MOSKALENKO, BOEV
1532
m/z 319 [M + H]+. Found, %: C 82.87; H 8.05; N 8.67.
C22H26N2. Calculated, %: C 83.02; H 8.18; N 8.81.
3 mmol of freshly distilled benzaldehyde in 10 ml of
toluene was heated under reflux over a period of 5 h.
The solvent was slowly distilled off under atmospheric
pressure, the residue was dissolved in ethyl acetate and
subjected to chromatography on silica gel. Compound
XIa or XIb was eluted with ethyl acetate–hexane
(1:2); their yields were 78 and 83%, respectively.
tert-Butyl 9-benzylideneamino-3-azabicyclo-
[3.3.1]nonane-3-carboxylate (XIb) was synthesized
in a similar way. Yield 79%, α/β ratio 43:57. IR spec-
1
trum, ν, cm–1: 1684 (C=O), 1608 (C=N). H NMR
spectrum, δ, ppm: 1.30 s (9H, t-Bu), 1.46–2.10 m (6H,
CH2), 2.38–2.42 m (2H, CH), 3.42 d (2H, NCH2),
3.62 d (2H, NCH2), 3.92 s (9-H, β), 4.05 s (9-H, α),
6.81 s (1H, =CH), 7.01–7.18 m (5H, C6H5). Mass spec-
trum, m/z: 329 [M + H]+, 272 [M – 57 + H]+, 228 [M –
101 + H]+. Found, %: C 73.31; H 8.45; N 8.37.
C20H28N2O2. Calculated, %: C 73.17; H 8.54; N 8.54.
Methyl 1-(3-benzyl-3-azabicyclo[3.3.1]non-9-yl)-
1H-1,2,3-triazole-4-carboxylate (XIIIa). A mixture
of 0.77 g (3 mmol) of azide VIa and 0.3 g (3.5 mmol)
of methyl prop-2-ynoate in 5 ml of toluene was heated
for 10 h under reflux (until the initial azide disap-
peared according to the TLC data). The solvent was
distilled off under reduced pressure, and the residue
was dissolved in ethyl acetate and purified by chroma-
tography on silica gel. Compound XIIIa was isolated
as a mixture of α- and β-epimers at a ratio of 45:55.
Yield 0.52 g (51%), mp 148–152°C (from hexane). IR
3-Benzyl-3-azabicyclo[3.3.1]nonan-9-amine
(XIIa). A solution of 2.56 g (10 mmol) of azide VIa in
20 ml of THF was added under argon to a suspension
of 0.2 g (5.2 mmol) of lithium tetrahydridoaluminate in
10 ml of anhydrous THF, and the mixture was stirred
for 5 h at room temperature (until the initial com-
pounds disappeared according to the TLC data). The
mixture was then treated with 30 ml of 10% aqueous
ammonium chloride, stirred for 1 h, and filtered, and
the filtrate was extracted with ethyl acetate (2×50 ml).
The extracts were combined, washed with water, and
dried over anhydrous sodium sulfate, the solvent was
distilled off under reduced pressure, and the residue
was crystallized from hexane on cooling to –20°C.
Compound XIIa was isolated as a mixture of α- and
β-epimers at a ratio of 35:65. Yield 1.48 g (64%),
mp 65–68°C. IR spectrum, ν, cm–1: 3367, 3358 (NH2).
1H NMR spectrum, δ, ppm: 1.36–2.04 m (6H, CH2),
2.12–2.21 m (2H, CH), 2.78 d (2H, NCH2), 2.85 d
(2H, NCH2), 3.36 s (2H, PhCH2), 3.62 m (9-H, β),
3.86 m (9-H, α), 4.22 br.s (2H, NH2), 7.02–7.17 m
(5H, C6H5). Mass spectrum: m/z 231 [M + H]+. Found,
%: C 78.41; H 9.36; N 12.08. C15H22N2. Calculated, %:
C 78.26; H 9.57; N 12.17.
1
spectrum: ν 1698 cm–1 (C=O). H NMR spectrum, δ,
ppm: 1.38–2.08 m (6H, CH2), 2.14–2.22 m (2H, CH),
2.79 d (2H, NCH2), 2.86 d (2H, NCH2), 3.38 s (2H,
PhCH2), 3.56 s (3H, OCH3), 3.72 s (9-H, β), 3.92 s
(9-H, α), 7.05–7.36 m (6H, 5-H, C6H5). Mass spec-
trum: m/z 341 [M + H]+. Found, %: C 65.84; H 7.15;
N 16.31. C19H24N4O2. Calculated, %: C 67.06; H 7.06;
N 16.47.
Methyl 1-(3-tert-butoxycarbonyl-3-azabicyclo-
[3.3.1]non-9-yl)-1H-1,2,3-triazole-4-carboxylate
(XIIIb) was synthesized in a similar way. Yield 49%,
α/β ratio 42:58. IR spectrum, ν, cm–1: 1698, 1684
1
(C=O). H NMR spectrum, δ, ppm: 1.32 s (9H, t-Bu),
1.48–2.15 m (6H, CH2), 2.34–2.39 m (2H, CH), 3.42 d
(2H, NCH2), 3.58 d (2H, NCH2), 3.68 s (3H, OCH3),
3.91 s (9-H, β), 4.08 s (9-H, α), 7.11 s (1H, 5-H). Mass
spectrum, m/z: 351 [M + H]+, 294 [M – 57 + H]+, 250
[M – 101 + H]+. Found, %: C 58.12; H 7.27; N 15.86.
C17H26N4O4. Calculated, %: C 58.29; H 7.43; N 16.00.
9-Hydroxy-3-azoniabicyclo[3.3.1]nonane
chloride (IIc). Compound IIb, 1.16 g (5 mmol), was
dissolved in 10 ml of anhydrous ethanol, 20 ml of
a saturated solution (16%) of hydrogen chloride in
anhydrous dioxane was added, and the mixture was
stirred for 1 h and then heated for 1 h under reflux. The
solvent was removed under reduced pressure, the
residue was treated with 30 ml of anhydrous diethyl
ether, and the mixture was left to stand for 20 h. The
precipitate was filtered off, washed with 20 ml of
diethyl ether, and dried under reduced pressure over
P2O5. Yield 0.82 g (92%), decomposition point 178–
183°C. IR spectrum, ν, cm–1: 3431 (OH), 3382 (+NH2).
1H NMR spectrum, δ, ppm: 1.51–2.24 m (6H, CH2),
tert-Butyl 9-amino-3-azabicyclo[3.3.1]nonane-3-
carboxylate (XIIb) was synthesized in a similar way.
Yield 62%, mp 87–90°C, α/β ratio 48:52. IR spectrum,
1
ν, cm–1: 3364, 3351 (NH2); 1684 (C=O). H NMR
spectrum, δ, ppm: 1.31 s (9H, t-Bu), 1.47–2.12 m (6H,
CH2), 2.36–2.41 m (2H, CH), 3.41 d (2H, NCH2),
3.60 d (2H, NCH2), 3.90 m (9-H, β), 4.06 m (9-H, α),
4.25 br.s (2H, NH2). Mass spectrum, m/z: 241 [M + H]+,
184 [M – 57 + H]+, 140 [M – 101 + H]+. Found, %:
C 64.83; H 9.93; N 11.52. C13H24N2O2. Calculated, %:
C 65.00; H 10.00; N 11.67.
Reaction of amines XIIa and XIIb with benzal-
dehyde. A mixture of 3 mmol of amine Xa or Xb and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 10 2010