R. Sott et al. / Tetrahedron 64 (2008) 4135e4142
4141
yielded 0.41 g of fluoro-PCB 81 (1.32 mmol, 66% yield, 99%
1
on Al O ) yielded 1.7 g of crude 15 (90% purity), which was
2 3
ꢀ
purity). Mp¼143e144 C. H NMR (CDCl ) d 7.26 (ddd,
converted into fluoro-PCB 166 according to the general proce-
dure for the deamination of amino-PCBs, using tert-butyl
nitrite (0.9 mL, 7.9 mmol) and DMF (2 mL). The overall yield
starting from 13 was 7% (98% purity). Mp¼130e
3
0
0
0
J ¼0.9 Hz, J ¼2.1 Hz, J ¼8.2 Hz, 1H, C PhC HC H), 7.33
1
2
3
0
0
0
(
dd, J ¼2.1 Hz, J ¼9.9 Hz, 1H, C PhC HC F), 7.48 (dd,
1 2
1
2
0
0
0
J ¼7.6 Hz, J ¼8.2 Hz, 1H, C PhC HC Cl), 7.55 (s, 2H,
1
3
ꢀ
1
CClCHCPh). C NMR (CDCl ) d 115.3 (d, J¼22.2 Hz, CH),
131 C. H NMR (CDCl ) d 6.96 (dd, J ¼8.2 Hz, J ¼2 Hz,
3
3
1
2
0
0
0
1
(
6
21.8 (d, J¼17.7 Hz, CCl), 123.4 (d, J¼3.7 Hz, CH), 127.2
CH), 131.5 (CC), 131.6 (CCl), 135.1 (CCl), 138.4 (d, J¼
.8 Hz, CH), 139.1 (d, J¼2.0 Hz, CC), 158.7 (d, J¼250.0 Hz,
CF). IR (KBr n ) 3018, 1542, 1436, 1215, 778, 742,
1H, C PhC HC H), 7.05 (dd, J ¼9.3 Hz, J ¼2 Hz, 1H,
1 2
1 2
0
0
0
0
0
C FC HC Ph), 7.53 (dd, J ¼8.2 Hz, J ¼7.6 Hz, 1H,
0
13
C HC HC Cl), 7.68 (s, 1H, CClCHCCl). C NMR (CDCl )
3
d 117.8 (d, J¼22.2 Hz, CH), 121.9 (d, J¼17.4 Hz, CCl),
125.9 (d, J¼3.7 Hz, CH), 130.9 (CH), 131.2 (CC), 132.0
max
ꢁ
1
6
69 cm . HRMS m/z calcd 309.9096, found 309.9098.
(
CCl), 132.5 (CCl), 137.4 (d, J¼7.4 Hz, CH), 140.5 (d,
0
0
0
4
.3.13. Fluoro-PCB 105 (2,3,3 ,4,4 -pentachloro-5 -
J¼1.7 Hz, CC), 158.3 (d, J¼250.5 Hz, CF). IR (KBr n
)
max
ꢁ
1
fluorobiphenyl)
3018, 1215, 740, 669 cm . HRMS m/z (Mꢁ1) calcd
Fluoro-PCB 105 was prepared according to the general
procedure for the Suzuki-coupling, using 6 (2 mmol), toluene
342.8797, found 342.8711.
0
0
0
(
10 mL), sodium carbonate (2 mL, 2 M), polymer-encapsu-
4.3.16. Fluoro-PCB 118 (2,3 ,4,4 ,5-pentachloro-5 -
fluorobiphenyl)
lated Pd(PPh3)4 (0.12 g, ꢃ0.06 mmol), 4 (1.0 mmol) and
ethanol (4 mL), which yielded 0.08 g of fluoro-PCB 81
ꢀ
Fluoro-PCB 118 was prepared according to the general proce-
dure for the Suzuki-coupling, using 2,4,5-trichlorobenzene
(1.3 mmol), toluene (5 mL), sodium carbonate (1 mL, 2 M),
polymer-encapsulated Pd(PPh3)4 (0.08 g, ꢃ0.04 mmol), 4
(1.9 mmol) and ethanol (2 mL), which yielded 0.18 g of fluoro-
PCB 118 (0.52 mmol, 40% yield, 97% purity). Mp¼120.5e
1
(
0.23 mmol, 11% yield, 97% purity). Mp¼109.5e111 C. H
NMR (CDCl ) d 7.14 (dd, J ¼8.8 Hz, J ¼1.9 Hz, 1H,
3
1
2
0
0
0
C PhC HC F), 7.16 (d, J¼8.5 Hz, 1H, CClCHCH), 7.31 (dd,
0
0
0
J ¼1.9 Hz, J ¼1.5 Hz, 1H, C PhC HC Cl), 7.47 (d, J¼8.5 Hz,
1
2
1
3
1
H, CHCHCPh). C NMR (CDCl ) d 116.1 (d, J¼22.8 Hz,
3
ꢀ
1
CH), 121.1 (d, J¼19.6 Hz, CCl), 126.7 (d, J¼3.4 Hz, CH),
121.5 C. H NMR (CDCl ) d 7.17 (dd, J ¼2.0 Hz, J ¼8.8 Hz,
3
1
2
0
0
0
1
28.7 (CH), 129.0 (CH), 132.9 (CC), 133.1 (CCl), 134.3
1H, C FC HC Ph), 7.34 (dd, J ¼1.5 Hz, J ¼2.0 Hz, 1H,
1 2
0 0 0
(
CCl), 134.7 (CCl), 138.0 (d, J¼2.0 Hz, CH), 138.7 (d, J¼
C PhC HC Cl), 7.43 (s, 1H, CClCHCCl), 7.62 (s, 1H,
1
3
8
1
3
.8 Hz, CCl), 158.6 (d, J¼251.9 Hz, CF). IR (KBr n ) 3020,
CClCHCPh). C NMR (CDCl ) d 116.1 (d, J¼22.8 Hz, CCl),
max
3
ꢁ
1
518, 1215, 750, 669 cm . HRMS m/z calcd 343.8711, found
43.8714.
121.3 (d, J¼19.6 Hz, CCl), 126.7 (d, J¼3.4 Hz, CH), 131.28
(CH), 131.76 (CH), 131.83 (CC), 132.12 (CCl), 133.7 (CCl),
1
34.4 (CCl), 137.20 (d, J¼2.0 Hz, CC), 137.27 (d, J¼9.0 Hz,
0
0
4
fluorobiphenyl)
.3.14. Fluoro-PCB 114 (2,3,4,4 ,5-pentachloro-3 -
CCl), 158.7 (d, J¼251.7 Hz, CF). IR (KBr n ) 3019, 1209,
max
ꢁ
1
786, 731, 669 cm . HRMS m/z (Mꢁ2) calcd 341.8740, found
Fluoro-PCB 114 was prepared according to the general
procedure for the Suzuki-coupling, using 10 (2 mmol), toluene
10 mL), sodium carbonate (2 mL, 2 M), Pd(PPh ) (0.08 g,
3
0.06 mmol), 3-fluoro-4-chlorophenylboronic acid (2.0 mmol)
and ethanol (4 mL), which yielded 0.17 g of fluoro-PCB 114
341.8742.
0
0
0
(
4.3.17. Fluoro-PCB 126 (3,3 ,4,4 ,5-pentachloro-5 -
fluorobiphenyl)
4
Fluoro-PCB 126 was prepared according to the general
procedure for the Suzuki-coupling, using 8 (2 mmol), toluene
(10 mL), sodium carbonate (2 mL, 2 M), polymer-encapsu-
lated Pd(PPh3)4 (0.12 g, ꢃ0.06 mmol), 4 (1.0 mmol) and
ethanol (4 mL), which yielded 0.35 g of fluoro-PCB 126
ꢀ
(
0.49 mmol, 25% yield, 99% purity). Mp¼107e108 C.
1
H NMR (CDCl ) d 7.10 (dd, J ¼2.1 Hz, J ¼8.1 Hz, 1H,
3
1
2
0
0
0
0
C HC HC Ph), 7.18 (dd, J ¼2.1 Hz, J ¼9.6 Hz, 1H,
1
2
0
0
C PhC HC F), 7.36 (s, 1H, CClCHPh), 7.47 (dd, J ¼8.1 Hz,
1
0
0
0
13
ꢀ
J ¼8.2 Hz, 1H, C HC HC Cl). C NMR (CDCl ) d 117.8
(1.02 mmol, 51% yield, 94% purity). Mp¼164.5e165.5 C.
2
3
1
(
d, J¼22.2 Hz, CH), 121.9 (d, J¼17.7 Hz, CCl), 125.9 (d,
J¼3.7 Hz, CH), 129.8 (CH), 130.9 (CC), 131.3 (CCl), 132.5
CCl), 133.0 (CCl), 134.4 (CCl), 138.0 (d, J¼7.4 Hz, CH),
H NMR (CDCl ) d 7.25 (dd, J ¼9.2 Hz, J ¼2.2 Hz, 1H,
3
1
2
0
0
0
0
C FC HC Ph), 7.44 (dd, J ¼2.2 Hz, J ¼1.5 Hz, 1H,
1
2
0
0
13
C PhC HC Cl), 7.54 (s, 2H, CPhCHCCl). C NMR (CDCl )
(
1
3
39.0 (d, J¼1.7 Hz, CC), 157.9 (d, J¼250.2 Hz, CF). IR
d 113.5 (d, J¼23.2 Hz, CH), 124.3 (d, J¼3.3 Hz, CH), 127.1
ꢁ
1
(
(
KBr n ) 3019, 1517, 1215, 750, 669 cm . HRMS m/z
(CH), 138.2 (CC), 135.3 (CCl), 138.0 (CCl), 138.1 (d,
J¼8.3 Hz, CCl), 159.0 (d, J¼252.1 Hz, CF). IR (KBr n
max
Mꢁ2) calcd 341.8740, found 341.8742.
)
max
ꢁ
1
3020, 3019, 2400, 1427, 1208, 1203, 787, 730, 669 cm
HRMS m/z calcd 343.8711, found 343.8718.
.
0 0
.3.15. Fluoro-PCB 117 (2,3,4 ,5,6-pentachloro-3 -
fluorobiphenyl)
Fluoro-PCB 166 was prepared according to the general
procedure for the Suzuki-coupling, using 13 (5.0 mmol), tolu-
ene (20 mL), sodium carbonate (5 mL, 2 M), Pd(PPh3)4
4
0
0
0
4.3.18. Fluoro-PCB 156 (2,3,3 ,4,4 ,5-hexachloro-5 -
fluorobiphenyl)
Fluoro-PCB 156 was prepared according to the general
procedure for the Suzuki-coupling, using 10 (2 mmol), toluene
(10 mL), sodium carbonate (2 mL, 2 M), Pd(PPh ) (0.08 g,
(0.17 g, 0.15 mmol), 12 (6.0 mmol) and ethanol (10 mL). Pu-
rification by column chromatography (80:20 n-hexane/acetone
3
4