Reaction of primary phosphines with elemental sulfur and alkali metal hydroxides (MOH, M = Na, K, Cs): A novel and facile three-component synthesis of trithiophosphonates

Article abstract of DOI:10.1016/j.tetlet.2010.11.075

Primary phosphines readily react with elemental sulfur and alkali metal hydroxides (MOH, M = Na, K, Cs) in the molar ratio 1:3:2 under mild conditions (70 °C, 0.5 h, ethanol) to afford alkali metal trithiophosphonates in good to high yields (72-90%).

Full text of DOI:10.1016/j.tetlet.2010.11.075

Tetrahedron Letters 52 (2011) 398–400
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Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
Reaction of primary phosphines with elemental sulfur and alkali metal
hydroxides (MOH, M = Na, K, Cs): a novel and facile three-component
synthesis of trithiophosphonates
Alexander V. Artem’ev a, Nina K. Gusarova a, Svetlana F. Malysheva a, Victor I. Mamatyuk b, Yurii V. Gatilov b,
Boris A. Trofimov a,
⇑
a A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russian Federation
b N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
Primary phosphines readily react with elemental sulfur and alkali metal hydroxides (MOH, M = Na, K, Cs)
in the molar ratio 1:3:2 under mild conditions (70 °C, 0.5 h, ethanol) to afford alkali metal trithiophosph-
onates in good to high yields (72–90%).
Received 13 October 2010
Revised 1 November 2010
Accepted 12 November 2010
Available online 18 November 2010
Ó 2010 Elsevier Ltd. All rights reserved.
Keywords:
Primary phosphines
Sulfur
Alkali metal hydroxides
Trithiophosphonates
Metal phosphonates have been studied extensively due to their
applications as ion exchangers, adsorbents, sensors, proton conduc-
tors, nonlinear optical and photochemically active materials,
catalysts, ligands for the design of metal complexes and supramo-
lecular structures.1 However, in stark contrast, very little is known
about the chemistry of the homologous metal trithiophosphonates,
although this is an area of growing interest. Trithiophosphonates
have gained significant attention due to their potential and re-
ported applications as ligands for the preparation of metal com-
plexes,2,3 as building-blocks for organic synthesis,4 as promising
extractants of heavy elements5 and as prospective intermediates
to produce single-source precursors of metal sulfide nanoparticles.6
In addition, metal trithiophosphonates are key intermediates to ob-
tain the corresponding trithiophosphonic acids and their esters.7
The latter represent efficient insecticides8 and potent iniferters.9
Conventional syntheses of trithiophosphonic acid salts are labo-
rious and require difficult to prepare synthons (e.g., dithiadiphos-
phatene disulfides), as well as moisture- and air-sensitive
organometallic reagents. Trithiophosphonates have been prepared
by the reaction of dithiadiphosphatene disulfides with either
ammonia,10 sodium hydrosulfide or lithium sulfide11 (itself pre-
pared from LiHBEt3 and S8 in THF). The reaction of heavy metal
complexes with dithiadiphosphatene disulfides gives metal trit-
hiophosphonates3,12 in low yields due to the formation of by-
products.
In 2004, the synthesis of sodium and magnesium trithiophosph-
onates was reported from a metallated cyclohexylphosphine (CyP-
HLi or CyPHMgBu) and elemental sulfur.2b However, this method
was tedious and only allowed the sodium and magnesium salts
to be prepared.
Therefore, the development of straightforward and ‘green’
routes to metal trithiophosphonates remains a challenge in orga-
nophosphorus chemistry.
This Letter reports an efficient one-pot synthesis of metal trit-
hiophosphonates via a novel three-component reaction between
readily available primary phosphines, elemental sulfur and alkali
metal hydroxides.
Thus, primary phosphines, that is, 1a,b, react with elemental
sulfur and MOH (M = Na, K, Cs) in the molar ratio 1:3:2, under mild
conditions (70 °C, 0.5 h, EtOH), to give trithiophosphonates 2a–e in
72–90% isolated yields13 (Scheme 1).
The reaction was not accompanied by the formation of any side-
products and hence can be considered ‘green’ (atom-economic and
utilizes a non-toxic, recoverable solvent).
The primary phosphines 1a,b employed in this work are avail-
able by the reaction of the phosphine/hydrogen mixture (gener-
ated from red phosphorus and the KOH/H2O/toluene medium)
with the corresponding alkenes (styrene14 or 4-vinylpyridine15
in the superbase system KOH/DMSO (Scheme 2).
)
⇑
Corresponding author. Tel.: +7 395242 14 11; fax: +7 395241 93 46.
E-mail address: boris_trofimov@irioch.irk.ru (B.A. Trofimov).
0040-4039/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2010.11.075

A. V. Artem’ev et al. / Tetrahedron Letters 52 (2011) 398–400
399
S
70 ºC, 0.5 h
+
3 S
+
2 MOH
R
P
S
S
2 M+
R
PH2
EtOH
1a R = Ph (CH2)2
1b R = 4-Py(CH2)2
M = Na, K, Cs
Scheme 1. Three-component synthesis of trithiophosphonates from primary phosphines, elemental sulfur and alkali metal hydroxides.
KOH
H2O/toluene
Ar
Pred
PH3/H2
R
PH2
KOH/DMSO(H2O)
1a R = Ph(CH2)2
1b R = 4-Py(CH2)2
Scheme 2. Synthesis of the primary phosphines 1a,b from red phosphorus and
styrene or 4-vinylpyridine.
All the products are stable and soluble in most organic solvents
and in water. Their structures were established by single-crystal
X-ray diffraction analysis and further confirmed by 1H, 13C and
31P NMR spectroscopic techniques.
Figure 1. ORTEP diagram of the molecular structure of trithiophosphonate 2c with
50% probability ellipsoids. Selected bond distances (Å) and angles (deg): C(1)–P(1)
1.836(2); P(1)–S(2) 2.0230(8); P(1)–S(1) 2.0243(9); P(1)–S(3) 2.0280(9); S(2)–P(1)–
S(1) 113.27(4); S(2)–P(1)–S(3) 111.13(4); S(1)–P(1)–S(3) 112.05(4); C(1)–P(1)–S(1)
105.80(9).
X-ray diffraction studies on compound 2c showed that its
solid-state structure was monomeric and consisted of a 2-phenyl-
ethyltrithiophosphonic acid anion, two caesium cations and two
molecules of water16 (Figure 1). The coordination geometry around
phosphorus is distorted tetrahedral with the bond angles ranging
102.4–114.46°. All the P–S distances (2.02–2.03 Å) are between
the expected P–S single (2.09 Å) and P = S double (1.95 Å) bond dis-
tances, indicating delocalization of the negative charge over the
[R2PS3]2À moiety, as published for analogous compounds.2b The
IR spectra of the trithiophosphonates showed strong absorptions
at 560–600 cmÀ1 which were assigned to the stretching vibrations
of the P–S bonds. The elemental analyses of the products were in
agreement with their structures.
yields. The advantages of the reaction are the accessibility of the
starting materials (primary phosphines, alkali metal hydroxides
and sulfur), mild conditions, short reaction times and simple
experimental procedure. The resulting trithiophosphonates are
prospective ligands for the design of single-source precursors of
metal sulfide nanoparticles and potential synthetic intermediates
for numerous chemical transformations in organic synthesis.
Acknowledgements
A plausible mechanism for the formation of trithiophospho-
nates 2 is as follows (Scheme 3). In the first stage (1), the primary
phosphine 1 reacts with 1 equiv of elemental sulfur to give primary
phosphine sulfide A. The latter is deprotonated by the alkali metal
hydroxide (MOH) to afford P,S-ambident anion B (stage 2), which
further reacts with a second equivalent of elemental sulfur to pro-
vide the dithiophosphonite C (stage 3). Deprotonation of C by MOH
(stage 4) leads to P,S-ambident anion D. In the final stage (5), reac-
tion of D with a third equivalent of sulfur affords the trit-
hiophosphonate 2.
This work has been carried out under financial support of lead-
ing scientific schools (Grant NSh-3230.2010.3) and young Russian
Scientists (Grant MK-629-2010.3) by the President of the Russian
Federation.
References and notes
1. For a review, see: Clearfield, A. Prog. Inorg. Chem. 1998, 47, 371.
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Raithby, P. R.; White, A. J. P. Dalton Trans. 2004, 3169; (c) Shi, W.; Shafaei-
Fallah, M.; Anson, C. E.; Rothenberger, A. Dalton Trans. 2006, 3257; (d) Shafaei-
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2008, 5705.
In summary, we have developed a new three-component reac-
tion between primary phosphines, elemental sulfur and alkali me-
tal hydroxides to afford metal trithiophosphonates in good to high
S
R
H
S
H
R
H
R
H
S
MOH
(2)
S
R
PH2
P
P
P
S
M
(1)
(3)
B
A
1
S
M
S
M
R
S
S
S
S
MOH
P
M
2 M
P
R
P
S
R
(4)
(5)
H
S
C
D
2
Scheme 3. A plausible mechanism for the formation of trithiophosphonates 2.

400
A. V. Artem’ev et al. / Tetrahedron Letters 52 (2011) 398–400
3. Shi, W. Syntheses and structures of new P/S and P/Se metal complexes;
673, 602, 593, 575, 500, 465. 1H NMR (400.13 MHz, D2O, ppm), d: 2.42–2.49
Dissertation Doktors der Naturwissenschaften, der Universität Fridericiana zu
Karlsruhe: Germany, 2007.
(m, 2H, CH2P), 3.01–3.07 (m, 2H, CH2Ph), 7.13–7.32 (m, 5H, Ph). 13C NMR
1
(100.62 MHz, D2O, ppm), d: 31.25 (CH2Ph), 54.42 (d, JP,C = 53.0 Hz, CH2P),
4. Edmundson, R. S. In The chemistry of Organophosphorus Compounds, Ter- and
Quinque-valent Phosphorus acids and Their Derivatives; Hartley, F. R., Ed.; John
Wiley and Sons: New York, 1996; Vol. 4, pp 397–494.
125.43 (C-p in Ph), 127.92 (C-o in Ph), 128.20 (C-m in Ph), 142.17 (d,
3JP,C = 20.0 Hz, C-i in Ph). 31P NMR (161.98 MHz, D2O, ppm), d: 82.40. Found (%):
C 31.04; H 2.88; P 9.76; S 30.63. Calcd for C8H9K2PS3 (%): C 30.94; H 2.92; P
9.97; S 30.98.
5. Flett, D. S. J. Organomet. Chem. 2005, 690, 2426.
6. (a) Byrom, C.; Malik, M. A.; O’Brien, P.; White, A. J. P.; Williams, D. J. Polyhedron
2000, 19, 211; (b) Malik, M. A.; Afzaal, M.; O’Brien, P. Chem. Rev. 2010, 110,
4417.
Compound 2c: Di-caesium 2-phenylethyltrithiophosphonate. White crystalline
powder, yield: 0.45 g (90%), mp > 250 °C (EtOH). IR (film, m
/cmÀ1): 3078, 3048,
3022, 2933, 2916, 2859, 1637, 1624, 1596, 1494, 1481, 1447, 1405, 1386, 1331,
1305, 1256, 1211, 1203, 1189, 1166, 1155, 1128, 1117, 1074, 1051, 1028, 997,
939, 908, 828, 812, 167, 747, 726, 697, 657, 576, 562, 503, 461. 1H NMR
(400.13 MHz, D2O, ppm), d: 2.26–2.32 (m, 2H, CH2P), 2.85–2.91 (m, 2H, CH2Ph),
6.96–7.17 (m, 5H, Ph). 13C NMR (100.62 MHz, D2O, ppm), d: 31.64 (CH2Ph),
55.04 (d, 1JP,C = 53.0 Hz, CH2P), 125.95 (C-p in Ph), 128.43 (C-o in Ph), 128.71 (C-
m in Ph), 142.80 (d, 3JP,C = 20.0 Hz, C-i in Ph). 31P NMR (161.98 MHz, D2O, ppm),
d: 82.10. Found (%): C 19.38; H 1.78; P 6.39; S 19.24. Calcd for C8H9Cs2PS3 (%): C
19.29; H 1.82; P 6.22; S 19.31.
7. (a) Hahn, J.; Nataniel, T. Z. Anorg. Allg. Chem. 1986, 543, 7; (b) Hahn, J.; Hopp, A.;
Borkowsky, A. Phosphorus, Sulfur Silicon Relat. Elem. 1992, 64–65, 129.
8. (a) Chavdarian, C. G.; Haag, W. G. U.S. Patent 4,544,651, 1985; Chem. Abstr.
1986, 104, 207446m.; (b) Shortt, A. B.; Haag, W. G. U.S. Patent 4,548,930, 1985;
Chem. Abstr. 1986, 104, 207451j.; (c) Haag, W. G.; Chavdarian, C. G. U.S. Patent
4,552,870, 1985; Chem. Abstr. 1985, 103, 178456m.; (d) Chavdarian, C. G.;
Kanne, D. B. U.S. Patent 4,565,809, 1986; Chem. Abstr. 1986, 104, 225048n.; (e)
Shortt, A. B. U.S. Patent 4,614,735, 1986; Chem. Abstr. 1987, 106, 133824a.; (f)
Chavdarian, C. G.; Shortt, A. B. U.S. Patent 4,636,495, 1987; Chem. Abstr. 1987,
106, 102558n.; (g) Shortt, A. B. U.S. Patent 4,654,430, 1987; Chem. Abstr. 1987,
107, 73845e.; (h) Chavdarian, C. G.; Heusinkveld, V. F. U.S. Patent 4,659,702,
1987; Chem. Abstr. 1986, 104, 225045j.; (i) Chavdarian, C. G. U.S. Patent
4,659,703, 1987; Chem. Abstr. 1987, 107, 78081z.; (j) Shortt, A. B.; Haag, W. G.
U.S. Patent 4,678,778, 1987; Chem. Abstr. 1987, 107, 176231t.; (k) Chavdarian,
C. G. U.S. Patent 4,686,210, 1987; Chem. Abstr. 1988, 108, 132050z.; (l)
Chavdarian, C. G.; Heusinkveld, V. F. U.S. Patent 4,737,490, 1988; Chem. Abstr.
1988, 109, 93322p.; (m) Chavdarian, C. G.; Chang, L. L.; Onisko, B. C.; Earhart, J.
P. U.S. Patent 4,752,604, 1988; Chem. Abstr. 1987, 106, 214126b.; (n)
Chavdarian, C. G. U.S. Patent 4,837,209, 1989; Chem. Abstr. 1990, 112, 32164d.
9. Gigmes, D.; Berin, D.; Marque, S.; Guerret, O.; Tordo, P. Tetrahedron Lett. 2003,
44, 1227.
Compound 2d. Di-sodium (4-pyridyl)ethyltrithiophosphonate. White
crystalline powder, yield: 0.21 g (75%), mp > 250 °C (EtOH). IR (film, m
/cmÀ1):
3073, 3051, 3020, 2995, 2920, 2890, 1628, 1607, 1554, 1500, 1448, 1422, 1397,
1360, 1313, 1274, 1239, 1222, 1195, 1174, 1164, 1133, 1084, 1070, 1026, 1004,
964, 943, 828, 803, 758, 746, 720, 677, 597, 571, 515, 485, 465. 1H NMR
(400.13 MHz, D2O, ppm), d: 2.42–2.49 (m, 2H, CH2P), 3.03–3.10 (m, 2H, CH2Py),
7.29 and 8.27 (d, 4H, Py). 13C NMR (100.62 MHz, D2O, ppm), d: 31.35 (CH2Py),
1
53.28 (d, JP,C = 54.0 Hz, CH2P), 124.38 and 148.34 (Py), 153.55 (d,
3JP,C = 20.9 Hz, Py). 31P NMR (161.98 MHz, D2O, ppm), d: 81.90. Found (%): C
30.18; H 2.78; N 5.10; P 11.01; S 34.54. Calcd for C7H8NNa2PS3 (%): C 30.10; H
2.89; N 5.02; P 11.09; S 34.44.
Compound 2e: Di-caesium (4-pyridyl)ethyltrithiophosphonate. White
crystalline powder, yield: 0.48 g (88%), mp > 250 °C (EtOH). IR (film, m
/cmÀ1):
10. (a) Fluck, E.; Binder, H. Z. Anorg. Allg. Chem. 1970, 377, 298; (b) Diemert, K.;
Kuchen, W.; Schepanski, H. Chem. Ztg. 1983, 107, 306.
11. Zank, G. A.; Rauchfuss, T. B. Organometallics 1984, 3, 1191.
3434, 3139, 2966, 2945, 2924, 2893, 2821, 2720, 1603, 1553, 1500, 1454, 1441,
1421, 1396, 1371, 1347, 1307, 1266, 1176, 1131, 1119, 1093, 1077, 1068, 1046,
1015, 992, 937, 887, 864, 844, 797, 752, 735, 720, 579, 565, 501, 465. Salt 2e
was obtained as solvate with one molecule of ethanol. 1H NMR (400.13 MHz,
D2O, ppm), d: 1.07 (t, 3H, 3JHH = 7.1 Hz, Me), 2.44–2.51 (m, 2H, CH2P), 3.06–3.13
(m, 2H, CH2Py), 3.51–3.57 (m, 2H, OCH2), 7.34 and 8.31 (d, 4H, JHH = 6.0 Hz, Py).
13C NMR (100.62 MHz, D2O, ppm), d: 16.43 (Me), 31.11 (CH2Py), 52.65 (d,
1JP,C = 55.5 Hz, CH2P), 57.05 (OCH2), 124.25 and 147.66 (Py), 153.70 (d,
3JP,C = 19.8 Hz, Py). 31P NMR (161.98 MHz, D2O, ppm), d: 83.69. Found (%): C
19.58; H 2.47; N 2.61; P 5.55; S 17.54. Calcd for C9H14Cs2NOPS3 (%): C 19.83; H
2.59; N 2.57; P 5.68; S 17.60.
12. (a) Jones, R.; Williams, D. J.; Wood, P. T.; Woollins, J. D. Polyhedron 1987, 6, 539;
(b) Slater, J. M.; Garner, C. D.; Clegg, W. Chem. Commun. 1990, 281; (c)
Kirschbaum, K.; Boenninghausen, U.; Gesing, E.; Greiwe, K.; Kuhlmann, U.;
Strasdeit, H.; Krebs, B.; Henkel, G. Z. Naturforsch. B. 1990, 45, 245; (d) Foreman,
M. R. S. J.; Slawin, A. M. Z.; Woollins, J. D. Dalton Trans. 1996, 3653; (e) van Zyl,
W. E.; Staples, R. J.; Fackler, J. P. Inorg. Chem. Commun. 1998, 1, 51; (f) Carmalt,
C. J.; Clyburne, J. A. C.; Cowley, A. H.; Lomeli, V.; McBurnett, B. G. Chem.
Commun. 1998, 243; (g) van Zyl, W. E.; Luzuriaga, J. M. L.; Mohamed, A. A.;
Staples, R. J.; Fackler, J. P. Inorg. Chem. 2002, 41, 4579; (h) Shi, W.; Shafaei-
Fallah, M.; Anson, C. E.; Rothenberger, A. Dalton Trans. 2005, 3909.
13. Experimental procedure: To a solution of primary phosphine 1 (1.0 mmol) in
EtOH (5 mL) were added consecutively a solution of MOHÁnH2O (n = 0 for Na;
n = 0.5 for K; n = 1 for Cs; 2.0 mmol) in EtOH (5 mL) and elemental (rhombic)
sulfur (0.096 g, 3.0 mmol) at rt under argon. The suspension was stirred until
14. Gusarova, N. K.; Arbuzova, S. N.; Malysheva, S. F.; Khilko, M. Y.; Tatarinova, A.
A.; Gorokhov, V. G.; Trofimov, B. A. Russ. Chem. Bull. 1995, 8, 1597.
15. Gusarova, N. K.; Trofimov, B. A.; Malysheva, S. F.; Shaukhudinova, S. I.;
Belogorlova, N. A.; Arbuzova, S. N.; Nepomnyashchikh, K. V.; Dmitriev, V. I.
Russ. J. Gen. Chem. 1997, 67, 65.
16. X-ray crystallographic data for compound 2c: C8H13Cs2O2PS3, Mr = 534.15,
monoclinic, space group C2/c, a = 37.0625(11) Å, b = 6.8983(2) Å and
complete dissolution of sulfur (ca. 0.5 h) at 70 °C to give
a dark-yellow,
transparent solution. The solvent was removed under reduced pressure and
the residue was washed with Et2O (8 mL Â 2) and dried in vacuo (1 Torr, 45 °C)
to afford salt 2.
c = 12.9721(4) Å, b = 96.063(2), V = 3298.00(17) Å3, Z = 8, dcalc = 2.152 g/cmÀ3
,
l
(MoK
160, R indices [I_2
studies were carried out on Bruker SMART KAPPA APEX-II CCD diffractometer
at 297 K (MoK radiation). The crystal structure was solved by direct methods
a
) = 4.883 mmÀ1
(I)]: R1 = 0.0325, wR2 (all data) = 0.0804. X-ray diffraction
, (h)max = 34.98°, data/restraints/parameters: 7155/6/
r
Compound 2a: Di-sodium 2-phenylethyltrithiophosphonate. white crystalline
powder, yield 0.20 g (72%), mp > 250 °C (EtOH). IR (KBr,
m
/cmÀ1): 3084, 3060,
a
3025, 2976, 2928, 2860, 1618, 1601, 1495, 1452, 1396, 1333, 1261, 1205, 1190,
1147, 1123, 1096, 1075, 1061, 1029, 1005, 938, 911, 828, 758, 737, 730, 697,
677, 590, 576, 564, 496, 463. 1H NMR (400.13 MHz, D2O, ppm), d: 2.39–2.46
(m, 2H, CH2P), 2.98–3.04 (m, 2H, CH2Ph), 7.09–7.29 (m, 5H, Ph). 13C NMR
followed by Fourier synthesis using SHELXS-97.17 The structure was refined
using full-matrix least-squares anisotropic approximation for all non-hydrogen
atoms with SHELXS-97.17 Coordinates of water hydrogen atoms were defined
experimentally, others geometrically and refined isotropically. Atomic
coordinates, bond lengths, bond angles and thermal parameters have been
deposited at the Cambridge Crystallographic Data Centre (CCDC). These data
can be obtained free of charge via www.ccdc.cam.uk.conts/retrieving.html (or
from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336
033; or deposit@ccdc.cam.ac.uk). Any request to the CCDC for data should
quote the full literature citation and CCDC reference number 789663.
17. Sheldrick, G. M. SHELXS-97, SHELXS-97, Programs for Crystal Structure
Determination and Refinement, Göttingen University, Göttingen, Germany,
1997.
1
(100.62 MHz, D2O, ppm), d: 31.55 (CH2Ph), 54.94 (d, JP,C = 53.1 Hz, CH2P),
125.80 (C-p in Ph), 128.40 (C-o in Ph), 128.75 (C-m in Ph), 142.77 (d,
3JP,C = 20.0 Hz, C-i in Ph). 31P NMR (161.98 MHz, D2O, ppm), d: 85.73. Found (%):
C 34.40; H 3.50; P 11.01; S 34.70. Calcd for C8H9Na2PS3 (%): C, 34.52; H, 3.26; P,
11.13; S, 34.57.
Compound 2b: Di-potassium 2-phenylethyltrithiophosphonate. White
crystalline powder, yield 0.28 g (90%), mp > 250 °C (EtOH). IR (KBr, m
/cmÀ1):
3083, 3058, 3029, 2928, 2860, 1598, 1450, 1368, 1308, 1203, 1187, 1171, 1153,
1125, 1171, 1074, 1052, 1030, 1001, 941, 917, 883, 854, 825, 766, 733, 703,