A polymeric amine–copper(II) complex as catalyst for the hydrolysis of 1,2,2‐trimethylpropyl methylphosphonofluoridate (soman) and bis (1‐methylethyl) phosphorofluoridate (DFP)

摘要

AbstractThe Cu (II) complex of poly‐4‐vinylpyridine, quaternized with 19 mol ethyl bromide and 36 mol 4‐chloromethyl‐4′‐methyl‐2,2′‐bipyridine, was examined as a catalyst for the hydrolysis of the toxic organophosphorous compounds bis (1‐methylethyl) phosphorofluoridate (1,Registry no.:1, 55‐91‐4;2, 96‐64‐0.DFP) and 1,2,2‐trimethylpropyl methylphosphonofluoridate (2,soman). Studies were carried out at 25.0 and 37.0°C for both substrates in MOPS buffer at pH 7.0. In the presence of 7.31 × 10−3Mcatalyst at 25.0°C, soman is hydrolyzed with a first‐order rate constant of 0.019 min−1(t1/2= 37.5 min), whereas DFP hydrolyzes with a rate constant of 0.011 min−1(t1/2= 63.8 min). For soman, this represents a 14‐fold increase over the uncatalyzed rate in the same buffer. Other studies examined the effect of a strongly sorptive polymeric resin on catalysis by this copper‐containing polymer and found a dramatic decrease in the hydrolysis rate of so