Hz), 62.6, 33.4 (t, J ) 23 Hz), 31.8, 29.5, 29.3, 29.2, 29.1, 29.0,
22.6, 21.3, 14.0, 13.9 ppm. HRMS (CI) (m/z): (MH)+ calcd for
C14H27F2O2, 265.1979; found, 265.1980. Anal. Calcd for
Eth yl 2,2-d iflu or o-3-m eth ylbu ta n oa te (4 g)4 was prepared
from 3g as described above, resulting in 65% yield of an oil. IR
cm-1: 1760. 1H NMR: 4.32 (2 H, q, J ) 7 Hz), 2.36 (1 H, m),
1.35 (3 H, t, J ) 7 Hz), 1.03 ppm (6 H, d, J ) 7 Hz). 19F NMR:
-115.0 ppm (d, J ) 15 Hz). 13C NMR: 164.4 (t, J ) 33 Hz),
117.7 (t, J ) 250 Hz), 62.9, 33.0 (t, J ) 23 Hz), 14.7, 14.0 ppm.
C
14H26F2O2: C, 63.61; H, 9.91; F, 14.37. Found: C, 63.44; H,
10.26; F, 13.95.
Eth yl 3-cycloh exyl-2,2-d iflu or op r op a n oa te (4b) was pre-
pared from 3b as described above, resulting in 75% yield of an
Eth yl 2,2-d iflu or o-8-ch lor oocta n oa te (4h ) was prepared
from 3h as described above, resulting in 55% yield of an oil. IR
1
oil. IR cm-1:1761. H NMR: 4.32 (2 H, q, J ) 7 Hz), 1.95 (2 H,
td, J 1 ) 17 Hz, J 2 ) 6 Hz), 1.35 ppm (3 H, t, J ) 7 Hz). 19F
NMR: -103.8 ppm (t, J ) 17 Hz). 13C NMR: 164.5 (t, J ) 33
Hz), 116.4 (t, J ) 250 Hz), 62.6, 41.4 (t, J ) 22 Hz), 33.4, 31.8,
25.9, 13.8 ppm. HRMS (CI) (m/z): (MH)+ calcd for C11H19F2O2,
221.1353; found, 221.1352. Anal. Calcd for C11H18F2O2: C, 59.98;
H, 8.24; F, 17.25. Found: C, 59.67; H, 8.02; F, 18.00.
1
cm-1: 1761. H NMR: 4.31 (2 H, q, J ) 7 Hz), 3.52 (2 H, t, J )
7 Hz), 2.05 (2 H, m), 1.77 (2 H, m), 1.44 (6 H, m), 1.34 ppm (3 H,
t, J ) 7 Hz). 19F NMR: -106.4 ppm (t, J ) 17 Hz). 13C NMR:
164.3 (t, J ) 34 Hz), 116.2 (t, J ) 250 Hz), 62.7, 44.8, 34.2 (t, J
) 24 Hz), 32.2, 28.2, 26.4, 21.2, 13.9 ppm. HRMS (CI) (m/z):
(MH)+ calcd for C10H17ClF2O2, 243.0963; found, 243.0963. Anal.
Calcd for C10H17ClF2O2: C, 49.49; H, 7.06. Found: C, 50.04; H,
7.18.
Eth yl 4-eth yl-2,2-d iflu or oocta n oa te (4c) was prepared
from 3c as described above, resulting in 75% yield of an oil. IR
1
cm-1: 1761. H NMR: 4.31 (2 H, q, J ) 7 Hz), 2.00 (2 H, td, J 1
) 18 Hz, J 2 ) 6 Hz), 0.92-0.81 ppm (6 H, m). 19F NMR: -104.2
ppm (td, J 1 ) 18, J 2 ) 4 Hz). 13C NMR: 164.5 (t, J ) 33 Hz),
116.7 (t, J ) 250 Hz), 62.6, 37.8 (t, J ) 22 Hz), 33.1, 32.9, 28.3,
26.1, 22.7, 13.9, 13.8, 10.1 ppm. HRMS (CI) (m/z): (MH)+ calcd
for C12H23F2O2, 237.1666; found, 237.1663. Anal. Calcd for
Eth yl 2,2-d iflu or o-7-k etoocta n oa te (4i)19 was prepared
from 3i as described above, resulting in 65% yield of an oil.
HRMS (CI) (m/z): (MH)+ calcd for C10H17F2O3, 223.1146; found,
223.1142. All other spectral data are in full agreement with the
literature.
C
12H22F2O2: C, 60.99; H, 9.38; F, 16.08. Found: C, 61.29; H,
2,2-Diflu or od od eca n oic a cid (5a )15 was obtained in almost
quantitative yield by heating 150 mg of 4a in refluxing 5%
aqueous KOH (20 mL) and 2 mL of EtOH. After acidification,
the aqueous layer was extracted with ether, dried over MgSO4,
and evaporated. The acid was purified by flash chromatography
(Merck silica gel 60H) using petrol ether-ethyl acetate as eluent
9.30; F, 16.59.
Eth yl 2,2-d iflu or o-5,9-d im eth yld eca n oa te (4d ) was pre-
pared from 3d as described above, resulting in 70% yield of an
oil. IR cm-1: 1763. 1H NMR: 4.33 (2 H, q, J ) 7 Hz), 2.21-1.90
(2 H, m), 1.12-0.85 ppm (9 H, m). 19F NMR: -106.5 ppm (t, J
) 16 Hz). 13C NMR: 164.4 (t, J ) 33 Hz), 116.5 (t, J ) 250 Hz),
62.6, 39.1, 36.6, 32.2, 32.1 (t, J ) 23 Hz), 28.0, 27.8, 24.5, 22.5,
19.2, 13.9 ppm. HRMS (CI) (m/z): (MH)+ calcd for C14H27F2O2,
265.1979; found, 265.1979. Anal. Calcd for C14H26F2O2: C, 63.61;
H, 9.91; F, 14.37. Found: C, 62.95; H, 9.73; F, 14.80.
Eth yl 2,2-d iflu or o-4-n or bor n a n ebu ta n oa te (4e) was pre-
pared from 3e as described above, resulting in 75% yield of an
1
to yield an oil. IR cm-1: 1757. H NMR: 8.99 (1 H, br), 2.00 (2
H, m), 1.51 (2 H, m), 0.88 ppm (3 H, t, J ) 7 Hz). 19F NMR:
-107.0 ppm (t, J ) 17 Hz). 13C NMR: 169.0 (t, J ) 34 Hz), 116.0
(t, J ) 250 Hz), 34.1 (t, J ) 23 Hz), 32.0, 29.6, 29.4, 29.3, 29.2,
29.1, 29.0, 23.0, 21.0, 14.0 ppm. HRMS (CI) (m/z): (MH)+ calcd
for C12H23F2O2, 237.1661; found, 237.1666. Anal. Calcd for
C12H22F2O2: C, 60.99; H, 9.38. Found: C, 61.39; H, 9.54.
1
oil. IR cm-1: 1762. H NMR: 4.32 (2 H, q, J ) 7 Hz), 1.35 ppm
(3 H, t, J ) 7 Hz). 19F NMR: -106.3 ppm (t, J ) 17 Hz). 13C
NMR: 164.3 (t, J ) 33 Hz), 116.3 (t, J ) 250 Hz), 62.6, 41.6,
40.8, 37.8, 36.4, 35.1, 32.9 (t, J ) 24 Hz), 29.9, 28.5, 28.0, 13.9
ppm. HRMS (CI) (m/z): (MH)+ calcd for C13H21F2O2, 247.1509;
found, 247.1512. Anal. Calcd for C13H20F2O2: C, 63.40; H, 8.18;
F, 15.43. Found: C, 63.69; H, 8.30; F, 15.48.
2,2-Diflu or o-4-n or bor n a n ebu ta n oic a cid (5e) was pre-
pared from 4e as described above in the almost quantitative yield
of an oil. IR cm-1: 1758. 1H NMR: 5.10 (1 H, br), 2.20-1.91
ppm (4 H, m). 19F NMR: -107.0 ppm (t, J ) 17 Hz). 13C NMR:
167.0 (t, J ) 33 Hz), 116.0 (t, J ) 250 Hz), 41.6, 40.9, 37.8, 36.4,
35.1, 32.8 (t, J ) 22 Hz), 29.9, 28.6, 28.0 ppm. HRMS (CI) (m/z):
(MH)+ calcd for C11H17F2O2, 219.1196; found, 219.1192.
Eth yl 2,2-d iflu or o-3-m eth ylu n d eca n oa te (4f) was pre-
pared from 3f as described above, resulting in 70% yield of an
1
oil. IR cm-1: 1759. H NMR: 4.32 (2 H, q, J ) 7 Hz), 1.35 (3 H,
Ack n ow led gm en t. This research was supported by
the USA-Israel Binational Science Foundation (BSF),
J erusalem, Israel.
t, J ) 7 Hz), 1.02 (3 H, t, J ) 7 Hz), 0.88 ppm (3 H, t, J ) 7 Hz).
19F NMR: -113.3 ppm (dd, J 1 ) 40, J 2 ) 15 Hz). 13C NMR: 164.4
(t, J ) 33 Hz), 117.8 (t, J ) 250 Hz), 62.5, 37.7 (t, J ) 22 Hz),
31.7, 29.5, 29.4, 29.3, 28.7, 22.5, 13.9, 13.2, 11.8 ppm. HRMS
(CI) (m/z): (MH)+ calcd for C14H27F2O2, 265.1979; found, 265.1983.
J O034829I
J . Org. Chem, Vol. 68, No. 21, 2003 8289