G
A. K. Cooper et al.
Paper
Synthesis
1H NMR (CDCl3, 400 MHz): = 7.70–7.54 (m, 4 H, Ar CH), 7.41–7.37
(m, 4 H, Ar CH), 7.31 (d, J = 7.0 Hz, 1 H, Ar CH), 7.13 (d, J = 16.7 Hz, 1 H,
CH=CH), 7.06 (d, J = 16.7 Hz, 1 H, CH=CH).
MS (GC-MS, EI): m/z = 270.1 [M]+.
Analytical data are consistent with the literature.35
13C{1H} NMR (CDCl3, 101 MHz): = 136.5, 135.8, 131.3, 128.9, 128.3,
127.5, 127.4, 126.9, 126.1, 120.8.
MS (GC-MS, EI): m/z = 258 [M]+.
Methyl(4′-methyl-[1,1′-biphenyl]-4-yl)sulfane (P7)
Synthesised according to the general procedure for synthetic cross-
coupling reactions using 4-bromothioanisole (203.8 mg, 1 mmol),
4-tolylboronic acid (148.5 mg, 1.1 mmol), 2 (7.1 mg, 1 mol%), and
K3PO4 (636.9 mg, 3 mmol) in a 4/1 (v/v) THF/H2O mixture (2 mL). The
desired product was purified by recrystallisation from hexane/DCM
to yield a white solid; yield: 171.2 mg (80%); mp 120–122 °C.
1H NMR (CDCl3, 400 MHz): = 7.55–7.49 (m, 4 H, Ar CH), 7.35 (d,
J = 9.1 Hz, 2 H, Ar CH), 7.27 (d, J = 9.1 Hz, 2 H, Ar CH), 2.55 (s, 3 H,
SCH3), 2.42 (s, 3 H, ArCH3).
(E)-1-(4-Bromophenyl)-N-phenylmethanimine (S12)
4-Bromobenzaldehyde (501.2 mg, 2.7 mmol) was added to a micro-
wave vial equipped with a stirrer bar and molecular sieves. The vial
was closed using a septum-fitted crimp cap and purged and back-
filled with N2. Aniline (0.246 mL, 2.7 mmol, 1 equiv.) and anhyd tolu-
ene (2.5 mL) were added and the mixture was heated using micro-
wave irradiation at 200 °C for 4 h. Once cooled to r.t., the reaction
mixture was extracted with H2O (150 mL) and Et2O (3 × 50 mL). The
organic layers were combined, dried (MgSO4), and filtered. The sol-
vent was removed under reduced pressure and the product was re-
crystallised from DCM/pentane to give a yellow amorphous solid;
yield: 100.3 mg (14%).
13C{1H} NMR (CDCl3, 101 MHz): = 137.6 (Ar C), 137.2 (Ar C), 136.7
(Ar C), 136.5 (Ar C), 129.0 (Ar CH), 126.8 (Ar CH), 126.6 (Ar CH), 126.2
(Ar CH), 20.6 (SCH3), 15.5 (ArCH3).
MS (GC-MS, EI): m/z = 214.1 [M]+.
4-Methyl-4′-(phenylethynyl)-1,1′-biphenyl (P8)
IR (ATR, neat): 3040, 2880, 1904, 1622, 1584, 1564, 1501, 1485 cm–1
.
Synthesised according to the general procedure for synthetic cross-
coupling reactions using 1-bromo-4-(phenylethynyl)benzene (257.4
mg, 1 mmol), 4-tolylboronic acid (149.3 mg, 1.1 mmol), 2 (7.4 mg, 1
mol%), and K3PO4 (638.1 mg, 3 mmol) in anhyd toluene (2 mL). The
desired product was purified by passing the reaction mixture through
a pad of silica gel and evaporating the solvent under reduced pressure
to yield a white solid; yield: 141.2 mg (53%); mp 160–162 °C.
1H NMR (CD3CN, 400 MHz): = 8.55 (s, 1 H, CHN), 7.88–7.84 (m, 2 H,
Ar CH), 7.72–7.70 (m, 2 H, Ar CH), 7.47–7.43 (m, 2 H, Ar CH), 7.29–
7.26 (m, 2 H, Ar CH), 7.23 (d, J = 6.1 Hz, 1 H, Ar CH).
13C{1H} NMR (CD3CN, 101 MHz): = 158.8, 131.5, 129.7, 129.5, 128.8,
125.7, 124.7, 120.6, 120.4.
MS (GC-MS, EI): m/z = 259.0 [M]+.
IR (ATR, neat): 3021, 1578, 1493 cm–1
.
1H NMR (CDCl3, 400 MHz): = 7.65–7.58 (m, 6 H, Ar CH), 7.56 (d,
J = 8.1 Hz, 2 H, Ar CH), 7.42–7.37 (m, 3 H, Ar CH), 7.30 (d, J = 7.8 Hz, 2
H, Ar CH), 2.44 (s, 3 H, CH3).
13C{1H} NMR (CDCl3, 101 MHz): = 140.4 (Ar C), 137.02 (Ar C), 136.99
(Ar C), 131.5 (Ar CH), 131.1 (Ar CH), 129.1 (Ar CH), 127.9 (Ar CH),
127.7 (A r C), 126.4 (Ar CH), 126.3 (Ar CH), 122.9 (Ar C), 121.4 (Ar C),
89.5 (C≡C), 88.9 (C≡C), 20.6 (CH3).
1-Bromo-4-(methylsulfinyl)benzene (S15)
4-Bromothioanisole (998.6 mg, 4.9 mmol) was added to a 100 mL
round-bottomed flask equipped with a stirrer bar and dissolved in
DCM (20 mL). A solution of mCPBA (1.593 g, 1.2 equiv.) in DCM (10
mL) was added to the solution at 0 °C over 5 min, and the reaction
mixture was stirred at r.t. for 12 h. The reaction mixture was diluted
with sat. aq NaHCO3 (100 mL) and extracted with DCM (2 × 50 mL).
The organic layers were combined, dried (MgSO4), and filtered. The
solvent was removed under reduced pressure and the product was re-
crystallised from DCM/hexane to give a white solid; yield: 472.0 mg
(47%); mp 80–82 °C.
MS (GC-MS, EI): m/z = 268.1 [M]+.
Analytical data are consistent with the literature.36
IR (ATR, neat): 2990, 2911, 1570, 1470 cm–1
1H NMR (CDCl3, 400 MHz): = 7.70 (d, J = 8.1 Hz, 2 H, Ar CH), 7.5 (d,
J = 8.4 Hz, 2 H, Ar CH), 2.74 (s, 3 H, CH3).
13C{1H} NMR (CDCl3, 101 MHz): = 144.4, 132.1, 125.0, 124.7, 43.5.
Analytical data are consistent with the literature.34
.
(E)-1-(4′-Methyl-[1,1′-biphenyl]-4-yl)-N-phenylmethanimine
(P12)
Synthesised according to the general procedure for synthetic cross-
coupling reactions using (E)-1-(4-bromophenyl)-N-phenylmethan-
imine (261.0 mg, 1 mmol), 4-tolylboronic acid (149.4 mg, 1.1 mmol),
2 (7.2 mg, 1 mol%), and K3PO4 (637.1 mg, 3 mmol) in a 4:1 (v/v)
THF/H2O mixture (2 mL). The desired product was purified by recrys-
tallisation from hexane/DCM to yield a pale orange/brown solid;
yield: 225.1 mg (83%); mp 134–136 °C.
(E)-4-Methyl-4′-styryl-1,1-biphenyl (P6)
Synthesised according to the general procedure for synthetic cross-
coupling reactions using (E)-1-bromo-4-styrylbenzene (259.5 mg, 1
mmol), 4-tolylboronic acid (149.2 mg, 1.1 mmol), 2 (6.8 mg, 1 mol%),
and K3PO4 (635.7 mg, 3 mmol) in a 4:1 (v/v) THF/H2O mixture (2 mL).
The desired product was purified by recrystallisation from hex-
ane/DCM to yield a white solid; yield: 251.9 mg (93%); mp 226–
228 °C.
IR (ATR, neat): 3048, 2976, 2355, 1531 cm–1
.
1H NMR (CD3CN, 400 MHz): = 8.61 (s, 1 H, CHN), 8.00 (d, J = 8.1 Hz, 2
H, Ar CH), 7.79 (d, J = 8.1 Hz, 2 H, Ar CH), 7.64 (d, J = 8.1 Hz, 2 H, Ar
CH), 7.46 (t, J = 8.6 Hz, 2 H, Ar CH), 7.34 (d, J = 8.6 Hz, 2 H, Ar CH),
7.29–7.27 (m, 3 H, Ar CH), 2.42 (s, 3 H, CH3).
13C{1H} NMR (CD3CN, 101 MHz): = 159.6, 151.6, 143.1, 137.6, 136.5,
134.8, 129.2, 128.8, 128.7, 126.6, 126.4, 125.5, 120.4, 19.7.
IR (ATR, neat): 3021, 2914, 2046, 1755, 1578, 1493 cm–1
.
1H NMR (CDCl3, 400 MHz): = 7.61 (s, 4 H, Ar CH), 7.56–7.54 (m, 4, Ar
CH), 7.41–7.38 (m, 2, Ar CH), 7.27 (s, 1 H, Ar CH), 7.17 (s, 2 H, CH),
2.43 (CH3).
MS (GC-MS, EI): m/z = 268.1 [M]+.
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–I