Name
Title | ||
|---|---|---|
Mechanistic Investigation Inspired "On Water" Reaction For Hydrobromic Acid-Catalyzed Friedel-Crafts-Type Reaction Of Beta-Naphthol And Formaldehyde |
Abstract | ||
|---|---|---|
The mechanism of the HBr-catalyzed Friedel-Crafts-type reaction between -naphthol and HCHO was investigated by DFT to improve this reaction. The HBr-H2O co-catalyzed the preferential pathway undergoes the concerted nucleophilic addition and hydrogen shift, stepwise followed by H2O elimination and the CC bond formation. The origin of the high catalytic activity of HBr is ascribed to CHBr- and OHBr- interactions, which suggest that the active species is Br-. Moreover, water molecules efficiently assist in improving the activity of Br-. The computational results show that solvent polarity profoundly affects the activation barriers. To our delight, the activation barrier of the rate-determining step for the favored pathway in water is comparable (0.6 kcal/mol difference) with that in acetonitrile. The experimental observation further confirmed our results and demonstrated that the title reaction can be successfully achieved on water. Therefore, we open a new efficient and green strategy for the synthesis of biphenol derivatives. (c) 2017 Wiley Periodicals, Inc. |
Year | DOI | Venue |
|---|---|---|
2017 | 10.1002/jcc.24877 | JOURNAL OF COMPUTATIONAL CHEMISTRY |
Keywords | Field | DocType |
density functional theory, "on water" reaction, mechanism, HBr-catalyzed, non-covalent interaction | Catalysis,Molecule,Chemistry,Acetonitrile,Nucleophilic addition,Hydrobromic acid,Solvent,Friedel–Crafts reaction,Photochemistry,On water reaction | Journal |
Volume | Issue | ISSN |
38 | 26 | 0192-8651 |
Citations | PageRank | References |
0 | 0.34 | 1 |
Authors | ||
6 | ||
Name | Order | Citations | PageRank |
|---|---|---|---|
| Shanshan Cao | 1 | 0 | 0.34 |
| Haiyan Yuan | 2 | 0 | 1.69 |
| Yang Yang | 3 | 612 | 174.82 |
| Mang Wang | 4 | 0 | 0.34 |
| Xiaoying Zhang | 5 | 0 | 0.34 |
| Jingping Zhang | 6 | 9 | 7.30 |