Theoretical Studies on the Tautomerism of 1,5,6,7-Tetrahydro-4H-indazol-4-ones 英文参考文献.docVIP

Molecules 2006, 11, 415-420 molecules ISSN 1420-3049 Communication Theoretical Studies on the Tautomerism of 1,5,6,7-Tetrahydro-4H-indazol-4-ones Carlos Pérez Medina*, Concepción López * and Rosa M. Claramunt ? Departamento de Química Orgánica y Bio-Orgánica, Facultad de Ciencias, UNED Senda del Rey 9, E-28040 Madrid (Spain); ? e-mail: rclaramunt@ccia.uned.es * Authors to whom correspondence may be addressed; e-mails: cperez@bec.uned.es, clopez@ccia.uned.es Received: 7 June 2006 / Accepted: 9 June 2006 / Published: 12 June 2006 Abstract: Computational studies on three tautomeric forms of four 1,5,6,7-tetrahydro- 4H-indazol-4-one derivatives: 1,5,6,7-tetrahydro-4H-indazol-4-one (1), 6,6-dimethyl- 1,5,6,7-tetrahydro-4H-indazol-4-one (2), 3-methyl-1,5,6,7-tetrahydro-4H-indazol-4-one (3) and 3,6,6-trimethyl-1,5,6,7-tetrahydro-4 H-indazol-4-one (4), have been performed at different levels, ranging from semiempirical AM1, ab initio Hartree-Fock HF/6-31G* and HF/6-31G** to B3LYP/6-31G** density functional calculations. These calculations have been used to establish the most stable tautomer, which in all cases was in agreement with the experimental data. Keywords: Tautomerism, tetrahydroindazoles, theoretical calculations Introduction Annular tautomerism of pyrazole and indazole derivatives has been investigated in depth both theoretically and experimentally [1,2]. A theoretical estimation of the annular tautomerism of 52 N H- indazoles concluded that although in most cases the 1H-tautomer is the most stable, in some indazoles, the 2H-tautomer was more stable than the 1H one [3]. Recently we approached the study of the tautomerism of tetrahydroindazoles (also known as tetramethylenepyrazoles) bearing a trifluoromethyl group at the 3-position and we found that in all cases they exist as 1H-3-CF3 tautomers [4]. We present here our studies on the tautomerism of a more complex case,