Method for synthesizing five-membered oxygen-containing heterocyclic compound

A technology of heterocyclic compounds, synthesis methods, applied in the field of organic catalysis

Active Publication Date: 2021-07-06
NANJING UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the [3+2] cyclization reaction of epoxides and heterocumulative dienes is the most efficient method for the synthesis of five-membered oxygen-containing heterocyclic compounds, selectivity has always been the biggest challenge of this method. How to efficiently target and synthesize a single Five-membered oxygen-containing heterocyclic compounds have always been the focus of researchers

Method used

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  • Method for synthesizing five-membered oxygen-containing heterocyclic compound
  • Method for synthesizing five-membered oxygen-containing heterocyclic compound
  • Method for synthesizing five-membered oxygen-containing heterocyclic compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0077] The 250mL reaction bottle was fully dried and filled with inert gas protection. Add 1,3-(2,6-diisopropylphenyl)imidazolium chloride (4.25g, 10mmol, 1.0equiv.), and add 100mL of anhydrous dichloromethane to dissolve it, then add N-iodo Succinimide (2.36g, 10.5mmol, 1.05equiv.), after stirring at 40°C for 2 hours, the reaction solution was washed with deionized water 50×3, the organic phases were combined, dried, and the solvent was removed under reduced pressure to obtain catalyst 1 , as light yellow powder, yield 98%. 1 HNMR (400MHz, DMSO-d 6 )δ8.63(s, 2H), 7.69(t, J=7.8Hz, 2H), 7.55(d, J=7.8Hz, 4H), 2.24(p, J=6.7Hz, 6H), 1.23(dd, J=19.3,6.8Hz,12H). 13 C NMR (101MHz, DMSO-d 6 )δ144.83, 132.24, 131.98, 127.57, 125.00, 120.16, 39.60, 28.98, 24.19, 22.91.

Embodiment 2

[0079] Dissolve catalyst 1 (0.55g, 1.0mmol, 1.0equiv.) in anhydrous dichloromethane, add sodium tetrafluoroborate (0.12g, 1.1mmol, 1.1equiv.) to form a suspension, and stir at room temperature for 2 hours, After filtration, the filtrate was spin-dried to obtain the tetrafluoroborate of Catalyst 1. Ethyl acetate was added to the dried tetrafluoroborate of Catalyst 1 (0.6 g, 1.0 mmol, 1.0 equiv.) to form a suspension. Configure a saturated solution of sodium iodide in acetone (0.6g, 4mmol, 4.0equiv.) and add the saturated solution dropwise to the above suspension, stir the mixed reaction solution at room temperature for 12 hours, filter, and dilute the filter residue with ethyl acetate The ester and a small amount of acetone were washed, and the filter residue was dried to obtain catalyst 2 as a white powder. 1 H NMR (400MHz, DMSO-d 6 )δ8.65(s, 2H), 7.69(t, J=7.8Hz, 2H), 7.56(d, J=7.8Hz, 4H), 2.24(p, J=6.7Hz, 6H), 1.24(dd, J=18.3,6.8Hz,12H). 13 C NMR (101MHz, DMSO-d 6 )δ144...

Embodiment 3

[0081] The 250mL reaction bottle was fully dried and filled with inert gas protection. Add 1,3-(2,6-diisopropylphenyl)-4,5-methylimidazolium chloride (4.53 g, 10 mmol, 1.0 equiv.), and add 100 mL of anhydrous dichloromethane to dissolve it , then added N-iodosuccinimide (2.36g, 10.5mmol, 1.05equiv.), stirred at 40°C for 2 hours, washed the reaction solution with deionized water 50×3, combined the organic phases, dried, and reduced The solvent was removed under pressure to obtain Catalyst 3 as a light yellow powder with a yield of 96%. 1 H NMR (400MHz, DMSO-d 6 )δ7.89–7.68 (m, 2H), 7.60 (d, J = 7.8Hz, 4H), 2.24 (p, J = 6.8Hz, 4H), 2.17 (s, 6H), 1.23 (dd, J = 6.8 ,2.9Hz,24H). 13 C NMR (101MHz, DMSO-d 6 )δ145.02, 132.45, 131.71, 129.84, 125.57, 107.02, 28.66, 23.60 (d, J=19.9Hz), 10.06.

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Abstract

The invention discloses a method for synthesizing a five-membered oxygen-containing heterocyclic compound, which is characterized in that epoxide and hetero-accumulated diene are used as raw materials, and the five-membered oxygen-containing heterocyclic compound is obtained by reaction with a catalyst of formula I provided by the invention. Reagents used in the method are cheap and easy to obtain, the product can be synthesized through a one-step method, conditions are mild, no metal residues exist in the whole reaction system, no by-products are generated, and a single product is obtained with high selectivity.

Description

technical field [0001] The invention belongs to the technical field of organic catalysis, and in particular relates to a method for producing five-membered oxygen-containing heterocyclic compounds through [3+2] cyclization reaction of epoxide and carbon disulfide or isocyanate. Background technique [0002] Three-membered heterocyclic compounds are of great interest in organic synthesis due to their high ring strain. The ring expansion reactions of these heterocycles, especially the [3+2] annulation of epoxides and heterocumdienes, are considered to be efficient methods for the synthesis of multi-substituted five-membered oxygen-containing heterocycles. Heterocumulative dienes such as carbon disulfide and isocyanate are important reagents in organic synthesis. The carbon atoms in them have high electrophilicity, making them easy to be attacked by nucleophiles, which is beneficial to [3+2] with epoxides. Cycloaddition reaction. [0003] [0004] The product of the [3+2] ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D263/24C07D263/22C07D263/20C07D233/68B01J31/02C07D327/04
CPCC07D263/24C07D263/20C07D263/22C07D327/04C07D233/68B01J31/0271B01J31/0244
Inventor 郭凯陈恺李振江
Owner NANJING UNIV OF TECH
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