Cyanation of adamantane and diamantane with acetonitrile and tetrabromomethane in the presence of Mo(CO)6

Full text of DOI:10.1134/S1070428008070245

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 7, pp. 1084−1086. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © R.I. Khusnutdinov, N.A. Shchadieva, L.F. Mukhametshina, U.M. Dzhemilev, 2008, published in Zhurnal Organicheskoi Khimii,
2008, Vol. 44, No. 7, pp. 1093−1095.
SHORT
COMMUNICATIONS
Cyanation of Adamantane and Diamantane
with Acetonitrile and Tetrabromomethane
in the Presence of Mo(CO)6
R. I. Khusnutdinov, N. A. Shchadieva, L. F. Mukhametshina, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, Ufa, 450075 Russia
e-mail: ink@anrb.ru
Received December 20, 2007
DOI: 10.1134/S1070428008070245
1-Adamantanecarbonitrile and its derivatives are
initial raw material for preparation of a valuable drug
Rimantadine, 1,2-dioxetane diagnosticums, and they are
also used in the synthesis of polyurethanes underlying
the production of stable to light polymer materials of
high transparency, low optical density, high resistance
against UV irradiataion and enhanced hydrolytic stability
[1].
mantanecarboxamide by its boiling with SOCl2 in benz-
ene. In [7] a one-stage synthesis was reported of
1-adamantanecarbonitrile (II) and 1-diamantanecarbo-
nitrile (V) from 1-chloro(1-bromo)adamantane (1-bromo-
diamantane) and trimethylsilyl cyanide catalyzed by
Lewis acids (SnCl4, AlBr3). The yield of compounds II
and V reached 59–90%. The reaction completed in 23–
55 h in the presence of stoichiometric amounts of
catalysts in anhydrous medium for the Me3SiCN was
easily hydrolyzed forming hydrocyanic acid.
1-Adamantanecarbonitriles substituted in the position
3 are commonly prepared from adamantane (I) deriv-
atives already possessing functional groups like COOH,
CONH2, OH, Cl, Br [1–4].
We performed a direct cyanation of adamantane (I)
with acetonitrile in the presence of molybdenum hexa-
carbonyl Mo(CO)6 and tetrabromomethane CBr4. The
reaction proceeded at 140–160°C for 6 h and resulted in
85% yield of compound II at the total conversion of
2- and 3-Substituted nitriles of the adamantane series
have been known since 1962 [5], the simplest 1-adaman-
tanecarbonitrile (II) was obtained in 1974 from 1-ada-
Br
CN
I
CHBr3
140oC, 6 h , ~100%
III, 15%
II, 85%
CN
Mo(CO)6
CBr4 + CH3CN
Br
IV
160oC, 5 h , 68%
CHBr3
CN
Br
VII
VI
VIII
V
1084

CYANATION OF ADAMANTANE AND DIAMANTANE
1085
adamantane (I). The side product, 1-bromoadamantane
(III), was isolated in 15% yield. Under similar conditions
we obtained from diamantane (IV) at 68% conversion
a mixture of 1- diamantanecarbonitrile (V), 4-di-
amantanecarbonitrile (VI), 1- (VII) and 4-(VIII)
bromodiamantanes in the ratio 1.5:1:0.3:0.2.°
The catalysts and reagents were used in the molar
ratio [Mo(CO)6]:[AdH or DAH]:[CBr4]:[CH3CN]
1:100:100:2000.
graphy on aluminum oxide of the II grade of activity,
eluent the mixture dichloromethane–hexane, 1:1 v/v. The
main fraction in reaction with adamantane after removing
the solvent was colorless crystalline substance, mp 193–
194°C, identical to authentic nitrile II (yield 85%). The
second fraction (eluent dichloromethane) contained
1-bromoadamantane (III) (~15%), mp 119–120°C.
1- and 4-Diamantanecarbonitriles were isolated by
column chromatography after a vacuum distillation, bp
90°C (10 mm Hg). IR spectrum, ν, cm–1: 2200 (C°N).
In the reaction mixture alongside compounds II, III,
V–VIII we found by GLC and GC-MS methods also
bromoform as the main reaction product thus indicating
that CBr4 was involved not only into the bromination
but also into the cyanation of adamantane and diamantane
with acetonitrile. The reaction did not occur without
CBr4.
1-Adamantanecarbonitrile (II). IR spectrum, ν,
1
cm–1: 2250 (C°N). H NMR spectrum, δ, ppm: 1.75 t
(6H, 3CH2), 2.05 m (3H, 3CH), 1.60 t (6H, 3CH2).
13C NMR spectrum, δ, ppm: 29.51 (C1), 39.20 (C2, C8,
C9), 26.43 (C3, C5, C7), 35.07 (C4, C6, C10), 124.33
(Ca”N). Mass spectrum, m/z (Irel, %): [M]+ (0), 39 (12),
41 (12), 53 (5), 55 (5), 65 (5), 67 (10), 77 (10), 79 (21),
81 (7), 91 (7), 93 (17), 97 (7), 135 (100). Found, %:
C 82.01; H 9.37; N 8.62. C11H15N. Calculated, %:
C 81.93; H 9.38; N 8.69.
Considering the formation of 1-bromoadamantane
(III) as the minor reaction product it was reasonable to
suggest a two-stage mechanism of nitrile II formation
via 1-bromoadamantane (III). However the reaction of
1-bromoadamantane (III) with CH3CN in the presence
of Mo(CO)6, but without CBr4, provided nitrile II in no
more than 15% yield. On adding CBr4 into the system
the reaction turned to the formation of 1,3-dibromo-
adamantane (IX). The results of our experiments suggest
that the governing part in the formation of 1-ada-
mantaneacarbonitrile (II) belongs evidently to the catal-
yst, in particular, to the nitrile complex of molybdenum
that forms from Mo(CO)6 and CH3CN.
1-Diamantanecarbonitrile (V). 13C NMR spectrum,
δ, ppm: 25.35 (C4), 25.94 (C9), 33.53 (C3, C14), 36.44
(C8, C10), 36.72 (C6), 37.44 (C7, C11), 37.76 (C1), 38.66
(C2, C12), 38.80 (C5), 40.76 (C13), 124.86 (C°N). Found,
%: C 84.08; H 8.82; N 7.1. C15H19N. Calculated, %: C
84.45; H 8.98; N 6.57.
4-Diamantanecarbonitrile (VI). 13C NMR spectrum,
δ, ppm: 25.35 (C9), 25.94 (C2, C6, C12), 29.82 (C4), 35.94
(C1, C7, C11), 37.17 (C8, C10, C13), 41.67 (C3, C5, C14),
124.54 (C°N). Found, %: C 84.21; H 8.85; N 6.94.
C15H19N. Calculated, %: C 84.45; H 8.98; N 6.57.
The structure of 1-bromo-, 1,3-dibromoadamantanes,
1- and 4-bromodiamantanes was proved by comparison
with authentic samples and published data [1, 8, 9].
The reaction products were analyzed by GLC on
instruments Tsvet-102 and Chrom-5, flame-ionization
detector, column 1200 mm × 3 mm, stationary phase
silicon SE-30 (5%) on Chromaton N-AW-HMDS (1.125–
0.160 mm), carrier gas helium, flow rate 50 ml/min, ramp
from 50 to 220°C. IR spectra were recorded on a
spectrophotometer UR-20 from pellets with KBr or mulls
in mineral oil. 1H and 13C NMR spectra were registered
on a spectrometer Jeol FXG at operating frequencies 90
and 22.5 MHz respectively, solvent CDCl3, chemical
shifts reported in δ, ppm, from TMS. Mass spectra
(electron impact, 70 eV) were taken on a GC-MS
instrument Finnigan MAT-112 S. Elemental analyses
were determined on an analyzer Karlo Erba, model 1106.
On replacement of CBr4 by CHBr3 the yield of nitrile
II reduced to 30%.
The reaction was performed in a glass ampule of
20 ml capacity or in a pressure stainless-steel micro-
reactor (17 ml). Results of parallel runs were materially
identical. Into a microreactor (ampule) under an argon
atmosphere was charged 0.1 mmol of Mo(CO)6, 10 mmol
of adamantane (or 10 mmol of diamantane), 10 mmol of
CBr4, and 200 mmol of acetonitrile (CH3CN was
simultaneously a reagent and a solvent). The reactor was
hermetically closed (the ampule was sealed) and heated
at 140–160°C for 6 h with stirring. On completion of the
reaction the microreactor (the ampule) was cooled to
room temperature, opened, the excess acetonitrile was
distilled off, the residue was dissolved in
dichloromethane and subjected to column chromato-
The study was carried out under a financial support
of the Russian foundation for Basic Research (grant no.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

KHUSNUTDINOV et al.
1086
no. 16, p. 3.
08-03-97005) and of the Program of the Presidium of
the Russian Academy of Sciences no. 8.
4. Davis, R. and Untch, K.G., J. Org. Chem., 1984, vol. 46,
p. 2985.
5. Reinhardt, H.F., J. Org. Chem., 1962, vol. 27, p. 3258.
6. Shvekhgeimer, G.A., Kuz’micheva, L.K., and Novi-
kov, S.S., Izv. Akad. Nauk SSSR, Ser. Khim., 1974, p. 144.
7. Olah, G.A., Farooq, O., and Prakash, G.K.S., Synthesis,
1985, p. 1140.
REFERENCES
1. Bagrii, E.I., Adamantany (Adamantanes), Moscow: Nauka,
1989, 264 p.
8. Fort, R.C., Adamantane: The Chemistry of Diamond
Molecules, New York: Marcel Dekker, 1976, 386 p.
9. Courtney, T., Johnston, D.E., MsKervey, M.A., and Roo-
ney, J.J., J. Chem. Soc., Perkin Trans. 1, 1972, p. 2691.
2. Meier, M. and Ruchardt, C., Tetrahedron Lett., 1984,
vol. 25, p. 3441.
3. Zosim, L.A., Verpovskii, N.S., andYurchenko,A.G., Vestn.
Kiev. Politekhn. Inst., Khim. Mashinostr. Tekhnol., 1979,
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