Reaction of trimethylsilyl phosphites with functionalyzed aromatic aldehydes

Full text of DOI:10.1007/s11176-006-0023-1

Russian Journal of General Chemistry, Vol. 75, No. 12, 2005, pp. 1965 1967. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 12, 2005,
pp. 2055 2057.
Original Russian Text Copyright
2005 by Prishchenko, Livantsov, Novikova, Livantsova, Maryashkin.
LETTERS
TO THE EDITOR
Reaction of Trimethylsilyl Phosphites
with Functionalyzed Aromatic Aldehydes
A. A. Prishchenko, M. V. Livantsov, O. P. Novikova,
L. I. Livantsova, and A. V. Maryashkin
Lomonosov Moscow State University, Moscow, Russia
Received May 5, 2005
Reactions of trimethylsilyl esters of trivalent phos-
(XO)2POSiMe3 + ArCHO
(XO)2PCH(OSiMe3)Ar,
phorus acids with various carbonyl compounds is a
convenient method for preparing a series of substi-
tuted hydroxymethylphosphonic and -phosphinic acids
which present interest as promising ligands and bio-
logically active compounds [1]. In the present work
we studied reactions of diethyl trimethylsilyl and tris-
(trimethylsilyl) phosphites with various functiona-
lyzed aromatic aldehydes. It was found that phos-
phites A smoothly add in methylene chloride across
the carbonyl group of aldehydes to form phosphonates
Ia Id in high yields.
O
A
Ia Id
Ar = 4-FC6H4 (a), 4-MeOC6H4 (b), 4-Me2NC6H4 (c)
(d); X = Me3Si (a c), Et (d).
N
Aldehydes B and C containing the hydroxy or
carboxy group in the aromatic ring react with excess
phosphites A to form phosphonates Ie Ig. Under
these conditions, hydroxyl-containing groups, too, are
readily silylated.
2A
OSiMe3
(XO)2P CH
O OSiMe3
Ie, If
OH
H(O)C
(XO)2P(O)H
OMe
B
X = Et (e), Me3Si (f).
2(EtO)2POSiMe3
(EtO)2P(O)H
COOH
(EtO)2P CH
COOSiMe3
H(O)C
O OSiMe3
OMe
OMe
C
Ig
Phosphonates Ie and If are also formed by the
addition of phosphites A to trimethylsilyl vanillin
derivative II that was specially prepared by the reac-
tion of vanillin B with excess chlorotrimethylsilane
(cf. [2]).
Treatment of phosphonates Ia Ic and If with
excess methanol gives substituted phosphonic acids
as white hygroscopic crystals.
3MeOH
Ia Ic
(HO)2PCH(OH)Ar,
3Me3SiOMe
A
Me3SiCl
HCl
O
OSiMe3
OMe
Ie, If
B
H(O)C
III V
Ar = 4-FC6H4 (III), 4-MeOC6H4 (IV), 4-Me2NC6H4 (V).
1070-3632/05/7512-1965 2005 Pleiades Publishing, Inc.
II

1966
PRISHCHENKO et al.
Bis(trimethylsilyl) [[3-methoxy-4-(trimethyl-
4MeOH
OH
OMe
(HO)2P CH
O OSiMe3
VI
If
siloxy)phenyl](trimethylsiloxy)methyl]phosphonate
4Me3SiOMe
1
(Ie). Yield 85%, bp 170 C (1 mm Hg), mp 60 C. H
2
NMR spectrum, , ppm: 4.73 d (C1H, JPH 16 Hz),
3.75 s (CH3O). 13C NMR spectrum, C, ppm: 72.17 d
1
(C1, JPC 180 Hz), 131.74 s (C2), 55.39 s (CH3O),
The NMR spectra of compounds I VI contain
characteristic signals of the PC1H(OSiMe3)C2 and
aromatic fragments.
144.14 s and 150.56 s (OC=). 31P NMR spectrum,
ppm: 4.08 s.
,
P
Diethyl [[4-(trimethylsiloxycarbonyl)phenyl]-
Bis(trimethylsilyl) [(4-fluorophenyl)(trimethyl-
siloxy)methyl]phosphonate (Ia). To a solution of
10.7 g of tris(trimethylsilyl) phosphite in 30 ml of
methylene chloride, a solution of 3.7 g of 4-fluoro-
benzaldehyde in 10 ml of methylene chloride was
added dropwise with stirring at 10 C. The reaction
mixture was stirred for 0.5 h and heated to boil. The
solvent was removed, and the residue was distilled in
a vacuum to give 10.5 g of phosphonate Ia, yield
(trimethylsiloxy)methyl]phosphonate (Ig). Yield
1
82%, bp 182 C (1 mm Hg). H NMR spectrum, ,
2
ppm: 4.95 d (C1H, JHH 16 Hz). 13C NMR spectrum,
1
C, ppm: 71.57 d (C1, JPC 170 Hz), 130.84 s (C2),
166.30 s (C=O). 31P NMR spectrum, , ppm: 19.36 s.
3-Methoxy-4-(trimethylsiloxy)benzaldehyde
(II). A mixture of 7.6 g of vanillin and 30 g of chloro-
trimethylsilane was refluxed under argon until hydro-
gen chloride no longer evolved. The solvent was re-
moved, and the residue was distilled in a vacuum to
give 8.7 g (87%) of compound II, bp 133 C (1 mm
1
83%, bp 133 C (1 mm Hg), mp 69 C. H NMR spec-
2
trum, , ppm: 4.51 d (C1H, JPH 12 Hz). 13C NMR
1
spectrum, C, ppm: 71.31 (C1, JPC 178 Hz), 133.79 s
1
(C2), 162.05 d (CF, 1JCF 246 Hz). 31P NMR spectrum,
Hg). H NMR spectrum, , ppm: 0.24 s (CH2Si),
P, ppm: 3.28 s.
3.83 s (CH3O), 6.9 7.4 m (C6H3), 9.80 s (CHO). 13C
NMR spectrum, C, ppm: 0.45 s (CH3Si), 55.40 s
(CH3O), 150.81 s and 151.44 s (OC=), 190.87 s
(CHO).
Phophonates Ib Ig were obtained analogously.
Bis(trimethylsilyl) [( p-methoxyphenyl)(tri-
methylsiloxy)methyl]phosphonate (Ib). Yield 80%,
1
[(4-Fluorophenyl)hydroxymethyl]phosphonic
acid (III). A solution of 10.5 g of phosphonate Ia in
10 ml of diethyl ether was added dropwise with stir-
ring at 10 C to 20 ml of methanol. The resulting mix-
ture was heated to boil, the solvent was distilled off,
and the residue was kept in a vacuum (1 mm Hg) for
1 h to give 4.9 g (95%) of acid III. 1H NMR spectrum,
, ppm: 4.79 d (C1H, 2JPH 12 Hz). 13C NMR spectrum,
bp 152 C (2 mm Hg). H NMR spectrum, , ppm:
2
4.62 d (C1H, JPH 12 Hz), 3.56 s (CH3O). 13C NMR
1
spectrum, C, ppm: 71.76 d (C1, JPC 180 Hz),
129.92 s (C2), 54.89 s (CH3O), 159.20 s (OC=). 31P
NMR spectrum, P, ppm: 3.96 s.
Bis(trimethylsilyl) [[4-(dimethylamino)phenyl]-
(trimethylsiloxy)methyl]phosphonate (Ic). Yield
1
89%, bp 164 C (1 mm Hg), mp 55 C. H NMR spec-
1
C, ppm: 70.05 d (C1, JPC 160 Hz), 136.76 d (CF,
2
trum, , ppm: 4.64 d (C1H, JPH 16 Hz), 2.78 s
1JFC 244 Hz). 31P NMR spectrum, P, ppm: 18.51 s.
Found, %: C 40.65; H 4.05. C7H8FO4P. Calculated,
%: C 40.79; H 3.91.
(CH3N). 13C NMR spectrum, C, ppm: 71.76 d (C1,
1JPC 182 Hz), 125.16 s (C2), 40.09 s (CH3N),
149.91 s (NC=). 31P NMR spectrum, P, ppm: 4.44 s.
Diethyl [3-pyridyl(trimethylsiloxy)methyl]phos-
Acids IV VI were prepared analogously.
1
[Hydroxy(p-methoxyphenyl)methyl]phosphonic
phonate (Id). Yield 78%, bp 152 C (2 mm). H
1
2
acid (IV). Yield 98%. H NMR spectrum, , ppm:
NMR spectrum, , ppm: 4.70 d (C1H, JPH 14.4 Hz).
2
4.63 d (C1H, JPH 12 Hz), 3.73 s (CH3). 13C NMR
1
13C NMR spectrum, C, ppm: 69.25 d C1, JPC
1
spectrum, C, ppm: 70.23 d (C1, JPC 160 Hz),
172.5 Hz, 132.94 s (C2). 31P NMR spectrum, P, ppm:
16.51 s.
132.28 s (C2), 55.50 s (CH3), 158.79 s (OC=). 31P
NMR spectrum, P, ppm: 19.44 s. Found, %: C 43.90;
H 5.12. C8H11O5P. Calculated, %: C 44.05; H 5.08.
Diethyl [[3-methoxy-4-(trimethylsiloxy)phenyl]-
(trimethylsiloxy)methyl]phosphonate (Ie). Yield
1
81%, bp 168 C (1 mm Hg). H NMR spectrum, ,
{[4-(Dimethylamino)phenyl]hydroxymethyl}-
2
1
ppm: 4.73 d (C1H, JPH 12 Hz), 3.66 s (CH3O). 13C
phosphonic acid (V). Yield 96%. H NMR spectrum,
1
2
NMR spectrum, C, ppm: 71.56 d (C1, JPC 172 Hz),
, ppm: 4.54 d (C1H, JPH 12 Hz), 2.86 s (CH3N). 13
C
130.60 s (C2), 55.26 s (CH3O), 144.25 s and 150.50 s
(OC=). 31P NMR spectrum, P, pm: 20.64 s.
NMR spectrum, C, ppm: 70.51 d (C1, JPC 161 Hz),
1
128.09 s (C2), 40.89 s (CH3N), 150.10 s (NC=). 31P
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 12 2005

REACTION OF TRIMETHYLSILYL PHOSPHITES
NMR spectrum, P, ppm: 19.44 s. Found, %: C 46.64;
1967
REFERENCES
H 6.16. C9H14NO4P. Calculated, %: C 46.76; H 6.10.
1. Wozniak, L. and Choinowski, J., Tetrahedron, 1989,
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Davydochkina, O.V., Zh. Obshch. Khim., 1986, vol. 56,
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1986, vol. 56, no. 8, p. 1813.
[(4-Hydroxy-3-methoxyphenyl)hydroxymethyl]-
phosphonic acid (VI). Yield 95%. 1H NMR spectrum,
2
, ppm: 4.20 d (C1H, JPH 16 Hz), 3.74 s (CH3O). 13
C
NMR spectrum, C, ppm: 80.85 d (C1, JPC 164 Hz),
127.41 s (C2), 55.97 s (CH3O), 146.64 s and 147.59 s
(OC=). 31P NMR spectrum, P, ppm: 19.57 s. Found,
%: C 40.95; H 4.81. C8H11O6P. Calculated, %:
C 41.04, H 4.74.
1
The NMR spectra were obtained on a Bruker
Avance 400 spectrometer in CDCl3 or DMSO (acids
III VI) against TMS (1H, 13C) and 85% H3PO4 in
D2O (31P).
ACKNOWLEDGMENTS
The work was financially supported by the Russian
Foundation for Basic Research (project no. 05-03-
34864).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 12 2005