TW202005963A - Benzimidazole-substituted diphenylpyrimidine compounds and organic electroluminescent devices using the same - Google Patents

Abstract

The present invention provides benzimidazole-substituted diphenylpyrimidine compounds of formula (I) and an organic electroluminescent device using the same: wherein X1, Ar and n are as defined in the description.

Description

Diphenylpyrimidine compound substituted by benzimidazole and its organic electroluminescence element

The invention relates to a benzimidazole-substituted diphenylpyrimidine compound and an organic electroluminescence device using the compound.

Organic luminescence refers to the use of organic materials to convert electrical energy into light energy. Since organic light-emitting devices are used in displays, they have self-luminous, long life, color saturation, wide color gamut, high efficiency, low driving voltage and low cost. The advantages have attracted much attention, and in order to apply the organic electroluminescent device to various occasions and fields, all circles have especially focused on the development and research of novel organic materials.

The OLED element has at least one organic layer between the anode and the cathode. When a voltage is applied, holes and electrons are injected into the one or more organic layers from the anode and cathode, respectively, and the injected holes and electrons each migrate to the opposite charged electrode. When electrons and holes are confined to the same molecule, they will recombine to form "excitons", which are localized electron-hole pairs in the excited state (in theory, 25% of the excited state % Is the singlet excited state, and the other 75% is the triplet excited state), and when the exciton returns from the excited state to the ground state, it will release energy in the form of light or heat. In order to improve the charge transfer capability and luminous efficiency of the device, in addition to using appropriate electrons, hole transport/injection materials or improving the transmission/injection materials, it can also be achieved by improving the structure of the organic electroluminescent device, such as The transport layer and/or hole transport layer, or the electron blocking layer and/or hole blocking layer are laminated on the light-emitting layer, it is generally considered that this multilayer structure was first invented by the US Kodak Company, the multilayer structure invented by Kodak Company The anode, hole transport layer, light emitting and electron transport layer and cathode are sequentially stacked on the substrate. In addition, by doping the host material with the guest material, the luminous efficiency can also be improved and the chromaticity can be adjusted. Several OLED materials and device configurations are described in U.S. Patent Nos. 4,769,292, 5,844,363, 5,707,745, 6,596,415, and 6,465,115, which are incorporated by reference in their entirety. Yulei Optoelectronics Technology has applied in 2016 and obtained the Republic of China Patent No. I582081 in 2017. The electronic transmission material of this patent has certain novelty and effect.

Since the mobility of holes and electrons in organic materials is different, in order to avoid quenching of the recombination area of holes and electrons near the electrode, an OLED device with a multi-layer thin film structure has been developed. As mentioned above, since the mobility of electrons and holes is different in organic materials, if proper hole transport and electron transport layers are used, holes and electrons can be effectively transported to the light-emitting layer, making the light-emitting layer The density of the electrons and holes in the balance increases the recombination rate of electrons and holes, thereby increasing the luminous efficiency. In addition, the efficiency and life of the device can be improved by properly combining the above organic layers. However, it is still difficult to find organic materials that meet the needs of all actual display applications, especially organic materials with good thermal stability and long life that can be applied to lighting.

Therefore, there is an urgent need for an organic material that can significantly improve the lifetime and heat resistance of organic electroluminescence devices to meet the needs of diverse applications.

式（I） 其中，X₁ 表示經取代或未經取代之（C6-C30）芳基、經取代或未經取代之（5-至30-員）雜芳基； Ar表示經取代或未經取代之（C6-C30）芳基、經取代或未經取代之（5-至30-員）雜芳基； X₁ 及Ar為相同或相異，且至少有一個為經取代或未經取代之（5-至30-員）雜芳基； n表示1或2之整數，當n表示2時，Ar各自為相同或相異。 又，本發明提供一種有機電激發光元件，包含： 陰極； 陽極；以及 有機層：介於該陰極與陽極之間，含有本發明以式（I）表示之經苯并咪唑取代之二苯基嘧啶化合物。 藉由本發明的以式（I）表示之經苯并咪唑取代之二苯基嘧啶化合物，可提供一種壽命長、耐熱性良好的有機材料，能夠滿足車用顯示器及照明用途相關方面之需求，特別適合作為照明光源。An object of the present invention is to provide an organic material having a long life and good heat resistance. The present invention provides a diphenylpyrimidine compound substituted by benzimidazole, which is represented by the following formula (I),

Formula (I) where X ₁ represents a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (5- to 30-membered) heteroaryl group; Ar represents a substituted or unsubstituted Substituted (C6-C30) aryl, substituted or unsubstituted (5- to 30-membered) heteroaryl; X ₁ and Ar are the same or different, and at least one is substituted or unsubstituted (5- to 30-membered) heteroaryl; n represents an integer of 1 or 2, when n represents 2, Ar is the same or different. In addition, the present invention provides an organic electroluminescence device, comprising: a cathode; an anode; and an organic layer: interposed between the cathode and the anode, containing the benzimidazole-substituted diphenyl group represented by formula (I) of the present invention Pyrimidine compound. The benzimidazole-substituted diphenylpyrimidine compound represented by formula (I) of the present invention can provide an organic material with a long life and good heat resistance, which can meet the needs of automotive displays and lighting applications, especially Suitable as a lighting source.

The following describes the implementation of the present invention through specific specific examples. Those skilled in the art can easily understand the advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied by other different embodiments. The details in this specification can also be modified and changed based on different viewpoints and applications without departing from the spirit disclosed by the present invention. In addition, all ranges and numerical values herein are inclusive and combinable. Any value or point that falls within the range described herein, for example, any integer can be used as the minimum or maximum value to derive the lower range.

式（I） 其中，X₁ 表示經取代或未經取代之（C6-C30）芳基、經取代或未經取代之（5-至30-員）雜芳基； Ar表示經取代或未經取代之（C6-C30）芳基、經取代或未經取代之（5-至30-員）雜芳基； X₁ 及Ar為相同或相異，且至少有一個為經取代或未經取代之（5-至30-員）雜芳基； n表示1或2之整數，當n表示2時，Ar各自為相同或相異。The diphenylpyrimidine compound substituted by benzimidazole of the present invention is represented by the following formula (I),

Formula (I) where X ₁ represents a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (5- to 30-membered) heteroaryl group; Ar represents a substituted or unsubstituted Substituted (C6-C30) aryl, substituted or unsubstituted (5- to 30-membered) heteroaryl; X ₁ and Ar are the same or different, and at least one is substituted or unsubstituted (5- to 30-membered) heteroaryl; n represents an integer of 1 or 2, when n represents 2, Ar is the same or different.

式（I-1）

式（I-2）

式（I-3） 其中，X₁ 表示經取代或未經取代之（C6-C30）芳基、經取代或未經取代之（5-至30-員）雜芳基； Ar表示經取代或未經取代之（C6-C30）芳基、經取代或未經取代之（5-至30-員）雜芳基； X₁ 及Ar為相同或相異，且至少有一個為經取代或未經取代之（5-至30-員）雜芳基； n表示1或2之整數，當n表示2時，Ar各自為相同或相異。In a specific embodiment, the benzimidazole substituted diphenylpyrimidine compound represented by formula (I) above is represented by the following formula (I-1), formula (I-2) or formula (I-3 ) Structure representation:

Formula (I-1)

Formula (I-2)

Formula (I-3) where X ₁ represents a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (5- to 30-membered) heteroaryl group; Ar represents a substituted or Unsubstituted (C6-C30) aryl, substituted or unsubstituted (5- to 30-membered) heteroaryl; X ₁ and Ar are the same or different, and at least one is substituted or unsubstituted Substituted (5- to 30-membered) heteroaryl; n represents an integer of 1 or 2, when n represents 2, Ar is the same or different.

Ar of the benzimidazole-substituted diphenylpyrimidine compound represented by formula (I) in the present invention is a substituted or unsubstituted (C6-C30) aryl group, substituted or unsubstituted (5- to 30) -Member) Heteroaryl groups, the reason is that the more planar structures, the more helpful the molecular stacking and increase the carrier transmission effect, but the number of carbon groups should not be too much to avoid the formation of unnecessary crystals.

In the present invention, the benzimidazole-substituted diphenylpyrimidine compound represented by formula (I) wherein X ₁ is a substituted or unsubstituted (C6-C30) aryl group, substituted or unsubstituted (5- to 30-member) Heteroaryl, has the effect of inhibiting molecular crystallization. In a specific embodiment, X ₁ is pyridyl, quinolinyl or naphthyl.

其中，Xr表示氫、氟、氰基、C1-4烷基或未經取代之C6-18芳基。In another specific embodiment, X ₁ in the benzimidazole-substituted diphenylpyrimidine compound represented by formula (I) of the present invention is selected from one of the following groups:

Among them, Xr represents hydrogen, fluorine, cyano, C1-4 alkyl or unsubstituted C6-18 aryl.

其中，L表示O或S； Ar₁ 至Ar₆ 各獨立表示氫、未經取代之C6-18芳基； R₁ 至R₄ 各獨立表示氫、經取代或未經取代之C6-12芳基、R₁ 和R₂ 與相連接的碳原子共同形成C6-18稠合芳香環系統，或R₃ 和R₄ 與相連接的碳原子共同形成C6-18稠合芳香環系統；以及 Y₁ 及Y₂ 之其中一者為單鍵並連接於式（I）化合物，另一者為氫。In a specific embodiment, Ar in the benzimidazole-substituted diphenylpyrimidine compound represented by formula (I) of the present invention is selected from one of the following groups:

Among them, L represents O or S; Ar ₁ to Ar ₆ each independently represent hydrogen, unsubstituted C6-18 aryl; R ₁ to R ₄ each independently represent hydrogen, substituted or unsubstituted C6-12 aryl , R ₁ and R ₂ and the connected carbon atoms together form a C6-18 fused aromatic ring system, or R ₃ and R ₄ and the connected carbon atoms together form a C6-18 fused aromatic ring system; and Y ₁ and One of Y ₂ is a single bond and is connected to the compound of formula (I), and the other is hydrogen.

式（I-4）

式（I-5）In a specific embodiment, when n is 1, the compound of formula (I) is represented by formula (I-4) or formula (I-5).

Formula (I-4)

Formula (I-5)

式（I-6）In a specific embodiment, when n is 2, the compound of formula (I) is represented by formula (I-6).

Formula (I-6)

In another specific embodiment, when the compound of formula (I) is represented by formula (I-6), Ar has the same structure.

In this specification, "substituted" in the so-called "substituted or unsubstituted" refers to the replacement of a hydrogen atom in a functional group by another atom or group (ie, a substituent). Each of these substituents is independently selected from at least one of the group consisting of deuterium, halogen, C1-30 alkyl, C1-30 alkoxy, C6-30 aryl, C5-30 heteroaryl , C5-30 heteroaryl substituted by C6-30 aryl, benzimidazolyl, C3-30 cycloalkyl, C5-7 heterocycloalkyl, tri-C1-30 alkylsilyl, tri-C1-30 aromatic Silane group, di C1-30 alkyl group C6-30 aryl silane group, C1-30 alkyl di C6-30 aryl silane group, C2-30 alkenyl group, C2-30 alkynyl group, cyano group, di C1- 30 alkyl amine group, di C6-30 aryl boron group, di C1-30 alkyl boryl group, C1-30 alkyl group, C6-30 aryl group C1-30 alkyl group, C1-30 alkyl C6-30 aryl group Group, carboxyl group, nitro group and hydroxyl group.

基、稠四苯基、苝基、蒯基、萘并萘基、丙烯合茀基、丙二烯合茀基、苯并丙烯合茀基等。In this specification, "aryl" means an aryl or (extended) aryl group, which refers to a monocyclic ring or fused ring derived from an aromatic hydrocarbon, for example, phenyl, biphenyl, biphenyl Triphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, stilbyl, phenyl stilbyl, benzyl, dibenzyl, phenanthryl, phenylphenanthryl, benzo Phenanthrenyl, anthracenyl, benzanthryl, indenyl, triphenylene, pyrenyl,

Group, condensed tetraphenyl group, perylene group, quinyl group, naphthyl naphthyl group, propylene synyl group, propadiene synyl group, benzopropenyl synyl group, etc.

In this specification, "heteroaryl" means a heteroaryl or (extended) heteroaryl, which may be a monocyclic ring, for example, furanyl, thienyl, pyrrolyl, imidazolyl, pyridine Oxazolyl, thiazolyl, thiadiazolyl, isoxazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triyl, tetrayl, triazolyl, tetrazolyl, furyl, pyridyl, Pyryl, pyrimidinyl, tadyl, piperidinyl, etc., or a fused ring condensed with at least one benzene ring, for example: benzofuranyl, benzothienyl, isobenzofuranyl, dibenzo Furyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisopyrazolyl, benzodioxyl, benzpyrazolyl, or may be quinoline, for example Porphyrinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinolinyl, carbazolyl, phenazolidinyl, pyridinyl, dihydroacridinyl, imidazolidinyl, pyridinyl, oxinyl , Acridinyl, morpholinyl, indolyl, morphine, etc.

In specific embodiments, the preferred form of the benzimidazole-substituted diphenylpyrimidine compound represented by formula (I) of the present invention is shown in Table 1 below, but is not limited thereto.

[Table 1]

In the present invention, the benzimidazole-substituted diphenylpyrimidine compound represented by formula (I) has a glass transition temperature (T _g ) between 125°C and 180°C, and a thermal cracking temperature (T _d ) It is between 486°C and 566°C, so it can withstand the long-term high temperature inside the car, so it is especially suitable for organic electroluminescent devices of car displays.

The invention further provides an organic electroluminescence device, comprising: a cathode; an anode; and an organic layer: interposed between the cathode and the anode, containing the benzimidazole-substituted diphenylpyrimidine represented by the formula (I) of the invention Compound.

The organic layer of the organic electroluminescence element of the present invention may be an electron transport layer, an electron injection layer, a light emitting layer, a hole blocking layer or an electron blocking layer, and in addition to the organic layer, the organic electroluminescence element may also contain Different from the organic layer, at least one layer selected from the group consisting of an electron transport layer, an electron injection layer, a light emitting layer, a hole blocking layer, and an electron blocking layer, wherein the light emitting layer contains fluorescent or phosphorescent guest dopants and Host material corresponding to fluorescent or phosphorescent guest doping.

In a specific embodiment, the organic layer containing the benzimidazole-substituted diphenylpyrimidine compound represented by formula (I) of the present invention is preferably an electron transport layer, and its thickness is preferably from 20 nm to 30 Nano; wherein, the electron transport layer can use the benzimidazole-substituted diphenylpyrimidine compound of the formula (I) as a single material, or the benzimidazole-substituted two of the formula (I) Phenylpyrimidine compounds are used in combination with electrically conductive dopants.

In another specific embodiment, the electron transport layer further contains an N-type electrically conductive dopant, wherein the N-type electrically conductive dopant is substituted with the benzimidazole having the structure of formula (I) of the present invention. Phenylpyrimidine compounds will produce chelation, which allows electrons to be more easily injected from the cathode into the electron transport layer, so it can solve the phase separation and quenching caused by the poor compatibility of metals and electron transport materials in the prior art The problem of extinction can effectively improve the transmission efficiency of the electron transport layer.

The N-type electrically conductive dopant used in the electron transport layer may be an organic alkali metal/alkaline earth metal nitrate, carbonate, phosphate or quinolinate, for example, lithium carbonate, lithium quinolate, Liq), lithium azide, rubidium carbonate, silver nitrate, barium nitrate, magnesium nitrate, zinc nitrate, cesium nitrate, cesium carbonate, cesium fluoride, cesium azide, etc., where the N-type electrical conductivity The doping substance is preferably lithium quinolinate.

In a specific embodiment, the content of the N-type electrically conductive dopant is 5% to 50% by weight based on the weight of the electron transport layer.

The structure of the organic electroluminescence device of the present invention will be described below using drawings. FIG. 1 is a schematic cross-sectional view of an embodiment of the organic electroluminescence device of the present invention. The organic electroluminescence device 100 includes a substrate 110, an anode 120, a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, an electron injection layer 170, and a cathode 180. The organic electroluminescence device 100 can be manufactured by sequentially depositing the above layers. 2 is a schematic cross-sectional view of another embodiment of the organic electroluminescence device of the present invention. The organic electroluminescence device 200 includes a substrate 210, an anode 220, a hole injection layer 230, a hole transport layer 240, an exciton blocking layer 245, a light emitting layer 250, an electron transport layer 260, an electron injection layer 270, and a cathode 280, and The difference between 1 is that the exciton blocking layer 245 is provided between the hole transport layer 240 and the light emitting layer 250. 3 is a schematic cross-sectional view of still another embodiment of the organic electroluminescence device of the present invention. The organic electroluminescence device 300 includes a substrate 310, an anode 320, a hole injection layer 330, a hole transport layer 340, a light emitting layer 350, an exciton blocking layer 355, an electron transport layer 360, an electron injection layer 370, and a cathode 380, and The difference between 1 is that the exciton blocking layer 355 is provided between the light emitting layer 350 and the electron transport layer 360.

The organic electroluminescence device can be manufactured according to the reverse structure of the device shown in FIGS. 1 to 3. In addition, for these inverted structures, one or more layers can be added or removed according to the demand.

The materials of the hole injection layer, hole transmission layer, exciton blocking layer, electron blocking layer, and electron injection layer can be selected from conventional materials. For example, the electron transport material forming the electron transport layer is different from the material of the light emitting layer And, it has hole transportability, so that holes can migrate in the electron transport layer, and can prevent the accumulation of carriers caused by the dissociation energy difference between the light emitting layer and the electron transport layer.

The benzimidazole-substituted diphenylpyrimidine compound represented by formula (I) of the present invention has a triplet energy level higher than 2.2 eV (to be confirmed by customers), a HOMO energy level deeper than 6.0 eV and good The carrier mobility, when used in the case of an electron transport layer, can help to increase excitons to relax in the light-emitting layer and emit light.

In addition, the US Patent No. 20170005275A1 revealed that the p-type doped hole transport layer was doped with HT-D2 in HT3, and the patent also doped Lithium quinolate (Liq) as the n-type doped material in the electron transport material In (ET3), these contents are cited in the present invention. In addition, for example, the entire contents of the cathodes disclosed in U.S. Patent Nos. 5,703,436 and 5,77,745 are cited in the present invention. The composition of the cathode is, for example, magnesium/silver (Mg: Ag), and a transparent conductive layer (ITO Layer) is formed by sputtering deposition . In addition, the present invention refers to the entire contents of the applications and principles of each barrier layer disclosed in US Patent Nos. 6,097,147 and 20030230980. In addition, the present invention also refers to the relevant content of the injection layer and the protective layer exemplified in US Patent No. 20040174116.

The present invention can also be applied to other structures and materials, such as organic electroluminescence elements containing polymer materials (PLEDs) disclosed in US Patent No. 5,247,190. Furthermore, the organic electroluminescence device with only a single organic layer or the multiple organic electroluminescence device as disclosed in US Pat. No. 5,707,745, the invention is also applicable.

Unless otherwise specified, any layer in each embodiment can be formed using any suitable method. For the organic layer, preferred forming methods are the vapor deposition method and spray printing method disclosed in the US Patent Nos. 6013982 and 6087196, and the organic vapor phase deposition (OVPD) method disclosed in the US Patent No. 6337102. The disclosure by organic vapor jet printing (OVJP) disclosed in Patent No. 10/233470, the present invention refers to the relevant content of these patent applications. Other suitable methods include spin coating and solution-based processes. The solution-based process is preferably carried out in an environment where oxidation is not likely to occur, such as a nitrogen or inert gas environment. For other layers, a preferred method includes, for example, a vapor deposition method. Preferred patterning methods include processes using masks as disclosed in US Pat. Nos. 6,294,398 and 6,468,819, and processes that integrate deposition and patterning by jet printing or organic vapor jet printing. The present invention refers to this related content. Of course, other methods can also be used.

The benzimidazole-substituted diphenylpyrimidine compound represented by formula (I) of the present invention can be prepared and applied to organic electricity by vacuum deposition, wet coating method (including spin coating method, inkjet method) or printing method Amorphous film of excitation light element.

The organic electroluminescence device of the present invention can be applied to active or passive structures. Compared with conventional devices, the organic electroluminescence device of the present invention can significantly improve thermal stability and life. In addition, by doping the phosphorescent guest dopant, the organic electroluminescence device of the present invention can emit white light and cooperate with the filter to realize a full-color or multi-color display panel.

The following describes in detail the many properties and effects of the present invention by means of synthesis examples and examples. However, these synthetic examples and examples are only for illustrating and understanding the present invention, and the present invention is not limited to these examples.

將4-(1-苯基-1H-苯并[d]咪唑-2-基)苯基硼酸 (150 g，753.61 mmol)與1-(4-溴基-苯基)-乙酮(1-(4-Bromo-phenyl)-ethanone)(260.42 g，828.97 mmol)，以及碳酸鉀(260.37 g，1884 mmol)置於反應瓶，再加入甲苯 2250 ml、EtOH 366 ml、DI H₂ O 732 ml並架上N₂ 與冷凝管並將反應移至油鍋中，加熱使溫度上升至80 ℃，取Pd(PPh₃ )₄ (43.52 g，37.68 mmol)加入於反應中將溫度上升至80 ℃回流反應16小時，反應完後降溫，將水層移除後濃縮至黏稠後，加入甲苯加熱通過管柱(100 g Al₂ O₃ ／200 g SiO₂ )，將濾液濃縮至黏稠後倒入燒杯靜置析出過濾後，得到灰色固體，烘乾後得到260 g白色固體化合物A，產率： 88.5%。

將化合物A(163.15 g，419.99 mmol)，3-溴基-苯甲醛 (74 g，399.99 mmol)，ETOH：3263 ml加入反應瓶內攪拌，最後加入叔丁醇鈉(Sodium-t-butoxide)(58.2 g，600 mmol)，於室溫攪拌，待反應已完全後加入去離子水2000 ml攪拌過濾，過濾固體以去離子水跟甲醇清洗，固體再以1000 ml去離子水與2000 ml甲醇攪拌30分鐘過濾，重複2次將固體烘乾得到220 g淡黃色固體化合物B，產率94.5%。

將化合物B(124 g，223.23 mmol)、3-吡啶甲脒鹽酸鹽(52.77 g，334.83 mmol)與磷酸鉀(165.84 g，781.31 mmol)、二甲苯 1240 ml放至反應瓶內加熱攪拌維持140 ℃回流。反應完全後降溫至90℃，加入去離子水 500 ml攪拌5 min，移除水層後，將有機層濃縮至乾後有固體析出，再以乙酸乙酯來沖洗固體與過濾得到白色固體，烘乾後得到64 g白色固體化合物C，產率：43.66%。 將4-二苯并呋喃硼酸 (5.8 g，27.35 mmol)、化合物C (15 g，22.84 mmol)與碳酸鉀(7.9 g，57.1 mmol)置入於反應瓶，加入甲苯 225 ml、乙醇38 ml、去離子水76 ml並架上N₂ 與冷凝管並將反應移至油鍋中，加熱攪拌80 ℃。將四(三苯基膦)鈀(1.32 g，1.14 mmol)加入反應瓶，待反應完全後且有許多固體析出，移除油浴降溫後先行過濾，將濾餅倒入燒杯中，並加入去離子水 100 ml攪拌10 mins後過濾，將濾餅挖入燒杯中，並加入四氫呋喃 3000 ml加熱攪拌至全溶，通過管柱(20 g SiO₂ )，將濾液濃縮至乾有白色固體析出後，用乙酸乙酯沖洗過濾，烘乾得到13 g白色固體化合物1-2，產率76.3%。 以下顯示¹ H NMR之測定結果。 1H NMR (CDCl3, 400MHz) δ 9.96(s, 1H), 8.99(d, 1H), 8.84(s, 1H), 8.76(d, 1H), 8.38(d, 2H), 8.34(d, 1H), 8.19(s, 1H),8.13(d,1H), 8.03(d, 2H), 7.92(d, 1H), 7.81-7.71(m, 6H), 7.65-7.64(m, 3H), 7.57-7.47(m, 6H), 7.41-7.35(m, 4H), 7.31-7.27(m, 2H).[Synthesis Example 1]

Combine 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (150 g, 753.61 mmol) with 1-(4-bromo-phenyl)-ethanone (1- (4-Bromo-phenyl)-ethanone) (260.42 g, 828.97 mmol), and potassium carbonate (260.37 g, 1884 mmol) were placed in the reaction flask, and then added toluene 2250 ml, EtOH 366 ml, DI H ₂ O 732 ml and Put N ₂ and a condenser on the rack and move the reaction to an oil pan, heat to raise the temperature to 80 ℃, take Pd(PPh ₃ ) ₄ (43.52 g, 37.68 mmol) into the reaction and raise the temperature to 80 ℃ to reflux. After 16 hours, the temperature was lowered after the reaction was completed. After removing the water layer and concentrating to a thick layer, toluene was added and heated through the column (100 g Al ₂ O ₃ /200 g SiO ₂ ). The filtrate was concentrated to a thick layer and poured into a beaker and allowed to stand After precipitation and filtration, a gray solid was obtained, and after drying, 260 g of a white solid compound A was obtained, yield: 88.5%.

Compound A (163.15 g, 419.99 mmol), 3-bromo-benzaldehyde (74 g, 399.99 mmol), ETOH: 3263 ml were added to the reaction flask and stirred, and finally sodium-t-butoxide (Sodium-t-butoxide) ( 58.2 g, 600 mmol), stirred at room temperature. After the reaction is complete, add 2000 ml of deionized water and stir to filter. The solid is filtered and washed with deionized water and methanol. The solid is then stirred with 1000 ml of deionized water and 2000 ml of methanol for 30 Filtration in minutes and drying the solid twice were repeated to obtain 220 g of light yellow solid compound B with a yield of 94.5%.

Compound B (124 g, 223.23 mmol), 3-pyridinecarboxamidine hydrochloride (52.77 g, 334.83 mmol), potassium phosphate (165.84 g, 781.31 mmol), and xylene 1240 ml were placed in a reaction flask and heated and stirred to maintain 140 ℃ reflux. After the reaction was completed, the temperature was lowered to 90°C, 500 ml of deionized water was added, and the mixture was stirred for 5 min. After removing the water layer, the organic layer was concentrated to dryness and a solid precipitated out. The solid was washed with ethyl acetate and filtered to obtain a white solid. After drying, 64 g of white solid compound C was obtained with a yield of 43.66%. Put 4-dibenzofuranboronic acid (5.8 g, 27.35 mmol), compound C (15 g, 22.84 mmol) and potassium carbonate (7.9 g, 57.1 mmol) into the reaction flask, add toluene 225 ml, ethanol 38 ml, 76 ml of deionized water was placed on the N ₂ and condenser tube, and the reaction was transferred to the oil pot, heated and stirred at 80 ℃. Add tetrakis(triphenylphosphine)palladium (1.32 g, 1.14 mmol) to the reaction flask. After the reaction is complete and a lot of solids are precipitated, remove the oil bath to cool down and filter first. Pour the filter cake into the beaker and add After 100 ml of ionized water was stirred for 10 mins and filtered, the filter cake was dug into a beaker, and 3000 ml of tetrahydrofuran was added and stirred with heating until completely dissolved. The filtrate was concentrated to a dry white solid after passing through a column (20 g SiO ₂ ). The filter was washed with ethyl acetate and dried to obtain 13 g of a white solid compound 1-2 with a yield of 76.3%. The measurement results of ¹ H NMR are shown below. 1H NMR (CDCl3, 400MHz) δ 9.96(s, 1H), 8.99(d, 1H), 8.84(s, 1H), 8.76(d, 1H), 8.38(d, 2H), 8.34(d, 1H), 8.19(s, 1H), 8.13(d,1H), 8.03(d, 2H), 7.92(d, 1H), 7.81-7.71(m, 6H), 7.65-7.64(m, 3H), 7.57-7.47( m, 6H), 7.41-7.35(m, 4H), 7.31-7.27(m, 2H).

將化合物A (30 g，77.22 mmol)、4-溴基-苯甲醛(13.6 g，73.55 mmol)、乙醇600 ml加入反應瓶內攪拌，最後加入叔丁醇鈉(13.6 g，220.65 mmol)於室溫攪拌，待反應完全後加入去離子水500 ml攪拌過濾，過濾固體以去離子水跟甲醇清洗，固體再以500 ml去離子水、500 ml甲醇攪拌30分鐘後過濾，重複2次將固體烘乾得到40 g淡黃色固體化合物D，產率92.9%。

將化合物D(33 g，59.41 mmol)、 3-吡啶甲脒(14 g，89.11 mmol)與磷酸(44.14 g，207.93 mmol)、二甲苯 3300 ml放至反應瓶內加熱攪拌維持140 ℃回流，待反應完全後降溫至90 ℃，加入去離子水500 ml攪拌5 min後，移除水層後，將有機層濃縮至乾後有固體析出用乙酸乙酯來沖洗固體與過濾得到白色固體，烘乾得到16 g白色固體化合物E，產率41.1%。

將4-二苯并呋喃硼酸 (5.8 g，27.35 mmol)、化合物E(15 g，22.84 mmol)與碳酸鉀(7.9 g，57.1 mmol)置於反應瓶，再加入甲苯225 ml、乙醇38 ml、去離子水76 ml並架上N₂ 與冷凝管並將反應移至油鍋中，加熱攪拌80 ℃，將四(三苯基膦)鈀(1.32 g，1.14 mmol)加入反應瓶，待反應完全後且有許多固體析出，移除油浴降溫後先行過濾，將濾餅倒入燒杯中，並加入去離子水100 ml攪拌10 mins後過濾。將濾餅挖入燒杯中並加入四氫呋喃3000 ml加熱攪拌至全溶，通過管柱(20 g SiO₂ )，將濾液濃縮至乾有白色固體析出後，用乙酸乙酯來沖洗過濾，烘乾得到14 g白色固體化合物1-3，產率82.4%。 以下顯示¹ H NMR之測定結果。 1H NMR (CDCl3, 400MHz) δ 9.95(s, 1H), 8.99(d, 1H), 8.78(d, 1H), 8.48(d, 2H), 8.38(d, 2H), 8.18(t, 3H), 8.02-8.00(m, 2H), 7.91(d, 1H), 7.81(d, 2H), 7.70-7.67(m, 3H), 7.66-7.62(m, 3H), 7.58-7.48(m, 6H), 7.41-7.36(m, 4H), 7.33-7.28(m, 2H).[Synthesis Example 2]

Compound A (30 g, 77.22 mmol), 4-bromo-benzaldehyde (13.6 g, 73.55 mmol), and 600 ml of ethanol were added to the reaction flask and stirred. Finally, sodium tert-butoxide (13.6 g, 220.65 mmol) was added to the chamber. Stir gently, add 500 ml of deionized water after the reaction is complete, stir and filter, wash the solid with deionized water and methanol, and then solidify with 500 ml of deionized water and 500 ml of methanol for 30 minutes, then filter, repeat twice to dry the solid Drying gave 40 g of light yellow solid compound D with a yield of 92.9%.

Put compound D (33 g, 59.41 mmol), 3-pyridinecarboxamidine (14 g, 89.11 mmol), phosphoric acid (44.14 g, 207.93 mmol), xylene 3300 ml into the reaction flask, heat and stir to maintain reflux at 140 ℃, wait After the reaction was completed, the temperature was lowered to 90°C, 500 ml of deionized water was added, and the mixture was stirred for 5 min. After removing the water layer, the organic layer was concentrated to dryness. After solid precipitation, rinse the solid with ethyl acetate and filter to obtain a white solid. 16 g of white solid compound E was obtained with a yield of 41.1%.

Put 4-dibenzofuranboronic acid (5.8 g, 27.35 mmol), compound E (15 g, 22.84 mmol) and potassium carbonate (7.9 g, 57.1 mmol) in the reaction flask, then add toluene 225 ml, ethanol 38 ml, Deionized water 76 ml and put N ₂ and condenser tube on the rack and transfer the reaction to an oil pot, heat and stir at 80 ℃, add tetrakis(triphenylphosphine)palladium (1.32 g, 1.14 mmol) to the reaction bottle, and wait until the reaction is complete After a lot of solids precipitated, the oil bath was removed to cool down and then filtered, the filter cake was poured into a beaker, and 100 ml of deionized water was added, stirred for 10 mins and filtered. Dig the filter cake into a beaker and add 3000 ml of tetrahydrofuran and stir with heating until it is completely dissolved. After passing through the column (20 g SiO ₂ ), the filtrate is concentrated to dryness and a white solid is precipitated. Rinse and filter with ethyl acetate and dry to obtain 14 g of white solid compound 1-3, yield 82.4%. The measurement results of ¹ H NMR are shown below. 1H NMR (CDCl3, 400MHz) δ 9.95(s, 1H), 8.99(d, 1H), 8.78(d, 1H), 8.48(d, 2H), 8.38(d, 2H), 8.18(t, 3H), 8.02-8.00(m, 2H), 7.91(d, 1H), 7.81(d, 2H), 7.70-7.67(m, 3H), 7.66-7.62(m, 3H), 7.58-7.48(m, 6H), 7.41-7.36(m, 4H), 7.33-7.28(m, 2H).

分別將1-(4-溴基苯基)乙酮 (19.9 g，100 mmole)、氫氧化鉀(1.68 g，30 mmole)與4-溴基苯甲醛 (18.5 g，100 mmole)置於1000 mL雙頸圓底瓶中，加入300 mL乙醇，室溫下攪拌4小時。進行過濾，得到35.5 g乳白色固體化合物F，產率97.0%。

分別將化合物F(9.15 g，25 mmole)、3-吡啶甲脒鹽酸鹽(3.94 g，25 mmole) 與氫氧化鉀(1.68 g，30 mmole)置入500 mL雙頸圓底瓶中，加入150 mL乙醇，加熱至迴流。反應3小時後，靜置回溫至室溫，進行過濾，以乙醇清洗固體，得到8.45g白色固體化合物G，產率72.4%。

分別將Pd(PPh₃ )₄ (1.65 g，1.45 mmole)、K₂ CO₃ (10.0 g，72.8 mmole)、化合物G (8.5 g，18.2 mmole)與4-(1-苯基-1H-苯并[d]咪唑-2-基)苯基硼酸 (12.6 g，40.1 mmole)置入500 mL雙頸圓底瓶中，加入80 mL 甲苯、55 mL乙醇和25 mL去離子水，加熱至迴流。反應隔夜後，加入50 mL乙酸乙酯進行萃取，將萃取後濾液加入以填充矽膠進行層析法純化，濃縮至濃稠，加入甲醇 30 mL 加強析出，有機層合併過濾固體，得到8.5g乳白色固體化合物1-5，產率55.1%。 以下顯示¹ H NMR之測定結果。¹ H NMR (CDCl₃ , 400MHz) d 9.93(s, 1H), 8.96(dt, 1H), 8.76(dd, 1H), 8.37(d, 4H), 8.12(s, 1H), 7.92(d, 2H), 7.81(d, 2H), 7.57-7.71(m, 4H), 7.65-7.63(m, 4H), 7.57-7.52(m, 6H), 7.40~7.35(m, 6H), 7.31-7.27(m, 5H).[Synthesis Example 3]

Place 1-(4-bromophenyl)ethanone (19.9 g, 100 mmole), potassium hydroxide (1.68 g, 30 mmole) and 4-bromobenzaldehyde (18.5 g, 100 mmole) in 1000 mL Add 300 mL of ethanol to the double-neck round-bottom flask and stir at room temperature for 4 hours. It was filtered to obtain 35.5 g of milky white solid compound F with a yield of 97.0%.

Put compound F (9.15 g, 25 mmole), 3-pyridinecarboxamidine hydrochloride (3.94 g, 25 mmole) and potassium hydroxide (1.68 g, 30 mmole) into a 500 mL double-necked round bottom flask, add 150 mL ethanol, heated to reflux. After reacting for 3 hours, it was left to warm to room temperature, filtered, and the solid was washed with ethanol to obtain 8.45 g of white solid compound G with a yield of 72.4%.

Pd(PPh ₃ ) ₄ (1.65 g, 1.45 mmole), K ₂ CO ₃ (10.0 g, 72.8 mmole), compound G (8.5 g, 18.2 mmole) and 4-(1-phenyl-1H-benzo [d] Imidazol-2-yl) phenylboronic acid (12.6 g, 40.1 mmole) was placed in a 500 mL double-necked round bottom flask, 80 mL of toluene, 55 mL of ethanol and 25 mL of deionized water were added, and heated to reflux. After the reaction overnight, 50 mL of ethyl acetate was added for extraction, and the filtrate after extraction was filled with silica gel for chromatography purification, concentrated to a thick, 30 mL of methanol was added to enhance precipitation, and the organic layer was combined to filter solid to obtain 8.5 g of milky white solid Compound 1-5, yield 55.1%. The measurement results of ¹ H NMR are shown below. ¹ H NMR (CDCl ₃ , 400MHz) d 9.93(s, 1H), 8.96(dt, 1H), 8.76(dd, 1H), 8.37(d, 4H), 8.12(s, 1H), 7.92(d, 2H ), 7.81(d, 2H), 7.57-7.71(m, 4H), 7.65-7.63(m, 4H), 7.57-7.52(m, 6H), 7.40~7.35(m, 6H), 7.31-7.27(m , 5H).

分別將1-(4-溴基苯基)乙酮 (19.9 g，100 mmole)、氫氧化鉀(1.68 g，30 mmole)與3-溴基苯甲醛 (18.5 g，100 mmole)置於1000 mL雙頸圓底瓶中，加入300 mL乙醇，室溫下攪拌4小時。過濾，得到34.4 g乳白色固體化合物H，產率93.7%。

分別將化合物H (9.15 g，25 mmole)、3-吡啶甲脒鹽酸鹽(3.94 g，25 mmole) 與氫氧化鉀(1.68 g，30 mmole)置入500 mL雙頸圓底瓶中，加入150 mL乙醇，加熱至迴流。反應3小時後，靜置回溫至室溫，過濾，以乙醇清洗固體，得到9.34克白色固體化合物I，產率80%。

分別將Pd(PPh₃ )₄ (1.65 g，1.45 mmole)、K₂ CO₃ (10.0 g，72.8 mmole)、化合物I (8.5 g，18.2 mmole)與4-(1-苯基-1H-苯并[d]咪唑-2-基)苯基硼酸 (12.6 g，40.1 mmole)置入500 mL雙頸圓底瓶中，加入80 mL 甲苯、55 mL乙醇和25 mL去離子水，加熱至迴流。反應隔夜後，加入50 mL乙酸乙酯進行萃取，將萃取後濾液加入以填充矽膠進行層析法純化，濃縮至濃稠，加入甲醇 30 mL 加強析出，有機層合併過濾固體，得到8.1g乳白色固體化合物1-6，產率52.3%。 以下顯示¹ H NMR之測定結果。¹ H NMR (CDCl₃ , 400MHz) d 9.92(s, 1H), 8.95(d, 1H), 8.76(d, 1H), 8.47(s, 1H), 8.37(d, 2H), 8.25(d, 1H), 8.11(s, 1H), 7.92(d, 2H), 7.80-7.77(m, 3H), 7.74-7.70(m, 4H), 7.68-7.58(m, 5H), 7.57-7.51(m, 5H), 7.49-7.46(m, 1H), 7.41-7.35(m, 6H), 7.31-7.27(m, 4H).[Synthesis Example 4]

Place 1-(4-bromophenyl)ethanone (19.9 g, 100 mmole), potassium hydroxide (1.68 g, 30 mmole) and 3-bromobenzaldehyde (18.5 g, 100 mmole) in 1000 mL Add 300 mL of ethanol to the double-neck round-bottom flask and stir at room temperature for 4 hours. Filtration gave 34.4 g of milky white solid compound H with a yield of 93.7%.

Put Compound H (9.15 g, 25 mmole), 3-pyridinecarboxamidine hydrochloride (3.94 g, 25 mmole) and potassium hydroxide (1.68 g, 30 mmole) into a 500 mL double-necked round bottom flask, add 150 mL ethanol, heated to reflux. After reacting for 3 hours, it was left to warm to room temperature, filtered, and the solid was washed with ethanol to obtain 9.34 g of white solid compound I with a yield of 80%.

Pd(PPh ₃ ) ₄ (1.65 g, 1.45 mmole), K ₂ CO ₃ (10.0 g, 72.8 mmole), compound I (8.5 g, 18.2 mmole) and 4-(1-phenyl-1H-benzo [d] Imidazol-2-yl) phenylboronic acid (12.6 g, 40.1 mmole) was placed in a 500 mL double-necked round bottom flask, 80 mL of toluene, 55 mL of ethanol and 25 mL of deionized water were added, and heated to reflux. After the reaction overnight, 50 mL of ethyl acetate was added for extraction, and the filtrate after extraction was filled with silica gel for chromatography purification, concentrated to a thick, 30 mL of methanol was added to enhance precipitation, and the organic layer was combined to filter the solid to obtain 8.1 g of milky white solid Compound 1-6, yield 52.3%. The measurement results of ¹ H NMR are shown below. ¹ H NMR (CDCl ₃ , 400MHz) d 9.92(s, 1H), 8.95(d, 1H), 8.76(d, 1H), 8.47(s, 1H), 8.37(d, 2H), 8.25(d, 1H ), 8.11(s, 1H), 7.92(d, 2H), 7.80-7.77(m, 3H), 7.74-7.70(m, 4H), 7.68-7.58(m, 5H), 7.57-7.51(m, 5H ), 7.49-7.46(m, 1H), 7.41-7.35(m, 6H), 7.31-7.27(m, 4H).

將化合物C (10 g，15.23 mmole)與(3-(吡啶-3-基)苯基)硼酸 (3.18 g，15.99 mmole)置於反應槽，，加入甲苯 120 ml。將K₂ CO₃ (7.38 g，53.3 mmole)溶於70 ml去離子水後加入反應槽，加入四(三苯基膦)鈀 (1.23 g，0.76 mmole)及EtOH 30 ml開啟加熱及攪拌。加熱至80 ℃反應整晚。反應完後加入300 ml DI water，攪拌30分鐘，靜置使其分層，進行萃取，將萃取後濾液加入以填充矽膠進行層析法純化，濃縮至濃稠後加入己烷 300 mL 加強析出，有機層合併過濾固體，得到5.5 g乳白色固體化合物1-7，產率49.4%。 以下顯示¹ H NMR之測定結果。 1H NMR (CDCl₃ , 400MHz) d 9.93 (s, 1H), 8.97-8.95(m, 2H), 8.77(d, 1H), 8.63(d, 1H), 8.53(s, 1H), 8.37(d, 2H), 8.29(d, 1H), 8.14(s, 1H), 7.98(t, 1H), 7.92(d, 1H), 7.88(s, 1H), 7.84(d, 1H), 7.80(d, 2H), 7.77-7.75(m, 1H), 7.72-7.67(m, 3H), 7.65-7.64(m, 4H), 7.58-7.50(m, 3H), 7.49-7.47(m, 1H), 7.43-7.35(m, 4H), 7.31-7.26(m, 2H).[Synthesis Example 5]

Compound C (10 g, 15.23 mmole) and (3-(pyridin-3-yl)phenyl)boronic acid (3.18 g, 15.99 mmole) were placed in the reaction tank, and 120 ml of toluene was added. Dissolve K ₂ CO ₃ (7.38 g, 53.3 mmole) in 70 ml of deionized water and add it to the reaction tank. Add tetrakis(triphenylphosphine)palladium (1.23 g, 0.76 mmole) and EtOH 30 ml to start heating and stirring. Heated to 80 ℃ to react overnight. After the reaction, 300 ml of DI water was added, stirred for 30 minutes, and allowed to stand to separate layers for extraction. The extracted filtrate was added with silica gel for chromatography purification. After concentrated to a thick concentration, 300 mL of hexane was added to enhance precipitation. The organic layers were combined and the solid was filtered to obtain 5.5 g of milky white solid compound 1-7 in a yield of 49.4%. The measurement results of ¹ H NMR are shown below. 1H NMR (CDCl ₃ , 400MHz) d 9.93 (s, 1H), 8.97-8.95(m, 2H), 8.77(d, 1H), 8.63(d, 1H), 8.53(s, 1H), 8.37(d, 2H), 8.29(d, 1H), 8.14(s, 1H), 7.98(t, 1H), 7.92(d, 1H), 7.88(s, 1H), 7.84(d, 1H), 7.80(d, 2H ), 7.77-7.75(m, 1H), 7.72-7.67(m, 3H), 7.65-7.64(m, 4H), 7.58-7.50(m, 3H), 7.49-7.47(m, 1H), 7.43-7.35 (m, 4H), 7.31-7.26(m, 2H).

將3-(咔唑-9-基)苯基硼酸 (7.21 g，25.13 mmol)、化合物C (15 g，22.84 mmol)與碳酸鉀(7.9 g，57.1 mmol)置於反應瓶，再加入甲苯225 ml、乙醇38 ml、去離子水76 ml，並架上N₂ 與冷凝管並將反應移至油鍋中，加熱攪拌80 ℃。將四(三苯基膦)鈀(1.32 g，1.14 mmol)加入反應瓶，待反應完全後且有許多固體析出，移除油浴降溫後先行過濾，將濾餅倒入燒杯中，並加入去離子水100 ml攪拌10 mins後過濾，將濾餅挖入燒杯中，並加入四氫呋喃3000 ml加熱攪拌至全溶，通過管柱(20 g SiO₂ )，將濾液濃縮至乾有白色固體析出後，用乙酸乙酯來沖洗過濾，烘乾得到11.5 g白色固體化合物1-9，產率 61.6%。 以下顯示¹ H NMR之測定結果。 1H NMR (CDCl3, 400MHz) δ 9.92(s, 1H), 8.95(d, 1H), 8.74(d, 1H), 8.54(s, 1H), 8.33(d, 2H), 8.30(d, 1H), 8.17(t, 3H), 7.91(d, 2H), 7.83-7.71(m, 6H), 7.69-7.68(m, 3H), 7.66-7.63(m, 3H), 7.55-7.51(m, 5H), 7.49-7.42(m, 3H), 7.41-7.28(m, 6H).[Synthesis Example 6]

Place 3-(carbazol-9-yl)phenylboronic acid (7.21 g, 25.13 mmol), compound C (15 g, 22.84 mmol) and potassium carbonate (7.9 g, 57.1 mmol) in the reaction flask, and add toluene 225 ml, ethanol 38 ml, deionized water 76 ml, and put N ₂ and condenser tube on the rack and move the reaction to the oil pot, heating and stirring at 80 ℃. Add tetrakis(triphenylphosphine)palladium (1.32 g, 1.14 mmol) to the reaction flask. After the reaction is complete and a lot of solids are precipitated, remove the oil bath to cool down and filter first. Pour the filter cake into the beaker and add After 100 ml of ionized water was stirred for 10 mins and filtered, the filter cake was dug into a beaker, and 3000 ml of tetrahydrofuran was added and stirred with heating until completely dissolved. The filtrate was concentrated to a dry white solid after passing through a column (20 g SiO ₂ ). Rinse and filter with ethyl acetate and dry to obtain 11.5 g of white solid compound 1-9 with a yield of 61.6%. The measurement results of ¹ H NMR are shown below. 1H NMR (CDCl3, 400MHz) δ 9.92(s, 1H), 8.95(d, 1H), 8.74(d, 1H), 8.54(s, 1H), 8.33(d, 2H), 8.30(d, 1H), 8.17(t, 3H), 7.91(d, 2H), 7.83-7.71(m, 6H), 7.69-7.68(m, 3H), 7.66-7.63(m, 3H), 7.55-7.51(m, 5H), 7.49-7.42(m, 3H), 7.41-7.28(m, 6H).

[Synthesis Example 7] (9-phenyl-9H-carbazol-2-yl)boronic acid (7.21 g, 25.13 mmol), compound C (15 g, 22.84 mmol) and potassium carbonate (7.9 g, 57.1 mmol) were placed In the reaction bottle, add 225 ml of toluene, 38 ml of ethanol, 76 ml of deionized water and put N ₂ and a condenser on the rack and move the reaction to an oil pot, heat and stir at 80 ℃, and palladium tetrakis(triphenylphosphine) (1.32 g, 1.14 mmol) was added to the reaction flask. After the reaction was complete and many solids were precipitated, remove the oil bath to cool down and filter first, pour the filter cake into the beaker, add 100 ml of deionized water and stir for 10 minutes, then filter , Dig the filter cake into a beaker, add 3000 ml of tetrahydrofuran and stir with heating until it is completely dissolved. After passing through the column (20 g SiO ₂ ), the filtrate is concentrated to dryness and a white solid is precipitated. Rinse the filter with ethyl acetate and dry it. After drying, 14 g of white solid compound 1-10 was obtained with a yield of 75%. The measurement results of ¹ H NMR are shown below. 1H NMR (CDCl3, 400MHz) δ 9.92(s, 1H), 8.95(d, 2H), 8.76(s, 1H), 8.53(s, 1H), 8.37(d, 2H), 8.20-8.18(m, 3H ), 8.13(s, 1H), 8.92-8.90(d, 1H), 7.78-7.72(m, 3H), 7.65-7.63(m, 9H), 7.58-7.47(m, 5H), 7.45-7.42(m , 2H), 7.37-7.32(m, 5H).

將喹啉-8-硼酸 (4.35 g，25.13 mmol)、化合物C (15 g，22.84 mmol) 與碳酸鉀(7.9 g，57.1 mmol)置於反應瓶，再加入甲苯225 ml、乙醇38 ml、去離子水76 ml並架上N₂ 與冷凝管並將反應移至油鍋中，加熱攪拌80 ℃。將四(三苯基膦)鈀(1.32 g，1.14 mmol)加入反應瓶，待反應完全後且有許多固體析出，移除油浴降溫後先行過濾，將濾餅倒入燒杯中，並加入去離子水100 ml攪拌10 mins後過濾，將濾餅挖入燒杯中並加入四氫呋喃3000 ml加熱攪拌至全溶，通過管柱(20 g SiO₂ )，將濾液濃縮至乾有白色固體析出後，用乙酸乙酯來沖洗過濾，烘乾後得到12 g白色固體化合物1-11，產率74.5%。 以下顯示¹ H NMR之測定結果。 1H NMR (CDCl3, 400MHz) δ 9.90(s, 1H), 8.98-8.97(m, 2H), 8.73-8.72(d, 1H), 8.59(s, 1H), 8.36(d, 3H), 8.25(d, 1H), 8.15(s, 1H), 7.90(d, 3H), 7.89-7.86(m, 1H), 7.77(d, 2H), 7.72-7.65(m, 4H), 7.64-7.61(m, 2H), 7.53-7.50(m, 3H), 7.48-7.44(m, 2H), 7.37-7.33(m, 3H), 7.28-7.24(m, 2H).[Synthesis Example 8]

Place quinoline-8-boronic acid (4.35 g, 25.13 mmol), compound C (15 g, 22.84 mmol) and potassium carbonate (7.9 g, 57.1 mmol) in the reaction flask, then add toluene 225 ml, ethanol 38 ml, remove Ionized water 76 ml and put N ₂ and condensing tube on the rack and transfer the reaction to the oil pot, heating and stirring at 80 ℃. Add tetrakis(triphenylphosphine)palladium (1.32 g, 1.14 mmol) to the reaction flask. After the reaction is complete and a lot of solids are precipitated, remove the oil bath to cool down and filter first. Pour the filter cake into the beaker and add 100 ml of deionized water was stirred for 10 mins and then filtered. The filter cake was dug into a beaker and heated with 3000 ml of tetrahydrofuran and stirred to complete dissolution. After passing through the column (20 g SiO ₂ ), the filtrate was concentrated until a white solid precipitated out. Ethyl acetate was used to rinse and filter. After drying, 12 g of white solid compound 1-11 was obtained with a yield of 74.5%. The measurement results of ¹ H NMR are shown below. 1H NMR (CDCl3, 400MHz) δ 9.90(s, 1H), 8.98-8.97(m, 2H), 8.73-8.72(d, 1H), 8.59(s, 1H), 8.36(d, 3H), 8.25(d , 1H), 8.15(s, 1H), 7.90(d, 3H), 7.89-7.86(m, 1H), 7.77(d, 2H), 7.72-7.65(m, 4H), 7.64-7.61(m, 2H ), 7.53-7.50(m, 3H), 7.48-7.44(m, 2H), 7.37-7.33(m, 3H), 7.28-7.24(m, 2H).

將 化合物C (10 g，15.23 mmole)與(10-苯基蒽-9-基)硼酸 (4.99 g，16.75 mmole)置於反應槽，加入甲苯 120 ml。將K₂ CO₃ (7.36 g，53.3 mmole)溶於70 ml去離子水後加入反應槽，加入四(三苯基膦)鈀 (0.88 g，0.76 mmole)及乙醇 30 ml開啟加熱及攪拌。加熱至80 ℃反應整晚。反應完後加入300 ml DI water，攪拌30min，靜置使其分層，進行萃取，將萃取後濾液加入以填充矽膠進行層析法純化，濃縮至濃稠後加入己烷 300 mL加強析出，有機層合併過濾固體，得到7g淡黃色固體化合物1-13，產率55.4%。 以下顯示¹ H NMR之測定結果。¹ H NMR (CDCl₃ , 400MHz) d 9.90(s,1H), 8.95-8.93(m, 1H), 8.74-8.73 (m, 1H), 8.58(d, 1H), 8.38(s, 1H), 8.33(d, 2H), 8.14(s, 1H), 7.91(d, 1H), 7.86(t, 1H), 7.74-7.50(m, 17H), 7.49-7.43(m, 1H), 7.38-7.34(m, 7H), 7.30-7.25(m, 4H).[Synthesis Example 9]

Compound C (10 g, 15.23 mmole) and (10-phenylanthracene-9-yl)boronic acid (4.99 g, 16.75 mmole) were placed in the reaction tank, and 120 ml of toluene was added. Dissolve K ₂ CO ₃ (7.36 g, 53.3 mmole) in 70 ml of deionized water and add it to the reaction tank. Add tetrakis(triphenylphosphine)palladium (0.88 g, 0.76 mmole) and 30 ml of ethanol to turn on heating and stirring. Heated to 80 ℃ to react overnight. After the reaction, add 300 ml of DI water, stir for 30min, let stand for layer separation, and perform extraction. The filtrate after extraction is filled with silica gel for chromatographic purification. After concentration to a thick concentration, 300 mL of hexane is added to enhance precipitation. Organic The solids were combined and filtered to obtain 7g of light yellow solid compound 1-13, yield 55.4%. The measurement results of ¹ H NMR are shown below. ¹ H NMR (CDCl ₃ , 400MHz) d 9.90(s,1H), 8.95-8.93(m, 1H), 8.74-8.73 (m, 1H), 8.58(d, 1H), 8.38(s, 1H), 8.33 (d, 2H), 8.14(s, 1H), 7.91(d, 1H), 7.86(t, 1H), 7.74-7.50(m, 17H), 7.49-7.43(m, 1H), 7.38-7.34(m , 7H), 7.30-7.25(m, 4H).

將1-芘硼酸(2.6 g，10.6 mmol)、化合物C (5.8 g，8.8 mmol) 與碳酸鉀(2.4 g，17.6 mmol)置於反應瓶，再加入甲苯160 ml、乙醇110 ml、去離子水50 ml並架上N₂ 與冷凝管並將反應移至油鍋中，加熱攪拌80 ℃。將四(三苯基膦)鈀(0.5 g，0.44 mmol)加入反應瓶。反應隔夜後，移除油浴降溫後，加入乙酸乙酯100 ml萃取，收集有機層、濃縮，加入甲醇20 ml析出固體，過濾烘乾後得到3.94 g灰色固體化合物1-20，產率57.4%。 以下顯示¹ H NMR之測定結果。 1H NMR (CDCl3, 400MHz) δ 9.91(s, 1H), 8.92(d, 1H), 8.73(d, 1H), 8.51(s, 1H), 8.42(d, 1H), 8.34(d, 2H), 8.28(d, 1H), 8.23-8.17(m, 3H), 8.15-8.13(m, 3H), 8.09-8.01(m, 3H), 7.91(d, 1H), 7.84-7.82(m, 1H), 7.79-7.74(m, 3H), 7.69-7.68(m, 2H), 7.56-7.50(m, 3H), 7.44-7.41(m, 1H), 7.37-7.34(m, 3H), 7.29-7.25(m, 2H).[Synthesis Example 10]

Put 1-pyreneboronic acid (2.6 g, 10.6 mmol), compound C (5.8 g, 8.8 mmol) and potassium carbonate (2.4 g, 17.6 mmol) in the reaction flask, then add 160 ml of toluene, 110 ml of ethanol, and deionized water Place 50 ml of N ₂ and a condenser tube and transfer the reaction to an oil pan, heating and stirring at 80 ℃. Tetrakis(triphenylphosphine)palladium (0.5 g, 0.44 mmol) was added to the reaction flask. After the reaction overnight, after removing the oil bath and cooling, add ethyl acetate 100 ml for extraction, collect the organic layer, concentrate, add methanol 20 ml to precipitate solid, filter and dry to obtain 3.94 g of gray solid compound 1-20, yield 57.4% . The measurement results of ¹ H NMR are shown below. 1H NMR (CDCl3, 400MHz) δ 9.91(s, 1H), 8.92(d, 1H), 8.73(d, 1H), 8.51(s, 1H), 8.42(d, 1H), 8.34(d, 2H), 8.28(d, 1H), 8.23-8.17(m, 3H), 8.15-8.13(m, 3H), 8.09-8.01(m, 3H), 7.91(d, 1H), 7.84-7.82(m, 1H), 7.79-7.74(m, 3H), 7.69-7.68(m, 2H), 7.56-7.50(m, 3H), 7.44-7.41(m, 1H), 7.37-7.34(m, 3H), 7.29-7.25(m , 2H).

Table 2 shows the physical property values of the above materials. The measurement method of each physical property value is as follows. (1) Thermal cracking temperature (T _d ) was measured using a thermogravimetric analyzer (Perkin Elmer, TGA8000), under normal pressure and under a nitrogen atmosphere, at a programmed heating rate of 20° C./min. The thermal cracking property is measured, and the temperature at which the weight is reduced to 95% of the initial weight is the thermal cracking temperature (T _d ). (2) Glass transition temperature (T _g ) A differential scanning thermal analyzer (DSC; Perkin Elmer, DSC8000) was used to measure the prepared compound at a programmed heating rate of 20° C./min. (3) The energy level of the highest occupied molecular orbital (HOMO) In addition, the compound is made into a thin film state, and its ionization potential value is measured under the atmosphere using a photoelectron spectrophotometer (Riken Keiki, Surface Analyzer), and its value is further converted The latter is the HOMO energy level value. (4) The energy level of the lowest unoccupied molecular orbital (LUMO) The film of the above compound is measured by UV/VIS spectrophotometer (Perkin Elmer, Lambda20) to measure the boundary value (onset) of its absorption wavelength, and this value is converted To obtain the energy gap value, the energy gap value is subtracted from the value of the HOMO energy level to obtain the LUMO energy level. (5) Triplet energy value (E _T ) Use a fluorescence spectrometer (Perkin Elmer, LS55) to measure the luminescence spectrum at a temperature of 77K, and then calculate it to obtain E _T.

[Table 2]

Example 1: Manufacture of organic electroluminescence device Before loading the substrate into the evaporation system, the substrate was first cleaned with solvent and ultraviolet ozone for degreasing. After that, the substrate is transferred to the vacuum deposition chamber, and all layers are deposited on top of the substrate. At a vacuum of about 10-6 Torr, use a heated evaporation boat (boat) to sequentially deposit the following layers as shown in Figure 2: a) Anode thickness 135nm b) Hole injection layer: thickness 20nm, including HTM doped with 9% p-type electrically conductive dopant, wherein the p-type electrically conductive dopant is purchased from Shanghai Hanfeng Chemical Co., Ltd., and the HTM is purchased from Merck & Co., Inc.; c ) Hole transmission layer: thickness 170 nm, HTM; d) Exciton barrier layer: thickness 10 nm, HT (made by Yura Optoelectronics); e) Light emitting layer: thickness 25 nm, including 4% by volume Compared with EBH of BD, where BD and EBH are prepared by Yulei Optoelectronics; f) Electron transport layer: 25 nm thick, containing compound 1-2 (to be confirmed by customers) and doped lithium quinoline (Liq, Yulei Optoelectronic preparation), volume ratio is 1:1; g) electron injection layer: thickness 0.5 nm, lithium fluoride (LiF); and h) cathode, thickness about 180 nm, including A1.

The device structure can be expressed as: ITO/HTM: p-type electrically conductive dopant (20 nm)/HTM (170 nm)/HT (10 nm)/EBH: BD (25 nm)/Compound 1-2 : Liq (25nm)/LiF (0.5nm)/Al (180nm).

After depositing and forming the above-mentioned layers, the device is transferred from the deposition chamber to a drying oven, and then encapsulated with a UV curable epoxy resin and a glass cover plate containing a moisture absorbent. The organic electroluminescence element has a light emitting area of 9 square millimeters.

Examples 2 to 5: Manufacture of organic electroluminescence elements except that compound 1-2 of the electron transport layer in Example 1 was replaced with compounds 1-3, 1-7, 1-12, and 1-13, respectively. The organic electroluminescence elements were manufactured in the same manner as in Example 1. In addition, the layer structure of Examples 2 to 5 is the same as that of Example 1.

Comparative Example 1: Fabrication of organic electroluminescence element The structure of the organic electroluminescence element was made similar to the layer structure of Example 1, except that compound 1-2 of the electron transport layer in Example 1 was replaced with compound EET09. The structure of the organic electroluminescence element can be expressed as: ITO/HTM: p dopant (20 nm)/HTM (170 nm)/HT (10 nm)/EBH: BD (25 nm)/compound EET09: Liq ( 25 nm)/LiF (0.5 nm)/Al (180 nm). Among them, the compound EET09 is as described in Japanese Patent No. 2011003793A. The electrical excitation properties of the organic electroluminescence elements made above are all using constant current source (KEITHLEY 2400 Source Meter, made by Keithley Instruments, Inc., Cleveland, Ohio) and photometer (PHOTO RESEARCH SpectraScan PR 650, made by PhotoResearch , Inc., Chatsworth, Calif.) The luminescence properties were measured at room temperature, based on the organic electroluminescence element of the comparative example (standard value is 1), and the values of its driving voltage, luminous efficiency and LT95 are listed于表3。 In Table 3. Among them, the LT95 value is defined as the time it takes for the brightness level to decrease to 95% of the initial brightness, and it is used as a measurement standard for evaluating the service life or stability of the organic electroluminescence element.

[table 3]

As shown in Table 2, relative to the comparative example, the benzimidazole substituted diphenylpyrimidine compound represented by formula (I) of the present invention has a higher thermal cracking temperature (T _d ) and glass transition temperature (T _g ) And, as shown in Table 3, the organic electroluminescence device made of the benzimidazole-substituted diphenylpyrimidine compound represented by formula (I) of the present invention has a better lifetime than the comparative example.

Therefore, the benzimidazole-substituted diphenylpyrimidine compound represented by formula (I) of the present invention having high thermal cracking temperature, high glass transition temperature and long life can improve the problems of the prior art and has extremely high technical value, and The organic electroluminescent element made of diphenylpyrimidine compound substituted by benzimidazole represented by formula (I) is especially suitable for vehicle display or OLED lighting source.

The above-mentioned embodiments are only illustrative and not intended to limit the present invention. The scope of protection of the rights of the present invention is defined by the patent application scope of the present invention. In addition, any person who is familiar with this skill can modify, replace, omit, or convert the present invention without departing from the spirit and scope of the present invention, which are included in the patent application scope of the present invention.

100, 200, 300 ‧‧‧ organic electroluminescence element 110, 210, 310 ‧ ‧‧ substrate 120, 220, 320 ‧ ‧ ‧ anode 130, 230, 330 ‧ ‧ ‧ hole injection layer 140, 240, 340 ‧ ‧Electron transport layer 150, 250, 350 ‧‧‧ Light emitting layer 160, 260, 360 ‧‧‧ Electron transport layer 170, 270, 370 ‧‧‧ Electron injection layer 180, 280, 380 ‧‧‧ Cathode 245, 355‧ ‧‧Exciton barrier

1 is a schematic cross-sectional view of an embodiment of an organic electroluminescence device of the present invention. 2 is a schematic cross-sectional view of another embodiment of the organic electroluminescence device of the present invention. 3 is a schematic cross-sectional view of still another embodiment of the organic electroluminescence device of the present invention.

200‧‧‧ organic electroluminescence element

210‧‧‧ substrate

220‧‧‧Anode

230‧‧‧hole injection layer

240‧‧‧Electric transmission layer

245‧‧‧ exciton blocking layer

250‧‧‧luminous layer

260‧‧‧Electronic transmission layer

270‧‧‧Electron injection layer

280‧‧‧Cathode

Claims (15)

A diphenylpyrimidine compound substituted by benzimidazole is represented by the following formula (I),

Formula (I) where X ₁ represents a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (5- to 30-membered) heteroaryl group; Ar represents a substituted or unsubstituted Substituted (C6-C30) aryl, substituted or unsubstituted (5- to 30-membered) heteroaryl; X ₁ and Ar are the same or different, and at least one is substituted or unsubstituted (5- to 30-membered) heteroaryl; n represents an integer of 1 or 2, when n represents 2, Ar is the same or different. The benzimidazole substituted diphenylpyrimidine compound as described in claim 1, which is represented by the structure of formula (I-1), formula (I-2) or formula (I-3):

Formula (I-1)

Formula (I-2)

Formula (I-3) where X ₁ represents a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (5- to 30-membered) heteroaryl group; Ar represents a substituted or Unsubstituted (C6-C30) aryl, substituted or unsubstituted (5- to 30-membered) heteroaryl; X ₁ and Ar are the same or different, and at least one is substituted or unsubstituted Substituted (5- to 30-membered) heteroaryl; n represents an integer of 1 or 2, when n represents 2, Ar is the same or different. The benzimidazole-substituted diphenylpyrimidine compound according to claim 1, wherein X ₁ is pyridyl, quinolinyl, or naphthyl. The benzimidazole-substituted diphenylpyrimidine compound according to claim 1 or 2, wherein X ₁ is one selected from the group consisting of:

Among them, Xr represents hydrogen, fluorine, cyano, C1-4 alkyl or unsubstituted C6-18 aryl. The benzimidazole-substituted diphenylpyrimidine compound according to claim 1 or 2, wherein Ar is selected from one of the following groups:

Among them, L represents O or S; Ar ₁ to Ar ₆ each independently represent hydrogen, unsubstituted C6-18 aryl; R ₁ to R ₄ each independently represent hydrogen, substituted or unsubstituted C6-12 aryl , R ₁ and R ₂ and the connected carbon atoms together form a C6-18 fused aromatic ring system or R ₃ and R ₄ and the connected carbon atoms together form a C6-18 fused aromatic ring system; and Y ₁ and Y _{One of 2} is a single bond and is connected to the compound of formula (I), and the other is hydrogen. The benzimidazole-substituted diphenylpyrimidine compound according to claim 5, wherein the unsubstituted C6-18 aryl group is phenyl, and the unsubstituted C6-12 aryl group is phenyl. The benzimidazole-substituted diphenylpyrimidine compound according to claim 1, wherein, when n is 1, the compound of formula (I) is represented by formula (I-4) or formula (I-5):

Formula (I-4)

Formula (I-5). The benzimidazole substituted diphenylpyrimidine compound according to claim 1, wherein, when n is 2, the compound of formula (I) is represented by formula (I-6),

Formula (I-6). The benzimidazole-substituted diphenylpyrimidine compound according to claim 8, wherein the Ar has the same structure. The benzimidazole-substituted diphenylpyrimidine compound described in 7 or 8 is one of the following compounds (1-1) to (1-36):

. The benzimidazole-substituted diphenylpyrimidine compound according to claim 1 or 2, wherein the heteroaryl group contains at least one heteroatom selected from the group consisting of N, O, and S. An organic electroluminescence element, comprising: a cathode; an anode; and an organic layer: interposed between the cathode and the anode, containing diphenylpyrimidine substituted with benzimidazole according to any one of claims 1 to 11 Compound. The organic electroluminescence device according to claim 12, wherein the organic layer is at least one selected from the group consisting of an electron transport layer, an electron injection layer, a light emitting layer, a hole blocking layer, and an electron blocking layer. The organic electroluminescence device according to claim 12 or 13, wherein the organic layer is an electron transport layer, and the thickness thereof is 20 nm to 30 nm. The organic electroluminescence device according to claim 13 or 14, wherein the electron transport layer contains an N-type electrically conductive dopant, and the content of the N-type electrically conductive dopant is 0% to 50% by weight.

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