Acetylene phosphorylation with elemental phosphorus in the KOH-DMSO system

Article abstract of DOI:10.1134/S1070363214120081

Reaction of red phosphorus with acetylene in multiphase superbasic KOH-DMSO system has been studied. The phosphorylation of acetylene results in poly(divinylphosphinic acid).

Full text of DOI:10.1134/S1070363214120081

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 12, pp. 2401–2404. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © B.A. Trofimov, S.F. Malysheva, A.V. Artem’ev, N.A. Belogorlova, L.V. Klyba, N.K. Gusarova, 2014, published in Zhurnal Obshchei
Khimii, 2014, Vol. 84, No. 12, pp. 1983–1986.
Acetylene Phosphorylation with Elemental Phosphorus
in the KОН–DMSO System
B. A. Trofimov, S. F. Malysheva, A. V. Artem’ev,
N. A. Belogorlova, L. V. Klyba, and N. K. Gusarova
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: boris_trofimov@irioch.irk.ru
Received August 4, 2014
Abstract—Reaction of red phosphorus with acetylene in multiphase superbasic KOH–DMSO system has been
studied. The phosphorylation of acetylene results in poly(divinylphosphinic acid).
Keywords: acetylene, red phosphorus, hydrophosphorylation, polymer of divinylphosphinic acid
DOI: 10.1134/S1070363214120081
Direct reactions of elemental phosphorus with
organic electrophiles in superbasic systems like alkali
hydroxide: polar aprotic solvent (dimethylsulfoxide
DMSO, hexamethylphosphoramide HPMA) or under
conditions of interphase catalysis are convenient pre-
paration methods for organophosphorus compounds,
alternative to conventional procedures [1–3]. Basing
on this approach, such electrophiles as phenylace-
tylene, aryl- and hetarylalkenes, and organyl halides
have been phosphorylated, opening a way to simple
preparation of previously unknown or difficultly ac-
cessible phosphines, phosphine oxides, and organo-
phosphorus acids [1–3]. The reaction of acetylene and
elementary (red) phosphorus has been poorly studied;
it is known to yield traces of trivinylphosphine [4]. The
reaction has been carried out in a KOH–H2O–N2H4–
HPMA system at 105–115°С in a pressure reactor
(acetylene pressure of 15 at).
multiphase superbasic KОН–DMSO (H2O) medium.
Minor admixture of water (~4 vol % with respect to
DMSO) was applied to accelerate proton transfer process.
Polymer of divinylphosphinic acid (I) was formed
within 3 h at 100°С in the described system (pressure
reactor, initial acetylene pressure of 14 at, room
temperature), the product yield was 18% with respect
to phosphorus. The side organophosphorus products,
ethylphosphinic acid II and trivinylphosphine oxide
III were isolated in 5% and 2% yields respectively
(Scheme 1).
Polymer I was a light-brown powder, insoluble in
water and organic solvents but almost completely
(80%) soluble in aqueous alkali. The presence of the
fraction insoluble in aqueous alkali pointed to the
formation of crosslinked (three-dimensional) struc-
tures. Elemental analysis data for compound I
coincided with the theoretical composition of poly(di-
vinylphosphinic acid). Acid-base titration data were in
line with the polymeric acid structure as well. IR
Here we present preliminary results of investigation
of red phosphorus reaction with acetylene in a
Scheme 1.
O
H
l
O
KOH_DMSO (H2O)
P
O
P
HC CH + Pn
+
+
HO
P
100oC, 3 h
OH
m
I (18%)
II (2%)
III (5%)
2401

2402
TROFIMOV et al.
Scheme 2.
P
P
−OH, HC≡CH
P
P
HC≡CH
P
P
P
−OH
C
A
Pn
P
P
−OH, HC≡CH
P
P
O
OH
H
O
OH
O
HC≡CH
P
P
P
O
P
P
+
+
O
II
E
F
B
D
O
OH
H
[H]
E
P
III
l
nF
HO P
O
m
I
Scheme 3.
O
H3C
H2O
−OH
HC≡CH
−OH
n
H
OH
IV
spectrum of polymer I contained the absorption band
at 961 cm–1, typical of P–OH group; the band at
1157 cm–1 was assigned to the P=O vibrations, and the
band at 753 cm–1 was assigned to the P–C vibration.
Broad bands at 3450–3300 and 1650–1630 cm–1 cor-
responded to vibrations of the OH end groups.
Stretching and bending vibrations of the С–H bonds
gave rise to the bands at 2920–2890 and 1412 cm–1,
respectively.
divinylphosphinic (F) acids (from phosphonite anions).
The acid E hydrogenation with hydrogen evolving in
the course of reaction of red phosphorus with alkali
gave ethylphosphinic acid III, whereas anionic poly-
merization of divinylphosphinic acid F yielded poly-
mer I (Scheme 2).
Traces of polyacetaldehyde IV were identified
among the reaction products as well. Under the reac-
tion conditions, acetaldehyde might be formed via
base-catalyzed hydration of acetylene (water vinyla-
tion) (Scheme 3).
According to the commonly accepted views [1–3],
the cleavage of the P–P bonds of elemental phosphorus
in the KОН–DMSO system led to generation of
polyphosphide (A) and polyphosphinite (B) anions. In
the studied case, the expected pathway was the anions
addition to acetylene, and the subsequent splitting of
the rest P–P bonds in the formed intermediate C and D
should yield trivinylphosphine (from phosphide ions)
along with phosphine oxide II, mono- (E) and
Mass spectrum of polymer IV (MALDI) contained
mainly the peaks assigned to polyacetaldehyde of
various polymerization degree (see figure).
The optimized phosphorylation reaction of
acetylene can be used for preparation of polydivinyl-
phosphinic acid, a new promising fire-retarding agent
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 12 2014

ACETYLENE PHOSPHORYLATION WITH ELEMENTAL PHOSPHORUS
2403
Irel × 104
m/z
MALDI mass spectrum of polymer IV cations. m/z 749 H[–C2H4O–]17, n = 23, Mn = 1041.030; m/z 765 HO[–C2H4O–]17, n = 22,
Mn = 998.230; and m/z 777 C2H5[–C2H4O–]17, n = 24, Mn = 1072.050.
to be applied for fabrics and polymeric materials. The
polyacid can be used as efficient cationite and ion
sorbent as well (after crosslinking).
to pH ~ 1. The formed precipitate was filtered off,
washed with DMSO (2 × 10 mL), water (4 × 20 mL),
and ethanol (2 × 10 mL), and dried in a vacuum
(1.5 mmHg, 40–45°С). The DMSO-soluble fraction
(polymer IV) was identified by means of MALDI mass
spectroscopy. Yield of polymer I 2.1 g (18%).
EXPERIMENTAL
IR spectra were recorded using a Bruker Vertex 70
Water and DMSO were distilled off from the
filtrate in a vacuum (~1.5 mmHg), the residue was
diluted with ethanol, acidified with conc. HCl (3 mL),
and evaporated to dryness. The residue was diluted
with water (≈15 mL) and extracted with chloroform
(3 × 10 mL). The extract was dried over MgSO4, the
solvent was eliminated, and the residue was dried in a
vacuum. Yield of ethylphosphinic acid III 0.45 g
(5%).
1
spectrometer. Н, 13С, and 31Р NMR spectra were
registered with a Bruker DPX-400 spectrometer (400.13,
101.61, and 161.98 MHz, respectively) in CDCl3
solution with 85% Н3РО4 as an external reference
(31Р). Mass spectrum (MALDI) was recorded using a
UltrafleXtreme III TOF/TOF (Bruker Daltonics) mass
spectrometer equipped with a nitrogen laser (337 nm)
operating in the reflectron mode. The results were
processed using FlexAnalysis 3.3 (Bruker Daltonics)
software. The sampling was performed following the
dried drop method.
Gaseous reaction products were condensed from
the reactor into a cooled trap (–78°С). The condensate
(0.6 g) was a colorless liquid containing trivinyl-
phosphine (δP –26.7 ppm) and trivinylphosphine oxide
(δP 17.8 ppm). Trivinylphosphine oxide (0.23 g, 2%)
was isolated from the mixture after 1 d keeping in air
at 23°C and subsequent chromatographic separation
(silica gel, chloroform as eluent).
Reaction of red phosphorus with acetylene in
KОН–DMSO. A mixture of red phosphorus (3.1 g,
0.100 mol), KОН·0.5H2O powder (8.00 g, 0.123 mol),
50 mL of DMSO, and 2 mL of water was placed in a
1 L rotating steel reactor and saturated with acetylene
to the pressure of 14 at. Acetylene was then released to
eliminate air from the reaction mixture, and then the
reactor was again saturated with acetylene to 14 at (at
room temperature). The reaction mixture was heated at
100°C during 3 h. After cooling, the reaction mixture
was diluted with water (50 mL) and acidified with HCl
Polymer of divinylphosphinic acid (I). Yield 2.1 g
(18%), light-brown powder, carbonized upon heating
in a vacuum at > 210°C. IR spectrum, ν, cm–1: 3450–
3300 s (O–H), 2920–2890 s (C–H), 1650–1630 s
[δ(O–H)], 1412 m [δ(C–H)], 1157 s (P=O), 961 m
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 12 2014

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TROFIMOV et al.
[δ(P–OH)], 753 m (C–P). Found, %: С 41.01; Н 6.21;
P 27.50. (C4H7O2P)n. Calculated, %: С 40.69; Н 5.98;
P 26.23. Acid–base titration: 14.9% of OН groups (cal-
culated 14.4%).
25.41; Н 7.37; P 32.71. C2H7O2P. Calculated, %: С
25.54; Н 7.50; P 32.93.
ACKNOWLEDGMENTS
Trivinylphosphine oxide (II). Yield 0.23 g (2%),
1
This work was financially supported by President
of the Russian Federation (program of support of
leading scientific schools, grant NSh-156.2014.3).
colorless crystals, mp 95–97°C. Н NMR spectrum, δ,
ppm: 6.27 m (1H), 6.18 m (1H), 6.23 m (1H, 2JHH 2.0,
3
2
3
3
3JHH 12.5, JHH 18.9, JPH 23.6, JPH 41.9, JPH
22.5 Hz). 13C NMR spectrum, δС, ppm: 134.1 (CH2),
130.54 (CH, JPC 99.6 Hz). 31P NMR spectrum: δР
1
REFERENCES
17.7 ppm. Found, %: С 56.11; Н 7.17; P 24.01.
C6H9OP. Calculated, %: С 56.25; Н 7.08; P 24.18.
1. Trofimov, B.A., Rakhmatulina, T.N., Gusarova, N.K.,
and Malysheva, S.F., Russ. Chem. Rev., 1991, vol. 60,
no. 12, p. 1360.
2. Trofimov, B.A. and Gusarova, N.K., Mendeleev
Commun., 2009, vol. 19, p. 295. DOI: 10.1016/
j.mencom.2009.11.01.
3. Gusarova, N.K., Arbuzova, S.N., and Trofimov, B.A.,
Pure Appl. Chem., 2012, vol. 84, p. 439. DOI: 10.1351/
PAC-CON-11-07-11.
4. Potapov, V.Α., Amosova, S.V., and Khangurov, A.V.,
Russ. Chem. Bull., 1989, p. 195.
Ethylphosphinic acid (III). Yield 0.45 g (5%),
colorless powder, mp 142°C. IR spectrum, ν, cm–1:
1
2360 s (P–H), 1171 s (P=O). Н NMR spectrum, δ,
3
3
ppm: 1.11 d.t (3H, Me, JHH 7.7 Hz, JPH 21.2 Hz),
1.72 d.q (2H, 3JHH 7.7 Hz, JPH 16.2 Hz, JHPCH 1.7 Hz,
2
3
1
3
CH2P, 6.99 d.t (1H, PH, JPH 541 Hz, JHPCH 1.7 Hz),
10.95 s (1H, OH). 13C NMR spectrum, δС, ppm: 4.4
2
2
31
(Me, J 3.3 Hz), 22.0 d (CH2P, J 93.2 Hz). P NMR
spectrum: δР 41.27 ppm (d, J 541 Hz). Found, %: С
1
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 12 2014