Cross-Coupling of N-(2′-Phenylphenyl)benzenesulfonamides
J . Org. Chem., Vol. 63, No. 15, 1998 5215
5,6-Dih yd r o-5-[(4′-ch lor op h en yl)su lfon yl]p h en a n th r i-
d in e-6-a ceton itr ile (8): mp 171.5-172.5 °C; 1H NMR δ 2.49
(dd, 1H, J ) 7.8, 16.6 Hz), 2.64 (dd, 1H, J ) 7.3, 16.6 Hz),
5.61 (t, 1H, J ) 7.8 Hz), 6.88 (d, 2H, J ) 8.8 Hz), 6.94 (d, 2H,
J ) 8.8 Hz), 7.20-7.34 (m, 4H), 7.42 (dt, 1H, J ) 1.5, 7.3 Hz),
7.47 (dt, 1H, J ) 1.5, 7.3 Hz), 7.64 (dd, 1H, J ) 2.0, 7.8 Hz),
7.84 (dd, 1H, J ) 1.5, 7.8 Hz); 13C NMR δ 23.85, 55.27, 115.94,
123.62, 123.90, 127.02, 128.08, 128.33, 128.47, 128.52, 129.12,
129.15, 129.18, 129.27, 129.47, 131.19, 131.42, 134.64, 139.22;
3-P h en ylisocou m a r in (19): mp 84-85 °C (lit.14 mp 87-
88 °C); 1H NMR δ 6.95 (s, 1H), 7.40-7.51 (m, 5H), 7.72 (t, 1H,
J ) 7.3 Hz), 7.88 (dt, 2H, J ) 1.5, 8.1 Hz), 8.31 (d, 1H, J ) 8.0
Hz); 13C NMR δ 101.78, 120.55, 125.24, 125.95, 128.13, 128.81,
129.65, 129.95, 131.96, 134.83, 137.50, 153.63, 162.28; HRMS
m/z (M+) calcd for C15H10O2 222.0681, found 222.0662.
6-Meth oxy-3-p h en ylisocou m a r in (20):16 mp 136.5-137
1
°C; H NMR δ 3.93 (s, 3H), 6.88 (d, 1H, J ) 2.4 Hz), 6.89 (s,
1H), 7.03 (dd, 1H, J ) 2.4, 8.8 Hz), 7.42-7.48 (m, 3H), 7.83
(dd, 2H, J ) 1.5, 8.5 Hz), 8.23 (d, 1H, J ) 8.8 Hz); HRMS m/z
(M+) calcd for C16H12O3 252.0786, found 252.0786.
MS CI m/z 395, 397 ([M + H]+). Anal. Calcd for C21H15
-
ClN2O2S: C, 63.88; H, 3.83; N, 7.09. Found: C, 63.63; H, 3.81;
N, 7.02.
(Z)-3-Ben zylid en e-5-m eth oxyp h th a lid e (21): mp 137.5-
1
138 °C; H NMR δ 3.95 (s, 3H, CH3O), 6.36 (s, 1H, Ha), 7.05
Eth yl 5,6-d ih yd r o-5-(p h en ylsu lfon yl)p h en a n th r id in e-
6-a ceta te (9): mp 117.5-118.0 °C; 1H NMR δ 1.29 (t, 3H, J )
6.8 Hz), 2.42 (dd, 1H, J ) 6.8, 15.1 Hz), 2.55 (dd, 1H, J ) 8.3,
15.1 Hz), 4.18 (dq, 2H, J ) 2.4, 6.8 Hz), 5.82 (t, 1H, J ) 7.8
Hz), 6.90 (t, 2H, J ) 7.8 Hz), 7.04-7.18 (m, 6H), 7.24 (d, 1H,
J ) 7.3 Hz), 7.35 (dt, 1H, J ) 1.0, 7.3 Hz), 7.42 (dt, 1H, J )
1.5, 7.3 Hz), 7.58 (dd, 1H, J ) 1.5, 7.8 Hz), 7.79 (dd, 1H, J )
1.0, 7.8 Hz); HRMS m/z (M+) calcd for C23H21NO4S 407.1208,
found 407.1204. Anal. Calcd for C23H21NO4S: C, 67.80; H,
5.19; N, 3.44. Found: C, 67.75; H, 5.21; N, 3.41.
Eth yl 5,6-dih ydr o-5-[(4′-m eth ylph en yl)su lfon yl]ph en an -
th r id in e-6-a ceta te (10): mp 103.0-104.0 °C; 1H NMR δ 1.28
(t, 3H, J ) 6.8 Hz), 2.14 (s, 3H), 2.42 (dd, 1H, J ) 7.3, 15.1
Hz), 2.55 (dd, 1H, J ) 8.3, 15.1 Hz), 4.17 (dq, 2H, J ) 2.4, 6.8
Hz), 5.80 (dd, 1H, J ) 7.3, 8.3 Hz), 6.67 (d, 2H, J ) 8.3 Hz),
6.91(d, 2H, J ) 8.3 Hz), 7.08-7.17 (m, 3H), 7.23-7.25 (m, 1H),
7.34 (dt, 1H, J ) 1.5, 7.8 Hz), 7.40 (dt, 1H, J ) 2.0, 7.8 Hz),
7.58 (dd, 1H, J ) 2.0, 7.8 Hz), 7.78 (dd, 1H, J ) 1.5, 7.8 Hz);
MS m/z 421 (M+). Anal. Calcd for C24H23NO4S: C, 68.39; H,
5.50; N, 3.32; S, 7.61. Found: C, 68.18; H, 5.56; N, 3.28; S,
7.53.
(dd, 1H, J ) 7.3 Hz, H6), 7.14 (d, 1H, J ) 2.4 Hz, H4), 7.31 (t,
1H, J ) 7.3 Hz, H4′), 7.40 (t, 2H, J ) 7.3 Hz, H3′), 7.80-7.84
(m, 3H, H,7 H2′); 13C NMR δ 55.91, 102.68, 106.74, 116.06,
118.18, 127.01, 128.33, 128.72, 130.07, 133.10, 143.17, 144.50,
165.08, 166.70; HRMS m/z (M+) calcd for C16H12O3 252.0786,
found 252.0780. Anal. Calcd for C16H12O3: C, 76.18; H, 4.79.
Found: C, 76.28; H, 5.07.
(Z)-3-Ben zylid en e-7-m eth ylp h th a lid e (22):17 mp 158-
158.5 °C; 1H NMR δ 2.72 (s, 3H, CH3), 6.38 (s, 1H, Ha), 7.28-
7.33 (m, 2H, H,6 H4′), 7.41 (dt, 2H, J ) 1.5, 7.3 Hz, H3′), 7.55-
7.58 (m, 2H, H,4 H5), 7.84-7.86 (m, 2H, H2′); HRMS m/z (M+)
calcd for C16H12O2 236.0837, found 236.0845. Anal. Calcd for
C
16H12O2: C, 81.34; H, 5.12. Found: C, 81.05; H, 5.14. The
observed NOE peak enhancements in 21 and 22 were as
follows:
Eth yl 2-br om o-5,6-d ih yd r o-5-[(4′-m eth ylp h en yl)su lfo-
n yl]p h en a n th r id in e-6-a ceta te (11): mp 154.5-155.5 °C; 1H
NMR δ 1.28 (t, 3H, J ) 7.3 Hz), 2.15 (s, 3H), 2.41 (dt, 1H, J )
6.8, 14.6 Hz), 2.52 (dt, 1H, J ) 8.3, 14.6 Hz), 4.17 (dq, 2H, J
) 2.0, 7.3 Hz), 5.79 (dd, 1H, J ) 6.8, 7.3 Hz), 6.71 (d, 2H, J )
7.8 Hz), 6.94 (d, 2H, J ) 6.8 Hz), 7.11-7.21 (m, 4H), 7.52 (dd,
1H, J ) 2.0, 8.3 Hz), 7.66 (d, 1H, J ) 8.3 Hz), 7.72 (s, 1H); 13
C
NMR δ 14.21, 21.25, 40.37, 55.63, 60.94, 121.33, 123.35,
126.55, 126.7, 126.99, 127.97, 128.33, 128.50, 128.56, 131.08,
131.52, 131.55, 131.99, 133.90, 133.93, 143.20, 169.41; HRMS
m/z (M+) calcd for C24H22BrNO4S 499.0470, found 499.0468.
Anal. Calcd for C24H22BrNO4S: C, 57.61; H, 4.43; N, 2.80.
Found: C, 57.69; H, 4.41; N, 2.80.
Eth yl 5,6-d ih yd r o-5-(m eth ylsu lfon yl)p h en a n th r id in e-
6-a ceta te (12): mp 108.0-109.0 °C; 1H NMR δ 1.26 (t, 3H, J
) 6.8 Hz), 2.26 (s, 3H), 2.47 (dd, 1H, J ) 7.3, 15.1 Hz), 2.59
(dd, 1H, J ) 7.8, 15.1 Hz), 4.15 (dq, 2H, J ) 3.9, 6.8 Hz), 5.76
(dd, 1H, J ) 7.3, 7.8 Hz), 7.34-7.46 (m, 5H), 7.66-7.69 (m,
1H), 7.82-7.87 (m, 2H); GC/MS m/z 345 (M+). Anal. Calcd
for C18H19NO4S: C, 62.59; H, 5.54; N, 4.06; S, 9.28. Found:
C, 62.72; H, 5.57; N, 3.97; S, 9.13.
Rea ction of Ar om a tic Ca r boxylic Acid s w ith Alk en es.
In a 100-mL two-necked flask was placed MS 4A (400 mg),
which was then dried at 150 °C in vacuo overnight. Then,
Pd(OAc)2 (0.05-0.1 mmol) and Cu(OAc)2‚H2O (0.05-0.1 mmol)
were added. After the apparatus was evacuated by pumping,
nitrogen (750 mL) was introduced. Then, an acid (1 mmol), 2
(3 mmol), DMF (5 mL), and air (150 mL) were injected into
the flask, and the resulting mixture was stirred at 100-120
°C for 6-18 h. After cooling, the reaction mixture was
extracted with diethyl ether and dried over sodium sulfate.
Product was isolated by column chromatography on silica gel
using hexanes-ethyl acetate as eluent.
(Z)-3-Ben zylid en en a p h th o[1,2-c]fu r a n -1(3H)-on e (23):
mp 213.5-214.5 °C; H NMR δ 6.51 (s, 1H), 7.35 (t, 1H, J )
7.3 Hz), 7.44 (t, 2H, J ) 7.3 Hz), 7.63 (dt, 1H, J ) 1.0, 6.8 Hz),
7.73 (dt, 1H, J ) 1.0, 6.8 Hz), 7.76 (d, 1H, J ) 8.8 Hz), 7.91 (d,
2H, J ) 7.3 Hz), 7.95 (d, 1H, J ) 8.3 Hz), 8.13 (d, 1H, J ) 8.8
Hz), 8.90 (d, 1H, J ) 8.3 Hz); HRMS m/z (M+) calcd for
19H12O2 272.0837, found 272.0838. Anal. Calcd for
19H12O2: C, 83.81; H, 4.44. Found: C, 83.63; H, 4.46.
1H-3-P h en yln a p h th o[2,3-c]p yr a n -1-on e (24): mp 180.5-
1
C
C
181 °C; 1H NMR δ 7.07 (s, 1H), 7.41-7.50 (m, 3H), 7.55 (t,
1H, J ) 7.6 Hz), 7.64 (t, 1H, J ) 7.6 Hz), 7.91-7.92 (m, 4H),
8.02 (d, 1H, J ) 8.3 Hz), 8.93 (s, 1H); 13C NMR δ 101.92,
118.97, 124.30, 125.13, 126.67, 127.69, 128.81, 129.43, 129.76,
129.77, 132.00, 132.13, 132.21, 132.39, 136.61, 152.00, 162.62;
HRMS m/z (M+) calcd for C19H12O2: 222.0681, found 222.0662.
Anal. Calcd for C19H12O2: C, 83.81; H, 4.44. Found: C, 83.45;
H, 4.57.
Ack n ow led gm en t. This work was partly supported
by a Grant-in-aid for Scientific Research from the
Ministry of Education, Science, Sports, and Culture,
J apan. We thank Prof. K. Yamamoto of Science Uni-
versity of Tokyo in Yamaguchi for his useful suggestion
and Ms. Y. Miyaji and Ms. T. Muneishi of the Instru-
mental Analysis Center, Osaka University, for helpful
assistance in obtaining NMR spectra.
3-(Bu toxyca r bon yl)m eth ylp h th a lid e (18): oil; 1H NMR
δ 0.94 (t, 3H, J ) 7.3 Hz), 1.37 (tq, 2H, J ) 7.3, 7.3 Hz), 1.62
(m, 2H), 2.88 (dd, 1H, J ) 6.6, 16.6 Hz), 2.95 (dd, 1H, J ) 6.8,
16.6 Hz), 4.17 (t, 2H, J ) 6.8 Hz), 5.89 (t, 1H, J ) 6.8 Hz),
7.51 (d, 1H, J ) 7.8 Hz), 7.56 (t, 1H, J ) 7.3 Hz), 7.69 (dt, 1H,
J ) 1.0, 7.8 Hz), 7.92 (d, 1H, J ) 7.3 Hz); HRMS m/z (M+)
calcd for C14H16O4 248.1048, found 248.1046. Anal. Calcd for
J O980584B
(16) Elix, J . A.; Murphy, D. P. Aust. J . Chem. 1975, 28, 1559.
(17) J ones, P. R.; Weisman, G. R.; Baillargeon, M. J .; Gosink, T. A.
J . Org. Chem. 1980, 45, 3618.
C
14H16O4: C, 67.73; H, 6.50. Found: C, 67.67; H, 6.57.