Unprecedented temperature-dependent formation of 3- and 7-methyl-3H-azepine derivatives by the reaction of o-nitrotoluene with tributylphosphine in nucleophilic media

Siti Mariyah Ulfa, Hideki Okamoto, Kyosuke Satake

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Abstract

The reaction of o-methylphenylnitrene in the presence of alcohol and amine was expected to give isomeric pairs of 3- and 7-methyl-3H-azepine derivatives. The formation ratio between these isomers was found to be obviously influenced by reaction temperature, that is, reaction at 150°C gave 7-methyl-3Hazepine derivative, however, it became minor under 70°C in both media. The ratio between 3- and 7-methyl derivatives is explained by a scheme of kinetic- and thermodynamiccontrolled product distribution from o-methylphenylnitrene to 3- and 7-methyldehydroazepine intermediates which are trapped by nucleophilic media to give 3- and 7-methyl-3H-azepine derivatives.

Original languageEnglish
Pages (from-to)400-402
Number of pages3
JournalChemistry Letters
Volume41
Issue number4
DOIs
Publication statusPublished - 2012

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Azepines
Derivatives
Temperature
Isomers
Amines
Alcohols
Kinetics
2-nitrotoluene
tri-n-butylphosphine

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Unprecedented temperature-dependent formation of 3- and 7-methyl-3H-azepine derivatives by the reaction of o-nitrotoluene with tributylphosphine in nucleophilic media",
abstract = "The reaction of o-methylphenylnitrene in the presence of alcohol and amine was expected to give isomeric pairs of 3- and 7-methyl-3H-azepine derivatives. The formation ratio between these isomers was found to be obviously influenced by reaction temperature, that is, reaction at 150°C gave 7-methyl-3Hazepine derivative, however, it became minor under 70°C in both media. The ratio between 3- and 7-methyl derivatives is explained by a scheme of kinetic- and thermodynamiccontrolled product distribution from o-methylphenylnitrene to 3- and 7-methyldehydroazepine intermediates which are trapped by nucleophilic media to give 3- and 7-methyl-3H-azepine derivatives.",
author = "Ulfa, {Siti Mariyah} and Hideki Okamoto and Kyosuke Satake",
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T1 - Unprecedented temperature-dependent formation of 3- and 7-methyl-3H-azepine derivatives by the reaction of o-nitrotoluene with tributylphosphine in nucleophilic media

AU - Ulfa, Siti Mariyah

AU - Okamoto, Hideki

AU - Satake, Kyosuke

PY - 2012

Y1 - 2012

N2 - The reaction of o-methylphenylnitrene in the presence of alcohol and amine was expected to give isomeric pairs of 3- and 7-methyl-3H-azepine derivatives. The formation ratio between these isomers was found to be obviously influenced by reaction temperature, that is, reaction at 150°C gave 7-methyl-3Hazepine derivative, however, it became minor under 70°C in both media. The ratio between 3- and 7-methyl derivatives is explained by a scheme of kinetic- and thermodynamiccontrolled product distribution from o-methylphenylnitrene to 3- and 7-methyldehydroazepine intermediates which are trapped by nucleophilic media to give 3- and 7-methyl-3H-azepine derivatives.

AB - The reaction of o-methylphenylnitrene in the presence of alcohol and amine was expected to give isomeric pairs of 3- and 7-methyl-3H-azepine derivatives. The formation ratio between these isomers was found to be obviously influenced by reaction temperature, that is, reaction at 150°C gave 7-methyl-3Hazepine derivative, however, it became minor under 70°C in both media. The ratio between 3- and 7-methyl derivatives is explained by a scheme of kinetic- and thermodynamiccontrolled product distribution from o-methylphenylnitrene to 3- and 7-methyldehydroazepine intermediates which are trapped by nucleophilic media to give 3- and 7-methyl-3H-azepine derivatives.

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