Synthesis of Tris(2-pyridyl)phosphine from red phosphorus and 2-bromopyridine in the CsF-NaOH-DMSO superbasic system

Full text of DOI:10.1134/S0012500812080071

ISSN 0012ꢀ5008, Doklady Chemistry, 2012, Vol. 445, Part 2, pp. 164–165. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © S.F. Malysheva, A.O. Korocheva, N.A. Belogorlova, A.V. Artem’ev, N.K. Gusarova, B.A. Trofimov, 2012, published in Doklady Akademii Nauk, 2012,
Vol. 445, No. 6, pp. 637–638.
CHEMISTRY
Synthesis of Tris(2ꢀpyridyl)phosphine from Red Phosphorus
and 2ꢀBromopyridine in the CsF–NaOH–DMSO
Superbasic System
S. F. Malysheva, A. O. Korocheva, N. A. Belogorlova, A. V. Artem’ev,
N. K. Gusarova, and Academician B. A. Trofimov
Received April 5, 2012
DOI: 10.1134/S0012500812080071
Pyridylphosphines are widely used as polydentate
chemolabile P,N ligands for the design of multipurꢀ
N
pose metalꢀcomplex catalysts [1–3], highly reactive
building blocks in organic synthesis [4], and precurꢀ
sors in the preparation of new pharmaceuticals [5, 6].
Among pyridylphosphines, tris(2ꢀpyridyl)phosphine
is of special interest as a tripodal ligand of chelating
type due to the geminal arrangement of the nitrogen
atoms with respect to the phosphorus atom. Metal
complexes obtained from tris(2ꢀpyridyl)phosphine are
efficient catalysts for industrially important processes,
such as alkene hydroformylation [7], ethylene polyꢀ
merization [8], methoxycarbonylation of acetylenes
CsF/NaOH/DMSO
100°C, 3 h
P
N
Pred
+
N
Br
N
1
The reaction seems to proceed via initial cleavage
of the red phosphorus macromolecule under the
action of hydroxide anions to form phosphide anions
that further react with 2ꢀbromopyridine according to
the nucleophilic substitution scheme.
HO–
−
P P
P
+
HO P
[
9], and diene synthesis [10].
The known methods of preparation of tris(2ꢀ
pyridyl)phosphine based on the reactions of pyridylꢀ
lithium [11] or pyridylmagnesium halides [12] with
phosphorus chlorides are multistep and require special
experimental conditions (low temperatures, highꢀpurity
anhydrous solvents, isolation of the target phosphine by
column chromatography [11] or by solid–liquid extracꢀ
tion with a large amount of diethylamine [12]).
−
P
+
Br–
P
1
–
N
N
Br
The revealed reaction opens a convenient approach
to the oneꢀpot synthesis of tris(2ꢀpyridyl)phosphine, a
ligand necessary for the design of metal complexes and
a starting reagent to construct supramolecular strucꢀ
tures and pharmaceuticals. Obtained data provide a
fundamental contribution to the development of new
methodology of synthesis of organophosphorus comꢀ
pounds by the direct phosphorylation of electrophiles
with elemental phosphorus in the presence of strong
bases [15].
In this report, we disclose a fundamentally new
convenient method for the synthesis of tris(2ꢀ
pyridyl)phosphine 1 by the direct reaction of red phosꢀ
phorus with 2ꢀbromopyridine in the presence of a
strong base produced in the CsF–NaOH–DMSO sysꢀ
tem, which was previously used successfully in the reacꢀ
tions of nucleophilic addition to triple bond [13, 14].
The reaction occurs on heating the reagents (100°С, 3 h)
EXPERIMENTAL
The IR spectrum was recorded as KBr pellets on a
Bruker IFSꢀ25 spectrophotometer. The Н, С, and
P NMR spectra were obtained with a Bruker DPXꢀ
00 spectrometer (operating at 400.13, 101.61, and
61.98 MHz, respectively) using hexamethyldisiloxꢀ
ane as an internal reference and 85% Н РО as an
external reference ( P NMR). All experimental
in an inert atmosphere to give phosphine
yield (not optimized).
1 in 57%
1
13
3
1
4
1
Favorskii Institute of Chemistry, Siberian Branch,
Russian Academy of Sciences, ul. Favorskogo 1, Irkutsk,
64033 Russia
3
4
3
1
6
164

SYNTHESIS OF TRIS(2ꢀPYRIDYL)PHOSPHINE
165
manipulations were carried out in an inert atmosphere and the Council for Grants of the President of the
(
argon).
Russian Federation for Support of Leading Scientific
Schools (grant no. NShꢀ1550.2012.3).
A suspension of 3.1 g (100 mmol) of red phosphoꢀ
rus, 4.0 g (100 mmol) of NaOH, 15.2 g (100 mmol) of
CsF, 40 mL of DMSO, and 7.9 g (50 mmol) of 2ꢀbroꢀ
mopyridine was heated to 100 С and stirred for 3 h at
this temperature, and then cooled; 60 mL of water was
added, and the mixture was extracted with chloroform
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×
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1
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–
1
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IR (KBr, ν, cm ): 3039, 2961, 2900, 1572, 1558,
1
9
5
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δ
, ppm,
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.64 (m, 3H, HCꢀ4), 8.72 (d, 3H, HCꢀ6, 3JHH 3.70 Hz).
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3
(
7
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С, ppm): 122.5 (Cꢀ5), 128.9
δ
(
1
d, Cꢀ2, 2JPC 19.3 Hz), 135.6 (d, Cꢀ4, 3JPC 2.6 Hz), 10. Kuo, C.ꢀY., Fuh, Y.ꢀS., Shiue, J.ꢀY., et al., J. Orgaꢀ
nomet. Chem., 1999, vol. 588, pp. 260–267.
50.1 (d, Cꢀ6, 2JPC 19.3 Hz), 161.5 (d, Cꢀ2, 1JPC 2.6 Hz).
1
1. Bowen, R.J., Garner, A.C., BernersꢀPrice, S.J., et al.,
31
P NMR (CDCl3,
δ
Р, ppm): –1.86.
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For C H N P anal. calcd. (%): C, 67.92; H, 4.56;
12
N, 15.84; P, 11.68. Found (%): C, 67.75; H, 4.38;
N, 15.67; P, 11.43.
15
3
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ACKNOWLEDGMENTS
vol. 76, pp. 550–570.
This work was supported by the Russian Foundaꢀ
tion for Basic Research (project no. 11–03–00286a)
15. Trofimov, B.A. and Gusarova, N.K., Mendeleev Comꢀ
mun., 2009, vol. 19, pp. 295–302.
DOKLADY CHEMISTRY Vol. 445
Part 2
2012