A green procedure for the synthesis of 1,8-dioxodecahydroacridine derivatives under microwave irradiation in aqueous media without catalyst

Article abstract of DOI:10.1002/jhet.322

(Chemical Equation Presented) A green procedure for the synthesis of 1,8-dioxo-decahydroacridine derivatives is developed under microwave irradiation without catalyst in water. This method provides several advantages such as excellent yields (86-96%), simple workup procedure, and environment friendliness.

Full text of DOI:10.1002/jhet.322

March 2010
A Green Procedure for the Synthesis of
1,8-Dioxodecahydroacridine Derivatives under Microwave
Irradiation in Aqueous Media without Catalyst
363
Zi-Qiang Tang,a,b Yan Chen,a Chang-Ning Liu,a Ke-Ying Cai,a
and Shu-Jiang Tuc,d
*
aSchool of Chemistry and Chemical Engineering, Xuzhou Institute of Technology College,
Xuzhou, Jiangsu 221008, People’s Republic of China
bXuzhou Technician Institute, Xuzhou, Jiangsu 221151, People’s Republic of China
cSchool of Chemistry and Chemical Engineering, Xuzhou Normal University, Xuzhou,
Jiangsu 221119, People’s Republic of China
dKey Laboratory of Biotechnology on Medical Plant, Xuzhou Normal University, Xuzhou,
Jiangsu 221119, People’s Republic of China
*E-mail: laotu2001@263.net
Received December 22, 2008
DOI 10.1002/jhet.322
Published online 4 March 2010 in Wiley InterScience (www.interscience.wiley.com).
A green procedure for the synthesis of 1,8-dioxo-decahydroacridine derivatives is developed under
microwave irradiation without catalyst in water. This method provides several advantages such as excel-
lent yields (86–96%), simple workup procedure, and environment friendliness.
J. Heterocyclic Chem., 47, 363 (2010).
INTRODUCTION
be carried out catalyzed by p-dodecylben-zensulfonic
acid (DBSA) in water. However, these reactions must
be carried out by impetus of catalyst or in organic sol-
vents. Wang et al. [20] reported the same reaction pro-
ceeded in an ionic medium, and Wang and Miao [21]
achieved the reactions in aqueous solvent at traditional
heating. The reaction time was 10 h, the yield was 72–
75%. Arylamine used was only p-toluidine. Microwave-
assisted organic reaction using water as solvent has pe-
culiarity of ‘‘safe solvents’’ and ‘‘energy efficiency.’’ It
was widely used in the organic synthesis [22]. In this ar-
ticle, we would like to report the green synthesis of 1,8-
dioxo-9,10-diaryl-decahydracidines without catalyst via
the combination of aqueous solvent and microwave
heating, using a variety of arylamines including the ani-
lines contained electron-withdrawing groups and elec-
tron-donating groups (Scheme 1).
Water as a solvent has many advantages in organic
synthesis, both from economic and from environmental
points of view. Water has, therefore, become an attrac-
tive medium for many organic reactions. Many impor-
tant types of heterocyclic compounds, such as triazines
[1], acridines [2], quinolines [3], pyridines [4], indoles
[5], pyrazines [6], furans [7], and pyrimidines [8] have
been synthesized in aqueous media.
4-Aryl-1,4-dihydropyridines (1,4-DHPs) have proved
to be valuable as drugs for the treatment of cardiovascu-
lar disorders [9] and constitute an important class of cal-
cium channel blockers [10]. It is well established that
slight structural modification on the DHP ring may
result in remarkable change of pharmacological effect
[11–14]. With a 1,4-DHP parent nucleus, acridine-1,8-
diones have been shown to have very high lasing effi-
ciencies [15] and used as photoinitiators [16]. Recently,
many methods have become available for the synthesis
of these important class of derivatives, We have synthe-
sized these compounds from schiff’s base and dimedone
or 1,3-cyclohexanedione or three-component (aldehyde,
dimedone, and arylamines) in glycol under microwave
[17,18]. Jin et al. [19] reported that this reaction could
RESULTS AND DISCUSSION
When treating aldehyde 1 with dimedone or 1,3-
cyclohexanedione 2 and primary arylamines 3 under
microwave irradiation, the target compound 4 were
obtained.
C
V
2010 HeteroCorporation

364
Z.-Q. Tang, Y. Chen, C.-N. Liu, K.-Y. Cai, and S.-J. Tu
Vol 47
1
Scheme 1
and H NMR). In addition, the X-ray diffraction analysis
of product 4e [23], 4k [24], 4l [25], 4n [26], was carry
out to confirm its structure. The crystal structure of 4k
is shown in Figure 1.
In conclusion, we have developed a green chemistry
method for the synthesis of 1,8-dioxo-decahydroacridine
derivatives. Excellent yields were obtained not only for
anilines substituted with electron-donating groups but
also for ones containing electron-withdrawing groups,
The method avoided using organic solvents and had the
main advantages of convenient procedure and environ-
mental friendliness.
To demonstrate the efficiency and the applicability of
this method, we investigated the reaction of a variety of
aromatic aldehydes 1, dimedone, and a variety of primary
arylamines 3 at 140ꢀC in aqueous media. As shown in
Table 1, a series of 1 and 3, in which the aromatic ring
contained electron-withdrawing groups (such as halo or
nitro) or electron-donating groups (such as methyl or
methyloxy), reacted with 2a under the same reaction con-
ditions to give the corresponding product 4 in good yields
(entries 1–14), We thus concluded that there were no
obvious electronic effect of the substituents on the aro-
matic rings. To further expand the scope of the present
method, the replacement of dimedone 2a with 1,3-cyclo-
hexanedione 2b was examined. To our delight, under the
same conditions, the reactions proceeded steadily to afford
a series of 1,8-dioxo-decahydroacridine derivatives in
good yields (Table 1, entries 15–25).
EXPERIMENTAL
Microwave irradiation was carried out with microwave oven
EmrysTM Creator from Personal Chemistry, Uppsala, Sweden.
Melting points were determined in open capillaries and were
uncorrected. IR spectra were taken on a TENSOR 27 spec-
1
trometer in KBr and reported in cmꢁ1. H NMR spectra were
measured on a Bruke DPX 400 MHz spectrometer in DMSO-
d6 with chemical shift (d) given in ppm relative to TMS as in-
ternal standard, Elemental analyses were determined by using
a Perkin-Elmer 240c elemental analysis instrument. X-Ray
crystallographic analysis was performed with
SMART CCD and a Semens P4 diffractometer.
a Siemens
General procedure for the synthesis of compound 4 with
microwave irradiation. In a 10 mL EmrysTM reaction vial, an
aldehyde 1(1 mmol), dimedone or 1,3-cyclohexanedione 2(2
mmol), primary arylamines 3(1 mmol) and water (1.0 mL)
The structures of all the synthesized compounds were
established on the basis of their spectroscopic data (IR
Table 1
Physical data of compounds 4.
Entry
Product
Ar
2
Ar0-NH2
Time (min)
Mp (ꢀC)
Yield (%)
1
4a
4b
4c
4d
4e
4f
4g
4h
4i
4j
4k
4l
4m
4n
4o
4p
4q
4r
4s
4-Chlorophenyl
4-Bromophenyl
4-Nitrophenyl
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2b
2b
2b
2b
2b
2b
2b
2b
2b
2b
2b
2b
p-Toluidine
p-Toluidine
p-Toluidine
p-Toluidine
p-Toluidine
7
8
283–285
277–278
>300
241–243
263–264
>300
>300
>300
>300
>300
287–288
269–270
245–247
267–269
236–238
263–264
>300
>300
261–262
>300
270–272
298–300
255–257
288–290
290–291
96
93
87
90
92
90
88
89
87
85
88
87
92
95
89
93
89
87
88
92
86
91
89
92
87
2
3
4
8
4-Methoxyphenyl
Benzo[d][1,3]dioxol-5-yl
4-Chlorophenyl
4-Bromophenyl
4-Chlorophenyl
4-Bromophenyl
4-Nitrophenyl
Benzo[d][1,3]dioxol-5-yl
4-Methoxyphenyl
4-Bromophenyl
4-Fluorophenyl
10
10
8
5
6
4-Aminophenol
4-Aminophenol
4-Chlorobenzenamine
4-Chlorobenzenamine
4-Chlorobenzenamine
4-Chlorobenzenamine
4-Chlorobenzenamine
Aniline
7
8
8
8
9
8
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
8
10
8
8
p-Toluidine
p-Toluidine
p-Toluidine
p-Toluidine
p-Toluidine
p-Toluidine
8
8
Benzo[d][1,3]dioxol-5-yl
4-Fluorophenyl
8
4-Bromophenyl
4-Nitrophenyl
9
8
4-Methoxyphenyl
4-Chlorophenyl
4-Methoxyphenyl
4-Fluorophenyl
8
8
4t
4-Aminophenol
4-Chlorobenzenamine
4-Chlorobenzenamine
4-Chlorobenzenamine
Aniline
4u
4v
4w
4x
4y
8
8
4-Chlorophenyl
4-Chlorophenyl
4-Methoxyphenyl
8
8
8
Aniline
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

March 2010
A Green Procedure for the Synthesis of 1,8-Dioxodecahydroacridine Derivatives
under Microwave Irradiation in Aqueous Media without Catalyst
365
compound was obtained according to earlier general procedure.
IR (potassium bromide): 2959, 2930, 1639, 1573, 1512, 1343,
1222, 1146, 834. 1H NMR: 8.14–8.16 (m, 2H, ArH), 7.57–
7.59 (m, 2H, ArH), 7.42 (d, 2H, ArH, J ¼ 6.8), 7.35 (d, 2H,
ArH, J ¼ 7.6), 5.14 (s, 1H, CH), 2.43 (s, 3H, CH3), 2.19–2.24
(m, 4H, 2CH2), 2.00 (d, 2H, CH2, J ¼ 16.0 Hz), 1.80 (d, 2H,
CH2, J ¼ 17.2 Hz), 0.88 (s, 6H, CH3), 0.70 (s, 6H, CH3).
Anal calcd. for C30H32N2O4, C, 74.36; H, 6.66; N, 5.78.
Found: C, 74.16; H, 6.79; N, 5.73.
9-(4-Methoxyphenyl)-10-(4-tolyl)-3,3,6,6-tetrameth-yl-3,4,6,
7,9,10-hexahydroacridine-1,8-[2H,5H]-dione (4d). mp: 281–
283ꢀC. (lit. mp: 285–287ꢀC) [20]. This compound was
obtained according to earlier general procedure. IR (potassium
bromide): 3039, 2947, 2865, 1672, 1572, 1484, 1359, 1175,
1
1010, 837. H NMR: 7.41 (d, 3H, ArH, J ¼ 8.0 Hz), 7.20 (d,
3H, ArH, J ¼ 8.8 Hz), 7.80 (d, 2H, ArH, J ¼ 8.4 Hz), 4.98 (s,
1H, CH), 3.69 (s, 3H, OCH3), 2.43 (s, 3H, CH3), 2.16–2.22
(m, 4H, 2CH2), 1.99 (d, 2H, CH2, J ¼ 16.0 Hz), 1.76 (d, 2H,
CH2, J ¼ 17.2 Hz), 0.88 (s, 6H, CH3), 0.72 (s, 6H, CH3).
Anal calcd. for C31H35NO3. C, 79.28; H, 7.51; N, 2.98. Found:
C, 79.47; H, 7.62; N, 2.79.
9-(Benzo[d][1,3]dioxo-5-yl)-10-(p-tolyl)-3,3,6,6-tetra methyl-
3,4,6,7,9,10-hexahydroacridine-1,8-[2H,5H]-dione (4e). mp
263–264ꢀC. (lit. mp: 272–274ꢀC) [20]. This compound was
obtained according to earlier general procedure. IR (potassium
bromide): 2954, 2871, 1640, 1576, 1486, 1420, 1361, 1278,
1254, 1142, 1042, 813. 1H NMR: 7.16–7.21(m, 4H, ArH),
6.72–6.83 (m, 3H, ArH), 5.94 (s, 2H, CH2) 4.96 (s, 1H, CH),
2.50 (s, 3H, CH3), 2.16–2.20 (m, 4H, 2CH2), 2.02 (d, 2H,
CH2, J ¼ 16.0 Hz), 1.78 (d, 2H, CH2, J ¼ 17.2 Hz), 0.88 (s,
6H, CH3), 0.74 (s, 6H, CH3). Anal calcd. for C31H33NO4: C,
76.99; H, 6.88; N, 2.90. Found: C, 76.78; H, 6.98; N, 2.69.
9-(4-Chlorophenyl)-10-(4-hydroxyphenyl)-3,3,6,6-tetramethyl-
3,4,6,7,9,10-hexahydroacridine-1,8-[2H,5H]-dione (4f). mp
>300ꢀC. (lit. mp: >300ꢀC) [17]. This compound was obtained
according to earlier general procedure. IR (potassium bromide):
3262, 2960, 2875, 1642, 1640, 1566, 1515, 1451, 1364, 1316,
1264, 1225, 1177, 1145, 1090, 1013, 886, 852, 782. 1H NMR:
10.0 (s, 1H, OH), 6.92–7.30 (m, 8H, ArH), 5.01 (s, 1H, CH),
2.17–2.22 (m, 4H, 2CH2), 1.83–2.00 (m, 4H, 2CH2), 0.90 (s,
6H, CH3), 0.72 (s, 6H, CH3). Anal calcd. for C29H30ClNO3: C,
73.17; H, 6.35; N, 2.94. Found: C, 73.32; H, 6.21; N, 3.02.
9-(4-Bromophenyl)-10-(4-hydroxyphenyl)-3,3,6,6-tetramethyl-
3,4,6,7,9,10-hexahydroacridine-1,8-[2H,5H]-dione (4g). mp
>300ꢀC. (lit. mp: >300ꢀC) [17]. This compound was obtained
according to earlier general procedure. IR (potassium bro-
mide): 3162, 2958, 2875, 1638, 1564, 1513, 1463, 1365, 1316,
Figure 1. Molecular structure of 4k.
was mixed and then capped. The mixture was irradiated for a
given time at power of 200 W at 140ꢀC. Upon completion,
monitored by TLC, the reaction mixture was cooled to room
temperature. The solid product was filtered to give the crude
product, which was further purified by recrystallization from
EtOH (95%).
9-(4-Chlorophenyl)-10-(p-tolyl)-3,3,6,6-tetramethyl-3,4,6,7,9,
10-hexahydroacridine-1,8-[2H,5H]-dione (4a). mp 283–285ꢀC.
(lit. mp: 265–267ꢀC) [19]. This compound was obtained accord-
ing to earlier general procedure. IR (potassium bromide): 3058,
2958, 2888, 1639, 1575, 1511, 1486, 1450, 1361, 1278, 1221,
1144, 1089, 841. 1H NMR: 7.41 (d, 2H, ArH, J ¼ 8.4 Hz),
7.29–7.31 (m, 6H, ArH), 5.02 (s, 1H, CH), 2.50 (s, 3H, CH3),
2.17–2.22 (m, 4H, 2CH2), 2.00 (d, 2H, CH2, J ¼ 16.0 Hz), 1.77
(d, 2H, CH2, J ¼ 17.2 Hz), 0.88 (s, 6H, CH3), 0.71 (s, 6H,
CH3). Anal calcd. for C30H32ClNO2: C, 76.01; H, 6.80; N, 2.95.
Found: C, 76.25; H, 6.71; N, 3.02.
1
1264, 1178, 1146, 1070, 1009, 887, 850, 734, 779. H NMR:
9-(4-Bromophenyl)-10-(p-tolyl)-3,3,6,6-tetramethyl-3,4,6,7,9,
10-hexahydroacridine-1,8-[2H,5H]-dione (4b). mp 277–278ꢀC.
(lit. mp: 265–267ꢀC) [20]. This compound was obtained
according to earlier general procedure. IR (potassium bro-
mide): 3035, 2957, 2870, 1640, 1576, 1511, 1471, 1362, 1278,
1222, 1145, 1069, 842. 1H NMR: 7.40–7.45 (m, 4H, ArH),
7.25–7.32 (m, 4H, ArH), 5.00 (s, 1H, CH), 2.42 (s, 3H, CH3),
2.17–2.22 (m, 4H, 2CH2), 1.99 (d, 2H, CH2, J ¼ 16.0 Hz),
1.77 (d, 2H, CH2, J ¼ 16.0 Hz), 0.88 (s, 6H, CH3), 0.71(s,
6H, CH3). Anal calcd. for C30H32BrNO2: C, 69.50; H, 6.22; N,
2.70. Found: C, 69.39; H, 6.13; N, 2.82.
10.0 (s, 1H, OH), 7.42 (d, 2H, ArH, J ¼ 8.0 Hz), 7.24 (d, 2H,
ArH, J ¼ 8.0 Hz), 6.90–7.22 (m, 4H, ArH), 5.1 (s, 1H, CH),
2.16–2.23 (m, 4H, 2CH2), 1.83–2.00 (m, 4H, 2CH2), 0.90 (s,
6H, CH3), 0.72 (s, 6H, CH3). Anal calcd. for C29H30BrNO3. C,
66.92; H, 5.81; N, 2.69. Found: C, 67.08; H, 5.65; N, 2.54.
9-(4-Chlorophenyl)-10-(4-chlorophenyl)-3,3,6,6-tetramethyl-
3,4,6,7,9,10-hexahydroacridine-1,8-[2H,5H]-dione (4h). mp
>300ꢀC. (lit. mp: 284–286ꢀC) [20]. This compound was
obtained according to earlier general procedure. IR (potassium
bromide): 2958, 2870, 1639, 1578, 1490, 1361, 1361, 1263,
1221, 1145, 1090, 1014, 840, 739. 1H NMR: 7.68 (d, 2H,
ArH, J ¼ 12.0 Hz), 7.47–7.49 (m, 2H, ArH), 7.28–7.33 (m,
4H, ArH), 5.01 (s, 1H, CH), 2.17–2.22 (m, 4H, 2CH2), 2.01
9-(4-Nitrophenyl)-10-(4-tolyl)-3,3,6,6-tetramethyl-3,4,6,7,9,10-
hexahydroacridine-1,8-[2H,5H]dione (4c). mp >300ꢀC. This
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

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Z.-Q. Tang, Y. Chen, C.-N. Liu, K.-Y. Cai, and S.-J. Tu
Vol 47
(d, 2H, CH2, J ¼ 16.0 Hz), 1.77 (d, 2H, CH2, J ¼ 16.0 Hz),
0.89 (s, 6H, CH3), 0.72 (s, 6H, CH3). Anal calcd. for
C29H29Cl2NO2: C, 70.44; H, 5.91; N, 2.83. Found: C, 70.21;
H, 6.02; N, 2.71.
9-(4-Fluorophenyl)-10-(4-tolyl)-3,3,6,6-tetramethyl-3,4,6,7,9,10-
hexahydroacridine1,8-[2H,5H]-dione (4n). mp 267–269ꢀC. (lit.
mp: 262–294ꢀC) [17]. This compound was obtained according
to earlier general procedure. IR (potassium bromide): 3063,
2931, 2870, 1651, 1575, 1508, 1451, 1142, 1000, 843. 1H
NMR: 7.41 (d, 2H, ArH, J ¼ 7.6 Hz), 7.30–7.34 (m, 4H,
ArH), 7.04–7.08 (m, 2H, ArH), 5.03 (s, 1H, CH), 2.42 (s, 3H,
CH3), 2.20–2.22 (m, 4H, 2CH2), 2.00 (d, 2H, CH2, J ¼ 16.0
Hz), 1.77 (d, 2H, CH2, J ¼ 17.6 Hz), 0.88 (s, 6H, CH3), 0.71
(s, 6H, CH3). Anal calcd. for C30H32FNO2: C, 78.75; H, 7.05;
N, 3.06. Found: C, 78.94; H, 7.18; N, 3.02.
9-(4-Bromophenyl)-10-(4-chlorophenyl)-3,3,6,6-tetramethyl-
3,4,6,7,9,10-hexahydroacridine-1,8-[2H,5H]-dione (4i). mp:
254–256ꢀC. (lit. mp: 249–251ꢀC) [20]. This compound was
obtained according to earlier general procedure. IR (potassium
bromide): 2958, 2869, 1639, 1578, 1577, 1491, 1361, 1221,
1145, 1089, 1009, 839. 1H NMR: 7.68 (d, 2H, ArH, J ¼ 8.0
Hz), 7.42–7.48 (m, 4H, ArH), 7.26 (d, 2H, ArH, J ¼ 8.0 Hz),
4.99 (s, 1H, CH), 2.17–2.23 (m, 4H, 2CH2), 2.01 (d, 2H, CH2,
J ¼ 16.0 Hz), 1.76 (d, 2H, CH2, J ¼ 16.0 Hz), 0.89 (s, 6H,
CH3), 0.72 (s, 6H, CH3). Anal calcd. for C29H29BrClNO2: C,
64.63; H, 5.42; N, 2.60. Found: C, 64.81; H, 5.28; N, 2.68.
9-(4-Nitrophenyl)-10-(4-chlorophenyl)-3,3,6,6-tetra methyl-
3,4,6,7,9,10-hexahydroacridine-1,8-[2H,5H]-dione (4j). mp
>300ꢀC. This compound was obtained according to earlier
general procedure. IR (potassium bromide): 2959, 2870, 1638,
1577, 1491, 1361, 1342, 1222, 1145, 1089, 1009, 831. 1H
NMR: 7.67–7.70 (m, 2H, ArH), 7.48–7.50 (m, 2H, ArH),
7.28–7.33 (m, 4H, ArH), 5.01 (s, 1H, CH), 2.17–2.22 (m, 4H,
2CH2), 2.02 (d, 2H, CH2, J ¼ 16.0 Hz), 1.77 (d, 2H, CH2, J
¼ 16.0 Hz), 0.89 (s, 6H, CH3), 0.72 (s, 6H, CH3). Anal calcd.
for C29H29ClN2O4: C, 68.97; H, 5.79; N, 5.55. Found: C,
69.14; H, 5.61; N, 5.42.
9-(Benzo[d][1,3]dioxo-5-yl)-10-(4-chlorophenyl)-3,3, 6,6-tetra-
methyl-3,4,6,7,9,10-hexahydroacridine-1,8-[2H,5H]-dione
(4k). mp 287–288ꢀC. (lit. mp: 287–288ꢀC) [24]. This com-
pound was obtained according to earlier general procedure. IR
(potassium bromide): 2955, 2871, 1641, 1578, 1490, 1360,
1254, 1221, 1141, 1042, 921, 813. 1H NMR: 7.68 (d, 2H,
ArH, J ¼ 8.8 Hz), 7.42–7.45 (m, 2H, ArH), 6.77–6.79 (m, 3H,
ArH), 5.94 (s, 2H, CH2), 4.96 (s, 1H, CH), 2.16–2.20 (m, 4H,
2CH2), 2.03 (d, 2H, CH2, J ¼ 17.6 Hz), 1.78 (d, 2H, CH2, J
¼ 17.2 Hz), 0.89 (s, 6H, CH3), 0.75 (s, 6H, CH3). Anal calcd.
for C30H30ClNO4: C, 71.49; H, 6.00; N, 2.78. Found: C,
71.23; H, 6.18; N, 2.69.
9-(Benzo[d][1,3]dioxo-5-yl)-10-(4-tolyl)-3,4,6,7,9,10-hexahy-
droacridine-1,8-[2H,5H]-dione (4o). mp 236–238ꢀC. This com-
pound was obtained according to earlier general procedure. IR
(potassium bromide): 3031, 2945, 2888, 1642, 1570, 1486, 1362,
1
1285, 1231, 1135, 1040, 857, 799. H NMR: 7.37 (d, 3H, ArH,
J ¼ 8.0 Hz), 7.16–7.18 (m, 1H, ArH), 6.72–6.79 (m, 3H, ArH),
5.94 (s, 2H, CH2), 5.06 (s, 1H, CH), 2.97 (s, 3H, CH3), 2.18–
2.24 (m, 6H, 3CH2), 1.91–1.96 (m, 2H, CH2), 1.76–1.84 (m, 2H,
CH2), 1.59–1.65 (m, 2H, CH2). Anal calcd. for C27H25NO4: C,
75.86; H, 5.89; N, 3.28. Found: 75.81; H, 6.01; N, 3.41.
9-(4-Fluorophenyl)-10-(p-tolyl)-3,4,6,7,9,10-hexahy-droacri-
dine-1,8-[2H,5H]-dione (4p). mp 263–264ꢀC. This compound
was obtained according to earlier general procedure. IR (potas-
sium bromide): 3059, 2929, 2870, 1633, 1571, 1507, 1360,
1284, 1231, 1134, 839. 1H NMR: 7.37–7.39 (m, 3H, ArH),
7.19–7.31 (m, 3H, ArH), 7.02–7.07 (m, 2H, ArH), 5.13 (s, 1H,
CH), 2.40 (s, 3H, CH3), 2.18–2.22 (m, 6H, 3CH2), 1.92–1.97
(m, 2H, CH2), 1.79–1.84 (m, 2H, CH2), 1.63–1.65 (m, 2H,
CH2). Anal calcd. for C26H24FNO2: C, 77.78; H, 6.03; N,
3.49. Found: C, 77.94; H, 5.85; N, 3.31.
9-(4-Bromophenyl)-10-(p-tolyl)-3,4,6,7,9,10-hexahy-droacri-
dine-1,8-[2H,5H]-dione (4q). mp >300ꢀC. (lit. mp: > 300ꢀC)
[17]. This compound was obtained according to earlier general
procedure. IR (potassium bromide): 3040, 2923, 2867, 1644,
1572, 1510, 1485, 1361, 1283, 1230, 1134, 1069, 831. 1H
NMR: 7.37–7.43 (m, 5H, ArH), 7.24 (d, 2H, ArH, J ¼ 8.4
Hz), 7.14 (d, 1H, ArH, J ¼ 8.4 Hz), 5.10 (s, 1H, CH), 2.40 (s,
3H, CH3), 2.18–2.21 (m, 8H, 4CH2), 1.92–1.97 (m, 2H, CH2),
1.77–1.85 (m, 2H, CH2). Anal calcd. for C26H24BrNO2: C,
67.54; H, 5.23; N, 3.03. Found: C, 67.72; H, 5.06; N, 3.19.
9-(4-Nitrophenyl)-10-(p-tolyl)-3,4,6,7,9,10-hexahy-droacridine-
1,8-[2H,5H]-dione (4r). mp >300ꢀC. (lit. mp: > 300ꢀC) [17].
This compound was obtained according to earlier general pro-
cedure. IR (potassium bromide): 2953, 2915, 1631, 1600,
1574, 1511, 1342, 1284, 1230, 1179, 1132. 1H NMR: 7.31–
8.13 (m, 8H, ArH), 5.23 (s, 1H, CH), 2.40 (s, 3H, CH3), 1.94–
2.89 (m, 8H, 4CH2), 1.79–1.85 (m, 2H, CH2), 1.62–1.65 (m,
2H, CH2). Anal calcd. for C26H24N2O4: C, 72.88; H, 5.65; N,
6.54. Found: C, 72.72; H, 5.84; N, 6.70.
9-(4-Methoxyphenyl)-10-(4-chlorophenyl)-3,3,6,6-tetramethyl-
3,4,6,7,9,10-hexahydroacridine1,8-[2H,5H]-dione (4l). mp 269–
270ꢀC. (lit. mp: 269–271ꢀC) [27]. This compound was
obtained according to earlier general procedure. IR (potassium
bromide): 2952, 1641, 1578, 1491, 1361, 1259, 1173, 1140,
998, 834, 740. 1H NMR: 7.68 (d, 2H, ArH, J ¼ 8.0), 7.44–
7.47 (m, 2H, ArH ), 7.21 (d, 2H, ArH, J ¼ 8.0 Hz), 6.80 (d,
2H, ArH, J ¼ 8.0 Hz), 4.97 (s, 1H, CH), 3.69 (s, 3H, OCH3),
2.16–2.22 (m, 4H, 2CH2), 2.00 (d, 2H, CH2, J ¼ 16.0 Hz),
1.77 (d, 2H, CH2, J ¼ 17.6 Hz), 0.89 (s, 6H, CH3), 0.73 (s,
6H, CH3). Anal calcd. for C30H32ClNO3: C, 73.53; H, 6.58; N,
2.86. Found: C, 73.73; H, 6.62; N, 2.71.
9-(4-Bromophenyl)-10-phenyl-3,3,6,6-tetramethyl-3,4,6,7,9,10-
hexahydroacridine-1,8-[2H,5H]-dione (4m). mp 285–287ꢀC.
(lit. mp: > 300ꢀC) [20]. This compound was obtained accord-
ing to earlier general procedure. IR (potassium bromide):
3060, 2956, 2869, 1639, 1577, 1491, 1452, 1361, 1261, 1176,
1008, 838. 1H NMR: 7.55–7.64 (m, 3H, ArH), 7.45 (d, 4H,
ArH, J ¼ 8.0 Hz), 7.27 (d, 2H, ArH, J ¼ 8.0 Hz), 5.01 (s, 1H,
CH), 2.18–2.23 (m, 4H, 2CH2), 2.01 (d, 2H, CH2, J ¼ 16.0
Hz), 1.75 (d, 2H, CH2, J ¼ 16.0 Hz), 0.87 (s, 6H, CH3), 0.71
(s, 6H, CH3). Anal calcd. for C29H30BrNO2: C, 69.05; H, 5.99;
N, 2.78. Found: 69.18; H, 5.76; N, 2.54.
9-(4-Methoxyphenyl)-10-(p-tolyl)-3,4,6,7,9,10-hexahydroacridine-
1,8-[2H,5H]-dione (4s). mp 241.2–243.0ꢀC. (lit. mp: 256–
257ꢀC) [17]. This compound was obtained according to earlier
general procedure. IR (potassium bromide): 2938, 1637, 1569,
1509, 1360, 1287, 1232, 1181, 1130, 954, 913, 825, 758. 1H
NMR: 7.37–7.86 (m, 4H, ArH), 7.18 (d, 2H, ArH, J ¼ 8.8
Hz), 6.80 (d, 2H, ArH, J ¼ 8.4 Hz), 5.07 (s, 1H, CH), 3.70 (s,
3H, OCH3), 2.40 (s, 3H, CH3), 2.18–2.25 (m, 6H, 3CH2),
1.80–1.83 (m, 4H, 2CH2), 1.59–1.61 (m, 2H, CH2). Anal
calcd. for C27H27NO3: C, 78.42; H, 6.58; N, 3.39. Found: C,
78.69; H, 6.72; N, 3.12.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

March 2010
A Green Procedure for the Synthesis of 1,8-Dioxodecahydroacridine Derivatives
under Microwave Irradiation in Aqueous Media without Catalyst
367
Project (No.08QLT001), and the Foundation of Xuzhou Institute
of Technology College (No. XKY2007241) for the financial
support.
9-(4-Chlorophenyl)-10-(4-hydroxyphenyl)-3,4,6,7,9,10-hexa-
hydroacridine-1,8-[2H,5H]-dione (4t). mp >300ꢀC. (lit. mp:
>300ꢀC) [17]. This compound was obtained according to ear-
lier general procedure. IR (potassium bromide): 3161, 1636,
1561, 1489, 1453, 1385, 1362, 1269, 1234, 1140, 1088, 959.
1H NMR: 9.94 (s, 1H, OH), 6.89–7.28 (m, 8H, ArH), 5.11 (s,
1H, CH), 2.17–2.25 (m, 6H, 3CH2), 1.96–2.04(m, 2H, CH2),
1.80–1.86 (m, 2H, CH2), 1.59–1.67 (m, 2H, CH2). Anal calcd.
for C25H22ClNO3: C, 71.51; H, 5.28; N, 3.34. Found: C,
71.38; H, 5.32; N, 3.40.
REFERENCES AND NOTES
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Yoon, N. S. Tetrahedron 2000, 56, 7747.
9-(4-Methoxyphenyl)-10-(4-chlorophenyl)-3,4,6,7,9, 10-hexa-
hydro acridine-1,8-[2H,5H]-dione (4u). mp 270–272ꢀC. This
compound was obtained according to earlier general procedure.
IR (potassium bromide): 2938, 1634, 1569, 1509, 1363, 1284,
[4] Khadilkar, B. M.; Gaikar, V. G.; Chitnavis, A. A. Tetrahe-
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1
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1230, 1181, 1132, 955, 846, 756. H NMR: 7.68 (d, 2H, ArH,
J ¼ 12.0), 7.45–7.47 (m, 2H, ArH), 7.21 (d, 2H, ArH, J ¼ 8.0
Hz), 6.80 (d, 2H, ArH, J ¼ 8.0 Hz), 4.97 (s, 1H, CH), 3.69 (s,
3H, OCH3), 2.19–2.23 (m, 6H, 3CH2), 1.82–1.84 (m, 4H,
2CH2), 1.59–1.62 (m, 2H, CH2). Anal calcd. for C26H24ClNO3:
C, 71.97; H, 5.57; N, 3.23. Found: C, 72.12; H, 5.38; N, 3.32.
9-(4-fluorophenyl)-10-(4-chlorophenyl)-3,4,6,7,9,10-hexahy-
droacridine-1,8-[2H,5H]-dione (4v). mp 298–299ꢀC. This com-
pound was obtained according to earlier general procedure. IR (po-
tassium bromide): 2962, 1634, 1572, 1505, 1360, 1283, 1232, 1182,
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1
1132, 956, 839, 759. H NMR: 7.65 (d, 2H, ArH, J ¼ 8.0), 7.29–
7.33 (m, 3H, ArH), 7.02–7.06 (m, 3H, ArH), 5.12 (s, 1H, CH),
2.19–2.24 (m, 6H, 3CH2), 1.92–1.97 (m, 2H, CH2), 1.80–1.84 (m,
2H, CH2), 1.62–1.65 (m, 2H, CH2). Anal calcd. for C25H21ClFNO2:
C, 71.17; H, 5.02; N, 3.32. Found: C, 71.02; H, 5.18; N, 3.21.
9-(4-Chlorophenyl)-10-(4-chlorophenyl)-3,4,6,7,9,10-hexahydro-
acridine-1,8[2H,5H]-dione (4w). mp 255–257ꢀC. This com-
pound was obtained according to earlier general procedure. IR
(potassium bromide): 2946, 1633, 1571, 1489, 1362, 1284,
[13] Loev, B.; Goodman, M. M.; Snader, K. M.; Tedeschi, R.;
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1
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molecules 1993, 26, 4560.
1183, 1134, 1089, 858, 821, 757. H NMR: 7.63–7.66 (m, 2H,
ArH), 7.53–7.57 (m, 2H, ArH), 7.17–7.20 (m, 2H, ArH), 6.79
(d, 2H, ArH, J ¼ 8.0), 5.06 (s, 1H, CH), 2.18–2.26 (m, 6H,
3CH2), 1.91–1.97 (m, 2H, CH2), 1.80–1.85 (m, 2H, CH2),
1.59–1.65 (m, 2H, CH2). Anal calcd. For C25H21Cl2NO2: C,
68.50; H, 4.83; N, 3.20. Found: C, 68.38; H, 4.99; N, 3.07.
9-(4-Chlorophenyl)-10-phenyl-3,4,6,7,9,10-hexahydroacridine-
1,8-[2H,5H]-dione (4x). mp 288–290ꢀC. This compound was
obtained according to earlier general procedure. IR (potassium
bromide): 3044, 2953, 1637, 1570, 1489, 1425, 1360, 1269,
1281, 1137, 1088, 956, 835. 1H NMR: d7.53–7.60 (m, 3H,
ArH), 7.19–7.33 (m, 6H, ArH), 5.13 (s, 1H, CH), 2.19–2.25
(m, 6H, 3CH2), 1.90–1.95 (m, 2H, CH2), 1.79–1.81 (m, 2H,
CH2), 1.60–1.63 (m, 2H, CH2). Anal calcd. for C25H22ClNO2:
C, 74.34; H, 5.49; N, 3.47. Found: C, 74.18; H, 5.62; N, 3.31.
9-(4-Methoxyphenyl)-10-phenyl-3,4,6,7,9,10-hexa-hydro-
acridine-1,8-[2H,5H]-dione (4y). mp 290–291ꢀC. (lit. mp:
270–272ꢀC) [28]. IR (potassium bromide): 2943, 2887, 1635,
1569, 1509, 1359, 1284, 1229, 1181, 1132, 953, 857. 1H
NMR: 7.55–7.57 (m, 4H, ArH), 7.30–7.35 (m, 1H, ArH),
7.18–7.21 (m, 2H, ArH), 6.79–7.82 (m, 2H, ArH), 5.09 (s, 1H,
CH), 3.70 (s, 3H, OCH3), 2.19–2.24 (m, 6H, 3CH2), 1.84–1.90
(m, 2H, CH2), 1.79–1.81 (m, 2H, CH2),1.60–1.64 (m, 2H,
CH2). Anal calcd. for C26H25NO3: C, 78.17; H, 6.31; N, 3.51.
Found: C, 78.01; H, 6.52; N, 3.58.
[17] Tu, S. J.; Li, T. J.; Zhang, Y.; Shi, F.; Xu J. N.; Wang, Q.;
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[22] The 12 principles are as follows: prevention, atom econ-
omy, less hazardous chemical synthesis, designing safer chemicals,
safer solvents, design for energy efficiency, use of renewable feed-
stocks, reduce derivatives, catalysis, design for degradation, real-time
analysis for pollution prevention, inherently safer chemistry for acci-
dent prevention.
[23] Tang, Z. Q.; Cao, X. D.; Jiang, B.; Li, C. M.; Zhou, D. X.
Acta Cryst 2007, E63, o3811.
[24] Liu, Q. D.; Tang, Z. Q.; Du, X. H. Acta Cryst 2007, E63,
o3924.
[25] Chen, Y.; Hao, W. J.; Tang, Z. Q.; Jiang, B.; Li, C. M.
Acta Cryst 2007, E63, o3934.
[26] Tang, Z. Q.; Liu, C. N.; Hao, W. J.; Wu, S. S. Acta Cryst
2008, E64, o1844.
[27] Shi, D. Q.; Ni, S. N.; Yang, F.; Shi, J. W.; Dou, G. L.; Li,
X. Y.; Wang, X. S. J Heterocycl Chem 2008, 45, 653.
[28] Chandrasekhar, S.; Rao, Y. S.; Sreelakshmi, L.; Mahipal,
B.; Reddy, C. R. Synthesis 2008, 1737.
Acknowledgments. The authors thank the National Natural
Science Foundation of China (No. 20810102050), the Qing Lan
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet