TW201204729A

TW201204729A - Novel compounds for organic electronic material and organic electroluminescent device using the same

Info

Publication number: TW201204729A
Application number: TW100111966A
Authority: TW
Inventors: Soo-Yong Lee; Young-Jun Cho; Hyuck-Joo Kwon; Bong-Ok Kim; Sung-Min Kim
Original assignee: Rohm & Haas Elect Mat
Priority date: 2010-04-09
Filing date: 2011-04-07
Publication date: 2012-02-01
Also published as: KR20110113297A; WO2011126225A1

Abstract

Provided are novel compounds for organic electronic material and an organic electroluminescent device using the same. Since the compound for organic electric material exhibits excellent electron transport efficiency, it may prevent crystallization during the production of devices. Further, since it provides good layer formation, it may improve electrical current property of devices. Therefore, it may be used to manufacture OLED devices having reduced driving voltage and improved power efficiency.

Description

201204729 '六、發明說明：【發明所屬之技術領域】本發明係關於有機電子材料之新穎化合物，及使用該 -化合物之有機電場發光裝置。更特別地，該有機電子材料 ' 化合物係用作傳輸材料。 ’ 【先前技術】於顯示器裝置中，作為自發光顯示器駿置之電場發光 (electroluminescent，EL)裝置係有利地提供寬視角:傑出之對比度及快響應速度者。1987年，伊斯門_柯達 '、 (Eastman Kodak)首先研發了一種使用低分子量之芳香一胺及鋁之錯合物作為形成電場發光層之物質之有機置[dpp/. Zeii. 51，913，1987]。、有機EL裝置是一種於其中當將電荷施加至形成於電子注入電極（陰極）與電洞注入電極（陽極）之間的有機'膜時，電子與電洞成對並隨後伴隨發光而失效之裝置。聿置可形成於透明撓性基板如塑膠上。與電聚顯示器面板或無機EL顯示器相比’該裝置可以較低電壓（不超過1〇伏特操作，消耗相對較少之電能，但提供優異之色純度。於有機EL裝置中’決定其包括發光效率及操^壽命之效能的最重要因子係電場發光材料。該電場發光材料之若干需求係包括於固態之高榮光量子產率、高電子及電同遷移性、真空沉積過程中之抗分解性、形成均句薄膜之能力及安定性。 1=1 有機電場發光材觸常可分為高分子量材料及低分 95193 3 201204729 子量材料。該低分子量材料可根據分子結構分為金屬錯合物及不含金屬之純有機電場發光材料。此等電場發光材料係包括螯合錯合物如參（8-羥基喹啉）鋁錯合物、香豆素衍生物、四苯基丁二烯衍生物、雙（桂皮基伸芳基）衍生物及噚二唑衍生物。據報導，使用彼等材料可獲得自藍至紅可見光區域之電場發光。為了達成全彩有機發光二極體（〇LED)顯示器，使用了二種（紅、綠及藍）電場發光材料。為了提升有機電場發光 (EL)裝置之整體特性’重點為開發具有高效率及長壽命之紅、綠及藍電場發光㈣。電場發光材料從其功能方面可分為主體（host)材料及摻雜㈣料。通常認為，使用藉由將摻雜劑摻雜人主體材中而製備之電場發光層可製造具有最優異EL性質的裝置結構。最近，開發具有高效率及長壽 «ρ之有機EL裝置已成為急需解決的議題，而慮及_型至大型0LED面板所需之此性質’特別緊迫者係開發具有遠遠優於常規EL材料之EL性質的材料。又，作為常規電子傳輸材料之代表性實例係有紹錯合物’例如K_k於1987年宣伟了在多層薄膜瞻之前使用的參㈣!基料）㉖⑴丨）（Alq);以及鈹錯合物，例如曰本於腳年代中葉宣佈了雙（1M!基苯并[h]啥琳）鈹 (Bebq)[T. Satoet.al. J. Mater. Chem. 10(2000) i151] 〇然而，於彼等材料之例中，隨著自_年以來_的商業化’他們之局限性逐步浮現。由於自那時起業已研究且存在很多具有㈣能之電子傳輪材料，他們亟待商業化。 95193 4 201204729201204729 'VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to novel compounds of organic electronic materials, and organic electric field light-emitting devices using the same. More particularly, the organic electronic material 'compound is used as a transport material. [Prior Art] In the display device, an electroluminescent (EL) device which is a self-luminous display is advantageously provided with a wide viewing angle: excellent contrast and fast response speed. In 1987, Eastman Kodak first developed an organic compound using a low molecular weight aromatic-amine and aluminum complex as a substance for forming an electroluminescent layer [dpp/. Zeii. 51,913 , 1987]. An organic EL device is one in which when an electric charge is applied to an organic 'film formed between an electron injecting electrode (cathode) and a hole injecting electrode (anode), the electrons are paired with the holes and subsequently fail with the light emission. Device. The device can be formed on a transparent flexible substrate such as plastic. Compared with electro-polymerized display panels or inorganic EL displays, the device can operate at a lower voltage (no more than 1 volt operation, consumes relatively little power, but provides excellent color purity. In organic EL devices, it determines its inclusion of luminescence) The most important factor of efficiency and lifetime performance is the electric field luminescent material. Some requirements of the electric field luminescent material include high-growth quantum yield in solid state, high electron and electrical mobility, and resistance to decomposition during vacuum deposition. The ability to form a uniform film and stability. 1=1 Organic electric field luminescent materials can be divided into high molecular weight materials and low score 95193 3 201204729 sub-materials. The low molecular weight materials can be divided into metal complexes according to molecular structure. And metal-free pure organic electric field luminescent materials. These electroluminescent materials include chelating complexes such as ginseng (8-hydroxyquinoline) aluminum complex, coumarin derivatives, tetraphenylbutadiene derivatives. , bis (cinnaminyl) derivatives and oxadiazole derivatives. It has been reported that electric light luminescence from the blue to red visible region can be obtained using these materials. Color organic light-emitting diode (〇LED) display uses two kinds of (red, green and blue) electric field luminescent materials. In order to improve the overall characteristics of organic electroluminescent (EL) devices, the focus is on developing high efficiency and long life. Red, green and blue electric field luminescence (4). The electric field luminescent material can be divided into host material and doping (four) material from its functional aspect. It is generally considered that an electric field prepared by doping a dopant into a human body material is used. The light-emitting layer can produce a device structure having the most excellent EL properties. Recently, the development of an organic EL device having high efficiency and longevity has become an urgent problem to be solved, taking into account the nature required for the _ type to large OLED panel. The urgency is to develop materials with EL properties far superior to those of conventional EL materials. Also, as a representative example of conventional electron transport materials, there are complexes such as K_k, which was used in 1987 by Xuan Wei in the multilayer film. (4)! Base material) 26(1)丨)(Alq); and 铍合物 complex, such as 曰宣布 announced in the middle of the foot of the double (1M! Benzene [h] 啥 Lin) 铍 (Bebq) [T. Satoet .al. J. Mater. Chem 10(2000) i151] 〇 However, in the case of their materials, the limitations of commercialization since the beginning of the year have gradually emerged. Since they have been researched since then and there are many electronic transmission materials with (4) energy, they need to be commercialized. 95193 4 201204729

同時，作為非金屬錯合物系列，迄今為止所宣佈之具有良好性貝之電子傳輸材料係包括螺_PBD[n· Johansson et. al. Adv. Mater. 10(1998)1 136]、PyPySPyPy[M. Uchidaet. al· Chem. Mater. 13(2001) 2680]以及 Kodak 之 TPBI[Y.-T. Tao et.al. Appl. Phys· Lett. 77(2000)1575]。然而，於電場發光性質及操作壽命之觀點來的，仍存在大量所欲者。At the same time, as a series of non-metal complexes, the electron transport materials which have been announced so far have good properties, including spiro_PBD [n· Johansson et. al. Adv. Mater. 10 (1998) 1 136], PyPySPyPy [ M. Uchidaet. al. Chem. Mater. 13 (2001) 2680] and Kodak's TPBI [Y.-T. Tao et. al. Appl. Phys. Lett. 77 (2000) 1575]. However, there are still a large number of desires from the viewpoint of electric field luminescence properties and operational life.

TPBI ,常規電子傳輸材料之值得注意之事為，常規電子傳輸材料具有問題’如不同於所宣稱者，僅輕微改善之驅動電壓該裝置之操作壽命的顯著退劣化、或出現副作用性質包括對於個貞色之裝置操作壽命的偏離以及熱安定性之退化實際上’上揭之副作用性質業已成為達成目標的障礙如增加祕1 力率及亮度，料製造大尺寸 0LED面板的障礙。【發明内容】技術問題藉此’本發明之一目榡係提供補償常規電子傳輸材料 5 95193 201204729 之弱點的有機電子材料之新穎化合物，以及改善電子傳輪之效率、消耗功率及裝置操作壽命的有機電子材料之新穎化合物。本發明之另一目標係提供包括該有機電子材料之新穎化合物的有機電場發光裝置。技術解決方法本發明係提供藉由下述化學式（1)表示之有機電子材料化合物及使用該化合物之有機電場發光裝置。作為電子傳輸材料之根據本發明之有機電子材料化合物展現優異之電子傳輸效率’其可於該等裝置之製造過程中防止結晶。再者，由於其提供良好之層形成，其可改善裝置之電流性質。因此，其可用於製造具有降低之驅動電壓及改盖 + 〇 <功率效的0LED裝置。化學式（1)TPBI, a matter of note for conventional electron transport materials, is that conventional electron transport materials have problems 'if different from what is claimed, only slightly improved drive voltage, significant degradation of the operational life of the device, or side effects include The deviation of the operational life of the twilight device and the degradation of thermal stability have actually become the obstacles to achieving the goal, such as increasing the force rate and brightness, and creating obstacles for the manufacture of large-size OLED panels. SUMMARY OF THE INVENTION Technical Problem [One of the Inventions] provides novel compounds for compensating organic electronic materials that are weak points of conventional electron transport materials 5 95193 201204729, as well as organics that improve the efficiency, power consumption, and operational life of electronic transmission wheels. A novel compound of electronic materials. Another object of the present invention is to provide an organic electric field illuminating device comprising the novel compound of the organic electronic material. Technical Solution The present invention provides an organic electronic material compound represented by the following chemical formula (1) and an organic electric field light-emitting device using the same. The organic electronic material compound according to the present invention as an electron transporting material exhibits excellent electron transport efficiency, which can prevent crystallization during the manufacture of such devices. Furthermore, since it provides good layer formation, it improves the current quality of the device. Therefore, it can be used to manufacture an OLED device having a reduced driving voltage and a modified + 〇 < Chemical formula (1)

其中， X 係表示-C(R丨）（R2)---Si(R3)(R4)---S-或-〇〜；Wherein, X represents -C(R丨)(R2)---Si(R3)(R4)---S- or -〇~;

Ri至R4係獨立表示（C1-C30)烷基、（C6-C30)芳基气 (C3-C30)雜芳基，或者與R2或R3與R4可經由具有咬不具有稠合環之（C3-C12)伸烷基或（C3-C12)伸烯基相鏈結以形成螺環或稠環；Ri to R4 independently represent (C1-C30)alkyl, (C6-C30) aryl (C3-C30)heteroaryl, or R2 or R3 and R4 may have a fused ring via a bit (C3) -C12) an alkyl or (C3-C12)-alkenyl phase chain to form a spiro ring or a fused ring;

An至An係獨立表示氫、（C1-C30)烷基、鹵素、二 (C1-C30)烷基硼烷基、二（C6-C30)芳基硼烷基、氰基、 6 95193 201204729 (C3-C30)環烷基、N-嗎啉基、N-硫代嗎啉基、N-哌啶基、5員至7員雜環烷基、（C7_C30)雙環烷基、（C2_C3〇)烯基、（C2_C3〇) 炔基、（C6-C30)芳基、（C1-C30)烷氧基、（C6-C30)芳氧基、 (C3-C30)雜芳基、咔唑基、（C6_C3〇)芳基（cl_C3〇)烷基、 (C6-C30)芳硫基、單或二（q_c30)烷基胺基、單或二（C6-C30) 芳基胺基、三（C1-C30)烷基矽烷基、二（C1-C30)烷基（C6-C30) 芳基石夕烧基、三（C6-C30)芳基矽烷基、硝基或羥基；該h至R4之烷基、芳基或雜芳基，以及該△1*1至Ar4 之烷基、環烷基、雜環烷基、雙環烷基、烷基硼烷基、芳基硼烷基、烯基、炔基、芳基、烷氧基、芳氧基、雜芳基、芳基烷基、芳硫基、烷基胺基、芳基胺基、三烷基矽烷基、一烧基芳基矽烷基或三芳基矽烧基，可進一步經一個或多個選自下列所組成群組之取代基取代：氘、（(n-c3〇)烷基、齒（C1 一C30)院基、齒素、氰基、（C3-C30)環烷基、5員至7 員雜環烷基、（C7-C30)雙環烷基、（C2-C30)烯基、（C2-C30) 炔基、（C6_C30)芳基、（C1-C30)烷氧基、（C6-C30)芳氧基、 (C3—C30)雜芳基、經（C1-C30)烷基取代之（C3-C30)雜芳基、經（C6-C30)芳基取代之（C3_C3〇)雜芳基、（C6_C3〇)* 基（C1-C30)烧基、（C6-C3〇)芳硫基、單或二（cl_C3〇)烷基胺基、單或二（C6-C30)芳基胺基、三（C1-C30)烷基矽烷基、一（C1-C30)烷基（C6-C30)芳基矽烷基、三（C6-C30)芳基矽烧基、确基及經基；以及該雜環烧基或雜芳基可含有選自B、N、0、S、P(=0)、 Si及P之一個或多個雜原子。 7 95193 201204729 【實施方式】於本發明中，「烷基」係包括僅含有碳原子及氣原子之直鏈或分支鍵飽和單價烴基，或其組合。又，「嫁氧基」及「烷硫基」係分別為-〇-烷基及-S-烷基，其中，燐基係如上揭定義者。於本發明中，「芳基」係意指自芳香族烴去掉/個氫原子所獲得之有機基，且可包括4員至7員（尤其是5員或 6員）之單環或稠環，包括複數個其間具有單鍵之芳基。具體實例包括苯基、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)、丙二稀舍苐基 (fluoranthenyl)等’但並不限於此。該萘基係包栝1-萘基及2-萘基。該蒽基係包括1-蒽基、2-蒽基及9-蒽基，以及該薙基係包括卜苐基、2-g基、3-第基、4-第恭及9-薙基。於本發明中，「雜芳基」係意指含有作為芳香族環骨架原子之選自B、N、0、S、P(=〇)、Si及P的1個爻4個雜原子，以及作為剩餘芳香族環骨架原子之碳原子之芳基。該雜芳基可為5員或6員單環雜芳基、或為與苯環縮合所得之多環雜芳基，並可呈部分飽和。該雜芳基亦可包括其間具有單鍵之多個雜芳基。於本發明中，「（C1-C30)烷基、二（C1-C30)烷基硼烷基、單或二（a-C30)烷基胺基、三（C1-C30)烷基矽烷基、二（C1-C30)烷基（C6-C30)芳基矽烷基、（C6-C30)芳基 (C1-C30)烷基、（C1-C30)烷氧基」等之烷基部份可具有1 8 95193 201204729 個至20個碳原子，更具體1個至10個碳原子。「（C6_C3〇) 芳基、二（a-C30)烷基（C6-C30)芳基矽烷基、三（C6-C30) 芳基矽烷基、（C6-C30)芳基（C1-C30)烷基、（C6-C30)芳氧基、（C6-C30)芳硫基」等之芳基部份可具有6個至20個碳原子，更具體6個至12個碳原子。「（C3-C30)雜芳基」之雜芳基可具有4個至20個碳原子，更具體4個至12個碳原子。「（C3-C30)環烷基」之環烷基可具有3個至20個碳原子，更具體3個至7個碳原子》「（C2-C30)烯基或炔基」之烯基或炔基可具有2個至20個碳原子，更具體2個至 10個碳原子。於化學式（1)中 ’ X 係表示-CdXRO-、-Si(R〇(R4)-、、S-或;An to An is independently represented by hydrogen, (C1-C30)alkyl, halogen, di(C1-C30)alkylboranyl, di(C6-C30)arylboranyl, cyano, 6 95193 201204729 (C3 -C30)cycloalkyl, N-morpholinyl, N-thiomorpholinyl, N-piperidinyl, 5- to 7-membered heterocycloalkyl, (C7_C30)bicycloalkyl, (C2_C3〇)alkenyl , (C2_C3〇) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30)heteroaryl, carbazolyl, (C6_C3〇 ) aryl (cl_C3 〇) alkyl, (C6-C30) arylthio, mono or di(q_c30)alkylamino, mono or di(C6-C30) arylamine, tri(C1-C30) alkane Alkyl, di(C1-C30)alkyl (C6-C30) aryl fluorenyl, tris(C6-C30)aryldecyl, nitro or hydroxy; alkyl or aryl of h to R4 or a heteroaryl group, and an alkyl group, a cycloalkyl group, a heterocycloalkyl group, a bicycloalkyl group, an alkylboryl group, an arylboranyl group, an alkenyl group, an alkynyl group, an aryl group of the Δ1*1 to Ar4, Alkoxy, aryloxy, heteroaryl, arylalkyl, arylthio, alkylamino, arylamino, trialkylalkyl, monoalkylarylalkyl or triaryl The alkyl group may be further substituted with one or more substituents selected from the group consisting of ruthenium, ((n-c3〇)alkyl, dentate (C1 - C30), dentate, cyano, ( C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl, (C7-C30)bicycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6_C30)aryl, C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30)heteroaryl, (C3-C30)alkyl substituted (C3-C30)heteroaryl, by (C6-C30) (aryl) substituted (C3_C3〇)heteroaryl, (C6_C3〇)*yl (C1-C30)alkyl, (C6-C3〇)arylthio, mono or di(cl_C3〇)alkylamine, single Or di(C6-C30)arylamino, tri(C1-C30)alkyldecyl, mono(C1-C30)alkyl(C6-C30)aryldecyl,tri(C6-C30)arylindole And a heterocyclic alkyl or heteroaryl group may contain one or more heteroatoms selected from the group consisting of B, N, 0, S, P (=0), Si, and P. 7 95193 201204729 [Embodiment] In the present invention, the "alkyl group" includes a linear or branched bond saturated monovalent hydrocarbon group containing only a carbon atom and a gas atom, or a combination thereof. The "aryloxy" and "alkylthio" are respectively -〇-alkyl and -S-alkyl, wherein the fluorenyl group is as defined above. In the present invention, "aryl" means The aromatic hydrocarbon is removed from the organic group obtained by one hydrogen atom, and may include a monocyclic or fused ring of 4 to 7 members (particularly 5 or 6 members), and includes a plurality of aryl groups having a single bond therebetween. Specific examples include phenyl, naphthyl, biphenyl, anthracenyl, fluorenyl, fluorenyl, phenanthryl, triphenylenyl, fluorenyl, fluorenyl, chrysenyl, fused tetraphenyl ( Naphthacenyl), fluoranthenyl, etc. 'but is not limited thereto. The naphthyl group is a 1-naphthyl group and a 2-naphthyl group. The anthracene group includes a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group, and the anthracene group includes a fluorenyl group, a 2-g group, a 3-position group, a 4-thylene group, and a 9-fluorenyl group. In the present invention, the "heteroaryl group" means one 爻 4 hetero atoms selected from B, N, 0, S, P (= 〇), Si, and P as an aromatic ring skeleton atom, and An aryl group as a carbon atom of a remaining aromatic ring skeleton atom. The heteroaryl group may be a 5- or 6-membered monocyclic heteroaryl group or a polycyclic heteroaryl group obtained by condensation with a benzene ring, and may be partially saturated. The heteroaryl group may also include a plurality of heteroaryl groups having a single bond therebetween. In the present invention, "(C1-C30)alkyl, di(C1-C30)alkylboran, mono or di(a-C30)alkylamino, tri(C1-C30)alkyldecyl, An alkyl moiety of a di(C1-C30)alkyl (C6-C30) arylalkyl, (C6-C30) aryl (C1-C30) alkyl, (C1-C30) alkoxy group, or the like may have 1 8 95193 201204729 to 20 carbon atoms, more specifically 1 to 10 carbon atoms. "(C6_C3〇) aryl, bis(a-C30)alkyl (C6-C30) aryl decyl, tris(C6-C30) aryl decyl, (C6-C30) aryl (C1-C30) alkane The aryl moiety of the (C6-C30) aryloxy group, (C6-C30) arylthio group or the like may have 6 to 20 carbon atoms, more specifically 6 to 12 carbon atoms. The heteroaryl group of "(C3-C30)heteroaryl" may have 4 to 20 carbon atoms, more specifically 4 to 12 carbon atoms. The cycloalkyl group of "(C3-C30)cycloalkyl" may have from 3 to 20 carbon atoms, more specifically from 3 to 7 carbon atoms, "(C2-C30)alkenyl or alkynyl" alkenyl or An alkynyl group can have from 2 to 20 carbon atoms, more specifically from 2 to 10 carbon atoms. In the chemical formula (1), X represents -CdXRO-, -Si(R〇(R4)-, , S- or;

Ri至R4係獨立表示（C1-C30)烷基或（C6-C30)芳基，或者Ri與R2或R3與R4可經由具有或不具有稠合環之（C3-C12) 伸烷基或（C3-C12)伸烯基相鏈結以形成螺環或稠環；亦即’匕與R2可經由具有或不具有稠合環之伸烷基或伸烯基相鏈結以形成螺環或稠環，但並不限於此。Ri to R4 independently represent (C1-C30)alkyl or (C6-C30)aryl, or Ri and R2 or R3 and R4 may be via (C3-C12)alkyl or with or without a fused ring ( C3-C12) an alkenyl phase chain to form a spiro ring or a fused ring; that is, '匕 and R2 may be linked to an alkyl or alkenyl chain with or without a fused ring to form a spiro ring or a thick Ring, but not limited to this.

又’ R3與R4可經由具有或不具有稠合環之神烧基或伸烯基相鏈結以形成螺環或稠環，但並不限於此。Further, R3 and R4 may be linked to each other via a dialkyl or an extended alkenyl phase with or without a condensed ring to form a spiro ring or a fused ring, but is not limited thereto.

An至An係獨立選自下列所組成之群組：（C3_C3〇)環 9 95193 201204729 烧基、N-嗎淋基、N-硫代嗎琳基、（C7-C30)雙環燒基、 (C2-C30)稀基、（C2-C30)快基、（C6-C30)芳基、（C6-C30) 芳氧基、（C3-C30)雜芳基、°卡嗤基、（C6-C30)芳硫基、三 (C1-C30)烷基矽烷基、二（C1-C30)烷基（C6-C30)芳基石夕烧基或三（C6-C30)芳基矽烷基。又’該Ri至R4之烧基或芳基’以及該Ar 1.至Αγ4之環烷基、雙環烷基、烯基、炔基、芳基、芳氧基、雜芳基、芳硫基、三炫基石夕烧基、二烧基芳基石夕烧基或三芳基;g夕烧基’可進一步經一個或多個選自下列所組成群組之取代基取代：氘、（C1-C30)烷基、鹵（C1-C30)烷基、鹵素、歡基、 (C3-C30)環烧基、5員至7員雜環烧基、（C7-C30)雙環烧基、（C2-C30)烯基、（C2-C30)炔基、（C6-C30)芳基、（C1-C30) 烧氧基、（C6-C30)芳氧基、（C3-C30)雜芳基、經（C1-C30) 烷基取代之（C3-C30)雜芳基、經（C6-C30)芳基取代之 (C3-C30)雜芳基、（C6-C30)芳基（C1-C30)烷基、（C6-C30) 芳硫基、單或二（C1-C30)烷基胺基、單或二（C6-C30)芳基胺基、三（C1-C30)烷基矽烷基、二（C1-C30)烷基（C6-C30)芳基石夕烧基、三（C6-C30)芳基梦烧基、确基及經基。根據本發明之有機電子材料化合物可藉由具有下列結構之化合物例示之，但並不限於此。An to An are independently selected from the group consisting of: (C3_C3〇) ring 9 95193 201204729 alkyl, N-noryl, N-thio-allinyl, (C7-C30)bicycloalkyl, (C2 -C30) dilute group, (C2-C30) fast group, (C6-C30) aryl group, (C6-C30) aryloxy group, (C3-C30) heteroaryl group, °carbyl group, (C6-C30) Arylthio, tri(C1-C30)alkyldecyl, di(C1-C30)alkyl(C6-C30)arylcarbazide or tri(C6-C30)aryldecyl. And 'the alkyl or aryl group of Ri to R4' and the cycloalkyl, bicycloalkyl, alkenyl, alkynyl, aryl, aryloxy, heteroaryl, arylthio group of the Ar 1. to Αγ4, a succinyl group, a dialkyl aryl sulphate or a triaryl group; the sulphide group may be further substituted with one or more substituents selected from the group consisting of hydrazine, (C1-C30) Alkyl, halo(C1-C30)alkyl, halogen, oxime, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C7-C30)bicycloalkyl, (C2-C30) Alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, by (C1- C30) an alkyl-substituted (C3-C30)heteroaryl group, a (C6-C30) aryl-substituted (C3-C30)heteroaryl group, a (C6-C30)aryl(C1-C30)alkyl group, C6-C30) arylthio, mono or di(C1-C30)alkylamino, mono or di(C6-C30)arylamino, tri(C1-C30)alkyldecyl, di(C1-C30) An alkyl (C6-C30) aryl group, a tris(C6-C30) aryl group, an exact group and a mesogenic group. The organic electronic material compound according to the present invention can be exemplified by a compound having the following structure, but is not limited thereto.

10 95193 20120472910 95193 201204729

11 95193 24 20120472911 95193 24 201204729

12 95193 20120472912 95193 201204729

13 95193 20120472913 95193 201204729

式（1)製備之。反應式（1) cA^，n''CA>n〇、achn^cA> NHAc ^Prepared by formula (1). Reaction formula (1) cA^,n''CA>n〇, achn^cA> NHAc ^

其中， X及Ar,至An之定義係與化學式（1)中定義者相同。所提供者係有機電場發光裝置，其係包含第一電極；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，該有機層包含—種或多種化學式⑴ 表不之有機電子材料化合物1有機電子材料化合物係用 95193 14 201204729 Λ 作該電子傳輸層之材料。當將根據本發明之藉由化學式（1)表示之有機電子材料化合物用於電子傳輸層中時，由於獲得減小之驅動電壓及傑出之發光效率，該0LED之損耗功率得以顯著降低。又’該有機層係包含一層或多層包括藉由化學式（1) 表不之有機電子材料化合物的層，以及一層或多層包括螢光主體及螢光摻雜劑或包括磷光主體及構光摻雜劑的層。施用於本發明之有機電場發光裝置中之該螢光主體、螢光摻雜劑、磷光主體或磷光摻雜劑並無具體限制。於本發明之有機電子裝置中，該有機層除了包括化學气（1)表示之有機電子材料化合物之外，可進一步同時包括種或多種選自芳基胺化合物及苯乙稀基芳基胺化合物所組成群組之化合物。該芳基胺化合物或苯乙稀基芳基胺化〇物係於韓國專利申請案第1〇 2〇〇8_〇123276號、第 2008-G1G76G6 號或第 1Q_2_-G118428 號中例示之，但不限於此。再者，於本發明之有機電場發光裝置中，該有機層除了包括化學式⑴表示之有機電子材料化合物之外，可進一 'I括種或多種選自第i族之有機金屬、第2族、第4 ^與第5周期之過渡金屬、鑭系金屬及d-過渡元素組成、且之金屬’或錯合化合物。該有機層可包括電場發光及電荷產生層。再者，該有機材料化合物之外，層除了包括化學式（1)表示之有機電子可同時包括一層或多層發射藍光、綠光 95193 201204729 或紅光之有機電場發光層’以提供發射白光之有機電場發光裝置。該發射藍光、綠光或紅光之化合物可以於韓國專利申請案第號、第 10-2008-0107606 號及第10_2008_0118428號中揭示之化合物例示之，但不限於此。於本發明之有機電場發光裝置中，係將一層（後文中稱為「表面層」）選自硫屬化合物（chalcogenide)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一個或兩個電極的内表面上。更具體而言，可將矽或鋁之金屬硫屬化合物（包括氧化物）層設置於電場發光介質層之陽極表面上，並可將金屬函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。藉此可得到操作安定性。該硫屬化合物可為，諸如Si〇x(lSxS2)、AHUlSx ^1. 5)、SiON、SiAlON等。該金屬鹵化物可為，諸如LiF、 MgF2、CaF2、稀土金屬之氟化物等。該金屬氧化物可為，諸如 Cs2〇、Li2〇、MgO、SrO、BaO、CaO 等。於根據本發明之電場發光裝置中，亦較佳係將電子傳輸化合物與還原性摻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如是製造之電極對的至少一個表面上。於該例中，由於電子傳輸化合物被還原成陰離子’電子自混合區域注入與傳輸至電場發光介質變得更容易。此外，由於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輸至電場發光介質變得更容易。較佳之氧化性摻雜劑係包括各種路易士酸及接受者化合物 16 95193 201204729 (acceptor compound)。較佳之還原性摻雜劑係包括驗金屬化合物、驗土金屬、稀土金屬及其混合物。再者屬、可藉由使用還原性摻雜劑層作為電荷產生層來製備具層或多看電場發光層之發射白光之有機電場發光裝置。有益效果 ° 作為電子傳輸材料之根據本發明之有機電子材料化合物展現優異之電子傳輸效率，其可於裝置之製造過程中防止結晶。挨著’由於其提供良好之層形成，其可改善裝置之電流性質。因此，其可用以製造具有降低之驅動電壓、改善之功率效率及相同或更高之發光效率的〇LED裝置。發明模式將關於根據本發明之有機電子材化合物、該化合物之製備方法以及使用該化合物之裝置的發光性質以進一步闡述本發明。然而，下列實施例僅提供用於例示性說明用’ 而非意欲限制本發明之範圍。 [製備例1 ]化合物2之製備Wherein, the definitions of X and Ar, to An are the same as those defined in the chemical formula (1). Provided is an organic electric field illuminating device comprising: 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 or A plurality of organic electronic materials of the formula (1) are represented by the compound 1 organic electronic material compound using 95193 14 201204729 Λ as the material of the electron transport layer. When the organic electronic material compound represented by the chemical formula (1) according to the present invention is used in an electron transport layer, the loss power of the OLED is remarkably lowered due to the obtained reduced driving voltage and excellent luminous efficiency. Further, the organic layer comprises one or more layers comprising a compound of an organic electronic material represented by the chemical formula (1), and one or more layers comprising a fluorescent host and a fluorescent dopant or comprising a phosphorescent host and a light-doping dopant. Layer of the agent. The fluorescent host, the fluorescent dopant, the phosphorescent host or the phosphorescent dopant to be used in the organic electric field light-emitting device of the present invention is not particularly limited. In the organic electronic device of the present invention, the organic layer may further include one or more compounds selected from the group consisting of arylamine compounds and styrene arylamine compounds, in addition to the organic electron material compound represented by the chemical gas (1). Compounds of the group formed. The arylamine compound or the styrene arylamine amide is exemplified in Korean Patent Application No. 1〇2〇〇8_〇123276, 2008-G1G76G6 or 1Q_2_-G118428, but Not limited to this. Furthermore, in the organic electric field light-emitting device of the present invention, the organic layer may include an organic metal material selected from the group i, or a plurality of organic metals selected from the group i, the second group, in addition to the organic electronic material compound represented by the chemical formula (1). The transition metal, the lanthanide metal, and the d-transition element of the 4th and 5th cycles, and the metal' or the compound. The organic layer may include an electric field luminescence and a charge generating layer. Further, in addition to the organic material compound, the layer includes, in addition to the organic electron represented by the chemical formula (1), one or more layers of an organic electric field emitting layer that emits blue light, green light 95193 201204729 or red light to provide an organic electric field that emits white light. Light emitting device. The compound which emits blue light, green light or red light can be exemplified by the compounds disclosed in Korean Patent Application No. 10-2008-0107606 and No. 10_2008_0118428, but is not limited thereto. In the organic electric field light-emitting device of the present invention, a layer (hereinafter referred to as "surface layer") selected from a chalcogenide layer, a metal halide layer and a metal oxide layer is provided on the electrode pair. On the inner surface of one or both of the electrodes. More specifically, a layer of a metal chalcogenide (including an oxide) of ruthenium or aluminum may be disposed on the anode surface of the electric field luminescent medium layer, and a metal functional layer or a metal oxide layer may be disposed on the electric field luminescent medium layer. On the surface of the cathode. Thereby, operational stability can be obtained. The chalcogen compound may be, for example, Si〇x(lSxS2), AHUlSx^1. 5), SiON, SiAlON or the like. The metal halide may be, for example, a fluoride of LiF, MgF2, CaF2, a rare earth metal, or the like. The metal oxide may be, for example, Cs2〇, Li2〇, MgO, SrO, BaO, CaO or the like. In the electric field light-emitting device according to the present invention, it is also preferred to provide 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 in at least the electrode pair to be manufactured. On a surface. In this case, it becomes easier to inject and transport electron-transporting compounds into the anion-emitting region to the electric field illuminating medium since the electron-transporting compound is reduced to an anion. In addition, since the hole transporting compound is oxidized to a cation, it becomes easier to inject and transport the hole from the mixed region to the electric field illuminating medium. Preferred oxidizing dopants include various Lewis acids and acceptor compounds 16 95193 201204729 (acceptor compound). Preferred reducing dopants include metal-detecting compounds, soil-measuring metals, rare earth metals, and mixtures thereof. Further, an organic electric field light-emitting device which emits white light having a layer or a plurality of electric field light-emitting layers can be prepared by using a reducing dopant layer as a charge generating layer. Advantageous Effects The organic electronic material compound according to the present invention as an electron transporting material exhibits excellent electron transport efficiency, which can prevent crystallization during the manufacturing process of the device. Next, it improves the current properties of the device because it provides a good layer formation. Therefore, it can be used to manufacture a 〇LED device having a reduced driving voltage, improved power efficiency, and the same or higher luminous efficiency. Mode for Invention The invention will be further elucidated with respect to the organic electronic material compound according to the present invention, the preparation method of the compound, and the luminescent properties of the device 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 2

於氮氣氛下將2, 7-二溴苐（1〇公克（g)，0.037莫耳 95193 17 201204729 (mol))加入THF(200毫升（mL))中並冷卻至-78。〇之後，將 n-BuLi(2. 5M己烷溶液）（1· 2當量）緩慢加入其中。2小時後’加入1Μ HC1 ’將該混合物攪拌30分鐘，用ΕΑ及蒸館水洗滌三次。藉由旋轉型蒸發器移除，藉由以矽膠過濾器過渡所產生之有機層而得之殘餘液體中之溶劑後，獲得呈白色固體之化合物A(7g，97%) » 化合物B之製備將化合物A(10g，0. 05mol)溶解於乙酸（i〇〇mL)中。於〇°C將發烟硝酸（當量重量：50)及硫酸（3〇mL)加入該混合物之後’將該混合物緩慢加熱至室溫並攪拌3〇分鐘。減壓過濾所產生之固體’以乙酸洗滌兩次。減壓蒸餾所得有機層並移除溶劑之後，經管柱色層分析予以純化而獲得呈純黃固體之化合物B(4. 2g，30%)。化合物C之製備於氮氣氛下將鹽酸（30mL)、乙醇（i2mL)、SnCl2(4g) 及化合物B(4. 2g，0· 014mol)擾拌回流4小時之後，過濾、所得固體，以鹽酸洗滌該混合物。將乙酸（2〇mL)與無水乙酸（20mL)混合之後，於0°C緩慢加入所產生之白色固體 (3g)。20分鐘之後，將該混合物緩慢加熱至室溫並授拌24 小時。反應完成之後，將蒸餾水緩慢加入該混合物中，藉由旋轉型蒸發器移除溶劑。以二氣甲烷萃取之後，以蒸麵水洗務該反應混合物3次。減壓下蒸顧所得有機層並移除溶劑之後’藉由管柱色層分析予以純化而獲得呈純白色固體之化合物C(3. 5g, 75%)。 18 95193 201204729 化合物D之製備於-10°C將乙酸（10mL)與發烟硝酸（i〇mL)混合之後，於相同溫度緩慢加入化合物C(3. 5g，0. 〇145mol)。10分 , 鐘後，將反應物加入冷蒸餾水中並於減壓下過濾。藉由管柱色層分析純化所得有機材料而獲得呈純黃色固體之化合 -物 D(3.4g，59%)。化合物E之製備依序將硫酸（24mL)及蒸餾水（20mL)緩慢加入化合物 D(3. 4g，〇·〇〇9ιηο1)中。接著，於90°C回流下將反應物攪拌2小時。反應完成之後，將反應物加入冷蒸餾水中並於減壓下過濾。藉由管柱色層分析純化所得有機材料而獲得呈純黃色固體之化合物E(2g，70%)。化合物F之製備將溴苯（1. lg)、Pd(OAc)2(0. 04g)及 Cs2C〇3(4. lg)加入化合物E(2g，0. 006mol)之後，於氮氣氛下將甲苯（25mL) 及p(t-Bu)3(〇. 4mL)加入該混合物中。於80°C回流下攪拌該混合物12小時。反應完成之後，以EA及蒸餾水萃取該混合物，藉由旋轉型蒸發器移除溶劑。藉由管柱色層分析純化所得有機材料而獲得呈黃色固體之化合物F(2g， 71%) 〇化合物G之製備將乙醇（2〇mL)加入化合物F(2g，0. 0043mol)之後’將該混合物攪拌10分鐘，氫氣氛（5 psi)下於9(TC將Pd/C (0. 3§)攪拌回流4小時。反應完成之後，減壓下過濾反應 19 95193 201204729 物。藉由管柱色層分析純化所得有機材料而獲得呈黃色固體之化合物G(1.8g，74%)。化合物2之製備將2-萘酸（1· 4g)及乙酸（50mL)加入化合物g(1. 3g， 0. 0 0 3mo 1)之後’於回&下擾掉該處合物12小時。反應完成之後，以ΕΑ及蒸餾水萃取該混合物，藉由旋轉型蒸發器移除溶劑。藉由管柱色層分析純化所得有機材料而獲得呈象牙白色固體之化合物2(1.2g，55%)。 [製備例2]化合物49之製備2,7-Dibromoindole (1 gm (g), 0.037 mol 95193 17 201204729 (mol)) was added to THF (200 mL (mL)) under nitrogen and cooled to -78. After the hydrazine, n-BuLi (2.5 M hexane solution) (1.2 equivalent) was slowly added thereto. After 2 hours, the mixture was stirred for 30 minutes by adding 1 Μ HC1, and washed three times with hydrazine and steaming water. After removal by a rotary evaporator, the solvent in the residual liquid obtained by the transition of the organic layer produced by the silica gel filter gave Compound A (7 g, 97%) as a white solid. Compound A (10 g, 0.05 mol) was dissolved in acetic acid (i 〇〇 mL). After adding fuming nitric acid (equivalent weight: 50) and sulfuric acid (3 〇 mL) to the mixture at 〇 ° C, the mixture was slowly heated to room temperature and stirred for 3 Torr. The solid produced by the filtration under reduced pressure was washed twice with acetic acid. The obtained organic layer was evaporated under reduced pressure and purified, and then purified and purified by column chromatography to afford compound B (4.2 g, 30%). Preparation of Compound C Under a nitrogen atmosphere, hydrochloric acid (30 mL), ethanol (i2 mL), SnCl 2 (4 g) and Compound B (4.2 g, 0. 014 mol) were stirred and refluxed for 4 hours, and then filtered, and the obtained solid was washed with hydrochloric acid. The mixture. After mixing acetic acid (2 mL) with anhydrous acetic acid (20 mL), the white solid (3 g) which was formed was slowly added at 0 °C. After 20 minutes, the mixture was slowly warmed to room temperature and allowed to mix for 24 hours. After the reaction was completed, distilled water was slowly added to the mixture, and the solvent was removed by a rotary evaporator. After extraction with di-methane, the reaction mixture was washed three times with steamed water. After the obtained organic layer was evaporated under reduced pressure and the solvent was removed, purified by column chromatography to give Compound C (3.5 g, 75%) as a white solid. 18 95193 201204729 Preparation of Compound D After mixing acetic acid (10 mL) with fuming nitric acid (i 〇 mL) at -10 ° C, compound C (3.5 g, . 145 mol) was slowly added at the same temperature. After 10 minutes, the reaction was added to cold distilled water and filtered under reduced pressure. The obtained organic material was purified by column chromatography to give Compound D (3.4 g, 59%) as a pure yellow solid. Preparation of Compound E Sulfuric acid (24 mL) and distilled water (20 mL) were slowly added to Compound D (3.4 g, 〇·〇〇9ιηο1). Then, the reaction was stirred at 90 ° C for 2 hours under reflux. After the reaction was completed, the reactant was poured into cold distilled water and filtered under reduced pressure. The obtained organic material was purified by column chromatography to give Compound E (2 g, 70%) as a solid yellow solid. Preparation of Compound F After adding bromobenzene (1. lg), Pd(OAc) 2 (0. 04 g) and Cs2C〇3 (4. lg) to compound E (2 g, 0.006 mol), toluene under nitrogen atmosphere (25 mL) and p(t-Bu)3 (〇. 4 mL) were added to the mixture. The mixture was stirred at 80 ° C for 12 hours under reflux. After the reaction was completed, the mixture was extracted with EA and distilled water, and the solvent was removed by a rotary evaporator. The obtained organic material was purified by column chromatography to give Compound F (2 g, 71%) as a yellow solid. Preparation of 〇 Compound G After adding ethanol (2 〇mL) to compound F (2 g, 0.0043 mol) The mixture was stirred for 10 minutes, and hydrogen (5 psi) was stirred at reflux for 9 hours at TC (Pd/C (0.3 §). After the reaction was completed, the reaction was filtered under reduced pressure, 19 95193 201204729. The obtained organic material was purified by chromatography to give Compound G (1.8 g, 74%) as a yellow solid. Compound 2 was added 2-naphthic acid (1.4 g) and acetic acid (50 mL) to compound g (1.3 g, 0. 0 0 3mo 1) After the mixture was disturbed for 12 hours under the back & after the reaction was completed, the mixture was extracted with hydrazine and distilled water, and the solvent was removed by a rotary evaporator. The obtained organic material was purified by layer chromatography to obtain Compound 2 (1.2 g, 55%) as an ivory white solid. [Preparation 2] Preparation of Compound 49

化合物Η之製備將二笨并[b，d]噻吩（9. 2g, 0. 〇5mol)、過氧化氫（21. 6 mL)及甲醇（300mL)混合，於室溫攪拌5分鐘。接著，加入 Zl*Ch(46· 5§)，於室溫攪拌3分鐘。以CHCh及蒸餾水萃取之後’經管杈分離獲得化合物H(97%產率）。化合物I之製備 20 95193 201204729 將化合物 Η(8· 5g，〇. 〇42mol)、H2S〇4(36. 7mL)、AcOH (36. 7mL)及HN〇3(40mL)混合並於室溫攪拌2小時。反應完成之後，加入蒸餾水以產生固體。藉由過濾該固體獲得產 • 率為89%之化合物I。化合物J之製備將化合物 1(9. 2g，〇. 〇3mol)、HCl(60mL)、SnCl2(47 mL) 及AcOH(lOOmL)混合並攪拌12小時。反應完成之後，使用 HC1過濾之後以MeOH洗滌，獲得產率為74%之化合J。化合物K之製備將化合物 J(llg，0. 05mol)、CuBr2(22. 8g)、t-BuN〇2 (9.2mL)及乙腈（255mL)混合並於回流下攪拌12小時。反應完成之後’以EA及蒸德水萃取該反應混合物，經管柱色層分析獲得產率為70%之化合K。化合物L之製備將化合物 K(9. 7g，0. 03mol)、LiAlH4(l. 3g)及 THF (174niL)混合並於回流下攪拌3小時。反應完成之後，以 EA及蒸德水萃取該反應混合物，經管柱色層分析獲得產率為47%之化合L。化合物49之製備使用化合物L作為中間體，以實施例1之相同方式透過C-1至G-1之製程獲得產率為42%之化合物49。 [製備例3]化合物8之製備 95193 201204729 — > °^QrH0 — A-1 B-1 C-1Preparation of the compound hydrazine The mixture of dibenzo[b,d]thiophene (9.2 g, 0.15 mol), hydrogen peroxide (21. 6 mL) and methanol (300 mL) was stirred at room temperature for 5 min. Next, Zl*Ch (46·5 §) was added, and the mixture was stirred at room temperature for 3 minutes. After extraction with CHCh and distilled water, the compound H (97% yield) was obtained. Preparation of Compound I 20 95193 201204729 The compound Η (8·5g, 〇. 〇42mol), H2S〇4 (36.7mL), AcOH (36.7mL) and HN〇3 (40mL) were mixed and stirred at room temperature 2 hour. After the reaction was completed, distilled water was added to give a solid. A compound I having a yield of 89% was obtained by filtering the solid. Preparation of Compound J Compound 1 (9.2 g, 〇. 3 mol), HCl (60 mL), SnCl 2 (47 mL) and AcOH (100 mL) were mixed and stirred for 12 hours. After completion of the reaction, it was filtered with HCl and washed with MeOH to give a compound of yield of 74%. Preparation of Compound K Compound J (llg, 0.05 mol), CuBr2 (22.8 g), t-BuN 2 (9.2 mL) and acetonitrile (255 mL) were combined and stirred under reflux for 12 hours. After completion of the reaction, the reaction mixture was extracted with EA and steamed water, and a K of a yield of 70% was obtained by column chromatography. Preparation of Compound L Compound K (9.7 g, 0.03 mol), LiAlH4 (1.3 g) and THF (174niL) were mixed and stirred under reflux for 3 hours. After completion of the reaction, the reaction mixture was extracted with EA and distilled water, and a yield of 47% of compound L was obtained by column chromatography. Preparation of Compound 49 Using Compound L as an intermediate, Compound 49 was obtained in a yield of 42% by the procedure of C-1 to G-1 in the same manner as in Example 1. [Preparation Example 3] Preparation of Compound 8 95193 201204729 — > °^QrH0 — A-1 B-1 C-1

化合物A-l之製備於氮氣氛下將2,7-二溴苐（30居，0.109111〇1)加入1'册 (500mL)中之後，將該混合物冷卻至-78°C，將n-BuLi (2. 5M 己烷溶液）（52. 7mL，0. 131 mol)緩慢加入其中。1小時後，將水加入該混合物中，並完成反應。用EA萃取該混合物並藉由矽膠過濾器過濾。藉由旋轉型蒸發器移除所得殘餘液體後，獲得呈白色固體之化合物A-l(16g，75. 6«。化合物B-1之製備將化合物A-l(16g，0.082mol)溶解於乙酸（400mL)中。使用滴液漏斗於0°C加入發烟硝酸（172mL，4. lmol)及硫酸 (43mL)，並攪拌24小時。減壓過濾所產生之固體之後，以 22 95193 201204729 乙酸及蒸餾水洗滌該混合物。減壓蒸餾所得有機層並移除溶劑之後，經管柱色層分析予以純化而獲得化合物B-1 (16g，81.5%)。化合物C-1之製備 . 於氮氣氛下將化合物B-l(19g，〇. 〇67mol)、SnCl2 (120g，0. 536mol)、HCl(152mL)及乙醇（80mL)攪拌回流 4 小時，過濾所產生之固體。將乙酸（250mL)與無水乙酸 (lOOmL)混合’緩慢加入所得固體並於室溫回流下授拌24 小時。反應完成之後，經過濾獲得呈白色固體之化合物 C-l(l〇 g，48.4%)。化合物D-1之製備於-10°C將化合物C-l(10g，〇· 〇324mol)溶解於乙酸中之後，於相同溫度緩慢加入發烟硝酸（75mL)。10分鐘後，將反應物加入冷蒸餾水中並過濾以獲得固體。以蒸餾水及己烧洗務所得固體之後’經乾紐獲得呈黃色固體之化合物 D-l(5g，38. 7%)。化合物E-1之製備依序將硫酸（30mL)及蒸餾水（8mL)緩慢加入化合物 D-l(5g’ 〇· 〇i26mol)中之後，於150°C回流下搜拌反應物 2小時。反應完成之後，將該反應物加入冷蒸鶴水中並減壓過濾。藉由管柱色層分析純化所得有機材料而獲得呈血紅色固體之化合物E-l(3. 5g, 88. 4%)。化合物Η之製備將化合物Ε-1(0. 4g，〇· 〇78mol)溶解於乙醇（1〇此）中 95193 23 201204729 之後，將該混合物加入Pd/C(70毫克（mg))中，於90°C回流下攪拌4小時。反應完成之後，過濾反應物並加入鹽酸。移除溶劑之後，藉由再結晶（乙醇：THF = 1:1)獲得化合物 H(0.43g，91%)。化合物1-3之製備添加化合物I-l(13g)、化合物i-2(4g)、K2C〇3(4g)及銅（Cu)粉（0· 15g)並於220°C攪拌6小時。經蒸餾移除過量使用之化合物I-1之後，經甲醇再結晶獲得呈白色固體之化合物 I-3(6g，80%)。化合物卜4之製備將化合物I-3(lg)溶解於乙醇中之後，加入過量Κ0Η 溶液（10M水溶液）並攪拌。反應完成之後，以鹽酸萃取該混合物’經過濾獲得呈白色固體之化合物I_4(〇. 5g， 70〇/〇)。化合物J之製備將化合物H(〇. 5毫莫耳（mmol))及化合物（1-4)(1 mmol) 加入冰醋酸中並攪拌2小時。過濾所得固體之後，藉由管柱色層分析純化獲得化合物j(lg，33. 5%)。化合物8之製備添加化合物 J(lg，1.32_〇1)、蛾苯（5.3mmol)、Cul (0,07mmol)、18-冠-6(0. lmmol)及 1，2-二氯苯（50mL)並於 180°C回流下攪拌。反應完成之後，以ea萃取該混合物，藉由管柱色層分析純化獲得呈純固體之化合物8(lg， 83%) 〇 24 95193 201204729 根據製備例1至3製備有機電場發光化合物1至66，所製備有機電場發光化合物之1H NMR及MS/FAB數據如表 1所示。表1 化合物 1H NMR(CDCl3, 200 MHz) MS/FAB 測量值計算值 1 δ = 1.72(6H, s), 7·41-7_51(12Η，m), 7·56(2Η，s), 7.58(4Η· m), 7.84(2H, s), 8·28(4Η, m) 578.70 578.25 2 5 = 1.72(6H, s). 7.45-7.5(6H, m), 7.56(2H, s), 7.58-7.59(8H, m), 7.84(2H, s), 7.92(2H, m). 8(4H, m), 8.49(2H, m), 9.09(2H, m) 678.82 678.28 3 δ = 1.72(6H, s), 7.56(2H, s), 7.84(2H, s) 598.83 598.37 4 δ = 1.72(6H, s), 7.25(4H, m), 7.41-7.52(16H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 7.85(4H, m) 730.90 730,31 5 5 = 1.72(6H, s), 7.45-7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.82(4H, m), 7.84(2H, s), 7.88-7.93(6H, m), 8.12(4H( m), 8.93(4H, m) 778.94 778.31 6 5 = 1.72(6H, s), 2.53(12H, s), 7.12(2H, m), 7.34(2H, s). 7.45-7.5(6H, m). 7.56(2H, s), 7.58(4H, m), 7.77(2H, m), 7.84(2H, s). 8.07(2H, m), 8.32(2H, m) 839.00 838.35 7 δ = 1.72(6H. s), 7.25-7.33(4H, m), 7.41-7.51 (13H, m), 7.56(2H, s), 7.58-7.63(7H, m), 7.84(2H, s), 7.94~7.98(4H, m), 8.12(1H, m), 8.28(4H, 叫,8.55(1 H,m) 909.09 908.36 25 95193 201204729 8 δ = 1·72(6Η, s). 7·25~7.33(6Η· m), 7.45~7·5(8Η. m). 7.56(2Η. s), 7.58~7.68(10H. m), 7.79(4H, m), 7.84(2H, s), 7.94(2H, m). 8.12(2H, m), B.55(2H, m) 909.09 908.36 9 5 = 1.35(18H, s)t 1.72(6H, s). 7.38(4H, m). 7.45-7.5(6H, m), 7.56(2H1 s). 7.58(4H, m), 7.84(2H, s), 8_S6(4H, m) 690.92 690.37 10 5 = 1.72(6H· s), 3.83(6H, s), 7.05(4H，m), 7.45-7.5(6H, m), 7.56(2H, s), 7.58(4H· m), 7·84(2Η· s)· 7.97(4H, m) 638.76 638.27 11 δ = 1.72(6H, s). 7.45-7.5(6H, m), 7.56(2H, s). 7.58(4H, m), 7.69-7.73(4H, m). 7.84(2H, s), 7.88(2H, m), 8.56(2H, m) 628.72 628.24 12 5 = 1.72(6H, s), 7.44-7.5(8H, m), 7.56(2H. s), 7.58(6H, m), 7.84(2H, s). 8.28(2H. m). 8.64(2Hf m) 714.70 714.22 13 5 = 1.72(6H, s), 7.45-7.5(6H, m). 7.56(2H. s), 7.58(4H, m), 7.77(2H, m), 7.84(2H. s), 8.22(2H, m), 8.36(2H, m), 8.65(2H, m) 668.70 668.22 14 5 = 0.25(18H, s), 1.72(6H, s). 7.45-7.5(10H, m), 7.56(2H, s)t 7.58(4H, m)f 7.77(4H, m), 7.84(2H, s), (H,) 723.07 722.33 15 5 = 1.72(6H, s)( 7.37(12H, m). 7.45-7.55(28H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 7.89(4H, m) 1095.48 1094.42 16 5 = 1.72(18H, s), 7.28(2H, m), 7.38(2H, m), 7.45~7.55(8H, m), 7.56(2H, s), 7.58~7.63(6H, m), 7.77(2H, m), 7.84(2H, s), 7.87-7.93(4H, m) 811.02 810.37 17 δ = 1.72(6H, s), 7.25-7.33(3H, m), 7.45-7.5(13H, m), 7.56(2H, s), 7.58-7.63{9H, m), 7.69(1H, m), 7.77(2H, m), 7.84(2H, s), 7.87(1H, m), 7.94-8(2H, m), 8.12(1H, m), 8.18(1H, m), 8.55(1H, m) 909.09 * 908.36 18 5 = 1.72(6H( s)? 7.32-7.38(4H, m). 7.45-7.5(6H, m). 7.56(2Hf s), 7.58(4Hf m). 7.66-7.72(6Hf m)t 7.81(2H. m), 7.84(2H, s)t 7.89(2H, m) 758.86 758.27 19 5 = 1.72(6H, s), 7.45-7.52(1 OH. m), 7.56(2H, s), 7.58(4H, m), 7.8(2H. m). 7.84(2H, s), 7.86(2H, m). 7.98-8(4H, m). 8.45(2H, m) 790.99 790.22 20 5 = 0·66(12Η. s), 1·72(6Η· s), 7.33(2H, m)· 7.45-7.52(8H, m)· 7.56(2H, s), 7·58~7_61(8Η· m). 7.8(2H. m). 7.84(2H, s), 7.85-7.89(4H. m) 843.17 842.33 21 δ = 172(6H. s)% 7.45-7.5(6H, m)( 7.56(2HP s), 7.58(4Hf m), 7.67(4H. m), 7.8(4H. m), 7.84(2H, s). 8.7(2H, s) 682.77 682.26 22 δ = 1.72(6Hf s), 7.14(2H, m), 7.45-7.5(6H. m), 7.56(2Ht s)f 7.58(4H, m), 7.7(2H, m), 7.84(2HI s), 7.97(2H, m). 8.12(2H, m), 8.53(2Ht m), 9_26-9.3(4H, m) 734.85 734.29 23 δ = 1·72(6Η· s). 7.41(4H· m), 7·51(8Η, m)· 7,56(2H, s), 7.68(4H，m), 7.79(4H, m), 7.84(2Hf s), 8.05(4H, m). 8.28(4H( m) 866.96 866.31 24 5 = 1.72(6H, s), 7.41-7.51(18H, m)( 7.56(2H( s), 7.58(4H. m), 7.68(4H. nn), 7.79(4H, m), 7.84(2Ht s), 8.28(8H. m) 1017.19 1016.41 26 95193 201204729 25 δ = 1.72(6Η, s), 7.41-7.51(12Η, m), 7.56(2Η, s), 7.58(4ΗΡ m). 7.73-7.79(8Κ m), 7.84(2Η, s) 742.95 742.22 26 δ = 1·72(6Η, s), 7.07(4Η, m>，7.41-7_51(12Η· m), 7.56(2Η, s), 7·58(4Η, m). 7.84(2Η, s), 8.1(4Η, m) 710.82 710.27 27 δ = 1.72(6Η, s)f 7.33~7.45(12Η? m), 7.48(4Ht s), 7.5(4Η, m), 7.56(2Η, S), 7.58(4Η, m). 7.84(2Ht s) 836.74 838.11 28 δ = 1.72(6Η( s), 7.41-7.51(12Η, m), 7.56(2Η. s)( 7.58(4Η, m), 7.84(2HF s), 8_03(4Η, m) 746.90 746.20 29 δ = 1·72(6Η, s), 7·41~7·51(12Η, m), 7_56(2Η, s), 7.58(4Η, ητ〇, 7·84(2Η, s), 8.05(4Η· m) 714.77 714.25 30 δ = 1.72(6Η, s)f 7.45-7.52(12Η, m)( 7.56(2Η, s), 7.58(4Η, m), 7.83(4Η, m). 7.84(2Η, s) 640.69 842.09 31 δ = 0·14<12Η, s), 1·72(6Η, s), 7.04(4Η, s), 7.33~7·5<16Η, 7.56(2Η, s), 7.58(4Η, m), 7.84(2Hf s) 795.13 794.33 32 δ = 0.14(12Η. s), 1.72(6Η, s>, 7.04(2Η, s), 7.14-7·17(4Η, m>, 7.43-7.5(8Ht m), 7.56(2Η, s), 7.58(4Η, m), 7.65(2Η, s), 7.7(2Hf m), 7.84(2Η, s). 8.53(2Η, m), 9.19(2Η, m), 9.3(2Η, m) 951.27 950.37 33 δ = 1.72(6Η, s), 7.14(4Ht m), 7.41(2Η, m), 7.51(4Η, m), 7.56(2Ht s), 7.7(4Ht m). 7.84(2Η, s), 8.15(4Η, m)( 8.28(4Η, m), 8.53(4Η, m), 9.3(4Η, m) 889.02 888.34 34 δ = 1.72(6Η, s), 7.4-7.41 (4Η, m), 7.51 (4Η. m)( 7.56(2Η, s), 7.84(2Η, s). 7.9(2Η, m)( 8.01 (2Η, m), 8.28(4Η, m), 8.41 (2Η. m) 580.68 580.24 35 δ = 172(6H, s)f 7.36"7.4(4Η, m)r 7.56(2Η. s), 7.84(2Ht s)( 7.85-7.9(4H, m), 8.01 (2H, m), 8.38-8.41(4H, m), 8.59(2H, m) 582.66 582.23 36 δ = 1.72(6H. s), 7.45-7.5(6H, m)t 7.56(2H, s), 7.57»7.58(6H, m), 7.67-7.8(12H, m)( 7.84(2H, s), 8.24(2H, m), 8.7(2H, s) 834.97 834.32 37 δ = 1.72(6H· s)· 7.4W.5(8H，m), 7.56(2H, s), 7.58~7.6(6H, m), 7.78(2H, m), 7.84(2H, s), 7.98(2H, m), 8.06(2H, m), 8.44(2H, m) 680.80 680.27 38 δ = 1.72(6H, s), 2.61(6H( s), 7.06(2H, s), 7.45-7.5(6H, m). 7.56(2H, s), 7.58-7.59(6H, m), 7.75(2H, m), 7.84(2Ht s), 7.95(2H, m), 8.16(2H. m) 708.85 708.30 39 5 = 1.72(6H. s), 7.42-7.5(12H, m), 7.56(2H, s), 7.58-7.63(6H, m), 7.84(2H, s), 7.92(2H. m), 8.51(2Ht m) 680.80 680.27 40 5 = 1.72(6H, s), 2.36(6H, s), 6.83(2HI m), 7.31(2H, m), 7.45-7.5(6H( m), 7.56(2H, s)f 7.58(4Hf m), 7.84(2H, s), 7.85(8H, m) 771.00 770.25 41 5 = 1.72(6HP s), 2.3(6H, s), 6.08(2H, m). 6.95(2H, m), 7.45>7.5(6Ht m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 7.85(8H. m) 738.87 738.30 42 5 = 1.71(6H, m)f 1.72(6H, s)f 6.9(2H, m), 7.44-7.45(6H, m)f 7.48(2H, s), 864.79 666.14 27 95193 201204729 7.5(4H, m), 7.56(2H, s), 7.58(4H. m), 7.74(4H, m). 7.84(2H, s) 43 δ = 1·72(6Η· s), 2.64(6H. 3), 7,45-7.5(6H, m>· 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 7.85(8H, m) 774.96 774.23 44 5 = 1.72(6H, s)t 2.62(6H, s), 7.45-7.5(6H. m), 7.56(2H, s). 7.58(4H. m), 7.84(2H, s), 7.85(8H, m) 742.83 742.28 45 5 = 1.72(6H( s), 2(6Η, s), 7.45-7.5(6H, m), 7,56(2H, s), 7.58(4H, m)t 7.84(2H, s), 7·85-7.89(8Η, m) 868.75 870.12 46 δ = 1.72(6H, s)( 7.22(4H, m), 7.45-7.5(12Ht m), 7.56(2Hf s), 7.58-7.59(10H, m), 7.84(2H, s)t 7.85(8H, m), 8.56(2H, m) 963.14 962.38 47 δ = 0·66(6Η, s). 7.4W.51(12H, m), 7·58(4Η, m), 8.02(2H. s>· 8.04(2H, s)· 8.28(4H· m) 594.78 594.22 48 5 = 1.3(4H, m〉，1,45(4Hf m), 7·45~7·5(6Η, m), 7.58-7.59(8H· m)， 7.92(2H, m), 8(4H. m), 8.02(2H, s). 8.04(2H, s), 8.49(2H, m)t 9.09(2Hf m) 720.93 720.27 49 δ = 7.45-7.5(6H, m), 7.58-7.59(8Ht m), 7.78(2H, s). 7.86(2H, s), 7.92(2K m), 8(4H, m), 8.49(2H, m), 9.09(2H, m) 668.81 668.20 50 5 = 7.41(2H, m), 7.42(2H, s), 7.45(2H, m), 7.49(2H, s), 7.5-7.51(8H, m), 7.58(4Ht m), 8.28(4H, m) 552,62 552.20 51 5 = 1.72(12H, s), 7.28(2H, m), 7.38(2H, m), 7.42(2H, s), 7.45(2H, m), 7.49(2H, s), 7.5-7.63(12H, m), 7.77(2H, m), 7.87~7.93(4H, m) 784.94 784.32 52 δ = 1.72(6H, s). 7.41 (2Ht m), 7.51-7.53(8H, m), 7.56(2H( s), 7,68(4H, rr〇, 7·79(4Η, m), 7.84(2H, s), 8.01 (2H, m)· 8.18(2H, m), 8·28(4Η, m) 845.04 844.24 53 5 = 1.72(18H, s), 7.28(2H, m)t 7,38(2Hf m)t 7.53-7.55(6H( m), 7.56(2H, 5), 7.63-7.68(6H, m), 7.77-7.79(6H, m), 7.84(2Hf s), 7.87-7.93(4H. m), B.01(2H, m),8.18(2Hl m) 1077.36 1076.37 54 5 = 1.72(6H, s), 7·36"7·41(4Η, m), 7_51~7.53(8H, m). 7.56(2H· s)_ 7.83(2Ht m), 7.84(2H, s), 7.87-7.92(4H. m)f 8-8.01 (4Hf m), 8.18(2H, m)t B.28(4H, m), 8.34(2H, m) 945.16 944.28 55 5 = 1.72(6H, s), 7.41(4Hf m), 7.51-7.52(12H. m). 7.56(2H, s), 7.84(2H, 5), 7.88(2H, m), 7.96(2H. m), 8.28(4Ht m), 8.58(2Hf m) 732.87 732.30 56 5 = 1.48(12H, m), 1.72{6H, s), 1.73(8H. m), 2.72(2Hf m), 7.41(2H( m), 7.51-7.52(8H, m). 7.56(2H, s), 7.68(4H, m), 7.79(4H, m), 7.84(2H, s) 742.99 742.40 57 δ = 1.72(6H, s>, 3.65(8H, m)· 3.74(8H, m). 7.45-7·5(6Η, m), 7.56(2H，s) Γ.58(4Η, m). 7.84(2H. s) 596.72 596.29 58 δ = 1.72(6H，s), 5·6(2Η，m)，6.9(2H· m>, 7.33(2H, m), 7.4~7.41<6H, m), 7.51 (4H, m), 7.56(2H, s), 7.6(4H, m), 7.84(2H, s), 8.28(4H. m) 630.78 630.28 59 δ = 1.72(6H, s), 7.41~7.43(8H. m), 7·51~7·55(8Η. m), 7.56(2H· s), 7.84(2H, s). 8·28(4Η, m) 626.75 626.25 28 95193 201204729 60 5 = 1.72(6H, s), 6.95-7.01 (6H, m), 7.28(4H, m), 7.45-7.5(6H, m), 7.56(2H. s), 7.58(4Hf m), 7.84(2H, s) 610.70 610.24 61 δ = 1.72(6H, s). 7.23-7.29(6H, m), 7.39(4H, m). 7.45-7.5(6H. m)t 7.56(2H, s), 7.58(4H, m)t 7.84(2Ht s) 642.83 642.19 62 δ = -0.33(18Ht s). 1.72(6Ht ), 7.45(2H, m), 7.5(4H, m), 7.56(2H, s), 7.58(4Ht m), 7.84(2Hf s) 570.87 570.26 63 δ = 0.66(12H, S), 1.72(6H, s). 7.18(4H, m), 7.27(4H, m), 7.45-7.5(8H, m)· 7_56(2H, s), 7.58(4H, m), 7.84(2H, s) 695.01 694.29 64 δ = 1.72(6H. s), 7_37(12H, m>, 7.45~7.55(24H，m), 7_56(2H_ s), 7_58(4H, m)· 7.84(2H, s) 943.29 942.36 65 δ = 1.72(6Hf s)t 5.35(2H, s), 6.91(2Hf m). 7.04(2H, m). 7.34(2H. m), 7.45-7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.84(4H, s) 610.70 610.24 66 δ = 1.4*-1.43(18H, m)( 1.69(4H, m), 1.72(6Ht s), 1.81(2H, m). 2.71(2Ht m). 7.45-7.5(6H. m), 7.56(2H, s). 7.58(4H, m). 7.84(2H. s) 642.87 642.37 [實施例1至5]使用根據本發明之有機電子材料化合物之 0LED裝置之製造使用根據本發明之電子材料化合物製造了 0LED裝置。首先，使用超音波依序以三氯乙烯、丙酮、乙醇及蒸餾水清洗由0LED用玻璃（Samsung Corning)所得之透明電極ΙΤ0薄膜（15Ω/ΙΙΙ)，並儲存於異丙醇中備用。然後，將ΙΤ0基板裝配於真空氣相沉積裝置之基板夾中，將4,4’，4” -銮（N，N-(2-萘基）-苯基胺基）三苯基胺 (2-TMTA)置於該真空氣相沉積裝置之一小室中，隨後對該腔室内通風至10_6托（torr)真空。隨後，藉由對該小室施加電流來蒸發2-TNATA，從而在該ΙΤ0基板上形成厚度為 60奈米（nm)之電洞注入層。隨後，將N，Ν’ -雙（α-萘基）-Ν，Ν’ -二苯基-4,4’ -二胺（ΝΡΒ)置於該真空氣相沉積裝置之另一小室中，對該小室施加電流來蒸發ΝΡΒ，從而於該電洞注入層上形成厚度為20 nm之電洞傳輸層。 29 95193 201204729Preparation of Compound Al After adding 2,7-dibromoindole (30 Å, 0.109111 〇1) to a 1' book (500 mL) under a nitrogen atmosphere, the mixture was cooled to -78 ° C, n-BuLi (2) 5M hexane solution) (52.7 ml, 0.113 mol) was slowly added thereto. After 1 hour, water was added to the mixture and the reaction was completed. The mixture was extracted with EA and filtered through a silica gel filter. After removing the obtained residual liquid by a rotary evaporator, a compound A1 (16 g, 75.6) was obtained as a white solid. Preparation of Compound B-1 Compound Al (16 g, 0.082 mol) was dissolved in acetic acid (400 mL) The fuming nitric acid (172 mL, 4.1 mol) and sulfuric acid (43 mL) were added at 0 ° C and stirred for 24 hours. After the solid produced was filtered under reduced pressure, the mixture was washed with 22 95193 201204729 acetic acid and distilled water. The obtained organic layer was evaporated under reduced pressure and the solvent was evaporated, and then purified by column chromatography to give Compound B-1 (16 g, 81.5%). Preparation of Compound C-1. Compound B1 (19 g, 〇. 67mol), SnCl2 (120g, 0.536mol), HCl (152mL) and ethanol (80mL) were stirred under reflux for 4 hours, and the solid produced was filtered. Acetic acid (250 mL) was mixed with anhydrous acetic acid (100 mL). The obtained solid was stirred for 24 hours under reflux at room temperature. After completion of the reaction, compound Cl (1 g, 48.4%) was obtained as a white solid. 10g, 〇· 〇 324mol) after being dissolved in acetic acid, The fuming nitric acid (75 mL) was slowly added at the same temperature. After 10 minutes, the reactant was added to cold distilled water and filtered to obtain a solid. After distilling water and a solid obtained by washing, the compound D1 was obtained as a yellow solid. 5g, 38.7%) Preparation of Compound E-1 Sulfuric acid (30mL) and distilled water (8mL) were slowly added to the compound D1 (5g' 〇·〇i26mol), and then the reaction was carried out at 150 ° C under reflux. After the reaction is completed, the reaction is added to the cold-cold water and filtered under reduced pressure. The obtained organic material is purified by column chromatography to obtain a compound of the blood red solid El (3.5 g, 88. 4 %) Preparation of the compound 将 After the compound Ε-1 (0.4 g, 〇·〇78 mol) was dissolved in ethanol (1 〇) 95193 23 201204729, the mixture was added to Pd/C (70 mg (mg)) The mixture was stirred under reflux at 90 ° C for 4 hours. After the reaction was completed, the reaction mixture was filtered and hydrochloric acid was added. After the solvent was removed, Compound H (0.43 g, 91%) was obtained by recrystallization (ethanol: THF = 1:1). Preparation of Compound 1-3 Add Compound Il (13g), Compound i-2 ( 4g), K2C〇3 (4g) and copper (Cu) powder (0.15g) and stirred at 220 ° C for 6 hours. After the excess use of compound I-1 was removed by distillation, it was recrystallized from methanol to give a white solid. Compound I-3 (6 g, 80%). Preparation of Compound 4 After dissolving Compound I-3 (lg) in ethanol, an excess of hydrazine solution (10 M aqueous solution) was added and stirred. After completion of the reaction, the mixture was extracted with hydrochloric acid to give a compound I_4 (5 g, 70 〇 / 〇) as a white solid. Preparation of Compound J Compound H (〇. 5 mmol (mmol)) and Compound (1-4) (1 mmol) were added to glacial acetic acid and stirred for 2 hours. After filtration of the obtained solid, compound j (lg, 33.5%) was obtained by column chromatography. Preparation of Compound 8 Compound J (lg, 1.32_〇1), mothene (5.3 mmol), Cul (0,07 mmol), 18-crown-6 (0.1 mmol) and 1,2-dichlorobenzene (50 mL) were added. And stirred at 180 ° C under reflux. After completion of the reaction, the mixture was extracted with ea, and purified by column chromatography to obtain compound 8 as a pure solid ( lg, 83%) 〇 24 95193 201204729 Preparation of organic electroluminescent compounds 1 to 66 according to Preparations 1 to 3, The 1H NMR and MS/FAB data of the prepared organic electroluminescent compound are shown in Table 1. Table 1 Compound 1H NMR (CDCl3, 200 MHz) MS/FAB Measured value 1 δ = 1.72 (6H, s), 7·41-7_51 (12Η, m), 7·56(2Η, s), 7.58 ( 4Η· m), 7.84(2H, s), 8·28(4Η, m) 578.70 578.25 2 5 = 1.72(6H, s). 7.45-7.5(6H, m), 7.56(2H, s), 7.58- 7.59(8H, m), 7.84(2H, s), 7.92(2H, m). 8(4H, m), 8.49(2H, m), 9.09(2H, m) 678.82 678.28 3 δ = 1.72(6H, s), 7.56(2H, s), 7.84(2H, s) 598.83 598.37 4 δ = 1.72(6H, s), 7.25(4H, m), 7.41-7.52(16H, m), 7.56(2H, s) , 7.58(4H, m), 7.84(2H, s), 7.85(4H, m) 730.90 730,31 5 5 = 1.72(6H, s), 7.45-7.5(6H, m), 7.56(2H, s) , 7.58(4H, m), 7.82(4H, m), 7.84(2H, s), 7.88-7.93(6H, m), 8.12(4H( m), 8.93(4H, m) 778.94 778.31 6 5 = 1.72 (6H, s), 2.53(12H, s), 7.12(2H, m), 7.34(2H, s). 7.45-7.5(6H, m). 7.56(2H, s), 7.58(4H, m), 7.77(2H, m), 7.84(2H, s). 8.07(2H, m), 8.32(2H, m) 839.00 838.35 7 δ = 1.72(6H. s), 7.25-7.33(4H, m), 7.41- 7.51 (13H, m), 7.56(2H, s), 7.58-7.63(7H, m), 7.84(2H, s), 7.94~7.98(4H, m), 8.12(1H, m), 8.28(4H, Called, 8.55 (1 H, m) 909.09 908.36 25 95193 20 1204729 8 δ = 1·72(6Η, s). 7·25~7.33(6Η· m), 7.45~7·5(8Η. m). 7.56(2Η. s), 7.58~7.68(10H. m) , 7.79(4H, m), 7.84(2H, s), 7.94(2H, m). 8.12(2H, m), B.55(2H, m) 909.09 908.36 9 5 = 1.35(18H, s)t 1.72 (6H, s). 7.38(4H, m). 7.45-7.5(6H, m), 7.56(2H1 s). 7.58(4H, m), 7.84(2H, s), 8_S6(4H, m) 690.92 690.37 10 5 = 1.72(6H· s), 3.83(6H, s), 7.05(4H,m), 7.45-7.5(6H, m), 7.56(2H, s), 7.58(4H· m), 7·84 (2Η· s)· 7.97(4H, m) 638.76 638.27 11 δ = 1.72(6H, s). 7.45-7.5(6H, m), 7.56(2H, s). 7.58(4H, m), 7.69-7.73 (4H, m). 7.84(2H, s), 7.88(2H, m), 8.56(2H, m) 628.72 628.24 12 5 = 1.72(6H, s), 7.44-7.5(8H, m), 7.56(2H s), 7.58(6H, m), 7.84(2H, s). 8.28(2H.m). 8.64(2Hf m) 714.70 714.22 13 5 = 1.72(6H, s), 7.45-7.5(6H, m) 7.56(2H. s), 7.58(4H, m), 7.77(2H, m), 7.84(2H.s), 8.22(2H, m), 8.36(2H, m), 8.65(2H, m) 668.70 668.22 14 5 = 0.25(18H, s), 1.72(6H, s). 7.45-7.5(10H, m), 7.56(2H, s)t 7.58(4H, m)f 7.77(4H, m), 7.84( 2H, s), (H,) 723.07 722.33 15 5 = 1.72(6H, s)( 7.37(12H, m). 45-7.55(28H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 7.89(4H, m) 1095.48 1094.42 16 5 = 1.72(18H, s), 7.28( 2H, m), 7.38(2H, m), 7.45~7.55(8H, m), 7.56(2H, s), 7.58~7.63(6H, m), 7.77(2H, m), 7.84(2H, s) , 7.87-7.93(4H, m) 811.02 810.37 17 δ = 1.72(6H, s), 7.25-7.33(3H, m), 7.45-7.5(13H, m), 7.56(2H, s), 7.58-7.63{ 9H, m), 7.69(1H, m), 7.77(2H, m), 7.84(2H, s), 7.87(1H, m), 7.94-8(2H, m), 8.12(1H, m), 8.18 (1H, m), 8.55(1H, m) 909.09 * 908.36 18 5 = 1.72(6H( s)? 7.32-7.38(4H, m). 7.45-7.5(6H, m). 7.56(2Hf s), 7.58 (4Hf m). 7.66-7.72(6Hf m)t 7.81(2H.m), 7.84(2H, s)t 7.89(2H, m) 758.86 758.27 19 5 = 1.72(6H, s), 7.45-7.52(1 OH. m), 7.56(2H, s), 7.58(4H, m), 7.8(2H.m). 7.84(2H, s), 7.86(2H, m). 7.98-8(4H, m). 8.45 (2H, m) 790.99 790.22 20 5 = 0·66(12Η. s), 1·72(6Η· s), 7.33(2H, m)· 7.45-7.52(8H, m)· 7.56(2H, s) , 7.8(2H.m). 6H, m) ( 7.56 (2HP s), 7.58 (4Hf m), 7.67 (4H. m), 7.8 (4H. m), 7. 84(2H, s). 8.7(2H, s) 682.77 682.26 22 δ = 1.72(6Hf s), 7.14(2H, m), 7.45-7.5(6H.m), 7.56(2Ht s)f 7.58(4H, m), 7.7(2H, m), 7.84(2HI s), 7.97(2H, m). 8.12(2H, m), 8.53(2Ht m), 9_26-9.3(4H, m) 734.85 734.29 23 δ = 1 · 72(6Η· s). 7.41(4H· m), 7·51(8Η, m)· 7,56(2H, s), 7.68(4H,m), 7.79(4H, m), 7.84(2Hf s), 8.05(4H, m). 8.28(4H(m) 866.96 866.31 24 5 = 1.72(6H, s), 7.41-7.51(18H, m)( 7.56(2H( s), 7.58(4H. m) , 7.68(4H. nn), 7.79(4H, m), 7.84(2Ht s), 8.28(8H.m) 1017.19 1016.41 26 95193 201204729 25 δ = 1.72(6Η, s), 7.41-7.51(12Η, m) , 7.56(2Η, s), 7.58(4ΗΡ m). 7.73-7.79(8Κ m), 7.84(2Η, s) 742.95 742.22 26 δ = 1·72(6Η, s), 7.07(4Η, m>, 7.41 -7_51(12Η·m), 7.56(2Η, s), 7·58(4Η, m). 7.84(2Η, s), 8.1(4Η, m) 710.82 710.27 27 δ = 1.72(6Η, s)f 7.33 ~7.45(12Η?m), 7.48(4Ht s), 7.5(4Η, m), 7.56(2Η, S), 7.58(4Η, m). 7.84(2Ht s) 836.74 838.11 28 δ = 1.72(6Η( s ), 7.41-7.51(12Η, m), 7.56(2Η. s)( 7.58(4Η, m), 7.84(2HF s), 8_03(4Η, m) 746.90 746.20 29 δ = 1 ·72(6Η, s), 7·41~7·51(12Η, m), 7_56(2Η, s), 7.58(4Η, ητ〇, 7·84(2Η, s), 8.05(4Η· m) 714.77 714.25 30 δ = 1.72(6Η, s)f 7.45-7.52(12Η, m)( 7.56(2Η, s), 7.58(4Η, m), 7.83(4Η, m). 7.84(2Η, s) 640.69 842.09 31 δ = 0·14 <12Η, s), 1·72(6Η, s), 7.04(4Η, s), 7.33~7·5<16Η, 7.56(2Η, s), 7.58(4Η, m), 7.84(2Hf s) 795.13 794.33 32 δ = 0.14(12Η. s), 1.72(6Η, s>, 7.04(2Η, s), 7.14-7·17(4Η, m>, 7.43-7.5(8Ht m), 7.56(2Η, s), 7.58(4Η, m), 7.65(2Η, s), 7.7(2Hf m), 7.84(2Η, s). 8.53(2Η, m), 9.19(2Η, m), 9.3( 2Η, m) 951.27 950.37 33 δ = 1.72(6Η, s), 7.14(4Ht m), 7.41(2Η, m), 7.51(4Η, m), 7.56(2Ht s), 7.7(4Ht m). 7.84( 2Η, s), 8.15(4Η, m)( 8.28(4Η, m), 8.53(4Η, m), 9.3(4Η, m) 889.02 888.34 34 δ = 1.72(6Η, s), 7.4-7.41 (4Η, m), 7.51 (4Η. m)( 7.56(2Η, s), 7.84(2Η, s). 7.9(2Η, m)( 8.01 (2Η, m), 8.28(4Η, m), 8.41 (2Η. m) 580.68 580.24 35 δ = 172(6H, s)f 7.36"7.4(4Η, m)r 7.56(2Η. s), 7.84(2Ht s)( 7.85-7.9(4H, m), 8.01 (2H, m ), 8 .38-8.41(4H, m), 8.59(2H, m) 582.66 582.23 36 δ = 1.72(6H. s), 7.45-7.5(6H, m)t 7.56(2H, s), 7.57»7.58(6H, m), 7.67-7.8(12H, m)( 7.84(2H, s), 8.24(2H, m), 8.7(2H, s) 834.97 834.32 37 δ = 1.72(6H· s)· 7.4W.5(8H , m), 7.56(2H, s), 7.58~7.6(6H, m), 7.78(2H, m), 7.84(2H, s), 7.98(2H, m), 8.06(2H, m), 8.44( 2H, m) 680.80 680.27 38 δ = 1.72(6H, s), 2.61(6H( s), 7.06(2H, s), 7.45-7.5(6H, m). 7.56(2H, s), 7.58-7.59( 6H, m), 7.75(2H, m), 7.84(2Ht s), 7.95(2H, m), 8.16(2H.m) 708.85 708.30 39 5 = 1.72(6H. s), 7.42-7.5(12H, m ), 7.56(2H, s), 7.58-7.63(6H, m), 7.84(2H, s), 7.92(2H.m), 8.51(2Ht m) 680.80 680.27 40 5 = 1.72(6H, s), 2.36 (6H, s), 6.83(2HI m), 7.31(2H, m), 7.45-7.5(6H(m), 7.56(2H, s)f 7.58(4Hf m), 7.84(2H, s), 7.85( 8H, m) 771.00 770.25 41 5 = 1.72(6HP s), 2.3(6H, s), 6.08(2H, m). 6.95(2H, m), 7.45>7.5(6Ht m), 7.56(2H, s ), 7.58(4H, m), 7.84(2H, s), 7.85(8H.m) 738.87 738.30 42 5 = 1.71(6H, m)f 1.72(6H, s)f 6.9(2H, m), 7.44- 7.45(6H, m)f 7.48(2H, s), 864.79 666.14 27 95193 00 (4H, m) 3), 7,45-7.5(6H, m>· 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 7.85(8H, m) 774.96 774.23 44 5 = 1.72(6H , s)t 2.62(6H, s), 7.45-7.5(6H.m), 7.56(2H, s). 7.58(4H.m), 7.84(2H, s), 7.85(8H, m) 742.83 742.28 45 5 = 1.72(6H( s), 2(6Η, s), 7.45-7.5(6H, m), 7,56(2H, s), 7.58(4H, m)t 7.84(2H, s), 7· 85-7.89(8Η, m) 868.75 870.12 46 δ = 1.72(6H, s)( 7.22(4H, m), 7.45-7.5(12Ht m), 7.56(2Hf s), 7.58-7.59(10H, m), 7.84(2H, s)t 7.85(8H, m), 8.56(2H, m) 963.14 962.38 47 δ = 0·66(6Η, s). 7.4W.51(12H, m), 7·58(4Η, m), 8.02(2H. s>· 8.04(2H, s)· 8.28(4H· m) 594.78 594.22 48 5 = 1.3(4H, m〉,1,45(4Hf m), 7·45~7·5 (6Η, m), 7.58-7.59(8H·m), 7.92(2H, m), 8(4H.m), 8.02(2H, s). 8.04(2H, s), 8.49(2H, m)t 9.09(2Hf m) 720.93 720.27 49 δ = 7.45-7.5(6H, m), 7.58-7.59(8Ht m), 7.78(2H, s). 7.86(2H, s), 7.92(2K m), 8(4H , m), 8.49(2H, m), 9.09(2H, m) 668.81 668.20 50 5 = 7.41(2H, m), 7.42(2H, s), 7.45(2H, m), 7.49(2H, s), 7.5-7.51(8H, m), 7.58(4Ht m), 8.28(4H, m) 552,62 552.20 51 5 = 1.72(12H, s), 7.28(2H, m), 7.38(2H, m), 7.42(2H, s), 7.45(2H, m), 7.49(2H, s), 7.5-7.63(12H, m), 7.77(2H, m), 7.87~7.93(4H, m) 784.94 784.32 52 δ = 1.72(6H, s). 7.41 (2Ht m), 7.51-7.53(8H, m), 7.56(2H(s) ), 7,68(4H, rr〇, 7·79(4Η, m), 7.84(2H, s), 8.01 (2H, m)· 8.18(2H, m), 8·28(4Η, m) 845.04 844.24 53 5 = 1.72(18H, s), 7.28(2H, m)t 7,38(2Hf m)t 7.53-7.55(6H( m), 7.56(2H, 5), 7.63-7.68(6H, m) , 7.77-7.79(6H, m), 7.84(2Hf s), 7.87-7.93(4H.m), B.01(2H, m), 8.18(2Hl m) 1077.36 1076.37 54 5 = 1.72(6H, s) , 7·36"7·41(4Η, m), 7_51~7.53(8H, m). 7.56(2H· s)_ 7.83(2Ht m), 7.84(2H, s), 7.87-7.92(4H. m ) f 8-8.01 (4Hf m), 8.18(2H, m)t B.28(4H, m), 8.34(2H, m) 945.16 944.28 55 5 = 1.72(6H, s), 7.41(4Hf m), 7.51-7.52(12H.m). 7.56(2H, s), 7.84(2H, 5), 7.88(2H, m), 7.96(2H.m), 8.28(4Ht m), 8.58(2Hf m) 732.87 732.30 56 5 = 1.48(12H, m), 1.72{6H, s), 1.73(8H.m), 2.72(2Hf m), 7.4 1(2H(m), 7.51-7.52(8H, m). 7.56(2H, s), 7.68(4H, m), 7.79(4H, m), 7.84(2H, s) 742.99 742.40 57 δ = 1.72( 6H, s>, 3.65(8H, m)· 3.74(8H, m). 7.45-7·5(6Η, m), 7.56(2H,s) Γ.58(4Η, m). 7.84(2H. s 596.72 596.29 58 δ = 1.72(6H,s), 5·6(2Η,m),6.9(2H·m>, 7.33(2H, m), 7.4~7.41<6H, m), 7.51 (4H, m), 7.56(2H, s), 7.6(4H, m), 7.84(2H, s), 8.28(4H.m) 630.78 630.28 59 δ = 1.72(6H, s), 7.41~7.43(8H. m) , 7·51~7·55(8Η. m), 7.56(2H· s), 7.84(2H, s). 8·28(4Η, m) 626.75 626.25 28 95193 201204729 60 5 = 1.72(6H, s) , 6.95-7.01 (6H, m), 7.28(4H, m), 7.45-7.5(6H, m), 7.56(2H.s), 7.58(4Hf m), 7.84(2H, s) 610.70 610.24 61 δ = 1.72(6H, s). 7.23-7.29(6H, m), 7.39(4H, m). 7.45-7.5(6H.m)t 7.56(2H, s), 7.58(4H, m)t 7.84(2Ht s 642.83 642.19 62 δ = -0.33(18Ht s). 1.72(6Ht ), 7.45(2H, m), 7.5(4H, m), 7.56(2H, s), 7.58(4Ht m), 7.84(2Hf s) 570.87 570.26 63 δ = 0.66(12H, S), 1.72(6H, s). 7.18(4H, m), 7.27(4H, m), 7.45-7.5(8H, m)· 7_56(2H, s), 7.58 (4H, m), 7.84(2H, s) 695.01 694.29 64 δ = 1.72(6H. s), 7_37(12H, m>, 7.45~7.55(24H,m), 7_56(2H_ s), 7_58(4H, m)· 7.84(2H, s) 943.29 942.36 65 δ = 1.72(6Hf s)t 5.35(2H, s), 6.91(2Hf m). 7.04(2H, m). 7.34(2H.m), 7.45-7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.84(4H, s) 610.70 610.24 66 δ = 1.4*-1.43(18H, m)( 1.69(4H, m), 1.72(6Ht s), 1.81(2H, m). 2.71( 2Ht m). 7.45-7.5(6H.m), 7.56(2H, s). 7.58(4H, m). 7.84(2H.s) 642.87 642.37 [Examples 1 to 5] using the organic electronic material according to the present invention Manufacture of a compound OLED device An OLED device was fabricated using an electronic material compound according to the present invention. First, a transparent electrode ΙΤ0 film (15 Ω / ΙΙΙ) obtained from OLED glass (Samsung Corning) was washed with a mixture of trichloroethylene, acetone, ethanol and distilled water in the order of ultrasonic waves, and stored in isopropyl alcohol for use. Then, the ΙΤ0 substrate was assembled in a substrate holder of a vacuum vapor deposition apparatus, and 4,4',4"-銮(N,N-(2-naphthyl)-phenylamino)triphenylamine (2) -TMTA) is placed in a chamber of the vacuum vapor deposition apparatus, and then the chamber is ventilated to a 10-6 Torr vacuum. Subsequently, 2-TNATA is evaporated by applying a current to the chamber, thereby constituting the ΙΤ0 substrate. A hole injection layer having a thickness of 60 nm is formed thereon. Subsequently, N,Ν'-bis(α-naphthyl)-fluorene, Ν'-diphenyl-4,4'-diamine (ΝΡΒ) Placed in another chamber of the vacuum vapor deposition apparatus, an electric current is applied to the chamber to evaporate the crucible, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. 29 95193 201204729

形成該電洞注入層及電洞傳輸層之後，以下列方式於其上形成電場發光層。分別將為電場發光主體之叁（8-羥基喹啉）鋁（III) (Alq3)置於真空氣相沉積裝置之一小室中作為發光材料，將香豆素545T置於另一小室中作為電場發光摻雜劑。以不同速率蒸發該兩種材料，從而於該電洞傳輸層上氣相沉積厚度為30nm之電場發光層。基於Alq3，摻雜濃度可為2至5莫耳°/〇。After the hole injection layer and the hole transport layer are formed, an electric field light-emitting layer is formed thereon in the following manner. The octa (8-hydroxyquinoline) aluminum (III) (Alq3), which is an electric field illuminating body, is placed in a chamber of a vacuum vapor deposition apparatus as a luminescent material, and the coumarin 545T is placed in another chamber as an electric field. Luminescent dopant. The two materials were evaporated at different rates to vapor-deposit an electroluminescent layer having a thickness of 30 nm on the hole transport layer. The doping concentration may be 2 to 5 mTorr/〇 based on Alq3.

Alq3 接著，於該電場發光層上氣相沉積厚度為20nm之電子材料化合物（如化合物（2))作為電子傳輸層。然後，氣相沉積厚度為lnra至2nm之8-經基哇琳裡（lithium quinolate，Liq)作為電子注入層後，用另一真空氣相沉積裝置形成厚度為150nm之鋁（A1)陰極而製造出0LED。 30 95193 201204729Alq3 Next, an electron material compound (e.g., compound (2)) having a thickness of 20 nm is vapor-deposited on the electroluminescent layer as an electron transport layer. Then, a vapor-deposited thickness of lnra to 2 nm is obtained by using lithium quinolate (Liq) as an electron injecting layer, and then another vacuum vapor deposition apparatus is used to form an aluminum (A1) cathode having a thickness of 150 nm. Out of 0LED. 30 95193 201204729

於該0LED裝置中作為電場發光材料之各化合物係已於10_6 torr真空昇華予以純化者。 [比較例1]使用常規電子傳輸材料之0LED裝置之電場發光性質以實施例1之相同方式形成電洞注入層、電洞傳輸層及電場發光層之後，氣相沉積厚度為20 nm之叁（8-羥基喹啉）鋁（III) (Alq3)作為電子傳輸層。然後，氣相沉積厚度為1至2 nm之下述結構之8-羧基σ奎淋链（Liq)作為電子注入層後，用另一真空氣相沉積裝置形成厚度為150 nm之銘 (A1)陰極而製造出0LED。分別於1，000燭光（cd)/平方公尺（m2)測量實施例1至 5及比較例1中包含根據本發明之有機電子材料化合物或常規電子傳輸材料之0LED的驅動電壓及發光效率，結果係顯示於表2中。 31 95193 201204729 表2 編號電子傳輸材料於 1，000 cd/m2 測得之驅動電壓（V) 於 1，000cd/m2 測得之發光效率（cd/安培(A)) 實施例1 化合物2 5.0 12.2 實施例2 化合物19 4.9 12.5 實施例3 化合物26 4.6 13.1 實施例4 化合物52 4.5 13.3 實施例5 化合物54 5.1 11.8 比較例1 Alq3 6 11.6 一如表2所示，當將化合物52用作電子傳輸材料（實施例4)時，出現最高之功率效率。具體地，與使用常規Aiq3 作為電子傳輸層之例（比較例1)相比，化合物52(實施例 4)之功率效率顯示約15%之改善。與常規有機電場發光裝置（比較例1)相比’化合物16(實施例3)之驅動電壓顯示約1.4V之降低。自顯示於表2中之當使用本發明研發之化合物作為電子傳輸層所獲得之性質可知’自效能之觀點來看，本發明研發之化合物係優於常規材料。 [實施例6至8]使用根據本發明之有機電子材料化合物之 0LED裝置之製造使用根據本發明之電場發光化合物製造了 OLed裝置。首先，使用超音波依序以三氣乙稀、丙酮、乙醇及蒸餾水清洗由0LED用玻璃（Samsung Corning)所得之透明電極ΙΤ0薄膜（15Ω/ΕΙ1)，並儲存於異丙醇中備用。 95193 32 201204729 然後，將ΙΤ0基板裝配於真空氣相沉積裝置之基板夾中，將4, 4’，4” -叁（Ν，Ν-(2-萘基）-苯基胺基）三苯基胺 (2-ΤΝΑΤΑ)置於該真空氣相沉積裝置之一小室中，隨後對該腔室内通風至torr真空。隨後，藉由對該小室施加 .電流來蒸發2-TNATA，從而在該ΙΤ0基板上形成厚度為6〇 - 奈米（nm)之電洞注入層。隨後，將N，N，-雙（α-萘基）-Ν，Ν’ -二苯基-4,4，-二胺（ΝΡΒ)置於該真空氣相沉積裝置之另一小室中，對該小室施加電流來蒸發ΝρΒ，從而於該電洞注入層上形成厚度為2〇11[11之電洞傳輸層。將藉由在ΙΟ·6 torr真空昇華予以純化之根據本發明之化合物（如，化合物7)置於真空氣相沉積裝置之一小室中作為主體，並將電場發光摻雜劑（如化合物（piq)2lr(acac)) 置於另-小室中。以不同速率蒸發該兩種材料，從而透過以4至10重量％之摻雜而在該電洞傳輸層上氣相沉積厚度為30nm之電場發光層。Each of the compounds used as the electric field luminescent material in the OLED device was purified by vacuum sublimation at 10-6 torr. [Comparative Example 1] Electric field luminescence property of an OLED device using a conventional electron transport material After forming a hole injection layer, a hole transport layer, and an electric field light-emitting layer in the same manner as in Example 1, the vapor deposition thickness was 20 nm ( 8-hydroxyquinoline)aluminum (III) (Alq3) serves as an electron transport layer. Then, a vapor-deposited 8-carboxy σ quinine chain (Liq) having a thickness of 1 to 2 nm is used as an electron injecting layer, and another vacuum vapor deposition apparatus is used to form a thickness of 150 nm (A1). The cathode is fabricated to produce an OLED. The driving voltage and luminous efficiency of the OLEDs comprising the organic electronic material compound or the conventional electron transporting material according to the present invention in Examples 1 to 5 and Comparative Example 1 were measured at 1,000 cd/m 2 , respectively. The results are shown in Table 2. 31 95193 201204729 Table 2 Luminescent efficiency (cd/ampere (A)) measured at 1,000 cd/m2 as measured by a driving voltage (V) at 1,000 cd/m2 Example 1 Compound 2 5.0 12.2 Example 2 Compound 19 4.9 12.5 Example 3 Compound 26 4.6 13.1 Example 4 Compound 52 4.5 13.3 Example 5 Compound 54 5.1 11.8 Comparative Example 1 Alq3 6 11.6 As shown in Table 2, when Compound 52 was used as an electron transporting material At the time of (Example 4), the highest power efficiency occurred. Specifically, the power efficiency of Compound 52 (Example 4) showed an improvement of about 15% as compared with the case of using conventional Aiq3 as the electron transport layer (Comparative Example 1). The driving voltage of Compound 16 (Example 3) showed a decrease of about 1.4 V as compared with the conventional organic electroluminescent device (Comparative Example 1). From the properties obtained by using the compound developed by the present invention as an electron transport layer shown in Table 2, it is understood that the compound developed by the present invention is superior to the conventional material from the viewpoint of self-efficiency. [Examples 6 to 8] Manufacture of an OLED device using an organic electronic material compound according to the present invention An OLed device was produced using the electroluminescent compound of the present invention. First, a transparent electrode ΙΤ0 film (15 Ω / ΕΙ1) obtained from SOC glass (Samsung Corning) was washed with a mixture of three gases, acetone, ethanol and distilled water, and stored in isopropyl alcohol for use. 95193 32 201204729 Then, the ΙΤ0 substrate was assembled in a substrate holder of a vacuum vapor deposition apparatus, and 4, 4', 4"-叁(Ν,Ν-(2-naphthyl)-phenylamino)triphenyl An amine (2-ΤΝΑΤΑ) is placed in a chamber of the vacuum vapor deposition apparatus, and then the chamber is ventilated to a tor vacuum. Subsequently, a current is applied to the chamber to evaporate 2-TNATA, thereby constituting the substrate. A hole injection layer having a thickness of 6 〇-nano (nm) is formed thereon. Subsequently, N,N,-bis(α-naphthyl)-fluorene, Ν'-diphenyl-4,4,-diamine is formed. (ΝΡΒ) is placed in another chamber of the vacuum vapor deposition apparatus, and a current is applied to the chamber to evaporate ΝρΒ, thereby forming a hole transport layer having a thickness of 2〇11 [11] on the hole injection layer. The compound according to the present invention (for example, compound 7) purified by ΙΟ·6 torr vacuum sublimation is placed in a chamber of a vacuum vapor deposition apparatus as a host, and an electric field luminescent dopant (such as a compound (piq) 2lr) (acac)) placed in another chamber. The two materials are evaporated at different rates to pass through 4 to 10% by weight On the hole transport layer vapor-deposited with a thickness of 30nm of the electric field light emitting layer.

有下述結構之雙（2_曱基基啥琳）（對苯基盼）銘（III) (BAlq)作為電洞阻擋層。氣相沉積厚度為20 nm之具有下述結構之秦（8'經基啥琳）叙（出）（Alq3)作為電子傳輸層。然後’氣相沉積厚度為i至2 nm之上述結構之8_經 33 95193 201204729 基㈣链alq)作為電子注人層後，用另一衫氣相沉積裝置开^成厚度為l5G nm之銘（A1)陰極而製造出〇LED。The double structure (2_曱基基啥琳) (for phenyl phenyl) Ming (III) (BAlq) has the following structure as a hole barrier. A vapor-deposited layer of 20 nm has a structure of the above-mentioned Qin (8' 啥啥 ) )) (Alq3) as an electron transport layer. Then, after vapor deposition of the above structure of the thickness of i to 2 nm, 8_ via 33 95193 201204729 base (four) chain alq), as an electron injection layer, the thickness of the film is 155 nm. (A1) The cathode is used to produce a ruthenium LED.

[實施例9至1〇]使用根據本發明之有機電子材料化合物之0LED裝置之製造除了該電洞阻擋層之外，以實施例8之相同方式製造 0LED裝置。 [比較例2]使用常規電子傳輸材料之〇裝i之電場發光性質除了於真空氣相沉積裝置之一小室中使用4,4，_雙 (咔唑-9-基）聯笨（CBP)替代本發明之化合物之外，以實施例6之相同方式製造〇LED。分別於1，OOOcd/m2測量包含根據本發明之有機電場發光化合物之0LED(實施例6至8及實施例9幻〇)以及包含常規EL化合物之〇LED(比較例2)的驅動電壓及發光效率，結果係顯示於表3中。如表3所示，與常規材料相比’根據本發明之有機電場發光化合物係具有優異之發光性質。 95193 34 201204729 表3 主體材料發光材料電洞阻擋層 @l,000cd/m2 顏色驅動電壓(V) 發光效率 (cd/A)+ 實施例6 化合物7 (piqMr(acac) BAlq 7.1 7.2 紅實施例7 化合物8 (piq)2lr(acac) BAlq 6.8 7.3 紅實施例8 化合物15 (piqMr(acac) BAlq 6.9 7.4 紅實施例9 化合物33 (piqMr(acac) - 6.7 7.7 紅實施例10 化合物34 (piqMr(acac) - 7.0 7.6 紅比較例2 CBP (piqMr(acac) BAlq 7.3 6.8 紅如表3中所示，與常規材料相比，根據本發明之有機電場發光化合物係具有優異之發光性質。與比較例2之使用常規材料之裝置相比，他們具有傑出之電流性質。與比較例2之裝置相比，他們的驅動電壓下降約0.2 V或更多，他們還顯示約為比較例2之裝置之1. 1倍或更高的高功率效率。【圖式簡單說明】無【主要元件符號說明】無 35 95193[Examples 9 to 1] Production of an OLED device using an organic electronic material compound according to the present invention An OLED device was produced in the same manner as in Example 8 except for the hole blocking layer. [Comparative Example 2] Electric field luminescence property of armor i using a conventional electron transport material In addition to the use of 4,4,_bis(carbazol-9-yl) phenyl (CBP) in a chamber of a vacuum vapor deposition apparatus A ruthenium LED was produced in the same manner as in Example 6 except for the compound of the present invention. The driving voltage and luminescence of the OLED (Examples 6 to 8 and Example 9 illusion) containing the organic electroluminescent compound according to the present invention and the 〇LED (Comparative Example 2) containing the conventional EL compound were measured at 1,100 cd/m 2 , respectively. Efficiency, results are shown in Table 3. As shown in Table 3, the organic electric field luminescent compound according to the present invention has excellent luminescent properties as compared with conventional materials. 95193 34 201204729 Table 3 Host material Luminescent material hole barrier @l,000cd/m2 Color drive voltage (V) Luminous efficiency (cd/A) + Example 6 Compound 7 (piqMr(acac) BAlq 7.1 7.2 Red Example 7 Compound 8 (piq) 2lr(acac) BAlq 6.8 7.3 Red Example 8 Compound 15 (piqMr(acac) BAlq 6.9 7.4 Red Example 9 Compound 33 (piqMr(acac) - 6.7 7.7 Red Example 10 Compound 34 (piqMr(acac - 7.0 7.6 Red Comparative Example 2 CBP (piqMr(acac) BAlq 7.3 6.8 Red As shown in Table 3, the organic electroluminescent compound according to the present invention has excellent luminescent properties as compared with the conventional material. They have excellent current properties compared to devices using conventional materials. Their driving voltage drops by about 0.2 V or more compared to the device of Comparative Example 2, and they also show about 1. 1x or higher high power efficiency. [Simple description of the diagram] No [Main component symbol description] No 35 95193

Claims

201204729 七、申請專利範圍： 1. 一種化學式（1)表示之有機電子材料化合物：化學式（1)201204729 VII. Patent application scope: 1. A compound of organic electronic material represented by chemical formula (1): Chemical formula (1)

其中， X 係表不~C(Ri)(I^2)-、-Si(R3)(R4)-、-S-或; 匕至R4係獨立表示（C1_C30)烷基、（C6_C3〇)芳基或（C3-C30)雜芳基，或者^與R2或Ru與&可經由具有或不具有稠合環之（C3-C12)伸烷基或（C3-C12)伸烯基相鏈結以形成螺環或稠環； Αιί至Ar4係獨立表示氫、（C1-C30)烷基、鹵素、二（C1-C30)烷基硼烷基、二（C6-C30)芳基硼烷基、氰基、（C3-C30)環烷基、N-嗎啉基、N-硫代嗎啉基、N- 哌啶基、5員至7員雜環烷基、（C7-C30)雙環烷基、 (C2-C30)烯基、（C2-C30)炔基、（C6-C30)芳基、（C1-C30) 烷氧基、（C6-C30)芳氧基、（C3-C30)雜芳基、咔唑基、 (C6-C30)芳基（C1-C30)烷基、（C6-C30)芳硫基、單或二 (C1-C30)烷基胺基、單或二（C6-C30)芳基胺基、三 (C1-C30)烷基矽烷基、二（c卜C30)烷基（C6-C30)芳基矽烧基、二（C6-C30)芳基;ε夕烧基、硝基或經基；該Ri至R4之烷基、芳基或雜芳基，以及該Αη至 An之烷基、環烷基、雜環烷基、雙環烷基、烷基硼烷 95193 1 201204729 基、芳基喊基、烯基、炔基、芳基、烧氧基、芳氧基、雜芳基、芳隸基、芳硫基、絲胺基、芳基胺基、三烧基石夕烧H基芳基錢基或三絲魏基，可進 • —步經一個或多個選自下列所纽成群組之取代基取 - 代：氣、（ci-⑽院基、齒（C1_C30)燒基、齒素、氛基、 (C3-C：3(〇環烧基、5貞至7員雜環烧基、（C7_C3〇)雙環烧基、（C2-C30)稀基、（C2_C3〇)块基、（C6_c3〇)芳基、 ⑹-⑽烷氧基、⑽一C30)芳氧基、(C3_c3〇)雜芳基、經（C1-C30)烧基取代之（C3〜C3〇)雜芳基、經（c6_c3〇) 方基取代之（C3-C30)雜芳基、（C6_C3〇)芳基（cl_C3〇) 烷基、（C6-C30)芳硫基、單或二（cl_C3〇)烧基胺基、單或二（C6-G3G)芳基絲、三（G卜⑶滅基魏基、二 (C卜C3G)減（G6-G3{))芳基魏基、三⑽侧芳基石夕烷基、硝基及羥基；以及該雜環絲或雜芳基可含有選自B、N、〇、S、 P(-〇)、Si及p之一個或多個雜原子。 2.如申明專利範圍帛i項所述之有機電子材料化合物，其中，X 係表示-咖他)一、_Si(R3)(R4)_、I、或選自下列結構之二價基：Wherein, the X series is not ~C(Ri)(I^2)-, -Si(R3)(R4)-, -S- or; 匕 to R4 are independently represented by (C1_C30) alkyl, (C6_C3〇) aryl Or a (C3-C30)heteroaryl group, or a combination of R2 or Ru with & can be via a (C3-C12)alkyl or (C3-C12)alkylene chain with or without a fused ring To form a spiro ring or a fused ring; Αιί to Ar4 independently represent hydrogen, (C1-C30) alkyl, halogen, di(C1-C30)alkylboran, di(C6-C30)arylboran, Cyano, (C3-C30)cycloalkyl, N-morpholinyl, N-thiomorpholinyl, N-piperidinyl, 5- to 7-membered heterocycloalkyl, (C7-C30)bicycloalkyl (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl , carbazolyl, (C6-C30) aryl (C1-C30) alkyl, (C6-C30) arylthio, mono or di(C1-C30)alkylamino, mono or di (C6-C30 An arylamino group, a tri(C1-C30)alkyldecyl group, a di(c-C30)alkyl group (C6-C30) arylsulfonyl group, a di(C6-C30)aryl group; a nitro group or a aryl group; an alkyl group, an aryl group or a heteroaryl group of Ri to R4, and the Α An alkyl, cycloalkyl, heterocycloalkyl, bicycloalkyl, alkylborane 95193 1 201204729 base, aryl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, hetero An aryl group, an aryl group, an arylthio group, a silky amino group, an arylamino group, a tricalcium group, a H-aryl aryl group or a tri-silve group, which may be subjected to one or more selected from the following The substituents of the group are: gas, (ci-(10) yard base, tooth (C1_C30) base, dentate, aryl group, (C3-C:3 (〇环烧基, 5贞 to 7) Heterocyclic alkyl, (C7_C3〇)bicycloalkyl, (C2-C30) dilute, (C2_C3〇) block, (C6_c3〇) aryl, (6)-(10) alkoxy, (10)-C30) aryloxy (C3_c3〇)heteroaryl, (C3-C3〇)heteroaryl substituted by (C1-C30)alkyl, (C3-C30)heteroaryl substituted by (c6_c3〇) aryl, (C6_C3〇 Aryl (cl_C3〇) alkyl, (C6-C30) arylthio, mono or di(cl_C3〇)alkylamino, mono or di(C6-G3G) aryl, tris(G)(3) Wei Ji, II (C Bu C3G) minus (G6-G3{)) aryl-Wilyl, tris(10)-side aryl-based alkyl, nitro and hydroxy And wire or heterocyclic aryl group may contain heteroatoms selected from B, N, square, S, P (-〇), and p is a Si or more heteroatoms. 2. An organic electronic material compound as claimed in claim IA, wherein X represents -catha), _Si(R3)(R4)_, I, or a divalent group selected from the group consisting of:

• 傘傘匕至R4係獨立表示（c卜C30)烷基或（C6-C30)芳基； An至An係獨立表示（C3_C3〇)環烷基、^嗎啉基、 2 95193 201204729 N-硫代嗎淋基、（C7-C30)雙環烧基、（C2-C30)稀基、 (C2-C30)炔基、（C6-C30)芳基、（C6-C30)芳氧基、 (C3-C30)雜芳基、咔唑基、（C6-C30)芳硫基、三（C1_C3()) 烷基矽烷基、二（C1-C30)烷基（C6-C30)芳基碎烧基或三 (C6-C30)芳基矽烷基；以及該Ri至R4之烧基或芳基以及該An至Ar4之環燒基、雙環烷基、烯基、炔基、芳基、芳氧基、雜芳基、芳硫基、三烷基矽烷基、二烷基芳基矽烷基或三芳基矽烷基，可進一步經一個或多個選自下列所組成群組之取代基取代：氘、（C1-C30)烷基、函（C1-C30)烷基、齒素、氰基、（C3-C30)環烷基、5員至7員雜環烷基、（C7-C30) 雙環烷基、（C2-C30)烯基、（C2-C30)炔基、（C6-C30) 芳基、（C1-C30)烷氧基、（C6-C30)芳氧基、（C3-C30) 雜芳基、經（a-C30)烷基取代之（C3-C30)雜芳基、經 (C6-C30)芳基取代之（c*S-C30)雜芳基、（C6-C30)芳基 (C1-C30)烷基、（C6-C30)芳硫基、單或二（C1-C30)烷基知基、單或一（C6-C30)芳基胺基、三（C1-C30)烧基石夕烧基、二（C1-C30)烷基（C6-C30)芳基矽烷基、三（C6-C30) 芳基矽烷基、硝基及羥基。 3. —種有機電場發光裝置，係包含申請專利範圍第丨至2 項中任一項所述之有機電子材料化合物作為電子傳輸材料。 4. 如申請專利範圍第3項所述之有機電場發光裝置，其係包3第一電極，第二電極；以及一層或多層插置於該第 3 95193 201204729 j極與該第二電極間之有機層；其中，該有機層包含 :或多層包括藉由化學式⑴表示之有機電子材料化 2的層’以及―層或多層包括螢光主體及螢光摻雜劑或l括磷光主體及磷光摻雜劑的層。 •如申4專利㈣第4項所述之有機電場發光裝置，其中’该有機層進-步包含—種或多種選自由芳基胺化合物及苯乙縣綠胺化合物所組成群組之胺化合物。 6. 如申β月專利範圍$ 4項所述之有機電場發光裝置，其中’該有機層進-步包含—種或多種選自第β之有機金屬、第2族、第4周期與第5周期之過渡金屬、鑭系金屬及d-過渡元素所組成群組之金屬或錯合化合物。 7. 如申請專利範圍第4項所述之有機電場發光裝置，其中’該有機層包含電場發光層及電荷產生層。 8·如申凊專利範圍第4項所述之有機電場發光裝置，其係發射白光之有機電場發光裝置，其中，該有機層係同時包含一層或多層發射藍光、紅光或綠光之有機電場發光層。 9·如申請專利範圍第4項所述之有機電場發光裝置，其中，於該電極對中之一個或兩個電極的内表面上係設置還原性摻雜劑與有機物質之混合區域或氧化性摻雜劑與有機物質之混合區域。 4 95193 201204729 四、指定代表圖：本案無圖式 (一) 本案指定代表圖為：第（）圖。 (二) 本代表圖之元件符號簡單說明：五、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（1)• Umbrella to R4 stands for (c, C30) alkyl or (C6-C30) aryl; An to An stands for (C3_C3〇) cycloalkyl, ^morpholinyl, 2 95193 201204729 N-sulfur Substituted, (C7-C30)bicycloalkyl, (C2-C30), (C2-C30) alkynyl, (C6-C30) aryl, (C6-C30) aryloxy, (C3- C30) heteroaryl, carbazolyl, (C6-C30) arylthio, tri(C1_C3())alkyldecyl, di(C1-C30)alkyl(C6-C30)arylalkyl or tri (C6-C30) arylalkylalkyl; and the alkyl or aryl group of Ri to R4 and the cycloalkyl, bicycloalkyl, alkenyl, alkynyl, aryl, aryloxy, heteroaryl of the An to Ar4 a aryl group, an arylthio group, a trialkyl decyl group, a dialkyl aryl decyl group or a triaryl decyl group, which may be further substituted with one or more substituents selected from the group consisting of hydrazine, (C1-C30) Alkyl, functional (C1-C30) alkyl, dentate, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C7-C30)bicycloalkyl, (C2- C30) alkenyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30) heteroaryl (C3-C30)heteroaryl group substituted by (a-C30)alkyl group, (c*S-C30)heteroaryl group substituted by (C6-C30) aryl group, (C6-C30) aryl group ( C1-C30)alkyl, (C6-C30) arylthio, mono or di(C1-C30)alkyl, mono or mono(C6-C30)arylamino, tri(C1-C30) sulphur Anthracyl, di(C1-C30)alkyl (C6-C30) arylalkyl, tris(C6-C30) arylalkyl, nitro and hydroxy. An organic electric field light-emitting device comprising the organic electronic material compound according to any one of claims 2 to 2 as an electron transporting material. 4. The organic electric field light-emitting device according to claim 3, wherein the first electrode and the second electrode of the package 3 are; and one or more layers are interposed between the third electrode of the third 95193 201204729 and the second electrode. An organic layer; wherein the organic layer comprises: or a plurality of layers including the organic electronic materialization 2 represented by the chemical formula (1) and the layer or layers comprising a fluorescent host and a fluorescent dopant or a phosphorescent host and a phosphorescent dopant The layer of the dopant. The organic electroluminescence device of claim 4, wherein the organic layer further comprises one or more amine compounds selected from the group consisting of arylamine compounds and phenethylamine green amine compounds. . 6. The organic electric field illuminating device according to claim 4, wherein the organic layer further comprises one or more organometallics selected from the group consisting of β, the second group, the fourth period and the fifth A metal or a compound of a group consisting of a transition metal, a lanthanide metal, and a d-transition element. 7. The organic electroluminescent device of claim 4, wherein the organic layer comprises an electric field luminescent layer and a charge generating layer. 8. The organic electric field illuminating device according to claim 4, which is an organic electric field illuminating device that emits white light, wherein the organic layer simultaneously comprises one or more organic electric fields emitting blue light, red light or green light. Light-emitting layer. 9. The organic electric field light-emitting device according to claim 4, wherein a mixing region or an oxidizing property of the reducing dopant and the organic substance is disposed on an inner surface of one or both of the electrode pairs. A mixed region of a dopant and an organic substance. 4 95193 201204729 IV. Designated representative map: There is no schema in this case (1) The representative representative figure of this case is: (). (2) A brief description of the symbol of the representative figure: 5. 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)

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