4
32
Caprosu, Zbancioc, Moldoveanu, Mangalagiu:
(
500.4) calculated: 62.41% C, 3.63% H, 9.59% N; foun d: 62.38% C, 3.60% H, 9.40% N.
IR: 2950, 1770, 1717 (C=O im ide); 1688 (C=O keto); 1599, 1560, 1495, 1450 (C=C, C=N).
1
H NMR: 3.60–3.58 dd, J = 8.0, J = 8.4, 1 H (H-11a); 4.20–4.18 d, J = 8.0, 1 H (H-8a);
4
7
8
5
.66–4.64 d, J = 8.4, 1 H (H-11b); 5.90 s, 1 H (H-8); 7.04–7.02 d, J = 7.2, 2 H (H-17);
.40–7.11 m , 7 H (H-1, H-2, H-3, H-4, 2 × H-18, H-19); 7.49 s, 1 H (H-5); 7.78–7.76 d, J =
.8, 2 H (H-13); 8.24–8.22 d, J = 8.8, 2 H (H-13). C NMR: 46.90 (C-8a), 51.46 (C-11a),
1
3
9.69 (C-11b), 76.46 (C-8), 123.76 (C-4a), 126.25 (C-4), 126.65 (C-17), 128.08 (C-15), 128.28
(
(
C-19), 128.30 (C-1a), 129.04 (C-1), 129.26 (C-3), 129.41 (C-18), 130.09 (C-14), 131.20
C-13), 131.29 (C-2), 135.12 (C-16), 137.08 (C-12), 140.64 (C-5), 174.88 (C-11, keto im ide),
1
77.53 (C-9, keto im ide), 193.45 (C-8b, keto).
-(4-Fluorobenzoyl)-1,2,3,10b-tetrahydropyrrolo[2,1-a]phthalazine-1-carbonitrile (7a). Yield
3
8
4
1
1%; wh ite crystals, m .p. 179 °C (eth an ol). For C19H14FN O (319.3) calculated: 71.46% C,
3
.42% H, 13.16% N; foun d: 71.42% C, 4.39% H, 13.00 % N. IR: 3055, 2950, 2241 (CN);
1
697 (C=O keto); 1598, 1560, 1495, 1450 (C=C, C=N). H NMR: 2.42–2.36 8 lin es: dxdxd,
J2a,2b = 19.6, J2a,1 = 7.6, J2a,3 = 4.4, 1 H (H-2a); 2.69–2.62 8 lin es: dxdxd, J = 19.6, J = 15.6, J =
9
4
7
.2, 1 H (H-2b); 3.79–3.74 8 lin es: dxdxd, J1,2a = 7.6, J1,2b = 15.6, J1,10b = 7.4, 1 H (H-1);
.54–4.52 d, J = 7.4, 1 H (H-10b); 5.80–5.77 dd, J3,2b = 9.2, J3,2a = 4.4, 1 H (H-3); 7.49–
.33 m , 7 H (H-6, H-7, H-8, H-9, H-10, 2 × H-14); 8.23–8.20 q, J = 8.8, J = 8.6, 2 H (H-13).
C NMR: 28.93 (C-2), 34.89 (C-1), 59.15 (C-10b), 69.77 (C-3), 116.43 (C-14), 121.59 (C-1a,
1
3
CN), 124.73 (C-7), 126.25 (C-7), 127.34 (C-8), 129.05 (C-10a), 129.60 (C-9), 131.40 (C-10),
1
32.14 (C-12), 132.65 (C-13), 138.66 (C-6), 167.00 (C-15), 195.57 (C-11, keto).
-(4-Chlorobenzoyl)-1,2,3,10b-tetrahydropyrrolo[2,1-a]phthalazine-1-carbonitrile (7b ). Yield
3
8
4
0%; wh ite crystals, m .p. 175 °C (eth an ol). For C19H14ClN O (335.8) calculated: 67.96% C,
3
.20% H, 12.51% N; foun d: 67.89% C, 4.17% H, 12.40% N. IR: 3055, 2950, 2240 (CN); 1695
1
(
C=O keto); 1600, 1558, 1494, 1450 (C=C, C=N). H NMR: 2.36–2.30 8 lin es: dxdxd, J2a,2b
=
9.6, J2a,1 = 7.6, J2a,3 = 4.4, 1 H (H-2a); 2.98–2.91 8 lin es: dxdxd, J = 19.6, J = 15.6, J = 9.4,
H (H-2b); 3.38–3.33 8 lin es: dxdxd, J1,2a = 7.6, J1,2b = 15.6, J1,10b = 7.4, 1 H (H-1); 4.44–
.42 d, J = 7.4, 1 H (H-10b); 5.68–5.65 dd, J3,2b = 9.4, J3,2a = 4.4, 1 H (H-3); 7.12–7.10 d, J =
.0, 1 H (H-7); 7.30–7.28 d, J = 8.4, 1 H (H-10); 7.42–7.39 m , 2 H (H-8, H-9); 7.44 s, 1 H
1
1
4
8
1
3
(
(
(
(
H-6); 7.47–7.45 d, J = 8.8, 2 H (H-14); 8.15–8.12 d, J = 8.8, 2 H (H-13). C NMR: 28.57
C-2), 35.67 (C-1), 59.07 (C-10b), 70.82 (C-3), 120.18 (C-6a), 124.19 (C-1a, CN), 126.57
C-7), 126.68 (C-8), 128.15 (C-10a), 129.04 (C-14), 129.57 (C-9), 130.93 (C-13), 131.35
C-10), 133.19 (C-12), 140.13 (C-6), 140.40 (C-15), 194.67 (C-11, keto).
3
-(4-Bromobenzoyl)-1,2,3,10b-tetrahydropyrrolo[2,1-a]phthalazine-1-carbonitrile (7c). Yield
8
3
1%; wh ite crystals, m .p. 176 °C (eth an ol). For C19H14BrN O (380.24) calculated: 60.02% C,
3
.71% H, 11.05% N; foun d: 60.00% C, 3.68% H, 11.00% N. IR: 3053, 2950, 2240 (CN); 1694
1
(
C=O keto); 1602, 1560, 1490, 1450 (C=C, C=N). H NMR: 2.30–2.26 8 lin es: dxdxd, J2a,2b
=
9.6, J2a,1 = 7.6, J2a,3 = 4.4, 1 H (H-2a); 2.94–2.90 8 lin es: dxdxd, J = 19.6, J = 15.6, J = 9.4,
H (H-2b); 3.32–3.29 8 lin es: dxdxd, J1,2a = 7.6, J1,2b = 15.6, J1,10b = 7.4, 1 H (H-1); 4.40–
.38 d, J = 7.4, 1 H (H-10b); 5.60–5.56 dd, J3,2b = 9.4, J3,2a = 4.4, 1 H (H-3); 7.40–7.34 m , 5 H
1
1
4
(
1
H-6, H-7, H-8, H-9, H-10); 7.64–7.61 d, J = 8.8, 2 H (H-14); 7.85–7.82 d, J = 8.8, 2 H (H-13).
C NMR: 28.52 (C-2), 35.61 (C-1), 59.00 (C-10b), 70.76 (C-3), 120.10 (C-6a), 123.89 (C-1a,
3
CN), 126.46 (C-7), 126.60 (C-8), 128.06 (C-15), 128.10 (C-10a), 129.52 (C-9), 130.12 (C-14),
1
31.21 (C-13), 131.32 (C-10), 137.10 (C-12), 140.06 (C-6), 194.60 (C-11, keto).
Ethyl 3-(4-fluorobenzoyl)pyrrolo[2,1-a]phthalazine-1-carboxylate (9a ). Yield 79%; wh ite
crystals, m .p. 182 °C (eth an ol). For C21H15FN O (362.4) calculated: 69.61% C, 4.17% H,
2
3
7
.73% N; foun d: 69.38% C, 4.14% H, 7.56% N. IR: 3055, 2950, 1694 (C=O ester); 1663 (C=O
Collect. Czech. Chem. Commun. (Vol. 69) (2004)