Abundant Intramolecular Ring Rearrangements of

1-(N-Benzyloxycarbonylamino)arylmethylphosphonate Phenyl

Monoesters under Electrospray Ionization Conditions

Xinyao Li, Jiaxi Xu*

State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry,

Faculty of Science, Beijing University of Chemical Technology, Beijing 100029, China

Email: jxxu@mail.buct.edu.cn, Fax: 86-10-64435565; Tel: 86-10-64435565

Abstract

The mass spectrometric behavior of 1-(N-benzyloxycarbonylamino)arylmethylphosphonate

phenyl monoesters was investigated under positive ion electrospray ionization conditions. All

nitrogen-protonated title compounds undergo four- and/or six-membered ring rearrangements to

yield nitrogen-containing fragment ions by consecutive or simultaneous loss of a carbon dioxide

and phenyl hydrogen phosphonate or phenyl benzyl phosphonate or an arylmethylimine. All

oxygen-protonated title compounds undergo four- to six-membered ring rearrangements to

produce fragment ions by loss of a carbon dioxide plus an arylmethylimine, or phenyl benzyl

phosphonate, by consecutive or simultaneous loss of benzyl phenyl ether and isocyanic acid.

The fragmentation is obviously different from the corresponding

1-(N-benzyloxycarbonylamino)arylmethylphosphonate methyl and ethyl monoesters, which show

a tendency to undergo intramolecular four-membered ring rearrangements only.