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Method using carboxylic acid for ring opening of aziridine compound

An aziridine and carboxylic acid compound technology, applied in the field of organic synthesis, can solve the problems of low selectivity, few reports, low regioselectivity, etc., and achieve the effects of high yield, wide applicability, and environmental protection of the reaction

Active Publication Date: 2015-01-28
TAIYUAN UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Then, our research group used potassium hydroxide (KOH) as a catalyst to complete the research on the ring-opening reaction of various carboxylic acids to a series of aziridines (CN102875428A and CN102875421A). In this report, although the product yields are relatively High, but the disadvantage is that the amount of catalyst potassium hydroxide is 0.4 equivalent of the substrate aziridine, and the selectivity of most reactions is relatively low
[0005] In summary, although the research on the ring-opening reaction of aziridine has made some progress, there are relatively few reports on the ring-opening reaction of related carboxylic acid compounds to aziridine compounds, and all of them use catalysts, some Catalyst price is still very high, although the price of catalyst is suitable for some reactions, the regioselectivity of reaction is relatively low; The ring-opening reaction is carried out to make the reaction easier to operate, more environmentally friendly, and the product yield and regioselectivity are higher. It is worthy of further exploration and discovery

Method used

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  • Method using carboxylic acid for ring opening of aziridine compound
  • Method using carboxylic acid for ring opening of aziridine compound
  • Method using carboxylic acid for ring opening of aziridine compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] Add 0.2mmol of aziridine with the structural formula 1a in Table 1, 0.24mmol of p-nitrobenzoic acid, and 2.5mL of N,N-dimethylformamide into the test tube, heat to 70°C and stir the reaction for 35h, add K2 CO 3 The remaining acid was removed from the solution, and the crude product was obtained by extraction, washing and drying. The crude product was purified by silica gel chromatography to obtain a ring-opened product with a single configuration. The structural formula is shown in 3a in Table 1. The product was characterized by nuclear magnetic resonance to confirm the structure of the product.

[0046] Table 1 Reaction of aziridine 1a with p-nitrobenzoic acid

[0047]

[0048] 3a: white solid; mp 164-166°C; 1 H NMR (600MHz, CDCl 3 ):δ2.17(s,3H),2.39(d,J=1.8Hz,3H),3.39-3.50(m,1H),4.41-4.44(m,1H),5.27-5.30(t,J=7.2 Hz,1H),6.19-6.21(dd,J=9.0,4.2Hz,1H),7.02-7.03(d,J=8.4Hz,1H),7.07-7.08(d,J=7.2Hz,1H),7.13 -7.24(m,3H),7.29-7.30(d,J=7.8Hz,1H),7.52-7.53(m,1H),7.70-7.7...

Embodiment 2

[0056] Add 0.2mmol of aziridine with the structural formula 1b in Table 3, 0.24mmol of p-nitrobenzoic acid, and 1.5mL of N,N-dimethylformamide into the test tube, heat to 55°C and stir the reaction for 39h, add K 2 CO 3 The residual acid was removed from the solution, and the crude product was obtained by extraction, washing and drying. The crude product was purified by silica gel chromatography to obtain a ring-opened product with a single configuration. The structural formula is shown in 3b in Table 3. The product was characterized by nuclear magnetic resonance. The structure of the product.

[0057] Table 3 Reaction of aziridine 1b with p-nitrobenzoic acid

[0058]

[0059] 3b: white solid; mp 140-142°C; 1 H NMR (600MHz, CDCl 3 ):δ2.33(s,3H),2.40(s,3H),3.44-3.53(m,1H),4.43-4.54(m,1H),5.19-5.21(m,1H),5.96-5.98(dd ,J=7.8,4.2Hz,1H),7.05-7.08(m,2H),7.14-7.15(d,J=7.8Hz,2H),7.20-7.24(dd,J=12.0,8.4Hz,2H), 7.57-7.58(d, J=8.4Hz, 1H), 7.68-7.70(d, J=8.4Hz, 1H), 8.06-8.07(d, ...

Embodiment 3

[0067] Add 1mmol of aziridine, 1.1mmol of p-nitrobenzoic acid, and 10mL of N,N-dimethylformamide into a 50mL round-bottomed flask, and heat to 75°C and stir for 30h. Join K 2 CO 3 The residual acid was removed from the solution, and the crude product was obtained after extraction, washing and drying. The crude product was purified by silica gel chromatography to obtain a ring-opened product with a single configuration. The structural formula is shown in 3c in Table 5. The product was characterized by H NMR The structure of the product was confirmed.

[0068] Table 5 Reaction of aziridine 1c with p-nitrobenzoic acid

[0069]

[0070] 3c: white solid; mp 146-148°C; 1 H NMR (600MHz, CDCl 3 ):δ2.31(s,3H),3.44-3.49(m,1H),4.42-4.49(m,1H),4.45-4.76(td,J=7.8,1.8Hz,1H),6.17-6.19(d ,J=7.8Hz,1H),7.06-7.07(d,J=7.8Hz,1H),7.09-7.7.14(m,2H),7.17-7.18(m,1H),7.23-7.24(d,J =7.8Hz,1H),7.27-7.28(m,1H),7.56-7.57(m,1H),7.69-7.70(dd,J=7.8,6.0Hz,1H),8.04-8.20(m,4H)ppm .

[0071] The compar...

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Abstract

The invention discloses a method using carboxylic acid for ring opening of an aziridine compound; a tosyl activated aziridine compound is used as a starting material, in catalyst-free conditions, ring opening of the aziridine compound is performed in N, N-dimethyl formamide solvent by use of carboxylic acid as a nucleophilic reagent. The method is simple in reaction process, uses no catalyst, is mild in conditions, good in environmental protection property, and the method for ring opening has wide universality, and has higher yield and good regioselectivity on the aziridine compounds and carboxylic acid with different structures.

Description

technical field [0001] The invention relates to a method for ring-opening an aziridine compound with a carboxylic acid, belonging 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 nucleophilic ring-opening reaction can be used to synthesize β-substituted amino compounds, and then synthesize many compounds such as amino alcohols, amino acids, alkaloids and β-lactamides that have biological activity and have extremely promising application prospects in the pharmaceutical and chemical industries. [0003] A variety of nucleophiles (alcohols, phenols, amines and amides, thiols and thiophenols) can carry out rin...

Claims

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Application Information

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IPC IPC(8): C07C311/17C07C311/20C07C303/40C07D213/803C07D213/79
Inventor 李兴张照昱常宏宏魏文珑李彦威
Owner TAIYUAN UNIV OF TECH
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