69322-63-0Relevant academic research and scientific papers
Small-molecule cyclic models for the synthesis of new polyphosphazenes: Side-group construction via lithiophenoxy derivatives
Allcock,Evans,Fuller
, p. 1026 - 1030 (1980)
Hexakis(p-lithiophen oxy)cyclotriphosphazene, [NP(OC6H4Li-p)2]3 (IV), has been synthesized as an intermediate for the covalent attachment of metallo, phosphino, carboxylato, alkyl, or tertiary alcohol units to the side-group structure. These reactions are models for the preparation of the corresponding phosphazene high polymers. Intermediate IV was prepared by the metal-halogen exchange reaction between [NP(OC6H4Br-p)2]3 (III) or [NP(OC6H4I-p)2]3 and n-butyllithium in tetrahydrofuran at -40 to -60°C. The subsequent interaction of IV with deuterium oxide, diphenylchlorophosphine, carbon dioxide, butyl bromide, benzophenone, triphenyltin chloride, or (triphenylphosphine)gold(I) chloride yielded the para-substituted derivatives [NP(OC6H4D)2]3 (VII), [NP(OC6H4P(C6H5)2) 2]3 (VIII), [NP(OC6H4COOH)2]3 (IX), [NP(OC6H4C4H9)2] 3 (X), [NP(OC6H4C(OH)(C6H5) 2)2]3 (XI), [NP(OC6H4Sn(C6H5)3) 2]3 (XII), and [NP(OC6H4AuP(C6H5)3) 2]3 (XIII), respectively. Compounds VII-XIII cannot be obtained readily by other synthetic routes. For example, the reaction of III with NaP(C6H5)2 is a less efficient route to the preparation of VIII. Compound VIII is a model coordination carrier species for transition-metal catalysts. The possible extension of these reactions to linear phosphazene high polymers is discussed.
