HYDROAMINATION OF CARBONYL COMPOUNDS WITH OXIMES
383
1
Benzyl(propyl)amine (IV). A stainless-steel re-
45 g (54%) of amine XVIII. IR spectrum, cm : 3324,
actor 20 mm in diameter was charged with 20 cm3 of
3070, 3040, 3005, 2962, 2932, 2876, 2865, 1605,
1512, 1222, 826. H NMR spectrum (CDCl3), , ppm:
1
the catalyst 36% Cu/MgO (15% Cu/Al2O3
+
6% LiOH) which was reduced in hydrogen at 350 C
7.40 m (2H, Ar H), 7.00 t (2H, Ar H), 3.75 s (2H,
PhCH2), 2.85 m (1H, CH), 1.10 d (6H, 2Me).
for 3 h. A solution of 60 g of oxime I in 43 g of
1
propanal was passed at a volume rate of 0.3 h
Amines XIV XVII, XIX XXII were prepared in
a similar way. Their mass spectra contain [C7H6F]+
ion peaks at m/z 109.
through the catalyst bed at 210 C and a hydrogen
pressure of 1 MPa. Reaction products were treated
with dilute (1:3) hydrochloric acid. The hydrogen
chloride solution was treated with ten volumes of
diethyl ether to remove neutral reaction products and
then made weakly alkaline with 15% KOH, after
which amines were extracted with diethyl ether. The
ethereal layer was dried with K2CO3, the solvent was
removed, and the residue was distilled in a vacuum to
obtain 49 g (66% per taken oxime) of the target re-
Ethyl[1-(p-fluorophenyl)ethyl]amine (XL) was
prepared in a similar way using a solution of 77 g of
oxime II in 34 g of acetaldehyde. Yield 36 g (43%).
1H NMR spectrum (CDCl3), , ppm: 7.30 m (2H,
Ar H), 6.90 t (2H, Ar H), 3.69 m (CHMe), 2.43 q
(2H, CH2Me), 1.45 d, 1.01 t (3H, CH2Me).
Amines XXXVI XLV, XLI XLIII were prepared
in a similar way. Their mass spectra contain [C7H6F]+
ion peaks at m/z 109.
1
action product. IR spectrum, cm : 3320, 3005, 3032,
3068, 2815, 2878, 2962, 1600, 1494.
Benzyl(2-methylpropyl)amine (VI) was prepared
in a similar way using a solution of 60 g of oxime I
in 54 g of 2-methylpropanal. Vacuum distillation gave
REFERENCES
1
37 g (45%) of amine VI. IR spectrum, cm : 3330,
1. Tarasevich, V.A. and Kozlov, N.G., Usp. Khim., 1999,
3070, 3045, 3010, 2960, 2930, 2875, 2820, 1610,
vol. 68, no. 1, p. 61.
1
1510, 1385, 1364. H NMR spectrum (CDCl3),
,
2. Kozlov, N.S., Tarasevich, V.A., Naumova, L.V., and
Kozintsev, S.I., USSR Inventor’s Certificate 650994,
1977, Byull. Izobret., 1979, no. 9.
ppm: 7.19 m (5H, Ar H), 3.73 s, 2.39 d (2H, PhCH2),
1.69 m (1H, CH), 0.90 d (6H, 2Me).
Amines III VIII, IX XXIV were prepared in a
similar way. The mass spectra contain molecular ion
peaks with relative intensities of about 30% and the
following ion peaks (m/z): 120 [C6H5CH2NHCH2]+,
106 [C6H5CHNH2]+, 91 [C7H7]+, 77 [C6H5]+, 78
[C6H6]+, 79 [C6H7]+, 65 [C5H5].
3. Kozlov, N.S., Tarasevich, V.A., Kozintsev, S.I., and
Gladkikh, L.V., Dokl. Akad. Nauk Bel. SSR, 1983,
vol. 27, no. 7, p. 634.
4. Peshkova, V.M., Savostina, V.M., and Ivanova, E.K.,
Oksimy (Oximes), Moscow: Nauka, 1977.
p-Fluorobenzyl(isopropyl)amine (XVIII) was
prepared in a similar way using a solution of 70 g of
oxime II in 44 g of acetone. Vacuum distillation gave
5. Kozlov, N.S., Tarasevich, V.A., Kozintsev, S.I., and
Gladkikh, L.V., Dokl. Akad. Nauk SSSR, 1979, vol. 244,
no. 5, p. 1130.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 3 2004