Nanocomposites of red phosphorus as novel phosphorylating reagents

Full text of DOI:10.1134/S0012500809070027

ISSN 0012-5008, Doklady Chemistry, 2009, Vol. 427, Part 1, pp. 153–155. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © B.A. Trofimov, S.F. Malysheva, N.K. Gusarova, N.A. Belogorlova, V.A. Kuimov, B.G. Sukhov, N.P. Tarasova, Yu.V. Smetannikov, A.S. Vilesov,
L.M. Sinegovskaya, K.Yu. Arsent’ev, E.V. Likhoshvai, 2009, published in Doklady Akademii Nauk, 2009, Vol. 427, No. 1, pp. 54–56.
CHEMISTRY
Nanocomposites of Red Phosphorus
as Novel Phosphorylating Reagents
Academician B. A. Trofimov, S. F. Malysheva, N. K. Gusarova, N. A. Belogorlova,
V. A. Kuimov, B. G. Sukhov, Corresponding Member of the RAS N. P. Tarasova,
Yu. V. Smetannikov, A. S. Vilesov, L. M. Sinegovskaya,
K. Yu. Arsent’ev, and E. V. Likhoshvai
Received January 27, 2009
DOI: 10.1134/S0012500809070027
Red phosphorus in combination with superbasic acetylenes, organic halides, and alkene oxides (at
systems like KOH–nonhydroxylic polar solvent present, these syntheses are more frequently cited in the
(DMSO, HMPA)–water or in highly basic phase-trans- literature under the general name of the Trofimov–
fer catalytic systems is increasingly used at present as a Gusarova reaction [4–7]). For example, phosphorus-
reagent for the synthesis of difficult-to-obtain organo- centered nucleophiles produced by these reagents make
phosphorus compounds (phosphines, phosphine is possible to directly phosphorylate even weak electro-
oxides) [1–3] by the one-pot phosphorylation of avail- philes, such as styrenes, to form tertiary phosphine
able electrophiles, such as aryl- and hetarylalkenes, oxides [3, 8] (Scheme 1).
R
R
KOH–DMSO–H2O
P
Pn +
O
R
R
R = H, tert-Bu
Scheme 1.
As is known, common amorphous red phosphorus
consists of rather large particles with an average size of
40–60 µm [6, 9]. Nonetheless, the use of its nanosized
modifications may substantially enhance its reactivity
in phosphorylation reactions. We already noted the
increased reactivity of nanocomposites of red phospho-
rus in the phosphorylation of 4-vinylbenzyl chloride in
a concentrated aqueous solution of the KOH–dioxane–
phase-transfer catalyst system [10]. However, this phe-
nomenon has not been studied in detail before the
present work.
In this paper, we report new data on the synthesis,
structure, and higher reactivity of nanocomposites of
red phosphorus in comparison with its common amor-
phous modifications.
A sample of nanocomposite of red phosphorus with
organophosphorus compounds was obtained by radia-
tion-induced (gamma radiation of 60Co) polymerization
of white phosphorus in benzene at ambient temperature
(irradiation time 93 h, absorbed dose 117 kGy at a dose
rate of 0.35 Gy/s) (Scheme 2).
60Co
P4
nano-Pn(Ad);
C6H6
Ad = C, graphite,
organophosphorus compounds
Favorsky Institute of Chemistry, Siberian Branch,
Russian Academy of Sciences, ul. Favorskogo 1, Irkutsk,
664033 Russia
Mendeleev University of Chemical Technology
of Russia, Miusskaya pl. 9, Moscow, 125047 Russia
Limnological Institute, Siberian Branch,
Russian Academy of Sciences, ul. Ulan-Batorskaya 3,
Irkutsk, 664033 Russia
Scheme 2.
The obtained nanocomposite is a bright orange pow-
der (self-ignition temperature is 485 K [11]).According
to elemental analysis, this nanocomposite comprises
mainly phosphorus (80.48%) and minor components:
153

154
TROFIMOV et al.
1 µm
500 nm
(b)
(a)
Number of particles
160
140
120
100
80
(d)
60
40
20
0
200 nm
(c)
10 30 50 70 90 100 130 150
Diameter, nm
Fig. 1. Microscopic analysis of particle size of red phosphorus: (a) a general view of precipitate (SEM), (b, c) the size spread of
particles (TEM), (d) the size distribution of particles.
523 cm–1 (ν P–P) also shows low-intensity absorption
carbon (8.13%), hydrogen (0.68%), and oxygen (about
10.71%). The presence of carbon and hydrogen in the
sample indicates the chemical insertion of benzene
molecules into the polymeric structure of phosphorus
probably by the termination of chains with organic rad-
icals or radical cations produced by benzene under the
bands indicating the oxidation of red phosphorus in air
(IR, cm–1): 2311 (ν P–H), 1161 (ν P=O), 800–1050
(ν P–O, δ P–O–P, δ H–P–O), 744, 699 (δ P–P=O).
The Raman spectrum of the nanocomposite
action of gamma radiation. Thus, the obtained sample obtained shows the bands of bending and torsion vibra-
can be considered as a composite comprising the poly-
mers of red phosphorus with inclusions of organophos-
phorus polymers terminated with benzene molecules
and/or the products of its radiation destruction.
tions of P–P bonds (δ P–P–P, τ P–P–P–P) in the range
100–290 cm–1, intense bands at 356, 386, and 456 cm–1
(ν P–P) typical of cage species P9, P8, and P7, respec-
tively [13, 14], and the bands in the range 340–429 cm–1
that can be related to the disordered amorphous compo-
nent of the nanocomposite. It should be noted that the
Raman spectrum shows a specific set of narrow bands
at 465, 504, and 600 cm–1 (ν P–P) characteristic of P4
Indeed, the IR spectrum of the composite shows the
absorption bands of benzene ring at 1580 and 1477 cm–1
(ν C=C), 737 and 690 cm–1 (δ CH), and the bands of
stretching vibrations of P–C (740 cm–1) and P–P bonds
(485 and 519 cm–1) [12]. All these data indicate the
chemical binding of solvent fragments (benzene) to
the resulting phosphorus polymer [6]. Oxygen is
involved in the composite upon handling in air owing
to the oxidation of the most chemically reactive cites
(defects) [2, 9] and represented as functional groups
with phosphorus–oxygen bonds: IR (cm–1): 1143–
1161 (ν P=O), 850–1050 (ν P–O, δ P–O–C, δ P–O–
P, δ H–P–O) [12].
tetrahedron [15]. A weak band at 998 cm–1 is likely to
refer to the vibrations of benzene ring (δ C–H), bands
at 1350 and 1580 (ν C–C) seems to refer to graphite-
like structures, while P–H stretching vibrations appear
at 2247 cm–1. At the same time, the Raman spectrum of
technical amorphous red phosphorus shows no distinct
maxima.
The data of scanning and transmission electron
microscopy (SEM and TEM) indicate that the obtained
sample is indeed a nanocomposite and consists of
spherical or elliptical particles of 10–140 nm in size
It should be noted that the IR spectrum of common
red phosphorus of technical grade (State Standard
GOST 4133 no. 00N1338, batch 101 of November
2001) along with the expected absorption bands at (Figs. 1a–1c). Figure 1d shows the size distribution of
DOKLADY CHEMISTRY Vol. 427 Part 1 2009

NANOCOMPOSITES OF RED PHOSPHORUS AS NOVEL PHOSPHORYLATING REAGENTS
155
the particles, it is seen that the sample consists mainly heating (120°C, 3 h) of the reagents in a KOH–
(by 45%) of nanoparticles of 30–50 nm in size.
DMSO system and leads to the formation of sec-
ondary (1) and tertiary (2) phosphine oxides and
potassium phosphinite (3) in 95% total yield at the
ratio 4.9 : 1.8 : 1. The conversion of the red phos-
phorus nanocomposite and α-methylstyrene was
To estimate the phosphorylating ability of the
obtained nanocomposite of red phosphorus, we
studied its reaction with α-methylstyrene in com-
parison with common red phosphorus. The reaction
of the red phosphorus nanocomposite proceeds on 100 and 17%, respectively (Scheme 3).
Me
Me
H
P
KOH–DåSé–H2O
nano-Pn(Ad) +
+
O
Me
1
Me
Me
Me
P
+
H
O
P
Me
O
KO
2
3
Scheme 3.
4. Malysheva, S.F. and Arbuzova, S.N., in Sovremennyi
organicheskii sintez (Modern Organic Synthesis), Mos-
cow: Khimiya, 2003, p. 160.
Under these conditions, the reaction leads also to
minor amounts of phosphine and potassium hypophos-
phite, the products resulting from the reaction of ele-
mental phosphorus with aqueous potassium hydroxide
[8].
Technical amorphous red phosphorus reacts less
efficiently with α-methylstyrene under similar condi-
tions but more selectively to give tertiary phosphine
oxide 2 in only 15% yield (the conversions of phospho-
rus and α-methylstyrene are 82 and 18%, respectively).
Thus, we have shown that elemental phosphorus
nanocomposites obtained from white phosphorus with
the use of high-energy radiation have enhanced reactiv-
ity as compared with common red phosphorus. In the
presence of strong bases, these nanocomposites effi-
ciently phosphorylate even weak electrophile as
α-methylstyrene.
5. Sukhov, B., Malysheva, S., Vakul’skaya, T., et al.,
Arkivoc, 2003, vol. xiii, pp. 196–204.
6. Smetannikov, Yu.V., Doctoral (Chem.) Dissertation,
Moscow, 2005.
7. Malysheva, S.F., Smetannikov, Yu.V., Kuimov, V.A.,
et al., Abstracts of Papers XV International Conference
on Chemistry of Phosphorus Compounds, St. Peters-
burg, 2008, p. 393.
8. Malysheva, S.F., Gusarova, N.K., Kuimov, V.A., et al.,
Zh. Obshch. Khim., 2007, vol. 77, no. 3, pp. 449–454.
9. Skolnik, S., Tarbutton, G., and Bergman, E., J. Am.
Chem. Soc., 1946, vol. 68, no. 11, pp. 2310–2314.
10. Malysheva, S.F., Kuimov, V.A., Gusarova, N.K., et al.,
Zh. Obshch. Khim., 2007, vol. 77, no. 11, pp. 1823–
1829.
11. Tarasova, N.P., Phosphorus, Sulfur, Silicon, Relat. Elem.,
ACKNOWLEDGMENTS
2008, vol. 183, nos. 2/3, pp. 300–305.
12. Shagidullin, R.R., Mukhametov, F.S., Nigmatulina, R.B.,
et al., Atlas IK-spektrov fosfororganicheskikh soedinenii
(Atlas of IR Spectra of Organophosphorus Compounds),
Moscow: Nauka, 1984.
13. Fasol, G., Cardona, M., Honle, W., and von Schner-
ing, H.G., Solid State Commun., 1984, vol. 52, no. 3,
pp. 307–310.
This work was supported by the Russian Foundation
for Basic Research (project no. 08–03–00251).
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