TWI682921B - Oxime ester compounds, photopolymerization initiator and photopolymerizable composition containing the same, molded article and display device - Google Patents

Oxime ester compounds, photopolymerization initiator and photopolymerizable composition containing the same, molded article and display device Download PDF

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TWI682921B
TWI682921B TW105103739A TW105103739A TWI682921B TW I682921 B TWI682921 B TW I682921B TW 105103739 A TW105103739 A TW 105103739A TW 105103739 A TW105103739 A TW 105103739A TW I682921 B TWI682921 B TW I682921B
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diethyl
bis
reaction
oxime
fusel
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TW201634444A (en
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吳泉林
辛承林
申鍾一
安慶龍
全根
李得洛
趙鏞一
李敏善
李元重
李栽訓
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韓國化學研究院
南韓商三養公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/68—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with at least one of the esterifying carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

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Abstract

Provided are a novel oxime ester compound, and a photopolymerization initiator and a photopolymerizable composition containing the same, wherein the oxime ester compound of the present disclosure has excellent sensitivity, heat resistance, light resistance, chemical resistance, and resistance to a development property, thereby providing a photopolymerization initiator and a photopolymerizable composition that are effective for exposure and post-bake processes, etc., in a thin film transistor-liquid crystal display (TFT-LCD) manufacturing method even in a small amount.

Description

肟酯化合物、含有肟酯化合物之光聚合起始劑及可光聚合的組成物、模製物件及顯示器裝置 Oxime ester compound, photopolymerization initiator containing oxime ester compound and photopolymerizable composition, molded article and display device

本發明之態樣關於一種肟酯化合物及含有該肟酯化合物之光聚合起始劑及可光聚合的組成物。 The aspect of the present invention relates to an oxime ester compound, a photopolymerization initiator containing the oxime ester compound, and a photopolymerizable composition.

用於可光聚合的組成物之光聚合起始劑已知有多種類型，如苯乙酮衍生物、二苯甲酮衍生物、三嗪(triazine)衍生物、二咪唑衍生物、醯基膦氧化物(acylphosphine oxide)衍生物及肟酯衍生物等。彼等當中，肟酯衍生物的優點在於，該肟酯衍生物在吸收紫外線後呈現幾乎無色，且對產生自由基的效率高，並與可光聚合的組成物之材料的相容性及其穩定性優異。然而，最早開發的肟衍生物化合物的問題在於，在進行曝光圖案過程期間具有低的光引發效率，特別是低的敏感性，使得需要增加曝光量，且相應地降低生產量。 Various types of photopolymerization initiators for photopolymerizable compositions are known, such as acetophenone derivatives, benzophenone derivatives, triazine derivatives, diimidazole derivatives, and acetylphosphine Oxide (acylphosphine oxide) derivatives and oxime ester derivatives. Among them, the advantage of the oxime ester derivative is that the oxime ester derivative is almost colorless after absorbing ultraviolet rays, and is highly efficient for generating free radicals, and is compatible with the materials of the photopolymerizable composition and its Excellent stability. However, the problem with the earliest developed oxime derivative compounds is that they have low photoinitiation efficiency during the exposure patterning process, especially low sensitivity, making it necessary to increase the exposure amount and reduce the production amount accordingly.

因此，經由發展具有優異光敏性的光聚合起始劑，即使是少量的光聚合起始劑也能實現足夠的敏感性，使得成本可以降低，且由於優異的敏感性也可以降低曝光量，從而可以增加生產量。 Therefore, by developing a photopolymerization initiator having excellent photosensitivity, even a small amount of photopolymerization initiator can achieve sufficient sensitivity, so that the cost can be reduced, and the exposure can be reduced due to the excellent sensitivity, thereby Can increase production.

可用作可光聚合的組成物中的光聚合起始劑已知有由以下化學式A表示的多種肟酯化合物。 A variety of oxime ester compounds represented by the following chemical formula A are known as photopolymerization initiators that can be used as the photopolymerizable composition.

Figure 105103739-A0202-12-0002-2
Figure 105103739-A0202-12-0002-2

在由化學式A表示的肟酯化合物之實例中，適當的取代基可以分別被導入R、R'和R"，使得含有該肟酯化合物之光聚合起始劑的光吸收區域能夠被控制。 In the example of the oxime ester compound represented by the chemical formula A, appropriate substituents may be introduced into R, R′, and R″, respectively, so that the light absorption region of the photopolymerization initiator containing the oxime ester compound can be controlled.

肟酯化合物可聚合及固化具有不飽和鍵的聚合化合物，其係經波長為365nm(奈米)至435nm的光照到該可光聚合的組成物，藉此使該可光聚合的組成物能用於黑色矩陣、彩色過濾器、柱狀間隙物(column spacer)、可撓性絕緣膜、塗料層(overcoat)等。 The oxime ester compound can polymerize and cure a polymer compound having an unsaturated bond, which is irradiated to the photopolymerizable composition with light having a wavelength of 365 nm (nm) to 435 nm, thereby making the photopolymerizable composition usable For black matrix, color filter, column spacer, flexible insulating film, overcoat, etc.

因此，仍然需要一種新穎光起始劑，其對波長為 365nm至435nm之長波長的光源具有高敏感性與良好的光聚合反應性、容易被製備、具有高熱穩定性和儲存穩定性而可易於操作、以及滿足工業領域的要求如溶解度等，其對作為溶劑(丙二醇單甲基醚乙酸酯；PGMEA)為勝任的，藉此能適用於多種應用。 Therefore, there is still a need for a novel photoinitiator, which has a wavelength of The long wavelength light source of 365nm to 435nm has high sensitivity and good photopolymerization reactivity, is easy to be prepared, has high thermal stability and storage stability and can be easily handled, and meets the requirements of the industrial field such as solubility, etc. Solvents (propylene glycol monomethyl ether acetate; PGMEA) are competent and thus can be adapted to a variety of applications.

近年來，一直在積極進行的研究是用於薄膜顯示器如液晶顯示器裝置、有機發光二極體(OLEDs)等之可光聚合的組成物，更具體地，是研究含有高度敏感性光聚合起始劑之可光聚合的組成物，其經以鹼性顯影劑溶液顯影該可光聚合的組成物能夠形成圖案如液晶顯示器裝置(如薄膜電晶體液晶顯示器；TFT-LCD)之有機絕緣膜、柱狀間隙物、紫外線(UV)塗料層、紅色、綠色、藍色(R.G.B)彩色光阻及黑色矩陣等。 In recent years, researches that have been actively carried out are photopolymerizable compositions for thin-film displays such as liquid crystal display devices, organic light-emitting diodes (OLEDs), etc., more specifically, studies that contain highly sensitive photopolymerization initiation A photopolymerizable composition of an agent, which can be formed into a pattern such as an organic insulating film and a pillar of a liquid crystal display device (such as a thin film transistor liquid crystal display; TFT-LCD) by developing the photopolymerizable composition with an alkaline developer solution Spacer, ultraviolet (UV) paint layer, red, green, blue (RGB) color photoresist, black matrix, etc.

至於現有用於形成圖案之可光聚合的組成物，較佳是含有黏合劑樹脂之可光聚合的組成物、具有烯系(ethylenically)不飽和鍵的多官能性單體及光聚合組成物。然而，在使用該現有光聚合起始劑來形成圖案時具有的問題是，在形成圖案之曝光過程時由於低敏感性，使得該光聚合起始劑的使用量或曝光量需要增加，因此，使得光罩在該曝光過程可能受污染。再者，在高溫交聯時，由於在光聚合起始劑分解時所產生的副產物使得產量可能劣化，且由於增加曝光過程的時間所致的曝光量之增加使得產 量可能降低。 As for the existing photopolymerizable composition for forming a pattern, it is preferably a photopolymerizable composition containing a binder resin, a polyfunctional monomer having an ethylenically unsaturated bond, and a photopolymerizable composition. However, when using the existing photopolymerization initiator to form a pattern, there is a problem that the use amount or exposure amount of the photopolymerization initiator needs to be increased due to low sensitivity during the exposure process of forming a pattern. Therefore, Therefore, the photomask may be contaminated during the exposure process. Furthermore, during high-temperature crosslinking, the yield may be deteriorated due to by-products generated when the photopolymerization initiator decomposes, and the increase in exposure due to the increase in the time of the exposure process makes the yield The amount may be reduced.

因此，本案發明人致力於解決現有可光聚合的組成物之上述問題，發現一種新穎肟酯化合物，其對光的敏感性優異，以便具有高反應轉化率，且其熱穩定性和光穩定性優異，使得該肟酯化合物沒有在光引發後分解，從而實現高圖案穩定性及高殘餘厚度比率[A1]；以及一種含有該肟酯化合物之光聚合起始劑及可光聚合的組成物，從而完成本發明。 Therefore, the inventors of the present invention are devoted to solving the above problems of the existing photopolymerizable composition, and found a novel oxime ester compound which is excellent in light sensitivity so as to have a high reaction conversion rate and is excellent in thermal stability and light stability , So that the oxime ester compound does not decompose after photoinitiation, thereby achieving high pattern stability and high residual thickness ratio [A1]; and a photopolymerization initiator and photopolymerizable composition containing the oxime ester compound, thereby Complete the present invention.

[先前技術文獻] [Prior Technical Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本專利特許公開第2001-302871號(2001年10月31日)。 [Patent Document 1] Japanese Patent Laid-Open No. 2001-302871 (October 31, 2001).

[專利文獻2]WO02-100903(2002年12月19日)。 [Patent Document 2] WO02-100903 (December 19, 2002).

[專利文獻3]日本專利特許公開第2006-160634號(2006年6月22日)。 [Patent Document 3] Japanese Patent Laid-Open No. 2006-160634 (June 22, 2006).

[專利文獻4]日本專利特許公開第2005-025169號(2005年1月27日)。 [Patent Document 4] Japanese Patent Laid-Open No. 2005-025169 (January 27, 2005).

[專利文獻5]日本專利特許公開第2005-242279號(2005年9月8日)。 [Patent Document 5] Japanese Patent Laid-Open No. 2005-242279 (September 8, 2005).

[專利文獻6]WO07-071497(2007年6月28日)。 [Patent Document 6] WO07-071497 (June 28, 2007).

[專利文獻7]WO08-138733(2008年11月20日)。 [Patent Document 7] WO08-138733 (November 20, 2008).

[專利文獻8]WO08-078686(2008年7月3日)。 [Patent Document 8] WO08-078686 (July 3, 2008).

[專利文獻9]WO09-081483(2009年7月2日)。 [Patent Document 9] WO09-081483 (July 2, 2009).

[專利文獻10]韓國專利公開第2013-0049811號(2013年11月13日)。 [Patent Document 10] Korean Patent Publication No. 2013-0049811 (November 13, 2013).

[專利文獻11]韓國專利公開第2013-0115272號(2013年10月21日)。 [Patent Document 11] Korean Patent Publication No. 2013-0115272 (October 21, 2013).

本發明之實施例係關於提供一種肟酯化合物，其具有優異敏感性、耐熱性、耐光性、耐化學性；以及含有該肟酯化合物之光聚合起始劑及可光聚合的組成物。 Embodiments of the present invention relate to providing an oxime ester compound having excellent sensitivity, heat resistance, light resistance, and chemical resistance; and a photopolymerization initiator and a photopolymerizable composition containing the oxime ester compound.

本發明之另一實施例係關於提供一種模製物件，包括含有該肟酯化合物之可光聚合的組成物的固化產物。 Another embodiment of the present invention relates to providing a molded article including a cured product of a photopolymerizable composition containing the oxime ester compound.

本發明之又一實施例係關於提供一種顯示器裝置，其含有該模製物件。 Yet another embodiment of the present invention relates to providing a display device including the molded object.

根據本發明之一態樣，其關於一種由化學式1表示的肟酯化合物以及含有該肟酯化合物之光聚合起始劑及可光聚合的組成物。 According to one aspect of the present invention, it relates to an oxime ester compound represented by Chemical Formula 1, a photopolymerization initiator containing the oxime ester compound, and a photopolymerizable composition.

[化學式1]

Figure 105103739-A0202-12-0006-3
[Chemical Formula 1]
Figure 105103739-A0202-12-0006-3

化學式1中，R1至R3各自獨立為氫、鹵素、(C1-C20)烷基、(C6-C20)芳基、(C1-C20)烷氧基、(C6-C20)芳基(C1-C20)烷基、羥基(C1-C20)烷基、羥基(C1-C20)烷氧基(C1-C20)烷基、(C3-C20)環烷基或(C3-C20)環烷基(C1-C20)烷基；A為氫、鹵素、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、胺基、硝基、氰基或羥基；L1為直接鍵、-CO-或

Figure 105103739-A0202-12-0006-4
，R4及R5各自獨立為氫、鹵素、(C1-C20)烷基、(C6-C20)芳基、(C1-C20)烷氧基、(C6-C20)芳基(C1-C20)烷基、羥基(C1-C20)烷基、羥基(C1-C20)烷氧基(C1-C20)烷基、(C3-C20)環烷基或(C3-C20)環烷基(C1-C20)烷基，m為選自0至2的整數；及 n為1或2的整數。 In Chemical Formula 1, R 1 to R 3 are each independently hydrogen, halogen, (C 1 -C 20 )alkyl, (C 6 -C 20 )aryl, (C 1 -C 20 )alkoxy, (C 6 -C 20 )aryl (C 1 -C 20 )alkyl, hydroxy (C 1 -C 20 )alkyl, hydroxy (C 1 -C 20 )alkoxy (C 1 -C 20 )alkyl, (C 3 -C 20 )cycloalkyl or (C 3 -C 20 )cycloalkyl (C 1 -C 20 )alkyl; A is hydrogen, halogen, (C 1 -C 20 )alkyl, (C 6 -C 20 ) aryl, (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl, amine, nitro, cyano or hydroxy; L 1 is a direct bond, -CO- or
Figure 105103739-A0202-12-0006-4
, R 4 and R 5 are each independently hydrogen, halogen, (C 1 -C 20 )alkyl, (C 6 -C 20 )aryl, (C 1 -C 20 )alkoxy, (C 6 -C 20 ) Aryl (C 1 -C 20 ) alkyl, hydroxy (C 1 -C 20 ) alkyl, hydroxy (C 1 -C 20 ) alkoxy (C 1 -C 20 ) alkyl, (C 3 -C 20) cycloalkyl or (C 3 -C 20) cycloalkyl (C 1 -C 20) alkyl, m is an integer selected from 0 to 2; and n is an integer of 1 or 2.

本發明之術語「芳基」係從芳香烴中去除一個氫原子而形成的有機基團，且包括單環系或稠合環系，各環中適當含有4至7個環原子，較佳5或6個環原子，且更包含其中透過直接鍵連結之複數芳基。芳基之具體實例可包含苯基、萘基、聯苯基、聯三苯基、蒽基、茚基、茀基、菲基等，但本發明並不限於此。 The term "aryl" in the present invention is an organic group formed by removing one hydrogen atom from an aromatic hydrocarbon, and includes a single ring system or a condensed ring system, and each ring suitably contains 4 to 7 ring atoms, preferably 5 Or 6 ring atoms, and more including a plurality of aryl groups connected by a direct bond. Specific examples of the aryl group may include phenyl, naphthyl, biphenyl, triphenylphenyl, anthracenyl, indenyl, fluorenyl, phenanthrenyl, etc., but the present invention is not limited thereto.

本發明之術語「芳基烷基」意指經上述定義之芳基取代的烷基，且包含苯甲基等作為實例。 The term "arylalkyl" in the present invention means an alkyl group substituted with the above-defined aryl group, and includes benzyl group and the like as examples.

本發明之術語「羥基烷基」意指經羥基取代的烷基，且包含羥基甲基、羥基乙基、羥基丙基、羥基丁基、羥基戊基、羥基己基等作為實例。 The term "hydroxyalkyl" in the present invention means an alkyl group substituted with a hydroxy group, and includes hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl and the like as examples.

本發明之術語「羥基烷氧基烷基」意指經羥基烷氧基取代的烷基，且包含羥基甲氧基甲基、羥基甲氧基乙基、羥基甲氧基丙基、羥基甲氧基丁基、羥基乙氧基甲基、羥基乙氧基乙基、羥基乙氧基丙基、羥基乙氧基丁基、羥基乙氧基戊基、羥基乙氧基己基等作為實例。 The term "hydroxyalkoxyalkyl" in the present invention means an alkyl substituted with hydroxyalkoxy, and includes hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxy Examples include butylbutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl, hydroxyethoxyhexyl, and the like.

本發明之術語「環烷基」不僅指3至7個碳原子環之單環烷基，且亦指其中兩個或更多個單環烷基彼此稠合的 多環烷基。環烷基之具體實例包含環丙基、環丁基、環戊基、環己基等，但本發明並不限於此。 The term "cycloalkyl" in the present invention refers not only to a monocyclic alkyl group of 3 to 7 carbon atom rings, but also to a group in which two or more monocyclic alkyl groups are fused to each other Polycycloalkyl. Specific examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., but the present invention is not limited thereto.

本發明之術語「環烷基烷基」意指經上述定義之環烷基取代的烷基，且包含環丙基甲基、環丁基甲基、環戊基甲基、環丙基乙基等作為實例。 The term "cycloalkylalkyl" in the present invention means an alkyl group substituted with the above-defined cycloalkyl group, and includes cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclopropylethyl, etc. as Examples.

再者，本發明之「(C1-C20)烷基」基團較佳為(C1-C10)烷基，且更佳為(C1-C7)烷基。「(C6-C20)芳基」基團較佳為(C6-C18)芳基。「(C1-C20)烷氧基」基團較佳為(C1-C10)烷氧基，且更佳為(C1-C7)烷氧基。「(C6-C20)芳基(C1-C20)烷基」基團較佳為(C6-C18)芳基(C1-C10)烷基，且更佳為(C6-C18)芳基(C1-C7)烷基。本發明之「羥基(C1-C20)烷基」基團較佳為羥基(C1-C10)烷基，且更佳為羥基(C1-C7)烷基。「羥基(C1-C20)烷氧基(C1-C20)烷基」基團較佳為羥基(C1-C10)烷氧基(C1-C10)烷基，且更佳為羥基(C1-C7)烷氧基(C1-C7)烷基。「(C3-C20)環烷基」基團較佳為(C3-C10)環烷基。「(C3-C20)環烷基(C1-C20)烷基」基團較佳為(C3-C10)環烷基(C1-C10)烷基，且更佳為(C3-C10)環烷基(C1-C7)烷基。 Furthermore, the "(C 1 -C 20 )alkyl" group of the present invention is preferably (C 1 -C 10 )alkyl, and more preferably (C 1 -C 7 )alkyl. The "(C 6 -C 20 )aryl" group is preferably (C 6 -C 18 )aryl. The "(C 1 -C 20 )alkoxy" group is preferably (C 1 -C 10 )alkoxy, and more preferably (C 1 -C 7 )alkoxy. The "(C 6 -C 20 )aryl(C 1 -C 20 )alkyl" group is preferably (C 6 -C 18 )aryl(C 1 -C 10 )alkyl, and more preferably (C 6 -C 18 )aryl (C 1 -C 7 )alkyl. The "hydroxy(C 1 -C 20 )alkyl" group of the present invention is preferably a hydroxy(C 1 -C 10 )alkyl group, and more preferably a hydroxy(C 1 -C 7 )alkyl group. The "hydroxy(C 1 -C 20 )alkoxy(C 1 -C 20 )alkyl" group is preferably a hydroxy(C 1 -C 10 )alkoxy(C 1 -C 10 )alkyl group, and more Preferably, it is hydroxy(C 1 -C 7 )alkoxy(C 1 -C 7 )alkyl. The "(C 3 -C 20 )cycloalkyl" group is preferably (C 3 -C 10 )cycloalkyl. The "(C 3 -C 20 )cycloalkyl(C 1 -C 20 )alkyl" group is preferably (C 3 -C 10 )cycloalkyl(C 1 -C 10 )alkyl, and more preferably (C 3 -C 10 )cycloalkyl (C 1 -C 7 )alkyl.

化學式1中，當n為2，包括在每個肟酯基團中的R2及R3可以彼此相同或彼此不同，且當m為2時，R5可以彼此相同或彼此不同。 In Chemical Formula 1, when n is 2, R 2 and R 3 included in each oxime ester group may be the same as or different from each other, and when m is 2, R 5 may be the same as or different from each other.

鑒於對波長為365nm至435nm的光的優異敏感性，根據本發明之一例示性實施例的肟酯化合物可具有兩個或四個肟酯基團，類似於由化學式2至化學式3表示的肟酯化合物，但本發明並不限於此。 In view of the excellent sensitivity to light having a wavelength of 365 nm to 435 nm, the oxime ester compound according to an exemplary embodiment of the present invention may have two or four oxime ester groups, similar to the oxime represented by Chemical Formula 2 to Chemical Formula 3 Ester compound, but the invention is not limited thereto.

Figure 105103739-A0202-12-0009-5
Figure 105103739-A0202-12-0009-5

Figure 105103739-A0202-12-0009-6
Figure 105103739-A0202-12-0009-6

Figure 105103739-A0202-12-0009-7
Figure 105103739-A0202-12-0009-7

化學式2至化學式4中，R1至R5各自獨立為氫、鹵素、(C1-C20)烷基、(C6-C20)芳基、(C1-C20)烷氧基、(C6-C20)芳基(C1-C20)烷基、羥基(C1-C20)烷基、羥基(C1-C20)烷氧基(C1-C20)烷基、(C3-C20)環烷基或(C3-C20)環烷基(C1-C20)烷基；A為氫、鹵素、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、胺基、硝基、氰基或羥基；m為選自0至2的整數；及a及b為0或1的整數。 In Chemical Formula 2 to Chemical Formula 4, R 1 to R 5 are each independently hydrogen, halogen, (C 1 -C 20 )alkyl, (C 6 -C 20 )aryl, (C 1 -C 20 )alkoxy, (C 6 -C 20 )aryl (C 1 -C 20 )alkyl, hydroxy (C 1 -C 20 )alkyl, hydroxy (C 1 -C 20 )alkoxy (C 1 -C 20 )alkyl , (C 3 -C 20 )cycloalkyl or (C 3 -C 20 )cycloalkyl (C 1 -C 20 )alkyl; A is hydrogen, halogen, (C 1 -C 20 )alkyl, (C 6 -C 20 )aryl, (C 6 -C 20 )aryl (C 1 -C 20 )alkyl, amine, nitro, cyano or hydroxy; m is an integer selected from 0 to 2; and a And b is an integer of 0 or 1.

此處，較佳的是，由化學式3或化學式4表示的肟酯化合物中的A在茀(fluorene)的第4號位置處被導入。 Here, it is preferable that A in the oxime ester compound represented by Chemical Formula 3 or Chemical Formula 4 is introduced at the fourth position of fluorene.

在根據本發明之一例示性實施例的肟酯化合物的一例示性實施例中，R1至R5可各自獨立為(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、羥基(C1-C20)烷基、羥基(C1-C20)烷氧基(C1-C20)烷基、(C3-C20)環烷基或(C3-C20)環烷基(C1-C20)烷基；A為氫、鹵素、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、硝基或氰基，或者，在根據本發明之一例示性實施例的肟酯化合物 的另一例示性實施例中，R1至R3可各自獨立為(C1-C20)烷基、(C6-C20)芳基或(C3-C20)環烷基；R4可為氫、(C1-C20)烷基、(C3-C20)環烷基或(C3-C20)環烷基(C1-C20)烷基；R5可為氫、(C1-C20)烷基、(C3-C20)環烷基或(C3-C20)環烷基(C1-C20)烷基；及A可為氫、鹵素、(C1-C20)烷基、(C6-C20)芳基、硝基或氰基，但本發明並不限於此。 In an exemplary embodiment of the oxime ester compound according to an exemplary embodiment of the present invention, R 1 to R 5 may each independently be (C 1 -C 20 )alkyl, (C 6 -C 20 )aryl , (C 6 -C 20 )aryl (C 1 -C 20 )alkyl, hydroxy (C 1 -C 20 )alkyl, hydroxy (C 1 -C 20 )alkoxy (C 1 -C 20 )alkyl Group, (C 3 -C 20 )cycloalkyl or (C 3 -C 20 )cycloalkyl (C 1 -C 20 )alkyl; A is hydrogen, halogen, (C 1 -C 20 )alkyl, ( C 6 -C 20 )aryl, (C 6 -C 20 )aryl (C 1 -C 20 )alkyl, nitro or cyano, or, in an oxime ester compound according to an exemplary embodiment of the present invention In another exemplary embodiment, R 1 to R 3 may each independently be (C 1 -C 20 )alkyl, (C 6 -C 20 )aryl or (C 3 -C 20 )cycloalkyl; R 4 can be hydrogen, (C 1 -C 20 )alkyl, (C 3 -C 20 )cycloalkyl or (C 3 -C 20 )cycloalkyl (C 1 -C 20 )alkyl; R 5 can be Hydrogen, (C 1 -C 20 )alkyl, (C 3 -C 20 )cycloalkyl or (C 3 -C 20 )cycloalkyl (C 1 -C 20 )alkyl; and A may be hydrogen or halogen , (C 1 -C 20 )alkyl, (C 6 -C 20 )aryl, nitro or cyano, but the invention is not limited thereto.

在根據本發明之一例示性實施例的肟酯化合物中，較佳地，R1至R5可各自獨立為選自氫、溴、氯、碘、甲基、乙基、丙基、丁基、戊基、己基、苯基、萘基、聯苯基、聯三苯基、蒽基、茚基、菲基、甲氧基、乙氧基、丙氧基、丁氧基、苯甲基、羥基甲基、羥基乙基、羥基丙基、羥基丁基、羥基戊基、羥基己基、羥基甲氧基甲基、羥基甲氧基乙基、羥基甲氧基丙基、羥基甲氧基丁基、羥基乙氧基甲基、羥基乙氧基乙基、羥基乙氧基丙基、羥基乙氧基丁基、羥基乙氧基戊基、羥基乙氧基己基、環丙基、環戊基、環己基、環丙基甲基、環戊基甲基、環己基甲基等；及A可為選自氫、溴、氯、甲基、乙基、丙基、丁基、苯基、萘基、聯苯基、聯三苯基、蒽基、茚基、菲基、苯甲基、胺基、硝基、氰基及羥基，但本發明並不限於此。 In the oxime ester compound according to an exemplary embodiment of the present invention, preferably, R 1 to R 5 may each independently be selected from hydrogen, bromine, chlorine, iodine, methyl, ethyl, propyl, butyl , Pentyl, hexyl, phenyl, naphthyl, biphenyl, triphenylphenyl, anthracenyl, indenyl, phenanthrenyl, methoxy, ethoxy, propoxy, butoxy, benzyl, Hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl , Hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl, hydroxyethoxyhexyl, cyclopropyl, cyclopentyl, Cyclohexyl, cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, etc.; and A can be selected from hydrogen, bromine, chlorine, methyl, ethyl, propyl, butyl, phenyl, naphthyl , Biphenyl, biphenyl, anthracenyl, indenyl, phenanthrenyl, benzyl, amine, nitro, cyano and hydroxy, but the invention is not limited thereto.

根據本發明之肟酯化合物之一代表性實例可包含下列化合物，但本發明並不限於下列化合物：

Figure 105103739-A0202-12-0012-8
A representative example of the oxime ester compound according to the present invention may include the following compounds, but the present invention is not limited to the following compounds:
Figure 105103739-A0202-12-0012-8

Figure 105103739-A0202-12-0013-9
Figure 105103739-A0202-12-0013-9

Figure 105103739-A0202-12-0014-10
Figure 105103739-A0202-12-0014-10

Figure 105103739-A0202-12-0015-11
Figure 105103739-A0202-12-0015-11

Figure 105103739-A0202-12-0016-12
Figure 105103739-A0202-12-0016-12

Figure 105103739-A0202-12-0017-13
Figure 105103739-A0202-12-0017-13

Figure 105103739-A0202-12-0018-14
Figure 105103739-A0202-12-0018-14

Figure 105103739-A0202-12-0019-15
Figure 105103739-A0202-12-0019-15

根據本發明之由化學式1表示的肟酯化合物可以經由下方反應方案而製備。 The oxime ester compound represented by Chemical Formula 1 according to the present invention can be prepared through the following reaction scheme.

Figure 105103739-A0202-12-0019-16
Figure 105103739-A0202-12-0019-16

Figure 105103739-A0202-12-0020-17
Figure 105103739-A0202-12-0020-17

[反應方案3]

Figure 105103739-A0202-12-0021-18
[Reaction Scheme 3]
Figure 105103739-A0202-12-0021-18

在反應方案1至反應方案3中，R1至R5、A及m係如化學式2至化學式3中所定義者相同，且X1至X4各自獨立為鹵素。 In Reaction Scheme 1 to Reaction Scheme 3, R 1 to R 5 , A and m are the same as defined in Chemical Formula 2 to Chemical Formula 3, and X 1 to X 4 are each independently halogen.

再者，在另一態樣中，本發明提供一種含有由上述化學式1表示的肟酯化合物的光聚合起始劑。 Furthermore, in another aspect, the present invention provides a photopolymerization initiator containing the oxime ester compound represented by the above Chemical Formula 1.

此外，在又一態樣中，本發明提供一種含有由上述化學式1表示的肟酯化合物的可光聚合的組成物。 Furthermore, in still another aspect, the present invention provides a photopolymerizable composition containing the oxime ester compound represented by the above Chemical Formula 1.

在本發明中，由化學式1表示的肟酯化合物可被包含在可光聚合的組成物中作為光聚合起始劑。 In the present invention, the oxime ester compound represented by Chemical Formula 1 may be included in the photopolymerizable composition as a photopolymerization initiator.

本發明之可光聚合的組成物包含由化學式1表示的 肟酯化合物、黏合劑樹脂、具有烯系不飽和鍵的可光聚合的化合物、溶劑等，且具有控制圖案特性的優異能力及優異薄膜物理性能如耐熱性、耐化學性等。 The photopolymerizable composition of the present invention contains the formula 1 Oxime ester compounds, binder resins, photopolymerizable compounds with ethylenically unsaturated bonds, solvents, etc., and have excellent ability to control pattern characteristics and excellent film physical properties such as heat resistance, chemical resistance, etc.

再者，除了由化學式1表示的肟酯化合物以外，本發明之可光聚合的組成物可進一步包含本領域已知的至少一種光聚合起始劑，其選自下列所組成之群組：噻噸酮系(thioxanthone-based)化合物、苯乙酮系化合物、二咪唑系化合物、三嗪系化合物、硫醇系(thiol-based)化合物、O-醯基肟系化合物等。 Furthermore, in addition to the oxime ester compound represented by Chemical Formula 1, the photopolymerizable composition of the present invention may further include at least one photopolymerization initiator known in the art, which is selected from the group consisting of: A thioxanthone-based compound, an acetophenone-based compound, a diimidazole-based compound, a triazine-based compound, a thiol-based compound, an O-acetyl oxime-based compound, and the like.

噻噸酮系化合物之實例可包含噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等，且該噻噸酮系化合物可單獨使用或組合其兩種或更多種使用。苯乙酮系化合物之實例可包含2-甲基-1-[4-(甲基硫基)苯基]-2-嗎啉丙烷-1-酮、2-苯甲基-2-二甲基胺基-1-(4-嗎啉苯基)丁烷-1-酮、2-(4-甲基苯甲基)-2-(二甲基胺基)-1-(4-嗎啉苯基)丁烷-1-酮等，且該苯乙酮系化合物可單獨使用或組合其兩種或更多種使用。二咪唑系化合物之實例可包含2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基-1,2'-二咪唑、2,2'-雙(2,4-二氯苯基)-4,4',5,5'-四苯基-1,2'-二咪唑、2,2'-雙(2,4,6-三氯苯基)-4,4',5,5'-四苯基-1,2'-二咪唑等，且該二咪唑系化合物可單獨使用或組合 其兩種或更多種使用。三嗪系化合物之實例可包含2,4,6-叁(三氯甲基)-s-三嗪、2-甲基-4,6-雙(三氯甲基)-s-三嗪、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-s-三嗪、2-(4-乙氧基苯乙烯)-4,6-雙(三氯甲基)-s-三嗪、2-(4-n-丁氧基苯基)-4,6-雙(三氯甲基)-s-三嗪等，且該三嗪系化合物可單獨使用或組合其兩種或更多種使用。O-醯基肟系化合物之實例可包含1,2-辛二酮-1-[4-(苯基硫基)苯基]-2-(O-苯甲醯基肟)、乙酮-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-1-(O-乙醯基肟)、乙酮-1-[9-乙基-6-(2-甲基-4-四氫呋喃基甲氧基苯甲醯基)-9H-咔唑-3-基]-1-(O-乙醯基肟)、乙酮-1-[9-乙基-6-(2-甲基-4-(2,2-二甲基-1,3-二氧環戊基)甲氧基苯甲醯基-9H-咔唑-3-基]-1-(O-乙醯基肟)等，且該O-醯基肟系化合物可單獨使用或組合其兩種或更多種使用。為予以薄膜圖案更具可撓性的特性，以100重量%之可光聚合的組成物計，本領域中已知的光聚合起始劑的含量可為0.1至5.0重量%。 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-based compound can be used alone Use or combine two or more of them. Examples of the acetophenone-based compound may include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethyl Amino-1-(4-morpholinylphenyl)butane-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylbenzene Group) butane-1-one and the like, and the acetophenone-based compound may be used alone or in combination of two or more thereof. Examples of the diimidazole-based compound may include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis (2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4,6-trichlorophenyl )-4,4',5,5'-tetraphenyl-1,2'-diimidazole, etc., and the diimidazole-based compound can be used alone or in combination Two or more of them are used. Examples of the triazine-based compound may include 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2 -[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl ]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis( Trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2 -(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyrene)-4,6-bis(trichloromethyl) )-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, etc., and the triazine-based compound can be used alone or in combination Two or more of them are used. Examples of the O-acyl oxime-based compound may include 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), ethyl ketone-1 -[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl Yl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[ 9-ethyl-6-(2-methyl-4-(2,2-dimethyl-1,3-dioxocyclopentyl)methoxybenzyl-9H-carbazol-3-yl ]-1-(O-acetyl oxime), etc., and the O-acyl oxime compound can be used alone or in combination of two or more of them. In order to give the film pattern more flexible characteristics, to Based on 100% by weight of the photopolymerizable composition, the content of the photopolymerization initiator known in the art may be 0.1 to 5.0% by weight.

根據本發明之一例示性實施例，可使用丙烯酸系聚合物或在其側鏈上具有丙烯酸系不飽和鍵之丙烯酸系聚合物作為用於可光聚合的組成物之黏合劑樹脂。為了提供用 於控制圖案特性和薄膜物理性能如耐熱性、耐化學性等的能力，以100重量%之可光聚合的組成物計，黏合劑樹脂較佳具有3重量%至50重量%的含量，藉由丙烯酸系聚合物之凝膠滲透層析儀(GPC)測得之聚苯乙烯-轉化率重量平均分子量較佳為2,000至300,000，且丙烯酸系聚合物之分散度較佳為1.0至10.0，其中丙烯酸系聚合物之重量平均分子量更佳為4,000至100,000。 According to an exemplary embodiment of the present invention, an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond on its side chain can be used as the binder resin for the photopolymerizable composition. For the purpose of providing For the ability to control pattern characteristics and film physical properties such as heat resistance, chemical resistance, etc., based on 100% by weight of the photopolymerizable composition, the binder resin preferably has a content of 3% to 50% by weight, by The polystyrene-conversion rate weight average molecular weight measured by gel permeation chromatography (GPC) of acrylic polymer is preferably 2,000 to 300,000, and the dispersion degree of acrylic polymer is preferably 1.0 to 10.0, in which acrylic acid The weight average molecular weight of the polymer is more preferably 4,000 to 100,000.

丙烯酸系聚合物是包括下列單體的共聚物，該單體之實例包括甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、丙基(甲基)丙烯酸酯、丁基(甲基)丙烯酸酯、戊基(甲基)丙烯酸酯、己基(甲基)丙烯酸酯、環己基(甲基)丙烯酸酯、庚基(甲基)丙烯酸酯、辛基(甲基)丙烯酸酯、壬基(甲基)丙烯酸酯、癸基(甲基)丙烯酸酯、月桂基(甲基)丙烯酸酯、十二基(甲基)丙烯酸酯、十四基(甲基)丙烯酸酯、十六基(甲基)丙烯酸酯、異莰基(甲基)丙烯酸酯、金剛烷基(甲基)丙烯酸酯、二環戊基(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、苯甲基(甲基)丙烯酸酯、2-甲氧基乙基(甲基)丙烯酸酯、2-乙氧基乙基(甲基)丙烯酸酯、丙烯酸、甲基丙烯酸、伊康酸、順丁烯二酸、順丁烯二酐、順丁烯二酸單烷基酯、單烷基伊康酸酯、單烷基反丁烯二酸酯(fumarate)、環氧丙基丙烯酸酯、環氧丙基甲基丙烯酸酯、3,4-環氧基丁基(甲基)丙烯酸酯、2,3-環氧基環己基(甲基)丙烯酸酯、3,4-環氧基環己基甲基(甲基)丙烯酸酯、3-甲 基氧呾(oxetane)-3-甲基(甲基)丙烯酸酯、3-乙基氧呾-3-甲基(甲基)丙烯酸酯、苯乙烯、α-甲基苯乙烯、乙醯氧基苯乙烯(acetoxystryene)、N-甲基馬來亞醯胺、N-乙基馬來亞醯胺、N-丙基馬來亞醯胺、N-丁基馬來亞醯胺、N-環己基馬來亞醯胺、(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺等。該丙烯酸系聚合物可單獨使用或組合其兩種或更多種使用。 The acrylic polymer is a copolymer including the following monomers, and examples of the monomer include meth (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) Group) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (Meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl ( Methacrylates, isobranched (meth)acrylates, adamantyl (meth)acrylates, dicyclopentyl (meth)acrylates, dicyclopentenyl (meth)acrylates, benzene Meth (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, acrylic acid, methacrylic acid, itaconic acid, maleic acid Diacid, maleic dianhydride, maleic acid monoalkyl ester, monoalkyl itaconic acid ester, monoalkyl fumarate, epoxypropyl acrylate, epoxypropylene Methacrylate, 3,4-epoxybutyl (meth)acrylate, 2,3-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl ( Meth)acrylate, 3-methyl Oxetane-3-methyl(meth)acrylate, 3-ethyloxy-3-methyl(meth)acrylate, styrene, α-methylstyrene, acetoxy Styrene (acetoxystryene), N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexyl Maleimide, (meth)acrylamide, N-methyl (meth)acrylamide, etc. The acrylic polymer may be used alone or in combination of two or more kinds thereof.

在其側鏈上具有丙烯酸系不飽和鍵的丙烯酸系聚合物可為由環氧樹脂與含有羧酸之丙烯酸系共聚物的加成反應而獲得的共聚物。作為一實例，可使用黏合劑樹脂，其可由環氧樹脂(如環氧丙基丙烯酸酯、環氧丙基甲基丙烯酸酯、3,4-環氧基丁基(甲基)丙烯酸酯、2,3-環氧基環己基(甲基)丙烯酸酯、3,4-環氧基環己基甲基(甲基)丙烯酸酯等)與含有羧酸之丙烯酸系共聚物的加成反應而獲得，該丙烯酸系共聚物係由含有羧酸的丙烯酸系單體(如丙烯酸、甲基丙烯酸、伊康酸、順丁烯二酸、順丁烯二酸單烷基酯等)與選自下列之至少二個單體在40℃至180℃進行共聚合而獲得：烷基(甲基)丙烯酸酯包含甲基(甲基)丙烯酸酯、己基(甲基)丙烯酸酯等、環己基(甲基)丙烯酸酯、異莰基(甲基)丙烯酸酯、金剛烷基(甲基)丙烯酸酯、二環戊基(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、苯甲基(甲基)丙烯酸酯、2-甲氧基乙基(甲基)丙烯酸酯、2-乙氧基乙基(甲基)丙烯酸酯、苯乙烯、α-甲基苯乙烯、乙醯 氧基苯乙烯、N-甲基馬來亞醯胺、N-乙基馬來亞醯胺、N-丙基馬來亞醯胺、N-丁基馬來亞醯胺、N-環己基馬來亞醯胺、(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺等。 The acrylic polymer having an acrylic unsaturated bond in its side chain may be a copolymer obtained by the addition reaction of an epoxy resin and an acrylic copolymer containing a carboxylic acid. As an example, a binder resin can be used, which can be made of epoxy resin (such as epoxypropyl acrylate, epoxypropyl methacrylate, 3,4-epoxybutyl (meth)acrylate, 2 , 3-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, etc.) and the carboxylic acid-containing acrylic copolymer obtained by the addition reaction, The acrylic copolymer is composed of acrylic monomers containing carboxylic acid (such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid monoalkyl ester, etc.) and at least one selected from the following Two monomers are copolymerized at 40°C to 180°C to obtain: alkyl (meth)acrylates include methyl (meth)acrylates, hexyl (meth)acrylates, etc., cyclohexyl (meth)acrylic acid Ester, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth) Group) acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, styrene, α-methylstyrene, acetyl Oxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide Lemidine, (meth)acrylamide, N-methyl (meth)acrylamide, etc.

作為另一實例，在其側鏈上具有丙烯酸系不飽和鍵的丙烯酸系聚合物可為由羧酸與含有環氧基之丙烯酸系共聚物的加成反應所得的共聚物，且可使用黏合劑樹脂，其由含有羧酸的丙烯酸系單體(如丙烯酸、甲基丙烯酸、伊康酸、順丁烯二酸、順丁烯二酸單烷基酯等)與含有環氧基的丙烯酸系共聚物的加成反應而獲得，該丙烯酸系共聚物係藉由共聚合含有環氧基的丙烯酸系單體(如環氧丙基丙烯酸酯、環氧丙基甲基丙烯酸酯、3,4-環氧基丁基(甲基)丙烯酸酯、2,3-環氧基環己基(甲基)丙烯酸酯、3,4-環氧基環己基甲基(甲基)丙烯酸酯等)與選自下列之至少二種或更多種單體在40℃至180℃進行共聚合而獲得：烷基(甲基)丙烯酸酯包含甲基(甲基)丙烯酸酯、己基(甲基)丙烯酸酯等、環己基(甲基)丙烯酸酯、異莰基(甲基)丙烯酸酯、金剛烷基(甲基)丙烯酸酯、二環戊基(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、苯甲基(甲基)丙烯酸酯、2-甲氧基乙基(甲基)丙烯酸酯、2-乙氧基乙基(甲基)丙烯酸酯、苯乙烯、α-甲基苯乙烯、乙醯氧基苯乙烯、N-甲基馬來亞醯胺、N-乙基馬來亞醯胺、N-丙基馬來亞醯胺、N-丁基馬來亞醯胺、N-環己基馬來亞醯胺、(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺等。 As another example, the acrylic polymer having an acrylic unsaturated bond on its side chain may be a copolymer obtained by the addition reaction of a carboxylic acid and an epoxy-containing acrylic copolymer, and a binder may be used Resin, which is copolymerized with acrylic monomer containing carboxylic acid (such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid monoalkyl ester, etc.) and acrylic acid group containing epoxy group The acrylic copolymer is obtained by copolymerizing an acrylic monomer containing epoxy groups (such as glycidyl acrylate, glycidyl methacrylate, 3,4-cyclo Oxybutyl (meth)acrylate, 2,3-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, etc.) and selected from the following At least two or more monomers are copolymerized at 40°C to 180°C to obtain: alkyl (meth)acrylates include methyl (meth)acrylates, hexyl (meth)acrylates, etc. Hexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate , Benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, styrene, α-methylstyrene, ethyl Acetyloxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexyl Maleimide, (meth)acrylamide, N-methyl (meth)acrylamide, etc.

在本發明之可光聚合的組成物中，具有烯系不飽和鍵的聚合化合物可經由光反應來進行交聯，並在形成圖案時形成圖案，且可在高溫加熱組成物時交聯來提供耐化學性及耐熱性。以100重量%的可光聚合的組成物計，具有烯系不飽和鍵的聚合化合物較佳具有0.001至40重量%的量。當具有烯系不飽和鍵的聚合化合物過量時，交聯度會極高，使得圖案的延展性可能會退化。 In the photopolymerizable composition of the present invention, the polymerizable compound having an ethylenically unsaturated bond can be crosslinked by photoreaction, and a pattern can be formed when the pattern is formed, and can be provided by crosslinking when the composition is heated at a high temperature Chemical resistance and heat resistance. The polymer compound having an ethylenically unsaturated bond preferably has an amount of 0.001 to 40% by weight based on 100% by weight of the photopolymerizable composition. When the polymer compound having an ethylenically unsaturated bond is excessive, the degree of crosslinking will be extremely high, so that the ductility of the pattern may be deteriorated.

具體地，該具有烯系不飽和鍵的聚合化合物可包括(甲基)丙烯酸的烷基酯，如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯等、環氧丙基(甲基)丙烯酸酯、具有2至14個環氧乙烷基的聚乙二醇單(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、具有2至14個環氧乙烷基的聚乙二醇二(甲基)丙烯酸酯、具有2至14個環氧丙烷基的丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、雙酚A二環氧丙基醚丙烯酸加成物、β-羥乙基(甲基)丙烯酸酯之鄰苯二甲酸二酯、β-羥乙基(甲基)丙烯酸酯之二異氰酸甲苯加成物、經酯化多元醇與α，β-不飽和羧酸所得之化合物如三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、與二新戊四醇三(甲基)丙烯酸酯、多元環氧丙基化合物之 丙烯酸加成物如三羥甲基丙烷三環氧丙基醚丙烯酸加成物等。該具有烯系不飽和鍵的聚合化合物可單獨使用或組合其兩種或更多種使用。 Specifically, the polymer compound having an ethylenically unsaturated bond may include an alkyl ester of (meth)acrylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, etc., glycidoxypropyl (meth)acrylate, polyethylene glycol mono(meth) with 2 to 14 oxirane groups Group) acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate with 2 to 14 ethylene oxide groups, propylene glycol with 2 to 14 ethylene oxide groups Di(meth)acrylate, trimethylolpropane di(meth)acrylate, bisphenol A diglycidyl ether acrylic acid adduct, β-hydroxyethyl (meth)acrylate phthalate Formic acid diester, toluene adduct of β-hydroxyethyl (meth)acrylate diisocyanate, compounds obtained by esterifying polyol and α,β-unsaturated carboxylic acid such as trimethylolpropane tri( Methacrylic acid ester, neopentaerythritol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate Methacrylates, dipentaerythritol tris (meth)acrylates, polyepoxypropyl compounds Acrylic acid adducts such as trimethylolpropane triglycidyl ether acrylic acid adducts. The polymer compound having an ethylenically unsaturated bond may be used alone or in combination of two or more kinds thereof.

再者，使用由化學式1表示的肟酯化合物作為本發明可光聚合的組成物中的光聚合起始劑的添加量，是能增加透明度及最小化曝光量的含量，其中以100重量%的可光聚合的組成物計，由化學式1表示的肟酯化合物較佳具有0.01重量%至10重量%，更佳0.1重量%至5重量%的含量。 Furthermore, the use of the oxime ester compound represented by Chemical Formula 1 as the amount of the photopolymerization initiator added in the photopolymerizable composition of the present invention is a content that can increase transparency and minimize the exposure amount, of which 100% by weight Based on the photopolymerizable composition, the oxime ester compound represented by Chemical Formula 1 preferably has a content of 0.01% to 10% by weight, more preferably 0.1% to 5% by weight.

此外，本發明之可光聚合的組成物，若有需要，可進一步包含具有環氧基或胺基的矽系化合物作為黏著輔助劑。 In addition, if necessary, the photopolymerizable composition of the present invention may further contain a silicon-based compound having an epoxy group or an amine group as an adhesion aid.

在本發明之可光聚合的組成物中，矽系化合物在固化之後可改善銦錫氧化物(ITO)電極與可光聚合的組成物之間的黏著力及可增加耐熱性。該具有環氧基或胺基的矽系化合物可包括(3-環氧丙氧基丙基)三甲氧基矽烷、(3-環氧丙氧基丙基)三乙氧基矽烷、(3-環氧丙氧基丙基)甲基二甲氧基矽烷、(3-環氧丙氧基丙基)甲基二乙氧基矽烷、(3-環氧丙氧基丙基)二甲基甲氧基矽烷、(3-環氧丙氧基丙基)二甲基乙氧基矽烷、3,4-環氧基丁基三甲氧基矽烷、3,4-環氧基丁基三乙氧基矽烷、2-(3,4-環氧基環己基)乙基三 甲氧基矽烷、2-(3,4-環氧基環己基)乙基三乙氧基矽烷及胺基丙基三甲氧基矽烷等。該具有環氧基或胺基的矽系化合物可單獨使用或組合其兩種或更多種使用。以100重量%的可光聚合的組成物計，該具有環氧基或胺基的矽系化合物可具有0.0001重量%至3重量%的含量。 In the photopolymerizable composition of the present invention, the silicon-based compound after curing can improve the adhesion between the indium tin oxide (ITO) electrode and the photopolymerizable composition and can increase heat resistance. The silicon-based compound having an epoxy group or an amine group may include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3- Glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethyl Oxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxy Silane, 2-(3,4-epoxycyclohexyl) ethyl tri Methoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and aminopropyltrimethoxysilane etc. The silicon-based compound having an epoxy group or an amine group may be used alone or in combination of two or more kinds thereof. The silicon-based compound having an epoxy group or an amine group may have a content of 0.0001% to 3% by weight based on 100% by weight of the photopolymerizable composition.

此外，本發明之可光聚合的組成物，若有需要，可進一步包含具有相容性的添加劑如光敏劑、熱聚合抑制劑、消泡劑、整平劑等。 In addition, the photopolymerizable composition of the present invention, if necessary, may further contain compatible additives such as photosensitizers, thermal polymerization inhibitors, defoamers, and leveling agents.

本發明之可光聚合的組成物透過進行下列方法形成圖案：將溶劑旋塗到基材上並使用光罩將紫外線(UV)照射到該基材上，再以鹼性顯影劑顯影該基材，其中較佳是，以100重量%的可光聚合的組成物計，藉由添加10重量%至95重量%的溶劑以將黏度調整在1至50厘泊(cps)的範圍內。 The photopolymerizable composition of the present invention is patterned by performing the following method: spin-coating the solvent onto the substrate and irradiating the substrate with ultraviolet light (UV) using a photomask, and then developing the substrate with an alkaline developer Among them, preferably, based on 100% by weight of the photopolymerizable composition, the viscosity is adjusted within the range of 1 to 50 centipoise (cps) by adding a solvent of 10 to 95% by weight.

並不限制根據本發明之例示性實施例的光反應性化合物，只要它是具有光反應的化合物且是本領域中通常使用的。具體地，該光反應性化合物可以是選自下列化合物的至少一種：二新戊四醇六丙烯酸、新戊四醇三丙烯酸、三羥甲基丙烷三丙烯酸、乙二醇丙烯酸、雙酚A二環氧丙基醚丙烯酸加成物、三羥甲基丙烷三環氧丙基醚丙烯酸加成物、新戊四醇三甲基丙烯酸、二新戊四醇六丙烯酸、 三羥甲基丙烷三甲基丙烯酸、新戊四醇四丙烯酸、新戊二醇二甲基丙烯酸、三乙二醇二丙烯酸、三乙二醇二甲基丙烯酸、雙酚A之雙(丙烯醯氧基乙基)醚、3-甲基戊二醇二丙烯酸、3-甲基戊二醇二甲基丙烯酸等。此處，以100重量%的可光聚合的組成物計，該光反應性化合物可具有1重量%至25重量%的含量。 The photoreactive compound according to the exemplary embodiment of the present invention is not limited as long as it is a compound having photoreaction and is generally used in the art. Specifically, the photoreactive compound may be at least one selected from the following compounds: dipentaerythritol hexaacrylic acid, neopentaerythritol triacrylic acid, trimethylolpropane triacrylic acid, ethylene glycol acrylic acid, bisphenol A diacid Epoxypropyl ether acrylic acid adduct, trimethylolpropane triglycidyl ether acrylic acid adduct, neopentyl alcohol trimethacrylic acid, di neopentyl alcohol hexaacrylic acid, Trimethylolpropane trimethacrylic acid, neopentaerythritol tetraacrylic acid, neopentyl glycol dimethacrylic acid, triethylene glycol diacrylic acid, triethylene glycol dimethacrylic acid, bisphenol A bis (acrylic Oxyethyl) ether, 3-methylpentanediol diacrylic acid, 3-methylpentanediol dimethacrylic acid, etc. Here, the photoreactive compound may have a content of 1% to 25% by weight based on 100% by weight of the photopolymerizable composition.

考慮到與黏合劑樹脂、光起始劑、和其他化合物的相容性，溶劑如乙酸乙酯、乙酸丁酯、二乙二醇二甲醚、二乙二醇二甲基乙基醚、甲基甲氧基丙酸酯、乙基乙氧基丙酸酯(EEP)、乳酸乙酯、丙二醇單甲基醚乙酸酯(PGMEA)、丙二醇甲基醚丙酸酯(PGMEP)、丙二醇甲基醚、丙二醇丙基醚、甲基賽珞蘇乙酸酯(methyl cellosolve acetate)、乙基賽珞蘇乙酸酯、二乙二醇乙酸甲酯、二乙二醇乙酸乙酯、丙酮、甲基異丁基酮、環己酮、二甲基甲醯胺(DMF)、N,N-二甲基乙醯胺(DMAc)、N-甲基-2-吡咯烷酮(NMP)、γ-丁內酯、二***、乙二醇二甲醚、二甘二甲醚、四氫呋喃(THF)、甲醇、乙醇、丙醇、異丙醇、甲基賽珞蘇、乙基賽珞蘇、二乙二醇甲醚、二乙二醇***、二丙二醇甲醚、甲苯、二甲苯、己烷、庚烷、辛烷等，可單獨使用或組合其兩種或更多種使用，作為本發明之溶劑。 Considering the compatibility with binder resins, photoinitiators, and other compounds, solvents such as ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl alcohol Methoxy propionate, ethyl ethoxy propionate (EEP), ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether propionate (PGMEP), propylene glycol methyl Ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl Isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone , Diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, isopropanol, methylcellulose, ethylcellulose, diethylene glycol methyl alcohol Ether, diethylene glycol ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, octane, etc., can be used alone or in combination of two or more kinds thereof, as the solvent of the present invention.

根據本發明之例示性實施例的可光聚合的組成物可藉由使用旋塗機、輥塗機、棒塗機、模塗機、簾式塗布機、 各種類型的印刷、浸漬等的已知方法來施用至承載基材如鈉玻璃、石英玻璃、半導體基材、金屬、紙、塑料等。此外，在將可光聚合的組成物施用至承載基材(如膜等)上之後，該可光聚合的組成物可以被轉移到另一承載基材，且沒有限制所應用方法。 The photopolymerizable composition according to the exemplary embodiment of the present invention can be used by using a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, Various known methods of printing, dipping, etc. are applied to carrier substrates such as soda glass, quartz glass, semiconductor substrates, metals, paper, plastics, etc. In addition, after the photopolymerizable composition is applied to a carrier substrate (such as a film, etc.), the photopolymerizable composition can be transferred to another carrier substrate, and the method of application is not limited.

根據本發明之例示性實施例的可光聚合的組成物可使用於各種用途，如液晶彩色顯示器裝置如彩色電視、PC監視器、行動資訊終端機、數位相機等中的可光固化塗料或清漆、可光固化黏接劑、印刷電路板、或彩色過濾器、用於電漿顯示器面板的電極材料、粉末塗料、印刷油墨、印刷板、黏合劑、牙科組成物、凝膠塗料、電子工程光阻劑、電鍍抗蝕劑、蝕刻阻劑、液膜及乾膜的阻焊劑、形成製造具有多種顯示器用途之彩色矩陣的結構的抗蝕劑、或在電漿顯示器面板、電場發光顯示器裝置及LCD之製造過程的抗蝕劑、用於封裝電氣組件及電子組件的組成物、磁性記錄材料、精細機器組件、波導、光學開關、電鍍光罩、蝕刻光罩、彩色測試系統、玻璃纖維纜線塗料、絲網印刷模版、經由立體微影技術製造三維物體的材料、用於全像記錄的材料、圖像記錄材料、精細電子電路、脫色材料、用於圖像記錄材料的脫色材料、用於使用微膠囊之圖像記錄材料的脫色材料、用於印刷電路板的光阻劑材料、用於UV和可見激光導向圖像的光阻劑材料、形成在印刷電路板或保護膜依序層疊中的介電層所使用的光阻劑材 料等，但該用途並未特別限制於此。 The photopolymerizable composition according to the exemplary embodiment of the present invention can be used for various applications, such as photocurable paints or varnishes in liquid crystal color display devices such as color televisions, PC monitors, mobile information terminals, digital cameras, etc. , Photocurable adhesives, printed circuit boards, or color filters, electrode materials for plasma display panels, powder coatings, printing inks, printed boards, adhesives, dental compositions, gel coatings, electronic engineering light Resist, electroplating resist, etching resist, liquid film and dry film solder resist, resist to form a structure to manufacture a color matrix with multiple display uses, or in plasma display panel, electroluminescence display device and LCD Resists in the manufacturing process, compositions used to encapsulate electrical and electronic components, magnetic recording materials, fine machine components, waveguides, optical switches, electroplated photomasks, etched photomasks, color test systems, glass fiber cable coatings , Screen printing stencils, materials for manufacturing three-dimensional objects via stereolithography, materials for holographic recording, image recording materials, fine electronic circuits, bleaching materials, bleaching materials for image recording materials, for use Decolorizing materials for image recording materials of microcapsules, photoresist materials for printed circuit boards, photoresist materials for UV and visible laser-guided images, formed in a sequential lamination of printed circuit boards or protective films Photoresist material used in dielectric layer Materials, etc., but the use is not particularly limited to this.

此外，在又另一普通態樣中，本發明提供一種可光聚合的組成物，其進一步包括含有上述由化學式1表示的肟酯化合物的可光聚合的組成物中的著色劑。 Furthermore, in still another general aspect, the present invention provides a photopolymerizable composition, which further includes a coloring agent in the photopolymerizable composition containing the oxime ester compound represented by the above Chemical Formula 1.

包含在欲施用至用於形成彩色過濾器或黑色矩陣之抗蝕劑中的著色劑可包含青色、紫紅色、紅色的黃色和黑色顏料、綠色、藍色及深藍色混合物系統。該顏料可包含C.I.顏料黃12、13、14、17、20、24、55、83、86、93、109、110、117、125、137、139、147、148、153、154、166、168；C.I.顏料橙36、43、51、55、59、61；C.I.顏料紅9、97、122、123、149、168、177、180、192、215、216、217、220、223、224、226、227、228、240；C.I.顏料紫19、23、29、30、37、40、50；C.I.顏料藍15、15：1、15：4、15：6、22、60、64；C.I.顏料綠7、36；C.I.顏料棕23、25、26；C.I.顏料黑7；鈦黑；碳黑等。此處，以100重量%的可光聚合的組成物計，該著色劑可具有0.1重量%至2.0重量%的含量。 The coloring agent included in the resist to be applied to the color filter or black matrix may include a cyan, magenta, red yellow and black pigment, green, blue, and dark blue mixture system. The pigment may comprise CI Pigment Yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 166, 168 ; CI Pigment Orange 36, 43, 51, 55, 59, 61; CI Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226 , 227, 228, 240; CI Pigment Violet 19, 23, 29, 30, 37, 40, 50; CI Pigment Blue 15, 15: 1, 15: 4, 15: 6, 22, 60, 64; CI Pigment Green 7, 36; CI Pigment Brown 23, 25, 26; CI Pigment Black 7; Titanium Black; Carbon Black, etc. Here, the colorant may have a content of 0.1% to 2.0% by weight based on 100% by weight of the photopolymerizable composition.

使用根據本發明之例示性實施例之彩色可光聚合的組成物之實例之一者的彩色過濾器，可以藉由下述製造方法來製造，但本發明並不限於此。 The color filter using one of the examples of the color photopolymerizable composition according to the exemplary embodiment of the present invention can be manufactured by the following manufacturing method, but the present invention is not limited thereto.

上述彩色可光聚合的組成物例如係藉由適當方法如旋塗、輥塗、噴塗等在0.5μm至10μm厚度下施用至玻璃基材上，且該基材係以光照射而形成用於彩色過濾器所需的圖案。用於照射的光源可以包括紫外線(UV)、電子束或X射線，例如波長在190至450nm，具體為200nm至400nm的UV。此外，照射過程也可藉由使用光阻劑光罩來進行。在進行如上述的照射過程之後，藉由光源照射圖案化的彩色可光聚合的組成物係以顯影劑溶液處理。此處，在該彩色可光聚合的組成物層中的非曝光部分係被溶解，藉此形成用於彩色過濾器所需的圖案。具有所欲圖案的彩色過濾器可藉由重複根據所需顏色之數目的這些過程而獲得。再者，當藉由在過程中顯影所得的圖像圖案被重新加熱且藉由活性光線照射等被固化時，可實現具有改善抗裂性、耐溶劑性等的彩色過濾器。 The color photopolymerizable composition described above is applied to a glass substrate with a thickness of 0.5 μm to 10 μm by a suitable method such as spin coating, roll coating, spray coating, etc., and the substrate is formed by light irradiation for color The pattern required by the filter. The light source used for irradiation may include ultraviolet (UV), electron beam, or X-ray, for example, UV having a wavelength of 190 to 450 nm, specifically 200 nm to 400 nm. In addition, the irradiation process can also be performed by using a photoresist mask. After the irradiation process as described above, the patterned color photopolymerizable composition is irradiated with a light source and treated with a developer solution. Here, the non-exposed portion in the color photopolymerizable composition layer is dissolved, thereby forming a pattern required for a color filter. A color filter with a desired pattern can be obtained by repeating these processes according to the number of required colors. Furthermore, when the image pattern obtained by development in the process is reheated and cured by active light irradiation or the like, a color filter having improved crack resistance, solvent resistance, etc. can be realized.

此外，在又另一普通態樣中，本發明提供一種模製物件，其包含如上述可光聚合的組成物之固化產物。 Furthermore, in yet another general aspect, the present invention provides a molded article comprising the cured product of the photopolymerizable composition as described above.

根據本發明之模製物件可以包含陣列平坦化膜、絕緣膜、柱狀間隙物、黑色柱狀間隙物、黑色矩陣、彩色過濾器等。再者，在又另一普通態樣中，本發明提供一種顯示器裝置，其包含如上述模製物件。 The molded object according to the present invention may include an array planarizing film, an insulating film, a columnar spacer, a black columnar spacer, a black matrix, a color filter, and the like. Furthermore, in still another general aspect, the present invention provides a display device including the molded object as described above.

當本發明之肟酯化合物用作為可光聚合的組成物之光聚合起始劑，即使是少量，仍具有顯著優異的敏感性及優異的物理性能，如膜截留率(retention rate)、圖案穩定性、耐化學性、延展性等，從而最小化在曝光及後烘烤過程期間在薄膜電晶體液晶顯示器(TFT-LCD)製造方法中從光聚合起始劑所產生的逸氣作用，使得可以降低污染，從而使得可以最小化由於污染將產成的缺陷。 When the oxime ester compound of the present invention is used as a photopolymerization initiator of a photopolymerizable composition, even in small amounts, it still has remarkably excellent sensitivity and excellent physical properties, such as film retention rate and pattern stability Resistance, chemical resistance, ductility, etc., thereby minimizing the outgassing effect generated from the photopolymerization initiator in the manufacturing method of the thin film transistor liquid crystal display (TFT-LCD) during the exposure and post-baking process, making it possible Reduce pollution, thereby making it possible to minimize the defects that will be produced due to pollution.

下文中，為詳細了解本發明，將透過實例和比較實例詳細說明本發明之代表性化合物。因此，根據本發明之下列實例可經修改成多種實施例，且不應被解釋為限制本發明之範圍。本發明之例示性實施例係提供以使本領域中具有通常知識者可更完全了解本發明。 Hereinafter, in order to understand the present invention in detail, representative compounds of the present invention will be described in detail through examples and comparative examples. Therefore, the following examples according to the present invention can be modified into various embodiments, and should not be construed as limiting the scope of the present invention. Exemplary embodiments of the present invention are provided so that those with ordinary knowledge in the art can more fully understand the present invention.

[實例1]1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(6)之製備 [Example 1] Preparation of 1-(9,9-diethyl-9H-fusel-2-yl)butane-1,3-dione O,O-diethylenedioxime (6)

Figure 105103739-A0202-12-0035-19
Figure 105103739-A0202-12-0035-19

反應1：9,9-二乙基-9H-茀(2)之合成 Reaction 1: Synthesis of 9,9-diethyl-9H-fusel (2)

將茀(1)(200.0g)(1.20mol)、氫氧化鉀(268.8g)(4.80mol)和碘化鉀(19.9g)(0.12mol)在氮氣氛下溶解於無水二甲基亞碸(1L)，並使反應混合物維持在15℃，再於其內緩慢地加入溴乙烷(283.3g)(2.60mol)歷時2小時。反應混合物在15℃攪拌1小時。將蒸餾水(2L)加入反應混合物，並攪拌30分鐘，且生成混合物以二氯甲烷(2L)萃取。經萃取的有 機層以蒸餾水(2L)清洗2次，並在減壓下蒸餾經回收的有機層之溶劑。所得產物在減壓下進行分餾以獲得具有高黏性之淡黃色液體，9,9-二乙基-9H-茀(2)(248.6g)(93.3%)。 Dissolve stilbene (1) (200.0g) (1.20mol), potassium hydroxide (268.8g) (4.80mol) and potassium iodide (19.9g) (0.12mol) in anhydrous dimethyl sulfoxide (1L) under a nitrogen atmosphere The reaction mixture was maintained at 15°C, and bromoethane (283.3g) (2.60mol) was slowly added thereto for 2 hours. The reaction mixture was stirred at 15°C for 1 hour. Distilled water (2L) was added to the reaction mixture and stirred for 30 minutes, and the resulting mixture was extracted with dichloromethane (2L). Extracted The organic layer was washed twice with distilled water (2 L), and the solvent of the recovered organic layer was distilled under reduced pressure. The resulting product was subjected to fractional distillation under reduced pressure to obtain a light yellow liquid with high viscosity, 9,9-diethyl-9H-fusel (2) (248.6 g) (93.3%).

1H NMR(δ ppm；CDCl3)：0.31(6H,t),2.0(4H,q),7.26-7.31(6H,m),7.68(2H,d) 1 H NMR (δ ppm; CDCl 3 ): 0.31 (6H, t), 2.0 (4H, q), 7.26-7.31 (6H, m), 7.68 (2H, d)

MS(m/e)：222 MS( m/e ): 222

反應2：1-(9,9-二乙基-9H-茀-2-基)乙酮(3)之合成 Reaction 2: Synthesis of 1-(9,9-diethyl-9H-fusel-2-yl)ethanone (3)

將9,9-二乙基-9H-茀(2)(100.5g)(0.45mol)溶解於二氯甲烷(1L)且反應混合物冷卻至-5℃，再將氯化鋁(72.3g)(0.54mol)緩慢地加入其內。然後，小心地於其內緩慢地加入稀釋在二氯甲烷(50mL)中的乙醯氯(42.4g)(0.54mol)，歷時2小時，且反應混合物在-5℃攪拌1小時，使得反應混合物的溫度不升高。將反應混合物緩慢地倒入冰水(1L)並攪拌30分鐘以分離有機層，且經分離的有機層以蒸餾水(500mL)充分清洗。然後，在減壓下蒸餾經回收的有機層之溶劑。所得產物以乙醇再結晶，獲得淡黃色固體，1-(9,9-二乙基-9H-茀-2-基)乙酮(3)(77.6g)(65.2%)。 9,9-Diethyl-9H-fusel (2) (100.5g) (0.45mol) was dissolved in dichloromethane (1L) and the reaction mixture was cooled to -5°C, and then aluminum chloride (72.3g) ( 0.54 mol) was slowly added thereto. Then, acetochloride (42.4 g) (0.54 mol) diluted in dichloromethane (50 mL) was slowly slowly added thereto for 2 hours, and the reaction mixture was stirred at -5°C for 1 hour, so that the reaction mixture The temperature does not rise. The reaction mixture was slowly poured into ice water (1 L) and stirred for 30 minutes to separate the organic layer, and the separated organic layer was thoroughly washed with distilled water (500 mL). Then, the solvent of the recovered organic layer was distilled under reduced pressure. The resulting product was recrystallized from ethanol to obtain a light yellow solid, 1-(9,9-diethyl-9H-fusel-2-yl)ethanone (3) (77.6 g) (65.2%).

1H NMR(δ ppm；CDCl3)：0.80(6H,t),1.90(4H,q),2.53(3H,s),7.35-7.36(3H,m),7.75(2H,t),7.97(2H,d) 1 H NMR (δ ppm; CDCl 3 ): 0.80 (6H, t), 1.90 (4H, q), 2.53 (3H, s), 7.35-7.36 (3H, m), 7.75 (2H, t), 7.97 ( 2H,d)

MS(m/e)：264 MS( m/e ): 264

反應3：1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮(4)之合成 Reaction 3: Synthesis of 1-(9,9-diethyl-9H-fusel-2-yl)butane-1,3-dione (4)

將無水乙酸乙酯(50mL)維持在5℃氮氣氛下且於其內加入氫化鈉(1.8g)(60%於礦物油中，0.045mol)並攪拌30分鐘。加入溶解於乙酸乙酯(50mL)的1-(9,9-二乙基-9H-茀-2-基)-1-丙酮(3)(10.0g)(0.038mol)並攪拌1小時，再緩慢加入反應溶液並在60℃攪拌5小時以完成反應。將反應溶液冷卻至室溫，且於其內加入水(H2O)(30mL)並攪拌約30分鐘。然後，緩慢地滴加1%HCl水溶液(27mL)，使得反應混合物中和到具有6至7的pH值。將乙酸乙酯(100mL)加入反應溶液並攪拌30分鐘以分離有機層，且經分離的有機層以水充分清洗。然後，在減壓下蒸餾經回收的有機層之溶劑。所得產物使用矽膠管柱層析法純化(展開溶劑；乙酸乙酯：正己烷=1：4)以獲得1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮(4)(7.2g)(62.0%)。 Anhydrous ethyl acetate (50 mL) was maintained under a nitrogen atmosphere at 5°C and sodium hydride (1.8 g) (60% in mineral oil, 0.045 mol) was added thereto and stirred for 30 minutes. 1-(9,9-diethyl-9H-fusel-2-yl)-1-acetone (3) (10.0g) (0.038mol) dissolved in ethyl acetate (50mL) was added and stirred for 1 hour, then The reaction solution was slowly added and stirred at 60°C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, and water (H 2 O) (30 mL) was added thereto and stirred for about 30 minutes. Then, a 1% aqueous HCl solution (27 mL) was slowly added dropwise, so that the reaction mixture was neutralized to have a pH value 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 water. Then, the solvent of the recovered organic layer was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1:4) to obtain 1-(9,9-diethyl-9H-fusel-2-yl)butane-1 ,3-Dione (4) (7.2g) (62.0%).

1H NMR(δ ppm；CDCl3)：0.96(6H,t),1.91(4H,q),2.09(3H,s),3.68(2H,s),7.36-7.37(3H,m),7.74-7.76(2H,m),7.87-7.89(2H,m) 1 H NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.91 (4H, q), 2.09 (3H, s), 3.68 (2H, s), 7.36-7.37 (3H, m), 7.74 7.76(2H,m),7.87-7.89(2H,m)

MS(m/e)：306 MS( m/e ): 306

反應4：1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮二肟(5)之合成 Reaction 4: Synthesis of 1-(9,9-diethyl-9H-fusel-2-yl)butane-1,3-dione dioxime (5)

將1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮(4)(5.0g)(0.016mol)分散於乙醇(100mL)中，並於其中加入羥胺鹽酸鹽(3.34g)(0.048mol)和乙酸鈉(3.94g)(0.048mol)，且反應溶液緩慢加熱和回流1小時。將反應溶液冷卻至室溫，並於其中加入蒸餾水(100mL)和乙酸乙酯(200mL)並攪拌30分鐘以分離有機層，且在減壓下蒸餾經分離的有機層之溶劑。所得產物使用矽膠管柱層析法純化(展開溶劑；乙酸乙酯：正己烷=1：4)以獲得1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮二肟(5)(5.05g)(93.9%)。 Disperse 1-(9,9-diethyl-9H-fusel-2-yl)butane-1,3-dione (4) (5.0g) (0.016mol) in ethanol (100mL) Hydroxylamine hydrochloride (3.34g) (0.048mol) and sodium acetate (3.94g) (0.048mol) were added thereto, and the reaction solution was slowly heated and refluxed for 1 hour. The reaction solution was cooled to room temperature, and distilled water (100 mL) and ethyl acetate (200 mL) were added thereto and stirred for 30 minutes to separate the organic layer, and the solvent of the separated organic layer was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1:4) to obtain 1-(9,9-diethyl-9H-fusel-2-yl)butane-1 ,3-Dione dioxime (5) (5.05g) (93.9%).

1H NMR(δ ppm；CDCl3)：0.98(6H,t),1.86(3H,s)1.91(4H,m),2.89(2H,s),7.34-7.38(3H,m),7.80-7.86(2H,m),8.01-8.12(3H,m) 1 H NMR (δ ppm; CDCl 3 ): 0.98 (6H, t), 1.86 (3H, s) 1.91 (4H, m), 2.89 (2H, s), 7.34-7.38 (3H, m), 7.80-7.86 (2H,m),8.01-8.12(3H,m)

MS(m/e)：336 MS( m/e ): 336

反應5：1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(6)之合成 Reaction 5: Synthesis of 1-(9,9-diethyl-9H-fusel-2-yl)butane-1,3-dione O,O-diethylenedioxime (6)

在氮氣氛下將1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮二肟(5)(5.0g)(0.015mol)溶解於乙酸乙酯(50mL)中，使 反應混合物維持在-5℃，且於其中加入三乙胺(3.34g,0.033mol)。所得反應溶液攪拌30分鐘，將乙醯氯(2.59g,0.033mol)緩慢地加入其中，且反應溶液小心攪拌30分鐘使得反應混合物的溫度不升高。將蒸餾水(50mL)緩慢加入反應混合物，並使反應混合物攪拌30分鐘以分離有機層，且在減壓下蒸餾經分離的有機層之溶劑。所得產物使用矽膠管柱層析法純化(展開溶劑；乙酸乙酯：正己烷=1：4)以獲得1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(6)(5.82g)(92.3%)。 Dissolve 1-(9,9-diethyl-9H-fusel-2-yl)butane-1,3-dionedioxime (5) (5.0g) (0.015mol) in ethyl acetate under a nitrogen atmosphere Ester (50mL), make The reaction mixture was maintained at -5°C, and triethylamine (3.34 g, 0.033 mol) was added thereto. The resulting reaction solution was stirred for 30 minutes, acetyl chloride (2.59 g, 0.033 mol) was slowly added thereto, and the reaction solution was carefully stirred for 30 minutes so that the temperature of the reaction mixture did not rise. Distilled water (50 mL) was slowly added to the reaction mixture, and the reaction mixture was stirred for 30 minutes to separate the organic layer, and the solvent of the separated organic layer was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1:4) to obtain 1-(9,9-diethyl-9H-fusel-2-yl)butane-1 ,3-Diketone O,O-diacetyl oxime (6) (5.82g) (92.3%).

1H NMR(δ ppm；CDCl3)：0.96(6H,t),1.88(3H,s)1.91(4H,m),2.08(3H,s),2.11(3H,s),2.89(2H,s),7.34-7.38(3H,m),7.80-7.86(2H,m),8.01-8.12(3H,m) 1 H NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.88 (3H, s) 1.91 (4H, m), 2.08 (3H, s), 2.11 (3H, s), 2.89 (2H, s ), 7.34-7.38 (3H, m), 7.80-7.86 (2H, m), 8.01-8.12 (3H, m)

MS(m/e)：421 MS( m/e ): 421

[實例2]1-(9,9-二乙基-9H-茀-2-基)-2-甲基丁烷-1,3-二酮O,O-聯乙醯二肟(10)之製備 [Example 2] 1-(9,9-diethyl-9H-fusel-2-yl)-2-methylbutane-1,3-dione O,O-diethylenedioxime (10) preparation

Figure 105103739-A0202-12-0040-20
Figure 105103739-A0202-12-0040-20

根據上述實例1之反應2的條件使9,9-二乙基-9H-茀(2)與丙醯氯反應以製備1-(9,9-二乙基-9H-茀-2-基)-丙烷-1-酮(7)。然後，以與上述實例1之反應3至反應5的相同方法獲得1-(9,9-二乙基-9H-茀-2-基)-2-甲基丁烷-1,3-二酮O,O-聯乙醯二肟(10)(5.48g)(90.2%)。 According to the conditions of reaction 2 of Example 1 above, 9,9-diethyl-9H-fusel (2) was reacted with propyl chloride to prepare 1-(9,9-diethyl-9H-fusel-2-yl) -Propane-1-one (7). Then, 1-(9,9-diethyl-9H-fusel-2-yl)-2-methylbutane-1,3-dione was obtained in the same manner as in Reaction 3 to Reaction 5 of Example 1 above O,O-diacetyl oxime (10) (5.48g) (90.2%).

1H NMR(δ ppm；CDCl3)：0.96(6H,t),1.31(3H,d),1.88(3H,s)1.91(4H,m),2.07(3H,s),2.12(3H,s),2.89(2H,s),7.34-7.38(3H,m),7.80-7.86(2H,m),8.01-8.12(3H,m) 1 H NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.31 (3H, d), 1.88 (3H, s) 1.91 (4H, m), 2.07 (3H, s), 2.12 (3H, s ), 2.89 (2H, s), 7.34-7.38 (3H, m), 7.80-7.86 (2H, m), 8.01-8.12 (3H, m)

MS(m/e)：434 MS( m/e ): 434

[實例3]1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮O,O-二環己烷羰基二肟(11)之製備 [Example 3] Preparation of 1-(9,9-diethyl-9H-fusel-2-yl)butane-1,3-dione O,O-dicyclohexanecarbonyl dioxime (11)

Figure 105103739-A0202-12-0041-88
Figure 105103739-A0202-12-0041-88

根據上述實例1之反應5的條件使1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮二肟(5)與環己烷甲醯氯(cyclohexanecarbonyl chloride)反應以獲得1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮O,O-二環己烷羰基二肟(11)(7.36g)(88.1%)。 According to the conditions of Reaction 5 in Example 1 above, 1-(9,9-diethyl-9H-fusel-2-yl)butane-1,3-dione dioxime (5) and cyclohexanecarboxamide (cyclohexanecarbonyl chloride) reaction to obtain 1-(9,9-diethyl-9H-fusel-2-yl)butane-1,3-dione O,O-dicyclohexanecarbonyl dioxime (11)( 7.36g) (88.1%).

1H NMR(δ ppm；CDCl3)：0.96(6H,t),1.12-1.15(10H,m),1.60-1.66(10H,m),1.88(3H,s)1.91(4H,m),2.08(3H,s),2.27(2H,m),2.89(2H,s),7.34-7.38(3H,m),7.80-7.86(2H,m),8.01-8.12(3H,m) 1 H NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.12-1.15 (10H, m), 1.60-1.66 (10H, m), 1.88 (3H, s) 1.91 (4H, m), 2.08 (3H,s), 2.27(2H,m), 2.89(2H,s),7.34-7.38(3H,m),7.80-7.86(2H,m),8.01-8.12(3H,m)

MS(m/e)：557 MS( m/e ): 557

[實例4]1-(9,9-二乙基-9H-茀-2-基)丁烷-1,2-二酮O,O-二苯甲氧基二肟(12)之製備 [Example 4] Preparation of 1-(9,9-diethyl-9H-fusel-2-yl)butane-1,2-dione O,O-dibenzyloxy dioxime (12)

Figure 105103739-A0202-12-0042-22
Figure 105103739-A0202-12-0042-22

根據上述實例1之反應5的條件使1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮二肟(5)與苯甲醯氯反應以獲得1-(9,9-二乙基-9H-茀-2-基)丁烷-1,2-二酮O,O-二苯甲氧基二肟(12)(7.12g)(87.1%)。 According to the conditions of reaction 5 of Example 1 above, 1-(9,9-diethyl-9H-fusel-2-yl)butane-1,3-dione dioxime (5) was reacted with benzoyl chloride to 1-(9,9-diethyl-9H-fusel-2-yl)butane-1,2-dione O,O-dibenzyloxy dioxime (12) (7.12g) (87.1% ).

1H NMR(δ ppm；CDCl3)：0.96(6H,t),1.88(3H,s)1.91(4H,m),2.08(3H,s),2.27(2H,m),2.89(2H,s),7.34-7.38(3H,m),7.80-7.86(2H,m),7.90-8.01(4H,m),8.11-8.18(3H,m),8.21-8.32(6H,m) 1 H NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.88 (3H, s) 1.91 (4H, m), 2.08 (3H, s), 2.27 (2H, m), 2.89 (2H, s ), 7.34-7.38 (3H, m), 7.80-7.86 (2H, m), 7.90-8.01 (4H, m), 8.11-8.18 (3H, m), 8.21-8.32 (6H, m)

MS(m/e)：545 MS( m/e ): 545

[實例5]1-(9,9-二乙基-9H-茀-2-基)-2-甲基丁烷-1,3-二酮O,O-二環己烷羰基二肟(13)之製備 [Example 5] 1-(9,9-diethyl-9H-fusel-2-yl)-2-methylbutane-1,3-dione O,O-dicyclohexanecarbonyl dioxime (13 ) Preparation

Figure 105103739-A0202-12-0043-23
Figure 105103739-A0202-12-0043-23

根據上述實例1之反應5的條件使1-(9,9-二乙基-9H-茀-2-基)-2-甲基丁烷-1,3-二酮二肟(9)與環己烷甲醯氯反應以獲得1-(9,9-二乙基-9H-茀-2-基)-2-甲基丁烷-1,3-二酮O,O-二環己烷羰基二肟(13)(7.07g)(88.7%)。 According to the conditions of Reaction 5 in Example 1 above, 1-(9,9-diethyl-9H-fusel-2-yl)-2-methylbutane-1,3-dione dioxime (9) Hexamethyl chloride reaction to obtain 1-(9,9-diethyl-9H-fusel-2-yl)-2-methylbutane-1,3-dione O,O-dicyclohexanecarbonyl Dioxime (13) (7.07g) (88.7%).

1H NMR(δ ppm；CDCl3)：0.96(6H,t),1.12-1.15(10H,m),1.31(3H,d),1.60-1.66(10H,m),1.88(3H,s)1.91(4H,m),2.07(3H,s),2.12(3H,s),2.89(2H,s),7.34-7.38(3H,m),7.80-7.86(2H,m),8.01-8.12(3H,m) 1 H NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.12-1.15 (10H, m), 1.31 (3H, d), 1.60-1.66 (10H, m), 1.88 (3H, s) 1.91 (4H,m),2.07(3H,s),2.12(3H,s),2.89(2H,s),7.34-7.38(3H,m),7.80-7.86(2H,m),8.01-8.12(3H ,m)

MS(m/e)：571 MS( m/e ): 571

[實例6]1-(9,9-二乙基-9H-茀-2-基)-2-甲基丁烷-1,3-二酮O,O-二苯甲醯基二肟(14)之製備 [Example 6] 1-(9,9-diethyl-9H-fusel-2-yl)-2-methylbutane-1,3-dione O,O-dibenzoyl dioxime (14 ) Preparation

Figure 105103739-A0202-12-0044-24
Figure 105103739-A0202-12-0044-24

根據上述實例1之反應5的條件使1-(9,9-二乙基-9H-茀-2-基)-2-甲基丁烷-1,3-二酮二肟(9)與苯甲醯氯反應以獲得1-(9,9-二乙基-9H-茀-2-基)-2-甲基丁烷-1,3-二酮O,O-二苯甲醯基二肟(14)(6.69g)(85.6%)。 According to the conditions of reaction 5 in Example 1 above, 1-(9,9-diethyl-9H-fusel-2-yl)-2-methylbutane-1,3-dione dioxime (9) and benzene The reaction of methyl chloride to obtain 1-(9,9-diethyl-9H-fusel-2-yl)-2-methylbutane-1,3-dione O,O-dibenzoyl dioxime (14) (6.69g) (85.6%).

1H NMR(δ ppm；CDCl3)：0.96(6H,t),1.31(3H,d),1.88(3H,s)1.91(4H,m),2.07(3H,s),2.12(3H,s),2.89(2H,s),7.34-7.38(3H,m),7.80-7.86(2H,m),8.01-8.12(3H,m),7.90-8.01(4H,m),8.11-8.18(3H,m),8.21-8.32(6H,m) 1 H NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.31 (3H, d), 1.88 (3H, s) 1.91 (4H, m), 2.07 (3H, s), 2.12 (3H, s ), 2.89 (2H, s), 7.34-7.38 (3H, m), 7.80-7.86 (2H, m), 8.01-8.12 (3H, m), 7.90-8.01 (4H, m), 8.11-8.18 (3H ,m),8.21-8.32(6H,m)

MS(m/e)：559 MS( m/e ): 559

[實例7]1-(9,9-二丁基-7-硝基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(20)之製備 [Example 7] 1-(9,9-dibutyl-7-nitro-9H-fusel-2-yl)butane-1,3-dione O,O-diethylenedioxime (20) preparation

Figure 105103739-A0202-12-0045-25
Figure 105103739-A0202-12-0045-25

反應1：9,9-二-n-丁基-2-硝基-9H-茀(16)之合成 Reaction 1: Synthesis of 9,9-di-n-butyl-2-nitro-9H-fusel (16)

將2-硝基茀(15)(12.66g)(60mmol)、氫氧化鉀(21.0g)(0.3mol，純度=80%)和碘化鉀(1.01g)(6mmol)在氮氣氛下溶解於無水二甲基亞碸(200mL)，並使反應溫度維持在17℃，再於其內緩慢地加入n-溴丁烷(33mL)(0.3mol) 歷時2小時。反應混合物在17℃攪拌1小時。將蒸餾水(200mL)加入反應混合物，並攪拌約30分鐘，且生成混合物以二氯甲烷(300mL)萃取。經萃取的有機層以蒸餾水(100mL)清洗3次，並在減壓下蒸餾經回收的有機層之溶劑。所得產物使用矽膠管柱層析法純化(展開溶劑；二氯甲烷：正己烷=20：1)以獲得9,9-二-n-丁基-2-硝基-9H-茀(16)(15.4g)(79.5%)。 Dissolve 2-nitrostilbene (15) (12.66 g) (60 mmol), potassium hydroxide (21.0 g) (0.3 mol, purity = 80%) and potassium iodide (1.01 g) (6 mmol) in anhydrous nitrogen under a nitrogen atmosphere Methyl sulfoxide (200mL), and maintain the reaction temperature at 17 ℃, then slowly add n-bromobutane (33mL) (0.3mol) It took 2 hours. The reaction mixture was stirred at 17°C for 1 hour. Distilled water (200 mL) was added to the reaction mixture, and stirred for about 30 minutes, and the resulting mixture was extracted with dichloromethane (300 mL). The extracted organic layer was washed three times with distilled water (100 mL), and the solvent of the recovered organic layer was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; dichloromethane: n-hexane = 20:1) to obtain 9,9-di-n-butyl-2-nitro-9H-fusel (16) ( 15.4g) (79.5%).

1H NMR(δ ppm；CDCl3)：0.52-0.61(4H,m),0.66(6H,t),1.07(4H,sex),2.00-2.06(4H,m),7.38-7.42(3H,m),7.77-7.80(2H,d),8.20(1H,d),8.26(1H,dd) 1 H NMR (δ ppm; CDCl 3 ): 0.52-0.61 (4H, m), 0.66 (6H, t), 1.07 (4H, sex), 2.00-2.06 (4H, m), 7.38-7.42 (3H, m ), 7.77-7.80 (2H, d), 8.20 (1H, d), 8.26 (1H, dd)

MS(m/e)：323 MS( m/e ): 323

反應2：1-(9,9-二-n-丁基-7-硝基-9H-茀-2-基)-乙酮(17)之合成 Reaction 2: Synthesis of 1-(9,9-di-n-butyl-7-nitro-9H-fusel-2-yl)-ethanone (17)

將9,9-二-n-丁基-2-硝基-9H-茀(16)(7.0g)(21.7mmol)溶解於無水硝基苯(200mL)，再於其內加入無水氯化鋁(5.77g)(43.4mmol)。將反應混合物加熱至45℃，再於其內緩慢地加入乙醯氯(3.40g)(43.3mmol)溶解於無水硝基苯(40mL)的溶液歷時1小時，再使反應混合物加熱至65℃並攪拌1小時。然後，使反應混合物冷卻至室溫，再於其內加入蒸餾水(100mL)，隨後攪拌約30分鐘，且產物以二 氯甲烷(200mL)萃取。經萃取的有機層依序以飽和碳酸氫鈉水溶液(100mL)和蒸餾水(100mL)清洗，且經回收的有機層之溶劑在減壓下蒸餾以獲得固體產物。將所得固體產物分散在少量醚中，在室溫攪拌30分鐘，過濾，並乾燥以獲得1-(9,9-二-n-丁基-7-硝基-9H-茀-2-基)-乙酮(17)(5.44g)(68.7%)。 Dissolve 9,9-di-n-butyl-2-nitro-9H-fusel (16) (7.0g) (21.7mmol) in anhydrous nitrobenzene (200mL), then add anhydrous aluminum chloride to it (5.77g) (43.4mmol). The reaction mixture was heated to 45°C, and a solution of acetochloride (3.40g) (43.3mmol) dissolved in anhydrous nitrobenzene (40mL) was slowly added thereto for 1 hour, and then the reaction mixture was heated to 65°C and Stir for 1 hour. Then, the reaction mixture was cooled to room temperature, and distilled water (100 mL) was added thereto, followed by stirring for about 30 minutes, and the product Chloromethane (200mL) extraction. The extracted organic layer was washed sequentially with saturated aqueous sodium bicarbonate solution (100 mL) and distilled water (100 mL), and the solvent of the recovered organic layer was distilled under reduced pressure to obtain a solid product. The obtained solid product was dispersed in a small amount of ether, stirred at room temperature for 30 minutes, filtered, and dried to obtain 1-(9,9-di-n-butyl-7-nitro-9H-fusel-2-yl) -Ethanone (17) (5.44g) (68.7%).

1H NMR(δ ppm；CDCl3)：0.36-0.40(4H,m),0.56(6H,t),0.96(4H,sex),2.04-2.13(4H,m),2.62(3H,s),8.00-8.05(2H,m),8.10-8.18(2H,m),8.24-8.27(1H,m),8.36(1H,s) 1 H NMR (δ ppm; CDCl 3 ): 0.36-0.40 (4H, m), 0.56 (6H, t), 0.96 (4H, sex), 2.04-2.13 (4H, m), 2.62 (3H, s), 8.00-8.05(2H,m), 8.10-8.18(2H,m), 8.24-8.27(1H,m), 8.36(1H,s)

MS(m/e)：365 MS( m/e ): 365

反應3：1-(9,9-二丁基-7-硝基-9H-茀-2-基)丁烷-1,3-二酮(18)之合成 Reaction 3: Synthesis of 1-(9,9-dibutyl-7-nitro-9H-fusel-2-yl)butane-1,3-dione (18)

將無水乙酸乙酯(50mL)維持在5℃氮氣氛下且於其內加入氫化鈉(1.64g)(60%於礦物油中，0.041mol)並攪拌30分鐘。加入溶解於乙酸乙酯(50mL)的1-(9-9-二-n-丁基-7-硝基-9H-茀-2-基)-乙酮(17)(10.0g)(0.027mol))並攪拌1小時，再緩慢加熱反應溶液並在60℃攪拌5小時以完成反應。將反應溶液冷卻至室溫，且於其內加入水(H2O)(30mL)並攪拌約30分鐘。然後，緩慢地滴加1%HCl水溶液(27mL)，使得反應混合物中和到具有6至7的pH 值。將乙酸乙酯(100mL)加入反應溶液並攪拌30分鐘以分離有機層，且經分離的有機層以水充分清洗。然後，在減壓下蒸餾經回收的有機層之溶劑。所得產物使用矽膠管柱層析法純化(展開溶劑；乙酸乙酯：正己烷=1：4)以獲得1-(9,9-二丁基-7-硝基-9H-茀-2-基)丁烷-1,3-二酮(18)(6.63g)(60.3%)。 Anhydrous ethyl acetate (50 mL) was maintained under a nitrogen atmosphere at 5°C and sodium hydride (1.64 g) (60% in mineral oil, 0.041 mol) was added thereto and stirred for 30 minutes. Add 1-(9-9-di-n-butyl-7-nitro-9H-fusel-2-yl)-ethanone (17) (10.0g) (0.027mol) dissolved in ethyl acetate (50mL) )) and stirring for 1 hour, then slowly heating the reaction solution and stirring at 60°C for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, and water (H 2 O) (30 mL) was added thereto and stirred for about 30 minutes. Then, a 1% aqueous HCl solution (27 mL) was slowly added dropwise, so that the reaction mixture was neutralized to have a pH value 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 water. Then, the solvent of the recovered organic layer was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1:4) to obtain 1-(9,9-dibutyl-7-nitro-9H-fusel-2-yl ) Butane-1,3-dione (18) (6.63g) (60.3%).

1H NMR(δ ppm；DMSO-d 6 )：0.36-0.40(4H,m),0.56(6H,t),0.96(4H,sex),2.04-2.13(4H,m),2.09(3H,s),3.72(2H,s),8.00-8.05(2H,m),8.10-8.18(2H,m),8.24-8.27(1H,m),8.36(1H,s) 1 H NMR (δ ppm; DMSO- d 6 ): 0.36-0.40 (4H, m), 0.56 (6H, t), 0.96 (4H, sex), 2.04-2.13 (4H, m), 2.09 (3H, s ), 3.72 (2H, s), 8.00-8.05 (2H, m), 8.10-8.18 (2H, m), 8.24-8.27 (1H, m), 8.36 (1H, s)

MS(m/e)：408 MS( m/e ): 408

反應4：1-(9,9-二丁基-7-硝基-9H-茀-2-基)丁烷-1,3-二酮二肟(19)之合成 Reaction 4: Synthesis of 1-(9,9-dibutyl-7-nitro-9H-fusel-2-yl)butane-1,3-dione dioxime (19)

將1-(9,9-二丁基-7-硝基-9H-茀-2-基)丁烷-1,3-二酮(18)(5.0g)(0.012mol)分散於乙醇(100mL)中，於其內加入羥胺鹽酸鹽(2.50g)(0.036mol)和乙酸鈉(2.95g)(0.036mol)，且反應溶液緩慢加熱和回流歷時1小時。將反應溶液冷卻至室溫，再於其內加入蒸餾水(100mL)和乙酸乙酯(200mL)並攪拌約30分鐘，且有機層之溶劑在減壓下蒸餾。所得產物使用矽膠管柱層析法純化(展開溶劑；乙酸乙酯：正 己烷=1：4)以獲得1-(9,9-二丁基-7-硝基-9H-茀-2-基)丁烷-1,3-二酮二肟(19)(4.72g)(89.9%)。 Disperse 1-(9,9-dibutyl-7-nitro-9H-fusel-2-yl)butane-1,3-dione (18) (5.0g) (0.012mol) in ethanol (100mL ), 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 solution was cooled to room temperature, and distilled water (100 mL) and ethyl acetate (200 mL) were added thereto and stirred for about 30 minutes, and the solvent of the organic layer was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; ethyl acetate: positive Hexane=1:4) to obtain 1-(9,9-dibutyl-7-nitro-9H-fusel-2-yl)butane-1,3-dione dioxime (19) (4.72g ) (89.9%).

1H NMR(δ ppm；DMSO-d 6 )：0.38-0.41(4H,m),0.58(6H,t),0.96(4H,sex),2.04-2.13(4H,m),2.11(3H,s),3.74(2H,s),8.00-8.10(2H,m),8.12-8.18(2H,m),8.24-8.27(1H,m),8.38(1H,s) 1 H NMR (δ ppm; DMSO- d 6 ): 0.38-0.41 (4H, m), 0.58 (6H, t), 0.96 (4H, sex), 2.04-2.13 (4H, m), 2.11 (3H, s ), 3.74 (2H, s), 8.00-8.10 (2H, m), 8.12-8.18 (2H, m), 8.24-8.27 (1H, m), 8.38 (1H, s)

MS(m/e)：438 MS( m/e ): 438

反應5：1-(9,9-二丁基-7-硝基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(20)之合成 Reaction 5: Synthesis of 1-(9,9-dibutyl-7-nitro-9H-fusel-2-yl)butane-1,3-dione O,O-diethylenedioxime (20)

在氮氣氛下將1-(9,9-二丁基-7-硝基-9H-茀-2-基)丁烷-1,3-二酮二肟(19)(5.0g)(0.011mol)溶解於乙酸乙酯(50mL)中，使反應混合物維持在-5℃，並於其內加入三乙胺(2.54g)(0.025mol)。將所得反應溶液攪拌30分鐘，將乙醯氯(1.96g)(0.025mol)緩慢地加入其內，且反應溶液小心攪拌30分鐘，使得反應混合物的溫度不會升高。接著，將蒸餾水(50mL)緩慢加入反應混合物並攪拌30分鐘以分離有機層，經回收的有機層以無水硫酸鎂乾燥且溶劑在減壓下蒸餾。所得產物使用矽膠管柱層析法純化(展開溶劑；乙酸乙酯：正己烷=1：4)以獲得1-(9,9-二丁基-7-硝基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(20)(5.82g) (92.3%)。 Under a nitrogen atmosphere, 1-(9,9-dibutyl-7-nitro-9H-fusel-2-yl)butane-1,3-dione dioxime (19) (5.0g) (0.011mol ) Was dissolved in ethyl acetate (50 mL), the reaction mixture was maintained at -5°C, and triethylamine (2.54 g) (0.025 mol) was added thereto. The resulting reaction solution was stirred for 30 minutes, acetyl chloride (1.96 g) (0.025 mol) was slowly added thereto, and the reaction solution was carefully stirred for 30 minutes so that the temperature of the reaction mixture would 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 recovered organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1:4) to obtain 1-(9,9-dibutyl-7-nitro-9H-fusel-2-yl )Butane-1,3-dione O,O-diacetyl oxime (20) (5.82g) (92.3%).

1H NMR(δ ppm；CDCl3)：0.35-0.41(4H,m),0.60(6H,t),0.95(4H,sex),1.90(3H,s),2.00(3H,s),2.06-2.13(4H,m),2.11(3H,s),3.74(2H,s),8.00-8.10(2H,m),8.12-8.18(2H,m),8.24-8.27(1H,m),8.38(1H,s) 1 H NMR (δ ppm; CDCl 3 ): 0.35-0.41 (4H, m), 0.60 (6H, t), 0.95 (4H, sex), 1.90 (3H, s), 2.00 (3H, s), 2.06- 2.13(4H,m),2.11(3H,s),3.74(2H,s),8.00-8.10(2H,m),8.12-8.18(2H,m),8.24-8.27(1H,m),8.38( 1H,s)

MS(m/e)：522 MS( m/e ): 522

[實例8]1-(7-溴-9,9-二丁基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(26)之合成 [Example 8] Synthesis of 1-(7-bromo-9,9-dibutyl-9H-fusel-2-yl)butane-1,3-dione O,O-diethylenedioxime (26)

Figure 105103739-A0202-12-0050-26
Figure 105103739-A0202-12-0050-26

根據上述實例7之反應1的條件使2-溴茀(21)與n-溴丁烷反應以合成2-溴-9,9-二-n-丁基-9H-茀(22)。然後，根據上述實例7之反應3至反應5的條件獲得1-(7-溴-9,9- 二丁基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(26)(5.49g)(89.9%)。 The 2-bromostilbene (21) was reacted with n-bromobutane according to the conditions of reaction 1 of Example 7 above to synthesize 2-bromo-9,9-di-n-butyl-9H-stilbene (22). Then, according to the conditions of Reaction 3 to Reaction 5 of Example 7 above, 1-(7-bromo-9,9- Dibutyl-9H-fusel-2-yl)butane-1,3-dione O,O-diacetyldioxime (26) (5.49g) (89.9%).

1H NMR(δ ppm；CDCl3)：0.36-0.41(4H,m),0.58(6H,t),0.96(4H,sex),1.91(3H,s),2.02(3H,s),2.06-2.13(4H,m),2.14(3H,s),3.78(2H,s),8.01-8.10(2H,m),8.12-8.19(2H,m),8.26-8.30(1H,m),8.38(1H,s) 1 H NMR (δ ppm; CDCl 3 ): 0.36-0.41 (4H, m), 0.58 (6H, t), 0.96 (4H, sex), 1.91 (3H, s), 2.02 (3H, s), 2.06- 2.13 (4H, m), 2.14 (3H, s), 3.78 (2H, s), 8.01-8.10 (2H, m), 8.12-8.19 (2H, m), 8.26-8.30 (1H, m), 8.38 ( 1H,s)

MS(m/e)：556 MS( m/e ): 556

[實例9]1-(7-氰基-9,9-二丁基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(32)之合成 [Example 9] 1-(7-cyano-9,9-dibutyl-9H-fusel-2-yl)butane-1,3-dione O,O-diethylenedioxime (32) synthesis

Figure 105103739-A0202-12-0051-27
Figure 105103739-A0202-12-0051-27

反應1：2-氰基-9H-茀(27)之反應 Reaction 1: Reaction of 2-cyano-9H-fusel (27)

將2-溴茀(21)(30.0g)(0.12mol)加入二甲基甲醯胺(300mL)，且加入氰化銅(16.44g)(0.18mol)並加熱以回流6小時。將蒸餾水(300mL)和乙酸乙酯(300mL)加入反應混合物並攪拌約30分鐘以分離有機層，經分離的有機層以飽和氯化銨水溶液(200mL)清洗，並以蒸餾水(100mL)清洗3次，且在減壓下蒸餾經回收的有機層之溶劑。所得產物使用矽膠管柱層析法純化(展開溶劑；二氯甲烷：正己烷=1：5)以獲得2-氰基-9H-茀(27)(11.77g)(51.3%)。 2-Bromostilbene (21) (30.0 g) (0.12 mol) was added to dimethylformamide (300 mL), and copper cyanide (16.44 g) (0.18 mol) was added and heated to reflux for 6 hours. Distilled water (300 mL) and ethyl acetate (300 mL) were added to the reaction mixture and stirred for about 30 minutes to separate the organic layer, the separated organic layer was washed with saturated aqueous ammonium chloride solution (200 mL), and washed three times with distilled water (100 mL) And the solvent of the recovered organic layer was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; dichloromethane: n-hexane = 1:5) to obtain 2-cyano-9H-fusel (27) (11.77 g) (51.3%).

1H NMR(δ ppm；CDCl3)：7.35-7.42(3H,m),7.75-7.80(2H,d),8.21(1H,d),8.26(1H,dd) 1 H NMR (δ ppm; CDCl 3 ): 7.35-7.42 (3H, m), 7.75-7.80 (2H, d), 8.21 (1H, d), 8.26 (1H, dd)

MS(m/e)：191 MS( m/e ): 191

反應2：1-(7-氰基-9,9-二丁基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(32)之合成 Reaction 2: Synthesis of 1-(7-cyano-9,9-dibutyl-9H-fusel-2-yl)butane-1,3-dione O,O-diethylenedioxime (32)

根據上述實例7之反應1的條件使2-氰基-9H-茀(27)與n-溴丁烷反應以合成2-氰基-9,9-二-n-丁基-9H-茀(28)。然後，根據上述實例7之反應2至反應5的條件獲得1-(7-氰基-9,9-二丁基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(32)(5.49g)(89.9%)。 According to the conditions of Reaction 1 in Example 7 above, 2-cyano-9H-fusel (27) is reacted with n-bromobutane to synthesize 2-cyano-9,9-di-n-butyl-9H-fusel ( 28). Then, according to the conditions of Reaction 2 to Reaction 5 in Example 7 above, 1-(7-cyano-9,9-dibutyl-9H-fusel-2-yl)butane-1,3-dione O was obtained. O-diacetyldioxime (32) (5.49g) (89.9%).

1H NMR(δ ppm；CDCl3)：0.33-0.39(4H,m),0.56(6H, t),0.97(4H,sex),1.90(3H,s),2.01(3H,s),2.06-2.13(4H,m),2.19(3H,s),3.76(2H,s),8.00-8.09(2H,m),8.12-8.20(2H,m),8.24-8.30(1H,m),8.37(1H,s) 1 H NMR (δ ppm; CDCl 3 ): 0.33-0.39 (4H, m), 0.56 (6H, t), 0.97 (4H, sex), 1.90 (3H, s), 2.01 (3H, s), 2.06- 2.13(4H,m), 2.19(3H,s), 3.76(2H,s), 8.00-8.09(2H,m), 8.12-8.20(2H,m), 8.24-8.30(1H,m),8.37( 1H,s)

MS(m/e)：502 MS( m/e ): 502

[實例10]1-(9,9-二乙基-9H-茀-2-基)戊烷-1,4-二酮O,O-聯乙醯二肟(35)之合成 [Example 10] Synthesis of 1-(9,9-diethyl-9H-fusel-2-yl)pentane-1,4-dione O,O-diethylenedioxime (35)

Figure 105103739-A0202-12-0053-28
Figure 105103739-A0202-12-0053-28

根據上述實例1之反應5的條件使1-(9,9-二乙基-9H-茀-2-基)戊烷-1,4-二酮二肟(34)與乙醯氯反應以獲得1-(9,9-二乙基-9H-茀-2-基)戊烷-1,4-二酮O,O-聯乙醯二肟(35)(5.48g)(90.2%)。 1-(9,9-diethyl-9H-fusel-2-yl)pentane-1,4-dione dioxime (34) was reacted with acetyl chloride according to the conditions of reaction 5 in Example 1 above 1-(9,9-diethyl-9H-fusel-2-yl)pentane-1,4-dione O,O-diethylenedioxime (35) (5.48g) (90.2%).

1H NMR(δ ppm；CDCl3)：0.97(6H,t),1.59(4H,q),1.90(3H,s),2.08(3H,s),2.20(3H,s),2.66(2H,t),2.91(2H,t),7.34-7.37(3H,m),7.74-7.78(2H,m),7.87-7.90(2H,m) 1 H NMR (δ ppm; CDCl 3 ): 0.97 (6H, t), 1.59 (4H, q), 1.90 (3H, s), 2.08 (3H, s), 2.20 (3H, s), 2.66 (2H, t), 2.91(2H,t),7.34-7.37(3H,m),7.74-7.78(2H,m),7.87-7.90(2H,m)

MS(m/e)：434 MS( m/e ): 434

[實例11]1-(9,9-二乙基-9H-茀-2-基)戊烷-1,4-二酮O,O-二環己烷羰基二肟(36)之合成 [Example 11] Synthesis of 1-(9,9-diethyl-9H-fusel-2-yl)pentane-1,4-dione O,O-dicyclohexanecarbonyl dioxime (36)

Figure 105103739-A0202-12-0054-29
Figure 105103739-A0202-12-0054-29

根據上述實例1之反應5的條件使1-(9,9-二乙基-9H-茀-2-基)戊烷-1,4-二酮二肟(34)與環己烷甲醯氯反應以獲得1-(9,9-二乙基-9H-茀-2-基)戊烷-1,4-二酮O,O-二環己烷羰基二肟(36)(6.84g)(85.6%)。 1- (9,9-diethyl -9 H - fluorenyl-2-yl) The reaction conditions of Example 15 above in pentane-1,4-dione dioxime (34) cyclohexane carboxylic acyl Chlorine reaction to obtain 1-(9,9-diethyl-9H-fusel-2-yl)pentane-1,4-dione O,O-dicyclohexanecarbonyl dioxime (36) (6.84g) (85.6%).

1H NMR(δ ppm；CDCl3)：0.97(6H,t),1.11-1.14(5H,m),1.33-1.38(5H,m),1.59(1H,m),1.90(3H,s),2.66(2H,t),3.45(2H,t),7.30-7.35(3H,m),7.70-7.76(2H,m),7.82-7.86(2H,m) 1 H NMR (δ ppm; CDCl 3 ): 0.97 (6H, t), 1.11-1.14 (5H, m), 1.33-1.38 (5H, m), 1.59 (1H, m), 1.90 (3H, s), 2.66(2H,t),3.45(2H,t),7.30-7.35(3H,m),7.70-7.76(2H,m),7.82-7.86(2H,m)

MS(m/e)：571 MS( m/e ): 571

[實例12]1-(9,9-二乙基-9H-茀-2-基)戊烷-1,4-二酮 O,O-二苯甲醯基二肟(37)之合成 [Example 12] 1-(9,9-diethyl-9H-fusel-2-yl)pentane-1,4-dione Synthesis of O,O-dibenzoyl dioxime (37)

Figure 105103739-A0202-12-0055-30
Figure 105103739-A0202-12-0055-30

根據上述實例1之反應5的條件使1-(9,9-二乙基-9H-茀-2-基)戊烷-1,4-二酮二肟(34)與苯甲醯氯反應以獲得1-(9,9-二乙基-9H-茀-2-基)戊烷-1,4-二酮O,O-二苯甲醯基二肟(37)(6.90g)(88.2%)。 The reaction conditions of the above Example 15 1- (9,9-diethyl -9 H - fluorenyl-2-yl) pentane-1,4-dione dioxime (34) is reacted with benzoyl chloride To obtain 1-(9,9-diethyl-9H-fusel-2-yl)pentane-1,4-dione O,O-dibenzoyl dioxime (37) (6.90g) (88.2 %).

1H NMR(δ ppm；CDCl3)：0.97(6H,t),1.90(3H,s),2.66(2H,t),3.45(2H,t),7.30-7.35(3H,m),7.70-7.76(2H,m),7.82-7.86(2H,m) 1 H NMR (δ ppm; CDCl 3 ): 0.97 (6H, t), 1.90 (3H, s), 2.66 (2H, t), 3.45 (2H, t), 7.30-7.35 (3H, m), 7.70- 7.76(2H,m),7.82-7.86(2H,m)

MS(m/e)：559 MS( m/e ): 559

[實例13]2-環己基-1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(41)之合成 [Example 13] 2-cyclohexyl-1- (9,9-diethyl -9 H - fluorenyl-2-yl) butane-1,3-dione O, O- diacetyl dioxime (41) Synthesis

Figure 105103739-A0202-12-0056-31
Figure 105103739-A0202-12-0056-31

根據上述實例1之反應5的條件使2-環己基-1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮二肟(40)與乙醯氯反應以獲得2-環己基-1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(41)(2.78g)(92.3%)。 According to the conditions of reaction 5 of Example 1 above, 2-cyclohexyl-1-(9,9-diethyl-9H-fusel-2-yl)butane-1,3-dione dioxime (40) and ethyl Acetyl chloride reaction to obtain 2-cyclohexyl-1-(9,9-diethyl-9H-fusel-2-yl)butane-1,3-dione O,O-diethylenedioxime (41) (2.78g) (92.3%).

1H NMR(δ ppm；CDCl3)：0.89-0.92(5H,m),0.98(6H,t),1.32-1.36(6H,m),1.88(3H,s)1.91(4H,m),2.08(3H,s),2.11(3H,s),2.89(2H,s),7.34-7.38(3H,m),7.80-7.86(2H,m),8.01-8.12(3H,m) 1 H NMR (δ ppm; CDCl 3 ): 0.89-0.92 (5H, m), 0.98 (6H, t), 1.32-1.36 (6H, m), 1.88 (3H, s) 1.91 (4H, m), 2.08 (3H,s),2.11(3H,s),2.89(2H,s),7.34-7.38(3H,m),7.80-7.86(2H,m),8.01-8.12(3H,m)

MS(m/e)：503 MS( m/e ): 503

[實例14]2-環戊基甲基-1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(45)之合成 [Example 14] 2-cyclopentyl-1- (9,9-diethyl -9 H - fluorenyl-2-yl) butane-1,3-dione O, O- diacetyl dioxime (45) Synthesis

Figure 105103739-A0202-12-0057-32
Figure 105103739-A0202-12-0057-32

根據上述實例1之反應5的條件使2-環戊基甲基-1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮二肟(44)與乙醯氯反應以獲得2-環戊基甲基-1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(45)(2.75g)(91.3%)。 According to the conditions of Reaction 5 in Example 1 above, 2-cyclopentylmethyl-1-(9,9-diethyl-9H-fusel-2-yl)butane-1,3-dione dioxime (44 ) With acetyl chloride to obtain 2-cyclopentylmethyl-1-(9,9-diethyl-9H-fusel-2-yl)butane-1,3-dione O,O-diethyl Dioxime (45) (2.75g) (91.3%).

1H NMR(δ ppm；CDCl3)：0.90(3H,t),1.20-1.66(11H,m),1.91(4H,q),2.01(3H,s),2.12(3H,s),3.25(1H,t),7.36-7.38(3H,m),7.77-7.81(2H,m),8.01-8.12(2H,d) 1 H NMR (δ ppm; CDCl 3 ): 0.90 (3H, t), 1.20-1.66 (11H, m), 1.91 (4H, q), 2.01 (3H, s), 2.12 (3H, s), 3.25 ( 1H,t),7.36-7.38(3H,m),7.77-7.81(2H,m),8.01-8.12(2H,d)

MS(m/e)：503 MS( m/e ): 503

[實例15]1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮O,O-二丙醯基二肟(46)之合成 [Example 15] Synthesis of 1-(9,9-diethyl-9H-fusel-2-yl)butane-1,3-dione O,O-dipropionyldioxime (46)

Figure 105103739-A0202-12-0057-33
Figure 105103739-A0202-12-0057-33

根據上述實例1之反應5的條件使1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮二肟(5)與丙醯氯反應以獲得1-(9,9-二乙基-9H-茀-2-基)丁烷-1,3-二酮O,O-二丙醯基二肟(46)(5.99g)(89.1%)。 1- (9,9-diethyl -9 H - fluorenyl-2-yl) The reaction conditions of the above Example 15 3-dione dioxime (5) reacting with propionyl acyl chloride 1-(9,9-diethyl-9H-fusel-2-yl)butane-1,3-dione O,O-dipropionyldioxime (46) (5.99g) (89.1%) .

1H NMR(δ ppm；CDCl3)：0.91(6H,t),1.09(6H,t),1.92(3H,s),2.01(4H,q),2.21(4H,m),2.89(2H,s),7.32-7.35(3H,m),7.68-7.75(2H,m),8.01-8.12(3H,m) 1 H NMR (δ ppm; CDCl 3 ): 0.91 (6H, t), 1.09 (6H, t), 1.92 (3H, s), 2.01 (4H, q), 2.21 (4H, m), 2.89 (2H, s), 7.32-7.35(3H, m), 7.68-7.75(2H, m), 8.01-8.12(3H, m)

MS(m/e)：449 MS( m/e ): 449

[實例16]1-(9,9-二丁基-7-硝基-9H-茀-2-基)-2-甲基丁烷-1,3-二酮O,O-聯乙醯二肟(50)之合成 [Example 16] Synthesis of 1- (9,9-dibutyl-7-nitro -9 H - fluorenyl-2-yl) -2-methyl-butane-1,3-dione O, O- diacetyl Synthesis of Dioxime (50)

Figure 105103739-A0202-12-0058-34
Figure 105103739-A0202-12-0058-34

根據上述實例7之反應2的條件使9,9-二-n-丁基-2-硝 基-9H-茀(16)與丙醯氯反應以合成1-(9,9-二-n-丁基-7-硝基-9H-茀-2-基)-丙烷-1-酮(47)。然後，根據上述實例7之反應3至反應5的條件獲得1-(9,9-二丁基-7-硝基-9H-茀-2-基)-2-甲基丁烷-1,3-二酮O,O-聯乙醯二肟(50)(2.67g)(90.1%)。 According to the conditions of reaction 2 of Example 7 above, 9,9-di-n-butyl-2-nitro Yl-9H-fusel (16) reacts with propyl chloride to synthesize 1-(9,9-di-n-butyl-7-nitro-9H-fusel-2-yl)-propane-1-one (47 ). Then, according to the conditions of Reaction 3 to Reaction 5 in Example 7 above, 1-(9,9-dibutyl-7-nitro-9H-fusel-2-yl)-2-methylbutane-1,3 was obtained -Diketone O,O-diacetyl oxime (50) (2.67g) (90.1%).

1H NMR(δ ppm；CDCl3)：0.38-0.41(4H,m),0.60(6H,t),0.94(4H,sex),1.21(3H,t),1.84-1.92(4H,m),1.95(3H,s),2.08(3H,s),2.55(1H,q),7.88-7.92(2H,m),8.10-8.18(2H,m),8.24-8.27(1H,m),8.36(1H,s) 1 H NMR (δ ppm; CDCl 3 ): 0.38-0.41 (4H, m), 0.60 (6H, t), 0.94 (4H, sex), 1.21 (3H, t), 1.84-1.92 (4H, m), 1.95 (3H, s), 2.08 (3H, s), 2.55 (1H, q), 7.88-7.92 (2H, m), 8.10-8.18 (2H, m), 8.24-8.27 (1H, m), 8.36 ( 1H,s)

MS(m/e)：534 MS( m/e ): 534

[實例17]1-(7-溴-9,9-二丁基-9H-茀-2-基)-2-甲基丁烷-1,3-二酮O,O-聯乙醯二肟(54)之合成 [Example 17] Synthesis of 1- (7-bromo-9,9-dibutyl -9 H - fluorenyl-2-yl) -2-methyl-butane-1,3-dione O, O- diacetyl two Synthesis of oxime (54)

Figure 105103739-A0202-12-0059-35
Figure 105103739-A0202-12-0059-35

根據上述實例7之反應2的條件使2-溴-9,9-二-n-丁基 -9H-茀(22)與丙醯氯反應以合成1-(7-溴-9,9-二-n-丁基-9H-茀-2-基)-丙烷-1-酮(51)。然後，根據上述實例7之反應3至反應5的條件獲得1-(7-溴-9,9-二丁基-9H-茀-2-基)-2-甲基丁烷-1,3-二酮O,O-聯乙醯二肟(54)(2.93g)(90.5%)。 The reaction conditions for the above Example 2 of 7-bromo-2-butyl-9,9--n- -9 H - fluorene (22) with propan acyl chloride to synthesize 1- (7-bromo-9,9- two -n- butyl -9 H - fluorenyl-2-yl) - propan-1-one (51). Then, the reaction according to Example 7 of the above-described conditions for 3 to 5 obtained by reaction of 1- (7-bromo-9,9-dibutyl -9 H - fluorenyl-2-yl) -2-methylbutane 1,3 -Diketone O,O-diacetyl oxime (54) (2.93g) (90.5%).

1H NMR(δ ppm；CDCl3)：0.37-0.40(4H,m),0.56(6H,t),0.92(4H,sex),1.20(3H,t),1.80-1.85(4H,m),1.92(3H,s),2.05(3H,s),2.50(1H,q),7.80-7.84(2H,m),8.02-8.08(2H,m),8.20-8.23(1H,m),8.30(1H,s) 1 H NMR (δ ppm; CDCl 3 ): 0.37-0.40 (4H, m), 0.56 (6H, t), 0.92 (4H, sex), 1.20 (3H, t), 1.80-1.85 (4H, m), 1.92(3H,s),2.05(3H,s),2.50(1H,q),7.80-7.84(2H,m),8.02-8.08(2H,m),8.20-8.23(1H,m),8.30( 1H,s)

MS(m/e)：570 MS( m/e ): 570

[實例18]1-(7-氰基-9,9-二丁基-9H-茀-2-基)-2-甲基丁烷-1,3-二酮O,O-聯乙醯二肟(58)之合成 [Example 18] 1-(7-cyano-9,9-dibutyl-9H-fusel-2-yl)-2-methylbutane-1,3-dione O,O-diacetyl Synthesis of oxime (58)

Figure 105103739-A0202-12-0060-36
Figure 105103739-A0202-12-0060-36

根據上述實例1之反應5的條件使1-(7-氰基-9,9-二丁基-9H-茀-2-基)-2-甲基丁烷-1,3-二酮二肟(57)與乙醯氯反應以獲得1-(7-氰基-9,9-二丁基-9H-茀-2-基)-2-甲基丁烷-1,3-二酮O,O-聯乙醯二肟(58)(2.65g)(88.8%)。 The reaction conditions of the above Example 15 1- (7-cyano-9,9-dibutyl -9 H - fluorenyl-2-yl) -2-methyl-butane-1,3-dione two Oxime (57) reacts with acetyl chloride to obtain 1-(7-cyano-9,9-dibutyl-9H-fusel-2-yl)-2-methylbutane-1,3-dione O , O-diacetyl oxime (58) (2.65g) (88.8%).

1H NMR(δ ppm；CDCl3)：0.37-0.40(4H,m),0.55(6H,t),0.95(4H,sex),1.21(3H,t),1.80-1.85(4H,m),1.91(3H,s),2.04(3H,s),2.45(1H,q),7.76-7.80(2H,m),8.00-8.06(2H,m),8.15-8.20(1H,m),8.31(1H,s) 1 H NMR (δ ppm; CDCl 3 ): 0.37-0.40 (4H, m), 0.55 (6H, t), 0.95 (4H, sex), 1.21 (3H, t), 1.80-1.85 (4H, m), 1.91(3H,s),2.04(3H,s),2.45(1H,q),7.76-7.80(2H,m),8.00-8.06(2H,m),8.15-8.20(1H,m),8.31( 1H,s)

MS(m/e)：516 MS( m/e ): 516

[實例19]1-(9,9-二乙基-9H-茀-2-基)己烷-1,3-二酮O,O-聯乙醯二肟(61)之製備 [Example 19] Preparation of 1-(9,9-diethyl-9H-fusel-2-yl)hexane-1,3-dione O,O-diethylenedioxime (61)

Figure 105103739-A0202-12-0061-37
Figure 105103739-A0202-12-0061-37

根據上述實例1之反應5的條件使1-(9,9-二乙基-9H-茀-2-基)己烷-1,3-二酮二肟(60)與乙醯氯反應以獲得1-(9,9-二乙基-9H-茀-2-基)己烷-1,3-二酮O,O-聯乙醯二肟(61)(5.79g)(92.3%)。 1- (9,9-diethyl -9 H - fluorenyl-2-yl) The reaction conditions of the above Example 1 5 hexane-1,3-dione dioxime (60) reacting with acetyl chloride 1-(9,9-diethyl-9H-fusel-2-yl)hexane-1,3-dione O,O-diethylenedioxime (61) (5.79 g) (92.3%) was obtained.

1H NMR(δ ppm；CDCl3)：0.96(6H,t),1.00(3H,t),1.61(2H,m),1.88(3H,s)1.91(4H,m),2.08(3H,s),2.11(2H,t),2.89(2H,s),7.34-7.38(3H,m),7.80-7.86(2H,m), 8.01-8.12(3H,m) 1 H NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.00 (3H, t), 1.61 (2H, m), 1.88 (3H, s) 1.91 (4H, m), 2.08 (3H, s ), 2.11 (2H, t), 2.89 (2H, s), 7.34-7.38 (3H, m), 7.80-7.86 (2H, m), 8.01-8.12 (3H, m)

MS(m/e)：449 MS( m/e ): 449

[實例20]1-(9,9-二丁基-7-硝基-9H-茀-2-基)-3-苯基丙烷-1,3-二酮O,O-聯乙醯二肟(64)之合成 [Example 20] Synthesis of 1- (9,9-dibutyl-7-nitro -9 H - fluorenyl-2-yl) -3-phenylpropane-1,3-dione O, O- diacetyl two Synthesis of oxime (64)

Figure 105103739-A0202-12-0062-38
Figure 105103739-A0202-12-0062-38

根據上述實例16之反應2的條件使1-(9,9-二-n-丁基-7-硝基-9H-茀-2-基)-乙酮(17)與無水乙基苯甲酸反應以合成1-(9,9-二丁基-7-硝基-9H-茀-2-基)-3-苯基丙烷-1,3-二酮(62)。然後，根據上述實例16之反應3至反應4的條件獲得1-(9,9-二丁基-7-硝基-9H-茀-2-基)-3-苯基丙烷-1,3-二酮O,O-聯乙醯二肟(64)(4.28g)(91.7%)。 The reaction of 1-(9,9-di-n-butyl-7-nitro-9H-fu-2--2-yl)-ethanone (17) with anhydrous ethyl benzoic acid was carried out according to the conditions of reaction 2 in Example 16 above in synthesis of 1- (9,9-dibutyl-7-nitro -9 H - fluorenyl-2-yl) -3-phenylpropane-1,3-dione (62). Then, the reaction according to Example 16 of the above-described conditions for 3 to 4 obtained by the reaction of 1- (9,9-dibutyl-7-nitro -9 H - fluorenyl-2-yl) -3-phenylpropane-1,3 -Diketone O,O-diacetyldioxime (64) (4.28g) (91.7%).

1H NMR(δ ppm；CDCl3)：0.35-0.41(4H,m),0.60(6H, t),0.95(4H,sex),2.00(3H,s),2.06-2.13(4H,m),2.11(3H,s),3.74(2H,s),7.52-7.62(3H,m),7.80(2H,d),8.00-8.10(2H,m),8.12-8.18(2H,m),8.24-8.27(1H,m),8.38(1H,s) 1 H NMR (δ ppm; CDCl 3 ): 0.35-0.41 (4H, m), 0.60 (6H, t), 0.95 (4H, sex), 2.00 (3H, s), 2.06-2.13 (4H, m), 2.11 (3H, s), 3.74 (2H, s), 7.52-7.62 (3H, m), 7.80 (2H, d), 8.00-8.10 (2H, m), 8.12-8.18 (2H, m), 8.24 8.27(1H,m),8.38(1H,s)

MS(m/e)：584 MS( m/e ): 584

[實例21]1-環己基-3-(9,9-二丁基-7-硝基-9H-茀-2-基)丙烷-1,3-二酮O,O-聯乙醯二肟(67)之合成 [Example 21] 1-cyclohexyl-3- (7-nitro-9,9-dibutyl -9 H - fluorenyl-2-yl) propane-1,3-dione O, O- diacetyl two Synthesis of oxime (67)

Figure 105103739-A0202-12-0063-39
Figure 105103739-A0202-12-0063-39

根據上述實例16之反應2的條件使1-(9,9-二-n-丁基-7-硝基-9H-茀-2-基)-乙酮(17)與甲基環己烷羧酸反應以合成1-環己基-3-(9,9-二丁基-7-硝基-9H-茀-2-基)丙烷-1,3-二酮(65)。然後，根據上述實例16之反應3至反應4的條件獲得1-環己基-3-(9,9-二丁基-7-硝基-9H-茀-2-基)丙烷-1,3-二酮 O,O-聯乙醯二肟(67)(4.23g)(89.7%)。 According to the conditions of Reaction 2 in Example 16 above, 1-(9,9-di-n-butyl-7-nitro-9H-fusel-2-yl)-ethanone (17) and methylcyclohexane carboxyl Acid reaction to synthesize 1-cyclohexyl-3-(9,9-dibutyl-7-nitro-9H-fusel-2-yl)propane-1,3-dione (65). Then, according to the conditions of Reaction 3 to Reaction 4 of Example 16 above, 1-cyclohexyl-3-(9,9-dibutyl-7-nitro-9H-fusel-2-yl)propane-1,3- Dione O,O-diacetyldioxime (67) (4.23g) (89.7%).

1H NMR(δ ppm；CDCl3)：0.35-0.41(4H,m),0.60(6H,t),0.95(4H,sex),1.01-1.11(6H,m),1.45-1.51(5H,m),2.00(3H,s),2.06-2.13(4H,m),2.11(3H,s),3.74(2H,s),8.00-8.10(2H,m),8.12-8.18(2H,m),8.24-8.27(1H,m),8.38(1H,s) 1 H NMR (δ ppm; CDCl 3 ): 0.35-0.41 (4H, m), 0.60 (6H, t), 0.95 (4H, sex), 1.01-1.11 (6H, m), 1.45-1.51 (5H, m ), 2.00 (3H, s), 2.06-2.13 (4H, m), 2.11 (3H, s), 3.74 (2H, s), 8.00-8.10 (2H, m), 8.12-8.18 (2H, m), 8.24-8.27(1H,m), 8.38(1H,s)

MS(m/e)：590 MS( m/e ): 590

[實例22]1-(9,9-二丁基-7-甲基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(73)之合成 [Example 22] Synthesis of 1- (9,9-dibutyl-7-methyl--9 H - fluorenyl-2-yl) butane-1,3-dione O, O- diacetyl dioxime (73) Synthesis

Figure 105103739-A0202-12-0064-40
Figure 105103739-A0202-12-0064-40

根據上述實例7之反應1的條件使2-甲基茀(68)與乙醯氯反應以合成2-甲基-9,9-二-n-丁基-9H-茀(69)。然後，根據上述實例7之反應2至反應5的條件獲得1-(9,9-二丁基-7- 溴-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(73)(2.59g)(85.9%)。 The 2-methyl stilbene (68) was reacted with acetyl chloride according to the conditions of reaction 1 of Example 7 above to synthesize 2-methyl-9,9-di-n-butyl-9H-stilbene (69). Then, according to the conditions of Reaction 2 to Reaction 5 of Example 7 above, 1-(9,9-dibutyl-7- Bromo-9H-fusel-2-yl)butane-1,3-dione O,O-diethylenedioxime (73) (2.59g) (85.9%).

1H NMR(δ ppm；CDCl3)：0.36-0.41(4H,m),0.58(6H,t),0.96(4H,sex),1.91(3H,s),2.02(3H,s),2.06-2.13(4H,m),2.14(3H,s),2.40(3H,s),3.78(2H,s),8.01-8.10(2H,m),8.12-8.19(2H,m),8.26-8.30(1H,m),8.38(1H,s) 1 H NMR (δ ppm; CDCl 3 ): 0.36-0.41 (4H, m), 0.58 (6H, t), 0.96 (4H, sex), 1.91 (3H, s), 2.02 (3H, s), 2.06- 2.13 (4H, m), 2.14 (3H, s), 2.40 (3H, s), 3.78 (2H, s), 8.01-8.10 (2H, m), 8.12-8.19 (2H, m), 8.26-8.30 ( 1H,m),8.38(1H,s)

MS(m/e)：491 MS( m/e ): 491

[實例23]1-(9,9-二丁基-7-苯基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(76)之合成 [Example 23] Synthesis of 1- (9,9-dibutyl-7-phenyl -9 H - fluorenyl-2-yl) butane-1,3-dione O, O- diacetyl dioxime (76) Synthesis

Figure 105103739-A0202-12-0066-41
Figure 105103739-A0202-12-0066-41

反應1：1-(9,9-二丁基-7-苯基-9H-茀-2-基)丁烷-1,3-二酮(74)之合成 Reaction 1: 1- (9,9-dibutyl-7-phenyl -9 H - fluorenyl-2-yl) butane-1,3-dione (74) Synthesis of

將苯基硼酸(10.0g)(0.082mol)、1-(7-溴-9,9-二丁基-9H-茀-2-基)丁烷-1,3-二酮(24)(30.01g)(0.068mol)和四(三苯基膦)鈀(0)(8.09g)(0.007mol)加入反應器中並於其內加入四氫呋喃(300mL)。將2M-碳酸鉀水溶液(100mL)滴加到反應混合物。使反應混合物加熱至60℃並攪拌。當反應完成時，使反應混合物冷卻至室溫，並於其內加入乙酸乙酯(200mL)。有機層以蒸餾水(100mL)清洗，分離經清洗的有 機層，並在減壓下蒸餾經回收的有機層之溶劑。所得產物使用矽膠管柱層析法純化(展開溶劑；乙酸乙酯：正己烷=1：4)以獲得1-(9,9-二丁基-7-苯基-9H-茀-2-基)丁烷-1,3-二酮(74)(15.48g)(51.9%)。 Phenylboronic acid (10.0g) (0.082mol), 1-(7-bromo-9,9-dibutyl-9H-fusel-2-yl)butane-1,3-dione (24) (30.01 g) (0.068 mol) and tetrakis (triphenylphosphine) palladium (0) (8.09 g) (0.007 mol) were added to the reactor and tetrahydrofuran (300 mL) was added thereto. 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 (200 mL) was added thereto. The organic layer was washed with distilled water (100 mL), the washed organic layer was separated, and the solvent of the recovered organic layer was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1: 4) to obtain 1- (9,9-dibutyl-7-phenyl -9 H - fluorenyl -2- Group) butane-1,3-dione (74) (15.48g) (51.9%).

1H NMR(δ ppm；DMSO-d 6 )：0.38-0.42(4H,m),0.60(6H,t),0.91(4H,sex),2.05-2.13(4H,m),2.10(3H,s),3.75(2H,s),7.40-7.42(3H,m),7.72-7.75(2H,m),8.01-8.05(2H,m),8.12-8.20(2H,m),8.24-8.28(1H,m),8.37(1H,s) 1 H NMR (δ ppm; DMSO- d 6 ): 0.38-0.42 (4H, m), 0.60 (6H, t), 0.91 (4H, sex), 2.05-2.13 (4H, m), 2.10 (3H, s ), 3.75(2H,s),7.40-7.42(3H,m),7.72-7.75(2H,m),8.01-8.05(2H,m),8.12-8.20(2H,m),8.24-8.28(1H ,m),8.37(1H,s)

MS(m/e)：437 MS( m/e ): 437

反應2：1-(9,9-二丁基-7-苯基-9H-茀-2-基)丁烷-1,3-二酮二肟(75)之合成 Reaction 2: Synthesis of 1-(9,9-dibutyl-7-phenyl-9H-fusel-2-yl)butane-1,3-dione dioxime (75)

將1-(9,9-二丁基-7-苯基-9H-茀-2-基)丁烷-1,3-二酮(74)(10.00g)(0.023mol)分散於乙醇(100mL)中，並於其內加入羥胺鹽酸鹽(4.80g)(0.069mol)和乙酸鈉(5.66g)(0.069mol)，使反應溶液緩慢加熱和回流歷時1小時。使反應混合物冷卻至室溫，再於其內加入蒸餾水(100mL)和乙酸乙酯(200mL)並攪拌約30分鐘以分離有機層，且在減壓下蒸餾經回收的有機層之溶劑。所得產物使用矽膠管柱層析法純化(展開溶劑；乙酸乙酯：正己烷=1：4)以獲得1-(9,9-二丁基-7-苯基-9H-茀-2-基)丁烷-1,3-二酮二肟(75) (9.37g)(86.9%)。 Disperse 1-(9,9-dibutyl-7-phenyl-9H-fusel-2-yl)butane-1,3-dione (74) (10.00g) (0.023mol) in ethanol (100mL ), and hydroxylamine hydrochloride (4.80 g) (0.069 mol) and sodium acetate (5.66 g) (0.069 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, and the solvent of the recovered organic layer was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1:4) to obtain 1-(9,9-dibutyl-7-phenyl-9H-fusel-2-yl )Butane-1,3-dione dioxime (75) (9.37g) (86.9%).

1H NMR(δ ppm；DMSO-d 6 )：0.36-0.41(4H,m),0.60(6H,t),0.97(4H,sex),2.01-2.10(4H,m),2.12(3H,s),3.70(2H,s),7.38-7.40(3H,m),7.70-7.73(2H,m),8.02-8.10(2H,m),8.12-8.18(2H,m),8.25-8.28(1H,m),8.38(1H,s) 1 H NMR (δ ppm; DMSO- d 6 ): 0.36-0.41 (4H, m), 0.60 (6H, t), 0.97 (4H, sex), 2.01-2.10 (4H, m), 2.12 (3H, s ), 3.70 (2H, s), 7.38-7.40 (3H, m), 7.70-7.73 (2H, m), 8.02-8.10 (2H, m), 8.12-8.18 (2H, m), 8.25-8.28 (1H ,m),8.38(1H,s)

MS(m/e)：469 MS( m/e ): 469

反應3：1-(9,9-二丁基-7-苯基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(76)之合成 Reaction 3: 1- (9,9-dibutyl-7-phenyl -9 H - fluorenyl-2-yl) butane-1,3-dione O, O- diacetyl dioxime (76) of synthesis

在氮氣氛下將1-(9,9-二丁基-7-苯基-9H-茀-2-基)丁烷-1,3-二酮二肟(75)(7.50g)(0.016mol)溶解於乙酸乙酯(100mL)中，使反應混合物維持在-5℃，再於其內加入三乙胺(3.54g)(0.035mol)。將所得反應溶液攪拌30分鐘，將乙醯氯(2.75g)(0.035mol)緩慢地加入於其內，且反應溶液小心攪拌30分鐘，使得反應混合物的溫度不會升高。接著，將蒸餾水(100mL)緩慢加入反應混合物並攪拌30分鐘以分離有機層，且在減壓下蒸餾經回收的有機層之溶劑。所得產物使用矽膠管柱層析法純化(展開溶劑；乙酸乙酯：正己烷=1：4)以獲得1-(9,9-二丁基-7-苯基-9H-茀-2-基)丁烷-1,3-二酮O,O-聯乙醯二肟(76)(8.04g)(90.9%)。 Under a nitrogen atmosphere, 1-(9,9-dibutyl-7-phenyl-9H-fusel-2-yl)butane-1,3-dione dioxime (75) (7.50g) (0.016mol ) Was dissolved in ethyl acetate (100 mL), the reaction mixture was maintained at -5°C, and triethylamine (3.54 g) (0.035 mol) was added thereto. The resulting reaction solution was stirred for 30 minutes, acetyl chloride (2.75 g) (0.035 mol) was slowly added thereto, and the reaction solution was carefully stirred for 30 minutes so that the temperature of the reaction mixture would not rise. Next, distilled water (100 mL) was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, and the solvent of the recovered organic layer was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1:4) to obtain 1-(9,9-dibutyl-7-phenyl-9H-fusel-2-yl ) Butane-1,3-dione O,O-diacetyl oxime (76) (8.04g) (90.9%).

1H NMR(δ ppm；CDCl3)：0.36-0.41(4H,m),0.58(6H,t),0.96(4H,sex),1.91(3H,s),2.02(3H,s),2.06-2.13(4H,m),2.14(3H,s),3.78(2H,s),7.38-7.40(3H,m),7.70-7.73(2H,m),8.01-8.10(2H,m),8.12-8.19(2H,m),8.26-8.30(1H,m),8.38(1H,s) 1 H NMR (δ ppm; CDCl 3 ): 0.36-0.41 (4H, m), 0.58 (6H, t), 0.96 (4H, sex), 1.91 (3H, s), 2.02 (3H, s), 2.06- 2.13(4H,m), 2.14(3H,s),3.78(2H,s),7.38-7.40(3H,m),7.70-7.73(2H,m),8.01-8.10(2H,m),8.12- 8.19(2H,m), 8.26-8.30(1H,m), 8.38(1H,s)

MS(m/e)：553 MS( m/e ): 553

[實例24]1-(9,9-二乙基-7-苯基-9H-茀-2-基)丙烷-1,2-二酮O,O-聯乙醯二肟(79)之合成 [Example 24] Synthesis of 1- (9,9-diethyl-7-phenyl -9 H - fluorenyl-2-yl) propane-1,2-dione O, O- diacetyl dioxime (79) of synthesis

Figure 105103739-A0202-12-0069-42
Figure 105103739-A0202-12-0069-42

根據上述實例1之反應5的條件使1-(9,9-二乙基-9H-茀-2-基)-1,2-丙烷二酮二肟(78)與乙醯氯反應以獲得1-(9,9-二乙基-7-苯基-9H-茀-2-基)丙烷-1,2-二酮O,O-聯乙醯二肟(79)(8.93g)(70.9%)。 The reaction conditions of the above Example 15 1- (9,9-diethyl -9 H - fluorenyl-2-yl) propane-1,2-dione dioxime (78) is reacted with acetyl chloride to obtain 1-(9,9-diethyl-7-phenyl-9H-fusel-2-yl)propane-1,2-dione O,O-diethylenedioxime (79) (8.93g) (70.9 %).

1H NMR(δ ppm；CDCl3)：0.33(6H,t),2.01(4H,q),2.09(3H,s),2.13(3H,s),2.42(3H,s),7.26(2H,t),7.31-7.36(3H,m),7.75(2H,d) 1 H NMR (δ ppm; CDCl 3 ): 0.33 (6H, t), 2.01 (4H, q), 2.09 (3H, s), 2.13 (3H, s), 2.42 (3H, s), 7.26 (2H, t), 7.31-7.36(3H,m),7.75(2H,d)

MS(m/e)：406 MS( m/e ): 406

[實例25]1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(O-乙醯基肟)(84)之製備 [Example 25] 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-ethanone-1,1'-bis(O-acetoxyxime) (84 ) Preparation

Figure 105103739-A0202-12-0070-43
Figure 105103739-A0202-12-0070-43

反應1：9,9-二乙基-9H-茀(81)之合成 Reaction 1: Synthesis of 9,9-diethyl-9H-fusel (81)

在氮氣氛下將茀(80)(200.0g)(1.20mol)、氫氧化鉀(268.8g)(4.80mol)和碘化鉀(19.9g)(0.12mol)溶解於無水二甲基亞碸(1L)中，並使反應混合物維持在15℃，再於其內 緩慢地加入溴乙烷(283.3g)(2.60mol)歷時2小時。反應混合物在15℃攪拌1小時。接著，將蒸餾水(2L)加入反應混合物並攪拌30分鐘。然後，生成混合物以二氯甲烷萃取，經萃取的有機層以蒸餾水清洗，且經回收的有機層以無水硫酸鎂乾燥，然後在減壓下蒸餾溶劑。所得產物使用矽膠管柱層析法純化(展開溶劑；乙酸乙酯：正己烷=1：4)以獲得9,9-二乙基-9H-茀(81)(248.6g)(93.3%)。 Dissolve stilbene (80) (200.0g) (1.20mol), potassium hydroxide (268.8g) (4.80mol) and potassium iodide (19.9g) (0.12mol) in anhydrous dimethyl sulfoxide (1L) under a nitrogen atmosphere , And maintain the reaction mixture at 15 ℃, and then Ethylene bromide (283.3g) (2.60mol) was added slowly for 2 hours. The reaction mixture was stirred at 15°C for 1 hour. Next, distilled water (2 L) was added to the reaction mixture and stirred for 30 minutes. Then, the resulting mixture was extracted with dichloromethane, the extracted organic layer was washed with distilled water, and the recovered organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1:4) to obtain 9,9-diethyl-9H-fusel (81) (248.6 g) (93.3%).

1H-NMR(δ ppm；CDCl3)：0.31(6H,t),2.0(4H,q),7.26-7.31(6H,m),7.68(2H,d) 1 H-NMR (δ ppm; CDCl 3 ): 0.31 (6H, t), 2.0 (4H, q), 7.26-7.31 (6H, m), 7.68 (2H, d)

MS(m/e)：222 MS( m/e ): 222

反應2：1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-乙酮(82)之合成 Reaction 2: Synthesis of 1,1'-(9,9-diethyl-9 H -fu-2,7-diyl)bis-ethanone (82)

將9,9-二乙基-9H-茀(81)(100.5g)(0.45mol)溶解於二氯甲烷(1L)中，使反應混合物冷卻至-5℃，再將氯化鋁(151.8g)(1.14mol)緩慢地加入其內。然後，小心地於其內緩慢地加入稀釋在二氯甲烷(100mL)中的乙醯氯(88.8g)(1.14mol)歷時2小時，且反應混合物在-5℃攪拌1小時，使得反應混合物的溫度不升高。接著，將反應混合物緩慢地倒入冰水並攪拌30分鐘以分離有機層，且經分離的有機層以蒸餾水清洗。然後，在減壓下蒸餾經回收的有機層。所得產物使用 矽膠管柱層析法純化(展開溶劑；乙酸乙酯：正己烷=1：4)以獲得1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-乙酮(82)(81.6g)(59.2%)。 9,9-Diethyl-9H-fusel (81) (100.5g) (0.45mol) was dissolved in dichloromethane (1L), the reaction mixture was cooled to -5°C, and then aluminum chloride (151.8g) ) (1.14mol) was slowly added thereto. Then, acetochloride (88.8 g) (1.14 mol) diluted in dichloromethane (100 mL) was slowly slowly added thereto for 2 hours, and the reaction mixture was stirred at -5°C for 1 hour, so that the reaction mixture The temperature does not rise. Next, the reaction mixture was slowly poured into ice water and stirred for 30 minutes to separate the organic layer, and the separated organic layer was washed with distilled water. Then, the recovered organic layer was distilled under reduced pressure. Use of the resulting product Silica gel column chromatography purification (developing solvent; ethyl acetate: n-hexane = 1:4) to obtain 1,1'-(9,9-diethyl-9H-fu-2,7-diyl) bis -Ethanone (82) (81.6g) (59.2%).

1H-NMR(δ ppm；CDCl3)：0.82(6H,t),1.91(4H,q),2.53(6H,s),7.35-7.36(2H,m),7.75(2H,t),7.97(2H,d) 1 H-NMR (δ ppm; CDCl 3 ): 0.82 (6H, t), 1.91 (4H, q), 2.53 (6H, s), 7.35-7.36 (2H, m), 7.75 (2H, t), 7.97 (2H,d)

MS(m/e)：306 MS( m/e ): 306

反應3：1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(肟)(83)之合成 Reaction 3: Synthesis of 1,1'-(9,9-diethyl-9 H -fu-2,7-diyl)bis-ethanone-1,1'-bis(oxime) (83)

將1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-乙酮(82)(10.0g)(0.033mol)分散於乙醇(100mL)中，於其內加入羥胺鹽酸鹽(5.77g)(0.083mol)和乙酸鈉(6.81g)(0.083mol)，且反應溶液緩慢地加熱並回流歷時1小時。使反應混合物冷卻至室溫，再於其內加入蒸餾水(100mL)和乙酸乙酯(200mL)並攪拌約30分鐘以分離有機層。經分離的有機層以無水硫酸鎂乾燥，並在減壓下蒸餾有機層的溶劑。所得產物使用矽膠管柱層析法純化(展開溶劑；乙酸乙酯：正己烷=1：4)以獲得1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(肟)(83)(7.58g)(68.3%)。 Disperse 1,1'-(9,9-diethyl-9H-fu-2,7-diyl) bis-ethanone (82) (10.0g) (0.033mol) in ethanol (100mL) in Hydroxylamine hydrochloride (5.77 g) (0.083 mol) and sodium acetate (6.81 g) (0.083 mol) were added thereto, and the reaction solution was slowly heated and refluxed for 1 hour. The reaction mixture was allowed to cool 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 of the organic layer was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1:4) to obtain 1,1'-(9,9-diethyl-9H-fusel-2,7-di Radical) bis-ethanone-1,1'-bis(oxime) (83) (7.58g) (68.3%).

1H-NMR(δ ppm；DMSO-d 6 )：0.98(6H,t),1.86(6H,s) 1.91(4H,m),2.89(2H,s),7.34-7.38(2H,m),7.80-7.86(2H,m),8.01-8.12(2H,m),11.05(2H,s) 1 H-NMR (δ ppm; DMSO- d 6 ): 0.98 (6H, t), 1.86 (6H, s) 1.91 (4H, m), 2.89 (2H, s), 7.34-7.38 (2H, m), 7.80-7.86(2H,m), 8.01-8.12(2H,m), 11.05(2H,s)

MS(m/e)：336 MS( m/e ): 336

反應4：1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(O-乙醯基肟)(84)之合成 Reaction 4: 1,1 '- (9,9-diethyl -9 H - fluorene-2,7-diyl) bis - ethanone 1,1'-bis (0- acetyl oxime) (84 ) Synthesis

在氮氣氛下將1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(肟)(83)(5.0g)(0.015mol)溶解於乙酸乙酯(50mL)中，反應混合物維持在-5℃，再於其內加入三乙胺(3.84g)(0.038mol)。將所得反應溶液攪拌30分鐘，將乙醯氯(3.01g)(0.038mol)緩慢地加入其內，並小心攪拌反應溶液30分鐘使得反應混合物的溫度不升高。接著，將蒸餾水緩慢地加入反應混合物並攪拌30分鐘以分離有機層，且經回收的有機層以無水硫酸鎂乾燥，並在減壓下蒸餾有機層的溶劑。所得產物使用矽膠管柱層析法純化(展開溶劑；乙酸乙酯：正己烷=1：4)以獲得1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(O-乙醯基肟)(84)(4.87g)(77.2%)。 Under a nitrogen atmosphere, 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-ethanone-1,1'-bis(oxime)(83)(5.0g ) (0.015 mol) was dissolved in ethyl acetate (50 mL), the reaction mixture was maintained at -5°C, and triethylamine (3.84 g) (0.038 mol) was added thereto. The resulting reaction solution was stirred for 30 minutes, acetyl chloride (3.01 g) (0.038 mol) was slowly added thereto, and the reaction solution was stirred carefully for 30 minutes so that the temperature of the reaction mixture did not rise. Next, distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer, and the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent of the organic layer was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1:4) to obtain 1,1'-(9,9-diethyl-9H-fusel-2,7-di Group) bis-ethanone-1,1'-bis(O-acetyl oxime) (84) (4.87g) (77.2%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.88(6H,s)1.91(4H,m),2.08(6H,s),2.11(6H,s),2.89(2H,s),7.34-7.38(2H,m),7.80-7.86(2H,m),8.01-8.12(2H,m) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.88 (6H, s) 1.91 (4H, m), 2.08 (6H, s), 2.11 (6H, s), 2.89 (2H, s), 7.34-7.38(2H, m), 7.80-7.86(2H, m), 8.01-8.12(2H, m)

MS(m/e)：421 MS( m/e ): 421

[實例26]1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(O-乙醯基肟)(87)之製備 [Example 26] 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-2,2'-bis(O-acetyl Oxime) (87)

Figure 105103739-A0202-12-0074-44
Figure 105103739-A0202-12-0074-44

反應1：1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1-丙酮(85)之合成 Reaction 1: Synthesis of 1,1’-(9,9-diethyl-9H-fu-2,7-diyl)bis-1-acetone (85)

根據上述實例25之反應2的條件使9,9-二乙基-9H-茀(81)與丙醯氯反應以獲得1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1-丙酮(85)(58.6%)。 According to the conditions of reaction 2 in Example 25 above, 9,9-diethyl-9H-fusel (81) was reacted with propyl chloride to obtain 1,1'-(9,9-diethyl-9H-fusel-2 , 7-diyl)bis-1-acetone (85) (58.6%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.28(6H,s)1.91(4H,m),3.06(4H,q),7.35-7.36(2H,m),7.76(2H,t),7.98(2H,d) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.28 (6H, s) 1.91 (4H, m), 3.06 (4H, q), 7.35-7.36 (2H, m), 7.76 ( 2H,t),7.98(2H,d)

MS(m/e)：334 MS( m/e ): 334

反應2：1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(肟)(86)之合成 Reaction 2: 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-2,2'-bis(oxime)(86) Synthesis

將1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1-丙酮(85)(15.0g)(0.045mol)溶解於四氫呋喃(THF)(200mL)中，並將溶解於1,4-二噁烷(1,4-dioxane)的4N HCl(50mL)和亞硝酸異丁酯(13.9g)(0.135mol)依序加入混合物中，且所得生成混合物在25℃攪拌6小時。接著，將乙酸乙酯加入反應溶液並攪拌30分鐘以分離有機層，且經回收的有機層以蒸餾水清洗，並在減壓下蒸餾經回收的有機層之溶劑。所得產物使用矽膠管柱層析法純化(展開溶劑；乙酸乙酯：正己烷=1：4)以獲得1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(肟)(86)(8.67g)(49.1%)。 Dissolve 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1-acetone (85) (15.0g) (0.045mol) in tetrahydrofuran (THF) (200mL ), and 4N HCl (50 mL) dissolved in 1,4-dioxane (1,4-dioxane) and isobutyl nitrite (13.9 g) (0.135 mol) were added to the mixture in sequence, and the resulting product The mixture was stirred at 25°C for 6 hours. Next, ethyl acetate was added to the reaction solution and stirred for 30 minutes to separate the organic layer, and the recovered organic layer was washed with distilled water, and the solvent of the recovered organic layer was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1:4) to obtain 1,1'-(9,9-diethyl-9H-fusel-2,7-di Group) bis-1,2-propanedione-2,2'-bis(oxime) (86) (8.67g) (49.1%).

1H-NMR(δ ppm；DMSO-d 6 )：0.92(6H,t),1.26(6H,s)1.88(4H,m),7.34-7.36(2H,m),7.75(2H,t),7.98(2H,d),10.91(2H,s) 1 H-NMR(δ ppm; DMSO- d 6 ): 0.92(6H,t), 1.26(6H,s) 1.88(4H,m),7.34-7.36(2H,m),7.75(2H,t), 7.98(2H,d), 10.91(2H,s)

MS(m/e)：392 MS( m/e ): 392

反應3：1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(O-乙醯基肟)(87)之合成 Reaction 3: 1,1'-(9,9-diethyl-9H-fu-2,7-diyl) bis-1,2-propanedione-2,2'-bis(O-acetylidene Oxime) (87) Synthesis

根據上述實例25之反應4的條件使1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(肟)(86)與乙醯氯反應以獲得1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(O-乙醯基肟)(87)(75.2%)。 According to the conditions of reaction 4 in Example 25 above, 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-2,2'- Bis(oxime)(86) reacts with acetyl chloride to obtain 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-2 , 2'-bis (O-acetoxy oxime) (87) (75.2%).

1H-NMR(δ ppm；CDCl3)：0.92(6H,t),1.26(6H,s)1.88(4H,m),2.05(6H,s),7.35(2H,m),7.79(2H,t),8.00(2H,d) 1 H-NMR (δ ppm; CDCl 3 ): 0.92 (6H, t), 1.26 (6H, s) 1.88 (4H, m), 2.05 (6H, s), 7.35 (2H, m), 7.79 (2H, t),8.00(2H,d)

MS(m/e)：477 MS( m/e ): 477

[實例27]1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(O-苯甲醯基肟)(88)之製備 [Example 27] 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-ethanone-1,1'-bis(O-benzyl oxime) ( 88) Preparation

Figure 105103739-A0202-12-0076-46
Figure 105103739-A0202-12-0076-46

根據上述實例25之反應4的條件使1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(肟)(83)與苯甲醯氯反應以獲得1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙 (O-苯甲醯基肟)(88)(76.2%)。 According to the conditions of reaction 4 in Example 25 above, 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-ethanone-1,1'-bis(oxime) ( 83) Reaction with benzoyl chloride to obtain 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-ethanone-1,1'-bis (O-benzyl oxime) (88) (76.2%).

1H-NMR(δ ppm；CDCl3)：0.92(6H,t),1.26(6H,s)1.88(4H,m),2.05(6H,s),7.35(2H,m),7.45(4H,t),7.66(2H,t),7.79(2H,t),8.00(2H,d),8.11(4H,d) 1 H-NMR (δ ppm; CDCl 3 ): 0.92 (6H, t), 1.26 (6H, s) 1.88 (4H, m), 2.05 (6H, s), 7.35 (2H, m), 7.45 (4H, t), 7.66 (2H, t), 7.79 (2H, t), 8.00 (2H, d), 8.11 (4H, d)

MS(m/e)：544 MS( m/e ): 544

[實例28]1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(O-環己烷羰基肟)(89)之製備 [Example 28] 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-ethanone-1,1'-bis(O-cyclohexanecarbonyloxime) ( 89) Preparation

Figure 105103739-A0202-12-0077-47
Figure 105103739-A0202-12-0077-47

根據上述實例25之反應4的條件使1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(肟)(83)與環己烷甲醯氯反應以獲得1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(O-環己烷羰基肟)(89)(70.2%)。 According to the conditions of reaction 4 in Example 25 above, 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-ethanone-1,1'-bis(oxime) ( 83) Reaction with cyclohexane formyl chloride to obtain 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-ethanone-1,1'-bis(O -Cyclohexanecarbonyl oxime) (89) (70.2%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.21(6H,s)1.50-1.80(10H,m),1.7(5H,m),1.89-2.20(11H,m),8.01-8.12(4H,m),8.20(2H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.21 (6H, s) 1.50-1.80 (10H, m), 1.7 (5H, m), 1.89-2.20 (11H, m), 8.01-8.12(4H,m), 8.20(2H,s)

MS(m/e)：557 MS( m/e ): 557

[實例29]1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(O-苯甲醯基肟)(90)之製備 [Example 29] 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-2,2'-bis(O-benzoyl Preparation of Acyloxime) (90)

Figure 105103739-A0202-12-0078-48
Figure 105103739-A0202-12-0078-48

根據上述實例25之反應4的條件使1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(肟)(86)與苯甲醯氯反應以獲得1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(O-苯甲醯基肟)(90)(65.2%)。 The reaction conditions of the above Example 4 to make 25 1,1 '- (9,9-diethyl -9 H - fluorene-2,7-diyl) bis-propane-1,2-dione 2,2' - bis (oxime) (86) is reacted with benzoyl chloride to obtain 1,1 '- (9,9-diethyl -9 H - fluorene-2,7-diyl) bis-1,2-propanediyl Ketone-2,2'-bis( O -benzyl oxime) (90) (65.2%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.88(6H,s)1.92(4H,m),7.65-7.7(4H,m),7.90-7.93(2H,m),8.10-8.15(6H, m) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.88 (6H, s) 1.92 (4H, m), 7.65-7.7 (4H, m), 7.90-7.93 (2H, m), 8.10-8.15(6H, m)

MS(m/e)：601 MS( m/e ): 601

[實例30]1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(O-環己烷羰基肟)(91)之製備 [Example 30] 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-2,2'-bis( O -cyclohexane Preparation of alkylcarbonyl oxime) (91)

Figure 105103739-A0202-12-0079-49
Figure 105103739-A0202-12-0079-49

根據上述實例25之反應4的條件使1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(肟)(86)與環己烷甲醯氯反應以獲得1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(O-環己烷羰基肟)(91)(61.3%)。 According to the conditions of reaction 4 in Example 25 above, 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-2,2'- Bis(oxime)(86) reacts with cyclohexaneformyl chloride to obtain 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedi Ketone-2,2'-bis(O-cyclohexanecarbonyl oxime) (91) (61.3%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.2(6H,s)1.52-1.82(10H,m),1.60-1.93(5H,m),1.89-2.31(11H,m),7.90-7.94(2H,m),8.01-8.04(2H,m),8.12(2H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.2 (6H, s) 1.52-1.82 (10H, m), 1.60-1.93 (5H, m), 1.89-2.31 (11H, m ), 7.90-7.94 (2H, m), 8.01-8.04 (2H, m), 8.12 (2H, s)

MS(m/e)：613 MS( m/e ): 613

[實例31]1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(O-乙醯基肟)(93)之製備 [Example 31] 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-1,1',2,2'-Ran ( O -Acetyl oxime) (93) Preparation

Figure 105103739-A0202-12-0080-50
Figure 105103739-A0202-12-0080-50

反應1：1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(肟)(92)之合成 Reaction 1: 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-1,1',2,2'-Wan ( Synthesis of oxime) (92)

根據上述實例1之反應3的條件從1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(肟)(86)獲得1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(肟)(92)(58.3%)。 According to the conditions of reaction 3 in Example 1 above, from 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-2,2'- Bis(oxime)(86) obtains 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-1,1',2, 2'-Wan (oxime) (92) (58.3%).

1H-NMR(δ ppm；DMSO-d 6 )：0.98(6H,t),1.88-1.92(10H,m),8.01-8.10(4H,m),8.15-8.19(2H,m),11.04(2H,s),11.08(2H,s) 1 H-NMR (δ ppm; DMSO- d 6 ): 0.98 (6H, t), 1.88-1.92 (10H, m), 8.01-8.10 (4H, m), 8.15-8.19 (2H, m), 11.04 ( 2H,s),11.08(2H,s)

MS(m/e)：422 MS( m/e ): 422

反應2：1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(O-乙醯基肟)(93)之合成 Reaction 2: 1,1 '- (9,9-diethyl -9 H - fluorene-2,7-diyl) bis-propane-1,2-dione 1,1', 2,2'-store ( O -Acetyl oxime) (93) Synthesis

根據上述實例1之反應4的條件使1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(肟)(92)與乙醯氯反應以獲得1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(O-乙醯基肟)(93)(65.2%)。 According to the conditions of Reaction 4 in Example 1 above, 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-1,1', 2,2'-oxime (oxime) (92) reacts with acetyl chloride to obtain 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2- Propanedione-1,1',2,2'-an (O-acetyl oxime) (93) (65.2%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.88-1.91(10H,m),2.08(12H,s),8.0-8.10(4H,m),8.18-8.21(2H,m) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.88-1.91 (10H, m), 2.08 (12H, s), 8.0-8.10 (4H, m), 8.18-8.21 (2H, m)

MS(m/e)：591 MS( m/e ): 591

[實例32]1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(O-苯甲醯基肟)(94)之製備 [Example 32] 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-1,1',2,2'-Ran Preparation of (O-benzyl oxime) (94)

Figure 105103739-A0202-12-0082-51
Figure 105103739-A0202-12-0082-51

根據上述實例31之反應2的條件使1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(肟)(92)與苯甲醯氯反應以獲得1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(O-苯甲醯基肟)(94)(56.3%)。 According to the conditions of reaction 2 in Example 31 above, 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-1,1', 2,2'-oxime (oxime) (92) reacts with benzoyl chloride to obtain 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2 -Propane dione-1,1',2,2'-an (O-benzoyl oxime) (94) (56.3%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.89-1.92(10H,m),7.62-7.68(8H,m),7.75-7.80(4H,m),8.01-8.16(12H,m),8.19-8.22(2H,m) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.89-1.92 (10H, m), 7.62-7.68 (8H, m), 7.75-7.80 (4H, m), 8.01-8.16 ( 12H,m), 8.19-8.22(2H,m)

MS(m/e)：839 MS( m/e ): 839

[實例33]1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(O-環己烷羰基肟)(95)之製備 [Example 33] 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-1,1',2,2'-Ran Preparation of (O-cyclohexanecarbonyl oxime) (95)

Figure 105103739-A0202-12-0083-52
Figure 105103739-A0202-12-0083-52

根據上述實例31之反應2的條件使1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(肟)(92)與環己烷甲醯氯反應以獲得1,1’-(9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(O-環己烷羰基肟)(95)(55.9%)。 According to the conditions of reaction 2 in Example 31 above, 1,1'-(9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-1,1', 2,2'-oxime (oxime) (92) reacts with cyclohexanemethanyl chloride to obtain 1,1'-(9,9-diethyl- 9H -fu-2,7-diyl)bis-1 ,2-propanedione-1,1',2,2'-ran (O-cyclohexanecarbonyl oxime) (95) (55.9%).

1H-NMR(δ ppm；CDCl3)：0.98(6H,t),1.2(12H,s)1.38-1.55(20H,m),1.60-1.63(10H,m),1.88-2.30(12H,m),8.02-8.08(4H,m),8.18(2H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.98 (6H, t), 1.2 (12H, s) 1.38-1.55 (20H, m), 1.60-1.63 (10H, m), 1.88-2.30 (12H, m ), 8.02-8.08 (4H, m), 8.18 (2H, s)

MS(m/e)：863 MS( m/e ): 863

[實例34]1-(9,9-二乙基-7-(1-(乙醯基氧基亞胺基)丙 基)-9H-茀-2-基)-1-庚酮-O-乙醯基肟(99)之製備 [Example 34] 1-(9,9-diethyl-7-(1-(acetyloxyimino)propylene ))-9H-茀-2-yl)-1-heptanone-O-acetyl oxime (99)

Figure 105103739-A0202-12-0084-53
Figure 105103739-A0202-12-0084-53

反應1：1-(9,9-二乙基-9H-茀-2-基)-1-丙酮(96)之合成 Reaction 1: 1- (9,9-diethyl -9 H - fluorenyl-2-yl) -1-propanone (96) Synthesis of

將9,9-二乙基-9H-茀(81)(100.5g)(0.45mol)溶解於二氯甲烷(1L)且反應混合物冷卻至-5℃，再於其內緩慢地加入氯化鋁(72.3g)(0.54mol)。然後，小心地於其內緩慢地加入稀釋在二氯甲烷(50mL)中的丙醯氯(50.1g)(0.54mol)歷時2小時，且反應混合物在-5℃攪拌1小時，使得反應混合物的 溫度不升高。接著，將反應混合物緩慢地倒入冰水(1L)並攪拌30分鐘以分離有機層，隨後以蒸餾水(500mL)清洗，並在減壓下蒸餾經回收的有機層。所得產物使用矽膠管柱層析法純化(展開溶劑；乙酸乙酯：正己烷=1：4)以獲得淡黃色固體1-(9,9-二乙基-9H-茀-2-基)-1-丙酮(96)(75.8g)(60.6%)。 9,9-diethyl -9 H - fluorene (81) (100.5g) (0.45mol ) was dissolved in dichloromethane (1L) and the reaction mixture was cooled to -5 ℃, then slowly added thereto within chloride Aluminum (72.3g) (0.54mol). Then, carefully add acetyl chloride (50.1 g) (0.54 mol) diluted in dichloromethane (50 mL) slowly for 2 hours, and the reaction mixture was stirred at -5°C for 1 hour, so that the reaction mixture The temperature does not rise. Next, the reaction mixture was slowly poured into ice water (1 L) and stirred for 30 minutes to separate the organic layer, followed by washing with distilled water (500 mL), and the recovered organic layer was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1: 4) to obtain a pale yellow solid of 1- (9,9-diethyl -9 H - 2-fluorenyl) -1-acetone (96) (75.8g) (60.6%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.20(3H,t),1.93(4H,q),2.54(2H,q),7.25-7.35(2H,m),7.52-7.54(1H,m),7.84-7.92(2H,m),8.03-8.15(2H,m) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.20 (3H, t), 1.93 (4H, q), 2.54 (2H, q), 7.25-7.35 (2H, m), 7.52 -7.54(1H,m), 7.84-7.92(2H,m), 8.03-8.15(2H,m)

MS(m/e)：278 MS( m/e ): 278

反應2：1-(9,9-二乙基-7-丙醯基-9H-茀-2-基)-1-庚酮(97)之合成 Reaction 2: Synthesis of 1-(9,9-diethyl-7-propionyl-9H-fusel-2-yl)-1-heptanone (97)

將1-(9,9-二乙基-9H-茀-2-基)-1-丙酮(96)(10.0g)(0.036mol)溶解於二氯甲烷(100mL)且反應混合物冷卻至-5℃，再於其內緩慢地加入氯化鋁(5.76g)(0.043mol)。然後，小心地於其內緩慢地加入稀釋在二氯甲烷(10mL)中的庚醯氯(6.39g)(0.043mol)，且反應混合物在-5℃攪拌1小時，使得反應混合物的溫度不升高。接著，將反應混合物緩慢地倒入冰水(100mL)並攪拌30分鐘以分離有機層，隨後以蒸餾水(50mL)清洗，並在減壓下蒸餾經回收的有機層。所得產 物使用矽膠管柱層析法純化(展開溶劑；乙酸乙酯：正己烷=1：4)以獲得1-(9,9-二乙基-7-丙醯基-9H-茀-2-基)-1-庚酮(97)(7.83g)(55.7%)。 1-(9,9-Diethyl-9H-fusel-2-yl)-1-acetone (96) (10.0 g) (0.036 mol) was dissolved in dichloromethane (100 mL) and the reaction mixture was cooled to -5 At ℃, aluminum chloride (5.76g) (0.043mol) was slowly added thereto. Then, heptane chloride (6.39 g) (0.043 mol) diluted in dichloromethane (10 mL) was slowly slowly added thereto, and the reaction mixture was stirred at -5°C for 1 hour so that the temperature of the reaction mixture did not rise high. Next, the reaction mixture was slowly poured into ice water (100 mL) and stirred for 30 minutes to separate the organic layer, followed by washing with distilled water (50 mL), and the recovered organic layer was distilled under reduced pressure. Income The material was purified using silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1:4) to obtain 1-(9,9-diethyl-7-propionyl-9H-fusel-2-yl )-1-heptanone (97) (7.83g) (55.7%).

1H-NMR(δ ppm；CDCl3)：0.91(3H,t),0.96(6H,t),1.08(3H,t),1.28-1.35(6H,m),1.46-1.48(2H,m),1.92(4H,q),2.60(2H,q),2.96(2H,t),7.89-7.92(2H,m),8.03-8.13(4H,m) 1 H-NMR (δ ppm; CDCl 3 ): 0.91(3H,t), 0.96(6H,t), 1.08(3H,t), 1.28-1.35(6H,m),1.46-1.48(2H,m) , 1.92 (4H, q), 2.60 (2H, q), 2.96 (2H, t), 7.89-7.92 (2H, m), 8.03-8.13 (4H, m)

MS(m/e)：390 MS( m/e ): 390

反應3：1-(9,9-二乙基-7-(1-(羥基亞胺基)丙基)-9H-茀-2-基)-1-庚酮肟(98)之合成 Reaction 3: Synthesis of 1-(9,9-diethyl-7-(1-(hydroxyimino)propyl)-9H-fusel-2-yl)-1-heptanone oxime (98)

根據上述實例1之反應3的條件從1-(9,9-二乙基-7-丙醯基-9H-茀-2-基)-1-庚酮(97)獲得1-(9,9-二乙基-7-(1-(羥基亞胺基)丙基)-9H-茀-2-基)-1-庚酮肟(98)(65.3%)。 1-(9,9) was obtained from 1-(9,9-diethyl-7-propionyl-9H-fusel-2-yl)-1-heptanone (97) according to the conditions of Reaction 3 of Example 1 above -Diethyl-7-(1-(hydroxyimino)propyl)-9H-fusel-2-yl)-1-heptanone oxime (98) (65.3%).

1H-NMR(δ ppm；DMSO-d 6 )：0.91(3H,t),0.96(6H,t),1.09(3H,t),1.29-1.33(6H,m),1.48-1.50(2H,m),1.92(4H,q),2.72-2.76(4H,m),8.02-8.08(4H,m),8.18(2H,s),11.01(1H,s),11.09(1H,s) 1 H-NMR (δ ppm; DMSO- d 6 ): 0.91 (3H, t), 0.96 (6H, t), 1.09 (3H, t), 1.29-1.33 (6H, m), 1.48-1.50 (2H, m), 1.92 (4H, q), 2.72-2.76 (4H, m), 8.02-8.08 (4H, m), 8.18 (2H, s), 11.01 (1H, s), 11.09 (1H, s)

MS(m/e)：420 MS( m/e ): 420

反應4：1-(9,9-二乙基-7-(1-(乙醯基氧基亞胺基)丙基)-9H-茀-2-基)-1-庚酮-O-乙醯基肟(99)之合成 Reaction 4: 1-(9,9-diethyl-7-(1-(acetyloxyimino)propyl)-9H-fusel-2-yl)-1-heptanone-O-ethyl Synthesis of Acyl Oxime (99)

根據上述實例1之反應4的條件使1-(9,9-二乙基-7-(1-(羥基亞胺基)丙基)-9H-茀-2-基)-1-庚酮肟(98)與乙醯氯反應以獲得1-(9,9-二乙基-7-(1-(乙醯基氧基亞胺基)丙基)-9H-茀-2-基)-1-庚酮-O-乙醯基肟(99)(71.3%)。 According to the conditions of reaction 4 in Example 1 above, 1-(9,9-diethyl-7-(1-(hydroxyimino)propyl)-9H-fusel-2-yl)-1-heptanone oxime (98) Reaction with acetyl chloride to obtain 1-(9,9-diethyl-7-(1-(acetyloxyimino)propyl)-9H-fusel-2-yl)-1 -Heptanone-O-acetoxyxime (99) (71.3%).

1H-NMR(δ ppm；CDCl3)：0.91(3H,t),0.96(6H,t),1.08(3H,t),1.29-1.33(6H,m),1.51(2H,m),1.92(4H,q),2.20(4H,s),2.72-2.76(4H,m),8.02-8.08(4H,m),8.18(2H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.91 (3H, t), 0.96 (6H, t), 1.08 (3H, t), 1.29-1.33 (6H, m), 1.51 (2H, m), 1.92 (4H,q), 2.20(4H,s),2.72-2.76(4H,m),8.02-8.08(4H,m),8.18(2H,s)

MS(m/e)：504 MS( m/e ): 504

[實例35]1-(9,9-二乙基-7-(1-(苯甲醯基氧基亞胺基)丙基)-9H-茀-2-基)-1-庚酮-O-苯甲醯基肟(100)之製備 [Example 35] 1-(9,9-diethyl-7-(1-(benzyloxyimino)propyl)-9H-fusel-2-yl)-1-heptanone-O -Preparation of benzoyl oxime (100)

Figure 105103739-A0202-12-0088-54
Figure 105103739-A0202-12-0088-54

根據上述實例34之反應4的條件使1-(9,9-二乙基-7-(1-(羥基亞胺基)丙基)-9H-茀-2-基)-1-庚酮肟(98)與苯甲醯氯反應以獲得1-(9,9-二乙基-7-(1-(苯甲醯基氧基亞胺基)丙基)-9H-茀-2-基)-1-庚酮-O-苯甲醯基肟(100)(60.3%)。 According to the conditions of Reaction 4 in Example 34 above, 1-(9,9-diethyl-7-(1-(hydroxyimino)propyl)-9H-fusel-2-yl)-1-heptanone oxime (98) React with benzoyl chloride to obtain 1-(9,9-diethyl-7-(1-(benzyloxyimino)propyl)-9H-fusel-2-yl) -1-heptanone-O-benzyl oxime (100) (60.3%).

1H-NMR(δ ppm；CDCl3)：0.91(3H,t),0.96(6H,t),1.08(3H,t),1.29-1.33(6H,m),1.51(2H,m),1.92(4H,q),2.72-2.76(4H,m),7.60-7.65(4H,m),7.76-7.79(2H,m),8.02-8.08(4H,m),8.18-8.22(6H,m) 1 H-NMR (δ ppm; CDCl 3 ): 0.91 (3H, t), 0.96 (6H, t), 1.08 (3H, t), 1.29-1.33 (6H, m), 1.51 (2H, m), 1.92 (4H,q),2.72-2.76(4H,m),7.60-7.65(4H,m),7.76-7.79(2H,m),8.02-8.08(4H,m),8.18-8.22(6H,m)

MS(m/e)：628 MS( m/e ): 628

[實例36]1-(9,9-二乙基-7-(1-(環己烷羰基氧基亞胺基)丙基)-9H-茀-2-基)-1-庚酮-O-環己烷羰基肟(101)之製備 [Example 36] 1-(9,9-diethyl-7-(1-(cyclohexanecarbonyloxyimino)propyl)-9H-fusel-2-yl)-1-heptanone-O -Preparation of cyclohexanecarbonyl oxime (101)

Figure 105103739-A0202-12-0089-55
Figure 105103739-A0202-12-0089-55

根據上述實例34之反應4的條件使1-(9,9-二乙基-7-(1-(羥基亞胺基)丙基)-9H-茀-2-基)-1-庚酮肟(98)與環己烷甲醯氯反應以獲得1-(9,9-二乙基-7-(1-(環己烷羰基氧基亞胺基)丙基)-9H-茀-2-基)-1-庚酮-O-環己烷羰基肟(101)(58.1%)。 According to the conditions of Reaction 4 in Example 34 above, 1-(9,9-diethyl-7-(1-(hydroxyimino)propyl)-9H-fusel-2-yl)-1-heptanone oxime (98) Reaction with cyclohexanecarboxamide to obtain 1-(9,9-diethyl-7-(1-(cyclohexanecarbonyloxyimino)propyl)-9H-fusel-2- Group)-1-heptanone-O-cyclohexanecarbonyl oxime (101) (58.1%).

1H-NMR(δ ppm；CDCl3)：0.91(3H,t),0.96(6H,t),1.08(3H,t),1.12-1.14(6H,m),1.29-1.33(6H,m),1.38-1.50(6H,m),1.52-1.54(2H,m),1.59-1.62(5H,m),1.76-1.79(4H,m),1.92-2.23(5H,m),2.72-2.76(4H,m)8.02-8.08(4H,m),8.18-8.22(2H,m) 1 H-NMR (δ ppm; CDCl 3 ): 0.91 (3H, t), 0.96 (6H, t), 1.08 (3H, t), 1.12-1.14 (6H, m), 1.29-1.33 (6H, m) , 1.38-1.50 (6H, m), 1.52-1.54 (2H, m), 1.59-1.62 (5H, m), 1.76-1.79 (4H, m), 1.92-2.23 (5H, m), 2.72-2.76 ( 4H,m)8.02-8.08(4H,m),8.18-8.22(2H,m)

MS(m/e)：641 MS( m/e ): 641

[實例37]1-(9,9-二乙基-7-(2-(乙醯基氧基亞胺基)丙醯 基)-9H-茀-2-基)-1,2-庚烷二酮-2-O-乙醯基肟(103)之製備 [Example 37] 1-(9,9-diethyl-7-(2-(ethyloxyimino)propylene) ))-9H-茀-2-yl)-1,2-heptanedione-2-O-acetyl oxime (103)

Figure 105103739-A0202-12-0090-56
Figure 105103739-A0202-12-0090-56

根據上述實例34之反應4的條件使1-(9,9-二乙基-7-(2-(羥基亞胺基)丙醯基)-9H-茀-2-基)-1,2-庚烷二酮-2-肟(102)與乙醯氯反應以獲得1-(9,9-二乙基-7-(2-(乙醯基氧基亞胺基)丙醯基)-9H-茀-2-基)-1,2-庚烷二酮-2-O-乙醯基肟(103)(65.1%)。 According to the conditions of Reaction 4 in Example 34 above, 1-(9,9-diethyl-7-(2-(hydroxyimino)propionyl)-9H-fusel-2-yl)-1,2- Heptanedione-2-oxime (102) is reacted with acetyl chloride to obtain 1-(9,9-diethyl-7-(2-(acetoxyoxyimino)propionyl)-9H -Fu-2-yl)-1,2-heptanedione-2-O-acetyl oxime (103) (65.1%).

1H-NMR(δ ppm；CDCl3)：0.91(3H,t),0.96(6H,t),1.29-1.33(6H,m),1.45-1.50(2H,m),1.88-1.92(7H,m),2.09(6H,s),7.90-7.93(2H,m),8.02-8.10(4H,m) 1 H-NMR (δ ppm; CDCl 3 ): 0.91 (3H, t), 0.96 (6H, t), 1.29-1.33 (6H, m), 1.45-1.50 (2H, m), 1.88-1.92 (7H, m), 2.09 (6H, s), 7.90-7.93 (2H, m), 8.02-8.10 (4H, m)

MS(m/e)：532 MS( m/e ): 532

[實例38]1-(9,9-二乙基-7-(2-(苯甲醯基氧基亞胺基)丙醯基)-9H-茀-2-基)-1,2-庚烷二酮-2-O-苯甲醯基肟(104)之製備 [Example 38] 1-(9,9-diethyl-7-(2-(benzyloxyimino) propionyl)-9H-fusel-2-yl)-1,2-heptane Preparation of alkanedione-2-O-benzoyl oxime (104)

Figure 105103739-A0202-12-0091-58
Figure 105103739-A0202-12-0091-58

根據上述實例34之反應4的條件使1-(9,9-二乙基-7-(2-(羥基亞胺基)丙醯基)-9H-茀-2-基)-1,2-庚烷二酮-2-肟(102)與苯甲醯氯反應以獲得1-(9,9-二乙基-7-(2-(苯甲醯基氧基亞胺基)丙醯基)-9H-茀-2-基)-1,2-庚烷二酮-2-O-苯甲醯基肟(104)(55.3%)。 According to the conditions of Reaction 4 in Example 34 above, 1-(9,9-diethyl-7-(2-(hydroxyimino)propionyl)-9H-fusel-2-yl)-1,2- Heptanedione-2-oxime (102) is reacted with benzoyl chloride to obtain 1-(9,9-diethyl-7-(2-(benzyloxyimino)propionyl) -9H-茀-2-yl)-1,2-heptanedione-2-O-benzoyl oxime (104) (55.3%).

1H-NMR(δ ppm；CDCl3)：0.90(3H,t),0.97(6H,t),1.29-1.35(6H,m),1.47-1.50(2H,m),1.88-1.93(7H,m),7.63-7.67(4H,m),7.75-7.78(2H,m),7.93-8.03(4H,m),8.10-8.15(6H,m) 1 H-NMR (δ ppm; CDCl 3 ): 0.90 (3H, t), 0.97 (6H, t), 1.29-1.35 (6H, m), 1.47-1.50 (2H, m), 1.88-1.93 (7H, m), 7.63-7.67 (4H, m), 7.75-7.78 (2H, m), 7.93-8.03 (4H, m), 8.10-8.15 (6H, m)

MS(m/e)：657 MS( m/e ): 657

[實例39]1-(9,9-二乙基-7-(2-(環己烷羰基氧基亞胺基)丙醯基)-9H-茀-2-基)-1,2-庚烷二酮-2-O-環己烷羰基肟(105) 之製備 [Example 39] 1-(9,9-diethyl-7-(2-(cyclohexanecarbonyloxyimino) propionyl)-9H-fusel-2-yl)-1,2-heptane Alkanedione-2-O-cyclohexanecarbonyl oxime (105) Preparation

Figure 105103739-A0202-12-0092-59
Figure 105103739-A0202-12-0092-59

根據上述實例34之反應4的條件使1-(9,9-二乙基-7-(2-(羥基亞胺基)丙醯基)-9H-茀-2-基)-1,2-庚烷二酮-2-肟(102)與環己烷甲醯氯反應以獲得1-(9,9-二乙基-7-(2-(環己烷羰基氧基亞胺基)丙醯基)-9H-茀-2-基)-1,2-庚烷二酮-2-O-環己烷羰基肟(105)(55.0%)。 According to the conditions of Reaction 4 in Example 34 above, 1-(9,9-diethyl-7-(2-(hydroxyimino)propionyl)-9H-fusel-2-yl)-1,2- Heptanedione-2-oxime (102) reacts with cyclohexanecarboxamide to obtain 1-(9,9-diethyl-7-(2-(cyclohexanecarbonyloxyimino)propionamide Group)-9H-fusel-2-yl)-1,2-heptanedione-2-O-cyclohexanecarbonyl oxime (105) (55.0%).

1H-NMR(δ ppm；CDCl3)：0.91(3H,t),0.96(6H,t),1.12-1.14(6H,m),1.29-1.33(6H,m),1.52-1.54(2H,m),1.59-1.62(5H,m),1.69-1.81(10H,m),1.92-2.23(8H,m),7.91-7.93(2H,m),8.02-8.10(4H,m) 1 H-NMR (δ ppm; CDCl 3 ): 0.91 (3H, t), 0.96 (6H, t), 1.12-1.14 (6H, m), 1.29-1.33 (6H, m), 1.52-1.54 (2H, m), 1.59-1.62 (5H, m), 1.69-1.81 (10H, m), 1.92-2.23 (8H, m), 7.91-7.93 (2H, m), 8.02-8.10 (4H, m)

MS(m/e)：669 MS( m/e ): 669

[實例40]1-(7-(1,2-(雙乙醯基氧基亞胺基)丙醯基)-9,9-二乙基-9H-茀-2-基)-1,2-庚烷二酮-1,2-雙(O-乙醯基肟)(107)之製備 [Example 40] 1-(7-(1,2-(bisethoxyoxyimino)propionyl)-9,9-diethyl-9H-fusel-2-yl)-1,2 -Preparation of -heptanedione-1,2-bis(O-acetyl oxime) (107)

Figure 105103739-A0202-12-0093-60
Figure 105103739-A0202-12-0093-60

根據上述實例34之反應4的條件使1-(7-(1,2-(雙乙醯基氧基亞胺基)丙醯基)-9,9-二乙基-9H-茀-2-基)-1,2-庚烷二酮-1,2-雙(肟)(27)與乙醯氯反應以獲得1-(7-(1,2-(雙乙醯基氧基亞胺基)丙醯基)-9,9-二乙基-9H-茀-2-基)-1,2-庚烷二酮-1,2-雙(O-乙醯基肟)(28)(66.3%)。 According to the conditions of Reaction 4 in Example 34 above, 1-(7-(1,2-(bisethoxycarbonylimino)propionyl)-9,9-diethyl-9H-fusel-2- Group)-1,2-heptanedione-1,2-bis(oxime)(27) reacts with acetyl chloride to obtain 1-(7-(1,2-(bisacetoxyimino ) Propionyl)-9,9-diethyl-9H-fusel-2-yl)-1,2-heptanedione-1,2-bis(O-acetyl oxime) (28)(66.3 %).

1H-NMR(δ ppm；CDCl3)：0.91(3H,t),0.98(6H,t),1.29-1.35(6H,m),1.49-1.51(2H,m),1.89-1.92(7H,m),2.10(12H,s),8.01-8.10(4H,m),8.19(2H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.91 (3H, t), 0.98 (6H, t), 1.29-1.35 (6H, m), 1.49-1.51 (2H, m), 1.89-1.92 (7H, m), 2.10(12H,s), 8.01-8.10(4H,m), 8.19(2H,s)

MS(m/e)：647 MS( m/e ): 647

[實例41]1-(7-(1,2-(雙苯甲醯基氧基亞胺基)丙醯基)-9,9-二乙基-9H-茀-2-基)-1,2-庚烷二酮-1,2-雙(O-苯甲醯基肟)(108)之製備 [Example 41] 1-(7-(1,2-(bisbenzyloxyimino) propionyl)-9,9-diethyl-9H-fusel-2-yl)-1, Preparation of 2-heptanedione-1,2-bis(O-benzyl oxime) (108)

Figure 105103739-A0202-12-0094-61
Figure 105103739-A0202-12-0094-61

根據上述實例34之反應4的條件使1-(7-(1,2-(雙乙醯基氧基亞胺基)丙醯基)-9,9-二乙基-9H-茀-2-基)-1,2-庚烷二酮-1,2-雙(肟)(106)與苯甲醯氯反應以獲得1-(7-(1,2-(雙苯甲醯基氧基亞胺基)丙醯基)-9,9-二乙基-9H-茀-2-基)-1,2-庚烷二酮-1,2-雙(O-苯甲醯基肟)(108)(52.1%)。 According to the conditions of Reaction 4 in Example 34 above, 1-(7-(1,2-(bisethoxycarbonylimino)propionyl)-9,9-diethyl-9H-fusel-2- Group)-1,2-heptanedione-1,2-bis(oxime)(106) reacts with benzoyl chloride to obtain 1-(7-(1,2-(bisbenzoyloxyoxy (Amino)propanyl)-9,9-diethyl-9H-fusel-2-yl)-1,2-heptanedione-1,2-bis(O-benzyl oxime) (108 ) (52.1%).

1H-NMR(δ ppm；CDCl3)：0.91(3H,t),0.97(6H,t),1.29-1.35(6H,m),1.49-1.51(2H,m),1.89-1.92(7H,m),7.63-7.66(8H,m),7.78-7.80(4H,m),8.01-8.10(4H,m),8.14-8.20(10H,m) 1 H-NMR (δ ppm; CDCl 3 ): 0.91 (3H, t), 0.97 (6H, t), 1.29-1.35 (6H, m), 1.49-1.51 (2H, m), 1.89-1.92 (7H, m), 7.63-7.66 (8H, m), 7.78-7.80 (4H, m), 8.01-8.10 (4H, m), 8.14-8.20 (10H, m)

MS(m/e)：895 MS( m/e ): 895

[實例42]1-(7-(1,2-(雙環己烷羰基氧基亞胺基)丙醯 基)-9,9-二乙基-9H-茀-2-基)-1,2-庚烷二酮-1,2-雙(O-環己烷羰基肟)(109)之製備 [Example 42] 1-(7-(1,2-(bicyclohexanecarbonyloxyimino)propylene Yl)-9,9-diethyl-9H-茀-2-yl)-1,2-heptanedione-1,2-bis(O-cyclohexanecarbonyloxime) (109)

Figure 105103739-A0202-12-0095-62
Figure 105103739-A0202-12-0095-62

根據上述實例34之反應4的條件使1-(7-(1,2-(雙乙醯基氧基亞胺基)丙醯基)-9,9-二乙基-9H-茀-2-基)-1,2-庚烷二酮-1,2-雙(肟)(106)與環己烷甲醯氯反應以獲得1-(7-(1,2-(雙環己烷羰基氧基亞胺基)丙醯基)-9,9-二乙基-9H-茀-2-基)-1,2-庚烷二酮-1,2-雙(O-環己烷羰基肟)(109)(50.3%)。 According to the conditions of Reaction 4 in Example 34 above, 1-(7-(1,2-(bisethoxycarbonylimino)propionyl)-9,9-diethyl-9H-fusel-2- Group)-1,2-heptanedione-1,2-bis(oxime)(106) reacts with cyclohexaneformyl chloride to obtain 1-(7-(1,2-(bicyclohexanecarbonyloxy Imino)propionyl)-9,9-diethyl-9H-fusel-2-yl)-1,2-heptanedione-1,2-bis(O-cyclohexanecarbonyloxime) ( 109) (50.3%).

1H-NMR(δ ppm；CDCl3)：0.91(3H,t),0.96(6H,t),1.12-1.14(12H,m),1.29-1.33(6H,m),1.52-1.54(2H,m),1.59-1.62(10H,m),1.69-1.81(20H,m),1.92-2.23(9H,m),7.91-7.93(2H,m),8.02-8.10(4H,m) 1 H-NMR (δ ppm; CDCl 3 ): 0.91 (3H, t), 0.96 (6H, t), 1.12-1.14 (12H, m), 1.29-1.33 (6H, m), 1.52-1.54 (2H, m), 1.59-1.62 (10H, m), 1.69-1.81 (20H, m), 1.92-2.23 (9H, m), 7.91-7.93 (2H, m), 8.02-8.10 (4H, m)

MS(m/e)：919 MS( m/e ): 919

[實例43]1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(O-乙醯基肟)(114)之製備 [Example 43] 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-ethanone-1,1'-bis(O-acetyl Oxime) (114)

Figure 105103739-A0202-12-0096-63
Figure 105103739-A0202-12-0096-63

反應1：9,9-二乙基-4-硝基-9H-茀(111)之合成 Reaction 1: Synthesis of 9,9-diethyl-4-nitro-9H-fusel (111)

根據上述實例1之反應1的條件使4-硝基茀(110)與溴乙烷反應以獲得9,9-二乙基-4-硝基-9H-茀(111)(88.2%)。 4-Nitrostilbene (110) was reacted with bromoethane according to the conditions of Reaction 1 of Example 1 above to obtain 9,9-diethyl-4-nitro-9H-stilbene (111) (88.2%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),2.0(4H,q),7.26-7.30(2H,m),7.54-7.55(2H,m),7.84-7.93(3H,m) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 2.0 (4H, q), 7.26-7.30 (2H, m), 7.54-7.55 (2H, m), 7.84-7.93 (3H, m)

MS(m/e)：267 MS( m/e ): 267

反應2：1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-乙酮(112)之合成 Reaction 2: 1,1 '- (9,9-diethyl-4-nitro -9 H - fluorene-2,7-diyl) bis - ethanone (112) Synthesis of

根據上述實例1之反應2的條件使9,9-二乙基-4-硝基-9H-茀(111)與乙醯氯反應以獲得1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-乙酮(112)(59.2%)。 The reaction conditions of Example 12 above is 9,9-diethyl-4-nitro -9 H - fluorene (111) is reacted with acetyl chloride to obtain 1,1 '- (9,9-diethyl -4-nitro-9 H -fu-2,7-diyl)bis-ethanone (112) (59.2%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.90(4H,q),2.55(6H,s),7.94-7.95(2H,m),8.15(1H,s),8.54(1H,s),8.91(1H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.90 (4H, q), 2.55 (6H, s), 7.94-7.95 (2H, m), 8.15 (1H, s), 8.54 (1H,s),8.91(1H,s)

MS(m/e)：351 MS( m/e ): 351

反應3：1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(肟)(113)之合成 Reaction 3: 1,1 '- (9,9-diethyl-4-nitro -9 H - fluorene-2,7-diyl) bis - ethanone 1,1'-bis (oxime) (113 ) Synthesis

根據上述實例1之反應3的條件從1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-乙酮(112)獲得1,1’-(9,9-二乙基 -4-硝基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(肟)(113)(61.3%)。 According to the conditions of Reaction 3 in Example 1 above, 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-ethanone (112) was obtained 1, 1'-(9,9-diethyl -4-nitro-9H-fu-2,7-diyl)bis-ethanone-1,1'-bis(oxime) (113) (61.3%).

1H-NMR(δ ppm；DMSO-d 6 )：0.96(6H,t),1.89(6H,s),1.92(4H,q),8.02-8.08(2H,m),8.19(1H,s),8.58(1H,s),8.91(1H,s),11.01(1H,s),11.03(2H,s) 1 H-NMR (δ ppm; DMSO- d 6 ): 0.96 (6H, t), 1.89 (6H, s), 1.92 (4H, q), 8.02-8.08 (2H, m), 8.19 (1H, s) , 8.58 (1H, s), 8.91 (1H, s), 11.01 (1H, s), 11.03 (2H, s)

MS(m/e)：381 MS( m/e ): 381

反應4：1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(O-乙醯基肟)(114)之合成 Reaction 4: 1,1'-(9,9-diethyl-4-nitro-9H-fusel-2,7-diyl) bis-ethanone-1,1'-bis(O-acetyl acetyl Synthesis of oxime) (114)

根據上述實例1之反應4的條件使1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(肟)(113)與乙醯氯反應以獲得1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(O-乙醯基肟)(114)(70.7%)。 According to the conditions of reaction 4 in Example 1 above, 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-ethanone-1,1'- Bis(oxime)(113) reacts with acetyl chloride to obtain 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-ethanone-1 , 1'-bis (O-acetoxy oxime) (114) (70.7%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.89(6H,s),1.92(4H,q),2.08(6H,s),8.02-8.08(2H,m),8.19(1H,s),8.58(1H,s),8.91(1H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.89 (6H, s), 1.92 (4H, q), 2.08 (6H, s), 8.02-8.08 (2H, m), 8.19 (1H,s), 8.58(1H,s), 8.91(1H,s)

MS(m/e)：465 MS( m/e ): 465

[實例44]1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙- 乙酮-1,1’-雙(O-苯甲醯基肟)(115)之製備 [Example 44] 1,1’-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis- Preparation of Acetophenone-1,1’-bis(O-benzoyl oxime) (115)

Figure 105103739-A0202-12-0099-64
Figure 105103739-A0202-12-0099-64

根據上述實例43之反應4的條件使1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(肟)(113)與苯甲醯氯反應以獲得1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(O-苯甲醯基肟)(115)(63.2%)。 The conditions of the reaction so that the above-described Example 1, 1 of 43 4 '- (9,9-diethyl-4-nitro -9 H - fluorene-2,7-diyl) bis - ethanone 1,1' - bis (oxime) (113) is reacted with benzoyl chloride to obtain 1,1 '- (9,9-diethyl-4-nitro -9 H - fluorene-2,7-diyl) bis - acetate Ketone-1,1'-bis( O -benzyl oxime) (115) (63.2%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.89(6H,s),1.92(4H,q),7.64-7.66(4H,m),7.78-7.80(2H,m),8.02-8.05(2H,m),8.14-8.19(5H,s),8.58(1H,s),8.91(1H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.89 (6H, s), 1.92 (4H, q), 7.64-7.66 (4H, m), 7.78-7.80 (2H, m) , 8.02-8.05(2H, m), 8.14-8.19(5H, s), 8.58(1H, s), 8.91(1H, s)

MS(m/e)：590 MS( m/e ): 590

[實例45]1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(O-環己烷羰基肟)(116)之製備 [Example 45] 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-ethanone-1,1'-bis(O-cyclohexyl Preparation of alkylcarbonyl oxime) (116)

Figure 105103739-A0202-12-0100-65
Figure 105103739-A0202-12-0100-65

根據上述實例43之反應4的條件使1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(肟)(113)與環己烷甲醯氯反應以獲得1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-乙酮-1,1’-雙(O-環己烷羰基肟)(116)(61.3%)。 According to the conditions of reaction 4 of Example 43 above, 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-ethanone-1,1'- Bis(oxime)(113) reacts with cyclohexaneformyl chloride to obtain 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-ethyl Ketone-1,1'-bis(O-cyclohexanecarbonyl oxime) (116) (61.3%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.1-1.2(6H,m),1.39-1.54(5H,m),1.60-1.62(5H,m),1.89-1.91(7H,m),2.25-2.27(1H,m),8.02-8.05(2H,m),8.19(1H,s),8.58(1H,s),8.91(1H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.1-1.2 (6H, m), 1.39-1.54 (5H, m), 1.60-1.62 (5H, m), 1.89-1.91 ( 7H,m),2.25-2.27(1H,m),8.02-8.05(2H,m),8.19(1H,s),8.58(1H,s),8.91(1H,s)

MS(m/e)：602 MS( m/e ): 602

[實例46]1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(O-乙醯基肟)(119)之製備 [Example 46] 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-1,2-propanedione-2,2'-bis Preparation of (O-acetyl oxime) (119)

Figure 105103739-A0202-12-0101-66
Figure 105103739-A0202-12-0101-66

根據上述實例26之反應1的條件使9,9-二乙基-4-硝基-9H-茀(111)與丙醯氯反應以合成1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1-丙酮(117)。然後，根據上述實例26之反應2至反應3的條件獲得1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(O-乙醯基肟)(119)(67.1%)。 According to the conditions of Reaction 1 in Example 26 above, 9,9-diethyl-4-nitro-9H-fusel (111) was reacted with propyl chloride to synthesize 1,1'-(9,9-diethyl- 4-nitro-9H-fusel-2,7-diyl)bis-1-acetone (117). Then, 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-1,2 was obtained according to the conditions of Reaction 2 to Reaction 3 in Example 26 above -Propanedione-2,2'-bis(O-acetyl oxime) (119) (67.1%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.88(6H,s),1.91(4H,q),2.08(6H,s),7.92(1H,d),8.01(1H,d),8.18(1H,s),8.57(1H,s),8.94(1H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.88 (6H, s), 1.91 (4H, q), 2.08 (6H, s), 7.92 (1H, d), 8.01 (1H ,d),8.18(1H,s),8.57(1H,s),8.94(1H,s)

MS(m/e)：522 MS( m/e ): 522

[實例47]1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(O-苯甲醯基肟)(120)之製備 [Example 47] 1,1'-(9,9-diethyl-4-nitro-9H-fusel-2,7-diyl)bis-1,2-propanedione-2,2'-bis Preparation of (O-benzyl oxime) (120)

Figure 105103739-A0202-12-0102-67
Figure 105103739-A0202-12-0102-67

根據上述實例46之反應3的條件使1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(肟)(118)與苯甲醯氯反應以獲得1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(O-苯甲醯基肟)(120)(61.2%)。 According to the conditions of reaction 3 in Example 46 above, 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-1,2-propanedione- 2,2'-bis(oxime)(118) reacts with benzoyl chloride to obtain 1,1'-(9,9-diethyl-4-nitro-9H-fusel-2,7-diyl) Bis-1,2-propanedione-2,2'-bis(O-benzoyl oxime) (120) (61.2%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.88(6H,s),1.91(4H,q),7.63-7.65(4H,m),7.78-7.80(2H,m),7.93-8.03(2H,m),8.03-8.14(5H,m),8.49(1H,m),8.84(1H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.88 (6H, s), 1.91 (4H, q), 7.63-7.65 (4H, m), 7.78-7.80 (2H, m) , 7.93-8.03 (2H, m), 8.03-8.14 (5H, m), 8.49 (1H, m), 8.84 (1H, s)

MS(m/e)：646 MS( m/e ): 646

[實例48]1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(O-環己烷羰基肟)(121)之製備 [Example 48] 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-1,2-propanedione-2,2'-bis Preparation of (O-cyclohexanecarbonyloxime) (121)

Figure 105103739-A0202-12-0103-68
Figure 105103739-A0202-12-0103-68

根據上述實例46之反應3的條件使1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(肟)(118)與環己烷甲醯氯反應以獲得1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(O-環己烷羰基肟)(121)(56.2%)。 According to the conditions of reaction 3 in Example 46 above, 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-1,2-propanedione- 2,2'-bis(oxime)(118) reacts with cyclohexaneformyl chloride to obtain 1,1'-(9,9-diethyl-4-nitro-9H-fusel-2,7-di Group) bis-1,2-propanedione-2,2'-bis(O-cyclohexanecarbonyl oxime) (121) (56.2%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.11-1.13(6H,m),1.39-1.54(10H,m),1.59-1.61(5H,m),1.88(6H,s),1.91(4H,q),2.27(1H,m),7.93-8.03(2H,m),8.14(1H,m),8.49(1H,m),8.84(1H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.11-1.13 (6H, m), 1.39-1.54 (10H, m), 1.59-1.61 (5H, m), 1.88 (6H, s), 1.91 (4H, q), 2.27 (1H, m), 7.93-8.03 (2H, m), 8.14 (1H, m), 8.49 (1H, m), 8.84 (1H, s)

MS(m/e)：658 MS( m/e ): 658

[實例49]1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙 -1,2-丙烷二酮-1,1’,2,2’-肆(O-乙醯基肟)(123)之製備 [Example 49] 1,1’-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis -Preparation of 1,2-propanedione-1,1’,2,2’-O (O-acetyl oxime) (123)

Figure 105103739-A0202-12-0104-70
Figure 105103739-A0202-12-0104-70

根據上述實例26之反應2的條件從1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(肟)(118)合成1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(肟)(122)。然後，根據上述實例26之反應3的條件獲得1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(O-乙醯基肟)(123)(66.2%)。 According to the conditions of reaction 2 in Example 26 above, from 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-1,2-propanedione- 2,2'-bis(oxime)(118) synthesis of 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-1,2-propane Diketone-1,1',2,2'-Ran (oxime) (122). Then, according to the conditions of Reaction 3 in Example 26 above, 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-1,2-propanedi Ketone-1,1',2,2'-O (O-acetoxy oxime) (123) (66.2%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.88(6H,s),1.91(4H,q),2.08(12H,s),8.01-8.08(2H,m),8.18(1H,s),8.57(1H,s),8.94(1H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.88 (6H, s), 1.91 (4H, q), 2.08 (12H, s), 8.01-8.08 (2H, m), 8.18 (1H,s), 8.57(1H,s), 8.94(1H,s)

MS(m/e)：636 MS( m/e ): 636

[實例50]1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙 -1,2-丙烷二酮-1,1’,2,2’-肆(O-苯甲醯基肟)(124)之製備 [Example 50] 1,1’-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis -Preparation of -1,2-propanedione-1,1’,2,2’-O (O-benzoyl oxime) (124)

Figure 105103739-A0202-12-0105-71
Figure 105103739-A0202-12-0105-71

根據上述實例49之反應2的條件使1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(肟)(122)與苯甲醯氯反應以獲得1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(O-苯甲醯基肟)(124)(56.1%)。 According to the conditions of reaction 2 in Example 49 above, 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-1,2-propanedione- 1,1',2,2'-oxime (122) reacts with benzoyl chloride to obtain 1,1'-(9,9-diethyl-4-nitro-9H-fusel-2, 7-diyl)bis-1,2-propanedione-1,1',2,2'-an (O-benzyloxime) (124) (56.1%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.88(6H,s),1.91(4H,q),7.63-7.65(8H,m),7.77-7.79(4H,m),8.01-8.08(2H,m),8.14-8.19(9H,m),8.57(1H,s),8.94(1H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.88 (6H, s), 1.91 (4H, q), 7.63-7.65 (8H, m), 7.77-7.79 (4H, m) , 8.01-8.08 (2H, m), 8.14-8.19 (9H, m), 8.57 (1H, s), 8.94 (1H, s)

MS(m/e)：884 MS( m/e ): 884

[實例51]1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(O-環己烷羰基肟)(125)之製備 [Example 51] 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-1,2-propanedione-1,1',2 , Preparation of 2'-Ran (O-cyclohexanecarbonyloxime) (125)

Figure 105103739-A0202-12-0106-73
Figure 105103739-A0202-12-0106-73

根據上述實例49之反應2的條件使1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(肟)(122)與環己烷甲醯氯反應以獲得1,1’-(9,9-二乙基-4-硝基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-1,1’,2,2’-肆(O-環己烷羰基肟)(125)(55.1%)。 According to the conditions of reaction 2 in Example 49 above, 1,1'-(9,9-diethyl-4-nitro-9H-fu-2,7-diyl)bis-1,2-propanedione- 1,1',2,2'-oxime (122) is reacted with cyclohexanecarboxamide to obtain 1,1'-(9,9-diethyl-4-nitro-9H-fuselium- 2,7-diyl)bis-1,2-propanedione-1,1',2,2'-an (O-cyclohexanecarbonyl oxime) (125) (55.1%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.12-1.14(12H,m),1.59-1.62(10H,m),1.69-1.81(20H,m),1.87-1.89(6H,s),1.90-1.92(4H,q),2.25-2.28(2H,m),8.01-8.08(2H,m),8.18(1H,s),8.57(1H,s),8.94(1H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.12-1.14 (12H, m), 1.59-1.62 (10H, m), 1.69-1.81 (20H, m), 1.87-1.89 ( 6H,s),1.90-1.92(4H,q),2.25-2.28(2H,m),8.01-8.08(2H,m),8.18(1H,s),8.57(1H,s),8.94(1H, s)

MS(m/e)：908 MS( m/e ): 908

[實例52]1,1’-(4-氰基-9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(O-乙醯基肟)(131)之製備 [Example 52] 1,1 '- (4-cyano-9,9-diethyl -9 H - fluorene-2,7-diyl) bis-1,2-propane-2,2-dione Preparation of bis( O -acetyl oxime) (131)

Figure 105103739-A0202-12-0107-74
Figure 105103739-A0202-12-0107-74

反應1：4-溴-9,9-二乙基-9H-茀(127)之合成 Reaction 1: 4-Bromo-9,9-diethyl -9 H - fluorene (127) Synthesis of

根據上述實例25之反應1的條件使4-溴茀(126)與溴乙烷反應以獲得4-溴-9,9-二乙基-9H-茀(127)(78.2%)。 The reaction conditions of the above Example 25 1 4-bromo fluorene (126) with dibromoethane to obtain 4-bromo-9,9-diethyl -9 H - fluorene (127) (78.2%).

1H-NMR(δ ppm；CDCl3)：0.96(6H,t),1.92(4H,q),7.17-7.28(2H,m),7.54-7.55(2H,m),7.84-7.93(3H,m) 1 H-NMR (δ ppm; CDCl 3 ): 0.96 (6H, t), 1.92 (4H, q), 7.17-7.28 (2H, m), 7.54-7.55 (2H, m), 7.84-7.93 (3H, m)

MS(m/e)：301 MS( m/e ): 301

反應2：4-氰基-9,9-二乙基-9H-茀(128)之合成 Reaction 2: Synthesis of 4-cyano-9,9-diethyl-9H-fusel (128)

將4-溴-9,9-二乙基-9H-茀(127)(30.1g)(0.10mol)溶解於N-甲基-2-吡咯烷酮(NMP)(200mL)，再於其內加入氰化銅(13.43g)(0.15mol)，且反應溶液緩慢加熱和回流3小時。將蒸餾水和乙酸乙酯加入反應混合物，接著攪拌約30分鐘以分離有機層。將經分離的有機層以飽和氯化銨水溶液和蒸餾水清洗3次，且經回收的有機層以無水硫酸鎂乾燥，並在減壓下蒸餾溶劑。所得產物使用矽膠管柱層析法純化(展開溶劑；二氯甲烷：正己烷=1：4)以獲得4-氰基-9,9-二乙基-9H-茀(128)(12.66g)(51.6%)。 4-bromo-9,9-diethyl -9 H - fluorene (127) (30.1g) (0.10mol ) was dissolved in N - methyl-2-pyrrolidone (NMP) (200mL), then was added therein Copper cyanide (13.43 g) (0.15 mol), and the reaction solution was slowly heated and refluxed for 3 hours. Distilled water and ethyl acetate were added to the reaction mixture, followed by stirring for about 30 minutes to separate the organic layer. The separated organic layer was washed 3 times with saturated ammonium chloride aqueous solution and distilled water, and the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The resulting product was purified using silica gel column chromatography (developing solvent; dichloromethane: n-hexane = 1: 4) to obtain 4-cyano-9,9-diethyl -9 H - fluorene (128) (12.66g ) (51.6%).

1H-NMR(δ ppm；CDCl3)：0.95(6H,t),1.91(4H,q),7.17-7.28(2H,m),7.64-7.69(2H,m),7.84-7.93(3H,m) 1 H-NMR (δ ppm; CDCl 3 ): 0.95(6H,t), 1.91(4H,q), 7.17-7.28(2H,m),7.64-7.69(2H,m),7.84-7.93(3H, m)

MS(m/e)：247 MS( m/e ): 247

反應3：1,1’-(4-氰基-9,9-二乙基-9H-茀-2,7-二基)雙-1 -丙酮(129)之合成 Reaction 3: Synthesis of 1,1'-(4-cyano-9,9-diethyl-9 H -fu-2,7-diyl)bis-1 -acetone (129)

根據上述實例25之反應2的條件使4-氰基-9,9-二乙基-9H-茀(128)與丙醯氯反應以獲得1,1’-(4-氰基-9,9-二乙基-9H-茀-2,7-二基)雙-1-丙酮(129)(51.2%)。 The 4-cyano-9,9-diethyl-9H-fusel (128) was reacted with propyl chloride according to the conditions of Reaction 2 of Example 25 above to obtain 1,1'-(4-cyano-9,9 -Diethyl-9H-fusel-2,7-diyl)bis-1-acetone (129) (51.2%).

1H-NMR(δ ppm；CDCl3)：0.94(6H,t),1.19(6H,t),1.91(4H,q),2.52(4H,q),7.92(1H,d),8.01(1H,d),8.18(1H,s),8.57(1H,s),8.94(1H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.94 (6H, t), 1.19 (6H, t), 1.91 (4H, q), 2.52 (4H, q), 7.92 (1H, d), 8.01 (1H ,d),8.18(1H,s),8.57(1H,s),8.94(1H,s)

MS(m/e)：359 MS( m/e ): 359

反應4：1,1’-(4-氰基-9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(肟)(130)之合成 Reaction 4: 1,1'-(4-cyano-9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-2,2'-bis( Synthesis of oxime) (130)

根據上述實例25之反應3的條件從1,1’-(4-氰基-9,9-二乙基-9H-茀-2,7-二基)雙-1-丙酮(129)獲得1,1’-(4-氰基-9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(肟)(130)(46.3%)。 Obtain 1 from 1,1'-(4-cyano-9,9-diethyl-9H-fu-2,7-diyl)bis-1-acetone (129) according to the conditions of reaction 3 in Example 25 above ,1'-(4-cyano-9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-2,2'-bis(oxime) (130 ) (46.3%).

1H-NMR(δ ppm；DMSO-d 6 )：0.95(6H,t),1.89(6H,s),1.91(4H,q),7.93(1H,d),8.00(1H,d),8.17(1H,s),8.55(1H,s),8.92(1H,s),10.96(1H,s),11.00(1H,s) 1 H-NMR (δ ppm; DMSO- d 6 ): 0.95 (6H, t), 1.89 (6H, s), 1.91 (4H, q), 7.93 (1H, d), 8.00 (1H, d), 8.17 (1H,s), 8.55(1H,s), 8.92(1H,s), 10.96(1H,s), 11.00(1H,s)

MS(m/e)：417 MS( m/e ): 417

反應5：1,1’-(4-氰基-9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(O-乙醯基肟)(131)之合成 Reaction 5: 1,1'-(4-cyano-9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione-2,2'-bis( O-acetyl oxime) (131)

根據上述實例25之反應4的條件使1,1’-(4-氰基-9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(肟)(130)與乙醯氯反應以獲得1,1’-(4-氰基-9,9-二乙基-9H-茀-2,7-二基)雙-1,2-丙烷二酮-2,2’-雙(O-乙醯基肟)(131)(60.1%)。 According to the conditions of reaction 4 in Example 25 above, 1,1'-(4-cyano-9,9-diethyl-9H-fu-2,7-diyl)bis-1,2-propanedione- 2,2'-bis(oxime) (130) reacts with acetyl chloride to obtain 1,1'-(4-cyano-9,9-diethyl-9H-fu-2,7-diyl)bis -1,2-propanedione-2,2'-bis(O-acetyl oxime) (131) (60.1%).

1H-NMR(δ ppm；CDCl3)：0.95(6H,t),1.88(6H,s),1.90(4H,q),2.08(6H,s),7.92(1H,d),8.02(1H,d),8.17(1H,s),8.55(1H,s),8.92(1H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.95 (6H, t), 1.88 (6H, s), 1.90 (4H, q), 2.08 (6H, s), 7.92 (1H, d), 8.02 (1H ,d),8.17(1H,s),8.55(1H,s),8.92(1H,s)

MS(m/e)：501 MS( m/e ): 501

[實例53]1,1’-(4-氰基-9,9-二乙基-9H-茀-2,7-二基)雙-丙酮-1,1’-雙(O-乙醯基肟)(133)之製備 [Example 53] 1,1'-(4-cyano-9,9-diethyl-9H-fusel-2,7-diyl)bis-acetone-1,1'-bis(O-acetyl acetyl Preparation of oxime) (133)

Figure 105103739-A0202-12-0110-75
Figure 105103739-A0202-12-0110-75

根據上述實例52之反應5的條件使1,1’-(4-氰基-9,9-二乙基-9H-茀-2,7-二基)雙-丙酮-1,1’-雙(肟)(132)與乙醯氯反應以獲得1,1’-(4-氰基-9,9-二乙基-9H-茀-2,7-二基)雙-丙酮-1,1’-雙(O-乙醯基肟)(133)(71.7%)。 According to the conditions of reaction 5 in Example 52 above, 1,1'-(4-cyano-9,9-diethyl-9H-fu-2,7-diyl)bis-acetone-1,1'-bis (Oxime) (132) reacted with acetyl chloride to obtain 1,1'-(4-cyano-9,9-diethyl-9H-fu-2,7-diyl)bis-acetone-1,1 '-Bis(O-acetyl oxime) (133) (71.7%).

1H-NMR(δ ppm；CDCl3)：0.95(6H,t),1.05(6H,t),1.89(6H,s),2.08(6H,s),2.73(4H,q),8.02-8.08(2H,m),8.19(1H,s),8.58(1H,s),8.91(1H,s) 1 H-NMR (δ ppm; CDCl 3 ): 0.95 (6H, t), 1.05 (6H, t), 1.89 (6H, s), 2.08 (6H, s), 2.73 (4H, q), 8.02-8.08 (2H,m), 8.19(1H,s), 8.58(1H,s), 8.91(1H,s)

MS(m/e)：473 MS( m/e ): 473

<黏合劑樹脂之製備> <Preparation of binder resin>

a)黏合劑樹脂1之製備 a) Preparation of binder resin 1

將丙二醇甲基醚乙酸酯(PGMEA)(200mL)和偶氮二異丁腈(AIBN)(1.5g)加入500mL的聚合反應器，且甲基丙烯酸、環氧丙基甲基丙烯酸、甲基甲基丙烯酸和二環戊基丙烯酸以20：20：40：20的莫耳比率加入，其中丙烯酸系單體的固體含量為40重量%。反應混合物在70℃和氮氣氛下攪拌5小時以聚合，從而製備黏合劑樹脂1，其為丙烯酸系聚合物。經證實，如上述製備之共聚合物具有平均分子量為25,000及分散度為1.9。 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, epoxypropyl methacrylic acid, methyl Methacrylic acid and dicyclopentyl acrylic acid are added at a molar ratio of 20:20:40:20, where the solid content of the acrylic monomer is 40% by weight. The reaction mixture was stirred at 70° C. for 5 hours under a nitrogen atmosphere to polymerize, thereby preparing Binder Resin 1, which is an acrylic polymer. It was confirmed that the copolymer prepared as described above had an average molecular weight of 25,000 and a degree of dispersion of 1.9.

b)黏合劑樹脂2之製備 b) Preparation of binder resin 2

將丙二醇甲基醚乙酸酯(PGMEA)(200mL)和偶氮二異丁腈(AIBN)(1.0g)加入500mL的聚合反應器，且甲基丙烯酸、苯乙烯、甲基甲基丙烯酸和環己基甲基丙烯酸以40：20：20：20的莫耳比率加入，其中丙烯酸系單體的固體含量為40重量%。反應混合物在70℃和氮氣氛下攪拌5小時以聚合，從而合成共聚物。以100莫耳之整個單體的固體含量計，將N,N-二甲基苯胺(0.3g)和環氧丙基甲基丙烯酸以20的莫耳比率加入此反應器中，並在100℃攪拌10小時，從而製備黏合劑樹脂2，其為在其側鏈上具有丙烯酸系不飽和鍵的丙烯酸系聚合物。經證實，如上述製造之共聚物具有平均分子量為20,000及分散度為2.0。 Propylene glycol methyl ether acetate (PGMEA) (200 mL) and azobisisobutyronitrile (AIBN) (1.0 g) were added to a 500 mL polymerization reactor, and methacrylic acid, styrene, methylmethacrylic acid and cyclic Hexyl methacrylic acid was added at a molar ratio of 40:20:20:20, where the solid content of the acrylic monomer was 40% by weight. The reaction mixture was stirred at 70° C. for 5 hours under a nitrogen atmosphere to polymerize, thereby synthesizing a copolymer. Based on the solid content of 100 mol of the entire monomer, N,N-dimethylaniline (0.3 g) and epoxypropyl methacrylic acid were added to this reactor at a molar ratio of 20, and at 100 ℃ The mixture was stirred for 10 hours to prepare a binder resin 2 which is an acrylic polymer having an acrylic unsaturated bond on its side chain. It was confirmed that the copolymer manufactured as described above had an average molecular weight of 20,000 and a degree of dispersion of 2.0.

c)黏合劑樹脂3之製備 c) Preparation of binder resin 3

將丙二醇甲基醚乙酸酯(PGMEA)(200mL)和偶氮二異丁腈(AIBN)(1.0g)加入500mL的聚合反應器，且環氧丙基甲基丙烯酸、苯乙烯、甲基甲基丙烯酸和環己基甲基丙烯酸以40：20：20：20的莫耳比率加入，其中丙烯酸系單體的固體含量為40重量%。反應混合物在70℃和氮氣氛下攪拌5小時以聚合，從而合成共聚物。以100莫耳之整個單體的固體含量計，將N,N-二甲基苯胺(0.3g)和丙烯酸以20的莫耳比率加入此反應器中，並在100℃攪拌10小時，從而製備 黏合劑樹脂3，其為在其側鏈上具有丙烯酸系不飽和鍵的丙烯酸系聚合物。經證實，如上述製造之共聚物具有平均分子量為18,000及分散度為1.8。 Propylene glycol methyl ether acetate (PGMEA) (200 mL) and azobisisobutyronitrile (AIBN) (1.0 g) were added to a 500 mL polymerization reactor, and epoxypropyl methacrylic acid, styrene, methyl methyl Acrylic acid and cyclohexyl methacrylic acid were added at a molar ratio of 40:20:20:20, where the solid content of the acrylic monomer was 40% by weight. The reaction mixture was stirred at 70° C. for 5 hours under a nitrogen atmosphere to polymerize, thereby synthesizing a copolymer. Based on the solid content of the entire monomer of 100 moles, N,N-dimethylaniline (0.3g) and acrylic acid were added to this reactor at a mole ratio of 20, and stirred at 100°C for 10 hours to prepare The binder resin 3 is an acrylic polymer having an acrylic unsaturated bond on its side chain. It was confirmed that the copolymer manufactured as described above had an average molecular weight of 18,000 and a degree of dispersion of 1.8.

[實例54至實例88]可光聚合的組成物之製備 [Example 54 to Example 88] Preparation of photopolymerizable composition

根據下表1所示組分及含量，將黏合劑樹脂1至黏合劑樹脂3、光反應性化合物、本發明之光聚合起始劑和FC-430(購自3M公司的整平劑)作為添加劑依序加入配備有紫外線保護膜及攪拌器的反應混合槽中，並在室溫(23℃)下攪拌。然後，於其內加入丙二醇單甲基醚乙酸酯(PGMEA)作為溶劑，使得能製備具有整個含量為100重量%的組成物，從而製備可光聚合的組成物。 According to the components and contents shown in Table 1 below, binder resin 1 to binder resin 3, photoreactive compound, photopolymerization initiator of the present invention, and FC-430 (leveling agent purchased from 3M company) were used as The additives are sequentially added to the reaction mixing tank equipped with an ultraviolet protective film and a stirrer, and stirred at room temperature (23°C). Then, propylene glycol monomethyl ether acetate (PGMEA) is added as a solvent therein, so that a composition having the entire content of 100% by weight can be prepared, thereby preparing a photopolymerizable composition.

[實例89和實例91]黑色矩陣可光聚合的組成物之製備 [Example 89 and Example 91] Preparation of black matrix photopolymerizable composition

如下表1所示，將20重量%的黏合劑樹脂1、10重量%的二新戊四醇六丙烯酸酯、0.5重量%的光反應性化合物(實例7或實例26)、50重量%的碳黑(以固體含量為25重量%分散於PGMEA)、以及0.1重量%的FC-430(購自3M公司的整平劑)依序加入配備有紫外線保護膜及攪拌器的反應混合槽中，並在室溫下攪拌。然後，於其內加入PGMEA作為溶劑，使得製備具有整個含量為100重量%的組成物，從而製備黑 色矩陣可光聚合的組成物。 As shown in Table 1 below, 20% by weight of binder resin 1, 10% by weight of dipentaerythritol hexaacrylate, 0.5% by weight of photoreactive compound (Example 7 or Example 26), 50% by weight of carbon Black (dispersed in PGMEA at a solids content of 25% by weight), and 0.1% by weight of FC-430 (leveling agent purchased from 3M Company) are sequentially added to the reaction mixing tank equipped with an ultraviolet protective film and a stirrer, and Stir at room temperature. Then, PGMEA was added as a solvent therein to prepare a composition having the entire content of 100% by weight, thereby preparing black Color matrix photopolymerizable composition.

此外，經上述方法所製得之黑色矩陣可光聚合的組成物之評估係在玻璃基材上進行。測量該黑色矩陣可光聚合的組成物的性能，如敏感性、膜截留率(retention rate)、圖案穩定性、耐化學性、延展性等，且其評估結果顯示於下表2中。 In addition, the evaluation of the black matrix photopolymerizable composition prepared by the above method was performed on a glass substrate. The properties of the black matrix photopolymerizable composition were measured, such as sensitivity, film retention rate, pattern stability, chemical resistance, ductility, etc., and the evaluation results are shown in Table 2 below.

[實例90和實例92]紅色可光聚合的組成物之製備 [Example 90 and Example 92] Preparation of red photopolymerizable composition

如下表1所示，以與實例89或實例91相同方法製備紅色可光聚合的組成物，除了使用50重量%的具有固體含量為25重量%的顏料紅色177(P.R.177)分散溶液，而不是使用碳黑。 As shown in Table 1 below, a red photopolymerizable composition was prepared in the same manner as in Example 89 or Example 91, except that a 50% by weight dispersion solution of Pigment Red 177 (PR177) with a solid content of 25% by weight was used instead of Use carbon black.

Figure 105103739-A0202-12-0114-76
Figure 105103739-A0202-12-0114-76
Figure 105103739-A0202-12-0115-77
Figure 105103739-A0202-12-0115-77
Figure 105103739-A0202-12-0116-78
Figure 105103739-A0202-12-0116-78
Figure 105103739-A0202-12-0117-79
Figure 105103739-A0202-12-0117-79

[比較實例1]可光聚合的組成物之製備 [Comparative Example 1] Preparation of photopolymerizable composition

以與實例54相同方法製備可光聚合的組成物，除了使用下化學式B表示之光聚合起始劑，而不是使用實例1之化合物作為光聚合起始劑。 A photopolymerizable composition was prepared in the same manner as in Example 54 except that the photopolymerization initiator represented by the following Chemical Formula B was used instead of using the compound of Example 1 as the photopolymerization initiator.

Figure 105103739-A0202-12-0117-80
Figure 105103739-A0202-12-0117-80

[比較實例2]可光聚合的組成物之製備 [Comparative Example 2] Preparation of photopolymerizable composition

以與實例54相同方法製備可光聚合的組成物，除了使用實例1之3-(乙醯氧基亞胺基)-1-(6-硝基-9H-茀-3-基)丙烷-1-酮作為光聚合起始劑，而不是使用實例1之化合物。 A photopolymerizable composition was prepared in the same manner as in Example 54, except that 3-(ethoxyimidinyl)-1-(6-nitro-9H-fusel-3-yl)propane-1 of Example 1 was used -Ketone was used as a photopolymerization initiator instead of using the compound of Example 1.

[測試實例]可光聚合的組成物之評估 [Test example] Evaluation of photopolymerizable composition

根據實例54至實例92之可光聚合的組成物及比較實例1和比較實例2之評估係在玻璃基材上進行。測量該可光聚合的組成物的性能，如敏感性、膜截留率、圖案穩定性、耐化學性、延展性等，且其評估結果顯示於下表2中。 The evaluations of the photopolymerizable compositions according to Examples 54 to 92 and Comparative Examples 1 and 2 were performed on glass substrates. The properties of the photopolymerizable composition, such as sensitivity, film rejection, pattern stability, chemical resistance, ductility, etc. were measured, and the evaluation results are shown in Table 2 below.

1)敏感性 1) Sensitivity

將光阻劑旋塗到玻璃基板上並在100℃於加熱板上乾燥1分鐘，且經乾燥的光阻劑使用步進光罩(step mask)曝光，然後於0.04%的KOH水溶液中顯影。評估在其步進光罩圖案的厚度維持在80%的起始厚度時的暴露劑量作為敏感性。 The photoresist was spin-coated onto the 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 then developed in a 0.04% KOH aqueous solution. The sensitivity of the exposure dose when the thickness of its step mask pattern was maintained at 80% of the initial thickness was evaluated.

2)殘餘厚度比率 2) Residual thickness ratio

使用旋塗機將可光聚合的組成物塗布至基材上，並在100℃預烘烤1分鐘，且將經預烘烤的光阻劑在365奈米曝光，然後在230℃後烘烤20分鐘。然後，測量光阻劑膜在後烘烤之前及之後的厚度比率(%)。 Use a spin coater to apply the photopolymerizable composition to the substrate, and pre-bake at 100°C for 1 minute, and expose the pre-baked photoresist at 365 nm, then post-bake at 230°C 20 minutes. Then, the thickness ratio (%) of the photoresist film before and after post-baking was measured.

3)圖案穩定性 3) Pattern stability

將與光阻劑圖案形成的矽晶圓在孔圖案的垂直方向 上切割，並使用電子顯微鏡觀察該圖案的橫截面。當圖案的側壁相對於基材在55°或更大的角度被豎直且沒有觀察到膜厚度的減少時，則該可光聚合的組成物的圖案穩定性判定為「良好」，但若觀察到膜厚度的減少時，則圖案穩定性判定為「不佳(膜減)」。 Place the silicon wafer formed with the photoresist pattern in the vertical direction of the hole pattern Cut up and observe the cross section of the pattern using an electron microscope. When the side wall of the pattern is vertical at an angle of 55° or more with respect to the substrate and no reduction in film thickness is observed, the pattern stability of the photopolymerizable composition is judged to be "good", but if observed When the film thickness decreases, the pattern stability is judged to be "poor (film reduction).

4)耐化學性 4) Chemical resistance

使用旋塗機將可光聚合的組成物塗布到基材上，接著透過如預烘烤處理、後烘烤處理等的處理形成光阻膜。將所形成的光阻膜在40℃浸漬到剝除劑溶液10分鐘之後，觀察該光阻膜的透射率和厚度是否變化。當透射率和厚度的變化為2%或更低時，則耐化學性判定為「良好」，但當透射率和厚度的變化為超過2%時，則耐化學性判定為「不佳」。 The photopolymerizable composition is applied to the substrate using a spin coater, and then a photoresist film is formed through treatments such as pre-baking treatment and post-baking treatment. After the formed photoresist film was immersed in the stripper solution at 40° C. for 10 minutes, it was observed whether the transmittance and thickness of the photoresist film changed. When the change in transmittance and thickness is 2% or less, the chemical resistance is judged as "good", but when the change in transmittance and thickness is more than 2%, the chemical resistance is judged as "bad".

5)延展性 5) ductility

使用旋塗機將可光聚合的組成物塗布至基材上並在100℃預烘烤1分鐘之後，將經預烘烤的光阻劑在光阻劑的敏感性下曝光，然後於KOH水溶液中顯影，以形成圖案(20微米×20微米)。將所形成的圖案在230℃後烘烤20分鐘，從而交聯，並使用奈米壓痕器測量圖案的延展性。經奈米壓痕器所測量的結果，當以5克．力(5g．f)荷重的總變化量 為500奈米或更大時，則延展性判定為「良好」，但當總變化量為少於500奈米時，則延展性判定為「不佳」。 After applying the photopolymerizable composition onto the substrate using a spin coater and pre-baking at 100°C for 1 minute, the pre-baked photoresist is exposed to the sensitivity of the photoresist and then exposed to an aqueous solution of KOH Medium development to form a pattern (20 microns x 20 microns). The formed pattern was post-baked at 230° C. for 20 minutes to be cross-linked, and the ductility of the pattern was measured using a nano indenter. The result measured by the nano indenter should be 5 grams. Total change of force (5g.f) load When it is 500 nm or more, the ductility is judged as "good", but when the total change is less than 500 nm, the ductility is judged as "not good".

Figure 105103739-A0202-12-0120-81
Figure 105103739-A0202-12-0120-81
Figure 105103739-A0202-12-0121-82
Figure 105103739-A0202-12-0121-82

上表2證實，當使用本發明之肟酯化合物作為可光聚合的組成物的光聚合起始劑，即使是少量也能具有顯著優異的敏感性和優異的物理性質，如膜截留率、圖案穩定性、耐化學性、延展性等，從而可以最小化在曝光過程及後烘烤過程期間在薄膜電晶體液晶顯示器(TFT-LCD)製造過程中從光聚合起始劑所產生的逸氣作用，使得可以降低污染和最小化由於污染將生成的缺陷。 Table 2 above confirms that when the oxime ester compound of the present invention is used as a photopolymerization initiator of a photopolymerizable composition, even a small amount can have significantly excellent sensitivity and excellent physical properties, such as film rejection rate, pattern Stability, chemical resistance, ductility, etc., which can minimize the outgassing effect from the photopolymerization initiator during the manufacturing process of thin film transistor liquid crystal display (TFT-LCD) during the exposure process and the post-baking process , Making it possible to reduce pollution and minimize defects that will be generated due to pollution.

Figure 105103739-A0202-11-0003-1
Figure 105103739-A0202-11-0003-1

Claims (9)

一種肟酯化合物，係由以下化學式2至化學式4表示：
Figure 105103739-A0305-02-0125-1
Figure 105103739-A0305-02-0125-2
Figure 105103739-A0305-02-0125-3
 化學式2至化學式4中，R1至R5各自獨立為氫、鹵素、(C1-C20)烷基、(C6-C20)芳基、(C1-C20)烷氧基、(C6-C20)芳基(C1-C20)烷基、羥基(C1-C20)烷基、羥基(C1-C20)烷氧基(C1-C20)烷基、(C3-C20)環烷基或(C3-C20)環烷基(C1-C20)烷基；A為氫、鹵素、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、胺基、硝基、氰基或羥基；m為選自0至2的整數；及a及b為0或1的整數。 An oxime ester compound represented by the following Chemical Formula 2 to Chemical Formula 4:
Figure 105103739-A0305-02-0125-1
Figure 105103739-A0305-02-0125-2
Figure 105103739-A0305-02-0125-3
 In Chemical Formula 2 to Chemical Formula 4, R 1 to R 5 are each independently hydrogen, halogen, (C 1 -C 20 )alkyl, (C 6 -C 20 )aryl, (C 1 -C 20 )alkoxy, (C 6 -C 20 )aryl (C 1 -C 20 )alkyl, hydroxy (C 1 -C 20 )alkyl, hydroxy (C 1 -C 20 )alkoxy (C 1 -C 20 )alkyl , (C 3 -C 20 )cycloalkyl or (C 3 -C 20 )cycloalkyl (C 1 -C 20 )alkyl; A is hydrogen, halogen, (C 1 -C 20 )alkyl, (C 6 -C 20 )aryl, (C 6 -C 20 )aryl (C 1 -C 20 )alkyl, amine, nitro, cyano or hydroxy; m is an integer selected from 0 to 2; and a And b is an integer of 0 or 1. 如請求項1所記載之肟酯化合物，其中R1至R5各自獨立選自氫、溴、氯、碘、甲基、乙基、丙基、丁基、戊基、己基、苯基、萘基、聯苯基、聯三苯基、蒽基、茚基、菲基、甲氧基、乙氧基、丙氧基、丁氧基、苯甲基、羥基甲基、羥基乙基、羥基丙基、羥基丁基、羥基戊基、羥基己基、羥基甲氧基甲基、羥基甲氧基乙基、羥基甲氧基丙基、羥基甲氧基丁基、羥基乙氧基甲基、羥基乙氧基乙基、羥基乙氧基丙基、羥基乙氧基丁基、羥基乙氧基戊基、羥基乙氧基己基、環丙基、環戊基、環己基、環丙基甲基、環戊基甲基及環己基甲基。 The oxime ester compound according to claim 1, wherein R 1 to R 5 are each independently selected from hydrogen, bromine, chlorine, iodine, methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, naphthalene Group, biphenyl, triphenyl, anthracenyl, indenyl, phenanthrenyl, methoxy, ethoxy, propoxy, butoxy, benzyl, hydroxymethyl, hydroxyethyl, hydroxypropyl Group, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethyl Oxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl, hydroxyethoxyhexyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclo Amylmethyl and cyclohexylmethyl. 如請求項1所記載之肟酯化合物，其中A為選自氫、溴、氯、甲基、乙基、丙基、丁基、苯基、萘基、聯苯基、聯三苯基、蒽基、茚基、菲基、苯甲基、胺基、硝基、氰基及羥基。 The oxime ester compound according to claim 1, wherein A is selected from hydrogen, bromine, chlorine, methyl, ethyl, propyl, butyl, phenyl, naphthyl, biphenyl, biphenyl, anthracene Group, indenyl, phenanthrenyl, benzyl, amine, nitro, cyano and hydroxyl. 一種光聚合起始劑，包含請求項1所記載之肟酯化合物。 A photopolymerization initiator comprising the oxime ester compound described in claim 1. 一種可光聚合的組成物，包含請求項1所記載之肟酯化合物、黏合劑樹脂及光反應性化合物。 A photopolymerizable composition comprising the oxime ester compound described in claim 1, a binder resin, and a photoreactive compound. 如請求項5所記載之可光聚合的組成物，其中以100重量%之可光聚合的組成物計，該肟酯化合物的含量為0.01重量%至10重量%。 The photopolymerizable composition as described in claim 5, wherein the content of the oxime ester compound is 0.01% by weight to 10% by weight based on 100% by weight of the photopolymerizable composition. 如請求項5所記載之可光聚合的組成物，更包含該可光聚合的組成物中的著色劑。 The photopolymerizable composition as described in claim 5 further includes a coloring agent in the photopolymerizable composition. 一種模製物件，其包含請求項5或7所記載之可光聚合的組成物之固化產物。 A molded article comprising the cured product of the photopolymerizable composition described in claim 5 or 7. 一種顯示器裝置，其包含請求項8所記載之模製物件。 A display device including the molded object described in claim 8.
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