Stereoelectronic effects in ring-chain tautomerism of 1,3-diarylnaphth[1,2-e][1,3]oxazines and 3-alkyl-1-arylnaphth[1,2-e][1,3]oxazines

István Szatmári, Tamás A. Martinek, László Lázár, Andreas Koch, Erich Kleinpeter, Kari Neuvonen, Ferenc Fülöp

Research output: Contribution to journalArticle

68 Citations (Scopus)


The disubstitution effects of X and Y in 1-(Y-phenyl)-3-(X-phenyl)-2,3-dihydro-1H-naphth[1,2-e][1,3]oxazines on the ring-chain tautomerism, the delocalization of the nitrogen lone pair (anomeric effect), and the 13C NMR chemical shifts were analyzed by using multiple linear regression analysis. Study of the three-component equilibrium B ⇄ A ⇄C revealed that the chain ⇄ trans (A ⇄ B) equilibrium constants are significantly influenced by the inductive effect (σF) of substituent Y on the 1-phenyl ring. In contrast, no significant substituent dependence on Y was observed for the chain ⇄ cis (A ⇄ C) equilibrium. There was an analogous dependence for the epimerization (C ⇄ B) constants of 1-(Y-phenyl)-3-alkyl-2,3-dihydro-1H-naphth[1,2-e][1,3]oxazines. With these model compounds, significant overlapping energies of the nitrogen lone pair was observed by NBO analysis in the trans forms B (to σ* C1-C1′, σ*C1-C10b, and σ*C3-O4) and in the cis forms C (to σ* C1-H, σ*C1-C10b, and σ* C3-O4). The effects of disubstitution revealed some characteristic differences between the cis and trans isomers. However, the results do not suggest that the anomeric effect predominates in the preponderance of the trans over the cis isomer. When the 13C chemical shift changes induced by substituents X and Y (SCS) were subjected to multiple linear regression analysis, negative ρFY and ρF X values were observed at C-1 and C-3 for both the cis and trans isomers. In contrast, the positive ρRY values at C-1 and the negative ρRX values at C-3 observed indicated the contribution of resonance structures f (ρR > 0) and g (ρR < 0), respectively. The classical double bond-no-bond resonance structures proved useful in explaining the substituent sensitivities of the donation energies and the behavior of the SCS values.

Original languageEnglish
Pages (from-to)3645-3653
Number of pages9
JournalJournal of Organic Chemistry
Issue number11
Publication statusPublished - May 28 2004

ASJC Scopus subject areas

  • Organic Chemistry

Fingerprint Dive into the research topics of 'Stereoelectronic effects in ring-chain tautomerism of 1,3-diarylnaphth[1,2-e][1,3]oxazines and 3-alkyl-1-arylnaphth[1,2-e][1,3]oxazines'. Together they form a unique fingerprint.

  • Cite this