The Journal of Organic Chemistry
Article
7.10 (ddd, J = 1.2 Hz, 4.8 Hz, 7.6 Hz, 1H), 7.21 (d, J = 8.4 Hz, 1H),
7.48 (t, J = 0.8 Hz, 1H), 7.57 (dd, J = 7.2 Hz, 8.4 Hz, 1H), 7.62−7.68
(m, 3H), 7.88 (dd, J = 1.2 Hz, 8.0 Hz, 1H), 7.94 (dd, J = 1.6 Hz, 6.8
Hz, 1H), 8.00−8.05 (m, 2H), 8.08 (dd, J = 1.2 Hz, 8.4 Hz, 1H), 10.38
(s, 1H); 13C NMR (400 MHz, CDCl3) δ 21.4, 109.8, 119.9, 122.0,
123.1, 124.7, 125.5, 126.0, 126.2, 126.48, 126.54, 127.3, 131.9, 132.0,
132.5, 133.8, 135.2, 136.7, 142.3, 147.4, 149.2, 149.4, 162.9, 164.6;
HRMS (EI) m/z (M+) calcd for C24H17N3O2: 379.1321, found:
379.1320.
132.0, 135.2, 136.6, 147.4, 148.9, 149.1, 149.4, 151.8, 161.6, 162.7
(One signal was overlapped by other ones); HRMS (EI) m/z (M+)
calcd for C27H21N3O4: 451.1532, found: 451.1531.
N-[8-{5-(4-(Trifluoromethyl)phenyl)oxazol-2-yl}naphthalen-1-yl]-
picolinamide (3ah). Purified by column chromatography on silica gel
with hexane/ethyl acetate (2:1, v/v) as an eluent; 87 mg (76%), mp
128−129 °C (from hexane/ethyl acetate); 1H NMR (400 MHz,
CDCl3) δ 7.23 (ddd, J = 1.2 Hz, 4.8 Hz, 7.6 Hz, 1H), 7.32 (s, 1H),
7.47−7.59 (m, 6H), 7.66 (t, J = 8.0 Hz, 1H), 7.84 (ddd, J = 1.2 Hz, 2.8
Hz, 7.2 Hz, 2H), 7.91 (d, J = 8.4 Hz, 1H), 7.94 (d, J = 7.2 Hz, 1H),
8.08 (dd, J = 1.2 Hz, 8.4 Hz, 1H), 8.22 (ddd, J = 0.8 Hz, 1.6 Hz, 4.8
Hz, 1H), 9.99 (s, 1H); 13C NMR (400 MHz, CDCl3) δ 122.3, 122.8,
123.88 (q, J = 270 Hz), 123.93, 124.5, 124.8, 125.6 (q, J = 3.8 Hz),
126.1, 126.6, 126.9, 127.2, 127.6, 129.9 (q, J = 32 Hz), 130.7 (q, J = 1.0
Hz), 131.8, 131.8, 132.2, 135.3, 136.7, 147.4, 149.3, 150.4, 162.7,
163.3; 19F NMR (376 MHz, CDCl3) δ −62.65 (s); HRMS (EI) m/z
(M+) calcd for C26H16F3N3O2: 459.1195, found: 459.1196.
N-[8-{5-(4-Cyanophenyl)oxazol-2-yl}naphthalen-1-yl]-
picolinamide (3ai). Purified by column chromatography on silica gel
with hexane/ethyl acetate (2:1, v/v) as an eluent; 63 mg (61%), mp
201−202 °C (from hexane/ethyl acetate); 1H NMR (400 MHz,
CDCl3) δ 7.15−7.18 (m, 1H), 7.26 (s, 1H), 7.38 (d, J = 8.4 Hz, 2H),
7.51−7.44 (m, 4H), 7.58 (t, J = 8.0 Hz, 1H), 7.75−7.77 (m, 2H),
7.81−7.86 (m, 2H), 7.99 (d, J = 8.4 Hz, 1H), 8.14 (d, J = 4.0 Hz, 1H),
9.86 (s, 1H); 13C NMR (400 MHz, CDCl3) δ 111.2, 118.5, 122.2,
122.6, 124.1, 124.8, 125.5, 126.1, 126.6, 126.9, 127.2, 127.6, 131.3,
131.7, 131.8, 132.3, 132.4, 135.19, 136.8, 147.4, 149.2, 149.9, 162.6,
163.7; HRMS (EI) m/z (M+) calcd for C26H16N4O2: 416.1273, found:
416.1274
Methyl 4-[2-{8-(Picolinamido)naphthalen-1-yl}oxazol-5-yl]-
benzoate (3aj). Purified by column chromatography on silica gel
with hexane/ethyl acetate (1:1, v/v) as an eluent; 71 mg (63%), mp
59−61 °C (from hexane/ethyl acetate); 1H NMR (400 MHz, CDCl3)
δ 3.92 (s, 3H), 7.21 (ddd, J = 1.2 Hz, 4.8 Hz, 7.6 Hz, 1H), 7.33 (s,
1H), 7.45 (dt, J = 1.6 Hz, 8.4 Hz, 2H), 7.50 (dt, J = 1.6 Hz, 7.6 Hz,
1H), 7.55 (dd, J = 7.2 Hz, 8.0 Hz, 1H), 7.64 (t, J = 8.0 Hz, 1H), 7.82−
7.89 (m, 3H), 7.93−7.97 (m, 3H), 8.04−8.06 (m, 1H), 8.18 (ddd, J =
0.8 Hz, 1.6 Hz, 4.8 Hz, 1H), 10.03 (s, 1H); 13C NMR (400 MHz,
CDCl3) δ 52.1, 122.2, 122.7, 123.5, 124.6, 124.7, 126.0, 126.4, 126.7,
127.1, 127.5, 129.3, 129.8, 131.4, 131.7, 131.8, 132.1, 135.1, 136.7,
147.4, 149.2, 150.7, 162.7, 163.2, 166.4; HRMS (EI) m/z (M+) calcd
for C27H19N3O4: 449.1376, found: 449.1375.
N-{8-(5-Chlorobenzo[d]oxazol-2-yl)naphthalen-1-yl}-
picolinamide (3ac). Purified by column chromatography on silica gel
with hexane/ethyl acetate (2:1, v/v) as an eluent; 48 mg (48%), mp
188−190 °C (from hexane/ethyl acetate); 1H NMR (400 MHz,
CDCl3) δ 7.11 (dd, J = 2.0 Hz, 8.4 Hz, 1H), 7.19−7.24 (m, 2H), 7.59
(dd, J = 7.2 Hz, 8.0 Hz, 1H), 7.64−7.70 (m, 3H), 7.81 (ddd, J = 0.8
Hz, 1.6 Hz, 4.8 Hz, 1H), 7.91 (d, J = 7.2 Hz, 1H), 7.92 (dd, J = 1.6 Hz,
6.8 Hz, 1H), 7.99 (d, J = 7.6 Hz, 1H), 8.03 (dt, J = 1.2 Hz, 8.0 Hz,
1H), 8.12 (dd, J = 0.8 Hz, 8.0 Hz, 1H), 10.13 (s, 1H); 13C NMR (400
MHz, CDCl3) δ 111.2, 119.9, 122.2, 122.5, 124.7, 125.1, 125.9, 126.75,
126.81 (two signals were overlapped), 127.5, 129.6, 131.8, 132.0,
132.9, 135.2, 137.0, 143.2, 147.5, 149.1, 149.7, 162.9, 166.1; HRMS
(EI) m/z (M+) calcd for C23H14ClN3O2: 399.0775, found: 399.0773.
N-{8-(5-Phenyloxazol-2-yl)naphthalen-1-yl}picolinamide (3ad).
Purified by column chromatography on silica gel with hexane/ethyl
acetate (2:1, v/v) as an eluent; 62 mg (63%), mp 141−143 °C (from
hexane/ethyl acetate); 1H NMR (400 MHz, CDCl3) δ 7.20−7.30 (m,
4H), 7.23 (s, 1H), 7.41 (dd, J = 1.6 Hz, 8.4 Hz, 2H), 7.49−7.56 (m,
2H), 7.63 (t, J = 8.0 Hz, 1H), 7.83−7.88 (m, 3H), 7.98 (d, J = 7.2 Hz,
1H), 8.03 (d, J = 8.4 Hz, 1H), 8.18 (dd, J = 0.8 Hz, 4.4 Hz, 1H), 10.19
(s, 1H); 13C NMR (400 MHz, CDCl3) δ 122.2, 122.7, 123.1, 123.8,
124.7, 125.9, 126.35, 126.40, 126.9, 127.3, 127.4, 128.1, 128.5, 131.6,
131.9, 132.0, 135.2, 136.6, 147.4, 149.4, 151.7, 162.2, 162.8; HRMS
(EI) m/z (M+) calcd for C25H17N3O2: 391.1321, found: 391.1324.
N-[8-{5-(4-Methylphenyl)oxazol-2-yl}naphthalen-1-yl]-
picolinamide (3ae). Purified by column chromatography on silica gel
with hexane/ethyl acetate (2:1, v/v) as an eluent; 79 mg (78%), mp
65−66 °C (from hexane/ethyl acetate); 1H NMR (400 MHz, CDCl3)
δ 2.34 (s, 3H), 7.11 (d, J = 8.0 Hz, 2H), 7.18 (s, 1H), 7.22 (ddd, J =
1.2 Hz, 4.8 Hz, 7.6 Hz, 1H), 7.32 (d, J = 8.4 Hz, 2H), 7.54 (td, J = 1.6
Hz, 7.6 Hz, 2H), 7.63 (t, J = 7.6 Hz, 1H), 7.84−7.91 (m, 3H), 7.99 (d,
J = 7.2 Hz, 1H), 8.03 (dd, J = 1.2 Hz, 8.0 Hz, 1H), 8.20 (ddd, J = 0.8
Hz, 1.6 Hz, 4.8 Hz, 1H), 10.25 (s, 1H); 13C NMR (400 MHz, CDCl3)
δ 21.3, 122.1, 122.3, 123.2, 123.9, 124.77, 124.81, 126.0, 126.3, 126.4,
126.8, 127.3, 129.2, 131.6, 131.9, 132.1, 135.3, 136.7, 138.2, 147.4,
149.5, 152.1, 161.9, 162.8; HRMS (EI) m/z (M+) calcd for
C26H19N3O2: 405.1477, found: 405.1474.
N-[8-{5-(4-Nitrophenyl)oxazol-2-yl}naphthalen-1-yl]picolinamide
(3ak). Purified by column chromatography on silica gel with hexane/
ethyl acetate (2:1, v/v) as an eluent; 70 mg (64%), mp 216−218 °C
1
(from hexane/ethyl acetate); H NMR (400 MHz, CDCl3) δ 7.26
(ddd, J = 1.2 Hz, 4.8 Hz, 7.6 Hz, 1H), 7.40 (s, 1H), 7.51−7.60 (m,
4H), 7.67 (t, J = 8.0 Hz, 1H), 7.84−7.87 (m, 2H), 7.93 (t, J = 8.4 Hz,
2H), 8.09 (dd, J = 1.2 Hz, 8.0 Hz, 1H), 8.15 (dt, J = 2.0 Hz, 9.2 Hz,
2H), 8.24 (ddd, J = 0.8 Hz, 1.6 Hz, 4.8 Hz, 1H), 9.95 (s, 1H); 13C
NMR (400 MHz, CDCl3) δ 122.2, 122.5, 124.1, 124.2, 124.9, 126.1,
126.2, 126.6, 127.0, 127.2, 127.6, 131.7, 131.8, 132.4, 133.2, 135.2,
136.9, 146.9, 147.4, 149.3, 149.7, 162.6, 164.1; HRMS (EI) m/z (M+)
calcd for C25H16N4O4: 436.1172, found: 436.1174.
N-[8-{5-(Naphthalen-1-yl)oxazol-2-yl}naphthalen-1-yl]-
picolinamide (3al). Purified by column chromatography on silica gel
with hexane/ethyl acetate (2:1, v/v) as an eluent; 86 mg (78%), mp
153−154 °C (from hexane/ethyl acetate); 1H NMR (400 MHz,
CDCl3) δ 7.14 (ddd, J = 1.2 Hz, 4.8 Hz, 7.6 Hz, 1H), 7.43−7.52 (m,
5H), 7.45 (s, 1H), 7.57−7.62 (m, 2H), 7.66 (t, J = 8.0 Hz, 1H), 7.81−
7.95 (m, 4H), 8.03 (t, J = 7.2 Hz, 2H), 8.07 (dd, J = 1.2 Hz, 8.4 Hz,
1H), 8.25 (ddd, J = 1.2 Hz, 1.6 Hz, 4.8 Hz, 1H), 10.47 (s, 1H); 13C
NMR (400 MHz, CDCl3) δ 122.4, 123.2, 124.6, 124.8, 125.2, 126.0
(two signals were overlapped), 126.1, 126.3, 126.5, 126.7, 126.9, 127.3,
128.7, 129.3, 129.6, 131.7, 132.1, 132.2, 133.7, 135.4, 136.8, 147.6,
149.7, 150.7, 162.5, 162.9 (two signals were overlapped by other
ones); HRMS (EI) m/z (M+) calcd for C29H19N3O2: 441.1477, found:
441.1476.
N-[8-{5-(4-Methoxyphenyl)oxazol-2-yl}naphthalen-1-yl]-
picolinamide (3af). Purified by column chromatography on silica gel
with hexane/ethyl acetate (2:1, v/v) as an eluent; 79 mg (75%), mp
136−137 °C (from hexane/ethyl acetate); 1H NMR (400 MHz,
CDCl3) δ 3.80 (s, 3H), 6.83 (dd, J = 2.0 Hz, 6.8 Hz, 2H), 7.10 (s, 1H),
7.23 (ddd, J = 1.2 Hz, 4.8 Hz, 7.6 Hz, 1H), 7.34 (dd, J = 2.0 Hz, 6.8
Hz, 2H), 7.50−7.52 (m, 2H), 7.63 (t, J = 8.0 Hz, 1H), 7.83−7.90 (m,
3H), 7.98 (d, J = 7.2 Hz, 1H), 8.02 (dd, J = 1.2 Hz, 8.0 Hz, 1H), 8.21
(ddd, J = 1.2 Hz, 1.6 Hz, 4.8 Hz, 1H), 10.22 (s, 1H); 13C NMR (400
MHz, CDCl3) δ 55.2, 114.0, 120.4, 122.21, 122.19, 123.2, 124.7, 125.4,
125.9, 126.26, 126.32, 126.8, 127.3, 131.6, 131.8, 132.0, 135.2, 136.7,
147.4, 149.4, 151.8, 159.6, 161.6, 162.8; HRMS (EI) m/z (M+) calcd
for C26H19N3O3: 421.1426, found: 421.1423.
N-[8-{5-(3,4-Dimethoxyphenyl)oxazol-2-yl}naphthalen-1-yl]-
picolinamide (3ag). Purified by column chromatography on silica gel
with hexane/ethyl acetate (2:1, v/v) as an eluent; 80 mg (71%), mp
200−202 °C (from hexane/ethyl acetate); 1H NMR (400 MHz,
CDCl3) δ 3.88 (s, 3H), 3.89 (s, 3H), 6.76 (d, J = 8.4 Hz, 1H), 6.91 (d,
J = 2.0 Hz, 1H), 6.94 (dd, J = 2.0 Hz, 8.4 Hz, 1H), 7.11 (s, 1H), 7.22
(ddd, J = 1.2 Hz, 4.8 Hz, 7.6 Hz, 1H), 7.52−7.57 (m, 2H), 7.63 (t, J =
7.6 Hz, 1H), 7.83−7.89 (m, 3H), 7.97 (d, J = 7.2 Hz, 1H), 8.04 (d, J =
8.0 Hz, 1H), 8.24 (dd, J = 0.8 Hz, 4.0 Hz, 1H), 10.11 (s, 1H); 13C
NMR (400 MHz, CDCl3) δ 55.9, 55.9, 107.2, 111.1, 116.7, 120.6,
121.5, 122.1, 123.2, 124.8, 125.9, 126.3, 126.9, 127.3, 131.6, 131.8,
N-{8-(Benzo[d]oxazol-2-yl)-4-methoxynaphthalen-1-yl}-
picolinamide (3ba). Purified by column chromatography on silica gel
11049
dx.doi.org/10.1021/jo402078q | J. Org. Chem. 2013, 78, 11045−11052