M. G. Ferlin et al. / Bioorg. Med. Chem. 13 (2005) 3531–3541
3539
J7,6 = 9.3 Hz, HC-7), 7.64 (t, 1H, J9,10 = 2.63 and
0.9 Hz, HC-9), 7.78 (d, 1H, J6,7 = 9.3 Hz, HC-6), 8.37
1H NMR (DMSO-d6) d 3.78 (s, 3H, CH3), 7.03 (d,
= 9.1 Hz, HC-30and HC-50), 7.39 (s,
0
2H, J2 ,3
0
and 50,60
= 8.3 Hz, HC-20and HC-60), 8.69
1H, HC-10), 7.47 (d, 1H, J7ꢀ6 = 9.0 Hz, HC-7), 7.61
(s, 1H, HC-9), 7.74 (d, J6ꢀ7 = 9.0 Hz, HC-6), 8.23 (d,
2H, J2 ,3
0
(d, 2H, J2 ,3
0
and 60,50
(d, 1H, J4,3 = 6.4 Hz, HC-4), 11.75 (s, 1H, indole NH),
12.84 (s, 1 H, quinoline NH); 13C NMR (DMSO-d6) d
104.67 (C-10), 106.84 (C-3a), 112.11 (C-10b), 113.53
(C-6), 115.88 (C-7), 119.31 (C-20 and C-60), 121.66 (C-
10a), 124.51 (C-40), 127.60 (C-9), 129.54 (C-30 and C-
50), 131.04 (C-5a), 133.76 (C-7a), 137.42 (C-4), 141.42
(C-10), 144.92 (C-10c), 162.52 (C-3); HRMS (m/z)
301.10 (M + 1). Anal. Calcd for C18H12N4O: C, 71.99;
H, 4.03; N, 18.66. Found: C, 71.75; H, 3.81; N, 18.39.
= 9.1 Hz, HC-20and HC-60), 8.64 (s,
0
0
and 5,60
1H, HC-4), 11.71 (s, 1H, indole NH), 12.82 (s, 1H, quino-
line NH); 13C NMR (DMSO-d6) d 56.10 (CH3), 104.66
(C-3a), 106.09 (C-10), 112.13 (C-10b), 113.41 (C-6),
114.69 (C-30, C-50), 115.72 (C-7), 120.89 (C-20, C-60
and C-10a), 127.49 (C-9), 130.60 (C-5a), 133.71 (C-7a),
134.99 (C-10), 137.14 (C-4), 144.65 (C-10c), 156.53 (C-
40), 162.01 (C-3); HRMS (m/z) 331.12 (M + 1). Anal.
Calcd for C19H14N4O2: C, 69.08; H, 4.27; N, 16.96.
Found: C, 68.91; H, 4.05; N, 16.83.
More analytical data on HMQC, HMBC, COSY and
NOESY aimed at elucidating the exact structure of 7a
are given and discussed in Section 2.
4.1.6.6. 2-(4-Methoxy-phenyl)-8-methyl-5-hydro-2H-
pyrazolo[4,3-c]pyrrolo[3,2-f]quinolin-3-one (8b). Yield
45%; mp > 300 ꢁC; Rf 0.19 (ethyl acetate); IR (KBr)
4.1.6.3.
3-c]pyrrolo[3,2-f]quinolin-3-one
mp > 300 ꢁC; Rf 0.45 (ethyl acetate); IR (KBr) 3227,
3086, 2933, 1599 cmꢀ1 1H NMR (DMSO-d6) d 3.96
(s, 3H, CH3), 7.19 (t, 1H, J4 ,3 and
2-Phenyl-8-methyl-5-hydro-2H-pyrazolo[4,
1
(7b). Yield 62%,
3339, 3260, 2974, 1626 cmꢀ1; H NMR (DMSO-d6) d
3.79 (s, 3H, N–CH3), 3.95 (s, 3H, O–CH3), 7.04 (d,
2H, HC-30 and HC-50), 7.38 (d, 1H, J10,9 = 2.8 Hz,
HC-10), 7.54 (d, 1H, HC-7), 7.62 (d, 1H,
J9,10 = 2.8 Hz, HC-9), 7.84 (d, 1H, HC-6), 8.25 (d, 1H,
HC-20 and HC-60), 8.67 (d, 1H, HC-4), 12.83 (d, 1H,
NH); 13C NMR (DMSO-d6) d 32.50 (N–CH3), 54.73
(–OCH3), 106.09 (C-3a), 106.38 (C-10), 112.13 (C-6),
113.41 (C-10b), 114.69 (C-30 and C-50), 115.72 (C-7),
120.89 (C-20, C-60 and C-10a), 127.49 (C-9), 130.60 (C-
5a), 133.72 (C-7a), 134.99 (C-10), 137.14 (C-4), 144.65
(C-10), 156.53 (C-10c), 162.01 (C-3); HRMS (m/z)
345.16 (M + 1). Anal. Calcd for C20H16N4O2: C,
69.76; H, 4.68; N, 16.27. Found: C, 69.49; H, 4.30; N,
16.03.
;
0
0
40,50
= 7.5 Hz, HC-
40), 7.28 (d, 1H, J10,9 = 2.3 Hz, HC-10), 7.46 (t, 2H,
J3 ,2 = J3 ,5 ,4 = J5 ,6 = 7.5 Hz, HC-30 and HC-50), 7.54
(d, 1H, J6,7 = 9.0 Hz, HC-7), 7.63 (d, 1H,
J9,10 = 2.3 Hz, HC-9), 7.86 (d, 1H, J7,6 = 9.0 Hz, HC-
0
0
0
0
0
0
0
6), 8.37 (d, 2H, J2 ,3 = J6 ,5 = 7.6 Hz, HC-20 and HC-
60), 8.69 (d, 1H, J4,5 = 6.5 Hz, HC-4), 12.87 (d, 1H,
J5,4 = 6.5 Hz, quinoline HN); 13C NMR (DMSO-d6)
d 103.34 (C-3a), 106.38 (C-10), 111.62 (C-6), 112.95
(C-10b), 113.68 (C-7), 118.79 (C-20 and C-60), 121.44
(C-10a), 124.04 (C-40), 129.07 (C-30 and C-50), 130.60
(C-9), 131.39 (C-5a), 133.72 (C-7a), 137.03 (C-4),
140.88 (C-10), 144.26 (C-10c), 162.02 (C-3); HRMS
(m/z) 315.23 (M + 1). Anal. Calcd for C19H14N4O:
C, 72.70; H, 4.49; N, 17.82. Found: C, 72.53; H, 4.18;
N, 17.42.
0
0
0
0
4.1.6.7. 2-(4-Chloro-phenyl)-5,8-dihydro-2H-pyrazolo-
[4,3-c]pyrrolo[3,2-f]quinolin-3-one (9a). Yield 78%;
mp > 300 ꢁC; Rf 0.36 (ethyl acetate); IR (KBr) 3274,
1
2979, 1605, 745 cmꢀ1; H NMR (DMSO-d6) d 7.41 (m,
4.1.6.4.
3-c]pyrrolo[3,2-f]quinolin-3-one
2-Phenyl-8-ethyl-5-hydro-2H-pyrazolo[4,
(7c). Yield 51%;
1H, HC-10), 7.49 (d, 1H, J6,7 = 8.6 Hz, HC-6), 7.52 (d,
2H, J3 ,2 = J5 ,6 = 8.6 Hz, HC-30 and HC-50), 7.65 (t,
1H, J9,8 = J9,10 = 7.6 Hz, HC-9), 7.79 (d, 1H,
0
0
0
0
mp >300 ꢁC; Rf 0.26 (ethyl acetate); IR (KBr) 3069,
1
2872, 2932, 1626.2 cmꢀ1; H NMR (DMSO-d6) d 1.43
(t, 3H, J = 7.2 Hz, CH3), 4.36 (q, 2H, J = 7.2 Hz,
J7,6 = 8.6 Hz, HC-7), 8.43 (d, 2H, J2 ,3 = J6 ,5 = 8.6 Hz,
HC-20 and HC-60), 8.72 (d, 1H, J4,5 = 6.7 Hz, HC-4),
11.76 (sa, 1H, indole NH), 12.93 (d, 1H, J5,4 = 7.2 quino-
line NH); 13C NMR (DMSO-d6) d 105.27 (C-10), 107.20
(C-3a), 112.61 (C-10b), 114.14 (C-6), 116.63 (C-7),
121.22 (C-20 and C-60), 122.40 (C-10a), 128.27 (C-9),
130.09 (C-30 and C-50), 131.73 (C-5a), 134.39 (C-7a
and C-40), 137.02 (C-4), 140.85 (C-10), 145.82 (C-10c),
163.17 (C-3); HR MS (m/z) 336.78 (M + 1). Anal. Calcd
for C18H11N4OCl: C, 64.58; H, 3.31; N, 16.74; Cl, 10.59.
Found: C, 64.27; H, 3.10; N, 16.54; Cl, 10.73.
0
0
0
0
CH2), 7.17 (t, 1H, J4 ,3
= 7.2 Hz, HC-40), 7.41
0
0
and 40,50
(d, 1H, J10,9 = 2.8 Hz, HC-10), 7.47 (t, 2H, HC-30and
HC-50), 7.53 (d, 1H, J7,6 = 8.4 Hz, HC-7), 7.69 (d, 1H,
J9,10 = 2.8 Hz, HC-9), 7.90 (d, 1H, J6,7 = 8.4 Hz, HC-
6), 8.37 (d, 2H, HC-20and HC-60), 8.69 (d, 1H,
J4,NH = 7.1 Hz, HC-4); 12.86 (d, 1H, JNH,4 = 7.1 Hz,
NH); 13C NMR (DMSO-d6) d 15.70 (CH3), 40.68
(CH2), 103.13 (C-3a), 105.89 (C-10), 111.28 (C-6),
112.49 (C-10b), 113.21 (C-7), 118.41 (C-20 and C-60),
121.13 (C-10a), 123.64 (C-40), 128.58 (C-30 and C-50),
129.28 (C-9), 130.07 (C-5a), 132.28 (C-7a), 136.55 (C-
4), 140.33 (C-10), 143.82 (C-10c), 161.52 (C-3); HRMS
(m/z) 329.28 (M + 1). Anal. Calcd for C20H14N4O2: C,
73.15; H, 4.91; N, 17.01. Found: C, 72.93; H, 4.81; N,
16.70.
4.1.6.8.
2-(4-Chloro-phenyl)-8-methyl-5-hydro-2H-
pyrazolo[4,3-c]pyrrolo[3,2-f]quinolin-3-one (9b). Yield
58%; mp > 300 ꢁC; Rf 0.43 (ethyl acetate); IR (KBr)
3252, 3088, 1618, 801 cmꢀ1 1H NMR (DMSO-d6) d
;
3.97 (s, 3H, CH3), 7.39 (d, 1H, J10,9 = 2.8 Hz, HC-10),
7.51 (d, 2H, J3 ,2 = J5 ,6 = 8.6 Hz, HC-30 and HC-50),
7.54 (d, 1H, J6,7 = 9.0 Hz, HC-6), 7.64 (d, 1H,
J9,10 = 2.8 Hz, HC-9), 7.87 (d, 1H, J7,6 = 9.0 Hz, HC-
0
0
0
0
4.1.6.5. 2-(4-Methoxy-phenyl)-5,8-dihydro-2H-pyraz-
olo[4,3-c]pyrrolo[3,2-f]quinolin-3-one (8a). Yield 75%;
mp 356 ꢁC (dec.); Rf 0.41 (ethyl acetate/methanol 8:2);
7), 8.44 (d, 2H, J2 ,3 = J6 ,5 = 8.6 Hz, HC-20 and HC-
0
0
0
0
IR (KBr) 3339, 3260, 2974, 1622, 1596 and 1554 cmꢀ1
;
60), 8.73 (s, 1H, HC-4), 12.94 (s, 1H, NH); 13C NMR