A Facile Synthesis of Xanthene-1,8(2H)-dione Derivatives by Using Tetrapropylammonium Bromide as Catalyst

Article abstract of DOI:10.1002/jhet.3164

Several new derivatives of 9-aroyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione have been synthesized in yields varying from high to excellent by the condensation reaction of arylglyoxals with 1,3-diketones (cyclohexane-1,3-dione or dimedone) and TPAB

Full text of DOI:10.1002/jhet.3164

Month 2018
A Facile Synthesis of Xanthene-1,8(2H)-dione Derivatives by Using
Tetrapropylammonium Bromide as Catalyst
a
Sima Abdollahi,a Mahnaz Ezzati,a and Ebrahim Nemati-Kandeb
*
Ahmad Poursattar Marjani,
aDepartment of Organic Chemistry, Faculty of Chemistry, Urmia University, Urmia, Iran
bDepartment of Physical Chemistry, Faculty of Chemistry, Urmia University, Urmia, Iran
*
E-mail: a.poursattar@gmail.com; a.poursattar@urmia.ac.ir
Received December 29, 2017
DOI 10.1002/jhet.3164
Published online 00 Month 2018 in Wiley Online Library (wileyonlinelibrary.com).
Several new derivatives of 9-aroyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione have been synthe-
sized in yields varying from high to excellent by the condensation reaction of arylglyoxals with 1,3-
diketones (cyclohexane-1,3-dione or dimedone) and TPAB as an inexpensive, recoverable, and non-toxic
catalyst in the presence of ethanol/water under reflux conditions.
J. Heterocyclic Chem., 00, 00 (2018).
INTRODUCTION
xanthene-1,8(2H)-dione derivatives via the condensation
reaction of arylglyoxals 1 with 1,3-diketones 2, such as
cyclohexane-1,3-dione or dimedone, and TPAB in the
presence of ethanol/water under reflux conditions, in high
to excellent yields.
Among the fused organic heterocyclic compounds
containing-oxygen atom, xanthenes and their derivatives
are important because of their broad application in
several areas such as catalysis, materials science, as dyes
in laser technology, pH-sensitive fluorescent materials,
and for their biological properties [1,2].
RESULTS AND DISCUSSION
Such compounds have been intensively studied in
medicinal chemistry because they exhibit a wide range of
biological and pharmaceutical properties such as anti-
bacterial [3,4], anti-cancer [5–8], anti-inflammatory [9],
anti-fungal [10], anti-hypertensive [11], anti-malarial [12],
anti-plasmodial [13,14], and anti-viral [15].
Several methods for the synthesis of xanthene
derivatives appear in the literature [16], but the reported
methods are limited by low yields, high cost, use of toxic
solvents, high reaction temperatures, and the requirement
of special apparatus.
In attempting to develop a simple and short reaction
route to some novel substituted heterocyclic compounds
under mild conditions, we found that the reactions of
arylglyoxal monohydrates 1a–g with 2 eq of 1,3-diketone
[such as cyclohexane-1,3-dione (2a) or dimedone (2b)] as
active methylene compounds in the presence of
ethanol/water and TPAB under reflux conditions afforded
the corresponding new 9-aroyl-3,4,5,6,7,9-hexahydro-1H-
xanthene-1,8(2H)-diones 3a–n in 70–98% yield
(Scheme 1).
Tetrapropylammonium bromide is an inexpensive and
readily available phase transfer catalyst that has inherent
properties of environmental compatibility, operational
simplicity, being non-corrosive, and ease of reusability,
that has made it a suitable material in the preparation of
high silica zeolites of the ZSM type such as ZSM-5, and
also has many applications in different catalytic processes
[17,18].
In continuation of our interest in the development of
highly expedient methods for the synthesis of various
heterocyclic compounds with potential pharmaceutical
and biological properties [19–25], herein we report a
synthetic route for the synthesis of a new series of
In the absence of catalyst, no product was observed at
room temperature even after 24 h. Then, we evaluated the
yield and rate of reaction by using several catalysts such
as Alginate, Nano-Ag, SeO2, L-proline, sulfanilic acid,
p-TSA, and TPAB. The effects of solvent and
temperature for these catalysts are summarized in Table 1.
The best result in terms of yield (98%) and reaction time
(39 min) was obtained when the reaction was carried out
using TPAB as a catalyst in H2O/EtOH (1:3) (entry 11).
In this procedure, TPAB plays a crucial role in
accelerating the reaction, and its efficacy was examined
in various solvents such as water, ethanol, acetone, and
formic acid; H2O/EtOH proved to be the best.
© 2018 Wiley Periodicals, Inc.

A. Poursattar Marjani, S. Abdollahi, M. Ezzati, and E. Nemati-Kande
Vol 000
Scheme 1. The synthesis of compounds 3a–n. [Color figure can be viewed at wileyonlinelibrary.com]
Table 1
Optimizing the reaction condition for the synthesis of compound 3i.
Entry
Solvent
Catalyst (20 mol%)
Temperature (°C)
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
H2O
H2O
—
p-TSA
—
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
RT-Reflux
RT-Reflux
40
24
24
5
2
1
1
3
3
—
10
10
15
17
—
21
27
37
45
98
57
53
55
EtOH/H2O
EtOH/H2O
EtOH/H2O
EtOH/H2O
EtOH/H2O
EtOH/H2O
EtOH/H2O
EtOH/H2O
EtOH/H2O
EtOH
p-TSA
Sulfanilic acid
SeO2
Nano-Ag
Alginate
L-proline
L-proline
TPAB
TPAB
L-proline
L-proline
9
1
3
10
11
12
13
14
70
39 min
1.5
2
RT-Reflux
RT-Reflux
RT-Reflux
Acetone/H2O
HCO2H/H2O
4
After optimizing the reaction conditions, the scope of
this reaction was examined by using various electron rich
and deficient arylglyoxals to obtain a new series of
xanthene-1,8(2H)-dione derivatives 3a–n. The structure
of all products with their yields are shown in Figure 1.
The proposed mechanism for the formation of
compounds 3a–n is shown in Scheme 2. It involves the
initial Knoevenagel condensation of arylglyoxal 1a–g and
one mole of 1,3-diketone (cyclohexane-1,3-dione or
dimedone) to form the corresponding intermediate 4,
followed by Michael addition of another mole of 1,3-
diketone to this intermediate, followed by ring closure to
afford the compounds 3a–n.
ν = 1660–1666 cmÀ1 could be assigned to the vibration
of the carbonyl groups.
The recyclability of TPAB was also studied in the reaction
for synthesis of 3i. For this purpose, the recovered catalyst
was recycled and reused up to four times without any
significant loss of its catalytic performance.
The structures of products 3a–n were confirmed by
1
microanalysis and by their H-NMR, 13C-NMR, and FT-
IR spectral data, and X-ray crystallography of 3a. The
crystal structure of 3a and its crystal packing diagram is
shown in Figure 2. A summary of the crystal data and
experimental details of the data collections and structure
refinements are listed in Table 2.
The crystallographic data for structure 3a were
deposited at the Cambridge Crystallographic Data Center
(entry no. CCDC-1813573) and are available free of
charge upon request to CCDC, 12 Union Road,
Cambridge, UK (Fax: +44–1223-336033, e-mail:
deposit@ccdc.cam.ac.uk).
1
In the H-NMR spectra of the all compounds 3a–n, a
sharp singlet in the regions δ = 5.26–5.48 ppm was
attributed to the CH of the pyran ring. In the 13C-NMR
spectra of products 3a–n, signals located around
δ = 196.56–201.71 ppm were due to the carbonyl groups.
In the FT-IR spectra, the characteristic absorption band at
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2018
A Facile Synthesis of Xanthene-1,8(2H)-dione Derivatives
Figure 1. Structures of products synthesized. [Color figure can be viewed at wileyonlinelibrary.com]
EXPERIMENTAL
refluxed for an appropriate time (30–74 min) as monitored
by TLC (CH2Cl2:n-hexane:MeOH / 20:10:1 as eluents,
Rf = 0.78–0.93). After completion of the reaction, half of
the solvent was evaporated, and the precipitate was filtered,
washed with cold water, and recrystallized from ethanol to
afford the pure products 3a–n in 70–98%.
9-Benzoyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-
dione (3a). Orange crystals; yield 86%; mp 213–215°C
The chemicals used in this work were purchased from
Acros Organics or from Merck and were used without
purification. Melting points were determined on a digital
melting point apparatus (Electrothermal, Cole-Parmer,
1
Staffordshire, UK) and reported uncorrected. H and 13C
nuclear magnetic resonance (NMR) spectra were recorded
with a Bruker spectrometer at 300 and 75 MHz,
respectively (Bruker, Billerica, MA). The spectra were
measured in CDCl3 using TMS as the internal standard.
Infrared spectra were recorded on a Thermo Nicolet
(Nexus 670) FTIR spectrometer (Thermo Fisher
Scientific, Waltham, MA), using KBr disks. Elemental
analyses were performed using a Leco Analyzer 932
(Leco Corp., St. Joseph, MI).
[lit. [26], mp 210–212°C]. 1H-NMR δ (ppm): 8.30 (d,
J = 7.2 Hz, 2H, Ar H), 7.56 (t, J = 6.9 Hz, 1H, Ar
H), 7.48 (t, J = 7.2 Hz, 2H, Ar H), 5.44 (s, 1H, CH),
2.71 (t, J = 6.6 Hz, 1H), 2.65 (t, J = 6.6 Hz, 1H),
2.59 (t, J = 6.6 Hz, 1H), 2.53 (t, J = 6.6 Hz, 1H),
2.44–2.28 (m, 4H, 2 × CH2), 2.09–1.99 (m, 4H,
2 × CH2). 13C-NMR δ (ppm): 20.11, 27.19, 34.23,
36.42, 114.32, 128.14, 129.42, 132.93, 137.02, 165.87,
196.83, 201.71. FT-IR νmax: 3441, 3057, 2953, 2893,
General
procedure
for
the
synthesis
of
1663, 1435, 1351, 1180, 1128, 967, 736, 676 cmÀ1
.
9-aroyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione
3a–n. A mixture of arylglyoxal monohydrate (1 mmol),
cyclohexane-1,3-dione or dimedone (2 mmol), and TPAB
(20 mol%) in absolute ethanol and water (3:1) (5 mL) was
9-(4-Chlorobenzoyl)-3,4,5,6,7,9-hexahydro-1H-xanthene-
1,8(2H)-dione (3b). White crystals; yield 92%; mp 210–
1
212°C. H-NMR δ (ppm): 8.23 (dd, J = 8.4 Hz, 2H, Ar
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

A. Poursattar Marjani, S. Abdollahi, M. Ezzati, and E. Nemati-Kande
Vol 000
Scheme 2. Proposed mechanism for the synthesis of xanthene-1,8(2H)-diones 3a–n. [Color figure can be viewed at wileyonlinelibrary.com]
Figure 2. Crystal structure and crystal packing diagram of 3a. [Color figure can be viewed at wileyonlinelibrary.com]
H), 7.46 (d, J = 8.4 Hz, 2H, Ar H), 5.34 (s, 1H, CH), 2.72
(t, J = 5.7 Hz, 1H, CH), 2.68 (t, J = 6.6 Hz, 1H, CH), 2.55
(t, J = 6.6 Hz, 1H, CH), 2.50 (t, J = 5.7 Hz, 1H, CH),
2.43–2.28 (m, 4H, 2 × CH2), 2.11–2.02 (m, 4H,
2 × CH2). 13C-NMR δ (ppm): 20.11, 27.16, 34.40, 36.38,
114.23, 128.42, 130.76, 135.58, 139.23, 165.88, 196.86,
200.66. FT-IR νmax: 3432, 3065, 2950, 2894, 1664,
Anal. Calcd for C20H17ClO4: C, 67.33; H, 4.80. Found:
C, 67.42; H, 4.68%.
9-(4-Fluorobenzoyl)-3,4,5,6,7,9-hexahydro-1H-xanthene-
1,8(2H)-dione (3c). White crystals; yield 90%; mp 214–
216°C. 1H-NMR δ (ppm): 8.32 (d, J1 = 8.7 Hz,
J2 = 1.8 Hz, 2H, Ar H), 7.15 (t, J = 8.7 Hz, 2H, Ar H),
5.38 (s, 1H, CH), 2.72 (t, J = 8.7 Hz, 1H, CH), 2.66 (t,
J = 8.4 Hz, 1H, CH), 2.61 (t, J = 6.9 Hz, 1H, CH), 2.54
1587, 1353, 1182, 1133, 972, 850, 771, 531 cmÀ1
.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2018
A Facile Synthesis of Xanthene-1,8(2H)-dione Derivatives
2 × CH2), 2.06–1.97 (m, 4H, 2 × CH2). 13C-NMR δ
(ppm): 20.11, 27.19, 33.77, 36.47, 55.42, 113.38, 114.23,
Table 2
Crystal data and structure refinement for 3a.
129.78, 131.94, 163.53, 165.92, 196.84, 199.68. FT-IR
Empirical formula
C20H18O4
ν
max: 3303, 3065, 2955, 1661, 1606, 1509, 1444, 1356,
Formula weight (g molÀ1
Crystal size (mm3)
Crystal shape, color
Temperature (K)
Wavelength (Å)
Crystal system
Space group
)
322.34
0.46 × 0.23 × 0.10
Broken, Orange
1315, 1178, 1125, 1022, 961, 850, 783, 729, 681,
607 cmÀ1. Anal. Calcd for C21H20O5: C, 71.58; H, 5.72.
Found: C, 71.64; H, 5.66%.
296 (2)
0.71073
Monoclinic
P21/n
9-(3,4-Dimethoxybenzoyl)-3,4,5,6,7,9-hexahydro-1H-
xanthene-1,8(2H)-dione (3f). Yellow crystals; yield 71%;
1
mp 183–185°C. H NMR δ (ppm): 8.20 (d, J = 8.7 Hz,
a, b, c (Å)
11.299 (7), 9.134 (6), 15.454 (9)
1H, Ar H), 7.72 (s, 1H, Ar H), 6.99 (d, J = 7.8 Hz, 1H, Ar
H), 5.48 (s, 1H, CH), 3.97 (s, 3H, OCH3), 3.95 (s, 3H,
OCH3), 2.74–2.54 (m, 4H, 2 × CH2), 2.40–2.34 (m, 4H,
2 × CH2), 2.07–2.02 (m, 4H, 2 × CH2). 13C-NMR δ (ppm):
20.11, 27.23, 33.76, 36.51, 55.84, 55.96, 110.11, 111.59,
114.24, 125.09, 129.79, 148.53, 153.43, 165.93, 196.59,
199.53. FT-IR νmax: 3434, 3085, 2951, 2367, 1666, 1592,
1456, 1361, 1261, 1164, 953, 773, 638 cmÀ1. Anal. Calcd
α, γ
90
91.495 (8)
1594.3 (17)
4
1.343
0.093
β (°)
V (Å3)
Z
Density (Mg/m3)
Absorption coefficient μ
(mmÀ1
)
Maximum and minimum
transmission
θ range for data collection (°)
0.9907 and 0.9584
2.21–25.78
À13 ≤ ≤h ≤ 13, À11 ≤ k ≤ 11,
À18 ≤ l ≤ 18
for C22H22O6: C, 69.10; H, 5.80. Found: C, 69.00; H, 5.93%.
9-(4-Nitrobenzoyl)-3,4,5,6,7,9-hexahydro-1H-xanthene-
1,8(2H)-dione (3g). Orange crystals; yield 96%; mp 218–
Index ranges
Reflections collected
Independent reflections (Rint
11795
220°C. 1H-NMR δ (ppm): 8.39 (d, J = 8.4 Hz, 2H, Ar H),
8.31 (d, J = 8.4 Hz, 2H, Ar H), 5.26 (s, 1H, CH), 2.71–2.59
(m, 4H, 2 × CH2), 2.43–2.34 (m, 4H, 2 × CH2), 2.11–2.03
(m, 4H, 2 × CH2). 13C-NMR δ (ppm): 20.08, 27.09, 35.04,
36.23, 114.28, 122.32, 124.38, 130.82, 142.55, 166.01,
197.10, 201.02. FT-IR νmax: 3434, 3101, 2950, 2889,
1660, 1525, 1349, 1181, 1131, 972, 852, 740, 690,
532 cmÀ1. Anal. Calcd for C20H17NO6: C, 65.39; H,
)
3036 (0.0475)
Refinement method
Full-matrix least-squares on F2
1.028
Goodness-of-fit on F2
Final R indices [I > 2σ(I)]
R indices (all data)
R1 = 0.0662, wR2 = 0.1841
R1 = 0.1031, wR2 = 0.2178
0.584 and À0.244
Largest difference in peak
and hole (e ÅÀ3
)
(t, J = 6.6 Hz, 1H, CH), 2.44–2.28 (m, 4H, 2 × CH2), 2.09–
2.00 (m, 4H, 2 × CH2). 13C-NMR δ (ppm): 20.11, 27.17,
34.52, 36.40, 114.41, 114.21, 115.01, 133.09, 133.54,
165.90, 167.46, 196.86, 200.13. FT-IR νmax: 3433, 3072,
2956, 2894, 1663, 1590, 1353, 1207, 1182, 1132, 967,
850, 532 cmÀ1. Anal. Calcd for C20H17FO4: C, 70.58; H,
4.66; N, 3.81. Found: C, 65.43; H, 4.52; N, 3.75%.
9-Benzoyl-3,3,6,6-tetramethyl-3,4,5,6,7,9-hexahydro-1H-
xanthene-1,8(2H)-dione (3h). Yellow crystals; yield 86%;
mp 217–218°C [lit. [27], mp 219–220°C]. 1H-NMR δ
(ppm): 8.28 (d, J = 8.1 Hz, 2H, Ar H), 7.56 (t,
J = 6.9 Hz, 1H, Ar H), 7.48 (t, J = 6.6 Hz, 2H, Ar H),
5.42 (s, 1H, CH), 2.49 (s, 4H, 2 × CH2), 2.24 (s, 4H,
2 × CH2), 1.13 (s, 6H, 2 × CH3), 1.08 (s, 6H, 2 × CH3).
13C-NMR δ (ppm): 27.40, 29.00, 32.27, 40.97, 50.39,
113.13, 128.06, 129.29, 132.76, 137.29, 164.32, 196.61,
200.35. FT-IR νmax: 3427, 3079, 2954, 1666, 1453, 1360,
5.03. Found: C, 70.67; H, 4.90%.
9-(4-Methylbenzoyl)-3,4,5,6,7,9-hexahydro-1H-xanthene-
1,8(2H)-dione (3d). White crystals; yield 70%; mp 189–
1
191°C. H-NMR δ (ppm): 8.21 (d, J = 8.1 Hz, 2H, Ar
H), 7.28 (d, J = 6.9 Hz, 2H, Ar H), 5.45 (s, 1H, CH),
2.51–2.74 (m, 4H, 2 × CH2), 2.42 (s, 3H, CH3), 2.09–
2.00 (m, 4H, 2 × CH2), 2.36–2.28 (m, 4H, 2 × CH2).
13C-NMR (CDCl3) δ (ppm): 20.85, 28.40, 32.89, 37.76,
43.75, 113.75, 119.74, 128.91, 133.65, 136.45, 163.37,
195.05, 196.64. FT-IR νmax: 3426, 2903, 2855, 1664,
1580, 1499, 1420, 1368, 1254, 1160, 1016, 755. Anal.
1300, 1202, 1148, 995, 760, 677, 574 cmÀ1
.
9-(4-Chlorobenzoyl)-3,3,6,6-tetramethyl-3,4,5,6,7,9-hexahydro-
1H-xanthene-1,8(2H)-dione (3i). White crystals; yield 98%;
mp 199–201°C [lit. [27], mp 198–200°C]. 1H-NMR δ
(ppm): 8.21 (d, J = 8.4 Hz, 2H, Ar H), 7.45 (d, J = 8.7 Hz,
2H, Ar H), 5.32 (s, 1H, CH), 2.48 (s, 4H, 2 × CH2), 2.24
(s, 4H, 2 × CH2), 1.13 (s, 6H, 2 × CH3), 1.08 (s, 6H,
2 × CH3). 13C-NMR δ (ppm): 27.38, 28.95, 32.28, 40.91,
50.34, 113.01, 128.34, 130.70, 135.83, 139.05, 164.40,
196.72, 200.38. FT-IR νmax: 2963, 2935, 2874, 1666, 1571,
Calcd for C21H20O4: C, 74.98; H, 5.99. Found: C, 74.75;
H, 5.82%.
9-(4-Methoxybenzoyl)-3,4,5,6,7,9-hexahydro-1H-xanthene-
1,8(2H)-dione (3e).
White crystals; yield 73%; mp
1
1588, 1357, 1289, 1204, 1168, 1093, 988, 799 cmÀ1
.
204–205°C. H-NMR δ (ppm): 8.30 (d, J = 8.7 Hz, 2H,
Ar H), 6.96 (d, J = 8.7 Hz, 2H, Ar H), 5.42 (s, 1H, CH),
3.86 (s, 3H, OCH3), 2.70 (t, J = 5.7 Hz, 1H, CH), 2.64
(t, J = 5.7 Hz, 1H, CH), 2.56 (t, J = 6.9 Hz, 1H, CH),
2.51 (t, J = 6.6 Hz, 1H, CH), 2.42–2.26 (m, 4H,
9-(4-Fluorobenzoyl)-3,3,6,6-tetramethyl-3,4,5,6,7,9-
hexahydro-1H-xanthene-1,8(2H)-dione (3j). White crystals;
1
yield 82%; mp 178–180°C. H-NMR δ (ppm): 8.31 (dd,
J1 = 8.4 Hz, J2 = 1.8 Hz, 2H, Ar H), 7.15 (t, J = 8.4 Hz,
Journal of Heterocyclic Chemistry
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A. Poursattar Marjani, S. Abdollahi, M. Ezzati, and E. Nemati-Kande
Vol 000
2H, Ar H), 5.35 (s, 1H, CH), 2.49 (s, 4H, 2 × CH2), 2.24 (s,
CONCLUSIONS
4H, 2 × CH2), 1.12 (s, 6H, 2 × CH3), 1.08 (s, 6H, 2 × CH3).
13C-NMR δ (ppm): 27.55, 29.03, 32.33, 40.91, 50.36,
113.01, 115.90, 131.17, 132.95, 146.24, 164.45, 196.89,
199.96. FT-IR νmax: 3424, 3066, 2959, 2876, 2332, 1665,
1598, 1507, 1359, 1207, 1161, 811, 581 cmÀ1. Anal.
Calcd for C24H25FO4: C, 72.71; H, 6.36. Found: C,
In conclusion, an easy and efficient synthetic protocol
for the synthesis of xanthene-1,8(2H)-dione derivatives
has been described, by using a one-pot reaction of
arylglyoxals with 1,3-diketones in the presence of TPAB
as a catalyst. The method used has several advantages
including reusability of the catalyst, short reaction times,
high yield of the products, mild conditions, and easy
workup. These products may have great potential
pharmaceutical and biological applications.
72.60; H, 6.41%.
3,3,6,6-Tetramethyl-9-(4-methylbenzoyl)-3,4,5,6,7,9-hexahydro-
1H-xanthene-1,8(2H)-dione (3k).
White crystals; yield:
1
73%; mp 207–209°C [lit. [27], mp 210–212°C]. H NMR
δ (ppm): 8.18 (d, J = 8.1 Hz, 2H, Ar H), 7.27 (d,
J = 8.1 Hz, 2H, Ar H), 5.41 (s, 1H, CH), 2.49 (s, 4H,
2 × CH2), 2.41 (s, 3H, CH3), 2.23 (s, 4H, 2 × CH2), 1.11
(s, 6H, 2 × CH3), 1.07 (s, 6H, 2 × CH3). 13C-NMR δ
(ppm): 21.65, 27.39, 29.02, 32.27, 40.97, 50.43, 113.13,
128.82, 129.51, 134.65, 143.51, 164.29, 196.56, 200.75.
FT-IR νmax: 3433, 2953, 1665, 1590, 1514, 1359, 1262,
Acknowledgment. The authors are grateful to Urmia University
for financial support.
REFERENCES AND NOTES
1198, 1151, 1019, 891, 751, 640, 575 cmÀ1
.
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hexahydro-1H-xanthene-1,8(2H)-dione (3l).
Yellow
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Chem Rev 2008, 109, 190; (e) Feringa, B. L. J Org Chem 2007, 72, 6635.
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A. A.; Voulgarakis, N.; Aslanidis, P. Polyhedron 2014, 72, 122.
[4] Yunnikova, L. P.; Gorokhov, V. Y.; Makhova, T. V.;
Aleksandrova, G. A. Pharm Chem J 2013, 47, 139.
[5] Rewcastle, G. W.; Atwell, G. J.; Zhuang, L.; Baguley, B. C.;
Denny, W. A. J Med Chem 1991, 34, 217.
[6] Niu, S. L.; Li, Z. L.; Ji, F.; Liu, G. Y.; Zhao, N.; Liu, X. Q.;
Jing, Y. K.; Hua, H. M. Phytochemistry 2012, 77, 280.
crystals; yield 79%; mp 152–154°C [lit. [27], mp 154–
1
155°C]. H NMR δ (ppm): 8.29 (d, J = 7.2 Hz, 2H, Ar
H), 6.97 (d, J = 7.2 Hz, 2H, Ar H), 5.40 (s, 1H, CH),
3.87 (s, 3H, OCH3), 2.49 (s, 4H, 2 × CH2), 2.21 (s, 4H,
2 × CH2), 1.11 (s, 6H, 2 × CH3), 1.07 (s, 6H, 2 × CH3).
13C-NMR δ (ppm): 28.63, 32.32, 33.14, 34.12, 40.92,
50.41, 113.03, 129.99, 130.80, 131.91, 132.75, 164.40,
196.78, 199.40. FT-IR νmax: 3433, 2954, 1664, 1598,
1463, 1375, 1173, 1019, 808, 562 cmÀ1
.
[7] Lee, K. H.; Chai, H. B.; Tamez, P. A.; Pezzuto, J. M.; Cordell,
G. A.; Win, K. K.; Tin-Wa, M. Phytochemistry 2003, 64, 535.
[8] Tao, S. J.; Guan, S. H.; Wang, W.; Lu, Z. Q.; Chen, G. T.; Sha,
N.; Yue, Q. X.; Liu, X.; Guo, D. A. J Nat Prod 2008, 72, 117.
[9] Poupelin, J. P.; Saint-Ruf, G.; Foussard-Blanpin, O.; Marcisse,
G.; Uchida-Ernouf, G.; Lacroix, R. Eur J Med Chem 1978, 13, 67.
[10] Djoufack, G. L.; Valant-Vetschera, K. M.; Schinnerl, J.;
Brecker, L.; Lorbeer, E.; Robien, W. Nat Prod Commun 2010, 5, 1055.
[11] Diniz, T. F.; Pereira, A. C.; Capettini, L. S. A.; Santos, M. H.;
Nagem, T. J.; Lemos, V. S.; Cortes, S. F. Planta Med 2013, 79, 1495.
[12] Laphookhieo, S.; Syers, J. K.; Kiattansakul, R.;
Chantrapromma, K. Chem Pharm Bull 2006, 54, 745.
[13] Azebaze, A. G.; Meyer, M.; Valentin, A.; Nguemfo, E. L.;
Fomum, Z. T.; Nkengfack, A. E. Chem Pharm Bull 2006, 54, 111.
[14] Zelefack, F.; Guilet, D.; Fabre, N.; Bayet, C.; Chevalley, S. V.;
Ngouela, S.; Lenta, B. N.; Valentin, A.; Tsamo, E.; Dijoux-Franca, M.-G.
J Nat Prod 2009, 72, 954.
9-(3,4-Dimethoxybenzoyl)-3,3,6,6-tetramethyl-3,4,5,6,7,9-
hexahydro-1H-xanthene-1,8(2H)-dione (3m).
White
1
crystals; yield 88%; mp 116–118°C. H NMR δ (ppm):
8.17 (d, J = 8.1 Hz, 1H, Ar H), 7.69 (s, 1H, Ar H), 6.99
(d, J = 8.7 Hz, 1H, Ar H), 5.43 (s, 1H, CH), 3.97 (s, 3H,
OCH3), 3.95 (s, 3H, OCH3), 2.49 (s, 4H, 2 × CH2), 2.24
(s, 4H, 2 × CH2), 1.13 (s, 6H, 2 × CH3), 1.09 (s, 6H,
2 × CH3). 13C-NMR δ (ppm): 27.87, 28.63, 32.33, 33.12,
40.99, 50.47, 50.90, 110.58, 113.03, 125.86, 129.92,
148.41, 153.27, 158.69, 164.49, 196.79, 199.35. FT-IR
ν
max: 3433, 2953, 1665, 1514, 1359, 1262, 1152, 891,
751, 640, 575 cmÀ1. Anal. Calcd for C26H30O6: C, 71.21;
H, 6.90. Found: C, 71.38; H, 6.74%.
3,3,6,6-Tetramethyl-9-(4-nitrobenzoyl)-3,4,5,6,7,9-
[15] Jamison, J. M.; Krabill, K.; Hatwalkar, A.; Jamison, E.; Tsai,
C. C. Cell Biol Int Rep 1990, 14, 1075.
hexahydro-1H-xanthene-1,8(2H)-dione
(3n).
Orange
1
[16] (a) Singh, R.; Panda, G. Org Biomol Chem 2010, 8, 1097; (b)
Ziarani, G. M.; Badiei, A.-R.; Azizi, M. Sci Iran Trans C 2011, 18, 453;
(c) Böβ, E.; Hillringhaus, T.; Nitsch, J.; Klussmann, M. Org Biomol Chem
2011, 9, 1744; (d) Naidu, K. R. M.; Krishna, B. S.; Kumar, M. A.;
Arulselvan, P.; Khalivulla, S. I.; Lasekan, O. Molecules 2012, 17, 7543;
(e) Sashidhara, K. V.; Kumar, A.; Dodda, R. P.; Kumar, B. Tetrahedron Lett
2012, 53, 3281; (f) Pradeep, P.; Rao, J. S.; Shubha, J. Res J Chem Sci 2012,
2, 21; (g) Gazizov, A. S.; Smolobochkin, A. V.; Voronina, J. K.; Burilov, A.
R.; Pudovik, M. A. Tetrahedron 2015, 71, 445; (h) Mao, S.; Hua, Z.; Wu, X.;
Yang, Y.; Han, J.; Wang, L. Chem Select 2016, 3, 403.
crystals; yield 94%; mp 160–162°C. H NMR δ (ppm):
8.38 (d, J = 8.7 Hz, 2H, Ar H), 8.31 (d, J = 8.7 Hz, 2H,
Ar H), 5.26 (s, 1H, CH), 2.50 (s, 4H, 2 × CH2), 2.24 (s,
2H, CH2), 2.23 (s, 2H, CH2), 1.13 (s, 6H, 2 × CH3), 1.08
(s, 6H, 2 × CH3). 13C-NMR δ (ppm): 27.47, 28.83,
32.35, 40.85, 50.19, 113.06, 123.26, 129.90, 142.68,
149.84, 164.52, 196.99, 200.86. FT-IR νmax: 3439, 3094,
2956, 2878, 1662, 1521, 1465, 1352, 1199, 1158, 1000,
850, 753 cmÀ1. Anal. Calcd for C24H25NO6: C, 68.07; H,
5.95; N, 3.31. Found: C, 67.96; H, 6.07; N, 3.24%.
[17] Argauer, R. J.; Landolt, G. R.; US Pat 3 702 886, 1972.
[18] Bolm, C.; Magnus, A. S.; Hildebrand, J. P. Org Lett 2000,
2, 1173.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

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