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Monatshefte für Chemie / Chemical Monthly

, Volume 128, Issue 11, pp 1173–1180 | Cite as

The phosphonate-phosphate and phosphate-phosphonate rearrangement and their applications V. On the reaction ofs-butyllithium/TMEDA with symmetrical trialkyl phosphates

  • F. Hammerschmidt
  • S. Schmidt
Organische Chemie Und Biochemie

Summary

1-(Tributylstannyl)hexanol ((±)-8 is phosphorylated to give phosphate (±)-9 which is then transmetallated. The organolithium intermediate (±)-10 isomerizes to α-hydroxyphosphonate (±)-12. Similar intermediates are also formed upon direct deprotonation of triethyl, tri-n-propyl, and tri-n-butyl phosphate, which subsequently rearrange to α-hydroxyphosphonates (±)-14a–c.

Keywords

α-Hydroxyphosphonates Phosphates Phosphate-phosphonate rearrangement s-BuLi/TMEDA 

Die Phosphat-Phosphonat- und Phosphonat-Phosphat-Umlagerung und ihre Anwendungen, 5. Mitt. Über die Reaktion vons-Butyllithium/TMEDA mit symmetrischen Trialkylphosphaten

Zusammenfassung

1-(Tributylstanny)hexanol ((±)-8) wird phosphoryliert und liefert Phosphat (±)-9, das transmetalliert wird. Das lithiumorganische Zwischenprodukt (±)-10 isomerisiert zum α-Hydroxyphosphonat (±)-12. Ähnliche Intermediate werden auch bei der direkten Deprotonierung von Triethyl-, Tri-n-propyl- und Tri-n-butylphosphat gebildet, die anschließend zu den α-Hydroxy-phosphonaten (±)-14a–c umlagern.

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Copyright information

© Springer-Verlag 1997

Authors and Affiliations

  • F. Hammerschmidt
    • 1
  • S. Schmidt
    • 1
  1. 1.Institut für Organische ChemieUniversität WienWienAustria

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