Synthesis, structure, and hydrolysis of esters of strained and unstrained N-phosphonylureas

Ronald Kluger, Gregory R.J. Thatcher, William C. Stallings

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8 Scopus citations


Compounds 1-5 were prepared to compare reactivity patterns of cyclic and acyclic phosphonylurea esters. The rates and products of reactions of phosphonylurea esters (1-3) with hydroxide in aqueous acetonitrile were analyzed. In these compounds the phosphonate moiety is in a strained five-membered ring, which also contains the ureido group. Structural determination of 1 by X-ray crystallography indicates that the five-membered ring is planar and the internal ring angle at phosphorus is 93.1°. The endocyclic N-C-N angle of the ureido group is 111°. The compounds undergo hydrolysis in alkaline aqueous acetonitrile at 35°C with a rate about 106 times that of analogues (4, 5) in which the phosphonate group is exocyclic to the ureido ring. Compound 1 undergoes alkaline hydrolysis (k = 9.0 × 103 M-1 s-1) to release the phenoxy group to give 6. The hydrolysis of alkyl esters 2 (k = 2.4 × 104M-1 s-1) and 3(k = 1.3 × 103 M-1 s-1) leads to cleavage of the endocyclic P-N bond, producing 7 and 8 respectively. The exocyclic alkyl esters (4 and 5) also cleave at the P-N bond with respective rate constants of 6.5 × 10-3 M-1 s-1 and 4.4 × 10-2 M-1 s-1. The data are consistent with a mechanism in which hydroxide adds to 1 to form a pentacoordinate phosphorus intermediate with the phenoxy group in an equatorial position and the ureido ring in apical and equatorial positions (with nitrogen apical). The departure of the urea group is slower than pseudorotation of the intermediate and expulsion of phenoxide. In the isomerized intermediate, phenoxy is apical but the methylene group of the ring, which has low apicophilicity, must also be apical. Reactions of 2 and 3, which have more basic oxygen leaving groups, occur with P-N cleavage because expulsion from the isomerized intermediate in those cases is not sufficiently fast. These results fit reaction patterns at phosphorus that are determined by ring strain and electronegativity of ligands. Contributions from effects due to antiperiplanar interactions between bonding and nonbonding electrons are not detected.

Original languageEnglish (US)
Pages (from-to)1838-1844
Number of pages7
JournalCanadian Journal of Chemistry
Issue number8
StatePublished - Aug 1 1987
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry


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