Novel oxidations attending the photorearrangement of a nitrosamide and the photoaddition of nitrosamine are described and compared with the corresponding non-oxidative photoreactions.hWith proper filters, disproportionation during photorearrangement of N-nitrosohexylacetamide and tautomerization during nitrosopiperidine photoaddition to cyclohexene can be minimized togive improved yields of the antidimers of C-nitroso compounds. These side reactions are shown to be exclusively derived from secondary photoreactions of the C-nitroso compounds. In the presence of oxygen. the courses of the photoreactions are diverted cleanly to form nitrate esters. Oxygen reacts with nitric oxide, both in the free state and when paired with the C-radical thus diverting the course of the reaction. The rate constant of radical combination between a C-radical and nitric oxide is estimated to be in the range of 2 x lo7 s-l.De nouvelles oxydations accompagnant le photortarrangement de la nitrosamide et la photoaddition de la nitrosamine sont decrites et comparkes avec les photoreactions non-oxydantes correspondantes. Avec des filtres convenables, la dismutation durant le photorearrangement de la N-nitrosohexylacCtamide et la tautomerisation durant la photoaddition de la nitrosopiperidine au cyclohextne peuvent &tre reduites au minimum pourainsi donnerde meilleurs rendementsen dimeres-co~ti des composCsC-nitroso. Ces reactions parasites proviennent, tel qu'il a tte demontre, exclusivement de photoreactions secondaires descornposes C-nitroso. En presence d'oxygene, le cheminement des photorkactions est netternent rnodifii pour former des esters nitrate. L'oxygene reagit avec l'oxyde nitrique, a la fois a I'etat libreet lorsque pairk au C-radical, pour ainsi dCvier le chemin de la reaction. La constante de vitesse de la combinaison radicalaire entre le C-radical et I'oxyde nitrique semble se situer dans les alentours de 2 x lo7 s-I.[Traduit par le journa]] Can.

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Can. J. Chem. 56, 1657Chem. 56, (1978.Decompositions of tetramethyl-2-tetrazene (TMT) under acidic conditions were investigated by product analysis and by nmr and esr spectroscopic monitors. Photolysis in acetonitrile containing trifluoroacetic acid generated the dimethylaminium radical which added efficiently to an olefinic double bond. Some adducts contained a (CH3),NCH2-moiety, the immediate precursor of which could be CH2=N(CH3),+ species. Photolytic addition of TMT to norbornenes generated 2-norbornyl radicals that underwent coupling through the exo or endo side to give the dimers. Thermal decomposition in sulfuric acid in the presence of toluene gave N,N-dimethyltoluidines, N-methylphenethylamine, benzyltoluenes, and a plethora of other minor products in addition to a large amount of formylidene methylamine. The last compound was the major product when thermal decomposition of T M T was carried out in trifluoroacetic acid in the presence of toluene or anisol; amination products of aromatic substrates were low and contained only ortllo and porn isomers. TMT dissolved in these solvents exhibited the esr signal of the stable T M T t (the tetrazene cation radical) which did not react with cyclohexene. In concentrated sulfuric acid, T M T was decomposed in less than 15 min giving formylidene methylamine and dimethylamine as shown by nmr. In trifluoroacetic acid, the esr signal of tetramethylhydrazine cation radical ( T M H t ) emerged after the TMT solution was irradiated ; no dimethylaminium radical signal could be detected. The relationship of TMTf and TMHC with formation of the observed products remains unclear. Chem. 56, 1657Chem. 56, (1978.On a Ctudie, a I'aide de I'analyse des produits et par etudes spectroscopiques rmn et rpe la decomposition de la tetrarnethyltetrazene-2 (TMT) dans des conditions acides. La photolyse dans I'acetonitrile contenant de I'acide trifluoroacetique conduit a la formation de radical dimethylaminium qui s'additionne d'une f a~o n efficace a la double liaison olkfinique. Quelques produits contenaient une portion (CH3),NCH2-dont le prkcurseur immkdiat serait I'espece CH2N(CH3),+. L'addition photolytique du TMT aux norbornenes conduit a des radicaux norbornyl-2 qui subissent des couplages par les faces exo ou erldo pour conduire a des dimeres. La decomposition thermique dans I'acide sulfurique en presence de toluene conduit aux N,N-dimethyltoluidines, a la N-methylphenethylamine, aux benzyltoluenes et a toute une strie d'autres produits mineurs en plus d'une grande quantitt de formylidene methylamine. Ce dernier conrposk est le produit majeur lorsque la dCcomposition therrnique du TMT est effectuee dans I'acide trifluoroacetique en presence du toluene ou d'anisol; les produits d'amination des substrats aromatiques sont faibles et contiennent uniquement les isomeres orflro et pnrn. Lorsque le TMT est dissous dans ces solvants, il presente un signal rpe correspondant a I'entite T M T t (le radical cation tetraztne) qui ne rtagit pas avec le cyclohexene. Dans l'acide sulfurique co...

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