422 JOURNAL OF CHEMICAL RESEARCH 2018
Experimental
CAUTION: The manufacture and use for all purposes of the
compound 4-nitrobiphenyl (3d) is prohibited in the UK by the
Control of Substances Hazardous to Health (COSHH) regulations.
Compound 3d is a potent human carcinogen and the Journal of
Chemical Research strongly advises against its preparation.
All chemical reagents were obtained from commercial suppliers and used
without further purification. Gas chromatography–mass spectrometry
(GC–MS) was performed on an ISQ Trace 1300 instrument in the
electron ionisation (EI) mode. Helium was used as carrier gas at a constant
flow of 1 mL min–1. The following temperature programme was used:
70 °C for 0 min, heating rate 16 °C min–1, 300°C for 5.625 min, injection
temperature 250 °C, detection temperature 300 °C. Gas chromatography
(GC) analyses were performed on an Agilent 7890A instrument
(Column: Agilent 19091J-413: 30 m × 320 μm × 0.25 μm, carrier gas:
H2, FID detection. Nitrogen was used as carrier gas at a constant flow
of 0.4 mL min–1. The following temperature programne was used: 75
°C for 0 min, heating rate 15 °C min–1, 175 °C for 5 min, heating rate 15
°C min–1, 300 °C for 5 min, injection temperature 250 °C, detection
temperature 300 °C. TEM images were obtained using a Philips Tecnai
12 microscope operating at 120 kV. SEM images were obtained on a
field-emission scanning electron microscope (HITACHI S-4800) and
EDS was performed using an X-Max EDS system (Oxford Instruments).
All compounds were known, the structures of the products were analysed
by GC–MS and confirmed by comparing the GC traces with those of
commercially available products. 1H NMR spectra of the isolated products
were recorded on an AVANCE III Bruker spectrometer operating at 500
MHz and chemical shifts were reported in ppm.
4-Nitrobiphenyl (3d): Yellow solid; m.p. 111–115 °C (lit.6 112–114 °C);
1
yield 94%; MS (EI) m/z: 199 [M+]; H NMR (500 MHz, CDCl3): δ
7.36–7.44 (m, 3H), 7.50–7.53 (m, 2H), 7.56–7.65 (m, 2H), 8.14–8.22
(m, 2H). See literature6 NMR data.
4-Biphenylcarbaldehyde (3e): White solid; m.p. 59–61 °C (lit.6
1
59–60 °C); yield 99%; MS (EI) m/z: 182 [M+]; H NMR (500 MHz,
CDCl3): δ 7.31 (t, 1H), 7.38 (t, 2H), 7.53 (d, 2H), 7.65 (d, 2H), 7.85 (d,
2H), 9.95 (s, 1H). See literature6 NMR data.
4-Fluorobiphenyl (3f): Grey solid; m.p. 73–75 °C (lit.36 73–74 °C);
1
yield 94%; MS (EI) m/z: 172 [M+]; H NMR (500 MHz, CDCl3): δ
7.59–7.53 (m, 4H), 7.46 (dd, J = 7.5 Hz, 7.0 Hz, 2H), 7.35 (t, J = 7.5 Hz,
1H), 7.12 (dd, J = 8.0 Hz, 7.5 Hz, 2H). See literature36 NMR data.
4-Chlorobiphenyl (3g): White solid; m.p. 77–80 °C (lit.6 78–79 °C);
1
yield 98%; MS (EI) m/z: 188 [M+]; H NMR (500 MHz, CDCl3):
δ 7.63–7.58 (m, 2H); 7.56 (d, J = 8.2 Hz, 2H), 7.52–7.39 (m, 5H). See
literature6 NMR data.
4-tert-Butylbiphenyl (3h): White solid; m.p. 49–51 °C (lit.14
1
49–50 °C); yield 95%; MS (EI) m/z: 210 [M+]; H NMR (500 MHz,
Catalyst preparation
CDCl3): δ 7.71 (d, J = 7.8 Hz, 2H), 7.67 (d, J = 8.1 Hz, 2H), 7.58 (d,
J = 8.3 Hz, 2H), 7.52 (t, J = 7.6 Hz, 3H), 7.43 (q, J = 7.4 Hz, 1H), 1.48
(m, 9H). See literature14 NMR data.
3-Methoxybiphenyl (3i): Colourless oil; Yield 99%; MS (EI) m/z: 184
[M+]; 1H NMR (500 MHz, CDCl3): δ 3.58 (s, 3H), 6.64 (dd, J = 8.2, 2.4
Hz, 1H), 6.88–6.95 (m, 2H), 7.06–7.12 (m, 2H), 7.15 (t, J = 7.2 Hz, 2H),
7.33 (d, J = 7.2 Hz, 2H). See literature15 NMR data.
3-Methylbiphenyl (3j): Colourless oil; yield 96%; MS (EI) m/z: 168
[M+]; 1H NMR (500 MHz, CDCl3): δ 7.44 (d, J = 7.6 Hz, 2H), 7.29 (d,
J = 7.2 Hz, 2H), 7.25 (d, J = 8.8 Hz, 2H), 7.19 (t, J = 6.8 Hz, 2H), 7.02
(d, J = 7.2 Hz, 1H), 2.28 (s, 3H). See literature15 NMR data.
The nanocatalyst immobilised on ZrO2 was prepared by the
impregnation–reduction method and the composition of the bimetallic
nanoparticles was controlled by adjusting the ratio of the metal
precursors. In a typical procedure, Pd1Ni4 BMNPs supported on
ZrO2 were prepared as follows: ZrO2 (400 mg) was dispersed into
an aqueous solution (50 mL) of metal precursors (10 mg PdCl2 and
53.5 mg NiCl2·6H2O) under ultrasonic radiation. Lysine aqueous
solution (200 mg dissolved in 2 mL water) was then added to the
mixture with vigorous stirring for 30 min. Then, NaBH4 aqueous
solution (0.05 M, 22 mL) was added dropwise to this suspension.
The colour of the mixture turned to black immediately, indicating
the formation of metal particles. The mixture was further stirred for
30 min and then aged for 24 h. Finally, the solid was separated, washed
(with water and ethanol) and dried at room temperature under reduced
pressure.
3,5-Difluorobiphenyl (3k): Colourless liquid; yield 99%; MS (EI)
m/z: 190 [M+]; 1H NMR (500 MHz, CDCl3): δ 6.68 (tt, 1H), 6.96 (dd,
2H), 7.29 (t, 1H), 7.36 (t, 2H), 7.46 (d, 2H). See literature6 NMR data.
3,4-Dimethylbiphenyl (3l): Colourless liquid; yield 94%; MS (EI)
1
m/z: 182 [M+]; H NMR (500 MHz, CDCl3): δ 2.27 (s, 3H), 2.30 (s,
3H), 7.03 (d, J = 7.6 Hz, 1H), 7.12 (d, J = 7.6 Hz, 1H), 7.19 (t, J = 7.6 Hz,
1H), 7.26 (d, J = 12.8 Hz, 2H), 7.41 (t, J = 6.4 Hz, 3H). See literature16
NMR data.
2-Phenylnaphthalene (3m): White solid; m.p. 97–99 °C (lit.6
97–99 °C); yield 100%; MS (EI) m/z: 204 [M+]; 1H NMR (500 MHz,
CDCl3): δ 7.26−7.34 (m, 1H), 7.37−7.43 (m, 4H), 7.61−7.68 (m, 3H),
7.75−7.82 (m, 3H), 7.94 (s, 1H) See literature6 NMR data.
Suzuki–Miyaura reactions; typical procedure
In
a typical reaction procedure, bromobenzene (0.4 mmol),
4-methylbenzeneboronic acid (0.1 mmol), Pd1Ni4/ZrO2 alloy catalyst
and Na2CO3 (1 equiv.) were added into a reactor (10 mL) equipped
with a magnetic stirrer and EtOH (2 mL) was added as the solvent.
The reaction mixture was stirred at 80 °C under an N2 atmosphere
for 4 h. After reaction, the catalyst was separated by simple filtration
and the solution was analysed by GC and GC–MS. For isolation of the
products, the solvent was removed under reduced pressure. The residue
was purified by flash chromatography on a silica column, using ethyl
acetate and n-hexane as the eluent.
4-Phenoxybiphenyl (3n): Colourless oil; yield 89%; MS (EI) m/z: 246
[M+]; 1H NMR (500 MHz, CDCl3): δ 7.67–7.57 (m, 4H), 7.48 (dd, J = 10.5,
4.7 Hz, 2H), 7.44–7.35 (m, 3H), 7.21–7.08 (m, 5H); 13C NMR (126 MHz,
CDCl3): δ 156.2, 155.9, 139.6, 136.5, 135.3, 129.3, 128.9, 127.8 , 127.5,
126.4, 126.1, 125.9, 122.4, 118.1, 118.0. See literature17 NMR data.
4-Biphenylol (3o): White solid; m.p. 163–165 °C (lit.7 163–164 °C);
The NMR data for the products agreed with the literature.
1
yield 99%; MS (EI) m/z: 170 [M+]; H NMR (500 MHz, CDCl3):
4-Methylbiphenyl (3a): White solid; m.p. 46–48 °C (lit.6 46–47 °C);
yield 99%; MS (EI) m/z: 168 [M+]; 1H NMR (500 MHz, CDCl3): δ 7.49
(dd, J = 8.3, 1.3 Hz, 2H), 7.43–7.38 (m, 2H), 7.34 (t, J = 7.8 Hz, 2H),
7.24 (td, J = 7.2, 1.3 Hz, 1H), 7.16 (d, J = 7.9 Hz, 2H), 2.31 (s, 3H). See
literature6 NMR data.
δ 1.01 (br, 1H), 7.05–7.21 (m, 5H), 7.28 (d, J = 7.2 Hz, 2H), 7.37 (d,
J = 8.8 Hz, 2H). See literature7 NMR data.
4-Methoxybiphenyl (3p): White solid; m.p. 85–87 °C (lit.6
1
86–87 °C); yield 99%; MS (EI) m/z: 184 [M+]; H NMR (500 MHz,
CDCl3) δ 3.75 (s, 3H), 6.87 (d, 2H), 7.19 (t, 1H), 7.31 (t, 2H), 7.41 (m,
Biphenyl (3b): White solid; m.p. 68–70 °C (lit.6 69–70 °C); yield
100%; MS (EI) m/z: 154 [M+]; H NMR (500 MHz, CDCl3): δ 7.25
4H). See literature6 NMR data.
1
4-Biphenylsulfonamide (3q): White solid; m.p. 221–223 °C (lit.18
221–222 °C); yield 95%; MS (EI) m/z: 217 [M+]; 1H NMR (500MHz,
DMSO–d6): δ 6.62 (2H, s), 7.27 (3H, m), 7.59 (2H, d), 7.70 (2H, d), 7.84
(2H, d). See literature18 NMR data.
(2H, t), 7.35 (4H, t), 7.51 (d, 4H). See literature6 NMR data.
4-Biphenylcarbonitrile (3c): White solid; m.p. 86–87 °C (lit.7
85–87 °C); yield 100%; MS (EI) m/z: 179 [M+]; 1 H NMR (500 MHz,
CDCl3): δ 7.59 (d, J = 8.0 Hz, 2H), 7.58 (d, J = 8.4 Hz, 2H), 7.45 (d,
J = 7.6 Hz, 2H), 7.35 (t, J = 7.05 Hz, 2H), 7.29 (t, J = 7.2 Hz, 1H). See
literature7 NMR data.
2-Methylbiphenyl (3r): Colourless oil; yield 92%; MS (EI) m/z: 168
[M+]; 1H NMR (500 MHz, CDCl3): δ 7.28 (t, J = 8.0 Hz, 2H), 7.19 (m,
3H), 7.12 (m, 4H), 2.13 (s, 3H). See literature15 NMR data.