A novel method for the synthesis of acetyl phosphate

Article abstract of DOI:10.1080/10426500500536598

A facile method for the synthesis of acetyl phosphate by a reaction of 2-hydroxypropylphosphate with acetic acid is described. Copyright Taylor & Francis Group, LLC.

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Phosphorus, Sulfur, and Silicon
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A Novel Method for the
Synthesis of Acetyl Phosphate
a
Ivan T. Devedjiev
a
Institute of Polymers, Bulgarian Academy of
Sciences, Sofia, Bulgaria
Version of record first published: 01 Feb 2007.
To cite this article: Ivan T. Devedjiev (2006): A Novel Method for the Synthesis of
Acetyl Phosphate, Phosphorus, Sulfur, and Silicon and the Related Elements, 181:8,
1785-1787
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Phosphorus, Sulfur, and Silicon, 181:1785–1787, 2006
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500500536598
A Novel Method for the Synthesis of Acetyl Phosphate
Ivan T. Devedjiev
Institute of Polymers, Bulgarian Academy of Sciences, Sofia, Bulgaria
A facile method for the synthesis of acetyl phosphate by a reaction of 2-
hydroxypropylphosphate with acetic acid is described.
Keywords Acetyl phosphate; 2-hydroxypropyl phosphate; propylene oxide
INTRODUCTION
Many enzyme-catalyzed reactions consume adenosine triphosphate,
1
,2
which is regenerated by Acetyl Phosphate (AcP). Various methods
for the synthesis of AcP are known.3
–11
To obtain AcP, the acetylation
of phosphoric acid or its potassium salts with acetic anhydride is most
frequently used.
RESULTS
Now, I would like to report the preparation of AcP by the use of 2-
Hydroxypropyl Phosphate (2-HPP) as the starting reagent. The vicinal
hydroxy esters of phosphoric acid are known to hydrolyze in an acid
12
medium with phosphoryl group migration. A mechanism character-
1
3
ized by the release of the respective diol has been proposed. 2-hydroxy
esters of oxophosphoric acid have been used in the phosphorylation of
glucose, deoxynucleosides,1
4,15
and glycine.
16
The reported preparation of AcP is performed without the use of any
solvent and proceeds in two stages—the formation of 2-HPP and the
reaction of the latter with acetic acid, according to Scheme 1.
Received September 19, 2005; accepted November 8, 2005.
I would like to thank Professor Octavian Barzu from the Pasteur Institute, Paris, for
performing the enzyme analysis.
I gratefully acknowledge the financial support of the National Fund for Scientific
Studies at the Ministry of Education and Science, Bulgaria–Grant X-1309/2003.
Address correspondence to Ivan T. Devedjiev, Institute of Polymers, Bulgarian
Academy of Sciences, Acad. G. Bonchev Str., Building 103-A, Sofia, 1113 Bulgaria.
E-mail: idev@polymer.bas.bg
1785

1
786
I. T. Devedjiev
SCHEME 1
The removal of excess propylene glycol is necessary to avoid a further
reaction with AcP, leading to the formation of 2-hydroxypropyl acetate,
according to Scheme 2, which has been proved by gas-chromatography
with a standard compound. The acetyl phosphate thus produced may
be directly used or stored by a transformation into its dilithium salt.
SCHEME 2
EXPERIMENTAL
Acetyl Phosphate
One mole of H3PO4 (anhydrous) was treated with 1.3 mol of 1,2-
◦
propylene oxide. As the reaction was exothermic, a temperature of 20 C
was maintained by the use of a water bath. To the resulting oily prod-
uct one mole of AcOH was added. The characteristic smell of AcOH
disappeared in about 15–20 min. The formation of AcP in the reaction
1
mixture was monitored by H NMR spectroscopy in DMSO. Immedi-
ately after the addition of acetic acid to 2-HPP, the NMR spectrum of
the reaction mixture exhibited the signal at 1.91 for the CH3 group of
AcOH. This signal disappeared, and a dublet at 1.94 with JH,P 1.7 Hz
was observed instead 20 min after mixing. The latter signal was as-
signed to the methyl protons in AcP. The transformation was quanti-
tative. The oily product thus obtained was washed with diethyl ether
to eliminate propylene glycol and was stored in the presence of P2O5
under reduced pressure. Gas-chromatography: Carlo Erba 4100, HP-5
column, 25 m × 0.32 mm × 0.52 µm film thickness.
1
H-NMR (DMSO, Bruker DRX-250): δ 1.84 d, 3H, JH,P 1.7 Hz,
CH3C(O); C-HMR: δ 172.7 CH3C(O); 31P-NMR (101.26 MHz): δ 7.2;
IR (Bruker IFS 113v, in layer) (P=O) 1271 cm , (C=O) 1754 cm .
1
3
−
1
−1

A Novel Method for the Synthesis of Acetyl Phosphate
1787
Dilithium Acetyl Phosphate
The AcP was dissolved in a 1:1 ice:water medium and was potentiomet-
rically titrated with 1N LiOH. Intensive hydrolysis with pH 2.6 was
observed. Titration went up to pH 8.6. About 25% of the AcP was lost
in hydrolysis, as calculated by comparing the amount of phosphoric
acid used in the reaction and the equivalents of LiOH used in titra-
tion. The deposit formed during titration were discarded, and the fil-
trate was added to an equal volume of EtOH. After cooling, dilithium
acetyl phosphate crystallized. It was separated by filtration, washed
with ethanol and diethyl ether, and vacuum-dried. An enzyme analysis
of the dilithium salt thus prepared showed the presence of 60% pure
acetyl phosphate.
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