Studies in vacuum ultraviolet photochemistry IV. Diethyl ether

Abstract

Diethyl ether has been photolysed at 147 and 123 nm in the gas phase at pressures of 2–200 Torr and conversions <0·5%. The most important primary process is that involving C–O fission [reaction (i)]. Et–O–Et +hν→ Et + EtO (i) The majority of the ethoxyl radicals decompose in an early vibration by loss of a methyl radical [reaction (ii)]. EtO → Me + HCHO (ii) There is a small contribution from a second primary process [reaction (iii)] involving elimination of hydrogen. Et–O–Et +hν→ EtOCHCH₂+ H₂(or 2H)(iii) The ratio process (i): process (iii) is ca. 60. The overall photochemistry is interpreted in terms of these primary processes, and subsequent reaction of the radical products.