C‐Nitroso compounds. Part XXX. The mechanism of photolysis of chloro nitroso compounds; irradiation of 2‐chloro‐2‐nitrosoadamantane in methanol

摘要: The photolysis of gem-chloronitrosoalkanes 1 in methanol has been studied with the model compound 2-chloro-2-nitrosoadamantane (AdClNO) 1a. mechanism is outlined Scheme 1, and involves initial C-NO bond cleavage. generated chloroalkyl radicals 2 are captured by unchanged starting material giving key intermediate, a 1,1′-dichloro nitroxide 3. Although this process probably reversible inert solvents, 3 irreversibly removed alcohols conversion into N-(1-chloroalkyl)nitrone 4, which solvolysed to an equimolar mixture acetal oxime. During no ESR signals observed. Nevertheless, transient existence chloro nitroxides supported detection di-sec-alkylnitroxides 5, formed when photolyzed solution nitroso treated tri-n-butylstannane (reaction [7]). further AdClNO presence nitrosobenzene aprotic solvents isolation relatively stable hydrochloride nitrone: phenyladamantylideneamine oxide 6a.