ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 7, pp. 1307–1308. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © S.F. Malysheva, A.V. Artem’ev, N.A. Belogorlova, A.O. Korocheva, N.K. Gusarova, B.A. Trofimov, 2012, published in Zhurnal
Obshchei Khimii, 2012, Vol. 82, No. 7, pp. 1210–1211.
LETTERS
TO THE EDITOR
First Example of the Сsp –P Bond Formation in the Reaction
2
of Red Phosphorus with Hetaryl Halides
S. F. Malysheva, A. V. Artem’ev, N. A. Belogorlova,
A. O. Korocheva, N. K. Gusarova, and B. A. Trofimov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: boris_trofimov@irioch.irk.ru
Received February 20, 2012
DOI: 10.1134/S1070363212070213
Direct reactions of red and white phosphorus with
electrophiles (aryl- and hetarylalkenes, arylacetylenes,
alkyl, allyl, and benzyl halides) in superbasic systems
alkali metal hydroxide – dipolar aprotic solvent
(DMSO, HMPTA) or under the conditions of phase
transfer catalysis are now considered as a novel chlo-
rine-free method of formation of the С–P bond [1, 2].
Within this approach, the one-pot methods have been
elaborated for the synthesis of various phosphines,
phosphine oxides, and phospinic acids [1, 2] which had
earlier been obtained by multistep processes from
phosphorus halides. However, in the case of the
additives of water at heating (70°C, 3 h, argon) to form
tris(2-pyridyl)phosphine I in 55% yield.
This reaction is the first example of the formation
of the Сsp –P bond in the reaction of elemental phos-
2
phorus with hetaryl halides and it opens a convenient
route to the synthesis of the hitherto hardly accessible
tris(2-pyridyl)phosphine, a polydentate ligand for the
design of multipurpose metal complexes [4–7].
The obtained results contribute to the chemistry of
phosphorus, organophosphorus compounds, pyridine
and P,N-ligands, as well as to the theory of nucleo-
philic aromatic substitution.
substitution reaction only the Сsp –P bond was formed.
3
Recently, tris(1-naphthyl)phosphine was synthesized
from red phosphorus and 1-naphthyl bromide in the
system KОН–DMSO [3]. To the best of our
knowledge, there are no data in the literature on the
Tris(2-pyridyl)phosphine (I). To a mixture of red
phosphorus (3.1 g, 0.10 mol), KОН·0.5H2O (13.0 g,
0.20 mol), water (2 ml) and DMSO (40 ml) heated to
70°С, a solution of 2-bromopyridine (7.9 g, 0.05 mol)
in DMSO (10 ml) was added dropwise at stirring in the
course of 30 min. The reaction mixture was stirred for
4.5 h at 70°С, cooled, diluted with water (50 ml), and
extracted with chloroform (3×30 ml). The chloroform
extracts were washed with water (5×15 ml), dried over
potassium carbonate, the solvent was removed, the
residue was evacuated (44–50°C, 1 mm Hg), 1.5 g of
unreacted 2-bromopyridine was recovered (conversion
81%). The residue was crystallized from isopropanol
to give 1.96 g of phosphine I, yield 55% (to the reacted
2-bromopyridine). Colorless crystalline powder, mp
115–116°C (113°C [8]). IR spectrum, ν, (KBr), cm–1:
3038, 2963, 2904, 1575, 1560, 1451, 1425, 1415,
1282, 1278, 1145, 1086, 1043, 988, 962, 909, 897,
775, 767, 741, 723, 714, 620, 551, 515, 504, 498, 427,
formation of the Сsp –P in the reactions of elemental
2
phosphorus with hetaryl halides in superbasic systems.
In the present work we report for the first time on
the direct phosphination of hetaryl halides in the
system red phosphorus–strong base by the example of
2-bromopyridine.
Red phosphorus reacts with 2-bromopyridine in the
superbasic suspension KОН–DMSO with small
N
N
KOH/DMSO(H2O)
70oC, 3 h
Pred
+
P
N
N
Br
1
408, 395. Н NMR spectrum, δ, ppm (J, Hz): 7.19–
I
1307
Malysheva
