Synthetic Methods Studies On Ferrocenylketimines And Synthesis Of Tertiary Ferrocenylamines

This paper describes the optimized reaction conditions for the condensation reactions of acetylferrocene and a variety of anilines (p-methoxyanilines, p-methylaniline, aniline, p-chloroaniline, m-chloroaniline). Experimental results demonstrate that these reactions as mentioned above give normally the highest yields of products under the following conditions: TiCl₄ / Substartes mole ratio(FcCOCH₃:Aniline = 4:1) / Toluene/10h.The reactions of benzoylferrocene and three substituted benzylamines in toluene resulted in ferrocenylaldimines {(η⁵-C₅H₅)Fe(η⁵-C₅H₄C(C₆H₅)=N CH₂C₆H₄R), (R=4-OCH₃(a),4-CH₃(b),H(c)) in moderate yields. Reductions of these imines as mentioned before with lithium aluminum hydride in THF produced the corresponding secondary ferrocenylamines {(η⁵-C₅H₅)Fe(η⁵-C₅H₄CH(C₆H₅)NH CH₂C₆H₄R), (R=4-OCH₃(a),4-CH₃(b),H(c)). Reductive methylations of these secondary ferrocenylamines with aqueous formaldehyde, sodium cyanoborohydride and acetic acid afford the corresponding tertiary ferrocenylamines [(η⁵-C₅H₅)Fe(η⁵-C₅H₄CH(C₆H₅)-N(CH₃)CH₂C₆H₄-R)], (R=4-MeO(a), 4-Me(b), H(c)), respectively. All of these nine compounds were characterized by elemental analysis, IR and 1H NMR.