7
824
M. P. S. Ishar et al. / Tetrahedron 56 (2000) 7817±7828
1
00(M 11, 37), 299(M , 30), 298(M -1, 89), 273(6),
1
1
3
2
semisolid (contaminated with 14), nmax (CHCl ): 2363.3
3
1
72(40), 271(27), 270(100). 3 (R Cl, ,1%) as a white
(w), 1658 (sh), 1645.2 (br), 1615 (s), 1602 (m), 1572.5
(s), 1491.3 (s), 1470.0 (s), 1452.9 (s), 1393.0 (m), 1341.7
(m), 1311.8 (s), 1256.2 (w), 1149.4 (s), 1123.7 (m), 1076.7
crystalline solid (CHCl ), mp 208±2098C; [Found C,
3
64.25; H, 3.35; N, 4.65%. C H O ClN C, 64.21; H, 3.34;
N, 4.68%]; lmax (CH OH): 365, 312.1, 284.5 nm; nmax
16 10 3
2
1
(m), 1063.9 (m) cm . d (200 MHz, CDCl ): 8.33 (bs, 1H,
H 3
3
(
(
KBr): 3307 and 3250 (NH), 1688 (O-CvO), 1655
C4vO), 1616, 1595, 1580. dH (200 MHz, CDCl ): d
C2±H), 8.22 (d, 1H, J2.3 Hz, C5±H), 7.64 (dd, 1H,
J8.6, 2.5 Hz, C7±H), 7.48 (d, 1H, J8.4 Hz, C8±H),
7.35±7.25 (m, 2H), 7.14 -6.94 (m, 3H), 5.30 (dd, 1H,
3
13.43 and 11.95 (broad doublets, together 1H, ±NH in
isomeric structures), 9.01 and 8.87 (doublets, together 1H,
0
0
J7.0, 2.5 Hz, C5 ±H), 4.77 (t, 1H, J7.6 Hz, C3 ±H),
0
J14.6, 14.3 Hz respectively, C9±H in isomeric structures),
3.11±2.99 (m, 1H, C4 ±Ha), 2.82 (ddd, 1H, J13.2, 7.6,
0
1
1
8
.07 and 8.01 (doublets, together 1H, J2.6 Hz, C5±H in
2. 8 Hz, C4 ±Hb). 2 (R Cl, 10%). 3 (R Cl, ,1%).
1
isomers), 7.85±7.19 (m, 7H); m/z 300(20, M 11), 299 (48,
1
M ), 252 (18), 273 (16).
Reaction of 1b with styrene. Reaction of 1b with styrene
afforded exo-adduct (15, 77%) as an offwhite solid
(benzene/pet. ether 1:10); mp 54±558C; [Found C, 71.50;
H, 4.42; N, 3.40%. C H O NCl requires C, 71.46; H, 4.46;
Reaction of 1b with isobutyl vinyl ether. Reaction of 1b
with isobutyl vinyl ether afforded exo-adduct (13, 80%), as
light yellow solid (benzene/pet. ether 1:10); mp 89±908C;
2
4
18
3
N, 3.47%]; lmax (MeOH): 367, 317, 307 and 220 nm. nmax
(CHCl ): 1658(s), 1607(m), 1576(m), 1500(s), 1474(s),
[
Found C, 66.12; H, 5.46; N, 3.42%. C H O ClN requires
2
2
22
4
3
C, 66.16; H, 5.51; N, 3.50%]; lmax (MeOH): 365, 317, 306
and 231 nm. nmax (CHCl3): 1653.7(s), 1615.3(m),
1449(s), 1393(m), 1346(s), 1312(s), 1261(m), 1222(m),
1170(s), 1128(m), 1081(m), 1038(m), 1000(w) cm . d
2
1
H
1
1
1
1
8
2
1
606.7(m), 1576.8(m), 1512.7(m), 1495.6(s), 1474.1(s),
448.6(s), 1388.7(m), 1341.7(m), 1311.8(m), 1265(m),
205(m), 1162(m), 1128(w), 1102.4(m), 1059(m),
(200 MHz, CDCl ): 8.39 (s, 1H, C2±H), 8.16 (d, 1H,
3
J2.5 Hz, C5±H), 7.56 (dd, 1H, J8.8, 2.5 Hz, C7±H),
7.44±7.23 (m, 8H), 7.06 (d, 2H, J8.0 Hz), 6.95 (t, 1H,
0
0
046.8(m). dH (200 MHz, CDCl ): 8.28 (s, 1H, C2±H),
3
J7.2 Hz), 5.24±5.16 (m, 2H, C3 ±H and C5 ±H), 3.37
0
.16 (d, 1H, J2.5 Hz, C5±H), 7.55 (dd, 1H, J8.9,
.5 Hz, C7±H), 7.37 (d, 1H, J8.9 Hz, C8±H), 7.21 (bt,
H, J9.6 Hz), 6.98±6.88 (m, 3H), 5.39 (d, 1H,
(dt, 1H, J12.6, ,7.8 Hz, C4 ±Ha), 2.23 (ddd, 1H,
J12.6, 6.2, 5.8 Hz). d (50 MHz,CDCl ): 175.46 (C4),
C
3
154.90 (C8a), 154.21 (C2), 153.41 (quat. arom.), 137.92
(quat. arom.), 133.78 (C7), 131.12 (C6), 129.24 (CH),
128.78 (CH, arom.), 128.59 (CH, arom.), 126.77 (CH,
arom.), 125.82 (C4a), 125.15 (C5), 124.88 (C3), 121.94
(CH, arom.), 119.99 (C8), 114.01 (CH, arom.), 80.19
0
0
J5.6 Hz, C5 ±H), 4.86 (bd, 1H, J7.9 Hz, C3 ±H), 3.60
(
(
dd, 1H, J9.1, 6.8 Hz), 3.22 (dd, 1H, J9.1, 6.3 Hz), 2.80
0
ddd, 1H, J13.3, 7.9, 5.6 Hz, C4 ±Ha), 2.27 (dd, 1H,
0
J13.3, 1.8 Hz, C4 ±Hb), 1.92±1.73 (m, 1H), 0.86 (d,
0
0
0
1
6
H, J6.7 Hz, 2£CH ). d (50 MHz, CDCl ): 175.07
(C5 ), 63.65 (C3 ), 44.44 (C4 ). m/z 405(1.5, M 12),
404(1.3, M 11), 403(4, M ), 387(1), 298(18), 77 (100).
1 1
3
C
3
1
1
(
1
(
C4), 154.86 (C2), 154.64 (C8a), 150.58 (quat. arom.),
33.47 (C7), 130.86 (C6), 126.64 (CH, arom.), 125.11
C5), 124.82 (C4a), 124.71 (C3), 122.16 (CH, arom.),
2 (R Cl, 14%). 3 (R Cl, 2%).
0
1
19.70 (C8), 115.12 (CH, arom.), 102.29 (C5 ), 75.03
Reaction of 1b with methyl acrylate. Reaction of 1b with
methyl acrylate afforded mixture (3.5:1) of adducts (16 and
0
CH ). m/z 402 (1, M 13), 401 (3, M 12), 400 (2,
0
(
(
±OCH ), 60.23 (C3 ), 41.19 (C4 ), 28.37 (CH), 19.32
2
1
1
0
362, 310, 306 and 231 nm. nmax (CHCl ): 1742 (b,s),
1649.5(s), 1611(s), 1576.8(s), 1576.8(s), 1496.6(s),
16 , 90%) as a light yellow viscous material, l
(MeOH):
max
3
1
1
M 11), 399 (8, M ), 291 (47), 235 (90), 207 (100). 2
(
3
1
1
R Cl, 15%). 3 (R Cl, ,1%).
1474.2(s), 1448.6(m), 1393(m), 1346(s), 1316.1(s),
1217.8(s), 1183.6(m), 1149.4(m), 1128(m), 1081(m),
Reaction of 1b with acrylonitrile. Reaction of 1b with
acrylonitrile afforded exo-adduct (14, 50%) as light yellow
solid (benzene/pet. ether 1:10), mp 73±748C; [Found C,
1055.4(m); d (200 MHz, CDCl ): 8.25 (d, 1H, J0.7 Hz,
H
3
C2±H), 8.05 (d, 1H, J2.4 Hz, C5±H), 7.49 (dd, 1H,
J8.9, 2.4 Hz, C7±H), 7.32 (d, 1H, J8.9 Hz, C8±H),
7.21±7.05 (m, 2H), 7.04±6.85 (m, 3H), 5.18 (d, 1H,
6
6
4.92; H, 3.60; N, 7.91%. C H O N Cl requires C,
19 13 3 2
4.77; H, 3.69; N, 7.95%]; lmax (MeOH): 362, 312, 232
0
0
and 209 nm. nmax (CHCl3): 2316(w), 1649.5(s),
J5.3 Hz, C5 ±H in, 16 ), 5.03 (dd, 1H, J8.1, 2.2 Hz,
0
0
1
1
1
619.5(m), 1606.7(m), 1576.8(m), 1495.6(m), 1470(s),
448.6(m), 1393(m), 1346(m), 1316.1(m), 1149.4(m),
123.7(m), 1085(m), 1068.2(w), 1034.0(w). d (200 MHz,
C5 ±H 16), 4.68 (dd, 1H, J9.4, 5.6 Hz, C3 ±H in 16),
0
(singlets, ±OCH in 16 and 16, respectively), 2.90 (dt,
0
4.51 (t, 1H, J,7.1 Hz, C3 ±H in 16 ), 3.61 and 3.60
0
H
3
0
1H, C4 ±Ha in 16 ), 2.62- 2.46 (m, C4 ±H in 16 ), 2.40
CDCl ): 8.30 (d, 1H, J0.9 Hz, C2±H), 8.19 (d, 1H,
1H, J13.0, ,8.8 Hz, C4 ±Ha in 16), 2.86±2.74 (m,
3
0
0
0
0
J2.5 Hz, C5±H), 7.64 (dd, 1H, J8.9, 2.5 Hz, C7±H),
0
(50 MHz, CDCl ): 174.83 (C4), 170.03(±CO ± in16 ),
7
6
.46 (d, 1H, J8.8 Hz, C8±H), 7.33±7.25 (m, 2H), 7.08±
(ddd, 1H, J12.9, 5.6, 2.2 Hz, C4 ±Hb in 16); d
C
0
0
169.71(±CO ± in 16), 154.87 (C8a in 16 ), 154.35 (C8a in
.98 (m, 3H), 5.09 (dd, 1H, J8.2, 1.6 Hz, C5 ±H), 4.96
3
2
0
0
16), 154.23 (C2 in 16), 153.58 (C2 in 16 ), 150.24 and
(
8
dd, 1H, J9.3, 3.4 Hz, C3 ±H), 3.04 (ddd, 1H, J13.2, 9.3,
2
0
(50 MHz, CDCl ): 175.41 (C4), 154.88 (C8a), 154.43
0
0
149.84 (quat. arom. Cs in 16 and 16 ), 133.44 (C7 in 16 ),
.2 Hz, C4 ±Ha), 2.65 (dt, 1H, J13.2, ,3.0 Hz, C4 ±Hb).
0
0
133.34 (C7 in 4), 130.73 (C6 in 16 ), 130.62 (C6 in 16),
d
C
3
0
128.73 and 128.31 (CH in 16 and 16 , respectively), 124.62
(
C2), 147.77 (quat. arom.), 134.18 (C7), 131.52 (C6),
0
and 124.34 (CH in 16 and 16 , respectively), 124.02 (C4a in
1
1
6
29.26 (CH), 125.13 (C5), 124.66 (C4a), 123.89 (CH),
22.77 (C3), 120.10 (C8), 117.25 (CN), 115.50 (CH),
0
0
0
0
0
0
4.07 (C5 ), 61.61 (C3 ), 40.03 (C4 ); m/z 355 (0.5,
16 ), 123.51 (C4a in 16), 122.77 (C3 in 16 ), 122.45 (CH),
122.13 (C3 in 16), 121.27 (C8), 115.10 and 114.44 (CH in
16 and 16 respectively), 75.89 (C5 in 16 ), 74.88 (C5
1
1
1
M 13), 354 (0.4, M 12), 352 (1, M ), 298 (12), 296
0
0
0
0
0
(
16), 285 (18). endo-Adduct (14 , 35%) as a light yellow