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CN115652346A - Method for synthesizing 3-mercaptoindolizine compound by electrocatalytic oxidation - Google Patents

Method for synthesizing 3-mercaptoindolizine compound by electrocatalytic oxidation Download PDF

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CN115652346A
CN115652346A CN202211598009.8A CN202211598009A CN115652346A CN 115652346 A CN115652346 A CN 115652346A CN 202211598009 A CN202211598009 A CN 202211598009A CN 115652346 A CN115652346 A CN 115652346A
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李美超
刘雯璐
沈振陆
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Zhejiang University of Technology ZJUT
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Abstract

本发明涉及有机化合物合成技术领域,尤其是涉及一种电催化氧化合成3‑巯基吲哚嗪类化合物的方法,通过在含有支持电解质的有机溶剂中加入吲哚嗪类化合物、硫酚和碘化钾,然后对溶液通电,使得反应底物之间发生电催化氧化反应,合成3‑巯基吲哚嗪类化合物。本发明利用电化学反应,通过反应物在电极上得失电子实现产物的制备,不用加入额外的氧化剂,金属催化剂,减少了物质消耗,且反应的条件温和,工艺流程简单,操作简便安全,所得产物的收率高,为3‑巯基吲哚嗪类化合物的制备开拓了新的合成路线和方法,具有良好的应用潜力和研究价值。

Figure 202211598009

The present invention relates to the technical field of organic compound synthesis, in particular to a method for electrocatalyzed oxidation synthesis of 3-mercapto indolezine compounds, by adding indolezine compounds, thiophenol and potassium iodide to an organic solvent containing a supporting electrolyte, Then the solution is energized, so that an electrocatalytic oxidation reaction occurs between the reaction substrates to synthesize 3-mercapto indolazine compounds. The present invention utilizes the electrochemical reaction to realize the preparation of the product through gaining and losing electrons of the reactant on the electrode, without adding additional oxidants and metal catalysts, reducing material consumption, and the reaction conditions are mild, the process flow is simple, the operation is simple and safe, and the obtained product The yield is high, which opens up a new synthetic route and method for the preparation of 3-mercaptoindolezines, and has good application potential and research value.

Figure 202211598009

Description

一种电催化氧化合成3-巯基吲哚嗪类化合物的方法A kind of electrocatalytic oxidation synthesis method of 3-mercaptoindole azine compounds

技术领域technical field

本发明属于有机化合物合成技术领域,尤其是涉及一种电催化氧化合成3-巯基吲哚嗪类化合物的方法。The invention belongs to the technical field of organic compound synthesis, and in particular relates to a method for synthesizing 3-mercaptoindoleazine compounds by electrocatalytic oxidation.

背景技术Background technique

吲哚嗪类物质是许多天然产物中重要的杂环化合物,具有有效的药物活性和荧光特性。功能化的吲哚嗪类物质,特别是C-3位衍生物,能用于制备抗糖尿病、抗结核和抗炎活性药物。其中,3-巯基吲哚嗪类化合物已被认为是G蛋白偶联受体的配体,可用于治疗慢性呼吸道疾病,也可应用于生物活性分子的合成中间体以及荧光分子材料领域。Indoleazines are important heterocyclic compounds in many natural products with potent pharmaceutical activity and fluorescent properties. The functionalized indoleazine substances, especially the C-3 position derivatives, can be used to prepare anti-diabetic, anti-tuberculosis and anti-inflammatory drugs. Among them, 3-mercaptoindolezines have been considered as ligands of G protein-coupled receptors, which can be used to treat chronic respiratory diseases, and can also be used in the fields of synthetic intermediates of bioactive molecules and fluorescent molecular materials.

3-巯基吲哚嗪类化合物可以通过吲哚嗪类化合物和含硫亲核试剂的交叉偶联反应得到。主要的硫源可以有:三氟甲烷磺酰氯、苯亚磺酸钠、苯磺酰氯、二硫醚和硫醇。其中最常用且易得的是二硫醚和硫醇,但二硫醚一般以硫醇为原料合成。在含硫亲核试剂与吲哚嗪类化合物反应合成3-硫代吲哚类化合物的反应中,往往要用到过渡金属催化剂,或者化学计量的氧化剂,很多情况下还需要比较苛刻的反应条件,这些大大影响了其在实际生产的应用。3-Mercaptoindoleazines can be obtained by cross-coupling reactions between indoleazines and sulfur-containing nucleophiles. The main sulfur sources can be: trifluoromethanesulfonyl chloride, sodium benzenesulfinate, benzenesulfonyl chloride, disulfides and mercaptans. Among them, disulfide and mercaptan are the most commonly used and readily available, but disulfide is generally synthesized from mercaptan. In the reaction of sulfur-containing nucleophiles and indolazine compounds to synthesize 3-thioindole compounds, transition metal catalysts or stoichiometric oxidants are often used, and harsh reaction conditions are required in many cases , which have greatly affected its application in actual production.

文献(European Journal of Organic Chemistry 2019, 1588-1593)报道了在氯化钯和氯化铜的催化下,2-苯基吲哚嗪类化合物和二硫醚在120 oC下反应12小时制备双取代的硫代吲哚嗪化合物,但该方法只能制备双取代产物,并且二硫醚类化合物需以硫醇为原料制得。最近,有文献报道了以过氧化氢为氧化剂,在60 oC的条件下,以2-苯基吲哚嗪和芳基硫醇为原料合成硫代吲哚嗪的方法(Org Lett 2018, 20 (11), 3291-3295)。以上方法各有优点,但也存在限制,比如需要金属催化剂、额外的氧化剂、高温条件、反应收率不高等。因此,开发更加经济、环保、高效的方法合成具有多样性结构的3-巯基吲哚嗪骨架化合物具有重要的研究价值。The literature (European Journal of Organic Chemistry 2019, 1588-1593) reported that under the catalysis of palladium chloride and copper chloride, 2-phenylindole azine compounds and disulfides were reacted at 120 o C for 12 hours to prepare bis Substituted thioindolazine compounds, but this method can only prepare disubstituted products, and disulfide compounds need to be prepared from thiols. Recently, a method for the synthesis of thioindolezine from 2-phenylindolezine and aryl mercaptan was reported using hydrogen peroxide as oxidant at 60 o C (Org Lett 2018, 20 (11), 3291-3295). The above methods have their own advantages, but there are also limitations, such as the need for metal catalysts, additional oxidants, high temperature conditions, and low reaction yields. Therefore, it is of great research value to develop more economical, environmentally friendly and efficient methods to synthesize 3-mercaptoindolezine skeleton compounds with diverse structures.

发明内容Contents of the invention

本发明的目的是提供一种电催化氧化合成3-巯基吲哚嗪类化合物的方法,采用该方法制备3-巯基吲哚嗪类化合物,不用加入额外的金属催化剂、氧化剂,反应不需要高温条件,工艺流程简单,操作简便安全,收率高。The purpose of the present invention is to provide a method for electrocatalytic oxidation synthesis of 3-mercaptoindoleazine compounds. The method is used to prepare 3-mercaptoindoleazine compounds without adding additional metal catalysts and oxidants, and the reaction does not require high temperature conditions , the process flow is simple, the operation is convenient and safe, and the yield is high.

为实现上述发明目的,本发明通过以下技术方案实现:In order to achieve the above-mentioned purpose of the invention, the present invention is achieved through the following technical solutions:

一种电催化氧化合成3-巯基吲哚嗪类化合物的方法,包括以下步骤:A method for electrocatalytic oxidation synthesis of 3-mercaptoindole azine compounds, comprising the following steps:

(1)在含有支持电解质的有机溶剂中加入反应底物;(1) Add the reaction substrate in the organic solvent containing the supporting electrolyte;

所述反应底物包括吲哚嗪类化合物、硫酚和碘化钾;The reaction substrates include indole azines, thiophenols and potassium iodide;

(2)向步骤(1)中得到的溶液通电,使得反应底物之间发生电催化氧化反应,合成3-巯基吲哚嗪类化合物;(2) electrifying the solution obtained in step (1), so that an electrocatalytic oxidation reaction occurs between the reaction substrates to synthesize 3-mercaptoindolazine compounds;

所述吲哚嗪类化合物的结构式为

Figure DEST_PATH_IMAGE001
,所述硫酚的结构式为
Figure 208523DEST_PATH_IMAGE002
,The structural formula of the indolezines compound is
Figure DEST_PATH_IMAGE001
, the structural formula of the thiophenol is
Figure 208523DEST_PATH_IMAGE002
,

所述3-巯基吲哚嗪类化合物的结构式为

Figure DEST_PATH_IMAGE003
;The structural formula of the 3-mercapto indolazine compound is
Figure DEST_PATH_IMAGE003
;

其中,R1为H、卤素、C1~C4的烷基、C1~C4的烷氧基中的一种,R2为H、卤素、C1~C4的烷基、C1~C4的烷氧基中的一种,R3为苯基、取代的苯基、杂芳香基、取代的杂芳香基、萘基、取代的萘基中的一种。Wherein, R1 is one of H, halogen, C1~C4 alkyl, C1~C4 alkoxy, R2 is H, halogen, C1~C4 alkyl, C1~C4 alkoxy A kind of, R 3 is one of phenyl, substituted phenyl, heteroaryl, substituted heteroaryl, naphthyl, substituted naphthyl.

本发明采用电化学法合成3-巯基吲哚嗪类化合物,与最接近的现有关于硫代吲哚嗪类化合物的有机合成方法相比,不仅操作简便安全,具有在合成反应过程中不需要添加额外的金属催化剂、氧化剂,反应条件温和等优势,且产物的收率高,易分离提纯。The present invention adopts the electrochemical method to synthesize 3-mercaptoindolezines. Compared with the closest existing organic synthesis method about thioindoleazines, it is not only easy and safe to operate, but also has the advantages of not requiring The addition of additional metal catalysts and oxidants has the advantages of mild reaction conditions, high product yields, and easy separation and purification.

通过电化学催化合成3-巯基吲哚嗪类化合物的制备方案可描述为:采用三电极体系,阴极和阳极均为铂片电极,0.1 mol/L的硝酸银乙腈溶液作为参比电极。在含有支持电解质的有机溶剂中,加入吲哚嗪类化合物、硫酚和碘化钾,在一定温度、恒电压条件下搅拌电解,反应结束后,反应液经后处理得到产物3-巯基吲哚嗪类化合物。由于电化学反应是通过反应物在电极上得失电子实现的,不用加入额外的氧化剂,金属催化剂,减少了物质消耗,且反应的条件温和,这对节约能源、降低设备投资十分有利。The preparation scheme for the synthesis of 3-mercaptoindolezines by electrochemical catalysis can be described as follows: a three-electrode system is used, the cathode and anode are platinum electrodes, and 0.1 mol/L silver nitrate acetonitrile solution is used as a reference electrode. In an organic solvent containing a supporting electrolyte, add indoleazine compounds, thiophenol and potassium iodide, stir and electrolyze under certain temperature and constant voltage conditions, after the reaction is completed, the reaction solution is post-treated to obtain the product 3-mercaptoindoleazine compound. Since the electrochemical reaction is realized by the reactants gaining and losing electrons on the electrode, there is no need to add additional oxidants and metal catalysts, reducing material consumption, and the reaction conditions are mild, which is very beneficial to saving energy and reducing equipment investment.

上述的反应过程,可用下述的反应式表示:The above reaction process can be represented by the following reaction formula:

Figure 594505DEST_PATH_IMAGE004
Figure 594505DEST_PATH_IMAGE004

其中,R1为H、卤素、C1~C4的烷基、C1~C4的烷氧基中的一种,R2为H、卤素、C1~C4的烷基、C1~C4的烷氧基中的一种,R3为苯基、取代的苯基、杂芳香基、取代的杂芳香基、萘基、取代的萘基中的一种。R3中所述的杂芳香基可以是环内含N、O、S等杂原子的芳香基。所述的取代的苯基、取代的杂芳香基和取代的萘基是指苯环、杂芳香环和萘环上的氢被一个或多个取代基取代,所述的取代基各自独立选自下列之一:卤素、C1~C4的烷基、C1~C4的烷氧基、氨基和羟基。Wherein, R1 is one of H, halogen, C1~C4 alkyl, C1~C4 alkoxy, R2 is H, halogen, C1~C4 alkyl, C1~C4 alkoxy A kind of, R 3 is one of phenyl, substituted phenyl, heteroaryl, substituted heteroaryl, naphthyl, substituted naphthyl. The heteroaryl group described in R3 may be an aromatic group containing heteroatoms such as N, O, and S in the ring. The substituted phenyl, substituted heteroaryl and substituted naphthyl refer to the fact that the hydrogen on the benzene ring, heteroaromatic ring and naphthalene ring is substituted by one or more substituents, and each of the substituents is independently selected from One of the following: halogen, C1~C4 alkyl, C1~C4 alkoxy, amino and hydroxyl.

作为优选,所述R1为H、Cl、甲基中的一种,所述R2为H、甲基中的一种,所述R3为苯基、卤代苯基、烷基取代苯基、烷氧基取代苯基、噻吩基中的一种。Preferably, the R 1 is one of H, Cl, and methyl, the R 2 is one of H, methyl, and the R 3 is phenyl, halogenated phenyl, or alkyl-substituted benzene One of base, alkoxy substituted phenyl, thienyl.

作为优选,所述步骤(1)中的支持电解质为LiClO4 n Bu4NBF4 n Bu4ClO4、NaClO4中的一种,所述有机溶剂为N,N-二甲基甲酰胺或二甲基亚砜。Preferably, the supporting electrolyte in the step (1) is one of LiClO 4 , nBu 4 NBF 4 , nBu 4 ClO 4 , NaClO 4 , and the organic solvent is N,N-dimethylformamide or dimethyl sulfoxide.

作为优选,所述步骤(1)中的支持电解质为LiClO4,所述有机溶剂为N,N-二甲基甲酰胺。Preferably, the supporting electrolyte in the step (1) is LiClO 4 , and the organic solvent is N,N-dimethylformamide.

在通过电催化氧化合成3-巯基吲哚嗪类化合物的实验中,所添加的支持电解质为LiClO4 n Bu4NBF4 n Bu4ClO4、NaClO4中的一种,有机溶剂为N,N-二甲基甲酰胺或者二甲基亚砜。其中,在实验过程中发现,虽然选用这些支持电解质和有机溶剂均能实现3-巯基吲哚嗪类化合物的制备,但选用LiClO4作为支持电解质,选用N,N-二甲基甲酰胺作为有机溶剂的反应产率较高。In the experiment of synthesizing 3-mercaptoindolezines by electrocatalytic oxidation, the added supporting electrolyte was one of LiClO 4 , n Bu 4 NBF 4 , n Bu 4 ClO 4 , and NaClO 4 , and the organic solvent was N , N-dimethylformamide or dimethylsulfoxide. Among them, it was found during the experiment that although these supporting electrolytes and organic solvents can be used to realize the preparation of 3-mercaptoindolazine compounds, LiClO 4 is used as the supporting electrolyte and N,N-dimethylformamide is used as the organic solvent. The reaction yield of the solvent is higher.

作为优选,所述步骤(1)中的支持电解质在有机溶剂中的物质的量浓度为0.05~0.2 mol/L。Preferably, the concentration of the supporting electrolyte in the organic solvent in the step (1) is 0.05-0.2 mol/L.

作为优选,所述步骤(1)中吲哚嗪类化合物与硫酚、碘化钾的物质的量之比为100:100~200:10~40。Preferably, the ratio of the amount of indoleazine compounds to thiophenol and potassium iodide in the step (1) is 100:100~200:10~40.

作为优选,所述步骤(1)中吲哚嗪类化合物与硫酚、碘化钾的物质的量之比为100:120~180:10~20。Preferably, the ratio of the amount of indoleazine compounds to thiophenol and potassium iodide in the step (1) is 100:120~180:10~20.

作为优选,所述吲哚嗪类化合物在有机溶剂中的物质的量浓度为0.005~0.03mol/L。Preferably, the concentration of the indoleazine compounds in the organic solvent is 0.005-0.03 mol/L.

在合成实验中,吲哚嗪类化合物与硫酚、碘化钾的物质的量之比为100:100~200:10~40时均会有3-巯基吲哚嗪类化合物的收率,其中比例范围为100:120~180:10~20时产物的收率较高,且在实验过程中发现,采用吲哚嗪类化合物在有机溶剂中的物质的量浓度为0.005~0.03 mol/L时更有利于合成实验的顺利进行。In the synthesis experiment, when the ratio of the amount of indolezine compounds to thiophenol and potassium iodide is 100:100~200:10~40, there will be a yield of 3-mercaptoindolezine compounds, and the ratio range When the ratio is 100:120~180:10~20, the yield of the product is higher, and in the course of the experiment, it is found that when the concentration of the substance in the organic solvent is 0.005~0.03 mol/L, it is more effective It is beneficial to the smooth progress of the synthesis experiment.

作为优选,所述步骤(2)中的电解温度为15~45 ℃,电解电压为0.1~0.4 V,电解时间为3~8 h。Preferably, the electrolysis temperature in the step (2) is 15-45 °C, the electrolysis voltage is 0.1-0.4 V, and the electrolysis time is 3-8 h.

本发明还提供了一种由上述方法制备的3-巯基吲哚嗪类化合物的纯化方法,包括以下步骤:The present invention also provides a method for purifying 3-mercaptoindolezines prepared by the above method, comprising the following steps:

(1)取出电解反应结束后含有3-巯基吲哚嗪类化合物的溶液,减压蒸除溶剂,再进行柱层析分离,收集含目标化合物的洗脱液;(1) Take out the solution containing 3-mercaptoindoleazine compounds after the electrolysis reaction, evaporate the solvent under reduced pressure, and then perform column chromatography separation to collect the eluate containing the target compound;

(2)蒸除溶剂得到产物3-巯基吲哚嗪类化合物。(2) Evaporating the solvent to obtain the product 3-mercaptoindole azine compound.

反应结束后,取出反应液,对反应液进行减压蒸除溶剂,再进行柱层析分离,以乙酸乙酯/正己烷体积比1:60的混合液为洗脱剂,收集含目标化合物的洗脱液,蒸除溶剂即得产物3-巯基吲哚嗪类化合物。After the reaction, the reaction solution was taken out, the reaction solution was evaporated under reduced pressure to remove the solvent, and then separated by column chromatography, using a mixture of ethyl acetate/n-hexane with a volume ratio of 1:60 as the eluent to collect the mixture containing the target compound. The eluent was evaporated to remove the solvent to obtain the product 3-mercaptoindoleazine compounds.

本发明具有以下有益效果:The present invention has the following beneficial effects:

(1)本发明提供的电催化氧化合成3-巯基吲哚嗪类化合物的方法,所得产物的收率高,操作简便安全;(1) The method for synthesizing 3-mercaptoindolezines by electrocatalytic oxidation provided by the present invention has a high yield of the product and is easy and safe to operate;

(2)反应条件比较温和,不需要高温,也不需要额外的氧化剂和金属催化剂,减少了物质消耗,有利于产品的分离提纯;(2) The reaction conditions are relatively mild, no high temperature is required, and no additional oxidants and metal catalysts are required, which reduces material consumption and is conducive to the separation and purification of products;

(3)采用电化学法合成产物,由于使用了清洁的电能为氧化还原剂,电化学反应是通过反应物在电极上得失电子实现的,实验条件和过程更加绿色环保,不会产生过多的污染,大大降低了环境成本,可为3-巯基吲哚嗪类化合物的制备开拓新的合成路线和方法。(3) The product is synthesized by electrochemical method. Since the clean electric energy is used as the redox agent, the electrochemical reaction is realized by the reactant gaining and losing electrons on the electrode. The experimental conditions and process are more environmentally friendly and will not produce too much pollution, greatly reducing environmental costs, and can open up new synthetic routes and methods for the preparation of 3-mercaptoindolezines.

附图说明Description of drawings

图1为本发明实施例1所得化合物的核磁氢谱图。Fig. 1 is the H NMR spectrum of the compound obtained in Example 1 of the present invention.

图2为本发明实施例1所得化合物的核磁碳谱图。Figure 2 is the carbon NMR spectrum of the compound obtained in Example 1 of the present invention.

具体实施方式Detailed ways

下面结合说明书附图以及具体实施例对本发明做进一步描述。本领域普通技术人员在基于这些说明的情况下将能够实现本发明。此外,下述说明中涉及到的本发明的实施例通常仅是本发明一部分的实施例,而不是全部的实施例。因此,基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例,都应当属于本发明保护的范围。The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments. Those skilled in the art will be able to implement the present invention based on these descriptions. In addition, the embodiments of the present invention referred to in the following description are generally only some embodiments of the present invention, not all of them. Therefore, based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

下述实施例所制得的3-巯基吲哚嗪类化合物的结构式分别如式(I-1)~(I-17)所示:The structural formulas of the 3-mercaptoindolazines prepared in the following examples are shown in formulas (I-1) to (I-17):

Figure 108663DEST_PATH_IMAGE006
Figure 108663DEST_PATH_IMAGE006

Figure 97347DEST_PATH_IMAGE008
Figure 97347DEST_PATH_IMAGE008

Figure 646141DEST_PATH_IMAGE010
Figure 646141DEST_PATH_IMAGE010

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Figure 203024DEST_PATH_IMAGE012
.

实施例1:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 1: Preparation of 2-phenyl-3-p-chlorophenylthioindoxazine (Formula I-1)

反应采用三电极体系,阴极和阳极均为铂片电极,0.1 mol/L的硝酸银乙腈溶液作为参比电极。在30 mL的烧杯内加入含有0.1 mol/L LiClO4的N,N-二甲基甲酰胺(15 mL)、2-苯基吲哚嗪(0.2 mmol)、对氯苯硫酚(0.3 mmol)和碘化钾(0.03 mmol)。25 ℃,0.2 V恒电位电解,5h后反应结束。减压蒸除溶剂,再进行柱层析分离,以乙酸乙酯/正己烷体积比1:60的混合液为洗脱剂,收集含目标化合物的洗脱液,蒸除溶剂即得产物2-苯基-3-对氯苯硫基吲哚嗪,分离收率为85%。The reaction adopts a three-electrode system, the cathode and anode are platinum electrodes, and 0.1 mol/L silver nitrate acetonitrile solution is used as the reference electrode. In a 30 mL beaker, add N,N-dimethylformamide (15 mL), 2-phenylindolezine (0.2 mmol), p-chlorothiophenol (0.3 mmol) containing 0.1 mol/L LiClO and potassium iodide (0.03 mmol). 25 ℃, 0.2 V constant potential electrolysis, the reaction ended after 5 hours. The solvent was evaporated under reduced pressure, and then separated by column chromatography, using a mixture of ethyl acetate/n-hexane with a volume ratio of 1:60 as the eluent, the eluate containing the target compound was collected, and the solvent was evaporated to obtain the product 2- Phenyl-3-p-chlorophenylthioindoleazine, the isolated yield is 85%.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 8.01 (d, J=7.1 Hz, 1H), 7.55 (d, J=7.2 Hz,2H), 7.26-7.19 (m, 3H), 7.16-7.10 (m, 1H), 6.93 (d, J=8.4 Hz, 2H), 6.67 (d, J=6.7 Hz, 1H), 6.63 (d, J=6.9 Hz, 3H), 6.42-6.34 (m, 1H); 1 H NMR (400 MHz, CDCl 3 ) δ 8.01 (d, J =7.1 Hz, 1H), 7.55 (d, J =7.2 Hz,2H), 7.26-7.19 (m, 3H), 7.16-7.10 (m, 1H), 6.93 (d, J =8.4 Hz, 2H), 6.67 (d, J =6.7 Hz, 1H), 6.63 (d, J =6.9 Hz, 3H), 6.42-6.34 (m, 1H);

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 137.2, 136.1, 135.9, 135.0, 131.2, 129.4,128.9, 128.4, 127.3, 126.4, 123.8, 120.1, 118.9, 111.5, 104.0, 100.4。 13 C NMR (101 MHz, CDCl 3 ) δ 137.2, 136.1, 135.9, 135.0, 131.2, 129.4, 128.9, 128.4, 127.3, 126.4, 123.8, 120.1, 118.9, 111.5, 104.0,

实施例2:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 2: Preparation of 2-phenyl-3-p-chlorophenylthioindolezine (Formula I-1)

反应步骤同实施例1,所不同的是有机溶剂改成二甲基亚砜,2-苯基-3-对氯苯硫基吲哚嗪的分离收率为70%。The reaction steps are the same as in Example 1, except that the organic solvent is changed to dimethyl sulfoxide, and the isolated yield of 2-phenyl-3-p-chlorophenylthioindoleazine is 70%.

实施例3:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 3: Preparation of 2-phenyl-3-p-chlorophenylthioindoxazine (Formula I-1)

反应步骤同实施例1,所不同的是支持电解质改成nBu4NBF4,2-苯基-3-对氯苯硫基吲哚嗪的分离收率为57%。The reaction steps are the same as in Example 1, except that the supporting electrolyte is changed to n Bu 4 NBF 4 , and the isolated yield of 2-phenyl-3-p-chlorophenylthioindoleazine is 57%.

实施例4:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 4: Preparation of 2-phenyl-3-p-chlorophenylthioindoxazine (Formula I-1)

反应步骤同实施例1,所不同的是支持电解质改成nBu4ClO4,2-苯基-3-对氯苯硫基吲哚嗪的分离收率为72%。The reaction steps are the same as in Example 1, except that the supporting electrolyte is changed to n Bu 4 ClO 4 , and the isolated yield of 2-phenyl-3-p-chlorophenylthioindoleazine is 72%.

实施例5:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 5: Preparation of 2-phenyl-3-p-chlorophenylthioindoxazine (Formula I-1)

反应步骤同实施例1,所不同的是支持电解质改成NaClO4,2-苯基-3-对氯苯硫基吲哚嗪的分离收率为68%。The reaction steps are the same as in Example 1, except that the supporting electrolyte is changed to NaClO 4 , and the isolated yield of 2-phenyl-3-p-chlorophenylthioindoleazine is 68%.

实施例6:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 6: Preparation of 2-phenyl-3-p-chlorophenylthioindolezine (Formula I-1)

反应步骤同实施例1,所不同的是反应电压改为0.3 V,反应时间改为4h,2-苯基-3-对氯苯硫基吲哚嗪的分离收率为82%。The reaction steps were the same as in Example 1, except that the reaction voltage was changed to 0.3 V, the reaction time was changed to 4 h, and the separation yield of 2-phenyl-3-p-chlorophenylthioindoxazine was 82%.

实施例7:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 7: Preparation of 2-phenyl-3-p-chlorophenylthioindolezine (Formula I-1)

反应步骤同实施例1,所不同的是反应电压改为0.4 V,反应时间改为3h,2-苯基-3-对氯苯硫基吲哚嗪的分离收率为75%。The reaction steps were the same as in Example 1, except that the reaction voltage was changed to 0.4 V, the reaction time was changed to 3 h, and the separation yield of 2-phenyl-3-p-chlorophenylthioindoxazine was 75%.

施例8:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 8: Preparation of 2-phenyl-3-p-chlorophenylthioindolezine (Formula I-1)

反应步骤同实施例1,所不同的是反应电压改为0.1 V,反应时间改为8h,2-苯基-3-对氯苯硫基吲哚嗪的分离收率为42%。The reaction steps were the same as in Example 1, except that the reaction voltage was changed to 0.1 V, the reaction time was changed to 8 h, and the separation yield of 2-phenyl-3-p-chlorophenylthioindoxazine was 42%.

实施例9:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 9: Preparation of 2-phenyl-3-p-chlorophenylthioindoxazine (Formula I-1)

反应步骤同实施例1,所不同的是反应温度改为35 ℃, 2-苯基-3-对氯苯硫基吲哚嗪的分离收率为84%。The reaction steps were the same as in Example 1, except that the reaction temperature was changed to 35 °C, and the isolated yield of 2-phenyl-3-p-chlorophenylthioindoleazine was 84%.

实施例10:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 10: Preparation of 2-phenyl-3-p-chlorophenylthioindolezine (Formula I-1)

反应步骤同实施例1,所不同的是反应温度改为15 ℃,LiClO4的浓度改为0.2mol/L,2-苯基-3-对氯苯硫基吲哚嗪的分离收率为75%。The reaction steps are the same as in Example 1, except that the reaction temperature is changed to 15°C, the concentration of LiClO is changed to 0.2mol/L, and the isolated yield of 2-phenyl - 3-p-chlorophenylthioindolezine is 75%. %.

实施例11:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 11: Preparation of 2-phenyl-3-p-chlorophenylthioindolezine (Formula I-1)

反应步骤同实施例1,所不同的是反应温度改为45 ℃,LiClO4的浓度改为0.05mol/L,2-苯基-3-对氯苯硫基吲哚嗪的分离收率为80%。The reaction steps are the same as in Example 1, except that the temperature of reaction is changed to 45°C, the concentration of LiClO is changed to 0.05mol/L, and the separation yield of 2-phenyl - 3-p-chlorophenylthioindoxazine is 80% %.

实施例12:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 12: Preparation of 2-phenyl-3-p-chlorophenylthioindolezine (Formula I-1)

反应步骤同实施例1,所不同的是对氯苯硫酚加入量改为0.24mmol,碘化钾加入量改为0.02mmol,2-苯基-3-对氯苯硫基吲哚嗪的分离收率为79%。The reaction steps are the same as in Example 1, except that the p-chlorothiophenol add-on is changed to 0.24mmol, and the potassium iodide add-on is changed to 0.02mmol, and the separation yield of 2-phenyl-3-p-chlorophenylthioindoxazine 79%.

实施例13:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 13: Preparation of 2-phenyl-3-p-chlorophenylthioindolezine (Formula I-1)

反应步骤同实施例1,所不同的是对氯苯硫酚加入量改为0.36mmol,碘化钾加入量改为0.04mmol,2-苯基-3-对氯苯硫基吲哚嗪的分离收率为83%。The reaction steps are the same as in Example 1, except that the p-chlorothiophenol add-on is changed to 0.36mmol, and the potassium iodide add-on is changed to 0.04mmol, and the separation yield of 2-phenyl-3-p-chlorophenylthioindoxazine 83%.

实施例14:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 14: Preparation of 2-phenyl-3-p-chlorophenylthioindolezine (Formula I-1)

反应步骤同实施例1,所不同的是对氯苯硫酚加入量改为0.2mmol,碘化钾加入量改为0.08mmol,2-苯基-3-对氯苯硫基吲哚嗪的分离收率为61%。The reaction steps are the same as in Example 1, except that the p-chlorothiophenol add-on is changed to 0.2mmol, and the potassium iodide add-on is changed to 0.08mmol, and the separation yield of 2-phenyl-3-p-chlorophenylthioindoxazine 61%.

实施例15:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 15: Preparation of 2-phenyl-3-p-chlorophenylthioindolezine (Formula I-1)

反应步骤同实施例1,所不同的是对氯苯硫酚加入量改为0.4mmol,碘化钾加入量改为0.03mmol,2-苯基-3-对氯苯硫基吲哚嗪的分离收率为64%。The reaction steps are the same as in Example 1, except that the p-chlorothiophenol add-on is changed to 0.4mmol, and the potassium iodide add-on is changed to 0.03mmol, and the separation yield of 2-phenyl-3-p-chlorophenylthioindoxazine 64%.

实施例16:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 16: Preparation of 2-phenyl-3-p-chlorophenylthioindolezine (Formula I-1)

反应步骤同实施例1,所不同的是2-苯基吲哚嗪的加入量改为0.075mmol,对氯苯硫酚加入量改为0.105mmol,碘化钾加入量改为0.015mmol,2-苯基-3-对氯苯硫基吲哚嗪的分离收率为83%。The reaction steps are the same as in Example 1, except that the addition of 2-phenylindolezine is changed to 0.075mmol, the addition of p-chlorothiophenol is changed to 0.105mmol, and the addition of potassium iodide is changed to 0.015mmol. The isolated yield of -3-p-chlorophenylthioindoxazine was 83%.

实施例17:2-苯基-3-对氯苯硫基吲哚嗪(式I-1)的制备Example 17: Preparation of 2-phenyl-3-p-chlorophenylthioindolezine (Formula I-1)

反应步骤同实施例1,所不同的是2-苯基吲哚嗪的加入量改为0.45mmol,对氯苯硫酚加入量改为0.72mmol,碘化钾加入量改为0.045mmol,2-苯基-3-对氯苯硫基吲哚嗪的分离收率为72%。The reaction steps are the same as in Example 1, except that the addition of 2-phenylindolezine is changed to 0.45mmol, the addition of p-chlorothiophenol is changed to 0.72mmol, and the addition of potassium iodide is changed to 0.045mmol. The isolated yield of -3-p-chlorophenylthioindoxazine was 72%.

实施例18:2-苯基-3-对溴苯硫基吲哚嗪(式I-2)的制备Example 18: Preparation of 2-phenyl-3-p-bromophenylthioindolezine (Formula I-2)

反应步骤同实施例1,所不同的是对氯苯硫酚改为对溴苯硫酚,产物2-苯基-3-对溴苯硫基吲哚嗪的分离收率为80%。The reaction steps are the same as in Example 1, except that p-chlorothiophenol is changed to p-bromothiophenol, and the isolated yield of product 2-phenyl-3-p-bromophenylthioindoxazine is 80%.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 8.20-8.17 (m, 1H), 7.69-7.66 (m, 2H), 7.46(d, J=8.9 Hz, 1H), 7.41-7.36 (m, 2H), 7.33-7.26 (m, 3H), 6.90-6.84 (m, 1H),6.79 (s, 1H), 6.76-6.72 (m, 2H), 6.62-6.57 (m, 1H); 1 H NMR (400 MHz, CDCl 3 ) δ 8.20-8.17 (m, 1H), 7.69-7.66 (m, 2H), 7.46(d, J =8.9 Hz, 1H), 7.41-7.36 (m, 2H), 7.33-7.26 (m, 3H), 6.90-6.84 (m, 1H), 6.79 (s, 1H), 6.76-6.72 (m, 2H), 6.62-6.57 (m, 1H);

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 137.3, 136.7, 136.2, 135.1, 132.3, 129.0,128.5, 127.4, 126.8, 123.9, 120.2, 119.1, 119.0, 111.6, 103.9, 100.5。 13 C NMR (101 MHz, CDCl 3 ) δ 137.3, 136.7, 136.2, 135.1, 132.3, 129.0, 128.5, 127.4, 126.8, 123.9, 120.2, 119.1, 119.0, 111.6, 103.9,

实施例19:2-苯基-3-对氟苯硫基吲哚嗪(式I-3)的制备Example 19: Preparation of 2-phenyl-3-p-fluorophenylthioindolezine (Formula I-3)

反应步骤同实施例1,所不同的是对氯苯硫酚改为对氟苯硫酚,产物2-苯基-3-对氟苯硫基吲哚嗪的分离收率为88%。The reaction steps are the same as in Example 1, except that p-chlorothiophenol is changed to p-fluorothiophenol, and the isolated yield of the product 2-phenyl-3-p-fluorophenylthioindoxazine is 88%.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 8.23 (d, J=6.5 Hz, 1H), 7.73-7.68 (m, 2H),7.45 (d, J=8.9 Hz, 1H), 7.41-7.37 (m, 2H), 7.33-7.29 (m, 1H), 6.90-6.84 (m,5H), 6.79 (s, 1H), 6.63-6.58 (m, 1H); 1 H NMR (400 MHz, CDCl 3 ) δ 8.23 (d, J =6.5 Hz, 1H), 7.73-7.68 (m, 2H),7.45 (d, J =8.9 Hz, 1H), 7.41-7.37 (m, 2H), 7.33-7.29 (m, 1H), 6.90-6.84 (m, 5H), 6.79 (s, 1H), 6.63-6.58 (m, 1H);

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 161.0 (d, J=244.8 Hz), 136.8, 135.7, 134.9,131.9(d, J=3.0 Hz), 128.7, 128.2, 127.0, 126.7 (d, J=7.9 Hz), 123.6, 119.8,118.7, 116.1 (d, J=22.0 Hz), 111.2, 104.6, 100.1。 13 C NMR (101 MHz, CDCl 3 ) δ 161.0 (d, J =244.8 Hz), 136.8, 135.7, 134.9, 131.9 (d, J =3.0 Hz), 128.7, 128.2, 127.0, 126.7 (d, J =7.9 Hz), 123.6, 119.8, 118.7, 116.1 (d, J =22.0 Hz), 111.2, 104.6, 100.1.

实施例20:2-苯基-3-对甲苯硫基吲哚嗪(式I-4)的制备Example 20: Preparation of 2-phenyl-3-p-tolylthioindolezine (Formula I-4)

反应步骤同实施例1,所不同的是对氯苯硫酚改为对甲基苯硫酚,产物2-苯基-3-对甲苯硫基吲哚嗪的分离收率为78%。The reaction steps are the same as in Example 1, except that p-chlorothiophenol is changed to p-methylthiophenol, and the isolated yield of product 2-phenyl-3-p-tolylthioindoxazine is 78%.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 8.22 (d, J=8.0 Hz, 1H), 7.72 (d, J=7.1 Hz,2H), 7.42 (d, J=8.9 Hz, 1H), 7.39-7.35 (m, 2H), 7.31-7.26 (m, 1H), 6.97 (d, J=7.9 Hz, 2H), 6.84-6.77 (m, 4H), 6.57- 6.53 (m, 1H), 2.23 (s, 3H); 1 H NMR (400 MHz, CDCl 3 ) δ 8.22 (d, J =8.0 Hz, 1H), 7.72 (d, J =7.1 Hz,2H), 7.42 (d, J =8.9 Hz, 1H), 7.39-7.35 (m, 2H), 7.31-7.26 (m, 1H), 6.97 (d, J =7.9 Hz, 2H), 6.84-6.77 (m, 4H), 6.57- 6.53 (m, 1H), 2.23 (s, 3H );

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 136.9, 135.9, 135.4, 135.3, 133.6, 130.1,129.0, 128.4, 127.2, 125.3, 124.1, 119.9, 118.9, 111.3, 105.2, 100.2, 21.0。 13 C NMR (101 MHz, CDCl 3 ) δ 136.9, 135.9, 135.4, 135.3, 133.6, 130.1, 129.0, 128.4, 127.2, 125.3, 124.1, 119.9, 118.9, 111.3, 105.2, .

实施例21:2-苯基-3-对叔丁基苯硫基吲哚嗪(式I-5)的制备Example 21: Preparation of 2-phenyl-3-p-tert-butylphenylthioindolezine (Formula I-5)

反应步骤同实施例1,所不同的是对氯苯硫酚改为对叔丁基苯硫酚,产物2-苯基-3-对叔丁基苯硫基吲哚嗪的分离收率为78%。The reaction steps are the same as in Example 1, except that p-chlorothiophenol is changed to p-tert-butylthiophenol, and the isolated yield of product 2-phenyl-3-p-tert-butylphenylthioindolezine is 78% %.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 8.31- 8.21 (m, 1H), 7.74 (d, J=8.0 Hz, 2H),7.49 (d, J=7.7 Hz, 1H), 7.42-7.37 (m, 2H), 7.31-7.25 (m, 1H), 7.21-7.16 (m,3H), 6.84-6.78 (m, 4H), 6.63-6.54 (m, 1H), 1.23 (s, 9H); 1 H NMR (400 MHz, CDCl 3 ) δ 8.31- 8.21 (m, 1H), 7.74 (d, J =8.0 Hz, 2H),7.49 (d, J =7.7 Hz, 1H), 7.42-7.37 (m, 2H), 7.31-7.25 (m, 1H), 7.21-7.16 (m, 3H), 6.84-6.78 (m, 4H), 6.63-6.54 (m, 1H), 1.23 (s, 9H);

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 148.5, 136.9, 135.9, 135.4, 133.7, 130.8,129.1, 128.4, 128.0, 127.2, 126.4, 125.1, 124.2, 119.9, 118.8, 111.3, 105.2,100.2, 34.4, 31.5。 13 C NMR (101 MHz, CDCl 3 ) δ 148.5, 136.9, 135.9, 135.4, 133.7, 130.8,129.1, 128.4, 128.0, 127.2, 126.4, 125.1, 124.2, 119.9, 118.8, 111.3, 105.2,100.2, 34.4, 31.5 .

实施例22:2-苯基-3-对异丙基苯硫基吲哚嗪(式I-6)的制备Example 22: Preparation of 2-phenyl-3-p-isopropylphenylthioindolezine (Formula I-6)

反应步骤同实施例1,所不同的是对氯苯硫酚改为对异丙基苯硫酚,产物2-苯基-3-对异丙基苯硫基吲哚嗪的分离收率为81%。The reaction steps are the same as in Example 1, and the difference is that p-chlorothiophenol is changed to p-isopropylthiophenol, and the separation yield of product 2-phenyl-3-p-isopropylphenylthioindoxazine is 81 %.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 8.25 (d, J=7.0 Hz, 1H), 7.73 (d, J=7.3 Hz,2H), 7.44 (d, J=8.9 Hz, 1H), 7.40 -7.35 (m, 2H), 7.31-7.26 (m, 1H), 7.03 (d,J=8.2 Hz, 2H), 6.87-6.77 (m, 4H), 6.60- -6.53 (m, 1H), 1.17 (d, J=6.9 Hz,6H); 1 H NMR (400 MHz, CDCl 3 ) δ 8.25 (d, J =7.0 Hz, 1H), 7.73 (d, J =7.3 Hz,2H), 7.44 (d, J =8.9 Hz, 1H), 7.40 -7.35 (m, 2H), 7.31-7.26 (m, 1H), 7.03 (d, J =8.2 Hz, 2H), 6.87-6.77 (m, 4H), 6.60- -6.53 (m, 1H), 1.17 (d, J = 6.9 Hz, 6H);

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 146.3, 136.9, 135.9, 135.4, 134.0, 129.1,128.4, 127.5, 127.5, 127.2, 125.4, 124.2, 119.9, 118.9, 111.3, 105.3, 100.2,33.7, 24.0。 13 C NMR (101 MHz, CDCL 3 ) Δ 146.3, 136.9, 135.9, 135.4, 134.0, 129.1,128.4, 127.5, 127.2, 125.4, 124.2, 119.9, 111.3, 100.2,33.7, 24.0.

实施例23:2-苯基-3-邻氯苯硫基吲哚嗪(式I-7)的制备Example 23: Preparation of 2-phenyl-3-o-chlorophenylthioindolezine (Formula I-7)

反应步骤同实施例1,所不同的对氯苯硫酚改成邻氯苯硫酚,产物2-苯基-3-邻氯苯硫基吲哚嗪的分离收率为76%。The reaction steps are the same as in Example 1, except that the different p-chlorothiophenols are changed into o-chlorothiophenols, and the isolated yield of the product 2-phenyl-3-o-chlorophenylthioindoxazine is 76%.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 8.16 (d, J=Hz, 1H), 7.67 (d, J=Hz, 2H), 7.46(d, J=Hz, 1H), 7.40-7.26 (m, 4H), 7.03- 6.98 (m, 1H), 6.94- 6.85 (m, 2H),6.81 (s, 1H), 6.61-6.56 (m, 1H), 6.22 (d, J=7.9 Hz, 1H); 1 H NMR (400 MHz, CDCl 3 ) δ 8.16 (d, J =Hz, 1H), 7.67 (d, J =Hz, 2H), 7.46(d, J =Hz, 1H), 7.40-7.26 (m, 4H), 7.03- 6.98 (m, 1H), 6.94- 6.85 (m, 2H), 6.81 (s, 1H), 6.61-6.56 (m, 1H), 6.22 (d, J =7.9 Hz, 1H);

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 137.7, 136.4, 136.3, 135.0, 130.7, 129.9,128.9, 128.5, 127.5, 127.4, 126.3, 125.6, 124.0, 120.3, 119.0, 111.6, 103.0,100.6。 13 C NMR (101 MHz, CDCl 3 ) δ 137.7, 136.4, 136.3, 135.0, 130.7, 129.9, 128.9, 128.5, 127.5, 127.4, 126.3, 125.6, 124.0, 120.3, 1103.0, 6.0

实施例24:2-苯基-3-邻甲苯硫基吲哚嗪(式I-8)的制备Example 24: Preparation of 2-phenyl-3-o-tolylthioindolezine (Formula I-8)

反应步骤同实施例1,所不同的是对氯苯硫酚改成邻甲基苯硫酚,2-苯基-3-邻甲苯硫基吲哚嗪的分离收率为70%。The reaction steps are the same as in Example 1, except that p-chlorothiophenol is changed into o-methylthiophenol, and the isolated yield of 2-phenyl-3-o-tolylthioindoxazine is 70%.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 8.03 (d, J=7.1 Hz, 1H), 7.59 (d, J=7.6 Hz,2H), 7.33 (d, J=8.9 Hz, 1H), 7.28-7.23 (m, 2H), 7.19-7.15 (m, 1H), 7.04 (d, J=7.4 Hz, 1H), 6.90-6.86 (m, 1H), 6.80-6.70 (m, 3H), 6.45-6.41 (m, 1H), 6.18(d, J=Hz, 1H), 2.36 (s, 3H); 1 H NMR (400 MHz, CDCl 3 ) δ 8.03 (d, J =7.1 Hz, 1H), 7.59 (d, J =7.6 Hz,2H), 7.33 (d, J =8.9 Hz, 1H), 7.28-7.23 (m, 2H), 7.19-7.15 (m, 1H), 7.04 (d, J =7.4 Hz, 1H), 6.90-6.86 (m, 1H), 6.80-6.70 (m, 3H), 6.45-6.41 (m , 1H), 6.18(d, J =Hz, 1H), 2.36 (s, 3H);

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 137.3, 136.2, 136.1, 135.3, 134.7, 130.6,129.0, 128.4, 127.2, 126.9, 125.2, 124.1, 119.9, 118.9, 111.3, 104.0, 100.4,19.8。 13 C NMR (101 MHz, CDCl 3 ) δ 137.3, 136.2, 136.1, 135.3, 134.7, 130.6, 129.0, 128.4, 127.2, 126.9, 125.2, 124.1, 119.9, 118.9, 110.8, 4.

实施例25:2-苯基-3-间氯苯硫基吲哚嗪(式I-9)的制备Example 25: Preparation of 2-phenyl-3-m-chlorophenylthioindolezine (Formula I-9)

反应步骤同实施例1,所不同的是对氯苯硫酚改成间氯苯硫酚,2-苯基-3-间氯苯硫基吲哚嗪的分离收率为83%。The reaction steps are the same as in Example 1, except that p-chlorothiophenol is changed into m-chlorothiophenol, and the isolated yield of 2-phenyl-3-m-chlorophenylthioindoxazine is 83%.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 8.18 (d, J=Hz, 1H), 7.68 (d, J=Hz, 2H), 7.44(d, J=Hz, 1H), 7.40-7.35 (m, 2H), 7.32-7.26 (m, 1H), 7.08-7.02 (m, 2H), 6.91-6.83 (m, 2H), 6.79 (s, 1H), 6.69 (d, J=Hz, 1H), 6.61-6.55 (m, 1H); 1 H NMR (400 MHz, CDCl 3 ) δ 8.18 (d, J =Hz, 1H), 7.68 (d, J =Hz, 2H), 7.44(d, J =Hz, 1H), 7.40-7.35 (m, 2H), 7.32-7.26 (m, 1H), 7.08-7.02 (m, 2H), 6.91-6.83 (m, 2H), 6.79 (s, 1H), 6.69 (d, J =Hz, 1H), 6.61- 6.55 (m, 1H);

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 139.7, 137.4, 136.3, 135.3, 135.1, 130.4,129.0, 128.5, 127.4, 125.8, 124.9, 123.9, 123.2, 120.3, 119.0, 111.7, 103.5,100.6。 13 C NMR (101 MHz, CDCl 3 ) δ 139.7, 137.4, 136.3, 135.3, 135.1, 130.4, 129.0, 128.5, 127.4, 125.8, 124.9, 123.9, 123.2, 120.3, 110.0, 6.

实施例26:2-苯基-3-间甲苯硫基吲哚嗪(式I-10)的制备Example 26: Preparation of 2-phenyl-3-m-tolylthioindolezine (Formula I-10)

反应步骤同实施例1,所不同的是对氯苯硫酚改成间甲基苯硫酚,2-苯基-3-间甲基苯硫基吲哚嗪的分离收率为75%。The reaction steps are the same as in Example 1, except that p-chlorothiophenol is changed into m-methylthiophenol, and the isolated yield of 2-phenyl-3-m-methylphenylthioindoxazine is 75%.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 8.15 (d, J=Hz, 1H), 7.67-7.62 (m, 2H), 7.37(d, J=Hz, 1H), 7.33-7.27 (m, 2H), 7.24-7.19 (m, 1H), 6.99-6.94 (m, 1H), 6.83-6.69 (m, 4H), 6.57-6.47 (m, 2H), 2.14 (s, 3H); 1 H NMR (400 MHz, CDCl 3 ) δ 8.15 (d, J =Hz, 1H), 7.67-7.62 (m, 2H), 7.37(d, J =Hz, 1H), 7.33-7.27 (m, 2H) , 7.24-7.19 (m, 1H), 6.99-6.94 (m, 1H), 6.83-6.69 (m, 4H), 6.57-6.47 (m, 2H), 2.14 (s, 3H);

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 139.2, 137.1, 137.0, 136.0, 135.4, 129.1(d, J = 16.4 Hz), 128.4, 127.2, 126.4, 125.8, 124.1, 122.2, 120.0, 119.0,111.4, 104.9, 100.2, 21.6。 13 C NMR (101 MHz, CDCl 3 ) δ 139.2, 137.1, 137.0, 136.0, 135.4, 129.1(d, J = 16.4 Hz), 128.4, 127.2, 126.4, 125.8, 124.1, 122.2, 1119.0, 4, , 100.2, 21.6.

实施例27:2-苯基-3-间甲氧基苯硫基吲哚嗪(式I-11)的制备Example 27: Preparation of 2-phenyl-3-m-methoxyphenylthioindolezine (Formula I-11)

反应步骤同实施例1,所不同的是对氯苯硫酚改成间甲氧基苯硫酚,电压改为0.3V,2-苯基-3-间甲氧基苯硫基吲哚嗪的分离收率为85%。The reaction steps are the same as in Example 1, and the difference is that p-chlorothiophenol is changed into m-methoxythiophenol, and the voltage is changed into 0.3V. The isolated yield was 85%.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 8.21 (d, J=Hz, 1H), 7.72 (d, J=Hz, 2H),7.41-7.33 (m, 3H), 7.27 (d, J=Hz, 1H), 7.04-6.99 (m, 1H), 6.86 (d, J=Hz, 1H),6.83-6.77 (m, 3H), 6.62 (d, J=7.8 Hz, 1H), 6.54-6.50 (m, 1H), 2.18 (s, 3H); 1 H NMR (400 MHz, CDCl 3 ) δ 8.21 (d, J =Hz, 1H), 7.72 (d, J =Hz, 2H),7.41-7.33 (m, 3H), 7.27 (d, J =Hz, 1H), 7.04-6.99 (m, 1H), 6.86 (d, J =Hz, 1H),6.83-6.77 (m, 3H), 6.62 (d, J =7.8 Hz, 1H), 6.54-6.50 (m, 1H), 2.18 (s, 3H);

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 139.1, 137.1, 137.0, 136.0, 135.3, 129.2,129.0, 128.4, 127.2, 126.4, 125.8, 124.1, 122.2, 119.9, 118.8, 111.3, 104.8,100.2, 21.5。 13 C NMR (101 MHz, CDCL 3 ) Δ 139.1, 137.1, 137.0, 136.0, 135.3, 129.2, 129.0, 128.4, 127.4, 125.8, 122.2, 119.9, 111.3, 104.8,100.2, 21.5.

实施例28:2-苯基-3-(噻吩-2-基)硫基吲哚嗪(式I-12)的制备Example 28: Preparation of 2-phenyl-3-(thiophen-2-yl)thioindolezine (Formula I-12)

反应步骤同实施例1,所不同的对氯苯硫酚改成2-噻吩硫醇,反应时间改为6 h,产物2-苯基-3-(噻吩-2-基)硫基吲哚嗪的分离收率为78%。The reaction steps are the same as in Example 1, except that the different p-chlorothiophenol is changed to 2-thiophene thiol, and the reaction time is changed to 6 h, and the product 2-phenyl-3-(thiophen-2-yl)thioindoxazine The isolated yield is 78%.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 8.45-8.36 (m, 1H), 7.76-7.68 (m, 2H), 7.40-7.33 (m, 3H), 7.29-7.25 (m, 1H), 7.06-7.02 (m, 1H), 6.83-6.76 (m, 3H), 6.66-6.54 (m, 2H); 1 H NMR (400 MHz, CDCl 3 ) δ 8.45-8.36 (m, 1H), 7.76-7.68 (m, 2H), 7.40-7.33 (m, 3H), 7.29-7.25 (m, 1H), 7.06-7.02 (m, 1H), 6.83-6.76 (m, 3H), 6.66-6.54 (m, 2H);

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 136.2, 136.1, 135.7, 135.4, 129.4, 128.4,127.6, 127.3, 126.9, 124.0, 120.0, 119.0, 111.4, 107.6, 100.4。 13 C NMR (101 MHz, CDCl 3 ) δ 136.2, 136.1, 135.7, 135.4, 129.4, 128.4, 127.6, 127.3, 126.9, 124.0, 120.0, 119.0, 111.4, 107.6, 100.4.

实施例29:2-苯基-5-甲基-3-对氯苯硫基吲哚嗪(式I-13)的制备Example 29: Preparation of 2-phenyl-5-methyl-3-p-chlorophenylthioindolezine (Formula I-13)

反应步骤同实施例1,所不同的是2-苯基吲哚嗪改为2-苯基-5-甲基吲哚嗪, 产物2-苯基-5-甲基-3-对氯苯硫基吲哚嗪的分离收率为82%。The reaction steps are the same as in Example 1, except that 2-phenylindolezine is changed to 2-phenyl-5-methylindolezine, and the product 2-phenyl-5-methyl-3-p-chlorobenzenesulfide The isolated yield of base indoxazine was 82%.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 8.09 (d, J=7.1 Hz, 1H), 7.71-7.64 (m, 2H),7.40 – 7.35 (m, 2H), 7.31-7.27 (m, 1H), 7.22 (s, 1H), 7.15-7.12 (m, 2H),6.82-6.78 (m, 2H), 6.65 (s, 1H), 6.46-6.42 (m, 1H), 2.32 (s, 3H); 1 H NMR (400 MHz, CDCl 3 ) δ 8.09 (d, J =7.1 Hz, 1H), 7.71-7.64 (m, 2H),7.40 – 7.35 (m, 2H), 7.31-7.27 (m, 1H), 7.22 (s, 1H), 7.15-7.12 (m, 2H), 6.82-6.78 (m, 2H), 6.65 (s, 1H), 6.46-6.42 (m, 1H), 2.32 (s, 3H);

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 137.4, 136.6, 136.4, 135.3, 131.2, 130.7,129.4, 128.9, 128.5, 127.3, 126.4, 123.4, 117.3, 114.3, 102.9, 99.0, 21.2。 13 C NMR (101 MHz, CDCl 3 ) δ 137.4, 136.6, 136.4, 135.3, 131.2, 130.7, 129.4, 128.9, 128.5, 127.3, 126.4, 123.4, 117.3, 114.3, 9192.0, 9.

实施例30:2-苯基-6-甲基-3-对氯苯硫基吲哚嗪(式I-14)的制备Example 30: Preparation of 2-phenyl-6-methyl-3-p-chlorophenylthioindolezine (Formula I-14)

反应步骤同实施例1,所不同的是2-苯基吲哚嗪改为2-苯基-6-甲基吲哚嗪,产物2-苯基-6-甲基-3-对氯苯硫基吲哚嗪的分离收率为80%。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 2-phenyl-6-methyl indolezine, and product 2-phenyl-6-methyl-3-p-chlorobenzenesulfur The isolated yield of base indoxazine was 80%.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 7.93 (s, 1H), 7.60-7.56 (m, 2H), 7.31-7.27(m, 3H), 7.22-7.18 (m, 1H), 7.08-7.04 (m, 2H), 6.74-6.71 (m, 2H), 6.68-6.65(m, 2H), 2.15 (s, 3H); 1 H NMR (400 MHz, CDCl 3 ) δ 7.93 (s, 1H), 7.60-7.56 (m, 2H), 7.31-7.27(m, 3H), 7.22-7.18 (m, 1H), 7.08-7.04 (m , 2H), 6.74-6.71 (m, 2H), 6.68-6.65(m, 2H), 2.15 (s, 3H);

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 136.9, 136.4, 135.3, 135.1, 131.3, 129.4,128.9, 128.4, 127.2, 126.5, 123.5, 121.5, 121.2, 118.5, 103.6, 100.2, 18.7。 13 C NMR (101 MHz, CDCl 3 ) δ 136.9, 136.4, 135.3, 135.1, 131.3, 129.4, 128.9, 128.4, 127.2, 126.5, 123.5, 121.5, 121.2, 118.5, 100.2, 103.6,

实施例31:2-对甲苯基-3-对氯苯硫基吲哚嗪(式I-15)的制备Example 31: Preparation of 2-p-tolyl-3-p-chlorophenylthioindolezine (Formula I-15)

反应步骤同实施例1,所不同的是2-苯基吲哚嗪改为2-对甲苯基吲哚嗪,产物2-对甲基苯基-3-对氯苯硫基吲哚嗪的分离收率为72%。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 2-p-tolyl indolezine, and the separation of product 2-p-methylphenyl-3-p-chlorophenylindolezine The yield was 72%.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 8.13-8.07 (m, 1H), 7.49 (d, J=8.1 Hz, 2H),7.35 (d, J=Hz, 1H), 7.13-7.09 (m, 2H), 7.07-7.01 (m, 2H), 6.80-6.74 (m, 1H),6.73-6.67 (m, 3H), 6.52-6.46 (m, 1H), 2.27 (s, 3H); 1 H NMR (400 MHz, CDCl 3 ) δ 8.13-8.07 (m, 1H), 7.49 (d, J =8.1 Hz, 2H),7.35 (d, J =Hz, 1H), 7.13-7.09 (m, 2H ), 7.07-7.01 (m, 2H), 6.80-6.74 (m, 1H), 6.73-6.67 (m, 3H), 6.52-6.46 (m, 1H), 2.27 (s, 3H);

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 137.4, 137.2, 136.2, 136.1, 132.2, 131.3,129.4, 129.2, 128.8, 126.5, 123.9, 120.1, 118.9, 111.5, 104.0, 100.3, 21.3。 13 C NMR (101 MHz, CDCl 3 ) δ 137.4, 137.2, 136.2, 136.1, 132.2, 131.3, 129.4, 129.2, 128.8, 126.5, 123.9, 120.1, 118.9, 111.5, 104.0, 3,

实施例32:2-对氯苯基-3-对氯苯硫基吲哚嗪(式I-16)的制备Example 32: Preparation of 2-p-chlorophenyl-3-p-chlorophenylthioindolezine (Formula I-16)

反应步骤同实施例1,所不同的是2-苯基吲哚嗪改为2-对氯苯基吲哚嗪,产物2-对氯苯基-3-对氯苯硫基吲哚嗪的分离收率为77%。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 2-p-chlorophenylindolezine, and the separation of product 2-p-chlorophenyl-3-p-chlorophenylindolezine The yield was 77%.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 8.13-8.10 (m, 1H), 7.55-7.51 (m, 2H), 7.38(d, J=8.9 Hz, 1H), 7.29-7.25 (m, 2H), 7.08-7.05 (m, 2H), 6.84-6.80 (m, 1H),6.72-6.68 (m, 3H), 6.56-6.53 (m, 1H); 1 H NMR (400 MHz, CDCl 3 ) δ 8.13-8.10 (m, 1H), 7.55-7.51 (m, 2H), 7.38(d, J =8.9 Hz, 1H), 7.29-7.25 (m, 2H), 7.08-7.05 (m, 2H), 6.84-6.80 (m, 1H), 6.72-6.68 (m, 3H), 6.56-6.53 (m, 1H);

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 137.2, 136.1, 135.9, 135.0, 131.2, 129.4,128.9, 128.4, 127.3, 126.4, 123.8, 120.1, 118.9, 111.5, 104.0, 100.4。 13 C NMR (101 MHz, CDCl 3 ) δ 137.2, 136.1, 135.9, 135.0, 131.2, 129.4, 128.9, 128.4, 127.3, 126.4, 123.8, 120.1, 118.9, 111.5, 104.0,

实施例33:2-对氯苯基-5-甲基-3-对氯苯硫基吲哚嗪(式I-17)的制备Example 33: Preparation of 2-p-chlorophenyl-5-methyl-3-p-chlorophenylthioindolezine (Formula I-17)

反应步骤同实施例1,所不同的是2-苯基吲哚嗪改为2-对氯苯基-5-甲基吲哚嗪,产物2-对氯苯基-5-甲基-3-对氯苯硫基吲哚嗪的分离收率为73%。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 2-p-chlorophenyl-5-methyl indolezine, and product 2-p-chlorophenyl-5-methyl-3- The isolated yield of p-chlorophenylthioindoxazine was 73%.

所得产物的核磁共振氢谱的数据如下:The data of the proton nuclear magnetic resonance spectrum of gained product are as follows:

1H NMR (400 MHz, CDCl3) δ 8.00 (d, J=7.2 Hz, 1H), 7.53-7.50 (m, 2H),7.29 (s, 2H), 7.25 (d, J=8.6 Hz, 2H), 7.06-7.04 (m, 2H), 6.70-6.66 (m, 2H),6.53 (s, 1H), 6.38-6.35 (m, 1H), 2.23 (s, 3H); 1 H NMR (400 MHz, CDCl 3 ) δ 8.00 (d, J =7.2 Hz, 1H), 7.53-7.50 (m, 2H), 7.29 (s, 2H), 7.25 (d, J =8.6 Hz, 2H) , 7.06-7.04 (m, 2H), 6.70-6.66 (m, 2H), 6.53 (s, 1H), 6.38-6.35 (m, 1H), 2.23 (s, 3H);

所得产物的核磁共振碳谱的数据如下:The data of the carbon nuclear magnetic resonance spectrum of gained product are as follows:

13C NMR (101 MHz, CDCl3) δ 136.6, 136.1, 133.7, 133.2, 132.9, 131.8,131.4, 130.9, 130.1, 129.5, 128.6, 128.3, 126.4, 123.4, 117.3, 114.5, 103.1,98.9, 21.1。 13 C NMR (101 MHz, CDCL 3 ) Δ 136.6, 136.1, 133.7, 132.9, 131.8, 131.4, 130.9, 130.1, 129.5, 128.3, 126.4, 123.4, 117.5, 103.1,98.9, 21.1.

Claims (10)

1. a method for synthesizing 3-mercaptoindolizine compounds by electrocatalytic oxidation is characterized by comprising the following steps:
(1) Adding a reaction substrate to an organic solvent containing a supporting electrolyte;
the reaction substrate comprises indolizine compounds, thiophenol and potassium iodide;
(2) Electrifying the solution obtained in the step (1) to enable electrocatalytic oxidation reaction to occur between reaction substrates, and synthesizing the 3-mercaptoindolizine compound;
the structural formula of the indolizine compound is shown in the specification
Figure DEST_PATH_IMAGE002
The structural formula of the thiophenol is shown in the specification
Figure DEST_PATH_IMAGE004
The structural formula of the 3-mercaptoindolizine compound is shown in the specification
Figure DEST_PATH_IMAGE006
Wherein R is 1 Is one of H, halogen, C1-C4 alkyl and C1-C4 alkoxy, R 2 H, halogen, C1-C4 alkyl, C1-C4 alkoxyOne of the radicals, R 3 Is one of phenyl, substituted phenyl, heteroaromatic group, substituted heteroaromatic group, naphthyl and substituted naphthyl.
2. The method for synthesizing 3-mercaptoindolizines by electrocatalytic oxidation of claim 1, wherein R is 1 Is one of H, cl and methyl, and the R 2 Is one of H and methyl, and the R 3 Is one of phenyl, halogenated phenyl, alkyl substituted phenyl, alkoxy substituted phenyl and thienyl.
3. The method for synthesizing 3-mercaptoindolizines by electrocatalytic oxidation according to claim 1, wherein the supporting electrolyte in step (1) is LiClO 4 n Bu 4 NBF 4 n Bu 4 ClO 4 、NaClO 4 Wherein the organic solvent is N, N-dimethylformamide or dimethyl sulfoxide.
4. The method for synthesizing 3-mercaptoindolizines by electrocatalytic oxidation according to claim 1 or 3, wherein the supporting electrolyte in step (1) is LiClO 4 The organic solvent is N, N-dimethylformamide.
5. The method for synthesizing 3-mercaptoindolizines by electrocatalytic oxidation according to claim 1 or 3, wherein the supporting electrolyte in the organic solvent in the step (1) has a concentration of 0.05 to 0.2mol/L.
6. The method for synthesizing 3-mercaptoindolizines by electrocatalytic oxidation as set forth in claim 1, wherein the ratio of the amount of indolizines to the amount of thiophenol and potassium iodide in step (1) is 100:100 to 200:10 to 40.
7. The method for synthesizing 3-mercaptoindolizines by electrocatalytic oxidation as claimed in claim 1 or 6, wherein the ratio of the amount of indolizines to the amount of thiophenol and potassium iodide in step (1) is 100:120 to 180:10 to 20.
8. The method for synthesizing 3-mercaptoindolizine according to claim 1, wherein the concentration of the indolizine compound in the organic solvent is 0.005 to 0.03mol/L.
9. The method for synthesizing 3-mercaptoindolizines through electrocatalytic oxidation as claimed in claim 1, wherein the electrolysis temperature in step (2) is 15 to 45 ℃, the electrolysis voltage is 0.1 to 0.4V, and the electrolysis time is 3 to 8h.
10. A method for purifying a 3-mercaptoindolizine compound prepared by the method of any one of claims 1 to 9, comprising the steps of:
(1) Taking out the solution containing the 3-mercaptoindolizine compound after the electrolysis reaction is finished, evaporating the solvent under reduced pressure, performing column chromatography separation, and collecting the eluent containing the target compound;
(2) And evaporating to remove the solvent to obtain the product 3-mercaptoindolizine compound.
CN202211598009.8A 2022-12-14 2022-12-14 Method for synthesizing 3-mercaptoindolizine compound by electrocatalytic oxidation Pending CN115652346A (en)

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CN106544692A (en) * 2016-10-28 2017-03-29 华南理工大学 A kind of electrochemical preparation method of 3 selenium (hetero) aryl indole class compound
CN107620088A (en) * 2017-09-14 2018-01-23 浙江工业大学 A kind of method that electrochemical catalytic oxidation synthesizes 3 sulfydryl indole class compounds
CN114989053A (en) * 2022-05-10 2022-09-02 温州大学新材料与产业技术研究院 Method for synthesizing asymmetric disulfide by cross coupling of thiophenol and sulfoxide

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