SYNTHESIS OF CHIRAL BENZOACRIDINONE DERIVATIVES
1133
2
3
1
3Jendo,exo = 4 Hz), 1.52 d.t (1H, exo-6′-H, J = Jexo,exo
=
2
(C–O–C); 1160 (C–N–C); 810 (δC–Harom). H NMR
spectrum, δ, ppm: 0.67 s (3H, 1′-CH3), 0.72 s (3H, syn-
7′-CH3), 0.84 s (3H, anti-7′-CH3), 1.05 d.d.d (1H,
3
12, Jendo,exo = 4 Hz), 1.73 t.t.d (1H, exo-5′-H, J =
3
3
W
3Jexo,exo = 12, Jendo,exo = Jexo-5′,4′ = 4, Jexo-5′,exo-3′
=
3
3
2
3
3
2 Hz), 1.77 t (1H, 4′-H, J4′,exo-5′ = J4′,exo-3′ = 4 Hz),
endo-6′-H, J = 12, Jendo,endo = 8, Jendo,exo = 4 Hz),
2 3
2
4
2.17 d.d (1H, endo-3′-H, J = 16.4, J3′,11′ = 2 Hz),
1.21 d.d.d (1H, endo-5′-H, J = 12, Jendo,endo = 8,
2 3
2.71 d.d (1H, 9-Hax, J = 18, 3Jax,ax = 9 Hz), 2.94 d.d.t
3Jendo,exo = 4 Hz), 1.53 d.t (1H, exo-6′-H, J = Jexo,exo
=
2
2
3
W
3
2
(1H, exo-3′-H, J = 16.4, Jexo-3′,4′ = 4, Jexo-3′,exo-5′
=
=
12, Jendo,exo = 4 Hz), 1.69 t.t.d (1H, exo-5′-H, J =
3 3 W
4J3′,11′ = 2 Hz), 3.09 d.d (1H, 9-Heq, J = 18, Jax,eq
3Jexo,exo = 12, Jendo,exo = Jexo-5′,4′ = 4, Jexo-5′,exo-3′
=
3 3
2
3
3
4 Hz), 3.33d (1H, 11-Hax, Jax,ax = 9 Hz), 3.38 s (3H,
2 Hz), 1.78 t (1H, 4′-H, J4′,exo-5′ = J4′,exo-3′ = 4 Hz),
2 4
3
3
OCH3), 4.28 t.d (1H, 10-Hax, Jax,ax = 9, Jax,eq = 4 Hz),
2.18 br.d (1H, endo-3′-H, J = 16.4, J3′,11′ = 2 Hz),
2 3
4.64 d.t (1H, 11′-H, 3J = 10, 4J3′,11′ = 2 Hz), 4.91 d (1H,
2.82 d.d (1H, 9-Hax, J = 18, Jax,ax = 9 Hz), 2.96 d.d.t
3
2
3
W
7-H, J = 10 Hz), 6.02 s (2H, OCH2O), 6.82 d (2H,
(1H, exo-3′-H, J = 16.4, Jexo-3′,4′ = 4, Jexo-3′,exo-5′
=
=
=
=
3
2
3
H
arom), 6.88 s (1H, Harom), 7.18 d (1H, 4-H, J =
4J3′,11′ = 2 Hz), 3.28 d.d (1H, 9-Hex, J = 18, Jax,eq
8.5 Hz), 7.47 t (1H, 3-H, 3J = 8.5 Hz), 7.49 d (1H, 5-H,
4 Hz), 3.46 s (3H, OCH3), 3.63 d (1H, 11-Hax, Jax,ax
3
3J = 7 Hz), 7.56 t (1H, 2-H, J = 8.5 Hz), 7.87 d (1H,
9 Hz), 3.92 t.d (1H, 10-Hax, Jax,ax = 9 Hz, Jax,eq
3 4
3
3
3
3
3
6-H, J = 7 Hz), 8.36 d (1H, 1-H, J = 8.5 Hz), 9.19 s
4 Hz), 4.64 d.t (1H, 11′-H, J = 10, J3′,11′ = 2 Hz),
3
(1H, NH).
4.90 d (1H, 7-H, J = 9.6 Hz), 6.02 s (2H, OCH2O),
6.81 d (2H, Harom), 6.87 s (1H, Harom), 7.18 d (1H, 4-H,
Methyl (7S,10S,11R)-10-(3,4-methylenedioxy-
phenyl)-8-oxo-7-[(1S,4S)-1,7,7-trimethylbicyclo-
[2.2.1]hept-2-ylidenemethyl]-7,8,9,10,11,12-hexa-
hydrobenzo[c]acridine-11-carboxylate (VIIIf). IR
spectrum, ν, cm–1: 3300 (NH); 3060, 3020 (C–Harom);
2950, 2920, 2870 (C–Haliph); 1730 (C=O, ester); 1595
(HN–C=C–C=O); 1520, 1490 (C=Carom); 1250, 1220
3J = 8.5 Hz), 7.47 t (1H, 3-H, 3J = 8.5 Hz), 7.51 d (1H,
3
3
5-H, J = 7 Hz), 7.56 t (1H, 2-H, J = 8.5 Hz), 7.86 d
3
3
(1H, 6-H, J = 7 Hz), 8.37 d (1H, 1-H, J = 8.5 Hz),
9.12 s (1H, NH).
Methyl (7S,10R,11S)-10-(3,4-methylenedioxy-
phenyl)-8-oxo-7-[(1S,4S)-1,7,7-trimethylbicyclo-
[2.2.1]hept-2-ylidenemethyl]-7,8,9,10,11,12-hexahy-
drobenzo[c]acridine-11-carboxylate (Xf). IR spec-
trum, ν, cm–1: 3300 (NH); 3060, 3020 (C–Harom); 2950,
2920, 2870 (C–Haliph); 1730 (C=O, ester); 1595
(HN–C=C–C=O); 1520, 1495 (C=Carom); 1250, 1225
1
(C–O–C); 1160 (C–N–C); 810 (δC–Harom). H NMR
spectrum, δ, ppm: 0.68 s (3H, 1′-CH3), 0.70 s (3H, syn-
7′-CH3), 0.85 s (3H, anti-7′-CH3), 1.06 d.d.d (1H,
2
3
3
endo-6′-H, J = 12, Jendo,endo = 8, Jendo,exo = 4 Hz),
2
3
1.18 d.d.d (1H, endo-5′-H, J = 12, Jendo,endo = 8,
2
3
3Jendo,exo = 4 Hz), 1.50 d.t (1H, exo-6′-H, J = Jexo,exo
=
1
(C–O–C); 1160 (C–N–C); 810 (δC–Harom). H NMR
3
2
12, Jendo,exo = 4 Hz), 1.71 t.t.d (1H, exo-5′-H, J =
spectrum, δ, ppm: 0.68 s (3H, 1′-CH3), 0.72 s (3H, syn-
7′-CH3), 0.86 s (3H, anti-7′-CH3), 1.06 d.d.d (1H,
3
3
W
3Jexo,exo = 12, Jendo,exo = Jexo-5′,4′ = 4, Jexo-5′,exo-3′
=
3
3
2
3
3
2 Hz), 1.78 t (1H, 4′-H, J4′,exo-5′ = J4′,exo-3′ = 4 Hz),
2.67 m (2H, endo-3′-H, exo-3′-H), 2.84 d.d (1H, 9-Hax,
endo-6′-H, J = 12, Jendo,endo = 8, Jendo,exo = 4 Hz),
2
3
1.21 d.d.d (1H, endo-5′-H, J = 12, Jendo,endo = 8,
2J = 18, 3Jax,ax = 9 Hz), 3.31 d.d (1H, 9-Heq, J = 18,
2
2
3
3Jendo,exo = 4 Hz), 1.49 d.t (1H, exo-6′-H, J = Jexo,exo
=
3Jax,eq = 4 Hz), 3.33 d (1H, 11-Hax, Jax,ax = 9 Hz),
3
3
2
12, Jendo,exo = 4 Hz), 1.68 t.t.d (1H, exo-5′-H, J =
3
3Jexo,exo = 12, Jendo,exo = Jexo-5′,4′ = 4, Jexo-5′,exo-3′
=
3
3
W
3.43 s (3H, OCH3), 4.29 t.d (1H, 10-Hax, Jax,ax = 9,
3Jax,eq = 4 Hz), 4.70 d.t (1H, 11′-H, J = 10, J3′,11′
=
3
4
3
3
2 Hz), 1.77 t (1H, 4′-H, J4′,exo-5′ = J4′,exo-3′ = 4 Hz),
2.64 m (2H, endo-3′-H, exo-3′-H), 2.85 d.d (1H, 9-Hax,
3
2 Hz), 4.91 d (1H, 7-H, J = 10 Hz), 6.02 s (2H,
2J = 18, 3Jax,ax = 9 Hz), 3.30 d.d (1H, 9-Heq, J = 18,
2
OCH2O), 6.81 d (2H, Harom), 6.87 s (1H, Harom), 7.12 d
3
3
3Jax,eq = 4 Hz), 3.46 s (3H, OCH3), 3.58 d (1H, 11-Hax,
(1H, 4-H, J = 8.5 Hz), 7.46 t (1H, 3-H, J = 8.5 Hz),
3
3
3Jax,ax = 9 Hz), 3.93 t.d (1H, 10-Hax, Jax4,ax = 9, Jax,eq
=
3
3
7.48 d (1H, 5-H, J = 7 Hz), 7.55 t (1H, 2-H, J =
8.5 Hz), 7.86 d (1H, 6-H, 3J = 7 Hz), 8.37 d (1H, 1-H,
3J = 8.5 Hz), 9.21 s (1H, NH).
3
4 Hz), 4.70 d.t (1H, 11′-H, J = 10, J3′,11′ = 2 Hz),
3
4.90 d (1H, 7-H, J = 10 Hz), 6.02 s (2H, OCH2O),
6.81 m (2H, Harom), 6.86 s (1H, Harom), 7.11 d (1H, 4-H,
Methyl (7R,10S,11R)-10-(3,4-methylenedioxy-
phenyl)-8-oxo-7-[(1S,4S)-1,7,7-trimethylbicyclo-
[2.2.1]hept-2-ylidenemethyl]-7,8,9,10,11,12-hexahy-
drobenzo[c]acridine-11-carboxylate (IXf). IR spec-
trum, ν, cm–1: 3300 (NH); 3060, 3020 (C–Harom); 2950,
2920, 2870 (C–Haliph); 1730 (C=O, ester); 1595
(HN–C=C–C=O); 1520, 1495 (C=Carom); 1250, 1225
3J = 8.5 Hz), 7.45 t (1H, 3-H, 3J = 8.5 Hz), 7.48 d (1H,
3
3
5-H, J = 7 Hz), 7.57 t (1H, 2-H, J = 8.5 Hz), 7.86 d
3
3
(1H, 6-H, J = 7 Hz), 8.37 d (1H, 1-H, J = 8.5 Hz),
9.21 s (1H, NH).
5-{2-[(1S,4S)-1,7,7-Trimethylbicyclo[2.2.1]hept-
2-ylidene]ethylidene}hexahydropyrimidine-2,4,6-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 8 2010