Reaction of secondary phosphines with elemental sulfur and hydrazine: Atom-economic synthesis of dithiophosphinates

Full text of DOI:10.1134/S1070363210090306

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 9, pp. 1886–1888. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.V. Artem’ev, N.K. Gusarova, S.F. Malysheva, N.A. Belogorlova, M.L. Al’pert, B.A. Trofimov, 2010, published in Zhurnal
Obshchei Khimii, 2010, Vol. 80, No. 9, pp. 1571–1573.
LETTERS
TO THE EDITOR
Reaction of Secondary Phosphines
with Elemental Sulfur and Hydrazine:
Atom-Economic Synthesis of Dithiophosphinates
A. V. Artem’ev, N. K. Gusarova, S. F. Malysheva,
N. A. Belogorlova, M. L. Al’pert, and B. A. Trofimov
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 April 8, 2010
DOI: 10.1134/S1070363210090306
Here we for the first time report on the three-
component reaction of the secondary phosphines with
elemental sulfur and hydrazine. By the example of the
readily available [1–2] secondary phosphines Iа–Id it
was shown that heating of the reagents (molar ratio
R PH : S : N H = 1 : 2 : 1.1) at 70–75°С for 20 min in
2
2
4
ethanol led to hydrazinium dithiophosphinates IIа–IId
in 84–92% yield.
+
R
R
R
S
−
H N
EtOH
3
P H + 2 S + N H4 H O
P
2
2
NH2
R
S
Iа−Id
(а),
IIа−IId
R =
(b),
(c),
Me
(d).
N
N
S
The reaction is highly selective. No side products,
in particular, the expected polysulfides (the products of
the known reaction of elemental sulfur with hydrazine
S
S
N H
+
2
4
−
I
R2P
R2P
R2P
S
N H
2
5
−
H
[
3]) were found in the studied three-component reaction.
S
II
The dicovered three-component reaction, ap-
parently proceeds via the stage of formation of the
secondary phosphine sulfides from the secondary
phosphines I and one equivalent of elemental sulfur.
Further hydrazine, acting as a base, deprotonates the
secondary phosphine sulfides. The generated P,S-
ambident thiophosphinites enter the reaction with the
second equivalent of sulfur to afford hydrazinium
dithiophosphinates II.
ethyl)phosphine sulfide (III), elemental sulfur, and
hydrazine hydrate (EtOH, 70–75°С, 20 min).
S
EtOH
P
+ S + N H4 H O
IIа
2
2
H
The above scheme is indirectly proved by the fact
of formation of hydrazinium dithiophosphinate IIа in
the reaction of equivalent amounts of bis(2-phenyl-
III
Thus, it is shown for the first time that the reaction
of the secondary phosphines with elemental sulfur and
1
886

REACTION OF SECONDARY PHOSPHINES
1887
hydrazine is an effective atom-economic route to
hydrazinium dithiophosphinates, promising ligands for
designing metal complexes [4], antioxidants [5],
potentially biologically active compounds [6], and
reactive building blocks for organic and organo-
elemental synthesis [7].
ppm: 2.03–2.10 m (4Н, CH P), 2.95–3.01 m (4H,
2
CH Py), 7.10 s (5H, NH), 7.22 and 8.42 m (8Н, Py).
2
1
1
3
С NMR, δ , ppm: 29.27 (CH Py), 43.17 d (CH P,
С
2
2
JCP = 50.8 Hz), 123.86 (C-3, Py), 149.50 (C-2, Py),
3
31
152.06 d (C-4, Py, J = 17.3 Hz). Р NMR, δ , ppm:
CP
Р
67.46. Found, %: С 49.45; Н 6.20; N, 16.34; Р 8.87; S
9.02. C H N PS . Calculated, %: С 49.39; Н 6.22;
1
14
21
4
2
Synthesis of hydrazinium dithiophosphinates
N, 16.46; Р 9.10; S 18.84.
(IIа-IId) (general procedure). To the solution of a
secondary phosphine I (1.0 mmol) and hydrazine
hydrate (0.055 g, 1.1 mmol) in 10 ml of ethanol
rhombic sulfur (0.064 g, 2.0 mmol) was added at room
temperature. The mixture was stirred at 70–75°С for
Hydrazinium bis[2-(2-methylpyrid-5-yl)lethyl]di-
thiophosphinate (IIc), 0.31 g (84%), white powder,
–
1
mp 149–151ºС (ethanol). IR (KBr), cm : 3238, 3142,
3
1
1
8
4
076, 3035, 2918, 2766, 2694, 2605, 2106, 1604,
567, 1515, 1491, 1446, 1393, 1331, 1300, 1278,
245, 1202, 1138, 1099, 1037, 1013, 970, 943, 930,
2
0 min, filtered, the solvent was removed, the residue
was washed with ether (2×10 ml), and dried in a
vacuum (35–40°С, 1 mm Hg) to obtain salt II.
58, 827, 782, 734, 727, 709, 700, 655, 611, 557, 543,
1
94. Н NMR, δ, ppm: 2.60–2.67 m (4Н, CH P), 3.04
2
Reaction of bis(2-phenylethyl)phosphine sulfide
s (6H, Me), 3.51–3.57 m (4H, CH Py), 7.70 s (5H,
2
(
III) with elemental sulfur and hydrazine. To the
13
NH), 7.76 and 8.11 m (4Н, Py), 8.90 s (2H, Py).
С
solution of phosphine sulfide III (0.274 g, 1.0 mmol)
and hydrazine hydrate (0.055 g, 1.1 mmol) in 10 ml of
ethanol rhombic sulfur (0.032 g, 1.0 mmol) was added
at room temperature. The mixture was stirred at 70–
NMR, δ , ppm: 24.69 (Me), 27.76 (CH Py), 45.30 d
С
2
1
(
CH P, J = 49.8 Hz), 123.81 (C-3, Py), 136.23 d (C-5,
2 CP
Py, J = 15.2 Hz), 137.10 (C-4, Py), 149.69 (C-6,
Py), 156.06 (C-2, Py). Р NMR, δ , ppm: 67.68.
3
CP
3
1
Р
7
5°С for 20 min, filtered, the solvent was removed, the
Found, %: С 52.18; Н 6.87; N, 8.71; Р 8.32; S 17.65.
C H N PS . Calculated, %: С 52.15; Н 6.84; N,
residue was washed with ether (2×10 ml), and dried in
a vacuum (35–40°С, 1 mm Hg) to obtain 0.30 g (89%)
of dithiophosphinate IIа.
1
6
25
4
2
1
5.20; Р 8.41; S 17.40.
Hydrazinium diphenyldithiophosphinate (IId),
.26 g (92%), white powder, mp 96–98°С (ethanol).
IR (KBr), cm : 3302, 3245, 3140, 302, 2869, 2697,
Hydrazinium bis(2-phenylethyl)dithiophosphinate
0
(
(
IIа), 0.30 g (89%), white powder, mp 146–148°С
–
1
–
1
ethanol). IR (KBr), cm : 3305, 3234, 3187, 3161,
2
1
8
5
7
1
643, 2564, 1569, 1496, 1481, 1472, 1434, 1387,
303, 1224, 1173, 1158, 1094, 1067, 1024, 998, 932,
51, 752, 743, 702, 692, 653, 644, 628, 612, 607, 560,
3
2
1
1
9
6
2
081, 3059, 3023, 2973, 2931, 2811, 2676, 2642,
559, 1600, 1583, 1562, 1494, 1479, 1454, 1441,
392, 1266, 1229, 1213, 1198, 1179, 1162, 1147,
127, 1091, 1028, 1018, 1009, 1000, 989, 973, 948,
38, 910, 896, 852, 828, 769, 756, 743, 730, 695, 666,
1
26, 488. Н NMR, δ, ppm: 6.61 s (5H, NH), 7.19–
1
3
.27 and 7.96–8.01 m (10Н, Ph). С NMR, δ , ppm:
С
2
1
26.81 d (C-o, J = 12.2 Hz), 128.14 (C-р), 130.24 d
06, 577, 551, 508, 490, 479. Н NMR, δ, ppm: 2.00–
CP
3
1
(
C-m, J =10.2 Hz), 145.77 d (C-i, J = 77.2 Hz).
.07 m (4Н, CH P), 2.90-2.97 m (4H, CH Ph), 6.93 s
CP CP
2
2
3
1
1
3
Р NMR, δ , ppm: 61.61. Found, %: С 51.08; Н 5.39;
(
5H, NH), 7.12–7.27 m (10Н, Ph). С NMR, δ , ppm:
Р
С
1
N, 9.71; Р 10.69; S 22.84. C H N PS . Calculated,
%
2
9.79 (CH Ph), 44.47 d (CH P, J = 50.8 Hz), 125.51
12 15
2
2
2
2
CP
3
: С 51.04; Н 5.35; N, 9.92; Р 10.97; S 22.71.
(C-р), 128.10 (C-o), 128.29 (C-m), 143.0 d (C-i, J
=
CP
3
1
1
5
6.2 Hz). Р NMR, δ , ppm: 67.32. Found, %: С
Р
IR spectra were recorded on a Bruker IFS-25
6.70; Н 6.81; N, 8.30; Р 9.01; S 19.05. C H N PS .
1
13
31
1
6
23
2
2
spectrometer in KBr pellets. Н, С, and Р NMR
spectra were obtained on a Bruker DPX-400 spec-
trometer (400.13, 101.61 and 161.98 MHz, respect-
Calculated, %: С 56.78; Н 6.85; N, 8.28; Р 9.15; S
8.95.
1
Hydrazinium bis[2-(4-pyridyl)lethyl]dithiophos-
phinate (IIb), 0.31 g (91%), white powder, mp 193–
tively) in DMSO-d , external standard 85% Н РО
6 3 4
3
1
( Р). Secondary phosphines Iа, Ib, and Ic were
synthesized from red phosphorus, styrene [1], 4-
vinylpyridine [2] or 2-methyl-5-vinylpyridine [2],
respectively. Bis(2-phenylethyl)phosphine sulfide (III)
was obtained by oxidation of phosphine Iа with
elemental sulfur by the known procedure [8].
–
1
1
3
1
1
7
96ºС (ethanol). IR (KBr), cm : 3263, 3134, 3070,
036, 2899, 2581, 2089, 1603, 1556, 1499, 1448,
418, 1316, 1280, 1238, 1214, 1202, 1137, 1128,
081, 1070, 1003, 965, 947, 924, 828, 800, 772, 758,
1
42, 726, 714, 614, 603, 582, 512, 490. Н NMR, δ,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 9 2010

1
888
ARTEM’EV et al.
Diphenylphosphine was a commercial product (Aldrich,
009). Commercial 96% ethanol was used as a solvent.
Nepomnyashchikh, K.V., and Dmitriev, V.I., Russ. J.
Gen. Chem., 1997, vol. 67, no. 1, p. 65.
2
All experiments were run in an inert atmosphere (argon).
3. Deryagina, E.N., Levanova, E.P., Grabel’nykh, V.A.,
Sukhomazova, E.N., Russavskaya, N.V., and Korche-
vin, N.A., Russ. J. Gen. Chem., 2005, vol. 75, no. 2,
p. 194.
ACKNOWLEDGMENTS
4
5
.
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Walther, B., Coord. Chem. Rev., 1984, vol. 60, p. 67.
Rudnic, L.R., Lubricant Additives: Chemistry and
Applications, 2nd ed., New York, 2009, p. 51.
Mashkovskii, M.D,. Lekarstvennye sredstva (Drugs),
Мoscow: Meditsina, 1998, vol. 2, p. 360.
Mehrotra, R.C., Srivastava, G., and Chauhan, B.P.S.,
The work was carried out with the financial support
of Russian Fundation for Basic Research (grant no. 08-
0
3-00251).
6
7
.
.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 9 2010