AMIDATION OF ADAMANTANE AND DIAMANTANE WITH ACETONITRILE
1899
occurred at 140–150°C in 2–5 h and afforded 90–95%
of compound II, the conversion of initial adamantane
(I) being complete. 1-Bromoadamantane (III) was
formed as by-product (yield 5–10%). Under analogous
conditions, diamantane (IV) was completely converted
into a mixture of N-(1- and 4-diamantyl)acetamides V
and VI and 1- and 4-bromodiamantanes VII and VIII
at a ratio of 2:1:0.5:0.4. The reactant and catalyst
ratio Mo(CO)6–I (or IV)–BrCCl3–MeCN–H2O was
3:100:100:150:200.
Apart from compounds II, III, and V–VIII, the
reaction mixtures contained chloroform (according to
the GLC amd GC–MS data); the amount of the latter
was equal to the amount of compound II, indicating
direct participation of BrCCl3 in the amidation of I and
IV with acetonitrile. No reaction occurred in the
absence of BrCCl3. When BrCCl3 was replaced by
CBr4, the yield of amide II was 34%; a probable
reason for the lower yield of II is that the initial reac-
tants and the product are solids. In methylene chloride
the yield of II increased to 72%. The yield of amide II
was 22% in the presence of MoO(acac)2 as catalyst.
The structure of 1-bromoadamantane (III), and 1- and
4-bromodiamantanes VII and VIII was proved by
comparison with authentic samples [1, 12].
134 (25), 100 (8), 94 (45), 93 (18), 92 (16), 91 (17),
79 (15), 77 (14), 58 (8), 55 (7), 43 (31), 42 (12),
41 (21), 39 (14).
N-(1-Diamantyl)acetamide (V). Yield 52%,
mp 168–168.5°C (from ethanol); published data [12]:
mp 167–168°C (from acetone). IR spectrum, ν, cm–1:
3283 (NH), 1645 (C=O), 1572, 1549 (δNH). 13C NMR
spectrum, δC, ppm: 23.46 (CH3), 25.54 (C4), 28.57
(C9), 33.27 (C3, C14), 36.93 (C6), 37.50 (C5), 37.79 (C8,
C10), 39.13 (C7, C11), 40.37 (C2, C12), 41.66 (C13),
56.63 (C1), 171.44 (C=O).
N-(4-Diamantyl)acetamide (VI). Yield 26%,
sublimes at 98°C (10 mm). IR spectrum, ν, cm–1: 3280
13
(NH), 1645 (C=O), 1549 (δNH). C NMR spectrum,
δC, ppm: 23.46 (CH3), 25.36 (C9), 35.94 (C1, C7, C11),
37.15 (C8, C10, C13), 40.24 (C2, C6, C12), 42.26 (C3, C5,
C14), 54.19 (C4), 170.98 (C=O). Found, %: C 77.89;
H 9.18; N 5.59. C16H23NO. Calculated, %: C 78.32;
H 9.45; N 5.71.
The IR spectra were measured in the range from
3600 to 550 cm–1 on a Bruker Vertex 70V spectrometer
from samples pelleted with KBr or dispersed in
mineral oil. The 13C NMR spectra were recorded on
a Bruker Avance-400 spectrometer at 100.62 MHz
using CDCl3 as solvent. The mass spectra were
obtained on a Shimadzu QP-2010 Plus GC–MS system
(Supelco PTE-5 capillary column, 30 m×0.35 mm).
The elemental composition was determined on a Carlo
Erba 1106 analyzer.
The reactions were carried out in a 20-ml glass
ampule or in a 17-ml stainless-steel high-pressure
reactor; the results of parallel runs were almost similar.
A reactor (ampule) was charged with 0.1 mmol of
Mo(CO)6, 10 mmol of adamantane (I) or diamantane
(IV), 10 mmol of BrCCl3, 15 mmol of acetonitrile, and
20 mmol of water. The reactor was hermetically closed
(the ampule was sealed) and heated for 2–5 h at 140–
150°C. After cooling to room temperature, the reactor
(ampule) was opened, the organic phase was separated,
the aqueous phase was extracted with methylene
chloride (3×5 ml), the extracts were combined with
the organic phase, the solvent was distilled off, and the
residue was crystallized from ethanol. The yields are
given for the isolated compounds. Compounds II, V,
and VI were purified by column chromatography on
aluminum oxide of activity grade II using methylene
chloride–hexane (1:3, by volume) as eluent.
The progress of reactions and the purity of products
were monitored by GLC on a Khrom-5 chromatograph
equipped with a flame ionization detector (1.2- and
3-m columns, 3.3 mm i.d., stationary phase 5% of
SE-30 on Chromaton-N-HMDS, 0.125–0.160 mm; oven
temperature programming from 50 to 280°C at a rate
of 8 deg/min; carrier gas helium, flow rate 50 ml/min).
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).
REFERENCES
1. Bagrii, E.I., Adamantany. Poluchenie, svoistva, prime-
nenie (Adamantanes. Synthesis, Properties, and Applica-
tions), Moscow: Nauka, 1989.
2. Gerzon, K., Krumkalns, E., Brindle, R., Marshall, F., and
Root, M., J. Med. Chem., 1963, vol. 6, p. 760.
3. Kovtun, V.Yu. and Plakhotnik, V.M., Khim.-Farm. Zh.,
N-(1-Adamantyl)acetamide (II). Yield 90%,
mp 147–147.5°C (from ethanol); published data [9]:
mp 147–148°C (from petroleum ether). IR spectrum, ν,
cm–1: 3220 (NH), 1645 (C=O), 1545 (δNH). 13C NMR
spectrum, δC, ppm: 25.40 (CH3), 30.85 (C3, C5, C7),
36.42 (C4, C6, C10), 41.5 (C2, C8, C9), 51.61 (C1),
160.86 (C=O). Mass spectrum, m/z (Irel, %): 193 (43)
[M]+, 192 (9), 150 (7), 137 (8), 136 (100), 135 (24),
1987, p. 931.
4. Mashkovskii, M.D., Lekarstvennye sredstva (Drugs),
Moscow: Novaya Volna, 2005.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011
Khusnutdinov
