GENERAL PROCEDURE FOR THE SYNTHESIS OF SPIROCYCLIC 3-HYDROXY- ...
1093
room temperature, 100 ml of 10% aqueous sulfuric
acid was added, the mixture was filtered, the organic
phase was separated, and the aqueous phase was satu-
rated with sodium chloride and extracted with diethyl
ether. The extracts were combined with the organic
phase and dried over anhydrous sodium sulfate, and
the solvent was distilled off under reduced pressure.
Yield 11.4 g (90%), light yellow liquid. IR spectrum, ν,
CH NCH ), 5.18 m (2H, CH=CH ), 5.93 m (1H,
2
2
2
+
CH=CH ). Mass spectrum, m/z: 228 [M + H] , 171
2
+
+
[M – 57 + H] , 127 [M – 101 + H] . Found, %:
C 63.61; H 9.43; N 6.02. C H NO . Calculated, %:
1
2
21
3
C 63.44; H 9.25; N 6.17. M 227.
Compounds IVd and IVe were synthesized in
a similar way.
–
1
1
tert-Butyl 3-allyl-3-hydroxypiperidine-1-carbox-
ylate (IVd). Yield 98%, light yellow oily liquid. IR
cm : 3500 (OH), 1617 (C=C). H NMR spectrum, δ,
ppm: 1.58–1.65 m (4H, CH ), 1.81–1.87 m (4H, CH ),
2
2
–
1
spectrum, ν, cm : 3480 (OH), 1690 (C=O), 1608
2
.15 d (2H, 1-CH ), 3.16 s (1H, OH), 5.05 m (2H,
2
1
(
C=C). H NMR spectrum, δ, ppm: 1.48 s (9H, t-Bu),
CH=CH ), 5.85 m (1H, CH=CH ). Mass spectrum:
2
2
+
1
3
.54–1.78 m (4H, CH ), 2.27 m (3H, 3-CH , OH),
m/z 127 [M + H] . Found, %: C 76.28; H 11.18.
C H O. Calculated, %: C 76.19; H 11.11. M 126.
2
2
.03 d and 3.68 m (2H each, NCH ), 5.18 m (2H,
2
8
14
CH=CH ), 5.91 m (1H, CH=CH ). Mass spectrum,
2
2
Compounds IVb and IVf were synthesized in
a similar way.
+
+
m/z: 242 [M + H] , 185 [M – 57 + H] , 141 [M – 101 +
H] . Found, %: C 64.45; H 9.28; N 5.63. C H NO .
+
13
23
3
1
-Allylcyclohexan-1-ol (IVb). Yield 96%, light
Calculated, %: C 64.73; H 9.54; N 5.81. M 241.
–
1
yellow liquid. IR spectrum, ν, cm : 3496 (OH), 1612
C=C). H NMR spectrum, δ, ppm: 1.43–1.54 m (6H,
1
tert-Butyl 4-allyl-4-hydroxypiperidine-1-carbox-
ylate (IVe). Yield 100%, colorless oily liquid. IR spec-
(
CH ), 1.68–1.79 m (4H, CH ), 2.21 d (2H, 1-CH ),
2
2
2
–
1
trum, ν, cm : 3486 (OH), 1692 (C=O), 1610 (C=C).
3
.24 s (1H, OH), 5.06 m (2H, CH=CH ), 5.87 m (1H,
2
1
+
H NMR spectrum, δ, ppm: 1.39 s (9H, t-Bu), 1.45–
CH=CH ). Mass spectrum: m/z [M + 1] 141. Found,
2
1
.62 m (4H, CH ), 2.16 d (2H, 4-CH ), 2.28 s (1H,
%
: C 77.38; H 11.26. C H O. Calculated, %: C 77.14;
2
2
9
16
OH), 3.04 m and 3.64 m (2H each, NCH ), 5.08 m
H 11.43. M 140.
2
(
2H, CH=CH ), 5.88 m (1H, CH=CH ). Mass spec-
2
2
4
-Allyltetrahydropyran-4-ol (IVf). Yield 98%,
+
+
–
1
trum, m/z: 242 [M + H] , 185 [M – 57 + H] , 141
[M – 101 + H] . Found, %: C 64.68; H 9.41; N 5.56.
colorless liquid. IR spectrum, ν, cm : 3496 (OH),
615 (C=C). H NMR spectrum, δ, ppm: 1.42–1.53 m
+
1
1
C H NO . Calculated, %: C 64.73; H 9.54; N 5.81.
1
3
23
3
(
3H, CH , OH), 1.73 m (2H, CH ), 2.25 d (2H, 4-CH ),
2
2
2
M 241.
3
5
.80 m (4H, CH OCH ), 5.19 m (2H, CH=CH ),
2 2 2
.88 m (1H, CH=CH ). Mass spectrum: m/z 143
1-Oxaspiro[4.4]nonan-3-ol (Va). A solution of
2
+
[M + H] . Found, %: C 67.43; H 9.75. C H O . Calcu-
19 g (0.1 mol) of Na S O in 80 ml of water was added
8
14
2
2
2
5
lated, %: C 67.61; H 9.86. M 142.
dropwise over a period of 2 h to a mixture of 12.6 g
(
0.1 mol) of compound IVa, 21.4 g (0.1 mol) of NaIO4,
tert-Butyl 3-allyl-3-hydroxypyrrolidine-1-car-
boxylate (IVc). Zinc dust, 13 g (0.2 mol), was slowly
added under vigorous stirring to a mixture of 18.5 g
1
50 ml of tert-butyl alcohol, and 50 ml of water under
stirring at 50°C. The mixture was stirred for 10 h at
0°C and for 10 h at room temperature, the dark brown
5
(
(
0.1 mol) of tert-butyl 3-oxopyrrolidine-1-carboxylate
IIIc), 30.25 g (0.25 mol) of allyl bromide, 50 ml of
organic layer was separated, and the aqueous phase
was saturated with sodium chloride and extracted with
ethyl acetate. The extracts were combined with the
organic phase and washed with a saturated aqueous
solution of sodium thiosulfate, the resulting colorless
solution was dried over anhydrous sodium sulfate, the
solvent was removed under reduced pressure, and the
oily residue was purified by column chromatography
on silica gel using ethyl acetate–hexane (2:1) as
eluent. Yield 6.8 g (48%), colorless oily liquid. IR
spectrum: ν 3478 cm (OH). H NMR spectrum, δ,
ppm: 1.51–1.63 m (4H, CH ), 1.75–1.84 m (4H, CH ),
1.92 d (2H, CH ), 3.28 d (2H, OCH ), 3.87 m (1H,
CHO), 4.45 s (1H, OH). Found, %: C 67.52; H 9.73.
C H O . Calculated, %: C 67.61; H 9.86.
THF, and 100 ml of a saturated aqueous solution of
ammonium chloride in such a way that the temperature
did not exceed 40°C. The mixture was stirred for 12 h
at room temperature (TLC monitoring), 100 ml of
1
0% aqueous sulfuric acid was added, the mixture was
filtered, the organic phase was separated, and the
aqueous phase was extracted with ethyl acetate. The
extracts were combined with the organic phase and
dried over anhydrous sodium sulfate, and the solvent
was distilled off under reduced pressure. Yield 22.5 g
–
1
1
–
1
(
3
99%), light yellow oily liquid. IR spectrum, ν, cm :
2
2
1
486 (OH), 1689 (C=O), 1605 (C=C). H NMR spec-
trum, δ, ppm: 1.43 s (9H, t-Bu), 1.88 m (2H, CH2),
.25 d (2H, 3-CH ), 3.28 s (1H, OH), 3.51 d (4H,
2
2
2
2
8
14
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 7 2011