420
K. Nakamura, K. Takenaka / Tetrahedron: Asymmetry 13 (2002) 415–422
Other materials were purchased from Nacalai Tesque,
Inc, Tokyo Kasei Kogyo Co, Ltd, Wako Pure Chemi-
cal Industries, Ltd, and Aldrich Chemical Co, Inc.
3.1.6. 3-Benzoyloxy-1-heptyne 6b. Prepared using the
procedure described above. Yield 0.71 g (73%). 1H
NMR (CDCl3, 200 MHz) l (ppm) 0.86 (3H, t, J=7.1
Hz), 1.39 (4H, m), 1.83 (2H, m), 2.41 (1H, d, J=2.2
Hz), 5.52 (1H, m), 7.45 (3H, m) and 8.00 (2H, m); IR
(NaCl) w=2124 and 1725 cm−1. Anal. calcd for
C14H16O2: C, 77.75; H, 7.46. Found: C, 77.78; H,
7.53%.
3.1.1. 3-Benzoyloxy-1-butyne 2b. Benzoyl chloride (2.0
g, 14 mmol) was added to a solution of 2a (1.0 g, 14
mmol) in pyridine (5 mL) at 0–5°C. The resulting
mixture was stirred at room temperature for 2 h. Brine
(30 mL) was added and ether (30 mL) was added to the
mixture. The organic phase was separated and washed
with 5% aqueous HCl, saturated aqueous brine, satu-
rated aqueous NaHCO3, and saturated aqueous brine,
successively. The organic phase was dried over MgSO4
and the solvent was evaporated under reduced pressure.
The residue was purified with silica gel column chro-
matography using hexane–ethyl acetate (10:1) as eluent
3.1.7. 3-Benzoyloxy-1-octyne 7b. Prepared using the
procedure described above. Yield 0.80 g (87%). 1H
NMR (CDCl3, 200 MHz) l (ppm) 0.90 (3H, brt, J=6.8
Hz), 1.34 (4H, m), 1.55 (2H, m), 1.90 (2H, m), 2.48
(1H, d, J=2.2 Hz), 5.60 (1H, m), 7.48 (3H, m) and 8.08
(2H, m); IR (NaCl) w=2122 and 1725 cm−1. Anal. calcd
for C15H18O2: C, 78.23; H, 7.88. Found: C, 78.42; H,
8.03%.
1
to give white powder (2.1 g, 83%). Mp 44.9–45.1°C; H
NMR (CDCl3, 200 MHz) l (ppm) 1.63 (3H, d, J=6.8
Hz), 2.49 (1H, d, J=2.2 Hz), 5.68 (1H, m), 7.43 (2H,
m), 7.53 (1H, m) and 8.06 (1H, m); 13C NMR (CDCl3,
50 MHz) l (ppm) 165.3, 133.1, 129.7, 128.3, 82.1, 73.0,
60.5, and 21.3; IR (NaCl) w=2114 and 1713 cm−1.
Anal. calcd for C11H10O2: C, 75.84; H, 5.79. Found: C,
75.79; H, 5.73%.
3.1.8. 1-Benzoyloxy-1-phenylethane 8b. Prepared using
1
the procedure described above. Yield 0.87 g (94%). H
NMR (CDCl3, 200 MHz) l (ppm) 1.67 (3H, d, J=6.6
Hz), 6.14 (1H, m), 7.43 (8H, m) and 8.08 (2H, m); IR
(NaCl) w=1719 cm−1. Anal. calcd for C15H14O2: C,
79.62; H, 6.24. Found: C, 79.50; H, 6.23%.
3.1.9. 1-Benzoyloxy-1-phenyl-2,2,2-trifluoroethane 9b.
3.1.2. 2-Benzoyloxy-3-pentyne 3b. Prepared using the
procedure described above. Yield: 1.1 g (97%). 1H
NMR (CDCl3, 200 MHz) l (ppm) 1.58 (3H, d, J=6.8
Hz), 1.84 (3H, d, J=2.0 Hz), 5.65 (1H, m), 7.49 (3H,
m) and 8.06 (2H, m). 50 MHz 13C NMR (CDCl3) l
(ppm) 162.0, 133.0, 130.1, 129.7, 128.3, 106.1, 81.2,
77.8, 61.4, 21.8 and 3.6. IR (NaCl) w=2255 and 1721
cm−1. Anal. calcd for C12H12O2: C, 76.57; H, 6.43.
Found: C, 76.27; H, 6.50%.
Prepared using the procedure described above. Yield
1
0.28 g (88%). H NMR (CDCl3, 200 MHz) l (ppm)
6.37 (1H, m), 7.52 (8H, m) and 8.13 (2H, m); IR (NaCl)
w=1740 cm−1. Anal. calcd for C15H11O2F3: C, 64.29; H,
3.96. Found: C, 64.37; H, 4.01%.
3.1.10. 1-Chloro-2-benzoyloxypropane 10b. Prepared
using the procedure described above. Yield 0.83 g
1
(79%). H NMR (CDCl3, 200 MHz) l (ppm) 1.47 (3H,
d, J=6.4 Hz), 3.72 (2H, d, J=5.2 Hz), 5.36 (1H, m),
7.46 (2H, m), 7.58 (1H, m) and 8.07 (2H, m); IR (NaCl)
w=1721 cm−1. Anal. calcd for C10H11ClO2: C, 60.46; H,
5.58. Found: C, 60.32; H, 5.44%.
3.1.3. 2-Benzoyloxy-3-hexyne 1b. Prepared using the
procedure described above. Yield: 0.58 g (87%). 1H
NMR (CDCl3, 200 MHz) l (ppm) 1.13 (3H, t, J=7.5
Hz), 1.58 (3H, d, J=6.8 Hz), 2.22 (2H, m), 5.68 (1H,
m), 7.43 (2H, m), 7.55 (1H, m) and 8.06 (2H, m); 13C
NMR (CDCl3, 50 MHz) l (ppm) 165.4, 132.9, 130.1,
129.6, 128.2, 86.8, 77.9, 61.3, 21.8, 13.6 and 12.3. IR
(NaCl) w=2245 and 1723 cm−1. Anal. calcd for
C13H14O2: C, 77.20; H, 6.98. Found: C, 77.33; H,
7.10%.
3.1.11. 2-Benzoyloxy-3-butene 11b. Prepared using the
procedure described above. Yield 1.1 g (89%). 1H NMR
(CDCl3, 200 MHz) l (ppm) 1.46 (3H, d, J=6.6 Hz),
5.19 (1H, m), 5.34 (1H, m), 5.61 (1H, m), 5.97 (1H, m),
7.50 (3H, m) and 8.07 (2H, m); IR (NaCl) w=1719
cm−1. Anal. calcd for C11H10O2: C, 74.98; H, 6.86.
Found: C, 74.77; H, 6.90%.
3.1.4. 3-Benzoyloxy-1-pentyne 4b. Prepared using the
procedure described above. Yield 1.1 g (96%). 1H NMR
(200 MHz, CDCl3) l (ppm) 1.12 (3H, t, J=7.4 Hz),
1.96 (2H, m), 2.50 (1H, d, J=2.2 Hz), 5.57 (1H, m),
7.46 (2H, m), 7.58 (1H, m) and 8.09 (2H, m); IR (NaCl)
w=2124 and 1725 cm−1. Anal. calcd for C12H12O2: C,
76.57; H, 6.43. Found: C, 76.47; H, 6.49%.
3.1.12. 2-Benzoyloxybutane 12b. Prepared using the
procedure described above. Yield 1.1 g (94%). 1H NMR
(CDCl3, 200 MHz) l (ppm) 0.98 (3H, t, J=7.5 Hz),
1.34 (3H, d, J=6.6 Hz), 1.69 (2H, m), 5.10 (1H, m),
7.49 (3H, m) and 8.05 (2H, m); IR (NaCl) w=1717
cm−1. Anal. calcd for C11H14O2: C, 74.13; H, 7.92.
Found: C, 74.09; H, 7.94%.
3.1.5. 3-Benzoyloxy-1-hexyne 5b. Prepared using the
procedure described above. Yield 0.92 g (89%). 1H
NMR (CDCl3, 200 MHz) l (ppm) 0.99 (3H, t, J=7.3
Hz), 1.59 (2H, m), 1.92 (2H, m), 2.48 (1H, d, J=2.2
Hz), 5.61 (1H, m), 7.45 (2H, m), 7.56 (1H, m) and 8.06
(2H, m); IR (NaCl) w=2124 and 1725 cm−1. Anal. calcd
for C13H14O2: C, 77.20 H, 6.98. Found: C, 76.94; H,
7.00%.
3.1.13. 2-Benzoyloxy-1-butyronitrile 13b. Prepared using
1
the procedure described above. Yield 1.2 g (96%); H
NMR (CDCl3, 200 MHz) l (ppm) 1.78 (3H, d, J=7.0
Hz), 5.65 (1H, m), 7.48 (2H, m), 7.62 (1H, m) and 8.05
(1H, m); IR (NaCl) w=1732 cm−1. Anal. calcd for
C10H9NO2: C, 68.56; H, 5.18. Found: C, 68.50; H,
5.15%.