Reaction of Bis(trimethylsiloxy)phosphine with Methyl(phenyl)divinylsilane [3]

Full text of DOI:10.1023/A:1024990827222

Russian Journal of General Chemistry, Vol. 73, No. 3, 2003, pp. 492 493. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 3, 2003,
pp. 525 526.
Original Russian Text Copyright
2003 by Prishchenko, Livantsov, Livantsova, Novikova, Nikolaev, Grigor’ev.
LETTERS
TO THE EDITOR
Reaction of Bis(trimethylsiloxy)phosphine
with Methyl(phenyl)divinylsilane
A. A. Prishchenko, M. V. Livantsov, L. I. Livantsova,
O. P. Novikova, S. N. Nikolaev, and E. V. Grigor’ev
Lomonosov Moscow State University, Moscow, Russia
Received May 7, 2002
Bis(trimethylsiloxy)phosphine is successfully used
NaO
H
in various addition reactions to unsaturated synthons,
leading to promising types of organophosphorus
compounds [1]. We showed that the reaction of an
excess of bis(trimethylsiloxy)phosphine with methyl-
(phenyl)divinylsilane provides a mixture of phos-
phonite I and bisphosphonite II in equal amounts.
Phosphonites I and II were isolated in high yield. The
reaction was initiated with 2,2 -azobisisobutyronitrile
(AIBN) under conditions of its thermolysis (100
130 C).
MeONa, MeOH
2Me3SiOMe
PCH2CH2SiCH=CH2(Me)Ph
I
IV
O
NaO
H
II 2MeONa, 2MeOH
PCH2CH2 Si(Me)Ph
4Me3SiOMe
O
2
V
CH2CH2SiCH=CH2(Me)Ph
MeONa, MeOH
IIIa, IIIb
NaOP
O
CH2NR2
Me3SiOMe
n(Me3SiO)2PH + (CH2=CH)2Si(Me)Ph
R
VIa, VIb
(Me3SiO)2PCH2CH2SiCH=CH2(Me)Ph
I
R2N = Me2N (a),
N (b).
+ [(Me3SiO)2PCH2CH2]2Si(Me)Ph,
II
Salts IV VI are white hygroscopic crystals. The
1H NMR spectra of compounds I VI contain charac-
teristic signals of the PC1H2C2H2Si and PC3H2NC4Hn
R = Me2(NC)C
1
Phosphonite I is easily aminomethylated with bis-
(dialkylamino)methanes at 130 C in the presence of
zinc chloride as catalyst to form phosphinates IIIa
and IIIb in good yields.
fragments. Their parameters are listed below. In H
NMR spectra, the signals of these fragments partially
or completely overlap. The vinyl and phenyl proton
signals of these compounds are multiplets at 5.7 6.5
and 7.2 7.6 ppm, respectively.
CH2CH2SiCH=CH2(Me)Ph
(R2N)2CH2, ZnCl2
I
Me3SiOP
O
Me3SiNR2
CH2NR2
Bis(trimethylsilyl) [2-[methyl(phenyl)(vinyl)-
silyl]ethyl]phosphonite (I) and bis[2-bis(trimethyl-
siloxy)phosphinoethyl]methyl(phenyl)silane (II). A
mixture of 50 g of bis(trimethylsiloxy)phosphine,
12.7 g of methyl(phenyl)(divinyl)silane, and 0.4 g of
AIBN was heated to 100 C and, within 1 h, to 130 C.
After that the reaction mixture was distilled in a
vacuum to give 13.5 g of phosphonite I and 19.6 g of
bisphosphonite II. Phosphonite I, yield 48%, bp
133 C (1 mm). 13C NMR spectrum, C, ppm: 34.01 d
(C1, 1JPC 25.7 Hz), 4.20 d (C2, 2JPC 6.8 Hz). 31P NMR
spectrum, P, ppm: 157.34 s. Phosphonite II, yield
IIIa, IIIb
R2N = Me2N (a),
N (b).
Treatment of phosphonites I and II and phosphi-
nates III with dilute solutions of sodium methylate in
methanol gives water-soluble sodium phosphonates
IV and V and phosphinates VI, which contain stable
organosilicon fragments.
1070-3632/03/7303-0492$25.00 2003 MAIK Nauka/Interperiodica

REACTION OF BIS(TRIMETHYLSILOXY)PHOSPHINE
493
1
3
45%, bp 178 C (1 mm). 13C NMR spectrum, C, ppm:
ppm: 6.83 d.t (PH, JPH 499.2, JHH 1.8 Hz). 13C
1
2
33.58 d (C1, JPC 26.0 Hz), 3.01 d (C2, JPC 10.8 Hz).
NMR spectrum, C, ppm: 25.46 d (C1, JPC 88.0 Hz),
4.33 d (C2, 2JPC 5.4 Hz). 31P NMR spectrum, P, ppm:
1
31P NMR spectrum, P, ppm: 158.23 s.
Trimethylsilyl (dimethylaminomethyl)[2-[me-
thyl(phenyl)(vinyl)silyl]ethyl]phosphinate (IIIa). A
mixture of 4 g of phosphonite I, 2.4 g of bis(dimethyl-
amino)methane, and 0.1 g of zinc chloride was heated
at 110 130 C for 1.5 h and then distilled to give 3 g
31.06 s. Found, %: C 37.59; H 5.10. C11H18Na2O4
P2Si. Calculated, %: C 37.72; H 5.18.
Sodium dimethylaminomethyl[2-[methyl-
(phenyl)vinylsilyl]ethyl]phosphinate (VIa). Yield
of phosphinate III, yield 78%, bp 141 C (1 mm), nD20
1
2
95%. H NMR spectrum, , ppm: 2.49 d (C3H2, JPH
1
1.5019. H NMR spectrum, , ppm: 2.05 s (C4H3).
9.2 Hz), 2.23 s (C4H3). 13C NMR spectrum, C, ppm:
1
13C NMR spectrum, P, ppm: 21.81 d (C1, JPC
24.30 d (C1, JPC 89.7 Hz), 6.27 d (C2, JPC 6.4 Hz),
1
2
2
1
91.5 Hz), 4.84 d (C2, JPC 7.2 Hz), 57.14 d (C3, JPC
58.06 d (C3, JPC 99.4 Hz), 47.27 d (C4, JPC 7.9 Hz).
1
3
111.9 Hz), 47.08 d (C4, JPC 10.0 Hz). 31P NMR
3
31P NMR spectrum, P, ppm: 37.95 s. Found, %: C
52.57; H 7.12. C14H23NNaO2PSi. Calculated, %:
C 52.65; H 7.26.
spectrum, P, ppm: 42.99 s.
Phosphinate IIIb was obtained analogously.
Trimethylsilyl [2-[methyl(phenyl)(vinyl)silyl]-
Sodium [2-[methyl(phenyl)(vinyl)silyl]ethyl](N-
piperidinomethyl)phosphinate (VIb). Yield 93%.
ethyl](N-piperidinomethyl)phosphinate (IIIb).
Yield 72%, bp 189 C (2 mm), n2D0 1.5085. 13C NMR
2
1H NMR spectrum, , ppm: 2.50 d (C3H2, JPH
1
spectrum, C, ppm: 21.60 d (C1, JPC 91.2 Hz), 4.78 d
3
9.2 Hz), 2.42 t (C4H2, JHH 5.2 Hz). 13C NMR
2
1
(C2, JPC 6.7 Hz), 56.31 d (C3, JPC 117.7 Hz),
1
spectrum, C, ppm: 25.01 d (C1, JPC 88.5 Hz), 6.57 d
55.68 d (C4, JPC 8.3 Hz). 31P NMR spectrum,
,
3
2
1
(C2, JPC 6.6 Hz), 57.83 d (C3, JPC 98.6 Hz), 56.19 d
P
(C4, 3JPC 7.0 Hz). 31P NMR spectrum, P, ppm: 38.66.
ppm: 43.32 s.
Sodium [2-[methyl(phenyl)(vinyl)silyl]ethyl]-
phosphonite (IV). To a solution of 1.62 g of sodium
methylate in 50 ml of methanol, a solution of 11.5 g
of phosphonite in 10 ml of diethyl ether was added
with stirring at 10 C. The resulting mixture was
heated to boil, the solvent was removed, and the re-
sidue was kept in a vacuum (1 mm) for 1 h to obtain
Found, %: C 56.64; H 7.49. C17H27NNaO2PSi. Cal-
culated, %: C 56.80; H 7.57.
The NMR spectra were obtained on a Varian VXR-
400 spectrometer in CDCl3 or D2O (salts IV VI)
against TMS (1H, 13C) and 85% H3PO4 in D2O (31P).
1
REFERENCES
7.6 g (96%) of salt IV. H NMR spectrum, , ppm:
1
3
6.84 d.t (PH, JPH 495.6, JHH 1.6 Hz). 13C NMR
1. Prishchenko, A.A., Livantsov, M.V., Min’ko, S.V., and
Petrosyan, V.S., Zh. Obshch. Khim., 1992, vol. 62,
no. 6, pp. 1430 1432; Prishchenko, A.A., Livan-
tsov, M.V., Livantsova, L.I., Pol’shchikov, D.G., and
Grigor’ev, E.V., Zh. Obshch. Khim., 1997, vol. 67,
no. 10, pp. 1744 1745; Prishchenko, A.A., Livan-
tsov, M.V., Livantsova, L.I., Pol’shchikov, D.G., Ni-
kolaev, S.N., and Grigor’ev, E.V., Zh. Obshch. Khim.,
1999, vol. 69, no. 1, pp. 156 157.
spectrum, C, ppm: 25.84 d (C1, JPC 88.3 Hz), 5.23 d
(C2, JPC 5.2 Hz). 31P NMR spectrum, P, ppm:
1
2
30.93 s. Found, %: C 50.26; H 6.09. C11H16NaO2PSi.
Calculated, %: C 50.37; H 6.15.
Salts V and VI were obtained analogously.
Disodium 3-[methyl(phenyl)sila]pentane-1,5-di-
1
phosphonate (V). Yield 94%. H NMR spectrum, ,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 3 2003