63507-05-1Relevant articles and documents
Synthesis and characterisation of severely hindered P-OR compounds
Williams, D. Bradley G.,Netshiozwi, Takelani E.
experimental part, p. 9973 - 9982 (2010/02/27)
P-Cl substrates were converted into their P-OR analogues from hindered alcohols using an amine base. Where the system was severely hindered, more forcing conditions were required that necessitated the presence of a metal alkoxide nucleophile before succes
Quasiphosphonium Intermediates. Part 3. Preparation, Structure, and Reactivity of Alkoxyphosphonium Halides in the Reaction of Neopentyl Diphenylphosphinite, Dineopentyl Phenylphosphinite, and Trineopentyl Phosphite with Halogenomethanes and the Effect of Phenoxy-substituenst on the ...
Hudson, Harry R.,Kow, Aloysius,Roberts, John C.
, p. 1363 - 1368 (2007/10/02)
The reactions of neopenthyl diphenylphosphinite with chloro-, bromo-, or iodo-methane and of dineopentyl phenylphosphphonite with bromo- or iodo-methane yield crystalline alkoxyphosphonium halides.In deuteriochloroform these intermediates decompose by a first-order process which involves rate-determining collapse of the phosphonium halide ion-pair with SN2-type fission of the alkyl-oxygen bond.Rates for chloride, bromide, and iodide are similar.In a more ionising medium (deuterioacetonitrile) dissociation leads to stabilisation of the intermediates and to deviation from first-order decomposition.Previously determined X-ray diffraction data for the bromides, together with relative rates of decomposition in deuteriochloroform for intermediates in the series Phn(RO)3-nP+MeX- (n = 0,1, or 2) suggest that the stability and reactivity of alkoxyphosphonium intermediates are determined largely by inductive rather than mesomeric effects of ligands.The presence of phenoxy-substituents on phosphorus may cause a tendency towards SN1-type fission of the alkyl-oxygen bond in certain circumstances.
The Reactivity of Organophosphorus Compounds. Part 35. Pyrolysis of 3-Aryl- and 3-Alkyl-2,3-dihydro-1,3,2-benzoxazaphosph(V)oles
Cadogan, J. I. G.,Husband, James B.,McNab, Hamish
, p. 1489 - 1495 (2007/10/02)
Pyrolysis of 2,2-diphenyl-2-methoxy derivatives of the title compounds in the gas phase gives phosphinates or phosphinamidates derived from the substrate by formal loss of methylene.Control experiments show that the reaction involves radical cleavage initiated by rupture of the oxazaphosph(V)ole ring.Pyrolysis of 3-aryl-2,2-dimethoxy-2-phenyl derivatives of the title compounds under similar conditions results in the formation of 3-aryl-2,3-dihydro-2-oxo-2-phenyl-1,3,2-benzoxazaphospholes.No significant products could be isolated from 2,2,2-trimethoxy derivatives, though vigorous conditions were required for their complete breakdown.The pyrolysis of the corresponding 2,2-diphenyl-2-ethoxy, 2,2-diethoxy-2-phenyl, and 2,2,2-triethoxy compounds gave higher yields of similar products, possibly via a six-centre concerted elimination.
