Reactions of elemental phosphorus and phosphine with electrophiles in superbasic systems: XX. Phosphorylation of 4-vinylbenzyl chloride with elemental phosphorus

Article abstract of DOI:10.1134/S1070363207110060

4-Vinylbenzyl chloride reacts with white and red phosphorus, as well as with nanostructured "activated" red phosphorus (complex organophosphorus polymer prepared from white phosphorus under ionizing radiation) in the system concentrated aqueous KOH-dioxan

Full text of DOI:10.1134/S1070363207110060

ISSN 1070-3632, Russian Journal of General Chemistry, 2007, Vol. 77, No. 11, pp. 1880 1886.
Original Russian Text S.F. Malysheva, V.A. Kuimov, N.K. Gusarova, B.G. Sukhov, Yu.V. Smetannikov, N.P. Tarasova, B.A. Trofimov, 2007, published
in Zhurnal Obshchei Khimii, 2007, Vol. 77, No. 11, pp. 1823 1829.
Pleiades Publishing, Ltd., 2007.
Reactions of Elemental Phosphorus and Phosphine
with Electrophiles in Superbasic Systems:
XX.1 Phosphorylation of 4-Vinylbenzyl Chloride
with Elemental Phosphorus
S. F. Malyshevaa, V. A. Kuimova, N. K. Gusarovaa, B. G. Sukhova,
Yu. V. Smetannikovb, N. P. Tarasovab, and B. A. Trofimova
a Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: mal@irioch.irk.ru
b Mendeleev Russian University of Chemical Technology, Moscow, Russia
Received June 28, 2007
Abstract 4-Vinylbenzyl chloride reacts with white and red phosphorus, as well as with nanostructured
activated red phosphorus (complex organophosphorus polymer prepared from white phosphorus under ioniz-
ing radiation) in the system concentrated aqueous KOH dioxane phase-transfer catalyst (20 50 C, argon) to
form tris(4-vinylbenzyl)phosphine oxide, along with (4-vinylbenzyl)- and bis(4-vinylbenzyl)phosphinic acids,
the yield and product ratio being dependent on both the reaction conditions and the nature of the phosphorylat-
ing agent. The nanostructured activated red phosphorus is more reactive than ordinary commercial red
phosphorus.
DOI: 10.1134/S1070363207110060
Tertiary phosphine oxides are key objects in the
chemistry of organophosphorus compounds. They are
widely used as ligands for metal-complex catalysts
[2 5], intermediates for preparation of semiconductor
nanomaterials [6 8], extractants for noble, rare-earth,
and transuranium elements [9 12], flame retardants
for preparation of nonflammable polymers [13 15],
synthons used, e.g., in the Horner Wittig reaction
[16 21] or for preparation of corresponding phos-
phines. Of special interest are functionalized tertiary
phosphines and phosphine oxides possessing styryl
moieties, on the basis of which unique polymeric
catalysts of a new generation [22, 23] and new ma-
terials for nonlinear optics were created [24, 25]. One
of the most convenient synthetic approaches to tertiary
phosphine oxides, including functionally substituted,
unsaturated and chiral, involves direct phosphoryla-
tion of electrophiles with elemental phosphorus in
superbasic systems [1, 3, 26, 27]. In particular, red
phosphorus was reported to react with benzyl chloride
[28, 29] and styrene [30] in the presence of strong
bases, like KOH polar nonhydroxylic solvent (DMSO,
HMPA) or KOH organic solvent phase transfer
catalyst [26], to form, respectively, tribenzyl- and tris-
(2-phenylethyl)phosphine oxides.
We recently published a preliminary report on the
chemoselective formation of tris(4-vinylbenzyl)phos-
phine oxide from red phosphorus and 4-vinylbenzyl
chloride (bifunctional electrophile) under conditions
of phase-transfer catalysis [31].
In the present work with the aim to obtain further
evidence for the perspectiveness and generality of the
method of synthesis of popular organophosphorus
compounds, based on elemental phosphorus and super
bases, we performed a detailed study of the reaction
of white, ordinary (commercial) red phosphorus, and
so-called activated red phosphorus [32, 33] with 4-
vinylbenzyl chloride in the presence of a strong base.
Two samples of activated red phosphorus (1*Pn
and 2*Pn) with the phosphorus content of 70% were
used. The sample 1*Pn was prepared by the action of
1
ionizing radiation of (60Co, 0.78 Gy s ) on a satur-
ated benzene solution of white phosphorus at room
temperature, whereas the sample 2*Pn was synthesized
under similar conditions in the presence of elemental
1
sulfur at the power of absorbed dose of 0.55 Gy s .
For communication XIX, see [1].
Both samples (1*Pn and 2*Pn) contained carbon
1
1880

REACTIONS OF ELEMENTAL PHOSPHORUS AND PHOSPHINE... : XX.
1881
Phosphorylation of 4-vinylbenzyl chloride (11.5 mmol in exp. nos. 1, 3 5 and 5.4 mmol in exp. no. 2)a
Yield, b
%
Conversion of
Exp.
no.
P, mmol
4-vinylbenzyl
RP(O)H(OH)c
R2P(O)OHc
Phosphorus-
R3P=O (I)
chloridee, %
(II)
(III)
containing polymerd, g
f
f
f
f
1
2
3
4
5
Pn, 66.5
Pn, 66.5
P4, 32.3
1*Pn, 38.7
2*Pn, 28
55
49
42
44
54
0.36
0.17
0.25
0.1
98
98
88
86
90
11
2
5
9
6
7
0.4
a
Reaction temperature 45 50 C (exp. nos. 1, 2, 4, 5) and 20 50 C (exp. no. 3). Reaction time 3 h. In all experiments, 209 mmol of
b
KOH, 0.2 g of TEBAC, 0.1 g of hydroquinone, 6 ml of H O and 20 ml of dioxane were used. Yield per taken 4-vinylbenzyl
2
c
d
chloride. Acids II and III were isolated from the reaction mixture after treatment of its aqueous part with HCl. Polymers in
exp. nos. 3 5 were isolated from the organic phase and in exp. nos. 1, 2, after acidification of the reaction mixture. Estimated
e
1
f
from the H NMR spectra. No products formed.
( 10%) and oxygen ( 17%). In addition, 2*Pn con-
tained sulfur (1.3%). The IR spectra of these samples
contain, along with an absorption band at 500 cm
ca. 250 500 nm) [35]. In this case, the developed
surface of the phosphorus polymer provides a high
concentration of surface defects in it, thus enhancing
its chemical activity compared to ordinary commercial
red phosphorus [36 38] possessing no nanostructured
morphology [35].
1
[ (P P)], the following absorption bands: 720
[ (P C)], 1021 [ (P O C)], 1380 [ (P=O)], and
1
1460 cm [ (P OH)], implying chemical bonding of
solvent (benzene) fragments with the phosphorus
polymer formed [34]. In was also established that in
sample 2*Pn sulfur is incorporated into the polymeric
matrix [35].
The phosphorylation of 4-vinylbenzyl chloride with
the system red phosphorus KOH H2O organic sol-
vent (dioxane) phase-transfer catalyst (benzyltriethyl-
ammonium chloride) radical inhibitor (hydroquinone)
proceeds under mild conditions (45 50 C, 3 h)
chemoselectively to form tris(4-vinylbenzyl)phosphine
oxide (I) in up to 55% yield (see table, exp. nos. 1, 2).
The electron microscopy data indicate that the
samples of activated red phosphorus consist of
nanosized incomplete hollow spheres (particle size
3
4
7
1
2
5
6
P
O
Cl
KOH/H2O
(1)
Pn +
I
Under similar conditions, white and both modifi-
cations of activated red phosphorus react with
4-vinylbenzyl chloride to afford not only phosphine
oxide I, but also 4-vinylbenzyl (II) and bis(4-vinyl-
benzyl)phosphinic (III) acids which were isolated
after treatment of the reaction mixture with HCl. The
total yield of compounds I III was 52 66% (see
table, exp. nos. 3 5).
Earlier on the phosphorylation of benzyl chloride
[28], 4-methoxybenzyl chloride [39] and 1-(chloro-
methyl)naphthalene [38] with red phosphorus we ob-
served exclusive or preferential formation of tertiary
phosphine oxides, whereas with white or activated
red phosphorus these reactions stopped on the stages
of formation of secondary phosphine oxides and
phosphinic acids, that is, incomplete arylmethylation
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 11 2007

1882
MALYSHEVA et al.
Cl
P4 (or 1*Pn, 2*Pn) +
OK
H
O
O
OK
OH
H
O
O
OH
P
P
P
P
HCl/H2O
KOH/H2O
(2)
+
+
II
III
products. This result is explained by increased con-
centration of phosphinite or polyphosphinite anions
which are more readily formed upon P P bond
cleavage under the action of strong bases in the case
of white phosphorus (strained tetrahedral molecule) or
activated red phosphorus (contains biographical
defects [36]) as compared to ordinary red phosphorus
which is a reticulate homopolymer [35, 36].
phosphorus-containing dendrimers [40, 41], including
nanosized structures [42] widely used in coordination
chemistry and catalysis [43, 44]. Furthermore, this
phosphine oxide is an effective comonomer for pre-
paring nonflammable polymer compositions [45] and
promising polydentate ligands [23, 46].
The prepared phosphinic acids II and III can be
used as synthons in organic synthesis [47 51], in par-
ticular, for purposeful design of phosphaisocoumarins
[50, 51]. On the basis of polystyrenephosphonic acid,
highly effective hemo- and enterosorption materials
have been created [52], used, in particular, for extrac-
tion of radionuclides [53].
It should be mentioned that the phosphorylation of
4-vinylbenzyl chloride with elemental phosphorus
gives, along with the main products I III, phosphorus-
containing reticulate polymers insoluble in ordinary
organic solvents and water (9 32% of the total weight
of the compounds formed). Organophosphorus poly-
mers become virtually the main products, when the
reactions under consideration are carried out without
hydroquinone. The strong tendency of compounds I
III for oligo- and polymerization is already observed
at room temperature, but they are stable enough when
stored in a refrigerator (0 5 C).
EXPERIMENTAL
Electron microscopy of the samples of activated
red phosphorus was performed on a Tesla BS
340 scanning electron microscope. The IR spectra
were recorded on a Specord IR-75 instrument. The
1H, 13C and 31P NMR spectra were measured on a
Bruker DPX 400 spectrometer (400, 100, and
161.98 MHz, respectively) in CDCl3 solutions against
internal HMDS. All experiments were performed
under argon.
Since the samples of activated red phosphorus
contained P R bonds (where R is benzene fragment),
and the phosphorus sulfur sample 2*Pn, in addition,
P S bonds, we could expect that their phosphorylation
reactions with 4-vinylbenzyl chloride would provide
by-products having such fragments. Apparently, such
products are actually formed, as evidenced by the
presence in the 31P NMR spectra of unidentified
The samples of nanosized activated red phos-
phorus 1*Pn and 2*Pn were prepared at room tempera-
ture by the action of ionizing radiation of 60 C on
saturated benzene solutions of white phosphorus with
signals of low intensity at
12.41, 17.82, 24.02, and
P
29.64 ppm. However, we failed to isolate these com-
pounds and to prove their structure.
1
the power of the absorbed dose of 0.78 Gy s (1*Pn)
1
and of 0.55 Gy s (2*Pn; in the presence of sulfur)
Thus, the direct reaction of 4-vinylbenzyl chloride
with elemental phosphorus in the presence of strong
bases allows facile formation of C P bonds and pro-
vides promising organophosphorus compounds. Thus,
combining three vinyl substituents and a phosphine
oxide group in the molecule of phosphine oxide I
represents a principally new approach to the design of
and with the same absorbed dose of 190 kGy. The
resulting samples were washed with benzene to re-
move unreacted white phosphorus, dried under va-
cuum, and analyzed. Found, %: C 10.38; H 3.09;
P 69.23; O 17.3 (1*Pn) and C 10.19; H 2.22; P 70.63;
S 1.32; O 16.96 (2*Pn).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 11 2007

REACTIONS OF ELEMENTAL PHOSPHORUS AND PHOSPHINE... : XX.
1883
Reaction of 4-vinylbenzyl chloride with red
phosphorus: Synthesis of tris(4-vinylbenzyl)phos-
phine oxide (I) (exp. no. 1). To a heated (45 50 C)
suspension of 2.06 g of red phosphorus, 0.21 g of
benzyltriethylammonium chloride, 11.7 g of KOH,
6 ml of water, 15 ml of dioxane, and 0.1 g of hydro-
quinone, a solution of 1.76 g of 4-vinylbenzyl chlo-
ride in 5.5 ml of dioxane was added dropwise upon
stirring over the course of 1.5 h. The reaction mixture
was stirred for another 1.5 h at 45 50 C, diluted with
water, extracted with benzene (3 30 ml), the solvent
was removed under reduced pressure, and the residue
was dried in a vacuum to obtain 0.85 g of a crude
[ (OH)], 1512, 1423, 1400 [ (C=C Ph)], 1126
[ (P=O)], 997 [ (OH)], 850 [ (CH Ph)]. Found, %:
C 57.05; H 6.02; Cl 1.19; P 10.78; ash 24.96.
Reaction of 4-vinylbenzyl chloride with white
phosphorus: Synthesis of tris(4-vinylbenzyl)phos-
phine oxide (I) and 4-vinylbenzylphosphinic acid
(II) (exp. no. 3). To a mixture of 1.0 g of white phos-
phorus, 0.1 g of hydroquinone and 0.21 g of benzyl-
triethylammonium chloride in 20 ml of dioxane,
11.7 g of KOH and 6 ml of water were added and
then 1.76 g of 4-vinylbenzyl chloride was added
dropwise at room temperature over the course of 1 h.
The reaction mixture was stirred for another 1 h at
room temperature and 1 h at 45 50 C, cooled, diluted
with water, and extracted with benzene (3 30 ml).
Benzene was distilled off, and the residue dried in
vacuum to afford 0.90 g of product A (light yellow
1
product whose H NMR spectrum contained, along
with signals of phosphine oxide I, a singlet at
4.54 ppm, related to the starting 4-vinylbenzyl
chloride (conversion 98%).
waxy material) whose 31P NMR spectrum contained
the following signals, P, ppm: 47.34 (phosphinic acid
III), 41.28 (phosphine oxide I), and 36.14 (1JPH
458 Hz) [probably, bis(4-vinylbenzyl)phosphine oxide
which under further treatment is oxidized to phos-
phinic acid III]. The intensity ratio of the above
signals was 1:18.2:3, respectively. The 1H NMR
spectrum of product A, contained, along with the
above signals, a singlet at 4.54 ppm related to the
starting 4-vinylbenzyl chloride (conversion 88%).
Product A was dissolved in 5 ml of benzene. Product
B precipitated as a white powder and was separated
by filtration [0.25 g, (22% of the total weight of the
reaction products)]; the product is insoluble in water
and organic solvents and does not melt up to 300 C.
Phosphine oxide I, 0.84 g (55%), needles, mp 136
1
140 C (hexane). IR spectrum, cm : 3080, 3030
[ (=CH, =CH2)], 2990, 2950, 2850 [ (CH, CH2)],
1620 [ (C=C)], 1600, 1500, 1400 [ (C=C Ph)], 1180
1
[ (P=O)], 1110, 980, 900, 850 [ (CH Ph)]. H NMR,
2
, ppm, (J, Hz): 2.98 d (6H, H1, JPH 13.7), 5.22 d
3
3
(3H, H7, JHH 10.7), 5.71 d (3H, H7, JHH 17.6),
6.67 d.d (3H, H6), 7.17 7.33 m (12H, C6H4). 13C
NMR, C, ppm, (J, Hz): 35.27 d (C1, JPC 60.6),
1
113.89 C7, 126.58 C3, 130.01 C4, 131.17 d (C2, JPC
2
7.2), 136.28 C6, 136.38 C5. 31P NMR,
41.28 ppm.
P
Found, %: C 80.98; H 6.87; P 8.01. C27H27PO. Cal-
culated, %: C 81.38; H 6.83; P 7.77.
The aqueous layer was acidified with 35% HCl to
pH 4, and 15 ml of CHCl3 was added (no layer se-
paration occurred). The suspension that formed was
diluted with 15 ml of benzene, the solvents and water
were removed under reduced pressure, and a pasty
product was obtained. It was successively washed
with water (to remove KCl), acetone, and ether and
dried in vacuum to obtain 0.36 g of a product (30% of
the total weight of the reaction products) as a beige
powder insoluble in water and ordinary organic sol-
1
IR spectrum, cm : 3080, 3020, 3000 [ (=CH, =CH2)],
2900 [ (CH)], 2350, 1660 [ (OH)], 1620 [ (C=C)],
1600, 1500, 1400 [ (C=C Ph)], 1160 [ (P=O)], 1115
[ (OH)], 985, 900, 850 [ (CH Ph)]. Found, %: C
72.55; H 6.30; P 8.36. C27H27PO. Calcd, %: C 81.37;
H 6.83; P 7.77. The benzene solution was repreci-
pitated into hexane to obtain 0.64 g (42%) of phos-
phine oxide I.
1
The aqueous layer was acidified with 35% aqueous
HCl to pH 4 5, extracted with dichloromethane, and
the extract was dried over CaCl2. The solvent was
then removed, and the residue was dried in vacuum to
obtain 0.25 g of a product as a light yellow waxy
material which was dissolved in chloroform and re-
precipitated into ether to afford 0.23 g (11%) of
phosphinic acid II, mp 98 100 C (dichloromethane).
vents and not melting up to 300 C. IR spectrum, cm :
3032, 3018 [ (=CH, =CH2)], 2926, 2920, 2840
[ (CH)], 2330, 1637 [ (OH)], 1511, 1450, 1423, 1400
[ (C=C Ph)], 1232, 1126 [ (P=O)], 997 [ (OH)], 852
[ (CH Ph)]. Found, %: C 57.46; H 5.49; Cl 2.45;
P 11.74; ash 22.74.
Under similar conditions but with 0.83 g of 4-vinyl-
benzyl chloride (exp. no. 2), phosphine oxide I was
obtained in 49% yield, along with 0.17 g (32% of the
total weight of the reaction products) of a phosphorus-
containing reticulate polymer (insoluble in water and
organic solvents) with the following absorption bands
1
IR spectrum, cm : 3080, 3040, 3000 [ (=CH, =CH2)],
2900, 2850 [ (CH)], 2620 [ (OH)], 2410 [ (PH)],
2240, 2140, 1680 [ (OH)], 1620 [ (C=C)], 1500,
1400, 1390 [ (C=C Ph)], 1100 [ (P=O)], 980
[ (OH)], 960 [ (P=O)], 900, 820 [ (CH Ph)]. 1H
1
2
in the IR spectrum, cm : 2930 [ (CH)], 2323, 1638
NMR, , ppm, (J, Hz): 3.07 d (2H, H1, JPH 18.4),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 11 2007

1884
MALYSHEVA et al.
5.21 d (1H, H7, 3JHH 10.8), 5.70 d (1H, H7, 3JHH 17.6),
6.66 d.d (1H, H6), 6.93 d (1H, PH), 7.14 7.34 m (4H,
C6H4), 8.97 (1H, OH). 13C NMR, C, ppm, (J, Hz):
6.62 d.d (2H, H6), 7.12 7.30 m (8H, C6H4), 7.68 (1H,
1
OH). 13C NMR, C, ppm, (J, Hz): 35.17 d (C1, JPC
88.3), 113.75 C7, 126.34 and 126.37 C3, 130.15 and
2
130.20 C4, 130.70 (C2, JPC 8.1), 136.17, 136.21 C5,
37.37 d (C1, 1JPC 87.6), 114.07 C7, 126.69 C3, 128.94
1
136.29 C6. 31P NMR:
51.73 ppm, JPH 558.7 Hz.
C4, 130.02 (C2), 136.27 C6, 136.72 C5. 31P NMR:
36.82 ppm, JPH 558.7 Hz. Found, %: C 59.78; H
P
P
1
Found, %: C 71.97; H 6.33; P 10.59. Calculated, %:
C 72.47; H 6.42; P 10.38.
6.55; P 16.80. C9H11O2P. Calculated, %: C 59.34;
H 6.09; P 17.00.
Methylene chloride was removed to obtain 0.1 g of
a compound, containing, according to the 31P NMR
spectrum, acids II and III in a 9:1 ratio. The yield of
The yield of phosphinic acid III, estimated from
1
the H and 31P NMR spectra, was 9%.
1
acid II estimated from the H and 31P NMR spectra
Reaction of 4-vinylbenzyl chloride with ac-
tivated red phosphorus: Synthesis of bis(4-vinyl-
benzyl)phosphinic acid (III) (exp. no. 5). To a mix-
was 5%.
Under similar conditions, from red phosphorus
1*Pn compounds I III were obtained in 44, 2, and 6%
yields, respectively, along with 0.1 g (9% of the total
weight of the reaction products) of a phosphorus-
containing reticulate polymer insoluble in ordinary
organic solvents and water and not melting up to
ture 1.0 g of red phosphorus 2*Pn, 0.20 g of benzyltri-
ethylammonium chloride, and 0.1 g of hydroquinone
in 20 ml of dioxane, 11.7 g of KOH and 6 ml of water
were added and then 1.76 g of 4-vinylbenzyl chloride
was added dropwise at 45 50 C over the course of
1 h. The reaction mixture was stirred for another 2 h
at 45 50 C, cooled, and diluted with water. A pre-
cipitate formed and was filtered off, washed on the
filter with water to neutral reaction and then with
acetone and ether, and dried in a vacuum to obtain
0.4 g (28% of the total weight of the reaction pro-
ducts) of a beige powder insoluble in water and or-
ganic solvents, and not melting up to 300 C. IR spec-
1
300 C. IR spectrum, cm : 3080, 3020, 3000 [ (=CH,
=CH2)], 2900, 2850 [ (CH)], 2600, 2300, 1680
[ (OH)], 1620, 1600, 1500, 1400 [ (C=C Ph)], 1110
[ (P=O)], 970 [ (OH)], 950 [ (P=O)], 890, 840
[ (CH Ph)]. Found, %: C 59.62; H 5.78; P 10.25.
ACKNOWLEDGMENTS
1
This work was financially supported by the Rus-
sian Foundation for Basic Research (project no. 05-
03-32859) and Siberian Branch of the Russian
Academy of Sciences (integrative project no. 32).
trum, cm : 3080, 3020, 3000 [ (=CH, =CH2)], 2900,
2850 [ (CH)], 2640, 2330, 1680 [ (OH)], 1610, 1600,
1500, 1480, 1450, 1420, 1400 [ (C=C Ph)], 1110
[ (P=O)], 980 [ (OH)], 940 [ (P=O)], 900, 840
[ (CH Ph)]. Found, %: C 55.44; H 5.72; P 12.63.
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IR spectrum, cm : 3080, 3030 [ (=CH, =CH2)], 2900,
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