Synthesis and functionalisation of polyepichlorohydrin

Abstract

During this study, benzo-15-crown-5 was synthesised as sodium cation scavenging ligand. This crown ether moiety was then functionalised to 4’-formylbenzo-15-crown-5 and 4’-(hydroxymethyl)benzo-15-crown-5. The first synthesis of ferrocyl isocyanate is reported. The reaction between this compound and 4’-(hydroxymethyl)benzo-15-crown-5 provided a novel new benzo-15-crown-5 / ferrocene conjugate that is linked by a urethane bond. Epichlorohydrin was polymerised to polyepichlorohydrin derivatives having molar masses of 2 000 and 20 000 g mol-1 following a cationic ring-opening process and utilising a BF3 / phenol initiator system. The chloro-containing alkyl side chains of polyepichlorohydrin were then re-functionalised to -N3, -NH2, -NCO and -OH functional groups. The reactivity of the -NH2, -NCO and -OH functional groups on these polymers was tested through various model reactions. These included anchoring of the carboxylic acid-containing ferrocene series, Fc-(CH2)nCOOH with n = 0 – 3, onto the amine-functionalised polymer under the influence of the coupling reagent O-benzotriazolyl-N,N,N’,N’-tetramethyluronium hexafluorophosphate. The four newly obtained polymer-bound ferrocene derivatives may have appreciable anticancer activity. Through the course of this study eleven hitherto unknown compounds were synthesised for the first time. These include three highly reactive polymeric derivatives of polyepichlorohydrin, five polymer-bound ferrocene derivatives, a polymer-bound phenyl derivative, ferrocyl isocyanate and a ferrocene-crown ether conjugate. Keywords: benzo-15-crown-5, alcohol, aldehyde, polyepichlorohydrin, azide, amine, isocyanate, hydroxy, ferrocene