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Záletová et al.:
N3-(4-Ch loroph en yl)-1H-in dole-3-carboth ioam ide (9)
To a suspen sion of 6 (0.13 g, 0.48 m m ol) in dry toluen e (4 m l), Lawesson ’s reagen t (0.11 g,
0.27 m m ol) was added. Th e reaction m ixture was refluxed for 15 m in . After coolin g, th e
crystallin e precipitate was filtered off with suction an d crystallized from a m ixture of
dich lorom eth an e an d h exan e. Yield 86%, m .p. 202–205 °C. For C15H11ClN2S (286.8) calcu-
lated: 62.82% C, 3.87% H, 9.77% N; foun d: 63.00% C, 3.75% H, 9.81% N. IR: 1050 (C=S);
1656 (C=C); 3410 (in dole N–H); 3210 (N–H). 1H NMR: 6.55–7.44 m , 9 H (arom . H); 9.80 s,
2 H (N-H). 13C NMR: 112.29, 118.91, 121.00, 121.87, 122.52, 126.07 (q); 126.41 (q); 128.03,
128.37, 129.25 (q); 132.58 (q); 136.99 (q); 139.14 (arom . C); 191.14 (C=S). MS, m/z (%): 286
(M+, 45), 160 (75), 126 (100).
N3-(4-Meth oxyph en yl)-1H-in dole-3-carboth ioam ide (10)
To a suspen sion of 7 (1 g, 3.76 m m ol) in dry toluen e (15 m l), Lawesson ’s reagen t (0.96 g,
2.37 m m ol) was added an d th e reaction m ixture was refluxed for 15 m in . After coolin g, th e
form ed crystallin e precipitate was filtered off with suction an d crystallized from a m ixture of
dich lorom eth an e an d h exan e. Yield 78%, m .p. 193 °C. For C16H14N2OS (282.4) calculated:
68.06% C, 5.00% H, 9.92% N; foun d: 68.40% C, 5.10% H, 10.00% N. IR: 1075 (C=S); 1650
(C=C); 3210 (N–H); 3400 (N–H). 1H NMR: 3.78 s, 3 H (OCH3); 6.96–8.53 m , 9 H (arom . H);
10.96 s, 1 H (in dole N-H); 11.82 s, 1 H (N-H). 13C NMR: 55.31 (OCH3); 112.11, 113.51,
118.62 (q); 120.72, 121.86, 122.31 (q); 126.02, 126.48, 127.33 (q); 133.01, 136.83 (q); 156.93
(q) (arom . C); 190.51 (C=S). MS, m/z (%): 282 (M+, 50), 249 (40), 160 (80), 123 (100).
N3-(2,4-Dim eth ylph en yl)-1H-in dole-3-carboth ioam ide (11)
To a suspen sion of 8 (1 g, 3.78 m m ol) in dry toluen e (30 m l), Lawesson ’s reagen t (0.77 g,
1.90 m m ol) was added an d th e reaction m ixture was refluxed for 50 m in . After coolin g,
th e crystallin e precipitate was filtered off with suction an d crystallized from a m ixture of
dich lorom eth an e an d h exan e. Yield 90%, m .p. 188 °C. For C17H16N2S (280.4) calculated:
72.82% C, 5.64% H, 9.99% N; foun d: 73.00% C, 5.75% H, 10.00% N. IR: 1100 (C=S); 1650
(C=C); 3200 (N–H); 3450 (in dole N–H). 1H NMR: 2.23 s, 3 H (CH3); 2.33 s, 3 H (CH3);
7.05–8.59 m , 8 H (arom . H); 10.69 s, 1 H (in dole N-H); 11.74 s, 1 H (N-H). 13C NMR: 17.88
(CH3); 20.82 (CH3); 112.16, 117.82 (q); 120.82, 122.02, 122.36, 126.22 (q); 126.88, 127.38,
128.18 (q); 131.03, 135.10 (q); 136.27, 136.44 (q); 136.93 (q) (arom . C); 191.88 (C=S). MS,
m/z (%): 280 (M+, 90), 160 (75), 120 (100).
2-(1H-In dol-3-yl)-6-ch loro-1,3-ben zoth iazole (12)
To a suspen sion of 9 (515 m g, 1.80 m m ol) in ch loroform (18 m l), brom in e (290 m g,
1.81 m m ol) was added dropwise. Th e reaction m ixture was stirred for 1 h at room tem pera-
ture, th en n eutralized with trieth ylam in e (0.46 m l, 3.3 m m ol), poured in to water (150 m l)
an d extracted with dieth yl eth er (2 × 50 m l). Th e extract was dried with an h ydrous sodium
sulfate, evaporated an d purified by ch rom atograph y on silica gel (cycloh exan e–aceton e, 2:1).
Yield 45%, m .p. 143–145 °C (m eth an ol–water). For C15H9ClN2S (284.8) calculated: 63.27% C,
3.19% H, 9.84% N; foun d: 63.10% C, 3.20% H, 9.91% N. IR: 1173 (N–C); 1630 (C=N); 1640
(C–S); 3020 (C–H). 1H NMR: 6.75–8.55 m , 9 H (arom . H); 9.25 s, 1 H (N-H). 13C NMR:
104.67 (q); 111.63, 121.21, 122.18, 123.02 (q); 123.75, 124.08, 124.16, 125.16, 125.46 (q);
Collect. Czech. Chem. Commun. (Vol. 69) (2004)