KR101824429B1 - Novel di-oxime ester compounds and photopolymerization initiator and photoresist composition containing the same - Google Patents
Novel di-oxime ester compounds and photopolymerization initiator and photoresist composition containing the same Download PDFInfo
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- KR101824429B1 KR101824429B1 KR1020150012196A KR20150012196A KR101824429B1 KR 101824429 B1 KR101824429 B1 KR 101824429B1 KR 1020150012196 A KR1020150012196 A KR 1020150012196A KR 20150012196 A KR20150012196 A KR 20150012196A KR 101824429 B1 KR101824429 B1 KR 101824429B1
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- 0 *=C[C@](C(C1CCCCC1)=NO)C(c(cc1)ccc1-c(cc1)ccc1[N+]([O-])=O)=NO Chemical compound *=C[C@](C(C1CCCCC1)=NO)C(c(cc1)ccc1-c(cc1)ccc1[N+]([O-])=O)=NO 0.000 description 2
- DUQYPMKVOKRROF-KTIKCYFTSA-N C/C(/C(/c(cc1)ccc1-c(cc1)ccc1[N+]([O-])=O)=N\OC(C1CCCCC1)=O)=N\OC(C1CCCCC1)=O Chemical compound C/C(/C(/c(cc1)ccc1-c(cc1)ccc1[N+]([O-])=O)=N\OC(C1CCCCC1)=O)=N\OC(C1CCCCC1)=O DUQYPMKVOKRROF-KTIKCYFTSA-N 0.000 description 1
- LNHLJALTKGUSBZ-KTIKCYFTSA-N C/C(/C(/c(cc1)ccc1-c(cc1)ccc1[N+]([O-])=O)=N\OC(c1ccccc1)=O)=N\OC(c1ccccc1)=O Chemical compound C/C(/C(/c(cc1)ccc1-c(cc1)ccc1[N+]([O-])=O)=N\OC(c1ccccc1)=O)=N\OC(c1ccccc1)=O LNHLJALTKGUSBZ-KTIKCYFTSA-N 0.000 description 1
- XPCDQJKFYNPSKG-XCXBMYBGSA-N C/C(/C/C(/c(cc1)ccc1-c1ccccc1)=N/O)=N\O Chemical compound C/C(/C/C(/c(cc1)ccc1-c1ccccc1)=N/O)=N\O XPCDQJKFYNPSKG-XCXBMYBGSA-N 0.000 description 1
- WBOCLFMZKMQFDA-KIRJRVOOSA-N C/C(/C/C(/c(cc1)ccc1-c1ccccc1)=N/OC(C)=O)=N\OC(C)=O Chemical compound C/C(/C/C(/c(cc1)ccc1-c1ccccc1)=N/OC(C)=O)=N\OC(C)=O WBOCLFMZKMQFDA-KIRJRVOOSA-N 0.000 description 1
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- 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
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- 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
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- 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
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Abstract
The present invention relates to a novel dioxime ester compound, a photopolymerization initiator containing the same, and a photoresist composition. More particularly, the dioxime ester compound according to the present invention is represented by the following general formula (1).
[Chemical Formula 1]
In the above formula (1), A, R 1 to R 3 and n are each as defined in the description of the invention.
Description
The present invention relates to a novel dioxime ester compound, a photopolymerization initiator containing the same, and a photoresist composition.
As typical examples of the photopolymerization initiator used in the photoresist composition, various kinds of acetophenone derivatives, benzophenone derivatives, triazine derivatives, nonimidazole derivatives, acylphosphine oxide derivatives and oxime ester derivatives are known, Absorbs ultraviolet light to hardly show color, has a high radical generation efficiency, and is excellent in compatibility and stability with photoresist composition materials. However, the oxime derivative compounds initially developed have a low photoinitiator efficiency, and in particular, there is a problem that the sensitivity is low in the pattern exposure process to increase the exposure dose, thereby decreasing the yield.
Therefore, the development of a photopolymerization initiator having excellent photosensitivity can realize a sufficient sensitivity with a small amount, and the amount of exposure can be lowered due to the cost reduction effect and the excellent sensitivity, thereby increasing the production amount.
Various oxime ester compound derivatives represented by the following formula (A), which can be used as a photopolymerization initiator in a photoresist composition, are already known.
(A)
In the case of the photopolymerization initiator having an oxime ester group, it is easy to synthesize various photopolymerization initiators capable of regulating the absorption region of the photopolymerization initiator by introducing substituents suitable for R, R 'and R "of the compound.
The oxime ester compound can polymerize and cure the polymerizable compound having an unsaturated bond by irradiating the photoresist composition with light of 365-435 nm, and is useful for a black matrix, a color filter, a column spacer, a flexible insulating film, a photoresist composition for an overcoat .
Therefore, the photoinitiator has high sensitivity to long wavelength light source such as 365-435 nm, good photopolymerization reactivity, easy to manufacture, high thermal stability and storage stability, easy handling, and excellent compatibility with solvents (PGMEA: propylene glycol monomethyl ether acetate) There is a continuing need for new photoinitiators suitable for a variety of uses that can meet the needs of industrial sites, such as satisfactory solubility.
BACKGROUND ART Recently, a photoresist composition used for a liquid crystal display device and a thin film display such as an OLED, more specifically, an organic insulating film of a liquid crystal display device such as a TFT-LCD, a column spacer, a UV overcoat, Studies on a photoresist composition containing a color-resist and a high-sensitivity photopolymerization initiator capable of forming a pattern by a Black Matrix or the like have been conducted.
In general, as a resist composition used for forming a pattern, a photoresist composition containing a binder resin, a polyfunctional monomer having an ethylenically unsaturated bond, and a photopolymerization initiator is preferred.
However, when a conventional photopolymerization initiator is used to form a pattern, the sensitivity of the photopolymerization initiator is low during the exposure process for pattern formation, thereby increasing the amount of photopolymerization initiator used and increasing the amount of exposure, thereby contaminating the mask in the exposure process, There is a disadvantage in that the yield is lowered as a by-product which is generated after decomposition, and there is a problem that the production time is increased due to an increase in the exposure amount and the production amount is reduced.
Accordingly, it is an object of the present invention to provide a novel dioxime ester compound, a photopolymerization initiator containing the same, and a photoresist composition comprising the dioxime ester compound.
The present invention also relates to novel dioxime ester compounds; And a black coloring material or a coloring material for a black matrix or a color filter.
It is still another object of the present invention to provide a color filter or black matrix comprising the photoresist composition for the black matrix or for the color filter.
In order to achieve the above object, the present invention provides a dioxime ester compound represented by the following general formula (1), a photopolymerization initiator and a photoresist composition containing the same.
[Chemical Formula 1]
In Formula 1,
R 1 to R 3 are independently hydrogen, halogen, (C 1 -C 20) alkyl, respectively, (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 selected from the group consisting of hydrogen, halogen, (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl, (C 6 -C 20 ) aryl (C 1 -C 20 ) ego;
n is an integer of 0 to 2;
The term " halo " or " halogen " of the present invention means a fluorine, chlorine, bromine or iodine atom.
The term " alkyl " in the present invention means a monovalent straight-chain or branched saturated hydrocarbon radical consisting solely of carbon and hydrogen atoms, and specific examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, , Octyl, nonyl, and the like.
The term " aryl " of the present invention refers to an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, with a single or fused ring containing, suitably, 4 to 7, preferably 5 or 6, ring atoms in each ring And includes a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl and the like.
The term " alkoxy " of the present invention means an -O-alkyl radical, which may be exemplified by methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy and the like.
The term " arylalkyl " of the present invention is an alkyl group substituted with an aryl group as defined above, such as benzyl.
The term " hydroxyalkyl " of the present invention is an alkyl group substituted with hydroxy, and may be exemplified by hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl and the like.
The term " hydroxyalkoxyalkyl ", as used herein, refers to an alkyl group substituted with hydroxyalkoxy, such as hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, Hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl, hydroxyethoxyhexyl, and the like.
The term " cycloalkyl " in the present invention means a polycyclic alkyl group fused with two or more monocyclic alkyls as well as monocyclic alkyl groups having 3 to 7 carbon ring atoms. Specific examples thereof include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
The term " cycloalkylalkyl " in the present invention means an alkyl group substituted with a cycloalkyl group as defined above, and examples thereof include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclopropylethyl, and the like.
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 (C 1 -C 4) alkoxy. '(C 6 -C 20) aryl (C 1 -C 20) alkyl "is preferably a (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 a hydroxy (C 1 -C 10 ) alkoxy (C 1 -C 10 ) alkyl, more preferably a hydroxy (C 1 -C 4 ) alkoxy (C 1 -C 6 )) alkyl. '(C 3 -C 20) cycloalkyl "group is preferably (C 3 -C 10) cycloalkyl. '(C 3 -C 20) cycloalkyl (C 1 -C 20) alkyl "is preferably a (C 3 -C 10) cycloalkyl (C 1 -C 10) alkyl, more preferably (C 3 - C 10) a cycloalkyl (C 1 -C 6) alkyl.
In Formula 1, when n is 2, each R 1 may be the same as or different from each other.
More particularly the 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 - cyclohexyl, 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, hydroxyethyl 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;
A is selected from the group consisting of hydrogen, bromo, chloro, methyl, ethyl, n - propyl, i - propyl, n - butyl, i - butyl, t - butyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, Phenanthryl, benzyl, amino, nitro, cyano or hydroxy, but is not limited thereto.
Preferably, R 1 is selected from the group consisting of hydrogen, (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl, hydroxy (C 1 -C 20 ) (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.
More preferably, in the 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.
Examples of the dioxime ester compound according to the present invention include the following compounds, but the following compounds do not limit the present invention.
The dioxime ester compound represented by Formula 1 according to the present invention can be prepared, for example, as shown in Reaction Scheme 1 below.
[Reaction Scheme 1]
Wherein 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.
Also, the present invention provides a photopolymerization initiator comprising the dioxime ester compound represented by the general formula (1).
The present invention also provides a photoresist composition comprising the dioxime ester compound represented by Formula 1.
In the present invention, the dioxime ester compound represented by the general formula (1) may be included in a photoresist composition as a photopolymerization initiator.
The photoresist composition of the present invention includes a dioxime ester compound represented by the formula (1), a binder resin, a polymerizable compound having an ethylenically unsaturated bond, a solvent, and the like, and has properties of controlling the pattern characteristics and thin film properties such as heat resistance and chemical resistance outstanding.
According to one embodiment of the present invention, the binder resin used in the photoresist composition may be an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in its side chain, and may be used to control pattern properties and to improve physical properties such as heat resistance and chemical resistance It is preferable to use 3 to 50% by weight based on 100% by weight of the photoresist composition. The acrylic polymer preferably has an average molecular weight of 2,000 to 300 and a dispersion degree of 1.0 to 10.0, And a molecular weight of 4,000 to 10O,
(Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate and the like. Examples of monomers include, (Meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (Meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, isobonyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl Maleic acid monoalkyl ester, monoalkyl itaconate, monoalkyl fumarate, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth) acrylate, maleic anhydride, Acrylate, 3-methylcyclohexyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl cetane-3-methyl (meth) acrylate, styrene, α- methyl styrene, acetoxy-styrene, N - methyl maleimide, N - ethyl maleimide, N - propyl maleimide, N - butyl maleimide, N - cyclohexyl Maleimide, (meth) acrylamide and N -methyl (meth) acrylamide. These may be used alone or in combination of two or more.
The acrylic polymer having an acrylic unsaturated bond in the side chain is a copolymer obtained by addition reaction of an epoxy resin to an acrylic copolymer containing a carboxylic acid, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid monoalkyl ester, (Meth) acrylate such as methyl (meth) acrylate and hexyl (meth) acrylate, an alkyl (meth) acrylate such as cyclohexyl (meth) acrylate, isobonyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl 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 (Meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate at a temperature of 40 to 180 ° C. Can be used.
Another example of an acrylic polymer having an acryl-unsaturated bond in the side chain is a copolymer obtained by addition reaction of an acrylic copolymer containing an epoxy group to a carboxylic acid, such as glycidyl acrylate, glycidyl methacrylate, 3,4-epoxy Acrylate containing an epoxy group such as butyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) (Meth) acrylate such as cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, styrene,? -Methylstyrene, acetoxystyrene, N -methoxyethyl (meth) acrylate, 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 Acrylic acid, methacrylic acid, itaconic acid, maleic acid, and maleic acid monoalkyl ester) with an acrylic monomer containing a carboxylic acid, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and maleic acid monoalkyl ester, May be used as the binder resin.
In the photoresist composition of the present invention, the polymerizable compound having an ethylenically unsaturated bond is crosslinked by a photoreaction at the time of pattern formation to form a pattern, and is crosslinked upon heating at high temperature to impart chemical resistance and heat resistance. The polymerizable compound having an ethylenically unsaturated bond is preferably used in an amount of 0.001 to 40% by weight based on 100% by weight of the photoresist composition. When the polymerizable compound having an ethylenically unsaturated bond is added in an excess amount, the degree of crosslinking becomes too high and the ductility of the pattern is lowered.
The polymerizable compound having an ethylenically unsaturated bond is specifically exemplified by methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) (Meth) acrylate, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate having a number of ethylene oxide groups of 2 to 14, ethylene glycol di (meth) acrylate, ethylene oxide Propylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, trimethylolpropane di (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylate having 2 to 14 carbon atoms, Acrylic acid adducts, phthalic acid diesters of? -Hydroxyethyl (meth) acrylate, toluene diisocyanates of? -Hydroxyethyl (meth) (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, A compound obtained by esterifying a polyhydric alcohol and an alpha, beta -unsaturated carboxylic acid such as dipentaerythritol tri (meth) acrylate, an acrylic acid adduct of a polyglycidyl compound such as trimethylolpropane triglycidyl ether acrylic acid adduct These may be used alone or in combination of two or more.
The amount of the dioxime ester compound of Formula 1 used as a photopolymerization initiator in the photoresist composition of the present invention is preferably 0.01 to 10% by weight based on 100% by weight of the photoresist composition, It is more effective to use 0.1 to 5% by weight.
In addition, the photoresist composition of the present invention may further comprise a silicone compound having an epoxy group or an amine group as an adhesive aid, if necessary.
In the photoresist composition of the present invention, the silicone compound improves the adhesion between the ITO electrode and the photoresist composition, and can increase the heat resistance after curing. Examples of the silicone compound having an epoxy group or an amine group include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyl (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- Methoxysilane, and aminopropyltrimethoxysilane. These may be used alone or in combination of two or more. The silicone compound having an epoxy group or an amine group is 0.0001 to 3% by weight based on 100% by weight of the photoresist composition.
In addition, the photoresist composition of the present invention may further contain a compatibilizing additive such as a photosensitizer, a thermal polymerization inhibitor, a defoaming agent, and a leveling agent, if necessary.
The photoresist composition of the present invention forms a pattern by spin coating a substrate with a solvent and then developing it with an alkali developer by irradiating ultraviolet rays using a mask. % Solvent is added to adjust the viscosity to be in the range of 1 to 50 cps.
In view of compatibility with a binder resin, a photoinitiator and other compounds, the solvent may be ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate (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, , diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N, N - dimethylacetamide (DMAc), N - methyl-2-pyrrolidone (NMP),? -Butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, , Octane, etc. may be used alone or in combination of two or more.
The present invention also provides a colored photoresist composition comprising a black colorant and a colorant in a photoresist composition comprising the dioxime ester compound represented by the above formula (1).
Examples of a black coloring material or a coloring material to be applied as a color filter or a resist for forming a black matrix include cyan, magenta, yellow and black pigments of a mixture of red, green, blue and blue. As the pigment, 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 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 and carbon black.
The present invention also provides a color filter and black matrix comprising the colored photoresist composition.
The dioxime ester compound of the present invention is excellent in sensitivity even when a small amount is used when it is used as a photopolymerization initiator of a photoresist composition and exhibits excellent properties such as residual film ratio, pattern stability, chemical resistance and ductility, And the outgassing generated from the photopolymerization initiator in the postbake process can be minimized, so that the contamination can be reduced and the defects that may occur due to this can be minimized.
For a better understanding of the present invention, representative compounds of the present invention will be described in detail with reference to Examples and Comparative Examples. However, the embodiments according to the present invention can be modified into various other forms, Should not be construed as being limited to the embodiments described below. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.
[Example 1] Preparation of 1- (biphenyl-4-yl) butane-1,3-dione O, O-diacetyldioxime (4)
Reaction 1. Synthesis of 1- (biphenyl-4-yl) butane-1,3-dione ( 2 )
Under an atmosphere of nitrogen, 50 mL of anhydrous ethyl acetate was maintained at 5 캜, 3.08 g of sodium hydride (60% in mineral oil, 0.077 mol) was added, and the mixture was stirred for 30 minutes. 10.0 g (0.051 mol) of 4-acetylbiphenyl ( 1 ) dissolved in 50 mL of ethyl acetate was added and stirred for 1 hour. The reaction solution was gradually heated and stirred at 60 ° C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, and 30 mL of H 2 O was added. After stirring for 30 minutes, 40 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the reaction solution to a pH of 6-7. To the reaction solution was added 100 mL of ethyl acetate and the mixture was stirred for 30 minutes. The organic layer was separated and washed with H 2 O. 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 7.2% (62.0%) of 1- (biphenyl-4-yl) butane-1,3-dione ( 2 ) was obtained by purification by flash chromatography (eluent; ethyl acetate: n -hexane = 1: 4).
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 ): 238
Reaction 2. Synthesis of 1- (biphenyl-4-yl) butane-1,3-dione dioxime ( 3 )
5.0 g (0.021 mol) of 1- (biphenyl-4-yl) butane-1,3-dione ( 2 ) was dispersed in 100 mL of ethanol, and 4.38 g (0.063 mol) of hydroxylamine hydrochloride and 5.17 g mol), and then the reaction solution was gradually heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, and 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 resulting product was purified by silica gel column chromatography (Ethyl acetate: n -hexane = 1: 4) to obtain 5.23 g (92.9%) of 1- (biphenyl-4-yl) butane- 1,3-dione dioxime ( 3 ).
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 ): 268
Reaction 3. Synthesis of 1- (biphenyl-4-yl) butane-1,3-dione O, O-diacetyldioxime ( 4 )
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, 4.25 g (0.042 mol) of ethylamine was added and the reaction solution was stirred for 30 minutes. Then, 3.30 g (0.042 mol) of acetyl chloride was slowly added thereto and stirred for 30 minutes while careful not to raise the temperature of the reaction product. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n -hexane = 1: 4) to obtain 5.82 g (92.3%) of 1- (biphenyl-4-yl) butane- 1,3-dione O, O-diacetyldioxime ( 4 ).
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 (3 H, m)
MS ( m / e ): 352
[Example 2] Preparation of 1- (biphenyl-4-yl) butane-1,3-dione O, O-dipropionyldioxime (5)
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, 4.25 g (0.042 mol) of ethylamine was added and the reaction solution was stirred for 30 minutes. Then, 3.88 g (0.042 mol) of propionyl chloride was added slowly and stirred for 30 minutes while careful not to raise the temperature of the reaction. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n -hexane = 1: 4) to obtain 6.65 g (92.0%) of 1- (biphenyl-4-yl) butane-1,3-dione O, O-dipropionyldioxime ( 5 ).
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 (4 H, m), 8.01 - 8.05 (3 H, m)
MS ( m / e ): 380
[Example 3] Preparation of 1- (biphenyl-4-yl) butane-1,3-dione O, O-dicyclohexanecarbonyl dioxime (6)
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, 4.25 g (0.042 mol) of ethylamine was added and the reaction solution was stirred for 30 minutes. 6.16 g (0.042 mol) of cyclohexanecarbonyl chloride was slowly added thereto and stirred for 30 minutes while careful not to raise the temperature of the reaction product. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n - hexane = 1: 4) to give the 1- (biphenyl-4-yl) butane-1,3-dione O, O- dicyclohexyl hexane-carbonyl-di-oxime (6) 8.54 g (92.0% ) as a .
1 H NMR (? 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 ), 7.78-7.82 (4H, m), 8.01-8.05 (3H, m)
MS ( m / e ): 487
[Example 4] Preparation of 1- (biphenyl-4-yl) butane-1,3-dione O, O-dibenzoyldioxime (7)
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, 4.25 g (0.042 mol) of ethylamine was added and the reaction solution was stirred for 30 minutes. Then, 5.90 g (0.042 mol) of benzoyl chloride was slowly added thereto and stirred for 30 minutes while careful not to raise the temperature of the reaction product. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n -hexane = 1: 4) to obtain 8.26 g (91.2%) of 1- (biphenyl-4-yl) butane-1,3-dione O, O-dibenzoyldioxime ( 7 ).
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 ): 477
Example 5 Preparation of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione O, O-diacetyldioxime (11)
Reaction 1. Synthesis of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione ( 9 )
Under an atmosphere of nitrogen, 50 mL of anhydrous ethyl acetate was maintained at 5 캜, 2.88 g (60% in mineral oil, 0.072 mol) of sodium hydride was added, and the mixture was stirred for 30 minutes. 10.0 g (0.048 mol) of 4-propionylbiphenyl ( 8 ) dissolved in 50 mL of ethyl acetate was added and stirred for 1 hour. The reaction solution was gradually heated and stirred at 60 ° C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, and 30 mL of H 2 O was added. After stirring for 30 minutes, 40 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the reaction solution to a pH of 6-7. To the reaction solution was added 100 mL of ethyl acetate and the mixture was stirred for 30 minutes. The organic layer was separated and washed with H 2 O. 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 chromatography (developing solvent; ethyl acetate: n - hexane = 1: 4) Synthesis of 1- (biphenyl-4-yl) to give 2-methyl-butane-1, 3-dione (9) 7.07g (58.2%) of .
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 ): 252
Reaction 2. Synthesis of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione dioxime ( 10 )
5.0 g (0.020 mol) of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione ( 9 ) was dispersed in 100 mL of ethanol, and 4.18 g (0.060 mol) of hydrochloric acid hydroxylamine and sodium acetate After the addition of 4.92 g (0.060 mol), the reaction solution was gradually heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, and 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 resulting product was purified by silica gel column chromatography (Ethyl acetate: n -hexane = 1: 4) to obtain 5.02 g (88.9%) of 1- (biphenyl-4-yl) -2-methylbutane- 1,3-dione dioxime ( 10 ).
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 ): 282
Reaction 3. Synthesis of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione O, O-diacetyldioxime ( 11 )
5.0 g (0.018 mol) of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione dioxime ( 10 ) was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere, Then, 4.05 g (0.040 mol) of triethylamine was added thereto, and the reaction solution was stirred for 30 minutes. Then, 3.14 g (0.040 mol) of acetyl chloride was slowly added thereto and stirred for 30 minutes while careful not to raise the temperature of the reaction product. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n -hexane = 1: 4) to obtain 5.94 g (90.1%) of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione O, O-diacetyldioxime ( 11 ) ≪ / RTI >
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 (4 H, m), 8.01 - 8.12 (3 H, m)
MS ( m / e ): 366
[Example 6] Production of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione O, O-dicyclohexanecarbonyl dioxime (12)
5.0 g (0.018 mol) of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione dioxime ( 10 ) was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere, Then, 4.05 g (0.040 mol) of triethylamine was added, and the reaction solution was stirred for 30 minutes. Then, 5.86 g (0.040 mol) of cyclohexanecarbonyl chloride was added slowly and the mixture was stirred for 30 minutes Lt; / RTI > Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n - hexane = 1: 4) to obtain 1- (biphenyl-4-yl) -2-methyl-butane-1,3-dione O, O- dicyclohexyl hexane-carbonyl-di-oxime (12 a) 8.48 g ( 88.8%).
1 H NMR (? Ppm; CDCl 3 ): 1.12-1.14 (10H, m), 1.30 (3H, d), 1.62-1.66 7.36-7.38 (3H, m), 7.82-7.86 (4H, m), 8.01-8.08 (3H, m)
MS ( m / e ): 503
[Example 7] Production of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione O, O-dibenzoyldioxime (13)
5.0 g (0.018 mol) of 1- (biphenyl-4-yl) -2-methylbutane-1,3-dione dioxime ( 10 ) was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere, Then, 4.05 g (0.040 mol) of triethylamine was added thereto, and the reaction solution was stirred for 30 minutes. Then, 5.62 g (0.040 mol) of benzoyl chloride was slowly added thereto and stirred for 30 minutes while careful not to raise the temperature of the reaction product. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n - hexane = 1: 4) to obtain 1- (biphenyl-4-yl) -2-methyl-butane-1,3-dione O, O- dibenzoyl-D-oxime (13) 8.22 g (88.2% ) ≪ / RTI >
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 ): 491
[Example 8] Preparation of 1- (biphenyl-4-yl) -2-cyclohexylbutane-1,3-dione O, O-diacetyldioxime (18)
Reaction 1. Synthesis of 1- (biphenyl-4-yl) -2-cyclohexylethanol ( 15 )
Biphenyl ( 14 ) After dissolving 10.0 g (0.065 mol) in 100 mL of dichloromethane and cooling the reaction to -5 ° C, 10.40 g (0.78 mol) of aluminum chloride was added slowly, and 5 mL of dichloromethane 12.53 g (0.078 mol) of 2-cyclohexyl acetyl chloride diluted in dichloromethane was added slowly 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. The organic layer was separated, washed with 500 mL of distilled water, and the recovered organic layer was subjected to vacuum distillation to obtain a silica gel column chromatography (eluent: ethyl acetate: n- 1: 4) to obtain 11.07 g (61.2%) of 1- (biphenyl-4-yl) -2-cyclohexylethanol ( 15 ).
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 , < / RTI > m), 8.01-8.08 (2H, m)
MS ( m / e ): 278
Reaction 2. Synthesis of 1- (biphenyl-4-yl) -2-cyclohexylbutane-1,3-dione ( 16 )
Under an atmosphere of nitrogen, 50 mL of anhydrous ethyl acetate was maintained at 5 DEG C, 2.16 g (60% in mineral oil, 0.054 mol) of sodium hydride was added, and the mixture was stirred for 30 minutes. 10.0 g (0.036 mol) of 1- (biphenyl-4-yl) -2-cyclohexylethanol ( 15 ) dissolved in 50 mL of ethyl acetate was added and stirred for 1 hour. The reaction solution was gradually warmed up to 60 ° C. The reaction was completed by stirring for 5 hours. The reaction solution was cooled to room temperature, and 30 mL of H 2 O was added. After stirring for 30 minutes, 30 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the reaction solution to a pH of 6-7. To the reaction solution was added 100 mL of ethyl acetate and the mixture was stirred for 30 minutes. The organic layer was separated and washed with H 2 O. 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 chromatography (developing solvent; ethyl acetate: n - hexane = 1: 4) to obtain 1- (biphenyl-4-yl) -2-cyclohexyl-butane-1,3-dione in (16) 6.37 g (55.2% ) ≪ / RTI >
1 H NMR (? 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 ), 7.82-7.86 (4H, m), 8.01-8.08 (2H, m)
MS ( m / e ): 320
Reaction 3. Synthesis of 1- (biphenyl-4-yl) -2-cyclohexylbutane-1,3-dione dioxime ( 17 )
5.0 g (0.016 mol) of 1- (biphenyl-4-yl) -2-cyclohexylbutane-1,3-dione ( 16 ) was dispersed in 100 mL of ethanol, and 3.34 g (0.048 mol) of hydrochloric acid hydroxylamine and After 3.94 g (0.048 mol) of sodium was added, the reaction solution was gradually heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, and 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 resulting product was purified by silica gel column chromatography ; ethyl acetate: n - hexane = 1: 4) to give 1- (biphenyl-4-yl) -2-cyclohexyl-butane-1,3-dione di-oxime (17) 4.87 g (yield of 86.9%) .
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 (4 H, m), 8.01-8.06 (2H, m)
MS ( m / e ): 350
Reaction 4. Synthesis of 1- (biphenyl-4-yl) -2-cyclohexylbutane-1,3-dione O, O-diacetyldioxime ( 18 )
5.0 g (0.014 mol) of 1- (biphenyl-4-yl) -2-cyclohexylbutane-1,3-dione dioxime ( 17 ) was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere, 3.24 g (0.032 mol) of triethylamine was added thereto, and the reaction solution was stirred for 30 minutes. 2.51 g (0.032 mol) of acetyl chloride was slowly added thereto and stirred for 30 minutes while careful not to raise the temperature of the reaction product . Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : 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% ).
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 ): 435
[Example 9] Preparation of 1- (biphenyl-4-yl) -2- (cyclopentylmethyl) butane-1,3-dione O, O-diacetyldioxime (22)
Reaction 1. Synthesis of 1- (biphenyl-4-yl) -3-cyclopentylpropan-1-one ( 19 )
Biphenyl ( 14 ) After dissolving 10.0 g (0.065 mol) in 100 mL of dichloromethane and cooling the reaction to -5 ° C, 10.40 g (0.78 mol) of aluminum chloride was added slowly, and 5 mL of dichloromethane 12.53 g (0.078 mol) of 3-cyclopentylpropionyl chloride diluted in dichloromethane 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. The organic layer was separated, washed with 500 mL of distilled water, and the recovered organic layer was subjected to vacuum distillation to obtain a silica gel column chromatography (eluent: ethyl acetate: n- 1: 4) to yield 1- (biphenyl-4-yl) -3-cyclopentyl-propan-1-one (19) was obtained 10.64 g (58.8%).
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 ): 278
Reaction 2. Synthesis of 1- (biphenyl-4-yl) -2- (cyclopentylmethyl) butane-1,3-dione ( 20 )
Under an atmosphere of nitrogen, 50 mL of anhydrous ethyl acetate was maintained at 5 DEG C, 2.16 g (60% in mineral oil, 0.054 mol) of sodium hydride was added, and the mixture was stirred 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 and stirred for 1 hour, The reaction was completed by stirring at 60 DEG C for 5 hours. The reaction solution was cooled to room temperature, and 30 mL of H 2 O was added. After stirring for 30 minutes, 30 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the reaction solution to a pH of 6-7. To the reaction solution was added 100 mL of ethyl acetate and the mixture was stirred for 30 minutes. The organic layer was separated and washed with H 2 O. 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 (Cyclopentylmethyl) butane-1,3-dione ( 20 ) (6.37 g, yield: 40%) as a colorless oil (eluent: ethyl acetate: n -hexane = 1: 55.2%).
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 (4 H, m), 8.01-8.08 (2 H, m)
MS ( m / e ): 320
Reaction 3. Synthesis of 1- (biphenyl-4-yl) -2- (cyclopentylmethyl) butane-1,3-dione dioxime ( 21 )
5.0 g (0.016 mol) of 1- (biphenyl-4-yl) -2- (cyclopentylmethyl) butane-1,3-dione ( 20 ) was dispersed in 100 mL of ethanol and 3.34 g ) And sodium acetate (3.94 g, 0.048 mol) were added. The reaction solution was gradually heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, and 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 resulting product was purified by silica gel column chromatography ; ethyl acetate: n - hexane = 1: 4) to give 1- (biphenyl-4-yl) -2- (cyclopentylmethyl) butane-1,3-dione di-oxime (21) 4.94 g (88.1% ).
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 (4 H, m), 8.01-8.06 (2H, m)
MS ( m / e ): 350
Reaction 4. Synthesis of 1- (biphenyl-4-yl) -2- (cyclopentylmethyl) butane-1,3-dione O, O-diacetyldioxime ( 22 )
5.0 g (0.014 mol) of 1- (biphenyl-4-yl) -2- (cyclopentylmethyl) butane-1,3-dione dioxime 21 was dissolved in 50 mL of ethyl acetate under a nitrogen atmosphere, After maintaining at 5 ° C, 3.24 g (0.032 mol) of triethylamine was added and the reaction solution was stirred for 30 minutes. 2.51 g (0.032 mol) of acetyl chloride was slowly added thereto and the mixture was stirred for 30 minutes Lt; / RTI > Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n - hexane = 1: 4) Synthesis of 1- (biphenyl-4-yl) to yield 2- (cyclopentylmethyl) butane-1,3-dione O, O- di-acetyl-di-oxime (22) 5.49 g (90.3%).
1 H NMR (? Ppm; CDCl 3 ): 0.96 (6H, s), 1.35-1.60 (9H, m), 1.48 7.35 (3H, m), 7.80-7.82 (4H, m), 8.01-8.06 (2H, m)
MS ( m / e ): 435
[Example 10] Preparation of 1- (biphenyl-4-yl) hexane-1,3-dione O, O-diacetyldioxime (25)
Reaction 1. Synthesis of 1- (biphenyl-4-yl) hexane-1,3-dione ( 23 )
50 mL of anhydrous ethyl butyrate was maintained at 5 캜 in a nitrogen atmosphere, 3.08 g of sodium hydride (60% in mineral oil, 0.077 mol) was added, and the mixture was stirred for 30 minutes. 10.0 g (0.051 mol) of 4-acetylbiphenyl ( 1 ) dissolved in 50 mL of ethyl butyrate was added and stirred for 1 hour. The reaction solution was gradually heated and stirred at 60 ° C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, and 30 mL of H 2 O was added. After stirring for 30 minutes, 40 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the reaction solution to a pH of 6-7. To the reaction solution was added 100 mL of ethyl acetate and the mixture was stirred for 30 minutes. The organic layer was separated and washed with H 2 O. 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 (Ethyl acetate: n -hexane = 1: 4) to obtain 8.01 g (59.0%) of 1- (biphenyl-4-yl) hexane-1,3-dione ( 23 ).
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 ): 266
Reaction 2. Synthesis of 1- (biphenyl-4-yl) hexane-1,3-dione dioxime ( 24 )
5.0 g (0.019 mol) of 1- (biphenyl-4-yl) hexane-1,3-dione ( 23 ) were dispersed in 100 mL of ethanol and 3.97 g (0.057 mol) of hydrochloric acid hydroxylamine and 4.68 g mol), and then the reaction solution was gradually heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, and 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 resulting product was purified by silica gel column chromatography (Ethyl acetate: n -hexane = 1: 4) to obtain 5.01 g (88.9%) of 1- (biphenyl-4-yl) hexane-1,3-dione dioxime ( 24 ).
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 (4 H, m), 8.01 - 8.12 (2H, m)
MS ( m / e ): 296
Reaction 3. Synthesis of 1- (biphenyl-4-yl) hexane-1,3-dione O, O-diacetyl dioxime ( 25 )
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 nitrogen atmosphere, 3.74 g (0.037 mol) of ethylamine was added and the reaction solution was stirred for 30 minutes. 2.90 g (0.037 mol) of acetyl chloride was slowly added thereto and stirred for 30 minutes while careful not to raise the temperature of the reaction. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n -hexane = 1: 4) to obtain 5.84 g (90.3%) of 1- (biphenyl-4-yl) hexane-1,3-dione O and O-diacetyldioxime ( 25 ).
1 H NMR (? Ppm; CDCl 3 ): 0.94 (3H, t), 0.96 (6H, s), 1.61 (2H, q), 1.88 3H, m), 7.80-7.86 (4H, m), 8.01-8.12 (3H, m)
MS ( m / e ): 380
[Example 11] Preparation of 1- (biphenyl-4-yl) pentane-1,4-dione O, O-diacetyldioxime (11)
Reaction 1. Synthesis of 1- (biphenyl-4-yl) pentane-1,4-dione ( 26 )
Under an atmosphere of nitrogen, 50 mL of anhydrous ethyl acetate was maintained at 5 DEG C, and then 5.96 g (60% in mineral oil, 0.144 mol) of sodium hydride was added thereto, followed by stirring for 30 minutes. 20.0 g (0.096 mol) of 4-propionylbiphenyl ( 8 ) dissolved in 50 mL of ethyl acetate was added and stirred for 1 hour. The reaction solution was gradually heated and stirred at 60 ° C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, and 30 mL of H 2 O was added. After stirring for 30 minutes, 80 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the reaction solution to a pH of 6-7. To the reaction solution was added 100 mL of ethyl acetate and the mixture was stirred for 30 minutes. The organic layer was separated and washed with H 2 O. 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 (26.2%) of 1- (biphenyl-4-yl) pentane-1,4-dione ( 26 ) was obtained by purifying the residue by chromatography (eluent; ethyl acetate: n -hexane = 1: 4).
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 ): 252
Reaction 2. Synthesis of 1- (biphenyl-4-yl) pentane-1,4-dione dioxime ( 27 )
5.0 g (0.020 mol) of 1- (biphenyl-4-yl) pentane-1,4-dione ( 26 ) were dispersed in 100 mL of ethanol and 4.18 g (0.060 mol) of hydrochloric acid hydroxylamine and 4.92 g mol), and then the reaction solution was gradually heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, and 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 resulting product was purified by silica gel column chromatography (Ethyl acetate: n -hexane = 1: 4) to obtain 4.98 g (88.2%) of 1- (biphenyl-4-yl) pentane-1,4-dione dioxime ( 27 ).
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 ): 282
Reaction 3. Synthesis of 1- (biphenyl-4-yl) pentane-1,4-dione O, O-diacetyldioxime ( 28 )
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 nitrogen atmosphere, the reaction was maintained at -5 ° C, 4.05 g (0.040 mol) of ethylamine was added and the reaction solution was stirred for 30 minutes. Then, 3.14 g (0.040 mol) of acetyl chloride was slowly added thereto and stirred for 30 minutes while careful not to raise the temperature of the reaction product. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n -hexane = 1: 4) to obtain 5.88 g (89.1%) of 1- (biphenyl-4-yl) pentane-1,4-dione O and O-diacetyl dioxime ( 28 ).
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 (4 H, m), 8.01 - 8.12 (3 H, m)
MS ( m / e ): 366
[Example 12] Preparation of 1- (biphenyl-4-yl) pentane-1,4-dione O, O-dicyclohexanecarbonyl dioxime (29)
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 nitrogen atmosphere, the reaction was maintained at -5 ° C, 4.05 g (0.040 mol) of ethylamine was added and the reaction solution was stirred for 30 minutes. Cyclohexanecarbonyl chloride (5.86 g, 0.040 mol) was slowly added thereto and stirred for 30 minutes while careful not to raise the temperature of the reaction product. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n - hexane = 1: 4) to give the 1- (biphenyl-4-yl) pentane-1,4-dione O, O- dicyclohexyl hexane-carbonyl-di-oxime (29) 18.00g (89.5%) as a .
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 ): 503
[Example 13] Preparation of 1- (biphenyl-4-yl) pentane-1,4-dione O, O-dibenzoyldioxime (30)
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 nitrogen atmosphere, the reaction was maintained at -5 ° C, 4.05 g (0.040 mol) of ethylamine was added and the reaction solution was stirred for 30 minutes. Then, 5.62 g (0.040 mol) of benzoyl chloride was added slowly and the mixture was stirred for 30 minutes while careful not to raise the temperature of the reaction. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n -hexane = 1: 4) to obtain 17.36 g (88.5%) of 1- (biphenyl-4-yl) pentane-1,4-dione O and O-dibenzoyldioxime ( 30 ).
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 ): 491
[Example 14] Preparation of 1- (4'-nitrobiphenyl-4-yl) butane-1,3-dione O, O-diacetyldioxime (34)
Reaction 1. 1- (4'-Nitro-biphenyl-4-yl) ethanone ( 31 )
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 DEG C. Then, 12.1 g (0.12 mol) of potassium nitrate was slowly added over 3 hours, Was stirred at -10 < 0 > C for 30 min. Then, 400 mL of ethanol was added to the solution with care that the temperature of the reaction did not exceed 0 DEG C, and the mixture was stirred for about 1 hour, and the product was filtered. The solid product was dispersed in distilled water of 500mL was then stirred for 30 minutes at room temperature, filtered and thoroughly dried to gave the following 1 of light gray washed with distilled water obtained (4`- nitro-biphenyl-4-yl) ethanone (31) 17.8 g (67.2%) was obtained.
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 ): 241
Reaction 2. Synthesis of 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione ( 32 )
Under an atmosphere of nitrogen, 50 mL of anhydrous ethyl acetate was maintained at 5 캜, and then 5.00 g (60% in mineral oil, 0.125 mol) of sodium hydride was 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 and stirred for 1 hour. The reaction solution was gradually heated, The reaction was completed by stirring for 5 hours. The reaction solution was cooled to room temperature, and 30 mL of H 2 O was added. After stirring for 30 minutes, 80 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the reaction solution to a pH of 6-7. To the reaction solution was added 100 mL of ethyl acetate and the mixture was stirred for 30 minutes. The organic layer was separated and washed with H 2 O. 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 chromatography (developing solvent; ethyl acetate: n-hexane = 1: 4) to give 1- (4`- nitro-biphenyl-4-yl) butane-1,4-dione (32) 13.59 g (57.8% ) ≪ / RTI >
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 ): 283
Reaction 3. Synthesis of 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione dioxime ( 33 )
5.0 g (0.018 mol) of 1- (4'-nitro-biphenyl-4-yl) butane-1,4-dione ( 32 ) were dispersed in 100 mL of ethanol, and 3.76 g (0.054 mol) of hydroxylamine hydrochloride and After 4.43 g (0.054 mol) of sodium was added, the reaction solution was gradually heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, and 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 resulting product was purified by silica gel column chromatography ; ethyl acetate: n-hexane = 1: 4) to give 1- (4`- nitro-biphenyl-4-yl) butane-1,3-dione di-oxime (33) 4.97 g (yield 88.2%) .
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 ): 313
Reaction 4. Synthesis of 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione O, O-diacetyldioxime ( 34 )
5.0 g (0.016 mol) of 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione dioxime 33 was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere, After 3.56 g (0.035 mol) of triethylamine was added, the reaction solution was stirred for 30 minutes, 2.75 g (0.035 mol) of acetyl chloride was slowly added thereto, and the mixture was stirred for 30 minutes . Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n-hexane = 1: 4) to give 1- (4`- nitro-biphenyl-4-yl) butane-1,3-dione O, O- di-acetyl-di-oxime (34) 5.67 g (89.1% ).
1 H NMR (? Ppm; CDCl 3 ): 0.96 (6H, s), 1.90 (3H, s), 2.45 (2H, s), 7.70-7.76 2H, d)
MS ( m / e ): 397
[Example 15] Preparation of 1- (4'-nitrobiphenyl-4-yl) butane-1,3-dione O, O-dicyclohexanecarbonyl dioxime (35)
5.0 g (0.016 mol) of 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione dioxime 33 was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere, The reaction solution was stirred for 30 minutes, then 5.13 g (0.035 mol) of cyclohexanecarbonyl chloride was slowly added thereto, and the reaction was allowed to proceed for 30 minutes Lt; / RTI > Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n -hexane = 1: 4) to obtain 7.35 g of 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione O, O-dicyclohexanecarbonyl dioxime ( 35 ) (86.1%).
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 ): 534
[Example 16] Preparation of 1- (4'-nitrobiphenyl-4-yl) butane-1,3-dione O, O-dibenzoyldioxime (36)
5.0 g (0.016 mol) of 1- (4'-nitro-biphenyl-4-yl) butane-1,3-dione dioxime 33 was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere, 3.56 g (0.035 mol) of triethylamine was added thereto, and the reaction solution was stirred for 30 minutes. Then, 4.92 g (0.035 mol) of benzoyl chloride was slowly added thereto and stirred for 30 minutes while careful not to raise the temperature of the reaction product . Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n -hexane = 1: 4) to obtain 7.19 g (86.2%) of 1- (4'-nitro-biphenyl-4-yl) butane- 1,3-dione O, O-dibenzoyldioxime 36 , ).
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 ): 522
[Example 17] Preparation of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) propane-1,3-dione O, O-diacetyldioxime (39)
Reaction 1. Synthesis of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) propane-1,3-dione ( 37 )
50 mL of anhydrous ethyl cyclohexanecarboxylate was maintained at 5 캜 in a nitrogen atmosphere, and then 5.00 g (60% in mineral oil, 0.125 mol) of sodium hydride was 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 and stirred for 1 hour. And the mixture was stirred at 60 ° C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, and 30 mL of H 2 O was added. After stirring for 30 minutes, 80 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the reaction solution to a pH of 6-7. To the reaction solution was added 100 mL of ethyl acetate and the mixture was stirred for 30 minutes. The organic layer was separated and washed with H 2 O. 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 chromatography (developing solvent; ethyl acetate: n - hexane = 1: 4) to give 1-cyclohexyl-3- (4`- knitted lobby-4-yl) propane-1,3-dione (37) to 15.11 g (51.8%).
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 ): 351
Reaction 2. Synthesis of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) propane-1,3-dioneoxime ( 38 )
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 mol) and 6.89 g (0.054 mol) of sodium acetate. The reaction solution was gradually heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, and 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 resulting product was purified by silica gel column chromatography ; ethyl acetate: n - hexane = 1: 4) to provide 1-cyclohexyl-3- (4`- knitted lobby-4-yl) propane-1,3-dione di-oxime (38) 8.99 g (84.2 %).
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 ): 381
Reaction 3. Synthesis of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) propane-1,3-dione O, O-diacetyldioxime ( 39 )
5.0 g (0.013 mol) of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) propane-1,3-dione dioxime ( 38 ) was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere, After maintaining the temperature at -5 ° C, 2.93 g (0.029 mol) of triethylamine was added, and the reaction solution was stirred for 30 minutes. Then, 2.28 g (0.029 mol) of acetyl chloride was slowly added thereto, Lt; / RTI > Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n - hexane = 1: 4) to provide 1-cyclohexyl-3- (4`- knitted lobby-4-yl) propane-1,3-dione O, O- di-acetyl-di-oxime (39) 4.97 g (82.1%).
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 ): 466
[Example 18] Preparation of 1- (4'-nitrobiphenyl-4-yl) -2-pentylbutane-1,3-dione O, O-diacetyldioxime (44)
Reaction 1. Synthesis of 1- (biphenyl-4-yl) heptan-1-one ( 40 )
Biphenyl ( 14 ) After dissolving 10.0 g (0.065 mol) in 100 mL of dichloromethane and cooling the reaction to -5 ° C, 10.40 g (0.78 mol) of aluminum chloride was added slowly, and 5 mL of dichloromethane 11.59 g (0.078 mol) of heptanoyl chloride diluted in tetrahydrofuran was slowly added over 2 hours and the reaction was stirred at -5 DEG C for 1 hour. Then, the reaction mixture was slowly poured into 1 L of ice water and stirred for 30 minutes. The organic layer was separated, washed with 500 mL of distilled water, and the recovered organic layer was subjected to vacuum distillation to obtain a silica gel column chromatography (eluent: ethyl acetate: n- 1: 4) to obtain 10.56 g (61.0%) of 1- (biphenyl-4-yl) heptan-l-one ( 40 ).
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 ): 266
Reaction 2. Synthesis of 1- (4'-nitro-biphenyl-4-yl) heptan-1-one ( 41 )
10.0 g (0.038 mol) of 1- (biphenyl-4-yl) heptan-1-one ( 40 ) was dissolved in 100 mL of concentrated sulfuric acid, and the reaction solution was maintained at -10 ° C. Then, 4.65 g (0.046 mol) Was slowly added over 3 h and the reaction was stirred at -10 < 0 > C for 30 min. Then, 400 mL of ethanol was added to the solution with care that the temperature of the reaction did not exceed 0 ° C, and the mixture was stirred for about 1 hour, and then the product was filtered. The resulting 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 then dried to give a light yellow 1- (4'-nitro-biphenyl-4-yl) 7.36 g (62.2%) of ( 41 ) was obtained.
1 H-NMR (? Ppm; CDCl 3 ): 0.87 (3H, t), 1.28 (8H, m), 1.72 (2H, m), 7.71-7.78 (2H, d)
MS ( m / e ): 311
Reaction 3. Synthesis of 1- (biphenyl-4-yl) -2-pentylbutane-1,3-dione ( 42 )
Under an atmosphere of nitrogen, 50 mL of anhydrous ethyl acetate was maintained at 5 캜, 1.92 g (60% in mineral oil, 0.048 mol) of sodium hydride was added, and the mixture was stirred 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 and stirred for 1 hour, The reaction was completed by stirring at 60 DEG C for 5 hours. The reaction solution was cooled to room temperature, and 30 mL of H 2 O was added. After stirring for 30 minutes, 30 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the reaction solution to a pH of 6-7. To the reaction solution was added 100 mL of ethyl acetate and the mixture was stirred for 30 minutes. The organic layer was separated and washed with H 2 O. 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 chromatography (developing solvent; ethyl acetate: n - hexane = 1: 4) Synthesis of 1- (biphenyl-4-yl) to give butane-2-pentyl-1, 3-dione (42) 5.89 g (52.1% ) of .
1 H NMR (? Ppm; CDCl 3 ): 0.87 (3H, t), 1.28 (8H, m), 1.72 (1H, t), 2.10 (3H, s), 7.32-7.36 7.84 (4 H, m), 8.01 - 8.06 (2 H, m)
MS ( m / e ): 353
Reaction 4. Synthesis of 1- (biphenyl-4-yl) -2-pentylbutane-1,3-dione dioxime ( 43 )
5.0 g (0.014 mol) of 1- (biphenyl-4-yl) -2-pentylbutane-1,3-dione ( 42 ) was dispersed in 100 mL of ethanol and 2.92 g (0.042 mol) of hydrochloric acid hydroxylamine and sodium acetate 3.45 g (0.042 mol) of triethylamine were added and the reaction solution was slowly heated to reflux for 1 hour. The reaction mixture was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, and 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 resulting product was purified by silica gel column chromatography (Ethyl acetate: n -hexane = 1: 4) to obtain 4.45 g (82.9%) of 1- (biphenyl-4-yl) -2-pentylbutane- 1,3-dione dioxime ( 43 ).
1 H NMR (? Ppm; CDCl 3 ): 0.88 (3H, t), 1.29 (8H, m), 1.72 (1H, t), 2.09 3H, m), 7.80-7.82 (4H, m), 8.01-8.06 (2H, m)
MS ( m / e ): 383
Reaction 5. Synthesis of 1- (biphenyl-4-yl) -2-pentylbutane-1,3-dione O, O-diacetyldioxime 44
5.0 g (0.013 mol) of 1- (biphenyl-4-yl) -2-pentylbutane-1,3-dione dioxime ( 43 ) was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction was maintained at -5 Then, 2.93 g (0.029 mol) of triethylamine was added thereto, and the reaction solution was stirred for 30 minutes. Then, 2.28 g (0.029 mol) of acetyl chloride was slowly added thereto and stirred for 30 minutes while careful not to raise the temperature of the reaction product. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n - hexane = 1: 4) to obtain 1- (biphenyl-4-yl) butane-2-pentyl-1, 3-dione O, O- di-acetyl-di-oxime (44) 5.55 g (91.3% ) ≪ / RTI >
1 H NMR (? Ppm; CDCl 3 ): 0.86 (3H, t), 0.96 (6H, s), 1.28 (8H, m), 1.72 (1H, t), 7.33-7.35 7.82 (4 H, m), 8.01 - 8.06 (2 H, m)
MS ( m / e ): 468
[Example 19] Preparation of 1- (4'-nitrobiphenyl-4-yl) -2-pentylbutane-1,3-dione O, O-dibenzoyldioxime (45)
5.0 g (0.013 mol) of 1- (biphenyl-4-yl) -2-pentylbutane-1,3-dione dioxime ( 43 ) was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere and the reaction was maintained at -5 Then, 2.93 g (0.029 mol) of triethylamine was added and the reaction solution was stirred for 30 minutes. 4.07 g (0.029 mol) of benzoyl chloride was slowly added thereto and stirred for 30 minutes while careful not to raise the temperature of the reaction product. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n -hexane = 1: 4) to obtain 6.87 g (89.3%) of 1- (biphenyl-4-yl) -2-pentylbutane- 1,3-dione O, O-dibenzoyldioxime 45 , ≪ / RTI >
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 (4 H, m), 8.03 (2 H, d), 8.24 (2 H, d)
MS ( m / e ): 592
Example 20 Preparation of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) -2-pentylpropane-1,3-dione O, O-diacetyldioxime (48)
Reaction 1. Synthesis of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) -2-pentylpropane-1,3-dione ( 46 )
50 mL of anhydrous ethyl cyclohexanecarboxylate was maintained at 5 캜 in a nitrogen atmosphere, 2.16 g (60% in mineral oil, 0.054 mol) of sodium hydride was added, and the mixture was stirred 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, And the mixture was stirred at 60 DEG C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, and 30 mL of H 2 O was added. After stirring for 30 minutes, 30 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the reaction solution to a pH of 6-7. To the reaction solution was added 100 mL of ethyl acetate and the mixture was stirred for 30 minutes. The organic layer was separated and washed with H 2 O. 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 (Ethyl acetate: n -hexane = 1: 4) to obtain 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) -2-pentylpropane-1,3-dione 46 ) (6.76 g, 50.1%).
1 H NMR (? Ppm; CDCl 3 ): 0.87 (3H, t), 1.10-1.14 (10H, m), 1.28 (8H, m), 1.58-1.64 2.10 (3H, s), 7.32-7.36 (3H, m), 7.80-7.84 (4H, m), 8.01-8.06
MS ( m / e ): 422
Reaction 2. Synthesis of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) -2-pentylpropane-1,3-dione dioxime ( 47 )
5.0 g (0.012 mol) of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) -2-pentylpropane-1,3-dione ( 46 ) was dispersed in 100 mL of ethanol and hydroxylamine hydrochloride 2.50 g (0.036 mol) of sodium acetate and 2.95 g (0.036 mol) of sodium acetate were added thereto. The reaction solution was gradually heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, and 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 resulting product was purified by silica gel column chromatography ; ethyl acetate: n - hexane = 1: 4) to give 1-cyclohexyl-3- (4`- knitted lobby-4-yl) propan-2-pentyl-1, 3-dione as a di-oxime (47) 4.38 g (80.9%) was obtained.
1 H NMR (? Ppm; CDCl 3 ): 0.87 (3H, t), 1.10-1.14 (10H, m), 1.28 (8H, m), 1.58-1.64 2.10 (3H, s), 7.32-7.34 (3H, m), 7.80-7.82 (4H, m), 8.01-8.06
MS ( m / e ): 452
Reaction 3. Synthesis of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) -2-pentylpropane-1,3-dione O, O-diacetyldioxime ( 48 )
5.0 g (0.011 mol) of 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) -2-pentylpropane-1,3-dione dioxime 47 was dissolved in 50 mL of ethyl acetate After the reaction solution was maintained at -5 ° C, 2.43 g (0.024 mol) of triethylamine was added and the reaction solution was stirred for 30 minutes. Then, 1.88 g (0.024 mol) of acetyl chloride was slowly added thereto, ≪ / RTI > for 30 min. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n -hexane = 1: 4) to obtain 1-cyclohexyl-3- (4'-nitrobiphenyl-4-yl) -2-pentylpropane-1,3-dione O, O-diacetyldioxime ( 48 ) 5.14 g (87.3%).
1 H NMR (? 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 M), 7.80-7.83 (4H, m), 8.01-8.06 (2H, m), 7.31-7.
MS ( m / e ): 536
[Example 21] Preparation of 1- (4'-bromobiphenyl-4-yl) butane-1,3-dione O, O-diacetyldioxime (52)
Reaction 1. Synthesis of 1- (4'-bromobiphenyl-4-yl) butane-1,3-dione ( 50 )
Under an atmosphere of nitrogen, 50 mL of anhydrous ethyl acetate was maintained at 5 DEG C, 2.16 g (60% in mineral oil, 0.054 mol) of sodium hydride was added, and the mixture was stirred for 30 minutes. After adding 10.0 g (0.036 mol) of 4-acetyl-4'-bromobiphenyl ( 49 ) dissolved in 50 mL of ethyl acetate and stirring for 1 hour, the reaction solution was gradually heated and stirred at 60 ° C for 5 hours Completed. The reaction solution was cooled to room temperature, and 30 mL of H 2 O was added. After stirring for 30 minutes, 30 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the reaction solution to a pH of 6-7. To the reaction solution was added 100 mL of ethyl acetate and the mixture was stirred for 30 minutes. The organic layer was separated and washed with H 2 O. 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 chromatography (developing solvent; ethyl acetate: n - hexane = 1: 4) 1 - (4`--bromobiphenyl-4-yl) to give butane-1,3-dione (50) 5.97 g (52.3% ) of .
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 ): 317
Reaction 2. Synthesis of 1- (4'-bromobiphenyl-4-yl) butane-1,3-dione dioxime ( 51 )
5.0 g (0.016 mol) of 1- (4'-bromobiphenyl-4-yl) butane-1,3-dione ( 50 ) was dispersed in 100 mL of ethanol, and 3.34 g (0.048 mol) of hydrochloric acid hydroxylamine and sodium acetate 3.94 g (0.048 mol) was added thereto, and then the reaction solution was gradually heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, and 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 resulting product was purified by silica gel column chromatography Ethyl acetate: n -hexane = 1: 4) to obtain 4.72 g (84.9%) of 1- (4'-bromobiphenyl-4-yl) butane-1,3-dione dioxime ( 51 ).
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 ): 347
Reaction 3. Synthesis of 1- (4'-bromobiphenyl-4-yl) butane-1,3-dione O, O-diacetyldioxime ( 52 )
5.0 g (0.014 mol) of 1- (4'-bromobiphenyl-4-yl) butane-1,3-dione dioxime 51 was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere, Then, 3.14 g (0.031 mol) of triethylamine was added thereto, and the reaction solution was stirred for 30 minutes. Then, 2.43 g (0.031 mol) of acetyl chloride was slowly added thereto and stirred for 30 minutes while careful not to raise the temperature of the reaction. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n - hexane = 1: 4) 1 - (4`--bromobiphenyl-4-yl) butane-1,3-dione to give O, O- di-acetyl-di-oxime (52) 5.43 g (89.9% ) ≪ / RTI >
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 ): 431
[Example 22] Preparation of 1- (4'-cyanobiphenyl-4-yl) butane-1,3-dione O, O-diacetyldioxime (56)
Reaction 1. Synthesis of 4-acetyl-4'-cyanobiphenyl ( 53 )
(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 thereto. The solution was slowly warmed and refluxed for 3 hours. 300 mL of distilled water and 300 mL of ethyl acetate were added to the reaction mixture, and the mixture was stirred for about 30 minutes. The organic layer was separated, washed with 200 mL of saturated aqueous ammonium chloride solution and 100 mL of distilled water three times, The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent; dichloromethane: n -hexane = 1: 5) to obtain 8.23 g (51.3%) of 4-acetyl-4'-cyanobiphenyl ( 53 ).
1 H NMR (? Ppm; CDCl 3 ): 2.31 (3H, s), 7.72-7.76 (4H, m), 7.95
MS ( m / e ): 221
Reaction 2. Synthesis of 1- (4'-cyanobiphenyl-4-yl) butane-1,3-dione ( 54 )
Under an atmosphere of nitrogen, 50 mL of anhydrous ethyl acetate was maintained at 5 캜, 2.72 g (60% in mineral oil, 0.068 mol) of sodium hydride was added, and the mixture was stirred for 30 minutes. 10.0 g (0.045 mol) of 4-acetyl-4'-cyanobiphenyl ( 53 ) dissolved in 50 mL of ethyl acetate was added and stirred for 1 hour. The reaction solution was gradually warmed up and stirred at 60 ° C. for 5 hours, Completed. The reaction solution was cooled to room temperature, and 30 mL of H 2 O was added. After stirring for 30 minutes, 50 mL of 1% HCl aqueous solution was slowly added dropwise to neutralize the reaction solution to a pH of 6-7. To the reaction solution was added 100 mL of ethyl acetate and the mixture was stirred for 30 minutes. The organic layer was separated and washed with H 2 O. 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 chromatography (developing solvent; ethyl acetate: n - hexane = 1: 4) to give 1- (4`- cyanobiphenyl-4-yl) butane-1,3-dione (54) 6.18 g (52.2% ) of .
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 ): 263
Reaction 3. Synthesis of 1- (4'-cyanobiphenyl-4-yl) butane-1,3-dione dioxime ( 55 )
5.0 g (0.019 mol) of 11- (4'-cyanobiphenyl-4-yl) butane-1,3-dione ( 54 ) were dispersed in 100 mL of ethanol, and 3.97 g (0.057 mol) of hydrochloric acid hydroxylamine and sodium acetate 4.68 g (0.057 mol) of triethylamine were added thereto, and the reaction solution was slowly heated to reflux for 1 hour. The reaction mixture was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, and 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 resulting product was purified by silica gel column chromatography (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 ).
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 ): 293
Reaction 4. Synthesis of 1- (4'-cyanobiphenyl-4-yl) butane-1,3-dione O, O-diacetyldioxime 56
5.0 g (0.017 mol) of 1- (4'-cyanobiphenyl-4-yl) butane-1,3-dione dioxime ( 55 ) was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere, Then, 3.74 g (0.037 mol) of triethylamine was added thereto, and the reaction solution was stirred for 30 minutes. 2.90 g (0.037 mol) of acetyl chloride was slowly added thereto and stirred for 30 minutes while careful not to raise the temperature of the reaction. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n -hexane = 1: 4) to obtain 5.58 g (86.9%) of 1- (4'-cyanobiphenyl-4-yl) butane-1,3-dione O, O-diacetyldioxime 56 , ≪ / RTI >
1 H NMR (? Ppm; CDCl 3 ): 0.92 (6H, s), 1.88 (3H, s), 2.40 (2H, s), 7.72-7.75 2H, d)
MS ( m / e ): 377
[Example 23] Preparation of 1- (4'-tert-butylbiphenyl-4-yl) butane-1,3-dione O, O-diacetyldioxime (60)
Reaction 1. Synthesis of 1- (4'-tert-butylbiphenyl-4-yl) butane-1,3-dione ( 58 )
Under an atmosphere of nitrogen, 50 mL of anhydrous ethyl acetate was maintained at 5 캜, 2.40 g (60% in mineral oil, 0.060 mol) of sodium hydride was added, and the mixture was stirred for 30 minutes. 10.0 g (0.040 mol) of 4-acetyl-4'-tert-butylbiphenyl ( 57 ) dissolved in 50 mL of ethyl acetate was added and stirred for 1 hour. The reaction solution was gradually warmed and stirred at 60 ° C for 5 hours The reaction was complete. The reaction solution was cooled to room temperature, and 30 mL of H 2 O was added. After stirring for 30 minutes, 40 mL of 1% aqueous HCl solution was slowly added dropwise to neutralize the reaction solution to a pH of 6-7. To the reaction solution was added 100 mL of ethyl acetate and the mixture was stirred for 30 minutes. The organic layer was separated and washed with H 2 O. 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 6.16 g (52.3%) of 1- (4'-tert-butylbiphenyl-4-yl) butane-1,3-dione ( 58 ) was obtained by purification by flash chromatography (eluent; ethyl acetate: n -hexane = 1: ).
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 ): 294
Reaction 2. Synthesis of 1- (4'-tert-butylbiphenyl-4-yl) butane-1,3-dioneoxime ( 59 )
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 then the reaction solution was gradually heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, and 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 resulting product was purified by silica gel column chromatography ; ethyl acetate: n - hexane = 1: 4) to give the 1- (4`-tert- butyl-biphenyl-4-yl) butane-1,3-dione di-oxime (59) 4.57 g (82.9% ) as a .
1 H NMR (? Ppm; CDCl 3 ): 1.32 (9H, s), 1.95 (3H, s), 3.45 (2H, s), 7.72-7.76 2H, d)
MS ( m / e ): 324
Reaction 3. Synthesis of 1- (4'-tert-butylbiphenyl-4-yl) butane-1,3-dione O, O-diacetyldioxime ( 60 )
5.0 g (0.015 mol) of 1- (4'-tert-butylbiphenyl-4-yl) butane-1,3-dione dioxime 59 was dissolved in 50 mL of ethyl acetate under a nitrogen atmosphere, After stirring for 30 minutes, 2.59 g (0.033 mol) of acetyl chloride was slowly added thereto, and stirring was continued for 30 minutes to prevent the temperature of the reaction from rising, Respectively. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: 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 %).
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, < / RTI > d), 8.24 (2H, d)
MS ( m / e ): 408
[Example 24] 1- ( p -Terphenyl-4-yl) butane-1,3-dione O, O-diacetyl dioxime (61)
Phenylboronic acid 3.37 g (0.028 mol) and 1- (4`--bromobiphenyl-4-yl) butane-1,3-dione O, O- di-acetyl-di-oxime (52) 10.0 g (0.023 mol ) to the reactor , And 2.31 g (0.002 mol) of tetrakis (triphenylphosphine) palladium (0) were added thereto, and then 100 mL of tetrahydrofuran was added thereto. To the reaction mixture was added dropwise 100 mL of a 2 M aqueous potassium carbonate solution. The reaction mixture was heated to 60 DEG C and stirred. After the reaction was completed, the reaction mixture was cooled to room temperature and ethyl acetate (100 mL) was added thereto. The organic layer was washed with 50 mL of purified water and the organic layer was separated. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluting solvent ethyl acetate: n -hexane = 4) to obtain 5.11 g (51.9%) of 1- ( p -terphenyl-4-yl) butane-1,3-dione O, O-diacetyldioxime 61 .
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, < / RTI > d), 8.25 (2H, d)
MS ( m / e ): 428
[Example 25] 1- (1,1'-biphenyl-4-yl) -propane-1,2-dione O, O - Preparation of diacetyl dioxime (64)
Reaction 1. Synthesis of 1- (1,1'-biphenyl-4-yl) -1,2-propanedione-2-oxime (62)
19.2 g (0.091 mmol) of 4-propionylbiphenyl (8) was dissolved in 300 mL of tetrahydrofuran (THF), and 48 mL of 4 N HCl dissolved in 1,4-dioxane and 31 mL of isopentyl nitrite (0.233 mmol ) In turn, and the reaction was stirred at 25 < 0 > C for 6 hours. Then, 100 mL of ethyl acetate was added to the reaction solution and the mixture was washed with 200 mL of distilled water. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid product was purified by using ethyl acetate and hexane (1: v) 1- (1,1'- biphenyl-4-yl) -1,2-propane-dione-2-oxime (62) 13.9 g (63.8% ) by recrystallization using a mixed solvent and then dried to a light gray in ≪ / RTI >
1 H-NMR (? Ppm; CDCl 3 ): 2.19 (3H, s), 7.36 (1H, t), 7.43 (2H, t), 7.59 , < / RTI > s), 7.98 (2H, d)
MS ( m / e ): 239
Reaction 2. Synthesis of 1- (biphenyl-4-yl) -2-propanet-l, 2-dione dioxime ( 63 )
10.06 g (0.042 mol) of 1- (1,1'-biphenyl-4-yl) -1,2-propanedione-2-oxime (62) was dispersed in 100 mL of ethanol and 5.83 g mol) and 6.90 g (0.084 mol) of sodium acetate were added. The reaction solution was gradually heated and refluxed for 3 hours. The reaction mixture was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, and 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 resulting product was purified by silica gel column chromatography (Ethyl acetate: n -hexane = 1: 4) to obtain 9.02 g (84.3%) of 1- (biphenyl-4-yl) -2-propanet- l, 2-dione dioxime ( 63 ).
1 H NMR (? Ppm; DMSO d6 ): 2.21 (3H, s), 7.34-7.43 (3H, m), 7.58-7.62 11.45 (1H, s), 11.60 (1H, s)
MS ( m / e ): 254
Reaction 3. Synthesis of 1- (1,1'-biphenyl-4-yl) -propane-1,2-dione O, O -diacetyldioxime ( 64 )
3.81 g (0.015 mol) of 1- (biphenyl-4-yl) -2-propanetri-1,2-dione dioxime ( 63 ) was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere, Then, 3.34 g (0.033 mol) of triethylamine was added thereto, and the reaction solution was stirred for 30 minutes. 2.59 g (0.033 mol) of acetyl chloride was slowly added thereto and stirred for 30 minutes while careful not to raise the temperature of the reaction product. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n-hexane = 1: 4) to yield 1- (1,1'-biphenyl-4-yl) propane-1,2-dione O, O-di-acetyl-di-oxime (64) 4.32 g (85.2 %).
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 (1H, s), 7.98 (2H, d)
MS ( m / e ): 338
[Example 26] 1- (4'-Nitrobiphenyl-4-yl) -heptane-1,2-dione O, O - Preparation of diacetyl dioxime (67)
Reaction 1. Synthesis of 1- (4'-nitrobiphenyl-4-yl) -1,2-heptanedione-2-oxime (65)
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) 16 mL of 4 N HCl and 12 mL (0.078 mmol) of isopentyl nitrite were added in this order, and the reaction was stirred at 25 ° C for 6 hours. Then, 50 mL of ethyl acetate was added to the reaction solution, and the mixture was washed with 100 mL of distilled water. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid product was purified with ethyl acetate and hexane (1: v) a recrystallization using a mixed solvent and then dried to obtain a light gray of 1- (4'-knit lobby-4-yl) -1,2-heptane-dione-2-oxime (65) 6.41 g (62.8% ) of .
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
MS ( m / e ): 340
Reaction 2. Synthesis of 1- (4'-nitrobiphenyl-4-yl) heptane-1,2-dione dioxime ( 66 )
10.00 g (0.029 mol) of 1- (4'-nitrobiphenyl-4-yl) -1,2-heptanedione-2-oxime (65) was dispersed in 100 mL of ethanol, and hydroxylated hydrochloride (4.05 g, 0.058 mol ) And sodium acetate (4.75 g, 0.058 mol) were added. The reaction solution was gradually heated and refluxed for 3 hours. The reaction mixture was cooled to room temperature, 100 mL of distilled water and 200 mL of ethyl acetate were added, and 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 resulting product was purified by silica gel column chromatography ; ethyl acetate: n - hexane = 1: 4) to give 1- (4'-knit lobby-4-yl) heptane-1,2-dione di-oxime (66) was obtained 7.66 g (74.3%).
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
MS ( m / e ): 355
Reaction 3. Synthesis of 1- (4'-nitrobiphenyl-4-yl) -heptane-1,2-dione O, O -diacetyldioxime 67
5.00 g (0.014 mol) of 1- (4'-nitrobiphenyl-4-yl) heptane-1,2-dione dioxime ( 66 ) was dissolved in 50 mL of ethyl acetate under nitrogen atmosphere, Then, 3.14 g (0.031 mol) of triethylamine was added thereto, and the reaction solution was stirred for 30 minutes. Then, 2.43 g (0.031 mol) of acetyl chloride was slowly added thereto and stirred for 30 minutes while careful not to raise the temperature of the reaction. Then, 50 mL of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate : n-hexane = 1: 4) to give 1- (4'-knit lobby-4-yl) heptane-1,2-dione O, O-di-acetyl-di-oxime (67) 4.32 g (85.2% ).
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, d), 8.01 (2H, d), 8.30 (2H, d)
MS ( m / e ): 439
≪ Preparation of binder resin &
a) Preparation of binder resin 1
After adding 200 mL of propylene glycol methyl ether acetate (PGMEA) and 1.5 g of AIBN (azobisisobutyronitrile) to a 500 mL polymerization vessel, a solution of methacrylic acid, glycidyl methacrylic acid, methyl methacrylic acid, and dicyclopentanyl acrylic acid Was added in an amount of 40 wt% of the solid content of the acrylic monomer at a molar ratio of 20: 20: 40: 20, and then the mixture was stirred at 70 ° C for 5 hours under a nitrogen atmosphere to prepare an acrylic polymer binder resin 1. The copolymer thus prepared had an average molecular weight of 25,000 and a degree of dispersion of 1.9.
b) Preparation of binder resin 2
200 mL of propylene glycol methyl ether acetate and 1.0 g of AIBN were added to a 500 mL polymerization vessel, and then a solution of acrylic acid, styrene, methyl methacrylic acid, and cyclohexyl methacrylic acid in a molar ratio of 40:20:20:20, respectively, Was added in an amount of 40% by weight, and the mixture was polymerized under stirring in a nitrogen atmosphere at 70 캜 for 5 hours to synthesize a copolymer. To this reactor was added 0.3 g of N, N -dimethylaniline and 20 molar ratio of glycidyl methacrylic acid to 100 mol of the solid content of the whole monomers, followed by stirring at 100 DEG C for 10 hours to obtain an acrylic polymer binder having an acrylic unsaturated bond Resin 2 was prepared. The average molecular weight of the copolymer thus prepared was found to be 20, 00, and the degree of dispersion was 2.0.
c) Preparation of binder resin 3
200 mL of propylene glycol methyl ether acetate and 1.0 g of AIBN were added to a 500 mL polymerization vessel and glycidyl methacrylic acid, styrene, methyl methacrylic acid, and cyclohexyl methacrylic acid were added to the acrylic resin solution at a molar ratio of 40: 20: 20: The solid content of the monomer was added in an amount of 40% by weight, and the resulting mixture was polymerized under stirring in a nitrogen atmosphere at 70 캜 for 5 hours to synthesize a copolymer. To this reactor was added 0.3 g of N, N -dimethylaniline and 20 molar ratio of acrylic acid to 100 mol of the solid content of the entire monomer, and the mixture was stirred at 100 DEG C for 10 hours to prepare an acrylic polymer having acrylic unsaturated bonds in its side chain Respectively. The copolymer thus prepared had an average molecular weight of 18,000 and a dispersion degree of 1.8.
[Examples 27 to 43] Preparation of photoresist composition
In a reaction mixture tank equipped with an ultraviolet shielding film and a stirrer, binder resins 1 to 3 were prepared according to the components and contents shown in Table 1 below. Photoreactive compounds; A photopolymerization initiator of the present invention; And FC-430 (leveling agent of 3M) were sequentially added, and the mixture was stirred at room temperature. Then, PGMEA was added with a solvent so that the total amount of the composition was 100% by weight to prepare a photoresist composition.
[Example 44] Preparation of Black Matrix Photoresist Composition
As shown in Table 1, 20 parts by weight of binder resin 1, 10 parts by weight of dipentaerythritol hexaacrylate, 0.5 part by weight of compound 43 and 25 parts by weight of solid content were added to a reaction mixture tank equipped with an ultraviolet shielding film and a stirrer in PGMEA 50% by weight of dispersed carbon black and FC-430 (leveling agent of 3M company, 0.1% by weight) were sequentially added and stirred at room temperature. Then, PGMEA was added with a solvent so that the total amount of the composition was 100% A composition was prepared.
[Example 45] Preparation of Red photoresist composition
As shown in the following Table 1, a red photoresist composition was prepared in the same manner as in Example 44, except that 50 wt% of Pigment Red 177 (PR 177) dispersion with a solid content of 25 wt% was used instead of carbon black .
(weight%)
(weight%)
Initiator
(weight%)
(weight%)
(0.5)
(0.1)
(0.5)
(0.1)
Ethylene glycol diacrylic acid (10)
(0.5)
(0.1)
(0.5)
(0.1)
(0.5)
(0.1)
(0.5)
(0.1)
Ethylene glycol diacrylic acid (10)
(0.5)
(0.1)
(0.5)
(0.1)
(0.5)
(0.1)
Ethylene glycol diacrylic acid (10)
(0.5)
(0.1)
Ethylene glycol diacrylic acid (10)
(0.5)
(0.1)
(0.5)
(0.1)
(0.5)
(0.1)
(0.5)
(0.1)
(0.5)
(0.1)
2 (20)
(0.5)
(0.1)
3 (20)
(0.5)
(0.1)
(0.5)
Carbon black (50)
(0.5)
PR177 (50)
[Comparative Example 1] Preparation of photoresist composition
A photoresist composition was prepared in the same manner as in Example 27 except that a photopolymerization initiator of the following formula (B) was used instead of the compound (4) as a photopolymerization initiator.
[Chemical Formula B]
[Comparative Example 2] Preparation of photoresist composition
(6-nitro-9H-fluoren-3-yl) propan-1-one "was used instead of the compound 4 as a photopolymerization initiator as a photopolymerization initiator. 27, a photoresist composition was prepared.
[Test Example] Evaluation of photoresist composition
The evaluation of the photoresist compositions prepared in Examples 27 to 45 and Comparative Examples 1 and 2 was performed on a glass substrate and the performance of the photoresist composition such as sensitivity, residual film ratio, pattern stability, chemical resistance and ductility was measured The evaluation results are shown in Table 2 below.
1) Sensitivity
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 developed in 0.04% KOH aqueous solution. The exposure amount at which the step mask pattern was maintained at 80% thickness with respect to the initial thickness was evaluated as sensitivity.
2)
The photoresist composition was applied on the substrate using a spin coater, prebaked at 100 DEG C for 1 minute, exposed at 365 nm, postbaked at 230 DEG C for 20 minutes, The thickness ratio (%) after post-baking was measured.
3) Pattern stability
The silicon wafer on which the photoresist pattern was formed was cut from the vertical direction of the hole pattern and observed with an electron microscope in the cross-sectional direction of the pattern. The side wall of the pattern was erected at an angle of 55 degrees or more with respect to the substrate, the film was not reduced and the film was judged to be 'good'.
4) Chemical resistance
After the photoresist composition is applied on a substrate using a spin coater, a resist film formed by a process such as prebake and postbake is immersed in a stripper solution at 40 DEG C for 10 minutes, Transmittance and thickness were observed. It was judged as 'good' when the transmittance and thickness were less than 2% and 'bad' when the transmittance and thickness were more than 2%.
5) ductility
The photoresist composition was applied on the substrate by spin coating, prebaked at 100 DEG C for 1 minute, exposed with a photoresist sensitivity, and developed with a KOH aqueous solution to form a pattern of 20 mu x 20 mu m . The formed pattern was post-baked at 230 캜 for 20 minutes to crosslink, and the pattern was measured for ductility using a nanoindentor. The nanoindenter was evaluated as "good" when the total amount of shift was 500 nm or more, and "poor" when the total amount was 500 nm or less.
(mJ / cm 2 )
(%)
From Table 2, it can be seen that the dioxime ester compound according to the present invention, when used as a photopolymerization initiator in a photoresist composition, is excellent in sensitivity even when a small amount is used and has excellent properties such as residual film ratio, pattern stability, chemical resistance and ductility, It is possible to minimize the outgassing generated from the photopolymerization initiator in the exposure and postbake processes in the LCD manufacturing process, thereby reducing the contamination and minimizing the defects that may occur.
Claims (8)
[Chemical Formula 1]
In Formula 1,
R 1 to R 3 are independently hydrogen, (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl, each (C 1 - C 20) alkyl, (C 3 -C 20) cycloalkyl or (C 3 -C 20) cycloalkyl (C 1 -C 20) alkyl;
A is selected from the group consisting of hydrogen, halogen, (C 1 -C 20 ) alkyl, (C 6 -C 20 ) aryl, (C 6 -C 20 ) aryl (C 1 -C 20 ) ego;
n is an integer of 0 to 2;
Wherein the dioxime ester compound is contained in an amount of 0.01 to 10% by weight based on 100% by weight of the photoresist composition.
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| KR1020150012196A KR101824429B1 (en) | 2015-01-26 | 2015-01-26 | Novel di-oxime ester compounds and photopolymerization initiator and photoresist composition containing the same |
| PCT/KR2016/000635 WO2016122160A1 (en) | 2015-01-26 | 2016-01-21 | Novel dioximester compound, and photopolymerization initiator and photoresist composition containing same |
| TW105102204A TWI552981B (en) | 2015-01-26 | 2016-01-25 | Novel di-oxime ester compound and photopolymerization initiator and photoresist composition including the same |
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| 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 |
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| SG77689A1 (en) * | 1998-06-26 | 2001-01-16 | Ciba Sc Holding Ag | 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 |
| EP1395615B1 (en) | 2001-06-11 | 2009-10-21 | Basf Se | 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 |
| EP1963374B1 (en) | 2005-12-20 | 2010-02-17 | Basf Se | Oxime ester photoinitiators |
| EP2128132B1 (en) | 2006-12-27 | 2014-01-15 | Adeka Corporation | Oxime ester compound and photopolymerization initiator containing the same |
| US8349548B2 (en) | 2007-05-11 | 2013-01-08 | Basf Se | Oxime ester photoinitiators |
| CN101855201B (en) | 2007-12-25 | 2013-09-18 | 株式会社艾迪科 | Oxime esters and photopolymerization initiators containing the same |
| US8391887B2 (en) | 2010-08-13 | 2013-03-05 | Research In Motion Limited | Methods and apparatus to activate location measurements |
| EP2625166B1 (en) | 2010-10-05 | 2014-09-24 | 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 |
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| 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 |
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