CN115537853A - Direct electrochemical synthesis method of triarylamine compound - Google Patents
Direct electrochemical synthesis method of triarylamine compound Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- -1 triarylamine compound Chemical class 0.000 title claims description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 10
- 125000005259 triarylamine group Chemical group 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- NPFDZRLGEXMQGV-UHFFFAOYSA-N silver;acetonitrile;nitrate Chemical compound [Ag+].CC#N.[O-][N+]([O-])=O NPFDZRLGEXMQGV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 5
- 239000010439 graphite Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 229950000688 phenothiazine Drugs 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 8
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000004809 thin layer chromatography Methods 0.000 claims description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 125000001484 phenothiazinyl group Chemical class C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 52
- 238000002360 preparation method Methods 0.000 description 38
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- JBMKAUGHUNFTOL-UHFFFAOYSA-N Aldoclor Chemical class C1=C(Cl)C(S(=O)(=O)N)=CC2=C1NC=NS2(=O)=O JBMKAUGHUNFTOL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000002990 phenothiazines Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003451 thiazide diuretic agent Substances 0.000 description 2
- JWGBOHJGWOPYCL-UHFFFAOYSA-N 1-(10H-phenothiazin-2-yl)ethanone Chemical compound C1=CC=C2NC3=CC(C(=O)C)=CC=C3SC2=C1 JWGBOHJGWOPYCL-UHFFFAOYSA-N 0.000 description 1
- TUZVTRCMDIUEBE-UHFFFAOYSA-N 1-chloro-10h-phenothiazine Chemical compound S1C2=CC=CC=C2NC2=C1C=CC=C2Cl TUZVTRCMDIUEBE-UHFFFAOYSA-N 0.000 description 1
- XZSIGWOVDPSPMG-UHFFFAOYSA-N 10h-phenothiazine-2-carbonitrile Chemical compound C1=CC=C2NC3=CC(C#N)=CC=C3SC2=C1 XZSIGWOVDPSPMG-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- VPXGIHGJJJBJFP-UHFFFAOYSA-N 2-(4-methylphenyl)-1h-indole Chemical compound C1=CC(C)=CC=C1C1=CC2=CC=CC=C2N1 VPXGIHGJJJBJFP-UHFFFAOYSA-N 0.000 description 1
- RKGYJVASTMCSHZ-UHFFFAOYSA-N 2-(trifluoromethyl)-10H-phenothiazine Chemical compound C1=CC=C2NC3=CC(C(F)(F)F)=CC=C3SC2=C1 RKGYJVASTMCSHZ-UHFFFAOYSA-N 0.000 description 1
- KFZGLJSYQXZIGP-UHFFFAOYSA-N 2-chloro-10h-phenothiazine Chemical compound C1=CC=C2NC3=CC(Cl)=CC=C3SC2=C1 KFZGLJSYQXZIGP-UHFFFAOYSA-N 0.000 description 1
- DLYKFPHPBCTAKD-UHFFFAOYSA-N 2-methoxy-10H-phenothiazine Chemical compound C1=CC=C2NC3=CC(OC)=CC=C3SC2=C1 DLYKFPHPBCTAKD-UHFFFAOYSA-N 0.000 description 1
- OBVKBOLDEFIQDP-UHFFFAOYSA-N 2-methylsulfanyl-10h-phenothiazine Chemical compound C1=CC=C2NC3=CC(SC)=CC=C3SC2=C1 OBVKBOLDEFIQDP-UHFFFAOYSA-N 0.000 description 1
- KLLLJCACIRKBDT-UHFFFAOYSA-N 2-phenyl-1H-indole Chemical compound N1C2=CC=CC=C2C=C1C1=CC=CC=C1 KLLLJCACIRKBDT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000005266 diarylamine group Chemical group 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 125000005059 halophenyl group Chemical group 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002265 redox agent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
Description
(一)技术领域(1) Technical field
本发明涉及一种三芳基胺类化合物的直接电化学合成方法。The invention relates to a direct electrochemical synthesis method of triarylamine compounds.
(二)背景技术(2) Background technology
三芳基胺类化合物具有良好的空穴传输能力，在有机发光二极管、敏化太阳能电池和光致变色材料等领域有广泛应用。吩噻嗪类化合物作为一类较为特殊的二芳基胺化类合物，具有成熟的生产技术，价格便宜，用途广泛的等特点。此外，2-芳基吲哚嗪类化合物与吩噻嗪类化合物一样拥有良好的光电特性，因此以这二者为原料合成三芳基胺类化合物，在光电材料领域具有良好的发展前景。Triarylamine compounds have good hole transport ability and are widely used in the fields of organic light emitting diodes, sensitized solar cells and photochromic materials. As a special kind of diaryl aminated compounds, phenothiazine compounds have the characteristics of mature production technology, cheap price and wide application. In addition, 2-arylindoleazine compounds have the same good photoelectric properties as phenothiazine compounds, so the synthesis of triarylamine compounds using these two as raw materials has good development prospects in the field of photoelectric materials.
传统的三芳基胺类化合物的合成方式是以二芳基胺和芳烃为原料，通过C-N键的构建来制得，但是这些合成方法不可避免地需要使用化学氧化剂、过渡金属催化剂或光敏剂，并且会遇到异构体混合等问题。同时也不符合可持续发展和绿色化学的特点。The traditional synthesis of triarylamines is based on diarylamines and aromatic hydrocarbons through the construction of C-N bonds, but these synthesis methods inevitably require the use of chemical oxidants, transition metal catalysts or photosensitizers, and Problems such as isomer mixing will be encountered. At the same time, it does not meet the characteristics of sustainable development and green chemistry.
近年来，电化学作为一种环境友好、高效的合成方法，为绿色有机合成提供了新的可能。在电化学反应过程中，电充当了氧化还原剂以及催化剂，无需外部氧化剂和催化剂，不仅提高了原子利用率，也有利于产品的分离提纯。In recent years, electrochemistry, as an environmentally friendly and efficient synthesis method, has provided new possibilities for green organic synthesis. In the electrochemical reaction process, electricity acts as a redox agent and a catalyst, without the need for external oxidants and catalysts, which not only improves the utilization of atoms, but also facilitates the separation and purification of products.
(三)发明内容(3) Contents of the invention
本发明目的是提供一种三芳基胺类化合物的直接电化学合成方法。The purpose of the present invention is to provide a direct electrochemical synthesis method of triarylamine compounds.
本发明采用的技术方案是：The technical scheme adopted in the present invention is:
一种三芳基胺类化合物的直接电化学合成方法，所述方法包括：以结构式如式(II)所示的吩噻嗪类化合物和结构如式(III)所示的2-芳基吲哚嗪类化合物为反应原料，采用三电极体系，以石墨电极或Pt电极为阴极和阳极(阴极和阳极材料可以相同也可以不同)，以0.1mol/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，在15～45℃、 0.1～0.3V条件下搅拌进行电解反应，反应结束后经分离处理得到结构如式(I)所示的三芳基胺类化合物；所述支持电解质为LiClO4、nBu4NBF4、nBu4NPF6或NaClO4，优选为LiClO4，所述有机溶剂为N,N-二甲基甲酰胺、乙腈或乙酸乙酯，优选为N,N-二甲基甲酰胺；A direct electrochemical synthesis method of a triarylamine compound, the method comprising: a phenothiazine compound having a structural formula as shown in formula (II) and a 2-arylindole having a structure as shown in formula (III) Azine compounds are used as reaction raw materials, using a three-electrode system, with graphite electrodes or Pt electrodes as cathodes and anodes (cathode and anode materials can be the same or different), and 0.1mol/L silver nitrate acetonitrile solution as a reference electrode. In an organic solvent containing a supporting electrolyte, stirring at 15 to 45° C. and 0.1 to 0.3 V to carry out an electrolysis reaction, after the reaction is completed, a triarylamine compound having a structure as shown in formula (I) is obtained through separation and treatment; the supporting The electrolyte is LiClO 4 , nBu 4 NBF 4 , nBu 4 NPF 6 or NaClO 4 , preferably LiClO 4 , and the organic solvent is N,N-dimethylformamide, acetonitrile or ethyl acetate, preferably N, N-dimethylformamide;
式(I)～(III)中，In formula (I)～(III),
R1为H、C1～C4烷基、卤素、C1～C2烷氧基、硝基、氰基、三氟甲基或乙酰基；R1 is H, C1 ～C4 alkyl, halogen, C1～C2 alkoxy, nitro, cyano, trifluoromethyl or acetyl;
R2为苯基、取代苯基、萘基或取代萘基，所述的取代苯基和取代萘基的取代基(取代基可以是一个，也可以是多个)各自独立选自下列之一：卤素、硝基、C1～C4的烷基或C1～C4的烷氧基；R 2 is phenyl, substituted phenyl, naphthyl or substituted naphthyl, and the substituents of the substituted phenyl and substituted naphthyl (substituents can be one or more) are independently selected from one of the following : Halogen, nitro, C1-C4 alkyl or C1-C4 alkoxy;
R3为H、C1～C4的烷基、C1～C4的烷氧基、氯、溴或氟。R 3 is H, C1-C4 alkyl, C1-C4 alkoxy, chlorine, bromine or fluorine.
优选的，R1为H、Cl、甲氧基、甲硫基、三氟甲基、氰基或乙酰基，R2为苯基、卤代苯基、C1～C4烷基取代苯基、C1～C4烷氧基取代苯基或萘基，R3为H、甲基或溴。Preferably, R1 is H, Cl, methoxy, methylthio, trifluoromethyl, cyano or acetyl, R2 is phenyl, halophenyl , C1 ～C4 alkyl substituted phenyl, C1 ~C4 alkoxy substituted phenyl or naphthyl, R 3 is H, methyl or bromine.
所述吩噻嗪类化合物和吲哚嗪类化合物的物质的量比为100： 80～150，优选100：110～130。The molar ratio of the phenothiazine compound to the indolezine compound is 100:80-150, preferably 100:110-130.
本发明涉及的反应如下：The reaction that the present invention relates to is as follows:
反应机理如上所示：吲哚嗪在阳极失去一个电子，形成吲哚嗪阳离子自由基，吩噻嗪在阳极失去一个电子和一个氢离子，形成吩噻嗪自由基，吲哚嗪阳离子自由基和吩噻嗪自由基发生偶联后失去一个氢离子得到产物。该化学合成反应也可以采用恒电流方法合成，但产物收率低，主要原因是恒电流条件下原料会在电极表面发生聚合，本发明采用三电极体系，显著提高了产物收率。The reaction mechanism is as shown above: indolezine loses an electron at the anode to form indolezine cation radical, phenothiazine loses an electron and a hydrogen ion at the anode to form phenothiazine radical, indolezine cation radical and The phenothiazine radical loses a hydrogen ion after coupling to obtain the product. The chemical synthesis reaction can also be synthesized by a constant current method, but the product yield is low. The main reason is that the raw materials will polymerize on the electrode surface under the constant current condition. The present invention adopts a three-electrode system, which significantly improves the product yield.
三电极体系是为了排除电极电势因极化电流而产生较大误差而设计的，它在常规的两电极体系(工作电极和对电极)的基础上引入用以稳定工作电极的参比电极。The three-electrode system is designed to eliminate the large error caused by the polarization current of the electrode potential. It introduces a reference electrode to stabilize the working electrode on the basis of the conventional two-electrode system (working electrode and counter electrode).
支持电解质是提高化学电池中溶液导电率的电解质，本身不参与电化学反应。优选的，所述支持电解质在有机溶剂中的浓度为0.05～0.15mol/L。A supporting electrolyte is an electrolyte that increases the conductivity of a solution in a chemical cell and does not itself participate in electrochemical reactions. Preferably, the concentration of the supporting electrolyte in the organic solvent is 0.05-0.15 mol/L.
推荐的有机溶剂质量用量为反应底物吩噻嗪类化合物质量的 150～400倍。The recommended amount of organic solvent is 150 to 400 times the mass of the reaction substrate phenothiazine compound.
具体的，所述分离处理方法如下：反应结束后，减压蒸除溶剂，再进行薄层层析分离，以石油醚/乙酸乙酯体积比20：1的混合液为展开剂，收集含目标化合物的薄层，以二氯甲烷进行洗脱，过滤，滤液蒸除溶剂，即得所述三芳基胺类化合物。Specifically, the separation and treatment method is as follows: after the reaction is completed, the solvent is evaporated under reduced pressure, and then separated by thin layer chromatography, using a mixture of petroleum ether/ethyl acetate with a volume ratio of 20:1 as the developing solvent, and the The thin layer of the compound was eluted with dichloromethane, filtered, and the filtrate was evaporated to remove the solvent to obtain the triarylamine compound.
优选的，所述方法如下：以结构式如式(II)所示的吩噻嗪类化合物和结构如式(III)所示的2-芳基吲哚嗪类化合物为原料，采用三电极体系，阴极和阳极均为Pt电极，以0.1mol/L的硝酸银乙腈溶液作为参比电极，在含有0.05～0.15mol/L LiClO4的N,N-二甲基甲酰胺溶液中，在15～45℃、0.1～0.3V的条件下搅拌电解反应3.5～7.0h后，减压蒸除溶剂，再进行薄层层析分离，以石油醚/乙酸乙酯体积比20：1的混合液为展开剂，收集含目标化合物的薄层，以二氯甲烷进行洗脱，过滤，滤液蒸除溶剂，即得所述三芳基胺类化合物。Preferably, the method is as follows: using a phenothiazine compound as shown in formula (II) and a 2-aryl indole azine compound as shown in formula (III) as raw materials, using a three-electrode system, Both the cathode and the anode are Pt electrodes, with 0.1mol/L silver nitrate acetonitrile solution as the reference electrode, in the N,N-dimethylformamide solution containing 0.05~0.15mol/L LiClO 4 , at 15~45 After stirring the electrolysis reaction for 3.5-7.0 hours under the conditions of ℃ and 0.1-0.3V, evaporate the solvent under reduced pressure, and then conduct thin-layer chromatography separation, using a mixture of petroleum ether/ethyl acetate with a volume ratio of 20:1 as the developing solvent , collect the thin layer containing the target compound, elute with dichloromethane, filter, evaporate the filtrate to remove the solvent, and obtain the triarylamine compound.
本发明的有益效果主要体现在：(1)本发明使用了清洁的电能为氧化剂，降低了环境成本；(2)反应底物的普适性好；(3)产物收率高。The beneficial effects of the present invention are mainly reflected in: (1) the present invention uses clean electric energy as the oxidant, which reduces the environmental cost; (2) the universality of the reaction substrate is good; (3) the product yield is high.
(四)附图说明(4) Description of drawings
图1为10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-1))的核磁氢谱图；Fig. 1 is the nuclear magnetic hydrogen spectrogram of 10-(2-phenylindole-3-yl)-10H-phenothiazine (formula (I-1));
图2为10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-1))的核磁碳谱图。Fig. 2 is the carbon nuclear magnetic spectrum of 10-(2-phenylindolazin-3-yl)-10H-phenothiazine (formula (I-1)).
(五)具体实施方式(5) Specific implementation methods
下面结合具体实施例对本发明进行进一步描述，但本发明的保护范围并不仅限于此：The present invention is further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited thereto:
实施例所制得的三芳基胺类化合物的结构式分别如式(I-1)～(I-26) 所示：The structural formulas of the triarylamine compounds prepared in the examples are shown in formulas (I-1) to (I-26):
实施例1：10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-1))的制备Example 1: Preparation of 10-(2-phenylindole-3-yl)-10H-phenothiazine (formula (I-1))
反应采用三电极体系，阴极和阳极均为Pt电极，0.1mol/L的硝酸银乙腈溶液作为参比电极。在30ml的烧杯内加入0.1mol/L LiClO4的N,N- 二甲基甲酰胺溶液(15mL)、吩噻嗪(0.20mmol)、2-苯基吲哚嗪 (0.24mmol)。25℃，0.2V下恒电位电解，3.5h后反应结束。减压蒸除溶剂，再进行薄层层析分离，以石油醚/乙酸乙酯体积比20：1的混合液为展开剂，收集含目标化合物的薄层，以二氯甲烷进行洗脱，过滤，滤液蒸除溶剂即得产物10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(核磁氢谱图参见图 1，核磁碳谱图参见图2)，收率为85％。The reaction adopts a three-electrode system, the cathode and the anode are both Pt electrodes, and 0.1mol/L silver nitrate acetonitrile solution is used as the reference electrode. Add 0.1mol/L LiClO 4 in N,N-dimethylformamide solution (15mL), phenothiazine (0.20mmol), and 2-phenylindoleazine (0.24mmol) into a 30ml beaker. 25°C, constant potential electrolysis at 0.2V, the reaction ended after 3.5h. Evaporate the solvent under reduced pressure, then conduct thin-layer chromatography separation, use petroleum ether/ethyl acetate with a volume ratio of 20:1 as the developing solvent, collect the thin layer containing the target compound, elute with dichloromethane, and filter , the filtrate was evaporated to remove the solvent to obtain the product 10-(2-phenylindolezin-3-yl)-10H-phenothiazine (see Figure 1 for the H NMR spectrum, and Figure 2 for the C NMR spectrum), and the yield was 85%.
1H NMR(400MHz,CDCl3)δ7.87-7.83(m,3H),7.51-7.49(m,1H), 7.38-7.35(m,2H),7.26-7.25(m,1H),7.10-7.08(m,2H),6.95(s,1H), 6.86-6.79(m,5H),6.55-6.51(m,1H),6.13-6.11(m,2H).13C NMR(101MHz, CDCl3)δ141.6,134.0,131.0,128.9,127.7,127.2,127.1,127.0,125.6,123.6, 121.6,121.2,119.3,118.8,116.5,115.9,111.3,96.9.HRMS(ESI)calculated for C26H19N2S+[M+H]+:391.1263；found:391.1263. 1 H NMR (400MHz, CDCl 3 )δ7.87-7.83(m,3H),7.51-7.49(m,1H), 7.38-7.35(m,2H),7.26-7.25(m,1H),7.10-7.08 (m,2H),6.95(s,1H), 6.86-6.79(m,5H),6.55-6.51(m,1H),6.13-6.11(m,2H). 13 C NMR(101MHz, CDCl 3 )δ141 .6, 134.0, 131.0, 128.9, 127.7, 127.2, 127.1, 127.0, 125.6, 123.6, 121.6, 121.2, 119.3, 118.8, 116.5, 115.9, 111.3, 96.9.HRMS ( ESI ) calculated for C 22 H S 19 N M+H] + :391.1263; found: 391.1263.
实施例2：10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-1))的制备Example 2: Preparation of 10-(2-phenylindole-3-yl)-10H-phenothiazine (formula (I-1))
反应步骤同实施例1，所不同的是电压改为0.1V，反应时间为7.0h， 10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为82％。The reaction steps are the same as in Example 1, except that the voltage is changed to 0.1V, the reaction time is 7.0h, and the yield of 10-(2-phenylindolezin-3-yl)-10H-phenothiazine is 82%. .
实施例3：10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-1))的制备Example 3: Preparation of 10-(2-phenylindole-3-yl)-10H-phenothiazine (formula (I-1))
反应步骤同实施例1，所不同的是电压改为0.3V，反应时间为2.0h， 10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为79％。The reaction steps are the same as in Example 1, except that the voltage is changed to 0.3V, the reaction time is 2.0h, and the yield of 10-(2-phenylindolezin-3-yl)-10H-phenothiazine is 79%. .
实施例4：10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-1))的制备Example 4: Preparation of 10-(2-phenylindole-3-yl)-10H-phenothiazine (formula (I-1))
反应步骤同实施例1，所不同的是温度改为15℃，10-(2-苯基吲哚嗪 -3-基)-10H-吩噻嗪的收率为72％。The reaction steps are the same as in Example 1, except that the temperature is changed to 15° C., and the yield of 10-(2-phenylindole-3-yl)-10H-phenothiazine is 72%.
实施例5：10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-1))的制备Example 5: Preparation of 10-(2-phenylindole-3-yl)-10H-phenothiazine (formula (I-1))
应步骤同实施例1，所不同的是温度改为35℃，10-(2-苯基吲哚嗪-3- 基)-10H-吩噻嗪的收率为85％。The procedure was the same as in Example 1, except that the temperature was changed to 35° C., and the yield of 10-(2-phenylindolezin-3-yl)-10H-phenothiazine was 85%.
实施例6：10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-1))的制备Example 6: Preparation of 10-(2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-1))
反应步骤同实施例1，所不同的是2-苯基吲哚嗪用量改为0.20mmol， 10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为79％。The reaction steps are the same as in Example 1, except that the amount of 2-phenylindolezine is changed to 0.20mmol, and the yield of 10-(2-phenylindolezin-3-yl)-10H-phenothiazine is 79% %.
实施例7：10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-1))的制备Example 7: Preparation of 10-(2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-1))
反应步骤同实施例1，所不同的是2-苯基吲哚嗪用量改为0.30mmol， 10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为85％。The reaction steps are the same as in Example 1, except that the amount of 2-phenylindolezine is changed to 0.30mmol, and the yield of 10-(2-phenylindolezin-3-yl)-10H-phenothiazine is 85% %.
实施例8：10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-1))的制备Example 8: Preparation of 10-(2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-1))
反应步骤同实施例1，所不同的是溶剂改为乙腈，10-(2-苯基吲哚嗪 -3-基)-10H-吩噻嗪的收率为55％。The reaction steps are the same as in Example 1, except that the solvent is changed to acetonitrile, and the yield of 10-(2-phenylindole-3-yl)-10H-phenothiazine is 55%.
实施例9：10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-1))的制备Example 9: Preparation of 10-(2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-1))
反应步骤同实施例1，所不同的是支持电解质改为nBu4NBF4，10-(2- 苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为63％。The reaction steps were the same as in Example 1, except that the supporting electrolyte was changed to n Bu 4 NBF 4 , and the yield of 10-(2-phenylindoleazin-3-yl)-10H-phenothiazine was 63%.
实施例10：10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-1))的制备Example 10: Preparation of 10-(2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-1))
反应步骤同实施例1，所不同的是支持电解质改为nBu4NPF6，10-(2- 苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为67％。The reaction steps were the same as in Example 1, except that the supporting electrolyte was changed to n Bu 4 NPF 6 , and the yield of 10-(2-phenylindolezin-3-yl)-10H-phenothiazine was 67%.
实施例11：10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-1))的制备Example 11: Preparation of 10-(2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-1))
反应步骤同实施例1，所不同的是支持电解质改为NaClO4，10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为75％。The reaction steps were the same as in Example 1, except that the supporting electrolyte was changed to NaClO 4 , and the yield of 10-(2-phenylindolezin-3-yl)-10H-phenothiazine was 75%.
实施例12：10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-1))的制备Example 12: Preparation of 10-(2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-1))
反应步骤同实施例1，所不同的是阳极改为石墨电极，10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为80％。The reaction steps are the same as in Example 1, except that the anode is changed to a graphite electrode, and the yield of 10-(2-phenylindole-3-yl)-10H-phenothiazine is 80%.
实施例13：10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-1))的制备Example 13: Preparation of 10-(2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-1))
反应步骤同实施例1，所不同的是阴极和阳极均改为石墨电极，10-(2- 苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为75％。The reaction steps were the same as in Example 1, except that the cathode and anode were both changed to graphite electrodes, and the yield of 10-(2-phenylindolezin-3-yl)-10H-phenothiazine was 75%.
实施例14：2-氯-10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-2))的制备Example 14: Preparation of 2-chloro-10-(2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-2))
反应步骤同实施例1，所不同的是吩噻嗪改为2-氯吩噻嗪，2-氯-10-(2- 苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为79％。The reaction steps are the same as in Example 1, and the difference is that phenothiazine is changed into 2-chlorophenothiazine, and the yield of 2-chloro-10-(2-phenylindolezin-3-yl)-10H-phenothiazine is The rate is 79%.
1H NMR(500MHz,CDCl3)δ7.82-7.78(m,3H),7.51(d,J＝8.9Hz, 1H),7.39-7.36(m,2H),7.27-7.24(m,1H),7.07(m,1H),6.97(d,J＝8.2Hz, 1H),6.93(s,1H),6.88–6.79(m,4H),6.57-6.55(m,1H),6.08-6.07(m,2H). 13C NMR(125MHz,CDCl3)δ142.9,141.1,133.7,133.5,131.2,129.0,127.9, 127.6,127.3,127.2,127.0,125.7,124.0,123.6,121.3,120.8,119.7,119.5, 119.0,116.1,115.96,115.6,111.6,97.2.HRMS(ESI)m/zcalculated for C26H18ClN2S+[M+H]+425.0874,found 425.0870. 1 H NMR (500MHz, CDCl 3 ) δ7.82-7.78(m, 3H), 7.51(d, J=8.9Hz, 1H), 7.39-7.36(m, 2H), 7.27-7.24(m, 1H), 7.07(m,1H),6.97(d,J＝8.2Hz,1H),6.93(s,1H),6.88–6.79(m,4H),6.57-6.55(m,1H),6.08-6.07(m, 2H). 13 C NMR (125MHz, CDCl 3 ) δ142.9, 141.1, 133.7, 133.5, 131.2, 129.0, 127.9, 127.6, 127.3, 127.2, 127.0, 125.7, 124.0, 123.6, 121.3, 120.8, 119.5, 116.1, 115.96, 115.6, 111.6, 97.2. HRMS (ESI) m/z calculated for C 26 H 18 ClN 2 S + [M+H] + 425.0874, found 425.0870.
实施例15：2-三氟甲基-10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-3)) 的制备Example 15: Preparation of 2-trifluoromethyl-10-(2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-3))
反应步骤同实施例1，所不同的是吩噻嗪改为2-三氟甲基吩噻嗪，2- 三氟甲基-10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为72％。The reaction steps are the same as in Example 1, except that phenothiazine is changed into 2-trifluoromethyl phenothiazine, 2-trifluoromethyl-10-(2-phenylindole-3-yl)-10H - The yield of phenothiazine was 72%.
1H NMR(500MHz,CDCl3)δ7.83-7.81(m,1H),7.76-7.72(m,2H), 7.51(d,J＝9.0Hz,1H),7.35(t,J＝7.7Hz,2H),7.27-7.22(m,1H),7.12(d,J ＝8.0Hz,1H),7.07-7.06(m,2H),6.93(s,1H),6.90-6.81(m,3H),6.59-6.54 (m,1H),6.27(d,J＝0.8Hz,1H),6.09-6.07(m,1H).13C NMR(125MHz, CDCl3)δ142.3,141.2,133.8,131.3,130.0(q,JC-F＝32.8Hz),129.0,128.2, 127.34,127.26,127.2,127.1,126.1,124.2,123.7(q,JC-F＝273.4Hz),121.3,120.24,120.23(q,JC-F＝3.8Hz),119.5,119.0,116.2,115.3,112.4(q,JC-F＝ 3.8Hz),111.6,97.4.19F NMR(377MHz,CDCl3)δ-63.13(s).HRMS(ESI) m/z calculated forC27H18F3N2S+[M+H]+459.1137,found 459.1135. 1 H NMR (500MHz, CDCl 3 ) δ7.83-7.81(m, 1H), 7.76-7.72(m, 2H), 7.51(d, J=9.0Hz, 1H), 7.35(t, J=7.7Hz, 2H),7.27-7.22(m,1H),7.12(d,J＝8.0Hz,1H),7.07-7.06(m,2H),6.93(s,1H),6.90-6.81(m,3H),6.59 -6.54 (m,1H),6.27(d,J＝0.8Hz,1H),6.09-6.07(m,1H). 13 C NMR(125MHz, CDCl 3 )δ142.3,141.2,133.8,131.3,130.0(q, J CF ＝32.8Hz),129.0,128.2,127.34,127.26,127.2,127.1,126.1,124.2,123.7(q,J CF ＝273.4Hz),121.3,120.24,120.23(q,J CF ＝3.8Hz),119.5 ,119.0,116.2,115.3,112.4(q,J CF = 3.8Hz),111.6,97.4. 19 F NMR(377MHz,CDCl 3 )δ-63.13(s).HRMS(ESI) m/z calculated for C 27 H 18 F 3 N 2 S + [M+H] + 459.1137, found 459.1135.
实施例16：2-乙酰基-10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-4))的制备Example 16: Preparation of 2-acetyl-10-(2-phenylindole-3-yl)-10H-phenothiazine (formula (I-4))
反应步骤同实施例1，所不同的是吩噻嗪改为2-乙酰基吩噻嗪，2-乙酰基-10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为72％。The reaction steps are the same as in Example 1, except that phenothiazine is changed to 2-acetyl phenothiazine, 2-acetyl-10-(2-phenylindole-3-yl)-10H-phenothiazine The yield was 72%.
1H NMR(600MHz,CDCl3)δ7.89(d,J＝7.0Hz,1H),7.80(d,J＝7.7 Hz,2H),7.53(d,J＝9.0Hz,1H),7.44-7.42(m,1H),7.37(t,J＝7.7Hz,2H), 7.28-7.25(m,1H),7.15-7.06(m,2H),6.96(s,1H),6.92-6.81(m,3H),6.67(d, J＝1.3Hz,1H),6.57(t,J＝6.7Hz,1H),6.15(d,J＝8.0Hz,1H),2.14(s,3H). 13C NMR(151MHz,CDCl3)δ196.8,141.6,141.3,136.5,134.0,131.2, 129.0,128.23,128.21,127.3,127.2,127.0,126.8,126.1,124.0,123.4,121.3, 120.3,119.5,118.9,116.2,115.54,115.52,111.5,97.3,26.3.HRMS(ESI)m/zcalculated for C28H21N2OS+[M+H]+433.1369,found 433.1367. 1 H NMR (600MHz, CDCl3) δ7.89(d, J=7.0Hz, 1H), 7.80(d, J=7.7 Hz, 2H), 7.53(d, J=9.0Hz, 1H), 7.44-7.42( m,1H),7.37(t,J＝7.7Hz,2H), 7.28-7.25(m,1H),7.15-7.06(m,2H),6.96(s,1H),6.92-6.81(m,3H) ,6.67(d, J＝1.3Hz, 1H), 6.57(t, J＝6.7Hz, 1H), 6.15(d, J＝8.0Hz, 1H), 2.14(s, 3H). 13 C NMR (151MHz, CDCl3)δ196.8,141.6,141.3,136.5,134.0,131.2, 129.0,128.23,128.21,127.3,127.2,127.0,126.8,126.1,124.0,123.4,121.3, 120.3,119.5,118.9,116.2,115.54,115.52,111.5, 97.3, 26.3.HRMS(ESI)m/zcalculated for C 28 H 21 N 2 OS + [M+H] + 433.1369, found 433.1367.
实施例17：2-氰基-10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-5))的制备Example 17: Preparation of 2-cyano-10-(2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-5))
反应步骤同实施例1，所不同的是吩噻嗪改为2-氰基吩噻嗪，2-氰基 -10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪收率为41％。The reaction steps are the same as in Example 1, except that phenothiazine is changed to 2-cyanophenothiazine, 2-cyano-10-(2-phenylindole-3-yl)-10H-phenothiazine The yield was 41%.
1H NMR(600MHz,CDCl3)δ7.76-7.72(m,3H),7.52(d,J＝8.9Hz, 1H),7.36-7.34(m,2H),7.26-7.24(m,1H)7.05-7.01(m,3H),6.91(s,1H), 6.88-6.81(m,3H),6.58-6.56(m,1H),6.15(s,1H),6.04(d,J＝7.9Hz, 1H).13C NMR(151MHz,CDCl3)δ142.4,140.5,133.5,131.5,129.0,128.5, 128.3,127.4,127.3,127.1,127.0,125.7,124.4,121.0,119.7,119.4,119.2, 118.6,118.0,116.2,114.8,111.9,111.0,97.5.HRMS(ESI)m/z calculatedfor C27H17N3SNa+[M+Na]+438.1035,found 438.1036. 1 H NMR (600MHz, CDCl 3 ) δ7.76-7.72 (m, 3H), 7.52 (d, J = 8.9Hz, 1H), 7.36-7.34 (m, 2H), 7.26-7.24 (m, 1H) 7.05 -7.01(m,3H),6.91(s,1H), 6.88-6.81(m,3H),6.58-6.56(m,1H),6.15(s,1H),6.04(d,J＝7.9Hz, 1H ). 13 C NMR (151MHz, CDCl 3 ) δ142.4, 140.5, 133.5, 131.5, 129.0, 128.5, 128.3, 127.4, 127.3, 127.1, 127.0, 125.7, 124.4, 121.0, 119.7, 168.4, 1119.2, 1119.2, 1119.2, 1119.2, , 114.8, 111.9, 111.0, 97.5. HRMS (ESI) m/z calculated for C 27 H 17 N 3 SNa + [M+Na] + 438.1035, found 438.1036.
实施例18：2-甲硫基-10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-6))的制备Example 18: Preparation of 2-methylthio-10-(2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-6))
反应步骤同实施例1，所不同的是吩噻嗪改为2-甲硫基吩噻嗪，2-甲硫基-10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为86％。The reaction steps are the same as in Example 1, and the difference is that phenothiazine is changed into 2-methylthiophenothiazine, 2-methylthio-10-(2-phenylindole-3-yl)-10H-phen The yield of thiazide was 86%.
1H NMR(500MHz,CDCl3)δ7.85(d,J＝7.1Hz,1H),7.81-7.77(m, 2H),7.47(d,J＝8.9Hz,1H),7.34(t,J＝7.7Hz,2H),7.25-7.21(m,1H), 7.10-7.08(m,1H),6.97(d,J＝8.5Hz,1H),6.91(s,1H),6.87-6.84(m,1H), 6.82-6.77(m,2H),6.55-6.50(m,1H),6.43-6.41(m,1H),6.13-6.11(m,1H), 5.78(d,J＝2.5Hz,1H),3.43(s,3H).13C NMR(125MHz,CDCl3)δ159.8, 143.0,141.5,134.0,131.0,129.0,127.6,127.4,127.2,127.1,127.0,125.8, 123.6,121.9,121.6,119.3,118.8,116.3,116.1,112.0,111.3,108.5,103.3,97.0,55.2.HRMS(ESI)calculated for C27H21N2S2 +[M+H]+:437.1141；found: 437.1124. 1 H NMR (500MHz, CDCl 3 ) δ7.85(d, J=7.1Hz, 1H), 7.81-7.77(m, 2H), 7.47(d, J=8.9Hz, 1H), 7.34(t, J= 7.7Hz, 2H), 7.25-7.21(m, 1H), 7.10-7.08(m, 1H), 6.97(d, J＝8.5Hz, 1H), 6.91(s, 1H), 6.87-6.84(m, 1H ), 6.82-6.77(m,2H),6.55-6.50(m,1H),6.43-6.41(m,1H),6.13-6.11(m,1H), 5.78(d,J＝2.5Hz,1H), 3.43(s,3H) .13C NMR(125MHz,CDCl 3 )δ159.8, 143.0,141.5,134.0,131.0,129.0,127.6,127.4,127.2,127.1,127.0,125.8, 123.6,121.9,121.6,119. 118.8, 116.3, 116.1, 112.0, 111.3, 108.5, 103.3, 97.0, 55.2. HRMS (ESI) calculated for C 27 H 21 N 2 S 2 + [M+H] + :437.1141; found: 437.1124.
实施例19：2-甲氧基-10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-7))的制备Example 19: Preparation of 2-methoxy-10-(2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-7))
反应步骤同实施例1，所不同的是吩噻嗪改为2-甲氧基吩噻嗪，2-甲氧基-10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为88％。The reaction steps are the same as in Example 1, except that phenothiazine is changed into 2-methoxyphenothiazine, 2-methoxy-10-(2-phenylindole-3-yl)-10H-phen The yield of thiazide was 88%.
1H NMR(500MHz,CDCl3)δ7.89-7.86(m,1H),7.79-7.78(m,2H), 7.48(d,J＝9.0Hz,1H),7.35(t,J＝7.7Hz,2H),7.25-7.22(m,1H),7.10-7.08 (m,1H),6.97(d,J＝8.1Hz,1H),6.92(s,1H),6.89-6.77(m,3H),6.76-6.74 m,1H),6.55-6.52(m,1H),6.16-6.14(m,1H),6.06(d,J＝1.9Hz,1H),2.00 (s,3H).13C NMR(125MHz,CDCl3)δ142.1,141.6,138.0,134.0,131.0, 129.0,127.7,127.2,127.0,126.0,123.7,122.0,121.6,121.5,119.3,118.8,118.0,116.2,116.0,114.2,111.37,96.9,15.7.HRMS(ESI)calculated for C27H20KN2S+[M+K]+:459.0928；found:459.0931. 1 H NMR (500MHz, CDCl 3 )δ7.89-7.86(m,1H),7.79-7.78(m,2H), 7.48(d,J=9.0Hz,1H),7.35(t,J=7.7Hz, 2H),7.25-7.22(m,1H),7.10-7.08(m,1H),6.97(d,J＝8.1Hz,1H),6.92(s,1H),6.89-6.77(m,3H),6.76 -6.74 m, 1H), 6.55-6.52 (m, 1H), 6.16-6.14 (m, 1H), 6.06 (d, J＝1.9Hz, 1H), 2.00 (s, 3H). 13 C NMR (125MHz, CDCl 3 )δ142.1, 141.6, 138.0, 134.0, 131.0, 129.0, 127.7, 127.2, 127.0, 126.0, 123.7, 122.0, 121.6, 121.5, 119.3, 118.8, 118.0, 116.2, 116.29 HR, 161.7 MS (ESI) calculated for C 27 H 20 KN 2 S + [M+K] + :459.0928; found: 459.0931.
实施例20：1-氯-10-(2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-8))的制备Example 20: Preparation of 1-chloro-10-(2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-8))
反应步骤同实施例1，所不同的是吩噻嗪改为1-氯吩噻嗪，1-氯-10-(2- 苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为55％。The reaction steps are the same as in Example 1, except that phenothiazine is changed to 1-chlorophenothiazine, and the yield of 1-chloro-10-(2-phenylindolezin-3-yl)-10H-phenothiazine is The rate is 55%.
1H NMR(400MHz,CDCl3)δ7.85(d,J＝7.0Hz,1H),7.83-7.77(m, 2H),7.49(d,J＝9.0Hz,1H),7.37(t,J＝7.7Hz,2H),7.27-7.23(m,1H), 7.09-7.08(m,1H),6.95-6.75(m,5H),6.67(t,J＝8.1Hz,1H),6.57-6.53(m, 1H),6.04-6.01(m,1H),5.94-5.92(m,1H).13CNMR(101MHz,CDCl3)δ 142.5,140.7,133.7,131.1,130.9,129.0,128.1,127.6,127.3,127.2,127.1, 125.7,123.8,121.4,121.1,119.9,119.4,118.9,115.9,115.8,113.9,111.5, 96.99.HRMS(ESI)m/z calculated for C26H18ClN2S+[M+H]+425.0874, found425.0874. 1 H NMR (400MHz, CDCl3) δ7.85(d, J=7.0Hz, 1H), 7.83-7.77(m, 2H), 7.49(d, J=9.0Hz, 1H), 7.37(t, J=7.7 Hz,2H),7.27-7.23(m,1H), 7.09-7.08(m,1H),6.95-6.75(m,5H),6.67(t,J＝8.1Hz,1H),6.57-6.53(m, 1H),6.04-6.01(m,1H),5.94-5.92(m,1H). 13 CNMR(101MHz,CDCl 3 )δ 142.5,140.7,133.7,131.1,130.9,129.0,128.1,127.6,127.3,127.2, 127.1, 125.7, 123.8, 121.4, 121.1, 119.9, 119.4, 118.9, 115.9, 115.8, 113.9, 111.5, 96.99.HRMS(ESI)m/z calculated for C 26 H 18 ClN 2 S + [M+H] + 425.0874 , found425.0874.
实施例21：10-(2-(对甲苯基)吲哚嗪-3-基)-10H-吩噻嗪(式(I-9))的制备Example 21: Preparation of 10-(2-(p-tolyl)indolezin-3-yl)-10H-phenothiazine (formula (I-9))
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，10-(2-(对甲苯基)吲哚嗪-3-基)-10H-吩噻嗪的收率为87％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindole azine is changed into 2-(p-tolyl) indole azine, 10-(2-(p-tolyl) indole azin-3-yl)- The yield of 10H-phenothiazine was 87%.
1H NMR(500MHz,CDCl3)δ7.86(d,J＝7.2Hz,1H),7.73(d,J＝8.2 Hz,2H),7.48(d,J＝9.0Hz,1H),7.17(d,J＝8.1Hz,2H),7.09-7.07(M,2H), 6.92(s,1H),6.86-6.85(M,2H),6.82-6.77(m,3H),6.53-6.50(m,1H), 6.13-6.11(m,2H),2.33(s,3H).13C NMR(125MHz,CDCl3)δ141.7,136.9, 131.0,129.7,129.3,127.7,127.0,126.9,125.7,123.5,121.6,121.2,119.2, 118.7,116.2,116.0,111.1,96.7,21.3.HRMS(ESI)m/z calculated forC27H21N2S+[M+H]+405.1420,found 405.1415. 1 H NMR (500MHz, CDCl 3 ) δ7.86(d, J=7.2Hz, 1H), 7.73(d, J=8.2 Hz, 2H), 7.48(d, J=9.0Hz, 1H), 7.17(d ,J=8.1Hz,2H),7.09-7.07(M,2H),6.92(s,1H),6.86-6.85(M,2H),6.82-6.77(m,3H),6.53-6.50(m,1H ), 6.13-6.11(m,2H),2.33(s,3H). 13 C NMR(125MHz,CDCl 3 )δ141.7,136.9, 131.0,129.7,129.3,127.7,127.0,126.9,125.7,123.5,121.6,121.2 ,119.2, 118.7,116.2,116.0,111.1,96.7,21.3.HRMS(ESI)m/z calculated for C 27 H 21 N 2 S + [M+H] + 405.1420,found 405.1415.
实施例22：10-(2-(4-甲氧基苯基)吲哚嗪-3-基)-10H-吩噻嗪(式(I-10)) 的制备Example 22: Preparation of 10-(2-(4-methoxyphenyl)indolezin-3-yl)-10H-phenothiazine (formula (I-10))
反应步骤同实施例1，所不同的是2-苯基吲哚嗪改为2-(4-甲氧基苯基)吲哚嗪，10-(2-(4-甲氧基苯基)吲哚嗪-3-基)-10H-吩噻嗪的收率为91％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 2-(4-methoxyphenyl) indolezine, 10-(2-(4-methoxyphenyl)indolezine The yield of pyrazin-3-yl)-10H-phenothiazine was 91%.
1H NMR(500MHz,CDCl3)δ7.85-7.82(m,1H),7.77-7.72(m,2H), 7.46(d,J＝9.0Hz,1H),7.08-7.06(m,2H),6.91-6.88(m,2H),6.86-6.82(m, 3H),6.81-6.77(m,3H),6.52-6.50(m,1H),6.11-6.10(m,2H),3.78(s,3H). 13C NMR(125MHz,CDCl3)δ158.9,141.7,131.0,128.3,127.7,127.0,126.5, 125.5,123.6,121.6,121.2,119.1,118.7,115.94,115.86,114.4,111.0,96.4, 55.3.HRMS(ESI)m/z calculated for C27H21N2OS+[M+H]+421.1369,found 421.1366. 1 H NMR (500MHz, CDCl 3 )δ7.85-7.82(m,1H),7.77-7.72(m,2H), 7.46(d,J=9.0Hz,1H),7.08-7.06(m,2H), 6.91-6.88(m,2H),6.86-6.82(m,3H),6.81-6.77(m,3H),6.52-6.50(m,1H),6.11-6.10(m,2H),3.78(s,3H ). 13 C NMR (125MHz, CDCl 3 ) δ158.9, 141.7, 131.0, 128.3, 127.7, 127.0, 126.5, 125.5, 123.6, 121.6, 121.2, 119.1, 118.7, 115.94, 115.85, 114.4, 114.0, HR, (ESI)m/z calculated for C 27 H 21 N 2 OS + [M+H] + 421.1369, found 421.1366.
实施例23：10-(2-(4-溴苯基)吲哚嗪-3-基)-10H-吩噻嗪(式(I-11))的制备Example 23: Preparation of 10-(2-(4-bromophenyl)indolezin-3-yl)-10H-phenothiazine (formula (I-11))
反应步骤同实施例1，所不同的是2-苯基吲哚嗪改为2-(4-溴苯基)吲哚嗪，10-(2-(4-溴苯基)吲哚嗪-3-基)-10H-吩噻嗪的收率为75％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 2-(4-bromophenyl) indolezine, 10-(2-(4-bromophenyl) indolezine-3 The yield of -yl)-10H-phenothiazine was 75%.
1H NMR(500MHz,CDCl3)δ7.83-7.81(m,1H),7.69-7.64(m,2H), 7.50-7.44(m,3H),7.08-7.06(m,2H),6.87-6.83(m,3H),6.82-6.78(m,3H), 6.55-6.52(m,1H),6.05-6.03m,2H).13C NMR(125MHz,CDCl3)δ141.5, 132.9,132.1,131.1,128.7,127.8,127.1,124.4,123.7,121.7,121.2,121.1, 119.4,119.0,116.6,115.7,111.6,96.7.HRMS(ESI)m/zcalculated for C26H18BrN2S+[M+H]+469.0369,found 469.0369. 1 H NMR (500MHz, CDCl 3 )δ7.83-7.81(m,1H),7.69-7.64(m,2H), 7.50-7.44(m,3H),7.08-7.06(m,2H),6.87-6.83 (m,3H),6.82-6.78(m,3H), 6.55-6.52(m,1H),6.05-6.03m,2H). 13 C NMR(125MHz,CDCl 3 )δ141.5, 132.9,132.1,131.1 ,128.7,127.8,127.1,124.4,123.7,121.7,121.2,121.1, 119.4,119.0,116.6,115.7,111.6,96.7.HRMS(ESI)m/zcalculated for C 26 H 18 BrN 2 S + [M+H] + 469.0369,found 469.0369.
实施例24：10-(2-(4-氟苯基)吲哚嗪-3-基)-10H-吩噻嗪(式(I-12))的制备Example 24: Preparation of 10-(2-(4-fluorophenyl)indolezin-3-yl)-10H-phenothiazine (formula (I-12))
反应步骤同实施例1，所不同的是2-苯基吲哚嗪改为2-(4-氟苯基)吲哚嗪，展开剂为石油醚，10-(2-(4-氟苯基)吲哚嗪-3-基)-10H-吩噻嗪的收率为73％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 2-(4-fluorophenyl) indolezine, and developing agent is sherwood oil, 10-(2-(4-fluorophenyl The yield of )indolezin-3-yl)-10H-phenothiazine was 73%.
1H NMR(400MHz,CDCl3)δ7.85-7.78m,3H),7.50(d,J＝9.0Hz,1H), 7.13-7.01(m,4H),6.91-6.77(m,6H),6.56 -6.52m,1H),6.09(d,J＝8.0Hz, 2H).13C NMR(101MHz,CDCl3)δ162.09(d,JC-F＝246.4Hz),141.6,131.1, 130.1(d,JC-F＝3.1Hz),128.8(d,JC-F＝7.9Hz),127.7,127.1,124.6,123.7, 121.6,121.1,119.3,118.9,116.2,115.9,115.7(d,JC-F＝3.1Hz),111.4,96.7. 19F NMR(377MHz,CDCl3)δ-115.22(s).HRMS(ESI)m/z calculatedfor C26H18FN2S+[M+H]+409.1169,found 409.1169. 1 H NMR (400MHz, CDCl 3 )δ7.85-7.78m, 3H), 7.50(d, J=9.0Hz, 1H), 7.13-7.01(m, 4H), 6.91-6.77(m, 6H), 6.56 -6.52m, 1H), 6.09(d, J＝8.0Hz, 2H). 13 C NMR (101MHz, CDCl 3 ) δ162.09(d, J CF ＝246.4Hz), 141.6, 131.1, 130.1(d, J CF =3.1Hz),128.8(d,J CF =7.9Hz),127.7,127.1,124.6,123.7,121.6,121.1,119.3,118.9,116.2,115.9,115.7(d,J CF =3.1Hz),111.4, 96.7. 19 F NMR(377MHz,CDCl 3 )δ-115.22(s).HRMS(ESI)m/z calculated for C 26 H 18 FN 2 S + [M+H] + 409.1169,found 409.1169.
实施例25：10-(2-(4-氯苯基)吲哚嗪-3-基)-10H-吩噻嗪(式(I-13))的制备Example 25: Preparation of 10-(2-(4-chlorophenyl)indolezin-3-yl)-10H-phenothiazine (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-(4-氯苯基)吲哚嗪，10-(2-(4-氯苯基)吲哚嗪-3-基)-10H-吩噻嗪的收率为83％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 2-(4-chlorophenyl) indolezine, 10-(2-(4-chlorophenyl) indolezine-3 The yield of -yl)-10H-phenothiazine was 83%.
1H NMR(500MHz,CDCl3)δ7.84-7.82(m,1H),7.77-7.71(m,2H),7.49 (d,J＝9.0Hz,1H),7.34-7.29(m,2H),7.09-7.07(m,2H),6.89-6.78(m,6H), 6.56-6.51(m,1H),6.07-6.05(m,2H).13C NMR(125MHz,CDCl3)δ141.5, 132.9,132.4,131.1,129.1,128.4,127.7,127.1,124.4,123.7,121.6,121.2, 119.4,119.01,116.5,115.7,111.5,96.7.HRMS(ESI)m/z calculated for C26H18ClN2S+[M+H]+425.0874,found 425.0870. 1 H NMR (500MHz, CDCl 3 ) δ7.84-7.82 (m, 1H), 7.77-7.71 (m, 2H), 7.49 (d, J=9.0Hz, 1H), 7.34-7.29 (m, 2H), 7.09-7.07(m,2H),6.89-6.78(m,6H), 6.56-6.51(m,1H),6.07-6.05(m,2H). 13 C NMR(125MHz,CDCl 3 )δ141.5, 132.9 , 132.4,131.1,129.1,128.4,127.7,127.1,124.4,123.7,121.6,121.2 , 119.4,119.01,116.5,115.7,111.5,96.7 . [M+H] + 425.0874, found 425.0870.
实施例26：10-(2-(2-氟苯基)吲哚嗪-3-基)-10H-吩噻嗪(式(I-14))的制备Example 26: Preparation of 10-(2-(2-fluorophenyl)indolezin-3-yl)-10H-phenothiazine (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-(2-氟苯基)吲哚嗪，10-(2-(2-氟苯基)吲哚嗪-3-基)-10H-吩噻嗪的收率为70％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 2-(2-fluorophenyl) indolezine, 10-(2-(2-fluorophenyl) indolezine-3 The yield of -yl)-10H-phenothiazine was 70%.
1H NMR(400MHz,CDCl3)δ7.77(d,J＝7.0Hz,1H),7.74-7.70m,1H), 7.55(d,J＝9.0Hz,1H),7.25-7.04(m,6H),6.88-6.80(m,4H),6.58-6.52(m, 1H),6.04-6.02(m,2H).13CNMR(101MHz,CDCl3)δ160.3(d,JC-F＝249.3 Hz),141.7,130.7(d,JC-F＝1.4Hz),130.0(d,JC-F＝3.5Hz),128.7(d,JC-F＝ 8.5Hz),127.7,127.0,124.5(d,JC-F＝3.5Hz),123.5,121.8(d,JC-F＝12.4Hz), 121.5,120.7,119.7(d,JC-F＝8.0Hz),118.6,117.1,116.3,116.0,115.5,111.5, 100.0(d,JC-F＝9.5Hz).19F NMR(377MHz,CDCl3)δ-114.43(s).HRMS (ESI)m/z calculated for C26H18FN2S+[M+H]+409.1169,found 409.1169. 1 H NMR (400MHz, CDCl 3 ) δ7.77(d, J=7.0Hz, 1H), 7.74-7.70m, 1H), 7.55(d, J=9.0Hz, 1H), 7.25-7.04(m, 6H ),6.88-6.80(m,4H),6.58-6.52(m, 1H),6.04-6.02(m,2H). 13 CNMR(101MHz,CDCl 3 )δ160.3(d,J CF ＝249.3 Hz), 141.7,130.7(d,J CF ＝1.4Hz),130.0(d,J CF ＝3.5Hz),128.7(d,J CF ＝8.5Hz),127.7,127.0,124.5(d,J CF ＝3.5Hz), 123.5,121.8(d,J CF ＝12.4Hz), 121.5,120.7,119.7(d,J CF ＝8.0Hz),118.6,117.1,116.3,116.0,115.5,111.5, 100.0(d,J CF ＝9.5Hz) . 19 F NMR(377MHz,CDCl 3 )δ-114.43(s).HRMS (ESI)m/z calculated for C 26 H 18 FN 2 S + [M+H] + 409.1169,found 409.1169.
实施例27：10-(2-(2-氯苯基)吲哚嗪-3-基)-10H-吩噻嗪(式(I-15))的制备Example 27: Preparation of 10-(2-(2-chlorophenyl)indolezin-3-yl)-10H-phenothiazine (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-(2-氯苯基)吲哚嗪，10-(2-(2-氯苯基)吲哚嗪-3-基)-10H-吩噻嗪的收率为77％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 2-(2-chlorophenyl) indolezine, 10-(2-(2-chlorophenyl) indolezine-3 The yield of -yl)-10H-phenothiazine was 77%.
1H NMR(400MHz,DMSO)δ7.57-7.54(m,2H),7.39-7.37(m,1H), 7.20-7.07(m,3H),6.95-6.89(m,2H),6.84-6.70(m,6H),6.59-6.53(m,1H), 5.73-5.66(m,2H).13C NMR(101MHz,DMSO)δ141.3,132.6,132.5, 131.05,130.1,130.0,129.2,127.8,127.1,126.9,123.7,122.5,121.5,119.7, 119.0,18.9,116.8,114.6,111.9,100.3.HRMS(ESI)m/zcalculated for C26H18ClN2S+[M+H]+425.0874,found 425.0870. 1 H NMR (400MHz,DMSO)δ7.57-7.54(m,2H),7.39-7.37(m,1H), 7.20-7.07(m,3H),6.95-6.89(m,2H),6.84-6.70( m,6H),6.59-6.53(m,1H), 5.73-5.66(m,2H). 13 C NMR(101MHz,DMSO)δ141.3,132.6,132.5, 131.05,130.1,130.0,129.2,127.8,127.1,126.9 ,123.7,122.5,121.5,119.7, 119.0,18.9,116.8,114.6,111.9,100.3. HRMS(ESI)m/z calculated for C 26 H 18 ClN 2 S + [M+H] + 425.0874,found 425.0870.
实施例28：10-(2-(3-甲氧基苯基)吲哚嗪-3-基)-10H-吩噻嗪(式(I-16)) 的制备Example 28: Preparation of 10-(2-(3-methoxyphenyl)indolezin-3-yl)-10H-phenothiazine (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-(3-甲氧基苯基)吲哚嗪，10-(2-(3-甲氧基苯基)吲哚嗪-3-基)-10H-吩噻嗪的收率为88％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 2-(3-methoxyphenyl) indolezine, 10-(2-(3-methoxyphenyl)indolezine The yield of pyrazin-3-yl)-10H-phenothiazine was 88%.
1H NMR(500MHz,CDCl3)δ7.82-7.80(m,1H),7.50(d,J＝8.9Hz, 1H),7.43-7.36(m,2H),7.28-7.24(m,1H),7.06-7.05(m,2H),6.92(s,1H), 6.87-6.76(m,6H),6.54-6.51(m,1H),6.06-6.04(m,2H),3.69(s,3H).13C NMR(125MHz,CDCl3)δ156.0,141.6,135.2,131.0,129.8,127.7,126.9, 125.3,123.6,121.6,120.8,119.7,119.4,118.8,116.4,115.8,113.7,111.9, 111.3,97.1,55.1.HRMS(ESI)m/z calculated for C27H21N2OS+(M+H)+421.1369,found 421.1365. 1 H NMR (500MHz, CDCl 3 )δ7.82-7.80(m,1H),7.50(d,J=8.9Hz,1H),7.43-7.36(m,2H),7.28-7.24(m,1H), 7.06-7.05(m,2H),6.92(s,1H), 6.87-6.76(m,6H),6.54-6.51(m,1H),6.06-6.04(m,2H),3.69(s,3H). 13 C NMR (125MHz, CDCl 3 ) δ156.0, 141.6, 135.2, 131.0, 129.8, 127.7, 126.9, 125.3, 123.6, 121.6, 120.8, 119.7, 119.4, 118.8, 116.4, 115.8, 113.1, 111.1 .HRMS(ESI)m/z calculated for C 27 H 21 N 2 OS + (M+H) + 421.1369,found 421.1365.
实施例29：10-(2-(3-氯苯基)吲哚嗪-3-基)-10H-吩噻嗪(式(I-17))的制备Example 29: Preparation of 10-(2-(3-chlorophenyl)indolezin-3-yl)-10H-phenothiazine (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-(3-氯苯基)吲哚嗪，10-(2-(3-氯苯基)吲哚嗪-3-基)-10H-吩噻嗪的收率为82％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 2-(3-chlorophenyl) indolezine, 10-(2-(3-chlorophenyl) indolezine-3 The yield of -yl)-10H-phenothiazine was 82%.
1H NMR(500MHz,CDCl3)δ7.81-7.80(m,2H),7.67-7.66(m,1H), 7.50(d,J＝9.0Hz,1H),7.25–7.18(m,2H),7.08-7.07(m,2H),6.88(s,1H), 6.87-6.78(m,5H),6.56-6.52(m,1H),6.04-6.02(m,2H).13C NMR(125MHz, CDCl3)δ141.6,135.8,134.7,131.1,130.2,127.7,127.4,127.1,125.2,124.0, 123.7,121.7,121.3,119.5,119.1,116.9,115.7,115.2,111.6,97.0.HRMS (ESI)m/z calculated for C26H18ClN2S+[M+H]+425.0874,found425.0877. 1 H NMR (500MHz, CDCl 3 ) δ7.81-7.80(m, 2H), 7.67-7.66(m, 1H), 7.50(d, J=9.0Hz, 1H), 7.25–7.18(m, 2H), 7.08-7.07(m,2H),6.88(s,1H), 6.87-6.78(m,5H),6.56-6.52(m,1H),6.04-6.02(m,2H). 13 C NMR(125MHz, CDCl 3 ) δ141.6, 135.8, 134.7, 131.1, 130.2, 127.7, 127.4, 127.1, 125.2, 124.0, 123.7, 121.7, 121.3, 119.5, 119.1, 116.9, 115.7, 115.2, 111.6, 97.0 mS (ulESIcIz) for C 26 H 18 ClN 2 S + [M+H] + 425.0874, found 425.0877.
实施例30：10-(2-(3-溴苯基)吲哚嗪-3-基)-10H-吩噻嗪(式(I-18))的制备Example 30: Preparation of 10-(2-(3-bromophenyl)indolazin-3-yl)-10H-phenothiazine (Formula (I-18))
反应步骤同实施例1，所不同的是2-苯基吲哚嗪改为2-(3-溴苯基)吲哚嗪，10-(2-(3-溴苯基)吲哚嗪-3-基)-10H-吩噻嗪的收率为77％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 2-(3-bromophenyl) indolezine, 10-(2-(3-bromophenyl) indolezine-3 The yield of -yl)-10H-phenothiazine was 77%.
1H NMR(500MHz,CDCl3)δ7.97(t,J＝1.8Hz,1H),7.79(d,J＝7.0 Hz,1H),7.73-7.68(m,1H),7.52-7.45(m,1H),7.35-7.33(m,1H),7.17(t,J＝ 7.9Hz,1H),7.09-7.07(m,2H),6.88-6.78(m,6H),6.56-6.53(m,1H), 6.03-6.01(m,2H).13C NMR(125MHz,CDCl3)δ141.6,136.1,131.1,130.5, 130.3,123.0,127.7,127.1,125.6,123.8,123.7,123.0,121.7,121.3,119.6, 119.1,116.9,115.7,111.6,96.9.HRMS(ESI)m/z calculated forC26H18BrN2S+[M+H]+469.0369,found 469.0370. 1 H NMR (500MHz, CDCl 3 ) δ7.97(t, J=1.8Hz, 1H), 7.79(d, J=7.0 Hz, 1H), 7.73-7.68(m, 1H), 7.52-7.45(m, 1H),7.35-7.33(m,1H),7.17(t,J＝7.9Hz,1H),7.09-7.07(m,2H),6.88-6.78(m,6H),6.56-6.53(m,1H) , 6.03-6.01(m,2H). 13 C NMR(125MHz,CDCl 3 )δ141.6,136.1,131.1,130.5, 130.3,123.0,127.7,127.1,125.6,123.8,123.7,123.0,121.7,121.3,119. ,116.9,115.7,111.6,96.9.HRMS(ESI)m/z calculated for C 26 H 18 BrN 2 S + [M+H] + 469.0369,found 469.0370.
实施例31：10-(2-(3,4-二甲氧基苯基)吲哚嗪-3-基)-10H-吩噻嗪(式(I-19)) 的制备Example 31: Preparation of 10-(2-(3,4-dimethoxyphenyl)indolezin-3-yl)-10H-phenothiazine (Formula (I-19))
反应步骤同实施例1，所不同的是2-苯基吲哚嗪改为2-(3,4-二甲氧基苯基)吲哚嗪，10-(2-(3,4-二甲氧基苯基)吲哚嗪-3-基)-10H-吩噻嗪的收率为 84％。The reaction steps are the same as in Example 1, except that 2-phenylindolezine is changed into 2-(3,4-dimethoxyphenyl) indolezine, 10-(2-(3,4-dimethyl The yield of oxyphenyl)indolezin-3-yl)-10H-phenothiazine was 84%.
1H NMR(500MHz,CDCl3)δ7.81-7.75(m,1H),7.48(d,J＝8.9Hz, 1H),7.40-7.33(m,2H),7.04(dd,J＝7.4,1.7Hz,2H),6.90-6.77(m,7H), 6.51(td,J＝7.0,1.0Hz,1H),6.04-6.02m,2H),3.86(s,3H),3.71(s,3H).13C NMR(125MHz,CDCl3)δ149.0,148.2,141.5,131.1,127.8,126.9,126.8, 125.1,123.6,121.5,120.6,119.5,119.2,118.7,115.8,115.7,111.5,111.1, 110.4,96.6,55.9,55.6.HRMS(ESI)m/z calculated for C28H23N2O2S+ [M+H]+451.1475,found 451.1473. 1 H NMR (500MHz, CDCl 3 ) δ7.81-7.75 (m, 1H), 7.48 (d, J = 8.9Hz, 1H), 7.40-7.33 (m, 2H), 7.04 (dd, J = 7.4, 1.7 Hz,2H),6.90-6.77(m,7H), 6.51(td,J＝7.0,1.0Hz,1H),6.04-6.02m,2H),3.86(s,3H),3.71(s,3H). 13 C NMR (125MHz, CDCl 3 ) δ149.0, 148.2, 141.5, 131.1, 127.8, 126.9, 126.8, 125.1, 123.6, 121.5, 120.6, 119.5, 119.2, 118.7, 115.8, 115.55, 111.5, 110.6, 110.6 ,55.6.HRMS(ESI)m/z calculated for C 28 H 23 N 2 O 2 S + [M+H] + 451.1475,found 451.1473.
实施例32：10-(2-(3,4-二氯苯基)吲哚嗪-3-基)-10H-吩噻嗪(式(I-20)) 的制备Example 32: Preparation of 10-(2-(3,4-dichlorophenyl)indolezin-3-yl)-10H-phenothiazine (Formula (I-20))
反应步骤同实施例1，所不同的是2-苯基吲哚嗪改为2-(3,4-二氯苯基) 吲哚嗪，10-(2-(3,4-二氯苯基)吲哚嗪-3-基)-10H-吩噻嗪的收率为79％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 2-(3,4-dichlorophenyl) indolezine, 10-(2-(3,4-dichlorophenyl The yield of )indolezin-3-yl)-10H-phenothiazine was 79%.
1H NMR(400MHz,CDCl3)δ7.90(d,J＝2.1Hz,1H),7.78(d,J＝7.0 Hz,1H),7.62-7.60(m,1H),7.53-7.47(m,1H),7.37(d,J＝8.4Hz,1H), 7.10-7.07(m,2H),6.91-6.78(m,6H),6.58-6.54(m,1H),6.01-6.98(m,2H). 13C NMR(101MHz,CDCl3)δ141.5,134.1,132.8,131.2,130.9,129.1,127.8, 127.2,126.3,123.9,122.9,121.7,121.3,119.6,119.3,117.0,115.5,115.1, 111.8,96.8.HRMS(ESI)m/z calculated for C26H17Cl2N2S+(M+H)+459.0484, found 459.0482. 1 H NMR (400MHz, CDCl 3 ) δ7.90(d, J=2.1Hz, 1H), 7.78(d, J=7.0 Hz, 1H), 7.62-7.60(m, 1H), 7.53-7.47(m, 1H),7.37(d,J＝8.4Hz,1H), 7.10-7.07(m,2H),6.91-6.78(m,6H),6.58-6.54(m,1H),6.01-6.98(m,2H) . 13 C NMR (101MHz, CDCl 3 ) δ141.5, 134.1, 132.8, 131.2, 130.9, 129.1, 127.8, 127.2, 126.3, 123.9, 122.9, 121.7, 121.3, 119.6, 119.3, 117.0, 115.5, 115 HRMS(ESI)m/z calculated for C 26 H 17 Cl 2 N 2 S + (M+H) + 459.0484, found 459.0482.
实施例33：10-(8-甲基-2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-21))的制备Example 33: Preparation of 10-(8-methyl-2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-21))
反应步骤同实施例1，所不同的是2-苯基吲哚嗪改为8-甲基-2-苯基吲哚嗪，10-(8-甲基-2-苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为86％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 8-methyl-2-phenylindolezine, 10-(8-methyl-2-phenylindolezine-3 The yield of -yl)-10H-phenothiazine was 86%.
1H NMR(500MHz,CDCl3)δ7.84-7.82(m,2H),7.74(d,J＝6.9Hz, 1H),7.35(t,J＝7.7Hz,2H),7.24(d,J＝7.4Hz,1H),7.07-7.05(m,2H),6.90 (s,1H),6.85-6.77(m,4H),6.63(d,J＝6.5Hz,1H),6.48(t,J＝6.8Hz,1H), 6.10-6.08(m,2H),2.53(s,3H).13C NMR(125MHz,CDCl3)δ141.8,134.1, 131.9,128.9,128.4,127.7,127.2,127.0,126.9,125.1,123.5,121.1,119.7, 118.1,116.9,115.9,111.5,95.4,17.9.HRMS(ESI)m/z calculatedfor C27H21N2S+[M+H]+405.1420,found 405.1418. 1 H NMR (500MHz, CDCl 3 ) δ7.84-7.82(m, 2H), 7.74(d, J=6.9Hz, 1H), 7.35(t, J=7.7Hz, 2H), 7.24(d, J= 7.4Hz,1H),7.07-7.05(m,2H),6.90(s,1H),6.85-6.77(m,4H),6.63(d,J＝6.5Hz,1H),6.48(t,J＝6.8 Hz,1H), 6.10-6.08(m,2H),2.53(s,3H). 13 C NMR(125MHz,CDCl 3 )δ141.8,134.1, 131.9,128.9,128.4,127.7,127.2,127.0,126.9,125.1, 123.5, 121.1, 119.7, 118.1, 116.9, 115.9, 111.5, 95.4, 17.9. HRMS (ESI) m/z calculated for C 27 H 21 N 2 S + [M+H] + 405.1420, found 405.1418.
实施例34：10-(7-甲基-2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-22))的制备Example 34: Preparation of 10-(7-methyl-2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-22))
反应步骤同实施例1，所不同的是2-苯基吲哚嗪改为7-甲基-2-苯基吲哚嗪，10-(7-甲基-2-苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为90％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 7-methyl-2-phenylindolezine, 10-(7-methyl-2-phenylindolezine-3 The yield of -yl)-10H-phenothiazine was 90%.
1H NMR(400MHz,CDCl3)δ7.85-7.80(m,2H),7.76(d,J＝7.1Hz, 1H),7.40-7.33(m,2H),7.28-7.21(m,2H),7.11-7.06(m,2H),6.89-6.78(m, 5H),6.40-6.38(m,1H),6.13-6.10(m,2H),2.34(s,3H).13C NMR(101MHz, CDCl3)δ141.8,134.1,131.4,129.0,128.9,127.7,127.1,127.0,126.9,125.3, 123.5,121.2,121.1,117.4,115.9,115.7,114.0,95.2,21.2.HRMS(ESI)m/z calculated for C27H21N2S+(M+H)+405.1420,found 405.1418. 1 H NMR (400MHz, CDCl 3 )δ7.85-7.80(m,2H),7.76(d,J=7.1Hz,1H),7.40-7.33(m,2H),7.28-7.21(m,2H), 7.11-7.06(m,2H),6.89-6.78(m,5H),6.40-6.38(m,1H),6.13-6.10(m,2H),2.34(s,3H). 13 C NMR(101MHz, CDCl 3 ) δ141.8, 134.1, 131.4, 129.0, 128.9, 127.7, 127.1, 127.0, 126.9, 125.3, 123.5, 121.2, 121.1, 117.4, 115.9, 115.7, 114.0, 95.2, 21.2. 27 H 21 N 2 S + (M+H) + 405.1420, found 405.1418.
实施例35：10-(6-甲基-2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-23))的制备Example 35: Preparation of 10-(6-methyl-2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-23))
反应步骤同实施例1，所不同的是2-苯基吲哚嗪改为6-甲基-2-苯基吲哚嗪，10-(6-甲基-2-苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为85％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 6-methyl-2-phenylindolezine, 10-(6-methyl-2-phenylindolezine-3 The yield of -yl)-10H-phenothiazine was 85%.
1H NMR(500MHz,CDCl3)δ7.81-7.79(m,2H),7.63(s,1H),7.41(d,J ＝9.0Hz,1H),7.34(t,J＝7.7Hz,2H),7.23-7.20(m,1H),7.08-7.06(m,2H), 6.86-6.80(m,5H),6.67(d,J＝8.8Hz,1H),6.11-6.09(m,2H),2.19(d,J＝ 0.6Hz,3H).13C NMR(125MHz,CDCl3)δ141.7,134.1,130.0,129.5,128.9, 127.7,127.1,126.9,125.1,123.5,122.2,121.1,120.9,119.0,118.9,116.2, 115.9,115.3,18.8.HRMS(ESI)m/z calculated for C27H21N2S+[M+H]+405.1420,found 405.1415. 1 H NMR (500MHz, CDCl 3 ) δ7.81-7.79 (m, 2H), 7.63 (s, 1H), 7.41 (d, J = 9.0Hz, 1H), 7.34 (t, J = 7.7Hz, 2H) ,7.23-7.20(m,1H),7.08-7.06(m,2H), 6.86-6.80(m,5H),6.67(d,J＝8.8Hz,1H),6.11-6.09(m,2H),2.19 (d, J＝ 0.6Hz, 3H). 13 C NMR (125MHz, CDCl 3 ) δ141.7, 134.1, 130.0, 129.5, 128.9, 127.7, 127.1, 126.9, 125.1, 123.5, 122.2, 121.1, 120.9, 119.0, 118.9, 116.2, 115.9, 115.3, 18.8. HRMS(ESI) m/z calculated for C 27 H 21 N 2 S + [M+H] + 405.1420, found 405.1415.
实施例36：10-(7-溴-2-苯基吲哚嗪-3-基)-10H-吩噻嗪(式(I-24))的制备Example 36: Preparation of 10-(7-bromo-2-phenylindolezin-3-yl)-10H-phenothiazine (formula (I-24))
反应步骤同实施例1，所不同的是2-苯基吲哚嗪改为7-溴-2-苯基吲哚嗪，10-(7-溴-2-苯基吲哚嗪-3-基)-10H-吩噻嗪的收率为68％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 7-bromo-2-phenylindolezine, 10-(7-bromo-2-phenylindolezine-3-yl )-10H-phenothiazine yield was 68%.
1H NMR(400MHz,CDCl3)δ7.78(d,J＝1.2Hz,1H),7.62-7.54(m, 3H),7.36(t,J＝7.4Hz,2H),7.33-7.28(m,1H),7.02-6.98(m,2H),6.86-6.77 (m,5H),6.67-6.64(m,1H),5.96-5.94(m,2H).13C NMR(101MHz,CDCl3) δ141.5,131.5,129.6,129.4,128.6,128.0,127.7,127.1,126.2,123.8,122.6, 120.7,120.4,117.9,115.9,115.2,113.4,85.6.HRMS(ESI)m/z calculated for C26H18BrN2S+[M+H]+469.0369,found 469.0364. 1 H NMR (400MHz, CDCl 3 ) δ7.78(d, J=1.2Hz, 1H), 7.62-7.54(m, 3H), 7.36(t, J=7.4Hz, 2H), 7.33-7.28(m, 1H),7.02-6.98(m,2H),6.86-6.77(m,5H),6.67-6.64(m,1H),5.96-5.94(m,2H). 13 C NMR(101MHz,CDCl 3 ) δ141. 5 , 131.5, 129.6, 129.4, 128.6, 128.0, 127.7, 127.1 , 126.2, 123.8 , 122.6, 120.7, 120.4, 117.9, 115.9, 115.2, 113.4, 85.6. + [M+H] + 469.0369, found 469.0364.
实施例37：10-(2-(4-氯苯基)-7-甲基吲哚嗪-3-基)-10H-吩噻嗪(式(I-25)) 的制备Example 37: Preparation of 10-(2-(4-chlorophenyl)-7-methylindolezin-3-yl)-10H-phenothiazine (Formula (I-25))
反应步骤同实施例1，所不同的是2-苯基吲哚嗪改为2-(4-氯苯基)-7- 甲基吲哚嗪，10-(2-(4-氯苯基)-7-甲基吲哚嗪-3-基)-10H-吩噻嗪的收率为 75％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 2-(4-chlorophenyl)-7-methylindolezine, 10-(2-(4-chlorophenyl) The yield of -7-methylindolazin-3-yl)-10H-phenothiazine was 75%.
1H NMR(400MHz,CDCl3)δ7.78-7.70(m,3H),7.36-7.29(m,3H), 7.10-7.08(m,2H),6.89-6.80(m,4H),6.74(s,1H),6.41-6.39(m,1H), 6.08-6.05(m,2H),2.34(s,3H).13C NMR(101MHz,CDCl3)δ141.7,132.7, 132.6,131.5,129.5,129.0,128.3,127.7,127.0,124.1,123.6,121.2,121.1, 117.48,115.9,115.7,114.2,95.1,21.2.HRMS(ESI)m/z calculatedfor C27H20ClN2S+[M+H]+439.1030,found 439.1032. 1 H NMR (400MHz, CDCl 3 )δ7.78-7.70(m,3H),7.36-7.29(m,3H), 7.10-7.08(m,2H),6.89-6.80(m,4H),6.74(s ,1H),6.41-6.39(m,1H), 6.08-6.05(m,2H),2.34(s,3H). 13 C NMR(101MHz,CDCl 3 )δ141.7,132.7, 132.6,131.5,129.5,129.0, 128.3,127.7,127.0,124.1,123.6,121.2,121.1, 117.48,115.9,115.7,114.2,95.1,21.2.HRMS(ESI)m/z calculated for C 27 H 20 ClN 2 S + [M+H] + 439.1030, found 439.1032.
实施例38：10-(2-(萘-2-基)吲哚嗪-3-基)-10H-吩噻嗪(式(I-26))的制备Example 38: Preparation of 10-(2-(naphthalen-2-yl)indolazin-3-yl)-10H-phenothiazine (Formula (I-26))
反应步骤同实施例1，所不同的是2-苯基吲哚嗪改为2-(萘-2-基)吲哚嗪，10-(2-(萘-2-基)吲哚嗪-3-基)-10H-吩噻嗪(式26)的收率为73％。The reaction steps are the same as in Example 1, and the difference is that 2-phenylindolezine is changed into 2-(naphthalene-2-yl) indolezine, 10-(2-(naphthalene-2-yl) indolezine-3 The yield of -yl)-10H-phenothiazine (Formula 26) was 73%.
1H NMR(500MHz,CDCl3)δ8.41(d,J＝1.0Hz,1H),7.99-7.97(m, 1H),7.89-7.76(m,4H),7.54(d,J＝9.0Hz,1H),7.48-7.40(m,2H),7.13-7.11 (m,2H),7.08(s,1H),6.89-6.78(m,5H),6.57-6.54(m,1H),6.17-6.15(m, 2H).13C NMR(125MHz,CDCl3)δ141.8,133.7,132.6,131.3,131.2,128.5, 128.4,127.8,127.6,127.0,126.1,126.0,125.9,125.5,125.2,123.7,121.6, 121.3,119.4,118.8,117.0,115.9,111.4,97.1.HRMS(ESI)m/zcalculated for C30H21N2S+[M+H]+441.1420,found 441.1416. 1 H NMR (500MHz, CDCl 3 ) δ8.41(d, J=1.0Hz, 1H), 7.99-7.97(m, 1H), 7.89-7.76(m, 4H), 7.54(d, J=9.0Hz, 1H),7.48-7.40(m,2H),7.13-7.11(m,2H),7.08(s,1H),6.89-6.78(m,5H),6.57-6.54(m,1H),6.17-6.15( m, 2H). 13 C NMR (125MHz, CDCl 3 ) δ141.8, 133.7, 132.6, 131.3, 131.2, 128.5, 128.4, 127.8, 127.6, 127.0, 126.1, 126.0, 125.9, 125.5, 125.2, 123.7, 121. 119.4, 118.8, 117.0, 115.9, 111.4, 97.1. HRMS (ESI) m/z calculated for C 30 H 21 N 2 S + [M+H] + 441.1420, found 441.1416.
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| 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 |
| CN112195480A (en) * | 2020-09-30 | 2021-01-08 | 浙江工业大学 | A method for electrocatalytic synthesis of aromatic nitrile using aromatic methyl compounds as raw materials |
| CN113026036A (en) * | 2021-03-11 | 2021-06-25 | 南京工业大学 | Method for synthesizing sulfur ylide compounds by using continuous flow electrochemical oxidation |
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| 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 |
| CN112195480A (en) * | 2020-09-30 | 2021-01-08 | 浙江工业大学 | A method for electrocatalytic synthesis of aromatic nitrile using aromatic methyl compounds as raw materials |
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