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CN106957301A - A kind of preparation method of the hydroxycarbazole class compound of N heteroaryls 2 - Google Patents

A kind of preparation method of the hydroxycarbazole class compound of N heteroaryls 2Download PDF

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CN106957301A
CN106957301ACN201710321007.7ACN201710321007ACN106957301ACN 106957301 ACN106957301 ACN 106957301ACN 201710321007 ACN201710321007 ACN 201710321007ACN 106957301 ACN106957301 ACN 106957301A
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carbazole
heteroaryl
bromo
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ethyl acetate
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李贵杰
佘远斌
赵向东
方坤
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Zhejiang University of Technology ZJUT
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本发明公开了一种N‑杂芳基‑2‑羟基咔唑类化合物的制备方法，所述的方法按如下步骤进行：在氮气保护下,以N‑杂芳基‑2‑溴咔唑类化合物为原料，Cu盐为催化剂，N1,N2‑双(4‑羟基‑2,6‑二甲苯基)草酰胺为配体，在碱性物质作用下，在溶剂中，于80‑110℃下反应1‑72小时，所得反应液经后处理得到N‑杂芳基‑2‑羟基咔唑类化合物；本发明缩短了反应步骤，方便高效，原料和催化剂便宜易得，反应工艺及操作简单、收率高达98％且适于大量制备和工业化，具有广阔的应用前景。The invention discloses a preparation method of N-heteroaryl-2-hydroxycarbazole compounds. The method is carried out as follows: under the protection of nitrogen, the N-heteroaryl-2-bromocarbazole Compound is raw material, Cu salt is catalyst, N1 , N2 -bis(4-hydroxyl-2,6-xylyl) oxalamide is ligand, under the action of basic substance, in solvent, at 80-110 Reaction at ℃ for 1-72 hours, the resulting reaction solution is post-treated to obtain N-heteroaryl-2-hydroxycarbazole compounds; the present invention shortens the reaction steps, is convenient and efficient, and the raw materials and catalysts are cheap and easy to obtain, and the reaction process and operation It is simple, has a yield as high as 98%, is suitable for mass preparation and industrialization, and has broad application prospects.

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Translated fromChinese
一种N-杂芳基-2-羟基咔唑类化合物的制备方法A kind of preparation method of N-heteroaryl-2-hydroxycarbazole compound

技术领域technical field

本发明涉及一种N-杂-2-羟基咔唑类化合物的制备方法。The invention relates to a preparation method of N-hetero-2-hydroxycarbazole compounds.

背景技术Background technique

N-杂芳基-2-羟基咔唑类化合物是合成四齿环金属铂和钯配合物磷光材料分子极为重要的中间体，被广泛用于此类分子的合成之中。四齿环金属铂和钯配合物由于其中心重金属离子和有机配体之间的强自旋偶合作用，使其处于激发单线态或电子可以有效地进行系间蹿越而回到激发三线态，同时可以使处于激发三线态的分子可以进行高效地辐射转变释放能量回到基态，从而室温下即可高效地发出磷光，并且磷光量子效率可以高达100％,从而使这类金属有机配合物可以作为有机电致磷光发光材料而在显示和照明领域有着广泛的应用前景。其中N-(2-吡啶基)咔唑结构单元广泛存在于这种四齿环金属铂和钯配合物之中，且对此类分子的光物理性质、化学稳定性和热力学稳定性有着重要的影响(Angew.Chem.Int.Ed.2013,52,6753；Org.Electronics,2014,15,1862；Adv.Mater.2014,26,7116；ACS Appl.Mater.&Interfaces,2015,7,16240；Adv.Optical Mater.2015,3,390；Adv.Mater.2015,27,2533；US 20130168656；WO 2014031977；US 20160359125)。最近，美国亚利桑那州立大学的Jian Li教授小组报道了稳定而高效的全六元环螯合的四齿环金属铂配合物磷光器件，为蓝色磷光器件的进一步发展提供了新的方向(Chem.Mater.2016,28,3276)，而N-杂芳基-2-羟基咔唑类化合物正是合成此类分子不可或缺的重要中间体(式Ⅰ)。N-heteroaryl-2-hydroxycarbazole compounds are extremely important intermediates in the synthesis of tetradentate ring metal platinum and palladium complex phosphorescent material molecules, and are widely used in the synthesis of such molecules. Due to the strong spin coupling between the central heavy metal ion and the organic ligand, the tetradentate ring metal platinum and palladium complexes are in the excited singlet state or the electrons can effectively perform intersystem jumping and return to the excited triplet state. At the same time, the molecules in the excited triplet state can undergo efficient radiative transformation to release energy back to the ground state, so that phosphorescence can be efficiently emitted at room temperature, and the phosphorescence quantum efficiency can be as high as 100%, so that this type of metal-organic complex can be used as Organic electrophosphorescent luminescent materials have broad application prospects in the fields of display and lighting. Among them, the N-(2-pyridyl)carbazole structural unit widely exists in this tetradentate ring metal platinum and palladium complexes, and plays an important role in the photophysical properties, chemical stability and thermodynamic stability of such molecules. Impact (Angew.Chem.Int.Ed.2013,52,6753; Org.Electronics,2014,15,1862; Adv.Mater.2014,26,7116; ACS Appl.Mater.&Interfaces,2015,7,16240; Adv. .Optical Mater.2015,3,390; Adv.Mater.2015,27,2533; US 20130168656; WO 2014031977; US 20160359125). Recently, Professor Jian Li's group from Arizona State University reported a stable and efficient phosphorescent device of a tetradentate ring metal platinum complex with a full six-membered ring chelation, which provides a new direction for the further development of blue phosphorescent devices (Chem. Mater.2016, 28, 3276), and N-heteroaryl-2-hydroxycarbazole compounds are the indispensable and important intermediates (formula I) for the synthesis of such molecules.

目前文献中已报道的N-杂芳基-2-羟基咔唑类化合物合成方法主要有以下两种，其一是美国Universal Display Corporation(UDC)报道的以邻硝基碘苯和对甲氧基苯硼酸为原料，通过零价钯催化的Suzuki偶联反应生成2'-硝基-4-甲氧基联苯1；然后以三乙氧基磷为还原剂和溶剂进行关环反应生成2-甲氧基咔唑2；接着再与2-碘吡啶通过零价钯催化的C-N键的偶联反应得到N-(2-吡啶基)-2-甲氧基咔唑3；最后在200℃下脱掉甲基生成目标产物N-(2-吡啶基)-2-羟基咔唑4(路线1)(US 20130168656)。此合成路线有如下不足之处：其一，需四步反应，总收率低，只有22％；其二，其中有两步需要用到价格高昂的零价钯催化剂；其三，有两步反应温度很高，分别为165℃和200℃；其四，引入吡啶基团时需要用到价格昂贵的2-碘吡啶。The synthetic method of N-heteroaryl-2-hydroxyl carbazole compound that has been reported in the literature mainly contains following two kinds at present, and one is that U.S. Universal Display Corporation (UDC) reports with o-nitroiodobenzene and p-methoxy Phenylboronic acid was used as raw material to generate 2'-nitro-4-methoxybiphenyl 1 through Suzuki coupling reaction catalyzed by zero-valent palladium; Methoxycarbazole 2; followed by coupling reaction with 2-iodopyridine through a zero-valent palladium-catalyzed C-N bond to obtain N-(2-pyridyl)-2-methoxycarbazole 3; finally at 200 ° C The methyl group is removed to generate the target product N-(2-pyridyl)-2-hydroxycarbazole 4 (route 1) (US 20130168656). This synthetic route has following disadvantages: one, needs four-step reaction, and total yield is low, only has 22%; The reaction temperature is very high, respectively 165°C and 200°C; Fourthly, expensive 2-iodopyridine is needed to introduce the pyridine group.

第二种方法是美国亚利桑那州立大学Jian Li教授和Guijie Li于2014年报道的以2-羟基咔唑为原料，用苄基保护羟基后得到中间体5，然后通过零价钯催化的Suzuki偶联和4-叔丁基-溴吡啶反应生成N-[2-(4-叔丁基吡啶基)]-2-苄氧基咔唑6，最后用当量的三氟化硼脱掉苄基得到目标产物N-[2-(4-叔丁基吡啶基)]-2-羟基咔唑7(路线2)(Adv.Mater.2014,26,7116)。2016年Jian Li教授和Guijie Li用相似的方法报道了N-(2-吡啶基)-2-羟基咔唑4的合成 (路线3)(US 20160359125)。这两种方法虽然比路线1高效，但是亦有不足之处，其一，所用原料2-羟基咔唑价格昂贵，不利于反应的大量制备；其二，其中亦需要用到价格高昂的零价钯催化剂和配体JohnPhos；其三，需要用苄基做保护基团，总体来说原子经济性较差。The second method is reported by Professor Jian Li and Guijie Li of Arizona State University in 2014, using 2-hydroxycarbazole as a raw material, protecting the hydroxyl group with a benzyl group to obtain intermediate 5, and then passing Suzuki coupling catalyzed by zero-valent palladium React with 4-tert-butyl-bromopyridine to generate N-[2-(4-tert-butylpyridyl)]-2-benzyloxycarbazole 6, and finally remove the benzyl group with an equivalent amount of boron trifluoride to obtain the target Product N-[2-(4-tert-butylpyridyl)]-2-hydroxycarbazole 7 (Scheme 2) (Adv. Mater. 2014, 26, 7116). In 2016, Prof. Jian Li and Guijie Li reported the synthesis of N-(2-pyridyl)-2-hydroxycarbazole 4 using a similar method (Route 3) (US 20160359125). Although these two methods are more efficient than route 1, they also have shortcomings. One, the raw material 2-hydroxycarbazole is expensive, which is not conducive to the large-scale preparation of the reaction; Palladium catalyst and ligand JohnPhos; third, benzyl needs to be used as a protecting group, and overall atom economy is poor.

因此，如何发展一种便宜、高效制备N-杂芳基-2-羟基咔唑类化合物的方法， 对于磷光材料的开发，尤其是全六元环螯合的四齿环金属铂配合物磷光材料的发展将起到极大的促进作用。Therefore, how to develop a cheap and efficient method for preparing N-heteroaryl-2-hydroxycarbazole compounds, for the development of phosphorescent materials, especially the tetradentate ring metal platinum complex phosphorescent materials with full six-membered ring chelation development will be greatly promoted.

芳基溴化物比较便宜易得，如果可以实现将芳基溴化物直接进行官能团转换变为羟基，将为羟基芳烃类化合物的合成提供一种简便而高效的方法。Buchwald、Beller等小组实现了在大位阻的膦配体的辅助下金属钯化合物催化芳基卤化物制备羟基芳烃类化合物。但是由于膦配体和金属钯化合物的价格昂贵，使其应用，尤其是对于需要大量制备的反应受到很大限制(J.Am.Chem.Soc.2006,128,10694；Angew.Chem.,Int.Ed.2009,48,918；Angew.Chem.,Int.Ed.2009,48,7595)。而目前发展的廉价金属铜化合物催化的此类官能团的转化反应基本上只限于底物结构简单、位阻较小芳基碘化物和溴化物，且催化剂和配体的用量较大，反应温度也比较高，尤其是无法实现N-杂芳基-2-溴咔唑类化合物到N-杂芳基-2-羟基咔唑类化合物的官能团转化，极大的限制了此类反应在功能材料制备等领域的应用。Aryl bromides are relatively cheap and easy to obtain. If the direct functional group conversion of aryl bromides into hydroxyl groups can be realized, it will provide a simple and efficient method for the synthesis of hydroxyaromatic compounds. Buchwald, Beller and other groups realized the preparation of hydroxyarene compounds from aryl halides catalyzed by metal palladium compounds with the assistance of bulky phosphine ligands. However, due to the high price of the phosphine ligand and metal palladium compound, its application, especially for the reaction that requires a large amount of preparation, is greatly limited (J.Am.Chem.Soc.2006,128,10694; Angew.Chem., Int Ed. 2009, 48, 918; Angew. Chem., Int. Ed. 2009, 48, 7595). However, the conversion reaction of such functional groups catalyzed by cheap metal copper compounds developed at present is basically limited to aryl iodides and bromides with simple structure and small hindrance, and the amount of catalyst and ligand is relatively large, and the reaction temperature is also low. Relatively high, especially the functional group conversion of N-heteroaryl-2-bromocarbazole compounds to N-heteroaryl-2-hydroxycarbazole compounds, which greatly limits the use of such reactions in the preparation of functional materials applications in other fields.

综上所述，虽然金属钯和铜化合物催化的芳基卤化物转化为羟基芳烃类化合物的反应已得到发展，但是由N-杂芳基-2-溴咔唑类化合物直接转化为N-杂芳基-2-羟基咔唑类化合物反应尚未见文献报道，且N-杂芳基-2-羟基咔唑类化合物是合成四齿环金属铂和钯配合物磷光材料的重要中间体，因此如何实现此类化合物的高效转化将对磷光材料的合成发展起到重要的推动作用，可以极大地促进OLED等相关领域的发展。In summary, although metal palladium and copper compounds catalyzed the conversion of aryl halides to hydroxyaromatic compounds, the direct conversion of N-heteroaryl-2-bromocarbazoles to N-heteroaryl The reaction of aryl-2-hydroxycarbazole compounds has not been reported in the literature, and N-heteroaryl-2-hydroxycarbazole compounds are important intermediates for the synthesis of four-ring metal platinum and palladium complex phosphorescent materials, so how to Realizing the efficient conversion of such compounds will play an important role in promoting the synthesis and development of phosphorescent materials, which can greatly promote the development of OLED and other related fields.

发明内容Contents of the invention

本发明的目的在于提供一种N-杂芳基-2-羟基咔唑类化合物的制备方法。该方法可以廉价、简洁、高效地合成N-杂芳基-2-羟基咔唑类化合物化合物，可以实现此类化合物克级甚至更大量的制备，极大地促进了此类反应在磷光材料合成方面的应用，可以极大地促进OLED等相关领域的发展。The object of the present invention is to provide a kind of preparation method of N-heteroaryl-2-hydroxycarbazole compound. This method can synthesize N-heteroaryl-2-hydroxycarbazole compounds in a cheap, concise and efficient manner, and can realize the preparation of such compounds in grams or even larger quantities, which greatly promotes the application of such reactions in the synthesis of phosphorescent materials. The application of OLED can greatly promote the development of OLED and other related fields.

本发明采用的技术方案如下：The technical scheme that the present invention adopts is as follows:

一种N-杂芳基-2-羟基咔唑类化合物的制备方法，其特征在于：所述的方法按如下步骤进行：在氮气保护下,以N-杂芳基-2-溴咔唑类化合物为原料，Cu盐为催化剂，N 1,N 2-双(4-羟基-2,6-二甲苯基)草酰胺为配体，在碱性物质作用下，在溶剂中，于80-110℃下反应1-72小时，所述的N-杂芳基-2-溴咔唑类化合物如式(1)、式(2)、式(3)或式(4)所示所得反应液经后处理分别得到如式(Ⅰ)、(Ⅱ)、(Ⅲ)或(Ⅳ)所示的N-杂芳基-2-羟基咔唑类化合物；所述的N-杂芳基-2-溴咔唑类化合物与N 1,N 2-双(4-羟基-2,6-二甲苯基)草酰胺、碱性物质的物质的量之比为：1:0.01～0.1：1.0～5.0；所述配体N 1,N 2-双(4-羟基-2,6-二甲苯基)草酰胺与Cu(I)或Cu(II)盐催化剂物质的量之比为1～5:1；A preparation method of N-heteroaryl-2-hydroxycarbazole compounds, characterized in that: the method is carried out as follows: under the protection of nitrogen, with N-heteroaryl-2-bromocarbazole Compound as raw material, Cu salt as catalyst, N 1,N 2-bis(4-hydroxy-2,6-xylyl) oxalamide as ligand, under the action of alkaline substances, in a solvent, at 80-110 ℃ for 1-72 hours, the N-heteroaryl-2-bromocarbazole compound as shown in formula (1), formula (2), formula (3) or formula (4) obtained reaction solution Aftertreatment obtains the N-heteroaryl-2-hydroxyl carbazole compound shown in formula (I), (II), (III) or (IV) respectively; Described N-heteroaryl-2-bromo The ratio of the amount of carbazole compounds to N 1,N 2-bis(4-hydroxy-2,6-xylyl) oxalamide and basic substances is: 1:0.01～0.1:1.0～5.0; The ratio of the amount of ligand N 1,N 2-bis(4-hydroxy-2,6-xylyl) oxalamide to Cu(I) or Cu(II) salt catalyst substance is 1-5:1;

所述式(1)中R1、R2、R3分别与式(I)中的R1、R2、R3相同，所述式(2)中R4、R5、R6分别与式(Ⅱ)中R4、R5、R6相同，所述式(3)中分别与式(Ⅲ)中R7、R8、R9相同，所述式(4)中R10、R11、R12分别与式(Ⅳ)中R10、R11、R12相同，所述R1-R12各自独立为H或氘、C1－C12烷基或C1－C10烷氧基、C6－C20芳基、C10-C14杂芳基、烷基胺基，C1－C12芳基氨基，或杂芳环相邻的两个碳连接苯并环取代基。R1 , R2 , R3 in the formula (1) are respectively the same as R1 , R2 , R3 in the formula (I), and R4 , R5 , R6 in the formula (2) are respectively the same as R4 , R5 , and R6 in formula (II) are the same, R 7 , R 8 , and R 9 in formula (III) in formula (3) are the same as R7 , R8 , and R9 in formula (III), and R10 , R11 and R12 are respectively the same as R10 , R11 and R12 in formula (IV), and the R1 -R12 are each independently H or deuterium, C1 -C12 alkyl or C1 -C10 alkoxy C6 -C20 aryl, C10 -C14 heteroaryl, alkylamino, C1 -C12 arylamino, or a benzo ring substituent connected to two adjacent carbons of the heteroaryl ring.

进一步，所述的式(1)、式(2)、式(3)或式(4)所示的N-杂芳基-2-溴咔唑类化合物为2-溴-9-(2-吡啶基)咔唑、2-溴-9-[2-(3-甲基-吡啶基)]咔唑、2-溴-9-[2-(4-甲基-吡啶基)]咔唑、2-溴-9-(2-(5-甲基-吡啶基))咔唑、2-溴-9-(2-喹啉基)咔唑、2-溴-9-(2-异喹啉基)咔唑、2-溴-9-(2-嘧啶基)咔唑、2-溴-9-(2-吡嗪基)咔唑、2-溴-9-(2-噻唑基)咔唑、和或3-溴-9-(2-吡啶基)咔唑。Further, the N-heteroaryl-2-bromocarbazole compound represented by the formula (1), formula (2), formula (3) or formula (4) is 2-bromo-9-(2- pyridyl)carbazole, 2-bromo-9-[2-(3-methyl-pyridyl)]carbazole, 2-bromo-9-[2-(4-methyl-pyridyl)]carbazole, 2-bromo-9-(2-(5-methyl-pyridyl))carbazole, 2-bromo-9-(2-quinolyl)carbazole, 2-bromo-9-(2-isoquinoline Base) carbazole, 2-bromo-9-(2-pyrimidinyl)carbazole, 2-bromo-9-(2-pyrazinyl)carbazole, 2-bromo-9-(2-thiazolyl)carbazole , and or 3-bromo-9-(2-pyridyl)carbazole.

进一步，所述的催化剂Cu盐为氯化亚铜、溴化亚铜、碘化亚铜、醋酸铜或硫酸铜及其它们各自的水合物。Further, the catalyst Cu salt is cuprous chloride, cuprous bromide, cuprous iodide, copper acetate or copper sulfate and their respective hydrates.

进一步，所述的碱性物质为氢氧化锂、氢氧化钠、氢氧化钾、叔丁醇锂、叔丁醇钠、叔丁醇钾、甲醇钠、乙醇钠、碳酸铯、碳酸钾或磷酸钾。Further, the alkaline substance is lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, sodium ethoxide, cesium carbonate, potassium carbonate or potassium phosphate .

进一步，所述的溶剂为N,N-二甲基甲酰胺或二甲基亚砜/水的两种任意比的混合物。Further, the solvent is N,N-dimethylformamide or a mixture of two random ratios of dimethyl sulfoxide/water.

再进一步，所述溶剂的总加入量以N-杂芳基-2-溴咔唑类化合物的物质的量计为1～100mL/mmol。Still further, the total amount of the solvent added is 1-100 mL/mmol based on the amount of N-heteroaryl-2-bromocarbazole compounds.

再进一步，优选所述的N-杂芳基-2-溴咔唑类化合物与N 1,N 2-双(4-羟基-2,6-二甲苯基)草酰胺、碱性物质的物质的量之比为：1:0.01～0.05：1.5～3.0。Further, preferably the N-heteroaryl-2-bromocarbazole compound and N 1,N 2-bis(4-hydroxyl-2,6-xylyl) oxalamide, basic substances The ratio of quantity is: 1:0.01～0.05:1.5～3.0.

再进一步，优选所述的配体N 1,N 2-双(4-羟基-2,6-二甲苯基)草酰胺与Cu(I)或Cu(II)盐催化剂物质的量之比为1:1。Still further, it is preferred that the ratio of the amount of ligand N 1, N 2-bis(4-hydroxyl-2,6-xylyl) oxalamide to Cu(I) or Cu(II) salt catalyst substance is 1 :1.

本发明所述反应的后处理方法为：反应结束后，待反应液冷却，用乙酸乙酯萃取，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，得到目标产物。The post-processing method of the reaction of the present invention is as follows: after the reaction is completed, the reaction solution is cooled, extracted with ethyl acetate, the organic phases are combined, dried over anhydrous sodium sulfate, filtered, and the solvent is removed by distillation under reduced pressure, and the obtained crude product is passed through a silica gel column. Purify by chromatography to obtain the target product.

与现有技术相比，本发明的有益效果体现在：Compared with the prior art, the beneficial effects of the present invention are reflected in:

(1)合成目标产物N-杂芳基-2-羟基咔唑类化合物方便高效，与已报道的路线1-3相比，极大的缩短了反应步骤；(1) The synthesis of the target product N-heteroaryl-2-hydroxycarbazole compound is convenient and efficient, and compared with the reported route 1-3, the reaction steps are greatly shortened;

(2)所述原料N-杂芳基-2-溴咔唑类化合物易于制备，所需原料可以以便宜的2-溴咔唑和2-溴吡啶类化合物经过我们之前发展的CuCl催化的C-N键的偶联反应一步合成，且收率高，易于大规模制备(CN 201610769719.0；J.Org.Chem.2017,82,1024；见下式)。其中2-溴咔唑(500克/3600元)价格远远低于路线2和路线3中的起始原料2-羟基咔唑(5克/465元)。(2) The raw material N-heteroaryl-2-bromocarbazole compound is easy to prepare, and the required raw material can be catalyzed by the CuCl-catalyzed C-N The coupling reaction of the bond is synthesized in one step, and the yield is high, and it is easy to prepare on a large scale (CN 201610769719.0; J.Org.Chem.2017, 82, 1024; see the following formula). Among them, the price of 2-bromocarbazole (500 grams/3600 yuan) is far lower than the starting material 2-hydroxycarbazole (5 grams/465 yuan) in routes 2 and 3.

(3)所用催化剂便宜易得，不仅可以为碘化亚铜，甚至可以使用更为经济的溴化亚铜、氯化亚铜或醋酸铜。(3) The catalyst used is cheap and easy to get, not only cuprous iodide, but also more economical cuprous bromide, cuprous chloride or copper acetate can be used.

(4)反应溶剂无需进行处理、反应工艺及操作简单、收率高达98％且适于大量制备和工业化，具有广阔的应用前景。(4) The reaction solvent does not need to be treated, the reaction process and operation are simple, the yield is as high as 98%, and it is suitable for mass production and industrialization, and has broad application prospects.

(5)利用此反应可以方便高效地合成蓝光磷光材料PtNON和PtNON，同时为此类磷光材料的制备提供了一种最为经济高效的合成方法。(5) The blue phosphorescent materials PtNON and PtNON can be conveniently and efficiently synthesized by using this reaction, and at the same time, it provides a most economical and efficient synthesis method for the preparation of such phosphorescent materials.

具体实施方式detailed description

下面通过具体实施例对本发明作进一步说明，但本发明的保护范围并不仅限于此。The present invention will be further described below through specific examples, but the protection scope of the present invention is not limited thereto.

实施例1：2-羟基-9-(2-吡啶基)咔唑的制备Embodiment 1: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(323.2mg,1.00mmol,1.0eq)，氯化亚铜(5.0mg,0.05mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(16.4mg,0.05mmol,0.05eq)，一水合氢氧化锂(88.1mg,2.1mmol,2.1eq)。抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流12小时。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝10:1-3:1)，得白色固体206.9mg，收率79％。1H NMR(500MHz,DMSO-d6):δ6.79(dd,J＝8.5,2.0Hz,1H),7.18(d,J＝2.0Hz,1H),7.23-7.26(m,1H),7.32(td,J＝8.5,1.0Hz,1H),7.47(ddd,J＝7.5,5.0,1.0Hz,1H),7.69(d,J＝8.0Hz,1H),7.74(d,J＝8.0Hz,1H),7.99(d,J＝8.5Hz,1H),8.06(d,J＝7.5Hz,1H),8.11(td,J＝8.0,2.0Hz,1H),8.72(ddd,J＝5.0,2.0,0.5Hz,1H),9.61(s,1H).13C NMR(126MHz,DMSO-d6):δ97.10,110.34,110.77,115.85,119.01,119.12,120.78,121.08,121.80,124.02,124.48,138.79,139.29,140.54,149.45,150.88,157.02.HRMS(ESI):calcd for C17H13N2O[M+H]+261.1022,found 261.1028.2-Bromo-9-(2-pyridyl)carbazole (323.2mg, 1.00mmol, 1.0eq), cuprous chloride (5.0mg, 0.05mmol, 0.05eq ), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (16.4mg, 0.05mmol, 0.05eq), lithium hydroxide monohydrate (88.1mg, 2.1mmol, 2.1 eq). Nitrogen was purged three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 12 hours. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=10:1-3:1), to obtain 206.9 mg of a white solid, with a yield of 79%.1 H NMR (500MHz, DMSO-d6 ): δ6.79 (dd, J = 8.5, 2.0Hz, 1H), 7.18 (d, J = 2.0Hz, 1H), 7.23-7.26 (m, 1H), 7.32 (td, J=8.5,1.0Hz,1H),7.47(ddd,J=7.5,5.0,1.0Hz,1H),7.69(d,J=8.0Hz,1H),7.74(d,J=8.0Hz, 1H), 7.99(d, J=8.5Hz, 1H), 8.06(d, J=7.5Hz, 1H), 8.11(td, J=8.0, 2.0Hz, 1H), 8.72(ddd, J=5.0, 2.0 ,0.5Hz,1H),9.61(s,1H).13 C NMR(126MHz,DMSO-d6 ):δ97.10,110.34,110.77,115.85,119.01,119.12,120.78,121.08,121.80,124.02,124.48,138.79, 139.29,140.54,149.45,150.88,157.02.HRMS(ESI):calcd for C17 H13 N2 O[M+H]+ 261.1022,found 261.1028.

实施例2：2-羟基-9-(2-吡啶基)咔唑的制备Embodiment 2: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥三口烧瓶中依次加入2-溴-9-(2-吡啶基)咔唑(9.70g,30.00mmol,1.0eq)，氯化亚铜(148.5mg,1.50mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(493.0mg,1.50mmol,0.05eq)，一水合氢氧化锂(2.64g,63.0mmol,2.1eq)。抽换氮气三次，然后加入DMSO(37.5mL)和去离子水(9.5mL)。反应混合物于100℃下回流48小时，TLC薄层色谱监测至2-溴-9-(2-吡啶基)咔唑反应完毕。冷却，加入100mL乙酸乙酯稀释，硅藻土抽滤，用去离子水清洗有机相(50mL×3)，合并水相，用乙酸乙酯萃取水相(50mL×2)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得混合物用乙酸乙酯和石油醚各20mL重结晶于70℃回流24小时，抽滤，石油醚充分清洗得灰色固体5.61g。重结晶母液减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得白色固体425.5mg。固体共计6.04g,收率79％。产物经1H NMR确认，与实施例1中数据一致。Add 2-bromo-9-(2-pyridyl)carbazole (9.70g, 30.00mmol, 1.0eq), cuprous chloride (148.5mg, 1.50mmol, 0.05eq ), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (493.0mg, 1.50mmol, 0.05eq), lithium hydroxide monohydrate (2.64g, 63.0mmol, 2.1 eq). Nitrogen was purged three times, then DMSO (37.5 mL) and deionized water (9.5 mL) were added. The reaction mixture was refluxed at 100° C. for 48 hours, monitored by TLC until the reaction of 2-bromo-9-(2-pyridyl)carbazole was completed. Cool, add 100mL ethyl acetate to dilute, filter with diatomaceous earth, wash the organic phase with deionized water (50mL×3), combine the aqueous phase, extract the aqueous phase with ethyl acetate (50mL×2), combine the organic phase, Dry over sodium sulfate, filter, and distill off the solvent under reduced pressure. The resulting mixture was recrystallized with 20 mL each of ethyl acetate and petroleum ether, refluxed at 70° C. for 24 hours, filtered with suction, and thoroughly washed with petroleum ether to obtain 5.61 g of a gray solid. The recrystallized mother liquor was distilled off under reduced pressure to remove the solvent, and the resulting crude product was separated and purified by silica gel column chromatography with eluent (petroleum ether/ethyl acetate=3:1) to obtain 425.5 mg of white solid. The total solid is 6.04g, the yield is 79%. The product was confirmed by1 H NMR, which was consistent with the data in Example 1.

实施例3：2-羟基-9-(2-吡啶基)咔唑的制备Embodiment 3: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥三口烧瓶中依次加入2-溴-9-(2-吡啶基)咔唑(9.70g,30.00mmol,1.0eq)，氯化亚铜(148.5mg,1.50mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(493.0mg,1.50mmol,0.05eq)，叔丁醇钠(6.05g,63.0mmol,2.1eq)抽换氮气三次，然后加入DMSO(37.5mL)和去离子水(9.5mL)。反应混合物于100℃下回流48小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，加入100mL乙酸乙酯稀释，硅藻土抽滤，用去离子水清洗有机相3次(50mL/每次)，合并水相，用乙酸乙酯萃取水相(50mL×2)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂。所得混合物用乙酸乙酯和石油醚各10mL重结晶，70℃回流24小时，抽滤，石油醚充分清洗得灰色固体5.77g。重结晶母液减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得白色固体1.50g。固体共计7.27g,收率93％。产物经1H NMR确认，与实施例1中数据一致。Add 2-bromo-9-(2-pyridyl)carbazole (9.70g, 30.00mmol, 1.0eq), cuprous chloride (148.5mg, 1.50mmol, 0.05eq ), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (493.0mg, 1.50mmol, 0.05eq), sodium tert-butoxide (6.05g, 63.0mmol, 2.1eq ) was purged of nitrogen three times, then DMSO (37.5 mL) and deionized water (9.5 mL) were added. The reaction mixture was refluxed at 100°C for 48 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 100mL ethyl acetate to dilute, filter with diatomaceous earth, wash the organic phase 3 times with deionized water (50mL/each time), combine the aqueous phase, extract the aqueous phase with ethyl acetate (50mL×2), combine the organic phase phase, dried over anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to remove the solvent. The resulting mixture was recrystallized with 10 mL each of ethyl acetate and petroleum ether, refluxed at 70°C for 24 hours, filtered with suction, and thoroughly washed with petroleum ether to obtain 5.77 g of a gray solid. The recrystallization mother liquor was distilled off under reduced pressure to remove the solvent, and the resulting crude product was separated and purified by silica gel column chromatography with eluent (petroleum ether/ethyl acetate=3:1) to obtain 1.50 g of a white solid. The total solid was 7.27g, the yield was 93%. The product was confirmed by1 H NMR, which was consistent with the data in Example 1.

实施例4：2-羟基-9-(2-吡啶基)咔唑的制备Embodiment 4: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(161.6mg,0.5mmol,1.0eq)，溴化亚铜(3.6mg,0.03mmol,0.05eq)，N1,N2-双(4-羟基-2,6- 二甲苯基)草酰胺(8.2mg,0.03mmol,0.05eq)，一水合氢氧化锂(44.1mg,1.1mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝5:1-3:1)，得白色固体104.2mg，收率80％。产物经1H NMR确认，与实施例1中数据一致。2-Bromo-9-(2-pyridyl)carbazole (161.6mg, 0.5mmol, 1.0eq), cuprous bromide (3.6mg, 0.03mmol, 0.05eq ), N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.03mmol, 0.05eq), lithium hydroxide monohydrate (44.1mg, 1.1mmol, 2.1eq) Nitrogen was purged three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=5:1-3:1), to obtain 104.2 mg of a white solid, with a yield of 80%. The product was confirmed by1 H NMR, which was consistent with the data in Example 1.

实施例5：2-羟基-9-(2-吡啶基)咔唑的制备Embodiment 5: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(161.6mg,0.5mmol,1.0eq)，碘化亚铜(4.8mg,0.03mmol,0.05eq)，N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.03mmol,0.05eq)，一水合氢氧化锂(44.1mg,1.1mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝5:1-3:1)，得白色固体105.1mg，收率80％。产物经1H NMR确认，与实施例1中数据一致。2-Bromo-9-(2-pyridyl)carbazole (161.6mg, 0.5mmol, 1.0eq), cuprous iodide (4.8mg, 0.03mmol, 0.05eq ), N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.03mmol, 0.05eq), lithium hydroxide monohydrate (44.1mg, 1.1mmol, 2.1eq) Nitrogen was purged three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=5:1-3:1), to obtain 105.1 mg of a white solid, with a yield of 80%. The product was confirmed by1 H NMR, which was consistent with the data in Example 1.

实施例6：2-羟基-9-(2-吡啶基)咔唑的制备Embodiment 6: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(1.62g,5.0mmol,1.0eq)，醋酸铜(49.9mg,0.25mmol,0.05eq)，N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(82.1mg,0.25mmol,0.05eq)，一水合氢氧化锂(440.6mg,10.5mmol,2.1eq)抽换氮气三次，然后加入DMSO(4.0mL)和去离子水(1.0mL)。反应混合物于100℃下回流48小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入50.0mL乙酸乙酯和50.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(50mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝5:1-3:1)，得白色固体860.3mg，收率66％。产物经1H NMR确认，与实施例1中数据一致。To a dry reaction tube with a magnetic rotor, 2-bromo-9-(2-pyridyl)carbazole (1.62g, 5.0mmol, 1.0eq), copper acetate (49.9mg, 0.25mmol, 0.05eq) were sequentially added, N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (82.1mg, 0.25mmol, 0.05eq), replaced with lithium hydroxide monohydrate (440.6mg, 10.5mmol, 2.1eq) Nitrogen three times, then DMSO (4.0 mL) and deionized water (1.0 mL) were added. The reaction mixture was refluxed at 100°C for 48 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 50.0mL ethyl acetate and 50.0mL deionized water to the reaction system in turn, and transfer them to a separatory funnel for liquid separation, extract with ethyl acetate (50mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=5:1-3:1), and 860.3 mg of a white solid was obtained, with a yield of 66%. The product was confirmed by1 H NMR, which was consistent with the data in Example 1.

实施例7：2-羟基-9-(2-吡啶基)咔唑的制备Embodiment 7: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(161.6mg,0.5mmol,1.0eq)，五水硫酸铜(6.2mg,0.03mmol,0.05eq)，N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.03mmol,0.05eq)，一水合氢氧化锂(44.1mg,1.1mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝5:1-3:1)，得白色固体52.3mg，收率40％。产物经1H NMR确认，与实施例1中数据一致。Add 2-bromo-9-(2-pyridyl)carbazole (161.6mg, 0.5mmol, 1.0eq), copper sulfate pentahydrate (6.2mg, 0.03mmol, 0.05eq ), N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.03mmol, 0.05eq), lithium hydroxide monohydrate (44.1mg, 1.1mmol, 2.1eq) Nitrogen was purged three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=5:1-3:1), and 52.3 mg of a white solid was obtained, with a yield of 40%. The product was confirmed by1 H NMR, which was consistent with the data in Example 1.

实施例8：2-羟基-9-(2-吡啶基)咔唑的制备Embodiment 8: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(161.6mg,0.5mmol,1.0eq)，氯化亚铜(2.5mg,0.03mmol,0.05eq)，N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.03mmol,0.05eq)，一水合氢氧化锂(44.1mg,1.1mmol,2.1eq)抽换氮气三次，然后加入DMF(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝5:1-3:1)，得白色固体56.1mg，收率43％。产物经1H NMR确认，与实施例1中数据一致。2-Bromo-9-(2-pyridyl)carbazole (161.6mg, 0.5mmol, 1.0eq), cuprous chloride (2.5mg, 0.03mmol, 0.05eq ), N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.03mmol, 0.05eq), lithium hydroxide monohydrate (44.1mg, 1.1mmol, 2.1eq) Nitrogen was purged three times, then DMF (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=5:1-3:1), to obtain 56.1 mg of a white solid, with a yield of 43%. The product was confirmed by1 H NMR, which was consistent with the data in Example 1.

实施例9：2-羟基-9-(2-吡啶基)咔唑的制备Embodiment 9: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(161.6mg,0.5mmol,1.0eq)，氯化亚铜(2.5mg,0.03mmol,0.05eq)，N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.03mmol,0.05eq)，氢氧化钠(42.0mg,1.1mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取水相3次(每次25mL)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝5:1-3:1)，得棕色固体114.5mg，收率88％。产物经1H NMR确认，与实施例1中数据一致。2-Bromo-9-(2-pyridyl)carbazole (161.6mg, 0.5mmol, 1.0eq), cuprous chloride (2.5mg, 0.03mmol, 0.05eq ), N1 , N2 -bis(4-hydroxy-2,6-xylyl) oxalamide (8.2mg, 0.03mmol, 0.05eq), sodium hydroxide (42.0mg, 1.1mmol, 2.1eq) Nitrogen three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system successively, and transfer it to a separatory funnel for liquid separation, extract the aqueous phase 3 times with ethyl acetate (each 25mL), combine the organic phases, without Dry over sodium sulfate, filter, and distill off the solvent under reduced pressure. The resulting crude product is separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=5:1-3:1), to obtain 114.5 mg of a brown solid, the yield 88%. The product was confirmed by1 H NMR, which was consistent with the data in Example 1.

实施例10：2-羟基-9-(2-吡啶基)咔唑的制备Embodiment 10: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(161.6mg,0.5mmol,1.0eq)，氯化亚铜(2.5mg,0.03mmol,0.05eq)，N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.03mmol,0.05eq)，氢氧化钾(58.9mg,1.1mmol,2.1eq)，抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝5:1-3:1)，得白色固体107.8mg，收率83％。产物经1H NMR确认与实施例1中数据一致。2-Bromo-9-(2-pyridyl)carbazole (161.6mg, 0.5mmol, 1.0eq), cuprous chloride (2.5mg, 0.03mmol, 0.05eq ), N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.03mmol, 0.05eq), potassium hydroxide (58.9mg, 1.1mmol, 2.1eq), extraction Nitrogen was changed three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=5:1-3:1), to obtain 107.8 mg of a white solid, with a yield of 83%. The product was confirmed to be consistent with the data in Example 1 by1 H NMR.

实施例11：2-羟基-9-(2-吡啶基)咔唑的制备Example 11: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(161.6mg,0.5mmol,1.0eq)，氯化亚铜(2.5mg,0.03mmol,0.05eq)，N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.03mmol,0.05eq)，磷酸钾(222.9mg,1.1mmol,2.1eq)，抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝5:1-3:1)，得白色固体38.5mg，收率30％。产物经1H NMR确认，与实施例1中数据一致。2-Bromo-9-(2-pyridyl)carbazole (161.6mg, 0.5mmol, 1.0eq), cuprous chloride (2.5mg, 0.03mmol, 0.05eq ), N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.03mmol, 0.05eq), potassium phosphate (222.9mg, 1.1mmol, 2.1eq), exchange Nitrogen three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=5:1-3:1), and 38.5 mg of white solid was obtained, with a yield of 30%. The product was confirmed by1 H NMR, which was consistent with the data in Example 1.

实施例12：2-羟基-9-(2-吡啶基)咔唑的制备Example 12: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(161.6mg,0.5mmol,1.0eq)，氯化亚铜(2.5mg,0.03mmol,0.05eq)，N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.03mmol,0.05eq)，碳酸钾(145.1mg,1.1mmol,2.1 eq)，抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝5:1-3:1)，得白色固体32.7mg，收率25％。产物经1H NMR确认，与实施例1中数据一致。2-Bromo-9-(2-pyridyl)carbazole (161.6mg, 0.5mmol, 1.0eq), cuprous chloride (2.5mg, 0.03mmol, 0.05eq ), N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.03mmol, 0.05eq), potassium carbonate (145.1mg, 1.1mmol, 2.1 eq), exchange Nitrogen three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=5:1-3:1), and 32.7 mg of a white solid was obtained, with a yield of 25%. The product was confirmed by1 H NMR, which was consistent with the data in Example 1.

实施例13：2-羟基-9-(2-吡啶基)咔唑的制备Example 13: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(161.6mg,0.5mmol,1.0eq)，氯化亚铜(2.5mg,0.03mmol,0.05eq)，N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.03mmol,0.05eq)，碳酸铯(342.1mg,1.1mmol,2.1eq)，抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝5:1-3:1)，得白色固体84.4mg，收率65％。产物经1H NMR确认，与实施例1中数据一致。2-Bromo-9-(2-pyridyl)carbazole (161.6mg, 0.5mmol, 1.0eq), cuprous chloride (2.5mg, 0.03mmol, 0.05eq ), N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.03mmol, 0.05eq), cesium carbonate (342.1mg, 1.1mmol, 2.1eq), exchange Nitrogen three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=5:1-3:1), and 84.4 mg of white solid was obtained, with a yield of 65%. The product was confirmed by1 H NMR, which was consistent with the data in Example 1.

实施例14：2-羟基-9-(2-吡啶基)咔唑的制备Example 14: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(161.6mg,0.5mmol,1.0eq)，氯化亚铜(2.5mg,0.03mmol,0.05eq)，N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.03mmol,0.05eq)，叔丁醇锂(84.1mg,1.1mmol,2.1eq)，抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24.0小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝5:1-3:1)，得黄色固体114.6mg，收率88％。产物经1H NMR确认与实施例1中数据一致。2-Bromo-9-(2-pyridyl)carbazole (161.6mg, 0.5mmol, 1.0eq), cuprous chloride (2.5mg, 0.03mmol, 0.05eq ), N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.03mmol, 0.05eq), lithium tert-butoxide (84.1mg, 1.1mmol, 2.1eq), Nitrogen was purged three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24.0 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=5:1-3:1), and 114.6 mg of a yellow solid was obtained, with a yield of 88%. The product was confirmed to be consistent with the data in Example 1 by1 H NMR.

实施例15：2-羟基-9-(2-吡啶基)咔唑的制备Example 15: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(161.6mg,0.5mmol,1.0eq)，氯化亚铜(2.5mg,0.03mmol,0.05eq)，N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.03mmol,0.05eq)，叔丁醇钠(100.9mg,1.1mmol,2.1eq)，抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝5:1-3:1)，得黄色固体123.5mg，收率95％。产物经1H NMR确认与实施例1中数据一致。2-Bromo-9-(2-pyridyl)carbazole (161.6mg, 0.5mmol, 1.0eq), cuprous chloride (2.5mg, 0.03mmol, 0.05eq ), N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.03mmol, 0.05eq), sodium tert-butoxide (100.9mg, 1.1mmol, 2.1eq), Nitrogen was purged three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=5:1-3:1), to obtain 123.5 mg of a yellow solid, with a yield of 95%. The product was confirmed to be consistent with the data in Example 1 by1 H NMR.

实施例16：2-羟基-9-(2-吡啶基)咔唑的制备Example 16: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(161.6mg,0.5mmol,1.0eq)，氯化亚铜(2.5mg,0.03mmol,0.05eq)，N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.03mmol,0.05eq)，叔丁醇钾(117.8mg,1.1mmol,2.1eq)，抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝5:1-3:1)，得黄色固体119.3mg，收率92％。产物经1H NMR确认与实施例1中数据一致。2-Bromo-9-(2-pyridyl)carbazole (161.6mg, 0.5mmol, 1.0eq), cuprous chloride (2.5mg, 0.03mmol, 0.05eq ), N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.03mmol, 0.05eq), potassium tert-butoxide (117.8mg, 1.1mmol, 2.1eq), Nitrogen was purged three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=5:1-3:1), to obtain 119.3 mg of a yellow solid, with a yield of 92%. The product was confirmed to be consistent with the data in Example 1 by1 H NMR.

实施例17：2-羟基-9-(2-吡啶基)咔唑的制备Example 17: Preparation of 2-hydroxyl-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(161.6mg,0.5mmol,1.0eq)，氯化亚铜(2.5mg,0.03mmol,0.05eq)，N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.03mmol,0.05eq)，甲醇钠(56.7mg,1.1mmol,2.1eq)，抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子H2O充分清洗，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸 钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝5:1-3:1)，得黄色固体101.2mg，收率78％。产物经1H NMR确认与实施例1中数据一致。2-Bromo-9-(2-pyridyl)carbazole (161.6mg, 0.5mmol, 1.0eq), cuprous chloride (2.5mg, 0.03mmol, 0.05eq ), N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.03mmol, 0.05eq), sodium methoxide (56.7mg, 1.1mmol, 2.1eq), exchange Nitrogen three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. After cooling, add 25.0 mL of ethyl acetate and 25.0 mL of deionized H2 O to the reaction system in turn to fully wash, transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25 mL×3), combine the organic phases, and remove Dry over sodium sulfate, filter, and distill off the solvent under reduced pressure. The resulting crude product is separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=5:1-3:1), and 101.2 mg of a yellow solid is obtained. The yield 78%. The product was confirmed to be consistent with the data in Example 1 by1 H NMR.

实施例18：2-羟基-9-(2-吡啶基)咔唑的制备Example 18: Preparation of 2-hydroxy-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(161.6mg,0.5mmol,1.0eq)，氯化亚铜(2.5mg,0.03mmol,0.05eq)，N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.03mmol,0.05eq)，乙醇钠(71.9mg,1.1mmol,2.1eq)，抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝5:1-3:1)，得黄色固体116.1mg，收率89％。产物经1H NMR确认与实施例1中数据一致。2-Bromo-9-(2-pyridyl)carbazole (161.6mg, 0.5mmol, 1.0eq), cuprous chloride (2.5mg, 0.03mmol, 0.05eq ), N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.03mmol, 0.05eq), sodium ethoxide (71.9mg, 1.1mmol, 2.1eq), exchange Nitrogen three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=5:1-3:1), to obtain 116.1 mg of a yellow solid, with a yield of 89%. The product was confirmed to be consistent with the data in Example 1 by1 H NMR.

实施例19：2-羟基-9-(2-吡啶基)咔唑的制备Z-8-83(叔丁醇钠)Example 19: Preparation of 2-hydroxy-9-(2-pyridyl)carbazole Z-8-83 (sodium tert-butoxide)

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡啶基)咔唑(161.6mg,0.5mmol,1.0eq)，氯化亚铜(2.5mg,0.03mmol,0.05eq)，N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.03mmol,0.05eq)，叔丁醇钠(100.9mg,1.1mmol,2.1eq)，抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于80℃下回流2小时，TLC薄层色谱监测2-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝5:1-3:1)，得黄色固体75.7mg，收率58％。产物经1H NMR确认与实施例1中数据一致。2-Bromo-9-(2-pyridyl)carbazole (161.6mg, 0.5mmol, 1.0eq), cuprous chloride (2.5mg, 0.03mmol, 0.05eq ), N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.03mmol, 0.05eq), sodium tert-butoxide (100.9mg, 1.1mmol, 2.1eq), Nitrogen was purged three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 80°C for 2 hours, and 2-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=5:1-3:1), and 75.7 mg of a yellow solid was obtained, with a yield of 58%. The product was confirmed to be consistent with the data in Example 1 by1 H NMR.

实施例20：2-羟基-9-[2-(3-甲基-吡啶基)]咔唑的制备Example 20: Preparation of 2-hydroxy-9-[2-(3-methyl-pyridyl)]carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-[2-(3-甲基-吡啶基)]咔唑(337.2mg,1.00mmol,1.0eq)，氯化亚铜(5.0mg,0.05mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(16.4mg,0.05mmol,0.05eq)，一水合氢氧 化锂(88.1mg,2.1mmol,2.1eq)。然后抽换氮气三次，再加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子H2O充分清洗，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝10:1-3:1)，得红色固体245.2mg，收率89％。1H NMR(500MHz,DMSO-d6):δ2.01(s,3H),6.39(d,J＝2.0Hz,1H),6.75(dd,J＝8.5,2.5Hz,1H),6.96(d,J＝8.0Hz,1H),7.21(td,J＝7.5,1.0Hz,1H),7.27(td,J＝7.0,1.0Hz,1H),7.57(dd,J＝8.0,5.0Hz,1H),8.00(d,J＝8.5Hz,1H),8.04-8.07(m,2H),8.58(dd,J＝4.5,1.0Hz,1H),9.51(s,1H).13C NMR(100MHz,DMSO-d6):δ16.85,95.84,109.59,109.74,115.13,119.34,119.94,121.37,123.19,124.21,124.34,131.03,139.62,141.02,141.43,147.75,148.83,156.97.HRMS(ESI):calcd forC18H15N2O[M+H]+275.1179,found 275.1191.2-Bromo-9-[2-(3-methyl-pyridyl)]carbazole (337.2mg, 1.00mmol, 1.0eq), cuprous chloride (5.0 mg, 0.05mmol, 0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl) oxalamide (16.4mg, 0.05mmol, 0.05eq), lithium hydroxide monohydrate ( 88.1 mg, 2.1 mmol, 2.1 eq). Nitrogen was then purged three times, and DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24 hours. After cooling, add 25.0 mL of ethyl acetate and 25.0 mL of deionized H2 O to the reaction system in turn to fully wash, transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25 mL×3), combine the organic phases, and remove Dry over sodium sulfate, filter, and distill off the solvent under reduced pressure. The resulting crude product is separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=10:1-3:1), to obtain 245.2 mg of a red solid, which is obtained as The rate is 89%.1 H NMR (500MHz, DMSO-d6 ): δ2.01(s, 3H), 6.39(d, J=2.0Hz, 1H), 6.75(dd, J=8.5, 2.5Hz, 1H), 6.96(d ,J=8.0Hz,1H),7.21(td,J=7.5,1.0Hz,1H),7.27(td,J=7.0,1.0Hz,1H),7.57(dd,J=8.0,5.0Hz,1H) , 8.00(d, J=8.5Hz, 1H), 8.04-8.07(m, 2H), 8.58(dd, J=4.5, 1.0Hz, 1H), 9.51(s, 1H).13 C NMR (100MHz, DMSO -d6 ):δ16.85,95.84,109.59,109.74,115.13,119.34,119.94,121.37,123.19,124.21,124.34,131.03,139.62,141.02,141.43,147.75,148.97.1518 H15 N2 O[M+H]+ 275.1179, found 275.1191.

实施例21：2-羟基-9-[2-(3-甲基-吡啶基)]咔唑的制备Example 21: Preparation of 2-hydroxy-9-[2-(3-methyl-pyridyl)]carbazole

向带有磁力转子的干燥反应管中冷却，依次加入2-溴-9-(2-(3-甲基-吡啶基))咔唑(84.3mg,0.25mmol,1.0eq)，氯化亚铜(1.3mg,0.01mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(4.1mg,0.01mmol,0.05eq)，氢氧化钠(21.0mg,0.53mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于110℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-(3-甲基-吡啶基))咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得棕色固体65.2mg，收率91％。产物经1H NMR确认与实施例20中数据一致。Cool in a dry reaction tube with a magnetic rotor, add 2-bromo-9-(2-(3-methyl-pyridyl))carbazole (84.3mg, 0.25mmol, 1.0eq), cuprous chloride (1.3mg, 0.01mmol, 0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl) oxalamide (4.1mg, 0.01mmol, 0.05eq), sodium hydroxide ( 21.0 mg, 0.53 mmol, 2.1 eq) was purged of nitrogen three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 110°C for 24 hours, and 2-bromo-9-(2-(3-methyl-pyridyl))carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=3:1), to obtain 65.2 mg of a brown solid, with a yield of 91%. The product was confirmed to be consistent with the data in Example 20 by1 H NMR.

实施例22：2-羟基-9-[2-(3-甲基-吡啶基)]咔唑的制备Example 22: Preparation of 2-hydroxy-9-[2-(3-methyl-pyridyl)]carbazole

向带有磁力转子的干燥反应管中冷却，依次加入2-溴-9-(2-(3-甲基-吡啶基))咔唑(212.9mg,0.63mmol,1.0eq)，氯化亚铜(3.1mg,0.03mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(10.3mg,0.03mmol,0.05eq)，叔丁醇钠(127.1mg,1.32mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于110℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-(3-甲基-吡啶基))咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通 过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝10:1-3:1)，得棕色固体168.9mg，收率98％。产物经1H NMR确认与实施例20中数据一致。Cool in a dry reaction tube with a magnetic rotor, add 2-bromo-9-(2-(3-methyl-pyridyl))carbazole (212.9mg, 0.63mmol, 1.0eq), cuprous chloride (3.1mg, 0.03mmol, 0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (10.3mg, 0.03mmol, 0.05eq), sodium tert-butoxide (127.1 mg, 1.32 mmol, 2.1 eq) was purged of nitrogen three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 110°C for 24 hours, and 2-bromo-9-(2-(3-methyl-pyridyl))carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=10:1-3:1), to obtain 168.9 mg of a brown solid, with a yield of 98%. The product was confirmed to be consistent with the data in Example 20 by1 H NMR.

实施例23：2-羟基-9-(2-(4-甲基-吡啶基))咔唑的制备Example 23: Preparation of 2-hydroxy-9-(2-(4-methyl-pyridyl))carbazole

向带有磁力转子的干燥反应管中，依次加入2-溴-9-[2-(4-甲基-吡啶基)]咔唑(337.2mg,1.00mmol,1.0eq)，氯化亚铜(5.0mg,0.05mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(16.4mg,0.05mmol,0.05eq)，一水合氢氧化锂(88.1mg,2.1mmol,2.1eq)。然后抽换氮气三次，再依次加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子H2O充分清洗，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得白色固体258.4mg，收率94％。1H NMR(500MHz,DMSO-d6):δ2.48(s,3H),6.78(dd,J＝8.5,2.0Hz,1H),7.16(d,J＝2.0Hz,1H),7.23-7.26(m,1H),7.30-7.33(m,2H),7.57(s,1H),7.68(d,J＝8.5Hz,1H),7.99(d,J＝8.0Hz,1H),8.05(d,J＝7.5Hz,1H),8.57(d,J＝5.0Hz,1H),9.59(s,1H).13C NMR(100MHz,DMSO-d6):δ20.66,97.18,110.26,110.88,115.82,119.14,119.50,120.70,121.10,122.88,123.97,124.48,138.87,140.63,149.05,150.44,150.96,156.98.HRMS(ESI):calcd for C18H15N2O[M+H]+275.1179,found275.1190.To a dry reaction tube with a magnetic rotor, 2-bromo-9-[2-(4-methyl-pyridyl)]carbazole (337.2 mg, 1.00 mmol, 1.0 eq), cuprous chloride ( 5.0mg, 0.05mmol, 0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (16.4mg, 0.05mmol, 0.05eq), lithium hydroxide monohydrate (88.1 mg, 2.1 mmol, 2.1 eq). Then the nitrogen gas was exchanged three times, and then DMSO (2.0 mL) and deionized water (0.5 mL) were added sequentially. The reaction mixture was refluxed at 100°C for 24 hours. After cooling, add 25.0 mL of ethyl acetate and 25.0 mL of deionized H2 O to the reaction system in turn to fully wash, transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25 mL×3), combine the organic phases, and remove Dry over sodium sulfate, filter, and distill off the solvent under reduced pressure. The resulting crude product is separated and purified by silica gel column chromatography with eluent (petroleum ether/ethyl acetate=3:1) to obtain 258.4 mg of white solid with a yield of 94%.1 H NMR (500MHz, DMSO-d6 ): δ2.48(s, 3H), 6.78(dd, J=8.5, 2.0Hz, 1H), 7.16(d, J=2.0Hz, 1H), 7.23-7.26 (m,1H),7.30-7.33(m,2H),7.57(s,1H),7.68(d,J=8.5Hz,1H),7.99(d,J=8.0Hz,1H),8.05(d, J＝7.5Hz, 1H), 8.57(d, J＝5.0Hz, 1H), 9.59(s, 1H).13 C NMR (100MHz, DMSO-d6 ): δ20.66, 97.18, 110.26, 110.88, 115.82 ,119.14,119.50,120.70,121.10,122.88,123.97,124.48,138.87,140.63,149.05,150.44,150.96,156.98.HRMS(ESI):calcd for C18 H15 N2 O[M+Hound]+ 27575 .1190.

实施例24：2-羟基-9-(2-(4-甲基-吡啶基))咔唑的制备Example 24: Preparation of 2-hydroxy-9-(2-(4-methyl-pyridyl))carbazole

向带有磁力转子的干燥反应管中，依次加入2-溴-9-(2-(4-甲基-吡啶基))咔唑(84.3mg,0.25mmol,1.0eq)，氯化亚铜(1.3mg,0.01mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(4.1mg,0.01mmol,0.05eq)，氢氧化钠(21.0mg,0.53mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于110℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-(4-甲基-吡啶基))咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得棕色固体53.8mg，收率78％。产物经1H NMR确认与实施例23中数据一致。To a dry reaction tube with a magnetic rotor, 2-bromo-9-(2-(4-methyl-pyridyl))carbazole (84.3 mg, 0.25 mmol, 1.0 eq), cuprous chloride ( 1.3mg, 0.01mmol, 0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl) oxalamide (4.1mg, 0.01mmol, 0.05eq), sodium hydroxide (21.0 mg, 0.53 mmol, 2.1 eq) was purged of nitrogen three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 110°C for 24 hours, and 2-bromo-9-(2-(4-methyl-pyridyl))carbazole was monitored by TLC. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=3:1), to obtain 53.8 mg of a brown solid, with a yield of 78%. The product was confirmed to be consistent with the data in Example 23 by1 H NMR.

实施例25：2-羟基-9-(2-(4-甲基-吡啶基))咔唑的制备Example 25: Preparation of 2-hydroxy-9-(2-(4-methyl-pyridyl))carbazole

向带有磁力转子的干燥反应管中，依次加入2-溴-9-(2-(4-甲基-吡啶基))咔唑(210.0mg,0.62mmol,1.0eq)，氯化亚铜(3.1mg,0.03mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(10.2mg,0.03mmol,0.05eq)，叔丁醇钠(124.9mg,1.30mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于110℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-(4-甲基-吡啶基))咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得棕色固体150.1mg，收率88％。产物经1H NMR确认与实施例23中数据一致。To a dry reaction tube with a magnetic rotor, 2-bromo-9-(2-(4-methyl-pyridyl))carbazole (210.0 mg, 0.62 mmol, 1.0 eq), cuprous chloride ( 3.1mg, 0.03mmol, 0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl) oxalamide (10.2mg, 0.03mmol, 0.05eq), sodium tert-butoxide ( 124.9 mg, 1.30 mmol, 2.1 eq) was purged of nitrogen three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 110°C for 24 hours, and 2-bromo-9-(2-(4-methyl-pyridyl))carbazole was monitored by TLC. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=3:1), to obtain 150.1 mg of a brown solid, with a yield of 88%. The product was confirmed to be consistent with the data in Example 23 by1 H NMR.

实施例26：2-羟基-9-(2-(5-甲基-吡啶基))咔唑的制备Example 26: Preparation of 2-hydroxy-9-(2-(5-methyl-pyridyl))carbazole

向带有磁力转子的干燥反应管中，依次加入2-溴-9-(2-(5-甲基-吡啶基))咔唑(337.2mg,1.00mmol,1.0eq)，氯化亚铜(5.0mg,0.05mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(16.4mg,0.05mmol,0.05eq)，一水合氢氧化锂(88.1mg,2.1mmol,2.1eq)。然后抽换氮气三次，再加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子H2O充分清洗，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得白色固体226.6mg，收率83％。1H NMR(500MHz,DMSO-d6):δ2.43(s,3H),6.77(dd,J＝8.0,2.0Hz,1H),7.10(d,J＝2.0Hz,1H),7.22-7.25(m,1H),7.29-7.32(m,1H),7.62-7.64(m,2H),7.93(ddd,J＝8.5,2.5,0.5Hz,1H),7.98(d,J＝8.5Hz,1H),8.04-8.06(m,1H),8.55(dd,J＝2.0,1.0Hz,1H),9.59(s,1H).13C NMR(100MHz,DMSO-d6):δ17.53,96.97,110.20,110.66,115.75,118.63,119.15,120.61,121.12,123.89,124.46,131.30,138.97,139.63,140.73,148.57,149.45,157.01.HRMS(ESI):calcd for C18H15N2O[M+H]+275.1179,found275.1180.To a dry reaction tube with a magnetic rotor, 2-bromo-9-(2-(5-methyl-pyridyl))carbazole (337.2 mg, 1.00 mmol, 1.0 eq), cuprous chloride ( 5.0mg, 0.05mmol, 0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (16.4mg, 0.05mmol, 0.05eq), lithium hydroxide monohydrate (88.1 mg, 2.1 mmol, 2.1 eq). Nitrogen was then purged three times, and DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24 hours. After cooling, add 25.0 mL of ethyl acetate and 25.0 mL of deionized H2 O to the reaction system in turn to fully wash, transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25 mL×3), combine the organic phases, and remove Dry over sodium sulfate, filter, and distill off the solvent under reduced pressure. The resulting crude product is separated and purified by silica gel column chromatography with eluent (petroleum ether/ethyl acetate=3:1) to obtain 226.6 mg of white solid with a yield of 83%.1 H NMR (500MHz, DMSO-d6 ): δ2.43(s, 3H), 6.77(dd, J=8.0, 2.0Hz, 1H), 7.10(d, J=2.0Hz, 1H), 7.22-7.25 (m,1H),7.29-7.32(m,1H),7.62-7.64(m,2H),7.93(ddd,J＝8.5,2.5,0.5Hz,1H),7.98(d,J＝8.5Hz,1H ),8.04-8.06(m,1H),8.55(dd,J＝2.0,1.0Hz,1H),9.59(s,1H).13 C NMR(100MHz,DMSO-d6 ):δ17.53,96.97,110.20,110.66,115.75,118.63,119.15,120.61,121.12,123.89,124.46,131.30,138.97,139.63,140.73,148.57,149.45,157.01._ ]+ 275.1179, found 275.1180.

实施例27：2-羟基-9-(2-(5-甲基-吡啶基))咔唑的制备Example 27: Preparation of 2-hydroxy-9-(2-(5-methyl-pyridyl))carbazole

向带有磁力转子的干燥反应管中，依次加入2-溴-9-(2-(5-甲基-吡啶基))咔唑(55.7mg,0.17mmol,1.0eq)，氯化亚铜(0.8mg,0.01mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(2.6mg,0.01mmol,0.05eq)，氢氧化钠(13.9mg,0.35mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于110℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-(5-甲基-吡啶基))咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子 水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得白色固体39.0mg，收率86％。产物经1H NMR确认与实施例26中数据一致。To a dry reaction tube with a magnetic rotor, 2-bromo-9-(2-(5-methyl-pyridyl))carbazole (55.7 mg, 0.17 mmol, 1.0 eq), cuprous chloride ( 0.8mg, 0.01mmol, 0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl) oxalamide (2.6mg, 0.01mmol, 0.05eq), sodium hydroxide (13.9 mg, 0.35 mmol, 2.1 eq) was purged of nitrogen three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 110°C for 24 hours, and 2-bromo-9-(2-(5-methyl-pyridyl))carbazole was monitored by TLC. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=3:1), to obtain 39.0 mg of white solid, with a yield of 86%. The product was confirmed to be consistent with the data in Example 26 by1 H NMR.

实施例28：2-羟基-9-(2-(5-甲基-吡啶基))咔唑的制备Example 28: Preparation of 2-hydroxy-9-(2-(5-methyl-pyridyl))carbazole

向带有磁力转子的干燥反应管中，依次加入2-溴-9-(2-(5-甲基-吡啶基))咔唑(183.2mg,0.54mmol,1.0eq)，氯化亚铜(2.7mg,0.03mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.9mg,0.03mmol,0.05eq)，叔丁醇钠(109.0mg,1.13mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于110℃下回流24.0小时，TLC薄层色谱监测2-溴-9-(2-(5-甲基-吡啶基))咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得棕色固体133.9mg，收率90％。产物经1H NMR确认与实施例26中数据一致。To a dry reaction tube with a magnetic rotor, 2-bromo-9-(2-(5-methyl-pyridyl))carbazole (183.2 mg, 0.54 mmol, 1.0 eq), cuprous chloride ( 2.7mg, 0.03mmol, 0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl) oxalamide (8.9mg, 0.03mmol, 0.05eq), sodium tert-butoxide ( 109.0 mg, 1.13 mmol, 2.1 eq) was purged of nitrogen three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 110°C for 24.0 hours, and 2-bromo-9-(2-(5-methyl-pyridyl))carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=3:1), to obtain 133.9 mg of a brown solid, with a yield of 90%. The product was confirmed to be consistent with the data in Example 26 by1 H NMR.

实施例29：2-羟基-9-(2-喹啉基)咔唑的制备Example 29: Preparation of 2-hydroxy-9-(2-quinolyl)carbazole

向带有磁力转子的干燥反应管中，依次加入2-溴-9-(2-喹啉基)咔唑(93.3mg,0.25mmol,1.0eq)，氯化亚铜(1.3mg,0.013mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(4.1mg,0.013mmol,0.05eq)，一水合氢氧化锂(22.0mg,0.53mmol,2.1eq)。然后抽换氮气三次，再依次加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流48小时。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子H2O充分清洗，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得黄色固体33.8mg，收率44％。1H NMR(500MHz,DMSO-d6):δ6.83(dd,J＝8.5,2.0Hz,1H),7.28-7.31(m,1H),7.37(td,J＝8.0,1.0Hz,1H),7.40(d,J＝2.0Hz,1H),7.67-7.70(m,1H),7.86-7.89(m,1H),7.90(d,J＝8.0Hz,1H),7.94(d,J＝8.5Hz,1H),8.03(d,J＝8.5Hz,1H),8.09(t,J＝8.5Hz,2H),8.12-8.13(m,1H),8.66(d,J＝8.5Hz,1H),9.67(s,1H).13C NMR(100MHz,DMSO-d6):δ97.70,110.68,111.32,116.18,117.69,119.25,121.20,121.24,124.38,124.71,126.29,126.50,128.10(2C),130.58,138.75,139.48,140.53,146.95,150.36,157.14.HRMS(ESI):calcd for C21H15N2O[M+H]+311.1179,found 311.1170.To a dry reaction tube with a magnetic rotor, add 2-bromo-9-(2-quinolyl)carbazole (93.3mg, 0.25mmol, 1.0eq), cuprous chloride (1.3mg, 0.013mmol, 0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (4.1mg, 0.013mmol, 0.05eq), lithium hydroxide monohydrate (22.0mg, 0.53mmol ,2.1eq). Then the nitrogen gas was exchanged three times, and then DMSO (2.0 mL) and deionized water (0.5 mL) were added sequentially. The reaction mixture was refluxed at 100°C for 48 hours. After cooling, add 25.0 mL of ethyl acetate and 25.0 mL of deionized H2 O to the reaction system in turn to fully wash, transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25 mL×3), combine the organic phases, and remove Dry over sodium sulfate, filter, and distill off the solvent under reduced pressure. The obtained crude product is separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=3:1), and 33.8 mg of a yellow solid is obtained, with a yield of 44%.1 H NMR (500MHz, DMSO-d6): δ6.83 (dd, J = 8.5, 2.0Hz, 1H), 7.28-7.31 (m, 1H), 7.37 (td, J = 8.0, 1.0Hz, 1H), 7.40(d, J=2.0Hz, 1H), 7.67-7.70(m, 1H), 7.86-7.89(m, 1H), 7.90(d, J=8.0Hz, 1H), 7.94(d, J=8.5Hz ,1H),8.03(d,J=8.5Hz,1H),8.09(t,J=8.5Hz,2H),8.12-8.13(m,1H),8.66(d,J=8.5Hz,1H),9.67 (s,1H).13 C NMR(100MHz,DMSO-d6 ):δ97.70,110.68,111.32,116.18,117.69,119.25,121.20,121.24,124.38,124.71,126.29,126.50,125.10(2C),1380. ,139.48,140.53,146.95,150.36,157.14.HRMS(ESI):calcd for C21 H15 N2 O[M+H]+ 311.1179,found 311.1170.

实施例30：2-羟基-9-(2-喹啉基)咔唑的制备Example 30: Preparation of 2-hydroxy-9-(2-quinolyl)carbazole

向带有磁力转子的干燥反应管中，依次加入2-溴-9-(2-喹啉基)咔唑(93.3mg,0.25mmol,1.0eq)，氯化亚铜(1.3mg,0.013mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺((4.1mg,0.013mmol,0.05eq)，氢氧化钠(21.0mg,0.53mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于110℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-喹啉基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得黄色固体29.4mg，收率38％，原料转化率80％。产物经1H NMR确认与实施例29中数据一致。To a dry reaction tube with a magnetic rotor, add 2-bromo-9-(2-quinolyl)carbazole (93.3mg, 0.25mmol, 1.0eq), cuprous chloride (1.3mg, 0.013mmol, 0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide ((4.1mg, 0.013mmol, 0.05eq), sodium hydroxide (21.0mg, 0.53mmol, 2.1eq) nitrogen was replaced three times, then DMSO (2.0mL) and deionized water (0.5mL) were added. The reaction mixture was refluxed at 110° C. for 24 hours, and TLC thin layer chromatography monitored 2-bromo-9-(2-quinoline base) carbazole. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system successively, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, Dry over anhydrous sodium sulfate, filter, distill off the solvent under reduced pressure, separate and purify the obtained crude product by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=3:1), and obtain 29.4 mg of yellow solid, yield 38% , The raw material conversion rate is 80%. The product is consistent with the data in Example 29 as confirmed by1 H NMR.

实施例31：2-羟基-9-(2-喹啉基)咔唑的制备Example 31: Preparation of 2-hydroxy-9-(2-quinolyl)carbazole

向带有磁力转子的干燥反应管中，依次加入2-溴-9-(2-喹啉基)咔唑(93.3mg,0.25mmol,1.0eq)，氯化亚铜(1.3mg,0.013mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺((4.1mg,0.013mmol,0.05eq)，叔丁醇钠(50.5mg,0.53mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于110℃下回流24.0小时，TLC薄层色谱监测2-溴-9-(2-喹啉基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得黄色固体76.4mg，收率98％。产物经1H NMR确认与实施例29中数据一致。To a dry reaction tube with a magnetic rotor, add 2-bromo-9-(2-quinolyl)carbazole (93.3mg, 0.25mmol, 1.0eq), cuprous chloride (1.3mg, 0.013mmol, 0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl) oxalamide ((4.1mg, 0.013mmol, 0.05eq), sodium tert-butoxide (50.5mg, 0.53mmol , 2.1eq) to replace nitrogen three times, then add DMSO (2.0mL) and deionized water (0.5mL).The reaction mixture was refluxed at 110°C for 24.0 hours, and TLC thin layer chromatography monitored 2-bromo-9-(2-quinone (Phenyl) carbazole. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system successively, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), and combine the organic phases , dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=3:1), and 76.4 mg of a yellow solid was obtained, with a yield of 98 %. The product was confirmed to be consistent with the data in Example 29 by1 H NMR.

实施例32：2-羟基-9-(2-异喹啉基)咔唑的制备Example 32: Preparation of 2-hydroxy-9-(2-isoquinolyl)carbazole

向带有磁力转子的干燥反应管中，依次加入2-溴-9-(2-异喹啉基)咔唑(186.6mg,0.50mmol,1.0eq)，氯化亚铜(2.5mg,0.025mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.025mmol,0.05eq)，一水合氢氧化锂(44.1mg,1.05mmol,2.1eq)。然后抽换氮气三次，再依次加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24.0小时。冷却，依次分别 向反应体系加入25.0mL乙酸乙酯和25.0mL去离子H2O充分清洗，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝4:1-3:1)，得白色固体114.5mg，收率74％。1H NMR(500MHz,DMSO-d6):δ6.37(d,J＝2.0Hz,1H),6.78(dd,J＝8.5,2.0Hz,1H),6.96-6.98(m,1H),7.21-7.26(m,2H),7.48(d,J＝7.5Hz,1H),7.62-7.66(m,1H),7.88-7.92(m,1H),8.06(d,J＝8.0Hz,1H),8.12-8.13(m,2H),8.23(d,J＝8.0Hz,1H),8.66(d,J＝5.5Hz,1H),9.49(s,1H).13C NMR(100MHz,DMSO-d6):δ96.44,110.06,110.38,115.47,119.37,120.41,121.45,121.78,123.60,124.36,124.42,124.77,127.62,128.66,131.43,138.26,140.74,142.14,142.42,149.25,156.94.HRMS(ESI):calcd for C21H15N2O[M+H]+311.1179,found 311.1186.To a dry reaction tube with a magnetic rotor, add 2-bromo-9-(2-isoquinolyl)carbazole (186.6mg, 0.50mmol, 1.0eq), cuprous chloride (2.5mg, 0.025mmol ,0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.025mmol, 0.05eq), lithium hydroxide monohydrate (44.1mg, 1.05 mmol, 2.1 eq). Then the nitrogen gas was exchanged three times, and then DMSO (2.0 mL) and deionized water (0.5 mL) were added sequentially. The reaction mixture was refluxed at 100°C for 24.0 hours. After cooling, add 25.0 mL of ethyl acetate and 25.0 mL of deionized H2 O to the reaction system in turn to fully wash, transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25 mL×3), combine the organic phases, and remove Dry over sodium sulfate, filter, and distill off the solvent under reduced pressure. The obtained crude product is separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=4:1-3:1), and 114.5 mg of white solid is obtained. rate of 74%.1 H NMR (500MHz, DMSO-d6 ): δ6.37 (d, J = 2.0Hz, 1H), 6.78 (dd, J = 8.5, 2.0Hz, 1H), 6.96-6.98 (m, 1H), 7.21 -7.26(m,2H),7.48(d,J=7.5Hz,1H),7.62-7.66(m,1H),7.88-7.92(m,1H),8.06(d,J=8.0Hz,1H), 8.12-8.13 (m, 2H), 8.23 (d, J = 8.0Hz, 1H), 8.66 (d, J = 5.5Hz, 1H), 9.49 (s, 1H).13 C NMR (100MHz, DMSO-d6 ):δ96.44,110.06,110.38,115.47,119.37,120.41,121.45,121.78,123.60,124.36,124.42,124.77,127.62,128.66,131.43,138.26,140.74,142.14,142.42,149.25,156.94.HRMS(ESI):calcd for C21 H15 N2 O[M+H]+ 311.1179, found 311.1186.

实施例33：2-羟基-9-(2-异喹啉基)咔唑的制备Example 33: Preparation of 2-hydroxy-9-(2-isoquinolyl)carbazole

向带有磁力转子的干燥反应管中，依次加入2-溴-9-(2-异喹啉基)咔唑(93.3mg,0.25mmol,1.0eq)，氯化亚铜(1.3mg,0.01mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(4.1mg,0.01mmol,0.05eq)，氢氧化钠(21.0mg,0.53mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于110℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-异喹啉基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得白色固体56.3mg，收率73％。产物经1H NMR确认与实施例32中数据一致。To a dry reaction tube with a magnetic rotor, add 2-bromo-9-(2-isoquinolyl)carbazole (93.3mg, 0.25mmol, 1.0eq), cuprous chloride (1.3mg, 0.01mmol ,0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (4.1mg, 0.01mmol, 0.05eq), sodium hydroxide (21.0mg, 0.53mmol, 2.1 eq) Nitrogen was purged three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 110°C for 24 hours, and 2-bromo-9-(2-isoquinolyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=3:1), to obtain 56.3 mg of a white solid, with a yield of 73%. The product was confirmed to be consistent with the data in Example 32 by1 H NMR.

实施例34：2-羟基-9-(2-异喹啉基)咔唑的制备Example 34: Preparation of 2-hydroxy-9-(2-isoquinolyl)carbazole

向带有磁力转子的干燥反应管中，依次加入2-溴-9-(2-异喹啉基)咔唑(186.6mg,0.50mmol,1.0eq)，氯化亚铜(2.5mg,0.03mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.03mmol,0.05eq)，叔丁醇钠(100.9mg,1.05mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于110℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-异喹啉基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得棕色固体147.9mg，收率95％。产物经1H NMR确认与实施例32中数据一致。To a dry reaction tube with a magnetic rotor, add 2-bromo-9-(2-isoquinolyl)carbazole (186.6mg, 0.50mmol, 1.0eq), cuprous chloride (2.5mg, 0.03mmol ,0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.03mmol, 0.05eq), sodium tert-butoxide (100.9mg, 1.05mmol , 2.1 eq) was purged of nitrogen three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 110°C for 24 hours, and 2-bromo-9-(2-isoquinolyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=3:1), to obtain 147.9 mg of a brown solid, with a yield of 95%. The product was confirmed to be consistent with the data in Example 32 by1 H NMR.

实施例35：2-羟基-9-(2-嘧啶基)咔唑的制备Example 35: Preparation of 2-hydroxy-9-(2-pyrimidinyl)carbazole

向带有磁力转子的干燥反应管中，依次加入2-溴-9-(2-嘧啶基)咔唑(54.3mg,0.17mmol,1.0eq)，氯化亚铜(0.8mg,0.008mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(2.8mg,0.008mmol,0.05eq)，一水合氢氧化锂(15.0mg,0.36mmol,2.1eq)。然后抽换氮气三次，再依次加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24.0小时。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子H2O充分清洗，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1-1:1)，得黄色固体33.2mg，收率75％。1H NMR(500MHz,DMSO-d6):δ6.85(dd,J＝8.0,2.0Hz,1H),7.32(td,J＝7.5,1.0Hz,1H),7.37-7.40(m,1H),7.41(t,J＝4.5,1H),7.98(d,J＝8.5Hz,1H),8.05(dd,J＝7.5,0.5Hz,1H),8.25(d,J＝2.0Hz,1H),8.72(d,J＝8.0Hz,1H),8.99(d,J＝4.5Hz,2H),9.69(s,1H).13C NMR(100MHz,DMSO-d6):δ102.52,111.33,115.87,116.93,117.22,118.68,120.48,122.29,124.87,125.50,138.26,139.91,157.14,158.27,158.60(2C).HRMS(ESI):calcd for C16H12N3O[M+H]+262.0975,found 262.0977.To a dry reaction tube with a magnetic rotor, add 2-bromo-9-(2-pyrimidinyl)carbazole (54.3mg, 0.17mmol, 1.0eq), cuprous chloride (0.8mg, 0.008mmol, 0.05 eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (2.8mg, 0.008mmol, 0.05eq), lithium hydroxide monohydrate (15.0mg, 0.36mmol, 2.1eq). Then the nitrogen gas was exchanged three times, and then DMSO (2.0 mL) and deionized water (0.5 mL) were added sequentially. The reaction mixture was refluxed at 100°C for 24.0 hours. After cooling, add 25.0 mL of ethyl acetate and 25.0 mL of deionized H2 O to the reaction system in turn to fully wash, transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25 mL×3), combine the organic phases, and remove Dry over sodium sulfate, filter, distill off the solvent under reduced pressure, separate and purify the obtained crude product by silica gel column chromatography, and eluent (petroleum ether/ethyl acetate=3:1-1:1) to obtain 33.2 mg of a yellow solid, obtained rate of 75%.1 H NMR (500MHz, DMSO-d6 ): δ6.85 (dd, J＝8.0, 2.0Hz, 1H), 7.32 (td, J＝7.5, 1.0Hz, 1H), 7.37-7.40 (m, 1H) ,7.41(t,J=4.5,1H),7.98(d,J=8.5Hz,1H),8.05(dd,J=7.5,0.5Hz,1H),8.25(d,J=2.0Hz,1H), 8.72(d, J=8.0Hz, 1H), 8.99(d, J=4.5Hz, 2H), 9.69(s, 1H).13 C NMR(100MHz, DMSO-d6 ): δ102.52, 111.33, 115.87, 116.93 ,117.22,118.68,120.48,122.29,124.87,125.50,138.26,139.91,157.14,158.27,158.60(2C).HRMS(ESI):calcd for C16 H12 N3 O[M+H]+ 262.0972.09 7 .

实施例36：2-羟基-9-(2-嘧啶基)咔唑的制备Example 36: Preparation of 2-hydroxy-9-(2-pyrimidinyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-嘧啶基)咔唑(81.0mg,0.25mmol,1.0eq)，氯化亚铜(1.3mg,0.013mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(4.1mg,0.013mmol,0.05eq)，氢氧化钠(21.0mg,0.53mmol,2.1eq)，抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于110℃下回流24.0小时，TLC薄层色谱监测2-溴-9-(2-嘧啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝4:1-0:1)，得黄色固体17.1mg，收率26％。产物经1H NMR确认与实施例35中数据一致。2-Bromo-9-(2-pyrimidinyl)carbazole (81.0mg, 0.25mmol, 1.0eq), cuprous chloride (1.3mg, 0.013mmol, 0.05eq ), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (4.1mg, 0.013mmol, 0.05eq), sodium hydroxide (21.0mg, 0.53mmol, 2.1eq) , purged nitrogen three times, then added DMSO (2.0 mL) and deionized water (0.5 mL). The reaction mixture was refluxed at 110°C for 24.0 hours, and 2-bromo-9-(2-pyrimidinyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=4:1-0:1), to obtain 17.1 mg of a yellow solid, with a yield of 26%. The product was confirmed to be consistent with the data in Example 35 by1 H NMR.

实施例37：2-羟基-9-(2-吡嗪基)咔唑的制备Example 37: Preparation of 2-hydroxy-9-(2-pyrazinyl)carbazole

向带有磁力转子的干燥反应管中，依次加入2-溴-9-(2-吡嗪基)咔唑(54.3mg,0.17mmol,1.0eq)，氯化亚铜(0.8mg,0.008mmol,0.05eq)，配体N1,N2-双(4- 羟基-2,6-二甲苯基)草酰胺(2.8mg,0.008mmol,0.05eq)，一水合氢氧化锂(15.0mg,0.36mmol,2.1eq然后)。抽换氮气三次，再依次加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子H2O充分清洗，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝1:1)，得黄色固体39.2mg，收率88％。1H NMR(500MHz,DMSO-d6):δ6.83(dd,J＝8.5,2.0Hz,1H),7.23(d,J＝2.0Hz,1H),7.29(td,J＝7.5,1.0Hz,1H),7.33-7.37(m,1H),7.77(d,J＝8.0Hz,1H),8.02(d,J＝8.5Hz,1H),8.07-8.09(m,1H),8.71(d,J＝3.0Hz,1H),8.81(dd,J＝2.5,1.5Hz,1H),9.12(d,J＝1.0Hz,1H),9.70(s,1H).13C NMR(100MHz,DMSO-d6):δ97.16,110.89,110.96,116.22,119.32,121.32,121.54,124.45,124.83,138.46,140.24,140.70,141.94,143.80,147.79,157.26.HRMS(ESI):calcd for C16H12N3O[M+H]+262.0975,found262.0981.To a dry reaction tube with a magnetic rotor, add 2-bromo-9-(2-pyrazinyl)carbazole (54.3mg, 0.17mmol, 1.0eq), cuprous chloride (0.8mg, 0.008mmol, 0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (2.8mg, 0.008mmol, 0.05eq), lithium hydroxide monohydrate (15.0mg, 0.36mmol , 2.1eq then). The nitrogen gas was exchanged three times, and then DMSO (2.0 mL) and deionized water (0.5 mL) were added sequentially. The reaction mixture was refluxed at 100°C for 24 hours. After cooling, add 25.0 mL of ethyl acetate and 25.0 mL of deionized H2 O to the reaction system in turn to fully wash, transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25 mL×3), combine the organic phases, and remove Dry over sodium sulfate, filter, and distill off the solvent under reduced pressure. The resulting crude product is separated and purified by silica gel column chromatography with eluent (petroleum ether/ethyl acetate=1:1) to obtain 39.2 mg of a yellow solid with a yield of 88%.1 H NMR (500MHz, DMSO-d6 ): δ6.83(dd, J=8.5, 2.0Hz, 1H), 7.23(d, J=2.0Hz, 1H), 7.29(td, J=7.5, 1.0Hz ,1H),7.33-7.37(m,1H),7.77(d,J=8.0Hz,1H),8.02(d,J=8.5Hz,1H),8.07-8.09(m,1H),8.71(d, J＝3.0Hz, 1H), 8.81(dd, J＝2.5, 1.5Hz, 1H), 9.12(d, J＝1.0Hz, 1H), 9.70(s, 1H).13 C NMR (100MHz, DMSO-d6 ): δ97.16, 110.89, 110.96,116.22 , 119.32, 121.32, 121.54, 124.45, 124.83, 138.46, 140.24, 140.70, 141.94,143.80 ,147.79 , 157.26. M+H]+ 262.0975, found 262.0981.

实施例38：2-羟基-9-(2-吡嗪基)咔唑的制备Example 38: Preparation of 2-hydroxy-9-(2-pyrazinyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡嗪基)咔唑(81.0mg,0.25mmol,1.0eq)，氯化亚铜(1.3mg,0.013mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(4.1mg,0.013mmol,0.05eq)，氢氧化钠(21.0mg,0.53mmol,2.1eq)，抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于110℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-吡嗪基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1-1:1)，得黄色固体37.7mg，收率57％。产物经1H NMR确认与实施例37中数据一致。Add 2-bromo-9-(2-pyrazinyl)carbazole (81.0mg, 0.25mmol, 1.0eq), cuprous chloride (1.3mg, 0.013mmol, 0.05 eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (4.1mg, 0.013mmol, 0.05eq), sodium hydroxide (21.0mg, 0.53mmol, 2.1eq ), purged nitrogen three times, then added DMSO (2.0 mL) and deionized water (0.5 mL). The reaction mixture was refluxed at 110°C for 24 hours, and 2-bromo-9-(2-pyrazinyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=3:1-1:1), and 37.7 mg of a yellow solid was obtained, with a yield of 57%. The product was confirmed to be consistent with the data in Example 37 by1 H NMR.

实施例39：2-羟基-9-(2-吡嗪基)咔唑的制备Example 39: Preparation of 2-hydroxy-9-(2-pyrazinyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-吡嗪基)咔唑(81.0mg,0.25mmol,1.0eq)，氯化亚铜(1.3mg,0.013mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(4.1mg,0.013mmol,0.05eq)，叔丁醇钠(50.5mg,0.53mmol,2.1eq)，抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于110℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-吡嗪基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝4:1-3:1)，得黄色固体59.6mg，收率91％。产物经1H NMR确认与实施例37中数据一致。Add 2-bromo-9-(2-pyrazinyl)carbazole (81.0mg, 0.25mmol, 1.0eq), cuprous chloride (1.3mg, 0.013mmol, 0.05 eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (4.1mg, 0.013mmol, 0.05eq), sodium tert-butoxide (50.5mg, 0.53mmol, 2.1 eq), evacuated nitrogen three times, then added DMSO (2.0 mL) and deionized water (0.5 mL). The reaction mixture was refluxed at 110°C for 24 hours, and 2-bromo-9-(2-pyrazinyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=4:1-3:1), to obtain 59.6 mg of a yellow solid, with a yield of 91%. The product was confirmed to be consistent with the data in Example 37 by1 H NMR.

实施例40：2-羟基-9-(2-噻唑基)咔唑的制备Example 40: Preparation of 2-hydroxy-9-(2-thiazolyl)carbazole

向带有磁力转子的干燥反应管中依次加入2-溴-9-(2-噻唑基)咔唑(164.6mg,0.50mmol,1.0eq)，氯化亚铜(2.5mg,0.025mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.025mmol,0.05eq)，一水合氢氧化锂(44.1mg,1.05mmol,2.1eq)。然后抽换氮气三次，再依次加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得红色固体113.9mg，收率86％。1H NMR(500MHz,DMSO-d6):δ6.86(dd,J＝8.5,2.0Hz,1H),7.35(td,J＝7.5,1.0Hz,1H),7.42-7.45(m,1H),7.66(d,J＝2.0Hz,1H),7.76(d,J＝3.5Hz,1H),7.88(d,J＝3.5Hz,1H),8.03(d,J＝8.5Hz,1H),8.08-8.10(m,1H),8.15(d,J＝8.0Hz,1H),9.87(s,1H).13C NMR(100MHz,DMSO-d6):δ99.61,111.44,111.94,116.22,116.27,119.34,121.36,122.32,124.64,125.26,138.39,139.72,140.12,157.65,158.28.HRMS(ESI):calcd for C15H11N2OS[M+H]+267.0587,found 267.0575.2-Bromo-9-(2-thiazolyl)carbazole (164.6mg, 0.50mmol, 1.0eq), cuprous chloride (2.5mg, 0.025mmol, 0.05eq ), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.025mmol, 0.05eq), lithium hydroxide monohydrate (44.1mg, 1.05mmol, 2.1 eq). Then the nitrogen gas was exchanged three times, and then DMSO (2.0 mL) and deionized water (0.5 mL) were added sequentially. The reaction mixture was refluxed at 100°C for 24 hours. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=3:1), to obtain 113.9 mg of a red solid, with a yield of 86%.1 H NMR (500MHz, DMSO-d6 ): δ6.86 (dd, J＝8.5, 2.0Hz, 1H), 7.35 (td, J＝7.5, 1.0Hz, 1H), 7.42-7.45 (m, 1H) ,7.66(d,J=2.0Hz,1H),7.76(d,J=3.5Hz,1H),7.88(d,J=3.5Hz,1H),8.03(d,J=8.5Hz,1H),8.08 -8.10(m,1H),8.15(d,J＝8.0Hz,1H),9.87(s,1H).13 C NMR(100MHz,DMSO-d6 ):δ99.61,111.44,111.94,116.22,116.27,119.34 ,121.36,122.32,124.64,125.26,138.39,139.72,140.12,157.65,158.28.HRMS(ESI):calcd for C15 H11 N2 OS[M+H]+ 267.0587,found 267.0575.

实施例41：2-羟基-9-(2-噻唑基)咔唑的制备Example 41: Preparation of 2-hydroxy-9-(2-thiazolyl)carbazole

向带有磁力转子的干燥反应管中，依次加入2-溴-9-(2-噻唑基)咔唑(82.3mg,0.25mmol,1.0eq)，氯化亚铜(1.3mg,0.01mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(4.1mg,0.01mmol,0.05eq)，氢氧化钠(21.0mg,0.53mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于110℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-噻唑基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得白色固体64.7mg，收率97％。产物经1H NMR确认与实施例40中数据一致。To a dry reaction tube with a magnetic rotor, add 2-bromo-9-(2-thiazolyl)carbazole (82.3mg, 0.25mmol, 1.0eq), cuprous chloride (1.3mg, 0.01mmol, 0.05 eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (4.1mg, 0.01mmol, 0.05eq), sodium hydroxide (21.0mg, 0.53mmol, 2.1eq ) was purged of nitrogen three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 110°C for 24 hours, and 2-bromo-9-(2-thiazolyl)carbazole was monitored by TLC. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=3:1), to obtain 64.7 mg of a white solid, with a yield of 97%. The product was confirmed to be consistent with the data in Example 40 by1 H NMR.

实施例42：2-羟基-9-(2-噻唑基)咔唑的制备Example 42: Preparation of 2-hydroxy-9-(2-thiazolyl)carbazole

向带有磁力转子的干燥反应管中，依次加入2-溴-9-(2-噻唑基)咔唑(164.6mg,0.50mmol,1.0eq)，氯化亚铜(2.5mg,0.025mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(8.2mg,0.025mmol,0.05eq)，叔丁醇钠(100.9mg,1.05mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于110℃下回流24小时，TLC薄层色谱监测2-溴-9-(2-噻唑基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得白色固体122.8mg，收率92％。产物经1H NMR确认与实施例40中数据一致。To a dry reaction tube with a magnetic rotor, add 2-bromo-9-(2-thiazolyl)carbazole (164.6mg, 0.50mmol, 1.0eq), cuprous chloride (2.5mg, 0.025mmol, 0.05 eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (8.2mg, 0.025mmol, 0.05eq), sodium tert-butoxide (100.9mg, 1.05mmol, 2.1 eq) Nitrogen was purged three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 110°C for 24 hours, and 2-bromo-9-(2-thiazolyl)carbazole was monitored by TLC. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=3:1), to obtain 122.8 mg of a white solid, with a yield of 92%. The product was confirmed to be consistent with the data in Example 40 by1 H NMR.

实施例43：3-羟基-9-(2-吡啶基)咔唑的制备Example 43: Preparation of 3-hydroxy-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中依次加入3-溴-9-(2-吡啶基)咔唑(61.9mg,0.19mmol,1.0eq)，氯化亚铜(1.0mg,0.010mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(3.1mg,0.010mmol,0.05eq)，一水合氢氧化锂(16.7mg,0.40mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于100℃下回流24小时，TLC薄层色谱监测3-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子H2O充分清洗，并将其转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得白色固体37.1mg，收率75％。1H NMR(500MHz,DMSO-d6):δ6.95(dd,J＝9.0,2.5Hz,1H),7.25-7.29(m,1H),7.40-7.44(m,2H),7.53(d,J＝2.5Hz,1H),7.68(d,J＝9.0Hz,1H),7.74(d,J＝8.0Hz,1H),7.82(d,J＝8.5Hz,1H),8.06-8.09(m,1H),8.12(d,J＝8.0Hz,1H),8.70(ddd,J＝5.0,2.0,0.5Hz,1H),9.26(s,1H).13CNMR(100MHz,DMSO-d6):δ105.11,111.29,112.06,115.32,118.42,120.31,120.43,121.28,123.44,124.44,126.16,132.71,139.21,149.32,151.13,152.21.3-Bromo-9-(2-pyridyl)carbazole (61.9mg, 0.19mmol, 1.0eq), cuprous chloride (1.0mg, 0.010mmol, 0.05eq ), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (3.1mg, 0.010mmol, 0.05eq), lithium hydroxide monohydrate (16.7mg, 0.40mmol, 2.1 eq) Nitrogen was purged three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 100°C for 24 hours, and 3-bromo-9-(2-pyridyl)carbazole was monitored by TLC. After cooling, add 25.0 mL of ethyl acetate and 25.0 mL of deionized H2 O to the reaction system in turn to fully wash, transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25 mL×3), combine the organic phases, and remove Dry over sodium sulfate, filter, and distill off the solvent under reduced pressure. The resulting crude product is separated and purified by silica gel column chromatography with eluent (petroleum ether/ethyl acetate=3:1) to obtain 37.1 mg of white solid with a yield of 75%.1 H NMR (500MHz, DMSO-d6 ): δ6.95(dd, J=9.0, 2.5Hz, 1H), 7.25-7.29(m, 1H), 7.40-7.44(m, 2H), 7.53(d, J＝2.5Hz, 1H), 7.68(d, J＝9.0Hz, 1H), 7.74(d, J＝8.0Hz, 1H), 7.82(d, J＝8.5Hz, 1H), 8.06-8.09(m, 1H), 8.12(d, J＝8.0Hz, 1H), 8.70(ddd, J＝5.0, 2.0, 0.5Hz, 1H), 9.26(s, 1H).13 CNMR(100MHz, DMSO-d6 ):δ105 .11, 111.29, 112.06, 115.32, 118.42, 120.31, 120.43, 121.28, 123.44, 124.44, 126.16, 132.71, 139.21, 149.32, 151.13, 152.21.

实施例44：3-羟基-9-(2-吡啶基)咔唑的制备Example 44: Preparation of 3-hydroxy-9-(2-pyridyl)carbazole

向带有磁力转子的干燥反应管中冷却，依次加入3-溴-9-(2-吡啶基)咔唑(80.8mg,0.25mmol,1.0eq)，氯化亚铜(1.3mg,0.01mmol,0.05eq)，配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺(4.1mg,0.01mmol,0.05eq)，氢氧化钠(50.5mg,0.53mmol,2.1eq)抽换氮气三次，然后加入DMSO(2.0mL)和去离子水(0.5mL)。反应混合物于110℃下回流24小时，TLC薄层色谱监测3-溴-9-(2-吡啶基)咔唑。冷却，依次分别向反应体系加入25.0mL乙酸乙酯和25.0mL去离子水，并将其 转移至分液漏斗分液，乙酸乙酯萃取(25mL×3)，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，淋洗剂(石油醚/乙酸乙酯＝3:1)，得白色固体59.0mg，收率91％。产物经1H NMR确认与实施例43中数据一致。Cool in a dry reaction tube with a magnetic rotor, add 3-bromo-9-(2-pyridyl)carbazole (80.8mg, 0.25mmol, 1.0eq), cuprous chloride (1.3mg, 0.01mmol, 0.05eq), ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl)oxalamide (4.1mg, 0.01mmol, 0.05eq), sodium hydroxide (50.5mg, 0.53mmol, 2.1 eq) Nitrogen was purged three times, then DMSO (2.0 mL) and deionized water (0.5 mL) were added. The reaction mixture was refluxed at 110°C for 24 hours, and 3-bromo-9-(2-pyridyl)carbazole was monitored by TLC thin layer chromatography. Cool, add 25.0mL ethyl acetate and 25.0mL deionized water to the reaction system in turn, and transfer it to a separatory funnel for liquid separation, extract with ethyl acetate (25mL×3), combine the organic phases, and dry over anhydrous sodium sulfate , filtered, and the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate=3:1), to obtain 59.0 mg of a white solid, with a yield of 91%. The product was confirmed to be consistent with the data in Example 43 by1 H NMR.

Claims (9)

Translated fromChinese
1.一种N-杂芳基-2-羟基咔唑类化合物的制备方法，其特征在于：所述的方法按如下步骤进行：在氮气保护下,以N-杂芳基-2-溴咔唑类化合物为原料，Cu盐为催化剂，N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺为配体，在碱性物质作用下，在溶剂中，于80-110℃下反应1-72小时，所述的N-杂芳基-2-溴咔唑类化合物如式(1)、式(2)、式(3)或式(4)所示所得反应液经后处理分别得到如式(Ⅰ)、(Ⅱ)、(Ⅲ)或(Ⅳ)所示的N-杂芳基-2-羟基咔唑类化合物；所述的N-杂芳基-2-溴咔唑类化合物与N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺、碱性物质的物质的量之比为：1:0.01～0.1：1.0～5.0；所述配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺与Cu(I)或Cu(II)盐催化剂物质的量之比为1～5:1；1. A preparation method for N-heteroaryl-2-hydroxyl carbazole compounds, characterized in that: the method is carried out as follows: under nitrogen protection, with N-heteroaryl-2-bromocarbazole Azole compound is used as raw material, Cu salt is used as catalyst, N1 , N2 -bis(4-hydroxy-2,6-xylyl) oxalamide is used as ligand, under the action of alkaline substances, in a solvent, at 80 Reaction at -110°C for 1-72 hours, the reaction of the N-heteroaryl-2-bromocarbazole compound as shown in formula (1), formula (2), formula (3) or formula (4) After post-treatment, the N-heteroaryl-2-hydroxyl carbazole compounds as shown in formula (I), (II), (III) or (IV) are obtained respectively; the N-heteroaryl-2 The ratio of the amount of bromocarbazole compounds to N1 , N2 -bis(4-hydroxy-2,6-xylyl) oxalamide and basic substances is: 1:0.01～0.1:1.0～5.0 ; The ratio of the ligand N1 , N2 -bis(4-hydroxy-2,6-xylyl) oxalamide to the Cu(I) or Cu(II) salt catalyst substance is 1-5:1 ;所述式(1)中R1、R2、R3分别与式(I)中的R1、R2、R3相同，所述式(2)中R4、R5、R6分别与式(Ⅱ)中R4、R5、R6相同，所述式(3)中分别与式(Ⅲ)中R7、R8、R9相同，所述式(4)中R10、R11、R12分别与式(Ⅳ)中R10、R11、R12相同，所述R1-R12各自独立为H或氘、C1－C12烷基或C1－C10烷氧基、C6－C20芳基、C10-C14杂芳基、C1－C12烷基胺基、芳基氨基，或杂芳环相邻的两个碳连接苯并环取代基。R1 , R2 , R3 in the formula (1) are respectively the same as R1 , R2 , R3 in the formula (I), and R4 , R5 , R6 in the formula (2) are respectively the same as R4 , R5 , and R6 in formula (II) are the same, R 7 , R 8 , and R 9 in formula (III) in formula (3) are the same as R7 , R8 , and R9 in formula (III), and R10 , R11 and R12 are respectively the same as R10 , R11 and R12 in formula (IV), and the R1 -R12 are each independently H or deuterium, C1 -C12 alkyl or C1 -C10 alkoxy radical, C6 -C20 aryl, C10 -C14 heteroaryl, C1 -C12 alkylamino, arylamino, or a benzo ring substituent connected to two adjacent carbons of the heteroaryl ring.2.按照权利要求1所述的一种N-杂芳基-2-羟基咔唑类化合物的制备方法，其特征在于：所述的式(1)、式(2)、式(3)或式(4)所示的N-杂芳基-2-溴咔唑类化合物为:2-溴-9-(2-吡啶基)咔唑、2-溴-9-[2-(3-甲基-吡啶基)]咔唑、2-溴-9-[2-(4-甲基-吡啶基)]咔唑、2-溴-9-(2-(5-甲基-吡啶基))咔唑、2-溴-9-(2-喹啉基)咔唑、2-溴-9-(2-异喹啉基)咔唑、2-溴-9-(2-嘧啶基)咔唑、2-溴-9-(2-吡嗪基)咔唑、2-溴-9-(2-噻唑基)咔唑或3-溴-9-(2-吡啶基)咔唑。2. according to the preparation method of a kind of N-heteroaryl-2-hydroxycarbazole compound according to claim 1, it is characterized in that: described formula (1), formula (2), formula (3) or The N-heteroaryl-2-bromocarbazole compound shown in formula (4) is: 2-bromo-9-(2-pyridyl) carbazole, 2-bromo-9-[2-(3-methyl Base-pyridyl)]carbazole, 2-bromo-9-[2-(4-methyl-pyridyl)]carbazole, 2-bromo-9-(2-(5-methyl-pyridyl)) Carbazole, 2-bromo-9-(2-quinolyl)carbazole, 2-bromo-9-(2-isoquinolyl)carbazole, 2-bromo-9-(2-pyrimidinyl)carbazole , 2-bromo-9-(2-pyrazinyl)carbazole, 2-bromo-9-(2-thiazolyl)carbazole or 3-bromo-9-(2-pyridyl)carbazole.3.按照权利要求1所述的一种N-杂芳基-2-羟基咔唑类化合物的制备方法，其特征在于：所述的催化剂Cu盐为氯化亚铜、溴化亚铜、碘化亚铜、醋酸铜或硫酸铜及其它们各自的水合物。3. according to the preparation method of a kind of N-heteroaryl-2-hydroxycarbazole compound according to claim 1, it is characterized in that: described catalyst Cu salt is cuprous chloride, cuprous bromide, iodine Cuprous chloride, copper acetate or copper sulfate and their respective hydrates.4.按照权利要求1所述的一种N-杂芳基-2-羟基咔唑类化合物的制备方法，其特征在于：所述的碱性物质为氢氧化锂、氢氧化钠、氢氧化钾、叔丁醇锂、叔丁醇钠、叔丁醇钾、甲醇钠、乙醇钠、碳酸铯、碳酸钾或磷酸钾。4. according to the preparation method of a kind of N-heteroaryl-2-hydroxycarbazole compound according to claim 1, it is characterized in that: described alkaline substance is lithium hydroxide, sodium hydroxide, potassium hydroxide , lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, sodium ethoxide, cesium carbonate, potassium carbonate, or potassium phosphate.5.按照权利要求1所述的一种N-杂芳基-2-羟基咔唑类化合物的制备方法，其特征在于：所述的溶剂为N,N-二甲基甲酰胺或二甲基亚砜/水的两种任意比的混合物。5. according to the preparation method of a kind of N-heteroaryl-2-hydroxyl carbazole compound according to claim 1, it is characterized in that: described solvent is N,N-dimethylformamide or dimethyl A mixture of two arbitrary ratios of sulfoxide/water.6.按照权利要求1所述的一种N-杂芳基-2-羟基咔唑类化合物的制备方法，其特征在于：所述溶剂的总加入量以N-杂芳基-2-溴咔唑类化合物的物质的量计为1～100mL/mmol。6. according to the preparation method of a kind of N-heteroaryl-2-hydroxyl carbazole compound according to claim 1, it is characterized in that: the total addition amount of described solvent is N-heteroaryl-2-bromocarbazole The quantity of the substance of an azole compound is 1-100 mL/mmol.7.按照权利要求1所述的一种N-杂芳基-2-羟基咔唑类化合物的制备方法，其特征在于：所述的N-杂芳基-2-溴咔唑类化合物与N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺、碱性物质的物质的量之比为：1:0.01～0.05：1.5～3.0。7. according to the preparation method of a kind of N-heteroaryl-2-hydroxycarbazole compound according to claim 1, it is characterized in that: described N-heteroaryl-2-bromocarbazole compound and N1 , The ratio of N2 -bis(4-hydroxy-2,6-xylyl)oxalamide to the basic substance is: 1:0.01-0.05:1.5-3.0.8.按照权利要求1所述的一种N-杂芳基-2-羟基咔唑类化合物的制备方法，其特征在于：所述的配体N1,N2-双(4-羟基-2,6-二甲苯基)草酰胺与Cu(I)或Cu(II)盐催化剂物质的量之比为1:1。8. The preparation method of a kind of N-heteroaryl-2-hydroxycarbazole compound according to claim 1, characterized in that: said ligand N1 , N2 -bis(4-hydroxyl-2 , 6-xylyl) oxalamide and Cu(I) or Cu(II) salt catalyst species ratio is 1:1.9.按照权利要求1所述的一种N-杂芳基-2-羟基咔唑类化合物的制备方法，其特征在于：反应的后处理方法为：反应结束后，待反应液冷却，用乙酸乙酯萃取，合并有机相，无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，将所得粗品通过硅胶柱色谱分离纯化，得到目标产物。9. According to the preparation method of a kind of N-heteroaryl-2-hydroxyl carbazole compound according to claim 1, it is characterized in that: the post-treatment method of reaction is: after the reaction finishes, the reaction liquid is cooled, and the acetic acid Extract with ethyl ester, combine the organic phases, dry over anhydrous sodium sulfate, filter, distill off the solvent under reduced pressure, and separate and purify the obtained crude product by silica gel column chromatography to obtain the target product.
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