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Helvetica Chimica Acta Vol. 88 (2005)
J 8.2, HÀC(3')); 7.95 (d, J 5.2, HÀC(2''), HÀC(6'')); 8.08 (d, J 5.1, HÀC(6)); 8.25 (dd, J 8.2, 7.1,
HÀC(4')); 8.39 (d, J 6.0, HÀC(6')); 8.51 (s, HNÀCO); 13.47 (s, HN ). Anal.: see the Table.
4-O-Furoyltenoxicam Hydrochloride ( 2-Methyl-1,1-dioxido-3-[(pyridin-2-ylamino)carbonyl]-2H-thie-
no[2,3-e][1,2]thiazin-4-yl 2-Furoate; 10c). Accordingto GP 2. Yield: 24%. Yellowish-white crystals. M.p.
1848. UV (MeOH): 352 (3.08), 248 (3.25). 1H-NMR (CDCl3): 2.90 (s, MeN); 6.66 (dd, J 3.4, 1.7, HÀC(4''));
7.22 (dd, J 3.4, 0.9, HÀC(3'')); 7.36 (dd, J 7.2, 5.6, HÀC(5')); 7.46 (d, J 5.2, HÀC(7)); 7.76 (d, J 8.4,
HÀC(3')); 7.92 (dd, J 1.7, 0.9, HÀC(5'')); 8.05 (d, J 5.2, HÀC(6)); 8.21 (dd, J 8.4, 7.2, HÀC(4')); 8.36 (d,
J 5.6, HÀC(6')); 8.52 (s, HNÀCO); 13.54 (s, HN ). Anal.: see the Table.
4-O-Cinnamoyltenoxicam Hydrochloride ( 2-Methyl-1,1-dioxido-3-[(pyridin-2-ylamino)carbonyl]-2H-
thieno[2,3-e][1,2]thiazin-4-yl 3-Phenylprop-2-enoate; 10d). Accordingto GP 2. Yield: 39%. Yellowish-white
crystals. M.p. 2068. UV (MeOH): 352 (3.28), 272 (2.75). 1H-NMR (CDCl3): 2.91 (s, MeN); 6.53 (s, HÀC(1''));
7.18 7.27 (m, HÀC(4'') HÀC(5'') HÀC(6'') HÀC(7'') HÀC(8'')); 7.38 (dd, J 6.6, 6.2, HÀC(5')); 7.47 (d, J
5.2, HÀC(7)); 7.79 (d, J 8.6, HÀC(3')); 7.95 (s, HÀC(2'')); 8.08 (d, J 5.2, HÀC(6)); 8.23 (dd, J 8.6, 6.6,
HÀC(4')); 8.39 (d, J 6.2, HÀC(6')); 8.54 (s, HNÀCO); 13.50 (s, HN ). Anal.: see the Table.
5-Methyl-5H,6H-pyrido[2',1':2,3]pyrimido[5,4-c]thieno[2,3-e][1,2]thiazin-6-one 4,4-Dioxide (12). A soln.
of 1 (0.34 g, 1 mmol) in POCl3 (1 ml) was heated for 3 h at 1008 under N2 atmosphere. The mixture was slowly
poured onto H2O (15 ml). The resultingprecipitate was neutralized with Na CO3, suction-filtered, thoroughly
2
washed with H2O, dried at r.t., and recrystallized from EtOH to afford 0.18 g(56%) of 12. Yellowish-green solid.
M.p. 256 2588. UV (MeOH): 352 (3.88), 260 (3.52). IR (KBr): 1638w, 1615w, 1333m, 1166m. 1H-NMR
(CDCl3): 3.05 (s, MeN); 7.20 (d, J 5.1, HÀC(3)); 7.35 (dd, J 8.6, 1.2, HÀC(8)); 7.69 (d, J 5.1, HÀC(2));
7.88 (ddd, J 7.6, 6.7, 1.7, HÀC(10)); 8.37 (ddd, J 8.6, 6,7, 1.7, HÀC(9)); 9.07 (dd, J 7.6, 1.7, HÀC(11)). QP-
MS: 319 (M ). Anal.: see the Table.
4-Methyl-1-phenyl-1,4-dihydropyrazolo[4,3-c]thieno[2,3-e][1,2]thiazin-3(2H)-one 5,5-Dioxide (13). To a
suspension of 8 (0.7 g, 2 mmol) in toluene (8 ml), N,N-dimethylaniline (1 ml) and POCl3 (2 ml) were added.
The mixture was heated for 7 h at 1008 under N2 atmosphere. After cooling, the reaction was quenched with ice-
cold H2O (25 ml). The mixture was diluted with toluene (22 ml), the layers were separated, the aq. layer was
adjusted to pH 3 with conc. aq. NH4OH soln., and extracted with CHCl3 (3 Â 15 ml). The combined org. layers
were washed with 10% aq. Na2CO3 soln. (2 Â 10 ml) and H2O (2 Â 10 ml), dried (Na2SO4), decolorized over
charcoal, and evaporated in vacuo. The residue was purified by CC (SiO2; AcOEt/CH2Cl2 1 :1) and
recrystallization (i-PrOH) to afford 0.31 g(47%) of 13. Yellow solid. M.p. 209 2118. UV (MeOH): 362 (4.22),
1
265 (4.06). IR (KBr): 3253w, 1648w, 1623m, 1336m, 1157m. H-NMR (CDCl3): 3.17 (s, MeN); 6.66 7.10 (m,
HÀC(2'), HÀC(3'), HÀC(4'), HÀC(5'), HÀC(6')); 7.45 (d, J 5.1, HÀC(6)); 7.71 (d, J 5.1, HÀC(7)); 9.75
(s, HÀN). QP-MS: 333 (M ). Anal.: see the Table.
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