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Unexpected stoichiometry in the cleavage of bis(4‐nitrophenyl) phosphate and 4‐nitrophenyl phosphorochloridate by alkaline hydrogen peroxide
Author(s) -
MejíaRadillo Yamilet,
Yatsimirsky Anatoly K.,
Foroudian Houshang J.,
Gillitt Nicholas D.,
Bunton Clifford A.
Publication year - 2000
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/1099-1395(200009)13:9<505::aid-poc277>3.0.co;2-n
Subject(s) - chemistry , hydrogen peroxide , nucleophile , intramolecular force , medicinal chemistry , stoichiometry , yield (engineering) , cleavage (geology) , peroxide , substrate (aquarium) , kinetics , phosphate , inorganic chemistry , organic chemistry , catalysis , materials science , oceanography , geotechnical engineering , physics , quantum mechanics , fracture (geology) , engineering , metallurgy , geology
Reaction of alkaline hydrogen peroxide with bis(4‐nitrophenyl) phosphate ion proceeds with simultaneous liberation of ca 2 equiv. of 4‐nitrophenol per mole of substrate, and no evidence for build‐up of an intermediate. Reaction of HO 2 − with the more activated 4‐nitrophenyl phosphorochloridate gives 4‐nitrophenol in up to 40% yield with simple first‐order kinetics and no indication of a long‐lived intermediate. A fast intramolecular nucleophilic displacement of 4‐nitrophenolate ion by peroxide in the initially formed 4‐nitrophenyl peroxophosphate is proposed to explain this behavior. Copyright © 2000 John Wiley & Sons, Ltd.