Fast and efficient synthesis of 10-aryl-2,7-dimethyl-4,5-dioxo-3,6,9- trioxa-3,4,5,6,9,10-hexahydroanthracene under microwave irradiation without catalyst

Article abstract of DOI:10.1080/00397910701263601

A fast and efficient synthetic method for the title compounds is described. By heating aromatic aldehyde and triacetic acid lactone in ethylene glycol under microwave irradiation without catalyst for 3-5 min, 10-aryl-2,7-dimethyl- 4,5-dioxo-3,6,9-trioxa-3

Full text of DOI:10.1080/00397910701263601

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Fast and Efficient Synthesis of
10‐Aryl‐2,7‐dimethyl‐4,5‐dioxo‐3,6,9‐trioxa‐3,4,5
under Microwave Irradiation without Catalyst
Yuan Gao a , Shujiang Tu b , Feng Shi b , Qian Wang b , Xiaotong Zhu b &
Daqing Shi b
a Department of Chemistry , Shenzhen University , Guangdong, Shenzhen,
China
b Department of Chemistry , Xuzhou Normal University , Jiangsu, Xuzhou,
China
Published online: 22 May 2007.
To cite this article: Yuan Gao , Shujiang Tu , Feng Shi , Qian Wang , Xiaotong Zhu & Daqing Shi (2007) Fast
and Efficient Synthesis of 10‐Aryl‐2,7‐dimethyl‐4,5‐dioxo‐3,6,9‐trioxa‐3,4,5,6,9,10‐hexahydroanthracene
under Microwave Irradiation without Catalyst, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 37:10, 1603-1608, DOI: 10.1080/00397910701263601
To link to this article: http://dx.doi.org/10.1080/00397910701263601
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Synthetic Communicationsw, 37: 1603–1608, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910701263601
Fast and Efficient Synthesis of 10-Aryl-2,7-
dimethyl-4,5-dioxo-3,6,9-trioxa-3,4,5,6,9,10-
hexahydroanthracene under Microwave
Irradiation without Catalyst
Yuan Gao
Department of Chemistry, Shenzhen University, Guangdong,
Shenzhen, China
Shujiang Tu, Feng Shi, Qian Wang, Xiaotong Zhu, and Daqing Shi
Department of Chemistry, Xuzhou Normal University, Jiangsu,
Xuzhou, China
Abstract: A fast and efficient synthetic method for the title compounds is described. By
heating aromatic aldehyde and triacetic acid lactone in ethylene glycol under
microwave irradiation without catalyst for 3–5 min, 10-aryl-2,7-dimethyl-4,5-dioxo-
3,6,9-trioxa-3,4,5,6,9,10-hexahydroanthracenes were afforded with high yields.
Keywords: aromatic aldehyde, microwave irradiation, triacetic acid, trioxanthene
Pyrans and fused pyrans are biologically interesting compounds with antibac-
terial activity,[1,2] antifungal activity,[3] antitumor activity,[4] and hypotensive
effect.[5] On the other hand, some pyran derivatives also have various biologi-
cal properties such as antiproliferation effects,[6] molluscicidal activity,[7]
local anesthetic and antiarrhythmic activities,[8] antiallergic effects[9,10] and
hypolipidemic activity.[11] Among them, 2,7,10-trioxanthene ring system
was a class of important compounds, which had previously been obtained
Received April 12, 2006
Address correspondence to Shujiang Tu, Department of Chemistry, Xuzhou Normal
University, Jiangsu, Xuzhou 221116, China. E-mail: laotu2001@263.net
1603

1604
Y. Gao et al.
by two steps using toxic reagents such as triphenylphosphine, diethyl azodi-
carboxylate, and benzene.[12] So, this process did damage to our environment.
In our previous article, we reported the synthesis of 9-aryl-3,6-dimethyl-1,8-
dioxo-2,7,10-trioxanthenes (3), which contain a 4H-pyran unit by the
reaction of aromatic aldehydes (1) with 4-hydroxyl-6-methyl-2-pyranone (2)
using KF/Al2O3 as catalyst under traditional heating conditions. In this
method, however, the catalyst KF/Al2O3 was necessary, and the yield was
lower.[13] Here, we further report a fast, efficient, and simple method for the
synthesis of 9-aryl-3,6-dimethyl-1,8-dioxo-2,7,10-trioxanthenes (3) by the
reaction of aromatic aldehydes (1) with 4-hydroxyl-6-methyl-2-pyranone (2)
using a small quantity of glycol as energy-transferring agent under
microwave irradiation without catalyst (Scheme 1).
The main results for the syntheses of these compounds are given in
Table 1.
It is obvious that this reaction has the advantages of short reaction time,
good yields, convenient workup procedures, and environmentally friendliness.
This reaction took place through the mechanisms of condensation,
addition, and cyclization (Scheme 2).
All the products were characterized by IR and 1H NMR analysis. Further-
more, the structure of compound 3i was confirmed by an X-ray crystallographic
analysis (Figure 1). X-ray analysis of 3i: empirical formula C20H16O6, F.W.
352.33, T ¼ 298(2) K, monoclinic, space group P2(1)/c, a ¼ 9.702(1) nm,
b ¼ 11.090(2) nm, c ¼ 115.757(3) nm, a ¼ 908, b ¼ 96.84(1)8, g ¼ 908,
V ¼ 1683.2(3) nm3, Z ¼ 4, Dc ¼ 1.390 kg/m3, F(000) ¼ 736, R ¼ 0.0509,
wR ¼ 0.1365, l(Mo Ka) ¼ 0.71073nm, m ¼ 0.10 nm21, S ¼ 1.020, largest
3
˚
diff. peak and hole: 0.22 and 20.17 eA .
EXPERIMENTAL
Melting points were determined in open capillaries and are uncorrected. IR
1
spectra were recorded on a FT IR-8101 spectrometer. H NMR spectra were
measured on a Bruker DPX 400-MHz spectrometer using TMS as internal
standard and DCCl3 as solvent. Elemental analysis was determined using a
Perkin-Elmer 240c elemental analysis instrument. X-ray crystallographic
analysis was determined using Siemens P4 diffractometer. Microwave
Scheme 1.

Efficient Synthetic Method for the Title Compounds
1605
Table 1. Synthesis of 1,8-dioxo-2,7,10-trioxanthene (3)
Time
(min)
Yield (%)
(lit.)
Mp (8C)
(lit.)
Entry
Ar
3a
C6H5
4
3
5
5
4
5
5
5
5
4
85 (80)[12]
(77.7)[13]
296–297
(297–298)[12]
283–284
(282–284)[13]
272–274
(271–273)[13]
273–275
(273–275)[13]
294–295
(293–295)[13]
242–243
(242–244)[13]
281–283
(281–283)[13]
289–291
(289–291)[13]
270–271
(264–265)[12]
290–291
3b
3c
3d
3e
3f
4-CH3C6H4
2-ClC6H4
87 (73.5)[13]
90 (80.3)[13]
89 (76.2)[13]
95 (89.2)[13]
90 (60.3)[13]
92 (70.3)[13]
94 (80.0)[13]
88 (77)[12]
93
2-BrC6H4
4-BrC6H4
4-OHC6H4
3g
3h
3i
4-OH-3-OCH3C6H3
4-NO2C6H4
4-OCH3C6H4
3,4-OCH2O-C6H3
3j
Scheme 2.

1606
Y. Gao et al.
Figure 1. X-ray crystal structure of 3i.
irradiation was carried out with a modified commercial microwave oven
(2450 MHz, 650 W) under atmospheric pressure.
General Procedure
A dry flask (25 mL) was charged with aromatic aldeoxime 1 (1 mmol),
4-hydroxyl-6-methyl-2-pyranone 2, (2 mmol), and glycol (1 mL). The flask
was then connected with refluxing equipment. After microwave irradiation
for 3–5 min, the reaction mixture was cooled to room temperature, washed
with water, and then filtered to give the crude product, which was further
purified by recrystallization.
Data
10-Phenyl-2,7-dimethyl-4,5-dioxo-3,6,9-trioxa-3,4,5,6,9,10-hexahydroanthra
cene, 3a: IR (KBr, n): 3091, 1724, 1705, 1637, 1604, 1438, 1240, 1182, 1136,
1034, 974, 829, 752, 707, 599 cm21; 1H NMR (CDCl3, d): 2.24 (s, 6H, 2CH3),
4.83 (s, 1H, CH), 5.99 (s, 2H, 2C55CH), 7.17–7.35 (m, 5H, ArH). Found: C,
70.92; H, 4.28. C19H14O5 requires C, 70.80; H, 4.38%.
10-(4-Methylphenyl)-2,7-dimethyl-4,5-dioxo-3,6,9-trioxa-3,4,5,6,9,10-hexa
hydroanthracene, 3b: IR (KBr, n): 3091, 1720, 1611, 1518, 1442, 1377,
1
1349, 1247, 1180, 1138, 1043, 973, 835, 790, 738, 689, 675 cm21; H
NMR (CDCl3, d): 2.23 (s, 6H, 2CH3), 2.27 (s, 3H, CH3), 4.79 (s, 1H,
CH), 5.98 (s, 2H, 2C55CH), 7.10 (s, 2H, J ¼ 8.4 Hz, ArH), 7.20 (s, 2H,

Efficient Synthetic Method for the Title Compounds
1607
J ¼ 8.4 Hz, ArH). Found: C, 71.30; H, 4.64. C20H16O5 requires C, 71.42; H,
4.79%.
10-(2-Chlorophenyl)-2,7-dimethyl-4,5-dioxo-3,6,9-trioxa-3,4,5,6,9,10-hexa
hydroanthracene, 3c: IR (KBr, n): 3091, 1732, 1705, 1647, 1610, 1479,
1
1442, 1379, 1247, 1186, 1142, 1037, 972, 810, 756, 692 cm21; H NMR
(CDCl3, d): 2.24 (s, 6H, 2CH3), 5.07 (s, 1H, CH), 5.96 (s, 2H, 2C55CH),
7.14–7.53 (m, 4H, ArH). Found: C, 64.06; H, 3.60. C19H13ClO5 requires
C, 63.97; H, 3.67%.
10-(2-Bromophenyl)-2,7-dimethyl-4,5-dioxo-3,6,9-trioxa-3,4,5,6,9,10-hexa
hydroanthracene, 3d: IR (KBr, n): 3085, 1729, 1641, 1610, 1525, 1444,
;
1380, 1243, 1240, 1137, 1039, 968, 840, 794, 748 cm21 1H NMR
(CDCl3, d): 2.25 (s, 6H, 2CH3), 5.11 (s, 1H, CH), 5.96 (s, 2H, 2C55CH),
7.05–7.47 (m, 4H, ArH). Found: C, 56.98; H, 3.21. C19H13BrO5 requires
C, 56.88; H, 3.27%.
10-(4-Bromophenyl)-2,7-dimethyl-4,5-dioxo-3,6,9-trioxa-3,4,5,6,9,10-hexa
hydroanthracene, 3e: IR (KBr, n): 3085, 1749, 1718, 1639, 1604, 1490,
;
1375, 1242, 1186, 1132, 1075, 966, 815, 706, 698 cm21 1H NMR
(CDCl3, d): 2.25 (s, 6H, CH3), 4.79 (s, 1H, CH), 5.99 (s, 2H, C55CH),
7.21 (s, 2H, J ¼ 8.4 Hz, ArH), 7.34 (s, 2H, J ¼ 8.4 Hz, ArH). Found: C,
56.96; H, 3.34. C19H13BrO5 requires C, 56.88; H, 3.27%.
10-(4-Hydroxyphenyl)-2,7-dimethyl-4,5-dioxo-3,6,9-trioxa-3,4,5,6,9,10-hexah
ydroanthracene, 3f: IR (KBr, n): 3433, 3091, 1760, 1730, 1703, 1611, 1600, 150,
1
1438, 1377, 1242, 1201, 1186, 964, 916, 804, 742, 692, 670 cm21; H NMR
(CDCl3, d): 2.25 (s, 6H, 2CH3), 4.85 (s, 1H, CH), 5.99 (s, 2H, 2C55CH), 6.99
(s, 2H, J ¼ 8.4 Hz, ArH), 7.30 (s, 2H, J ¼ 8.4 Hz, ArH). Found: C, 67.58; H,
4.09. C19H14O6 requires C, 67.45; H, 4.17%.
10-(4-Hydroxy-3-methoxyphenyl)-2,7-dimethyl-4,5-dioxo-3,6,9-trioxa-
3,4,5,6,9,10-hexahydroanthracene, 3g: IR (KBr, n): 3415, 3097, 1768, 1728,
1640, 1602, 1500, 1442, 1377, 1241, 1137, 1029, 962, 900, 842 794, 702,
1
640 cm21; H NMR (CDCl3, d): 2.25(s, 6H, CH3), 3.85 (s, 3H, OCH3),
4.86 (s, 1H, CH), 5.99 (s, 2H, C55CH), 6.66–7.20 (m, 3H, ArH). Found: C,
65.32; H, 4.45. C20H16O7 requires C, 65.22; H, 4.38%.
10-(4-Nitrophenyl)-2,7-dimethyl-4,5-dioxo-3,6,9-trioxa-3,4,5,6,9,10-hexah
ydroanthracene, 3h: IR (KBr, n): 3085, 1722, 1639, 1608, 1515, 1440,
;
1348, 1245, 1188, 1136, 1035, 974, 839, 744, 692 cm21 1H NMR
(CDCl3, d): 2.27 (s, 6H, CH3), 4.92 (s, 1H, CH), 6.04 (s, 2H,
C55CH), 7.45 (s, 2H, J ¼ 8.6 Hz, ArH), 8.10 (s, 2H, J ¼ 8.6 Hz, ArH).
Found: C, 62.30; H, 3.46; N, 3.74. C19H13NO7 requires C, 62.13; H,
3.57; N, 3.81%.

1608
Y. Gao et al.
10-(4-Methoxyphenyl)-2,7-dimethyl-4,5-dioxo-3,6,9-trioxa-3,4,5,6,9,10-hexa
hydroanthracene, 3i: IR (KBr, n): 3093, 1735, 1640, 1604, 1535, 1512, 1442,
1380, 1242, 1180, 1134, 1033, 972, 802, 740 cm21; 1H NMR (CDCl3, d): 2.24
(s, 6H, 2CH3), 3.75 (s, 3H, OCH3), 4.78 (s, 1H, CH), 5.97 (s, 2H, 2C55CH),
6.79 (s, 2H, J ¼ 8.4 Hz, ArH), 7.25 (s, 2H, J ¼ 8.4 Hz, ArH). Found: C, 68.30;
H, 4.42. C20H16O6 requires C, 68.18; H, 4.58%.
10-(3,4-Methylenedioxyphenyl)-2,7-dimethyl-4,5-dioxo-3,6,9-trioxa-3,4,5,6,9,
10-hexahydroanthracene, 3j: IR (KBr, n): 3093, 1720, 1639, 1612, 1581,
1488, 1388, 1380, 1249, 1033, 972 cm21; 1H NMR (CDCl3, d): 2.25 (s, 6H,
2CH3), 4.73 (s, 1H, CH), 5.89 (s, 2H, 2C55CH), 6.99–6.84 (m, 3H, ArH).
Found: C, 65.72; H, 3.78. C20H14O7 requires C, 65.57; H, 3.85%.
ACKNOWLEDGMENT
We thank the Natural Science Foundation of Guangdong Province (No.
031792) for financial support.
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