ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 8, p. 1344.
Pleiades Publishing, Inc., 2006.
Original Russian Text M.Zh. Ovakimyan, A.S. Pogosyan, N.M. Kikoyan, M.G. Indzhikyan, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76,
No. 8, p. 1400.
LETTERS
TO THE EDITOR
Structural Isomerism of Diphenylphosphoryl-2-hydroxyethane
M. Zh. Ovakimyan, A. S. Pogosyan, N. M. Kikoyan, and M. G. Indzhikyan
Institute of Organic Chemistry, National Academy of Sciences of Armenia,
ul. Z. Kanakertsi 167a, Yerevan, 375091 Armenia
Received October 27, 2005
DOI: 10.1134/S1070363206080366
We found that diphenylphosphoryl-2-hydroxy-
+
Ph2P CH2CH2O
ethane prepared by base hydrolysis of triphenyl-2-
hydroxyethylphosphonium chloride [1], according to
1H, 31P, and 13C NMR and mass spectra, is a
mixture of two isomeric compounds in 1:3 ratio.
Ph2P CH2CH2OH
OH
O
A
B
The data obtained allow a conclusion that the
product under study exists as a mixture of the minor
form A and major form B. Existence of the third
isomeric form with a five-coordinate phosphorus atom
1
The H NMR spectrum taken in CDCl3 contains
two multiplets characteristic of PCH2 and OCH2
groups, and its 13C NMR spectrum contains two
doublets of PCH2 and two singlets of OCH2 groups.
is disapproved by the H NMR and 31P NMR data.
1
1
In the H NMR spectrum recorded in DMSO, the OH
Identification of the major product as form B was
based on the higher coupling constant and the lower
chemical shift of PCH2 carbon signal.
1H NMR spectra of CDCl3 and DMSO-d6 solutions,
31P NMR spectra of CDCl3 solutions, and 13C NMR
spectra of CDCl3 solutions were taken on a Varian
Mercury-300 (300 MHz) spectrometer. The mass
spectrum was recorded on an MKh-1321A device.
proton is manifested as a separate signal. Its integral
intensity shows that it belongs to the minor product.
For more exact assignment of these signals, the cor-
1
relation between the H and 13C NMR spectra was
carried out. The 31P NMR spectrum contains two
signals in the range characteristic of phosphonium
salts: at 34.90 and 30.10 ppm. The molecular ion peak
in the mass spectrum is observed at m/z 246. Note that
the compound under study was also obtained by the
similar procedure in [2].
REFERENCES
1. Aksnes, G., Acta Chem. Scand., 1961, vol. 15, no. 2,
p. 438.
2. Bondarenko, N.A., Matrosov, E.I., Tsvetkov, E.N., and
Kabachnik, M.I., Izv. Akad. Nauk SSSR, Ser. Khim.,
1980, no. 1, p. 106.
Heating the compound in benzene or toluene for
6 8 h in the absence as well as in the presence of an
alkali decreases the yield of the major product. The 1H
NMR spectrum shows that the isomer ratio becomes
1:2. Chlorination of the product studied with POCl3
according to [3] gives diphenylphosphoryl-2-chloro-
ethane in a high yield.
3. Bondarenko, N.A. and Tsvetkov, E.N., Zh. Obshch.
Khim., 1989, vol. 59, no. 7, p. 1533.
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Ovakimyan
