A reinvestigation of the reactions of enolate anions with cyclotriphosphazenes

Synthesis and Spectroscopy of N3P3X5OCHCH2(X = Cl, F, OCH3, OCH2CF3, N(CH3)2) and N3P3X4(OCHCH2)2(X = Cl, N(CH3)2). Correlations of Ultraviolet Photoelectron Spectroscopy and Nuclear Magnetic Resonance Data to Electronic and Geometrical Structure

“…These fractions were combined to give 2.44 g (11.2% of theory) of a colorless liquid, bp (68−72 °C). This compound has been previously prepared using a different method and was identified from the reported 1 H and 31 P NMR data. , …”

“…The reactions of enolate anions with halocyclophosphazenes lead to a wide range of vinyloxycyclophosphazenes. − We have explored the reactions of the simplest of these species, i.e., the enolate of acetaldehyde, in detail and reported the synthesis of the following derivatives: N 3 P 3 Cl 6 - n (OCHCH 2 ) n ( n = 1−6), ,, N 3 P 3 F 6 - n (OCHCH 2 ) n ( n = 1−5), and N 4 P 4 Cl 8 - n (OCHCH 2 ) 2 ( n = 1, 2) . Our interest in these materials has been focused on two areas: new organofunctional phosphazene monomers that can be converted to carbon chain polymers with cyclophosphazenes as substituents , and questions involving regio- and stereochemical control in the substitution reactions of cyclophosphazenes .…”

(Vinyloxy)chlorocyclotriphosphazenes

“…Recently, we have shown that the ambident enolate anions undergo reactions with the hexahalocyctriphosphazenes, N3P3X 6 (X -F,Cl), to yield the vinyloxypentahalocyclotriphosphenes, N 3 P 3 X 5 OCR-CH 2 . 8 The favorable combination of the hard acid (phosphorus (V)) with the hard base (oxygen) leads to exclusive attack at the oxygen end of the enolate anion and thus provides a route to previously inaccessible vinyl alcohol derivatives. In this paper, we present the synthesis and characterization of the series of vinyloxychlorocyclotriphosphazenes, N 3 P 3 C 6 -n(OCH=CH 2 ) n (n -1-6).…”

Transsilylation reactions of phosphazene precursors

“…The reactions of A-(trimethylsilyl)-/',/'-dimethyl-/'-(trifluoroethoxy)phosphoranimine (1) with various mono-and dichlorosilanes and some dichlorosiloxanes were studied in this work. Research in other laboratories5 has shown that triorgano-substituted (V-silylphosphoranimines such as Me3SiN=PMe3 undergo a variety of transsilylation reactions.…”

“…The iV-silyl-/'-(trifluoroethoxy)phosphoranimines such as Me3SiN=P(OCH2CF3)Me2 (1) are useful precursors to poly-(alkyl/arylphosphazenes) via a thermally induced condensation polymerization process.2 Aside from this important thermolysis reaction, however, the chemistry of these phosphazene precursors has not been studied in a systematic fashion. At least two major areas probably merit attention in this context:…”