1660
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 9, September, 2001
Kucherov and Zlotin
The yield of compound 8a was 0.25 g (90%), m.p.
327330 °C. Found (%): C, 61.03; H, 2.64; N, 9.67
C15H8N2O5. Calculated (%): C, 60.82; H, 2.72; N, 9.46.
1H NMR, δ: 7.938.02 (m, 3 H, H-6, H-7, NH2); 8.118.29
(m, 2 H, H-5, H-8); 8.19 (d, 1 H, H-4, J = 9.9 Hz); 8.44 (d,
1 H, H-3); 8.46 (s, 1 H, NH2).
m.p. 256260 °C. Found (%): C, 64.85; H, 3.51; N, 4.94,
S, 10.52 C16H11NO3S. Calculated (%): C, 64.63; H, 3.73;
1
N, 4.71, S, 10.78. H NMR, δ: 2.44 (s, 3 H, SMe); 7.75 (d,
1 H, H-4, J = 7.9 Hz); 7.78 (s, 1 H, NH2); 7.847.99 (m, 2 H,
H-6, H-7); 8.11 (d, 1 H, H-3); 8.138.22 (m, 3 H, H-5,
H-8, NH2).
N-Methyl-1-nitro-9,10-dioxo-9,10-dihydroanthracene-2-
carboxamide (8b). Yield 85%, m.p. 279281 °C. Found (%):
C, 61.72; H, 3.18; N, 9.32 C16H10N2O5. Calculated (%):
C, 61.94; H, 3.25; N, 9.03. 1H NMR, δ: 2.78 (d, 3 H, NMe,
J = 2.75 Hz); 7.907.98 (m, 2 H, H-6, H-7); 8.088.21
(m, 3 H, H-5, H-8, H-4); 8.43 (d, 1 H, H-3); 8.95
(br.s, 1 H, NH).
Amides 10bd were prepared analogously.
N-Methyl-1-methylthio-9,10-dioxo-9,10-dihydroan-
thracene-2-carboxamide (10b). Yield 87%, m.p. 227230 °C.
Found (%): C, 65.61; H, 4.32; N, 4.32, S, 10.21
C17H13NO3S. Calculated (%): C, 65.58; H, 4.21; N, 4.50,
S, 10.30. 1H NMR, δ: 2.39 (s, 3 H, SMe); 2.82 (d, 3 H,
NHMe), 7.75 (d, 1 H, H-4, J = 7.93 Hz); 7.898.01 (m, 2 H,
H-6, H-7); 8.098.22 (m, 3 H, H-5, H-8, H-3); 8.62 (q, 1 H,
NHMe, J = 4.0 Hz).
1-Nitro-9,10-dioxo-9,10-dihydroanthracene-2-carboxanilide
(8c). Yield 84%, m.p. 281283 °C (from THFethanol, 2 : 1).
Found (%):C, 67.93; H, 3.14; N, 7.36 C21H12N2O5. Calcu-
1-Methylthio-9,10-dioxo-9,10-dihydroanthracene-2-carb-
oxanilide (10c). Yield 75%, m.p. 225227 °C. Found (%):
C, 70.54; H, 4.34; N, 3.63, S, 8.62 C22H15NO3S. Calcu-
1
lated (%): C, 67.74; H, 3.25; N, 7.52. H NMR, δ: 7.17 (t,
1 H, (NHPh) Hp, J = 7.33 Hz); 7.40 (t, 2 H, (NHPh) Hm);
7.69 (d, 2 H, (NHPh) Ho); 7.948.02 (m, 2 H, H-6, H-7);
8.128.27 (m, 2 H, H-5, H-8); 8.37 (d, 1 H, H-4, J = 8.25 Hz);
8.52 (d, 1 H, H-1); 11.03 (s, 1 H, NH).
1
lated (%): C, 70.76; H, 4.05; N, 3.75, S, 8.59. H NMR, δ:
2.42 (s, 3 H, SMe); 7.12 (t, 1 H, (NHPh) H-p); 7.38 (dd, 2 H,
(NHPh) Hm, Jm,p = 6.9 Hz, Jm,o = 8.2 Hz); 7.74 (d, 2 H,
(NHPh) Ho); 7.92 (d, 1 H, H-4, J = 7.8 Hz); 7.888.01 (m,
2 H, H-6, H-7); 8.20 (d, 1 H, H-3); 8.158.23 (m, 2 H, H-5,
H-8); 10.74 (s, 1 H, NHPh).
N-Benzyl-1-nitro-9,10-dioxo-9,10-dihydroanthracene-2-
carboxamide (8d). Yield 82%, m.p. 262264 °C (THFetha-
nol, 2 : 1). Found (%): C, 68.57; H, 3.43; N, 7.37 C22H14N2O5.
Calculated (%): C, 68.39; H, 3.65; N, 7.25. 1H NMR, δ: 4.47
(d, 2 H, NCH2Ph, J = 5.5 Hz); 7.247.41 (m, 5 H, NCH2Ph);
7.928.01 (m, 2 H, H-6, H-7); 8.118.26 (m, 2 H, H-5,
H-8); 8.21 (d, 1 H, H-4, J = 8.4 Hz); 8.46 (d, 1 H, H-3); 9.58
(t, 1 H, NHCH2Ph).
N-Methoxycarbonylmethyl-1-nitro-9,10-dioxo-9,10-di-
hydroanthracene-2-carboxamide (8e). Methyl glycinate hydro-
chloride (0.14 g, 1.14 mmol) and NaOAc (0.093 g, 1.14 mmol)
were added with stirring to a solution of acid chloride 7 (0.30 g,
0.95 mmol) in anhydrous benzene (15 mL). The reaction
mixture was stirred at 15 °C for 2.5 h and worked up conven-
tionally to give compound 8e, yield 51%, m.p. 212215 °C
(THFethanol, 2 : 1). Found (%): C, 58.77; H, 3.15; N, 7.50
C18H12N2O7. Calculated (%): C, 58.70; H, 3.28; N, 7.61.
1H NMR, δ: 3.69 (s, 3 H, NHCH2COOMe); 4.05 (d, 2 H,
NHCH2COOMe); 7.938.01 (m, 2 H, H-6, H-7); 8.118.24
(m, 3 H, H-5, H-8, H-4); 8.49 (d, 1 H, H-3, J = 8.7 Hz); 9.54
(t, 1 H, NHCH2COOMe, J = 5.9 Hz).
N-Benzyl-1-methylthio-9,10-dioxo-9,10-dihydroanthracene-
2-carboxamide (10d). Yield 71%, m.p. 198200 °C. Found (%):
C, 71.65; H, 4.83; N, 3.21, S, 7.85 C24H19NO3S. Calcu-
lated (%): C, 71.80; H, 4.77; N, 3.49, S, 7.99. 1H NMR,
δ: 2.49 (s, 3 H, SMe); 4.49 (d, 2 H, NHCH2Ph, J = 5.2 Hz);
7.227.47 (m, 5 H, NHCH2Ph), 7.78 (d, 1 H, H-4, J = 7.2 Hz);
7.868.01 (m, 2 H, H-6, H-7); 8.088.25 (m, 3 H, H-3, H-5,
H-8); 9.22 (t, 1 H, NHCH2Ph, J = 4.6 Hz).
1-Ethylthio-9,10-dioxo-9,10-dihydroanthracene-2-carb-
oxamide (10e). A mixture of amide 8a (0.20 g, 0.68 mmol),
DMF (4 mL), and EtSNa (0.07 g, 0.83 mmol) was stirred at
15 °C for 12 h, poured into water (20 mL), and acidified with
HCl to acid reaction. The precipitate that formed was filtered
off, washed with water (3½10 mL), and recrystallized from
THFethanol (2 : 1) to give amide 10e, yield 0.17 g (81%),
m.p. 224226 °C. Found (%): C, 65.67; H, 4.34; N, 4.37,
S, 10.21 C17H13NO3S. Calculated (%): C, 65.58; H, 4.21;
N, 4.50, S, 10.30. 1H NMR, δ: 1.12 (t, 3 H, SCH2CH3,
J = 7.2 Hz); 2.94 (q, 2 H, SCH2CH3); 7.707.82 (m, 2 H,
H-4, NH); 7.997.84 (m, 2 H, H-6, H-7); 8.058.23 (m,
4 H, H-5, H-8, H-3, NH).
The reaction of N-benzyl-1-nitro-9,10-dioxo-9,10-di-
hydroanthracene-2-carboxamide (8d) with α-toluenethiol.
α-Toluenethiol (0.3 mL, 2.4 mmol) was added to a solution of
amide 8b (0.25 g, 0.9 mmol) in anhydrous DMF (3.5 mL).
Finely ground K2CO3 (0.1 g, 0.95 mmol) was then added with
vigorous stirring. The reaction mixture was stirred in an atmo-
sphere of argon at 50 °C for 5 h and poured into 5% HCl
(15 mL). The precipitate that formed was filtered off, washed
with water (3½10 mL), and chromatographed on silica gel
L (40/100) in toluene and then in tolueneethyl acetate (2 : 1)
to give a complex mixture of products (0.11 g) containing
N-methyl-6-oxo-1-phenyl-6H-anthra[1,9-bc]thiophene-3-carb-
Amides 10fh were prepared analogously.
1-Ethylthio-9,10-dioxo-9,10-dihydroanthracene-2-carb-
oxanilide (10f). Yield 86%, m.p. 194196 °C. Found (%):
C, 71.42; H, 4.35; N, 3.51, S, 8.44 C23H17NO3S. Calcu-
1
lated (%): C, 71.30; H, 4.42; N, 3.62, S, 8.28. H NMR, δ:
1.08 (t, 3 H, SCH2CH3, J = 7.2 Hz); 2.91 (q, 2 H, SCH2CH3);
7.13 (t, 1 H, (NHPh) Hp, Jm,p = 7.2 Hz); 7.37 (dd, 2 H,
(NHPh) Hm, Jm,o = 7.7 Hz); 7.73 (d, 2 H, (NHPh) Ho); 7.92
(d, 1 H, H-4, J = 8.2 Hz); 7.898.01 (m, 2 H, H-6, H-7);
8.23 (d, 1 H, H-3); 8.158.27 (m, 2 H, H-5, H-8); 10.67 (s,
1 H, NHPh).
1
oxamide (9) (1H NMR data). H NMR (9), δ: 2.91 (d, 3H,
NHMe, J = 5.5 Hz); 7.507.71 (m, 7 H, Ph, H-8, H-9);
8.298.36 (m, 2 H, H-7, H-10); 8.31 (d, 1 H, H-5, J = 7.8 Hz);
8.40 (d, 1 H, H-4); 9.10 (br.s, 1H, NHMe).
1-Methylthio-9,10-dioxo-9,10-dihydroanthracene-2-carb-
oxamide (10a). A mixture of amide 8a (0.20 g, 0.68 mmol),
DMF (4 mL), and MeSNa (0.06 g, 0.87 mmol) was stirred at
15 °C for 12 h, poured into water (20 mL), and acidified with
HCl to acid reaction. The precipitate that formed was filtered
off, washed with water (3½10 mL), and recrystallized from
THFethanol (2 : 1) to give amide 10a, yield 0.16 g (82%),
N-Benzyl-1-ethylthio-9,10-dioxo-9,10-dihydroanthracene-
2-carboxamide (10g). Yield 72%, m.p. 205206 °C. Found (%):
C, 71.80; H, 4.77; N, 3.49, S, 7.99 C24H19NO3S. Calcu-
1
lated (%): C, 71.80; H, 4.77; N, 3.49, S, 7.99. H NMR, δ:
1.03 (t, 3 H, S CH2CH3, J = 7.2 Hz); 2.78 (q, 2 H, SCH2CH3);
4.50 (d, 2 H, NHCH2Ph, J = 5.5 Hz); 7.267.46 (m, 5 H,
NHCH2Ph); 7.79 (d, 1 H, H-4, J = 8.2 Hz); 7.898.00 (m,
2 H, H-6, H-7); 8.148.24 (m, 3 H, H-5, H-8, H-3); 9.19 (t,
1 H, NHCH2Ph).