Fu and Snieckus
913
Pd(PPh3)4 (0.390 g, 0.34 mmol). Normal workup followed
by flash chromatography (1:1) afforded 1.80 g (78%) of 3g:
mp 105–107°C (hexane); IR (CHC13) 1630 cm–1; 1H NMR δ
0.65–0.71 (t, J = 7.1 Hz, 3 H), 0.85–1.00 (br, 3 H), 2.24 (s, 3
H), 2.80–3.15 (br, 2 H), 3.80–3.85 (m, 5 H), 6.90–6.94 (dd,
J = 8.4, 2.5 Hz, 1 H), 7.10–7.31 (m, 6 H); MS m/e (rel inten-
sity) 297 (M+, 11), 225 (39), 224 (28), 135 (49), 71 (100);
HRMS calcd. for C19H23NO2-H: 296.1652; found: 296.1650.
1 H); MS m/e (rel intensity) 340 (M+, 25), 297 (31), 240
(89), 194 (65), 165 (100). Anal. calcd. for C20H24N2O3: C
70.57, H 7.11, N 8.23; found: C 70.61, H 7.01, N 8.19.
N,N-Diethyl 2 ′-methyl-4 ′-nitrobiphenyl-2-carboxamide (3l):
According to method B, 2-bromo-5-nitrotoluene (1.08 g,
5.0 mmol) was coupled with 2-(N,N-diethylcarbox-
amido)phenylboronic acid (1.55 g, 7.0 mmol) in the pres-
ence of Pd(PPh3)4 (0.231 g, 0.20 mmol). Normal workup
followed by flash chromatography (1:1) afforded 1.27 g
(82%) of 3l: mp 94–95°C (hexane–CH2Cl2); IR (CHC13)
N,N-Diethyl 2 ′-methyl-4 ′-(N,N-diethylcarboxamido)biphenyl-
2-carboxamide (3h): According to method B, N,N-diethyl 3-
methyl-4-bromobenzamide (2.07 g, 7.7 mmol) was coupled
with 2-(N,N-diethylcarboxamido)phenylboronic acid (2.37 g,
10.7 mmol) in the presence of Pd(PPh3)4 (0.358 g,
0.31 mmol). Normal workup followed by flash chromatogra-
phy (1:1) afforded 2.19 g (77%) of 3h: bp 182–186°C
1
1621, 1518, 1348 cm–1; H NMR δ 0.73–0.78 (t, J = 7.1 Hz,
3 H), 0.96–1.02 (t, J = 7.1 Hz, 3 H), 2.31 (s, 3 H), 2.90–3.10
(br, 2 H), 3.20–3.50 (br, 2 H), 7.21–7.48 (m, 5 H), 7.99–8.04
(dd, J = 8.4, 2.3 Hz, 1 H), 8.12–8.13 (d, J = 2.3 Hz, 1 H);
MS m/e (rel intensity) 312 (M+, 11), 311 (36), 240 (56), 194
(100), 165 (96); HRMS calcd. for C18H20N2O3-H: 311.1397;
found: 311.1393.
1
(0.005 mm); IR (neat) 1635 cm–1; H NMR δ 0.70–0.76 (t,
J = 7.1 Hz, 3 H), 0.93–1.05 (2 br, 3 H), 1.10–1.40 (2 br, 6
H), 2.23 (s, 3 H), 2.80–3.80 (m, 8 H), 7.14–7.71 (m, 7 H);
MS m/e (rel intensity) 366 (M+, 24), 294 (100), 266 (22),
221 (22), 165 (20), 100 (23); HRMS calcd. for C23H30N2O2:
366.2309; found: 366.2310.
N,N-Diisopropyl 2′-methyl-4′-nitrobiphenyl-2-carboxamide (3m):
According to method B, 2-bromo-5-nitrotoluene (0.65 g,
3.0 mmol) was coupled with 2-(N,N-diisopropylcarbox-
amido)phenylboronic acid (1.05 g, 4.2 mmol) in the pres-
ence of Pd(PPh3)4 (0.139 g, 0. 12 mmol). Normal workup
followed by flash chromatography (1:1) afforded 1.00 g
(98%) of 3m: mp 139–141°C (hexane–CH2Cl2); IR (CHC13)
N,N-Diethyl 2 ′-methyl-5 ′-(N,N-diethylcarboxamido)biphenyl-
2-carboxamide (3i): According to method B, N,N-diethyl 3-
bromo-4-methylbenzamide (2.97 g, 11.0 mmol) was coupled
with 2-(N,N-diethylcarboxamido)phenyl boronic acid
(3.40 g, 15.4 mmol) in the presence of Pd(PPh3)4 (0.635 g,
0.55 mmol). Normal workup followed by flash chromatogra-
phy (1:1) afforded 3.30 g (82%) of 3i: bp 196–200°C (0.
1
1622, 1516, 1346 cm–1; H NMR δ 0.60–1.20 (m, 9 H),
1.45–1.48 (d, J = 6.6 Hz, 3 H), 2.33 (s, 3 H), 3.20–3.90 (2
br, 2 H), 7.23–7.45 (m, 5 H), 8.00–8.05 (dd, J = 8.4, 2.2 Hz,
1 H), 8.12–8.13 (d, J = 2.2 Hz, 1 H); MS m/e (rel intensity)
340 (M+, 10), 297 (26), 240 (27), 194 (36), 165 (100). Anal.
calcd. for C20H24N2O3: C 70.57, H 7.11, N 8.23; found: C
70.60, H 6.82, N 7.99.
1
1 mm); IR (neat) 1640, 1621 cm–1; H NMR δ 0.73–0.78 (t,
J = 7.1 Hz, 3 H), 0.93–0.99 (t, J = 7.0 Hz, 3 H), 1.02–1.17
(br, 6 H), 2.21 (s, 3 H), 2.90–3.70 (br, 8 H), 7.21–7.47 (m, 7
H); MS m/e (rel intensity) 366 (M+, 7), 209 (19), 193 (40),
192 (29), 121 (100), 105 (27); HRMS calcd. for
C23H30N2O2: 366.2309; found: 366.2300.
N,N-Diethyl 2 ′-methyl-5 ′-nitrobiphenyl-2-carboxamide (3n):
According to method B, 2-bromo-4-nitrotoluene (1.08 g,
5.0 mmol) was coupled with 2-(N,N-diethylcarbox-
amido)phenylboronic acid (1.55 g, 7.0 mmol) in the pres-
ence of Pd(PPh3)4 (0.231 g, 0.20 mmol). Normal workup
followed by flash chromatography (1:2) afforded 1.55 g
(99%) of 3n: mp 124–125°C (hexane); IR (CHC13) 1618,
N,N-Diisopropyl 2′-methyl-5 ′-(N,N-diethylcarboxamido)biphenyl-
2-carboxamide (3j): According to method B, N,N-diethyl 3-
bromo-4-methylbenzamide (2.83 g, 10.6 mmol) was coupled
with 2-(N,N-diisopropylcarboxamido)phenylboronic acid
(3.65 g, 14.7 mmol) in the presence of Pd(PPh3)4 (0.611 g,
0.53 mmol). Normal workup followed by flash chromatogra-
phy (1:1) afforded 3.27 g (79%) of 3j: mp 105–107°C (hex-
1
1517, 1348 cm-l; H NMR δ 0.66–0.73 (t, J = 7.1 Hz, 3 H),
1.03–1.10 (t, J = 7.1 Hz, 3 H), 2.30 (s, 3 H), 2.90–3.70 (2 br,
4 H), 7.22–7.51 (m, 5 H), 7.99 (br, 1 H), 8.07–8.13 (dd, J =
8.4, 2.5 Hz, 1 H); MS m/e (rel intensity) 312 (M+, 18), 295
(61), 240 (69), 165 (100). Anal. calcd. for C18H20N2O3: C
69.21, H 6.45, N 8.97; found: C 68.99, H 6.36, N 8.96.
1
ane); IR (CHC13) 1618, 1612 cm–1; H NMR δ 0.60–1.19
(m, 15 H), 1.44–1.47 (d, J = 6.8 Hz, 3 H), 2.23 (s, 3 H),
3.20–3.80 (2 br, 4 H), 7.21–7.42 (m, 7 H); MS m/e (rel in-
tensity) 394 (M+, 12), 393 (20), 322 (37), 294 (16), 266
(24), 221 (100), 207 (25), 195 (21), 165 (50). Anal. calcd.
for C25H34N2O2: C 76.10, H 8.69, N 7.10; found: C 76.23, H
8.70, N 7.08.
N,N-Diisopropyl 2′-methyl-5′-nitrobiphenyl-2-carboxamide (3o):
According to method B, 2-bromo-4-nitrotoluene (1.08 g,
5.0 mmol) was coupled with 2-(N,N-diisopropylcarbox-
amido)phenylboronic acid (1.74 g, 7.0 mmol) in the pres-
ence of Pd(PPh3)4 (0.231 g, 0.20 mmol). Normal workup
followed by flash chromatography (1:1) afforded 1.68 g
(99%) of 3o: mp 143.5–145°C (hexane–CH2Cl2); IR
N,N-Diisopropyl 2 ′-methyl-3 ′-nitrobiphenyl-2-carboxamide (3k):
According to method B, 2-bromo-6-nitrotoluene (0.65 g,
3.0 mmol) was coupled with 2-(N,N-diisopropylcarbox-
amido)phenylboronic acid (1.05 g, 4.2 mmol) in the pres-
ence of Pd(PPh3)4 (0.139 g, 0. 12 rnmol). Normal workup
followed by flash chromatography (1:1) afforded 0.98 g
(96%) of 3k: mp 97–98.5°C (hexane); IR (CHC13) 1621,
1
(CHC13) 1624, 1519, 1348 cm–1; H NMR δ 0.96–0.99 (d,
J = 6.8 Hz, 3 H), 1.12 (br, 6 H), 1.43–1.46 (d, J = 6.6 Hz, 3
H), 2.32 (s, 3 H), 3.20–3.40 (br, 1 H), 3.80–4.00 (br, 1 H),
7.26–7.45 (m, 5 H), 7.95 (br, 1 H), 8.08–8.12 (dd, J = 8.4,
2.5 Hz, 1 H); MS m/e (rel intensity) 340 (M+, 18), 240
(100), 165 (27). Anal. calcd. for C20H24N2O3: C 70.57, H
7.11, N 8.23; found: C 70.35, H 7.01, N 8.25.
1
1527, 1340 cm–1; H NMR δ 0.59–0.62 (d, J = 6.7 Hz, 3 H),
0.88–1.13 (m, 6 H), 1.43–1.49 (m, 3 H), 2.36 (s, 3 H), 3.19–
3.79 (m, 2 H), 7.24–7.46 (m, 6 H), 7.78–7.81 (d, J = 7.5 Hz,
© 2000 NRC Canada