐-4-일)-2-펜틸프로판-1,3-디온 O,O-디아세틸 디옥심(48)의 합성Reaction 3. Synthesis of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) -2-pentylpropane-1,3-dione O, O-diacetyl dioxime ( 48 )
Figure PCTKR2016000635-appb-I000056
Figure PCTKR2016000635-appb-I000056
1-시클로헥실-3-(4'-니트로비페닐-4-일)-2-펜틸프로판-1,3-디온 디옥심(47) 5.0 g (0.011 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 2.43 g (0.024 mol)을 가해주고 반응용액을 30분 동안 교반한 후 염화아세틸 1.88g (0.024 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-시클로헥실-3-(4'-니트로비페닐-4-일)-2-펜틸프로판-1,3-디온 O,O-디아세틸 디옥심(48) 5.14 g (87.3 %)을 얻었다.5.0 g (0.011 mol) of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) -2-pentylpropane-1,3-dione dioxime ( 47 ) was added to 50 mL of ethyl acetate under a nitrogen atmosphere. After dissolving and keeping the reaction at -5 ° C, 2.43 g (0.024 mol) of triethylamine was added, the reaction solution was stirred for 30 minutes, and then slowly added 1.88 g (0.024 mol) of acetyl chloride, and the reaction was not heated. Stir for 30 minutes being careful not to. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product obtained was subjected to silica gel column chromatography (developing solvent; ethyl acetate). : 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) -2-pentylpropane-1,3-dione O, O-diacetyl dioxime by purification with n -hexane = 1: 4) (48) 5.14 g to give a (87.3%).
1H NMR(δ ppm; CDCl3) : 0.86(3H, t), 0.94(6H, s), 1.10-1.14(10H, m), 1.28(8H, m), 1.57-1.62 (12H, m), 1.73(1H, t), 2.11 (3H, s), 7.33-7.35(3H, m), 7.80-7.83 (4H, m), 8.01-8.06 (2H, m) 1 H NMR (δ ppm; CDCl 3 ): 0.86 (3H, t), 0.94 (6H, s), 1.10-1.14 (10H, m), 1.28 (8H, m), 1.57-1.62 (12H, m), 1.73 (1H, t), 2.11 (3H, s), 7.33-7.35 (3H, m), 7.80-7.83 (4H, m), 8.01-8.06 (2H, m)
MS(m/e): 536MS ( m / e ): 536
[[ 실시예Example 21] 1-(4'- 21] 1- (4'- 브로모비페닐Bromobiphenyl -4-일)부탄-1,3--4-yl) butane-1,3- 디온Dion O,OO, O -- 디아세틸Diacetyl 디옥심(52)의Dioxim (52) 제조 Produce
반응 1. 1-(4'-브로모비페닐-4-일)부탄-1,3-디온(50)의 합성Reaction 1. Synthesis of 1- (4'-bromobiphenyl-4-yl) butane-1,3-dione ( 50 )
Figure PCTKR2016000635-appb-I000057
Figure PCTKR2016000635-appb-I000057
질소분위기 하에서 무수 초산 에틸 50 mL를 5℃로 유지한 다음 수소화 나트륨 2.16 g (60% in mineral oil, 0.054 mol)을 가한 후 30분 동안 교반하였다. 초산 에틸 50 mL에 용해한 4-아세틸-4'-브로모비페닐(49) 10.0 g (0.036 mol)을 가한 후 1시간 동안 교반한 후 반응 용액을 서서히 승온하여 60℃에서 5 시간 동안 교반하여 반응을 완결하였다. 반응용액을 실온으로 냉각시키고 H2O 30 mL을 가해준 다음 30분 정도 교반 후, 1% HCl 수용액 30 mL을 천천히 적가하여 반응물의 pH가 6~7이 되도록 중화하였다. 반응용액에 초산 에틸 100 mL을 가하여주고 30분 동안 교반하여 유기층을 분리한 후 H2O로 충분히 씻어준 다음, 회수한 유기층을 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-브로모비페닐-4-일)부탄-1,3-디온(50) 5.97 g (52.3 %)을 얻었다. 50 mL of anhydrous ethyl acetate was kept at 5 ° C. under a nitrogen atmosphere, and then 2.16 g of sodium hydride (60% in mineral oil, 0.054 mol) was added thereto, followed by stirring for 30 minutes. After adding 10.0 g (0.036 mol) of 4-acetyl-4'-bromobiphenyl ( 49 ) dissolved in 50 mL of ethyl acetate, the mixture was stirred for 1 hour, and then the reaction solution was gradually heated up and stirred at 60 ° C. for 5 hours. Completed The reaction solution was cooled to room temperature, 30 mL of H 2 O was added, followed by stirring for about 30 minutes, and 30 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 5.97 g (52.3%) of 1- (4'-bromobiphenyl-4-yl) butane-1,3-dione ( 50 ) was purified by chromatography (developing solvent; ethyl acetate: n -hexane = 1: 4). Got it.
1H NMR(δ ppm; CDCl3) : 1.88 (3H, s), 2.45 (2H, s), 7.72-7.78(4H, m), 8.01(2H, d), 8.26(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 1.88 (3H, s), 2.45 (2H, s), 7.72-7.78 (4H, m), 8.01 (2H, d), 8.26 (2H, d)
MS(m/e): 317MS ( m / e ): 317
반응 2. 1-(4'-브로모비페닐-4-일)부탄-1,3-디온 디옥심(51)의 합성Reaction 2. Synthesis of 1- (4'-bromobiphenyl-4-yl) butane-1,3-dione dioxime ( 51 )
Figure PCTKR2016000635-appb-I000058
Figure PCTKR2016000635-appb-I000058
1-(4'-브로모비페닐-4-일)부탄-1,3-디온(50) 5.0 g (0.016 mol)을 에탄올 100 mL에 분산시키고 염산히드록실아민 3.34 g (0.048 mol)과 초산나트륨 3.94 g(0.048 mol)을 가해준 다음, 반응용액을 서서히 승온하여 1 시간 동안 환류 반응하였다. 반응물을 실온으로 냉각하고 증류수 100 mL와 초산 에틸 200 mL를 가해준 다음, 30분 정도 교반하여 유기층을 분리한 후 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-브로모비페닐-4-일)부탄-1,3-디온 디옥심(51) 4.72 g (84.9 %)을 얻었다. 5.0 g (0.016 mol) of 1- (4'-bromobiphenyl-4-yl) butane-1,3-dione ( 50 ) is dispersed in 100 mL of ethanol, 3.34 g (0.048 mol) of hydroxylamine hydrochloride and sodium acetate 3.94 g (0.048 mol) was added, and the reaction solution was gradually heated to reflux for 1 hour. The reaction was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, the mixture was stirred for about 30 minutes, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product was purified by silica gel column chromatography (developing solvent). Ethyl acetate: n -hexane = 1: 4) to give 4.72 g (84.9%) of 1- (4'-bromobiphenyl-4-yl) butane-1,3-dione dioxime ( 51 ).
1H NMR(δ ppm; CDCl3) : 1.90 (3H, s), 2.46 (2H, s), 7.72-7.76(4H, m), 8.02(2H, d), 8.25(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 1.90 (3H, s), 2.46 (2H, s), 7.72-7.76 (4H, m), 8.02 (2H, d), 8.25 (2H, d)
MS(m/e):347MS ( m / e ): 347
반응 3. 1-(4'-브로모비페닐-4-일)부탄-1,3-디온 O,O-디아세틸 디옥심(52)의 합성Reaction 3. Synthesis of 1- (4'-bromobiphenyl-4-yl) butane-1,3-dione O, O-diacetyl dioxime ( 52 )
Figure PCTKR2016000635-appb-I000059
Figure PCTKR2016000635-appb-I000059
1-(4'-브로모비페닐-4-일)부탄-1,3-디온 디옥심(51) 5.0 g (0.014 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 3.14 g (0.031 mol)을 가해주고 반응용액을 30분 동안 교반한 후 염화아세틸 2.43 g (0.031 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-브로모비페닐-4-일)부탄-1,3-디온 O,O-디아세틸 디옥심(52) 5.43 g (89.9 %)을 얻었다.5.0 g (0.014 mol) of 1- (4'-bromobiphenyl-4-yl) butane-1,3-dione dioxime ( 51 ) is dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction is kept at -5 ° C. Then, 3.14 g (0.031 mol) of triethylamine was added, the reaction solution was stirred for 30 minutes, and then 2.43 g (0.031 mol) of acetyl chloride was added slowly, and the reaction mixture was stirred for 30 minutes while being careful not to raise the reaction temperature. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product obtained was subjected to silica gel column chromatography (developing solvent; ethyl acetate). : n - hexane = 1: 4) to give 1- (4'-bromobiphenyl-4-yl) butane-1,3-dione O, O- di-acetyl-di-oxime (52) 5.43 g (89.9% ) Got.
1H NMR(δ ppm; CDCl3) : 0.95(6H, s), 1.89 (3H, s), 2.45 (2H, s), 7.72-7.76(4H, m), 8.02(2H, d), 8.25(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 0.95 (6H, s), 1.89 (3H, s), 2.45 (2H, s), 7.72-7.76 (4H, m), 8.02 (2H, d), 8.25 ( 2H, d)
MS(m/e): 431MS ( m / e ): 431
[[ 실시예Example 22] 1-(4'- 22] 1- (4'- 시아노비페닐Cyanobiphenyl -4-일)부탄-1,3--4-yl) butane-1,3- 디온Dion O,OO, O -- 디아세틸Diacetyl 디옥심(56)의Dioxim (56) 제조 Produce
반응 1. 4-아세틸-4'-시아노비페닐(53)의 합성Reaction 1. Synthesis of 4-acetyl-4'-cyanobiphenyl ( 53 )
Figure PCTKR2016000635-appb-I000060
Figure PCTKR2016000635-appb-I000060
4-아세틸-4'-브로모비페닐(49) 20.0 g (0.073 mol)을 N-메틸-2-피롤리디논(NMP) 200 mL에 용해시키고 시안화구리 9.85 g (0.110 mol)을 가해준 다음 반응용액을 서서히 승온하여 3 시간 동안 환류 반응하였다. 반응물에 증류수 300 mL와 초산 에틸 300 mL를 가해주고 30분 정도 교반 후, 유기층을 분리하고, 분리한 유기층을 포화 염화암모늄 수용액 200 mL과 증류수 100 mL로 3회의 순서로 씻어준 다음 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하였다. 실리카겔 칼럼 그로마토그래피(전개용매 ; 디클로로메탄 : n-헥산 = 1 : 5)로 정제하여 4-아세틸-4'-시아노비페닐(53) 8.23 g (51.3%)을 얻었다.20.0 g (0.073 mol) of 4-acetyl-4'-bromobiphenyl ( 49 ) was dissolved in 200 mL of N -methyl-2-pyrrolidinone (NMP), and 9.85 g (0.110 mol) of copper cyanide was added. The solution was slowly heated to reflux for 3 hours. 300 mL of distilled water and 300 mL of ethyl acetate were added to the reaction mixture. After stirring for about 30 minutes, the organic layer was separated, and the organic layer was washed three times with 200 mL of saturated ammonium chloride solution and 100 mL of distilled water. It was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (developing solvent; dichloromethane: n -hexane = 1: 5) afforded 8.23 g (51.3%) of 4-acetyl-4'-cyanobiphenyl ( 53 ).
1H NMR(δ ppm; CDCl3) : 2.31 (3H, s),7.72-7.76(4H, m), 7.95(2H, d), 8.05(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 2.31 (3H, s), 7.72-7.76 (4H, m), 7.95 (2H, d), 8.05 (2H, d)
MS(m/e): 221MS ( m / e ): 221
반응 2. 1-(4'-시아노비페닐-4-일)부탄-1,3-디온(54)의 합성Reaction 2. Synthesis of 1- (4'-cyanobiphenyl-4-yl) butane-1,3-dione ( 54 )
Figure PCTKR2016000635-appb-I000061
Figure PCTKR2016000635-appb-I000061
질소분위기 하에서 무수 초산 에틸 50 mL를 5℃로 유지한 다음 수소화나트륨 2.72 g (60% in mineral oil, 0.068 mol)을 가한 후 30분 동안 교반하였다. 초산 에틸 50 mL에 용해한 4-아세틸-4'-시아노비페닐(53) 10.0 g (0.045 mol)을 가한 후 1시간 동안 교반한 후 반응 용액을 서서히 승온하여 60℃에서 5 시간 동안 교반하여 반응을 완결하였다. 반응용액을 실온으로 냉각시키고 H2O 30 mL을 가해준 다음 30분 정도 교반 후, 1% HCl 수용액 50 mL을 천천히 적가하여 반응물의 pH가 6~7이 되도록 중화하였다. 반응용액에 초산 에틸 100 mL을 가하여주고 30분 동안 교반하여 유기층을 분리한 후 H2O로 충분히 씻어준 다음, 회수한 유기층을 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-시아노비페닐-4-일)부탄-1,3-디온(54) 6.18 g (52.2 %)을 얻었다. 50 mL of anhydrous ethyl acetate was maintained at 5 ° C. under a nitrogen atmosphere, and then 2.72 g (60% in mineral oil, 0.068 mol) of sodium hydride was added thereto, followed by stirring for 30 minutes. After adding 10.0 g (0.045 mol) of 4-acetyl-4'-cyanobiphenyl ( 53 ) dissolved in 50 mL of ethyl acetate, the mixture was stirred for 1 hour, and the reaction solution was gradually heated up and stirred at 60 ° C. for 5 hours. Completed The reaction solution was cooled to room temperature, 30 mL of H 2 O was added thereto, stirred for about 30 minutes, and then slowly added dropwise 50 mL of an aqueous 1% HCl solution to neutralize the reactant to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 6.18 g (52.2%) of 1- (4'-cyanobiphenyl-4-yl) butane-1,3-dione ( 54 ) was purified by chromatography (developing solvent; ethyl acetate: n -hexane = 1: 4). Got it.
1H NMR(δ ppm; CDCl3) : 1.90 (3H, s), 2.45 (2H, s), 7.72-7.78(4H, m), 8.01(2H, d), 8.26(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 1.90 (3H, s), 2.45 (2H, s), 7.72-7.78 (4H, m), 8.01 (2H, d), 8.26 (2H, d)
MS(m/e):263MS ( m / e ): 263
반응 3. 1-(4'-시아노비페닐-4-일)부탄-1,3-디온 디옥심(55)의 합성Reaction 3. Synthesis of 1- (4'-cyanobiphenyl-4-yl) butane-1,3-dione dioxime ( 55 )
Figure PCTKR2016000635-appb-I000062
Figure PCTKR2016000635-appb-I000062
1-(4'-시아노비페닐-4-일)부탄-1,3-디온(54) 5.0 g (0.019 mol)을 에탄올 100 mL에 분산시키고 염산히드록실아민 3.97 g (0.057 mol)과 초산나트륨 4.68 g(0.057 mol)을 가해준 다음, 반응용액을 서서히 승온하여 1 시간 동안 환류 반응하였다. 반응물을 실온으로 냉각하고 증류수 100 mL와 초산 에틸 200 mL를 가해준 다음, 30분 정도 교반하여 유기층을 분리한 후 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-시아노비페닐-4-일)부탄-1,3-디온 디옥심(55) 4.79 g (85.9 %)을 얻었다. 5.0 g (0.019 mol) of 1- (4'-cyanobiphenyl-4-yl) butane-1,3-dione ( 54 ) is dispersed in 100 mL of ethanol, 3.97 g (0.057 mol) of hydroxylamine hydrochloride and sodium acetate 4.68 g (0.057 mol) was added, and the reaction solution was gradually heated to reflux for 1 hour. The reaction was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, the mixture was stirred for about 30 minutes, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethyl acetate: n -hexane = 1: 4) to obtain 4.79 g (85.9%) of 1- (4'-cyanobiphenyl-4-yl) butane-1,3-dione dioxime ( 55 ).
1H NMR(δ ppm; CDCl3) : 1.88 (3H, s), 2.46 (2H, s), 7.71-7.74(4H, m), 8.01(2H, d), 8.23(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 1.88 (3H, s), 2.46 (2H, s), 7.71-7.74 (4H, m), 8.01 (2H, d), 8.23 (2H, d)
MS(m/e):293MS ( m / e ): 293
반응 4. 1-(4'-시아노비페닐-4-일)부탄-1,3-디온 O,O-디아세틸 디옥심(56)의 합성Reaction 4. Synthesis of 1- (4'-cyanobiphenyl-4-yl) butane-1,3-dione O, O-diacetyl dioxime ( 56 )
Figure PCTKR2016000635-appb-I000063
Figure PCTKR2016000635-appb-I000063
1-(4'-시아노비페닐-4-일)부탄-1,3-디온 디옥심(55) 5.0 g (0.017 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 3.74 g (0.037 mol)을 가해주고 반응용액을 30분 동안 교반한 후 염화아세틸 2.90 g (0.037 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-시아노비페닐-4-일)부탄-1,3-디온 O,O-디아세틸 디옥심(56) 5.58 g (86.9 %)을 얻었다.5.0 g (0.017 mol) of 1- (4'-cyanobiphenyl-4-yl) butane-1,3-dione dioxime ( 55 ) is dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction is kept at -5 ° C. Then, 3.74 g (0.037 mol) of triethylamine was added, the reaction solution was stirred for 30 minutes, and then 2.90 g (0.037 mol) of acetyl chloride was added slowly, and the reaction solution was stirred for 30 minutes while being careful not to raise the reaction temperature. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product obtained was subjected to silica gel column chromatography (developing solvent; ethyl acetate). 5.58 g (86.9%) of 1- (4'-cyanobiphenyl-4-yl) butane-1,3-dione O, O-diacetyl dioxime ( 56 ) by purification with n -hexane = 1: 4) Got.
1H NMR(δ ppm; CDCl3) : 0.92(6H, s), 1.88 (3H, s), 2.40 (2H, s), 7.72-7.75(4H, m), 7.99(2H, d), 8.20(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 0.92 (6H, s), 1.88 (3H, s), 2.40 (2H, s), 7.72-7.75 (4H, m), 7.99 (2H, d), 8.20 ( 2H, d)
MS(m/e):377MS ( m / e ): 377
[[ 실시예Example 23] 1-(4'- 23] 1- (4'- terttert -- 부틸비페닐Butyl Biphenyl -4-일)부탄-1,3--4-yl) butane-1,3- 디온Dion O,OO, O -- 디아세틸Diacetyl 디옥심(60)의Dioxime (60) 제조 Produce
반응 1. 1-(4'-tert-부틸비페닐-4-일)부탄-1,3-디온(58)의 합성Reaction 1. Synthesis of 1- (4'-tert-butylbiphenyl-4-yl) butane-1,3-dione ( 58 )
Figure PCTKR2016000635-appb-I000064
Figure PCTKR2016000635-appb-I000064
질소분위기 하에서 무수 초산 에틸 50 mL를 5℃로 유지한 다음 수소화 나트륨 2.40 g (60% in mineral oil, 0.060 mol)을 가한 후 30분 동안 교반하였다. 초산 에틸 50 mL에 용해한 4-아세틸-4'-tert-부틸비페닐(57) 10.0 g (0.040 mol)을 가한 후 1시간 동안 교반한 후 반응 용액을 서서히 승온하여 60℃에서 5 시간 동안 교반하여 반응을 완결하였다. 반응용액을 실온으로 냉각시키고 H2O 30 mL을 가해준 다음 30분 정도 교반 후, 1% HCl 수용액 40 mL을 천천히 적가하여 반응물의 pH가 6~7이 되도록 중화하였다. 반응용액에 초산 에틸 100 mL을 가하여주고 30분 동안 교반하여 유기층을 분리한 후 H2O로 충분히 씻어준 다음, 회수한 유기층을 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-tert-부틸비페닐-4-일)부탄-1,3-디온(58) 6.16 g (52.3 %)을 얻었다. 50 mL of anhydrous ethyl acetate was maintained at 5 ° C. under a nitrogen atmosphere, and then 2.40 g of sodium hydride (60% in mineral oil, 0.060 mol) was added thereto, followed by stirring for 30 minutes. After adding 10.0 g (0.040 mol) of 4-acetyl-4'-tert-butylbiphenyl ( 57 ) dissolved in 50 mL of ethyl acetate, the mixture was stirred for 1 hour, and the reaction solution was gradually warmed up and stirred at 60 ° C. for 5 hours. The reaction was complete. The reaction solution was cooled to room temperature, 30 mL of H 2 O was added thereto, followed by stirring for about 30 minutes, and 40 mL of 1% HCl aqueous solution was slowly added dropwise to neutralize the pH of the reaction product to 6-7. 100 mL of ethyl acetate was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with H 2 O. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 6.16 g (52.3%) of 1- (4'-tert-butylbiphenyl-4-yl) butane-1,3-dione ( 58 ) by purification by chromatography (developing solvent; ethyl acetate: n -hexane = 1: 4). )
1H NMR(δ ppm; CDCl3) : 1.32 (9H, s), 2.01 (3H, s), 3.65 (2H, s), 7.72-7.78(4H, m), 8.01(2H, d), 8.26(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 1.32 (9H, s), 2.01 (3H, s), 3.65 (2H, s), 7.72-7.78 (4H, m), 8.01 (2H, d), 8.26 ( 2H, d)
MS(m/e):294MS ( m / e ): 294
반응 2. 1-(4'-tert-부틸비페닐-4-일)부탄-1,3-디온 디옥심(59)의 합성Reaction 2. Synthesis of 1- (4'-tert-butylbiphenyl-4-yl) butane-1,3-dione dioxime ( 59 )
Figure PCTKR2016000635-appb-I000065
Figure PCTKR2016000635-appb-I000065
1-(4'-tert-부틸비페닐-4-일)부탄-1,3-디온(58) 5.0 g (0.017 mol)을 에탄올 100 mL에 분산시키고 염산히드록실아민 3.55 g (0.051 mol)과 초산나트륨 4.18 g(0.051 mol)을 가해준 다음, 반응용액을 서서히 승온하여 1 시간 동안 환류 반응하였다. 반응물을 실온으로 냉각하고 증류수 100 mL와 초산 에틸 200 mL를 가해준 다음, 30분 정도 교반하여 유기층을 분리한 후 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-tert-부틸비페닐-4-일)부탄-1,3-디온 디옥심(59) 4.57 g (82.9 %)을 얻었다. 5.0 g (0.017 mol) of 1- (4'-tert-butylbiphenyl-4-yl) butane-1,3-dione ( 58 ) was dispersed in 100 mL of ethanol and 3.55 g (0.051 mol) of hydroxylamine hydrochloride. 4.18 g (0.051 mol) of sodium acetate was added, and the reaction solution was gradually heated to reflux for 1 hour. The reaction was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, the mixture was stirred for about 30 minutes, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 4.57 g (82.9%) of 1- (4'-tert-butylbiphenyl-4-yl) butane-1,3-dione dioxime ( 59 ) by purification with ethyl acetate: n -hexane = 1: 4) Got it.
1H NMR(δ ppm; CDCl3) : 1.32 (9H, s), 1.95 (3H, s), 3.45 (2H, s), 7.72-7.76(4H, m), 8.01(2H, d), 8.26(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 1.32 (9H, s), 1.95 (3H, s), 3.45 (2H, s), 7.72-7.76 (4H, m), 8.01 (2H, d), 8.26 ( 2H, d)
MS(m/e):324MS ( m / e ): 324
반응 3. 1-(4'-tert-부틸비페닐-4-일)부탄-1,3-디온 O,O-디아세틸 디옥심(60)의 합성Reaction 3. Synthesis of 1- (4'-tert-butylbiphenyl-4-yl) butane-1,3-dione O, O-diacetyl dioxime ( 60 )
Figure PCTKR2016000635-appb-I000066
Figure PCTKR2016000635-appb-I000066
1-(4'-tert-부틸비페닐-4-일)부탄-1,3-디온 디옥심(59) 5.0 g (0.015 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 3.34 g (0.033 mol)을 가해주고 반응용액을 30분 동안 교반한 후 염화아세틸 2.59 g (0.033 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-tert-부틸비페닐-4-일)부탄-1,3-디온 O,O-디아세틸 디옥심(60) 5.44 g (88.8 %)을 얻었다.5.0 g (0.015 mol) of 1- (4'-tert-butylbiphenyl-4-yl) butane-1,3-dione dioxime ( 59 ) is dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction is carried out at -5 ° C. After adding 3.34 g (0.033 mol) of triethylamine and stirring the reaction solution for 30 minutes, slowly adding 2.59 g (0.033 mol) of acetyl chloride and stirring for 30 minutes while being careful not to raise the reaction temperature. It was. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product obtained was subjected to silica gel column chromatography (developing solvent; ethyl acetate). : n - hexane = 1: 4) to give 1- (4'-tert- butyl-biphenyl-4-yl) butane-1,3-dione O, O- di-acetyl-di-oxime (60) 5.44 g (88.8 %) Was obtained.
1H NMR(δ ppm; CDCl3) : 0.92(6H, s), 1.34 (9H, s), 1.92 (3H, s), 3.47 (2H, s), 7.72-7.75(4H, m), 8.00(2H, d), 8.24(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 0.92 (6H, s), 1.34 (9H, s), 1.92 (3H, s), 3.47 (2H, s), 7.72-7.75 (4H, m), 8.00 ( 2H, d), 8.24 (2H, d)
MS(m/e):408MS ( m / e ): 408
[[ 실시예Example 24] 1-( 24] 1- ( pp -- 터페닐Terphenyl -4-일)부탄-1,3--4-yl) butane-1,3- 디온Dion O,OO, O -- 디아세틸Diacetyl 디옥심(61)의Dioxime (61) 제조 Produce
Figure PCTKR2016000635-appb-I000067
Figure PCTKR2016000635-appb-I000067
반응기에 페닐 보론산 3.37 g (0.028 mol)과 1-(4'-브로모비페닐-4-일)부탄-1,3-디온 O,O-디아세틸 디옥심(52) 10.0 g (0.023 mol), 테트라키스(트리페닐포스핀)팔라디움(0) 2.31g (0.002 mol)을 가한 후 테트라하이드로푸란 100 mL를 가하였다. 반응 혼합물에 2M-탄산칼륨 수용액 100mL를 적가하였다. 반응 혼합물을 60℃로 승온한 후 교반하였다. 반응이 종결되면 상온으로 냉각한 후 초산 에틸 100 mL를 가하였다. 유기층을 정제수 50 mL을 가하여 세척하고, 유기층을 분리한 후 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(p-터페닐-4-일)부탄-1,3-디온 O,O-디아세틸 디옥심(61) 5.11 g (51.9 %)을 얻었다.3.37 g (0.028 mol) of phenyl boronic acid and 1- (4'-bromobiphenyl-4-yl) butane-1,3-dione O, O-diacetyl dioxime ( 52 ) in the reactor 10.0 g (0.023 mol) 2.31 g (0.002 mol) of tetrakis (triphenylphosphine) palladium (0) was added, followed by 100 mL of tetrahydrofuran. To the reaction mixture was added 100 mL of a 2M aqueous potassium carbonate solution dropwise. The reaction mixture was raised to 60 ° C. and stirred. After the reaction was completed, the reaction mixture was cooled to room temperature, and 100 mL of ethyl acetate was added thereto. The organic layer was washed with 50 mL of purified water, the organic layer was separated, and the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product was purified by silica gel column chromatography (developing solvent; ethyl acetate: n -hexane = 1: 4) to give 5.11 g (51.9%) of 1- ( p -terphenyl-4-yl) butane-1,3-dione O, O-diacetyl dioxime ( 61 ).
1H NMR(δ ppm; CDCl3) : 0.95(6H, s), 1.89 (3H, s), 2.45 (2H, s), 7.27 (4H, m), 7.72-7.76(5H, m), 8.02(2H, d), 8.25(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 0.95 (6H, s), 1.89 (3H, s), 2.45 (2H, s), 7.27 (4H, m), 7.72-7.76 (5H, m), 8.02 ( 2H, d), 8.25 (2H, d)
MS(m/e):428MS ( m / e ): 428
[[ 실시예Example 25] 1-(1,1'-비페닐-4-일)-프로판-1,2- 25] 1- (1,1'-biphenyl-4-yl) -propane-1,2- 디온Dion O,OO, O -- 디아세틸Diacetyl 디옥심(64)의Dioxim (64) 제조 Produce
반응1. 1-(1,1'-비페닐-4-일)-1,2-프로판디온-2-옥심(62) 합성 Reaction 1. Synthesis of 1- (1,1'-biphenyl-4-yl) -1,2-propanedione-2-oxime (62)
Figure PCTKR2016000635-appb-I000068
Figure PCTKR2016000635-appb-I000068
4-프로피오닐비페닐(8) 19.2 g (0.091 mmol)을 테트라히드로푸란(THF) 300 mL에 용해시키고 1,4-디옥산에 용해된 4N HCl 48 mL과 이소펜틸아질산 31 mL (0.233 mmol)를 차례로 가해주고 반응물을 25 ℃에서 6시간 동안 교반하였다. 그런 다음 반응 용액에 에틸아세테이트 100 mL를 가해주고 증류수 200 mL로 씻어준 다음, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻어진 고체 생성물을 에틸아세테이트와 헥산(1:1, v/v)의 혼합용매를 사용하여 재결정한 다음 건조하여 연회색의 1-(1,1'-비페닐-4-일)-1,2-프로판디온-2-옥심(62) 13.9 g (63.8 %)을 얻었다. 19.2 g (0.091 mmol) of 4-propionylbiphenyl (8) was dissolved in 300 mL of tetrahydrofuran (THF), 48 mL of 4 N HCl dissolved in 1,4-dioxane, and 31 mL (0.233 mmol of isopentylnitrite). ) Was added sequentially and the reaction was stirred at 25 ° C for 6 h. Then, 100 mL of ethyl acetate was added to the reaction solution, which was then washed with 200 mL of distilled water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting solid product was diluted with ethyl acetate and hexane (1: 1, v / Recrystallized using a mixed solvent of v) and dried to give 13.9 g (63.8%) of light gray 1- (1,1'-biphenyl-4-yl) -1,2-propanedione-2-oxime (62) . Got.
1H-NMR(δ ppm ; CDCl3) : 2.19(3H, s), 7.36(1H, t), 7.43(2H, t), 7.59(2H, d), 7.63(2H, d), 7.78(1H, s), 7.98(2H, d) 1 H-NMR (δ ppm; CDCl 3 ): 2.19 (3H, s), 7.36 (1H, t), 7.43 (2H, t), 7.59 (2H, d), 7.63 (2H, d), 7.78 (1H , s), 7.98 (2H, d)
MS(m/e) : 239MS ( m / e ): 239
반응 2. 1-(비페닐-4-일)-2-프로판탄-1,2-디온 디옥심(63)의 합성Reaction 2. Synthesis of 1- (biphenyl-4-yl) -2-propanetan-1,2-dione dioxime ( 63 )
Figure PCTKR2016000635-appb-I000069
Figure PCTKR2016000635-appb-I000069
1-(1,1'-비페닐-4-일)-1,2-프로판디온-2-옥심(62) 10.06 g (0.042 mol)을 에탄올 100 mL에 분산시키고 염산히드록실아민 5.83 g (0.084 mol)과 초산나트륨 6.90 g (0.084 mol)을 가해준 다음, 반응용액을 서서히 승온하여 3 시간 동안 환류 반응하였다. 반응물을 실온으로 냉각하고 증류수 100 mL와 초산 에틸 200 mL를 가해준 다음, 30분 정도 교반하여 유기층을 분리한 후 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(비페닐-4-일)-2-프로판탄-1,2-디온 디옥심(63) 9.02 g (84.3 %)을 얻었다. 10.06 g (0.042 mol) of 1- (1,1'-biphenyl-4-yl) -1,2-propanedione-2-oxime (62) is dispersed in 100 mL of ethanol and 5.83 g (0.084) of hydroxylamine hydrochloride mol) and 6.90 g (0.084 mol) of sodium acetate were added, and the reaction solution was gradually heated to reflux for 3 hours. The reaction was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, the mixture was stirred for about 30 minutes, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethyl acetate: n -hexane = 1: 4) to obtain 9.02 g (84.3%) of 1- (biphenyl-4-yl) -2-propanetan-1,2-dione dioxime ( 63 ).
1H NMR(δ ppm; DMSOd6) : 2.21(3H, s), 7.34-7.43(3H, m), 7.58-7.62(4H, m), 7.79(1H, s), 8.00(2H, d), 11.45 (1H, s),11.60 (1H, s) 1 H NMR (δ ppm; DMSO d6 ): 2.21 (3H, s), 7.34-7.43 (3H, m), 7.58-7.62 (4H, m), 7.79 (1H, s), 8.00 (2H, d), 11.45 (1H, s), 11.60 (1H, s)
MS(m/e):254MS ( m / e ): 254
반응 3. 1-(1,1'-비페닐-4-일)-프로판-1,2-디온 O,O-디아세틸 디옥심(64)의 합성Reaction 3. Synthesis of 1- (1,1'-biphenyl-4-yl) -propane-1,2-dione O, O -diacetyl dioxime ( 64 )
Figure PCTKR2016000635-appb-I000070
Figure PCTKR2016000635-appb-I000070
1-(비페닐-4-일)-2-프로판탄-1,2-디온 디옥심(63) 3.81 g (0.015 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 3.34 g (0.033 mol)을 가해주고 반응용액을 30분 동안 교반한 후 염화아세틸 2.59 g (0.033 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(1,1'-비페닐-4-일)-프로판-1,2-디온 O,O-디아세틸 디옥심(64) 4.32 g (85.2 %)을 얻었다.3.81 g (0.015 mol) of 1- (biphenyl-4-yl) -2-propane-1,2-dione dioxime ( 63 ) is dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction is kept at -5 ° C. Then, 3.34 g (0.033 mol) of triethylamine was added, the reaction solution was stirred for 30 minutes, and then 2.59 g (0.033 mol) of acetyl chloride was added slowly, and the reaction mixture was stirred for 30 minutes while being careful not to raise the reaction temperature. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product obtained was subjected to silica gel column chromatography (developing solvent; ethyl acetate). 4.32 g (85.2) of 1- (1,1'-biphenyl-4-yl) -propane-1,2-dione O, O -diacetyl dioxime ( 64 ) by purification with n -hexane = 1: 4) %) Was obtained.
1H NMR(δ ppm; CDCl3) : 0.92(6H, s), 2.05 (3H, s), 2.21(3H, s), 7.36-7.42(3H, m), 7.57-7.62(4H, m), 7.78(1H, s), 7.98(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 0.92 (6H, s), 2.05 (3H, s), 2.21 (3H, s), 7.36-7.42 (3H, m), 7.57-7.62 (4H, m), 7.78 (1 H, s), 7.98 (2 H, d)
MS(m/e):338MS ( m / e ): 338
[[ 실시예Example 26] 1-(4'- 26] 1- (4'- 니트로비페닐Nitrobiphenyl -4-일)-헵탄-1,2--4-yl) -heptane-1,2- 디온Dion O,OO, O -- 디아세틸Diacetyl 디옥심(67)의 제조Preparation of Dioxime 67
반응1. 1-(4'-니트로비페닐-4-일)-1,2-헵탄디온-2-옥심(65) 합성 Reaction 1. Synthesis of 1- (4'-nitrobiphenyl-4-yl) -1,2-heptanedion-2-oxime (65)
Figure PCTKR2016000635-appb-I000071
Figure PCTKR2016000635-appb-I000071
1-(4'-니트로-비페닐-4-일)헵탄-1-온(41) 6.4 g (0.030 mmol)을 테트라히드로푸란(THF) 100 mL에 용해시키고 1,4-디옥산에 용해된 4N HCl 16 mL과 이소펜틸아질산 12 mL (0.078 mmol)를 차례로 가해주고 반응물을 25 ℃에서 6시간 동안 교반하였다. 그런 다음 반응 용액에 에틸아세테이트 50 mL를 가해주고 증류수 100 mL로 씻어준 다음, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻어진 고체 생성물을 에틸아세테이트와 헥산 (1:1, v/v)의 혼합용매를 사용하여 재결정한 다음 건조하여 연회색의 1-(4'-니트로비페닐-4-일)-1,2-헵탄디온-2-옥심(65) 6.41 g (62.8 %)을 얻었다. 6.4 g (0.030 mmol) of 1- (4'-nitro-biphenyl-4-yl) heptan-1-one (41) was dissolved in 100 mL of tetrahydrofuran (THF) and dissolved in 1,4-dioxane. 16 mL of 4 N HCl and 12 mL (0.078 mmol) of isopentyl nitric acid were added sequentially, and the reaction was stirred at 25 ° C. for 6 hours. 50 mL of ethyl acetate was added to the reaction solution, which was then washed with 100 mL of distilled water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting solid product was diluted with ethyl acetate and hexane (1: 1, v / recrystallized using a mixed solvent of v) and dried to give 6.41 g (62.8%) of light gray 1- (4'-nitrobiphenyl-4-yl) -1,2-heptanedion-2-oxime (65 ). Got it.
1H-NMR(δ ppm ; CDCl3) : 0.94 (3H, t), 1.35 (2H, m), 1.52 (2H, m), 1.78 (2H, m), 2.00(2H, t), 7.36(2H, d), 7.75(2H, d), 7.98(2H, d), 8.29(2H, d) 1 H-NMR (δ ppm; CDCl 3 ): 0.94 (3H, t), 1.35 (2H, m), 1.52 (2H, m), 1.78 (2H, m), 2.00 (2H, t), 7.36 (2H , d), 7.75 (2H, d), 7.98 (2H, d), 8.29 (2H, d)
MS(m/e) : 340MS ( m / e ): 340
반응 2. 1-(4'-니트로비페닐-4-일)헵탄-1,2-디온 디옥심(66)의 합성Reaction 2. Synthesis of 1- (4'-nitrobiphenyl-4-yl) heptan-1,2-dione dioxime ( 66 )
Figure PCTKR2016000635-appb-I000072
Figure PCTKR2016000635-appb-I000072
1-(4'-니트로비페닐-4-일)-1,2-헵탄디온-2-옥심(65) 10.00 g (0.029 mol)을 에탄올 100 mL에 분산시키고 염산히드록실아민 4.05 g (0.058 mol)과 초산나트륨 4.75 g (0.058 mol)을 가해준 다음, 반응용액을 서서히 승온하여 3 시간 동안 환류 반응하였다. 반응물을 실온으로 냉각하고 증류수 100 mL와 초산 에틸 200 mL를 가해준 다음, 30분 정도 교반하여 유기층을 분리한 후 무수황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-니트로비페닐-4-일)헵탄-1,2-디온 디옥심(66) 7.66 g (74.3 %)을 얻었다. 10.00 g (0.029 mol) of 1- (4'-nitrobiphenyl-4-yl) -1,2-heptanedion-2-oxime (65) is dispersed in 100 mL of ethanol and 4.05 g (0.058 mol) of hydroxylamine hydrochloride ) And sodium acetate 4.75 g (0.058 mol) were added, and the reaction solution was gradually heated to reflux for 3 hours. The reaction was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, the mixture was stirred for about 30 minutes, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethyl acetate: n -hexane = 1: 4) to obtain 7.66 g (74.3%) of 1- (4'-nitrobiphenyl-4-yl) heptan-1,2-dione dioxime ( 66 ).
1H NMR(δ ppm; DMSOd6) : 0.92 (3H, t), 1.35 (2H, m), 1.52 (2H, m), 1.80 (2H, m), 1.99(2H, t), 7.30(2H, d), 7.75(2H, d), 8.01(2H, d), 8.30(2H, d) 11.49 (1H, s),11.60 (1H, s) 1 H NMR (δ ppm; DMSO d6 ): 0.92 (3H, t), 1.35 (2H, m), 1.52 (2H, m), 1.80 (2H, m), 1.99 (2H, t), 7.30 (2H, d), 7.75 (2H, d), 8.01 (2H, d), 8.30 (2H, d) 11.49 (1H, s), 11.60 (1H, s)
MS(m/e):355MS ( m / e ): 355
반응 3. 1-(4'-니트로비페닐-4-일)-헵탄-1,2-디온 O,O-디아세틸 디옥심(67)의 합성Reaction 3. Synthesis of 1- (4'-nitrobiphenyl-4-yl) -heptan-1,2-dione O, O -diacetyl dioxime (67)
Figure PCTKR2016000635-appb-I000073
Figure PCTKR2016000635-appb-I000073
1-(4'-니트로비페닐-4-일)헵탄-1,2-디온 디옥심(66) 5.00 g (0.014 mol)을 질소 분위기하에서 초산 에틸 50 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 3.14 g (0.031 mol)을 가해주고 반응용액을 30분 동안 교반한 후 염화아세틸 2.43 g (0.031 mol)을 천천히 가해주고, 반응물이 승온되지 않도록 주의하면서 30분 동안 교반하였다. 그런 다음 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반하여 유기층을 분리한 후, 회수한 유기층을 무수 황산마그네슘으로 건조하고 용매를 감압 증류하여 얻은 생성물을 실리카겔 컬럼 크로마토그래피(전개용매 ; 초산 에틸 : n-헥산 = 1 : 4)로 정제하여 1-(4'-니트로비페닐-4-일)-헵탄-1,2-디온 O,O-디아세틸 디옥심(67) 4.32 g (85.2 %)을 얻었다.5.00 g (0.014 mol) of 1- (4'-nitrobiphenyl-4-yl) heptan-1,2-dione dioxime ( 66 ) are dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction is kept at -5 ° C. Then, 3.14 g (0.031 mol) of triethylamine was added, the reaction solution was stirred for 30 minutes, and then 2.43 g (0.031 mol) of acetyl chloride was added slowly, and the reaction mixture was stirred for 30 minutes while being careful not to raise the reaction temperature. Then, 50 mL of distilled water was slowly added to the reaction mixture, stirred for 30 minutes to separate the organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product obtained was subjected to silica gel column chromatography (developing solvent; ethyl acetate). 4.32 g (85.2% ) of 1- (4'-nitrobiphenyl-4-yl) -heptane-1,2-dione O, O -diacetyl dioxime (67) by purification with n -hexane = 1: 4) )
1H NMR(δ ppm; CDCl3) : 0.91 (3H, t), 1.35 (2H, m), 1.50 (2H, m), 1.80 (2H, m), 1.99(2H, t), 2.05 (3H, s), 2.21(3H, s), 7.33(2H, d), 7.80(2H, d), 8.01(2H, d), 8.30(2H, d) 1 H NMR (δ ppm; CDCl 3 ): 0.91 (3H, t), 1.35 (2H, m), 1.50 (2H, m), 1.80 (2H, m), 1.99 (2H, t), 2.05 (3H, s), 2.21 (3H, s), 7.33 (2H, d), 7.80 (2H, d), 8.01 (2H, d), 8.30 (2H, d)
MS(m/e):439MS ( m / e ): 439
<바인더 수지 제조><Binder resin manufacturing>
a) 바인더 수지 1의 제조a) Preparation of Binder Resin 1
500 mL 중합용기에 프로필렌글리콜메틸에테르아세테이트 (Propylene Glycol Methyl Ether Acetate ; PGMEA) 200 mL과 AIBN(azobisisobutyronitrile) 1.5 g을 첨가한 후, 메타아크릴산, 글리시딜메타아크릴산, 메틸메타아크릴산 및 디시클로펜타닐아크릴산을 각각 20:20:40:20의 몰비로 아크릴 모노머의 고형분을 40 중량%로 첨가한 다음, 질소 분위기 하에서 70 ℃에서 5시간 동안 교반하며 중합시켜 아크릴 중합체인 바인더 수지 1을 제조하였다. 이와 같이 제조된 공중합체의 겔 투과 크로마토그래피(GPC)에 의한 폴리스티렌 환산 중량 평균 분자량은 25,000, 분산도는 1.9로 확인되었다.200 mL of Propylene Glycol Methyl Ether Acetate (PGMEA) and 1.5 g of AIBN (azobisisobutyronitrile) were added to a 500 mL polymerization vessel, followed by methacrylic acid, glycidylmethacrylic acid, methylmethacrylic acid and dicyclopentanyl acrylic acid. The solid content of the acrylic monomer was added to 40% by weight in a molar ratio of 20: 20: 40: 20, respectively, and then polymerized while stirring at 70 ° C. for 5 hours under a nitrogen atmosphere to prepare a binder resin 1 as an acrylic polymer. The weight average molecular weight of polystyrene reduced by gel permeation chromatography (GPC) of the copolymer thus prepared was 25,000, and the degree of dispersion was found to be 1.9.
b) 바인더 수지 2의 제조b) Preparation of Binder Resin 2
500 mL 중합용기에 프로필렌글리콜메틸에테르아세테이트 200 mL과 AIBN 1.0 g을 첨가한 후, 메타아크릴산, 스틸렌, 메틸메타아크릴산 및 시클로헥실 메타아크릴산을 각각 40:20:20:20의 몰비로 아크릴 모노머의 고형분을 40 중량 %로 첨가한 다음, 질소 분위기 하에서 70 ℃에서 5시간 동안 교반하며 중합시켜 공중합체를 합성하였다. 이 반응기에 N,N-디메틸아닐린 0.3 g과 전체 단량체의 고형분 100몰에 대하여 글리시딜메타아크릴산 20 몰비를 첨가한 후 100 ℃에서 10시간 동안 교반하여 측쇄에 아크릴 불포화 결합을 갖는 아크릴 중합체인 바인더 수지 2를 제조하였다. 이와 같이 제조된 공중합체의 겔 투과 크로마토그래피(GPC)에 의한 폴리스티렌 환산 중량 평균 분자량은 2O,O00, 분산도는 2.0로 확인되었다.After adding 200 mL of propylene glycol methyl ether acetate and 1.0 g of AIBN to a 500 mL polymerization vessel, methacrylic acid, styrene, methylmethacrylic acid, and cyclohexyl methacrylic acid were added in a molar ratio of 40: 20: 20: 20, respectively. Was added to 40% by weight, and then polymerized by stirring with stirring at 70 ° C. for 5 hours under a nitrogen atmosphere. A binder of acrylic polymer having an acrylic unsaturated bond in the side chain was added by adding 20 molar ratios of glycidylmethacrylic acid to 0.3 g of N, N -dimethylaniline and 100 moles of solids of all monomers in the reactor. Resin 2 was prepared. The weight average molecular weight of polystyrene reduced by gel permeation chromatography (GPC) of the copolymer thus prepared was 20, 000 and the degree of dispersion was 2.0.
c) 바인더 수지 3의 제조c) preparation of binder resin 3
500 mL 중합용기에 프로필렌글리콜메틸에테르아세테이트 200 mL과 AIBN 1.0 g을 첨가한 후, 글리시딜메타아크릴산, 스틸렌, 메틸메타 아크릴산 및 시클로헥실메타아크릴산을 각각 40:20:20:20의 몰비로 아크릴 모노머의 고형분을 40 중량%로 첨가한 다음, 질소 분위기 하에서 70 ℃에서 5시간 동안 교반하며 중합시켜 공중합체를 합성하였다. 이 반응기에 N,N-디메틸아닐린 0.3 g과 전체 단량체의 고형분 100몰에 대하여 아크릴산 20 몰비를 첨가한 후 100 ℃에서 10시간 동안 교반하여 측쇄에 아크릴 불포화 결합을 갖는 아크릴 중합체인 바인더 수지 3을 제조하였다. 이와 같이 제조된 공중합체의 겔 투과 크로마토그래피(GPC)에 의한 폴리스티렌 환산 중량 평균 분자량은 18,000, 분산도는 1.8로 확인되었다.After 200 mL of propylene glycol methyl ether acetate and 1.0 g of AIBN were added to a 500 mL polymerization vessel, glycidylmethacrylic acid, styrene, methylmethacrylic acid and cyclohexylmethacrylic acid were each acrylic in a molar ratio of 40: 20: 20: 20. A solid content of the monomer was added at 40% by weight, and then polymerized by stirring with stirring at 70 ° C. for 5 hours under a nitrogen atmosphere. To this reactor, 0.3 g of N, N -dimethylaniline and 20 molar ratios of acrylic acid were added to 100 moles of solids of the entire monomer, followed by stirring at 100 ° C. for 10 hours to prepare binder resin 3, an acrylic polymer having an acrylic unsaturated bond in the side chain. It was. The weight average molecular weight of polystyrene reduced by gel permeation chromatography (GPC) of the copolymer thus prepared was 18,000, and the degree of dispersion was found to be 1.8.
[[ 실시예Example 27 내지 43]  27 to 43] 포토레지스트Photoresist 조성물의 제조 Preparation of the composition
자외선 차단막과 교반기가 설치되어 있는 반응 혼합조에 하기 표 1에 기재된 성분과 함량에 따라 바인더 수지 1 내지 3; 광반응성 화합물; 본 발명의 광중합 개시제; 및 FC-430(3M사의 레벨링제)을 순차적으로 첨가하고, 상온에서 교반한 다음, 조성물이 총 100 중량%가 되도록 용매로 PGMEA를 가하여 포토레지스트 조성물을 제조하였다.Binder resins 1 to 3 according to the components and contents shown in Table 1 below in the reaction mixing tank equipped with the ultraviolet shielding film and the stirrer; Photoreactive compounds; Photopolymerization initiator of the present invention; And FC-430 (a 3M leveling agent) were added sequentially, stirred at room temperature, and PGMEA was added to the solvent so that the composition totaled 100% by weight to prepare a photoresist composition.
[실시예 44]Example 44 Black Matrix 포토레지스트 조성물의 제조Preparation of Black Matrix Photoresist Composition
하기 표 1에 기재된 바와 같이, 자외선 차단막과 교반기가 설치되어 있는 반응 혼합조에 바인더 수지 1을 20 중량%, 디펜타에리스리톨헥사아크릴레이트 10 중량%, 화합물 43 0.5 중량%, 고형분 25 중량%로 PGMEA에 분산된 카본블랙 50 중량% 및 FC-430(3M사의 레벨링제, 0.1중량%)을 순차적으로 첨가하고, 상온에서 교반한 다음, 조성물이 총 100 중량%가 되도록 용매로 PGMEA를 가하여 Black Matrix 포토레지스트 조성물을 제조하였다.As shown in Table 1 below, 20% by weight of binder resin 1, 10% by weight of dipentaerythritol hexaacrylate, 0.5% by weight of compound 43, and 25% by weight of solid content were added to PGMEA in a reaction mixing tank equipped with a UV blocking film and a stirrer. 50% by weight of dispersed carbon black and FC-430 (3M leveling agent, 0.1% by weight) were added sequentially, stirred at room temperature, and then PGMEA was added with a solvent to make the composition 100% by weight. The composition was prepared.
[실시예 45] Red 포토레지스트 조성물의 제조Example 45 Preparation of Red Photoresist Composition
하기 표 1에 기재된 바와 같이, 상기 실시예 44에서 카본블랙 대신에 고형분 25 중량%의 Pigment Red 177(P.R. 177) 분산액을 50 중량%를 사용한 것을 제외하고는 동일한 방법으로 Red 포토레지스트 조성물을 제조하였다.As shown in Table 1 below, a red photoresist composition was prepared in the same manner except that 50 wt% of Pigment Red 177 (PR 177) dispersion having a solid content of 25 wt% was used instead of carbon black in Example 44. .
포토레지스트 조성물 제조Photoresist Composition Preparation
실시예Example 바인더 수지(중량%)Binder Resin (wt%) 광반응성 화합물(중량%)Photoreactive Compound (wt%) 광중합개시제(중량%)Photopolymerization Initiator (wt%) 첨가제(중량%)Additive (% by weight)
2727 1 (40)1 (40) 디펜타에리스리톨헥사아크릴산 (20)Dipentaerythritol hexaacrylic acid (20) 화합물 4(0.5)Compound 4 (0.5) FC-430(0.1)FC-430 (0.1)
2828 1 (40)1 (40) 펜타에리스리톨트리아크릴산 (20)Pentaerythritoltriacrylic acid (20) 화합물 34(0.5)Compound 34 (0.5) FC-430(0.1)FC-430 (0.1)
2929 1 (40)1 (40) 트리메틸올프로판트리아크릴산 (10)에틸렌글리콜디아크릴산 (10)Trimethylolpropanetriacrylic acid (10) Ethylene glycol diacrylic acid (10) 화합물 35(0.5)Compound 35 (0.5) FC-430(0.1)FC-430 (0.1)
3030 1 (40)1 (40) 디펜타에리스리톨펜타아크릴산 (20)Dipentaerythritol pentaacrylic acid (20) 화합물 36(0.5)Compound 36 (0.5) FC-430(0.1)FC-430 (0.1)
3131 1 (40)1 (40) 디펜타에리스리톨헥사아크릴산 (20)Dipentaerythritol hexaacrylic acid (20) 화합물 44(0.5)Compound 44 (0.5) FC-430(0.1)FC-430 (0.1)
3232 1 (40)1 (40) 펜타에리스리톨트리아크릴산 (20)Pentaerythritoltriacrylic acid (20) 화합물 48(0.5)Compound 48 (0.5) FC-430(0.1)FC-430 (0.1)
3333 1 (40)1 (40) 트리메틸올프로판트리아크릴산 (10)에틸렌글리콜디아크릴산 (10)Trimethylolpropanetriacrylic acid (10) Ethylene glycol diacrylic acid (10) 화합물 52(0.5)Compound 52 (0.5) FC-430(0.1)FC-430 (0.1)
3434 1 (40)1 (40) 디펜타에리스리톨헥사아크릴산 (20)Dipentaerythritol hexaacrylic acid (20) 화합물 56(0.5)Compound 56 (0.5) FC-430(0.1)FC-430 (0.1)
3535 1 (40)1 (40) 펜타에리스리톨트리아크릴산 (20)Pentaerythritoltriacrylic acid (20) 화합물 60(0.5)Compound 60 (0.5) FC-430(0.1)FC-430 (0.1)
3636 1 (40)1 (40) 트리메틸올프로판트리아크릴산 (10)에틸렌글리콜디아크릴산 (10)Trimethylolpropanetriacrylic acid (10) Ethylene glycol diacrylic acid (10) 화합물 61(0.5)Compound 61 (0.5) FC-430(0.1)FC-430 (0.1)
3737 1 (40)1 (40) 트리메틸올프로판트리아크릴산 (10)에틸렌글리콜디아크릴산 (10)Trimethylolpropanetriacrylic acid (10) Ethylene glycol diacrylic acid (10) 화합물 67(0.5)Compound 67 (0.5) FC-430(0.1)FC-430 (0.1)
3838 2 (40)2 (40) 비스페놀-A 디글리시딜에테르아크릴산 부가물 (20)Bisphenol-A diglycidyl ether acrylic acid adduct (20) 화합물 36(0.5)Compound 36 (0.5) FC-430(0.1)FC-430 (0.1)
3939 2 (40)2 (40) 트리메틸올프로판트리글리시딜에테르아크릴산 부가물 (20)Trimethylolpropanetriglycidyletheracrylic acid adduct (20) 화합물 44(0.5)Compound 44 (0.5) FC-430(0.1)FC-430 (0.1)
4040 3 (40)3 (40) 펜타에리스리톨트리아크릴산 (20)Pentaerythritoltriacrylic acid (20) 화합물 36(0.5)Compound 36 (0.5) FC-430(0.1)FC-430 (0.1)
4141 3 (40)3 (40) 펜타에리스리톨트리메타아크릴산(20)Pentaerythritol trimethacrylic acid (20) 화합물 44(0.5)Compound 44 (0.5) FC-430(0.1)FC-430 (0.1)
4242 1 (20)2 (20)1 (20) 2 (20) 디펜타에리스리톨헥사아크릴산 (20)Dipentaerythritol hexaacrylic acid (20) 화합물 44(0.5)Compound 44 (0.5) FC-430(0.1)FC-430 (0.1)
4343 1 (20)3 (20)1 (20) 3 (20) 디펜타에리스리톨헥사아크릴산 (20)Dipentaerythritol hexaacrylic acid (20) 화합물 44(0.5)Compound 44 (0.5) FC-430(0.1)FC-430 (0.1)
4444 1 (20)1 (20) 디펜타에리스리톨헥사아크릴산 (10)Dipentaerythritol hexaacrylic acid (10) 화합물 44(0.5)Compound 44 (0.5) FC-430 (0.1)카본블랙 (50)FC-430 (0.1) Carbon Black (50)
4545 1 (20)1 (20) 디펜타에리스리톨헥사아크릴산 (10)Dipentaerythritol hexaacrylic acid (10) 화합물 44(0.5)Compound 44 (0.5) FC-430 (0.1)P.R.177 (50)FC-430 (0.1) P.R. 177 (50)
[비교예 1] 포토레지스트 조성물의 제조Comparative Example 1 Preparation of Photoresist Composition
광중합 개시제로 화합물 4을 대신에 하기 화학식 B의 광중합 개시제를 사용한 것을 제외하고는 상기 실시예 27과 동일한 방법으로 포토레지스트 조성물을 제조하였다.A photoresist composition was prepared in the same manner as in Example 27, except that Compound 4 was used instead of Compound 4 as a photopolymerization initiator.
[화학식 B][Formula B]
Figure PCTKR2016000635-appb-I000074
Figure PCTKR2016000635-appb-I000074
[비교예 2] 포토레지스트 조성물의 제조Comparative Example 2 Preparation of Photoresist Composition
광중합 개시제로 화합물 4 대신에 "3-(아세톡시이미노)-1-(6-니트로-9H-플루오렌-3-일)프로판-1-온"을 광중합 개시제로 사용한 것을 제외하고는 상기 실시예 27과 동일한 방법으로 포토레지스트 조성물을 제조하였다.The above examples except that "3- (acetoxyimino) -1- (6-nitro-9H-fluoren-3-yl) propan-1-one" was used as the photoinitiator instead of compound 4 as the photoinitiator. A photoresist composition was prepared in the same manner as in 27.
[시험예] 포토레지스트 조성물 평가[Test Example] Evaluation of Photoresist Composition
상기 실시예 27 내지 45 및 비교예 1과 2에서 제조한 포토레지스트 조성물의 평가는 유리 기판 위에서 실시하였으며, 포토레지스트 조성물의 감도, 잔막율, 패턴 안정성, 내화학성 및 연성 등의 성능을 측정하여 그 평가 결과를 하기 표 2 에 나타냈다.The evaluation of the photoresist compositions prepared in Examples 27 to 45 and Comparative Examples 1 and 2 was carried out on a glass substrate, and the performance of the sensitivity, residual film ratio, pattern stability, chemical resistance and ductility of the photoresist composition was measured. The evaluation results are shown in Table 2 below.
1) 감도 1) Sensitivity
유리 기판 위에 포토레지스트를 스핀 코팅하여 100 ℃에서 1분 동안 핫플레이트에서 건조한 후 스텝 마스크를 이용하여 노광한 후 0.04% KOH 수용액에서 현상하였다. 스텝 마스크 패턴이 초기 두께 대비 80% 두께를 유지하는 노광량을 감도로 평가 하였다. The photoresist was spin coated on a glass substrate, dried on a hot plate at 100 ° C. for 1 minute, exposed using a step mask, and then developed in a 0.04% KOH aqueous solution. Sensitivity was evaluated for the exposure amount in which the step mask pattern maintains 80% of the initial thickness.
2) 잔막율2) Residual rate
포토레지스트 조성물을 기판위에 스핀 코터를 이용하여 도포한 후, 100 ℃에서 1분간 프리베이크(prebake)하고, 365 nm에서 노광시킨 후, 230 ℃에서 20분 동안 포스트베이크(postbake)를 실시하여 레지스트 막의 포스트베이크 전 후의 두께 비율(%)을 측정하였다.The photoresist composition was applied onto the substrate using a spin coater, then prebaked at 100 ° C. for 1 minute, exposed at 365 nm, and post-baked at 230 ° C. for 20 minutes to form a resist film. The thickness ratio (%) before and after the postbaking was measured.
3) 패턴 안정성3) pattern stability
포토레지스트 패턴을 형성한 실리콘 웨이퍼를 홀(Hole) 패턴의 수직방향에서부터 절단하고, 패턴의 단면 방향에서 전자현미경으로 관찰한 결과를 나타냈다. 패턴 사이드 벽(side wall)이 기판에 대하여 55도 이상의 각도로 세워져 있고, 막이 감소되지 않은 것을 '양호'로 하고, 막의 감소가 인정된 것을 '막감(膜減)'으로 판정하였다.The silicon wafer in which the photoresist pattern was formed was cut | disconnected from the vertical direction of a hole pattern, and the result observed with the electron microscope in the cross-sectional direction of the pattern was shown. The pattern side wall was erected at an angle of 55 degrees or more with respect to the substrate, the film was not reduced, and it was determined as 'good', and the reduction of the film was judged as 'film'.
4) 내화학성4) Chemical resistance
포토레지스트 조성물을 기판 위에 스핀 코터를 이용하여 도포한 후, 프리베이크(prebake) 및 포스트베이크(postbake) 등의 공정을 거쳐 형성된 레지스트 막을 스트리퍼(Stripper) 용액에 40 ℃에서 10분 동안 담근 후 레지스트 막의 투과율 및 두께의 변화가 있는지 살펴보았다. 투과율 및 두께의 변화가 2% 이하인 경우 '양호'로 하고, 투과율 및 두께의 변화가 2% 이상이면 '불량'으로 판정하였다.After the photoresist composition was applied onto the substrate using a spin coater, the resist film formed through a process such as prebake and postbake was immersed in a stripper solution for 10 minutes at 40 ° C., and then The change in transmittance and thickness was examined. When the change in transmittance and thickness is 2% or less, it is set as 'good', and when the change in transmittance and thickness is 2% or more, it is determined as 'poor'.
5) 연성5) Ductile
포토레지스트 조성물을 기판위에 스핀 코터를 도포한 후, 100 ℃에서 1분 동안 프리베이크(prebake)하고, 포토레지스트의 감도로 노광시킨 후, KOH 수용액으로 현상하여 20 um x 20 um의 패턴을 형성하였다. 형성된 패턴을 230 ℃에서 20분 동안 포스트베이크(postbake)를 실시하여 가교시키고, 이 패턴을 나노인덴터 (Nano indentor)를 이용하여 연성을 측정하였다. 나노인덴터의 측정은 5g.f 로딩으로 총 변이량이 500 nm 이상이면 '양호', 500 nm 이하이면 '불량'으로 판정하였다.After applying the spin coater onto the substrate, the photoresist composition was prebaked at 100 ° C. for 1 minute, exposed to the sensitivity of the photoresist, and then developed with a KOH aqueous solution to form a pattern of 20 um x 20 um. . The formed pattern was crosslinked by postbake at 230 ° C. for 20 minutes, and the ductility was measured using a nano indentor. The measurement of the nanoindenter was determined to be 'good' if the total variation was more than 500 nm with 5 g.f loading, and 'bad' if it was less than 500 nm.
실시예Example 감도 (mJ/cm2)Sensitivity (mJ / cm 2 ) 잔막율(%)Residual rate (%) 패턴안정성Pattern stability 내화학성Chemical resistance 연성ductility
2727 4545 9191 양호Good 양호Good 양호Good
2828 5050 9292 양호Good 양호Good 양호Good
2929 4545 9191 양호Good 양호Good 양호Good
3030 3535 9393 양호Good 양호Good 양호Good
3131 4545 9393 양호Good 양호Good 양호Good
3232 4040 9191 양호Good 양호Good 양호Good
3333 4040 9191 양호Good 양호Good 양호Good
3434 4545 9090 양호Good 양호Good 양호Good
3535 5050 9292 양호Good 양호Good 양호Good
3636 5050 9090 양호Good 양호Good 양호Good
3737 5050 8989 양호Good 양호Good 양호Good
3838 3030 9393 양호Good 양호Good 양호Good
3939 4545 9191 양호Good 양호Good 양호Good
4040 4545 9090 양호Good 양호Good 양호Good
4141 4040 9393 양호Good 양호Good 양호Good
4242 3535 9090 양호Good 양호Good 양호Good
4343 4040 9090 양호Good 양호Good 양호Good
4444 3535 9292 양호Good 양호Good 양호Good
4545 4040 9191 양호Good 양호Good 양호Good
비교예 1Comparative Example 1 200200 8787 막감Film 불량Bad 양호Good
비교예 2Comparative Example 2 250250 8080 막감Film 불량Bad 불량Bad
상기 표 2로부터 본 발명에 따른 디옥심에스테르 화합물은 포토레지스트 조성물의 광중합 개시제로 사용될 때 소량을 사용하여도 감도가 월등히 우수하며, 잔막율, 패턴안정성, 내화학성 및 연성 등의 물성이 뛰어나 TFT-LCD 제조 공정 중의 노광 및 포스트베이크 공정에서 광중합 개시제로부터 발생하는 아웃개싱을 최소화할 수 있어 오염을 줄일 수 있고 이로 인해 발생할 수 있는 불량을 최소화할 수 있음을 확인하였다.Dioxime ester compound according to the present invention from Table 2 is excellent in sensitivity even when using a small amount when used as a photopolymerization initiator of the photoresist composition, excellent properties such as residual film ratio, pattern stability, chemical resistance and ductility TFT- It was confirmed that the outgassing generated from the photopolymerization initiator can be minimized in the exposure and post-baking processes during the LCD manufacturing process, thereby reducing contamination and minimizing the defects that may occur.
본 발명의 디옥심에스테르 화합물은 포토레지스트 조성물의 광중합 개시제로 사용될 때 소량을 사용하여도 감도가 월등히 우수하며, 잔막율, 패턴안정성, 내화학성 및 연성 등의 물성이 뛰어나 TFT-LCD 제조 공정 중의 노광 및 포스트베이크 공정에서 광중합 개시제로부터 발생하는 아웃개싱을 최소화할 수 있어 오염을 줄일 수 있고 이로 인해 발생할 수 있는 불량을 최소화할 수 있는 장점이 있다.When used as a photoinitiator of the photoresist composition, the dioxime ester compound of the present invention has excellent sensitivity even when used in a small amount, and has excellent physical properties such as residual film ratio, pattern stability, chemical resistance, and ductility. And it is possible to minimize the outgassing from the photopolymerization initiator in the post-baking process can reduce the contamination and there is an advantage that can minimize the defects that can be caused by this.

Claims (9)

  1. 하기 화학식 1로 표시되는 디옥심에스테르 화합물: Dioxime ester compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2016000635-appb-I000075
    Figure PCTKR2016000635-appb-I000075
    상기 화학식 1에서, In Chemical Formula 1,
    R1 내지 R3은 각각 독립적으로 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, (C1-C20)알콕시, (C6-C20)아릴(C1-C20)알킬, 히드록시(C1-C20)알킬, 히드록시(C1-C20)알콕시(C1-C20)알킬, (C3-C20)사이클로알킬 또는 (C3-C20)사이클로알킬(C1-C20)알킬이고; R 1 to R 3 are each independently hydrogen, halogen, (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl, (C 1 -C 20 ) alkoxy, (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl, hydroxy (C 1 -C 20 ) alkyl, hydroxy (C 1 -C 20 ) alkoxy (C 1 -C 20 ) alkyl, (C 3 -C 20 ) cycloalkyl or (C 3 -C 20 ) cycloalkyl (C 1 -C 20 ) alkyl;
    A는 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, (C6-C20)아릴(C1-C20)알킬, 아미노, 니트로, 시아노 또는 히드록시이고;A is hydrogen, halogen, (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl, (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl, amino, nitro, cyano or hydroxy ego;
    n은 0 내지 2의 정수이다.n is an integer of 0-2.
  2. 제1항의 디옥심에스테르 화합물을 포함하는 광중합 개시제. The photoinitiator containing the dioxime ester compound of Claim 1.
  3. 제1항의 디옥심에스테르 화합물, 바인더 및 에틸렌계 불포화 결합을 가지는 화합물을 포함하는 포토레지스트 조성물.A photoresist composition comprising the dioxime ester compound of claim 1, a binder and a compound having an ethylenically unsaturated bond.
  4. 제3항에 있어서, The method of claim 3,
    상기 포토레지스트 조성물은 티옥산톤계 화합물, 아세토페논계 화합물, 비이미다졸계 화합물, 트리아진계 화합물, 티올계 화합물, 및 O-아실옥심계 화합물로 이루어지는 군으로부터 선택되는 1종 또는 2종 이상의 광중합 개시제를 더 포함하는 것을 특징으로 하는 포토레지스트 조성물.The photoresist composition is one or two or more photopolymerization initiators selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, thiol compounds, and O-acyl oxime compounds. A photoresist composition further comprising.
  5. 제3항에 있어서,The method of claim 3,
    상기 디옥심에스테르 화합물은 포토레지스트 조성물 100 중량%에 대하여 0.01 내지 10 중량%로 포함되는 것을 특징으로 하는 포토레지스트 조성물.The dioxime ester compound is a photoresist composition, characterized in that contained in 0.01 to 10% by weight based on 100% by weight of the photoresist composition.
  6. 제3항 또는 제4항에 있어서, The method according to claim 3 or 4,
    상기 포토레지스트 조성물은 착색재를 더 포함하는 것을 특징으로 하는 포토레지스트 조성물.The photoresist composition further comprises a coloring material.
  7. 제3항 또는 제4항의 포토레지스트 조성물의 경화물을 포함하는 성형물.A molded article comprising the cured product of claim 3 or 4.
  8. 제6항의 포토레지스트 조성물의 경화물을 포함하는 성형물.Molded article comprising the cured product of claim 6 photoresist composition.
  9. 제7항의 성형물을 포함하는 디스플레이 장치.A display device comprising the molding of claim 7.
PCT/KR2016/000635 2015-01-26 2016-01-21 Novel dioximester compound, and photopolymerization initiator and photoresist composition containing same WO2016122160A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2015-0012196 2015-01-26
KR1020150012196A KR101824429B1 (en) 2015-01-26 2015-01-26 Novel di-oxime ester compounds and photopolymerization initiator and photoresist composition containing the same

Publications (1)

Publication Number Publication Date
WO2016122160A1 true WO2016122160A1 (en) 2016-08-04

Family

ID=56543711

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2016/000635 WO2016122160A1 (en) 2015-01-26 2016-01-21 Novel dioximester compound, and photopolymerization initiator and photoresist composition containing same

Country Status (3)

Country Link
KR (1) KR101824429B1 (en)
TW (1) TWI552981B (en)
WO (1) WO2016122160A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190103370A (en) * 2017-02-17 2019-09-04 창저우 트론리 어드벤스드 일렉트로닉 머티어리얼스 컴퍼니, 리미티드 Fluorenylaminoketone photoinitiator, preparation method thereof and UV photocurable composition containing same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115160249B (en) * 2022-06-23 2024-04-02 济南立德医药技术有限公司 Preparation method of 5-methyl-3, 4-diphenyl isoxazole

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000006480A (en) * 1998-06-26 2000-01-25 에프. 아. 프라저, 에른스트 알테르 (에. 알테르), 한스 페터 비틀린 (하. 페. 비틀린), 피. 랍 보프, 브이. 스펜글러, 페. 아에글러 New O-acyloxime photoinitiators
JP2001302871A (en) * 2000-04-25 2001-10-31 Taiyo Ink Mfg Ltd Photocurable/thermosetting resin composition and printed wiring board having solder resist coating film and resin insulating layer formed by using the same
JP2007256845A (en) * 2006-03-24 2007-10-04 Fujifilm Corp Photosensitive composition, photosensitive film, method for forming permanent pattern, and printed circuit board
JP2007298538A (en) * 2006-04-27 2007-11-15 Fujifilm Corp Photosensitive composition, photosensitive film, permanent pattern forming method, and printed circuit board

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002100903A1 (en) 2001-06-11 2002-12-19 Ciba Specialty Chemicals Holding Inc. Oxime ester photoinitiators having a combined structure
TW200714651A (en) 2002-10-28 2007-04-16 Mitsubishi Chem Corp Photopolymerization composition and color filter using the same
JP4595374B2 (en) 2003-04-24 2010-12-08 住友化学株式会社 Black photosensitive resin composition
JP3798008B2 (en) 2004-12-03 2006-07-19 旭電化工業株式会社 Oxime ester compound and photopolymerization initiator containing the compound
ATE458010T1 (en) 2005-12-20 2010-03-15 Basf Se OXIMESTER PHOTOINITIATORS
JP5179379B2 (en) 2006-12-27 2013-04-10 株式会社Ａｄｅｋａ Oxime ester compound and photopolymerization initiator containing the compound
US8349548B2 (en) 2007-05-11 2013-01-08 Basf Se Oxime ester photoinitiators
US8202679B2 (en) 2007-12-25 2012-06-19 Adeka Corporation Oxime ester compound and photopolymerization initiator containing the same
US8391887B2 (en) 2010-08-13 2013-03-05 Research In Motion Limited Methods and apparatus to activate location measurements
WO2012045736A1 (en) 2010-10-05 2012-04-12 Basf Se Oxime ester derivatives of benzocarbazole compounds and their use as photoinitiators in photopolymerizable compositions
CN103819583B (en) * 2014-03-18 2016-05-18 常州强力电子新材料股份有限公司 A kind of containing two oxime ester lightlike initiating agents of nitro and its preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000006480A (en) * 1998-06-26 2000-01-25 에프. 아. 프라저, 에른스트 알테르 (에. 알테르), 한스 페터 비틀린 (하. 페. 비틀린), 피. 랍 보프, 브이. 스펜글러, 페. 아에글러 New O-acyloxime photoinitiators
JP2001302871A (en) * 2000-04-25 2001-10-31 Taiyo Ink Mfg Ltd Photocurable/thermosetting resin composition and printed wiring board having solder resist coating film and resin insulating layer formed by using the same
JP2007256845A (en) * 2006-03-24 2007-10-04 Fujifilm Corp Photosensitive composition, photosensitive film, method for forming permanent pattern, and printed circuit board
JP2007298538A (en) * 2006-04-27 2007-11-15 Fujifilm Corp Photosensitive composition, photosensitive film, permanent pattern forming method, and printed circuit board

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190103370A (en) * 2017-02-17 2019-09-04 창저우 트론리 어드벤스드 일렉트로닉 머티어리얼스 컴퍼니, 리미티드 Fluorenylaminoketone photoinitiator, preparation method thereof and UV photocurable composition containing same
KR102252495B1 (en) 2017-02-17 2021-05-14 창저우 트론리 어드벤스드 일렉트로닉 머티어리얼스 컴퍼니, 리미티드 Fluorenylaminoketone photoinitiator, preparation method thereof, and UV photocurable composition containing same

Also Published As

Publication number Publication date
KR101824429B1 (en) 2018-02-06
KR20160091721A (en) 2016-08-03
TWI552981B (en) 2016-10-11
TW201630874A (en) 2016-09-01

Similar Documents

Publication Publication Date Title
WO2016126070A1 (en) Novel oximester derivative compound, and photopolymerization initiator and photoresist composition containing same
WO2015108386A1 (en) Novel β-oximester fluorene compound, a photopolymerization initiator comprising same, and photoresist composition
WO2017057813A1 (en) Binder resin and photosensitive resin composition containing same
EP3057961A1 (en) Photoinitiator and photosensitive composition including the same
WO2017052351A1 (en) Oxime ester compound having excellent heat-resistant stability, photopolymerization initiator containing same, and photosensitive resin composition
WO2020139042A2 (en) Carbazole multi beta oxime ester derivative compound and photopolymerization initiator and photoresist composition comprising same
WO2020050590A1 (en) Compound, colorant composition, photosensitive material, color filter, and display device
WO2019107685A1 (en) Method for producing colorant composition, and colorant composition, colorant dispersion, photosensitive resin composition, color filter, liquid crystal display device produced using same
WO2018182136A9 (en) Blue photosensitive resin composition, color filter produced by using same, and image display device
WO2018008959A1 (en) High-sensitivity oxime ester photopolymerization initiator, and photopolymerizable composition containing same
WO2018182302A1 (en) Blue photosensitive resin composition, and color filter and image display device manufactured by using same
WO2019132138A1 (en) Xanthene-based compound and photosensitive resin composition comprising same
WO2015064958A1 (en) Novel oxime ester biphenyl compound, photo initiator and photosensitive resin composition containing same
WO2016122160A1 (en) Novel dioximester compound, and photopolymerization initiator and photoresist composition containing same
WO2019216600A1 (en) Novel oxime ester compound and photoresist composition comprising same
WO2022260283A1 (en) Photosensitive resin composition, photosensitive resin film using same, color filter and display device
WO2021221304A1 (en) Compound, anti-reflective film including same, and display device
WO2020022670A1 (en) Binder resin, photosensitive resin composition, photoresist, color filter, and display device
WO2022075673A1 (en) Resin, resin composition, and display device using same
WO2019164157A1 (en) Compound, colorant composition comprising same, and resin composition comprising same
WO2020197179A1 (en) Alkali-soluble, photocurable, and thermosetting copolymer, and photosensitive resin composition, photosensitive resin film, and color filter using same
WO2019194384A1 (en) Xanthene-based compound, and photosensitive resin composition, photosensitive material, color filter and display device including same
WO2021080267A1 (en) Polysiloxane copolymer, method for producing same, and resin composition comprising same
WO2019194381A1 (en) Quinophthalone-based compound, photosensitive resin composition comprising same, photosensitive material, color filter, and display device
WO2021075741A1 (en) Quantum dots, curable composition comprising same, cured film manufactured using composition, and color filter comprising cured film

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16743638

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16743638

Country of ref document: EP

Kind code of ref document: A1