Amidation of Ethyl N-Benzoyl-1-adamantylacetimidate

Full text of DOI:10.1023/A:1012332328978

Russian Journal of General Chemistry, Vol. 71, No. 2, 2001, pp. 317 318. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 2, 2001,
pp. 347 348.
Original Russian Text Copyright
2001 by No, Zotov, Shishkin, Klimov.
LETTERS
TO THE EDITOR
Amidation of Ethyl N-Benzoyl-1-adamantylacetimidate
B. I. No, Yu. L. Zotov, E. V. Shishkin, and D. S. Klimov
Volgograd State Technical University, Volgograd, Russia
Received April 17, 2000
We have for the first time prepared N1,N2-di-
and N1,N1,N2-trisubstituted amidines.
adamantylacetimidate (I). It was brough in reactions
with primary alkylarylamines (benzylamine), secon-
dary aliphatic amines (diethylamine), and primary
aromatic amines (aniline) .
As object for study we chose ethyl N-benzoyl-1-
NC(O)C6H5
C6H5CH2NH2
+ C2H5OH,
AdCH2C
AdCH2C
NHCH2C6H5
II
NC(O)C6H5
NC(O)C6H5
(C2H5)2NH
AdCH2C
OC2H5
I
+ C2H5OH,
+ C2H5OH,
N(C2H5)2
III
NC(O)C6H5
C6H5NH2
AdCH2C
NHC6H5
IV
.
Ad =
The syntheses were carried out in the media of the
corresponding amines. At 50 60 C, the reactions were
complete in one or, with aniline, two hours. The latter
fact can be explained by the lower basicity of the
aromatic amine.
equipped with a stirrer, a thermometer, and a reflux
condenser. The reaction mixture was stirred for 1 h at
50 60 C. Excess amine was removed in a vacuum,
and the residue was crystallized from ethanol to obtain
1.78 g (92%) of compound II, mp 128 129 C. IR
1
spectrum, , cm : 1650 (C=O), 1610 (C=N), 3460
The products are white crystalline substances with
fairly high well-defined melting points. Due to the
electron-donor effect of the amino groups, the C=N
and C=O absorption bands in the IR spectra are
(N H), 1248 (C N), 3080, 3040, 1595 (Ar), 1468,
1
1380, 1100, 985 (Ad). H NMR spectrum, , ppm:
1.38 s (6H, Ad), 1.51 s (6H, Ad), 1.74 s (3H, Ad),
2,51 s (2H, CH2), 3.44 t (1H, NH), 4.47 s (2H, CH2),
7.56, m (10H, 2 C6H5). Found, %: C 80.56; H 8.12;
N 7.30. C26H30N2O. Calculated, %: C 80.79; H 7.82;
1
shifted red by 10 20 cm .
N2-Benzoyl-N1-benzyl-1-adamantylacetamidine
(II). Compound I, 1.63 g, and 10 ml of benzylamine
were placed in a moisture-proof four-necked reactor N 7.25.
1070-3632/01/7102-0317$25.00 2001 MAIK Nauka/Interperiodica

318
NO et al.
placed in a moisture-proof four-necked reactor equip-
N2-Benzoyl-N1,N1-diethyl-1-adamantylacet-
ped with a stirrer, a thermometer, and a refluxed
condenser. The reaction mixture was stirred for 2 h at
507360 C. Excess amine was removed in a vacuum,
and the residue was crystallized from ethanol to obtain
1.79 g (96%) of compound IV, mp 126 127 C. IR
amidine (III). Compound I, 1.63 g, and 10 ml of di-
ethylamine were placed in a moisture-proof four-
necked reactor equipped with a stirrer, a thermometer,
and a reflux condenser. The reaction mixture was
stirred for 1 h under reflux. Excess amine was distil-
led off in a vacuum, and the residue was crystallized
from ethanol to obtain 1.61 g (91%) of compound III,
1
spectrum, , cm : 1645 (C=O), 1615 (C=N), 3470
(NH), 1265 (C N), 3080, 3050, 1595, 1480 (Ar),
1
1
1460, 1100, 985 (Ad). H NMR spectrum, , ppm:
mp 153 154 C. IR spectrum, , cm : 1640 (C=O),
1.45 s (6H, Ad), 1.58 s (6H, Ad), 1.80 s (3H, Ad),
2.09 s (1H, NH), 2.42 s (2H, CH2), 7.44 m (10H,
2C6H5). Found, %: C 80.73; H 7.82; N 7.85. C25H28
N2O. Calculated, %: C 80.61; H 7.85; N 7.52.
1610 (C=N), 1245 (C N), 3080, 3050, 1600, 1480
1
(Ar), 1460, 1373, 1100, 982 (Ad). H NMR spectrum,
, ppm: 1.20 t (6H, 2CH3), 1.46 s (6H, Ad), 1.58 s
(6H, Ad), 1.76 s (3H, Ad), 2.77 s (2H, CH2), 3.49 d
(4H, 2CH2), 7.64 m (5H, C6H5). Found, %: C 78.49;
H 9.42; N 8.12. C23H32N2O. Calculated, %: C 78.37;
H 9.15; N 7.95.
N2-Benzoyl-N1-phenyl-1-adamantylacetamidine
(IV). Compound I, 1.63 g, and 10 ml of aniline were
The IR spectra were recorded on a Perkin-Elmer
882 spectrometer in Vaseline oil using NaCl or KBr
1
prisms. The H NMR spectra were measured on a
Tesla BS-487 spectrometer (100 MHz) against HMDS
in CCl4, CDCl3, and acetone-d6.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 2 2001