Synthesis of New Phosphazene High Molecular Weight Polymers Containing Functionalized and Optically Active Spirocyclic Groups

The polymer [NPCl 2 ] n reacts with the functionalized biphenols bis(2-hydroxy-5-chlorophenyl)methane [(HOC 6 H 3 Cl) 2 CH 2 ], bis(2-hydroxyphenyl) ketone [(HOC 6 H 4 ) 2 CO], and [racemic(±)]-, [ R (+)]-, or [ S (−)]-1,1‘-binaphthyl-2-ol [(HOC 10 H 6 C 10 H 6 OH)] (binaphthol), in THF, or 1,4-dioxane in the presence of K 2 CO 3 or Cs 2 CO 3 to give respectively the spirocyclic phosphazene homopolymers [NP(O 2 C 13 H 8 Cl 2 )] n ( 1 ), [NP(O 3 C 13 H 8 )] n ( 2 ), (±)-[NP(O 2 C 20 H 12 )] n ( 5 ), (−)-[NP(O 2 C 20 H 12 )] n [(−)- 5b ], and (+)-[NP(O 2 C 20 H 12 )] n [(+)- 5b ], some of them also obtained as blends with poly(tetrahydrofuran). The reaction of [NPCl 2 ] n first with (HOC 6 H 3 Cl) 2 CH 2 or (HOC 6 H 4 ) 2 CO and subsequently with 2,2‘-biphenol ((HO)C 6 H 4 C 6 H 4 (OH)) in THF and in the presence of K 2 CO 3 gave the random mixed copolymers [NP(O 2 C 12 H 8 ) 0.6 (O 2 C 13 H 8 Cl 2 ) 0.4 ] n ( 3 ) and [NP(O 2 C 12 H 8 ) 0.6 (O 3 C 13 H 8 ) 0.4 ] n ( 4 ). For comparison with the polymers, the two cyclic enantiomers (+)-[N 3 P 3 (O 2 C 20 H 12 ) 3 ] [(+)- 6 ] and (−)-[N 3 P 3 (O 2 C 20 H 12 ) 3 ] [(−)- 6 ] have been prepared from [N 3 P 3 Cl 6 ] and [ S (−)]- or [ R (+)]-binaphthol, respectively, in acetone in the presence of Cs 2 CO 3 .