Photoreaction of Nitroso Compounds in Solution. Part XXXII: Synthesis and Reaction of 2-Nitrato-3-Aminonorbornanes

Abstract

K. SOMOSEKHAREN PILLAY, KAORU HANAYA, and YUAN L. CHOW. Can. J. Chem. 53, 3022 (1975).Oxidative photoaddition of nitrosamines to norbornene gave both cis-exo-and trans-2nitrato-3-aminonorbornanes that were stable in their protonated form under photolysis wnditions. The free bases underwent a novel cleavage reaction assisted by the lone pair of the amino group to give 1,3-bis(formy1)cyclopentane. In addition these nitrates also underwent solvolysis to give cis-exo-2-hydroxy-3-aminonorbornane. The mechanisms of these basic decompositions are discussed.K. SOMOSEKHAREN PILLAY, KAORU HANAYA et YUAN L. CHOW. Can. J. Chem. 53, 3022 (1975).La photoaddition oxydative des nitrosamines au norbornitne conduit aux cis-exo-et transnitrato-2 amino-3 norbornanes; dans les conditions de la photolyse, ces deux isomitres sont stables sous leur forme protonke. Les bases libres subissent une nouvelle rkaction de fission aid& par le doublet libre du groupe amino et fournissent le bis(formyl)l.3 cyclopentane. De plus ces nitrates subissent une solvolyse pour conduire aux cis-exo-hydroxy-2 amino-3 norbornane. On discute des mkanismes de ces dkompositions en milieu basique.[Traduit par le journal1 'For Part XXXI, see ref. 1. Part of the report was published in the preliminary communication (see ref. 2). of 3-exo-piperidino-endo-bicyclo[2.2.1]heptan-2-ZOn sabbatical leave from Yamagata University, 01 (7, R2 = -(CH2)5-)Was isolated as the Yamagata, Japan, 1973-1974 hydrochloride salt. To avoid the decomposition Can. J. Chem. Downloaded from www.nrcresearchpress.com by KAIYOKENKYU KAIHATSU KIKO on 11/20/14For personal use only.

Reactivities of amino and aminium radicals: oxidative photoaddition of tetramethyl-2-tetrazene to olefins

“…It is interesting to note that the average photon consumption per molecule of halomethane reacted (2100-8000) is far in excess of the [25][26][27][28][29][30][31][32][33][34][35] photons per molecule required for dissociation on thermochemical grounds. This disparity may be explained through the absorption of photons by many molecules in the focal region with only a few of these achieving sufficient energy to dissociate.…”