CYANOETHYLATION OF PYRAZOLES UNDER CONDITIONS
1133
1
1
(
3
.4880, mp 45 47 C. IR spectrum, , cm : 1520
pyrazole Vb. Yield 4 g (36%), bp 100 105 C (5 mm),
1
20
D
20
1
ring), 2250 (CN). H NMR spectrum (DMSO-d ,
00 MHz), , ppm (J, Hz): 2.15 s (3H, 3-CH ), 2.30 s
n
1.5065, d4 1.0424. IR spectrum, , cm : 1520
(ring), 3350 3400 (NH ). H NMR spectrum (DMSO-
6
1
3
2
(
3H, 5-CH ), 2.98 t (2H, CH CN, J 6.6), 4.20 t (2H,
d , 300 MHz), , ppm (J, Hz): 1.85 q (2H, CH , J 7.4,
3
2
6
2
CH N, J 6.6), 5.72 s (1H, 4-H). Found, %: C 64.64;
7.0), 1.85 br.s (2H, NH ), 2.60 t (2H, CH NH , J 7.4),
2
2 2 2
H 7.13; N 28.36. C H N . Calculated, %: C 64.43;
H 7.38; N 28.19.
4.15 t (2H, CH N, J 7.0), 5.95 d (1H, 4-H, J 1.9),
7.28 d (1H, 3-H, J 1.9). Found, %: C 60.18; H 9.09;
8
11
3
2
N 30.46. C H N . Calculated, %: C 60.43; H 9.35;
N 30.22.
7
13
3
3
-(3-Methyl-1H-pyrazol-1-yl)propan-1-amine
(
VIIa). A solution of 10 g of cyanoethylpyrazole Va
in 150 ml of anhydrous diethyl ether was added drop-
wise under stirring to a mixture of 7 g of lithium
tetrahydridoaluminate and 100 ml of anhydrous di-
ethyl ether at such a rate that the mixture evenly
boiled. The mixture was heated for 3 h under reflux
and cooled to room temperature, 25 ml of water was
carefully added in a dropwise fashion, and 30 ml of a
REFERENCES
1
2
3
4
. Grandberg, I.I. and Kost, A.N., Zh. Obshch. Khim.,
959, vol. 29, no. 4, p. 1099.
. Grandberg, I.I. and Kost, A.N., Zh. Obshch. Khim.,
961, vol. 31, no. 11, p. 3700.
1
1
. Auwers, K. and Schmidt, W., Chem. Ber., 1925,
vol. 58, p. 528.
3
0% solution of sodium hydroxide was added. The
organic phase was separated, the residue was washed
with diethyl ether (3 50 ml), the extract was dried,
the solvent was distilled off, and the residue was dis-
tilled under reduced pressure. Yield 3.4 g (30%), bp
. Auwers, K. and Stuhlmann, H., Chem. Ber., 1926,
vol. 59, p. 1043.
5. Bertrand, M., Elquero, J., Jacuier, R., and Le Gras, J.,
2
0
20
7
8 83 C (1 mm), n 1.5000, d 1.0319. IR spectrum,
C.R. Acad. Sci., 1966, vol. 262, p. 782.
D
4
1
1
,
cm : 1520 (ring), 3350 3400 (NH ). H NMR
2
6. Wiedeman, O.F. and Montgomery, W.H., J. Am. Chem.
Soc., 1945, vol. 67, p. 1994.
spectrum (DMSO-d , 300 MHz), , ppm (J, Hz):
6
1
2
4
.85 q (2H, CH , J 7.4, 7.0), 2.20 s (3H, 3-CH ),
2
3
7
8
9
. Buckle, F.J. and Saunders, B.C., J. Chem. Soc., 1949,
no. 11, p. 2774.
.58 t (2H, CH NH , J 7.4), 4.08 t (2H, CH N, J 7.0),
2
2
2
.08 br (2H, NH ), 5.88 d (1H, 4-H, J 2.2), 7.31 d
2
. Kost, A.N. and Yashunskii, V.G., Dokl. Akad. Nauk
SSSR, 1952, vol. 83, no. 1, p. 93.
(1H, 5-H, J 2.2). Found, %: C 60.25; H 9.57; N 30.08.
C H N . Calculated, %: C 60.43; H 9.35; N 30.22.
7
13
3
. Shostakovskii, M.F., Atavin, A.S., Vodbol’skaya, B.A.,
Gusarova, N.K., and Lavrov, V.I., Dokl. Akad. Nauk
SSSR, 1966, vol. 166, no. 9, p. 1381.
3
-(5-Methyl-1H-pyrazol-1-yl)propan-1-amine
(VIIb) was obtained in a similar way from 10 g of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 7 2006