TW201630874A - Novel di-oxime ester compound and photopolymerization initiator and photoresist composition including the same - Google Patents

Abstract

Provided are a novel di-oxime ester compound, a photopolymerization initiator and a photoresist composition including the same, wherein the di-oxime ester compound is represented by Chemical Formula 1 below: [Chemical Formula 1] in Chemical Formula 1, A, R1 to R3 and n are the same as defined in the detailed description of the present invention.

Description

Novel diterpene ester compounds and photopolymerization initiators and photoresist compositions including the same

This invention relates to novel di-oxime ester compounds, as well as photopolymerization initiators and photoresist compositions comprising the same.

A variety of photopolymerization initiators are generally known for use in photoresist compositions, for example, acetophenone derivatives, benzophenone derivatives, triazine derivatives, biimidazole derivatives. An acylphosphine oxide derivative, an oxime ester derivative or the like, wherein the oxime ester derivative has the following advantages: the oxime ester derivative absorbs UV, making the color difficult to display; the oxime ester derivative is free The base generation efficiency is high; and the material compatibility and stability between the oxime ester derivative and the material of the photoresist composition are excellent. However, the problem is that the initially developed anthracene-derived compounds have low initial light efficiency, especially during pattern exposure, the sensitivity of the steroid-derived compounds is low, and thus it is necessary to increase the amount of exposure, and thus Production is reduced.

Therefore, by developing a photopolymerization initiator with excellent light sensitivity, a small amount of photopolymerization initiator can achieve sufficient sensitivity, resulting in cost reduction, and lowering exposure due to its excellent sensitivity, thereby improving Production.

It is known that various oxime ester compound derivatives represented by the following chemical formula A can be used as a photopolymerization initiator in a photoresist composition:

In the case where the photopolymerization initiator has an oxime ester group, a plurality of photopolymerizations capable of controlling the absorption region of the photopolymerization initiator can be easily synthesized by introducing a suitable substituent to the R, R', and R" of the compound. Initial agent.

By irradiating the photoresist composition with light having a wavelength of from 365 nm to 435 nm, the oxime ester compound can polymerize and cure a polymer having an unsaturated bond, thereby being usable for a black matrix, a color filter, a column. A photoresist composition such as a spacer spacer, a flexible insulating film, or an overcoat.

Therefore, there is a continuing need for novel photoinitiators that are suitable for use in a variety of applications with high sensitivity and good photopolymerization for long wavelength sources of wavelengths from 365 nm to 435 nm; Preparation; easy to handle with high thermal stability and storage stability; and in line with industrial requirements (eg, solubility, etc., soluble in solvents (PGMEA (propylene glycol monomethyl ether acetate)).

In recent years, research on photoresist compositions for thin film displays (for example, liquid crystal display devices, organic light emitting diodes (OLEDs), etc.) has been actively carried out by developing a photoresist composition with an alkali developing solution. More specifically, research has been actively conducted on a pattern-forming composition including a high-sensitivity photopolymerization initiator and a photoresist composition which can be used for an organic insulating film such as a TFT of a liquid crystal display device. -LCD), column spacers, UV protective film, RGB color resist, black matrix, etc.

In general, as the resist composition for pattern formation, the photoresist composition preferably includes a binder resin, a multifunctional monomer having an ethylenically unsaturated bond, and a photopolymerization initiator.

However, when a pattern is formed by using an existing photopolymerization initiator, it is necessary to increase the amount of use or the amount of exposure of the photopolymerization initiator due to low sensitivity when performing the patterning exposure process, and therefore, in the exposure procedure The mask may be contaminated, and during the high-temperature crosslinking, the productivity may be lowered due to the impurities generated when the photopolymerization initiator is decomposed, and the exposure time may be increased by increasing the exposure amount, possibly This will lead to a reduction in production, and these problems have been tried to overcome.

[Related literature]

[Patent Document 1] JP 2001-302871 A (October 31, 2001)

[Patent Document 2] JP 2006-160634 A (June 22, 2006)

[Patent Document 3] JP 2005-025169 A (January 27, 2005)

[Patent Document 4] JP 2005-242279 A (September 8, 2005)

[Patent Document 5] WO 02/100903 (December 19, 2002)

[Patent Document 6] WO 07/071497 (June 28, 2007)

[Patent Document 7] WO 08/138733 (November 20, 2008)

[Patent Document 8] WO 08/078686 (July 3, 2008)

[Patent Document 9] WO 09/081483 (July 2, 2009)

[Patent Document 10] KR 2013-0124215 A (May 3, 2013)

[Patent Document 11] KR 2013-0115272 A (October 21, 2013)

One embodiment of the present invention is directed to providing a novel diterpene ester compound and a photopolymerization initiator and photoresist composition comprising the same.

Another embodiment of the present invention is directed to providing a molded article comprising a cured product of a photoresist composition comprising the novel diterpene ester compound.

Another embodiment of the present invention is directed to providing a display device including the molded article of the present invention.

In a general aspect, the present invention provides a diterpene ester compound represented by Chemical Formula 1, including a photopolymerization initiator thereof and a photoresist composition:

In Chemical Formula 1, R ₁ to R ₃ are each independently hydrogen, halogen, (C ₁ to C ₂₀ ) alkyl, (C ₆ to C ₂₀ ) aryl, (C ₁ to C ₂₀ ) alkoxy, ( C ₆ to C ₂₀ ) aryl (C ₁ to C ₂₀ ) alkyl, hydroxy (C ₁ to C ₂₀ ) alkyl, hydroxy (C ₁ to C ₂₀ ) alkoxy (C ₁ to C ₂₀ ) alkyl, (C ₃ to C ₂₀ ) cycloalkyl, or (C ₃ to C ₂₀ ) cycloalkyl (C ₁ to C ₂₀ ) alkyl; A hydrogen, halogen, (C ₁ to C ₂₀ ) alkyl, (C ₆ to C ₂₀ ) an aryl group, a (C ₆ to C ₂₀ ) aryl (C ₁ to C ₂₀ ) alkyl group, an amine group, a nitro group, a cyano group, or a hydroxyl group; and n is an integer of 0 to 2.

The term "halo" or "halogen" as used in the present invention means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

The term "alkyl" as used in the present invention means a monovalent straight-chain or branched saturated hydrocarbon group consisting of only carbon atoms and hydrogen atoms, including methyl, ethyl, propyl, isopropyl, butyl, isobutylene. The base, the tertiary butyl group, the pentyl group, the hexyl group, the octyl group, the fluorenyl group and the like are specific examples, but the invention is not limited thereto.

The term "aryl" as used in the present invention refers to an organic group derived by removing a hydrogen atom from an aromatic hydrocarbon, and includes a single ring system or a fused ring system suitably containing 4 to 7 ring atoms. Preferably, 5 or 6 ring atoms are included in each ring, and even include a form in which a plurality of aryl groups are linked by a single bond. Specific examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, an anthryl group, an indenyl group, a fluorenyl group, a phenanthryl group, etc., but the present invention does not Limited to this.

The term "alkoxy" as used in the present invention means -O-alkyl, and includes, for example, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy and the like.

The term "aralkyl" as used in the present invention means an alkyl group substituted with the aforementioned aryl group, and includes, for example, a benzyl group.

The term "hydroxyalkyl" as used in the present invention means an alkyl group substituted by a hydroxy group, and includes, for example, a methylol group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group and the like.

The term "hydroxyalkoxyalkyl" as used in the present invention means an alkyl group substituted with a hydroxyalkoxy group, and includes, for example, a hydroxymethoxymethyl group, a hydroxymethoxyethyl group, a hydroxymethoxypropyl group, a hydroxyl group. Methoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, Hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl, hydroxyethoxyhexyl, and the like.

The term "cycloalkyl" as used in the present invention means not only a monocyclic alkyl group of 3 to 7 carbon ring atoms but also a polycyclic alkyl group in which two or more monocyclic alkyl groups are fused to each other. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like, but the invention is not limited thereto.

The term "cycloalkylalkyl" as used in the present invention means an alkyl group substituted by the aforementioned cycloalkyl group, and includes, for example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclopropylethyl and the like.

Further, the "(C ₁ to C ₂₀ ) alkyl group" of the present invention is preferably a (C ₁ to C ₁₀ ) alkyl group, more preferably a (C ₁ to C ₆ ) alkyl group. The "(C ₆ to C ₂₀ ) aryl group" is preferably a (C ₆ to C ₁₈ ) aryl group. The "(C ₁ to C ₂₀ ) alkoxy group" is preferably a (C ₁ to C ₁₀ ) alkoxy group, more preferably a (C ₁ to C ₄ ) alkoxy group. "(C ₆ to C ₂₀ ) aryl (C ₁ to C ₂₀ ) alkyl" is preferably (C ₆ to C ₁₈ ) aryl (C ₁ to C ₁₀ ) alkyl, more preferably C ₆ to C ₁₈ ) Aryl (C ₁ to C ₆ ) alkyl. The "hydroxy (C ₁ to C ₂₀ ) alkyl group" of the present invention is preferably a hydroxyl group (C ₁ to C ₁₀ ) alkyl group, more preferably a hydroxyl group (C ₁ to C ₆ ) alkyl group. "Hydroxy (C ₁ to C ₂₀ ) alkoxy (C ₁ to C ₂₀ ) alkyl" is preferably a hydroxy (C ₁ to C ₁₀ ) alkoxy (C ₁ to C ₁₀ ) alkyl group, more preferably a hydroxyl group. (C ₁ to C ₄ ) alkoxy (C ₁ to C ₆ ) alkyl. The "(C ₃ to C ₂₀ ) cycloalkyl group" is preferably a (C ₃ to C ₁₀ ) cycloalkyl group. "(C ₃ to C ₂₀ )cycloalkyl (C ₁ to C ₂₀ ) alkyl" is preferably (C ₃ to C ₁₀ ) cycloalkyl (C ₁ to C ₁₀ ) alkyl, more preferably C ₃ To C ₁₀ ) cycloalkyl (C ₁ to C ₆ ) alkyl.

In Chemical Formula 1, when n is 2, each R ₁ may be the same as or different from each other.

More specifically, each of R ₁ to R ₃ is independently hydrogen, bromo, chloro, iodo, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl Base, n-pentyl, isopentyl, n-hexyl, isohexyl, phenyl, naphthyl, biphenyl, terphenyl, fluorenyl, fluorenyl, phenanthryl, methoxy, ethoxy, n-propoxy , isopropoxy, n-butoxy, isobutoxy, tert-butoxy, benzyl, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxy N-pentyl, hydroxyisopentyl, hydroxy-n-hexyl, hydroxyisohexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl , hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl, hydroxyethoxyhexyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclopropyl Methyl, cyclopentylmethyl, or cyclohexylmethyl; and in Chemical Formula 1, A may be hydrogen, bromo, chloro, methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, first Butyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, benzyl, amino, nitro, cyano, or hydroxy, but the present invention is not limited thereto.

Preferably, in Chemical Formula 1, R ₁ may be hydrogen, (C ₁ to C ₂₀ ) alkyl, (C ₆ to C ₂₀ ) aryl (C ₁ to C ₂₀ ) alkyl, hydroxy (C ₁ to C ₂₀ ) an alkyl group, a hydroxyl group (C ₁ to C ₂₀ ) alkoxy group (C ₁ to C ₂₀ ) alkyl group, (C ₃ to C ₂₀ ) cycloalkyl group, or (C ₃ to C ₂₀ ) cycloalkyl group (C) ₁ to C ₂₀ )alkyl; R ₂ and R ₃ may independently be independently (C ₁ to C ₂₀ ) alkyl, (C ₆ to C ₂₀ ) aryl, (C ₆ to C ₂₀ ) aryl (C ₁ to C ₂₀ ) alkyl, hydroxy (C ₁ to C ₂₀ ) alkyl, hydroxy (C ₁ to C ₂₀ ) alkoxy (C ₁ to C ₂₀ ) alkyl, (C ₃ to C ₂₀ ) cycloalkyl, or (C ₃ to C ₂₀ ) cycloalkyl (C ₁ to C ₂₀ ) alkyl; and A may be hydrogen, halogen, (C ₁ to C ₂₀ ) alkyl, (C ₆ to C ₂₀ ) aryl, (C ₆ to C ₂₀ ) an aryl (C ₁ to C ₂₀ ) alkyl group, a nitro group, or a cyano group.

More preferably, in Chemical Formula 1, R ₁ may be hydrogen, (C ₁ to C ₂₀ ) alkyl, (C ₃ to C ₂₀ ) cycloalkyl, or (C ₃ to C ₂₀ ) cycloalkyl (C ₁ To C ₂₀ )alkyl; R ₂ and R ₃ may independently be independently (C ₁ to C ₂₀ )alkyl, (C ₆ to C ₂₀ )aryl, or (C ₃ to C ₂₀ )cycloalkyl; It may be hydrogen, halogen, (C ₁ to C ₂₀ ) alkyl, (C ₆ to C ₂₀ ) aryl, nitro, or cyano.

Representative examples of diterpene ester compounds according to the present invention may include, but are not limited to, the following compounds:

For example, the diterpene ester compound represented by Chemical Formula 1 of the present invention can be produced by the following Reaction Formula 1: [Reaction Formula 1]

In Reaction Formula 1, A, R ₁ to R ₃ and n are the same as defined in the above Chemical Formula 1, and X ₁ and X ₂ are each independently hydrogen.

In other general aspects, a photopolymerization initiator comprising a diterpene ester compound represented by the aforementioned Chemical Formula 1 is provided.

In other general aspects, a photoresist composition comprising the diterpene ester compound represented by the aforementioned Chemical Formula 1 is provided.

In the present invention, the photoresist composition may include a diterpene ester compound represented by the aforementioned Chemical Formula 1 as a photopolymerization initiator.

The photoresist composition of the present invention includes a diterpene ester compound represented by Chemical Formula 1, a binder resin, a polymer compound having an ethylenic unsaturated bond, a solvent, and the like, and the photoresist composition of the present invention has excellent adjustment pattern characteristics. Ability and excellent film physical properties (such as heat resistance, chemical resistance, etc.).

Further, the photoresist composition of the present invention may further comprise, in addition to the diterpene ester compound represented by Chemical Formula 1, at least one known photopolymerization initiator from the group consisting of: thioxanthone- a compound, an acetophenone-based compound, a biimidazole-based compound, a triazine-based compound, a thiol-based compound, and an O-fluorenyl group. O-acyloxime-based compound.

Examples of the thioxanthone-based compound may include: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4 -dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc., and the thioxanthone compound can be used alone Use or mix two or more. Examples of the acetophenone-based compound may include: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinepropan-1-one, 2-benzyl-2-dimethylamine 1-(-4-morpholinylphenyl)-butan-1-one, 2-(4-methylindolyl)-2-(dimethylamino)-1-(4-morpholinylphenyl) )-butan-1-one or the like, and the acetophenone-based compound may be used singly or in combination of two or more. Examples of the biimidazole-based compound may include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorobenzene The group is -4,4',5,5'-tetraphenyl-1,2'-biimidazole or the like, and the biimidazole-based compound may be used singly or in combination of two or more. Examples of the triazine-based compound may include: 2,4,6-tris(trichloromethyl)-symmetric-triazine, 2-methyl-4,6-bis(trichloromethyl)-symmetric-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-symmetric-triazine, 2-[2-(furan-2-yl)ethylene 4-[6,6-bis(trichloromethyl)-symmetric-triazine, 2-[2-(4-dimethylamino-2-methylphenyl)vinyl]-4,6-double (trichloromethyl)-symmetric-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-symmetric-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-symmetric-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloro) Methyl)-symmetric-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-symmetric-triazine, etc., and the triazine compound can be used alone or in two Or a mixture of more. The O-mercapto lanthanide compound may include: 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzamide), ethyl ketone-1-[9 -ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl]-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzobenzhydryl)-9H-carbazol-3-yl]-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-(2) ,2-dimethyl-1,3-dioxolan)methoxybenzylidene-9H-carbazol-3-yl]-1-(O-acetamidine), etc., and O-fluorenyl The lanthanoid compounds may be used singly or in combination of two or more. Based on 100% by weight of the photoresist composition, 0.1% by weight to 5.0% by weight of a known photopolymerization initiator may be used to impart a better shape for forming a flexible film. characteristic.

According to an exemplary embodiment of the present invention, an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in a side chain can be used as a binder resin in a photoresist composition. In order to provide the ability to adjust pattern characteristics and film physical properties (eg, heat resistance, chemical resistance, etc.), the binder resin is preferably used in an amount of from 3% by weight to 50% by weight based on 100% by weight of the photoresist composition. Further, the acrylic polymer preferably has a weight average molecular weight of 2,000 to 300,000 as measured by gel permeation chromatography (GPC), and has a dispersion of 1.0 to 10.0, more preferably The acrylic polymer has a weight average molecular weight of 4,000 to 100,000.

The acrylic polymer is a copolymer of monomers of the following monomer examples: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (A) Butyl acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, (methyl) ) decyl acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylate Tetraester, hexadecyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, (meth) acrylate Cyclopentyl ester (dicyclopentanyl (meth)acrylate), dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate (2-methoxyethyl) (meth)acrylate), 2-ethoxyethyl(meth)acrylate, acrylic acid, methacrylic acid, itaconic acid, maleic acid, cis-butane Alkylene dianhydride, monoalkyl maleate, monoalkyl itaconate, monoalkyl fumarate, glycidyl acrylate, glycidyl methacrylate, (a) 3,4-epoxybutyl acrylate, 2,3-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-(meth)acrylate 3-methyloxetane-3-methyl(meth)acrylate, 3-ethyloxetane-3-methyl (meth)acrylate, styrene, α-A Styrene, ethoxylated styrene, N-methyl maleimide, N-ethyl maleimide, N-propyl maleic acid Imine, N-butyl maleimide, N-cyclohexyl cis Two acyl imine, (meth) acrylamide, N- methyl (meth) acrylamide and the like. The acrylic polymer may be used singly or in combination of two or more.

The acrylic polymer having a propylene unsaturated bond in the side chain may be a copolymer obtained by subjecting an epoxy resin to an addition reaction of a carboxylic acid-containing acrylic copolymer. For example, an epoxy resin, a carboxylic acid-containing acrylic copolymer may be subjected to an addition reaction at a temperature of from 40 ° C to 180 ° C to obtain a binder resin, wherein the epoxy resin may be, for example, glycidyl acrylate. , glycidyl methacrylate, 3,4-epoxy-butyl (meth)acrylate, 2,3-epoxycyclohexyl (meth)acrylate, 3,4-epoxy ring (meth)acrylate a hexyl methyl ester, or an analogue thereof; the carboxylic acid-containing acrylic copolymer is obtained by copolymerizing a carboxylic acid-containing acrylic monomer (for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, and maleic acid) Diacid monoalkyl ester, or The analog thereof is obtained by copolymerization with at least two monomers selected from the group consisting of alkyl (meth)acrylate (including methyl (meth)acrylate, hexyl (meth)acrylate, etc.), (meth)acrylic acid Cyclohexyl ester, isodecyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate , 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, styrene, α-methylstyrene, ethoxylated styrene, N-methyl cis-butyl Equinone imine, N-ethyl maleimide, N-propyl maleimide, N-butyl maleimide, N-cyclohexylbutylene Amine, (meth) acrylamide, N-(meth) propylene methamine, and the like.

As another example, the acrylic polymer having a propylene unsaturated bond in the side chain may be a copolymer obtained by subjecting a carboxylic acid to an addition reaction of an epoxy group-containing acrylic copolymer, and a binder. The resin can also be obtained by subjecting a carboxylic acid-containing acrylic monomer to an epoxy group-containing acrylic copolymer at a temperature of 40 ° C to 180 ° C, wherein the carboxylic acid-containing acrylic monomer can be obtained. For example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid monoalkyl ester, or the like; the epoxy group-containing acrylic copolymer may contain a ring by copolymerization Oxygen group of acrylic monomers (for example, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxy-butyl (meth)acrylate, 2,3-epoxycyclohexane (meth)acrylate The ester, 3,4-epoxycyclohexyl (meth)acrylate, or the like thereof is obtained by copolymerization with at least two monomers selected from the group consisting of alkyl (meth)acrylates (including (meth)acrylic acid) Methyl ester, hexyl (meth) acrylate, etc., cyclohexyl (meth) acrylate, (methyl) Isodecyl enoate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylate 2 -methoxyethyl ester, 2-ethoxyethyl (meth)acrylate, styrene, α-methylstyrene, ethoxylated styrene, N-methyl cis Butylene diimide, N-ethyl maleimide, N-propyl maleimide, N-butyl maleimide, N-cyclohexyl maleic acid Imine, (meth) acrylamide, N-methyl (meth) acrylamide, and the like.

In the photoresist composition of the present invention, a polymer having an ethylenically unsaturated bond is patterned by photoreaction by photoreaction, and crosslinked under high temperature heating to provide chemical resistance and heat resistance. Sex. The polymer having an ethylenically unsaturated bond is preferably used in an amount of from 0.001% by weight to 40% by weight based on 100% by weight of the photoresist composition. When an excessive amount of a polymer having an ethylenically unsaturated bond is added, the degree of crosslinking may be extremely high to deteriorate the ductility of the pattern.

Specifically, the polymer compound having an ethylenic unsaturated bond may include an alkyl ester of (meth)acrylic acid (for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, etc., glycidyl (meth)acrylate, polyethylene glycol having 2 to 14 ethylene oxide groups Polyethylene glycol mono(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups , propylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups, trimethylolpropane di (meth) acrylate (trimethylolpropane di (meth) Acrylate), bisphenol A diglycidyl ether acrylic acid adduct, β-hydroxy ethyl (meth)acrylate Ethyl toluene diisocyanate of ester, ethyl (meth) acrylate β hydroxy ester (toluene diisocyanate Adduct), a compound obtained from an esterified polyol and an α,β-unsaturated carboxylic acid (for example, trimethylolpropane tri(meth)acrylate, neopentyl alcohol (methyl) propylene Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(methyl) propyl ester, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate And an acrylic acid adduct of dipentaerythritol tri(meth)acrylate) or a polyhydric glycidyl compound (for example, trimethylolpropane triglycidyl triacrylate) Ether acrylic acid adduct). The polymer having an ethylenically unsaturated bond may be used singly or in combination of two or more.

Further, the amount of the diterpene ester compound represented by Chemical Formula 1 used as the photopolymerization initiator in the photoresist composition of the present invention is added to increase the transparency and minimize the amount of exposure, wherein The diterpene ester compound represented by Chemical Formula 1 is preferably used in an amount of from 0.01% by weight to 10% by weight, more preferably from 0.1% by weight to 5% by weight, based on 100% by weight of the resist composition.

Further, the photoresist composition of the present invention may further comprise a silicone-based compound having an epoxy group or an amine group as a desired aid.

In the photoresist composition of the present invention, the siloxane compound can enhance the adhesion strength between the ITO electrode and the photoresist composition, and can enhance the heat resistance after curing. The oxoxane compound having an epoxy group or an amine group may include (3-glycidoxypropyl)trimethoxynonane, (3-glycidoxypropyl)triethoxy group. Decane, (3-glycidoxypropyl)methyldimethoxydecane, (3-glycidoxypropyl)methyldiethoxydecane, (3-glycidoxypropyl) Dimethyl methoxy decane, (3-glycidoxypropyl) dimethyl ethoxy decane, 3,4-epoxybutyl trimethoxy decane, 3,4-epoxy butyl Ethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, Aminopropyltrimethoxy The decane-based compound may be used singly or in combination of two or more. The use of the oxirane compound having an epoxy group or an amine group based on 100% by weight of the photoresist composition The amount is from 0.0001% by weight to 3% by weight.

Further, the photoresist composition of the present invention may further comprise a desired additive having a compatibility, for example, a photosensitizer, a thermal polymerization initiator, an antifoaming agent, a leveling agent ( Leveling agent) and so on.

The photoresist composition of the present invention is spin-coated on a substrate through a solvent and patterned by UV light on the substrate using a mask, and the substrate is developed with an alkali developer. Among them, it is preferred to adjust the viscosity to 1 centipoise (cp) to 50 centipoise by adding a solvent of 10% by weight to 95% by weight based on 100% by weight of the photoresist composition.

Considering the compatibility of the binder resin, the photoinitiator, and other compounds, the solvents exemplified below may be used singly or in combination of two or more as the solvent of the present invention: ethyl acetate, butyl acetate, diethylene glycol. Dimethyl ether, diethylene glycol dimethyl ether, methyl methoxypropionate, 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, ethyl cyproterone acetate, diethylene glycol methyl acetate, two Ethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl -2-pyrrolidone (NMP), γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, isopropanol, Methyl cyproterone, ethyl cyproterone, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, octane, or the like Things.

A known method (for example, spin coating, roll coater, bar coating, die coater, curtain coating, various printing methods, dipping) can be used. (dippings), etc.) Applying a photoresist composition according to an exemplary embodiment of the present invention to a support substrate (for example, soda glasses, quartz glass, semiconductor substrates, metals, paper, plastics, etc.) . Further, after the photoresist composition is applied to a support substrate (for example, forming a film), the photoresist composition can be transferred to other support substrates, and the method of its implementation is not limited.

The photoresist composition according to an embodiment of the present invention can be used in various applications such as photocurable coatings or lacquers, photocurable adhesives, color displays (eg, printed substrates, color televisions, personal computer screens, portable Color filter in liquid crystal display device of type information terminal, digital camera, etc., electrode material for plasma display panel, powder coating, printing ink, printing plate, adhesive, dental composition , gel coats, electronically engineered photoresists, electroplated resists, etching resists, solder resists for liquid and dry films, used to form color matrices for a variety of display applications Or a resist of a structure in the manufacturing process of a plasma display, an electroluminescence display device, and an LCD, a composition for packaging electrical and electronic components, a magnetic recording material, a fine machine component Component), waveguide, optical switche, plating mask, etching hood, color test system, fiberglass cable coating , screen printing stencils, materials for manufacturing three-dimensional objects by stereo printing, materials for holographic recording, image recording materials, precision electronic circuits, decolorizing materials, Decolorizing materials for image recording materials, decolorizing materials using microcapsules for image recording, photoresist materials for printed circuit boards, photoresist materials for UV and visible laser guided images, for use in printed circuits A photoresist material or the like which forms a dielectric layer in a sequential lamination of a board or a protective mold, but the use thereof is not limited thereto.

In a further aspect, the photoresist composition comprising the diterpene ester compound represented by Chemical Formula 1 is further included in the coloring agent.

The photoresist composition can be prepared by adding a colorant according to the use, wherein the colorant can be various, such as black, red, yellow, green, blue, and the like. Specifically, a black colorant may be added to make a black matrix, and various coloring agents showing R.G.B. color or the like may be used to manufacture a color filter.

The coloring agent included in the resist for forming a molded article (for example, a color filter, a black matrix, or the like) may include a cyan, magenta, yellow, red, green, blue, and dark blue mixture system. And black pigments. The pigment may include 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; Pig pigment Orange (Pigment Orange) 36, 43, 51, 55, 59, 61; CI Pigment Red (Pigment Red) 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240; Pigment Violet 19, 23, 29, 30, 37, 40, 50; CI Pigment Blue 15 , 15:1, 15:4, 15:6, 22, 60, 64; CI Pigment Green 7, 36; CI Pigment Brown 23, 25, 26; CI Pigment Black 7; titanium black; carbon black and the like.

Further, in a further aspect, the molded article provided includes a cured product of the foregoing photoresist composition.

Further, the molded article may be an array planarization film, an insulating film, a pillar spacer, a black pillar spacer, a black matrix, or a color filter.

Further, in a further aspect, the display device provided includes the aforementioned molded article.

When the diterpene ester compound of the present invention is used as a photopolymerization initiator as a photoresist composition, even in a small amount, it has remarkably excellent sensitivity, and excellent physical properties (for example, film retention rate, Pattern stability, chemical resistance, ductility, etc., thereby causing exhaust from the photopolymerization initiator during exposure and post-bake process of a thin film transistor liquid crystal display (TFT-LCD) manufacturing method (outgassing) is minimized, thus reducing contamination and minimizing defects that occur.

[Detailed description of the implementation]

Hereinafter, the representative compounds of the present invention will be described in detail through the detailed description of the examples and comparative examples. Therefore, the following embodiments of the present invention may be modified to various embodiments and should not be construed as limiting the scope of the present invention. The embodiments of the present invention are provided to enable those skilled in the art to have a more thorough understanding of the present invention.

[Example 1]

Preparation of 1-(biphenyl-4-yl)butane-1,3-dione O,O-diethylhydrazine dioxime (4)

Reaction 1

Synthesis of 1-(biphenyl-4-yl)butane-1,3-dione (2)

Anhydrous ethyl acetate (50 ml) was maintained under a nitrogen atmosphere at 5 ° C, and sodium hydride (3.08 g, 60% in mineral oil, 0.077 mol) was added thereto and stirred for 30 minutes. 4-Ethylbiphenyl (1) (10.0 g, 0.051 mol) dissolved in ethyl acetate (50 mL) was added and stirred for 1 hour, and the reaction solution was slowly heated and stirred at 60 ° C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, H ₂ O (30 mL) was added and stirred for about 30 minutes. Next, a 1% aqueous HCl solution (40 ml) was slowly added dropwise to neutralize the reaction mixture to a pH of 6 to 7. Ethyl acetate (100 ml) was added to the reaction solution and stirred for 30 minutes to separate the organic layer, and the separated organic layer was sufficiently washed with H ₂ O. The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(biphenyl-4-yl)butane-1,3-dione. (2) (7.2 grams) (62.0%).

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)

1-(Biphenyl-4-yl)butane-1,3-dione (2) (5.0 g, 0.021 mol) was dispersed in ethanol (100 ml) and hydroxylamine hydrochloride (4.38) Glucose, 0.063 mol, and sodium acetate (5.17 g, 0.063 mol) were added thereto, and the reaction solution was slowly heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, and distilled water (100 ml) and ethyl acetate (200 ml) were added thereto and stirred for about 30 minutes to separate the organic layer. The separated organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(biphenyl-4-yl)butane-1,3-dione. Two (3) (5.23 grams) (92.9%).

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-diethylhydrazine dioxime (4)

1-(Biphenyl-4-yl)butane-1,3-dione dioxime (3) (5.0 g, 0.019 mol) was dissolved in ethyl acetate (50 mL) under a nitrogen atmosphere. It was maintained at -5 ° C and triethylamine (4.25 g, 0.042 mol) was added thereto. The obtained reaction solution was stirred for 30 minutes, and ethyl hydrazine chloride (3.30 g, 0.042 mol) was slowly added, and the reaction solution was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(biphenyl-4-yl)butane-1,3-dione. O, O-diethyl fluorenyl (4) (5.82 g) (92.3%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.96 (6H, s), 1.88 (3H, s), 2.89 (2H, s), 7.34-7.38 (3H, m), 7.80-7.86 (4H, m), 8.01-8.12(3H, m)

MS( m/e ):352

[Example 2] Preparation of 1-(biphenyl-4-yl)butane-1,3-dione-O,O dipropenyldifluoride (5)

1-(Biphenyl-4-yl)butane-1,3-dione dioxime (3) (5.0 g, 0.019 mol) was dissolved in ethyl acetate (50 mL) under a nitrogen atmosphere. It was maintained at -5 ° C and triethylamine (4.25 g, 0.042 mol) was added thereto. The obtained reaction solution was stirred for 30 minutes, and propionyl chloride (3.88 g, 0.042 mol) was slowly added, and the reaction solution was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(biphenyl-4-yl)butane-1,3-dione. -O,O dipropenyl dioxime (5) (6.65 g) (92.0%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.96 (6H, t), 1.88 (3H, s), 2.27 (4H, q), 2.69 (2H, s), 7.35-7.38 (3H, m), 7.78- 7.82 (4H, m), 8.01-8.05 (3H, m)

MS( m/e ):380

[Example 3] Preparation of 1-(biphenyl-4-yl)butane-1,3-dione-O,O-dicyclohexanecarbonyldifluoride (6)

1-(Biphenyl-4-yl)butane-1,3-dione dioxime (3) (5.0 g, 0.019 mol) was dissolved in ethyl acetate (50 mL) under a nitrogen atmosphere. It was maintained at -5 ° C and triethylamine (4.25 g, 0.042 mol) was added thereto. The obtained reaction solution was stirred for 30 minutes, and cyclohexanecarbonyl chloride (6.16 g, 0.042 mol) was slowly added, and the reaction solution was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(biphenyl-4-yl)butane-1,3-dione. -O,O-Dicyclohexanecarbonyldiindole (6) (8.54 g) (92.0%).

¹ H NMR (δ ppm; CDCl ₃ ): 1.12-1.15 (10H, m), 1.60-1.66 (12H, m), 1.88 (3H, s), 2.69 (2H, s), 7.35-7.38 (3H, m ), 7.78-7.82 (4H, m), 8.01-8.05 (3H, m)

MS( m/e ):487

[Example 4] Preparation of 1-(biphenyl-4-yl)butane-1,3-dione O,O-dibenzimidoxime (7)

1-(Biphenyl-4-yl)butane-1,3-dione dioxime (3) (5.0 g, 0.019 mol) was dissolved in ethyl acetate (50 mL) under nitrogen atmosphere. The system was maintained at -5 ° C and triethylamine (4.25 g, 0.042 mol) was added thereto. The obtained reaction solution was stirred for 30 minutes, and benzamidine chloride (5.90 g, 0.042 mol) was slowly added, and the reaction solution was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(biphenyl-4-yl)butane-1,3-dione. O, O-benzophenone dioxime (7) (8.26 g) (91.2%).

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-diethylhydrazine dioxime (11)

Reaction 1

Synthesis of 1-(biphenyl-4-yl)-2-methylbutane-1,3-dione (1-(biphenyl-4-yl)-2-methylbutane-1,3-dione)(9)

Anhydrous ethyl acetate (50 ml) was maintained under a nitrogen atmosphere at 5 ° C, sodium hydride (2.88 g, 60% in mineral oil, 0.072 mol) was added and stirred for 30 minutes. 4-propenylbiphenyl (8) (10.0 g, 0.048 mol) dissolved in ethyl acetate (50 mL) was added and stirred for 1 hour, and the reaction solution was slowly heated and stirred at 60 ° C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, H ₂ O (30 mL) was added and stirred for about 30 minutes. Next, a 1% aqueous HCl solution (40 ml) was slowly added dropwise to neutralize the reaction mixture to a pH of 6 to 7. Ethyl acetate (100 ml) was added to the reaction solution and stirred for 30 minutes to separate the organic layer, and the separated organic layer was sufficiently washed with H ₂ O. The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to afford 1-(biphenyl-4-yl)-2-methylbutane-1 , 3-dione (9) (7.07 g) (58.2%).

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

1-(biphenyl-4-yl)-2-methylbutane-1,3-dione di-oxime (1-(biphenyl-4-yl)-2-methylbutane-1,3-dione di-oxime) Preparation of (10)

1-(Biphenyl-4-yl)-2-methylbutane-1,3-dione (9) (5.0 g, 0.020 mol) was dispersed in ethanol (100 mL) and hydroxylamine hydrochloride ( 4.18 g, 0.060 mol) and sodium acetate (4.92 g, 0.060 mol) were added thereto, the reaction solution was slowly heated and refluxed 1 hour. The reaction mixture was cooled to room temperature, and distilled water (100 ml) and ethyl acetate (200 ml) was added thereto and stirred for about 30 minutes to separate the organic layer, and the separated organic layer was dried over anhydrous magnesium sulfate and under reduced pressure. Distill the solvent. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to afford 1-(biphenyl-4-yl)-2-methylbutane-1 , 3-dione dioxime (10) (5.02 g) (88.9%).

^{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

Preparation of 1-(biphenyl-4-yl)-2-methylbutane-1,3-dione O,O-diethylhydrazine dioxime (11)

1-(Biphenyl-4-yl)-2-methylbutane-1,3-dione dioxime (10) (5.0 g, 0.018 mol) was dissolved in ethyl acetate (50 mL). The reaction mixture was maintained at -5 ° C and triethylamine (4.05 g, 0.040 mol) was added. The obtained reaction solution was stirred for 30 minutes, and ethyl hydrazine chloride (3.14 g, 0.040 mol) was slowly added, and the reaction mixture was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to afford 1-(biphenyl-4-yl)-2-methylbutane-1 , 3- Diketone O, O-diethylhydrazine dioxime (11) (5.94 g) (90.1%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.96 (6H, s), 1.32 (3H, d), 1.88 (3H, s), 3.89 (1H, m), 7.34-7.38 (3H, m), 7.80- 7.86 (4H, m), 8.01-8.12 (3H, m)

MS( m/e ):366

[Example 6] Preparation of 1-(biphenyl-4-yl)-2-methylbutane-1,3-dione-O, O-dicyclohexanecarbonyldifluorene (12)

1-(Biphenyl-4-yl)-2-methylbutane-1,3-dione dioxime (10) (5.0 g, 0.018 mol) was dissolved in ethyl acetate (50 mL). The reaction mixture was maintained at -5 ° C and triethylamine (4.05 g, 0.040 mol) was added. The obtained reaction solution was stirred for 30 minutes, and cyclohexanecarbonyl chloride (5.86 g, 0.040 mol) was slowly added, and the reaction solution was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to afford 1-(biphenyl-4-yl)-2-methylbutane-1 , 3-dione-O, O-dicyclohexanecarbonyldifluorene (12) (8.48 g) (88.8%).

¹ H NMR (δ ppm; CDCl ₃ ): 1.12-1.14 (10H, m), 1.30 (3H, d), 1.62-1.66 (12H, m), 1.90 (3H, s), 3.85 (1H, m), 7.36-7.38(3H,m),7.82-7.86(4H,m),8.01-8.08(3H,m)

MS( m/e ):503

[Embodiment 7]

Preparation of 1-(biphenyl-4-yl)-2-methylbutane-1,3-dione O,O-dibenzimidoxime (13)

1-(Biphenyl-4-yl)-2-methylbutane-1,3-dione dioxime (10) (5.0 g, 0.018 mol) was dissolved in ethyl acetate (50 mL). The reaction mixture was maintained at -5 ° C and triethylamine (4.05 g, 0.040 mol) was added. The obtained reaction solution was stirred for 30 minutes, and benzamidine chloride (5.62 g, 0.040 mol) was slowly added, and the reaction mixture was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to afford 1-(biphenyl-4-yl)-2-methylbutane-1 , 3-dione O, O-benzophenone dioxime (13) (8.22 g) (88.2%).

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-diethylhydrazine dioxime (18)

Reaction 1

Synthesis of 1-(biphenyl-4-yl)-2-cyclohexylethanone (15)

Biphenyl (14) (10.0 g, 0.065 mol) was dispersed in dichloromethane (100 mL) and the reaction mixture was cooled to -5 C and aluminum chloride (10.40 g, 0.78 m) was slowly added. Then, 2-cyclohexylethenyl chloride (12.53 g, 0.078 mol) diluted in dichloromethane (5 ml) was slowly and carefully added over 2 hours so that the temperature of the reaction mixture did not rise and then The reaction mixture was stirred at -5 °C for 1 hour. Next, the reaction mixture was slowly poured into ice water (1 liter) and stirred for 30 minutes to separate the organic layer, and the collected organic layer was washed with distilled water (500 ml) and distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(biphenyl-4-yl)-2-cyclohexyl ketone (15). ) (11.07 grams) (61.2%).

¹ H NMR (δ ppm; CDCl ₃ ): 1.12-1.14 (10H, m), 1.62-1.66 (12H, m), 2.51 (2H, d), 7.36-7.38 (3H, m), 7.82-7.86 (4H ,m), 8.01-8.08 (2H, m)

MS( m/e ):278

Reaction 2

Synthesis of 1-(biphenyl-4-yl)-2-cyclohexylbutane-1,3-dione (16)

Anhydrous ethyl acetate (50 ml) was maintained under a nitrogen atmosphere at 5 ° C, sodium hydride (2.16 g, 60% in mineral oil, 0.054 mol) was added thereto and stirred for 30 minutes. Add 1-(biphenyl-4-yl)-2-cyclohexylethanone (15) (10.0 g, 0.036 mol) dissolved in ethyl acetate (50 mL) and stir for 1 hour, slowly heat the reaction solution and The reaction was completed by stirring at 60 ° C for 5 hours. The reaction solution was cooled to room temperature, H ₂ O (30 mL) was added and stirred for about 30 minutes. Next, a 1% aqueous HCl solution (30 ml) was slowly added dropwise to neutralize the reaction mixture to a pH of 6 to 7. Ethyl acetate (100 ml) was added to the reaction solution and stirred for 30 minutes to separate the organic layer, and the separated organic layer was sufficiently washed with H ₂ O. The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to afford 1-(biphenyl-4-yl)-2-cyclohexylbutane-1 , 3-dione (16) (6.37 g) (55.2%).

¹ H NMR (δ ppm; CDCl ₃ ): 1.12-1.14 (10H, m), 1.62-1.66 (12H, m), 2.10 (3H, s), 3.51 (1H, d), 7.36-7.38 (3H, m ), 7.82-7.86 (4H, m), 8.01-8.08 (2H, m)

MS( m/e ):320

Reaction 3

1-(biphenyl-4-yl)-2-cyclohexylbutane-1,3-dione dioxime Synthesis of (1-(biphenyl-4-yl)-2-cyclohexylbutane-1,3-dione di-oxime)(17)

1-(Biphenyl-4-yl)-2-cyclohexylbutane-1,3-dione (16) (5.0 g, 0.016 mol) was dispersed in ethanol (100 mL) and hydroxylamine hydrochloride ( 3.34 g, 0.048 mol) and sodium acetate (3.94 g, 0.048 mol) were added thereto, and the reaction solution was slowly heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, and distilled water (100 ml) and ethyl acetate (200 ml) was added thereto and stirred for 30 minutes to separate the organic layer, and the separated organic layer was dried over anhydrous magnesium sulfate and distilled under reduced pressure. Solvent. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to afford 1-(biphenyl-4-yl)-2-cyclohexylbutane-1 , 3-dione dioxime (17) (4.87 g) (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 (4H, 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-diethylhydrazine dioxime (18)

1-(Biphenyl-4-yl)-2-cyclohexylbutane-1,3-dione II under a nitrogen atmosphere Toluene (17) (5.0 g, 0.014 mol) was dissolved in ethyl acetate (50 mL). The mixture was maintained at -5[deg.] C. and triethylamine (3.24 g, 0.032 mole) was added. The obtained reaction solution was stirred for 30 minutes, and ethyl hydrazine chloride (2.51 g, 0.032 mol) was slowly added, and the reaction mixture was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to afford 1-(biphenyl-4-yl)-2-cyclohexylbutane-1 , 3-dione O, O-diethylhydrazine dihydrazide (18) (5.49 g) (90.3%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.96 (6H, s), 1.10 - 10.12 (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-diethylhydrazinedi(22)

Reaction 1

Synthesis of 1-(biphenyl-4-yl)-3-cyclopentylpropane-1-one (19)

Dispersion of biphenyl (14) in dichloromethane (100 ml) (10.0 g, 0.065 Mohr) and the reaction mixture was cooled to -5 ° C, and aluminum chloride (10.40 g, 0.78 mol) was slowly added thereto. The 3-cyclopentylpropane chloride (12.53 g, 0.078 mol) diluted in dichloromethane (5 mL) was slowly and carefully added over 2 hours so that the temperature of the reaction mixture did not rise and The reaction mixture was stirred at -5 °C for 1 hour. Next, the reaction mixture was slowly poured into ice water (1 liter) and stirred for 30 minutes to separate the organic layer, and the collected organic layer was washed with distilled water (500 ml) and distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to give 1-(biphenyl-4-yl)-3-cyclopentylpropane-1 - Ketone (19) (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

1-(biphenyl-4-yl)-2-cyclopentylmethyl)butane-1,3-dione (1-(biphenyl-4-yl)-2-cyclopentylmethyl)butane-1,3-dione ) (20) synthesis

Anhydrous ethyl acetate (50 ml) was maintained under a nitrogen atmosphere at 5 ° C, sodium hydride (2.16 g, 60% in mineral oil, 0.054 mol) was added thereto and stirred for 30 minutes. Add 1-(biphenyl-4-yl)-3-cyclopentylpropan-1-one (19) (10.0 g, 0.036 mol) dissolved in ethyl acetate (50 mL) and stir for 1 hour. The reaction solution was stirred at 60 ° C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, H ₂ O (30 mL) was added and stirred for about 30 minutes. Next, a 1% aqueous HCl solution (30 ml) was slowly added dropwise to neutralize the reaction mixture to a pH of 6 to 7. Ethyl acetate (100 ml) was added to the reaction solution and stirred for 30 minutes to separate the organic layer, and the separated organic layer was sufficiently washed with H ₂ O. The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to give 1-(biphenyl-4-yl)-2-cyclopentylmethyl) Butane-1,3-dione (20) (6.37 g) (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 (4H, m), 8.01-8.08 (2H, m)

MS( m/e ):320

Reaction 3

1-(biphenyl-4-yl)-2-cyclopentylmethyl)butane-1,3-dione dioxime (1-(biphenyl-4-yl)-2-cyclopentylmethyl)butane-1,3 Synthesis of -dione di-oxime)(21)

1-(Biphenyl-4-yl)-2-cyclopentylmethyl)butane-1,3-dione (20) (5.0 g, 0.016 mol) dispersed in ethanol (100 mL), hydroxylamine Hydrochloride (3.34 g, 0.048 mol) and sodium acetate (3.94 g, 0.048 mol) were added thereto, and the reaction solution was slowly heated and refluxed for 1 hour. Cool the reaction mixture to room temperature, distilled water (100 mL) and acetic acid Ethyl acetate (200 ml) was added thereto and stirred for about 30 minutes to separate an organic layer, the separated organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to give 1-(biphenyl-4-yl)-2-cyclopentylmethyl) Butane-1,3-dione dioxime (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 (4H, 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-diethylhydrazine dioxime (22)

1-(Biphenyl-4-yl)-2-cyclopentylmethyl)butane-1,3-dione dioxime (21) (5.0 g, 0.014 mol) was dissolved in acetic acid B under a nitrogen atmosphere The ester (50 ml) was maintained at -5 °C and triethylamine (3.24 g, 0.032 mol) was added. The obtained reaction solution was stirred for 30 minutes, and ethyl hydrazine chloride (2.51 g, 0.032 mol) was slowly added, and the reaction mixture was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. Obtained by gel column chromatography Product (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(biphenyl-4-yl)-2-cyclopentylmethyl)butane-1,3-dione O, O-diethylhydrazine dioxime (22) (5.49 g) (90.3%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.96 (6H, s), 1.35-1.60 (9H, m), 1.48 (2H, m), 2.05 (3H, s), 2.42 (2H, t), 7.33 7.35(3H,m), 7.80-7.82(4H,m),8.01-8.06(2H,m)

MS( m/e ):435

[Example 10] Preparation of 1-(biphenyl-4-yl)hexane-1,3-dione O,O-diethylhydrazine dioxime (25)

Reaction 1

Synthesis of 1-(biphenyl-4-yl)-hexane-1,3-dione (23)

Anhydrous ethyl acetate (50 ml) was maintained under a nitrogen atmosphere at 5 ° C, and sodium hydride (3.08 g, 60% in mineral oil, 0.077 mol) was added thereto and stirred for 30 minutes. 4-Ethylbiphenylbiphenyl (1) (10.0 g, 0.051 mol) dissolved in butyl acetate (50 mL) was added and stirred for 1 hour, and the reaction solution was slowly heated and stirred at 60 ° C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, H ₂ O (30 mL) was added and stirred for about 30 minutes. Next, a 1% aqueous HCl solution (40 ml) was slowly added dropwise to neutralize the reaction mixture to a pH of 6 to 7. Ethyl acetate (100 ml) was added to the reaction solution and stirred for 30 minutes to separate the organic layer, and the separated organic layer was sufficiently washed with H ₂ O. The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(biphenyl-4-yl)-hexane-1,3-di. Ketone (23) (8.01 g) (59.0%).

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 di-oxime (24)

1-(Biphenyl-4-yl)-hexane-1,3-dione (23) (5.0 g, 0.019 mol) was dispersed in ethanol (100 mL) and hydroxylamine hydrochloride (3.97 g, 0.057) Mol) and sodium acetate (4.68 g, 0.057 mol) were added thereto, and the reaction solution was slowly heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, and distilled water (100 ml) and ethyl acetate (200 ml) was added thereto and stirred for about 30 minutes to separate the organic layer, and the separated organic layer was dried over anhydrous magnesium sulfate and under reduced pressure. Distill the solvent. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(biphenyl-4-yl)hexane-1,3-dione. Two (24) (5.01 grams) (88.9%).

^{1 H NMR (δ ppm; CDCl} 3): 0.95 (3H, t), 1.61 (2H, q), 1.86 (3H, s), 2.89 (2H, s), 7.34-7.38 (3H, m), 7.80- 7.86(4H,m), 8.01-8.12(2H,m)

MS( m/e ):296

Reaction 3

Synthesis of 1-(biphenyl-4-yl)hexane-1,3-dione O,O-diethylhydrazinedifluoride (25)

1-(Biphenyl-4-yl)hexane-1,3-dione dioxime (24) (5.0 g, 0.017 mol) was dissolved in ethyl acetate (50 mL) under nitrogen atmosphere. At -5 ° C, triethylamine (3.74 g, 0.037 mol) was added. The obtained reaction solution was stirred for 30 minutes, and ethyl hydrazine chloride (2.90 g, 0.037 mol) was slowly added, and the reaction mixture was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(biphenyl-4-yl)hexane-1,3-dione. O, O-diethyl fluorenyl (25) (5.84 g) (90.3%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.94 (3H, t), 0.96 (6H, s), 1.61 (2H, q), 1.88 (3H, s), 2.89 (2H, s), 7.34-7.38 (3H,m) 7.80-7.86(4H,m),8.01-8.12(3H,m)

MS( m/e ):380

[Example 11] Preparation of 1-(biphenyl-4-yl)pentane-1,4-dione O,O-diethylhydrazine dioxime (28)

Reaction 1

Synthesis of 1-(biphenyl-4-yl)pentane-1,4-dione (26)

Anhydrous ethyl acetate (50 ml) was maintained under a nitrogen atmosphere at 5 ° C, sodium hydride (5.96 g, 60% in mineral oil, 0.144 mol) was added and stirred for 30 minutes. 4-Propanylbiphenyl (8) (20.0 g, 0.096 mol) dissolved in ethyl acetate (50 mL) was added and stirred for 1 hour, and the reaction solution was slowly heated and stirred at 60 ° C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, H ₂ O (30 mL) was added and stirred for about 30 minutes. Next, a 1% aqueous HCl solution (80 ml) was slowly added dropwise to neutralize the reaction mixture to a pH of 6 to 7. Ethyl acetate (100 ml) was added to the reaction solution and stirred for 30 minutes to separate the organic layer, and the separated organic layer was sufficiently washed with H ₂ O. The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(biphenyl-4-yl)pentane-1,4-dione. (26) (6.35 grams) (26.2%).

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 di-oxime (27)

1-(Biphenyl-4-yl)pentane-1,4-dione (26) (5.0 g, 0.020 mol) was dispersed in ethanol (100 mL) and hydroxylamine hydrochloride (4.18 g, 0.060 Mo) The ear) and sodium acetate (4.92 g, 0.060 mol) were added thereto, and the reaction solution was slowly heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, and distilled water (100 ml) and ethyl acetate (200 ml) was added thereto and stirred for about 30 minutes to separate the organic layer, and the separated organic layer was dried over anhydrous magnesium sulfate and under reduced pressure. Distill the solvent. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(biphenyl-4-yl)pentane-1,4-dione. Two (27) (4.98 grams) (88.2%).

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-diethylhydrazine dioxime (28)

1-(Biphenyl-4-yl)pentane-1,4-dione dioxime (27) (5.0 g, 0.018 mol) was dissolved in ethyl acetate (50 mL) under nitrogen atmosphere. At -5 ° C, triethylamine (4.05 g, 0.040 mol) was added. The obtained reaction solution was stirred for 30 minutes, and ethyl hydrazine chloride (3.14 g, 0.040 mol) was slowly added, and the reaction mixture was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(biphenyl-4-yl)pentane-1,4-dione. O, O-diethylhydrazine dioxime (28) (5.88 g) (89.1%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.96 (6H, s), 1.90 (3H, s), 2.45 (2H, t), 2.96 (2H, t), 7.34-7.38 (3H, m), 7.80- 7.86 (4H, m), 8.01-8.12 (3H, m)

MS( m/e ):366

[Embodiment 12]

Preparation of 1-(biphenyl-4-yl)pentane-1,4-dione-O,O-dicyclohexanecarbonyldifluorene (29)

1-(Biphenyl-4-yl)pentane-1,4-dione dioxime (27) (5.0 g, 0.018 mol) was dissolved in ethyl acetate (50 mL) under nitrogen atmosphere. At -5 ° C, triethylamine (4.05 g, 0.040 mol) was added. Stir the obtained reaction solution for 30 minutes Clock, and slowly add cyclohexanecarbonyl chloride (5.86 g, 0.040 mol), and carefully stir the reaction mixture for 30 minutes so that its temperature does not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(biphenyl-4-yl)pentane-1,4-dione. -O,O-dicyclohexanecarbonyldifluorene (29) (18.00 g) (89.5%).

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-benzophenone dioxime (30)

1-(Biphenyl-4-yl)pentane-1,4-dione dioxime (27) (5.0 g, 0.018 mol) was dissolved in ethyl acetate (50 mL) under nitrogen atmosphere. At -5 ° C, triethylamine (4.05 g, 0.040 mol) was added. The obtained reaction solution was stirred for 30 minutes, and benzamidine chloride (5.62 g, 0.040 mol) was slowly added, and the reaction mixture was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, and the collected organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(biphenyl-4-yl)pentane-1,4-dione. O, O-benzophenone dioxime (30) (17.36 g) (88.5%).

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), 8.01-8.043H, 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-diethylenedifluoride (34)

Reaction 1

Synthesis of 1-(4'-nitro-biphenyl-4-yl)ethanone (31)

4-Ethylbiphenyl (1) (21.6 g, 0.11 mol) was dissolved in concentrated sulfuric acid (150 ml), the reaction mixture was maintained at -10 ° C, and potassium nitrate was slowly added over 3 hours. 12.1 grams, 0.12 moles, and the reaction mixture was stirred at -10 °C for 30 minutes. Next, ethanol (400 ml) was carefully added so that the temperature of the reaction mixture did not exceed 0 ° C, and the reaction product was stirred for 1 hour and filtered. The obtained solid product was dispersed in distilled water (500 ml) and stirred at room temperature for 30 minutes, filtered and thoroughly washed with distilled water, and the product was dried to obtain light-colored 1-(4'-nitro-biphenyl- 4-yl)ethanone (31) (17.8 g) (67.2%).

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

1-(4'-Nitro-biphenyl-4-yl)butane-1,3-dione (1-(4'-nitro-biphenyl-4-yl)butane-1,3-dione) (32 )Synthesis

Anhydrous ethyl acetate (50 ml) was maintained under a nitrogen atmosphere at 5 ° C, sodium hydride (5.00 g, 60% in mineral oil, 0.125 mol) was added thereto and stirred for 30 minutes. Add 1-(4'-nitro-biphenyl-4-yl)ethanone (31) (20.0 g, 0.083 mol) dissolved in ethyl acetate (50 mL) and stir for 1 hour. The reaction was completed by stirring at 60 ° C for 5 hours. The reaction solution was cooled to room temperature, H ₂ O (30 mL) was added and stirred for about 30 minutes. Next, a 1% aqueous HCl solution (80 ml) was slowly added dropwise to neutralize the reaction mixture to a pH of 6 to 7. Ethyl acetate (100 ml) was added to the reaction solution and stirred for 30 minutes to separate the organic layer, and the separated organic layer was sufficiently washed with H ₂ O. The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(4'-nitro-biphenyl-4-yl)butane- 1,3-diketone (32) (13.59 g) (57.8%).

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

1-(4'-nitro-biphenyl-4-yl)butane-1,3-dione dioxime (1-(4'-nitro-biphenyl-4-yl)butane-1,3-dione di Synthesis of -oxime)(33)

1-(4'-Nitro-biphenyl-4-yl)butane-1,3-dione (32) (5.0 g, 0.018 mol) was dispersed in ethanol (100 mL). (3.76 g, 0.054 mol) and sodium acetate (4.43 g, 0.054 mol) were added thereto, and the reaction solution was slowly heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, and distilled water (100 ml) and ethyl acetate (200 ml) was added thereto and stirred for about 30 minutes to separate the organic layer, and the separated organic layer was dried over anhydrous magnesium sulfate and under reduced pressure. Distill the solvent. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(4'-nitro-biphenyl-4-yl)butane- 1,3-diketone dipoxide (33) (4.97 g) (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-diethylhydrazine dioxime (34)

1-(4'-Nitro-biphenyl-4-yl)butane-1,3-dione dioxime (33) under nitrogen atmosphere (5.0 g, 0.016 mol) was dissolved in ethyl acetate (50 mL). The reaction mixture was maintained at -5[deg.] C. and triethylamine (3.56 g, 0.035 m) was added. The obtained reaction solution was stirred for 30 minutes, and ethyl hydrazine chloride (2.75 g, 0.035 mol) was slowly added, and the reaction mixture was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(4'-nitro-biphenyl-4-yl)butane- 1,3-diketone O, O-diethylhydrazine diazide (34) (5.67 g) (89.1%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.96 (6H, s), 1.90 (3H, s), 2.45 (2H, s), 7.70-7.76 (4H, m), 8.00 (2H, d), 8.25 ( 2H,d)

MS (m / e): 397

[Example 15] Preparation of 1-(4'-nitrobiphenyl-4-yl)butane-1,3-dione-O,O-dicyclohexanecarbonyldifluorene (35)

1-(4'-Nitro-biphenyl-4-yl)butane-1,3-dione dioxime (33) (5.0 g, 0.016 mol) was dissolved in ethyl acetate (50 mL). The reaction mixture was maintained at -5 ° C and triethylamine (3.56 g, 0.035 mol) was added. The obtained reaction solution was stirred for 30 minutes, and cyclohexanecarbonyl chloride (5.13 g, 0.035 mol) was slowly added, and the reaction solution was carefully stirred for 30 minutes so that the temperature did not rise. Pick up, slowly add distilled water (50 ml) to the reaction The mixture was stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(4'-nitrobiphenyl-4-yl)butane-1 , 3-dione-O, O-dicyclohexanecarbonyldifluorene (35) (7.35 g) (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-benzophenone dioxime (36)

1-(4'-Nitro-biphenyl-4-yl)butane-1,3-dione dioxime (33) (5.0 g, 0.016 mol) was dissolved in ethyl acetate (50 mL). The reaction mixture was maintained at -5 ° C and triethylamine (3.56 g, 0.035 mol) was added. The obtained reaction solution was stirred for 30 minutes, and benzamidine chloride (4.92 g, 0.035 mol) was slowly added, and the reaction solution was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(4'-nitrobiphenyl-4-yl)butane-1 , 3-dione O, O- Dibenzopyrene (36) (7.19 g) (86.2%).

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-diethylhydrazine dioxime (17)

Reaction 1

1-cyclohexyl-3-(4'-nitrobiphenyl-4-yl)propane-1,3 -dione) Synthesis of (37)

Anhydrous ethyl acetate (50 ml) was maintained under a nitrogen atmosphere at 5 ° C, sodium hydride (5.00 g, 60% in mineral oil, 0.125 mol) was added thereto and stirred for 30 minutes. Add 1-(4'-nitro-biphenyl-4-yl)ethanone (31) (20.0 g, 0.083 mol) dissolved in ethyl cyclohexanecarboxylate (50 mL) and stir. After 1 hour, the reaction solution was slowly heated and stirred at 60 ° C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, H ₂ O (30 mL) was added and stirred for about 30 minutes. Next, a 1% aqueous HCl solution (80 ml) was slowly added dropwise to neutralize the reaction mixture to a pH of 6 to 7. Ethyl acetate (100 ml) was added to the reaction solution and stirred for 30 minutes to separate the organic layer, and the separated organic layer was sufficiently washed with H ₂ O. The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-cyclohexyl-3-(4'-nitrobiphenyl-4-yl) Propane-1,3-dione (37) (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

1-cyclohexyl-3-(4'-nitrobiphenyl-4-yl)propane-1,3-cyclohexyl-3-(4'-nitrobiphenyl-4-yl)propane-1 ,3-dione di-oxime)(38) Synthesis

1-Cyclohexyl-3-(4'-nitrobiphenyl-4-yl)propane-1,3-dione (37) (10.0 g, 0.028 mol) dispersed in ethanol (100 mL), hydroxylamine Hydrochloride (5.85 g, 0.084 mol) and sodium acetate (6.89 g, 0.084 mol) were added thereto, and the reaction solution was slowly heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, and distilled water (100 ml) and ethyl acetate (200 ml) was added thereto and stirred for about 30 minutes to separate the organic layer, and the separated organic layer was dried over anhydrous magnesium sulfate and under reduced pressure. Distill the solvent. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-cyclohexyl-3-(4'-nitrobiphenyl-4-yl) Propane-1,3-dione dioxime (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-diethylhydrazine dioxime (39)

Dissolving 1-cyclohexyl-3-(4'-nitrobiphenyl-4-yl)propane-1,3-dione dioxime (38) (5.0 g, 0.013 mol) in ethyl acetate under nitrogen atmosphere (50 ml), the reaction mixture was maintained at -5 ° C, and triethylamine (2.93 g, 0.029 mol) was added. The obtained reaction solution was stirred for 30 minutes, and ethyl hydrazine chloride (2.28 g, 0.029 mol) was slowly added, and the reaction mixture was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-cyclohexyl-3-(4'-nitrobiphenyl-4-yl) Propane-1,3-dione O, O-diethylhydrazine dioxime (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-diethylhydrazine dioxime (44)

Reaction 1

Synthesis of 1-(biphenyl-4-yl)heptane-1-one (40)

Biphenyl (14) (10.0 g, 0.065 mol) was dispersed in dichloromethane (100 mL) and the reaction mixture was cooled to -5 C and aluminum chloride (10.40 g, 0.78 m) was slowly added. The addition of heptyl chloride (11.59 grams, 0.078 moles) diluted in dichloromethane (5 mL) was slowly and carefully added over 2 hours so that the temperature of the reaction mixture did not rise and the reaction mixture was Stir at -5 ° C for 1 hour. Next, the reaction mixture was slowly poured into ice water (1 liter) and stirred for 30 minutes to separate the organic layer, and the collected organic layer was washed with distilled water (500 ml) and distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to give 1-(biphenyl-4-yl)heptane-1-one (40) (10.56 grams) (61.0%).

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

1-(4'-nitro-biphenyl-4-yl)heptane-1-one (1-(4'-nitro-biphenyl-4-yl)heptane-1-one) Synthesis of (41)

Dissolving 1-(biphenyl-4-yl)heptan-1-one (40) (10.0 g, 0.038 mol) in concentrated sulfuric acid (100 mL), maintaining the reaction mixture at -10 °C, and Potassium nitrate (4.65 grams, 0.046 moles) was slowly added over 3 hours and the reaction mixture was stirred at -10 °C for 30 minutes. Next, ethanol (400 ml) was carefully added so that the temperature of the reaction mixture did not exceed 0 ° C, and the reaction product was stirred for 1 hour and filtered. The obtained solid product was dispersed in distilled water (500 ml) and stirred at room temperature for about 30 minutes, filtered and thoroughly washed with distilled water, and the product was dried to obtain a light gray 1-(4'-nitro-biphenyl. 4-yl)heptane-1-one (41) (7.36 g) (62.2%).

^{1 H-NMR (δ ppm;} CDCl 3): 0.87 (3H, t), 1.28 (8H, m), 1.72 (2H, m), 7.71-7.78 (4H, m), 8.05 (2H, d), 8.31 (2H,d)

MS( m/e ):311

Reaction 3

1-(4'-nitro-biphenyl-4-yl)-2-pentylbutane-1,3-dione (1-(4'-nitro-biphenyl-4-yl)-2-pentylbutane- Synthesis of 1,3-dione) (42)

Anhydrous ethyl acetate (50 ml) was maintained under a nitrogen atmosphere at 5 ° C, sodium hydride (1.92 g, 60% in mineral oil, 0.048 m) was added and stirred for 30 minutes. Add 1-(4'-nitro-biphenyl-4-yl)heptane-1-one (41) (10.0 g, 0.032 mol) dissolved in ethyl acetate (50 mL) and stir for 1 hour, slowly The reaction solution was heated and stirred at 60 ° C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, H ₂ O (30 mL) was added and stirred for about 30 minutes. Next, a 1% aqueous HCl solution (30 ml) was slowly added dropwise to neutralize the reaction mixture to a pH of 6 to 7. Ethyl acetate (100 ml) was added to the reaction solution and stirred for 30 minutes to separate the organic layer, and the separated organic layer was sufficiently washed with H ₂ O. The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to give 1-(4'-nitro-biphenyl-4-yl)-2- Butylbutane-1,3-dione (42) (5.89 g) (52.1%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.87 (3H, t), 1.28 (8H, m), 1.72 (1H, t), 2.10 (3H, s), 7.32-7.36 (3H, m), 7.80- 7.84(4H,m), 8.01-8.06(2H,m)

MS( m/e ):353

Reaction 4

1-(4'-Nitro-biphenyl-4-yl)-2-pentylbutane-1,3-dione dioxime (1-(4'-nitro-biphenyl-4-yl)-2- Synthesis of pentylbutane-1,3-dione di-oxime)(43)

1-(4'-Nitro-biphenyl-4-yl)-2-pentylbutane-1,3-dione (42) (5.0 g, 0.014 mol) was dispersed in ethanol (100 mL). Hydroxylamine hydrochloride (2.92 g, 0.042 mol) and sodium acetate (3.45 g, 0.042 mol) were added thereto, and the reaction solution was slowly heated and Reflux for 1 hour. The reaction mixture was cooled to room temperature, and distilled water (100 ml) and ethyl acetate (200 ml) was added thereto and stirred for about 30 minutes to separate the organic layer, and the separated organic layer was dried over anhydrous magnesium sulfate and under reduced pressure. Distill the solvent. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to give 1-(4'-nitro-biphenyl-4-yl)-2- Amyl butane-1,3-dione dioxime (43) (4.45 g) (82.9%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.88 (3H, t), 1.29 (8H, m), 1.72 (1H, t), 2.09 (3H, s), 3.44 (1H, d), 7.32-7.34 ( 3H, m), 7.80-7.82 (4H, m), 8.01-8.06 (2H, m)

MS( m/e ): 383

Reaction 5

Synthesis of 1-(4'-nitro-biphenyl-4-yl)-2-pentylbutane-1,3-dione O,O-diethylhydrazine dioxime (44)

Dissolving 1-(4'-nitro-biphenyl-4-yl)-2-pentylbutane-1,3-dione dioxime (43) (5.0 g, 0.013 mol) in a nitrogen atmosphere Ethyl acetate (50 mL), the reaction mixture was maintained at -5 °C, and triethylamine (2.93 g, 0.029 m) was added. The obtained reaction solution was stirred for 30 minutes, and ethyl hydrazine chloride (2.28 g, 0.029 mol) was slowly added, and the reaction mixture was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. Purified by gel column chromatography Product (eluent; ethyl acetate: n-hexane = 1:4) to give 1-(4'-nitro-biphenyl-4-yl)-2-pentylbutane-1,3-dione O O-diethyl fluorenyl dihydrazide (44) (5.55 g) (91.3%).

^{1 H NMR (δ ppm; CDCl} 3): 0.86 (3H, t), 0.96 (6H, s), 1.28 (8H, m), 1.72 (1H, t), 7.33-7.35 (3H, m), 7.80- 7.82 (4H, m), 8.01-8.06 (2H, m)

MS( m/e ):468

[Example 19] Preparation of 1-(4'-nitrobiphenyl-4-yl)-2-pentylbutane-1,3-dione O,O-benzophenanthridine (45)

Dissolving 1-(4'-nitro-biphenyl-4-yl)-2-pentylbutane-1,3-dione dioxime (43) (5.0 g, 0.013 mol) in a nitrogen atmosphere Ethyl acetate (50 mL), the reaction mixture was maintained at -5 °C, and triethylamine (2.93 g, 0.029 m) was added. The obtained reaction solution was stirred for 30 minutes, and benzamidine chloride (4.07 g, 0.029 mol) was slowly added, and the reaction mixture was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(4'-nitrobiphenyl-4-yl)-2-pentene Butadiene-1,3-dione O, O-benzophenone dioxime (45) (6.87 g) (89.3%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.88 (3H, t), 1.28 (8H, m), 1.74 (1H, t), 7.56-7.58 (6H, m), 7.71-7.75 (4H, m), 7.80-7.82 (4H, m), 8.03 (2H, d), 8.24 (2H, d)

MS( m/e ):592

[Example 20] 1-cyclohexyl-3-(4'-nitrobiphenyl-4-yl)-2-pentylpropane-1,3-dione O,O-diethylhydrazine dioxime (48 Preparation

Reaction 1

1-cyclohexyl-3-(4'-nitrobiphenyl-4-yl)-2-pentylpropane-1,3-dione (1-cyclohexyl-3-(4'-nitrobiphenyl-4-yl) Synthesis of -2-pentylpropane-1,3-dione) (46)

Anhydrous ethylcyclohexanecarboxylate (50 ml) was maintained under a nitrogen atmosphere at 5 ° C, sodium hydride (2.16 g, 60% in mineral oil, 0.054 mol) was added thereto and stirred for 30 minutes. Add 1-(4'-nitro-biphenyl-4-yl)heptane-1-one (41) (10.0 g, 0.032 mol) dissolved in ethylcyclohexanecarboxylate (50 mL) and stir After 1 hour, the reaction solution was slowly heated and stirred at 60 ° C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, H ₂ O (30 mL) was added and stirred for about 30 minutes. Next, a 1% aqueous HCl solution (30 ml) was slowly added dropwise to neutralize the reaction mixture to a pH of 6 to 7. Ethyl acetate (100 ml) was added to the reaction solution and stirred for 30 minutes to separate the organic layer, and the separated organic layer was sufficiently washed with H ₂ O. The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; 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 (δ ppm; CDCl ₃ ): 0.87 (3H, t), 1.10-1.14 (10H, m), 1.28 (8H, m), 1.58-1.64 (12H, m), 1.72 (1H, t), 2.10(3H,s), 7.32-7.36(3H,m), 7.80-7.84(4H,m),8.01-8.06(2H,m)

MS( m/e ):422

Reaction 2

1-cyclohexyl-3-(4'-nitrobiphenyl-4-yl)-2-pentylpropane-1,3-dione dioxime (1-cyclohexyl-3-(4'-nitrobiphenyl-4- Synthesis of yl)-2-pentylpropane-1,3-dione di-oxime)(47)

1-Cyclohexyl-3-(4'-nitrobiphenyl-4-yl)-2-pentylpropane-1,3-dione (46) (5.0 g, 0.012 mol) dispersed in ethanol (100 ml) Among them, hydroxylamine hydrochloride (2.50 g, 0.036 mol) and sodium acetate (2.95 g, 0.036 mol) were added thereto, and the reaction solution was slowly heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, and distilled water (100 ml) and ethyl acetate (200 ml) was added thereto and stirred for about 30 minutes to separate the organic layer, and the separated organic layer was dried over anhydrous magnesium sulfate and under reduced pressure. Distill the solvent. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-cyclohexyl-3-(4'-nitrobiphenyl-4-yl) 2-pentylpropane-1,3-dione dioxime (47) (4.38 g) (80.9%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.87 (3H, t), 1.10-1.14 (10H, m), 1.28 (8H, m), 1.58-1.64 (12H, m), 1.72 (1H, t), 2.10(3H,s), 7.32-7.34(3H,m), 7.80-7.82(4H,m),8.01-8.06(2H,m)

MS( m/e ):452

Reaction 3

Synthesis of 1-cyclohexyl-3-(4'-nitrobiphenyl-4-yl)-2-pentylpropane-1,3-dione O,O-diethylhydrazine dioxime (48)

1-Cyclohexyl-3-(4'-nitrobiphenyl-4-yl)-2-pentylpropane-1,3-dione dioxime (47) (5.0 g, 0.011 mol) under a nitrogen atmosphere Dissolved in ethyl acetate (50 ml), the reaction mixture was maintained at -5 ° C, and triethylamine (2.43 g, 0.024 mol) was added. The obtained reaction solution was stirred for 30 minutes, and ethyl hydrazine chloride (1.88 g, 0.024 mol) was slowly added, and the reaction solution was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine 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-diethylhydrazine dioxime (48) (5.14 g) (87.3%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.86 (3H, t), 0.94 (6H, s), 1.10-1.14 (10H, m), 1.28 (8H, m), 1.57-1.62 (12H, m), 1.73 (1H, t), 2.11 (3H, s), 7.33-7.35 (3H, m), 7.80-7.83 (4H, m), 8.01-8.06 (2H, m)

MS( m/e ):536

[Example 21] Preparation of 1-(4'-bromobiphenyl-4-yl)butane-1,3-dione O,O-diethylhydrazine dioxime (52)

Reaction 1

Synthesis of 1-(4'-bromobiphenyl-4-yl)butane-1,3-dione (1-(4'-bromobiphenyl-4-yl)butane-1,3-dione)(50)

Anhydrous ethyl acetate (50 ml) was maintained under a nitrogen atmosphere at 5 ° C, sodium hydride (2.16 g, 60% in mineral oil, 0.054 mol) was added thereto and stirred for 30 minutes. Add 4-acetyl-4'-bromobiphenyl (49) (10.0 g, 0.036 mol) dissolved in ethyl acetate (50 mL) and stir for 1 hour, slowly The reaction solution was heated and stirred at 60 ° C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, H ₂ O (30 mL) was added and stirred for about 30 minutes. Next, a 1% aqueous HCl solution (30 ml) was slowly added dropwise to neutralize the reaction mixture to a pH of 6 to 7. Ethyl acetate (100 ml) was added to the reaction solution and stirred for 30 minutes to separate the organic layer, and the separated organic layer was sufficiently washed with H ₂ O. The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(4'-bromobiphenyl-4-yl)butane-1. 3-diketone (50) (5.97 g) (52.3%).

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

1-(4'-bromobiphenyl-4-yl)butane-1,3-dione dioxime (1-(4'-bromobiphenyl-4-yl)butane-1,3-dione di-oxime) ( Synthesis of 51)

1-(4'-bromobiphenyl-4-yl)butane-1,3-dione (50) (5.0 g, 0.016 mol) was dispersed in ethanol (100 mL) and hydroxylamine hydrochloride (3.34) Glucose (0.048 mol) and sodium acetate (3.94 g, 0.048 mol) were added thereto, and the reaction solution was slowly heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, and distilled water (100 ml) and ethyl acetate (200 ml) was added thereto and stirred for about 30 minutes to separate the organic layer, and the separated organic layer was dried over anhydrous magnesium sulfate and under reduced pressure. Distill the solvent. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(4'-bromobiphenyl-4-yl)butane-1. 3-diketone dioxime (51) (4.72 g) (84.9%).

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-diethylhydrazine dioxime (52)

1-(4'-bromobiphenyl-4-yl)butane-1,3-dione dioxime (51) under nitrogen atmosphere (5.0 g, 0.014 mol) was dissolved in ethyl acetate (50 mL). The mixture was maintained at -5[deg.] C. and triethylamine (3.14 g, 0.031 mole) was added. The obtained reaction solution was stirred for 30 minutes, and acetonitrile chloride (2.43 g, 0.031 mol) was slowly added, and the reaction mixture was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(4'-bromobiphenyl-4-yl)butane-1. 3-Dione O, O-diethylhydrazine dioxime (52) (5.43 g) (89.9%).

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-diethylhydrazine dioxime (56)

Reaction 1

Synthesis of 4-acetyl-4'-cyanobiphenyl (53)

4-Ethyl-4'-bromobiphenyl (49) (20.0 g, 0.073 mol) was dissolved in N-methyl-2-pyrrolidinone (NMP) (200 mL) And copper cyanide (9.85 g, 0.110 mol) was added, and the reaction solution was slowly heated and refluxed for 3 hours. Distilled water (300 ml) and ethyl acetate (300 ml) were added to the reaction mixture and stirred for 30 minutes to separate the organic layer, followed by a saturated aqueous solution of ammonium chloride (200 ml) and distilled water (100) The separated organic layer was washed 3 times, and the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:5) to afford 4-ethyl succinyl-4'-cyanobiphenyl (53) (8.23 g) ) (51.3%).

¹ H NMR (δ ppm; CDCl ₃ ): 2.31 (3H, s), 7.72-7.76 (4H, m), 7.95 (2H, d), 8.05 (2H, d)

MS( m/e ):221

Reaction 2

Synthesis of 1-(4'-cyanobiphenyl-4-yl)butane-1,3-dione (1-(4'-cyanobiphenyl-4-yl)butane-1,3-dione)(54)

Anhydrous ethyl acetate (50 ml) was maintained under a nitrogen atmosphere at 5 ° C, sodium hydride (2.72 g, 60% in mineral oil, 0.068 mol) was added thereto and stirred for 30 minutes. Add 4-ethylindolyl-4'-cyanobiphenyl (53) (10.0 g, 0.036 mol) dissolved in ethyl acetate (50 mL) and stir for 1 hour, slowly heat the reaction solution and stir at 60 °C. Hours to complete the reaction. The reaction solution was cooled to room temperature, H ₂ O (30 mL) was added and stirred for about 30 minutes. Next, a 1% aqueous HCl solution (50 ml) was slowly added dropwise to neutralize the reaction mixture to pH 6 to 7. Ethyl acetate (100 ml) was added to the reaction solution and stirred for 30 minutes to separate the organic layer, and the separated organic layer was sufficiently washed with H ₂ O. The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(4'-cyanobiphenyl-4-yl)butane-1 , 3-dione (54) (6.18 g) (52.2%).

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

1-(4'-cyanobiphenyl-4-yl)butane-1,3-dione di-oxime (1-(4'-cyanobiphenyl-4-yl)butane-1,3-dione di-oxime) Synthesis of (55)

1-(4'-Cyanobiphenyl-4-yl)butane-1,3-dione (54) (5.0 g, 0.019 mol) was dispersed in ethanol (100 mL) and hydroxylamine hydrochloride ( 3.97 g, 0.057 mol) and sodium acetate (4.68 g, 0.057 mol) were added thereto, and the reaction solution was slowly heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, and distilled water (100 ml) and ethyl acetate (200 ml) was added thereto and stirred for about 30 minutes to separate the organic layer, and the separated organic layer was dried over anhydrous magnesium sulfate and under reduced pressure. Distill the solvent. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to give 1-(4'-cyanobiphenyl-4-yl)butane-1 , 3-dione dioxime (55) (4.79 g) (85.9%).

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-diethylhydrazine dioxime (56)

1-(4'-Cyanobiphenyl-4-yl)butane-1,3-dione dioxime (55) (5.0 g, 0.017 mol) was dissolved in ethyl acetate (50 mL). The reaction mixture was maintained at -5 ° C and triethylamine (3.74 g, 0.037 mol) was added. The obtained reaction solution was stirred for 30 minutes, and ethyl hydrazine chloride (2.90 g, 0.037 mol) was slowly added, and the reaction mixture was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to give 1-(4'-cyanobiphenyl-4-yl)butane-1 , 3-dione O, O-diethylhydrazine dioxime (56) (5.58 g) (86.9%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.92 (6H, s), 1.88 (3H, s), 2.40 (2H, s), 7.72-7.75 (4H, m), 7.99 (2H, d), 8.20 ( 2H,d)

MS( m/e ):377

[Example 23] Preparation of 1-(4'-t-butylbiphenyl-4-yl)butane-1,3-dione O,O-diethylhydrazine dioxime (60)

Reaction 1

1-(4'-tert-butylbiphenyl-4-yl)butane-1,3-dione (1-(4'-tert-butylbiphenyl-4-yl)butane-1,3-dione) ( Synthesis of 58)

Anhydrous ethyl acetate (50 ml) was maintained under a nitrogen atmosphere at 5 ° C, sodium hydride (2.40 g, 60% in mineral oil, 0.060 mol) was added and stirred for 30 minutes. 4-(4-Butyl-4'-tert-butylbiphenyl) (57) (10.0 g, 0.040 mol) dissolved in ethyl acetate (50 mL) was added and stirred. After 1 hour, the reaction solution was slowly heated and stirred at 60 ° C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, H ₂ O (30 mL) was added and stirred for about 30 minutes. Next, a 1% aqueous HCl solution (40 ml) was slowly added dropwise to neutralize the reaction mixture to a pH of 6 to 7. Ethyl acetate (100 ml) was added to the reaction solution and stirred for 30 minutes to separate the organic layer, and the separated organic layer was sufficiently washed with H ₂ O. The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(4'-t-butyl-biphenyl-4-yl)butane. -1,3-dione (58) (6.16 g) (52.3%).

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

1-(4'-Tertiary Butyl-4-yl)butane-1,3-dione dioxime (1-(4'-tert-butylbiphenyl-4-yl)butane-1,3-dione Synthesis of di-oxime) (59)

1-(4'-Tertiary Butyl-4-yl)butane-1,3-dione (58) (5.0 g, 0.017 mol) dispersed in ethanol (100 mL), hydroxylamine hydrochloride Salt (3.55 g, 0.051 mol) and sodium acetate (4.18 g, 0.051 mol) were added thereto, and the reaction solution was slowly heated and refluxed for 1 hour. The reaction mixture was cooled to room temperature, and distilled water (100 ml) and ethyl acetate (200 ml) was added thereto and stirred for about 30 minutes to separate the organic layer, and the separated organic layer was dried over anhydrous magnesium sulfate and under reduced pressure. Distill the solvent. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(4'-t-butyl-biphenyl-4-yl)butane. -1,3-dione dioxime (59) (4.57 g) (82.9%).

¹ H NMR (δ ppm; CDCl ₃ ): 1.32 (9H, s), 1.95 (3H, s), 3.45 (2H, s), 7.72-7.76 (4H, m), 8.01 (2H, d), 8.26 ( 2H,d)

MS( m/e ):324

Reaction 3

Synthesis of 1-(4'-Tertiary Butylbiphenyl-4-yl)butane-1,3-dione O,O-Diethylhydrazine Dioxime (60)

1-(4'-Tertiary Butyl-4-yl)butane-1,3-dione dioxime (59) (5.0 g, 0.015 mol) was dissolved in ethyl acetate under a nitrogen atmosphere (50) In ml), the reaction mixture was maintained at -5 ° C, and triethylamine (3.34 g, 0.033 mol) was added thereto. The obtained reaction solution was stirred for 30 minutes, and ethyl hydrazine chloride (2.59 g, 0.033 mol) was slowly added, and the reaction solution was carefully stirred for 30 minutes so that the temperature did not rise. Then, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, and the collected was dried over anhydrous magnesium sulfate. The organic layer was evaporated under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(4'-t-butyl-biphenyl-4-yl)butane. -1,3-dione O,O-diethylhydrazine dioxime (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,d), 8.24 (2H,d)

MS( m/e ):408

[Example 24] Preparation of 1-(p-terphenyl-4-yl)butane-1,3-dione O,O-diethylhydrazine dioxime (61)

To the reactor was added phenylboronic acid (3.37 g, 0.028 mol), 1-(4'-bromobiphenyl-4-yl)butane-1,3-dione O, O-diethylhydrazine dioxime ( 52) (10.0 g, 0.023 mol), tetrakis(triphenylphosphine) palladium (0) (2.31 g, 0.002 mol), and tetrahydrofuran (100 ml). A 2M-potassium carbonate aqueous solution (100 ml) was added dropwise to the reaction mixture. The reaction mixture was heated to 60 ° C and stirred. When the reaction was completed, the reaction mixture was cooled to room temperature and ethyl acetate (100 ml). The organic layer was washed with distilled water (50 ml), and the organic layer was separated and evaporated. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(p-terphenyl-4-yl)butane-1,3-di Ketone O, O-diethylhydrazine dioxime (61) (5.11 g) (51.9%).

¹ H NMR (δ ppm; CDCl ₃ ): 0.95 (6H, s), 1.89 (3H, s), 2.45 (2H, s), 7.27 (4H, m), 7.72-7.76 (5H, m), 8.02 ( 2H, d), 8.25 (2H, d)

MS( m/e ):428

[Example 25] Preparation of 1-(1,1'-biphenyl-4-yl)-propane-1,2-dione O,O-diethylhydrazine difluorene (64)

Reaction 1

1-(1,1'-biphenyl-4-yl)-1,2-propane-2-one-1-(1-(1,1'-biphenyl-4-yl)-1,2-propanedione-2 Synthesis of -oxime)(62)

4-propenylbiphenyl (8) (19.2 g) (0.091 mmol) was dissolved in tetrahydrofuran (THF) (300 ml) and added to the mixture in 1,4-dioxane. 4N HCl (48 ml) and isoamyl nitrite (31 ml, 0.233 mmol) were stirred at 25 ° C for 6 hours. Then, ethyl acetate (100 ml) was added to the reaction mixture, and the mixture was washed with distilled water (200 ml). The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give a solid product. The obtained solid product was recrystallized from a mixed solvent of ethyl acetate and hexane (1:1, v/v) and dried to obtain light-colored 1-(1,1'-biphenyl-4-yl)- 1,2-propanedione-2-indole (62) (13.9 g) (63.8%).

¹ H-NMR (δ ppm; CDCl ₃ ): 2.19 (3H, s), 7.36 (1H, t), 7.43 (2H, t), 7.59 (2H, d), 7.63 (2H, d), 7.78 (1H) , s), 7.98 (2H, d)

MS( m/e ):239

Reaction 2

1-(biphenyl-4-yl)-2-propanetane-1,2-dione di-oxime)(1-(biphenyl-4-yl)-2-propanetane-1,2-dione di-oxime) Synthesis of 63)

1-(1,1'-biphenyl-4-yl)-1,2-propanedione-2-indole (62) (10.06 g, 0.042 mol) dispersed in ethanol (100 ml), hydroxylamine salt An acid salt (5.83 g, 0.084 mol) and sodium acetate (6.90 g, 0.084 mol) were added thereto, and the reaction solution was slowly heated and refluxed for 3 hours. The reaction mixture was cooled to room temperature, and distilled water (100 ml) and ethyl acetate (200 ml) was added thereto and stirred for about 30 minutes to separate the organic layer, and the separated organic layer was dried over anhydrous magnesium sulfate and under reduced pressure. Distill the solvent. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to give 1-(biphenyl-4-yl)-2-propanedione-1, 2-Dione dioxime (63) (9.02 g) (84.3%).

¹ H NMR (δ ppm; DMSO _d6 ): 2.21 (3H, s), 7.34-7.43 (3H, m), 7, 58-7.62 (4H, m), 7.79 (1H, s), 8.00 (2H, d ), 11.45 (1H, s), 11.60 (1H, s)

MS( m/e ):254

Reaction 3

Synthesis of 1-(1,1'-biphenyl-4-yl)-propane-1,2-dione O,O-diethylhydrazine difluorene (64)

1-(Biphenyl-4-yl)-2-propanedione-1,2-dione dioxime (63) (3.81 g, 0.015 mol) was dissolved in ethyl acetate (50 mL). The reaction mixture was maintained at -5 ° C and triethylamine (3.34 g, 0.033 mol) was added. The obtained reaction solution was stirred for 30 minutes, and acetonitrile chloride (2.59 g, 0.033 mol) was slowly added, and the reaction mixture was carefully stirred for 30 minutes so that the temperature did not rise. Next, distilled water (50 ml) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, the collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(1,1'-biphenyl-4-yl)-propane- 1,2-Dione O, O-diethylhydrazine dioxime (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] Preparation of 1-(4'-nitrobiphenyl-4-yl)-heptane-1,2-dione-O,O-didecyldifluoride (67)

Reaction 1

1-(4'-Nitrobiphenyl-4-yl)-1,2-heptanedione-2-indole-1-(1'-nitrobiphenyl-4-yl)-1,2-heptanedione-2- Synthesis of oxime)(65)

Dissolve 1-(4'-nitro-biphenyl-4-yl)heptan-1-one (41) (6.4 g) (0.030 mmol) in tetrahydrofuran (THF) (100 mL) and 4N HCl (48 ml) dissolved in 1,4-dioxane (1,4-dioxane) and isoamyl nitrite (12 ml, 0.078 mmol) were added to the mixture, and stirred at 25 ° C. The mixture was obtained for 6 hours. Then, ethyl acetate (50 ml) was added to the reaction mixture, and the mixture was washed with distilled water (100 ml). The collected organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give a solid product. The obtained solid product was recrystallized from a mixed solvent of ethyl acetate and hexane (1:1, v/v) and dried to obtain light-colored 1-(4'-nitrobiphenyl-4-yl)- 1,2-heptanedione-2-indole (65) (6.41 g) (62.8%).

^{1 H-NMR (δ ppm;} CDCl 3): 0.94 (3H, t), 1.35 (2H, m), 1.52 (2H, m), 1.78 (2H, m), 2.00 (2H, t), 7.36 (2H , d), 7.75 (2H, d), 7.98 (2H, d), 8.29 (2H, d)

MS( m/e ):340

Reaction 2

1-(4'-Nitrobiphenyl-4-yl)heptane-1,2-dione di-oxime (1-(4'-nitrobiphenyl-4-yl)heptane-1,2-dione di-oxime) Synthesis of (66)

1-(4'-Nitrobiphenyl-4-yl)-1,2-heptanedione-2-indole (65) (10.00 g, 0.029 mol was dispersed in ethanol (100 ml), hydroxylamine hydrochloride (4.05 g, 0.058 mol) and sodium acetate (4.75 g, 0.058 mol) were added thereto, and the reaction solution was slowly heated and refluxed for 3 hours. The reaction mixture was cooled to room temperature, and distilled water (100 ml) and ethyl acetate (200 ml) was added thereto and stirred for about 30 minutes to separate the organic layer, and the separated organic layer was dried over anhydrous magnesium sulfate and under reduced pressure. Distill the solvent. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(4'-nitrobiphenyl-4-yl)heptane-1 , 2-dione dioxime (66) (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 (2H, d) 11.49 (1H, s), 11.60 (1H, s)

MS( m/e ):355

Reaction 3

Synthesis of 1-(4'-nitrobiphenyl-4-yl)-heptane-1,2-dione O,O-diethylhydrazine dioxime (67)

1-(4'-Nitrobiphenyl-4-yl)heptane-1,2-dione dioxime (66) (5.00 g, 0.014 mol) was dissolved in ethyl acetate (50 mL). The reaction mixture was maintained at -5 ° C and triethylamine (3.14 g, 0.031 mol) was added. The obtained reaction solution was stirred for 30 minutes, and acetonitrile chloride (2.43 g, 0.031 mol) was slowly added, and the reaction mixture was carefully stirred for 30 minutes so that the temperature did not rise. Then, slowly add distilled water (50 ml) to the reaction mixture and stir for 30 minutes to separate the organic layer, and dry it with anhydrous magnesium sulfate. The layers were taken and the solvent was distilled under reduced pressure. The obtained product was purified by hydrazine column chromatography (eluent; ethyl acetate: n-hexane = 1:4) to obtain 1-(4'-nitrobiphenyl-4-yl)-heptane- 1,2-Dione O, O-diethylhydrazine dioxime (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, s), 2.21 (3H, s), 7.33 (2H, d), 7.80 (2H, d), 8.01 (2H, d), 8.30 (2H, d)

MS( m/e ): 439

<Preparation of binder resin>

a) Preparation of binder resin 1

Propylene glycol methyl ether acetate (PGMEA) (200 ml) and azobisisobutyronitrile (AIBN) (1.5 g) were added to a 500 ml polymerization reactor, and methacrylic acid and methacrylic acid were shrunk. Glyceride, methyl methacrylate, and dicyclopentanyl acrylate were added at a molar ratio of 20:20:40:20, wherein the acrylic monomer had a solids content of 40% by weight. The reaction mixture was stirred under a nitrogen atmosphere at 70 ° C for 5 hours to polymerize the reaction mixture, thereby preparing a binder resin 1 as an acrylic polymer. The copolymer prepared as described above had a weight average molecular weight of 25,000 and a dispersion of 1.9 by GPC measurement using a PS standard.

b) Preparation of binder resin 2

Add propylene glycol methyl ether acetate (PGMEA) (200 ml) and azobisisobutyronitrile (AIBN) (1.0 g) to a 500 ml polymerization reactor, and methacrylic acid, styrene, methacrylic acid Methyl ester, and cyclohexyl methacrylate are added at a molar ratio of 40:20:20:20, wherein the acrylic monomer has 40% by weight solids content. The reaction mixture was stirred under a nitrogen atmosphere at 70 ° C for 5 hours to polymerize the reaction mixture, thereby preparing a copolymer. N,N-dimethylaniline (0.3 g) was added to the reactor, and a 20 mol ratio of glycidyl methacrylate in a solid amount of 100 mol of the total monomer solids was stirred at 100 ° C. For 10 hours, a binder resin 2 having an acrylic polymer having an acrylic unsaturated bond in a side chain was prepared. The copolymer prepared as described above had a weight average molecular weight of 20,000 and a degree of dispersion of 2.0 by GPC measurement using a PS standard.

c) Preparation of binder resin 3

Propylene glycol methyl ether acetate (PGMEA) (200 ml) and azobisisobutyronitrile (AIBN) (1.0 g) were added to a 500 ml polymerization reactor, and glycidyl methacrylate, styrene, Methyl methacrylate, and cyclohexylmethyl methacrylate were added at a molar ratio of 40:20:20:20, wherein the acrylic monomer had a solids content of 40% by weight. The reaction mixture was stirred under a nitrogen atmosphere at 70 ° C for 5 hours to polymerize the reaction mixture, thereby preparing a copolymer. N,N-dimethylaniline (0.3 g) was added to the reactor, and 20 mol of acrylic acid in a solid amount of 100 mol of all monomers was stirred at 100 ° C for 10 hours to prepare. A binder resin 3 having an acrylic polymer having an acrylic unsaturated bond in a side chain. The copolymer prepared as described above had a weight average molecular weight of 18,000 and a degree of dispersion of 1.8 by GPC measurement using a PS standard.

[Examples 27 to 43] Preparation of Photoresist Composition

The binder resins 1 to 3, the photoreactive compound, the photopolymerization initiator of the present invention, and FC-430 (3M company's leveling agent) were sequentially added to the ultraviolet protective film and according to the group shown in Table 1 below. The mixture of the ingredients and the agitator is mixed in a reaction tube and stirred at room temperature. In addition, the addition of PGMEA as a solvent allows the prepared composition to have a total amount of 100% by weight. A photoresist composition was prepared.

[Example 44] Preparation of black matrix photoresist composition

As shown in Table 1 below, 20% by weight of the binder 1, 10% by weight of dipentaerythritol hexaacrylate, and 0.5% by weight of the compound 43 were dispersed in a solid content of 25% by weight. 50% by weight of carbon black of PGMEA and 0.1% by weight of FC-430 (a leveling agent of 3M Company) were placed in a reaction mixing tube equipped with an ultraviolet protective film and a stirrer, and stirred at room temperature. Next, PGMEA as a solvent was added so that the prepared composition had a total amount of 100% by weight to prepare a black matrix resist composition.

[Example 45] Preparation of Red Photoresist Composition

As shown in Table 1 below, the same method as in Example 44 was carried out except that 50% by weight of a pigment red 177 (PR177) dispersion having a solid content of 25% by weight was used instead of the carbon black used in Example 44. A red photoresist composition was prepared.

[Comparative Example 1] Preparation of Photoresist Composition

A photoresist composition was prepared by the same method as in Example 27 except that the photopolymerization initiator represented by the following Chemical Formula B was used instead of using Compound 4 as a photopolymerization initiator.

[Comparative Example 2] Preparation of Photoresist Composition

In addition to the use of 3-(ethyloxyimino)-1-(6-nitro-9H-indol-3-yl)propan-1-one (3-(acetoxyimino)-1-(6-nitro-9H) A photoresist composition was prepared by the same method as in Example 27 except that -fluorene-3-yl)propane-1-one was used instead of Compound 4 as a photopolymerization initiator.

[Testing Examples] Evaluation of Photoresist Compositions

The evaluation of the photoresist compositions according to Examples 27 to 45 and Comparative Examples 1 and 2 was carried out on a glass substrate to measure the properties of the photoresist composition, such as sensitivity, film retention, pattern stability, Chemical resistance, ductility, etc., and the evaluation results are shown in Table 2 below.

1) Sensitivity

The photoresist composition was spin-coated on a glass substrate and dried on a hot plate at 100 ° C for 1 minute, and the dried photoresist was exposed using a step mask and developed with a 0.04% KOH aqueous solution. Wherein the thickness of the step mask pattern is maintained at 80% of the initial thickness The exposure was evaluated as sensitivity.

2) Membrane retention

The photogroup composition was coated on a substrate using a spin coater and pre-baked at 100 ° C for 1 minute, and the pre-baked photoresist was exposed at 365 nm and then baked at 230 ° C for 20 minutes. Then, the thickness ratio (%) of the photoresist film before and after the post-baking was measured.

3) Pattern stability

The tantalum wafer with the photoresist pattern was cut in the vertical direction of the entire pattern, and the cross-sectional direction of the pattern was observed by a microscope. When the side walls of the pattern stand at 55 degrees or more to the substrate and no decrease in film thickness is observed, the pattern stability of the photoresist composition is judged to be "better", and when the film thickness is observed to decrease The pattern stability was judged as "film thickness reduction".

4) Chemical resistance

The photoresist composition is applied onto a substrate using a spin coater, and subjected to, for example, a pre-baking treatment, a post-baking treatment, or the like to form a photoresist film. After the photoresist film was formed, it was immersed in a stripper solution at 40 ° C for 10 minutes to observe whether the transmittance and thickness of the photoresist film were changed. When the change in transmittance and thickness is 2% or less, the chemical resistance is judged as "good", and when the change in transmittance and thickness is more than 2%, the chemical resistance is judged as "poor". .

5) ductility

After the photoresist composition was coated on the substrate using a spin coater and pre-baked at 100 ° C for 1 minute, the pre-baked photoresist was exposed to light sensitivity and developed with KOH aqueous solution. A pattern was formed (20 microns x 20 microns). The pattern formed by burning at 230 ° C for 20 minutes from Crosslinking is produced and the ductility of the pattern is measured by a nanoindenter. According to the results measured by the nanoindenter, when the total change amount at a load of 5 gram force (gf) is 500 nm or more, the ductility is judged as "good", when the total change amount is less than 500 In the case of nanometers, the ductility system was judged as "poor".

It is confirmed from the foregoing Table 2 that when the diterpene ester compound of the present invention is used as a photopolymerization initiator of a photoresist composition, the sensitivity may be remarkably excellent in spite of a small amount, such as film retention, pattern stability, and resistance. Physical properties such as chemical properties and ductility can be excellent, thereby minimizing exhaust gas generated from the photopolymerization initiator during exposure and post-baking of a thin film transistor liquid crystal display (TFT-LCD) manufacturing method, and thus Reduce pollution and minimize defects.

Claims (9)

A di-oxime ester compound represented by the following Chemical Formula 1: In Chemical Formula 1, R ₁ to R ₃ are each independently hydrogen, halogen, (C ₁ to C ₂₀ ) alkyl, (C ₆ to C ₂₀ ) aryl, (C ₁ to C ₂₀ ) alkoxy, ( C ₆ to C ₂₀ ) aryl (C ₁ to C ₂₀ ) alkyl, hydroxy (C ₁ to C ₂₀ ) alkyl, hydroxy (C ₁ to C ₂₀ ) alkoxy (C ₁ to C ₂₀ ) alkyl, (C ₃ to C ₂₀ ) cycloalkyl, or (C ₃ to C ₂₀ ) cycloalkyl (C ₁ to C ₂₀ ) alkyl; A hydrogen, halogen, (C ₁ to C ₂₀ ) alkyl, (C ₆ to C ₂₀ ) an aryl group, a (C ₆ to C ₂₀ ) aryl (C ₁ to C ₂₀ ) alkyl group, an amine group, a nitro group, a cyano group, or a hydroxyl group; and n is an integer of 0 to 2. A photopolymerization initiator comprising the diterpene ester compound of claim 1. A photoresist composition comprising the diterpene ester compound of claim 1, a binder, and a compound having an ethylenically unsaturated bond. The photoresist composition of claim 3, further comprising at least one photopolymerization initiator selected from the group consisting of: a thioxanthone-based compound, an acetophenone-based compound, and a biimidazole-based (biimidazole- A compound, a triazine compound, a thiol compound, and an O-acyloxime-based compound. The photoresist composition of claim 3, wherein the diterpene ester compound is contained in an amount of from 0.01% by weight to 10% by weight based on 100% by weight of the photoresist composition. The photoresist composition of claim 3 or 4 further comprising a colorant. A molded article comprising a cured product of the photoresist composition of claim 3 or 4. A molded article comprising a cured product of the photoresist composition of claim 6. A display device comprising the molded article of claim 7.