Multicomponent, solvent-free synthesis of 12-aryl-8,9,10,12- tetrahydrobenzo[a]-xanthen-11-one derivatives catalysed by cyanuric chloride

Article abstract of DOI:10.1007/s12039-010-0049-0

An efficient and direct protocol for the preparation of 12-aryl-8,9,10,12-tetrahydro-benzo[a] xanthen-11-one derivatives employing a three-component one-pot reaction of aryl aldehydes, 2-naphthol and cyclic 1,3-dicarbonyl compounds in the presence of a ca

Full text of DOI:10.1007/s12039-010-0049-0

J. Chem. Sci., Vol. 122, No. 3, May 2010, pp. 427–432. © Indian Academy of Sciences.
Multicomponent, solvent-free synthesis of 12-aryl-8,9,10,12-
tetrahydrobenzo[a]-xanthen-11-one derivatives catalysed by
cyanuric chloride
ZHAN-HUI ZHANG*, PENG ZHANG, SHU-HONG YANG, HONG-JUAN WANG and
JIA DENG
The College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang 050016,
P.R. China
e-mail: zhanhui@126.com
MS received 4 May 2009; revised 12 July 2009; accepted 15 July 2009
Abstract. An efficient and direct protocol for the preparation of 12-aryl-8,9,10,12-tetrahydro-benzo[a]
xanthen-11-one derivatives employing a three-component one-pot reaction of aryl aldehydes, 2-naphthol
and cyclic 1,3-dicarbonyl compounds in the presence of a catalytic amount of cyanuric chloride (2,4,6-
trichloro-1,3,5-triazine, TCT) under solvent-free conditions is described. The desired products are
obtained in high yields with short reaction times.
Keywords. Xanthenes; aldehydes; 2-naphthol; multicomponent reactions; cyanuric chloride; solvent-
free condition.
1. Introduction
methods for the preparation of heterocyclic com-
pounds containing xanthone fragment remains an
interesting challenge.
Xanthenes and its derivatives are known as an im-
portant class of heterocyclic compounds widely used
as leco-dye,1 in laser technology,2 and pH sensitive
fluorescent materials.3 They possess a broad range
of useful pharmacological activities, including
antibacterial,4 antiviral,5 and anti-inflammatory
activities.6 These compounds are also utilized as
antagonists for paralyzing action of zoxazolamine7
and in photodynamic therapy.8 The high profile of
biological applications of compounds with xanthene
structures has prompted extensive studies for their
synthesis.9–12 A few methods have been developed
for the synthesis of 12-aryl-8,9,10,12-tetrahydro-
benzo[a]xanthen-11-one derivative; the most com-
mon method is the condensation of an ary aldehyde,
2-naphthol and cyclic 1,3-dicarbonyl compound in
boiling 1,2-dichloroethane in the presence of Na-
Recently, multicomponent reactions (MCRs) have
attracted considerable attention due to significant
advantages such as simplicity of operation, reduc-
tion of isolation and purification steps, and minimi-
zation of costs, time, and waste production.15 MCRs
are particularly useful to provide expedient appro-
aches to a wide range of compounds of biological
and pharmaceutical interest. In the context of MCR,
ortho-quinone methides (o-QMs) have been utilized
in many elegant tandem processes.16 Recently,
we demonstrated that a mixture of aldehydes, 2-
naphthol and amide when heated at 100°C in the
presence of cyanuric chloride under solvent-free
condition, afforded amidolky naphthol derivatives.17
This reaction proceeds through in situ formation of
ortho-quinone methide intermediates. Previously,
we also reported the synthesis 1,8-dioxo-octahydro-
xanthenes by treatment of aromatic aldehydes and
5,5-dimethylcyclohexane-1,3-dione.18 Due to our
interest in the multicomponent syntheses and in con-
tinuation of our work on the development of new
synthetic methodologies,19 we report here, a simple
and facile protocol for the synthesis of a series of
12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-one
HSO4⋅SiO2 or strontium triflate.14 However, in
13
spite of their potential utility, some of these methods
suffer drawbacks such as the use of toxic and
hazardous solvents, unsatisfactory product yields,
expensive catalyst, and proloned reaction times.
Hence, the development of new and simple synthetic
*For correspondence
427

428
Zhan-Hui Zhang et al
Scheme 1. Synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-one
derivatives.
derivatives from aldehydes, 2-naphthol and cyclic 7⋅22–7⋅38 (m, 4H), 7⋅43 (d, J = 8.0 Hz, 1H), 7⋅76 (d,
1,3-dicarbonyl compounds using cyanuric chloride J = 7.6 Hz, 2H), 8⋅01 (d, J = 8⋅4 Hz, 1H); 13C NMR
as a catalyst under solvent-free conditions (scheme 1). (100 MHz, CDCl3): δ = 21⋅1, 27⋅3, 29⋅3, 32⋅6, 34⋅3,
41⋅4, 50⋅9, 114⋅4, 117⋅1, 117⋅9, 123⋅7, 124⋅9, 127⋅0,
128⋅3, 128⋅4, 128⋅7, 129⋅0, 131⋅4, 131⋅5, 135⋅7,
141⋅9, 147⋅7, 163⋅8, 197⋅0; ESI-MS m/z = 369
2. Experimental
(M + 1)+; Anal. Calcd for C26H24O2: C, 84⋅75; H,
Melting points were recorded on X-4 apparatus
(Beijing Tech Instrument Co., Ltd) and are uncor-
rected. IR spectra were recorded on a Shimadzu
6⋅57. Found: C, 85⋅02; H, 6⋅38.
1
2.1b 12-(4-Fluorophenyl)-9,9-dimethyl-8,9,10,12-
tetrahydrobenzo[a]xanthen-11-one (4e): White solid,
m.p. 185–186°C; IR (KBr) 3037, 2954, 2881, 1651,
1618, 1595, 1508, 1398, 1375, 1226, 1184, 1026,
FTIR-8900 spectrophotometer with KBr optis. H
NMR and 13C NMR spectra were recorded with
Varian 400 spectrometer using TMS as an internal
standard. Mass spectra were recorded on a Ther-
moFinnigan LCQ Advantage instrument with an ESI
source (4⋅5 KeV). Elemental analyses were carried
out using a Vario EL III CHNOS Elemental Ana-
lyzer.
1
839 cm–1; H NMR (400 MHz, CDCl3): δ = 0⋅96
(s, 3H), 1⋅12 (s, 3H), 2⋅24 and 2⋅31 (AB system,
J = 16⋅4 Hz, 2H), 2⋅57 (s, 2H), 5⋅70 (s, 1H), 6⋅85
(t, J = 8⋅8 Hz, 2H), 7⋅28–7⋅46 (m, 5H), 7⋅78
(t, J = 8⋅0 Hz, 2H), 7⋅93 (d, J = 8⋅4 Hz, 1H); 13C
NMR (100 MHz, CDCl3): δ = 27⋅1, 29⋅4, 32⋅2, 34⋅0,
41⋅4, 50⋅9, 114⋅1, 114⋅9, 115⋅1, 117⋅1, 117⋅4, 123⋅6,
125⋅0, 127⋅1, 128⋅5, 129⋅1, 129⋅9, 131⋅3, 131⋅5,
140⋅6, 147⋅7, 163⋅9, 196⋅9; ESI-MS m/z = 373
(M + 1)+; Anal. Calcd for C25H21FO2: C, 80⋅62; H,
5⋅68. Found: C, 80⋅80; H, 5⋅45.
2.1 Typical procedure for the preparation of 4b
2,4,6-Trichloro-1,3,5-triazine (TCT) (0⋅05 mmol)
was added to a mixture of 2-naphthol (1 mmol), 4-
methylbenzaldehyde (1⋅0 mmol) and dimedone
(1⋅2 mmol) and the reaction mixture was heated at
80°C. The progress of the reaction was monitored by
TLC. After completion of the reaction, water
(10 mL) was added and the mixture was extracted
with ethyl acetate (3 × 10 mL). The extract was
dried (MgSO4) and evaporated to give the crude
product. The crude product was purified by chroma-
tography over silica gel using ethyl acetate/
cyclohexane as eluent to afford pure product.
2.1c 12-(3,4-Dichlorophenyl)-9,9-dimethyl-8,9,10,
12-tetrahydrobenzo[a]xanthen-11-one (4g): White
solid, m.p. 181–182°C; IR (KBr) 3138, 2962, 1649,
1637, 1618, 1596, 1558, 1398, 1384, 1373, 1234,
1
1202, 1070, 819 cm–1; H NMR (400 MHz, CDCl3):
δ = 0⋅98 (s, 3H), 1.12 (s, 3H), 2⋅24 and 2⋅30 (AB
system, J = 16⋅4 Hz, 2H), 2⋅58 (s, 2H), 5⋅70 (s, 1H),
7⋅19–7⋅24 (m, 1H), 7⋅30–7⋅48 (m, 5H), 7⋅78–7⋅85
(m, 2H), 7⋅86 (d, J = 8⋅4 Hz, 1H); 13C NMR
(100 MHz, CDCl3): δ = 27⋅2, 29⋅2, 32⋅3, 34⋅1, 41⋅3,
50⋅7, 113⋅3, 116⋅3, 117⋅1, 123⋅2, 125⋅1, 127⋅3, 128⋅0,
129⋅4, 130⋅1, 130⋅3, 131⋅0, 131⋅5, 132⋅2, 144⋅9,
147⋅7, 164⋅3, 196⋅8; ESI–MS m/z = 423 (M + 1)+;
Anal. Calcd for C25H20Cl2O2: C, 70⋅93; H, 4⋅76.
Found: C, 71⋅05; H, 4⋅68.
2.1a 9,9-Dimethyl-12-p-tolyl-8,9,10,12-tetrahydro-
benzo[a]xanthen-11-one (4b): White solid, m.p.
175–176°C; IR (KBr) 3014, 2870, 1647, 1618, 1597,
1400, 1371, 1226, 1186, 1147, 1028, 812 cm–1; H
1
NMR (400 MHz, CDCl3): δ = 0⋅98 (s, 3H), 1⋅12 (s,
3H), 2⋅25 and 2⋅29 (AB system, J = 16⋅4 Hz, 2H),
2⋅57 (s, 2H), 5⋅67 (s, 1H), 6⋅98 (d, J = 7.6 Hz, 2H),

Multicomponent, solvent-free synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]-xanthen-11-one
429
2.1d 12-(4-Bromophenyl)-9,9-dimethyl-8,9,10,12- 306°C; IR (KBr) 3024, 2951, 2893, 2829, 1651,
tetrahydrobenzo[a]xanthen-11-one (4h): White 1618, 1508, 1456, 1402, 1336, 1226, 1188, 1176,
1
solid, m.p. 208–209°C; IR (KBr) 3064, 1643, 1618, 1126, 999, 954 cm–1; H NMR (400 MHz, CDCl3):
1593, 1514, 1483, 1400, 1375, 1220, 1174, 1008, δ = 1⋅91–1⋅94 (m, 2H), 2⋅21 (s, 3H), 2⋅31–2⋅48 (m,
1
837 cm–1; H NMR (400 MHz, CDCl3): δ = 0⋅97 (s, 2H), 2⋅56–2⋅76 (m, 2H), 5⋅70 (s, 1H), 6⋅98 (d,
3H), 1⋅12 (s, 3H), 2⋅25 and 2⋅30 (AB system, J = 8⋅0 Hz, 1H), 7⋅03 (d, J = 8⋅0 Hz, 1H), 7⋅19 (d,
J = 16⋅4 Hz, 2H), 2⋅57 (s, 2H), 5⋅67 (s, 1H), 7⋅20– J = 8⋅0 Hz, 1H), 7⋅25 (d, J = 8⋅0 Hz, 1H), 7⋅31–7⋅44
7⋅46 (m, 7H), 7⋅78 (d, J = 7⋅6 Hz, 2H), 7⋅90 (d, (m, 3H), 7⋅76 (t, J = 8⋅0 Hz, 2H), 7⋅97 (d, J =
13
J = 8⋅4 Hz, 1H); 13C NMR (100 MHz, CDCl3): 8⋅4 Hz, 1H); C NMR (100 MHz, CDCl3): δ = 20⋅3,
δ = 27⋅1, 29⋅4, 32⋅3, 34⋅3, 41⋅4, 50⋅9, 113⋅7, 116⋅9, 21⋅1, 27⋅2, 27⋅7, 34⋅2, 37⋅1, 115⋅7, 117⋅0, 117⋅8,
117⋅1, 120⋅2, 123⋅4, 125⋅0, 127⋅1, 128⋅5, 129⋅1, 130⋅2, 123⋅7, 124⋅9, 127⋅0, 128⋅3, 128⋅4, 128⋅8, 129⋅0,
131⋅2, 131⋅3, 1315, 143⋅8, 147⋅7, 164⋅1, 19⋅9; ESI-MS 131⋅4, 135⋅7, 142⋅2, 147⋅7, 163⋅9, 165⋅6, 196⋅6; ESI-
m/z = 433 (M + 1)+; Anal. Calcd for C25H21BrO2: C, MS m/z = 341 (M + 1)+; Anal. Calcd for C24H20O2:
69⋅29; H, 4⋅88. Found: C, 69⋅53; H, 4⋅52.
C, 84⋅68; H, 5⋅92. Found: C, 84⋅82; H, 6⋅05.
2.1e 9,9-Dimethyl-12-(3-nitrophenyl)-8,9,10,12-
tetrahydrobenzo[a]xanthen-11-one (4i): White solid,
m.p. 166–167°C; IR (KBr) 3139, 2958, 2912, 1649,
1618, 1597, 1400, 1375, 1348, 1224, 1176, 1085,
2.1h 12-(4-Fluophenyl)-8,9,10,12-tetrahydrobenzo
[a]xanthen-11-one (4q): White solid, m.p. 210–
212°C; IR (KBr) 3134, 1652, 1618, 1600, 1506,
1438, 1398, 1382, 1359, 1226, 1188, 1178, 999,
1
812 cm–1; H NMR (400 MHz, CDCl3): δ = 0⋅94 (s,
1
846 cm–1; H NMR (400 MHz, CDCl3): δ = 1⋅95–
3H), 1⋅12 (s, 3H), 2⋅23 and 2⋅31 (AB system,
J = 16⋅4 Hz, 2H), 2⋅59 (s, 2H), 5⋅80 (s, 1H), 7⋅32–
7⋅39 (m, 3H), 7⋅34 (d, J = 7⋅6 Hz, 1H), 7⋅77–7⋅80
(m, 3H), 7⋅85 (d, J = 8.4 Hz, 1H), 7⋅91 (d,
J = 8⋅0 Hz, 1H), 8⋅14 (d, J = 8⋅0 Hz, 1H); 13C NMR
(100 MHz, CDCl3): δ = 27⋅1, 29⋅3, 32⋅2, 34⋅7, 41⋅3,
50⋅7, 113⋅1, 116⋅0, 117⋅3, 121⋅6, 123⋅1, 123⋅2,
125⋅2, 127⋅4, 128⋅7, 129⋅1, 129⋅6, 130⋅9, 131⋅6,
134⋅8, 146⋅8, 147⋅8, 148⋅3, 164⋅6, 196⋅9; ESI-MS
m/z = 400 (M + 1)+; Anal. Calcd for C25H21NO4: C,
75⋅17; H, 5⋅30; N, 3⋅51. Found: C, 75⋅32; H, 5⋅12;
N, 3⋅70.
2⋅07 (m, 2H), 2⋅31–2⋅44 (m, 2H), 2⋅54–2⋅71 (m, 2H),
5⋅66 (s, 1H), 6⋅61 (d, J = 8⋅4 Hz, 1H), 6⋅66 (d,
J = 8⋅4 Hz, 1H), 7⋅14 (d, J = 8⋅4 Hz, 1H), 7⋅18 (d,
J = 8⋅4 Hz, 1H), 7⋅30–7⋅42 (m, 3H), 7⋅76 (t,
J = 8⋅4 Hz, 2H), 7⋅94 (d, J = 8⋅4 Hz, 1H); 13C NMR
(100 MHz, CDCl3): δ = 27⋅1, 31⋅1, 33⋅9, 37⋅0,
114⋅7, 114⋅9, 115⋅1, 117⋅0, 125⋅0, 127⋅0, 128⋅5,
129⋅0, 129⋅9, 130⋅0, 131⋅2, 131⋅5, 140⋅8, 147⋅7,
164⋅0, 165⋅7, 197⋅1; ESI-MS m/z = 345 (M + 1)+;
Anal. Calcd for C23H17FO2: C, 80⋅22; H, 4⋅98.
Found: C, 80⋅13; H, 5⋅12.
2.1i 12-(4-Bromophenyl)-8,9,10,12-tetrahydro-
benzo[a]xanthen-11-one (4t): White solid, m.p.
208–209°C; IR (KBr) 2941, 2899, 1651, 1616, 1595,
1485, 1400, 1385, 1229, 1190, 1130, 1010, 833 cm–1;
1H NMR (400 MHz, CDCl3): δ = 1⋅98–2⋅08 (m, 2H),
2⋅31–2⋅44 (m, 2H), 2⋅56–2⋅73 (m, 2H), 5⋅69 (s, 1H),
7⋅17–7⋅22 (m, 1H), 7⋅28–7⋅45 (m, 6H), 7⋅77–7⋅80
(m, 2H), 7⋅87 (d, J = 8⋅4 Hz, 1H); 13C NMR
(100 MHz, CDCl3): δ = 20⋅3, 27⋅1, 34⋅2, 36⋅9,
115⋅0, 116⋅9, 117⋅0, 120⋅1, 123⋅4, 125⋅0, 127⋅1,
128⋅5, 129⋅1, 130⋅3, 131⋅2, 131⋅4, 144⋅1, 147⋅7,
164⋅2, 165⋅8, 197⋅1; ESI-MS m/z = 405 (M + 1)+;
Anal. Calcd for C23H17BrO2: C, 68⋅16; H, 4⋅23.
Found: C, 68⋅32; H, 4⋅08.
2.1f 12-[4-(9,9-Dimethyl-8-oxo-8,9,10,11-tetra-
hydro-7H-benzo[c]xanthen-7-yl)-phenyl]-9,9-
dimethyl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-
one (4k): White solid, m.p. 310–311°C; IR (KBr)
3055, 1670, 1618, 1508, 1375, 1226, 1174, 1130,
954, 819 cm–1; 1H NMR (400 MHz, CDCl3):
δ = 0⋅79 (s, 6H), 1⋅04 (s, 3H), 1⋅06 (s, 3H), 2⋅10–
2⋅24 (m, 4H), 2⋅46 (s, 2H), 2⋅50 (s, 2H), 5⋅56 (s,
1H), 5⋅60 (s, 1H), 7⋅09 (d, J = 8⋅0 Hz, 4H), 7⋅28–
7⋅34 (m, 6H), 7⋅69–7⋅87 (m, 6H); 13C NMR
(100 MHz, CDCl3): δ = 27⋅2, 29⋅0, 32⋅2, 33⋅8, 41⋅3,
50⋅9, 114⋅3, 117⋅0, 117⋅6, 123⋅9, 124⋅8, 126⋅9,
128⋅1, 128⋅2, 128⋅6, 131⋅3, 131⋅4, 142⋅3, 147⋅9,
163⋅9, 197⋅0; ESI-MS m/z = 631 (M + 1)+; Anal.
Calcd for C44H38O4: C, 83⋅78; H, 6⋅07. Found: C,
83⋅96; H, 5⋅91.
3. Results and discussion
Initial studies were conducted using the model reac-
tion of 2-naphthol (1 mmol), 4-chlorobenzaldehyde
2.1g 12-p-Tolyl-8,9,10,12-tetrahydrobenzo[a]
xanthen-11-one (4m): White solid, m.p. 305–

430
Zhan-Hui Zhang et al
Table 1. The synthesis of 12-(4-chlorophenyl)-9,9-dimethyl-8,9,10,12-tetra-
hydrobenzo-[a]xanthen-11-one (4f) under different conditionsa.
Entry
Catalyst
Catalyst loading (mol%) Time (h) Yield (%)b
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
No
12
1
1
1
1
1
1
1
1
1
0.5
0.5
1
1
3
Trace
48
59
46
75
68
70
52
55
Benzeneboronic acid
Sulfamic acid
N-Bromosuccinimide
ZrOCl2⋅8H2O
KAl(SO4)2⋅12H2O
KAl(SO4)2⋅12H2O/SiO2
SbCl3/SiO2
SbCl3/montmorillonite K-10
TCT
TCT
10
10
10
10
10
10
10
10
1
5
10
5
5
5
75
92
TCT
TCT
TCT
TCT
90
0c
80d
36e
aThe reaction was carried out according to general experimental procedure. bIsolated
c
d
yields. The reaction was carried out at room temperature. The reaction carried out
at 50°C. eThe reaction carried out in boiling 1,2-dichloroethane.
(1 mmol), and 5,5-dimethyl-1,3-cyclohexanedione divergent aromatic aldehydes, cyclic 1,3-dicarbonyl
(1⋅2 mmol) under various conditions. The results are compounds and 2-naphthol were tested and the re-
summarized in table 1. Only a trace amount of the sults are summarized in table 2. Unlike previously
product was obtained when the reaction was carried reported method where 4–7 h were required for
out in the absence of catalyst even after 12 h (table completion of this reaction in the presence of
1, entry 1). TCT was the most effective catalyst in NaHSO4⋅SiO2 in refluxing 1,2-dichloreethane,13 the
terms of yield of product (92%) while other catalysts present methodology afforded high yields of the
such as benzeneboronic acid, sulfamic acid, N- products 4a–4v within short times (30–70 min). In
bromosuccinimide, ZrOCl2⋅8H2O, KAl(SO4)2⋅12H2O, general, aldehydes bearing electron-donating groups
SbCl3/SiO2, and SbCl3/montmorillonite K-10, the need slightly longer times to complete the reaction
yield of the product was lower (46–75%). as compared to aldehydes containing electron-
Further, TCT is a stable, non-volatile, inexpensive, withdrawing groups. Various functional groups such
commercially available and easy–to–handle re- as NO2, Cl, Br, OH and OCH3 were tolerated. This
agent.20 It has been utilized for many synthetic reaction was further explored for the synthesis of
transformations.21 Optimization of the reaction bis-benzo[a]xanthen-11-one compound (table 2, en-
conditions was undertaken using TCT as a catalyst. try 4k) in high yields by the reaction of terephtha-
The result showed that 5 mol% of TCT was suffi- laldehyde with 2 equiv. 2-naphthol and 5,5-
cient to get a fairly high yield (table 1, entry 11). dimethyl-1,3-cyclohexanedione under similar condi-
With 1 mol% of TCT, a lower yield was observed tions (scheme 2).
even after 1 h. An higher amount of the catalyst
A possible mechanism for the formation of 4a–4v
(10 mol%) scale did not improve the yield. We is proposed in scheme 3. Adventitious entry of mois-
also tested the effect of reaction temperature on ture leads to the release of HCl. The in situ gener-
the catalysed reaction. When it was carried out at ated HCl acts as a protic acid to activate the
80°C, the maximum yield was obtained in a short carbonyl oxygen. The reaction proceeds through the
duration. Lower yield was obtained when intermediate o-QMs, formed in situ by the reaction
the reaction was carried out in boiling 1,2- of 2-naphthol with aromatic aldehydes as reported in
dichloroethane (table 1, entry 15).
the literature.22 Subsequent addition of dimedone to
After optimizing the conditions, we next evalu- the o-QMs forms intermediate 5, followed by cycli-
ated the generality and scope of this TCT catalysed zation to give the corresponding products 4, accom-
reaction. An array of structurally and electronically panied by loss of H2O.

Multicomponent, solvent-free synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]-xanthen-11-one
431
Table 2. Synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-one derivatives.
Entry
Aldehyde
R
Time (min)
Yield (%)a
m.p. (°C)
a
b
c
d
e
f
g
h
i
j
k
l
m
n
o
p
q
r
s
PhCHO
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
H
H
H
H
H
H
H
H
H
50
70
70
50
30
30
30
30
35
30
50
50
70
70
70
60
30
30
30
30
30
30
90
87
86
84
91
92
92
93
85
93
84
88
86
85
83
85
92
91
91
90
92
90
149–15023
175–17623
207–20813
151–15213
185–186
4-MeC6H4CHO
4-MeOC6H4CHO
4-OHC6H4CHO
4-FC6H4CHO
4-ClC6H4CHO
3,4-Cl2C6H3CHO
4-BrC6H4CHO
3-NO2C6H4CHO
4-NO2C6H4CHO
4-CHOC6H4CHO
PhCHO
4-MeC6H4CHO
4-MeOC6H4CHO
4-OHC6H4CHO
3-OMe-4-OHC6H3CHO
4-FC6H4CHO
3-ClC6H4CHO
4-ClC6H4CHO
4-BrC6H4CHO
3-NO2C6H4CHO
4-NO2C6H4CHO
188–18913
181–182
186–187
166–167
175–17623
310–311
189–19013
205-20623
181–18223
269–270
193–19423
210–212
209–21024
205–20623
208–209
t
u
v
H
H
235–23623
234–23523
aYields refer to isolated yield.
Scheme 2. Synthesis of bis-benzo[a]xanthen-11-one compound (4k).
Scheme 3. A proposed mechanism.

432
Zhan-Hui Zhang et al
13. Das B, Laxminarayana K, Krishnaiah M and Srinivas
Y 2007 Synlett 3107
3. Conclusions
14. Li J, Tang W, Lu L and Su W 2008 Tetrahedron Lett.
49 7117
In conclusion, we have described a very simple,
convenient and practical method for the synthesis of
12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-one
derivatives through a three-component one-pot reac-
tion of aryl aldehydes, 2-naphthol and cyclic 1,3-
dicarbonyl compounds. The procedure clearly dem-
onstrates that TCT is an excellent catalyst for the
synthesis of xanthene-based compounds.
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Acknowledgements
We are grateful for financial support from National
Natural Science Foundation of China (20872025),
Nature Science Foundation of Hebei Province
(B2008000149), Natural Science Foundation of
Hebei Education Department (2006318) and Science
17. Zhang P and Zhang Z-H 2009 Monatsh. Chem. 140
199
18. Zhang Z-H and Liu Y-H 2008 Catal. Commun. 9
1715
Foundation
(L20061314).
of
Hebei
Normal
University
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Tetrahedron Lett. 50 916; (f) Liu Y-H, Tao X-Y, Lei
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