Alkyl derivatives secondary alkylamines

Photoamination via Category III has been investigated in polycyclic arenes such as phenanthrene (la) and its derivatives (Ib-li), anthracene (Ij), and naphthalene derivatives (Ik-lv) [36-37], A typical example was photoamination of la with NHj, which was performed by the irradiation of an ammonia-saturated MeCN-H O solution containing la and m-DCB for 17 h to give the Type I aminated product, 9-amino-9,10-dihydrophenanthrene (10a), in 84% yield (Scheme 6.11). It was apphed to photoamination with primary amines such as alkylamines, ethanolamine, allylamine, and glycine ethyl ester and so on, which gave efficiently A-alkyl derivatives of 10a. But photoamination with secondary alkylamines such as dimethylamine and diethylamine were inefficient [38]. 

Formamidine acetate was prepared in similar high yield by a similar procedure but with glacial acetic acid as solvent.804 A A-Disubstituted formamidine and acetamidine derivatives have been obtained analogously from orthoesters and alkylamines in the presence of glacial acetic acid805 or boron trifluoride etherate 806 In the reaction of orthoesters with secondary amines in the presence of toluenesulfonic acid the formation of ketene aminals (alkyl l -amino-vinyl ethers) was also observed.807... 

Preparation of secondary amines by reductive alkylation of ammonia is not such a general reaction as that of primary amines. In the aliphatic series treating ammonia with 2 moles of a carbonyl compound usually affords a mixture of mono-, di-, and tri-alkylamines. However, 80-90% yields of the corresponding dibenzylamine are obtained from benzaldehyde or its o-chloro or o-methyl derivative.996... 

There have been several papers dealing with the oxidation reactions of nitrogen and sulfur-based compounds. Hindered amines, such as substituted 2,2,6,6-tetramethylpiperidines, are easily oxidized by electron-transfer reactions to the corresponding cation, by the sulfate radical anion, and by sensitized electron transfer to carbonyl triplets. Radicals derived from tertiary piperidines were observed directly by optical spectroscopy and deprotonated to a-alkylamine radicals. The amine radical cation derived from secondary piperidines deprotonated to give aminyl radicals. In the presence of oxygen, both classes were oxidized to give nitroxyl radicals, but by different proposed mechanisms. Both oxidation and fragmentation pathways have been observed in the photochemical reaction of alkyl phenyl sulfides with tetranitromethane. The oxidation of various A-(arylthio)-4-substituted-2,6-diarylanilines (18) with PbOa yielded, in most cases, persistent radicals that could... 

Di(linear-alkyl)amines (N-(Linear-alkyl)alkylamines) Heterocyclic secondary amines N-Alkylarylamines Pyrrole derivatives Pyrrole... 

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