ADAMANTYLATION OF AZOLES BY 1,3-DEHYDROADAMANTANE: I.
1733
N-adamantylimidazoles IIIa–IIIc in 78–89% yields.
1-(1-Adamantyl)benzimidazole (IIIc). Yield 78%,
mp 183–185°C (2-propanol) (mp 180–184°C [6]).
GC-MS analysis of the reaction mixtures showed that
the main direction of the reaction was the N-adamantyl-
ation at the mobile proton of the NH bond in the imidazole
or benzimidazole ring, therewith as side products formed
a little (≥10%) of C-adamantylated into the imidazole or
benzimidazole ring derivatives.
1
H NMR spectrum (CDCl ), δ, ppm: 1.83 m (6H),
3
2.29 m (3H), 2.34 m (6H, Ad), 7.25 m (2H), 7.70 m (1H),
7
.85 m (1H ). Mass spectrum, m/z (I , %): 252 (86)
arom
rel
+
+
+
[
M] , 201 (10) [M – CH ] , 159 (50) [M – C H ] , 135
3 4 9
+
+
+
(
100) [Ad] , 117 (8) [M – Ad] , 93 (18) [Ad – C H ] ,
3 6
+
7
9 (20) [Ad – C H ] .
4 8
This method makes it possible to obtain N-adamantyl-
containing imidazole under relatively mild conditions and
with a good yield.
1H NMR spectra of compounds obtained were
registered on a spectrometer Varian Mercury-300
300 MHz). GC-MS measurements were performed on
(
The structure of synthesized N-adamantylimidazoles
an instrument HP GC 5890 II/MSD 5972 in direct
admission mode. Energy of ionizing electrons 70 eV. 1,3-
Dehydroadamantane (I) was obtained by procedure [8].
The study was carried out in the framework of the
Federal R&D program “Research and Development in
the Priority Directions of Science and Technology” for
1
IIIa–IIIc was confirmed by H NMR and mass spectra,
and the composition of products obtained was revealed
by GC-MS method.
1-(1-Adamantyl)imidazole (IIIa). To 5 g (0.037 mol)
of 1,3-dehydroadamantane (I) in 30 ml of anhydrous ethyl
ether was added a solution of 2.92 g (0.041 mol) of
imidazole (IIa) in 20 ml of anhydrous ethyl ether. The
mixture was heated to complete evaporation of ether and
then for 5 h at 100°C. The reaction mixture was washed
with water, then kept at reduced pressure, and the residue
was recrystallized from 2-propanol. Yield 6.57 g
2
002-2006 and “Scientific Investigations Carried out by
Young Scientists”, state contract no. 02.442.11.7533.
REFERENCES
1
. Shvekhgeimer, G.A. and, and Litvinov, V.P., Zh. Org. Khim.,
990, vol. 35, p. 183.
. Shvekhgeimer, G.A., Usp. Khim., 1996, vol. 65, p. 606.
. Shvekhgeimer, G.A., and Litvinov, V.P., Zh. Org. Khim., 1999,
vol. 35, p. 190.
(
0.032 mol, 88%), colorless crystals, mp 109–113°C (mp
1
1
1
1
2
7
2
7
06–111°C [6]). H NMR spectrum (DMSO-d ), δ, ppm:
6
2
3
.72–1.77 d (6H, CH , Ad), 1.98–2.05 d (6H, CH , Ad),
2
2
.16–2.22 d (3H, CH, Ad), 6.81–6.87 t (2H, CH, Imd),
.38–7.42 t (1H, CH, Imd). Mass spectrum, m/z (I , %):
rel
4. Gavrilov,A.S. and Golod, E.L., Zh. Org. Khim., 1999, vol. 35,
+
+
+
02 (37) [M] , 135 (100) [Ad] , 93 (23) [Ad – C H ] ,
3
6
p. 1260.
+
9 (25) [Ad – C H ] .
4
8
5. Gavrilov,A.S., Golod, E.L., Kachalov, V.V., and Ugrak, B.I. ,
Compounds IIIb and IIIc were obtained similarly.
Zh. Org. Khim., 2001, vol. 37, p. 1822.
1
-(Adamantyl)-2-methylimidazole (IIIb). Yield
6. Raenko, G.F., Korotkikh, N.I., Pekhtereva, T.M., Shvaika, O.P.,
Zh. Org. Khim., 2001, vol. 37, p. 1212.
7. Pozharskii,A.F., Usp. Khim., 1966, vol. 35, p. 261.
8. Pincock, R.E., Schmidt, J., Scott, W.B., and Torupka, E.J.,
Canad. J. Chem., 1972, vol. 50, p. 3958.
8
9%, mp 123–125°C (2- propanol) (mp 123–125°C [6]).
Mass spectrum, m/z (I , %): 216 (100) [M] , 201 (10)
M – CH ] , 159 (50) [M – C H ] , 135 (88) [Ad] , 93
3 4 9
22) [Ad – C H ] , 79 (30) [Ad – C H ] .
+
rel
+
+
+
[
(
+
+
3
6
4
8
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 11 2009