CN102516284A

Movatterモバイル変換

Info

Publication number: CN102516284A
Application number: CN2011103892990A
Authority: CN
Inventors: 邱化玉; 赵祖金; 尹守春
Original assignee: Hangzhou Normal University
Current assignee: Jiangsu Zhaofang Intelligent Equipment Co ltd; Nantong Wote Optoelectronics Technology Co ltd
Priority date: 2011-11-30
Filing date: 2011-11-30
Publication date: 2012-06-27
Anticipated expiration: 2031-11-30
Also published as: CN102516284B

Abstract

本发明公开了一种式V所示的含联三吡啶的双边相同取代噻咯类化合物，并公开了所述含联三吡啶的双边相同取代噻咯类化合物的制备方法，以及其作为发光材料的应用。

The invention discloses a double-tripyridine-containing double-identical substituted silole compound represented by formula V, and discloses a preparation method of the double-tripyridine-containing double-side identically-substituted silole compound, and its use as a light-emitting material Applications.

Description

Translated fromChinese

含联三吡啶的取代噻咯类化合物及其制备和应用Substituted silole compounds containing tripyridine and its preparation and application

技术领域technical field

本发明涉及含联三吡啶的双边相同取代噻咯类化合物及其作为光电材料在电致发光中的应用。本发明还涉及含联三吡啶的双边相同取代噻咯类化合物的制备方法。The present invention relates to double-tripyridine-containing identically substituted silole compounds and their application in electroluminescence as a photoelectric material. The invention also relates to a preparation method of silole compounds with double-side identical substitutions containing tripyridine.

背景技术Background technique

噻咯具有的新颖独特的电子结构赋予了其良好的电子亲合力和电子迁移率，使它在光电子材料领域有着广阔的应用前景，它可以作为有机电致发光器件(OLED)中的电子传输材料，也可以作为发光材料。上世纪90年代以来，围绕着噻咯及其衍生物的合成，以及它们作为光电材料的应用等，研究者已做了比较多的工作。The novel and unique electronic structure of silole endows it with good electron affinity and electron mobility, which makes it have broad application prospects in the field of optoelectronic materials. It can be used as an electron transport material in organic electroluminescent devices (OLEDs) , can also be used as a luminescent material. Since the 1990s, researchers have done a lot of work on the synthesis of silole and its derivatives, and their application as optoelectronic materials.

而联三吡啶作为重要的超分子结构单元，与其他配合物相比具有独特的磁、光物理和电化学性质。如果对联三吡啶配体结构进行修饰，可以方便地调控配合物放入光物理及电化学性质，因此利用这些特性可以设计很多新颖的功能化材料，用于光电子器件、信息存储、分子开关、分子机器和太阳能电池等。As an important supramolecular structural unit, biterpyridine has unique magnetic, photophysical and electrochemical properties compared with other complexes. If the structure of the tripyridine ligand is modified, the photophysical and electrochemical properties of the complex can be easily adjusted. Therefore, many novel functional materials can be designed by using these properties for optoelectronic devices, information storage, molecular switches, molecular machines and solar cells etc.

近年的研究分析表明，噻咯-联三吡啶配合物有优良的光致发光和电致发光性能。所以本发明的目的是提供一种新型的光电材料，研究其具体的发光效率，为光电领域提供具有应用价值前景的光电功能新材料。Research and analysis in recent years have shown that silole-biterpyridine complexes have excellent photoluminescence and electroluminescence properties. Therefore, the purpose of the present invention is to provide a new type of optoelectronic material, study its specific luminous efficiency, and provide new optoelectronic functional materials with promising application value for the optoelectronic field.

发明内容Contents of the invention

本发明的目的在于提供一种含联三吡啶的双边相同取代噻咯类化合物。The object of the present invention is to provide a double-side identically substituted silole compound containing tripyridine.

本发明的另一目的在于提供一种含联三吡啶的双边相同取代噻咯类化合物的制备方法。Another object of the present invention is to provide a method for preparing bipyridine-containing double-side identically substituted silole compounds.

本发明的又一目的在于提供一种含联三吡啶的双边相同取代噻咯类化合物作为发光材料的应用。Another object of the present invention is to provide the application of a bipyridine-containing double-side identically substituted silole compound as a light-emitting material.

本发明采用的技术方案是：The technical scheme adopted in the present invention is:

如式V所示的含联三吡啶的双边相同取代噻咯类化合物：Bilateral identically substituted silole compounds containing tripyridines as shown in formula V:

R₁、R₂各自独立为氢、C1～C10的烷基、C3～C6的环烷基或苯基；优选R₁、R₂各自独立为甲基、或苯基。R₁ and R₂ are independently hydrogen, C1-C10 alkyl, C3-C6 cycloalkyl or phenyl; preferably R₁ and R₂ are independently methyl or phenyl.

R₃为氢、C1～C10的烷基、C3～C6的环烷基或苯基中的任意一种或两种以上的组合；优选为氢、甲基、乙基或苯基中的任意一种或两种以上的组合。_R3 is any one or a combination of two or more of hydrogen, C1-C10 alkyl, C3-C6 cycloalkyl or phenyl; preferably any one of hydrogen, methyl, ethyl or phenyl one or a combination of two or more.

R₄为氢、C1～C6的烷基、C3～C6的环烷基或苯基中的任意一种或两种以上的组合；优选为氢、甲基、乙基、或苯基中的任意一种或两种以上的组合。R₄ is any one or a combination of two or more of hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, or phenyl; preferably hydrogen, methyl, ethyl, or any of phenyl One or a combination of two or more.

式V中，不同位置的R₃表示相同的基团，不同位置的R₄表示相同的基团。In formula V, R₃ at different positions represent the same group, and R₄ at different positions represent the same group.

更进一步，本发明所述含联三吡啶的双边相同取代噻咯类化合物最优选为下列式IX、式XI或式XII所示化合物。Furthermore, the bi-terpyridine-containing double-side identically substituted silole compounds of the present invention are most preferably compounds represented by the following formula IX, formula XI or formula XII.

本发明还提供所述如式V所示的含联三吡啶的双边相同取代噻咯类化合物的制备方法，所述方法为：The present invention also provides a preparation method of the biterpyridine-containing double-side identically substituted silole compounds shown in formula V, the method is:

式I所示化合物与式III所示化合物在氮气保护下进行Suzuki偶联反应，以四-(三苯基磷)钯为催化剂，在四氢呋喃和水的混合溶剂中，加入碱性物质保持反应液pH值为7～9，回流反应72～100小时，反应结束反应液后处理得到式V所示化合物；所述式I所示化合物与式III所示化合物的物质的量之比为1∶3；The compound shown in formula I and the compound shown in formula III are subjected to Suzuki coupling reaction under the protection of nitrogen, using tetrakis-(triphenylphosphine) palladium as a catalyst, in a mixed solvent of tetrahydrofuran and water, adding an alkaline substance to keep the reaction solution The pH value is 7-9, reflux reaction for 72-100 hours, after the reaction, the reaction solution is processed to obtain the compound shown in formula V; the ratio of the amount of the compound shown in the formula I to the compound shown in the formula III is 1:3 ;

式I或式III中，R₁、R₂各自独立为氢、C1～C10的烷基、C3～C6的环烷基或苯基；In formula I or formula III, R₁ and R₂ are each independently hydrogen, C1-C10 alkyl, C3-C6 cycloalkyl or phenyl;

式I中，R₃为氢、C1～C10的烷基、C3～C6的环烷基或苯基中的任意一种或两种以上的组合；In formula I,_R3 is any one or a combination of two or more of hydrogen, C1-C10 alkyl, C3-C6 cycloalkyl or phenyl;

式III中，R₄为氢、C1～C6的烷基、C3～C6的环烷基或苯基中的任意一种或两种以上的组合；In formula III,_R4 is any one or a combination of two or more of hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl or phenyl;

式I中，不同位置的R₃表示相同的基团；式III中，不同位置的R₄表示相同的基团。In formula I, R₃ at different positions represent the same group; in formula III, R₄ at different positions represent the same group.

所述催化剂四-(三苯基磷)钯的物质的量用量通常为式I所示化合物的物质的量的10％。The amount of the catalyst tetrakis-(triphenylphosphine)palladium is usually 10% of the amount of the compound represented by formula I.

所述加入碱性物质保持反应液pH值为7～9，通常加入常用碱类例如碳酸钾、碳酸钠或氢氧化钠等，保持反应液的pH值为碱性即可。所述反应液后处理方法为：反应结束后，反应液加水猝灭反应，过滤，取滤饼用四氢呋喃溶解，用KOH溶液洗涤后加入Et₂O萃取，取有机层蒸除溶剂，得到式V所示化合物粗品混合物，式V所示混合物粗品经柱层析分离，以石油醚与乙酸乙酯体积比4∶1混合溶液为洗脱剂，所得洗脱液蒸除溶剂，制得式V所示化合物纯品。The adding of alkaline substances keeps the pH value of the reaction solution at 7-9. Commonly used alkalis such as potassium carbonate, sodium carbonate or sodium hydroxide are usually added to keep the pH value of the reaction solution alkaline. The post-treatment method of the reaction solution is as follows: after the reaction is completed, add water to the reaction solution to quench the reaction, filter, take the filter cake and dissolve it in tetrahydrofuran, wash it with KOH solution and add_Et2O for extraction, take the organic layer and evaporate the solvent to obtain the formula V The crude product mixture of the compounds shown, the crude product of the compound shown in the formula V is separated by column chromatography, and the mixed solution of petroleum ether and ethyl acetate with a volume ratio of 4:1 is used as the eluent, and the obtained eluent is evaporated to remove the solvent, and the compound of the formula V is obtained. shows pure compounds.

所述方法中，所述四氢呋喃和水的混合溶剂通常是四氢呋喃与水以体积比1∶0.3～0.8的混合，所述四氢呋喃和水的混合溶剂的总体积用量以式I所示化合物的质量计为30～100mL/g。In the method, the mixed solvent of tetrahydrofuran and water is usually a mixture of tetrahydrofuran and water at a volume ratio of 1:0.3 to 0.8, and the total volume of the mixed solvent of tetrahydrofuran and water is based on the mass of the compound shown in formula I 30-100mL/g.

本发明所述式I所示化合物可按以下方法制备得到：Compound shown in formula I of the present invention can be prepared according to the following method:

氮气保护下，金属锂与萘溶于四氢呋喃中，室温下反应4小时后，滴加式vi所示的化合物，反应10分钟～1小时，然后冷却至-10℃，加入ZnCl₂-TMEDA络合物和四氢呋喃，反应1～2小时后，加入4-溴碘苯和催化剂PdCl₂(PPh₃)₂，在30℃下反应12小时，反应结束后反应液加入1N盐酸猝灭反应，依次用水、饱和NaCl溶液洗涤后加入无水乙醚萃取，取有机层干燥，得到粗产物过硅胶柱提纯，以石油醚为洗脱剂，洗脱液蒸除溶剂即得式I所示化合物；所述金属锂、萘、式vi所示的化合物、ZnCl₂-TMEDA络合物、4-溴碘苯的物质的量之比为1∶1～1.1∶0.25∶1∶0.5。所述催化剂PdCl₂(PPh₃)₂的物质的量用量通常为式vi所示的化合物的物质的量的2～5％。Under the protection of nitrogen, metal lithium and naphthalene were dissolved in tetrahydrofuran. After reacting at room temperature for 4 hours, the compound represented by formula vi was added dropwise, and reacted for 10 minutes to 1 hour, then cooled to -10°C, and ZnCl₂ -TMEDA was added for complexation After reacting for 1 to 2 hours, add 4-bromoiodobenzene and catalyst PdCl₂ (PPh₃ )₂ and react at 30°C for 12 hours. After the reaction is completed, add 1N hydrochloric acid to the reaction liquid to quench the reaction, and then water, After washing with a saturated NaCl solution, add anhydrous ether for extraction, take the organic layer and dry it to obtain a crude product that is purified through a silica gel column, using petroleum ether as the eluent, and distilling the eluent to remove the solvent to obtain the compound shown in formula I; the metal lithium , naphthalene, the compound represented by formula vi, the ZnCl₂ -TMEDA complex, and 4-bromoiodobenzene have a ratio of 1:1 to 1.1:0.25:1:0.5. The amount of the catalyst PdCl₂ (PPh₃ )₂ is generally 2-5% of the amount of the compound represented by formula vi.

式vi中，R₃为氢、C1～C10的烷基、C3～C6的环烷基或苯基中的任意一种或两种以上的组合，并且，不同位置的R₃表示相同的基团。In formula vi, R₃ is any one or a combination of two or more of hydrogen, C1-C10 alkyl, C3-C6 cycloalkyl or phenyl, and R₃ at different positions represents the same group .

所述四氢呋喃的总用量以萘的物质的量计为2～4mL/mmol，其中，用于溶解金属锂与萘的四氢呋喃的用量以萘的物质的量计为1～2mL/mmol，与ZnCl₂-TMEDA络合物一起加入反应液的四氢呋喃的用量以萘的物质的量计为1～2mL/mmol。The total amount of tetrahydrofuran used is 2 to 4 mL/mmol based on the amount of naphthalene, wherein the amount of tetrahydrofuran used to dissolve lithium metal and naphthalene is 1 to 2 mL/mmol based on the amount of naphthalene, and ZnCl₂ The amount of tetrahydrofuran added to the reaction solution together with the -TMEDA complex is 1-2 mL/mmol in terms of the amount of naphthalene.

这是本领域技术人员公知的制备方法。This is a preparation method well known to those skilled in the art.

所述式III所述化合物通常可按以下方法制备得到：式II所示化合物和双戊酰二硼以Pd(dppf)Cl₂为催化剂，加入醋酸钾，以DMSO为溶剂，加热回流反应8～10小时，然后加入甲苯萃取，取有机层用水洗涤后干燥，减压蒸除溶剂后得到式III所示粗产物，式III所示粗产物过硅胶柱提纯，以石油醚与乙酸乙酯体积比4∶1的混合溶液为洗脱剂，洗脱液蒸除溶剂得到式III所示化合物纯产物，所述式II所示化合物、双戊酰二硼、Pd(dppf)Cl₂、醋酸钾的物质的量之比为1∶1～1.1∶0.005～0.02∶2～4。The compound described in the formula III can usually be prepared according to the following method: the compound shown in the formula II and bis-valeryl diboron use Pd(_dppf )Cl as a catalyst, add potassium acetate, and use DMSO as a solvent, and heat and reflux for 8～ 10 hours, then add toluene for extraction, get the organic layer, wash with water and dry, evaporate the solvent under reduced pressure to obtain the crude product shown in formula III, the crude product shown in formula III is purified by silica gel column, and the volume ratio of sherwood oil and ethyl acetate is The mixed solution of 4_: 1 is the eluent, and the eluent is evaporated to remove the solvent to obtain the pure product of the compound shown in formula III. The ratio of the amount of substances is 1:1-1.1:0.005-0.02:2-4.

所述反应式如下：Described reaction formula is as follows:

式II中，R₄为氢、C1～C6的烷基、C3～C6的环烷基或苯基中的任意一种或两种以上的组合，并且，不同位置的R₄表示相同的基团。In formula II, R₄ is any one or a combination of two or more of hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl or phenyl, and R₄ at different positions represents the same group .

所述式II所示化合物可按以下方法制备得到：The compound shown in the formula II can be prepared as follows:

4-溴苯甲醛的甲醇溶液中，加入式A所示吡啶类化合物、NaOH和浓氨水，加热回流反应72～80小时，然后冷却到室温，得到黄色沉淀过滤，滤饼依次用水、甲醇洗涤后干燥得到式II所示化合物，所述4-溴苯甲醛、式A所示吡啶类化合物、NaOH、浓氨水中NH₃·H₂O的物质的量之比为1∶2∶1～2∶70～100。Add pyridine compounds shown in Formula A, NaOH and concentrated ammonia water to the methanol solution of 4-bromobenzaldehyde, heat and reflux for 72-80 hours, then cool to room temperature to obtain a yellow precipitate and filter, and the filter cake is washed with water and methanol in turn Dry to obtain the compound shown in formula II, the ratio of the amount of substance of said 4-bromobenzaldehyde, pyridine compound shown in formula A, NaOH, NH in concentrated ammonia water H₃ ·H₂ O is 1: 2: 1～2: 70-100.

所述反应式如下：Described reaction formula is as follows:

式A中，R₄为氢、C1～C6的烷基、C3～C6的环烷基或苯基中的任意一种或两种以上的组合。In formula A, R₄ is any one or a combination of two or more of hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, or phenyl.

最优选的，本发明所述制备方法按以下步骤进行：Most preferably, the preparation method of the present invention is carried out according to the following steps:

式I所示化合物与式III所示化合物在氮气保护下进行suzuki偶联反应，以四-(三苯基磷)钯为催化剂，在四氢呋喃和水的混合溶剂中，加入碱性物质保持反应液pH值为7～9，回流反应72～100小时，反应结束反应液加水猝灭反应，过滤，取滤饼用四氢呋喃溶解，用KOH溶液洗涤后加入Et₂O萃取，取有机层蒸除溶剂，得到式V所示化合物粗品，式V所示化合物粗品经柱层析分离，以石油醚与乙酸乙酯体积比4∶1混合溶液为洗脱剂，所得洗脱液蒸除溶剂，制得IV和式V所示化合物纯品；所述式I所示化合物与式III所示化合物的物质的量之比为1∶3；所述四-(三苯基磷)钯的物质的量用量为式I所示化合物的物质的量的10％。The compound shown in formula I and the compound shown in formula III are subjected to suzuki coupling reaction under the protection of nitrogen, using tetrakis-(triphenylphosphine) palladium as a catalyst, in a mixed solvent of tetrahydrofuran and water, adding an alkaline substance to keep the reaction solution The pH value is 7-9, and the reaction is refluxed for 72-100 hours. After the reaction is completed, add water to the reaction liquid to quench the reaction, filter, take the filter cake and dissolve it in tetrahydrofuran, wash it with KOH solution, add Et₂ O for extraction, take the organic layer and evaporate the solvent, The crude product of the compound shown in formula V was obtained, and the crude product of the compound shown in formula V was separated by column chromatography, using a mixed solution of petroleum ether and ethyl acetate with a volume ratio of 4:1 as the eluent, and the obtained eluent was evaporated to remove the solvent to obtain IV and the compound pure product shown in formula V; the ratio of the amount of substance of the compound shown in the formula I and the compound shown in the formula III is 1: 3; the amount of substance of the four-(triphenylphosphine) palladium is 10% of the amount of the compound represented by formula I.

本发明提供的含联三吡啶的双边相同取代噻咯类化合物具有发光性能，可应用作为发光材料。进一步，可应用于需要发光材料的有机电子器件中。The bilaterally identically substituted silole compounds containing tripyridine provided by the invention have luminescent properties and can be used as luminescent materials. Furthermore, it can be applied to organic electronic devices that require light-emitting materials.

本发明还提供一种如式IV所示的含联三吡啶的不对称取代噻咯类化合物：The present invention also provides an asymmetrically substituted silole compound containing biterpyridine as shown in formula IV:

式IV中，R₁、R₂各自独立为氢、C1～C10的烷基、C3～C6的环烷基或苯基；优选R₁、R₂各自独立为甲基、或苯基。In Formula IV, R₁ and R₂ are independently hydrogen, C1-C10 alkyl, C3-C6 cycloalkyl or phenyl; preferably R₁ and R₂ are independently methyl or phenyl.

式IV中，不同位置的R₃表示相同的基团，不同位置的R₄表示相同的基团。In formula IV, R₃ at different positions represent the same group, and R₄ at different positions represent the same group.

所述式IV所示的含联三吡啶的不对称取代噻咯类化合物最优选为下列式VIII或式X所示化合物：The terpyridine-containing asymmetrically substituted silole compound represented by the formula IV is most preferably the compound represented by the following formula VIII or formula X:

所述如式IV所示的含联三吡啶的不对称取代噻咯类化合物的制备方法为：The preparation method of the asymmetrically substituted silole compound containing terpyridine as shown in formula IV is:

式I所示化合物与式III所示化合物在氮气保护下进行Suzuki偶联反应，以四-(三苯基磷)钯为催化剂，在四氢呋喃和水的混合溶剂中，加入碱性物质保持反应液pH值为7～9，回流反应10～15小时，反应结束反应液后处理得到式IV所示化合物；所述式I所示化合物与式III所示化合物的物质的量之比为1∶3；The compound shown in formula I and the compound shown in formula III are subjected to Suzuki coupling reaction under the protection of nitrogen, using tetrakis-(triphenylphosphine) palladium as a catalyst, in a mixed solvent of tetrahydrofuran and water, adding an alkaline substance to keep the reaction solution The pH value is 7-9, reflux reaction for 10-15 hours, after the reaction, the reaction solution is processed to obtain the compound shown in formula IV; the ratio of the amount of the compound shown in the formula I to the compound shown in the formula III is 1:3 ;

所述反应液后处理方法为：反应结束后，反应液加水猝灭反应，过滤，取滤饼用四氢呋喃溶解，用KOH溶液洗涤后加入Et₂O萃取，取有机层蒸除溶剂，得到式IV所示化合物粗品混合物，式IV所示混合物粗品经柱层析分离，以石油醚与乙酸乙酯体积比4∶1混合溶液为洗脱剂，所得洗脱液蒸除溶剂，制得式IV所示化合物纯品。The post-treatment method of the reaction solution is as follows: after the reaction, add water to the reaction solution to quench the reaction, filter, take the filter cake and dissolve it in tetrahydrofuran, wash it with KOH solution and add_Et2O for extraction, take the organic layer and evaporate the solvent to obtain the formula IV The crude compound mixture shown in formula IV is separated by column chromatography, and the mixed solution of petroleum ether and ethyl acetate with a volume ratio of 4:1 is used as the eluent, and the obtained eluent is evaporated to remove the solvent to obtain the compound of formula IV shows pure compounds.

所述如式IV所示的含联三吡啶的不对称取代噻咯类化合物具有发光性能，可应用作为发光材料。进一步，可应用于需要发光材料的有机电子器件中。The terpyridine-containing asymmetrically substituted silole compound shown in formula IV has luminescent properties and can be used as a luminescent material. Furthermore, it can be applied to organic electronic devices that require light-emitting materials.

本发明提供式V与式IV两种新化合物，，通过测试，具有良好的光学性能，并且具有反应条件简单，原料易得，产率较高，生成化合物稳定，存放简单等优点。The invention provides two new compounds of formula V and formula IV, which have good optical properties through testing, and have the advantages of simple reaction conditions, readily available raw materials, high yield, stable formed compounds, and simple storage.

具体实施方式Detailed ways

下面结合具体实例对本发明作进一步阐述，但本发明的保护范围不限于此。The present invention will be further described below in conjunction with specific examples, but the protection scope of the present invention is not limited thereto.

下述制备例中所用试剂，均为市售试剂：The reagents used in the following preparation examples are commercially available reagents:

实施例1：Example 1:

R₁R₁ R₂R₂ R₃R₃ R₄R₄ 化合物compound 熔点melting point 甲基Methyl 己基Hexyl -- -- VIVI 80℃80℃

1-甲基-2-己基-3，4-二苯基-2，5-二溴噻咯的制备Preparation of 1-methyl-2-hexyl-3,4-diphenyl-2,5-dibromosilole

氮气保护下，向锂粒(83mg，12mmol)和萘(1.54g，12.1mmol)的混合物中加入THF(12mL)制备萘基锂溶液，4小时后，缓慢加入二苯乙炔基甲基己基硅烷(991mg，3.0mmol))，时间超过10分钟。反应物冷却到-10℃，加入ZnCl₂-TMEDA(3.0g，12mmol)和THF(20ml)。反应一小时后，加入4-溴碘苯(1.7g，6mmol)和PdCl₂(PPh₃)₂(70mg，0.1mmol)，在30℃下反应12小时。加入10mL HCl(1N)猝灭反应，水洗，饱和NaCl溶液洗，50ml无水乙醚萃取，取有机层干燥。得到粗产物过硅胶柱提纯，石油醚为洗脱剂，洗脱液蒸除溶剂即得式VI所示化合物3.1g，收率71.8％。Under nitrogen protection, THF (12mL) was added to a mixture of lithium particles (83mg, 12mmol) and naphthalene (1.54g, 12.1mmol) to prepare a naphthyllithium solution. After 4 hours, diphenylethynylmethylhexylsilane ( 991 mg, 3.0 mmol)) over 10 minutes. The reactant was cooled to -10°C, and ZnCl₂ -TMEDA (3.0 g, 12 mmol) and THF (20 ml) were added. After reacting for one hour, 4-bromoiodobenzene (1.7 g, 6 mmol) and PdCl₂ (PPh₃ )₂ (70 mg, 0.1 mmol) were added, and reacted at 30°C for 12 hours. Add 10 mL of HCl (1N) to quench the reaction, wash with water, wash with saturated NaCl solution, extract with 50 mL of anhydrous ether, and take the organic layer to dry. The obtained crude product was purified by a silica gel column, using petroleum ether as the eluent, and the solvent was evaporated from the eluent to obtain 3.1 g of the compound represented by formula VI, with a yield of 71.8%.

取0.2g量的产物，在真空3*10^-4Pa下，涂抹成单层膜，再放入SSP3110LED光电参数综合测试机中，检测其最大亮度，得到产物最大亮度为600cd/cm²。Take 0.2g of the product, apply it into a single-layer film under a vacuum of 3*10^-4 Pa, and then put it into the SSP3110 LED photoelectric parameter comprehensive testing machine to test its maximum brightness, and the maximum brightness of the product is 600cd/cm² .

¹HNMR(400MHz，CDCl3)，dZ7.26(d，4H，Ph-H)，7.03(m，6H，Ph-H)，6.80(m，8H，Ph-H)，0.47(s，3H，-CH₃-)，0.96(m，2H，-CH₂-)，0.92(m，8H，-CH₂-)，1.30(s，3H，-CH₃-).¹ HNMR (400MHz, CDCl3), dZ7.26 (d, 4H, Ph-H), 7.03 (m, 6H, Ph-H), 6.80 (m, 8H, Ph-H), 0.47 (s, 3H, - CH₃ -), 0.96(m, 2H, -CH₂ -), 0.92(m, 8H, -CH₂ -), 1.30(s, 3H, -CH₃ -).

实施例2：Example 2:

2，2’：6’2”-联三吡啶-4’-苯基-4，4，5，5-四甲基-1，3，2-二氧杂环戊硼烷2,2': 6'2"-Terpyridine-4'-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

R₁R₁ R₂R₂ R₃R₃ R₄R₄ 化合物compound 熔点melting point -- -- -- Hh VIIVII --

500ml的圆底烧瓶中，向4-溴苯甲醛(1.0g，5.40mmol)的甲醇(120ml)溶液中，加入2-乙酰基吡啶(2.2g，10.80mmol)，NaOH(0.22g，5.4mmol)和30ml浓氨水(28％)，加热到70℃回流72小时。冷却到室温后，得到黄色沉淀过滤，取滤饼依次用水洗，甲醇洗，干燥得到2-溴苯基-2，2’：6’2”-联三吡啶(1.8g，86％)。将2-溴苯基-2，2’：6’2”-联三吡啶(1.8g，4.6mmol)，Pd(dppf)Cl2(116mg，0.038mmol)，KOAc(1.35g，13.8mmol)和双戊酰二硼(1.2g，4.83mmol)置于25ml圆底烧瓶中，加入10ml DMSO，在85℃下回流8小时后，加入50ml甲苯萃取，取有机层用水(3*100mL)洗去DMSO后干燥，旋掉溶剂，得到粗产物。粗产物过硅胶柱提纯，以石油醚/乙酸乙酯(v/v＝4∶1)为洗脱剂，得到纯产物式VII所示化合物(0.84g，收率42％)。1H NMR(400MHz，CDCl3)8.76(s，2H，H3)，8.75(dm，2H，J 4.8，0.9，H6)，8.66(d，2H，J 7.8，H3)，7.98(d，2H，J 8.4，Hphenyl)，7.93(d，2H，J8.4，Hphenyl)，7.86(td，2H，J 7.8，1.5，H4)，7.34(ddd，2H，J 7.5，6.3，1.2Hz，H5)，1.39(s，12H)In a 500ml round bottom flask, in methanol (120ml) solution of 4-bromobenzaldehyde (1.0g, 5.40mmol), add 2-acetylpyridine (2.2g, 10.80mmol), NaOH (0.22g, 5.4mmol) and 30ml of concentrated ammonia water (28%), heated to 70°C for reflux for 72 hours. After cooling to room temperature, the obtained yellow precipitate was filtered, and the filter cake was washed successively with water and methanol, and dried to obtain 2-bromophenyl-2,2':6'2"-biterpyridine (1.8g, 86%). 2-bromophenyl-2,2':6'2"-terpyridine (1.8g, 4.6mmol), Pd(dppf)Cl2 (116mg, 0.038mmol), KOAc (1.35g, 13.8mmol) and dipentamyl Acyl diboron (1.2g, 4.83mmol) was placed in a 25ml round bottom flask, 10ml DMSO was added, after reflux at 85°C for 8 hours, 50ml of toluene was added for extraction, the organic layer was washed with water (3*100mL) to remove DMSO and dried , and spin off the solvent to obtain the crude product. The crude product was purified by silica gel column, using petroleum ether/ethyl acetate (v/v=4:1) as the eluent, to obtain the pure compound represented by formula VII (0.84 g, yield 42%). 1H NMR (400MHz, CDCl3) 8.76(s, 2H, H3), 8.75(dm, 2H, J 4.8, 0.9, H6), 8.66(d, 2H, J 7.8, H3), 7.98(d, 2H, J 8.4 , Hphenyl), 7.93 (d, 2H, J8.4, Hphenyl), 7.86 (td, 2H, J 7.8, 1.5, H4), 7.34 (ddd, 2H, J 7.5, 6.3, 1.2Hz, H5), 1.39 ( s, 12H)

实施例3：Example 3:

R₁R₁ R₂R₂ R₃R₃ R₄R₄ 化合物compound 熔点melting point

甲基Methyl 甲基Methyl 氢hydrogen Hh VIIIVIII 380℃380°C

1，1-二甲基-3，4-二苯基-2-(2，2’：6’2”-联三吡啶)苯基-5-溴苯基噻咯的制备Preparation of 1,1-dimethyl-3,4-diphenyl-2-(2,2':6'2"-biterpyridine)phenyl-5-bromophenylsilole

在N₂保护下，1，1-二甲基-3，4-二苯基-2，5-二溴苯基噻咯(0.23g，0.4mmol)，2，2’：6’2”-联三吡啶-4’-苯基-4，4，5，5-四甲基-1，3，2-二氧杂环戊硼烷VII(0.52g，1.2mmol)，碳酸钾(0.16g，1.2mmol)，催化剂Pd(PPh₃)₄0.04mmol，在10ml四氢呋喃和5ml水溶剂中，加热到70℃回流反应12小时。反应结束后，先用10ml水猝灭反应，过滤，滤饼用20ml四氢呋喃溶解。用5％的KOH溶剂洗涤，30mlEt₂O萃取，取有机层蒸除溶剂，得到粗产物过硅胶柱提纯，用石油醚与乙酸乙酯(体积比4∶1)为洗脱剂，所得洗脱液蒸除溶剂得式VIII所示产物(0.11g，收率35％)。Under_N protection, 1,1-dimethyl-3,4-diphenyl-2,5-dibromophenylsilole (0.23g, 0.4mmol), 2,2':6'2"- Tripyridine-4'-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane VII (0.52g, 1.2mmol), potassium carbonate (0.16g, 1.2mmol), catalyst Pd(PPh₃ )₄ 0.04mmol, in 10ml tetrahydrofuran and 5ml water solvent, heated to 70°C for reflux reaction for 12 hours. After the reaction, first quench the reaction with 10ml water, filter, and filter the cake with 20ml THF was dissolved. Washed with 5% KOH solvent, extracted with_30mlEt2O , the organic layer was evaporated to remove the solvent, and the crude product was purified by a silica gel column, using petroleum ether and ethyl acetate (volume ratio 4:1) as the eluent, The obtained eluate was evaporated to remove the solvent to obtain the product represented by formula VIII (0.11 g, yield 35%).

产物最大亮度为620cd/cm²。测试方法同实施例1。The maximum brightness of the product is 620cd/cm² . Test method is the same as embodiment 1.

¹HNMR(400MHz，CDCl₃)，8.68-8.78(m，6H)，7.96-7.98(d，J＝8.4Hz，2H)，7.87-7.91(m，2H)，7.69-7.71(d，J＝8.4Hz，2H)，7.45-7.47(d，J＝8.4Hz，2H)，7.35-7.38(m，2H)，7.24-7.26(d，J＝8Hz，2H)，7.02-7.07(m，8H)，6.80-6.87(m，6H)，0.52(s，6H).¹ HNMR (400MHz, CDCl₃ ), 8.68-8.78(m, 6H), 7.96-7.98(d, J=8.4Hz, 2H), 7.87-7.91(m, 2H), 7.69-7.71(d, J=8.4 Hz, 2H), 7.45-7.47(d, J=8.4Hz, 2H), 7.35-7.38(m, 2H), 7.24-7.26(d, J=8Hz, 2H), 7.02-7.07(m, 8H), 6.80-6.87(m, 6H), 0.52(s, 6H).

其中1，1-二甲基-3，4-二苯基-2，5-二溴苯基噻咯按以下方法制备：Wherein 1,1-dimethyl-3,4-diphenyl-2,5-dibromophenylsilole is prepared by the following method:

氮气保护下，向锂粒(83mg，12mmol)和萘(1.54g，12.1mmol)的混合物中加入THF(12mL)制备萘基锂溶液，4小时后，缓慢加入二苯乙炔基二甲基硅烷(800mg，3.0mmol))，时间超过10分钟。反应物冷却到-10℃，加入ZnCl₂-TMEDA(3.0g，12mmol)和THF(20ml)。反应一小时后，加入4-溴碘苯(1.7g，6mmol)和PdCl₂(PPh3)2(70mg，0.1mmol)，在30℃下反应12小时。加入10ml HCl(1N)猝灭反应，水洗，饱和NaCl溶液洗，50ml无水乙醚萃取，取有机层干燥。得到粗产物过柱提纯，石油醚为洗脱剂，洗脱液蒸除溶剂即得1，1-二甲基-3，4-二苯基-2，5-二溴苯基噻咯0.90g。Under nitrogen protection, THF (12mL) was added to a mixture of lithium particles (83mg, 12mmol) and naphthalene (1.54g, 12.1mmol) to prepare a naphthyllithium solution. After 4 hours, diphenylethynyldimethylsilane ( 800mg, 3.0mmol)) over 10 minutes. The reactant was cooled to -10°C, and ZnCl₂ -TMEDA (3.0 g, 12 mmol) and THF (20 ml) were added. After reacting for one hour, 4-bromoiodobenzene (1.7 g, 6 mmol) and PdCl₂ (PPh3) 2 (70 mg, 0.1 mmol) were added and reacted at 30° C. for 12 hours. Add 10ml of HCl (1N) to quench the reaction, wash with water, wash with saturated NaCl solution, extract with 50ml of anhydrous ether, and take the organic layer to dry. The obtained crude product was purified by column, petroleum ether was used as the eluent, and the eluent was evaporated to remove the solvent to obtain 0.90 g of 1,1-dimethyl-3,4-diphenyl-2,5-dibromophenylsilole .

实施例4：Example 4:

R₁R₁ R₂R₂ R₃R₃ R₄R₄ 化合物compound 熔点melting point 甲基Methyl 甲基Methyl 氢hydrogen 氢hydrogen IXIX 450℃450℃

1，1-二甲基-3，4-二苯基-2，5-双(2，2’：6’2”-联三吡啶)苯基噻咯的制备Preparation of 1,1-dimethyl-3,4-diphenyl-2,5-bis(2,2':6'2"-biterpyridyl)phenylsilole

在N₂保护下，按实施例3方法制得的1，1-二甲基-3，4-二苯基-2，5-二溴苯基噻咯(0.23g，0.4mmol)，2，2’：6’2”-联三吡啶-4’-苯基-4，4，5，5-四甲基-1，3，2-二氧杂环戊硼烷(0.52g，1.2mmol)，碳酸钾0.1g，催化剂Pd(PPh₃)₄0.04mmol，在10ml四氢呋喃和5ml水溶剂中，加热到70℃回流反应72小时，反应结束后，先加10ml水猝灭反应，过滤，滤饼用20ml四氢呋喃溶解。用5％的KOH溶剂洗涤，30ml Et₂O萃取，取有机层蒸除溶剂，得到粗产物用柱层析提纯，用石油醚与乙酸乙酯(体积比4∶1)为洗脱剂，所得洗脱液蒸除溶剂得式IX所示产物(0.19g，收率45％)。Under the protection of_N2 , 1,1-dimethyl-3,4-diphenyl-2,5-dibromophenylsilole (0.23g, 0.4mmol) prepared according to the method of Example 3, 2, 2': 6'2"-Terpyridine-4'-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.52g, 1.2mmol) , Potassium carbonate 0.1g, catalyst Pd(PPh₃ )₄ 0.04mmol, in 10ml tetrahydrofuran and 5ml water solvent, heated to 70°C for reflux reaction for 72 hours, after the reaction, first add 10ml water to quench the reaction, filter, filter cake Dissolve with 20ml tetrahydrofuran. Wash with 5% KOH solvent, extract with 30ml Et₂ O, get the organic layer to evaporate the solvent, obtain the crude product and purify it with column chromatography, and use sherwood oil and ethyl acetate (volume ratio 4: 1) as Eluant, the obtained eluate was evaporated to remove the solvent to obtain the product shown in formula IX (0.19 g, yield 45%).

产物最大亮度为650cd/cm²。测试方法同实施例1。The maximum brightness of the product is 650cd/cm² . Test method is the same as embodiment 1.

¹HNMR(400MHz，CDCl₃)，8.71-8.75(m，8H)，8.64-8.66(d，J＝8Hz，4H)，7.93-7.95(d，J＝8Hz，5H)，7.82-7.86(t，J＝6.8Hz，5H)，7.67-7.69(d，J＝8Hz，5H)，7.45-7.47(d，J＝7.6Hz，4H)，7.30-7.33(t，J＝5.2Hz，5H)，7.07(s，7H)，6.91(m，3H)，0.59(s，6H).¹ HNMR (400MHz, CDCl₃ ), 8.71-8.75(m, 8H), 8.64-8.66(d, J=8Hz, 4H), 7.93-7.95(d, J=8Hz, 5H), 7.82-7.86(t, J=6.8Hz, 5H), 7.67-7.69(d, J=8Hz, 5H), 7.45-7.47(d, J=7.6Hz, 4H), 7.30-7.33(t, J=5.2Hz, 5H), 7.07 (s, 7H), 6.91 (m, 3H), 0.59 (s, 6H).

实施例5：Example 5:

R₁R₁ R₂R₂ R₃R₃ R₄R₄ 化合物compound 熔点melting point 甲基Methyl 己基Hexyl 氢hydrogen 氢hydrogen Xx 450℃450℃

在N₂保护下，按实施例1方法制得的1-甲基-2己基-3，4-二苯基-2，5-二溴苯基噻咯(0.35g，0.4mmol)，2，2’：6’2”-联三吡啶-4’-苯基-4，4，5，5-四甲基-1，3，2-二氧杂环戊硼烷(0.52g，1.2mmol)，催化剂Pd(PPh₃)₄0.04mmol，碳酸钾0.1g，在10ml四氢呋喃和5ml水溶剂中，回流反应12小时。反应结束后，先用10ml水猝灭反应，过滤，滤饼用20ml四氢呋喃溶解。用5％的KOH溶剂洗涤，30ml Et₂O萃取，取有机层蒸除溶剂，得到粗产物用柱层析提纯，用石油醚与乙酸乙酯(体积比4∶1)为洗脱剂，所得洗脱液蒸除溶剂得式X所示产物(0.14g，收率40％)。Under the protection of_N2 , 1-methyl-2-hexyl-3,4-diphenyl-2,5-dibromophenylsilole (0.35g, 0.4mmol) prepared according to the method of Example 1, 2, 2': 6'2"-Terpyridine-4'-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.52g, 1.2mmol) , catalyst Pd(PPh₃ )₄ 0.04mmol, potassium carbonate 0.1g, in 10ml tetrahydrofuran and 5ml water solvent, reflux reaction for 12 hours. After the reaction, first quench the reaction with 10ml water, filter, and dissolve the filter cake with 20ml tetrahydrofuran Wash with 5% KOH solvent, extract with 30ml Et₂ O, take the organic layer and distill off the solvent to obtain the crude product and purify it by column chromatography, using petroleum ether and ethyl acetate (volume ratio 4:1) as eluent, The obtained eluate was evaporated to remove the solvent to obtain the product represented by formula X (0.14 g, yield 40%).

产物最大亮度为640cd/cm²，测试方法同实施例1。The maximum brightness of the product is 640cd/cm² , and the test method is the same as that in Example 1.

¹HNMR(400MHz，CDCl₃)，8.68-8.78(m，6H)，7.96-7.98(d，J＝8.4Hz，2H)，7.87-7.91(m，2H)，7.69-7.71(d，J＝8.4Hz，2H)，7.45-7.47(d，J＝8.4Hz，2H)，7.35-7.38(m，2H)，7.24-7.26(d，J＝8Hz，2H)，7.02-7.07(m，8H)，6.80-6.87(m，6H)，1.42-1.21(m，8H)，1.09-0.99(m，2H)，0.86-0.83(t，J＝6.8Hz，3H)，0.50(s，3H)..¹ HNMR (400MHz, CDCl₃ ), 8.68-8.78(m, 6H), 7.96-7.98(d, J=8.4Hz, 2H), 7.87-7.91(m, 2H), 7.69-7.71(d, J=8.4 Hz, 2H), 7.45-7.47(d, J=8.4Hz, 2H), 7.35-7.38(m, 2H), 7.24-7.26(d, J=8Hz, 2H), 7.02-7.07(m, 8H), 6.80-6.87(m, 6H), 1.42-1.21(m, 8H), 1.09-0.99(m, 2H), 0.86-0.83(t, J=6.8Hz, 3H), 0.50(s, 3H)..

实施例6：Embodiment 6:

R₁R₁ R₂R₂ R₃R₃ R₄R₄ 化合物compound 熔点melting point 甲基Methyl 己基Hexyl 氢hydrogen 氢hydrogen XIXI 430℃430℃

在N₂保护下，按实施例2方法制得的1-甲基-2己基-3，4-二苯基-2，5-二溴苯基噻咯(0.26g，0.4mmol)，2，2’：6’2”-联三吡啶-4’-苯基-4，4，5，5-四甲基-1，3，2-二氧杂环戊硼烷(0.52g，1.2mmol)，催化剂Pd(PPh₃)₄0.04mmol，碳酸钾0.1g，在10ml四氢呋喃和5ml水溶剂中，回流反应72小时。反应结束后，先用10ml水猝灭反应，过滤，滤饼用20ml四氢呋喃溶解。用5％的KOH溶剂洗涤，30ml Et₂O萃取，取有机层蒸除溶剂，得到粗产物过柱提纯，用石油醚与乙酸乙酯(体积比4∶1)为洗脱剂，所得洗脱液蒸除溶剂得式XI所示产物(0.22g，收率50％)。Under the protection of_N2 , 1-methyl-2-hexyl-3,4-diphenyl-2,5-dibromophenylsilole (0.26g, 0.4mmol) prepared according to the method of Example 2, 2, 2': 6'2"-Terpyridine-4'-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.52g, 1.2mmol) , catalyst Pd(PPh₃ )₄ 0.04mmol, potassium carbonate 0.1g, in 10ml tetrahydrofuran and 5ml water solvent, reflux reaction for 72 hours. After the reaction, first quench the reaction with 10ml water, filter, and dissolve the filter cake with 20ml tetrahydrofuran Wash with 5% KOH solvent, extract with 30ml Et₂ O, take the organic layer and distill off the solvent to obtain the crude product through column purification, using petroleum ether and ethyl acetate (volume ratio 4:1) as eluent, the obtained wash The solvent was evaporated to obtain the product represented by formula XI (0.22 g, yield 50%).

产物最大亮度为660cd/cm²，测试方法同实施例1。The maximum brightness of the product is 660cd/cm² , and the test method is the same as that in Example 1.

¹HNMR(400MHz，CDCl₃)，8.71-8.75(m，8H)，8.64-8.66(d，J＝8Hz，4H)，7.93-7.95(d，J＝8Hz，5H)，7.82-7.86(t，J＝6.8Hz，5H)，7.67-7.69(d，J＝8Hz，5H)，7.45-7.47(d，J＝7.6Hz，4H)，7.30-7.33(t，J＝5.2Hz，5H)，7.07(s，7H)，6.91(m，3H)，1.42-1.21(m，8H)，1.09-0.99(m，2H)，0.86-0.83(t，J＝6.8Hz，3H)，0.50(s，3H)..¹ HNMR (400MHz, CDCl₃ ), 8.71-8.75(m, 8H), 8.64-8.66(d, J=8Hz, 4H), 7.93-7.95(d, J=8Hz, 5H), 7.82-7.86(t, J=6.8Hz, 5H), 7.67-7.69(d, J=8Hz, 5H), 7.45-7.47(d, J=7.6Hz, 4H), 7.30-7.33(t, J=5.2Hz, 5H), 7.07 (s, 7H), 6.91(m, 3H), 1.42-1.21(m, 8H), 1.09-0.99(m, 2H), 0.86-0.83(t, J=6.8Hz, 3H), 0.50(s, 3H ) ..

实施例7：Embodiment 7:

R₁R₁ R₂R₂ R₃R₃ R₄R₄ 化合物compound 熔点melting point 己基Hexyl 己基Hexyl 氢hydrogen 氢hydrogen XIIXII 450℃450℃

在N₂保护下，1，1-二己基-3，4-二苯基-2，5-二溴苯基噻咯(0.28g，0.4mmol)，2，2’：6’2”-联三吡啶-4’-苯基-4，4，5，5-四甲基-1，3，2-二氧杂环戊硼烷(0.52g，1.2mmol)，催化剂Pd(PPh₃)₄ 0.04mmol，碳酸钾0.1g，在10ml四氢呋喃和5ml水溶剂中，回流反应72小时。反应结束后，先用10ml水猝灭反应，过滤，滤饼用20ml四氢呋喃溶解。用5％的KOH溶剂洗涤，30ml Et₂O萃取，取有机层蒸除溶剂，得到粗产物经柱层析提纯，以石油醚与乙酸乙酯(体积比4∶1)为洗脱剂，所得洗脱液蒸除溶剂得式XII所示产物(0.21g，46％)。Under_N2 protection, 1,1-dihexyl-3,4-diphenyl-2,5-dibromophenylsilole (0.28g, 0.4mmol), 2,2':6'2"-bi Tripyridine-4'-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.52g, 1.2mmol), catalyst Pd(PPh₃ )₄ 0.04 mmol, salt of wormwood 0.1g, in 10ml tetrahydrofuran and 5ml water solvent, reflux reaction 72 hours.After reaction finishes, quench reaction with 10ml water earlier, filter, filter cake dissolves with 20ml tetrahydrofuran.With the KOH solvent washing of 5%, Extract with 30ml_Et2O , take the organic layer and evaporate the solvent to obtain the crude product and purify it by column chromatography, using petroleum ether and ethyl acetate (volume ratio 4:1) as the eluent, and evaporate the solvent from the obtained eluent to obtain the formula Product shown in XII (0.21 g, 46%).

产物最大亮度为680cd/cm²，测试方法同实施例1。The maximum brightness of the product is 680cd/cm² , and the test method is the same as that in Example 1.

¹HNMR(400MHz，CDCl₃)，8.71-8.75(m，8H)，8.64-8.66(d，J＝8Hz，4H)，7.93-7.95(d，J＝8Hz，5H)，7.82-7.86(t，J＝6.8Hz，5H)，7.67-7.69(d，J＝8Hz，5H)，7.45-7.47(d，J＝7.6Hz，4H)，7.30-7.33(t，J＝5.2Hz，5H)，7.07(s，7H)，6.91(m，3H)，1.42-1.21(m，16H)，1.09-0.99(m，4H)，0.86-0.83(t，J＝6.8Hz，6H).¹ HNMR (400MHz, CDCl₃ ), 8.71-8.75(m, 8H), 8.64-8.66(d, J=8Hz, 4H), 7.93-7.95(d, J=8Hz, 5H), 7.82-7.86(t, J=6.8Hz, 5H), 7.67-7.69(d, J=8Hz, 5H), 7.45-7.47(d, J=7.6Hz, 4H), 7.30-7.33(t, J=5.2Hz, 5H), 7.07 (s, 7H), 6.91 (m, 3H), 1.42-1.21 (m, 16H), 1.09-0.99 (m, 4H), 0.86-0.83 (t, J=6.8Hz, 6H).

其中1，1-二己基-3，4-二苯基-2，5-二溴苯基噻咯按以下方法制备：Wherein 1,1-dihexyl-3,4-diphenyl-2,5-dibromophenylsilole is prepared by the following method:

氮气保护下，向锂粒(83mg，12mmol)和萘(1.54g，12.1mmol)的混合物中加入THF(12mL)制备萘基锂溶液，4小时后，缓慢加入二苯乙炔基二己基硅烷(900mg，3.0mmol))，时间超过10分钟。反应物冷却到-10℃，加入ZnCl₂-TMEDA(3.0g，12mmol)和THF(20ml)。反应一小时后，加入4-溴碘苯(1.7g，6mmol)和PdCl₂(PPh₃)₂(70mg，0.1mmol)，在30℃下反应12小时。加入10ml HCl(1N)猝灭反应，水洗，饱和NaCl溶液洗，50ml无水乙醚萃取，取有机层干燥。得到粗产物过柱提纯，石油醚为洗脱剂，洗脱液蒸除溶剂即得1，1-二己基-3，4-二苯基-2，5-二溴苯基噻咯0.91g。Under nitrogen protection, THF (12mL) was added to a mixture of lithium particles (83mg, 12mmol) and naphthalene (1.54g, 12.1mmol) to prepare a naphthyllithium solution. After 4 hours, diphenylethynyl dihexylsilane (900mg , 3.0mmol)) for more than 10 minutes. The reactant was cooled to -10°C, and ZnCl₂ -TMEDA (3.0 g, 12 mmol) and THF (20 ml) were added. After reacting for one hour, 4-bromoiodobenzene (1.7 g, 6 mmol) and PdCl₂ (PPh₃ )₂ (70 mg, 0.1 mmol) were added, and reacted at 30°C for 12 hours. Add 10ml of HCl (1N) to quench the reaction, wash with water, wash with saturated NaCl solution, extract with 50ml of anhydrous ether, and take the organic layer to dry. The obtained crude product was purified by column using petroleum ether as the eluent, and the solvent was evaporated from the eluent to obtain 0.91 g of 1,1-dihexyl-3,4-diphenyl-2,5-dibromophenylsilole.

Claims

1. cough up compounds suc as formula the bilateral identical replacement thiophene that contains ter cycloheptapyridine shown in the V:

Among the formula V, R₁, R₂Independent separately is the alkyl of hydrogen, C1～C10, naphthenic base or the phenyl of C3～C6; R₃Be the naphthenic base of the alkyl of hydrogen, C1～C10, C3～C6 or any one or two or more combinations in the phenyl;

R₄Be the naphthenic base of the alkyl of hydrogen, C1～C6, C3～C6 or any one or two or more combinations in the phenyl;

Among the formula V, the R of different positions₃Represent identical group, the R of different positions₄Represent identical group.

2. compound as claimed in claim 1 is characterized in that said R₁Be methyl or phenyl; R₂Be methyl or phenyl; R₃Be any one or the two or more combinations in hydrogen, methyl, ethyl or the phenyl; R₄Be any one or the two or more combinations in hydrogen, methyl, ethyl or the phenyl.

3. the preparation method of compound as claimed in claim 1 is characterized in that said method is:

Compound shown in compound shown in the formula I and the formula III carries out the Suzuki linked reaction under nitrogen protection; With four-(triphenyl phosphorus) palladiums is catalyzer; In the mixed solvent of THF and water; Adding alkaline matter maintenance reacting liquid pH value is 7～9 salt of wormwood, back flow reaction 72～100 hours, and reaction finishes the reaction solution aftertreatment and obtains compound shown in the formula V; Compound shown in the said formula I is 1: 3 with the ratio of the amount of substance of compound shown in the formula III;

In formula I or the formula III, R₁, R₂Independent separately is the alkyl of hydrogen, C1～C10, naphthenic base or the phenyl of C3～C6;

Among the formula I, R₃Be the naphthenic base of the alkyl of hydrogen, C1～C10, C3～C6 or any one or two or more combinations in the phenyl;

In the formula III, R₄Be the naphthenic base of the alkyl of hydrogen, C1～C6, C3～C6 or any one or two or more combinations in the phenyl;

Among the formula I, the R of different positions₃Represent identical group; In the formula III, the R of different positions₄Represent identical group.

4. method as claimed in claim 3 is characterized in that said reaction solution post-treating method is: after reaction finished, reaction solution added water quencher reaction, filters, and gets filter cake and dissolves with THF, with adding Et behind the KOH solution washing₂The O extraction is got the organic layer steaming and is desolventized, and obtains compound bullion shown in the formula V; The bullion of compound shown in the formula V is through column chromatography for separation; With sherwood oil and 4: 1 mixing solutionss of ETHYLE ACETATE volume ratio is eluent, and the gained elutriant steams and desolventizes, and makes the pure article of compound shown in the formula V.

5. method as claimed in claim 3 is characterized in that compound prepares by following method shown in the said formula I:

Under the nitrogen protection, metallic lithium and naphthalene are dissolved in the THF, and reaction dripped the compound shown in the formula vi after 4 hours under the room temperature, reacted 10 minutes～1 hour, was cooled to-10 ℃ then, added ZnCl₂-TMEDA complex compound and THF reacted after 1～2 hour, added 4-bromo-iodobenzene and catalyst P dCl₂(PPh₃)₂Reacted 12 hours down at 30 ℃, reaction finishes afterreaction liquid and adds 1N hydrochloric acid quencher reaction, adding anhydrous diethyl ether extraction behind water, the saturated NaCl solution washing successively; Get the organic layer drying; Obtaining crude product and cross the post purification, is eluent with the sherwood oil, and elutriant steams to desolventize and promptly gets compound shown in the formula I; Compound shown in said metallic lithium, naphthalene, the formula vi, ZnCl₂The ratio of the amount of substance of-TMEDA complex compound, 4-bromo-iodobenzene is 1: 1～1.1: 0.25: 1: 0.5;

Among the formula vi, R₃Be the naphthenic base of the alkyl of hydrogen, C1～C10, C3～C6 or any one or two or more combinations in the phenyl, and, the R of different positions₃Represent identical group.

6. method as claimed in claim 3 is characterized in that the step of said method is:

Compound shown in compound shown in the formula I and the formula III carries out the suzuki linked reaction under nitrogen protection, be catalyzer with four-(triphenyl phosphorus) palladiums, in the mixed solvent of THF and water; Adding alkaline matter maintenance reacting liquid pH value is 7～9; Back flow reaction 72～100 hours, reaction finish reaction solution and add water quencher reaction, filter; Get filter cake and dissolve, with adding Et behind the KOH solution washing with THF₂The O extraction is got the organic layer steaming and is desolventized, and obtains compound bullion shown in the formula V; The bullion of compound shown in the formula V is through column chromatography for separation; With sherwood oil and 4: 1 mixing solutions of ETHYLE ACETATE volume ratio is eluent, and the gained elutriant steams and desolventizes, and makes the pure article of compound shown in the formula V; Compound shown in the said formula I is 1: 3 with the ratio of the amount of substance of compound shown in the formula III; The amount of substance consumption of said four-(triphenyl phosphorus) palladiums be compound shown in the formula I amount of substance 10%.

7. the bilateral identical replacement thiophene that contains ter cycloheptapyridine as claimed in claim 1 is coughed up the application of compounds as luminescent material.

8. cough up compounds suc as formula the asymmetric replacement thiophene that contains ter cycloheptapyridine shown in the IV:

Among the formula IV, R₁, R₂Independent separately is the alkyl of hydrogen, C1～C10, naphthenic base or the phenyl of C3～C6; R₃Be the naphthenic base of the alkyl of hydrogen, C1～C10, C3～C6 or any one or two or more combinations in the phenyl;

Among the formula IV, the R of different positions₃Represent identical group, the R of different positions₄Represent identical group.

9. the preparation method of compound as claimed in claim 8 is characterized in that said method is:

Compound shown in compound shown in the formula I and the formula III carries out the Suzuki linked reaction under nitrogen protection; With four-(triphenyl phosphorus) palladiums is catalyzer; In the mixed solvent of THF and water; Adding alkaline matter maintenance reacting liquid pH value is 7～9, back flow reaction 10～15 hours, and reaction finishes the reaction solution aftertreatment and obtains compound shown in the formula IV; Compound shown in the said formula I is 1: 3 with the ratio of the amount of substance of compound shown in the formula III;

10. the asymmetric replacement thiophene that contains ter cycloheptapyridine as claimed in claim 8 is coughed up the application of compounds as luminescent material.