CN115108960A - Preparation method and application of polysubstituted indole compound - Google Patents

Preparation method and application of polysubstituted indole compound Download PDF

Info

Publication number
CN115108960A
CN115108960A CN202210849941.7A CN202210849941A CN115108960A CN 115108960 A CN115108960 A CN 115108960A CN 202210849941 A CN202210849941 A CN 202210849941A CN 115108960 A CN115108960 A CN 115108960A
Authority
CN
China
Prior art keywords
compound
reaction
indole
polysubstituted
indole compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210849941.7A
Other languages
Chinese (zh)
Inventor
李先纬
李仲元
霍延平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Wanzhida Enterprise Management Co ltd
Original Assignee
Guangdong University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong University of Technology filed Critical Guangdong University of Technology
Priority to CN202210849941.7A priority Critical patent/CN115108960A/en
Publication of CN115108960A publication Critical patent/CN115108960A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electromagnetism (AREA)
  • Indole Compounds (AREA)

Abstract

The application relates to a series reaction of oxidation Heck and multiple dehydrocyclization of N-alkyl-N-aryl nitrosamide and aryl ethylene catalyzed by a trivalent rhodium catalyst, and realizes the high-efficiency synthesis of polysubstituted indole compounds. The patent application discloses a first-case indole synthesis reaction which is free of trace in metal catalysis, promoted by an intramolecular oxidant and molecular oxygen and realized through a multiple dehydrogenation strategy. Specifically, under the condition of an inert solvent, oxygen is used as a co-oxidant, and various polysubstituted indole compounds are quickly constructed while small molecules (nitrous oxide and water) are released through multiple dehydrogenation reactions of N-aryl nitrosamides and aryl ethylene catalyzed by trivalent rhodium. The method has the characteristics of green oxidation, chemical selectivity, good regioselectivity and the like, and meanwhile, the method only uses the simple and easily obtained arylamine derivative as a traceless internal oxidation guiding group to realize multiple dehydrogenation reactions with terminal olefin of a large number of chemicals. The conversion steps are few, the operation is simple and convenient, and the obtained product is easy to further convert.

Description

Preparation method and application of polysubstituted indole compound
Technical Field
The patent application relates to the field of organic compound synthesis reaction, and more specifically relates to a preparation method and application of a polysubstituted indole compound.
Background
Indole is used as a ubiquitous core skeleton in functional materials such as natural products (such as alkaloids), drug molecules (such as indomethacin), fluorescent probes, dyes and the like, and the simple construction thereof attracts the continuous attention of synthetic chemists. The classical synthesis of indole is as follows: fischer indole synthesis (J.Am.chem.Soc.,2002,124,11342-11348.), Bartoli indole synthesis (J.Org.chem.,1996,61,9055-9059.), Hemetsberger indole synthesis (J.chem.Soc., Perkin Trans.1,2000, 1045-1075.). The above strategy provides an important way for the high-efficiency synthesis of indole natural products, medicines, functional materials and the like.
However, the above methods still have some limitations to be solved by the synthesis method itself:
1) multifunctional starting materials prepared beforehand are often required, for example for Fischer indole synthesis, when carbonyl compounds are used whose substrates contain two different substituents in the alpha position, the selectivity of the product obtained is poor; for the Bartoli indole synthesis method, a substituent is required to be contained at the ortho-position of nitrobenzene serving as a substrate, and the steric hindrance of the substituent has direct influence on the reaction yield; for Hemetsberger indole synthesis, the complicated preparation process of the substrate azido acrylate limits the application potential of the method.
2) The traditional reaction uses stoichiometric amount of protonic acid or Grignard reagent, which also causes additional stoichiometric amount of alkali or acid to be added during the post-treatment, therefore, the process is not in accordance with the concept of modern green chemistry;
3) the operation process is long and has danger hidden danger, for example, when a large amount of azide is added to participate in the reaction, if the feeding speed is not strictly controlled, a large amount of nitrogen can be rapidly released in the system, and potential explosion risks exist.
Therefore, it is still highly desirable to develop a more atomic, cost effective and selective green and efficient synthesis method. In recent years, carbon-hydrogen bond activation reactions based on transition metal catalysis are developed to widen an indole synthetic molecule library, and the reactions have the advantages of higher atom economy and rapid and simple construction of indole molecules; however, the transition metal catalyzed indole synthesis described above often presents the following challenges:
1) the substrate often needs to be modified in advance and is not easy to leave and convert after the reaction. For example, in 2016, Glorius achieved the reaction of NH-Boc phenylhydrazine derivatives with the synthesis of indoles with internal alkynes under divalent cobalt catalyzed conditions (Angew. chem. int. Ed.2016,55,3208-3211.), but such NH-Boc phenylhydrazines were not easily synthesized and the "footprint" of the substrate was present in the product, which was not easily removed. Such functional groups, which are not susceptible to subsequent transformation, thus hinder the continued potential of such methods for the synthesis of biologically active molecules;
2) it is difficult to control the regioselectivity of the synthetic indoles. For example, in 2013, the Zhu task group reported the reaction of N-nitrosoaniline with 1, 2-disubstituted internal alkyne to synthesize indole (J.Am.chem.Soc.2013,135, 16625-16631). The alkynes compound often face the problem of difficult-to-regulate regioselectivity in the type of indole synthesis by metal-catalyzed carbon-hydrogen bond activation, so that regioisomers are obtained by reaction when asymmetric alkynes are used;
3) in the process of synthesizing indole by the metal-catalyzed oxidation of carbon-hydrogen bond activation, a stoichiometric amount of non-environment-friendly oxidant such as cupric salt and monovalent silver salt is often required to be additionally introduced into a catalytic system, which also limits the application of the catalyst in large-scale production.
Content of the patent application
To overcome at least one of the problems of the prior art described above, the present patent application provides a process for preparing a polysubstituted indole compound. According to the preparation method, under the assistance of molecular oxygen and an intramolecular oxidant, the N-aryl nitrosamide and aryl ethylene are subjected to multiple dehydrogenation reactions under the catalysis of trivalent rhodium, so that a multi-substituted indole compound is synthesized while small molecules are released. (a substrate with a substituted functional group at the meta position, a plurality of carbon-hydrogen bonds with different chemical environments and different activities exist, the synthesis of indole is difficult to realize with good regioselectivity conventionally, in addition, the reaction activity and the site selectivity of the pyridine substrate which is very challenging in the activation of the carbon-hydrogen bonds through traditional metal catalysis are often difficult to obtain, and in the application, the synthesis of azaindole compatible with the pyridine substrate is realized, and the azaindole is also a core framework of an antimalarial inhibitor and an organic light-emitting semiconductor material, and not only is the multiple dehydrogenation reaction of the polysubstituted N-aryl nitrosamide and aryl ethylene realized, but also the synthesis of azaindole compatible with the pyridine substrate is realized)
It is a further object of the present application to provide the use of the above polysubstituted indole compounds.
In order to solve the technical problem, the technical scheme adopted by the patent application is as follows:
a preparation method of a polysubstituted indole compound is characterized by comprising the following steps: in an inert solvent, under the action of a trivalent rhodium catalyst, reacting an N-aryl nitrosamide compound (formula II) with an aryl ethylene compound (formula III) to obtain a polysubstituted indole compound (formula I):
Figure BDA0003753074140000021
wherein Ar is 1 Is a para-position, meta-position, ortho-position and other multi-substituted benzene ring or heterocyclic compound, Ar 2 Is para-position and meta-position substituted benzene ring or condensed ring, and R is functional group substituted benzene ring or alkyl.
Preferably, the inert solvent is any one or more of toluene, tetrahydrofuran, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, 1, 2-dichloroethane, ethanol and water.
Preferably, the trivalent rhodium catalyst is any one or more of pentamethylcyclopentadienylrhodium chloride dimer, pentamethylcyclopentadienyliridium chloride dimer and acetonitrile-pentamethylcyclopentadienylrhodium chloride dimer.
Preferably, a halogen ion capture agent is added in the reaction, and the halogen ion capture agent is any one or more of silver hexafluoroantimonate and silver bis (trifluoromethanesulfonyl) imide.
Preferably, an additive is added in the reaction, and the additive is any one or more of sodium acetate, sodium trifluoroacetate, sodium pivalate, sodium glycinate, sodium propionate and sodium 2,4, 6-trimethylbenzoate.
Preferably, the reaction molar ratio of the N-aryl nitrosamide compound (formula II) to the terminal olefin compound (formula III) is 1: 1.5-1: 2.
Preferably, the trivalent rhodium catalyst is used in an amount of 2 mol% based on the amount of the N-alkyl-N-arylnitrosamide compound (formula II).
Preferably, the reaction is carried out at 80-120 ℃; the reaction is carried out for 12-24 hours.
The preparation method of the polysubstituted indole compound in some preferred embodiments of the present patent application comprises the following specific steps:
s1: in a reactor, in the air, 2.5mg of pentamethylcyclopentadienylrhodium dichloride dimer, 3.9mg of silver trifluoromethanesulfonylimide, 27.2mg of sodium trifluoroacetate, 1.0mL of 1, 2-dichloroethane, 27.2mg of N-methyl-N-phenylnitrosamide and 31.2mg of styrene were added in this order;
s2: reacting the reaction solution at 100 ℃ for 12 hours;
s3: and after the reaction is finished, separating the mixture by using a column chromatography separation technology to obtain the target compound.
The application also provides a solar cell, wherein the solar cell is a perovskite solar cell, and the hole transport material in the perovskite solar cell adopts the polysubstituted indole compound prepared by the preparation method as claimed in claim 1.
Under the condition of an inert solvent, through trivalent rhodium catalysis and under the assistance of molecular oxygen, simple and easily-obtained N-aryl nitrosamide and aryl ethylene are used as reaction substrates, so that chemoselectivity (the example of the application can obtain target molecules with single product structures in good yield and has better chemoselectivity) and regioselectivity (when the meta-position of the reaction substrate is substituted by a functional group, multiple reaction active sites are provided, a single selective product can be obtained through reaction, the regioselectivity is proved to be good, and the examples 3 and 4 are detailed) are used for carrying out modular synthesis on an indole compound which has good application prospects and multiple substitution prospects in the fields of biology, medicines and photoelectric materials.
Compared with the prior art, the beneficial effect of this patent application is:
the preparation method of the polysubstituted indole compound provided by the application has the characteristics of traceless orientation, green oxidation and multiple dehydrogenation, and the obtained indole product shows good performance in a hole transport layer material in a solar cell (the indole skeleton in the application can obtain the power conversion efficiency of 17.59%).
Drawings
FIG. 1 is a NMR chart of Compound 1a prepared in example 1 of the present patent application;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of Compound 1a prepared in example 1 of the present patent application;
FIG. 3 is a NMR spectrum of Compound 1b prepared in example 2 of the present application;
FIG. 4 is a NMR carbon spectrum of Compound 1b prepared in example 2 of the present application;
FIG. 5 is a NMR spectrum of Compound 1c prepared in example 3 of the present application;
FIG. 6 shows the NMR spectrum of Compound 1c prepared in example 3 of the present application;
FIG. 7 is a NMR spectrum of Compound 1d prepared in example 4 of the present application;
FIG. 8 is a nuclear magnetic resonance fluorine spectrum of Compound 1d prepared in example 4 of the present patent application;
FIG. 9 shows a NMR spectrum of Compound 1d prepared in example 4 of the present application;
FIG. 10 is a NMR spectrum of Compound 1e prepared in example 5 of the present application;
FIG. 11 is a NMR spectrum of Compound 1e prepared in example 5 of the present application;
FIG. 12 is a NMR spectrum of Compound 1f prepared in example 6 of the present application;
FIG. 13 is a NMR carbon spectrum of Compound 1f prepared in example 6 of the present application;
FIG. 14 is a NMR spectrum of 1g of compound prepared in example 7 of the present application;
FIG. 15 is a NMR spectrum of 1g of compound prepared in example 7 of the present application;
FIG. 16 is a NMR spectrum of compound 1h prepared in example 8 of the present application for hydrogen;
FIG. 17 is a NMR spectrum of Compound 1h prepared in example 8 of the present application for C;
FIG. 18 is a NMR spectrum of Compound 1i prepared in example 9 of the present application;
FIG. 19 is a NMR carbon spectrum of Compound 1i prepared in example 9 of the present patent application;
fig. 20 is a graph showing the distribution of the front-line orbitals of the compound li prepared in example 9 of the present patent application as a hole transport material for perovskite solar cells.
Fig. 21 is a J-V test graph corresponding to the compound li prepared in example 9 of the present patent application as a hole transport material of a perovskite solar cell.
Detailed Description
Embodiments of the present patent application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present patent application and should not be construed as limiting the scope of the present patent application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
It should be noted that:
all embodiments and preferred methods mentioned herein can be combined with each other to form new solutions, if not specifically stated in the present patent application.
In this patent application, percentages (%) or parts refer to percentages or parts by weight relative to the composition, if not otherwise specified.
In the present patent application, the components referred to or the preferred components thereof may be combined with each other to form new solutions, if not specifically stated.
In this patent application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "12 to 24" means that all real numbers between "12 to 24" have been listed herein, and "12 to 24" is only a shorthand representation of the combination of these numerical values.
The "range" disclosed in this patent application may be in the form of one or more lower limits and one or more upper limits, respectively, in the form of lower limits and upper limits.
In this application, unless otherwise indicated, individual reactions or process steps may be performed sequentially or in sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. Moreover, any methods or materials similar or equivalent to those described herein can also be used in the present application.
The application provides a preparation method of a polysubstituted indole compound, which comprises the following steps: in an inert solvent, under the action of a trivalent rhodium catalyst, reacting an N-aryl nitrosamide compound (formula II) with an aryl ethylene compound (formula III) to obtain a polysubstituted indole compound (formula I):
Figure BDA0003753074140000061
wherein Ar is 1 Is a para-position, meta-position, ortho-position and other multi-substituted benzene ring or heterocyclic compound, Ar 2 Is para-position and meta-position substituted benzene ring or condensed ring, and R is (cyclo) alkyl or functional group substituted benzene ring.
The patent application discloses an indole synthesis reaction which is promoted by an intramolecular oxidant (namely N-nitroso) and is realized by a multiple dehydrogenation strategy, wherein the first metal catalysis is traceless (the traceless refers to that N-nitroso is used as a traceless guiding group and guides C-H to be activated and then is converted into a part of target molecules. Specifically, under the condition of an inert solvent, oxygen in the air is used as a co-oxidant, and various polysubstituted indole compounds are quickly constructed while small molecules (nitrous oxide and water) are released through multiple dehydrogenation reactions of N-aryl nitrosamide and aryl ethylene catalyzed by trivalent rhodium. The method has the characteristics of green oxidation, chemical selectivity, good regioselectivity and the like. In addition, the halide ion capturing agent of the present patent application is monovalent silver salt, but the amount thereof is only 5 mol%, and the halide ion capturing agent does not participate in the reaction as a stoichiometric oxidant, but only acts as a catalyst ligand exchange. Thus. The synthetic reactions involved in this patent application are green in nature as a whole.
Meanwhile, the method only uses simple and easily obtained arylamine derivatives as traceless internal oxidation guide groups to realize multiple dehydrogenation reactions with terminal olefins of bulk chemicals. The conversion steps are few, the operation is simple and convenient, the obtained product is easy to further convert subsequently, more importantly, the polysubstituted indole product obtained by the strategy is subjected to coupling reaction to construct a perovskite solar cell hole transport layer material, and the power conversion efficiency can reach 17.6%.
In some embodiments, the inert solvent is any one or more of toluene, tetrahydrofuran, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetonitrile, 1, 2-dichloroethane, ethanol, water.
In some embodiments, the trivalent rhodium catalyst is any one or more of pentamethylcyclopentadienylrhodium chloride dimer, pentamethylcyclopentadienyliridium chloride dimer, and triacetonitrile-pentamethylcyclopentadienylrhodium chloride dimer.
In some embodiments, the reaction further comprises adding a halogen ion capturing agent, wherein the halogen ion capturing agent is any one or more of silver hexafluoroantimonate and silver bis (trifluoromethanesulfonyl) imide.
In some embodiments, the reaction further comprises an additive, wherein the additive is any one or more of sodium acetate, sodium trifluoroacetate, sodium pivalate, sodium glycinate, sodium propionate and sodium 2,4, 6-trimethylbenzoate.
In some embodiments, the reaction molar ratio of the N-aryl nitrosamide compound (formula II) to the terminal olefin compound (formula III) is from 1:1.5 to 1: 2.
In some embodiments, the trivalent rhodium catalyst is used in an amount of 2 mol% of the amount of the N-aryl nitrosamide compound (formula II).
In some embodiments, the reaction is carried out at 80-120 ℃; the reaction is carried out for 12-24 hours.
Next, the preparation of the polysubstituted indole compounds of the present patent application will be described in detail with reference to specific examples.
1. Preparation example
EXAMPLE 11 preparation of methyl-2-phenyl-1H-indole (1a)
Figure BDA0003753074140000071
To a 15mL Schlenk reaction tube under an atmospheric air atmosphere were added N-methyl-N-phenylnitrosamide 2a (27.2mg,0.20mmol), styrene 3a (31.3mg,0.30mmol), and a trivalent rhodium catalyst [ Cp Rh (CH) 3 CN) 3 Cl 2 ] 2 (3.3mg,0.004mmol), silver trifluoromethanesulfonylimide (3.9mg,0.01mmol), sodium trifluoroacetate (27.2mg,0.2mmol), 1, 2-dichloroethane (DCE,1.0mL) at a temperature of 100 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 99: 1, the product 1-methyl-2-phenyl-1H-indole (1a) was obtained in 46% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the chemical combination prepared in example 1 are shown in fig. 1 and fig. 2. From FIG. 1, it can be seen that 1 H NMR(400MHz,CDCl 3 )δ7.63(d,J＝8.0Hz,1H),7.52-7.50(m,2H),7.46(t,J＝7.2Hz,2H),7.41-7.37(m,1H),7.36(d, J ═ 8.4Hz,1H),7.26-7.22(m,1H),7.15-7.11(m,1H),6.55(s,1H),3.74(s, 3H). The molecular hydrogen spectrum peak energy and the target products are in one-to-one correspondence, and the quantity is reasonable. As can be seen from fig. 2: 13 C NMR(100MHz,CDCl 3 ) δ 141.6,138.3,132.9,129.4,128.5,128.0,127.8,121.6,120.5,119.8,109.6,101.6, 31.1. The molecular carbon spectrum wave peak energy and the target product correspond to each other one by one, and the quantity is reasonable. The results of the nuclear magnetic hydrogen spectrum and the carbon spectrum show that the product obtained in example 1 is 1-methyl-2-phenyl-1H-indole (1 a).
EXAMPLE 25 preparation of chloro-1-methyl-2-phenyl-1H-indole (1b)
Figure BDA0003753074140000081
To a 15mL Schlenk reaction tube under an atmospheric air atmosphere were added N- (4-chlorophenyl) -N-methylnitrosamide 2b (34.0mg,0.20mmol), styrene 3a (31.3mg,0.30mmol), and a trivalent rhodium catalyst [ Cp. multidot. RhCl ] in this order 2 ] 2 (2.5mg,0.004mmol), silver hexafluoroantimonate (3.6mg,0.01mmol), sodium trifluoroacetate (27.2mg,0.2mmol), 1, 2-dichloroethane (DCE,1.0mL) at a temperature of 100 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 99: 1, the product 5-chloro-1-methyl-2-phenyl-1H-indole (1b) is obtained in 61% yield
The nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum of the compound prepared in example 2 are shown in fig. 3 and 4. As can be seen from fig. 3: 1 H NMR(400MHz,CDCl 3 ) δ 7.59(d, J ═ 2.0Hz,1H),7.51-7.46(m,4H),7.44-7.42(m,1H),7.28(s,1H),7.19(dd, J ═ 2.0Hz,8.8Hz,1H),6.50(s,1H),3.73(s, 3H). As can be seen from fig. 4: 13 C NMR(100MHz,CDCl 3 ) δ 142.9,136.7,132.4,129.3,128.9,128.6,128.1,125.5,121.8,119.8,110.6,101.2, 31.3. The results of the nuclear magnetic hydrogen spectrum and the carbon spectrum show that the product obtained in example 2 is 5-chloro-1-methyl-2-phenyl-1H-indole (1 b).
The chemical conversion in the embodiment can rapidly construct multi-substituted indole molecules, and the ring contains a halogen functional group which is easy to convert, thereby providing a platform for the construction of more complex molecules.
Example 32- (4- (tert-butyl) phenyl) -5, 6-dihydro-4H-pyrrolo [3,2,1-ij]Preparation of quinoline (1c)
Figure BDA0003753074140000082
To a 15mL Schlenk reaction tube, 1-nitroso-1, 2,3, 4-tetrahydroquinoline 2c (52.0mg,0.20mmol), 4-tert-butylstyrene 3b (32.0mg,0.30mmol), and a trivalent rhodium catalyst [ Cp. RhCl ] were sequentially added under an atmospheric air atmosphere 2 ] 2 (2.5mg,0.004mmol), silver hexafluoroantimonate (3.6mg,0.01mmol), sodium trifluoroacetate (27.2mg,0.2mmol), 1, 2-dichloroethane (DCE,1.0mL) at a temperature of 100 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 99: 1, the product 2- (4- (tert-butyl) phenyl) -5, 6-dihydro-4H-pyrrolo [3,2,1-ij is obtained in 42% yield]Quinoline (1 c).
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the compound prepared in example 3 are shown in fig. 5 and 6. As can be seen from fig. 5: 1 H NMR(400MHz,CDCl 3 ) δ 7.61-7.50 (m,5H), 7.16-7.07 (m,1H), 7.04-6.97 (m,1H),6.62(s,1H),4.28(t, J ═ 6.0Hz,2H),3.08(t, J ═ 6.1Hz,2H),2.25(p, J ═ 5.9Hz,2H),1.46(s, 9H). As can be seen from fig. 6: 13 C NMR(100MHz,CDCl 3 ) δ 150.6,139.9,135.2,131.6,129.8,128.3,128.2,126.0,125.5,121.9,119.8,118.4,117.7,100.2,77.3,77.0,76.7,43.7,34.6,31.4,31.3,31.3,25.0, 23.1. The results of the nuclear magnetic hydrogen spectrum and the carbon spectrum show that the product obtained in example 3 is 2- (4- (tert-butyl) phenyl) -5, 6-dihydro-4H-pyrrolo [3,2,1-ij]Quinoline (1 c).
The chemical transformations in this example can be applied to fused ring based materials, biologically active molecules.
EXAMPLE 46 preparation of chloro-5-fluoro-1-methyl-2- (naphthalen-2-yl) -1H-indole (1d)
Figure BDA0003753074140000091
To a 15mL Schlenk reaction tube under an atmospheric air atmosphere were added N- (3-chloro-4-fluorophenyl) -N-methylnitrosamide 2d (37.6mg,0.20mmol), 4-tert-butylstyrene 3c (32.0mg,0.30mmol), and a trivalent rhodium catalyst [ Cp. RhCl 2 ] 2 (2.5mg,0.004mmol), silver trifluoromethanesulphonimide (3.9mg,0.01mmol), sodium pivalate (28.4mg,0.2mmol), 1, 2-dichloroethane (DCE,1.0mL) were reacted at 100 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 99: 1, the product 6-chloro-5-fluoro-1-methyl-2- (naphthalen-2-yl) -1H-indole (1d) was obtained in 42% yield.
The nuclear magnetic hydrogen spectrum, fluorine spectrum and carbon spectrum of the compound prepared in example 4 are shown in fig. 7, 8 and 9 in this order. As can be seen from fig. 7: 1 H NMR(400MHz,CDCl 3 ) δ 7.96-7.89 (m,4H),7.60(dd, J ═ 1.7Hz,8.5Hz,1H), 7.57-7.53 (m,2H), 7.41-7.36 (m,2H),6.60(s,1H),3.77(s, 3H); as can be seen from fig. 8: 19 F NMR(376MHz,CDCl 3 ) Delta-127.0; as can be seen from fig. 9: 13 C NMR(100MHz,CDCl 3 ) δ 153.2(d, J-238.0 Hz),143.6,135.0,133.2,132.9,129.4,128.6,128.4(d, J-13.0 Hz),128.0(d, J-37.0 Hz),126.8,126.7(d, J-4.0 Hz),115.2(d, J-21.0 Hz),110.8,110.5(d, J-25.0 Hz),108.5(d, J-9.0 Hz),106.3(d, J-23.0 Hz),102.0(d, J-5.0 Hz),100.7(d, J-5.0 Hz), 31.6. The results of the nuclear magnetic hydrogen, fluorine and carbon spectra were combined to show that the product obtained in example 4 was 6-chloro-5-fluoro-1-methyl-2- (naphthalen-2-yl) -1H-indole (1 d).
The chemical conversion in this embodiment can be compatible with fluorine elements widely used in the fields of materials and medicines. More importantly, the transformation has excellent site selectivity for N-nitrosamide compounds with multiple potential active sites. For a poly-substituted (m-and p-containing functional groups) N-nitrosoaniline substrate, the C-H bond in the ortho position of the functional group is affected, and different activities are shown. The above-mentioned "active site" refers to C with different chemical environment on the benzene ring SP2 -a H bond. The polysubstituted N-nitrosoaniline has different activity C-H bonds but still can activate N-The C-H bond adjacent to the NO director provides a single target product and thus has excellent site selectivity (regioselectivity).
Example 52- (4- (tert-butyl) phenyl) -1-methyl-1H-pyrrolo [2,3-b ]]Preparation of pyridine (1e)
Figure BDA0003753074140000101
To a 15mL Schlenk reaction tube under an atmospheric air atmosphere were added N-methyl-N- (pyridin-2-yl) nitrosamide 2e (27.4mg,0.20mmol), 4-tert-butylstyrene 3b (32.0mg,0.30mmol), and a trivalent rhodium catalyst [ Cp. RhCl ] in that order 2 ] 2 (2.5mg,0.004mmol), silver trifluoromethanesulfonylimide (3.9mg,0.01mmol), sodium trifluoroacetate (27.2mg,0.2mmol), 1, 2-dichloroethane (DCE,1.0mL) at 100 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 99: 1, the product 2- (4- (tert-butyl) phenyl) -1-methyl-1H-pyrrolo [2,3-b ] is obtained in 31% yield]Pyridine (1 e).
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the compound prepared in example 5 are shown in fig. 10 and 11 in this order. As can be seen from fig. 10: 1 H NMR(400MHz,CDCl 3 ) δ 8.34(dd, J ═ 1.6Hz,4.8Hz,1H),7.90(dd, J ═ 1.6Hz,7.8Hz,1H), 7.54-7.46 (m,4H),7.08(dd, J ═ 4.8Hz,7.7Hz,1H),6.50(s,1H),3.89(s,3H),1.39(s, 9H). As can be seen from fig. 11: 13 C NMR(100MHz,CDCl 3 ) δ 151.4,149.1,142.3,141.9,129.4,128.8,128.0,125.5,120.7,116.0,99.1,34.7,31.3, 29.9. From the results of the nuclear magnetic hydrogen spectrum and the carbon spectrum, it was found that the product obtained in example 5 was 2- (4- (tert-butyl) phenyl) -1-methyl-1H-pyrrolo [2,3-b ]]Pyridine (1 e).
It is worth mentioning that in the metal-catalyzed inert bond activation reaction realized by the conventional guiding strategy, the strongly coordinated compound is difficult to synthesize the target product with selectivity due to the characteristics of easy complexation with metal and difficult dissociation. In the application, the strongly coordinating heterocycle such as pyridine and quinoline can be well involved in the synthesis of the indole, and the azaindole derivative which is difficult to synthesize simply by a conventional strategy is realized.
In the prior art, the compound with strong coordination is difficult to synthesize a target product with selectivity due to the characteristic that the compound is easy to complex with metal and difficult to dissociate, and the implementation in the embodiment is realized by releasing small molecules (N) in the reaction 2 O，H 2 O), aromatization is used as a driving force, the complexation of a strong coordination heterocyclic ring and metal is overcome, namely the limitation of the strong coordination heterocyclic ring in the metal-catalyzed aromatic ring carbon-hydrogen bond activation reaction assisted by a conventional guiding strategy is overcome, and the method is also the first method for constructing azaindole by applying the metal-catalyzed aromatic amine derivative carbon-hydrogen bond activation strategy. Moreover, the chemical transformation in this example can be widely applied to the field of biomedicine of azaindoles.
EXAMPLE 62 preparation of- (3-chlorophenyl) -1-methyl-1H-indole (1f)
Figure BDA0003753074140000111
To a 15mL Schlenk reaction tube under an atmospheric air atmosphere were added N-methyl-N-phenylnitrosamide 2a (27.4mg,0.20mmol), 3-chlorostyrene 3d (40.8mg,0.30mmol), and trivalent rhodium catalyst [ Cp. multidot. RhCl ] in that order 2 ] 2 (2.5mg,0.004mmol), silver trifluoromethanesulfonylimide (3.9mg,0.01mmol), sodium acetate (16.4mg,0.2mmol), 1, 2-dichloroethane (DCE,1.0mL) at 100 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 99: 1, the product 2- (3-chlorophenyl) -1-methyl-1H-indole (1f) was obtained in 61% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the compound prepared in example 6 are shown in fig. 12 and 13 in this order. As can be seen from fig. 12: 1 H NMR(400MHz,CDCl 3 ) δ 7.63(d, J ═ 8.0Hz,1H),7.50(s,1H),7.40-7.35(m,1H),7.28-7.24(m,1H),7.14(t, J ═ 7.2Hz,2H),7.14-7.10(m,1H),6.57(s,1H),3.74(s, 3H); as can be seen from fig. 13: 13 C NMR(100MHz,CDCl 3 ) δ 139.9,138.5,134.6,134.4,129.7,129.2,127.9,127.8,127.4,122.1,120.6,120.0,109.7,102.3, 31.2. Incorporating the above nuclear magnetic hydrogenAs a result of spectroscopy and a carbon spectrum analysis, the product obtained in example 6 was 2- (3-chlorophenyl) -1-methyl-1H-indole (1 f).
The chemical transformation in this example can rapidly construct multi-substituted indole molecules, and combines easily transformable halogen functional groups, thereby providing a platform for the construction of more complex molecules.
EXAMPLE 75 preparation of iodo-1-methyl-2- (naphthalen-2-yl) -1H-indole (1g)
Figure BDA0003753074140000121
To a 15mL Schlenk reaction tube under an atmospheric air atmosphere were added N- (4-iodophenyl) -N-methylnitrosamide 2f (52.2mg,0.20mmol), 2-vinylnaphthalene 3c (46.2mg,0.30mmol), and a trivalent rhodium catalyst [ Cp. RhCl ] in that order 2 ] 2 (2.5mg,0.004mmol), silver trifluoromethanesulfonylimide (3.9mg,0.01mmol), sodium 2,4, 6-trimethylbenzoate (37.2mg,0.2mmol), 1, 2-dichloroethane (DCE,1.0mL) at 100 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 99: 1, the product 5-iodo-1-methyl-2- (naphthalen-2-yl) -1H-indole (1g) was obtained in 67% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the compound prepared in example 7 are shown in fig. 14 and 15 in this order. As can be seen from fig. 14: 1 H NMR(400MHz,CDCl 3 ) δ 7.99-7.89 (m,5H), 7.64-7.59 (m,2H), 7.56-7.53 (m,1H),7.51(dd, J ═ 1.7Hz,8.6Hz,1H),7.17(d, J ═ 8.6Hz,1H),6.58(s,1H),3.78(s, 3H); as can be seen from fig. 15: 13 C NMR(100MHz,CDCl 3 ) δ 142.3,140.6,137.8,137.6,133.2,132.7,131.9,130.0,129.2,128.5,128.2,128.1,127.8,127.0,126.7,126.6,111.6,101.2,77.3,77.0,76.7, 31.4. From the results of the nuclear magnetic hydrogen spectrum and the carbon spectrum, it was found that the product obtained in example 7 was 5-iodo-1-methyl-2- (naphthalen-2-yl) -1H-indole (1 g).
The chemical conversion in this embodiment can be compatible with aryl iodides that are difficult to be compatible with conventional carbon-hydrogen bond activation reactions, and the aryl iodides have good chemical activities, such as palladium-catalyzed coupling reactions, Ullmann (Ullmann) coupling reactions, and the like, thereby providing a platform for the construction of more complex molecules.
EXAMPLE 85 preparation of methoxy-1- (4-methoxyphenyl) -2- (naphthalen-2-yl) -1H-indole (1H)
Figure BDA0003753074140000131
To a 15mL Schlenk reaction tube under an atmospheric air atmosphere were added N, N-bis (4-methoxyphenyl) nitrosamide 2g (78.3mg,0.20mmol), 2-vinylnaphthalene 3c (46.2mg,0.30mmol), and a trivalent rhodium catalyst [ Cp. RhCl ] in this order 2 ] 2 (2.5mg,0.004mmol), silver trifluoromethanesulphonimide (3.9mg,0.01mmol), sodium glycinate (Gly-Na,19.4mg,0.2mmol), 1, 2-dichloroethane (DCE,1.0mL) at 100 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 99: 1, the product 5-methoxy-1- (4-methoxyphenyl) -2- (naphthalen-2-yl) -1H-indole (1H) was obtained in 52% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the compound prepared in example 8 are shown in fig. 16 and 17 in this order. As can be seen from fig. 16: 1 H NMR(400MHz,CDCl 3 ) δ 7.81-7.76 (m,2H), 7.74-7.67 (m,2H), 7.48-7.43 (m,2H),7.36(dd, J ═ 1.8Hz,8.6Hz,1H), 7.23-7.19 (m,2H), 7.19-7.16 (m,2H), 6.94-6.90 (m,2H),6.87(dd, J ═ 2.4Hz,9.0Hz,1H),6.84(s,1H),3.91(s,3H),3.83(s, 3H); as can be seen from fig. 17: 13 C NMR(100MHz,CDCl 3 ) δ 158.5,154.8,141.2,134.9,133.2,132.3,131.5,130.1,129.0,128.5,128.1,127.7,127.6,126.7,126.2,126.1,114.5,112.5,111.4,103.3,102.0,55.9, 55.4. The results of the nuclear magnetic hydrogen spectroscopy and the carbon spectroscopy show that the product obtained in example 8 is 5-methoxy-1- (4-methoxyphenyl) -2- (naphthalen-2-yl) -1H-indole (1H).
Diarylamine is used as an organic synthetic block, and the organic block is an organic functionalized molecule, namely a basic component for organic synthesis. They can be used for bottom-up modular assembly of molecular structures such as supramolecular complexes, metal-organic frameworks, organic molecular constructs, and nanoparticles. They therefore play a fundamental role in medicinal, organic and material chemistry. The chemical conversion in the embodiment uses a synthetic block diarylamine group as a raw material, so the reaction provides a new strategy for the high value-added conversion of bulk aniline chemicals, and the N-aryl indole product can be applied to the fields of biomedicine, organic photoelectric materials and the like.
2. Application example
Example 9 perovskite solar cell hole transport material molecules: preparation of 5,5 '- (4, 8-bis (hexyloxy) benzo [1,2-b:4,5-b' ] dithiophene-2, 6-diyl) bis (1-methyl-2- (naphthalen-2-yl) -1H-indole) (1i) and Material characterization
Figure BDA0003753074140000141
Preparation of intermediate 5-bromo-1-methyl-2- (naphthalen-2-yl) -1H-indole (1 ii): to a 15mL Schlenk reaction tube under an atmospheric air atmosphere were added sequentially N- (4-bromophenyl) -N-methylnitrosamide 2h (43.0mg,0.20mmol), 2-vinylnaphthalene 3c (46.2mg,0.30mmol), and trivalent rhodium catalyst [ Cp. RhCl ] 2 ] 2 (2.5mg,0.004mmol), silver trifluoromethanesulfonylimide (3.9mg,0.01mmol), sodium acetate (16.4mg,0.2mmol), 1, 2-dichloroethane (DCE,1.0mL) at 100 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 99: 1, intermediate 5-bromo-1-methyl-2- (naphthalen-2-yl) -1H-indole (1ii) was obtained in 63% yield.
Figure BDA0003753074140000142
Preparation of target compound (1 i): the indole derivative obtained by the preparation method of the patent application is subjected to coupling reaction to simply synthesize a material molecule taking dibenzothiophene as a pi unit, and the specific method is as follows: under nitrogen atmosphere, 5-bromo-1-methyl-2- (naphthalen-2-yl) -1H-Indole 1ii (83.8mg,0.25mmol), 4, 8-bis (hexyloxy) benzo [1,2-b:4,5-b']Dithiophene (39.1mg,0.1mmol), palladium acetate catalyst Pd (OAc) 2 (4.5mg,0.02mmol), di-tert-butylmethylphosphonium tetrafluoroborate (14.9mg,0.06mmol), potassium carbonate (82.9mg,0.8mmol), silver trifluoromethanesulfonate (102.8mg,0.4mmol), N, N-dimethylacetamide (DMA,1.0mL), and reacted at 150 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the dichloromethane is 1.5: 1, the product 5,5 ' - (4, 8-bis (hexyloxy) benzo [1,2-b:4,5-b ' was obtained in 56% yield ']Dithiophene-2, 6-diyl) bis (1-methyl-2- (naphthalen-2-yl) -1H-indole) (1 i).
In the material characterization of 1i molecule, we found that it exhibited good performance of hole transport material, specifically, it is known from fig. 20 that the Highest Occupied Molecular Orbital (HOMO) of 1i was delocalized throughout the molecule, facilitating charge transport, the Lowest Unoccupied Molecular Orbital (LUMO) was mainly located on the core skeleton, the overlap of HOMO and LUMO orbitals facilitated hole extraction, and E of 1i was calculated from density functional theory (DFT for short) to obtain HOMO Or E LUMO The value is-5.05/-1.52 eV, which meets the requirements of hole transport materials of perovskite solar cells, and surprisingly, the molecules show good performance in the test. Next, application of the indole derivative to a perovskite solar cell will be described in detail.
2.5mg of Compound 1i was dissolved in 1mL of chlorobenzene solvent, spin-coated on the washed conductive glass at 4000rpm, and then annealed at 100 ℃ for 10 minutes. After cooling, the perovskite precursor solution is sequentially spin-coated on a substrate at the rotation speeds of 1000rpm and 5000rpm, and annealed at 100 ℃ for 30 min. After cooling to room temperature [6,6 ]]A chlorobenzene solution of phenyl-C61-isopropyl butyrate (PCBM) was spin coated on the perovskite layer, annealed at 65 ℃ for 10min, cooled and then Bathocuproine (BCP) was spin coated on the PCBM, annealed at 65 ℃ for 5 min. Finally, metal electrodes are evaporated under the high vacuum condition. The J-V curve is measured under 1 sunlight, and the optimal device performance is as follows: the short-circuit current density is 23.25mA cm -2 Open circuit voltage of 0.98V, fill factor of 77.42%, powerThe conversion efficiency was 17.6%. Through the analysis of the corresponding photovoltaic parameters, the 1i can realize the transfer of the interface carriers, which is consistent with the expectation.
Figure BDA0003753074140000151
Figure BDA0003753074140000161
In summary, the application provides a method for synthesizing polysubstituted indole compounds with good application prospects in the fields of biology, medicines and photoelectric materials in a chemically selective and regioselective modular manner by using simple and easily available N-alkyl-N-arylnitrosamides and aryl ethylene as reaction substrates under the conditions of an inert solvent, catalysis of trivalent rhodium and assistance of molecular oxygen. The synthesis method of the polysubstituted indole does not need a pre-prepared multifunctional raw material, has the characteristics of internal oxidation and traceless guidance, does not need to use stoichiometric protonic acid or Grignard reagent, has the characteristic of green oxidation by taking oxygen in the air as a co-oxidant, has the characteristics of multiple dehydrogenation and strong coordination compatibility, and shows good performance in a hole transport layer of a solar cell (the indole skeleton in the application can obtain power conversion efficiency of 17.59%).
In the description herein, references to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples" or the like mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present patent application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While several embodiments of the present patent application have been shown and described, it will be appreciated by those of ordinary skill in the art that: numerous changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the present patent application, the scope of which is defined by the claims and their equivalents.

Claims (10)

1. A method for preparing a polysubstituted indole compound, which is characterized by comprising the following steps: in an inert solvent, under the action of a trivalent rhodium catalyst, reacting an N-aryl nitrosamide compound (formula II) with an aryl ethylene compound (formula III) to obtain a polysubstituted indole compound (formula I):
Figure FDA0003753074130000011
wherein Ar is 1 Is a para-position, meta-position, ortho-position and other multi-substituted benzene ring or heterocyclic compound, Ar 2 Is para-position and meta-position substituted benzene ring or condensed ring, and R is (cyclo) alkyl or functional group substituted benzene ring.
2. The process for producing a polysubstituted indole compound according to claim 1, characterized in that: the solvent is any one or more of toluene, tetrahydrofuran, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, 1, 2-dichloroethane, ethanol and water.
3. The process for producing a polysubstituted indole compound according to claim 1, wherein: the trivalent rhodium catalyst is any one or more of pentamethylcyclopentadienyl rhodium chloride dimer, pentamethylcyclopentadienyl iridium chloride dimer and acetonitrile-pentamethylcyclopentadienyl rhodium chloride dimer.
4. The process for producing a polysubstituted indole compound according to claim 1, wherein: the halide ion capturing agent is any one or more of silver hexafluoroantimonate and bis (trifluoromethanesulfonimide) silver.
5. The process for producing a polysubstituted indole compound according to claim 1, wherein: and an additive is also required to be added in the reaction, and the additive is any one or more of sodium acetate, sodium trifluoroacetate, sodium pivalate, sodium glycinate, sodium propionate and sodium 2,4, 6-trimethyl benzoate.
6. The process for producing a polysubstituted indole compound according to claim 1, wherein: the reaction molar ratio of the N-aryl nitrosamide compound (formula II) to the terminal olefin compound (formula III) is 1: 1.5-1: 2.
7. The process for preparing a polysubstituted indole compound according to claim 3, characterized in that: the amount of the trivalent rhodium catalyst was 2 mol% of the amount of the N-arylnitrosamide compound (formula II).
8. The process for producing a polysubstituted indole compound according to claim 1, characterized in that: the reaction is carried out at 80-120 ℃; the reaction is carried out for 12-24 hours.
9. A process for the preparation of a polysubstituted indole compound according to claim 1 and characterized in that: the method comprises the following specific steps:
s1: in a reactor, in the air, 2.5mg of pentamethylcyclopentadienylrhodium dichloride dimer, 3.9mg of silver trifluoromethanesulfonylimide, 27.2mg of sodium trifluoroacetate, 1.0mL of 1, 2-dichloroethane, 27.2mg of N-methyl-N-phenylnitrosamide and 31.2mg of styrene were added in this order;
s2: reacting the reaction solution at 100 ℃ for 12 hours;
s3: and after the reaction is finished, separating the mixture by using a column chromatography separation technology to obtain the target compound.
10. A solar cell, characterized by: the solar cell is a perovskite solar cell, and the hole transport material in the perovskite solar cell adopts the polysubstituted indole compound prepared by the preparation method as claimed in claim 1.
CN202210849941.7A 2022-07-19 2022-07-19 Preparation method and application of polysubstituted indole compound Pending CN115108960A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210849941.7A CN115108960A (en) 2022-07-19 2022-07-19 Preparation method and application of polysubstituted indole compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210849941.7A CN115108960A (en) 2022-07-19 2022-07-19 Preparation method and application of polysubstituted indole compound

Publications (1)

Publication Number Publication Date
CN115108960A true CN115108960A (en) 2022-09-27

Family

ID=83331278

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210849941.7A Pending CN115108960A (en) 2022-07-19 2022-07-19 Preparation method and application of polysubstituted indole compound

Country Status (1)

Country Link
CN (1) CN115108960A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115504933A (en) * 2022-10-13 2022-12-23 广东工业大学 Preparation method and application of polysubstituted quinolinone compound
CN115650914A (en) * 2022-11-09 2023-01-31 广东工业大学 Preparation method of indenoquinoline derivative

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111138451A (en) * 2020-01-20 2020-05-12 淮阴工学院 Doping-free hole transport material based on indeno [2,1-b ] carbazole and preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111138451A (en) * 2020-01-20 2020-05-12 淮阴工学院 Doping-free hole transport material based on indeno [2,1-b ] carbazole and preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JYOTI PRASAD ET AL.: "\'V\' Shape A-D-A-Type Designed Small Hole Conductors for Efficient Indoor and Outdoor Staging from Solid Dye-Sensitized Solar Cells and Perovskite Solar Cells", 《SOLAR RRL》, vol. 5, no. 8, pages 2100206 *
LIANG, YUJIE ET AL.: "Cationic Cobalt(III) Catalyzed Indole Synthesis: The Regioselective Intermolecular Cyclization of N-Nitrosoanilines and Alkynes", 《ANGEWANDTE CHEMIE, INTERNATIONAL EDITION》, vol. 55, no. 12, pages 4035 - 4039 *
WANG, CHENGMING ET AL.: "Traceless Directing Strategy: Efficient Synthesis of N-Alkyl Indoles via Redox-Neutral C-H Activation", 《ORGANIC LETTERS》, vol. 15, no. 20, pages 5294 - 5297 *
WENSEN OUYANG ET AL.: "Modular construction of functionalized anilines via switchable C-H and N-alkylations of traceless N-nitroso anilines with olefins", 《ORGANIC CHEMISTRY FRONTIERS》, vol. 9, no. 10, pages 2746 - 2752 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115504933A (en) * 2022-10-13 2022-12-23 广东工业大学 Preparation method and application of polysubstituted quinolinone compound
CN115650914A (en) * 2022-11-09 2023-01-31 广东工业大学 Preparation method of indenoquinoline derivative

Similar Documents

Publication Publication Date Title
CN115108960A (en) Preparation method and application of polysubstituted indole compound
Suijkerbuijk et al. Merging porphyrins with organometallics: synthesis and applications
Kumar et al. Palladium-catalyzed [2+ 2+ 2] annulation via transformations of multiple C–H bonds: one-pot synthesis of diverse indolo [3, 2-a] carbazoles
CN110156660B (en) Isoindoline derivative and preparation method thereof
CN115093410B (en) Preparation method of beta-carboline compound
CN115197138B (en) Preparation method of isoquinoline derivative
CN112480050B (en) Synthesis method of fullerene spiro-derivative
CN109134372B (en) Preparation method of pyridoindene compounds
Zou et al. Palladium‐Catalyzed Intramolecular Dehydrogenative Arylboration of Alkenes
Jiang et al. Merging Visible Light Photocatalysis and P (III)‐Directed C− H Activation by a Single Catalyst: Modular Assembly of P‐Alkyne Hybrid Ligands
CN109810147B (en) Pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex, and preparation and application thereof
CN108640944B (en) Conjugated eneyne amide compounds and preparation method and application thereof
CN112430206B (en) Preparation method of chiral/racemic 6-substituted indole compound
CN113845509B (en) Synthetic method of indolyl-substituted spiro [ cyclobutane-1,1' -indene ] compound
CN111004164B (en) Preparation method of polysubstituted 2-aryl indole derivative
CN109897039B (en) Method for preparing pyrrolo [3,2,1-ij ] quinolinone compound
CN109776546B (en) Method for preparing indolopyrrolidone compound
CN111892528A (en) Preparation method of 7-amide indole compound
CN117143017A (en) Method for constructing isoquinoline compound based on aryl migration strategy, hole transport material molecule and preparation method thereof, perovskite solar cell and preparation method thereof
CN109851558B (en) Azepine condensed ring derivative and preparation method and application thereof
Shaw et al. Harnessing photocatalytic and electrochemical approaches for C–H bond trifluoromethylation and fluoroalkylation
CN109796399B (en) N-alpha, beta-unsaturated ketone-containing compound and preparation method and application thereof
CN113735832B (en) Preparation method of 7-succinimidyl indole compound
Das et al. Rhodium-catalyzed annulation for the construction of indole core: An update
CN110862347B (en) Preparation method of 2-aryl substituted quinoline nitroxide compound

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20240403

Address after: 1003, Building A, Zhiyun Industrial Park, No. 13 Huaxing Road, Tongsheng Community, Dalang Street, Longhua District, Shenzhen City, Guangdong Province, 518000

Applicant after: Shenzhen Wanzhida Enterprise Management Co.,Ltd.

Country or region after: China

Address before: 510006 No. 100 West Ring Road, Panyu District University, Guangdong, Guangzhou

Applicant before: GUANGDONG University OF TECHNOLOGY

Country or region before: China