326
cyclopenta[a]indene-4,4,5,5-tetracarbonitrile (14)
43.1 (CH), 42.1 (CH), 37.0 (CH), 32.7 (CH2), 24.8 (CH2), 24.2
Colorless solid, mp: 169-170 °C, Rf (pentane / Et2O = 3 / 1) (CH2), 22.3 (CH2), 21.4 (CH2), 16.8 (CH), 16.3 (CH), 15.9
= 0.37. (CH).
1H NMR (600 MHz, CDCl3): δ = 3.16 (1 H, sbr), 3.11 (1 H,
LRMS (EI): m/z (%) = 91 (17), 104 (5), 115 (12), 141 (16),
d, J = 18.3 Hz), 2.94 (1 H, dd, J = 18.3, 1.2 Hz), 2.84 (1 H, t, J 175 (19), 197 (100), 343 (5), 371 (81, M+).
= 1.7 Hz), 2.54 (1 H, t, J = 2.2 Hz), 2.22 (1 H, sbr), 1.80 (3 H,
HRMS (EI): C25H25NO2: Calcd: m/z = 371.1885. Found:
m), 1.71 (1 H, d, J = 11.2 Hz), 1.67 (1 H, d, J = 11.2 Hz), 1.42 371.1852.
(1 H, td, J = 4.6, 1.0 Hz), 1.34 (1 H, td, J = 5.1, 1.5 Hz), 1.23 (1
H, td, J = 5.3, 0.9 Hz).
IR (neat): ν (cm–1) = 3069 (m), 2930 (s), 2864 (s), 1770 (m),
1706 (ss), 1598 (m), 1453 (m), 1387 (s), 762 (m), 751 (m).
13C NMR (75 MHz, CDCl3): δ = 136.3 (Cq), 118.8 (Cq),
111.6 (Cq), 111.5 (2 Cq), 109.8 (Cq), 46.9 (CH), 46.4 (CH),
44.2 (CH), 41.2 (Cq), 39.9 (CH), 39.5 (Cq), 38.6 (CH2), 31.9
(CH2), 18.3 (CH3), 17.4 (CH), 14.4 (CH), 13.9 (CH).
LRMS (EI) m/z (%) = 129 (29), 143 (100), 158 (94), 166
(8), 180 (8), 193 (21), 207 (17), 218 (23), 232 (11), 244 (24),
258 (9), 271 (22), 286 (96, M+).
HRMS (EI): C18H14N4: Calcd: m/z = 286.1218. Found:
286.1223.
IR (neat): ν (cm–1) = 3090 (m), 3004 (s), 2963 (s), 2945 (s),
2872 (s), 2255 (m), 1630 (m), 1438 (s), 1385 (m), 1359 (m).
7,8,10-Metheno-4,6-dimethyl-3,5,6b,7,8,9,9a,10,10a,10b-
decahydropentaleno[2,1-a]naphthalene-1,1,2,2-
tetracarbonitrile (16)
Colorless solid, mp = 205–206 °C (dec), Rf (pentane/Et2O
= 5/1) = 0.29.
1H NMR (600 MHz, CDCl3): δ = 3.14 (1 H, dd, J = 17.8, 1.1
Hz), 3.04 (1 H, d, J = 20.9 Hz), 2.89 (1 H, d , J = 17.8 Hz), 2.77–
2.74 (2 H, m), 2.71 (1 H, sbr), 2.63 (1 H, d, J = 20.9 Hz), 2.45
(1 H, d, J = 11.4 Hz), 1.94 (1 H, sbr), 1.78 (3 H, sbr), 1.72 (3 H,
sbr), 1.69 (1 H, d, J = 11.1 Hz), 1.64 (1 H, d, J = 11.1 Hz), 1.32
(1 H, t, J = 4.3 Hz), 1.15–1.13 (1 H, m), 1.10-1.08 (1 H, m).
13C NMR (151 MHz, CDCl3): 139.6 (Cq), 127.4 (Cq), 120.3
(Cq), 120.2 (Cq), 112.8 (Cq), 111.4 (Cq), 110.8 (Cq), 109.1 (Cq),
46.0 (CH), 45.7 (CH), 45.3 (CH), 43.9 (CH), 42.2 (Cq), 40.0
(CH), 39.4 (Cq), 37.2 (CH2), 34.6 (CH2), 32.0 (CH2), 19.0
(CH3), 18.8 (CH3), 16.1 (CH), 14.8 (CH), 14.5 (CH).
LRMS (EI) m/z (%) = 91 (37), 128 (27), 158 (34), 224 (48),
245 (7), 272 (12), 310 (9), 337 (12), 352 (100, M+).
HRMS (EI): C23H20N4: Calcd: m/z = 352.1688. Found:
352.1709.
trans,cis,trans-3a,3b,4,5,6,7,7c,8,9,10,10a,11,11a,11b-
Tetradecahydro-8,9,11-metheno-2-phenyl-1H-
benzo[e]pentaleno[1,2-g]isoindole-1,3(2H)-dione (exo-
product) (15b)
Colorless solid, Rf (pentane/Et2O = 5/1) = 0.17.
1H NMR (300 MHz, CDCl3): δ = 7.51–7.43 (2 H, m), 7.41–
7.36 (1 H, m), 7.34–7.28 (2 H, m), 2.72 (1 H, sbr), 2.67 (1H, dd,
J = 8.9, 6.9 Hz), 2.60–2.46 (4 H, m), 2.44–2.34 (1 H, m), 2.18–
2.05 (2 H, m), 1.89 (1 H, sbr), 1.82–1.24 (8 H, m), 1.06–0.97
(2 H, m).
13C NMR (75 MHz, CDCl3): δ = 178.7 (Cq), 178.2 (Cq),
139.8 (Cq), 132.1 (Cq), 129.2 (2 CH), 128.5 (CH), 127.3 (Cq),
126.6 (2 CH), 47.2 (CH), 46.0 (CH), 45.0 (CH), 44.5 (CH),
44.2 (CH), 41.4 (CH), 35.1 (CH), 33.0 (CH2), 31.9 (CH2), 27.1
(CH2), 23.9 (CH2), 23.3 (CH2), 16.0 (CH), 15.6 (CH), 15.1
(CH).
IR (neat): ν (cm–1) = 3065 (m), 2972 (s), 2958 (s), 2931 (s),
2867 (s), 2255 (w), 2629 (m), 1444 (s), 1379 (m).
3a,4,6,7b,8,9,10,10a,11,11a,11b,11c-Dodecahydro-8,9,11-
metheno-5,7-pentamethyl-2-phenyl-1H-cyclopenta[1,2]-
indeno[4,5-e]isoindole-1,3(2H)-dione (exo-product) (17)
Colorless solid, Rf (pentane/Et2O = 3/1) = 0.10.
1H NMR (300 MHz, CDCl3): δ = 7.51–7.32 (3 H, m), 7.19–
7.11 (2 H, m), 3.33–3.20 (2 H, m), 3.00 (1 H, d, J = 11.5 Hz),
2.79 (1 H, d, J = 16.4 Hz), 2.72–2.63 (2 H, m), 2.56 (1 H, d, J
= 16.4 Hz), 2.26–2.20 (2 H, m), 1.95–1.72 (8 H, m), 1.58 (2 H,
sbr), 1.29–1.16 (2 H, m), 1.08–1.04 (1 H, m).
13C NMR (75 MHz, CDCl3) δ = 179.2 (Cq), 177.5 (Cq),
142.8 (Cq), 132.5 (Cq), 132.3 (Cq), 129.2 (2 CH), 128.6 (CH),
126.7 (2 CH), 125.5 (Cq), 121.2 (Cq), 45.9 (CH), 45.1 (CH),
42.3 (CH), 42.2 (CH), 41.6 (CH), 41.5 (CH), 41.1 (CH), 32.2
(CH2), 32.1 (CH2), 31.8 (CH2), 19.6 (CH3), 19.3 (CH3), 16.0
(CH), 15.4 (CH), 15.4 (CH).
LRMS (EI) m/z (%) = 91 (19), 104 (5), 115 (12), 141, (18),
197 (14), 317 (53), 343 (7), 371 (100, M+).
HRMS (EI): C25H25NO2: Calcd: m/z = 371.1885. Found:
371.1883.
IR (neat): ν (cm–1) = 3069 (w), 2931 (m), 2860 (m), 1775
(w), 1712 (ss), 1633 (m), 1598 (w), 1498 (m), 1450 (w), 1376
(s), 748 (m).
cis,cis,cis-3a,3b,4,5,6,7,7c,8,9,10,10a,11,11a,11b-
Tetradecahydro-8,9,11-metheno-2-phenyl-1H-
benzo[e]pentaleno[1,2-g]isoindole-1,3(2H)-dione
(endo-product) (15a)
Colorless solid, mp = 153–155 °C, Rf (pentane/Et2O = 5/1) 3a,4,6,7b,8,9,10,10a,11,11a,11b,11c-Dodecahydro-8,9,11-
= 0.12.
metheno-5,7-pentamethyl-2-phenyl-1H-cyclopenta[1,2]-
1H NMR (300 MHz, CDCl3): δ = 7.47–7.39 (2 H, m), 7.37– indeno[4,5-e]isoindole-1,3(2H)-dione (endo-product) (18)
7.31 (1 H, m), 7.19–7.13 (2 H, m), 3.28 (1 H, dd, J = 9.3, 8.5
Hz), 3.12 (1 H, dd, J = 8.5, 4.3 Hz), 2.62–2.46 (4 H, m), 2.41–
Colorless solid, Rf (pentane/Et2O = 3 / 1) = 0.08.
1H NMR (600 MHz, CDCl3): δ = 7.45–7.22 (3 H, m), 7.20–
2.34 (1 H, m), 2.30–2.24 (2 H, m), 1.92–1.31 (8 H, m), 1.27 (1 7.12 (2 H, m), 3.21 (1 H, t, J = 7.3 Hz), 3.11–3.03 (2 H, m),
H, td, J = 4.8, 1.0 Hz), 1.07–0.98 (2 H, m).
2.80 (1 H, sbr), 2.77 (1 H, sbr), 2.62 (1 H, sbr), 2.55 (1 H, d, J =
13C NMR (75 MHz, CDCl3): δ = 178.0 (Cq), 177.4 (Cq), 14.3 Hz), 2.38-2.21 (2 H, m), 2.11 (1 H, dd, J = 14.5, 5.8 Hz),
139.4 (Cq), 132.3 (Cq), 129.2 (2 CH), 128.6 (Cq)128.5 (CH), 1.89 (3 H, sbr), 1.78 (3 H, sbr), 1.71 (1 H, sbr), 1.58–1.53 (2 H,
126.6 (2 CH), 45.7 (CH), 44.3 (CH), 43.8 (CH), 43.7 (CH), sbr), 1.22 (1 H, t, J = 4.7 Hz), 1.01 (1 H, t, J = 4.7 Hz), 0.95
Israel Journal of Chemistry
41
2001