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An aziridine compound cyclizing method adopting a ketoxime

An aziridine and compound technology, applied in the field of organic synthesis, can solve the problems of difficult separation of by-products, low yield and the like, and achieve the effects of low reaction cost, high yield and wide applicability

Active Publication Date: 2016-04-06
TAIYUAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Finally, the author tried to directly react N-benzyl-2-methylaziridine with oxime in dichloromethane to generate the desired product (45% yield), because the yield was low and the by-products were difficult to separate, so The authors did not conduct further research
[0005] In summary, although some progress has been made in the research on the cycloaddition reaction of aziridine, there are relatively few reports on the cycloaddition reaction of ketoxime and aziridine. Therefore, it is especially important to find greener reaction conditions. It is to use the reaction conditions of a simpler and cheaper catalyst to complete the ring-forming reaction of ketoxime and aziridine, so that the reaction is easier to operate, more environmentally friendly, and the product yield and regioselectivity are higher. It is worth further exploration and research. Find

Method used

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  • An aziridine compound cyclizing method adopting a ketoxime
  • An aziridine compound cyclizing method adopting a ketoxime
  • An aziridine compound cyclizing method adopting a ketoxime

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] Add 0.32mmol of ketoxime 2a, 0.3mmol of aziridine 1a, 20mol% (the mole percentage here is calculated based on the aziridine compound, the same below) KOH with the structural formula shown in Table 1. , acetonitrile 1.5mL, heated to 60°C and stirred for 7h. The crude product was purified by silica gel column chromatography to obtain a single-configuration ring-forming product. The structural formula is shown in Table 1. Characterization confirmed the structure of the product.

[0044] The reaction of table 1 aziridine 1a and acetophenone oxime 2a

[0045]

[0046] 3aWhitesolid; mp120-121℃; 1 HNMR (600MHz, CDCl 3 ):δ7.63-7.64(d,J=8.3Hz,2H),7.54-7.57(m,2H),7.36-7.39(m,3H),7.13-7.15(d,J=8.0Hz,2H), 5.56-5.57(d,J=3.1Hz,1H),3.90-3.95(m,1H),3.11-3.16(m,1H),2.32-2.35(m,4H),2.02-2.06(m,1H), 1.93(s,3H),1.71-1.75(m,1H),1.64-1.66(m,1H),1.31-1.40(m,2H),1.23-1.28(m,2H),ppm; 13 CNMR (150MHz, CDCl 3 ): δ157.8, 145.8, 140.3, 138.8, 132.3, 132.3, 131.4, 130.0, 128.8, 85.6, 60.8, ...

Embodiment 2

[0048] Ketoxime 2b0.45mmol, aziridine 1a0.4mmol, 10mol% K are added to the test tube with the structural formula shown in Table 2 2 CO 3 , acetonitrile 2.0mL, heated to 50°C and stirred for 8h. The crude product was purified by silica gel chromatography to obtain a ring-forming product with a single configuration. The structural formula is shown in Table 2. Characterization confirmed the structure of the product.

[0049] The reaction of table 2 aziridine 1a and oxime 2b

[0050]

[0051] 3b Colourless liquid; 1 HNMR (600MHz, CDCl 3 ): δ7.64-7.66(d, J=8.1Hz, 2H), 7.54-7.56(m, 2H), 7.37-7.38(t, J=3.5Hz, 3H), 7.14-7.16(d, J=8.0 Hz,2H),5.61-5.62(d,J=2.5Hz,1H),3.89-3.94(m,1H),3.12-3.17(m,1H),2.44-2.51(m,1H),2.34-2.37( m,1H),2.33(s,3H),2.03-2.06(m,1H),1.71-1.74(m,1H),1.62-1.66(m,1H),1.32-1.40(m,2H),1.23- 1.31(m,2H),0.96-0.99(t,J=7.4Hz,3H),ppm; 13 CNMR (150MHz, CDCl 3 ): δ162.9, 145.8, 140.2, 137.8, 132.3, 132.2, 131.5, 130.0, 129.0, 85.4, 60.7, 35.7, 33.5, 26.9, 26.7, 24...

Embodiment 3

[0053] Add 0.22mmol of ketoxime 2c, 0.2mmol of aziridine 1a, 25mol% KOH, and 1.2mL of acetonitrile into the test tube, heat to 60°C and stir for 7h. The crude product is purified by silica gel chromatography. A ring-forming product with a single configuration was obtained, the structural formula of which is shown in Table 3 3c, and the structure of the product was confirmed by NMR and high-resolution mass spectrometry.

[0054] Table 3 Reaction of aziridine 1a with oxime 2c

[0055]

[0056]

[0057] 3c Colourless liquid; 1 HNMR (600MHz, CDCl 3 ): δ7.62-7.65(dt, J=2.2,1.9Hz,2H),7.48-7.50(dt,J=2.2,2.3Hz,2H),7.32-7.35(dt,J=2.3,2.3Hz,2H ),7.13-7.15(dd,J=0.6,0.7Hz,2H),5.42-5.43(d,J=3.5Hz,1H),3.89-3.94(m,1H),3.13-3.19(m,1H), 2.34(s,3H),2.28-2.33(m,1H),2.02-2.06(m,1H),1.93(s,3H),1.71-1.75(m,1H),1.63-1.67(m,1H), 1.33-1.41(m,2H),1.27-1.31(m,2H),ppm; 13 CNMR (150MHz, CDCl 3 ): δ156.7, 145.9, 140.4, 138.2, 137.3, 132.3, 131.6, 130.0, 129.9, 85.8, 60.5, 35.9, 33.5, 26.9, 26.8...

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Abstract

The invention discloses an aziridine compound cyclizing method adopting a ketoxime. According to the method, an aziridine compound activated with tosyl is adopted as an initial raw material, the ketoxime is adopted as a nucleophilic reagent, and the aziridine compound is subjected to cycloaddition in acetonitrile or chloroform under the catalytic functions of potassium hydroxide, potassium carbonate, potassium tert-butoxide or triethylamine. Reaction processes of the method are simple. The method adopts the potassium hydroxide or the triethylamine as a catalyst and is environmental friendly, mild in conditions and wide in universality. High yields and good regioselectivity can be achieved for aziridine compounds with different structures and ketoximes with different structures.

Description

technical field [0001] The invention relates to a method for ring-forming an aziridine compound by using ketoxime, and belongs to the technical field of organic synthesis. Background technique [0002] Aziridine compounds are important building blocks and intermediates in organic synthesis. They exist in many natural products and have good antiviral, antitumor and other biological activities. Aziridine can undergo a series of important reactions, such as ring-forming reaction, cycloaddition reaction, reduction and elimination reaction, etc. Its cycloaddition reaction can be used to synthesize five-membered or six-membered ring compounds, and then synthesize many compounds with biological activity and extremely promising application prospects in the pharmaceutical and chemical industries. [0003] Reports on the ring-forming reactions of nucleophiles and aziridines have been frequently seen, but people's enthusiasm for research on aziridine-related reactions remains undimini...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D273/04C07D413/04
CPCC07D273/04C07D413/04
Inventor 李兴张照昱魏文珑常宏宏高文超
Owner TAIYUAN UNIV OF TECH
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