Synthesis of tris(organylthioethyl)phosphines and their derivatives on the basis of the reaction of phosphine with vinyl sulfides

Article abstract of DOI:10.1134/S1070363211030042

Phosphine generated from the red phosphorus in the system KOH-H₂O-toluene adds regio- and chemoselectively to vinyl sulfides under radical initiation conditions with the formation of tris(2-organylthioethyl) phosphines, which are easily oxidized by elemental sulfur and selenium to the corresponding phosphine sulfides and phosphine selenides in 54-78% yield. The obtained adducts are split when treated with sodium amide in THF to give trivinylphosphine and trivinylphosphine chalcogenides.

Full text of DOI:10.1134/S1070363211030042

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 3, pp. 470–473. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © N.A. Chernysheva, V.L. Mikhailenko, N.K. Gusarova, S.V. Fedorov, B.А. Тrоfimov, 2011, published in Zhurnal Obshchei Khimii,
2011, Vol. 81, No. 3, pp. 373–376.
Synthesis of Tris(organylthioethyl)phosphines
and Their Derivatives on the Basis of the Reaction
of Phosphine with Vinyl Sulfides
N. A. Chernysheva, V. L. Mikhailenko, N. K. Gusarova, S. V. Fedorov, and B. А. Тrоfimov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: gusarova@irioch.irk.ru
Received April 1, 2010
Abstract—Phosphine generated from the red phosphorus in the system KOH–Н2О–toluene adds regio- and
chemoselectively to vinyl sulfides under radical initiation conditions with the formation of tris(2-
organylthioethyl)phosphines, which are easily oxidized by elemental sulfur and selenium to the corresponding
phosphine sulfides and phosphine selenides in 54–78% yield. The obtained adducts are split when treated with
sodium amide in THF to give trivinylphosphine and trivinylphosphine chalcogenides.
DOI: 10.1134/S1070363211030042
Tertiary phosphines and phosphine chalcogenides
containing organylthio groups are efficient polydentate
(chemilabile) ligands [1–3]. On their basis, 99mТс-
complexes for myocardial diagnostics [4], as well as
the metal complexes for the alkylation [2] and hydro-
formylation [3] reactions were obtained. Besides,
tertiary organylthiophosphines and phosphine chalco-
genides are used as building blocks in organic syn-
thesis (for example, for preparation of vinyl phosphine
oxides [5]) and the models for investigation of the
fundamental problem of the relative ability of the
phosphorus and sulfur atoms of different valence to
stabilize the adjacent carbanions [5–7].
on the use the simplest representative of the РН-
addends, phosphine РН3, in this reaction are scarce. A
short communication [11] reported that phosphine
added to vinyl sulfides under radical initiation condi-
tions to form a mixture of primary, secondary, and
tertiary phosphines. The conditions for the predominant
formation of tris(organylthioethyl)phosphine oxides
were found [11].
The goal of the present study was to elaborate an
expedient approach to the synthesis of functional tertiary
phosphines, phosphine sulfides, and phosphine sele-
nides containing organylthio groups on the basis of the
reaction of phosphine with vinyl sulfides, and the
investigation of some properties of these compounds.
One of convenient approaches to the synthesis of
these compounds is the reaction of secondary phos-
phines [7, 8] and phosphine chalcogenides [9] with the
available vinyl sulfides [10]. At the same time, the data
To this end the initial phosphine was generated in a
separate flask from red phosphorus in the system
RS
RS
SR
SR
RS
Xn
KOH/H2O
toluene
I, II
Pn
P
PH3
P
AIBN, dioxane
X
SR
III_VI
SR
R = C7H15 (I), Ph (II); R = C7H15, X = S (III); R = C7H15, X = Se (IV); R = Ph, X = S (V); R = Ph, X = Se (VI).
470

SYNTHESIS OF TRIS(ORGANYLTHIOETHYL)PHOSPHINES
471
KOH–Н2О–toluene [12] and passed in the course of 4–
6 h at the atmospheric pressure through the solution of
vinyl sulfide I, II in dioxane containing catalytic
amounts of AIBN heated to 68–80°С. Then the
bubbling of phosphine was stopped and the unreacted
phosphine was removed by an argon stream. To the
reaction mixture a portion of vinyl sulfide (30% of the
initial amount) was added, and the heating was con-
tinued for another 1.5 h at 68–80°С till the exhaustive
sulfinylethylation of phosphine. Under these condition
the reaction proceeded regio- and chemoselectively
leading to the corresponding tris(2-organylthioethyl)-
phosphines III–VI. The latter are easily oxidized
(without isolation and purification) with elemental sulfur
or selenium (20–40°С) to the corresponding phosphine
sulfides and phosphine selenides in 54–78% yield.
We failed to obtain trivinylphosphine selenide X
from phosphine selenide VI and sodium amide under
these conditions: a substantial amount of elemental
selenium was formed in the reaction mixture.
However, compound X is easily obtained by oxidation
of trivinylphosphine VIII with elemental selenium
(THF, room temperature).
Se
P
VIII
THF
Se
X
The obtained trivinylphosphine and trivinylphos-
phine chalcogenides are promising cross-linking agents
for noncombustible materials and reactive building
blocks for organic synthesis [13]. In particular,
trivinylphosphine oxides are used in the metathesis
reactions for preparation of Р-stereogenic phosphine
oxides with three different alkenyl groups [14].
Besides, they are convenient models for physico-
chemical investigations [15], and for solving a funda-
mental problem of competitive deprotonation in the
vicinal fragment X=PCH2CH2S (Х = LP, S, Se) [5–7].
By the example of the reaction of phosphine with
vinyl phenyl sulfide it was shown that the intermediate
tris(2-phenylthioethyl)phosphine VII can be isolated
from the reaction mixture in 73% yield and of up to
90% purity. It contained as an impurity the unreacted
vinyl phenyl sulfide identified by the 1Н NMR method.
The individual phosphine VII was obtained in 94%
yield by the reduction of tris(2-phenylthioethyl)phos-
phine selenide VI with sodium metal in toluene at
108–110°С.
Thus, on the basis of the reaction of phosphine and
vinylsulfides the earlier unknown representatives of tris
(organylthioethyl)phosphines, phosphine sulfides, and
phosphine selenides are synthesized. The obtained
adducts are convenient intermediates in the synthesis of
trivinylphosphine and its chalcogenides, whereas the
known methods of their preparation are laborious and
based on the reactions of aggressive phosphorus
chlorides with organometal compounds [14, 16, 17].
SPh
PhS
Na
VI
P
toluene
SPh
VII
The synthesized functional tertiary phosphines and
phosphine chalcogenides are convenient intermediates
for preparation of, for example, trivinylphosphines and
trivinylphosphine chalcogenides. Thus, phosphine VII
and phosphine sulfide V when treated with sodium
amide in THF (63–64°С) form trivinylphosphine VIII
and trivinylphosphine sulfide IX in the yield of 86%
and 82%, respectively.
EXPERIMENTAL
1Н, 13C, and 31Р NMR spectra were recorded on a
Bruker DPX-400 spectrometer (400.13, 101.62, and
161.98 MHz, respectively), in CDCl3, internal
reference HMDS, external reference 85% Н3РО4. IR
spectra were obtained on a Bruker IFS 25 spectrometer
in thin films and KBr pellets.
PhS
SPh
NaNH2/THF
Tris(organylthioethyl)phosphine chalcogenides
(III–VI) (general procedure). The solution of 0.06 g
of AIBN in 25 ml of dioxane was flushed with argon
and saturated with phosphine in the course of 15 min.
To the obtained solution, at 68–80°С, while stirring
with a magnetic stirrer and passing the phosphine, the
solution of 9.3 mmol of the corresponding vinyl-
organyl sulfide I, II in 6 ml of hexane was added
dropwise during 1 h; the passing of phosphine was
P
P
_PhSNa
_NH3
X
X
SPh
V, VII
VIII, IX
X = LP (VII, VIII), S (V, IX).1
1 LP is lone electron pair.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 3 2011

472
CHERNYSHEVA et al.
continued during 3–5 h, then stopped, the reaction
mixture was flushed with argon, and 3.2 mmol of the
corresponding vinylorganyl sulfide in 3 ml of dioxane
and 0.03 g of AIBN was added. The mixture was
stirred for 1.5 h and 4.2 mmol of elemental sulfur was
added (at room temperature) or of selenium (at 40–45°С).
Dioxane was removed in a vacuum, the residue was
crystallized from ethanol.
molar excess of Na (0.46 g) was added. The reaction
mixture was vigorously stirred for 2 h 20 min at reflux
(108–110°С), cooled, the formed precipitate was
filtered off (under argon), washed with toluene,
toluene was removed in a vacuum to obtain 1.66 g
(94%) of tris(2-phenylthio)phosphine. White paraffin-
1
like mass. Н NMR spectrum, δ, ppm: 1.85 m (6H,
PCH2), 3.03 m (6H, SCH2), 7.32 m (15Н, Ph). 31P
NMR spectrum, δP, ppm: –27.01. Found, %: C 65.37;
H 6.38; P 6.75; S 21.52. C24H27PS3. Calculated, %: C
65.12; H 6.15; P 7.00; S 21.73.
Tris(2-heptylthioethyl)phosphine sulfide (III).
Yield 1.26 g (56%). Light-yellow oil. IR spectrum
(film), ν, cm–1: 581 (P=S). 1Н NMR spectrum, δ, ppm:
3
Trivinylphosphine (VIII). A three-neck flask
equipped with a thermometer, a condenser and an inlet
tube for passing argon was charged with the solution
of 1.37 g (3.1 mmol) of tris(2-phenylthioethyl)phos-
phine VII in 25 ml of anhydrous THF, flushed with
argon and heated to 40–45°С. Then 0.62 g (16 mmol)
of NaNH2 was added at stirring with a magnetic stirrer,
the reaction mixture was heated to 64°С for 5.5 h. The
formed precipitate was filtered off, washed with THF,
THF was removed under the atmospheric pressure in
the stream of argon. 0.3 g (86%) of trivinylphosphine
VIII was obtained. 1Н NMR spectrum, δ, ppm: 6.26 m
(1Н, НX); 5.78 m (1Н, НA); 5.63 m (1Н, НB); 2J(НAНB)
0.90 t (9H, CH3 JHH 6.8 Hz) 1.29 m (24H, C4H8), 1.60
m (6H, CH2C5H11), 2.19 m (6H, PCH2), 2.56 t (6H,
3
SCH2C6H13 JHH 7.4 Hz), 2.81 m (6Н, SCH2CH2P). 31P
NMR spectrum, δP, ppm: 47.03. Found, %: C 59.87; H
10.41; P 5.29; S 23.59. C27H57PS4. Calculated, %: C
59.94; H 10.62; P 5.73; S 23.71.
Tris(2-heptylthioethyl)phosphine selenide (IV).
Yield 1.41 g (58%). Light-yellow oil. IR spectrum
1
(film), ν, cm–1: 460 (P=Se). Н NMR spectrum, δ,
3
ppm: 0.88 t (9H, CH3 JHH 6.8 Hz) 1.28 m (24H,
C4H8), 1.59 m (6H, CH2C5H11), 2.29 m (6H, PCH2),
3
2.55 t (6H, SCH2C6H13 JHH 7.3 Hz), 2.79 m (6Н,
SCH2CH2P). 31P NMR spectrum, δP, ppm: 36.45.
Found, %: C 55.39; H 9.80; P 5.06; S 16.52; Se 13.81.
C27H57PS3Se. Calculated, %: C 55.16; H 9.77; P 5.27;
S 16.36; Se 13.43.
3
3
2
1.9 Hz; J(НAНX) 11.7 Hz; J(НBНX) 18.5 Hz; J(РНX)
12.0 Hz; 3J(РНA) 30.8 Hz; 3J(РНB) 14.0 Hz. С NMR
13
2
spectrum, δC, ppm: 127.50 (=СН2, JPC 19.7 Hz),
136.55 (=СН, JPC 11.3 Hz). 31P NMR spectrum, δP,
1
Tris(2-phenylthioethyl)phosphine sulfide (V).
ppm: –17.9. Physicochemical characteristics are identical
to those described in [17].
Yield 2.31 g (78%). White needle crystals, mp 71°С
1
(ethanol). IR spectrum (KBr), ν, cm–1: 577 (P=S). Н
Trivinylphosphine sulfide (IX) was prepared
similar to phosphine VIII from 0.4 g (0.84 mmol) of
phosphine sulfide V and 0.17 g (4.4 mmol) of NaNH2.
Yield 0.098 g (82%). 1Н NMR spectrum, δ, ppm: 6.36
m (1Н, НX); 6.17 m (1Н, НA); 6.30 m (1Н, НB);
2J(НAНB) 0.7 Hz; 3J(НAНX) 11.7 Hz; 3J(НBНX) 17.8 Hz;
NMR spectrum, δ, ppm: 2.27 m (6H, PCH2), 3.24 m
(6H, SCH2), 7.41 m (15Н, Ph). 31P NMR spectrum, δP,
ppm: 47.15. Found, %: C 61.02; H 5.71; P 6.20; S
27.45. C24H27PS4. Calculated, %: C 60.72; H 5.73; P
6.52; S 27.02.
3
3
2J(РНX) 24.6 Hz; J(РНA) 46.2 Hz; J(РНB) 24.8 Hz.
Tris(2-phenylthioethyl)phosphine selenide (VI).
13С NMR spectrum, δC, ppm: 133.67 (=СН2, 2JPC 1.5 Hz),
Yield 1.18 g (54%). White crystals, mp 68°С
1
(ethanol). IR spectrum (KBr), ν, cm–1: 482 (P=Se). Н
130.50 (=СН, JPC 80.3 Hz). 31P NMR spectrum, δP,
1
NMR spectrum, δ, ppm: 2.21 m (6H, PCH2), 3.07 m
(6H, SCH2), 7.24 m (15Н, Ph). 31P NMR spectrum, δP,
ppm: 36.04. Found, %: C 55.25; H 5.21; P 5.85; S
18.25; Se 15.31. C24H27PS3Se. Calculated, %: C 55.26;
H 5.22; P 5.94; S 18.44; Se 15.14.
ppm: 29.2. Physicochemical characteristics are identical
to those described in [17].
Trivinylphosphine selenide (X). To a solution of
0.18 g (1.6 mmol) of trivinylphosphine VIII in 10 ml
of anhydrous THF at stirring with a magnetic stirrer at
room temperature 0.13 g (1.6 mmol) of elemental
selenium was added in small portions. The reaction
mixture was stirred to complete disappearance of
selenium (1 h), THF was removed in vacuum to obtain
0.3 g (97%) of phosphine selenide X. 1Н NMR
spectrum, δ, ppm: 6.37 m (1Н, НX); 6.16 m (1Н, НA);
Tris(2-phenylthioethyl)phosphine (VII). A three-
neck flask equipped with a thermometer, a condenser
and an inlet tube for passing argon was charged with
2.09 g (4.0 mmol) of tris(2-phenylthioethyl)phosphine
selenide dissolved in 15 ml of anhydrous toluene,
flushed with argon, heated to 75–80°С, and a five-fold
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 3 2011

SYNTHESIS OF TRIS(ORGANYLTHIOETHYL)PHOSPHINES
473
6.29 m (1Н, НB); 2J(НAНB) 1.0 Hz; 3J(НAНX) 11.8 Hz;
va, S.N., Bogdanova, M.V., Malysheva, S.F., Belo-
gorlova, N.A., Ushakov, I.A., Vitkovskaya, N.M.,
Kobychev, V.B., and Trofimov, B.A., Lett. Org. Chem.,
2006, vol. 3, no. 9, p. 720.
2
3
3J(НBНX) 18.0 Hz; J(РНX) 23.9 Hz; J(РНA) 47.4 Hz;
13
3J(РНB) 25.7 Hz. С NMR spectrum, δC, ppm: 134.58
2
1
31
(=СН2, JPC 1.5 Hz), 129.45 (=СН, JPC 71.9 Hz). P
NMR spectrum, δP, ppm: 22.6. Physicochemical
character-istics are identical to those described in [17].
6. Minami, T., Okauchi, T., Matsuki, H., Nakamura, M.,
Ichikawa, J., and Ishida, M., J. Org. Chem., 1996, vol. 61,
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ACKNOWLEDGMENTS
This work was performed with a financial support
from the Council on Grants of the President of the
Russian Federation (Program of the State Support of
the Leading Scientific Schools, grant no. NSh-
3230.2010.3).
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