TW201226394A - Electron transport material and organic electroluminescent device using the same - Google Patents
Electron transport material and organic electroluminescent device using the same Download PDFInfo
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Abstract
Description
201226394 六、發明說明: 【發明所屬之技術領域】 電子傳輪材 (以T,有 本發明疋有關於一種具有π比咬基的新賴 料、使用該電子傳輸材料的有機電激發光元件 時簡稱為有機EL元件,或僅簡稱為元件)等 近年來,錢EL元件料次世代的全 (func〇lorflatpaneldisplay)而備受_目=不器 躍地對其進行研究。為了促進有機EL元件的實=正活 件驅動崎低、壽命延長是何或缺的要素 = 現這些要素,業界-直在開發新的電子傳輸材料。2 = 須貫現藍色元件的驅動糕降低、壽命延長。專利& (曰本專利特開20〇3·1239δ3號公報)中記載有如^ 況.措由將作為啡琳(phenanthroline)衍生物或其類似物^ 2,2’♦㈣化合物祕電子傳輸材料,能以低電壓驅動有 機EL TL件。然而,該文獻的實例所報告的元件特性(驅 動電壓、發光效率等)僅為以比較例為基準的相對值,並 未記載可判斷為實用值的實測值。此外,將2,2,-聯吡啶化 合物用於電子傳輸材料的例子在非專利文獻1 (Proceedings of the 10th International Workshop on201226394 VI. Description of the Invention: [Technical Field According to the Invention] An electron transfer wheel (for T, there is a novel material having a π-bite base, and an organic electroluminescence element using the electron transport material) In recent years, in recent years, the money EL element has been studied for the next generation (func〇 lor flat panel display) and has been studied. In order to promote the real-life of the organic EL element, the low-level operation and the longevity of the life-saving elements are indispensable. Now, these factors, the industry, are directly developing new electronic transmission materials. 2 = The driving force of the blue component is reduced and the life is extended. The patent & (Japanese Patent Laid-Open Publication No. 20 〇 3·1239 δ 3) describes the case as a phenanthroline derivative or an analog thereof. 2, 2' ♦ (4) compound secret electron transport material The organic EL TL device can be driven at a low voltage. However, the element characteristics (driving voltage, luminous efficiency, etc.) reported by the examples of this document are only relative values based on comparative examples, and actual measured values which can be judged to be practical values are not described. Further, an example in which a 2,2,-bipyridyl compound is used for an electron transporting material is disclosed in Non-Patent Document 1 (Proceedings of the 10th International Workshop on
Inorganic and Organic Electroluminescence,第十屆無機及 有機電激發光國際研討會文集)、專利文獻2 (日本專利特 開2002-158093號公報)及專利文獻3 (國際公開 2007/86552手冊)中有揭示。非專利文獻1中記載的化合 201226394 物之Tg低’並不實用。專利文獻2及專利文獻3中記載 的化合物雖然能以相對低電壓來驅動有機EL元件,但實 際應用時仍期待能進一步使壽命延長。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開2003-123983號公報 [專利文獻2]日本專利特開2〇〇2_158〇93號公報 [專利文獻3]國際公開2007/86552手冊 [非專利文獻] [非專利文獻 l]Proceedings of the 1〇* Internati〇nal shop 〇n Inorganic and Organic Electroluminescence (2000)(第十屆無機及有機電激發光國際研討會文集 (2000)) 【發明内容】 本發明是繁於此種先前技術所存在的課題研究而成。 月的課題在於提供—财助於有機EL元件的壽命延 =的電子傳輸材料。此外,本發_課題在於提供一種 使用該電子傳輸材料的有機EL元件。 於八者等人經過努力研究,結果發現:藉由將如下 ==苯基中的任-個上具W基、;=本ΐ ;且6苯Γ萘環及物上的至少-個氮被取 代為厌數為1〜6狀基或碳數為3〜6的環絲的化合 201226394 物’基於該發現而完成本發明。 上述的課題是藉由以下所示的各項而解決 [1]一種化合物,其以下述式(1)表示,Inorganic and Organic Electroluminescence, the 10th International Symposium on Inorganic and Organic Electroluminescence, and Patent Document 2 (Japanese Patent Laid-Open Publication No. 2002-158093) and Patent Document 3 (International Publication No. 2007/86552) disclose. The low Tg of the compound 201226394 described in Non-Patent Document 1 is not practical. Although the compound described in Patent Document 2 and Patent Document 3 can drive the organic EL element at a relatively low voltage, it is expected to further extend the life in practical use. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-123983 (Patent Document 2) Japanese Patent Laid-Open Publication No. Hei No. Hei. 86552 manual [Non-patent literature] [Non-Patent Document 1] Proceedings of the 1〇* Internati〇nal shop 〇n Inorganic and Organic Electroluminescence (2000) (The 10th International Symposium on Inorganic and Organic Electroluminescence (2000)) SUMMARY OF THE INVENTION The present invention has been developed in the field of the prior art. The problem of the month is to provide an electron transport material that contributes to the life extension of the organic EL element. Further, the present invention has been made in an object of providing an organic EL device using the electron transporting material. After eight studies by eight people and others, it was found that at least one nitrogen on the 6 phenylene naphthalene ring was obtained by having any of the following == phenyl groups; The present invention was completed based on the discovery, in place of the compound 201226394, which is a loop wire having an anisotropy of 1 to 6 or a carbon number of 3 to 6. The above problem is solved by the following items [1] a compound represented by the following formula (1).
Py獨立為式(2)、(3)或(4)所表示的基; <}-〇 -^0 (2) … … n 為 0 或 1,m + n: 、* 1 Al 1 » jim_ 5 # a ( j丨、)中的苯環、萘環及咣啶環上的至少一個氫被 ^為1〜6的烧基或碳數為3〜6的環炫基。 n如上述[1]項所述之化合物,其以下述式(1-1) 、丄-2 )表示,Py is independently a group represented by the formula (2), (3) or (4); <}-〇-^0 (2) ... n is 0 or 1, m + n: , * 1 Al 1 » jim_ At least one hydrogen on the benzene ring, the naphthalene ring and the acridine ring in 5 # a ( j丨,) is a carbonyl group of 1 to 6 or a cyclodext group having a carbon number of 3 to 6. n The compound according to the above [1], which is represented by the following formula (1-1), 丄-2),
201226394 式(1-1)及(1-2)中,201226394 In the formulas (1-1) and (1-2),
Py為式(2)、(3)或(4)所表示的基;Py is a group represented by the formula (2), (3) or (4);
並且’式(M)及(1-2)中的笨環、萘環及η比啶環 上的至少一個氫被取代為碳數為1〜6的烷基或碳數為3〜 6的環烷基。 [3]如上述[1]項所述之化合物,其以下述式0-3)、 (1-4)、(1-5)、或(1-6)表示,And at least one hydrogen on the stupid ring, the naphthalene ring and the η-pyridine ring in the formulae (M) and (1-2) is substituted with an alkyl group having a carbon number of 1 to 6 or a ring having a carbon number of 3 to 6 alkyl. [3] The compound according to the above [1], which is represented by the following formulas 0-3), (1-4), (1-5), or (1-6).
式(1-3)〜(1-6)中,In the formula (1-3) to (1-6),
Py為式(2)、(3)或(4)所表示的基; Ό -Ck!) (2) ⑶ (4) 7 201226394 並且’式(1-3)〜(1-6)中的苯環、萘環及吼啶環 上的至少一個氫被取代為碳數為1〜6的烷基或碳數為3〜 6的環烷基。 [4]如上述[1]所述之化合物,其以下述式(丨_7)或(u) 表示,Py is a group represented by the formula (2), (3) or (4); Ό -Ck!) (2) (3) (4) 7 201226394 and benzene in the formula (1-3) to (1-6) At least one hydrogen on the ring, naphthalene ring and acridine ring is substituted with an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. [4] The compound according to the above [1], which is represented by the following formula (丨_7) or (u),
式(1-7)及(1-8)中,In the formulas (1-7) and (1-8),
Py為式(2)、(3)或(4)所表示的基; (2) (3) (4) R為碳數為1〜6的烧基或碳數為3〜6的環院基;並 I, p為1〜5的整數。 [5]如上述[η項所述之化合物,其以下述式(或 (1-10)表示,Py is a group represented by the formula (2), (3) or (4); (2) (3) (4) R is a group having a carbon number of 1 to 6 or a ring having a carbon number of 3 to 6 And I, p is an integer from 1 to 5. [5] The compound according to the above [nth item, which is represented by the following formula (or (1-10),
II 201226394 式(^9)及(ι_ι〇)中,II 201226394 In the formula (^9) and (ι_ι〇),
Py為式(2)、(3)或(4)所表示的基; -C)夺i) ^0 (2) ⑶ ⑷ R為碳數為1〜6的烧基或碳數為3〜6的環烧基;並 且, q為1〜5的整數。 ’其以下述式(1-11)或 [6]如上述[1]項所述之化合物 (1-12)表示,Py is a group represented by the formula (2), (3) or (4); -C) is i) ^0 (2) (3) (4) R is a carbon group having a carbon number of 1 to 6 or a carbon number of 3 to 6 And a q is an integer of 1 to 5. It is represented by the following formula (1-11) or [6] as the compound (1-12) described in the above [1],
式(1-H)及(1_12)中,In the formulas (1-H) and (1_12),
Py為式(2’)、(3’)或(4')所表示的基;Py is a group represented by the formula (2'), (3') or (4');
式(2’)、(3,)及(4’)中,R為碳數為j〜6的烷基或 201226394 碳數為3〜6的環烷基;並且,s為i〜4的整數。 [7]如上述[丨]項所述之化合物,其以下述式(1-13)或 (1-14 )表示,In the formulae (2'), (3), and (4'), R is an alkyl group having a carbon number of j 6 or a cyclic alkyl group having a carbon number of 3 to 6 in 201226394; and s is an integer of i 4 . [7] The compound according to the above [丨], which is represented by the following formula (1-13) or (1-14),
式(1-13 )及(1_14)中,In equations (1-13) and (1_14),
Py為式(2’)、(3’)或(4')所表示的基;Py is a group represented by the formula (2'), (3') or (4');
^式(2’)、(3,)或(4,)中,R為碳數為】〜6的烷基或 碳數為3〜6的環燒基;並且,s為j〜4的整數。 [8]如上述[丨]項所述之化合物,其以下述式(1-15)或 (1-16)表示,In the formula (2'), (3,) or (4,), R is an alkyl group having a carbon number of 〜6 or a cycloalkyl group having a carbon number of 3 to 6; and, s is an integer of j 4 . [8] The compound according to the above [丨], which is represented by the following formula (1-15) or (1-16),
201226394 4U55Upif 式(1-15)及(1-16)中,201226394 4U55Upif type (1-15) and (1-16),
Py為式(2)、(3)或(4)所表示的基;Py is a group represented by the formula (2), (3) or (4);
R為碳數為1〜6的烷基或碳數為3〜6的環烷基;並 且,t為1〜4的整數。 [9]如上述[1]項所述之化合物,其以下述式(1-7-26) 表示R is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms; and t is an integer of 1 to 4. [9] The compound according to [1] above, which is represented by the following formula (1-7-26)
[10]如上述[1]項所述之化合物,其以下述式(1-7-74) 表示[10] The compound according to the above [1], which is represented by the following formula (1-7-74)
[11]如上述[1]項所述之化合物,其以下述式(1-7-98) 表示 11[11] The compound according to the above [1], which is represented by the following formula (1-7-98) 11
201226394 HUJ201226394 HUJ
[12]如上述[1]項所述之化合物,其以下述式(1-7-96) 表示[12] The compound according to [1] above, which is represented by the following formula (1-7-96)
[13]如上述[1]項所述之化合物,其以下述式(1-14-14) 表示[13] The compound according to [1] above, which is represented by the following formula (1-14-14)
[14]如上述[1]項所述之化合物,其以下述式 (M1-1)、( 1-11-2)、( 1-11-3)、( M1-4)、( 1-11-5)、 (1-11-6)、( 1-11-8)、( 1-11-18)、( 1-11-39)、( 1-14-2)、 12 201226394 (1-14-3 )、( 1-14-11 )、( 1-14-12)、( 1-14-13)、( 1-14-15)、 (1-14-16)、(1-14-17)、(1-14-18)、及(1-14-20)中的任 一個表示[14] The compound according to the above [1], which is represented by the following formula (M1-1), (1-11-2), (1-11-3), (M1-4), (1-11). -5), (1-11-6), (1-11-8), (1-11-18), (1-11-39), (1-14-2), 12 201226394 (1-14 -3 ), ( 1-14-11 ), ( 1-14-12), ( 1-14-13), ( 1-14-15), (1-14-16), (1-14-17 Any one of (1-14-18), and (1-14-20)
13 20122639413 201226394
[15]—種電子傳輸材料,其含有如上述[1]至[14]中任 14 201226394 40550pif 一項所述之化合物。 [16] —種有機電激發光元件,其包括:包含陽極及陰 極的一對電極、配置在該一對電極之間的發光層、及配置 在上述陰極與該發光層之間且含有如上述[15]項所述之電 子傳輸材料的電子傳輸層及/或電子注入層。 [Π]如上述[16]項所述之有機電激發光元件,其中上述 電子傳輸層及電子注入層中的至少一層更包括選自由羥基 喧琳系金屬錯合物、聯π比咬衍生物、啡淋衍生物及爛烧衍 生物所組成的群中的至少一種。 [18]如上述[16]或[17]項所述之有機電激發光元件,其 中電子傳輸層及電子注入層中的至少一層更包括選自由驗 金屬、鹼土金屬、稀土金屬、齡屬的氧化物、驗金屬的 ,化物、驗土金屬的氧化物、驗土金屬的鹵化物、稀土金 物、稀土金屬的鹵化物、鹼金屬的有機錯合物、 群中錯合物及稀土金屬的有機錯合物所組成的 L 5¾ %叼双果] 另外,即使在薄膜狀態下施加電壓亦穩定, 合用作;的特徵。本發明的化合物適 化合物用於有機EL、1傳難料。藉由將本發明的 可獲得具有層蝴電子注入層, 機EL元件,可製作全 件」猎由使用本發明的有 【實施方式】 八、、不荨的尚性能顯示器裝置。 201226394 4〇550pif 以下,更詳細地說明本發明。此外,在本說明書中, 例如有時將「式(1-7-26)所表示的化合物」稱為「化合 物(1-7-26)」。有時將「式(1_7·74)所表示的化合物」稱 為「化合物(1-7-74)」。其他式的符號、式的編號亦相同。 <化合物的說明> 本案的第1發明是-種下述式⑴所表示的具有吼咬 基、聯吡啶基或吡啶基苯基的化合物。[15] An electron transporting material comprising the compound according to any one of the above [1] to [14], wherein the one of the ones of the ones of the above-mentioned. [16] An organic electroluminescence device comprising: a pair of electrodes including an anode and a cathode; a light-emitting layer disposed between the pair of electrodes; and a cathode disposed between the cathode and the light-emitting layer and containing the above The electron transport layer and/or the electron injection layer of the electron transport material according to [15]. The organic electroluminescent device of the above-mentioned item [16], wherein at least one of the electron transport layer and the electron injecting layer further comprises a metal conjugate selected from the group consisting of a hydroxy phthalocyanine metal complex and a π ratio bite derivative At least one of the group consisting of a morphine derivative and a rotten derivative. [18] The organic electroluminescent device of the above-mentioned [16] or [17], wherein at least one of the electron transport layer and the electron injecting layer further comprises a metal selected from the group consisting of a metal, an alkaline earth metal, a rare earth metal, and a genus Oxide, metallurgical, chemical, earth metal oxide, earth metal halide, rare earth gold, rare earth metal halide, alkali metal organic complex, group complex and rare earth metal organic L 53⁄4 % 叼 double fruit composed of the complex compound. Further, even if a voltage is applied in a thin film state, it is stable and used as a feature. The compound suitable for use in the present invention is used in organic EL and is difficult to transfer. According to the present invention, it is possible to produce a full-piece display device by using the EL element of the layer, and the EL device of the present invention. 201226394 4〇550pif Hereinafter, the present invention will be described in more detail. In the present specification, for example, "the compound represented by the formula (1-7-26)" may be referred to as "the compound (1-7-26)". The compound represented by the formula (1_7·74) is sometimes referred to as "compound (1-7-74)". The symbols and formulas of other formulas are also the same. <Description of the Compound> The first invention of the present invention is a compound having a thiol group, a bipyridyl group or a pyridylphenyl group represented by the following formula (1).
(2) (3) (4) 式⑴中,Py獨立為式⑺、(3)或⑷所表示 二m及n為〇或bm + d。並且’式⑴中的苯稽 不衣及吡。疋裱上的至少一個氫被取代為碳數為1〜.6的 基或碳數為3〜6的環烷基是本化合物的特徵。 式(2)所表示的吡啶基具體為2·吡啶基、孓吡 4·0比。定基。 土 式(3)所表示的聯吡啶基具體為2,2,-聯吼啶_5_基 2,2’-聯°比。定_6-基、2,2,-聯 t定-4-基、2,3,,π比咬_5_基、2 聯口比。定-6-基、2,3,_聯吡咬_4_基、2,4,令比咬_5_基、土2,心(2) (3) (4) In the formula (1), Py is independently represented by the formula (7), (3) or (4), and m and n are 〇 or bm + d. And the benzene in the formula (1) is not coated with pyridine. The substitution of at least one hydrogen on the oxime to a group having a carbon number of 1 to 6. or a cycloalkyl group having a carbon number of 3 to 6 is a feature of the present compound. The pyridyl group represented by the formula (2) is specifically a 2·pyridyl group or a pyridyl group. Set the foundation. The bipyridyl group represented by the formula (3) is specifically a 2,2,-biindole-5-yl 2,2'-linked ratio. _6-based, 2,2,-linked t-1,4-yl, 2,3,,π ratio bite _5_ base, 2 joint ratio. -6-based, 2,3, _ _ _ _ _ 4 _ base, 2, 4, let the bite _5_ base, soil 2, heart
16 201226394 40550pif 吡啶-6-基、2,4’-聯吡啶-4_基、3,2'-聯吡啶-6-基、3,2,-聯吡 咬-5-基、3,3'-聯°比咬-6·基、3,3'-聯°比咬-5-基、3,4,_聯吡。定 -6-基、3,4’-聯吡啶-5-基、4,2,-聯吡啶-3-基、4,3’-聯吡啶-3-基、或4,4’-聯》比啶-3-基。 式(4)所表示的响啶基苯基具體為4-(2-°比啶基)苯基、 4-(3-吡啶基)苯基、4_(4_吡啶基)苯基、3_(2_吡啶基)苯基、 3-(3-吼啶基)苯基、3-(4-吼啶基)苯基、2-(2-°比啶基)笨基、 2-(3-n比啶基)苯基、或2·(4_β比啶基)苯基。 式(1)中,Py所連結的位置在苯基、2-萘基上均可 為任意位置’在苯基上較佳為4位及3位,在2-萘基上較 佳為ό位及7位。就不擴大共軛體系方面、及不降低lum〇 (lowest unoccupied molecular orbital ’ 最低未佔用分子軌 域)的能階方面而言,尤佳為苯基的3位。另外,就原料 容易獲得方面而言,尤佳為2-萘基的6位。 式(1)中的苯環、萘環、及吡啶環上所取代的碳數 1〜6的烧基的例子為:甲基'乙基、正丙基、異丙基、正 丁基、異丁基、第三丁基、正戊基、異戊基、2,2-二曱美 盆正己基、及異己基。其愤佳的烧基為甲基、乙基, 〜6的〜览… Μ基及第二丁基。碳數為3 6的壤烧基的例子為環丙基、環丁基、環戊基、環己夷。 、,若考慮到原料的獲得、合成的容易程;s:, 環燒基為虹基。 *餘度’職佳的 所的化合物具體為下述式(⑷或(叫 17 20122639416 201226394 40550pif Pyridine-6-yl, 2,4'-bipyridin-4-yl, 3,2'-bipyridyl-6-yl, 3,2,-bipyridyl-5-yl, 3,3' - 联 ° bit -6 · base, 3, 3 '- ̄ ° ° bite 5--base, 3, 4, _ _ _ _ _ D--6-yl, 3,4'-bipyridin-5-yl, 4,2,-bipyridin-3-yl, 4,3'-bipyridin-3-yl, or 4,4'-linked Bipyridin-3-yl. The fluorenylphenyl group represented by the formula (4) is specifically 4-(2-pyridinyl)phenyl, 4-(3-pyridyl)phenyl, 4-(4-pyridyl)phenyl, 3-(( 2_pyridyl)phenyl, 3-(3-acridinyl)phenyl, 3-(4-oxaridinyl)phenyl, 2-(2-pyridyl)phenyl, 2-(3- N-pyridyl)phenyl, or 2·(4_β-pyridyl)phenyl. In the formula (1), the position at which Py is bonded may be any position on the phenyl group or the 2-naphthyl group. The position is preferably 4 and 3 on the phenyl group, and preferably the position on the 2-naphthyl group. And 7 digits. In terms of not expanding the conjugated system and not lowering the energy level of the lum〇 (lowest unoccupied molecular orbital ‘ minimum unoccupied molecular orbital domain), it is particularly preferred to be the 3-position of the phenyl group. Further, in terms of easy availability of the raw material, it is particularly preferably a 6-position of 2-naphthyl group. Examples of the benzene ring, the naphthalene ring, and the alkyl group having 1 to 6 carbon atoms substituted in the pyridine ring in the formula (1) are: methyl 'ethyl, n-propyl, isopropyl, n-butyl, and iso- Butyl, tert-butyl, n-pentyl, isopentyl, 2,2-dioxime, n-hexyl, and isohexyl. Its succinct base is methyl, ethyl, ~6 ~ Μ Μ and second butyl. Examples of the soil burnt group having a carbon number of 36 are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. If the raw material is obtained and the ease of synthesis is taken into consideration; s:, the ring-burning group is a rainbow base. *The compound of the 'Yujia' is the following formula ((4) or (called 17 201226394)
式(1-1)及(1-2)中的Py的定義與上述相同。 式(〇所表示的化合物更具體而言為下述式(卜3) (1-6)中的任一個所表示的化合物。The definitions of Py in the formulae (1-1) and (1-2) are the same as described above. More specifically, the compound represented by the formula (〇) is a compound represented by any one of the following formulas (Bu 3) (1-6).
式(1-3)〜(1·6)中的Py的定義與上述相同。 式(1)所表示的化合物更具體為下述式(17)〜^⑴ 中的任一個所表示的化合物。The definition of Py in the formulae (1-3) to (1.6) is the same as described above. The compound represented by the formula (1) is more specifically a compound represented by any one of the following formulas (17) to (1).
201226394 HUD^Upif201226394 HUD^Upif
式(1-7)〜(MO)中的Py及R的定義與上述相同。 式(1-7)及(1-8)中的p為1〜5的整數,較佳為1〜2 的整數’更佳為1。R所取代的苯基的位置並無限制,較 佳為3位或4位。式(1-9)及(1-10)中的q為1〜5的 整數,較佳為1〜2的整數,更佳為1。R所取代的萘基的 位置並無限制’較佳為6位或7位。 另外’式(1 )所表示的化合物更具體為下述式(1_11) 〜(M4)中的任一個所表示的化合物。The definitions of Py and R in the formulae (1-7) to (MO) are the same as described above. In the formulae (1-7) and (1-8), p is an integer of 1 to 5, preferably an integer of 1 to 2' is more preferably 1. The position of the phenyl group substituted by R is not limited, and is preferably 3 or 4 positions. q in the formulae (1-9) and (1-10) is an integer of 1 to 5, preferably an integer of 1 to 2, more preferably 1. The position of the naphthyl group substituted by R is not limited to the position of 6 or 7 positions. Further, the compound represented by the formula (1) is more specifically a compound represented by any one of the following formulas (1-11) to (M4).
19 201226394 40550pif 式(1-11)〜(1-14)中的Py1的定義與上述相同。上 述式(2〇、(3')或(4〇中的R的定義與上述相同。s為 1〜4的整數,較佳為1或2,更佳為1。R所取代的吡啶 基的位置並無特別限制。 另外,式(1)所表示的化合物更具體為下述式(1-15) 或(1-16)所表示的化合物。19 201226394 40550pif The definition of Py1 in the formulas (1-11) to (1-14) is the same as described above. The definition of R in the above formula (2〇, (3') or (4〇 is the same as above. s is an integer of 1 to 4, preferably 1 or 2, more preferably 1. Pyridyl group substituted by R. The compound represented by the formula (1) is more specifically a compound represented by the following formula (1-15) or (1-16).
式(1-15)及(1-16)中的Py及R的定義與上述相同。 t為1〜4的整數,較佳為1或2,更佳為1。R所取代的伸 苯基的位置並無限制,若考慮到合成的容易程度,則在為 1,4-伸苯基的情況下以與蒽連結的碳為基準較佳為3位。 在為1,3-伸苯基的情況下以與蒽連結的碳為基準較佳為4 位。 具體而言,如上述式(1)所表示的化合物大致分為式 (1-7)〜(1-16)所表示的化合物。該等中,較佳的結構 為式(1-7)、式(1-9)〜(1-11)及式(1-13)〜(1-16), 更佳的結構為式(1-7)。 <化合物的具體例> 本發明的化合物的具體例可揭示為以下所列舉的式, 但本發明並不限定於這些具體結構的揭示。 20 201226394 4imupif <式(1-7)所表示的化合物的具體例> 式(1-7)所表示的化合物的具體例如下述式(1-7-1) 〜(1-7-144)所示。該等中,較佳的化合物為式(卜7-1 ) 〜(卜7-6)、式(1-7-10)〜(1-7-12)、式(1-7-16)〜(1-7-30)、 式(卜7_34)〜(H36)、式(1-7-40)〜(1-7-48)、式 (1-7-73 )〜(1-7-78 )、式(1-7-82 )〜(1-7-84 )、式(1-7-88 ) 〜(卜7_102)、式(1-7-106)〜(1-7-108)及式(1-7-112) 〜(1-7-120)。The definitions of Py and R in the formulae (1-15) and (1-16) are the same as described above. t is an integer of 1 to 4, preferably 1 or 2, more preferably 1. The position of the phenyl group substituted by R is not limited, and in view of the ease of synthesis, in the case of 1,4-phenylene, the position is preferably 3 in terms of carbon bonded to hydrazine. In the case of a 1,3-phenylene group, it is preferably 4 positions based on the carbon bonded to the hydrazine. Specifically, the compound represented by the above formula (1) is roughly classified into the compounds represented by the formulae (1-7) to (1-16). Among these, preferred structures are the formula (1-7), the formulas (1-9) to (1-11), and the formula (1-13) to (1-16), and the more preferable structure is the formula (1). -7). <Specific Example of Compound> Specific examples of the compound of the present invention can be disclosed as the following formulas, but the present invention is not limited to the disclosure of these specific structures. 20 201226394 4imupif <Specific Example of Compound represented by Formula (1-7)> Specific examples of the compound represented by Formula (1-7) are, for example, the following formula (1-7-1) to (1-7-144) ) shown. Among these, preferred compounds are of the formula (b-7)~(Bu 7-6), formula (1-7-10)~(1-7-12), formula (1-7-16)~ (1-7-30), formula (Bu 7_34) ~ (H36), formula (1-7-40) ~ (1-7-48), formula (1-7-73) ~ (1-7-78 ), formula (1-7-82)~(1-7-84), formula (1-7-88)~(Bu 7_102), formula (1-7-106)~(1-7-108) and Formula (1-7-112) ~ (1-7-120).
(1-7-9) 21 201226394 40550pif (1-7-11)(1-7-9) 21 201226394 40550pif (1-7-11)
22 20122639422 201226394
(1-7-32) (1-7-33) 23 201226394 4U»Upif(1-7-32) (1-7-33) 23 201226394 4U»Upif
24 201226394 40550pif24 201226394 40550pif
(1-7-47)(1-7-47)
2525
201226394t I \y ij l L201226394t I \y ij l L
201226394201226394
27 201226394 40550pif27 201226394 40550pif
28 201226394 40550pif28 201226394 40550pif
29 201226394 40550pif29 201226394 40550pif
30 201226394 40550pif30 201226394 40550pif
31 201226394 40550pif31 201226394 40550pif
201226394 t <式(1-8)所表示的化合物的具體例> 式(1-8)所表示的化合物的具體例如下述式(1-8-1) 〜(1-8-105)所示。Specific examples of the compound represented by the formula (1-8) > Specific examples of the compound represented by the formula (1-8) are, for example, the following formula (1-8-1) to (1-8-105). Shown.
33 201226394 40550pif33 201226394 40550pif
s 34 201226394 jvjjifs 34 201226394 jvjjif
35 201226394 40550pif35 201226394 40550pif
36 201226394 40550pif36 201226394 40550pif
37 201226394 40550pif37 201226394 40550pif
38 20122639438 201226394
39 201226394 40550pif39 201226394 40550pif
40 201226394 40550pif40 201226394 40550pif
41 201226394 40550pif41 201226394 40550pif
<式(1-9)所表示的化合物的具體例> 式(1-9)所表示的化合物的具體例如下述式 〜(^948)所示。該等中,較佳的化合物為式(1_9_ 〜(1-9-12)、(1-9-16)〜(1-9-18)、式(1-9-34)〜(1 g ; 及式(1-9-40)〜(19-42)。 - ·36) 42 201226394 40550pif<Specific example of the compound represented by the formula (1-9)> The compound represented by the formula (1-9) is specifically represented by the following formula: (^948). Among these, preferred compounds are of the formula (1_9_~(1-9-12), (1-9-16)~(1-9-18), and the formula (1-9-34)~(1 g ; And (1-9-40)~(19-42). - ·36) 42 201226394 40550pif
(1-9-9)(1-9-9)
43 20122639443 201226394
201226394 40550pif201226394 40550pif
(1-9-25)(1-9-25)
(1-9-26)(1-9-26)
(1-9-28) (1-9-27)(1-9-28) (1-9-27)
(1-9-29) (1-9-30)(1-9-29) (1-9-30)
(1-9-32) (1-9-31)(1-9-32) (1-9-31)
(1-9-33) 45 201226394 40550pif(1-9-33) 45 201226394 40550pif
(1-9-35) (1-9-37) (1-9-39)(1-9-35) (1-9-37) (1-9-39)
(1-9-41)(1-9-41)
46 201226394 ^fU^DUpif <式(1-10)所表示的化合物的具體例> 式(1-10)所表示的化合物的具體例如下述式(1-10-1) 〜(1-10-48)所示。該等中,較佳的化合物為式(1-10-1) 〜(1-10-6)、(1-10-10)〜(1-10-12)及(1-10-16)〜 (1-10-21)。46 201226394 ^fU^DUpif <Specific Example of Compound represented by Formula (1-10)> Specific examples of the compound represented by Formula (1-10) are, for example, the following formula (1-10-1) to (1- 10-48) shown. Among these, preferred compounds are the formulae (1-10-1) to (1-10-6), (1-10-10) to (1-10-12) and (1-10-16)~ (1-10-21).
47 201226394 'tvjjjupif47 201226394 'tvjjjupif
(1-10-10) (1-10-12) (1-10-14) (1-10-18) (1-10-21) (1-10-16)(1-10-10) (1-10-12) (1-10-14) (1-10-18) (1-10-21) (1-10-16)
(1-10-19)(1-10-19)
(1-10-23)(1-10-23)
48 201226394 40550pif48 201226394 40550pif
(1-10-26) (1-10-28) (1-10-30) (1-10-32) 49 201226394 40550pif(1-10-26) (1-10-28) (1-10-30) (1-10-32) 49 201226394 40550pif
50 201226394 40550pif <式(1-11)所表示的化合物的具體例> 式(1-11)所表示的化合物的具體例如下述式(1-11-1) 〜(1-11-60)所示。該等中,較佳的化合物為式(1-11-3) 〜(1-11-10)、(1-11-25)〜(1-11-28)及(1-11-51)〜 (1-11-60)。50 201226394 40550pif <Specific example of the compound represented by the formula (1-11)> Specific examples of the compound represented by the formula (1-11) are, for example, the following formula (1-11-1) to (1-11-60) ) shown. Among these, preferred compounds are the formulae (1-11-3) to (1-11-10), (1-11-25) to (1-11-28) and (1-11-51)~ (1-11-60).
51 201226394 40550pif51 201226394 40550pif
52 s 20122639七52 s 20122639 seven
(1-11-35) (1-11-37)(1-11-35) (1-11-37)
53 201226394 40550pif53 201226394 40550pif
54 201226394 40550pif54 201226394 40550pif
<式(M2)所表示的化合物的具體例> 式(1-12)所表示的化合物的具體例如下述式(1-12-1) 〜(1-12-60)所示。 55 201226394 4U55Upif<Specific Example of the Compound of the Formula (M2)> Specific examples of the compound represented by the formula (1-12) are shown by the following formula (1-12-1) to (1-12-60). 55 201226394 4U55Upif
(1-12-1)(1-12-1)
(1-12-2) (1-12-3) (1-12-5) (1-12-7) (1-12-9)(1-12-2) (1-12-3) (1-12-5) (1-12-7) (1-12-9)
(1-12-6) (1-12-8) (1-12-10) (1-12-4) s 56 201226394t • ^ L·^ ίί.(1-12-6) (1-12-8) (1-12-10) (1-12-4) s 56 201226394t • ^ L·^ ίί.
(1-12-12) (1-12-11)(1-12-12) (1-12-11)
(1-12-14) (1-12-16) (1-12-18)(1-12-14) (1-12-16) (1-12-18)
(1-12-20)(1-12-20)
j j (1-12-22)j j (1-12-22)
(1-12-23)(1-12-23)
丫、(1-12-24) s 57 201226394 40550pif丫, (1-12-24) s 57 201226394 40550pif
(1-12-25)(1-12-25)
(1-12-26) (1-12-27)(1-12-26) (1-12-27)
(1-12-33) (1-12-31)(1-12-33) (1-12-31)
(1-12-34)(1-12-34)
(1-12-35)(1-12-35)
(1-12-37)(1-12-37)
NT 58 s 201226394 40550pifNT 58 s 201226394 40550pif
(1-12-41)(1-12-41)
(1-12-40) (1-12-42) (1-12-43)(1-12-40) (1-12-42) (1-12-43)
(1-12-47) (1-12-49) (1-12-45)(1-12-47) (1-12-49) (1-12-45)
(1-12-48) (1-12-50)(1-12-48) (1-12-50)
59 201226394 40550pif59 201226394 40550pif
<式(1-13)所表示的化合物的具體例> 式(1-13)所表示的化合物的具體例如下述式(1-13-1) 〜(1-13-60)所示。該等中,較佳的化合物為式(1-13-21) 〜(1-13-28)及式(1-13-31)〜(1-31-40)。 201226394 40550pif<Specific example of the compound represented by the formula (1-13)> Specific examples of the compound represented by the formula (1-13) are shown by the following formula (1-13-1) to (1-13-60). . Among these, preferred compounds are the formulae (1-13-21) to (1-13-28) and the formula (1-13-31) to (1-31-40). 201226394 40550pif
(1-13-2) (1-13-4) (1-13-6)(1-13-2) (1-13-4) (1-13-6)
6 61 201226394 40550pif6 61 201226394 40550pif
62 201226394 40550pif62 201226394 40550pif
63 20122639463 201226394
S 64 201226394 ^fu^^upifS 64 201226394 ^fu^^upif
<式(1-14)所表示的化合物的具體例> 式(1-14)所表示的化合物的具體例如下述式(1-14-1) 〜(1-14-60)所示。該等中,較佳的化合物為式(1-14-1) 〜(1-14-18)。 65 201226394 40550pif<Specific example of the compound represented by the formula (1-14)> Specific examples of the compound represented by the formula (1-14) are shown by the following formula (1-14-1) to (1-14-60). . Among these, preferred compounds are the formulae (1-14-1) to (1-14-18). 65 201226394 40550pif
66 201226394 40550pif66 201226394 40550pif
67 20122639467 201226394
68 201226394 40550pif68 201226394 40550pif
69 201226394 40550pif69 201226394 40550pif
<式(1-15)所表示的化合物的具體例> 式(M5)所表示的化合物的具體例如下述式(1-15-1) 〜(1-15-48)所示。該等中,較佳的化合物為式(1-15-10) 〜(1-15-12)、(1-15-16)〜(1-15-18)、式(1-15-34)〜 (1-15-36)及(1-15-40)〜(1-15-42)。 201226394 40550pif (1-15-2)<Specific Example of the Compound of the Formula (1-15)> The specific formula of the compound represented by the formula (M5) is, for example, the following formula (1-15-1) to (1-15-48). Among these, preferred compounds are the formulas (1-15-10) to (1-15-12), (1-15-16) to (1-15-18), and the formula (1-15-34). ~ (1-15-36) and (1-15-40) ~ (1-15-42). 201226394 40550pif (1-15-2)
(1-15-8) (1-15-9) 71 201226394 40550pif(1-15-8) (1-15-9) 71 201226394 40550pif
201226394201226394
(1-15-29) (1-15-30)(1-15-29) (1-15-30)
73 201226394 *u73 201226394 *u
<式(1-16)所表示的化合物的具體例> 式(1-16)所表示的化合物的具體例如下述式(1-16-1 ) 〜(1-16-24)所示。該等中,較佳的化合物為式(1-16-1 ) 〜(1-16-5)。<Specific Example of Compound represented by Formula (1-16)> Specific examples of the compound represented by Formula (1-16) are shown by the following formula (1-16-1) to (1-16-24) . Among these, preferred compounds are the formulae (1-16-1) to (1-16-5).
S 74 201226394 40550pifS 74 201226394 40550pif
(1-16-1) (1-16-3) (1-16-5) (1-16-7) (1-16-9)(1-16-1) (1-16-3) (1-16-5) (1-16-7) (1-16-9)
(1-16-2) (1-16-4) (1-16-6) (1-16-8) 75 201226394 40550pif(1-16-2) (1-16-4) (1-16-6) (1-16-8) 75 201226394 40550pif
s 76 201226394t <化合物的合成方法> 以F ’對本發明的化合物的合成方法進行說明。本發 明的化合物可藉由適宜組合利用通用的已知合成方法而合 成。 。 <式(1-7-1)〜式(1-7-144)所表示的化合物的合成 方法> 反應1s 76 201226394t <Synthesis method of compound> A method for synthesizing the compound of the present invention will be described by F '. The compounds of the present invention can be synthesized by a suitable combination using a general known synthetic method. . <Synthesis of a compound represented by the formula (1-7-1) to the formula (1-7-144)> Reaction 1
m : 1至5的整數 首先,藉由反應1合成苯基經烷基(環烷基)取代的 9-苯基葱。使經烷基取代的溴苯在THF中與金屬鎂反應, 製成格林納試劑(Grignard reagent),在觸媒的存在下使其 與9-溴蒽反應,製成苯基經烷基(環烷基)取代的9-苯基 蒽。將苯環與蒽環偶合並不限定於上述方法,例如可採用 使用鋅錯合物的根岸偶合反應、使用硼酸或硼酸酯的鈴木 偶合反應等,可根據狀況而適宜使用該等常規方法。 77 201226394 HUO^Upif 反應2m : an integer of 1 to 5 First, a 9-phenyl onion substituted with an alkyl group (cycloalkyl group) is synthesized by the reaction 1. The alkyl-substituted bromobenzene is reacted with magnesium metal in THF to prepare a Grignard reagent, which is reacted with 9-bromoindole in the presence of a catalyst to form a phenyl group through an alkyl group (ring). Alkyl) substituted 9-phenylindole. The combination of the benzene ring and the anthracene ring is not limited to the above method. For example, a root-shore coupling reaction using a zinc complex or a Suzuki coupling reaction using boric acid or a boric acid ester may be employed, and these conventional methods may be suitably used depending on the situation. 77 201226394 HUO^Upif Reaction 2
反應2是使用N-溴琥珀醯亞胺而將苯基經烷基(環燒 基)取代的9-苯基蒽的10位溴化。此處,亦可使用漠 琥珀醯亞胺以外的常用溴化劑。Reaction 2 is a bromination at the 10-position of 9-phenylindole substituted with an alkyl group (cycloalkyl) using N-bromosuccinimide. Here, a common brominating agent other than the amber succinimide can also be used.
反應3是將蒽環與萘環偶合。首先依據常規方法將2_ 溴-6-甲氧基萘製成格林納試劑,在觸媒的存在下使其與反 應2所合成的9-溴蒽衍生物反應,合成9_(6_甲氧基萘_2_ 基)-10-苯基蒽衍生物。與反應丨同樣地,將苯環與蒽環偶 合並不限定於上述;^法,例如可採帛使用辞錯合物的根岸 偶合反應、使用硼酸或硼酸酯的鈴木偶合反應等,可根據 狀況而適宜使用該等常規方法。Reaction 3 is the coupling of an anthracene ring to a naphthalene ring. Firstly, 2_ bromo-6-methoxynaphthalene is prepared into a Grignard reagent according to a conventional method, and reacted with a 9-bromoindole derivative synthesized in the reaction 2 in the presence of a catalyst to synthesize 9_(6-methoxy group). Naphthalene-2-yl)-10-phenylindole derivative. In the same manner as the reaction oxime, the benzene ring and the oxime ring are not limited to the above; for example, a root-shore coupling reaction using a rhodium complex or a Suzuki coupling reaction using boric acid or a boric acid ester can be used. It is appropriate to use these conventional methods.
78 201226394 -IT 丄 178 201226394 -IT 丄 1
反應4是將9-(6-甲氧基萘-2-基)-10-苯基蒽衍生物的 曱氧基脫曱基而形成萘酚。此處,亦可適宜使用脫曱基化 反應常用的試劑。 反應5Reaction 4 is a dehydration group of a 9-(6-methoxynaphthalen-2-yl)-10-phenylindole derivative to form a naphthol. Here, a reagent which is commonly used for the demethylation reaction can also be suitably used. Reaction 5
反應5是將萘酚的-OH轉化為三氟曱磺酸酯 (triflate )。反應式中的-OTf為-OS02CF3的簡稱。 反應6Reaction 5 is the conversion of the -OH of naphthol to triflate. -OTf in the reaction formula is an abbreviation of -OS02CF3. Reaction 6
Br · HCI i-PrMgCl i-PrMgClBr · HCI i-PrMgCl i-PrMgCl
ZnCl2 · TMEDAZnCl2 · TMEDA
THFTHF
反應6是藉由根岸偶合(Negishi coupling)反應使°比咬 79 201226394 40550pif 環與萘環結合。首先,將4_溴吡喷制 由於是使用對原料穩定的4如^鹽_劑。此處’ 莫耳的異丙基氣化錢,但對於不必用2倍 為等莫耳亦無妨。向格林納試劑中添加二=乙: 胺錯合物,合成t定的氣化鋅錯合物,在_媒的$在; 使其與反應5所獲得的三氟反應,而合成目標物。 反應6除根岸偶合反應以外,亦可適宜使用鈴木偶合 (Suzuki coupling)反應等常用偶合反應。在使用鈴木偶合反 應的情況下’根據目標物來準備最適合的硼酸或硼酸酯即 可,例如可使用下述反應7所示的硼酸酯來獲得目標物。 反應7Reaction 6 was carried out by a Negishi coupling reaction to bind a naphthalene ring to a bite 79 201226394 40550 pif ring. First, 4_bromopyrazine is sprayed because it is a salt which is stable to the raw material. Here, 'Mer's isopropyl gasification money, but it doesn't matter if you don't have to use 2 times. To the Grignard reagent, a bis:ethylamine complex is added, and a zinc hydride complex of t-form is synthesized, and the target is obtained by reacting with trifluoroethylene obtained in the reaction 5. In addition to the root-coupling reaction, the reaction 6 may suitably employ a conventional coupling reaction such as a Suzuki coupling reaction. In the case of using Suzuki coupling reaction, the most suitable boric acid or boric acid ester can be prepared according to the target. For example, a boric acid ester represented by the following reaction 7 can be used to obtain a target product. Reaction 7
作為偶合反應所使用的鈀觸媒的具體例,可列舉: Pd(PPh3)4、PdCl2(PPh3)2、Pd(OAc)2、三(二亞苄基丙酮)二 201226394 40550pif 飽(〇)、三(二亞苄基丙酮)二鈀(〇)氯仿錯合物、雙(二 亞节基丙酮)鈀(〇)、雙(三第三丁基膦基)鈀(〇)、或(1,Γ_ 雙(二苯基膦基)二茂鐵)二氣鈀(II)。 另外’為了促進反應,亦可視情況向該等|巴化合物中 添加膦化合物。作為此膦化合物的具體例,可列舉:三(第 二丁基)膦、三環己基膦、1_(N,n_二甲基胺基甲基)_2_(二第 三丁基膦基)二茂鐵、1 _(N,N_二丁基胺基甲基)_2_(二第三丁 基膦基)二茂鐵、1-(甲氧基甲基)-2-(二第三丁基膦基)二茂 鐵、U’-雙(二第三丁基膦基)二茂鐵、2,2,_雙(二第三丁基 膦基)-ι,ι,-聯萘、2_甲氧基_2’_(二第三丁基膦基) 萘、或2·二環己基膦基_2’,6,-二甲氧基聯苯。 作為反應所使用的鹼的具體例,可列舉:碳酸納、碳 酸鉀、碳酸鉋、碳酸氫鈉、氫氧化鈉、氫氧化鉀、氫氧= 鋇、乙醇鈉、第三丁醇鈉、乙酸鈉、磷酸三鉀、或氟化鉀。 另外,作為反應所使用的溶劑的具體例,可列舉:笨、 曱苯、二甲苯、1,2,4-三曱基苯、Ν,Ν-二甲基甲醯胺、四氫 呋喃、二乙基醚、第三丁基甲基醚、丨,4_二噁烷、甲醇、 乙醇、環戊基甲基醚或異丙醇。該等溶劑可適宜選擇,可 單獨使用,亦可製成混合溶劑使用。 〈式(1-8-1)〜式(1-8-105)所表示的化合物的合 方法> 在上述反應3中’若使用2-溴-7-曱氧基萘代替2_溴 甲氧基萘,則可同樣地進行合成。 〈式(1-9-1)〜式(1-9-48)及式(l-io])〜式(11〇 48) 201226394 4U55Upif 所表示的化合物的合成方法> 藉由使用此等苯骨架與萘骨架經取代的原料代替上述 反應1〜反應3中所使用的原料,可與上述同樣地進行合 成。即’將2-溴蒽的格林納試劑與9_溴蒽偶合,依據反應 2將葱的^⑽化’接著使職化物與對f氧基絲或間 曱氧基、絲的格軸試航應,而獲得9_(4_或3•甲氧基苯 基)-10-(2-萘基)蒽。針對該化合物’曱氧基的脫甲基化反 應以後的順序依據上述進行即可。此外,除具體例示的化 合物以外,當然亦可藉由根據目標物適宜使用原料,依據 上述合成方法進行合成。 〈式(1-11-1 )〜式(M1_60)、式(M2])〜式 (1-12_60)、式(1-13-1)〜式(1-13-60)及式(i-14-l) 〜式(1-10-60)所表示的化合物的合成方法> 藉由使用經烷基或環烷基取代的吡啶衍生物代替上述 反應6或反應7所使用的原料的„比啶衍生物作為原料,可 與上述同樣地進行合成。 經烧基或環烷基取代的吡啶衍生物可如下述反應8〜 反應9所示進行合成。此處,雖然例示了式(1-11-11)、 式(1-12-11)、式(M311)及式(M4-11)所表示的化 合物中的吡啶部位的合成方法,但藉由適宜變更原料,可 合成各種經燒基或環烧基取代的η比σ定衍生物。Specific examples of the palladium catalyst used for the coupling reaction include Pd(PPh3)4, PdCl2(PPh3)2, Pd(OAc)2, and tris(dibenzylideneacetone) 2 201226394 40550pif satiety (〇), Tris(dibenzylideneacetone)dipalladium (yttrium) chloroform complex, bis(diphenylideneacetone)palladium (ruthenium), bis(tri-t-butylphosphino)palladium (ruthenium), or (1, Γ_bis(diphenylphosphino)ferrocene) digas palladium (II). Further, in order to promote the reaction, a phosphine compound may be added to the phenol compounds as the case may be. Specific examples of the phosphine compound include tris(t-butyl)phosphine, tricyclohexylphosphine, and 1-(N,n-dimethylaminomethyl)_2-(di-t-butylphosphino)di Ferrocene, 1 _(N,N-dibutylaminomethyl)_2_(di-t-butylphosphino)ferrocene, 1-(methoxymethyl)-2-(di-t-butyl Phosphyl)ferrocene, U'-bis(di-t-butylphosphino)ferrocene, 2,2,_bis(di-t-butylphosphino)-ι,ι,-binaphthyl, 2_ Methoxy 2'-(di-t-butylphosphino) naphthalene, or 2·dicyclohexylphosphino-2',6,-dimethoxybiphenyl. Specific examples of the base to be used in the reaction include sodium carbonate, potassium carbonate, carbonic acid planer, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, hydrogen oxygen = hydrazine, sodium ethoxide, sodium butoxide, sodium acetate. , tripotassium phosphate, or potassium fluoride. Further, specific examples of the solvent to be used in the reaction include stupid, indene, xylene, 1,2,4-trimercaptobenzene, anthracene, fluorene-dimethylformamide, tetrahydrofuran, and diethyl. Ether, tert-butyl methyl ether, hydrazine, 4-dioxane, methanol, ethanol, cyclopentyl methyl ether or isopropanol. These solvents may be appropriately selected and used singly or as a mixed solvent. <Method for Combining Compounds Represented by Formula (1-8-1) to Formula (1-8-105)> In the above Reaction 3, 'If 2-bromo-7-methoxynaphthalene is used instead of 2-bromo The oxynaphthalene can be synthesized in the same manner. <Formula (1-9-1) to Formula (1-9-48) and Formula (l-io)) to Formula (11〇48) 201226394 Method for synthesizing the compound represented by 4U55Upif> By using such benzene The raw material substituted with the skeleton and the naphthalene skeleton may be used in the same manner as described above instead of the raw materials used in the above Reactions 1 to 3. That is, 'the 2-Bromopurine Grenner reagent is coupled with 9-bromoindole, and according to the reaction 2, the onion is ^(10)', then the precursor is tested with the lattice of the f-oxygen or m-methoxy group and the silk. And 9_(4_ or 3•methoxyphenyl)-10-(2-naphthyl)anthracene is obtained. The order after the demethylation reaction of the compound 'oximeoxy group' may be carried out in accordance with the above. Further, in addition to the specifically exemplified compound, it is of course possible to carry out the synthesis according to the above synthesis method by suitably using a raw material according to the target. <Formula (1-11-1) to Formula (M1_60), Formula (M2)) to Formula (1-12_60), Formula (1-13-1) to Formula (1-13-60), and Formula (i- 14-l) Synthesis method of the compound represented by the formula (1-10-60)> by using an alkyl group or a cycloalkyl-substituted pyridine derivative instead of the raw material used in the above reaction 6 or reaction 7 The pyridyl derivative can be synthesized in the same manner as described above. The pyridine derivative substituted with a decyl group or a cycloalkyl group can be synthesized as shown in the following Reaction 8 to Reaction 9. Here, the formula (1) is exemplified. 11-11) A method for synthesizing a pyridine moiety in a compound represented by the formula (1-12-11), the formula (M311), and the formula (M4-11), but various calcinations can be synthesized by appropriately changing a raw material. Or a cycloalkyl substituted η than a sigma derivative.
82 201226394 40550pif 反應8 Br82 201226394 40550pif Reaction 8 Br
反應9Reaction 9
1) RLi 或 Mg 或 RMgX2) ZnCI2 或 ZnCI2.TMEDA1) RLi or Mg or RMgX2) ZnCI2 or ZnCI2.TMEDA
cizn-〇-Cizn-〇-
BrBr
Pd-觸媒Pd-catalyst
<式(1-15-1)〜式(1-15-48)及式(卜16-1)〜式 (1-16-24)所表.示的化合物的合成方法> 在上述「式(1-9-1)〜式(1-9-48)及式(1-10-1) 〜式(M0-48)所表示的化合物的合成方法」中的苯基的 導入步驟中,使用經烷基或環烷基取代的苯基即可。例如 可使用下述反應10所示的合成方法。 反應1 〇<Formula (1-15-1) to Formula (1-15-48) and Formula (Bu 16-1) to Formula (1-16-24), the method for synthesizing the compound > In the step of introducing a phenyl group in the method for synthesizing a compound represented by the formula (1-9-1) to the formula (1-9-48) and the formula (1-10-1) to the formula (M0-48), A phenyl group substituted with an alkyl group or a cycloalkyl group may be used. For example, the synthesis method shown in the following reaction 10 can be used. Reaction 1 〇
式中的R的定義與上述相同。〇為1〜4的整數。可奸 據目標化合物在苯環的任意位置僅連結所需數量的汉。乂 在將本發明的化合物用於有機EL元件中的雷 層或電子傳輸層的情況Ύ,在施加電場龜 _ /入 表示本發明的化合物作為電激發光型元件的、子二:: 83 201226394 4U^5Upif 料、或電子傳輸材料優異。此處所謂電子注入戶 的層;所謂電子傳_ 用於將主人的電子傳輸至發光層的層1外,電子傳輸層 注入層。各層所使用的材料稱為電子注入材 料及電子傳輸材料。 <有機EL元件的說明> 2發明是在電子注人層、或電子傳輸層中包 3明的式⑴所表示的化合物的有機EL元件。本發 明的有機EL元件的驅動電壓低,驅動時的耐久性高。 本發明的有機EL元件的結構有各種㈣,基本為在 圣與陰極之間至少夾持有電洞傳輸層、發光層、電子傳 ^層的多層結構。元件的具體構成的例子為:⑴陽極/ 同傳輸層/發光層/電子傳輸層/陰極、⑴陽極/電洞注入 曰/電'同傳輸層/發光層/電子傳輸層/陰極、(3)陽極/電洞注 入層/電洞傳輸層/發光層/電子傳輸層/電子注入層/陰極等。 本發月的化合物由於具有兩的電子注入性及電子傳輸 _故而"J單獨或與其他材料併用而用於電子注入層、或 電子傳輸層。本發明的有機EL元件藉由組合在本發明的 電子傳輸材料中使用其他材料的電洞注入層、電洞傳輸 層、^光層等’亦可獲得藍色、綠色、紅色或白色的發光。 ‘可用於本發明的有機EL元件的發光材料或發光性摻 雜劑為:S分子學會編、高分子機能材料㈣「光機能材 料f共同出版(1991 )、p236所記載的日光色螢光材料、 螢光增白劑、雷射色素、有機閃爍體(scintillator)、各種螢The definition of R in the formula is the same as described above. 〇 is an integer from 1 to 4. According to the target compound, only the required amount of Han is linked at any position of the benzene ring. In the case where the compound of the present invention is used for a layer of a germanium layer or an electron transport layer in an organic EL device, the application of the electric field turtle _ / in indicates that the compound of the present invention is used as an electroluminescent element, Sub 2:: 83 201226394 Excellent for 4U^5Upif materials or electron transport materials. Here, the layer of the electron injecting unit; the so-called electron transfer _ is used to transport the electrons of the host to the layer 1 of the light-emitting layer, and the electron transport layer is injected into the layer. The materials used for each layer are referred to as electron injecting materials and electron transporting materials. <Description of Organic EL Element> 2 The invention is an organic EL element of a compound represented by the formula (1) which is contained in an electron injecting layer or an electron transporting layer. The organic EL device of the present invention has a low driving voltage and high durability at the time of driving. The organic EL device of the present invention has various (four) structures, and is basically a multilayer structure in which at least a hole transport layer, a light-emitting layer, and an electron transport layer are sandwiched between a saint and a cathode. Examples of specific components of the component are: (1) anode/same transmission layer/light-emitting layer/electron transport layer/cathode, (1) anode/hole injection/electrical transmission layer/light-emitting layer/electron transport layer/cathode, (3) Anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode, and the like. The compound of the present month has two electron injecting properties and electron transports, so that it is used alone or in combination with other materials for the electron injecting layer or the electron transporting layer. The organic EL device of the present invention can also obtain blue, green, red or white light by using a hole injection layer, a hole transport layer, a light layer or the like of other materials in combination with the electron transport material of the present invention. The luminescent material or luminescent dopant which can be used in the organic EL device of the present invention is: S molecular engineering, polymer functional material (4) "Photonic material f co-published (1991), p236, the daylight fluorescent material , fluorescent brightener, laser pigment, organic scintillator, various kinds of firefly
84 201226394 40550pif 光分析試劑等發光材料·,城戶淳二主編、「有機虹材難 =器」CMC社出版⑽1)pi55〜156所記載 劑 材料、P170〜172所記載的三重態材料的發光材料等。 可用作發光材料或發光性摻雜劑的化合物為:多 香族化合物、雜環芳香族化合物、有機金屬錯合物、色 =分子祕光材料、苯乙烯基衍生物、㈣族胺衍生物、 ^素衍生物、概衍生物、。㈣衍生物、具有螺環的化 惡何生物、騎生物等。多環芳香族化合物的 歹,_ 二何生物、菲衍生物、細苯射物、絲生物、 物、茈何生物、蔻衍生物、紅螢烯衍生物等。 方香純合物_子為:具有二絲胺基或二芳基胺 :的嗔二餘生物、財並料衍生物、喊触物”比 ^衍生物、料衍生物、♦雜職二烯魅物、具有三苯 η基的Γ吩魅物、十丫烟魅物等。有機金屬錯合 =例二辞、銘、鈹、销、試、鋼、銀、翻、鐵、金 經基钟衍生物、苯聽讀生物、苯並料衍生物、 ri°坐街生物n衍生物、苯並咪飾生物、料衍 可2與Γ定衍生物、啡琳衍生物等的錯合物。色素的例子 為·咕噸(酬hene)衍生物、聚次甲基衍生物、外啉 香丑素衍生物、二氰基亞甲基吼喃衍生物、二氰 二亞甲基麵魅物、縫絲並s衍生物、喹侧衍生 2 ί衍生物、笨並°驗衍生物、苯並料衍生物、苯並 厂二生物等色素。高分子系發光材料的例子為:聚對苯 稀何生物、聚售吩衍生物、聚乙魅㈣衍生物、聚石夕 85 201226394 40550pif 烷衍生物、聚第衍生物、聚對苯衍生物等。苯乙烯基衍生 物的例子為:含胺的苯乙烯基衍生物、苯乙烯基伸芳基衍 生物等。 。本發明的有機EL元件所使用的其他電子傳輸材料可 自可在光導電材料中用作電子傳遞化合物的化合物、可用 =有機EL元件的電子傳輸層及f子注人層的化合物 忍選擇使用。 此種電子傳輸材料的具體例為:經基喧淋系金屬錯合 …聯吡。疋衍生物、啡啉衍生物、聯苯醌衍生物、茈 惡坐街生物、嗟吩衍生物、三°坐衍生物、嗟二 何物、8·經基料衍生物的金屬錯合物、㈣琳衍生 :哇=衍生物的聚合物、,朵類化合物、鎵錯合物、 物、笨亂伸苯基魅物、三嗪衍生物、吼嗪衍生 關於υ’τ生物、咪倾対衍生物、概衍生物等。 電洞傳卜材^明ϊ有機el元件所使用的電洞注入材料及 傳用:從先前在光導電材料中作為電洞的電荷 ==化合物、或有機el元件的電洞注入層 此等的具二為使:二眾:知的材料中任意選擇使用。 生物等。咔坐何生物、三芳基胺衍生物、酞菁衍 層的材料以is有件的各層可藉由將應構成各 而形成。如此而形成法等方法製成薄膜 材料的性質而適宜設膜;並無特別限定,可根據 又疋,I ¥為2 nm〜5〇〇〇 nm的範圍。 86 201226394 40550pif 此外’將發光材料薄膜㈣方法較佳為_ 因在於易獲得均質的膜,且不易生成小孔(pinh〇les)/。、在 使用療鍍法進打薄膜化的情況下,其蒸錢條件根據本發明 的,光材料的種類*有所不㈤。蒸鐘條件通常較佳為在如 下範圍内適宜設定:加熱舟溫度為耽〜伽^、真空度 為10·6 Pa〜10-3 Pa、蒸錢速度為〇 01 nm/秒〜5〇細,ς ^ 基板溫度為-150°C〜+30CTC、膜厚為5ηιη〜5μιη。 本發明的有機EL元件無論為上述任何結構,均較佳 板支撐。基板只要具有機械強度、熱穩定性及透明 P可’可使用玻璃、透明塑膠膜等。陽極物質可使用功 稱料Sn02、z二屬CUI氧化銦錫(以下’簡 陰極物質可使用功函數小於4ev的金屬、合 =化合物、及該等的混合物。其具體例為H弼、鎮、 、、鎮合金、銘合金等。合金的具體 化、、 /鐘、鎂/銀、鎂/銦等。為了效率良好地取出有 的發光,較理想為至少一饱雷減^』有機EL讀 為電極的片電阻電極的透先率為10%以上。作 r於電極材料的性質,但通常在10則二= 二400 nm的範圍内設定。此種電極可藉由使用上述 由蒸鍍或賤錢等方法形成薄獏而製作。 件的;:的-ί/吏二tt明二巧材料來製作有機EL元 3上述險極/電洞注入層/電洞傳輸 87 201226394 本發明的電子傳輸材料/陰極的有機EL元件的 料的薄在適當基板上藉由蒸鑛法形卿 洞傳輸%極後’在雜極上形成電洞注入層及電 上真*膜。在其上形成發光層的薄膜。在該發光層 上發明的電子傳輸材料,形成薄膜,而製成電 而藉由蒸躲形成包含陰極用物質的薄膜, 古Μ *亟,藉此獲得目標有機EL元件。此外,在上述 L it件的製作亦可顛倒製作順序,而以陰極、 順序進^製作發光11贿輸層、制注人層、陽極的 在,如此而獲得的有機EL元件施加直流電壓的情況 下以陽極作為+的極性且以陰極作為-的極性施加電壓即 可,若施加2 V〜40 V左右的電壓,則可從透明或半透明 的電極侧(陽極或陰極、及雙方)觀測到發光。另外,該 有機EL元件在施加交流電壓的情況下亦發光。此外,所 施加的交流電的波形可為任意。 [實例] 以下,基於實例更詳細地說明本發明。首先,對實例 所使用的化合物的合成例說明如下。 [合成例1]化合物(1-7-74)的合成 < 9-(4-第三丁基苯基)蒽的合成> 在氮氣環境下,將添加有9-溴蒽31 g、4-第三丁基苯 基硼酸25 g、Pd(PPh3)41.3 g、磷酸鉀51 g及1,2,4-三甲基 苯150 ml的燒瓶在回流溫度下攪拌21小時。將反應液冷 201226394 40550pif 卻至室溫後’添加水 _ separation)。藉由吸遽採华仃液體分離(hqmd 固體,利用曱醇洗淨由用=讀除去溶劑而析出的 第三丁基苯細28g ㈣酸乙S旨洗淨,獲得9普 <9_漠-1叫第三了基苯基)蒽的合成> 向添加有9-(4-第三丁基笨基 3〇〇 ml S , 19g。在室溫下攪拌丨n± ^ n戌坭j自醞亞月女 1* /5 /¾。# ’、夺,添加硫代硫酸鈉水溶液而停 反應合液轉移至液體分離漏斗中,利用氡仿進行 萃取。藉*吸餘集!隸祕進饤 f,接著從氣減蒸 _㈣出的固 體,接者從虱本中進行再結晶,獲得 苯基)蒽29 g。 、乐一 < 3-(6-溴萘-2-基)吡啶的合成> 將,”臭i〇g及THF 6()ml的燒瓶在冰浴中 冷卻,在祕環境下,-邊獅—邊滴加請的異丙基氯 化鎮的THF溶液35 m卜滴加完畢後暫時升溫到室溫後, 在冰水中冷卻,-邊祕—邊添加氣化鋅四曱基乙二胺錯 合物I7g。其後’在室溫下_ H、時後,添加三氣甲: 酸6-溴萘丨酯18 g及PdCl2 (dppp) 1.6 g,在回流溫度下 擾拌3小時。將反應液冷卻至室溫後’為了除去觸媒的金 屬離子,而添加將相對於目標化合物約相當於3倍莫耳的 乙二胺四乙酸•四納鹽二水合物溶解到適量的水中而成的 溶液(以下,簡稱為EDTA · 4Na水溶液)及甲苯進行液 體分離。在減壓蒸餾除去溶劑後,藉由矽膠管柱層析法(曱 89 201226394 本/乙酸乙g旨=7/3 基)吡啶12 g。 (各積比))進行純化,獲得3·(6_溴萘_2_ 〈化合物(1-7々4)的合成〉 將添加有3-Γ6 '、自贫1 5.9 s、雔卜ν甘奈_2·基)吼啶6.2 g、聯硼酸頻那醇酯 Γ 卞土丙酮)鈀(0) 0.4§、三環己基膦〇.5g、 在回产π h 氧基乙烧5〇 ml的燒瓶在氮氣環境下, :丁*見半4小時。向該溶液中添加9_漠·1〇-(4_第 二本土)蒽8.6 g、磷酸鉀9.3 g及1,2,4-三曱基苯50 」用迪達克管將二曱氧基乙絲常溫下加熱蒸顧 矛、添加第二丁醇5 ml、水5 m卜雙(二亞节基丙酮)把 (〇) 0.4 g及二j衣己基鱗〇5g,在回流溫度下進一步搜拌 ^小時。將反驗冷㈣室溫,進行水洗碰麟解後, 藉由吸濾採集固體。利用曱醇洗淨所獲得的固體,再利用 乙酸乙酯洗淨後,藉由矽膠管柱層析法(曱苯/乙酸乙酯= 9/1(容積比))進行純化,獲得化合物(hm): 3-(6-(1〇-(4_ 第三丁基)苯基)蒽冬基)萘_2_基)吡啶丨〇 g。藉由NMR測 定而確認化合物的結構。 ^-NMR (CDC13) : δ = 9.07 (m,lH) ,8.68 (dd,lH), 8.23 (m,lH) ,8.15 (d,lH) ,8.08 (m,lH) ,8.03 (m,2H), 7.83 (dd,lH) ,7.78 (d,2H) ,7.72 (d,2H) ,7.68 (dd,lH), 7.63 (d,2H) ,7.42-7.48 (m,3H) ,7.30-7.38 (m,4H) , 1.49 (s,9H)。 [合成例2]化合物(1-7-26)的合成 < 9-(3-甲苯基)蒽的合成> 201226394 40550pif 環境下’將添加有9_漠葱36 g、3_甲基苯基棚 二i , PPh3)41 4g4_ 59§及丨,2,4^·甲基苯 150 在回流溫度下_ 2 5小時。狀驗冷卻至室 所二曱苯進行液體分離。利用短碎膠管柱純化 中=虫甲苯洛液後’減壓蒸顧除去溶劑。向所獲得的油 t加庚燒,藉由吸渡採集析出的固體,獲得9分曱苯 恩 31 g 〇 <9-溴-10_(3_曱苯基)蒽的合成> ,添加有9-(3-曱苯基)蒽3〇 §及循2〇〇 mi的燒瓶 中’在线環境下在冰財冷卻,添加_琥舰亞胺 蛾^ 1 §。在至溫下_ 15小時,添加硫代硫酸納 洛液而停止反應。將該溶液轉移至液體分離漏斗中,利 ==進行萃取後’驗卿管㈣行。減壓蒸顧除去溶 向所獲得的溶液中添加舰,藉由吸親集析出的固 體,獲得9_漠-10-(3-曱苯基)蒽3〇 g。 <4,4,5,5-四曱基-2-(10-(3_曱笨基)葱冬基Η”二氧 雜蝴戊環的合成> 將添加有9备10-(3_甲苯基)g 3〇 g、聯蝴酸頻那醇醋 g、雙(二亞节基丙酮)把(〇) i 5 g、三環己基膦】4 g、 上酸钟15 g、碳酸鉀12 g及環戊基曱_ 1〇〇 ml的燒瓶 =氣環境下,在回起度下_ 1M、時。肢應液冷卻 至溫後,添加水及甲苯進行液體分離,利用短矽膠管柱 純化所獲得的曱苯溶液。減壓蒸餾除去溶劑,向所獲得的 油中添加庚烷,藉由吸濾採集析出的固體,獲得4,4,5,5· 91 201226394 40550pif g。甲(1G(3·甲本基)S,9·基)-1,3,2·二氣_戊環μ 〈化合物(1,的合成> 將添加有4 4 s < ^2.^1; ': Ψ & -2-(1〇-(3- ^ ^ ) t -9-84 201226394 40550pif Luminescent materials such as photo-analytical reagents, etc., edited by the CMC Society, edited by the CMC, "organic rainbow materials", (10) 1) the materials described in pi55 to 156, and the luminescent materials of the triplet materials described in P170 to 172. . Compounds which can be used as luminescent materials or luminescent dopants are: polyaromatic compounds, heterocyclic aromatic compounds, organometallic complexes, color=molecular secret materials, styryl derivatives, (tetra) amine derivatives , a derivative, a derivative, and. (4) Derivatives, with the formation of spiro rings, evil organisms, riding creatures, etc. Polycyclic aromatic compounds, bismuth, bis, phenanthrene derivatives, fine benzene emitters, silk organisms, organisms, strontium derivatives, red fluorene derivatives, and the like. Fragrant incense _ sub-: is a di-silyl or diarylamine: 嗔 余 生物 生物 、 、 、 生物 生物 生物 生物 、 、 、 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Matter, styrofoam with triphenyl η group, Shiyan fascinating object, etc. Organic metal mismatch = example two words, Ming, 铍, pin, test, steel, silver, turn, iron, gold-based clock derivative, An example of a benzene-reading organism, a benzoate derivative, a ri° street-native n-derivative, a benzo-imiding organism, a derivative 2, a deuterated derivative, a morphine derivative, etc. · 咕 ( 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬Derivatives, quinar-derived 2 ί derivatives, stupid derivatives, benzoic acid derivatives, benzoic acid, etc. Examples of polymer-based luminescent materials are: poly(p-phenylene), biosynthesis Phenanthene derivatives, polyethylene scent (tetra) derivatives, polylith eve 85 201226394 40550pif alkane derivatives, poly derivatives, polyparaphenyl derivatives, etc. Styryl derivatives Examples are: an amine-containing styryl derivative, a styryl aryl derivative, etc. The other electron transporting material used in the organic EL device of the present invention can be used as a compound which can be used as an electron transporting compound in a photoconductive material. It can be used as an electron transport layer of an organic EL element and a compound of a ferrite layer. Specific examples of such an electron transport material are: a ruthenium-based metal complex...bipyrene, anthracene derivative, phenanthroline Derivatives, biphenyl hydrazine derivatives, abominable sitting organisms, porphin derivatives, tri-sit derivatives, bismuth, and metal complexes of base derivatives, (4) lin derivative: wow = Derivatives of polymers, compounds, gallium complexes, phenylenes, triazine derivatives, pyridazine derivatives, υ'τ bio, imipenem derivatives, derivatives, etc. Hole injection material and hole injection material used for organic EL element: from the previous charge in the photoconductive material as a hole == compound, or hole injection layer of organic el element The second is to make: two people: any choice of materials The use of biological, etc.. The material of the living organism, the triarylamine derivative, and the phthalocyanine derivative layer can be formed by the respective constituents of the composition. The properties of the film material can be formed by the formation method or the like. It is suitable to form a film; it is not particularly limited, and may be in the range of 2 nm to 5 〇〇〇 nm according to the enthalpy. 86 201226394 40550pif In addition, the method of the luminescent material film (four) is preferably _ because it is easy to obtain a homogeneous Membrane, and it is not easy to generate pinholes/. In the case of thinning using the electroplating method, the steaming condition is different according to the invention, and the type of the photomaterial* is not (5). Generally, it is preferably set in the following range: the temperature of the heating boat is 耽~gamma^, the degree of vacuum is 10.6 Pa~10-3 Pa, and the speed of steaming is 〇01 nm/sec~5 〇 fine, ς ^ substrate The temperature is -150 ° C to +30 CTC, and the film thickness is 5 ηιη to 5 μιη. The organic EL device of the present invention is preferably supported by any of the above structures. As long as the substrate has mechanical strength, thermal stability, and transparency, a glass, a transparent plastic film, or the like can be used. For the anode material, it is possible to use the alloys Sn02 and z, which are CUI indium tin oxides (hereinafter, the 'smooth cathode material can use a metal having a work function of less than 4 ev, a compound = a compound, and a mixture thereof. Specific examples thereof are H弼, town, , alloys, alloys, etc. alloys, / bell, magnesium / silver, magnesium / indium, etc. In order to efficiently extract some of the light, it is desirable to at least one full reduction of the organic EL read as The sheet resistance electrode of the electrode has a permeability of 10% or more. It is a property of the electrode material, but is usually set in the range of 10 = 2 = 2 nm. Such an electrode can be used by evaporation or ruthenium by using the above. The method of forming a thin enamel by money, etc. is made of: - ί / 吏 二 tt Ming qiaoqiao material to make the organic EL element 3 above the dangerous pole / hole injection layer / hole transmission 87 201226394 The electron transport material of the present invention The thin material of the cathode/organic EL element is formed on the appropriate substrate by a vapor-deposited hole to form a hole injection layer and a positive electrode on the impurity electrode. A film on which the light-emitting layer is formed is formed. An electron transporting material invented on the light-emitting layer is formed into a film By electroporation, a thin film containing a substance for a cathode is formed by steaming, thereby obtaining a target organic EL element. Further, in the above-described production of the Lit member, the order of fabrication can be reversed, and the cathode can be sequentially fabricated. In the case where a DC voltage is applied to the organic EL element obtained as described above, the light is applied to the organic EL element obtained in this way, and the voltage is applied to the polarity of the anode and the polarity of the cathode is -, if 2 V is applied. When the voltage is about 40 V, the light can be observed from the transparent or translucent electrode side (anode, cathode, and both), and the organic EL element emits light even when an alternating voltage is applied. The waveform of the alternating current can be arbitrary. [Examples] Hereinafter, the present invention will be described in more detail based on examples. First, a synthesis example of the compound used in the examples will be described below. [Synthesis Example 1] Synthesis of Compound (1-7-74) <Synthesis of 9-(4-t-butylphenyl)anthracene> Under a nitrogen atmosphere, 31 g of 9-bromoindole, 25 g of 4-tert-butylphenylboronic acid, and Pd (PPh3) were added. 41.3 g, potassium phosphate 51 g and 1,2,4-trimethylbenzene 150 The flask of ml was stirred at reflux temperature for 21 hours. The reaction solution was cooled to 201226394 40550 pif but was taken to room temperature and then water was added _separation. Separation by liquid extraction (hqmd solid, washing with decyl alcohol, and washing with a third butyl benzene fine 28 g (tetra) acid S S which is precipitated by reading the solvent to obtain 9 gram of <9_ desert -1 is the synthesis of the third phenyl group) & Added 9-(4-tert-butyl phenyl 3 〇〇 ml S, 19 g. Stir at room temperature 丨n± ^ n戌坭j Since the 酝月月女1* /5 /3⁄4.# ', 夺, add sodium thiosulfate aqueous solution and stop the reaction mixture to transfer to the liquid separation funnel, using the imitation to extract. Borrow * suction set!饤f, followed by steam reduction from the gas _ (four) solid, and then recrystallized from the sputum to obtain phenyl) 蒽 29 g. , Le Yi <Synthesis of 3-(6-bromonaphthalen-2-yl)pyridine> The flasks of "smelly i 〇g and THF 6 () ml were cooled in an ice bath, in a secret environment, - side The lion - while adding isopropyl chloride chlorinated THF solution 35 m after the completion of the dropwise addition, temporarily warmed to room temperature, cooled in ice water, while adding secret zinc - tetramethyl ethanediamine The complex I7g. Afterwards, at room temperature _H, after the addition of trisole: acid 6-bromonaphthyl ester 18 g and PdCl2 (dppp) 1.6 g, was scrambled for 3 hours at reflux temperature. After the reaction liquid is cooled to room temperature, in order to remove the metal ions of the catalyst, an ethylenediaminetetraacetic acid/tetraammine salt dihydrate which is equivalent to about 3 times the molar amount of the target compound is added and dissolved in an appropriate amount of water. The solution (hereinafter, abbreviated as EDTA · 4Na aqueous solution) and toluene were separated by liquid. After distilling off the solvent under reduced pressure, the column was chromatographed by ruthenium column chromatography (曱89 201226394本/乙乙格为=7/3 base) Pyridine 12 g. (Production ratio)) Purification to obtain 3·(6-bromonaphthalene_2_<compound of compound (1-7々4)> 3-Γ6′, self-poor 1 5.9 s, 雔Bu wu _2 · · 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 The flask was placed under nitrogen for a period of 4 hours. To the solution, 9_Mo·1〇-(4_Second native)蒽8.6 g, potassium phosphate 9.3 g and 1,2,4-triazole were added to the solution. Benzene 50" using Didike tube to heat the dimethoxyethyl wire at room temperature, add 2 ml of second butanol, 5 m of water (di-mercaptoacetone), 0.4 g and 2 g of hexyl sulphate 5 g, further mixing at reflux temperature for 2 hours. The mixture was cooled (4) at room temperature, and after washing with water, the solid was collected by suction filtration. The obtained solid was washed with decyl alcohol, washed with ethyl acetate, and purified by hydrazine column chromatography (benzene/ethyl acetate = 9/1 (volume ratio)) to obtain a compound (hm). ): 3-(6-(1〇-(4_t-butyl)phenyl)indoleyl)naphthalene-2-ylpyridinium g. The structure of the compound was confirmed by NMR measurement. ^-NMR (CDC13): δ = 9.07 (m, lH), 8.68 (dd, lH), 8.23 (m, lH), 8.15 (d, lH), 8.08 (m, lH), 8.03 (m, 2H) , 7.83 (dd, lH), 7.78 (d, 2H), 7.72 (d, 2H), 7.68 (dd, lH), 7.63 (d, 2H), 7.42-7.48 (m, 3H), 7.30-7.38 (m , 4H), 1.49 (s, 9H). [Synthesis Example 2] Synthesis of Compound (1-7-26) <Synthesis of 9-(3-Tolyl)purine> 201226394 Under the environment of 40550pif, 9 g of onion 36 g, 3-methylbenzene was added Base shed II i, PPh3) 41 4g4_ 59 § and 丨, 2, 4 ^ · methyl benzene 150 at reflux temperature _ 2 5 hours. The test is cooled to the chamber to distill off the benzene to perform liquid separation. After purifying the medium = insect toluene solution using a short-slurry hose column, the solvent was removed under reduced pressure. The oil t obtained was added to the obtained oil t, and the precipitated solid was collected by aspiration to obtain a synthesis of 9 minutes of benzophenone 31 g 〇 <9-bromo-10_(3_ phenylphenyl) hydrazine. 9-(3-Phenylphenyl)蒽3〇§ and in a 2〇〇mi flask in the 'online environment in the ice crunch, add _ hu ship imino moth ^ 1 §. At a temperature of -15 hours, the reaction was stopped by adding sodium thiosulfate solution. The solution was transferred to a liquid separation funnel, and the == inspection tube (4) was taken after extraction. The ship was added under reduced pressure to remove the solution obtained by the solution, and the precipitated solid was sucked to obtain 9-di-10-(3-indolyl) 蒽3〇 g. <Synthesis of 4,4,5,5-tetradecyl-2-(10-(3_曱 基)) Onion Η Η 二 Dioxopentane Ring> 9 备10-(3 _tolyl)g 3〇g, conjugated acid vinegar vinegar g, bis(diphenylidene acetonide) put (〇) i 5 g, tricyclohexylphosphine] 4 g, acid clock 15 g, potassium carbonate 12 g and cyclopentyl hydrazine _ 1 〇〇 ml flask = gas environment, under the degree of return _ 1M, when the limb solution is cooled to warm, add water and toluene for liquid separation, using a short 矽 rubber column The obtained toluene solution was purified, the solvent was distilled off under reduced pressure, and heptane was added to the obtained oil, and the precipitated solid was collected by suction filtration to obtain 4,4,5,5·91 201226394 40550 pif g. A (1G (3. Abenyl) S,9·yl)-1,3,2·diqi_pentane μ <Compound (1, synthesis > 4 4 s <^2.^1; : Ψ & -2-(1〇-(3- ^ ^ ) t -9-
Pd(PPh3M"g g W酉夂鉀13Π2,4_三曱基笨刈如、 丁,m及水1〇mi的燒瓶在回流溫度下授拌 了 =應液冷教室溫後,添加水及T苯進行液體分離,、 °藉由娜管柱層析法(甲苯/乙酸乙卜 201=))純化所獲得的粗產物後,從甲苯 合分、、文進仃再結晶,獲得化合i : 甲苯基)蒽-9-基)萘基)„比—7 , #丄 ^ (1〇-(3- 化合物的結構。 (化。錯由NMR測定而確認 HNMR (CDC13) : 5 = 9.06 (m,lH) ,8.67 (dd,lH) 8.22 m 1=,8.14 (d,1H),8 〇6 (m, ’ ’ 7.81(m,lH),7.75(d,2H),77 ,, 7.50(t,lH),7.45(m,1H),72 ,;,7.㈤,1H), [合成例挪合物⑽987-)7.=/H),2.5心 <9-(3-第三丁基苯基)葱的合成口> 在氮氣環境下,將添加有9_溴箴 苯基)_4,4,5,5_四甲基],3,2_二氧雜‘^ 3.1g、磷酸鉀37g、l,2,4-三曱其贫,衣g ( Ph3)4 及水3㈣的燒瓶在回流溫度;第三丁醇編 卻至室溫後,添加水及甲笨;小時。將反應液冷 订液體分離。利用短矽膠管Pd (PPh3M " gg W 酉夂 potassium 13 Π 2, 4 _ tridecyl alum, such as, butyl, m and water 1 〇mi flask was mixed at reflux temperature = should be liquid cold after teaching room temperature, add water and T benzene The liquid separation is carried out, and the obtained crude product is purified by Na-column chromatography (toluene/acetic acid ethylbenzene 201 =)), and then recrystallized from toluene fraction and hydrazine to obtain a compound i: tolyl group蒽-9-yl)naphthyl) „比—7 , #丄^ (1〇-(3- structure of the compound. (Chemical error confirmed by NMR to confirm HNMR (CDC13): 5 = 9.06 (m, lH ), 8.67 (dd, lH) 8.22 m 1=, 8.14 (d, 1H), 8 〇 6 (m, ' ' 7.81 (m, lH), 7.75 (d, 2H), 77,, 7.50 (t, lH) ), 7.45 (m, 1H), 72,;, 7. (5), 1H), [Synthesis Example (10) 987-) 7.=/H), 2.5 hearts <9-(3-tert-butylbenzene Synthetic port of onion) > In a nitrogen atmosphere, 9-bromoindole phenyl)_4,4,5,5-tetramethyl], 3,2-dioxa'^ 3.1 g, potassium phosphate was added. 37g, l,2,4-triterpene is lean, the flasks of g ( Ph3) 4 and water 3 (iv) are at reflux temperature; after the third butanol is compiled to room temperature, water and stupid are added; Cold set liquid separation Using short silicone tubes
92 S 201226394 40550pif 所㈣的f苯溶液,減錢顧除去溶劑,藉由吸遽 9由添加甲醇而析出的固體,獲得9-(3-第三丁基苯基) 4 24 g。 < 9->臭-1 〇_(3_第三丁基苯基)蒽的合成>92 S 201226394 40550pif The f-benzene solution of (iv) was reduced in weight to remove the solvent, and 9-(3-t-butylphenyl) 4 24 g was obtained by sucking 9 a solid precipitated by adding methanol. <9->Synthesis of odor-1 〇_(3_t-butylphenyl)anthracene>
向添加有9_(3-第三丁基苯基)蒽23g、碘O.lg及THF 0 ,燒瓶中’在氮氣環境下添加N_漠號站酿亞胺η I在至下攪拌丨小時,添加硫代硫酸鈉水溶液而停止反 應。將該溶液轉移至液體分離漏斗中,利用甲苯進行萃取。 !!=石夕膠:柱純化所獲得的甲苯溶液’在減壓蒸德除去 二甘',進行曱笨/曱醇再沈澱,獲得9备10_(3_第三丁基 本基)葱23 g。 〈化合物(1-7-98)的合成〉 將,加有3-(6->臭萘_2_基户比咬6·2 g、聯石朋酸頻那醇酷 7 f、雙(二亞节基丙_巴(〇) 〇·4 g、三環己基膦〇.5 g、 =3·9 g及二曱氧基乙燒5〇 ml的燒瓶在氣氣環境下’ —回始皿度下勝4小時。向該溶液中添加9養1〇_(3_第 二Λί苯基)葱8·6 8、鱗酸鉀9·3 g及1,2,4·三甲基苯5〇 用迪恩-斯達克管,將二甲氧基乙絲常 第,5如、水5ml、雙(二亞节基丙嗣) , ‘ g及一%己基膦〇·5 g,在回流溫度下進一步攪 將反應液冷卻到室溫,進行水洗而使鹽溶解後, 二由吸制體。错_膠f柱層析法(曱苯/乙酸乙醋 处曰^tb))純化所獲得的固體後’從甲苯中進行再 、—獲得化合物(1々8):3_(6__•第三τ基苯基) 93 201226394 蒽-9-基)萘-2-基)。比啶1.5 g。藉由NMR測定而確認化合物 的結構。 !H-NMR ( CDC13) : δ = 9.07 (m,lH) ,8.68 (dd,lH), 8.23 (s,lH) ,8.16 (d,lH) ,8.08 (m,lH) ,8.03 (m,2H), 7.83 (m,lH) ,7.75 (d,2H),7.72 (d,2H),7.68 (m,lH), 7.52-7.61 (m,3H),7.46 (m,lH) , 7.30-7.38 (m,5H),1.41 (s,9H)〇 [合成例4]化合物(1-7-96)的合成 < 2-(10-(4-第三丁基苯基)蒽-9-基)_4,4,5,5-四甲基 -1,3,2-二氧雜硼戊環的合成〉 將添加有9-溴-10-(4-第三丁基苯基)蒽7.8 g、聯硼酸 頻那醇酯6.1 g、雙(二亞苄基丙酮)鈀(0) 0.3 g、三環己基 膦〇.3 g、乙酸鉀3 9g、碳酸鉀2.8 g、及環戊基甲基醚4C ml的燒瓶在氮氣環境下,在回流溫度下攪拌6 5小時。將 ,應液冷卻至室溫後,添加水及曱苯進行液體分離 ,減壓 劑。向所獲得的油中添加庚烷,藉由吸濾採集 四曱義1 3 2獲Γ 2供(4-第三丁基苯基)蒽斗基)_4,4,5,5· 甲基-1,3,2·二氧雜爛戊環6 9g。 二合成〉 THF2〇ml的燒瓶在^、=有M3·絲基)如定9.8 g及 滴加2.6M的正丁義鐘甲醇浴令冷卻到-70X:以下,緩慢 拌0.5小時,添加氣化丨7 111卜滴加完畢後,在同溫度下攪 在室溫下攪拌〇5小時、四曱基乙二胺錯合物12 g。其後, 、谈’泰加三氟甲磺酸溴萘_2_酯15To the addition of 23 g of 9-(3-t-butylphenyl)anthracene, iodine O.lg and THF 0, the flask was stirred in a nitrogen atmosphere, and N-glycol was added to the yttrium I. The reaction was stopped by adding an aqueous sodium thiosulfate solution. The solution was transferred to a liquid separation funnel and extracted with toluene. !!=石夕胶: The toluene solution obtained by column purification 'removal of digan' under reduced pressure, and then reprecipitated by hydrazine/sterol to obtain 9 g of 10_(3_t-butyl-based) onion 23 g . <Synthesis of Compound (1-7-98)> Addition of 3-(6-> Odornaphthalene_2_base to bite 6.2 g, chlorpyrifos pinacol 7 f, double ( Two subunits, propylene, argon, argon, arsenic, arsenic, arsenic, arsenic, arsenic, arsenic, arsenic, argon The dish is won for 4 hours. To the solution, 9 〇 1 〇 (3_2Λ 苯基 phenyl) onion 8·6 8 , potassium citrate 9·3 g and 1,2,4·trimethylbenzene are added to the solution. 5 迪Den-Stark tube, dimethoxyethyl wire often, 5, water 5ml, bis (dipyridyl propyl hydrazine), 'g and one% hexylphosphine 〇 · 5 g, in After further stirring at reflux temperature, the reaction solution is cooled to room temperature, washed with water to dissolve the salt, and then purified by a mixture of the wrong body, gel column chromatography (benzene/acetic acid ethyl acetate 曰^tb). After obtaining the solid, 'repeating from toluene--obtaining compound (1々8): 3_(6__•third τ-phenyl) 93 201226394 蒽-9-yl)naphthalen-2-yl). 1.5 g. The structure of the compound was confirmed by NMR measurement. !H-NMR (CDC13) : δ = 9.07 (m, lH) , 8.68 (dd, lH), 8.23 (s, lH) , 8.16 (d, lH) , 8.08 (m, lH) , 8.03 (m, 2H) ), 7.83 (m, lH), 7.75 (d, 2H), 7.72 (d, 2H), 7.68 (m, lH), 7.52-7.61 (m, 3H), 7.46 (m, lH), 7.30-7.38 ( m, 5H), 1.41 (s, 9H) 〇 [Synthesis Example 4] Synthesis of Compound (1-7-96) < 2-(10-(4-T-butylphenyl)fluoren-9-yl) Synthesis of _4,4,5,5-tetramethyl-1,3,2-dioxaborolane> 9-bromo-10-(4-t-butylphenyl)phosphonium 7.8 g, 6.1 g of pinacol borate, bis(dibenzylideneacetone)palladium(0) 0.3 g, tricyclohexylphosphine 〇.3 g, potassium acetate 39 g, potassium carbonate 2.8 g, and cyclopentyl methyl ether The 4 C ml flask was stirred at reflux temperature for 6 5 hours under a nitrogen atmosphere. After the solution is cooled to room temperature, water and benzene are added for liquid separation and decompression. Add heptane to the obtained oil, and collect tetrahydropyrene 1 3 2 to obtain Γ 2 for (4-t-butylphenyl) sulfonyl)_4,4,5,5·methyl- by suction filtration. 1,3,2· Dioxolane pentane 6 9g. The second synthesis > THF2 〇 ml flask in ^, = M3 · silk base) such as 9.8 g and dropwise addition of 2.6M n-butyl kiln methanol bath to cool -70X: below, slowly mix for 0.5 hours, add gasification 丨7 After completion of the dropwise addition of 111, the mixture was stirred at room temperature for 5 hours at room temperature, and 12 g of tetradecylethylenediamine complex. After that, talk about 'Tega bromine naphthalene 2 - ester 15
S 201226394 40550pif ^丙_巴(〇)及以雙(二苯基膦基)丙烧〇·5 g,在回起度下祕丨小時。反應完雜,添加edta · ΤΙ水f夜、乙酸乙酯進行液體分離,在減壓蒸餾除去溶 劑,’ It由活性氧她f柱層析* (f苯/乙酸乙醋=9/1 (容積比))進行純化。接著,利用甲醇洗淨,從乙酸乙醋 /曱醇混合溶财騎躲晶,翁4_(3_(6_錢_2乂苯基) 0比口定 5.3 g。 <化合物(1-7-96)的合成> 將添加有2-(1〇-(4-第三丁基苯基)蒽_9-基)-4,4,5,5-四 甲基-1,3,2-二氧雜硼戊環6.1 g、4-(3-(6-溴萘-2-基)苯基)吡 唆 5.0 g、Pd(PPh3)40.5 g、碳酸鉀 3.0 g、1,2,4-三曱基笨 25 ml、第三丁醇5 ml及水5 ml的燒瓶在回流溫度下攪拌6 小時。將反應液冷卻至室溫後,添加EDTA · Na水及曱笨 進行液體分離,減壓蒸餾除去溶劑。藉由活性氧化鋁管柱 層析法(曱苯/乙酸乙酯=9/1 (容積比))純化所獲得的粗 產物。利用乙酸乙酯將減壓蒸餾除去溶劑而獲得的固體洗 淨後,從曱苯中進行再結晶,獲得化合物(1-7-96 ) : 4 (3-(6-(10-(4-第三丁基苯基)蕙-9-基)萘-2-基)苯基)。比啶 3.3 g。藉由NMR測定而確認化合物的結構。 ^-NMR ( CDC13) : 8.73 (dd,2H) ,8.27(m,lH) ,8.15 (d,lH),8.03 (m,3H),7.99 (m,2H),7.78 (d,2H),7·73 (d,2H) ,7.61-7.70 ( m,7H),7.44 ( m,2H),7.30〜7.38 (m,4H)、1.49 (s,9H)。 [合成例5]化合物(1-14-14)的合成 95 201226394 40550pif <9-(3-乙氧基苯基)_1Q_(萘_2基)蒽的合成〉 向燒瓿中添加1春3-乙氧基苯72 4 g、(10_(萘·2·基) 蒽-9-基)硼酸 104.5 g、Pd(pph3)4 1〇 4 g、磷酸鉀 127 4 g、 1,2,4-三甲基苯600 ml、2-内醇12〇 m卜及水12〇 m卜在氮 氣環U ’在回流溫度下_ M、時。將反餘冷卻至室 >皿後’藉由吸遽採集液中的固體,利用曱醇洗淨,獲得 乙氧基苯基)-10-(萘-2-基)蒽82§。 < 3-(10-(萘_2_基)蒽_9·基)笨_合成〉 向燒瓶中添加9♦乙氧基苯基)_1〇·(萘-2-基)蒽82 及°比._ 446.G g ’錢氣環境下,在回流溫度下攪拌 =時。將反應液冷卻至室溫後,添加水,料吸據 析出的固H,利用甲醇洗淨,再利用曱苯洗淨,獲得 3-(10-(秦-2-基)蒽_9·基)苯齡 % 〇 g。 〉<三氟甲烧雜3.(蔡-2-基)蒽冬基)苯醋的合成 將添加有3供(萘·2^9_基)⑽(则g)及吼 疋—W燒升瓦在冰浴中冷卻,在氣氣環境下,向其中滴 =甲續酸肝65.0 g。滴加完畢後,進一步在室溫下擾 苯醋9(^ g。’獲付二乱甲燒續酸3_(10•(萘_2_基)葱冬基) Α) 1〈3 Γ:5:5-四甲基_2你(1〇-(萘_2_基)葱冬基)苯 丞)-1,3,2-—氧雜硼戊環的合成> 向:^瓶中添加三氟甲燒細3_(1〇_(蔡_2基)葱斗基) 96 201226394 40550pif 苯酯90.3 g、聯硼酸頻那醇酯521 g、雙(二亞苄基丙酮) 鈀(〇) 7.4 g、三環己基膦7 2 g、乙酸鉀33 6 g、碳酸鉀 23.6 g、及苯曱醚5〇〇 ml,在回流溫度下攪拌5小時。將 反應液冷卻至室溫後,利用塗敷有矽藻土的桐山漏斗進行 吸濾而除去不溶物,利用EDTA · 4Na水將濾液洗淨。利 用庚炫•將減壓蒸餾除去濾液的溶劑而獲得的固體洗淨,獲 得 4,4,5,5-四曱基_2-(3_(10_(萘·2_基)蒽-9-基)苯基)'3 2: 氧雜硼戊環(52.0 g)。 ’ <化合物(1-14-14)的合成〉 向燒瓶中添加4,4,5,5-四曱基-2-(3-(10-(萘-2-基)蒽_9_ 基)本基)-1,3,2-一氣雜蝴戊環8.6 g、藉由曰本專利特開 2009-124114中記載的方法而合成的5,_溴甲基-2,2,聯吡 11 定 5.1 g、Pd(PPh3)4〇.6 g、填酸鉀 7.2 g、1,2,4-三甲基苯 25 ml、第三丁醇5 ml、及水1 ml,在回流溫度下搜拌2.5小 時。將反應液冷卻至室溫後,添加水後,藉由吸濾採集液 中的固體,利用曱醇洗淨。藉由矽膠管柱層析法(曱苯/ 乙酸乙酯二9/1 (容積比))純化該固體’接著藉由活性碳 管柱層析法進一步純化。濃縮溶液,從氯苯中進行再結晶, 獲得化合物(1-14-14): 3-曱基-5,-(3-(10-(萘-2-基)蒽-9-基) 苯基)-2,2’-聯吡啶2.3 g。藉由NMR測定而確認化合物的結 構。 'H-NMRC CDC13) : 6 = 9.05 ( m,lH) , 8.55 ( d,lH) , 8.11 (dd,lH), 8.09( d,lH), 8.02( m,lH), 8.00( s,lH), 7.73-7.95 (m,9H),7.60 (m,5H),7.30-7.40 (m,4H),7.23 (m,lH), 97 201226394 2.56 (s,3H)。 [合成例6]化合物(1-11-1)的合成 < 2-曱基-4-(6-(10-苯基葱-9-基)萘_2_基)吡啶的合成〉 將4,4,5,5-四曱基-2-(6-(10-苯基蒽_9·基)萘_2_ 基)-1,3,2-二氧雜硼戊環(2.0 g)、4-溴-2-曱基吡咬(0 8 g)、 Pd(PPh3)4(0.3 g)、構酸lf( 1.7 g)、1,2,4-三曱基苯(2〇 mi)、 第三丁醇(5 ml)及水(1 ml)添加到燒瓶中,在氮氣環 境下在回流溫度下擾拌7.5小時。加熱完畢後,將反應液 冷卻到室溫,添加水及甲苯進行液體分離。減壓蒸顧除去 >谷劑’藉由石夕膠管柱層析法(展開液(developing solvent): 曱苯/乙酸乙酯=95/5)純化所獲得的固體。接著,將所獲 得的溶出液通入短活性碳管柱’除去著色成分。採集減壓 蒸顧除去所獲得的濾液的過程中析出的結晶,獲得 (1-11-1)所表示的化合物2-甲基-4-(6-(10-苯基蒽-9-基) 蔡-2-基)B 比 σ定(〇.7g)。 藉由NMR測定而確認化合物的結構。 ^-NMR ( CDC13) : δ = 8.66 ( d,lH),8.30 ( S,1H),8.17 (d,lH),8.03 (m,2H),7.87 (d,lH) ,7.72-7.78 (m,4H), 7.70 (d,lH),7.65 (m,2H),7.58 (m,2H) ,7.56 (m,3H), 7.31-7.39 (m,4H) ,2.73 (s,3H)。 [合成例7]化合物(MI-2)的合成 <3_曱基_4·(6·(10-苯基蒽-9-基)萘_2·基)吡啶的合成> 將4,4,5,5-四曱基-2-(6-(10-苯基蒽-9-基)萘-2· 基一氧雜石朋戊環(2.0 g )、4->臭-3-曱基°比。定鹽酸鹽S 201226394 40550pif ^ C-bar (〇) and bis(diphenylphosphino)-propanone · 5 g, the secret time of the recovery. After completion of the reaction, add edta · hydrazine f night, ethyl acetate for liquid separation, and distill off the solvent under reduced pressure, 'It is by active oxygen her f column chromatography* (f benzene / acetic acid vinegar = 9 / 1 (volume More than)) to carry out purification. Then, it was washed with methanol, and mixed with acetic acid/methanol to dissolve the crystal, and Weng 4_(3_(6_钱_2乂phenyl) 0 was 5.3 g. <Compound (1-7- Synthesis of 96) will be added with 2-(1〇-(4-t-butylphenyl)phosphonium-9-yl)-4,4,5,5-tetramethyl-1,3,2- Dioxaborolane 6.1 g, 4-(3-(6-bromonaphthalen-2-yl)phenyl)pyridinium 5.0 g, Pd(PPh3) 40.5 g, potassium carbonate 3.0 g, 1,2,4- The flask containing 25 ml of triterpene, 5 ml of tributanol and 5 ml of water was stirred at reflux temperature for 6 hours. After cooling the reaction solution to room temperature, EDTA·Na water and hydrazine were added for liquid separation and decompression. The solvent was distilled off, and the obtained crude product was purified by active alumina column chromatography (benzene/ethyl acetate = 9/1 (volume ratio)). After washing with solid, recrystallization from benzene to give compound (1-7-96): 4 (3-(6-(10-(4-t-butylphenyl)fluoren-9-yl)naphthalene 2-yl)phenyl). 3.3 g of pyridine. The structure of the compound was confirmed by NMR. ^-NMR (CDC13): 8.73 (dd, 2H), 8.27 (m, lH), 8.15 (d, lH) ), 8.03 (m, 3H), 7.99 (m, 2H), 7.78 (d, 2H), 7.73 (d, 2H), 7.61-7.70 (m, 7H), 7.44 (m, 2H), 7.30~7.38 (m , 4H), 1.49 (s, 9H) [Synthesis Example 5] Synthesis of Compound (1-14-14) 95 201226394 40550pif <9-(3-ethoxyphenyl)_1Q_(naphthalene-2-yl)anthracene Synthesis> Add 1 spring 3-ethoxybenzene 72 4 g, (10_(naphthalene-2-yl)phosphonium-9-yl)boronic acid 104.5 g, Pd(pph3)4 1〇4 g, phosphoric acid Potassium 127 4 g, 1,2,4-trimethylbenzene 600 ml, 2-internal alcohol 12 〇m b and water 12 〇m b in the nitrogen ring U 'at reflux temperature _ M, time. To the chamber > after the dish 'by washing the solid in the collection liquid, washing with decyl alcohol to obtain ethoxyphenyl)-10-(naphthalen-2-yl) fluorene 82 §. < 3-(10-(naphthalene-2-yl)phosphonium-9-yl) stupid_synthesis> Add 9♦ ethoxyphenyl)_1〇·(naphthalen-2-yl)fluorene 82 and ° to the flask Than ._ 446.G g 'money gas environment, stirring at reflux temperature = time. After cooling the reaction solution to room temperature, water was added to absorb the precipitated solid H, washed with methanol, and washed with benzene to obtain 3-(10-(qin-2-yl)indole-9. ) Benzene age 〇g. 〉<Trifluoromethane-3. (Cai-2-yl) 蒽冬基) The synthesis of benzene vinegar will be added with 3 (naphthalene·2^9_yl) (10) (g) and 吼疋-W The riser tile is cooled in an ice bath, and in an airy environment, it is dropped into the acid liver 65.0 g. After the addition is completed, further disturb the benzene vinegar at room temperature 9 (^ g. 'Pay the two chaotic smoldering acid 3_(10•(naphthalene-2-yl) onion winter base) Α) 1<3 Γ:5 :5-Tetramethyl-2 (1〇-(naphthalene-2-yl) onion-based) phenylhydrazine)-1,3,2--oxaborolane synthesis > Add to: Trifluoromethane 3_(1〇_(Cai_2) onion) 96 201226394 40550pif phenyl ester 90.3 g, boranoic acid pinacol ester 521 g, bis(dibenzylideneacetone) palladium (〇) 7.4 g, 7 2 g of tricyclohexylphosphine, 33 6 g of potassium acetate, 23.6 g of potassium carbonate, and 5 〇〇ml of phenyl hydrazine, and stirred at reflux temperature for 5 hours. After cooling the reaction solution to room temperature, the insoluble matter was removed by suction filtration using a Kiriyama funnel coated with diatomaceous earth, and the filtrate was washed with EDTA · 4Na water. The solid obtained by distilling off the solvent of the filtrate under reduced pressure was washed with Geng Hyun to obtain 4,4,5,5-tetradecyl-2-(3_(10-(naphthalene-2-yl)fluoren-9-yl) Phenyl) '3 2: oxaborolane (52.0 g). '<Synthesis of Compound (1-14-14)> To the flask was added 4,4,5,5-tetradecyl-2-(3-(10-(naphthalen-2-yl)indole_9_yl) 5,_bromomethyl-2,2,bipyridyl 11 which is synthesized by the method described in JP-A-2009-124114. 5.1 g, Pd(PPh3)4〇.6 g, potassium 7.2 g, 1,2,4-trimethylbenzene 25 ml, third butanol 5 ml, and water 1 ml, mix at reflux temperature 2.5 hours. After the reaction solution was cooled to room temperature, water was added, and the solid in the collected liquid was collected by suction filtration, and washed with decyl alcohol. The solid was purified by ruthenium column chromatography (benzene/ethyl acetate 2/1 (volume ratio)) and then further purified by activated carbon column chromatography. The solution is concentrated and recrystallized from chlorobenzene to obtain the compound (1-14-14): 3-mercapto-5,-(3-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl )-2,2'-bipyridyl 2.3 g. The structure of the compound was confirmed by NMR measurement. 'H-NMRC CDC13) : 6 = 9.05 ( m,lH) , 8.55 ( d,lH) , 8.11 (dd,lH), 8.09( d,lH), 8.02( m,lH), 8.00( s,lH) , 7.73-7.95 (m, 9H), 7.60 (m, 5H), 7.30-7.40 (m, 4H), 7.23 (m, lH), 97 201226394 2.56 (s, 3H). [Synthesis Example 6] Synthesis of Compound (1-11-1) <Synthesis of 2-Mercapto-4-(6-(10-phenyl onion-9-yl)naphthalene-2-yl)pyridine> 4 ,4,5,5-tetradecyl-2-(6-(10-phenylindole-9)naphthalene-2-yl)-1,3,2-dioxaborolan (2.0 g), 4-bromo-2-indenylpyridine (0 8 g), Pd(PPh3) 4 (0.3 g), acid lf (1.7 g), 1,2,4-trimethylbenzene (2〇mi), Third butanol (5 ml) and water (1 ml) were added to the flask, and the mixture was stirred at reflux temperature for 7.5 hours under a nitrogen atmosphere. After the completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added to carry out liquid separation. The obtained solid was purified by vacuum distillation to remove >granules' by chromatography on silica gel column chromatography (developing solvent: benzene/ethyl acetate = 95/5). Next, the obtained eluate was passed through a short activated carbon tube column to remove the coloring component. The crystals precipitated during the removal of the obtained filtrate were collected under reduced pressure to obtain the compound 2-methyl-4-(6-(10-phenylfluoren-9-yl) represented by (1-11-1). Cai-2-yl) B is determined by σ (〇.7g). The structure of the compound was confirmed by NMR measurement. ^-NMR (CDC13): δ = 8.66 (d, lH), 8.30 (S, 1H), 8.17 (d, lH), 8.03 (m, 2H), 7.87 (d, lH), 7.72-7.78 (m, 4H), 7.70 (d, lH), 7.65 (m, 2H), 7.58 (m, 2H), 7.56 (m, 3H), 7.31-7.39 (m, 4H), 2.73 (s, 3H). [Synthesis Example 7] Synthesis of Compound (MI-2) <3_Mercapto- 4·(Synthesis of 6-(10-phenylfluoren-9-yl)naphthalene-2-yl)pyridine> 4,5,5-tetradecyl-2-(6-(10-phenylfluoren-9-yl)naphthalene-2·yl-oxazepene (2.0 g), 4-> odor-3 - thiol ratio.
S 98 201226394 (1.0 g )、Pd(PPh3)4 ( 0.3 g )、石粦酸鉀(1 7 g )、1,2,4-三曱 基本(20 ml)、第二丁醇(5 mi)及水(丨^1)添加到燒瓶 中,在氮氣環境下,在回流溫度下攪拌24.5小時。加熱完 畢後,將反應液冷卻到室溫,添加水及甲苯進行液體分離。 減壓蒸顧除去溶劑,藉由梦膠管柱層析法(展開液:曱苯/ 乙酸乙酯= 95/5)純化所獲得的固體。接著,將所獲得的 溶出液通入短活性碳管柱,除去著色成分。採集減壓蒸餾 除去所獲得的遽液的過程中析出的結晶,進一步在甲苯中 進行再結晶,獲得(1-11-2)所表示的化合物3_甲基 -4-(6-(10-苯基蒽-9-基)萘-2-基)吡啶(〇.5 g)。 藉由NMR測定而確認化合物的結構。 ^-NMRCCDCla): 6=8.62 (s,lH) , 8.58 ( d,lH) , 8.13 (d,lH) , 8.06 (s51H) , 8.02 (d,lH) , 7.99 (s,lH) , 7.75 (d,4H) ,7.70 (dd,lH) ,7.65 (t,2H) ,7.59 (t,2H) ,7.53 (m,2H) ,7.33-7.39 (m,5H) ,2.44 (s,3H)° [合成例8]化合物(mi-3)的合成 < 2-甲基-5-(6-(10-苯基蒽-9-基)萘-2-基)吡啶的合成> 將4,4,5,5-四甲基_2·(6-(1〇-苯基蒽_9_基)萘-2- 基)-1,3,2-一氧雜硼戊環(2.0 g)、5-溴-2-曱基。比啶(〇.8 g)、 Pd(PPh3)4 (0.15 g)、構酸鉀(1.7g)、1,2,4-三甲基苯(20 ml)、第二丁醇(5 ml)及水(1 ml)添加到燒瓶中,在氮 氣環境下,在回流溫度下攪拌5小時。加熱完畢後,將反 應液冷卻到室溫,添加水及曱苯進行液體分離。減壓蒸餾 除去溶劑,藉由矽膠管柱層析法(展開液:曱苯/乙酸乙酯 99 201226394. TV J J v^if = 95/5)純化所獲得的固體。將減壓蒸餾除去溶劑而獲得 的固體從甲苯中進行再結晶,獲得(M1_3)所表示的化 合物2-曱基-5-(6-(10-苯基g-9-基)萘_2_基)吡啶(】2 g)。 藉由NMR測定而確認化合物的結構。 H-NMR(CDC13) : 5=8.95 (m,lH), 8.20(s,lH) ,8.14 (d,lH) , 8.01 ( m,2H) , 7.96 ( dd,lH), 7.81 ( dd,lH) , 7.74 (m,4H) , 7.67 (dd,lH) , 7.63 (t,2H) , 7.57 (t,lH) , 7.52 (m,2H),7.30-7.37 (m,5H),2.67 (S,3H)。 [合成例9]化合物(MI-4)的合成 < 3-曱基-5-(6-(10-苯基蒽-9-基)萘-2-基)n比η定的合成> 將4,4,5,5-四曱基-2-(6-(10-苯基蒽基)萘-2· 基)-1,3,2-二氧雜硼戊環(2.0 g)、3-溴-5-曱基吼啶(〇.8g)、 Pd(PPh3)4(0.3 g)、填酸鉀(1.7 g)、1,2,4-三曱基苯(20 ml)、 第二丁醇(5 ml)及水(1 ml)添加到燒瓶中,在氮氣環 境下’在回流溫度下撥拌7.5小時。加熱完畢後,將反應 液冷卻到室溫,添加水及甲苯進行液體分離。減壓蒸顧除 去溶劑’藉由石夕膠管柱層析法(展開液:曱苯/乙酸乙酯二 95/5)純化所獲得的固體。接著,將所獲得的溶出液通入 短活性碳管柱,除去著色成分。減壓蒸餾除去溶劑,添加 庚烷進行再沈澱,獲得(1-11-4)所表示的化合物3_甲基 -5-(6-(10-苯基蒽冬基)萘-2-基)吼啶(1.3 g)。 藉由NMR測定而確認化合物的結構。 'H-NMR (CDC13) : 6=8.87 (m,lH) ,8.51 (m,lH), 8.22 (S,1H) ,8.15 (d,lH) ,8.03 (m,2H) ,7.89 (m,lH)S 98 201226394 (1.0 g ), Pd(PPh3)4 (0.3 g), potassium citrate (1 7 g), 1,2,4-trimium (20 ml), second butanol (5 mi) Water (丨^1) was added to the flask, and the mixture was stirred at reflux temperature for 24.5 hours under a nitrogen atmosphere. After the completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was removed by evaporation under reduced pressure, and the obtained solid was purified by methylene chloride column chromatography (yield: benzene/ethyl acetate = 95/5). Next, the obtained eluate was passed through a short activated carbon tube column to remove the coloring component. The crystals precipitated during the distillation of the obtained mash were distilled under reduced pressure, and further recrystallized in toluene to obtain the compound represented by (1-11-2), 3-methyl-4-(6-(10-). Phenylfluoren-9-yl)naphthalen-2-yl)pyridine (〇.5 g). The structure of the compound was confirmed by NMR measurement. ^-NMRCCDCla): 6=8.62 (s,lH) , 8.58 ( d,lH) , 8.13 (d,lH) , 8.06 (s51H) , 8.02 (d,lH) , 7.99 (s,lH) , 7.75 (d , 4H), 7.70 (dd, lH), 7.65 (t, 2H), 7.59 (t, 2H), 7.53 (m, 2H), 7.33-7.39 (m, 5H), 2.44 (s, 3H) ° [Synthesis Example 8] Synthesis of Compound (mi-3) <Synthesis of 2-Methyl-5-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)pyridine> 4, 4, 5,5-tetramethyl-2·(6-(1〇-phenylindole-9-yl)naphthalen-2-yl)-1,3,2-oxaborolan (2.0 g), 5 -Bromo-2-indenyl. Bipyridine (〇.8 g), Pd(PPh3)4 (0.15 g), potassium citrate (1.7 g), 1,2,4-trimethylbenzene (20 ml), second butanol (5 ml) Water (1 ml) was added to the flask, and the mixture was stirred at reflux temperature for 5 hours under a nitrogen atmosphere. After the heating was completed, the reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography (eluent: benzene/ethyl acetate 99 201226394. TV J J v^if = 95/5). The solid obtained by distilling off the solvent under reduced pressure was recrystallized from toluene to obtain the compound 2-mercapto-5-(6-(10-phenylg-9-yl)naphthalene_2_ represented by (M1_3). Base) pyridine (] 2 g). The structure of the compound was confirmed by NMR measurement. H-NMR (CDC13): 5 = 8.95 (m, lH), 8.20 (s, lH), 8.14 (d, lH), 8.01 (m, 2H), 7.96 ( dd, lH), 7.81 ( dd, lH) , 7.74 (m,4H) , 7.67 (dd,lH) , 7.63 (t,2H) , 7.57 (t,lH) , 7.52 (m,2H),7.30-7.37 (m,5H),2.67 (S,3H ). [Synthesis Example 9] Synthesis of Compound (MI-4) <Synthesis of 3-mercapto-5-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)n Ratio η Setting> 4,4,5,5-tetradecyl-2-(6-(10-phenylfluorenyl)naphthalen-2-yl)-1,3,2-dioxaborolan (2.0 g), 3-bromo-5-mercaptoacridine (〇.8g), Pd(PPh3)4 (0.3 g), potassium acetate (1.7 g), 1,2,4-trimethylbenzene (20 ml), Dibutanol (5 ml) and water (1 ml) were added to the flask, and the mixture was stirred at reflux temperature for 7.5 hours under a nitrogen atmosphere. After the completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added to carry out liquid separation. The solvent was distilled off under reduced pressure. The obtained solid was purified by chromatography on silica gel column chromatography (eluent: benzene/ethyl acetate). Next, the obtained eluate was passed through a short activated carbon tube column to remove the coloring component. The solvent was distilled off under reduced pressure, and heptane was added for reprecipitation to obtain a compound represented by (1-11-4): 3-methyl-5-(6-(10-phenylindolinyl)naphthalen-2-yl) Acridine (1.3 g). The structure of the compound was confirmed by NMR measurement. 'H-NMR (CDC13): 6=8.87 (m,lH), 8.51 (m,lH), 8.22 (S,1H), 8.15 (d,lH), 8.03 (m,2H), 7.89 (m,lH) )
100 201226394 4U55Upif 7.83 (dd,lH),7.73 (m,4H) , 7.67 (dd,lH),7.63 (m,2H), 7.57( t,lH) , 7.52(m,2H) , 7.30-7.37 (m,4H), 2.49( s,3H) ° [合成例10]化合物(1-11-5)的合成 <4·甲基-3-(6-(10-苯基蒽-9-基)萘·2_基定的合成〉 將4,4,5,5-四甲基-2-(6-(10-苯基蒽-9-基)萘_2- 基)-1,3,2-一氧雜棚戊壞(2.0 g )、3-漠-4_曱基n比Ί定鹽酸鹽 (1.0 g)、Pd(PPh3)4 (0.3 g)、磷酸鉀(1.7 g)、1,2,4·三曱 基苯(20ml)、第三丁醇(5ml)及水(1 ml)添加到燒瓶 中,在氮氣環境下,在回流溫度下攪拌7小時。加熱完畢 後’將反應液冷卻到室溫,添加水及甲苯進行液體分離。 減壓蒸餾除去溶劑’藉由矽膠管柱層析法(展開液:甲苯/ 乙酸乙酯=95/5)純化所獲得的固體。接著,將所獲得的 溶出液通入短活性碳管柱,除去著色成分。減壓蒸餾除去 溶劑’將所獲得的固體從曱苯中進行再結晶,獲得(M1_5) 所表示的化合物4-曱基-3-(6-( 10-苯基蒽-9-基)萘-2-基)吡 啶(0.6 g )。 藉由NMR測定而確認化合物的結構。 ^-NMR( CDC13) · 6=8.64(s,lH) , 8.55 (d,lH) , 8.14 (d,lH) , 8.06 (s,lH) , 8.02 (d,lH) , 7.99 (s,lH) , 7.76 (m,4H) ,7.70( dd,lH) ,7.63 (m,2H) , 7.59 ( t,2H) , 7.53 (m,2H) ,7.32-7.39 (m,4H) ,7.30 (d,lH) ,2.45 (s,3H) 〇 [合成例11]化合物(1-11-6)的合成 <2-曱基-3-(6-(10-苯基蒽-9-基)萘-2-基比。定的合成〉 將4,4,5,5-四曱基-2-(6-(10-苯基蒽-9-基)萘-2- 101 201226394 基)-l,3,2-二氧雜硼戊環(2.0 g)、3-溴-2-甲基吡啶(0.8 g)、 Pd(PPh3)4 (0.15 g)、磷酸鉀(1.7 g)、1,2,4-三曱基苯(20 ml)、第三丁醇(5 ml)及水(1 ml)添加到燒瓶中,在氮 氣環境下,在回流溫度下攪拌4小時。加熱完畢後,將反 應液冷卻到室溫,添加水及曱苯進行液體分離《減壓蒸顧 除去溶劑’藉由矽膠管柱層析法(展開液:曱笨/乙酸乙酯 = 95/5)純化所獲得的固體。接著,將所獲得的溶出液通 入短活性碳管柱’除去著色成分。減壓蒸餾除去溶劑,添 加庚烧進行再沈殿’獲得(1-11-6)所表示的化合物2-甲 基_3-(6_(10-苯基g-9-基)萘_2·基)《比啶(U g)。 藉由NMR測定而確認化合物的結構。 ^-NMRCCDCls): 6=8.60(m,lH), 8.11 (d,lH), 8.05 (s,lH),8.00 (d,lH),7.96 (s,lH),7·74 (m,4H) ,7.69 (m,2H),7.63( m,2H),7.57( m,2H), 7.52( m,2H),7.30-7.37 (m,4H),7_28 (m,lH),2.66 (s,3H)。 [合成例12]化合物(1-11-8)的合成 < 5-甲基-2-(6-(10-苯基-9-基)萘-2-基)η比α定的合成> 將4,4,5,5-四曱基-2-(6-(10-笨基蒽冬基)萘_2- 基)-1,3,2-二氧雜硼戊環(2.5 g)、3#-2-曱基吡啶(10g)、 Pd(PPh3)4 (0.15 g)、磷酸鉀(2.1 g)、1,2,4-三曱基苯(2〇 ml)、第二丁醇($ mi)及水(1 mi)添加到燒瓶中,在氮 氣環境下,在回流溫度下攪拌18小時。加熱完畢後,將反 應液冷卻到室溫,藉由吸濾採集析出的固體。藉由矽膠管 柱層析法(展開液:曱苯)純化所獲得的固體。接著,將100 201226394 4U55Upif 7.83 (dd,lH), 7.73 (m,4H), 7.67 (dd,lH), 7.63 (m,2H), 7.57( t,lH) , 7.52(m,2H) , 7.30-7.37 (m , 4H), 2.49 (s, 3H) ° [Synthesis Example 10] Synthesis of Compound (1-11-5) <4·methyl-3-(6-(10-phenylfluoren-9-yl)naphthalene · Synthesis of 2_基定> 4,4,5,5-tetramethyl-2-(6-(10-phenylfluoren-9-yl)naphthalene-2-yl)-1,3,2- Oxygen sulphate glutamine (2.0 g), 3-wet-4 曱 n n Ί 盐 盐 盐 (1.0 g), Pd (PPh3) 4 (0.3 g), potassium phosphate (1.7 g), 1, 2,4·trimethylbenzene (20 ml), third butanol (5 ml) and water (1 ml) were added to the flask, and stirred under reflux for 7 hours under a nitrogen atmosphere. The mixture was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was distilled off under reduced pressure. The obtained solid was purified by silica gel column chromatography (developing solvent: toluene / ethyl acetate = 95/5). The obtained eluate is passed through a short activated carbon tube column to remove the coloring component. The solvent is distilled off under reduced pressure. The obtained solid is recrystallized from toluene to obtain a compound represented by (M1_5) 4-mercapto- 3-(6-( 10-Phenylfluoren-9-yl)naphthalen-2-yl)pyridine (0.6 g). The structure of the compound was confirmed by NMR measurement. ^-NMR (CDC13) · 6 = 8.64 (s ,lH) , 8.55 (d,lH) , 8.14 (d,lH) , 8.06 (s,lH) , 8.02 (d,lH) , 7.99 (s,lH) , 7.76 (m,4H) ,7.70( dd, lH) , 7.63 (m, 2H) , 7.59 ( t, 2H) , 7.53 (m, 2H) , 7.32 - 7.39 (m, 4H) , 7.30 (d, lH) , 2.45 (s, 3H) 〇 [Synthesis Example 11] Synthesis of compound (1-11-6) <2-mercapto-3-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl ratio. Synthesis] 4, 4 ,5,5-tetradecyl-2-(6-(10-phenylfluoren-9-yl)naphthalene-2-101 201226394 base)-l,3,2-dioxaborolane (2.0 g) , 3-bromo-2-methylpyridine (0.8 g), Pd(PPh3)4 (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml), third Alcohol (5 ml) and water (1 ml) were added to the flask, and stirred at reflux temperature for 4 hours under a nitrogen atmosphere. After the heating is completed, the reaction solution is cooled to room temperature, and water and benzene are added for liquid separation. "Removing the solvent under reduced pressure" is carried out by a ruthenium column chromatography (developing solution: stupid / ethyl acetate = 95/5 The solid obtained was purified. Next, the obtained eluate was passed through a short activated carbon tube column to remove the coloring component. The solvent was distilled off under reduced pressure, and the compound represented by (1-11-6) was obtained by adding heptane to obtain the compound 2-methyl-3-(6-(10-phenylg-9-yl)naphthalene-2-yl group represented by (1-11-6). ) "Bitidine (U g). The structure of the compound was confirmed by NMR measurement. ^-NMRCCDCls): 6=8.60 (m, lH), 8.11 (d, lH), 8.05 (s, lH), 8.00 (d, lH), 7.96 (s, lH), 7·74 (m, 4H) , 7.69 (m, 2H), 7.63 ( m, 2H), 7.57 ( m, 2H), 7.52 ( m, 2H), 7.30-7.37 (m, 4H), 7_28 (m, lH), 2.66 (s, 3H) ). [Synthesis Example 12] Synthesis of Compound (1-11-8) <Synthesis of 5-methyl-2-(6-(10-phenyl-9-yl)naphthalen-2-yl)n Ratio α ; 4,4,5,5-tetradecyl-2-(6-(10-phenylidene)-naphthalene-2-yl)-1,3,2-dioxaborolane (2.5 g ), 3#-2-mercaptopyridine (10g), Pd(PPh3)4 (0.15 g), potassium phosphate (2.1 g), 1,2,4-trimethylbenzene (2〇ml), second Alcohol ($ mi) and water (1 mi) were added to the flask and stirred at reflux temperature for 18 hours under nitrogen. After the completion of the heating, the reaction solution was cooled to room temperature, and the precipitated solid was collected by suction filtration. The obtained solid was purified by ruthenium column chromatography (developing solution: benzene). Next, will
102 201226394 40550pif 所獲得的溶出液通入短活性碳管枉,除去著色成分。減壓 蒸餾除去溶劑,添加乙酸乙酯進行再沈澱,獲得(1-11-8) 所表示的化合物5-曱基-2-(6-(10-苯基蒽-9-基)萘-2-基)吡 啶(1.5 g)。 藉由NMR測定而確認化合物的結構。 ^-NMR (CDC13) : 5=8.63 (m,2H) ,8.23 (dd,lH), 8.16 (d,lH) ,8.00 (m,2H) ,7.86 (d,lH),7.73 (m,4H), 7.60-7.67 (m,4H) ,7.56 (t,lH),7.51 (m,2H),7.30-7.36 (m,4H),2.44 (s,3H)。 [合成例13]化合物(Ml-39)的合成 < 5-漠甲基-3,4’-聯°比°定的合成〉 將添加有4-溴-2-曱基吡啶(13.8 g)及甲苯(i5〇ml) 的燒瓶在丙酮/乾冰浴中冷卻。向該溶液中滴加1.6 Μ的正 丁基鐘的己烧溶液(55 ml)。滴加完畢後’ 一邊在丙明/乾 冰浴中冷卻一邊攪拌1小時,添加氣化鋅四曱基乙二胺 (29.3 g)及THF (45 ml),撤去丙酮/乾冰浴並升溫。在 升溫到室溫後,添加曱苯(20 ml)、3,5-二溴η比咬(no g) 及Pd(PPh3)4 (2.8 g),在回流溫度下攪拌2小時。將反應 液冷卻至室溫後,為了除去觸媒的金屬離子,而添加將相 對於目標化合物約相當於3倍莫耳的乙二胺四乙酸•四鈉 鹽一水合物溶解到適量的水中而成的溶液(以下,簡稱為 EDTA· 4Na水溶液)及曱苯進行液體分離。在減壓蒸餾除 去溶劑後,藉由矽膠管柱層析法(展開液:甲苯/乙酸乙酯) 純化所獲得的固體。此時,參考「有機化學實驗入門(1) 103 201226394 -物質處理法與公魅^ ,,..102 201226394 40550pif The obtained eluate is passed into a short activated carbon tube to remove the coloring component. The solvent was distilled off under reduced pressure, and ethyl acetate was added for reprecipitation to obtain the compound 5-(indolyl-2-(6-phenyl)-9-yl)naphthalene-2 represented by (1-11-8). -yl)pyridine (1.5 g). The structure of the compound was confirmed by NMR measurement. ^-NMR (CDC13): 5 = 8.63 (m, 2H), 8.23 (dd, lH), 8.16 (d, lH), 8.00 (m, 2H), 7.86 (d, lH), 7.73 (m, 4H) , 7.60-7.67 (m, 4H), 7.56 (t, lH), 7.51 (m, 2H), 7.30-7.36 (m, 4H), 2.44 (s, 3H). [Synthesis Example 13] Synthesis of Compound (M1-39) <5-Methyl-methyl-3,4'-linked ratio synthesis> 4-bromo-2-mercaptopyridine (13.8 g) was added The flask with toluene (i5 〇 ml) was cooled in an acetone/dry ice bath. To the solution was added dropwise a 1.6 Torr solution of n-butyl hexane (55 ml). After completion of the dropwise addition, the mixture was stirred for 1 hour while cooling in a propylene/dry ice bath, and zinc hydride tetradecylethylenediamine (29.3 g) and THF (45 ml) were added thereto, and the acetone/dry ice bath was removed and the temperature was raised. After warming to room temperature, toluene (20 ml), 3,5-dibromo-n-batch (no g) and Pd(PPh3) 4 (2.8 g) were added, and the mixture was stirred at reflux temperature for 2 hours. After cooling the reaction liquid to room temperature, in order to remove the metal ions of the catalyst, ethylenediaminetetraacetic acid tetrasodium salt monohydrate which is equivalent to about 3 times the molar amount of the target compound is added and dissolved in an appropriate amount of water. The resulting solution (hereinafter, abbreviated as EDTA·4Na aqueous solution) and benzene were separated by liquid. After removing the solvent under reduced pressure, the obtained solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate). At this time, refer to "Introduction to Organic Chemistry Experiment (1) 103 201226394 - Substance Treatment Method and Public Charm ^ , ,..
的合成> 將4,4,5,5·四曱基_2_(6_(1〇_苯基蒽冬基)萘_2_ 土)-1,3,2_二氧雜爛戊環(2 5 g)、5養2,_甲基_3,4,_聯吼咬 (匕1 g)、Pd(PPh3)4 (〇.i5g)、填酸鉀 u 7g)、124_ 三曱 基苯(20 =、第三丁醇(5ml)及水(i mi)添加到燒瓶 中’在氮氣環境下’在回流溫度下祕3小時。加熱完畢 後^將反應液冷卻到室溫,添加水及甲苯進行液體分離。 減壓蒸餾除去溶劑,藉由矽膠管柱層析法(展開液:曱苯/ 乙酸乙酯= 1/1)純化所獲得的固體。減壓蒸餾除去溶劑’ 將所獲得的固體從曱苯中進行再結晶,獲得(M1_39)所 表示的化合物2,-曱基-5-(6-(10-苯基蒽-9-基)萘-2-基)-3,4,-聯0比咬(0.3 g )。 藉由NMR測定而確認化合物的結構。 1H-NMR(CDC13): δ = 9.11(ιη,1Η), 8.92(m,lH),8.65 (d,lH),8.28 (m,2H),8·17 (d,lH),8·05 (m,2H),7.87 (d,lH),.7.68-7.75 (m,5H),7.61 (m,2H),7.56 (t,lH), 7.51(m,3H),7.45(m,lH),7.30-7.37(m,4H),2.70(s,3H)。 [合成例14]化合物(1-14-2)的合成 s 104 201226394 40550pif < 3_曱基-4_(3-(10_(萘_2·基)蒽-9-基)苯基)吼咬的合成 > 添加4,4,5,5-四甲基-2-(3-(10-(萘-2-基)蒽-9-基)苯 基)-1,3,2-二氧雜侧戊環(2.5 g)、4-漠-3-曱基吼咬鹽酸鹽 (1.3 g)、Pd(PPh3)4 (0.35 g)、填酸鉀(3.2 g)、1,2,4-三曱 基苯20 ml、第三丁醇5 ml、及水1 ml,在回流溫度下擾 拌11.5小時。將反應液冷卻至室溫後,添加曱苯及水進行 液體分離。減壓蒸餾除去溶劑,藉由矽膠管柱層析法(展 開液:曱苯/乙酸乙酯=95/5)純化所獲得的固體。接著, 將所獲得的溶出液通入短活性碳管柱,除去著色成分。減 壓蒸餾除去溶劑,添加庚烷進行再沈澱,獲得(M4_2) 所表示的化合物3-曱基-4-(3-(10-(萘-2·基)蒽-9-基)苯基)吡 啶(1.4g)。 藉由NMR測定而確認化合物的結構。 ^-NMRCCDC^) : 5=8.53 (s,lH) , 8.50 (d,lH) , 8.08 (dd,lH), 8.02(m,lH),7.97(d,lH),7.92(m,lH),7.70-7.78 (m,5H) , 7.48-7.63 (m,6H) , 7.35-7.39 (m,2H) , 7.29-7.34 (m,3H),2.41 (s,3H)。 [合成例15]化合物(1-14-3)的合成 < 2-曱基-5-(3_(10-(萘_2_基)蒽_9·基)苯基)吼咬的合成 > 添加4,4,5,5-四曱基_2_(3-(1〇-(萘_2_基)蒽冬基)苯 基)-1,3,2·二氧雜硼戊環(2.5 g)、5-溴-2-曱基。比啶(1.〇 g)、 Pd(PPh3)4(0.35 g)、填酸鉀(3.2 g)、1,2,4-三曱基苯 20 m卜 105 201226394 40550pif 第二丁醇5 m卜及水1 ml,在回流溫度下攪拌8 5小時。 將反應液冷卻至室溫後,藉由吸濾採集析出的固體。藉由 石夕膠管柱層析法(展開液:甲苯/乙酸乙酯=95/5)純化所 獲得的固體。接著,將所獲得的溶出液通入短活性碳管柱, 除去著色成分。減壓蒸餾除去溶劑,將所獲得的 乙酸乙醋洗淨,獲得(1-14_3)所表示的化合物2體= -5-(3-(10-(萘-2-基)蒽-9-基)苯基)π比啶(丨5 g)。 藉由NMR測定而確認化合物的結構。 ^-NMRCCDC^): 6=8.45(m,lH), 8.08(d,lH)5 8.03 (m,lH),7.99(S,1H),7.93(m,lH),7.87(dd,lH),7.70-7.81 (m,7H),7.57-7.63( m,3H),7.54( m,lH), 7.30-7.40( m4H) 7.23 (d,lH),2.61 (S,3H)。 ’ 人 [合成例16]化合物(i-14-u)的合成 < 5-演-6’-甲基-2,2’-聯吡啶的合成〉 =加有2|6·甲基㈣(5.2g)及環戊基甲基鱗⑼ 甲醇/乾冰財冷卻。向該溶液中滴加_ 丁基鐘的己烧溶液(22 ml)。滴加完畢後,一邊在甲 ^乾冰冷中冷卻一邊授拌2小時,添加氣化鋅四甲A乙二 Π.3 g) ’撤以醇/乾冰浴並升溫。在升溫到室〉U 添加2,5-一溴吡啶丨g)及pd(pp 溫度下繪挑1 S丨irt勿 · g) ’在回流Synthesis> 4,4,5,5·tetradecyl_2_(6_(1〇_phenylindolinyl)naphthalene_2_土)-1,3,2-dioxolane (2) 5 g), 5 养 2, _methyl _3, 4, _ 吼 匕 (匕 1 g), Pd (PPh3) 4 (〇.i5g), potassium hydride u 7g), 124_ tridecyl benzene ( 20 =, tert-butanol (5ml) and water (i mi) were added to the flask 'under nitrogen atmosphere' for 3 hours at reflux temperature. After heating, the reaction solution was cooled to room temperature, water and toluene were added. The liquid was separated. The solvent was evaporated under reduced pressure, and the obtained solid was purified by silica gel column chromatography (eluent: benzene/ethyl acetate = 1/1). Recrystallization from benzene to obtain the compound 2 represented by (M1_39), -mercapto-5-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)-3,4,- The structure of the compound was confirmed by NMR measurement. 1H-NMR (CDC13): δ = 9.11 (ιη, 1 Η), 8.92 (m, lH), 8.65 (d, lH), 8.28 (m,2H),8·17 (d,lH),8·05 (m,2H),7.87 (d,lH),.7.68-7.75 (m,5H),7.61 (m,2H),7.56 ( t,lH), 7.51(m,3H), 7.45(m,lH), 7.30-7.37 (m, 4H), 2.70 (s, 3H) [Synthesis Example 14] Synthesis of compound (1-14-2) s 104 201226394 40550pif < 3_mercapto-4_(3-(10_(naphthalene) Synthesis of _2·yl) -9-yl)phenyl) occlusion> Addition of 4,4,5,5-tetramethyl-2-(3-(10-(naphthalen-2-yl)indole- 9-yl)phenyl)-1,3,2-dioxapentanyl (2.5 g), 4-oxa-3-mercaptopurine hydrochloride (1.3 g), Pd(PPh3)4 (0.35 g), potassium acetate (3.2 g), 20 ml of 1,2,4-tridecylbenzene, 5 ml of third butanol, and 1 ml of water, and stirred at reflux temperature for 11.5 hours. The reaction solution was cooled to After the room temperature, the benzene and water were added for liquid separation, and the solvent was evaporated under reduced pressure, and the obtained solid was purified by silica gel column chromatography (eluent: benzene/ethyl acetate = 95/5). The obtained eluate was passed through a short activated carbon tube column to remove the coloring component. The solvent was distilled off under reduced pressure, and heptane was added for reprecipitation to obtain a compound represented by (M4_2) 3-mercapto-4-(3-( 10-(Naphthalen-2-yl)fluoren-9-yl)phenyl)pyridine (1.4 g) The structure of the compound was confirmed by NMR measurement. ^-NMRCCDC^) : 5=8.53 (s,lH) , 8.50 (d,lH) , 8.08 (dd,lH), 8.02 (m,lH), 7.97 (d,lH), 7.92 (m,lH), 7.70-7.78 (m, 5H), 7.48-7.63 (m, 6H), 7.35-7.39 (m, 2H), 7.29-7.34 (m, 3H), 2.41 (s, 3H). [Synthesis Example 15] Synthesis of Compound (1-14-3) <Synthesis of 2-indolyl-5-(3_(10-(naphthalene-2-yl)indole-9(yl)phenyl)) Add 4,4,5,5-tetradecyl_2_(3-(1〇-(naphthalen-2-yl)indoleyl)phenyl)-1,3,2·dioxaborolan ( 2.5 g), 5-bromo-2-indenyl. Bipyridine (1.〇g), Pd(PPh3)4 (0.35 g), potassium acidate (3.2 g), 1,2,4-trimethylbenzene 20 m Bu 105 201226394 40550pif second butanol 5 m 1 ml of water was stirred at reflux temperature for 8 5 hours. After the reaction solution was cooled to room temperature, the precipitated solid was collected by suction filtration. The obtained solid was purified by Shih Hose column chromatography (eluent: toluene / ethyl acetate = 95/5). Next, the obtained eluate was passed through a short activated carbon tube column to remove the coloring component. The solvent was distilled off under reduced pressure, and the obtained ethyl acetate was washed to obtain the compound 2 represented by (1-14_3) = -5-(3-(10-(naphthalen-2-yl)fluoren-9-yl) Phenyl) π is pyridine (丨 5 g). The structure of the compound was confirmed by NMR measurement. ^-NMRCCDC^): 6=8.45(m,lH), 8.08(d,lH)5 8.03 (m,lH), 7.99 (S,1H), 7.93 (m,lH), 7.87 (dd,lH), 7.70-7.81 (m,7H), 7.57-7.63 (m,3H), 7.54 (m,lH), 7.30-7.40 ( m4H) 7.23 (d,lH), 2.61 (S,3H). 'Synthesis of compound [Synthesis Example 16] Compound (i-14-u) < Synthesis of 5-act-6-methyl-2,2'-bipyridyl> = 2|6·methyl(tetra) ( 5.2g) and cyclopentylmethyl scale (9) methanol / dry ice cooling. To the solution was added dropwise a hexane solution of butyl ketone (22 ml). After the completion of the dropwise addition, the mixture was stirred for 2 hours while being cooled in a dry ice, and zinc hydride was added to the aluminum/blue dry bath and the temperature was raised. In the room temperature > U added 2,5-monobromopyridinium g) and pd (pp at the temperature of 1 S丨irt do not g)
• 4N H 時。將反應液冷卻至室溫後,添加EDTA 後减及曱苯進行液體分離。在賴f4顧除去溶劑 後糟由矽膠管柱層析法(展開液:甲 所獲传的固體。此時,緩慢地增加展開液中的乙^乙酉^ 106 201226394 4U550pif 2率,使目標物溶出。接著,減壓蒸餾除去溶劑,將所獲 付的固體從庚烷中進行再結晶,獲得5_溴_6,-曱基-22, 吡啶(1.4 g)。 ’ < 61-甲基·5-(3_(10_(萘_2_基)蒽冬基)苯基从2,,〇比啶 的合成> 添加4,4,5,5-四曱基_2_(3_(10_(萘_2·基)蒽_9_基)苯 基)-1,3,2-二氧雜硼戊環(2 〇 g)、5_漠_6,_曱基-2,2,_聯吡啶 (1·0 g)、Pd(pph3)4 ( 0.15 g)、鱗酸钟(1.7 g)、ι,2,4-三甲 基笨20 ml、第三丁醇5 m卜及水1 m卜在回流溫度下搜 拌7.5小時。將反應液冷卻至室溫後,藉由吸濾採集析出 的固體。藉由矽膠管柱層析法(展開液:甲苯/乙酸乙酯= 95/5)純化所獲得的固體,將所獲得的溶出液直接使用塗 敷有活性碳的桐山漏斗進行吸濾,除去著色成分。減壓蒸 餾除去溶劑,添加乙酸乙酯進行再沈澱,獲得(1—14-11) 所表示的化合物6’-曱基-5-(3-(10-(萘-2-基)蒽-9-基)苯 基)-2,2’-聯吡啶(l.2g)。 藉由NMR測定而確認化合物的結構。 ^-NMR (CDC13) : 5 = 9.03 (m,lH) , 8.49 (dd,lH), 8.22 (d,lH) , 8.09 (m,2H) , 8.03 (m,lH) , 8.00 (s,lH), 7.93 (ιη,ΙΗ) ,7.87 (d,lH) ,7.68-7.83 (m,7H) ,7.55-7.64 (m,4H) ,7.30-7.40 (m,4H) ,7.17 (d,lH) ,2.65 (s,3H)。 [合成例17]化合物(1-14-12)的合成 < 5-溴-5’-曱基-2,2’-聯吡啶的合成〉 將添加有2-溴-5-曱基吡啶(1.7 g)及THF (5 ml)的 107 201226394 40550pif 的THFfr ’向該溶液中滴加2以的異丙基氯化鎮 拌3 5小睹< ·5ϊη1)。滴加完畢後,撤去冰浴在室溫下攪 二胳,再次在冰浴中冷卻,添加氯化辞四甲基乙 ^ (2d f撤去冰浴並升溫到室溫後,添加2,5-二溴吡 二寺。將〜(G.35 g) ’在回流溫度下授拌U 及甲苯液冷部至室溫後,添加EDTA · 4Na水溶液 管柱層析。在減壓蒸餾除去溶劑後,藉由矽膠 的η液:曱苯/乙酸乙酯=9/ι)純化所獲得 5、拿==壓驗除去溶劑,添加錢進行再沈殿,獲得 5_>臭-5-甲基_2,2.♦比〇定(15g)。 I 于 的合:甲基_5L(M1G•(萘·2·細冬基)苯基)·2,2,♦比咬 ^ ^,5’5,甲基邻⑽·(萘_2基)蒽_9基)苯 ^,氧雜爛戊環(2 〇 g)、5_演.5,_甲基_2,2,_聯。比口定 美策i、Γ(ρρί3)4⑶·15 g)、磷酸鉀(1.7 g)、似-三甲 IΓ、第三丁醇5 m卜及水1 m卜在回流溫度下攪 液冷卻至室溫後’添加甲苯及水進_ 減反条餾除去溶劑,藉由矽膠管柱層析法(展開 ^1=/^乙醋=95/5)純化所獲得的固體,將所獲得 贿性碳管柱,除去著色成分。賴蒸顧除 冷劑’添加乙酸乙g旨進行再沈殿,將所獲得的固體進— ^=本中進行再結晶’獲得(M4_12)所表示的化合物 5·曱基-5·-(3.(萘·2_基)葱斗基)苯基)2,2,导比咬(丄2• When 4N H. After cooling the reaction solution to room temperature, EDTA was added and the benzene was reduced to carry out liquid separation. After the removal of the solvent, the residue was removed by a gel column chromatography (expansion liquid: a solid obtained by a solution. At this time, the rate of ethyl acetonitrile in the developing solution was slowly increased to dissolve the target. Then, the solvent was distilled off under reduced pressure, and the obtained solid was recrystallized from heptane to obtain 5-bromo-6,-mercapto-22, pyridine (1.4 g). ' < 61-methyl· Synthesis of 5-(3_(10_(naphthalene-2-yl)indolinyl)phenyl from 2,,indenidine> Addition of 4,4,5,5-tetradecyl_2_(3_(10_(naphthalene) _2·yl)蒽_9_yl)phenyl)-1,3,2-dioxaborolan (2 〇g), 5_ desert_6,_mercapto-2,2,_bipyridine (1·0 g), Pd(pph3)4 (0.15 g), squaring clock (1.7 g), ι, 2,4-trimethyl stupid 20 ml, third butanol 5 m b, and water 1 m The mixture was stirred at reflux temperature for 7.5 hours. After the reaction mixture was cooled to room temperature, the precipitated solid was collected by suction filtration. Purified by column chromatography (eluent: toluene/ethyl acetate = 95/5) The obtained solid was directly suction-filtered using a Kiriyama funnel coated with activated carbon to remove the colored component. The solvent was removed, and ethyl acetate was added for reprecipitation to obtain a compound 6'-mercapto-5-(3-(10-(naphthalen-2-yl)fluoren-9-yl) represented by (1-14-11). Phenyl)-2,2'-bipyridyl (1. 2g). The structure of the compound was confirmed by NMR. ^-NMR (CDC13): 5 = 9.03 (m,lH), 8.49 (dd,lH), 8.22 (d,lH) , 8.09 (m,2H) , 8.03 (m,lH) , 8.00 (s,lH), 7.93 (ιη,ΙΗ) , 7.87 (d,lH) , 7.68-7.83 (m,7H) , 7.55-7.64 (m, 4H), 7.30-7.40 (m, 4H), 7.17 (d, 1H), 2.65 (s, 3H). [Synthesis Example 17] Synthesis of Compound (1-14-12) < Synthesis of 5-bromo-5'-fluorenyl-2,2'-bipyridine > THFfr ' of 107 201226394 40550pif added with 2-bromo-5-mercaptopyridine (1.7 g) and THF (5 ml) To the solution, 2 parts of isopropyl chloride was added dropwise for 3 5 hours of hydrazine < 5ϊη1). After the addition was completed, the ice bath was removed and stirred at room temperature, and cooled again in an ice bath to add chlorine. Derivatives of tetramethyl bethane (2d f after removing the ice bath and warming to room temperature, add 2,5-dibromopyridinium. Add ~(G.35 g)' to mix U and toluene at reflux temperature Add EDTA · 4Na aqueous column after cold to room temperature Chromatography. After distilling off the solvent under reduced pressure, it was purified by purifying the η solution of phthalocyanine: benzene/ethyl acetate = 9/m. 5. The solvent was removed by pressing ==, and the money was added to re-deep the temple to obtain 5_> 5-methyl-2, 2.♦ ratio (15g). Combination of I: methyl _5L (M1G•(naphthalene·2·fine) phenyl)·2,2,♦ than bite ^ ^, 5'5, methyl o (10) · (naphthalene-2-yl)蒽_9 base) benzene ^, oxalate pentane (2 〇 g), 5 _ .5, _ methyl 2, 2, _. It is better than the mouth to determine the best policy i, Γ (ρρί3) 4 (3) · 15 g), potassium phosphate (1.7 g), like - trimethyl I Γ, third butanol 5 m and water 1 m b at the reflux temperature to cool the liquid to the chamber After warming, add toluene and water to remove the solvent, and purify the obtained solid by ruthenium column chromatography (expanded ^1=/^ vinegar = 95/5) to obtain the brittle carbon tube. Column to remove the coloring component. Lai steam de-cooling agent 'addition of acetic acid, the purpose of re-sinking, the obtained solids into - ^ = recrystallization in the present 'obtained (M4_12) represented by the compound 5 · mercapto-5 ·- (3. (naphthalene·2_base) onion) phenyl) 2,2, lead bite (丄2
Ο JΟ J
S 108 201226394 藉由NMR測定而確認化合物的結構。 ^-NMRCCDC^): 5 = 9.03(m,lH), 8.52(s,lH), 8.44 (dd,lH) , 8.33 (d,lH) , 8.09 (m,lH) , 8.03 (m,lH) , 8.00 (s,2H) ,7.93 (m,lH) ,7.87 (m,lH) ,7.73-7.83 (m,6H), 7.56-7.66 (m,5H) ,7.31-7.39 (m,4H) ,2.41 (s,3H)。 [合成例18]化合物(1-14-13)的合成 < 5’-溴-4-甲基-2,2’-聯吡啶的合成〉 將添加有2-溴-4-曱基吡〇定(6.9 g)及THF (20 ml) 的燒瓶在冰浴中冷卻,向該溶液中滴加2Μ的異丙基氣化 鎂的THF溶液(24 ml)。滴加完畢後,撤去冰浴在室溫下 授拌1小時後’再次在冰浴中冷卻’添加氣化鋅四甲基乙 二胺(12.1 g)。撤去冰浴並升溫到室溫後,添加2,5_二溴 0比咬(9.5 g)及Pd(PPh3)4 ( 1.4 g) ’在回流溫度下攪拌2 5 小時。將反應液冷卻至室溫後,添加EDTA · 4Na水溶液 及甲苯進行液體分離。在減壓蒸餾除去溶劑後,藉由矽膠 官柱層析法(展開液:甲苯/乙酸乙醋=9/1 )純化所獲得 的固體。減壓蒸餾除去溶劑,將所獲得的固體從庚烷中進 行再結晶,獲得5,·演-4-曱基·2,2,_聯吡啶(5.5g)。 <4_曱基_5’-〇(1〇·(萘_2_基)蒽_9_基)苯基)_2,2,·聯吡啶 的合成> 添加4,4,5,5-四曱基_2_(3_(10_(萘_2_基)蒽_9_基)笨 基)-1,3,2-二氧雜蝴戊環(2.〇 g)、溴_4·甲基聯d比咬 (1.2 g)、Pd(PPh3)4 (0.15 g)、鱗酸钟(1 7 g)、丄又斗·三甲 基笨20 m卜第三丁醇5 m卜及水1 ^卜在回流溫度下攪 109 201226394 40550pif 拌16小時。將反應液冷卻至室溫後,添加甲苯及水進行液 體分離。減壓蒸德除去溶劑,藉由矽膠管柱層析法(展開 液:曱苯/乙酸乙酯=95/5 )純化所獲得的固體,將所獲得 的溶出液通入短活性碳管柱,除去著色成分。減壓蒸镏除 去溶劑,利用庚烷洗淨,藉此獲得(1-14-13)所表示的化 合物4-甲基_5’-(3-(10-(萘基)蒽冬基)苯基)_2,2,_聯吡唆 (1.4 g) 〇 藉由NMR測定而確認化合物的結構。 b-NlVtRXCDCls): δ = 9·04(πι,1Η),8.55(d,lH),8.47 (dd,lH),8.28 (S,1H),8.11 (dd,lH),8.09 (d,lH),8.03 (m,lH),8.00(s,lH),7.93(m,lH),7.88(d,lH),7.73.7 83 (m,6H),7.57_7.63(m,4H),7.30-7.40(m,4H),7_14(d ih) 2.45 (s,3H)。 ’ ’ ’ [合成例19]化合物(1-14-15)的合成 <5-溴-6'-曱基-2,3'-聯吡啶的合成> 將添加有5-溴-2-曱基°比啶(3.4 g)及THF ( 1〇 mi 的燒瓶在冰浴中冷卻,向該溶液中滴加2M的異丙基氣 鎂的THF溶液(llml)。滴加完畢後,撤去冰溫 授拌3小時後,再次在冰浴中冷卻,添加氣化鋅四甲= 二胺(5.5 g)。撤去冰浴並升溫到室溫後,添加2 5_二$ 咬(4.7 g)及Pd(PPh3)4 (0·7 g),在回流溫度下授掉5 時。將反應液冷卻至室溫後,添加EDTA · 4Na水七略 才δ。)及曱苯進行液體分離。在減壓蒸鶴除去 由石夕膠管柱層析法(展:甲笨/乙酸乙醋=7/3)交純 110 201226394 40550pif 所獲得的固體’獲得5·溴-6,-曱基-2,3'-聯吡啶(1.5 g)。 <6’-曱基-5-(3·(10·(萘_2_基)蒽_9_基)苯基)_2,3,_聯吡啶 的合成> 添加4,4,5,5-四甲基-2-(3-(10-(萘-2-基)蒽-9-基)笨 基)-1,3,2-一氧雜爛戊環(2 〇 g)、5-漠-6’-曱基-2,3'-聯η比〇定 (1.2 g)、Pd(PPh3)4 (0.15 g)、磷酸鉀(1.7 g)、1,2,4-三甲 基笨25 m卜第三丁醇5 ml、及水1 m卜在回流溫度下搜 拌5小時。將反應液冷卻至室溫後,藉由吸濾採集析出的 固體’利用曱醇洗淨,再利用乙酸乙酯洗淨。接著,藉由 矽膠管柱層析法(展開液:曱笨/乙酸乙酯=4/1)進行純 化’將所獲得的溶出液通入短活性碳管柱,除去著色成分。 減壓蒸餾除去溶劑,將所獲得的固體進一步從氣苯中進行 再結晶’獲得(M4-15 )所表示的化合物6,-曱基 -5-(3-(10-(萘-2-基)蒽-9-基)苯基)-2,3’-聯。比啶(1.3 g)。 藉由NMR測定而確認化合物的結構。 ^-NMR (CDC13) * 5 = 9.13 (m,lH) , 9.07 (m,lH), 8.28(dd,lH), 8.01-8.ll(m33H), 8.00( s,lH), 7.93( m,lH), 7.86(m,lH), 7.73-7.83(m,7H), 7.57-7.64(m,4H), 7.31-7.39 (m,4H) ,7.28 (d,lH) ,2.63 (s,3H)° [合成例20]化合物(1-14-16)的合成 < 5-溴曱基-2,3r-聯吡啶的合成〉 將添加有3·溴-5-曱基吡啶(3.4 g)及THF ( 10 ml) 的燒瓶在冰浴中冷卻,向該溶液中滴加2Μ的異丙基氯化 鎂的THF溶液(11 ml)。滴加完畢後,撤去冰浴在室溫下 111 201226394 攪拌1.5小時後,再次在冰浴中冷卻,添加氣化鋅四甲基 乙二胺(5.5 g)。撤去冰浴並升溫到室溫後,添加2,5_二溴 吼咬(4.7 g)及Pd(PPh3)4 (0.7 g) ’在回流溫度下攪拌5 小時。將反應液冷卻至室溫後,添加EDTA · 4Na水溶液 及甲苯進行液體分離。在減壓蒸餾除去溶劑後,藉由矽膠 管柱層析法(展開液:甲苯/乙酸乙酯=7/3)純化所獲得 的固體,獲得5-演-5'-甲基-2,3'-聯吡啶(1.4 g)。 < 5’-甲基_5_(3-(1〇-(萘·2_基)蒽_9_基)苯基)_2,3’_聯吡啶 的合成> 添加4,4,5,5-四甲基_2_(3_(10_(萘_2_基)蒽冬基)苯 基)-1,3,2-二氧雜硼戊環(2.〇 g)、5_漠_6,_甲基_2,3,·聯吡咬 (l_2g)、Pd(PPh3)4 (〇.i5g)、磷酸鉀(i.7g)、1>2,4_三甲 基本25 ml、第二丁醇5 ml、及水1 ml,在回流溫度下搜 拌5小時。將反應液冷卻至室溫後,藉由吸濾採集析出的 固體,利用甲醇洗淨,再利用乙酸乙酯洗淨。接著,藉由 矽膠管柱層析法(展開液:曱苯/乙酸乙酯=4/1)進行純 化,再將所獲得的溶出液通入短活性碳管柱,除去著色成 分。減壓蒸餾除去溶劑,將所獲得的固體進一步從氣苯中 進行再結晶’獲得(1-14-16 )所表示的化合物5'-曱基 -5_(3·(1〇-(萘基)葱_9·基)苯基)-2,3,-聯吡啶(1.3 g)。 藉由NMR測定而確認化合物的結構。 'H-NMRC CDC13) : 6 = 9.08 ( m,lH) , 9.04 ( s,lH) , 8.50S 108 201226394 The structure of the compound was confirmed by NMR measurement. ^-NMRCCDC^): 5 = 9.03(m,lH), 8.52(s,lH), 8.44 (dd,lH) , 8.33 (d,lH) , 8.09 (m,lH) , 8.03 (m,lH) , 8.00 (s,2H) , 7.93 (m,lH) , 7.87 (m,lH) , 7.73 - 7.83 (m,6H), 7.56-7.66 (m,5H) ,7.31-7.39 (m,4H) ,2.41 ( s, 3H). [Synthesis Example 18] Synthesis of Compound (1-14-13) < Synthesis of 5'-Bromo-4-methyl-2,2'-bipyridine> 2-Bromo-4-indolylpyridinium added A flask of 6.9 g and THF (20 ml) was cooled in an ice bath, and a solution of 2% isopropylmagnesium hydride in THF (24 ml) was added dropwise. After the completion of the dropwise addition, the ice bath was removed and the mixture was stirred at room temperature for 1 hour, and then cooled again in an ice bath to add zinc trimethylethylenediamine (12.1 g). After removing the ice bath and warming to room temperature, 2,5-dibromo 0 was added (9.5 g) and Pd(PPh3) 4 (1.4 g) was stirred at reflux temperature for 25 hours. After the reaction solution was cooled to room temperature, an aqueous solution of EDTA·4Na and toluene were added to carry out liquid separation. After distilling off the solvent under reduced pressure, the obtained solid was purified by silica gel column chromatography (eluent: toluene/ethyl acetate = 9/1). The solvent was distilled off under reduced pressure, and the obtained solid was recrystallized from heptane to give 5,················ <4_曱基_5'-〇(1〇·(Naphthalene_2_yl)蒽_9_yl)phenyl)_2,2,·bipyridine Synthesis> Add 4,4,5,5 -tetradecyl_2_(3_(10_(naphthalen-2-yl)indole-9)yl)-1,3,2-dioxapentane (2.〇g), bromine_4· Methylation d ratio bite (1.2 g), Pd (PPh3) 4 (0.15 g), squaric acid clock (1 7 g), 丄 斗 · · trimethyl stupid 20 m dibutanol 5 m b and water 1 ^ Bu stirred at reflux temperature 109 201226394 40550pif mixed for 16 hours. After the reaction solution was cooled to room temperature, toluene and water were added to carry out liquid separation. The solvent was removed by vacuum distillation, and the obtained solid was purified by a silica gel column chromatography (eluent: benzene/ethyl acetate = 95/5), and the obtained solvent was passed through a short activated carbon column. Remove the coloring ingredients. The solvent was distilled off under reduced pressure, and washed with heptane to obtain the compound 4-methyl-5'-(3-(10-(naphthyl)anthracene)benzene represented by (1-14-13). Base)_2,2,_bipyridinium (1.4 g) The structure of the compound was confirmed by NMR measurement. b-NlVtRXCDCls): δ = 9·04 (πι, 1Η), 8.55 (d, lH), 8.47 (dd, lH), 8.28 (S, 1H), 8.11 (dd, lH), 8.09 (d, lH) , 8.03 (m, lH), 8.00 (s, lH), 7.93 (m, lH), 7.88 (d, lH), 7.73.7 83 (m, 6H), 7.57_7.63 (m, 4H), 7.30 -7.40 (m, 4H), 7_14 (d ih) 2.45 (s, 3H). [ 'Synthesis Example 19] Synthesis of Compound (1-14-15) <Synthesis of 5-Bromo-6'-fluorenyl-2,3'-bipyridine]> 5-Bromo-2- A flask of hydrazinium (3.4 g) and THF (1 〇mi was cooled in an ice bath, and 2 M of isopropylmagnesium THF solution (ll ml) was added dropwise to the solution. After the addition was completed, the ice was removed. After warming for 3 hours, it was cooled again in an ice bath, and zinc hydride tetramethylamine (5.5 g) was added. After removing the ice bath and warming to room temperature, add 2 5 _ 2 $ bite (4.7 g) and Pd(PPh3)4 (0·7 g), 5 hours at the reflux temperature. After cooling the reaction solution to room temperature, EDTA · 4Na water was added to δ.) and benzene was used for liquid separation. The solid obtained in the decompression of the steamed crane by the Shixi rubber column chromatography (Exhibition: A stupid / acetic acid ethyl acetate = 7 / 3) pure 110 201226394 40550pif 'obtained 5 · bromo-6,-mercapto-2 , 3'-bipyridyl (1.5 g). <6'-Mercapto-5-(3·(10·(naphthalene-2-yl)fluorene-9-yl)phenyl)_2,3,-bipyridine Synthesis> Add 4,4,5, 5-tetramethyl-2-(3-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl)-1,3,2-oxaoxalan (2 〇g), 5 -Mix-6'-mercapto-2,3'-linked η 〇 〇 (1.2 g), Pd (PPh3) 4 (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethyl Stupid 25 m of third butanol 5 ml, and 1 m of water were mixed for 5 hours at reflux temperature. After cooling the reaction mixture to room temperature, the precipitated solid was collected by suction filtration, washed with decyl alcohol, and washed with ethyl acetate. Subsequently, purification was carried out by a silica gel column chromatography (developing solution: hydrazine/ethyl acetate = 4/1). The obtained eluate was passed through a short activated carbon tube column to remove the coloring component. The solvent was distilled off under reduced pressure, and the obtained solid was further recrystallized from gas benzene to obtain the compound 6 represented by (M4-15), -mercapto-5-(3-(10-(naphthalen-2-yl)蒽-9-yl)phenyl)-2,3'-linked. Bisidine (1.3 g). The structure of the compound was confirmed by NMR measurement. ^-NMR (CDC13) * 5 = 9.13 (m, lH), 9.07 (m, lH), 8.28 (dd, lH), 8.01-8.ll (m33H), 8.00 (s, lH), 7.93 (m, lH), 7.86 (m, lH), 7.73-7.83 (m, 7H), 7.57-7.64 (m, 4H), 7.31-7.39 (m, 4H), 7.28 (d, lH), 2.63 (s, 3H) [Synthesis Example 20] Synthesis of Compound (1-14-16) <Synthesis of 5-bromoindolyl-2,3r-bipyridyl> 3·Bromo-5-mercaptopyridine (3.4 g) and A flask of THF (10 ml) was cooled in an ice bath, and a solution of 2% isopropylmagnesium chloride in THF (11 ml) was added dropwise. After the completion of the dropwise addition, the ice bath was removed and stirred at room temperature for 111 hours at room temperature for 111 hours. Then, it was cooled again in an ice bath, and zinc tetramethylethylenediamine (5.5 g) was added. After removing the ice bath and warming to room temperature, 2,5-dibromo-bite (4.7 g) and Pd(PPh3)4 (0.7 g) were added and stirred at reflux temperature for 5 hours. After the reaction solution was cooled to room temperature, an aqueous solution of EDTA·4Na and toluene were added to carry out liquid separation. After distilling off the solvent under reduced pressure, the obtained solid was purified by silica gel column chromatography (eluent: toluene/ethyl acetate = 7/3) to give 5---5--methyl-2,3 '-Bipyridine (1.4 g). <5'-Methyl_5_(3-(1〇-(naphthalene-2-yl)indole-9-yl)phenyl)_2,3'-bipyridine Synthesis> Add 4, 4, 5, 5-Tetramethyl-2-(3_(10-(naphthalene-2-yl)indoleyl)phenyl)-1,3,2-dioxaborolan (2.〇g), 5-__6 , _methyl_2,3,· 吡 咬 (l_2g), Pd(PPh3)4 (〇.i5g), potassium phosphate (i.7g), 1> 2,4_trimethyl 25ml, second 5 ml of alcohol and 1 ml of water were mixed for 5 hours at reflux temperature. After the reaction solution was cooled to room temperature, the precipitated solid was collected by suction filtration, washed with methanol, and washed with ethyl acetate. Subsequently, it was purified by ruthenium column chromatography (developing solution: benzene/ethyl acetate = 4/1), and the obtained eluate was passed through a short activated carbon tube column to remove the colored component. The solvent was distilled off under reduced pressure, and the obtained solid was further recrystallized from gas benzene to obtain the compound 5'-mercapto-5-(3·(1〇-(naphthyl)) represented by (1-14-16). Onion _9·yl)phenyl)-2,3,-bipyridine (1.3 g). The structure of the compound was confirmed by NMR measurement. 'H-NMRC CDC13) : 6 = 9.08 ( m,lH) , 9.04 ( s,lH) , 8.50
UlH),8.21 (s,ih),8.09 (m,2H),8.04 (m,lH) ,8.00 (s,lH) ,7.93 (m,lH) ,7.73-7.88 (m,8H) ,7.62 (m,4H),UlH), 8.21 (s, ih), 8.09 (m, 2H), 8.04 (m, lH), 8.00 (s, lH), 7.93 (m, lH), 7.73-7.88 (m, 8H), 7.62 (m , 4H),
S 112 201226394 40550pif 7.31-7.40 (m,4H),2.45 (s,3H)。 [合成例21]化合物的合成 <5_漠_4’-曱基_2,3’_聯吼σ定的奋成> 將添加有3-漠-4-甲基吼喷(5 2g)及丁 的燒瓶在冰浴中冷卻,向該溶液中滴加2 鎂的THF溶液〇7m〗)。滴加完畢,二丙基氦化 攪拌9小時後,再次在冰浴中冷 1在室溫下 一 \ hit 添加虱化鋅四尹其7 撤去冰浴並升溫到室溫 啶⑺g)、Pd-】37 (英國莊信萬豐公 广—肩°比S 112 201226394 40550pif 7.31-7.40 (m, 4H), 2.45 (s, 3H). [Synthesis Example 21] Synthesis of a compound <5_漠_4'-mercapto-2,3'_吼吼σ定的奋成> 3-Dimethyl-4-methylindole spray (5 2g) The flask was cooled in an ice bath, and a solution of 2 mg of THF was added dropwise to the solution, 7 m). After the dropwise addition was completed, the dipropyl oxime was stirred for 9 hours, and then again cooled in an ice bath. 1 at room temperature. Next, add zinc telluride, and then remove the ice bath and warm to room temperature (7) g). Pd- 】37 (British Johnson letter Wanfeng Gongguang - shoulder ratio
(25 ml),在回流溫度下擾拌6小時。將反應^及雇P :蒸:=广水溶液”苯進行:體二 苯/乙酸S;/ 由靖柱層析法(展開液··甲 乙自曰一7/3)純化所獲得的固體。 ,,將所獲得的固_庚燒洗淨,獲得5^:4=C;r 聯錢(2.4 g)。 ^^T^-2,3- 甲基5-(3-(10-(奈_2-基)蒽-9-基)苯基)_2,3'-聯α比。定 的合成> =加一4,4 5,5_四甲基邻聊(萘_2基)蒽冬基)苯 暴—,亡二氧雜爛戊環(2〇g)、5_漠_6,_甲基_2,3|_聯„比咬 f ^、Pd(PPh3)4(0.15g)、構酸鉀(1.7g)、1,2,4-三曱 暴本25 mi、笛—^ 摔5小 矛二丁醇5 ml、及水1 ml,在回流溫度下攪 艚八Μ 、。、將反應液冷卻至室温後’添加甲苯及水進行液 液刀甲減壓*蒸鶴除去溶劑,藉由矽膠管柱層析法(展開 义 求/乙酸乙S旨=7/3)純化所獲得的固體,再將所獲 113 201226394 40550pif 得的溶出液通入短活性碳管柱,除去著色成分。減壓蒸顧 除去溶劑,將所獲得的固體進一步從曱苯中進行再結晶, 獲得(1-14-17)所表示的化合物4'-曱基-5-(3-(10-(萘-2-基) 蒽-9-基)苯基)-2,3'-聯°比咬(0.7 g)。 藉由NMR測定而確認化合物的結構。 ^-NMR ( CDC13) : 6 = 9.09 (s,lH) , 8.67 (s,lH) , 8.51 (d,lH) , 8.09 (m,2H) , 8.03 (m,lH) , 8.00 (m,lH) , 7.93 (m,lH) ,7.88 (d,lH),7.73-7.84 (m,6H),7.61 (m,4H), 7.52 ( d, 1H) , 7.31-7.40( m,4H) , 7.23 ( d,lH) , 2.46 ( s,3H) 〇 [合成例22]化合物(1-14-18)的合成 <5-漠-2’-曱基-2,3’-聯吡啶的合成> 將添加有3-溴-2-甲基吡啶(5.2 g)及THF (10 ml) 的燒瓶在冰浴中冷卻,向該溶液中滴加2μ的異丙基氯化 鎂的THF溶液(π ml)。滴加完畢後,撤去冰浴在室溫下 攪拌2小時後,再次在冰浴中冷卻,添加氣化辞四曱基乙 二胺(8.3 g)。撤去冰浴並升溫到室溫後,添加2,5_二溴吡 =(7.1 g)、Pd(PPh3)4 (l.〇g)及二甲苯(1〇ml),在回流(25 ml), spoiled for 6 hours at reflux temperature. The reaction and the employment of P: steaming: = wide aqueous solution "benzene": diphenyl / acetic acid S; / purified by Jingzhu chromatography (expansion liquid · · · · · · · · · , the obtained solid _ gen is washed and washed to obtain 5^:4=C; r lianqi (2.4 g). ^^T^-2,3-methyl 5-(3-(10-(奈_ 2-based) fluoren-9-yl)phenyl)_2,3'-linked alpha ratio. Synthesis of synthesis > = addition of a 4,4 5,5-tetramethyl-neo(naphthalene-2-yl) anthracene Base) benzene storm -, dioxin pentoxide ring (2 〇 g), 5 _ desert _6, _ methyl 2, 3 | _ „ „ 咬 咬 ^ ^, Pd (PPh3) 4 (0.15g) Potassium acid (1.7g), 1,2,4-trisole 25mi, flute-^ fell 5 spear dibutanol 5 ml, and water 1 ml, stir the gossip at reflux temperature. After the reaction solution was cooled to room temperature, 'toluene and water were added to carry out liquid-liquid knife decompression*, and the solvent was removed by steaming, and the solvent was purified by silica gel column chromatography (extraction/acetic acid ethyl acetate = 7/3). The solid obtained was passed through a short activated carbon tube column of the obtained 113 201226394 40550 pif to remove the coloring component. The solvent was removed by distillation under reduced pressure, and the obtained solid was further recrystallized from toluene to obtain the compound 4'-mercapto-5-(3-(10-(naphthalene)- represented by (1-14-17). 2-based) 蒽-9-yl)phenyl)-2,3'-linked ratio (0.7 g). The structure of the compound was confirmed by NMR measurement. ^-NMR (CDC13): 6 = 9.09 (s,lH) , 8.67 (s,lH) , 8.51 (d,lH) , 8.09 (m,2H) , 8.03 (m,lH) , 8.00 (m,lH) , 7.93 (m,lH) , 7.88 (d,lH), 7.73-7.84 (m,6H), 7.61 (m,4H), 7.52 ( d, 1H) , 7.31-7.40 ( m,4H) , 7.23 ( d ,1H), 2.46 ( s,3H) 〇 [Synthesis Example 22] Synthesis of Compound (1-14-18) <Synthesis of 5-N--2'-Mercapto-2,3'-bipyridyl> A flask to which 3-bromo-2-methylpyridine (5.2 g) and THF (10 ml) were added was cooled in an ice bath, and 2 μ of a solution of isopropylmagnesium chloride in THF (π ml) was added dropwise. After completion of the dropwise addition, the ice bath was removed and stirred at room temperature for 2 hours, and then cooled again in an ice bath, and gasified tetradecylethylenediamine (8.3 g) was added. After removing the ice bath and warming to room temperature, 2,5-dibromopyridyl = (7.1 g), Pd(PPh3)4 (l.〇g) and xylene (1 〇ml) were added at reflux.
溫度下攪拌7小時。將反應液冷卻至室溫後,添加EDTA 4Na水;谷液及曱苯進行液體分離。在減壓蒸德除去溶劑 後,藉由矽膠管柱層析法(展開液:甲苯/乙酸乙酯=4/1) 純化所獲得的固體,獲得5-溴-2,-曱基-2,3,-聯吡啶(1.3 g)。 <2’·曱基-HHIO-(萘基)蒽-9_基)苯基)_2,3,_聯0比啶 的合成> 添加M,5,5·四甲基_2_(3_(10(萘_2_基)蒽冬基)苯 114 201226394 40550pif 基)_1,3,2-—氧雜侧戊環ζ2 〇 ς& 基苯25 m卜第三丁醇5 %、(Ug)、1,2,4·二曱 姓19丨眩。膝G _ V、、 及水lm卜在回流溫度下攪 體八離in 溫後’添加甲苯及水進行液 體刀離。祕_除麵劑,藉料膠管柱續法(展開 ί的乙广4/1)純化所獲得的固體,再將所獲 3 Γ生碳管柱,除去著色成分。減壓蒸餾 除去溶劑,猎由吸義集析出的_ ί示的化合物2’·甲基鄭(蔡心基❹ 基)-2,3’-聯吡啶(0·8 g)。 猎由NMR測疋而確認化合物的結構。 ^-NMR CCDCI3): 6 = 9.08 (m5lH) ,8.57 (mlH) 7.99-8.10 (m,4H) ,7.92 (m,lH) ,7.88 (d,lH) , 7.73-7.83 (m,7H) , 7.61 (m,4H) , 7.51 (dd,lH) , 7.30-7.40 (m 4H) 7.25 (m,lH) ,2.66 (s,3H)。 ’ ’ [合成例23]化合物(1-14-20)的合成 < 5-溴-3’-曱基-2,4'-聯吡啶的合成〉 將添加有4-溴-3-甲基°比。定(5.0 g)及THF ( 30 ml) 的燒瓶在乾冰/甲醇浴中冷卻,向該溶液中滴加2M的異丙 基氯化鎂的THF溶液(16 ml)。滴加完畢後,撤去冷卻用 浴’在室溫下攪拌2.5小時後,在冰浴中冷卻,添力I氣化 鋅四甲基乙二胺(8.0 g)。撤去冰浴並升溫到室溫後,添 加 2,5-二溴n比咬(7.6 g)及 Pd(PPh3)4 ( 1.0 g),在回流^ 度下攢:拌2小時。將反應液冷卻至室溫後’泰加edta · 115 201226394 4Na水溶液及乙酸乙酯進行液體分離。在減壓蒸餾除去溶 劑後,藉由矽膠管柱層析法(展開液:曱苯/乙酸乙酯=5/1 ) 純化所獲得的固體,獲得5_溴_31_曱基_2,4,_聯吡啶(5.6 g)。 <3’-甲基·5·(3-(1〇-(萘_2_基)蒽_9-基)苯基)-2,4,·聯吡咬 的合成> 添加4,4,5,5·四曱基-2-(3-(10-(萘-2-基)蒽-9-基)苯 基)-1,3,2-二氧雜硼戊環(2.〇g)、5-溴-3’-甲基-2,4,-聯吡啶 (1.2 g)、Pd(PPh3)4 ( 0.15 g)、磷酸鉀(1.7 g)、1,2,4-三甲 基本1 ml、第三丁醇1 ml、及水1 ml ’在回流溫度下擾拌 4小時。將反應液冷卻至室溫後,添加水,藉由吸濾採集 析出物。將所獲得的固體利用水及曱醇洗淨後,藉由NH 基修飾矽膠(DM1020:富士矽化學公司製造)管柱層析 法(展開液:甲苯)進行純化,獲得(1-14-20)所表示的 化合物3,·甲基-5-(3-(10-(萘-2-基)蒽-9-基)苯基)-2,4,-聯吡 啶(1.7g)。 藉由NMR測定而確認化合物的結構。 1H-NMR(CDC13) · 5 = 9.09(m,lH) , 8.56(s,lH), 8.55 (d,lH) ,8.10(m,2H) ,8.03 (m,lH) ,8.00(d,lH) ,7.93 (d,lH),7.88 (d,lH),7.73-7.83 (m,6H) ,7.61 (m,4H), 7.53 (d,lH) ,7.31-7.41 (m,5H),2.44 (s,3H)。 [合成例24]化合物(1-11-18)的合成 < 2’-曱基-5-(6-(10-苯基蒽-9-基)萘-2-基)2,3’·聯。比咬 的合成> 將4,4,5,5-四曱基-2-(6-(10-苯基蒽-9-基)萘-2-Stir at temperature for 7 hours. After the reaction solution was cooled to room temperature, EDTA 4Na water was added; the solution and the benzene were separated by liquid. After removing the solvent under reduced pressure, the obtained solid was purified by silica gel column chromatography (eluent: toluene/ethyl acetate = 4/1) to afford 5-bromo-2,-indole-2. 3,-bipyridine (1.3 g). <2'·Mercapto-HHIO-(naphthyl)fluoren-9-yl)phenyl)_2,3,_0-pyridine synthesis> Add M,5,5·tetramethyl_2_(3_ (10(naphthalene-2-yl)anthracene)benzene 114 201226394 40550pif base)_1,3,2-oxaxahedral oxime 2 〇ς& phenyl benzene 25 m butylbutanol 5%, (Ug) 1, 2, 4 · 2 surnames 19 glare. Knee G _ V, and water lm are agitated at reflux temperature, and then added toluene and water to remove the liquid. Secret _ remove agent, the obtained solid was purified by the hose column continuation method (expanded 乙乙广4/1), and the obtained 3 carbon tube column was removed to remove the coloring component. The solvent was removed by distillation under reduced pressure, and the compound 2'·methyl Zheng (Caixin thiol)-2,3'-bipyridine (0.8 g) which was precipitated by the absorption set was hunted. The structure of the compound was confirmed by NMR measurement. ^-NMR CCDCI3): 6 = 9.08 (m5lH), 8.57 (mlH) 7.99-8.10 (m,4H), 7.92 (m,lH), 7.88 (d,lH), 7.73-7.83 (m,7H), 7.61 (m, 4H), 7.51 (dd, lH), 7.30-7.40 (m 4H) 7.25 (m, lH), 2.66 (s, 3H). [Synthesis Example 23] Synthesis of Compound (1-14-20) <Synthesis of 5-bromo-3'-fluorenyl-2,4'-bipyridine> 4-Bromo-3-methyl group was added ° ratio. A flask of fixed (5.0 g) and THF (30 ml) was cooled in a dry ice/methanol bath, and a 2M solution of isopropylmagnesium chloride in THF (16 ml) was added dropwise. After the completion of the dropwise addition, the cooling bath was removed and stirred at room temperature for 2.5 hours, and then cooled in an ice bath to add zinc trimethylethylenediamine (8.0 g). After removing the ice bath and warming to room temperature, 2,5-dibromo-n-bit (7.6 g) and Pd(PPh3)4 (1.0 g) were added, and the mixture was refluxed for 2 hours. After the reaction solution was cooled to room temperature, a liquid separation was carried out by aqueous solution of Taiga edta·115 201226394 4Na and ethyl acetate. After distilling off the solvent under reduced pressure, the obtained solid was purified by silica gel column chromatography (eluent: benzene/ethyl acetate = 5/1) to obtain 5-bromo-31-mercapto-2,4 , _bipyridine (5.6 g). <3'-Methyl·5·(3-(1〇-(naphthalen-2-yl)indole-9-yl)phenyl)-2,4,·Synthesis of hydrazine bite> Add 4,4 ,5,5·tetradecyl-2-(3-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl)-1,3,2-dioxaborolan (2.〇 g), 5-bromo-3'-methyl-2,4,-bipyridyl (1.2 g), Pd(PPh3)4 (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethyl 1 ml, 1 ml of third butanol, and 1 ml of water were stirred at reflux temperature for 4 hours. After the reaction solution was cooled to room temperature, water was added, and the precipitate was collected by suction filtration. The obtained solid was washed with water and decyl alcohol, and then purified by an NH-based modified silicone (DM1020: manufactured by Fuji Chemical Co., Ltd.) column chromatography (developing solution: toluene) to obtain (1-14-20). The compound 3, methyl-5-(3-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl)-2,4,-bipyridine (1.7 g). The structure of the compound was confirmed by NMR measurement. 1H-NMR (CDC13) · 5 = 9.09 (m, lH), 8.56 (s, lH), 8.55 (d, lH), 8.10 (m, 2H), 8.03 (m, lH), 8.00 (d, lH) , 7.93 (d, lH), 7.88 (d, lH), 7.73-7.83 (m, 6H), 7.61 (m, 4H), 7.53 (d, lH), 7.31-7.41 (m, 5H), 2.44 (s , 3H). [Synthesis Example 24] Synthesis of Compound (1-11-18) < 2'-Mercapto-5-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl) 2,3'· Union. Synthesis of specific bite > 4,4,5,5-tetradecyl-2-(6-(10-phenylfluoren-9-yl)naphthalene-2-
S 116 201226394 40550pif 基)-l,3,2-二氧雜硼戊環(2〇g)、5|2 (W),編 g),( ^ 基苯(20ml)、第三丁醇(5ml)及水 ^ U,4-二甲 中,在氮氣環境下,在回流溫度下_8=添加到燒瓶 後’將反應液冷卻至室溫後,藉由吸據採集:出=畢 利用曱S予洗淨,再利用乙酸乙酯洗淨。 — — 柱層析法(展開液:甲苯/乙膠管 將所獲得的溶出液通入短活性碳管桎::、=,再 壓蒸餾除去溶劑,藉由吸滹採隹 者色成/刀。減 n n ^ "稭由及/慮知集析出的固體,獲得 i 2:,I二化合物2’_甲基_5你⑽苯基葱-9-基) 奈_2·基)2,3 -聯 η比咬(1 1 g)。 } 藉由NMR測定而確職合物的結構。 8 23(^1= (RCDCl3) : δ = 9·17 U,1H),8.6G (_), 8.23^3,1H), 8.19 (m,2H), 8.06 (m,2H),7.87(dd5lH) 7. 5( dd,lH), 7.73( m,4H), 7.69( dd?lH), 7.55-7.65( m^H)5 7.51 Cm,2H),7.26-7.37 (m,5H),2.73 (s3H)〇 , 可藉由適宜變更原料的化合物,並藉由依據上述合成 例的方法’而合成本發_其簡生物化合物。 以下,為了進-步詳細說明本發明,而揭示使用本發 ^=化口物的有機EL元件的實例,但本發明並不限定於 該等0 製作實例1至實例4及比較例!至比較例2的元件, 为別測定怪定電流驅動試驗中的㈣開始電壓⑺、保持 初始值的90%以上的亮度的時間(小時)。以下,詳細地 117 201226394 說明實例及比較例。 將所製作的實例1至實例4及比較例1至比較例2的 元件中的各層的材料構成示於下述表1。 表1S 116 201226394 40550pif base)-l,3,2-dioxaborolan (2〇g), 5|2 (W), ed.), ( ^ phenylbenzene (20ml), third butanol (5ml) And water ^ U, 4- dimethyl, under nitrogen atmosphere, at reflux temperature _8 = added to the flask 'after cooling the reaction solution to room temperature, by suction data collection: out = 曱 曱 S Washed and washed with ethyl acetate. — Column chromatography (developing solution: toluene / E-tank) The obtained eluate was passed into a short activated carbon tube::, =, and the solvent was removed by distillation. By sucking the picker color / knife. minus nn ^ " straw and / / know the solids precipitated, get i 2:, I two compounds 2 '_ methyl _ 5 you (10) phenyl onion-9 -Base) Nai 2·yl) 2,3 - η than bite (1 1 g). } The structure of the complex was determined by NMR. 8 23(^1= (RCDCl3) : δ = 9·17 U,1H), 8.6G (_), 8.23^3,1H), 8.19 (m,2H), 8.06 (m,2H),7.87(dd5lH 7. 5( dd,lH), 7.73( m,4H), 7.69( dd?lH), 7.55-7.65( m^H)5 7.51 Cm,2H), 7.26-7.37 (m,5H),2.73 ( s3H) 〇, the simple biological compound can be synthesized by a compound which is suitable for changing the raw material, and by the method according to the above synthesis example. Hereinafter, in order to explain the present invention in detail, an example of an organic EL device using the present invention is disclosed, but the present invention is not limited to the above-described 0 production examples 1 to 4 and comparative examples! In the element of Comparative Example 2, the time (hour) at which the (IV) start voltage (7) and the brightness of 90% or more of the initial value were maintained in the strange current drive test were measured. Hereinafter, an example and a comparative example will be described in detail in 117 201226394. The material compositions of the respective layers of the produced Examples 1 to 4 and Comparative Examples 1 to 2 are shown in Table 1 below. Table 1
電洞注 入層 電洞傳輸 層 發光層 電子傳輸層 主體 摻雜劑 實例1 HI NPD A B 1-7-74 實例2 HI NPD A B 1-7-26 實例3 HI NPD A B 1-7-98 實例4 HI NPD A B 1-7-96 比較例1 HI NPD A B C 比較例2 HI NPD A B D 在表1中,「HI」為N4,N4'-二苯基-N4,N4'-雙(9-苯基-9H-咔唑-3-基)-[1,Γ-聯苯]-4,4'-二胺’「NPD」為 N4,N4’-二(萘-1-基)-N4,N4'-二苯基-[Ι,Γ-聯苯]-4,4’-二胺,化合物(A)為9-苯基-10-(4_苯基萘-1-基)慧,化合物(Β)為Ν5,Ν5,Ν9,Ν9-7,7-六苯基-711-苯並[(;]葬-5,9-二胺,化合物(〇為9,10-二([2,2'-聯吼啶]-5-基)蒽,化合物(D)為9,10-雙(4十比啶-3-基)萘 -1-基)蒽。將該等化合物與形成在電子傳輸層與陰極之間 的層所使用的「Liq」的化學結構一併揭示如下。Hole injection layer hole transport layer light-emitting layer electron transport layer host dopant example 1 HI NPD AB 1-7-74 Example 2 HI NPD AB 1-7-26 Example 3 HI NPD AB 1-7-98 Example 4 HI NPD AB 1-7-96 Comparative Example 1 HI NPD ABC Comparative Example 2 HI NPD ABD In Table 1, "HI" is N4, N4'-diphenyl-N4, N4'-bis (9-phenyl-9H) -oxazol-3-yl)-[1,Γ-biphenyl]-4,4'-diamine 'NPD' is N4,N4'-di(naphthalen-1-yl)-N4,N4'- Phenyl-[Ι,Γ-biphenyl]-4,4'-diamine, compound (A) is 9-phenyl-10-(4-phenylnaphthalen-1-yl) oxime, compound (Β) is Ν5,Ν5,Ν9,Ν9-7,7-hexaphenyl-711-benzo[[;;] burial-5,9-diamine, compound (〇9,10-二([2,2'-linked Acridine]-5-yl)anthracene, compound (D) is 9,10-bis(tetradecyridin-3-yl)naphthalen-1-yl)anthracene. These compounds are formed in an electron transport layer and a cathode. The chemical structure of "Liq" used in the layer between them is revealed as follows.
118 201226394 40550pif118 201226394 40550pif
[實例1] 〈將^合物(l·7·74)㈣電子傳輸層的元件〉 以將藉由濺鍍製成厚度為丨⑽nm的膜的IT〇研磨至 150 nm的26 mmx28 mmx〇.7麵的玻璃基板(〇pt〇如· i ΐΐ)作為透明支撐基板。將該透明支撐基板固 持置(昭和真空(股份)製造)的基板固 鍍;钥ΓΪΓ:有HI的蒸_舟、添加有丽^的華 鍍用翻舟、添加有化合物(A)的蒸錄用麵舟^ 119 201226394 4 11 B物(B)的蒸鍍用銦舟、添加有化合 用鉬舟、添加有Liq的蒸鍍用鉬舟、苏 -4)的蒸鍍 加有銀的蒸鍍用鎢舟。 〇有鎂的鉬舟及添 在透明支撐基板的IT0膜上,依 真空槽減壓到5xl〇·4 Pa,首先,加埶./战下述各層。將 舟,以膜厚成為4〇 nm的方式加有HI的蒸鑛用 層,接著,加熱添加有NPD的蒸鍍用f t而形成電洞注入 的方式進行蒸鍍而形成電洞傳輪^。复Γ膜厚成為3〇 nm 有化合物⑷岐制舟與私魏二’^加熱添加 舟’以膜厚成為35 nm的方式進行# 的蒸鑛用 化合物⑷與化合物⑻的重量比二= 發光層。以 調節蒸鍍速度。料,加熱添加有彳5 : 5的方式 鍍用舟’以膜厚成為15nm的方式 (_7:74)的蒸 輸層。各層的蒸錢速度為〇.〇1 nm/秒〜==、形成電子傳 其後’加熱添加有Liq的蒸鑛用 的方式以⑽nm/秒〜G]職/秒_ ^成為1⑽ 同時力她有錤的舟與添加有 100啦的方式進行蒸鍍而形成陰極。此時,以J厚成為 0.1⑽/秒〜_速度,以蒸链速度成為 元件。0nm/秒的方式形成陰極,獲得有機電激發光 加直流心二且以鎮/銀電極作為陰極而施 獍于波長約為460 nm的藍色發光。另外, 曰於獲得初始亮度漏cd/m2的電流密度而實施怪定[Example 1] <Elements of the electron transport layer of (1·7·74) (IV)> The IT〇 of a film having a thickness of 丨(10) nm by sputtering was polished to 26 mm×28 mm×〇 at 150 nm. A 7-sided glass substrate (〇pt〇··i ΐΐ) is used as a transparent supporting substrate. The transparent support substrate is held by a substrate (manufactured by Showa Vacuum Co., Ltd.); key ΓΪΓ: steamed _ boat with HI, rafted with Hua plating added with Li, and steamed with compound (A) added舟 ^ 119 201226394 4 11 B (B) vapor deposition indium boat, addition of a molybdenum boat for compounding, molybdenum boat for vapor deposition with Liq, Su-4), vapor deposition with silver and vapor deposition Tungsten boat. The molybdenum boat with magnesium is added to the IT0 film of the transparent support substrate, and the pressure is reduced to 5xl〇·4 Pa according to the vacuum chamber. First, the following layers are twisted. The kiln layer for HI was added to the boat so that the film thickness was 4 〇 nm, and then vapor deposition was carried out by heating the surface of the NPD to form a hole transfer method. The retanning film thickness is 3 〇 nm. There are compounds (4) 岐 舟 与 私 私 私 私 私 ' ' ' 加热 加热 加热 加热 加热 加热 加热 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' . To adjust the evaporation rate. The material was heated to have a 彳5:5 plating method. The plating layer was used to form a vapor deposition layer having a film thickness of 15 nm (_7: 74). The evaporation rate of each layer is 〇.〇1 nm/sec~==, and the formation of electrons is followed by 'heating the method of adding Liq to the steam. (10)nm/sec~G] position/sec _ ^ becomes 1 (10) The crucible boat was vapor-deposited in a manner of adding 100 to form a cathode. At this time, the J-thickness becomes 0.1 (10) / sec to _ speed, and the element becomes the element at the vapor chain speed. The cathode was formed in a manner of 0 nm/sec, and organic electroluminescence light was obtained by adding a DC core and applying a galvanic/silver electrode as a cathode to a blue luminescence having a wavelength of about 460 nm. In addition, it is difficult to obtain the current density of the initial luminance leak cd/m2.
S 120 201226394 40550pif 電流驅動試驗,結果驅動試驗開始電壓為7.33 V,保持初 始值的90°/。( 1800 cd/m2)以上的亮度的時間為45小時。 [實例2] <將化合物(1-7-26)用於電子傳輸層的元件> 除了將化合物(1-7-74)換為化合物(1-7-26)以外, 藉由依據實例2的方法獲得有機EL元件。以IT〇電極作 為陽極,以鎂/銀電極作為陰極,藉由用於獲得初始亮度 2000 cd/m的電流密度而實施恆定電流驅動試驗。驅動試 驗開始電壓為6·36 V,保持初始值的9〇%以上的亮度的時 間為151小時。 [實例3] <將化合物(1-7-98)用於電子傳輸層的元件> 除了將化合物(1-7-74)換為化合物(1-7-98)以外, 藉由依據實例2的方法獲得有機EL元件。以ΙΤ〇電極作 為陽極,以鎂/銀電極作為陰極,藉由用於獲得初始亮度 2000 cd/m2的電流密度而實施恆定電流驅動試驗。驅動試 驗開始電壓為7.34 V,保持初始值的9〇%以上的亮度的時 間為265小時。 [實例4] <將化合物(1-7-96)用於電子傳輸層的元件> 除了將化合物(1-7-74)換為化合物(^7—96)以外, 藉由依據實例2的方法獲得有機EL元件。以IT〇電極作 為陽極,關/銀電_為陰極,如躲麟初始亮度 2000 cd/m2的電絲度而實施怪定電流_試驗。驅動試 121 201226394 40550pif 驗開始電壓為5.33 V ’保持初始值的娜以上的亮度的時 間為103小時。 [比較例1] 除了將化3物(H96)換為化合物(C)以外,藉由 依據實例1的方法獲得有機EL元件。以ΙΤ0電極作為陽 極’ 2以鎂/銀1極作為陰極,藉由用於獲得初始亮度 2000 cdm 、"丨〔在、度而實施恆定電流驅動試驗 。結果驅動試驗 開始電坚為5.G6 V,保持初始值的冒。以上的亮度的時間 為6小時。 [比較例2] 除了將化合物(1_7_96)換為化合物(D)以外,藉由 依據實例1的方法獲得有機EL元件。以ITQ電極作為陽 極’ 2以鎮/銀電極作為陰極’藉由用於獲得初始亮度2_ cd/m2的電度而實紐定電赫動試驗。結果驅動試驗 開始電壓為5.05 V ’保持初始值的9()%以上的亮度的時間 為10小時。 將以上結果匯總於表2。S 120 201226394 40550pif Current drive test, the result of driving the test start voltage is 7.33 V, maintaining the initial value of 90 ° /. The brightness of (1800 cd/m2) or more is 45 hours. [Example 2] <Component for using compound (1-7-26) for electron transport layer> Except that compound (1-7-74) was replaced with compound (1-7-26), by way of example The method of 2 obtained an organic EL element. A constant current driving test was carried out by using an IT crucible electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m. The drive test start voltage was 6·36 V, and the brightness of the initial value of 9〇% or more was maintained at 151 hours. [Example 3] <Component for using compound (1-7-98) for electron transport layer> Except that compound (1-7-74) was replaced with compound (1-7-98), by way of example The method of 2 obtained an organic EL element. A constant current driving test was carried out by using a ruthenium electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m2. The drive test start voltage was 7.34 V, and the brightness of the initial value of 9〇% or more was maintained for 265 hours. [Example 4] <Component for using compound (1-7-96) for electron transport layer> Except that compound (1-7-74) was replaced with compound (^7-96), by way of example 2 The method of obtaining an organic EL element. Taking the IT 〇 electrode as the anode and the off/silver _ as the cathode, the strange current _ test was carried out, such as the initial brightness of 2000 cd/m2. Drive test 121 201226394 40550pif The test start voltage is 5.33 V. The time for maintaining the brightness of the initial value or more is 103 hours. [Comparative Example 1] An organic EL device was obtained by the method according to Example 1, except that the compound (H96) was replaced by the compound (C). The constant current driving test was carried out by using a ΙΤ0 electrode as an anode '2 with a magnesium/silver 1 pole as a cathode for obtaining an initial luminance of 2000 cdm and "丨. As a result, the driving test was started at 5.G6 V, keeping the initial value. The above brightness time is 6 hours. [Comparative Example 2] An organic EL device was obtained by the method according to Example 1, except that the compound (1-7-96) was replaced by the compound (D). The ITQ electrode was used as the anode '2 with the town/silver electrode as the cathode' by the electro-mechanical test for obtaining the initial luminance of 2 cd/m2. As a result, the driving test start voltage was 5.05 V', and the time for maintaining the brightness of 9 ()% or more of the initial value was 10 hours. The above results are summarized in Table 2.
表2 電子傳輸層 維持初始值的90«^_ 以上的亮度的時間 (小時) 開始電壓(V) 實例1 1-7-74 45 7.33 實例2 1-7-26 151 6.36 實例3 1-7-98 265 7.34 實例4 1-7-96 103 5.33 — ' 丨!· 5.06 比較例1 C 比較例2 D 10 5.05 122 201226394 40550pif 製作實例5至實例20及比較例3至比較例5的元件, 分別測定恆定電流驅動試驗中的驅動開始電壓(V)、保持 初始值的90%以上的亮度的時間(小時)。以下,詳細地 說明實例及比較例。 將所製作的實例5至實例20及比較例3至比較例5 的元件中的各層的材料構成示於下述表3。 表3Table 2 Time (hours) at which the electron transport layer maintains the brightness above 90«^_ of the initial value. Starting voltage (V) Example 1 1-7-74 45 7.33 Example 2 1-7-26 151 6.36 Example 3 1-7- 98 265 7.34 Example 4 1-7-96 103 5.33 - ' 丨!· 5.06 Comparative Example 1 C Comparative Example 2 D 10 5.05 122 201226394 40550pif The components of Example 5 to Example 20 and Comparative Example 3 to Comparative Example 5 were prepared and measured separately. The drive start voltage (V) in the constant current drive test and the time (hour) at which the luminance of 90% or more of the initial value is maintained. Hereinafter, examples and comparative examples will be described in detail. The material constitution of each of the elements of Examples 5 to 20 and Comparative Examples 3 to 5 produced was shown in Table 3 below. table 3
電洞注入 層 電洞傳輸 層 發光層 電子傳輸 層 主體 摻雜劑 實例5 HI HT E F 1-11-1 實例6 HI HT E F 1-11-2 實例7 HI HT E F 1-11-3 實例8 HI HT E F 1-11-4 實例9 HI HT E F 1-11-5 實例10 HI HT E F 1-11-39 實例11 HI HT E F 1-14-2 實例12 HI HT E F 1-14-3 實例13 HI HT E F 1-14-11 實例14 HI HT E F 1-14-12 實例15 HI HT E F 1-14-14 實例16 HI HT E F 1-14-15 實例17 HI HT E F 1-14-16 實例1.8 HI HT E F 1-14-18 實例19 HI HT E F 1-14-20 實例20 HI HT E F 1-11-18 比較例3 HI HT E F G 比較例4 HI HT E F Η 比較例5 HI HT E F I 在表3中,HT為Ν-([1,Γ-聯苯]-4-基)-9,9-二曱基 123 201226394 _____^11 _N-(4_(9-苯基-9H-咔唑-3-基)苯基)-9H-S-2-胺,化合物(E) 為9-(4-(萘-1-基)苯基)_1〇_苯基蒽,化合物(F)為4,4’-((7,7-二苯基-7H-苯並[c]第-5,9-二基)雙((苯基)胺基))二¥腈,化 合物(G)為 4,-(4_(1〇-(萘_2_基)蒽-9-基)苯基)-2,2,:6,,2,,-三 聯°比咬’化合物(H)為3-(6-(10-苯基蒽-9-基)萘-2-基)口比 咬’化合物(I)為6-(4_(1〇-(萘小基)蒽冬基)苯基)_2,4,· 聯°比咬。Hole injection layer hole transport layer light-emitting layer electron transport layer host dopant example 5 HI HT EF 1-11-1 Example 6 HI HT EF 1-11-2 Example 7 HI HT EF 1-11-3 Example 8 HI HT EF 1-11-4 Example 9 HI HT EF 1-11-5 Example 10 HI HT EF 1-11-39 Example 11 HI HT EF 1-14-2 Example 12 HI HT EF 1-14-3 Example 13 HI HT EF 1-14-11 Example 14 HI HT EF 1-14-12 Example 15 HI HT EF 1-14-14 Example 16 HI HT EF 1-14-15 Example 17 HI HT EF 1-14-16 Example 1.8 HI HT EF 1-14-18 Example 19 HI HT EF 1-14-20 Example 20 HI HT EF 1-11-18 Comparative Example 3 HI HT EFG Comparative Example 4 HI HT EF Η Comparative Example 5 HI HT EFI In Table 3 , HT is Ν-([1,Γ-biphenyl]-4-yl)-9,9-diindenyl 123 201226394 _____^11 _N-(4_(9-phenyl-9H-carbazol-3-yl) Phenyl)-9H-S-2-amine, compound (E) is 9-(4-(naphthalen-1-yl)phenyl)_1〇_phenylindole, and compound (F) is 4,4'- ((7,7-diphenyl-7H-benzo[c]-5,9-diyl)bis((phenyl)amino))bisacetonitrile, compound (G) is 4,-(4_ (1〇-(naphthalene-2-yl)fluoren-9-yl)phenyl)-2,2,:6,,2,,-triplet ratio bite compound (H) 3-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl) hydroxy-' compound (I) is 6-(4-(1〇-(naphthalenyl)anthraceyl)phenyl ) _2, 4, · 联 ° bite.
[實例5][Example 5]
S 124 201226394 4U55Upif 〈將化合物用於電子傳輸層的元件> 以將藉由雜製成厚度為180 nm的膜的ΙΤΟ研磨至 150 nm 的 26 mm,mmx〇.7 mm 的玻璃基板(〇pt。 (股份)製造)作為相支縣板。將該翻支樓基板固 =市售的蒸織置(昭和真空(股份)製造)的基板固 田Π絲添加有111的蒸錢用翻舟、添加有HT的蒸鍍 物⑺的蒸鍵用錮舟、1力添加有化合 钥舟、添加有Liq的‘用:合物⑴1·1)的蒸鑛用 有銀的蒸顧鶴舟。一用鉬舟、添加有_目舟及添加 空槽序形成爾層。將真 的方式進行: :力巧:加有HT的蒸鍍用舟: 熱添加有:: 膜厚成為35nm的方式進口4勿⑺的蒸鍍用舟,以 ⑻與化合物(F) 了錢㈣毅光層。以化合物 鍍速度。其次,同時加為約95:5的方式調節蒸 用舟與添加有Liq的"有化合物(MM)的蒸鍍 進行蒸鑛㈣成’叫厚^ 25⑽的方式 的重量比成為約1:1的二與Llq 度為0.01 nrn/秒〜i nm/秒式5周即瘵鍍速度。各層的蒸鍍速 加熱添加有Llq的蒸鍍用舟,以膜厚成為lnm 125 201226394 40550pif 的方式以G.Gl nm/秒〜ο」⑽ 著,同時加埶添^ 迷度進行蒸鑛。接 A ,,、’、、力有鎂的舟與添加有銀的舟,$ & 10一的方式進行蒸錢而形成陰極。此時:= 子數比成為10:1的方f Μ鎂與銀的原 0.1 nm/秒〜1Gnm/y二速度’以蒸鑛速度成為 元件。 蛛的方切成陰極,獲得麵電激發光 直4:::電ί!為陽極,以鎂⑽ 直抓電壓,則獲得波長約為魏nm的藍 藉由用於獲得初始亮度2__2的€流密^實施值定 電流驅動試驗,結果购試驗開始祕為4術,保持初 始值的9G% (l_ed/m2)以上的亮度的時 時。 [實例6] ^ 〈將化合物(1·11·2)用於f子傳輸層的元件〉 除了將化合物(M1])換為化合物(M12)以外, 赭由依據實例5的方法獲得有機EL元件。以ITO電極作 為陽極’ ^/銀電極作騎極,藉㈣於獲得初始亮户 誦cd/m的f絲度而實施缺電流㈣試驗。驅動^ 驗開始電壓為4.12 V,保持初始值的9()%以上的亮度的 間為85小時。 、 [實例7] 〈將化合物(1·11·3)用於電子傳輸層的元件〉 除了將化合物(1-11-1)換為化合物(1113)以外, 藉由依據實例5的方法獲得有機EL元件。以ΙΤ0電極作 為陽極,以鎂/銀電極作糖極,藉㈣於獲得初始亮度 126 201226394 40550pif 2000 cd/m2的電流密度而實施恆定電流驅動試驗。驅動試 驗開始電壓為3·78 V,保持初始值的9〇%以上的亮度的時 間為97小時0 [實例8] <將化合物(^1-4)用於電子傳輸層的元件〉 除了將化合物(Μ1·1 )換為化合物(1_H_4)以外, 藉由依據實例5的方法獲得有機EL元件。以ΙΤΟ電極作 為陽極,以鎂/銀電極作為陰極,藉由用於獲得初始亮度 2000 cd/m2的電流密度而實施恆定電流驅動試驗。驅動試 驗開始電壓為3.95 V,保持初始值的9〇%以上的亮度的時 間為83小時。 [實例9] <將化合物0-11-5)用於電子傳輸層的元件> 除了將化合物(i-U-l)換為化合物(1-11-5)以外, 藉由依據實例5的方法獲得有機EL元件。以ITO電極作 為陽極,以旗/銀電極作為陰極,藉由用於獲得初始亮度 2000 cd/m的電流岔度而實施恆定電流驅動試驗。驅動試 驗開始電壓為3.88 V ’保持初始值的90%以上的亮度的時 間為93小時。 [實例10] <將化合物(1-11-39)用於電子傳輸層的元件> 除了將化合物(Mi-ι)換為化合物(M1_39)以外, 藉由依據實例5的方法獲得有機EL元件。以IT〇電極作 為陽極’賴/銀電極作騎極,藉_於獲得初始亮度 127 201226394 40550pif 2000 cd/m2的電流密度而實施恆定電流驅動試驗。驅動試 驗開始電壓為4.16 V,保持初始值的以上的亮度的時 間為74小時。 [實例11] <將化合物(1-14_2)用於電子傳輸層的元件> 除了將化合物(1-1M)換為化合物(卜14-2)以外, 藉由依據實例5的方法獲得有機el元件。以ITO電極作 為陽極,以鎂/銀電極作為陰極,藉由用於獲得初始亮度 2000 cd/m2的電流密度而實施恆定電流驅動試驗。驅動試 驗開始電壓為3.61 V ’保持初始值的9〇%以上的亮度的時 間為76小時。 [實例12] <將化合物(1-14-3)用於電子傳輸層的元件> 除了將化合物(Mlq)換為化合物(M4_3) 以外, 藉由依據實例5的方法獲得有機EL元件。以IT〇電極作 為陽極,以鎂/銀電極作為陰極,藉由用於獲得初始亮度 2000 cd/m2的電流密度而實施恆定電流驅動試驗。驅動試 驗開始電壓為3.85 V,保持初始值的9G%以上的亮度的 間為141小時。 [實例13] 〈將化合物㈤叫)用於電子傳輸層的元件> 除了將化合物(1-U_1)換為化合物(M4-11)以外, 藉由依據實例5的方法獲得有機EL元件。以IT0電極作 為陽極’⑽/銀f極作為陰極,藉㈣於獲得初始亮度S 124 201226394 4U55Upif <Components for Compounds for Electron Transport Layers> Glass substrates of 26 mm, mm x 〇.7 mm which were ground to 150 nm by a ruthenium made of a film having a thickness of 180 nm (〇pt (Stock) manufacturing) as a phase branch board. The slab of the slab of the slab of the steamed slab (7) The shovel, the 1st force, the addition of a compound key boat, and the addition of Liq's 'use: compound (1)1·1) are steamed with silver and steamed. One uses a molybdenum boat, adds a _ _ boat and adds an empty groove to form a layer. The way to be true: : Li Qiao: The boat for vapor deposition with HT: The heat is added as follows: The film thickness is 35nm, the inlet is 4 (7), the evaporation boat is used, (8) and the compound (F) are used for money (4) Yiguang layer. The plating rate of the compound is used. Secondly, the weight ratio of the steaming boat and the method of adding the compound (MM) to the steaming (4) into a thickness of 25 (10) is about 1:1. The second and the Llq degrees are 0.01 nrn / sec ~ i nm / sec. The vapor deposition rate of each layer is heated by adding a boat for vapor deposition of Llq, and the film thickness is 1 nm 125 201226394 40550 pif, and G.Gl nm/sec to ο" (10) is added, and the vaporization is performed by adding 迷. A, ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, At this time: = the sub-ratio is 10:1 square f Μ magnesium and silver original 0.1 nm / sec ~ 1Gnm / y two speed ' at the steaming speed to become the component. The side of the spider is cut into a cathode, and the surface electric excitation light is obtained straight 4:::electric ί! is the anode, and the magnesium (10) is directly grasped the voltage, and the blue wavelength of about Wei nm is obtained by using the flow for obtaining the initial brightness 2__2. The density is controlled by a constant current drive test, and the result is that the start of the test is 4, and the brightness of the initial value of 9 G% (l_ed/m2) or more is maintained. [Example 6] ^ Element for the compound (1·11·2) for the f-transport layer> In addition to the compound (M1)), the organic EL device was obtained by the method according to Example 5 except that the compound (M1) was replaced with the compound (M12). . The ITO electrode was used as the anode '^/silver electrode as the riding pole, and the current-deficient (four) test was carried out by (4) obtaining the f-filament of the initial bright 诵 cd/m. The drive start voltage is 4.12 V, and the brightness between 9 ()% or more of the initial value is maintained for 85 hours. [Example 7] <Element for using the compound (1·11·3) for the electron transport layer> An organic method was obtained by the method according to Example 5 except that the compound (1-11-1) was replaced with the compound (1113). EL component. A constant current drive test was carried out using a ΙΤ0 electrode as an anode and a magnesium/silver electrode as a saccharide electrode by (4) obtaining a current density of an initial luminance of 126 201226394 40550 pif 2000 cd/m 2 . The driving test starting voltage was 3·78 V, and the time for maintaining the luminance of 9 〇% or more of the initial value was 97 hours. [Example 8] <Component (^1-4) used for the electron transport layer element> An organic EL element was obtained by the method according to Example 5, except that the compound (Μ1·1) was replaced by the compound (1_H_4). A constant current driving test was carried out by using a ruthenium electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m2. The drive test start voltage was 3.95 V, and the brightness of the initial value of 9〇% or more was maintained for 83 hours. [Example 9] <Component for using compound 0-11-5) for an electron transport layer> An organic method was obtained by the method according to Example 5 except that the compound (iU1) was replaced with the compound (1-11-5). EL component. A constant current driving test was carried out by using an ITO electrode as an anode and a flag/silver electrode as a cathode to obtain a current intensity of an initial luminance of 2000 cd/m. The driving test start voltage was 3.88 V', and the time to maintain the brightness of 90% or more of the initial value was 93 hours. [Example 10] <Component for using compound (1-11-39) for electron transport layer> Organic EL was obtained by the method according to Example 5 except that the compound (Mi-ι) was changed to the compound (M1_39) element. The IT crucible electrode was used as the anode of the anode and the silver electrode was used as the riding pole, and the constant current driving test was carried out by obtaining the current density of the initial luminance of 127 201226394 40550 pif 2000 cd/m 2 . The drive test start voltage was 4.16 V, and the time above the initial value was 74 hours. [Example 11] <Component for using compound (1-14_2) for electron transport layer> In addition to the compound (1-1M) was changed to the compound (Bu 14-2), organic was obtained by the method according to Example 5. El component. A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m2. The drive test start voltage was 3.61 V' while maintaining the brightness of 9 % or more of the initial value for 76 hours. [Example 12] <Component for using compound (1-14-3) for electron transport layer> An organic EL device was obtained by the method according to Example 5, except that the compound (Mlq) was replaced with the compound (M4_3). A constant current driving test was carried out by using an IT crucible electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m2. The drive test start voltage was 3.85 V, and the brightness between 9 G% or more of the initial value was maintained at 141 hours. [Example 13] <Element of Compound (V)) for Electron Transport Layer> An organic EL element was obtained by the method according to Example 5 except that the compound (1-U_1) was replaced with the compound (M4-11). Taking the IT0 electrode as the anode '(10)/silver f pole as the cathode, by (iv) obtaining the initial brightness
128 201226394^ 2000 cd/m的電流雄度而實施恆定電流驅動試驗。驅動試 驗開始電壓為4.16 V,保持初始值的9〇%以上的亮度的時 間為162小時。 [實例H] <將化合物(1-14-12)用於電子傳輸層的元件〉 除了將化合物(MM )換為化合物(114-12)以外, 藉由依據實例5的方法獲得有機EL元件。以IT〇電極作 為陽極,以鎂/銀電極作為陰極,藉由用於獲得初始亮度 2000 cd/m2的電流密度而實施恆定電流驅動試驗。驅動試 驗開始電壓為3.87 V,保持初始值的9〇%以上的亮度的時 間為75小時。 [實例15] <將化合物(1-14-14)用於電子傳輸層的元件> 除了將化合物(MM )換為化合物(M4_14)以外, 藉由依據實例5的方法獲得有機EL元件。以IT〇電極作 為陽極’_/銀電極作為陰極,藉㈣於獲得初始亮度 2000 cd/m2的電流密度而實施恒^電流驅動試驗。驅動試 驗開始電壓為3·82 V ’保持被值的9()%以上的亮度的時 間為227小時。 [實例16] 〈將化合物(1-1M5)祕電子傳輸層的元件〉 除了將化合物(1-11-1)換為化合物(114·15)以外, 藉由依據實例5的方法獲得有機肛元件。以ΙΤ〇電極作 為陽極,祕/㈣師為陰極,#由歸·初始亮度 129 201226394 40550pif 2000 cd/m2的電流密度而實施恆定電流驅動試驗。驅動試 驗開始電壓為3.98V,保持初始值的90。/。以上的亮度的時 間為101小時。 [實例1力 <將化合物(M4_16)用於電子傳輸層的元件> 除了將化合物(MM)換為化合物(1-14-16)以外, 藉由依據實例5的方法獲得有機EL元件。以IT〇電極作 為陽極,以鎂/銀電極作為陰極,藉由用於獲得初始亮度 2000 cd/m2的電流密度而實雜定電流驅動試驗。驅動試 驗開始電壓為4.25 V,保持初始值的90%以上的亮度的時 間為70小時。 [實例18] <將化合物(1-14-18)用於電子傳輸層的元件> 除了將化合物(MM )換為化合物(Μ4·18)以外, 藉由依據實例5的方法獲得有機EL元件。以ΙΤ〇電極作 為陽極’祕/銀電極作為陰極,藉由用於獲得初始直产 2_ cd/m2的電流密度而實練定電流鱗試驗。驅^ 驗開始電壓為3.75 V,保持初始值的9〇%以上的亮度的 間為125小時。 又 ' [實例19] 〈將化合物(1~14-2G)用於電子傳輸層的元件〉 除了將化合物⑴⑷換為化合物(Μ4-20)以外, 藉祕據實例5的方法獲得有機EL元件。以Ιτ〇電 為陽極’以Μ/銀電極作為陰極’藉由用於獲得初始亮度128 201226394^ 2000 Constant current drive test was carried out with a current male of cd/m. The drive test start voltage was 4.16 V, and the brightness of the initial value of 9〇% or more was maintained for 162 hours. [Example H] <Component for using compound (1-14-12) for electron transport layer> An organic EL device was obtained by the method according to Example 5 except that the compound (MM) was replaced with the compound (114-12). . A constant current driving test was carried out by using an IT crucible electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m2. The drive test start voltage was 3.87 V, and the brightness of the initial value of 9〇% or more was maintained for 75 hours. [Example 15] <Component for using compound (1-14-14) for electron transport layer> An organic EL device was obtained by the method according to Example 5, except that the compound (MM) was replaced with the compound (M4_14). The IT 〇 electrode was used as the anode '_/silver electrode as the cathode, and the constant current driving test was carried out by (4) obtaining a current density of an initial luminance of 2000 cd/m 2 . The driving test start voltage was 3·82 V ', and the time required to maintain the brightness of 9 ()% or more of the value was 227 hours. [Example 16] <Element of Compound (1-1M5) Electron Transport Layer> An organic anal element was obtained by the method according to Example 5 except that the compound (1-11-1) was changed to the compound (114·15). . Using a ruthenium electrode as the anode and a secret/(four) division as the cathode, the constant current drive test was carried out by the current density of 129 201226394 40550pif 2000 cd/m2. The drive test start voltage is 3.98V, which maintains the initial value of 90. /. The above brightness time is 101 hours. [Example 1 Force < Element for using compound (M4_16) for electron transport layer> An organic EL element was obtained by the method according to Example 5, except that the compound (MM) was replaced with the compound (1-14-16). Using an IT crucible electrode as an anode and a magnesium/silver electrode as a cathode, the test was driven by a constant current using a current density of 2000 cd/m2 for an initial luminance. The driving test start voltage was 4.25 V, and the brightness of 90% or more of the initial value was maintained for 70 hours. [Example 18] <Component for using compound (1-14-18) for electron transport layer> An organic EL was obtained by the method according to Example 5 except that the compound (MM) was changed to the compound (Μ4·18). element. Using a ruthenium electrode as the anode 'secret/silver electrode as the cathode, the current scale test was practiced by obtaining a current density of 2 cd/m2 for initial production. The drive start voltage was 3.75 V, and the brightness between the initial value of 9〇% or more was 125 hours. Further [Example 19] <Element for using the compound (1 to 14-2G) for the electron transport layer> An organic EL device was obtained by the method of Example 5 except that the compound (1) (4) was replaced with the compound (Μ4-20). Taking Ιτ〇 as the anode 'with the Μ/silver electrode as the cathode' by obtaining the initial brightness
S 130 201226394 -TV*/ 2〇00 cd/m2的電流密度而實施怪定電流驅動試驗。驅動試 驗開始電壓為4.19 V ’保持初始值的嶋以上的亮度的 間為63小時。 [實例20] 〈將化合物(1-11-18)用於電子傳輸層的元件〉 除了將化合物(1-11-1)換為化合物(MM8)以外, 藉由依據實例5的方法獲得有機EL元件。以IT〇電極作 為陽極,以鎂/銀電極作為陰極,藉由用於獲得初始亮度 2000 cd/m2的電流密度而實施恆定電流驅動試驗。驅動試 驗開始電壓為4.29 V,保持初始值的9〇%以上的亮度的時 間為60小時。 [比較例3] 除了將化合物(Ml-ι)換為化合物(G)以外,藉由 依據實例5的方法獲得有機EL元件。以ITO電極作為陽 極,以鎂/銀電極作為陰極,藉由用於獲得初始亮度2〇〇〇 c d/m2的電流密度而實施恆定電流驅動試驗。結果驅動試驗 開始電壓為5.36 V,保持初始值的90%以上的亮度的時間 為2小時。 [比較例4] 除了將化合物(1-11-1)換為化合物(H)以外,藉由 依據實例5的方法獲得有機EL元件。以ITO電極作為陽 極’以鎮/銀電極作為陰極,藉由用於獲得初始亮度2〇〇〇 cd/m2的電流密度而實施怪定電流驅動試驗。結果驅動試驗 開始電壓為4.12 V,保持初始值的90%以上的亮度的時間 為26小時。 131 201226394 40550pif [比較例5] 除了將化合物(1-11-1)換為化合物(I)以外,藉由 依據實例5的方法獲得有機EL元件。以ITO電極作為陽 極,以鎂/銀電極作為陰極,藉由用於獲得初始亮度2000 cd/m2的電流密度而實施恆定電流驅動試驗。結果驅動試驗 開始電壓為4.15 V,保持初始值的90%以上的亮度的時間 為30小時。 將以上結果匯總於表4。S 130 201226394 -TV*/ 2〇00 cd/m2 current density and a strange current drive test was performed. The drive test start voltage was 4.19 V ′ and the brightness between the 嶋 or more of the initial value was 63 hours. [Example 20] <Element for using the compound (1-11-18) for the electron transport layer> An organic EL was obtained by the method according to Example 5 except that the compound (1-11-1) was replaced with the compound (MM8). element. A constant current driving test was carried out by using an IT crucible electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m2. The drive test start voltage was 4.29 V, and the brightness of the initial value of 9〇% or more was maintained for 60 hours. [Comparative Example 3] An organic EL device was obtained by the method according to Example 5, except that the compound (M1-?) was changed to the compound (G). A constant current drive test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2 〇〇〇 c d/m 2 . As a result, the driving test start voltage was 5.36 V, and the time for maintaining the brightness of 90% or more of the initial value was 2 hours. [Comparative Example 4] An organic EL device was obtained by the method according to Example 5, except that the compound (1-11-1) was replaced by the compound (H). The ITO electrode was used as the anode, and the town/silver electrode was used as the cathode, and the strange current driving test was carried out by obtaining the current density of the initial luminance of 2 〇〇〇 cd/m 2 . As a result, the driving test start voltage was 4.12 V, and the time for maintaining the brightness of 90% or more of the initial value was 26 hours. 131 201226394 40550pif [Comparative Example 5] An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was replaced with the compound (I). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m2. As a result, the driving test start voltage was 4.15 V, and the time for maintaining the brightness of 90% or more of the initial value was 30 hours. The above results are summarized in Table 4.
表4 電子傳輸層 維持初始值的90% 以上的亮度的時間 (小時) 開始電壓(V) 實例5 1-11-1 87 4.00 實例6 1-11-2 85 4.12 實例7 1-11-3 97 3.78 實例8 1-11-4 83 3.95 實例9 1-11-5 93 3.88 實例10 1-11-39 74 4.16 實例11 1-14-2 76 3.61 實例12 1-14-3 141 3.85 實例13 1-14-11 162 4.16 實例14 1-14-12 75 3.87 實例15 1-14-14 227 3.82 實例16 1-14-15 101 3.98 實例17 1-14-16 70 4.25 實例18 1-14-18 125 3.75 實例19 1-14-20 63 4.19 實例20 1-11-18 60 4.29 比較例3 G 2 5.36 比較例4 Η 26 4.12 比較例5 I 30 4.15 132 201226394 40550pif [產業上之可利用性] 根據本發明的較佳型態,可提供一種尤其提昇發光元 件的壽命,與驅動電壓的平衡性亦優異的有機電激發光元 件、具備其的顯示裝置及具備其的照明裝置等。 【圖式簡單說明】 無。 【主要元件符號說明】 無0 133Table 4 Time (hours) at which the electron transport layer maintains more than 90% of the initial value. Starting voltage (V) Example 5 1-11-1 87 4.00 Example 6 1-11-2 85 4.12 Example 7 1-11-3 97 3.78 Example 8 1-11-4 83 3.95 Example 9 1-11-5 93 3.88 Example 10 1-11-39 74 4.16 Example 11 1-14-2 76 3.61 Example 12 1-14-3 141 3.85 Example 13 1- 14-11 162 4.16 Example 14 1-14-12 75 3.87 Example 15 1-14-14 227 3.82 Example 16 1-14-15 101 3.98 Example 17 1-14-16 70 4.25 Example 18 1-14-18 125 3.75 Example 19 1-14-20 63 4.19 Example 20 1-11-18 60 4.29 Comparative Example 3 G 2 5.36 Comparative Example 4 Η 26 4.12 Comparative Example 5 I 30 4.15 132 201226394 40550pif [Industrial Applicability] According to the present invention In a preferred embodiment, an organic electroluminescence device which is excellent in balance between the driving voltage and the display device, and an illumination device including the same can be provided. [Simple description of the diagram] None. [Main component symbol description] No 0 133
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