CN111822047B - Method for synthesizing indole derivatives through magnetic mesoporous polymeric ionic liquid supported catalysis - Google Patents

Method for synthesizing indole derivatives through magnetic mesoporous polymeric ionic liquid supported catalysis Download PDF

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CN111822047B
CN111822047B CN202010689818.4A CN202010689818A CN111822047B CN 111822047 B CN111822047 B CN 111822047B CN 202010689818 A CN202010689818 A CN 202010689818A CN 111822047 B CN111822047 B CN 111822047B
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catalyst
ionic liquid
indole
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CN111822047A (en
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刘中秋
应安国
李胜男
刘宪钦
王杰
刘玉静
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Dou Weihua
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Qufu Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
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Abstract

The invention discloses a preparation method of a magnetic mesoporous polymerization ionic liquid catalyst, which comprises the following steps: 1) dissolving equimolar amounts of 2-bromoethyl acrylate and triethylene diamine in a methanol solution, heating and refluxing for reaction for a certain time at 50-60 ℃ under the protection of vacuum nitrogen, and carrying out reduced pressure concentration and vacuum drying to obtain a light yellow viscous ionic liquid; 2) mixing the ionic liquid obtained in the step 1) with terminal alkene modified Fe3O4Dissolving divinylbenzene and azodiisobutyronitrile in methanol, heating and refluxing at 60-80 deg.c in vacuum until the reaction is completed, and vacuum drying to obtain the final catalyst. The invention also discloses the catalyst and application thereof in synthesizing indole derivatives and seven-element fused indole. The method has the advantages of high yield, simple operation, simple catalyst recovery, good reusability of a catalytic reaction system, mild reaction conditions and good green industrial prospect.

Description

Method for synthesizing indole derivatives by magnetic mesoporous polymeric ionic liquid supported catalysis
The technical field is as follows:
the invention relates to the technical field of organic compound synthesis, in particular to a magnetic mesoporous polymerization ionic liquid catalyst and application thereof in preparation of multi-component synthetic indole derivatives and seven-membered ring fused indoles.
Background art:
the indole compound is an important fine chemical raw material, becomes a hot heterocyclic chemical raw material at home and abroad, and has a wide development prospect. Indole compounds widely exist in nature, mostly have biological activity, and are widely applied in the fields of pesticides, medicines, dyes, feeds, foods, additives and the like. The multi-component reaction is a one-pot method, molecules with complex structures are directly obtained, and the method is an effective means for synthesizing molecular diversity and complexity and has economical efficiency and environmental friendliness. Therefore, the indole compound prepared by utilizing the multi-component reaction has the advantages of economy, high efficiency, simplicity, convenience, easy operation and environmental friendliness.
In recent years, the polymerized ionic liquid as a new type of novel ionic polymer has certain special physicochemical properties, and the ionic liquid is combined into a polymer skeleton, so that the dual advantages of the ionic liquid and a high-molecular polymer are combined. The mesoporous polymeric ionic liquid is a novel porous material formed by copolymerizing ionic liquid, a cross-linking agent and other monomers, and has the dual characteristics of the mesoporous material and the polymeric ionic liquid. The mesoporous polymeric ionic liquid has the characteristics of adjustable porosity and easiness in modifying functional groups by designing ion parts of specific tasks, and is widely applied to membranes, electrolytes of electrochemical super capacitors, pH, heat, light, solvents and CO2Responsive materials, and the like. And the preparation of the supported polymeric ionic liquid is more beneficial to the recovery and the recycling after the reaction. Compared with the traditional catalyst, the catalyst has a mesoporous structure, so that the catalytic efficiency can be greatly improved, the catalyst and a product can be more easily separated after reaction, and the problems of catalyst recovery and separation are better solved.
The invention content is as follows:
the invention aims to replace the traditional method for synthesizing indole compounds by catalytic catalysis of catalysts, and provides a method for synthesizing indole derivatives and seven-membered fused indoles, which is environment-friendly, efficient and recyclable.
The invention provides a preparation method of a magnetic mesoporous polymerization ionic liquid catalyst, which comprises the following steps:
1) dissolving 2-bromoethyl acrylate and triethylene diamine in equal molar weight in methanol solution, heating and refluxing for reaction for a certain time at 50-60 ℃ under the protection of vacuum nitrogen, concentrating under reduced pressure, and drying under vacuum to obtain faint yellow viscous ionic liquid;
2) mixing the ionic liquid obtained in the step 1) with terminal alkene modified Fe3O4Dissolving divinylbenzene and an initiator in methanol, heating and refluxing at 60-80 ℃ in vacuum until the reaction is complete, and drying in vacuum after the reaction is finished to obtain the final catalyst.
In one embodiment according to the present invention, the ionic liquid has a molecular structure as shown in formula I.
Figure BDA0002588906420000021
In one embodiment according to the invention, the alkene-modified Fe in step 2) is3O4The molar ratio of the initiator to the divinylbenzene to the ionic liquid is 1: 1: 4: 4. preferably, the initiator is azobisisobutyronitrile.
The invention also provides a magnetic mesoporous polymerization ionic liquid catalyst, which is prepared according to the preparation method.
In one embodiment according to the present invention, the molecular structure of the catalyst is represented by structural formula II.
Figure BDA0002588906420000022
In another aspect of the present invention, there is provided a method for synthesizing an indole derivative and a seven-membered ring fused indole, comprising:
and (2) adding indole, a methyl active compound, aromatic aldehyde and the catalyst into ethanol serving as a solvent, uniformly mixing, and reacting for 6-10 hours to obtain the corresponding indole derivative and seven-membered ring fused indole.
Preferably, after the reaction is finished, the catalyst is separated and recovered by an external magnetic field; the residue is concentrated under reduced pressure to remove the solvent, and the product is obtained by column chromatography separation.
In one embodiment according to the present invention, the molar ratio of indole, methyl active compound and aromatic aldehyde is 1: 1: 1.
in one embodiment according to the present invention, the molar amount of the catalyst is 0.01 to 0.03 times that of indole.
In one embodiment according to the present invention, the indoles are selected from one of 1-H indole, 2-methyl indole or 5-methoxy indole; the methyl active compound is one of malononitrile and ethyl cyanoacetate; the aromatic aldehyde is selected from one of formaldehyde, p-chlorobenzaldehyde, p-fluorobenzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldehyde, p-nitrobenzaldehyde, p-trifluoromethylbenzaldehyde, 2-chlorobenzaldehyde, m-nitrobenzaldehyde or 3, 4-dimethoxybenzaldehyde.
The invention also provides the indole derivative and the seven-membered ring fused indole prepared according to the synthesis method.
The invention has the beneficial effects that:
1) after the reaction of the catalyst provided by the invention is finished, the catalyst can be separated and recovered by using a magnet;
2) the recovered catalyst is washed by ethanol, and can be used for the next batch of reaction after vacuum drying, the catalyst is repeatedly used for 10 times, and the reaction yield is not obviously reduced.
3) The synthesis method of the indole derivative and the seven-element fused indole has the advantages of high yield, simple operation, simple catalyst recovery, good reusability of a catalytic reaction system, mild reaction conditions and good green industrialization prospect.
The specific implementation mode is as follows:
the following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention and to clearly and clearly define the scope of the present invention.
EXAMPLE 1 preparation of the catalyst
1) The preparation process of the functionalized mesoporous polymeric ionic liquid comprises the following steps:
dissolving 2-bromoethyl acrylate and triethylene diamine in equal molar weight in methanol solution, protecting with vacuum nitrogen, heating and refluxing at 55 deg.C for 24 hr, concentrating under reduced pressure, and vacuum drying to obtain light yellowA viscous liquid. For the preparation of ionic liquids1The structure was confirmed by H NMR. The molecular structure of the ionic liquid is shown as a structural formula I:
Figure BDA0002588906420000041
2) the obtained ionic liquid and the terminal alkene modified Fe3O4Divinylbenzene and initiator azobisisobutyronitrile are dissolved in methanol, wherein, the terminal alkene modified Fe3O4The molar ratio of the initiator to the divinylbenzene to the ionic liquid is 1: 1: 4: and 4, heating and refluxing for 24 hours at 70 ℃ in vacuum, and drying at 70 ℃ in vacuum after the reaction is finished to obtain the final catalyst. As shown in structure ii.
Figure BDA0002588906420000042
Example 2
Sequentially adding indole (1mmol), malononitrile (1mmol), p-chlorobenzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) into a 50mL single-neck bottle, stirring for 6 hours at 60 ℃, detecting by TLC (thin layer chromatography), allowing the raw materials to basically disappear, separating the catalyst and the product by using external magnetic force, concentrating the obtained product under reduced pressure, and finally separating by column chromatography to obtain the product with the yield of 95%.
2-((4-chlorophenyl)(1H-indol-3-yl)methyl)malononitrile.1H NMR(400MHz, CDCl3,TMS)(ppm):δ 8.33(s,1H),7.39(m,6H),7.39(m,6H),7.24(m,2H),7.08 (m,1H),4.91(d,J＝4.8Hz,1H),4.44(d,J＝4.6Hz,1H)。
Example 3
Sequentially adding indole (1mmol), malononitrile (1mmol), p-fluorobenzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) into a 50mL single-mouth bottle, stirring for 6 hours at 60 ℃, detecting by TLC (thin layer chromatography), enabling the raw materials to basically disappear, separating the catalyst and the product by using external magnetic force, concentrating the obtained product under reduced pressure, and finally separating by column chromatography to obtain the product with the yield of 85%.
2-((4-fluorophenyl)(1H-indol-3-yl)methyl)malononitrile.1H NMR(400MHz, CDCl3,TMS)(ppm):δ 8.34(s,1H),7.24(m,3H),7.40(m,3H),7.07(m,3H),4.91(d,J ＝4.6Hz,1H),4.43(d,J＝8.8Hz,1H)；13C NMR(100MHz,CDCl3)165.26,136.41, 130.19,122.45,119.91,118.74,115.66,111.60。
Example 4
Indole (1mmol), malononitrile (1mmol), p-trifluoromethylbenzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) are sequentially added into a 50mL single-mouth bottle, the mixture is stirred for 7 hours at 60 ℃, TLC (thin layer chromatography) detects that the raw materials basically disappear, the catalyst and the product are separated by external magnetic force, the obtained product is concentrated under reduced pressure, and finally the product is obtained by column chromatography separation with the yield of 83%.
2-((1H-indol-3-yl)(4-(trifluoromethyl)phenyl)methyl)malononitrile.1H NMR (400MHz,CDCl3,TMS)(ppm):δ 8.35(s,1H),7.65(d,J＝8.8Hz,2H),7.57(d,J＝ 7.6Hz,2H),7.39(m,2H),7.25(m,2H),7.09(m,1H),4.99(d,J＝8.4Hz,1H),4.47 (d,J＝5.2Hz,1H)；13C NMR(100MHz,CDCl3)141.02,136.31,128.74,126.21, 125.62,123.35,120.53,118.52,111.94,43.78,29.26。
Example 5
Indole (1mmol), malononitrile (1mmol), 2-chlorobenzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) are sequentially added into a 50mL single-mouth bottle, the mixture is stirred for 8 hours at 60 ℃, TLC detection is carried out, the raw materials basically disappear, the catalyst and the product are separated by external magnetic force, the obtained product is decompressed and concentrated, and finally, the product is obtained by column chromatography separation, and the yield is 78%.
2-((2-chlorophenyl)(1H-indol-3-yl)methyl)malononitrile.1H NMR(400MHz, CDCl3,TMS)(ppm):δ 8.38(s,1H),7.46(m,2H),7.30(m,1H),7.26(m,5H), 7.15(m,1H),5.53(d,J＝8.6Hz,1H),4.51(d,J＝4.4Hz,1H)；13C NMR(100MHz, CDCl3)136.21,134.64,133.59,130.09,127.77,126.03,123.20,122.56,120.36, 118.62,112.15,111.70,111.11,40.03,27.78。
Example 6
Indole (1mmol), malononitrile (1mmol), p-methoxybenzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) are sequentially added into a 50mL single-neck bottle, the mixture is stirred for 6 hours at 60 ℃, TLC (thin layer chromatography) detects that raw materials basically disappear, the catalyst and products are separated by external magnetic force, the obtained products are concentrated under reduced pressure, and finally the products are obtained by column chromatography separation with the yield of 83%.
2-((1H-indol-3-yl)(4-methoxyphenyl)methyl)malononitrile.1H NMR(400 MHz,CDCl3,TMS)(ppm):δ 8.34(s,1H),7.34(m,4H),7.32(d,J＝4.8Hz,2H), 7.24(s,1H),7.21(m,2H),4.85(d,J＝8.8Hz,1H),4.37(d,J＝4.4Hz,1H),3.77(s, 3H)。
Example 7
Indole (1mmol), malononitrile (1mmol), 3, 4-dimethoxybenzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) are sequentially added into a 50mL single-mouth bottle, stirred for 6 hours at 60 ℃, TLC detection shows that the raw materials basically disappear, the catalyst and the product are separated by external magnetic force, the obtained product is concentrated under reduced pressure, and finally the product is obtained by column chromatography separation with the yield of 88%.
2-((3,4-dimethoxyphenyl)(1H-indol-3-yl)methyl)malononitrile.1H NMR(400 MHz,CDCl3,TMS)(ppm):δ 8.40(s,1H),7.38(m,2H),7.29(m,1H),7.23(m,1H), 7.07(m,2H),6.95(d,J＝7.2Hz,1H),6.86(d,J＝6.8Hz,1H),4.87(d,J＝4.4Hz, 1H),4.45(d,J＝8.4Hz,1H),3.87(s,3H),3.82(s,3H)；13C NMR(100MHz,CDCl3) 149.28,136.32,131.72,129.50,123.09,122.05,120.43,118.77,112.52,111.46, 55.95,43.95,29.87。
Example 8
Indole (1mmol), ethyl cyanoacetate (1mmol), benzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) are sequentially added into a 50mL single-neck bottle, the mixture is stirred for 6 hours at 60 ℃, TLC (thin layer chromatography) detects that the raw materials basically disappear, the catalyst and the product are separated by external magnetic force, the obtained product is concentrated under reduced pressure, and finally the product is obtained by column chromatography separation with the yield of 86%.
ethyl 2-cyano-3-(1H-indol-3-yl)-3-phenylpropanoate.1H NMR(400MHz, CDCl3，TMS)(ppm)：8.34(d，J＝18.4Hz,1H),7.40(m,8H),7.33(m,2H),5.05 (m,1H),4.32(d,J＝8.8Hz,1H),4.31(d,J＝5.2Hz,2H),4.09(m,2H),1.05(m, 1H)。
Example 9
Indole (1mmol), ethyl cyanoacetate (1mmol), 2-chlorobenzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) are sequentially added into a 50mL single-neck bottle, stirred for 7 hours at 60 ℃, TLC detects that the raw materials basically disappear, the catalyst and the product are separated by external magnetic force, the obtained product is decompressed and concentrated, and finally the product is obtained by column chromatography separation with the yield of 82%.
ethyl 3-(2-chlorophenyl)-2-cyano-3-(1H-indol-3-yl)propanoate.1H NMR (400MHz,CDCl3,TMS)(ppm):δ 8.50(s,1H),7.59(s,1H),7.24(m,4H),7.05(m, 4H),5.66(d,J＝4.8Hz,1H),4.39(d,J＝8.4Hz,1H),4.10(d,J＝9.2Hz,2H),1.04 (m,3H)。
Example 10
Indole (1mmol), ethyl cyanoacetate (1mmol), p-chlorobenzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) are sequentially added into a 50mL single-neck flask, stirred for 6 hours at 60 ℃, TLC detects that the raw materials basically disappear, the catalyst and the product are separated by external magnetic force, the obtained product is decompressed and concentrated, and finally the product is obtained by column chromatography separation with the yield of 86%.
ethyl 3-(4-chlorophenyl)-2-cyano-3-(1H-indol-3-yl)propanoate.1H NMR (400MHz,CDCl3,TMS)(ppm):δ 8.26(d,J＝19.2Hz,1H),7.19(m,8H),6.95(m, 1H),4.95(m,1H),4.08(d,J＝8.4Hz,1H),4.01(m,2H),1.02(m,3H)。
Example 11
Sequentially adding indole (1mmol), ethyl cyanoacetate (1mmol), p-fluorobenzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) into a 50mL single-mouth bottle, stirring for 6 hours at 60 ℃, detecting by TLC (thin layer chromatography), basically removing raw materials, separating the catalyst and a product by using external magnetic force, concentrating the obtained product under reduced pressure, and finally separating by column chromatography to obtain the product with the yield of 91%.
Ethyl 2-cyano-3-(4-fluorophenyl)-3-(1H-indol-3-yl)propanoate.1H NMR (400MHz,CDCl3,TMS)(ppm):δ 8.26(d,J＝19.2Hz,1H),7.37(m,4H),7.14(m, 4H),5.07(d,J＝7.6Hz,1H),4.30(d,J＝6.4Hz,1H),4.12(m,2H),1.04(m,3H)；13C NMR(100MHz,CDCl3)165.18,138.32,136.17,133.59,129.21,126.46,122.46, 119.89,118.84,116.22,112.73,111.48,63.14,44.92,42.63,13.80。
Example 12
Sequentially adding 2-methylindole (1mmol), malononitrile (1mmol), 2-chlorobenzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) into a 50mL single-mouth bottle, stirring for 10 hours at 60 ℃, detecting by TLC (thin layer chromatography), basically eliminating raw materials, separating the catalyst and a product by using external magnetic force, concentrating the obtained product under reduced pressure, and finally separating by column chromatography to obtain the product with the yield of 90%.
2-((2-chlorophenyl)(2-methyl-1H-indol-3-yl)methyl)malononitrile.1H NMR (400MHz,CDCl3,TMS)(ppm):δ 8.02(s,1H),7.71(m,1H),7.42(m,3H),7.29(m, 2H),7.12(m,1H),7.03(m,1H),5.29(d,J＝11.6Hz,1H),2.54(s,3H)。
Example 13
Sequentially adding 2-methoxyindole (1mmol), malononitrile (1mmol), benzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) into a 50mL single-mouth bottle, stirring for 10 hours at 60 ℃, detecting by TLC (thin layer chromatography), enabling the raw materials to basically disappear, separating the catalyst and the product by using external magnetic force, concentrating the obtained product under reduced pressure, and finally separating by column chromatography to obtain the product with the yield of 92%.
2-((5-methoxy-1H-indol-3-yl)(phenyl)methyl)malononitrile.1H NMR(400 MHz,CDCl3,TMS)(ppm):δ 8.19(s,1H),7.45(m,2H),7.36(m,4H),7.29(d,J＝ 8.4Hz,1H),6.87(m,1H),6.68(s,1H),4.88(d,J＝4.8Hz,1H),4.44(d,J＝8.4Hz, 1H),3.72(s,3H)。
Example 14
Sequentially adding 4-hydroxyindole (1mmol), malononitrile (1mmol), benzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) into a 50mL single-mouth bottle, stirring for 10 hours at 60 ℃, detecting by TLC (thin layer chromatography), enabling the raw materials to basically disappear, separating the catalyst and the product by using external magnetic force, concentrating the obtained product under reduced pressure, and finally separating by column chromatography to obtain the product with the yield of 90%.
(E)-2-amino-4-phenyl-4,6-dihydrooxepino[4,3,2-cd]indole-3-carbonitrile.1H NMR(400MHz,CDCl3,TMS)(ppm):δ 8.26(s,1H),7.29(m,2H),7.21(m,4H), 7.08(d,J＝9.6Hz,1H),6.74(d,J＝8.8Hz,1H),6.65(m,1H),4.84(s,1H),4.66(s, 2H)。
Example 15
Sequentially adding 4-hydroxyindole (1mmol), malononitrile (1mmol), p-nitrobenzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) into a 50mL single-mouth bottle, stirring at 60 ℃ for 510 hours, detecting by TLC (thin layer chromatography), basically eliminating raw materials, separating the catalyst and a product by using external magnetic force, concentrating the obtained product under reduced pressure, and finally separating by column chromatography to obtain the product with the yield of 88%.
(E)-2-amino-4-(4-nitrophenyl)-4,6-dihydrooxepino[4,3,2-cd]indole-3-carbon itrile.1H NMR(400MHz,CDCl3,TMS)(ppm):δ 8.36(s,1H),8.16(d,J＝9.2Hz, 2H),7.38(d,J＝11.Hz,2H),7.25(m,1H),7.11(d,J＝9.6Hz,1H),6.66(m,2H), 4.97(s,1H),4.79(s,2H)。
Example 16
Sequentially adding 4-hydroxyindole (1mmol), malononitrile (1mmol), 2-chlorobenzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) into a 50mL single-neck bottle, stirring for 5 hours at 60 ℃, detecting by TLC (thin layer chromatography), basically eliminating raw materials, separating the catalyst and a product by using external magnetic force, concentrating the obtained product under reduced pressure, and finally separating by column chromatography to obtain the product with the yield of 91%.
(E)-2-amino-4-(2-chlorophenyl)-4,6-dihydrooxepino[4,3,2-cd]indole-3-carbo nitrile.1H NMR(400MHz,CDCl3,TMS)(ppm):δ 8.36(s,1H),7.36(d,j＝9.6Hz, 1H),7.20(m,1H),7.16(m,3H),7.06(d,9.2Hz,1H),6.78(d,9.6Hz,1H),6.64(m, 1H),5.51(s,1H),4.72(s,2H)。
Example 17
Sequentially adding 4-hydroxyindole (1mmol), malononitrile (1mmol), p-trifluoromethylbenzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) into a 50mL single-mouth bottle, stirring for 5 hours at 60 ℃, detecting by TLC (thin layer chromatography), basically eliminating raw materials, separating the catalyst and a product by using external magnetic force, concentrating the obtained product under reduced pressure, and finally separating by column chromatography to obtain the product with the yield of 70%.
(E)-2-amino-4-(4-(trifluoromethyl)phenyl)-4,6-dihydrooxepino[4,3,2-cd]ind ole-3-carbonitrile.1H NMR(400MHz,CDCl3,TMS)(ppm):δ 8.35(d,J＝19.6Hz, 1H),7.55(d,J＝8.0Hz,2H),7.33(d,J＝7.6Hz,2H),7.23(d,J＝4.0Hz,1H),7.10(d, J＝8.0Hz,1H),6.68(m,2H),4.91(d,J＝2.0Hz,1H),4.75(d,J＝8.0Hz,2H)。
Example 18
Sequentially adding 4-hydroxyindole (1mmol), malononitrile (1mmol), p-fluorobenzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) into a 50mL single-mouth bottle, stirring for 6 hours at 60 ℃, detecting by TLC (thin layer chromatography), basically eliminating raw materials, separating the catalyst and a product by using external magnetic force, concentrating the obtained product under reduced pressure, and finally separating by column chromatography to obtain the product with the yield of 81%.
(E)-2-amino-4-(4-fluorophenyl)-4,6-dihydrooxepino[4,3,2-cd]indole-3-carbo nitrile.1H NMR(400MHz,CDCl3,TMS)(ppm):δ 8.29(s,1H),7.17-7.23(m,3H), 7.09(d,J＝7.7Hz,1H),6.98(m,2H),6.70(d,J＝8.4Hz,1H),6.65(m,1H),4.84(s, 1H),4.68(s,2H)；13C NMR(100MHz,CDCl3)159.16,141.29,136.28,129.55, 124.55,122.94,120.18,116.86,115.62,115.41,111.96,108.50,99.12,58.51,40.30, 18.45。
Example 19
Sequentially adding 4-hydroxyindole (1mmol), malononitrile (1mmol), m-nitrobenzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) into a 50mL single-mouth bottle, stirring for 6 hours at 60 ℃, detecting by TLC (thin layer chromatography), basically eliminating raw materials, separating the catalyst and a product by using external magnetic force, concentrating the obtained product under reduced pressure, and finally separating by column chromatography to obtain the product with the yield of 85%.
(E)-2-amino-4-(3-nitrophenyl)-4,6-dihydrooxepino[4,3,2-cd]indole-3-carbon itrile.1H NMR(400MHz,CDCl3,TMS)(ppm):δ 8.33(s,1H),8.10(m,1H),8.05 (m,2H),7.63(d,J＝7.6,2H),7.49(m,1H),7.24(d,J＝2.8Hz,1H),7.11(d,J＝ 9.2Hz,1H),6.67(m,2H),4.99(s,1H),4.79(s,2H)；13C NMR(100MHz,CDCl3) 159.59,148.60,147.68,136.52,134.22,129.67,124.84,122.95,122.55,122.26, 117.02,110.66,108.83,99.22,58.49,40.91,29.71,18.43。
Example 20
Sequentially adding 4-hydroxyindole (1mmol), malononitrile (1mmol), p-tolualdehyde (1mmol), 20mg of catalyst and ethanol (10mL) into a 50mL single-mouth bottle, stirring for 7 hours at 60 ℃, detecting by TLC (thin layer chromatography), enabling raw materials to basically disappear, separating the catalyst and a product by using external magnetic force, concentrating the obtained product under reduced pressure, and finally separating by column chromatography to obtain the product with the yield of 85%.
(E)-2-amino-4-p-tolyl-4,6-dihydrooxepino[4,3,2-cd]indole-3-carbonitrile.1H NMR(400MHz,CDCl3,TMS)(ppm):δ 8.30(s,1H),7.18(d,J＝4.4Hz,1H),7.09 (s,4H),7.05(m,1H),6.72(d,J＝13.2Hz,1H),6.63(d,J＝4.4Hz,1H),4.79(s,1H), 4.64(s,2H),2.29(s,3H)。
Example 21
Sequentially adding 4-hydroxyindole (1mmol), malononitrile (1mmol), 3, 4-dimethoxybenzaldehyde (1mmol), 20mg of catalyst and ethanol (10mL) into a 50mL single-neck bottle, stirring at 60 ℃ for 8 hours, detecting by TLC (thin layer chromatography), basically eliminating raw materials, separating the catalyst and the product by using external magnetic force, concentrating the obtained product under reduced pressure, and finally separating by column chromatography to obtain the product with the yield of 76%.
(E)-2-amino-4-(3,4-dimethoxyphenyl)-4,6-dihydrooxepino[4,3,2-cd]indole-3- carbonitrile.1H NMR(400MHz,CDCl3,TMS)(ppm):δ 8.31(s,1H),7.21(d,J＝ 4.8Hz,1H),7.08(d,J＝9.6Hz,1H),6.78(m,4H),6.65(s,H),4.80(s,1H),4.66(s, 2H),3.84(s,3H),3.8(s,3H)。
Example 22
Indole (1mmol), malononitrile (1mmol) and p-chlorobenzaldehyde (1mmol) in example 1, the catalyst and ethanol (10mL) which are recovered by an external magnet at 50 ℃ and dried under vacuum for 5 hours are sequentially added into a 50mL single-mouth bottle, stirred at 60 ℃ for 6 hours, detected by TLC, the raw materials basically disappear, the catalyst and the product are separated by external magnetic force, the obtained product is concentrated under reduced pressure, and finally the product is obtained by column chromatography separation with the yield of 95%. The catalyst was used repeatedly 10 times, and no significant decrease in yield was observed, as shown in table 1.
TABLE 1 catalyst Performance test Table
Figure BDA0002588906420000111
Figure BDA0002588906420000121
The above summary and the detailed description are intended to demonstrate the practical application of the technical solutions provided by the present invention, and should not be construed as limiting the scope of the present invention. Various modifications, equivalent substitutions, or improvements may be made by those skilled in the art within the spirit and principles of the invention. The scope of the invention is to be determined by the appended claims.

Claims (7)

1. The preparation method of the magnetic mesoporous polymerization ionic liquid catalyst is characterized by comprising the following steps:
1) dissolving equimolar amounts of 2-bromoethyl acrylate and triethylene diamine in a methanol solution, heating and refluxing for reaction for a certain time at 50-60 ℃ under the protection of vacuum nitrogen, and carrying out reduced pressure concentration and vacuum drying to obtain a light yellow viscous ionic liquid;
2) mixing the ionic liquid obtained in the step 1) with terminal alkene modified Fe3O4Dissolving divinylbenzene and an initiator in methanol, heating and refluxing at 60-80 ℃ in vacuum until the reaction is complete, and drying in vacuum after the reaction is finished to obtain the final catalyst;
the molecular structure of the ionic liquid is shown as a structural formula I;
Figure FDA0003600503010000011
2. the method of claim 1, wherein the terminal alkene-modified Fe in step 2)3O4The molar ratio of the initiator to the divinylbenzene to the ionic liquid is 1: 1: 4: 4.
3. a magnetic mesoporous polymeric ionic liquid catalyst, characterized in that the catalyst is prepared according to the preparation method of claim 1 or 2.
4. The catalyst of claim 3, wherein the molecular structure of the catalyst is represented by structural formula II;
Figure FDA0003600503010000012
Figure FDA0003600503010000021
5. a method for synthesizing indole derivatives, which comprises the following steps:
taking ethanol as a solvent, adding indole, a methyl active compound, aromatic aldehyde and the catalyst of claim 3 or 4, mixing uniformly and reacting for 6-10 hours to obtain a corresponding indole derivative;
the indole is selected from one of 1-H indole, 2-methylindole or 5-methoxyindole; the methyl active compound is one of malononitrile and ethyl cyanoacetate; the aromatic aldehyde is selected from one of formaldehyde, p-chlorobenzaldehyde, p-fluorobenzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldehyde, p-nitrobenzaldehyde, p-trifluoromethylbenzaldehyde, 2-chlorobenzaldehyde, m-nitrobenzaldehyde or 3, 4-dimethoxybenzaldehyde.
6. The method of synthesis according to claim 5,
the mol ratio of the indole and methyl active compounds to the aromatic aldehyde is 1: 1: 1.
7. the synthesis method of claim 5, wherein the molar amount of the catalyst is 0.01-0.03 times that of indole.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994010171A1 (en) * 1992-11-02 1994-05-11 Pfizer Inc. 5-arylindole derivatives and their use as serotonin (5-ht1) agonists
JP2004115671A (en) * 2002-09-26 2004-04-15 Sekisui Plastics Co Ltd Vinyl polymer particle and method for producing the same
CN103880728A (en) * 2014-03-21 2014-06-25 台州学院 Method for preparing diindolylmethane compound
CN105126780A (en) * 2015-07-29 2015-12-09 厦门大学 Polyion liquid-based chelated absorbent and preparation method thereof
CN106582831A (en) * 2016-12-06 2017-04-26 河南工业大学 SBA-15-suported polymeric acidic ionic liquid catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994010171A1 (en) * 1992-11-02 1994-05-11 Pfizer Inc. 5-arylindole derivatives and their use as serotonin (5-ht1) agonists
JP2004115671A (en) * 2002-09-26 2004-04-15 Sekisui Plastics Co Ltd Vinyl polymer particle and method for producing the same
CN103880728A (en) * 2014-03-21 2014-06-25 台州学院 Method for preparing diindolylmethane compound
CN105126780A (en) * 2015-07-29 2015-12-09 厦门大学 Polyion liquid-based chelated absorbent and preparation method thereof
CN106582831A (en) * 2016-12-06 2017-04-26 河南工业大学 SBA-15-suported polymeric acidic ionic liquid catalyst

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