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tele Nucleophilic Substitutions of Hydrogen in m-(Trichloromethyl)nitrobenzenes with Cyano and Ester Carbanions

✍ Scribed by Marek Surowiec; Dimitris Belekos; Mieczysław Mąkosza; George Varvounis

Book ID
102174383
Publisher
John Wiley and Sons
Year
2010
Tongue
English
Weight
170 KB
Volume
2010
Category
Article
ISSN
1434-193X

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✦ Synopsis

Abstract

Stabilized carbanions of malonates, 2‐phenylacetonitrile, or isopropyl 2‐phenylacetate add to m‐(trichloromethyl)nitrobenzene derivatives to form σ^H^ adducts that lose a chloride ion to give intermediate exo‐dichloromethylene nitrocyclohexadienes. These undergo re‐aromatization through 1,5‐hydrogen shift to yield tele substitution mono adducts. Depending on the stoichiometry of the nitroarene to the carbanion, further addition of the nucleophile to the tele mono adduct can yield a mixture of products that are either double or triple adducts. At low temperature, the σ^H^ adducts undergo direct 1,2‐addition in competition with chloride ion elimination/1,5‐hydrogen shift.

📜 SIMILAR VOLUMES

Tele vs. Oxidative Substitution of Hydro
Tele vs. Oxidative Substitution of Hydrogen in meta Monochloromethyl, Dichloromethyl, and Trichloromethyl Nitrobenzenes in the Reaction with Grignard Reagents
✍ Mieczysław Mąkosza; George Varvounis; Marek Surowiec; Thomas Giannopoulo 📂 Article 📅 2003 🏛 John Wiley and Sons 🌐 English ⚖ 137 KB

## Abstract Grignard reagents add to nitrobenzene derivatives containing trichloromethyl, dichloromethyl, and monochloromethyl groups in the __meta__ position to form σ^H^ adducts, which are either further converted through departure of a chloride anion, giving products of __tele__ substitution, or