| Autor: |
Yonekawa, Sayuri, Goodpaster, Aaron M., Abel, Benjamin A., Paulin, Rodney G., Sexton, Charles W., Poole, James S., Storhoff, Bruce N., Fanwick, Phillip E. |
| Zdroj: |
Journal of Heterocyclic Chemistry; May 2006, Vol. 43 Issue: 3 p689-694, 6p |
| Abstrakt: |
5Azido2methoxy1,3xylyl18crown5 has been prepared by reacting ptoluenesulfonyl azide with the carbanion generated from the reaction of 5bromo2methoxy1,3xylyl18crown5 with nbutyl lithium. The asymmetric N3stretch of this product has been observed as a single band at 2110 cm−1in dichloromethane solution. Addition of solid NaSCN, KSCN and CsSCN shifts this band to 2115, 2113 and 2112 cm−1, respectively. Computational studies of this azide at the B3LYP631G level in the presence and absence of Napredicted these bands to be at 2173 cm−1and 2184 cm−1. For the saltcontaining solutions, additional bands were observed at 2066 cm−1, 2056 cm−1and 2055 cm−1, respectively, which are in the range expected for CN stretches. The Xray structure of this azide has been determined. The terminal and internal NN bond lengths were found to be 1.1272 and 1.2452 Δ, respectively, which is the usual pattern for aromatic azides. The crown ether is looped over the face of the aromatic ring resulting in an angle of 38.94° between the plane defined by the aromatic ring and that defined by the five ring oxygen atoms. In addition, the CH3group is rotated out of the plane of the phenyl ring with C1C18O181C182 and C17C18O181C182 dihedral angles of 93.8114° and 90.5414°, respectively. |
| Databáze: |
Supplemental Index |
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