Synthesis of hyrdroxylamine analogues of polyamines

Novel analogues of spermine and spermidine with terminal H2N-CH2-group substituted by H2N-O-group, were prepared starting the synthesis from EtO(Me)C=NOH and subsequent extension of a polyamine backbone. To prepare their earlier unknown tritium labelled analoques, omega-[[(1'-ethoxyethylidene)amino]oxy]-poly-(iminomethylene) nitriles were reduced to amines by NaBT2/CoCl2 complex, which did not effect the N-O or C=N bonds of ethoxyethylidene group, whereas aminooxy group deprotection was performed at the final step of synthesis by mild acidic hydrolysis. Novel monoacetylated (AcHN- or AcNHO-) analogues of spermidine were also synthesised. Copyright (C) 1996 Elsevier Science Ltd