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7.84 (d, J = 7.3 Hz, 1H), 7.99 (s, 1H); 13C NMR (100 MHz, CDCl3) δ
31.4, 34.5, 36.7, 118.5, 119.9, 125.1, 125.2, 125.7, 125.8, 126.76,
126.80, 126.9, 138.7, 140.0, 141.6, 142.0, 142.2, 143.6, 150.2; HRMS
m/z calcd for C23H22 (M+) 298.1722, found 298.1724.
2H), 7.25 (d, J = 8.1 Hz, 2H), 7.44 (s, 2H); 13C NMR (100 MHz,
CDCl3) δ 21.0, 21.6, 83.0, 120.6, 124.4, 125.3, 128.8, 129.0, 136.6,
138.8, 139.7, 140.6, 148.2; HRMS m/z calcd for C22H20O (M+)
300.1514, found 300.1512.
3-Methoxy-9H-fluorene (2g):19 mp 79−80 °C, 61 mg (62%); H
1
9-(2-Methylphenyl)-9H-fluoren-9-ol (4g):23 mp 117−118 °C, 43
mg (32%); 1H NMR (400 MHz, CDCl3) δ 1.31 (s, 3H), 2.33 (s, 1H),
6.95 (d, J = 7.3 Hz, 1H), 7.16−7.24 (m, 5H), 7.34−7.39 (m, 3H), 7.68
(d, J = 7.8 Hz, 2H), 8.32 (d, J = 6.9 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 19.4, 82.7, 120.2, 124.3, 125.7, 126.5, 127.5, 128.6, 129.1,
131.4, 135.1, 140.0, 140.2, 149.3; HRMS m/z calcd for C20H16O (M+)
272.1201, found 272.1199.
NMR (400 MHz, CDCl3) δ 3.83 (s, 2H), 3.89 (s, 3H), 6.87 (dd, J =
2.8, 8.2 Hz, 1H), 7.28−7.32 (m, 2H), 7.37 (t, J = 6.4, 7.3 Hz, 1H), 7.43
(d, J = 8.2 Hz, 1H), 7.53 (d, J = 7.3 Hz, 1H), 7.75 (d, J = 7.3 Hz, 1H);
13C NMR (100 MHz, CDCl3) δ 36.1, 55.5, 104.8, 113.2, 119.8, 125.0,
125.5, 126.6, 126.7, 135.3, 141.6, 143.0, 144.3, 159.1; HRMS m/z
calcd for C14H12O (M+) 196.0888, found 196.0890.
11H-Benzo[a]fluorene (2h): mp 183−184 °C (lit.21 mp 177 °C),
54 mg (50%); 1H NMR (400 MHz, CDCl3) δ 4.13 (s, 2H), 7.28−7.32
(m, 1H), 7.39 (t, J = 7.3 Hz, 1H), 7.42−7.46 (m, 1H), 7.49−7.53 (m,
1H), 7.60 (d, J = 7.3 Hz, 1H), 7.83−7.90 (m, 4H), 7.97 (d, J = 8.3 Hz,
1H); 13C NMR (100 MHz, CDCl3) δ 35.6, 118.7, 119.6, 124.1, 124.9,
125.3, 126.3, 126.4, 126.8, 127.8, 128.9, 130.7, 132.8, 138.9, 139.8,
142.6, 143.3; HRMS m/z calcd for C17H12 (M+) 216.0939, found
216.0938.
9-(4-(Trifluoromethyl)phenyl)-9H-fluoren-9-ol (4h)24 + 9-phenyl-
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3-(trifluoromethyl)-9H-fluoren-9-ol (4h′): 106 mg (65%); H NMR
(400 MHz, CDCl3) δ 2.71 (s, 1H), 7.18−7.48 (m, 10H), 7.64 (t, J =
7.2 Hz, 1.27H), 7.86 (s, 0.73H); 13C NMR (100 MHz, CDCl3) δ
83.27, 83.31, 117.0 (q, J = 3.8 Hz), 120.2, 120.5, 124.2 (q, J = 272.8
Hz), 124.7, 124.9, 125.09, 125.12, 125.16, 125.21, 125.3 (q, J = 3.8
Hz), 125.8, 127.5, 128.3, 128.6, 129.1, 129.3, 129.39, 129.42, 131.3 (q,
J = 32.4 Hz), 138.1, 139.5, 140.2, 142.1, 147.3, 149.7, 150.3, 153.8;
HRMS m/z calcd for C20H13F3O (M+) 326.0918, found 326.0921.
9-(4-Methylphenyl)-9H-fluoren-9-ol (4i)24 + 3-methyl-9-phenyl-
9H-fluoren-9-ol (4i′):25 78 mg (57%); 1H NMR (400 MHz, CDCl3) δ
2.27 (s, 1H), 2.39−2.44 (m, 3H), 7.02−7.05 (m, 1.36H), 7.15−7.36
(m, 9H), 7.45 (s, 0.62H), 7.60−7.64 (m, 1.38H); 13C NMR (100
MHz, CDCl3) δ 21.0, 21.5, 83.3, 83.5, 119.9, 120.0, 120.7, 124.5,
124.68, 124.71, 125.25, 125.33, 127.1, 128.1, 128.3, 128.4, 128.88,
128.93, 129.0, 129.2, 136.8, 139.0, 139.5, 139.6, 139.7, 140.2, 143.3,
147.6, 150.5, 150.8; HRMS m/z calcd for C20H16O (M+) 272.1201,
found 272.1205.
11H-Benzo[b]fluorene (2i): mp 198−199 °C (lit.19 mp 207−208
1
°C), 36 mg (33%); H NMR (400 MHz, CDCl3) δ 4.05 (s, 2H),
7.32−7.36 (m, 1H), 7.38−7.48 (m, 3H), 7.55 (d, J = 7.2 Hz, 1H),
7.83−7.85 (m, 1H), 7.90−7.92 (m, 3H), 8.17 (s, 1H); 13C NMR (100
MHz, CDCl3) δ 36.4, 117.8, 120.6, 123.3, 125.25, 125.30, 125.4, 126.9,
127.5, 127.8, 128.1, 133.0, 133.1, 140.5, 141.1, 141.2, 143.7; HRMS m/
z calcd for C17H12 (M+) 216.0939, found 216.0941.
3,9-Di-tert-butyl-6,12-dihydroindeno[1,2-b]fluorene (2j): mp
1
246−247 °C, 26 mg (14%); H NMR (400 MHz, CDCl3) δ 1.41
(s, 18H), 3.92 (s, 4H), 7.34 (dd, J = 1.8, 7.7 Hz, 2H), 7.48 (d, J = 7.7
Hz, 2H), 7.84 (d, J = 1.3 Hz, 2H), 7.95 (s, 2H); 13C NMR (100 MHz,
CDCl3) δ 31.7, 34.8, 36.3, 116.2, 116.3, 123.7, 124.5, 140.8, 140.9,
141.8, 142.7, 149.9; HRMS m/z calcd for C28H30 (M+) 366.2348,
found 366.2346.
12-(Naphthalen-2-yl)-12H-dibenzo[b,h]fluoren-12-ol (4j) + 7-
(naphthalen-2-yl)-7H-dibenzo[b,g]fluoren-7-ol (4j′): 112 mg
(55%); 1H NMR (400 MHz, CDCl3) δ 2.70 (s, 0.43H), 2.82 (s,
0.57H), 7.06 (dd, J = 1.8, 8.7 Hz, 0.43H), 7.11 (dd, J = 1.8, 8.7 Hz,
0.43H), 7.35−7.94 (m, 15H), 8.21−8.22 (m, 1.21H), 8.28 (s, 0.86H),
8.60 (s, 0.43H), 8.86 (d, J = 8.7 Hz, 0.43H); 13C NMR (100 MHz,
CDCl3) δ 82.91, 82.94, 119.2, 122.0, 122.3, 123.5, 123.9, 124.3,
124.35, 124.44, 124.6, 125.8, 125.9, 126.05, 126.09, 126.11, 126.2,
126.5, 126.6, 126.8, 127.4, 127.5, 127.8, 127.87, 127.91, 128.17,
128.22, 128.26, 128.29, 128.59, 128.62, 129.4, 129.5, 130.4, 131.8,
132.5, 132.6, 133.0, 133.1, 133.2, 133.9, 134.2, 134.37, 134.43, 134.7,
137.3, 138.8, 140.6, 141.9, 148.7, 149.3, 149.4; HRMS m/z calcd for
C31H20O (M+) 408.1514, found 408.1512.
9-Phenyl-9H-fluoren-9-ol (4a): mp 91−92 °C (lit.22 mp 90 °C), 90
1
mg (70%); H NMR (400 MHz, CDCl3) δ 2.48 (s, 1H), 7.18−7.37
(m, 11H), 7.65 (d, J = 7.3 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ
83.6, 120.1, 124.8, 125.4, 127.2, 128.2, 128.4, 129.1, 139.5, 143.1,
150.4; HRMS m/z calcd for C19H14O (M+) 258.1045, found 258.1050.
3,6-Dibromo-9-(4-bromophenyl)-9H-fluoren-9-ol (4b): mp 126−
127 °C, 189 mg (76%); 1H NMR (400 MHz, CDCl3) δ 2.51 (s, 1H),
7.11 (d, J = 8.2 Hz, 2H), 7.15−7.18 (m, 2H), 7.35−7.40 (m, 4H), 7.73
(d, J = 1.4 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 82.6, 121.7,
123.6, 123.8, 126.2, 127.0, 131.5, 132.1, 140.2, 140.9, 148.8; HRMS m/
z calcd for C19H11Br3O (M+) 491.8360, found 491.8362.
12H-Dibenzo[b,h]fluoren-12-one (5):26 mp 281−282 °C, 10 mg
(7%); 1H NMR (400 MHz, CDCl3) δ 7.46−7.50 (m, 2H), 7.54−7.58
(m, 2H), 7.86 (d, J = 8.3 Hz, 2H), 7.90 (d, J = 7.8 Hz, 2H), 8.07 (s,
2H), 8.25 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 119.6, 125.7,
126.9, 128.7, 129.0, 130.8, 133.6, 134.3, 137.2, 138.8, 192.8; HRMS m/
z calcd for C21H12O (M+) 280.0888, found 280.0886.
3,6-Dichloro-9-(4-chlorophenyl)-9H-fluoren-9-ol (4c): mp 90−91
°C, 132 mg (73%); 1H NMR (400 MHz, CDCl3) δ 2.60 (s, 1H), 7.14
(d, J = 7.8 Hz, 2H), 7.21−7.23 (m, 6H), 7.56 (d, J = 1.8 Hz, 2H); 13C
NMR (100 MHz, CDCl3) δ 82.4, 120.8, 125.9, 126.7, 128.5, 129.1,
133.4, 135.5, 139.9, 140.5, 148.5; HRMS m/z calcd for C19H11Cl3O
(M+) 359.9875, found 359.9879.
3,6-Difluoro-9-(4-fluorophenyl)-9H-fluoren-9-ol (4d): mp 109−
110 °C, 109 mg (70%); 1H NMR (400 MHz, CDCl3) δ 2.54 (s, 1H),
6.90−6.97 (m, 4H), 7.21 (dd, J = 5.0, 8.2 Hz, 2H), 7.24−7.32 (m,
4H); 13C NMR (100 MHz, CDCl3) δ 82.2, 107.7 (d, J = 24.0 Hz),
115.2 (d, J = 21.0 Hz), 115.8 (d, J = 23.0 Hz), 126.1 (d, J = 8.7 Hz),
127.0 (d, J = 8.6 Hz), 138.2 (d, J = 2.9 Hz), 140.5 (dd, J = 2.9, 8.6 Hz),
146.4 (d, J = 2.8 Hz), 162.2 (d, J = 246.3 Hz), 163.8 (d, J = 247.3 Hz);
HRMS m/z calcd for C19H11F3O (M+) 312.0762, found 312.0766.
3,6-Bis(trifluoromethyl)-9-(4-(trifluoromethyl)phenyl)-9H-fluoren-
ASSOCIATED CONTENT
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S
* Supporting Information
1
Copies of H and 13C NMR spectra of products. This material
AUTHOR INFORMATION
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1
Corresponding Author
9-ol (4e): mp 174−175 °C, 175 mg (76%); H NMR (400 MHz,
CDCl3) δ 2.68 (s, 1H), 7.42 (d, J = 7.8 Hz, 2H), 7.45 (d, J = 8.3 Hz,
2H), 7.55 (d, J = 8.3 Hz, 2H), 7.59 (d, J = 7.8 Hz, 2H), 7.98 (s, 2H);
13C NMR (100 MHz, CDCl3) δ 83.0, 117.8 (q, J = 3.8 Hz), 123.8 (q, J
= 272.2 Hz), 124.0 (q, J = 272.2 Hz), 125.4, 125.6 (q, J = 3.8 Hz),
125.7, 126.6 (q, J = 3.8 Hz), 130.2 (q, J = 32.6 Hz), 132.4 (q, J = 32.6
Hz), 139.0, 145.2, 153.2; HRMS m/z calcd for C22H11F9O (M+)
462.0666, found 462.0663.
Present Address
∥Present address: Department of Chemistry, Graduate School
of Engineering Science, Osaka University, Toyonaka, Osaka
560-8531, Japan
3,6-Dimethyl-9-(4-methylphenyl)-9H-fluoren-9-ol (4f): mp 109−
1
Notes
110 °C, 69 mg (46%); H NMR (400 MHz, CDCl3) δ 2.28 (s, 3H),
2.33 (s, 1H), 2.40 (s, 6H), 7.02−7.06 (m, 4H), 7.17 (d, J = 7.7 Hz,
The authors declare no competing financial interest.
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dx.doi.org/10.1021/jo4000465 | J. Org. Chem. 2013, 78, 1365−1370