Medicinal Chemistry Research
was obtained 8, separated by suction and washed with about
0 ml of cold water. The precipitate solid was then dis-
persed in 40 ml of cold water, whereupon a solution of
sodium azide (8 g in 20 ml water) was added portion-wise
116.3; Anal. Calcd. for C H BrN O S (351.963): C, 40.81;
H, 2.57; N, 15.86; S, 9.08; Found: C, 41.90; H, 2.84; N,
15.73; and S, 9.21.
1
2
9
4
2
8
till evolution of N ceased. After that sodium chloride (30 g)
4-Azido-4-chlorophenyl-benzenesulfonamide 10c Puri®-
cation was achieved using flash chromatography (ethyl
2
was added to salt out. The resulting precipitate was filtered
off and dried in vacuum to yield a yellowish-white pre-
cipitate. 5 g of the resultant azido derivative was dissolved
in thionyl chloride (20 ml) and three drops of DMF and
heated till boiling for 30 min. After completion of the
reaction, the excess thionyl chloride was removed under
vacuum and residue was extracted with diethyl ether
acetate/hexane, 4:6) which provided 10c as a buff solid
1
(71%). mp 122–124 °C; H NMR (DMSO-d , 500 MHz), δ
6
10.42 (s, 1H, –SO NH), 7.73 (app. ddd, J = 2, 3 and 5 Hz,
2
2H, Ar–H), 7.30–7.24 (m, 4H, Ar–H), 7.08 (m, 2H, Ar–H);
1
3
C NMR (DMSO-d , 125 MHz) δ 144.3, 136.6, 135.1,
6
129.2 (2CH ), 128.7 (2CH ), 128.3, 121.7 (2CH ), 119.9
Ar
Ar
Ar
(
100 ml). The etherial extract was evaporated under vacuum
(2CH ); Anal. Calcd. for C H ClN O S (308.0135): C,
Ar 12 9 4 2
to afford 4-azidobenzene sulfonyl chloride 9 as a yellowish-
white solid (4.1 g, 76%). mp 59–61 °C; H NMR (DMSO-
46.68; H, 2.94; N, 18.15; S, 10.39 Found: C, 47.04; H,
3.17; N, 18.41; and S, 10.20.
1
d , 500 MHz) δ 7.04–7.07 (m, 2H, Ar–H), 7.60–7.63 (m,
6
1
3
2
1
H, Ar–H); C NMR(DMSO-d , 125 MHz) δ 144.9, 139.5,
4-Azido-4-methoxyphenyl-benzenesulfonamide 10d Puri-
fication was achieved using flash chromatography (ethyl
acetate/hexane, 3:7) which provided 10d as a white solid
6
27.5 (2CH ), 118.4 (2CH ).
Ar
Ar
1
General procedure for synthesis of 4-azido-(un)substituted-
(63%). mp 74–75 °C (Mirian et al. 2011); H NMR
phenyl-benzenesulfonamides, compounds 10a–f
(DMSO-d , 500 MHz), δ 10.15 (s, 1H, SO NH), 7.77 (app.
6
2
dd, J = 2 & 4 Hz, 2H, Ar–H), 7.68–7.65 (m, 2H, Ar–H),
6.99 (m, 2H, Ar–H), 6.75 (m, 2H, Ar–H), 3.80 (s, 3H,
To a solution of 9 (0.01 mmol), appropriate anilines were
added (0.01 mmol) in dry pyridine (1 ml) at 0 °C. After
addition, the reaction was stirred for 16 h at room tem-
perature, and then pyridine was azeotropically removed
with toluene under vacuum. The residue was dissolved in
ethyl acetate, washed with water and brine, and then dried
with Na SO , filtered, and concentrated under vacuum.
1
3
OCH3); C NMR (DMSO-d , 125 MHz) δ 149.9, 144.3,
6
136.6, 135.1, 129.2 (2CH ), 128 (2CH ), 121.7 (2 CH ),
Ar
Ar
Ar
115.9 (2CH ); Anal. Calcd. for C H N O S (304.063): C,
Ar
13 12
4
3
51.31; H, 3.97; N, 18.41; S, 10.54; Found: C, 51.09; H,
3.89; N, 18.63; and S, 10.48.
2
4
4-Azido-4-nitrophenyl-benzenesulfonamide 10e Puri®ca-
4
-Azido-phenyl-benzenesulfonamide 10a Purification was
tion was achieved using flash chromatography (ethyl acet-
achieved using flash chromatography (ethyl acetate/hexane,
ate/hexane, 1:9) which provided 10e as a yellow solid
1
3
9
5
:7) which provided 10a as a faint buff solid (78%). mp
4–96 °C (Mirian et al. 2011); H NMR (DMSO-d6,
(81%). mp 104–105 °C; H NMR (DMSO-d , 500 MHz), δ
6
1
10.93 (s, 1H, SO NH), 8.12–8.10 (m, 2H, Ar–H), 7.93–7.84
2
00 MHz), δ 10.36 (brs, 1H, SO NH), 8.14 (app. dd, 2H,
(m, 2H, Ar–H), 7.27 (m, 2H, Ar–H), 6.58 (app. dd, J = 2
2
1
3
J = 2.5 and 2 Hz, Ar–H), 7.91 (app. t, 2H, J = 2 and 7 Hz,
Ar–H), 7.22 (app. dd, J = 5 and 7 Hz, 2H, Ar–H);
and 5.5 Hz, 2H, Ar–H); C NMR (DMSO-d , 125 MHz) δ
6
155.8, 144.9, 142.2, 142.7, 128.9 (2CH ), 126.5 (2CH ),
Ar
Ar
1
3
7
.17–7.04 (m, 2H, Ar–H), 6.59–6.57 (m, 1H, Ar–H);
C
120.3 (2CHAr), 112.5 (2CHAr). Anal. Calcd. for
C H N O S (319.0375): C, 45.14; H, 2.84; N, 21.93; S,
NMR (DMSO-d , 125 MHz) δ 145.1, 143.8, 138, 128.9
6
12
9
5
4
(
2CH ), 126.5 (2CH ), 120.1 (2CH ), 118.3 (CH ),
10.04; Found: C, 45.39; H, 2.97; N, 22.23; and S, 9.89.
Ar
Ar
Ar
Ar
1
16.0 (2CH ). Anal. Calcd. for C H N O S (274.0524):
Ar 12 10 4 2
C, 52.54; H, 3.67; N, 20.43; S, 11.69; Found: C, 52.31; H,
4-Azido-3-nitrophenyl-benzenesulfonamide 10f Puri®ca-
tion was achieved using flash chromatography (ethyl acet-
3
.90; N, 20.65; and S, 11.47.
ate/hexane, 1:9) which provided 10f as a yellow solid
1
4
-Azido-4-bromophenyl-benzenesulfonamide 10b Puri®-
(76%). mp 98–100 °C; H NMR (DMSO-d , 500 MHz), δ
6
cation was achieved using flash chromatography (ethyl
10.93 (s, 1H, SO NH), 7.92 (app. t, J = 2.5 Hz, 1H, Ar–H),
2
acetate/hexane, 4:6) which provided 10b as a brown solid
7.88–7.86 (m, 1H, Ar–H), 7.80–7.78 (m, 1H, Ar–H),
1
13
(
66%). mp 112–114 °C; H NMR (DMSO-d , 500 MHz), δ
7.55–7.49 (m, 2H, Ar–H), 7.28–7.23 (m, 3H, Ar–H);
C
6
1
2
0.44 (s, 1H, SO NH), 7.73 (app. dd, J = 2.5 and 8.5 Hz,
NMR (DMSO-d , 125 MHz) δ 150.1, 148.2, 144.8, 139,
2
6
H, Ar–H), 7.41 (m, 2H, Ar–H), 7.25 (m, 2H, Ar–H), 7.03
130.9, 128.8 (2CH ), 125.5, 120.1 (2CH ), 109.9, 107.1
Ar
Ar
13
(
(
(
apparent ddd, J = 2, 2.5 and 4.5 Hz, 2H, Ar-H); C NMR
DMSO-d , 125 MHz) δ 144.3, 137.0, 135.1, 132.1
2CH ), 128.7 (2CH ), 121.9 (2CH ), 119.9 (2CH ),
(C ); Anal. Calcd. for C H N O S (319.0375): C, 45.14;
Ar 12 9 5 4
H, 2.84; N, 21.93; S, 10.04; Found: C, 45.43; H, 3.06; N,
22.07; and S, 9.93.
6
Ar
Ar
Ar
Ar