11008
L. Fang et al. / Tetrahedron 69 (2013) 11004e11009
1
4
.2.5.4. Compound 10d. A yellow oil. Yield: 78%. H NMR (CDCl
3
,
4
00 MHz):
d 1.19 (m, 2H), 1.39 (s, 54H), 1.75 (m, 2H), 1.91 (t,
J¼8.0 Hz, 12H), 2.17 (t, J¼8.0 Hz, 12H), 2.27 (t, J¼6.8 Hz, 4H), 2.51 (t,
1
3
J¼7.6 Hz, 2H), 2.72 (t, J¼6.8 Hz, 4H), 6.76 (s, 2H); C NMR (CDCl
3
,
1
00 MHz): 14.3, 28.2, 30.0, 30.2, 34.7, 49.9, 52.7, 57.5, 60.5, 80.8,
71.3, 172.9. HRMS (ESI): m/z [MþH] calcd for C57
d
þ
1
95 9 3 14
H F N O :
1216.6670; found: 1216.6666.
4
.2.6. Typical procedure for the preparation of compound 1e. A
I (1.6 mL, 10 equiv) in
. After the evaporation of
€
Scheme 4. The Friedlander reaction between 2-aminoarylketones and various
methylene ketones.
a-
mixture of 10e (3.70 g, 2.61 mmol), CH
CH CN was refluxed for 12 h under N
3
3
2
the solvent, the residue was stirred in HCOOH (20 mL) for 24 h.
The solvent was removed in vacuo, affording a yellow oil, which
was washed with acetone (3ꢁ20 mL) to give a yellow solid
mixture was solid at room temperature. The catalyst was essen-
tially insoluble in ethyl acetate when the product could be easily
dissolved. Then after filtration, the catalyst could be recovered.
The crude mixture was purified by silica gel column chromatog-
raphy with petroleum ether and ethyl acetate (4:1) to give the
pure product (13aeo).
ꢀ
1
(
1.97 g, yield: 85%). Mp 165e168 C.
6
H NMR (DMSO-d ,
4
00 MHz):
d
1.83 (t, J¼7.6 Hz, 12H), 1.98 (br, 2H), 2.12 (t, J¼7.6 Hz,
1
4
2
2H), 2.30 (m, 2H), 2.63 (s, 4H), 2.99 (s, 3H), 3.34 (m, 2H), 3.48 (s,
13
H), 7.96 (s, 2H); C NMR (DMSO-d
9.1, 29.3, 47.6, 57.1, 57.8, 167.6, 175.1. HRMS (ESI): m/z [MꢂI]
6
, 100 MHz):
d
13.7, 28.6, 28.8,
þ
calcd for C38
procedure was followed for the preparation of the compound
aed.
H
49
F
17
N
3
O
14: 1094.2943; found: 1094.2930. This
4.3.1. 9-Methyl-1,2,3,4-tetrahydroacridine (13a). 1H NMR (CDCl
400 MHz):
1.94 (m, 4H), 2.56 (s, 3H), 2.90 (t, J¼7.6 Hz, 2H), 3.12 (t,
J¼7.6 Hz, 2H), 7.46 (t, J¼7.6 Hz, 1H), 7.60 (t, J¼7.6 Hz, 1H), 7.95e7.99
m, 2H).
3
,
d
1
(
4
.2.6.1. Compound 1a. A yellow solid. Yield: 83%. Mp
ꢀ
1
4.3.2. 2,3,4-Trimethylquinoline (13b). 1H NMR (CDCl
2.43 (s, 3H), 2.63 (s, 3H), 2.73 (s, 3H), 7.49 (t, J¼7.6 Hz, 1H), 7.62 (t,
J¼7.6 Hz, 1H), 7.96e8.04 (m, 2H).
1
75e177 C. H NMR (DMSO-d
0H),1.61 (s, 2H),1.81 (s,12H), 2.10 (s,12H), 2.61 (s, 4H), 2.91 (s, 3H),
.16 (s, 2H), 3.42 (s, 4H), 7.47 (s, 2H); C NMR (DMSO-d , 100 MHz):
6
14.2,15.4, 21.8, 22.3, 26.0, 28.3, 28.7, 29.1, 29.3, 31.4, 47.8, 57.2, 57.7,
6
, 400 MHz):
d
0.82 (s, 3H), 1.23 (s,
3
, 400 MHz):
1
3
d
d
13
þ
(13c). 1
H
1
7
68.0, 174.8. HRMS (ESI): m/z [MꢂI] calcd for C35
H
60
N
3
O
14
:
4.3.3. 9-Methyl-2,3-dihydro-1H-cyclopenta[b]quinoline
NMR (CDCl , 400 MHz): 2.17e2.25 (m, 2H), 2.60 (s, 3H), 3.07 (t,
46.4075; found: 746.4077.
3
d
J¼7.6 Hz, 2H), 3.17 (t, J¼7.6 Hz, 2H), 7.48 (t, J¼7.6 Hz, 1H), 7.61 (t,
4
.2.6.2. Compound 1b. A yellow solid. Yield: 85%. Mp
J¼7.6 Hz, 1H), 7.93e8.02 (m, 2H).
ꢀ
1
1
1
1
(
2
1
61e163 C. H NMR (DMSO-d
.24 (s, 18H), 1.63 (s, 2H), 1.85 (t, J¼8.0 Hz, 12H), 2.12 (t, J¼8.0 Hz,
2H), 2.62 (s, 3H), 2.93 (s, 3H), 3.17e3.19 (m, 2H), 3.44 (s, 4H), 7.61
s, 2H); C NMR (DMSO-d
8.6, 28.8, 28.9, 29.0, 29.1, 29.2, 30.8, 31.4, 47.5, 57.0, 57.4, 61.0,167.6,
6
, 400 MHz):
d
0.85 (t, J¼6.8 Hz, 3H),
4.3.4. 9-Methyl-3,4-dihydroacridin-1(2H)-one
(CDCl , 400 MHz):
(s, 3H), 3.28 (t, J¼6.4 Hz, 2H), 7.56 (t, J¼7.6 Hz, 1H), 7.65 (t, J¼7.6 Hz,
1H), 7.99e8.22 (m, 2H).
(13d). 1
H
NMR
3
d
2.17e2.24 (m, 2H), 2.81 (t, J¼6.4 Hz, 2H), 3.05
13
6
, 100 MHz):
d
14.0, 21.6, 22.2, 25.9, 28.3,
þ
74.7. HRMS (ESI): m/z [MꢂI] calcd for C39
68 3
H N O14: 802.4701;
found: 802.4692.
4.3.5. 9-Methyl-2,3-dihydro-1H-cyclopenta[b]quinolin-1-one
1
(
13e). H NMR (CDCl
3
, 400 MHz):
d
2.86 (t, J¼6.8 Hz, 2H), 3.01 (s,
4
.2.6.3. Compound 1c. A yellow solid. Yield: 86%. Mp
3H), 3.36 (t, J¼6.8 Hz, 2H), 7.60 (t, J¼7.6 Hz, 1H), 7.83 (t, J¼7.6 Hz,
ꢀ
1
1
1
29e131 C. H NMR (DMSO-d
.23 (s, 26H), 1.63 (s, 2H), 1.85 (t, J¼7.6 Hz, 12H), 2.12 (t, J¼7.6 Hz,
2H), 2.61 (s, 4H), 2.94 (s, 3H), 3.18 (m, 2H), 3.44 (s, 4H), 7.75 (s, 2H);
6
, 400 MHz):
d
0.85 (t, J¼6.8 Hz, 3H),
1H), 8.07e8.22 (m, 2H).
1
4.3.6. 9-Phenyl-1,2,3,4-tetrahydroacridine (13f). 1H NMR (CDCl
400 MHz): 1.75e1.82 (m, 2H), 1.93e1.98 (m, 2H), 2.60 (t,
3
,
1
3
C NMR (DMSO-d
6
, 100 MHz):
d
14.1, 22.2, 25.9, 28.5, 28.7, 28.8,
d
2
9.0, 29.1, 29.2, 29.3, 30.8, 31.4, 47.6, 57.1, 57.5, 167.7, 174.8. HRMS
J¼6.8 Hz, 2H), 3.20 (t, J¼6.8 Hz, 2H), 7.22e7.60 (m, 8H), 8.01 (d,
þ
(
8
ESI): m/z [MꢂI] calcd for C43
76 3
H N O14: 858.5327; found:
J¼8.4 Hz, 1H).
58.5330.
4
.3.7. 2,3-Dimethyl-4-phenylquinoline (13g). 1
400 MHz): 2.18 (s, 3H), 2.76 (s, 3H), 7.23e7.64 (m, 8H), 8.03 (d,
J¼8.4 Hz, 1H).
H
3
NMR (CDCl ,
4
.2.6.4. Compound 1d. A yellow solid. Yield: 82%. Mp
d
ꢀ
1
155e157 C. H NMR (DMSO-d
6
, 400 MHz): d 1.84 (s, 12H), 1.98 (s,
2
2
d
H), 2.12 (s, 12H), 2.33 (m, 2H), 2.63 (s, 4H), 3.00 (s, 3H), 3.33 (m,
13
(13h). 1
H
H), 3.48 (s, 4H), 7.98 (s, 2H); C NMR (DMSO-d
6
, 100 MHz):
4.3.8. 9-Phenyl-2,3-dihydro-1H-cyclopenta[b]quinoline
NMR (CDCl , 400 MHz):
2.14e2.21 (m, 2H), 2.91 (t, J¼7.2 Hz, 2H),
3.23 (t, J¼7.2 Hz, 2H), 7.26e8.08 (m, 8H), 8.06 (d, J¼8.8 Hz, 1H).
13.8, 26.9, 28.8, 29.0, 29.5, 30.8, 47.7, 57.2, 57.8, 167.6, 175.2.
3
d
þ
HRMS (ESI): m/z [MꢂI] calcd for C34
49 17 3
H F N O14: 894.3071;
found: 894.3063.
4
.3.9. 9-Phenyl-3,4-dihydroacridin-1(2H)-one NMR
(13i). 1
H
(
CDCl , 400 MHz):
3
d
2.22e2.28 (m, 2H), 2.71 (t, J¼6.4 Hz, 2H), 3.38
4
.3. Preparation of quinolines under solvent-free conditions
A mixture of 2-aminoaryl ketone (11aec, 1 mmol) and
(t, J¼6.4 Hz, 2H), 7.16e7.78 (m, 8H), 8.06 (d, J¼8.4 Hz, 1H).
a
-
4.3.10. 9-Phenyl-2,3-dihydro-1H-cyclopenta[b]quinolin-1-one
1
methylene ketone (12, 1.2 mmol) was added to 2 mol % of com-
pound 1c or 1e (Scheme 4). The reaction mixture was heated at
the appropriate temperature with stirring for about 3 h (Table 2).
The extent of reaction was monitored by TLC. After completion of
the reaction, the mixture was added ethyl acetate (5 mL) when the
(13j). H NMR (CDCl
3
, 400 MHz):
d
2.84 (t, J¼7.2 Hz, 2H), 3.45 (t,
J¼7.2 Hz, 2H), 7.34e7.85 (m, 8H), 8.15 (d, J¼8.4 Hz, 1H).
4.3.11. 7-Chloro-9-phenyl-1,2,3,4-tetrahydroacridine (13k). 1H NMR
(CDCl , 400 MHz): d 1.76e1.80 (m, 2H), 1.94e1.98 (m, 2H), 2.59 (t,
3