REACTION OF BIS(TRIMETHYLSILYL) INDEN-2-YLPHOSPHONATE
1457
14.8 Hz), 140.92 d (C3, JPC 11.9 Hz), 138.92 d (C4,
2
3
4
2
3JPC 17.0 Hz), and 141.61 d (C4, JPC 12.1 Hz),
2MeONa, MeOH
2Me3SiOMe
1
(NaO)2P
O
I
137.08 s (C5), 159.96 s (=CO), 55.18 s (CH3O). 31P
NMR spectrum, P, ppm: 2.55 s.
4
2
III
Bis(trimethylsilyl) (1-furfurylideneinden-2-yl)-
phosphonate (IIc). Yield 74%, bp 210 C (2 mm Hg),
mp 61 C. 13C NMR spectrum, C, ppm: 133.82 d (C1,
3
4
2MeONa, MeOH
2Me3SiOMe
1
IIa IId
(NaO)2P
O
2
1JPC 205.6 Hz), 135.51 d (C2, JPC 15.6 Hz),
2
4
2
3
140.60 d (C3, JPC 12.3 Hz), 134.93 d (C4, JPC
XCH
IVa IVd
16.4 Hz) and 141.40 d (C4, JPC 21.7 Hz), 127.84 s
3
(C5), 144.88 s (=CHO), 151.69 s (=CO). 31P NMR
spectrum, P, ppm: 2.22 s.
(c),
(d).
X = Ph (a), 4-MeO C6H4 (b),
N
Bis(trimethylsilyl) [1-(pyridin-3-ylmethylene)-
inden-2-yl]phosphonate (IId). Yield 72%, bp 200 C
(1 mm Hg), mp 65 C. 13C NMR spectrum, C, ppm:
spectra, the signals of these fragments partially or
completely overlap in the range 6.5 8.00 ppm.
1
2
133.33 d (C1, JPC 208.2 Hz), 135.85 d (C2, JPC
2
12.3 Hz), 142.70 d (C3, JPC 12.5 Hz), 141.25 d (C4,
Bis(trimehylsilyl) inden-2-ylphosphonate (I).
A mixture of 100 g of bis(trimethylsilyl)amine and
43 g of inden-2-ylphosphonic acid prepared according
to [2] was refluxed until ammonia no longer evolved
and then distilled in a vacuum to give 66.4 g of ester
3
3JPC 15.9 Hz) and 141,93 d (C4, JPC 20.9 Hz),
136.75 s (C5), 149.10 s (C=N) and 149.53 s (C=N).
31P NMR spectrum, P, ppm: 3.3 s.
1
I, yield 89%, bp 149 C (1 mm), mp 52 C. H NMR
Disodium inden-2-ylphosphonate (III). To a
solution of 1.1 g of sodium methylate in 30 ml of
methanol, a solution of 3.4 g of phosphonate I in 5 ml
of diethyl ether was added with stirring and cooling
to 10 C. The resulting mixture was heated to boiling,
the solvent was distilled off, and the residue was kept
in a vacuum (1 mm Hg) for 1 h to give 2.3 g (96%)
spectrum, , ppm: 3.50 s (C2H2), 7.1 7.4 m (5CH,
C9H7), 0.21 d (Me6Si2, JPH 4.8 Hz). 13C NMR spec-
4
trum, C, ppm: 137.31 d (C1, JPC 208.2 Hz), 39.57 d
1
(C2, JPC 15.2 Hz), 141.86 d (C3, JPC 14.7 Hz),
2
2
142.54 d (C4, JPC 21.3 Hz) and 144.6 d (C4, JPC
3
3
12.3 Hz), 0.60 s (CSi). 31P NMR spectrum, P, ppm:
1.11 s.
of salt III. H NMR spectrum, , ppm: 3.65 s (C2H2),
1
7.2 7.6 m (5 CH, C9H7). 13C NMR spectrum,
,
C
1
2
ppm: 147.11 d (C1, JPC 176.2 Hz), 40.68 d (C2, JPC
Bis(trimethylsilyl) (1-benzylideneinden-2-yl)-
phosphonate (IIa). To a solution of 4.5 g of phos-
phonate I in 10 ml of diethyl ether, 1.6 g of N-benzyl-
idene-N-methylamine and 0.1 g of sodium hydride
was added with stirring. After 2 h, the solvent was
removed, and the residue was distilled in a vacuum to
give 4.3 g of phosphonate IIa, yield 75%, bp 212 C
(2 mm Hg), mp 74 C. 13C NMR spectrum, C, ppm:
2
11.9 Hz), 135.91 d (C3, JPC 10.7 Hz), 144.64 d (C4,
3
3JPC 18.9 Hz) and 145.62 d (C4, JPC 10.7 Hz).
31P NMR spectrum, P, ppm: 10.70 s. Found, %: C
44.91; H 3.03. C9H7Na2O3P. Calculated, %: C 45.02;
H 2.94.
Salts IVa IVd were prepared in a similar way.
135.93 d (C1, JPC 208.3 Hz), 136.25 d (C2, JPC
1
2
Disodium (1-benzylideneinden-2-yl)phospho-
14.9 Hz), 141.94 d (C3, JPC 12.3 Hz), 139.14 d (C4,
2
nate (IVa). Yield 97%. 13C NMR spectrum, C, ppm:
3JPC 16.0 Hz) and 141.71 d (C4, JPC 18.4 Hz),
3
1
2
143.22 d (C1, JPC 174,4 Hz), 136.09 d (C2, JPC
136.83 d (C4, JPC 6,1 Hz). 31P NMR spectrum,
,
3
8.4 Hz), 136.68 d (C3, JPC 9.8 Hz), 139.98 d (C4,
2
P
3JPC 12.09 Hz) and 143.64 d (C4, JPC 20.4 Hz),
3
ppm: 2.87 s.
136.43 s (C4). 31P NMR spectrum, P, ppm: 7.81 s.
Found, %: C 58.43; H 3.41. C16H11Na2O3P. Calcu-
lated, %: C 58.55; H 3.38.
Phosphonates IIb IId were prepared in a similar
way.
Bis(trimethylsilyl) (4-methoxybenzylidene-
inden-2-yl)phosphonate (IIb). Yield 78%, bp 210 C
Disodium (4-methoxybenzylideneinden-2-yl)-
1
1
(1.5 mm Hg), mp 89 C. H NMR spectrum, , ppm:
phosphonate (IVb). Yield 97%. H NMR spectrum,
3.84 s (CH3O). 13C NMR spectrum. C, ppm:
, ppm: 3.78 s (CH3O). 13C NMR spectrum, C, ppm:
1
2
1
2
135.28 d (C1, JPC 206.2 Hz), 136.14 d (C2, JPC
143.31 d (C1, JPC 172.9 Hz), 135.97 d (C2, JPC
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 9 2004