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2
444
He and Kwon
N-[1-(2-Diethylamino-ethylamino)-9-oxo-9H-thioxanthen-4-ylmethyl]-
ꢀ
acetamide (6). Fifty grams (0.85 mol) of acetamide was heated to 140 C in
an oil bath. One gram (2.8 mmol) of hycanthone (2) was added. The
mixture was vigorously stirred and 32 drops of sulfuric acid (0.42 mL,
8.02 mmol) in 12 mL of acetic acid was added. After 10 min, the reaction
flask was cooled down by tap water. Fifty milliliters of water was added.
The solution was basified by addition of sodiumcarbonate, the mixture
extracted with 3 ꢁ 35 mL of methylene chloride, dried over sodium sulfate
and concentrated. The crude product was initially purified on a silica gel
column using EtOAc/TEA (19.5:1) and EtOAc/EtOH (1:1) as eluent. The
resulting product was further purified on a silica gel column using eluent
EtOAc/EtOH (1:1) as eluent to give 48 mg (1.2 mmol, 43%) of pure
ꢀ
[14]
ꢀ
product (6): m.p. 182–184 C (lit.
EtOAc/TEA (19.5:0.5); Rf 0.13 in EtOH/EtOAc (1:1). H NMR
182–183 C). TLC Rf 0.25 in
1
(
CDCl , 400 MHz): ꢀ 1.10 (t, 6H, J ¼ 7.1 Hz), 2.03 (s, 3H), 2.64 (q, 4H,
3
J ¼ 7.1 Hz), 2.81 (t, 2H, J ¼ 6.9 Hz), 3.34 (dd, 2H, J ¼ 11.9, 6.65 Hz), 4.51
(
4
1
d, 2H, J ¼ 5.3 Hz), 5.79 (b, 1H), 6.56 (d, 1H, J ¼ 8.7 Hz), 7.36–7.54 (m,
H), 8.49 (d, 1H, J ¼ 8.1 Hz), 10.3 (b, 1H). IR (KBr): 3326, 2969, 1648,
ꢂ1
619, 1560, 1435, 1370, 1289, 1254, 1229, 1098, 810, 753 cm
N-[1-(2-Diethylamino-ethylamino)-7-methoxy-9-oxo-9H-thioxanthen-
.
4
-ylmethyl]-formamide (7). The mixture of 2.11 g (5.46 mmol) of 7-me-
ꢀ
thoxy-hycanthone (4) and 118 mL of formamide was warmed to 140 C
in an oil bath. The mixture was vigorously stirred and 13 mL of acetic
acid was added first, and followed by addition of 0.99 mL of sulfuric acid
in 13 mL of acetic acid. After 10 min, the reaction mixture was immedi-
ately poured into ice water. The solution was basified by addition of
sodium carbonate, the mixture extracted with methylene chloride, dried
over sodiumsulfate and concentrated. The crude product was purified on
a silica gel column using EtOAc/EtOH (1:1) as eluent to give 1.15 g
ꢀ
[14]
(
9
2.77 mmol, 50.7%) of pure product (7): m.p. 108–110 C (lit.
ꢀ
1
5–99 C). H NMR (CDCl ) ꢀ 1.09 (t, 6H, J ¼ 7.13), 2.64 (q, 4H,
3
J ¼ 7.13), 2.79 (t, 2H, J ¼ 6.86), 3.30 (m, 2H), 3.88 (s, 3H), 4.53 (d, 2H,
J ¼ 4.49), 6.04 (b, 1H), 6.50 (m, 1H), 6.85 (m, 1H), 6.94 (m, 1H), 7.30 (m,
1
1
1
H), 8.29 (s, 1H), 8.39 (m, 1H), 10.32 (s, 1H). IR (KBr): 3276.75, 2966.41,
648.64, 1600.89, 1559.82, 1508.53, 1406.14, 1385.95, 1237.68, 1184.62,
ꢂ1
068.24, 1033.45, 801.21, 658.20 cm
.
REFERENCES
1
2
. Kikuth, W.R. Naturwiss. 1946, 8, 253.
. Mauss, H. Ber. 1948, 81, 19–31.