Complexes of 18-crown-6 macrocyclic ethers containing both an alkali metal phenoxide salt and phenol. Crown:salt:phenol ratios of 1:1:1 and 1:1:2

Autor: Rodrigue, André, Bovenkamp, John W., Murchie, Michael P., Buchanan, Gerald W., Fortier, Suzanne
Zdroj: Canadian Journal of Chemistry; November 1987, Vol. 65 Issue: 11 p2551-2557, 7p
Abstrakt: Sodium and potassium phenoxide, in the presence of one equivalent of dicyclohexano-18-crown-6 (cis–anti–cisisomer) and dibenzo-18-crown-6, form complexes that have a ratio of 1:1:1 (crown:salt:phenol) in ethereal solvents containing excess phenol. On the other hand, complexes having 1:1:2 ratios (crown:salt:phenol) are obtained under the same conditions when the macrocycle is 18-crown-6 or dicyclohexano-18-crown-6 (cis–syn–cisisomer). When only one equivalent of phenol is present, then 1:1:1 complexes are obtained with 18-crown-6 and dicyclohexano- 18-crown-6 (cis–syn–cisisomer). No complexes containing only the metal salts were isolated from these solutions. The infrared spectral data obtained from the complexes show that the phenol hydroxyl hydrogens in the complexes form either strong or very strong hydrogen bonds. The nuclear magnetic resonance chemical shifts of the phenol protons in the complexes have been obtained from deuterated dimethoxyethane solutions. Comparisons are made with the chemical shifts of the phenol hydroxyl protons obtained from the corresponding solutions containing only the equivalent salt/phenol solutions.
Databáze: Supplemental Index