Reaction of bis(trimethylsiloxy)phosphine with trimethylsilane

Article abstract of DOI:10.1134/S1070363209060061

Bis(trimethylsilyl) [3-(trimethylsilyl)propyl]phosphonate and trimethylsilyl [3-(trimethylsilyl)propyl]-phosphinate are obtained by the reaction of bis(trimethylsiloxy)phosphine with trimethylallylsilane and converted into [3-(trimethylsilyl)propyl]phosphinic and [3-(trimethylsilyl) propyl]phosphonic acid, respectively, by the reaction with methanol.

Full text of DOI:10.1134/S1070363209060061

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 6, pp. 1080–1082. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © M.G. Voronkov, А.Е. Pestunovich, A.I. Albanov, V.A. Kukhareva, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79,
No. 6, pp. 908–910.
Reaction of Bis(Trimethylsiloxy)phosphine
with Trimethylsilane
M. G. Voronkov, А. Е. Pestunovich, A. I. Albanov, and V. A. Kukhareva
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: voronkov@irioch.irk.ru
Received January 12, 2009
Abstract—Bis(trimethylsilyl) [3-(trimethylsilyl)propyl]phosphonate and trimethylsilyl [3-(trimethylsilyl)propyl]-
phosphinate are obtained by the reaction of bis(trimethylsiloxy)phosphine with trimethylallylsilane and
converted into [3-(trimethylsilyl)propyl]phosphinic and [3-(trimethylsilyl)propyl]phosphonic acid, respectively,
by the reaction with methanol.
DOI: 10.1134/S1070363209060061
Bis(trimethylsiloxy)phosphine (Me3SiO)2PH was
first synthesized by the reaction of ammonium
hypophosphite with trimethyl(diethylamino)silane or
hexamethyldisilazane [1]. It was found that bis
(trimethylsiloxy)phosphine is readily oxidized to bis-
(trimethylsilyl)phosphonate (Me3SiO)2P(O)H and is
self-ignited in air.
(0.03 mol %) without solvent in the argon atmosphere.
After reflux of the reaction mixture during 7 h, 70% of
the starting trimethylallylsilane remained intact;
therefore, the reaction is sluggish under the studied
conditions. Further operations in the contact with air
and investigation of the reaction mixture led to
substantial changes of the composition of the reaction
mixture due to interaction with the atmospheric
oxygen and moisture. The methods of 1H, 13C, 29Si, 31P
NMR and IR spectroscopy revealed the presence of
unreacted bis(trimethylsiloxy)phosphine, trimethylsilyl-
hypophosphite (I), bis(trimethylsilyl) phosphonate (II),
bis(trimethylsilyl) [3-(trimethylsilyl)propyl]phosphonate
(III), trimethylsilyl [3-(trimethylsilyl)propyl]phosphonite
(IV), tris(trimethylsilyl) phosphate (V). The expected
product of addition of bis(trimethylsiloxy)phosphine to
trimethylallylsilane, bis(trimethylsilyl) [3-(trimethyl-
silyl)propyl]phosphonite was not detected. The forma-
tion of the above products is the result of the following
reactions.
Addition of bis(trimethylsiloxy)phosphine to the
C=C and C=O bonds was first realized in [1, 2]. Later
on, the reactions of addition of bis(trimethylsiloxy)-
phosphine to double bonds attracted great interest
since they lead to the earlier unknown or hardly
accessible organophosphorus compounds. Addition of
bis(trimethylsiloxy)phosphine to the С=С bond pro-
ceeds without a catalyst or in the presence of
azoisobutyronitrile (AIBN) [1–5]. It was reported that
bis(trimethylsiloxy)phosphine is readily added to N,N-
diethyl(vinyl)sulfonamide in the absence of a catalyst
to give the adduct in 78% yield. Along with this, a side
product of addition of trimethylsilylhypophosphite to
two molecules of N,N-diethyl(vinyl)sulfonamide was
isolated in 12% yield [3]. The addition of bis(trimethyl-
siloxy)phosphine to the derivatives of vinylsilanes
(CH2=CH)nSiX4–n (X = Alk, AlkO, n = 1, 2) is
thoroughly studied [1, 2, 5]. However, its reaction with
Si-substituted allylsilanes CH2=CHCH2SiX3 proceeds
with difficulty and, hence, is poorly studied [2].
(Me3SiO)2PH + H2O → Me3SiOP(=O)H2 + Me3SiOH,
I
+ 0.5 О2
(Me3SiO)2PH
(Me3SiO)2P(=O)H,
II
(Me3SiO)2PH + CH2=CHCH2SiMe3
→ [(Me3SiO)2PCH2CH2CH2SiMe3]
We have studied the possibility of addition of bis-
(trimethylsiloxy)phosphine to trimethylallylsilane in
the molar ratio of 1:1 in the presence of AIBN
+ 0.5 О2
(Me3SiO)2P(=O)CH2CH2CH2SiMe3,
III
1080

REACTION OF BIS(TRIMETHYLSILOXY)PHOSPHINE WITH TRIMETHYLSILANE
1081
Bis(trimethylsilyl) [3-(trimethylsilyl)propyl]phos-
phonate (III) and trimethylsilyl [3-(trimethylsilyl)-
propyl]phosphinate (IV). Mixture of 6.2 g of bis-
(trimethylsiloxy)phosphine, 4.6 g of trimethylallyl-
silane and 0.05 g AIBN was refluxed during 7 h. After
vacuum distillation, 3.3 g of unreacted trimethylallyl-
silane was isolated and 2.7 g of a fraction with bp 53–
80°С (10 mm Hg), consisting of bis(trimethylsiloxy)
phosphine, trimethylsilylhypophosphite I and bis-
(trimethylsilyl) phosphonate II. Trimethylsilyl hypo-
phosphite I has the structure corresponding to formula
Me3SiOP(=O)РH2 trimethylsilyl phosphonite rather
than Me3SiOPHOH. This is unequivocally proved by
splitting of the phosphorus signal (δP –2.0 ppm) into a
triplet on two hydrogen atoms with JP–H 552.37 Hz. A
higher-boiling fraction with bp 85–90°С (5 mm Hg)
contains, from the 31Р NMR data, 0.35 g of bis(tri-
methylsilyl) phosphonate II and 0.1 g of tris(trimethyl-
silyl) phosphate V. 31P NMR of V, δP, ppm: –25.36.
The high-boiling fraction with bp 108–111°С (4 mm
Hg) contains, from the 31Р NMR data, 0.12 g of O,O-
bis(trimethylsilyl) [3-(trimethyl)silylpropyl]phosphonate
III and 0.45 g of trimethylsilyl [3-(trimethyl)silyl-
propyl]phosphinate IV. Bis(trimethylsilyl) [3-(trimethyl)-
Me3SiOP(=O)H2 + CH2=CHCH2SiMe3
I
→ (Me3SiO)HP(=O)CH2CH2CH2SiMe3,
IV
(Me3SiO)2PH + Me3SiOH → [(Me3SiO)3P]
+ 0.5 О2
(Me3SiO)3P=O.
V
Bis(trimethylsilyl) [3-(trimethylsilyl)propyl]phosphonate
(Me3SiO)2P(=O)(CH2)3SiMe3 (III) and trimethylsilyl
[3-(trimethylsilyl)propyl]phosphonite (Me3SiO)HP·
(=O)CH2CH2CH2SiMe3 (IV) were not known so far.
Their yields were 1 and 6%, respectively, calculated to
the starting bis(trimethylsiloxy)phosphine. In the IR
spectrum of phosphinate IV the bands at 2380 (Р–Н),
1240 (Р=О), 850 (SiMe3), 1050 (Si–О–Р) cm–1 are
present.
By the reaction with methanol, compounds IV and
III were converted into the liquid 3-(trimethylsilylpropyl)-
phosphinic VI and crystalline 3-(trimethylsilyl)propyl)-
phosphonic VII acids.
1
(Me3SiO)HP(=O)(CH2)3SiMe3 + MeOH
silylpropyl]phosphonate III, Н NMR, δ, ppm: 0.67
IV
(CH2Si), 1.61–1.80 (CH2CH2P), 0.36 (Me3SiO), 0.00
(Me3SiCH2). 13C NMR, δC, ppm: 17.60 (CH2Si), 32.08
→ (HO)HP(=O)(CH2)3SiMe3 + Me3SiOMe,
1
VI
(CH2P, JC–P 142 Hz), 0.05 (Me3SiO), –2.32 (Me3Si).
31P NMR, δP, ppm: 13.45. 29Si NMR, δSi, ppm: 18.7.
Trimethylsilyl [3-(trimethylsilyl)propyl]phosphinate IV,
1H NMR, δ, ppm: 0.67 (CH2Si), 1.61–1.80
(CH2CH2P), 0.36 (Me3SiO), 0.00 (Me3Si), 7.1 (P–H).
13С NMR, δС, ppm: 17.50 (CH2Si), 15.34 (CH2), 34.1
(Me3SiO)2P(=O)(CH2)3SiMe3 + 2 MeO
III
→ (HO)2P(=O)(CH2)3SiMe3 + 2 Me3SiOMe.
VII
1
The ionization constant pK1 of 3-(trimethylsilyl)pro-
pyl)phosphinic acid (HO)HP(=O)(CH2)3SiMe3 (VI)
determined by the method of potentiometric titration in
water is 3.85. Hence, it is weaker than the acids of
general formula (HО)2P(=O)(CH2)nSiMe3, n = 1–3 [6].
(CH2P, JC–P 92.8 Hz), 0.41 (Me3SiO), –2.32 (Me3Si).
31P NMR, δP, ppm: 26.6, JPH 535 Hz. 29Si NMR, δSi,
ppm: 22.05 (Me3SiO), 0.24 (Me3SiCH2), 2JSi–P 5.83 Hz.
Trimethylsilylpropylphosphinic acid (VI). Mix-
ture of 0.3 g of phosphonate III, phosphinate IV, 2 ml
of methanol, 2 ml of methylene chloride was heated to
reflux for 1.5 h. Low-boiling compounds were
removed under vacuum, the residue dried for 1 h at
3 mm Hg. The mixture of liquid trimethylsilyl-
propylphosphinic acid VI and crystalline phosphonic
acid VII was isolated. Trimethylsilylpropylphosphinic
Compounds III and IV were isolated as a binary
mixture and investigated by the methods of
multinuclear NMR and IR spectroscopy. The structure
of the hitherto unknown acid VI was proved by the
method of multinuclear NMR.
EXPERIMENTAL
1
acid VI, Н NMR, δ, ppm: 0.66 (CH2Si), 1.67 (C–
IR spectra were recorded in thin layer on a Specord
IR-75 spectrophotometer.
CH2–C), 1.86 (P–CH2), 0.04 (Me3Si), 10.82 (OH),
3
7.15 (Р–Н). 13С NMR, δС, ppm: 18.12 (СН2Si, JC–P
1
NMR spectra of 5–10% solutions of compounds in
С6D6 and CDCl3 were obtained on a Bruker DPX 400
spectrometer using HMDS as an internal standard.
14.19 Hz), 15.58 (С–СН2–С), 32.68 (СН2Р, JC–P
92.4 Hz), –1.7 (SiMe3). 31P NMR, δР, ppm: 39.11, JP–H
543.6 Hz. 29Si NMR, δSi, ppm: 0.89. Found, %: P
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 6 2009

1082
VORONKOV et al.
Phosporus, London: Harwood Academic Publishers,
1991, vol. 2.
3. Prishchenko, А.А., Livantsov, M.V., Livantsova, L.I.,
Pol’shchikov, D.G., and Grigor’ev, E.V., Russ. J. Gen.
Chem., 1997, vol. 67, no. 10, p. 1641.
4. Prishchenko, А.A., Livantsov, M.V., Livantsova, L.I.,
Novikova, O.P., and Grigor’ev, E.V., Russ. J. Gen.
Chem., 1996, vol. 66, no. 12, p. 1999; Livantsova, L.I.,
Prishchenko, А.А., Livantsov, M.V., Nikolaev, S.N., and
Grigor’ev, E.V., Russ. J. Gen. Chem., 2000, vol. 70, no. 7,
p. 1147; Livantsov, M.V., Prishchenko, А.А., Livan-
tsova, L.I., Nikolaev, S.N., Meleshenkova, N.N., and
Grigor’ev, E.V., Russ. J. Gen. Chem., 2003, vol. 73, no. 1,
p. 153.
17.19. C6H17PO2Si. Calculated, %: P 17.10. The struc-
ture of the earlier described crystalline trimethylsilyl-
propylphosphonic acid VII [2] was proved by multi-
nuclear NMR. Trimethylsilylpropylphosphonic acid
1
VII, Н NMR, ppm: 6.88 (Р–Н). 13С NMR, δС, ppm:
18.30 (CH2Si), 17.16 (C–CH2–C), 30.13 (CH2P). 31Р
NMR, δР, ppm: 35.32. 29Si NMR, δSi, ppm: 0.88.
ACKNOWLEDGMENTS
This work was performed with support from the
Council on Grants of the President of Russian
Federation (grant no. NSh-255.2008.3)
5. Prishchenko, А.А., Livantsov, M.V., Livantsova, L.I.,
Pol’shchikov, D.G., Nikolaev, S.N., and Grigor’ev, E.V.,
Russ. J. Gen. Chem., 1999, vol. 69, no. 1, p. 149; Livan-
tsov, M.V., Prishchenko, А.А., Livantsova, L.I.,
Nikolaev, S.N., and Grigor’ev, E.V., Russ. J. Gen.
Chem., 2003, vol. 73, no. 3, p. 492; Prishchenko, А.А.,
Livantsov, M.V., Novikova, L.I., and Livantsova, L.I.,
Russ. J. Gen. Chem., 2005, vol. 75, no. 2, p. 312.
6. Borisov, S.N., Voronkov, M.G., and Lukevits, E.Ya.,
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