ABINITIO AND SEMIEMPIRICAL CALCULATIONS ON THE TAUTOMERIC EQUILIBRIA OF N-UNSUBSTITUTED AND N-SUBSTITUTED BENZOTRIAZOLES

被引:56
作者
KATRITZKY, AR
YANNAKOPOULOU, K
ANDERS, E
STEVENS, J
SZAFRAN, M
机构
[1] UNIV ERLANGEN NURNBERG,INST ORGAN CHEM,W-8520 ERLANGEN,GERMANY
[2] THREE M CO,ST PAUL,MN 55144
[3] ADAM MICKIEWICZ UNIV,DEPT CHEM,PL-60780 POZNAN,POLAND
关键词
D O I
10.1021/jo00309a009
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The geometries, relative stabilities, ionization potentials, and dipole moments for benzotriazole tautomers and their (dimethylamino)methyl derivatives were calculated by PM3, AMI, and MNDO semiempirical methods with full geometry optimization and with an ab initio 3-21G basis set. The geometries optimized by semiempirical methods are comparable with those obtained with partial optimization ab initio (6-31G and 3-21G levels) and available crystallographic data. Ab initio and semiempirical calculations failed to reproduce the N2-N3 bond length in 1 H-benzotriazole. The X-ray dimensions of compound 4, which due to its structural and electronic properties can be considered as a model compound for the 1 -[ (dimethylamino)methyl]benzotriazole 2a, indicate that the “small” 3-21G basis set predicts bond lengths for this 1-substituted derivative, which are close to experimental data. The PM3 method gives NH{ in agreement with ab initio calculations, but both the AMI and the MNDO methods do not. For benzotriazole, both semiempirical and ab initio calculations predict a large energy preference of the 1H over the 2H form. For the JV- [(dimethylamino)methyl] derivatives, the ab initio results correctly predict an almost equal stability of the two forms (2a and 2b) but the semiempirical methods fail. The influence of the fused benzo ring, together with the electronic properties of the N substituents, determines the relative stabilities of 1- and 2-substituted benzotriazoles. © 1990, American Chemical Society. All rights reserved.
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页码:5683 / 5687
页数:5
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