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A non‐enzymatic model based on an acyl transfer reaction for the formation of energy‐rich acetyl phosphate in organic solvents and in a biphasic system
Author(s) -
Giusti Luciano A.,
Machado Vanderlei G.
Publication year - 2010
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/poc.1645
Subject(s) - chemistry , nucleophile , hydrolysis , phosphate , solvent , medicinal chemistry , acetonitrile , catalysis , salt (chemistry) , trimethyl phosphate , base (topology) , organic chemistry , mathematical analysis , mathematics
Abstract The formation of acetyl phosphate (AcP), an energy‐rich phosphate compound, was studied through the reaction of 2,4‐dinitrophenyl acetate with H 2 PO 4 −solubilized with Kryptofix® 222 or as a tetra‐ n ‐butylammonium (( n ‐C 4 H 9 ) 4 N + ) salt in organic media. The results indicated that the rate of the reaction in acetonitrile is strongly inhibited by the addition of water, suggesting that the water added to the medium preferentially solvates the H 2 PO 4 −anion, inhibiting its action as a nucleophile and allowing it to act as a general base catalyst, which leads to the hydrolysis of the ester. The utilization of various organic solvents in the acetyl transfer process demonstrated that the specific interaction of the solvent with water accelerates the process, by desolvation of H 2 PO 4 − , which can act as a nucleophile. Finally, a formation/transformation cycle of AcP was studied in a biphasic system (water/CH 2 Cl 2 ) using Kryptofix® 222 and ( n ‐C 4 H 9 ) 4 N + BF 4 −as both the carrier and solubilizing agent for KH 2 PO 4 . Copyright © 2010 John Wiley & Sons, Ltd.