Free radical reactions to generate alkenes and/or ionic reactions to generate hydroximoyl chlorides when ß-nitrostyrenes react with triethylaluminium or diethylaluminium chloride

Cheng Ming Chu, Ju Tsung Liu, Wen-Wei Lin, Ching-Fa Yao

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

ß-Nitrostyrenes l react with triethylaluminium or diethylaluminium chloride in diethyl ether solution and under nitrogen or argon to generate the alkenes 2 and the hydroximoyl chlorides 3 after work-up with ice-cold, cone, hydrochloric acid. The formation of the alkenes 2 is proposed to be a free-radical reaction via NO2/alkyl substitution since the yields of the alkenes 2 are increased in the presence of benzoyl peroxide (Bz2O2) and decreased in the presence of galvinoxyl. Only the alkenes 2 are produced with a high stereoselectivity for the E isomers when ß-nitrostyrenes react with triethylaluminium in the presence of one to two equivalents of Bz2O2 as free-radical initiator.. The mechanism of the generation of the hydroximoyl chlorides 3 is proposed to proceed through a 1,4-addition pathway to produce nitronates A, then the protonated nitronates B or the nitroso cations C are trapped by chloride ion to form the final products. The yields of compounds 3 are also improved by the presence of Lewis acids such as MgCl2. Medium to high yields of the hydroximoyl chlorides 3 and traces or low yields of the alkenes 2 are generated when triethylaluminium or diethylaluminium chloride react with ß-nitrostyrenes in the presence of three equivalents of MgCl2 under argon.

Original languageEnglish
Pages (from-to)47-52
Number of pages6
JournalJournal of the Chemical Society - Perkin Transactions 1
Issue number1
DOIs
Publication statusPublished - 1999 Jan 1

Fingerprint

Free radical reactions
Alkenes
Chlorides
Magnesium Chloride
Argon
Benzoyl Peroxide
Stereoselectivity
Lewis Acids
Hydrochloric Acid
Ice
Isomers
Ether
Free Radicals
triethylaluminum
Cations
Cones
Substitution reactions
Nitrogen
Ions

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{cd32161d1cbe445ea7767fd749cdf24e,
title = "Free radical reactions to generate alkenes and/or ionic reactions to generate hydroximoyl chlorides when {\ss}-nitrostyrenes react with triethylaluminium or diethylaluminium chloride",
abstract = "{\ss}-Nitrostyrenes l react with triethylaluminium or diethylaluminium chloride in diethyl ether solution and under nitrogen or argon to generate the alkenes 2 and the hydroximoyl chlorides 3 after work-up with ice-cold, cone, hydrochloric acid. The formation of the alkenes 2 is proposed to be a free-radical reaction via NO2/alkyl substitution since the yields of the alkenes 2 are increased in the presence of benzoyl peroxide (Bz2O2) and decreased in the presence of galvinoxyl. Only the alkenes 2 are produced with a high stereoselectivity for the E isomers when {\ss}-nitrostyrenes react with triethylaluminium in the presence of one to two equivalents of Bz2O2 as free-radical initiator.. The mechanism of the generation of the hydroximoyl chlorides 3 is proposed to proceed through a 1,4-addition pathway to produce nitronates A, then the protonated nitronates B or the nitroso cations C are trapped by chloride ion to form the final products. The yields of compounds 3 are also improved by the presence of Lewis acids such as MgCl2. Medium to high yields of the hydroximoyl chlorides 3 and traces or low yields of the alkenes 2 are generated when triethylaluminium or diethylaluminium chloride react with {\ss}-nitrostyrenes in the presence of three equivalents of MgCl2 under argon.",
author = "Chu, {Cheng Ming} and Liu, {Ju Tsung} and Wen-Wei Lin and Ching-Fa Yao",
year = "1999",
month = "1",
day = "1",
doi = "10.1039/a807156j",
language = "English",
pages = "47--52",
journal = "Journal of the Chemical Society, Perkin Transactions 1",
issn = "1470-4358",
publisher = "Chemical Society",
number = "1",

}

TY - JOUR

T1 - Free radical reactions to generate alkenes and/or ionic reactions to generate hydroximoyl chlorides when ß-nitrostyrenes react with triethylaluminium or diethylaluminium chloride

AU - Chu, Cheng Ming

AU - Liu, Ju Tsung

AU - Lin, Wen-Wei

AU - Yao, Ching-Fa

PY - 1999/1/1

Y1 - 1999/1/1

N2 - ß-Nitrostyrenes l react with triethylaluminium or diethylaluminium chloride in diethyl ether solution and under nitrogen or argon to generate the alkenes 2 and the hydroximoyl chlorides 3 after work-up with ice-cold, cone, hydrochloric acid. The formation of the alkenes 2 is proposed to be a free-radical reaction via NO2/alkyl substitution since the yields of the alkenes 2 are increased in the presence of benzoyl peroxide (Bz2O2) and decreased in the presence of galvinoxyl. Only the alkenes 2 are produced with a high stereoselectivity for the E isomers when ß-nitrostyrenes react with triethylaluminium in the presence of one to two equivalents of Bz2O2 as free-radical initiator.. The mechanism of the generation of the hydroximoyl chlorides 3 is proposed to proceed through a 1,4-addition pathway to produce nitronates A, then the protonated nitronates B or the nitroso cations C are trapped by chloride ion to form the final products. The yields of compounds 3 are also improved by the presence of Lewis acids such as MgCl2. Medium to high yields of the hydroximoyl chlorides 3 and traces or low yields of the alkenes 2 are generated when triethylaluminium or diethylaluminium chloride react with ß-nitrostyrenes in the presence of three equivalents of MgCl2 under argon.

AB - ß-Nitrostyrenes l react with triethylaluminium or diethylaluminium chloride in diethyl ether solution and under nitrogen or argon to generate the alkenes 2 and the hydroximoyl chlorides 3 after work-up with ice-cold, cone, hydrochloric acid. The formation of the alkenes 2 is proposed to be a free-radical reaction via NO2/alkyl substitution since the yields of the alkenes 2 are increased in the presence of benzoyl peroxide (Bz2O2) and decreased in the presence of galvinoxyl. Only the alkenes 2 are produced with a high stereoselectivity for the E isomers when ß-nitrostyrenes react with triethylaluminium in the presence of one to two equivalents of Bz2O2 as free-radical initiator.. The mechanism of the generation of the hydroximoyl chlorides 3 is proposed to proceed through a 1,4-addition pathway to produce nitronates A, then the protonated nitronates B or the nitroso cations C are trapped by chloride ion to form the final products. The yields of compounds 3 are also improved by the presence of Lewis acids such as MgCl2. Medium to high yields of the hydroximoyl chlorides 3 and traces or low yields of the alkenes 2 are generated when triethylaluminium or diethylaluminium chloride react with ß-nitrostyrenes in the presence of three equivalents of MgCl2 under argon.

UR - http://www.scopus.com/inward/record.url?scp=2442691014&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=2442691014&partnerID=8YFLogxK

U2 - 10.1039/a807156j

DO - 10.1039/a807156j

M3 - Article

AN - SCOPUS:2442691014

SP - 47

EP - 52

JO - Journal of the Chemical Society, Perkin Transactions 1

JF - Journal of the Chemical Society, Perkin Transactions 1

SN - 1470-4358

IS - 1

ER -