European Journal of Organic Chemistry
10.1002/ejoc.201600982
1
9
1
26.7, 124.7 (d, J = 6.3 Hz), 124.5, 121.2 (d, J = 2.5 Hz), 121.0 (d, J = 13.8
121.3 (d, J = 3.8 Hz), 119.5 (d, J = 5.0 Hz); F NMR (CDCl
3
, 376 MHz): δ
1
9
+
Hz), 116.7 (d, J = 6.3 Hz), 35.4, 31.2; F NMR (CDCl
3
, 376 MHz): δ -
-128.6 (s); GC-MS (EI, 70 eV): m/z (%) = 358 (11) [M ]; HRMS (EI) for
+
1
29.1 (s); GC-MS (EI, 70 eV): m/z (%) = 304 (12) [M ]; HRMS (EI) for
C
23
H
12ClFO: calcd. 358.0561, found 358.0554.
C
21
H
17FO: calcd. 304.1263, found 304.1258.
5-(tert-butyl)-7-(3-chlorophenyl)-11H-benzo[b]fluoren-11-one
(3i):
-
1
5
-fluoro-9-methyl-11H-benzo[b]fluoren-11-one (2e): Yellow solid (31.5
Yellow solid (68.5 mg, 57.5%); m.p. 159−160 ºC; IR (KBr, cm ): ν =
-
1
1
1
mg, 40%); m.p. 185−186 ºC; IR (KBr, cm ): ν = 1707 (C=O); H NMR
500 MHz, CDCl ): δ 8.20 (s, 1H), 7.97(d, J = 8.5 Hz, 1H), 7.90 (d, J = 7.5
Hz, 1H), 7.78 (d, J = 7.5 Hz, 1H), 7.62−7.59 (m, 1H), 7.51 (t, J = 7.5 Hz,
1707(C=O); H NMR (500 MHz, CDCl
3
): δ 8.45 (s, 1H), 8.04 (s, 1H), 7.90
(
3
(d, J = 8.0 Hz, 2H), 7.80 (d, J = 7.0 Hz, 1H), 7.67 (t, J = 7.5 Hz, 1H),
7.61−7.56 (m, 3H), 7.45 (t, J = 7.5 Hz, 1H), 7.41−7.39 (m, 1H), 7.33 (t, J =
1
3
13
1
1
H), 7.38 (t, J = 7.5 Hz, 2H), 2.73 (s, 3H); C NMR (125 MHz, CDCl
3
): δ
7.5 Hz, 1H), 1.86 (s, 9H); C NMR (125 MHz, CDCl
3
): δ 192.8, 148.1,
92.5 (d, J = 2.5 Hz), 153.3 (d, J = 257.5 Hz), 142.2 (d, J = 2.5 Hz), 137.8
145.9, 143.1, 138.3, 138.0, 137.7, 136.4, 135.0, 134.8, 133.7, 133.4, 131.2,
(
d, J = 2.5 Hz), 135.9, 135.4, 134.3 (d, J = 3.75 Hz), 133.2 (d, J = 6.3 Hz),
29.1, 129.0 (d, J = 1.3 Hz), 128.9, 128.4 (d, J = 15.0 Hz), 124.8 (d, J = 6.3
Hz), 124.6, 120.6 (d, J = 13.8 Hz), 119.6 (d, J = 6.3 Hz), 118.1 (d, J = 2.5
130.3, 129.0, 128.2, 127.8, 127.5, 126.3, 125.5, 125.0, 124.2, 123.2, 37.7,
+
1
33.1; GC-MS (EI, 70 eV): m/z (%) = 396 (10) [M ]; HRMS (EI) for
27
C H21ClO: calcd. 396.1281, found 396.1274.
19
Hz), 19.7; F NMR (CDCl
3
, 376 MHz): δ -127.7 (s); GC-MS (EI, 70 eV):
11FO: calcd. 262.0794, found
7-(4-chlorophenyl)-5-fluoro-11H-benzo[b]fluoren-11-one (2j): Yellow
+
-1
m/z (%) = 262 (35) [M ]; HRMS (EI) for C18
H
solid (20.3 mg, 18.9%); m.p. 226−227 ºC; IR (KBr, cm ): ν = 1703(C=O);
1
2
62.0785.
-fluoro-9-(m-tolyl)-11H-benzo[b]fluoren-11-one (2f): Yellow solid (56.8
3
H NMR (500 MHz, CDCl ): δ 8.26 (s, 1H), 8.05 (s, 1H), 7.99 (d, J = 8.5
5
Hz, 1H), 7.95 (d, J = 7.5 Hz, 1H), 7.80 (d, J = 7.0 Hz, 1H), 7.76 (dd, J
8.5 Hz, J = 1.5 Hz, 1H), 7.77−7.68 (m, 2H), 7.65−7.62 (m, 1H), 7.52−7.50
3
(m, 2H), 7.42−7.39 (m, 1H); C NMR (125 MHz, CDCl ): δ 192.0, 153.1
1
=
-1
1
mg, 56%); m.p. 184−185 ºC; IR (KBr, cm ): ν = 1707 (C=O); H NMR
500 MHz, CDCl ): δ 8.09 (d, J =8.5 Hz, 1H), 8.07 (s, 1H), 7.90(d, J = 7.5
2
13
(
3
Hz, 1H), 7.74 (d, J = 7.5 Hz, 1H), 7.64 (t, J = 8.0 Hz, 1H), 7.59 (t, J = 7.5
Hz, 1H), 7.46 (d, J = 7.0 Hz, 1H), 7.42 (t, J = 7.5 Hz, 1H), 7.35 (t, J = 7.0
(d, J = 258.8 Hz), 152.8, 142.0, 140.9, 138.5, 135.9, 135.4, 134.5, 134.3 (d,
J = 3.8 Hz), 131.3 (d, J = 2.5 Hz), 129.3, 128.7, 128.6 (d, J = 16.3 Hz),
128.5, 127.1, 124.9 (d, J = 5.0 Hz), 124.7, 121.4 (d, J = 2.5 Hz), 120.3 (d, J
13
Hz, 1H), 7.30 (d, J = 7.5 Hz, 1H), 7.26−7.24 (m, 2H), 2.48(s, 3H);
NMR (125 MHz, CDCl ): δ 192.2 (d, J = 2.5 Hz), 153.0 (d, J = 158.8 Hz),
43.7 (d, J = 2.5 Hz), 141.9 (d, J = 1.3 Hz), 139.5, 138.3, 135.9, 135.3,
C
19
3
= 15 Hz), 119.2 (d, J = 5.0 Hz); F NMR (CDCl
3
, 376 MHz): δ -128.7 (s);
+
1
1
1
5
GC-MS (EI, 70 eV): m/z (%) = 358 (13) [M ]; HRMS (EI) for C23
calcd. 358.0561, found 358.0569.
H12FO:
33.5 (d, J = 3.8 Hz), 133.4 (d, J = 5.0 Hz), 130.5, 129.1, 128.9, 128.7,
28.6 (d, J = 1.3 Hz), 128.49 (d, J = 16.3 Hz), 128.48, 127.0, 124.8 (d, J =
.0 Hz), 124.6, 120.56, 120.55 (d, J = 13.8 Hz), 120.3 (d, J = 3.8 Hz), 21.5;
5-(tert-butyl)-7-(4-chlorophenyl)-11H-benzo[b]fluoren-11-one
(3j):
-
1
Yellow solid (56.1 mg, 47.1%); m.p. 207−208 ºC; IR (KBr, cm ): ν = 1705
1
9
1
F NMR (CDCl
3
, 376 MHz): δ -127.9 (s);GC-MS (EI, 70 eV): m/z (%) =
(C=O); H NMR (500 MHz, CDCl
3
): δ 8.46 (s, 1H), 8.06 (s, 1H), 7.92−7.89
+
3
38 (23) [M ]; HRMS (EI) for C24H15FO: calcd. 338.1107, found 338.1115.
(m, 2H), 7.81 (d, J = 7.0 Hz, 1H), 7.64−7.61 (m, 3H), 7.57 (t, J = 7.5 Hz,
1
3
5
-fluoro-7-(p-tolyl)-11H-benzo[b]fluoren-11-one (2g): Yellow solid (62.9
1H), 7.50 (d, J = 8.5 Hz, 2H), 7.34 (t, J = 7.5 Hz, 1H), 1.86 (s, 9H);
C
-
1
1
mg, 62%); m.p. 186−187 ºC; IR (KBr, cm ): ν = 1707 (C=O); H NMR
500 MHz, CDCl ): δ 8.28 (s, 1H), 8.04 (s, 1H), 7.98 (d, J = 8.0 Hz, 1H),
.94 (d, J = 7.5 Hz, 1H), 7.80 (dd, J = 8.0 Hz, J = 1.5 Hz, 2H), 7.66 (d, J
8.0 Hz, 2H), 7.64−7.60 (m, 1H), 7.41−7.38 (m, 1H), 7.34 (d, J = 8.0 Hz,
NMR (125 MHz, CDCl ): δ 192.9, 148.1, 145.9, 139.7, 138.4, 138.1, 138.0,
3
(
3
136.4, 134.7, 134.0, 133.7, 133.3, 131.2, 129.2, 129.0, 128.6, 128.2, 126.1,
7
1
2
125.0, 124.2, 123.3, 37.7, 33.1; GC-MS (EI, 70 eV): m/z (%) = 396 (12)
+
=
[M ]; HRMS (EI) for C27
H21ClO: calcd. 396.1281, found 396.1276.
13
2
H), 2.46 (s, 3H); C NMR (125 MHz, CDCl
Hz), 149.9, 142.1, 138.3, 137.2, 135.9, 135.3, 134.0 (d, J = 3.8 Hz), 133.5
d, J = 5.0 Hz), 131.1 (d, J = 2.5 Hz), 129.8, 129.1, 128.6 (d, J = 16.3 Hz),
3
): δ 192.1, 153.2 (d, J = 258.8
7-(4-(tert-butyl)phenyl)-5-fluoro-11H-benzo[b]fluoren-11-one
(2k):
-
1
Yellow soild (57.8 mg, 48%); m.p. 178−179 ºC; IR (KBr, cm ): ν = 1706
1
(
(C=O); H NMR (500 MHz, CDCl
3
): δ 8.29 (s, 1H), 8.03 (s, 1H), 7.97 (d, J
1
27.3, 127.3, 124.9 (d, J = 5.0 Hz), 124.6, 121.4 (d, J = 2.5 Hz), 121.3 (d, J
= 8.5 Hz, 1H), 7.93 (d, J = 7.5 Hz, 1H), 7.81−7.80 (m, 2H), 7.72−7.69 (m,
1
9
=
13.8 Hz), 118.9 (d, J = 5.0 Hz), 21.2; F NMR (CDCl
3
, 376 MHz): δ -
2H), 7.63−7.59 (m, 1H), 7.58−7.55 (m, 2H), 7.40−7.37 (m, 1H), 1.41 (s,
+
13
1
28.8 (s); GC-MS (EI, 70 eV): m/z (%) = 338 (21) [M ]; HRMS (EI) for
9H); C NMR (125 MHz, CDCl
3
): δ 192.1 (d, J = 2.5 Hz), 153.2 (d, J =
C
24
H
15FO: calcd. 338.1107, found 338.1113.
258.8 Hz), 151.5, 142.1 (d, J = 1.3 Hz), 142.0 (d, J = 1.3 Hz), 137.1, 135.9,
135.3, 134.0 (d, J = 3.8 Hz), 133.5 (d, J = 5.0 Hz), 131.1 (d, J = 2.5 Hz),
129.1, 128.5 (d, J = 15.0 Hz), 127.4, 127.1, 126.1, 124.8 (d, J = 5.0 Hz),
124.6, 121.4 (d, J = 2.5 Hz), 121.3 (d, J = 13.8 Hz), 119.0 (d, J = 5.0 Hz),
5
-fluoro-7-(m-tolyl)-11H-benzo[b]fluoren-11-one (2h): Yellow solid
-
1
1
(
67.0 mg, 66%); m.p. 180−181 ºC; IR (KBr, cm ): ν = 1708 (C=O); H
NMR (500 MHz, CDCl ): δ 8.25(s, 1H), 8.00(s, 1H), 7.94 (d, J = 8.5 Hz,
H), 7.90 (d, J = 7.5 Hz, 1H), 7.77 (d, J = 7.0 Hz, 2H), 7.59 (t, J = 7.5 Hz,
H), 7.54 (d, J = 8.5 Hz, 2H), 7.42 (t, J = 7.5 Hz, 1H), 7.37 (t, J = 7.5 Hz,
3
19
1
1
1
1
34.7, 31.4; F NMR (CDCl
3
, 376 MHz): δ -128.8 (s); GC-MS (EI, 70 eV):
+
m/z (%) = 380 (11) [M ]; HRMS (EI) for C27
H21FO: calcd. 380.1576, found
1
3
H), 7.26 (d, J = 8.0 Hz, 1H), 2.49 (s, 3H); C NMR (125 MHz, CDCl
3
): δ
380.1570.
92.0 (d, J = 1.3 Hz), 153.1 (d, J = 258.8 Hz), 142.2 (d, J = 1.3 Hz), 142.0
5-(tert-butyl)-7-(4-(tert-butyl)phenyl)-11H-benzo[b]fluoren-11-one (3k):
-
1
(
d, J = 1.3 Hz), 140.0, 138.7, 135.9, 135.3, 134.1 (d, J = 3.8 Hz), 133.5 (d, J
5.0 Hz), 131.0 (d, J = 2.5 Hz), 129.1, 129.01, 129.0, 128.4 (d, J = 15.0
Hz), 128.2, 127.4, 124.84, 124.79, 124.6, 121.4, 121.3 (d, J = 16.3 Hz),
Yellow solid (20.1 mg, 16%); m.p. 163−164 ºC; IR (KBr, cm ): ν =
1
=
1704(C=O); H NMR (500 MHz, CDCl
3
): δ 8.51(s, 1H), 8.07 (s, 1H), 7.91
(d, J = 8.0 Hz, 2H), 7.81 (d, J = 7.0 Hz, 1H), 7.69−7.66 (m, 3H), 7.58−7.55
19
13
1
19.2 (d, J = 5.0 Hz), 21.6; F NMR (CDCl
3
, 376 MHz): δ -128.7 (s);GC-
15FO: calcd.
(m, 3H), 7.33 (t, J = 7.0 Hz, 1H), 1.87 (s, 9H), 1.41 (s, 9H); C NMR (125
+
MS (EI, 70 eV): m/z (%) = 338 (25) [M ]; HRMS (EI) for C24
H
3
MHz, CDCl ): δ 193.1, 150.1, 148.2, 145.9, 139.1, 138.21, 138.15, 138.1,
3
38.1107, found 338.1116.
-(3-chlorophenyl)-5-fluoro-11H-benzo[b]fluoren-11-one (2i): Yellow
136.5, 134.4, 133.6, 133.0, 131.0, 129.0, 128.1, 127.1, 126.03, 125.98,
7
125.4, 124.1, 123.4, 37.7, 34.7, 33.1, 31.4; GC-MS (EI, 70 eV): m/z (%) =
-
1
+
solid (12.4 mg, 11.5%); m.p. 211−212 ºC; IR (KBr, cm ):
ν
=
418 (7) [M ]; HRMS (EI) for C31
H30O: calcd. 418.2297, found 418.2289.
1
1
8
7
706(C=O); H NMR (500 MHz, CDCl
3
): δ 8.29 (s, 1H), δ 8.06 (s, 1H),
5-fluoro-9-phenyl-11H-benzo[b]fluoren-11-one (2l): Yellow solid (28.2
-
1
1
.02 (d, J = 7.5 Hz, 1H), 7.97 (d, J = 7.5 Hz, 1H), 7.81 (d, J = 7.5 Hz, 1H),
.78−7.74 (m, 2H), 7.65−7.62 (m, 2H), 7.47 (t, J = 7.5 Hz, 1H), 7.44−7.40
mg, 29%); m.p. 230−231 ºC; IR (KBr, cm ): ν = 1707 (C=O); H NMR
(500 MHz, CDCl ): δ 8.12 (d, J = 8.0 Hz, 1H), 8.07 (s, 1H), 7.92 (d, J = 7.5
Hz, 1H), 7.75 (d, J = 7.0 Hz, 1H), 7.67−7.64 (m, 1H), 7.61−7.58 (m, 1H),
3
13
(m, 2H); C NMR (125 MHz, CDCl
3
): δ 192.0, 153.1 (d, J = 260.0 Hz),
13
1
3
1
50.1, 142.0 (d, J = 6.3 Hz), 140.7, 139.8, 135.9, 135.5, 135.1, 134.4 (d, J =
3
7.56−7.45 (m, 6H), 7.36 (t, J = 7.5 Hz, 1H); C NMR (125 MHz, CDCl ): δ
.8 Hz), 131.3 (d, J = 2.5 Hz), 130.3, 129.3, 128.5 (d, J = 15.0 Hz), 128.3,
27.6, 127.1, 125.6, 124.9 (d, J = 5.0 Hz), 124.7, 121.6 (d, J = 13.8 Hz),
192.1 (d, J = 1.3 Hz), 153.1 (d, J = 258.8 Hz), 143.6 (d, J = 2.5 Hz), 142.0
(d, J = 2.5 Hz), 139.6, 136.0, 135.3, 133.5 (d, J = 6.3 Hz), 133.4 (d, J = 3.8
Submitted to the European Journal of Organic Chemistry
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