Y. Han et al. / Tetrahedron 67 (2011) 2313e2322
2319
3H, CH3). 13C NMR (150 MHz, CDCl3)
d
187.7, 139.7, 138.2, 138.1,
product was recrystallized in chloroform/ethanol to give the pure
product for analysis.
136.6, 132.0, 130.3, 129.7, 129.6, 128.8, 128.6, 128.5, 127.7, 127.2,
124.4, 124.0, 123.6, 122.3, 117.5, 115.1, 86.8, 21.2. MS (m/z): 387.04
([Mþ1]þ, 100%). Anal. Calcd for C27H18N2O: C 83.92, H 4.69, N 7.25.
Found: C 83.57, H 4.90, N 6.88.
Compound 4m: White solid, yield: 67%, mp 210 ꢀC, IR (KBr):
3079 (w), 2970 (w), 2934 (w), 2208 (s), 1614 (vs),1550 (m), 1521 (s),
1486 (m), 1458 (s), 1376 (s), 1275 (m), 1152 (w), 1082 (w), 798 (m).
Compound 4i: White solid, yield: 68%, mp 206 ꢀC, IR (KBr): 2963
(w), 2219 (m), 1629 (s), 1521 (s), 1454 (m), 1429 (m), 1394 (s), 1349
(s), 1250 (vs), 1176 (m), 967 (m), 896 (m), 800 (s). 1H NMR
1H NMR (600 MHz, CDCl3)
d (ppm): 8.95 (s, 1H, CH), 8.02 (d,
J¼6.8 Hz, 1H, CH), 7.70 (d, J¼6.4 Hz, 1H, ArH), 7.64 (d, J¼7.6 Hz, 3H,
ArH), 7.59 (d, J¼6.0 Hz, 1H, ArH), 7.47 (t, J¼7.5 Hz, 2H, ArH),
7.43e7.40 (m, 1H, ArH), 7.07 (d, J¼7.1 Hz, 1H, ArH), 3.82 (q, J¼6.3 Hz,
1H, CH2), 3.28 (q, J¼6.3 Hz,1H, CH2), 3.13 (q, J¼6.5 Hz,1H, CH2), 2.75
(q, J¼6.8 Hz, 1H, CH2), 1.17 (t, J¼6.9 Hz, 3H, CH3), 0.62 (t, J¼6.8 Hz,
(600 MHz, CDCl3)
d
(ppm): 9.12 (d, J¼7.3 Hz, 1H, CH), 9.06 (d,
J¼6.8 Hz, 1H, CH), 7.79 (d, J¼6.3 Hz, 1H, ArH), 7.69 (d, J¼3.6 Hz, 2H,
ArH), 7.51 (d, J¼7.4 Hz, 2H, ArH), 7.27 (t, J¼7.5 Hz, 1H, ArH), 7.23 (d,
J¼7.3 Hz, 1H, ArH), 7.17 (d, J¼7.4 Hz, 2H, ArH), 7.10 (t, J¼7.2 Hz, 2H,
ArH), 6.66 (d, J¼7.4 Hz, 2H, ArH), 3.72 (s, 3H, CH3O). 13C NMR
3H, CH3). 13C NMR (150 MHz, CDCl3)
d 161.9, 134.9, 131.4, 129.3,
129.0, 128.9, 128.7, 128.6, 128.5, 128.4, 127.3, 124.3, 123.3, 122.7,
119.2, 118.0, 114.5, 83.5, 43.0, 39.3, 13.8, 12.3. MS (m/z): 368.75
([Mþ1]þ, 100%). Anal. Calcd for C24H21N3O: C 78.45, H 5.76, N 11.44.
Found: C 78.41, H 6.22, N 11.27.
(150 MHz, CDCl3)
d 187.7, 159.5, 139.5, 138.2, 136.7, 132.2, 131.7,
129.7,128.6, 127.8, 127.2,124.4,124.0,123.8, 123.6, 122.3, 117.6, 115.1,
113.7, 86.7, 55.2. MS (m/z): 403.80 ([Mþ1]þ, 100%). Anal. Calcd for
C27H18N2O2: C 80.58, H 4.51, N 6.96. Found: C 80.70, H 4.83, N 6.75.
Compound 4j: White solid, yield: 62%, mp 162 ꢀC, IR (KBr): 3055
(w), 2218 (m), 1627 (s), 1516 (m), 1450 (w), 1404 (m), 1378 (m), 1348
(vs), 1252 (w), 1172 (w), 895 (m), 798 (m). 1H NMR (600 MHz,
Compound 4n: White solid, yield: 73%, mp 270 ꢀC, IR (KBr): 2972
(w), 2210 (m), 1617 (vs), 1554 (w), 1521 (m), 1456 (m), 1375 (m),
1273 (m), 1150 (m), 1084 (w), 797 (m). 1H NMR (600 MHz, CDCl3)
d
(ppm): 8.94 (d, J¼8.1 Hz,1H, CH), 8.02 (d, J¼7.4 Hz,1H, CH), 7.70 (t,
CDCl3)
d
(ppm): 9.12 (d, J¼7.5 Hz, 1H, ArH), 9.06e9.04 (m, 1H, CH),
J¼7.8 Hz, 1H, ArH), 7.64 (t, J¼7.6 Hz, 1H, ArH), 7.58 (t, J¼7.4 Hz, 1H,
ArH), 7.52 (d, J¼7.8 Hz, 2H, ArH), 7.28 (d, J¼8.3 Hz, 2H, ArH), 7.06 (d,
J¼7.4 Hz, 1H, ArH), 3.82 (q, J¼6.7 Hz, 1H, CH2), 3.30 (q, J¼6.7 Hz, 1H,
CH2), 3.14 (q, J¼7.0 Hz, 1H, CH2), 2.76 (q, J¼7.0 Hz, 1H, CH2), 2.40 (s,
7.82e7.80 (m, 1H, CH), 7.71 (t, J¼3.7 Hz, 2H, ArH), 7.49 (d, J¼7.7 Hz,
2H, ArH), 7.33 (t, J¼7.4 Hz, 1H, ArH), 7.26e7.25 (m, 3H, ArH),
7.14e7.11 (m, 3H, ArH), 7.10 (s, 1H, ArH). 13C NMR (150 MHz, CDCl3)
d
187.4, 138.2, 138.0, 136.8, 132.4, 131.8, 131.3, 130.6, 130.0, 129.7,
3H, CH3), 1.19 (t, J¼7.1 Hz, 3H, CH3), 0.64 (t, J¼7.1 Hz, 3H, CH3). 13
C
129.6, 128.8, 127.9, 127.3, 124.4, 124.1, 123.6, 122.7, 122.4, 117.1, 115.1,
86.6. MS (m/z): 451.63 ([Mþ1]þ, 100%), 453.49 ([Mþ1]þ, 97%). Anal.
Calcd for C26H15BrN2O: C 69.19, H 3.35, N 6.21. Found: C 68.84, H
3.78, N 5.96.
NMR (150 MHz, CDCl3) d 162.0, 138.5, 134.9, 129.7, 129.4, 128.9,
128.7, 128.5, 128.4, 127.3, 124.3, 123.4, 122.7, 118.9, 118.1, 114.4, 83.5,
43.0, 39.3, 21.3, 13.9, 12.3. MS (m/z): 382.72 ([Mþ1]þ, 100%). Anal.
Calcd for C25H23N3O: C 78.71, H 6.08, N 11.02. Found: C 78.65, H
6.50, N 10.76.
Compound 4k: White solid, yield: 78%, mp 140 ꢀC, IR (KBr): 3137
(w), 3088 (w), 2220 (m), 1626 (s), 1521 (m), 1456 (m), 1398 (s), 1350
(vs), 969 (m), 903 (m), 805 (m), 755 (m). 1H NMR (600 MHz, CDCl3)
Compound 4o: White solid, yield: 80%, mp 226 ꢀC, IR (KBr): 2971
(w), 2209 (m), 1619 (vs), 1550 (m), 1520 (m), 1455 (m), 1375 (m),
1247 (m), 1175 (w), 872 (w), 795 (w). 1H NMR (600 MHz, CDCl3)
d
(ppm): 9.15 (d, J¼6.2 Hz,1H, CH), 9.06 (d, J¼6.1 Hz,1H, CH), 7.81 (s,
1H, ArH), 7.72 (d, J¼4.0 Hz, 2H, ArH), 7.50 (d, J¼7.0 Hz, 2H, ArH),
d
(ppm): 8.92 (d, J¼8.1 Hz, 1H, CH), 8.01 (d, J¼7.4 Hz, 1H, CH), 7.68
7.28e7.27 (m, 2H, ArH), 7.21 (s, 1H, ArH), 7.15e7.10 (m, 5H, ArH). 13C
(d, J¼7.8 Hz, 1H, ArH), 7.62 (t, J¼7.6 Hz, 1H, ArH), 7.57 (d, J¼7.9 Hz,
3H, ArH), 7.05 (d, J¼7.4 Hz, 1H, ArH), 7.01 (d, J¼8.4 Hz, 2H, ArH),
3.85 (s, 3H, CH3O), 3.82 (q, J¼6.7 Hz, 1H, CH2), 3.29 (q, J¼6.7 Hz, 1H,
CH2), 3.15 (q, J¼7.0 Hz, 1H, CH2), 2.77 (q, J¼7.0 Hz, 1H, CH2), 1.19 (t,
J¼7.0 Hz, 3H, CH3), 0.66 (t, J¼7.1 Hz, 3H, CH3). 13C NMR (150 MHz,
NMR (150 MHz, CDCl3)
d 187.5, 138.2, 137.9, 136.8, 133.9, 133.3,
132.4, 130.7, 129.9, 129.8, 129.5, 129.4, 128.9, 128.3, 127.9, 127.3,
124.4, 124.1, 123.6, 122.6, 116.9, 115.6, 87.7. MS (m/z): 407.73
([Mþ1]þ,100%), 409.26 ([Mþ1]þ, 55%). Anal. Calcd for C26H15ClN2O:
C 76.75, H 3.72, N 6.89. Found: C 76.45, H 4.17, N 6.50.
CDCl3)
d 162.0, 159.9, 134.8, 130.2, 129.1, 128.6, 128.5, 128.4, 127.3,
Compound 4l: White solid, yield: 63%, mp 136e138 ꢀC, IR (KBr):
3026 (w), 2217 (w), 1620 (m), 1524 (m), 1445 (w), 1395 (w), 1349
124.2, 123.7, 123.3, 122.7, 118.8, 118.1, 114.4, 83.4, 55.4, 43.0, 39.4,
13.9, 12.4. MS (m/z): 398.72 ([Mþ1]þ, 100%). Anal. Calcd for
C25H23N3O2: C 75.54, H 5.83, N 10.57. Found: C 75.21, H 6.17, N
10.40.
(vs), 970 (w), 913 (w), 868 (w). 1H NMR (600 MHz, CDCl3)
d (ppm):
9.21 (d, J¼7.5 Hz, 1H, ArH), 9.07e9.05 (m, 1H, CH), 7.99 (d, J¼8.2 Hz,
1H, CH), 7.96 (t, J¼1.7 Hz, 1H, ArH), 7.86e7.84 (m, 1H, ArH),
7.76e7.74 (m, 2H, ArH), 7.70 (d, J¼7.7 Hz, 1H, ArH), 7.48 (d, J¼7.3 Hz,
2H, ArH), 7.40 (t, J¼7.9 Hz, 1H, ArH), 7.33 (d, J¼7.5 Hz, 1H, ArH), 7.23
(t, J¼7.5 Hz, 1H, ArH), 7.08 (t, J¼7.7 Hz, 2H, ArH). 13C NMR (150 MHz,
Compound 4p: White solid, yield: 75%, mp 247 ꢀC, IR (KBr): 2973
(w), 2207 (m), 1616 (vs), 1524 (s), 1435 (m), 1377 (m), 1345 (s), 1270
(m),1212 (w),1151 (w),1077 (w), 861 (w), 794 (w), 698 (w). 1H NMR
(600 MHz, CDCl3)
d
(ppm): 8.91 (d, J¼8.1 Hz, 1H, CH), 7.97 (d,
CDCl3)
d
187.1, 147.5, 138.1, 136.9, 136.8, 135.7, 133.4, 132.5, 130.2,
J¼7.4 Hz, 1H, CH), 7.70 (d, J¼7.8 Hz, 1H, ArH), 7.64 (t, J¼7.5 Hz, 1H,
ArH), 7.62e7.57 (m, 3H, ArH), 7.52 (d, J¼8.1 Hz, 2H, ArH), 7.08 (d,
J¼7.4 Hz, 1H, ArH), 3.81 (q, J¼6.7 Hz, 1H, CH2), 3.33 (q, J¼6.7 Hz, 1H,
CH2), 3.13 (q, J¼7.0 Hz, 1H, CH2), 2.79 (q, J¼6.9 Hz, 1H, CH2), 1.21 (t,
J¼6.9 Hz, 3H, CH3), 0.69 (t, J¼7.0 Hz, 3H, CH3). 13C NMR (150 MHz,
129.8, 129.5, 129.3, 129.0, 128.0, 127.4, 125.8, 124.4, 124.0, 123.5,
122.9, 122.8, 116.6, 116.0, 86.8. MS (m/z): 418.56 ([Mþ1]þ, 100%).
Anal. Calcd for C26H15N3O3: C 74.81, H 3.62, N 10.07. Found: C 74.67,
H 3.99, N 9.64.
CDCl3)
d 161.6, 134.9, 132.2, 130.5, 128.9, 128.7, 128.4, 127.7, 127.4,
3.4. General procedure for the synthesis of pyrrolo[2,1-a]-
isoquinolines 4mer
124.1, 123.3, 122.9, 122.5, 119.2, 117.7, 114.8, 83.3, 43.1, 39.4, 14.0,
12.4. MS (m/z): 448.64 ([Mþ1]þ, 100%), 446.55 ([Mþ3]þ, 80%). Anal.
Calcd for C24H20BrN3O: C 64.58, H 4.52, N 9.41. Found: C 64.25, H
4.79, N 9.11.
In a 50 mL round bottom flask a mixture of N,N-diethyl chlor-
oacetamide (2.2 mmol, 0.329 g) and isoquinoline (3.0 mmol,
0.388 g) in 10 mL of ethanol was heated at 50 ꢀC for about 5 h. Then
aromatic aldehyde (2.0 mmol), cyanoacetamide (2.0 mmol,
0.168 g), and triethylamine (4.0 mmol, 0.404 g) were added to it.
The solution was stirred at 50 ꢀC for additional 6e8 h . Then the
DDQ (4.0 mmol, 0.908 g) was added. The resulting mixture was
stirred at room temperature for 8 h. The resulting precipitates were
collected by filtration and washed with cold alcohol. The crude
Compound 4q: White solid, yield: 60%, mp 196 ꢀC, IR (KBr): 2960
(w), 2224 (w), 1621 (w), 1523 (m), 1480 (w), 1459 (m), 1347 (m),
1380 (m), 1312 (w), 1278 (w), 1212 (w), 788 (m). 1H NMR (600 MHz,
CDCl3)
d
(ppm): 8.92 (d, J¼7.7 Hz, 1H, CH), 8.00 (d, J¼7.3 Hz, 1H,
ArH), 7.71 (d, J¼7.7 Hz, 1H, CH), 7.66e7.63 (m, 1H, ArH), 7.61e7.57
(m, 3H, ArH), 7.45e7.39 (m, 2H, ArH), 7.09 (d, J¼7.3 Hz, 1H, ArH),
3.93 (q, J¼6.7 Hz, 1H, CH2), 3.22 (q, J¼6.7 Hz, 1H, CH2), 3.14 (q,
J¼7.0 Hz, 1H, CH2), 2.77 (q, J¼7.0 Hz, 1H, CH2), 1.20 (t, J¼7.0 Hz, 3H,