C-phosphorylation of azoles in synthesis of novel fused phosphorus-containing heterocycles

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C-Phosphorylation of Azoles in Synthesis of Novel
Fused Phosphorus-Containing Heterocycles
Alexander M. Pinchuk a , Vladimir V. Ivanov a , Evgenij V. Zarudnizkii a , Alexej O.
Pushechnikov a & Andrej A. Tolmachev a
a Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine
Version of record first published: 27 Oct 2010
To cite this article: Alexander M. Pinchuk, Vladimir V. Ivanov, Evgenij V. Zarudnizkii, Alexej O. Pushechnikov & Andrej A.
Tolmachev (2002): C-Phosphorylation of Azoles in Synthesis of Novel Fused Phosphorus-Containing Heterocycles, Phosphorus,
Sulfur, and Silicon and the Related Elements, 177:6-7, 1767-1769
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Phosphorus, Sulfur and Silicon, 2002, Vol. 177:1767–1769
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DOI: 10.1080/10426500290092992
C-PHOSPHORYLATION OF AZOLES IN SYNTHESIS
OF NOVEL FUSED PHOSPHORUS-CONTAINING
HETEROCYCLES
Alexander M. Pinchuk, Vladimir V. Ivanov,
Evgenij V. Zarudnizkii, Alexej O. Pushechnikov,
and Andrej A. Tolmachev
Institute of Organic Chemistry, National Academy
of Sciences of Ukraine, Kiev, Ukraine
(Received July 29, 2001; accepted December 25, 2001)
Keywords: Azole; fused phosphorus-containing heterocyclic systems;
phosphorylation
Direct C-phosphorylation with phosphorus(III) halides in basic medium
has proved to be an efficient and convenient method for the introduction
of a variety of phosphorus functions in the electron-rich heteroaromatic1
compounds. When applied to functionalized pyrroles,2 this reaction has
afforded a number of novel phosphorus-containing fused heterocycles.
Herein, we report on our recent findings concerning the construction of
phosphorus-containing fused heterocycles having azole nuclei.
Readily available derivatives of 5-amino-1-aryl-3-methylpyrazoles—
amides, ureas, and azomethines3—have been subjected to the phospho-
rylation with P(III) halides in basic medium to produce bi- and even
tricyclic (as in the last case) heterocyclic compounds having an endo-
cyclic phosphorus atom (Figure 1).
We explored the same approach concerning 1,3-azoles, known
to be phosphorylated via a different mechanism.4 We have shown
that the amide 5 (X = CH) reacts with phosphorus tribromide as
well as with dibromophenylphosphine in basic medium to yield the
4,5-dihydrobenzo[e]imidazo[2,1-c][1,4,2]diazaphosphinine derivatives,
which could be converted into P(V) derivatives 8 and 95 (Figure 2).
Address correspondence to Alexander M. Pinchuk, Institute of Organic Chemistry,
National Academy of Sciences of Ukraine, Murmanskaya, 5, Kiev-094, 02094, Ukraine.
E-mail: hetfos@ukrpack.net
1767

1768
A. M. Pinchuk et al.
FIGURE 1
FIGURE 2
It has been found that the similar amide 5 (X = N) bearing the
1,2,4-triazole moiety could also be phosphorylated, although less ac-
tivity of this compound is noted.
Moreover, phosphorus(V) acid chlorides, known as phosphorylating
agents of less reactivity, were shown to react with the parent im-
idazolylaniline of 5 to furnish the 4,5-dihydrobenzo[e]imidazo[2,1-c]
[1,4,2]diazaphosphinine derivatives, such as 10. The phosphorylation
of the amide of 3,5-dimethoxybenzoic acid (11) with PBr3 yielded the
cyclic bromophosphonite 12, which underwent intramolecular ring clo-
sure under heating to produce the pentacyclic compound 13 (Figure 3).
FIGURE 3

C-Phosphorylation of Azoles
1769
FIGURE 4
We have found very recently that imidazole can be phosphorylated
not only at the meso position but also at position 5 when the pre-
ferred 2-position is blocked by an SCH3 group, as in 14 (Figure 4).
However, the reaction of the 2-methylimidazole derivative 16 with di-
bromophenylphosphine proceeded through the phosphorylation of the
methyl group and resulted in the construction of a seven-membered
heterocycle (17, 18).
In conclusion, we have shown that in spite of the difference in the
phosphorylation mechanisms, a number of functionalized derivatives
of both pyrazoles and 1,3-azoles could be successfully employed in the
design of phosphorus-containing fused heterocyclic systems via their
reaction with phosphorus(III) halides.
REFERENCES
[1] (a) S. P. Ivonin, T. E. Terikovska, A. A. Chaikovskaya, A. P. Marchenko, G. N. Koydan,
A. M. Pinchuk, and A. A. Tolmachev, Heteroatom Chem., 10, 213 (1999); (b) A. A.
Tolmachev, A. I. Sviridon, A. N. Kostyuk, and A. M. Pinchuk, Heteroatom Chem., 6,
449 (1995).
[2] (a) S. P. Ivonin, A. O. Pushechnikov, and A. A. Tolmachev, Heteroatom Chem., 11, 107
(2000); (b) A. A. Tolmachev, S. I. Dovgopoly, A. N. Kostyuk, E. S. Kozlov, and A. O.
Pushechnikov, Heteroatom Chem., 8, 495 (1997).
[3] (a) A. A. Tolmachev, S. I. Dovgopoly, A. N. Kostyuk, E. S. Kozlov, A. O. Pushech-
nikov, and W. Holzer, Heteroatom Chem., 10, 391 (1999); (b) A. A. Tolmachev, A. O.
Pushechnikov, D. G. Krotko, S. P. Ivonin, and A. N. Kostyuk, Chem. Heterocycl.
Compd., 34(9), 1098 (Eng.) (1998, pub. 1999).
[4] A. A. Tolmachev, A. A. Yurchenko, A. S. Merkulov, M. G. Semenova, E. V. Zarudnitskii,
V. V. Ivanov, and A. M. Pinchuk, Heteroatom Chem., 10, 585 (1999).
[5] V. V. Ivanov, A. A. Yurchenko, A. N. Chernega, A. M. Pinchuk, and A. A. Tolmachev,
Heteroatom Chem., in press.