1666
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 9, September, 2001
Barabanov et al.
2 H, C(6)H, C(7)H); 8.108.40 (m, 2 H, C(5)H, C(8)H). IR,
ν/cm1: 1645, 1675 (C=O); 3335, 3495 (NH2); 3600 (OH).
2-Hydroxymethylnaphtho[2,3-g]indole-6,11-dione (4). Al-
cohol 1 (0.12 g, 0.4 mmol) in 5 mL of piperidine was stirred at
80 °C for 3 h 15 min and poured into 400 mL of water. The
products were extracted with 150 mL of benzene. The extract
was washed with water and concentrated in vacuo to 5 mL.
Pentane was added (20 mL), and the crystals that formed were
filtered off. The yield of product 4 was 0.07 g (58.3%), m.p.
222223 °C (benzene). Found (%): C, 73.55; H, 3.93; N, 5.08.
C23H17NO3. Calculated (%): C, 73.64; H, 4.00; N, 5.05.
1H NMR (DMSO-d6), δ: 4.72 (d, 2 H, CH2, J = 5.0 Hz); 5.46
(t, 1 H, OH, J = 5.0 Hz); 6.50 (s, 1 H, C(3)H); 7.607.95 (m,
4 H, C(4)H, C(5)H, C(8)H, C(9)H); 7.958.40 (m, 2 H,
C(7)H, C(10)H); 11.57 (br.s, 1 H, NH). IR, ν/cm1: 1670
(C=O); 3450 (NH).
2-(1-Hydroxybutyl)naphtho[2,3-g]indole-6,11-dione (5) was
obtained analogously (refluxing for 18 h), yield 76.7%, m.p.
135137 °C (benzene). Found (%): C, 75.31; H, 5.34; N, 4.35.
C20H17NO3. Calculated (%): C, 75.22; H, 5.37; N, 4.39.
1H NMR, δ: 1.00 (t, 3 H, CH3, J = 7.3 Hz); 1.202.20 (m,
4 H, CH2CH2); 2.57 (d, 1 H, OH, J = 4.2 Hz); 4.94 (m, 1 H,
CHO); 6.31 (d, 1 H, C(3)H, J = 1.9 Hz); 7.558.00 (m,
4 H, C(4)H, C(5)H, C(8)H, C(9)H); 8.008.45 (m, 2 H,
C(7)H, C(10)H); 10.53 (br.s, 1 H, NH). IR, ν/cm1: 1670
(C=O); 3450 (NH); 3600 (OH).
1-Amino-2-(2-benzoyl-1-piperidinovinyl)-9,10-anthra-
quinone (6a). Alcohol 3 (0.40 g, 1.2 mmol) and piperidine
(0.50 g, 5.8 mmol) were heated in 10 mL of dioxane at 75 °C
for 7 h. The solvent and the excess of piperidine were removed
in vacuo. The residue was dissolved in 30 mL of benzene,
and 30 mL of pentane was added. The precipitate that
formed was separated to give compound 6a (0.33 g, 66.8%),
decomp. < 195 °C (ether). The product is identical to an-
thraquinone 6a synthesized by the addition of piperidine to
ketone 8.13
1-Amino-2-(2-benzoyl-1-butylaminovinyl)-9,10-anthra-
quinone (6c) was obtained analogously from alcohol 3 and
BuNH2 (refluxing for 2.5 h), yield 66.7%, m.p. 193195 °C
(ether). The product is identical to that synthesized from
ketone 8.13
1-Amino-2-(2-benzoyl-1-diethylaminovinyl)-9,10-anthra-
quinone (6b). Alcohol 3 (0.60 g, 1.7 mmol) in 10 mL of Et2NH
was heated at 40 °C for 3.5 h (monitoring by TLC on Silufol in
CHCl3), concentrated in vacuo to 4 mL, and diluted with
60 mL of pentane. The precipitate that formed was filtered off
and chromatographed on SiO2 in CHCl3 to give compound 6b
(0.55 g, 76.3%), m.p. 193195 °C (benzenepentane). The
product is identical to that synthesized according to the known
procedure.13
4-Piperidino-2-phenylnaphtho[2,3-h]quinoline-7,12-dione
(7a). Ketone 6a (0.15 g, 0.3 mmol) was vigorously stirred with
conc. H2SO4 (0.1 mL) in 40 mL of benzene at 20 °C for
30 min. The precipitate that formed was separated and treated
with aqueous NaHCO3, and compound 7a was extracted with
benzene (100 mL), yield 0.10 g (69.5%), m.p. 233235 °C
(benzenepentane). The product is identical to that synthe-
sized according to the known procedure.13
The same procedure was used to obtain 4-diethylamino-2-
phenylnaphtho[2,3-h]quinoline-7,12-dione (7b), yield 99.2%,
m.p. 168169 °C (benzenepentane)13 and 4-butylamino-2-
phenylnaphtho[2,3-h]quinoline-7,12-dione (7c), yield 55.0%,
m.p. 190192 °C (benzene).13
4-Morpholino-2-phenylnaphtho[2,3-h]quinoline-7,12-dione
(7d). Alcohol 3 (0.15 g, 0.4 mmol) was heated in 5 mL of
morpholine at 120 °C for 1 h and diluted with 50 mL of water.
The starting alcohols 13 were synthesized by the
coupling of 1-amino-2-iodo-9,10-anthraquinone (10)
with the corresponding hydroxyacetylenes in aqueous
pyridine in the presence of Pd(PPh3)2Cl2, CuI, and
Na2CO3 according to the known procedure.20 Ketone 8
was obtained by the oxidation of alcohol 3 by the
Collins reagent (CrO32Py) in CH2Cl2 at 20 °C.
Experimental
1
H NMR spectra were recorded on Bruker AM-250 and
JEOL-FX-90 spectrometers in CDCl3 at 25 °C. IR spectra
were recorded on a UR-20 spectrophotometer in CHCl3. The
course of the reaction was monitored by TLC on Silufol plates
in a benzeneether solvent system.
1-Amino-2-(3-hydroxyprop-1-ynyl)-9,10-anthraquinone (1).
Propargyl alcohol (0.04 g, 0.7 mmol) was added with stirring in
an atmosphere of Ar at 75 °C to anthraquinone 10 (0.20 g,
0.6 mmol), Pd(PPh3)2Cl2 (5 mg), and CuI (3 mg) in 4 mL of
pyridine. Then a solution of Na2CO3 (0.06 g, 0.6 mmol) in
1.9 mL of water preheated to 80 °C was rapidly added, and
stirring was continued at 75 °C for 5 min. The reaction mixture
was diluted with 100 mL of CHCl3 and washed with dilute HCl
and water. Chromatography on SiO2 in CHCl3 gave compound
1 (0.13 g, 81.8%), m.p. 225227 °C (CHCl3pentane).
Found (%): C, 73.70; H, 3.94; N, 5.01. C17H11NO3. Calcu-
lated (%): C, 73.64; H, 4.00; N, 5.05. 1H NMR (DMSO-d6), δ:
4.40 (d, 2 H, CH2, J = 5.8 Hz); 5.45 (t, 1 H, OH, J = 5.8 Hz);
7.39 (d, 1 H, C(3/4)H, J = 7.7 Hz); 7.65 (d, 1 H, C(4/3)H,
J = 7.7 Hz); 7.757.95 (m, 2 H, C(6)H, C(7)H); 8.058.25
(m, 2 H, C(5)H, C(8)H).
The same procedure was used to obtain 1-amino-2-(3-hydr-
oxyhex-1-ynyl)-9,10-anthraquinone (2) (15 min, 80 °C), yield
91.2%, m.p. 161.5162.5 °C (benzene). Found (%): C, 75.13;
H, 5.26; N, 4.28. C20H17NO3. Calculated (%): C, 75.22;
H, 5.37; N, 4.39. 1H NMR, δ: 1.02 (t, 3 H, CH3, J = 7.0 Hz);
1.402.00 (m, 4 H, CH2CH2); 2.10 (d, 1 H, OH, J = 5.3 Hz);
4.74 (m, 1 H, CHO); 7.59 (s, 2 H, C(3)H, C(4)H); 7.508.00
(m, 2 H, C(6)H, C(7)H); 8.158.40 (m, 2 H, C(5)H, C(8)H).
IR, ν/cm1: 1650, 1675 (C=O); 3345, 3485 (NH2); 3600 (OH).
1-Amino-2-(3-hydroxy-3-phenylprop-1-ynyl)-9,10-anthra-
quinone (3) (7 min, 85 °C), yield 90.8%, m.p. 172.5173.5 °C
(CHCl3). Found (%): C, 78.07; H, 4.56; N, 3.87. C23H25NO3.
Calculated (%): C, 78.17; H, 4.28; N, 3.96. 1H NMR, δ: 2.38
(br.s, 1 H, OH); 5.79 (br.s, 1 H, CHO); 7.307.50 (m, 3 H,
3 HPh); 7.61 (s, 2 H, C(3)H, C(4)H); 7.508.05 (m, 4 H,
C(6)H, C(7)H, 2 HPh); 8.108.40 (m, 2 H, C(5)H, C(8)H).
IR, ν/cm1: 1660, 1675 (C=O); 3345, 3495 (NH2); 3600 (OH).
1-Amino-2-benzoylethynyl-9,10-anthraquinone (8). Alco-
hol 3 (0.80 g, 2.3 mmol) was oxidized with CrO32Py (3.00 g,
11.6 mmol) in 225 mL of anhydrous CH2Cl2 at 20 °C for 1.5 h.
The yield of 8 was 0.77 g (96.8%), m.p. 254256 °C (CHCl3).13
Z-1-Amino-2-(3-hydroxy-3-phenylprop-1-enyl)-9,10-an-
thraquinone (12). Alcohol 3 (0.11 g, 0.3 mmol) in 12 mL of
peroxide-free dioxane was hydrogenated in the presence of
Pd/CaCO3 at 20 °C until the starting compound 3 disappeared;
0.7 mmol of H2 was absorbed. Chromatography on SiO2 in a
mixture of toluene and ether (7 : 3) gave compound 12 (0.09 g,
81.4%), m.p. 161162 °C (benzenehexane). Found (%):
C, 77.67; H, 4.70; N, 4.20. C23H17NO3. Calculated (%):
C, 77.73; H, 4.70; N, 3.94. 1H NMR, δ: 2.05 (br.s, 1 H, OH);
5.33 (d, 1 H, CHO, J = 8.3 Hz); 6.056.60 (m, 2 H,
CH=CH); 7.05 (br.s, 2 H, NH2); 7.257.45 (m, 6 H, 5 HPh,
C(3/4)H); 7.65 (d, 1 H, C(4/3)H, J = 8.0 Hz); 7.507.85 (m,