Facile and rapid synthesis of 9-aryl 1,8-dioxooectahydroxanthenes derivatives using tungstate sulfuric acid

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Facile and Rapid Synthesis of 9-Aryl 1,8-
dioxoöctahydroxanthenes Derivatives
using Tungstate Sulfuric Acid
a
a
b
Bahador Karami , Khalil Eskandari , Sedigheh Gholipour & Masih
a
Jamshidi
a
Department of Chemistry, P. O. Box 353 , Yasouj University ,
Yasouj , 75918-74831 , Iran
b
Department of Chemistry, Gachsaran Branch , Islamic Azad
University , Gachsaran , Iran
To cite this article: Bahador Karami , Khalil Eskandari , Sedigheh Gholipour & Masih Jamshidi (2013)
Facile and Rapid Synthesis of 9-Aryl 1,8-dioxoöctahydroxanthenes Derivatives using Tungstate Sulfuric
Acid, Organic Preparations and Procedures International: The New Journal for Organic Synthesis, 45:3,
220-226, DOI: 10.1080/00304948.2013.764790
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Organic Preparations and Procedures International, 45:220–226, 2013
Copyright © Taylor & Francis Group, LLC
ISSN: 0030-4948 print / 1945-5453 online
DOI: 10.1080/00304948.2013.764790
Facile and Rapid Synthesis of 9-Aryl
,8-dioxo o¨ ctahydroxanthenes Derivatives
using Tungstate Sulfuric Acid
1
1
1
2
Bahador Karami, Khalil Eskandari, Sedigheh Gholipour,
and Masih Jamshidi1
1Department of Chemistry, P. O. Box 353, Yasouj University,
Yasouj 75918-74831, Iran
2
Department of Chemistry, Gachsaran Branch, Islamic Azad University,
Gachsaran, Iran
Xanthenes and its derivatives have received significant attention in recent years due to
1
–3
their wide range of biological and therapeutic properties. Xanthenes and its deriva-
tives have been prepared by various methods such as the reaction of aryloxymagne-
4
sium halides with triethyl orthoformate, cyclodehydration of a Mannich base (formed
from piperidine, formaldehyde and 2-hydroxy-5,7,8-trimethoxy-1,4-naphtoquinone) with a
5
6
phenol, trapping of benzynes with phenols, coupling of 3-(dimethoxymethyl)phenol with
7
2
-bromoacetophenone, followed by intramolecular phenyl–carbonyl coupling reaction,
cyclocondensation between 2-hydroxy aromatic aldehydes with 2-tetralone, and conden-
sation of β-naphthol with aldehydes or acetals. Furthermore xanthene derivatives may be
8
9
obtained by reaction of aldehydes, β-naphthol and cyclic 1,3-diketones in the presence of
10
catalysts such as tetra-(n-butyl) ammonium fluoride in various solvents. However, some of
these methods involve long reaction times, unsatisfactory yields, harsh reaction conditions
and often expensive catalysts.
Solid acids play a significant role in green chemistry, especially in chemical man-
ufacturing processes,1
1–14
generally have high turnover numbers and can be easily
separated from the organic components.15 Tungstate sulfuric acid (TSA) has been re-
ported as a new inorganic solid acid prepared by an improved, shorter and safer proce-
dure from anhydrous sodium tungstate with chlorosulfonic acid (1:2 mole) in n-hexane
16–18
(
Scheme 1).
We now describe the use of TSA for the synthesis of 1,8-dioxo o¨ ctahydroxanthenes 3
by condensation of 1,3-cyclohexanediones 1 with aromatic aldehydes 2 under solvent-free
conditions (Scheme 2). The structures of the products were deduced from their IR, NMR
spectroscopic data and their melting points.
Received December 10, 2012; in final form December 9, 2012.
Address correspondence to Bahador Karami, Department of Chemistry, P. O. Box 353, Yasouj
University, Yasouj, 75918-74831, Iran. E-mail: karami@mail.yu.ac.ir
220

Synthesis of 9-Aryl 1,8-dioxo o¨ ctahydroxanthenes Derivatives
221
Scheme 1
Scheme 2
Under the given conditions several aromatic aldehydes 2 containing electron-donating
as well as electron-withdrawing groups with different substitution patterns were effec-
tively cyclized to give 9-aryl-substituted 1,8-dioxo o¨ ctahydroxanthenes 3. No apprecia-
ble yields of products were obtained with aliphatic aldehydes and ketones, possibly
due to enolization; cinnamaldehyde gave the expected xanthene in 95% yield product
while other cyclic diketones such as 1,3-cyclopentane- and cycloheptanediones led to
pyrans.
The best molar ratio of the catalyst for this reaction was found to be 5 mol% for
the model reaction whereas larger amounts of the catalyst did not improve the results.
Comparison of this catalyst with other methods for the synthesis of 3,3,6,6-tetramethyl-9-
phenyl-1,2,3,4,5,6,7,8-octahydro-9H-xanthene-1,8-dione show that TSA provide the best
yields for the synthesis of xanthene derivatives (Table 1).
This method provides a simple, efficient and practical approach for the synthesis of
xanthene derivatives in the presence of tungstate sulfuric acid as an eco-friendly catalyst
◦
with high catalytic activity at 100 C under solvent-free conditions. The catalyst is recyclable
(up to five times) without significant loss of activity.
Experimental Section
Melting points were measured on an elecrtothermal KSB1N apparatus. IR spectra were
1
13
recorded in the matrix of KBr with JASCO FT-IR-680 plus spectrometer. H NMR and C
NMR spectra were determined on a FT-NMR Bruker Avance Ultra Shield Spectrometer at
400.13 and 100.62 MHz in CDCl3 as solvent in the presence of tetramethylsilane as internal
standard. TLC was performed on TLC-Grade silica gel-G/UV 254 nm plates (n-hexane,
ethyl acetate 2:1). Chemicals were purchased from Aldrich, Fluka and Merck chemical

222
Karami et al.
Table 1
Comparison of the Results for the Synthesis
of 3,3,6,6-Tetramethyl-9-phenyl-1,2,3,4,5,6,7,8-octahydro-9H-xanthene-1,8-dione
(
Table 2, Entry 1) with Other Catalysts
◦
Catalyst
Mol (%)
Solvent/Temp. ( C)
Time (min.) Yield (%)
[Ref.]
TSA
p-TsOH
DBSA
TMSClc
TBAHS
NaHSO4.SiO2
Selectfluor
PPA-SiO2f
5
5
Solvent free/100
MeOH, H2O/50
H2O-Ultrasonic/25–30
CH3CN/Reflux
Dioxane, H2O/Reflux
CH3CN/reflux
Solvent free/120
Solvent free/140
Solvent free/140
Solvent free/120
60
20
60
420
210
390
60
30
180
50
96
80
89
95
88
90
95
93
32
93
This work
a
19
b
20
21
22
10
100
10
50
10
10
10
10
d
23
TM e
24
25
2
5
6
HClO4-SiO2
SbCl3-SiO2
2
a) p-Toluenesulfonic acid. b) p-Dodecylbenzenesulfonic acid. c) Trimethylsilyl chloride.
d) Tetrabutylammonium bisulfate. e) 1-(Chloromethyl)-4-fluoro-1,4-diazoniabicyclo[2,2,2]octane
bis(tetrafluoroborate). f) Polyphosphoric acid supported on silica.
companies. All compounds were characterized by comparison with authentic samples and
combustion analyses.
Preparation of Catalyst
1
6–18
To 1 L of dry n-hexane in a 2 L round bottom flask, equipped with overhead stirrer
and cooled in an ice bath, was added 59 g (0.2 mol) of anhydrous sodium tungstate; then
7 mL (0.4 mol) of chlorosulfonic acid (CAUTION) was added dropwise over 30 min. This
mixture was stirred for 1.5 h. Afterwards the reaction mixture was gradually poured into
L of chilled distilled water with stirring. The yellowish catalyst which separated out was
2
1
collected, washed with distilled water (100 mL) five times until the filtrate showed negative
◦
test for chloride ion. Drying at 120 C for 5 h gave 80 g (98%) of the yellowish catalyst,
◦
17
◦
mp. 285 C (dec.). lit. 285 C.
General Procedure for the Preparation of 9-Aryl 1,8-Dioxo o¨ ctahydroxanthenes
A mixture of dimedone (28 g, 0.2 mol), aldehyde (0.1 mol) and TSA (3 g, 0.005 mol) was
◦
heated at 100 C for the time indicated in Table 2. The progress of the reaction was monitored
by TLC on silica gel (SILG/UV 254) plates (n-hexane, ethyl acetate 2:1). After completion
of the reaction, the reaction mixture was cooled to room temperature and washed with
CHCl3 (0.5 L), then was filtered to remove the catalyst and the filtrate was concentrated
in vacuum to afford the crude product which was recrystallized from EtOH to afford the
◦
crystalline pure product. The catalyst was washed with ethanol, dried at 120 C for 1 h, and
reused five times in other reactions.

Synthesis of 9-Aryl 1,8-dioxo o¨ ctahydroxanthenes Derivatives
223
Table 2
TSA-catalyzed Synthesis of 9-Aryl Substituted 1,8-Dioxo o¨ ctahydroxanthenes
Time
(min) (%)/[lit.]
Yield
a
◦
mp ( C)/[lit.]
Entry
Aldehyde 2
Product 3
1
60
45
96 (93)25 202–204 (201–202)25
90 (85)25 230–232 (230–232)25
2
3
4
90
30
88 (75)27 215–217 (216–217)27
95 (88)27 219–221 (221–223)27
5
6
60
60
89 (76)28 226–227 (226–228)28
93 (95)26 209–211 (210–212)26
7
35
92(90)28 223–225 (224–226)28

224
Karami et al.
Table 2
TSA-catalyzed Synthesis of 9-Aryl Substituted 1,8-Dioxo o¨ ctahydroxanthenes
(Continued)
Time
(min) (%)/[lit.]
Yield
a
◦
Entry Aldehyde 2
Product 3
mp ( C)/[lit.]
8
50
90 (88)29 250–252 (249–252)29
9
110
86 (75)30 189–191 (190–191)5,30
10
90
88 (80)5
238–239 (236–239)5
1
1
2
45
65
95 (82)31 271–273 (272–273)31
89 (84)25 260–262 (262–263)25
1
1
3
4
30
55
92 (84)32 224–227 (224–226)32
1
88 (80)4
250–252 (249–252)4
(Continued on next page)

Synthesis of 9-Aryl 1,8-dioxo o¨ ctahydroxanthenes Derivatives
225
Table 2
TSA-catalyzed Synthesis of 9-Aryl Substituted 1,8-Dioxo o¨ ctahydroxanthenes
(Continued)
Time
(min)
Yield
(%)/[lit.]
a
◦
mp ( C)/[lit.]
Entry
Aldehyde 2
Product 3
1
5
60
50
86 (84)33
170–172 (169–171)33
176–177 (175–177)20
16
95 (93)20
a) Identified by comparison with authentic samples.
Acknowledgment
Financial support from Yasouj University of Iran is gratefully acknowledged. The author is
grateful to Mrs. Abbaspour for useful cooperation in chemistry library of Tabriz University
of Iran.
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