Short Communication
1539
hydrochloride IIIa, m.p. 180–183 °C. For spectral measurements the base was liberated by addition
of aqueous potassium hydroxide and taken up in ether. The ethereal extract was dried over magne-
sium sulfate and the solvent was evaporated. The spectral data of IIIa agreed with those given in the
literature16
.
4-Carbamoyl-1-(3-hydroxypropyl)piperidinium Chloride (IIIb)
Pyridinium salt IIb (17.55 g, 81 mmol) was hydrogenated as described in the preceding experiment.
Yield 17.56 g (97%) of hydrochloride IIIb, m.p. 178–180 °C. For C9H19ClN2O2 (222.7) calculated:
48.54% C, 8.60% H, 15.92% Cl, 12.58% N; found: 48.26% C, 8.84% H, 15.66% Cl, 12.31% N. Base IIIb:
1
IR spectrum (CHCl3, cm–1): 3 360 (NH2), 1 652 (CO). H NMR spectrum: 1.56 m, 1 H (CH); 1.89 t,
J = 6.1 (CH2); 2.32 m, 2 H, 2.48 t, 2 H (2 × CH2); 2.84 m, 2 H, 3.12 m, 2 H, 3.43 t, 2 H, J = 6.1
(3 × CH2); 4.78 t, 2 H (CH2OH); 6.91 s and 7.42 s, 2 H (NH2).
4-Cyano-1-(3-chloropropyl)piperidinium Chloride Hydrochloride (IVb)
A mixture of hydrochloride IIIb (12.05 g, 54.1 mmol), thionyl chloride (50.0 g, 420 mmol) and dry
acetonitrile (130 ml) was refluxed for 3 h. The solvent was evaporated and the residue crystallized
from isopropyl alcohol to give 8.80 g (73%) of hydrochloride IVb, m.p. 162–164 °C. For C9H16Cl2N2
(223.1) calculated: 48.44% C, 7.23% H, 31.78% Cl, 12.55% N; found: 48.18% C, 7.36% H, 31.40% Cl,
12.22% N.
Base IVb was liberated by aqueous potassium hydroxide and taken up in chloroform (3 × 50 ml).
After drying over anhydrous magnesium sulfate and evaporation of the solvent, the base IVb was
1
isolated as an oil. IR spectrum (CHCl3, cm–1): 2 240 (CN). H NMR spectrum: 1.89 m, 3 H (CH + CH2);
1.91 t, 2 H, J = 6.1; 2.31 t, 2 H, 2.43 t, 2 H, J = 7.0; 2.62 m, 4 H (5 × CH2); 3.58 t, 2 H, J = 6.5
(CH2Cl).
Hydrochloride IVa was prepared according to ref.16; m.p. 176–178 °C (reported16 m.p. 176–178 °C).
Quinuclidine-4-carbonitrile (Va)
Hydrochloride IVa (5.0 g, 23.9 mmol) was added at –78 °C under nitrogen to a solution of lithium
diisopropylamide in tetrahydrofuran, prepared from 12.5 ml of diisopropylamine and 37.5 ml of 2 M
butyllithium in hexane. After stirring for 10 min, the cooling bath was removed and the mixture was
slowly warmed to 0 °C (during 30 min) and held at this temperature for 2 h. Saturated solution of
ammonium chloride (25 ml) was added, the organic layer was separated and the aqueous one washed
with ether (25 ml). The combined organic solutions were washed with saturated sodium chloride sol-
ution, dried over anhydrous magnesium sulfate and the solvent was evaporated. Crystallization from
hexane afforded 2.46 g (76%) of nitrile Va, m.p. 138–140 °C (reported16 m.p. 133 °C).
1-Azabicyclo[3.2.2]nonane-5-carbonitrile (Vb)
Base IVb (1.82 g, 9.75 mmol) in dry tetrahydrofuran (1 200 ml) was cyclized analogously as des-
cribed in the preceding experiment. Column chromatography on silica gel in chloroform–methanol
afforded 0.48 g (32%) of compound Vb. For C9H14N2 (150.2) calculated: 71.96% C, 9.39% H,
1
18.65% N; found: 71.71% C, 9.44% H, 18.37% N. IR spectrum (KBr, cm–1): 2 231 (CN). H NMR
spectrum: 1.44 dt, 2 H, J = 3.6 and J = 13.0; 1.63 m, 4 H, 1.94 d, 2 H, J = 12.6; 2.23 t, 2 H, J = 12.0;
2.39 t, 2 H, J = 5.4; 2.80 d, 2 H, J = 12.1 (7 × CH2). Mass spectrum (m/z, %): 150 (M+, 40), 149
(M+ – 1, 50), 135 (28), 123 (100), 122 (10), 121 (10), 96 (17), 82 (56), 84 (12), 69 (30), 68 (44), 67 (15),
56 (18), 55 (38), 54 (21).
Collect. Czech. Chem. Commun. (Vol. 60) (1995)