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7c: Yellow plates (methanol), mp 171—172 °C. IR (KBr) cmꢀ1: 2187,
1681, 1624, 824, 750, 736. 1H-NMR (CDCl3) d: 3.80 (3H, s, OMe), 5.70
(2H, s, CH2), 6.94 (2H, d, Jꢁ6.6 Hz, H-aromatic), 7.19—7.32 (4H, m, H-
aromatic), 7.41—7.42 (2H, m, H-aromatic), 7.60 (1H, d, Jꢁ7.7 Hz, H-aro-
matic), 7.74 (1H, d, Jꢁ9.5 Hz, H-4), 8.28 (1H, d, Jꢁ9.5 Hz, H-3). 13C-NMR
(CDCl3) d: 51.69, 58.27, 118.69, 120.79, 123.53, 124.92, 124.95, 126.23,
127.78, 128.52, 128.84 (C2), 131.14, 135.73 (C2), 136.02, 139.51, 160.68
(C2), 166.72. MS m/z: 316 (Mꢂ), 257, 91. HR-MS Calcd for C20H16N2O2,
316.1212. Found: 316.1222.
8.40 (1H, s, H-3), 8.54 (1H, dd, Jꢁ1.5, 8.4 Hz, H-5). 13C-NMR (CDCl3) d:
16.43, 33.80 (C2), 37.17, 110.50, 114.35, 114.86, 123.46, 124.91, 132.76,
133.68, 140.69, 152.59, 159.01, 201.61 (C2). MS m/z: 285 (Mꢂ). HR-MS
Calcd for C16H15NO2S, 285.0823. Found: 285.0805.
General Procedure for the Cyclization Reactions of 7a, d, e with
Acetic Anhydride A mixture of 7a (0.349 g, 1.0 mmol) and acetic anhy-
dride (4 ml) was refluxed for 4 h and then concentrated in vacuo. The
residure was purified by silica gel column chromatography, in which the first
fraction eluted with hexane–ether (1 : 1) gave methyl 2-acetoxy-3-
phenylpyrrolo[1,2-a]quinolinyl-1-carboxylate (11a, 0.232 g, 65%). Reaction
of 7d with acetic anhydride was carried out similarly to give methyl 2-
methyl-3-phenylpyrrolo[1,2-a]quinolinyl-1-carboxylate (11d, 75%) and 2-
acetoxy-1-acetyl-3-phenylpyrrolo[1,2-a]quinoline (12d, 21%); reaction of
7e with acetic anhydride afforded 1-acetyl-2-methyl-3-phenylpyrrolo[1,2-
a]quinoline (11e, 86%).
7d: Yellow plates (methanol), mp 105—106 °C. IR (KBr) cmꢀ1: 1655,
1
1608, 1581, 825, 751, 716. H-NMR (CDCl3) d: 2.54 (3H, s, COMe), 3.69
(3H, s, OMe), 5.80 (2H, s, CH2), 6.98—7.00 (2H, m, H-Ph), 7.14—7.27
(3H, m, H-Ph), 7.46 (1H, ddd, Jꢁ1.0, 7.3, 7.3 Hz, H-aromatic), 7.56 (1H,
ddd, Jꢁ1.5, 7.3, 8.8 Hz, H-aromatic), 7.76—7.82 (2H, m, H-aromatic), 7.89
(1H, d, Jꢁ9.1 Hz, H-4), 8.06 (1H, d, Jꢁ9.1 Hz, H-3). 13C-NMR (CDCl3) d:
29.80, 50.28, 57.79, 98.75, 120.08, 126.37 (C2), 126.57 (C2), 126.94,
127.77, 128.90, 128.95, 129.80, 131.53, 135.88, 138.02, 138.31, 165.38,
168.38, 190.91. MS m/z: 333 (Mꢂ), 230, 91. HR-MS Calcd for C21H19NO3,
333.1365. Found: 333.1377.
11a: Yellow plates (acetone), mp 165—166 °C. IR (KBr) cmꢀ1: 1761,
1
1694, 1605, 791, 773, 761. H-NMR (CDCl3) d: 2.25 (3H, s, COMe), 3.95
(3H, s, OMe), 6.93 (1H, d, Jꢁ7.3 Hz, H-3), 7.45—7.63 (8H, m, H-aro-
matic), 7.83 (1H, d, Jꢁ7.3 Hz, H-4), 9.39 (1H, ddd, Jꢁ0.7, 1.4, 8.3 Hz, H-
aromatic). 13C-NMR (CDCl3) d: 20.64, 51.60, 101.44, 113.70, 119.17,
121.31, 125.38, 126.61, 126.91, 127.61, 127.65, 127.83, 128.82, 129.02,
129.13 (C2), 129.80, 130.06 (C2), 137.30, 164.77, 170.01. MS m/z: 359
(Mꢂ), 285. HR-MS Calcd for C22H17NO4, 359.1158. Found: 359.1172.
11d: The second fraction: Yellow needles (acetone), mp 185—186 °C. IR
(KBr) cmꢀ1: 1764, 1718, 1655, 1604. 1H-NMR (CDCl3) d: 2.15 (3H, s,
COMe), 2.51 (3H, s, OCOMe), 7.14 (1H, dd, Jꢁ1.6, 7.1 Hz, H-5 or 8),
7.16—7.36 (2H, m, H-6, 7), 7.40—7.54 (6H, m, H-Ph, 3), 7.71 (1H, dd,
Jꢁ1.5, 8.1 Hz, H-5 or 8), 8.50 (1H, d, Jꢁ9.4 Hz, H-4). 13C-NMR (CDCl3) d:
20.69, 30.00, 108.22, 117.76, 118.92, 121.10, 124.46, 125.49, 125.55,
127.76, 128.95, 129.01 (C2), 129.07, 130.5 (C2), 131.26, 132.75, 133.31,
138.47, 169.60, 192.12. MS m/z: 343 (Mꢂ), 301, 286. HR-MS Calcd for
C22H17NO3, 343.1208. Found: 343.1222.
7e: Yellow plates (methanol), mp 166—167 °C. IR (KBr) cmꢀ1: 1681,
1615, 1608, 832, 760, 750. 1H-NMR (CDCl3) d: 2.43 (6H, s, COMeꢃ2),
5.92 (2H, s, CH2), 7.05 (2H, dd, Jꢁ1.6, 8.1 Hz, H-Ph), 7.16—7.28 (3H, m,
H-Ph), 7.56 (1H, ddd, Jꢁ1.0, 8.0, 9.0 Hz, H-aromatic), 7.64 (1H, ddd,
Jꢁ1.6, 7.1, 8.7 Hz, H-aromatic), 7.83—7.87 (2H, m, H-aromatic), 7.90 (1H,
d, Jꢁ8.8 Hz, H-4), 8.25 (1H, d, Jꢁ8.8 Hz, H-3). 13C-NMR (CDCl3) d: 25.48
(C2), 51.23, 119.65, 124.90, 125.68, 126.99 (C2), 127.51, 127.66, 128.76,
128.66 (C2), 130.34, 135.45, 135.76 (C2), 138.73, 163.52, 168.51 (C2). MS
m/z: 317 (Mꢂ), 274, 232, 91. HR-MS Calcd for C21H19NO2, 317.1416.
Found: 317.1422.
7f: Yellow needles (acetone), mp 270—275 °C. IR (KBr) cmꢀ1: 1620,
1566, 757, 751, 718. 1H-NMR (CDCl3) d: 1.97—2.16 (2H, m, CH2), 2.48—
2.57 (4H, m, COCH2ꢃ2), 5.89 (2H, s, NCH2), 7.00 (2H, dd, Jꢁ1.6, 8.3 Hz,
H-Ph), 7.08—7.27 (3H, m, H-Ph), 7.50 (1H, ddd, Jꢁ1.0, 7.1, 8.6 Hz, H-aro-
matic), 7.60 (1H, ddd, Jꢁ1.6, 7.1, 8.6 Hz, H-aromatic), 7.83 (1H, dd, Jꢁ1.6,
8.6 Hz, H-aromatic), 7.91 (1H, dd, Jꢁ1.0, 8.6 Hz, H-aromatic), 8.07 (1H, d,
Jꢁ8.9 Hz, H-4), 8.25 (1H, d, Jꢁ8.9 Hz, H-3). 13C-NMR (CDCl3) d: 21.40,
34.59 (C2), 56.89, 108.59, 119.55, 124.60, 125.44 (C2), 126.10, 126.58,
127.44, 128.32 (C2), 129.00, 132.06, 134.99, 136.89, 140.40, 158.58,
201.00 (C2). MS m/z: 329 (Mꢂ), 321, 91. HR-MS Calcd for C22H19NO2,
329.1416. Found: 329.1394.
12d: The first fraction: Yellow plates (acetone), mp 123 °C. IR (CHCl3)
cmꢀ1: 1718, 1700, 1605. 1H-NMR (CDCl3) d: 2.66 (3H, s, CMe), 3.56 (3H,
s, OMe), 7.14 (1H, ddd, Jꢁ1.6, 7.1, 8.7 Hz, H-aromatic), 7.21—7.39 (2H,
m, H-aromatic), 7.44 (1H, d, Jꢁ9.4 Hz, H-3), 7.53 (5H, s, H-Ph), 7.69 (1H,
dd, Jꢁ1.5, 7.7 Hz, H-aromatic), 8.51 (1H, d, Jꢁ9.4 Hz, H-4). 13C-NMR
(CDCl3) d: 20.64, 31.60, 101.44, 113.70, 119.17, 121.31, 125.38, 126.61,
126.91, 127.61, 127.65, 127.83, 128.82, 129.02, 129.13 (C2), 129.80,
130.06 (C2), 137.30, 170.01. MS m/z: 315 (Mꢂ), 300, 284. HR-MS Calcd
for C21H17NO2, 315.1259. Found: 315.1227.
7g: Yellow needles (acetone), mp 239—240 °C. IR (KBr) cmꢀ1: 1657,
1605, 836, 755, 718. 1H-NMR (CDCl3) d: 2.60 (4H, s, CH2ꢃ2), 5.99 (2H, s,
NCH2), 6.86 (2H, dd, Jꢁ1.5, 6.9 Hz, H-Ph), 7.13—7.23 (3H, m, H-Ph), 7.51
(1H, ddd, Jꢁ1.0, 7.0, 7.0 Hz, H-6 or 7), 7.62 (1H, ddd, Jꢁ1.5, 7.0, 8.5 Hz,
H-6 or 7), 7.82—7.87 (2H, m, H-5,8), 8.32 (1H, d, Jꢁ9.1 Hz, H-3 or 4),
8.40 (1H, d, Jꢁ9.1 Hz, H-3 or 4). 13C-NMR (CDCl3) d: 33.95 (C2), 57.89,
109.58, 119.64, 125.49, 125.99 (C2), 126.70, 126.88, 127.87, 128.98 (C2),
129.19, 132.06, 135.57, 138.79, 140.30, 157.68, 200.47 (C2). MS m/z: 315
(Mꢂ), 230, 181, 91. HR-MS Calcd for C21H17NO2, 315.1259. Found:
315.1278.
11e: Yellow needles (acetone), mp 110—111 °C. IR (KBr) cmꢀ1: 1693,
1
1642, 1601, 821, 805, 748. H-NMR (CDCl3) d: 2.30 (3H, s, COMe), 2.65
(3H, s, CMe), 7.09 (1H, ddd, Jꢁ1.6, 6.9, 8.5 Hz, H-aromatic), 7.15—7.29
(2H, m, H-aromatic), 7.35—7.40 (3H, m, H-3, aromatic), 7.42—7.60 (3H,
m, H-aromatic), 7.67 (1H, dd, Jꢁ1.5, 7.9 Hz, H-aromatic), 8.42 (1H, d,
Jꢁ9.4 Hz, H-4). 13C-NMR (CDCl3) d: 13.05, 31.68, 100.51, 115.92, 117.77,
118.91, 123.89, 123.95, 124.59, 125.45, 127.39, 128.51, 128.60, 128.63,
129.08 (C2), 131.24, 133.43, 134.41, 134.71, 195.04. MS m/z: 299 (Mꢂ),
284. HR-MS Calcd for C21H17NO, 299.1310. Found: 299.1321.
7h: Yellow needles (acetone), mp 220 °C. IR (KBr) cmꢀ1: 1681, 1651,
1547, 1174, 820, 752, 711. 1H-NMR (CDCl3) d: 2.64 (4H, s, CH2CH2), 2.82
(3H, s, SMe), 5.83 (2H, s, NCH2), 7.05 (2H, dd, Jꢁ2.6, 7.8 Hz, H-Ph),
7.31—7.40 (3H, m, H-Ph), 7.49—7.56 (2H, m, H-7, 8), 7.68 (1H, ddd,
Jꢁ1.5, 6.8, 8.3 Hz, H-6), 8.47 (1H, s, H-3), 8.58 (1H, dd, Jꢁ1.5, 8.3 Hz, H-
5). 13C-NMR (CDCl3) d: 16.42, 33.82 (C2), 53.48, 110.81, 114.51, 115.71,
123.64, 124.98, 125.70 (C2), 128.52, 129.40 (C2), 132.46, 132.69, 133.87,
140.59, 152.98, 159.26, 201.73 (C2). MS m/z: 361 (Mꢂ), 270, 91. HR-MS
Calcd for C22H19NO2S, 361.1137. Found: 361.1157.
References
1) Tomisawa H., Tanbara T., Kato H., Hongo H., Fujita R., Heterocycles,
15, 277—280 (1981).
2) Tominaga Y., Matsuda Y., J. Syn. Org. Chem. Jpn., 43, 669—679
(1985). References cited therein.
3) Roberts E. M., Gates M., Boekelheide V., J. Org. Chem., 20, 1443—
1447 (1955).
4) Hurst J., Melton T., Wibberley D. G., J. Chem. Soc., 1965, 2948—2955
(1965).
10g: Pale yellow columns (methanol), mp 236—238 °C. IR (KBr) cmꢀ1
:
1660, 830, 750. 1H-NMR (CDCl3) d: 2.63 (4H, s, CH2ꢃ2), 4.15 (3H, s,
NMe), 7.61 (1H, ddd, Jꢁ1.5, 7.4, 8.9 Hz, H-aromatic), 7.80—7.90 (2H, m,
H-aromatic), 7.96 (1H, dd, Jꢁ0.8, 9.4 Hz, H-5 or 8), 8.19 (1H, d, Jꢁ9.0 Hz,
H-4), 8.33 (1H, d, Jꢁ9.0 Hz, H-3). 13C-NMR (CDCl3) d: 34.08 (C2), 42.70,
108.99, 117.96, 125.18, 126.03, 126.80, 129.05, 132.47, 139.22, 139.85,
156.56, 200.57 (C2). MS m/z: 239 (Mꢂ). HR-MS Calcd for C15H13NO2,
239.0946. Found: 239.0949.
5) Melton T., Taylor J., Wibberley D. G., J. Chem. Soc. Chem. Commun.,
1965, 151—152 (1965).
6) Henrick C. A., Ritchie E., Taylor W. C., Aust. J. Chem., 20, 2467—
2477 (1967).
7) Irwin W. J., Wibberley D. G., J. Chem. Soc., Perkin Trans 1, 1974,
250—252 (1974).
8) Komatsu M., Kasano Y., Yamaoka S., Minakata S., Synthesis, 2003,
1398—1402 (2003).
10h: Pale yellow columns (methanol), mp ꢄ300 °C. IR (KBr) cmꢀ1
:
1600, 840, 750. 1H-NMR (CDCl3) d: 2.61 (4H, s, CH2ꢃ2), 2.83 (3H, s,
SMe), 4.13 (3H, s, NMe), 7.55 (1H, ddd, Jꢁ1.5, 6.9, 8.4 Hz, H-6 or 7), 7.69
(1H, dd, Jꢁ1.5, 8.4 Hz, H-8), 7.80 (1H, ddd, Jꢁ1.5, 6.9, 8.4 Hz, H-6 or 7),
9) Boultadakis E., Chung B., Elsegood M. R. J., Weaver G. W., Synlett,
2002, 1547—1549 (2002).