Name
Title | ||
|---|---|---|
Mechanism For The Reaction Of 2-Naphthol With N-Methyl-N-Phenyl-Hydrazine Suggested By The Density Functional Theory Investigations |
Abstract | ||
|---|---|---|
For the first time the computed mechanisms for the novel reaction of 2-naphthol with N-methyl-N-phenylhydrazine, leading to 1-amino-2-naphthol (Tang et al., J Am Chem Soc 2008, 130, 5840), have been investigated using the density functional theory. Four distinct possible pathways were evaluated: two amination mechanisms with the attack of NH2 group respectively at the alpha-position C1 and beta-position C3 atoms of 2-naphthol (pathways 1 and 2) as well as two rearrangement processes with displacement of the phenolic hydroxyl group followed by the benzidine-like rearrangement at the alpha-position C1 and beta-position C3 atoms of 2-naphthol, respectively (pathways 3 and 4). Solvent effect has been tested based on the optimized geometries of the stationary points in solution at the B3LYP/PCM/6-31+G(d,p) level of theory with an averaged dielectric constant of binary solvent. Single-point energies of the optimized structures have been calculated using three hybrid density functionals, B3LYP, MPW3LYP, and B3PW91 with the 6-311++G(3df,2p) basis set. Our computed results clearly manifest that pathway 1 (alpha-amination) has the highest possibility to occur, with the Gibbs free energies being lower by 6 to 20 kcal/mol compared with the other three pathways, which leads to 1-amino-2-naphthol and N-methylaniline as products. It is in excellent agreement with the experimental observation. (C) 2011 Wiley Periodicals, Inc. J Comput Chem 33: 220-230, 2012 |
Year | DOI | Venue |
|---|---|---|
2012 | 10.1002/jcc.21967 | JOURNAL OF COMPUTATIONAL CHEMISTRY |
Keywords | Field | DocType |
N-methyl-N-phenylhydrazine, 2-naphthol, direct ortho amination, dielectric constant of binary solvents, polarizable continuum model | Polarizable continuum model,Amination,Molecule,Computational chemistry,Chemistry,Density functional theory,Solvent,Basis set,Gibbs free energy,Solvent effects | Journal |
Volume | Issue | ISSN |
33 | 2 | 0192-8651 |
Citations | PageRank | References |
0 | 0.34 | 0 |
Authors | ||
6 | ||
Name | Order | Citations | PageRank |
|---|---|---|---|
| Jie Ying Gao | 1 | 0 | 0.34 |
| Cheng Hua Zhang | 2 | 0 | 0.34 |
| Mei Ming Luo | 3 | 0 | 0.34 |
| Chan Kyung Kim | 4 | 20 | 7.00 |
| W. Chu | 5 | 2 | 1.05 |
| Ying Xue | 6 | 97 | 11.99 |