UNSYMMETRICAL DIBENZOTHIOPHENES
503
7.49–7.54 (m, 2H), 7.87 (d, J ¼ 8 Hz, 1H), 8.02–8.06 (m, 1H), 8.37–8.41 (m, 1H);13C
NMR (100 MHz, DMSO-d6): d 22.1, 120.6, 122.9, 124.6, 125.0, 126.1, 126.4, 127.1,
133.0, 134.6, 135.8, 138.7, 138.9. CHNS: Calculated for C13H10S: C, 78.75; H, 5.08;
S, 16.17. Found: C, 78.30; H, 5.05; S, 16.11.
Methyldibenzo[b,d]thiophene-3-carboxylate (1d). White solid, mp:
138 ꢀC; IR (KBr): nmax 2939, 1712, 1597, 1442, 1388, 1288, 1253, 1112, 974, 848,
754 cmꢁ1 1H NMR (400 MHz, DMSO-d6): d 3.90 (s, 3H), 7.55–7.60 (m, 2H),
;
8.04–8.10 (m, 2H), 8.44–8.47 (m, 1H), 8.51 (d, J ¼ 8.4 Hz, 1H), 8.67 (d, J ¼ 1.6 Hz,
1H); 13C NMR (100 MHz, DMSO-d6): d 52.3, 122.0, 122.9, 123.0, 124.0, 125.0,
125.1, 127.9, 128.1, 134.0, 138.1, 138.7, 140.2, 165.9. CHNS: Calculated for
C14H10O2S: C, 69.40; H, 4.16; S, 13.23. Found: C, 69.48; H, 4.17; S, 13.41.
3-Nitrodibenzo[b,d]thiophene (1e). Yellow solid; mp: 150 ꢀC; IR (KBr):
1
nmax 2962, 1604, 1518, 1448, 1330, 1261, 1103, 1022, 879, 771, 738 cmꢁ1; H NMR
(400 MHz, DMSO-d6): d 7.61–7.66 (m, 2H), 8.14 (d, J ¼ 8 Hz, 1H), 8.32 (dd,
J ¼ 8.8 Hz, 2 Hz, 1H), 8.52 (d, J ¼ 8 Hz, 1H), 8.60 (d, J ¼ 8.8 Hz, 1H), 9.08 (d,
J ¼ 2 Hz, 1H);13C NMR (100 MHz, DMSO-d6): d 118.5, 119.6, 122.5, 123.3, 123.5,
125.3, 128.8, 133.2, 139.1, 140.0, 141.3, 145.8; ESI-MS: m=z: 230 (M þ H)þ, CHNS:
Calculated for C12H7NO2S: C, 62.87; H, 3.08; N, 6.11; S, 13.99. Found: C, 62.86; H,
3.10; N, 6.10; S, 13.95.
Methyl 2-methoxydibenzo[b,d]thiophene-3-carboxylate (1f). White
solid, mp: 128 ꢀC; IR (KBr): nmax 3347, 1610, 1450, 1366, 1345, 1250, 891, 840,
760, 740 cmꢁ1;1H NMR (400 MHz, DMSO-d6): d 3.82 (s, 3H), 3.96 (s, 3H),
7.51–7.57 (m, 2H), 8.03 (d, J ¼ 8.4 Hz, 1H), 8.10 (s, 1H), 8.29 (s, 1H), 8.49 (d,
J ¼ 8.4 Hz, 1H); 13C NMR (100 MHz, DMSO-d6): d 52.0, 56.3, 105.3, 120, 123.0,
23.1, 124.6, 125.2, 127.9, 129.5, 134.4, 139.0, 140.8, 156.1, 165.9; ESI-MS: m=z:
273 (M þ H)þ. CHNS: Calculated for C15H12O3S: C, 66.16; H, 4.44; S, 11.77.
Found: C, 66.15; H, 4.51; S, 11.65.
1-(9-Methyldibenzo[b,d]thiophen-2-yl)ethanone (1g). White solid, mp:
1678, 1356, 1313, 1244, 879, 840, 767 cmꢁ1 1H NMR
;
125 ꢀC; IR (KBr): n
max
(400 MHz, DMSO-d6): d 2.72 (s, 3H), 2.94 (s, 3H), 7.38 (d, J ¼ 7.2 Hz, 1H), 7.49
(t, J ¼ 7.6 Hz, 1H), 7.95 (d, J ¼ 8 Hz, 1H), 8.11 (dd, J ¼ 8.4, 1.6 Hz, 1H), 8.21 (d,
J ¼ 8.4 Hz, 1H), 8.90 (d, J ¼ 1.6 Hz, 1H); 13C NMR (100 MHz, DMSO-d6): d 21.8,
26.7, 120.8, 121.9, 124.6, 125.5, 127, 127.5, 132.5, 133.3, 134.9, 135.6, 139.3, 143.8,
197.3; ESI-MS: m=z: 240.8 (M þ H)þ; CHNS. Calculated for C15H12OS: C, 74.97;
H, 5.03; S, 13.34. Found: C, 74.90; H, 4.99; S, 13.10.
8-Ethyl-1-methyldibenzo[b,d]thiophene (1h). Semisolid, IR (KBr): nmax
1
2999, 1460, 1217, 1033, 758 cmꢁ1; H NMR (400 MHz, DMSO-d6): d 1.30 (t, 3H),
2.83 (q, 2H), 7.29 (d, J ¼ 7.6 Hz, 1H), 7.38 (d, J ¼ 7.6 Hz, 1H), 7.40 (d, J ¼ 8.4 Hz,
1H), 7.85 (d, J ¼ 7.6 Hz, 1H), 7.94 (d, J ¼ 8.4 Hz, 1H), 8.20 (d, J ¼ 0.8 Hz, 1H);
13C NMR (100 MHz, DMSO-d6): d 16.0, 22.2, 28.4, 120.6, 122.6, 124.0, 126.2,
126.4, 127.0, 133.0, 134.6, 135.9, 136.0, 139.2, 140.2. CHNS: Calculated for
C15H14S: C, 79.60; H, 6.23; S, 14.17; Found. C, 79.37; H, 6.33; S, 14.32.
1-(Dibenzo[b,d]thiophen-2-yl)ethanone (1i). White solid, mp: 125 ꢀC; IR
;
(KBr): nmax 1664, 1446, 1354, 1269, 964, 754, 603 cmꢁ1 1H NMR (400 MHz,