Fragmentation of a phenylphosphonamidic acid as a new technique for the generation of phenyl dioxophosphorane

Article abstract of DOI:10.1080/10426509608037956

N-(1-Adamantyl) phenylphosphonamidic acid (3), an easily prepared solid, on heating in toluene or 1,2-dichloroethane gave the crystalline adamantylamine salt of the anhydride PhP(O)(NHAd)-O-PPh(O)(OH). The mechanism is proposed to involve first the fragmentation of 3 to form phenyl dioxophosphorane, PhPO₂, which then acts as a phosphorylating agent to unreacted 3. This mechanism was supported by the observation of first-order kinetics for the consumption of 3. When the phosphonamidic acid was fragmented in the presence of an alcohol, the intermediate PhPO₂ was trapped as the monoalkyl phenylphosphonate. The OH groups on the surface of silica gel were also phosphonylated by PhPO₂. The acidic OH group of a phosphoric acid monoester (thymyl phosphate) was phosphonylated to give Thy-O-P(O)(OH)-O-PPh(O)(OH). It is concluded from this study that N-(1-adamantyl) phenylphosphonamidic acid is a useful precursor of phenyl dioxophosphorane, which can perform valuable phosphonylation operations.

Full text of DOI:10.1080/10426509608037956

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Phosphorus, Sulfur, and Silicon and
the Related Elements
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FRAGMENTATION OF A
PHENYLPHOSPHONAMIDIC ACID
AS A NEW TECHNIQUE FOR
THE GENERATION OF PHENYL
DIOXOPHOSPHORANE
Gyöngyi Szakal Quin a , Stefan Jankowski a b & Louis D. Quin a
a Department of Chemistry , University of Massachusetts , Box
34510, Amherst, MA, 01003-4510, USA
b Chemistry Department , Technical University of Lodz
Published online: 24 Sep 2006.
To cite this article: Gyöngyi Szakal Quin , Stefan Jankowski & Louis D. Quin (1996)
FRAGMENTATION OF A PHENYLPHOSPHONAMIDIC ACID AS A NEW TECHNIQUE FOR THE GENERATION
OF PHENYL DIOXOPHOSPHORANE, Phosphorus, Sulfur, and Silicon and the Related Elements, 115:1,
93-98, DOI: 10.1080/10426509608037956
To link to this article: http://dx.doi.org/10.1080/10426509608037956
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