6302-02-9Relevant articles and documents
SRN1 reactions of aryl halides with carbanions initiated by sodium amalgam in liquid ammonia
Austin, Eduardo,Ferrayoli, Carlos G.,Alonso, Ruben A.,Rossi, Roberto A.
, p. 4495 - 4502 (2007/10/02)
The reaction of 1-chloronaphthalene with acetone (2a) and acetophenone (2b) enolate ions was initiated by sodium amalgam [Na(Hg)] in liquid ammonia giving good yields of the substitution products 3a and 3b respectively. 2-Chloroquinoline and 2-chloropyridine gave good yields of substitution product with 2b, and moderate to good yields with 2a. 4-Bromobenzophenone and 2a gave 78% of the substitution product 5. With aryl halides whose radical anions fragment fast and consequently close to the Na(Hg) surface, such as bromobenzene and p-bromoanisole, only dehalogenation products were observed. However, when benzonitrile was used as a redox catalyst, about 50% of the substitution product 6 was obtained with p-bromoanisole and 2a. However, with the more reactive carbanionic nucleophile, such as anthrone anion 4, good yields of the substitution product 7 were obtained with bromobenzene. In all these reactions neither reduction of the aromatic moiety nor the ketone functionality was observed. It is therefore suggested that Na(Hg) amalgam initiates these SRN1 reactions.
TAUTOMERISM OF AZINE DERIVATIVES. 11. 14N-NMR AND 17O-NMR INVESTIGATION OF INTRACHELATE TAUTOMERISM OF ACYLMETHYLPYRIDINES
Lapachev, V. V.,Stekhova, S. A.,Mainagashev, I. Ya.,Fedotov, M. A.,Khall, V. E.,Mamaev, V. P.
, p. 633 - 639 (2007/10/02)
Intrachelate -sigmatropic tautomerism in a series of acylmethylpyridines has been studied by 14N- and 17O-NMR specroscopy.Principles of tautomer modelling or simulation have been proposed and examined, nitrogen ond oxygen chemical shift spectra have been determined, and the accuracy of this method for the determination of tautomer composition has been evaluated.The presence of acceptor (electron withdrawing) substituents in the acylmethyl side-chain fragment has been found to stabilize the NH-tautomer.
