Yuguchi et al.
quenched with 2 N HCl solution (2 mL), diluted with water
(10 mL), and extracted with Et2O (20 mL × 2). The combined
organic layers were washed with water (10 mL) and brine (10
mL) and dried over MgSO4. The extract was concentrated, and
the residue was subjected to column chromatography on silica
gel (3:1 hexane/EtOAc) to afford dione 3a (247 mg, 59%) as a
colorless oil, bp 145 °C/1.0 mmHg [lit.30 bp 105-107 °C/0.01
1-(4-Cya n op h en yl)h exa n e-2,5-d ion e (3h ): recrystallized
from Et2O-hexane; colorless crystals (40%); mp 107.9-110.4
°C (Et2O-hexane); IR (neat) 2226, 1702, 1608, 1505 cm-1; 1H
NMR (400 MHz) δ 2.18 (s, 3H), 2.74 (s, 4H), 3.86 (s, 2H), 7.31
(d, J ) 7.8 Hz, 2H), 7.62 (d, J ) 8.3 Hz, 2H); 13C NMR (100
MHz) δ 29.8 (q), 36.0 (t), 37.1 (t), 49.6 (t), 100.5 (s), 118.7 (s),
130.4 (d), 132.3 (d), 139.4 (s), 205.3 (s); EI-MS m/z (rel
intensity) 215 (M+, 2), 116 (21), 99 (100), 71 (13). Anal. Calcd
for C13H13NO2: C, 72.54; H, 6.09; N, 6.51. Found: C, 72.21;
H, 6.14; N, 6.34.
1
mmHg]; IR (neat) 1713 cm-1; H NMR (400 MHz) δ 2.16 (s,
3H), 2.73-2.66 (m, 4H), 3.75 (d, J ) 4.6 Hz, 2H), 7.37-7.20
(m, 5H); 13C NMR (100 MHz) δ 29.9 (q), 35.5 (t), 37.0 (t), 50.0
(t), 127.0 (d), 128.6 (d), 129.4 (d), 134.1 (s), 207.0 (s), 207.1 (s);
EI-MS m/z (rel intensity) 190 (M+, 8), 99 (100), 91 (31), 71 (12).
These spectral data were essentially identical with those
reported previously.30,31
1-(Biph en yl-4-yl)h exan e-2,5-dion e (3i): 4:1 hexane/EtOAc;
colorless crystals (64%); mp 73.9-76.2 °C (Et2O-hexane); IR
(neat) 1704, 1490 cm-1 1H NMR (400 MHz) δ 2.18 (s, 3H),
;
2.73 (m, 4H), 3.78 (s, 2H), 7.27 (m, 2H), 7.34 (m, 1H), 7.43 (m,
2H), 7.57 (m, 4H); 13C NMR (100 MHz) δ 29.9 (q), 35.6 (t), 37.0
(t), 49.6 (t), 127.0 (d), 127.3 (s), 127.4 (d), 128.7 (d), 129.9 (d),
133.1 (s), 139.0 (s), 140.7 (s), 206.9 (s), 207.2 (s); EI-MS m/z
(rel intensity) 266 (M+, 31), 167 (52), 99 (100), 71 (7). Anal.
Calcd for C18H18O2: C, 81.17; H, 6.81. Found: C, 81.27; H,
6.94.
1-(4-Ch lor op h en yl)h exa n e-2,5-d ion e (3b): Column chro-
matography with 5:1 hexane/EtOAc; colorless crystals (52%);
mp 60.5-62.3 °C (Et2O-hexane); IR (neat) 1705, 1492 cm-1
;
1H NMR (400 MHz) δ 2.17 (s, 3H), 2.71 (s, 4H), 3.74 (s, 2H),
7.13 (d, J ) 8.3 Hz, 2H), 7.30 (d, J ) 8.5 Hz, 2H); 13C NMR
(100 MHz) δ 29.8 (q), 35.6 (t), 37.0 (t), 49.1 (t), 128.7 (d), 130.8
(d), 132.5 (s), 132.9 (s), 206.3 (s), 207.5 (s); EI-MS m/z (rel
intensity) 224 (M+, 12), 125 (23), 99 (100), 71 (13). Anal. Calcd
for C12H13ClO2: C, 64.15; H, 5.83; Cl, 15.78. Found: C, 64.25;
H, 5.98; Cl, 15.83.
1-(2-Ch lor op h en yl)h exa n e-2,5-d ion e (3j): 5:1 hexane/
EtOAc; a colorless oil (78%); bp 131 °C/0.2 mmHg [lit.30 bp
140-144 °C/0.01 mmHg]; IR (neat) 1712, 1574, 1475 cm-1; 1H
NMR (270 MHz) δ 2.17 (s, 3H), 2.78-2.68 (m, 4H), 3.89 (s,
2H), 7.39-7.19 (m, 4H); 13C NMR (68 MHz) δ 29.8 (q), 35.8
(t), 36.8 (t), 47.4 (t), 126.9 (d), 128.5 (d), 129.3 (d), 131.7 (d),
132.5 (s), 134.2 (s), 205.5 (s), 207.0 (s); EI-MS m/z (rel intensity)
1-(4-Br om op h en yl)h exa n e-2,5-d ion e (3c): 3:1 hexane/
EtOAc; colorless crystals (68%); mp 75.0-75.6 °C (Et2O-
hexane); IR (neat) 1703, 1488 cm-1; 1H NMR (400 MHz) δ 2.17
(s, 3H), 2.71 (s, 4H), 3.72 (s, 2H), 7.09 (d, J ) 8.1 Hz, 2H),
7.44 (d, J ) 8.1 Hz, 2H); 13C NMR (100 MHz) δ 29.9 (q), 35.6
(t), 37.0 (t), 49.2 (t), 121.0 (s), 131.2 (d), 131.7 (d), 133.0 (s),
206.2 (s), 207.0 (s); EI-MS m/z (rel intensity) 268 (M+, 7), 169
(12), 99 (100), 71 (14). Anal. Calcd for C12H13BrO2: C, 53.55;
H, 4.87; Br, 29.69. Found: C, 53.74; H, 4.90; Br, 29.47.
1-(4-F lu or op h en yl)h exa n e-2,5-d ion e (3d ): 3:1 hexane/
EtOAc; a colorless oil (51%); bp 119 °C/0.3 mmHg; IR (neat)
1714, 1603, 1511 cm-1; 1H NMR (400 MHz) δ 2.19 (s, 3H), 2.72
(s, 4H), 3.74 (s, 2H), 7.01 (m, 2H), 7.16 (m, 2H); 13C NMR (100
MHz) δ 29.9 (q), 35.5 (t), 37.0 (t), 48.9 (t), 115.4 (d), 115.6 (d),
129.8 (s), 130.9 (d), 131.0 (d), 163.1 (s), 206.7 (s), 207.1 (s);
EI-MS m/z (rel intensity) 208 (M+, 13), 109 (39), 99 (100), 71
(14). Anal. Calcd for C12H13FO2: C, 69.22; H, 6.29; F, 9.12.
Found: C, 69.21; H, 6.34; F, 9.02.
1-(4-Tolyl)h exa n e-2,5-d ion e (3e): 5:1 hexane/EtOAc; a
colorless oil (52%); bp 180 °C/30 mmHg; IR (neat) 1711, 1515
cm-1; 1H NMR (270 MHz) δ 2.16 (s, 3H), 2.32 (s, 3H), 2.68 (m,
4H), 3.70 (s, 2H), 7.09 (d, J ) 8.3 Hz, 2H), 7.14 (d, J ) 8.3 Hz,
2H); 13C NMR (100 MHz) δ 21.1 (q), 29.9 (q), 35.4 (t), 37.0 (t),
49.7 (t), 129.3 (d), 129.4 (d), 131.1 (s), 136.7 (s), 207.19 (s),
207.23 (s); EI-MS m/z (rel intensity) 204 (M+, 28), 105 (41), 99
(100), 71 (12). These spectral data were essentially identical
with those reported by Kametani.4b
1-(4-Meth oxyp h en yl)h exa n e-2,5-d ion e (3f): 2:1 hexane/
EtOAc; a colorless oil (19%); bp 155 °C/0.2 mmHg [lit.30 bp
120-123 °C/0.01 mmHg]; IR (neat) 1711, 1611, 1584, 1513
cm-1; 1H NMR (270 MHz) δ 2.16 (s, 3H), 2.69 (m, 4H), 3.68 (s,
2H), 3.79 (s, 3H), 6.86 (d, J ) 8.6 Hz, 2H), 7.12 (d, J ) 8.6 Hz,
2H); 13C NMR (68 MHz) δ 29.9 (q), 35.3 (t), 37.0 (t), 49.1 (q),
55.2 (t), 113.9 (d), 128.6 (s), 130.4 (d), 158.6 (s), 207.2 (s), 207.4
(s).
1-[(4-Me t h o x y c a r b o n y l)p h e n y l]h e x a n e -2,5-d io n e
(3g): 2:1 hexane/EtOAc; a colorless oil (80%); bp 206 °C/1.5
mmHg; IR (neat) 1718, 1714, 1613, 1576, 1510 cm-1; 1H NMR
(270 MHz) δ 2.17 (s, 3H), 2.71 (m, 4H), 3.82 (s, 2H), 3.90 (s,
3H), 7.28 (d, J ) 8.3 Hz, 2H), 8.00 (d, J ) 8.3 Hz, 2H); 13C
NMR (68 MHz) δ 29.8 (q), 35.7 (t), 37.0 (t), 49.7 (t), 52.0 (q),
128.8 (s), 129.5 (d), 129.8 (d), 139.2 (s), 166.8 (s), 205.9 (s),
206.9 (s); EI-MS m/z (rel intensity) 248 (M+, 4), 217 (11), 150
(22), 118 (8), 99 (100), 71 (13). Anal. Calcd for C14H16O4: C,
67.73; H, 6.50. Found: C, 67.53; H, 6.47.
224 (M+, 2), 125 (11), 99 (100), 71 (12). Anal. Calcd for C12H13
-
ClO2: C, 64.15; H, 5.83; Cl, 15.78. Found: C, 64.13; H, 5.92;
Cl, 15.83.
1-(2,6-Dich lor op h en yl)h exa n e-2,5-d ion e (3k ): 5:1 hex-
ane/EtOAc; colorless crystals (76%); mp 58.7-59.4 °C (Et2O-
hexane); IR (neat) 1733, 1720, 1583, 1562 cm-1; 1H NMR (270
MHz) δ 2.16 (s, 3H), 2.83-2.71 (m, 4H), 4.13 (s, 2H), 7.13 (dd,
J ) 8.6, 7.3 Hz, 1H), 7.29 (d, J ) 7.3 Hz, 2H); 13C NMR (68
MHz) δ 29.6 (q), 35.6 (t), 36.6 (t), 44.8 (t), 127.7 (d), 128.6 (d),
131.4 (s), 135.7 (s), 203.8 (s), 206.6 (s); EI-MS m/z (rel intensity)
258 (M+, 0.1), 159 (7), 99 (100), 71 (13). Anal. Calcd for C12H12
-
Cl2O2: C, 55.62; H, 4.67; Cl, 27.36; O, 12.35. Found: C, 55.75;
H, 4.81; Cl, 27.36.
1-(2-Tolyl)h exa n e-2,5-d ion e (3l): 5:1 hexane/EtOAc; a
colorless oil (82%); bp 149 °C/1.3 mmHg; IR (neat) 1715, 1493
cm-1; 1H NMR (400 MHz) δ 2.16 (s, 3H), 2.24 (s, 3H), 2.68 (s,
4H), 3.76 (s, 2H), 7.20-7.13 (m, 4H); 13C NMR (100 MHz) δ
19.6 (q), 29.8 (q), 35.4 (t), 36.9 (t), 48.1 (t), 126.2 (d), 127.3 (d),
130.35 (d), 130.37 (d), 133.0 (s), 136.9 (s), 206.9 (s), 207.1 (s);
EI-MS m/z (rel intensity) 204 (M+, 9), 105 (27), 99 (100), 71
(12). Anal. Calcd for C13H16O2: C, 76.44; H, 7.90. Found: C,
76.44; H, 8.01.
1-(2,4,6-Tr im eth ylp h en yl)h exa n e-2,5-d ion e (3m ): 3:1
hexane/EtOAc; a colorless oil (60%); bp 129 °C/0.2 mmHg, mp
29-31 °C (Et2O-hexane) [lit.32 mp 32 °C]; IR (neat) 1711,
1
1614, 1486 cm-1; H NMR (270 MHz) δ 2.16 (s, 3H), 2.21 (s,
6H), 2.25 (s, 3H), 2.66 (m, 4H), 3.77 (s, 2H), 6.86 (s, 2H); 13C
NMR (68 MHz) δ 20.2 (t), 20.8 (t), 29.8 (t), 35.3 (t), 36.9 (t),
43.9 (t), 128.8 (d), 136.3(s), 136.7 (s), 207.06 (s), 207.09 (s); EI-
MS m/z (rel intensity) 232 (M+, 14), 133 (88), 99 (100), 71 (7).
4-Oxo-5-p h en ylp en ta n a l (7a ): 4:1 hexane/EtOAc; a color-
less oil (48%); bp 108 °C/0.4 mmHg; IR (neat) 2730, 1721, 1714,
1
1604, 1497 cm-1; H NMR (270 MHz) δ 2.74 (m, 4H), 3.75 (s,
2H), 7.36-7.16 (m, 5H), 9.77 (s, 1H); 13C NMR (68 MHz) δ
34.0 (t), 37.5 (t), 50.0 (t), 127.1 (d), 128.7 (d), 129.4 (d), 134.1
(s), 200.4 (d), 206.3 (s); EI-MS m/z (rel intensity) 176 (M+, 24),
91 (56), 85 (100), 57 (7). Anal. Calcd for C14H16O2: C, 74.98;
H, 6.86. Found: C, 74.88; H, 6.66.
4-Oxo-5-(4-flu or op h en yl)p en t a n a l (7b ): 3:1 hexane/
EtOAc; a colorless oil (33%); bp 117 °C/0.4 mmHg; IR (neat)
1
2734, 1718, 1604, 1510 cm-1; H NMR (400 MHz) δ 2.76 (s,
4H), 3.74 (s, 2H), 7.02 (m, 2H), 7.16 (m, 2H), 9.77 (s, 1H); 13C
(30) Stetter, H.; Lorenz, G. Chem. Ber. 1985, 118, 1115.
(31) Pecunioso, A.; Menicagli R. J . Org. Chem. 1988, 53, 2614.
(32) Eberhardt, U.; Deppisch, B.; Musso, H. Chem. Ber. 1983, 116,
119.
912 J . Org. Chem., Vol. 69, No. 3, 2004