A Novel Reaction of Aldeoxime with Dimedone under Microwave Irradiation

Article abstract of DOI:10.1081/SCC-120030317

The reaction of aldeoxime with dimedone and ammonium acetate in glycol under microwave irradiation has been carried out, elimination and cyclization happened and acridine derivatives were obtained. The structure of the product has been thoroughly studied by x-ray crystallographic analysis.

Full text of DOI:10.1081/SCC-120030317

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A Novel Reaction of Aldeoxime with Dimedone Under
Microwave Irradiation
Shujang Tu a , Yuan Gao b , Chunbao Miao a , Tuanjie Li a , Xiaojing Zhang a , Songlei Zhu
a , Fang Fang a & Daqing Shi a
a Department of Chemistry, Key Laboratory of Biotechnology on Medical Plant , Xuzhou
Normal University , Jiangsu, Xuzhou, Jiangsu, 221009, P.R. China
b Department of Chemistry , Shenzhen University , Shenzhen, Guangdong, P.R. China
Published online: 21 Aug 2006.
To cite this article: Shujang Tu , Yuan Gao , Chunbao Miao , Tuanjie Li , Xiaojing Zhang , Songlei Zhu , Fang Fang &
Daqing Shi (2004) A Novel Reaction of Aldeoxime with Dimedone Under Microwave Irradiation, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 34:7, 1289-1294, DOI: 10.1081/
SCC-120030317
To link to this article: http://dx.doi.org/10.1081/SCC-120030317
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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 7, pp. 1289–1294, 2004
A Novel Reaction of Aldeoxime
with Dimedone Under
Microwave Irradiation
2
1
1
Shujang Tu,1, Yuan Gao, Chunbao Miao, Tuanjie Li,
*
Xiaojing Zhang,1 Songlei Zhu,1 Fang Fang,1 and Daqing Shi1
1Department of Chemistry, Key Laboratory of Biotechnology on Medical
Plant, Xuzhou Normal University, Jiangsu, Xuzhou, Jiangsu, P.R. China
2Department of Chemistry, Shenzhen University, Shenzhen,
Guangdong, P.R. China
ABSTRACT
The reaction of aldeoxime with dimedone and ammonium acetate in
glycol under microwave irradiation has been carried out, elimination and
cyclization happened and acridine derivatives were obtained. The structure
of the product has been thoroughly studied by x-ray crystallographic
analysis.
Key Words: Aldeoxime; Dimedone; Microwave irradiation; Cyclization.
*
Correspondence: Shujang Tu, Department of Chemistry, Key Laboratory of Biotech-
nology on Medical Plant, Xuzhou Normal University, Jiangsu, Xuzhou, Jiangsu
221009, P.R. China; E-mail: laotu200l@263.net.
1289
DOI: 10.1081/SCC-120030317
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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Tu et al.
INTRODUCTION
Since microwave heating was used for organic synthesis by Gedye[1] in
1986, the microwave organic chemistry has been a topic of continuing interest.
In continuation to our works to the synthesis of heterocyclic compounds,[2–6]
we hoped to synthesize 5 by the reaction of aldeoxime (1) with dimedone under
microwave irradiation. However, when aldeoxime (1) and dimedone (2) were
reacted with ammonium acetate (4) under microwave irradiation, they gave
acridine derivatives (3) in 80–92% yields instead of the expected 5 (Sch. 1).
The reactions take place only a few minutes and give the products in high yield.
These reactions take place by addition, elimination, addition and cycliza-
tion mechanism. The Michael addition between aldeoxime and dimedone
gave the intermediate 6 which on elimination of aldeoxime gave 2-aryl-
lidene-5,5-dimethyl-1,3-cyclohexanedione 7, Michael addition between 7
and 8 (obtained from dimetone 2 and ammonium acetate) then furnishes the
intermediate 9, which isomerizes to 10. Cyclodehydration of 10 gives 3.
The structures of 3d and 3g were determined by single crystal x-ray (Fig. 1).
In the molecules the pyridine ring has a boat conformation. The results are
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 conformed by X-ray diffraction studies on single crystal of 3d and 3g.a,b

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Novel Reaction of Aldeoxime with Dimedone
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Scheme 1.
EXPERIMENTAL
Melting points were determined in a capillary tube and are uncorrected.
1
The H NMR spectra were recorded on a DPX 300 MHz. Spectrometer with
TMS as internal standard. The IR spectra were obtained with SE-1730 instru-
ment as potassium bromide pellets. Elemental analyses were determined by
Figure 1. X-ray crystal structure of 3g.

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Tu et al.
Table 1. The reaction of aldeoxime with dimedone and ammonium acetate.
Entry
Ar
Time
Yield (%)
M.p. (8C)
3a
3b
3c
3d
3e
3f
3-O2NC6H4
2-ClC6H4
4-ClC6H4
6
5
5
6
5
5
5
80
86
92
88
84
80
88
285–286
221–223
296–298
264–266
258–260
324–326
269–270
4-N(CH3)2C6H3
3,4-(CH3O)2C6H3
3,4-(OCH2O)C6H3
4-CH3OC6H4
3g
using Perkin–Elmer 240C elemental analyzer. Crystal structure was obtained
with CAD4 diffractometer. Microwave irradiation was carried out with a mod-
ificatory commercial microwave oven (2450 MHz, 650 W) under atmospheric
pressure.
General Procedure
A dry flask (25 mL) was charged with the aromatic aldeoxime 1 (1 mmol),
dimedone 2 (1 mmol), ammonium acetate 4 (2 mmol), and glycol 3 mL. The
flask was then connected with refluxing equipment. After microwave
irradiation for 5–6 min, the reaction mixture was cooled to room temperature
and washed with water, then filtered to give the crude product, which was
further purified by recrystallization.
3a: M.p. 283–2858C. (lit. 285–2868C).[8]
3b: M.p. 221–2238C. (lit. 222–2248C).[8]
3c: M.p. 296–2988C, IR (KBr, n, cm21): 3383 (NH), 1623 (C55O), 1603
(N–C55O); H NMR (DCCl3, d, ppm): 0.93 (s, 6H, 2CH3), 1.05 (s, 6H,
1
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; Cacld for: C23H26ClNO2: C, 71.96; H, 6.83; N, 3.65.
3d: M.p. 263–2658C. (lit. 264–2668C).[9]
3e: M.p. 258–2608C. IR (KBr, n, cm21): 3384 (NH), 1623 (C55O), 1602
1
(N–C55O); H NMR (DCCl3, d, 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; Cacld for: C25H31NO4: C, 73.32; H, 7.63;
N, 3.42.
3f: M.p. 324–3268C. IR (KBr, n, cm21): 3280 (NH), 1620 (C550), 1601
1
(N–C55O); H NMR (DCCl3, d, ppm): 1.00 (s, 6H, 2CH3), 1.10 (s, 6H,

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Novel Reaction of Aldeoxime with Dimedone
1293
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; Cacld for: C24H27NO4: C, 73.26; H, 6.92; N, 3.56.
3g: M.p. 269–2708C. (lit. 270–2728C).[9]
ACKNOWLEDGMENTS
We thank the Nature Science Foundation of the Jiangsu Province (No.
BK2001142) and the Nature Science Foundation of Jiangsu Education Depart-
ment (No. 01KJB150008) and the Key Laboratory of Chemical Engineering
and Technology of the Jiangsu Province Open Foundation (No. KJS02060)
for financial support.
NOTES
a. X-ray analysis of 3d: Empirical formula C25H32N2O2, F.W. 392.54,
˚
T ¼ 296(2) K, orthorhombic, space group Pna2(1), a ¼ 14.181(3) A,
˚
˚
b ¼ 13.509(3) A, c ¼ 11.719(2) A, a ¼ 908, b ¼ 908, g ¼ 908,
V ¼ 2245.0(8) A , Z ¼ 4, Dc ¼ 1.161 mg/m3, F(000) ¼ 848,
l
3
˚
(Mo Ka) ¼ 0.71073 A, m ¼ 0.073 mm21, 2.088 , u , 26.008, R ¼
˚
0.0395, wR ¼ 0.0706. S ¼ 0.844, Largest diff. Peak and hole: 0.112
3
and 20.118 e A .
˚
b. X-ray analysis of 3g: Empirical formula C24H29NO3, F.W. 379.48,
T ¼ 293(2) K, orthorhombic, space group Pca2(1), a ¼
˚
˚
3
˚
14.1862(3)A, b ¼ l5.1896(3) A, c ¼ 20.7611(2)A, a ¼ 908, b ¼ 908,
3
˚
g ¼ 908, V ¼ 4473.66(13) A , Z ¼ 8, Dc ¼ 1.127 mg/m , F(000) ¼
1632, l (Mo Ka) ¼ 0.71073 A, m ¼ 0.074 mm21, 1.348 , u ,
˚
25.028, R ¼ 0.0652, wR ¼ 0.1510. S ¼ 1.144, Largest diff. Peak
3
and hole: 0.223 and 20.220 e A .
˚
REFERENCES
1. Gedye, R.; Smith, F.; Westawaym, K.; Humera, A.; Baldisern, L.;
Laberge, L. J. Tetrahedron Lett. 1986, 27, 279.
2. Tu, S.J.; Zhou, J.F.; Lu, Z.S.; Deng, X.; Shi, D.Q.; Wang, S.H. Synth.
Commun. 2002, 19, 3063.
3. Tu, S.J.; Wei, Q.H.; Ma, H.J.; Shi, D.Q.; Gao, Y.; Cui, G.Y. Synth.
Commun. 2001, 17, 2675.

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4. Tu, S.J.; Zhou, J.F.; Cai, P.J.; Wang, H.; Feng, J.C. Synth. Commun. 2001,
24, 3729.
5. Tu, S.J.; Gao, Y.; Guo, C.; Shi, D.Q.; Lu, Z.S. Synth. Commun. 2002, 14,
2137.
6. Tu, S.J.; Zhou, J.F.; Cai, P.J.; Wang, H.; Feng, J.C. Synth. Commun. 2002,
1, 147.
7. Suarez, M.; Loupy, A.; Salfran, E.; Moran, L.; Rolando, E. Heterocycles
1999, 51, 21.
8. Martin, N.; Quinteiro, M.; Seoane, C. et al. J. Heterocycl. Chem. 1995,
32, 235.
9. Suarez, M.; Loupy, A.; Salfran, E.; Moran, L.; Rolando, E. Heterocycles
1999, 51, 21.
Received in Japan July 28, 2003

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