PHOSPHORUS-CONTAINING DENDRIMERS - SYNTHESIS OF MACROMOLECULES WITH MULTIPLE TRIFUNCTIONALIZATION AND TETRAFUNCTIONALIZATION

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(5)], 7-[G(7 )]) have been tri- and tetrafunctionalized. Selective monosubstitution of P(X)Cl-2 (X = S, O) 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(1)], 11-[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 t erminal P(S)[N-(ally(2))](Cl) fragments, with propargylamine afforded trifunctionalized dendrimers 14-[G(1)] and 14-[G(4)]. Multiply trifunc tionalized 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)]-15-[G(3) ] and 16-[G(1)]-16-[G(3)] with P(O)(NK-allyl)(OC6H4CHO) and P(O)(NH-pr opargyl)(OC6H4CHO) termini were also synthesized. Reaction of hydrazin e or cyanomethylenetriphenylphosphorane (17) with compounds 15-[G(1)] 15-[G(3)], and 16-[G(1)]-16-[G(3)] led to the multiply tetrafunctional ized dendrimers 18-[G(1)], 18-[G(3)], 19-[G(1)], 20-[G(1)]-20-[G(3)], 21-[G(1)], and 21-[G(2)].