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

Abstract

Abstract A variety of dendrimers up to generation 7 possessing terminal P(S)Cl 2 , (3‐[G 1 ]‐3‐[G 7 ]) or P(O)Cl 2 , (7‐[G 1 ]‐7‐[G 3 ], 7‐[G 3 , 7‐[G 7 ) have been tri‐ and tetrafunctionalized. Selective monosubstitution of P(X)Cl 2 (X = S, 0) termini with allylamine or propargylamine gave the trifunctionalized dendrimers 5‐[G 1 ], 5‐[G 7 ], 8‐[G 1 ], 8‐[G 3 ], 10[G 1 ], 11‐[G 4 ], ll‐[G 4 ], 12‐[G 1 ]‐12‐[G 3 ], 12‐[G 5 ], and 12‐[G 7 ]. Reaction of dendrimers 4‐[G 1 ] and 4‐[G 4 ], possessing terminal P(S)[N‐allyl) fragments, with propargylamine afforded trifunctionalized dendrimers l4‐[G 1 and l4‐[G 4 ]. Multiply trifunctionalized macromolecules 13‐[G 2 ] and 13‐[G 3 ] with P(S)(NH‐allyl)(NH‐propargyl) moieties at the surface were prepared by treatment of 8‐[G 2 ] and 8‐[G 3 ] with propargylamine. Dendrimers 15‐[G 1 ]‐l5‐[G 3 ] and l6‐[G 1 ]‐l6‐[G 3 ] with P(O)(NH‐allyl)(OC 6 H 4 CHO) and P(O)(NH‐propargyl)(OC 6 H 4 CHO) termini were also synthesized. Reaction of hydrazine or cyanomethylenetriphenylphosphorane (17) with compounds 15‐[G 1 ], 15‐[G 3 ], and 16‐[G 1 ]‐16‐[G 3 ] led to the multiply tetrafunctionalized dendrimers 18‐[G 1 ], 18‐[G 3 ], 19‐[G 1 ], 20‐[G 1 ]‐20‐[G 3 ], 21‐[G 1 ], and 21‐[G 2 ].