3
24
ODINOKOV et al.
b. Alkene I, 2 g (5 mmol), in 20 ml of Freon-113
alcohol IV, 0.75 ml of acetic anhydride, and 0.8 ml
of pyridine was stirred for 72 h. It was then acidified
with 5% hydrochloric acid and extracted with diethyl
ether (3 10 ml). After appropriate treatment, the
product was purified by chromatography on silica gel
using 3:1 pentane diethyl ether as eluent. Yield 0.5 g
was ozonized as described above. The solvent was
distilled off, and 10 ml of anhydrous THF was added
to the residue. Sodium tetrahydridoborate, 0.38 g
10 mmol), and 10 ml of THF were then added in
portions while stirring at room temperature. After
h, 5 ml of 2 N hydrochloric acid was added, and
(
1
1
3
(90%). IR spectrum, , cm : 1760 s (C O). H NMR
the mixture was stirred for an additional 3 h and
extracted with ethyl acetate (3 20 ml). The extract
spectrum (CDCl ), , ppm (J, Hz): 2.16 s (3H, CH ),
3
3
3
13
4
.59 t [2H, CH , J(HF) = 13.0]. C NMR spectrum,
2
was dried over MgSO and evaporated to obtain
4
, ppm (J, Hz): 20.00 s (CH ), 59.61 t [CH ,
C
3
2
0
.82 g (45%) of acid III which was identical (in the
2
J(CF) = 27.8], 99.1 136.4 m (CF , CF ), 169.31 s
2
3
1
13
IR and H and C NMR spectra) to a sample prepared
(
CO). Found, %: C 24.96; H 1.09. C H F O . Cal-
8 5 13 2
as described in a.
culated, %: C 25.28; H 1.33.
c. Alkene I, 2 g (5 mmol), in 20 ml of Freon-113
containing 0.4 ml (10 mmol) of MeOH was ozonized
as described above. The solvent was distilled off to
isolate 1.56 g (86%) of acid III which was identical
Perfluoroheptanamide (VI). To a solution of
.8 g (5 mmol) of acid III in 15 ml of anhydrous
1
methanol we added with stirring 0.7 g (13 mmol) of
anhydrous ammonium chloride, and the mixture was
kept for 3 days at room temperature. It was then
made alkaline by adding a 10% solution of sodium
methoxide in methanol and evaporated under reduced
pressure (40 C). The residue was extracted with
diethyl ether (3 20 ml), and the extract was washed
with a saturated solution of sodium chloride, dried
(
IR, NMR) to a sample prepared as desribed in a.
,2,3,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-1-heptanol
IV). a. A solution of ozonide II in 20 ml of anhy-
2
(
drous THF (prepared from 2 g of alkene I by the
above procedure) was slowly added (dropwise) with
vigorous stirring (argon, 0 C) to a suspension of
0
.37 g (9.6 mmol) of LiAlH in 8 ml of anhydrous
4
over MgSO , and evaporated. Yield 0.94 g (48%),
4
THF. The mixture was stirred for 4 h at room tem-
perature and was left overnight, 30 ml of 5% hydro-
chloric acid was slowly added, and the mixture was
extracted with Freon-113 (2 30 ml). The extract was
washed in succession with saturated solutions of
NaHCO and NaCl and dried over MgSO , and the
1
mp 136 C (decomp.). IR spectrum, , cm : 1675 s
C O), 3350 br, s (NH, Wh/2 = 450 cm ). H NMR
1
1
(
spectrum (CD OD), , ppm: 5.17 (NH , W = 9 Hz).
3
2
h/2
1
3
C NMR spectrum (CD OD),
104.9 118.1 m (CF ), 118.6 q.t [CF , J(CF) =
287.45, J(CF) = 33.3], 163.5 t [CONH , J(CF) =
, ppm (J, Hz):
3
C
1
3
4
2
3
2
2
solvent was removed. Yield of alcohol IV 1.57 g
2
1
(
3
90%). IR spectrum, , cm : 3350 br.s (OH, W
=
31.0]. Mass spectrum (PICI), m/z (I , %): 393 (1)
h/2
rel
1
1
+
+
42 cm ). H NMR spectrum (CDCl ), , ppm
[M+C H ] , 379 (17) [M+CH ] , 366 (4), 365 (100)
[M+H ] , 347 (11) [M NH ] , 165 (3), 151 (8),
2 2
3
2 6 4
+
+
(
J, Hz): 3.96 t [2H, CH O, J(HF) = 13.2], 4.6 br.s
2
(
1H, OH, Wh/2 = 20 Hz).
b. To a suspension of 0.1 g (2.3 mmol) of LiAlH4
137 (12), 127 (15), 123 (13), 113 (14), 111 (15), 108
13), 100 (8). Mass spectrum (NICI), m/z (I , %):
344 (100) [M F] , 328 (74) [M FNH2] , 316 (31)
(
rel
in 20 ml of THF we added dropwise with stirring
argon, 0 C) a solution of 1.3 g (3 mmol) of acid III
(
[M F CO] , 310 (12) [M F NH] , 300 (59) [M
2
in 10 ml of THF. The mixture was then treated as
described above in a. Yield 1.22 g (70%). The product
was identical (IR, H NMR) to a sample prepared as
FNH2 CO] , 290 (27) [M F NH HF] , 262 (46)
2
[M F NH HF CO] , 224 (11) [M F NH HF
2
2
1
CO F ] , 216 (12) [M F CO C F ] , 212 (3),
2 2 4
described in a.
c. To a suspension of 0.18 g (4.7 mmol) of LiAlH4
in 20 ml of THF we added dropwise with stirring
166 (5). Mass spectrum (EI), m/z (I , %): 319 (1)
rel
+
+
[
[
[
(
M CONH ] , 300 (1) [M CONH F] , 281 (2)
2 2
+
+
M CONH2 F ] , 231 (9) [C F ] , 197 (3), 181 (14)
2
5 9
+
+
C F ] , 169 (9), 131 (100) [C F ] , 119 (19), 100
16) [C F ] , 69 (49) [CF ] , 45 (51). Found, %:
(argon, 0 C) a solution of 1.8 g (4.7 mmol) of ester
4
7
3 5
+
+
VII or 1.84 g (4.7 mmol) of ester VIII. The mixture
was then treated as described in a. The yield of IV
was 1.48 g (85%) from ester VII or 1.4 g (80%) from
ester VIII. The product was identical (IR, H NMR)
to a sample prepared as described in a.
2
4
3
C 22.87; H 0.48; N 3.55. C7H2F13NO. Calculated, %:
C 23.15; H 0.56; N 3.86.
1
Methyl perfluoroheptanoate (VII). Alkene I,
2
g (5 mmol), in 20 ml of Freon-113 containing
2
,2,3,3,4,4,5,5,6,6,7,7,7-Tridecafluoroheptyl
0.8 ml (20 mmol) of methanol was ozonized by the
above procedure. Removal of the solvent gave 1.55 g
acetate (V). A mixture of 0.52 g (1.5 mmol) of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 3 2001