Generation of nitroalkanes, hydroximoyl halides and nitrile oxides from the reactions of β-nitrostyrenes with Grignard or organolithium reagents
Journal
Tetrahedron
Journal Volume
54
Journal Issue
44687
Pages
791-822
Date Issued
1998
Author(s)
Yao, Ching-Fa
Kao, Kuo-Hsi
Liu, Ju-Tsung
Chu, Cheng-Ming
Wang, Yeh
Lin, Yu-Mei
Lin, Wen-Wei
Yan, Ming-Chung
Liu, Jing-Yuan
Chuang, Ming-Ching
Shiue, Jin-Lien
Abstract
The β-nitrostyrenes 1 or 2 react with Grignard or organolithium reagents in ether or THF solution to generate by 1,4-addition the intermediate nitronates A. When A is treated with dilute hydrochloric acid, high yields of the nitroalkanes 3 (and oximes 4) or 5 are obtained Hydroximoyl halides 6, 8 or nitrile oxides 7 can be isolated when the intermediate A is slowly added to the ice cold concentrated hydrohalic acid. The same products 6 and/or 7 are observed if the nitronates, generated from the substrate 1a, are added to 85% aqueous H2SO4 but only the hydrolyzed carboxylic acids 9 are generated when the β-nitrostyrenes 2 are reacted with Grignard reagents and worked up under the same condition. The nitrile oxides 7 can undergo 1,3-dipolar cycloaddition with alkenes or alkynes to generate 2-isoxazolines or isoxazoles. A one-pot synthesis of the [n,3,0] bicyclic (n = 3 or 4) compounds 23-27 by intramolecular nitrile oxide-olefin cycloadditions is reported.
SDGs
Other Subjects
halide; nitrile; nitroalkane; organolithium compound; styrene derivative; article; electron transport; hydrolysis; nuclear magnetic resonance; priority journal; reaction analysis; synthesis
Type
journal article