Synthesis of aryl-substituted trimethylsilyl (trimethylsiloxymethyl) phosphonites

Full text of DOI:10.1007/s11176-005-0486-5

Russian Journal of General Chemistry, Vol. 75, No. 10, 2005, pp. 1669 1671. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 10, 2005,
pp. 1748 1750.
Original Russian Text Copyright
2005 by Prishchenko, Livantsov, Novikova, Livantsova, Kashulin.
LETTERS
TO THE EDITOR
Synthesis of Aryl-Substituted Trimethylsilyl
(Trimethylsiloxymethyl)phosphonites
A. A. Prishchenko, M. V. Livantsov, O. P. Novikova, L. I. Livantsova, and I. A. Kashulin
Moscow State University, Moscow, Russia
Received March 1, 2005
Functionalized trimethylsilyl alkylphosphonites
Me3SiO
containing highly reactive PH fragments are key com-
pounds for preparing various functionalized phos-
phinates, which are of interest as potential ligands and
biologically active compounds [1]. This study con-
cerns the reaction of bis(trimethylsiloxy)phosphine A
with various aromatic aldehydes and development on
its basis of a convenient route to aryl-substituted
trimethylsilyl trimethylsiloxymethylphosphonites I.
Phosphine A in methylene chloride readily adds to
the carbonyl group of various aromatic aldehydes to
form phosphonites Ia Ie in high yields:
PCH(OSiMe3)Ar
(Me3SiO)2PH + ArCHO
H
O
Ia Ie
A
Ar = Ph (a), 4-FC6H4 (b), 4-MeOC6H4 (c),
4-Me2NC6H4 (d), (e).
N
The reactions of aldehydes B and C containing a
hydroxy or carboxy group in the aromatic ring with
excess phosphine A under the similar conditions yield
phosphonites If and Ig. Their formation is accom-
panied by trimethylsilylation of these groups:
Me3SiO
2A
OSiMe3
P CH
OH
OMe
H(O)C
Me3SiOP(O)H2
H
O OSiMe3
OMe
If
B
Me3SiO
2A
COOH
H(O)C
COOSiMe3
OMe
P CH
Me3SiOP(O)H2
H
O OSiMe3
Ig
OMe
C
Treatment of phosphonites Ib and Ic with dilute
solutions of sodium methylate in methanol yields
water-soluble salts III and IV, which are white hygro-
scopic crystals.
The NMR spectra of I III contain the character-
istic signals of the HPC1H(OSiMe3)C2 fragments and
also the signals of aromatic fragments (see below).
According to the NMR spectra, compounds I are
mixtures of two stereoisomers. Their ratio was eval-
uated by 31P NMR spectroscopy. Data for the major
isomer are given first.
MeONa,
2MeOH
NaO
Ib, Ic
PCH(OH)Ar
Me3SiOMe
H
O
Trimethylsilyl [phenyl(trimethylsiloxy)methyl]-
phosphonite Ia. To a solution of 20 g of bis(trimethyl-
siloxy)phosphine A in 50 ml of methylene chloride,
a solution of 5.3 g of benzaldehyde in 25 ml of
II, III
Ar = 4-FC6H4 (II), 4-MeOC6H4 (III).
1070-3632/05/7510-1669 2005 Pleiades Publishing, Inc.

1670
PRISHCHENKO et al.
1
methylene chloride was added dropwise with stirring
at 10 C. The resulting mixture was stirred for 0.5 h
and then heated to reflux. After that, the solvent was
removed and the residue was distilled to give 13.1 g
(83%) of phosphonite Ia, bp 144 C (2 mm). First
Second isomer. H NMR spectrum, , ppm: 4.59 d
(C1H, JPH 7.9 Hz), 6.71 d (PH, JPH 550.9 Hz),
2
1
2.78 s (CH3N). 13C NMR spectrum, C, ppm: 73.25 d
(C1, JPC 121 Hz), 122.49 s (C2), 39.80 s (CH3N),
1
149.99 s (NC=). 31P NMR spectrum, P, ppm: 23.81
1
d.d (1JPH 550.9, JPH 7.9 Hz).
2
isomer (60% content). H NMR spectrum, , ppm:
2
1
4.78 d (C1H, JPH 4 Hz), 6.82 d (PH, JPH 556.9 Hz).
13C NMR spectrum, C, ppm: 72.83 d (C1, JPC
1
Trimethylsilyl [piryd-3-yl(trimethylsiloxy)-
methyl]phosphonite Ie. Yield 78%, bp 162 C
118 Hz), 135.07 d (C2, JPC 3 Hz). 31P NMR spec-
2
1
(2 mm). First isomer (57% content). H NMR spec-
trum, P, ppm: 23.04 d.d (1JPH 556.9, JPH 4 Hz).
2
2
trum, , ppm: 4.72 d (C1H, JPH 4 Hz), 6.73 d (PH,
1
1JPH 560.9 Hz). NMR spectrum, C, ppm: 70.63 d
Second isomer. H NMR spectrum, , ppm: 4.67 d
(C1H, JPH 11.9 Hz), 6.72 d (PH, JPH 556.9 Hz). 13C
2
1
(C1, JPC 116 Hz), 130.78 d (C2, 2JPC 3 Hz). 31P NMR
1
NMR spectrum, C, ppm: 73.47 d (C1, JPC 117 Hz),
1
spectrum, P, ppm: 21.44 d.d (1JPH 560.9, JPH 4 Hz).
2
135.48 s (C2). 31P NMR spectrum, P, ppm: 23.40 d.d
1
Second isomer. H NMR spectrum, , ppm: 4.60 d
2
(1JPH 556.9, JPH 11.9 Hz).
2
1
(C1H, JPH 13.9 Hz), 6.65 d (PH, JPH 562.8 Hz). 13C
NMR spectrum, C, ppm: 71.16 d (C1, JPC 117 Hz),
1
Phosphonites Ib Ig were prepared similarly.
131.26 s (C2). 31P NMR spectrum, P, ppm: 22.03 d.d
Trimethylsilyl [4-fluorophenyl(trimethylsiloxy)-
(1JPH 562.8, JPH 13.9 Hz).
2
methyl]phosphonite Ib. Yield 87%, bp 142 C
1
(2 mm), mp 49 C. First isomer (58% content). H
Trimethylsilyl [3-methoxy-4-trimethylsiloxy-
phenyl(trimethylsiloxy)methyl]phosphonite If.
Yield 82%, bp 164 C (1 mm). First isomer (57%
2
NMR spectrum, , ppm: 4.80 d (C1H, JPH 4 Hz),
1
6.84 d (PH, JPH 556.9 Hz). 13C NMR spectrum,
,
C
ppm: 72.33 d (C1, JPC 118 Hz), 131.02 s (C2),
1
content). H NMR spectrum, , ppm: 4.67 d (C1H,
1
162.34 d (CF, JPC 245 Hz). 31P NMR spectrum,
,
1
2JPH 4 Hz), 6.77 d (PH, JPH 554.8 Hz), 3.63 s
1
P
ppm: 22.39 d (1JPH 556.9). Second isomer. H NMR
1
(CH3O). 13C NMR spectrum, C, ppm: 72.71 d (C1,
spectrum, , ppm: 4.68 d (C1H, JPH 12 Hz), 6.73 d
2
2
1JPC 119.4 Hz), 128.59 d (C2, JPC 2.5 Hz), 54.90 s
(PH, JPH 550.9 Hz). 13C NMR spectrum, C, ppm:
1
1
(CH3O), 143.97 s and 150.30 s (OC=). 31P NMR
72.97 d (C1, JPC 118 Hz), 131.56 s (C2), 162.34 d
2
1
spectrum, P, ppm: 23.20 d.d (1JPH 554.8, JPH
(CF, JPC 245 Hz). 31P NMR spectrum, P, ppm:
1
4 Hz). Second isomer. H NMR spectrum, , ppm:
23.25 d (1JPH 550.9 Hz).
4.54 d (C1H, 2JPH 9.9 Hz), 6.70 d (PH, 1JPH 554.9 Hz),
3.62 s (CH3O). 13C NMR spectrum, C, ppm: 73.33 d
Trimethylsilyl [ p-anisyl(trimethylsiloxy)me-
thyl]phosphonite Ic. Yield 86%, bp 172 C (3 mm).
(C1, JPC 119.4 Hz), 128.83 s (C2), 54.90 s (CH3O),
1
1
First isomer (55% content). H NMR spectrum,
,
144.16 s and 150.40 s (OC=). 31P NMR spectrum,
,
ppm: 4.67 d.d (C1H, 2JPH 8, 3JHH 4 Hz), 6.74 d.d (PH,
P
ppm: 22.93 d.d (1JPH 554.9, JPH 9.9 Hz).
2
1JPH 552.9, JHH 4 Hz), 3.57 s (CH3O). 13C NMR
3
1
Trimethylsilyl [4-trimethylsiloxycarbonyl-
phenyl(trimethylsiloxy)methyl]phosphonite Ig.
Yield 82%, bp 178 C (1 mm), mp 66 C. First isomer
spectrum, C, ppm: 72.44 d (C1, JPC 120.2 Hz),
126.90 d (C2, JPC 3 Hz), 54.57 s (CH3O), 159.08 s
2
(OC=). 31P NMR spectrum, P, ppm: 22.74 d (1JPH
552.9 Hz). Second isomer. 1H NMR spectrum, , ppm:
4.56 d (C1H, 2JPH 10 Hz), 6.65 d (PH, 1JPH 552.9 Hz),
1
(59% content). H NMR spectrum, , ppm: 5.01 d.d
2
3
1
(C1H, JPH 7.9, JHH 4 Hz), 6.99 d.d (PH, JPH 562.8,
3JHH 4 Hz). 13C NMR spectrum, C, ppm: 72.97 d (C1,
3.58 s (CH3O). 13C NMR spectrum, C, ppm: 73.00 d
2
1JPC 115 Hz), 131.04 d (C2, JPC 4 Hz), 166.35 s
(C1, JPC 120 Hz), 127.31 s (C2), 54.53 s (CH3O),
1
(C=O). 31P NMR spectrum, P, ppm: 22.38 d.d (1JPH
159.17 s (OC=). 31P NMR spectrum, P, ppm:
2
1
562.8, JPH 7.9 Hz). Second isomer. H NMR spec-
trum, , ppm: 4.89 d (C1H, 2JPH 13.8 Hz), 6.85 d (PH,
1JPH 560.8 Hz). 13C NMR spectrum, C, ppm: 73.66
23.44 d.d (1JPH 552.9, JPH 10 Hz).
2
Trimethylsilyl [4-dimethylaminophenyl(tri-
d (C1, JPC 114 Hz), 131.24 d (C2, JPC 4 Hz),
1
2
methylsiloxy)methyl]phosphonite Id. Yield 83%, bp
1
166.29 s (C=O). 31P NMR spectrum, P, ppm: 23.15
159 C (1 mm). First isomer (53% content). H NMR
2
spectrum, , ppm: 4.69 d (C1H, JPH 4 Hz), 6.80 d
d.d (1JPH 560.8, JPH 13.8 Hz).
2
1
(PH, JPH 548.9 Hz), 2.79 s (CH3N). 13C NMR spec-
Sodium 4-fluorophenyl(hydroxy)methylphos-
phonite II. A solution of 10 g of phosphonite Ib in
20 ml of diethyl ether was added with stirring at 10 C
to a solution of 1.6 g of sodium methylate in 30 ml
1
trum, C, ppm: 72.75 d (C1, JPC 121.9 Hz), 122.19 d
2
(C2, JPC 2.5 Hz), 39.88 s (CH3N), 149.99 s (NC=).
31P NMR spectrum, P, ppm: 23.09 d (1JPH 548.9 Hz).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 10 2005

SYNTHESIS OF ARYL-SUBSTITUTED TRIMETHYLSILYL
1671
of methanol. The mixture was heated to reflux, the
solvent was removed, and the residue was kept in a
vacuum (1 mm) for 1 h to give 6 g (95%) of salt II.
II and III) against TMS (1H, 13C) and 85% phos-
phoric acid in D2O (31P).
2
1H NMR spectrum, , ppm: 4.60 d (C1H, JPH 8 Hz),
ACKNOWLEDGMENTS
1
6.75 d (PH, JPH 520 Hz). 13C NMR spectrum,
,
C
ppm: 73.01 d (C1, JPC 105.3 Hz), 133.07 s (C2),
1
The study was financially supported by the Russian
Foundation for Basic Research (project no. 05-03-
32864).
162.14 d (CF, JFC 246.3 Hz). 31P NMR spectrum, ,
1
ppm: 26.3 d (1JPH 520 Hz). Found, %: C 39.49; H
3.38. C7H7FNaO3P. Calculated, %: C 39.64; H 3.33.
REFERENCES
Compound III was prepared similarly.
1. Prishchenko, A.A., Lorentz, K.-L., Livantsov, M.V.,
Min’ko, S.V., Grigor’ev, E.V., and Luzikov, Yu.N.,
Zh. Obshch. Khim., 1994, vol. 64, no. 9, p. 1579; Pri-
shchenko, A.A., Livantsov, M.V., Livantsova, L.I.,
Pol’shchikov, D.G., and Grigor’ev, E.V., Zh. Obshch.
Khim., 1996, vol. 66, no. 11, p. 1924; Prishchenko, A.A.,
Livantsov, M.V., Novikova, O.P., Pol’shchikov, D.G.,
and Grigor’ev, E.V., Zh. Obshch. Khim., 2000, vol. 70,
no. 6, p. 1042; Prishchenko, A.A., Livantsov, M.V.,
Novikova, O.P., and Livantsova, L.I., Zh. Obshch.
Khim., 2005, vol. 75, no. 2, p. 344.
Sodium p-anisyl(hydroxy)methylphosphonite
1
III. Yield 97%. H NMR spectrum, , ppm: 4.57 d
2
1
(C1H, JPH 7,9 Hz), 6.76 d (PH, JPH 517.2 Hz),
3.74 s (CH3). 13C NMR spectrum, , ppm: 72.98 d
(C1, JPC 106.2 Hz), 129.63 s (C2), 55.33 s (CH3),
1
158.50 s (OC=). 31P NMR spectrum, P, ppm: 27.13
d.d (1JPH 517.2, JPH 7.9 Hz). Found, %: C 42.69;
2
H 4.57. C8H10NaO4P. Calculated, %: C 42.87; H 4.50.
The NMR spectra were measured on a Bruker
Avance 400 NMR spectrometer in CDCl3 or D2O (for
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 10 2005