Reaction of adamantan-2-one with acetonitrile in basic media

Full text of DOI:10.1023/B:RUJO.0000010230.77371.3b

Russian Journal of Organic Chemistry, Vol. 39, No. 9, 2003, pp. 1360 1361. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 9, 2003,
pp. 1432 1433.
Original Russian Text Copyright
2003 by Skomorokhov, Leonova, Shiryaev, Klimochkin.
SHORT
COMMUNICATIONS
Reaction of Adamantan-2-one with Acetonitrile
in Basic Media
M. Yu. Skomorokhov, M. V. Leonova, A. K. Shiryaev, and Yu. N. Klimochkin
Samara State Technical University, ul. Molodogvardeiskaya 244, Samara, 443100 Russia
Received May 6, 2003
Substituted acetonitriles containing an activated
methylene group are capable of reacting with ketones
in the presence of strong bases [1]. We have found
that adamantan-2-one (I) reacts with acetonitrile in
the presence of powdered potassium hydroxide and
dicyclohexano-18-crown-6 to give 2-adamantylidene-
acetonitrile (II). Under these conditions, inter-
mediate 2-(2-hydroxy-2-adamantyl)acetonitrile (III)
readily undergoes dehydration to nitrile II which is
obtained as the major product (up to 90%, according
to the GLC data). The dehydration is favored by
elimination of steric strain, which accompanies the
Hydroxy nitrile III was reduced with lithium tetra-
hydridoaluminate in tetrahydrofuran. As a result,
2-(2-aminoethyl)-2-hydroxyadamantane was obtained,
which was isolated as hydrochloride IV.
2
-Adamantylideneacetonitrile (II). Finely
3
transition from the sp -hybridized bridging carbon
powdered potassium hydroxide, 5 g (0.09 mol), and
dicyclohexano-18-crown-6, 0.2 g, in 3 ml of aceto-
nitrile were added to a mixture of 5 g (0.03 mol) of
compound I in 15 ml of acetonitrile. The mixture
was heated under reflux with stirring and poured into
water, and the precipitate was filtered off, washed
with water, dried, and recrystallized from hexane.
2
atom in hydroxy nitrile III to sp in II. 2-Adamantyli-
deneacetonitrile (II) was synthesized previously by
the Knoevenagel condensation of adamantan-2-one
with cyanoacetic acid [2]. Nitrile II characteristically
1
showed in the H NMR spectrum signals from non-
equivalent protons in the bridgehead positions neigh-
boring to the double bond ( 2.64 and 3.13 ppm).
Yield 4.5 g (80%), mp 74 75 C; published data [3]:
1
7
1
3
4.0 74.6 C. H NMR spectrum (DMSO-d CCl ,
6
4
:3), , ppm: 1.78 2.1 m (12H, Ad), 2.64 s (1H, Ad),
.13 s (1H, Ad), 5.12 s (1H, CHCN).
2
-(2-Hydroxy-2-adamantyl)acetonitrile (III).
Sodium hydride, 9 g (0.37 mol), was added in small
portions with stirring to 150 ml of anhydrous DMSO,
and 25 ml of acetonitrile and 6 g (0.04 mol) of com-
pound I were added on cooling. The mixture was
stirred for 1 h and poured into water, and the precip-
itate was filtered off, washed with water, dried at
a temperature not exceeding 100 C, and recrystallized
from ethyl acetate. Yield 3.9 g (60%), mp 140 141 C.
The reaction of compound I with acetonitrile in
dimethyl sulfoxide in the presence of sodium hydride
afforded 2-(2-hydroxy-2-adamantyl)acetonitrile (III)
as the major product. The composition of the reaction
mixture (30% of I and 70% of III, according to the
GLC data) did not depend on the molar ratio of
sodium hydride and ketone I.
1
IR spectrum, , cm : 3433, 2256, 1292, 1172, 1124,
1
1076, 565. H NMR spectrum (CDCl ), , ppm:
3
1.56 s (1H, OH), 1.6 2.02 m (12H, Ad), 2.12 2.52 m
(2H, Ad), 2.77 s (2H, CH CN). Found, %: C 77.51;
2
H 8.82; N 7.36. C H NO. Calculated, %: C 77.35;
1
2
17
H 8.96; N 7.32.
1
070-4280/03/3909-1360$25.00 2003 MAIK Nauka/Interperiodica

REACTION OF ADAMANTAN-2-ONE WITH ACETONITRILE
1361
2
-(2-Aminoethyl)-2-hydroxyadamantane hydro- C 63.06; H 9.12; N 6.39. C H ClNO. Calculated,
1
2
22
chloride (IV). A solution of 2.6 g (0.02 mol) of com-
pound III in 80 ml of tetrahydrofuran was added
dropwise with stirring to a suspension of 6.4 g
%: C 62.19; H 9.57; N 6.04.
The IR spectra were recorded on a Shimadzu
1
FTIR-8400S instrument, and the H NMR spectra
(
0.16 mol) of lithium tetrahydridoaluminate in 50 ml
were obtained on a Bruker AM-300 spectrometer
of tetrahydrofuran. The mixture was stirred for 1 h,
the precipitate was filtered off and washed with THF,
and the filtrate was combined with the washings and
saturated with dry hydrogen chloride. The precipitate
(300 MHz) using HMDS as internal reference.
REFERENCES
of hydrochloride IV was filtered off and dried. Yield
1
2
.
.
Jonczyk, A. and Owczarczyk, Z., Synthesis, 1986,
p. 297.
Gaspert, B., Hromadko, S., and Vranesic, B., Croat.
Chem. Acta, 1976, vol. 43, p. 169.
1
2
3
.5 g (82%), mp 280 283 C. IR spectrum, , cm :
250, 2110, 1615, 1550, 1160, 920, 610. H NMR
1
spectrum (DMSO-d ), , ppm: 1.45 m (2H, AdCH ),
6
2
+
1
4
.65 2.05 m (14H, Ad), 2.27 m (2H, CH NH ),
.15 s (1H, OH), 8.12 s (3H, NH ). Found, %:
3. Burkhard, J., Vais, J., and Landa, S., Collect. Czech.
Chem. Commun., 1973, vol. 38, 1263.
2
3
+
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003