Facile one-pot synthesis of tetrahydrobenzo[a]xanthene-11-one and aryl-14H-dibenzo[a.j]xanthene

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Facile One-Pot Synthesis of
Tetrahydrobenzo[a]xanthene-11-one and
Aryl-14H-dibenzo[a.j]xanthene
a
b
Ramin Ghorbani-Vaghei & Seyedeh Mina Malaekehpoor
a
Department of Organic Chemistry, Faculty of Chemistry, Bu-Ali Sina
University, Hamedan, Iran
b
Payame Noor University, Hamedan, Iran
Published online: 01 Oct 2010.
To cite this article: Ramin Ghorbani-Vaghei & Seyedeh Mina Malaekehpoor (2010) Facile One-Pot
Synthesis of Tetrahydrobenzo[a]xanthene-11-one and Aryl-14H-dibenzo[a.j]xanthene, Organic
Preparations and Procedures International: The New Journal for Organic Synthesis, 42:5, 494-498,
DOI: 10.1080/00304948.2010.514802
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Organic Preparations and Procedures International, 42:494–498, 2010
Copyright © Taylor & Francis Group, LLC
ISSN: 0030-4948 print
DOI: 10.1080/00304948.2010.514802
OPPI BRIEFS
Facile One-Pot Synthesis
of Tetrahydrobenzo[a]xanthene-11-one
and Aryl-14H-dibenzo[a.j]xanthene
Ramin Ghorbani-Vaghei and Seyedeh Mina Malaekehpoor2
1
1Department of Organic Chemistry, Faculty of Chemistry, Bu-Ali Sina
University, Hamedan, Iran
2
Payame Noor University, Hamedan, Iran
In recent years, xanthenes and benzoxanthenes have been of great interest because they have
1
2
been found to possess useful biological activities such as anti-inflammatory, antiviral, and
3
antibacterial activities. They also are being utilized as antagonists for the paralyzing ac-
4
5
6
tion of zoxazolamine, in photodynamic therapy, as leuco-dyes in laser technology, and as
7
pH-sensitive fluorescent materials for visualization of biomolecules. Several methods have
been reported for the synthesis of xanthene derivatives by the condensation of β-naphthol
8
with aldehydes and of β-naphthol, aldehydes and dimedone catalyzed by BF3.SiO2,
9
10
11
12
13
Sr(OTf)2, NaHSO4.SiO2, H14[NaP5W30O110], NH4H2PO4/SiO2, Amberlyst-15,
14
and p-TSA. However, many of these procedures suffer from harsh reaction conditions,
long reaction times, and difficult work-up.
In continuation of our interest in the application of N,N’-dibromo-N,N’-1,2-ethanediyl
bis(p-toluenesulfonamide) [BNBTS]1
5,16
in organic synthesis,
17,18
we report here a con-
venient method for the preparation of tetrahydrobenzo[a]xanthene-11-ones (4) in solution
and under solvent-free conditions (Scheme 1).
Me
Br
N
S
C
H
2
O O
2
BNBTS
Submitted June 4, 2009.
Address correspondence to Ramin Ghorbani-Vaghei, Department of Organic Chemistry, Faculty
of Chemistry, Bu-Ali Sina University, 65174, Hamedan, Iran. E-mail: rgvaghei@yahoo.com
494

Synthesis of Tetrahydrobenzo[a]xanthene-11-one
495
ArCHO
1
Ar
O
O
O
O
°
BNBTS, EtOH/H O/ 60 C
2
+
+
°
OH
Solvent-free/ 90 C
3
4a-j
2
a) Ar = C H b) Ar = p-CH C H c) Ar = p-CH OC H d) Ar = p-ClC H e) Ar = p-NO C H
2 6 4
6
5
3
6
4
3
6
4
6
4
f) Ar = m-NO C H g) Ar = o-ClC H h) Ar = 2-HO-5-BrC H i) Ar = p-HOC H j) Ar = o-CH OC H
6 4
2
6
4
6
4
6
3
6
4
3
Scheme 1
Among the solvents screened such as chloroform, ethylene chloride, toluene and aqueous
ethanol, the latter (70:30) proved to be the best (Table 1). No by-products were detected
under either conditions (in solution or under solvent-free conditions).
Similarly, dibenzo[a,j]xanthenes (5a-j) were obtained by the condensation of aromatic
aldehydes with two equivalents of β-naphthol under solvent-free conditions (Scheme 2,
Table 2); however, only poor yields (30–40%) were obtained when this reaction was
performed in solution.
Ar
OH
BNBTS
ArCHO +
2
°
Solvent-free/90 C
O
1
2
a) Ar = C H b) Ar = p-CH C H c) Ar = p-CH OC H d) Ar = p-ClC H4 e) Ar = p-NO C H
2 6 4
6
5
3
6
4
3
6
4
6
f) Ar = m-NO C H g) Ar = o-ClC H h) Ar = p-BrC H4 i) Ar = p-HOC H4 j) Ar = o-CH OC H
2
6
4
6
4
6
6
3
6
4
Scheme 2
In both cases, the reaction of aldehydes substituted with either electron-donating or
electron-withdrawing groups proceeded smoothly and gave the expected compounds in high
yields. However, aliphatic aldehydes gave very low yields (15–20%) of the corresponding
products 4 and 5. Since BNBTS contains bromine atoms attached to nitrogen atoms, it
+
15,17
is likely that it releases Br in situ, which acts as a catalyst in the reaction medium.
9
,10,13
Therefore, the mechanism shown in Scheme 3 can be suggested for this conversion.
Although the yields and reaction times using other reagents are approximately the same
Table 2), BNBTS is an inexpensive and mild catalyst which reacts under homogeneous
(
conditions. BNBTS is re-usable (after evaporation of ethanol) and after four runs, the
catalytic activity of the BNBTS was only reduced to about 35%.
ꢀ
ꢀ
In conclusion, we have introduced the novel catalytic reagent N,N -dibromo-N,N -1,2-
ethanediylbis(p-toluenesulfonamide) [BNBTS] as the activator for the reaction between
aldehydes and β-naphthol under solvent-free conditions and for the reaction of aldehydes,
β-naphthol and dimedone in solution or under solvent-free conditions. All the products
1
13
were characterized by their melting points, IR, H NMR and C NMR spectroscopic data.

496
Ghorbani-Vaghei and Malaekehpoor
ArCHOBr
OH
H+
BNBTS
β-naphthol
ArCHO
ArCHOBr
-
HOBr
ArCH+
H+
OH
dimedone or
4a-j
5a-j
+
BNBTS
or
β−naphthol
-H O
2
Scheme 3
Short reaction times, high yields, a reusable and inexpensive catalyst and easy work-up are
the advantages of this method.
Experimental Section
Substrates, solvents and other chemicals were purchased from Fluka, Merck and Aldrich
chemical companies. The progress of the reactions was monitored by TLC (SiO2-n-
hexane:acetone). IR spectra (KBr) were recorded on a Shimadzu Fx-90 infrared spec-
trophotometer and the NMR spectra were obtained on a JEOL 90 MHz spectrometer using
TMS as the internal standard. BNBTS was prepared according to our previously reported
1
5,16
procedure.
Table 1
Yields and mps of Tetrahydrobenzoxanthenes catalyzed by BNBTS.
a
Solvent-free
In Solutionb
◦
Cmpd
Yield
%)
Time
(min)
Yield
(%)
Time
(min)
mp. ( C)
lit. mp.
( C)
◦
(
9
4
4
4
4
4
4
4
4
4
4
a
b
c
d
e
f
g
h
i
93
90
93
97
88
87
95
97
92
95
92
80
25
93
60
95
45
20
52
42
90
92
90
92
86
87
90
92
90
91
100
120
30
60
50
190
60
20
60
87
147–149
174–176
203–205
178–180
177–179
170–172
175–177
265–267
227–229
158–160
151–153
20
176–178
204–205
180–182
178–180
168–170
179–180
266–268
223–225
163–165
9
9
20
9
20
20
10
20
j
a) Products were characterized from their physical properties, by comparison with authentic
samples, and by spectroscopic methods. b) In 70:30 ethanol-water.

Synthesis of Tetrahydrobenzo[a]xanthene-11-one
497
Table 2
Yields and mps of Aryl-14H-dibenzoxanthenes catalyzed by BNBTS.a
Solvent-free
◦
◦
Cmpd
Yield (%)
Time (min)
mp. ( C)
lit. mp. ( C)
8
5
5
5
5
5
5
5
5
5
5
a
b
c
d
e
f
g
h
i
90
88
87
96
95
93
90
89
89
90
24
70
120
50
90
74
100
76
45
180–182
224–226
208–209
283–285
308–310
215–217
198–200
295–297
138–140
261–263
183
228
204
8
8
8
286–288
8
310
213
19
8
8
203–205
296–298
11
140
2608
j
65
a) Products were characterized from their physical properties, by comparison with authentic
samples, and by spectroscopic methods.
Preparation of Aryl Tetrahydrobenzo[a]xanthen-11-ones (4a–j) under Solvent-free
Conditions. General Procedure
A mixture of the aldehyde (2 mmol), 2-naphthol (0.28 g, 2 mmol), 5,5-
dimethylcyclohexane-1,3-dione (0.31 g, 2.2 mmol) and BNBTS (0.1 g, 0.2 mmol) was
◦
stirred using a magnetic stirrer at 90 C. The progress of the reaction was monitored by
TLC (SiO2-n-hexane:acetone [8:2]). After completion of the reaction, ethanol (15 mL) was
added, stirred (6–7 min) and cooled. The precipitated product was collected and recrys-
tallized from methanol. Evaporation of the filtrate under reduced pressure gave BNBTS,
◦
characterized by its mp. 92–94 C, in nearly quantitative yield.
Preparation of Aryl Tetrahydrobenzo[a]xanthen-11-ones (4a–j) in Solution.
General Procedure
A mixture of the aldehyde (2 mmol), 2-naphthol (0.28 g, 2 mmol), 5,5-
dimethylcyclohexane-1,3-dione (0.31 g, 2.2 mmol), ethanol/water (2 mL) and BNBTS
◦
(
0.1 g, 0.2 mmol) was stirred using a magnetic stirrer at 60 C. The progress of the reac-
tion was monitored by TLC (n-hexane:acetone [8:2]). After completion of the reaction,
the solution was cooled. The precipitated product was collected and recrystallized from
methanol. Evaporation of the filtrate under reduced pressure gave BNBTS, characterized
◦
by its mp. 92–94 C, in nearly quantitative yield.
Preparation of Aryl 14H-Dibenzo[a]xanthen-11-ones (5a–j) under Solvent-free
Conditions. General Procedure
A mixture of the aldehyde (2 mmol), 2-naphthol (0.57 g, 4 mmol) and BNBTS (0.1 g,
◦
0
.2 mmol) was stirred using a magnetic stirrer at 90 C. The progress of the reaction was
monitored by TLC (n-hexane:acetone [8:2]). After completion of the reaction, ethanol (15

498
Ghorbani-Vaghei and Malaekehpoor
mL) was added and stirred (6–7 min) and cooled. The precipitated product was collected
and recrystallized from methanol. Evaporation of the filtrate under reduced pressure gave
◦
BNBTS, characterized by its mp. 92–94 C, in nearly quantitative yield.
Acknowledgement
We are thankful to Bu-Ali Sina University, Center of Excellence and Development of
Chemical Methods (CEDCM) for financial support.
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