temperature, the solvent was evaporated. Purification by column
chromatography, eluting with CH2Cl2–MeOH (97 : 3), gave the
cycloadduct 5 (130 mg, 71%) as an oil; Rf 0.5 [CH2Cl2–MeOH
(95 : 5)]; nmax/cm-1 2930, 1460;1H NMR (400 MHz, C6D6) d =
6.10 (1H, s), 4.0–3.96 (1H, m), 3.35 (1H, d, J 9.5 Hz), 3.27–3.25
(1H, m), 2.89–2.82 (1H, m), 1.57–1.37 (3H, m), 1.32–1.22 (2H,
m), 1.10–1.0 (3H, m), 0.98–0.78 (2H, m), 0.60 (3H, t, J 7.5 Hz);
13C NMR (100 MHz, C6D6) d = 141.4, 68.4, 53.6, 50.0, 44.5, 33.4,
30.7, 30.5, 28.2, 19.1, 7.7; HRMS (ES) Found: MH+, 179.1540.
C11H19N2 requires MH+, 179.1548; LRMS m/z (ES) 180 (20%),
179 (100, MH+).
363 (20%), 362 (100, MH+). Data for 10a¢: m.p. 106–110 ◦C; Rf 0.35
[CH2Cl2–MeOH (98 : 2)]; nmax/cm-1 3075, 2930, 1720, 1665, 1460;
1H NMR (400 MHz, CDCl3) d = 7.43–7.24 (6H, m), 7.18–7.12
(3H, m), 5.79 (1H, d, J 8.5 Hz), 4.78 (1H, d, J 8.5 Hz), 4.05 (1H,
t, J 8.5 Hz), 3.40–3.36 (1H, m), 3.23–3.15 (1H, m), 2.90–2.79 (2H,
m), 2.32 (3H, s); 13C NMR (100 MHz, CDCl3) d = 173.0, 172.9,
132.9, 131.5, 129.2, 129.1, 128.8, 128.6, 128.5, 127.9, 126.2, 125.6
(two overlapping CH), 65.3, 58.2, 50.7, 50.2, 29.6, 21.0; HRMS
(ES) Found: MH+, 362.1490 C21H20N3O3 requires MH+, 362.1505;
LRMS m/z (ES) 363 (15%), 362 (100, MH+).
(7aS*,10aR*,10bS*)-/(7aS*,10aR*,10bR*)-7-Benzyl-9-phen-
yl-5,6,7,7a,10a,10b-hexahydro-6a,7,9-triaza-pentaleno[1,2-a]naph-
thalene-8,10-dione 10b and 10b¢. The aldehyde 99 (262 mg, 1.23
mmol), benzylhydrazine dihydrochloride (264 mg, 1.35 mmol)
and N,N-diisopropylethylamine (0.53 mL, 3.08 mmol) in PhMe
(15 mL) were heated at 60 ◦C for 30 min. N-Phenyl maleimide
(319 mg, 1.85 mmol) was added and the mixture was heated at
60 ◦C for 6 h. After cooling to room temperature, the solvent was
evaporated. Purification by column chromatography, eluting with
petrol–EtOAc (8 : 2), gave the cycloadduct 10b (237 mg, 47%) as
an amorphous solid and the cycloadduct 10b¢ (112 mg, 22%) as
an amorphous solid. Data for 10b: m.p. 58–62 ◦C; Rf 0.64 [petrol–
In addition to cycloadduct 5, the following compound (formed
in 6% yield) was isolated as an oil and characterized: N,N¢-
Bis(2-(3-chloropropyl)-2-ethylhex-5-enylidene)hydrazine 6: Rf 0.95
[CH2Cl2–MeOH (95 : 5)];
n
max/cm-1 2930, 1460;1H NMR
(400 MHz, CDCl3) d = 7.56 (2H, s), 5.82 (2H, ddt, J 17, 10, 6.5),
5.05–4.95 (4H, m), 3.55 (4H, t, J 6 Hz), 2.02–1.96 (4H, m), 1.75–
1.54 (16H, m), 0.85 (6H, t, J 7.5 Hz); 13C NMR (100 MHz, CDCl3)
d = 169.2, 139.0, 114.9, 46.0, 43.6, 34.3, 31.7, 28.3, 27.8, 27.4, 8.3;
HRMS (ES) Found: MH+, 401.2482. C22H39Cl2N2 requires MH+,
401.2490; LRMS m/z (ES) 403 (60%), 401 (100, MH+).
(2aR*,4aS*,7bS*)-1-Benzyl-4a-ethyl-decahydro-1,7a-diaza-cy-
clopenta[cd]indene 8. The aldehyde 72d (212 mg, 1.21 mmol),
benzylhydrazine dihydrochloride (284 mg, 1.46 mmol) and N,N-
diisopropylethylamine (0.95 mL, 5.45 mmol) in PhMe (18 mL)
were heated under reflux for 2 h. After cooling to room tem-
perature, the solvent was evaporated. Purification by column
chromatography, eluting with CH2Cl2–MeOH (98 : 2), gave the
cycloadduct 8 (145 mg, 50%) as an amorphous solid: m.p. 155–
159 ◦C; Rf 0.55 [CH2Cl2–MeOH (98 : 2)]; nmax/cm-1 2940, 2865,
1460;1H NMR (500 MHz, CDCl3) d = 7.34–7.26 (5H, m), 4.40
(1H, d, J 12 Hz), 4.21 (1H, t, J 7.5 Hz), 3.90 (1H, d, J 12 Hz), 3.52
(1H, d, J 14.5 Hz), 3.35 (1H, t, J 9 Hz), 3.19–3.13 (1H, m), 3.00
(1H, q, J 7.5 Hz), 2.90 (1H, d, J 9 Hz), 2.14–2.08 (1H, m), 2.06–
1.97 (1H, m), 1.91–1.70 (4H, m), 1.66–1.58 (2H, m), 1.48–1.45 (1H,
m); 13C NMR (125 MHz, CDCl3) d = 135.6, 128.6, 128.4, 128.0,
66.2, 62.5, 56.9, 46.0, 40.4, 37.4, 33.4, 30.7, 23.5, 13.1; HRMS (ES)
Found: MH+, 243.1851 C16H23N2 requires MH+, 243.1861; LRMS
m/z (ES) 244 (25), 243 (100%, MH+).
1
EtOAc (7 : 3)]; nmax/cm-1 3075, 2940, 2865, 1720, 1665, 1460; H
NMR (500 MHz, C6D6, 60 ◦C) d = 7.87–7.85 (1H, m), 7.43–7.41
(2H, m), 7.38–7.35 (2H, m), 7.20–6.98 (8H, m), 6.83–6.81 (1H, m),
4.41 (1H, bs), 4.37 (1H, d, J 14.5 Hz), 4.09 (1H, d, J 14.5 Hz), 3.65
(1H, d, J 8.5 Hz), 3.06 (1H, dd, J 8.5, 7 Hz), 2.73–2.72 (1H, m),
2.54–2.47 (3H, m); 13C NMR (125 MHz, C6D6, 60 ◦C) d = 175.4,
173.4, 138.4, 135.8, 134.1, 132.9, 129.1, 128.9, 128.5, 128.3, 128.0,
127.8, 127.4, 127.3, 127.2, 126.8, 66.1, 64.2, 54.0, 28.3; HRMS
(ES) Found: MH+, 410.1875 C26H24N3O2 requires MH+, 410.1869;
LRMS m/z (ES) 412 (10%), 411 (30), 410 (100, MH+); Data for
10b¢: m.p. 151–155 ◦C; Rf 0.46 [petrol–EtOAc (7 : 3)]; nmax/cm-1
3075, 2940, 2865, 1720, 1665, 1460; 1H NMR (400 MHz, CDCl3)
d = 7.56–7.10 (14H, m), 5.0 (1H, d, J 8.5 Hz), 4.29 (1H, d, J 13 Hz),
4.25 (1H, d, J 8.5 Hz), 4.13 (1H, d, J 13 Hz), 4.01 (1H, t, J 8.5 Hz),
3.27 (1H, ddd, J 10.5, 5, 2 Hz), 3.04–2.96 (1H, m), 2.80–2.74 (1H,
m), 2.69–2.64 (1H, m); 13C NMR (100 MHz, CDCl3) d = 175.6,
173.9, 137.9, 134.2, 131.8, 130.4, 129.3 (two overlapping CH),
129.2, 129.0, 128.5, 128.4, 127.5, 127.2, 126.5, 125.8, 125.7, 67.3,
63.5, 62.6, 52.5, 50.8, 30.2; HRMS (ES) Found: MH+, 410.1875
C26H24N3O2 requires MH+, 410.1869; LRMS m/z (ES) 412 (5%),
411 (30), 410 (100, MH+).
(7aS*,10aR*,10bS*)-/(7aS*,10aR*,10bR*)-7-Acetyl-9-phenyl-
5,6,7,7a,10a,10b-hexahydro-6a,7,9-triaza-pentaleno[1,2-a]naphth-
alene-8,10-dione 10a and 10a¢. The aldehyde 99 (215 mg, 1 mmol)
and acetylhydrazine (148 mg, 2 mmol) in PhMe (11 mL) were
heated at 60 ◦C for 30 min. N-Phenyl maleimide (3◦81 mg, 2.2
mmol) was added and the mixture was heated at 60 C for 5 h.
After cooling to room temperature, the solvent was evaporated.
Purification by column chromatography, eluting with CH2Cl2–
MeOH (98 : 2), gave the cycloadduct 10a (185 mg, 52%) as an
amorphous solid and the cycloadduct 10a¢ (80 mg, 22%) as an
amorphous solid. Data for 10a: m.p. 227–231 ◦C; Rf 0.21 [CH2Cl2–
MeOH (98 : 2)]; nmax/cm-1 3075, 2930, 1720, 1665, 1460; 1H NMR
(400 MHz, CDCl3) d = 7.52–7.37 (6H, m), 7.29–7.27 (2H, m), 7.20–
7.18 (1H, m), 5.34 (1H, d, J 8.5 Hz), 4.60 (1H, d, J 8.5 Hz), 3.85
(1H, t, J 8.5 Hz), 3.28–3.20 (2H, m), 2.92–2.84 (2H, m), 2.37 (3H,
s); 13C NMR (100 MHz, CDCl3) d = 173.0, 172.9, 132.5, 132.0,
131.3, 129.2, 128.9, 128.3, 128.2, 128.0, 126.9, 126.3, 65.2, 59.9,
52.9, 29.0 (two overlapping CH2), 22.2; HRMS (ES) Found: MH+,
362.1508 C21H20N3O3 requires MH+, 362.1505; LRMS m/z (ES)
(7aS*,10aR*,10bS*)-/(7aS*,10aR*,10bR*)-9-Phenyl-5,6,7,7a,
10a,10b-hexahydro-6a,7,9-triaza-pentaleno[1,2-a]naphthalene-8,
10-dione 10c and 10c¢. The aldehyde 99 (220 mg, 1.03 mmol)
and hydrazine monohydrate (0.064 mL, 2.06 mmol) in PhMe
(15 mL) were heated under reflux for 30 min. N-Phenyl maleimide
(268 mg, 1.55 mmol) was added and the mixture was heated under
reflux for 5 h. After cooling to room temperature, the solvent was
evaporated. Purification by column chromatography, eluting with
CH2Cl2–MeOH (98 : 2), gave the cycloadduct 10c (177 mg, 54%) as
an amorphous solid and the cycloadduct 10c¢ (55 mg, 17%) as an
amorphous solid. Data for 10c: m.p. 73–75 ◦C; Rf 0.43 [CH2Cl2–
MeOH (98 : 2)]; nmax/cm-1 3075, 2930, 1720, 1665, 1460; 1H NMR
(500 MHz, CDCl3) d = 7.57–7.16 (9H, m), 4.66 (1H, d, J 5 Hz), 4.55
(1H, d, J 8 Hz), 3.76 (1H, dd, J 8, 5 Hz), 3.27 (1H, ddd, J 12, 7, 5.5
Hz), 3.20 (1H, ddd, J 12, 7, 5.5 Hz), 3.01 (1H, ddd, J 12, 7, 5.5 Hz),
This journal is The Royal Society of Chemistry 2011
Org. Biomol. Chem., 2011, 9, 7921–7928 | 7925
©