A convenient synthesis of 9-aryl-3,3,6,6-tetramethyl-1,2,3,4,5,6,7,8,9,10-decahydroacridine-1,8-diones under microwave irradiation without solvent

Article abstract of DOI:10.1081/SCC-120005427

A convenient synthetic method for the title compounds are described. Heating 1, 2 and 3 under microwave irradiation for 3-5 min to afford 4. The structure of the compound 4c has been thoroughly studied by X-ray crystallographic analysis.

Full text of DOI:10.1081/SCC-120005427

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A CONVENIENT SYNTHESIS OF 9-ARYL-3,3,6,6-
TETRAMETHYL-1,2,3,4,5,6,7,8,9,10-
DECAHYDROACRIDINE-1,8-DIONES UNDER MICROWAVE
IRRADIATION WITHOUT SOLVENT
Shu-Jiang Tu a , Zaisheng Lu a , Daqing Shi a , Changsheng Yao a , Yuan Gao b & Cheng Guo c
a Department of Chemistry, Xuzhou Normal University, Xuzhou, Jiangsu, 221009, P.R. China
b Department of Chemistry, Shenzheng University, Shenzheng, 518000, P.R. China
c Department of Applied Chemistry, Nanjing University of Chemical Technology, Nanjing,
210009, P.R. China
Version of record first published: 18 Oct 2011.
To cite this article: Shu-Jiang Tu , Zaisheng Lu , Daqing Shi , Changsheng Yao , Yuan Gao & Cheng Guo (2002): A CONVENIENT
SYNTHESIS OF 9-ARYL-3,3,6,6-TETRAMETHYL-1,2,3,4,5,6,7,8,9,10-DECAHYDROACRIDINE-1,8-DIONES UNDER MICROWAVE
IRRADIATION WITHOUT SOLVENT, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 32:14, 2181-2185
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SYNTHETIC COMMUNICATIONS
Vol.32, No.14, pp.2181–2185, 2002
A CONVENIENT SYNTHESIS OF 9-ARYL-
3,3,6,6-TETRAMETHYL-1,2,3,4,5,6,7,8,9,10-
DECAHYDROACRIDINE-1,8-DIONES
UNDER MICROWAVE IRRADIATION
WITHOUT SOLVENT
Shu-Jiang Tu,1, Zaisheng Lu,1 Daqing Shi,1
*
Changsheng Yao,1 Yuan Gao,2 and Cheng Guo3
1Department of Chemistry, Xuzhou Normal University,
Jiangsu, Xuzhou, 221009, P.R. China
2Department of Chemistry, Shenzheng University,
Shenzheng, 518000, P.R. China
3Department of Applied Chemistry, Nanjing University
of Chemical Technology, 210009, Nanjing, P.R. China
ABSTRACT
A convenient synthetic method for the title compounds are
described.Heating 1, 2 and 3 under microwave irradiation for
3–5 min to afford 4.The structure of the compound 4c has
been thoroughly studied by X-ray crystallographic analysis.
*Corresponding author.E-mail: laotu2001@263n. et
2181
DOI: 10.1081/SCC-120005427
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

2182
TU ET AL.
Since microwave heating was used for organic synthesis by Gedye[1]
in 1986, the microwave organic chemistry has been a topic of continuing
interest.Another area that has been drawing many researches in organic
synthesis is organic reaction under dry condition.[2] We are currently
studying new synthetic methods for heterocyclic compounds by taking
advantage of both microwave irradiation and dry reaction condition.1,4-
Dihydropyridines (1,4-DHPs) are well-known compounds as a consequence
of their pharmacological profile as calcium channel modulators.[3] The
chemical modifications carried out on the DHP ring such as the presence
of different substituents,[4] heteroatoms[5] have allowed expansion of the
receptor level.However, bearing three fused ring have been less well studied.
By refluxing dimedone, aromatic aldehyde in ammonium hydroxide solution
4 was obtained,[6] and the yields were poor.Margarita Suarez et al.reported
that 4 was synthesized by reaction of aromatic aldehyde, dimedone, ammo-
nium (acetate using two types of alumina (neutral or basic) as mineral solid
supports, DMF as energy transfer medium under microwave irradiation,
only five products were synthesized.[7] Here, we would like to report another
method, thus, using ammonium bicarbonate instead of ammonium acetate
under microwave irradiation without solid supports and energy transfer
medium, and the yields were higher.We also present a structure study of
4c by X-ray analysis.
The results were listed in Table 1.
All the compounds obtained gave analysis for C, H, N in good
agreement with calculated values.The structures were established on the
basis of spectroscopic data and confirmed by X-ray diffraction studies on
monocrystal of 4c (Figure 1).[8]
EXPERIMENTAL
Melting points were determined in a capillary tube and are uncor-
rected.The 1H NMR spectra were recorded on a DPX 300 MHz spectro-
meter with TMS as internal standard.The IR spectra were obtained with

9-ARYL-1,8-DIONES
2183
Table 1. The Synthesis of 4
Entry
Ar
Time (min)
Yield (%)
4a
4b
4c
4d
4e
4f
C6H5
2-ClC6H4
4-ClC6H4
4-(CH3)2NC6H4
3-O2NC6H4
3,4-(CH3O)2C6H3
3,4-(OCH2O)C6H3
4-CH3OC6H4
5
4
4
7
4
6
6
7
90
85
92
91
83
89
91
89
4g
4h
Figure 1. X-ray crystal structure of 4c.
SE-1730 instrument as potassium bromide pellets.Elemental analyses were
determined by using Perkin-Elmer 240c elemental analyser.Crystal struc-
ture was obtained with CAD4 diffractometer.Benzaldehyde was distilled
before used, all other reagents were commercially available used without

2184
TU ET AL.
further purification.Microwave irradiation was carried out with a modifi-
catory commercial microwave oven (2450 MHz, 650 W) under atmospheric
pressure.
General Procedure
A dry flask (25 mL) was charged with the aromatic aldehyde 1 (5 mmol),
dimedone 2 (10 mmol) and ammonium bicarbonate 3 (7.5 mmol). The flask
was then connected with refluxing equipment.After microwave irradiation
for 4 ꢀ 7 min, the reaction mixture was cooled and washed with ethanol
(3 mL).The crude products were purified by recrystallization from 95%
ethanol to afford 4.
4a: M.p. 190–192ꢁC.(lit.190–192 ꢁC).[6]
4b: M.p. 221–223ꢁC.(lit.222–224 ꢁC).[7]
4c: M.p. 296–298ꢁC, IR (KBr, ꢀ, cmꢂ1): 3383 (NH), 1623 (C¼O), 1603
(N-C¼O); 1H NMR (CDCl3, ꢁ, ppm): 0.93 (s, 6H, 2CH3), 1.05 (s, 6H,
2CH3), 2.21–2.25 (m, 8H, 4CH), 5.06 (s, 1H, CH), 7.12–7.32 (m, 4H,
ArH), 7.72 (s, 1H, NH). Elementary analysis: found (%): C, 72.03, H,
6.72, N, 3.50; Calcd. for: C23H26ClNO2: C, 71.96, H, 6.83, N, 3.65.
4d: M.p. 263–265ꢁC.(lit.264–266 ꢁC).[6]
4e: M.p. 283–285ꢁC.(lit.285–286 ꢁC).[7]
4f: M.p. 258–260ꢁC.IR (KBr, ꢀ, cmꢂ1): 3384 (NH), 1623 (C¼O), 1602
1
(N-C¼O); H NMR (CDCl3, ꢁ, ppm): 0.934 (s, 6H, 2CH3), 1.05 (s, 6H,
2CH3), 2.10–2.30 (m, 8H, 4CH), 3.76 (s, 6H, 2CH3O), 5.05 (s, 1H, CH),
6.74–6.93 (m, 3H, ArH), 8.18 (s, 1H, NH). Elementary analysis: found (%):
C, 73.43, H, 7.54, N, 3.31; Calcd. for: C25H31NO4: C, 73.32, H, 7.63, N, 3.42.
4g: M.p. 324–326ꢁC.IR (KBr, ꢀ, cmꢂ1): 3280 (NH), 1620 (C¼O), 1601
(N-C¼O); 1H NMR (CDCl3, ꢁ, ppm): 1.00 (s, 6H, 2CH3), 1.10 (s, 6H, 2CH3),
2.16–2.40 (m, 8H, 4CH), 5.00 (s, 1H, CH), 5.85 (s, 2H, OCH2O), 6.63–6.85
(m, 3H, ArH), 7.27 (s, 1H, NH). Elementary analysis: found (%): C, 73.42,
H, 6.81, N, 3.44; Calcd. for: C24H27NO4: C, 73.26, H, 6.92, N, 3.56.
4h: M.p. 269–270ꢁC.(lit.270–272 ꢁC).[6]
REFERENCES
1. Gedye, R.; Smith, F.; Westawaym, K.; Humera, A.; Baldisern, L.;
Laberge, L.J.Tetrahedron Lett. 1986, 27, 279.
2. Christopher, R.; Robert, S.; Trainor, W. Aust. J. Chem. 1995, 48, 1665;
Loupy, A.Topics in Current Chemistry 1999, 206, 153; Tanaka, K.;
Toda, F.Chem.Rev. 2000, 100, 1025.

9-ARYL-1,8-DIONES
2185
3. Janis, R.A.; Silver, P.J.; Triggle, D. J. Adv. Drug Res. 1987, 16, 309;
Bossert, F.; Vater, W. Med. Res. Rev. 1989, 9, 291.
4.Eisner, U; .Kuthan, JC. hemR. ev. 1972, 72, 1; Stout, D.M.; Meyers,
A.I. Chem. Rev. 1982, 82, 223; Bossert, F.; Meyers, H.; Mehinger, E.
Angew.Chem.Int.Ed.Engl.1981
Ind.Eng.Chem.Prod.Res.Dev.
, 20, 762; Kuthan, J.; Kurfurst, A.
1982, 211, 191.
5. Chorvat, R.J.; Rorig, K.J. J. Org. Chem. 1988, 53, 5779; Kappe, C.O.;
Fabian, W.M.F. Tetrahedron 1997, 53, 2803; Kappe, C.O. Tetrahedron
1993, 49, 6937.
6. Martin, N.; Quinteiro, M.; Seoane, C. et al. J. Heterocyclic Chem. 1995,
32, 235.
7. Suarez, M.; Loupy, A.; Salfran, E.; Moran, L.; Rolando, E.
Heterocycles 1999, 51, 21.
8.X-ray analysis of 4c: Empirical formula C23H26ClNO2, F.W. 383.90,
T ¼ 293(2) K, orthorhombic, space group Pna2(1), a ¼ 14.125(3) A, b ¼
14.118(3) A, c ¼ 10.719(2) A, ꢂ ¼ 90ꢁ, ꢃ ¼ 90ꢁ, ꢄ ¼ 90ꢁ, V ¼ 2137.5(7) A3,
Z ¼ 4, Dc ¼ 1.193 Mg/m3, F(000) ¼ 816, ꢅ (MoKꢂ) ¼ 0.71073 A, ꢆ ¼
0.195 mmꢂ1, 2.04ꢁ<ꢇ<24.96ꢁ, R ¼ 0.0507, wR ¼ 0.1536. S ¼ 1.034,
largest diff.peak and hole: 03. 41 and ꢂ0.317 eA3.
Received in Japan February 24, 2001