Features of phenolysis of phenylphosphonous acid tetraethydiamide

Full text of DOI:10.1134/S1070363207080294

ISSN 1070-3632, Russian Journal of General Chemistry, 2007, Vol. 77, No. 8, p. 1465.
Pleiades Publishing, Ltd., 2007.
Original Russian Text
E.E. Nifant’ev, D.A. Ganin, A.T. Teleshev, V.Yu. Mishina, I.V. Abrashina, 2007, published in Zhurnal Obshchei Khimii, 2007,
Vol. 77, No. 8, p. 1388.
LETTERS
TO THE EDITOR
Features of Phenolysis
of Phenylphosphonous Acid Tetraethydiamide
E. E. Nifant’ev, D. A. Ganin, A. T. Teleshev, V. Yu. Mishina, and I. V. Abrashina
Moscow Pedagogical State University,
Nesvizhskii per., 3, Moscow, 119021 Russia
e-mail: chemdept@mtu-net.ru
Received May 18, 2007
DOI: 10.1134/S1070363207080294
Previously we reported that alcohols and phenols
react with trivalent phosphorus acid amides by similar
schemes, that is, both alcohols and phenols in the
reaction with equivalent amount of a phosphorus
amide substitute completely its >P N bonds [1]:
yields diester III and phenyl N,N-diethylphenylphos-
phonamidite IV. The ratio of the formed diester III
and monoester IV, according to 31P NMR spectra,
depends on the reaction temperature. Actually, an
equilibrium is attained:
>P NR2 + HOR
>P OR + HNR2.
PhP(NEt ) + 2PhOH
PhP(NEt )OPh + [Et NH ]OPh
2 2 2
2 2
I
IV
Here we report that phenylphosphonous tetraethyl-
diamide I reacts with phenols and alcohols quite dif-
ferently. With hexane-1-ol at 110 C, phosphorylating
PhP(OPh) + 2HNEt .
(2)
2
2
III
agent I reacts in 1:2 molar ratio in a closed system to
give the diester of phenylphosphonous acid II:
1
Similar results were obtained in the reactions of
equimolar amounts of phosphonous amide I with
hexane-1,6-diol [complete phosphorylation, reaction
PhP(NEt ) + 2CH (CH ) CH OH
2
2
3
2 4
2
(1)] and 4,4 -dihydroxybiphenyl or hydroquinone
partial phosphorylation, equilibrium, reaction (2)].
I
[
PhP[O(CH ) CH ] + 2HNEt .
(1)
2
5
3 2
2
II
REFERENCES
On the contrary, reaction of phosphonous amide I
with phenol in 1:2 molar ratio in a closed system
1. Nifantiev, E.E., Gratchev, M.K., and Burmistrov, Yu.V.,
Chem. Rev., 2000, vol. 100, no. 10, p. 3755.
1
In all the cases reagent I contained small amounts of diethyl-
amine hydrochloride which catalyzes phosphorylation [1].
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