352 Devedjiev and Ganev
phosphate with the release of propylene glycol.
Acetyl phosphate reacts with ethanol to give ethyl
acetate as the final product. This stepwise interac-
tion may be accomplished in the presence of water
too. Experiments 11 and 12 show that the isolation of
ꢀ-hydroxypropyl acetate may be avoided by the in-
troduction of another alcohol which to be acety-
lated in the system. For this purpose, experiments
were carried out with other hydroxyl compounds.
Methanol, n-propanol, and n-butanol produced
methyl acetate, propyl acetate, and butyl acetate,
respectively. The reaction pattern of the formation
of ethyl acetate is observed in these cases. How-
ever, the attempt to synthesize phenyl acetate was
unsuccessful, leaving the added phenol unchanged.
This is an indirect evidence of the intermediate
participation of acetyl phosphate in the presented
scheme, as the nucleophile attack may proceed only
on the apically oriented substituents of the phospho-
ryl group. In the case of phenol, the reaction can-
not take place due to the steric requirements of the
benzene ring.
mixed with 29 g (34.4 mL, 0.5 mol) of propylene ox-
ide, at the initial temperature of 20◦C. During the
interaction of propylene oxide and phosphoric acid,
the temperature was gradually raised up to 40◦C for
1 h. The reflux condenser was then replaced by a
Vigreux rectification column and a condenser, and
the reaction mixture was heated to the appropriate
temperature for distillation of the respective acetate.
By this procedure, the following products were ob-
tained: methyl acetate 18 g, 81%; ethyl acetate 22 g,
84%; n-propyl acetate 24 g, 78%; n-butyl acetate 28 g,
80%.
REFERENCES
[1] Breslow, R, Chem Soc Rev 1972, 1, 553–561.
[2] (a) Lynen, F. Chem Ber 1940, 73, 367–375;
(b) Lipmann, F.; Tuttle, C. J Biol Chem 1944, 153,
571–582; (c) Benetley, R. J. J Am Chem Soc 1948, 70,
2183–2185; (d) Lipmann, F.; Stadtman, E. R. J Biol
Chem 1950, 185, 549–551; (e) Koshland, D. E. J Am
Chem Soc 1951, 73, 4103–4108; (f) Avison, A. W. D.
J Chem Soc 1955, 732–738.
[3] (a) Porter, R. W.; Modebe, M. O.; Stark, G. R.
J Biol Chem 1969, 244, 1846–1859; (b) Heyde,
E.; Nagabhushanian, A.; Morrison, J. F. Biochem
1973, 12, 4718–4726; (c) Whitesides, G. M.; Siegel,
M.; Garrett, P. J Org Chem 1975, 40, 2516–2519;
(d) Yamaguchi, K.; Kamimura, T.; Hata, T. J Am Chem
Soc 1980, 102(13), 4534–4536.
MATERIALS AND METHODS
All reagents and materials were commercial prod-
ucts of Fluka and were used without preliminary
treatment. NMR-spectrometer Bruker DRX-250, IR-
spectrometer “IFS 113v,” and gas chromatograph
Carlo Erba 4100 with HP-5 column were used.
[4] (a) Rios-Mercadillo, V. M.; Whitesides, G. M. J Am
Chem Soc 1979, 101, 5828–5829; (b) Whitesides,
G. M.; Wong, C.-H.; Pollak, A. Adv Chem Ser 1982,
185, 205–218.
[5] (a) Wong, C.-H.; Pollak, A.; McCurry, S. D.; Sue, M.
M.; Knowles, J. R.; (b) Whitesides, G. M. Methods
Enzymol 1982, 89, 108–121.
[6] Tzokov, S. B.; Devedjiev, I. T.; Bratovanova, E. K.;
Petkov, D. D. Angew Chem, Int Ed Engl 1994, 33,
2302–2303.
[7] Tzokov, S. B.; Devedjiev, I. T.; Petkov, D. D. J Org Chem
1996, 61, 12–13.
[8] Devedjiev, I. T.; Petrova, K.; Glavchev, I. Synth Com-
mun 2000, 30(24), 4411–4415.
EXPERIMENTAL
General Method of Preparation of Esters
A flask, equipped with a magnetic stirrer and a re-
flux condenser, was filled with 11.53 g of 85% aque-
ous solution of phosphoric acid, 18 g (0.3 mol) of
acetic acid, 0.4 mol of the chosen alcohol (methanol,
ethanol, n-propanol, or n-butanol) and stepwise
Heteroatom Chemistry DOI 10.1002/hc