Monatshefte für Chemie / Chemical Monthly

, Volume 121, Issue 11, pp 909–921 | Cite as

Application of organolithium and related reagents in synthesis, part VI. A general study of the lithiation of secondary picoline- and isonicotine amides

  • Jan Epsztajn
  • Andrzej Jóźwiak
  • Krzysztof Czech
  • Aleksandra K. Szcześniak
Organische Chemie Und Biochemie
Received:
Accepted:

Summary

The lithiation of secondary picoline- (1) and isonicotine-amides (2) and the subsequent reaction of the corresponding (N- and 3-)lithiated amides (3 and4) with N,N-dimethylbenzamide towards the synthesis of the C3-benzoylated picoline (12 a) and isonicotine acids (13 a) has been investigated. The effect of the N-substituent upon the generation of the lithiated amides3 and4 has been studied. As a result it was found that the anilide function should be considered the best choice for direct metallation of the masked picoline- and isonicotinecarboxylic acids. The effects at various temperatures upon the generation of the lithiated reactive intermediates and the problems concerning their reactions with an acid (deuteriation) and an carbonyl electrophile are discussed.

Keywords

Secondary picoline- and isonicotine amides Lithiation Lithiated reactive intermediates — dual behaviour Protonation Benzoylation 

Anwendungen von Organolithium und verwandten Reagenzien in organischen Synthesen, Teil VI. Zur Metallierung von sekundären Picolinsäure- und Isonicotinsäureamiden

Zusammenfassung

Die Metallierung sekundärer Amide von Picolin- (1) und Isonicotinsäure (2) und nachfolgende Reaktion der entsprechenden (N- und 3-)metallierten Amide3 und4 mit N,N-Dimethylbenzamid — zur Synthese von C3-benzoylierten Picolin- (12 a) und Isonicotinsäuren (13 a) — wurde untersucht. Der Einfluß des N-Substituenten auf die Bildung der metallierten Amide3 and4 wurde studiert und dabei festgestellt, daß der Anilidrest für eine direkte Metallierung der maskierten Picolin- und Isonicotinsäure gut geeignet ist. Der beobachtete Einfluß des Substituenten bei verschiedenen Temperaturen bei Bildung der metallierten Spezies und die Probleme ihrer Reaktivität gegen Säuren (MeOD) und Carbonyl-Elektrophilen wurden diskutiert.

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Copyright information

© Springer-Verlag 1990

Authors and Affiliations

  • Jan Epsztajn
    • 1
  • Andrzej Jóźwiak
    • 1
  • Krzysztof Czech
    • 1
  • Aleksandra K. Szcześniak
    • 1
  1. 1.Department of Organic Chemistry, Institute of ChemistryUniversity of ŁódźŁódźPoland

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