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M.-L. Yang et al. / Tetrahedron 62 (2006) 10900–10906
4.2.3. (9H-b-Carbolin-1-yl)-phenyl-methanol (1c). Yel-
low powder (EtOAc), mp 141–144 ꢀC; IR (KBr) nmax
3352, 1627 cmꢂ1; 1H NMR (DMSO-d6, 300 MHz) d 11.26
(1H, br s, D2O exchangeable, NH), 8.23 (1H, d, J¼5.0 Hz,
H-3), 8.17 (1H, d, J¼7.8 Hz, H-5), 7.98 (1H, d, J¼5.0 Hz,
H-4), 7.72 (1H, d, J¼8.2 Hz, H-8), 7.60 (2H, d, J¼7.4 Hz,
H-20 and -60), 7.50 (1H, t, J¼7.5 Hz, H-7), 7.29–7.17 (3H,
m, H-30, -50, and -6), 6.51 (1H, d, J¼3.8 Hz, OH), 6.14
(1H, d, J¼3.8 Hz, CHOH); 13C NMR (DMSO-d6,
75 MHz) d 147.7, 144.0, 140.9, 137.1, 132.4, 128.9, 128.2,
127.2, 126.5, 121.6, 120.6, 119.4, 113.8, 112.8, 76.1.
EIMS m/z 274 [M]+ (50), 255 (100); HREIMS m/z
274.1109 [M]+ (calcd for C18H14N2O, 274.1106). Anal.
Calcd for C18H14N2O: C, 78.81; H, 5.14; N, 10.21. Found:
C, 78.62; H, 5.24; N, 10.07.
Anal. Calcd for C19H16N2O: C, 79.14; H, 5.59; N, 9.72.
Found: C, 79.27; H, 5.66; N, 9.72.
4.2.7. (3-Hydroxy-9H-b-carbolin-1-yl)-p-tolyl-metha-
none (2d). Orange powder (EtOAc), mp 171–175 ꢀC; IR
1
(KBr) nmax 3360, 1659, 1631 cmꢂ1; H NMR (DMSO-d6,
300 MHz) d 11.56 (1H, br s, D2O exchangeable, NH),
10.33 (1H, br s, D2O exchangeable, OH), 8.21 (1H, d,
J¼8.6 Hz, H-5), 8.18 (2H, d, J¼8.4 Hz, H-20 and -60), 7.69
(1H, s, H-4), 7.67 (1H, d, J¼8.1 Hz, H-8), 7.53 (1H, t,
J¼7.5 Hz, H-7), 7.36 (2H, d, J¼8.1 Hz, H-30 and -50), 7.20
(1H, t, J¼7.5 Hz, H-6), 2.41 (3H, s, CH3); 13C NMR
(DMSO-d6, 75 MHz) d 192.6, 154.8, 143.4, 142.7, 136.0,
135.2, 132.9, 132.0, 131.2, 129.4, 128.8, 122.3, 120.0,
119.6, 112.8, 104.6, 21.4; EIMS m/z 302 [M]+ (100), 287
(34); HREIMS m/z 302.1058 [M]+ (calcd for C19H14N2O2,
302.1055).
4.2.4. 1-(4-Methyl-benzoyl)-9H-b-carboline-3-carboxy-
lic acid (2a). Yellow powder (EtOAc–MeOH), mp 259–
260 ꢀC; IR (KBr) nmax 3256, 1766, 1731, 1639,
4.2.8. 1-(4-Bromo-benzoyl)-9H-b-carboline-3-carboxylic
acid (3a). Yellow powder (EtOAc–MeOH), mp 290–291 ꢀC;
1
1620 cmꢂ1; H NMR (DMSO-d6, 300 MHz) d 12.35 (1H,
br s, D2O exchangeable, NH), 9.15 (1H, s, H-4), 8.46 (1H,
d, J¼7.7 Hz, H-5), 8.34 (2H, d, J¼7.6 Hz, H-20 and -60),
7.83 (1H, d, J¼7.9 Hz, H-8), 7.63 (1H, t, J¼7.5 Hz, H-7),
7.38 (2H, d, J¼7.8 Hz, H-30 and -50), 7.35 (1H, t,
J¼7.5 Hz, H-6), 2.42 (3H, s, CH3); 13C NMR (DMSO-d6,
75 MHz) d 192.2, 166.7, 143.4, 142.2, 136.8, 136.4, 136.1,
134.4, 131.6, 131.5, 129.5, 128.9, 122.4, 121.1, 120.7,
120.5, 113.4, 21.4; EIMS m/z 330 [M]+ (100), 315 (35),
302 (18), 285 (79), 271 (22), 258 (70); HREIMS m/z
330.1007 [M]+ (calcd for C20H14N2O3, 330.1004). Anal.
Calcd for C20H14N2O3: C, 72.72; H, 4.27; N, 8.48. Found:
C, 72.91; H, 4.35; N, 8.51.
IR (KBr) nmax 3276, 1731, 1640, 1621 cmꢂ1 1H NMR
;
(DMSO-d6, 300 MHz) d 12.41 (1H, br s, D2O exchangeable,
NH), 9.16 (1H, s, H-4), 8.47 (1H, d, J¼7.8 Hz, H-5), 8.34
(2H, d, J¼8.2 Hz, H-20 and -60), 7.84 (1H, d, J¼8.8 Hz,
H-8), 7.81 (2H, d, J¼8.2 Hz, H-30 and -50), 7.65 (1H, t,
J¼7.5 Hz, H-7), 7.37 (1H, t, J¼7.5 Hz, H-6); 13C NMR
(DMSO-d6, 75 MHz) d 191.9, 166.7, 142.4, 137.0, 136.6,
136.2, 135.5, 133.5, 131.9, 131.5, 129.8, 127.3, 122.6,
121.4, 121.0, 120.8, 113.6; EIMS m/z 396 [M+2]+ (22),
394 [M]+ (23), 349 (13), 322 (12), 271 (12), 241 (12);
HREIMS m/z 393.9957 [M]+ (calcd for C19H11N2O3Br,
393.9953).
4.2.5. (9H-b-Carbolin-1-yl)-p-tolyl-methanone (2b). Yel-
low needle (EtOAc), mp 158–161 ꢀC; IR (KBr) nmax 3395,
1621, 1604 cmꢂ1; 1H NMR (DMSO-d6, 300 MHz) d 12.02
(1H, br s, D2O exchangeable, NH), 8.52 (1H, d, J¼5.0 Hz,
H-3), 8.44 (1H, d, J¼5.0 Hz, H-4), 8.32 (1H, d, J¼7.6 Hz,
H-5), 8.14 (2H, d, J¼8.0 Hz, H-20 and -60), 7.79 (1H, d,
J¼7.9 Hz, H-8), 7.60 (1H, dd, J¼7.9, 7.4 Hz, H-7), 7.38
(2H, d, J¼8.0 Hz, H-30 and -50), 7.31 (1H, dd, J¼7.6,
7.4 Hz, H-6), 2.42 (3H, s, CH3); 13C NMR (DMSO-d6,
75 MHz) d 193.4, 142.9, 141.8, 137.3, 136.8, 135.9, 134.9,
131.2, 131.1, 129.1, 128.8, 122.0, 120.3, 120.2, 118.9,
113.1, 21.4; EIMS m/z 286 [M]+ (100), 271 (74), 258
(100); HREIMS m/z 286.1102 [M]+ (calcd for C19H14N2O,
286.1106). Anal. Calcd for C19H14N2O: C, 79.70; H, 4.93;
N, 9.78. Found: C, 79.92; H, 5.03; N, 9.84.
4.2.9. (4-Bromo-phenyl)-(9H-b-carbolin-1-yl)-metha-
none (3b). Yellow needle (EtOAc), mp 194–196 ꢀC; IR
(KBr) nmax 3389, 1644 cmꢂ1
;
1H NMR (DMSO-d6,
300 MHz) d 12.09 (1H, br s, D2O exchangeable, NH), 8.51
(1H, d, J¼4.9 Hz, H-3), 8.44 (1H, d, J¼4.9 Hz, H-4), 8.31
(1H, d, J¼7.8 Hz, H-5), 8.15 (2H, d, J¼8.5 Hz, H-20 and
-60), 7.82 (1H, d, J¼8.2 Hz, H-8), 7.77 (2H, d, J¼8.5 Hz,
H-30 and -50), 7.60 (1H, t, J¼7.5 Hz, H-7), 7.31 (1H, t,
J¼7.5 Hz, H-6); 13C NMR (DMSO-d6, 75 MHz) d 192.8,
141.9, 137.4, 136.6, 136.0, 133.0, 131.3, 131.2, 129.2,
126.5, 122.0, 120.4, 120.2, 119.3, 113.2; EIMS m/z 352
[M+2]+ (17), 350 [M]+ (18), 322 (14), 279 (27), 185 (71),
183 (79), 167 (44), 149 (100); HREIMS m/z 350.0055
[M]+ (calcd for C18H11N2OBr, 350.0055). Anal. Calcd for
C18H11N2OBr: C, 61.56; H, 3.16; N, 7.98. Found: C,
61.76; H, 3.21; N, 7.94.
4.2.6. (9H-b-Carbolin-1-yl)-p-tolyl-methanol (2c). Yellow
powder (EtOAc), mp 184–185 ꢀC; IR (KBr) nmax 3360,
4.2.10. (4-Bromo-phenyl)-(9H-b-carbolin-1-yl)-metha-
nol (3c). Yellow powder (EtOAc), mp 157–159 ꢀC; IR
1
1625 cmꢂ1; H NMR (DMSO-d6, 300 MHz) d 11.23 (1H,
br s, D2O exchangeable, NH), 8.22 (1H, d, J¼5.2 Hz,
H-3), 8.17 (1H, d, J¼7.6 Hz, H-5), 7.97 (1H, d, J¼5.2 Hz,
H-4), 7.72 (1H, d, J¼7.9 Hz, H-8), 7.50 (1H, dd, J¼7.9,
7.4 Hz, H-7), 7.47 (2H, d, J¼7.7 Hz, H-20 and -60), 7.19
(1H, dd, J¼7.6, 7.4 Hz, H-6), 7.07 (2H, d, J¼7.7 Hz, H-30
and -50), 6.46 (1H, d, J¼4.0 Hz, OH), 6.10 (1H, d,
J¼4.0 Hz, CHOH); 13C NMR (DMSO-d6, 75 MHz)
d 147.8, 140.9, 140.8, 137.0, 136.1, 132.3, 128.7, 128.7,
128.0, 126.4, 121.5, 120.5, 119.2, 113.7, 112.7, 75.8, 20.8;
EIMS m/z 288 [M]+ (100), 269 (56), 255 (92); HREIMS
m/z 288.1265 [M]+ (calcd for C19H16N2O, 288.1263).
(KBr) nmax 3441, 1628 cmꢂ1 1H NMR (DMSO-d6,
;
300 MHz) d 11.27 (1H, br s, D2O exchangeable, NH), 8.23
(1H, d, J¼5.3 Hz, H-3), 8.17 (1H, d, J¼7.6 Hz, H-5), 7.99
(1H, d, J¼5.3 Hz, H-4), 7.71 (1H, d, J¼8.0 Hz, H-8), 7.55
(2H, d, J¼8.5 Hz, H-20 and -60), 7.51 (1H, dd, J¼8.0,
7.5 Hz, H-7), 7.47 (2H, d, J¼8.5 Hz, H-30 and -50), 7.20
(1H, dd, J¼7.6, 7.5 Hz, H-6), 6.62 (1H, d, J¼4.1 Hz, OH),
6.14 (1H, d, J¼4.1 Hz, CHOH); 13C NMR (DMSO-d6,
75 MHz) d 147.1, 143.3, 140.9, 137.1, 132.4, 131.1, 129.0,
128.7, 128.2, 121.6, 120.6, 120.3, 119.4, 114.0, 112.7,
75.2; EIMS m/z 354 [M+2]+ (34), 352 [M]+ (35), 335 (24),