The synthesis of 4-(3,3-dimethyl-3H-pyrrolo[2,3-f] quinolin-2-yl)pyrazoles and 4-(3,3-dimethyl-3H-pyrrolo[3,2-h] quinolin-2-yl)pyrazoles

Article abstract of DOI:10.1002/jhet.18

(Chemical Equation Presented) 5-Hydrazinoquinoline and 8-hydrazinoquinoline were converted via Fischer syntheses with 3-methylbutan-2-one into pyrido-indolenines 2,3,3-trimethyl-3H-pyrrolo[2,3-f]quinoline 7 and 2,3,3-trimethyl-3H-pyrrolo[ 3,2-h]quinoline 11, respectively. Exposure of the indolenines to the Vilsmeier reagent produced aminomethylene-malondialdehydes 8 and 12, which reacted with hydrazine or arylhydrazines to give 4-(3H-pyrrolo[2,3-f]quinolin-2-yl)- and 4-(3H-pyrrolo[3,2-h]quinolin-2-yl)- pyrazoles, 9 and 13.

Full text of DOI:10.1002/jhet.18

428
The Synthesis of 4-(3,3-Dimethyl-3H-pyrrolo[2,3-f]
quinolin-2-yl)pyrazoles and 4-(3,3-Dimethyl-3H-pyrrolo[3,2-h]
quinolin-2-yl)pyrazoles
Vol 46
A. Rashidi,a A. Afghan,a Mehdi M. Baradarani,a* and John A. Jouleb
aDepartment of Chemistry, Faculty of Science, University of Urmia, Urmia 57135, Iran
bThe School of Chemistry, The University of Manchester, Manchester M13 9PL, United Kingdom
*E-mail: m.baradarani@mail.urmia.ac.ir
Received August 14, 2008
DOI 10.1002/jhet.18
Published online 26 May 2009 in Wiley InterScience (www.interscience.wiley.com).
5-Hydrazinoquinoline and 8-hydrazinoquinoline were converted via Fischer syntheses with 3-methyl-
butan-2-one into pyrido-indolenines 2,3,3-trimethyl-3H-pyrrolo[2,3-f]quinoline 7 and 2,3,3-trimethyl-3H-
pyrrolo[3,2-h]quinoline 11, respectively. Exposure of the indolenines to the Vilsmeier reagent produced
aminomethylene-malondialdehydes 8 and 12, which reacted with hydrazine or arylhydrazines to give 4-
(3H-pyrrolo[2,3-f]quinolin-2-yl)- and 4-(3H-pyrrolo[3,2-h]quinolin-2-yl)-pyrazoles, 9 and 13.
J. Heterocyclic Chem., 46, 428 (2009).
INTRODUCTION
pound 6 with isopropyl methyl ketone in a Fischer reac-
tion [5] produced the pyrido-indolenine (2,3,3-trimethyl-
We recently described the reaction of 2,3,3-trimethy-
lindolenines (3H-indoles) 1 with the Vilsmeier reagent
formed from dimethylformamide and phosphorus oxy-
chloride to produce aminomethylene malondi-aldehydes
2 [1,2]. Additionally, we showed that these intriguing
polyfunctional compounds reacted well with hydrazine
or arylhydrazines to produce 4-(3,3-dimethyl-3H-indol-
2-yl)-substituted pyrazoles, 3, with migration of the dou-
ble bond into the dihydropyrrole ring thus restoring the
indolenine structure from which the sequence started [2]
(Scheme 1). We have now been able to show that the
principles embodied in these transformations can be
incorporated into more complex heterocyclic systems
and thus have prepared several 4-(3,3-dimethyl-3H-pyr-
rolo[2,3-f]quinolin-2-yl)pyrazoles and 4-(3,3-dimethyl-
3H-pyrrolo[3,3-h]quinolin-2-yl)pyrazoles.
For the mechanism of formation of the aminomethy-
lene malondialdehydes, we suggested that a small
equilibrium concentration of an enamine tautomer 4 is
successively C-substituted and thus, before hydrolysis
during work-up, species 5 is present (Scheme 2). We
suggest that a comparable mechanism operates in the
work described herein.
3H-pyrrolo[2,3-f]quinoline)
7
in acceptable yield
(Scheme 3). Similarly, 8-hydrazinoquinoline, prepared
by prolonged heating of 8-hydroxyquinoline with hydra-
zine hydrate [6], reacted with isopropyl methyl ketone
in hot acetic acid to give the isomeric pyrido-indolenine
(2,3,3-trimethyl-3H-pyrrolo[3,2-h]quinoline [7]) 11 in
60% yield (Scheme 4). The structures of the two key
pyrido-indolenines were evident from their molecular
formulae, the six-hydrogen singlets for the geminal
methyl groups, at d 1.35 and 1.37 ppm for 7 and 11,
and singlet signals for the imine-methyl groups, resonat-
ing at d 2.38 and 2.41 ppm, respectively. Each com-
pound had an AB system for the ortho-related benzene
ring protons, in addition to the three pyridine ring sig-
nals in normal positions. Each of the pyrido-indolenines
was now reacted with the Vilsmeier reagent and, in
yields of 94% and 81%, respectively, aminomethylene
malondialdehydes 8 and 12 were obtained (Schemes 3
and 4).
The structures of the aminomethylene malon-dialde-
hydes rests on the observation of two one-hydrogen sin-
glets at d 9.83 and d 9.86 for 8 and d 9.82 and d 9.90 for
12 corresponding to aldehyde protons. Absorptions at 3164
cmꢀ1 and 3160 cmꢀ1 for 8 and 12, respectively, were evi-
dence for the presence of NAH bonds, further confirmed
by 1H NMR one-hydrogen signals for the N-hydrogens
appearing at d 14.03 (8) and d 14.45 (12), respectively.
As in our previous work [2], the aminomethylene
malondialdehydes reacted smoothly with hydrazine and
various arylhydrazines to give pyrazoles, with migration
RESULTS AND DISCUSSION
Reduction of 5-nitroquinoline [3] with hydrazine and
iron(III) chloride gave 5-aminoquinoline, diazotization
of which, then reduction of the diazonium salt with
tin(II) chloride, produced the corresponding 5-hydra-
zino-quinoline 6 [4] dihydrochloride. Reaction of com-
C
V
2009 HeteroCorporation

May 2009
The Synthesis of 4-(3,3-Dimethyl-3H-pyrrolo[2,3-f]quinolin-2-yl)pyrazoles
and 4-(3,3-Dimethyl-3H-pyrrolo[3,2-h]quinolin-2-yl)pyrazoles
429
Scheme 1
General procedure for the synthesis of (7) and (11). A
mixture of quinolinylhydrazine dihydrochloride (5 g, 21 mmol)
and isopropyl methyl ketone (1.85 g, 21 mmol) was refluxed
in acetic acid (100 mL) for 3–5 h and then cooled, diluted
with water (100 mL), and neutralized with NaOH 2 M, then
extracted with ethyl acetate (4 ꢂ 100 mL). The organic layer
was dried over Na2SO4. The solvent was evaporated and the
resulting viscous oil recrystallized from EtOH to give the quin-
olinyl-indolenines identified as (7) or (11).
of the double bond to reform the imine unit (Schemes 3
and 4). For pyrazoles 9a–g, the newly formed five-mem-
bered heterocyclic ring protons resonated in the range d
8.30–9.70 and for the isomers, 13a–e, in the range d
8.30–9.10.
EXPERIMENTAL
2,3,3-Trimethyl-3H-pyrrolo[2,3-f]quinoline (7). 65% Yield;
1
Melting points were recorded on a Philip Harris C4954718
1
mp 115–118 ꢁC; IR: 2964, 2928, 1561, 1366 cmꢀ1; H NMR
apparatus and are uncorrected. H and 13C NMR spectra were
(CDCl3): d 1.35 (s, 6H), 2.38 (s, 3H), 7.44 (dd, 1H, J ¼ 8.4,
4.2 Hz), 7.64 (d, 1H, J ¼ 8.4 Hz), 7.98 (d, 1H, J ¼ 8.4 Hz),
8.84 (dd, 1H, J ¼ 8.4, 1.8 Hz), 8.90 (dd, 1H, J ¼ 4.2, 1.8
Hz); 13C NMR (CDCl3): d 15.57, 22.50, 54.77, 121.11,
121.87, 122.54, 126.47, 131.80, 142.28, 148.21, 148.67,
149.90, 189.72; m/z: 210 [M]þ, 195 (100), 181, 169, 154, 129,
84. Found: Mþ 210.1158, C14H14N2 requires Mþ 210.1157.
2,3,3-Trimethyl-3H-pyrrolo[3,2-h]quinoline (11). 80% Yield;
recorded on a Bruker Avance AQS 300 MHz spectrometer, at
300 MHz and 75 MHz, respectively. Chemical shifts d are in
parts per million (ppm) measured in CDCl3 as solvent and rel-
ative to TMS as the internal standard. Infrared spectra were
recorded on a Thermonicolet-Nexus 670 FTIR instrument and
elemental analyses were carried out on an Exeter analytical
model CE440 C, H and N elemental analyzer. High resolution
mass spectra were recorded on an Agilent Technology (HP),
MS Model: 5973 Network Mass, selective detector ion source:
electron impact (EI) 70 eV, ion source temperature: 230 ꢁC,
Analyzer: quadrupole, analyzer temperature: 150 ꢁC, and rela-
tive abundances of fragments are quoted in parentheses after
the m/z values.
1
mp 114–116 ꢁC; IR: 2966, 1686, 1515, 1359 cmꢀ1; H NMR
(CDCl3): d 1.37 (s, 6H), 2.41 (s, 3H), 7.38 (dd, 1H, J ¼ 8.4,
4.2 Hz), 7.50 (d, 1H, J ¼ 8.1 Hz), 7.70 (d, 1H, J ¼ 8.1 Hz),
8.17 (dd, 1H, J ¼ 8.4, 1.8 Hz), 9.00 (dd, 1H, J ¼ 4.2, 1.8
Hz); 13C NMR (CDCl3): d 15.58, 22.43, 55.45, 120.37,
120.97, 125.37, 128.36, 136.59, 140.40, 146.03, 148.64,
150.58, 189.87; m/z: 210 Mþ, 195 (100), 181, 169, 154, 129,
84. Found: Mþ 210.1157, C14H14N2 requires Mþ 210.1157.
General procedure for the synthesis of (8) and (12). To
N,N-dimethylformamide (10 mL) cooled in an ice bath was
added dropwise phosphorus oxychloride (7 mL, 75 mmol)
with stirring at below 10 ꢁC. After this addition, a solution of
(7) or (11) (25 mmol, 5.25 g) in DMF (10 mL) was added
dropwise. The coolingꢁbath was removed and the reaction mix-
ture was stirred at 75 C for 4–6 h. The resulting solution was
added to ice-cooled water and made alkaline with NaOH(aq.)
solution. The resulting precipitate was collected by filtration,
dried in air, recrystallized from ethanol, and identified as (8)
or (12).
5-Aminoquinoline. A mixture of 5-nitroquinoline (2.65 g,
15.2 mmol), activated carbon (600 mg), ferric chloride hex-
ahydrate (250 mg), and methanol (50 mL) was refluxed for 10
min with stirring. Hydrazine hydrate (3.75 g, 80%) was added
over 30 min to the boiling solution. The mixture was stirred
under reflux for an additional 12 h, cooled, and evaporated.
The resulting slurry was dissolved in dichloromethane
(50 mL), washed with water (2 ꢂ 20 mL), and dried (MgSO4).
Evaporation of the solvent yielded a yellow solid, which was
identified as 5-aminoquinoline. Yield 85%; mp: 108–110 ꢁC
(lit. 110 ꢁC); IR: 3196, 1585, 1365, 792 cmꢀ1 1H NMR
;
(CDCl3): d 4.22 (bs, 2H), 6.77 (dd, 1H, J ¼ 8.4, 1.2 Hz), 7.26
(dd, 1H, J ¼ 8.4, 4.2 Hz), 7.47 (t, 1H, J ¼ 8.4 Hz), 7.56 (d,
1H, J ¼ 8.4 Hz), 8.14 (dd, 1H, J ¼ 8.4, 1.8 Hz), 8.84 (dd, 1H,
J ¼ 4.2, 1.8 Hz); 13C NMR (CDCl3): d 109.95, 118.69,
119.55, 119.97, 129.60, 130.05, 142.42, 149.10, 150.21.
(3,3-Dimethyl-3H-pyrrolo[2,3-f]quinolin-2-ylidene)malondial-
dehyde (8). 94% Yield; mp 180–183 ꢁC; IR: NH 3164, 2965,
1
2763, 1679, 1601, 1518, 1363, 1166, 814, 771 cmꢀ1; H NMR
Scheme 2
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

430
A. Rashidi, A. Afghan, M. M. Baradarani, and J. A. Joule
Vol 46
Scheme 3
Hz), 7.60 (d, 1H, J ¼ 8.1 Hz), 7.74 (d, 1H, J ¼ 8.1 Hz), 8.28
(d, 1H, J ¼ 8.4 Hz), 8.73 (s, 2H), 9.18 (d, 1H, J ¼ 3.9 Hz);
13C NMR (CDCl3): d 24.26, 54.34, 116.25, 121.07, 122.16,
122.30, 126.44, 132.16, 134.21, 142.80, 148.42, 149.28,
150.08, 179.99. Found: % C 73.29; H 5.41; N 21.19.
C16H14N4 requires % C 73.26; H 5.38; N 21.36.
General procedure for the synthesis of (9b–g) and (13b–
g). A mixture of the malondialdehyde (8) or (12) (0.5 mmol)
and the arylhydrazine (0.55 mmol) in absolute ethanol
(15 mL) was heated with stirring at reflux for 2–3 h. After
cooling and concentrating the solution, the resulting crystals
were collected by filtration and recrystallized from EtOH to
give the corresponding pyrazoles.
1-Phenyl-4-(3,3-dimethyl-3H-pyrroꢁlo[2,3-f]quinolin-2-yl)-pyr-
azole (9b). 70% Yield; mp 168–170 C; IR: 3059, 2968, 2928,
2576, 1572, 1561, 1497, 1377, 950 cmꢀ1 1H NMR (CDCl3):
;
d 1.61 (s, 6H), 7.34 (dd, 1H, J ¼ 8.4, 4.5 Hz), 7.43–7.51 (m,
3H), 7.70 (d, 1H, J ¼ 8.4 Hz), 7.77 (m, 2H), 8.07 (d, 1H, J ¼
8.4 Hz), 8.38 (s, 1H), 8.68 (s, 1H), 8.94 (dd, 1H, J ¼ 4.5, 1.8
Hz), 9.00 (dt, 1H, J ¼ 8.4, 0.9 Hz); 13C NMR (CDCl3): d
24.18, 54.36, 118.06, 119.52, 121.15, 122.18, 122.74, 125.56,
127.22, 127.43, 129.48, 129.61, 133.06, 139.42, 140.75,
143.14, 147.25, 149.35, 179.77. Found: % C 78.29; H 5.26; N
16.41. C22H18N4 requires % C 78.08; H 5.36; N 16.56.
(CDCl3): d 1.86 (s, 6H), 7.55 (dd, 1H, J ¼ 8.4, 4.2 Hz), 7.72
(d, 1H, J ¼ 8.70 Hz), 8.06 (d, 1H, J ¼ 8.70 Hz), 8.34 (dd,
1H, J ¼ 8.4, 1.8 Hz), 9.02 (dd, 1H, J ¼ 4.2, 1.8 Hz), 9.83 (s,
1H), 9.86 (s, 1H,), 14.03 (bs, 1H); 13C NMR (CDCl3): d
22.84, 52.43, 110.17, 115.82, 121.79, 122.74, 127.55, 129.20,
134.34, 137.27, 148.08, 150.98, 180.33, 187.62, 192.68.
Found: % C 72.02; H 5.38; N 10.63. C16H14N2O2 requires %
C 72.16; H 5.30; N 10.52.
1-(2-Chlorophenyl)-4-(3,3-dimethyl-3H-pyrrolo[2,3-f]quinolin-
ꢁ
2-yl)pyrazole (9c). 90% Yield; mp 100–103 C; IR: 2958, 2927,
1
1580, 1559, 1491, 1451, 1365, 940, 816, 755 cmꢀ1; H NMR
(CDCl3): d 1.58 (s, 6H), 7.36–7.41 (m, 2H), 7.53–7.58 (m,
2H), 7.65 (dd, 1H, J ¼ 7.5, 1.8 Hz), 7.76 (d, 1H, J ¼ 8.4 Hz),
8.14 (d, 1H, J ¼ 8.4 Hz), 8.45 (s, 1H), 8.59 (s, 1H), 8.95 (dd,
1H, J ¼ 4.2, 1.5 Hz), 9.10 (d, 1H, J ¼ 8.4 Hz); 13C NMR
(3,3-Dimethyl-3H-pyrrolo[3,2-h]quinolin-2-ylidene)malondial-
ꢁ
(CDCl3):
d 24.21, 54.48, 117.25, 121.04,122.27, 123.28,
dehyde (12). 81% Yield; mp 166–168 C; IR: NH 3160, 2966,
1
124.90, 127.66, 127.92, 128.24, 129.78, 130.81, 131.81,
134.12, 137.43, 140.77, 143.47, 146.27, 148.67, 149.26,
179.90. Found: % C 70.71; H 4.68; Cl 9.41; N 15.16.
C22H17ClN4 requires % C 70.87; H 4.60; Cl 9.51; N 15.03.
1-(3-Chlorophenyl)-4-(3,3-dimethyl-3H-pyrrolo[2,3-f]quinolin-
2-yl)pyrazole (9d). 90% Yield; mp 151–153 ꢁC; IR: 2961,
2928, 1578, 1563, 1488, 1415, 1365, 1033, 959, 839, 772
2763,1673, 1602, 1504, 1325, 1161, 816, 768 cmꢀ1; H NMR
(CDCl3): d 1.87 (s, 6H), 7.50 (dd, 1H, J ¼ 8.4, 4.2 Hz), 7.54
(d, 1H, J ¼ 8.1 Hz), 7.73 (d, 1H, J ¼ 8.1 Hz), 8.23 (dd, 1H,
J ¼ 8.4, 1.5 Hz), 8.97 (dd, 1H, J ¼ 4.2, 1.5 Hz), 9.82 (s, 1H),
9.90 (s, 1H), 14.45 (bs, 1H); 13C NMR (CDCl3): d 22.75,
53.05, 110.03, 120.02, 121.87, 125.34, 128.26, 135.85, 136.08,
139.95, 150.94, 150.95, 179.05, 187.99, 192.21. Found: % C
71.98; H; 5.31; N 10.44. C16H14N2O2 requires % C 72.16; H
5.30; N 10.52.
cmꢀ1
;
1H NMR (CDCl3): d 1.58 (s, 6H), 7.30 (dt, 1H, J ¼
General procedure for the synthesis of (9a) and (13a). A
mixture of the malondialdehyde (8) or (12) (0.5 mmol) and
hydrazine monohydrate (0.05 g, 1 mmol) in absolute ethanol
(1 mL) was stirred at room temperature for 24 h (R ¼ H).
After concentrating the solution, the resulting crystals were
collected by filtration and recrystallized from EtOH to give the
(9a) and (13a).
Scheme 4
4-(3,3-Dimethyl-3H-pyrrolo[2,3-f]quinolin-2-yl)pyrazole (9a). 60%
Yield; mp 130–132 ꢁC; IR: 3137, 2969, 2926, 1570, 1486,
1
1330, 1062, 924, 832, 822 cmꢀ1; H NMR (CDCl3): d 1.60 (s,
6H), 3.50 (bs, 1H, NH), 7.51 (dd, 1H, J ¼ 8.4, 4.3 Hz), 7.74
(d, 1H, J ¼ 8.4 Hz), 8.04 (d, 1H, J ¼ 8.4 Hz), 8.35 (s, 2H),
8.95–9.01 (m, 2H); 13C NMR (CDCl3): d 24.28, 54.34, 116.24,
119.55, 121.07, 122.15, 122.28, 126.47, 132.12, 134.22,
142.77, 148.45, 150.12, 179.96. Found: % C 73.07; H 5.32; N
21.49. C16H14N4 requires % C 73.26; H 5.38; N 21.36.
4-(3,3-Dimethyl-3H-pyrrolo[3,3-h]quinolin-2-yl)pyrazole (13a). 65%
Yield; mp 135–139 ꢁC; IR: 3163, 2965, 2927, 1566, 1512,
1466, 1326, 1068, 940, 832, 727 cmꢀ1 1H NMR (CDCl3): d
;
1.62 (s, 6H), 4.10 (bs, 1H, NH), 7.49 (dd, 1H, J ¼ 8.4, 3.75
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

May 2009
The Synthesis of 4-(3,3-Dimethyl-3H-pyrrolo[2,3-f]quinolin-2-yl)pyrazoles
and 4-(3,3-Dimethyl-3H-pyrrolo[3,2-h]quinolin-2-yl)pyrazoles
431
8.1, 0.9 Hz), 7.40 (t, 1H, J ¼ 8.1 Hz), 7.47 (dd, 1H, J ¼ 8.4,
4.2 Hz), 7.66 (t, 1H, J ¼ 0.9 Hz), 7.70 (d, 1H, J ¼ 8.4 Hz),
7.83–7.84 (m, 1H), 8.03 (d, 1H, J ¼ 8.4 Hz), 8.39 (s, 1H),
8.63 (s, 1H), 8.95 (d, 2H, J ¼ 8.1 Hz); 13C NMR (CDCl3): d
24.17, 54.31, 117.29, 118.73, 119.73, 119.74, 121.15, 122.19,
126.83, 126.86, 127.28, 130.65, 131.95, 135.43, 140.39,
141.07, 142.84, 148.49, 149.18, 150.20, 179.02. Found: % C
70.93; H 4.61; Cl 9.43; N 14.91. C22H17ClN4 requires % C
70.87; H 4.60; Cl 9.51; N 15.03.
1-(3-Chlorophenyl)-4-(3,3-dimethyl-3H-pyrrolo[3,3-h]-quino-
ꢁ
lin-2-yl)pyrazole (13c). 80% Yield; mp 110–113 C; IR: 2962,
1
2926, 1594, 1570, 1488, 1458, 1074, 940, 833, 772 cmꢀ1; H
NMR (CDCl3): d 1.60 (s, 6H), 7.30–7.41 (m, 3H), 7.57–7.80
(m, 4H), 8.21–8.24 (m, 1H), 8.40 (s, 1H), 8.87 (s, 1H), 9.06–
9.08 (m, 1H); 13C NMR (CDCl3): d 24.11, 54.62, 117.11,
118.72, 119.75, 119.95, 120.94, 125.67, 127.21, 127.88,
128.88, 130.67, 135.47, 136.72, 140.43, 140.83, 141, 146.89,
149.22, 150.68, 178.98. Found: % C 70.78; H 4.66; Cl 9.67; N
14.94. C22H17ClN4 requires % C 70.87; H 4.60; Cl 9.51 N
15.03.
1-(4-Chlorophenyl)-4-(3,3-dimethyl-3H-pyrrolo[2,3-f]quinolin-
2-yl)pyrazole (9e). 90% Yield; mp 176–177 ꢁC; IR: 2967,
1
2927, 1577, 1562, 1492, 1421, 1067, 948, 824, 812 cmꢀ1; H
1-(4-Chlorophenyl)-4-(3,3-dimethyl-3H-pyrrolo[3,3-h]-qui-
nolin-2-yl)pyrazole (13d). 85% Yield; mp 128–131 ꢁC; IR:
NMR (CDCl3): d 1.62 (s, 6H), 7.48–7.52 (m, 3H), 7.75 (t, 3H,
J ¼ 8.4), 8.05 (d, 1H, J ¼ 8.40 Hz), 8.40 (s, 1H), 8.64 (s,
1H), 8.95–8.96 (m, 2H); 13C NMR (CDCl3): d 24.18, 54.30,
118.65, 120.60, 121.12, 122.17, 126.80, 126.85, 129.70,
131.92, 132.89, 138.05, 140.88, 142.81, 148.52, 149.21,
150.19, 179.11. Found: % C 70.81; H 4.50; Cl 9.56; N 15.10.
C22H17ClN4 requires % C 70.87; H 4.60; Cl 9.51;N 15.03.
1-(4-Methoxyphenyl)-4-(3,3-dimethyl-3H-pyrrolo[2,3-f]-qui-
nolin-2-yl)pyrazole (9f). 75% Yield; mp 139–141 ꢁC; IR:
2964, 2931, 1575, 1560, 1518, 1502, 1259, 1250, 1038, 958,
1
2967, 2930, 1573, 1496, 1378, 1267, 1076, 950, 817 cmꢀ1; H
NMR (CDCl3): d 1.65 (s, 6H), 7.48 (d, 1H, J ¼ 8.7 Hz), 7.56
(dd, 1H, J ¼ 8.1, 4.2 Hz), 7.67 (d, 1H, J ¼ 8.1 Hz), 7.77–7.83
(m, 4H), 8.36–8.38 (m, 1H), 8.39 (s, 1H), 9.07 (s, 1H), 9.17
(d, 1H, J ¼ 4.2, Hz); 13C NMR (CDCl3): d 24.00, 54.76,
118.13, 120.51, 120.67, 120.99, 125.72, 127.75, 128.27,
128.66, 129.58, 132.69, 137.85, 138.35, 138.78, 140.82,
147.77, 149.42, 179.55. Found: % C 70.83; H 4.61; Cl 9.50; N
15.08. C22H17ClN4 requires % C 70.87; H 4.60; Cl 9.51; N
15.03.
817 cmꢀ1 1H NMR (CDCl3): d 1.55 (s, 6H), 3.80 (s, 3H),
;
6.93–6.97 (m, 2H), 7.44 (dd, 1H, J ¼ 8.4, 4.2 Hz), 7.64–7.69
(m, 3H), 8.00 (d, 1H, J ¼ 8.4 Hz), 8.33 (s, 1H), 8.56 (s, 1H),
8.9 (dd, 1H, J ¼ 4.1, 1.8 Hz), 8.94 (d, 1H, J ¼ 9 Hz); 13C
NMR (CDCl3): d 24.25, 54.25, 55.55, 114.62, 117.92, 121.05,
121.12, 122.11, 122.23, 126.52, 127.04, 132.04, 133.15,
140.28, 142.78, 148.42, 149.28, 150.09, 158.82, 179.55.
Found: % C 74.71; H 5.39; N 15.29. C23H20N4O requires % C
74.98; H 5.47; N 15.21.
4-(3,3-Dimethyl-3H-pyrrolo[2,3-f]quinolin-2-yl)-1-(quinolin-
8-yl)pyrazole (9g). 30% Yield; mp 186–188 ꢁC; IR: 3055,
2969, 2926, 1580, 1561, 1471, 1409, 1050, 942, 825, 786
cmꢀ1 1H NMR (CDCl3): d 1.62 (s, 6H), 7.55–7.59 (m, 2H),
;
1-(4-Methoxyphenyl)-4-(3,3-dimethyl-3H-pyrrolo[3,3-h]-quino-
lin-2-yl)pyrazole (13e). 75% Yield; mp 187–189 ꢁC; IR: 2964,
1
2929, 1572, 1519, 1495, 1257, 1032, 953, 831 cmꢀ1; H NMR
(CDCl3): d 1.64 (s, 6H), 3.88 (s, 3H), 7.03 (d, 2H, J ¼ 9.0
Hz), 7.45 (dd, 1H, J ¼ 8.4, 4.2 Hz), 7.60 (d, 1H, J ¼ 8.1 Hz),
7.69–7.76 (m, 3H), 8.23 (dd, 1H, J ¼ 8.4, 1.2 Hz), 8.39 (s,
1H), 8.83 (s, 1H), 9.09 (dd, 1H, J ¼ 4.2, 1.2 Hz); 13C NMR
(CDCl3): d 24.27, 54.55, 55.61, 114.71, 118.01, 119.86,
120.88, 120.98, 125.40, 128.01, 128.67, 133.29, 136.39,
140.26, 141.16, 146.70, 149.53, 150.78, 158.81, 179.40.
Found: % C 75.06; H 5.40; N 15.25. C23H20N4O requires % C
74.98; H 5.47; N 15.21.
7.71 (t, 1H, J ¼ 7.8 Hz), 7.80 (d, 1H, J ¼ 8.4 Hz), 7.87–7.90
(m, 1H), 8.13 (d, 1H, J ¼ 8.4 Hz), 8.29–8.38 (m, 2H), 8.57 (s,
1H), 8.97–8.99 (m, 1H), 9.07–9.09 (m, 1H), 9.13 (d, 1H, J ¼
8.4 Hz), 9.67 (s, 1H); 13C NMR (CDCl3): d 24.46, 54.45,
117.18, 120.88, 121.76, 122.25, 122.94, 123.79, 125.39,
126.53, 127.43, 129.27, 133.54, 134.25, 136.23, 136.61,
140.46, 140.67, 143.27, 147.18, 149.16, 149.55, 150.60,
180.26. Found: % C 76.92; H 4.81; N 17.93. C25H19N5
requires % C 77.10; H 4.92; N 17.98.
Acknowledgments. The authors are grateful to the University of
Urmia for financial support of this work.
REFERENCES AND NOTES
[1] Helliwell, M.; Afgan, A.; Baradarani, M. M.; Joule, J. A.
Acta Crystallogr Sect E 2006, 62, o737.
1-(2-Chlorophenyl)-4-(3,3-dimethyl-3H-pyrrolo[3,3-h]-quino-
lin-2-yl)pyrazole (13b). 75% Yield; mp 97–100 ꢁC; IR: 2965,
[2] Baradarani, M. M.; Afghan, A.; ZebarJadi, F.; Hasanzadeh,
K.; Joule, J. A. J Heterocycl Chem 2006, 43, 1591.
[3] Riego, J. M.; Sedin, Z.; Zaldivar, J. M.; Marziano, N. C.;
Tortato, C. Tetrahedron Lett 1996, 37, 513.
[4] Ferlin, M. G.; Chiarelotto, G.; Basadonna, O.; Gia, O.;
Mobilo, S.; Baccichetti, F.; Carlassare, F. Il Farmaco 1989, 44, 1141.
[5] Robinson, B. The Fischer Indole Synthesis; Wiley: New
York, 1982.
1
2926, 1571, 1488, 1444, 1073, 940, 834, 759 cmꢀ1; H NMR
(CDCl3): d 1.63 (s, 6H), 7.36–7.46 (m, 3H), 7.56–7.60 (m,
2H), 7.68 (dd, 1H, J ¼ 8.1, 1.8 Hz), 7.75 (d, 1H, J ¼ 8.1 Hz),
8.23 (d, 1H, J ¼ 8.4 Hz), 8.57 (s, 1H), 8.73 (s, 1H), 9.08 (dd,
1H, J ¼ 4.5, 1.5 Hz); 13C NMR (CDCl3): d 24.28, 54.60,
117.63, 119.82, 120.88, 125.52, 127.62, 127.86, 128.11,
128.64, 129.54, 130.84, 132.04, 136.30, 137.62, 141.03,
141.33, 146.75, 149.66, 150.85, 179.05. Found: % C 70.69; H
4.53; Cl 9.61; N 15.12. C22H17ClN4 requires % C 70.87;H
4.60; Cl 9.51; N 15.03.
[6] Hegde, V.; Hung, C. Y.; Madhukar, P.; Cunningham, R.;
Hopfner, T.; Thummel, R. P. J Am Chem Soc 1993, 115, 872.
[7] Romanov, N. N.; Kolesnikov, A. M. Ukr Khim Zh 1991,
57, 965.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet