Ceric-sulfate-catalyzed synthesis of 14-aryl- or 14-alkyl-14H-dibenzo[aj] xanthene under conventional heating and microwave irradiation

Article abstract of DOI:10.1139/V07-116

A simple and facile procedure for the synthesis of 14-aryl- or 14-alkyl-14H-dibenzo[oj]xanthenes is described. The procedure takes place by the one-pot condensation of 2-naphthol with aldehydes in the presence of anhydrous eerie sulfate as the catalyst un

Full text of DOI:10.1139/V07-116

9
89
Ceric-sulfate-catalyzed synthesis of 14-aryl- or
4-alkyl-14H-dibenzo[aj]xanthene under
1
conventional heating and microwave irradiation
Nagarajan Panneer Selvam, Gnanamani Shanthi, and Paramasivan T. Perumal
Abstract: A simple and facile procedure for the synthesis of 14-aryl- or 14-alkyl-14H-dibenzo[aj]xanthenes is de-
scribed. The procedure takes place by the one-pot condensation of 2-naphthol with aldehydes in the presence of anhy-
drous ceric sulfate as the catalyst under solvent-free conventional heating and microwave irradiation.
Key words: xanthene, one-pot condensation, aldehyde, 2-naphthol, ceric sulfate, solvent-free, microwave irradiation.
Résumé : On a mis au point une méthode simple et efficace d’effectuer la synthèse de 14-aryl- ou 14-alkyl-14H-
dibenzo[aj]xanthènes qui implique une réaction de condensation monotope du 2-naphtol avec des aldéhydes en pré-
sence de sulfate cérique anhydre agissant comme catalyseur, en l’absence de solvant et faisant appel à des chauffages
conventionnels ou des irradiations de microondes.
Mots-clés : xanthène, condensation monotope, aldéhyde, 2-naphtol, sulfate cérique, sans solvant, irradiation de microondes.
[
Traduit par la Rédaction] Selvam et al. 995
Introduction
Fig. 1. Examples of xanthene derivatives.
Recently, much attention has been focused on the synthe-
sis of aryl-14H-dibenzo[aj]xanthenes because of their signif-
icant biological activities as antibacterials (1), antivirals (2),
anti-inflammatory agents (3), in photodynamic therapy (4),
and for their role as antagonists of the paralyzing action of
zoxazolamine (5). Xanthene-based compounds have also
been investigated for agricultural bactericide activity, and
some other benzoxanthenes find applications in industries,
such as dyes in laser technology (6) and fluorescent materi-
als for visualization of biomolecules (7). A number of
xanthene-based skeletons are also available from natural
sources; for example, tetrahydroxanthene 1, ehretianone 2
O
HO
O
O
O
1
2
1
-methanol (15), formamide (16), carbon monoxide (17),
(
Fig. 1), and santalin pigments have been isolated from a
and aldehyde acetals (18). Khosropour et al. (19) reported
the synthesis of alkyl-14H-dibenzo[aj]xanthenes from alde-
hydes, β-naphthol, and p-toluenesulfonic acid in 1,2-
dichloroethane as solvent and under solvent-free condition.
The reaction required extended time as long as 2.5–24 h, and
yields of some of the products were not satisfactory. Hence,
practical methods of obtaining benzoxanthenes are of great
interest in the lead optimization process of drug discovery.
To avoid these limitations, we have started the search for a
new catalyst with high catalytic activity and non-hazardous
method with shorter reaction time involving simple work-up
procedure. Recent literature has shown considerable interest
in the use of Ce(IV) reagents, especially cerium(IV)
ammonium nitrate (CAN) (20), in the construction of
carbon–carbon and carbon–heteroatom bonds. The use of
Ce(IV) sulfate (21) as Lewis acid catalyst is very scarce.
As part of our research program directed towards the de-
velopment of highly expedient methods and the syntheses of
diverse heterocyclic compounds of biological significance
number of plant species (8).
Various procedures have been reported for the synthesis of
xanthene derivatives, including the reaction of aryloxy mag-
nesium halides with triethyl orthoformate (9), cyclodehy-
dration (10), trapping of benzynes by phenols (11),
intramolecular phenyl carbonyl coupling reaction of
benzaldehyde and acetophenones (12), cyclization of
polycyclic aryl triflate esters (13), and cyclocondensation
between 2-hydroxy aromatic aldehydes and 2-tetralones
(
14). Additionally, 14H-dibenzoxanthenes and its analogues
are prepared by the reaction of 2-naphthol with 2-naphthol-
Received 21 June 2007. Accepted 20 August 2007. Published
on the NRC Research Press Web site at canjchem.nrc.ca on
1
7 October 2007.
1
N.P. Selvam, G. Shanthi, and P.T. Perumal. Organic
Chemistry Division, Central Leather Research Institute,
Chennai 600 020, India.
(
22), we herein disclose a new, convenient, and one-pot
synthesis of aryl-14H-dibenzo[aj]xanthene and alkyl-14H-
1Corresponding author (e-mail: ptperumal@gmail.com).
Can. J. Chem. 85: 989–995 (2007)
doi:10.1139/V07-116
© 2007 NRC Canada

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Can. J. Chem. Vol. 85, 2007
Scheme 1. Synthesis of 14H-dibenzoxanthene.
R
O
OH
Ce(SO ) , 100 °C
4
2
RCHO + 2
Ce(SO ) , MWI
4
2
Scheme 2. Synthesis of acetamidophenol.
Cl
Cl
O
H
N
OH
+
Ce(SO ) (1 equiv.)
4
2
OH
CH CN, 85 °C, 24 h
3
CHO
Table 1. Screening of various solvents.
Table 2. Optimization of the reaction conditions.
Entry
Solvent
Time (h)
Yield (%)a
Yields (%)a
Entry
Catalyst (equiv.)
Time (h)
1
2
3
4
5
6
Dichloroethane
Toluene
Acetonitrile
Methanol
1,4-Dioxane
Neat
4
4
24
8
4
2
70
72
5
75
80
85
1
2
3
4
5
6
1
2
2
2
2
2
2
85
88
90
94
94
88
0.5
0.4
0.3
0.2
0.1
Note: Reactions were carried out in 2 mmol scale.
Isolated yields.
Note: Reactions were carried out in 2 mmol scale.
Isolated yields.
a
a
dibenzo[aj]xanthene from aldehydes and β-naphthol cata-
ety of substituents on araldehydes. The nature of functional
groups on the aromatic ring of the aldehyde exerted a strong
influence on the reaction time. An increase in the reaction
rate was observed with aryl aldehydes bearing electron-
withdrawing group.
lyzed by Ce(SO ) under solvent-free conventional and
4
2
microwave conditions in excellent yields (Scheme 1).
Results and discussion
The reaction with pyrazolyl aldehyde afforded new
pyrazolyl xanthene in good yield (Scheme 4). The structure
of the product 3 was confirmed by single crystal X-ray anal-
This work is an extension of our previous results describ-
ing the synthesis of acetamidophenols (23) by Ritter-type re-
action from 2-naphthol and araldehydes in acetonitrile in the
2
ysis (Fig. 2) and spectral data.
presence of anhyd. Ce(SO ) , where acetonitrile is involved
4
2
Encouraged by these results, we extended our protocol by
using substituted phenols (e.g., 4-methoxyphenol, 4-
chlorophenol, 3-nitrophenol, and 1-naphthol) instead of 2-
naphthol. The reactions were very sluggish, and no product
formation was observed.
in the reaction sequence as a nucleophile (Scheme 2).
In an initial endeavor, we carried out the reaction of 2-
naphthol with 4-chlorobenzaldehyde in the presence of
one equiv. of the catalyst under different reaction conditions
using various solvents (Table 1). Excellent results were ob-
tained when the reaction was carried out neat. Similarly, the
mole ratio of Ce(SO ) was studied, and the results are listed
Conclusion
4
2
in Table 2. It was found that the amount of Ce(SO ) affects
In summary, we have developed a convenient and efficient
method for the synthesis of aryl- or alkyl-14H-
dibenzo[aj]xanthenes, via three-component reaction offering
various advantages, such as shorter reaction time, milder
condition, high yield, general applicability, and the use of in-
expensive and commercially available cerium(IV)sulfate.
4
2
the yield of the product, with 20 mol% of Ce(SO ) being
4
2
optimum (Scheme 3).
The substrate scope of the reaction under the optimized
conditions was investigated, and the results were summa-
rized in Table 3. The reaction was amenable to a wide vari-
2
Supplementary data for this article are available on the journal Web site (canjchem.nrc.ca) or may be purchased from the Depository of Un-
published Data, Document Delivery, CISTI, National Research Council Canada, Ottawa, ON K1A 0S2, Canada. DUD 5223. For more in-
formation on obtaining material, refer to cisti-icist.nrc-cnrc.gc.ca/irm/unpub_e.shtml. CCDC 654516 contains the crystallographic data for
this manuscript. These data can be obtained, free of charge, via www.ccdc.cam.ac.uk/conts/retrieving.html (Or from the Cambridge Crystal-
lographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax +44 1223 336033; or deposit@ccdc.cam.ac.uk).
©
2007 NRC Canada

Selvam et al.
991
Table 3. Syntheses of various substituted 14-aryl- and 14-alkyl-14H-dibenzo[aj]xanthenes.
Method A
Method B
Time [min] Yield [%]a
Entry
Aldehyde
Mp [°C]
Yield [%]a
Time [h]
1
2
CHO
2.0
1.5
92
90
2.0
2.0
94
93
1
83–185 (19)
CHO
212–214 (19)
Cl
Cl
3
4
Cl
Cl
CHO
CHO
2.0
2.0
2.0
94
86
2.0
2.0
2.0
95
90
286–289 (19)
252–254 (24a)
5
6
7
F
CHO
CHO
CHO
85
93
96
88
94
95
237–239 (19)
306–308 (19)
210–211 (19)
O N
1.5
2.0
1.5
2.0
2
O N
2
8
9
CHO
1.5
2.5
88
84
2.0
2.0
90
88
290–291 (24b)
NO2
CHO
MeO
202–204 (19)
1
0
H C
CHO
CHO
2.0
2.5
78
80
2.0
2.0
80
84
224–227 (19)
148–151 (19)
3
1
1
2
H C
3
CHO
1
2.5
5.0
86
65
3.5
8.0
90
70
202–204
200–202
HO
CHO
1
3
4
CHO
1
2.5
92
3.0
94
198–200
a
Isolated yields and all products were characterized by comparison of their NMR, IR, mass, and physical data with those of
authentic samples.
©
2007 NRC Canada

9
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Can. J. Chem. Vol. 85, 2007
Scheme 3. Synthesis of 14-(4-chloro-phenyl)-14H-dibenzo[aj]xanthene.
Cl
Cl
OH
Ce(SO4)2 (0.2 equiv.)
+
1
00 °C
CHO
O
Scheme 4. Synthesis of pyrazolyl xanthene.
N
N
Ph
OH
Ce(SO ) (0.2 equiv.)
4
2
+
N
CHO
N
or MW
O
0% - 82%
8
3
chased from S.D. Fine-Chem. Limited and used as received.
Fig. 2. ORTEP diagram of compound 3.
Acetonitrile was distilled from CaH under nitrogen and
2
stored over 4 Å molecular sieves. DMSO-d was purchased
6
from Aldrich. Melting points were determined in open capil-
lary tubes and are uncorrected. IR measurements were car-
ried out using KBr pellets in PerkinElmer Spectrometer
1
13
RXI–FTIR. H NMR and C NMR spectra were recorded in
JEOL 500 MHz high-resolution NMR spectrometer with
TMS as an internal standard. Mass spectra were obtained us-
ing JEOL DX–303 in EI ionization mode at 70 eV. TLC was
performed on precoated Polygram SIL G/UV254 sheets.
Typical experimental procedure for the synthesis of
aryl-14H-dibenzo[aj]xanthenes
Method A
A mixture of the aldehyde (2 mmol), 2-naphthol
4 mmol), and anhyd. ceric sulfate (0.4 mmol) was stirred at
00 °C for the appropriate time as mentioned in Table 3.
(
1
Completion of the reaction was confirmed by TLC. The re-
action mixture was extracted with dichloromethane (3 ×
1
5 mL), ceric sulfate was filtered off, and the filtrate was
concentrated under reduced pressure. The solid obtained was
recrystallized from ethyl alcohol.
Method B
A mixture of the aldehyde (2 mmol), 2-naphthol
4 mmol), and anhyd. ceric sulfate (0.4 mmol) was inserted
(
Experimental
in a microwave oven (BPL BMG 800 TS model) on a silica
gel solid support and irradiated at 300 W for the appropriate
time as mentioned in Table 3. Completion of the reaction
was confirmed by TLC. The reaction mixture was extracted
with dichloromethane (3 × 15 mL), ceric sulfate was filtered
Materials and general
Glassware were hot-air oven-dried prior to use. Ce-
rium(IV) sulfate and 4-methoxy phenol were purchased from
Lancaster Research Chemicals. All other reagents were pur-
©
2007 NRC Canada

Selvam et al.
993
off, and the filtrate was concentrated under reduced pres-
sure. The solid obtained was recrystallized from ethyl alco-
hol.
126.9, 128.9, 129.1, 129.7, 129.7, 131.1, 131.4, 140.9, 148.,
160.2, 162.08. MS m/z: 377.1 (M + 1).
1
4-(4-Nitrophenyl)-14H-dibenzo[aj]xanthene (Table 3,
1
4-Phenyl-14H-dibenzo[aj]xanthene (Table 3, entry 1)
entry 6)
White solid, mp 183–185 °C (lit. value 185 °C) (19). IR
Pink-brown solid, mp 306–308 °C (lit. value 310 °C) (19).
–
1
1
–1
1
(
KBr) ν
cm : 3021, 1623, 1592, 1402, 1250, 805. H
IR (KBr) ν
cm : 2930, 1594, 1517, 1343, 1241, 828. H
max
max
NMR (500 MHz, CDCl ) δ: 6.55 (s, 1H), 7.03 (t, 1H, J =
NMR (500 MHz, CDCl ) δ: 6.93 (s, 1H), 7.50 (m, 2H), 7.67
3
3
13
7
7
9
9
1
1
.6 Hz), 7.17 (t, 2H, J = 7.6 Hz), 7.42 (t, 2H, J = 6.9 Hz),
.52 (d, 2H, J = 9.2 Hz), 7.58 (m, 4H), 7.79 (d, 2H, J =
.15 Hz), 7.83 (d, 2H, J = 7.65 Hz), 8.42 (d, 2H, J =
(m, 4H), 8.03 (m, 8H), 8.71 (d, 2H, J = 8.4 Hz). C NMR
(125 MHz, CDCl ) δ: 36.4, 116.2, 117.7, 123.1, 123.6,
124.7, 127.2, 128.7, 129.6, 130.7, 130.8, 145.9, 148.1,
152.6. MS m/z: 403 (M ).
3
1
3
+
.15 Hz). C NMR (125 MHz, CDCl ) δ: 38.2, 117.4,
3
18.2, 122.8, 124.4, 126.53, 126.9, 128.4, 128.6, 128.9,
29.0, 131.2, 131.6, 145.2, 148.8. MS m/z: 358 (M ).
+
1
4-(3-Nitrophenyl)-14H-dibenzo[aj]xanthene (Table 3,
entry 7)
1
4-(2-Chlorophenyl)-14H-dibenzo[aj]xanthene (Table 3,
Yellow solid, mp 210–211 °C (lit. value 211 °C) (19). IR
–
1
1
entry 2)
White solid, mp 212–214 °C (lit. value 215 °C) (19). IR
(KBr) ν
cm : 3077, 1592, 1527, 1347, 1250, 810. H
max
NMR (500 MHz, CDCl ) δ: 6.55 (s, 1H), 7.23 (t, 1H, J =
3
–
1
1
(
KBr) ν
cm : 3026, 1601, 1583, 1422, 1249, 820. H
7.65 Hz), 7.41 (t, 2H, J = 6.9 Hz), 7.49 (d, 2H, J = 8.4 Hz),
7.59 (t, 2H, J = 7.6 Hz), 7.79 (m, 6H), 8.27 (d, 2H, J =
max
NMR (500 MHz, CDCl ) δ: 6.79 (s, 1H), 6.88 (p, 2H, J =
3
1
3
8
7
2
8
.4 Hz), 7.25 (d, 1H, J = 7.6 Hz), 7.38 (d, 1H, J = 7.6 Hz),
.42 (t, 2H, J = 7.6 Hz), 7.48 (d, 2H, J = 8.4 Hz), 7.61 (t,
H, J = 8.4 Hz), 7.78 (d, 2H, J = 8.4 Hz), 7.81 (d, 2H, J =
8.4 Hz), 8.41 (s, 1H). C NMR (125 MHz, CDCl ) δ: 37.8,
115.9, 118.2, 121.8, 122.1, 122.8, 124.7, 127.3, 129.2,
3
129.6, 129.7, 131.1, 134.4, 147.0, 148.3, 148.8. MS m/z: 403
1
3
+
.4 Hz), 8.73 (d, 2H, J = 8.4 Hz). C NMR (125 MHz,
(M ).
CDCl ) δ: 34.7, 118.1, 118.2, 123.6, 124.5, 127.0, 127.9,
1
1
3
28.0, 128.8, 129.2, 129.7, 130.2, 130.9, 131.9, 131.9,
43.7. MS m/z: 393 (M + 1).
1
4-(2-Nitrophenyl)-14H-dibenzo[aj]xanthene (Table 3,
entry 8)
Yellow solid, mp 290–291 °C (lit. value 293 °C) (24b). IR
–
1
1
1
4-(4-Chlorophenyl)-14H-dibenzo[aj]xanthene (Table 3,
(
(
KBr) ν
cm : 2921, 1581, 1350, 1241, 809. H NMR
max
entry 3)
White solid, mp 286–289 °C (lit. value 289 °C) (19). IR
500 MHz, CDCl ) δ: 7.02 (t, 1H, J = 7.6 Hz), 7.18 (t, 1H,
3
J = 7.65 Hz) 7.41 (t, 2H, J = 6.85 Hz), 7.47 (t, 3H, J =
8.4 Hz), 7.54 (s, 1H), 7.58 (t, 2H, J = 7.6 Hz), 7.78 (t, 5H,
–
1
1
(
KBr) ν
cm : 2925, 1590, 1484, 1242, 1083, 807. H
max
1
3
NMR (500 MHz, CDCl ) δ: 6.71 (s, 1H), 7.16 (d, 2H, J =
J = 7.65 Hz), 8.51 (d, 2H, J = 8.4 Hz). C NMR (125 MHz,
3
7
7
7
1
1
.6 Hz), 7.4 (t, 4H, J = 7.6 Hz), 7.51 (d, 2H, J = 8.4 Hz),
.60 (m, 4H), 7.89 (d, 4H, J = 7.6 Hz), 8.62 (d, 2H, J =
CDCl ) δ: 32.6, 117.6, 118.1, 122.7, 124.8, 125.0, 127.4,
3
127.7, 128.8, 129.5, 131.0, 131.8, 132.3, 134.2, 140.9,
1
3
.6 Hz). C NMR (125 MHz, CDCl ) δ: 39.9, 117.5, 118.2,
147.1, 149.5. MS m/z: 404.69 (M + 1).
3
23.8, 125.1, 127.6, 128.9, 129.2, 129.8, 130.2, 131.2,
31.3, 131.4, 145.0, 148.5. MS m/z: 393 (M + 1).
1
4-(4-Methoxyphenyl)-14H-dibenzo[aj]xanthene
(
Table 3, entry 9)
1
4-(2,4-Dichlorophenyl)-14H-dibenzo[aj]xanthene
Yellow solid, mp 202–204 °C (lit. value 204 °C) (19). IR
–
1
1
(
Table 3, entry 4)
(
(
KBr) ν
cm : 2922, 1592, 1510, 1030, 810. H NMR
max
White solid, mp 252–254 °C (lit. value 253–255 °C)
500 MHz, CDCl ) δ: 3.60 (s, 3H), 6.44 (s, 1H), 6.66 (d, 2H,
3
–
1
(
8
1
24a). FTIR (KBr) ν cm : 3059, 1620, 1590, 1465, 1247,
max
J = 8.4 Hz), 7.39 (m, 4H), 7.47 (d, 2H, J = 8.4 Hz), 7.56 (t,
2H, J = 8.4 Hz), 7.77(d, 2H, J = 9.15 Hz), 7.81 (d, 2H, J =
1
06. H NMR (500 MHz, CDCl ) δ: 6.74 (s, 1H), 6.87 (d,
3
1
3
H, J = 8.45 Hz), 7.26 (m, 2H), 7.42 (m, 4H), 7.60 (t, 2H,
8
.4 Hz), 8.37 (d, 2H, J = 8.4 Hz). C NMR (125 MHz,
J = 6.9 Hz), 7.78 (d, 2H, J = 9.2 Hz), 7.81 (d, 2H, J =
8
CDCl ) δ: 34.3, 117.5, 118.2, 123.2, 124.6, 127.1, 128.5,
1
1
CDCl ) δ: 37.18, 55.1, 113.9, 117.6, 118.1, 122.8, 124.3,
3
.4 Hz), 8.63 (d, 2H, J = 8.4 Hz). 13C NMR (125 MHz,
1
26.9, 128.8, 128.9, 129.2, 131.1, 131.5, 137.5, 148.7,
3
157.9. MS m/z: 389.8 (M + 1).
28.8, 129.2, 129.4, 130.7, 130.9, 131.7, 132.8, 132.9,
42.3, 148.9. MS m/z: 428 (M + 2).
1
4-(4-Methylphenyl)-14H-dibenzo[aj]xanthene (Table 3,
entry 10)
1
4-(4-Fluorophenyl)-14H-dibenzo[aj]xanthene (Table 3,
Light-brown solid, mp 224–227 °C (lit. value 229 °C)
entry 5)
Brown solid, mp 237–239 °C (lit. value 239 °C) (19). IR
–1
1
(
19). IR (KBr) ν
cm : 2925, 1590, 1520, 1250, 810. H
max
NMR (500 MHz, CDCl ) δ: 2.13 (s, 3H), 6.46 (s, 1H), 6.96
3
–
1
1
(
KBr) ν
cm : 3068, 1623, 1592, 1242, 959, 744. H
max
(d, 2H, J = 7.65 Hz), 7.42 (t, 4H, J = 7.6 Hz), 7.49 (d, 2H,
J = 9.2 Hz), 7.57 (t, 2H, J = 8.4 Hz), 7.78 (d, 2H, J =
NMR (500 MHz, CDCl ) δ: 6.47 (s, 1H), 6.80 (t, 2H, J =
3
9
2
7
.15 Hz), 7.40 (t, 2H, J = 7.65 Hz), 7.45 (m, 4H), 7.57 (t,
H, J = 7.65 Hz), 7.78 (d, 2H, J = 9.15 Hz), 7.82 (d, 2H, J =
9
.2 Hz), 7.82 (d, 2H, J = 7.6 Hz), 8.40 (d, 2H, J = 8.4 Hz).
C NMR (125 MHz, CDCl ) δ: 21.0, 37.7, 109.6, 117.5,
18.1, 122.8, 124.3, 126.8, 128.2, 128.9, 129.2, 131.1,
13
3
1
3
.6 Hz), 8.32 (d, 2H, J = 8.4 Hz). C NMR (125 MHz,
1
CDCl ) δ: 37.3, 115.3, 115.5, 117.2, 118.1, 122.6, 124.4,
3
131.5, 136.0, 142.2, 148.8. MS m/z: 373 (M + 1).
©
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Can. J. Chem. Vol. 85, 2007
1
4-Ethyl-14H-dibenzo[aj]xanthene (Table 3, entry 11)
126.98, 128.41, 128.46, 128.75, 128.80, 129.25, 129.98,
131.02, 134.15, 139.73, 149.17, 151.47. EI-MS m/z: 501
(M + 1). Anal. calcd. for C H N O: C, 86.38; H, 4.83; N,
White solid, mp 148–151 °C (lit. value 152 °C) (19). IR
–
1
1
(
KBr) ν
cm : 3062, 2926, 1623, 1588, 1049, 1395. H
max
36 24
2
NMR (500 MHz, CDCl ) δ: 0.55 (t, 3H, J = 7.65 Hz), 2.10
5.60. Found: C, 86.50; H, 4.84; N, 5.58.
3
(
p, 2H, J = 4.6 Hz), 5.58 (t, 1H, J = 3.8 Hz), 7.37 (d, 2H, J =
8
7
2
3
1
.4 Hz), 7.44 (t, 2H, J = 6.9 Hz), 7.60 (t, 2H, J = 7.65 Hz),
.77 (d, 2H, J = 8.4 Hz), 7.87 (d, 2H, J = 8.4 Hz), 8.25 (d,
Acknowledgments
1
3
H, J = 8.4 Hz). C NMR (125 MHz, CDCl ) δ: 9.1, 28.4,
3
One of the authors, N.P., thanks the Council of Scientific
and Industrial Research, New Delhi, India, for the research
fellowship.
1.7, 116.0, 117.6, 122.6, 124.2, 126.7, 128.3, 128.9, 131.1,
31.6, 150.2. MS m/z: 311 (M + 1).
1
4-Naphthalen-1-yl-14H-dibenzo[aj]xanthene (Table 3,
References
entry 12)
–
1
White solid, mp 202–204 °C. IR (KBr) ν
cm : 3049,
max
1
2
. T. Hideo. JP 56 005 480. 1981.
. J.P. Poupelin, G. Saint-Rut, O. Foussard-Blanpin, G. Narcisse,
G. Uchida-Ernouf, and R. Lacroix. Eur. J. Med. Chem. 13, 67
1
1
590, 1397, 1245, 806. H NMR (500 MHz, CDCl ) δ: 7.11
3
(
s, 1H), 7.20 (t, 1H, J = 7.7 Hz), 7.29 (t, 2H, J = 6.7 Hz),
7
6
.36 (t, 2H, J = 8.4 Hz), 7.48 (m, 4H), 7.69 (d, 1H, J =
.9 Hz), 7.75 (m, 6H), 8.46 (d, 2H, J = 8.4 Hz), 9.14 (d, 1H,
(
1978).
3
4
. R.W. Lambert, J.A. Martin, J.H.K.E.B. Merrett, and G.J.
Thomas. WO 9 706 178, 1997.
. (a) R.M. Ion. Prog. Catal. 2, 55 (1997); (b) R.M. Ion, D.
Frackowiak, A. Planner, and K. Wiktroowicz. Acta. Biochim.
Pol. 45, 833 (1998).
1
3
J = 9.2 Hz). C NMR (125 MHz, CDCl ) δ: 34.53, 118.28,
3
1
1
1
18.47, 122.77, 123.51, 123.53, 125.28, 125.95, 126.56,
26.73, 127.61, 128.78, 128.94, 129.40, 129.66, 130.14,
31.12, 132.08, 133.91, 142.61, 148.68. EI-MS m/z: 410
(
M + 2); Anal. calcd. for C H O: C, 91.15; H, 4.93.
5. (a) G. Saint-Ruf and H.T. Hieu. Bull. Chim. Ther. 7, 83
(1972); (b) G. Saint-Ruf, H.T. Hieu, and J.P. Poupelin.
Naturwissenschaften, 62, 584 (1975).
3
1
20
Found: C, 91.08; H, 4.94.
6
. S.M. Mechen, S.C. Benson, J.Y.L. Lam, W. Zhen, D. Sun,
B.B. Rosenblum, S.H. Khan, and M. Taing. US Patent
6 583 168, 2003.
4
1
-(14H-Dibenzo[aj]xanthen-14-yl)-phenol (Table 3, entry
3)
–
1
White solid, mp 200–204 °C. IR (KBr) ν
cm : 3373,
max
1
7. C.G. Knight and T. Stephens. Biochem. J. 258, 683 (1989).
8
1
4
593, 1511, 1243, 815, 744. H NMR (500 MHz, CDCl ) δ:
.78 (s (br), 1H), 6.42 (s, 1H), 6.56 (d, 2H, J = 8.4 Hz), 7.35
3
. (a) O. Sirkeeioglu, N. Talinli, and A. Akar. J. Chem. Res.
Synop. 502 (1995); (b) M. Ahmad, T.A. King, Do-K. Ko, B.H.
Cha, and J. Lee. J. Phys. D: Appl. Phys. 35, 1473 (2002).
. (a) G. Casiraghi, G. Casnati, and M. Cornia. Tetrahedron Lett.
(
d, 2H, J = 8.4 Hz), 7.39 (t, 2H, J = 6.9 Hz), 7.46 (d, 2H, J =
9
7
.2 Hz), 7.56 (t, 2H, J = 7.6 Hz), 7.77 (d, 2H, J = 8.4 Hz),
9
1
3
.81 (d, 2H, J = 7.7 Hz), 8.35 (d, 2H, J = 8.4 Hz). C NMR
1
4, 679 (1973); (b) G. Casiraghi, G. Casnati, M. Catellini, and
M. Cornia. Synthesis, 564 (1974).
0. (a) A. Bekaert, J. Andrieux, and M. Plat. Tetrahedron Lett. 33,
805 (1992); (b) R.J. Sarma and J.B Baruah. Dyes Pigm. 64,
(
125 MHz, CDCl ) δ: 37.17, 115.37, 117.55, 118.08,
3
1
1
22.74, 124.32, 126.85, 128.83, 128.89, 129.45, 131.12,
31.44, 137.56, 148.72, 153.90. EI-MS m/z: 375 (M + 1).
1
1
2
Anal. calcd. for C H O : C, 86.61; H, 4.85. Found: C,
8
2
7
18
2
91 (2005).
6.45; H, 4.86.
1. (a) D.W. Knight and P.B. Little. Synlett. 1141 (1998);
(
b) D.W. Knight and P.B. Little. J. Chem. Soc., Perkin Trans. I.
1
4-Naphthalen-2-yl-14H-dibenzo[aj]xanthene (Table 3,
15, 1771 (2001).
entry 14)
12. C.-W. Kuo and J.-M. Fang. Synth. Commun. 31, 877. (2001).
13. J.-Q. Wang and R.G. Harvey. Tetrahedron, 58, 5927 (2002).
14. A. Jha and J. Beal. Tetrahedron Lett. 45, 8999 (2004).
15. R.N. Sen and N. Sarkar. J. Am. Chem. Soc. 47, 1079 (1925).
–
1
Pale-yellow solid, mp 198–200 °C. IR (KBr) ν
cm :
max
1
3
052, 1594, 1430, 1250, 813, 742. H NMR (500 MHz,
CDCl ) δ: 6.67 (s, 1H), 7.31 (t, 1H, J = 7.7 Hz), 7.37 (m,
3
1
6. P. Papini and R. Cimmarusti. Gazz. Chim. Ital. 77, 142 (1947).
3
8
H), 7.54 (d, 2H, J = 9.2 Hz), 7.58 (m, 5H), 7.81 (m, 5H),
.09 (s, 1H), 8.51 (d, 2H, J = 8.4 Hz). 1 C NMR (125 MHz,
3
17. K. Ota and T. Kito. Bull. Chem. Soc. Jpn. 49, 1167 (1976).
1
1
2
8. J.A. Van Allan, D.D. Giannini, and T.H. Whitesides. J. Org.
Chem. 47, 820 (1982).
9. A.R. Khosropour, M.M. Khodaei, and H. Oghannian. Synlett.
CDCl ) δ: 38.42, 117.12, 118.14, 122.82, 124.38, 125.70,
1
1
1
3
26.09, 126.67, 126.95, 127.55, 127.98, 128.64, 128.94,
29.13, 131.20, 131.61, 132.18, 133.23, 133.91, 142.44,
48.85. EI-MS m/z: 410 (M + 2). Anal. calcd. for C H O:
9
55 (2005).
3
1
20
0. (a) J.R. Hewe, K.-L. Chen, and S. Anahan. J. Chem. Soc.,
Chem. Commun. 1425 (1994); (b) M.V.R. Reddy, B. Malhotra,
and Y.D. Vanker. Tetrahedron Lett. 36, 486 (1995); (c) E.
Manzo, G. Barone, E. Bedini, A. Iadonisi, L. Mangoni, and M.
Parrilli. Tetrahedron, 58, 129 (2002); (d) P. Goswami and P.
Chowdhury. New J. Chem. 24, 955 (2000); (e) X.-F. Zeng,
S.-J. Ji, and S.-Y. Wang. Tetrahedron, 61, 10235 (2005); ( f) G.
Savitha and P.T. Perumal. Tetrahedron Lett. 47, 3589 (2006).
1. (a) M.E. Armenta-Armenta and A.F. Diaz. Environ. Sci.
Technol. 39, 5872 (2005); (b) X.-C. Guo and Q.-Y. Chen. J.
Fluorine Chem. 88, 63 (1998); (c) H. Yan and N. Toshima.
Synthetic Metals, 69, 151 (1995); (d) J.A. Posten, Jr., R.V.
C, 91.15; H, 4.93. Found: C, 90.98; H, 4.94.
3
-(14H-Dibenzo[aj]xanthen-14-yl)-1,4-diphenyl-1H-
pyrazole (3)
–
1
White solid, mp 234–236 °C. IR (KBr) ν
594, 1502, 1401, 1243, 742, 688. H NMR (500 MHz,
cm : 3057,
max
1
1
CDCl ) δ: 6.53 (s, 1H), 7.14 (t, 1H, J = 7.7 Hz), 7.29 (t, 2H,
3
J = 8.4 Hz), 7.35 (d, 2H, J = 8.4 Hz), 7.40 (m, 6H), 7.51 (m,
2
5
8
1
H), 7.75 (d, 2H, J = 9.2 Hz), 7.83 (m, 3H), 8.13 (d, 2H, J =
.4 Hz). C NMR (125 MHz, CDCl ) δ: 27.87, 117.67,
18.08, 119.02, 122.83, 124.37, 126.23, 126.34, 126.64,
1
3
3
©
2007 NRC Canada

Selvam et al.
995
Siriwardane, E.P. Fisher, and A.L. Miltz. Appl. Surf. Sci. 214,
3 (2003).
Makesh, and P.T. Perumal. Bioorg. Med. Chem. Lett. 14, 2035
(2004).
8
2
2. (a) G. Sivaprasad, P.T. Perumal, V.R. Prabavathy, and N.
Mathivanan. Bioorg. Med. Chem. Lett. 16, 6302 (2006); (b) K.
Sujatha, P. Shanmugam, P. T. Perumal, D. Muralidharan, and
M. Rajendran. Bioorg. Med. Chem. Lett. 16, 4893 (2006);
23. N. Panneer Selvam, and P.T. Perumal. Tetrahedron Lett. 47,
7481 (2006).
24. (a) L. Nagarapu, S. Kanveri, V. Mahankhali, and S. Apuri. J.
Mol. Catal. A: Chem. 266, 104 (2007); (b) B. Rajitha, B.S.
Kumar, Y.T. Reddy, P.N. Reddy, and N. Sreenivasulu. Tetrahe-
dron Lett. 46, 8691 (2005).
(
c) R. Sridhar, P.T. Perumal, S. Etti, G. Shanmugam, M.N.
Ponnuswamy, V.R. Prabavathy, and N. Mathivanan. Bioorg.
Med. Chem. Lett. 14, 6035 (2004); (d) C.J. Magesh, S.V.
©
2007 NRC Canada