Hg-Sensitized Photolysis of Diethylamine in the Absence and Presence of O2 or N2O

Article abstract of DOI:10.1021/j100410a033

The Hg-sensitized photolysis of diethylamine (DEA) was studied in the absence and presence of O2 or N2O at room temperature.In the absence of foreign gases, the products were H2, CH3CH=NC2H5, and N,N'-diethylbutane-2,3-diamine (III), with respective quantum yields of 1.0, 1.0, and ca. 0.02.Thus CH3C^.HNHC2H5 radicals are produced exclusively and they are removed by self reaction: 2CH3C^.NHC2H5-> DEA+CH3CH=NC2H5 (4a) and 2CH3C^.NHC2H5->diamine (III) (4b), with k_4a/k_4b=47.0+/-5.6.In the presence of O2 the radicals are scavenged exclusively by abstraction of the H atom on the nitrogen to give the imine CH3CH=NC2H5 as the exclusive product :CH3CH^.NHC2H5+O2-> CH3CH=NC2H5+ H2O (5).The Hg-sensitized photolysis of N2O gives O(³P)atoms, which in the presence of DEA react to give the imine and (C2H5)NOH (DEHA) as products in concerted parallel steps: O(³P)+(C2H5)2NH -> CH3CH=NC2H5+H2O (9a) and O(³P)+ (C2H5)2NH-> (C2H5)2NOH (9b), with k_9a/k_9b ca. 9.5 +/- 1.7.