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Method for synthesizing cyclopropyl alkyl aromatic compound

A technology for aromatic compounds and cyclopropane groups, applied in the field of synthesis of cyclopropane group aromatic compounds, can solve the problems of large amount of catalyst, long reaction time, harsh reaction conditions, etc., and achieves wide applicability, mild reaction conditions, and substrate range. wide effect

Inactive Publication Date: 2012-03-28
TETRANOV PHARMA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] The purpose of the present invention is to provide a synthetic method of cyclopropanyl aromatic compounds, which overcomes the existing problems of large amount of catalyst, harsh reaction conditions, and long reaction time in the synthesis of cyclopropanyl aromatic compounds.

Method used

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  • Method for synthesizing cyclopropyl alkyl aromatic compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Preparation of 3-cyclopropanylnitrobenzene

[0026] Take 0.012 mmol of ferroceneimine cyclopalladium-phosphine adduct, 0.72 mmol of cyclopropanylboronic acid, K 3 PO 4 ·7H 2 Add 1.5 mmol of O into a 10 ml Schlenk tube, and repeatedly evacuate and fill with N 2 5 times. N 2 Add 0.6 mmol 3-bromonitrobenzene and 2 ml toluene under protection. Stir at room temperature for 5 minutes, then place in an oil bath heated to 100°C, and react for 3 hours. Stop the reaction and cool to room temperature. The reaction solution was diluted with ethyl acetate, filtered, washed once with water, and the organic phase was washed with Na 2 SO 4 Dry, filter and concentrate. The residue was separated by thin-layer chromatography using ethyl acetate / petroleum ether=1 / 20 as a developing solvent to obtain 90 mg of the target product with a yield of 94%. The nuclear magnetic characterization of this compound is as follows: 1H NMR (CDCl 3 , 400MHz, ppm): δ 7.71 (d, J= 7.45 Hz, 1 H), 7.6...

Embodiment 2

[0028] Preparation of 3-cyclopropanylnitrobenzene

[0029] Take 0.012 mmol of ferroceneimine cyclopalladium-phosphine adduct, 0.72 mmol of cyclopropylboronic acid, Cs 2 CO 3 Add 1.5 mmol into a 10 ml Schlenk tube, repeatedly evacuate and fill with N 2 5 times. N 2 Add 0.6 mmol 3-bromonitrobenzene and 2 ml toluene under protection. Stir at room temperature for 5 minutes, then place in an oil bath heated to 100°C, and react for 3 hours. Stop the reaction and cool to room temperature. The reaction solution was diluted with ethyl acetate, filtered, washed once with water, and the organic phase was washed with Na 2 SO 4 Dry, filter and concentrate. The residue was separated by thin-layer chromatography using ethyl acetate / petroleum ether=1 / 20 as a developing solvent to obtain 83 mg of the target product with a yield of 86%.

Embodiment 3

[0031] Preparation of 3-cyclopropanylnitrobenzene

[0032] Take 0.012 mmol of ferroceneimine cyclopalladium-phosphine adduct, 0.72 mmol of cyclopropylboronic acid, and 1.5 mmol of NaOH into a 10 ml Schlenk tube, and repeatedly vacuumize and fill with N 2 5 times. N 2 Add 0.6 mmol 3-bromonitrobenzene and 2 ml toluene under protection. Stir at room temperature for 5 min, then place in an oil bath heated to 100 °C, and react for 3 h. Stop the reaction and cool to room temperature. The reaction solution was diluted with ethyl acetate, filtered, washed once with water, and the organic phase was washed with Na 2 SO 4 Dry, filter and concentrate. The residue was separated by thin-layer chromatography using ethyl acetate / petroleum ether=1 / 20 as a developing solvent to obtain 78 mg of the target product with a yield of 81%.

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Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to application of a cyclopalladated ferrocenylimines-phosphine adduct in the synthesis of a cyclopropyl alkyl aromatic compound. Halogenated aromatic hydrocarbon Aryl-X, alkali and cyclopropyl borate which serve as raw materials, and the cyclopalladated ferrocenylimines-phosphine adduct is used as a catalyst. The catalyst has high stability, efficient catalytic activity and wide application range, and a corresponding coupling product can be synthesized in a mode of high yield (which is up to 96 percent) on the premise of small catalytic quantity; and the method is mild in reaction condition, wide in range of substrates and high in specifity of reaction.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, in particular to a synthesis method of cyclopropanyl aromatic compounds. Background technique [0002] Cyclopropanyl aromatic compounds are a class of organic synthesis intermediates with a wide range of uses, and have important application value in pharmaceutical production, organic synthesis and asymmetric catalysis. In recent years, chemists have been trying to introduce cyclopropyl groups into aromatic and heterocyclic compounds through palladium catalysis. Some catalytic systems have been successfully applied to this reaction, and some research results have been obtained. However, there are many problems, such as the large amount of catalyst used, harsh reaction conditions, long reaction time, the need for phosphorus ligands with complex structures, less research on heterocyclic bromides and chlorides, and so on. Contents of the invention [0003] The object of the present inve...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B37/04B01J31/24C07C205/06C07C205/12C07C201/12C07C69/78C07C67/343C07C255/50C07C253/30C07C13/28C07C1/32C07C47/546C07C49/792C07C45/68C07D241/12C07D213/16C07D213/74C07D213/73C07D333/38
Inventor 崔秀灵吴豫生张敏王连会李敬亚吴养洁
Owner TETRANOV PHARMA CO LTD
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