Direct phosphorylation of β-alkylstyrenes with elemental phosphorus under Trofimov-Gusarova reaction conditions

Full text of DOI:10.1134/S1070428013120233

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 12, pp. 1839–1841. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.V. Artem’ev, S.F. Malysheva, A.O. Korocheva, S.V. Fedorov, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49,
No. 12, pp. 1857–1858.
SHORT
COMMUNICATIONS
Direct Phosphorylation of β-Alkylstyrenes with Elemental
Phosphorus under Trofimov–Gusarova Reaction Conditions
A. V. Artem’ev, S. F. Malysheva, A. O. Korocheva, and S. V. Fedorov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: chemisufarm@yandex.ru
Received June 21, 2013
DOI: 10.1134/S1070428013120233
In the past decades, the Trofimov–Gusarova reac-
tion of red phosphorus with electrophilic reagents in
heterogeneous strongly basic media, e.g., in a system
alkali metal hydroxide–polar aprotic solvent (DMSO,
HMPA) or under conditions of phase-transfer catalysis,
has been successfully developed and opened new pros-
pects in chlorine-free and environmentally acceptable
syntheses of previously unknown or difficultly acces-
sible organic phosphines, phosphine oxides, and phos-
phonic and phosphinic acids [1–3]. Alkenes (styrenes
[4], 1H-indene [5], allylbenzenes [6], vinylpyridines
[7]), alkynes [8, 9], and alkyl [10], allyl [11], benzyl
[12], aryl [13], and hetaryl halides [14] were used as
electrophiles in these reactions. We recently showed
that 1-methoxy-2-[(E)-prop-1-en-1-yl]benzene reacts
with red phosphorus in KOH–DMSO to give
2-(2-methoxyphenyl)-1-methylethylphosphinic acid in
63% yield [15].
(in the presence of a small amount of water) at 120°C
(2.5 h) to afford previously unknown phosphinic acids
IIa–IIc in 34–40% yield (unoptimized). The reaction
mixtures also contained unreacted styrenes Ia–Ic
(1H NMR) and primary phosphines (31P NMR).
In summary, the direct phosphorylation of various
β-alkylstyrenes with elemental phosphorus is readily
realized under Trofimov–Gusarova reaction condi-
tions to afford previously unknown phosphinic acids
with high selectivity. The products attract interest as
promising intermediate products for organic synthesis
[16] and ligands for the preparation of metal com-
plexes [17].
1-Phenylpentan-2-ylphosphinic acid (IIa). A mix-
ture of 3.10 g (100 mmol) of red phosphorus, 8.00 g
(123 mmol) of powdered KOH · 0.5 H2O, 5.85 g
(40 mmol) of 1-phenylpent-1-ene (Ia), 30 mL of
DMSO, and 1 mL of water was heated for 2.5 h at
120°C under vigorous stirring in an argon atmosphere.
The mixture was cooled, diluted with water (50 mL),
and extracted with chloroform (3×20 mL). The com-
bined extracts were washed with water (2×30 mL),
dried over K2CO3, and evaporated. The residue was
a yellowish oily material which contained (according
In this work we made an attempt to accomplish
direct phosphorylation of styrenes having a C3–C5
alkyl group in the β-position with elemental phos-
phorus in superbasic medium. The presence of such
groups may hamper nucleophilic addition of phos-
phorus-centered anions generated by cleavage of P–P
bonds of elemental phosphorus under the action of
hydroxide ions. In fact, β-alkylstyrenes Ia–Ic reacted
with red phosphorus in a KOH/DMSO suspension
1
to the H and 31P NMR data) unreacted alkene Ia and
1
1-phenylpentan-2-ylphosphine (δP –123 ppm, t, JPH
=
190.6 Hz).
O
(1) KOH–DMSO/H2O, 120°C, 2.5 h
(2) HCl/H2O, 20–25°C
R
P
OH
H
+
P (red)
R
Ia–Ic
IIa–IIc, 34–40%
R = Pr (a), Bu (b), C5H11 (c).
1839

ARTEM’EV et al.
1840
The aqueous phase was acidified with 35% aqueous
The IR spectra were recorded on a Bruker IFS-25
1
spectrometer from thin films. The H, 13C, and 31P
HCl to pH 1 and extracted with chloroform (3×
20 mL). The combined extracts were washed with
water (3×15 mL) and dried over Na2SO4, the solvent
was distilled off, and the residue was dried under
reduced pressure (35–40°C, 1 mm). Yield 3.38 g
(40%), yellowish oily substance. IR spectrum, ν, cm–1:
NMR spectra were measured on a Bruker DPX-400
instrument at 400.13, 101.61, and 161.98 MHz, respec-
tively, using CDCl3 as solvent and 85% H3PO4 as
external reference for 31P. Alkenes Ia–Ic were synthe-
sized by dehydration of the corresponding 1-phenyl-
alkan-1-ols in the presence of p-toluenesulfonic acid.
Red phosphorus was commercial product (KSAN SIA,
China).
1
2366 s (P–H), 1172 s (P=O). H NMR spectrum, δ,
3
ppm: 0.91 t (3H, Me, J = 6.7 Hz), 1.41–1.59 m and
1.66–1.80 m [4H, (CH2)2Me], 2.01–2.11 m (1H, CHP),
2.72–2.82 m and 3.08–3.16 m (1H each, CH2Ph),
7.04 d (1H, PH, 1J = 542 Hz), 7.26–7.37 m (5H, Ph),
12.08 br.s (1H, OH). 13C NMR spectrum, δC, ppm:
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 12-03-31097-mol_a) and by the President of the
Russian Federation (Program for Support of Leading
Scientific Schools, project no. NSh-1550.2012.3).
3
13.9 (Me), 20.5 d (CH2Me, J = 8.6 Hz), 28.3 d
(CH2Et, 2J = 1.7 Hz), 33.0 (CH2Ph), 39.5 d (CHP, 1J =
95.7 Hz), 126.4 (Cp), 128.4 and 129.0 (Co, Cm), 138.6 d
3
(Ci, J = 12.4 Hz). 31P NMR spectrum: δP 41.86 ppm
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(1J = 542 Hz). Found, %: C 62.25; H 8.07; P 14.59.
C11H17O2P. Calculated, %: C 62.11; H 8.17; P 14.44.
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Phosphinic acids IIb and IIc were synthesized in
a similar way from alkenes Ib and Ic.
1-Phenylhexan-2-ylphosphinic acid (IIb). Yield
38%, yellowish oily substance. IR spectrum, ν, cm–1:
1
2384 s (P–H), 1174 s (P=O). H NMR spectrum, δ,
ppm: 0.82 t (3H, Me, 3J = 7.1 Hz); 1.19–1.28 m, 1.30–
1.53 m, 1.60–1.75 m [6H, (CH2)3Me]; 1.92–2.02 m
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1
CH2Ph), 6.97 d (1H, PH, J = 539 Hz), 7.19–7.64 m
(5H, Ph), 11.60 br.s (1H, OH). 13C NMR spectrum, δC,
2
ppm: 13.7 (Me), 22.6 (CH2Me), 25.9 d (CH2Pr, J =
3
1.7 Hz), 29.4 d (CH2Et, J = 7.8 Hz), 33.0 (CH2Ph),
1
39.7 d (CHP, J = 94.8 Hz), 126.4 (Cp), 128.5 and
3
129.0 (Co, Cm), 138.6 d (Ci, J = 12.4 Hz). 31P NMR
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C 63.70; H 8.46; P 13.69. C12H19O2P. Calculated, %:
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1
2383 s (P–H), 1155 s (P=O). H NMR spectrum, δ,
ppm: 0.81 t (3H, Me, 3J = 7.0 Hz); 1.14–1.25 m, 1.29–
1.51 m, 1.59–1.74 m [8H, (CH2)4Me]; 1.91–2.01 m
(1H, CHP), 2.65–2.74 m and 3.00–3.08 m (1H each,
1
CH2Ph), 6.96 d (1H, PH, J = 541 Hz), 7.18–7.29 m
(5H, Ph), 12.71 br.s (1H, OH). 13C NMR spectrum, δC,
ppm: 14.0 (Me), 22.4 (CH2Me), 26.3 (CH2Bu), 27.1 d
3
(CH2Pr, J = 7.8 Hz), 31.8 (CH2Et), 33.1 (CH2Ph),
1
39.9 d (CHP, J = 94.8 Hz), 126.5 (Cp), 128.6 and
3
129.2 (Co, Cm), 138.9 d (Ci, J = 12.5 Hz). 31P NMR
spectrum: δP 41.15 ppm (1J = 541 Hz). Found, %:
C 64.98; H 8.81; P 12.89. C13H21O2P. Calculated, %:
C 64.84; H 8.77; P 12.61.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 12 2013

DIRECT PHOSPHORYLATION OF β-ALKYLSTYRENES
1841
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