POPOV et al.
24
trum, δ, ppm: 1.56 m (4H, CH2), 1.75 br.s (2H, CH2),
2.09 m (2H, CH2), 2.31 m (2H, CH2), 3.41 br.s (1H,
NH), 3.64 s (3H, OCH3), 6.43 d (2H, Harom, J =
0.7 Hz), 6.66 d (2H, Harom, J = 0.7 Hz). Found, %:
C 72.98; H 9.92; N 12.19. C14H18N2O. Calculated, %:
C 73.01; H 9.88; N 12.16.
ammonia was observed during the process. Acetone
was distilled off, and the residue was distilled under
reduced pressure. Yield 3.3 g (75%), bp 173–175°C
(15 mm); published data: bp 278–280°C [7], 190–
1
193°C (20 mm) [11]. H NMR spectrum, δ, ppm:
1.20 s (1H, NH), 1.43–2.24 m (14H, Ad), 2.68 s (1H,
OH), 3.01 t (2H, CH2N, J = 12.2 Hz), 3.59 t (2H,
CH2O, J = 14.0 Hz).
2-(Morpholin-4-yl)adamantane-2-carbonitrile
(IIg). a. A mixture of 3 g (17 mmol) of nitrile Id, 3.8 g
(44 mmol) of morpholine, and 0.05 g of potassium
carbonate was stirred for 1.5 h at 80–100°C. Excess
morpholine was distilled off under atmospheric
pressure, and the residue was distilled under reduced
pressure. Yield 2.8 g (67%), bp 219–221°C (20 mm);
published data [11]: bp 170–180°C (15 mm). 1H NMR
spectrum, δ, ppm: 1.38–2.13 m (14H, Ad), 2.56 t (4H,
CH2N), 3.72 t (4H, CH2O).
2-(Piperazin-1-yl)adamantane-2-carbonitrile
(IIk) was synthesized in a similar way from 3 g
(20 mmol) of adamantan-2-one, 2.5 g (30 mmol) of
nitrile Ia, and 3.5 g (41 mmol) of piperazine using
0.05 g of potassium carbonate. Yield 2.8 g (57%),
bp 223–225°C (20 mm), mp 116–117°C; published
1
data [7]: mp 117–118°C. H NMR spectrum, δ, ppm:
1.67–2.35 m (15H, Ad, and 1H, NH), 2.80 t (4H,
CH2N, J = 13.1 Hz), 2.95 t (4H, CH2N, J = 14.0 Hz).
Found, %: C 73.39; H 9.49; N 17.12. C15H23N3O.
Calculated, %: C 73.43; H 9.45; N 17.13.
b. A mixture of 3 g (20 mmol) of adamantan-2-one,
3 g (36 mmol) of nitrile Ia, 3.5 g (40 mmol) of
morpholine, and 0.1 g of potassium carbonate was
stirred for 1.5 h at 80–100°C. Gaseous ammonia
evolved during the process. Acetone and excess
morpholine were distilled off under reduced pressure,
and the residue was subjected to fractional distillation
under reduced pressure. Yield 3.2 g (65%).
REFERENCES
1. Strecker, A., Ann. Chem. Pharm., 1850, vol. 75, p. 27.
2. Bucherer, Η.T. and Steiner, W., J. Prakt. Chem., 1934,
vol. 140, p. 291.
3. Evans, D.A., Truesdale, L.K., and Carroll, G.L.,
Compounds IIh and IIi were synthesized in a sim-
ilar way.
J. Chem. Soc., Chem. Commun., 1973, p. 55.
4. Bauer, O.W. and Teter, J.W., US Patent no. 2552026;
Chem. Abstr., 1951, vol. 45, p. 9074.
5. Domkin, V.D. and Kur’yanovich, A.A., Zh. Org. Khim.,
1976, vol. 12, p. 908.
6. Brown, T., Shaw, G., and Durant, G.J., J. Chem. Soc.,
Perkin Trans. 1, 1980, p. 2310.
7. Popov, Yu.V., Mokhov, V.M., Tankabekyan, N.A., and
Safronova, O.Yu., Russ. J. Appl. Chem., 2012, vol. 85,
p. 1387.
2-(3-Hydroxypropylamino)adamantane-2-carbo-
nitrile (IIh) was synthesized from 3 g (17 mmol) of
nitrile Id, 2.25 g (30 mmol) of 3-aminopropan-1-ol,
and 0.05 g of potassium carbonate. Yield 3.4 g (86%),
1
bp 175–178°C (20 mm). H NMR spectrum, δ, ppm:
1.39–2.13 m (14H, Ad, and 2H, CH2), 2.84 t (2H,
CH2N, J = 10.4 Hz), 2.76 br.s (1H, NH), 3.63 br.s (1H,
OH), 3.71 t (2H, CH2O, J = 11.1 Hz). Found, %:
C 71.81; H 9.47; N 11.91. C14H22N2O. Calculated, %:
C 71.76; H 9.46; N 11.95.
8. Shakhidayatov, Kh., Zh. Org. Khim., 1973, vol. 9,
p. 1373.
2-(Cyclohexylamino)adamantane-2-carbonitrile
(IIi) was synthesized from 3.5 g (20 mmol) of nitrile
Id, 3 g (30 mmol) of cyclohexylamine, and 0.05 g of
K2CO3. Yield 3.8 g (74%), bp 170–172°C (20 mm),
mp 93–94°C; published data [7]: mp 93–94°C.
9. Shafran, Yu.M., Bakulev, V.Α., and Mokrushin, V.S.,
Usp. Khim., 1989, vol. 58, p. 250.
10. Freifelder, M. and Hasbrouck, R.B., J. Am. Chem. Soc.,
1960, vol. 82, p. 696.
11. Popov, Yu.V., Mokhov, V.M., and Tankabekyan, N.A.,
2-(2-Hydroxyethylamino)adamantane-2-carbo-
nitrile (IIj). A mixture of 3 g (20 mmol) of adaman-
tan-2-one, 4 g (47 mmol) of nitrile Ia, 3 g (49 mmol)
of 2-aminoethanol, and 0.05 g of potassium carbonate
was stirred for 1.5 h at 80–100°C. Evolution of
Russ. J. Org. Chem., 2013, vol. 49, p. 1135.
12. Wendelin, W., Kern, W., Zmolnig, I., and Schramm, H.,
Monatsh. Chem., 1981, vol. 112, p. 1091.
13. Barreau, M., Chottard, J.-C., Le Peco, J-B., and
Mailliet, P., US Patent no. 5225207, 1993.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 1 2014