Oxidation of adamantane with hypobromous acid generated in situ from CHnBr4-n and H2O in the presence of molybdenum complexes

Full text of DOI:10.1134/S1070428007040240

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 4, pp. 623–624. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © R.I. Khusnutdinov, N.A. Shchadneva, R.Yu. Burangulova, T.M. Oshnyakova, U.M. Dzhemilev, 2007, published in Zhurnal
Organicheskoi Khimii, 2007, Vol. 43, No. 4, pp. 625–626.
SHORT
COMMUNICATIONS
Oxidation of Adamantane with Hypobromous Acid
Generated in situ from CHnBr4 – n and H2O in the Presence
of Molybdenum Complexes
R. I. Khusnutdinov, N. A. Shchadneva, R. Yu. Burangulova,
T. M. Oshnyakova, and U. M. Dzhemilev
Institute of Petroleum Chemistry and Catalysis, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
e-mail: ink@anrb.ru
Received March 20, 2006
DOI: 10.1134/S1070428007040240
Oxidation of hydrocarbons of the adamantane (I)
series underlie important preparative procedures for
the synthesis of their oxygen-containing derivatives, in
particular of adamantan-1-ol (II). Adamantan-1-ol is
used as starting material for the preparation of such
important drugs as Amantadine (Symmetrel), Reman-
tadine, and Kemantan [1].
also catalyze oxidation of adamantane with sodium
periodate at 40°C [11]. The reaction involves mainly
the bridgehead carbon atom in molecule I. However,
despite prolonged heating (26 h), the conversion did
not exceed 81%, and the fraction of adamantan-1-ol
(II) in the reaction mixture was 82%.
We performed selective oxidation of adamantane
(I) to adamantan-1-ol (II) with the system CBr4–H2O–
Mo(CO)6. The reaction was complete in 3 h at 150°C,
and the yield of II was about 85%, the conversion of I
being 85%. The catalyst and reactant ratio [Mo(CO)6]:
[I]:[CBr4 or CHBr3]:[H2O] was 1:100:100:(1000–
2000). Apart from adamantan-1-ol (II), the reaction
mixture contained bromoform (major product) and
a small amount of CH2Br2 (according to the GLC and
MS data), indicating that CBr4 is involved in the oxida-
tion process. No reaction occurred in the absence of
CBr4. Iodometric titration of the reaction mixture
revealed active bromine; this means that hypobromous
acid (HOBr) is generated in the system. The concentra-
tion of HOBr was estimated at 0.9 mg/ml; therefore,
we presumed that hypobromous acid is the true oxidant
in this reaction.
Adamantan-1-ol (II) can be synthesized by cata-
lytic oxidation of adamantane (I) with such oxidants as
oxygen, hydrogen peroxide, alkyl hydroperoxides, and
iodosylbenzene in the presence of Co, Mn, Fe, and Ru
complexes [1–12]. Catalytic oxidation of adamantane
(I) generally gives mixtures of products. For example,
the oxidation of I with atmospheric oxygen in pyri-
dine–acetic acid in presence of an iron catalyst and
zinc at 40°C afforded a mixture of adamantan-1-ol and
adamantan-2-ol whose ratio ranged, depending on the
conditions, from 10:1 to 24.8:1, the overall yield
being 6–16% [8].
Porphyrin manganese complexes catalyze oxidation
of adamantane (I) with such oxidants as NaClO2, mag-
nesium monoperoxyphthalate, and potassium peroxo-
sulfate; in these cases, the reaction occurred preferen-
tially at the tertiary carbon atom [9]. Catalytic oxida-
tion of adamantane (I) with formation of three oxygen-
containing products, adamantan-1-ol (II, 68%), ada-
mantane-1,3-diol (III, 25%), and adamantan-2-one
(IV, 1%) was reported in [10]; here, 2,6-dichloro-
pyridine N-oxide was used as oxidant in the presence
of (tetraphenylporphyrinato)(carbonyl)ruthenium
[Ru(TPP)(CO)] as catalyst. Ruthenium compounds
OH
Mo(CO)6
150°C, 3 h
+ CBr4 + H2O
+ CHBr3
85%
I
II
Mo(CO)6, 150°C, 20 min
CBr4 + H2O
HOBr + CHBr3
623

KHUSNUTDINOV et al.
624
The conversion of adamantane (I) attains 100% on
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 220°C. The 13C NMR spectra were re-
corded on a JEOL FXQ instrument at 22.5 MHz using
tetramethylsilane as internal reference.
prolonged reaction; however, the product mixture be-
comes more complex due to formation of 1-bromo-
adamantane (V), 3-bromoadamantan-1-ol (VI), and
adamantane-1,3-diol (VII), the molar ratio II:V:VI:
VII being 5 : 1 : 4 : 2. Replacement of CBr4 in the
oxidizing system by CHBr3 leads to reduced conver-
sion of adamantane (I) (50%), and the reaction be-
comes less selective. After 1 h, the reaction mixture
contained adamantan-1-ol (II), 3-bromoadamantan-
1-ol (VI), and adamantane-1,3-diol (VII) at a ratio of
5:1:1.
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water. The reactor was hermetically capped (the am-
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(VI), and adamantane-1,3-diol (VII) were identified by
comparing their properties with those of authentic
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The products were analyzed by gas–liquid chroma-
tography on Tsvet-102 and Chrom-5 instruments
equipped with flame ionization detectors; 1.2-m×3-
2004.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 4 2007