Iron pentacarbonyl, efficient promoter of aromatic compounds alkylation with bromoadamantane

Full text of DOI:10.1134/S1070428014050236

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 5, pp. 752–754. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © A.A. Ambartsumyan, T.T. Vasil’eva, O.V. Chakhovskaya, N.E. Mysova, K.A. Kochetkov, 2014, published in Zhurnal Organicheskoi
Khimii, 2014, Vol. 50, No. 5, pp. 762–764.
SHORT
COMMUNICATIONS
Iron Pentacarbonyl, Efficient Promoter of Aromatic Compounds
Alkylation with Bromoadamantane
A. A. Ambartsumyan, T. T. Vasil’eva, O. V. Chakhovskaya,
N. E. Mysova, and K. A. Kochetkov
Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences,
ul. Vavilova 28, Moscow, 119991 Russia
e-mail: const@ineos.ac.ru
Received September 15, 2013
DOI: 10.1134/S1070428014050236
We have repeatedly demonstrated the large oppor-
,
Δ
Fe(CO)5
PhR
tunities of iron pentacarbonyl Fe(CO)5 application [1–7]
as initiator of versatile organic reactions leading to the
formation of bonds С–С, С–О, С–Hlg, etc. Fe(CO)5 is
a promoter of addition of α-halocarboxylic acids esters
and nitriles to aldehydes and ketones along the Refor-
matsky type reaction [2, 3]; the reaction proceeds
especially successful with polyfluorinated aldehydes
and ketones [3, 4]. Using Fe(CO)5 we succeeded to
perform a diastereoselective hydrodimerization of
aromatic aldehydes with transition to diols [5], and
also to carry out the addition of С4F9I [6] and benzyl
bromide [7, 8] to pentafluorobenzaldehyde by the type
of Zaitsev–Barbier reaction. However it was
established that iodohexane under similar conditions
did not react with pentafluorobenzaldehyde and
formed dihexyl ketone [6].
Br
R
II_V
I
R = H (II, 80°C), Me (III, 80°C), Cl (IV, 110°C), Br
(V, 110°C).
Since a new reaction direction was discovered, we
carried out the alkylation of a series of typical aromatic
compounds under similar conditions. In all cases the
arenes alkylation products II–V were obtained in good
yields. Thus we discovered for the first time the ability
of Fe(CO)5 to initiate alkylation with 1-bromoada-
mantane in Friedel–Krafts reaction. These reactions do
not occur without initiator, besides, the yield of com-
pounds II–V does not virtually decrease at reducing
the amount of Fe(CO)5 to 0.5 mol per 1 mol of 1-
bromoadamantane. Under similar conditions nitro-
benzene, dichlorobenzene, and cyclohexane do not
undergo alkylation. The alkylation with 1-bromo-
adamantane under the action of Friedel–Krafts
catalysts is known [9, 10], but metal carbonyls have
not been used in these processes. Besides in the known
examples the alkylation product yields in some cases
were lower, and higher temperature was required along
with prolonged stirring, inert environment and as a rule
larger (1–2 mol) amounts of initiator. Therewith the
reactions catalyzed with Lewis acids occurred mainly
in heterogenic conditions [9, 10], and the use of FeCl3
and SbCl5, for instance, resulted in a partial
chlorination of adamantane [17].
In this study we have continued the investigation of
the initiating effect of Fe(CO)5 using as a halogen-
containing addend the sterically hindered 1-bromo-
adamantane (I) that is often utilized in alkylation [9–
11] and cross-coupling [12, 13] reactions for the intro-
duction of bulky adamantly fragment providing the
final products with special physicochemical properties
[14] and modifying their physiological action [11, 15, 16].
The attempt to add 1-bromoadamantane (I) to
pentafluorobenzaldehyde by the type of Zaitsev–
Barbier reaction in the presence of Fe(CO)5 in benzene
at 80°С was unsuccessful, but here the alkylation
occurred of usually inert solvent with the formation of
1-phenyladamantane (II).
752

IRON PENTACARBONYL, EFFICIENT PROMOTER OF AROMATIC COMPOUNDS
753
The mechanism of the process may be presented as
follows: Fe(CO)5 forms an intermediate complex with
bromoadamantane activating the haloalkane. We
formerly observed the result of such interaction
manifested in the shift of the absorption bands in the
UV spectrum to the longwave region in the mixtures of
Fe(CO)5 with a haloalkane [18]. As a result of this
activation the haloalkane may suffer a dimerization as
in the case of benzyl bromide [7, 8], or form an active
radical as has been suggested for iodohexane [6]. The
formation of ion-radical is also possible [19, 20] with
subsequent aldehyde alkylation to give the corres-
ponding alcohol (like the cases described in [2–4, 7,
8]), yet this is hardly probable for the bulky ada-
mantine fragment. In the reaction conditions under
consideration apparently a sterically hindered electro-
philic species appears or an ion-radical [19, 20]. It is
presumable that the formed electrophile is unable to
attack the “hard” carbonyl site of the pentafluoro-
benzaldehyde [3, 4] but efficiently alkylates the
aromatic compound present in the mixture along the
type of Friedel–Krafts reaction [9, 10].
(6H, CH2, Ad), 2.10 s (6H, CH2, Ad), 2.28 s (3H, CH,
Ad), 2.51 s (3H, CH3), 7.33–7.45 m (4Harom). Mass
spectrum, m/z (Irel, %): 226 (95) [M]+, 169 (100) [M –
C4H9]+, 183 (25) [M – C3H7]+, 91 (25) [M – Ad]+.
1-(4-Chlorophenyl)adamantane (IV). Yield
1
0.0696 g (62%), mp 89°С (mp 90–91°С [22]). Н
NMR spectrum, δ, ppm: 1.85 s (6H, CH2, Ad), 1.99 s
(6H, CH2, Ad), 2.17 s (3H, CH, Ad), 7.35 m (4Harom).
Mass spectrum, m/z (Irel, %): 246 (100) [M]+, 189 (80)
[M – C4H9]+, 153 (25) [M – C4H9 – HCl]+, 135 (100) [Ad]+.
1-(4-Bromophenyl)adamantane (V). Yield 0.0863 g
(64%), mp 99–100°С [10]. 1Н NMR spectrum, δ, ppm:
1.86 s (6H, CH2, Ad), 2.0 м (6H, CH2, Ad), 2.17 s (3H,
CH, Ad), 7.30–7.50 m (4Harom). Mass spectrum, m/z
(Irel, %): 290 (100) [M]+, 233 (30) [M – C4H9]+, 154
(75) [M – Ad]+, 135 (40) [Ad]+.
Mass spectra were recorded on a mass spectrometer
Finnigan SSQ-700 (ionizing electrons energy 70 eV).
1Н NMR spectra were registered on spectrometers
Bruker Avance 300 and Bruker Avance 400 (300 and
400 MHz respectively) in CDCl3 at 30°C, chemical
shifts measured with respect to TMS. The melting
points were measured in a sealed capillary with a
melting point indicator Electrothermal IA 9000. GLC
was performed on a chromatograph LKhM-80, steel
column (1300 × 3 mm), statiorary phase SKTFT-50Х
on Chromaton N-AW, carrier gas helium, detector
katharometer, ramp in the range 50–250°С, heating
rate 6 deg min–1.
This example once again shows wide opportunities
of Fe(CO)5 application [1] as the initiator of versatile
organic reaction of С–С bond formation not only in
aliphatic [2], but also in aromatic series.
Arenes alkylation with 1-bromoadamantane in
the presence of iron pentacarbonyl. In a flask
equipped with a reflux condenser and gas-washing
bottle for monitoring СО liberation to a mixture of 0.1
g (0.5 mmol) of reagent I and 1 mL of arene was
added 0.135 mL (1 mmol) of Fe(CO)5 and a drop
(~1%) of benzene solution of CBrCl3 as activator. The
mixture was stirred for 5 h at the necessary tempera-
ture till the end of gas liberation and the pressure
decrease. Then the reaction mixture was treated with
30 mL of 1N HCl, thrice washed with water, the
organic layer was dried with Na2SO4, evaporated in a
vacuum, the residue was chromatographed on a
column packed with silica gel (eluent benzene).
All organic reagents were purified by distillation or
recrystallization. Bromoadamantane (I) was purchased
from Aldrich. Fe(CO)5 of Fluka (98%) was used
without additional purification.
The study was carried out under the financial
support of the Presidium of the Russian Academy of
Sciences (program Р5 “Fundamental Science applica-
tion to medicine”), of the Department of chemistry and
materials science of the Russian Academy of Sciences
(program no. 09 “Biomolecular and medical
chemistry”), and of the Russian Foundation for Basic
Research (grants nos. 09-03-01097 and 11-04-01245).
1-Phenyladamantane (II). Yield 0.0883 g (92%),
mp 79–80°С [21]. At using 0.5 and 0.25 mmol of
1
Fe(CO)5 the yield decreased to 84%. Н NMR spec-
trum, δ, ppm: 1.87 s (6H, CH2, Ad), 2.02 s (6H, CH2,
Ad), 2.19 s (3H, CH, Ad), 7.25–7.40 m (5Harom). Mass
spectrum, m/z (Irel, %): 212 (80) [М]+, 169 (13) [М –
С3Н7]+, 155 (100) [М – С4Н9]+, 135 (2) [Ad]+.
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1-(4-Tolyl)adamantane (III). Yield 0.1 g (95%),
1
mp 102°C [10]. Н NMR spectrum, δ, ppm: 1.97 s
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AMBARTSUMYAN ET AL.
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