484
C. Pirat et al.
PAPER
IR (KBr): 1674 (CON).
1H NMR (CDCl3): d = 3.55 (s, 3 H, NCH3), 6.91 (d, J = 3.7 Hz, 1 H,
HAr), 7.37 (d, J = 3.7 Hz, 1 H, HAr), 7.50 (d, J = 8.2 Hz, 1 H, H7),
7.51 (d, J = 1.6, 1 H, H4), 7.61 (dd, J = 8.2, 1.6 Hz, 1 H, H6), 9.68
(s, 1 H, CHO).
13C NMR (CDCl3): d = 29.4, 106.8, 108.1, 120.4, 123.0, 124.0,
124.4, 127.5, 138.5, 152.1, 158.6, 169.8, 177.1.
1H NMR (CDCl3): d = 2.68 (s, 3 H, COCH3), 3.52 (s, 3 H, NCH3),
7.24 (d, J = 1.7 Hz, 1 H, H4), 7.42 (dd, J = 8.0, 1.7 Hz, 1 H, H6), 7.52
(d, J = 8.1 Hz, 1 H, H7), 7.58 (t, J = 7.7 Hz, 1 H, HAr), 7.81 (ddd,
J = 7.7, 1.7, 1.1 Hz, 1 H, HAr), 7.97 (ddd, J = 7.7, 1.7, 1.1 Hz, 1 H,
HAr), 8.20 (t, J = 1.7 Hz, 1 H, HAr).
13C NMR (CDCl3): d = 26.8, 29.2, 109.1, 122.2, 122.4, 122.9, 126.7,
127.8, 129.3, 131.8, 137.7, 138.4, 139.0, 141.0, 170.1, 198.0.
MS (APCI+): m/z = 260.1 [M + H]+.
MS (APCI+): m/z = 283.9 [M + H]+.
Acknowledgment
3-(3-Methyl-2-oxo-2,3-dihydro-1,3-benzothiazol-5-yl)benzoni-
trile (21)
Yield: 89%; mp 197–198 °C.
The 300 MHz NMR facilities were funded by the Région Nord-Pas
de Calais (France), the Ministère de la Jeunesse, de l’Education Na-
tionale et de la Recherche (MJENR), and the Fonds Européens de
Développement Régional (FEDER).
IR (KBr): 2230 (CN), 1693 (CON).
1H NMR (CDCl3): d = 3.54 (s, 3 H, NCH3), 7.20 (d, J = 1.7 Hz, 1 H,
H4), 7.38 (dd, J = 8.1, 1.7 Hz, 1 H, H6), 7.54 (d, J = 8.1 Hz, 1 H, H7),
7.60 (t, J = 7.7 Hz, 1 H, HAr), 7.68 (dt, J = 7.7, 1.5 Hz, 1 H, HAr),
7.85 (dt, J = 7.7, 1.5 Hz, 1 H, HAr), 7.89 (t, J = 1.5 Hz, 1 H, HAr).
13C NMR (CDCl3): d = 29.2, 109.0, 113.2, 118.7, 122.2, 123.0,
123.1, 129.9, 130.7, 131.1, 131.5, 137.7, 138.5, 141.7, 170.0.
References
(1) Yous, S.; Poupaert, J.-H.; Lesieur, I.; Depreux, P.; Lesieur,
D. J. Org. Chem. 1994, 59, 1574.
(2) Diouf, O.; Carato, P.; Depreux, P.; Bonte, J.-P.; Caignard,
D.-H.; Guardiola-Lemaître, B.; Rettori, M. C.; Belzung, C.;
Lesieur, D. Bioorg. Med. Chem. Lett. 1997; 7, 2579.
(3) Diouf, O.; Carato, P.; Lesieur, I.; Rettori, M. C.; Caignard,
D.-H. Eur. J. Med. Chem. 1999, 34, 9.
MS (APCI+): m/z = 266.2 [M + H]+.
5-(3-Aminophenyl)-3-methyl-1,3-benzothiazol-2(3H)-one (22)
(4) Lesieur, D.; Carato, P.; Bonte, J.-P.; Depreux, P.; Caignard,
D.-H.; Millan, M.; Newman-Tancredi, A.; Renard, P.;
Rettori, M. C. EP0841330 1998; Chem. Abstr. 1998, 129,
4662x.
(5) Carato, P.; Depreux, P.; Lesieur, D.; Millan, M.; Newman-
Tancredi, A.; Rettori, M. C.; Caignard, D.-H. Drug Des.
Discovery 2000, 17, 73.
(6) Blanc-Delmas, E.; Lebegue, N.; Wallez, V.; Leclerc, V.;
Yous, S.; Carato, P.; Farce, A.; Bennejean, C.; Renard, P.;
Caignard, D.-H.; Audinot-Bouchez, V.; Chomarat, P.;
Boutin, J.; Hennuyer, N.; Louche, K.; Carmona, M. C.;
Staels, B.; Penicaud, L.; Casteilla, L.; Lonchampt, M.;
Dacquet, C.; Chavatte, P.; Berthelot, P.; Lesieur, D. Bioorg.
Med. Chem. 2006, 14, 7377.
(7) Takao, T.; Hisashi, T. EP0120589 1984.
(8) Aichaoui, H.; Poupaert, J. H.; Lesieur, D.; Hénichart, J.-P.
Tetrahedron 1991, 47, 6649.
Yield: 83%; mp 166–167 °C.
IR (KBr): 3351 (NH2), 1665 (CON).
1H NMR (CDCl3): d = 3.52 (s, 3 H, NCH3), 3.75 (br s, 2 H, NH2),
6.73 (ddd, J = 7.7, 1.9, 1.0 Hz, 1 H, HAr), 6.92 (t, J = 1.9 Hz, 1 H,
HAr), 7.00 (ddd, J = 7.7, 1.9, 1.0 Hz, 1 H, HAr), 7.21 (d, J = 1.7 Hz,
1 H, H4), 7.27 (t, J = 7.7 Hz, 1 H, HAr), 7.38 (dd, J = 8.0, 1.7 Hz, 1
H, H6), 7.48 (d, J = 8.0 Hz, 1 H, H7).
13C NMR (CDCl3): d = 29.1, 109.1, 113.7, 114.5, 117.5, 121.4,
122.3, 122.6, 129.9, 138.1, 140.4, 141.7, 147.0, 170.3.
MS (APCI+): m/z = 257 [M + H]+.
5-(3-Hydroxyphenyl)-3-methyl-1,3-benzothiazol-2(3H)-one
(23)
Yield: 72%; mp 182–183 °C.
IR (KBr): 3304 (OH), 1660 (CON)
(9) Aichaoui, H.; Lesieur, I.; Hénichart, J.-P. Synthesis 1990, 8,
679.
(10) Tzanova, T.; Gerova, M.; Petrov, O.; Karaivanova, M.;
Bagrel, D. Eur. J. Med. Chem. 2009, 44, 2724.
(11) Nishiguchi, I.; Konishi, K.; Hirashima, T. Heterocycles
1984, 21, 455.
(12) Konishi, K.; Nishiguchi, I.; Hirashima, T. Synthesis 1984,
254.
(13) Hodgson, W. J. Chem. Soc. 1925, 127, 442.
(14) Zhifang, L.; Yongmin, Z. Heteroat. Chem. 2003, 14, 46.
(15) Heiss, C.; Andersson, J.; Phillips, R. Org. Biomol. Chem.
2003, 1, 288.
1H NMR (DMSO-d6): d = 3.48 (s, 3 H, NCH3), 6.80 (ddd, J = 8.0,
2.3, 1.0 Hz, 1 H, HAr), 7.10 (t, J = 1.9 Hz, 1 H, HAr), 7.15 (dt, J =
8.0, 1.6 Hz, 1 H, HAr), 7.28 (t, J = 8.0 Hz, 1 H, HAr), 7.44 (dd, J =
8.1, 1.7 Hz, 1 H, H6), 7.50 (d, J = 1.5 Hz, 1 H, H4), 7.71 (d, J = 8.2
Hz, 1 H, H7), 9.57 (br s, 1 H, OH).
13C NMR (DMSO-d6): d = 29.5, 110.0, 114.2, 115.1, 118.2, 120.9,
122.1, 123.5, 130.4, 138.7, 139.7, 141.6, 158.3, 169.4.
MS (APCI+): m/z = 257.9 [M + H]+.
5-(3-Methyl-2-oxo-2,3-dihydro-1,3-benzothiazol-5-yl)-2-fur-
aldehyde (24)
Yield: 54%; mp 150–151 °C.
(16) Carato, P.; Cherry, K.; Lebegue, N.; Berthelot, P.; Yous, S.
Heterocycles 2007, 71, 2041.
(17) Cherry, K.; Lebegue, N.; Leclerc, V.; Carato, P.; Yous, S.;
Berthelot, P. Tetrahedron Lett. 2007, 48, 5751.
IR (KBr): 1687 (CON), 1662 (CHO).
Synthesis 2011, No. 3, 480–484 © Thieme Stuttgart · New York