Phosphorus‐Containing Dendrimers: Synthesis of Macromolecules with Multiple Tri‐ and Tetrafunctionalization

Abstract

AbstractA variety of dendrimers up to generation 7 possessing terminal P(S)Cl2, (3‐[G1]‐3‐[G7]) or P(O)Cl2, (7‐[G1]‐7‐[G3], 7‐[G3, 7‐[G7) have been tri‐ and tetrafunctionalized. Selective monosubstitution of P(X)Cl2 (X = S, 0) termini with allylamine or propargylamine gave the trifunctionalized dendrimers 5‐[G1], 5‐[G7], 8‐[G1], 8‐[G3], 10[G1], 11‐[G4], ll‐[G4], 12‐[G1]‐12‐[G3], 12‐[G5], and 12‐[G7]. Reaction of dendrimers 4‐[G1] and 4‐[G4], possessing terminal P(S)[N‐allyl) fragments, with propargylamine afforded trifunctionalized dendrimers l4‐[G1 and l4‐[G4]. Multiply trifunctionalized macromolecules 13‐[G2] and 13‐[G3] with P(S)(NH‐allyl)(NH‐propargyl) moieties at the surface were prepared by treatment of 8‐[G2] and 8‐[G3] with propargylamine. Dendrimers 15‐[G1]‐l5‐[G3] and l6‐[G1]‐l6‐[G3] with P(O)(NH‐allyl)(OC6H4CHO) and P(O)(NH‐propargyl)(OC6H4CHO) termini were also synthesized. Reaction of hydrazine or cyanomethylenetriphenylphosphorane (17) with compounds 15‐[G1], 15‐[G3], and 16‐[G1]‐16‐[G3] led to the multiply tetrafunctionalized dendrimers 18‐[G1], 18‐[G3], 19‐[G1], 20‐[G1]‐20‐[G3], 21‐[G1], and 21‐[G2].