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Cycloaddition method of amidine compound and aziridine compound

A technology of aziridine and heterocyclopropane, which is applied in the field of organic synthesis, can solve the problems of few reports on the cycloaddition reaction of amidine compounds, and achieve the effects of strong tolerance, high yield, and wide applicability

Active Publication Date: 2019-09-20
山西省产品质量监督检验研究院
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  • Description
  • Claims
  • Application Information

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Problems solved by technology

This method utilizes the reaction of N-arylbenzamidine and macromolecular aziridine to form imidazole five-membered ring. The author also expanded the variety of substrates under the optimal reaction conditions obtained by optimization and screening. The result is that all substrates Both can be converted into the desired imidazoles in moderate yields; however, so far there are no reports on the reaction of aziridines with amidines to form six-membered cycloaddition products
[0005] In summary, although the research on the aziridine cycloaddition reaction has made some progress, there are very few reports on the cycloaddition reaction between amidine compounds and aziridine compounds. The example of generating six-membered ring cycloaddition products has not been reported; therefore, looking for green reaction conditions, especially the reaction conditions using simpler and cheaper catalysts or accelerators to complete the [3+ 3] Ring formation reaction, to make the reaction easier to operate, more environmentally friendly, higher product yield and regioselectivity, it is worthy of further exploration and discovery

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  • Cycloaddition method of amidine compound and aziridine compound
  • Cycloaddition method of amidine compound and aziridine compound
  • Cycloaddition method of amidine compound and aziridine compound

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Experimental program
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Embodiment 1

[0034] The present invention is further illustrated by the following examples, but the following examples should not be construed as limiting the protection scope of the present invention. Without departing from the technical scope of the present invention, any non-essential improvements and changes to the present invention shall be included in the technical scope of the present invention.

[0035] An example of the annulation reaction of p-toluenesulfonyl-activated styrene-derived aziridine 1a with different amidines is first given below.

[0036]

[0037] Example 1:

[0038] Add 0.25mmol of aziridine, 0.15mmol of amidine 2a, 70mol% LiOH, and 0.8mL of acetonitrile into the test tube, heat to 80°C and stir for 24h, then extract, wash and dry to obtain the crude product; crude The product was purified by silica gel chromatography to obtain a single-configuration ring-forming product. The structural formula is shown in 3a in Table 1. The product was characterized by H NMR, C...

Embodiment 2

[0043] Add 0.40mmol of aziridine, 0.23mmol of amidine 2b, 70mol% NaOH, and 1.2mL of acetonitrile into the test tube, heat to 70°C and stir for 30h, then extract, wash and dry to obtain the crude product; crude The product was purified by silica gel chromatography to obtain a ring-forming product with a single configuration. The structural formula is shown in 3b in Table 2. The product was characterized by H NMR, C NMR and high-resolution mass spectrometry to confirm the structure of the product.

[0044] The reaction of table 2 aziridine 1a and amidine 2b

[0045]

[0046] 3b White solid; mp 90-91°C; 1 H NMR (400MHz, CDCl 3 ),δ=2.45(s,3H),2.52(s,3H),3.40(dd,J=11.2,2.4Hz,1H),3.73(t,J=11.2Hz,1H),4.65-4.71(m, 1H), 6.47(dd, J=11.2, 2.4Hz, 2H), 6.55(d, J=7.6Hz, 1H), 6.81(t, J=7.6Hz, 2H), 7.13-7.15(m, 5H), 7.24(d, J=7.6Hz, 4H), 7.34(d, J=8.0Hz, 2H), 7.87(d, J=8.0Hz, 2H)ppm; 13 C NMR (CDCl 3 ,100MHz):δ=17.93,21.47,55.94,59.12,126.54,126.79,126.86,127.28,127.38,128.00,128.33,1...

Embodiment 3

[0048] Add 0.55mmol of aziridine, 0.30mmol of amidine 2c, 70mol% KOH, and 2.0mL of 1,2-dichloroethane into the test tube, heat to 70°C and stir for 20h, after extraction and washing and drying to obtain a crude product; the crude product is purified by silica gel chromatography to obtain a single-configuration ring-forming product, the structural formula is shown in 3c in Table 3, and the product is characterized by proton nuclear magnetic resonance, carbon and high-resolution mass spectrometry. The structure of the product.

[0049] The reaction of table 3 aziridine 1a and amidine 2c

[0050]

[0051] 3c White solid; mp 100-101°C; 1 H NMR (400MHz, CDCl 3 ),δ=2.16(d,J=6.0Hz,6H),2.39(s,3H),3.03(dd,J=14.4,2.0Hz,1H),4.50(dd,J=10.8,2.4Hz,1H) ,4.85(q,J=11.2Hz,1H),6.06(d,J=7.2Hz,1H),6.56(d,J=8.0Hz,1H),6.86(s,1H),7.11-7.20(m, 12H), 7.64 (d, J=8.0Hz, 2H) ppm; 13 C NMR (CDCl 3 ,100MHz):δ=20.80,21.52,22.45,58.47,58.99,124.74,125.76,126.22,127.19,127.65,127.95,128.22,128.51,129....

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Abstract

The invention discloses a cycloaddition method of an amidine compound and an aziridine compound, and a p-toluenesulfonyl aziridine compounds as a starting material and the amidine compound as a nucleophile are subjected to cycloaddition reaction in an organic solvent under the action of an inorganic base. The cycloaddition method has simple reaction process, MOH (M = lithium, sodium, potassium or rubidium) as a promoter, an alkane reagent as a solvent, mild conditions, good environmental friendliness, wide universality, and high yields of products by reacting the aziridine compounds with the amidine compounds of different structures.

Description

technical field [0001] The invention relates to a method for ring-forming an amidine compound and an aziridine compound, 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-opening 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 biologically active compounds. And compounds with great application prospects in the pharmaceutical and chemical industries. [0003] Reports on the ring-opening reactions of various nucleophiles and aziridines are common, but people’s enthusiasm for research on aziridine-related reactions remains undiminishe...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D253/06
CPCC07D253/06Y02P20/55
Inventor 成斌王锦明白云飞李慧青李兴
Owner 山西省产品质量监督检验研究院