New data on the malonic ester phosphorylation

Full text of DOI:10.1134/S1070363211100264

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 10, pp. 2198–2199. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © L.K. Sal’keeva, E.K. Taishibekova, M.T. Nurmaganbetova, E.V. Minaeva, A.K. Shibaeva, A.K. Sal’keeva, 2011, published in
Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 10, pp. 1746–1747.
LETTERS
TO THE EDITOR
New Data on the Malonic Ester Phosphorylation
L. K. Sal’keeva, E. K. Taishibekova, M. T. Nurmaganbetova,
E. V. Minaeva, A. K. Shibaeva, and A. K. Sal’keeva
Buketov Karaganda State University, ul. Universitetskaya 28, Karaganda 100028 Kazakhstan
e-mail: LSalkeeva@mail.ru
Received April 25, 2011
DOI: 10.1134/S1070363211100264
Phosphorylation reaction of malonic ester so
far attracts the researchers attention that is ob-
viously associated with a possibility of its wide
chemical modifications for the synthesis of compounds
with the practically useful properties. Previously
was shown [1] that the reaction of diethyl
bromomalonate with triethyl phosphite and the
reaction of diethyl chlorophosphate with sodium
malonic ester proceed to afford the C-phosphorylation
product.
(
C H OOC) CHBr + P(OC H )
2 5 2 2 5 3
O
(
C H OOC) CHP(OC H )
2
5
2
2 5 2
I
(
C H O) POCl + C H OOCCH=C(ONa)OC H
2 5 2 2 5 2 5
Later was shown [2] that the reaction of
chlorophosphate with sodium malonic ester occurs by
an O-phosphorylation scheme. The phosphorylation of
malonic ester with diethyl chlorophosphite in the
presence of triethylamine was shown to give a C-phos-
phorylation product, which was converted into diethyl
dicarboethoxymethylphosphonate I [3].
found to be essentially dependent on the methods of
reagents mixing and dilution. Thus, at the slow adding
bromomalonic ester to a benzene solution of diethyl
sodium phosphite the reaction proceeds by an
elimination scheme. A significant exothermic effect
was observed together with the NaBr precipitating.
After the precipitate separation, white crystals of the
compound II formed. Identification of the latter
showed that they are ethyl ethylenetetracarboxylate,
mp 53–54°C (literature data: mp 53–54°C). Distillation
of the remaining filtrate yields diethyl hydrogen
phosphite III.
In view of these conflicting literature data, we
studied the reaction of bromomalonic ester with
diethyl sodium phosphite by the scheme of Michaelis–
Becker reaction. The direction of this process was
(
C H OOC) C=C(COOC H ) + (RO) PHO
2
5
2
2
5 2
2
II
III
(
C H OOC) CHBr + (RO) PONa
2 5 2 2
−NaBr
O
(
C H OOC) CHP(OC H )
2 5 2
2
5
2
I
At the reverse order of mixing the reagents the
NaBr precipitation was also observed. After distilla-
tion, ester I was isolated, whose structure and
physicochemical constants are identical to those
described previously [1]: bp 160–161 (10 mm Hg), nD
1.4453.
2
0
2
198

NEW DATA ON THE MALONIC ESTER PHOSPHORYLATION
2199
A small amount of the compound II crystals (mp
5–56°C) was isolated as a by-product. At a high
dilution of the reagents, the compound II formation
was not practically observed.
Boetius device (measurement error ±0.1°C). The
reaction progress and individuality of the obtained
compounds were monitored by TLC on Silufol UV-
254 plates, eluting with a benzene–ethanol mixture
5
(
6:1) and detecting with iodine vapors.
The IR spectrum of the ester I contains the
–
1
absorption bands at 1744 and 1731 cm belonging to
the carbonyl groups. The absorption band of P=O bond
REFERENCES
–
1
was observed at 1202 cm , which corresponds to the
data [3].
1. Pudovik, A.N. and Moshkina, T.M., Zh. Org. Khim.,
1957, vol. 27, no. 6, p. 1611.
2
.
Kolodyazhnyi, O.I., Kalyagin, G.A., and Gololobov, Yu.G.,
Zh. Org. Khim., 1973, vol. 43, no. 8, p. 1859.
The IR spectra were recorded on a Nicolet Avatar-
3
±
60 spectrometer from KBr pellets (measurement error
0.2 cm ). The melting point was determined on a
3. Kolodyazhnyi, O.I., Repin, L.A., and Gololobov, Yu.G.,
–
1
Zh. Org. Khim., 1974, vol. 44, no. 6, p. 1275.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 10 2011