PHOSPHORUS-CONTAINING DENDRIMERS - EASY ACCESS TO NEW MULTI-DIFUNCTIONALIZED MACROMOLECULES

Phosphorus-containing dendrimers 1-[G'(1)]-1-[G'(4)] (generation 1 to generation 4) possessing terminal aldehyde groups reacted with a varie ty of hydrazino compounds. Addition of hydrazine itself to 1-[G'(1)]-1 -[G(4)] afforded the corresponding dendrimers 2-[G(1)]-2-[G(4)] with h ydrazono groups at the periphery. Addition of methylhydrazine to 1-[G' (4)],1-[G'(4)] gave the dendrimers 3-[G(1)],3-[G(4)]. A Schiff reactio n between 1-G'(1)]-1[G'(4)] and 1-amino-4-(2-hydroxyethyl)piperazine l ed to dendrimers 5-[G(1)]-5-[G(4)] possessing up to 48 alcohol chain e nds. Treatment of 1-[G'(1)], 1-[G'(3)] with fluorenone hydrazone gave rise to macromolecules 7-[G(1)], 7-[G(3)] while the reaction of 1-[G'( 1)], 1-[G'(2)], 1-[G'(4)] with 4-aminobenzo-15-crown-5 afforded the ma cromolecules 9-[G(1)], 9-[G(2)], 9-[G(4)] in which up to 48 crown ethe r units are anchored on the surface. Wittig reactions between 1-[G'(1) ]-1-[G'(4) with (acetylmethylene)triphenylphosphorane (10) or (cyanome thylene)triphenylphosphorane (12) allowed the formation of dendrimers 11-[G(1)]-11-[G(4)] or 13-[G(1)], 13-[G(4)] with alpha,beta unsaturate d ketones or cinnamonitrile units, respectively, on the surface. Disub stitution of terminal P(S)Cl-2 groups of dendrimers 1-[G(1)]-1-[G(7)] with allylamine, propargylamine, or N-(trimethylsilyl)imidazole easily occurred to give macromolecules 14-[G(1)]-14-[G(7)], 15-[G(1)], 15-[G (4)], 16-[G(1)], 16-[G(4)].