First example of alkylation of secondary phosphine selenides

Full text of DOI:10.1134/S1070363208080288

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 8, pp. 1628–1630. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © N.K. Gusarova, N.I. Ivanova, S.F. Malysheva, A.V. Artem’ev, B.V. Timokhin, B.A. Trofimov, 2008, published in Zhurnal Obshchei
Khimii, 2008, Vol. 78, No. 8, pp. 1393–1395.
LETTERS
TO THE EDITOR
First Example of Alkylation of Secondary Phosphine Selenides
N. K. Gusarova, N. I. Ivanova, S. F. Malysheva, A. V. Artem’ev,
B. V. Timokhin, and B. A. Trofimov
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: gusarova@irioch.irk.ru
Received April 8, 2008
DOI: 10.1134/S1070363208080288
The secondary phosphine selenides I that recently
has become available [1] are promising synthons for
the synthesis of various organophosphorus-selenium
compounds [2–7]. For example, their alkylation may
result in derivatives of three- or four-coordinated
phosphorus since they, similar to the corresponding
Se
P
H
phosphine oxides [8–10] and phosphine sulfides [10–
I
12], might exist in the two tautomeric forms A and B.
Se
MeI/KOH/THF
20_22oC
Se
(2)
P
P
P
SeH
(1)
Me
H
II
A
B
Molar ratio of phosphine selenides I : MeI:KOH = 1:1:1
However, to the best of our knowledge, there are no
published data on the alkylation of secondary
phosphine selenides under basic conditions. At the
same time, investigation of this reaction promises to
open not only a new general preparative route to
synthesis of unsymmetrical tertiary phosphine
selenides but also to throw the light on the problem of
their tautomerism.
Apparently, the contribution of tautomer B in Eq. (1) is
negligible since the nucleophilicity of its anion must
exceed that of the P-centered anion of the tautomeric
form A and, therefore, it would have reacted with
methyl iodide with a higher rate.
Semiempirical quantum chemical calculations of
the conjugate anion of dimethylphosphine selenide by
PM3 method have shown that the HOMO is localized
mainly on the selenium atom. Calculations of the
relative energies of the products of methylation of this
anion suggest the thermodynamic preference of
trimethylphosphine selenide (0 kcal mol–1) whereas the
methyl ester of dimethylselenophosphinous acid is by
15 kcal mol–1 more endothermic.
Our experiments showed that phosphine selenide I
when treated with methyl iodide in the presence of
equimolar amount of KОН (room temperature, THF)
afforded tertiary phosphine selenide II in 74% yield.
No products of methylation of the possible
tautomeric form B were found. The obtained result
suggests that alkylation of secondary phosphine
selenides provides a possibility to synthesize dificultly
available unsymmetrical phosphine selenides under
mild conditions in a satisfactory preparative yield.
Carrying out the methylation of phosphine selenide
I with molar excess of methyl iodide and KOH at
1628

FIRST EXAMPLE OF ALKYLATION
1629
heating (50–60°С) led to a complete replacement of
the selenium atom by oxygen, namely, to the formation
of the corresponding tertiary phosphine oxide III.
65.8 Hz), 27.77 CH2Ph, 31.96 d (PCH2, 1JCP 65.1 Hz),
126.44 Cр, 127.99 Co, 128.66 Cm, 140.79 d (Ci, JCP
3
13.1 Hz). 31Р NMR, δР, ppm: 44.45. IR spectrum
(KBr), cm–1: 3103, 3079, 3060, 3026, 3000 [ν(=CH)];
2978, 2923, 2900, 2861 [ν(CH)]; 1603, 1584, 1508,
1497 [ν(C=C)]; 1454, 1418 [δ(CH2)]; 1296 [δ(CH3)];
1166, 1134 [ν (P=O)]; 1071, 1030, 968, 957, 943, 915,
895, 871 [δ(CH–Ph)]; 767, 753 [δ(P–C)]. Mass spec-
trum, m/z: 272 [M]+.
O
MeI/KOH/THF
50_60oC
(3)
I
P
Me
III
IR spectra were recorded on a Bruker IFS-25
1
spectrometer in KBr. Н, 13С, 31Р and 77Se were taken
Molar ratio of phosphine selenides I : MeI:KOH = 1:5:4
on a Bruker DPX-400 spectrometer (400.13, 101.61,
161.98 and 76.31 MHz, respectively) in CDCl3,
internal reference HMDS, external reference 85%
Н3РО4 (31Р NMR), and internal reference Me2Se (77Se
NMR). Electron impact mass spectra (70 eV) were
obtained on a GCMS-QP5050A SHIMADZU instru-
ment (quadrupole mass analyzer, range of detected
masses 34-450 D, capillary column, phase SPB-5). The
reaction was monitored by 31Р NMR spectroscopy.
Methyl[di(2-phenethyl)]phosphine selenide (II).
To the suspension of 0.056 g of ground KOH in 0.5 ml
of THF the solution of 0.321 g of phosphine selenide I
in 1 ml of THF was added, dry argon was bubbled
through the mixture, and the solution of 0.141 g of MeI
in 0.5 ml of THF was added dropwise in the course of
3 min. The reaction mixture was stirred for 3.5 h at
room temperature, diluted with 2.5 ml of water and
extracted with chloroform (2.5×3 ml). The chloroform
extract was dried with sodium sulfate, the solvent was
removed, the residue was washed with hexane and
dried in a vacuum to afford 0.25 g (74%) of phosphine
REFERENCES
1. Sukhov, B.G., Gusarova, N.K., Ivanova, N.I., Bogda-
nova, M.V., Kazheva, O.N., Aleksandrov, G.G., D’ya-
chenko, O.A., Sinegovskaya, L.M., Malysheva, S.F.,
and Trofimov, B.A., Zh.. Strukt. Khim., 2005, vol. 46,
no. 6, p. 1114.
1
selenide II, yellowish oil. H NMR, δ, ppm: 1.78 d
2
(3H, CH3, JНP 12.6 Hz), 2.23–2.29 m (4H, PCH2),
2.95–3.00 m (4H, PhCH2), 7.21–7.29 m (10H, Ph). 13С
1
NMR, δС, ppm: 18.85 d (CH3, JCP 45.9 Hz), 29.09
2. Gusarova, N.K., Malysheva, S.F., Belogorlova, N.A.,
Sukhov, B.G., and Trofimov B.А., Synthesis, 2007, no. 18,
p. 2849.
CH2Ph, 34.16 d (PCH2, 1JCP 43.1 Hz), 126.38 Cр, 128.09
Co, 128.50 Cm, 140.08 d (Ci, 3JCP 14.4 Hz). 31Р NMR, δР,
ppm: 28.55 (1JPSe 693.8 Hz). 77Se NMR, δSe, ppm: –341.62
d (1JSeP 694.9 Hz). Mass spectrum, m/z: 336 [M]+.
3. Gusarova, N.K., Ivanova, N.I., Konovalova, N.A., Al-
banov, A.I., Sinegovskaya, L.M., Avseenko, N.D., Su-
khov, B.G., Mikhaleva, A.I., Gusarov, A.V., and Tro-
fimov, B.A., Russ. J. Gen. Chem., 2007, vol. 77, no. 3,
p. 409.
Methyl[di(2-phenethyl)]phosphine oxide (III).
To the suspension of 0.21 g of ground KOH in 0.5 ml
of THF the solution of 0.30 g of phosphine selenide I
in 2 ml of THF was added, dry argon was bubbled
through the mixture, and it was heated at 50–60°С,
then the solution of 0.66 g of MeI in 0.5 ml of THF
was added in the course of 5 min. The reaction mixture
was stirred for 1.5 h at 60°С and for another 5 h at
room temperature, diluted with water (3 ml), extracted
with chloroform (2.5×3 ml), the extract was dried over
sodium sulfate, the solvent was removed, the residue
was washed with 2 ml of diethyl ether and dried in a
vacuum. 0.2 g (80%) of phosphine oxide III was
obtained as a sandy powder, mp 58–60°С. 1H NMR, δ,
4. Gusarova, N.K., Ivanova, N.I., Konovalova, N.A., Su-
khov, B.G., Baikalova, L.V., Sinegovskaya, L.M., Pav-
lov, D.V., and Trofimov, B.A., Synthesis, 2006, no. 24,
p. 4159.
5. Davies, R., Martinelli, G., and White, A., Chem.
Commun., 2006, p. 3240.
6. Walther, B., Coord. Chem. Rew., 1984, vol. 60, p. 67.
7. Hoskin, A. and Stephan, D., Organometallics, 1999, vol. 18,
p. 2479.
8. Mastryukova, T.A. and Kabachnik, M.I., Russ. Chem.
Rev., 1991, vol. 60, no. 10, p. 1115.
2
ppm: 1.47 d (3H, CH3, JНP 12.2 Hz), 2.03–2.12 m
(4H, PCH2), 2.93–3.00 m (4H, PhCH2), 7.22–7.35 m
9. Well, M. and Schmutzler, R., Phosphorus, Sulfur and
Silicon, 1992, vol. 72, p. 171.
1
(10H, Ph). 13С NMR, δС, ppm: 14.39 d (CH3, JCP
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 8 2008

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GUSAROVA et al.
10. Kabachnik, M.I. and Mastryukova, T.A., Mezhfaznyi ka-
taliz v fosfororganicheskoi khimii (Phase-Transfer Catalyst
in Organophosphorus Chemistry), Moscow: URSS, 2002.
Kazheva O.N., Ale-xandrov G.G., D’yachenko, O.A.,
and Trofimov, B.A., Synthesis, 2005, no. 18, p. 3103.
12. Arbuzova, S.N., Gusarova, N.K., Bogdanova, M.V.,
Ivanova, N.I., Ushakov, I.A., Mal’kina, A.G., and
Trofimov, B.A., Mendeleev Commun., 2005, no. 5, p. 183.
11. Gusarova, N.K., Bogdanova, M.V., Ivanova, N.I.,
Сhernysheva, N.А., Sukhov, B.G., Sinegovskaya, L.M.,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 8 2008