TW202007760A - 9,9-spirobifluorene-substituted diphenylpyrimidines compounds and organic electroluminescent devices using the same - Google Patents

Abstract

The present invention provides 9,9-spirobifluorene-substituted diphenylpyrimidines compounds of formula (I) and an organic electroluminescent device using the same: wherein X1, A1 and n are as defined in the description.

Description

Diphenylpyrimidine compound substituted with 9,9-spirobifluorene and its organic electroluminescence element

The invention relates to a diphenylpyrimidine compound substituted with 9,9-spirobifluorene 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, and when the excitons are out of the excited state When returning to the ground state, energy is released 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. 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, until now it has been difficult to find organic materials that meet the needs of all practical display applications, especially those that require high temperature resistance and long life characteristics for automotive displays or lighting sources.

Therefore, there is an urgent need for an organic material that can significantly improve the life of organic electroluminescence devices, have good luminous efficiency, and have good heat resistance, so as 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； A₁ 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A₁ 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，A₁ 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9,9-螺二芴取代之二苯基嘧啶化合物。 藉由本發明的以式（I）表示之經9,9-螺二芴取代之二苯基嘧啶化合物，可提供一種壽命長、發光效率佳及耐熱性良好的有機材料，能夠滿足顯示器實際應用之需求，特別適合作為車用顯示器或OLED照明光源。The object of the present invention is to provide an organic material having a long life, good luminous efficiency and good heat resistance. The present invention provides a diphenylpyrimidine compound substituted with 9,9-spirobifluorene, 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; A ₁ represents a substituted or unsubstituted Substituted (C6-C30) aryl, substituted or unsubstituted (5- to 30-membered) heteroaryl; X ₁ and A ₁ 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, A ₁ 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 9,9-spirobifluorene substituted by the present invention represented by formula (I) The diphenyl pyrimidine compound. The diphenylpyrimidine compound substituted by 9,9-spirobifluorene represented by formula (I) of the present invention can provide an organic material with long life, good luminous efficiency and good heat resistance, which can meet the practical application of the display Demand, especially suitable as a car display or OLED 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； A₁ 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A₁ 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，A₁ 各自為相同或相異。The diphenylpyrimidine compound substituted with 9,9-spirobifluorene 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; A ₁ represents a substituted or unsubstituted Substituted (C6-C30) aryl, substituted or unsubstituted (5- to 30-membered) heteroaryl; X ₁ and A ₁ 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, A ₁ 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； A₁ 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A₁ 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，A₁ 各自為相同或相異。In a specific embodiment, the above-mentioned diphenylpyrimidine compound substituted with 9,9-spirobifluorene represented by formula (I) is represented by the following formula (I-1), formula (I-2) or formula (I-3) Structural 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; A ₁ represents a substituted Or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5- to 30-membered) heteroaryl; X ₁ and A ₁ 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, A ₁ is the same or different.

In the present invention, A ₁ of the diphenylpyrimidine compound substituted with 9,9-spirobifluorene represented by formula (I) is a substituted or unsubstituted (C6-C30) aryl group, substituted or unsubstituted (5- to 30-member) heteroaryl groups, the reason is that the more plane structures, the more helpful the molecular stacking and increase the transmission effect of their carriers, but the group carbon number should not be too much to avoid the formation Unnecessary crystallization.

In the present invention, X ₁ of the diphenylpyrimidine compound substituted by 9,9-spirobifluorene represented by formula (I) 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 diphenylpyrimidine compound substituted by 9,9-spirobifluorene 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, A ₁ in the diphenylpyrimidine compound substituted by 9,9-spirobifluorene 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-2) or formula (I-3).

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 embodiment, when n is 2, the A _{1 has} a different 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, isothiazolyl, isooxazolyl, oxazolyl, oxadiazolyl, three wells, four wells, triazolyl, tetrazolyl, furan Xyl, pyridyl, pyridyl, pyrimidinyl, tachydyl, piperidinyl, etc., or a fused ring condensed with at least one benzene ring, for example, benzofuranyl, benzothienyl , Isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisooxazolyl, benzodioxazolyl , Benzopyrazolyl, or, for example, may be quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinolozinyl, carbazolyl, morpholinium, porazolyl, dipyridyl Hydroacridinyl, imidazolidinyl, mouthnetidinyl, oxacinyl, acridinyl, morpholinyl, indolyl, morphine, etc.

In specific embodiments, the preferred form of the diphenylpyrimidine compound substituted with 9,9-spirobifluorene represented by the formula (I) in the present invention is shown in Table 1 below, but is not limited thereto.

[Table 1]

The diphenylpyrimidine compound substituted by 9,9-spirobifluorene represented by the formula (I) in the present invention can withstand the long-term high temperature inside the automobile because its glass transition temperature is between 146°C and 223°C. It is especially suitable for organic electro-luminescence device of car display.

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 9,9-spirobifluorene substituted by the invention represented by formula (I) Diphenylpyrimidine 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 diphenylpyrimidine compound substituted by 9,9-spirobifluorene represented by formula (I) of the present invention is preferably an electron transport layer, and the thickness thereof is preferably 20 Nanometer to 30 nanometers; wherein, the electron transport layer can use the diphenylpyrimidine compound substituted with 9,9-spirobifluorene having the structure of formula (I) as a single material, or have the structure of formula (I) The diphenylpyrimidine compound substituted by 9,9-spirobifluorene is used in combination with an electrically conductive dopant.

In another specific embodiment, the electron transport layer further contains an N-type electrically conductive dopant, wherein the n-type electrically conductive dopant and the present invention have the structure of formula (I) through the 9,9-spiro two Fluorine-substituted diphenylpyrimidine compounds will produce chelation, which can make electrons easier to be injected from the cathode into the electron transport layer, so it can solve the problems caused by the poor compatibility of metals and electron transport materials in the prior art. The problems of phase separation and quenching 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 diphenylpyrimidine compound substituted by 9,9-spirobifluorene represented by the formula (I) of the present invention has a triplet energy level higher than 2.2 eV, a HOMO energy level deeper than 6.0 eV and good carriers Mobility, so when used in the case of an electron transport layer, can help promote 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 application and principle of each barrier layer disclosed in US Patent Nos. 6,097,147 and 20030230980, and all contents thereof. 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 diphenylpyrimidine compound substituted by 9,9-spirobifluorene represented by formula (I) in the present invention can be made by vacuum deposition, wet coating method (including spin coating method, inkjet method) or printing method Amorphous thin film used in organic electroluminescence devices.

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 the luminous efficiency and lifespan. 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-溴苯乙酮（10g，50.23mmole）與9,9'-螺二[茀]-2-基硼酸（18.45g，52.12mmole）置於反應槽，加入甲苯120ml。將K₂ CO₃ （24.3g，175.8mmole）溶於70ml去離子水後加入反應槽，加入Pd（PPh₃ ）₄ （1.74g，1.507mmole）及EtOH 30ml開啟加熱及攪拌。加熱至80℃反應整晚。反應完後加入300ml去離子水，攪拌30min後停止攪拌，靜置使其分層，去除水層後，用矽膠層析法純化，濃縮至濃稠後加入己烷300ml析出，有機層合併過濾固體，得到乳白色固體A（約15g）。

將化合物A（10g，23.01mmole）與3-溴苯甲醛（5.11g，27.6mmole）置於反應槽，充分除水後加入Ethanol 150ml，開啟攪拌，並添加氫氧化鈉（0.276g，6.9mmole），於室溫攪拌16hr。其後，添加3-吡啶偕胺肟鹽（3-Amidinopyridinium chloride）（3.97g，25.2mmole）與氫氧化鈉（1.3g，34.4mmole），並追加入甲苯20ml，打開加熱裝置。加熱至75℃反應整晚。反應完後，過濾取固體用甲苯250ml，加熱攪拌過濾固體，得到乳白色固體B（約6.4g）。

將化合物B（10g，14.23mmole）與萘-1-基硼酸（2.93g，17.07mmole）置於反應槽，加入甲苯120ml。將K₂ CO₃ （6.88g，49.8mmole）溶於70ml去離子水後加入反應槽，加入Pd（PPh₃ ）₄ （0.65g，0.56mmole）及EtOH 30ml開啟加熱及攪拌。加熱至80℃反應整晚。反應完後加入300ml去離子水，攪拌30min，靜置使其分層，然後進行萃取，加入矽膠進行層析法純化，濃縮至濃稠後加入己烷300mL加強析出，有機層合併過濾固體，得到乳淡黃色固體化合物1-9（約5.5g）。 以下顯示¹ H NMR之測定結果。¹ H NMR（CDCl₃ , 400MHz） d 9.86（s, 1H）, 8.91-8.89（m, 1H）, 8.73-8.70（m, 1H）, 8.36-8.30（m, 2H）, 8.26（d, 2H）, 8.07（s, 1H）, 7.97-7.85（m, 6H）, 7.72-7.66（m, 3H）, 7.54-7.52（m, 3H）, 7.50-7.49（m, 2H）, 7.48-7.36（m,6H）, 7.15（t, 3H）, 7.03-7.02（m, 1H）, 6.80（d, 2H）, 6.74（d, 1H）.Synthesis Example 1: Synthesis of Compounds 1-9

4-Bromoacetophenone (10g, 50.23mmole) and 9,9'-spirobis[fu]]-2-ylboronic acid (18.45g, 52.12mmole) were placed in the reaction tank, and 120ml of toluene was added. The _{K 2 CO 3 (24.3g, 175.8mmole} ) was dissolved in 70ml reaction vessel was added deionized water, was added _{Pd (PPh 3) 4 (1.74g} , 1.507mmole) and EtOH 30ml turn heating and stirring. Heat to 80°C to react overnight. After the reaction was completed, 300ml of deionized water was added. After stirring for 30min, the stirring was stopped and allowed to stand to separate layers. After the water layer was removed, it was purified by silica gel chromatography. After concentrated to a thick concentration, 300ml of hexane was added to separate out. The organic layer was combined to filter the solid. To obtain milky white solid A (about 15g).

Place compound A (10g, 23.01mmole) and 3-bromobenzaldehyde (5.11g, 27.6mmole) in the reaction tank. After fully removing water, add Ethanol 150ml, start stirring, and add sodium hydroxide (0.276g, 6.9mmole) And stirred at room temperature for 16 hr. Thereafter, 3-Amidinopyridinium chloride (3.97g, 25.2mmole) and sodium hydroxide (1.3g, 34.4mmole) were added, followed by 20ml of toluene, and the heating device was turned on. Heated to 75°C to react overnight. After the reaction was completed, 250 ml of toluene was taken by filtration, and the solid was filtered by heating and stirring to obtain milky white solid B (about 6.4 g).

Compound B (10g, 14.23mmole) and naphthalene-1-ylboronic acid (2.93g, 17.07mmole) were placed in the reaction vessel, and 120ml of toluene was added. After the _{K 2 CO 3 (6.88g, 49.8mmole} ) was dissolved in 70ml deionized water was added the reaction vessel, was added _{Pd (PPh 3) 4 (0.65g} , 0.56mmole) and EtOH 30ml turn heating and stirring. Heat to 80°C to react overnight. After the reaction was completed, 300ml of deionized water was added, stirred for 30min, and allowed to stand for layer separation, and then extracted. Silica gel was added for chromatography purification. After concentration to thick, 300mL of hexane was added to enhance precipitation. The organic layer was combined and filtered to obtain solid Milky yellow solid compound 1-9 (about 5.5g). The measurement results of ¹ H NMR are shown below. ¹ H NMR (CDCl ₃ , 400MHz) d 9.86 (s, 1H), 8.91-8.89 (m, 1H), 8.73-8.70 (m, 1H), 8.36-8.30 (m, 2H), 8.26 (d, 2H) , 8.07 (s, 1H), 7.97-7.85 (m, 6H), 7.72-7.66 (m, 3H), 7.54-7.52 (m, 3H), 7.50-7.49 (m, 2H), 7.48-7.36 (m, 6H), 7.15 (t, 3H), 7.03-7.02 (m, 1H), 6.80 (d, 2H), 6.74 (d, 1H).

將化合物B（10g，14.23mmole）與二苯并[b,d]呋喃-4-基硼酸（3.16g，14.9mmole）置於反應槽，加入甲苯120ml。將K₂ CO₃ （6.88g，49.8mmole）溶於70ml去離子水後加入反應槽，加入Pd（PPh₃ ）₄ （0.82g，0.71mmole）及EtOH 30ml開啟加熱及攪拌。加熱至80℃反應整晚。反應完後加入300ml去離子水，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300ml加強析出，有機層合併過濾固體，得到乳白色固體化合物1-10（約6.1g）。 以下顯示¹ H NMR之測定結果。¹ H NMR（CDCl₃ , 400MHz） d 9.90（s, 1H）, 8.93（d, 1H）, 8.80（s, 1H）, 8.74-8.73（m, 1H）, 8.29-8.28（m, 3H）, 8.11-8.10（m, 2H）, 7.96-7.94（m, 1H）, 7.88-7.87（m, 1H）, 7.72-7.71（m, 1H）, 7.71-7.70（m, 3H）, 7.50-7.35（m, 9H）, 7.14（t, 7H）, 7.05（s, 1H）, 6.74（d, 2H）, 6.69（d, 1H）.Synthesis Example 2: Synthesis of Compounds 1-10

Compound B (10g, 14.23mmole) and dibenzo[b,d]furan-4-ylboronic acid (3.16g, 14.9mmole) were placed in the reaction tank, and 120ml of toluene was added. After the _{K 2 CO 3 (6.88g, 49.8mmole} ) was dissolved in 70ml deionized water was added the reaction vessel, was added _{Pd (PPh 3) 4 (0.82g} , 0.71mmole) and EtOH 30ml turn heating and stirring. Heat to 80°C to react overnight. After the reaction, 300 ml of deionized water was added, stirred for 30 min, and allowed to stand to separate layers for extraction. The filtrate after extraction was filled with silica gel for chromatography purification. After concentrating to a thick concentration, 300 ml of hexane was added to enhance precipitation, and the organic layer was combined and filtered to obtain a milky white solid compound 1-10 (about 6.1 g). The measurement results of ¹ H NMR are shown below. ¹ H NMR (CDCl ₃ , 400MHz) d 9.90 (s, 1H), 8.93 (d, 1H), 8.80 (s, 1H), 8.74-8.73 (m, 1H), 8.29-8.28 (m, 3H), 8.11 -8.10 (m, 2H), 7.96-7.94 (m, 1H), 7.88-7.87 (m, 1H), 7.72-7.71 (m, 1H), 7.71-7.70 (m, 3H), 7.50-7.35 (m, 9H), 7.14 (t, 7H), 7.05 (s, 1H), 6.74 (d, 2H), 6.69 (d, 1H).

將化合物B（10g，14.23mmole）與二苯并[b,d]噻吩-4-基硼酸（3.4g，14.9mmole）置於反應槽，加入甲苯120ml。將K₂ CO₃ （6.88g，49.8mmole）溶於70ml去離子水後加入反應槽，加入Pd（PPh₃ ）₄ （0.82g，0.71mmole）及EtOH 30ml開啟加熱及攪拌。加熱至80℃反應整晚。反應完後加入300ml去離子水，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300ml加強析出，有機層合併過濾固體，得到乳白色固體化合物1-11（約5g）。 以下顯示¹ H NMR之測定結果。¹ H NMR（CDCl₃ , 400MHz） d 9.88（s, 1H）, 8.39（s, 1H）, 8.73-8.72（m, 1H）, 8.72（s, 1H）, 8.35（d, 1H）, 8.33-8.32（m, 4H）, 8.22（s, 1H）, 7.96-7.83（m, 6H）, 7.74-7.71（m, 2H）, 7.63-7.60（m, 4H）, 7.50-7.34（m, 6H）, 7.18（t, 3H）, 7.04（s, 1H）, 6.82（d, 2H）, 6.73（s, 1H）.Synthesis Example 3: Synthesis of Compound 1-11

Compound B (10g, 14.23mmole) and dibenzo[b,d]thiophen-4-ylboronic acid (3.4g, 14.9mmole) were placed in the reaction tank, and 120ml of toluene was added. After the _{K 2 CO 3 (6.88g, 49.8mmole} ) was dissolved in 70ml deionized water was added the reaction vessel, was added _{Pd (PPh 3) 4 (0.82g} , 0.71mmole) and EtOH 30ml turn heating and stirring. Heat to 80°C to react overnight. After the reaction, 300ml of deionized water was added, stirred for 30min, and allowed to stand to separate layers for extraction. The extracted filtrate was filled with silica gel and purified by chromatography. After concentration to a thick concentration, 300ml of hexane was added to enhance precipitation. The organic layer The filtered solids were combined to give milky white solid compounds 1-11 (about 5g). The measurement results of ¹ H NMR are shown below. ¹ H NMR (CDCl ₃ , 400MHz) d 9.88 (s, 1H), 8.39 (s, 1H), 8.73-8.72 (m, 1H), 8.72 (s, 1H), 8.35 (d, 1H), 8.33-8.32 (M, 4H), 8.22 (s, 1H), 7.96-7.83 (m, 6H), 7.74-7.71 (m, 2H), 7.63-7.60 (m, 4H), 7.50-7.34 (m, 6H), 7.18 (T, 3H), 7.04 (s, 1H), 6.82 (d, 2H), 6.73 (s, 1H).

將化合物B（10g，14.23mmole）與（3-（吡啶-3-基）苯基）硼酸（3.4g，14.9mmole）置於反應槽，加入甲苯120ml。將K₂ CO₃ （6.88g，49.8mmole）溶於70ml去離子水後加入反應槽，加入Pd（PPh₃ ）₄ （0.82g，0.71mmole）及EtOH 30ml開啟加熱及攪拌。加熱至80℃反應整晚。反應完後加入300ml去離子水，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300ml加強析出，有機層合併過濾固體，得到乳白色固體化合物1-12（約5.5g）。 以下顯示¹ H NMR之測定結果。¹ H NMR（CDCl₃ , 400MHz） d 9.87（s, 1H）, 8.94-8.91（m, 2H）, 8.87-8.74（m, 1H）, 8.64-8.63（m, 1H）, 8.49（s, 1H）, 8.26（d, 3H）, 8.07（s, 1H）, 7.91（d, 2H）, 7.89-7.88（m, 4H）, 7.88（d, 1H）, 7.82-7.67（m, 7H）, 7.64-7.64（m, 5H）, 7.17（t, 3H）, 7.07-7.04（m, 1H）, 6.83（d, 2H）, 6.78（d, 1H）.Synthesis Example 4: Synthesis of Compounds 1-12

Compound B (10g, 14.23mmole) and (3-(pyridin-3-yl)phenyl)boronic acid (3.4g, 14.9mmole) were placed in the reaction vessel, and 120ml of toluene was added. After the _{K 2 CO 3 (6.88g, 49.8mmole} ) was dissolved in 70ml deionized water was added the reaction vessel, was added _{Pd (PPh 3) 4 (0.82g} , 0.71mmole) and EtOH 30ml turn heating and stirring. Heat to 80°C to react overnight. After the reaction, 300ml of deionized water was added, stirred for 30min, and allowed to stand to separate layers for extraction. The extracted filtrate was filled with silica gel and purified by chromatography. After concentration to a thick concentration, 300ml of hexane was added to enhance precipitation. The organic layer The filtered solids were combined to obtain milky white solid compounds 1-12 (about 5.5 g). The measurement results of ¹ H NMR are shown below. ¹ H NMR (CDCl ₃ , 400MHz) d 9.87 (s, 1H), 8.94-8.91 (m, 2H), 8.87-8.74 (m, 1H), 8.64-8.63 (m, 1H), 8.49 (s, 1H) , 8.26 (d, 3H), 8.07 (s, 1H), 7.91 (d, 2H), 7.89-7.88 (m, 4H), 7.88 (d, 1H), 7.82-7.67 (m, 7H), 7.64-7.64 (M, 5H), 7.17 (t, 3H), 7.07-7.04 (m, 1H), 6.83 (d, 2H), 6.78 (d, 1H).

將化合物B（10g，14.23mmole）與（10-苯基蒽-9-基）硼酸（5.09g，17.01mmole）置於反應槽，加入甲苯120ml。將K₂ CO₃ （6.88g，49.8mmole）溶於70ml去離子水後加入反應槽，加入Pd（PPh₃ ）₄ （0.82g，0.71mmole）及EtOH 30ml開啟加熱及攪拌。加熱至80℃反應整晚。反應完後加入300ml去離子水，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300ml加強析出，有機層合併過濾固體，得到淡黃色固體化合物1-13（約4.3g）。 以下顯示¹ H NMR之測定結果。¹ H NMR（CDCl₃ , 400MHz） d 9.85（s, 1H）, 8.91-8.89（m, 1H）, 8.73-8.78（m, 1H）, 8.53-8.51（m, 1H）, 8.34（t, 1H）, 8.23-8.2（m, 2H）, 8.07（s, 1H）, 7.94（d, 1H）, 7.89-7.81（m, 4H）, 7.77-7.50（m, 14H）, 7.42-7.34（m, 8H）, 7.16-7.10（m, 3H）, 7.01（d, 1H）, 6.78（d, 1H）, 6.75-6.72（m, 1H）.Synthesis Example 5: Synthesis of Compound 1-13

Compound B (10g, 14.23mmole) and (10-phenylanthracene-9-yl)boronic acid (5.09g, 17.01mmole) were placed in the reaction tank, and 120ml of toluene was added. After the _{K 2 CO 3 (6.88g, 49.8mmole} ) was dissolved in 70ml deionized water was added the reaction vessel, was added _{Pd (PPh 3) 4 (0.82g} , 0.71mmole) and EtOH 30ml turn heating and stirring. Heat to 80°C to react overnight. After the reaction, 300ml of deionized water was added, stirred for 30min, and allowed to stand to separate layers for extraction. The extracted filtrate was filled with silica gel and purified by chromatography. After concentration to a thick concentration, 300ml of hexane was added to enhance precipitation. The organic layer The filtered solids were combined to give a light yellow solid compound 1-13 (about 4.3g). The measurement results of ¹ H NMR are shown below. ¹ H NMR (CDCl ₃ , 400MHz) d 9.85 (s, 1H), 8.91-8.89 (m, 1H), 8.73-8.78 (m, 1H), 8.53-8.51 (m, 1H), 8.34 (t, 1H) , 8.23-8.2 (m, 2H), 8.07 (s, 1H), 7.94 (d, 1H), 7.89-7.81 (m, 4H), 7.77-7.50 (m, 14H), 7.42-7.34 (m, 8H) , 7.16-7.10 (m, 3H), 7.01 (d, 1H), 6.78 (d, 1H), 6.75-6.72 (m, 1H).

分別將1-（4-溴苯基）乙酮（1-(4-bromophenyl)ethanone）（19.9g，100mmole）、氫氧化鉀（1.68g，30mmole）與3-溴苯甲醛（18.5g，100mmole）置於1000ml雙頸圓底瓶中，加入300ml乙醇，室溫下攪拌4小時。進行過濾後，得到乳白色固體產物化合物C（約34.4g）。

分別將（E）-3-（3-溴苯基）-1-（4-溴苯基）丙-2-烯-1-酮（9.15g，25mmole）、烟脒鹽酸鹽（nicotinamidine hydrochloride）（3.94g，25mmole）與氫氧化鉀（1.68g，30mmole）置入500ml雙頸圓底瓶中，加入150ml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，得到白色固體化合物D（約9.34克）。

分別將Pd（PPh₃ ）₄ （3.30g，2.9mmole）、K₂ CO₃ （20.1g，145.6mmole）、化合物D（17.0g，36.4mmole）與9,9’-螺二茀-2-基-硼酸（28.8g，80.1mmole）置入1000ml雙頸圓底瓶中，加入160ml 甲苯、110ml乙醇和50ml去離子水，加熱至迴流。反應隔夜後，加入100ml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 50ml加強析出，有機層合併過濾固體，得到乳白色固體化合物1-14 （約20.5克）。 以下顯示¹ H NMR之測定結果。¹ H NMR（CDCl₃ , 400MHz）, d 9.83（s, 1H）, 8.82（t, 1H）, 8.72（d, 1H）, 8.30（s, 1H）, 8.19（d, 2H）, 8.08（d, 1H）, 7.97-7.95（m, 3H）, 7.89（t, 4H）, 7.85（d, 2H）, 7.73~7.70（m, 2H）, 7.59（d, 2H）, 7.54（d, 1H）, 7.48-7.34（m, 10H）, 7.15-7.10（m, 5H）, 7.03（d, 2H）, 6.80（d, 3H）, 6.75（d, 2H）.Synthesis Example 6: Synthesis of Compound 1-14

Separately, 1-(4-bromophenyl)ethanone (1-(4-bromophenyl)ethanone) (19.9g, 100mmole), potassium hydroxide (1.68g, 30mmole) and 3-bromobenzaldehyde (18.5g, 100mmole) ) Place in a 1000ml double neck round bottom bottle, add 300ml of ethanol, and stir at room temperature for 4 hours. After filtration, compound C (about 34.4 g) was obtained as a milky white solid product.

Separately, (E)-3-(3-bromophenyl)-1-(4-bromophenyl)prop-2-en-1-one (9.15g, 25mmole) and nicotinamidine hydrochloride (3.94g, 25mmole) and potassium hydroxide (1.68g, 30mmole) were placed in a 500ml double neck round bottom bottle, 150ml of ethanol was added, and heated to reflux. After reacting for 3 hours, the mixture was left to warm to room temperature, filtered, and the solid was washed with ethanol to obtain a white solid compound D (about 9.34 g).

Separately, Pd(PPh ₃ ) ₄ (3.30 g, 2.9 mmole), K ₂ CO ₃ (20.1 g, 145.6 mmole), compound D (17.0 g, 36.4 mmole) and 9,9′-spirobifult-2-yl -Boric acid (28.8g, 80.1mmole) was placed in a 1000ml double-necked round bottom flask, 160ml of toluene, 110ml of ethanol and 50ml of deionized water were added and heated to reflux. After the reaction overnight, 100 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, 50 ml of methanol was added to enhance precipitation, and the organic layer was combined to filter the solid to obtain a milky white solid compound 1-14 (About 20.5 grams). The measurement results of ¹ H NMR are shown below. ¹ H NMR (CDCl ₃ , 400MHz), d 9.83 (s, 1H), 8.82 (t, 1H), 8.72 (d, 1H), 8.30 (s, 1H), 8.19 (d, 2H), 8.08 (d, 1H), 7.97-7.95 (m, 3H), 7.89 (t, 4H), 7.85 (d, 2H), 7.73~7.70 (m, 2H), 7.59 (d, 2H), 7.54 (d, 1H), 7.48 -7.34 (m, 10H), 7.15-7.10 (m, 5H), 7.03 (d, 2H), 6.80 (d, 3H), 6.75 (d, 2H).

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

分別將化合物E（9.15g，25mmole）、烟脒鹽酸鹽（3.94g，25mmole）與氫氧化鉀（1.68g，30mmole）置入500ml雙頸圓底瓶中，加入150ml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，得到白色固體化合物F （約8.45克）。

分別將Pd（PPh₃ ）₄ （1.65g，1.45mmole）、K₂ CO₃ （10.0g，72.8mmole）、化合物F（8.5g，18.2mmole）與9,9’-螺二茀-2-基-硼酸（14.4g，40.1mmole）置入500ml雙頸圓底瓶中，加入80ml 甲苯、55ml乙醇和25ml去離子水，加熱至迴流。反應隔夜後，加入50ml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 30ml加強析出，有機層合併過濾固體，得到乳白色固體化合物1-15 （約9.5克）。 以下顯示¹ H NMR之測定結果。¹ H NMR（CDCl₃ , 400MHz） d 9.84（s, 1H）, 8.89（t, 1H）, 8.71（d, 1H）, 8.20（d, 4H）, 7.95（d, 3H）, 7.90-7.86（m, 6H）, 7.70（d, 2H）, 7.60（d, 4H）, 7.43-7.37（m, 7H）, 7.12（t, 6H）, 7.03（s, 2H）, 6.80（d, 4H）, 6.74（d, 2H）.Synthesis Example 7: Synthesis of Compounds 1-15

Place 1-(4-bromophenyl)ethanone (19.9g, 100mmole), potassium hydroxide (1.68g, 30mmole) and 4-bromobenzaldehyde (18.5g, 100mmole) in 1000ml double neck round bottom bottles , Add 300ml of ethanol and stir at room temperature for 4 hours. After filtration, a milky white solid compound E (about 35.5 g) was obtained.

Put compound E (9.15g, 25mmole), nicotinamide hydrochloride (3.94g, 25mmole) and potassium hydroxide (1.68g, 30mmole) into 500ml double-necked round bottom flask, add 150ml of ethanol and heat to reflux. After reacting for 3 hours, it was left to warm to room temperature, and filtered, and the solid was washed with ethanol to obtain Compound F (about 8.45 g) as a white solid.

Separately, Pd(PPh ₃ ) ₄ (1.65 g, 1.45 mmole), K ₂ CO ₃ (10.0 g, 72.8 mmole), compound F (8.5 g, 18.2 mmole) and 9,9′-spirobifult-2-yl -Boric acid (14.4g, 40.1mmole) was placed in a 500ml double-necked round bottom flask, 80ml of toluene, 55ml of ethanol and 25ml of deionized water were added, and heated to reflux. After the reaction overnight, 50ml of ethyl acetate was added for extraction, and the filtrate after extraction was filled with silica gel for chromatographic purification, concentrated to a thick, 30ml of methanol was added to enhance precipitation, and the organic layer was combined to filter the solid to obtain a milky white solid compound 1-15 (About 9.5 grams). The measurement results of ¹ H NMR are shown below. ¹ H NMR (CDCl ₃ , 400MHz) d 9.84 (s, 1H), 8.89 (t, 1H), 8.71 (d, 1H), 8.20 (d, 4H), 7.95 (d, 3H), 7.90-7.86 (m , 6H), 7.70 (d, 2H), 7.60 (d, 4H), 7.43-7.37 (m, 7H), 7.12 (t, 6H), 7.03 (s, 2H), 6.80 (d, 4H), 6.74 ( d, 2H).

將化合物B（10g，14.23mmole）與芘-1-基硼酸）（3.85g，15.6mmole）置於反應槽，加入甲苯120ml。將K₂ CO₃ （6.88g，49.8mmole）溶於70ml去離子水後加入反應槽，加入Pd（PPh₃ ）₄ （0.82g，0.71mmole）及EtOH 30ml開啟加熱及攪拌。加熱至80℃反應整晚。反應完後加入300ml去離子水，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300ml加強析出，有機層合併過濾固體，得到乳白色固體化合物1-16（約5.1g）。 以下顯示¹ H NMR之測定結果。¹ H NMR（CDCl₃ , 400 MHz） d 9.87（s, 1H）, 8.62-8.91（m, 1H）, 8.72-8.71（m, 1H）, 8.49（s, 1H）, 8.39（d, 1H）, 8.28（d, 1H）, 8.24-8.12（m, 7H）, 8.09-8.02（m,4H）, 7.94（d, 1H）, 7.90-7.68（m, 6H）, 7.60（d, 2H）, 7.42-7.35（m, 4H）, 7.15-7.10（m, 3H）, 7.01（d, 1H）, 6.89（d, 2H）, 6.84（d, 1H）.Synthesis Example 8: Synthesis of Compounds 1-16

Compound B (10g, 14.23mmole) and pyrene-1-ylboronic acid) (3.85g, 15.6mmole) were placed in the reaction vessel, and 120ml of toluene was added. After the _{K 2 CO 3 (6.88g, 49.8mmole} ) was dissolved in 70ml deionized water was added the reaction vessel, was added _{Pd (PPh 3) 4 (0.82g} , 0.71mmole) and EtOH 30ml turn heating and stirring. Heat to 80°C to react overnight. After the reaction, 300ml of deionized water was added, stirred for 30min, and allowed to stand to separate layers for extraction. The extracted filtrate was filled with silica gel and purified by chromatography. After concentration to a thick concentration, 300ml of hexane was added to enhance precipitation. The organic layer The filtered solids were combined to give milky white solid compounds 1-16 (about 5.1 g). The measurement results of ¹ H NMR are shown below. ¹ H NMR (CDCl ₃ , 400 MHz) d 9.87 (s, 1H), 8.62-8.91 (m, 1H), 8.72-8.71 (m, 1H), 8.49 (s, 1H), 8.39 (d, 1H), 8.28 (d, 1H), 8.24-8.12 (m, 7H), 8.09-8.02 (m, 4H), 7.94 (d, 1H), 7.90-7.68 (m, 6H), 7.60 (d, 2H), 7.42- 7.35 (m, 4H), 7.15-7.10 (m, 3H), 7.01 (d, 1H), 6.89 (d, 2H), 6.84 (d, 1H).

將化合物B（10g，14.23mmole）與聯伸三苯-2-基硼酸（4.06g，14.9mmole）置於反應槽，加入甲苯120ml。將K₂ CO₃ （6.88g，49.8mmole）溶於70ml去離子水後加入反應槽，加入Pd（PPh₃ ）₄ （0.82g，0.71mmole）及EtOH 30ml開啟加熱及攪拌。加熱至80℃反應整晚。反應完後加入300ml去離子水，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300ml加強析出，有機層合併過濾固體，得到乳白色固體化合物1-17（約5g）。 以下顯示¹ H NMR之測定結果。¹ H NMR（CDCl₃ , 400MHz） d 9.92（s, 1H）, 8.96-8.95（m, 2H）, 8.80-8.62（m, 7H）, 8.31-8.27（m, 3H）, 8.12（s, 1H）, 8.02-7.89（m, 5H）, 7.72-7.69（m, 7H）, 7.65-7.63（m, 2H）, 7.48-7.36（m, 4H）, 7.15-7.12（m, 3H）, 7.04（d, 1H）, 6.81（d, 2H）, 6.76（d, 1H）.Synthesis Example 9: Synthesis of Compounds 1-17

Compound B (10g, 14.23mmole) and triphenyl-2-ylboronic acid (4.06g, 14.9mmole) were placed in the reaction vessel, and 120ml of toluene was added. After the _{K 2 CO 3 (6.88g, 49.8mmole} ) was dissolved in 70ml deionized water was added the reaction vessel, was added _{Pd (PPh 3) 4 (0.82g} , 0.71mmole) and EtOH 30ml turn heating and stirring. Heat to 80°C to react overnight. After the reaction, 300ml of deionized water was added, stirred for 30min, and allowed to stand to separate layers for extraction. The extracted filtrate was filled with silica gel and purified by chromatography. After concentration to a thick concentration, 300ml of hexane was added to enhance precipitation. The organic layer The filtered solids were combined to give milky white solid compounds 1-17 (about 5g). The measurement results of ¹ H NMR are shown below. ¹ H NMR (CDCl ₃ , 400MHz) d 9.92 (s, 1H), 8.96-8.95 (m, 2H), 8.80-8.62 (m, 7H), 8.31-8.27 (m, 3H), 8.12 (s, 1H) , 8.02-7.89 (m, 5H), 7.72-7.69 (m, 7H), 7.65-7.63 (m, 2H), 7.48-7.36 (m, 4H), 7.15-7.12 (m, 3H), 7.04 (d, 1H), 6.81 (d, 2H), 6.76 (d, 1H).

將化合物A (10 g，23.03 mmole)與3,5-二溴苯甲醛(3,5-dibromobenzaldehyde) (6.63 g，25.12 mmole)置於反應槽，充分除水後加入150毫升的乙醇，開啟攪拌，並添加甲醇鈉(0.33 g，6.2 mmole)，於室溫攪拌16小時。其後，添加 3-吡啶偕胺肟鹽(3-Amidinopyridinium chloride)( 3.96 g, 25.13 mmole)與氫氧化鈉( 1.6 g, 40.3 mmole)，並追加入30毫升的甲苯，打開加熱裝置，加熱直至75 ℃並反應隔夜。待反應完後，過濾取固體，再以250毫升的甲苯加熱攪拌並過濾固體，得到乳白色固體化合物G(約4.7克)。

將化合物G (10 g，12.8 mmole)與1-萘基硼酸(1-Naphthalenylboronic acid)( 4.4g， 25.6 mmole)置於反應槽，加入120毫升的甲苯。將碳酸鉀 (18.768 g，135.8 mmole)溶於70毫升的去離子水後加入反應槽，加入四(三苯基膦)鈀(Pd(PPh₃ )₄ )( 2 g， 1.73 mmole)及30毫升的乙醇開啟加熱及攪拌，加熱直至80 ℃反應並隔夜。待反應完後，加入300毫升的去離子水，攪拌30分鐘後，停止攪拌靜置使其分層，進行過濾，收到粗品，使用索氏萃取器加入矽膠進行層析法純化，濃縮至濃稠態加入300毫升的己烷加強析出，有機層合併過濾固體，得到乳白色固體化合物1-37(約6.29 克)。 以下顯示¹ H NMR之測定結果。¹ H NMR (CDCl₃ ,400MHz), d 9.916(s, 1H), 8.96 (d, 1H), 8.72(dd, 1H), 8.50(d, 2H), 8.32(d, 2H), 8.20-8.23(m, 2H), 8.11(d, 2H), 7.92(m, 4H), 7.84(m, 4H), 7.80(d, 1H), 7.61-7.67(m, 4H), 7.50-7.35（m, 6H）, 7.14（t, 7H）, 7.05（s, 1H）, 6.74（d, 2H）, 6.69（d, 1H）Synthesis Example 10: Synthesis of Compound 1-37

Place compound A (10 g, 23.03 mmole) and 3,5-dibromobenzaldehyde (3,5-dibromobenzaldehyde) (6.63 g, 25.12 mmole) in the reaction tank. After fully removing water, add 150 ml of ethanol and start stirring And, sodium methoxide (0.33 g, 6.2 mmole) was added and stirred at room temperature for 16 hours. After that, add 3-Amidinopyridinium chloride (3-96 g, 25.13 mmole) and sodium hydroxide (1.6 g, 40.3 mmole), and add 30 ml of toluene, turn on the heating device and heat until 75 ℃ and react overnight. After the reaction was completed, the solid was collected by filtration, heated and stirred with 250 ml of toluene, and the solid was filtered to obtain a compound G (about 4.7 g) as a milky white solid.

Compound G (10 g, 12.8 mmole) and 1-Naphthalenylboronic acid (4.4 g, 25.6 mmole) were placed in the reaction tank, and 120 ml of toluene was added. Potassium carbonate (18.768 g, 135.8 mmole) was dissolved in 70 ml of deionized water and added to the reaction tank. Tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ) (2 g, 1.73 mmole) and 30 ml The ethanol is turned on and stirred, heated to 80 ℃ reaction and overnight. After the reaction is completed, add 300 ml of deionized water, and after stirring for 30 minutes, stop stirring and allow it to separate into layers, and then filter. After receiving the crude product, use Soxhlet extractor to add silica gel for chromatography purification and concentration to concentration In a thick state, 300 ml of hexane was added to enhance precipitation, and the organic layer was combined to filter the solid to obtain a milky white solid compound 1-37 (about 6.29 g). The measurement results of ¹ H NMR are shown below. ¹ H NMR (CDCl ₃ ,400MHz), d 9.916(s, 1H), 8.96 (d, 1H), 8.72(dd, 1H), 8.50(d, 2H), 8.32(d, 2H), 8.20-8.23( m, 2H), 8.11(d, 2H), 7.92(m, 4H), 7.84(m, 4H), 7.80(d, 1H), 7.61-7.67(m, 4H), 7.50-7.35(m, 6H) , 7.14 (t, 7H), 7.05 (s, 1H), 6.74 (d, 2H), 6.69 (d, 1H)

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, the following layers shown in Figure 2 are deposited in sequence using a heated evaporation boat (a) Anode: thickness 135nm b) Hole injection layer: thickness 20nm, Contains 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 transport layer: Thickness 170 nm, HTM; d) Exciton barrier layer: Thickness 10 nm, HT (prepared by Yulei Optoelectronics); e) Light emitting layer: Thickness 25 nm, including 4% doping EBH of volume ratio BD, where BD and EBH are prepared by Yulei Optoelectronics; f) Electron transport layer: 25 nm thick, containing compounds 1-10 and doped lithium quinoline (Liq, prepared by Yulei Optoelectronics), volume The 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 4: Manufacture of organic electroluminescence elements Except that the compounds 1-10 of the electron transport layer in Example 1 were replaced with compounds 1-12, 1-13, and 1-14, the rest were implemented with Example 1 The organic electroluminescence element was manufactured in the same manner. In addition, the layer structure of Examples 2 to 4 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-type electrically conductive 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, the diphenylpyrimidine compound substituted by 9,9-spirobifluorene represented by the formula (I) of the present invention has a higher thermal cracking temperature (T _d ) and glass transition than the comparative example Temperature (T _g ), and as shown in Table 3, the organic electroluminescence device made of the diphenylpyrimidine compound substituted with 9,9-spirobifluorene represented by the formula (I) of the present invention has a comparative example Good luminous efficiency and lifespan. .

Therefore, the diphenylpyrimidine compound substituted by 9,9-spirobifluorene represented by formula (I) of the present invention with good luminous efficiency and life can improve the problems of the prior art, and has extremely high technical value, and is used in The organic electroluminescent element made of diphenylpyrimidine compound substituted by 9,9-spirobifluorene represented by formula (I) is especially suitable for automotive displays or OLED lighting in the field where extremely high driving voltage is not required light 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 with 9,9-spirobifluorene 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; A ₁ represents a substituted or unsubstituted Substituted (C6-C30) aryl, substituted or unsubstituted (5- to 30-membered) heteroaryl; X ₁ and A ₁ 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, A ₁ is the same or different. The diphenylpyrimidine compound substituted with 9,9-spirobifluorene 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; A ₁ represents a substituted Or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5- to 30-membered) heteroaryl; X ₁ and A ₁ 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, A ₁ is the same or different. The diphenylpyrimidine compound substituted with 9,9-spirobifluorene according to claim 1, wherein X ₁ is pyridyl, quinolinyl or naphthyl. A diphenylpyrimidine compound substituted with 9,9-spirobifluorene as described in claim 1 or 2, wherein X ₁ is selected from one of the following groups:

Among them, Xr represents hydrogen, fluorine, cyano, C1-4 alkyl or unsubstituted C6-18 aryl. A diphenylpyrimidine compound substituted with 9,9-spirobifluorene as described in claim 1 or 2, wherein A ₁ 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 diphenylpyrimidine compound substituted with 9,9-spirobifluorene as described in claim 5, wherein the unsubstituted C6-18 aryl group is a phenyl group, and the unsubstituted C6-12 aryl group Department of phenyl. The diphenylpyrimidine compound substituted with 9,9-spirobifluorene as described in claim 1, wherein, when n is 1, the compound of formula (I) is formula (I-4) or formula (I-5 ) Shown:

Formula (I-4)

Formula (I-5). The diphenylpyrimidine compound substituted with 9,9-spirobifluorene as described in claim 1, wherein, when n is 2, the compound of formula (I) is represented by formula (I-6),

Formula (I-6). The diphenylpyrimidine compound substituted with 9,9-spirobifluorene as described in claim 8, wherein A ₁ has the same structure. The diphenylpyrimidine compound substituted with 9,9-spirobifluorene described in 7 or 8 is one of the following compounds (1-1) to (1-38):

. The diphenylpyrimidine compound substituted with 9,9-spirobifluorene as described in 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 9,9-spirobifluorene substituted as described in any one of claims 1 to 11 Diphenylpyrimidine 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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