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Structure and Mechanism of Hydrolysis of the Product of Reaction of Phosphorus Pentoxide and Ethyl Ether

Abstract

THE product of reaction of phosphorus pentoxide and ethyl ether which has the composition of a metaphosphate ester [PO3(C2H5)]n has been the subject of recent discussion. Rätz and Thilö1 have shown that the product of hydrolysis of this ester could result from the splitting of a mixture of the two following compounds: However, the nuclear magnetic resonance spectrum obtained by Van Wazer2 on the crude compound shows the presence of three peaks, the chemical shifts of which are characteristics of terminal (t), middle (m) and branched (b) phosphorus atoms, but in the proportions Pt = 25 per cent, Pm = 72 per cent, Pb = 3 per cent. The inequality of Pb and Pt seemed to rule out the proposed structure.

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References

  1. Rätz, R., and Thilö, E., Ann. Ber. Chem., 272, 173 (1951).

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  2. Van Wazer, J., Callis, C. F., Shoolery, J. N., and Jones, R. C., J. Amer. Chem. Soc., 74, 5715 (1956).

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  3. Schramm, G., and Wissmann, H., Chem. Ber., 91, 1073 (1955). Schramm, G., Grötsch, H., and Pollmann, W., Angew. Chem. Intern. Ed., 1, 1 (1962).

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  4. Pollmann, W. (private communication).

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WEILL, G., KLEIN, M. & CALVIN, M. Structure and Mechanism of Hydrolysis of the Product of Reaction of Phosphorus Pentoxide and Ethyl Ether. Nature 200, 1005–1006 (1963). https://doi.org/10.1038/2001005a0

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