solution and solid state (cpmas) nmr studies of the tautomerism of six-membered heterocyclic compounds related to 2-pyridones解决方案和固态(cpmas)的核磁共振研究2-pyridones六元杂环化合物的互变现象相关.pdfVIP

Spectroscopy 14 (2000) 121–126 121 IOS Press Solution and solid state (CPMAS) NMR studies of the tautomerism of six-membered heterocyclic compounds related to 2-pyridones Concepción López a,, Rosa María Claramunt a,, Ibon Alkorta b and José Elguero b a Departamento de Química Orgánica y Biología, Facultad de Ciencias, UNED, Senda del Rey 9, E-28040 Madrid, Spain b Instituto de Química Médica, CSIC, Juan de la Cierva, 3, E-28006 Madrid, Spain Received October 1999 Accepted January 2000 Abstract. Several 13C and 15N chemical shifts of 2-pyridone (1), 4(3H)-pyrimidone (2), uracil (3) and cytosine (4) have been measured in solution and in the solid state. These data have been discussed in relation with the tautomerism of the four hete- rocycles. GIAO ab initio calculations of absolute shieldings have been carried out to identify the predominant tautomers in the case of compounds (1) and (2). 1. Introduction A recent survey of the physical methods to study tautomerism [1] reveals that there are no examples of the use of solid state NMR (13C and 15N) to establish the tautomer present in the solid state in the case of six-membered heterocyclic rings (azines). On the contrary, examples of application to five-membered rings (azoles) abound [2–8]. To demonstrate the possibilities of CPMAS NMR for the study of the tau- tomerism of azines, four “classical” compounds were selected: 2-pyridone (1), 4(3H)-pyrimidone (2), uracil (3) and cytosine (4). These compounds can exist in several tautomeric forms: two for pyridone, three for pyrimidone and six for uracil and cytosine (Scheme 1). Previous information [9] indicates that pyridone exists in solution as tautomer 1b, 4(3H)-pyrimidone in water is a 50 : 50 mixture of 2b and 2c (in other solvents, 2c seems predominant); uracil both in solution and in solid state exists as pyrimidine-2,4-dione (3f) [10], finall