D. Michel, M. Schlosser / Tetrahedron 56 (2000) 4253±4260
4257
Allyloxycyclododecane (3c-Hu1-H). See above (imme-
diately after the General working procedure).
J26.5, 7.5, 5.0, 1.4 Hz), 4.7 (1H, dm, J48.1 Hz), 2.09
(3H, s), 1.4 (20H, m). 19F NMR: d 2128.1 (m). Analysis:
calcd for C14H25FO2 (244.36) C 68.82, H 10.31; found C
69.03, H 10.08%.
cis-1-Allyloxy-2-¯uorocyclododecane (cis-3-F). With allyl
bromide as the halide; mp 258 to 2578C; bp 118±1208C/
3 mmHg; n2D0 1.4739; 88%. 1H NMR: d 5.92 (1H, symm. m),
5.3 (1H, dm, J17.2 Hz), 5.2 (1H, dm, J10.2 Hz), 4.75
(1H, symm. dm, J48.0 Hz), 4.17 (1H, symm. dm, J
13.0 Hz), 4.04 (1H, symm. dm, J13.0 Hz), 3.64 (1H,
symm. dm, J22.0 Hz), 1.4 (20H, m). 19F NMRp: d
2124.5 (m). Analysis: calcd for C15H27FO (242.38) C
74.33, H 11.23; found C 74.19, H 11.21%.
trans-2-Fluorocyclododecyl acetate (trans-4a-F). Mp
1
239 to 2378C; n2D0 1.4662; 41%. H NMR: d 5.26 (1H,
ddt, J12.6, 8.0, 4.5 Hz), 4.68 (1H, ddt, J49.0, 8.3,
4.5 Hz), 2.11 (3H, s), 1.4 (20H, m). 19F NMR: d 2130.4
(dm, J49 Hz). Analysis: calcd for C14H25FO2 (244.36) C
68.82, H 10.31; found C 69.13, H 10.20%.
cis-2-Methylcyclododecyl acetate (cis-4a-C). Mp 239 to
2378C; n2D0 1.4712; 83%. 1H NMR: d 5.1 (1H, m), 2.04 (3H,
s), 1.7 (2H, m), 1.4 (18H, m), 1.1 (1H, m), 0.89 (3H, d,
J6.8 Hz). Analysis: calcd for C15H28O2 (240.39) C
74.95, H 11.74; found C 75.26, H 11.75%.
trans-1-Allyloxy-2-¯uorocyclododecane (trans-3-F). With
allyl bromide as the halide; mp 270 to 2678C; bp 120±
1218C/1 mmHg; n2D0 1.4730; 80%. 1H NMR: d 6.0 (1H, m),
5.3 (1H, dm, J17.0 Hz), 5.2 (1H, dm, J10.2 Hz), 4.66
(1H, symm. dm, J49.5 Hz), 4.2 (1H, dm, J12.0 Hz), 4.1
(1H, dm, J12.0 Hz), 3.6 (1H, m), 1.4 (20H, m). 19F NMR:
d 2128.3 (m). Analysis: calcd for C15H27FO (242.38) C
74.33, H 11.23; found C 74.31, H 11.15%.
trans-2-Methylcyclododecyl acetate (trans-4a-C). Mp
1
242 to 2408C; n2D0 1.4713; 83%. H NMR: d 4.95 (1H,
symm. m), 2.03 (3H, s), 1.8 (2H, m), 1.4 (18H, m), 1.1 (1H,
m), 0.87 (3H, d, J6.7 Hz). Analysis: calcd for C15H28O2
(240.39) C 74.95, H 11.74; found C 74.73, H 11.78%.
cis-1-Allyloxy-2-methylcyclododecane (cis-3-C). With
allyl bromide as the halide; mp 270 to 2668C; bp 110±
1138C/1 mmHg; n2D0 1.4788; 64%. H NMR: d 5.92 (1H,
Cyclododecyl propionate24 (4b-H). Bp 97±998C/
0.8 mmHg; n2D0 1.4700; 69%.
1
ddt, J17.1, 10.5, 6.0 Hz), 5.26 (1H, ddt, J17.1, 1.9,
1.5 Hz), 5.15 (1H, ddt, J10.5, 1.9, 1.5 Hz), 4.16 (2H,
symm. m), 3.6 (1H, m), 1.4 (20H, m), 0.91 (3H, d, J
7.0 Hz). Analysis: calcd for C16H30O (238.42) C 80.61, H
12.68; found C 80.81, H 12.87%.
cis-2-Fluorocyclododecyl propionate (cis-4b-F). Mp 247
1
to 2458C; n2D0 1.4644; 85%. H NMR: d 5.18 (1H, dddd,
J26.5, 7.5, 5.0, 1.4 Hz), 4.66 (1H, dddd, J48.3, 8.0, 6.1,
1.4 Hz), 2.37 (2H, q, J7.5 Hz), 1.7 (4H, m), 1.4 (16H, m),
1.15 (3H, t, J7.5 Hz). 19F NMR: d 2128.1 (m). Analysis:
calcd for C15H27FO2 (258.38) C 69.73, H 10.53; found C
70.13, H 10.76%.
trans-1-Allyloxy-2-methylcyclododecane (trans-3-C). With
allyl bromide as the halide; mp 272 to 2718C; bp 103±
1
1068C/0.9 mmHg; n2D0 1.4796; 40%. H NMR: d 5.92 (1H,
ddt, J17.1, 10.0, 5.9 Hz), 5.27 (1H, ddt, J17.1, 1.9,
1.5 Hz), 5.14 (1H, ddt, J10.0, 1.9, 1.5 Hz), 4.10 (1H,
ddt, J12.9, 6.1, 1.5 Hz), 3.88 (1H, ddt, J12.9, 6.1,
1.5 Hz), 3.25 (1H, td, J7.1, 3.0 Hz), 1.4 (20H, m), 1.0
(1H, m), 0.95 (3H, d, J7.0 Hz). Analysis: calcd for
C16H30O (238.42) C 80.61, H 12.68; found C 80.74, H
12.52%.
trans-2-Fluorocyclododecyl propionate (trans-4b-F). Mp
250 to 2498C; n2D0 1.4656; 48%. 1H NMR: d 5.25 (1H, ddt,
J12.8, 8.1, 5.0 Hz), 4.67 (1H, ddt, J49.0, 8.1, 4.5 Hz),
2.35 (1H, q, J7.7 Hz), 2.35 (1H, q, J7.3 Hz), 1.4 (20H,
m), 1.16 (3H, t, J7.5 Hz). 19F NMR: d 2130.5 (dm,
J49 Hz). Analysis: calcd for C15H27FO2 (258.38) C
69.73, H 10.53; found C 69.68, H 10.35%.
Ester
cis-2-Methylcyclododecyl propionate (cis-4b-C). Mp
1
250 to 2488C; 1.4700; 95%. H NMR: d 5.0 (1H, m),
General working procedure. The acyl chloride (25 mmol),
pyridine (2.0 mL, 2.0 g, 25 mmol) and the alcohol
(25 mmol) were consecutively dissolved in dichloro-
methane (50 mL). After 5 h at 258C, the mixture was
absorbed on silica gel (10 m) if the product was a cyclodo-
decanol derivative. It was eluted with a 1/10 (v/v) mixture of
diethyl ether and pentane from a column ®lled with silica
gel (0.10 mL). If the ester was a derivative of 2-propen-1-ol,
2-¯uoro-2-propen-1-ol, 2-methyl-2-propen-1-ol or 2-
phenylethanol, the mixture was washed with water
(2£10 mL) and brine (10 mL) before being dried and
evaporated. The product was isolated by distillation under
reduced pressure.
2.32 (2H, q, J7.5 Hz), 1.7 (2H, m), 1.4 (18H, m), 1.15
(3H, t, J7.5 Hz), 1.1 (1H, m), 0.89 (3H, d, J6.8 Hz).
Analysis: calcd for C16H30O2 (254.42) C 75.54, H 11.89;
found C 75.76, H 11.82%.
trans-2-Methylcyclododecyl propionate (trans-4b-C). Mp
1
257 to 2558C; n2D0 1.4703; 73%. H NMR: d 4.97 (1H,
symm. m), 2.32 (2H, q, J7.6 Hz), 1.8 (2H, m), 1.4 (18H,
m), 1.14 (3H, t, J7.6 Hz), 1.1 (1H, m), 0.87 (3H, d,
J6.7 Hz). Analysis: calcd for C16H30O2 (254.42) C
75.54, H 11.89; found C 75.88, H 11.88%.
Cyclododecyl isobutyrate (4c-H). Bp 263 to 2618C; bp
1
60±638C/0.3 mmHg; n2D0 1.4668; 80%. H NMRp: d 5.00
Cyclododecyl acetate23 (4a-H). Bp 141±1428C/11 mmHg;
n2D0 1.4719; 85%.
(1H, tt, J7.2, 4.7 Hz), 2.51 (1H, sept, J7.0 Hz), 1.7
(2H, m), 1.4 (20H, m), 1.17 (6H, d, J7.0 Hz). Analysis:
calcd for C16H30O2 (254.42) C 75.54, H 11.89; found C
75.94, H 12.02%.
cis-2-Fluorocyclododecyl acetate (cis-4a-F). Mp 237 to
1
2368C; n2D0 1.4719; 83%. H NMR: d 5.15 (1H, dddd,