16
Z. Brzozowski, J. Sławiński, and K. Szafrański
Vol 51
3,8‐Diethoxy‐1,10‐bis(3‐nitrobenzenesulfonylimino)deca‐
2,4,6,8‐tetraene‐2,9‐disulfonamide (10). Starting from
250–251°C; IR (KBr) 3370, 3270 (SO2NH2), 1645 (C O), 1610,
1600 (NO2), 1345, 1160 (SO2) cm−1 1H‐NMR (dimethyl
;
4‐ethoxy‐3‐pyridinesulfonamide 1c (1.01 g), the title compound
10 was obtained (1.6 g, 82%): m.p. 175–176°C; IR (KBr) 3300,
3200 (SO2NH2), 2925, 2850 (EtO), 1635, 1190 (NO2), 1355,
sulfoxide‐d6) δ 6.52 (d, J = 7.8 Hz, 1H, H‐5, pyrid.), 7.02
(s, 2H, SO2NH2), 8.02 (dd, Jortho = 7.8 Hz, Jmeta = 2.3 Hz, 1H,
H‐6 pyrid.), 8.18 (d, J = 8.7 Hz, 1H, H‐6, 2,4‐diO2NPh), 8.52
(d, Jmeta = 2.3 Hz, 1H, H‐2, pyrid.), 8.74 (dd, Jortho = 8.7 Hz,
Jmeta = 2.6 Hz, 1H, H‐5 di‐O2NPh ), 8.98 (d, Jmeta = 2.6 Hz,
1H, H‐3, 2,4‐di O2NPh) ppm; 13C‐NMR (dimethyl sulfoxide‐d6)
δ 119.98, 121.70, 129.82, 130.99, 132.24, 139.88, 141.30,
142.13, 144.35, 147.87, 172.86 ppm. Analysis calculated for
C11H8N4O7S (340.27): C, 38.82; H, 2.37; N, 16.45. Found: C,
38.83; H, 2.41; N, 16.47.
1
1145 (SO2) cm−1; H‐NMR (dimethyl sulfoxide‐d6) δ 1.44 (t, J =
7.0 Hz, 6H, 3,8‐di CH3CH2O), 4.55 (q, J = 7.0 Hz, 4H, 3,8‐di
CH3CH2O), 7.61 (t, J = 7.7 Hz, 2H, H‐5, and H‐5′, benzene
rings), 7.71 (d, J = 6.6 Hz, 2H, H‐5 and H‐6), 7.79 (s, 4H, 2,9‐
di‐SO2NH2), 8.04 (d, J = 7.7 Hz, 2H, H‐6 and H‐6′, benzene
rings), 8.19 (d, J = 7.8 Hz, 2H, H‐4 and H‐4′, benzene rings),
8.33 (s, 2H, H‐2, and H‐2′, benzene rings), 8.87 (d, J = 6.6 Hz,
2H, H‐4 and H‐7), 8.96 (s, 2H, H‐1 and H‐10) ppm. Analysis
calculated for C26H28N6O14S4 (776.81): C, 40.20; H, 3.63; N,
10.81. Found: C, 40.22; H, 3.65; N, 10.92.
The acetonitrile filtrate was evaporated to 1/3 volume at nor-
mal pressure and left to stand at room temperature for three days.
The precipitate of title compound 14 was filtrated off, washed
with acetonitrile (1.5 mL) and recrystallized from acetonitrile.
Yield: 1.0 g (53%): m.p. 246–247°C; IR (KBr) 3350, 3150
3,8‐Di(2,4‐dichlorophenoxy)‐1,10‐bis(3‐nitrobenzenesulfony-
limino)deca‐2,4,6,8‐tetraene‐2,9‐disulfonamide (11).
Starting
1
(SO2NH2), 1650 (C O), 1330, 1160 (SO2) cm−1; H‐NMR (di-
from 4‐(2,4‐dichlorophenoxy)‐3‐pyridinesulfonamide 3d (1.6 g),
the title compound 11 was obtained (2.1 g, 83%): m.p. 175–176°
C; IR (KBr) 3230, 3165 (SO2NH2), 1630, 1180 (NO2), 1355,
methyl sulfoxide‐d6) δ 3.73 (s, 3H, CH3), 6.35 (d, J = 7.5 Hz,
1H, H‐5), 6.79 (s, 2H, SO2NH2), 7.76 (dd, Jortho = 7.5 Hz, Jmeta
= 2.2 Hz, 1H, H‐6), 8.29 (d, Jmeta = 2.2 Hz, 1H, H‐2) ppm;
13C‐NMR (dimethyl sulfoxide‐d6) δ 43.65, 120.04, 129.93,
142.19, 143.45, 172.34 ppm. Analysis calculated for C6H8N2O3S
(188.20): C, 38.29; H, 4.28; N, 14.88. Found: C, 38.34; H, 4.30;
N, 14.90.
1
1145 (SO2) cm−1; H‐NMR (dimethyl sulfoxide‐d6) δ 7.09 (d, J
= 6.3 Hz, 2H, H‐5 and H‐6), 7.30 (s, 4H, 2,9‐di‐SO2NH2), 7.49
(d, J = 8.7 Hz, 2H, H‐6 and H‐6′, 2,4‐diClPh), 7.62 (d, Jmeta
=
2.0 Hz, 2H, H‐3 and H‐3′, 2,4‐diClPh), 7.68 (d, J = 7.6 Hz, 2H,
H‐5 and H‐5′, 3‐O2NPh), 7.93 (dd, Jortho = 8.7 Hz, 2H, H‐5 and
H‐5′, 2,4‐diClPh), 8.03 (d, J = 7.6 Hz, 2H, H‐6 and H‐6′,
3‐O2NPh), 8.19 (dd, Jortho = 7.6 Hz, Jmeta = 1.1 Hz, 2H, H‐4 and
H‐4′, 3‐O2NPh), 8,32 (s, 2H, H‐2 and H‐2′, 3‐O2NPh), 8.74 (d, J
= 6.3 Hz, 2H, H‐4 and H‐7), 9.06 (s, 2H, H‐1 and H‐10) ppm;
13C‐NMR (dimethyl sulfoxide‐d6) δ 112.06, 120.33, 123.69,
125.45, 127.30, 129.56, 129.86, 130.07, 130.97, 132.22, 132.29,
146.30, 147.31, 147.49, 150.14, 151.84, 152.87 ppm. Analysis
calculated for C34H24Cl4N6O14S4 (1010.68): C, 40.40; H, 2.39;
N, 8.31. Found: C, 40.40; H, 2.41; N, 8.32.
Synthesis of 4‐dimethylaminopyridinium 4‐methoxy‐N‐
(2,5‐dichlorophenylsulfonyl)‐3‐pyridinesulfonamidate
and 1H+‐pyridinium‐4‐methoxy‐3‐[N‐(2,5‐dichlorophenyl)
sulfonyl]sulfonamidate (16). To a stirred suspension of
(15)
4‐methoxy‐3‐pyridinesulfonamide 1b (1.5 g, 8 mmol) and
4‐dimethyaminopyridine (2.1 g, 17 mmol) in acetonitrile (25
mL), the 2,5‐dichlorobenzenesulfonyl chloride 2a (2.0 g, 8.1
mmol) was added portion wise. The reaction mixture was stirred
at room temp. for 12 h, followed at reflux for 6 h. The solution
obtained was cooled to room temperature and the resulting
suspension was left overnight. The precipitate of title compound
15 was filtered off, washed successively with water (4× 2 mL)
and tetrahydrofuran (3× 2 mL) and dried. Yield: 3.8 g (91%);
m.p. 185–186°C; IR (KBr) 3225 (NH), 2925 (CH3), 2850,
2805, 2690 (NH+), 1645 (C N), 1580, 1555 (C C), 1315, 1160
3,8‐Di(4‐cyanophenoxy)‐1,10‐bis(3‐nitrobenzenesulfonyli-
mino)deca‐2,4,6,8‐tetraene‐2,9‐disulfonamide (12).
Starting
from 4‐(4‐cyanophenoxy)‐3‐pyridinesulfonamide 1e (1.4 g), the
title compound 12 was obtained (1.6 g, 69%): m.p. 274–275°C;
IR (KBr) 3350, 3250 (SO2NH2), 2235 (C N), 1690, 1175 (NO2),
1
1350, 1150 (SO2) cm−1; H‐NMR (dimethyl sulfoxide‐d6) δ 7.22
(SO2) cm−1 1H‐NMR (dimethyl sulfoxide‐d6) δ 3.17 (s, 6H,
;
(d, J = 8.0 Hz, 4H, H‐3,3′ and H‐5,5′, PhC N), 7.45 (d, J = 8.0
Hz, 4H, H‐2,2′ and H‐6,6′, PhC N), 7.56 (s, 4H, 2,9‐di‐SO2NH2),
7.15 (d, J = 6.2 Hz, 2H, H‐5 and H‐6), 7.96 (d, J = 7.6 Hz, 2H,
H‐5,5′, 3‐O2NPh), 8.02 (d, J = 7.6 Hz, 2H, H‐6,6′, 3‐O2NPh),
8.17 (d, J = 7.6 Hz, 2H, H‐4,4′, 3‐O2NPh), 8.30 (s, 2H, H‐2,2′,
3‐O2NPh), 8.76 (d, J = 6.2 Hz, 2H, H‐4 and H‐7), 9.06 (s, 2H,
H‐1 and H‐10) ppm; 13C‐NMR (dimethyl sulfoxide‐d6) δ 109.00,
113.58, 118.24, 120.06, 121.89, 123.42, 129.81, 130.47, 131.96,
135.09, 146.58, 146.75, 149.90, 152.12, 156.54, 162.14 ppm.
Analysis calculated for C36H26N8O14S4 (922.93): C, 46.85; H,
2.84; N, 12.14. Found: C, 46.81; H, 2.30; N, 12.12.
Synthesis of 1,4‐dihydro‐1‐(2,4‐dinitrophenyl)‐4‐oxo‐3‐
pyridinesulfonamide (13) and 1,4‐dihydro‐1‐methyl‐4‐oxo‐
3‐pyridinesulfonamide (14) in the reaction of 4‐metoxy‐3‐
pyridinesulfonamide (1b) with 2,4‐dinitrobenzenesulfonyl
chloride. A mixture of pyridinesulfonamide 1b (1.89 g, 0.01
mol) and 2,4‐dinitrobenzenesulfonyl chloride 2f (2.72 g, 0.0102
mol) in dry acetonitrile (35 mL) was stirred at room temperature
for 48 h, followed at reflux for 40 h, and then left to stand
overnight. The title compound 13 thus obtained was collected
by filtration, washed with acetonitrile (3× 1.5 mL), (filtrates was
left for further work‐up), and dried. Yield: 0.85 g (25%): m.p.
CH3‐ N‐CH3), 3.35 (s, 1H, NH), 3.71 (s, 3H, CH3O), 6.90 (d, J
= 5.8 Hz, 1H, H‐5, Py‐SO2N), 6.98 (d, J = 7.1 Hz, 2H,
DMAP), 7.41 (s, 2H, H‐3 and H‐4, 2,5‐diClPh), 7.49 (s, 1H, H‐
6, 2,5‐diClPh), 8.21 (d, J = 7.1 Hz, 2H, DMAP), 8.40 (d, J =
5.8 Hz, 1H, H‐6, Py‐SO2N), 8.49 (s, 1H, H‐2, Py‐SO2N) ppm.
Analysis calculated for C19H20Cl2 N4O5S2 (519.44): C, 43.93;
H, 3.88; N, 10.78. Found: C, 43.90; H, 3.92; N, 10.80.
To a stirred suspension of dimethylamino pyridinium‐3‐
pyridinesulfonamidate 15 (2.08 g, 4 mmol) in water (25 mL)
was slowly acidified to pH 1 with 1% hydrochloric acid. After 2
h of stirring, the title compound 16 was filtered off, washed with
water (4× 5 mL) and methanol (3× 1.5 mL), and dried. Yield: 1.5
g (94%); m.p. 269–270°C; IR (KBr) 3090 (CH‐arom) 2920
(CH3O), 2785, 2610 (NH+), 1635 (C N), 1555, 1495 (C C),
1330, 1145 (SO2) cm−1 1H‐NMR (dimethyl sulfoxide‐d6) δ
;
4.00 (s, 3H, CH3O), 7.42 (d, J = 7.4 Hz, 1H, H‐5, Py‐SO2N),
7.50 (s, 2H, H‐3 and H‐4, 2,5‐diClPh), 7.61 (s, 1H, H‐6, 2,5‐
diClPh), 8.21 (br.s, 1H, NH+), 8.70 (d, J = 7.4 Hz, 1H, H‐6,
Py‐SO2N), 8.76 (s, 1H, H‐2, Py‐SO2N) ppm. Analysis calculated
for C12H10Cl2 N2O5S2 (397.26): C, 36.28; H, 2.53; N, 7.05.
Found: C, 36.30; H, 2.64; N, 7.10.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet