Trimethylamine photolysis

Tertiary Amines. The trimethylamine photolysis was studied by ESR at 77 K, neat and in an aqueous matrix (205). Me2N and CH were observed, but not Me2NCH2. The photodecomposition... 

Photolysis of aryl azides in amine solution, with a tertiary amine as cosolvent to promote stabilization of the singlet nitrene, has met with some success. For example, the yield of 2-piperidino-3 W-azepme. obtained by the photolysis of phenyl azide in piperidine, is increased from 35 to 58% in the presence of A A /V. /V -tetramethylethylenediamine (TMLDA).180 Also, an improved yield (36 to 60 %) of A,(V-diethyl-3W-azepin-2-amine (38, R = Et) can be obtained by irradiating phenyl azide in triethylamine, rather than in dicthylaminc, solution.181 Photolysis (or thermolysis) of phenyl azide in TMEDA produces, in each case, 38 (R = Et) in 40% yield.181 In contrast, irradiation of phenyl azide in aniline with trimethylamine as cosolvent furnishes jV-phenyl-377-azepin-2-amine (32, R = Ph) in only low yield (2%).35... 

Dimethylamino. There are many more known sources of this radical than of the methylamino radical. Photolysis of dimethyl- and trimethylamine yields the radical by Reactions 10 and 11... 

In pure trimethylamine, the strongly shifted IR absorptions of n-adduct 12 also disappeared upon irradiation with 254 nm light. By comparison with the IR spectra of an authentic sample it could be shown that under these conditions the only photoproduct was bis(AT,Al-dimethylamino)-dimethylsilane (16). The absence of the rearrangement product 15 could be demonstrated by comparison with the spectra of an authentic sample of 15 which was generated by photolysis of trimethylsilylazide 17 in pure NMes. 

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