Sonochemical syntheses of xanthene derivatives using zeolite-supported transition metal catalysts in aqueous media

Article abstract of DOI:10.1007/s11164-015-2192-1

An efficient green method for the syntheses of biologically active xanthene derivatives by use of zeolite-supported transition metal catalysts is described. A Fe-Cu/ZSM-5 heterogeneous catalyst has the highest activity in the one-pot syntheses with a wide

Full text of DOI:10.1007/s11164-015-2192-1

Res Chem Intermed
DOI 10.1007/s11164-015-2192-1
Sonochemical syntheses of xanthene derivatives using
zeolite-supported transition metal catalysts in aqueous
media
Kazem D. Safa1 Elham Taheri1 Maryam Allahvirdinesbat1
Aligholi Niaei2
•
•
•
Received: 20 May 2015 / Accepted: 24 July 2015
Ó Springer Science+Business Media Dordrecht 2015
Abstract An efficient green method for the syntheses of biologically active
xanthene derivatives by use of zeolite-supported transition metal catalysts is
described. A Fe-Cu/ZSM-5 heterogeneous catalyst has the highest activity in the
one-pot syntheses with a wide range of aldehydes and cyclic 1,3-diketones, under
ultrasonic irradiation in water at ambient temperatures. The three-component con-
densation in the presence of supported metal catalysts is operationally simple,
requires no expensive or toxic reagents, and gives high yields in short reaction
times.
Keywords Xanthenes Á Fe-Cu/ZSM-5 Á Ultrasonic irradiation Á MCRs Á
Supported catalyst Á Water
Introduction
In green chemistry, which covers all chemical processes that minimize the use and
generation of substances injurious to human health [1], catalysis is a key area. The
use of metal oxides supported on various inorganic solid supports has attracted wide
attention [2]. Zeolites, such as Cu-modified HY, H-USY, H-Beta, mordenite, and
ZSM-5 [4], have been used in the synthesis of specialty and fine chemicals because
Electronic supplementary material The online version of this article (doi:10.1007/s11164-015-2192-
1) contains supplementary material, which is available to authorized users.
&
Kazem D. Safa
dsafa@tabrizu.ac.ir
1
2
Organosilicon Research Laboratory, Faculty of Chemistry, University of Tabriz,
Tabriz 5166614766, Iran
Department of Applied Chemistry and Chemical Engineering, Faculty of Chemistry, University
of Tabriz, Tabriz 5166614766, Iran
123

K. D. Safa et al.
of their tunable acidity, the variety of their structures and pore dimensions, and their
excellent thermal stability [3]. For the development of green syntheses, however,
the catalysts must be effective in aqueous solution [1, 5–7]. Multicomponent
coupling reactions (MCRs) with fewer steps, lower energy consumption, and less
waste are particularly suitable for the synthesis of new biologically and pharma-
ceutically active compounds [3].
Derivatives of xanthenes and benzoxanthenes have been investigated because of
their antiviral, antibacterial, anti-inflammatory, anticancer, and antitumor activities
[8–11]. They are also used as pH-sensitive fluorescent materials for visualization of
biomaterials, in laser technologies, and as luminescent dyes [12, 13]. These wide-
ranging applications show that the development of synthetic procedures is
important. Established reaction procedures [14–16] have been much improved by
the use of ultrasonic radiation to achieve more efficient mixing and chemical
selectivity, with lower reaction temperatures, better yields, and shorter reaction
times. To the best of our knowledge, no reports are available on the synthesis of
xanthenes and benzoxanthenes by use of zeolite-supported bimetallic nanostructures
as catalysts. We describe here the use of sonochemistry in the one-pot syntheses of
xanthene derivatives in the presence of heterogeneous M-Cu/ZSM-5 (M: Mn, Co
and Fe) zeolite eco-friendly and inexpensive catalysts in aqueous solution.
Results and discussion
Because of the wide use of acidic zeolites in organic chemistry and our continuing
interest in the use of various catalysts in multicomponent reactions (MCR) [3, 17–
21], we wish to report the synthesis of xanthenes and benzoxanthenes by a one-pot
three-component condensation of 2-naphthol or a series of cyclic 1,3-diketones with
O
O
O
R
O
R'
R'
2
R'
R'
O
R'
R'
O
O
1a-1i
O
M/SAPO-34 or ZSM-5
+
M-Cu/ZSM-5
H2O,((((
R
H
R'
R'
R
O
1
2
R' =Me, H
M= Mn, Co, Fe, Cu as nitrates
R'
OH
O
1j-1o
R'
3
Scheme 1 Preparation of xanthene and benzoxanthene derivatives using zeolite-supported transition
metal catalysts
123

Sonochemical syntheses of xanthene derivatives using…
a wide range of aldehydes in the presence of zeolite-supported transition metal
catalysts as recyclable catalysts in water under ultrasonic irradiation at ambient
temperature (Scheme 1).
Initially, the catalysts with various transition metals (Mn, Fe, Co, and Cu)
deposited on ZSM-5 or silicoaluminophosphate-34 (SAPO-34) supports were
prepared by the homogeneous deposition precipitation (HDP) method [29], and
tested for the synthesis of xanthene derivatives. In order to optimize the reaction
parameters, the catalytic influence of different transition metals supported on the
zeolites, the weight loadings of metal (wt%), the acidity of supports, the amounts of
catalysts, and different reaction media were investigated for the cyclo-condensation
reaction of 5,5-dimethylcyclohexane-1,3-dione (dimedone), 2-naphthol and ben-
zaldehyde as a model reaction for the preparation of 9,10-dihydro-9,9-dimethyl-12-
phenyl-8H-benzo[a]xanthene-11(12H)-one (1j). It has been reported that the
Table 1 Optimization of the reaction conditions
H
O
O
catalyst
+
O
H2O, ((((
OH
O
1j
O
Entry
Catalyst
Time (min)
Yield (%)a
1
Mn/SAPO-34
Co/SAPO-34
Fe/SAPO-34
Cu/SAPO-34
Mn/ZSM-5
Co/ZSM-5
45
45
45
45
45
45
45
45
10
10
7
21
35
48
52
25
39
55
58
52
75
94
31
35
2
3
4
5
6
7
Fe/ZSM-5
8
Cu/ZSM-5
9
Mn-Cu/ZSM-5
Co-Cu/ZSM-5
Fe-Cu/ZSM-5
H-SAPO-34
H-ZSM-5
10
11
12
13
1 h
1 h
Reaction conditions: benzaldehyde (1 mmol), dimedone (1 mmol), 2-naphthol (1 mmol), and (5 wt%
from monometallic catalyst) and (3 wt% from bimetallic catalyst) in water under ultrasonic irradiation at
ambient temperature at 40 % power of the processor
a
Yields refer to isolated products
123

K. D. Safa et al.
activity of catalysts with a loading of 10 wt% is lower than that with a loading of
5 mol%. The decrease is attributed to metal agglomeration leading to inactive metal
particles. Zeolite H-ZSM-5 with 5 wt% Cu loading gave 1j in 58 % yield under
ultrasonic irradiation in water. Cu-ZSM-5 showed higher activity than the Cu-
SAPO-34 perhaps because the ZSM-5 acidity is greater than that of SAPO-34. The
nature of the transition metal in the zeolite-supported catalysts has more influence
than the support on catalyst activity.
The incorporation of other transition metals into Cu/ZSM-5 to give a series of
M-Cu/ZSM-5 (M: Mn, Co, and Fe) bimetallic oxide nano-catalysts has been
studied. Incorporation of Fe into Cu/ZSM-5 increased the product yield to 94 % and
reduced the reaction time (7 min) with decreased catalyst loading (3 wt%) (Table 1,
entry 11). Ultrasound irradiation provides well mixing and acoustic cavitations
appear to facilitate the bringing together of the reactants on the catalyst surface [14,
15]. We studied the effect of various solvents under ultrasound irradiation and also
solvent-free conditions on a model reaction with Fe-Cu/ZSM-5 catalyst. As can be
seen from Table 2, the polar solvents and solvent-free conditions afforded better
yield than the non-polar ones and the best result was obtained in aqueous medium.
To show the applicability of this method, the preparation of derivatives (1a–1o)
with variety of aromatic aldehydes bearing both electron-withdrawing and electron-
donating groups was investigated under the same experimental conditions and the
corresponding products were obtained in high yields without the formation of
detectable side products (Table 3). Some of the xanthene derivatives are known
compounds and their identity was confirmed by IR, NMR, elemental analyses, and
melting points [8, 27, 28].
On 4H-pyran-4-one (4-pyrone) derivatives are widely distributed in a variety of
bio-active compounds [22–26]. We have therefore designed a synthetic strategy for
molecules bearing both xanthene and pyrone fragments. The three-component
reaction of 5-(benzyloxy)-4-oxo-4H-pyran-2-carbaldehyde, with a cyclic 1,3-
diketone 2 and 2-naphthol 3 in the presence of Cu-Fe/ZSM-5 in water under
ultrasonic irradiation gave the expected xanthene derivatives (1h, 1i, and 1l) in high
yields.
As shown in Scheme 2, 5-(benzyloxy)-4-oxo-4H-pyran-2-carbaldehyde was
obtained from commercially available Kojic acid [5-hydroxy-2-(hydroxymethyl)-
4H-pyran-4-one] by benzylation of the phenolic OH [26], followed by oxidation of
Table 2 Synthesis of 9,10-
Entry
Conditions
Time (min)
Yield (%)a
dihydro-9,9-dimethyl-12-
phenyl-8H-benzo[a]xanthen-
11(12H)-one (1j) using (3 wt%)
Fe-Cu/ZSM-5 bimetallic
catalyst
1
2
3
4
5
6
7
Ethanol
20
20
20
20
7
50
52
48
70
94
20
84
Methanol
Acetonitrile
Ethanol/water
Water
CH2Cl2
50
10
a
Yields refer to isolated
Solvent-free (120 °C)
product
123

Sonochemical syntheses of xanthene derivatives using…
123

K. D. Safa et al.
123

Sonochemical syntheses of xanthene derivatives using…
123

K. D. Safa et al.
123

Sonochemical syntheses of xanthene derivatives using…
123

K. D. Safa et al.
O
O
O
O
O
i
HO
Ph
O
Ph
O
ii
CH2OH
H
CH2OH
O
O
Scheme 2 (i) PhCH2Br (1eq), NaOH (1eq), MeOH/H2O: 10/1, 60 °C, 4 h. (ii) IBX, DMSO/H2O: 90/10,
80 °C, 2 h
the hydroxymethyl group with 2-iodobenzoic acid (IBX) in DMSO:H2O (90:10)
[17].
In a possible mechanism (Scheme 3), the carbonyl group of the aromatic
aldehyde is initially activated by the Fe-Cu/ZSM-5 catalyst to give the intermediate
I. This is then attacked by b-naphthol (A) to afford II as a Michael acceptor.
Michael addition of dimedone (B) with intermediate II gives intermediate III.
Finally by elimination of H2O from III, the tetrahydrobenzoxanthene derivative IV
is produced.
The synthesis of 1,8-dioxooctahydroxanthene derivatives (Scheme 4) could
proceed similarly. The activated carbonyl group of the aromatic aldehyde (I) is
attacked by the cyclic 1,3-diketone (B). Then Michael addition of the cyclic 1,3-
diketone (B) gives III and elimination of H2O gives IV [33, 34].
Conclusions
The zeolite H-ZSM-5, impregnated with Cu(II) and Fe(III) by treatment with metal
nitrates, has been used as an efficient supported catalyst for an improved one-pot
synthesis of tetrahydrobenzoxanthene and 1,8-dioxooctahydroxanthene derivatives
in water under ultrasound irradiation. The simple procedures, combined with easy
recovery and reuse of this catalyst, make this method economically and
environmentally benign. Xanthene derivatives possessing pyrone moieties were
prepared under the same experimental conditions and the corresponding products
were obtained in high yields.
..
OH
OH
+
O
R
R
O
O
A
OH
Cyclization
-H2O
R
H
R'
R'
R'
R'
O
O
II
R'
OH
R
HO
B
R'
IV
III
I
= Fe-Cu/ZSM-5
Scheme 3 Possible mechanism for the synthesis of tetrahydrobenzoxanthene
123

Sonochemical syntheses of xanthene derivatives using…
.
.
OH
..
OH
R'
R'
O
R
O
O
O
O
R
O
O
+
R'
OH
R'
R
H
R'
R'
Cyclization
-H2O
R'
R'
O
R'
R'
R'
O
O
OH
HO
R'
R'
R'
I
R
IV
O
B
III
II
R'
R'
B
= Fe-Cu/ZSM-5
Scheme 4 Possible mechanism for the synthesis of 1,8-dioxooctahydroxanthene derivatives
Experimental
Materials and technique
Chemicals were either prepared in our laboratory or purchased from Merck, Fluka,
1
and Aldrich. Commercial products were used without further purification. The H
and 13C NMR spectra were recorded with a Bruker FT-400 MHz spectrometer at
room temperature and with CDCl3 as solvent. The FTIR spectra were recorded on a
Bruker Tensor 270 spectrometer. The reactions were carried out by used of an
ultrasonic processor probe (SONOPULS Ultrasonic homogenizers). The elemental
analyses were carried out with an Elementar Vario EL III instrument. The
abbreviations used for NMR signals are: s = singlet, d = doublet, t = triplet and
m = multiplet. Melting points were recorded on a Bu¨chi B-545 apparatus in open
capillary tubes.
Synthesis of nanocatalysts
The catalysts were prepared as indicated by Niaei et al. [29]. The characterization of
Fe-Cu/ZSM-5 catalyst is described in supporting information.
General procedure for preparation of 1,8-dioxo-octahydroxanthene derivatives
(1a–1o)
In a typical experiment, various aromatic aldehyde (1 mmol), cyclic 1,3-diketone
(2 mmol) and 3 wt% of Fe-Cu/ZSM-5 in 2 ml water was introduced in a 20-ml
heavy-walled, pear-shaped, two-necked flask with nonstandard tapered outer joint.
The flask was attached to a 12-mm-tip diameter probe and the reaction mixture was
sonicated at ambient temperature at 40 % power of the processor. After completion
of the reaction (monitored by TLC, within 5–10 min), the solid product was filtered,
washed with water, dried, and recrystallized from ethanol. The zeolite-supported
transition metal catalysts was washed three times with water and ethanol and dried
under vacuum before reuse.
123

K. D. Safa et al.
The spectral data of some of the selected products
3,4,6,7-Tetrahydro-3,3,6,6-tetramethyl-9-phenyl-2H-xanthene-1,8(5H,9H)-dione
(1a)
White powder; yield 92 %; M.P. = 200–202 °C; FTIR (KBr, cm-1): 3031 (Ar–H),
2957 (C–H), 1661 (C=O), 1626 (C=C), 1362, 1199, 1163 (C–O), 968, 699. 1H NMR
(400 MHz, CDCl3, ppm): d 0.98 (s, 6H, 2CH3), 1.09 (s, 6H, 2CH3), 2.16 (d,
J = 16.2 Hz, 2H, 2CH2), 2.23 (d, J = 16.3 Hz, 2H, 2CH2), 2.46 (s, 4H, 2CH2),
4.74 (s, 1H, CH), 7.09 (t, J = 7.3 Hz, 1H, Ar–H), 7.21 (t, J = 7.6 Hz, 2H, Ar–H),
7.28 (d, J = 6.8 Hz, 2H, Ar–H). 13C NMR (100 MHz, CDCl3, ppm): d 26.27,
28.23, 30.77, 31.15, 39.80, 49.68, 114.60, 125.31, 126.99, 127.32, 143.03, 161.22,
195.38. Anal. Calc. for C23H26O3: C 78.83, H 7.48 %. Found: C 78.69, H 7.24 %.
3,4,6,7-Tetrahydro-9-(4-hydroxyphenyl)-3,3,6,6-tetramethyl-2H-xanthene-
1,8(5H,9H)-dione (1b)
White powder; yield 90 %; M.P. = 245–247 °C; FTIR (KBr, cm-1): 3412 (O–H),
3022 (Ar–H), 2960 (C–H), 1653 (C=O), 1615 (C=C), 1365, 1197, 1137 (C–O), 931,
1
698. H NMR (400 MHz, CDCl3, ppm): d 0.99 (s, 6H, 2CH3), 1.09 (s, 6H, 2CH3),
2.17 (d, J = 16.3 Hz, 2H, 2CH2), 2.23 (d, J = 16.3 Hz, 2H, 2CH2), 2.45 (s, 4H,
2CH2), 4.67 (s, 1H, CH), 6.20 (s, 1H, OH, exchanged with D2O), 6.57 (d,
J = 8.4 Hz, 2H, Ar–H), 7.08 (d, J = 8.4 Hz, 2H, Ar–H). 13C NMR (100 MHz,
CDCl3, ppm): d 26.35, 28.15, 29.92, 31.24, 39.81, 49.71, 114.19, 114.82, 128.33,
134.65, 153.57, 161.37, 196.19. Anal. Calc. for C23H26O4: C 75.38, H 7.15 %.
Found: C 75.47, H 7.10 %.
3,4,6,7-Tetrahydro-3,3,6,6-tetramethyl-9-(4-nitrophenyl)-2H-xanthene-1,8(5H,9H)-
dione (1c)
White powder; yield 95 %; M.P. = 222–224 °C; FTIR (KBr, cm-1): 3081 (Ar–H),
2962 (C–H), 1666 (C=O), 1615, 1519, 1467 (C=C), 1352, 1200, 1165, 1138 (C–O),
1
911, 699. H NMR (400 MHz, CDCl3, ppm): d 0.92 (s, 6H, 2CH3), 1.05 (s, 6H,
2CH3), 2.10 (d, J = 16.3 Hz, 2H, 2CH2), 2.19 (d, J = 16.3 Hz, 2H, 2CH2), 2.43 (s,
4H, 2CH2), 4.76 (s, 1H, CH), 7.41 (d, J = 8.6 Hz, 2H, Ar–H), 8.03 (d, J = 8.6 Hz,
2H, Ar–H). 13C NMR (100 MHz, CDCl3, ppm): d 26.21, 28.22, 31.21, 31.31, 39.77,
49.53, 113.47, 122.41, 128.32, 145.40, 150.49, 161.92, 195.29. Anal. Calc. for
C23H25NO5: C 69.86, H 6.37, N 3.54 %. Found: C 69.71, H 6.24, N 3.65 %.
9-(4-Bromophenyl)-3,4,6,7-tetrahydro-3,3,6,6-tetramethyl-2H-xanthene-
1,8(5H,9H)-dione (1d)
White powder; yield 92 %; M.P. = 235–236 °C; FTIR (KBr, cm-1): 3042 (Ar–H),
2957 (C–H), 1661 (C=O), 1618, 1486, 1468 (C=C), 1362, 1198, 1162, 1140 (C–O),
1
942, 696. H NMR (400 MHz, CDCl3, ppm): d 0.98 (s, 6H, 2CH3), 1.10 (s, 6H,
2CH3), 2.15 (d, J = 16.3 Hz, 2H, 2CH2), 2.23 (d, J = 16.3 Hz, 2H, 2CH2), 2.46 (s,
123

Sonochemical syntheses of xanthene derivatives using…
4H, 2CH2), 4.69 (s, 1H, CH), 7.17 (d, J = 8.4 Hz, 2H, Ar–H), 7.33 (d, J = 8.4 Hz,
2H, Ar–H). 13C NMR (100 MHz, CDCl3, ppm): d 26.25, 28.26, 28.67, 30.52, 31.18,
39.79, 49.63, 114.14, 119.21, 129.15, 130.12, 142.18, 161.43, 195.37. Anal. Calc.
for C23H25BrO3: C 64.34, H 5.87 %. Found: C 64.51, H 5.69 %.
9-(Benzo[d] [1, 3] dioxol-5-yl)-3,4,6,7-tetrahydro-3,3,6,6-tetramethyl-2H-
xanthene-1,8(5H,9H)-dione (1f)
White powder; yield 94 %; M.P. = 220–222 °C; FTIR (KBr, cm-1): 3052 (Ar–H),
2959 (C–H), 1665 (C=O), 1619, 1483, 1436 (C=C), 1364, 1198, 1165, 1144 (C–O),
1
930, 690. H NMR (400 MHz, CDCl3, ppm): d 1.00 (s, 6H, 2CH3), 1.09 (s, 6H,
2CH3), 2.17 (d, J = 16.3 Hz, 4H, 2CH2), 2.23 (d, J = 16.3 Hz, 4H, 2CH2), 2.45 (s,
4H, 2CH2), 4.66 (s, 1H, CH), 5.87 (s, 2H, O–CH2–O), 6.65 (d, J = 8.0 Hz, 1H, Ar–
H), 6.73 (d, J = 8.4 Hz, 1H, Ar–H), 6.80 (s, 1H, Ar–H). 13C NMR (100 MHz,
CDCl3, ppm): d 26.39, 28.20, 28.68, 30.41, 31.17, 39.79, 49.71, 99.73, 106.84,
108.07, 114.62, 120.49, 137.24, 144.90, 146.26, 161.16, 195.54. Anal. Calc. for
C24H26O5: C 73.08, H 6.64 %. Found: C 73.23, H 6.72 %.
9-(Benzo[d][1,3]dioxol-5-yl)-3,4,6,7-tetrahydro-2H-xanthene-1,8(5H,9H)-dione
(1g)
White powder; yield 95 %; M.P. = 243–245 °C; FTIR (KBr, cm-1): 3055 (Ar–H),
2956 (C–H), 1655 (C=O), 1619, 1500, 1481, 1439 (C=C), 1360, 1200, 1177, 1133
1
(C–O), 925, 634. H NMR (400 MHz, CDCl3, ppm): d 1.91–2.08 (m, 4H, 2CH2),
2.31–2.38 (m, 4H, 2CH2), 2.55–2.63 (m, 4H, 2CH2), 4.72 (s, 1H, CH), 5.87 (s, 2H,
O–CH2–O), 6.65 (d, J = 8.5, 1H, Ar–H), 6.78–6.79 (m, 2H, Ar–H). 13C NMR
(100 MHz, CDCl3, ppm): d 19.25, 26.10, 30.22, 35.94, 99.75, 106.87, 107.94,
115.89, 120.62, 137.45, 144.95, 146.29, 162.78, 195.61. Anal. Calc. for C20H18O5:
C 70.99, H 5.36 %. Found: C 70.74, H 5.51 %.
9-(5-(Benzyloxy)-4-oxo-4H-pyran-2-yl)-3,4,6,7-tetrahydro-3,3,6,6-tetramethyl-2H-
xanthene-1,8(5H,9H)-dione (1h)
White powder; yield 95 %; M.P. = 190–192 °C; FTIR (KBr, cm-1): 3099 (Ar–
H), 2963 (C–H), 1660 (C=O), 1640 (C=O pyrone), 1581, 1498, 1456 (C=C), 1390,
1
1360, 1201, 1167, 1137 (C–O), 928, 699. H NMR (400 MHz, CDCl3, ppm): d
1.03 (s, 6H, 2CH3), 1.11 (s, 6H, 2CH3), 2.27 (s, 4H, 2CH2), 2.44 (s, 4H, 2CH2),
4.56 (s, 1H, CH), 4.99 (s, 2H, O–CH2), 6.28 (s, 1H, H-3 pyrone), 7.30–7.38 (m,
5H, Ar–H), 7.51 (s, 1H, H-6 pyrone). 13C NMR (100 MHz, CDCl3, ppm): d 26.43,
28.03, 30.02, 31.17, 39.83, 49.50, 70.76, 110.66, 113.07, 126.75, 127.28, 127.62,
139.60, 162.89, 195.12. Anal. Calc. for C29H30O6: C 73.40, H 6.37 %. Found: C
73.61, H 6.23 %.
123

K. D. Safa et al.
9-(5-(Benzyloxy)-4-oxo-4H-pyran-2-yl)-3,4,6,7-tetrahydro-2H-xanthene-
1,8(5H,9H)-dione (1i)
White powder; yield 96 %; M.P. = 188–190 °C; FTIR (KBr, cm-1): 3032 (Ar–H),
2922 (C–H), 1657 (C=O), 1637 (C=O pyrone), 1580, 1498, 1455 (C=C), 1358,
1
1360, 1206, 1178, 1128 (C–O), 989, 696. H NMR (400 MHz, CDCl3, ppm): d
2.03–2.04 (m, 4H, 2CH2), 2.32–2.46 (m, 4H, 2CH2), 2.52–2.65 (m, 4H, 2CH2), 4.62
(s, 1H, CH), 4.98 (s, 2H, O–CH2), 6.25 (s, 1H, H-3 pyrone), 7.29–7.36 (m, 5H, Ar–
H), 7.50 (s, 1H, H-6 pyrone). 13C NMR (100 MHz, CDCl3, ppm): d 18.96, 26.10,
29.83, 35.59, 70.65, 111.72, 113.00, 126.56, 127.21, 127.59, 134.83, 139.65,
164.54, 167.75, 173.78, 195.07. Anal. Calc. for C25H22O6: C 71.76, H 5.30 %.
Found: C 71.88, H 5.19 %.
General procedure for preparation of tetrahydrobenzoxanthene derivatives (1j–1o)
In a typical experiment, various aromatic aldehyde (1 mmol), cyclic 1,3-diketone
(1 mmol), b-naphtol (1 mmol) and 3 wt% of Fe-Cu/ZSM-5 in 2 ml of water was
introduced in a 20-ml, heavy-walled, pear-shaped, two-necked flask with nonstan-
dard tapered outer joint. The flask was attached to a 12-mm tip diameter probe and
the reaction mixture was sonicated at ambient temperature at 40 % power of the
processor. After completion of the reaction (monitored by TLC, within 5–10 min),
the solid product was filtered washed with water, dried, and recrystallized from
ethanol. The zeolite-supported transition metal catalysts was washed three times
with water and ethanol and dried under vacuum before reuse.
The spectral data of products
9,10-Dihydro-9,9-dimethyl-12-phenyl-8H-benzo[a]xanthen-11(12H)-one (1j)
White powder; yield 94 %; M.P. = 150–152 °C; FTIR (KBr, cm-1): 3053 (Ar–H),
2956 (C–H), 1650 (C=O), 1619, 1595, 1515, 1489, 1451 (C=C), 1374, 1142, 1117
(C–O), 975, 698. 1H NMR (400 MHz, CDCl3, ppm): d 0.96 (s, 3H, 1CH3), 1.12 (s,
3H, 1CH3), 2.24 (d, J = 16.3 Hz, 1H, CH2), 2.26 (d, J = 16.3 Hz, 1H, CH2), 2.57
(s, 2H, 2CH2), 5.71 (s, 1H, CH), 7.05 (t, J = 7.3 Hz, 1H, Ar–H), 7.17 (t,
J = 7.3 Hz, 2H, Ar–H), 7.32–7.45 (m, 5H, Ar–H), 7.77 (t, J = 7.5 Hz, 2H, Ar–H),
8.00 (d, J = 8.4 Hz, 1H, Ar–H). 13C NMR (100 MHz, CDCl3, ppm): d 26.15,
28.27, 28.69, 31.25, 33.67, 40.39, 49.88, 116.02, 116.67, 122.66, 123.86, 125.20,
125.97, 127.20, 127.40, 127.79, 130.37, 130.46, 143.71, 146.71, 162.86. Anal. Calc.
for C25H22O2: C 84.72, H 6.26 %. Found: C 84.91, H 6.13 %.
12-(5-(Benzyloxy)-4-oxo-4H-pyran-2-yl)-9,10-dihydro-9,9-dimethyl-8H-
benzo[a]xanthen-11(12H)-one (1l)
White powder; yield 94 %; M.P. = 196–198 °C; FTIR (KBr, cm-1): 3071 (Ar–H),
2927 (C–H), 1656 (C=O), 1639 (C=O pyrone), 1621, 1593, 1517, 1497, 1453
1
(C=C), 1369, 1142, 1114 (C–O), 979, 691. H NMR (400 MHz, CDCl3, ppm): d
123

Sonochemical syntheses of xanthene derivatives using…
1.12 (s, 3H, 1CH3), 1.19 (s, 3H, 1CH3), 2.40 (s, 2H, CH2), 2.62 (d, J = 18.0 Hz, 1H,
CH2), 2.68 (d, J = 18.0 Hz, 1H, CH2), 4.96 (d, J = 12.4 Hz, 1H, O–CH2), 5.00 (d,
J = 12.4 Hz, 1H, O–CH2), 5.65 (s, 1H, CH), 6.41 (s, 1H, H-3 pyrone), 7.30–7.34
(m, 6H, Ar–H), 7.45 (s, 1H, H-6 pyrone), 7.52 (t, J = 7.4 Hz, 1H, Ar–H), 7.60 (t,
J = 7.4 Hz, 1H, Ar–H), 7.86 (d, J = 8.8 Hz, 1H, Ar–H), 7.88 (d, J = 8.8 Hz, 1H,
Ar–H), 8.03 (d, J = 8.4 Hz, 1H, Ar–H). 13C NMR (100 MHz, CDCl3, ppm): d
26.32, 28.21, 28.68, 31.24, 32.45, 49.63, 70.69, 108.48, 111.81, 113.54, 116.12,
121.67, 124.44, 126.68, 127.27, 127.59, 127.71, 128.97, 130.12, 130.38, 134.67,
139.93, 145.84, 147.03, 165.24, 167.06, 173.66, 195.29. Anal. Calc. for C31H26O5:
C 77.81, H 5.48 %. Found: C 77.62, H 5.55 %.
Acknowledgments We thank Dr. J.D. Smith for his helpful comments. The authors also would like to
acknowledge the financial support from University of Tabriz and Iranian Nanotechnology Initiative.
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