TW202110808A - A spiroacridane-based compound, a hole transport material including the same, and an organic electronic device including the same in a hole transport layer - Google Patents

A spiroacridane-based compound, a hole transport material including the same, and an organic electronic device including the same in a hole transport layer Download PDF

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TW202110808A
TW202110808A TW109121457A TW109121457A TW202110808A TW 202110808 A TW202110808 A TW 202110808A TW 109121457 A TW109121457 A TW 109121457A TW 109121457 A TW109121457 A TW 109121457A TW 202110808 A TW202110808 A TW 202110808A
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佐藤輝幸
西尾太一
吉廣大佑
岩井新
新內聰暢
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日商關東化學股份有限公司
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Abstract

A problem to be solved by the present invention is to provide a compound capable of being used as a hole transport material, which has excellent hole injection/transport performance, electron blocking performance, light stability, electrical stability, and thermal stability; and, to provide a hole transport material including the compound; also, to provide an organic electronic device including an organic EL element or an organic photoelectric conversion element, especially an organic electronic device including an organic EL element with a long service life and high luminous efficiency, wherein the organic EL element or the organic photoelectric conversion element is provided with a hole transport layer including the compound. The solution of the present invention is a compound represented by general formulas (1-1) to (1-3), wherein n, L, R, and Ar 1 to Ar 5 are as defined in the specification.

Description

螺環二氫吖啶系化合物、含有該化合物之電洞傳輸材料、及在電洞傳輸層中包含該化合物之有機電子裝置Spirocyclic dihydroacridine compound, hole transport material containing the compound, and organic electronic device containing the compound in the hole transport layer

本發明有關提供一種新穎的化合物、利用該化合物作為電洞傳輸材料或有機電子裝置用材料、及提供一種有機電子裝置，該有機電子裝置使用了該化合物。The present invention relates to providing a novel compound, using the compound as a hole transport material or a material for an organic electronic device, and providing an organic electronic device using the compound.

作為能夠將電能與光能相互轉換的有機電子裝置，已知包含有機電致發光元件(有機EL元件)或有機光電轉換元件之有機電子裝置。As an organic electronic device capable of mutually converting electrical energy and light energy, an organic electronic device including an organic electroluminescence element (organic EL element) or an organic photoelectric conversion element is known.

其中，有機EL元件具有以陰極與陽極來夾持發光材料而成之結構，該發光材料能夠藉由電場來發光。有機EL元件是一種元件，其藉由從電極注入的電洞與電子在發光層內進行再結合，來使發光材料發光。Among them, the organic EL device has a structure in which a light-emitting material is sandwiched between a cathode and an anode, and the light-emitting material can emit light by an electric field. An organic EL device is a device that recombines holes and electrons injected from an electrode in a light-emitting layer to make a light-emitting material emit light.

有機EL元件是自發光型，視角較廣，且視認性優異。因此，有機EL元件用來作為顯示器等的顯示元件。又，有機EL元件是薄型固態元件，能夠輕量化，且強度亦優異。因此，使用有機EL元件而得的顯示器，不僅電視等的定置型，在行動裝置用途上亦有用。進一步，使用有機EL元件而得的顯示器，能夠易於改變大小，並以整個面發光，因此作為照明用途亦是有用的。The organic EL element is a self-luminous type, has a wide viewing angle, and is excellent in visibility. Therefore, organic EL elements are used as display elements such as displays. In addition, the organic EL device is a thin solid-state device, which can be lightened and has excellent strength. Therefore, displays using organic EL elements are useful not only for stationary types such as televisions, but also for mobile device applications. Furthermore, a display using an organic EL element can easily change the size and emit light on the entire surface, so it is also useful for lighting purposes.

作為有機EL元件的問題，可列舉發光效率的提升和長壽命化。為了解決上述問題，至今已進行各種手段。 例如，在有機EL元件中經常設置有電極和發光層、以及電洞注入層、電洞傳輸層、電子傳輸層、電子注入層。通常這些層是以下述順序積層：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。藉由設置電極和發光層、以及這些層，能夠提高電洞與電子在發光層內進行再結合的機率，且能夠提升有機EL元件的發光效率。As a problem of organic EL elements, improvement of luminous efficiency and life extension are mentioned. In order to solve the above problems, various measures have been carried out so far. For example, an organic EL element is often provided with electrodes and light-emitting layers, as well as a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer. Usually these layers are laminated in the following order: anode, hole injection layer, hole transport layer, light emitting layer, electron transport layer, electron injection layer, cathode. By providing electrodes and light-emitting layers, and these layers, the probability of recombination of holes and electrons in the light-emitting layer can be increased, and the light-emitting efficiency of the organic EL device can be improved.

一般是在被稱為主體材料的電荷傳輸性化合物中摻雜被稱為客體材料的螢光性化合物或磷光性化合物，來製作有機EL元件的發光層。從電極注入的電洞與電子在由主體材料和客體材料所形成的發光層中進行再結合，被激發的主體材料的能量移動至客體材料，且藉由該能量激發客體材料，並作為光能釋放，藉此能夠獲得有效率的發光。Generally, a charge-transporting compound called a host material is doped with a fluorescent compound or a phosphorescent compound called a guest material to produce a light-emitting layer of an organic EL device. The holes and electrons injected from the electrodes are recombined in the light-emitting layer formed by the host material and the guest material, the energy of the excited host material is transferred to the guest material, and the guest material is excited by the energy and used as light energy Release, thereby enabling efficient light emission.

為了提升電洞與電子的再結合機率，效率良好地傳遞兩種電荷至發光層變得重要，因此需要調整電洞與電子的傳輸平衡。 為了調整電洞與電子的傳輸平衡，必須在考慮了電洞注入材料、電洞傳輸材料的電洞遷移率、或電子注入材料、電子傳輸材料的電子遷移率、層界面中的電荷注入阻障、或是個別的膜的厚度等許多因子的情況下，來調整平衡。 然而，材料本身所擁有的電洞與電子的傳輸性因材料而異，並且由不同材料所形成的層的界面會產生電荷注入阻障，因此使電洞與電子在發光層內均衡地進行再結合並不容易。作為電荷注入和傳輸的平衡較差的例子，電洞或電子的任一者可能較少、或任一者可能極端地較多而在未進行再結合的情況下通過。亦存在一種方法，當電荷流出到對電極時，設置能夠阻擋電荷的層來將電荷封閉在發光層內，從而提高再結合效率。進一步，亦能夠藉由下述效果來獲得高發光效率：將發光層中生成的激發能加以封閉。通常，大多是電洞傳輸層或電子傳輸層承擔將流出的電荷和激發能封閉在發光層內的角色，因此電洞傳輸材料所發揮的作用非常重要。In order to increase the probability of recombination of holes and electrons, it is important to efficiently transfer the two kinds of charges to the light-emitting layer. Therefore, it is necessary to adjust the transfer balance of holes and electrons. In order to adjust the transfer balance between holes and electrons, it is necessary to consider the hole mobility of hole injection materials, hole transport materials, or electron injection materials, electron mobility of electron transport materials, and charge injection barriers in the layer interface. , Or in the case of many factors such as the thickness of individual films, adjust the balance. However, the transport properties of holes and electrons possessed by the material vary from material to material, and the interface of layers formed by different materials will produce charge injection barriers, so that holes and electrons are reproduced in a balanced manner in the light-emitting layer. Combining is not easy. As an example of a poor balance between charge injection and transport, there may be fewer holes or electrons, or either may be extremely large and pass without recombination. There is also a method, when the charge flows out to the counter electrode, a layer that can block the charge is provided to confine the charge in the light-emitting layer, thereby improving the recombination efficiency. Furthermore, high luminous efficiency can also be obtained by the following effect: the excitation energy generated in the light-emitting layer is blocked. Generally, most of the hole transport layer or electron transport layer plays the role of confining the outflowing charge and excitation energy in the light emitting layer, so the role played by the hole transport material is very important.

對於用來提高有機EL元件的再結合效率的電洞傳輸材料要求的特性，除了電洞傳輸性高且電子傳輸性低以外，能帶隙(bandgap)或游離電位(IP)、電子親和力(Ea)的值具有適當的值也很重要。電洞傳輸材料的游離電位，較佳是成為陽極的功函數或電洞注入材料的游離電位與發光材料的游離電位之間的值，藉此能夠縮小對發光層注入電洞的阻障。電洞傳輸材料的電子親和力，較佳是大於發光材料的電子親和力，藉此能夠獲得電子阻擋效果。再者，有時使用與電荷注入特性的指標之一也就是游離電位(IP)幾乎同義的最高占據分子軌域(HOMO)能階，並使用與電子親和力(Ea)機乎同義的最低未占分子軌域(LUMO)能階。The properties required for hole transport materials used to improve the recombination efficiency of organic EL elements include high hole transport and low electron transport, bandgap or free potential (IP), and electron affinity (Ea). It is also important that the value of) has an appropriate value. The free potential of the hole transport material is preferably a value between the work function of the anode or the free potential of the hole injection material and the free potential of the light-emitting material, thereby reducing the barrier to the hole injection of the light-emitting layer. The electron affinity of the hole transport material is preferably greater than the electron affinity of the luminescent material, so that the electron blocking effect can be obtained. Furthermore, one of the indicators of charge injection characteristics is sometimes used, which is the highest occupied molecular orbital (HOMO) energy level, which is almost synonymous with free potential (IP), and the lowest unoccupied energy level, which is synonymous with electron affinity (Ea), is sometimes used. Molecular orbital (LUMO) energy level.

關於有機EL元件的壽命，材料的光穩定性和電穩定性很重要(例如參照非專利文獻1和非專利文獻2)。若是光穩定性較低的材料，則因發光層內的激發能導致材料劣化。又，如果電洞傳輸層的激發能小於發光層的激發能，則發光層中生成的激發能移動至電洞傳輸層，促進電洞傳輸材料的劣化，並且亦導致元件的低效率化，因此電洞傳輸層的激發能較佳是高於發光層的激發能。另一方面，若是電穩定性較低的材料，則材料因電洞和電子而劣化，成為低效率和短壽命的原因。Regarding the life of the organic EL element, the light stability and electrical stability of the material are important (for example, refer to Non-Patent Document 1 and Non-Patent Document 2). If it is a material with low light stability, the material will deteriorate due to excitation energy in the light-emitting layer. In addition, if the excitation energy of the hole transport layer is less than the excitation energy of the light emitting layer, the excitation energy generated in the light emitting layer moves to the hole transport layer, which promotes the deterioration of the hole transport material and also causes the inefficiency of the device. The excitation energy of the hole transport layer is preferably higher than the excitation energy of the light-emitting layer. On the other hand, if it is a material with low electrical stability, the material deteriorates due to holes and electrons, which causes low efficiency and short life.

耐熱性和非晶性對於元件的長壽命化亦同樣地重要。若是耐熱性較低的材料，則元件驅動時因熱而發生熱分解，從而材料劣化。若是非晶性較低的材料，則容易發生結晶化，從而促進元件的劣化。因此，用於元件的材料要求耐熱性高、非晶性良好的性質。 作為表示非晶性的尺度，是使用玻璃轉化溫度(Tg)，當材料的Tg較低時，即便在室溫條件下，如果經過長時間，則仍會結晶化並變化成不均勻的膜，因此有機EL材料的Tg越高越佳。考慮到元件的使用環境，Tg較佳是至少135℃以上。Heat resistance and amorphous properties are equally important for the longevity of the device. If it is a material with low heat resistance, thermal decomposition occurs due to heat when the element is driven, and the material deteriorates. If it is a low amorphous material, crystallization is likely to occur, which promotes the deterioration of the device. Therefore, materials used for components require high heat resistance and good amorphous properties. As a measure of amorphousness, the glass transition temperature (Tg) is used. When the Tg of the material is low, even at room temperature, if it elapses for a long time, it will still crystallize and change into a non-uniform film. Therefore, the higher the Tg of the organic EL material, the better. Considering the use environment of the device, the Tg is preferably at least 135°C or higher.

在有機光電轉換元件中亦可能產生相同的問題。The same problem may also occur in organic photoelectric conversion devices.

例如，專利文獻1報告了一種由下述式表示的化合物(P)，作為用於電洞傳輸層的電洞傳輸材料。化合物(P)，具有苯基作為取代基，不同於本發明的對應化合物所具有的二氫吖啶(acridan)骨架的亞甲基的取代基，因此電穩定性和熱穩定性可能變低。另一方面，專利文獻1所記載的合成方法無法獲得包含本發明的螺環二氫吖啶骨架之化合物，就連用以預測該化合物的優異效果的線索都沒有。For example, Patent Document 1 reports a compound (P) represented by the following formula as a hole transport material for a hole transport layer. The compound (P) has a phenyl group as a substituent, and is different from the methylene substituent of the dihydroacridan skeleton of the corresponding compound of the present invention, so electrical stability and thermal stability may be lowered. On the other hand, the synthesis method described in Patent Document 1 cannot obtain a compound containing the spirocyclic dihydroacridine skeleton of the present invention, and there is even no clue to predict the excellent effect of the compound.

Figure 02_image003
Figure 02_image003

又，專利文獻2報告了一種由下述式表示的化合物(Q)，作為用於電洞傳輸層的電洞傳輸材料。化合物(Q)，具有甲基作為取代基，不同於本發明的對應化合物所具有的二氫吖啶骨架的亞甲基的取代基，因此電穩定性和熱穩定性可能變低。另一方面，專利文獻2所記載的合成方法無法獲得包含本發明的螺環二氫吖啶骨架之化合物，就連用以預測該化合物的優異效果的線索都沒有。In addition, Patent Document 2 reports a compound (Q) represented by the following formula as a hole transport material for the hole transport layer. The compound (Q) has a methyl group as a substituent and is different from the methylene substituent of the dihydroacridine skeleton possessed by the corresponding compound of the present invention, so electrical stability and thermal stability may be lowered. On the other hand, the synthesis method described in Patent Document 2 cannot obtain a compound containing the spirocyclic dihydroacridine skeleton of the present invention, and there is even no clue to predict the superior effect of the compound.

Figure 02_image005
Figure 02_image005

進一步，專利文獻3報告了一種由下述式表示的化合物(R)，作為用於電洞傳輸層的電洞傳輸材料。專利文獻3所記載的合成方法無法獲得包含本發明的螺環二氫吖啶骨架之化合物，就連用以預測該化合物的優異效果的線索都沒有。Furthermore, Patent Document 3 reports a compound (R) represented by the following formula as a hole transport material for the hole transport layer. The synthesis method described in Patent Document 3 cannot obtain a compound containing the spirocyclic dihydroacridine skeleton of the present invention, and there is even no clue to predict the excellent effect of the compound.

Figure 02_image007
Figure 02_image007

又，專利文獻4報告了一種由下述式表示的化合物(S)，作為具有本發明的螺環二氫吖啶骨架之材料。化合物(S)，是作為延遲螢光材料來用於發光層，因此用途與包含本發明的螺環二氫吖啶骨架之化合物不同。In addition, Patent Document 4 reports a compound (S) represented by the following formula as a material having the spirocyclic dihydroacridine skeleton of the present invention. The compound (S) is used as a delayed fluorescent material for the light-emitting layer, so its use is different from the compound containing the spirocyclic dihydroacridine skeleton of the present invention.

Figure 02_image009
[先前技術文獻] (專利文獻)
Figure 02_image009
[Prior Art Document] (Patent Document)

專利文獻1：日本專利第6279647號 專利文獻2：日本專利第6193215號 專利文獻3：歐洲專利第1840120號 專利文獻4：國際公開第2018/207750號 (非專利文獻)Patent Document 1: Japanese Patent No. 6279647 Patent Document 2: Japanese Patent No. 6193215 Patent Document 3: European Patent No. 1840120 Patent Document 4: International Publication No. 2018/207750 (Non-patent literature)

非專利文獻1：Adv.Mater.,24,3212(2012) 非專利文獻2：Adv.Mater.,22,2468(2010)Non-Patent Document 1: Adv. Mater., 24, 3212 (2012) Non-Patent Document 2: Adv. Mater., 22, 2468 (2010)

[發明所欲解決的問題][The problem to be solved by the invention]

本發明所欲解決的問題在於提供一種能夠作為電洞傳輸材料使用的化合物，其電洞注入性能或電洞傳輸性能、電子阻擋性能、光穩定性、電穩定性及熱穩定性優異。 又，本發明所欲解決的問題在於：提供一種含有上述化合物之電洞傳輸材料；以及，提供一種包含有機EL元件或有機光電轉換元件之有機電子裝置、尤其是包含長壽命且發光效率高的有機EL元件之有機電子裝置，該有機EL元件或有機光電轉換元件具備包含上述化合物之電洞傳輸層。 [解決問題的技術手段]The problem to be solved by the present invention is to provide a compound that can be used as a hole transport material, which has excellent hole injection performance or hole transport performance, electron blocking performance, light stability, electrical stability and thermal stability. In addition, the problem to be solved by the present invention is to provide a hole transport material containing the above-mentioned compound; and, to provide an organic electronic device containing an organic EL element or an organic photoelectric conversion element, especially a long life and high luminous efficiency An organic electronic device of an organic EL element, the organic EL element or organic photoelectric conversion element is provided with a hole transport layer containing the above-mentioned compound. [Technical means to solve the problem]

發明人進行各種研究，結果發現能夠成功合成以下所示的由通式(1-1)～(1-3)表示的新穎化合物，進一步該化合物作為有機電子裝置中包含的有機EL元件或有機光電轉換元件的電洞傳輸材料極為有用，尤其能夠使有機EL元件高效率化、長壽命化、及以低電壓來驅動，從而完成本發明。The inventors conducted various studies, and as a result, found that the following novel compounds represented by the general formulas (1-1) to (1-3) can be successfully synthesized, and the compounds are further used as organic EL elements or organic photoelectric devices contained in organic electronic devices. The hole transport material of the conversion element is extremely useful, and in particular, the organic EL element can be driven with high efficiency, long life, and low voltage, thereby completing the present invention.

藉由將由下述通式(1-1)～(1-3)表示的化合物作為電洞傳輸層材料使用，能夠使有機電子裝置中包含的有機EL元件或有機光電轉換元件高效率化和長壽命化，發明人推測其理由如以下所示。 亦即，由下述通式(1-1)～(1-3)表示的化合物，藉由包含相同通式所規定的螺環二氫吖啶骨架，使材料成為蓬鬆且堅硬的結構，能夠抑制分子彼此堆疊(stacking)。推測藉此該化合物能夠顯示較高的激發能，從而抑制能量從發光層轉移，並使元件高效率化。又，推測化合物的堅硬性增加，從而電穩定性、光穩定性及熱穩定性增加，亦有助於有機電子裝置中包含的有機EL元件或有機光電轉換元件的長壽命化。By using the compounds represented by the following general formulas (1-1) to (1-3) as the hole transport layer material, it is possible to increase the efficiency and length of the organic EL element or the organic photoelectric conversion element contained in the organic electronic device. The reason for the increase in life expectancy is as follows. That is, the compounds represented by the following general formulas (1-1) to (1-3), by including the spirocyclic dihydroacridine skeleton defined by the same general formula, make the material a fluffy and hard structure, Inhibition molecules are stacked on top of each other. It is presumed that this compound can exhibit high excitation energy, thereby suppressing energy transfer from the light-emitting layer, and increasing the efficiency of the device. In addition, it is estimated that the increase in the hardness of the compound increases the electrical stability, light stability, and thermal stability, which also contributes to the long life of the organic EL element or the organic photoelectric conversion element included in the organic electronic device.

本發明的主旨如以下所述。 [1] 一種由通式(1-1)表示的化合物，The gist of the present invention is as follows. [1] A compound represented by the general formula (1-1),

Figure 02_image011
Figure 02_image011

式(1-1)中， n是0或1； L表示單鍵、伸苯基、伸萘基、或由吡啶環、吡嗪環、嘧啶環、噠嗪環及三嗪環中的任一種環所形成之二價芳香族雜環基，該伸苯基、該伸萘基或該二價芳香族雜環基可進一步具有取代基； Ar1 ～Ar5 各自相互獨立地為可具有取代基之芳香族烴基、可具有取代基之芳香族雜環基、或可具有取代基之稠合多環芳香族基； 但是，下述化合物(T)除外，

Figure 02_image013
。In formula (1-1), n is 0 or 1; L represents a single bond, a phenylene group, a naphthylene group, or any one of a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, and a triazine ring A divalent aromatic heterocyclic group formed by a ring, the phenylene group, the naphthylene group, or the divalent aromatic heterocyclic group may further have a substituent; Ar 1 to Ar 5 are each independently an optionally substituted group The aromatic hydrocarbon group, the aromatic heterocyclic group which may have a substituent, or the condensed polycyclic aromatic group which may have a substituent; However, the following compound (T) is excluded,
Figure 02_image013
.

[2] 一種由通式(1-2)或(1-3)表示的化合物，[2] A compound represented by the general formula (1-2) or (1-3),

Figure 02_image015
Figure 02_image015

式(1-2)、(1-3)中， n是0或1； L表示單鍵、伸苯基、伸萘基、或由吡啶環、吡嗪環、嘧啶環、噠嗪環及三嗪環中的任一種環所形成之二價芳香族雜環基，該伸苯基、該伸萘基或該二價芳香族雜環基可進一步具有取代基； Ar1 ～Ar5 各自相互獨立地為可具有取代基之芳香族烴基、可具有取代基之芳香族雜環基、或可具有取代基之稠合多環芳香族基； R是氫、氘、鹵素基、可具有取代基之直鏈狀、支鏈狀或環狀的烷基、可具有取代基之直鏈狀、支鏈狀或環狀的烷氧基、或可具有取代基之芳香族烴基。In the formulas (1-2) and (1-3), n is 0 or 1; L represents a single bond, a phenylene group, a naphthylene group, or is composed of a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring and three A divalent aromatic heterocyclic group formed by any one of the azine rings, the phenylene group, the naphthylene group, or the divalent aromatic heterocyclic group may further have a substituent; Ar 1 to Ar 5 are independent of each other Ground is an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a condensed polycyclic aromatic group which may have a substituent; R is a hydrogen, deuterium, halogen group, which may have a substituent A linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent.

[3] 如[1]或[2]所述之化合物，其中，L是單鍵、伸苯基或伸萘基。 [4] 如[1]～[3]中任一項所述之化合物，其中，Ar4 、Ar5 各自相互獨立地為伸苯基、伸聯苯基、或伸萘基。 [5] 如[2]～[4]中任一項所述之化合物，其中，R是氫或苯基。 [6] 一種電洞傳輸材料，其含有[1]～[5]中任一項所述之化合物。[3] The compound according to [1] or [2], wherein L is a single bond, phenylene or naphthylene. [4] The compound according to any one of [1] to [3], wherein Ar 4 and Ar 5 are each independently a phenylene group, a biphenylene group, or a naphthylene group. [5] The compound according to any one of [2] to [4], wherein R is hydrogen or phenyl. [6] A hole transport material containing the compound described in any one of [1] to [5].

[7] 一種有機電子裝置，其包含有機電致發光元件或有機光電轉換元件，該等元件在陰極與陽極之間具備電洞傳輸層，該有機電子裝置的特徵在於： 前述電洞傳輸層包含前述[1]～[5]中任一項所述之化合物。[7] An organic electronic device comprising an organic electroluminescence element or an organic photoelectric conversion element, the elements are provided with a hole transport layer between a cathode and an anode, and the organic electronic device is characterized by: The hole transport layer contains the compound described in any one of [1] to [5].

[8] 如前述[7]所述之有機電子裝置，其中，包含有機電致發光元件，該元件在電洞傳輸層與陰極之間具有發光層。 [9] 如前述[8]所述之有機電子裝置，其中，發光層包含主體材料、及由發光材料所構成的客體材料，該主體材料是電子傳輸性材料、或具有電洞傳輸性和電子傳輸性的雙極性電荷傳輸性材料。 [發明的功效][8] The organic electronic device described in [7] above, which includes an organic electroluminescence element having a light-emitting layer between the hole transport layer and the cathode. [9] The organic electronic device according to the aforementioned [8], wherein the light-emitting layer includes a host material and a guest material composed of the light-emitting material, and the host material is an electron-transporting material or has hole-transporting properties and electrons. Transportable bipolar charge transporting material. [Effect of Invention]

本發明的化合物能夠用來作為一種電洞傳輸性材料，其能夠獲得一種光穩定性、以及電穩定性和熱穩定性優異的電洞傳輸層。 尤其，本發明的有機EL元件是一種具備電洞傳輸層之有機EL元件，該電洞傳輸層包含本發明的化合物，包含該有機EL元件之有機電子裝置為長壽命且發光效率高，能夠以低電壓來驅動。The compound of the present invention can be used as a hole-transporting material, which can obtain a hole-transporting layer with excellent light stability, electrical stability and thermal stability. In particular, the organic EL device of the present invention is an organic EL device provided with a hole transport layer, the hole transport layer contains the compound of the present invention, and the organic electronic device containing the organic EL device has a long life and high luminous efficiency, and can be Low voltage to drive.

以下，進一步詳細地說明本發明。 本發明有關一種由通式(1-1)表示的化合物，Hereinafter, the present invention will be explained in further detail. The present invention relates to a compound represented by the general formula (1-1),

Figure 02_image011
Figure 02_image011

式(1-1)中， n是0或1； L表示單鍵、伸苯基、伸萘基、或由吡啶環、吡嗪環、嘧啶環、噠嗪環及三嗪環中的任一種環所形成之二價芳香族雜環基，該伸苯基、該伸萘基或該二價芳香族雜環基可進一步具有取代基； Ar1 ～Ar5 各自相互獨立地為可具有取代基之芳香族烴基、可具有取代基之芳香族雜環基、或可具有取代基之稠合多環芳香族基。 但是，從由通式(1-1)表示的化合物中將下述化合物(T)除外。

Figure 02_image013
。In formula (1-1), n is 0 or 1; L represents a single bond, a phenylene group, a naphthylene group, or any one of a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, and a triazine ring A divalent aromatic heterocyclic group formed by a ring, the phenylene group, the naphthylene group, or the divalent aromatic heterocyclic group may further have a substituent; Ar 1 to Ar 5 are each independently an optionally substituted group The aromatic hydrocarbon group, the aromatic heterocyclic group which may have a substituent, or the condensed polycyclic aromatic group which may have a substituent. However, the following compound (T) is excluded from the compounds represented by the general formula (1-1).
Figure 02_image013
.

又，本發明有關一種由通式(1-2)或(1-3)表示的化合物，Furthermore, the present invention relates to a compound represented by the general formula (1-2) or (1-3),

Figure 02_image015
Figure 02_image015

式(1-2)、(1-3)中， n是0或1； L表示單鍵、伸苯基、伸萘基、或由吡啶環、吡嗪環、嘧啶環、噠嗪環及三嗪環中的任一種環所形成之二價芳香族雜環基，該伸苯基、該伸萘基或該二價芳香族雜環基可進一步具有取代基； Ar1 ～Ar5 各自相互獨立地為可具有取代基之芳香族烴基、可具有取代基之芳香族雜環基、或可具有取代基之稠合多環芳香族基； R是氫、氘、鹵素基、可具有取代基之直鏈狀、支鏈狀或環狀的烷基、可具有取代基之直鏈狀、支鏈狀或環狀的烷氧基、或可具有取代基之芳香族烴基。In the formulas (1-2) and (1-3), n is 0 or 1; L represents a single bond, a phenylene group, a naphthylene group, or is composed of a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring and three A divalent aromatic heterocyclic group formed by any one of the azine rings, the phenylene group, the naphthylene group, or the divalent aromatic heterocyclic group may further have a substituent; Ar 1 to Ar 5 are independent of each other Ground is an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a condensed polycyclic aromatic group which may have a substituent; R is a hydrogen, deuterium, halogen group, which may have a substituent A linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent.

通式(1-1)～(1-3)中的L，更佳是單鍵、伸苯基、伸萘基。 通式(1-1)～(1-3)中的n是0或1，如果綜合地判斷由通式(1-1)～(1-3)表示的化合物的電穩定性、熱穩定性、成膜性、以及合成和精製的容易程度等，較佳是1。L in the general formulae (1-1) to (1-3) is more preferably a single bond, a phenylene group, or a naphthylene group. If n in the general formulas (1-1) to (1-3) is 0 or 1, if the electrical stability and thermal stability of the compounds represented by the general formulas (1-1) to (1-3) are judged comprehensively , Film-forming properties, and ease of synthesis and purification, etc., preferably 1.

作為通式(1-1)～(1-3)中的Ar1 ～Ar3 中的芳香族烴基、芳香族雜環基及稠合多環芳香族基、或R之中的芳香族烴基，可列舉例如：苯基、聯苯基、三聯苯基、萘基、蒽基、菲基、茀基、茚基、芘基、苝基、熒蒽基(fluoranthenyl)、聯伸三苯基(triphenylenyl)、吡啶基、嘧啶基、三嗪基、呋喃基、吡咯基、噻吩基、喹啉基、異喹啉基、苯并呋喃基、苯并噻吩基、吲哚基、咔唑基、苯并噁唑基、苯并噻唑基、喹噁啉基(quinoxalinyl)、苯并咪唑基、吡唑基、二苯并呋喃基、二苯并噻吩基、萘啶基(naphthyridinyl)、啡啉基(phenanthrolinyl)、吖啶基、及咔啉基(carbolinyl)。 作為 Ar1 ～Ar3 中的芳香族烴基、芳香族雜環基及稠合多環芳香族基，較佳是形成環的碳和雜原子合計為6～25的基團，更佳是形成環的碳和雜原子合計為6～20的基團，進一步更佳是形成環的碳和雜原子合計為6～18的基團。As the aromatic hydrocarbon group, aromatic heterocyclic group and condensed polycyclic aromatic group in Ar 1 to Ar 3 in the general formulas (1-1) to (1-3), or the aromatic hydrocarbon group in R, Examples include phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, stilbene, indenyl, pyrenyl, perylene, fluoranthenyl, and triphenylenyl. , Pyridyl, pyrimidinyl, triazinyl, furyl, pyrrolyl, thienyl, quinolinyl, isoquinolinyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoxanyl Azolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, naphthyridinyl, phenanthrolinyl , Acridinyl, and carbolinyl (carbolinyl). As the aromatic hydrocarbon group, aromatic heterocyclic group and condensed polycyclic aromatic group in Ar 1 to Ar 3 , a group having a total of 6 to 25 carbons and heteroatoms forming a ring is preferred, and a ring is more preferred A group having a total of 6 to 20 carbons and heteroatoms, and more preferably a group having a total of 6 to 18 carbons and heteroatoms forming a ring.

作為通式(1-1)～(1-3)中的Ar1 ～Ar3 中的芳香族烴基、芳香族雜環基及稠合多環芳香族基可具有的取代基、R之中的芳香族烴基可具有的取代基、或L可具有的取代基，可列舉例如：氘原子；氰基；硝基；鹵素基；甲基、乙基、丙基、異丙基、丁基、異丁基、三級丁基等的直鏈狀或分枝狀的烷基；甲氧基、乙氧基、丙氧基等的烷氧基；乙烯基、烯丙基等的烯基；苯氧基、苯三氧基等的芳氧基；苯甲氧基等的芳烷氧基；苯基、聯苯基、三聯苯基、萘基、蒽基、菲基、茀基、茚基、芘基、苝基、熒蒽基、聯伸三苯基等的芳香族烴基或稠合多環芳香族基；吡啶基、嘧啶基、三嗪基、呋喃基、吡咯基、噻吩基、喹啉基、異喹啉基、苯并呋喃基、苯并噻吩基、吲哚基、咔唑基、苯并噁唑基、苯并噻唑基、喹噁啉基、苯并咪唑基、吡唑基、二苯并呋喃基、二苯并噻吩基、萘啶基、啡啉基、吖啶基、及咔啉基等的芳香族雜環基或稠合多環芳香族基；苯乙烯基、萘乙烯基等的芳乙烯基；乙醯基等的醯基。 可存在二個以上的前述取代基，當存在二個以上時，各自可不同。As the substituents that the aromatic hydrocarbon group, the aromatic heterocyclic group, and the condensed polycyclic aromatic group in Ar 1 to Ar 3 in the general formulas (1-1) to (1-3) may have, among R The substituents that the aromatic hydrocarbon group may have, or the substituents that L may have, include, for example, a deuterium atom; a cyano group; a nitro group; a halogen group; a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isopropyl group. Straight-chain or branched alkyl such as butyl and tertiary butyl; alkoxy such as methoxy, ethoxy, and propoxy; alkenyl such as vinyl and allyl; phenoxy Aryloxy groups such as benzyl and benzenetrioxy groups; aralkyloxy groups such as benzyloxy groups; phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, stilbyl, indenyl, and pyrene Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as pyridyl, perylene, fluoranthene, and triphenylene; pyridyl, pyrimidinyl, triazinyl, furanyl, pyrrolyl, thienyl, quinolinyl, Isoquinolinyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxolinyl, benzimidazolyl, pyrazolyl, diphenyl Aromatic heterocyclic groups or condensed polycyclic aromatic groups such as furanyl, dibenzothienyl, naphthyridinyl, phenanthrinyl, acridinyl, and carboline; styryl, naphthalene vinyl, etc. The aryl vinyl group; the acetyl group such as acetyl group. Two or more of the aforementioned substituents may be present, and when two or more are present, each may be different.

如果綜合地判斷電穩定性、熱穩定性、成膜性、以及合成和精製的容易程度等，作為通式(1-1)～(1-3)中的Ar1 ～Ar3 中的芳香族烴基、芳香族雜環基及稠合多環芳香族基可具有的取代基，在上述的例子之中，較佳是碳數1～10的直鏈烷基、或是可取代有一個或二個以上的碳數1～5的直鏈烷基的苯基、聯苯基、三聯苯基或萘基，更佳是甲基、乙基、丙基或丁基、或是可取代有一個或二個以上的碳數1～3的直鏈烷基的苯基或聯苯基，最佳是甲基或苯基。If the electrical stability, thermal stability, film-forming properties, ease of synthesis and purification, etc. are comprehensively judged, it is regarded as the aromatics in Ar 1 to Ar 3 in general formulas (1-1) to (1-3). The hydrocarbon group, aromatic heterocyclic group and condensed polycyclic aromatic group may have substituents. Among the above examples, it is preferably a linear alkyl group having 1 to 10 carbons, or may be substituted with one or two Phenyl, biphenyl, terphenyl or naphthyl of more than one C1-C5 linear alkyl group, more preferably methyl, ethyl, propyl or butyl, or may be substituted with one or Two or more phenyl groups or biphenyl groups of linear alkyl groups having 1 to 3 carbon atoms are preferably methyl or phenyl groups.

通式(1-1)～(1-3)中的Ar3 ，較佳是可在任意位置與L鍵結且可具有取代基之苯基、聯苯基、三聯苯、萘基、咔唑基、二苯并呋喃基、二苯并噻吩基，特佳是可在任意位置與L鍵結且可具有取代基之萘基、咔唑基、二苯并呋喃基。 Ar 3 in the general formulae (1-1) to (1-3) is preferably phenyl, biphenyl, terphenyl, naphthyl, carbazole which can be bonded to L at any position and may have a substituent Group, dibenzofuranyl, dibenzothienyl, particularly preferably naphthyl, carbazolyl, and dibenzofuranyl which can be bonded to L at any position and may have a substituent.

作為通式(1-1)～(1-3)中的Ar4 、Ar5 中的芳香族烴基、芳香族雜環基及稠合多環芳香族基，可列舉例如：伸苯基、伸聯苯基、伸三聯苯基、伸萘基、伸茀基、聯伸三苯基、伸苯并呋喃基、伸苯并噻吩基、伸咔唑基、二苯并呋喃基、及二苯并噻吩基。 作為Ar4 、Ar5 中的芳香族烴基、芳香族雜環基及稠合多環芳香族基，較佳是形成環的碳和雜原子合計為6～18的基團，更佳是形成環的碳和雜原子合計為6～12的基團。 As the Ar 4 in the general formulas (1-1) to (1-3), the aromatic hydrocarbon group, the aromatic heterocyclic group and the condensed polycyclic aromatic group in Ar 5 include, for example, phenylene, ethylene Biphenyl, terphenylene, naphthylene, tetraphenylene, triphenylene, benzofuranyl, benzothienyl, carbazolyl, dibenzofuranyl, and dibenzothiophene base. As the aromatic hydrocarbon group, aromatic heterocyclic group, and condensed polycyclic aromatic group in Ar 4 and Ar 5 , a group having a total of 6 to 18 carbon and heteroatoms forming a ring is preferred, and a ring forming group is more preferred. The total number of carbon and heteroatoms is 6-12.

通式(1-1)中的連接Ar4 與Ar5 的曲線，表示可在任意位置鍵結的單鍵。當Ar4 或Ar5 是包含2個以上的環之芳香族烴基、芳香族雜環基、或稠合多環芳香族基時，該包含2個以上的環之芳香族烴基、芳香族雜環基、或稠合多環芳香族基可藉由該單鍵來與另一個Ar4 或Ar5 的2個以上的環之中的任一個環鍵結。 又，通式(1-2)和(1-3)中，Ar4 和Ar5 是藉由以實線表示的鍵結來與共有該實線的五員環或六員環的螺環一起形成稠合環。 The curve connecting Ar 4 and Ar 5 in the general formula (1-1) represents a single bond that can be bonded at any position. When Ar 4 or Ar 5 is an aromatic hydrocarbon group, aromatic heterocyclic group, or condensed polycyclic aromatic group containing two or more rings, the aromatic hydrocarbon group or aromatic heterocyclic group containing two or more rings The group or the condensed polycyclic aromatic group can be bonded to any one of the two or more rings of another Ar 4 or Ar 5 through the single bond. In addition, in the general formulas (1-2) and (1-3), Ar 4 and Ar 5 are combined with the five-membered ring or the six-membered spiro ring that shares the solid line by the bond represented by the solid line. A fused ring is formed.

作為通式(1-1)～(1-3)中的Ar4 、Ar5 中的芳香族烴基、芳香族雜環基及稠合多環芳香族基可具有的取代基，可列舉例如：氘原子；氰基；硝基；鹵素基；甲基、乙基、丙基、異丙基等的直鏈狀或分枝狀的烷基；甲氧基、乙氧基等的烷氧基；乙烯基、烯丙基等的烯基；可具有取代基之苯氧基、苯三氧基等的芳氧基；可具有取代基之苯甲氧基等的芳烷氧基；可具有取代基之苯基、聯苯基、三聯苯基、萘基、茀基、聯伸三苯基等的芳香族烴基或稠合多環芳香族基；可具有取代基之苯并呋喃基、苯并噻吩基、吲哚基、咔唑基、二苯并呋喃基、二苯并噻吩基、萘啶基、及啡啉基等的芳香族雜環基或稠合多環芳香族基；可具有取代基之苯乙烯基、萘乙烯基等的芳乙烯基；乙醯基等的醯基。 可存在二個以上的前述取代基，當存在二個以上時，各自可不同。 As the substituents that Ar 4 in the general formulas (1-1) to (1-3), the aromatic hydrocarbon group, the aromatic heterocyclic group, and the condensed polycyclic aromatic group in Ar 5 may have, for example: Deuterium atoms; cyano groups; nitro groups; halogen groups; linear or branched alkyl groups such as methyl, ethyl, propyl, and isopropyl; alkoxy groups such as methoxy and ethoxy; Alkenyl groups such as vinyl and allyl groups; aryloxy groups such as phenoxy and benzenetrioxy which may have substituents; aralkyloxy groups such as benzyloxy which may have substituents; may have substituents Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as phenyl, biphenyl, terphenyl, naphthyl, stilbene, triphenylene, etc.; benzofuranyl and benzothienyl which may have substituents , Indolyl, carbazolyl, dibenzofuranyl, dibenzothienyl, naphthyridinyl, and phenanthryl and other aromatic heterocyclic groups or condensed polycyclic aromatic groups; those that may have substituents Aryl vinyl groups such as styryl and naphthalene vinyl groups; acetyl groups such as acetyl groups. Two or more of the aforementioned substituents may be present, and when two or more are present, each may be different.

如果綜合地判斷電穩定性、熱穩定性、成膜性、以及合成和精製的容易程度等，作為通式(1-1)～(1-3)中的Ar4 、Ar5 中的芳香族烴基、芳香族雜環基及稠合多環芳香族基可具有的取代基，在上述的例子之中，較佳是碳數1～10的直鏈烷基、或是可取代有一個或二個以上的碳數1～5的直鏈烷基的苯基、聯苯基、三聯苯基或萘基，更佳是甲基、乙基、丙基或丁基、或是可取代有一個或二個以上的碳數1～3的直鏈烷基的苯基或聯苯基，最佳是甲基或苯基。If the electrical stability, thermal stability, film-forming properties, ease of synthesis and purification, etc. are comprehensively judged, it can be regarded as the aromatics in Ar 4 and Ar 5 in general formulas (1-1) to (1-3). The hydrocarbon group, aromatic heterocyclic group and condensed polycyclic aromatic group may have substituents. Among the above examples, it is preferably a linear alkyl group having 1 to 10 carbons, or may be substituted with one or two Phenyl, biphenyl, terphenyl or naphthyl of more than one C1-C5 linear alkyl group, more preferably methyl, ethyl, propyl or butyl, or may be substituted with one or Two or more phenyl groups or biphenyl groups of linear alkyl groups having 1 to 3 carbon atoms are preferably methyl or phenyl groups.

作為通式(1-3)中的R之中的直鏈狀的烷基，可列舉例如：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基。 作為通式(1-3)中的R之中的支鏈狀的烷基，可列舉例如：1-甲基乙基、1-甲基丙基、1-乙基丙基、1-正丙基丙基、1-甲基丁基、1-乙基丁基、1-丙基丁基、1-正丁基丁基、1-甲基戊基、1-乙基戊基、1-正丙基戊基、1-正戊基戊基、1-甲基己基、1-乙基己基、1-正丙基己基、1-正丁基己基、1-正戊基己基、1-正己基己基、1-甲基庚基、1-乙基庚基、1-正丙基庚基、1-正丁基庚基、1-正戊基庚基。Examples of the linear alkyl group in R in the general formula (1-3) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. , Decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl. Examples of the branched alkyl group in R in the general formula (1-3) include 1-methylethyl, 1-methylpropyl, 1-ethylpropyl, and 1-n-propyl. Propyl, 1-methylbutyl, 1-ethylbutyl, 1-propylbutyl, 1-n-butylbutyl, 1-methylpentyl, 1-ethylpentyl, 1-n Propylpentyl, 1-n-pentylpentyl, 1-methylhexyl, 1-ethylhexyl, 1-n-propylhexyl, 1-n-butylhexyl, 1-n-pentylhexyl, 1-n-hexyl Hexyl, 1-methylheptyl, 1-ethylheptyl, 1-n-propylheptyl, 1-n-butylheptyl, 1-n-pentylheptyl.

作為通式(1-3)中的R之中的環狀的烷基，可列舉例如：環丙基、環丁基、環戊基、環己基、環庚基、環辛基等的環烷基；或，雙環烷基、三環烷基等的多環烷基。 作為通式(1-3)中的R之中的直鏈狀、支鏈狀或環狀的烷氧基，可列舉例如氧原子位於上述直鏈狀、支鏈狀或環狀的烷基的1位上之烷氧基。 從玻璃轉化溫度和立體阻礙(steric hindrance)等的觀點來看，上述直鏈狀、支鏈狀或環狀的烷基或烷氧基較佳是碳數為1～25，更佳是碳數為1～15，進一步更佳是碳數為1～8。Examples of the cyclic alkyl group in R in the general formula (1-3) include cycloalkanes such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Group; or, polycyclic alkyl such as bicycloalkyl, tricycloalkyl, etc. Examples of the linear, branched, or cyclic alkoxy group in R in the general formula (1-3) include those in which the oxygen atom is located in the above-mentioned linear, branched or cyclic alkyl group. Alkoxy at the 1-position. From the viewpoints of glass transition temperature and steric hindrance, the above-mentioned linear, branched or cyclic alkyl or alkoxy group preferably has 1 to 25 carbon atoms, more preferably carbon number It is 1-15, More preferably, the carbon number is 1-8.

作為通式(1-3)中的R之中的直鏈狀、支鏈狀或環狀的烷基可具有的取代基、或是直鏈狀、支鏈狀或環狀的烷氧基可具有的取代基，可列舉例如烷氧基和鹵素基。 可存在二個以上的前述取代基，當存在二個以上時，各自可不同。As a substituent that the linear, branched, or cyclic alkyl group in R in the general formula (1-3) may have, or a linear, branched, or cyclic alkoxy group can be Examples of the substituents include an alkoxy group and a halogen group. Two or more of the aforementioned substituents may be present, and when two or more are present, each may be different.

如果綜合地判斷由通式(1-3)表示的化合物的電穩定性、熱穩定性、成膜性、以及合成和精製的容易程度等，R最佳是各自相互獨立地為氫或苯基。If the electrical stability, thermal stability, film-forming properties, and ease of synthesis and purification of the compound represented by the general formula (1-3) are comprehensively judged, it is best that R is independently hydrogen or phenyl. .

藉由通式(1-1)～(1-3)的二氫吖啶骨架的亞甲基部分被二個規定的(雜)芳基取代且該(雜)芳基利用單鍵來形成環、以及二氫吖啶骨架的苯環被Ar2 取代，從而使化合物成為蓬鬆且堅硬的分子結構，能夠抑制分子彼此堆疊。推測藉此化合物能夠顯示較高的激發能，並抑制能量從發光層轉移至包含該化合物之電洞傳輸層，因此包含有機EL元件之電子裝置能夠高效率化。 又，推測藉由通式(1-1)～(1-3)的二氫吖啶骨架的亞甲基部分被二個規定的(雜)芳基且該(雜)芳基利用單鍵來形成環、以及二氫吖啶骨架的苯環被Ar2 取代，從而化合物的堅硬性增加，因此電穩定性、光穩定性及熱穩定性增加，亦有助於包含有機EL元件或有機光電轉換元件之有機電子裝置的長壽命化，該等元件在電洞傳輸層中包含該化合物。 進一步，推測藉由通式(1-1)～(1-3)的二氫吖啶骨架的亞甲基部分被二個規定的(雜)芳基取代且該(雜)芳基利用單鍵來形成環、以及二氫吖啶骨架的苯環被Ar2 取代，從而能夠立體地抑制親核化合物或親電子化合物攻擊N原子，因此電穩定性、光穩定性及熱穩定性增加，亦有助於包含有機EL元件或有機光電轉換元件之有機電子裝置的長壽命化，該等元件在電洞傳輸層中包含該化合物。 由通式(1-1)～(1-3)表示的化合物所顯示的高激發能，尤其有利於用在包含藍色發光有機EL元件之電子裝置。The methylene moiety of the dihydroacridine skeleton of the general formulas (1-1) to (1-3) is substituted by two prescribed (hetero)aryl groups and the (hetero)aryl group utilizes a single bond to form a ring , And the benzene ring of the dihydroacridine skeleton is replaced by Ar 2 , so that the compound becomes a fluffy and hard molecular structure, which can prevent the molecules from stacking on each other. It is speculated that the compound can exhibit higher excitation energy and suppress energy transfer from the light-emitting layer to the hole transport layer containing the compound, so that the electronic device containing the organic EL element can be highly efficient. In addition, it is estimated that the methylene moiety of the dihydroacridine skeleton of the general formulas (1-1) to (1-3) is defined by two (hetero)aryl groups, and the (hetero)aryl group is formed by a single bond. The benzene ring forming the ring and the dihydroacridine skeleton is replaced by Ar 2 to increase the hardness of the compound, so the electrical stability, light stability and thermal stability are increased, which also contributes to the inclusion of organic EL devices or organic photoelectric conversion To extend the life of the organic electronic device of the device, the device contains the compound in the hole transport layer. Furthermore, it is speculated that the methylene moiety of the dihydroacridine skeleton of the general formulas (1-1) to (1-3) is substituted with two prescribed (hetero)aryl groups and the (hetero)aryl group utilizes a single bond To form the ring and the benzene ring of the dihydroacridine skeleton is replaced by Ar 2 , it can sterically inhibit the attack of the nucleophilic compound or electrophilic compound on the N atom, so the electrical stability, light stability and thermal stability are increased, and there is also It contributes to the longevity of organic electronic devices including organic EL elements or organic photoelectric conversion elements, and these elements include the compound in the hole transport layer. The high excitation energy exhibited by the compounds represented by the general formulas (1-1) to (1-3) is particularly advantageous for use in electronic devices including blue light-emitting organic EL devices.

以下，示出由通式(1-1)～(1-3)表示的化合物的具體例，但是不特別限定於這些例子。Hereinafter, specific examples of the compounds represented by general formulas (1-1) to (1-3) are shown, but they are not particularly limited to these examples.

Figure 02_image017
Figure 02_image017

Figure 02_image019
Figure 02_image019

Figure 02_image021
Figure 02_image021

Figure 02_image023
Figure 02_image023

Figure 02_image025
Figure 02_image025

Figure 02_image027
Figure 02_image027

Figure 02_image029
Figure 02_image029

作為上述具體例來示出的化合物之中，從電荷注入特性、電荷傳輸特性、電穩定性及熱穩定性的觀點等來看，作為特佳的化合物的例子，可列舉由以下化學式表示的化合物(A)～(I)。Among the compounds shown as the above specific examples, from the viewpoints of charge injection characteristics, charge transport characteristics, electrical stability, and thermal stability, etc., as examples of particularly preferable compounds, compounds represented by the following chemical formulas can be cited (A)～(I).

Figure 02_image031
Figure 02_image031

Figure 02_image033
Figure 02_image033

Figure 02_image035
Figure 02_image035

Figure 02_image037
Figure 02_image037

Figure 02_image039
Figure 02_image039

Figure 02_image041
Figure 02_image041

Figure 02_image043
Figure 02_image043

Figure 02_image045
Figure 02_image045

Figure 02_image047
Figure 02_image047

由通式(1-1)～(1-3)表示的化合物具有前述特性，因此能夠作為有機電子裝置中包含的有機EL元件用材料或有機光電轉換元件用材料來使用，尤其能夠適合用於有機EL元件的電洞傳輸層，較佳是藍色發光有機EL元件的電洞傳輸層。前述化合物，尤其可使有機電子裝置中包含的有機EL元件能夠高效率化和長壽命化。 又，本發明亦有關一種電洞傳輸材料，其含有由通式(1-1)～(1-3)表示的化合物。The compounds represented by the general formulas (1-1) to (1-3) have the aforementioned characteristics, and therefore can be used as materials for organic EL elements or organic photoelectric conversion elements contained in organic electronic devices, and can be particularly suitably used for The hole transport layer of the organic EL device is preferably the hole transport layer of the blue light-emitting organic EL device. The aforementioned compounds can particularly increase the efficiency and life of organic EL elements included in organic electronic devices. In addition, the present invention also relates to a hole transport material containing compounds represented by general formulas (1-1) to (1-3).

能夠藉由高效能液相層析(HPLC)來實行由通式(1-1)～(1-3)表示的化合物的純度的測定。高效能液相層析是一種方法，其藉由下述方式來測定試料的純度：對導入試料後的移動相施加壓力，並以高流速來使溶劑通過移動相，然後以管柱來分離試料(混合物)，並以偵測器來偵測經分離後的試料。The purity of the compounds represented by the general formulas (1-1) to (1-3) can be measured by high performance liquid chromatography (HPLC). High performance liquid chromatography is a method that measures the purity of the sample by applying pressure to the mobile phase after the sample is introduced, and passing the solvent through the mobile phase at a high flow rate, and then separating the sample with a column (Mixture), and use a detector to detect the separated sample.

能夠藉由質譜法(MS)來實行由通式(1-1)～(1-3)表示的化合物的分子量的測定。能夠藉由下述方式來實行質譜法：在真空中對從試料導入部所導入的試料施加高電壓，來使試料游離化，並根據質量電荷比來將離子分離，然後以偵測部來進行偵測。 試料導入部能夠直接連接氣相層析儀(GC/MS)、高效能液相層析儀(LC/MS)、毛細管電泳儀(CE/MS)，能夠測定分子量，並且亦能夠實行純度的測定。再者，有時亦能夠採用直接使試料游離化的直接進樣方式(DI/MS)。 能夠對離子源採用各種游離化的方式。可列舉例如：電子游離法(EI)、快速原子撞擊法(FAB)、電噴灑游離法(ESI)、感應耦合電漿法(ICP)等。The molecular weight of the compounds represented by the general formulas (1-1) to (1-3) can be measured by mass spectrometry (MS). Mass spectrometry can be carried out by applying a high voltage to the sample introduced from the sample introduction part in a vacuum to dissociate the sample, separating the ions according to the mass-to-charge ratio, and then performing the detection part. Detection. The sample introduction part can be directly connected to gas chromatograph (GC/MS), high performance liquid chromatograph (LC/MS), capillary electrophoresis (CE/MS), can measure molecular weight, and can also perform purity measurement . In addition, the direct injection method (DI/MS) that directly dissociates the sample can also be used in some cases. Various ionization methods can be used for the ion source. Examples include the electron ionization method (EI), the fast atom impact method (FAB), the electrospray ionization method (ESI), and the inductively coupled plasma method (ICP).

能夠將核磁共振光譜(NMR)用於由通式(1-1)～(1-3)表示的化合物的鑑定。NMR測定中，能夠根據原子的鍵結狀態等而得知化學位移或耦合的資訊，因此能夠獲得化合物固有的光譜，並且能夠鑑定化合物。能夠將少量的試料溶於各種氘代溶劑(deuterated solvent)來實行測定。 能夠藉由示差掃描熱分析(DSC)來實行由通式(1-1)～(1-3)表示的化合物的熱穩定性的評估。能夠藉由在試料產生相變和熔化等的熱變化的情況下偵測與標準試料的熱量差異，來實行DSC測定。DSC測定中，能夠得知化合物的熔點和玻璃轉化溫度。Nuclear magnetic resonance spectroscopy (NMR) can be used for the identification of the compounds represented by the general formulas (1-1) to (1-3). In NMR measurement, chemical shift or coupling information can be known based on the bonding state of atoms, etc., so a spectrum unique to the compound can be obtained and the compound can be identified. A small amount of sample can be dissolved in various deuterated solvents to perform measurement. The evaluation of the thermal stability of the compounds represented by the general formulae (1-1) to (1-3) can be performed by differential scanning calorimetry (DSC). The DSC measurement can be performed by detecting the difference in heat from the standard sample when the sample undergoes thermal changes such as phase change and melting. In the DSC measurement, the melting point and glass transition temperature of the compound can be known.

藉由測定由通式(1-1)～(1-3)表示的化合物的紫外線可見光吸收光譜(UV/VIS)、螢光光譜(PL)、磷光光譜，不僅能夠得知化合物特有的UV吸收波長、螢光波長、磷光波長，還能夠得知化合物的能隙(bandgap)、螢光量子產率、三重態能量等的資訊。 能夠藉由循環伏安法(CV)，來測定由通式(1-1)～(1-3)表示的化合物的最高占據分子軌域(HOMO)能階和最低未占分子軌域(LUMO)能階。又，亦能夠使用游離電位(IP)來作為與HOMO能階相同的指標。 進一步，亦能夠使用下述方法：根據UV吸收波長來求得光學能隙，並根據HOMO能階(或IP)，以計算來求得LUMO能階(或Ea)。By measuring the ultraviolet visible light absorption spectrum (UV/VIS), fluorescence spectrum (PL), and phosphorescence spectrum of the compounds represented by the general formulas (1-1) to (1-3), not only the unique UV absorption of the compound can be known Wavelength, fluorescence wavelength, phosphorescence wavelength, and information such as the bandgap, fluorescence quantum yield, and triplet energy of the compound can also be known. The highest occupied molecular orbital (HOMO) energy level and the lowest unoccupied molecular orbital (LUMO) of the compounds represented by the general formulas (1-1) to (1-3) can be determined by cyclic voltammetry (CV) ) Energy level. In addition, the free potential (IP) can also be used as the same index as the HOMO energy level. Further, it is also possible to use the following method: obtain the optical energy gap according to the UV absorption wavelength, and obtain the LUMO energy level (or Ea) by calculation according to the HOMO energy level (or IP).

本發明的有機電子裝置的一態樣，包含有機EL元件，較佳是包含藍色發光有機EL元件，該有機EL元件在陰極與陽極之間具備發光層及電洞傳輸層，該電洞傳輸層配置於前述發光層的前述陽極側，前述電洞傳輸層包含由通式(1-1)～(1-3)表示的化合物。 第1圖是用以說明本發明的有機電子裝置中包含的有機EL元件的一例的概略剖面圖。第1圖所示的有機EL元件1，具有積層結構，該積層結構是在基板2上依序形成第1電極9(陽極)、電洞注入層8、電洞傳輸層7、發光層6、電子傳輸層5、電子注入層4、及第2電極3(陰極)而成。 本發明的有機電子裝置中包含的有機EL元件，可具有經積層1層或2層以上的電洞傳輸層。又，同樣地，本發明的有機EL元件的其他層(例如發光層和電子傳輸層)亦可以是經積層1層或2層以上的態樣。An aspect of the organic electronic device of the present invention includes an organic EL element, preferably a blue light-emitting organic EL element, the organic EL element is provided with a light-emitting layer and a hole transport layer between the cathode and the anode, and the hole transport The layer is arranged on the anode side of the light-emitting layer, and the hole transport layer contains compounds represented by general formulas (1-1) to (1-3). FIG. 1 is a schematic cross-sectional view for explaining an example of the organic EL element included in the organic electronic device of the present invention. The organic EL element 1 shown in FIG. 1 has a laminated structure in which a first electrode 9 (anode), a hole injection layer 8, a hole transport layer 7, a light emitting layer 6, and a light emitting layer 6 are sequentially formed on a substrate 2. The electron transport layer 5, the electron injection layer 4, and the second electrode 3 (cathode) are formed. The organic EL element included in the organic electronic device of the present invention may have a hole transport layer in which one layer or two or more layers are laminated. In addition, similarly, the other layers (for example, the light-emitting layer and the electron transport layer) of the organic EL device of the present invention may be formed by stacking one layer or two or more layers.

第1圖所示的有機EL元件1，其形成於基板2上的構成有機EL元件的積層結構全部都是由有機化合物所構成。 再者，第1圖所示的有機EL元件1，亦可以是混成有機-無機電場發光元件(HOILED元件)，其在形成於基板2上的構成有機EL元件1的積層結構中包含由無機化合物所構成的層。此時，例如能夠設為：在第1圖所示的有機EL元件1中，設置有作為由無機化合物所構成的層的由無機氧化物所構成的電子注入層4、及由無機氧化物所構成的電洞注入層8。與有機化合物相比，無機化合物較穩定，因此與不含由無機化合物所構成的層之有機EL元件相比，HOILED元件對於氧或水的耐性較高而較佳。In the organic EL element 1 shown in FIG. 1, all the layered structures constituting the organic EL element formed on the substrate 2 are made of organic compounds. Furthermore, the organic EL element 1 shown in FIG. 1 may also be a hybrid organic-inorganic electroluminescent element (HOILED element), which includes an inorganic compound in the multilayer structure forming the organic EL element 1 formed on the substrate 2 The layers constituted. At this time, for example, the organic EL element 1 shown in FIG. 1 is provided with an electron injection layer 4 made of an inorganic oxide as a layer made of an inorganic compound, and an electron injection layer 4 made of an inorganic oxide. Constructed hole injection layer 8. Compared with organic compounds, inorganic compounds are more stable. Therefore, HOILED elements are more resistant to oxygen or water than organic EL elements that do not contain a layer composed of inorganic compounds.

又，第1圖所示的有機EL元件1中，雖然舉出設置了電子注入層4和電洞注入層8的情況為例來進行說明，但是例如可以沒有電子注入層4及/或電洞注入層8。又，第1圖所示的有機EL元件1中，可設置由無機化合物所構成的電子注入層來取代由有機化合物所構成的電子注入層4，亦可設置由無機化合物所構成的電洞注入層來取代由有機化合物所構成的電洞注入層8。In addition, in the organic EL element 1 shown in FIG. 1, although the case where the electron injection layer 4 and the hole injection layer 8 are provided is taken as an example for description, for example, the electron injection layer 4 and/or the hole may not be provided. Injection layer 8. In addition, in the organic EL element 1 shown in Fig. 1, an electron injection layer composed of an inorganic compound may be provided instead of the electron injection layer 4 composed of an organic compound, or a hole injection layer composed of an inorganic compound may be provided. Layer to replace the hole injection layer 8 composed of an organic compound.

第1圖所示的有機EL元件1，可以是在基板2側的相反側取出光的上發光(top emission)型，亦可以是在基板2側取出光的下發光型(bottom emission)。 又，第1圖所示的有機EL元件1，是下述順序結構：在基板2與發光層6之間配置有作為陽極來發揮功能的第1電極9。The organic EL element 1 shown in FIG. 1 may be a top emission type that extracts light on the side opposite to the substrate 2 side, or a bottom emission type that extracts light on the substrate 2 side. In addition, the organic EL element 1 shown in FIG. 1 has a sequential structure in which a first electrode 9 that functions as an anode is arranged between the substrate 2 and the light-emitting layer 6.

作為基板2的材料，可列舉：聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚丙烯、環烯烴聚合物、聚醯胺、聚醚碸、聚甲基丙烯酸甲酯、聚碳酸酯、聚丙烯酸酯這樣的樹脂材料；或，石英玻璃、鈉玻璃這樣玻璃材料等；能夠使用這些材料的1種或2種以上。Examples of the material of the substrate 2 include: polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyether chrysene, polymethyl methacrylate, poly Resin materials such as carbonate and polyacrylate; or glass materials such as quartz glass and soda glass; one or two or more of these materials can be used.

當有機EL元件1是下發光型時，作為基板2的材料，是使用透明的材料。 當有機EL元件1是上發光型時，作為基板2的材料，不僅能夠使用透明的材料，亦能夠使用不透明的材料。作為不透明基板，可列舉例如：由氧化鋁這樣的陶瓷材料所構成的基板、在不銹鋼這樣的金屬基板的表面形成氧化膜(絕緣膜形成而得的基板、由樹脂材料所構成的基板。When the organic EL element 1 is a down-emission type, a transparent material is used as the material of the substrate 2. When the organic EL element 1 is an upper emission type, as the material of the substrate 2, not only a transparent material but also an opaque material can be used. Examples of the opaque substrate include a substrate made of a ceramic material such as alumina, an oxide film formed on the surface of a metal substrate such as stainless steel (a substrate obtained by forming an insulating film, and a substrate made of a resin material.

第1圖所示的有機EL元件1中的第1電極9，是作為陽極來發揮功能機能。作為第1電極9的材料，可列舉例如：氧化銦錫(ITO)、氧化銦鋅(IZO)、氟摻雜氧化錫(FTO)、In3 O3 、SnO2 、含Sb之SnO2 、含Al之ZnO等的氧化物。其中，較佳是使用ITO、IZO、FTO來作為第1電極9的材料。The first electrode 9 in the organic EL element 1 shown in FIG. 1 functions as an anode. Examples of materials for the first electrode 9 include indium tin oxide (ITO), indium zinc oxide (IZO), fluorine-doped tin oxide (FTO), In 3 O 3 , SnO 2 , Sb-containing SnO 2 , Al oxides such as ZnO. Among them, it is preferable to use ITO, IZO, or FTO as the material of the first electrode 9.

能夠根據陽極的功函數與電洞傳輸層的IP的關係、電荷傳輸特性等的觀點，來選擇用於電洞注入層8的材料。能夠使用例如：聚(3,4-伸乙二氧基噻吩)：聚(苯乙烯磺酸鹽)(簡稱：PEDOT:PSS)、以銅酞青(簡稱：CuPc)作為代表的酞青化合物、鉬氧化物(MoOx )、氧化釩(V2 O5 )、2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮雜聯伸三苯(HAT-CN)這樣的受體性雜環化合物。只要是具有適當的IP和電荷傳輸特性的化合物，不論低分子、高分子，能夠選擇各種有機化合物、無機化合物。又，亦能夠將2種以上的這些材料組合使用。The material used for the hole injection layer 8 can be selected from the viewpoint of the relationship between the work function of the anode and the IP of the hole transport layer, charge transport characteristics, and the like. For example, poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (abbreviation: PEDOT:PSS), phthalocyanine compound represented by copper phthalocyanine (abbreviation: CuPc), Molybdenum oxide (MoO x ), vanadium oxide (V 2 O 5 ), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazaxane Acceptor heterocyclic compounds such as benzene (HAT-CN). As long as it is a compound with appropriate IP and charge transport properties, regardless of low molecular weight or high molecular weight, various organic compounds and inorganic compounds can be selected. In addition, two or more of these materials can also be used in combination.

電洞傳輸層7，包含由通式(1-1)～(1-3)表示的化合物。該化合物，藉由具有前述通式所規定的2-取代茀骨架，能夠具有適當的HOMO能階和LUMO能階，且光穩定性、電穩定性及熱穩定性優異。因此，能夠提高發光層内的電荷的再結合效率，並且能夠實現一種更高發光效率且長壽命的有機EL元件。The hole transport layer 7 contains compounds represented by general formulas (1-1) to (1-3). This compound, by having the 2-substituted sulphur skeleton defined by the aforementioned general formula, can have an appropriate HOMO energy level and LUMO energy level, and is excellent in light stability, electrical stability, and thermal stability. Therefore, the recombination efficiency of charges in the light-emitting layer can be improved, and an organic EL element with higher light-emitting efficiency and long life can be realized.

由通式(1-1)～(1-3)表示的化合物亦能夠單獨作為電洞傳輸材料來使用，亦能夠與1種或2種以上的既有的電洞傳輸性材料混合使用。作為既有的電洞傳輸性材料，能夠使用例如：N,N-二聯苯基-N’-三聯苯基-N’-苯基聯苯胺(簡稱：HT1)、N,N’-二苯基-N,N’-二(α-萘基)聯苯胺(簡稱：NPD)、N,N’-二苯基-N,N’-二(間甲苯基)聯苯胺(簡稱：TPD)、1,1-雙[4-[N,N-二(對甲苯基)胺基]苯基]環己烷(簡稱：TAPC)等的芳香族胺化合物；或，4,4’,4’’-三-9-咔唑基三苯基胺(簡稱：TCTA)、1,3-雙(咔唑-9-基)苯(簡稱：mCP)等的咔唑衍生物。The compounds represented by the general formulas (1-1) to (1-3) can also be used alone as a hole-transporting material, or can be used in combination with one or more types of existing hole-transporting materials. As an existing hole-transporting material, for example, N,N-diphenyl-N'-terphenyl-N'-phenylbenzidine (abbreviation: HT1), N,N'-diphenyl can be used -N,N'-bis(α-naphthyl)benzidine (abbreviation: NPD), N,N'-diphenyl-N,N'-bis(m-tolyl)benzidine (abbreviation: TPD), 1,1-bis[4-[N,N-bis(p-tolyl)amino]phenyl]cyclohexane (abbreviation: TAPC) and other aromatic amine compounds; or, 4,4',4'' -Carbazole derivatives such as tri-9-carbazolyl triphenylamine (abbreviation: TCTA) and 1,3-bis(carbazol-9-yl)benzene (abbreviation: mCP).

能夠將螢光材料、或磷光材料用於發光層6。發光材料，亦能夠使能夠實行電荷傳輸和電荷再結合的主體材料中含有發光材料(客體材料)來加以使用。 主體材料，能夠使用具有電洞傳輸性和電子傳輸性的雙極性電荷傳輸性的材料。又，由於本發明的電洞傳輸材料的電子阻止性能亦優異，因此亦能夠將電子傳輸性的材料用於主體材料。A fluorescent material or a phosphorescent material can be used for the light-emitting layer 6. The luminescent material can also be used by including a luminescent material (guest material) in a host material capable of charge transport and charge recombination. The host material can be a bipolar charge-transporting material with hole-transporting properties and electron-transporting properties. In addition, since the hole transport material of the present invention also has excellent electron blocking performance, it is also possible to use electron transporting materials for the host material.

作為主體材料，能夠使用例如：鋁錯合物、鈹錯合物等的金屬錯合物；蒽衍生物、噁二唑衍生物、苯并咪唑衍生物、菲衍生物。As the host material, for example, metal complexes such as aluminum complexes and beryllium complexes; anthracene derivatives, oxadiazole derivatives, benzimidazole derivatives, and phenanthrene derivatives can be used.

發光材料並無特別限定，作為螢光材料，能夠使用例如：喹吖啶酮、香豆素、紅螢烯(rubrene)、苝及其衍生物；苯并吡喃衍生物、玫瑰紅(rhodamine)衍生物、胺基苯乙烯基衍生物、芘衍生物、芳香族胺衍生物、稠四苯(tetracene)衍生物。又，作為磷光材料，能夠使用例如銥和鉑等的金屬錯合物。能夠使用Ir(ppy)3 等的綠色用發光材料、FIrpic等的藍色用發光材料、(Btp)2 Ir(acac)等的紅色用發光材料。The luminescent material is not particularly limited. As the fluorescent material, for example, quinacridone, coumarin, rubrene, perylene and its derivatives; benzopyran derivatives, rhodamine can be used Derivatives, amino styryl derivatives, pyrene derivatives, aromatic amine derivatives, tetracene derivatives. In addition, as the phosphorescent material, for example, metal complexes such as iridium and platinum can be used. Green light-emitting materials such as Ir(ppy) 3 , blue light-emitting materials such as FIrpic, and red light-emitting materials such as (Btp) 2 Ir(acac) can be used.

作為用於電子傳輸層5的材料，能夠使用例如：以Alq3 、BAlq為首的喹啉酚(quinolinol)衍生物的金屬錯合物；蒽衍生物；吡啶衍生物；嘧啶衍生物；苯并咪唑衍生物；喹噁啉衍生物；啡啉衍生物；三嗪衍生物；咔唑衍生物；***衍生物。 如果將包含適當的LUMO能階的材料之電子傳輸層設置於發光層與陰極或電子注入層之間，則能夠緩和從陰極或電子注入層對電子傳輸層注入電子的電子注入障壁，進一步緩和從電子傳輸層對發光層注入電子的電子注入障壁。又，如果該材料具有適當的HOMO能階，則能夠阻擋在發光層中不進行再結合的情形下流出到相對電極之電洞，並將電洞限制在發光層内，從而提高在發光層内的再結合效率。As a material for the electron transport layer 5, for example , metal complexes of quinolinol derivatives including Alq 3 and BAlq; anthracene derivatives; pyridine derivatives; pyrimidine derivatives; benzimidazoles can be used. Derivatives; Quinoxaline Derivatives; Phenanthroline Derivatives; Triazine Derivatives; Carbazole Derivatives; Triazole Derivatives. If an electron transport layer containing a material with an appropriate LUMO energy level is provided between the light-emitting layer and the cathode or electron injection layer, the electron injection barrier for injecting electrons from the cathode or the electron injection layer to the electron transport layer can be relaxed, and the The electron transport layer is an electron injection barrier for injecting electrons into the light-emitting layer. Moreover, if the material has an appropriate HOMO energy level, it can block the holes that flow out to the opposite electrode without recombination in the light-emitting layer, and confine the holes in the light-emitting layer, thereby increasing the amount of holes in the light-emitting layer. The recombination efficiency.

能夠根據陰極的功函數和電子傳輸層的LUMO能階等的觀點，來選擇用於電子注入層4的材料。當不設置電子傳輸層時，能夠考量發光材料或下述主體材料的LUMO能階來選擇。電子注入材料可以是有機化合物，亦可以是無機化合物。 當電子注入層是由無機化合物所構成時，能夠使用例如：鹼金屬和鹼土類金屬、以及氟化鋰、氟化鈉、氟化鉀、氟化銫、碳酸銫。The material used for the electron injection layer 4 can be selected from the viewpoints of the work function of the cathode and the LUMO energy level of the electron transport layer. When the electron transport layer is not provided, it can be selected in consideration of the LUMO energy level of the luminescent material or the host material described below. The electron injection material can be an organic compound or an inorganic compound. When the electron injection layer is made of an inorganic compound, for example, alkali metals and alkaline earth metals, as well as lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, and cesium carbonate can be used.

有機EL元件的陰極，負責將電子注入電子注入層或電子傳輸層。能夠將功函數相對較小的各種金屬材料、各種合金等作為來陰極發揮作用的材料用於陰極。可列舉例如：鋁、銀、鎂、鈣、金、氧化銦錫(ITO)、氧化銦鋅(IZO)、鎂銦合金(MgIn)、銀合金。 當採用下發光方式時，能夠將由金屬所構成的不透明電極用於陰極。又，亦能夠將陰極設為反射電極。 當採用上發光方式時，能夠將ITO、IZO等的透明電極用於陰極。此處，ITO由於功函數較大，因此變得難以進行電子注入，並且，為了形成ITO膜而使用濺鍍法或離子束蒸鍍法，但是成膜時可能對電子傳輸層等造成損傷。因此，為了改善電子注入並且在成膜時減少對於電子傳輸層的損傷，亦能夠在電子傳輸層與ITO之間設置鎂層或銅酞青層。The cathode of the organic EL element is responsible for injecting electrons into the electron injection layer or electron transport layer. Various metal materials and various alloys with relatively small work functions can be used for the cathode as materials that function as the cathode. Examples include aluminum, silver, magnesium, calcium, gold, indium tin oxide (ITO), indium zinc oxide (IZO), magnesium indium alloy (MgIn), and silver alloy. When the lower emission method is adopted, an opaque electrode made of metal can be used for the cathode. In addition, the cathode can also be used as a reflective electrode. When the upper emission method is adopted, transparent electrodes such as ITO and IZO can be used as the cathode. Here, since ITO has a large work function, it becomes difficult to inject electrons. In order to form an ITO film, a sputtering method or an ion beam vapor deposition method is used, but the electron transport layer or the like may be damaged during film formation. Therefore, in order to improve electron injection and reduce damage to the electron transport layer during film formation, it is also possible to provide a magnesium layer or a copper phthalocyanine layer between the electron transport layer and ITO.

本發明的有機電子裝置中包含的有機光電轉換元件，亦能夠依照上述有機EL元件來製作。 [實施例]The organic photoelectric conversion element included in the organic electronic device of the present invention can also be produced in accordance with the above-mentioned organic EL element. [Example]

以下，參照本發明的實施例來更詳細地進行說明，但是這只是示出本發明的特定的具體例，本發明不限定於這些實施例。Hereinafter, a more detailed description will be given with reference to the embodiments of the present invention, but these are only specific specific examples of the present invention, and the present invention is not limited to these embodiments.

[化合物的合成] (實施例1) 根據以下所示的合成途徑來合成化合物(A)。[Synthesis of compounds] (Example 1) The compound (A) was synthesized according to the synthesis route shown below.

Figure 02_image049
Figure 02_image049

根據以下所示的方法來合成化合物(a-1)。 在具備攪拌子且經氬氣取代的500mL的四口燒瓶中，裝入2-溴三苯基胺(5.31g、16.4mmol)及四氫呋喃(328mL)，並加以攪拌，然後冷卻到－78℃為止。對其滴入正丁基鋰(1.6M己烷溶液、12.5mL、19.7mmol)。攪拌1小時後，加入茀酮(4.43g、24.6mmol)，進一步攪拌1小時。慢慢地添加蒸餾水(50mL)，來使反應停止。將内容物移入分液漏斗，並加入乙酸乙酯，來使有機相與水相分離，然後去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由矽膠管柱層析(展開溶劑：己烷/二氯甲烷＝3/1)來精製所獲得的混合物，而獲得目標的化合物(a-1)(產量為6.21g，產率為89%)。The compound (a-1) was synthesized according to the method shown below. In a 500 mL four-necked flask equipped with a stir bar and replaced with argon, place 2-bromotriphenylamine (5.31 g, 16.4 mmol) and tetrahydrofuran (328 mL), stir, and then cool to -78°C . To this, n-butyllithium (1.6M hexane solution, 12.5 mL, 19.7 mmol) was dropped. After stirring for 1 hour, ketone (4.43 g, 24.6 mmol) was added, and the mixture was further stirred for 1 hour. Slowly add distilled water (50 mL) to stop the reaction. The contents were transferred to a separatory funnel, and ethyl acetate was added to separate the organic phase from the water phase, then the water phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 3/1) to obtain the target compound (a-1) (yield: 6.21 g, yield: 89%) ).

根據以下所示的方法來合成化合物(a-2)。 在具備攪拌子且經氬氣取代的500mL的單口燒瓶中，裝入化合物(a-1)(6.21g、14.6mmol)、二氯甲烷(292mL)、及三氟甲磺酸(0.50mL、5.65mmol)，在室溫攪拌30分鐘。然後，對其慢慢地添加飽和碳酸氫鈉水溶液(30mL)，來使反應停止。將内容物移入分液漏斗，並使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由以甲醇進行清洗來精製所獲得的混合物，而獲得目標的化合物(a-2)(產量為5.41g，產率為91%)。The compound (a-2) was synthesized according to the method shown below. In a 500 mL single-necked flask equipped with a stir bar and substituted with argon, compound (a-1) (6.21 g, 14.6 mmol), dichloromethane (292 mL), and trifluoromethanesulfonic acid (0.50 mL, 5.65 mmol) and stirred at room temperature for 30 minutes. Then, a saturated sodium bicarbonate aqueous solution (30 mL) was slowly added thereto to stop the reaction. Move the contents into a separatory funnel and separate the organic phase from the water phase, then remove the water phase, and further wash the organic phase with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was purified by washing with methanol to obtain the target compound (a-2) (yield: 5.41 g, yield: 91%).

根據以下所示的方法來合成化合物(a-3)。 在具備攪拌子且經氬氣取代的300mL的舒倫克管(Schlenk tube)中，裝入化合物(a-2)(2.00g、4.91mmol)、及二氯甲烷(98mL)，並加以攪拌，然後對其滴入溴(0.78mL、15.2mmol)。在室溫攪拌3小時。然後，將反應容器冷卻到0℃為止，並對其慢慢地添加飽和硫代硫酸鈉水溶液(30mL)，來使反應停止。將内容物移入分液漏斗，並使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由以甲醇進行清洗來精製所獲得的混合物，而獲得目標的化合物(a-3)(產量為2.96g，產率為94%)。The compound (a-3) was synthesized according to the method shown below. In a 300 mL Schlenk tube equipped with a stir bar and substituted with argon, compound (a-2) (2.00 g, 4.91 mmol) and dichloromethane (98 mL) were charged and stirred. Then bromine (0.78 mL, 15.2 mmol) was dropped into it. Stir at room temperature for 3 hours. Then, the reaction container was cooled to 0°C, and a saturated sodium thiosulfate aqueous solution (30 mL) was slowly added thereto to stop the reaction. Move the contents into a separatory funnel and separate the organic phase from the water phase, then remove the water phase, and further wash the organic phase with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was purified by washing with methanol to obtain the target compound (a-3) (yield: 2.96 g, yield: 94%).

根據以下所示的方法來合成化合物(A)。 在具備攪拌子且經氬氣取代的300mL的舒倫克管中，裝入化合物(a-3)(2.96g、4.60mmol)、1-萘硼酸(2.45g、14.2mmol)、碳酸鉀(2.54g、18.4mmol)、甲苯(83mL)、水(9.2mL)、及肆(三苯基膦)鈀(0)(212mg、0.184mmol)，並加以密封後，在100℃攪拌2小時。然後，將反應容器放置冷卻到室溫附近為止。將内容物移入分液漏斗，並使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由矽膠管柱層析(展開溶劑：己烷/乙酸乙酯＝30/1)來精製經濃縮後的所獲得的混合物，然後，以己烷來加以清洗，藉此獲得目標的目標的化合物(A)(產量為928mg，產率為26%)。MS：m/z＝785The compound (A) was synthesized according to the method shown below. In a 300 mL Schlenk tube equipped with a stir bar and replaced by argon, compound (a-3) (2.96 g, 4.60 mmol), 1-naphthaleneboronic acid (2.45 g, 14.2 mmol), potassium carbonate (2.54 g, 18.4 mmol), toluene (83 mL), water (9.2 mL), and tetraphenylphosphine palladium (0) (212 mg, 0.184 mmol) were sealed, and then stirred at 100°C for 2 hours. Then, the reaction vessel was left to cool to around room temperature. Move the contents into a separatory funnel and separate the organic phase from the water phase, then remove the water phase, and further wash the organic phase with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. Purify the obtained mixture after concentration by silica gel column chromatography (developing solvent: hexane/ethyl acetate=30/1), and then wash it with hexane to obtain the target compound (A) (The yield is 928 mg, and the yield is 26%). MS: m/z=785

(實施例2) 根據以下所示的合成途徑來合成化合物(B)。(Example 2) The compound (B) is synthesized according to the synthesis route shown below.

Figure 02_image051
Figure 02_image051

根據以下所示的方法來合成化合物(B)。 在具備攪拌子且經氬氣取代的300mL的舒倫克管中，裝入化合物(a-3)(3.21g、4.99mmol)、2-萘硼酸(2.66g、15.5mmol)、碳酸鉀(2.76g、19.9mmol)、甲苯(90mL)、水(10mL)、及肆(三苯基膦)鈀(0)(231mg、0.199mmol)，並加以密封後，在100℃攪拌3小時。然後，將反應容器放置冷卻到室溫附近為止。將内容物移入分液漏斗，並使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由矽膠管柱層析(展開溶劑：己烷/二氯甲烷＝1/1)來精製經濃縮後的所獲得的混合物，然後，以乙酸乙酯來加以清洗，藉此獲得目標的化合物(B)(產量為1.42g，產率為36%)。MS：m/z＝785The compound (B) was synthesized according to the method shown below. In a 300 mL Schlenk tube equipped with a stir bar and replaced by argon, compound (a-3) (3.21 g, 4.99 mmol), 2-naphthaleneboronic acid (2.66 g, 15.5 mmol), potassium carbonate (2.76 g, 19.9 mmol), toluene (90 mL), water (10 mL), and tetrakis (triphenylphosphine) palladium (0) (231 mg, 0.199 mmol) were sealed, and then stirred at 100°C for 3 hours. Then, the reaction vessel was left to cool to around room temperature. Move the contents into a separatory funnel and separate the organic phase from the water phase, then remove the water phase, and further wash the organic phase with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane=1/1), and then washed with ethyl acetate to obtain the target compound ( B) (The yield is 1.42 g, and the yield is 36%). MS: m/z=785

(實施例3) 根據以下所示的合成途徑來合成化合物(C)。(Example 3) The compound (C) is synthesized according to the synthesis route shown below.

Figure 02_image053
Figure 02_image053

根據以下所示的方法來合成化合物(C)。 在具備攪拌子且經氬氣取代的300mL的舒倫克管中，裝入化合物(a-3)(2.92g、4.53mmol)、二苯并呋喃-4-硼酸(3.07g、14.5mmol)、碳酸鉀(2.50g、18.1mmol)、甲苯(65mL)、水(26mL)、及肆(三苯基膦)鈀(0)(209mg、0.181mmol)，並加以密封後，在100℃攪拌2小時。然後，將反應容器放置冷卻到室溫附近為止。將内容物移入分液漏斗，並使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由矽膠管柱層析(展開溶劑：己烷/乙酸乙酯＝3/1)來精製經濃縮後的所獲得的混合物，然後，以己烷來加以清洗，藉此獲得目標的目標的化合物(C)(產量為900mg，產率為22%)。MS：m/z＝905The compound (C) was synthesized according to the method shown below. In a 300 mL Schlenk tube equipped with a stir bar and substituted with argon, compound (a-3) (2.92 g, 4.53 mmol), dibenzofuran-4-boronic acid (3.07 g, 14.5 mmol), Potassium carbonate (2.50g, 18.1mmol), toluene (65mL), water (26mL), and Si (triphenylphosphine) palladium(0) (209mg, 0.181mmol) were sealed, and then stirred at 100°C for 2 hours . Then, the reaction vessel was left to cool to around room temperature. Move the contents into a separatory funnel and separate the organic phase from the water phase, then remove the water phase, and further wash the organic phase with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. Purify the obtained mixture after concentration by silica gel column chromatography (developing solvent: hexane/ethyl acetate=3/1), and then wash it with hexane to obtain the target compound (C) (Yield is 900 mg, and the yield is 22%). MS: m/z=905

(實施例4) 根據以下所示的合成途徑來合成化合物(D)。(Example 4) The compound (D) was synthesized according to the synthesis route shown below.

Figure 02_image055
Figure 02_image055

根據以下所示的方法來合成化合物(d-1)。 在具備攪拌子且經氬氣取代的300mL的四口燒瓶中，裝入10H-螺[吖啶-9,9’-茀](2.43g、7.34mmol)、N,N-二甲基甲醯胺(147mL)、及1,3-二溴-5,5-二甲基乙內醯脲(2.31g、8.08mmol)，在室溫攪拌2小時。然後，將反應容器冷卻到0℃為止，並對其慢慢地添加飽和硫代硫酸鈉水溶液(30mL)，來使反應停止。將内容物移入分液漏斗，並加入甲苯，來使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由矽膠管柱層析(展開溶劑：己烷/乙酸乙酯＝3/1)來精製所獲得的混合物，而獲得目標的化合物(d-1)(產量為2.60g，產率為72%)。The compound (d-1) was synthesized according to the method shown below. In a 300mL four-necked flask equipped with a stir bar and replaced by argon, put 10H-spiro[acridine-9,9'-茀](2.43g, 7.34mmol), N,N-dimethylformamide Amine (147 mL) and 1,3-dibromo-5,5-dimethylhydantoin (2.31 g, 8.08 mmol) were stirred at room temperature for 2 hours. Then, the reaction container was cooled to 0°C, and a saturated sodium thiosulfate aqueous solution (30 mL) was slowly added thereto to stop the reaction. The contents were transferred to a separatory funnel, and toluene was added to separate the organic phase from the water phase, then the water phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate = 3/1) to obtain the target compound (d-1) (yield 2.60 g, yield 72%) ).

根據以下所示的方法來合成化合物(d-2)。 在具備攪拌子且經氬氣取代的50mL的舒倫克管中，裝入化合物(d-1)(1.17g、2.93mmol)、二苯并呋喃-4-硼酸(1.06g、5.02mmol)、磷酸鉀(870mg、7.17mmol)、甲苯(16mL)、水(4mL)、及二氯雙[二-三級丁基(4-二甲基胺基苯基)膦]鈀(II)(16.9mg、0.0239mmol)，並加以密封後，在100℃攪拌3小時。然後，將反應容器放置冷卻到室溫附近為止。將内容物移入分液漏斗，並加入二氯甲烷，來使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。以己烷來清洗所獲得的混合物，藉此獲得目標的化合物(d-2)(產量為1.47g，產率為92%)。The compound (d-2) was synthesized according to the method shown below. In a 50 mL Schlenk tube equipped with a stir bar and substituted with argon, compound (d-1) (1.17 g, 2.93 mmol), dibenzofuran-4-boronic acid (1.06 g, 5.02 mmol), Potassium phosphate (870mg, 7.17mmol), toluene (16mL), water (4mL), and dichlorobis[di-tertiarybutyl(4-dimethylaminophenyl)phosphine]palladium(II) (16.9mg , 0.0239mmol) and sealed, and then stirred at 100°C for 3 hours. Then, the reaction vessel was left to cool to around room temperature. The contents were transferred to a separatory funnel, and dichloromethane was added to separate the organic phase from the water phase, then the water phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was washed with hexane, thereby obtaining the target compound (d-2) (yield 1.47 g, yield 92%).

根據以下所示的方法來合成化合物(D)。 在具備攪拌子且經氬氣取代的50mL的舒倫克管中，裝入化合物(d-2)(1.46g、2.19mmol)、2-(4-溴苯基)萘(682mg、2.41mmol)、雙(三-三級丁基膦)鈀(0)(11.2mg、0.0219mmol)、甲苯(22mL)、及三級丁氧基鈉(316mg、3.29mmol)，並加以密封後，在100℃攪拌2小時。然後，將反應容器放置冷卻到室溫附近，並對其加入水(30mL)。將内容物移入分液漏斗，並加入二氯甲烷，來使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由矽膠管柱層析(展開溶劑：己烷/二氯甲烷＝2/1)來精製經濃縮後的所獲得的混合物，然後，以甲苯來加以清洗，藉此獲得目標的化合物(D)(產量為1.52g，產率為80%)。MS：m/z＝865The compound (D) was synthesized according to the method shown below. In a 50 mL Schlenk tube equipped with a stir bar and substituted with argon, compound (d-2) (1.46 g, 2.19 mmol), 2-(4-bromophenyl) naphthalene (682 mg, 2.41 mmol) were charged , Bis (tri-tertiary butyl phosphine) palladium (0) (11.2 mg, 0.0219 mmol), toluene (22 mL), and tertiary butoxy sodium (316 mg, 3.29 mmol), and seal them at 100°C Stir for 2 hours. Then, the reaction vessel was left to cool to around room temperature, and water (30 mL) was added to it. The contents were transferred to a separatory funnel, and dichloromethane was added to separate the organic phase from the water phase, then the water phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 2/1), and then washed with toluene to obtain the target compound (D) (The yield is 1.52g, and the yield is 80%). MS: m/z=865

(實施例5) 根據以下所示的合成途徑來合成化合物(E)。(Example 5) The compound (E) was synthesized according to the synthesis route shown below.

Figure 02_image057
Figure 02_image057

根據以下所示的方法來合成化合物(e-1)。 在具備攪拌子且經氬氣取代的100mL的舒倫克管中，裝入化合物(d-1)(3.35g、6.84mmol)、2-萘硼酸(2.59g、15.0mmol)、碳酸鉀(2.84g、20.5mmol)、甲苯(31mL)、水(3.4mL)、及二氯雙[二-三級丁基(4-二甲基胺基苯基)膦]鈀(II)(14.5mg、0.0205mmol)，並加以密封後，在100℃攪拌3小時。然後，將反應容器放置冷卻到室溫附近，並對其加入己烷(30mL)，然後濾取析出物。以己烷來清洗所獲得的析出物，藉此獲得目標的化合物(e-1)(產量為3.42g，產率為86%)。The compound (e-1) was synthesized according to the method shown below. In a 100 mL Schlenk tube equipped with a stir bar and replaced by argon, compound (d-1) (3.35 g, 6.84 mmol), 2-naphthaleneboronic acid (2.59 g, 15.0 mmol), potassium carbonate (2.84 g, 20.5mmol), toluene (31mL), water (3.4mL), and dichlorobis[di-tertiary butyl (4-dimethylaminophenyl) phosphine] palladium (II) (14.5mg, 0.0205) mmol), and after sealing, the mixture was stirred at 100°C for 3 hours. Then, the reaction vessel was left to cool to around room temperature, and hexane (30 mL) was added thereto, and then the precipitate was collected by filtration. The obtained precipitate was washed with hexane to obtain the target compound (e-1) (yield: 3.42 g, yield: 86%).

根據以下所示的方法來合成化合物(E)。 在具備攪拌子且經氬氣取代的100mL的舒倫克管中，裝入化合物(e-1)(1.80g、3.08mmol)、2-溴-9,9’-螺雙[9H-茀](1.34g、3.39mmol)、雙(三-三級丁基膦)鈀(0)(15.8mg、0.0308mmol)、甲苯(32mL)、及三級丁氧基鈉(445mg、3.73mmol)，並加以密封後，在100℃攪拌4小時。然後，將反應容器放置冷卻到室溫附近，並對其加入水(30mL)。將内容物移入分液漏斗，並使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由矽膠管柱層析(展開溶劑：環己烷/甲苯＝1/1)來精製經濃縮後的所獲得的混合物，然後，以乙酸乙酯來加以清洗，藉此獲得目標的化合物(E)(產量為1.29g，產率為42%)。MS：m/z＝897The compound (E) was synthesized according to the method shown below. In a 100 mL Schlenk tube equipped with a stir bar and substituted with argon, compound (e-1) (1.80 g, 3.08 mmol), 2-bromo-9,9'-spirobis[9H-茀] (1.34g, 3.39mmol), bis(tri-tertiary butylphosphine) palladium(0) (15.8mg, 0.0308mmol), toluene (32mL), and tertiary butoxide sodium (445mg, 3.73mmol), and After sealing, it was stirred at 100°C for 4 hours. Then, the reaction vessel was left to cool to around room temperature, and water (30 mL) was added to it. Move the contents into a separatory funnel and separate the organic phase from the water phase, then remove the water phase, and further wash the organic phase with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture after concentration was purified by silica gel column chromatography (developing solvent: cyclohexane/toluene=1/1), and then washed with ethyl acetate to obtain the target compound (E ) (The yield is 1.29 g, and the yield is 42%). MS: m/z=897

(實施例6) 根據以下所示的合成途徑來合成化合物(F)。(Example 6) The compound (F) is synthesized according to the synthesis route shown below.

Figure 02_image059
Figure 02_image059

根據以下所示的方法來合成化合物(F)。 在具備攪拌子且經氬氣取代的200mL的舒倫克管中，化合物(d-2)(1.65g、2.48mmol)、9-(4-溴苯基)咔唑(1.04g、3.23mmol)、雙(三-三級丁基膦)鈀(0)(50.8mg、0.0993mmol)、甲苯(60mL)、及三級丁氧基鈉(358mg、3.73mmol)，並加以密封後，在100℃攪拌23小時。然後，將反應容器放置冷卻到室溫附近，並對其加入水(30mL)。將内容物移入分液漏斗，並使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由矽膠管柱層析(展開溶劑：己烷/二氯甲烷＝3/1)來精製經濃縮後的所獲得的混合物，然後，以己烷來加以清洗，藉此獲得目標的化合物(F)(產量為862mg，產率為38%)。MS：m/z＝904The compound (F) was synthesized according to the method shown below. In a 200 mL Schlenk tube equipped with a stir bar and replaced by argon, compound (d-2) (1.65 g, 2.48 mmol), 9-(4-bromophenyl) carbazole (1.04 g, 3.23 mmol) , Bis (tri-tertiary butyl phosphine) palladium (0) (50.8mg, 0.0993mmol), toluene (60mL), and tertiary butoxy sodium (358mg, 3.73mmol), and sealed, at 100 ℃ Stir for 23 hours. Then, the reaction vessel was left to cool to around room temperature, and water (30 mL) was added to it. Move the contents into a separatory funnel and separate the organic phase from the water phase, then remove the water phase, and further wash the organic phase with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The mixture obtained after concentration was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 3/1), and then washed with hexane to obtain the target compound (F ) (The yield is 862 mg, and the yield is 38%). MS: m/z=904

(實施例7) 根據以下所示的合成途徑來合成化合物(G)。(Example 7) The compound (G) was synthesized according to the synthesis route shown below.

Figure 02_image061
Figure 02_image061

根據以下所示的方法來合成化合物(g-1)。 在具備攪拌子且經氬氣取代的200mL的舒倫克管中，2-溴苯胺(5.00g、29.1mmol)、1-氯-4-碘苯(17.3g、72.7mmol)、雙(三-三級丁基膦)鈀(0)(594mg、1.16mmol)、甲苯(291mL)、及三級丁氧基鈉(6.98g、72.7mmol)，並加以密封後，在100℃攪拌15小時。然後，將反應容器放置冷卻到室溫附近，並對其加入水(30mL)。將内容物移入分液漏斗，並使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由矽膠管柱層析(展開溶劑:己烷/二氯甲烷＝25/1)來精製經濃縮後的所獲得的混合物，而獲得目標的化合物(g-1)(產量為6.49g，產率為57%)。The compound (g-1) was synthesized according to the method shown below. In a 200 mL Schlenk tube equipped with a stir bar and replaced by argon, 2-bromoaniline (5.00 g, 29.1 mmol), 1-chloro-4-iodobenzene (17.3 g, 72.7 mmol), bis(tri- Tertiary butyl phosphine) palladium (0) (594 mg, 1.16 mmol), toluene (291 mL), and tertiary butoxy sodium (6.98 g, 72.7 mmol) were sealed, and then stirred at 100°C for 15 hours. Then, the reaction vessel was left to cool to around room temperature, and water (30 mL) was added to it. Move the contents into a separatory funnel and separate the organic phase from the water phase, then remove the water phase, and further wash the organic phase with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture after concentration was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane=25/1) to obtain the target compound (g-1) (yield 6.49g, yield The rate is 57%).

根據以下所示的方法來合成化合物(g-2)。 在具備攪拌子且經氬氣取代的500mL的四口燒瓶中，裝入化合物(g-1)(9.11g、23.2mmol)及四氫呋喃(232mL)，並加以攪拌，然後冷卻到－78℃為止。對其滴入正丁基鋰(1.6M己烷溶液、17.7mL、27.8mmol)。攪拌1小時後，加入茀酮(6.27g、34.8mmol)，進一步攪拌1小時。然後，對其慢慢地添加蒸餾水(50mL)，來使反應停止。將内容物移入分液漏斗，並加入乙酸乙酯，來使有機相與水相分離，然後去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由矽膠管柱層析(展開溶劑：己烷/二氯甲烷＝3/1)來精製所獲得的混合物，而獲得目標的化合物(g-2)(產量為4.54g，產率為40%)。The compound (g-2) was synthesized according to the method shown below. A 500 mL four-necked flask equipped with a stir bar and substituted with argon was charged with compound (g-1) (9.11 g, 23.2 mmol) and tetrahydrofuran (232 mL), stirred, and then cooled to -78°C. To this, n-butyllithium (1.6M hexane solution, 17.7 mL, 27.8 mmol) was dropped. After stirring for 1 hour, ketone (6.27 g, 34.8 mmol) was added, and the mixture was further stirred for 1 hour. Then, distilled water (50 mL) was slowly added thereto to stop the reaction. The contents were transferred to a separatory funnel, and ethyl acetate was added to separate the organic phase from the water phase, then the water phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane=3/1) to obtain the target compound (g-2) (yield: 4.54g, yield: 40%) ).

根據以下所示的方法來合成化合物(g-3)。 在具備攪拌子且經氬氣取代的500mL的單口燒瓶中，裝入化合物(g-2)(4.64g、9.39mmol)、二氯甲烷(188mL)、及三氟甲磺酸(0.25mL、2.82mmol)，並在室溫攪拌1小時。然後，對其慢慢地添加飽和碳酸氫鈉水溶液(30mL)，來使反應停止。將内容物移入分液漏斗，並使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。以己烷來清洗所獲得的混合物，藉此獲得目標的化合物(g-3)(產量為2.68g，產率為60%)。The compound (g-3) was synthesized according to the method shown below. In a 500 mL single-necked flask equipped with a stir bar and replaced with argon, compound (g-2) (4.64 g, 9.39 mmol), dichloromethane (188 mL), and trifluoromethanesulfonic acid (0.25 mL, 2.82 mmol) and stirred at room temperature for 1 hour. Then, a saturated sodium bicarbonate aqueous solution (30 mL) was slowly added thereto to stop the reaction. Move the contents into a separatory funnel and separate the organic phase from the water phase, then remove the water phase, and further wash the organic phase with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was washed with hexane, thereby obtaining the target compound (g-3) (yield 2.68 g, yield 60%).

根據以下所示的方法來合成化合物(G)。 在具備攪拌子且經氬氣取代的300mL的舒倫克管中，裝入化合物(g-3)(2.68g、5.61mmol)、二苯并呋喃-4-硼酸(4.17g、19.7mmol)、磷酸鉀(4.77g、22.5mmol)、二噁烷(112mL)、及雙(二-三級丁基(4-二甲基胺基苯基)膦)二氯鈀(Ⅱ)(159mg、0.225mmol)，並加以密封後，在110℃攪拌30小時。然後，將反應容器放置冷卻到室溫附近為止。將内容物移入分液漏斗，並加入水，來使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由矽膠管柱層析(展開溶劑：己烷/二氯甲烷＝1/1)來精製經濃縮後的所獲得的混合物，然後，以己烷來加以清洗，藉此獲得目標的化合物(G)(產量為1.45g，產率為35%)。MS：m/z＝739The compound (G) was synthesized according to the method shown below. In a 300 mL Schlenk tube equipped with a stir bar and substituted with argon, compound (g-3) (2.68 g, 5.61 mmol), dibenzofuran-4-boronic acid (4.17 g, 19.7 mmol), Potassium phosphate (4.77g, 22.5mmol), dioxane (112mL), and bis(di-tertiary butyl (4-dimethylaminophenyl) phosphine) dichloropalladium (II) (159mg, 0.225mmol) ), and after sealing, it was stirred at 110°C for 30 hours. Then, the reaction vessel was left to cool to around room temperature. The contents are transferred to a separatory funnel, and water is added to separate the organic phase from the water phase, then the water phase is removed, and the organic phase is further washed with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The mixture obtained after concentration was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane=1/1), and then washed with hexane to obtain the target compound (G ) (The yield is 1.45 g, and the yield is 35%). MS: m/z=739

(實施例8) 根據以下所示的合成途徑來合成化合物(H)。(Example 8) The compound (H) is synthesized according to the synthesis route shown below.

Figure 02_image063
Figure 02_image063

根據以下所示的方法來合成化合物(h-1)。 在具備攪拌子且經氬氣取代的200mL的舒倫克管中，裝入2-溴-9-茀酮(2.50g、9.65mmol)、苯基硼酸(1.29g、10.6mmol)、碳酸鉀(2.67g、19.3mmol)、甲苯(87mL)、水(9.7mL)、及肆(三苯基膦)鈀(0)(223mg、0.193mmol)，並加以密封後，在100℃攪拌4小時。然後，將反應容器放置冷卻到室溫附近為止。將内容物移入分液漏斗，並使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。以己烷來清洗經濃縮後的所獲得的混合物，藉此獲得目標的化合物(h-1)(產量為2.33g，產率為94%)。The compound (h-1) was synthesized according to the method shown below. In a 200mL Schlenk tube equipped with a stir bar and replaced by argon, fill with 2-bromo-9-chondone (2.50g, 9.65mmol), phenylboronic acid (1.29g, 10.6mmol), potassium carbonate ( 2.67 g, 19.3 mmol), toluene (87 mL), water (9.7 mL), and tetraphenylphosphine palladium (0) (223 mg, 0.193 mmol) were sealed, and then stirred at 100°C for 4 hours. Then, the reaction vessel was left to cool to around room temperature. Move the contents into a separatory funnel and separate the organic phase from the water phase, then remove the water phase, and further wash the organic phase with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was washed with hexane, thereby obtaining the target compound (h-1) (yield 2.33 g, yield 94%).

根據以下所示的方法來合成化合物(h-2)。 在具備攪拌子且經氬氣取代的500mL的四口燒瓶中，裝入2-溴三苯基胺(2.60g、8.02mmol)和四氫呋喃(160mL)，並加以攪拌，然後冷卻到－78℃為止。對其滴入正丁基鋰(1.6M己烷溶液、6.13mL、9.62mmol)。攪拌1小時後，加入化合物(h-1)(2.45g、9.62mmol)，進一步攪拌1小時。慢慢地添加蒸餾水(50mL)，來使反應停止。將内容物移入分液漏斗，並加入乙酸乙酯，來使有機相與水相分離，然後去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由矽膠管柱層析(展開溶劑：己烷/二氯甲烷＝3/1)來精製所獲得的混合物，而獲得目標的化合物(h-2)(產量為3.63g，產率為90%)。The compound (h-2) was synthesized according to the method shown below. In a 500mL four-necked flask equipped with a stir bar and replaced by argon, charge 2-bromotriphenylamine (2.60g, 8.02mmol) and tetrahydrofuran (160mL), stir, and then cool to -78°C . N-butyllithium (1.6M hexane solution, 6.13 mL, 9.62 mmol) was dropped into it. After stirring for 1 hour, compound (h-1) (2.45 g, 9.62 mmol) was added, and the mixture was further stirred for 1 hour. Slowly add distilled water (50 mL) to stop the reaction. The contents were transferred to a separatory funnel, and ethyl acetate was added to separate the organic phase from the water phase, then the water phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 3/1) to obtain the target compound (h-2) (yield 3.63 g, yield 90%) ).

根據以下所示的方法來合成化合物(h-3)。 在具備攪拌子的300mL的單口燒瓶中，裝入化合物(h-2)(3.63g、7.24mmol)、二氯甲烷(145mL)、及三氟甲磺酸(0.25mL、2.82mmol)，在室溫攪拌30分鐘。然後，對其慢慢地添加飽和碳酸氫鈉水溶液(30mL)，來使反應停止。將内容物移入分液漏斗，並使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。以甲醇來清洗所獲得的混合物，藉此獲得目標的化合物(h-3)(產量為3.22g，產率為92%)。The compound (h-3) was synthesized according to the method shown below. In a 300 mL single-necked flask equipped with a stir bar, compound (h-2) (3.63 g, 7.24 mmol), dichloromethane (145 mL), and trifluoromethanesulfonic acid (0.25 mL, 2.82 mmol) were charged in the chamber. Warm stirring for 30 minutes. Then, a saturated sodium bicarbonate aqueous solution (30 mL) was slowly added thereto to stop the reaction. Move the contents into a separatory funnel and separate the organic phase from the water phase, then remove the water phase, and further wash the organic phase with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was washed with methanol, thereby obtaining the target compound (h-3) (the yield was 3.22 g, the yield was 92%).

根據以下所示的方法來合成化合物(h-4)。 在具備攪拌子且經氬氣取代的300mL的舒倫克管中，裝入化合物(h-3)(3.22g、6.66mmol)和二氯甲烷(133mL)，並加以攪拌，對其滴入溴(1.20mL、23.3mmol)。在室溫攪拌2小時。然後，將反應容器冷卻到0℃為止，並對其慢慢地添加飽和硫代硫酸鈉水溶液(30mL)，來使反應停止。將内容物移入分液漏斗，並使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。以甲醇來清洗所獲得的混合物，藉此獲得目標的化合物(h-4)(產量為5.01g，產率為100%)。The compound (h-4) was synthesized according to the method shown below. In a 300 mL Schlenk tube equipped with a stir bar and substituted with argon, compound (h-3) (3.22 g, 6.66 mmol) and dichloromethane (133 mL) were charged, and stirred, and bromine was added dropwise to it. (1.20 mL, 23.3 mmol). Stir at room temperature for 2 hours. Then, the reaction container was cooled to 0°C, and a saturated sodium thiosulfate aqueous solution (30 mL) was slowly added thereto to stop the reaction. Move the contents into a separatory funnel and separate the organic phase from the water phase, then remove the water phase, and further wash the organic phase with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was washed with methanol, thereby obtaining the target compound (h-4) (yield of 5.01 g, yield of 100%).

根據以下所示的方法來合成化合物(H)。 在具備攪拌子且經氬氣取代的100mL的舒倫克管中，裝入化合物(h-4)(3.46g、4.80mmol)、2-萘硼酸(2.64g、15.4mmol)、碳酸鉀(2.65g、19.2mmol)、甲苯(22mL)、水(2.4mL)、及雙(二-三級丁基(4-二甲基胺基苯基)膦)二氯鈀(Ⅱ)(34.0mg、0.0480mmol)，並加以密封後，在100℃攪拌3小時。然後，將反應容器放置冷卻到室溫附近為止。將内容物移入分液漏斗，並使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由矽膠管柱層析(展開溶劑：二氯甲烷)來精製經濃縮後的所獲得的混合物，然後，以乙酸乙酯來加以清洗，藉此獲得目標的化合物(H)(產量為734mg，產率為18%)。MS：m/z＝861The compound (H) was synthesized according to the method shown below. In a 100 mL Schlenk tube equipped with a stir bar and replaced by argon, compound (h-4) (3.46 g, 4.80 mmol), 2-naphthaleneboronic acid (2.64 g, 15.4 mmol), potassium carbonate (2.65 g, 19.2mmol), toluene (22mL), water (2.4mL), and bis(di-tertiary butyl (4-dimethylaminophenyl) phosphine) dichloropalladium (Ⅱ) (34.0mg, 0.0480 mmol), and after sealing, the mixture was stirred at 100°C for 3 hours. Then, the reaction vessel was left to cool to around room temperature. Move the contents into a separatory funnel and separate the organic phase from the water phase, then remove the water phase, and further wash the organic phase with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture after concentration was purified by silica gel column chromatography (developing solvent: dichloromethane), and then washed with ethyl acetate to obtain the target compound (H) (yield: 734 mg, The yield is 18%). MS: m/z=861

(實施例9) 根據以下所示的合成途徑來合成化合物(I)。(Example 9) The compound (I) was synthesized according to the synthesis route shown below.

Figure 02_image065
Figure 02_image065

根據以下所示的方法來合成化合物(i-1)。 在具備攪拌子且經氬氣取代的500mL的四口燒瓶中，裝入2-溴二苯基胺(2.50g、10.1mmol)和三級丁基甲基醚(50mL)，並加以攪拌，然後冷卻到0℃為止。對其滴入正丁基鋰(1.6M己烷溶液、13.0mL、20.2mmol)。攪拌1小時後，加入11H-苯并[b]茀-11-酮(4.64g、20.2mmol)，進一步攪拌1小時。然後，對其慢慢地添加蒸餾水(20mL)，來使反應停止。將内容物移入分液漏斗，並加入乙酸乙酯，來使有機相與水相分離，然後去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。將所獲得的混合物裝入具備攪拌子的200mL的單口燒瓶中，並裝入二氯甲烷(34mL)和三氟甲磺酸(0.267mL、3.02mmol)，然後在室溫攪拌30分鐘。然後，對其慢慢地添加飽和碳酸氫鈉水溶液(30mL)，來使反應停止。將内容物移入分液漏斗，並使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由矽膠管柱層析(展開溶劑：己烷/二氯甲烷＝3/1)來精製所獲得的混合物，而獲得目標的化合物(i-1)(產量為3.78g，產率為98%)。The compound (i-1) was synthesized according to the method shown below. In a 500 mL four-neck flask equipped with a stir bar and substituted with argon, charge 2-bromodiphenylamine (2.50 g, 10.1 mmol) and tertiary butyl methyl ether (50 mL), stir, and then cool to Up to 0°C. N-butyllithium (1.6M hexane solution, 13.0 mL, 20.2 mmol) was dropped into it. After stirring for 1 hour, 11H-benzo[b]茀-11-one (4.64 g, 20.2 mmol) was added, and the mixture was further stirred for 1 hour. Then, distilled water (20 mL) was slowly added thereto to stop the reaction. The contents were transferred to a separatory funnel, and ethyl acetate was added to separate the organic phase from the water phase, then the water phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was charged into a 200 mL single-necked flask equipped with a stirring bar, dichloromethane (34 mL) and trifluoromethanesulfonic acid (0.267 mL, 3.02 mmol) were charged, and then stirred at room temperature for 30 minutes. Then, a saturated sodium bicarbonate aqueous solution (30 mL) was slowly added thereto to stop the reaction. Move the contents into a separatory funnel and separate the organic phase from the water phase, then remove the water phase, and further wash the organic phase with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 3/1) to obtain the target compound (i-1) (yield 3.78 g, yield 98%) ).

根據以下所示的方法來合成化合物(i-2)。 在具備攪拌子且經氬氣取代的300mL的舒倫克管中，裝入化合物(i-1)(3.78g、9.91mmol)、N,N-二甲基甲醯胺(99mL)、及1,3-二溴-5,5-二甲基乙內醯脲(2.85g、9.91mmol)，並在室溫攪拌1小時。然後，對其慢慢地添加5%亞硫酸鈉水溶液(20mL)，來使反應停止。將内容物移入分液漏斗，並加入甲苯，來使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。以己烷來清洗所獲得的混合物，藉此獲得目標的化合物(i-2)(產量為4.31g，產率為81%)。The compound (i-2) was synthesized according to the method shown below. In a 300 mL Schlenk tube equipped with a stir bar and replaced by argon, compound (i-1) (3.78 g, 9.91 mmol), N,N-dimethylformamide (99 mL), and 1 ,3-Dibromo-5,5-dimethylhydantoin (2.85 g, 9.91 mmol), and stirred at room temperature for 1 hour. Then, a 5% sodium sulfite aqueous solution (20 mL) was slowly added thereto to stop the reaction. The contents were transferred to a separatory funnel, and toluene was added to separate the organic phase from the water phase, then the water phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was washed with hexane, thereby obtaining the target compound (i-2) (yield: 4.31 g, yield: 81%).

根據以下所示的方法來合成化合物(i-3)。 在具備攪拌子且經氬氣取代的100mL的舒倫克管中，裝入化合物(i-2)(2.30g、4.27mmol)、2-萘硼酸(1.64g、9.38mmol)、碳酸鉀(1.77g、12.8mmol)、甲苯(19mL)、水(2.1mL)、及雙(二-三級丁基(4-二甲基胺基苯基)膦)二氯鈀(Ⅱ)(9.1mg、0.0128mmol)，並加以密封後，在100℃攪拌3小時。然後，將反應容器放置冷卻到室溫附近為止。對其加入蒸餾水(5mL)、己烷(20mL)，並濾取析出物，藉此獲得目標的化合物(i-3)(產量為2.35g，產率為87%)。The compound (i-3) was synthesized according to the method shown below. In a 100 mL Schlenk tube equipped with a stir bar and replaced by argon, compound (i-2) (2.30 g, 4.27 mmol), 2-naphthaleneboronic acid (1.64 g, 9.38 mmol), potassium carbonate (1.77 g, 12.8mmol), toluene (19mL), water (2.1mL), and bis (di-tertiary butyl (4-dimethylaminophenyl) phosphine) dichloropalladium (II) (9.1mg, 0.0128) mmol), and after sealing, the mixture was stirred at 100°C for 3 hours. Then, the reaction vessel was left to cool to around room temperature. Distilled water (5 mL) and hexane (20 mL) were added thereto, and the precipitate was collected by filtration, thereby obtaining the target compound (i-3) (yield 2.35 g, yield 87%).

根據以下所示的方法來合成化合物(I)。 具備攪拌子且經氬氣取代的150mL的舒倫克管中，裝入化合物(i-3)(2.94g、4.65mmol)、2-(4-溴苯基)萘(1.45g、5.11mmol)、雙(三-三級丁基膦)鈀(0)(23.7mg、0.047mmol)、甲苯(67mL)、及三級丁氧基鈉(670mg、6.97mmol)，並加以密封後，在100℃攪拌2小時。然後，將反應容器放置冷卻到室溫附近，並對其加入水(30mL)。將内容物移入分液漏斗，並使有機相與水相分離後，去除水相，進一步對有機相進行水洗。以硫酸鈉來使有機相乾燥。然後，藉由過濾來去除硫酸鈉，並濃縮有機相。藉由矽膠管柱層析(展開溶劑：環己烷/四氫呋喃＝1/1)來精製經濃縮後的所獲得的混合物，然後，以乙酸乙酯來加以清洗，藉此獲得目標的化合物(I)(產量為1.67g，產率為35%)。MS：m/z＝835The compound (I) was synthesized according to the method shown below. A 150 mL Schlenk tube equipped with a stir bar and replaced by argon is charged with compound (i-3) (2.94 g, 4.65 mmol), 2-(4-bromophenyl) naphthalene (1.45 g, 5.11 mmol) , Bis (tri-tertiary butyl phosphine) palladium (0) (23.7mg, 0.047mmol), toluene (67mL), and tertiary butoxy sodium (670mg, 6.97mmol), and after sealing, at 100 ℃ Stir for 2 hours. Then, the reaction vessel was left to cool to around room temperature, and water (30 mL) was added to it. Move the contents into a separatory funnel and separate the organic phase from the water phase, then remove the water phase, and further wash the organic phase with water. The organic phase was dried with sodium sulfate. Then, the sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture after concentration was purified by silica gel column chromatography (developing solvent: cyclohexane/tetrahydrofuran=1/1), and then washed with ethyl acetate to obtain the target compound (I ) (The yield is 1.67 g, and the yield is 35%). MS: m/z=835

(實施例10) 實行上述實施例1中合成的化合物(A)、上述實施例2中合成的化合物(B)、上述實施例3中合成的化合物(C)、上述實施例4中合成的化合物(D)、上述實施例5中合成的化合物(E)、上述實施例6中合成的化合物(F)、上述實施例7中合成的化合物(G)、上述實施例8中合成的化合物(H)、上述實施例9中合成的化合物(I)、及下述比較化合物(X)～(Z)的DSC測定。

Figure 02_image067
(Example 10) The compound (A) synthesized in Example 1 above, the compound (B) synthesized in Example 2 above, the compound (C) synthesized in Example 3 above, and the compound synthesized in Example 4 above were carried out. (D), the compound (E) synthesized in the above embodiment 5, the compound (F) synthesized in the above embodiment 6, the compound (G) synthesized in the above embodiment 7 and the compound (H) synthesized in the above embodiment 8 ), DSC measurement of the compound (I) synthesized in the above-mentioned Example 9 and the following comparative compounds (X) to (Z).
Figure 02_image067

Tg和分解溫度如表1所示。Tg and decomposition temperature are shown in Table 1.

[表1]

Figure 02_image069
[Table 1]
Figure 02_image069

如表1所示，可知本發明的化合物具有135℃以上的Tg，並且分解溫度較高，是熱穩定性優異的材料。認為是通式(1-1)～(1-3)的二氫吖啶骨架的亞甲基部分被二個規定的(雜)芳基取代且該(雜)芳基利用單鍵來形成環、以及二氫吖啶骨架的苯環被Ar2 取代，作為帶來適合的熱穩定性的要因之一來發揮作用。As shown in Table 1, it can be seen that the compound of the present invention has a Tg of 135°C or higher, has a high decomposition temperature, and is a material with excellent thermal stability. It is considered that the methylene moiety of the dihydroacridine skeleton of the general formulas (1-1) to (1-3) is substituted with two prescribed (hetero)aryl groups and the (hetero)aryl group utilizes a single bond to form a ring , And the benzene ring of the dihydroacridine skeleton is substituted with Ar 2 and functions as one of the factors that bring about suitable thermal stability.

[有機EL元件的製作] (實施例11) 在形成有膜厚為110nm的ITO(氧化銦錫)膜之玻璃基板上真空蒸鍍10nm厚度的下述結構式的化合物HAT-CN，來形成電洞注入層。在電洞注入層上真空蒸鍍80nm厚度的下述結構式的化合物HT1，來形成第1電洞傳輸層。繼而，在第1電洞傳輸層上真空蒸鍍10nm厚度的前述製造的化合物(A)，來形成第2電洞傳輸層。繼而，在第2電洞傳輸層上使用作為客體材料的下述結構式的化合物BD1，並使用作為主體材料的下述結構式的化合物BH1，形成厚度為25nm的發光層，該發光層中的客體材料的含有量設為4重量%。繼而，在發光層上依序真空蒸鍍下述結構式的化合物HB1(25nm)和下述結構式的化合物ET1(10nm)，來形成電子傳輸層。繼而，在電子傳輸層上依序真空蒸鍍氟化鋰(LiF)(1nm)和鋁(80nm)來製成電子注入層和陰極。[Production of organic EL element] (Example 11) The compound HAT-CN of the following structural formula with a thickness of 10 nm was vacuum-evaporated on a glass substrate on which an ITO (Indium Tin Oxide) film with a thickness of 110 nm was formed to form a hole injection layer. The compound HT1 of the following structural formula was vacuum-evaporated on the hole injection layer to a thickness of 80 nm to form the first hole transport layer. Then, the compound (A) produced above was vacuum-evaporated on the first hole transport layer to a thickness of 10 nm to form a second hole transport layer. Then, on the second hole transport layer, a compound BD1 of the following structural formula as a guest material and a compound BH1 of the following structural formula as a host material were used to form a light-emitting layer with a thickness of 25 nm. The content of the guest material is set to 4% by weight. Then, the compound HB1 (25 nm) of the following structural formula and the compound ET1 (10 nm) of the following structural formula were sequentially vacuum-evaporated on the light-emitting layer to form an electron transport layer. Then, lithium fluoride (LiF) (1 nm) and aluminum (80 nm) were vacuum-evaporated sequentially on the electron transport layer to form an electron injection layer and a cathode.

Figure 02_image071
Figure 02_image071

(實施例12) 除了將第2電洞傳輸層的材料替換成化合物(B)以外，與實施例11同樣地進行，來形成有機EL元件。(Example 12) Except for replacing the material of the second hole transport layer with the compound (B), the same procedure as in Example 11 was carried out to form an organic EL element.

(實施例13) 除了將第2電洞傳輸層的材料替換成化合物(C)以外，與實施例11同樣地進行，來形成有機EL元件。(Example 13) Except for replacing the material of the second hole transport layer with the compound (C), the same procedure as in Example 11 was carried out to form an organic EL element.

(實施例14) 除了將第2電洞傳輸層的材料替換成化合物(D)以外，與實施例11同樣地進行，來形成有機EL元件。(Example 14) Except that the material of the second hole transport layer was replaced with the compound (D), the same procedure as in Example 11 was carried out to form an organic EL element.

(實施例15) 除了將第2電洞傳輸層的材料替換成化合物(E)以外，與實施例11同樣地進行，來形成有機EL元件。(Example 15) Except for replacing the material of the second hole transport layer with the compound (E), the same procedure as in Example 11 was carried out to form an organic EL element.

(實施例16) 除了將第2電洞傳輸層的材料替換成化合物(F)以外，與實施例11同樣地進行，來形成有機EL元件。(Example 16) Except for replacing the material of the second hole transport layer with the compound (F), the same procedure as in Example 11 was carried out to form an organic EL element.

(實施例17) 除了將第2電洞傳輸層的材料替換成化合物(H)以外，與實施例11同樣地進行，來形成有機EL元件。(Example 17) Except that the material of the second hole transport layer was replaced with the compound (H), the same procedure as in Example 11 was carried out to form an organic EL element.

(實施例18) 除了將第2電洞傳輸層的材料替換成化合物(I)以外，與實施例11同樣地進行，來形成有機EL元件。(Example 18) Except that the material of the second hole transport layer was replaced with compound (I), the same procedure as in Example 11 was carried out to form an organic EL element.

(比較例1) 除了將第2電洞傳輸層的材料替換成上述比較化合物(Ⅹ)以外，與實施例11同樣地進行，來形成有機EL元件。(Comparative example 1) Except that the material of the second hole transport layer was replaced with the above-mentioned comparative compound (X), the same procedure as in Example 11 was carried out to form an organic EL element.

(比較例2) 除了將第2電洞傳輸層的材料替換成上述比較化合物(Y)以外，與實施例11同樣地進行，來形成有機EL元件。(Comparative example 2) Except that the material of the second hole transport layer was replaced with the above-mentioned comparative compound (Y), the same procedure as in Example 11 was carried out to form an organic EL element.

(比較例3) 除了將第2電洞傳輸層的材料替換成上述比較化合物(Z)以外，與實施例11同樣地進行，來形成有機EL元件。(Comparative example 3) Except that the material of the second hole transport layer was replaced with the above-mentioned comparative compound (Z), the same procedure as in Example 11 was carried out to form an organic EL element.

對於所獲得的實施例11～19及比較例1～3的有機EL元件，測定輝度1000cd/m2 時的電壓、外部量子效率、及色度座標。又，測定元件壽命，結果如以下表2所示。 元件壽命，是設為在100mA/cm2 的定電流測定中，元件的發光輝度(初期輝度)衰減到50%為止的時間來加以測定。For the obtained organic EL elements of Examples 11 to 19 and Comparative Examples 1 to 3 , the voltage at a luminance of 1000 cd/m 2 , the external quantum efficiency, and the chromaticity coordinates were measured. In addition, the device life was measured, and the results are shown in Table 2 below. The life of the device is measured as the time until the luminous brightness (initial brightness) of the device decays to 50% in a constant current measurement of 100 mA/cm 2.

[表2]

Figure 02_image073
[Table 2]
Figure 02_image073

實施例11～18以及比較例1～3的有機EL元件皆發射藍光。 如表2所示，實施例11～18的有機EL元件具有包含本發明的化合物之電洞傳輸層，能夠以低電壓來驅動，並且顯示較高的外部量子效率和長期的元件壽命。認為藉由式(1-1)～(1-3)的二氫吖啶骨架的亞甲基部分被二個規定的(雜)芳基取代且該(雜)芳基利用單鍵來形成環、以及二氫吖啶骨架的苯環被Ar2 取代置換，從而能夠成為一種熱穩定性優異的材料，並且能夠立體地抑制親核化合物或親電子化合物攻擊N原子，從而成為一種光穩定性和電穩定性優異的材料，而能夠達成在電洞傳輸層中包含該化合物之有機EL元件的低電壓化、以及高效率化和長壽命化。 另一方面，比較例1～3的有機EL元件具有包含比較化合物之電洞傳輸層，驅動電壓和外部量子效率不一定良好，進一步，元件壽命明顯較短，因此無法獲得足以用於顯示器或照明等的特性。The organic EL elements of Examples 11 to 18 and Comparative Examples 1 to 3 all emit blue light. As shown in Table 2, the organic EL devices of Examples 11 to 18 have a hole transport layer containing the compound of the present invention, can be driven at a low voltage, and exhibit high external quantum efficiency and long-term device life. It is considered that the methylene moiety of the dihydroacridine skeleton of formulas (1-1) to (1-3) is substituted with two prescribed (hetero)aryl groups and the (hetero)aryl group utilizes a single bond to form a ring , And the benzene ring of the dihydroacridine skeleton is replaced by Ar 2 , which can become a material with excellent thermal stability, and can sterically inhibit nucleophilic or electrophilic compounds from attacking the N atom, thereby becoming a kind of light stability and A material with excellent electrical stability can achieve low voltage, high efficiency, and long life of the organic EL device containing the compound in the hole transport layer. On the other hand, the organic EL devices of Comparative Examples 1 to 3 have a hole transport layer containing a comparative compound, and the driving voltage and external quantum efficiency are not necessarily good. Furthermore, the device life is significantly shorter, so it cannot be used in displays or lighting. And other characteristics.

1:有機EL元件 2:基板 3:第2電極(陰極) 4:電子注入層 5:電子傳輸層 6:發光層 7:電洞傳輸層 8:電洞注入層 9:第1電極(陽極)1: Organic EL element 2: substrate 3: The second electrode (cathode) 4: Electron injection layer 5: Electron transport layer 6: Light-emitting layer 7: Hole transmission layer 8: Hole injection layer 9: The first electrode (anode)

第1圖是用以說明本發明的有機電子裝置中包含的有機EL元件的一例的概略剖面圖。FIG. 1 is a schematic cross-sectional view for explaining an example of the organic EL element included in the organic electronic device of the present invention.

國內寄存資訊(請依寄存機構、日期、號碼順序註記) 無 國外寄存資訊(請依寄存國家、機構、日期、號碼順序註記) 無Domestic deposit information (please note in the order of deposit institution, date and number) no Foreign hosting information (please note in the order of hosting country, institution, date, and number) no

1:有機EL元件 1: Organic EL element

2:基板 2: substrate

3:第2電極(陰極) 3: The second electrode (cathode)

4:電子注入層 4: Electron injection layer

5:電子傳輸層 5: Electron transport layer

6:發光層 6: Light-emitting layer

7:電洞傳輸層 7: Hole transmission layer

8:電洞注入層 8: Hole injection layer

9:第1電極(陽極) 9: The first electrode (anode)

Claims (9)

一種由通式(1-1)表示的化合物，
Figure 03_image011
式(1-1)中，n是0或1； L表示單鍵、伸苯基、伸萘基、或由吡啶環、吡嗪環、嘧啶環、噠嗪環及三嗪環中的任一種環所形成之二價芳香族雜環基，該伸苯基、該伸萘基或該二價芳香族雜環基可進一步具有取代基； Ar1 ～Ar5 各自相互獨立地為可具有取代基之芳香族烴基、可具有取代基之芳香族雜環基、或可具有取代基之稠合多環芳香族基； 但是，下述化合物(T)除外，
Figure 03_image075
。A compound represented by the general formula (1-1),
Figure 03_image011
In formula (1-1), n is 0 or 1; L represents a single bond, a phenylene group, a naphthylene group, or any one of a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring and a triazine ring A divalent aromatic heterocyclic group formed by a ring, the phenylene group, the naphthylene group, or the divalent aromatic heterocyclic group may further have a substituent; Ar 1 to Ar 5 are each independently an optionally substituted group The aromatic hydrocarbon group, the aromatic heterocyclic group which may have a substituent, or the condensed polycyclic aromatic group which may have a substituent; However, the following compound (T) is excluded,
Figure 03_image075
. 一種由通式(1-2)或(1-3)表示的化合物，
Figure 03_image076
式(1-2)、(1-3)中，n是0或1； L表示單鍵、伸苯基、伸萘基、或由吡啶環、吡嗪環、嘧啶環、噠嗪環及三嗪環中的任一種環所形成之二價芳香族雜環基，該伸苯基、該伸萘基或該二價芳香族雜環基可進一步具有取代基； Ar1 ～Ar5 各自相互獨立地為可具有取代基之芳香族烴基、可具有取代基之芳香族雜環基、或可具有取代基之稠合多環芳香族基； R是氫、氘、鹵素基、可具有取代基之直鏈狀、支鏈狀或環狀的烷基、可具有取代基之直鏈狀、支鏈狀或環狀的烷氧基、或是可具有取代基之芳香族烴基。A compound represented by the general formula (1-2) or (1-3),
Figure 03_image076
In formulas (1-2) and (1-3), n is 0 or 1; L represents a single bond, a phenylene group, a naphthylene group, or a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring and three A divalent aromatic heterocyclic group formed by any one of the azine rings, the phenylene group, the naphthylene group, or the divalent aromatic heterocyclic group may further have a substituent; Ar 1 to Ar 5 are independent of each other Ground is an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a condensed polycyclic aromatic group which may have a substituent; R is a hydrogen, deuterium, halogen group, which may have a substituent A linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. 如請求項1或2所述之化合物，其中，L是單鍵、伸苯基或伸萘基。The compound according to claim 1 or 2, wherein L is a single bond, phenylene or naphthylene. 如請求項1或2所述之化合物，其中，Ar4 、Ar5 各自相互獨立地為伸苯基、伸聯苯基、或伸萘基。The compound according to claim 1 or 2, wherein Ar 4 and Ar 5 are each independently a phenylene group, a biphenylene group, or a naphthylene group. 如請求項2所述之化合物，其中，R是氫或苯基。The compound according to claim 2, wherein R is hydrogen or phenyl. 一種電洞傳輸材料，其含有請求項1～5中任一項所述之化合物。A hole transport material containing the compound according to any one of claims 1 to 5. 一種有機電子裝置，其包含有機電致發光元件或有機光電轉換元件，該等元件在陰極與陽極之間具備電洞傳輸層，該有機電子裝置的特徵在於： 電洞傳輸層包含請求項1～5中任一項所述之化合物。An organic electronic device comprising an organic electroluminescence element or an organic photoelectric conversion element. The elements are provided with a hole transport layer between a cathode and an anode. The organic electronic device is characterized by: The hole transport layer contains the compound described in any one of claims 1 to 5. 如請求項7所述之有機電子裝置，其中，包含有機電致發光元件，該元件在電洞傳輸層與陰極之間具有發光層。The organic electronic device according to claim 7, which comprises an organic electroluminescence element having a light-emitting layer between the hole transport layer and the cathode. 如請求項8所述之有機電子裝置，其中，發光層包含主體材料、及由發光材料所構成的客體材料，該主體材料是電子傳輸性材料、或具有電洞傳輸性和電子傳輸性的雙極性電荷傳輸性材料。The organic electronic device according to claim 8, wherein the light-emitting layer includes a host material and a guest material composed of a light-emitting material, and the host material is an electron-transporting material or a double Polar charge transport material.
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