124
K. Takai et al. / Journal of Fluorine Chemistry 128 (2007) 120–126
1
9
1
(
J = 10.70 Hz).
2H, t, J = 6.70 Hz). F NMR (CDCl ) ppm: À3.51 (3F, t,
H NMR (CDCl ) d: 1.28–1.54 (14H, m), 1.55–1.69 (4H, m),
3
3
1.94–2.08 (2H, m), 2.11–2.19 (4H, m), 2.35 (2H, t,
1
9
J = 7.61 Hz).
À55.34 (2F, t, J = 18.73 Hz). IR (neat): 1725 cm (C O).
F NMR (CDCl ) ppm: À22.54 (3F, s),
3
À1
3
.2.1.6. 18,18,18-Trifluorostearolic acid (1a). To 7a (253 mg,
.79 mmol) in acetone (4 mL) was added Jones reagent at room
+
ESI-MS (m/z): calcd. for C H F O [M] 370.1931, found
370.1923.
0
1
8 27 5 2
temperature until the brownish color of the chromium(VI) ion
remained for 30 min. The reaction mixture was quenched with
2-propanol followed by filtration and removal of the solvent.
The residue was extracted with EtOAc, washed with satd NaCl
3.2.3. Synthesis of 16,16,17,17,18,18,18-
heptafluorostearolic acid (1c)
aq, and dried over MgSO , affording 18,18,18-trifluorostearolic
4
3.2.3.1. 1-(2-Tetrahydropyranyloxy)pentadec-14-en-9-yne
(4B). 4B was prepared from 3 and 5-bromo-1-pentene in the
acid (1a) (233 mg, 88%) after purification using column
chromatography and eluting with n-hexane/EtOAc (3:1).
same manner as 4A (not purified).
1
1
H NMR (CDCl ) d: 1.26–1.43 (12H, m), 1.43–1.51 (4H, m),
3
H NMR (CDCl ) d: 1.25–1.43 (8H, m), 1.41–1.64 (10H, m),
3
1
2
.51–1.59 (2H, m), 1.57–1.65 (2H, m), 1.99–2.12 (2H, m),
1.67–1.76 (1H, m), 1.78–1.88 (1H, m), 2.11–2.22 (6H, m), 3.38
(1H, dt, J = 9.44, 6.70 Hz), 3.47–3.54 (1H, m), 3.73 (1H, dt,
J = 9.44, 7.01 Hz, H1), 3.84–3.91 (1H, m), 4.57 (1H, dd,
J = 4.27, 3.05 Hz), 4.97 (1H, ddt, J = 10.05, 1.83, 1.22 Hz),
5.03 (1H, dq, J = 17.05, 1.83 Hz), 5.80 (1H, ddt, J = 17.05,
1
.09–2.18 (4H, m), 2.32 (2H, t, J = 7.61 Hz). F NMR (CDCl )
9
3
À1
ppm: À3.51 (3F, t, J = 10.70 Hz). IR (neat): 1711 cm (C O).
+
ESI-MS (m/z): calcd. for C H F O [M] 334.2120, found
1
8 29 3 2
3
34.2120.
10.05, 6.70 Hz).
3
.2.2. Synthesis of 17,17,18,18,18-pentafluorostearolic
acid (1b)
.2.2.1. 17,17,18,18,18-Pentafluoro-15-iodooctadec-9-yn-1-ol
3.2.3.2. Pentadec-14-en-9-yn-1-ol (5B). 5B was prepared
3
from 4B in the same manner as 5A (87%, two steps).
1
(
6b). 5A (733 mg, 4.03 mmol), perfluoroethyl iodide
0.48 mL, 4.03 mmol), NaHCO (130 mg, 1.55 mmol), 80%
H NMR (CDCl ) d: 1.26–1.42 (8H, m), 1.42–1.51 (2H, m),
3
(
Na S O (377 mg, 1.55 mmol), acetonitrile (3.1 mL) and
1.53–1.61 (4H, m), 2.11–2.19 (6H, m), 3.64 (2H, t,
J = 6.70 Hz), 4.97 (1H, ddt, J = 10.05, 1.83, 1.22 Hz), 5.03
(1H, dq, J = 17.05, 1.83 Hz), 5.80 (1H, ddt, J = 17.05, 10.05,
6.70 Hz).
3
2
2 4
deionized water (1.6 mL) were placed and filled up with
acetonitrile in the stainless-steel reactor as noted above. Then,
the mixture was stirred overnight at room temperature. The
reaction mixture was diluted with deionized water, extracted
with CH Cl , washed with satd NaCl aq, and dried over
3.2.3.3. 16,16,17,17,18,18,18-Heptafluoro-14-iodooctadec-9-
yn-1-ol (6c). 6c was prepared from 5B and perfluoropropyl
2
2
MgSO , affording 17,17,18,18,18-pentafluoro-15-iodooctadec-
4
iodide in the same manner as 6b (86%).
1
9
next reaction without further purification.
-yn-1-ol (6b) (1.58 g) as a crude product. This was used in the
H NMR (CDCl ) d: 1.25–1.41 (8H, m), 1.42–1.51 (2H, m),
3
1.52–1.67 (3H, m), 1.70–1.80 (1H, m), 1.86–1.99 (2H, m), 2.14
(2H, tt, J = 7.00, 2.44 Hz), 2.22 (2H, tt, J = 7.00, 2.44 Hz),
2.70–2.87 (1H, m), 2.84–3.02 (1H, m), 3.64 (2H, t,
19
J = 6.70 Hz), 4.33–4.40 (1H, m). F NMR (CDCl ) ppm:
1
H NMR (CDCl ) d: 1.26–1.42 (8H, m), 1.45–1.73 (8H, m),
3
1
2
.74–1.89 (2H, m), 2.12–2.17 (2H, m), 2.16–2.22 (2H, m), 2.67–
1
9
F
.96 (2H, m), 3.64 (2H, t, J = 6.71 Hz), 4.27–4.36 (1H, m).
3
NMR (CDCl ) ppm: À22.94 (3F, s), À52.39 to À56.43 (2F, m).
À17.42 (3F, t, J = 10.70 Hz), À49.12 to À53.43 (2F, m),
À64.84 to À65.07 (2F, m).
3
3
.2.2.2. 17,17,18,18,18-Pentafluorooctadec-9-yn-1-ol
7b). 6b (1.58 mg, 3.27 mmol, crude product) was added to a
mixture of Zn powder (427 mg, 6.54 mmol), NiCl Á6H O
(
3.2.3.4. 16,16,17,17,18,18,18-Heptafluorooctadec-9-yn-1-ol
(7c). 1.6 M n-BuLi/hexane (4.61 mL, 7.19 mmol) was
dropped into a solution of 6c (1.69 g, 3.27 mmol) in dry
2
2
(
77.7 mg, 3.27 mmol) in dry THF (5.0 mL), and deionized
water (five drops). This mixture was stirred overnight at room
temperature. The reaction mixture was quenched with satd
NaHCO aq, extracted with CH Cl , washed with satd NaCl aq,
Et O (25 mL) at À78 8C under nitrogen, and then stirred for
2
4 h. To the mixture was added pre-cooled (À78 8C) MeOH
(4.6 mL), and then allowed to 0 8C. The reaction mixture was
3
2
2
and dried over MgSO , 17,17,18,18,18-pentafluorooctadec-9-
4
poured into satd NH Cl aq, extracted with EtOAc, washed with
satd NaCl aq, dried over MgSO , affording 16,16,17,17,18,
4
yn-1-ol (7b) (593 mg, 51% two steps yield) after purification
using column chromatography and eluting with n-hexane/
EtOAc (2:3).
4
18,18-heptafluorooctadec-9-yn-1-ol (7c) (660 mg, 51%) after
purification using column chromatography and eluting with n-
hexane/EtOAc (3:1).
1
H NMR (CDCl ) d: 1.26–1.55 (16H, m), 1.51–1.64 (4H, m),
3
1
1
J = 6.70 Hz).
.94–2.08 (2H, m), 2.10–2.20 (4H, m), 3.64 (2H, t,
1
H NMR (CDCl ) d: 1.25–1.42 (8H, m), 1.43–1.67 (10H, m),
3
9
F NMR (CDCl ) ppm: À22.57 (3F, s),
1.98–2.13 (2H, m), 2.10–2.21 (4H, m), 3.64 (2H, t,
9
3
1
À55.35 (2F, t, J = 18.74 Hz).
J = 6.70 Hz).
J = 10.57 Hz), À52.38 to À52.62 (2F, m), À64.94 (2F, brs).
F NMR (CDCl ) ppm: À17.69 (3F, t,
3
3.2.2.3. 17,17,18,18,18-Pentafluorostearolic acid (1b). 7b
was oxidized with Jones reagent to afford 17,17,18,18,18-
3.2.3.5. 16,16,17,17,18,18,18-Heptafluorostearolic acid
(1c). 7c was oxidized with Jones reagent to afford
pentafluorostearolic acid (1b) in the same manner as 1a (74%).