Month 2015
Spiro[3H-pyrazole-3,3′-oxindoles] Derived from 1,2,3,4-Tetrahydroquinoline
Table 1
75.19, %H 5.59, %N 13.80. C H N O requires %C
19 17 3
Yields of products 5, 6, and 7
75.23, %H 5.65, %N 13.85.
5
-(4-Nitrophenyl)-2,4,5′,6′-tetrahydro-2′H,4′H-spiro[pyrazole-
R
H
Compound (%)
Compound (%)
Compound (%)
3
(
,1′-pyrrolo[3,2,1-ij]quinolin]-2′-one (7b).
81mg, 87%) mp 239°C; νmax (KBr): 3263, 1695, 1629,
1599, 1506, 1481, 1339cm ; δH (300MHz, CDCl3):
.04–2.08 (m, 2H), 2.82 (t, 2H, J=5.7Hz), 3.42 (d, 1H,
J=16.5Hz), 3.72 (d, 1H, J= 16.5Hz), 3.77 (t, 2H, J=6.0Hz),
.31 (s, 1H, NH), 6.97 (dd, 1H, Ar-H, J =7.5Hz, J =9Hz),
7.14 (t, 2H, Ar-H, J= 9Hz), 7.81 (d, 2H, Ar-H, J=8.7Hz),
.26 (d, 2H, Ar-H, J=8.7Hz); δ (75MHz, CDCl ): 175.2,
Yellow crystals
5a (79)
5b (92)
5c (91)
5d (88)
5e (96)
5f (90)
5g (86)
6a (71)
6b (88)
6c (85)
6d (86)
6e (94)
6f (89)
6g (83)
7a (64)
7b (87)
7c (87)
7d (68)
7e (91)
7f (82)
7g (77)
À1
4
3
4
4
4
3
-NO
-NO
-Br
-F
-Cl
-OMe
2
2
2
6
1
2
8
C
3
1
1
%
47.9, 147.6, 138.2, 133.1, 129.4, 129.0, 126.7, 124.0, 123.1,
20.9, 120.8, 71.2, 43.5, 39.2, 24.4, 20.9. Found: %C 65.39,
H 4.58, %N 16.01. C H N O requires %C 65.51, %H
1
-Hydroxy-1-(2-oxo-2-phenylethyl)-5,6-dihydro-1H-pyrrolo
[
3,2,1-ij]quinolin-2(4H)-one (5a). White solid (90 mg, 79%)
mp 195°C. ν
443 cm ; δ (300 Hz, DMSO-d ): 1.89–1.94 (m, 2H),
.72 (m, 2H), 3.59 (d, 1H, J = 17.1 Hz), 3.60 (t, 2H,
19 16 4 3
(KBr): 3310, 2944, 1704, 1684, 1902,
max
H
4
.63, %N 16.08.
À1
1
2
6
5-(3-Nitrophenyl)-2,4,5′,6′-tetrahydro-2′H,4′H-spiro[pyrazole-
3
,1′-pyrrolo[3,2,1-ij]quinolin]-2′-one (7c).
Yellow crystals
J = 4.8 Hz), 4.06 (d, 1H, J = 17.1 Hz), 6.1 (1H, OH),
(71mg, 87%) mp 236°C. νmax (KBr): 3271, 1695, 1629,
6
7
7
.80 (t, 1H, Ar-H, J= 7.5Hz), 7.00 (d, 1H, Ar-H, J=7.5Hz),
.14 (d, 1H, Ar-H, J=7.5Hz), 7.32–7.65 (m, 3H, Ar-H),
.86 (d, 1H, Ar-H, J = 8.1 Hz), 7.95 (d, 1H, Ar-H,
À1
1
2
602, 1527, 1480, 1350cm , δH (300MHz, CDCl3):
.04–2.06 (m, 2H), 2.81 (t, 2H, J=5.6Hz), 3.44 (d, 1H,
J=16.5Hz), 3.73 (d, 1H, J= 16.8Hz), 3.75 (t, 2H, J=5.8Hz),
.23 (s, 1H, NH), 6.96–6.98 (m, 1H, Ar-H), 7.10–7.16
m, 2H, Ar-H), 7.59 (dd, 1H, Ar-H, J =7.2Hz, J =6.9Hz),
J=8.1Hz); δ (75MHz, DMSO-d ): 197.1, 176.0, 140.5,
C
6
6
(
1
1
5
%
36.4, 134.7, 133.1, 130.3, 129.8, 128.1, 127.5, 123.5,
20.5, 74.6, 47.7, 27.0, 24.3, 21.0. Found: %C 74.19, %H
.81, %N 4.49; C H NO requires %C 74.25, %H 5.85,
1
2
8
.05 (d, 1H, Ar-H, J=7.2Hz), 8.20 (d, 1H, Ar-H,
19
17
3
J=6.9Hz), 8.45 (s, 1H, Ar-H); δC (75MHz, CDCl3):
N 4.56.
1
1
2
75.4, 148.5, 148.1, 138.6, 133.9, 131.7, 129.6, 129.5,
28.9, 123.4, 123.1, 121.0, 120.9, 120.8, 71.1, 43.7, 39.2,
4.4, 20.9. Found: %C 65.43, %H 4.56, %N 15.99.
(Z)-1-(2-oxo-2-phenylethylidene)-5,6-dihydro-4H-pyrrolo[3,2,1-
ij]quinolin-2(1H)-one (6a). Red crystals (60mg, 71%) mp
92°C. ν
458 cm , δH (300MHz, CDCl ): 2.02–2.12 (m, 2H),
.80 (t, 2H, J= 6 Hz), 3.80 (t, 2H, J=5.7Hz) 6.97 (t, 1H,
1
1
2
(KBr): 3425, 2932, 1707, 1652, 1604,
max
C H N O requires %C 65.51, %H 4.63, %N 16.08.
19 16 4 3
À1
3
5-(4-Bromophenyl)-2,4,5′,6′-tetrahydro-2′H,4′H-spiro[pyrazole-
,1′-pyrrolo[3,2,1-ij]quinolin]-2′-one (7d). White crystals (63 mg,
3
Ar-H, J= 7.8Hz), 7.18 (d, 1H, Ar-H, J=7.8Hz), 7.29
d, 1H, Ar-H, J=7.8Hz), 7.86 (s, 1H), 8.27 (d, 3H, Ar-H,
J=8.7Hz), 8.39 (d, 2H, ArH, J=8.4Hz); δC (75MHz,
DMSO-d ): 190.5, 166.0, 150.3, 137.6, 136.5, 133.5,
6
8%) mp 221°C. ν
(KBr): 3272, 1695, 1627, 1598,
max
À1
(
1482cm ; δ (300MHz, CDCl ): 2.03–2.06 (m, 2H), 2.80
H
3
(t, 2H, J=5.7Hz), 3.36 (d, 1H, J= 16.5Hz) 3.67 (d, 1H,
J= 16.8Hz), 3.75 (t, 2H, J= 5.7Hz), 6.08 (bs, 1H, NH),
6
1
4
31.9, 131.5, 130.2, 126.6, 125.7, 125.1, 124.3, 121.2,
0.6, 24.2, 20.8. Found: %C 78.76, %H 5.19, %N 4.75;
6.95 (t, 1H, Ar-H, J=7.5Hz), 7.12 (dd, 2H, Ar-H, J =7.8,
1
J2 =7.2Hz), 7.53 (bs, 4H, Ar-H); δC (75MHz, CDCl3)
175.6, 150.8, 149.7, 138.5, 131.8, 131.1, 130.0, 128.7,
C H NO requires %C 78.87, %H 5.23, %N 4.84.
19
15
2
Typical procedure for the preparation of compounds
127.8, 123.3, 123.0, 120.8, 70.9, 43.9, 39.2, 24.4, 20.9.
(
7a–g). A mixture of compound 6a–g (0.05g, 0.172mmol)
Found: %C 59.58, %H 4.17, %N 10.91. C H BrN O
19
16
3
and hydrazine hydrate 50% (0.6 mmol) in EtOH (5 mL)
was stirred and heated at 70–80°C for 7–8h then cooled
slowly to 4°C. The solid that separated was filtered off
and recrystallized from EtOH.
requires %C 59.70, % H 4.22, %N 10.99.
5-(4-Fluorophenyl)-2,4,5′,6′-tetrahydro-2′H,4′H-spiro[pyrazole-
3,1′-pyrrolo[3,2,1-ij]quinolin]-2′-one (7e).
White crystals
(KBr): 3276, 1701, 1629,
(69 mg, 92%) mp 206°C. ν
max
À1
5-Phenyl-2,4,5′,6′-tetrahydro-2′H,4′H-spiro[pyrazole-3,1′-pyrrolo
1512, 1481cm ; δH (300MHz, CDCl ): 2.03–2.06 (m,
3
[
3,2,1-ij]quinolin]-2′-one (7a). White crystals (54 mg, 64%)
2H), 2.80 (t, 2H, J=5.7Hz), 3.37 (d, 1H, J=16.5Hz), 3.68
(d, 1H, J=16.5Hz), 3.75 (t, 2H, J=5.7Hz), 6.05 (s, 1H,
NH), 6.95 (t, 1H, Ar-H, J=7.8Hz), 7.0–7.2 (m, 4H, Ar-H),
7.66 (dd, 2H, Ar-H, J =8.1Hz, J =5.7Hz); δ (75MHz,
mp 188°C; ν
(KBr): 3271, 2937, 1706, 1613,
max
À1
1
477 cm ; δH (300MHz, CDCl ): 2.03–2.07 (m, 2H),
3
2
.80 (t, 2H, J= 5.7Hz), 3.41 (d, 1H, J= 16.5Hz) 3.71
1
2
C
(d, 1H, J = 16.5Hz), 3.77 (t, 2H, J = 5.7Hz), 6.6 (bs, 1H,
CDCl ): 175.8, 164.9, 161.6, 149.8, 138.6, 130.1, 128.6,
3
NH), 6.94 (t, 1H, Ar-H, J= 7.5Hz) 7.12 (d, 2H, Ar-H,
J =7.5 Hz), 7.39–7.41 (d, 3H, Ar-H, J =6.3 Hz), 7.69
128.4, 128.2, 123.0, 120.7, 115.8, 70.8, 44.2, 39.2, 24.4,
20.9. Found: %C, 70.02, %H, 4.96, %N, 13.03.
C H FN O requires %C 71.01, %H 5.02, %N 13.08.
(
m, 2H, Ar-H); δC (75 MHz, CDCl ): 175.8, 150.8,
3
19 16
3
1
1
48.5, 138.4, 132.1, 130.3, 129.2, 128.6, 127.6, 126.4,
23.0, 120.7, 70.8, 44.2, 39.2, 24.4, 21.0. Found: %C
5-(4-Chlorophenyl)-2,4,5′,6′-tetrahydro-2′H,4′H-spiro[pyrazole-
3,1′-pyrrolo[3,2,1-ij]quinolin]-2′-one (7f).
White crystals
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet