Syntheses of 1-(4-methylsulfonylphenyl)-5-aryl-1,2,3-triazoles and 1-(4-aminosulfonylphenyl)-5-aryl-1,2,3-triazoles

Article abstract of DOI:10.1002/jhet.5570420106

Condensation of 4-methylsulfonylaniline with aryl aldehyde in ethanol-tetrahydrofuran afforded the imino compound 3.1,3-Cycloaddtion of diazomethane with compound 3 followed by oxidazation of the triazoline 4 with potassium permanganate gave 1-(4-methylsulfonylphenyl)-5-aryl-1,2,3-triazoles 5. Similarly, condensation of 4-(N,N-dibenzylaminosulfonyl)anilme with aryl aldehyde followed by 1,3-cycloaddition of diazomethane with the imino compound 11 and the subsequent oxidation of triazoline 12 with potassium permanganate yielded the triazole 13. Debenzylation of compound 13 with sulfuric acid gave the desired compound 1-(4-aminosulfonylphenyl)-5-aryl-1,2,3-triazoles 14.

Full text of DOI:10.1002/jhet.5570420106

Jan-Feb 2005
33
Syntheses of 1-(4-Methylsulfonylphenyl)-5-aryl-1,2,3-triazoles and
1-(4-Aminosulfonylphenyl)-5-aryl-1,2,3-triazoles
a
a
b
c
c*
F. Johari Daha , H. Matloubi , S. A. Tabatabi , B. Shafii and A. Shafiee
a
b
Nuclear Research Center/ AEOI, Chemical Division, 11365-3486, Tehran/Iran; Faculty of Pharmacy,
c
Shaheed Beheshti University of Medical Sciences, Tehran/Iran; Pharmaceutical Sciences Research Center,
Faculty of Pharmacy, Tehran University of Medical Sciences, Tehran/Iran
* Corresponding author: e.mail: ashafieee@ams.ac.ir
Condensation of 4-methylsulfonylaniline with aryl aldehyde in ethanol-tetrahydrofuran afforded the
imino compound 3. 1,3-Cycloaddtion of diazomethane with compound 3 followed by oxidazation of the tri-
azoline 4 with potassium permanganate gave 1-(4-methylsulfonylphenyl)-5-aryl-1,2,3-triazoles 5. Similarly,
condensation of 4-(N,N-dibenzylaminosulfonyl)aniline with aryl aldehyde followed by l,3-cycloaddition of
diazomethane with the imino compound 11 and the subsequent oxidation of triazoline 12 with potassium
permanganate yielded the triazole 13. Debenzylation of compound 13 with sulfuric acid gave the desired
compound 1-(4-aminosulfonylphenyl)-5-aryl-1,2,3-triazoles 14.
J. Heterocyclic Chem., 42, 33 (2005).
The use of nonsterioal antiflammatory drugs (NSAIDs)
for the treatment of inflammation and pain is often accom-
panied by gastrointestinal ulcerations and bleeding. The
inhibition of cyclooxygenase (COX) was considered to be
responsible for both the therapeutic and side effect of
NSAIDs. In 1990 the existence of a second COX enzyme,
named COX-2 was described [1,2]. COX-2 was postulated
to be the isoform involved in inflammatory process [1].
1,2-Diaryl heterocycles such as rofecoxib and celecoxib
are selective COX-2 inhibitors with superior gastrointesti-
nal safety profile. In this work we report the syntheses of
the title compounds as possible COX-2 inhibitors.
The synthesis of 1-(4-methylsulfonylphenyl)-5-aryl-
1,2,3-triazoles 5 is shown in Scheme 1.
Reaction of 4-methylsulfonylaniline 1 with substituted
benzaldehyde in ethanol according to the method reported
previously [3] did not give the desired imino compound 3.
However, in mixture of ethanol/THF compound 3 was
obtained in good yield (Table 1).
1,3-Cycloaddition of diazomethane in ether with com-
pound 3 was attempted according to the literature [4].
However, the cycloaddition was not observed and
unchanged starting material was isolated. Finally, cycload-
dtion could be achieved with diazomethane in dioxane/water
[5] and 1-(4-methylsulfonylphenyl)-5-aryl-4,5-dihydro-1H-
[1,2,3] triazole 4 was obtained in moderate yield (Table 2).
Potassium permanganate oxidation of 4 in an acetone
solution gave low yield of the desired product 1-(4-methyl-
sulfonylphenyl)-5-aryl-1,2,3-triazole 5 [6]. However, com-
pound 5 could be obtained in moderate to good yield using
potassium permanganate in a two phase system in the pres-
ence of a phase transfer catalyst, namely tetrabutylammo-
nium chloride [7](Table 3).
Table 1
Physical Data for 3 and 11
Comp
X
Mp(°C)
Yield (%)
Formula
Calcd
Found
C%
Calcd
Found
H%
Calcd Found
N%
3a
3b
3c
3d
11a
11b
11c
H
CH
Cl
F
167-169
168-170
167-169
138-140
115-117
127-130
106-108
82
67
83
91
65
60
62
C
C
H
NO S
64.86
65.93
57.24
60.65
74.01
68.49
70.80
64.98
65.71
57.46
60.42
74.16
68.70
70.94
5.02
5.49
4.09
4.33
5.73
4.85
5.01
4.85
5.28
4.23
4.54
5.55
4.66
5.14
5.40
5.13
4.77
5.05
6.17
5.90
6.10
5.21
5.01
4.98
5.26
6.33
6.12
6.26
14 13
2
H NO S
3
15 15 2
C H ClNO S
14 12 2
C H FNO S
14 12 2
CH
Cl
F
C H N O S
3
28 26 2 2
C
H ClN O S
H FN O S
27 23 2 2
C
27 23 2 2

34
F. Johari Daha, H. Matloubi, S. A. Tabatabi, B. Shafii and A. Shafiee
Vol. 42
Table 2
Physical Data for 4 and 13
Comp
X
Mp(°C)
Yield (%)
Formula
Calcd
Found
C%
Calcd
Found
H%
Calcd Found
N%
4a
4b
4c
4d
12a
12b
12c
H
CH
Cl
F
150-152
133-135
163-165
158-159
90-92
50
50
57
55
62
67
74
C
H
H
N O S
N O S
59.80
60.95
53.65
56.43
70.16
65.05
67.20
59.97
61.04
53.46
56.62
70.02
65.00
67.38
4.98
5.40
4.17
4.39
5.64
4.84
5.00
5.06
5.63
4.01
4.58
5.45
4.67
5.18
13.95
13.33
12.52
13.17
11.29
10.84
11.20
13.76
13.11
12.33
13.38
11.08
10.98
11.45
15 15
3 2
C
3
16 17 3 2
C H Cl N O S
15 14 3 2
C H FN O S
15 14 3 2
CH
Cl
F
C H N O S
3
29 28 4 2
73-75
113-115
C H ClN O S
28 25 4 2
C H FN O S
28 25 4 2
Table 3
Physical Data for Compounds 5, 13 and 14
Comp
X
Mp(°C)
Yield (%)
Formula
Calcd
Found
C%
Calcd
Found
H%
Calcd Found
N%
5a
5b
5c
5d
13a
13b
13c
14a
14b
14c
H
CH
Cl
F
CH
Cl
F
CH
Cl
F
168-170
134-135
171-173
180-182
108-110
131-133
134-135
58-60
50
40
50
52
30
35
45
20
45
49
C
H
H
N O S
N O S
60.20
61.34
53.97
56.78
70.44
65.31
67.47
57.32
50.22
52.83
60.02
61.56
53.76
56.89
70.65
65.52
67.29
57.14
50.35
52.95
4.35
4.79
3.60
3.79
5.26
4.47
4.62
4.46
3.29
3.46
4.17
4.60
3.42
3.96
5.45
4.69
4.81
4.68
3.45
3.68
14.05
13.42
12.59
13.25
11.34
10.88
11.24
17.83
16.74
17.61
14.26
13.61
12.38
13.06
11.72
10.69
11.08
17.96
16.85
17.80
15 13
3 2
C
3
3
3
16 15 3 2
C H Cl N O S
15 12 3 2
C H FN O S
15 12 3 2
C H N O S
29 26 4 2
H ClN O S
C
28 23 4 2
C
H FN O S
28 23 4 2
C H N O S
C H ClN O S
14 11 4 2
15 14 4 2
170-172
171-173
C
H FN O S
14 11 4 2
1-(4-Aminosulfonylphenyl)-5-aryl-1,2,3-triazoles 14
were obtained according to Scheme 2.
Cycloadition of diazomethane in dioxane with the imino
compound 6 did not give the desired compound 14.
Instead, methylation of the sulfonamide group occurred
and compound 7 was isolated. Therefore, we have decided
to protect the amino group of the sulfonamide group of
compound 6. Reaction of dibenzylamine with 4-acetami-
dobenzenesulfonyl chloride in triethylamine followed by
hydrolysis afforded 4-amino-N,N-dibenzylbenzensulfon-
amide 10. Coupling of compound 10 with aryl aldehyde 2
under the condition explained above did not give the Schiff
base 11. However, the condensation could be achieved in
toluene using p-toluenesulfonic acid as catalyst. 1,3-
Cycloaddition of diazomethane in dioxane with compound
11 followed by oxidation of the intermediate 12 with
potassium permanganate gave 1-(4-N,N-dibenzy-
laminosulfonylphenyl)-5-aryl-1,2,3-triazoles 13.
Deprotection of 13 was achieved using sulfuric acid to
give the desired product 14.
EXPERIMENTAL
Melting points were determined on a Kofler hot stage appara-
tus and are uncorrected. The ir spectra were obtained using a
Perkin-Elmer Model 781 or Nicollet FT-IR Magna 550 spectro-
1
graphs. The H NMR spectra were obtained on a Bruker FT-80
spectrometer or a Varian unity plus 400 spectrometer (400 MHz)
and Chemical shifts (δ) are in ppm relative to internal tetram-
ethylsilane. Elemental microanalyses were within ± 0.4% of the-
oretical values for C, H and N.

Jan-Feb 2005
Syntheses of 1-(4-Methylsulfonylphenyl)-5-aryl-1,2,3-triazoles
35
1
General Procedure for Synthesis of Compound 3.
The following spectral properties were observed: H NMR
(DMSO-d ): δ 7.80 (d, J=8.8 Hz, 2H, Ar-H), 7.42 (d, J=8.4 Hz, 2H,
Ar-H), 7.35 (d, J=8.8 Hz, 2H, Ar-H), 7.21 (d, J=8.4 Hz, 2H, Ar-H),
6
4-Methylsulfonylaniline (1, 1 mmol) and appropriate aldehyde
(2, 1 mmol) were condensed by refluxing the reaction mixture for
10 h in EtOH (0.4 ml) and THF (0.4 ml). The solvent was evapo-
rated and the residue was crystallized from THF/hexane to give
compound 3.
5.38 (dd, J=6.4, 12.4 Hz, 1H, C-H ), 4.94 (dd, J=12.4, 17.6 Hz, 1H,
5
C-H ), 4.41 (dd, J=6.4, 17.6 Hz, 1H, C-H ), 3.13 (s, 3H, CH ).
4
4
3
1-(4-Methylsulfonylphenyl)-5-(4-flourophenyl)-4,5-dihydo-1H-
[1,2,3]triazole (4d).
4-Methylsulfonyl-N-benzylidenaniline (3a).
1
The following spectral properties were observed: H NMR
The following spectral properties were observed: IR (KBr) ν:
(DMSO-d ): δ 7.80 (d, J=8.8 Hz, 2H, Ar-H), 7.36 (d, J=8.8 Hz,
6
3100 (Ar-H), 1638 (HC=N), 1305 (SO ), 1142 (SO ), 770 (Ar-H).
2
2
2H, Ar-H), 7.23 (m, 4H, Ar-H), 5.38 (dd, J=12.4, 6.4 Hz, 1H, C-
1
H NMR (DMSO-d ): δ 8.65 (s, 1H, HC=N), 7.95 (m, 4H, Ar-H),
6
H ), 4.94 (dd, J=17.6, 12.4 Hz, 1H, C-H ), 4.40 (dd, J=17.6, 6.4
5
5
7.56 (m, 3H, Ar-H), 7.45 (d, J=8.4 Hz, 2H, Ar-H), 3.23 (s, 3H, CH ).
3
Hz, 1H, C-H ), 3.13 (s, 3H, CH ).
4
3
4-Methylsulfonyl-N-(4-methylbenzyliden)aniline (3b).
General Procedure for Synthesis of Compound 5.
The following spectral properties were observed: IR (KBr) ν:
1
A mixture of compound 4 (0.67 mmol) in benzene (17 ml),
potassium permanganate (0.525 g) in water (34 ml) and tetra-
butylammonium chloride (0.042 mmol) was heated under reflux
with stirring for 5 h. The benzene was separated. The aqueous
layer was extracted with benzene (2 x 17 ml). Any potassium per-
manganate remaining in the organic layer was destroyed by using
sodium sulfite. The organic layer was dried (Na SO ), filtered
3100(Ar-H), 1638 (HC=N), 1305 (SO ), 1142 (SO ), H NMR
2
2
(DMSO-d ): δ 8.59 (s, 1H, HC=N), 7.90 (m, 4H, Ar-H), 7.41 (m,
6
4H, Ar-H), 3.23 (s, 3H, CH ), 2.40 (s, 3H, CH ).
3
3
4-Methylsulfonyl-N-(4-chlorobenzyliden)aniline (3c).
The following spectral properties were observed: IR (KBr) ν:
1
3050 (Ar-H), 1622 (HC=N), 1297 (SO ), 1142 (SO ), H NMR
2
4
2
2
and evaporated. The residue was purified by column chromatog-
raphy (silica gel, EtOAc/hexane 40:60)[7].
(DMSO-d ): δ 8.67 (s, 1H, HC=N), 7.98 (m, 4H, Ar-H), 7.63 (d,
J=8.8 Hz, 2H, Ar-H), 7.46 (d, J=8.8 Hz, 2H, Ar-H), 3.23 (s, 3H,
6
CH ), 2.40 (s, 3H, CH ).
3
3
1-(4-Methylsulfonylphenyl)-5-phenyl-1,2,3-triazole (5a).
4-Methylsulfonyl-N-(4-flourobenzyliden)aniline (3d).
1
The following spectral properties were observed: H NMR
The following spectral properties were observed: IR (KBr) ν:
(DMSO-d ): δ 8.14 (s, 1H, C-H ), 8.08 (d, J=8.4 Hz, 2H, Ar-H),
7.70 (d, J=8.4 Hz, 2H, Ar-H), 7.45 (m, 3H, Ar-H), 7.34 (m, 2H,
6 4
1
3050 (Ar-H), 1622 (HC=N), 1289 (SO ), 1142 (SO ), H NMR
2
2
(DMSO-d ): δ 8.66 (s, 1H, HC=N), 8.03 (m, 2H, Ar-H), 7.96 (d,
Ar-H), 3.32 (s, 3H, CH ).
6
3
J=8.4 Hz, 2H, Ar-H), 7.45 (d, 2H, J=8.4 Hz, Ar-H), 7.40 (m, 2H,
1-(4-Methylsulfonylphenyl)-5-(4-methylphenyl)-1,2,3-triazole
(5b).
Ar-H), 3.24 (s, 3H, CH ).
3
General Procedure for Synthesis of Compound 4.
1
The following spectral properties were observed: H NMR
Proper Schiff base (3, 1 mmol) was added with shaking to a
cold freshly prepared solution of diazomethane (3 mmol) in diox-
ane/water (4.5 ml)[5]. A cork stopper was then placed in the flask
and the reaction mixture was allowed to stand at room tempera-
ture for 5-10 days. At the end of this period, the mixture was fil-
tered, cooled, and diluted with cold water with shaking. The
resulting solid 4 was collected by filtration and the crude product
was crystallized from ethanol.
(DMSO-d ): δ 8.14 (s, 1H, C-H ), 8.08 (d, J=8.4 Hz, 2H, Ar-H),
6
4
7.69 (d, J=8.4 Hz, 2H, Ar-H), 7.25 (d, J=8.8 Hz, 2H, Ar-H), 7.21
(d, J=8.4 Hz, 2H, Ar-H), 3.32 (s, 3H, CH ), 2.32 (s, 3H, CH ).
3
3
1-(4-Methylsulfonylphenyl)-5-(4-chlorophenyl)-1,2,3-triazole (5c).
1
The following spectral properties were observed: H NMR
(DMSO-d ): δ 8.22 (s, 1H, C-H ), 8.09 (d, J=8.4 Hz, 2H, Ar-H),
6
4
7.71 (d, J=8.8 Hz, 2H, Ar-H), 7.53 (d, J=8.4 Hz, 2H, Ar-H), 7.36
(d, J=8.8 Hz, 2H, Ar-H), 3.31 (s, 3H, CH ).
3
1-(4-Methylsulfonylphenyl)-5-phenyl-4,5-dihydro-1H-[1,2,3]tri-
azole (4a).
4-methylaminosulfonyl-N-(4-methylbenzylidene)aniline (7).
1
The following spectral properties were observed: H NMR
Compound 6 (70 mg, 0.255 mmol) was added with shaking to
a cold freshly prepared solution of diazomethane (0.85 mmol) in
dioxan/water (1.3 ml) [5]. The reaction mixture was allowed to
stand at room temperature for 8 days. The mixture was filtered,
cooled, and diluted with cold water with shaking. The resulting
solid was collected by filtration and crystallized from
(DMSO-d ): δ 7.78 (d, J=8.8 Hz, 2H, Ar-H), 7.36 (d, J=8.8 Hz,
2H, Ar-H), 7.29 (m, 3H, Ar-H), 7.18 (m, 2H, Ar-H), 5.34 (dd,
J=6.4, 12.4 Hz, 1H, C-H ), 4.94 (dd, J=12.4, 17.6 Hz, 1H, C-H ),
4.38 (dd, J=6.4, 17.6 Hz, 1H, C-H ), 3.12 (s, 1H, CH ).
6
5
4
4
3
1-(4-Methylsulfonylphenyl)-5-(4-methylphenyl)-4,5-dihydro-
THF/hexane to give 30 mg (40%) of compound 7; mp143-145°C;
1H-[1,2,3]triazole (4b).
1
H NMR (DMSO-d ): δ 8.74 (s, 1H, HC=N), 8.13 (d, J=8.4 Hz,
6
1
The following spectral properties were observed: H NMR
2H, Ar-H), 7.90 (d, J=8.4 Hz, 2H, Ar-H), 7.60 (bs, 1H, NH), 7.25
(DMSO-d ): δ 7.78 (d, J=8.8 Hz, 2H, Ar-H), 7.35 (d, J=8.8 Hz,
2H, Ar-H), 7.14 (d, J=8.0 Hz, 2H, Ar-H), 7.06 (d, J=8.0 Hz, 2H,
Ar-H), 5.30 (dd, J=6.4, 12.4 Hz, 1H, C-H ), 4.91 (dd, J=12.4,
6
(s, 4H, Ar-H), 2.44 (s, 3H, CH ), 2.34 (s, 3H, CH ).
3
3
Anal. Calcd. for C
H N O S: C, 62.50; H, 5.56; N, 9.72.
15 16 2 2
5
Found: C, 62.31; H, 5.38; N, 9.53.
17.6 Hz, 1H, C-H ), 4.35 (dd, J=6.4, 17.6 Hz, 1H, C-H ), 3.12 (s,
4
4
1H, CH ), 2.25 (s, 3H, CH ).
N-[4-(Dibenzylaminosulfonyl-phenyl)-acetamide (9).
3
3
1-(4-Methylsulfonylphenyl)-5-(4-chlorophenyl)-4,5-dihydro-
A solution of 1.2 g (9 mmol) of 4-acetamidobenzenesulfonyl
1H-[1,2,3]triazole (4c).
chloride 8 in 5.9 ml anhydrous THF, was added dropwise to a

36
F. Johari Daha, H. Matloubi, S. A. Tabatabi, B. Shafii and A. Shafiee
Vol. 42
mixture of 1.47 ml (11 mmol) of dibenzylamine and 1.1 ml (11
mmol) of triethylamine in 8.8 ml of anhydrous THF. After stir-
ring at room temperature overnight, water was added to the mix-
ture and extracted with ethyl acetate. The solvent was evaporated
and the residue was crystallized from ethyl acetate to give 2.32 g
of compound 9. Yield 57%; mp 127-129°C. IR (KBr) ν: 3380
1-[4-(N,N-Dibenzylaminosulfonyl)phenyl]-5-(4-methylphenyl)-
4,5-dihydro-1H-[1,2,3]triazole (12a).
1
This compound was prepared similar to compound 4;
H
NMR (DMSO-d ): δ 7.75 (d, J=8.8 Hz, 2H, Ar-H), 7.33 (d,
6
J=8.4 Hz, 2H, Ar-H), 7.17 (m, 10H, Ar-H), 7.02 (m, 4H, Ar-H),
5.32 (dd, J=5.6, 12 Hz, 1H, C-H ), 4.91 (dd, J=12, 13.6 Hz, 1H,
5
(NH), 3070 (Ar-H), 1708 (C=O), 1329 (SO ), 1140 (SO ), 780
2
2
C-H ), 4.38 (dd, J=5.6, 13.6 Hz, 1H, C-H ), 4.23 (s, 4H, CH ),
1
4
4
2
(Ar-H). H NMR (DMSO-d ): δ 7.81 (s, 4H, Ar-H), 7.44 (bs,
6
2.27 (s, 3H, CH ). Compounds 12b and 12c were Prepared
3
1H, N-H), 7.20 (m, 6H, Ar-H), 7.07 (m, 4H, Ar-H), 4.25 (s, 4H,
Similarly ( Table 2).
CH ), 2.10 (s, 3H, CH ).
2
3
Anal. Calcd for C
Found: C, 67.22; H, 5.39; N, 7.02.
H N O S: C, 67.01; H, 5.58; N, 7.11.
22 22 2 3
1-[4-(N,N-Dibenzylaminosulfonyl)phenyl]-5-(4-chlorophenyl)-
4,5-dihydro-1H-[1,2,3]triazole (12b).
4-(N,N-Dibenzylaminosulfonyl)aniline (10).
1
The following spectral properties were observed: H NMR
Compound 9 (3.94 g, 0.01 mole) was refluxed with 24 ml con-
centrated hydrochloric acid and 10 ml EtOH for 1 h. After cool-
ing, the mixture was made alkaline with 32% ammonia solution
and the precipitate was filtered. The residue were crystallized
from ethanol-water to give 2.99 g (85%) of compound 10; mp
(DMSO-d ): δ 7.76 (d, J=8.8 Hz, 2H, Ar-H), 7.45 (d, J=8.8 Hz,
2H, Ar-H), 7.32 (d, J=8.8 Hz, 2H, Ar-H), 7.23 (d, J=8.8 Hz, 2H,
Ar-H), 7.11 (m, 6H, Ar-H), 7.02 (m, 4H, Ar-H), 5.39 (dd, J=6.4,
6
12.4 Hz, 1H, C-H ), 4.94 (dd, J=12.4, 17.8 Hz 1H, C-H ), 4.41
5
4
(dd, J=6.4, 17.8Hz, 1H, C-H ).
4
107-109 °C. IR (KBr) ν: 3481 (NH ), 3380 (NH ), 1313 (SO ),
2
2
2
1-[4-(N,N-Dibenzylaminosulfonyl)phenyl]-5-(4-flourophenyl)-
4,5-dihydro-1H-[1,2,3]triazole (12c).
1
1135 (SO ). H NMR (DMSO-d ): δ 7.50 (d, J=8.7 Hz, 2H, Ar-
2
6
H), 7.16 (m, 10H, Ar-H), 6.67 (d, J=8.7 Hz, 2H, Ar-H), 4.18 (s,
4H, CH ), 3.95 (bs, 2H, NH ).
1
2
2
The following spectral properties were observed: H NMR
Anal. Calcd. for C
H N O S: C, 68.18; H, 5.68; N, 7.95.
20 20 2 2
(DMSO-d ): δ 7.76 (d, J=8.8 Hz, 2H, Ar-H), 7.33 (d, J=8.8 Hz,
6
Found: C, 68.39; H, 5.99; N, 8.06.
2H, Ar-H), 7.23 (m, 4H, Ar-H), 7.17 (m, 6H, Ar-H), 7.03 (m, 4H,
Ar-H), 5.39 (dd, J=6.4, 12.4 Hz, 1H, C-H ), 4.93 (dd, J=12.4,
General Procedure for the Preparation of Compound 11.
5
17.6 Hz, 1H, C-H ), 4.40 (dd, J=6.4, 17.8 Hz, 1H, C-H ), 4.24 (s,
4
4
To a solution of 10 (1 mmol) and p-toluenesulfonic acid (0.4
mg) in toluene (5 ml) at reflux temperature using Dean-stark
apparatus for separation of water a solution of appropriate alde-
hyde 2 (1 mmol) in toluene (2 ml) was added dropwise. After
refluxing for 5 h, 1 g of 4 Å molecular sieve was added followed
by another overnight heating. The molecular sieve was removed
by filtration at room temperature and the solution was evaporated
under reduced pressure. The residual oil was triturated with
petroleum ether and the precipitate was collected by filtratoin.
4H, CH ).
2
1-[4-(N,N-Dibenzylaminosulfonyl)phenyl]-5-(4-methylphenyl)-
1,2,3-triazole (13a).
1
This compound was prepared similar to compound 5.
H
NMR (DMSO-d ): δ 8.41 (s, 1H, C-H ), 8.02 (d, J=8.8 Hz, 2H,
6
4
Ar-H), 7.62 (d, J=8.4 Hz, 2H, Ar-H), 7.22 (m, 10H, Ar-H), 7.09
(m, 4H, Ar-H), 4.36 (s, 4H, CH ), 2.33 (s, 3H, CH ). Compounds
2
3
13b and 13c were prepared similarly (Table 3).
4-Dibenzylaminosulfonyl-N-(4-methylbenzylidene)aniline
(11a).
1-[4-(N,N-Dibenzylaminosulfonyl)phenyl]-5-(4-chlorophenyl)-
1,2,3-triazole (13b).
The following spectral properties were observed: IR (KBr) ν:
1
3050 (Ar-H), 1630 (CH=N), 1330 (SO ), 1150 (SO ), 700 (Ar-
The following spectral properties were observed: H NMR
2
2
1
H). H NMR (DMSO-d ): δ 8.62 (s, 1H, HC=N), 7.89 (m, 4H,
(DMSO-d ): δ 8.22 (s, 1H, C-H ), 8.02 (d, J=8.0 Hz, 2H, Ar-H),
6
6
4
Ar-H), 7.41 (d, J=8 Hz, 2H, Ar-H), 7.37(d, J=8 Hz, 2H, Ar-H),
7.21 (m, 6H, Ar-H), 7.1 (m, 4H, Ar-H), 4.31 (s, 4H, CH ), 2.40
7.64 (d, J=8.0 Hz, 2H, Ar-H), 7.51 (d, J=8.0 Hz, 2H, Ar-H), 7.51
(d, J=8.0 Hz, 2H, Ar-H), 7.53 (d, J=8.0 Hz, 2H, Ar-H), 7.23 (m,
2
(s, 3H, CH ).
6H, Ar-H), 7.09 (m, 4H, Ar-H), 4.34 (s, 4H, CH ).
3
2
4-(Dibenzylaminosulfonyl)-N-(4-chlorobenzyliden)aniline
(11b).
1-[4-(N,N-Dibenzylaminosulfonyl)phenyl]-5-(4-flourophenyl)-
1,2,3-triazole (13c).
The following spectral properties were observed: IR (KBr) ν:
1
The following spectral properties were observed: H NMR
1
3060 (Ar-H), 1627 (CH=N), 1335 (SO ), 1156 (SO ). H NMR
2
2
(DMSO-d ): δ 8.18 (s, 1H, C-H ), 8.01 (d, J=8.2 Hz, 2H, Ar-
H), 7.49 (d, J=8.2 Hz, 2H, Ar-H), 7.39 (m, 2H, Ar-H), 7.29 (m,
3H, Ar-H), 7.21 (m, 5H, Ar-H), 7.08 (m, 4H, Ar-H), 4.35 (s,
6
4
(DMSO-d ): δ 8.69 (s, 1H, HC=N), 8.01 (d, J=8.4 Hz, 2H, Ar-H),
6
7.92 (d, J=8.4 Hz, 2H, Ar-H), 7.64 (d, J=8.4 Hz, 2H, Ar-H), 7.44
(d, J=8.4 Hz, 2H, Ar-H), 7.22 (m, 6H, Ar-H), 7.09 (m, 4H, Ar-
4H, CH ).
2
H), 4.32 (s, 4H, CH ).
2
General Procedure for the Preparation of Compound 14.
4-(Dibenzylaminosulfonylphenyl)-N-(4-flourobenzyliden)ani-
line (11c).
A suspension of 1 mmol of compound 13 in 1.4 ml of con-
centrated H SO was stirred at room temperature for 20 min.
The following spectral properties were observed: IR (KBr) ν:
2
4
1
The mixture was poured into ice. The resulting solid was col-
lected by filtration, washed with water, and dried. Purification
by flash chromatography, eluting with EtOAc/hexane (80:20)
gave compound 14.
3090 (Ar-H), 1633 (CH=N), 1333 (SO ), 1151 (SO ). H NMR
2
2
(DMSO-d ): δ 8.69 (s, 1H, HC=N), 8.06 (m, 2H, Ar-H), 7.92(m,
6
2H, Ar-H), 7.42 (m, 4H, Ar-H), 7.21 (m, 6H, Ar-H), 7.1 (m, 4H,
Ar-H), 4.32 (s, 4H, CH ).
2

Jan-Feb 2005
Syntheses of 1-(4-Methylsulfonylphenyl)-5-aryl-1,2,3-triazoles
37
1-(4-Aminosulfonylphenyl)-5-(4-methylphenyl)-1,2,3-triazole
Acknowledgement.
(14a).
This research was partially supported by the Tehran University
of Medical Sciences research council and Iran Chapter of TWAS.
1
The following spectral properties were observed: H NMR
(DMSO-d ): δ 8.10 (s, 1H, C-H ), 7.92 (d, J=7.3 Hz, 2H, Ar-H),
6
4
7.60 (d, J=7.3 Hz, 2H, Ar-H), 7.53 (bs, 2H, NH ), 7.21 (m, 4H,
2
REFERENCES AND NOTES
Ar-H), 2.32 (s, 3H, CH ).
3
1-(4-Aminosulfonylphenyl)-5-(4-chlorophenyl)-1,2,3-triazole
(14b).
[1] J. Y. Fu, J. L. Msferrer, K. Siebert, A. Raz and P.
Needleman, J Biol. Chem., 265, 16737 (1990).
[2] W. Xie, J. G. Chipman, D. L. Robertson, R. L. Erikson
and D. L. Simmons, Proc Natl. Acad. Sci. USA, 88, 1692 (1991).
[3] P. K. Kadaba, Tetrahedron, 22, 2453 (1966).
[4] G. D. Buckley, J. Chem. Soc,. 1850 (1954).
[5] P. K. Kadaba, Synthesis, 71 (1973).
1
The following spectral properties were observed: H NMR
(DMSO-d ): δ 8.19 (s, 1H, C-H ), 7.95 (d, J=8.8 Hz, 2H, Ar-H),
6
4
7.63 (d, J=8.8 Hz, 2H, Ar-H), 7.56 (bs, 2H, NH ), 7.53 (d, J=8.4
2
Hz, 2H, Ar-H), 7.35 (d, J=8.4 Hz, 2H, Ar-H).
1-(4-Aminosulfonylphenyl)-5-(4-flourophenyl)-1,2,3-triazole (14c).
1
[6] R. Huisgen, G. Szeimies and L. Mobius, Chem. Ber.,
475 (1966).
The following spectral properties were observed: H NMR
(DMSO-d ): δ 8.16 (s, 1H, C-H ), 7.95 (d, J=8.4 Hz, 2H, Ar-H), 7.62
6
4
(d, J=8.4 Hz, 2H, Ar-H), 7.58 (bs, 1H, NH ), 7.39 (m, 4H, Ar-H).
[7] P. K. Kadaba, Synthesis, 694 (1978).
2