Substitutionsreaktionen mit metallorganischen Verbindungen, II. Mitteil.: Über die Darstellung 2‐substituierter 3‐Methoxy‐benzonitrile

Aromatic Nucleophilic Substitution Reactions.

“…Alkoxy groups are also replaced by Grignard reagents in some cases; 2,3dimethoxybenzonitrile and ethylmagnesium bromide form 60 per cent of 2-ethyl-3-methoxybenzonitrile (478,479) (equation 11). Most other Grignard reagents react similarly, but the methyl Grignard reagent prefers to add to the cyano group, giving 2,3-dimethoxyacetophenone and some o-hydroxy ketone (3,17).…”

Replacement of Nuclear Alkoxyl Groups by the Action of Grignard Reagents

“…It was discovered by Richtzenhain and Nippus that replacement of the 2alkoxyl group in 2,3-dialkoxybenzonitriles could be effected by the action of Grignard reagents (1,2). Efforts to bring about a similar replacement in 2methoxy-l-naphthonitrile were unsuccessful, however (3).…”

The Behavior of Conjugated Systems Containing Aromatic Double Bonds towards Organometallic Reagents.

“…activation by the sluggish cyano grouping, combined with flanking by a second methoxyl group, also permitted replacement of the ortho methoxyl group 2-substituted compounds (XCIII) (47,48). The structure of the ethyl derivative was proved by successive hydrolysis to the amide, degradation to the amine, diazotization, and hydrolysis to 2-ethylresorcinol.…”