Quinoneimines in the Nenitzescu reaction
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 7, July, 2005
1699
of quinone 1 (1.25 g, 4.8 mmol) in acetone (25 mL). The stirring
was continued for 4 h. The precipitate was filtered off, washed
with water, and dried to give 0.3 g of compound 18. The acetone
mother liquor was concentrated and the residue was triturated
with ethanol. The precipitate was filtered off and recrystallized
from ethanol to give additionally 0.57 g of compound 18. The
ethanol mother liquor was concentrated and the residue was
chromatographed on a column with silica gel. Elution with chloꢀ
roform gave 0.19 g of compound 20.
10аꢀPiperidinoꢀ7ꢀtosylaminoꢀ2,3,5,5а,10аꢀhexahydrobenzoꢀ
furo[2,3ꢀc]azepinꢀ1(1H )ꢀone (21). Enamine 10 (1.14 g,
5.9 mmol) was added at 20 °C to a stirred solution of quinone 1
(1.53 g, 5.9 mmol) in acetone (12 mL). The stirring was continꢀ
ued for 3 h. The precipitate was filtered off, washed with hot
acetone, and dried to give 2.0 g of compound 21.
9ꢀTosylaminoꢀ1,2,3,4ꢀtetrahydroꢀ5Hꢀchromeno[3,4ꢀb]pyriꢀ
dineꢀ5ꢀone (22) and 7ꢀtosylaminoꢀ2,3,4,5ꢀtetrahydroꢀ
1H[1]benzofuro[2,3ꢀc]azepinꢀ1ꢀone (23). A suspension of comꢀ
pound 21 (3.16 g, 6.9 mmol) in AcOH (45 mL) was stirred for
20 min at 17—18 °C and refluxed for 2.5 h. The reaction mixture
was cooled to 20 °C and diluted with water (400 mL). The
precipitate was filtered off, washed with water, dried, and
chromatographed on a column with silica gel. Elution with ethyl
acetate gave 2.2 g of compound 22 and 0.11 g of compound 23.
Compound 23. 1H NMR (DMSOꢀd6), δ: 2.01 (m, 2 H, H(4));
2.87 (t, 2 H, H(5), J1 = J2 = 6.4 Hz); 3.26 (m, 2 H, H(3), J1 =
J2 = 6.4 Hz, J3 = 4.8 Hz); 7.12 (dd, 1 H, H(8)), Jo = 8.4 Hz,
Jm = 1.8 Hz); 7.31, 7.61 (both m, 2 H each, C6H4); 7.35 (d, 1 H,
H(6), Jm = 1.8 Hz); 7.47 (d, 1 H, H(9), Jo = 8.4 Hz); 8.02 (t,
1 H, N(2)H, Jo = 4.8 Hz); 10.05 (br.s, 1 H, NH(C(7)).
9ꢀAminoꢀ1,2,3,4ꢀtetrahydroꢀ5Hꢀchromeno[3,4ꢀb]pyridinꢀ5ꢀ
one (24). A suspension of compound 20 (1.1 g, 3 mmol) in 75%
H2SO4 (20 mL) was stirred for 3.5 h at 75—80 °C. The reaction
mixture was poured onto ice, filtered, and cooled to 10—15 °C.
A solution of ammonia was added to pH ~8. The precipitate was
filtered off, washed with water, and dried to give 0.63 g of comꢀ
pound 24.
3ꢀAcetylꢀ5ꢀ(2,4ꢀdinitrophenylamino)ꢀ2ꢀmethylbenzofurans
(25) was prepared similarly to compound 13. The reaction of
quinone 2 (0.54 g, 2 mmol) 11 with enamine 5 (0.56 g, 2.2 mmol)
gave 0.2 g of benzofuran 25.
3ꢀBenzoylꢀ5ꢀ(2,4ꢀdinitrophenylamino)ꢀ2ꢀmethylbenzofuran
(26) was prepared similarly to compound 13. The reaction of
quinone 2 (0.27 g, 1 mmol) with enamine 6 (0.28 g, 1.1 mmol)
gave 0.08 g of benzofuran 26.
3ꢀBenzoylꢀ5ꢀ(2,4ꢀdinitrophenylamino)benzofuran (27) was
prepared similarly to compound 13. The reaction of compound
(0.5 g, 2 mmol) 2 with enamine 7 (0.38 g, 2.2 mmol) gave 0.17 g
of benzofuran 27.
5ꢀ(2,4ꢀDinitrophenyl)aminoꢀ2ꢀmethylꢀ3ꢀnitrobenzofuran
(28). pꢀToluenesulfonic acid (0.17 g, 1 mmol) and enamine 8
(0.21 g, 1.1 mmol) were added successively at 20 °C to a stirred
suspension of quinone 2 (0.27 g, 1 mmol) in AcOH (3 mL). The
stirring was continued for 30 min. The precipitate was filtered
off, washed with AcOH and water, and dried to give 0.31 g of
compound 28.
7ꢀ(2,4ꢀDinitrophenyl)aminoꢀ10аꢀpiperidinoꢀ2,3,5,5а,10аꢀ
hexahydrobenzofuro[2,3ꢀc]azepinꢀ1(1H )ꢀone (29) was prepared
similarly to compound 21. The reaction of quinone 2 (2.18 g,
8 mmol) with enamine 10 (1.55 g, 2.2 mmol) gave 1.8 g of
compound 29.
9ꢀ(2,4ꢀDinitrophenyl)aminoꢀ1,2,3,4ꢀtetrahydroꢀ5Hꢀchroꢀ
meno[3,4ꢀb]pyridinꢀ5ꢀone (30). A suspension of compound 29
(1.8 g, 3.8 mmol) in AcOH (35 mL) was stirred for 20 min at
17—18 °C and refluxed for 3 h. The reaction mixture was cooled
to 20 °C and stirred for 2 h. The precipitate was filtered off,
washed with AcOH and water, and dried to give 1.13 g of comꢀ
pound 30.
1ꢀBenzylꢀ5ꢀ(4ꢀmethoxyphenyl)aminoꢀ2ꢀmethylꢀ3ꢀnitroindole
(31) and 5ꢀ(4ꢀmethoxyphenyl)aminoꢀ2ꢀmethylꢀ3ꢀnitrobenzofuran
(32). pꢀToluenesulfonic acid (0.17 g, 1 mmol) and enamine 8
(0.21 g, 1.1 mmol) were added successively at 20 °C to a stirred
solution of quinone 3 (0.213 g, 1 mmol) 12 in AcOH (3 mL). The
stirring was continued for 1 h. The reaction mixture was diluted
with water (30 mL) and the precipitate was filtered off, washed
with water, dried, and chromatographed on a column with silica
gel. Elution with benzene gave 0.022 g of indole 31 and 0.038 g
of benzofuran 32.
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Received May 27, 2005