TW201213501A - Novel organic electroluminescent compounds and organic electroluminescent device using the same - Google Patents

Novel organic electroluminescent compounds and organic electroluminescent device using the same Download PDF

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TW201213501A
TW201213501A TW100126954A TW100126954A TW201213501A TW 201213501 A TW201213501 A TW 201213501A TW 100126954 A TW100126954 A TW 100126954A TW 100126954 A TW100126954 A TW 100126954A TW 201213501 A TW201213501 A TW 201213501A
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TW100126954A
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Soo-Yong Lee
Young-Jun Cho
Bong-Ok Kim
Sung-Min Kim
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Rohm & Haas Elect Mat
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  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Provided are novel organic electroluminescent compounds and an organic electroluminescent device using the same. Because the organic electroluminescent device using the organic electroluminescent compound as a hole transport material or a hole injection material exhibits good luminous efficiency and excellent lifetime properties, it is used to manufacture OLED devices having superior operating lifetime and consuming less power due to improved power efficiency.

Description

201213501 . 六、發明說明： 【發明所屬之技術領域】 本發明係關於新穎有機電場發光化合物及包含該化合 物之有機電場發光裝置’且更特別地，本發明係關於適合 用作為電洞傳輸材料或電洞注入材料之新穎有機電場發光 化合物及使用該化合物之有機電場發光裝置。 【先前技術】 目前廣泛可得的液晶顯示器（LCD)為非發光型 (non-emissive)顯示器裝置，其具有低功率消耗且重量輕， 但卻有複雜的操作系統及不令人滿意的性質，包含反應時 間與對比。因此，最近已對號稱下一代平面顯示器而受到 極大注目之有機電場發光裝置進行積極地研究。 在顯不器裝置中，電場發光（EL)裝置有利於作為自身 發光顯裝置’其提供有寬角視野、較高對比及快速反 μ速率在1987年’伊斯門柯達（Eastman K〇dak)首先發 展出使用低分子量芳香族二胺及⑮錯合物以形成電場發光 層之有 置[A_. Phys. Lett. 51，913，1987]。 、有機EL裂置之發光機制為，將電荷注入至形成於電 子入電極（陰極）與電洞注入電極（陽極）之間的有機層， 而形成電子〜電洞配對，然後衰退而發光。該裝置可於可撓 ，透j基板（如塑膠）上形成’且與電漿顯示面板或無機EL ^不盗相比’該裳置可於較低電壓（1G伏特⑺或更低）下 木作1可呈現相對少的功率消耗及較優異顏色。 有機EL裝置之有機材料主要分為發光材料及電荷產 3 95299 201213501 先材抖係與所發射之顏色及發光效率直接相 、 些要未包含於固相之高螢光量子產率、電 U同之呵移動性、於真空沉積過程中之低分解、以及 形成均勻安定的薄膜。 同時’電洞>主入及傳輸材料包含酞青銅（CuPc)、NpB、 TPD'MTDATA(4’4’，4” -參（3-曱基苯基苯基胺基）三苯基 胺）等。於電洞注入層及電洞傳輸層中包含有此等材料之裝 置因為降低的效率及壽命而存在問題。這是因為，當於高 電流操作該有機EL裝置時，於陽極與該電洞注入層之間出 現熱應力，且此熱應力可造成該裝置的壽命性質驟降。再 者’由於用於電洞注入層之該有機材料具有非常高的電洞 移動性，因此打破該電洞_電子電荷平衡，並因此減少量子 產率（燭光（cd)/安培（A))。 為了增加該有機EL裝置的耐用性（durabi 1 i ty)，已報 導使用具有良好薄膜安定性之化合物與具有高非結晶性之 化合物呈現咼薄膜安定性。就這點來說，玻璃轉移溫度（Tg) 係用於作為非結晶性的指數。傳統MTDATA之Tg為76。〇 , 故不被認為具有非結晶性。此等材料在有機EL裝置之耐用 性及基於電及傳輸性質之發光效率方面不能令人滿 意。 【發明内容】 技術問題 鑑此，本發明已記取相關技術領域所遭遇的問題，且 本發明之目的係提供有機EL化合物，該化合物之骨架提供 95299 4 201213501 與傳統電洞注入或電洞傳輸材料相比較高之發光效率及裝 置壽命；以及使用該新穎有機EL化合物作為電洞注入層或 電洞傳輸層之有機EL裝置。 技術解決方案 本發明係提供下列化學式1表示之有機EL化合物、及 包含該化合物之有機EL裝置。本發明之有機EL化合物係 包含於該有機EL裝置之電洞注入層或電洞傳輸層中，因此 其係降低該裝置之操作電壓並增加其發光效率。 在一態樣中，本發明係提供下列化學式1表示之有機 EL化合物。 化學式1201213501 . 6. Description of the Invention: [Technical Field] The present invention relates to novel organic electroluminescent compounds and organic electroluminescent devices comprising the same, and more particularly, the present invention relates to suitable use as a hole transport material or A novel organic electroluminescent compound for injecting a material into a material and an organic electric field illuminating device using the same. [Prior Art] A currently widely available liquid crystal display (LCD) is a non-emissive display device which has low power consumption and is light in weight, but has a complicated operating system and unsatisfactory properties. Contains reaction time and comparison. Therefore, an organic electric field light-emitting device which has been attracting attention as a next-generation flat panel display has been actively studied recently. In the display device, an electric field illumination (EL) device is advantageous as a self-luminous display device which provides a wide-angle field of view, a high contrast and a fast inverse μ rate in 1987 'Eastman K〇dak' First, the use of low molecular weight aromatic diamines and 15 complexes to form an electroluminescent layer has been developed [A_. Phys. Lett. 51, 913, 1987]. The luminescence mechanism of the organic EL cleavage is to inject a charge into an organic layer formed between the electron-in electrode (cathode) and the hole injection electrode (anode) to form an electron-hole pairing, and then decay to emit light. The device can be formed on a flexible, transparent substrate (such as plastic) and can be placed at a lower voltage (1G volt (7) or lower) than a plasma display panel or inorganic EL. A 1 can exhibit relatively little power consumption and a superior color. The organic materials of organic EL devices are mainly divided into luminescent materials and charge generations. 3 95299 201213501 The materials of the first material are directly related to the emitted color and luminous efficiency, and the high fluorescence quantum yields of the solid phase are not included in the solid phase. Mobility, low decomposition during vacuum deposition, and formation of a uniform film. At the same time, 'hole> primary and transport materials include beryllium bronze (CuPc), NpB, TPD'MTDATA (4'4', 4" - ginseng (3-mercaptophenylphenylamino) triphenylamine) Etc. Devices containing such materials in the hole injection layer and the hole transport layer have problems due to reduced efficiency and longevity because, when operating the organic EL device at high current, the anode and the electricity Thermal stress occurs between the hole injection layers, and this thermal stress can cause a sudden drop in the life properties of the device. Furthermore, since the organic material used for the hole injection layer has a very high hole mobility, the electricity is broken. Hole_Electronic charge balance, and thus reduced quantum yield (candle light (cd) / ampere (A)). In order to increase the durability of the organic EL device, it has been reported to use a compound having good film stability. The film is stable with a compound having high non-crystallinity. In this regard, the glass transition temperature (Tg) is used as an index of non-crystallinity. The Tg of the conventional MTDATA is 76. Therefore, it is not considered to have Non-crystalline. These materials are in organic EL The durability and the luminous efficiency based on electrical and transmission properties are unsatisfactory. SUMMARY OF THE INVENTION Technical Problem Accordingly, the present invention has been made to solve the problems encountered in the related art, and an object of the present invention is to provide an organic EL compound. The skeleton of the compound provides 95299 4 201213501 with higher luminous efficiency and device lifetime than conventional hole injection or hole transport materials; and an organic EL device using the novel organic EL compound as a hole injection layer or a hole transport layer. Technical Solution The present invention provides an organic EL compound represented by the following Chemical Formula 1, and an organic EL device comprising the same. The organic EL compound of the present invention is contained in a hole injection layer or a hole transport layer of the organic EL device. Therefore, it lowers the operating voltage of the device and increases its luminous efficiency. In one aspect, the present invention provides an organic EL compound represented by the following Chemical Formula 1.

在化學式1中，X表示-0---S---C(RnR12)-或 _Si (R13R14)-，其中_ ’ Ru至Rh係獨立表示.氫、沉、鹵素、 經取代或未經取代之（C1-C30)烷基、經取代或未經取代之 (C6-C30)芳基、經取代或未經取代之（C3-C30)雜芳基、經 取代或未經取代之5至7員雜環烷基、或經取代或未經取 代之（C3-C30)環烷基，或Rn至Ru係鏈結至相鄰取代基以 形成環； 5 95299 201213501 至侧立表錢H素、經取代或未經取代 之(a-c3〇)烷基、經取代或未經取代之(c6_⑽芳基、經 取代或未經取代之⑽基、___取^ (C3-C3G)魏基、經取代或未絲代之5 ^ 了貞雜環燒武、 經取代或未餘代之〇：6_G3㈣基（叫3Q)絲、盘一^固 或多個祕基稠合之經取代或未經取代之（心⑽）芳基、 與-個或辣經取代或未經取代之芳香環稠合之5至7員 雜環烧基、或與-個或多個經取代或未經取代之芳香環祠 合之〇：3-_環絲、經取代或未經取代之（π_⑽錢 基、氰基、石肖基或财，其中當1至1係以複數存在者， 則它們可互相鏈結以形成環狀結構； r5及ΐΜ絲示氫、m經取代或未經取代之 (C1-C30)烷基、經取代或未經取代之（C6_C3〇)芳基、經取 代或未經取狀⑽-⑽）雜綠、核取代絲經取代之 5員至7員雜環絲，< &及Re係鏈結至相鄰取代基 成環；In Chemical Formula 1, X represents -0---S---C(RnR12)- or _Si(R13R14)-, wherein _ 'Ru to Rh is independently represented. Hydrogen, sink, halogen, substituted or unsubstituted Substituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30)heteroaryl, substituted or unsubstituted 5 to a 7-membered heterocycloalkyl group, or a substituted or unsubstituted (C3-C30) cycloalkyl group, or a Rn-to-Ru chain to an adjacent substituent to form a ring; 5 95299 201213501 To the side of the table Substituted or unsubstituted (a-c3〇)alkyl, substituted or unsubstituted (c6_(10) aryl, substituted or unsubstituted (10) group, ___ taken (C3-C3G) Wei group Substituted or unsubstituted 5 ^ 贞 贞 贞 、, substituted or unrepresented 〇: 6_G3 (tetra) ( (called 3Q) silk, disk Substituted (heart (10)) aryl, 5 to 7 membered heterocycloalkyl fused to a sulphur-substituted or unsubstituted aromatic ring, or substituted with one or more substituted or unsubstituted Aromatic ring entanglement: 3-_cyclofilament, substituted or unsubstituted (π_(10) Money base, cyano group, stone succinyl or sylvanic, wherein when 1 to 1 are present in plural, they may be linked to each other to form a cyclic structure; r5 and fluorene are hydrogen, m is substituted or unsubstituted (C1) -C30) an alkyl group, a substituted or unsubstituted (C6_C3〇) aryl group, a substituted or unsubstituted (10)-(10)) heterochloro, a nuclear substituted silk substituted 5 to 7 membered heterocyclic ring, <;&&; and Re-links to adjacent substituents to form a ring;

Li及b係獨立表示化學鍵、經取代或未經取代之 (C6-C30)伸芳基、或經取代或未經取代之（(：3_⑽）伸雜芳 基，排除其中Li及L2皆為化學鍵之例；Li and b are independently represented by a chemical bond, a substituted or unsubstituted (C6-C30) extended aryl group, or a substituted or unsubstituted ((:3_(10)) extended heteroaryl group, excluding that both Li and L2 are chemical bonds Example

Ar係表示經取代或未經取代之（C6-C30)芳基、除了咔 唑以外之經取代或未經取代之（C3_C3〇)雜芳基、經取代或 未經取代之5至7員雜環烷基、與一個或多個環烷基稠合 之經取代或未經取代之（C6_C3〇)芳基、與一個或多個經取 代或未經取代之芳香環稠合之經取代或未經取代之 6 95299 201213501 • (C3-C30)雜芳基、與一個或多個經取代或未經取代之芳香 環稍合之5至7員雜環烧基’或者Ar係經由具有或不耳有 • 稠合環之（C3-C30)伸烷基或（C3-C30)伸烯基鏈結至相鄰取 代基以形成脂環族環及單環或多環之芳香環； a至d係獨立表示〇至4的整數，其中，當3至（^為 -2或更大的整數時，R!、L、R3及L係互相為相同或不同， 且Ri、R2、R3及R4係鍵結至相鄰取代基以形成環；以及 談雜環燒基及雜芳基含有一個或多個選自B、n、〇、S、 P(=0)、Si及P之雜原子。 進一步取代於匕至R4、r5及r6、心至Ri4、Ll、[2及 Ar之取代基係獨立表示一個或多個選自下列者：氘、鹵素、 經鹵素取代或未經取代之（C1_C3〇)烷基、（C6_C3〇)芳基、 經（C6-C30)芳基取代或未經取代之（C3_C3〇)雜芳基、5至1 員雜環烷基、與一個或多個芳香環稠合之5至7員雜環烷 基、（C3-C30)環烷基、與一個或多個芳香環稠合之（C6_c3^ 環烷基、R2,R22R23Si-、（C2-C30)烯基、（C2-C30)炔基、氰 基、咔唾基、NR24R25、BR26R27、PR28R29、p(=〇)R3qR3i、（C6_C3〇) 芳基（C1-C30)院基、（n-C30)烧基（C6_C3〇)芳基、、 R33〇— ιωχ=0)-' R35C(=0)0一、羧基、硝基及羥基，其令 R21至R33係獨立表示氫、I、_素、經取代或未經取代之 (C1-C3G)炫基、經取代或未經取代之（C6_⑽）芳基、經取 代或未A取代之（C3-C30)雜芳基、或經取代或未經取代之 5至7員雜環絲，或者心至^係經由具有或不具有祠 合環之經取代或未經取代之（C3-C30)伸燒基或經取代或未 95299 7 201213501 經取代之⑹-⑽）伸縣鏈結至相鄰取代基以形成脂環族 環及單環或多環之芳香環，該形成的脂賴環及單環或多 環之芳香環的碳原子可經一個或多個選自氮、氧、及硫之 雜原子取代及r34及]^録示（e卜⑽）烧基、（c卜⑽ 烷氧基、（C6-C30)芳基或（C6-C30)芳氧基。 【實施方式】 於本發明中’、、烧基，，、及含有1基β部份之其他取 代基係包含直鏈及分支鏈兩者。於本發明中，、、環烧基，，係 包含單環烴及多環烴，例如經取代或未經取代之金剛烷基 或經取代或未經取代之（C7-C30)雙環烷基。於本發明中， 芳基意指自芳香烴去除一個氫原子後所得之有機基團， 且可包含4至7員，尤指5員或6員，之單環或稠合環， 亦包含複數個藉由單鍵鏈結之芳基。其具體實例包含，但 不限於：苯基、萘基、聯苯基、蒽基、茚基、苐基、菲基、 聯伸三苯基（triphenylenyl)、芘基、茈基、蒯基 (chrysenyl)、稠四苯基（naphthacenyl)、丙二烯合第基 (于111〇『3111;1^叩1)等。該萘基係包含1-萘基及2-萘基，該 蒽基係包括1-蒽基、2-蒽基及9-蒽基，以及該苐基係包括 1_苐基、2_第基、3*·第基、4_苐基及9_.苐基。於本發明中， '"雜芳基〃意指含有作為芳香環骨架原子之選自b、n、o、 S、P〇〇)、Si及Se的1至4個雜原子，以及作為剩餘芳 香環骨架原子之碳原子之芳基，且係以5員或6員單環雜 芳基及與一個或多個苯環縮合之多環雜芳基（其可呈部分 飽和）例示之。該雜芳基包含二價芳基，其中，該環中之雜 8 95299 201213501 • 原子可經氧化或四級化（quaternized)以形成諸如氣化 物或四級鹽。其具體實例包含，但不限於：單環雜芳臭 諸如吱喃基、嗟吩基、吼《各基、咪嗤基、吼唾基、嗟β坐義 -噻二唑基、異噻唑基、異噚唑基、噚唑基、噚二唑基、 . 畊基、四畊基' 三唑基、四唑基、呋咕基、吡啶基、η比啡 - 基、嘧啶基、嗒啡基等；多環雜芳基，諸如苯并呋喃基、 本并°塞吩基、異苯并吱喃基、苯并咪α坐基、苯并售嗅展 本并異°塞β坐基、苯并異曙嗤基、苯并曙嗤基、異π弓丨π朵義、 吲哚基、吲唑基、苯并噻二唑基、喹啉基、異喹琳基、咖 啉基、喹唑啉基、喹哄基、喹噚啉基、咔唑基、啡啶基、 本并一卩亏呢基（benzodioxoly 1 )、萘咬基、二苯并。夫喃茂 二苯并11 塞吩基等；其Ν-氧化物（例如》比咬基Ν-氧化物、嗦 啉基Ν-氧化物）；其四級鹽等。 於本發明中，（C1-C30)烷基或（C6-C30)芳基（C1—C3〇) 烷基〃之烷基部份係包含（C1-C20)烷基，更具體為（C1—Cl〇) 烷基。該、（C6-C30)芳基及（C6-C30)芳基（C1-C30)烷基" 之芳基部份係包含（C6-C20)芳基’更具體為（C6-C12)芳基。 又，、、（C3-C30)雜芳基係包含（C3-C20)雜芳基，更具體為 (C3-C12)雜芳基，以及"（C3-C30)環烷基〃係包含（C3_C2〇) 環烧基’更具體為（C3-C7)環院基。又，、、（C3~C30)伸烧基 或伸烯基〃係包含（C3-C20)伸烷基或伸烯基，更具體為 (C3-C10)伸烷基或伸烯基。 在本文所用之術語、、經取代或未經取代〃中之'經取 代夕意指未經取代之取代基進一步經取代。 95299 9 201213501 再者，本發明之有機EL化合物係選自下列化學式2 至5表示之化合物： 化學式2The Ar system represents a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (C3_C3〇) heteroaryl group other than a carbazole, a substituted or unsubstituted 5 to 7 member hetero a cycloalkyl group, a substituted or unsubstituted (C6_C3 fluorene) aryl group fused to one or more cycloalkyl groups, substituted or unfused with one or more substituted or unsubstituted aromatic rings Substituted 6 95299 201213501 • (C3-C30)heteroaryl, 5 to 7 membered heterocyclic alkyl group or Ar system slightly coupled with one or more substituted or unsubstituted aromatic rings via or without ear Having a fused ring (C3-C30) alkyl or (C3-C30) an alkenyl chain to an adjacent substituent to form an alicyclic ring and a monocyclic or polycyclic aromatic ring; a to d Independently represents an integer of 〇4, wherein, when 3 to (^ is an integer of -2 or more, R!, L, R3, and L are the same or different from each other, and Ri, R2, R3, and R4 are key The substituents are bonded to adjacent substituents to form a ring; and the heterocycloalkyl and heteroaryl groups contain one or more heteroatoms selected from the group consisting of B, n, fluorene, S, P(=0), Si, and P. Further substitution Yu Yu to R4, r5 The substituents of r6, heart to Ri4, L1, [2 and Ar independently represent one or more selected from the group consisting of hydrazine, halogen, halogen-substituted or unsubstituted (C1_C3〇)alkyl, (C6_C3〇). An aryl group, a (C6-C30) aryl-substituted or unsubstituted (C3_C3〇)heteroaryl group, a 5- to 1-membered heterocycloalkyl group, a 5- to 7-membered heterocyclic ring fused to one or more aromatic rings An alkyl group, a (C3-C30) cycloalkyl group, fused to one or more aromatic rings (C6_c3^cycloalkyl, R2, R22R23Si-, (C2-C30)alkenyl, (C2-C30) alkynyl, Cyano, oxime, NR24R25, BR26R27, PR28R29, p(=〇)R3qR3i, (C6_C3〇) aryl (C1-C30), (n-C30) alkyl (C6_C3〇) aryl, R33 〇— ιωχ=0)-' R35C(=0)0, carboxy, nitro and hydroxy, which make R21 to R33 independently represent hydrogen, I, _, substituted or unsubstituted (C1-C3G) Hyunyl, substituted or unsubstituted (C6_(10)) aryl, substituted or unsubstituted (C3-C30)heteroaryl, or substituted or unsubstituted 5 to 7 membered heterocyclic, or heart To be substituted or unsubstituted with or without a chelating ring ( C3-C30) extended or substituted or not 95299 7 201213501 substituted (6)-(10)) extension of the county to adjacent substituents to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, the formation of The carbon atoms of the aliphatic lanthanide ring and the monocyclic or polycyclic aromatic ring may be substituted by one or more hetero atoms selected from nitrogen, oxygen, and sulfur, and r34 and ^^ are recorded (ebu(10)), (c (10) alkoxy, (C6-C30) aryl or (C6-C30) aryloxy. [Embodiment] In the present invention, the substituents, the alkyl group, and the other substituent groups containing the 1-based β moiety include both a straight chain and a branched chain. In the present invention, a cycloalkyl group is a monocyclic hydrocarbon and a polycyclic hydrocarbon such as a substituted or unsubstituted adamantyl group or a substituted or unsubstituted (C7-C30) bicycloalkyl group. In the present invention, aryl means an organic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and may comprise 4 to 7 members, especially 5 or 6 members, a monocyclic or fused ring, and also includes plural An aryl group linked by a single bond. Specific examples thereof include, but are not limited to, phenyl, naphthyl, biphenyl, anthracenyl, fluorenyl, fluorenyl, phenanthryl, triphenylenyl, fluorenyl, fluorenyl, chrysenyl , thick tetraphenyl (naphthacenyl), propadiene diradyl (in 111 〇 "3111; 1 ^ 叩 1) and so on. The naphthyl group comprises 1-naphthyl and 2-naphthyl, and the anthracenyl group includes a 1-fluorenyl group, a 2-fluorenyl group and a 9-fluorenyl group, and the anthracene group includes a 1 -fluorenyl group and a 2 -diyl group. , 3*·diyl, 4_mercapto and 9_. fluorenyl. In the present invention, '"heteroaryl" means 1 to 4 hetero atoms selected from the group consisting of b, n, o, S, P), Si and Se as an aromatic ring skeleton atom, and as a remainder The aryl group of the carbon atom of the aromatic ring skeleton atom is exemplified by a 5- or 6-membered monocyclic heteroaryl group and a polycyclic heteroaryl group condensed with one or more benzene rings, which may be partially saturated. The heteroaryl group comprises a divalent aryl group wherein the heterocycle in the ring is 8 95299 201213501 • The atom may be oxidized or quaternized to form, for example, a gasification or a quaternary salt. Specific examples thereof include, but are not limited to, a monocyclic heteroaromatic odor such as a fluorenyl group, a fluorenyl group, a fluorene group, a mercapto group, a hydrazino group, a hydrazone group, a thiazolidine group, an isothiazolyl group, Isoxazolyl, oxazolyl, oxadiazolyl, . cultivating, tetra-negative 'triazolyl, tetrazolyl, furazolyl, pyridyl, η-pyridyl-yl, pyrimidinyl, morphine, etc. Polycyclic heteroaryl, such as benzofuranyl, exemplified, benzophenanyl, isobenzopyranyl, benzimidazo, benzophenone, and snail Isoindolyl, benzofluorenyl, iso-π-丨 丨 π, fluorenyl, carbazolyl, benzothiadiazolyl, quinolyl, isoquinolinyl, morpholinyl, quinazoline Base, quinacridyl, quinoxalinyl, oxazolyl, phenanthryl, benzodioxoly 1, naphthalene, dibenzo. A benzoanyl group such as a benzophenone group; a sulfonium-oxide (for example, a bismuth-oxide, a porphyrin quinone-oxide); a quaternary salt thereof. In the present invention, the alkyl moiety of the (C1-C30)alkyl or (C6-C30)aryl (C1-C3〇)alkylhydrazine comprises (C1-C20)alkyl, more specifically (C1- Cl〇) alkyl. The (C6-C30) aryl group and the (C6-C30) aryl (C1-C30) alkyl group have an aryl group containing (C6-C20) aryl group, more specifically (C6-C12) aryl base. Further, the (C3-C30)heteroaryl group contains a (C3-C20)heteroaryl group, more specifically a (C3-C12)heteroaryl group, and a "(C3-C30)cycloalkylfluorene system ( C3_C2〇) The cycloalkyl group is more specifically a (C3-C7) ring-based base. Further, the (C3 to C30) alkylene group or the extended alkenyl group contains (C3-C20) an alkyl group or an alkenyl group, more specifically a (C3-C10) alkyl group or an alkenyl group. As used herein, the term ', substituted or unsubstituted oxime', is taken to mean that the unsubstituted substituent is further substituted. 95299 9 201213501 Furthermore, the organic EL compound of the present invention is selected from the compounds represented by the following Chemical Formulas 2 to 5: Chemical Formula 2

化學式3 «5 R.Chemical formula 3 «5 R.

化學式4Chemical formula 4

10 95299 201213501 . 化學式510 95299 201213501 . Chemical Formula 5

mDmD

在化學式2至5中，X、R〗至R4、R5及R6、L·、L2、Ar 及a至d之定義係與化學式1中定義者相同。 更具體地，Ar係選自下列結構者，但其並不限於此。In Chemical Formulas 2 to 5, the definitions of X, R to R4, R5 and R6, L·, L2, Ar and a to d are the same as those defined in Chemical Formula 1. More specifically, the Ar system is selected from the following structures, but it is not limited thereto.

11 95299 20121350111 95299 201213501

更具體地，本發明之有機EL化合物係藉由下列化合物 例示之，但本發明並不限於此。 12 95299 201213501More specifically, the organic EL compound of the present invention is exemplified by the following compounds, but the present invention is not limited thereto. 12 95299 201213501

95299 13 20121350195299 13 201213501

14 95299 20121350114 95299 201213501

15 95299 20121350115 95299 201213501

16 95299 20121350116 95299 201213501

本發明之有機EL化合物可藉由，例如下示方案1來製 備，但其並不限於此。 方案1The organic EL compound of the present invention can be produced, for example, by the following Scheme 1, but it is not limited thereto. plan 1

[在方案 1 中，X、Ri 至 R4、Rs 及 Re、Li、L2、Ar 及 a 至 d 之定義係與化學式1中定義者相同。] 此外，本發明係提供有機EL裝置，其中本發明之有機 E L化合物係用作為電洞注入材料或電洞傳輸材料。 17 95299 201213501 本發明之有機EL裝置包括第一電極；第二電極；以及 一層或多層插置於該第一電極與該第二電極間之有機層， 其中，該有機層包括一種或多種化學式1表示之有機EL 化合物。 本發明之有機EL裝置包含化學式1表示之有機EL化 合物，且可進一步包含一種或多種選自芳基胺系化合物及 苯乙烯基胺系化合物之化合物，且該芳基胺系化合物或苯 乙烯基胺系化合物之具體實例係揭露於韓國專利申請案第 10-2008-0060393號中第&lt;212〉至&lt;224〉段，但其並不限於 此。 在本發明之有機EL裝置中，該有機層除了包括化學 式1表示之有機EL化合物之外，可進一步包括一種或多種 選自下列之金屬：元素週期表之第1族、第2族、第4周 期與第5周期之過渡金屬、鑭系金屬及d-過渡元素之有機 金屬；或錯合物化合物。該有機層亦可包括電場發光層及 電荷產生層。 本發明可實現具有獨立發光模式之像素結構的有機EL 裝置；其中，該有機EL裝置包含本發明之化學式1表示之 有機EL化合物作為次像素；以及一種或多種包括選自11·、 Pt、Pd、Rh、Re、Os、Tl、Pb、Bi、In、Sn、Sb、Te、Au 及Ag之一種或多種金屬化合物之次像素，其係同時經平行 圖案化。 再者，該有機層除了包含有機EL化合物之外，可復 包含一層或多層發射紅光、綠光或藍光之有機電場發光 18 95299 201213501 層’以製造發射白光之有機EL裝置。該發射紅光、綠光或 藍光之化合物係例示於韓國專利申請案第 10-2008-0123276 號、第 10_2〇〇8_〇1〇76〇6 號及第 10-2008-0118428號，但其並不限於此。 在本發明之有機EL裝置中，可將一層（後文中稱為'、表 面層）選自硫屬化合物（chaicogenide)層、金屬鹵化物層 及金屬氧化物層之層體設置於該電極對之至少一個電極的 内表面上。更具體而言，可將矽或鋁之硫屬化合物（包括氧 化物）層设置於電場發光介質層之陽極表面上，並可將金屬 齒化物層或金屬氧化物層設置於電場發光介質層之陰極表 面上，藉此得到操作安定性。該硫屬化合物可包括例如： Si〇x(l^x^2)、Α10χ(1$χ$15)、Si⑽、⑽腿等。該 金屬鹵化物可包含例如：LiF、_、抓、稀土金屬氣化 物等。該金屬氧化物可包含例如：Cs2〇、Li2〇、Mg〇、、 BaO、CaO 等。 在本發明之有機EL裝置中，較佳亦可將電子傳輸化 合物與還原性雜劑之混合區域或電洞傳輸化合物與氧化 性摻雜劑之混合區域設置於前述所製造之電極對的至少一 者的表面上。在這種情況下，因為電子傳輸化合物被還原 j陰離子，電子自混合區域注人與傳輸至電場發光介質變 得更容易。此外，因為電洞傳輸化合物被氧化成陽離子， 電洞自混合區域注入與傳輪至電場發光介質變得更容易。 較佳的氡化性摻雜劑係包含各種路易士酸及接受者化合物 (acceptor compound)。較佳的還原性摻雜劑係包含鹼金 19 95299 201213501 屬、驗金屬化合物、驗土金屬、稀土金屬及其混合物。再 者，可藉由摻雜還原性摻雜劑層作為電荷產生層來製造具 有兩層或更多層電場發光層之發射白光之有機EL裝置。 有益效果 根據本發明，可使用有機EL化合物作為電洞傳輸材 料或電洞注入材料，可使製得之有機EL裝置具有良好的發 光效率及優異的材料壽命性質，因此可使用該化合物來製 造具有極高操作壽命之0LED裝置。 最佳模式 本發明將進一步關於本發明之有機EL化合物、該化 合物之製備方法、以及使用該化合物所製造之裝置之電場 發光性質而說明。然而，下列實施例僅提供用於說明用， 而非意欲限制本發明之範疇。 [製備例1]化合物3之製備[In Scheme 1, the definitions of X, Ri to R4, Rs, and Re, Li, L2, Ar, and a to d are the same as those defined in Chemical Formula 1. Further, the present invention provides an organic EL device in which the organic EL compound of the present invention is used as a hole injecting material or a hole transporting material. 17 95299 201213501 The organic EL device of the present invention comprises a first electrode; a second electrode; and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more chemical formulas An organic EL compound represented. The organic EL device of the present invention comprises the organic EL compound represented by Chemical Formula 1, and may further comprise one or more compounds selected from the group consisting of arylamine-based compounds and styrylamine-based compounds, and the arylamine-based compound or styryl group A specific example of the amine compound is disclosed in paragraphs <212> to <224> of Korean Patent Application No. 10-2008-0060393, but it is not limited thereto. In the organic EL device of the present invention, the organic layer may further comprise, in addition to the organic EL compound represented by Chemical Formula 1, one or more metals selected from the group consisting of Group 1, Periodic Table 2, Group 4 of the Periodic Table of the Elements. An organometallic with a transition metal of the cycle and the fifth cycle, a lanthanide metal and a d-transition element; or a complex compound. The organic layer may also include an electric field luminescent layer and a charge generating layer. The present invention can realize an organic EL device having a pixel structure of an independent light-emitting mode; wherein the organic EL device includes the organic EL compound represented by Chemical Formula 1 of the present invention as a sub-pixel; and one or more includes a selected from the group consisting of 11·, Pt, and Pd Sub-pixels of one or more metal compounds of Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag, which are simultaneously parallel patterned. Further, the organic layer may comprise, in addition to the organic EL compound, one or more layers of organic electric field light emitting red, green or blue light to produce an organic EL device that emits white light. The compound which emits red light, green light or blue light is exemplified in Korean Patent Application No. 10-2008-0123276, No. 10_2〇〇8_〇1〇76〇6 and No. 10-2008-0118428, but Not limited to this. In the organic EL device of the present invention, a layer (hereinafter referred to as 'the surface layer') selected from the group consisting of a chaicogenide layer, a metal halide layer and a metal oxide layer may be disposed on the electrode pair. On the inner surface of at least one of the electrodes. More specifically, a layer of chalcogenide (including oxide) of bismuth or aluminum may be disposed on the anode surface of the electric field luminescent medium layer, and a metal dentide layer or a metal oxide layer may be disposed on the electric field luminescent medium layer. On the surface of the cathode, operational stability is thereby obtained. The chalcogenide compound may include, for example, Si〇x (l^x^2), Α10χ (1$χ$15), Si(10), (10) legs, and the like. The metal halide may contain, for example, LiF, _, scratch, rare earth metal gasification, and the like. The metal oxide may include, for example, Cs2〇, Li2〇, Mg〇, BaO, CaO, or the like. In the organic EL device of the present invention, preferably, a mixed region of the electron transporting compound and the reducing dopant or a mixed region of the hole transporting compound and the oxidizing dopant may be provided in at least one of the electrode pairs manufactured as described above. On the surface. In this case, since the electron transporting compound is reduced by the j anion, it becomes easier for the electrons to be injected from the mixed region and transmitted to the electric field illuminating medium. In addition, since the hole transporting compound is oxidized to a cation, it becomes easier for the hole to be injected into the transfer region from the mixing region to the electric field illuminating medium. Preferred deuterated dopants include various Lewis acids and acceptor compounds. Preferred reducing dopants include the alkali metal 19 95299 201213501 genus, metal compound, soil test metal, rare earth metal, and mixtures thereof. Further, an organic EL device for emitting white light having two or more layers of an electroluminescent layer can be produced by doping a reducing dopant layer as a charge generating layer. Advantageous Effects According to the present invention, an organic EL compound can be used as a hole transporting material or a hole injecting material, and the obtained organic EL device can have good luminous efficiency and excellent material life property, and thus can be produced by using the compound. Very high operating life OLED device. BEST MODE The present invention will be further described with respect to the organic EL compound of the present invention, the method for producing the compound, and the electric field luminescent properties of the device produced using the compound. However, the following examples are provided for illustrative purposes only and are not intended to limit the scope of the invention. [Preparation Example 1] Preparation of Compound 3

化合物1-1之製備 在100°〇加熱下攪拌30克4)4-溴聯苯（128.7 111111〇1)、 27 毫升（mL)氨水（772 mmol)、2. 45 克 Cul(12. 87 mmol)、 12. 9 毫升乙酿丙酮（128· 7 mmol)、83. 9 克 Cs2C〇3( 257. 4 20 95299 201213501 . mmol)及1000毫升DMF 12小時。反應完成後，反應產物以 蒸餾水洗滌’再以乙酸乙酯萃取，之後所得有機層以MgS〇4 . 乾燥，使用旋轉蒸發器蒸發以移除溶劑，接著使用管柱色 . 層分析純化，獲得15.2克化合物卜1(88. 64 mmol)。 - 化合物1-2之製備 - 在l〇〇C加熱下攪拌15克化合物1-1(88. 64 mmol)、 24· 1 克 2-溴-9, 9-二甲基-9H-苐（88. 64 mmol)、0. 6 克 Pd(0Ac)2(2. 7 mmol).、3. 6 毫升 P(t-Bu)3 (8. 9 mmol)、25. 5 克NaOt-Bu(266 mmol)及1000毫升曱苯12小時。反應完 成後，反應產物以蒸餾水洗滌，再以乙酸乙酯萃取，之後 所得有機層以MgS〇4乾燥，使用旋轉蒸發器蒸發以移除溶 劑，接著使用管柱色層分析純化，獲得11. 2克化合物1-2 (30. 98 mmol)。 化合物1-3之製備 在120°C回流下攪拌1〇克4-二苯并噻吩硼酸（44 mmol)、 31克1，4-二溴苯（1321111〇〇1)、2.5克？(1(??^13)4(2.2丽〇1)、 132 毫升 1M Na2C〇3(132 mmol)、500 毫升甲苯、及 200 毫 升乙醇12小時。反應完成後，反應產物以蒸餾水洗滌，再 以乙酸乙酯萃取，之後所得有機層以MgS〇4乾燥，使用旋 轉蒸發器蒸發以移除溶劑，接著使用管柱色層分析純化， 獲得6. 7克化合物1-3(19. 8 mmol)。 化合物3之製備 在100 C回流下授拌7. 9克化合物1-3 (23. 28 mmol)、 7 克化合物 1-2(19. 4 mmol)、0. 13 克 Pd(OAc)2(0. 58 mmol)、 21 95299 201213501 0. 94 毫升 P(t-Bu)3(2. 32 mmol)、6· 7 克 NaOt-Bu(69. 84 mmol)及500毫升曱苯12小時。反應完成後，反應產物以 蒸餾水洗滌’再以乙酸乙酯萃取，之後所得有機層以MgS〇4 乾燥’使用旋轉蒸發器蒸發以移除溶劑，接著使用管柱色 層分析純化，及再結晶，獲得8. 0克化合物3 (12. 9 mmol， 66%)。 XH NMR(CDC13, 200 MHz) 6 = 1.72(6H, s) , 6.58(1H, m), 6.69~6.75(5H, m) , 7.28(1H, m), 7.38~7.41(2H, m), 7.5-7.62(13H, m), 7.87(1H, m) , 7.98(1H, m) , 8.2(1H, m) , 8.41~8.45(2H, m); MS/FAB實測值 620,計箕伹619.82 製備例2化合物9之製備Preparation of Compound 1-1 30 g of 4) 4-bromobiphenyl (128.7 111111〇1), 27 ml (mL) of aqueous ammonia (772 mmol), 2.45 g of Cul (12.87 mmol) were stirred under heating at 100 °C. ), 12. 9 ml of ethyl acetate (128·7 mmol), 83.9 g of Cs2C〇3 (257. 4 20 95299 201213501 .mmol) and 1000 ml of DMF for 12 hours. After completion of the reaction, the reaction product was washed with distilled water and then extracted with ethyl acetate. The organic layer obtained was then dried with &lt;RTI ID=0.0&gt;&gt; Compound 1 (88. 64 mmol). - Preparation of Compound 1-2 - 15 g of compound 1-1 (88.64 mmol), 24.1 g of 2-bromo-9,9-dimethyl-9H-indole (88) were stirred under heating at 10 °C. 64 mmol), 0.6 g Pd(0Ac)2 (2.7 mmol), 3. 6 ml P(t-Bu)3 (8.9 mmol), 25.5 g NaOt-Bu (266 mmol) ) and 1000 ml of terpene for 12 hours. After the completion of the reaction, the reaction product was washed with distilled water, and then extracted with ethyl acetate, and then the organic layer was dried with MgSO 4 , and evaporated using a rotary evaporator to remove solvent. Compound 1-2 (30. 98 mmol). Preparation of Compound 1-3 1 g of 4-dibenzothiopheneboronic acid (44 mmol), 31 g of 1,4-dibromobenzene (1321111〇〇1), 2.5 g were stirred under reflux at 120 °C. (1 (??^13) 4 (2.2 〇 1), 132 ml of 1 M Na2C 〇 3 (132 mmol), 500 ml of toluene, and 200 ml of ethanol for 12 hours. After the reaction is completed, the reaction product is washed with distilled water, and then After the extraction with ethyl acetate, the resulting organic layer was dried with EtOAc (EtOAc). The compound 3 was prepared by mixing 7.9 g of compound 1-3 (23. 28 mmol), 7 g of compound 1-2 (19. 4 mmol), and 0.1 g of Pd(OAc) 2 (0. 58 mmol), 21 95299 201213501 0. 94 ml of P(t-Bu)3 (2.32 mmol), 6.7 g of NaOt-Bu (69.84 mmol) and 500 ml of toluene for 12 hours. The reaction product was washed with distilled water and then extracted with ethyl acetate, then the organic layer was dried with MgSO 4 to evaporate using a rotary evaporator to remove solvent, and then purified by column chromatography and recrystallized to obtain 8. 0g compound 3 (12. 9 mmol, 66%). XH NMR (CDC13, 200 MHz) 6 = 1.72 (6H, s), 6.58 (1H, m), 6.69~6.75 (5H, m), 7.28 (1H , m), 7.38~7.41(2H, m), 7.5-7.62(1 3H, m), 7.87(1H, m), 7.98(1H, m), 8.2(1H, m), 8.41~8.45(2H, m); MS/FAB 620, 619.82 Preparation Example 2 Preparation of 9

化合物2-1之製備 將 20. 0 克 2-萘酚（138· 8 mmol)、28. 8 克 NaHS〇3 (277. 4 mmol)、160毫升蒸餾水、及31· 2毫升4-溴苯基肼（166. 4 匪〇1)加熱至12(TC。12小時後，將蒸餾水加入反應混合 物’且將產生的固體經真空過濾。將前述所得固體加至鹽 酸水溶液並加熱至l〇〇°c。丨小時後，所得產物以二氯甲烷 22 95299 201213501 萃取，以蒸德水及NaOH水溶液洗務，經管柱分離純化，獲 得 9.2 克化合物 2-1 (31.0 mmol)。 . 化合物2-2之製備 • 將 9_ 2 克化合物 2-1(31. 0 mmol)、2. 0 克 Cu(31. 0 - nrniol)、0. 4 克 18-冠-6 驗（1· 6 mmol)、12. 8 克 K2CO3 (93. 2 - mmol)及100毫升1，2-二氯苯混合，並於18〇。(：回流授拌 12小時。反應混合物冷卻至室溫’真空蒸餾，以二氯曱炫 萃取然後以蒸餾水洗滌，接著以MgS(K乾燥，真空蒸顧， 並管柱分離，獲得7· 6克化合物2-2 (20. 4 mmol)。 化合物2-3之製備 在100°C加熱下攪拌35.2克2-溴-9,9-二曱基-911-苐 (128. 7 mmol)、27 毫升氨水（772 mmol)、2· 45 克 Cul (12. 87 mmol)、12. 9 毫升乙醯丙酮（128. 7 mmol)、83. 9 克Cs2C〇3 (257.4 mmol)及1000毫升DMF 12小時。反應完 成後，反應產物以蒸餾水洗滌，再以乙酸乙酯萃取，之後 所得有機層以MgS〇4乾燥，使用旋轉蒸發器蒸發以移除溶 劑，接著使用管柱色層分析純化，獲得11. 3克化合物2-3 (54 mmol) 〇 化合物2-4之製備 在100°C加熱下攪拌18. 5克化合物2-3 (88. 64 mmol)、 33 克化合物 2-2 (88. 64 mmol)、0. 6 克 Pd(0Ac)2 2. 7 mmol)、3. 6 毫升 P(t-Bu)3(8. 9 minol)、25..5 克 NaOt-Bu (266 mmol)及1000毫升甲苯12小時。反應完成後，反應產物以 蒸餾水洗滌，再以乙酸乙酯萃取，之後所得有機層以MgS〇4 23 95299 201213501 乾燥’使用旋轉蒸發器蒸發以移除溶劑，接著使用管柱色 層分析純化，獲得14. 2克化合物2-4 (28. 4 mmol)。 化合物9之製備 在l〇〇°C回流下攪拌7. 9克化合物1-3 (23. 28 mmol)、 9. 7 克化合物 2-4 (19. 4 mmol)、〇. 13 克 Pd(OAc)2(0. 58 mmol)、0. 94 毫升 p(t-Bu)3(2· 32 mmol)、6. 7 克 NaOt-Bu (69. 84 mmol)及500毫升曱苯12小時。反應完成後，反應 產物以蒸餾水洗滌，再以乙酸乙酯萃取，之後所得有機層 以MgS〇4乾燥，使用旋轉蒸發器蒸發以移除溶劑，使用管 柱色層分析純化’及再結晶，獲得7 3克化合物9 (9 62 mmol, 50%)。Preparation of compound 2-1: 20.0 g of 2-naphthol (138·8 mmol), 28.8 g of NaHS〇3 (277. 4 mmol), 160 ml of distilled water, and 31.2 ml of 4-bromophenyl肼(166. 4 匪〇1) was heated to 12 (TC. After 12 hours, distilled water was added to the reaction mixture' and the resulting solid was vacuum filtered. The obtained solid was added to aqueous hydrochloric acid and heated to l 〇〇 °c After 丨 hours, the obtained product was extracted with dichloromethane 22 95299 201213501, washed with distilled water and aqueous NaOH solution, and purified by column chromatography to obtain 9.2 g of compound 2-1 (31.0 mmol). Preparation of compound 2-2 • 9_ 2 g of compound 2-1 (31.0 mmol), 2.0 g of Cu (31.0- nrniol), 0.4 g of 18-crown-6 test (1.6 mmol), 12.8 g K2CO3 (93. 2 - mmol) and 100 ml of 1,2-dichlorobenzene were mixed at 18 〇. (: reflux mixing for 12 hours. The reaction mixture was cooled to room temperature. Vacuum distillation, extraction with dichloropurine and then Washed with distilled water, followed by MgS (K dry, vacuum distillation, and column separation, to obtain 7.6 g of compound 2-2 (20.4 mmol). Preparation of compound 2-3 was heated at 100 ° C Mix 35.2 g of 2-bromo-9,9-dimercapto-911-苐 (128. 7 mmol), 27 ml of ammonia (772 mmol), 2·45 g of Cul (12.87 mmol), 12. 9 ml B Acetone (128. 7 mmol), 83.9 g Cs2C〇3 (257.4 mmol) and 1000 ml of DMF for 12 hours. After the reaction was completed, the reaction product was washed with distilled water and then extracted with ethyl acetate. 〇4 was dried, evaporated using a rotary evaporator to remove the solvent, and then purified by column chromatography to obtain 11.3 g of compound 2-3 (54 mmol). Preparation of oxime compound 2-4 was stirred under heating at 100 °C. 18. 5 g of compound 2-3 (88.64 mmol), 33 g of compound 2-2 (88.64 mmol), 0.6 g of Pd(0Ac)2 2. 7 mmol), 3. 6 ml of P(t -Bu)3 (8.99 minol), 25..5 g of NaOt-Bu (266 mmol) and 1000 ml of toluene for 12 hours. After completion of the reaction, the reaction product was washed with distilled water and extracted with ethyl acetate. The layer was purified by a column chromatography to give 14.2 g of compound 2-4 (28. 4 mmol). </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; Preparation of compound 9 was stirred under reflux at 7.5 ° C. 9. 9 g of compound 1-3 (23. 28 mmol), 9. 7 g of compound 2-4 (19.4 mmol), 〇. 13 g Pd (OAc 2 (0. 58 mmol), 0.94 ml of p(t-Bu)3 (2·32 mmol), 6.7 g of NaOt-Bu (69.84 mmol) and 500 ml of benzene. After completion of the reaction, the reaction product was washed with distilled water and extracted with ethyl acetate, and then the organic layer was dried with &lt;RTI ID=0.0&gt;&gt; 7 3 g of compound 9 (9 62 mmol, 50%).

95299 NMR(CDC13, 200 ΜΗζ)δ = 1.72 (6H, s), 5.93(1H, m), 6.58(1H, m), 6.69-6.75 (3H, m), 7.28(1H, m) , 7.38(1H, m), 7·45(1Η, m), 7.5(3H, m), 7.52(1H, m), η .54-7.62(13H, m), 7·87(1Η, m), 7.98(1H, m) , 8.16-8.2(2H, m), 8.41~8.45(2H, m), 8·54(1Η, m); MS/FAB 測值 759,計算值 758 97 製備例3化合物28之製備 24 201213501 化合物3-1之製備 在120〇回流下擾摔5.4克苯基删酸（44 111111〇1)、18.9 克 1,4-二溴萘（66 mmol)、2. 0 克 Pd(PPh3)4(1.76 _〇1)、 14. 0克Na2C〇3( 132 mmol)、200毫升甲苯、及1〇〇毫升乙 醇12小時。反應完成後，反應產物以蒸鶴水洗蘇，再以乙 酸乙酯萃取，之後所得有機層以MgS〇4乾燥，使用旋轉蒸 發器蒸發以移除溶劑’接著使用管柱色層分析純化，獲得 9. 1 克化合物 3-1 (32. 14 mmol)。 化合物3-2之製備 在100°C加熱下攪拌18. 6克化合物2-3 (88. 64 mmol)、 25 克化合物 3-1(88· 64 mmol)、0. 6 克 Pd(0AcM2. 7 mmol)、 3. 6 毫升 P(t-Bu)3(8. 9 minol)、25. 5 克 NaOt-Bu (266 mmol) 及1000毫升甲苯12小時。反應完成後，反應產物以蒸餾 水洗滌’再以乙酸乙酯萃取，之後所得有機層以MgSCU乾 燥，使用旋轉蒸發器蒸發以移除溶劑，接著使用管柱色層 分析純化’獲得14. 2克化合物3-2(34. 5 mmol)。 化合物28之製備 在100°C回流下攪拌7. 9克化合物1-3(23. 28 mmol)、 8. 0 克化合物 3-2(19. 4 mmol)、0. 13 克 Pd(OAcM〇. 58 mmol)、〇. 94 毫升 P(t-Bu)3(2. 32 mmol)、6. 7 克 NaOt-Bu (69. 84 mmol)及500毫升曱苯12小時。反應完成後，反應 產物以蒸餾水洗滌’再以乙酸乙酯萃取，之後所得有機層 以MgS〇4乾燥’使用旋轉蒸發器蒸發以移除溶劑，使用管 柱色層分析純化’然後再結晶，獲得7. 3克化合物28 (10. 9 25 95299 201213501 mmol, 45%) 〇 XH NMR(CDC13, 200 ΜΗζ)δ = 1.72 (6H, s), 6.58 (1H, m), 6.69〜6.75(3H,m),7.04(lH,m),7.28(lH,m),7.38~7.41(2H,m), 7.5〜7.53(11H, m), 7.78~7.79(3H, m), 7.87(1H, m), 7.·98(1Η, m), 8.07(1H, m), 8.2(1H, m), 8·41~8.49(3Η, m); MS/FAB 實測值 670, 計算值 669.87 製備例4化合物30之製備95299 NMR (CDC13, 200 ΜΗζ) δ = 1.72 (6H, s), 5.93 (1H, m), 6.58 (1H, m), 6.69-6.75 (3H, m), 7.28 (1H, m), 7.38 (1H , m), 7·45(1Η, m), 7.5(3H, m), 7.52(1H, m), η .54-7.62(13H, m), 7·87(1Η, m), 7.98(1H , m), 8.16-8.2 (2H, m), 8.41~8.45 (2H, m), 8·54 (1 Η, m); MS/FAB s. 759, calculated 758 97 Preparation of compound 28 of Preparation 3 201213501 Preparation of compound 3-1 under a reflux of 120 Torr, 5.4 g of phenyl-decanoic acid (44 111111〇1), 18.9 g of 1,4-dibromonaphthalene (66 mmol), 2.0 g of Pd(PPh3)4 (1.76 _〇1), 14. 0 g of Na2C〇3 (132 mmol), 200 ml of toluene, and 1 ml of ethanol for 12 hours. After completion of the reaction, the reaction product was washed with steamed crane water and extracted with ethyl acetate, and then the organic layer was dried over MgS 4 and evaporated using a rotary evaporator to remove solvent, and then purified by column chromatography. . 1 g of compound 3-1 (32. 14 mmol). The compound 3-2 was stirred under heating at 100 ° C. 18.6 g of compound 2-3 (88.64 mmol), 25 g of compound 3-1 (88·64 mmol), 0.6 g of Pd (0 AcM 2. 7 Methyl), 3. 6 ml of P(t-Bu)3 (8.9 min), 25.5 g of NaOt-Bu (266 mmol) and 1000 ml of toluene for 12 hours. After the completion of the reaction, the reaction product was washed with distilled water and then extracted with ethyl acetate. The resulting organic layer was dried with EtOAc (EtOAc). 3-2 (34. 5 mmol). The compound 28 is stirred at 100 ° C under reflux. 7.9 g of compound 1-3 (23. 28 mmol), 8. 0 g of compound 3-2 (19.4 mmol), 0.13 g of Pd (OAcM〇. 58 mmol), 〇. 94 ml of P(t-Bu)3 (2.32 mmol), 6.7 g of NaOt-Bu (69.84 mmol) and 500 ml of terpene for 12 hours. After completion of the reaction, the reaction product was washed with distilled water and then extracted with ethyl acetate, and then the organic layer was dried over MgS 4 to evaporate using a rotary evaporator to remove solvent, which was purified by column chromatography and then recrystallized. 7. 3 g of compound 28 (10. 9 25 95299 201213501 mmol, 45%) 〇XH NMR (CDC13, 200 ΜΗζ) δ = 1.72 (6H, s), 6.58 (1H, m), 6.69~6.75 (3H, m ), 7.04(lH,m), 7.28(lH,m), 7.38~7.41(2H,m), 7.5~7.53(11H, m), 7.78~7.79(3H, m), 7.87(1H, m), 7.·98(1Η, m), 8.07(1H, m), 8.2(1H, m), 8·41~8.49(3Η, m); MS/FAB found 670, calculated 669.87 Preparation Example 4 Compound 30 Preparation

化合物4-1之製備 在100°C回流下攪拌8. 2克2, 7-二溴-9, 9-二甲基-犯-苐（23· 28 mmol)、3. 2 克咔唑（19. 4 mmol)、0. 13 克 Pd(0Ac)2 (0. 58 mmol)、0· 94 毫升 P(t-Bu)3(2. 32 mmol)、6. 7 克 Na0t-Bu(69.84 mmol)及200毫升曱苯12小時。反應完成 後’反應產物以蒸餾水洗滌，再以乙酸乙酯萃取，之後所 得有機層以MgS〇4乾燥，使用旋轉蒸發器蒸發以移除溶劑， 使用管柱色層分析純化，然後再結晶，獲得5 8克化合物 4-1(13.2 mmol)。 化合物4-2之製備 在l〇〇°C加熱下攪拌8. 3克苯胺（88. 64 mmol)、38. 9 26 95299 201213501 克化合物 4-1 (88· 64 mmol)、〇. 6 克 Pd(0Ac)2 (2· 7 mmol)、 3. 6 毫升 P(t-Bu)3 (8. 9 mmol)、25. 5 克 NaOt-Bu (266 mmol) 及800毫升曱苯12小時。反應完成後，反應產物以蒸館水 洗滌，再以乙酸乙酯萃取，之後所得有機層以MgS〇4乾燥， 使用旋轉蒸發器蒸發以移除溶劑，再使用管柱色層分析純 - 化’獲得Π. 2克化合物4-2 (38. 2 mmol)。 化合物30之製備 在100°C回流下攪拌7. 9克化合物1-3 (23. 28 mmol)、 8. 7 克化合物 4-2(19. 4 mmol)、0. 13 克 Pd(OAc)2(0. 58 mmol)、0. 94 毫升 P(t-Bu)3(2. 32 mmol)、6. 7 克 NaOt-Bu (69. 84 mmol)及500毫升甲苯12小時。反應完成後，反應 產物以蒸餾水洗滌，再以乙酸乙酯萃取，之後所得有機層 以MgS〇4乾燥，使用旋轉蒸發器蒸發以移除溶劑，使用管 柱色層分析純化，然後再結晶，獲得7.0克化合物30 (9. 9 mmol，50%)。 XH NMR(CDC13, 200 MHz) δ = 1.72(6Η, s) , 6.37 (1Η,叫， 6.54(1Η, m) , 6.63(2Η, m) , 6.69(2Η, m), 6.81 (1Η, m) / 7.17-7.34(7Η, m) , 7.5~7.63(8Η, m) , 7.87(1Η, m) , 7.94~7.98(2η, m), 8.12(1Η, m) , 8.2(1Η, m) , 8.41~8.45(2Η, m) , 8.55(1Η, m). MS/FAB實測值709,计算值708.91 製備例5化合物32之製備 27 95299 201213501The preparation of the compound 4-1 was stirred at 100 ° C under reflux of 8.2 g of 2,7-dibromo-9,9-dimethyl-p-quinone (23·28 mmol), 3.2 g of carbazole (19 4 mmol), 0.13 g Pd(0Ac)2 (0. 58 mmol), 0·94 ml P(t-Bu)3 (2.32 mmol), 6.7 g Na0t-Bu (69.84 mmol) And 200 ml of terpene for 12 hours. After the completion of the reaction, the reaction product was washed with distilled water and then extracted with ethyl acetate. The organic layer was then dried with MgSO 4 , evaporated using a rotary evaporator to remove solvent, purified by column chromatography and then recrystallized. 5 8 g of compound 4-1 (13.2 mmol). The preparation of the compound 4-2 was stirred under heating at 1300 ° C. 8. 3 g of aniline (88.64 mmol), 38. 9 26 95299 201213501 g of compound 4-1 (88·64 mmol), 〇. 6 g Pd (0Ac) 2 (2.7 mmol), 3. 6 ml of P(t-Bu)3 (8.9 mmol), 25.5 g of NaOt-Bu (266 mmol) and 800 ml of benzene. After completion of the reaction, the reaction product was washed with steaming water and then extracted with ethyl acetate. The organic layer was then dried over MgS 〇 4, evaporated using a rotary evaporator to remove solvent, and then purified by column chromatography. Obtained 2 g of compound 4-2 (38. 2 mmol). The compound 30 is stirred at 100 ° C under reflux. 7.9 g of compound 1-3 (23. 28 mmol), 8. 7 g of compound 4-2 (19.4 mmol), 0.13 g of Pd(OAc)2 (0. 58 mmol), 0.94 ml of P(t-Bu)3 (2.32 mmol), 6.7 g of NaOt-Bu (69.84 mmol) and 500 ml of toluene for 12 hours. After completion of the reaction, the reaction product was washed with distilled water and extracted with ethyl acetate, and then the organic layer was dried with &lt;RTI ID=0.0&gt;&gt; 7.0 g of compound 30 (9. 9 mmol, 50%). XH NMR (CDC13, 200 MHz) δ = 1.72 (6Η, s), 6.37 (1Η, ,, 6.54(1Η, m) , 6.63(2Η, m) , 6.69(2Η, m), 6.81 (1Η, m) / 7.17-7.34(7Η, m) , 7.5~7.63(8Η, m) , 7.87(1Η, m) , 7.94~7.98(2η, m), 8.12(1Η, m) , 8.2(1Η, m) , 8.41 ~8.45(2Η, m), 8.55(1Η, m). MS/FAB found 709, calculated 708.91 Preparation of compound 32 of Preparation 5 27 95299 201213501

β(ΡΗ)2 ^ρό+ Β,~〇·〇· 化合物5-1之製備 在100°C加熱下攪拌8. 3克苯胺（88. 64 mmol)、24. 1 克2-溴-9,9-二曱基-911-苐（88.64 111111〇1)、0.6克？(1(0八〇)2 (2. 7 mmol)、3. 6 毫升 P(t-Bu)3(8. 9 _〇1)、25. 5 克 NaOt-Bu(266 mmol)及800毫升甲苯12小時。反應完成後， 反應產物以蒸餾水洗滌，再以乙酸乙酯萃取，之後所得有 機層以MgS〇4乾燥，使用旋轉蒸發器蒸發以移除溶劑，再 使用管柱色層分析純化，獲得14. 2克化合物5-1(49. 8 _〇1)。 化合物5-2之製備 在120°C回流下攪拌10克4-二苯并噻吩硼酸（44 mmol)、 41.2 克 1，4-二溴聯苯（132 mmol)、2.5 克 Pd(PPh3)4(2.2 mmol)、132 毫升 1M Na2C〇3(132 mmol)、500 毫升曱苯、及 200毫升乙醇12小時。反應完成後，反應產物以蒸餾水洗 滌，再以乙酸乙酯萃取，之後所得有機層以MgS〇4乾燥， 使用旋轉蒸發器蒸發以移除溶劑，再使用管柱色層分析純 化，獲得15. 3克化合物5-2(36. 8 mmol)。 化合物32之製備 28 95299 •201213501 * 在l〇0°C回流下攪拌9. 7克化合物5-2(23. 28 mmol)、5. 54 克化合物 5-1(19· 4 mraol)、〇· 13 克 Pd(〇Ac)2(〇. 58 mm〇1)、 0· 94 毫升 P(t-Bu)3(2. 32 mmol)、6. 7 克 NaOt-Bu (69. 84 mmol)及500毫升甲苯12小時。反應完成後，反應產物以 蒸餾水洗滌，再以乙酸乙酯萃取，之後所得有機層以MgS〇4 . 乾燥，使用旋轉蒸發器蒸發以移除溶劑，使用管柱色層分 析純化’並再結晶，獲得5.8克化合物32 (9.4 mmol，48 %)。 H NMR(CDC13/ 200 ΜΗζ)δ = 1.72(6H, s) , 6.58~6.63 (3H, in), 6.69-6.8K4H, m) f 7.2~7.28(7H, m) , 7.38(1H, m) , 7.5~7.62(7H, m&gt;, 7.87(1H, ra), 7.98(1H, m), 8.2(1H, m&gt;, 8.41~8.45(2H, m); MS/FAB實測值620,計算值619.82 製備例6化合物37之製備克 苯 ΡΗ 88 88 88 88 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 9-dimercapto-911-苐 (88.64 111111〇1), 0.6 g? (1 (0 〇) 2 (2.7 mM), 3.6 ml of P(t-Bu) 3 (8.9 g _〇1), 25.5 g of NaOt-Bu (266 mmol) and 800 ml of toluene After the completion of the reaction, the reaction product was washed with distilled water and then extracted with ethyl acetate. The organic layer was then dried with MgSO 4 and evaporated using a rotary evaporator to remove solvent and purified by column chromatography. 14. 2 g of compound 5-1 (49. 8 _〇1). Preparation of compound 5-2 10 g of 4-dibenzothiopheneboronic acid (44 mmol), 41.2 g of 1,4-propane were stirred at 120 ° C under reflux. Dibromobiphenyl (132 mmol), 2.5 g Pd(PPh3) 4 (2.2 mmol), 132 ml 1 M Na2C〇3 (132 mmol), 500 ml of toluene, and 200 ml of ethanol for 12 hours. The gram of the compound 5-2 (1 g of the compound 5-2) was obtained by the purification of the column chromatography using a rotary evaporator to remove the solvent. 36. 8 mmol) Preparation of Compound 32 28 95299 • 201213501 * Stirring at 7.5 ° C under reflux of 9. 7 g of compound 5-2 (23. 28 mmol), 5. 54 g of compound 5-1 (19· 4 mraol), 〇 · 13 g Pd(〇Ac) 2 (〇. 58 mm〇1), 0·94 ml P(t-Bu)3 (2.32 mmol), 6.7 g NaOt-Bu (69.84 mmol) and 500 ml of toluene for 12 hours. After the reaction was completed, the reaction product was washed with distilled water and then extracted with ethyl acetate, and then the organic layer was dried with MgSO 4 and evaporated using a rotary evaporator to remove solvent. Purification and recrystallization afforded 5.8 g of compound 32 (9.4 mmol, 48%). H NMR (CDC13/200 ΜΗζ) δ = 1.72 (6H, s), 6.58~6.63 (3H, in), 6.69-6.8K4H, m) f 7.2~7.28(7H, m) , 7.38(1H, m) , 7.5~7.62(7H, m&gt;, 7.87(1H, ra), 7.98(1H, m), 8.2(1H, m&gt;, 8.41 ~8.45(2H, m); MS/FAB found 620, calculated 619.82 Preparation of compound 37 of Preparation 6

化合物6-1之製備 將 150 克 2, 7-二溴-9, 9-二曱基苐（426 mmol)溶於 2. 1 公升（L)四氫呋喃’並冷卻至-78°C，之後於其内緩慢滴加 29 95299 201213501 170毫升n-BuLi (2.5M，於己烧中，426 mmol)，並攪拌1 小時。 於其内加入53毫升三曱基棚酸（469 mmol)，並攪拌 12小時。反應完成後，以2M HC1終止反應，且反應產物 以EA/HzO萃取’以MgS〇4脫水，真空蒸餾，並管柱分離， 獲得70克化合物6-1 (220.8 mmol)。 化合物6-2之製備 在90°C下攪拌70克化合物6-1 (220 mmol)、50克2-蛾石肖基苯（200 mmol)、7 克 Pd(PPh3)4 (6 mmol)、64 克 Na2C〇3 (600 mmol)、1公升曱苯、〇. 5公升乙醇、及〇· 3公升水 7. 5小時。反應完成後，反應產物以ea/H2〇萃取，以MgS〇4 脫水’再真空蒸餾而獲得化合物6-2，其不另外純化接著 立即進行下一程序。 化合物6-3之製備 將90克化合物6-2及750毫升P(OEt)3溶於750毫升 1’2-二氯苯，並在i50°c攪拌9小時，之後該攪拌的溶液 以蒸餾水洗滌及經處理以移除溶劑，所得紅色液體接著進 行管柱分離，獲得26克化合物6_3 (79 69咖〇1)。 化合物6-4之製備 在100°C回流下攪拌2.6克氯苯（23. 28 mmol)、7.0 克化合物 6-3(19.4mmol)、〇· 13 克 Pd(0Ac)2 (〇 58mm〇1)、 〇. 94 毫升 p(t-Bu)3(2. 32 mm〇i)、6. 7 克 NaOt-Bu (69. 84 mmol)及200毫升曱苯12小時。反應完成後，反應產物以 蒸餾水洗滌，再以乙酸乙酯萃取，之後所得有機層以MgS〇4 30 95299 201213501 乾燥’使用旋轉蒸發器蒸發以移除溶劑，使用管柱色層分 Φί純化’並再結日日’獲得6 8克化合物6-4 (15· 5 mmo 1)。 化合物6-5之製備 在100°c加熱下攪拌18. 6克化合物2-3(88. 64 mmol)、 38. 9 克化合物 6-4(88. 64 mm〇i)、〇. 6 克 Pd(0Ac)2(2. 7 • mmol)、3. 6 毫升 (8. 9 mmol)、25. 5 克 NaOt-Bu(266 mmol)及800毫升甲苯12小時。反應完成後，反應產物以 蒸顧水洗滌’再以乙酸乙酯萃取，之後所得有機層以MgS〇4 乾燥’使用旋轉蒸發器蒸發以移除溶劑，並使用管柱色層 分析純化’獲得15. 6克化合物6-5(27. 5 mmol)。 化合物37之製備 在100°C回流下攪拌7. 9克化合物卜3(23. 28 mmol)、11 克化合物 6-5 (19.4mmol)、〇.l3 克 Pd(OAc)2(0. 58mmol)、 〇. 94 毫升 P(t-Bu)3(2. 32 mmol)、6. 7 克 Na0t-Bu(69. 84 mmol)及500毫升曱苯12小時。反應完成後，反應產物以 蒸餾水洗滌，再以乙酸乙酯萃取，之後所得有機層以MgS〇4 乾燥’使用旋轉蒸發器蒸發以移除溶劑，使用管柱色層分 析純化，並再結晶，獲得6. 9克化合物37(8.4匪〇1，43 %)。 XH NMR(CDC13, 200 ΜΗζ)δ = 1.72(12H, s), 6.58~6.81 (6H, m), 7.28~7.29(2H, m), 7.38(1H, m) , 7.45~7.52(6H, m), 7.54(3H, s), 7.54-7.63(6H, m) , 7.84~7.87(2H, m) , 7.98(1H, m) , 8.12(1H, m), 8.2(1^111),8.41~8.45(214,111),8.85(113),(1&gt;;^^/找8實測值 825,計算值 825.07 31 95299 201213501 製備例7化合物43之製備Preparation of Compound 6-1 150 g of 2,7-dibromo-9,9-diindenylhydrazine (426 mmol) was dissolved in 2.1 liters (L) of tetrahydrofuran and cooled to -78 ° C, after which 29 95299 201213501 170 ml of n-BuLi (2.5 M in hexane, 426 mmol) was slowly added dropwise and stirred for 1 hour. 53 ml of triterpene succinic acid (469 mmol) was added thereto and stirred for 12 hours. After the completion of the reaction, the reaction was quenched with 2M HCl, and the product was extracted with EA/HzO, dehydrated with &lt;RTI ID=0.0&gt;&gt; Preparation of Compound 6-2 70 g of Compound 6-1 (220 mmol), 50 g of 2-Mothyl succinylbenzene (200 mmol), 7 g of Pd(PPh3)4 (6 mmol), 64 g of Na2C were stirred at 90 °C.小时3 (600 mmol), 1 liter of benzene, 〇. 5 liters of ethanol, and 〇 3 liters of water for 7.5 hours. After completion of the reaction, the reaction product was extracted with ea/H 2 hydrazine, dehydrated with &lt;RTI ID=0.0&gt;&gt; Preparation of compound 6-3 90 g of compound 6-2 and 750 ml of P(OEt) 3 were dissolved in 750 ml of 1'2-dichlorobenzene and stirred at i50 ° C for 9 hours, after which the stirred solution was washed with distilled water. And treated to remove the solvent, the resulting red liquid was then subjected to column separation to obtain 26 g of compound 6-3 (79 69 Curry 1). Preparation of Compound 6-4 2.6 g of chlorobenzene (23.28 mmol), 7.0 g of compound 6-3 (19.4 mmol), and 〇13 g of Pd(0Ac)2 (〇58 mm〇1) were stirred under reflux at 100 °C. 〇. 94 ml p(t-Bu)3 (2. 32 mm〇i), 6.7 g NaOt-Bu (69.84 mmol) and 200 ml of terpene for 12 hours. After completion of the reaction, the reaction product was washed with distilled water and extracted with ethyl acetate, and then the organic layer was dried with &lt;RTI ID=0.0&gt;&gt;&&&&&&&&&&&&&&&&&&& On the end of the day, we obtained 6 8 grams of compound 6-4 (15·5 mmo 1). Preparation of compound 6-5 was stirred under heating at 100 ° C 18.6 g of compound 2-3 (88.64 mmol), 38.9 g of compound 6-4 (88.64 mm〇i), 〇. 6 g Pd (0Ac) 2 (2.7 mM), 3.6 ml (8.99 mmol), 25.5 g NaOt-Bu (266 mmol) and 800 ml of toluene for 12 hours. After completion of the reaction, the reaction product was washed with water and then extracted with ethyl acetate, then the organic layer was dried with &lt;RTI ID=0.0&gt;&gt; 6 g of compound 6-5 (27.5 mmol). Preparation of compound 37 was stirred under reflux at 100 ° C. 7. 9 g of compound b 3 (23. 28 mmol), 11 g of compound 6-5 (19.4 mmol), 〇.13 g of Pd(OAc) 2 (0. 58 mmol) 〇. 94 ml of P(t-Bu)3 (2.32 mmol), 6.7 g of Na0t-Bu (69.84 mmol) and 500 ml of terpene for 12 hours. After completion of the reaction, the reaction product was washed with distilled water and then extracted with ethyl acetate, and then the organic layer was dried with &lt;RTI ID=0.0&gt;&gt; 6. 9 g of compound 37 (8.4 匪〇 1, 43%). XH NMR (CDC13, 200 ΜΗζ) δ = 1.72 (12H, s), 6.58~6.81 (6H, m), 7.28~7.29(2H, m), 7.38(1H, m) , 7.45~7.52(6H, m) , 7.54(3H, s), 7.54-7.63(6H, m) , 7.84~7.87(2H, m) , 7.98(1H, m) , 8.12(1H, m), 8.2(1^111), 8.41~8.45 (214,111), 8.85 (113), (1); ^^/ find 8 measured value 825, calculated value 825.07 31 95299 201213501 Preparation of compound 43 of Preparation Example 7

化合物7-1之製備 在100°(：加熱下攪拌41.7克4-溴-^二苯基苯胺 (128.7 111111〇1)、27毫升氨水（772 111111〇1)、2.45克（：111(12.87 腦1〇1)、12.9毫升乙酿丙_(128.7 111111〇1)、83.9克〇32€〇3 (257.4 mmol)及1000毫升DMF 12小時。反應完成後，反 應產物以蒸餾水洗滌，再以乙酸乙酯萃取，之後所得有機 層以MgS〇4乾燥，使用旋轉蒸發器蒸發以移除溶劑，接著 使用管柱色層分析純化，獲得12. 2克化合物7-1 (46. 9 mmol)。 化合物7-2之製備 在100°C加熱下攪拌23. 1克化合物7-1(88. 64 mmol)、 24. 1 克 2-溴-9, 9-二曱基-9H-苐（88. 64 mmol)、0. 6 克 Pd(0Ac)2(2. 7 mmol)、3. 6 毫升 P(t-Bu)3(8. 9 _〇1)、25. 5 克NaOt-Bu(266 mmol)及1000毫升曱苯12小時。反應完 成後，反應產物以蒸餾水洗滌，再以乙酸乙酯萃取，之後 所得有機層以MgS〇4乾燥，使用旋轉蒸發器蒸發以移除溶 32 95299 201213501 劑，接著使用管柱色層分析純化，獲得18. 4克化合物7-2 (40.65 mmol)。 化合物43之製備 在100°C回流下攪拌7. 9克化合物1-3(23. 28 mmol)、 8. 8 克化合物 7-2(19. 4 mmol)、0. 13 克 Pd(OAc)2(0. 58 mmol)、0. 94 毫升 P(t-Bu)3(2. 32 mmol)、6. 7 克 NaOt-Bu (69. 84 mmol)及500毫升甲苯12小時。反應完成後，反應 產物以蒸餾水洗滌，再以乙酸乙酯萃取，之後所得有機層 以MgS〇4乾燥，使用旋轉蒸發器蒸發以移除溶劑，使用管 柱色層分析純化，並再結晶，獲得5. 7克化合物43(8. 0 mmol ， 41%) 〇 XH NMR(CDC13, 200 ΜΗζ)δ = 1.72(6Η, s) , 6.38 (4Η, τη), 6.58~6.63(5Η, m) , 6.69~6.81(5Η, m) , 7.2(4Η, m) , 7.28(1Η, m), 7.38(1Η, m), 7.5~7.62(7Η, m) , 7..87(1Η, m) , 7.98(1Η, πι) , 8.2(1Η, ία), 8.41~8·45(2Η, m); MS/FAB 實測值 711,計算值 710·93 製備例8化合物69之製備Preparation of Compound 7-1: 41.7 g of 4-bromo-diphenylaniline (128.7 111111〇1), 27 ml of ammonia (772 111111〇1), 2.45 g (:111 (12.87 brain) were stirred at 100 ° (with heating). 1〇1), 12.9 ml of ethyl propylene _ (128.7 111111 〇 1), 83.9 g 〇 32 〇 3 (257.4 mmol) and 1000 ml of DMF for 12 hours. After the reaction is completed, the reaction product is washed with distilled water and then with acetic acid 2克化合物7-1 (46. 9 mmol). Compound 7 was obtained. The organic layer was dried with EtOAc (EtOAc). Preparation of -2 was stirred under heating at 100 ° C. 23.1 g of compound 7-1 (88.64 mmol), 24. 1 g of 2-bromo-9,9-dimercapto-9H-indole (88.64 mmol) ), 0.6 g Pd(0Ac) 2 (2.7 mmol), 3.6 ml P(t-Bu) 3 (8.9 g _〇1), 25.5 g NaOt-Bu (266 mmol) and 1000 ml of toluene was allowed to stand for 12 hours. After the reaction was completed, the reaction product was washed with distilled water and extracted with ethyl acetate, and then the organic layer was dried over MgSO 4 and evaporated using a rotary evaporator to remove solvent 32 95299 201213501. Column chromatography analysis 18. g of compound 7-2 (40.65 mmol). Preparation of compound 43 was stirred under reflux at 100 ° C. 7. 9 g of compound 1-3 (23. 28 mmol), 8. 8 g of compound 7-2 ( 19. 4 mmol), 0. 13 g Pd(OAc) 2 (0. 58 mmol), 0.94 ml P(t-Bu) 3 (2.32 mmol), 6.7 g NaOt-Bu (69. 84 mmol) and 500 ml of toluene for 12 hours. After the reaction was completed, the reaction product was washed with distilled water and extracted with ethyl acetate, and then the organic layer was dried with MgSO 4 and evaporated using a rotary evaporator to remove solvent. Chromatography analysis and purification, and recrystallization, 5.7 g of compound 43 (8.0 mmol, 41%) 〇XH NMR (CDC13, 200 ΜΗζ) δ = 1.72 (6 Η, s), 6.38 (4 Η, τη), 6.58~6.63(5Η, m), 6.69~6.81(5Η, m), 7.2(4Η, m), 7.28(1Η, m), 7.38(1Η, m), 7.5~7.62(7Η, m), 7. .87(1Η, m) , 7.98(1Η, πι) , 8.2(1Η, ία), 8.41~8·45(2Η, m); MS/FAB 711, calculated 710·93 Preparation Example 8 Compound 69 Preparation

化合物8-1之製備 在120°C回流下攪拌10克2-二苯并噻吩硼酸（44 mmol)、 31 克 1，4-二溴苯（132 mmol)、2. 5 克 Pd(PPh3)4(2. 2 mmol)、 132 毫升 1M Na2C〇3(132 mmol)、500 毫升曱苯、及 200 毫 33 95299 201213501 升乙醇12小時。反應完成後，反應產物以蒸餾水洗滌，再 以乙酸乙酯萃取，之後所得有機層以MgSCU乾燥，使用旋 轉蒸發器蒸發以移除溶劑，再使用管柱色層分析純化，獲 得 12. 9 克化合物 8-1(38. 0 mmol)。 化合物69之溆備 在100°C回流加熱下攪拌7. 9克化合物8-1(23. 28 mmol)、7 克化合物 1-2(19. 4 mmol)、0· 13 克 Pd(OAcM〇. 58 mmol)、0. 94 毫升 P(t-Bu)3(2. 32 mmol)、6. 7 克 NaOt-Bu (69. 84 mmol)及500毫升甲苯12小時。反應完成後，反應 產物以蒸餾水洗滌，再以乙酸乙酯萃取，之後所得有機層 以MgS〇4乾燥，使用旋轉蒸發器蒸發以移除溶劑，使用管 柱色層分析純化，並再結晶’獲得7. 1克化合物69 (11. 5 mmol } 59%) 0 XH NMR(CDC13, 200 ΜΗζ)δ = 1.72(6H, s), 5.93(1H, m), 6.38(4H, m) , 6.58-6.63(3H, m), 6.69~6.81(4H, m) , 7.2(2H, m), 7.28〜7.29(2H,m),7.38(lH,n〇,7.45q.54(15H,m),7.69(lH,m), 7.87(1H, m), 7.98(1H, m), 8.12(1h,⑴，8.2(1H, m) r 8.41~8.45(2H, n〇; &amp;S/FAB 實測值 620,计算值 619 82 製備例9化合物76之製備Preparation of Compound 8-1 10 g of 2-dibenzothiopheneboronic acid (44 mmol), 31 g of 1,4-dibromobenzene (132 mmol), 2.5 g of Pd(PPh3)4 were stirred under reflux at 120 °C. (2.2 mmol), 132 ml of 1 M Na2C〇3 (132 mmol), 500 ml of toluene, and 200 ml of 33 95299 201213501 liters of ethanol for 12 hours. After the completion of the reaction, the reaction product was washed with distilled water, and then extracted with ethyl acetate, and then the organic layer was dried with a MgSO. 8-1 (38. 0 mmol). The compound of the compound 69 was stirred under reflux with heating at 100 ° C. 7. 9 g of compound 8-1 (23. 28 mmol), 7 g of compound 1-2 (19.4 mmol), 0·13 g of Pd (OAcM〇. 58 mmol), 0.94 ml of P(t-Bu)3 (2.32 mmol), 6.7 g of NaOt-Bu (69.84 mmol) and 500 ml of toluene for 12 hours. After completion of the reaction, the reaction product was washed with distilled water and then extracted with ethyl acetate, and then the organic layer was dried with MgSO 4 , evaporated on a rotary evaporator to remove solvent, purified by column chromatography and recrystallized. 7. 1 g of compound 69 (11.5 mmol) 59%) 0 XH NMR (CDC13, 200 ΜΗζ) δ = 1.72 (6H, s), 5.93 (1H, m), 6.38 (4H, m), 6.58-6.63 (3H, m), 6.69~6.81(4H, m), 7.2(2H, m), 7.28~7.29(2H,m), 7.38(lH,n〇,7.45q.54(15H,m), 7.69( lH,m), 7.87(1H, m), 7.98(1H, m), 8.12(1h,(1),8.2(1H, m) r 8.41~8.45(2H, n〇; &amp;S/FAB measured value 620, Calculated value 619 82 Preparation of compound 76 of Preparation 9

化合物9-1之製備 95299 34 201213501 在120°C回流下攪拌10. 5克9, 9-二曱基-9H-苐-2-基硼 酸（44 mmol)、31 克 1，4-二溴苯（132 mmol)、2. 5 克 Pd(PPh3)4(2. 2 mmol)、132 毫升 1M Na2C〇3(132 mmol)、500 毫升曱苯、及200毫升乙醇12小時。反應完成後，反應產 物以蒸餾水洗滌，再以乙酸乙酯萃取，之後所得有機層以 MgS〇4乾燥，使用旋轉蒸發器蒸發以移除溶劑，再使用管柱 色層分析純化，獲得11. 5克化合物9-2 (32. 9 mmol)。 化合物76之製備 在100°C回流下攪拌8. 1克化合物9-1 (23. 28 mmol)、 8. 7 克化合物 1-2(19. 4 mmol)、0. 13 克 PcKOAcMO. 58 mmol)、0. 94 毫升 P(t-Bu)3(2. 32 mmol)、6· 7 克 NaOt-Bu (69. 84匪〇1)及500毫升曱苯12小時。反應完成後，反應 產物以蒸餾水洗滌，再以乙酸乙酯萃取，之後所得有機層 以MgS〇4乾燥，使用旋轉蒸發器蒸發以移除溶劑，使用管 柱色層分析純化，並再結晶，獲得6.5克化合物76(9.0 mmol，47%) 〇 ΧΗ NMR(CDC13, 200 MHz) δ = 1.72 (12H, s) , 6.58(1H, m),Preparation of Compound 9-1 95199 34 201213501 Stir at 105 ° C under reflux of 10. 5 g of 9,9-dimercapto-9H-indol-2-ylboronic acid (44 mmol), 31 g of 1,4-dibromobenzene (132 mmol), 2.5 g of Pd(PPh3)4 (2.2 mmol), 132 ml of 1 M Na2C〇3 (132 mmol), 500 ml of toluene, and 200 ml of ethanol for 12 hours. After the completion of the reaction, the reaction product was washed with distilled water, and then extracted with ethyl acetate, and then the organic layer was dried with MgSO 4 , and evaporated using a rotary evaporator to remove the solvent. Compound 9-2 (32. 9 mmol). The preparation of the compound 76 was stirred under reflux at 100 ° C. 8. 1 g of compound 9-1 (23. 28 mmol), 8. 7 g of compound 1-2 (19.4 mmol), 0. 13 g of PcKOAcMO. 58 mmol) 0. 94 ml of P(t-Bu)3 (2.32 mmol), 6.7 g of NaOt-Bu (69.84匪〇1) and 500 ml of terpene for 12 hours. After completion of the reaction, the reaction product was washed with distilled water and extracted with ethyl acetate, and then the organic layer was dried with &lt;RTI ID=0.0&gt;&gt; 6.5 g of compound 76 (9.0 mmol, 47%) NMR (CDC13, 200 MHz) δ = 1.72 (12H, s), 6.58 (1H, m),

6.69-6.75 (5H, m) , 7.28(2H, m) , 7.38~7.41 (3H, in), 7.51~7.55 (10H, m), 7.62~7.63(2H, m) , 7.77 (1H, m) , 7.87~7.93(3H, m) ; MS/FAB 實測值630,計算值629.83 製備例10化合物78之製備 35 95299 2012135016.69-6.75 (5H, m) , 7.28(2H, m) , 7.38~7.41 (3H, in), 7.51~7.55 (10H, m), 7.62~7.63(2H, m) , 7.77 (1H, m) , 7.87~7.93(3H, m); MS/FAB found 630, calculated 629.83 Preparation of compound 78 of Preparation 10 35 95299 201213501

化合物10-1之製備 將40克2-溴苯甲酸甲酯（152. 6 mmol)、31. 5克萘-1- 基硼酸（183. 2 mmol)、及8. 8克肆（三苯基膦）鈀[pd(pph3)4] (7. 62 mmol)放置到2頸燒瓶中。於其内將1公升甲笨加入 時’進行擾拌，再於其内加入228毫升2M碳酸鉀（458 mmol) 及228毫升乙醇。在100°C下進行回流5小時。反應終止 後，反應產物冷卻至室溫，再以蒸顧水及乙酸乙醋萃取。 所得有機層以MgS〇4乾燥，使用旋轉蒸發器蒸發以移除溶 劑，使用己烧及乙酸乙S旨作為展開液進行管柱層析法，獲 得35克化合物10-1 (87%)。 化合物10-2之製備 將24克化合物10-1(91.49 mmol)放置到1頸燒瓶中， 使該燒瓶為真空並填充氬氣。於其内加入1公升四氫吱 喃，在-75°C進行攪拌1〇分鐘。隨後，於其内加入257毫 升（0. 41mol)MeLi(l· 6M，於己烷中），在-75°c 攪拌 八 鐘’及在室溫攪拌3小時。反應終止後’反應產物以蒸麵 水及乙酸乙酯萃取。所得有機層以MgS〇4乾燥，使用旋轉 95299 36 201213501 蒸發器蒸發以移除溶劑’使用己烷及乙酸乙酯作為展開液 進行管柱層析法，獲得20克化合物i〇_2(83%)。 化合物10-3之製備 將20克化合物10-2(76. 23 mmol)放置到1頸燒瓶中， 並於其内加入3〇〇毫升AcOH並在〇。(：攪拌1〇分鐘。反應 混合物加入4〇〇毫升HsPO4並在室溫攪拌1小時。反應終止 後’反應產物以Na〇H中和’並以蒸餾水及乙酸乙酯萃取。 所得有機層以MgS〇4乾燥，使用旋轉蒸發器蒸發以移除溶 劑’並使用己烷及乙酸乙酯作為展開液進行管柱層析法， 獲得13.5克化合物10-3(72%)。 化合物10-4之製備 將13. 5克化合物1〇_3 (55. 25 mmol)放置到1頸燒瓶 中’使該燒瓶為真空並填充氬氣。於其内加入500毫升四 氫°夫喃’在0¾進行攪拌分鐘。隨後，反應混合物加入 19· 6克NBS (〇. 11 mol)並在室溫攪拌一天。反應終止後， 反應產物以蒸餾水及乙酸乙酯萃取。所得有機層.以MgSChPreparation of Compound 10-1 40 g of methyl 2-bromobenzoate (152. 6 mmol), 31.5 g of naphthalen-1-ylboronic acid (183. 2 mmol), and 8.8 g of hydrazine (triphenyl) Palladium [pd(pph3)4] (7. 62 mmol) was placed in a 2-neck flask. During the addition of 1 liter of Azure, the mixture was stirred and 228 ml of 2M potassium carbonate (458 mmol) and 228 ml of ethanol were added thereto. The reflux was carried out at 100 ° C for 5 hours. After the reaction was terminated, the reaction product was cooled to room temperature, and extracted with water and ethyl acetate. The obtained organic layer was dried with MgSO 4 , evaporated using a rotary evaporator to remove solvent, and column chromatography was carried out using hexane and ethyl acetate as a solvent to obtain 35 g of compound 10-1 (87%). Preparation of Compound 10-2 24 g of Compound 10-1 (91.49 mmol) was placed in a 1-neck flask, and the flask was vacuumed and filled with argon. One liter of tetrahydrofuran was added thereto, and the mixture was stirred at -75 ° C for 1 minute. Subsequently, 257 ml (0.41 mol) of MeLi (1.6 M in hexane) was added thereto, stirred at -75 ° C for eight hours and stirred at room temperature for 3 hours. After the reaction was terminated, the reaction product was extracted with distilled water and ethyl acetate. The obtained organic layer was dried over MgS 〇 4 and evaporated using a rotary s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s ). Preparation of Compound 10-3 20 g of Compound 10-2 (76.23 mmol) was placed in a 1-neck flask, and 3 mL of AcOH was added thereto and placed in hydrazine. (: stirring for 1 hr. The reaction mixture was added to 4 ml of HsPO4 and stirred at room temperature for 1 hour. After the reaction was terminated, the reaction product was neutralized with Na〇H and extracted with distilled water and ethyl acetate. The crucible 4 was dried, evaporated using a rotary evaporator to remove the solvent, and subjected to column chromatography using hexane and ethyl acetate as a solvent to obtain 13.5 g of compound 10-3 (72%). Preparation of Compound 10-4 13.5 g of compound 1 〇 3 (55. 25 mmol) was placed in a 1-necked flask. 'The flask was vacuumed and filled with argon. 500 ml of tetrahydrofuran was added thereto and stirred at 03⁄4. Subsequently, the reaction mixture was added to 19.6 g of NBS (〇.11 mol) and stirred at room temperature for one day. After the reaction was terminated, the reaction product was extracted with distilled water and ethyl acetate.

—，J - 化合物 在 10〇h , 克化合物1 之製備 上6亳升P(t〜Bu) 及8〇〇毫升曱笨—, J - compound at 10 〇h, gram of compound 1 was prepared by 6 liters of P(t~Bu) and 8 〇〇ml

拌 8. 3 克苯胺（88. 64 mmol)、28. 6 • b4 mmol)、0. 6 克 Pd(0AcM2. 7 mmol)、 &gt;3(8. 9 mmol)、25· 5 克 NaOt-Bu (266 mmol) 12小時。反應完成後，反應產物以蒸餾水 37 95299 201213501 洗滌’再以乙酸乙酯萃取，之後所得有機層以MgS〇4乾燥， 使用旋轉蒸發器蒸發以移除溶劑，並使用管柱色層分析純 化，獲得10. 1克化合物10-5(30. 1 mmol)。 化合物78之製備 在100°C回流下攪拌7. 9克化合物卜3(23. 28 mmol)、 6. 5 克化合物 10-5(19. 4 mmol)、0. 13 克 Pd(OAcM〇. 58 mmol)、0. 94 毫升 P(t-Bu)3(2. 32 mmol)、6. 7 克 NaOt-Bu (69. 84 mmol)及500毫升曱苯12小時。反應完成後，反應 產物以蒸餾水洗滌，再以乙酸乙酯萃取，之後所得有機層 以MgS〇4乾燥，使用旋轉蒸發器蒸發以移除溶劑，使用管 柱色層分析純化，並再結晶，獲得6. 0克化合物78 (10. 1 mmol，52%) 〇 XH NMR(CDC13, 200 ΜΗζ)δ = 1.78(βΗ, s) , 6.63~β.69(5Η, m), 6.8K2H, m), 7.14(1Η, m) , 7.2(2Η, m) , 7.5~7.58(7Η, m) , 7.84(1Η, m), 7.98(2Η, m), 8.09(1Η, m), 8.2(1Η, m), 8.41〜8·45(2Η, m), 8.52(1Η, m); MS/FAB 實測值 594,計算值 593.78 [實施例1]使用本發明之有機EL化合物之0LED裝置的製 造 使用本發明之發光材料製造0LED裝置。首先，使用 超音波依序以三氯乙烯、丙酮、乙醇及蒸餾水清洗取自 0LED用玻璃（Samsung-Corning所製得）之透明電極IT0薄 膜（15Ω/口），並儲存於異丙醇中備用。然後，將π〇基板 裝配於真空氣相沉積裝置之基板夾中’並將4,4，，4” -參 (N，N-(2-萘基）-苯基胺基）三苯胺（2-TNATA)置於該真空氣 38 95299 201213501 相沉積裝置之一小室中，然後抽氣使該腔室内達到1〇-6托 (torr)真空。然後，對該小室施加電流以蒸發2_tnata , 從而於該ΙΤ0基板上沉積厚度為60奈米（nm)之電洞注入 層。接著，將本發明之化合物13置於該真空氣相沉積裝置 之另一小室中，並對該小室施加電流以蒸發化合物13，從 而於該電洞注入層上沉積厚度為20 nm之電洞傳輸層。形 成該電洞注入層及電洞傳輸層之後’於所形成的層上沉積 電場發光層。具體而言，將4,4’ -N，N’ -二咔唑_聯苯（CpB) 主體置於該真空沉積裝ί之一小室中’並將雙~(卜苯基異 喹啉基）銥（III)乙醯丙酮（（PiqMr(acac))摻雜劑置於另 一小室中。然後，以不同速率蒸發該兩種材料，從而以4 至10重量％之摻雜而於該電洞傳輸層上沉積厚度為3〇nm 之電場發光層。接著，於該電場發光層上沉積厚度為10nm 之包含雙（2-甲基-8-羥基喧琳基）（對-苯基酚基）鋁（in) (Balq)之電洞阻隔層，之後，沉積厚度為20nm之包含參 羥基喹啉）鋁（III)(Alq)l電子傳輸層。然後’沉積厚度為 1 至 2nm 之 8-羥基喹啉鏍（lithium Quinolate，Liq)作為 電子注入層，及使用另真工;儿積裝置沉積厚度為15〇ηιη 之鋁（Α1)陰極，從而製造出0LED裝置。 用於該0LED裝置作為發光材料之各個化合物皆是已 藉由在10-6 torr真空昇華而純化者。 結果，7.0 V電壓下有電流15.3毫安培（mA)/平方公 分（cm2)流動，獲得1120燭光（Cd)/cm2之紅色發光。 [實施例2]使用本發明之有機EL化合物之〇LED裝置的製 95299 39 201213501 造 除了使用本發明之化合物3作為電洞傳輸材料之外， 根據實施例1所述之相同方法製造0LED裝置。 結果，7.2V電壓下有電流15. ImA/cm2流動，獲得1075 cd/cm2之紅色發光。 [實施例3]使用本發明之有機EL化合物之OLED裝置的製 造 除了使用本發明之化合物35作為電洞傳輸材料之外， 根據實施例1所述之相同方法製造0LED裝置。 結果，7. 3V電壓下有電流16.3 mA/cm2流動，獲得1115 cd/cm2之紅色發光。 [實施例4]使用本發明之有機EL化合物之0LED裝置的製 造 除了改於電場發光層使用本發明之化合物49作為電 洞傳輸材料及使用有機銥錯合物參（2-苯基。比啶）銥 (Ir(ppy)3)作為電場發光層中之換雜劑之外，根據實施例 1所述之相同方法製造0LED裝置。 結果，6. 8 V電壓下有電流4. 0 mA/cm2流動，獲得1160 cd/cm2之綠色發光。 [實施例5]使用本發明之有機EL化合物之0LED裝置的製 造 除了使用本發明之化合物58作為電洞傳輸材料之外， 根據實施例4所述之相同方法製造OLED裝置。 結果，7. 1 V電壓下有電流4. 2 mA/cm2流動，獲得1230 40 95299 201213501 cd/cm2之綠色發光。 [實施例6]使用本發明之有機EL化合物之OLED裝置的製 造 除了使用本發明之化合物4作為電洞傳輸材料之外， 根據實施例4所述之相同方法製造0LED裝置。 結果，7. 2 V電壓下有電流5. 0 mA/cm2流動，獲得1570 cd/cm2之綠色發光。 [實施例7]使用本發明之有機EL化合物之0LED裝置的製 造 除了使用本發明之化合物61作為電洞傳輸材料之外， 根據實施例4所述之相同方法製造0LED裝置。 結果，7. 0 V電壓下有電流3. 9 mA/cm2流動，獲得1300 cd/cm2之綠色發光。 [實施例8]使用本發明之有機EL化合物之0LED裝置的製 造 除了使用本發明之化合物42代替2-TNATA(4,4’，4” -參（N，N-(2-萘基）-苯基胺基）三苯胺）作為電洞注入材料之 外，根據實施例1所述之相同方法製造0LED裝置。 結果，6.8V電壓下有電流13.5mA/cm2流動，獲得1040 cd/cm2之紅色發光。 [實施例9]使用本發明之有機EL化合物之0LED裝置的製 造 除了使用本發明之化合物45代替2-TNATA(4,4’，4” -參（N，N-(2-萘基）-苯基胺基）三苯胺）作為電洞注入材料之 41 95299 201213501 外，根據實施例4所述之相同方法製造0LED裝置。 結果，6.6V電壓下有電流4. OmA/cm2流動’獲得1235 cd/cm2之綠色發光。 [實施例10]使用本發明之有機EL化合物之0LED裝置的 製造 除了使用本發明之化合物46代替2-TNATA(4,4’，4” -參（N，N-(2-萘基）-苯基胺基）三苯胺）作為電洞注入材料之 外，根據實施例1所述之相同方法製造0LED裝置。 結果，7. 2V電壓下有電流13.7mA/cm2流動，獲得 1005cd/cm2之紅色發光。 [比較例1]使用傳統發光材料之0LED之發光性質 除了於真空沉積裝置之一小室中改成使用N，N’ -雙 (α-萘基）_n，n’ -二苯基-4,4’ -二胺（NPB)代替本發明之 化合物作為電洞傳輸材料之外，根據實施例1所述之相同 方法製造0LED裝置。 結果’7. 5V電壓下有電流i5.3mA/cm2流動，獲得1〇〇〇 cd/cm2之紅色發光。 [比較例2]使用傳統發光材料之0LED之發光性質 除了於真空沉積裝置之一小室中改成使用N，N’一雙 (α_萘基）~N，N’ _二苯基〜4,4, _二胺（NPB)代替本發明之 化合物作為電洞傳輸材料之外，根據實施例4所述之相同 方法製造0LED裝置。 結果，7. 5V電壓下有電流3. 8mA/cm2流動，獲得1〇〇〇 cd/cm2之綠色發光。 42 95299 201213501 與傳統材料相比，本發明之有機EL化合物具有優異之 發光性質。又，使用本發明之有機EL化合物作為電洞傳輸 材料或電洞注入材料的有機E L裝置可提高L U Μ 0 (最低未經 佔據分子軌道）及增加三重態（tr iρ 1 et)，從而增強電洞阻 擔效應（blocking effect)，獲得良好填光效率及較高材料 壽命性質。再者，可降低操作電壓，及可增加功率效率， 從而製造出優異之0LED裝置。 雖然本發明之較佳具體實施例業揭示作為說明目的， 但此技術領域中具有通常知識者應了解，可對該等較佳具 體實施例進行各種修飾、增加及取代而不悖離後附申請專 利範圍所界定之本發明所揭示内容的精神與範疇。 【圖式簡單說明】 無 【主要元件符號說明】 無 43 95299Mix 8.3 g of aniline (88.64 mmol), 28.6 • b4 mmol), 0.6 g of Pd (0 AcM 2. 7 mmol), &gt; 3 (8.9 mmol), 25 · 5 g of NaOt-Bu (266 mmol) 12 hours. After completion of the reaction, the reaction product was washed with distilled water 37 95299 201213501 and then extracted with ethyl acetate. The organic layer obtained was then dried with MgSO 4 , evaporated using a rotary evaporator to remove solvent and purified by column chromatography. 10. 1 g of compound 10-5 (30. 1 mmol). The preparation of the compound 78 was stirred under reflux at 100 ° C. 7. 9 g of compound b 3 (23. 28 mmol), 6. 5 g of compound 10-5 (19.4 mmol), 0.13 g of Pd (OAcM〇. 58 Methyl), 0.94 ml of P(t-Bu)3 (2.32 mmol), 6.7 g of NaOt-Bu (69.84 mmol) and 500 ml of toluene for 12 hours. After completion of the reaction, the reaction product was washed with distilled water and extracted with ethyl acetate, and then the organic layer was dried with &lt;RTI ID=0.0&gt;&gt; 6. 0g compound 78 (1. 1 mmol, 52%) 〇XH NMR (CDC13, 200 ΜΗζ) δ = 1.78 (βΗ, s) , 6.63~β.69 (5Η, m), 6.8K2H, m), 7.14(1Η, m) , 7.2(2Η, m) , 7.5~7.58(7Η, m) , 7.84(1Η, m), 7.98(2Η, m), 8.09(1Η, m), 8.2(1Η, m) , 8.41 to 8.45 (2Η, m), 8.52 (1Η, m); MS/FAB measured value 594, calculated value 593.78 [Example 1] Manufacture of an OLED device using the organic EL compound of the present invention using the present invention The luminescent material is manufactured as an OLED device. First, the transparent electrode IOT film (15 Ω/□) taken from the OLED glass (made by Samsung-Corning) was washed with trichloroethylene, acetone, ethanol and distilled water in the order of ultrasonic waves, and stored in isopropyl alcohol. . Then, the π-inch substrate was assembled in the substrate holder of the vacuum vapor deposition apparatus 'and 4,4,,4"-parameter (N,N-(2-naphthyl)-phenylamino)triphenylamine (2 -TNATA) is placed in a chamber of the vacuum gas 38 95299 201213501 phase deposition device, and then evacuated to bring the chamber to a vacuum of 1 〇 to Torr. Then, a current is applied to the chamber to evaporate 2_tnata, thereby A hole injection layer having a thickness of 60 nm is deposited on the substrate. Next, the compound 13 of the present invention is placed in another chamber of the vacuum vapor deposition apparatus, and an electric current is applied to the chamber to evaporate the compound. 13. Depositing a hole transport layer having a thickness of 20 nm on the hole injection layer. After forming the hole injection layer and the hole transport layer, an electric field light-emitting layer is deposited on the formed layer. Specifically, 4,4'-N,N'-dicarbazole-biphenyl (CpB) is placed in a chamber of the vacuum deposition apparatus' and will be bis(p-phenylisoquinolinyl)ruthenium(III) The argon acetone ((PiqMr(acac))) dopant is placed in another chamber. Then, the two materials are evaporated at different rates to 4 to 10% by weight of doping to deposit an electric field luminescent layer having a thickness of 3 〇 nm on the hole transport layer. Then, a thickness of 10 nm is deposited on the electroluminescent layer containing bis(2-methyl-8- a hole-blocking layer of (p-phenylphenolyl)aluminum (in) (Balq), followed by deposition of a thickness of 20 nm comprising a quinolinol) aluminum (III) (Alq) l electron transport layer Then, 'lithium Quinolate (Liq) with a thickness of 1 to 2 nm is deposited as an electron injecting layer, and an aluminum (Α1) cathode having a thickness of 15 〇ηηη is deposited by using a device; An OLED device was fabricated. Each of the compounds used as the luminescent material for the OLED device has been purified by vacuum sublimation at 10-6 torr. As a result, a current of 15.3 milliamperes (mA) per square centimeter at a voltage of 7.0 V ( Cm2) flow, obtaining red light emission of 1120 candelas (Cd)/cm2. [Example 2] 9529999 39 201213501 using 〇LED device of the organic EL compound of the present invention The use of the compound 3 of the present invention as a hole transport material was eliminated. In addition, the 0L is manufactured in the same manner as described in Embodiment 1. ED device. As a result, a current of 15. ImA/cm2 was flowed at a voltage of 7.2 V, and red light emission of 1075 cd/cm 2 was obtained. [Example 3] Production of an OLED device using the organic EL compound of the present invention except that the compound of the present invention was used. 35. As the hole transporting material, an OLED device was fabricated in the same manner as described in Example 1. As a result, a current of 16.3 mA/cm2 was flowed at a voltage of 7.3 V, and red light emission of 1,115 cd/cm2 was obtained. [Example 4] Production of OLED device using the organic EL compound of the present invention In addition to the electroluminescent layer, the compound 49 of the present invention was used as a hole transporting material and an organic ruthenium complex (2-phenyl group) was used. An erbium (Ir (ppy) 3) was used as the dopant in the electric field light-emitting layer, and an OLED device was fabricated in the same manner as in Example 1. As a result, a current of 4. 0 mA/cm 2 was flowed at a voltage of 6.8 V, and green light of 1160 cd/cm 2 was obtained. [Example 5] Production of OLED device using the organic EL compound of the present invention An OLED device was produced in the same manner as in Example 4, except that the compound 58 of the present invention was used as the hole transporting material. As a result, a current of 4.2 mA/cm2 was flowed at a voltage of 7. 1 V, and green light of 1230 40 95299 201213501 cd/cm 2 was obtained. [Example 6] Production of OLED device using the organic EL compound of the present invention An OLED device was produced in the same manner as in Example 4, except that the compound 4 of the present invention was used as the hole transporting material. As a result, a current of 5.0 mA/cm2 was flowed at a voltage of 7.2 V, and green light of 1570 cd/cm2 was obtained. [Example 7] Production of OLED device using organic EL compound of the present invention An OLED device was produced in the same manner as in Example 4, except that the compound 61 of the present invention was used as the hole transporting material. As a result, a current of 3. 9 mA/cm 2 was flowed at a voltage of 7.0 V, and green light of 1300 cd/cm 2 was obtained. [Example 8] Production of an OLED device using the organic EL compound of the present invention, except that the compound 42 of the present invention was used instead of 2-TNATA (4,4',4"-parameter (N,N-(2-naphthyl)- Phenylamino)triphenylamine) As the hole injecting material, an OLED device was produced in the same manner as in Example 1. As a result, a current of 13.5 mA/cm 2 was flowed at a voltage of 6.8 V, and a red color of 1040 cd/cm 2 was obtained. [Example 9] Production of an OLED device using the organic EL compound of the present invention, except that the compound 45 of the present invention was used instead of 2-TNATA (4,4',4"-parameter (N,N-(2-naphthyl) )-Phenylamino)triphenylamine) As a hole injecting material 41 95299 201213501, an OLED device was produced in the same manner as in Example 4. As a result, there was a current of 4. OmA/cm2 flowing at a voltage of 6.6 V to obtain green light emission of 1235 cd/cm2. [Example 10] Production of an OLED device using the organic EL compound of the present invention, except that the compound 46 of the present invention was used instead of 2-TNATA (4,4',4"-parameter (N,N-(2-naphthyl)- Phenylamino)triphenylamine) As the hole injecting material, an OLED device was produced in the same manner as in Example 1. As a result, a current of 13.7 mA/cm2 was flowed at a voltage of 7.2 V, and a red color of 1005 cd/cm2 was obtained. [Comparative Example 1] Luminescence properties of OLEDs using conventional luminescent materials were changed to use N,N'-bis(α-naphthyl)_n,n'-diphenyl-4 in addition to one of the chambers of the vacuum deposition apparatus. An OLED device was fabricated in the same manner as described in Example 1 except that the 4'-diamine (NPB) was used as the hole transporting material. Results '7. Current at a voltage of 5 V was flowed at i5.3 mA/cm2 , a red luminescence of 1 〇〇〇 cd/cm 2 was obtained. [Comparative Example 2] The luminescent property of OLED using a conventional luminescent material was changed to use N, N'-double (α-naphthyl group) in addition to one chamber of a vacuum deposition apparatus. )~N,N' _diphenyl~4,4,diamine (NPB) instead of the compound of the present invention as a hole transport material The OLED device was fabricated in the same manner as described in Example 4. As a result, a current of 3. 8 mA/cm 2 was flowed at a voltage of 7.5 V, and green luminescence of 1 〇〇〇 cd/cm 2 was obtained. 42 95299 201213501 Compared with conventional materials The organic EL compound of the present invention has excellent luminescent properties. Further, an organic EL device using the organic EL compound of the present invention as a hole transporting material or a hole injecting material can improve LU Μ 0 (minimum unoccupied molecular orbital) and Increasing the triplet state (tr iρ 1 et), thereby enhancing the blocking effect of the hole, achieving good filling efficiency and high material lifetime properties. Furthermore, the operating voltage can be lowered and the power efficiency can be increased to manufacture DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT OF THE INVENTION While the preferred embodiments of the present invention are disclosed for purposes of illustration, it will be understood by those of ordinary skill in the art The spirit and scope of the disclosure of the present invention as defined by the appended claims is not exhausted. [Simplified illustration] No [main component symbol] Ming None 4,395,299

Claims (1)

201213501 七、申請專利範圍： 1. 一種下列化學式丨表示之有機電場發光化合物：201213501 VII. Patent application scope: 1. An organic electric field luminescent compound represented by the following chemical formula: 其中，X 表示-0-、-S-、-c(RllRl2)一或—Si(RnRi4)_， 其中’ Ru至R14係獨立表示氫、氘、齒素、經取代咬未 經取代之（C1-C30)烷基、經取代或未經取代之（C6_a〇) 芳基、經取代或未經取代2(C3_C3〇)雜芳基、經取代或 未經取代之5至7員雜環烷基、或經取代或未經取代之 (C3-C30)環烷基，或心至Ru係鏈結至相鄰取代基以形 成壞， Ri至R4係獨立表示氫、氘、鹵素、經取代或未經 取代之（C1-C30)烷基、經取代或未經取代之（C6_C3〇) 芳基、經取代或未經取代2(C3_C3〇)雜芳基、經取代或 未經取代之（C3-C30)環烷基、經取代或未經取代之5 至7員雜環烷基、經取代或未經取代之（C6_C3〇)芳基 (C卜C30)烷基、與一個或多個環烷基稠合之經取代或未 經取代之（C6-C30)芳基、與一個或多個經取代或未經取 代之芳香環稠合之5至7貝雜環絲或與-個或多個經 取代或未經取代之芳香環稠合之（C3-C30)環烷基、經取 95299 1 201213501 代或未經取代之（C1_C30)石夕烧基、氰基、硝基或經基 其中當仏至匕係以複數存在者，則它們互相鍵結以形 成環狀結構； R5及R6係表示氫、氘、鹵素、經取代或未經取代 • 之（C1_C3〇)烷基、經取代或未經取代之（C6-C30)芳基、 * 娜代絲經取代之⑹-⑽雜芳基、或經取代或^經 取代之5員至雜環絲，或&amp;及Re係鏈結至相鄰 取代基以形成環； L!及L2係獨立表示化學鍵、經取代或未經取代之 (C6-C3())伸芳基、或經取代或未經取代之（G3—⑽）伸雜 芳基，排除其中Li及L2皆為化學鍵之例； Ar係表示經取代或未經取代之（C6_C3〇)芳基、除 了咔唑以外之經取代或未經取代之（C3-C30)雜芳基、經 取代或未經取代之5至7員雜環烷基、與一個或多1個環 烷基稠合之經取代或未經取代之（C6-C30)芳基、與一個 或多個經取代或未經取代之芳香環稠合之經取代或未 經取代之（C3-C30)雜芳基、與一個或多個經取代或未經 取代之芳香環稠合之5至7員雜環烧基，或者紅係^ 由具有或不具有稠合環之（C3-C30)伸烷基或（C3_C3^’ 伸烯基鏈結至相鄰取代基以形成脂環族環及單環或夕 環之芳香環； 夕 a至d係獨立表示〇至4的整數，其中，當8至4 為2或更大的整數時，Ri、及心係互相為相同或 不同，且Rl、R”R3及匕係鏈結至相鄰取代基以形成環； 95299 2 201213501 以及 該雜環烷基及雜芳基含有一個或多個選自b、n、 〇、S、P(=0)、Si及p所組成群組之雜原子。 2.如申請專利範圍第1項所述之有機電場發光化合物，其 中，該進一步取代於Ri至R4、R5及、R&quot;至Rl4、Ll、 及Ar之取代基係表示一個或多個選自下列所組成群 組者：氘、鹵素、經il素取代或未經取代之（C1-C30)烷 基、（C6-C30)芳基、經（C6-C30)芳基取代或未經取代之 (C3-C30)雜芳基、5至7員雜壞烧基、與一個或多個芳 香環稠合之5至7員雜環烷基、（C3-C30)環烷基、與一 個或多個芳香環稠合之（C6-C30)環烧基u22R23si_、 (C2-C30)烯基、（C2-C30)炔基、氰基、咔唑基、NR24R25、 BR26R27、PR28R29、P(=0)R3〇R3i、（C6-C30)芳基（C1-C30) 烷基、（a-C30)烷基（C6-C30)芳基、r32s-、r33〇-、 R34C(=0)-、R35c(=0)0-、羧基、硝基及羥基，其中r2i 至R33係獨立表示氫、氘、鹵素、經取代或未經取代之 (C1-C30)烷基、經取代或未經取代之（C6_C3〇)芳基、經 取代或未經取代之（C3-C30)雜芳基、或經取代或未經取 代之5至7員雜環烷基，或者心至^係經由具有或不 具有稠合ί哀之經取代或未經取代之（C3_C3〇)伸烷基或 經取代或未經取代之（C3_C3〇)伸烯基鏈結至相鄰取代 f以=成脂環族環及單環❹環之料環，該形成之脂 裱族壞及單環或多環之芳香環的碳原子可經 一個或多 個選自氮、氧、及硫所組成群組之雜原子取代；以及 3 95299 201213501 R34及R35係表不（C1-C30)烧基、（C]_—c3〇)烧氧基、 (C6-C30)芳基或（C6-C3.0)芳氧基。 3.如申請專利範圍第丨項所述之有機電場發光化合物，其 中’ 5玄化學式1之有機電場發光化合物包括下列化學式 2至5表示之化合物： 化學式2Wherein X represents -0-, -S-, -c(RllRl2)- or -Si(RnRi4)_, wherein 'Ru to R14 are independently hydrogen, hydrazine, dentate, substituted bite unsubstituted (C1 -C30)alkyl, substituted or unsubstituted (C6_a〇) aryl, substituted or unsubstituted 2(C3_C3〇)heteroaryl, substituted or unsubstituted 5 to 7 membered heterocycloalkyl Or a substituted or unsubstituted (C3-C30) cycloalkyl group, or a core to Ru chain to an adjacent substituent to form a bad, Ri to R4 independently represent hydrogen, deuterium, halogen, substituted or not Substituted (C1-C30)alkyl, substituted or unsubstituted (C6_C3〇) aryl, substituted or unsubstituted 2(C3_C3〇)heteroaryl, substituted or unsubstituted (C3- C30) cycloalkyl, substituted or unsubstituted 5 to 7 membered heterocycloalkyl, substituted or unsubstituted (C6_C3 fluorene) aryl (C-C30) alkyl, and one or more naphthenes a fused or substituted (C6-C30) aryl group, a 5 to 7-shell heterocyclic ring fused to one or more substituted or unsubstituted aromatic rings, or with one or more Substituted or unsubstituted aromatic ring fused (C3-C30)cycloalkyl, taken 95259 1 201213501 or unsubstituted (C1_C30), cyano, nitro or thiol, wherein when 仏 to 匕 are present in plural, then they Bonded to form a cyclic structure; R5 and R6 represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1_C3〇) alkyl, substituted or unsubstituted (C6-C30) aryl, * Nades is substituted by (6)-(10)heteroaryl, or substituted or substituted 5 member to heterocyclic, or & and Re chain to adjacent substituent to form a ring; L! and L2 Independently means a chemical bond, a substituted or unsubstituted (C6-C3()) extended aryl group, or a substituted or unsubstituted (G3—(10)) heteroaryl group, excluding a case where both Li and L2 are chemical bonds. ; Ar represents a substituted or unsubstituted (C6_C3〇) aryl group, substituted or unsubstituted (C3-C30) heteroaryl group other than carbazole, substituted or unsubstituted 5 to 7 members a heterocycloalkyl group, a substituted or unsubstituted (C6-C30) aryl group fused to one or more cycloalkyl groups, and one or more substituted or unsubstituted a substituted or unsubstituted (C3-C30)heteroaryl group substituted with one or more substituted or unsubstituted aromatic rings, or a 5- to 7-membered heterocyclic alkyl group fused, or Red system ^ consists of a (C3-C30) alkyl group with or without a fused ring or a (C3_C3^' extended alkenyl chain to an adjacent substituent to form an alicyclic ring and a monocyclic or oxime ring ; 夕 a to d are independent integers representing 〇 to 4, wherein when 8 to 4 are integers of 2 or more, Ri and the heart are mutually the same or different, and R1, R"R3 and the lanthanide chain Junction to an adjacent substituent to form a ring; 95299 2 201213501 and the heterocycloalkyl and heteroaryl group containing one or more groups selected from the group consisting of b, n, 〇, S, P(=0), Si, and p Group of heteroatoms. 2. The organic electroluminescent compound according to claim 1, wherein the substituent further substituted with Ri to R4, R5 and R&quot; to R14, L1, and Ar means one or more selected from the group consisting of Groups of the following: hydrazine, halogen, il-substituted or unsubstituted (C1-C30) alkyl, (C6-C30) aryl, substituted by (C6-C30) aryl or unsubstituted (C3-C30)heteroaryl, 5 to 7 membered oxalate, 5 to 7 membered heterocycloalkyl fused to one or more aromatic rings, (C3-C30)cycloalkyl, with one or more Aromatic ring fused (C6-C30) cycloalkyl group u22R23si_, (C2-C30) alkenyl, (C2-C30) alkynyl, cyano, carbazolyl, NR24R25, BR26R27, PR28R29, P(=0) R3〇R3i, (C6-C30) aryl (C1-C30) alkyl, (a-C30)alkyl (C6-C30) aryl, r32s-, r33〇-, R34C(=0)-, R35c( =0) 0-, carboxy, nitro and hydroxy, wherein r2i to R33 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6_C3 Anthracene, substituted or unsubstituted (C3-C30)heteroaryl, or substituted or unsubstituted Substituting a 5- to 7-membered heterocycloalkyl group, or a substituted or unsubstituted (C3_C3 fluorene) alkyl group with or without a fused condensed alkyl group or substituted or unsubstituted (C3_C3) 〇) extending an alkenyl chain to an adjacent substituent f to = a cycloaliphatic ring and a monocyclic anthracene ring, the formed aliphatic steroidal and monocyclic or polycyclic aromatic ring may have a carbon atom Or a plurality of hetero atom substitutions selected from the group consisting of nitrogen, oxygen, and sulfur; and 3 95299 201213501 R34 and R35 are represented by (C1-C30) alkyl, (C)_-c3〇 alkoxy, (C6-C30) aryl or (C6-C3.0) aryloxy. 3. The organic electroluminescent compound according to claim 5, wherein the organic electroluminescent compound of the formula 5 comprises the compounds represented by the following chemical formulas 2 to 5: Chemical formula 2 化學式3Chemical formula 3 化學式4Chemical formula 4 4 95299 201213501 化學式5 (R3)c4 95299 201213501 Chemical Formula 5 (R3)c 在化學式2至5中，X、Ri至R4、Rs及R6、Li、L2、 Ar及a至d之定義係如化學式1中之定義。 4.如申請專利範圍第1項所述之有機電場發光化合物，其 係選自下列化合物所組成群組者：In Chemical Formulas 2 to 5, X, Ri to R4, Rs and R6, Li, L2, Ar and a to d are as defined in Chemical Formula 1. 4. The organic electroluminescent compound according to claim 1, wherein the organic electroluminescent compound is selected from the group consisting of the following compounds: 5 95299 2012135015 95299 201213501 6 95299 2012135016 95299 201213501 95299 20121350195299 201213501 95299 20121350195299 201213501 5. —種有機電場發光裝置，係包括申請專利範圍第1至4 項中任一項所述之有機電場發光化合物。 6. 如申請專利範圍第5項所述之有機電場發光裝置，其 中，該有機電場發光化合物係用作為電洞注入材料或電 洞傳輸材料。 7. 如申請專利範圍第6項所述之有機電場發光裝置，其係 包括第一電極；第二電極；以及一層或多層插置於該第 95299 201213501 / : 一電極與該第二電極間之有機層，其中，該有機層包括 鬌 一種或多種化學式1之有機電場發光化合物。 8. 如申請專利範圍第7項所述之有機電場發光裝置，其中， 該有機層進一步包括一種或多種選自下列組成群組之 金屬：元素週期表之第1族、第2族、第4周期與第5 • 周期之過渡金屬、鑭系金屬及d-過渡元素之有機金屬； 或錯合物化合物。 9. 如申請專利範圍第7項所述之有機電場發光裝置，其 中，該有機層包括電場發光層及電荷產生層兩者。 10. 如申請專利範圍第7項所述之有機電場發光裝置，其 中，該有機層進一步包括一層或多層發射紅光、綠光或 藍光之有機電場發光層以發射白光。 10 95299 201213501 四 、指定代表圖： (一) 本案指定代表圖為：第（）圖。（本案無圖式) (二) 本代表圖之元件符號簡單說明：（無） 本案若有化學式時，請揭示最能顯示發明特徵的化學式： 化學式15. An organic electric field illuminating device, comprising the organic electroluminescent compound according to any one of claims 1 to 4. 6. The organic electroluminescent device according to claim 5, wherein the organic electroluminescent compound is used as a hole injecting material or a hole transporting material. 7. The organic electric field illuminating device according to claim 6, comprising a first electrode; a second electrode; and one or more layers interposed between the electrode 95299 201213501 / : an electrode and the second electrode An organic layer, wherein the organic layer comprises one or more organic electroluminescent compounds of Chemical Formula 1. 8. The organic electroluminescent device of claim 7, wherein the organic layer further comprises one or more metals selected from the group consisting of: Group 1, Periodic, and Fourth of the Periodic Table of the Elements; An organometallic with a transition metal, a lanthanide metal, and a d-transition element in the cycle and the 5th cycle; or a compound of a complex. 9. The organic electroluminescent device of claim 7, wherein the organic layer comprises both an electric field luminescent layer and a charge generating layer. 10. The organic electroluminescent device of claim 7, wherein the organic layer further comprises one or more layers of an organic electroluminescent layer emitting red, green or blue light to emit white light. 10 95299 201213501 IV. Designated representative map: (1) The representative representative of the case is: (). (There is no picture in this case) (2) The symbol of the symbol of this representative figure is simple: (none) If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: Chemical Formula 1 2 952992 95299
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