KR20150055895A - Xanthene dye compounds and method for producing thereof - Google Patents
Xanthene dye compounds and method for producing thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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Abstract
Description
본 발명은 컬러필터용 크산텐계 염료 화합물에 관한 것으로서, 더욱 상세하게는 유기용매에 대한 용해도가 높고, 내열성이 우수한 것을 특징으로 하는 크산텐계 염료 화합물과 이의 제조방법에 관한 것이다.The present invention relates to a xanthene-based dye compound for a color filter, and more particularly to a xanthene-based dye compound having a high solubility in an organic solvent and excellent heat resistance and a method for producing the same.
염료 화합물은 화합물의 색 흡수 내지 투과하는 성질에 의해 여러 가지 분야에 응용이 되고 있다. 특히, 섬유 착색제 등으로 활용되는 섬유 산업 분야, 디스플레이 소재 분야, 잉크젯 잉크 조성물 등의 분야에서 널리 사용되고 있다.Dye compounds have been applied to various fields due to their color absorption or transmission properties. In particular, it is widely used in the fields of textile industry, display materials, inkjet ink compositions and the like, which are used as fiber colorants.
이러한 염료 화합물 중에서 크산텐계 화합물에 해당하고, 널리 사용되고 있는 하기 로다민 B(Rhodamine B) 화합물의 경우, 유기용매에 대한 용해도 및 내열성이 좋지 않아 그 활용분야가 섬유산업 및 잉크젯 잉크에 한정되어 사용되고 있는 실정이다.Among these dye compounds, Rhodamine B compounds, which are widely used as xanthene compounds, have poor solubility and heat resistance to organic solvents, and their application fields are limited to the textile industry and inkjet inks It is true.
[Rhodamine B][Rhodamine B]
또한, 이러한 한계점을 개선하기 위하여, 아래 [반응식 Ⅰ]과 같이 로다민 B의 카르복시산 기를 산염화물로 바꾼 후에 1차 아민과 반응시켜 아마이드로 바꾸려는 일부 시도들이 진행되었으나, 반응 진행 시 생성물이 pH에 따라 색이 바뀌는 로다민 락탐 화합물이 부산물로 얻어진다. (J. Org. Chem. 2013, 78, 10134-10143, 미국등록특허 US4,290,955)In order to overcome this limitation, some attempts have been made to replace the carboxylic acid group of rhodamine B with an acid chloride by reacting with a primary amine to convert it to amide as shown in Reaction Scheme I below, Rhodamine lactam compounds that change color are obtained as by-products. (J. Org. Chem. 2013, 78, 10134-10143, U.S. Pat. No. 4,290,955)
[반응식 Ⅰ][Reaction Scheme I]
상기 반응식에서 Y는 알킬기이다.In the above reaction formula, Y is an alkyl group.
또한, 본 발명의 연구자들의 실험결과에 의하면 하기 [반응식 Ⅱ]와 같이 하이드록시기를 가진 1차 아민을 반응에 사용할 경우, 원하는 아마이드 화합물 외에도 부생성물인 에스터화합물이 생성되는 것이 확인되었다.Further, according to the experimental results of the inventors of the present invention, it was confirmed that when a primary amine having a hydroxy group is used in the reaction as shown in the following reaction scheme [II], an ester compound as a byproduct is produced in addition to the desired amide compound.
[반응식 Ⅱ][Reaction Scheme II]
상기 반응식에서 W는 알킬렌기이다.In the above reaction formula, W is an alkylene group.
따라서 본 발명이 해결하고자 하는 과제는 상기의 문제점을 해결하기 위한 것으로서, 유기용매에 대한 용해도 및 내열성이 우수하여 다양한 분야에서 활용할 수 있고, 특히 염료에 대한 요구 조건이 까다로운 디스플레이 분야까지 적용이 가능한 신규한 크산텐 염료 화합물 및 이의 제조방법을 제공하고자 한다.Accordingly, it is an object of the present invention to overcome the above-mentioned problems, and it is an object of the present invention to provide a novel organic solvent capable of being applied to various fields such as solubility and heat resistance, A xanthan dyestuff compound and a process for producing the same.
본 발명은 상기 과제를 해결하기 위하여, 하기 [화학식 1]로 표시되는 염료 화합물을 제공한다.In order to solve the above problems, the present invention provides a dye compound represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 [화학식 1]에서, X-는 노나플루오르부탄술폰산 음이온, 비스(트리플루오르메탄)술폰이미드 음이온 또는 테트라키스(펜타플루오르페닐)보레이트 음이온이다.In the above formula (1), X - is a nonafluorobutanesulfonic acid anion, a bis (trifluoromethanesulfonimide) anion or a tetrakis (pentafluorophenyl) borate anion.
상기 [화학식 1]에서, R1, R2, R3 및 R4는 각각 독립적으로 수소, 치환 또는 비치환된 탄소수 1 내지 10의 알킬기, 알릴기, 치환 또는 비치환된 탄소수 6 내지 10의 방향족 탄화수소 및 하기 [구조식 1] 또는 [구조식 2]로 표시되는 R8 중에서 선택된다.R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an allyl group, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms Hydrocarbon and R 8 represented by the following structural formula 1 or structural formula 2 .
[구조식 1][Structural formula 1]
[구조식 2][Structural formula 2]
상기 [구조식 1] 및 [구조식 2]에서, R9는 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이고, R10은 수소 또는 메틸이다.In the above structural formulas 1 and 2, R 9 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and R 10 is hydrogen or methyl.
상기 [화학식 1]에서, R5 및 R6는 각각 독립적으로 치환 또는 비치환된 탄소수 1 내지 5의 알킬렌기이며, Z는 N 또는 C-H이다.In the above formula (1), R 5 And R 6 are each independently a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, and Z is N or CH.
상기 [화학식 1]에서, R7은 하기 [구조식 3] 또는 [구조식 4]이다.In the above formula (1), R 7 is [Structural Formula 3] or [Structural Formula 4].
[구조식 3][Structural Formula 3]
[구조식 4][Structural Formula 4]
상기 [구조식 3] 및 [구조식 4]에서, R11은 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이고, R12는 수소 또는 메틸이다.
In the above structural formulas 3 and 4, R 11 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and R 12 is hydrogen or methyl.
또한, 본 발명은 하기 [반응식 1]에 따라 하기 [화학식 E]로부터 유기 용매 하에서 치환하고자 하는 염 수용액을 이용하여 음이온을 교환하여 하기 [화학식 1]로 표시되는 본 발명에 따른 크산텐 염료 화합물의 합성방법을 제공한다.The present invention also relates to a process for the preparation of the xanthene dyestuff according to the present invention represented by the following formula (1) by exchanging anions using an aqueous salt solution to be substituted from the following formula (E) Lt; / RTI >
[반응식 1][Reaction Scheme 1]
[E] [화학식 1] [E] [Chemical Formula 1]
본 발명의 일 실시예에 의하면, 상기 [화학식 E]는 하기 [반응식 2]에 따라 하기 [화학식 D]로부터 아크릴화 또는 메타아크릴화 반응을 수행하여 합성할 수 있다.According to one embodiment of the present invention, the above-mentioned formula (E) can be synthesized by performing an acrylating or methacrylating reaction from the following formula (D) according to the following Reaction Scheme 2.
[반응식 2][Reaction Scheme 2]
[D] [E] [D] [E]
본 발명의 일 실시예에 의하면, 상기 [화학식 D]는 하기 [반응식 3]에 따라 하기 [화학식 A]를 티오닐클로라이드와 이용하여 산염화물을 제조한 후에, 하기 [화학식 B] 또는 [화학식 C]와 반응시켜 합성할 수 있다.According to one embodiment of the present invention, the above-mentioned formula (D) can be prepared by reacting a compound represented by the following formula (B) or (C) with a thiol compound represented by the following formula [ And the like.
[반응식 3][Reaction Scheme 3]
[A] [D] [A] [D]
상기 [반응식 1] 내지 [반응식 3]에서, X-, R1, R2, R3, R4, R5, R6 및 R7은 상기 [화학식 1]에서의 정의와 동일하고, R13은 하이드록시기 또는 치환 또는 비치환된 탄소수 1 내지 10의 하이드록시알킬이다.The [Reaction Scheme 1] to the [Reaction Scheme 3], X -, R 1 , R 2, R 3, R 4, R 5, R 6 And R < 7 > are the same as defined in the above formula (1), and R < 13 > is a hydroxy group or a substituted or unsubstituted hydroxyalkyl of 1 to 10 carbon atoms.
본 발명에 따른 크산텐 염료 화합물은 유기 용매에 대한 용해도가 높고, 내열성이 우수하여 다양한 분야에서 염료 소재로 적용이 가능하고, 특히 디스플레이용 소재에까지 적용이 가능하다.The xanthene dye compound according to the present invention has high solubility in an organic solvent and is excellent in heat resistance, so that it can be applied as a dye material in various fields, and can be applied particularly to a display material.
이하, 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명에 따른 화합물은 유기 용제에 대한 우수한 용해성과 높은 내열성을 가져서 섬유 소재, 잉크 조성물, 디스플레이 소재 등 다양한 분야에 활용할 수 있는 신규한 크산텐 염료 화합물에 관한 것으로서, 하기 [화학식 1]로 표시되는 크산텐 염료 화합물인 것을 특징으로 한다.The present invention relates to a novel xanthene dye compound having excellent solubility in an organic solvent and high heat resistance and being applicable to various fields such as a fiber material, an ink composition, a display material, and the like. And is a xanthene dye compound.
[화학식 1][Chemical Formula 1]
상기 [화학식 1]에서, X-는 노나플루오르부탄술폰산 음이온, 비스(트리플루오르메탄)술폰이미드 음이온 또는 테트라키스(펜타플루오르페닐)보레이트 음이온이다.In the above formula (1), X - is a nonafluorobutanesulfonic acid anion, a bis (trifluoromethanesulfonimide) anion or a tetrakis (pentafluorophenyl) borate anion.
상기 [화학식 1]에서, R1, R2, R3 및 R4는 각각 독립적으로 수소, 치환 또는 비치환된 탄소수 1 내지 10의 알킬기, 알릴기, 치환 또는 비치환된 탄소수 6 내지 10의 방향족 탄화수소 및 하기 [구조식 1] 또는 [구조식 2]로 표시되는 R8 중에서 선택된다.R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an allyl group, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms Hydrocarbon and R 8 represented by the following structural formula 1 or structural formula 2 .
[구조식 1][Structural formula 1]
[구조식 2][Structural formula 2]
상기 [구조식 1] 및 [구조식 2]에서, R9는 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이고, R10은 수소 또는 메틸이다.In the above structural formulas 1 and 2, R 9 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and R 10 is hydrogen or methyl.
상기 [화학식 1]에서, R5 및 R6는 각각 독립적으로 탄소수 1 내지 5의 치환 또는 비치환 알킬렌기이며, Z는 N 또는 C-H이다.In the above formula (1), R 5 And R 6 are each independently a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, and Z is N or CH.
상기 [화학식 1]에서, R7은 하기 [구조식 3] 또는 [구조식 4]이다.In the above formula (1), R 7 is [Structural Formula 3] or [Structural Formula 4].
[구조식 3][Structural Formula 3]
[구조식 4][Structural Formula 4]
상기 [구조식 3] 및 [구조식 4]에서, R11은 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이고, R12는 수소 또는 메틸이다.In the above structural formulas 3 and 4, R 11 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and R 12 is hydrogen or methyl.
본 발명에 따른 크산텐 화합물의 치환기 중 탄소수 1 내지 10의 알킬기는 구체적으로 메틸기, 에틸기, n-프로필기, n-부틸기 등의 노멀 탄화수소기 등일 수 있고, 이소프로필, 이소부틸, 이소펜틸, 2-에틸헥실, t-부틸 등의 알킬기 치환기를 더 갖는 탄화수소기일 수도 있다. 또한, 클로로, 브로모, 아이오도 등의 할로겐기로 더 치환된 할로겐화 알킬기일 수도 있고, 메톡시, 에톡시, 프로폭시, 부톡시 등의 알콕시기로 더 치환된 탄화수소기 등일 수도 있다.The alkyl group having 1 to 10 carbon atoms in the substituent of the xanthene compound according to the present invention may specifically be a normal hydrocarbon group such as a methyl group, ethyl group, n-propyl group or n-butyl group, and isopropyl, isobutyl, 2-ethylhexyl, t-butyl, and the like. Further, a halogenated alkyl group further substituted with a halogen group such as chloro, bromo, or iodo, or a hydrocarbon group further substituted with an alkoxy group such as methoxy, ethoxy, propoxy, butoxy, or the like.
또한, 탄소수 6 내지 10의 방향족 탄화수소기는 구체적으로 페닐기, 나프틸기, 바이페닐기 등을 들 수 있으며, 각각에 알킬기, 알콕시기, 할로겐기 등이 더 치환된 것일 수도 있다.Specific examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, a naphthyl group, and a biphenyl group, and each of them may be further substituted with an alkyl group, an alkoxy group, a halogen group, or the like.
본 발명에 따른 [화학식 1]로 표시되는 크산텐 염료 화합물은 이에 한정되는 것은 아니나, 보다 구체적으로 하기 [화학식 2] 내지 [화학식 7]로 표시되는 화합물일 수 있다.The xanthene dye compound represented by the formula (1) according to the present invention is not limited thereto, but may be more specifically a compound represented by the following formulas (2) to (7).
[화학식 2](2)
[화학식 3](3)
[화학식 4][Chemical Formula 4]
[화학식 5][Chemical Formula 5]
[화학식 6][Chemical Formula 6]
[화학식 7](7)
본 발명의 다른 측면은 상기 [화학식 1]로 표시되는 크산텐 염료 화합물의 합성방법에 관한 것으로서, 하기 [반응식 1] 내지 [반응식 3]에 따라서 합성하는 것을 특징으로 한다.Another aspect of the present invention relates to a method for synthesizing a xanthene dye compound represented by the above formula (1), wherein the synthesis is carried out according to the following Reaction Schemes 1 to 3.
먼저 하기 [반응식 3]에 따라서 [화학식 A] 화합물을 용매 하에서 티오닐클로라이드와 반응시켜 산염화물을 합성한 후에, 이를 [화학식 B] 또는 [화학식 C]를 트리메틸아민과 같은 염기와 함께 투입하여 반응시켜 [화학식 D]를 합성한다.First, a compound of the formula (A) is reacted with thionyl chloride in accordance with the following reaction scheme [3] to synthesize an acid chloride, which is then reacted with a base such as trimethylamine in the formula (B) [Formula D] is synthesized.
[반응식 3][Reaction Scheme 3]
[A] [D] [A] [D]
상기 용매는 벤젠, 톨루엔 등과 같은 방향족 탄화수소, 클로로벤젠, 디클로로벤젠, 디클로로에탄, 디클로로메탄, 클로로포름 등의 할로겐화 탄화수소 등을 들 수 있다.Examples of the solvent include aromatic hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloroethane, dichloromethane and chloroform.
상기 [반응식 3]에서, 티오닐클로라이드의 사용량은 1-5 당량이 바람직하고, 반응온도 및 반응시간은 30-130 ℃, 1-4 시간이 바람직하다. 또한, 상기 [화학식 B] 또는 [화학식 C], 트리에틸아민 등의 염기 사용량은 1-5 당량이 바람직하다.In the above Reaction Scheme 3, the amount of thionyl chloride to be used is preferably 1-5 equivalents, and the reaction temperature and the reaction time are preferably 30-130 DEG C and 1-4 hours. The amount of the base such as [Formula B], [Formula C] and triethylamine is preferably 1-5 equivalents.
다음으로, 하기 [반응식 2]에 따라서 [화학식 D] 화합물을 산 촉매하에서 아크릴산 또는 메타아크릴산과 반응시켜 [화학식 E]를 합성하거나, 또는 염기 존재 하에서 아크릴산무수물 또는 메타아크릴산무수물과 반응시켜 [화학식 E]를 합성한다.Next, the compound of the formula (D) is reacted with acrylic acid or methacrylic acid under acid catalysis according to the following reaction scheme 2 to synthesize the compound of the formula (E) or reacted with acrylic acid anhydride or methacrylic acid anhydride in the presence of a base [ ].
[반응식 2][Reaction Scheme 2]
[D] [E] [D] [E]
상기 [반응식 2]에서, 상기 산 촉매의 사용량은 0.05-1 당량이 바람직하고, 아크릴산, 메타아크릴산은 1-10 당량이 바람직하다. 또한, 상기 염기, 아크릴산무수물, 메타아크릴산무수물은 1-10 당량이 바람직하다.In the above Reaction Scheme 2, the amount of the acid catalyst to be used is preferably 0.05 to 1 equivalent, and the amount of acrylic acid and methacrylic acid is preferably 1-10 equivalents. The base, acrylic acid anhydride and methacrylic acid anhydride are preferably used in an amount of 1-10 equivalents.
다음으로, 하기 [반응식 1]에 따라서 [화학식 E] 화합물을 메탄올, 에탄올 등의 알코올에 용해시키거나, 또는 디클로로메탄, 클로로포름과 같은 할로겐화 탄화수소에 용해시킨 후에, 치환하고자 하는 음이온 염을 물에 용해한 후에 이를 적가하여 교반시켜 [화학식 1]을 합성한다.Next, the compound of the formula (E) is dissolved in an alcohol such as methanol or ethanol, or dissolved in a halogenated hydrocarbon such as dichloromethane or chloroform according to the following reaction scheme 1, and then the anion salt to be substituted is dissolved in water Then, the mixture is added dropwise and stirred to synthesize [Formula 1].
[반응식 1][Reaction Scheme 1]
[E] [화학식 1] [E] [Chemical Formula 1]
상기 [반응식 1]에서, 치환하고자 하는 염의 당량은 1-3 당량이 바람직하다.In the above Reaction Scheme 1, the equivalent of the salt to be substituted is preferably 1-3 equivalents.
본 발명에 따른 [화학식 1]로 표시되는 크산텐 염료 화합물의 합성방법은 상기와 같은 방법으로 [화학식 1] 화합물 합성 후에, 필요에 따라 재결정 등의 방법으로 정제하는 과정을 더 포함할 수 있다.The method for synthesizing the xanthene dye compound represented by the formula (1) according to the present invention may further include a step of purifying the compound by recrystallization or the like after synthesis of the compound represented by the formula (1).
상기 [반응식 1] 내지 [반응식 3]에서, X-, R1, R2, R3, R4, R5, R6 및 R7은 상기 [화학식 1]에서의 정의와 동일하고, R13은 하이드록시기 또는 치환 또는 비치환된 탄소수 1 내지 10의 하이드록시알킬이다.
The [Reaction Scheme 1] to the [Reaction Scheme 3], X -, R 1 , R 2, R 3, R 4, R 5, R 6 And R < 7 > are the same as defined in the above formula (1), and R < 13 > is a hydroxy group or a substituted or unsubstituted hydroxyalkyl of 1 to 10 carbon atoms.
이하, 바람직한 실시예를 들어 본 발명을 더욱 상세하게 설명한다. 그러나, 이들 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 범위가 이에 의하여 제한되지 않고, 본 발명의 범주 및 기술서상 범위 내에서 다양한 변경 및 수정이 가능함은 당업계의 통상의 지식을 가진 자에게 자명할 것이다.
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as defined by the appended claims. It will be clear to those who have knowledge.
<실시예><Examples>
합성예 1 내지 6 : [화학식 2] 내지 [화학식 7] 화합물의 합성Synthesis Examples 1 to 6: Synthesis of Compounds (2) to (7)
(1) [화학식 I] 화합물의 합성(1) Synthesis of Compound (I)
하기 반응식에 따라 [화학식 I]로 표시되는 화합물을 합성하였다.A compound represented by formula (I) was synthesized according to the following reaction formula.
[로다민 B] [화학식 I] [Rhodamine B] (I)
반응기에 로다민 B 21.00 mmol, DMF 10.00 mmol에 디클로로메탄 200.00 g을 첨가하여 교반 용해시킨 후에, 티오닐클로라이드 63.00 mmol을 적가하고 40 ℃로 승온하여 1시간 동안 반응시켰다. 감압증류하여 디클로로메탄과 잔여 티오닐클로라이드를 제거하여 산염화물을 합성하였다.To the reactor, 21.00 mmol of rhodamine B and 10.00 mmol of DMF were added with 200.00 g of dichloromethane, followed by dissolution with stirring. Then, 63.00 mmol of thionyl chloride was added dropwise, and the mixture was heated to 40 ° C and reacted for 1 hour. The dichloromethane and the remaining thionyl chloride were removed by distillation under reduced pressure to synthesize an acid chloride.
별도의 반응기에 4-하이드록시피페리딘 42.00 mmol, 트리에틸아민 42.00 mmol을 디클로로메탄 200.00 g에 용해한 후, 0 ℃ 이하로 냉각하였다.In a separate reactor, 42.00 mmol of 4-hydroxypiperidine and 42.00 mmol of triethylamine were dissolved in 200.00 g of dichloromethane, followed by cooling to 0 占 폚 or lower.
상기에 얻어진 산염화물을 디클로로메탄 100 g에 용해하여 반응기 온도를 0 ℃ 이하로 유지하면서 2 시간 동안 적가하였다.The obtained acid chloride was dissolved in 100 g of dichloromethane, and the solution was added dropwise for 2 hours while maintaining the temperature of the reactor at 0 캜 or lower.
반응완료 후, 물을 투입하고 세정하여 트리에틸아민을 제거한 후, 정제하여 [화학식 I] 화합물 16.49 mmol을 얻었다.
After completion of the reaction, water was added and washed to remove triethylamine, and then purified to obtain 16.49 mmol of the compound of the formula (I).
(2) [화학식 Ⅱ] 화합물의 합성(2) Synthesis of Compound of Formula (II)
하기 반응식에 따라 [화학식 Ⅱ] 화합물을 합성하였다.Compound [II] was synthesized according to the following reaction scheme.
[화학식 I] [화학식 Ⅱ](I) [Formula II]
[화학식 I] 화합물 12.00 mmol, 트리에틸아민 24.00 mmol에 디클로로메탄 70.00 g을 첨가하여 교반 용해하였다. 그 후, 메타아크릴산 무수물 24.00 mmol을 투입한 후, 40 ℃로 승온하고 유지하였다. 반응종료 후, 물을 첨가하고 교반하여 세정하였다. 층분리 후, 유기층을 감압농축하고 정제하여 [화학식 Ⅱ] 화합물 10.95 mmol을 얻었다.
Compound (12.00 mmol) and triethylamine (24.00 mmol) were dissolved in dichloromethane (70.00 g) and dissolved by stirring. Thereafter, 24.00 mmol of methacrylic anhydride was added, and the temperature was raised to 40 캜 and maintained. After completion of the reaction, water was added, and the mixture was stirred and washed. After layer separation, the organic layer was concentrated under reduced pressure and purified to obtain 10.95 mmol of the compound of the formula (II).
(3) 합성예 1 : [화학식 2] 화합물의 합성(3) Synthesis Example 1: Synthesis of Compound (2)
하기 반응식에 따라 [화학식 2] 화합물을 합성하였다.[Chemical Formula 2] was synthesized according to the following reaction formula.
[화학식 Ⅱ] [화학식 2][Formula II] (2)
[화학식 Ⅱ] 화합물 10.95 mmol에 디클로로메탄 90.00 g을 첨가하여 교반 용해하였다. 리튬 비스(트리플루오르메탄)술폰이미드 12.05 mmol을 20% 수용액으로 용해하여 투입한 후, 상온에서 1 시간 교반하였다. 층분리하여 유기층을 물로 세척하고 감압농축 후, 정제하여 [화학식 2] 화합물 9.77 mmol을 얻었다.
[Formula II] 90.00 g of dichloromethane was added to 10.95 mmol of the compound and dissolved by stirring. 12.05 mmol of lithium bis (trifluoromethane) sulfonimide was dissolved in 20% aqueous solution, and the mixture was stirred at room temperature for 1 hour. Layer separation. The organic layer was washed with water, concentrated under reduced pressure, and purified to obtain 9.77 mmol of a compound represented by the formula (2).
(4) 합성예 2 : [화학식 3] 화합물의 합성(4) Synthesis Example 2: Synthesis of Compound (3)
하기 반응식에 따라 [화학식 3] 화합물을 합성하였다.[Chemical Formula 3] was synthesized according to the following reaction formula.
[화학식 Ⅱ] [화학식 3][Formula II] (3)
[화학식 Ⅱ] 화합물 10.95 mmol에 디클로로메탄 90.00 g을 첨가하여 교반 용해하였다. 리튬 노나플루오르부탄술포네이트 12.05 mmol을 20% 수용액으로 용해하여 투입한 후, 상온에서 1시간 교반하였다. 층분리하여 유기층을 물로 세척하고 감압농축 후, 정제하여 [화학식 3] 화합물 9.34 mmol을 얻었다.
[Formula II] 90.00 g of dichloromethane was added to 10.95 mmol of the compound and dissolved by stirring. 12.05 mmol of lithium nonafluorobutanesulfonate was dissolved in 20% aqueous solution, and the mixture was stirred at room temperature for 1 hour. The organic layer was washed with water, concentrated under reduced pressure, and purified to obtain 9.34 mmol of a compound of the formula (3).
(5) 합성예 3 : [화학식 4] 화합물의 합성(5) Synthesis Example 3: Synthesis of Compound (4)
하기 반응식에 따라 [화학식 4] 화합물을 합성하였다.[Chemical Formula 4] was synthesized according to the following reaction formula.
[화학식 Ⅱ] [화학식 4][Formula II] [Chemical Formula 4]
[화학식 Ⅱ] 화합물 10.95 mmol에 디클로로메탄 90.00 g을 첨가하여 교반 용해하였다. 칼륨 테트라키스(펜타플루오르페닐)보레이트 12.05 mmol을 20% 수용액으로 용해하여 투입한 후, 상온에서 1시간 교반하였다. 층분리하여 유기층을 물로 세척하고 감압농축 후, 정제하여 [화학식 4] 화합물 9.57 mmol을 얻었다.
[Formula II] 90.00 g of dichloromethane was added to 10.95 mmol of the compound and dissolved by stirring. 12.05 mmol of potassium tetrakis (pentafluorophenyl) borate was dissolved in 20% aqueous solution, and the mixture was stirred at room temperature for 1 hour. The organic layer was washed with water, concentrated under reduced pressure, and purified to obtain 9.57 mmol of a compound represented by the following formula (4).
(6) [화학식 Ⅲ] 화합물의 합성(6) Synthesis of Compound (III)
하기 반응식에 따라 [화학식 Ⅲ]로 표시되는 화합물을 합성하였다.A compound represented by the formula (III) was synthesized according to the following reaction formula.
[로다민 B] [화학식 Ⅲ][Rhodamine B] [Formula (III)
반응기에 로다민 B 21.00 mmol, DMF 10.00 mmol에 디클로로메탄 200.00 g을 첨가하여 교반 용해하였다. 그 후, 티오닐클로라이드 63.00 mmol을 적가하고 40 ℃로 승온하여 1시간 반응하였다. 감압증류하여 디클로로메탄과 잔여 티오닐클로라이드를 제거하여 산염화물을 합성하였다.To the reactor were added 21.00 mmol of rhodamine B, 10.00 mmol of DMF, and 200.00 g of dichloromethane, followed by dissolving with stirring. Then, 63.00 mmol of thionyl chloride was added dropwise, and the temperature was raised to 40 占 폚 and reacted for 1 hour. The dichloromethane and the remaining thionyl chloride were removed by distillation under reduced pressure to synthesize an acid chloride.
별도의 반응기에 1-(2-하이드록시에틸)피페라진 0.042 mol, 트리에틸아민 0.042 mol을 디클로로메탄 200.00 g에 용해한 후, 0 ℃ 이하로 냉각하였다.In a separate reactor, 0.042 mol of 1- (2-hydroxyethyl) piperazine and 0.042 mol of triethylamine were dissolved in 200.00 g of dichloromethane and then cooled to 0 占 폚 or lower.
상기에 얻어진 산염화물을 디클로로메탄 100 g에 용해하여 반응기 온도를 0 ℃ 이하로 유지하면서 2 시간 동안 적가하였다.The obtained acid chloride was dissolved in 100 g of dichloromethane, and the solution was added dropwise for 2 hours while maintaining the temperature of the reactor at 0 캜 or lower.
반응완료 후, 물을 투입하고 세정하여 트리에틸아민을 제거한 후, 정제하여 [화학식 Ⅲ] 15.58 mmol을 얻었다.
After completion of the reaction, water was added and washed to remove triethylamine, and then purified to obtain 15.58 mmol of [Formula III].
(7) [화학식 Ⅳ] 화합물의 합성(7) Synthesis of compound of formula (IV)
하기 반응식에 따라 [화학식 Ⅳ]로 표시되는 화합물을 합성하였다.A compound represented by the formula (IV) was synthesized according to the following reaction formula.
[화학식 Ⅲ] [화학식 Ⅳ][Formula (III) [Formula IV]
[화학식 Ⅲ] 화합물 12.00 mmol, 트리에틸아민 24.00 mmol에 디클로로메탄 70.00 g을 첨가하여 교반 용해하였다. 그 후, 메타아크릴산 무수물 24.00 mmol을 투입한 후, 40 ℃로 승온하고 유지하였다. 반응종료 후, 물을 첨가하고 교반하여 세정하였다. 층분리 후, 유기층을 감압농축하고 정제하여 [화학식 Ⅳ] 화합물 10.06 mmol을 얻었다.
[Chemical Formula III] Dichloromethane (70.00 g) was added to the compound (12.00 mmol) and triethylamine (24.00 mmol) and dissolved by stirring. Thereafter, 24.00 mmol of methacrylic anhydride was added, and the temperature was raised to 40 캜 and maintained. After completion of the reaction, water was added, and the mixture was stirred and washed. After layer separation, the organic layer was concentrated under reduced pressure and purified to obtain 10.06 mmol of the compound of the formula (IV).
(8) 합성예 4 : [화학식 5] 화합물의 합성(8) Synthesis Example 4: Synthesis of Compound (5)
하기 반응식에 따라 [화학식 5]로 표시되는 화합물을 합성하였다.A compound represented by formula 5 was synthesized according to the following reaction formula.
[화학식 Ⅳ] [화학식 5][Formula IV] [Chemical Formula 5]
[화학식 Ⅳ] 화합물 10.06 mmol에 디클로로메탄 90.00 g을 첨가하여 교반 용해하였다. 리튬 비스(트리플루오르메탄)술폰이미드 11.07 mmol을 20% 수용액으로 용해하여 투입한 후, 상온에서 1시간 교반하였다. 층분리하여 유기층을 물로 세척하고 감압농축 후, 정제하여 [화학식 5] 화합물 8.76 mmol을 얻었다.
90.06 g of dichloromethane was added to 10.06 mmol of the compound of the formula (IV) and dissolved by stirring. Lithium bis (trifluoromethane) sulfonimide (11.07 mmol) was dissolved in 20% aqueous solution, and the mixture was stirred at room temperature for 1 hour. The organic layer was washed with water, concentrated under reduced pressure, and purified to obtain 8.76 mmol of a compound represented by the following formula (5).
(9) 합성예 5 : [화학식 6] 화합물의 합성(9) Synthesis Example 5: Synthesis of Compound (6)
하기 반응식에 따라 [화학식 6]으로 표시되는 화합물을 합성하였다.A compound represented by the formula (6) was synthesized according to the following reaction formula.
[화학식 Ⅳ] [화학식 6][Formula IV] [Chemical Formula 6]
[화학식 Ⅳ] 화합물 10.06 mmol에 디클로로메탄 90.00 g을 첨가하여 교반 용해하였다. 리튬 노나플루오르부탄술포네이트 11.07 mmol을 20% 수용액으로 용해하여 투입한 후, 상온에서 1시간 교반하였다. 층분리하여 유기층을 물로 세척하고 감압농축 후, 정제하여 [화학식 6] 화합물 8.47 mmol을 얻었다.
90.06 g of dichloromethane was added to 10.06 mmol of the compound of the formula (IV) and dissolved by stirring. Lithium nonafluorobutanesulfonate (11.07 mmol) was dissolved in a 20% aqueous solution, and the mixture was stirred at room temperature for 1 hour. The organic layer was washed with water, concentrated under reduced pressure, and purified to obtain 8.47 mmol of a compound represented by the following formula (6).
(10) 합성예 6 : [화학식 7] 화합물의 합성(10) Synthesis Example 6: Synthesis of Compound (7)
하기 반응식에 따라 [화학식 7]로 표시되는 화합물을 합성하였다.A compound represented by the formula (7) was synthesized according to the following reaction formula.
[화학식 Ⅳ] [화학식 7][Formula IV] (7)
[화학식 Ⅳ] 화합물 10.06 mmol에 디클로로메탄 90.00 g을 첨가하여 교반 용해하였다. 칼륨 테트라키스(펜타플루오르페닐)보레이트 11.07 mmol을 20% 수용액으로 용해하여 투입한 후, 상온에서 1시간 교반하였다. 층분리하여 유기층을 물로 세척하고 감압농축 후, 정제하여 [화학식 7] 화합물 8.55 mmol을 얻었다.
90.06 g of dichloromethane was added to 10.06 mmol of the compound of the formula (IV) and dissolved by stirring. 11.07 mmol of potassium tetrakis (pentafluorophenyl) borate was dissolved in 20% aqueous solution, and the mixture was stirred at room temperature for 1 hour. Layer separation. The organic layer was washed with water, concentrated under reduced pressure, and purified to obtain 8.55 mmol of a compound of the formula (7).
실험예 1. 용해도 평가Experimental Example 1. Evaluation of solubility
합성예 1 내지 합성예 6에 따른 염료 화합물과 비교예 1(로다민 B)를 프로필렌글리콜 모노메틸 에테르 아세테이트(PGMEA)에 용해하여 용해도를 확인하였고, 그 결과를 하기 [표 1]에 나타내었다.The dye compound of Synthesis Examples 1 to 6 and Comparative Example 1 (rhodamine B) were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to confirm solubility. The results are shown in Table 1 below.
상기 [표 1]에서 보는 바와 같이, 비교예 1 화합물은 1% 미만의 낮은 용해도를 보이는 데 비해, 본 발명에 따른 합성예 1 내지 6의 크산텐 염료 화합물은 PGEMA에 5% 이상의 높은 용해도를 가지는 것을 확인할 수 있다. 따라서, 본 발명의 화합물은 유기 용매에 대하여 우수한 용해도 특성을 가짐을 알 수 있다.
As shown in the above Table 1, the compound of Comparative Example 1 has a low solubility of less than 1%, whereas the xanthene dye compound of Synthesis Examples 1 to 6 according to the present invention has a solubility of 5% or more in PGEMA . Therefore, it can be seen that the compound of the present invention has excellent solubility characteristics with respect to an organic solvent.
실험예 2. 내열성 평가Experimental Example 2. Evaluation of heat resistance
내열성 평가를 위해 아래와 같이 실시예 1 내지 6의 수지 조성물과 비교예 1의 수지 조성물을 제조하였다.For evaluation of heat resistance, the resin compositions of Examples 1 to 6 and Comparative Example 1 were prepared as follows.
(1) 실시예 1 : 수지 조성물의 제조(1) Example 1: Preparation of resin composition
다음과 같은 조성으로 수지 조성물을 제조하였다.A resin composition was prepared in the following composition.
(a) 바인더수지 : 벤질메타아크릴레이트/메타아크릴산(60 : 40 질량비)의 공중합체(Mw=20000) 2.7 g(a) Binder resin: 2.7 g of a copolymer (Mw = 20000) of benzylmethacrylate / methacrylic acid (60: 40 mass ratio)
(b) 아크릴 모노머 : 디펜타에리트리톨 헥사아크릴레이트 10 g(b) Acrylic monomer: 10 g of dipentaerythritol hexaacrylate
(c) 염료 화합물 : 합성예 1 2.3 g(c) Dye compound: Synthesis Example 1 2.3 g
(d) 광중합 개시제 : BASF사의 Irgacure OXE-01 2 g(d) Photopolymerization initiator: 2 g of Irgacure OXE-01 manufactured by BASF
(e) 용제 : 프로필렌글리콜 모노메틸에테르 아세테이트 83 g
(e) Solvent: Propylene glycol monomethyl ether acetate 83 g
(2) 실시예 2 내지 6 및 비교예 2 : 수지 조성물의 제조(2) Examples 2 to 6 and Comparative Example 2: Production of resin composition
상기 실시예 1과 동일한 조성과 동일하게 수지 조성물을 제조하였으며, 다만 염료 화합물을 합성예 1 대신 하기 [표 2]와 같이 화합물을 바꾸어 수지 조성물을 제조하였다.A resin composition was prepared in the same manner as in Example 1 except that the dye compound was changed to the compound shown in Table 2 instead of the compound of Synthesis Example 1 to prepare a resin composition.
(3) 내열성 측정(3) Heat resistance measurement
내열성 측정을 위해 10 ㎝ × 10 ㎝의 유리기판 위에 상기 실시예 및 비교예에서 제조한 수지 조성물을 각각 2 ㎛ 두께로 스핀 코팅하여 90 ℃의 핫플레이트에서 3 분 동안 프리베이크(pre-bake)를 수행한 후, 상온에서 1 분 동안 냉각하였다. 이를 노광기를 이용하여 100 mJ/㎠의 노광량(365 ㎚ 기준)으로 노광하였다.For the measurement of the heat resistance, the resin compositions prepared in the above Examples and Comparative Examples were each spin-coated on a glass substrate of 10 cm x 10 cm in thickness of 2 mu m and pre-baked on a hot plate at 90 DEG C for 3 minutes And then cooled at room temperature for 1 minute. This was exposed using an exposure machine at an exposure amount of 100 mJ / cm 2 (based on 365 nm).
이후, 230 ℃의 컨벡션 오븐(convection oven)에서 30 분 동안 포스트베이크(postbake)를 수행한 후, 분광광도계인 Otsuka electronic사의 MCPD3700을 사용하여 색 특성을 확인하고, 230 ℃ 컨벡션 오븐에서 1시간 추가로 열처리를 진행한 후, 다시 색 특성을 확인하여 ΔEab*값을 구하여 하기 [표 3]에 나타내었다.After post-baking in a convection oven at 230 ° C for 30 minutes, color characteristics were confirmed using a spectrophotometer, MCPD 3700 from Otsuka electronic Co., After the heat treatment, the color characteristic was confirmed again and the value of? Eab * was determined and shown in Table 3 below.
일반적으로 ΔEab* 3 이하를 만족하여야 신뢰성을 만족하는 것으로 알려져있다. 비교예 2의 경우, 내열성이 크게 떨어지는 것을 알 수 있으며, 본 발명에 따른 화합물은 내열성이 우수함을 알 수 있다.Generally, it is known that satisfies the reliability because it satisfies ΔEab * 3 or less. In the case of Comparative Example 2, it can be seen that the heat resistance is greatly lowered, and the compound according to the present invention is excellent in heat resistance.
Claims (5)
[화학식 1]
상기 [화학식 1]에서,
X-는 노나플루오르부탄술폰산 음이온, 비스(트리플루오르메탄)술폰이미드 음이온 또는 테트라키스(펜타플루오르페닐)보레이트 음이온이고,
R1, R2, R3 및 R4는 각각 독립적으로 수소, 치환 또는 비치환된 탄소수 1 내지 10의 알킬기, 알릴기, 치환 또는 비치환된 탄소수 6 내지 10의 방향족 탄화수소 및 하기 [구조식 1] 또는 [구조식 2]로 표시되는 R8 중에서 선택되며,
[구조식 1]
[구조식 2]
상기 [구조식 1] 및 [구조식 2]에서,
R9는 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이고, R10은 수소 또는 메틸이고,
R5 및 R6는 각각 독립적으로 치환 또는 비치환된 탄소수 1 내지 5의 알킬렌기이며,
Z는 N 또는 C-H이고,
R7은 하기 [구조식 3] 또는 [구조식 4]이며,
[구조식 3]
[구조식 4]
상기 [구조식 3] 및 [구조식 4]에서,
R11은 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이고, R12는 수소 또는 메틸이다.A xanthene dye compound represented by the following formula 1:
[Chemical Formula 1]
In the above formula (1)
X - is a nonafluorobutanesulfonic acid anion, a bis (trifluoromethanesulfonimide) anion or a tetrakis (pentafluorophenyl) borate anion,
R 1 , R 2 , R 3 and R 4 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an allyl group, a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms, Or R < 8 > Lt; / RTI >
[Structural formula 1]
[Structural formula 2]
In the above-mentioned structural formulas 1 and 2,
R 9 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, R 10 is hydrogen or methyl,
R 5 And R 6 are each independently a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms,
Z is N or CH,
R 7 is [Structural Formula 3] or [Structural Formula 4]
[Structural Formula 3]
[Structural Formula 4]
In the above Structural Formula 3 and Structural Formula 4,
R 11 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and R 12 is hydrogen or methyl.
상기 [화학식 1]은 하기 [화학식 2] 내지 [화학식 7]로 표시되는 화합물 중에서 선택되는 것을 특징으로 하는 크산텐 염료 화합물:
[화학식 2]
[화학식 3]
[화학식 4]
[화학식 5]
[화학식 6]
[화학식 7]
The method according to claim 1,
The xanthene dye compound according to claim 1, wherein the compound represented by the formula (1) is selected from compounds represented by the following formulas (2) to (7)
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
[Chemical Formula 6]
(7)
[반응식 1]
[E] [화학식 1]
상기 [반응식 1]에서,
X-, R1, R2, R3, R4, R5, R6 및 R7은 상기 제1항의 [화학식 1]에서의 정의와 동일하다.Following [Scheme 1] according to [Formula E] After the compound is dissolved in an alcohol and a halogenated hydrocarbon, an anion (X -) is added dropwise a salt solution, followed by stirring process for producing a xanthene dye compound represented by Formula 1:
[Reaction Scheme 1]
[E] [Formula 1]
In the above Reaction Scheme 1,
X - , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 And R < 7 > are the same as defined in the above formula (1).
상기 [화학식 E] 화합물은 하기 [반응식 2]에 따라,
하기 [화학식 D] 화합물을 산 촉매 하에서 아크릴산 또는 메타아크릴산과 반응시키거나,
또는 하기 [화학식 D] 화합물을 염기 촉매 하에서 아크릴산 무수물 또는 메타아크릴산 무수물과 반응시켜 제조되는 것을 특징으로 하는 크산텐 염료 화합물의 제조방법:
[반응식 2]
[D] [E]
상기 [반응식 2]에서,
R1, R2, R3, R4, R5, R6 및 R7은 상기 제1항의 [화학식 1]에서의 정의와 동일하고, R13은 하이드록시기 또는 치환 또는 비치환된 탄소수 1 내지 10의 하이드록시알킬이다.The method of claim 3,
[Formula (E)] < / RTI >
Reacting a compound represented by the following formula [D] with acrylic acid or methacrylic acid under an acid catalyst,
Or a compound of the following formula [D] is reacted with acrylic acid anhydride or methacrylic acid anhydride under base catalysis:
[Reaction Scheme 2]
[D] [E]
In the above Reaction Scheme 2,
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 And R < 7 > are the same as defined in the above formula (1), and R < 13 > is a hydroxy group or a substituted or unsubstituted hydroxyalkyl of 1 to 10 carbon atoms.
상기 [화학식 D] 화합물은 하기 [반응식 3]에 따라,
(c) [화학식 A] 화합물을 용매 하에서 티오닐클로라이드와 반응시켜 산염화물을 합성하는 단계; 및
(d) 상기 산염화물을 하기 [화학식 B] 또는 [화학식 C] 화합물 반응시키는 단계;를 포함하여 제조되는 것을 특징으로 하는 크산텐 염료 화합물의 제조방법:
[반응식 3]
[A] [D]
상기 [반응식 3]에서,
R1, R2, R3, R4, R5 및 R6은 상기 제1항의 [화학식 1]에서의 정의와 동일하고, R13은 하이드록시기 또는 치환 또는 비치환된 탄소수 1 내지 10의 하이드록시알킬이다.5. The method of claim 4,
The compound [Formula D] may be prepared according to the following Reaction Scheme 3,
(c) reacting a compound of formula (A) with thionyl chloride in a solvent to synthesize an acid chloride; And
(d) reacting the acid chloride with a compound represented by the following formula (B) or (C):
[Reaction Scheme 3]
[A] [D]
In the above reaction scheme 3,
R 1 , R 2 , R 3 , R 4 , R 5 And R < 6 > are the same as defined in the above formula (1), and R < 13 > is a hydroxy group or a substituted or unsubstituted hydroxyalkyl of 1 to 10 carbon atoms.
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