Exploring the catalytic activity of Lewis-acidic uranyl complexes in the nucleophilic acyl substitution of acid anhydrides
| Autor: | Koichiro Takao, Shin Akashi |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2017 |
| Předmět: |
010405 organic chemistry
General Chemical Engineering Ethyl acetate Nucleophilic acyl substitution General Chemistry 010402 general chemistry Uranyl 01 natural sciences Medicinal chemistry 0104 chemical sciences Catalysis Acylation chemistry.chemical_compound Acetic anhydride Acetic acid chemistry Nucleophile Organic chemistry |
| Zdroj: | RSC Advances. 7(No. 20):12201-12207 |
| Popis: | The catalytic activities of several uranyl complexes, such as N,N′-disalicylidene-o-phenelyenediaminato(ethanol)dioxouranium(VI) (UO2(salophen)EtOH), bis(dibenzoylmethanato)(ethanol)dioxouranium(VI) (UO2(dbm)2EtOH), pentakis(N,N-dimethylformamide)dioxouranium(VI) ([UO2(DMF)5]2+), and tetrakis(triphenylphosphine oxide)dioxouranium(VI) ([UO2(OPPh3)4]2+), were examined in the nucleophilic acyl substitution of acid anhydrides. Among them, [UO2(OPPh3)4]2+ was the most efficient to give ethyl acetate and acetic acid from acetic anhydride (Ac2O) and ethanol, and was resistant towards decomposition during the catalytic reaction. Several nucleophiles were also subjected to the catalytic acylation reaction using acetic and pivalic anhydride. Kinetic and spectroscopic studies suggested that [UO2(OPPh3)4]2+ interacts with Ac2O to form [UO2(Ac2O)(OPPh3)3]2+. Interaction of this actual catalyst with additional Ac2O determines the rate of the overall nucleophilic acyl substitution reaction. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|