ChemInform Abstract: Photo-CIDNP in the Vacuum-UV: Di-tert-butyl Ether and 2,2,5,5-Tetramethyltetrahydrofuran in Aqueous Solution.
Abstract
When irradiated with 193 nm (ArF excimer laser), non-aqueous solutions (neat ether or in cyclo-C6D12) as well as aqueous solutions of prim., sec., or mono-tert. ethers show no polarized NMR signals.
ChemInform Abstract
When irradiated with 193 nm (ArF excimer laser), non-aqueous solutions (neat ether or in cyclo-C6D12) as well as aqueous solutions of prim., sec., or mono-tert. ethers show no polarized NMR signals. Only solutions of di-tert-butyl ether (I) (and the furan (VI)) in O2-free D2O give 1H NMR signals which are interpreted as arising from CH3D and CH3-CH3. It is proposed that photoionization leads to the radical cation (I)·+ and a solvated electron, the former splitting off ·CH3 radicals, while the latter with D+ gives D atoms, so that CH3D may be formed in-cage; CH3-CH3 then is believed to be an out-of-cage product.
