3273-26-5Relevant articles and documents
C-Nitroso compunds. Part XXXVII. The reactivity of α-chloronitroso compounds towards organoaluminium reagents
Lub, J.,Beekes, M. L.,Boer, Th. J. de
, p. 22 - 27 (2007/10/02)
With sterically unhindered and certain moderately hindered α-chloronitroso compounds 1 trimethylaluminium at low temperature gives, via complexes 2 and 3, the methyl nitrones 4 (Scheme 1).Several intermediate complexes 3 lose methane upon heating and rearrange to α-chloroimines 5 (Scheme 2), the structure of which is determined by that of the precursors (E- or Z-geometry; cf.Scheme 6).More sterically hindered α-chloronitroso compounds containing quaternary carbon undergo C-C rupture when treated with trimethylaluminium, thus forming hydroxamic acid chlorides, formally HCl adducts of nitrile oxides (cf. 8j in Scheme 3; 8k in Scheme 4).In the latter case, subsequent reactions lead to overall ring enlargement, i. e. formation of the seven-membered cyclic oxime 12.With triethylaluminium and triisobutylaluminium, α-chloronitroso compounds are mainly reduced to oximes and the isomeric amides (Scheme 7).
