An improved and benign synthesis of 9,10-diarylacridine-1,8-dione and indenoquinoline derivatives from 3-anilino-5,5-dimethylcyclohex-2-enones, benzaldehydes, and 1,3-dicarbonyl compounds in an ionic liquid medium

Article abstract of DOI:10.1055/s-2006-950365

Improved and green syntheses of 9,10-diarylacridine-1,8-dione and indenoquinoline derivatives were accomplished by the reactions of 3-anilino-5,5-dimethylcyclohex-2-enones, benzaldehydes, and 1,3-dicarbonyl compounds in the ionic liquid medium [bmim⁺

Full text of DOI:10.1055/s-2006-950365

PAPER
4187
An Improved and Benign Synthesis of 9,10-Diarylacridine-1,8-dione and
Indenoquinoline Derivatives from 3-Anilino-5,5-dimethylcyclohex-2-enones,
Benzaldehydes, and 1,3-Dicarbonyl Compounds in an Ionic Liquid Medium
atives han Wang,* Mei-Mei Zhang, Hong Jiang, Da-Qing Shi, Shu-Jiang Tu,a,c Xian-Yong Wei,b
a,b,c
a
c
a,c
S
X
ynthesis of 9,10-D
i
iaryla
a
cridine-1,8-
n
dione and In
g
denoquinolin
-
e
D
eriv
S
b
Zhi-Min Zong
a
Department of Chemistry, Xuzhou Normal University, Xuzhou Jiangsu, 221116, P. R. of China
School of Chemical Engineering, China University of Mining and Technology, Xuzhou Jiangsu 221008, P. R. of China
The Key Laboratory of Biotechnology for Medical Plant of Jiangsu Province, Xuzhou Jiangsu 221116, P. R. of China
Fax +86(516)83403164; E-mail: xswang1974@yahoo.com
b
c
Received 6 July 2006; revised 22 August 2006
5
6
water, under microwave irradiation, or by green chemis-
Abstract: Improved and green syntheses of 9,10-diarylacridine-
7
try in ionic liquids. Acridines are also important com-
1
,8-dione and indenoquinoline derivatives were accomplished by
8
9
10
pounds possessing antitumor, cytotoxic, anticancer,
the reactions of 3-anilino-5,5-dimethylcyclohex-2-enones, benzal-
dehydes, and 1,3-dicarbonyl compounds in the ionic liquid medium
antimicrobial,11 anti-multidrug-resistant, fungicidal,
12
13,14
+
–
4
14
[
bmim ][BF ]. Not only the substituted anilines containing elec- and antibacterial activity.
tron-donating groups, but also those with electron-withdrawing
groups all gave excellent yields. Furthermore, the interesting un-
symmetrical 9,10-diarylacridine-1,8-dione moiety with different
groups in the 3- and 6-positions and indenoquinoline derivatives
To the best of our knowledge, only a few studies on 9,10-
diarylacridine-1,8-diones have been reported in the litera-
ture.1
5–17
We have synthesized these compounds from
were obtained and are reported here for the first time in the litera- benzaldehydes, dimedone, and p-toluidine in ethylene
15
16
ture. The Knoevenagel condensation and Michael addition interme- glycol under microwave irradiation. Jin et al. reported
diates were obtained successfully. A possible mechanism of the
reaction is discussed in detail.
that the same reactions could be carried out catalyzed by
p-dodecylbenzenesulfonic acid (DBSA) in water. Howev-
er, it should be noted that that only p-toluidine was select-
Key words: 9,10-diarylacridine-1,8-diones, indenoquinolines, ion-
ic liquids, green chemistry
ed as substrate. The other substituted anilines either did
17
not react, or gave low yields, especially the anilines con-
taining electron-withdrawing groups. Furthermore, the
Because of the toxicity and volatility of many organic sol- known 9,10-diarylacridine-1,8-diones are symmetrical,
vents, room-temperature ionic liquids have been booming containing the same functional groups (methyl) on the 3-
recently as effective solvents for ‘green’ processes. Espe- and 6-positions. To solve the abovementioned problems,
cially those based on 1-alkyl-3-methylimidazolium and in view of the emerging importance of ionic liquids as
1
cations have shown great promise as attractive alterna- novel reaction media, we investigated the preparation of
tives to conventional solvents, and have been the subject these compounds. We here report the synthesis of sym-
of considerable current interest as environmentally benign metrical and unsymmetrical 9,10-diarylacridine-1,8-di-
reaction media in organic synthesis, owing to their unique ones and indenoquinoline derivatives by a three-
properties of nonvolatility, nonflammability, recyclabili- component, one-pot reaction of 3-anilino-5,5-dimethyl-
ty, and solubility in a wide range of organic components. cyclohex-2-enones, benzaldehydes, and 1,3-dicarbonyl
In the past few years, a variety of ionic liquids have been compounds in an ionic liquid.
demonstrated to be efficient and practical alternatives to
The reactions of benzaldehydes 1, 3-anilino-5,5-dimeth-
organic solvents for many important organic transforma-
ylcyclohex-2-enones 2,18 and 1,3-dicarbonyl compounds
2
tions.
+
–
3
in the ionic liquid medium [bmim ][BF ] (bmim = 1-
4
1
,4-Dihydropyridine and its derivatives are well-known butyl-3-methylimidazolium) at 90 °C gave the desired
compounds, widely prescribed as calcium b-blockers, and 9,10-diarylacridine-1,8-dione derivatives 4 in high yields
used for the treatment of hypertension and heart defibril- within a few hours (Scheme 1).
3
lation. Recently many methods have become available
for the synthesis of tricyclic compounds containing 1,4-
dihydropyridine moieties, such as 9-arylacridine deriva-
tives, from aldehydes, dimedones, and ammonium ace-
tates by traditional heating in organic solvents, under
triethylbenzyl ammonium chloride (TEBAC) catalysis in
We began our study of this reaction (Scheme 1) by opti-
mizing the conditions for the preparation of 9,10-diaryl-
1
2
1
acridine-1,8-dione 4a (R = R = Me; Ar = 4-Tol). A
summary of the optimization experiment is provided in
Table 1. It turned out that no reaction takes place at room
temperature (Table 1, entry 1), while the reaction goes
smoothly at 90 °C, giving 4a in high yield. To find the op-
timum reaction time, the reaction was carried out in the
4
SYNTHESIS 2006, No. 24, pp 4187–4199
x
x.
x
x
.
2
0
0
6
+
–
4
Advanced online publication: 13.11.2006
DOI: 10.1055/s-2006-950365; Art ID: F10406SS
Georg Thieme Verlag Stuttgart · New York
ionic liquid [bmim ][BF
] for 1, 3, and 5 hours (Table 1,
entries 3, 4, and 5); this gave 4a in 86, 98, and 98% yield,
©

4
188
X.-S. Wang et al.
PAPER
respectively. Thus, a reaction temperature of 90 °C and a To demonstrate the efficiency and the applicability of this
reaction time of three hours were chosen. Different ionic method, we investigated the reactions of a variety of benz-
liquids, with different alkyl substituents on the methylim- aldehydes 1, 3-anilino-5,5-dimethylcyclohex-2-enones 2,
idazolium, and different anions, were studied, and and 1,3-dicarbonyl compounds 3 at 90 °C in the ionic liq-
+
–
+
–
[
bmim ][BF ] was found to be the best medium for this uid medium [bmim ][BF ]. As shown in Table 3, a series
4
4
reaction.
of 1 and 2, in which the aromatic ring contained electron-
withdrawing groups (such as halo or nitro) or electron-
donating groups (such as alkoxy or alkyl), reacted with 3
under the same reaction conditions to give the correspond-
ing products 4 in high yields. We thus concluded that
there were no obvious electronic or other effects of the
substituents on the aromatic rings. In addition, unsymmet-
rical products could be prepared, e.g. 9,10-diarylacridine-
Ar1
N
O
O
O
O
R2
IL
1
R2
Ar CHO +
+
NH
R1
R2 90 °C
R2
O
R1
1
2
3
4
1
,8-diones 4 with no substituents on the 6-position
IL = ionic liquid
(
Table 3, entries 16–25).
Scheme 1
The products 4 were completely characterized by IR and
1
H NMR spectroscopy and elemental analysis. The data
Table 1 Synthesis of 4a under Different Reaction Conditionsa
corresponded to their structures, and the melting points of
the known compounds corresponded to those reported in
the literature. In addition, the X-ray diffraction analysis19
of product 4r was carried out to confirm its structure. The
crystal structure of 4r is shown in Figure 1.
Temp (°C) Ionic liquidb
c
Entry
Time (h) Yield (%)
+
–
1
2
3
4
5
6
7
8
9
r.t.
50
90
90
90
90
90
90
90
90
[bmim ][BF ]
3
3
1
3
5
3
3
3
3
3
0
56
86
98
98
90
92
92
94
95
4
+
–
[bmim ][BF ]
4
+
–
[bmim ][BF ]
4
+
–
[bmim ][BF ]
4
+
–
[bmim ][BF ]
4
+
–
[emim ]Br
+
–
[pmim ]Br
+
–
[bmim ]Br
+
–
[emim ][BF ]
4
+
–
1
a
0
[pmim ][BF ]
4
1
2
1
Reagents and conditions for the synthesis of 4a (R = R = Me; Ar =
1
1
2
4
-Tol): 1 (Ar = 4-Tol; 1 mmol), 2 (R = Me; 1 mmol), 3 (R = Me; 1
mmol), ionic liquid solvent (5 mL).
b
bmim = 1-butyl-3-methylimidazolium; emim = 1-ethyl-3-methyl-
imidazolium; pmim = 1-methyl-3-propylimidazolium.
c
Isolated yields.
At completion, as monitored by TLC, the reaction mixture
was allowed to cool to room temperature, and the solid
was isolated by filtration. The filtrate of the ionic liquid
Figure 1 ORTEP drawing of 4r
+
–
[
bmim ][BF ] could be recycled easily by drying at 80 °C
4
Although the detailed mechanism of the above reaction
has not been clarified, the formation of 9,10-diarylacri-
dine-1,8-dione derivatives 4 can be tentatively explained
by the pathway presented in Scheme 2. Product 5 of
Knoevenagel condensation may be formed as an interme-
diate, which cannot be obtained in this ionic liquid sys-
tem. It has been reported that a 2,2¢-(benzylidene)bis(3-
hydroxy-5,5-dimethylcyclohex-2-en-1-one) is obtained
when a benzaldehyde is treated with 5,5-dimethylcyclo-
hexane-1,3-dione, even when the molar ratio is kept at 1:1
in vacuo for several hours. The recycling was investigated
for the synthesis of 4a. A summary of the effect of succes-
sive reuse of the ionic liquid is shown in Table 2. Even in
the fourth run, the yield of product 4a was fairly high.
+
– a
Table 2 Study of the Reuse of the Ionic Liquid [bmim ][BF ]
4
Run
1
2
3
4
b
Yield (%)
98
95
94
94
a
1
2
1
Reagents and conditions for the synthesis of 4a (R = R = Me; Ar =
20
in water. In the following step, the Michael addition re-
action may give intermediate 6, followed by intramolecu-
lar cyclization to afford 4.
1
1
2
4
-Tol): 1 (Ar = 4-Tol; 1 mmol), 2 (R = Me; 1 mmol), 3 (R = Me; 1
mmol), ionic liquid solvent (5 mL), 90 °C, 3 h.
b
Isolated yields.
Synthesis 2006, No. 24, 4187–4199 © Thieme Stuttgart · New York

PAPER
Synthesis of 9,10-Diarylacridine-1,8-dione and Indenoquinoline Derivatives
4189
Table 3 Synthesis of 4 in Ionic Liquida
b
Entry
Ar1
R1
Me
Me
Me
Me
H
R2
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
H
Time (h)
Product
4a
4b
4c
Yield (%)
1
2
3
4
5
6
7
8
9
4-Tol
3
3
3
4
3
3
3
4
4
4
4
5
5
5
5
3
3
3
3
3
4
4
4
4
5
98
3,4-(OCH O)C H
3
93
2
6
4-BrC H
96
6
4
3,4-Cl C H
4d
4e
95
2
6
4
3
4-ClC H
96
6
4-BrC H
H
4f
94
6
4
3-O NC H
4
H
4g
4h
4i
98
2
6
4-ClC H
F
95
6
4
4
4-ClC H
Cl
94
6
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
4-Tol
4-Tol
Br
I
4j
95
4k
4l
98
4-ClC H
NO2
NO2
NO2
NO2
Me
Me
Me
H
94
6
4
4
2-ClC H
4m
4n
4o
4p
4q
4r
93
6
4-BrC H
97
6
4
4-Tol
98
4-ClC H
94
6
4
4-FC H
H
99
6
4
4-Tol
4-Tol
H
98
H
4s
98
4-BrC H
H
H
4t
92
6
4
4-ClC H
F
H
4u
4v
4w
4x
4y
93
6
4
4-BrC H
Cl
H
93
6
4
4-ClC H
Br
I
H
94
6
4
3,4-Me C H
3
H
97
2
6
4-Tol
NO2
H
98
a
Reagents and conditions: 1 (1 mmol), 2 (1 mmol), 3 (1 mmol), ionic liquid (5 mL).
Isolated yields.
b
To prove the mechanism, we decided to perform the reac- result possibly indicates that a Michael addition reaction
tion in the ionic liquid in the presence of water, as we took place in the above reaction.
think intermediates 6 may be obtained in that case. As ex-
Encouraged by this result, we synthesized a number of de-
1
pected, aniline derivative 6a (Ar = Ph) was obtained, in
rivatives 6b–g by this method (Scheme 3, Table 4). Simi-
good yield, from the reaction between 5,5-dimethyl-3-(4-
larly, compounds 6b–g smoothly reacted in ionic liquid to
methylanilino)cyclohex-2-enone (2a), benzaldehyde (1,
give the corresponding 9,10-diarylacridine-1,8-diones
1
Ar = Ph), and 5,5-dimethylcyclohexane-1,3-dione (3a) in
4
ab–ag in high yields (Table 4, entries 2–7).
a medium of ionic liquid and water at 90 °C (Scheme 3,
We were interested in the intermediate 2-benzylidenecy-
clohexane-1,3-dione 5, and therefore decided to prepare
Table 4). The structure of compound 6a was also con-
firmed by X-ray crystal structure analysis (Figure 2).21
2
-(4-bromobenzylidene)-1H-indene-1,3(2H)-dione, a cy-
clopentanedione equivalent of 5, from indene-1,3-dione
7) as the 1,3-dicarbonyl compound. The Knoevenagel
We were pleased to find that 6a smoothly gave the corre-
sponding 9,10-diarylacridine-1,8-dione 4aa by intramo-
lecular cyclization as expected (Table 4, entry 1). This
(
condensation product, 2-(4-bromobenzylidene)-1H-in-
Synthesis 2006, No. 24, 4187–4199 © Thieme Stuttgart · New York

4
190
X.-S. Wang et al.
PAPER
O
O
O
R2
R2
R2
1
CH Ar1
Ar CHO
+
R2
O
O
1
3
5
Ar1
Ar1 OH
O
O
O
O
R2
R2
Ar1 CH
R2
R2
.
.
NH
Ar2
O
N
R2
NH
Ar2
R2
O
O
Ar2
2
6
Ar1
N
Ar1
O
O
O
O
–
H2O
4
R2
R2
.
.
NH
R2
Ar2OH R2
O
Ar2
Ar2 = (4-R )C6H4
1
Scheme 2
Ar1 OH
O
O
O
IL
1
Ar CHO+
+
H2O
NH
NH
O
O
1
3a
2a
6a–g
Me
IL
Me
Ar1
N
O
O
Figure 2 ORTEP drawing of 6a
Me
dene-1,3(2H)-dione was obtained in 98% yield when 4-
1
4
aa–ag
bromobenzaldehyde (1, Ar = 4-BrC H ) was treated with
6
4
indene-1,3-dione in ionic liquid (Scheme 4). As expected,
intermediate smoothly reacted with 2a to give the corre-
sponding indeno[1,2-b]quinolinedione 8a (Scheme 4,
Scheme 3
Table 4 Synthesis of 6a–f and 4aa–af
Ar1
Ph
Product 6
Time (h)
15
Yield (%)
a
Product 4
4aa
Time (h)
Yield (%)
a
6a
6b
6c
6d
6e
6f
83
89
88
85
82
86
88
2
1
1
1
3
1
1
97
96
95
98
96
98
98
2
3
4
4
3
-ClC H4
12
4ab
6
-ClC H4
12
4ac
6
-ClC H4
14
4ad
6
-Tol
16
4ae
-O NC H
4
12
4af
2
6
4
-FC H4
6g
10
4ag
6
a
Isolated yields.
Synthesis 2006, No. 24, 4187–4199 © Thieme Stuttgart · New York

PAPER
Synthesis of 9,10-Diarylacridine-1,8-dione and Indenoquinoline Derivatives
4191
O
O
O
IL
1
CH Ar1
Ar CHO
+
O
1
7
2
2
three-component
reaction
Ar1
O
O
N
Ar2
8
Scheme 4
Table 5). This result suggests that a Knoevenagel conden-
sation took place during the reaction. On the basis of this
discovery, a series of indenoquinolines 8a–i was synthe-
sized by one-pot three-component reactions between aro-
matic aldehydes 1, 3-anilino-5,5-dimethylcyclohex-2- Figure 3 ORTEP drawing of 8b with DMF solvate
enones 2, and indene-1,3-dione (7) in the ionic liquid me-
+
–
dium [bmim ][BF ]. The results are summarized in
4
Table 5. The structure of product 8b was confirmed by X- Melting points were determined in open capillaries and are uncor-
2
2
ray diffraction analysis, and is shown in Figure 3.
rected. IR spectra of samples prepared in KBr pellets were recorded
1
on a TENSOR 27 spectrometer. H NMR spectra of DMSO-d or
6
CDCl solutions with TMS as internal standard were obtained on a
Table 5 Synthesis of 8a–8i
3
Bruker-400 spectrometer. Elemental analyses were carried out on a
Carlo Erba 1110 analyzer. X-ray crystal-structure determinations
were determined on a Rigaku Mercury or CCD area diffractometer.
Product 8 Ar1
Ar2
Time (h) Yield (%)
8
8
8
8
8
8
8
8
8
a
b
c
d
e
f
4-BrC H4
4-Tol
4-Tol
5
5
6
6
6
7
7
8
8
98
96
97
98
95
96
96
95
97
6
9
,10-Diarylacridine-1,8-diones 4a–y; General Procedure
6
4-FC H4
A mixture of benzaldehyde 1 (1.0 mmol), 3-anilino-5,5-dimethyl-
cyclohex-2-enone 2 (1.0 mmol), 1,3-dicarbonyl compound 3 (1.0
mmol), and ionic liquid medium [bmim ][BF ] (5 mL) was stirred
at 90 °C for several hours to complete the reaction (monitored by
TLC). The mixture was cooled to r.t. and the yellow solid was col-
lected by filtration. The filtrate of the ionic liquid [bmim ][BF ]
could then be recycled after drying at 80 °C for several hours in
vacuo. The crude product was washed with H O and purified by re-
crystallization from DMF–H O; this gave 4.
4-BrC H4
4-BrC H
6
4
4
4
6
+
–
4
4-FC H4
4-BrC H
6
6
+
–
2,4-Cl C H
4-BrC H
2
6
3
6
4
3-ClC H4
1-naphthyl
1-naphthyl
1-naphthyl
1-naphthyl
6
2
2
g
h
i
2-ClC H4
6
3
,3,6,6-Tetramethyl-9,10-bis(4-tolyl)-3,4,6,7,9,10-hexahydro-
acridine-1,8(2H,5H)-dione (4a)
Pale yellow crystals; mp 296–297 °C (Lit. 296–297 °C).
4-Tol
1
5
4-FC H4
6
9
3
-(1,3-Benzodioxol-5-yl)-3,3,6,6-tetramethyl-10-(4-tolyl)-
,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4b)
1
5
Pale yellow crystals; mp 278–280 °C (Lit. 278–279 °C).
In conclusion, we have developed a novel synthetic meth-
od for the synthesis of 9,10-diarylacridine and indeno-
quinoline derivatives in excellent yields by using the ionic
9
3
-(4-Bromophenyl)-3,3,6,6-tetramethyl-10-(4-tolyl)-
,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4c)
+
–
liquid [bmim ][BF ] as medium. Excellent yields were
4
Pale yellow crystals; mp 270–272 °C.
obtained, not only for anilines substituted with electron-
donating groups, but also for ones containing electron-
withdrawing groups, in contrast to other methods.1
Furthermore, the interesting unsymmetrical 9,10-diaryl-
acridine-1,8-dione moiety with different groups in 3- and
IR (KBr): 3035, 2956, 2869, 1638, 1576, 1511, 1483, 1450, 1405,
–1
1
361, 1301, 1278, 1221, 1176, 1144, 1211, 1069, 1009, 841 cm .
5–17
1
H NMR (400 MHz, DMSO-d ): d = 0.71 (s, 6 H, 2 CH ), 0.87 (s, 6
6
3
H, 2 CH ), 1.77 (d, J = 17.2 Hz, 2 H, 2 CH), 2.00 (d, J = 16.0 Hz, 2
3
H, 2 CH), 2.17–2.22 (m, 4 H, 4 CH), 2.42 (s, 3 H, CH ), 5.00 (s, 1
3
6
-positions were obtained. The ionic liquid medium H, CH), 7.25–7.31 (m, 4 H, ArH), 7.41 (d, J = 8.8 Hz, 2 H, ArH),
+
–
[
bmim ][BF ] was chosen as a green solvent, which 7.44 (d, J = 8.4 Hz, 2 H, ArH).
4
could be reused for several rounds without significant loss
of activity.
13
C NMR (100 MHz, DMSO-d ): d = 21.0, 26.3, 29.4, 32.0, 32.1,
6
41.1, 49.6, 112.6, 118.9, 130.0, 131.0, 135.9, 139.1, 145.8, 151.0,
95.3.
1
Synthesis 2006, No. 24, 4187–4199 © Thieme Stuttgart · New York

4
192
X.-S. Wang et al.
PAPER
Anal. Calcd for C H BrNO : C, 69.50; H, 6.22; N, 2.70. Found: C,
H, 2 CH), 5.15 (s, 1 H, CH), 7.45–7.67 (m, 4 H, ArH), 7.79 (d, J =
30
32
2
6
9.38; H, 6.30; N, 2.78.
8.0 Hz, 1 H, ArH), 8.02 (dd, J = 8.0, 1.2 Hz, 1 H, ArH), 8.15 (s, 1
H, ArH).
9
3
-(3,4-Dichlorophenyl)-3,3,6,6-tetramethyl-10-(4-tolyl)-
,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4d)
13
C NMR (100 MHz, DMSO-d ): d = 26.2, 29.3, 32.2, 32.6, 41.1,
6
4
1
9.5, 112.3, 121.2, 122.2, 129.8, 129.9, 130.2, 134.4, 138.3, 147.6,
48.4, 151.3, 195.4.
Pale yellow crystals; mp 251–253 °C.
IR (KBr): 3035, 2957, 2869, 1642, 1573, 1510, 1469, 1359, 1301,
Anal. Calcd for C H N O : C, 74.02; H, 6.43; N, 5.95. Found: C,
–
1
29 30
2
4
1
279, 1218, 1142, 1121, 1023, 1000, 879, 834, 735 cm .
7
4.10; H, 6.44; N, 5.82.
1
H NMR (400 MHz, DMSO-d ): d = 0.72 (s, 6 H, 2 CH ), 0.88 (s, 6
6
3
H, 2 CH ), 1.79 (d, J = 17.6 Hz, 2 H, 2 CH), 2.02 (d, J = 16.0 Hz, 2
9-(4-Chlorophenyl)-10-(4-fluorophenyl)-3,3,6,6-tetramethyl-
3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4h)
Pale yellow crystals; mp >300 °C.
3
H, 2 CH), 2.20 (d, J = 16.8 Hz, 4 H, 4 CH), 2.42 (s, 3 H, CH ), 4.99
3
(
s, 1 H, CH), 7.22–7.33 (m, 4 H, ArH), 7.41–7.45 (m, 2 H, ArH),
7
.54 (d, J = 8.4 Hz, 1 H, ArH).
IR (KBr): 3061, 2956, 2933, 2869, 1639, 1578, 1507, 1486, 1412,
1361, 1302, 1279, 1262, 1177, 1144, 1119, 1089, 1013, 980, 934,
888, 840, 805, 780, 743, 714 cm .
1
3
C NMR (100 MHz, CDCl ): d = 21.3, 26.6, 29.6, 32.46, 32.48,
3
–
1
4
1
1.4, 49.8, 112.4, 128.2, 128.7, 130.2, 130.7, 130.9, 136.0, 139.5,
47.7, 151.6, 195.6.
1
H NMR (400 MHz, DMSO-d ): d = 0.72 (s, 6 H, 2 CH ), 0.89 (s, 6
6
3
Anal. Calcd for C H Cl NO : C, 70.86; H, 6.15; N, 2.75. Found:
H, 2 CH ), 1.77 (d, J = 17.2 Hz, 2 H, 2 CH), 2.01 (d, J = 16.4 Hz, 2
30
31
2
2
3
C, 70.70; H, 6.25; N, 2.66.
H, 2 CH), 2.17–2.22 (m, 4 H, 4 CH), 5.01 (s, 1 H, CH), 7.29–7.53
(m, 8 H, ArH).
9
-(4-Chlorophenyl)-3,3,6,6-tetramethyl-10-phenyl-3,4,6,7,9,10-
13
C NMR (100 MHz, DMSO-d ): d = 26.3, 29.4, 31.9, 32.1, 41.1,
6
hexahydroacridine-1,8(2H,5H)-dione (4e)
Pale yellow crystals; mp 244–246 °C.
4
1
9.6, 112.8, 117.0, 128.1, 129.6, 130.4, 134.8, 145.3, 150.8, 160.8,
63.3, 195.3.
IR (KBr): 3063, 2956, 2870, 1634, 1575, 1489, 1452, 1409, 1361,
Anal. Calcd for C H ClFNO : C, 72.87; H, 6.12; N, 2.93. Found:
C, 72.80; H, 6.22; N, 2.88.
2
9
29
2
1
7
1
299, 1274, 1224, 1141, 1122, 1088, 1014, 1000, 942, 920, 839,
70, 705 cm .
–1
H NMR (400 MHz, DMSO-d ): d = 0.71 (s, 6 H, 2 CH ), 0.88 (s, 6
9,10-Bis(4-chlorophenyl)-3,3,6,6-tetramethyl-3,4,6,7,9,10-
hexahydroacridine-1,8(2H,5H)-dione (4i)
Pale yellow crystals; mp 284–286 °C.
6
3
H, 2 CH ), 1.75 (d, J = 17.6 Hz, 2 H, 2 CH), 2.01 (d, J = 16.0 Hz, 2
3
H, 2 CH), 2.20 (d, J = 16.0 Hz, 2 H, 2 CH), 2.21 (d, J = 17.6 Hz, 2
H, 2 CH), 5.03 (s, 1 H, CH), 7.29–7.35 (m, 4 H, ArH), 7.43 (b, 2 H,
ArH), 7.58–7.64 (m, 3 H, ArH).
IR (KBr): 3051, 2958, 2869, 1639, 1578, 1490, 1406, 1361, 1302,
–1
1
278, 1263, 1177, 1145, 1121, 1089, 1014, 888, 839, 739, 713 cm .
1
3
C NMR (100 MHz, DMSO-d ): d = 26.3, 29.4, 31.9, 32.1, 41.1,
1
6
H NMR (400 MHz, DMSO-d ): d = 0.72 (s, 6 H, 2 CH ), 0.89 (s, 6
6
3
4
1
9.6, 112.7, 128.1, 129.57, 129.64, 130.2, 130.4, 138.5, 145.4,
50.7, 195.3.
H, 2 CH ), 1.78 (d, J = 17.6 Hz, 2 H, 2 CH), 2.01 (d, J = 16.0 Hz, 2
3
H, 2 CH), 2.19 (d, J = 16.0 Hz, 2 H, 2 CH), 2.20 (d, J = 17.6 Hz, 2
H, 2 CH), 5.01 (s, 1 H, CH), 7.30–7.49 (m, 6 H, ArH), 7.68 (d, J =
8.8 Hz, 2 H, ArH).
Anal. Calcd for C H ClNO : C, 75.72; H, 6.57; N, 3.04. Found: C,
29
30
2
7
5.58; H, 6.70; N, 3.12.
1
3
C NMR (100 MHz, DMSO-d ): d = 26.2, 29.4, 31.9, 32.2, 41.1,
6
9
-(4-Bromophenyl)-3,3,6,6-tetramethyl-10-phenyl-3,4,6,7,9,10-
4
9.7, 112.8, 128.1, 129.6, 130.5, 134.2, 137.4, 145.2, 150.5, 195.3.
hexahydroacridine-1,8(2H,5H)-dione (4f)
Anal. Calcd for C H Cl NO : C, 70.44; H, 5.91; N, 2.83. Found:
C, 70.28; H, 6.05; N, 2.90.
Pale yellow crystals; mp 238–240 °C.
29 29
2
2
IR (KBr): 3061, 2959, 2869, 1659, 1638, 1576, 1485, 1467, 1451,
1
8
1
406, 1360, 1300, 1277, 1225, 1145, 1122, 1093, 1067, 1008, 921,
40, 771, 706, 659 cm .
1
3
0-(4-Bromophenyl)-9-(4-methoxyphenyl)-3,3,6,6-tetramethyl-
,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4j)
–
1
H NMR (400 MHz, DMSO-d ): d = 0.71 (s, 6 H, 2 CH ), 0.88 (s, 6
Pale yellow crystals; mp 247–248 °C.
6
3
H, 2 CH ), 1.75 (d, J = 17.6 Hz, 2 H, 2 CH), 2.01 (d, J = 16.0 Hz, 2
H, 2 CH), 2.18–2.23 (m, 4 H, 4 CH), 5.01 (s, 1 H, CH), 7.27 (d, J =
8
3
IR (KBr): 3050, 3006, 2956, 2836, 1641, 1608, 1580, 1508, 1489,
1
9
1
472, 1440, 1361, 1299, 1260, 1176, 1141, 1121, 1104, 1037, 1013,
.4 Hz, 2 H, ArH), 7.44–7.46 (m, 4 H, ArH), 7.58–7.64 (m, 3 H,
–1
99, 920, 886, 863, 834, 738 cm .
ArH).
H NMR (400 MHz, DMSO-d ): d = 0.73 (s, 6 H, 2 CH ), 0.89 (s, 6
1
3
6
3
C NMR (100 MHz, DMSO-d ): d = 26.3, 29.4, 32.0, 32.1, 41.1,
6
H, 2 CH ), 1.76 (d, J = 17.6 Hz, 2 H, 2 CH), 2.00 (d, J = 16.0 Hz, 2
3
4
1
9.6, 112.6, 118.9, 129.6, 130.0, 130.2, 131.0, 138.5, 145.8, 150.7,
95.3.
H, 2 CH), 2.18 (d, J = 16.0 Hz, 2 H, 2 CH), 2.19 (d, J = 17.6 Hz, 2
H, 2 CH), 3.69 (s, 3 H, CH O), 4.97 (s, 1 H, CH), 6.80 (d, J = 8.4
3
Anal. Calcd for C H BrNO : C, 69.05; H, 5.99; N, 2.78. Found: C,
Hz, 2 H, ArH), 7.20 (d, J = 8.4 Hz, 2 H, ArH), 7.39 (b, 2 H, ArH),
7.81 (d, J = 8.4 Hz, 2 H, ArH).
29
30
2
6
8.91; H, 5.96; N, 2.90.
1
3
C NMR (100 MHz, DMSO-d ): d = 26.2, 29.4, 31.1, 32.1, 41.1,
6
3
,3,6,6-Tetramethyl-9-(3-nitrophenyl)-10-phenyl-3,4,6,7,9,10-
4
1
9.8, 55.0, 113.4, 113.5, 122.7, 128.6, 133.2, 138.0, 138.6, 150.0,
57.5, 195.3.
hexahydroacridine-1,8(2H,5H)-dione (4g)
Pale yellow crystals; mp 245–247 °C.
Anal. Calcd for C H BrNO : C, 67.41; H, 6.03; N, 2.62. Found: C,
3
0
32
3
IR (KBr): 3062, 2951, 2871, 1638, 1574, 1526, 1490, 1472, 1452,
6
7.52; H, 6.22; N, 2.66.
1
8
1
422, 1361, 1301, 1262, 1222, 1123, 1091, 1020, 1002, 922, 899,
18, 733, 708, 688 cm .
–
1
1
0-(4-Iodophenyl)-9-(4-methoxyphenyl)-3,3,6,6-tetramethyl-
H NMR (400 MHz, DMSO-d ): d = 0.70 (s, 6 H, 2 CH ), 0.87 (s, 6
3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4k)
6
3
H, 2 CH ), 1.79 (d, J = 17.6 Hz, 2 H, 2 CH), 2.02 (d, J = 16.0 Hz, 2
Pale yellow crystals; mp 259–262 °C.
3
H, 2 CH), 2.23 (d, J = 16.0 Hz, 2 H, 2 CH), 2.25 (d, J = 17.6 Hz, 2
Synthesis 2006, No. 24, 4187–4199 © Thieme Stuttgart · New York

PAPER
Synthesis of 9,10-Diarylacridine-1,8-dione and Indenoquinoline Derivatives
4193
1
3
IR (KBr): 3031, 2956, 2871, 1644, 1581, 1508, 1442, 1422, 1368,
C NMR (100 MHz, DMSO-d ): d = 26.5, 28.2, 31.8, 32.6, 41.3,
6
–
1
1
301, 1261, 1218, 1140, 1102, 1033, 1009, 850, 833 cm .
47.1, 113.3, 114.6, 119.3, 125.7, 129.3, 130.0, 131.1, 131.3, 144.5,
148.2, 195.7.
1
H NMR (400 MHz, DMSO-d ): d = 0.73 (s, 6 H, 2 CH ), 0.89 (s, 6
6
3
H, 2 CH ), 1.76 (d, J = 17.2 Hz, 2 H, 2 CH), 2.00 (d, J = 16.0 Hz, 2
Anal. Calcd for C H BrN O : C, 63.39; H, 5.32; N, 5.10. Found:
3
29 29
2
4
H, 2 CH), 2.18 (d, J = 16.0 Hz, 2 H, 2 CH), 2.19 (d, J = 17.6 Hz, 2
C, 63.21; H, 5.60; N, 5.12.
H, 2 CH), 3.69 (s, 3 H, CH O), 4.97 (s, 1 H, CH), 6.80 (d, J = 8.4
3
Hz, 2 H, ArH), 7.20 (d, J = 8.4 Hz, 4 H, ArH), 7.97 (d, J = 8.4 Hz,
9-(4-Methoxyphenyl)-3,3,6,6-tetramethyl-10-(4-nitrophenyl)-
3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4o)
Pale yellow crystals; mp >300 °C.
2
H, ArH).
1
3
C NMR (100 MHz, DMSO-d ): d = 26.2, 29.4, 31.2, 41.1, 49.8,
6
5
1
5.0, 96.2, 113.4, 113.5, 128.6, 138.4, 138.6, 139.1, 150.0, 157.5,
95.3.
IR (KBr): 3070, 2959, 2871, 2836, 1667, 1608, 1591, 1532, 1508,
1491, 1465, 1390, 1361, 1301, 1262, 1170, 1143, 1032, 1008, 889,
–
1
8
65, 850, 833, 706, 656 cm .
Anal. Calcd for C H INO : C, 61.97; H, 5.55; N, 2.41. Found: C,
3
0
32
3
1
6
1.82; H, 5.70; N, 2.54.
H NMR (400 MHz, DMSO-d ): d = 0.73 (s, 6 H, 2 CH ), 0.88 (s, 6
6
3
H, 2 CH ), 1.77 (d, J = 17.6 Hz, 2 H, 2 CH), 2.02 (d, J = 16.0 Hz, 2
3
9
3
-(4-Chlorophenyl)-3,3,6,6-tetramethyl-10-(4-nitrophenyl)-
,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4l)
H, 2 CH), 2.19 (d, J = 16.0 Hz, 2 H, 2 CH), 2.20 (d, J = 17.6 Hz, 2
H, 2 CH), 3.70 (s, 3 H, CH O), 4.98 (s, 1 H, CH), 8.01 (d, J = 8.4
3
Pale yellow crystals; mp >300 °C.
Hz, 2 H, ArH), 7.23 (d, J = 8.4 Hz, 2 H, ArH), 7.24 (d, J = 8.4 Hz,
2
H, ArH), 8.44 (d, J = 8.4 Hz, 2 H, ArH).
IR (KBr): 3067, 2958, 2871, 1640, 1608, 1592, 1525, 1487, 1362,
1
3
1
7
1
346, 1298, 1278, 1261, 1224, 1178, 1087, 1013, 921, 863, 842,
08 cm .
C NMR (100 MHz, CDCl ): d = 26.9, 29.7, 31.8, 32.6, 42.0, 50.1,
3
–1
55.2, 113.6, 115.5, 125.4, 128.8, 131.2, 138.1, 145.0, 147.97,
148.03, 157.9, 195.7.
H NMR (400 MHz, DMSO-d ): d = 0.72 (s, 6 H, 2 CH ), 0.89 (s, 6
6
3
H, 2 CH ), 1.79 (d, J = 17.2 Hz, 2 H, 2 CH), 2.03 (d, J = 16.0 Hz, 2
Anal. Calcd for C H N O : C, 71.98; H, 6.44; N, 5.60. Found: C,
3
30 32
2
5
H, 2 CH), 2.21 (d, J = 16.8 Hz, 4 H, 4 CH), 5.02 (s, 1 H, CH), 7.31
71.82; H, 6.58; N, 5.52.
(
d, J = 8.4 Hz, 2 H, ArH), 7.34 (d, J = 8.4 Hz, 2 H, ArH), 7.77 (d,
J = 8.8 Hz, 2 H, ArH), 8.45 (d, J = 8.8 Hz, 2 H, ArH).
9-(4-Chlorophenyl)-3,3-dimethyl-10-(4-tolyl)-3,4,6,7,9,10-
hexahydroacridine-1,8(2H,5H)-dione (4p)
Pale yellow crystals; mp 244–245 °C.
1
3
C NMR (100 MHz, DMSO-d ): d = 26.2, 29.3, 31.9, 32.3, 41.0,
6
4
1
9.7, 113.1, 125.4, 128.0, 128.1, 129.7, 131.7, 144.2, 145.1, 150.0,
95.4.
IR (KBr): 3054, 2957, 2868, 1644, 1573, 1510, 1485, 1448, 1427,
1
8
1
408, 1361, 1292, 1266, 1183, 1149, 1134, 1093, 1014, 977, 915,
57, 836, 769, 723 cm .
Anal. Calcd for C H ClN O : C, 68.97; H, 5.79; N, 5.55. Found:
C, 68.79; H, 5.92; N, 5.50.
29
29
2
4
–1
H NMR (400 MHz, DMSO-d ): d = 0.71 (s, 3 H, CH ), 0.88 (s, 3
6
3
9
3
-(2-Chlorophenyl)-3,3,6,6-tetramethyl-10-(4-nitrophenyl)-
,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4m)
H, CH ), 1.61–2.27 (m, 10 H, 5 CH ), 2.41 (s, 3 H, CH ), 5.06 (s, 1
H, CH), 7.24–7.41 (m, 8 H, ArH).
3
2
3
Pale yellow crystals; mp >300 °C.
13
C NMR (100 MHz, DMSO-d ): d = 20.85, 20.91, 26.2, 27.9, 29.5,
6
IR (KBr): 3065, 2960, 2871, 1643, 1592, 1579, 1524, 1425, 1366,
31.5, 32.1, 36.3, 41.1, 49.7, 112.7, 113.5, 128.1, 129.5, 130.0,
130.4, 130.8, 135.9, 139.1, 145.6, 150.8, 153.1, 195.4, 195.6.
–
1
1
345, 1303, 1263, 1224, 1177, 1145, 1014, 862, 741, 707 cm .
1
H NMR (400 MHz, DMSO-d ): d = 0.74 (s, 6 H, 2 CH ), 0.87 (s, 6
Anal. Calcd for C H ClNO : C, 75.41; H, 6.33; N, 3.14. Found: C,
75.29; H, 6.55; N, 3.12.
6
3
28 28
2
H, 2 CH ), 1.76 (d, J = 17.6 Hz, 2 H, 2 CH), 1.96 (d, J = 16.0 Hz, 2
3
H, 2 CH), 2.12 (d, J = 16.0 Hz, 2 H, 2 CH), 2.16 (d, J = 17.2 Hz, 2
H, 2 CH), 5.27 (s, 1 H, CH), 7.10–7.14 (m, 1 H, ArH), 7.23–7.28
9-(4-Fluorophenyl)-3,3-dimethyl-10-(4-tolyl)-3,4,6,7,9,10-
hexahydroacridine-1,8(2H,5H)-dione (4q)
Pale yellow crystals; mp 261–264 °C.
(
m, 2 H, ArH), 7.52 (d, J = 7.6 Hz, 1 H, ArH), 7.76 (d, J = 8.8 Hz,
2
H, ArH), 8.45 (d, J = 8.8 Hz, 2 H, ArH).
1
3
C NMR (100 MHz, CDCl ): d = 26.7, 29.6, 32.3, 34.6, 42.1, 49.9,
IR (KBr): 3062, 2960, 2870, 1644, 1571, 1503, 1449, 1429, 1415,
1361, 1292, 1265, 1183, 1151, 1133, 1089, 1041, 1017, 977, 916,
894, 848, 809, 769, 736, 723, 659 cm .
3
1
1
12.8, 125.4, 126.2, 127.5, 130.1, 131.3, 133.3, 133.8, 141.6, 144.8,
47.9, 149.3, 195.6.
–
1
1
Anal. Calcd for C H ClN O : C, 68.97; H, 5.79; N, 5.55. Found:
C, 68.82; H, 5.90; N, 5.59.
H NMR (400 MHz, DMSO-d ): d = 0.71 (s, 3 H, CH ), 0.88 (s, 3
29
29
2
4
6
3
H, CH ), 1.50–2.23 (m, 10 H, 5 CH ), 2.41 (s, 3 H, CH ), 5.07 (s, 1
3
2
3
H, CH), 7.06 (t, J = 8.8 Hz, 2 H, ArH), 7.23–7.41 (m, 6 H, ArH).
9
3
-(4-Bromophenyl)-3,3,6,6-tetramethyl-10-(4-nitrophenyl)-
,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4n)
13
C NMR (100 MHz, DMSO-d ): d = 20.86, 20.91, 26.2, 27.9, 29.5,
6
3
1
1.2, 32.1, 36.4, 41.1, 49.7, 113.0, 113.8, 114.7, 114.9, 129.3,
29.4, 136.0, 139.1, 142.88, 142.91, 150.7, 153.0, 159.4, 161.8,
Pale yellow crystals; mp 291–293 °C.
IR (KBr): 3049, 2958, 2969, 1642, 1579, 1487, 1361, 1301, 1263,
195.4, 195.6.
1
7
1
177, 1144, 1122, 1100, 1069, 1010, 946, 921, 888, 838, 773, 736,
11, 669, 615 cm .
Anal. Calcd for C H FNO : C, 78.30; H, 6.57; N, 3.26. Found: C,
–
1
28 28
2
7
8.29; H, 6.68; N, 3.20.
H NMR (400 MHz, DMSO-d ): d = 0.73 (s, 6 H, 2 CH ), 0.89 (s, 6
6
3
H, 2 CH ), 1.78 (d, J = 17.6 Hz, 2 H, 2 CH), 2.01 (d, J = 16.0 Hz, 2
9-(4-Methoxyphenyl)-3,3-dimethyl-10-(4-tolyl)-3,4,6,7,9,10-
hexahydroacridine-1,8(2H,5H)-dione (4r)
Pale yellow crystals; mp 254–256 °C.
3
H, 2 CH), 2.21 (d, J = 17.6 Hz, 2 H, 2 CH), 2.27 (d, J = 16.0 Hz, 2
H, 2 CH), 5.01 (s, 1 H, CH), 7.13 (d, J = 8.4 Hz, 2 H, ArH), 7.42 (d,
J = 8.4 Hz, 2 H, ArH), 7.77 (d, J = 8.8 Hz, 2 H, ArH), 8.45 (d, J =
IR (KBr): 3035, 2943, 2870, 2840, 1634, 1573, 1509, 1455, 1423,
8
.8 Hz, 2 H, ArH).
1
8
361, 1302, 1289, 1264, 1225, 1187, 1149, 1123, 1032, 979, 894,
31, 767, 737, 658 cm .
–
1
Synthesis 2006, No. 24, 4187–4199 © Thieme Stuttgart · New York

4
194
X.-S. Wang et al.
PAPER
1
H NMR (400 MHz, DMSO-d ): d = 0.72 (s, 3 H, CH ), 0.88 (s, 3
IR (KBr): 3052, 2957, 2868, 1640, 1576, 1489, 1404, 1361, 1285,
1268, 1227, 1185, 1138, 1088, 1069, 1010, 981, 937, 858, 828, 746
cm .
6
3
H, CH ), 1.60–2.22 (m, 10 H, 5 CH ), 2.41 (s, 3 H, CH ), 3.69 (s, 3
H, CH O), 5.02 (s, 1 H, CH), 6.80 (d, J = 8.8 Hz, 2 H, ArH), 7.20
3
2
3
–
1
3
(
1
d, J = 8.4 Hz, 3 H, ArH), 7.39 (d, J = 8.0 Hz, 3 H, ArH).
1
H NMR (400 MHz, DMSO-d ): d = 0.73 (s, 3 H, CH ), 0.89 (s, 3
6
3
3
C NMR (100 MHz, DMSO-d ): d = 20.9, 26.2, 27.8, 29.5, 30.7,
H, CH ), 1.61–1.66 (m, 1 H, CH), 1.76–1.86 (m, 2 H, 2 CH), 1.92–
2.04 (m, 2 H, 2 CH), 2.16–2.22 (m, 5 H, 5 CH), 5.05 (s, 1 H, CH),
7.26 (d, J = 8.4 Hz, 2 H, ArH), 7.42 (d, J = 8.4 Hz, 2 H, ArH), 7.50
6
3
3
1
2.1, 36.4, 41.1, 49.8, 50.1, 113.4, 113.5, 114.3, 128.5, 128.9,
30.8, 136.1, 139.0, 150.3, 152.6, 157.5, 195.4, 195.6.
(
1
b, 2 H, ArH), 7.67 (d, J = 8.4 Hz, 2 H, ArH).
Anal. Calcd for C H NO : C, 78.88; H, 7.08; N, 3.17. Found: C,
29
31
3
3
7
8.76; H, 7.29; N, 3.25.
C NMR (100 MHz, DMSO-d ): d = 20.9, 26.2, 27.9, 29.4, 31.6,
6
3
2.1, 36.3, 41.0, 49.7, 106.2, 112.8, 113.6, 119.0, 130.0, 131.0,
9
-(4-Methoxyphenyl)-3,3-dimethyl-10-phenyl-3,4,6,7,9,10-
134.1, 137.4, 145.9, 150.4, 152.7, 195.4, 195.6.
hexahydroacridine-1,8(2H,5H)-dione (4s)
Pale yellow crystals; mp 256–258 °C.
Anal. Calcd for C H BrClNO : C, 63.48; H, 4.93; N, 2.74. Found:
2
7
25
2
C, 63.34; H, 5.12; N, 2.78.
IR (KBr): 3063, 2978, 2953, 2870, 1634, 1570, 1507, 1493, 1454,
–
1
1
1
361, 1286, 1226, 1148, 1136, 1103, 1031, 980, 892, 834, 707 cm .
10-(4-Bromophenyl)-9-(4-chlorophenyl)-3,3-dimethyl-
3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4w)
Pale yellow crystals; mp 257–259 °C.
H NMR (400 MHz, DMSO-d ): d = 0.73 (s, 3 H, CH ), 0.88 (s, 3
H, CH ), 1.60–1.62 (m, 1 H, CH), 1.72–2.03 (m, 4 H, 4 CH), 2.16–
6
3
3
2
.26 (m, 5 H, 5 CH), 3.70 (s, 3 H, CH O), 5.03 (s, 1 H, CH), 6.81
IR (KBr): 3059, 2958, 2867, 1650, 1579, 1486, 1448, 1405, 1293,
1269, 1184, 1135, 1092, 1066, 1011, 978, 916, 851, 831, 769, 726,
626, 579 cm .
3
(
(
1
d, J = 8.4 Hz, 2 H, ArH), 7.21 (d, J = 8.4 Hz, 2 H, ArH), 7.40–7.62
m, 5 H, ArH).
–
1
3
1
C NMR (100 MHz, DMSO-d ): d = 20.9, 26.3, 27.9, 30.8, 32.1,
H NMR (400 MHz, DMSO-d ): d = 0.72 (s, 3 H, CH ), 0.89 (s, 3
6
6
3
3
1
6.4, 41.1, 49.8, 55.0, 113.4, 113.5, 114.3, 128.6, 129.5, 130.3,
38.7, 139.0, 150.1, 152.3, 157.5, 195.4, 195.6.
H, CH ), 1.62–1.64 (m, 1 H, CH), 1.73–1.83 (m, 2 H, 2 CH), 1.90–
3
2.04 (m, 2 H, 2 CH), 2.17–2.22 (m, 5 H, 5 CH), 5.06 (s, 1 H, CH),
7
.29 (d, J = 8.4 Hz, 2 H, ArH), 7.31 (d, J = 8.4 Hz, 2 H, ArH), 7.44
Anal. Calcd for C H NO : C, 78.66; H, 6.84; N, 3.28. Found: C,
28
29
3
(b, 2 H, ArH), 7.80 (d, J = 8.8 Hz, 2 H, ArH).
7
8.53; H, 6.85; N, 3.26.
1
3
C NMR (100 MHz, DMSO-d ): d = 20.9, 26.2, 27.9, 31.5, 32.1,
6
9
-(4-Bromophenyl)-3,3-dimethyl-10-phenyl-3,4,6,7,9,10-
36.3, 41.1, 49.7, 112.9, 113.7, 122.8, 129.6, 130.5, 133.1, 137.8,
145.4, 150.3, 152.7, 195.4, 195.6.
hexahydroacridine-1,8(2H,5H)-dione (4t)
Pale yellow crystals; mp 239–240 °C.
Anal. Calcd for C H BrClNO : C, 63.48; H, 4.93; N, 2.74. Found:
2
7
25
2
IR (KBr): 3048, 2959, 2928, 2884, 1636, 1592, 1574, 1490, 1452,
C, 63.38; H, 5.10; N, 2.98.
–
1
1
361, 1285, 1267, 1185, 1136, 1068, 980, 834, 707 cm .
1
9-(3,4-Dimethylphenyl)-10-(4-iodophenyl)-3,3-dimethyl-
,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4x)
Pale yellow crystals; mp 258–261 °C.
H NMR (400 MHz, DMSO-d ): d = 0.71 (s, 3 H, CH ), 0.87 (s, 3
6
3
3
H, CH ), 1.60–1.64 (m, 1 H, CH), 1.73–2.04 (m, 4 H, 4 CH), 2.18–
2
3
.28 (m, 5 H, 5 CH), 5.06 (s, 1 H, CH), 7.26 (d, J = 7.6 Hz, 2 H,
ArH), 7.43–7.60 (m, 2 H, ArH).
IR (KBr): 3014, 2957, 2884, 1650, 1574, 1483, 1454, 1418, 1361,
1284, 1266, 1186, 1136, 1121, 1008, 978, 936, 843, 793, 736 cm .
–
1
1
3
C NMR (100 MHz, DMSO-d ): d = 20.9, 26.2, 27.9, 29.4, 31.6,
6
1
3
1
2.6, 36.3, 41.1, 49.7, 112.7, 113.5, 119.0, 129.6, 130.0, 130.2,
31.0, 138.5, 146.0, 150.7, 152.9, 195.4, 195.6.
H NMR (400 MHz, DMSO-d ): d = 0.75 (s, 3 H, CH ), 0.90 (s, 3
6
3
H, CH ), 1.57–1.62 (m, 1 H, CH), 1.77–1.84 (m, 2 H, 2 CH), 1.90–
3
2
.03 (m, 2 H, 2 CH), 2.18–2.25 (m, 10 H, 2 CH + 4 CH), 5.00 (s, 1
3
Anal. Calcd for C H BrNO : C, 68.07; H, 5.50; N, 2.94. Found: C,
27
26
2
H, CH), 6.98–7.04 (m, 3 H, ArH), 7.21 (b, 2 H, ArH), 7.96 (d, J =
8
6
7.90; H, 5.65; N, 2.90.
.4 Hz, 2 H, ArH).
1
3
9
3
-(4-Chlorophenyl)-10-(4-fluorophenyl)-3,3-dimethyl-
,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4u)
C NMR (100 MHz, DMSO-d ): d = 19.1, 19.8, 20.9, 26.2, 27.9,
6
29.5, 31.1, 32.2, 36.4, 41.0, 49.8, 96.1, 113.4, 114.5, 124.8, 129.1,
129.4, 132.3, 133.6, 135.3, 138.5, 139.0, 144.1, 150.0, 152.0, 195.4,
Pale yellow crystals; mp 237–239°C.
1
95.6.
IR (KBr): 3064, 2957, 2870, 1683, 1632, 1572, 1506, 1454, 1411,
1
8
1
362, 1308, 1286, 1265, 1186, 1138, 1088, 1013, 981, 936, 894,
55, 832, 792, 771 cm .
Anal. Calcd for C H INO : C, 63.16; H, 5.48; N, 2.54. Found: C,
63.10; H, 5.63; N, 2.65.
2
9
30
2
–
1
H NMR (400 MHz, DMSO-d ): d = 0.73 (s, 3 H, CH ), 0.89 (s, 3
6
3
9
3
-(4-Methoxyphenyl)-3,3-dimethyl-10-(4-nitrophenyl)-
,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4y)
H, CH ), 1.62–1.65 (m, 1 H, CH), 1.75–1.86 (m, 2 H, 2 CH), 1.94–
2
7
3
.04 (m, 2 H, 2 CH), 2.17–2.29 (m, 5 H, 5 CH), 5.07 (s, 1 H, CH),
.28–7.33 (m, 4 H, ArH), 7.43 (b, 3 H, ArH), 7.57 (b, 1 H, ArH).
Pale yellow crystals; mp 259–261 °C.
1
3
IR (KBr): 3065, 2954, 1645, 1592, 2527, 1507, 1455, 1362, 1268,
C NMR (100 MHz, DMSO-d ): d = 21.1, 26.5, 28.2, 29.7, 31.8,
6
–1
1
228, 1137, 1037, 980, 939, 863, 831 cm .
3
1
2.4, 36.6, 41.4, 50.0, 113.2, 113.9, 128.4, 129.9, 130.8, 135.06,
35.09, 145.8, 151.0, 153.3, 161.1, 162.8, 195.7, 195.9.
1
H NMR (400 MHz, DMSO-d ): d = 0.74 (s, 3 H, CH ), 0.89 (s, 3
6
3
H, CH ), 1.61–1.66 (m, 1 H, CH), 1.75–1.85 (m, 2 H, 2 CH), 1.92–
3
Anal. Calcd for C H ClFNO : C, 72.07; H, 5.60; N, 3.11. Found:
C, 72.00; H, 5.67; N, 3.15.
27
25
2
2
5
.05 (m, 2 H, 2 CH), 2.17–2.28 (m, 5 H, 5 CH), 3.70 (s, 3 H, CH O),
.03 (s, 1 H, CH), 6.81 (d, J = 8.4 Hz, 2 H, ArH), 7.22 (d, J = 8.4
3
Hz, 2 H, ArH), 7.75 (d, J = 8.8 Hz, 2 H, ArH), 8.43 (d, J = 8.8 Hz,
9
3
-(4-Bromophenyl)-10-(4-chlorophenyl)-3,3-dimethyl-
,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4v)
2
H, ArH).
1
3
Pale yellow crystals; mp 249–251 °C.
C NMR (100 MHz, DMSO-d ): d = 20.9, 26.2, 27.9, 29.4, 30.8,
6
3
1
2.2, 36.4, 41.0, 49.8, 55.1, 113.5, 113.8, 114.7, 125.3, 128.7,
31.7, 138.7, 144.4, 147.8, 149.4, 151.6, 157.5, 195.4, 195.6.
Synthesis 2006, No. 24, 4187–4199 © Thieme Stuttgart · New York

PAPER
Synthesis of 9,10-Diarylacridine-1,8-dione and Indenoquinoline Derivatives
4195
Anal. Calcd for C H N O : C, 71.17; H, 5.97; N, 5.93. Found: C,
1 H, CH), 7.05–7.09 (m, 4 H, ArH), 7.17–7.30 (m, 4 H, ArH), 9.97
(s, 1 H, NH), 13.11 (s, 1 H, OH).
2
8
28
2
5
7
1.02; H, 6.12; N, 6.05.
1
3
C NMR (100 MHz, DMSO-d ): d = 21.0, 27.87, 27.94, 28.2, 28.5,
6
Aniline Derivatives 6a–g; General Procedure
3
1
2
1.2, 31.9, 32.7, 33.4, 44.1, 49.5, 110.5, 113.7, 114.4, 125.1, 125.6,
25.8, 127.1, 130.1, 130.3, 133.2, 135.9, 136.0, 143.6, 151.2, 196.2,
00.3.
A mixture of benzaldehyde 1 (3.0 mmol), 5,5-dimethyl-3-(4-meth-
ylanilino)cyclohex-2-enone (2a, 3.0 mmol), and 5,5-dimethylcy-
clohexane-1,3-dione (3a, 3.0 mmol) in a mixture of the ionic liquid
+
–
4
Anal. Calcd for C H ClNO : C, 73.23; H, 6.96; N, 2.85. Found: C,
30 34 3
7
[
bmim ][BF ] (5.0 mL) and H O (5.0 mL) was stirred at 90 °C for
2
3.11; H, 7.00; N, 2.98.
several hours to complete the reaction (monitored by TLC). The
mixture was then cooled to r.t. and the yellow solid was collected
+
–
2-{(4-Chlorophenyl)[4,4-dimethyl-2-(4-methylanilino)-6-oxo-
cyclohex-1-enyl]methyl}-3-hydroxy-5,5-dimethylcyclohex-2-
enone (6d)
by filtration. The filtrate of ionic liquid [bmim ][BF ] and H O was
4
2
then recycled for later use. The crude product was washed with H O
and purified by recrystallization from 95% EtOH; this gave 6a–g.
2
Pale yellow crystals; mp 147–148 °C.
2
-{[4,4-Dimethyl-2-(4-methylanilino)-6-oxocyclohex-1-
enyl](phenyl)methyl}-3-hydroxy-5,5-dimethylcyclohex-2-enone
6a)
IR (KBr): 3252, 3122, 3029, 2956, 2868, 1678, 1638, 1579, 1513,
1
9
1
488, 1467, 1400, 1330, 1312, 1276, 1222, 1161, 1094, 1037, 1011,
42, 921, 863, 830, 818 cm .
(
–1
Pale yellow crystals; mp 209–211 °C.
H NMR (400 MHz, DMSO-d ): d = 0.91 (s, 3 H, CH ), 1.04 (s, 6
6
3
IR (KBr): 3256, 3171, 3060, 2956, 2869, 1643, 1575, 1512, 1477,
H, 2 CH ), 1.10 (s, 3 H, CH ), 2.15 (d, J = 16.4 Hz, 1 H, CH), 2.28–
3
3
1
1
1
451, 1424, 1362, 1301, 1278, 1261, 1222, 1177, 1143, 1122, 1022,
2
1
.43 (m, 9 H, CH + 6 CH), 2.63 (d, J = 16.4 Hz, 1 H, CH), 5.57 (s,
H, CH), 7.06 (d, J = 8.0 Hz, 2 H, ArH), 7.10 (d, J = 8.4 Hz, 2 H,
3
–
1
000, 921, 840, 803, 744, 697 cm .
ArH), 7.23 (d, J = 8.0 Hz, 2 H, ArH), 7.29 (d, J = 8.4 Hz, 2 H, ArH),
.99 (s, 1 H, NH), 13.14 (s, 1 H, OH).
H NMR (400 MHz, DMSO-d ): d = 0.93 (s, 3 H, CH ), 1.06 (s, 6
6
3
9
H, 2 CH ), 1.11 (s, 3 H, CH ), 2.16 (d, J = 16.8 Hz, 1 H, CH), 2.28–
3
3
2
1
.42 (m, 9 H, CH + 6 CH), 2.64 (d, J = 17.6 Hz, 1 H, CH), 5.59 (s,
13
3
C NMR (100 MHz, DMSO-d ): d = 21.0, 21.3, 26.6, 28.0, 28.5,
6
H, CH), 6.96–7.26 (m, 9 H, ArH), 10.03 (s, 1 H, NH), 13.21 (s, 1
2
1
9.7, 31.9, 32.4, 32.7, 33.2, 41.4, 49.9, 113.0, 125.0, 128.2, 128.3,
29.0, 129.9, 130.1, 130.3, 135.9, 136.0, 145.7, 151.2, 195.6, 200.3.
H, OH).
1
3
C NMR (100 MHz, DMSO-d ): d = 21.0, 28.0, 28.27, 28.31, 28.6,
6
Anal. Calcd for C H ClNO : C, 73.23; H, 6.96; N, 2.85. Found: C,
30 34 3
3
1
1.77, 31.83, 32.7, 33.5, 41.2, 49.5, 111.1, 114.1, 114.9, 125.0,
25.5, 126.9, 127.1, 128.3, 130.3, 135.8, 136.0, 140.6, 196.4, 200.3.
7
3.10; H, 6.98; N, 3.01.
2
-{[4,4-Dimethyl-2-(4-methylanilino)-6-oxocyclohex-1-enyl](4-
Anal. Calcd for C H NO : C, 78.74; H, 7.71; N, 3.06. Found: C,
30
35
3
methoxyphenyl)methyl}-3-hydroxy-5,5-dimethylcyclohex-2-
enone (6e)
7
8.60; H, 7.80; N, 3.18.
Pale yellow crystals; mp 144–146 °C.
2
-{(2-Chlorophenyl)[4,4-dimethyl-2-(4-methylanilino)-6-oxo-
cyclohex-1-enyl]methyl}-3-hydroxy-5,5-dimethylcyclohex-2-
enone (6b)
Pale yellow crystals; mp 171–173 °C.
IR (KBr): 3257, 3119, 3029, 2955, 2924, 2868, 2830, 1636, 1517,
1
8
1
509, 1465, 1420, 1330, 1276, 1246, 1162, 1125, 1038, 893, 835,
20, 750 cm .
–1
IR (KBr): 3255, 3169, 3029, 2955, 2925, 2869, 1630, 1600, 1511,
H NMR (400 MHz, DMSO-d ): d = 0.93 (s, 3 H, CH ), 1.05 (s, 6
6
3
1
7
1
467, 1408, 1326, 1248, 1151, 1120, 1101, 1035, 914, 830, 811,
65, 746, 718 cm .
H, 2 CH ), 1.11 (s, 3 H, CH ), 2.15 (d, J = 16.0 Hz, 1 H, CH), 2.27–
3
3
–
1
2
.41 (m, 9 H, CH + 6 CH), 2.62 (d, J = 16.0 Hz, 1 H, CH), 3.71 (s,
3
3 H, CH O), 5.53 (s, 1 H, CH), 6.81 (d, J = 8.0 Hz, 2 H, ArH), 6.99–
H NMR (400 MHz, DMSO-d ): d = 0.91 (s, 3 H, CH ), 0.97 (s, 3
3
6
3
7
.06 (m, 4 H, ArH), 7.23 (d, J = 8.4 Hz, 2 H, ArH), 10.05 (s, 1 H,
H, CH ), 1.01 (s, 6 H, 2 CH ), 2.09 (d, J = 16.4 Hz, 1 H, CH), 2.19
3
3
NH), 13.27 (s, 1 H, OH).
(
(
d, J = 16.0 Hz, 2 H, 2 CH), 2.26–2.46 (m, 8 H, CH + 5 CH), 5.74
s, 1 H, CH), 6.98 (d, J = 8.0 Hz, 2 H, ArH), 7.14–7.26 (m, 4 H,
3
13
C NMR (100 MHz, DMSO-d ): d = 21.0, 21.2, 27.9, 28.0, 28.3,
6
ArH), 7.30–7.33 (m, 2 H, ArH), 9.00 (s, 1 H, NH), 12.28 (s, 1 H,
OH).
2
1
8.4, 31.8, 32.4, 32.6, 32.7, 44.2, 49.5, 55.4, 113.7, 113.8, 123.7,
25.0, 128.1, 128.9, 130.1, 130.3, 135.8, 136.1, 150.7, 157.3, 196.3,
1
3
200.4.
C NMR (100 MHz, DMSO-d ): d = 20.9, 21.3, 26.5, 28.0, 28.2
6
2
1
1
9.8, 32.0, 32.2, 32.5, 33.8, 42.0, 49.9, 111.1, 112.2, 125.1, 126.8,
27.8, 129.8, 129.9, 130.0, 130.3, 133.1, 136.4, 139.4, 143.6, 151.5,
95.3, 200.3.
Anal. Calcd for C H NO : C, 76.36; H, 7.65; N, 2.87. Found: C,
3
1
37
4
7
6.29; H, 7.80; N, 2.99.
2
-{[4,4-Dimethyl-2-(4-methylanilino)-6-oxocyclohex-1-enyl](3-
Anal. Calcd for C H ClNO : C, 73.23; H, 6.96; N, 2.85. Found: C,
30
34
3
nitrophenyl)methyl}-3-hydroxy-5,5-dimethylcyclohex-2-enone
6f)
7
3.18; H, 7.07; N, 2.90.
(
Pale yellow crystals; mp 190–192 °C.
2
-{(3-Chlorophenyl)[4,4-dimethyl-2-(4-methylanilino)-6-oxo-
cyclohex-1-enyl]methyl}-3-hydroxy-5,5-dimethylcyclohex-2-
enone (6c)
Pale yellow crystals; mp 217–218 °C.
IR (KBr): 3250, 3091, 3027, 2956, 2868, 1681, 1629, 1585, 1525,
1
7
1
475, 1396, 1306, 1282, 1238, 1156, 1096, 1040, 942, 924, 804,
59, 732 cm .
–1
IR (KBr): 3256, 3178, 3061, 2953, 2907, 2867, 1680, 1629, 1582,
H NMR (400 MHz, DMSO-d ): d = 0.95 (s, 3 H, CH ), 1.08 (s, 6
6
3
1
9
1
512, 1475, 1421, 1394, 1327, 1313, 1272, 1154, 1113, 1039, 943,
22, 821, 790, 744 cm .
H, 2 CH ), 1.13 (s, 3 H, CH ), 2.20 (d, J = 16.8 Hz, 1 H, CH), 2.28–
3
3
–
1
2
.48 (m, 9 H, CH + 6 CH), 2.62 (d, J = 17.2 Hz, 1 H, CH), 5.73 (s,
3
1 H, CH), 7.08 (d, J = 8.0 Hz, 2 H, ArH), 7.24 (d, J = 8.0 Hz, 2 H,
ArH), 7.53–7.59 (m, 3 H, ArH), 8.01 (d, J = 7.6 Hz, 1 H, ArH),
H NMR (400 MHz, DMSO-d ): d = 0.92 (s, 3 H, CH ), 1.05 (s, 6
6
3
H, 2 CH ), 1.10 (s, 3 H, CH ), 2.16 (d, J = 16.0 Hz, 1 H, CH), 2.28–
3
3
1
0.01 (s, 1 H, NH), 13.15 (s, 1 H, OH).
2
.43 (m, 9 H, CH + 6 CH), 2.63 (d, J = 17.6 Hz, 1 H, CH), 5.60 (s,
3
Synthesis 2006, No. 24, 4187–4199 © Thieme Stuttgart · New York

4
196
X.-S. Wang et al.
PAPER
1
3
1
C NMR (100 MHz, DMSO-d ): d = 20.8, 21.1, 26.3, 27.9, 28.0,
H NMR (400 MHz, DMSO-d ): d = 0.71 (s, 6 H, 2 CH ), 0.87 (s, 6
6
6
3
2
1
1
9.5, 31.6, 32.3, 32.4, 32.7, 41.2, 49.6, 112.4, 121.3, 122.3, 125.0,
30.0, 130.1, 134.5, 135.6, 135.8, 143.3, 147.7, 148.0, 148.6, 151.6,
95.5, 195.9.
H, 2 CH ), 1.77 (d, J = 17.6 Hz, 2 H, 2 CH), 2.00 (d, J = 16.0 Hz, 2
H, 2 CH), 2.17–2.22 (m, 4 H, 4 CH), 2.42 (s, 3 H, CH ), 5.03 (s, 1
H, CH), 7.06 (d, J = 8.0 Hz, 2 H, ArH), 7.30–7.33 (m, 4 H, ArH),
3
3
7
.41 (d, J = 7.6 Hz, 2 H, ArH).
Anal. Calcd for C H N O : C, 71.69; H, 6.82; N, 5.57. Found: C,
3
0
34
2
5
1
3
7
1.50; H, 6.95; N, 5.60.
C NMR (100 MHz, DMSO-d ): d = 20.9, 26.5, 28.4, 32.4, 32.7,
2.5, 50.6, 113.2, 114.9, 115.1, 123.7, 129.6, 129.7, 130.1, 134.2,
6
4
2
-{[4,4-Dimethyl-2-(4-methylanilino)-6-oxocyclohex-1-enyl](4-
136.9, 139.4, 151.1, 161.0, 195.6.
fluorophenyl)methyl}-3-hydroxy-5,5-dimethylcyclohex-2-
enone (6g)
Pale yellow crystals; mp 170–172 °C.
Anal. Calcd for C H FNO : C, 78.75; H, 7.05; N, 3.06. Found: C,
3
0
32
2
7
8.66; H, 7.25; N, 3.22.
IR (KBr): 3250, 3060, 2958, 2865, 1680, 1589, 1504, 1470, 1395,
Indenoquinoline 8a via a 2-Benzylideneindene-1,3-dione Inter-
mediate; Typical Procedure
–
1
1
327, 1271, 1227, 1155, 1115, 1038, 942, 871, 819, 800, 735 cm .
1
A mixture of 4-bromobenzaldehyde (0.35 g, 2.0 mmol) and indene-
H NMR (400 MHz, DMSO-d ): d = 0.91 (s, 3 H, CH ), 1.04 (s, 6
6
3
1
,3-dione (7; 0.30 g, 2.0 mmol) in the ionic liquid medium
H, 2 CH ), 1.10 (s, 3 H, CH ), 2.15 (d, J = 16.0 Hz, 1 H, CH), 2.29–
3
3
+
–
[bmim ][BF ] (5 mL) was stirred at 90 °C for 2 hours to complete
4
2
1
9
.42 (m, 9 H, CH + 6 CH), 2.64 (d, J = 17.6 Hz, 1 H, CH), 5.56 (s,
3
the reaction (monitored by TLC). The mixture was then cooled to
r.t. and the yellow solid was collected by filtration. The filtrate of
H, CH), 7.04–7.12 (m, 6 H, ArH), 7.23 (d, J = 8.0 Hz, 2 H, ArH),
.99 (s, 1 H, NH), 13.18 (s, 1 H, OH).
+
–
the ionic liquid [bmim ][BF ] was then recovered for reuse by dry-
4
1
3
C NMR (100 MHz, DMSO-d ): d = 20.9, 27.9, 28.0, 28.4, 28.6,
6
ing at 80 °C for several hours in vacuo. The crude yellow product
3
1
1
1.8, 32.4, 32.7, 33.0, 44.2, 49.5, 114.2, 114.8, 115.1, 123.7, 125.0,
28.75, 128.83, 130.3, 135.8, 136.0, 139.4, 151.1, 159.4, 161.8,
96.3, 200.3.
was washed with H O and purified by recrystallization from 95%
2
EtOH; this gave 2-(4-bromobenzylidene)-1H-indene-1,3(2H)-di-
one. A mixture of this intermediate (0.33 g, 1.0 mmol) and 5,5-di-
methyl-3-(4-methylanilino)cyclohex-2-enone (2a, 1.0 mmol) in
Anal. Calcd for C H FNO : C, 75.76; H, 7.21; N, 2.95. Found: C,
7
30
34
3
+
–
[
bmim ][BF ] (5 mL) was stirred at 90 °C for 2 h to complete the
5.62; H, 7.25; N, 3.10.
4
reaction (monitored by TLC). The mixture was then cooled to r.t.,
the red solid was collected by filtration, and the filtrate of the ionic
9
,10-Diarylacridine-1,8-diones 4aa–ag; General Procedure
+
–
liquid [bmim ][BF ] was then recovered for reuse by drying at 80
A mixture of the appropriate aniline derivative 6 (1.0 mmol) in the
4
+
–
°C for several hours in vacuo. The crude red product was washed
ionic liquid medium [bmim ][BF ] (5 mL) was stirred at 90 °C for
several hours to complete the reaction (monitored by TLC). The
mixture was then cooled to r.t. and the yellow solid was collected
by filtration. The filtrate of the ionic liquid [bmim ][BF ] was then
recovered for reuse by drying at 80 °C several hours in vacuo. The
crude product was washed with H O and purified by recrystalliza-
tion from DMF–H O; this gave 4aa–ag.
4
with H O, purified by recrystallization from DMF–H O, and dried
2
2
at 80 °C for several hours in vacuo; this gave 8a; yield: 97%.
+
–
4
2
-(4-Bromobenzylidene)-1H-indene-1,3(2H)-dione (8a)
Pale yellow crystals; mp 179–181 °C.
IR (KBr): 3054, 1690, 1632, 1593, 1483, 842, 738, 707 cm–1.
2
2
1
H NMR (400 MHz, DMSO-d ): d = 7.81 (d, J = 8.4 Hz, 2 H, ArH),
6
3
,3,6,6-Tetramethyl-9-phenyl-10-(4-tolyl)-3,4,6,7,9,10-hexa-
7
.85 (s, 1 H, ArH), 7.97–8.04 (m, 4 H, ArH), 8.45 (d, J = 8.4 Hz, 2
hydroacridine-1,8(2H,5H)-dione (4aa)
Pale yellow crystals; mp 262–263 °C (Lit.15 262–263 °C).
H, ArH).
1
3
C NMR (100 MHz, DMSO-d ): d = 123.6, 129.3, 130.2, 132.1,
6
9
3
-(2-Chlorophenyl)-3,3,6,6-tetramethyl-10-(4-tolyl)-
135.9, 136.5, 136.6, 138.4, 140.0, 142.4, 144.2, 189.1, 189.7.
,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4ab)
Anal. Calcd for C H BrO : C, 61.37; H, 2.90; Found: C, 61.30; H,
1
5
16
9
3
Pale yellow crystals; mp 286–288 °C (Lit. 285–287 °C).
2
.91.
9
3
-(3-Chlorophenyl)-3,3,6,6-tetramethyl-10-(4-tolyl)-
Indenoquinolines 8a–i by Three-Component Reactions between
Benzaldehydes 1, 3-Anilino-5,5-dimethylcyclohex-2-enones 2,
and Indene-1,3-dione (7); General Procedure
,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4ac)
1
6
Pale yellow crystals; mp >300 °C (Lit. 315–317 °C).
A mixture of benzaldehyde 1 (1.0 mmol), 3-anilino-5,5-dimethyl-
9
3
-(4-Chlorophenyl)-3,3,6,6-tetramethyl-10-(4-tolyl)-
cyclohex-2-enone 2 (1.0 mmol), indene-1,3-dione (7; 0.15 g, 1.0
,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4ad)
+
–
mmol) and the ionic liquid medium [bmim ][BF ] (5 mL) was
1
5
4
Pale yellow crystals; mp 284–286 °C (Lit. 282–283 °C).
stirred at 90 °C for several hours to complete the reaction (moni-
tored by TLC). The mixture was then cooled to r.t., and the red solid
was collected by filtration. The filtrate of the ionic liquid
9
3
-(4-Methoxyphenyl)-3,3,6,6-tetramethyl-10-(4-tolyl)-
,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4ae)
+
–
[
bmim ][BF ] was then recovered for reuse by drying at 80 °C for
1
5
4
Pale yellow crystals; mp 274–276 °C (Lit. 273–274 °C).
several hours in vacuo. The crude red product was washed with
H O, purified by recrystallization from DMF–H O, and dried at 80
2
2
3
,3,6,6-Tetramethyl-9-(3-nitrophenyl)-10-(4-tolyl)-3,4,6,7,9,10-
°C for several hours in vacuo; this gave 8a–i.
hexahydroacridine-1,8(2H,5H)-dione (4af)
1
6
Pale yellow crystals; mp 285–286 °C (Lit. 285–287 °C).
1
0-(4-Bromophenyl)-7,7-dimethyl-5-(4-tolyl)-6,7,8,10-tetra-
hydro-5H-indeno[1,2-b]quinoline-9,11-dione (8a)
Red crystals; mp 275–277 °C.
9
3
-(4-Fluorophenyl)-3,3,6,6-tetramethyl-10-(4-tolyl)-
,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (4ag)
IR (KBr): 3050, 2960, 2887, 1693, 1642, 1588, 1557, 1511, 1485,
Pale yellow crystals; mp 259–261 °C.
1
8
455, 1396, 1366, 1255, 1223, 1170, 1140, 1101, 1057, 1012, 889,
42, 763, 728, 710 cm .
IR (KBr): 3060, 2957, 2869, 1641, 1575, 1511, 1643, 1410, 1361,
1
–1
–
1
300, 1280, 1262, 1177, 1145, 1121, 999, 921, 843, 812, 715 cm .
Synthesis 2006, No. 24, 4187–4199 © Thieme Stuttgart · New York

PAPER
Synthesis of 9,10-Diarylacridine-1,8-dione and Indenoquinoline Derivatives
4197
1
13
H NMR (400 MHz, DMSO-d ): d = 0.80 (s, 3 H, CH ), 0.94 (s, 3
C NMR (100 MHz, DMSO-d ): d = 26.1, 30.9, 32.0, 32.8, 40.2,
6
3
6
H, CH ), 1.99 (d, J = 17.6 Hz, 1 H, CH), 2.05 (d, J = 16.0 Hz, 1 H,
49.6, 111.8, 114.8, 115.0, 120.7, 121.2, 123.8, 129.8, 129.9, 130.0,
3
CH), 2.27 (d, J = 16.0 Hz, 1 H, CH), 2.39 (d, J = 17.6 Hz, 1 H, CH),
132.2, 132.3, 132.8, 133.2, 136.8, 137.5, 141.8, 150.8, 154.2, 159.7,
162.1, 191.2, 195.6.
2
7
.50 (s, 3 H, CH ), 4.83 (s, 1 H, CH), 5.21 (d, J = 7.6 Hz, 1 H, ArH),
.01–7.04 (m, 1 H, ArH), 7.19–7.25 (m, 2 H, ArH), 7.33 (d, J = 8.4
3
Anal. Calcd for C H BrFNO : C, 68.19; H, 4.39; N, 2.65. Found:
3
0
23
2
Hz, 2 H, ArH), 7.45–7.50 (m, 4 H, ArH), 7.54–7.61 (m, 2 H, ArH).
C, 68.10; H, 4.45; N, 2.70.
1
3
C NMR (100 MHz, DMSO-d ): d = 21.0, 26.2, 29.4, 32.0, 33.1,
6
4
1
1
0.6, 49.6, 111.2, 114.5, 120.9, 121.0, 128.2, 129.9, 130.0, 130.5,
30.9, 132.0, 133.0, 135.6, 136.9, 140.3, 144.7, 151.5, 154.8, 191.1,
95.9.
5-(4-Bromophenyl)-10-(2,4-dichlorophenyl)-7,7-dimethyl-
6,7,8,10-tetrahydro-5H-indeno[1,2-b]quinoline-9,11-dione (8e)
Red crystals; mp 288–290 °C.
Anal. Calcd for C H BrNO : C, 71.00; H, 5.00; N, 2.67. Found:
C, 70.79; H, 5.09; N, 2.70.
IR (KBr): 3062, 2954, 2871, 1683, 1636, 1591, 1582, 1566, 1489,
1470, 1396, 1368, 1301, 1257, 1226, 1193, 1169, 1154, 1101, 1063,
31
26
2
–
1
1
012, 889, 860, 765, 734, 703 cm .
1
0-(4-Fluorophenyl)-7,7-dimethyl-5-(4-tolyl)-6,7,8,10-tetra-
1
H NMR (400 MHz, DMSO-d ): d = 0.83 (s, 3 H, CH ), 0.94 (s, 3
6
3
hydro-5H-indeno[1,2-b]quinoline-9,11-dione (8b)
Red crystals; mp 218–220 °C.
H, CH ), 1.98 (d, J = 17.6 Hz, 1 H, CH), 2.01 (d, J = 16.0 Hz, 1 H,
3
CH), 2.24 (d, J = 16.0 Hz, 1 H, CH), 2.33 (d, J = 17.6 Hz, 1 H, CH),
5.20 (s, 1 H, CH), 5.23 (d, J = 7.6 Hz, 1 H, ArH), 7.07–7.11 (m, 1
H, ArH), 7.21–7.23 (m, 2 H, ArH), 7.33 (dd, J = 8.4, 1.6 Hz, 1 H,
ArH), 7.47 (d, J = 1.6 Hz, 1 H, ArH), 7.53 (d, J = 8.4 Hz, 1 H, ArH),
7.67–7.75 (m, 2 H, ArH), 7.89–7.92 (m, 2 H, ArH).
IR (KBr): 3050, 2959, 2892, 2838, 1673, 1633, 1601, 1588, 1558,
1
1
1
498, 1455, 1398, 1362, 1255, 1222, 1191, 1158, 1139, 1102, 1091,
–
1
061, 1017, 888, 852, 766, 705 cm .
H NMR (400 MHz, DMSO-d ): d = 0.79 (s, 3 H, CH ), 0.94 (s, 3
6
3
1
3
H, CH ), 1.99 (d, J = 17.6 Hz, 1 H, CH), 2.02 (d, J = 16.0 Hz, 1 H,
C NMR (100 MHz, CDCl ): d = 26.9, 29.7, 32.2, 33.7, 41.1, 49.9,
3
3
CH), 2.26 (d, J = 16.0 Hz, 1 H, CH), 2.52 (d, J = 17.6 Hz, 1 H, CH),
114.3, 120.7, 121.5, 124.5, 127.0, 129.7, 129.9, 131.5, 131.7, 132.8,
133.1, 133.2, 133.4, 134.1, 134.5, 136.8, 137.7, 139.9, 151.2, 154.7,
191.6, 195.9.
2
7
2
.50 (s, 3 H, CH ), 4.85 (s, 1 H, CH), 5.20 (d, J = 7.6 Hz, 1 H, ArH),
3
.02–7.11 (m, 3 H, ArH), 7.16–7.24 (m, 2 H, ArH), 7.37–7.41 (m,
H, ArH), 7.48 (d, J = 7.6 Hz, 2 H, ArH), 7.53–7.61 (m, 2 H, ArH).
Anal. Calcd for C H BrCl NO : C, 62.20; H, 3.83; N, 2.42.
Found: C, 62.11; H, 3.85; N, 2.58.
3
0
22
2
2
1
3
C NMR (100 MHz, DMSO-d ): d = 21.1, 26.2, 29.5, 32.0, 32.8,
6
4
1
1
0.3, 50.0, 111.5, 114.7, 114.8, 115.0, 120.9, 121.0, 129.7, 129.8,
29.9, 132.0, 133.0, 135.6, 137.0, 140.3, 141.98, 142.01, 151.3,
54.6, 159.7, 162.5, 191.2, 195.6.
10-(3-Chlorophenyl)-7,7-dimethyl-5-(1-naphthyl)-6,7,8,10-
tetrahydro-5H-indeno[1,2-b]quinoline-9,11-dione (8f)
Red crystals; mp 225–226 °C.
Anal. Calcd for C H FNO : C, 80.32; H, 5.65; N, 3.02. Found: C,
31
26
2
8
0.15; H, 5.68; N, 3.12.
IR (KBr): 3054, 2960, 2871, 1689, 1652, 1635, 1590, 1563, 1468,
1
455, 11391, 1363, 1301, 1260, 1226, 1191, 1171, 1134, 1004, 890,
–
1
5
,10-Bis(4-bromophenyl)-7,7-dimethyl-5-(4-tolyl)-6,7,8,10-
728, 730, 685 cm .
tetrahydro-5H-indeno[1,2-b]quinoline-9,11-dione (8c)
1
H NMR (400 MHz, DMSO-d ): d = 0.79 (s, 3 H, CH ), 0.80 (s, 3
6
3
Red crystals; mp 271–273 °C.
H, CH ), 1.94 (d, J = 17.4 Hz, 1 H, CH), 2.11 (d, J = 16.0 Hz, 1 H,
3
IR (KBr): 3089, 2959, 2883, 1692, 1645, 1608, 1590, 1559, 1487,
CH), 2.25 (d, J = 16.4 Hz, 2 H, 2 CH), 4.68 (d, J = 7.6 Hz, 1 H,
ArH), 4.98 (s, 1 H, CH), 6.72–6.76 (m, 1 H, ArH), 6.76–7.45 (m, 6
H, ArH), 7.65–7.70 (m, 2 H, ArH), 7.80–7.85 (m, 2 H, ArH), 8.03
(d, J = 6.4 Hz, 1 H, ArH), 8.20 (d, J = 7.2 Hz, 1 H, ArH), 8.34 (d,
J = 8.4 Hz, 1 H, ArH).
1
1
1
455, 1395, 1365, 1301, 1254, 1223, 1191, 1169, 1141, 1100, 1070,
010, 976, 888, 841, 791, 763, 705 cm .
–
1
H NMR (400 MHz, DMSO-d ): d = 0.80 (s, 3 H, CH ), 0.94 (s, 3
6
3
H, CH ), 1.98 (d, J = 17.6 Hz, 1 H, CH), 2.05 (d, J = 16.0 Hz, 1 H,
3
1
3
CH), 2.26 (d, J = 16.0 Hz, 1 H, CH), 2.38 (d, J = 17.6 Hz, 1 H, CH),
C NMR (100 MHz, DMSO-d ): d = 27.3, 28.6, 32.5, 34.2, 40.6,
6
4
.82 (s, 1 H, CH), 5.26 (d, J = 7.6 Hz, 1 H, ArH), 7.07–7.12 (m, 1
H, ArH), 7.19–7.26 (m, 2 H, ArH), 7.34 (d, J = 8.0 Hz, 2 H, ArH),
.45 (d, J = 8.0 Hz, 2 H, ArH), 7.72 (b, 2 H, ArH), 7.90 (d, J = 8.4
Hz, 2 H, ArH).
50.0, 111.5, 114.8, 120.7, 121.4, 122.4, 126.6, 126.7, 127.2, 128.0,
128.4, 128.9, 129.2, 129.4, 130.2, 130.6, 131.5, 131.8, 132.2, 133.1,
133.2, 134.1, 134.6, 136.7, 148.4, 152.1, 155.2, 191.5, 196.0.
7
Anal. Calcd for C H ClNO : C, 79.14; H, 5.08; N, 2.71. Found: C,
3
4
26
2
1
3
C NMR (100 MHz, DMSO-d ): d = 26.5, 29.7, 32.3, 34.5, 40.6,
78.95; H, 5.21; N, 2.70.
6
4
1
9.8, 111.9, 114.8, 119.8, 121.1, 121.7, 124.1, 130.3, 130.7, 131.4,
32.5, 132.6, 133.1, 137.1, 137.8, 145.3, 151.4, 154.6, 191.4, 195.9.
10-(2-Chlorophenyl)-7,7-dimethyl-5-(1-naphthyl)-6,7,8,10-
tetrahydro-5H-indeno[1,2-b]quinoline-9,11-dione (8g)
Red crystals; mp 260–263 °C.
Anal. Calcd for C H Br NO : C, 61.14; H, 3.93; N, 2.38. Found:
C, 61.00; H, 3.98; N, 2.49.
3
0
23
2
2
IR (KBr): 3056, 3013, 2952, 2868, 1695, 1633, 1606, 1560, 1507,
1467, 1457, 1395, 1363, 1261, 1227, 1192, 1172, 1132, 1037, 1005,
890, 782, 766, 733, 700 cm .
5
-(4-Bromophenyl)-10-(4-fluorophenyl)-7,7-dimethyl-6,7,8,10-
–
1
tetrahydro-5H-indeno[1,2-b]quinoline-9,11-dione (8d)
Red crystals; mp 280–282 °C.
1
H NMR (400 MHz, DMSO-d ): d = 0.79 (s, 3 H, CH ), 0.82 (s, 3
6
3
IR (KBr): 3047, 2955, 2891, 1686, 1650, 1636, 1592, 1566, 1503,
H, CH ), 1.93 (d, J = 17.4 Hz, 1 H, CH), 2.03 (d, J = 16.4 Hz, 1 H,
3
1
1
1
488, 1453, 1398, 1369, 1312, 1259, 1225, 1191, 1170, 1155, 1101,
012, 978, 940, 888, 852, 764, 734, 705 cm .
CH), 2.11 (d, J = 17.2 Hz, 1 H, CH), 2.22 (d, J = 16.4 Hz, 1 H, 1
CH), 4.66 (d, J = 7.6 Hz, 1 H, ArH), 5.38 (s, 1 H, CH), 6.72–6.76
(m, 1 H, ArH), 7.05–7.35 (m, 5 H, ArH), 7.61 (dd, J = 7.6, 1.2 Hz,
–
1
H NMR (400 MHz, DMSO-d ): d = 0.80 (s, 3 H, CH ), 0.94 (s, 3
6
3
1
(
H, ArH), 7.66–7.69 (m, 2 H, ArH), 7.80–7.91 (m, 2 H, ArH), 8.01
d, J = 7.2 Hz, 2 H, ArH), 8.19–8.22 (m, 1 H, ArH), 8.34 (d, J = 8.4
Hz, 1 H, ArH).
H, CH ), 1.98 (d, J = 17.6 Hz, 1 H, CH), 2.05 (d, J = 16.0 Hz, 1 H,
CH), 2.26 (d, J = 16.0 Hz, 1 H, CH), 2.38 (d, J = 17.6 Hz, 1 H, CH),
3
4
.84 (s, 1 H, CH), 5.26 (d, J = 7.6 Hz, 1 H, ArH), 7.06–7.10 (m, 3
H, ArH), 7.19–7.26 (m, 2 H, ArH), 7.38–7.42 (m, 2 H, ArH), 7.71
b, 2 H, ArH), 7.90 (d, J = 8.8 Hz, 2 H, ArH).
1
3
C NMR (100 MHz, DMSO-d ): d = 27.2, 28.7, 32.4, 36.3, 40.6,
6
(
50.1, 115.0, 120.6, 121.2, 122.3, 126.6, 127.6, 128.0, 128.3, 129.1,
Synthesis 2006, No. 24, 4187–4199 © Thieme Stuttgart · New York

4
198
X.-S. Wang et al.
PAPER
1
1
29.2, 129.4, 129.7, 130.2, 131.4, 131.9, 132.0, 132.1, 133.1, 133.2,
34.1, 134.7, 136.7, 152.3, 155.4, 162.8, 191.2, 195.7.
(2) (a) da Silveira Neto, B. A.; Ebeling, G.; Goncalves, R. S.;
Gozzo, F. C.; Eberlin, M. N.; Dupont, J. Synthesis 2004,
1
155. (b) Yeung, K. S.; Farkas, M. E.; Qiu, Z.; Yang, Z.
Anal. Calcd for C H ClNO : C, 79.14; H, 5.08; N, 2.71. Found: C,
34
26
2
Tetrahedron Lett. 2002, 43, 5793. (c) Fraga-Dubreuil, J.;
Bazureau, J. P. Tetrahedron 2003, 59, 6121. (d) Yadav, J.
S.; Reddy, B. V. S.; Basak, A. K.; Narsaiah, A. V.
Tetrahedron Lett. 2003, 44, 1047. (e) Su, C.; Chen, Z. C.;
Zheng, Q. G. Synthesis 2003, 555. (f) Hakkou, H.; Jacques,
J.; Eynde, V.; Hamelin, J.; Bazureau, J. P. Synthesis 2004,
7
8.90; H, 5.24; N, 2.75.
1
0-(4-Methoxyphenyl)-7,7-dimethyl-5-(1-naphthyl)-6,7,8,10-
tetrahydro-5H-indeno[1,2-b]quinoline-9,11-dione (8h)
Red crystals; mp 256–258 °C.
IR (KBr): 3056, 2995, 2960, 2932, 2877, 2832, 2685, 1654, 1633,
1
793.
3) (a) Janis, R. A.; Silver, P. J.; Triggle, D. J. Adv. Drug Res.
987, 16, 309. (b) Shan, R.; Velazquez, C.; Knaus, E. E. J.
1
1
1
589, 1562, 1508, 1455, 1392, 1364, 1300, 1251, 1226, 1192, 1170,
134, 1037, 1004, 889, 784, 763, 708 cm .
(
–
1
1
Med. Chem. 2004, 41, 254. (c) Dulhunty, A. F.; Curtis, S.
H NMR (400 MHz, DMSO-d ): d = 0.80 (s, 6 H, 2 CH ), 1.95 (d,
6
3
M.; Watson, S.; Cengia, L.; Marco, G. J. Biol. Chem. 2004,
J = 16.8 Hz, 1 H, CH), 2.07 (d, J = 16.0 Hz, 1 H, CH), 2.18 (d, J =
6.8 Hz, 1 H, CH), 2.24 (d, J = 16.0 Hz, 1 H, 1 CH), 3.74 (s, 3 H,
CH O), 4.66 (d, J = 7.6 Hz, 1 H, ArH), 4.91 (s, 1 H, CH), 6.70–6.74
279, 11853.
1
(
(
4) Martin, N.; Quinteiro, M.; Seoane, C.; Mora, L.; Suarez, M.;
Ockoa, E.; Morales, A. J. Heterocycl. Chem. 1995, 51, 235.
5) (a) Wang, X. S.; Zhang, M. M.; Zeng, Z. S.; Shi, D. Q.; Tu,
S. J.; Wei, X. Y.; Zong, Z. M. Tetrahedron Lett. 2005, 46,
3
(
m, 1 H, ArH), 6.86 (d, J = 8.4 Hz, 2 H, ArH), 7.03–7.19 (m, 2 H,
ArH), 7.36 (d, J = 8.4 Hz, 2 H, ArH), 7.65–7.68 (m, 4 H, ArH), 7.99
d, J = 7.2 Hz, 2 H, ArH), 8.19–8.21 (m, 1 H, ArH), 8.33 (d, J = 8.4
Hz, 1 H, ArH).
(
7169. (b) Wang, X. S.; Shi, D. Q.; Zhang, Y. F.; Wang, S.
H.; Tu, S. J. Chin. J. Org. Chem. 2004, 24, 430.
6) Tu, S. J.; Miao, C. B.; Gao, Y.; Feng, Y. J.; Feng, J. C. Chin.
J. Chem. 2002, 20, 703.
7) Li, Y. L.; Zhang, M. M.; Wang, X. S.; Shi, D. Q.; Tu, S. J.;
Wei, X. Y.; Zong, Z. M. J. Chem. Res. 2005, 600.
1
3
C NMR (100 MHz, DMSO-d ): d = 26.9, 28.5, 32.2, 32.7, 38.9,
6
(
(
4
1
1
9.8, 55.1, 112.3, 113.7, 115.4, 120.2, 121.0, 122.1, 126.3, 127.7,
28.5, 128.9, 129.1, 129.7, 131.1, 131.6, 131.8, 133.0, 133.8, 134.5,
36.6, 138.2, 151.0, 154.5, 157.9, 191.3, 195.7.
Anal. Calcd for C H NO : C, 82.17; H, 5.71; N, 2.74. Found: C,
(8) Mikata, Y.; Yokoyama, M.; Mogami, K.; Kato, M.; Okura,
35
29
3
8
2.00; H, 5.92; N, 2.81.
I.; Chikira, M.; Yano, S. Inorg. Chim. Acta 1998, 279, 51.
(
9) Antonini, I.; Polucci, P.; Kelland, L. R.; Menta, E.; Pescalli,
1
0-(4-Fluorophenyl)-7,7-dimethyl-5-(1-naphthyl)-6,7,8,10-
N.; Martelli, S. J. Med. Chem. 1999, 42, 2535.
tetrahydro-5H-indeno[1,2-b]quinoline-9,11-dione (8i)
(10) Gamage, S. A.; Spicer, J. A.; Atwell, G. J.; Finlay, G. J.;
Red crystals; mp 267–270 °C.
Baguley, B. C.; Denny, W. A. J. Med. Chem. 1999, 42, 2383.
(
(
(
11) Eid, N. M.; Safwat, H. M.; Ramadan, M. A.; Shouman, S.
A.; El-Esawy, A. A. Bull. Fac. Pharm. (Cairo Univ.) 1995,
33, 25.
12) Gallo, S.; Atifi, S.; Mahamoud, A.; Santelli-Rouvier, C.;
Wolfart, K.; Molnar, J.; Barbe, J. Eur. J. Med. Chem. 2003,
38, 19.
IR (KBr): 3059, 2954, 2868, 1683, 1652, 1631, 1591, 1563, 1505,
1
7
1
455, 1393, 1363, 1263, 1226, 1192, 1156, 1128, 1005, 889, 864,
86, 768, 707 cm .
–
1
H NMR (400 MHz, DMSO-d ): d = 0.78 (s, 3 H, CH ), 0.79 (s, 3
6
3
H, CH ), 1.95 (d, J = 17.2 Hz, 1 H, CH), 2.09 (d, J = 16.4 Hz, 1 H,
3
CH), 2.18 (d, J = 17.2 Hz, 1 H, CH), 2.24 (d, J = 16.4 Hz, 1 H, 1
CH), 4.67 (d, J = 7.6 Hz, 1 H, ArH), 4.98 (s, 1 H, CH), 6.71–6.75
13) Srivastava, A.; Nizamuddin, C. Indian J. Heterocycl. Chem.
2004, 13, 261.
(m, 1 H, ArH), 7.04–7.22 (m, 4 H, ArH), 7.47–7.50 (m, 2 H, ArH),
(
(
14) Ferencz, L.; Peter, M. Farmacia 2003, 51, 52.
15) Wang, X. S.; Shi, D. Q.; Wang, S. H.; Tu, S. J. Chin. J. Org.
Chem. 2003, 23, 1291.
7
.65–7.71 (m, 2 H, ArH), 7.79–7.85 (m, 2 H, ArH), 8.02 (d, J = 7.2
Hz, 2 H, ArH), 8.19–8.21 (m, 1 H, ArH), 8.34 (d, J = 8.0 Hz, 1 H,
ArH).
(16) Jin, T. S.; Zhang, J. S.; Guo, T. T.; Wang, A. Q.; Li, T. S.
1
3
C NMR (100 MHz, DMSO-d ): d = 28.7, 29.7, 32.5, 33.4, 40.6,
Synthesis 2004, 2001.
6
5
1
1
0.1, 112.0, 115.1, 115.3, 120.6, 121.3, 122.4, 126.6, 128.0, 128.9,
29.2, 129.4, 130.1, 130.2, 130.3, 131.4, 131.9, 132.2, 133.2, 134.1,
34.7, 136.8, 142.4, 151.7, 155.1, 160.0, 162.4, 191.5, 196.0.
(17) (a) Chebanov, V. A.; Saraev, V. E.; Kobzar, K. M.; Desenko,
S. M.; Orlov, V. D.; Gura, E. A. Chem. Heterocycl. Compd.
2004, 40, 475. (b) El-Sadek, M. I.; Al-Ashmawi, M. A.; El-
Bermawy, M. A.; Mohamed, A. K.; Al-Sabbagh, O. I.
Zagazig, J. Pharm. Sci. 1994, 3, 144.
Anal. Calcd for C H FNO : C, 81.74; H, 5.25; N, 2.80. Found: C,
8
34
26
2
1.68; H, 5.30; N, 2.88.
(
18) Abdel-Gawad, S. M.; El-Gaby, M. S. A.; Heiba, H. I.; Aly,
H. M.; Ghorab, M. M. J. Chin. Chem. Soc. 2005, 52, 1227.
19) Crystal structure data for 4r: C H NO , M = 441.55, pale
(
2
9
31
3
Acknowledgment
3
yellow block crystals, 0.50 × 0.47 × 0.26 mm , triclinic,
space group P–1, a = 9.6382 (15), b = 11.5847 (15),
We are grateful to the Natural Science Foundation (04KJB150139)
of Jiangsu Education Committee for financial support.
c = 12.4722 (11) Å, a = 66.075 (9), b = 70.176 (9),
3
–3
g = 85.800(13)°, V = 1194.1 (3) Å , Z = 2, D = 1.228 g·cm ,
c
–
1
F(000) = 472, m(Mo Ka) = 0.079 mm . Intensity data were
collected on a Rigaku Mercury diffractometer with graphite
monochromated Mo-Ka radiation (l = 0.71070 Å) using the
w scan mode with 3.07° < q < 25.34°; 4332 unique
References
(
1) (a) Welton, T. Chem. Rev. 1999, 99, 2071.
b) Wasserscheid, P.; Keim, W. Angew. Chem. Int. Ed. 2000,
9, 3773. (c) Sheldon, R. Chem. Commun. 2001, 2399.
d) Wilkes, J. S. Green Chem. 2002, 4, 73.
(
3
(
reflections were measured and 3733 reflections with I >
2s(I) were used in the refinement. The structure was solved
by direct methods and expanded using Fourier techniques.
The final cycle of full-matrix least-squares technique refined
to R = 0.0539 and wR = 0.1204.
(
20) Shi, D. Q.; Zhuang, Q. Y.; Chen, J.; Wang, X. S.; Tu, S. J.;
Hu, H. W. Chin. J. Org. Chem. 2003, 23, 694.
Synthesis 2006, No. 24, 4187–4199 © Thieme Stuttgart · New York

PAPER
Synthesis of 9,10-Diarylacridine-1,8-dione and Indenoquinoline Derivatives
4199
(
21) Crystal structure data for 6a: C H NO , M = 457.59, pale
(22) Crystal structure data for 8b: C H FN O , M = 536.62, red
3
0
35
3
34 33
2
3
3
3
yellow block crystals, 0.20 × 0.15 × 0.10 mm , monoclinic,
space group P21/c, a = 10.2337 (13), b = 17.077 (2),
c = 15.2788 (19) Å, a = 90.00, b = 106.329 (3), g = 90.00°,
block crystals, 0.40 × 0.21 × 0.20 mm , monoclinic, space
group P21/n, a = 113.0147 (18), b = 9.5006 (12), c = 22.985
(3) Å, a = 90.00, b = 102.850 (3), g = 90.00°, V = 2770.9 (6)
3
–3
3
–3
V = 2562.4 (5) Å , Z = 4, D = 1.186 g·cm , F(000) = 984,
Å , Z = 4, D = 1.286 g·cm , F(000) = 1136, m(Mo
c
c
–
1
–1
m(Mo Ka) = 0.076 mm . Intensity data were collected on a
CCD area diffractometer with graphite monochromated Mo-
Ka radiation (l = 0.71073Å) using the j and w scan modes
with 2.07° < q < 26.00°; 4985 unique reflections were
measured and 1823 reflections with I > 2s(I) were used in
the refinement. The structure was solved by direct methods
and expanded using Fourier techniques. The final cycle of
full-matrix least-squares technique refined to R = 0.0617
and wR = 0.1201.
Ka) = 0.087 mm . Intensity data were collected on a Rigaku
Mercury diffractometer with graphite monochromated Mo-
Ka radiation (l = 0.71070Å) using the j and w scan modes
with 3.03° < q < 25.34°; 3830 unique reflections were
measured and 1823 reflections with I > 2s(I) were used in
the refinement. The structure was solved by direct methods
and expanded using Fourier techniques. The final cycle of
full-matrix least-squares technique refined to R = 0.0789
and wR = 0.1544.
Synthesis 2006, No. 24, 4187–4199 © Thieme Stuttgart · New York