TY - JOUR
T1 - The deep oxidation of chemical warfare agent models
T2 - Facile catalytic oxidative cleavage of phosphorus-carbon and sulfur-carbon bonds using dioxygen
AU - Hogan, Terrence
AU - Simpson, Robert
AU - Lin, Minren
AU - Sen, Ayusman
PY - 1997
Y1 - 1997
N2 - In water metallic palladium on carbon was found to catalyze the deep oxidation of organophosphorus and organosulfur compounds by dioxygen at 90°C in the presence of carbon monoxide. This sysytem presents the first examples of catalytic cleavage of phosphorus-carbon bonds. Starting with trimethylphosphine oxide, the phosphorus-containing products of formed by sequeential C Cleavage were dimethylphosphine acid, methylphosphonic acid, and phosphoric acid. A similar reaction sequence was also observed for triethylphosphine oxide, except that products formed by partial oxidation of the ethyl groups, such as phosphonoacetic acid, were also seen as intermediates. The deep oxidation of dimethyl sulfides proceeded through the intermediacy of the corresponding sulfoxides. For the methyl derivatives, the ease of oxidation decresed in the order: (CH3)2S >CH3)2SO > (CH3)SO2 and is consistent with the system acting as an electrophilic oxidant.
AB - In water metallic palladium on carbon was found to catalyze the deep oxidation of organophosphorus and organosulfur compounds by dioxygen at 90°C in the presence of carbon monoxide. This sysytem presents the first examples of catalytic cleavage of phosphorus-carbon bonds. Starting with trimethylphosphine oxide, the phosphorus-containing products of formed by sequeential C Cleavage were dimethylphosphine acid, methylphosphonic acid, and phosphoric acid. A similar reaction sequence was also observed for triethylphosphine oxide, except that products formed by partial oxidation of the ethyl groups, such as phosphonoacetic acid, were also seen as intermediates. The deep oxidation of dimethyl sulfides proceeded through the intermediacy of the corresponding sulfoxides. For the methyl derivatives, the ease of oxidation decresed in the order: (CH3)2S >CH3)2SO > (CH3)SO2 and is consistent with the system acting as an electrophilic oxidant.
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U2 - 10.1023/a:1019088818029
DO - 10.1023/a:1019088818029
M3 - Article
AN - SCOPUS:0002477014
SN - 1011-372X
VL - 49
SP - 59
EP - 63
JO - Catalysis Letters
JF - Catalysis Letters
IS - 1-2
ER -