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Helvetica Chimica Acta – Vol. 92 (2009)
30.1 (t); 29.5 (t); 27.0 (t); 23.4 (t); 22.9 (t); 19.0 (t, C(11)). GC/MS (EI): 372 (59, Mþ), 343 (28), 329 (100),
315 (25), 223 (43). Anal. calc. for C26H32N2: C 83.82, H 8.66, N 7.52; found: C 82.57, H 8.57, N 7.38.
3. Reaction of Hemiacetal 2 with 2-Aminophenol. 7,7a,8,9,10,11,12,12a,13,14,15,16-Dodecahydro-6H-
11a,16a-epoxy-6,11b-propanobenzo[a][1,3]benzoxazolo[2,3-e]acridine (17a/17b). A mixture of
2
(0.636 g, 2 mmol), 2-aminophenol (0.24 g, 2.2 mmol), and TsOH (30 mg) in p-xylene (12 ml) was
refluxed for 10 h following the GP. The resulting solid was filtered (0.24 g, 31%) and analyzed by GC/MS.
It consisted of two diastereoisomers 17a and 17b (in a ratio of 1:1), which were separated by CC (Al2O3;
light PE). Isomers 17a and 17b were white crystals with the same Rf and IR. Rf 0.84. IR: 2965, 2931, 2853,
1
1586, 1481, 1458, 1446, 1357, 1267, 1236, 1173, 996, 740. H- and 13C-NMR: Table 2. Selected HMBC
Correlations: CH2(13)/C(2), C(7), C(12), C(14), C(15); HꢀC(12)/C(7), C(13); HꢀC(20)/C(7), C(15).
Selected COSY correlations: HaxꢀC(13)/HꢀC(12), HeqꢀC(13).
(5aS,6R,7aS,11aS,11bS,12aR,16aS)-7,7a,8,9,10,11,12,12a,13,14,15,16-Dodecahydro-6H-11a,16a-ep-
oxy-6,11b-propanobenzo[a][1,3]benzoxazolo[2,3-e]acridine (17a). M.p. 248 – 2498. tR 15.40 (GC). GC/
MS (EI): 391 (100, Mþ), 363 (21), 320 (19), 294 (3.8, [M ꢀ 97]þ), 283 (58), 281 (3.8). Anal. calc. for
C26H33NO2: C 79.79, H 8.44, N 3.58; found: C 79.95, H 8.58, N 3.65.
(5aS,6R,7aS,11aS,11bS,12aS,16aS)-7,7a,8,9,10,11,12,12a,13,14,15,16-Dodecahydro-6H-11a,16a-ep-
oxy-6,11b-propanobenzo[a][1,3]benzoxazolo[2,3-e]acridine (17b). M.p. 179 – 1818. tR 15.10 (GC). GC/
MS (EI): 391 (100, Mþ), 363 (4.8), 320 (4.8), 294 (73, [M ꢀ 97]þ), 283 (19), 281 (66.6). Anal. calc. for
C26H33NO2: C 79.79, H 8.44, N 3.58; found: C 79.91, H 8.52, N 3.70.
4. Reaction of Hemiacetal 2 with Phenylene-1,2-diamine. (5aR,6R,7aS,11aS,11bR,12aR,16aS)-7,7a,8,
9,10,11,12,12a,13,14,15,16-dodecahydro-5H,6H-11a,16a-epoxy-6,11b-propanobenzimidazo[2,1-e]ben-
zo[a]acridine (18). A mixture of 2 (0.636 g, 2 mmol), phenylene-1,2-diamine (0.24 g, 2.2 mmol), and
TsOH (30 mg) in p-xylene (12 ml) was refluxed for 6 h following the GP. The resulting solid was filtered
(0.529 g) and analyzed by GC/MS. It consisted of 18 (85%) and 15 (15%), which were separated by CC
(Al2O3; light PE). Yield 0.45 g (57.7%). Colorless crystals. M.p. 206 – 2088. tR 18.71 (GC). Rf 0.6 (green
1
spot). IR: 3403, 3036, 2966, 2926, 2852, 1597, 1488, 1383, 1261, 1008, 738. H- and 13C-NMR: Table 2.
Selected HMBC correlations: CH2(13)/C(2), C(7), C(12), C(14), C(15); HꢀC(20)/C(7), C(15).
Selected COSY correlations: HaxꢀC(13)/HꢀC(12); HeqꢀC(13); HꢀC(1)/NH. Selected NOESY
correlation: HꢀC(1)/NH. GC/MS (EI): 390 (100, Mþ), 293 (100), 280 (31), 145 (38), 132 (28). Anal.
calc. for C26H34N2O: C 79.96, H 8.77, N 7.17; found: C 80.10, H 8.85, N 7.21.
5. Reaction of Ketone 5 with 2-Aminophenol. A mixture of 5 (0.3 g, 1 mmol), 2-aminophenol (0.12 g,
1.1 mmol), and TsOH (30 mg) in p-xylene (12 ml) was refluxed the Dean – Stark apparatus for 13 h.
Reaction was monitored by GC/MS. In 13 h the content of 17a reached 87%.
6. Reaction of Ketone 5 with Phenylene-1,2-diamine. A mixture of 5 (0.3 g, 1 mmol), phenylene-1,2-
diamine (0.12 g, 1.1 mmol), and TsOH (30 mg) in p-xylene (12 ml) was refluxed in the Dean – Stark
apparatus for 5 h (monitored by TLC every h) and analyzed by GC/MS. It consisted of 18 (85%), 15
(5%), and 5 (10%).
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Received December 15, 2008