ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 1, pp. 155 156.
Pleiades Publishing, Ltd., 2008.
Original Russian Text
M.A. Pudovik, L.K. Kibardina, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 1, pp. 163 164.
LETTERS
TO THE EDITOR
Synthesis of 1,3,4-Diazaphospholidine by the Reaction
of Phenyl (Chloromethyl)phosphonoisocyanatidate
with Diphenyl [Phenyl(phenylamino)methyl]phosphonate
M. A. Pudovik and L. K. Kibardina
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, ul. Akad. Arbuzova 8, Kazan, Tatarstan, 420088 Russia
e-mail: pudovik@iopc.knc.ru
Received July 17, 2007
DOI: 10.1134/S1070363208010301
The chemistry of -aminoalkylphosphonates has
progressed over the past decade. Thus, methods of
their synthesis have been developed and improved [1],
and the biologic activity of these compounds has been
studied. Much effort has been directed to chemical
modification of -aminophosphonates [2]. It is known
that in the presence of triethylamine as catalyst these
compounds can add to alkyl iso(thio)cyanates with
formation of N,N -disubstituted (thio)ureas. The latter
are stable compounds which undergo cyclization into
1,4,2-diazaphospholidines only under rigid conditions
in the presence of 1,4-diazabicyclo[2,2,2]octane as
catalyst [3]. Proceeding with the development of
synthetic approaches to new heterophosphacyclanes
with endocyclic P C bonds on the basis of functional
-substituted alkylphosphonates [4, 5], we explored
the reactions of diphenyl -(phenylamino)benzyl-
phosphonate I with aromatic and phosphorylated iso-
(thio)cyanates. We found that phosphonate I reacts
with phenyl isocyanate and phenyl isothiocyanate
neither under heating nor in the presence of any ca-
talysts (such as 1,4-diazabicyclo[2,2,2]octane and tri-
ethylamine), probably due to reduced basicity of the
nitrogen atom in this compound. We succeeded in
accomplishing this reaction with a more active phos-
phorylated isocyanate II. The reaction gave diaza-
phospholidine V and chloromethylphosphonate VI
and occurred by the following scheme involving
intermediate formation of urea III and its cyclization
into phospholidine IV with phenol liberation. Sub-
sequent phenolysis of heterocycle IV results in P N
bond rupture and formation of the final products.
O
O
O
Ph
O
OPh
PhO
(PhO)2P CH NC(O)NHP
(PhO)2P CH NHPh +
PNCO
ClCH2
CH2Cl
Ph
Ph
I
II
III
Ph
O
Ph
O
O
PhO
PhO
O
CH
CH
P
P
PhOH
PhOH
N Ph + ClCH2P(OPh)2
N Ph
HN
N
C
O
C
PhO
P
O
IV
ClCH2
V
VI
1,5-Diphenyl-4-phenoxy-1,3,4 5-diazaphospho-
lidin-2-one 4-oxide (V). A mixture of 7.06 g of phos-
phonate I and 3.76 g of isocyanate II in 20 ml of an-
hydrous chloroform was heated at 70 C for 3 h. One
day later, 3.2 g (44%) of compound V was separated,
1
According to the H NMR spectra of the reaction
mixture, phosphpholidine V consists of a mixture of
two diastereomers in a 76:24 ratio. The composition
and structure of product V were confirmed by means
of high-resolution mass spectrometry.
155
Pudovik
