SYNTHESIS AND SOME PROPERTIES OF 4-PHOSPHORYLATED DERIVATIVES
53
the solvent was removed in a vacuum, to the residue
was added 30 ml of water, the product was extracted
with diethyl ether (3×25 ml). The extract was dried
over MgSO4, the solvent was removed in vacuo, and
compound IVa, IVb was used without purification for
further transformations.
b. A solution of 0.01 mol of a compound VIIa,
VIIc–VIIg, IXb in 15 ml of anhydrous acetic acid
saturated with hydrogen bromide was kept for 24 h at
20–25°C. The solvent was then removed in vacuo, the
residue was treated with water, filtered, dried, and
analyzed without further purification. The compounds
Xa, Xc–Xg, XIb yield was 82–86%.
Diethyl 2-methyl(4-methylphenyl)-5-ethylthio-
1,3-oxazole-4-ylphosponates (Va, Vb). To a solution
of 0.01 mol of one of compound IVa, IVb in 30 ml of
anhydrous tetrahydrofuran was added 0.02 mol of
anhydrous potassium carbonate and 0.015 mol of ethyl
iodide. The mixture was stirred for 24 h at 20–25°C,
the precipitate was filtered off, the solvent was
removed in a vacuum, and compound Va, Vb was
purified by column chromatography (eluent dichloro-
methane:methanol, 95:5).
Mixed samples of compounds Xa, Xc–Xg, XIb
obtained by the methods a or b, did not show melting
1
point depression, and their IR and H NMR spectra
were identical.
{1-Acetamido-2-[(4-methylphenyl)sulfanyl]-2-oxo-
ethyl}phosphonic acid (XII). To a solution of
0.01 mol of the monosodium salt VIb in 10 ml of
water was added conc. hydrochloric acid to pH ~1–2.
The mixture was kept for 24 h at 5–10°C, the
precipitate was filtered off, dried, and then dispersed in
10 ml of dichloromethane. The mixture was boiled for
2 min, cooled, the precipitate was filtered off, dried in
a vacuum, and analyzed without further purification.
Sodium monoethyl 2-methyl(aryl)-5-ethyl(aryl)-
thio-1,3-oxazole-4-ylphosphonates (VIa–VIg, VIIa,
VIIb). To a solution of 0.01 mol of compound IIIa–
IIIg, Va, Vb in 30 ml of ethanol was added a solution
of 0.03 mol of sodium hydroxide in 50 ml of ethanol.
The mixture was stirred for 8 h at 20–25°C, the solvent
was removed in a vacuum, and compound VIa–VIg,
VIIa, VIIb) was used for further transformation
without purification.
REFERENCES
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Monoethyl 2-methyl(aryl)-5-ethyl(aryl)thio-1,3-
oxazol-4-ylphosphonates (VIIIa, VIIIc–VIIIg, IXb).
To a solution of 0.01 mol of a compound VIa, VIc–
VIg, VIIb in 15 ml of water was added conc.
hydrochloric acid to pH ~1–2, the mixture was kept for
12 h at 20–25°C, the precipitate was filtered off, dried,
and oxazole VIIIa, VIIIc–VIIIg, IXb was purified by
recrystallisation.
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2-Methyl(aryl)-5-ethyl(aryl) thio-1,3-oxazol-4-
ylphosphonic acids (Xa–Xg, XIa, XIb). a. A solution
of 0.01 mole of compound IIIa–IIIg, Va, Vb in 15 ml
of anhydrous acetic acid saturated with hydrogen
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was then removed in vacuo, the residue was treated
with water, filtered, dried, and analysed without further
purification.
5. Vinogradova, T.K., Kisilenko, A.A., and Drach, B.S.,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 1 2013
Kondratyuk
