A subject of the polyamine compounds which are homologous structural spermidine .

摘要

Spermidine homologues of formula (I) (n=3-5; R=1-4C alkyl), are prepared by reacting dibenzylamine with an alkyl vinyl ketone of formula CH2=CHCOR (II) in a solvent (methanol) at 0-60 deg C for 5-24 hours, to form (C6H5CH2)2N(CH2)2COR (III). The keto group is reduced (NaBH4) in a solvent (ethanol) at 15-25 deg C for 2-12 hrs to form (C6H5CH2)2N(CH2)2CHOHR (IV) and this is catalytically reduced (H2/Pd on C; methanol; 10-40 deg C; atmos. pressure) to give C6H5CH2NH(CH2)2CHOHR (V). This is then reacted with an w-cyanoalkyl halide of formula Hal(CH2)n-1CN (Hal = Cl or Br) in refluxing butanol in the presence of an alkaline carbonate and opt. in the presence of an iodide for 2-24 hrs to give (VI). The alcohol function is esterified using methane sulphonyl chloride in diethylether or a halogen solvent, in the presence of an aprotic base e.g. triethylamine or pyridine at -20 - 35 deg C for 1-24 hrs, to give (VII). Reaction with sodium azide in DMSO at 20-60 deg C for 4-20 hours gives (VIII). This is then reacted with hydrogen in the presence of di tert. butyl dicarbonate and a catalyst (Pd/C), under a H2 pressure of 1.5-5.1x105 Pa, in a solvent e.g. ethyl acetate, at ambient temp. for 5-20 hrs, to give (IX). Hydrogenation of (IX) in the presence of Raney nickel in ethanol saturated with ammonia gas at a pressure of 2-40x105 Pa for 6-24 hours gives (I).