1214 Bull. Chem. Soc. Jpn., 78, No. 7 (2005)
BCSJ AWARD ARTICLE
0.85 (d, 3H, J ¼ 7:2 Hz), 0.96 (t, 3H, J ¼ 7:4 Hz), 1.37 (tq, 2H,
J ¼ 7:4 Hz, J ¼ 7:4 Hz), 1.50–1.73 (m, 2H), 2.35–2.48 (m, 1H),
3.05 (dd, 1H, J ¼ 11:7 Hz, J ¼ 3:6 Hz), 3.25–3.50 (m, 2H), 3.60
(dd, 1H, J ¼ 11:6 Hz, J ¼ 5:0 Hz), 5.40 (d, 1H, J ¼ 2:7 Hz),
7.28–7.42 (m, 5H). 13C NMR (75 MHz, CDCl3) ꢂ 11.3, 13.8,
19.9, 29.0, 31.5, 49.1, 50.1, 80.2, 125.5, 127.7, 128.2, 137.5,
153.0. IR (KBr) 2961, 1689, 1489, 1279 cmꢁ1. LRMS (EI) m=z
247 (Mþ), 232 (Mþ ꢁ Me), 204 (Mþ ꢁ C3H7). HRMS (EI) calcd
for C15H21NO2 (Mþ): 247.1572, found: 247.1573.
3-Butyl-5,6-diphenyl-3,4-dihydro-2H-1,3-oxazin-2-one. Pre-
pared from 1 (10.0 mL, 0.496 mmol) andꢂdiphenylacetylene (73.5
mg, 0.412 mmol) by Method A (X ¼ 0 C): Isolated yield 48%
(64.0 mg, purified with flash chromatography, hexane/ethyl ace-
tate 10:1): TLC Rf 0.47 (hexane/ethyl acetate 3:1). 1H NMR
(600 MHz, CDCl3) ꢂ 0.97 (t, 3H, J ¼ 7:6 Hz), 1.41 (tq, 2H, J ¼
7:6 Hz, J ¼ 7:6 Hz), 1.64–1.71 (m, 2H), 3.47 (t, 2H, J ¼ 7:6 Hz),
4.20 (s, 2H), 7.08–7.35 (m, 10H). 13C NMR (150 MHz, CDCl3) ꢂ
13.8, 20.0, 28.5, 48.6, 50.6, 109.4, 127.7, 127.8, 128.66, 128.74,
128.79, 132.2, 135.8, 145.3, 150.5. IR (neat) 3060, 2959, 1728,
1447 cmꢁ1. LRMS (EI) m=z 307 (Mþ). HRMS (EI) calcd for
C20H21NO2 (Mþ): 307.1572, found: 307.1574.
3-Butyl-6-(p-trifluoromethylphenyl)perhydro-1,3-oxazin-2-
one. Prepared from 1 (10.0 mL, 0.503 mmol) and p-(trifluoro-
methyl)styrene (73.8 mg, 0.429 mmol) by Method A (X ¼ 0
ꢂC): Isolated yield 63% (80.9 mg, purified with flash chromatog-
3-Butyl-5,6-dimethyl-3,4-dihydro-2H-1,3-oxazin-2-one. Pre-
pared from 1 (10.0 mL, 0.496 mmol) and 2-butyne (46.3 mg,
0.421 mmol) by Method A (X ¼ 0 ꢂC): Isolated yield 64%
(64.0 mg, purified with flash chromatography, hexane/ethyl ace-
tate 10:1): TLC Rf 0.50 (hexane/ethyl acetate 3:1). 1H NMR
(600 MHz, CDCl3) ꢂ 0.89 (t, 3H, J ¼ 6:8 Hz), 0.90 (t, 3H, J ¼
7:6 Hz), 0.92 (t, 3H, J ¼ 7:6 Hz), 1.33 (tq, 2H, J ¼ 7:6 Hz, J ¼
7:6 Hz), 1.39 (tq, 2H, J ¼ 7:6 Hz, J ¼ 7:6 Hz), 1.50–1.61 (m,
4H), 1.96 (t, 2H, J ¼ 7:6 Hz), 2.11 (t, 2H, J ¼ 7:5 Hz), 3.32 (t,
2H, J ¼ 8:3 Hz), 3.68 (s, 2H). 13C NMR (150 MHz, CDCl3) ꢂ
13.6, 13.7, 13.8, 19.9, 20.1, 21.0, 28.4, 30.5, 30.7, 48.29, 48.34,
1
raphy, hexane/ethyl acetate 2:1). H NMR (300 MHz, CDCl3) ꢂ
0.95 (t, 3H, J ¼ 7:5 Hz), 1.23–1.42 (m, 2H), 1.49–1.70 (m, 2H),
2.01–2.17 (m, 1H), 2.21–2.36 (m, 1H), 3.22–3.55 (m, 4H), 5.35
(dd, 1H, J ¼ 1:8 Hz, J ¼ 9:9 Hz), 7.49 (s) and 7.52 (s) (2H),
7.62 (s) and 7.65 (s) (2H). 13C NMR (75 MHz, CDCl3) ꢂ 13.6,
19.8, 28.9, 29.5, 44.0, 49.1, 77.1, 125.39, 125.43, 125.8, 143.0,
152.9. IR (KBr) 2965, 1682, 1489, 1329 cmꢁ1. LRMS (EI) m=z
301 (Mþ), 282 (Mþ ꢁ F), 258 (Mþ ꢁ C3H7). HRMS (EI) calcd
for C15H18F3NO2 (Mþ): 301.1290, found: 301.1287.
3-Butyl-6-octyl-3,4-dihydro-2H-1,3-oxazin-2-one. Prepared
from 1 (10.0 mL, 0.503 mmol) and 1-octyne (46.8 mg, 0.425
mmol) by Method A (X ¼ 0 ꢂC): Isolated yield 64% (64.6 mg, pu-
rified with flash chromatography, hexane/ethyl acetate 15:1): TLC
Rf 0.32 (hexane/ethyl acetate 10:1). 1H NMR (300 MHz, CDCl3)
ꢂ 0.88 (t, 3H, J ¼ 7:2 Hz), 0.94 (t, 3H, J ¼ 7:2 Hz), 1.20–1.65 (m,
12H), 2.09 (dt, 2H, J ¼ 0:9 Hz, J ¼ 7:5 Hz), 3.34 (dd, 2H, J ¼
8:6 Hz, J ¼ 7:5 Hz), 3.49–3.68 (m, 2H), 4.78 (t, 2H, J ¼ 3:2
Hz). 13C NMR (75 MHz, CDCl3) ꢂ 13.8, 14.0, 19.9, 22.5, 25.9,
28.3, 28.6, 31.5, 32.3, 45.2, 48.6, 93.6, 150.7, 151.8. IR (neat)
2957, 1725, 1456, 1173 cmꢁ1. LRMS (EI) m=z 239 (Mþ), 238
(Mþ ꢁ H). HRMS (EI) calcd for C14H25NO2 (Mþ): 239.1885,
found: 239.1883.
105.6, 145.9, 151.2. IR (neat) 3337, 2963, 1725, 1466 cmꢁ1
.
LRMS (EI) m=z 239 (Mþ), 224 (Mþ ꢁ Me), 196 (Mþ ꢁ C3H7).
HRMS (EI) calcd for C14H25NO2 (Mþ): 239.1889, found:
239.1885.
3-Butyl-6-phenylperhydro-1,3-oxazin-2-one.19
Prepared
from 1 (10.0 mL, 0.492 mmol) and styrene (43.2 mg, 0.414 mmol)
by Method A: Isolated yield 57% (55.3 mg, purified with flash
chromatography, hexane/ethyl acetate 2:1) with polymeric prod-
uct (15.5 mg, 35% yield based on styrene, purified with gel perme-
ation chromatography): Prepared from 1 (10.0 mL, 0.492 mmol)
and styrene (43.2 mg, 0.414 mmol) by Method B: Isolated yield
20% (19.4 mg, purified with flash chromatography, hexane/ethyl
acetate 2:1) with polymeric product (43.3 mg, 98% yield based on
styrene, purified with gel permeation chromatography): Prepared
from 1 (10.0 mL, 0.497 mmol) and styrene (43.1 mg, 0.414 mmol)
by Method C: Isolated yield 55% (53.0 mg, purified with flash
chromatography, hexane/ethyl acetate 2:1) with polymeric prod-
uct (24.5 mg, 56% yield based on styrene, purified with gel perme-
ation chromatography): Prepared from 1 (10.0 mL, 0.491 mmol)
and styrene (45.3 mg, 0.435 mmol) by micromixing: Isolated yield
79% (79.8 mg, purified with flash chromatography, hexane/ethyl
acetate 2:1) with polymeric product (10.1 mg, 23% yield based on
styrene, purified with gel permeation chromatography): TLC Rf
0.32 (hexane/ethyl acetate 1:1). 1H NMR (300 MHz, CDCl3) ꢂ
0.95 (t, 3H, J ¼ 6:3 Hz), 1.35 (tq, 2H, J ¼ 7:4 Hz, J ¼ 7:4 Hz),
1.52–1.69 (m, 2H), 2.02–2.34 (m, 2H), 3.21–3.52 (m, 4H), 5.28
(dd, 1H, J ¼ 2:7 Hz, J ¼ 9:6 Hz), 7.25–7.42 (m, 5H). 13C NMR
(75 MHz, CDCl3) ꢂ 13.8, 19.9, 29.1, 29.6, 44.2, 49.2, 77.9,
125.5, 128.2, 128.5, 139.0, 153.4.
3-Butyl-6-p-chlorophenylperhydro-1,3-oxazin-2-one. Pre-
pared from 1 (10.0 mL, 0.500 mmol) and p-chlorostyrene (60.9
mg, 0.440 mmol) by Method A: Isolated yield 43% (50.1 mg, pu-
rified with flash chromatography, hexane/ethyl acetate 2:1) with
polymeric product (39.2 mg, 64% yield based on p-chlorostyrene,
purified with gel permeation chromatography): Prepared from 1
(10.0 mL, 0.500 mmol) and p-chlorostyrene (60.9 mg, 0.440
mmol) by Method B: Isolated yield 12% (14.6 mg, purified with
flash chromatography, hexane/ethyl acetate 2:1) with polymeric
product (50.9 mg, 83% yield based on p-chlorostyrene, purified
3-Butyl-6-pheny-3,4-dihydro-2H-1,3-oxazin-2-one.
pared from 1 (10.0 mL, 0.500 mmol) and phenylacetylene (43.0
Pre-
ꢂ
mg, 0.421 mmol) by Method A (X ¼ 0 C): Isolated yield 46%
(44.6 mg, purified with flash chromatography, hexane/ethyl ace-
tate 10:1): TLC Rf 0.76 (hexane/ethyl acetate 1:1). 1H NMR
(300 MHz, CDCl3) ꢂ 0.96 (t, 3H, J ¼ 7:2 Hz), 1.38 (dd, 2H, J ¼
7:4 Hz, J ¼ 7:4 Hz), 1.57–1.70 (m, 2H), 3.41 (dd, 2H, J ¼ 6:6 Hz,
J ¼ 8:4 Hz), 4.01 (d, 2H, J ¼ 3:3 Hz), 5.56 (t, 1H, J ¼ 3:6 Hz),
7.34–7.43 (m, 3H), 7.57–7.69 (m, 2H). 13C NMR (75 MHz,
CDCl3) ꢂ 13.8, 19.9, 28.4, 45.5, 48.7, 65.8, 94.1, 124.5, 128.4,
129.1, 131.7, 148.8, 150.4. IR (neat) 2959, 1723, 1449, 1227
cmꢁ1. LRMS (EI) m=z 231 (Mþ), 203 (Mþ ꢁ CO), 187 (Mþ ꢁ
CO2). HRMS (EI) calcd for C14H17NO2 (Mþ): 231.1259, found:
231.1258.
3-Butyl-6-(trimethylsilyl)-3,4-dihydro-2H-1,3-oxazin-2-one.
Prepared from 1 (10.0 mL, 0.504 mmol) and (trimethylsilyl)acety-
lene (41.2 mg, 0.419 mmol) by Method A (X ¼ 0 ꢂC): Isolated
yield 90% (85.5 mg, purified with flash chromatography, hex-
ane/ethyl acetate 10:1): TLC Rf 0.69 (hexane/ethyl acetate
3:1). 1H NMR (300 MHz, CDCl3) ꢂ 0.16 (s, 9H), 0.94 (t, 3H, J ¼
7:2 Hz), 1.35 (tq, 2H, J ¼ 7:6 Hz, J ¼ 7:6 Hz), 1.52–1.66 (m,
2H), 3.33 (dd, 2H, J ¼ 6:6 Hz, J ¼ 8:4 Hz), 3.85 (d, 2H, J ¼
3:3 Hz), 5.25 (t, 1H, J ¼ 3:5 Hz). 13C NMR (75 MHz, CDCl3)
ꢂ 3.1, 13.7, 19.8, 28.2, 45.7, 48.7, 108.5, 150.8, 158.0. IR (neat)
2959, 1717, 1483, 1250 cmꢁ1. LRMS (EI) m=z 227 (Mþ), 212
(Mþ ꢁ Me), 199 (Mþ ꢁ CO). HRMS (EI) calcd for C11H21NO2Si
(Mþ): 227.1342, found: 227.1342.