Tautomerism heterocycles

General accounts of prototropic tautomerism have been presented by Ingold and Baker" these include an outline of the historical development of the subject in which heteroaromatic compounds are discussed incidentally, and, therefore, such a historical account will not be given here. Of historical interest are Eistert s book on tautomerism and mesomerism which was published in 1938, a review on — NH-CO— tautomerism by Arndt and Eistert published in 1938, and Heller s account of heterocyclic tautomerism which appeared in 1925. Although more recent works on heterocyclic chemistry (e.g., references 9-11) have dealt incidentally with tautomerism, no unified... 

Tliis is one of the most actively developing and closely watched fields of heterocyclic tautomerism—only the study of purines and pyrimidines is of comparable contemporary interest. Tire number of references is so high that many relevant works have had to be neglected, whereas in other sections of this chapter relatively minor contributions have been commented on because they pertained to a field where few contributions are available. Tire selection criteria were (1) all pertinent authors are quoted at least once, (2) full papers are preferred to communications or letters, and (3) recent works are preferred to earlier ones because they usually quote the previous publications. 

Tautomeric studies of equilibria between enamino and methylene imino form have been reported for several heterocycles. Tautomerism of 1,2,4-tri-azino[4,3- ]quinoxalin-5-ones was deduced to be solvent dependent the enamino form 170b is predominant in DMSO-dg ( H NMR), whereas 170a is the major tautomer in the solid state (IR in nujol) (90JHC691 95H2057) (cf. Section III,B). 

Abstract This chapter reviews the theoretical background for continuum models of solvation, recent advances in their implementation, and illustrative examples of their use. Continuum models are the most efficient way to include condensed-phase effects into quantum mechanical calculations, and this is typically accomplished by the using self-consistent reaction field (SCRF) approach for the electrostatic component. This approach does not automatically include the non-electrostatic component of solvation, and we review various approaches for including that aspect. The performance of various models is compared for a number of applications, with emphasis on heterocyclic tautomeric equilibria because they have been the subject of the widest variety of studies. For nonequilibrium applications, e.g., dynamics and spectroscopy, one must consider the various time scales of the solvation process and the dynamical process under consideration, and the final section of the review discusses these issues. 

The present chapter thus provides an overview of the current status of continuum models of solvation. We review available continuum models and computational techniques implementing such models for both electrostatic and non-electrostatic components of the free energy of solvation. We then consider a number of case studies, with particular focus on the prediction of heterocyclic tautomeric equilibria. In the discussion of the latter we center attention on the subtleties of actual chemical systems and some of the dangers of applying continuum models uncritically. We hope the reader will emerge with a balanced appreciation of the power and limitations of these methods. 

Kenny, P.W. Handling heterocyclic tautomerism. Mug-99. Santa Fe, NM, 23-26 February 1999, http //www.daylight.com/meetings/ mug99/Kenny/kenny mug99.htm. 

NMR longitudinal relaxation times can be used for determination of the site of protonation in polyfunctional acids and bases (93JCS(P2)283). Thus, the 14N NMR spectrum of 4-aminopyridine shows clearly from the sharpening of the signal for the ring nitrogen that protonation has occurred here. This procedure is an important innovation in the elucidation of heterocyclic tautomeric structures, especially for the cases of fast exchange. 

Applications of the Born—Kirkwood-Onsager model at the ab initio level include investigations of solvation effects on sulfamic acid and its zwitterion,23i an examination of the infrared spectra of formamide and formamidic acid,222 and a number of studies focusing on heterocyclic tautomeric equilibria.222,232,233 a more detailed comparison of some of the heterocyclic results is given later. The gas phase dipole moment depends on basis set, and systematic studies of this dependence are available. Furthermore, the effects of basis set choice and level of correlation analysis have been explored in solvation studies as well,222,233 but studies to permit identification of particular trends in their impact on the solvation portion of the calculation are as yet insufficient. 

New Developments in Heterocyclic Tautomerism Desmotropes, Carbenes and Betaines... 

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