Page 9 of 22
The Journal of Organic Chemistry
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139.5, 134.6, 134.5, 133.5, 132.4, 131.3, 129.9, 129.8, 129.0, 128.9, 128.5, 128.4, 127.4, 127.3, 126.8,
125.3, 121.9, 119.6, 119.4, 115.1, 113.3, 113.2, 112.9, 112.8, 112.7, 55.3, 55.2; LRMS (EI); Mass calcd
for C13H11ClO [M]+: 218.0; found 218.0.
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n-Chloro-4'-methyl-1,1'-biphenyl (3ad).14 Prepared according to the general procedure A using
chlorobenzene and 4-methylbenzene diazonium tetrafluoroborate. The reaction mixture was stirred and
irradiated by 5 W white LEDs (430 – 660 nm) at room temperature under Ar atmosphere for 18 h. The
reaction mixture was purified by flash chromatography using 2% EtOAc/hexane to afford 101 mg (83%
yield, o : m : p =4.7 : 2 : 1) of product as a pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.57 (t, J =
1.9 Hz, 1H), 7.53 – 7.44 (m, 5H), 7.42 – 7.33 (m, 7H), 7.32 – 7.29 (m, 3H), 7.29 – 7.27 (m, 5H), 7.27
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– 7.25 (m, 3H), 2.43 (s, 3H), 2.41 (s, 6H); C{1H} NMR (101 MHz, CDCl3) δ 142.9, 140.4, 139.5,
137.7, 137.4, 137.3, 137.0, 136.9, 136.5, 134.6, 133.0, 132.5, 131.3, 129.9, 129.8, 129.6, 129.5, 129.3,
128.8, 128.7, 128.3, 128.1, 127.0, 126.9, 126.8, 126.7, 125.0, 21.2, 21.1; LRMS (EI); Mass calcd for
C13H11Cl [M]+: 202.0; found 202.0.
n-Chloro-2-nitro-1,1'-biphenyl (3ae).16 Prepared according to the general procedure A using
chlorobenzene and 2-nitrobenzene diazonium tetrafluoroborate. The reaction mixture was stirred and
irradiated by 5 W white LEDs (430 – 660 nm) at room temperature under Ar atmosphere for 18 h. The
reaction mixture was purified by flash chromatography using 20% EtOAc/hexane to afford 103 mg
(73% yield, o : m : p = 2.3 : 1 : 1) of product as a yellow oil. 1H NMR (400 MHz, CDCl3) δ 8.09 (dd, J
= 8.2, 1.3 Hz, 1H), 7.88 (td, J = 8.7, 1.2 Hz, 1H), 7.70 – 7.65 (m, 2H), 7.64 – 7.59 (m, 2H), 7.58 – 7.54
(m, 1H), 7.54 – 7.52 (m, 1H), 7.52 – 7.48 (m, 1H), 7.48 – 7.42 (m, 2H), 7.42 – 7.36 (m, 4H), 7.36 –
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7.31 (m, 5H), 7.29 – 7.21 (m, 3H), 7.19 – 7.15 (m, 1H); C{1H} NMR (101 MHz, CDCl3) δ 149.0,
148.9, 148.5, 139.2, 137.1, 135.8, 135.1, 134.9, 134.4, 134.3, 134.2, 133.0, 132.6, 132.5, 132.4, 132.3,
131.8, 131.7, 129.8, 129.4, 129.3, 129.2, 128.9, 128.8, 128.7, 128.5, 128.3, 128.0, 126.9, 126.1, 124.3,
124.2; LRMS (EI); Mass calcd for C12H8ClNO2 [M]+: 233.0; found 233.0.
n-Chloro-2'-fluoro-1,1'-biphenyl (3af).17 Prepared according to the general procedure A using
chlorobenzene and 2-fluorobenzene diazonium tetrafluoroborate. The reaction mixture was stirred and
irradiated by 4 W blue LEDs (460 nm) at room temperature under Ar atmosphere for 18 h. The reaction
mixture was purified by flash chromatography using 2% EtOAc/hexane to afford 114 mg (92% yield,
o : m : p = 1.7 : 1 : 1) of product as a pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.55 – 7.52 (m,
1H), 7.51 – 7.45 (m, 3H), 7.44 – 7.34 (m, 7H), 7.33 – 7.28 (m, 7H), 7.23 – 7.19 (m, 3H), 7.18 – 7.16
(m, 1H), 7.16 – 7.11 (m, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 159.6 (d, J = 247.9 Hz), 159.6 (d, J
= 248.5 Hz), 159.6 (d, J = 247.6 Hz), 137.5, 134.9, 134.3, 133.7, 131.6 (d, J = 1.1 Hz), 131.5 (d, J =
3.2 Hz), 130.6 (d, J = 3.2 Hz), 130.5 (d, J = 3.4 Hz), 130.3 (d, J = 3.1 Hz), 129.8 (d, J = 8.0 Hz), 129.7,
129.6, 129.5, 129.3, 129.2, 129.1, 128.6, 127.8, 127.7, 127.6, 127.2 (d, J = 3.1 Hz), 127.1, 126.9, 124.5
(d, J = 3.7 Hz), 124.4 (d, J = 3.8 Hz), 123.8 (d, J = 3.8 Hz), 116.2 (d, J = 22.6 Hz), 115.6 (d, J = 22.1
Hz); LRMS (EI); Mass calcd for C12H8ClF [M]+: 206.0; found 206.0.
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