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A photocatalytic method for the preparation of α-azide ketone compounds

A technology for azide ketones and compounds, which is applied in the field of photocatalytic preparation of α-azide ketone compounds, can solve the problems of cumbersome operation steps, many by-products, harsh conditions, etc., and achieve safe and reliable process, simplified operation, and mild reaction conditional effect

Active Publication Date: 2021-01-15
QUFU NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0014] In summary, most of the currently known synthetic methods have obvious disadvantages: cumbersome operation steps are required, or an equivalent amount of inorganic oxidant, metal reagent, or harsh conditions, high energy consumption, and many by-products

Method used

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  • A photocatalytic method for the preparation of α-azide ketone compounds
  • A photocatalytic method for the preparation of α-azide ketone compounds
  • A photocatalytic method for the preparation of α-azide ketone compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0120]

[0121] At room temperature, add styrene 20.8mg, azidotrimethylsilane 46mg, photocatalyst Rose Bengal 2.03mg, diphenyl diselenide 3.14mg and acetonitrile 2ml in sequence in a 15mL reaction tube Under the irradiation of a colored LED lamp, the reaction was stirred in the air for 2 h. After the reaction is detected by TLC, it is concentrated to solvent-free under vacuum (0.08Mpa) to obtain the crude product, which is then washed with a mixed eluent of petroleum ether and ethyl acetate with a volume ratio of 20:1, and the silica gel column is quickly Through column chromatography, the α-azide ketone product of this example was obtained as 29.6 mg of a yellow oily solid, with a yield of 92%.

[0122] 1 H NMR (CDCl 3 ,500 MHz,ppm):δ7.91(d,J=7.3 Hz,2H),7.63(t,J=7.5 Hz,1H),7.50(t,J=8.0 Hz,2H),4.56(s,2H ); 13 C NMR (CDCl 3 ,125MHz,ppm): δ 193.2,134.4,134.2,129.0,127.9,54.9; HRMS calc.for C 8 h 7 N 3 ONa(M+Na) + , 184.0487; found, 184.0491.

Embodiment 2

[0124]

[0125] At room temperature, add 23.6mg of 4-methylstyrene, 46mg of azidotrimethylsilane, 2.03mg of photocatalyst Rose Bengal, 3.14mg of diphenyldiselenide and 2ml of acetonitrile into a 15mL reaction tube, and mix well , and then under the irradiation of a 3w blue LED lamp, the reaction was stirred in the air for 2h. After the reaction is detected by TLC, it is concentrated to solvent-free under vacuum (0.08Mpa) to obtain the crude product, which is then washed with a mixed eluent of petroleum ether and ethyl acetate with a volume ratio of 20:1, and the silica gel column is quickly Column chromatography obtained the α-azide ketone product of this embodiment, which was 33.9 mg of white oily solid, with a yield of 97%.

[0126] 1 H NMR (CDCl 3 ,500 MHz,ppm):δ7.80(d,J=8.2 Hz,2H),7.29(d,J=8.0 Hz,2H),4.53(s,2H),2.42(s,3H); 13 C NMR (CDCl 3 ,125MHz,ppm): δ192.8,145.2, 131.9,129.7,128.0,54.8,21.8; HRMS calc.for C 9 h 9 N 3 ONa(M+Na) + ,198.0643; found, 198.0647. ...

Embodiment 3

[0128]

[0129] At room temperature, add 23.6mg of 3-methylstyrene, 46mg of azidotrimethylsilane, 2.03mg of photocatalyst Rose Bengal, 3.14mg of diphenyldiselenide and 2ml of acetonitrile into a 15mL reaction tube, and mix well , and then under the irradiation of a 3w blue LED lamp, the reaction was stirred in the air for 2h. After the completion of the reaction detected by TLC, it was concentrated to solvent-free under vacuum (0.08Mpa) to obtain the crude product, which was then washed with a mixed eluent of petroleum ether and ethyl acetate with a volume ratio of 20:1, and the silica gel column was quickly Through column chromatography, the α-azide ketone product of this example was obtained as 33.8 mg of a yellow solid with a yield of 96%.

[0130] 1 H NMR (CDCl 3 ,500 MHz,ppm):δ7.71(s,1H),7.67(d,J=7.7 Hz,1H),7.43(d, J=7.6 Hz,1H),7.37(t,J=7.7 Hz,1H ),4.54(s,2H),2.41(s,3H); 13 C NMR (CDCl 3 , 125MHz,ppm): δ193.4,138.9,134.9,134.4,128.8,128.4,125.1,54.9,21.3; HRMS cal...

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Abstract

The invention discloses a method for preparing alpha-azidoketone compounds based on photocatalysis. The method is based on a reaction formula shown in the description, wherein R<1> is optionally-substituted aryl, heteroaryl or 1-12 carbon alkyl; R<2> is optionally-substituted aryl, heteroaryl or 1-12 carbon alkyl, or a hydrogen atom. One substance represented by a general formula I is set as one olefin, a substance represented by a general formula II is set as azidotrimethylsilane (TMSN3), and one substance represented by a general formula III is set as one alpha-azidoketone compound, one alpha-azidoketone compound is synthesized under visible light catalysis. According to the method disclosed by the invention, a photocatalyst is designed, one alpha-azidoketone compound is synthesized by adopting air as an oxidant under the visible light catalysis, an equivalent-weight inorganic oxidant, metal reagent and pre-prepared complex raw material are not used, so that the reaction conditions are reduced, and the reaction safety is improved.

Description

[0001] 1. Technical field [0002] The invention relates to a method for preparing α-azide ketone compounds, in particular to a method for preparing α-azide ketone compounds based on photocatalysis. [0003] 2. Background technology [0004] Azide compounds are widely used in fine chemical and pharmaceutical industries. Azide derivatives can be used in the production of rubber hardeners, polymer crosslinking agents, tire binders, dyes, medicines, pesticides and herbicides. In particular, α-azide compounds have very important application value in the field of pharmaceutical synthesis, and they can be used as key intermediates to synthesize triazoles, aziridines, 2-acyl imidazoles and other types of biologically active heterocycles. compound. These compounds generally have significant anti-allergic, antibacterial, anti-AIDS and other biological activities (Molecules.2015,20,14699; Acs.Comb.Sci.2014,16,466; Eur.J.Org.Chem.2002,285; 2001, 11, 849; Bioorg. Med. Chem. Lett. 2011, 2...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C247/10C07C247/14
CPCC07C247/10C07C247/14C07C2602/10
Inventor 魏伟杨道山崔环环
Owner QUFU NORMAL UNIV
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