Synthesis method of 2-acylindole compound under photocatalysis

The technology of an acyl indole compound and a synthesis method, which is applied in the field of synthesis of 2-acyl indole compounds under photocatalysis, can solve the problems that the synthesis method of 2-acyl indole compounds is less involved, and achieves lower reaction activation energy and easier separation. , the effect of high yield

Active Publication Date: 2020-06-02
SHAANXI UNIV OF SCI & TECH
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  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the above method effectively introduces an acyl group into the compound, some of the acylating reagents used require pretreatment, and there are few references to the synthetic methods of 2-acylindole compounds.

Method used

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  • Synthesis method of 2-acylindole compound under photocatalysis
  • Synthesis method of 2-acylindole compound under photocatalysis
  • Synthesis method of 2-acylindole compound under photocatalysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Preparation of 2-(2-Benzoyl-1H-indol-3-yl)acetonitrile

[0054] 1mmol of 3-(2-isocyanophenyl)acrylonitrile and 2mmol of benzoylformic acid were dissolved in a reactor filled with 10mL of DMF, and 0.02mmol[Ir(dF(CF 3 )ppy) 2 (d t b-bpy)]PF 6 as catalyst, 2mmolK 2 HPO 4 It is a base, stirred under 20W blue light irradiation in the air atmosphere at room temperature for 12 hours, monitored the progress of the reaction with TLC, extracted with ethyl acetate, concentrated, and separated by column chromatography to obtain 159 mg of a light yellow solid with a yield of 61%. The product structure is as follows:

[0055]

[0056] Such as figure 1 and figure 2 Shown, product NMR characterization: 1 H NMR(400MHz,DMSO)δ11.90(s,1H), 7.87(d,J=8.1Hz,1H),7.83(d,J=7.7Hz,2H),7.77–7.69(m,1H),7.66 – 7.58(m, 2H), 7.52(d, J=8.3Hz, 1H), 7.37(t, J=7.6Hz, 1H), 7.21(t, J=7.5Hz, 1H), 4.21(s, 2H) . 13 C NMR (101MHz, DMSO) δ188.0, 138.1, 136.5, 132.8, 131.4, 129.1, 128.8, 126.3, 125....

Embodiment 2

[0058] Preparation of 2-(2-Benzoyl-5-methyl-1H-indol-3-yl)acetonitrile

[0059] Dissolve 1mmol of 3-(2-isocyano-5-methylphenyl)acrylonitrile and 2mmol of benzoylformic acid in a reactor filled with 10mL of DMF, add 0.02mmol[Ir(dtb-bpy)(ppy) 2 ]PF 6 as catalyst, 2mmolK 2 HPO 4 It is a base, stirred under 20W blue light irradiation in the air atmosphere at room temperature for 12 hours, monitored the progress of the reaction by TLC, extracted with ethyl acetate, concentrated, and separated by column chromatography to obtain 137 mg of a light yellow solid with a yield of 50%. The structural formula of the product obtained is as follows:

[0060]

[0061] Such as image 3 and Figure 4 Shown, product NMR characterization: 1 H NMR (400MHz,DMSO)δ11.77(s,1H), 7.81(d,J=7.6Hz,2H),7.74–7.79(m,1H),7.66–7.56(m,3H),7.41(d, J=8.4Hz, 1H), 7.21(d, J=8.5Hz, 1H), 4.16(s, 2H), 2.43(s, 3H). 13 C NMR(101MHz, DMSO)δ187.9,138.2,135.0,132.7,131.4,129.6,129.1,128.8,127.9,126.6, 119.1,118.6,...

Embodiment 3

[0063] Preparation of 2-(2-Benzoyl-6-methoxy-1H-indol-3-yl)acetonitrile

[0064] Dissolve 1mmol of 3-(2-isocyano-4-methoxyphenyl)acrylonitrile and 2mmol of benzoylformic acid in a reactor filled with 10mL of DMF, add 0.02mmol [Ir(dF(CF 3 )ppy) 2 (1,10-Phen)]PF 6 as catalyst, 2mmolK 2 HPO 4 It is a base, stirred under 20W blue light irradiation in the air atmosphere at room temperature for 12 hours, monitored the progress of the reaction with TLC, extracted with ethyl acetate, concentrated, and separated by column chromatography to obtain 151 mg of a light yellow solid with a yield of 52%. The product structure is as follows:

[0065]

[0066] Such as Figure 5 and Figure 6 Shown, product NMR characterization: 1 H NMR (400MHz,DMSO)δ11.70(s,1H), 7.83–7.73(m,3H),7.73–7.67(m,1H),7.65–7.57(m,2H),6.94(s,1H), 6.87 (d, J=8.9Hz, 1H), 4.17(s, 2H), 3.81(s, 3H). 13 C NMR (101MHz, DMSO) δ 187.2, 158.9, 138.5, 137.9, 132.4, 130.5, 128.9, 128.8, 121.2, 120.9, 118.6, 112.8, 112.2...

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Abstract

The invention discloses a synthesis method of a 2-acylindole compound under photocatalysis. The preparation method comprises the following steps: adding o-alkenyl aryl isocyanide, alpha-carbonylcarboxylic acid, a catalyst and an alkali into a solvent, carrying out a decarboxylation addition cyclization reaction, extracting after the reaction is completed, and separating and purifying to obtain the2-acylindole compound, wherein the reaction is carried out under the irradiation of 20 W blue light in an air atmosphere at room temperature. The synthesis method is simple and efficient. The o-alkenyl aryl isonitrile compound and the alpha-carbonylcarboxylic acid which are stable in air and easy to obtain are used as reaction raw materials, the catalyst and the alkali are added in the presence of the solvent, and the 2-acylindole compound is efficiently synthesized under mild reaction conditions.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a method for synthesizing 2-acylindole compounds under photocatalysis. Background technique [0002] 2-acylindole-containing compounds and their derivatives occupy an important position in the fields of organic synthesis, natural products, pesticides, dyes and so on. The introduction of acyl groups at the C-2 position of traditional indole is usually catalyzed by transition metals such as palladium under the control of directing groups or ligands [(a) Kumar, G.; Sekar, G.RSC Adv.2015, 5, 28292 .(b) Wang, W.; Liu, J.; Gui, Q.; Tan, Z. Synlett2015, 26, 771. (c) Li, C.; Zhu, W.; Shu, S.; Wu, X.; Liu, H. Eur. J. Org. Chem.2015, 3743. (d) Pan, C.; Jin, H.; Liu, X.; Cheng, Y.; Zhu, C. Chem. Commun.2013, 49 , 2933.(e) Zhou, B.; Yang, Y.; Li, Y. Chem. Commun.2012, 48, 5163. (f) Wu, Y.; Li, B.; Mao, F.; X.; Kwong, F.-Y. Org. Lett. 2011, 13, 3258. (g) Sharma, U.K.; Gemoets, ...

Claims

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Application Information

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Patent Type & AuthorityApplications(China)
IPC IPC(8): C07D209/18
CPCC07D209/18
Inventor李翔朱培元张晓斐张瑞红
OwnerSHAANXI UNIV OF SCI & TECH