An exceptionally reactive phosphotriester

Cyclodextrin-Mediated Hydrolyses of Novel Phosphotriesters

“…We have noted that PNPNP is ideally constructed for nucleophilic displacement: The 1,8-naphthalenedioxy unit is "tied back," so that nucleophile access to PNPNP at P is less hindered than for PNPDPP with its 2 "floppy" phenoxy groups. 6 Additionally, there will be no phenyl/phenyl nonbonded interactions in the trigonal bipyramidal transition state (or short-lived intermediate) 18 derived from OHand PNPNP, in contrast to PNPDPP, where such interactions will be present and energetically costly. 19 The composite result is a reactivity advantage of ∼130 for PNPNP over PNPDPP.…”

“…[2][3][4][5] Recently, we described p-nitrophenyl 1,8-naphthyl phosphate (2, PNPNP), an analogue of PNPDPP, in which "fusion" of the phenyl residues of 1 into the naphthyl moiety of 2 led to substantial reactivity enhancements with many of the nucleophiles deployed in phosphorolytic reactions. 6 PNPNP is thus a very sensitive nerve agent simulant. Similarly, we have prepared p-nitrophenyl biphenyl phosphate (3, PNPBPP) by the reaction of 2,2′biphenol with p-nitrophenyl phosphorodichloridate in the presence of triethylamine.…”

“…Recently, we described p -nitrophenyl 1,8-naphthyl phosphate ( 2 , PNPNP), an analogue of PNPDPP, in which “fusion” of the phenyl residues of 1 into the naphthyl moiety of 2 led to substantial reactivity enhancements with many of the nucleophiles deployed in phosphorolytic reactions . PNPNP is thus a very sensitive nerve agent simulant.…”

Micellar Effects on Hypochlorite Catalyzed Decontamination of Toxic Phosphorus Esters

“…The substrates p -nitrophenyl diphenyl phosphate (PNPDPP; 1 ) and p -nitrophenyl isopropyl methylphosphonate (PNPIMP; 2 ) were selected because large amounts of kinetic data are available on PNPDPP substrate for comparison and because PNPIMP is a closer analogue of sarin, with almost equal toxicity. Simulants may provide useful information on the relative reactivity of decontaminants, but corroboration of simulant results with data on the actual target compound is essential 5b.…”

Rapid phosphorus triester hydrolysis catalyzed by bimetallic tetrabenzimidazole complexes

“…PNPDPP has become the unofficial standard simulant for phosphorus triester hydrolysis reactions. 12,13 Its extensive use allows for straightforward comparison of kinetic data obtained with many different catalysts under widely varying reaction conditions. The kinetic studies were conducted by monitoring the formation of the p-nitrophenolate anion (at 401 nm) using UVvisible spectrometry for greater than 4 half-lives.…”