Method for preparing 3-aryl purrocoline derivative

A technology of indene derivatives and aryl groups, which is applied in the field of organic synthetic chemistry and achieves the effects of simple and feasible process method, simplified process flow and reduced preparation cost

Active Publication Date: 2013-05-08
常熟紫金知识产权服务有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there are certain difficulties in the synthesis of 3-aryl indolizine derivatives in the prior art. Not only is the reaction process long and many steps are required, expensive ligands and excessive metal oxidants are also required, and the requirements of anhydrous and oxygen-free environment must be met. Harsh reaction conditions, resulting in high preparation costs

Method used

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  • Method for preparing 3-aryl purrocoline derivative
  • Method for preparing 3-aryl purrocoline derivative
  • Method for preparing 3-aryl purrocoline derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] as attached figure 1 The technological process of taking 1-N,N-dimethylcarbonamido-indolizine is 38.0 mg (equivalent to 0.20 mmol), phenylboronic acid is 25.0 mg (equivalent to 0.20 mmol), palladium acetate is 0.5 mg (equivalent to 0.0025 mmol), pyridine-2-carboxylic acid 0.3 mg (equivalent to 0.0025 mmol), potassium bicarbonate 20.0 mg (equivalent to 0.20 mmol) and 0.4 mL of dimethyl sulfoxide, under 1 atmosphere of oxygen , heated and stirred at 100 degrees Celsius for 48 hours, and 45.6 mg of the first numbered target product, 3-aryl indolizine derivative, was isolated (86% yield).

[0033] The first target product was analyzed by nuclear magnetic resonance spectrometer (model: AVANCE 400MHz, manufacturer: Bruker, Switzerland) to obtain figure 2 The H NMR spectra shown and image 3 The carbon NMR spectrum shown. The parameters of the former are 1 H NMR (CDCl 3 , 400MHz): 8.23 ​​(d, J = 7.1 Hz, 1H), 7.96 (d, J = 9.1 Hz, 1H), 7.53 (d, J = 7.2 Hz, 2H), 7.48...

Embodiment 2

[0035] Take 1,2-dicarbotoethyl-indolizine as 52.2 mg (equivalent to 0.20 mmol), phenylboronic acid as 50.0 mg (equivalent to 0.40 mmol), palladium acetate as 2.2 mg (equivalent to 0.01 mmol ), without nitrogen-containing ligands, 60.0 mg of potassium acetate (equivalent to 0.60 mmol), 0.6 ml of dimethyl sulfoxide and 1.4 ml of N-methylpyrrolidone were heated and stirred at 100 degrees Celsius for 2 hours under 1 atmosphere of oxygen, and separated 44.5 mg of the second number target product was obtained (66% yield).

[0036] The second target product was analyzed by a nuclear magnetic resonance spectrometer (model: AVANCE 400MHz, manufacturer: Bruker, Switzerland) to obtain Figure 4 The H NMR spectra shown and Figure 5 The carbon NMR spectrum shown. The parameters of the former are 1 H NMR (CDCl 3 , 400MHz): 8.27 (d, J= 9.1 Hz, 1H), 8.04 (d, J = 7.0 Hz, 1H), 7.59 -7.43 (m, 5 H), 7.12 (dd, J = 8.8, 6.9 Hz, 1H), 6.72 (t, J = 6.9 Hz, 1H), 4.39 (q, J = 7.1 Hz, 2H),...

Embodiment 3

[0038] Take 2,5-dimethyl-1-cyano-indolizine as 34.0 mg (equivalent to 0.20 mmol), 2-methyl-phenylboronic acid as 68.0 mg (equivalent to 0.40 mmol), palladium acetate as 4.5 mg (equivalent to 0.02 mmol), 8-hydroxyquinoline 5.8 mg (equivalent to 0.04 mmol), sodium bicarbonate 33.6 mg (equivalent to 0.40 mmol) and 2.0 mL of N,N-dimethylformamide in Under 1 atmosphere of oxygen, heated and stirred at 80°C for 24 hours, 31.8 mg of the third target product was isolated (61% yield).

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Abstract

The invention discloses a method for preparing a 3-aryl purrocoline derivative. The 3-aryl purrocoline derivative is prepared by arylboronic acid in the presence of a palladium catalyst based on oxygen as a final oxidant. The process comprises the following steps of: placing purrocoline substituted by hydrogen in site 3, arylboronic acid, the palladium catalyst, nitrogen-containing ligands or nitrogen-free ligands and alkaline components in a reactor utensil according to a molar ratio of 1:(1.0-3.0):(0.0125-0.10):(0.0125-0.30) or 0.0:(1.0-5.0); adding 2.0-20ml of solvent; heating and stirring under oxygen atmosphere to react; pouring a mixture after reaction to water; and filtering, washing and drying, and recrystalizing or performing column chromatography isolation to obtain the 3-aryl purrocoline derivative. The method provided by the invention is short in process flow, simple and accessible, and the nitrogen--containing ligands or nitrogen-free ligands which are not expensive can be selected. The final oxidant is oxygen in air which is green and environment-friendly, so that the reaction condition is loose, the preparation cost is lowered, and the 3-aryl purrocoline derivative in rich source can be provided for manufacturing related products in the field of biology, pesticides and medicines.

Description

Technical field: [0001] The invention relates to organic synthesis chemistry technology, in particular to a preparation method of indolizine derivatives, in particular to a new method for preparing 3-aryl indolizine derivatives. Background technique: [0002] Indolizine derivatives are widely used in the fields of biology, pesticides, medicine and luminescent materials, and are necessary for the production of drugs, dyes and organic luminescent materials. For example: it is an active ingredient in pigments, herbicides, latent phospholipase inhibitors, anti-Leishmania and antiviral drugs; in addition, it also exhibits anti-mycobacterial activity; it is a synthetic compound with important physiological activities Key intermediates of alkaloids. In recent years, studies have confirmed that the biological activity of indolizine derivatives has also played a positive role in anti-tumor, anti-bacterial, anti-virus, acaricidal, anti-inflammatory, anti-arrhythmic, anti-hypertensi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D471/04
Inventor 胡华友阚玉和张宇支三军李国栋
Owner 常熟紫金知识产权服务有限公司
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