The Mercury Photohyphen;Sensitized Hydrogenation of the Butenes and the Photolysis of Dihyphen;nhyphen;butylmercury

摘要

The Hgsngbnd;3P1photohyphen;sensitized hydrogenations of isobutene, buteneminus;1, and buteneminus;2 have been studied from 24 to 300deg;C at an H2:C4H8ratio of 10:1. Mass spectrometer analyses of the products have led to the following conclusions: (1) When a H atom adds to isobutene, the tertiary butyl radical is formed. Any isobutyls decompose immediately into methyl and propene. (2) Addition of a H atom to buteneminus;2 produces littlesec.hyphen;butyl, mostly methyl plus propene. (3) Addition of a H atom to buteneminus;1 produces considerablesec.hyphen;butyl. Anynhyphen;butyls decompose into ethyl and ethene. (4) The isomeric constitution of the octanes suggests that radicals add to olefinic double bonds at the carbon atom with highest electron density. Products from the photolysis of dihyphen;nhyphen;butylmercury at lgr;=2537A indicate thatnhyphen;C4H9=C2H5+C2H4has an activation energy of around 35 kcal.