Pirrung et al.
9.4, 7.3. IR (KBr): 3450, 3386, 3061, 1676, 1650, 1561, 1448,
1273, 1241, 1032, 882, 745 cm-1. Anal. Calcd for C17H11Cl2-
NO2: C, 61.47; H, 3.34; N, 4.22. Found: C, 61.71; H, 3.36; N,
4.20.
2,5-Dich lor o-3-(2-p h e n yl-1H -in d ol-3-yl)[1,4]b e n zo-
qu in on e (11). Blue crystals from benzene/hexane. Mp: 170-
171 °C. Yield: 89%. 1H NMR (CDCl3): δ 7.20 (1H, m), 7.21
(1H, s), 7.28-7.31 (2H, m), 7.36-7.43 (5H, m), 7.47 (1H, m),
8.61 (1H, br s). 13C NMR (CDCl3): δ 104.7, 111.9, 120.4, 121.3,
123.3, 127.3, 127.5, 129.1, 129.4, 132.4, 133.4, 136.2, 139.6,
140.5, 141.3, 144.7, 176.5, 177.8. IR (KBr): 3384, 3056, 1683,
1565, 1446, 1248 cm-1. Anal. Calcd for C20H11Cl2NO2: C, 65.24;
H, 3.01; N, 3.73. Found: C, 64.61; H, 3.14; N, 3.76.
2,5-Dich lor o-3-(1-m e t h yl-1H -in d ol-3-yl)[1,4]b e n zo-
qu in on e (12). Blue crystals from benzene/hexane. Yield: 85%.
Mp: 156.1-156.2 °C. IR (KBr): 3142, 3057, 2911, 1683, 1656,
1559, 749 cm-1. 1H NMR (CDCl3): δ 3.91 (3H, s), 7.21 (1H, s),
7.23 (1H, m), 7.31 (1H, m), 7.39 (1H, d, J ) 9.3 Hz), 7.40 (1H,
dd, J ) 0.9, 6.9 Hz). 13C NMR (CDCl3): δ 33.9, 105.6, 110.3,
121.1, 122.3, 122.9, 126.0, 133.5, 134.4, 137.0, 138.4, 144.1,
178.0. Anal. Calcd for C15H9Cl2NO2: C, 58.85; H, 2.97; N, 4.58.
Found: C, 58.69; H, 3.07; N, 4.57.
11.00 (1H, br s), 7.39 (1H, d, J ) 8.4 Hz), 7.32 (1H, d, J ) 1.8
Hz), 7.08 (1H, dd, J ) 1.8, 8.4 Hz), 2.37 (3H, s). 13C NMR (d6-
acetone): δ 175.3, 172.0, 141.2, 140.1, 139.8, 139.4, 134.5,
128.7, 125.3, 121.5, 119.2, 112.5, 104.5, 13.0. HRMS (EI): m/z
calcd for C15H7Cl4NO2 [M+] 372.9231, found 372.9232.
2,5-Dich lor o-3-[2-(1-m eth ylcycloh exyl)-1H-in d ol-3-yl]-
[1,4]ben zoqu in on e (19). Blue needles from benzene/hexane.
Mp: 184-185 °C. 1H NMR (d6-acetone): δ 1.36 (3H, s), 1.38-
1.66 (10H, m), 6.96 (1H, dt, J ) 1.2, 7.2 Hz), 7.08 (1H, dt, J )
1.2, 7.2 Hz), 7.23 (1H, d, J ) 7.8 Hz), 7.37 (1H, d, J ) 8.1 Hz),
7.45 (1H, s), 10.39 (1H, br s). 13C NMR (d6-acetone): δ 22.6,
22.8, 26.2, 27.4, 37.5, 37.8, 38.2, 102.4, 111.2, 118.5, 119.5,
121.5, 127.4, 134.0, 135.6, 142.4, 142.8, 143.9, 145.0, 177.8.
IR (KBr): 3421, 3320, 3054, 2936, 2863, 1672, 1618, 1573,
1515, 1457, 1205, 1024 cm-1. Anal. Calcd for C21H19Cl2NO2:
C, 64.96; H, 4.93; N, 3.61. Found: C, 65.04; H, 4.89; N, 3.63.
3-(4-F lu o r o -1H -in d o l-3-y l)-2,5-d ic h lo r o [1,4]b e n zo -
qu in on e (20). Blue needles from benzene/hexane. Mp: 161-
1
162 °C. H NMR (d6-acetone): δ 6.79 (1H, ddd, J ) 0.7, 7.6,
11.2 Hz), 7.15 (1H, dt, J ) 5.2, 7.6 Hz), 7.34 (1H, d, J ) 8 Hz),
7.38 (1H, s), 7.66 (1H, d, J ) 2.8 Hz), 11.15 (1H, s). 13C NMR
(d6-acetone): δ 104.5, 105.7, 105.9, 108.6, 123.1, 123.2, 129.2,
133.6, 139.1, 143.6, 154.9, 157.2, 177.5 177.8. IR (KBr): 3386,
2,5-D ic h lo r o -3-(2-e t h y l-1H -in d o l-3-y l)[1,4]b e n zo -
qu in on e (13). This compound was synthesized according to
general procedure A from 2-ethyl-1H-indole (100 mg, 0.689
mmol) and 2,5-dichloro-1,4-benzoquinone (244 mg, 1.38 mmol)
and obtained as a blue solid (209 mg, 95%). Mp: 143-144 °C.
Rf ) 0.38 (3:7, EtOAc/hexane). 1H NMR (CDCl3): δ 8.48 (br s,
NH), 7.29 (m, 1H), 7.20 (s, 1H), 7.19-7.08 (m, 3H), 2.61 (qd,
3067, 1671, 1577, 1505, 1422, 1318, 1265, 1226, 1019 cm-1
.
Anal. Calcd for C14H6Cl2FNO2: C, 54.22; H, 1.95; N, 4.52.
Found: C, 54.15; H, 1.89; N, 4.58.
3-(4-C h lo r o -1H -in d ol-3-y l)-2,5-d ic h lor o[1,4]b e n zo -
qu in on e (21). Blue needles from benzene/hexane. Mp: 204-
205 °C. 1H NMR (d6-acetone): δ 7.07 (1H, dd, J ) 0.8, 7.6 Hz),
7.15 (1H, t, J ) 7.6 Hz), 7.40 (1H, s), 7.49 (1H, dd, J ) 0.8, 8.0
Hz), 7.60 (1H, d, J ) 2.8 Hz), 11.17 (1H, br s). 13C NMR (d6-
acetone): δ 106.3, 111.4, 121.0, 123.2, 124.4, 125.0, 128.4,
133.6, 137.9, 140.5, 140.9, 143.9, 177.7, 177.9. IR (KBr): 3350,
1
J ) 7.5, 3.0 Hz, 2H), 1.27 (t, J ) 7.5 Hz, 3H); H NMR (d6-
acetone): δ 10.62 (1H, br s), 7.40 (1H, s), 7.38 (1H, d, J ) 8.1
Hz), 7.24 (1H, d, J ) 8.1 Hz), 7.09 (1H, t, J ) 8.1 Hz), 7.01
(1H, t, J ) 8.1 Hz), 7.71 (2H, q, J ) 7.8 Hz), 1.30 (3H, t, J )
7.8). 13C NMR (CDCl3): δ 177.7, 176.6, 144.3, 142.1, 140.2,
139.5, 135.2, 133.0, 126.4, 121.9, 120.5, 119.6, 110.9, 103.7,
21.2, 13.4. IR (KBr): 3394, 3050, 2973, 1677, 1646, 1563, 1447,
1241, 1038, 746 cm-1. Anal. Calcd for C16H11Cl2NO2: C, 60.02;
H, 3.46; Cl, 22.15; N, 4.37. Found: C, 59.99; H, 3.51; N, 4.18.
2,5-Dich lor o-3-(2-isop r op yl-1H -in d ol-3-yl)[1,4]b en zo-
qu in on e (14). This compound was synthesized according to
general procedure A from 2-isoprenyl-1H-indole (50 mg, 0.314
mmol) and 2,5-dichloro-1,4-benzoquinone (111 mg, 0.629 mmol)
and obtained as a blue solid (74 mg, 70%). Mp: 187-188 °C.
Rf ) 0.26 (1:4, EtOAc/hexane). 1H NMR (CDCl3): δ 8.40 (br s,
NH), 7.36 (m, 1H), 7.22 (s, 1H), 7.21-7.08 (m, 3H), 2.88 (septet,
J ) 6.9 Hz, 1H), 1.35 (d, J ) 6.9 Hz, 3H), 1.27 (d, J ) 6.9 Hz,
3H). 13C NMR (CDCl3): δ 177.7, 176.6, 145.8, 144.4, 140.9,
139.7, 135.1, 133.1, 126.1, 122.0, 120.4, 119.5, 111.0, 102.6,
27.4, 22.9, 22.3. IR (KBr): 3421, 3312, 3053, 2963, 1671, 1569,
3115, 3068, 1673, 1659, 1572, 1416, 1274, 1196, 1023 cm-1
.
Anal. Calcd for C14H6Cl3NO2: C, 51.49; H, 1.85. Found: C,
51.33; H, 2.00.
3-(4-B r o m o -1H -in d o l-3-y l)-2,5-d ic h lo r o [1,4]b e n zo -
qu in on e (22). Blue needles from benzene/hexane. Mp: 247-
1
248 °C. H NMR (d6-acetone): δ 7.09 (1H, t, J ) 8.0 Hz), 7.25
(1H, dd, J ) 0.8, 8.0 Hz), 7.41 (1H, s), 7.54 (1H, dd, J ) 0.8,
8.0 Hz), 7.60 (1H, d, J ) 3.2 Hz), 11.11 (1H, br s). 13C NMR
(d6-acetone): δ 107.3, 111.2, 111.9, 113.1, 123.5, 124.3, 126.0,
128.2, 133.6, 137.7, 141.0, 144.1, 177.6, 177.9. IR (KBr): 3367,
3116, 3068, 1651, 1613, 1570, 1517, 1480, 1412, 1021, 875
cm-1. Anal. Calcd for C14H6BrCl2NO2: C, 45.32; H, 1.63.
Found: C, 45.38; H, 1.84.
2,5-Dich lor o-3-(4-m et h oxy-1H -in d ol-3-yl)[1,4]b en zo-
qu in on e (23). Blue needles from benzene/hexane. Mp: 195-
1
196 °C. H NMR (d6-acetone): δ 3.76 (1H, s), 6.58 (1H, dd, J
1440, 1241, 1031, 759 cm-1. HRMS (EI): m/z calcd for C17H13
-
) 3.6, 5.1 Hz), 7.11 (1H, s), 7.12(1H, d, J ) 1.5 Hz), 7.35 (1H,
s), 7.56 (1H, d, J ) 3 Hz), 10.86 (1H, br s). 13C NMR
(d6-acetone): δ 55.0, 101.2, 105.4, 106.5, 123.6, 126.8, 127.0,
133.2, 136.4, 138.0, 141.9, 143.6, 153.3, 177.6, 177.8. IR
(KBr): 3324, 3042, 2967, 1676, 1638, 1546, 1486, 1260, 1229,
1009 cm-1. Anal. Calcd for C15H9Cl2NO3: C, 55.93; H, 2.82;
N, 4.35. Found: C, 56.09; H, 2.87; N, 4.32.
Cl2NO2 [M+] 333.0323, found 333.0313.
2,5-Dich lor o-3-(2-ter t-b u t yl-1H -in d ol-3-yl)[1,4]b en zo-
qu in on e (15). Mp: 235-236 °C. IR (KBr): 3419, 3317, 3059,
2965, 1673, 1585, 1462, 1245, 1029, 742 cm-1 1H NMR (d6-
.
acetone): δ 10.40 (1H, br s), 7.47 (1H, s), 7.35 (1H, d, J ) 7.8
Hz), 7.23(1H, d, J ) 7.8 Hz), 7.08 (1H, t, J ) 7.8 Hz), 6.95
(1H, t, J ) 7.8 Hz), 1.38 (9H, s). 13C NMR (CDCl3): δ 178.0,
177.7, 145.3, 145.1, 143.2, 142.7, 134.9, 133.5, 127.1, 122.6,
120.6, 118.3, 111.1, 102.1, 33.6, 30.5. HRMS (EI): m/z calcd
for C18H15Cl2NO2 [M+] 347.0480, found 347.0491.
2,3,5-Tr ich lor o-6-(5-m eth oxy-2-m eth yl-1H-in d ol-3-yl)-
[1,4]ben zoqu in on e (16). Mp: 203-204 °C. IR (KBr): 3351,
2937, 2833, 1673, 1557, 1482, 1205, 1085 cm-1.1H NMR
(CDCl3): δ 8.25 (1H, br s), 7.22 (1H, d, J ) 8.7 Hz), 6.83 (1H,
dd, J ) 2.4, 8.7 Hz), 6.59 (1H, d, J ) 2.4 Hz), 3.80 (3H, s),
2.32 (3H, s). 13C NMR (CDCl3): δ 175.3, 172.1, 155.1, 141.7,
140.9, 139.8, 139.0, 138.2, 130.4, 127.5, 122.4, 111.8, 105.1,
102.6, 56.1, 14.3. HRMS (EI): m/z calcd for C16H10Cl3NO2 [M+]
368.9726, found 368.9726.
3-(4-Ben zyloxy-1H-in d ol-3-yl)-2,5-d ich lor o[1,4]b en zo-
qu in on e (24). Blue needles from benzene/hexane. Mp: 193-
1
194 °C. H NMR (d6-acetone): δ 5.01 (2H, s), 6.64 (1H, dd, J
) 2.4, 6.4 Hz), 7.06 (1H, s), 7.4-7.7 (2H, m), 7.23-7.34 (5H,
m), 7.45 (1H, d, J ) 2.8 Hz), 10.79 (1H, br s). 13C NMR (d6-
acetone): δ 70.3, 102.1, 105.6, 106.3, 117.8, 123.5, 126.3, 127.8,
128.0, 128.6, 132.9, 137.5, 138.1, 141.7, 143.8, 152.7, 177.2,
177.8. IR (KBr): 3346, 3116, 3063, 3034, 1673, 1656, 1572,
1508, 1453, 1423, 1270 cm-1. Anal. Calcd for C21H13Cl2NO3:
C, 63.34; H, 3.29. Found: C, 63.26; H, 3.40.
2,5-D ic h lo r o -(4-m e t h y l-1H -in d o l-3-y l)[1,4]b e n zo -
qu in on e (25). Blue needles from benzene/hexane. Mp: 192-
1
193 °C. H NMR (d6-acetone): δ 2.28 (3H,s), 6.83 (1H, dt, J )
2,3,5-Tr ich lor o-6-(5-ch lor o-2-m eth yl-1H-in d ol-3-yl)[1,4]-
ben zoqu in on e (17). Mp: 228-229 °C. IR (KBr): 3350, 1674,
1564, 1468, 1247, 1158, 1089 cm-1.1H NMR (d6-acetone): δ
0.6, 5.4 Hz), 7.06 (1H, t, J ) 5.7 Hz), 7.32 (1H, d, J ) 6 Hz),
7.39 (1H d6-acetone,s), 7.44 (1H, d, J ) 2.1 Hz), 10.77 (1H, br
s). 13C NMR (d6-acetone): δ 19.3, 107.1, 110.0, 122.0, 122.5,
8382 J . Org. Chem., Vol. 67, No. 24, 2002