UNUSUAL REACTION OF ADAMANTANE-1-CARBOXYLIC ACID
1253
tor (or ampule) was charged with 0.01 mmol of
Found, %: C 61.93; H 7.48; Cl 16.45; N 6.54.
VO(acac) , 10 mmol of freshly distilled acetonitrile,
C H ClNO. Calculated, %: C 61.97; H 7.51;
11 16
2
1
0 mmol of compound I or II, and 20 mmol of CCl4
Cl 16.43; N 6.57.
(
1.8 ml of water was added in the synthesis of IV). The
The purity of the products was checked, and com-
position of the reaction mixtures was monitored, by
GLC on a Khrom-5 chromatograph using a 1.2-m×3-
mm column packed with 5% of SE-30 on Chromaton
N-AW–HMDS (0.125–0.160 mm); carrier gas helium,
flow rate 50 ml/min; oven temperature programming
from 50 to 270°C at a rate of 8 deg/min. The IR
reactor was hermetically closed (the ampule was
sealed), and the mixture was heated for 1–3 h at 125–
1
the reactor (ampule) was cooled to room temperature
and opened, the mixture was filtered through a layer of
Al O , unreacted acetonitrile and carbon tetrachloride
were distilled off, and the residue was distilled under
reduced pressure using an air condenser or recrystal-
lized from methanol.
50°C under stirring. When the reaction was complete,
2
3
–1
spectra were measured in the range 550–3600 cm on
a Bruker Vertex 79V spectrometer from samples dis-
1
13
persed in KBr or mineral oil. The H and C NMR
spectra were measured on a Bruker Avance-400Q
instrument at 400.13 and 100.62 MHz, respectively,
3
-Chloroadamantane-1-carbonitrile (III).
mp 208.5–209°C (from MeOH); published data [5]:
mp 208–209°C. IR spectrum, ν, cm : 2248 (C≡N),
7
CH ), 1.97 br.s (2H, CH ), 2.05 br.s (4H, CH ),
2
spectrum, δ , ppm: 27.94 (C , C ), 29.09 (C ), 30.21
–
1
from solutions in CDCl . The mass spectra were run on
3
1
63 (C–Cl). H NMR spectrum, δ, ppm: 1.84 br.s (2H,
a Shimadzu QP-2010 Plus GC–MS system (Supelco
PTE-5 capillary column, 30 m×0.35 mm). The ele-
mental compositions were determined on a Carlo Erba
1106 analyzer.
2
2
2
1
3
.14 br.s (2H, CH), 2.33 br.s (4H, CH ). C NMR
2
5
7
3
C
6
4
10
8
9
2
(
(
(
(
C ), 39.25 (C , C ), 45.52 (C , C ), 47.15 (C ), 65.92
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation (state contract no. 02.740.11.0631).
1
C ), 123.95 (C≡N). Mass spectrum, m/z (I , %): 195
rel
+
12) [M] , 168 (7.1), 161 (12), 160 (100), 159 (7), 128
6.5), 118 (10), 105 (6.3), 104 (14), 93 (13.4), 92 (10),
9
(
1 (13), 79 (10), 77 (13), 65 (11), 55 (6), 53 (8.1), 51
7.3), 41 (21.4), 39 (25).
-Chloroadamantane-1-carboxamide (IV).
REFERENCES
3
1
2
. Sasaki, T., Shimizu, K., and Ohno, M., Chem. Pharm.
Bull., 1984, vol. 32, no. 4, p. 1433.
–
1
mp 137–138°C. IR spectrum ν, cm : 3580–3300,
2
1
900, 2365, 1675, 1440, 1415, 765. H NMR spec-
. Yagrushkina, I.N., Zemtsova, M.N., and Moiseev, I.K.,
trum, δ, ppm: 1.65–1.73 m (4H, CH ), 1.84 br.s (2H,
Russ. J. Org. Chem., 1995, vol. 31, p. 579.
2
CH ), 2.01 br.s (2H, CH), 2.14 br.s (2H, CH ),
2
2
3. Stetter, H. and Mayer, J., Chem. Ber., 1962, vol. 95,
2
.31 br.s (4H, CH ), 5.70 br.s and 6.27 br.s (1H each,
p. 667.
2
1
3
5
7
NH2). C NMR spectrum, δ , ppm: 28.74 (C , C ),
3
5
C
4. Stepanov, F.N. and Srebrodol’skii, Yu.I., Sintezy prirod-
nykh soedinenii, ikh analogov i fragmentov (Syntheses of
Natural Compounds and Their Analogs and Fragments),
Moscow: Nauka, 1967.
6
4
10
8
9
3
7.45 (C ), 38.34 (C , C ), 49.07 (C , C ), 51.02 (C ),
5.16 (C ), 67.63 (C ), 162.02 (C=O). Mass spectrum,
2
1
+
m/z (I , %): 213 (39) [M] , 178 (17), 177 (12), 169
rel
(
(
100), 171 (33), 133 (24), 93 (15), 91 (42), 79 (18), 77
5), 67 (10), 65 (15), 55 (12), 53 (8), 41 (20), 39 (23).
5. Petrov, K.A., Repin, V.N., and Sorokin, V.D., Zh. Org.
Khim., 1992, vol. 28, p. 129.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 9 2012