1300
E. S. Fondjo, J. Tsemeugne, B. L. Sondengam, T. Oppenlaender, H. K. Wabo, P. Tane,
J. D. Connolly, W. Dehaen, T. Rohand, H. Kikuchi, and Y. Oshima
Vol 48
1.3 Hz), 7.66 (s, 1H, 6"-H), 7.64 (broad s, 3H, NH3þ, deute-
rium oxide-exchangeable), 7.30 (d, 1H, 6’-H, J ¼ 1.2 Hz),
7.27 (dd, 1H, 4’-H, J ¼ 1.2, 6.7 Hz), 7.24 (dd, 1H, 5’-H, J ¼
1.2, 6.3 Hz), 7.23 (d, 1H, 3’-H, J ¼ 1.2 Hz), 7.22 (d, 1H, 3"-
H, J ¼ 1.2 Hz), 7.19 (s, 1H, 5-H); 13C(1H)-NMR (DMSO-d6,
300 MHz) d 184.3 (COOH), 154.9 (C-2’), 153.4 (C-3), 153.4
(C-2"), 147.3 (C-4), 135.4 (C-5"), 135.2 (C-2), 128.9 (C-4’),
128.9 (C-6’), 125.4 (C-5), 125.4 (C-4"), 125.4 (C-6"), 125.3
(C-1’), 119.9 (C-1"), 117.1 (C-5’), 116.9 (C-3"), 114.9 (C-3’);
ms: (FABþ) m/z (%) 384 (1), 383 (1), 307 (60), 429 (11), 248
(100), 154 (91). Anal. Calcd. for C17H14N4O9S2: C, 42.32; H,
2.92; N, 11.61. Found: C, 42.25; H, 3.01; N, 11,69.
(4H)-3-Amino-1-phenylazo-1-thieno[3,4-c]chromen-4-one(10).
mp 238–239ꢀC [lit. [28] 232–234ꢀC from DMF/ethanol (5:3)];
IR (potassium bromide): 3207, 3107, 3062, 2896, 2875, 2845,
2580, 1874, 1731, 1683, 1488, 1404 cmꢁ1; kmax (THF) (log e)
211 (3.67), 253 (4.11), 291 (3.89), 336 (3.66), 478 nm (4.12);
1H-NMR (DMSO-d6, 300 MHz) d 8.84 (dd, 1H, H-9, J ¼ 7.9,
1.4 Hz), 7.74 (d, 1H, H-2’ and H-6’, J ¼ 7.4 Hz), 7.59 (ddd,
1H, H-7, J ¼ 1.5, 7.7, 7.7 Hz), 7.54 (dd, 1H, H-3’ and H-5’, J
¼ 7.5, 8.0 Hz), 7.40 (d, 1H, H-4’, J ¼ 7.4 Hz), 7.45 (ddd, 1H,
H-8, J ¼ 1.1, 7.7, 7.6 Hz), 7.35 (dd, 1H, H-6, J ¼ 7.4, 8.3
Hz); 13C(1H)-NMR (DMSO-d6, 300 MHz) d 168.2 (C-3),
158.2 (C-4a), 152.6 (C-1’ and C-8a), 151.9 (C-2), 134.9 (C-9),
133.0 (C-8b), 131.5 (C-7), 129.4 (C-3’ and C-5’), 129.0 (C-6),
128.8 (C-8), 125.1 (C-4’), 121.7 (C-2’ and C-6’), 117.2 (C-5),
117.0 (C-2a); ms: (EI) m/z (%) 321 (6), 280 (22), 247 (22 ),
208 (100 ), 190 (24). Anal. Calcd. for C17H11N3O2S: C, 63.54;
H, 3.45; N, 13.08. Found C, 63.43; H, 3.50; N, 13.15.
2-Amino-4-(2-hydroxyphenyl)-5-phenylazothiophene-3-car-
boxylic acid(11). mp 150ꢀC; IR (potassium bromide): 3425,
3315, 3143, 3056, 3028, 1741, 1676, 1483, 1460 cmꢁ1; kmax
(THF) (log e) 203 (3.87), 212 (3.78), 220 (3.91), 247 (4.47),
258 (4.48), 288 (4.33), 345 (4.02), 461 (4.52), 471 nm (4.54).
Anal. Calcd. for C17H13N3O3S: C, 60.18; H, 3.83; N, 12.39.
Found: C, 60.05; H, 3.71; N, 12.46.
Azo bis[4-(2-hydroxyphenyl)-thiophene-3-carboxylic acid-2-
yl](8). b-Naphthol (0.384 g; 3 mmol) was dissolved in DMSO
(10 mL) and then cooled in an ice-bath at 0–5ꢀC. The diazo-
nium solution 3 previously prepared was added dropwise over
1 h, and then 15 mL of sodium acetate solution (10%) was
added in the mixture. The solid precipitate was filtered and
crystallized from methanol to give the title compound 8 (31.3
mg, 20%) as yellow powder mp > 230ꢀC; IR (potassium bro-
mide): 3807, 3484, 2299, 1750, 1726, 1444; kmax (THF) (log
e) 203 (4.60), 215 (4.59), 234 (4.92), 276 (4.94), 281 (4.96),
1
325 (4.61), 385 nm (4.34); H-NMR (DMSO-d6, 300 MHz) d
14.38 (broad s, 1H, COOH, deuterium oxide-exchangeable);
8.70 (dd, 1H, 3’-H, J ¼ 0.9 and 6.00 Hz); 8.05 (broad s, 1H,
NH, deuterium oxide-exchangeable); 7.85 (ddd, 1H, 4’-H, J ¼
0.9, 5.4 and 6.3 Hz); 7.60 (s, 2H, 5-H), 7.51 (ddd, 2H, 5’-H, J
¼ 0.9, 5.4, 10.8 Hz), 7.31 (d, 2H, 6’-H, J ¼ 6.6 Hz), 6.98
(broad s, 2H, OH, deuterium oxide-exchangeable); 13C(1H)-
NMR (DMSO-d6, 300 MHz) d 184.1 (COOH), 154.9 (C-2’),
153.8 (C-3), 153.4 (C-1’), 147.7 (C-4), 135.5 (C-2), 128.8 (C-
6’), 125.4 (C-5), 120.0 (C-5’), 117.1 (C-3’), 114.8 (C-4’); ms:
(EI) m/z(%) 364 (2), 402 (1), 248 (12), 247 (100), 231 (40),
214 (12), 203 (14), 189 (24), 144 (28), 77 (10). Anal. Calcd.
for C22H16N2O10S3: C, 46.80; H, 2.86; N, 4.96. Found C,
46.65; H, 2.88; N, 4.80.
5,5’-Diamino-3,3’-bis-(2-hydroxyphenyl)-[2,2’]bithiophenyl-
4,4’-dicarboxylic acid (12). The reaction mixture of the diazo-
nium sulfate of 1a and 1b was worked up as above to afford
the title compound 12 (340 mg, 24%). Crystallization from
methanol gave the title compound 12 as a brown powder, mp
> 283ꢀC; IR (potassium bromide): 3658, 3253, 3137, 2991,
2948, 2831, 2198, 1976, 1928, 1758, 1693 cmꢁ1; kmax (THF)
(log e) 204 (4.15), 213 (4.17), 234 (4.49), 274 (4.53), 281
(4.54), 301 (3.86), 364 (3.67), 527 nm (4.24); 1H-NMR
(DMSO-d6, 300 MHz) d 15.20 (broad s, 2H, OH, deuterium
oxide-exchangeable), 13.49 (broad s, 2H, COOH, deuterium
oxide-exchangeable), 9.51 (dd, 2H, H-5’, J ¼ 1.50, 8.10 Hz),
8.64 (broad s, 2H, NH2, deuterium oxide-exchangeable), 8.32
(2H, ddd, J 1.0, 8.5, 5.4 Hz, H-3’), 8.29 (d, 2H, H-6’, J ¼ 8.3
Hz), 7.85 (dd, 2H, H-4’, J ¼ 5.4, 6.3 Hz), 7.60 (broad s, 2H,
OH, deuterium oxide-exchangeable); 13C (1H)-NMR (DMSO-
d6, 300 MHz) d 184.2 (COOH), 154.9 (C-2’), 153.9 (C-2),
153.5 (C-5), 147.8 (C-4), 135.5 (C-6’), 128.8 (C-4’), 125.4 (C-
5’), 120.0 (C-3), 117.1 (C-3’), 114.9 (C-1’); ms: (EI) m/z (%)
347 (1), 331 (1), 300 (2), 285 (1), 255 (4), 247 (12), 231 (1),
211 (3), 181 (4), 167 (7). Anal. Calcd. for C22H16N2O6S2: C,
56.40; H, 3.44; N, 5.98. Found C, 56.49; H, 3.53; N, 5.85.
(4H)-2-(2-Amino-5-nitrophenyl) thieno [3,4-c]chromen-4-
one hydrogen sulfate(9). mp 238–239ꢀC; IR (potassium bro-
mide) 3556, 3351, 3105, 3001, 2794, 2700, 2690, 2599, 1728,
1679 cmꢁ1; kmax (THF) (log e) 203 (4.39), 213 (4.38), 239
1
(4.90), 267 (4.85), 286 (4.84), 324 (4.86), 383 nm (4.44); H-
NMR (DMSO-d6, 300 MHz) d 14.35 (broad s, 1H, HSO4-,
deuterium oxide-exchangeable), 8.02 (d, 1H, 4’-H, J ¼ 1.1
Hz), 8.01 (d, 1H, 3’-H, J ¼ 1.5 Hz), 7.85 (ddd, 1H, 7-H, J ¼
1.5, 8.3, 11.8 Hz), 7.78 (ddd, 1H, 8-H, J ¼ 1.5, 9.4, 11.9 Hz),
7.78 (d, 1H, 6-H, J ¼ 9.5 Hz), 7.55 (s, 1H, 6’-H), 7.49 (d, 1H,
9-H, J ¼ 1.1 Hz), 7.46 (s, 1H, 1-H), 3.36 (3H, NH3þ, deute-
rium oxide-exchangeable); ms: (EI) m/z (%) 436 (1), 425 (51),
392 (1), 362 (7), 310 (11), 268 (76 ), 235 (1), 228 (82 ), 201
(43), 186 (1), 121 (6), 157 (13). Anal. Calcd. for
C17H12N2O8S2: C, 46.79; H, 2.77; N, 6.42. Found: C, 46.69;
H, 2.68; N, 6.51.
Preparation of 10 and 11. Compound 1a (0.651 g; 3
mmol) was dissolved in DMSO (10 mL) and then cooled in an
ice-bath at 0–5ꢀC. The diazonium solution of 4a previously
prepared was added dropwise over 1 h, and then 15-mL sodium
acetate solution (10%) was added to the mixture. The solid ma-
terial that was formed, was filtered, and crystallized from hot
water to afford the title compound 11 (370 mg, 26%) as a red
powder. The solid residue was crystallized from methanol to
yield the title compound 10 (388 mg, 40%) as a red powder.
Acknowledgment. E.S.F. gratefully acknowledges financial
support from DAAD (grant No A/09/07421) for a current three
´
months Scholarship. The Reichert Thermovar microscope and
the SHIMADZU FTIR-8400S spectrometer were donated by the
Swedish foundation IPICS (International Programme in the
Chemical Sciences). The authors are grateful to the University of
Dschang research grants committee for financial support. Thanks
are equally due to Dr. Mathieu Tene and Dipl. -Ing. Miss Helga
Weinschrott for their technical assistance.
REFERENCES AND NOTES
[1] Habibi, M. H.; Hassanzadeh, A.; Isfahani, A. Dyes Pigm
2006, 69, 93.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet