One-pot microwave synthesis of tertiary phosphine sulfides directly from aromatic alkenes, elemental phosphorus and sulfur in KOH-DMSO system

Article abstract of DOI:10.1080/17415993.2013.809454

Aromatic alkenes (vinylbenzene, 1-(tert-butyl)-4-vinylbenzene, 1-chloro-4-vinylbenzene) react with red phosphorus and elemental sulfur in the superbasic system KOH-DMSO(H2O) under microwave irradiation (600 W, 6-8 min, Ar) in the presence of hydroquinone to afford tris(2-phenylethyl)-, tris[2-(4- ^tBu-phenyl)ethyl]- and tris[2-(4-Cl-phenyl)ethyl]phosphine sulfides in 53%, 38% and 42% yield, respectively.

Full text of DOI:10.1080/17415993.2013.809454

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One-pot microwave synthesis of
tertiary phosphine sulfides directly
from aromatic alkenes, elemental
phosphorus and sulfur in KOH–DMSO
system
Vladimir A. Kuimova, Svetlana F. Malyshevaa, Nina K. Gusarovaa,
Anastasiya O. Korochevaa & Boris A. Trofimova
a Siberian Branch of the Russian Academy of Sciences, A. E.
Favorsky Irkutsk Institute of Chemistry, 1 Favorsky Str., 664033
Irkutsk, Russian Federation
Published online: 26 Jul 2013.
To cite this article: Vladimir A. Kuimov, Svetlana F. Malysheva, Nina K. Gusarova, Anastasiya O.
Korocheva & Boris A. Trofimov (2014) One-pot microwave synthesis of tertiary phosphine sulfides
directly from aromatic alkenes, elemental phosphorus and sulfur in KOH–DMSO system, Journal of
Sulfur Chemistry, 35:2, 137-144, DOI: 10.1080/17415993.2013.809454
To link to this article: http://dx.doi.org/10.1080/17415993.2013.809454
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Journal of Sulfur Chemistry, 2014
Vol. 35, No. 2, 137–144, http://dx.doi.org/10.1080/17415993.2013.809454
One-pot microwave synthesis of tertiary phosphine sulfides
directly from aromatic alkenes, elemental phosphorus and
sulfur in KOH–DMSO system
Vladimir A. Kuimov, Svetlana F. Malysheva, Nina K. Gusarova, Anastasiya O. Korocheva and
Boris A. Trofimov*
Siberian Branch of the RussianAcademy of Sciences,A. E. Favorsky Irkutsk Institute of Chemistry, 1 Favorsky
Str., 664033 Irkutsk, Russian Federation
(Received 15 April 2013; final version received 23 May 2013)
Aromatic alkenes (vinylbenzene, 1-(tert-butyl)-4-vinylbenzene, 1-chloro-4-vinylbenzene) react with
red phosphorus and elemental sulfur in the superbasic system KOH–DMSO(H2O) under microwave
irradiation (600W, 6–8 min, Ar) in the presence of hydroquinone to afford tris(2-phenylethyl)-, tris[2-
(4-tBu-phenyl)ethyl]- and tris[2-(4-Cl-phenyl)ethyl]phosphine sulfides in 53%, 38% and 42% yield,
respectively.
Keywords: aromatic alkenes; red phosphorus; elemental sulfur; microwave irradiation; tertiary phos-
phine sulfides
1. Introduction
Tertiary phosphine sulfides find application as extractants for noble rare-earth metals and
radionuclides,[1–4] modifiers for synthetic rubbers and petroleum resins,[5] surfactants, chemi-
cal sensitizers in photographic materials,[6–11] additives to lubricating oils and electrolytes,[12]
adhesive compositions,[13] as well as components of insect repellents, insecticides and fungi-
=
cides. The functional P S group constitutes an important part of some pharmacophores.[14,15]
Tertiary phosphine sulfides are also used as ligands in the design of new metal complex cata-
lysts [16–25] showing, in some cases, better catalytic activity than that of the complexes with
tertiary phosphines [20,22]. In several reactions, tertiary phosphine sulfides are employed as co-
catalysts.[26,27]Apart from that, phosphine sulfides are valuable building blocks in the synthesis
*Corresponding author. Email: boris_trofimov@irioch.irk.ru
© 2013 Taylor & Francis

138 V.A. Kuimov et al.
of corresponding tertiary phosphines,[28] as well as co-reagents for the preparation of CdS–CdSe
nanocrystal dots and rods.[29]
A number of methods have been proposed for the synthesis of tertiary phosphine sulfides. In
=
general, they are prepared by the reaction of S PCl3 with organometallic reagents.[30] Among
other methods for their synthesis are oxidation of the tertiary phosphines with elemental sulfur
or reoxidation of tertiary phosphine oxides with less accessible sulfurizing reactants such as
B2S3,[31] P2S5,[32] Lawesson’s reagent,[33–38] and POCl3–H2S.[39,40]
Here, we report a new approach for the synthesis of tertiary phosphine sulfides via one-
pot reaction of aromatic alkenes with red phosphorus and elemental sulfur in the superbase
multicomponent suspension KOH–DMSO.
It is known [41–43] that aromatic alkenes are phosphorylated with the triad Pred –KOH–
DMSO(H2O) at 90–130◦C for 3 h to form tertiary phosphine oxides in 30–77% yields. Using
microwave irradiation the reaction affords the phosphine oxides in 82–85% yields in 4–6 min
[41–43] (Scheme 1).
Scheme 1. Reaction of red phosphorus with aromatic alkenes in the KOH–DMSO system under
microwave assistance.
Elemental sulfur alone also reacts with vinylbenzene in the KOH–DMSO–H2O suspension
under microwave irradiation (600W, 4 min) to give 2,4- and 2,5-diphenylthiophenes in 30% total
yield [44] (Scheme 2).
Scheme 2. Reaction of elemental sulfur with vinylbenzene in the KOH–DMSO system under
microwave assistance.
The three-component reaction between aromatic alkenes, red phosphorus and elemental sulfur
had not been previously reported in the literature.
2. Results and discussion
Aromatic alkenes 1a–c were shown to react with red phosphorus and elemental sulfur (1:1:1
molar ratio) in the superbasic system KOH–DMSO(H2O) under microwave irradiation (600W,
6–8 min, Ar, hydroquinone, as a radical processes inhibitor) to afford tris(2-phenylethyl)-, tris[2-
(4-tBu-phenyl)ethyl]- and tris[2-(4-Cl-phenyl)ethyl]phosphine sulfides 2a–c in 53%, 38% and
42% yields, respectively (Table 1). Noteworthy, it was necessary to introduce sulfur to the reaction
mixture in a second step 5–7 min after the alkene 1–Pred–KOH–MSO–(H2O) suspension was

Journal of Sulfur Chemistry 139
Table 1. One-pot reaction of aromatic alkenes with red phosphorus and sulfur in a KOH–DMSO
suspension.a
Aromatic alkenes
1a–c (mmol)
Pred
mmol
,
S8,
mmol
KOH,
mmol
Products 2, 3
Yield of
(their molar ratio)b
2, %c
=
PhCH CH2, 1a (100)
100
32.2
7.0
100
30.0
7.2
178.5
89.2
12.5
2a,3a (2.3:1)
2b,3b (4.5:1)
2c,3c (1.4:1)
2a, 53
2b, 38
2c, 42
t
=
4- BuC6H4CH CH2, 1b (30.0)
=
4-ClC6H4CH CH2, 1c (7.2)
aAll steps of the experiments were carried out under microwave irradiation (600W, 6–8 min) in argon atmosphere.
bMolar ratio of the compounds 2 and 3 were calculated from the 31P NMR spectra of the crude products. In the reaction
mixture formed at the first step of the reaction (before addition of elemental sulfur), the corresponding tertiary phosphines
4a–c were also detected (31P NMR data).
cIsolated yield.
irradiated. The process was finished after an additional 1 min of MW-irradiation. Under these
conditions the corresponding tertiary phosphine oxides 3a–c are also formed (Table 1).
Cleavage of the P–P bonds in red phosphorus with hydroxide anions [45] is a key step in this new
reaction. This step is likely to form highly active P-centered nucleophiles such as polyphosphide
A and polyphosphinite B anions. These anions then subsequently react with electrophiles 1a–c
to give tertiary phosphines 4a–c or phosphine oxides 3a–c. The phosphines 4a–c are further
sulfurized by elemental sulfur to afford phosphine sulfides 2a–c (Scheme 3).
Scheme 3. Plausible mechanism for the multi-component reaction between aromatic alkenes,
red phosphorus and elemental sulfur in the KOH–DMSO(H2O) system.
Using vinylbenzene as an example, it has been shown that simultaneous irradiation (600W,
7 min, Ar) of all of the components of the reaction mixture (1a–Pred–S8–KOH–DMSO–H2O–
hydroquinone) decreases the total yield of phosphine chalcogenides, 2a and 3a, down to ∼33%
(their molar ratio 1:1.5) as well as producing 2,4- and 2,5-diphenylthiophenes in 21% total yield
(data of mass spectrometry) (Scheme 4).

140 V.A. Kuimov et al.
Scheme 4. Simultaneous irradiation of vinylbenzene, red phosphorus and elemental sulfur in
the KOH–DMSO suspension.
Without microwave activation, the reaction between vinylbenzene, red phosphorus and
elemental sulfur proceeds in the KOH–DMSO(H2O) suspension upon heating (90–95◦C) for
3 h to give phosphine sulfide 2a and phosphine oxide 3a in a 49% total yield (their molar ratio
∼1:10).
The addition of elemental sulfur to a pre-heated (90–95◦C) suspension of vinylbenzene–
Pred–S8–KOH–DMSO–H2O–hydroquinone via three portions in 20 min equal time spans and
subsequent additional heating of the resultant reaction mixture (90–95◦C, 2 h) affords phosphine
sulfide 2a and phosphine oxide 3a in a 57% total yield (their molar ratio ∼1:1).
It has been reported,[46] that tris(2-phenylethyl)phosphine chalcogenides 2a and 3a are
effective extracting agents of gold from low-acidic solutions. Additionally, phosphine sulfide
2a is known to exert high extracting ability towards silver.[46]
In addition, we have found that phosphine sulfide 2a or its mixture with phosphine oxide 3a
(∼1:1) can be successfully employed for extraction of palladium, platinum, lead and cadmium
from hydrochloride solutions. These investigations are now under way and their results will be
published as a full paper elsewhere.
3. Conclusion
Thus, we have developed a straightforward facile synthesis of tertiary phosphine sulfides via the
one-pot multi-component reaction of aromatic alkenes, red phosphorus and elemental sulfur in
the KOH–DMSO(H2O) system. The reaction is activated by MW-irradiation to afford the target
compounds in good yields. The synthesized tertiary phosphine sulfides are effective extractants
of diverse metals, prospective ligands for metal complexes, modifiers for synthetic rubbers and
petroleum resins, additives to lubricating oils and electrolytes, precursors to agrochemicals and
building blocks for organic synthesis.
4. Experimental
4.1. General
Melting points (uncorrected) were measured on a Kofler micro hot-stage apparatus.
The microanalyses were performed on a Thermo Scientific Flash 2000 organic element analyzer.
Fourier transform IR spectra were run on a Bruker Vertex 70 instrument. Raman spectra were
run on a Varian FT-Raman. The 1H, 13C and 31P spectra were recorded on a BrukerAV-400 spec-
trometer (400.13, 100.61 and 161.98 MHz, respectively) and referenced to H3PO4 (31P NMR).
Chemical shifts (δ) are expressed in ppm downfield from hexamethyldisiloxane, CHCl3 as internal
standards. One should note that phosphine sulfides 2a,c were spectrally characterized in this paper
for the first time. All steps of the experiment were carried out in argon atmosphere. Red phos-
phorus (KSAN “SIA”), 1-(tert-butyl)-4-vinylbenzene (Alfa-Aesar), 1-(chloro)-4-vinylbenzene
(Alfa-Aesar), KOH (∼15% water content) and DMSO (1% water content) were used as purchased.

Journal of Sulfur Chemistry 141
The MW-assisted reactions were carried out in a microwave reactor Samsung M181DNR (max
power level 850W) equipped with reflux condenser. Mass spectra were run on a Hewlett-Packard
HP-5971A instrument with EI ionization (70 eV).
4.2. Synthesis of tertiary phosphine sulfides from aromatic alkenes, red phosphorus and
elemental sulfur in the KOH–DMSO under microwave irradiation
4.2.1. Tris(2-phenethyl)phosphine sulfide (2a)
A mixture of the vinylbenzene 1a (10.45 g, 100.0 mmol) and red phosphorus (3.10 g, 100 mmol),
hydroquinone (0.10 g), KOH (10.00 g, 178.5 mmol), water (1.5 ml) and DMSO (40 ml) was
irradiated (600W, temperature reached 190–200◦C) for 7 min. Then elemental sulfur (3.2 g,
100.0 mmol) was added and the reaction mixture was irradiated for 1 min additionally. The reac-
tion mixture was cooled, diluted with water (60 ml), the unreacted red phosphorus was filtered
off and the filtrate was extracted with benzene (3 × 20 ml). The combined benzene extracts were
washed with 5% NaOH aq. solution and 10% KCl aq. solution (3 × 20 ml) and dried over K2CO3.
The benzene was removed under vacuum. The 31P NMR spectrum of the residue contains the fol-
lowing signals: 48.44 ppm (phosphine sulfide 2a) and 47.85 ppm (phosphine oxide 3a).According
to 31P NMR, molar ratio 2a:3a ∼2.3:1. The resulting product so obtained was precipitated from
dichloromethane with hexane twice to afford 6.70 g of phosphine sulfide of 3a (yield 53%).
1
White powder; yield: 6.70 g (53%); mp 96◦C (hexane). H NMR (400 MHz, CDCl3): δ =
2.11 − 2.17 (m, 6 H, CH2P), 2.89–2.99 (m, 6 H, CH2Ph), 7.16 and 7.23 (m, 15 H, Ph). 13C NMR
2
1
(100 MHz, CDCl3): δ = 28.57 (d, JCP = 2.7 Hz, CH2Ph), 32.84 (d, JCP = 47.9 Hz, CH2P),
126.52 (p−CPh), 128.19 (o−CPh), 128.68 (m−CPh), 140.52 (d, JCP = 13.4 Hz, i−CPh). 31P
3
NMR (161.98 Hz, CDCl3): δ = 48.74. IR (KBr, ν, cm−1): 3105, 3084, 3061, 2930, 3001, 2930,
1601, 1496, 1453, 1401, 1297, 1270, 1226, 1216, 1208, 1173, 1159, 1136, 1070, 1029, 1013,
960, 944, 911, 836, 774, 768, 753, 720, 706, 697, 621, 607, 543, 498. Raman (150 mw, solid, ν,
cm−1): 3053, 3037, 2934, 2903, 2868, 1603, 1584, 1450, 1403, 1208, 1180, 1159, 1031, 1004,
829, 623, 598, 544, 500, 475, 218.
Anal. Calc. for C24H27PS (378.51): C, 76.16; H, 7,19; P, 8.18; S, 8.47. Found: C, 76.28; H,
7.09; P, 7.99; S, 8.35%.
4.2.2. Tris[4-(tert-butyl)phenethyl]phosphine sulfide (2b)
A mixture of the 1-(tert-butyl)-4-vinylbenzene 1b (4.80 g, 30.0 mmol) and red phosphorus (1.0 g,
32.2 mmol), hydroquinone (0.10 g), KOH (5.00 g, 89.2 mmol), water (0.75 ml), and DMSO
(20 ml) was irradiated (600W, temperature reached 190–200) for 7 min. Then elemental sul-
fur (0.96 g, 30.0 mmol) was added and the reaction mixture was irradiated for 1 min additionally.
The reaction mixture was cooled, diluted with water (30 ml), the unreacted red phosphorus was
filtered off and the filtrate was extracted with benzene (3 × 10 ml). The combined benzene extracts
were washed with 5% NaOH aq. solution and 10% KCl aq. solution (3 × 10 ml) and dried over
K2CO3. The benzene was removed under vacuum. The 31P NMR spectrum of the residue con-
tains the following signals: 48.94 ppm (phosphine sulfide 2b) and 47.78 ppm (phosphine oxide
3b). According to 31P NMR, molar ratio 2b:3b ∼4.5:1. The residue was treated in cold methanol
(10 × 3 ml) and the insoluble white powder was filtered off on Schott filter, dried in vacuum to
afford 2.07 g of2b (38%).
1
White powder; yield: 2.07 g (38%); mp 145–146◦C (hexane). H NMR (400 MHz, CDCl3):
δ = 1.31 (s, 27 H, Me), 2.11–2.15 (m, 6 H, CH2P), 2.91-2.93 (m, 6 H, CH2C6H4), 7.12 and
2
7.32 (m, 12 H, C6H4). 13C NMR (100 MHz, CDCl3) : δ = 28.17 (d, JCP = 2.0 Hz, CH2Ph),

142 V.A. Kuimov et al.
31.44 (Me), 32.80 (d, 1JCP = 47.7 Hz, CH2P), 34.47 (CMe), 125.70 (o−CAr), 127.68 (m−CAr),
137.32 (d, 3JCP = 13.6 Hz, i−CAr), 149.62 (p−CAr). 31P NMR (161.98 Hz, CDCl3) : δ = 48.76.
IR (KBr, ν, cm−1): 3134, 3094, 3057, 2962, 2904, 2865, 1646, 1517, 1474, 1463, 1448, 1414,
1393, 1363, 1269, 1218, 1206, 1143, 1109, 1020, 963, 936, 855, 839, 815, 771, 742, 704, 589,
563, 550, 524. Anal. Calc. for C36H51PS (546.83): C, 79.07; H, 9.40; P, 5.66; S, 5.86. Found: C,
79.15; H, 9.29; P, 5.59; S, 5.75%.
4.2.3. Tris(4-chlorophenethyl)phosphine sulfide (2c)
A mixture of the 1-(chloro)-4-vinylbenzene 1c (1 g, 7.25 mmol) and red phosphorus (0.22 g,
7.0 mmol), hydroquinone (0.01 g), KOH (0.70 g, 12.5 mmol), water (0.11 ml) and DMSO (10 ml)
was irradiated (600W, temperature reached 190–200◦C) for 5 min. Than elemental sulfur (0.23 g,
7.25 mmol) was added and the reaction mixture was irradiated for 1 min additionally. The reaction
mixture was cooled, diluted with water (15 ml), the unreacted red phosphorus was filtered off and
the filtrate was extracted with benzene (3 × 15 ml). The combined benzene extracts were washed
with 5% NaOH aq. solution and 10% KCl aq. solution (3 × 5 ml) and dried over CaCl2. The
benzene was removed under vacuum. The 31P NMR spectrum of the residue contains the following
signals: 48.82 ppm (phosphine sulfide 2c) and 48.02 ppm (phosphine oxide 3c). According to 31P
NMR, molar ratio 2c:3c ∼1.4:1. The residue was recrystallized from hot hexane three times. The
residue obtained was dried in vacuum (5Torr, 30◦C) to afford 0.49 g of 3c.
1
Pale powder; yield: 0.49 g (42%); mp 120◦C (hexane). H NMR (400 MHz, CDCl3): δ =
2.01 − 2.10 (m, 6 H, CH2P), 2.83–2.90 (m, 6 H, CH2C6H4), 7.08 and 7.23 (m, 12 H, C6H4).
13C NMR (100 MHz, CDCl3): δ = 28.0 (d, 2JCP = 2.3 Hz, CH2C6H4), 32.82 (d, 1JCP = 47.9 Hz,
CH2P), 128.75 (o−CAr), 129.52 (m−CAr), 132.34 (p−CAr), 138.87 (d, 3JCP = 13.0 Hz, i−CAr).
31P NMR (161.98 Hz, CDCl3): δ = 48.76. IR (KBr, ν, cm−1): 3084, 3064, 3042, 3026, 2923,
2868, 2858, 1648, 1596, 1575, 1492, 1451, 1433, 1407, 1350, 1269, 1222, 1178, 1148, 1132,
1091, 1042, 1015, 950, 847, 834, 808, 774, 750, 718, 693, 653, 585, 567, 518, 509, 492, 484.
Anal. Calc. for C24H24Cl3PS (481.85): C, 59.82; H, 5.02; Cl, 22.07; P, 6.43; S, 6.65. Found: C,
59.78; H, 5.17; Cl, 22.23; P, 6.59; S, 6.77%.
4.3. Reaction of vinylbenzene with red phosphorus and elemental sulfur in the
KOH–DMSO system at 90–95◦C
(a) A mixture of the vinylbenzene1a (2.17 g, 20.8 mmol), red phosphorus (0.62 g, 20 mmol),
elemental sulfur (0.70 g, 21.9 mmol), hydroquinone (0.02 g), KOH (2.00 g, 35.7 mmol), water
(0.3 ml) and DMSO (8 ml) was stirred for 3 h at 90–95◦C. The reaction mixture was cooled, diluted
with water (12 ml), the unreacted red phosphorus was filtered off and the filtrate was extracted with
benzene (3 × 10 ml). The combined benzene extracts were washed with 5% NaOH aq. solution
and 10% KCl aq. solution (3 × 10 ml) and dried over K2CO3. The benzene was removed under
vacuum to afford 1.27 g of the solid. The 31P NMR spectrum of the latter contains the following
signals: 49.28 ppm (phosphine sulfide 2a) and 48.76 ppm (phosphine oxide 3a). According to 31
NMR, molar ratio 2a:3a ∼1:10, (total yield of 2a and 3a ∼49%).
P
(b)Amixtureofthevinylbenzene 1a (10.87 g, 104.4 mmol), redphosphorus(3.10 g, 100 mmol),
elemental sulfur (0.50 g), hydroquinone (0.10 g), KOH (10.00 g, 178.5 mmol), water (1.5 ml) and
DMSO (40 ml) was stirred for 20 min at 90–95◦C. Then to a suspension obtained, equal portions of
elemental sulfur (3 × 1 g) were consecutively added for every 20 min. Then the reaction mixture
was stirred for 2 h additionally at the same temperature. The reaction mixture was cooled, diluted
with water (60 ml), the unreacted red phosphorus was filtered off and the filtrate was extracted
with benzene (3 × 20 ml). The combined benzene extracts were washed with 5% NaOH solution

Journal of Sulfur Chemistry 143
and 10% KCl aq. solution (3 × 20 ml) and dried over K2CO3. The benzene was removed under
vacuum to afford 7.33 g of the solid, the 31P NMR spectrum of which contained the following
signals: 48.94 ppm (phosphine sulfide 2a) and 47.78 ppm (phosphine oxide 3a). According to 31
NMR, molar ratio 2a:3a ∼1:0.9, (total yield of 2a and 3a ∼57%).
P
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