A clean synthesis of polyhydroacridine and indenoquinoline derivatives catalyzed by triethylbenzylammonium chloride in aqueous media

Article abstract of DOI:10.1002/jhet.5570430426

An efficient and convenient synthesis of benzo[a]acridines and indeno[1,2-b]benzo[f]quinolines was achieved in high yields by the reaction of N-arylidenenaphthalen-2-amine with 1,3-dicarbonyl compounds catalyzed with triethylbenzylammmonium chloride (TEBA

Full text of DOI:10.1002/jhet.5570430426

Jul-Aug 2006
A Clean Synthesis of Polyhydroacridine and Indenoquinoline Derivatives
Catalyzed by Triethylbenzylammonium Chloride in Aqueous Media
989
Xiang-Shan Wang*[a,b,c], Mei-Mei Zhang[a], Zhao-Sen Zeng[a], Da-Qing Shi[a,b],
Shu-Jiang Tu[a,b], Xian-Yong Wei[c], Zhi-Min Zong[c]
[a]Department of Chemistry, Xuzhou Normal University, Xuzhou, Jiangsu 221116 China
[b]The Key Laboratory of Biotechnology for Medical Plant of Jiangsu Province, Xuzhou, Jiangsu 221116 China
[c]School of Chemical Engineering, China University of Mining and Technology, Xuzhou, Jiangsu 221008 China
Received October 11, 2005
O
O
O
Ar
O
Ar
R
N
CH Ar
O
R
O
TEBAC
H2O
R
TEBAC
H2O
N
H
N
H
R
An efficient and convenient synthesis of benzo[a]acridines and indeno[1,2-b]benzo[f]quinolines was
achieved in high yields by the reaction of N-arylidenenaphthalen-2-amine with 1,3-dicarbonyl compounds
catalyzed with triethylbenzylammmonium chloride (TEBAC) in aqueous media. The structures were
established by spectroscopic data and further confirmed by X-ray analysis. This method provides several
advantages such as neutral conditions, high yields and simple work-up procedure. In addition, water was
chosen as a green and recyclable solvent.
J. Heterocyclic Chem., 43, 989 (2006).
Introduction.
that water is an attractive media for many organic
reactions resulting in less expensive, less dangerous and
environment-friendly, such as Diels-Alder reactions [9],
Claisen Rearrangement reactions [10], Reformatsky
reactions [11] and Pinacol-coupling reactions [12]. As
part of our current studies on the development of new
routes to heterocyclic systems [13], we now report an
efficient and clean synthetic route to the derivatives of
benzo[a]acridine and indeno[1,2-b]benzo[f]quinoline in
aqueous media catalyzed by TEBAC, through the reaction
of N-arylidenenaphthalen-2-amine with 1,3-dicarbonyl
compounds.
Nitrogen-containing heteroaromatic compounds often
play important roles as the scaffolds of bioactive
substances. Quinoline is one of the most popular N-
heteroaromatics incorporated into the structure of many
pharmaceuticals. It is known that many quinoline
containing compounds exhibit a wide spectrum of
pharmacological activities such as antiasthmatic, anti-
inflammatory and antimalarial [1]. In addition, acridine
derivatives containing 1,4-dihydropyridine (1,4-DHP), are
reported as well-known compounds for their pharma-
cological profile in calcium channel modulations [2]. The
chemical modifications on the DHP ring, such as different
substituents [3] or heteroatoms [4], have allowed the
study of the extended structure and activity relationship,
and also provided some insight into the molecular
interactions at the receptor level. The general method for
the synthesis of acridine derivatives are in conventional
organic solvents [5-7]. In order to avoid the disadvantages
such as toxicity and instability that many organic solvents
inherently have, we have working to find a new procedure
that will be environmentally friendly, and easy to operate
for the synthesis of those above-mentioned compounds.
Specifically, we focused our attention on the use of water
as reaction medium. They were considered very
promising and attractive substitutes for volatile organic
solvents and were widely used in the Green Chemistry
area, since Breslow [8] demonstrated hydrophobic effects
could strongly enhance the rate of some organic reactions
and rediscovered the use of water as solvent in organic
chemistry in 1980s. There has been growing recognition
Results and Discussion.
When the reaction of N-arylidenenaphthalen-2-amine
1a-1v and substituted 1,3-cyclohexadione
2
was
performed in water in the presence of TEBAC at 100 °C,
high yields of benzo[a]acridine derivatives 3 were
obtained (Scheme 1).
Scheme 1
O
O
Ar
N
CH Ar
+
TEBAC
H2O
R
R
O
N
H
R
R
1
2
3
In order to apply this reaction to a library synthesis,
various kinds of 1a-1u and 2 were selected to give the
corresponding acridine 3, and representative examples are

990
X. S. Wang, M. M. Zhang, Z. S. Zeng, D. Q. Shi, S. J. Tu, X. Y. Wei, Z. M. Zong
Vol 43
shown in Table 1. All of the 1a-1v gave expected
products in quantitative yields and purity. The isolated
acridines 3 were characterized by IR, 1H NMR and
elemental analyses. The analysis were in agreement with
Table 1
Results of the reaction 1 and 2 in water at 100 ºC [a].
Entry
R
Ar
Time (h) Yields (%)[b]
3a
3b
3c
3d
3e
3f
3g
3h
3i
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
H
C6H5
8
2
2
3
3
2
10
8
5
4
6
12
10
3
88
99
87
98
92
96
96
87
97
87
95
99
89
94
98
86
85
89
88
82
80
81
2,4-Cl2C6H3
3,4-Cl2C6H3
4-ClC6H4
3-NO2C6H4
3-ClC6H4
3,4-(CH3O)2C6H3
4-OHC6H4
4-CH3OC6H4
4-BrC6H4
3,4-(CH3)2C6H3
3-OH-4-CH3OC6H3
4-(CH3)2NC6H4
2-ClC6H4
2-thiophenyl
4-BrC6H4
4-CH3OC6H4
4-FC6H4
4-ClC6H4
3-ClC6H4
Figure 1. The crystal structure of the product 3d.
3j
3k
3l
Lastly, we studied the reuse of the water and TEBAC.
After disappearance of starting materials monitered by
TLC, a reaction mixture was allowed to cool down to
room temperature, the solid products were isolated by
filtration, and the filtrate of the water together with
TEBAC could be reused directly. The yield of the product
3a is fairly high (87%) even in the fourth cycle.
3m
3n
3o
3p
3q
3r
3s
3t
5
10
10
8
8
8
H
H
H
H
H
H
To expand the reaction scope of Schiff base with 1,3-
dicarbonyl compounds, we tried the reaction of 1 with
1,3-indenedione 4, as is expected, when the substituted
1,3-cyclohexadione 2 was replaced by 1,3-indenedione,
indeno[1,2-b]benzo[f] quinoline 5 were obtained under
the same reaction conditions in good yields (Scheme 2).
The results are summarized in Table 2.
3u
3v
C6H5
4-OHC6H4
12
12
[a] Reaction conditions: 10 mL water, 0.1 g TEBAC, 2 mmoles of 1
and 2 mmoles of 2; [b] Isolated yields.
their structures. The IR spectra for 3a exhibited sharp
1
bands at 3236 cm-1 (NH). The H NMR spectrum of 3a
exhibited a singlet identified as methine (5.79 ppm) along
with multiplets (6.97–7.95 ppm) for aromatic protons.
The NH proton resonance at 9.71 ppm disappeared after
addition of D2O to the DMSO-d6 solution of 3a.
Table 2
Results of the reaction 1 and 4 in water at 100 ºC [a].
Entry Ar
Time (h)
Yields (%)b
It is interesting that the positions of the two methyl groups
are different due to the conformation of the hexagonal ring:
one methyl is in the pseudoaxial site while the other is in the
pseudoequatorial site, so they exhibit two singlets at 0.84 and
1.03 ppm respectively, due to the different shielding degree.
Furthermore the four protons of the methylene also form four
double peaks at 2.03 (16.0 Hz), 2.22 (16.0 Hz), 2.40 (16.8
Hz) and 2.55 (16.8 Hz), respectively, due to the
conformation of the hexagonal ring. In order to further
confirm the structure of the product, X-ray analysis [14] of
3d was carried out. The structure of 3d is shown in Figure 1.
5a
5b
5c
5d
5e
5f
5g
5h
5i
2-thiophenyl
4-CH3OC6H4
4-FC6H4
3-ClC6H4
C6H5
18
18
10
10
18
12
12
12
20
12
87
90
95
92
93
94
80
84
92
92
4-ClC6H4
2,4-Cl2C6H3
3,4-Cl2C6H3
4-OHC6H4
3,4-(CH3)2C6H3
5j
[a] Reaction condition: 10 mL water, 0.1 g TEBAC, 2 mmoles of
1 and 2 mmoles of 4; [b] Isolated yields.
Scheme 2
O
O
Ar
N
CH Ar
TEBAC
H2O
+
O
N
H
1
4
5

Jul-Aug 2006
A Clean Synthesis of Polyhydroacridine and Indenoquinoline Derivatives
991
(DMSO-d6): ꢁ 0.85 (s, 3H, CH3), 1.03 (s, 3H, CH3), 2.05 (d, J =
16.0 Hz, 1H, CH), 2.24 (d, J = 16.0 Hz, 1H, CH), 2.41 (d, J =
16.4 Hz, 1H, CH), 2.56 (d, J = 16.4 Hz, 1H, CH), 5.83 (s, 1H,
CH), 7.14 (dd, J = 8.4 Hz, J’ = 2.0 Hz, 1H, ArH), 7.32~7.35 (m,
2H, ArH), 7.39 (d, J = 8.4 Hz, 1H, ArH), 7.44 (d, J = 8.0 Hz,
1H, ArH), 7.46 (d, J = 2.0 Hz, 1H, ArH), 7.83 (d, J = 8.8 Hz,
2H, ArH), 7.91 (d, J = 8.4 Hz, 1H, ArH), 9.83 (s, 1H, NH).
Anal. Calcd. for C25H21Cl2NO: C 71.10, H 5.01, N 3.32.
Found: C 71.03, H 5.15, N 3.31.
In conclusion, an efficient green chemistry method for
the synthesis of benzo[a]acridine and indeno[1,2-b]benzo-
[f]quinoline derivatives by condensation reaction of 1,3-
dicarbonyl compounds and N-arylidenenaphthalen-2-
amine was successfully established.
EXPERIMENTAL
Melting points were determined in open capillaries and are
uncorrected. IR spectra were recorded on a TENSOR 27
spectrometer in KBr pellet. H NMR spectra were obtained in
12-(4-Chlorophenyl)-9,9-dimethyl-8,9,10,12-tetrahydro-7H-
benzo[a]acridin-11-one (3d)
1
This compound was obtained as pale yellow crystals, mp
>300 °C; ir (KBr): ꢀmax 3257, 3076, 2956, 2935, 2873, 1635,
1578, 1540, 1519, 1500, 1488, 1468, 1429, 1387, 1286, 1258,
DMSO-d6 with Me4Si as internal standard using a Bruker-400
spectrometer. Elemental analyses were carried out using Carlo
Erba 1110 analyzer. X-ray diffraction was measured on a
Rigaku Mercury diffractometer.
1
1248, 1190, 1150, 1035, 843, 820, 748; H nmr (DMSO-d6): ꢁ
0.84 (s, 3H, CH3), 1.03 (s, 3H, CH3), 2.02 (d, J = 16.0 Hz, 1H,
CH), 2.23 (d, J = 16.0 Hz, 1H, CH), 2.39 (d, J = 16.4 Hz, 1H,
CH), 2.56 (d, J = 16.4 Hz, 1H, CH), 5.79 (s, 1H, CH), 7.19 (d, J
= 8.4 Hz, 2H, ArH), 7.24 (d, J = 8.4 Hz, 2H, ArH), 7.30~7.34
(m, 2H, ArH), 7.40~7.44 (m, 1H, ArH), 7.79~7.82 (m, 2H,
ArH), 7.90 (d, J = 8.8 Hz, 1H, ArH), 9.77 (s, 1H, NH).
Anal. Calcd. for C25H22ClNO: C 77.41, H 5.72, N 3.61.
Found: C 77.29, H 5.88, N 3.56.
General Procedure for the Synthesis of Benzo[a]acridines (3).
A suspension of a mixture of N-arylidenenaphthalen-2-
amine 1 (2 mmoles), substituted 1,3-cyclohexadione 2 (2
mmoles) and TEBAC (0.1 g) was stirred in water (10 mL) at 100
ºC for 2-12 hours. The crystalline precipitates were collected by
filtration, washed with water and recrystallized from DMF and
water to give pure benzo[a]acridines 3.
9,9-Dimethyl-12-phenyl-8,9,10,12-tetrahydro-7H-benzo[a]acridin-
11-one (3a).
9,9-dimethyl-12-(3-nitrophenyl)-8,9,10,12-tetrahydro-7H-benzo-
[a]acridin-11-one (3e)
This compound was obtained as pale yellow crystals, mp
>300 °C (Lit [7] 336~337 ºC); ir (KBr): ꢀmax 3236, 3077, 3021,
2961, 1578, 1520, 1467, 1428, 1386, 1337, 1261, 1237, 1152,
This compound was obtained as pale yellow crystals, mp
>300 °C; ir (KBr): ꢀmax 3257, 2958, 2871, 1637, 1581, 1522,
1501, 1468, 1383, 1347, 1299, 1255, 1224, 1154, 1121, 811,
742, 729, 687; 1H nmr (DMSO-d6): ꢁ 0.82 (s, 3H, CH3), 1.04 (s,
3H, CH3), 2.04 (d, J = 16.0 Hz, 1H, CH), 2.25 (d, J = 16.0 Hz,
1H, CH), 2.43 (d, J = 16.8 Hz, 1H, CH), 2.54 (d, J = 16.8 Hz,
1H, CH), 5.97 (s, 1H, CH), 7.31~7.35 (m, 1H, ArH), 7.36 (d, J =
8.8 Hz, 1H, ArH), 7.40~7.46 (m, 1H, ArH), 7.47 (d, J = 8.0 Hz,
1H, ArH), 7.70 (d, J = 7.6 Hz, 1H, ArH), 7.82~7.86 (m, 2H,
ArH), 7.89 (dd, J = 8.0 Hz, J’ = 1.6 Hz, 1H, ArH), 7.94 (d, J =
8.8 Hz, 1H, ArH), 8.06 (s, 1H, ArH), 9.88 (s, 1H, NH).
1
1035, 816, 765, 752, 729, 698; H nmr (DMSO-d6): ꢁ 0.84 (s,
3H, CH3), 1.03 (s, 3H, CH3), 2.03 (d, J = 16.0 Hz, 1H, CH), 2.22
(d, J = 16.0 Hz, 1H, CH), 2.40 (d, J = 16.8 Hz, 1H, CH), 2.55 (d,
J = 16.8 Hz, 1H, CH), 5.79 (s, 1H, CH), 6.97~7.01 (m, 1H,
ArH), 7.12 (t, J = 7.6 Hz, 2H, ArH), 7.22~7.25 (m, 2H, ArH),
7.29~7.33 (m, 2H, ArH), 7.40~7.44 (m, 1H, ArH), 7.77~7.81
(m, 2H, ArH), 7.95 (d, J = 8.4 Hz, 1H, ArH), 9.71 (s, 1H, NH).
Anal. Calcd. for C25H23NO: C 84.95, H 6.56, N 3.96. Found:
C 84.78, H 6.54, N 4.07.
Anal. Calcd. for C25H22N2O3: C 75.36, H 5.57, N 7.03. Found:
C 75.28, H 5.54, N 7.14.
12-(2,4-Dichlorophenyl)-9,9-dimethyl-8,9,10,12-tetrahydro-7H-
benzo[a]acridin-11-one (3b).
12-(3-Chlorophenyl)-9,9-dimethyl-8,9,10,12-tetrahydro-7H-benzo-
[a]acridin-11-one (3f).
This compound was obtained as pale yellow crystals, mp
>300 °C; ir (KBr): ꢀmax 3244, 3078, 2956, 2932, 1580, 1557,
1521, 1467, 1428, 1382, 1259, 1245, 1184, 1150, 1099, 1035,
This compound was obtained as pale yellow crystals, mp
>300 °C; ir (KBr): ꢀmax 3268, 3087, 2960, 2873, 1598, 1521,
1469, 1383, 1306, 1259, 1178, 1145, 1080, 1034, 881, 810, 794,
777, 744, 691; 1H nmr (DMSO-d6): ꢁ 0.85 (s, 3H, CH3), 1.04 (s,
3H, CH3), 2.05 (d, J = 16.0 Hz, 1H, CH), 2.24 (d, J = 16.0 Hz,
1H, CH), 2.42 (d, J = 16.8 Hz, 1H, CH), 2.55 (d, J = 16.8 Hz,
1H, CH), 5.82 (s, 1H, CH), 7.05~7.08 (m, 1H, ArH), 7.16~7.17
(m, 2H, ArH), 7.25 (s, 1H, ArH), 7.32~7.36 (m, 2H, ArH),
7.43~7.47 (m, 1H, ArH), 7.82 (d, J = 8.8 Hz, 2H, ArH), 7.93 (d,
J = 8.4 Hz, 1H, ArH), 9.79 (s, 1H, NH).
1
1044, 869, 846, 819, 787, 757, 745; H nmr (DMSO-d6): ꢁ 0.87
(s, 3H, CH3), 1.04 (s, 3H, CH3), 1.99 (d, J = 16.4 Hz, 1H, CH),
2.22 (d, J = 16.4 Hz, 1H, CH), 2.40 (d, J = 16.4 Hz, 1H, CH),
2.59 (d, J = 16.4 Hz, 1H, CH), 5.99 (s, 1H, CH), 7.21 (dd, J =
8.4 Hz, J’ = 2.4 Hz, 1H, ArH), 7.28~7.34 (m, 3H, ArH), 7.38 (d,
J = 2.4 Hz, 1H, ArH), 7.42~7.46 (m, 1H, ArH), 7.79 (d, J = 8.8
Hz, 1H, ArH), 7.80 (d, J = 7.6 Hz, 1H, ArH), 8.06 (d, J = 8.4 Hz,
1H, ArH), 9.84 (s, 1H, NH).
Anal. Calcd. for C25H22ClNO: C 77.41, H 5.72, N 3.61.
Found: C 77.26, H 5.75, N 3.50.
Anal. Calcd. for C25H21Cl2NO: C 71.10, H 5.01, N 3.32.
Found C 70.92, H 5.24, N 3.13.
12-(3,4-Dimethoxylphenyl)-9,9-dimethyl-8,9,10,12-tetrahydro-
7H-benzo[a]acridin-11-one (3g)
12-(3,4-Dichlorophenyl)-9,9-dimethyl-8,9,10,12-tetrahydro-7H-
benzo[a]acridin-11-one (3c).
This compound was obtained as pale yellow crystals, mp
This compound was obtained as pale yellow crystals, mp
>300 °C; ir (KBr): ꢀmax 3292, 2937, 2899, 2828, 2602, 1583,
1512, 1469, 1418, 1381, 1339, 1266, 1234, 1137, 1029, 823,
>300 °C; ir (KBr): ꢀmax 3272, 3073, 2957, 1600, 1582, 1519,
1
1467, 1428, 1194, 1149, 1130, 1030, 817, 781, 744; H nmr

992
X. S. Wang, M. M. Zhang, Z. S. Zeng, D. Q. Shi, S. J. Tu, X. Y. Wei, Z. M. Zong
Vol 43
1
815, 748; H nmr (DMSO-d6): ꢀ 0.89 (s, 3H, CH3), 1.04 (s, 3H,
CH3), 2.05 (d, J = 16.0 Hz, 1H, CH), 2.23 (d, J = 16.0 Hz, 1H,
CH), 2.40 (d, J = 16.8 Hz, 1H, CH), 2.55 (d, J = 16.8 Hz, 1H,
CH), 3.60 (s, 3H, CH3O), 3.63 (s, 3H, CH3O), 5.75 (s, 1H, CH),
6.58 (dd, J = 8.0 Hz, J’ = 2.0 Hz, 1H, ArH), 6.67 (d, J = 8.0 Hz,
1H, ArH), 6.96 (d, J = 2.0 Hz, 1H, ArH), 7.30~7.33 (m, 2H,
ArH), 7.41~7.45 (m, 1H, ArH), 7.77 (d, J = 8.8 Hz, 1H, ArH),
7.80 (d, J = 8.0 Hz, 1H, ArH), 8.00 (d, J = 8.8 Hz, 1H, ArH),
9.67 (s, 1H, NH).
This compound was obtained as pale yellow crystals, mp
>300 °C; ir (KBr): ꢁmax 3279, 3089, 3052, 2960, 2914, 2878,
1601, 1583, 1519, 1496, 1468, 1427, 1397, 1382, 1258, 1236,
1183, 1147, 1033, 822, 745, 699; 1H nmr (DMSO-d6): ꢀ 0.87 (s,
3H, CH3), 1.03 (s, 3H, CH3), 2.03~2.06 (m, 7H, CH + 2 CH3),
2.21 (d, J = 16.0 Hz, 1H, CH), 2.40 (d, J = 16.4 Hz, 1H, CH),
2.49 (d, J = 16.8 Hz, 1H, CH), 5.71 (s, 1H, CH), 6.85 (d, J = 7.6
Hz, 1H, ArH), 6.91 (dd, J = 8.0 Hz, J’ = 1.6 Hz, 1H, ArH), 7.03
(s, 1H, ArH), 7.29~7.32 (m, 2H, ArH), 7.40~7.43 (m, 1H, ArH),
7.76 (d, J = 8.4 Hz, 1H, ArH), 7.79 (d, J = 7.6 Hz, 1H, ArH),
7.96 (d, J = 8.4 Hz, 1H, ArH), 9.64 (s, 1H, NH).
Anal. Calcd. for C27H27NO3: C 78.42, H 6.58, N 3.39. Found:
C 78.26, H 6.57, N 3.22.
Anal. Calcd. for C27H27NO: C 85.00, H 7.13, N 3.67. Found:
C 85.19, H 7.24, N 3.55.
9,9-Dimethyl-12-(4-hydroxylphenyl)-8,9,10,12-tetrahydro-7H-
benzo[a]acridin-11-one (3h).
12-(3-Methoxyl-4-hydroxylphenyl)-9,9-dimethyl-8,9,10,12-tetra-
hydro-7H-benzo[a]acridin-11-one (3l).
This compound was obtained as pale yellow crystals, mp
>300 °C (Lit. [7] 315~316 ºC) ; ir (KBr): ꢁmax 3304, 3250, 3014,
2946, 1634, 1602, 1578, 1519, 1469, 1441, 1399, 1384, 1235,
This compound was obtained as pale yellow crystals, mp
>300 °C; ir (KBr): ꢁmax 3524, 3265, 3087, 2958, 1600, 1584,
1519, 1469, 1430, 1385, 1267, 1240, 1208, 1149, 1121, 1034,
827, 816, 747; 1H nmr (DMSO-d6): ꢀ 0.88 (s, 3H, CH3), 1.04 (s,
3H, CH3), 2.04 (d, J = 16.0 Hz, 1H, CH), 2.22 (d, J = 16.0 Hz,
1H, CH), 2.39 (d, J = 16.8 Hz, 1H, CH), 2.54 (d, J = 16.8 Hz,
1H, CH), 3.64 (s, 3H, CH3O), 5.97 (s, 1H, CH), 6.48 (s, 2H,
ArH), 6.91 (s, 1H, ArH), 7.28~7.33 (m, 2H, ArH), 7.41~7.45
(m, 1H, ArH), 7.76 (d, J = 8.8 Hz, 1H, ArH), 7.80 (d, J = 7.6 Hz,
1H, ArH), 8.00 (d, J = 8.4 Hz, 1H, ArH), 8.60 (s, 1H, OH), 9.04
(s, 1H, NH).
1
1170, 1149, 1123, 1034, 982, 837, 816, 747; H nmr (DMSO-
d6): ꢀ 0.86 (s, 3H, CH3), 1.03 (s, 3H, CH3), 2.02 (d, J = 16.0 Hz,
1H, CH), 2.21 (d, J = 16.0 Hz, 1H, CH), 2.38 (d, J = 16.8 Hz,
1H, CH), 2.53 (d, J = 16.8 Hz, 1H, CH), 5.68 (s, 1H, CH), 6.50
(d, J = 8.4 Hz, 2H, ArH), 7.00 (d, J = 8.4 Hz, 2H, ArH),
7.30~7.42 (m, 3H, ArH), 7.75 (d, J = 8.8 Hz, 1H, ArH), 7.79 (d,
J = 7.6 Hz, 1H, ArH), 7.94 (d, J = 8.8 Hz, 1H, ArH), 9.02 (s, 1H,
OH), 9.62 (s, 1H, NH).
Anal. Calcd. for C25H23NO2: C 81.27, H 6.27, N 3.79. Found:
C 81.22, H 6.31, N 3.83.
Anal. Calcd. for C26H25NO3: C 78.18, H 6.31, N 3.51. Found:
C 78.00, H 6.24, N 3.63.
12-(4-Methoxylphenyl)-9,9-dimethyl-8,9,10,12-tetrahydro-7H-
benzo[a]acridin-11-one (3i).
12-(4-Dimethylaminophenyl)-9,9-dimethyl-8,9,10,12-tetrahydro-
7H-benzo[a]acridin-11-one (3m).
This compound was obtained as pale yellow crystals, mp
>300 °C (Lit [7] 297~298 ºC) ; ir (KBr): ꢁmax 3268, 3088, 2959,
2928, 2833, 1598, 1584, 1498, 1469, 1426, 1398, 1383, 1302,
This compound was obtained as pale yellow crystals, mp
>300 °C (Lit [7] 346~347 ºC) ; ir (KBr): ꢁmax 3265, 3073, 2956,
2932, 2904, 1598, 1581, 1522, 1498, 1467, 1443, 1397, 1384,
1
1259, 1239, 1176, 1148, 1033, 833, 811, 746; H nmr (DMSO-
d6): ꢀ 0.86 (s, 3H, CH3), 1.03 (s, 3H, CH3), 2.03 (d, J = 16.0 Hz,
1H, CH), 2.22 (d, J = 16.0 Hz, 1H, CH), 2.39 (d, J = 16.8 Hz,
1H, CH), 2.54 (d, J = 16.8 Hz, 1H, CH), 3.61 (s, 3H, CH3O),
5.74 (s, 1H, CH), 6.68 (d, J = 8.4 Hz, 2H, ArH), 7.13 (d, J = 8.4
Hz, 2H, ArH), 7.28~7.32 (m, 2H, ArH), 7.39~7.43 (m, 1H,
ArH), 7.77 (d, J = 8.8 Hz, 1H, ArH), 7.79 (d, J = 8.4 Hz, 1H,
ArH), 7.94 (d, J = 8.4 Hz, 1H, ArH), 9.66 (s, 1H, NH).
Anal. Calcd. for C26H25NO2: C 81.43, H 6.57, N 3.65. Found:
C 81.32, H 6.48, N 3.57.
1
1343, 1264, 1239, 1125, 820, 780, 744; H nmr (DMSO-d6): ꢀ
0.88 (s, 3H, CH3), 1.04 (s, 3H, CH3), 2.02 (d, J = 16.0 Hz, 1H,
CH), 2.21 (d, J = 16.0 Hz, 1H, CH), 2.39 (d, J = 16.4 Hz, 1H,
CH), 2.53 (d, J = 16.4 Hz, 1H, CH), 2.74 (s, 6H, 2 CH3), 5.66 (s,
1H, CH), 6.48 (d, J = 8.8 Hz, 2H, ArH), 7.03 (d, J = 8.8 Hz, 2H,
ArH), 7.23~7.31 (m, 2H, ArH), 7.39~7.43 (m, 1H, ArH), 7.74
(d, J = 8.8 Hz, 1H, ArH), 7.78 (d, J = 8.0 Hz, 1H, ArH), 7.96 (d,
J = 8.0 Hz, 1H, ArH), 9.60 (s, 1H, NH).
Anal. Calcd. for C27H28N2O: C 81.78, H 7.12, N 7.06. Found:
C 81.69, H 7.06, N 7.00.
12-(4-Bromophenyl)-9,9-dimethyl-8,9,10,12-tetrahydro-7H-benzo-
[a]acridin-11-one (3j).
12-(2-Chlorophenyl)-9,9-dimethyl-8,9,10,12-tetrahydro-7H-benzo-
[a]acridin-11-one (3n).
This compound was obtained as pale yellow crystals, mp
>300 °C; ir (KBr): ꢁmax 3263, 3086, 2960, 2927, 2873, 1595,
1519, 1493, 1468, 1428, 1418, 1383, 1259, 1238, 1186, 1169,
This compound was obtained as pale yellow crystals, mp
>300 °C; ir (KBr): ꢁmax 3241, 3076, 2958, 2880, 159, 1522,
1467, 1381, 1317, 1259, 1236, 1152, 1034, 979, 815, 765, 742;
1H nmr (DMSO-d6): ꢀ 0.87 (s, 3H, CH3), 1.05 (s, 3H, CH3), 1.99
(d, J = 16.0 Hz, 1H, CH), 2.22 (d, J = 16.0 Hz, 1H, CH), 2.43 (d,
J = 16.8 Hz, 1H, CH), 2.59 (d, J = 16.8 Hz, 1H, CH), 6.02 (s,
1H, CH), 6.99~7.04 (m, 1H, ArH), 7.08~7.13 (m, 1H, ArH),
7.24 (dd, J = 8.0 Hz, J’ = 1.2 Hz, 1H, ArH), 7.28~7.33 (m, 3H,
ArH), 7.42~7.46 (m, 1H, ArH), 7.76~7.80 (m, 2H, ArH), 8.15
(d, J = 8.4 Hz, 1H, ArH), 9.79 (s, 1H, NH).
1
1147, 1011, 835, 809, 741; H nmr (DMSO-d6): ꢀ 0.84 (s, 3H,
CH3), 1.04 (s, 3H, CH3), 2.03 (d, J = 16.0 Hz, 1H, CH), 2.23 (d,
J = 16.0 Hz, 1H, CH), 2.39 (d, J = 16.4 Hz, 1H, CH), 2.55 (d, J =
16.4 Hz, 1H, CH), 5.79 (s, 1H, CH), 7.18 (d, J = 8.4 Hz, 2H,
ArH), 7.31~7.34 (m, 4H, ArH), 7.40~7.44 (m, 1H, ArH),
7.79~7.82 (m, 2H, ArH), 7.90 (d, J = 8.4 Hz, 1H, ArH), 9.76 (s,
1H, NH).
Anal. Calcd. for C25H22BrNO: C 69.45, H 5.13, N 3.24.
Found: C 69.21, H 5.10, N 3.23.
Anal. Calcd. for C25H22ClNO: C 77.41, H 5.72, N 3.61.
Found: C 77.31, H 5.79, N 3.66.
9,9-Dimethyl-12-(3,4-dimethylphenyl)-8,9,10,12-tetrahydro-7H-
benzo[a]acridin-11-one (3k).

Jul-Aug 2006
A Clean Synthesis of Polyhydroacridine and Indenoquinoline Derivatives
993
9,9-Dimethyl-12-(2-thiophenyl)-8,9,10,12-tetrahydro-7H-benzo-
[a]acridin-11-one (3o).
This compound was obtained as pale yellow crystals, mp
>300 °C; ir (KBr): ꢀmax 3265, 3087, 2950, 2888, 1684, 1600,
1581, 1519, 1494, 1467, 1428, 1385, 1317, 1286, 1237, 1191,
This compound was obtained as pale yellow crystals, mp
1
1139, 1124, 1088, 1014, 835, 811, 750; H nmr (DMSO-d6): ꢁ
>300 °C; ir (KBr): ꢀmax 3265, 2956, 1586, 1558, 1520, 1472,
1.75~1.79 (m, 1H, CH), 1.91~ 1.95 (m, 1H, CH), 2.23~2.32 (m,
2H, CH2), 2.60~2.63 ( m, 2H, CH2), 5.84 (s, 1H, CH), 7.19 (d, J
= 8.4 Hz, 2H, ArH), 7.22 (d, J = 8.4 Hz, 2H, ArH), 7.30~7.34
(m, 2H, ArH), 7.40~7.44 (m, 1H, ArH), 7.79~7.82 (m, 2H,
ArH), 7.88 (d, J = 8.4 Hz, 1H, ArH), 9.80 (s, 1H, NH).
Anal. Calcd. for C23H18ClNO: C 76.77, H 5.04, N 3.89.
Found: C 76.80, H 5.14, N 3.93.
1
1383, 1346, 1261, 1236, 811, 781, 775; H nmr (DMSO-d6): ꢁ
0.96 (s, 3H, CH3), 1.06 (s, 3H, CH3), 2.12 (d, J = 16.0 Hz, 1H,
CH), 2.27 (d, J = 16.0 Hz, 1H, CH), 2.42 (d, J = 16.8 Hz, 1H,
CH), 2.56 (d, J = 16.8 Hz, 1H, CH), 6.12 (s, 1H, CH), 6.61 (d, J
= 3.2 Hz, 1H, ArH), 6.72 (dd, J = 4.8 Hz, J’ = 3.2 Hz, 1H, ArH),
7.11 (dd, J = 4.8 Hz, J’ = 0.8 Hz, 1H, ArH), 7.29 (d, J = 8.8 Hz,
1H, ArH), 7.32 (t, J = 7.2 Hz, 1H, ArH), 7.47~7.51 (m, 1H,
ArH), 7.81 (d, J = 8.8 Hz, 1H, ArH), 7.84 (d, J = 8.0 Hz, 1H,
ArH), 8.00 (d, J = 8.4 Hz, 1H, ArH), 9.82 (s, 1H, NH).
Anal. Calcd. for C23H21NOS: C 76.84, H 5.89, N 3.90. Found:
C 76.71, H 5.93, N 3.90.
12-(3-Chlorophenyl)-8,9,10,12-tetrahydro-7H-benzo[a]acridin-
11-one (3t).
This compound was obtained as pale yellow crystals, mp
>300 °C; ir (KBr): ꢀmax 3273, 3064, 2933, 1654, 1601, 1582,
1519, 1493, 1467, 1427, 1397, 1379, 1282, 1237, 1191, 1137,
1123, 1079, 957, 817, 750, 688; 1H nmr (DMSO-d6): ꢁ
1.72~1.80 (m, 1H, CH), 1.90~1.97 (m, 1H, CH), 2.25~2.30 (m,
2H, CH2), 2.63~2.65 ( m, 2H, CH2), 5.86 (s, 1H, CH), 7.06~7.19
(m, 3H, ArH), 7.21~7.24 (m, 1H, ArH), 7.31~7.35 (m, 2H,
ArH), 7.42~7.46 (m, 1H, ArH), 7.82 (d, J = 8.8 Hz, 2H, ArH),
7.89 (d, J = 8.8 Hz, 1H, ArH), 9.84 (s, 1H, NH).
12-(4-Bromophenyl)-8,9,10,12-tetrahydro-7H-benzo[a]acridin-
11-one (3p).
This compound was obtained as pale yellow crystals, mp
>300 °C; ir (KBr): ꢀmax 3264, 3086, 2946, 1683, 1599, 1581,
1518, 1494, 1467, 1427, 1397, 1384, 1336, 1317, 1286, 1237,
1
1191, 1140, 1124, 1010, 831, 811, 749; H nmr (DMSO-d6): ꢁ
1.75~1.81 (m, 1H, CH), 1.91~ 1.97 (m, 1H, CH), 2.20~2.28 (m,
2H, 2.60~2.62 ( m, 2H, CH2), 5.82 (s, 1H, CH), 7.16 (d, J = 8.4
Hz, 2H, ArH), 7.30~7.34 (m, 4H, ArH), 7.40~7.44 (m, 1H,
ArH), 7.69~7.82 (m, 2H, ArH), 7.87 (d, J = 8.8 Hz, 1H, ArH),
9.80 (s, 1H, NH).
Anal. Calcd. for C23H18ClNO: C 76.77, H 5.04, N 3.89.
Found: C 76.79, H 5.05, N 3.88.
12-Phenyl-8,9,10,12-tetrahydro-7H-benzo[a]acridin-11-one
(3u).
Anal. Calcd. for C23H18BrNO: C 68.33, H 4.49, N 3.46.
Found: C 68.20, H 4.52, N 3.29.
This compound was obtained as pale yellow crystals, mp
>300 °C; ir (KBr): ꢀmax 3251, 3079, 2952, 2925, 2882, 1662,
1617, 1597, 1583, 1519, 1493, 1468, 1425, 1384, 1335, 1280,
1235, 1190, 1138, 1010, 958, 809, 744, 717, 697; 1H nmr
(DMSO-d6): ꢁ 1.73~1.80 (m, 1H, CH), 1.92~1.96 (m, 1H, CH),
2.23~2.28 (m, 2H, CH2), 2.60~2.63 ( m, 2H, CH2), 5.83 (s, 1H,
CH), 6.97~7.01 (m, 1H, ArH), 7.12 (t, J = 7.6 Hz, 2H, ArH),
7.22 (d, J = 7.6 Hz, 2H, ArH), 7.29~7.33 (m, 2H, ArH),
7.39~7.43 (m, 1H, ArH), 7.77~7.81 (m, 2H, ArH), 7.92 (d, J =
8.4 Hz, 1H, ArH), 9.77 (s, 1H, NH).
12-(4-Methoxylphenyl)-8,9,10,12-tetrahydro-7H-
benzo[a]acridin-11-one (3q).
This compound was obtained as pale yellow crystals, mp
>300 °C; ir (KBr): ꢀmax 3268, 3089, 2941, 2825, 1662, 1598,
1582, 1519, 1495, 1426, 1426, 1399, 1380, 1286, 1258, 1238,
1189, 1174, 1137, 1120, 813, 756; 1H nmr (DMSO-d6): ꢁ
1.70~1.80 (m, 1H, CH), 1.91~1.96 (m, 1H, CH), 2.20~2.30 (m,
2H, CH2), 2.59~2.62 ( m, 2H, CH2), 3.61 (s, 3H, CH3O), 5.77 (s,
1H, CH), 6.68 (d, J = 8.8 Hz, 2H, ArH), 7.11 (d, J = 8.8 Hz, 2H,
ArH), 7.28~7.32 (m, 2H, ArH), 7.39~7.43 (m, 1H, ArH), 7.77
(d, J = 8.8 Hz, 1H, ArH), 7.79 (d, J = 8.4 Hz, 1H, ArH), 7.91 (d,
J = 8.4 Hz, 1H, ArH), 9.71 (s, 1H, NH).
Anal. Calcd. for C23H19NO: C 84.89, H 5.89, N 4.30. Found:
C 84.91, H 5.74, N 4.15.
12-(4-Hydroxylphenyl)-8,9,10,12-tetrahydro-7H-benzo[a]acridin-
11-one (3v).
Anal. Calcd. for C24H21NO2: C 81.10, H 5.96, N 3.94. Found:
C 81.23, H 5.82, N 4.01.
This compound was obtained as pale yellow crystals, mp
>300 °C; ir (KBr): ꢀmax 3153, 2940, 1651, 1637, 1615, 1595,
1562, 1509, 1455, 1390, 1361, 1291, 1263, 1234, 1171, 1135,
12-(4-Fluorophenyl)-8,9,10,12-tetrahydro-7H-benzo[a]acridin-
11-one (3r).
1
955, 868, 846, 776, 756; H nmr (DMSO-d6): ꢁ 1.53~1.62 (m,
1H, CH), 1.77~1.82 (m, 1H, CH), 2.19~2.22 (m, 2H, CH2),
2.24~2.32 ( m, 2H, CH2), 5.07 (s, 1H, CH), 6.67 (d, J = 7.6 Hz,
2H, ArH), 7.13 (d, J = 7.6 Hz, 2H, ArH), 7.41 (s, 1H, OH),
7.64~7.66 (m, 2H, ArH), 8.06~8.14 (m, 4H, ArH), 9.12 (s, 1H,
NH).
This compound was obtained as pale yellow crystals, mp
>300 °C; ir (KBr): ꢀmax 3264, 3087, 295, 1685, 1601, 1582,
1519, 1495, 1427, 1385, 1283, 1236, 1219, 1189, 1137, 1092,
1
957, 837, 815, 800, 742; H nmr (DMSO-d6): ꢁ 1.73~1.81 (m,
1H, CH), 1.91~1.97 (m, 1H, CH), 2.21~2.28 (m, 2H, 2.60~2.63
( m, 2H, CH2), 5.84 (s, 1H, CH), 6.95 (t, J = 8.8 Hz, 2H, ArH),
7.22 (dd, J = 6.0 Hz, J’ = 8.4 Hz, 2H, ArH), 7.30~7.34 (m, 2H,
ArH), 7.40~7.44 (m, 1H, ArH), 7.78~7.82 (m, 2H, ArH), 7.90
(d, J = 8.4 Hz, 1H, ArH), 9.78 (s, 1H, NH).
Anal. Calcd. for C23H19NO2: C 80.92, H 5.61, N 4.10. Found:
C 80.78, H 5.54, N 4.12.
General Procedure for the Synthesis of Indeno[1,2-b]benzo[f]-
quinolines (5).
Anal. Calcd. for C23H18FNO: C 80.45, H 5.28, N 4.08. Found:
C 80.28, H 5.40, N 4.05.
The mixture of N-arylidenenaphthalen-2-amine 1 (2 mmol),
1,3-indenedione 4 (2 mmol) and TEBAC (0.1 g) was stirred in
water (10 mL) at 100 ºC for 10-20 h. The crystalline powder
formed was collected by filtration, washed with water and
12-(4-Chlorophenyl)-8,9,10,12-tetrahydro-7H-benzo[a]acridin-
11-one (3s).

994
X. S. Wang, M. M. Zhang, Z. S. Zeng, D. Q. Shi, S. J. Tu, X. Y. Wei, Z. M. Zong
Vol 43
recrystallized from DMF and water to give pure indeno[1,2-
b]benzo[f]quinolines 5.
696; 1H nmr (DMSO-d6): ꢁ 5.78 (s, 1H, CH), 7.04 (t, J = 7.2 Hz,
1H, ArH), 7.17 (t, J = 7.6 Hz, 2H, ArH), 7.24~7.27(m, 3H,
ArH), 7.34~7.47(m, 4H, ArH), 7.53 (d, J = 8.8 Hz, 1H, ArH),
7.62 (d, J = 7.2 Hz, 1H, ArH), 7.86~7.91 (m, 2H, ArH), 7.93 (d,
J = 8.8 Hz, 1H, ArH), 11.94 (s, 1H, NH).
13-(2-Thiophenyl)-7,13-dihydroindeno[1,2-b]benzo[f]quinolin-
12-one (5a).
This compound was obtained as red crystals, mp >300 °C; ir
(KBr): ꢀmax 3220, 3065, 1663, 1626, 1604, 1575, 1523, 1509,
1468, 1431, 1404, 1366, 1238, 1209, 1192, 1135, 901, 809, 654;
1H nmr (DMSO-d6): ꢁ 6.11 (s, 1H, CH), 6.79 (dd, J = 8.0 Hz, J’
= 1.6 Hz, 1H, ArH), 6.89 (d, J = 8.0 Hz, 1H, ArH), 7.16 (dd, J =
8.0Hz, J’ = 1.6 Hz, 1H, ArH), 7.34~7.50 (m, 6H, ArH), 7.63 (d,
J = 8.4 Hz, 1H, ArH), 7.89 (d, J = 8.4 Hz, 1H, ArH), 7.93 (d, J =
8.8 Hz, 1H, ArH), 8.08 (d, J = 8.8 Hz, 1H, ArH), 11.04 (s, 1H,
NH).
Anal. Calcd. for C26H17NO: C 86.88, H 4.77, N 3.90. Found:
C 86.73, H 4.58, N 3.92.
13-(4-Chlorophenyl)-7,13-dihydroindeno[1,2-b]benzo[f]quinolin-
12-one (5f).
This compound was obtained as red crystals, mp >300 °C; ir
(KBr): ꢀmax 3226, 3063, 1661, 1627, 1604, 1574, 1533, 1468,
1406, 1365, 1239, 1200, 1145, 1072, 900, 809, 741, 698; 1H nmr
(DMSO-d6): ꢁ 5.82 (s, 1H, CH), 7.22~7.28(m, 5H, ArH),
7.35~7.46(m, 4H, ArH), 7.53 (d, J = 8.8 Hz, 1H, ArH), 7.63 (d, J
= 6.8 Hz, 1H, ArH), 7.85~7.89 (m, 2H, ArH), 7.94 (d, J = 8.8
Hz, 1H, ArH), 10.98 (s, 1H, NH).
Anal. Calcd. for C24H15NOS: C 78.88, H 4.14, N 3.83. Found:
C 78.75, H 4.23, N 3.69.
13-(4-Methoxylphenyl)-7,13-dihydroindeno[1,2-b]benzo[f]-
quinolin-12-one (5b).
Anal. Calcd. for C26H16ClNO: C 79.29, H 4.09, N 3.56.
Found: C 79.19, H 4.04, N 3.62.
This compound was obtained as red crystals, mp >300 °C; ir
(KBr): ꢀmax 3218, 3098, 3065, 1660, 1627, 1605, 1574, 1533,
108, 167, 1405, 1253, 1203, 1174, 1106, 1031, 900, 821, 808,
13-(2,4-Dichlorophenyl)-7,13-dihydroindeno[1,2-b]benzo[f]-
quinolin-12-one (5g).
1
742, 701; H nmr (DMSO-d6): ꢁ 3.62 (s, 1H, CH), 5.72 (s, 1H,
This compound was obtained as red crystals, mp >300 °C; ir
(KBr): ꢀmax 3269, 3050, 1663, 1630, 1606, 1574, 1532, 1469,
1404, 1240, 1198, 1146, 1102, 1046, 902, 860, 839, 813, 743,
CH), 6.73 (d, J = 8.8 Hz, 2H, ArH), 7.14 (d, J = 8.8 Hz, 2H,
ArH), 7.25 (d, J = 8.4 Hz, 1H, ArH), 7.33~7.47 (m, 4H, ArH),
7.51 (d, J = 8.4 Hz, 1H, ArH), 7.61 (d, J = 8.0 Hz, 1H, ArH),
7.86 (d, J = 8.8 Hz, 1H, ArH), 7.91 (d, J = 8.8 Hz, 2H, ArH),
11.91 (s, 1H, NH).
1
700; H nmr (DMSO-d6): ꢁ 6.09 (s, 1H, CH), 7.19 (dd, J = 8.4
Hz, J’ = 1.6 Hz, 1H, ArH), 7.27 (d, J = 8.4 Hz, 1H, ArH),
7.37~7.68(m, 7H, ArH), 7.81 (d, J = 8.4 Hz, 1H, ArH), 7.88 (d, J
= 8.4 Hz, 1H, ArH), 7.94 (d, J = 8.8 Hz, 1H, ArH), 8.11 (d, J =
8.8 Hz, 1H, ArH), 11.08 (s, 1H, NH).
Anal. Calcd. for C26H15Cl2NO: C 72.91, H 3.53, N 3.27.
Found: C 72.86, H 3.49, N 3.10.
Anal. Calcd. for C27H19NO2: C 83.27, H 4.92, N 3.60. Found:
C 83.09, H 4.90, N 3.53.
13-(4-Fluorophenyl)-7,13-dihydroindeno[1,2-b]benzo[f]quinolin-
12-one (5c).
This compound was obtained as red crystals, mp >300 °C; ir
(KBr): ꢀmax 3218, 3064, 1661, 1602, 1573, 1533, 1468, 1432,
1406, 1366, 1224, 1201, 1177, 1146, 1136, 901, 830, 811, 740,
700; 1H nmr (DMSO-d6): ꢁ 5.82 (s, 1H, CH), 7.00 (t, J = 8.8 Hz,
2H, ArH), 7.25~7.28 (m, 3H, ArH), 7.36~7.48 (m, 4H, ArH),
7.53 (d, J = 9.2 Hz, 1H, ArH), 7.63 (d, J = 7.2 Hz, 1H, ArH),
7.88 (d, J = 8.4 Hz, 2H, ArH), 7.93 (d, J = 8.8 Hz, 1H, ArH),
10.96 (s, 1H, NH).
13-(3,4-Dichlorophenyl)-7,13-dihydroindeno[1,2-b]benzo[f]-
quinolin-12-one (5h).
This compound was obtained as red crystals, mp >300 °C; ir
(KBr): ꢀmax 3253, 3028, 1686, 1627, 1608, 1573, 1520, 1513,
1468, 1404, 1363, 1203, 1184, 1146, 1031, 905, 812, 735, 701;
1H nmr (DMSO-d6): ꢁ 5.88 (s, 1H, CH), 7.12 (dd, J = 8.4 Hz, J’
= 2.0 Hz, 1H, ArH), 7.29 (d, J = 8.4 Hz, 1H, ArH), 7.36~7.49(m,
5H, ArH), 7.54 (d, J = 8.8 Hz, 1H, ArH), 7.56 (d, J = 2.0 Hz,
1H, ArH), 7.64 (d, J = 8.0 Hz, 1H, ArH), 7.85~7.91 (m, 2H,
ArH), 8.01 (d, J = 8.8 Hz, 1H, ArH), 11.05 (s, 1H, NH).
Anal. Calcd. for C26H15Cl2NO: C 72.91, H 3.53, N 3.27.
Found: C 72.81, H 3.44, N 3.19.
Anal. Calcd. for C26H16FNO: C 82.74, H 4.27, N 3.71. Found:
C 82.70, H 4.25, N 3.61.
13-(3-Chlorophenyl)-7,13-dihydroindeno[1,2-b]benzo[f]quinolin-
12-one (5d).
This compound was obtained as red crystals, mp >300 °C; ir
(KBr): ꢀmax 3277, 3062, 1660, 1625, 1601, 1590, 1568, 1508,
1468, 1430, 1401, 1366, 1234, 1196, 1178, 1133, 1081, 898,
13-(4-Hydroxylphenyl)-7,13-dihydroindeno[1,2-b]benzo[f]quinolin-
12-one (5i).
1
814, 765, 743, 719, 692; H nmr (DMSO-d6): ꢁ 5.85 (s, 1H,
This compound was obtained as red crystals, mp >300 °C; ir
(KBr): ꢀmax 3442, 3219, 3068, 1660, 1626, 1604, 1575, 1532,
1509, 1405, 1405, 1269, 1202, 1135, 1072, 900, 834, 812, 742,
702; 1H nmr (DMSO-d6): ꢁ5.65 (s, 1H, CH), 6.54 (d, J = 8.4 Hz,
2H, ArH), 7.02 (d, J = 8.4 Hz, 2H, ArH), 7.25 (d, J = 8.4 Hz,
1H, ArH), 7.32~7.46 (m, 4H, ArH), 7.50 (d, J = 8.4 Hz, 1H,
ArH), 7.60 (d, J = 7.6 Hz, 1H, ArH), 7.87 (d, J = 8.8 Hz, 1H,
ArH), 7.89~7.92 (m, 2H, ArH), 9.13 (s, 1H, OH), 10.87 (s, 1H,
NH).
CH), 7.11~7.48 (m, 9H, ArH), 7.54 (d, J = 8.8 Hz, 1H, ArH),
7.64 (d, J = 7.2 Hz, 1H, ArH), 7.89 (d, J = 8.0 Hz, 2H, ArH),
7.96 (d, J = 8.8 Hz, 1H, ArH), 11.01 (s, 1H, NH).
Anal. Calcd. for C26H16ClNO: C 79.29, H 4.09, N 3.56.
Found: C 79.13, H 3.99, N 3.57.
13-Phenyl-7,13-dihydroindeno[1,2-b]benzo[f]quinolin-12-one
(5e)
This compound was obtained as red crystals, mp >300 °C; ir
(KBr): ꢀmax 3218, 3053, 1660, 1626, 1603, 1575, 1532, 1468,
1431, 1405, 1366, 1263, 1136, 1070, 910, 896, 831, 806, 746,
Anal. Calcd. for C26H17NO2: C 83.13, H 4.56, N 3.73. Found:
C 82.97, H 4.50, N 3.84.

Jul-Aug 2006
A Clean Synthesis of Polyhydroacridine and Indenoquinoline Derivatives
995
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Heterocyclic Chem., 27, 363 (1990).
[8a] R. Breslow and D. C. Rideout, J. Am. Chem. Soc., 102, 7816
(1980); [b] R. Breslow, Acc. Chem. Res., 24, 159 (1991).
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[b] J. Y. Zhou, G. D. Lu and S. H. Wu, Synth. Commun., 22, 481 (1992).
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398 (1989).
13-(3,4-Dimethylphenyl)-7,13-dihydroindeno[1,2-b]benzo[f]-
quinolin-12-one (5j).
This compound was obtained as red crystals, mp >300 °C; ir
(KBr): ꢀmax 3278, 3037, 2970, 1662, 1628, 1602, 1575, 1529,
1468, 1443, 1400, 1339, 1233, 1193, 1179, 1133, 901, 810, 768,
1
745, 710; H nmr (DMSO-d6): ꢁ 2.05 (s, 3H, CH3), 2.06 (s, 3H,
CH3), 5.68 (s, 1H, CH), 6.91 (s, 2H, ArH), 7.01 (s, 1H, ArH),
7.25 (d, J = 8.4 Hz, 1H, ArH), 7.32~7.46 (m, 4H, ArH), 7.52 (d,
J = 8.8 Hz, 1H, ArH), 7.60 (d, J = 7.6 Hz, 1H, ArH), 7.86 (d, J =
8.8 Hz, 1H, ArH), 7.89~7.92 (m, 2H, ArH), 10.92 (s, 1H, NH).
Anal. Calcd. for C28H21NO: C 86.79, H 5.46, N 3.61. Found:
C 86.92, H 5.51, N 3.33.
Acknowledgments.
[13a] X. S. Wang, M. M. Zhang, Z. S. Zeng, D. Q. Shi, X. Y. Wei,
and Z. M. Zong, Chem. Lett., 34, 1316 (2005); [b] X. S. Wang, D. Q.
Shi, Y. L. Li, H. Chen, X. Y. Wei and Z. M. Zong, Synth. Commun., 35,
97 (2005); [c] X. S. Wang, D. Q. Shi, Y. F. Zhang, S. H. Wang and S. J.
Tu, Chin. J. Org. Chem., 24, 430 (2004).
We are grateful to the Foundation (04KJB150139) of the
Education Committee of Jiangsu Province for financial support.
REFERENCES AND NOTES
[14] Crystal data for 5a: C25H22ClNO; M = 387.89, colorless block
crystals, 0.40 ꢀ 0.35 ꢀ 0.12 mm, monoclinic, space group P21/n, a =
[1] A. Arcadi, M. Chiarini, S. D. Giuseppe and F. Marinelli,
Synlett, 203 (2003).
10.4242(14), b = 11.777(2), c = 16.173(3) Å,
= 91.024(5)°, V =
1985.1(5) Å3, Z = 4, Dc = 1.298 g.cm-3. F(000) = 816, (MoKꢀ) = 0.208
mm-1. Intensity data were collected on a Rigaku Mercury diffractometer
with graphite monochromated MoKꢀ radiation (ꢁ=0.71070Å) using the
ꢂ scan mode with 3.06°<ꢃ<25.35°. 3622 unique reflections were
measured and 3006 reflections with I>2ꢄ(I) were used in the refinement.
Structure solved by direct methods and expanded using Fourier
techniques. The final cycle of full-matrix least squares technique to R =
0.0571 and wR = 0.1186.
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