jo016293b_si_002.pdf (171.13 kB)
Download file

(1Z,3Z)-1,4-Di(pyridin-2-yl)buta-1,3-diene-2,3-diol:  The Planar Highly Conjugated Symmetrical Enediol with Multiple Intramolecular Hydrogen Bonds

Download (171.13 kB)
journal contribution
posted on 17.04.2002, 00:00 authored by Borys Ośmiałowski, Erkki Kolehmainen, Maija Nissinen, Tadeusz M. Krygowski, Ryszard Gawinecki
1H, 13C, and 15N NMR spectral data show that in chloroform solution (1Z,3Z)-1,4-di(pyridin-2-yl)buta-1,3-diene-2,3-diol, OO, is in ca. 9:1 equilibrium with (3Z)-3-hydroxy-1,4-di(pyridin-2-yl)but-3-en-2-one, OK, while no 1,4-di(pyridin-2-yl)-2,3-butanedione, KK, was detected. The species present in the tautomeric mixture were identified by comparing their experimental chemical shifts with those known for similar compounds as well as with the theoretically calculated (GIAO-HF/DFT) values. Ab initio calculations show that OK and especially the highly conjugated OO forms are preferred in the tautomeric mixtures both in vacuo and in chloroform solution. Comparison of experimental (Arrhenius) and calculated (ab initio) energies of OK shows that the MP2/6-31G**//RHF/6-31G** method gives the most precise results. There are one and two strong O−H···N hydrogen bonds present in the molecules of the former and latter compound, respectively. Other tautomeric forms, e.g., dienaminedione [(1Z,4Z)-1,4-di[pyridin-2(1H)-ylidene]butane-2,3-dione], and their rotamers were found to have higher energies. The single-crystal X-ray diffraction studies show that dienediol OO is the only tautomeric form present in the crystal at 173 K. Its almost perfectly planar molecule is stabilized by two strong intramolecular O−H···N hydrogen bonds.

History