Nucleophilic addition of phosphine to vinyl sulfoxides

Full text of DOI:10.1134/S1070363208050319

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 5, pp. 1011–1013. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © N.K. Gusarova, S.I. Verkhoturova, T.I. Kazantseva, N.A. Chernysheva, V.L. Mikhailenko, S.F. Malysheva, B.A. Trofimov, 2008,
published in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 5, pp. 868–870.
LETTERS
TO THE EDITOR
Nucleophilic Addition of Phosphine to Vinyl Sulfoxides
N. K. Gusarova, S. I. Verkhoturova, T. I. Kazantseva, N. A. Chernysheva,
V. L. Mikhailenko, S. F. Malysheva, and B. A. Trofimov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: gusarova@irioch.irk.ru
Received February 5, 2008
DOI: 10.1134/S1070363208050319
Reaction of addition of phosphine to multiple
bonds represents an obvious alternative to the
synthesis of organophosphorus compounds by the use
of phosphorus halogenides, opening the route to atom-
sparing design of various phosphines and their
derivatives. In spite of its attractiveness up to now this
alternative has not been systematically developed
although the addition of phosphine to some alkenes
and acetylenes is described in a number of publications
[1, 2]. So far nothing is known about the addition of
phosphine to vinyl sulfoxides. At the same time, this
reaction opens a direct one-step route to difficultly
accessible phosphines with sulfoxide groups,
promising semilabile chelating ligands [3, 4] and
intermediates for preparation of, e.g., radioactive
diagnosticums [5–7].
Our attempts to perform this reaction under radical
conditions (butyl vinyl sulfoxide, DINIZ, 65°С, 5 h)
failed.
At the same time, nucleophilic addition of
phosphine to vinyl sulfoxides Iа, Ib in superbasic
system KOH–DMSO [8] was possible. The reaction
proceeded at room temperature (phosphine was passed
into the suspension consisting of vinyl sulfoxide,
KOH, DMSO). The formation of all possible
phosphines was observed (31P NMR): primary IIа, IIb,
secondary IIIа, IIIb and tertiary IVа, IVb.
R
R
KOH/DMSO
H
S
+ PH3
S
20−22oC
P
O
O
H
IIа, IIb
Iа, Ib
R
R
S
R
R
S
(1)
S
+
S
+
P
P
O
O
O
O
H
S
R
O
IIIа, IIIb
IVа, IVb
R = Bu (а), Ph (b).
1011

1012
GUSAROVA et al.
Note that a less basic catalytic system KOH–di-
saturating with phosphine, 0.60 g of butyl vinyl sulf-
oxide Iа in 10 ml of DMSO was added dropwise
during 1 h at room temperature with simultaneous
passing of phosphine; passing of phosphine continued
for another 2 h, then it was stopped, the reaction
mixture was flushed with argon. In the 31Р NMR
spectrum (δР, ppm) of the reaction mixture the
following signals were present: –135.0 t (1JPH 194 Hz),
–67.8 d (1JPH 198 Hz), and –26.2 in a 2:37:1 ratio,
belonging to primary IIа, secondary IIIа, and tertiary
IVа phosphines, respectively. The reaction mixture
was diluted with equal volume of water, extracted
successively with ether and chloroform, ethereal
extracts were dried with potassium carbonate, ether
was removed, the residue was dried in a vacuum. 0.10 g
of the mixture of primary IIа and secondary IIIа
phosphines was obtained in the ratio 1 : 4 (31Р NMR).
Chloroform extracts were dried with potassium
carbonate, chloroform removed under reduced pressure
to 3/4 of the initial volume. After 7 days the precipitate
formed was filtered off, washed with ether, and dried
in a vacuum to give 0.25 g (35%) of bis[2-(butyl-
sulfinyl)ethyl]phosphine oxide (V) as a white powder,
oxane turned out to be ineffective.
By controlling the conditions of reaction (1) it was
possible to selectively obtain the secondary phosphine
IIIа isolated as the corresponding phosphine oxide V
(nonoptimized preparative yield of pure product was
35%).
Bu
Bu
O
P
O2
S
IIIа
S
(2)
O
O
H
V
In the case of vinyl phenyl sulfoxide Ib during
treatment of the reaction mixture it was possible to
identify by comparison with authentic sample [9] (1Н,
31Р NMR) trivinyl phosphine oxide VI, the product of
elimination of three molecules of phenylsulfenic acid
from tertiary phosphine oxide VII (formed by air
oxidation of the corresponding phosphine IVb).
Ph
Ph
O
P
1
O2
mp 166–168°С (ether). Н NMR (CDCl3), δ, ppm:
S
IVb
S
3
0.98 t (6Н, Me, JНH 7.3 Hz), 1.50 m (4Н, СН2Me),
O
O
1.76 m (4Н, СН2Et), 2.37 m (4Н, СН2Р), 2.70 m, 2.78
m, 2.88 m, 3.08 m (8Н, СН2SO). 31Р NMR (CDCl3),
δР, ppm: 30.6 d (1JPH 474 Hz). IR spectrum (KBr, cm-1):
1009 (S=O), 1163 (P=O), 2368 (P–H). Found, %: С
45.57; Н 8.88; Р 9.88; S 19.90. C12H27O3PS2.
Calculated, %: С 45.84; Н 8.65; Р 9.85; S 20.40.
S
Ph
O
VII
KOH/DMSO
Trivinyl phosphine oxide (VI). To a mixture of
1.80 g of powdered KOH, 16 ml of DMSO, and 1 ml
of Н2O after flushing with argon and saturating with
phosphine 0.91 g of vinyl phenyl sulfoxide Ib in 10 ml
of DMSO was added dropwise during 2 h at room
temperature with simultaneous passing of phosphine.
Phosphine was bubbled for another 2 h, then it was
stopped, the reaction mixture was flushed with argon
and analyzed by 31P NMR. The following signals were
present in the spectrum (δР, ppm): –134.8 t (1JPH 196 Hz),
–68.2 d (1JPH 200 Hz), –26.7 and 25.9 in the ratio
2 : 8 : 1 : 2, belonging to primary IIb, secondary IIIb,
tertiary IVb phosphines, and tertiary phosphine oxide
VII, respectively. To the reaction mixture 0.64 g of
vinyl phenyl sulfoxide Ib in 12 ml of DMSO was
added, the mixture was stirred for another 5 h, diluted
with equal amount of water, extracted with
chloroform, dried with potassium carbonate, solvent
was removed, the residue was dried in a vacuum. 0.25 g
P
(3)
−PhSOK
O
VI
Therefore, nucleophilic addition of phosphine to
vinyl sulfoxides, an important class of functional
alkenes, was performed for the first time. It provides a
simple and convenient approach to the synthesis of
new demanded phosphines and phosphine oxides with
sulfoxide groups.
Phosphine was generated in a separate flask from
red phosphorus and KOH in water-toluene medium
[10].
Bis[2-(butylsulfinyl)ethyl]phosphine oxide (V).
To a mixture of 1.80 g of powdered KOH, 16 ml of
DMSO, and 1 ml of Н2O after flushing with argon and
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 5 2008

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NUCLEOPHILIC ADDITION OF PHOSPHINE TO VINYL SULFOXIDES
3. Leung, P.-H., Siah, S.-Y., White, A.J.P., and Wil-
liams, D.J.J., Chem. Soc., Dalton Trans., 1998, p. 893.
of the product was obtained containing, according to
the 31Р NMR spectrum (δР, CDCl3) trivinyl phosphine
oxide VI (18.2 ppm) and phosphine oxide VII (25.6 ppm)
4. Hiroi, K., Suzuki, Y., and Kawagishi, R., Tetrahedron
Lett., 1999, no. 40, p. 715.
1
in the ~2:1 ratio (yield 18 and 10%, respectively). H
and 31Р NMR spectra of individual trivinyl phosphine
oxide (isolated by sublimation) are identical to those of
an authentic sample [9].
5. Archer, C.M., Dilworth, J.R., Griffiths, D.V., Hughes, J.M.,
Kelly, J.D., and Morton, S., Technetium in Chemistry
and Nuclear Medicine, Nicolini, M., Bandoli, G., and
Mazzi, U., Eds., Padova: SGEditoriali, 1995, p. 173.
1Н and 31Р NMR spectra were registered on a
Bruker DPX-400 spectrometer (400.13 and 161.98 МHz,
respectively), internal standard HMDS, external
standard 85% Н3РO4. IR spectra were taken on a
Bruker-IFS 25 instrument in KBr pellets.
6. Griffiths, D.V., Caesar, J.C., Hughes, J.M., Mahoney, P.M.,
Swetnam, S.P., Walton, G., and Yorkm D.C., Phosph.
Sulphur, Silicon, 1999, no. 146, p. 485.
7. Griffiths, D.V., Groombridge, H.J., Mahoney, P.M.,
Swetnam, S.P., Walton, G., and York, D.C.,
Tetrahedron, 2005, no. 61, p. 4595.
ACKNOWLEDGMENTS
8. Trofimov, B.A., Sovremennye problemy organicheskoi
khimii (Modern Problems of Organic Chemistry),
Potekhin, A.A., Kostikov, R.R., and Berd, M.S., Eds.,
St-Petersburg: ВВМ, 2004, no. 14, p. 131.
This work was performed with financial support from
the Russian Foundation for Basic Research (Grant No.
07-03-00562) and SD RAS (Integration Project No. 32).
9. Gusarova, N.K., Chernysheva, N.A., Arbuzova, S.N.,
Bogdanova, M.V., Ivanova, N.I., Kudryavtsev, A.A.,
and Trofimov, B.A., Mendeleev Commun., 2006, no. 1,
p. 31.
REFERENCES
1. Trofimov, B.A., Arbuzova, S.N., and Gusarova, N.K.,
Russ. Chem. Rev., 1999, vol. 68, no. 3, p. 215.
10. Trofimov, B.A., Gusarova, N.K., Malysheva, S.F.,
Shaikhudinova, S.I., Belogorlova, N.A., Kazantseva, T.I.,
Sukhov, B.I., and Plotnikova, G.V., Russ. J. Gen. Chem.,
2005, vol. 75, no 5, p. 684.
2. Arbuzova, S.N., Gusarova, N.K., and Trofimov, B.A.,
Arkivoc, 2006, Part V, p. 12.
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