PAPER
Synthesis of Aromatic Aminosulfonic Acid Nitroamides
1821
1
3
min at this temperature. The mixture was then poured onto ice to
C NMR (75 MHz, DMSO-d ): d = 46.35, 117.86, 125.61, 125.69,
6
form a precipitate. The product was filtered, washed with H O (10
126.33, 126.75, 129.33, 130.09, 139.37, 142.49.
HRMS: m/z [M]+ calcd for C H N O S: 295.0627; found:
2
2
1
6
mL), and dried in vacuo over P O . Additionally 2a was recrystal-
2
5
1
2
13
3
4
lised from H O and 2b from MeCN, respectively, giving samples
2
95.0628.
with correct elemental analyses.
N-Nitro-3-pyridinesulfonamide (2h)
1
N -Nitrosulfanilamide (2a)
1
H NMR (300 MHz, DMSO-d ): d = 7.85 (dd, J = 8.0, 5.2 Hz, 1 H,
1
6
H NMR (300 MHz, DMSO-d ): d = 7.14 (d, J = 8.8 Hz, 2 H, H-
,5), 7.73 (d, J = 8.8 Hz, 2 H, H-2,6).
6
H-5), 8.5 (dt, J = 8.0, 1.8 Hz, 1 H, H-6), 8.86 (dd, J = 5.2, 1.4 Hz, 1
3
H, H-4), 9.09 (d, J = 1.7 Hz, 1 H, H-2).
1
3
C NMR (75 MHz, DMSO-d ): d = 119.36, 129.74, 136.74,
40.59.
13
6
C NMR (75 MHz, DMSO-d ): d = 125.58, 139.43, 139.66,
6
1
1
46.68, 150.21.
Anal. Calcd for C H N O S: C, 33.18; H, 3.26; N, 19.34; S, 14.76.
Found: C, 32.98; H, 3.29; N, 19.35; S, 14.71.
+
6
7
3
4
HRMS: m/z [M] calcd for C H N O S: 203.0001; found: 202.999.
5
5
3
4
Sodium 4-[4-(Dimethylamino)phenylazo]benzenesulfamoylni-
tronate (2j)
4
-Dimethylamino-N-nitrobenzenesulfonamide (2b)
1
H NMR (300 MHz, DMSO-d ): d = 2.98 (s, 6 H, CH ), 6.77 (d,
J = 9.1 Hz, 2 H, H-3,5), 7.58 (d, J = 9.1 Hz, 2 H, H-2,6).
6
3
The scaled down procedure for methyl orange synthesis was adopt-
24
ed with some modifications. The crude 2a (81% pure, 1.08 g, 4.05
1
3
C NMR (75 MHz, DMSO-d ): d = 40.53, 111.65, 128.17, 129.65,
mmol) was used instead of sulfanilic acid. Acid form of 2j was fil-
6
1
51.25.
tered, washed with H O (20 mL), suspended in aq 1 M NaOH (34
2
mL) and warmed at 70–80 °C until the suspension had been dis-
solved. Crystalline product separated as the solution cooled. The
Anal. Calcd for C H N O S: C, 39.18; H, 4.52; N, 17.13; S, 13.07.
Found: C, 39.18; H, 4.54; N, 17.03; S, 13.11.
8
11
3
4
solid obtained was filtered, recrystallised from H O, and dried in a
2
1
vacuum oven at 156 °C for 3 h over P
dish-orange crystals.
2 5
O ; yield: 888 mg (59%); red-
4
-Aminomethyl-N -nitrobenzenesulfonamide (2c)
This product was contaminated with 8% of 3.
1H NMR (300 MHz, DMSO-d
J = 9.1 Hz, 2 H, XX¢ from C H SO ), 7.79–7.93 (6 H, m, AA¢BB¢
): d = 3.08 (6 H, s, CH ), 6.85 (d,
3
1
6
H NMR (300 MHz, DMSO-d ): d = 4.1 (q, J = 5.7 Hz, 2 H, CH ),
.55 (d, J = 8.5 Hz, 2 H, H-3,5), 7.81 (d, J = 8.5 Hz, 2 H, H-2,6),
6
2
6
4
2
7
8
+
from Me
13C NMR (75 MHz, DMSO-d
28.95, 142.34, 142.51, 152. 84, 153.84.
Anal. Calcd for C14 NaO S: C, 45.28; H, 3.80; N, 18.86; S,
2
NC
6
H
4
overlapped with AA¢ from C
6 4 2
H SO ).
.16 (br s, 3 H, NH ).
3
1
3
6
): d = 39.91, 111.53, 121.26, 125.20,
C NMR (75 MHz, DMSO-d ): d = 41.93, 128.12, 128.62, 137.18,
6
1
1
42.60.
+
H
16
N
5
5
ESIMS (negative ion): m/z (%) = 230 (100, M – H ), 186 (30, M –
N O – H ), 120 (10).
+
8.63. Found: C, 45.29; H, 3.98; N, 18.82; S, 8.59.
2
1
4-Benzenediazoniumsulfamoylnitronate (4)
When the preparation of 2j was stopped just after the diazotisation
stage by pouring the reaction mixture into cold H O, the precipitate
of 4 was isolated quantitatively as described earlier for nitroamides;
mp 119 °C (exploded).
3
-Amino-4-methyl-N -nitrobenzenesulfonamide (2d)
1
H NMR (300 MHz, DMSO-d ): d = 2.34 (s, 3 H, CH ), 7.43 (d,
J = 8.3 Hz, 1 H, H-5), 7.62 (dd, J = 7.9, 1.8 Hz, 1 H, H-6), 7.77 (d,
J = 1.9 Hz, 1 H, H-2).
6
3
2
1
3
C NMR (75 MHz, DMSO-d ): d = 17.01, 121.95, 126.31, 130.99,
31.55, 134.49, 141.15.
6
IR (KBr): 2302 cm–1.
1
1H NMR (300 MHz, DMSO-d
.79 (d, J = 9.2 Hz, 2 Harom).
): d = 8.31 (d, J = 9.0 Hz, 2 Harom),
+
6
HRMS: m/z [M] calcd for C H N O S: 231.0314; found: 231.0337.
7
9
3
4
8
1
13
3
-Amino-4-chloro-N -nitrobenzenesulfonamide (2e)
C NMR (75 MHz, DMSO-d ): d = 118.42, 129.61, 133.0, 153.14.
6
1
H NMR (300 MHz, DMSO-d ): d = 7.00 (dd, J = 8.4, 2.2 Hz, 1 H,
H-6), 7.34 (d, J = 2.2 Hz, 1 H, H-2) overlapped with 7.34 (d, J = 8.4
6
4-Sulfobenzylamine (3)14
Hz, 1 H, H-5).
To the cooled 95% H SO (1 mL), was added crude 2c (125 mg, 0.5
2
4
1
3
mmol) portionwise, and the resulting suspension was stirred contin-
uously and allowed to warm to r.t. After the suspension had dis-
C NMR (75 MHz, DMSO-d ): d = 115.77, 117.40, 121.06,
6
1
28.94, 142.04, 142.46.
solved, the mixture was stirred for 30 min at r.t. N O had then
2
HRMS: m/z [M]+ calcd for C H ClN O S: 250.9768; found:
2
6
6
3
4
stopped evolving and the mixture was poured onto ice. The solid
50.9778.
obtained was filtered, washed with H O (5 mL) and dried; yield: 56
2
mg (60%).
1
2
-Amino-N -nitrobenzenesulfonamide (2f)
13C NMR (75 MHz, DMSO-d
48.65.
): d = 42.03, 125.78, 128.24, 133.95,
1
6
H NMR (300 MHz, DMSO-d ): d = 7.03 (ddd, J = 8.0, 8.1, 1.1 Hz,
H, H-5) overlapped with 7.04 (dd, J = 7.1, 1.0 Hz, 1 H, H-3), 7.41
6
1
1
(
ddd, J = 8.1, 7.1, 1.4 Hz, 1 H, H-4), 7.68 (dd, J = 8.1, 1.5 Hz, 1 H,
H-6).
Acknowledgment
1
3
C NMR (75 MHz, DMSO-d ): d = 120.16, 121.17, 127.97,
6
The author thanks Eliza Zajler MSc for experimental support and
Dr. Włodzimierz Gałęzowski for helpful suggestions. The financial
support from MNiSW, grant no. N204 087 32/2496 is gratefully
acknowledged.
1
30.54, 132.98, 139.23.
+
HRMS: m/z [M] calcd for C H N O S: 217.0157; found: 217.0165.
6
7
3
4
N-Nitrodansylamide (2g)
1
H NMR (300 MHz, DMSO-d ): d = 3.15 (s, 6 H, CH ), 7.64–7.82
m, 2 H ), 7.77 (dd, J = 8.4, 7.5 Hz, 1 H ), 8.25 (dd, J = 7.5, 0.8
6
3
(
arom arom
Hz, 1 Harom), 8.42 (d, J = 8.5 Hz, 1 Harom), 8.6–8.7 (m, 1 Harom).
Synthesis 2007, No. 12, 1819–1822 © Thieme Stuttgart · New York