PRISHCHENKO Et al.
3 of 5
|
−2.9 (s). Anal. Calcd for C22H29O3PSi2. C 61.65; H 6.82.
Found: C 61.56; H 6.71.
4.1
Diethyl 1H-inden-2-ylphosphonate (2a)
|
A mixture of triethyl orthoformate (101 g, 0.68 mol) and 1H-
inden-2-ylphosphonic acid 1 (33.3 g, 0.17 mol) prepared ac-
cording to[9] was refluxed for 2 hours and then distilled in
a vacuum to give 34.7 g of ester 2a, yield 81%, bp 144°C
(1 mm Hg). 1H NMR (CDCl3, 400 MHz), δ, ppm: 1.2 (t, 6H,
3JHH = 7.2 Hz, 2 Me), 3.50 (s, 2H, C2H2), 4.0-4.1 (m, 4 H, 2
OCH2), 7.2-7.4 (m, 4H, 4 CArH), 7.5 (d, 1H, 3JPH = 10.4 Hz,
C3H). 13C NMR (CDCl3, 100 MHz), δ, ppm: 1.2 (t,
Phosphonates 3b-d were obtained similarly.
4.4
Bis(trimethylsilyl) [1-(4-
|
methoxybenzylidene)-1H-inden-2-yl]
phosphonate (3b)
1
Yield 78%, bp 210°C(1.5 mm Hg), mp 89°C. H NMR
(CDCl3, 400 MHz), δ, ppm: 0.29 (s, 18H, 2 Me3Si), 3.84
(s, 3H, MeO), 6.81-7.60 (m, 8H, 4 CArH, 4 CPhH), 7.64
3JPC = 6.2 Hz, Me), 39.6 (d, JPC = 14.0 Hz, C2), 61.3 (d,
2
2JPC = 5.5 Hz, OCH2), 122.3 (s, CAr), 123.5 (s, CAr), 126.3 (s,
CAr), 126.6 (s, CAr), 133.1 (d, 1JPC = 198.9 Hz, C1), 142.1 (d,
3JPC = 21.1 Hz, C4), 144.6 (d, 2JPC = 13.9 Hz, C3), 144.8 (d,
3JPC = 11.9 Hz, C4). 31P NMR (CDCl3, 162 MHz), δ, ppm:
17.7 (s). Anal. Calcd for C13H17O3P. C 61.90; H 6.79. Found:
C 61.74; H 6.68.
(d, 1H, JPH = 8.4 Hz, C3H), 7.83 (s, 1H, C5H). 13C NMR
3
(CDCl3, 100 MHz), δ, ppm: 0.03 (s, 2 Me3Si), 55.2 (s,
MeO), 113.8 (s, 2 CPh), 122.3 (s, CAr), 123.4 (s, CAr), 126.7
(s, CAr), 127.8 (s, CAr), 131.0 (s, 2 CPh), 136.5 (s, CPh),
135.3 (d, JPC = 206.2 Hz, C1), 136.1 (d, JPC = 14.8 Hz,
1
2
C2), 137.1 (s, C5), 138.9 (d, JPC3 = 17.0 Hz, C4), 140.9 (d,
3
2JPC = 11.9 Hz, C3), 141.6 (d, JPC = 12.1 Hz, C4), 160.0
(s, CPhO). 31P NMR (CDCl3, 162 MHz), δ, ppm: −2.6 (s).
Anal. Calcd for C23H31O4PSi2. C 60.23; H 6.81. Found: C
60.06; H 6.69.
4.2
Bis(trimehylsilyl) 1H-inden-2-
|
ylphosphonate (2b)
A mixture of bis(trimethylsilyl)amine (100 g, 0.62 mol) and
1H-inden-2-ylphosphonic acid 1 (43 g, 0.22 mol) prepared
according to[9] was refluxed until ammonia no longer evolved
and then distilled in a vacuum to give 66.4 g of ester 2b, yield
4.5
Bis(trimethylsilyl) [1-(furan-2-
|
ylmethylene)-1H-inden-2-yl]phosphonate (3c)
1
1
89%, bp 149°C (1 mm Hg), mp 52°C. H NMR (CDCl3,
Yield 74%, bp 210°C (2 mm Hg), mp 61°C. H NMR
4
400 MHz), δ, ppm: 0.21 (d, 18H, JPH = 4.8 Hz, 2 Me3Si),
(CDCl3, 400 MHz), δ, ppm: 0.42 (s, 18H, 2 Me3Si), 6.57-
3.50 (s, 2H, C2H2), 7.1-7.4 (m, 5H, C9H7). 13C NMR (CDCl3,
100 MHz), δ, ppm: 0.60 (s, 2 Me3Si), 39.6 (d, 2JPC = 15.2 Hz),
122.2 (s, CAr), 123.6 (s, CAr), 126.3 (s, 2 CAr), C2, 137.3 (d,
7.60 (m, 7H, 4 CArH, 3 CFurH), 7.7 (s, 1H, C5H), 8.7 (d,
1H, JPH = 7.6 Hz, C3H). 13C NMR (CDCl3, 100 MHz),
3
δ, ppm: 0.91 (s, 2 Me3Si), 112.8 (s, CFur), 118.4 (s, CFur),
120.9 (s, CAr), 122.3 (s, CAr), 124.9 (s, CAr), 127.2 (s, CAr),
1JPC = 208.2 Hz, C1), 141.9 (d, JPC = 14.7 Hz, C3), 142.5
2
3
3
(d, JPC = 21.3 Hz, C4), 144.6 (d, JPC = 12.3 Hz, C4). 31P
NMR (CDCl3, 162 MHz), δ, ppm: −1.1 (s). Anal. Calcd for
C15H25O3PSi2. C 52.91; H 7.40. Found: C 52.76 H 7.26.
127.8 (s, C5), 133.8 (d, JPC = 205.6 Hz, C1), 134.9 (d,
1
3JPC = 16.4 Hz, C4), 135.5 (d, JPC = 15.6 Hz, C2), 140.6
2
(d, JPC = 12.3 Hz, C3), 141.4 (d, JPC = 21.7 Hz, C4),
144.9 (s, CFurHO), 151.7 (s, CFurO). 31P NMR (CDCl3,
162 MHz), δ, ppm: −2.2 (s). Anal. Calcd for C20H27O4PSi2.
C 57.39; H 6.50. Found: C 57.23; H 6.42.
2
3
4.3
Bis(trimethylsilyl) (1-benzylidene-1H-
|
inden-2-yl)phosphonate (3a)
To a solution of phosphonate 2b (4.5 g, 0.013 mol) in di-
ethyl ether (10 mL), N-benzylidene-N-methylamine (1.6 g,
0.013 mol) and sodium hydride (0.1 g, 0.004 mol) were
added with stirring. After 2 hours, the solvent was removed,
and the residue was distilled in a vacuum to give 4.3 g of
phosphonate 3a, yield 77%, bp 212°C (2 mm Hg), mp 74°C.
1H NMR (CDCl3, 400 MHz), δ, ppm: 0.43 (s, 18H, 2 Me3Si),
4.6
Bis(trimethylsilyl) [(1-(pyridin-3-
|
ylmethylene)-1H-inden-2-yl]phosphonate (3d)
1
Yield 72%, bp 200°C (1 mm Hg), mp 65°C. H NMR
(CDCl3, 400 MHz), δ, ppm: 0.45 (s, 18H, 2 Me3Si), 7.05-
7.86 (m, 8H, 4 CArH, 4 CPyH,), 8.66 (d, 1H, 3JPH = 9.7 Hz,
C3H), 8.78 (s, 1H, C5H). 13C NMR (CDCl3, 100 MHz),
δ, ppm: 1.1 (s, 2 Me3Si), 122.2 (s, CAr), 123.7 (s, CPy),
127.4 (s, CAr), 128.6 (s, CAr), 132.1 (s, CAr), 132.7 (s, CPy),
3
6.80-7.60 (m, 9H, 5 CPhH). 7.52 (d, 1H, JPH = 6.8 Hz,
C3H), 7.97 (s, 1H, C5H). 13C NMR (CDCl3, 100 MHz), δ,
ppm: 1.9 (s, 2 Me3Si), 122.5 (s, CAr), 123.6 (s, CAr), 127.0
(s, CAr), 128.3 (s, CPh), 128.5 (s, CPh), 129.1 (s, CPh), 129.2
(s, CPh), 136.5 (s, CAr), 135.9 (d, 1JPC = 208.3 Hz, C1), 136.3
(d, 2JPC = 14.9 Hz, C2), 139.1 (d, 3JPC = 16.0 Hz, C4), 141.9
(d, 2JPC = 12.3 Hz, C3), 141.7 (d, 3JPC = 18.4 Hz, C4), 136.8
(d, 3JPC = 6.1 Hz, C5). 31P NMR (CDCl3, 162 MHz), δ, ppm:
133.3 (d, JPC = 208.2 Hz, C1), 135.9 (d, JPC = 12.3 Hz,
1
2
C2), 136.8 (s, C5), 141.3 (d, JPC2 = 15.9 Hz, C4), 141.9 (d,
3
3JPC = 20.9 Hz, C4), 142.7 (d, JPC = 12.5 Hz, C3), 149.1
(s, CPyN), 149.5 (s, CPyN). 31P NMR (CDCl3, 162 MHz), δ,
ppm: −3.3 (s). Anal. Calcd for C21H28NO3PSi2. C 58.71; H
6.57. Found: C 58.62; H 6.52.