Nucleophilic diaddition of secondary phosphine sulfides to acetylene and methylacetylene

Article abstract of DOI:10.1007/s11172-009-0035-1

Secondary phosphine sulfides react with acetylene and methylacetylene in the system KOH-DMSO (50 °C, 2-3 h) to form the corresponding tertiary bis-phosphine sulfides in high yield (up to 97%). Specific features of the NMR spectra (¹H, ¹³

Full text of DOI:10.1007/s11172-009-0035-1

Russian Chemical Bulletin, International Edition, Vol. 58, No. 1, pp. 234—237, January, 2009
234
Nucleophilic diaddition of secondary phosphine sulfides
to acetylene and methylacetylene*
N. K. Gusarova, S. F. Malysheva, N. A. Belogorlova, V. A. Kuimov, I. A. Ushakov, and B. A. Trofimov
A. E. Favorsky Irkutsk Institute of Chemistry,
Siberian Branch of the Russian Academy of Sciences,
1 ul. Favorskogo, 664033 Irkutsk, Russian Federation.
Fax: +7 (395) 241 9346. Eꢀmail: gusarova@irioch.irk.ru
Secondary phosphine sulfides react with acetylene and methylacetylene in the system
КOH—DMSO (50 °C, 2—3 h) to form the corresponding tertiary bisꢀphosphine sulfides in
high yield (up to 97%). Specific features of the NMR spectra (1H, 13C, and 31P) of compounds
obtained are discussed.
Key words: acetylene, methylacetylene, alkynes, phosphine sulfides.
Bisꢀphosphine sulfides are under intensive study as
red phosphorus, and elementary sulfur, to acetylene and
methylacetylene has been studied.17,18
efficient polydentate ligands for the design of metal comꢀ
plex catalysts,1—4 antipyrenes,5 intermediate products for
the development of fluorescent and electroluminescent
sensors,6 as well as promising solvents and intermediates
for the preparation of semiconducting nanomaterials.7 Bisꢀ
phosphine sulfides with chiral centers are of particular
value.8 Reduction of the latter leads to the corresponding
optically active bisꢀphosphines,9 which are widely used in
the catalytic stereoselective synthesis.10,11 At the same
time, methods for the preparation of bisꢀphosphine sulꢀ
fides, as a rule, are multistep and laborious and are based
on toxic phosphorus halides and organometallic reagents.12
One of the most convenient approaches to the synthesis
of tertiary bisꢀphosphine chalcogenides is the reaction of
nucleophilic addition of two molecules of secondary phosꢀ
phine chalcogenide to acetylenes. This reaction is at the
time under intensive study on the example of “activated”
acetylenes with the triple bond bearing electronꢀwithꢀ
drawing groups.13—16 The reaction of acetylene and its
first and the most available homolog (methylacetylene)
with secondary phosphine sulfides has not been impleꢀ
mented so far. Moreover, it was reported13 that diphenylꢀ
phosphine sulfide does not react with electronꢀsaturated
acetylenes (hexyne, phenylacetylene) under nucleophilic
conditions, for example, in the system КОH—H2O—
MeCN.
Experiments showed that virtually no reaction takes
place in the system КОH—THF. At the same time, when
superbasic catalytic system КОH—DMSO19 was used, the
nucleophilic addition of two molecules of secondary phosꢀ
phine sulfide proceeds efficiently at mild temperatures
(50 °C, 2—3 h) under pressure of acetylene (autoclave,
the initial pressure of 14 atm) or in the channel system
(in the case of methylacetylene) with the formation of
bisꢀadducts 2a—c in high yield (Scheme 1).
Scheme 1
In the present work, in order to develop a straightꢀ
forward method for the synthesis of new bisꢀphosphine
sulfides, the reaction of nucleophilic addition of secondꢀ
ary phosphine sulfides 1a,b, easily available from styrenes,
* Dedicated to Academician A. I. Konovalov in honor of his
75th anniversary.
R1 = R2 = H (a); R1 = But, R2 = H (b); R1 = H, R2 = Me (c)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 232—234, January, 2009.
1066ꢀ5285/09/5801ꢀ234 © 2009 Springer Science+Business Media, Inc.

Bisꢀphosphine sulfides
PCH2CH2Ph
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 1, January, 2009
235
a
PCH2CH2Ph
PCH2CH2P
33.0
31.5
30.0
28.5
27.0
25.5
24.0
δ,
м.д.
b
33.0
31.5
30.0
28.5
27.0
25.5
24.0
δ
Fig. 1. Fragments of experimental (a) and simulated (b) 13C NMR spectra of compound 2a.
Certain specific features are observed in the NMR
spectra (1H, 13C, and 31P) of compounds obtained.
Thus, in the 1H NMR spectra of compounds 2a,b, the
signals of the bridged CH2 groups for the methylene proꢀ
tons in the fragment (S)PCH2CH2P(S) are present as a
broad singlet in the region 2.0 ppm, that, probably, results
from the retarded rotation around the C—C bond. The
signals for the protons of the CH2 group of the phenylethyl
fragment are represented by two multiplets at 2.0—2.2 ppm
((S)PCH2) and 2.8—3.0 ppm (CH2Ph).
in the 13C NMR spectra results from the isotopic shift of
the 31P NMR signal for the phosphorus atom bonded to
the 13C carbon atoms in the system AA´XX´ under conꢀ
sideration. Assignment of the 1H and 13C signals was made
using 2Dꢀheteronuclear NMR spectroscopy methods
HSQC and HMBC, which confirm structures of the comꢀ
pounds.
In the 31P NMR spectra of compounds 2a,b, the phosꢀ
phorus atoms resonate as singlets with chemical shifts
characteristic of tertiary phosphine sulfides.21
For unsymmetric compound 2c, four lines are
observed in the 31P NMR spectrum and additional signals
appear in the 13C NMR spectrum.
In conclusion, the use of superbasic system КОH—DMSO
allowed us to accomplish for the first time the reaction of
nucleophilic addition of two molecules of secondary phosꢀ
phine sulfides to acetylene and methylꢀacetylene and to
obtain the corresponding bisꢀphosphine sulfides in high
yields.
In the 13C NMR spectra of 2a,b, the signals of the
PhCH2CH2P(S) and (S)PCH2CH2P(S) groups are repreꢀ
sented by complex multiplets (Fig. 1, a). Earlier, in Ref. 20
dealt with the study of polyphosphines with the ethylene
bridge, it has been reported that the signals for the 13C
carbon atoms of the PCH2CH2P group are triplets and
this was the basis for the suggestion on the equivalence of
1
2
the JC,P and JC,P spinꢀspin coupling constant values in
such a fragment. Taking into account the complex charꢀ
acter of the multiplets observed in the 13C NMR spectra,
we simulated the 13C NMR spectrum using the gNMR 5.0
program, which allows one to perform the iteration selecꢀ
tion of spectral parameters (Fig. 1, b). The calculations
Experimental
IR spectra were recorded on a Specord IRꢀ75 spectrometer
in KBr pellets. 1H, 13C, and 31P NMR spectra were recorded on
a Bruker DPX 400 spectrometer (400, 100, and 161.98 MHz,
respectively) in CDCl3 with HMDS as the internal standard. To
assign signals in the 1H and 13C NMR spectra, twoꢀdimensional
homoꢀ and heteronuclear methods of NMR spectroscopy
1
2
3
result in determination of precise JC,P, JC,P, and JP,P
spinꢀspin coupling constant values, which differ from
those measured directly from the spectrum and agree with
the values observed by us earlier for phosphine sulfide
series.21 A decrease in the intensity of central component

236
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 1, January, 2009
Gusarova et al.
(NOESY, HSQC) were used. Analysis of the crossꢀsections in
the 2Dꢀspectrum HSQC allowed us to determine positions of
the resonance signals for the aliphatic protons, which are
complex overlapping multiplets resulted from the homonuclear
1Hꢀ1H and heteronuclear 1Hꢀ31P spinꢀspin interactions. The
nonequivalence of the protons in the fragments CH2P=S results
from their diastereotopy.
Experiments with acetylene were carried out in a 0.25ꢀL
autoclave under pressure of acetylene (the initial pressure at
room temperature was ~14 bar, the residual pressure, ~11 bar).
2.01—2.03 (m, 1 H, PCH); 2.15—2.17 (m, 8 H, PCH2),
2.48—2.64 (m, 1 H, CH2), 2.79—2.98 (m, 8 H, PhCH2),
7.19—7.28 (m, 20 H, Ph). 13C NMR (CDCl3), δ: 15.42
2
(Me), 28.66 (d, CH2Ph, JP,C = 2.9 Hz), 29.79 (d, CHP,
1
1JP,C = 45.7 Hz), 30.03 (d, CH2P, JP,C = 46.4 Hz), 30.40
and 30.57 (d, Me, 1JP,C = 45.7 Hz), 33.76 and 34.68 (d, CH2P,
1JP,C = 47.9 Hz), 126.31 (pꢀCPh), 127.96 (oꢀCPh), 128.42 (mꢀ
CPh), 140.11 (d, ipsoꢀCPh, 3JP,C = 12.8 Hz). 31P NMR (CDCl3),
3
3
δ: 50.43 (d, JP,P = 26.9 Hz) and 60.41 (d, JP,P = 26.9 Hz).
IR (KBr), ν/cm–1: 3103, 3083, 3062, 3024, 3000 (=CH ring);
2970, 2949, 2928, 2900, 2864 (C—H); 1601, 1583, 1495, 1452
(C=C ring); 744, 698 δ(CH ring); 560, 545 (P=S). Found (%):
C, 71.45; H, 7.17; P, 10.89, S, 10.59. C35H42P2S2. Calculated (%):
C, 71.40; H, 7.19; P, 10.52; S, 10.89. The 1Hꢀ1H COSY
twoꢀdimensional homonuclear NMR procedure with decoupling
1,2ꢀBis[bis(2ꢀphenylethyl)thiophosphoryl]ethane
(2a).
A suspension of bis(2ꢀphenylethyl)phosphine sulfide (1a) (0.3 g,
1.1 mmol), КОH (1.04 g, 18.6 mmol) in DMSO (35 mL) was
saturated with acetylene, stirred for 3 h at 50 °C, cooled, diluted
with water, and extracted with benzene. The benzene extracts
were washed with water and dried with K2CO3, benzene was
evaporated, the residue was dried in vacuo to obtain compound
2a (0.3 g, 97%), white powder, m.p. 166—168 °C (hexane). 1H NMR
(CDCl3), δ: 1.94 (br.s, 4 H, PCH2CH2P), 2.04—2.06 (m, 8 H,
PCH2), 2.90—2.92 (m, 8 H, PhCH2), 7.17—7.27 (m, 20 H, Ph).
13C NMR (CDCl3), δ: 24.07 (m, PCH2CH2P, 1JP,C = 56.1 Hz),
1
on the 31P nucleus was used to assign signals in the H NMR
spectra.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 07ꢀ03ꢀ00562a).
1
28.49 (m, PhCH2CH2P), 32.55 (m, PCH2CH2Ph, JP,C = 48.9
References
Hz), 126.71 (pꢀCPh), 128.44 (оꢀCPh), 128.87 (mꢀCPh), 140.24
3
(m, ipsoꢀCPh, JP,C = 12.8 Hz). 31P NMR (CDCl3): δ 51.32.
P
IR (KBr), ν/cm–1: 3100, 3079, 3063, 3025, 3000 (=CH ring);
2895, 2864, 2851 (CH); 1601, 1583, 1494 (C=C ring); 1452,
1436, 1401 δ(CH2); 1189, 1180, 1141, 952, 858; δ(CH ring); 780
δ(CH2); 759 (P—C); 746, 702 δ(CH ring); 545 (P=S); 503 δ
(CPC). Found (%): C, 70.65; H, 7.58; P, 10.89, S, 11.03.
C34H40P2S2. Calculated (%): C, 71.05; H, 7.01; P, 10.78; S, 11.16.
1,2ꢀBis{bis[2ꢀ(4ꢀtertꢀbutylphenyl)ethyl]thiophosphoryl}ethane
(2b). Compound 2b (0.21 g, 68%) was synthesized under
conditions for compound 2a from bis[2ꢀ(4ꢀtertꢀbutylphenyl)ꢀ
ethyl]phosphine sulfide (1b) (0.3 g, 0.78 mmol), white powder,
m.p. 242 °C (hexane). 1H NMR (CDCl3), δ: 1.25 (s, 36 H,
CH3), 2.01—2.07 (br.s, 12 H, CH2PCH2CH2), 2.85—2.88 (m,
8 H, CH2C6H4), 7.09—7.27 (m, 16 H, C6H4). 13C NMR
1. O. Crespo, G. M. Concepcion, P. G. Jones, A. Laguna,
Inorg. Chem., 1994, 33, 6128.
2. D. Belletti, C. Graiff, V. Lostao, R. Pattacini, G. Predieri,
A. Tiripicchio, Inorg. Chim. Acta, 2003, 347, 137.
3. D. W. Allen, in Organophosphorus Chemistry, Eds. D. W. Allen,
J. C. Tebby, The Royal Society of Chemistry, London, 2005,
34, 1.
4. V. Matulova, S. Man, M. Necas, Polyhedron, 2007, 26, 2569.
5. US Pat. 3284543; RZhKhim. [Abstr. J. Chem], 1968, 10C,
385P (in Russian).
6. M.ꢀH. HaꢀThi, M. Penhoat, V. Michelet, I. Leray, Org.
Lett., 2007, 9, 1133.
7. H. Liu, J. S. Owen, A. P. Alivisatos, J. Am. Chem. Soc., 2007,
129, 305.
1
(CDCl3), δ: 23.94 (m, PCH2CH2P, JP,C = 45.0 Hz). 28.04
8. S. Hiroshi, M. Satoru, I. Tsuneo, Nippon Kagakkai Koen
Yokoshu, 2001, 79, 1260.
(PCH2CH2C6H4), 31.38 (CH3), 32.76 (m, PCH2CH2C6H4,
1JP,C = 48.0 Hz), 34.44 [C(CH )], 125.68 (oꢀCC H ), 127.96
6
4
3
,
3JP,C = 13.3 Hz), 149.63
9. Ch. J. Chapman, Ch. G. Frost, M. P. GillꢀCarey, G. Kociokꢀ
Köhn, M. F. Mahon, A. S. Weller, M. C. Willis, Tetrahedron
Asymmetry, 2003, 14, 705.
(mꢀCC H ), 137.15 (m, ipsoꢀCC H
(pꢀCC H ). 31P NMR (CDCl3): δ4 51.45. IR (KBr), ν/cm–1
:
6
4
6
6
4
3094, 3055, 3024 (=CH ring); 29P62, 2933, 2902, 2866 (CH);
1516 (C=C ring); 1474, 1463, 1446 δ(CH2); 1410, 1394, 1363,
1269 δ(CH3); 811 δ(CH ring); 561, 552 (P=S). Found (%):
C, 75.09; H, 9.06; P, 7.15, S, 8.24. C50H72P2S2. Calculated (%):
C, 75.14; H, 9.08; P, 7.75; S, 8.02.
10. Catalytic Asymmetric Synthesis, Ed. I. Ojima, 2nd ed., WileyꢀVCH,
Weinheim, 2000.
11. Phosphorus Ligands in Asymmetric Catalysis: Synthesis and
Applications, Ed. A. Börner, V. 1, WileyꢀVCH, Weinheim,
2008, 1546 p.
12. Von R.Weisheit, R. Stendel, B. Messbauer, C. Langer,
B. Walther, Z. Anorg. Allg. Chem., 1983, 504, 147.
13. D. Semenzin, G. EtemadꢀMoghadam, D. Albouy, O. Diallo,
M. Koenig, J. Org. Chem., 1997, 62, 2414.
14. S. N. Arbuzova, N. K. Gusarova, M. V. Bogdanova, N. I.
Ivanova, I. A. Ushakov, A. G. Mal’kina, B. A. Trofimov,
Mendeleev Commun., 2005, 183.
15. T. E. Glotova, M. Yu. Dvorko, S. N. Arbuzova, I. A.
Ushakov, S. I. Verkhoturova, N. K. Gusarova, B. A. Trofimov,
Lett. Org. Chem., 2007, 109.
1,2ꢀBis[bis(2ꢀphenylethyl)thiophosphoryl]propane (2c).
A suspension of КОH (1.04 g, 18.6 mmol) in DMSO (10 mL)
was saturated with methylacetylene and a solution of phosphine
sulfide 1a (0.26 g, 1.0 mmol) in DMSO (5 mL) was added
dropwise for 0.5 h at 50 °C with simultaneous bubbling of
methylacetylene. The reaction mixture was stirred for additional
0.5 h followed by addition of another portion of phosphine sulfide
1a (0.07 g) in DMSO (1 mL), the mixture was stirred for 1 h at
50 °C, cooled, diluted with water, and extracted with benzene.
The benzene extracts were washed with water and dried with
K2CO3, benzene was evaporated, the residue was dried in vacuo
to obtain compound 2c (0.3 g, 94%), colorless clear crystals,
m.p. 106 °C (hexane). 1H NMR (CDCl3), δ: 1.37 (dd, 3 H, Me,
16. T. E. Glotova, M. Yu. Dvorko, N. K. Gusarova, S. N.
Arbuzova, I. A. Ushakov, T. I. Kazantseva, B. A. Trofimov,
Phosphorus, Sulfur, Silicon, Relat. Elem., 2008, 183, 1396.
3
3JH,H = 7.1 Hz, JH,P = 17.6 Hz); 1.54—1.58 (m, 1 H, CH2);

Bisꢀphosphine sulfides
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 1, January, 2009
237
17. N. K. Gusarova, M. V. Bogdanova, N. I. Ivanova, N. A.
Chernysheva, B. G. Sukhov, L. M. Sinegovskaya, O. A.
Kazheva, G. G. Alexandrov, O. A. D’yachenko, B. A. Trofimov,
Synthesis, 2005, 3103.
18. S. N. Arbuzova, N. K. Gusarova, B. A. Trofimov, Arkivoc,
2006, (V), 12.
20. R. B. King, J. C. Cloyd, J. Chem. Soc., Perkin Trans. 2,
1975, 938.
21. N. K.Gusarova, N. I. Ivanova, M. V. Bogdanova, S. F.
Malysheva, N. A. Belogorlova, B. G. Sukhov, B. A. Trofimov,
Mendeleev Commun., 2004, 216.
19. B. A. Trofimov, in Sovremennye problemy organicheskoi khimii
[Modern Problems of Organic Chemistry], Eds A. A. Potekhin,
R. R. Kostikov, M. S. Baird, VVM, St.ꢀPetersburg, 2004,
131 (in Russian).
Received July 29, 2008;
in revised form December 25, 2008