The Journal of Organic Chemistry
Article
8,10,11-Trimethyl-5,6-diphenyl-11H-benzo[a]carbazole 3k (62%,
51 mg), mp = 239−240 °C; H NMR (400 MHz, CDCl3): δ 8.59
3-Fluoro-11-methyl-5,6-di-p-tolyl-11H-benzo[a]carbazole 3r (72%,
61 mg), mp = 217−218 °C; H NMR (400 MHz, CDCl3): δ 8.69−
1
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8.74 (m, 1 H), 7.47 (d, J = 8.0 Hz, 1 H), 7.27−7.38 (m, 3 H), 7.03−
7.12 (m, 8 H), 6.92−6.95 (m, 1 H), 6.66 (d, J = 8.0 Hz, 1 H), 4.35 (s,
3 H), 2.36 (s, 3 H), 2.31 (s, 3 H); 13C NMR (100 MHz, CDCl3):
161.1, 158.7, 141.0, 137.0, 136.2, 136.1, 135.8, 135.0, 134.7, 134.6,
131.4, 130.6, 130.5, 129.8, 128.7, 128.4, 124.3, 124.2, 123.2, 122.0,
119.4, 118.8, 117.5, 114.2, 113.9, 112.3, 112.1, 108.7, 34.3, 21.4, 21.2;
IR (neat, cm−1): 2920, 1619, 1448, 1384, 1067, 1017, 755; HRMS
(APCI) m/z: calcd for C31H24NF: M + H = 430.1966; found:
430.1973.
(d, J = 8.4 Hz, 1 H), 7.68 (d, J = 8.4 Hz, 1 H), 7.55−7.59 (m, 1 H),
7.39−7.43 (m, 1 H), 7.18−7.28 (m, 11 H), 6.94 (s, 1 H), 6.21 (s, 1
H), 4.45 (s, 3 H), 2.84 (s, 3 H), 2.15 (s, 3 H); 13C NMR (100 MHz,
CDCl3): 141.4, 140.3, 139.6, 138.4, 134.7, 132.7, 131.8, 131.4, 130.2,
129.2128.9, 128.3, 127.8, 127.4, 126.6, 126.2, 125.1, 124.7, 124.4,
122.8, 121.6, 120.7, 119.8, 118.6, 38.6, 21.2, 20.5; IR (neat, cm−1):
2921, 1598, 1448, 1383, 1102, 1070, 1025, 759, 700; HRMS (APCI)
m/z: calcd for C31H25N: M + H = 412.2060; found: 412.2072.
3l (mixture, total yield: 72%, 56 mg) 1H NMR (300 MHz, CDCl3):
δ 8.82 (d, J = 9.0 Hz, 0.4 H), 8.64 (d, J = 9.0 Hz, 1 H), 7.64−7.73 (m,
1.4 H), 7.45−7.62 (m, 3.6 H), 7.42−7.43 (m, 3.7 H), 7.09−7.40 (m,
16.6 H), 6.90−6.95 (m, 2 H), 6.63−6.67 (m, 2 H), 4.88−4.95 (m, 2
H), 4.45 (s, 1.3 H), 1.75 (t, J = 7.4 Hz, 3 H); 13C NMR (75 MHz,
CDCl3): 140.4, 140.3, 139.6, 134.9, 133.9, 132.7, 131.8, 130.9, 130.2,
128.5, 128.3, 127.9, 127.4, 126.7, 126.2, 125.0, 124.8, 124.7, 124.4,
123.2, 122.0, 121.9, 121.8, 121.4, 119.3, 117.9, 108.7, 108.5, 40.8, 34.4,
15.1; IR (neat, cm−1): 2921, 1600, 1441, 1382, 1069, 1026, 768, 700;
HRMS (APCI) m/z: calcd for C30H23N: M + H = 398.1903; found:
398.1908; calcd for C29H21N: M + H = 384.1747; found: 384.1752.
11-Methyl-5,6-di-p-tolyl-11H-benzo[a]carbazole 3m (68%, 56 mg),
5-(4-Methoxyphenyl)-11-methyl-6-phenyl-11H-benzo[a]carbazole
with 6-(4-methoxyphenyl)-11-methyl-5-phenyl-11H-benzo[a]-
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carbazole (3:2) 3s (total yield: 60%, 49 mg), H NMR (400 MHz,
CDCl3): δ 8.79 (d, J = 8.0 Hz, 1 H), 7.68−7.74 (m, 1 H), 7.55−7.59
(m, 1 H), 7.50−7.57 (m, 1 H), 7.40−7.44 (m, 2 H), 7.09−7.43 (m, 8
H), 6.92−6.97 (m, 1 H), 6.79−6.83 (m, 1 H), 6.75−6.77 (m, 1 H),
4.43 (s, 3 H), 3.79 (s, 1.8 H), 3.76 (m, 1.2 H); 13C NMR (100 MHz,
CDCl3): 158.2, 157.9, 141.2, 140.4, 139.8, 135.1, 134.5, 133.1, 132.8,
132.7, 132.6, 131.8, 131.4, 131.2, 130.6, 130.2, 128.3, 127.9, 127.5,
126.7, 126.1, 124.8, 124.7, 124.6, 124.4, 123.2, 123.1, 122.1, 121.9,
121.8, 119.2, 118.1, 113.3, 112.9, 108.7, 55.1, 34.4; IR (neat, cm−1):
2919, 1604, 1509, 1243, 1028, 745, 701; HRMS (APCI) m/z: calcd for
C30H23NO: M + H = 414.1852; found: 414.1856.
5-(4-Methoxyphenyl)-11-methyl-6-(4-nitrophenyl)-11H-benzo[a]-
carbazole with 6-(4-methoxyphenyl)-11-methyl-5-(4-nitrophenyl)-
11H-benzo[a]carbazole (2:1) 3t (total yield: 78%, 71 mg); 1H
NMR (400 MHz, CDCl3): δ 8.80−8.84 (m, 1 H), 8.06−8.13 (m, 2
H), 7.72−7.74 (m, 0.4 H), 7.59−7.65 (m, 1 H), 7.53−7.56 (m, 1.8 H),
7.43−7.48 (m, 2.2 H), 7.39−7.41 (m, 0.7 H), 7.28−7.36 (m, 1.5 H),
7.01−7.06 (m, 1.5 H), 6.93−6.99 (m, 1.9 H), 6.74−6.79 (m, 2.9 H),
6.59−6.61 (m, 0.4 H), 4.44 (s, 3 H), 3.80 (s, 2 H), 3.77 (s, 1 H); 13C
NMR (100 MHz, CDCl3): 158.6, 158.2, 147.9, 147.6, 146.7, 146.3,
141.2, 141.1, 135.5, 134.7, 132.8, 132.7, 132.5, 131.7, 131.5, 131.3,
131.0, 130.7, 130.6, 128.9, 128.4, 127.4, 125.3, 125.2, 125.0, 124.7,
123.2, 123.0, 122.8, 122.4, 122.2, 121.9, 121.8, 121.3, 119.6, 119.5,
117.9, 113.6, 113.2, 109.1, 108.9, 55.1, 34.4; IR (neat, cm−1): 2920,
1596, 1512, 1344, 1244, 1028, 744; HRMS (APCI) m/z: calcd for
C30H22N2O3: M + H = 459.1703; found: 459.1720.
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mp = 182−184 °C; H NMR (400 MHz, CDCl3): δ 8.79 (d, J = 8.4
Hz, 1 H), 7.69 (d, J = 8.4 Hz, 1 H), 7.49−7.58 (m, 2 H), 7.35−7.42
(m, 2 H), 7.04−7.14 (m, 8 H), 6.91−6.95 (m, 1 H), 6.67−6.69 (m, 1
H), 4.42 (s, 3 H), 2.36 (s, 3 H), 2.32 (s, 3 H); 13C NMR (100 MHz,
CDCl3): 141.2, 137.3, 136.6, 136.0, 135.5, 135.0, 134.9, 133.0, 131.6,
131.1, 129.9, 128.7, 128.4, 128.2, 124.7, 124.6, 124.3, 123.2, 122.1,
122.0, 121.9, 119.1, 118.0, 108.7, 34.4, 21.4, 21.2; IR (neat, cm−1):
2919, 1599, 1460, 1429, 1383, 1068, 1025, 757; HRMS (APCI) m/z:
calcd for C31H25N: M + H = 412.2060; found: 412.2075.
5,6-Bis(4-chlorophenyl)-11-methyl-11H-benzo[a]carbazole 3n
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(70%, 63 mg), mp > 250 °C; H NMR (400 MHz, CDCl3): δ 8.76
(d, J = 8.4 Hz, 1 H), 7.56−7.62 (m, 2 H), 7.49−7.51 (m, 1 H), 7.37−
7.44 (m, 2 H), 7.24−7.26 (m, 2 H), 7.19−7.22 (m, 2 H), 7.08−7.10
(m, 2 H), 7.03−7.05 (m, 2 H), 6.95−6.99 (m, 1 H), 6.68−6.70 (m, 1
H), 4.38 (s, 3 H); 13C NMR (100 MHz, CDCl3): 141.1, 138.4, 137.8,
135.2, 133.6, 132.9, 132.4, 131.5, 129.7, 128.4, 127.9, 125.1, 125.0,
124.6, 122.8, 122.2, 121.9, 121.7, 119.5, 117.3, 108.9, 34.3; IR (neat,
cm−1): 2923, 1489, 1090, 1017, 760; HRMS (APCI) m/z: calcd for
C29H19NCl2: M + H = 452.0967; found: 452.0986.
2,3,11-Trimethyl-5,6-diphenyl-11H-benzo[a]carbazole with 3,4,11-
trimethyl-5,6-diphenyl-11H-benzo[a]carbazole (1:1) 3u (total yield:
1
60%, 49 mg), mp = 216−218 °C; H NMR (400 MHz, CDCl3): δ
3-Fluoro-6,11-dimethyl-5-phenyl-11H-benzo[a]carbazole 3o (45%,
8.54−8.57 (m, 1 H), 7.40−7.50 (m, 3 H), 7.06−7.37 (m, 10 H), 6.87−
6.92 (m, 1 H), 6.63 (d, J = 8.0 Hz, 0.5 H), 6.46 (d, J = 8.0 Hz, 0.5 H),
4.42 (s, 1.5 H), 4.37 (s, 1.5 H), 2.52 (s, 1.5 H), 2.40 (s, 1.5 H), 2.32 (s,
1.5 H), 1.88 (s, 1.5 H); 13C NMR (100 MHz, CDCl3): 143.4, 141.7,
141.1, 140.9, 140.5, 139.8, 136.5, 135.9, 135.0, 134.8, 134.6, 134.4,
134.1, 134.0, 132.5, 131.9, 131.8, 131.6, 130.4, 130.3, 130.2, 127.9,
127.8, 127.7, 127.5, 127.4, 126.8, 126.6, 126.4, 126.1, 125.4, 124.2,
124.0, 123.3, 123.2, 122.0, 121.9, 121.8, 121.7, 120.6, 120.0, 119.3,
119.0, 117.2, 116.9, 108.8, 108.6, 34.8, 34.3, 21.6, 20.7, 20.3; IR (neat,
cm−1): 2919, 2858, 1600, 1446, 1383, 1069, 1025, 753, 701; HRMS
(APCI) m/z: calcd for C31H25N: M + H = 412.2060; found: 412.2066.
2,11-Dimethyl-5,6-diphenyl-11H-benzo[a]carbazole with 4,11-di-
methyl-5,6-diphenyl-11H-benzo[a]carbazole (2:1) 3v (total yield:
1
30 mg), mp = 174−175 °C; H NMR (400 MHz, CDCl3): δ 8.70−
8.74 (m, 1 H), 8.33 (d, J = 8.0 Hz, 1 H), 7.59−7.61 (m, 1 H), 7.50−
7.55 (m, 3 H), 7.45−7.49 (m, 1 H), 7.25−7.34 (m, 4 H), 7.15−7.19
(m, 1 H), 4.41 (s, 3 H), 2.74 (s, 3 H); 13C NMR (100 MHz, CDCl3):
141.0, 140.1, 135.2, 131.2, 128.5, 127.1, 124.2, 124.1, 123.7, 122.4,
119.7, 117.9, 113.5, 113.3, 111.9, 111.6, 108.9, 34.4, 19.2; IR (neat,
cm−1): 2921, 1598, 1467, 1450, 1102, 1068, 1029, 769; HRMS (APCI)
m/z: calcd for C24H18NF: M + H = 340.1496; found: 340.1498.
(11-Methyl-5-phenyl-11H-benzo[a]carbazole-6-yl)methanol 3p
1
(40%, 27 mg), mp = 170−171 °C; H NMR (400 MHz, CDCl3): δ
8.77 (d, J = 8.4 Hz, 1 H), 8.43−8.75 (m, 1 H), 7.48−7.62 (m, 7 H),
7.34−7.43 (m, 4 H), 5.05−5.06 (m, 2 H), 4.43 (s, 3 H), 1.69 (s, 1 H);
13C NMR (100 MHz, CDCl3): 141.2, 139.3, 135.9, 132.7, 132.2, 131.1,
130.7, 128.7, 128.3, 127.3, 125.1, 124.8, 124.7, 122.5, 122.3, 122.2,
122.0, 120.1, 117.2, 109.1, 61.2, 34.4; IR (neat, cm−1): 3394, 2922,
1599, 1466, 1382, 1025, 755, 700; HRMS (APCI) m/z: calcd for
C24H19NO: M + H = 338.1539; found: 338.1548.
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64%, 50 mg), H NMR (400 MHz, CDCl3): δ 8.72−8.74 (m, 0.5
H), 8.58 (s, 1 H), 7.36−7.61 (m, 5 H), 7.09−7.31 (17.5 H), 6.88−6.94
(m, 1.7 H), 6.65 (d, J = 8.0 Hz, 1 H), 6.44 (d, J = 8.0 Hz, 0.5 H), 4.47
(s, 3 H), 4.43 (s, 1.5 H), 2.63 (s, 3 H); 13C NMR (100 MHz, CDCl3):
141.2, 140.3, 139.7, 137.1, 134.8, 134.3, 133.9, 132.1, 131.8, 131.2,
130.9, 130.3, 128.2, 127.9, 127.7, 127.4, 126.8, 126.7, 126.4, 126.2,
125.9, 124.5, 124.3, 123.2, 123.1, 122.1, 121.9, 121.4, 121.1, 119.3,
119.1, 117.8, 108.9, 108.7, 34.5, 22.2; IR (neat, cm−1): 2919, 1598,
1437, 1384, 1068, 1025, 758, 700; HRMS (APCI) m/z: calcd for
C30H23N: M + H = 398.1903; found: 398.1908.
3,11-Dimethyl-5,6-di-p-tolyl-11H-benzo[a]carbazole 3q (62%, 52
mg), mp = 218−219 °C; 1H NMR (400 MHz, CDCl3): δ 8.67 (d, J =
8.8 Hz, 1 H), 7.47−7.49 (m, 2 H), 7.33−7.40 (m, 2 H), 7.04−7.13 (m,
8 H), 6.89−6.94 (m, 1 H), 6.64−6.66 (m, 1 H), 4.39 (s, 3 H), 2.41 (s,
3 H), 2.36 (s, 3 H), 2.32 (s, 3 H); 13C NMR (100 MHz, CDCl3):
141.0, 137.5, 136.7, 135.9, 135.4, 135.2, 135.0, 134.3, 133.3, 131.6,
130.6, 129.9, 128.6, 128.2, 127.5, 126.5, 124.0, 123.4, 121.9, 119.9,
119.1, 117.4, 108.6, 34.3, 21.8, 21.4, 21.3; IR (neat, cm−1): 2920, 1469,
1381, 1330, 1113, 1024, 814, 753; HRMS (APCI) m/z: calcd for
C32H27N: M + H = 426.2216; found: 426.2223.
4-(3-Methoxy-5,6-diphenyl-11H-benzo[a]carbazol-11-yl)butyl piva-
late 3w (55%, 61 mg), mp > 250 °C; 1H NMR (400 MHz, CDCl3): δ
8.47−8.49 (m, 1 H), 7.48−7.51 (m, 1 H), 7.33−7.36 (m, 1 H), 7.18−
7.29 (m, 11 H), 7.06 (s, 1 H), 6.89−6.93 (m, 1 H), 6.58−6.60 (m, 1
H), 4.83−4.87 (m, 2 H), 4.18−4.21 (m, 2 H), 3.70 (s, 3 H), 2.19−2.27
G
dx.doi.org/10.1021/jo301741j | J. Org. Chem. XXXX, XXX, XXX−XXX