CN110818608B - Application of rare earth silicon amide as catalyst in preparation of indole or indole derivatives - Google Patents

Application of rare earth silicon amide as catalyst in preparation of indole or indole derivatives Download PDF

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CN110818608B
CN110818608B CN201911019734.3A CN201911019734A CN110818608B CN 110818608 B CN110818608 B CN 110818608B CN 201911019734 A CN201911019734 A CN 201911019734A CN 110818608 B CN110818608 B CN 110818608B
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章俊芳
蔡文选
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Wenzhou Medical University
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    • 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
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Abstract

The invention belongs to the technical field of chemical industry, and particularly provides an application of rare earth silicon amide as a catalyst in preparation of indole or indole derivatives, wherein a reaction raw material comprises a compound I, the general formula of the compound I is shown as the following formula, wherein R is hydrogen, methyl, chlorine, fluorine, bromine or methoxy,
Figure DDA0002246807100000011
rare earth silicon amide M [ N (SiMe)3)2]3Is a catalyst, wherein M is a rare earth element. The invention takes rare earth silicon amide as a catalyst and takes compound I and pinacolboron as raw materials to prepare indole or indole derivatives. The method is simple and convenient to operate and high in reaction selectivity; the synthesized indole derivative has good product quality and high yield.

Description

Application of rare earth silicon amide as catalyst in preparation of indole or indole derivatives
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to application of rare earth silicon amide as a catalyst in preparation of indole or indole derivatives, and a method for preparing indole or indole derivatives through catalysis.
Background
Indole derivatives are important organic compounds and widely exist in molecular frameworks of biological medicines, foods, cosmetics, pesticides and natural products, so that the research on the efficient synthesis method of the indole derivatives has great application value and wide application prospect.
In the prior art, the methods for synthesizing indole have been reported more, and most importantly, the Fischer indole synthesis method (Tetrahedron 2010,66, 573-577; org. Prep. proce. int.1993,25,609.) is adopted. However, the method has two main limitations, firstly, the starting materials are limited to phenylhydrazine derivatives and ketone, and the substrate range is narrow; secondly, the reaction lacks selectivity, and the synthesis of complex products is difficult to realize. Thereafter, a series of cyclization reactions starting from aniline derivatives have been developed for the preparation of indoles, and N-arylalkynylamine intramolecular cyclization reactions have been reported in the literature (org. Lett.2013,15,3112-3115) which, however, require the use of tert-butyllithium. The tert-butyl lithium is a reagent with extremely high activity, and is easy to cause experimental accidents due to improper operation in the operation process. From another perspective, dehydroreduction of indolines to produce indoles is also a highly efficient process. The literature (chem.Sci.2019,10, 4883-4889) reports the preparation of indoles by dehydroreduction of indolines using a platinum catalyst.
The method for synthesizing the isoindole derivative has the advantages of complex process, non-extensive sources of raw materials such as functionalized amine, indoline and complex catalysts, complex preparation method and high cost.
Disclosure of Invention
In order to solve the problems, the invention provides an application of rare earth silicon amide as a catalyst in preparation of indole or indole derivatives.
In order to achieve the purpose, the invention adopts the following technical scheme:
the rare earth silicon amide is used as a catalyst in the application of preparing indole or indole derivatives, the reaction raw material comprises a compound I, the general formula of the compound I is shown as the following formula, wherein R is hydrogen, methyl, chlorine, fluorine, bromine or methoxy,
Figure BDA0002246807080000021
rare earth silicon amide M [ N (SiMe)3)2]3Is a catalyst, wherein M is a rare earth element; the reaction raw material also comprises a hydrogen transfer reagent, and the carbonyl in the compound I is hydrogenated and reduced to finally generate the indole or the indole derivative in the reaction process.
Preferably, M is one of La, Nd, Sm, Gd, Yb, Lu and Y.
Preferably, the method comprises the following steps: under the anhydrous and oxygen-free atmosphere, taking a compound I and a compound II pinacol borane as raw materials, taking rare earth silicon amide as a catalyst and an organic solvent as a reaction solvent, and carrying out a rare earth catalytic hydrogen transfer reduction reaction to prepare a compound III, wherein the reaction formula of the catalytic reaction is as follows:
Figure BDA0002246807080000022
preferably, the reaction solvent is one or more of toluene, xylene, n-hexane, tetrahydrofuran and 1, 2-dichloroethane.
Preferably, the reaction solvent is toluene, xylene or n-hexane, or a mixed solution of toluene and xylene.
Preferably, the molar ratio of the compound I, the compound II and the rare earth silicon amide is 1.0/2.4/0.05-0.10, the reaction temperature is 80-120 ℃, and the reaction time is 24-36 h.
Preferably, the anhydrous and oxygen-free atmosphere is an inert gas atmosphere, and the inert gas is nitrogen or argon.
In the above catalytic reaction, the present application proposes a possible reaction mechanism, taking the product as indole, as shown in fig. 1. In fig. 1, a trisilamido rare earth catalyst reacts with pinacol borane to generate a rare earth hydride intermediate A, a rare earth-hydrogen bond is inserted into acyl to form an intermediate B, and the borane reacts with the intermediate B to obtain a borate intermediate C and generate the intermediate A. Intermediate C is then converted to iminium cation intermediate D. D reacts with pinacolborane to generate an imine E intermediate, and hydrogen and boron ester are released. The imine intermediate undergoes tautomerism to obtain the product indole.
The application is based on the application of the rare earth silicon amide as a catalyst in the preparation of indole or indole derivatives, and also provides a method for preparing the indole or indole derivatives through catalysis.
A catalytic process for preparing indole or indole derivative from RE silicon amide M [ N (SiMe)3)2]3Wherein M is one of La, Nd, Sm, Gd, Yb, Lu and Y, the reaction raw material comprises a compound I and a hydrogen transfer reagent, the general formula of the compound I is shown as the following formula, wherein R is hydrogen, methyl, chlorine, fluorine, bromine or methoxyl,
Figure BDA0002246807080000031
further, the method specifically comprises the following steps: under the atmosphere of no water and no oxygen, taking a compound I and a compound II pinacol borane as reaction raw materials, taking a rare earth silicon amide as a catalyst and an organic solvent as a reaction solvent, and carrying out a rare earth catalytic hydrogen transfer reduction reaction to prepare a compound III, wherein the molar ratio of the compound I, the compound II and the rare earth silicon amide is 1.0/2.4/0.05-0.10, the reaction temperature is 80-120 ℃, preferably 100-120 ℃, and the reaction formula of the catalytic reaction is as follows:
Figure BDA0002246807080000032
further, the reaction solvent is one or more of toluene, xylene, n-hexane, tetrahydrofuran and 1, 2-dichloroethane; preferably, the reaction solvent is toluene, xylene or n-hexane, or a mixed solution of toluene and xylene.
Further, the anhydrous and oxygen-free atmosphere is an inert gas atmosphere.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with other reaction raw materials in the prior art, the raw material compound I and the compound II selected by the application have the advantages of wide sources, easy preparation and easy storage, and have high reaction yield during preparation; the catalyst can be directly purchased in a commercial mode or easily synthesized directly and simply, and can be used for actual production.
(2) The indole or indole derivative prepared by the method has the advantages of high quality, high product yield, good economical efficiency of reaction atoms, simple and convenient preparation process and product separation and purification, strong flexibility, safe and stable process, simple and convenient operation and high reaction selectivity.
Drawings
FIG. 1 shows the mechanism of the catalytic reaction according to the present invention.
Detailed Description
The rare earth silicon amide is used as a catalyst in the application of preparing indole or indole derivatives, the reaction raw material comprises a compound I, the general formula of the compound I is shown as the following formula, wherein R is hydrogen, methyl, chlorine, fluorine, bromine or methoxy,
Figure BDA0002246807080000041
rare earth silicon amide M [ N (SiMe)3)2]3Is a catalyst, wherein M is a rare earth element; the reaction raw material also comprises a hydrogen transfer reagent, and the carbonyl in the compound I is hydrogenated and reduced to finally generate the indole or the indole derivative in the reaction process. The invention takes a compound I as a raw material and takes M [ N (SiMe)3)2]3Is used as a catalyst, in the reaction process, carbonyl in the compound I is subjected to hydrogenation reduction to finally generate indole or indole derivatives, and compared with other raw materials used in the prior art, the compound I has the advantages of wide sources or easy preparation and easy storage, and M [ N (SiMe)3)2]3The catalyst has the advantages of easy purchase or direct and simple synthesis.
Wherein M is La, Nd, Sm, Gd, Yb, Lu or Y. Through a series of screening comparison, Y [ N (SiMe) is found3)2]3The catalyst has better reaction effect than other catalysts, and Y [ N (SiMe)3)2]3Catalyst precursor Y2O3Since it is inexpensive, Y [ N (SiMe) is preferred3)2]3。
Preferably, the method specifically comprises the following steps: under the anhydrous and oxygen-free atmosphere, taking a compound I and a compound II pinacol borane as raw materials, taking rare earth silicon amide as a catalyst and an organic solvent as a reaction solvent, and carrying out a rare earth catalytic hydrogen transfer reduction reaction to prepare a compound III, wherein the reaction formula of the catalytic reaction is as follows:
Figure BDA0002246807080000042
the reaction reducing agent is pinacol borane as a hydrogen transfer reagent, the pinacol borane is cheap and easy to obtain, and compared with common hydrogen negative reagents such as silane, the pinacol borane has the characteristic of being stable to air and convenient to store and transport, and at present, literature research finds that the borane participates in the hydrogen transfer reduction 2-indolone reaction and is not reported. The method takes the compound I and the compound II pinacol borane as reaction raw materials, takes rare earth silicon amide as a catalyst and takes an organic solvent as a reaction solvent, and the reaction system has high reaction selectivity and is beneficial to realizing the synthesis of complex products.
Preferably, the reaction solvent is one or more of toluene, xylene, n-hexane, tetrahydrofuran and 1, 2-dichloroethane. The kind of solvent greatly affects the yield of the product, and the invention selects the organic solvent as the reaction solvent, wherein, the reaction effect of toluene, xylene and normal hexane is best, the yield can reach 90% or more, and the reaction can also proceed with tetrahydrofuran and 1, 2-dichloroethane as the reaction solvent, but the yield is greatly degraded, wherein, the yield is less than 60% when tetrahydrofuran is used as the reaction solvent, and the yield is less than 40% when 1, 2-dichloroethane is used as the reaction solvent. Therefore, toluene, n-hexane, xylene are the most preferable reaction solvents.
Preferably, the molar ratio of the compound I, the compound II and the rare earth silicon amide is 1.0/2.4/0.05-0.10, the reaction temperature is 80-120 ℃, and the reaction time is 24-36 h. The amount of pinacol borane used in the reaction process is 2.4 equivalents, because 2 equivalents of pinacol borane are involved in the reaction, and a slight excess of pinacol borane is more favorable for the forward direction of the reaction. Further increase of borane amount did not promote the reaction, so 2.4 equivalents of pinacolborane were selected. The dosage of the catalyst is 5-10%.
Preferably, the reaction temperature is 100-.
Preferably, the anhydrous and oxygen-free atmosphere is an inert gas atmosphere, and preferably, the inert gas is nitrogen or argon.
The present invention will be further described with reference to the following examples, which are intended to illustrate only some, but not all, of the embodiments of the present invention. All other embodiments that can be obtained by a person skilled in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention.
Example 1
The synthesis of indole has the following chemical structure:
Figure BDA0002246807080000051
under the protection of nitrogen, adding 0.5mmol of raw material 2-indolone, 1.2mmol of pinacolborane and catalyst Y [ N (SiMe)3)2]30.05mmol of toluene and 3mL of toluene react at 120 ℃ for 36h, and the isolated yield of the product is 92%.
1H NMR(CDCl3,500MHz,ppm):δ8.06(brs,1H),7.71(d,J＝7.8Hz,1H),7.41(d,J＝8.1Hz,1H),7.27-7.24(m,1H),7.20-7.17(m,2H),6.61(s,1H).13C NMR(CDCl3,125MHz,ppm):δ135.9,128.0,124.3,122.1,120.9,120.0,111.2,102.7.
Example 2
5-fluoroindole, the chemical structure is as follows:
Figure BDA0002246807080000052
under the protection of nitrogen, adding 0.5mmol of raw material 5-fluoro-2-indolone, 1.2mmol of pinacol borane and catalyst Y [ N (SiMe)3)2]30.05mmol of toluene and 3mL of toluene react at 120 ℃ for 36h, and the isolated yield of the product is 92%.
1H NMR(CDCl3,500MHz,ppm):δ8.11(brs,1H),7.35(dd,J＝2.4Hz,J＝9.6Hz,1H),7.30(dd,J＝4.4Hz,J＝8.8Hz,1H),7.24(t,J＝2.8Hz,1H),7.00(td,J＝2.5Hz,J＝9.1Hz,1H),6.57-6.55(m,1H).13C NMR(CDCl3,125MHz,ppm):δ158.1(d,J＝233.9Hz),132.5,128.4(d,J＝10.3Hz),126.1,111.7(d,J＝9.8Hz),110.5(d,J＝26.4Hz),105.5(d,J＝23.4Hz),102.9(d,J＝4.7Hz).
Example 3
The synthesis of 6-chloroindole has the following chemical structure:
Figure BDA0002246807080000061
under the protection of nitrogen, adding 0.5mmol of raw material 6-chloro-2-indolone, 1.2mmol of pinacol borane and catalyst Y [ N (SiMe)3)2]30.05mmol of toluene and 3mL of toluene react at 120 ℃ for 36 hours, and the isolation yield of the product is 83 percent.
1H NMR(CDCl3,500MHz,ppm):δ8.07(brs,1H),7.58(d,J＝8.4Hz,1H),7.36(s,1H),7.18(t,J＝2.6Hz,1H),7.14(dd,J＝1.8Hz,J＝8.4Hz,1H),6.56-6.55(m,1H).13C NMR(CDCl3,125MHz,ppm):δ136.3,128.0,126.6,125.0,121.7,120.7,111.1,102.9.
Example 4
The synthesis of 5-methylindole has the following chemical structure:
Figure BDA0002246807080000062
under the protection of nitrogen, adding 0.5mmol of raw material 5-methyl-2-indolone, 1.2mmol of pinacol borane and catalyst Y [ N (SiMe)3)2]30.05mmol of toluene and 3mL of toluene react at 120 ℃ for 36 hours, and the isolation yield of the product is 87%.
1H NMR(CDCl3,500MHz,ppm):δ7.44(m,2H),7.26(d,J＝8.5Hz,1H),7.12(d,J＝3.0Hz,1H),6.44(d,J＝3.0Hz,1H),2.39(s,3H).13C NMR(CDCl3,125MHz,ppm):δ148.0,138.6,134.0,130.2,121.2,119.4,94.8,20.9.
Example 5
The synthesis of 6-methylindole has the following chemical structure:
Figure BDA0002246807080000063
under the protection of nitrogen, addingRaw material 0.5mmol of 6-methyl-2-indolone, 1.2mmol of pinacolborane and catalyst Y [ N (SiMe)3)2]30.05mmol of toluene and 3mL of toluene react at 120 ℃ for 36 hours, and the isolation yield of the product is 89%.
1H NMR(CDCl3,500MHz,ppm):δ7.89(s,1H),7.61(d,J＝8.0Hz,1H),7.18(s,1H),7.15–7.09(m,1H),7.05(d,J＝8.0Hz,1H),6.62–6.53(m,1H),2.55(s,3H).13C NMR(CDCl3,125MHz,ppm):δ136.3,131.8,125.7,123.6,121.7,120.4,111.1,102.4,21.8.
Example 6
The synthesis of 4-methoxyindole has the following chemical structure:
Figure BDA0002246807080000064
under the protection of nitrogen, adding 0.5mmol of raw material 4-methoxy-2-indolone, 1.2mmol of pinacol borane and catalyst Y [ N (SiMe)3)2]30.05mmol of toluene and 3mL of toluene react at 120 ℃ for 36h, and the isolated yield of the product is 92%.
1H NMR(CDCl3,500MHz,ppm):δ8.15(s,1H),7.15(t,J＝8.0Hz,1H),7.12–7.09(m,1H),7.03(d,J＝8.2Hz,1H),6.72–6.66(m,1H),6.56(d,J＝7.7Hz,1H),3.98(s,3H).13C NMR(CDCl3,125MHz,ppm):δ153.4,137.3,122.9,122.8,118.6,104.7,99.73,99.66,55.4.
Example 7
The synthesis of 6-methoxyindole has the following chemical structure:
Figure BDA0002246807080000071
under the protection of nitrogen, adding 0.5mmol of raw material 6-bromo-2-indolone, 1.2mmol of pinacol borane and catalyst Y [ N (SiMe)3)2]30.05mmol of toluene and 3mL of toluene react at 120 ℃ for 36 hours, and the isolation yield of the product is 90%.
1H NMR(CDCl3,500MHz,ppm):δ6.52(m,1H),7.15-7.20(m,1H),7.23-7.24(m,1H),7.47(s,1H),7.52-7.53(m,1H),8.11(bs,1H)；13C NMR(CDCl3,125MHz,ppm):δ102.8,113.9,115.4,121.9,123.1,124.9。
Example 8
And (3) synthesis of indole: under the protection of nitrogen, adding 0.5mmol of raw material 2-indolone, 1.2mmol of pinacolborane and catalyst Y [ N (SiMe)3)2]30.05mmol of xylene and 3mL of xylene, and the product is separated and obtained in the yield of 92 percent after the reaction is carried out for 36 hours at 120 ℃.
Example 9
And (3) synthesis of indole: under the protection of nitrogen, adding 0.5mmol of raw material 2-indolone, 1.2mmol of pinacolborane and catalyst Y [ N (SiMe)3)2]30.05mmol of the product and 3mL of n-hexane react for 36h at 120 ℃, and the separation yield of the product is 90%.
Example 10
And (3) synthesis of indole: under the protection of nitrogen, adding 0.5mmol of raw material 2-indolone, 1.2mmol of pinacolborane and catalyst Y [ N (SiMe)3)2]30.05mmol of tetrahydrofuran and 3mL of tetrahydrofuran are reacted at 120 ℃ for 36h, and the isolation yield of the product is 58%.
Example 11
And (3) synthesis of indole: under the protection of nitrogen, adding 0.5mmol of raw material 2-indolone, 1.2mmol of pinacolborane and catalyst Y [ N (SiMe)3)2]30.05mmol of 1, 2-dichloroethane is reacted for 36 hours at 120 ℃, and the isolation yield of the product is 31%.
Example 12
And (3) synthesis of indole: under the protection of argon, adding 0.5mmol of raw material 2-indolone, 1.2mmol of pinacolborane and catalyst Y [ N (SiMe)3)2]30.05mmol, 1.5mL of toluene and 1.5mL of xylene, and the product is isolated in a yield of 91 percent after reacting for 36 hours at 120 ℃.
Example 13
And (3) synthesis of indole: under the protection of argon, adding 0.5mmol of raw material 2-indolone, 1.2mmol of pinacolborane and catalyst La [ N (SiMe)3)2]30.025mmol and 3ml of toluene, and the product is isolated and obtained in 66% yield after 24h reaction at 80 ℃.
Example 14
And (3) synthesis of indole: under the protection of argon, adding 0.5mmol of raw material 2-indolone, 1.2mmol of pinacolborane and catalyst Nd [ N (SiMe)3)2]30.03mmol and 3ml of toluene react at 90 ℃ for 26 hours, and the isolation yield of the product is 52 percent.
Example 15
And (3) synthesis of indole: under the protection of argon, adding 0.5mmol of raw material 2-indolone, 1.2mmol of pinacolborane and catalyst Sm [ N (SiMe)3)2]30.035mmol of toluene and 3ml of toluene react for 28h at 100 ℃, and the isolation yield of the product is 68%.
Example 16
And (3) synthesis of indole: under the protection of argon, adding 0.5mmol of raw material 2-indolone, 1.2mmol of pinacolborane and a catalyst Gd [ N (SiMe)3)2]30.04mmol of toluene and 3ml of toluene react for 30 hours at 110 ℃, and the isolation yield of the product is 77%.
Example 17
And (3) synthesis of indole: under the protection of argon, adding 0.5mmol of raw material 2-indolone, 1.2mmol of pinacolborane and catalyst Yb [ N (SiMe)3)2]30.045mmol, 3ml of toluene, and reaction at 120 ℃ for 32h, wherein the isolation yield of the product is 81%.
Example 18
And (3) synthesis of indole: under the protection of argon, adding 0.5mmol of raw material 2-indolone, 1.2mmol of pinacolborane and catalyst Lu [ N (SiMe)3)2]30.05mmol of toluene and 3ml of toluene are reacted for 34h at 120 ℃, and the isolation yield of the product is 87%.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.

Claims (11)

1. The application of rare earth silicon amide as a catalyst in the preparation of indole or indole derivatives is characterized in that reaction raw materials comprise a compound I and a compound II pinacol borane, wherein the general formula of the compound I is shown as the following formula, wherein R is hydrogen, methyl, chlorine, fluorine, bromine or methoxy,
Figure 976007DEST_PATH_IMAGE001
the structural formula of the indole or indole derivative is shown as a compound III
Figure 150636DEST_PATH_IMAGE002
，
Rare earth silicon amide M [ N (SiMe)3)2]3 Is a catalyst, wherein M is a rare earth element, and M is one of La, Nd, Sm, Gd, Yb, Lu and Y.
2. Use of a rare earth silicon amide as a catalyst in the preparation of indole or indole derivatives according to claim 1, characterized in that it comprises the following steps: under the anhydrous and oxygen-free atmosphere, taking a compound I and a compound II pinacol borane as reaction raw materials, taking rare earth silicon amide as a catalyst and an organic solvent as a reaction solvent, and carrying out a rare earth catalytic hydrogen transfer reduction reaction to prepare a compound III, wherein the reaction formula of the catalytic reaction is as follows:
Figure 220223DEST_PATH_IMAGE003
。
3. the use of a rare earth silicide as a catalyst in the preparation of indole or indole derivatives according to claim 2, wherein the reaction solvent is one or more of toluene, xylene, n-hexane, tetrahydrofuran and 1, 2-dichloroethane.
4. The use of a rare earth silicide as a catalyst in the preparation of indole or indole derivatives according to claim 2, wherein the molar ratio of compound I/compound II/rare earth silicide is 1.0/2.4/0.05-0.10, the reaction temperature is 80-120 ℃, and the reaction time is 24-36 h.
5. The use of rare earth silicon amides as catalysts for the preparation of indoles or indole derivatives as claimed in claim 4 wherein the reaction temperature is 100-120 ℃.
6. Use of a rare earth silicon amide as a catalyst in the preparation of indole or indole derivatives according to claim 2, characterized in that the anhydrous and oxygen-free atmosphere is an inert gas atmosphere.
7. A method for preparing indole or indole derivatives by catalysis is characterized in that a catalyst is rare earth silicon amide M [ N (SiMe)3)2]3Wherein M is one of La, Nd, Sm, Gd, Yb, Lu and Y, the reaction raw material comprises a compound I and a compound II pinacolborane, the general formula of the compound I is shown as the following formula, wherein R is hydrogen, methyl, chlorine, fluorine, bromine or methoxyl,
Figure 480303DEST_PATH_IMAGE004
the structural formula of the indole or indole derivative is shown as a compound III
Figure 90276DEST_PATH_IMAGE005
。
8. The process of claim 7, wherein the process comprises the steps of: under the anhydrous and oxygen-free atmosphere, taking a compound I and a compound II pinacol borane as reaction raw materials, taking a rare earth silicon amide as a catalyst and an organic solvent as a reaction solvent, and carrying out a rare earth catalytic hydrogen transfer reduction reaction to prepare a compound III, wherein the molar ratio of the compound I, the compound II and the rare earth silicon amide is 1.0/2.4/0.05-0.10, the reaction temperature is 80-120 ℃, and the reaction formula of the catalytic reaction is as follows:
Figure 384991DEST_PATH_IMAGE006
。
9. the process of claim 8, wherein the reaction temperature is 100-120 ℃.
10. The method for preparing indole or indole derivatives with catalysis as claimed in claim 8, wherein the reaction solvent is one or more of toluene, xylene, n-hexane, tetrahydrofuran and 1, 2-dichloroethane; the anhydrous and oxygen-free atmosphere is an inert gas atmosphere.
11. The method for catalytic preparation of indole or indole derivatives as claimed in claim 10, wherein the reaction solvent is toluene, xylene or n-hexane, or a mixed solution of toluene and xylene.
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