H. Maekawa, Y. Nishiyama / Tetrahedron 71 (2015) 6694e6700
6699
834, 787 (cmꢀ1). LRMS (EI): m/z 309 [Mþ]. HRMS (EI): Calcd for
16H14NO2F3: 309.0977, found: 309.0997.
1028, 949, 797, 755 (cmꢀ1). LRMS (EI): m/z 309 [Mþ]. Anal. Calcd for
16H14NO2F3: C, 62.13, H, 4.56, N, 4.53. Found: C, 61.94, H, 4.65, N,
C
C
4.55.
4.2.4. 1,1,1-Trifluoro-4-(4-methylphenyl)-4-(4-pyridyl)butan-2-one
(3d). Eluent hexane: ethyl acetate¼1:1, Rf¼0.3, yellow oil. Isolated
4.2.9. 1,1,1-Trifluoro-3-(4-methylphenyl)-4-(4-pyridyl)butan-2-one
(3i). Eluent hexane: ethyl acetate¼1:1, Rf¼0.3, yellow oil. Isolated
Yield¼64%. 1H NMR (400 MHz, CDCl3)
d (ppm): 2.31 (3H, s), 3.48
(2H, d, J¼7.3 Hz), 4.59 (1H, t, J¼7.3 Hz), 7.07e7.15 (6H, m), 8.49 (2H,
Yield¼82%.1H NMR (400 MHz, CDCl3)
d (ppm): 2.32 (3H, s), 3.04 (1H,
dd, J¼1.7 Hz, J¼4.6 Hz). 13C NMR (100 MHz, CDCl3)
d
(ppm): 20.83,
dd, J¼7.5 Hz, J¼13.9 Hz), 3.37 (1H, dd, J¼7.5 Hz, J¼13.9 Hz), 4.28 (1H, t,
J¼7.5 Hz), 6.96 (2H, dd, J¼1.7 Hz, J¼4.4 Hz), 7.03 (2H, d, J¼7.8 Hz), 7.14
(2H, d, J¼7.8 Hz), 8.44 (2H, dd, J¼1.7 Hz, J¼4.4 Hz).13C NMR (100 MHz,
41.51, 43.50, 115.26 (q, 1JCF¼292.2 Hz), 122.61, 127.28, 129.65, 137.19,
137.58, 149.93, 151.48, 188.77 (q, 2JCF¼35.9 Hz). 19F NMR (376 MHz,
CDCl3)
d
(ppm): ꢀ80.27. IR (neat): 3025, 2937, 1765, 1603, 1513,
CDCl3)
d
(ppm): 20.62, 37.46, 53.28,115.34 (q, 1JCF¼293.8 Hz),123.98,
1419, 1294, 1212, 1170, 1146, 1009, 809, 759 (cmꢀ1). LRMS (EI): m/z
293 [Mþ]. Anal. Calcd for C16H14NOF3: C, 65.52, H, 4.81, N, 4.78.
Found: C, 65.27, H, 4.89, N, 4.78.
128.05,129.73,130.33,138.24,146.72,149.28,190.10 (q, 2JCF¼33.9 Hz).
19F NMR (376 MHz, CDCl3)
d
(ppm): ꢀ77.38. IR (neat): 3033, 2930,
1754, 1605, 1561, 1513, 1418, 1207, 1154, 949, 823, 725 (cmꢀ1). LRMS
(EI): m/z 293 [Mþ]. Anal. Calcd for C16H14NOF3: C, 65.52, H, 4.81, N,
4.78. Found: C, 65.25, H, 4.93, N, 4.75.
4.2.5. 1,1,1-Trifluoro-3-phenyl-4-(4-pyridyl)butan-2-one
(3e). Eluent hexane: ethyl acetate¼1:1, Rf¼0.3, yellow oil. Isolated
Yield¼80%. 1H NMR (400 MHz, CDCl3)
d
(ppm): 3.06 (1H, dd,
4.2.10. 3-(4-Chlorophenyl)-1,1,1-trifluoro-4-(4-pyridyl)butan-2-one
(3j). Eluent hexane: ethyl acetate¼1:3, Rf¼0.3, yellow oil. Isolated
J¼7.3 Hz, J¼13.8 Hz), 3.40 (1H, dd, J¼7.3 Hz, J¼13.8 Hz), 4.31 (1H, t,
J¼7.3 Hz), 6.96 (2H, d, J¼5.6 Hz), 7.15 (2H, d, J¼7.3 Hz), 7.33e7.34
Yield¼75%. 1H NMR (400 MHz, CDCl3)
d (ppm): 3.03 (1H, dd,
(3H, m), 8.44 (2H, d, J¼5.6 Hz). 13C NMR (100 MHz, CDCl3)
d
(ppm):
J¼7.5 Hz, J¼13.9 Hz), 3.38 (1H, dd, J¼7.5 Hz, J¼13.9 Hz), 4.30 (1H, t,
J¼7.5 Hz), 6.95 (2H, d, J¼5.4 Hz), 7.10 (2H, d, J¼8.3 Hz), 7.32 (2H, d,
1
37.88, 53.95, 115.52 (q, JCF¼293.0 Hz), 124.21, 128.41, 128.63,
129.33, 133.69, 146.75, 149.72, 190.28 (q, JCF¼34.8 Hz). 19F NMR
J¼8.3 Hz), 8.46 (2H, d, J¼5.4 Hz). 13C NMR (100 MHz, CDCl3)
d (ppm):
2
(376 MHz, CDCl3)
d
(ppm): ꢀ77.38. IR (neat): 3033, 2930, 1754,
37.71, 53.13, 115.40 (q, 1JCF¼293.0 Hz), 124.10, 129.52, 129.64, 132.11,
1605, 1512, 1418, 1207, 1154, 948, 822, 725 (cmꢀ1). LRMS (EI): m/z
279 [Mþ]. Anal. Calcd. For C15H12NOF3: C, 64.51, H, 4.33, N, 5.02.
Found: C, 64.29, H, 4.48, N, 5.05.
134.73, 146.27, 149.72, 189.91 (q, JCF¼34.8 Hz). 19F NMR (376 MHz,
2
CDCl3)
d
(ppm): ꢀ77.51. IR (neat): 3032, 2850,1758,1608,1493,1420,
1212, 1156, 1093, 1014, 833, 755 (cmꢀ1). LRMS (EI): m/z 313 [Mþ].
HRMS (EI): Calcd for C15H11NOF3Cl: 313.0481, found: 313.0508.
4.2.6. 1,1,1-Trifluoro-3-(4-methoxyphenyl)-4-(4-pyridyl)butan-2-one
(3f). Eluent hexane: ethyl acetate¼1:1, Rf¼0.25, yellow oil. Isolated
4.2.11. 1,1,1-Trifluoro-3-(1-naphthyl)-4-(4-pyridyl)butan-2-one
(3k). Eluent hexane: ethyl acetate¼1:1, Rf¼0.25, yellow oil.
Yield¼76%. 1H NMR (400 MHz, CDCl3)
d (ppm): 3.04 (1H, dd,
J¼7.5 Hz, J¼13.8 Hz), 3.36 (1H, dd, J¼7.5 Hz, J¼13.8 Hz), 3.80 (3H, s),
4.25 (1H, t, J¼7.5 Hz), 6.86 (2H, d, J¼6.8 Hz), 6.96 (2H, dd, J¼1.7 Hz,
J¼4.4 Hz), 7.07 (2H, d, J¼6.8 Hz), 8.45 (2H, dd, J¼1.7 Hz, J¼4.4 Hz).
Yield¼75%. 1H NMR (400 MHz, CDCl3)
d (ppm): 3.12 (1H, dd,
J¼7.1 Hz, J¼13.9 Hz), 3.54 (1H, dd, J¼7.1 Hz, J¼13.9 Hz), 5.18 (1H, t,
J¼7.1 Hz), 7.01 (2H, d, J¼5.8 Hz), 7.28 (1H, d, J¼7.3 Hz), 7.44 (1H, t,
J¼7.3 Hz), 7.50e7.57 (2H, m), 7.84 (1H, d, J¼8.3 Hz), 7.88 (1H, d,
J¼8.3 Hz), 7.98 (1H, d, J¼7.3 Hz), 8.37 (2H, d, J¼5.8 Hz). 13C NMR
13C NMR (100 MHz, CDCl3)
d (ppm): 37.76, 53.06, 55.16, 114.69,
1
115.54 (q, JCF¼293.0 Hz), 124.26, 125.28, 129.61, 147.02, 149.53,
159.70, 190.33 (q, 2JCF¼33.9 Hz). 19F NMR (376 MHz, CDCl3)
d
(ppm):
(100 MHz, CDCl3)
d
(ppm): 37.67, 49.15, 115.47 (1JCF¼293.0 Hz),
ꢀ77.29. IR (neat): 3036, 2957, 2840, 1753, 1609, 1513, 1253, 1179,
121.77, 124.05, 125.26, 125.85, 126.23, 127.16, 129.31, 129.35, 130.06,
835, 757 (cmꢀ1). LRMS (EI): m/z 309 [Mþ]. HRMS (EI): Calcd for
130.86, 134.27, 146.94, 149.69, 190.43 (2JCF¼34.8 Hz). 19F NMR
C
16H14NO2F3: 309.0977, found: 309.0997.
(376 MHz, CDCl3)
d
(ppm): ꢀ77.13. IR (neat): 3050, 2951, 1754, 1561,
1561, 1513, 1418, 1286, 1213, 1156, 1069, 946, 794, 759 (cmꢀ1). LRMS
(EI): m/z 329 [Mþ]. Anal. Calcd. for C19H14NOF3: C, 69.30, H, 4.28, N,
4.25. Found: C, 69.10, H, 4.47, N, 4.25.
4.2.7. 1,1,1-Trifluoro-3-(3-methoxyphenyl)-4-(4-pyridyl)butan-2-one
(3g). Eluent hexane: ethyl acetate¼1:2, Rf¼0.3, yellow oil.
Yield¼87%. 1H NMR (400 MHz, CDCl3)
d (ppm): 3.05 (1H, dd,
J¼7.5 Hz, J¼13.9 Hz), 3.38 (1H, dd, J¼7.5 Hz, J¼13.9 Hz), 3.77 (3H, s),
4.28 (1H, t, J¼7.5 Hz), 6.68 (1H, s), 6.74 (1H, d, J¼8.0 Hz), 6.85 (1H, d,
J¼8.0 Hz), 6.97 (2H, d, J¼5.4 Hz), 7.25 (1H, t, J¼8.0 Hz), 8.46 (2H, d,
4.2.12. Ethyl
4-[3,3,3-trifluoro-2-oxo-1-(4-pyridylmethyl)propyl]
benzoate (3l). Eluent hexane: ethyl acetate¼1:2, Rf¼0.25, yellow oil.
Isolated Yield¼31%. 1H NMR (400 MHz, CDCl3)
d (ppm): 1.39 (3H, t,
J¼5.4 Hz). 13C NMR (100 MHz, CDCl3)
d
(ppm): 37.84, 53.90, 55.22,
J¼7.1 Hz), 3.08 (1H, dd, J¼7.1 Hz, J¼13.1 Hz), 3.42 (1H, dd, J¼7.1 Hz,
J¼13.1 Hz), 4.38 (2H, q, J¼7.1 Hz), 4.39 (1H, t, J¼7.1 Hz), 6.95 (2H, d,
J¼5.8 Hz), 7.24 (2H, d, J¼8.3 Hz), 8.02 (2H, d, J¼8.3 Hz), 8.46 (2H, d,
1
113.81, 114.22, 115.54 (q, JCF¼293.0 Hz), 120.66, 124.14, 130.32,
135.15, 146.60, 149.88, 160.17, 190.17 (q, JCF¼34.8 Hz). 19F NMR
2
(376 MHz, CDCl3)
d
(ppm): ꢀ77.41. IR (neat): 3030, 2963, 2838,
J¼5.8 Hz). 13C NMR (100 MHz, CDCl3)
d (ppm): 14.21, 37.77, 53.83,
1755, 1602, 1586, 1561, 1602, 1586, 1489, 1455, 1439, 1417, 1287,
1261, 1209, 1153, 1050, 778, 758, 719, 696 (cmꢀ1). LRMS (EI): m/z
309 [Mþ]. Anal. Calcd for C16H14NO2F3: C, 62.13, H, 4.56, N, 4.53.
Found: C, 62.08, H, 4.57, N, 4.60.
61.20, 115.45 (1JCF¼293.0 Hz), 124.08, 128.40, 130.48, 130.91, 138.48,
146.06, 149.96, 165.74, 189.81 (2JCF¼34.8 Hz). 19F NMR (376 MHz,
CDCl3)
d
(ppm): ꢀ77.54. IR (neat): 3037, 2983,1758,1714,1608,1563,
1418, 1278, 1210, 1157, 1110, 1022, 911, 855, 812, 765, 737 (cmꢀ1).
LRMS (EI): m/z 351 [Mþ]. Anal. Calcd for C18H16NO3F3: C, 61.54, H,
4.59, N, 3.99. Found: C, 61.41, H, 4.59, N, 4.02.
4.2.8. 1,1,1-Trifluoro-3-(2-methoxyphenyl)-4-(4-pyridyl)butan-2-one
(3h). Eluent hexane: ethyl acetate¼1:1, Rf¼0.3, yellow oil.
Yield¼84%. 1H NMR (400 MHz, CDCl3)
d
(ppm): 3.00 (1H, dd,
4.2.13. Ethyl 4-(4-pyridylethyl)benzoate (9). Eluent hexane: ethyl
acetate¼1:2, Rf¼0.45, white solid, mp 43.5e45.0 ꢁC. Isolated
J¼7.1 Hz, J¼13.9 Hz), 3.35 (1H, dd, J¼7.1 Hz, J¼13.9 Hz), 3.72 (3H, s),
4.70 (1H, t, J¼7.1 Hz), 6.85e6.97 (5H, m), 7.26e7.30 (1H, m), 8.42
Yield¼39%. 1H NMR (400 MHz, CDCl3)
d (ppm): 1.36 (3H, t,
J¼7.1 Hz), 2.88e2.98 (4H, m), 4.33 (1H, q, J¼7.1 Hz), 7.03 (2H, d,
(2H, d, J¼5.4 Hz). 13C NMR (100 MHz, CDCl3)
d
(ppm): 36.12, 47.68,
1
55.26, 111.03, 115.50 (q, JCF¼293.0 Hz), 120.94, 122.53, 124.28,
J¼6.1 Hz), 7.17 (2H, d, J¼8.3 Hz), 7.93 (2H, d, J¼8.3 Hz), 8.45 (2H, d,
128.87, 129.69, 147.24, 149.44, 156.70, 190.63 (q, JCF¼33.9 Hz). 19
F
J¼6.1 Hz). 13C NMR (100 MHz, CDCl3)
d (ppm): 14.28, 36.44, 36.54,
60.82, 123.83, 128.38, 128.63, 129.73, 145.81, 149.72, 149.86, 166.45.
IR (neat): 3073, 2989, 2933, 2872, 1706, 1601, 1557, 1417, 1279, 1182,
2
NMR (376 MHz, CDCl3)
1606, 1562, 1495, 1466, 1441, 1420, 1290, 1251, 1152, 1070, 1052,
d
(ppm): ꢀ77.17. IR (neat): 3032, 2841, 1755,