Nanocomposites of red phosphorus in the reaction with 4-methoxystyrene

Full text of DOI:10.1134/S1070363210070303

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 7, pp. 1380–1382. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © S.F. Malysheva, N.K. Gusarova, N.A. Belogorlova, V.A. Kuimov, A.V. Artem’ev, N.P. Tarasova, Yu.V. Smetannikov, B.A. Trofimov,
2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 7, pp. 1214–1216.
LETTERS
TO THE EDITOR
Nanocomposites of Red Phosphorus in the Reaction
with 4-Methoxystyrene
S. F. Malysheva, N. K. Gusarova, N. A. Belogorlova, V. A. Kuimov,
A. V. Artem’ev, N. P. Tarasova, Yu. V. Smetannikov, and B. A. Trofimov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: gusarova@irioch.irk.ru
Received March 11, 2010
DOI: 10.1134/S1070363210070303
The development of the new method of activation
of red phosphorus based on the use of heterogeneous
superbasic catalytic media and reagents has led to the
creation of nontraditional methods for the formation of
the carbon-phosphorus bond and allowed a direct
introduction of the phosphorus atom into the available
organic compounds (organyl halides, acetylenes,
vinylpyridines, styrene, etc.) [1–3]. As a result, new
one-pot syntheses of diverse organic phosphines,
phosphine oxides, and phosphinic acids have been
developed [1–3], which earlier were prepared by
multistep reactions from toxic and aggressive phos-
phorus halides.
modifications of red phosphorus [4, 5]. These
nanocomposites are prepared by the radiation-induced
polymerization of white phosphorus in the presence of
terminating additives (benzene, graphite, sulfur, etc.) [6].
Here, we first report on the reaction of red phos-
phorus and its nanocomposite with 4-methoxystyrene
in the superbasic system KOH–DMSO. The possibility
of realization of such a reaction was not evident since
4-methoxystyrene was known to be a weak elec-
trophilic alkene [7–10].
The experiments showed that heating (100оС, 3 h)
of the suspension of the nanocomposite of red phos-
phorus, 4-methoxystyrene, KOH and DMSO in the
presence of small amounts of water results in the
formation of a mixture of tris[2-(4-methoxyphenyl)-
ethyl]phosphine oxide (I), bis[2-(4-methoxyphenyl)-
ethyl]phosphine oxide (II), and 2-(4-methoxyphenyl)-
Recently, new phosphorylating reagents were
introduced into the organophosphorus synthesis: nano-
composites of red phosphorus possessing a higher re-
activity with respect to conventional amorphous
Nano-Pn
+
OMe
MeO
OMe
OMe
OMe
OMe
H
H
KOH/DMSO(H2O)
100oC, 3 h
+
+
P
P
P
HO
O
O
O
OMe
I
II
III
1380

NANOCOMPOSITES OF RED PHOSPHORUS
1381
ethyl]phosphinic acid (Ш) in the total yield of 34%
and the ratio of 1 : 1.3 : 1.2 (from the 31Р NMR spec-
troscopy data).
Under similar conditions, (KOH–DMSO, 100оС, 3 h)
amorphous red phosphorus reacts with 4-methoxy-
styrene to give the tertiary phosphine oxide I in a low
yield (~3%).
m (2Н, CH2P), 2.7–-2.82 m (2H, CH2Ar), 3.83 s (3H,
1
OMe), 6.94 d (1H, PH, JPH 505.7 Hz), 6.94 and 7.48
m (4Н, Ar), 8.02 br. s (1H, OH). 13C NMR spectrum
1
(CDCl3), δ, ppm: 25.94 (CH2Ar), 32.72 d (CH2P, JPC
94.2 Hz), 54.95 (OMe), 113.80 (Cо), 129.01 (Cm),
31
134.27 (Ci), 147.61 (Cp). P NMR spectrum (D2О), δ,
1
ppm: 30.18 d, JPH 505.8 Hz. IR (KBr, ν, cm–1): 3436,
2956, 2935, 2837, 2295, 2100, 2600, 1629, 1613,
1585, 1514, 1465, 1443, 1421, 1302, 1250, 1210,
1176, 1129, 1057, 1036, 938, 919, 903, 847, 817, 783,
736, 637, 620, 581, 549, 520, 490, 474, 442. Found,
%: С, 54.27; H, 6.73; P, 15.76. C9H13O3P. Calculated,
%: С, 54.00; H, 6.55; P, 15.47.
Therefore, nanocomposites of elemental phos-
phorus synthesized from white phosphorus using high
energies possess enhanced reactivity relative to the
conventional technical red phosphorus. In the presence
of strong bases these nanocomposites rather ef-
fectively phosphorylate even such weakly electrophilic
alkene as 4-methoxystyrene.
Tris[2-(4-methoxyphenyl)ethyl]phosphine oxide
(I) was prepared under the above conditions from
0.34 g of technical amorphous red phosphorus in the
yield of 3%. Colorless powder, mp 129–131°C (hot
hexane). 1Н NMR spectrum (CDCl3), δ, ppm: 1.93–2.0
m (6H, CH2P), 2.79–2.86 m (6H, CH2C6H4), 3.74 m
(9H, Me), 6.80–6.83 and 7.06–7.08 m (12H, C6H4). 13С
NMR spectrum (CDCl3), δС, ppm: 26.91 (CH2Ar),
30.40 d (CH2P, 1JPC 61.5 Hz), 55.28 (Me), 114.11 (Cо),
Nanocomposite of red phosphorus (nano-Pn) was
prepared by radiation-induced (γ-radiation of 60Сo)
polymerization of white phosphorus in benzene at
room temperature (time of irradiation 93 h, absorbed
dose 117 kGy at the dose rate of 0.35 Gy s–1). From the
data of the scanning and transmission electron
microscopy, the nanocomposite consists mainly of
particles of spherical or elliptic form of 30–50 nm size
[5]. Elemental analysis: Р (80.48%), С (8.13%), Н
(0.68%), О (10.71%).
3
129.04 (Cm), 132.87 d (Ci, JPC 12.5 Hz), 158.3 (Сp).
31Р NMR spectrum (CDCl3), δР, ppm: 47.01. IR
spectrum (KBr), cm–1: 3058, 3016, 2955, 2932, 2908,
2870, 2836, 1610, 1583, 1512, 1461, 1440, 1419,
1337, 1320, 1301, 1275, 1243, 1180, 1161, 1129,
1099, 1033, 1010, 955, 948, 851, 832, 816, 788, 751,
722, 675, 553, 541, 525, 469. Found, %: С 71.57; H
7.33; P 6.70. C27H33O4P. Calculated, %: С 71.66; H
7.35; P 6.84.
Reaction of the nanocomposite of red phos-
phorus with 4-methoxystyrene in the system KОН–
DMSO. The mixture of 0.34 g of the nanocomposite
of red phosphorus, 0.84 g of ground KОН·5Н2О,
15 ml of DMSO, 0.07 ml of water, 1.78 g of 4-
methoxystyrene and 0.01 g of hydroquinone was
stirred for 3 h at 100оС. The reaction mixture was
cooled, diluted with equivalent amount of water,
extracted with chloroform (100% conversion of
phosphorus). The chloroform extracts were washed
with water, dried over potassium carbonate, solvent
was removed under reduced pressure, the residue was
kept in a vacuum to remove unreacted 4-methoxy-
styrene, 0.85 g (48% conversion). The residue was
dried in a vacuum to obtain 0.21 g of the mixture
containing, according to the 31Р NMR spectroscopy
data, phosphine oxide I (47.01 ppm) and phosphine
IR spectra were taken on a Bruker IFS-25 in thin
1
layer and in KBr pellets. Н, 13С, 31Р NMR spectra
were recorded on a Bruker DPX 400 spectrometer
(400, 100, 162 MHz, respectively), internal standard
HMDS, external standard 85% Н3РО4 (31Р).
ACKNOWLEDGMENTS
This work was supported by Russian Foundation
for basic research (grant no. 08-03-00251).
1
oxide II (33.11 ppm, d, JPH 456 Hz) in the ratio of
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1: 1.4. Yield 9% and 12%, respectively. The water
layer was treated with 30% aqueous HCl to рН 4–5,
extracted with chloroform, the extracts were dried with
calcium chloride, chloroform was removed, the residue
was dried in a vacuum to obtain 0.15 g of acid III.
Yield 11%; colorless powder, mp 229–232°C
(ethanol). 1H NMR spectrum (D2О), δ, ppm: 1.80–1.88
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