1
3
1
1
4
9
32.3, 130.9, 130.8, 129.0, 128.9, 127.0, 125.9, 124.3, 124.3,
-7.00 (m, 1H), 6.62 - 6.58 (m, 1H), 3.95 (s, 3H); C NMR (100
ACCEPTED MANUSCRIPT
24.0, 114.8, 55.4; HRMS (ESI-TOF) m/z calcd for C H BrO ,
MHz, CDCl ) (δ, ppm) 193.3, 159.6, 145.3, 145.0, 139.6, 136.6,
135. 8, 134.5, 132.7, 131.9, 130.5, 130.4, 129.7, 128.3, 124.4,
124.1, 123.1, 118.7, 114.5, 55.4; HRMS (ESI-TOF) m/z calcd for
24
16
2
3
+
17.0308 [M+H] ; found 417.0325 .
-Bromo-6-chloro-5-(4-methoxyphenyl)-11H-
+
benzo[b]fluoren-11-one (2g)o
Yellow solid, mp 240-242 C; IR (KBr, ν, cm ) 3005, 1715,
1
C
22
H
15
O
2
S, 343.0788 [M+H] ; found 343.0801.
-1
7-Chloro-5-phenyl-11H-benzo[b]fluoren-11-one (2m)
1
o
-1
628, 1172, 963, 674; H NMR (400 MHz, CDCl ) (δ, ppm) 8.74
Yellow solid, mp 223-224 C; IR (KBr, ν, cm ) 3060, 1708,
3
1
(
8
(
s, 1H), 7.76 - 7.74 (m, 1H), 7.66 (d, J = 8.4 Hz, 1H), 7.37 (d, J =
.0 Hz, 1H), 7.28 - 7.26 (m, 1H), 7.26 - 7.23 (m, 2H), 7.22 - 7.18
m, 1H), 7.07 - 7.05 (m, 2H), 6.07 (d, J = 7.6 Hz, 1H), 3.96 (s,
1539, 1189, 949, 622; H NMR (400 MHz, CDCl ) (δ, ppm) 8.20
(s, 1H), 7.89-7.86 (m, 1H), 7.75 - 7.73 (m, 1H), 7.64 - 7.61 (m,
3H), 7.44 - 7.38 (m, 4H), 7.25 - 7.18 (m, 2H), 6.32-6.30 (m, 1H);
C NMR (100 MHz, CDCl ) (δ, ppm) 192.8, 144.7, 137.8,
136.6, 136.5, 135.3, 134.8, 133.8, 132.8, 132.0, 131.7, 129.6,
129.5, 129.0, 128.7, 127.6, 126.2, 124.8, 124.38, 124.0; HRMS
(ESI-TOF) m/z calcd for C H ClO, 341.0728 [M+H] ; found
3
13
13
3
1
1
5
H); C NMR (100 MHz, CDCl ) (δ, ppm) 192.4, 159.7, 145.0,
3
3
39.4, 136.4, 135.1, 134.5, 134.2, 134.1, 133.4, 132.83, 132.7,
31.1, 131.0, 130.8, 129.3, 125.2, 125.1, 124.9, 124.3, 114.2,
5.4; HRMS (ESI-TOF) m/z calcd for C H BrClO , 450.9918
+
24
14
2
23 14
+
[
M+H] ; found 450.9937.
341.0745.
7
-Chloro-5-(4-methoxyphenyl)-11H-benzo[b]fluoren-11-one
7,9-Dichloro-5-phenyl-11H-benzo[b]fluoren-11-one (2n)
o
-1
(2h)
Yellow solid, mp 230-232 C; IR (KBr, ν, cm ) 3051, 1712,
o
-1
1
Yellow solid, mp 233-234 C; IR (KBr, ν, cm ) 3068, 1703,
1
1632, 1190, 919, 652; H NMR (400 MHz, CDCl ) (δ, ppm) 8.65
3
1
624, 1178, 950, 628; H NMR (400 MHz, CDCl ) (δ, ppm) 8.16
(d, J = 0.8Hz, 1H), 7.77-7.74 (m, 1H), 7.65-7.63 (m, 3H), 7.55
(d, J = 2.0 Hz, 1H), 7.39 -7.36 (m, 2H), 7.34 -7.33 (m, 1H), 7.30-
7.26 (m, 1H), 7.23 - 7.19 (m, 1H), 6.29 (d, J = 7.2 Hz, 1H); C
3
(s, 1H), 7.85 (d, J = 8.4 Hz, 1H), 7.74-7.72 (m, 1H), 7.45 (d, J =
1
3
2
2
.0 Hz, 1H), 7.42-7.39 (m, 1H), 7.30-7.28 (m, 2H), 7.25-7.20 (m,
13
H), 7.17-7.13 (m, 2H), 6.45-6.42 (m, 1H), 3.98 (s, 3H);
C
NMR (100 MHz, CDCl ) (δ, ppm) 192.4, 144.3, 138.7, 137.3,
3
NMR (100 MHz, CDCl ) (δ, ppm) 192.9, 160.4, 144.6, 138.5,
136.5, 136.4, 135.8, 135.0, 134.3, 133.9, 133.4, 129.6, 129.5,
129.4, 128.9, 127.6, 125.3, 124.4, 124.1, 121.5; HRMS (ESI-
3
1
1
36.7, 136.3, 136.1, 134.5, 134.4, 132.4, 132.0, 131.2, 130.6,
+
29.7, 128.8, 128.4, 125.4, 124.2, 123.5, 118.2, 106.7, 55.3;
TOF) m/z calcd for C H Cl O, 375.0338 [M+H] ; found
23
13
2
+
HRMS (ESI-TOF) m/z calcd for C H ClO , 371.0834 [M+H] ;
375.0352.
7-Bromo-5-phenyl-11H-benzo[b]fluoren-11-one (2o)
24
16
2
found 371.0840.
-(4-Methoxyphenyl)-11H-benzo[b]fluoren-11-one (2i)
o
-1
5
Yellow solid, mp 227-229 C; IR (KBr, ν, cm ) 3008, 1705,
o
-1
1
Yellow solid, mp 213-214 C; IR (KBr, ν, cm ) 3055, 1703,
1
1618, 1187, 943, 638; H NMR (400 MHz, CDCl ) (δ, ppm) 8.18
3
1
623, 1174, 945, 633; H NMR (400 MHz, CDCl ) (δ, ppm) 8.22
(s, 1H), 7.80 (d, J = 8.4 Hz, 1H), 7.75-7.73 (m, 1H), 7.65-7.54
3
(
3
6
s, 1H), 7.95 - 7.92 (m, 1H), 7.75 - 7.72 (m, 1H), 7.49 - 7.43 (m,
(m, 5H), 7.40-7.37 (m, 2H), 7.25-7.17 (m, 2H), 6.32-6.19 (m,
13
H), 7.33 - 7.31 (m, 2H), 7.24-7.21 (m, 2H), 7.15 - 7.13 (m, 2H),
1H); C NMR (100 MHz, CDCl ) (δ, ppm) 192.8, 144.7, 138.1,
3
13
.47-6.44 (m, 1H), 3.97 (s, 3H); C NMR (100 MHz, CDCl ) (δ,
136.6, 136.5, 134.84, 133.7, 132.8, 132.1, 131.9, 130.2, 129.6,
129.5, 129.4, 129.0, 128.7, 124.8, 124.3, 124.0, 123.8; HRMS
3
ppm) 193.3, 159.6, 145.3, 137.4, 136.5, 135.6, 134.7, 134.5,
1
1
+
33.4, 132.6, 130.9, 130.8, 129.4, 128.9, 128.6, 127.5, 126.8,
(ESI-TOF) m/z calcd for C H BrO, 387.0202 [M+H] ; found
23
14
25.1, 124.2 123.9, 114.7, 55.4; HRMS (ESI-TOF) m/z calcd for
387.0221.
5-Phenyl-11H-benzo[b]fluoren-11-one (2p)
+
C H O , 337.1224 [M+H] ; found 337.1241.
24
17
2
o
-1
5
(
-(4-Methoxyphenyl)-7-methyl-11H-benzo[b]fluoren-11-one
2j)
Yellow solid, mp 247-249 C; IR (KBr, ν, cm ) 3043, 1702,
Yellow solid, mp 208-210 C; IR (KBr, ν, cm ) 3043, 1706,
1
1623, 1160, 944, 640; H NMR (400 MHz, CDCl ) (δ, ppm) 8.24
3
o
-1
(s, 1H), 7.96-7.94 (m, 1H), 7.75 -7.73 (m, 1H), 7.63 - 7.59 (m,
3H), 7.50 - 7.44 (s, 3H), 7.42 - 7.40 (m, 2H), 7.23 - 7.16 (m, 2H),
1
1
623, 1174, 957, 636; H NMR (400 MHz, CDCl ) (δ, ppm) 8.18
3
13
(
(
(
(
s, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.73 - 7.71 (m, 1H), 7.32 - 7.29
m, 3H), 7.24 (d, J = 0.8 Hz, 1H), 7.22 - 7.20 (m, 2H), 7.16 - 7.14
m, 2H), 6.41 - 6.39 (m, 1H), 3.98 (s, 3H), 2.39 (s, 3H); C NMR
100 MHz, CDCl ) (δ, ppm) 193.4, 159.5, 145.3, 139.3, 137.5,
6.34-6.32 (m, 1H); C NMR (100 MHz, CDCl ) (δ, ppm) 193.2,
3
145.2, 137.4, 136.9, 136.5, 135.3, 134.7, 134.7, 133.4, 132.6,
130.8, 129.7, 129.3, 128.9, 128.7, 128.3, 127.1, 126.8, 125.2,
13
124.2, 123.8; HRMS (ESI-TOF) m/z calcd for C H O,
3
23 15
+
1
1
36.6, 135.8, 134.6, 133.9, 131.8, 131.5, 130.9, 130.6, 129.6,
307.1118 [M+H] ; found 307.1131.
28.9, 128.5, 126.5, 125.0, 124.1, 123.8, 114.7, 55.4, 22.1;
7-Methyl-5-phenyl-11H-benzo[b]fluoren-11-one (2q)
+
o
-1
HRMS (ESI-TOF) m/z calcd for C H O , 351.1380 [M+H] ;
Yellow solid, mp 217-219 C; IR (KBr, ν, cm ) 3051, 1705,
25
19
2
1
found 351.1389.
-Methoxy-5-(4-methoxyphenyl)-11H-benzo[b]fluoren-11-one
2k)
Yellow solid, mp 244-246 C; IR (KBr, ν, cm ) 2994, 1701,
1622, 1109, 902, 642; H NMR (400 MHz, CDCl ) (δ, ppm) 8.20
3
7
(
(s, 1H), 7.84 (d, J = 8.4 Hz, 1H), 7.73-7.71 (m, 1H), 7.62-7.60
(m, 3H), 7.41-7.39 (m, 2H), 7.32 - 7.30 (m, 1H), 7.21-7.17 (m,
o
-1
13
3H), 6.27 (d, J = 7.2 Hz, 1H), 2.39 (s, 3H); C NMR (100 MHz,
1
1
607, 1173, 919, 633; H NMR (400 MHz, CDCl ) (δ, ppm) 8.15
CDCl ) (δ, ppm) 193.3, 145.2, 139.4, 137.6, 137.1, 136.6, 135.5,
3
3
(
s, 1H), 7.83 (d, J = 8.8 Hz, 1H), 7.72 - 7.70 (m, 1H), 7.33 - 7.31
134.6, 134.1, 131.8, 131.5, 130.6, 129.7, 129.3, 128.9, 128.5,
128.2, 126.4, 125.1, 124.1, 123.7, 22.1; HRMS (ESI-TOF) m/z
(m, 2H), 7.22 - 7.17 (m, 2H), 7.15 - 7.10 (m, 3H), 6.81 (d, J = 2.8
13
+
Hz, 1H), 6.41 - 6.39 (m, 1H), 3.97 (s, 3H), 3.73 (s, 3H);
C
calcd for C H O, 321.1274 [M+H] ; found 321.1290.
24
17
NMR (100 MHz, CDCl ) (δ, ppm) 193.2, 160.2, 159.5, 145.1,
7-Bromo-5-(4-chlorophenyl)-11H-benzo[b]fluoren-11-one (2r)
3
o
-
1
1
1
39.2, 136.7, 136.5, 134.4, 133.3 132.3, 130.7, 129.6, 128.6,
Yellow solid, mp 228-230 C; IR (KBr, ν, cm ) 3053, 1707,
1
28.5, 125.0, 124.0, 123.8, 118.1, 114.8, 107.0, 55.4, 55.3;
1623, 1175, 948, 669; H NMR (400 MHz, CDCl ) (δ, ppm) 8.20
3
+
HRMS (ESI-TOF) m/z calcd for C H O , 367.1329 [M+H] ;
(s, 1H), 7.81 (d, J = 8.8 Hz, 1H), 7.78-7.75 (m, 1H), 7.64-7.62
25
19
3
found 367.1342.
-(4-Methoxyphenyl)-9H-fluoreno[2,3-b]thiophen-9-one (2l)
(m, 2H), 7.59 - 7.56 (m, 1H), 7.53 (s, 1H), 7.37-7.34 (m, 2H),
7.30 - 7.26 (m, 2H), 6.40-6.38 (m, 1H); C NMR (100 MHz,
13
4
o
-1
Yellow solid, mp 206-208 C; IR (KBr, ν, cm ) 3043, 1692,
CDCl ) (δ, ppm) 192.6, 144.4, 137.9, 136.6, 136.5, 135.1, 135.0,
3
1
1
609, 1174, 941, 632; H NMR (400 MHz, CDCl ) (δ, ppm) 8.17
134.8, 132.8, 132.3, 132.2, 131.9, 131.2, 130.4, 129.9, 129.3,
129.1, 125.2, 124.5, 124.0, 123.8; HRMS (ESI-TOF) m/z calcd
3
(d, J = 0.8 Hz, 1H), 7.68 - 7.65 (m, 1H), 7.51 (d, J = 5.6 Hz, 1H),
+
7
.38 - 7.36 (m, 2H), 7.19 -7.17 (m, 2H), 7.11 - 7.09 (m, 2H), 7.02
for C H BrClO, 420.9813 [M+H] ; found 420.9821.
23
13