Mechanistic insights into the amidolysis of a phosphate triester: the antagonistic role of water

The breakdown of O , O -diethyl-2,4-dinitrophenyl phosphate in formamide (FMD) solutions is assessed using kinetic studies and 31 P nuclear magnetic resonance (NMR) analysis. Regiospecific nucleophilic amidolysis via P-O bond cleavage is observed, leading to non-toxic diester and FMD regeneration. I...

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Bibliographic Details
Published in:Organic & biomolecular chemistry 2022-03, Vol.2 (12), p.2462-2466
Main Authors: Jacobs, Amanda K, Menezes, Leociley R. A, Fernandes, Juliano M, Kosteczka, Guilherme L, Sassaki, Guilherme L, Campos, Renan B
Format: Article
Language:English
Subjects:
Breakdown
Hydrogen bonding
Kinetics
Magnetic Resonance Spectroscopy
NMR
Nuclear magnetic resonance
Organophosphates - chemistry
Phosphates - chemistry
Reaction intermediates
Systems analysis
Water - chemistry
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Summary:The breakdown of O , O -diethyl-2,4-dinitrophenyl phosphate in formamide (FMD) solutions is assessed using kinetic studies and 31 P nuclear magnetic resonance (NMR) analysis. Regiospecific nucleophilic amidolysis via P-O bond cleavage is observed, leading to non-toxic diester and FMD regeneration. In the systems evaluated, water plays an antagonistic role: while it is key for the breakdown of the reaction intermediate, it inhibits the nucleophilic activity of FMD by hydrogen bonding effects. Aqueous formamide solutions can promote catalytic amidolysis of an activated organophosphate in a regiospecific process.
ISSN:1477-0520
1477-0539
DOI:10.1039/d2ob00180b