4936
R. Abonia et al. / Tetrahedron 57 <2001) 4933±4938
1
3
8
3
[
1
.03 ꢀd, J7.6 Hz, 1H); C NMR ꢀCDCl ): [20.1], 20.8,
Anal. calcd for C H N ꢀ235.11): C, 86.77; H, 7.28; N,
17 17
5.95. Found: C, 86.74; H, 7.29; N, 5.93.
3
8.5, 59.3, 61.0 [66.2], 109.0 [109.7], 111.5, 119.7
120.6], 121.3, 125.4 [126.1], 126.4 [127.8], 129.0, 130.1,
34.3 [145.6], 147.6, 150.7; MS m/z ꢀ%): 264 ꢀ35) [M ],
46 ꢀ100) [M2ꢀBtH)]; Anal. calcd for C H N ꢀ264.12):
C, 72.70; H, 6.10; N, 21.20. Found: C, 72.73; H, 6.08; N,
1
z
4.3.4. 4,5,6a,7,8,9a-Hexahydro-6H-9-oxa-5a-aza-cyclo-
penta[e]acenaphthylene ꢀmixture of the two racemic
diastereomers 9a). These compounds were obtained
from 2,3-dihydrofuran as pale yellow oil, 67% yield.
Some NMR peaks corresponding to the trans isomer are
1
1
6
16
4
2
1.17.
given in square brackets, the others are overlapped with
the cis isomer signals; H NMR ꢀCDCl ): 1.68±1.74 ꢀm,
1
4.3. General procedure for preparingthe pyrrolo-
quinoline derivatives ꢀ6±10)a and ꢀ6±10)b
3
1H, 7-H) [1.85±1.91 ꢀm, 1H, 7-H)], [2.10±2.13 ꢀm, 1H,
0
0
7
-H)], 2.20±2.27 ꢀm, 1H, 7 -H), [2.44±2.55 ꢀm, 1H, 6a-
A mixture of 5a or b ꢀ1.99 mmol), alkene ꢀ4.00 mmol) and
p-toluenesulfonic acid ꢀ50 mg) in anhydrous methanol
H)], 2.57±2.63 ꢀm, 1H, 6a-H), 2.92 ꢀdd, J13.2, 7.4 Hz,
1H, 6-H), 3.00±3.05 ꢀm. 1H, 4-H), 3.12 ꢀdd, 1H, J13.2,
0
ꢀ
15 ml) was stirred at room temperature for 1±3 h, TLC
9.1 Hz, 6 -H), [3.18 ꢀdd, J13.1, 7.5 Hz, 1H, 6-H)], 3.32±
0
0
control. The solvent was removed under reduced pressure
and the residue was dissolved in ethyl acetate and washed
with aq. NaOH solution ꢀ5%, 20 mL), followed by water
and dried with anhydrous Na SO . The solvent was removed
3.45 ꢀm, 2H, 4 H, 5-H), 3.48±3.53 ꢀm, 1H, 5 -H), [3.94±
3.97 ꢀm, 1H, 8-H)], 3.98±4.03 ꢀm, 1H, 8-H), 4.06±4.10 ꢀm,
0
1H, 8 -H), 4.91 ꢀs, 1H, 9a-H) [4.95 ꢀd, J4.5 Hz, 1H,
9a-H)], 6.54 ꢀd, J7.8 Hz, 1H, 1-H) [6.58 ꢀd, J8.1 Hz,
1H, 1-H)], [6.69 ꢀt, J7.3 Hz, 1H, 2-H)], 6.72 ꢀt, J
2
4
under vacuum and the residue was puri®ed by column
chromatography ꢀgradient hexane/ethyl acetate). For the
mixtures of compounds 10a and b, it was possible to recover
two fractions of products with different Rf.
1
7.3 Hz, 1H, 2-H), 7.14 ꢀbrd, 1H, 3-H); C NMR ꢀCDCl ):
3
3
d 28.5, 30.0 [43.5], 45.2 [48.5], 52.2, 53.9, 55.2, 66.5 ꢀ6-C),
[104.4], 106.7 [107.8], [117.2], [117.8], 124.2, 124.5, 127.3,
1
29.5, 152.5 ꢀbr) ꢀ9c-C); MS m/z ꢀ%): 201 ꢀ59) [M ], 157
z
1
ꢀ17) [M2C H O], 156 ꢀ100) [M2 ꢀC H O1H)]; Anal.
4.3.1. ꢀ^)-6-ꢀN-Pyrrolidin-2-onyl)-1,2,5,6-tetrahydro-4H-
pyrrolo[3,2,1-ij]quinoline ꢀ6a). This compound was
obtained from 1-vinyl-2-pyrrolidinone as white crystal,
2
4
2
4
calcd for C H NO ꢀ201.12): C, 77.58; H, 7.51; N, 6.96.
13 15
Found: C, 77.62; H, 7.49; N, 6.94.
1
6% yield; mp 1118C; H NMR ꢀCDCl ): 1.90±2.04 ꢀm,
6
2
3
6
7
1
3
p
p
4.3.5. ꢀ^)-ꢀ7aR ,11aS )-5,6,7a,9,10,11a-Hexahydro-4H,7H,
H), 2.10±2,19 ꢀm, 2H), 2.46 ꢀt, J7.8 Hz, 2H), 2.88±
.25 ꢀm, 6H), 3.27±3.42 ꢀm, 2H), 5.44 ꢀt, J7.8 Hz, 1H,
-H), 6.63 ꢀt, J7.3 Hz, 1H, 8-H), 6.72 ꢀd, J7.0 Hz, 1H,
0
pound was obtained from 2,3-dihydropyran as pale yellow
8H-11-oxa-6a-azabenzo[de]antracene ꢀ10 a). This com-
1
3
1
-H), 7.02 ꢀd, J6.8 Hz, 1H, 9-H); C NMR ꢀCDCl ): d
oil, 38% yield, R 0.31 ꢀCH Cl ); H NMR ꢀCDCl ): 1.25±
3
f
2
2
3
0
ꢀm, 1H, 8 -H), 2.45±2. 78 ꢀm, 2H, 7a-H, 5-H), 2.82±3.35
8.1, 27.5, 28.9, 31.3, 43.2, 45.9, 46.5, 54.9 ꢀ6-C), 116.9
1.45 ꢀm, 1H, 9H), 1.57±1.92 ꢀm, 2H, 9 -H, 8-H), 2.05±2.39
0
0
ꢀ
6a-C), 118.9 ꢀ8-C), 123.2 ꢀ9-C), 124.9 ꢀ7-C), 129.2 ꢀ9a-C),
1
z
0
0
1
51.0 ꢀ3a-C), 175.3 ꢀCvO); MS m/z ꢀ%): 242 ꢀ54) [M ],
57 ꢀ52) [M2C H NO], 156 ꢀ100) [M2ꢀC H NO1H)];
Anal. calcd for C H N O ꢀ242.10): C, 74.35; H, 7.49; N,
ꢀm, 4H, 5 H, 6-H, 7,7 -H), 3.41±3.62 ꢀm, 1H, 6 -H), 3.69±
4.15 ꢀm, 2H, 10-H), 4.66 ꢀd, J6.2 Hz, 1H, 11a-H), 6.73 ꢀt,
J7.2 Hz, 1H, 2-H), 7.05 ꢀd, J7.4 Hz, 1H, 1-H), 7.15 ꢀd,
1
4
7
4
7
1
5
18
2
1
3
1
1.56. Found: C, 74.32; H, 7.51; N, 11.55.
J7.0 Hz, 1H, 3-H); C NMR ꢀCDCl ): d 29.4 ꢀ9-C), 30.1
3
ꢀbr, 5-C, 8-C), 38.2 ꢀ7a-C), 49.8 ꢀ7-C), 55.5 ꢀ6-C), 66.3
ꢀ10-C), 74.5 ꢀ11a-C), 119.2 ꢀ2-C), 120.5 ꢀ4-C), 124.0 ꢀ3-
4
.3.2. ꢀ^)-6-Dodecyloxy-1,2,5,6-tetrahydro-4H-pyrrolo-
3,2,1-ij]quinoline ꢀ7a). This compound was obtained
[
from dodecyl vinyl ether as pale yellow oil, 60% yield; H
C), 127.2 ꢀ1-C), 127.6 ꢀ11b-C), 150.0 ꢀ11c-C); MS m/z
ꢀ%): 215 ꢀ63) [M ], 157 ꢀ24) [M2C H O], 156 ꢀ100)
1
1z
3
6
NMR ꢀCDCl ): 0.80ꢀm, 5H), 1.01±1.56 ꢀbrs, 20H), 2.10±
3
[M2 ꢀC H O1H)]; Anal. calcd for C H NO ꢀ215.15):
3 6 14 17
2
3
8
9
3
1
.52 ꢀm, 2H), 2.82±3.02 ꢀm, 1H), 3.35±3.58 ꢀm, 4H), 3.61±
.92 ꢀm, 1H), 4.57 ꢀbrd, 1H, 6-H), 6.65 ꢀt, J7.1 Hz, 1H,
-H), 6.94 ꢀd, J7.2 Hz, 1H, 7-H), 7.10 ꢀd, J7.0 Hz, 1H,
C, 78.10; H, 7.96; N, 6.51. Found: C, 78.05; H, 7.94; N,
6.54.
1
3
p
4.3.6. ꢀ^)-ꢀ7aS ,11aS )-5,6,7a,9,10,11a-Hexahydro-4H,7H,
p
-H); C NMR ꢀCDCl ): d 13.6, 22.2, 28.6, 28.8, 29.3,
3
00
1.5, 32.4, 37.6, 49.2, 54.7, 62.8, 65.4, 73.8, 76.8 ꢀ6-C),
18.2 ꢀ6a-C), 119.1 ꢀ8-C), 123.4 ꢀ9-C), 127.0 ꢀ7-C), 128.8
8H-11-oxa-6a-azabenzo[de]antracene ꢀ10 a). This com-
pound was obtained from 2,3-dihydropyran as pale yellow
1
z
1
ꢀ
9a-C), 150.7 ꢀ3a-C); MS m/z ꢀ%): 343 ꢀ35) [M ], 157 ꢀ52)
M2C H OH], 156 ꢀ100) [M2ꢀC H OH1H)]; Anal.
calcd for C H NO ꢀ343.24): C, 80.41; H, 10.86; N, 4.08.
oil, 27% yield, R 0.43 ꢀCH Cl ); H NMR ꢀDMSO-d ):
f
2
2
6
0
1.79 ꢀm, 1H, 8-H), 1.83±1.98 ꢀm, 1H, 8 -H), 2.02±2.12 ꢀm,
[
1.32±1.44 ꢀm, 1H, 9-H), 1.52±1.68 ꢀm, 1H, 9 -H), 1.71±
1
2
25
12 25
0
1H, 7a-H), 2.80±3.08 ꢀm, 5H, 5,5 -H, 6-H, 7,7 -H), 3.38±
2
3
37
0
0
Found: C, 80.45; H, 10.85; N, 4.06.
0
3
.47 ꢀm, 1H, 6 -H), 3.55 ꢀtd, J10.9, 2.7 Hz, 1H, 10-H),
0
4.3.3. ꢀ^)-6-Phenyl-1,2,5,6-tetrahydro-4H-pyrrolo[3,2,1-
ij]quinoline ꢀ8a). This compound was obtained from
3.72±3.81 ꢀm, 1H, 10 -H), 4.37 ꢀd, J3.2 Hz, 1H, 11a-H),
13
6.54 ꢀt, J7.40 Hz, 1H, 2-H), 6.88 ꢀd, J7.5 Hz, 1H, 1-H),
1
styrene as pale yellow oil, 70% yield; H NMR ꢀCDCl ):
6.95 ꢀd, J7.1 Hz, 1H, 3-H); CNMR ꢀDMSO-d ): d 22.3
3
6
1
4
6
4
1
.51±1.80 ꢀm, 2H), 2.05±2.55 ꢀm, 1H), 2.70±3.65 ꢀm, 5H),
.10 ꢀt, J7.4 Hz, 1H, 6-H), 6.40 ꢀbrt, 1H), 6.70 ꢀbrt, 1H),
ꢀ9-C), 25.6 ꢀ8-C), 28.3 ꢀ5-C), 33.5 ꢀ7a-C), 47.1 ꢀ7-C), 54.0
ꢀ6-C), 66.8 ꢀ10-C), 71.3 ꢀ11a-C), 117.5 ꢀ2-C), 118.5 ꢀ4-C),
123.5 ꢀ3-C), 126.7 ꢀ1-C), 128.3 ꢀ11b-C), 149.9 ꢀ11c-C); MS
1
3
.95±7.50 ꢀm, 6H); C NMR ꢀCDCl ): d 29.4, 35.0, 41.4,
3
1
z
6.3, 55.5 ꢀ6-C), 121.4, 122.9, 126.0, 127.3, 128.3, 128.8,
29.1, 132.9, 146.4, 148.2 ꢀ3a-C); MS m/z ꢀ%): 235 ꢀ68)
m/z ꢀ%): 215 ꢀ61) [M ], 157 ꢀ18) [M2C H O], 156 ꢀ100)
3 6
[M2ꢀC H O1H)]; Anal. calcd for C H NO ꢀ215.15): C,
3 6 14 17
78.10; H, 7.96; N, 6.51. Found: C, 78.06; H, 7.93; N, 6.53.
1
z
[
M ], 157 ꢀ52) [M2C H ], 156 ꢀ100) [M2 ꢀC H 1H)];
6
6
6
6