Oxidation of adamantane with 2,3,4,5,6-pentafluoroperoxybenzoic acid in the presence of RuCl3 · 3H2O

Full text of DOI:10.1134/S1070428015010224

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2015, Vol. 51, No. 1, pp. 123–124. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © R.I. Khusnutdinov, T.M. Oshnyakova, 2015, published in Zhurnal Organicheskoi Khimii, 2015, Vol. 51, No. 1, pp. 125–126.
SHORT
COMMUNICATIONS
Oxidation of Adamantane
with 2,3,4,5,6-Pentafluoroperoxybenzoic Acid
in the Presence of RuCl3·3H2O
R. I. Khusnutdinov and T. M. Oshnyakova
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
e-mail: ink@anrb.ru
Received May 16, 2014
DOI: 10.1134/S1070428015010224
Adamantan-1-ol (1, 1-AdOH) is the most important
adamantane derivative. It is used as starting compound
in the synthesis of memantine and rimantadine, and
1-adamantyl ethers are efficient antioxidant additives
to oils and transmission fluids, which simultaneously
improve their rheological characteristics at low tem-
peratures [1].
A known procedure for the synthesis of alcohol 1 is
based on the catalytic oxidation of adamantane (2)
with m-chloroperoxybenzoic acid in the presence of
metal complexes. In particular, the yield of 1 in the
presence of Ni, Fe, Mn, and Co complexes [2–5]
ranges from 1 to 12%. Ruthenium-containing catalysts
ensured preparation of adamanatan-1-ol in 66% yield
[6]. However, in the latter case the reaction was ac-
companied by side processes leading to adamantan-
2-ol, adamantan-2-one, and 1-chloroadamantane.
In this communication we report for the first time
the oxidation of adamantane (2) with 2,3,4,5,6-penta-
fluoroperoxybenzoic acid (3) catalyzed by RuCl3 ·
3H2O. 2,3,4,5,6-Pentafluoroperoxybenzoic acid (3) is
a stable compound whose synthesis and application
were reported for the first time in [7, 8]. Peroxy acid 3
efficiently oxidizes ∆5-steroids [7] and α,β-unsaturated
esters [8] to the corresponding epoxy derivatives in
almost quantitative yield even in the absence of a cata-
lyst. Taking into account unusually high activity of
acid 3 in reactions with olefins, we anticipated that it
can be used for the selective transformation of ada-
mantane (2) into practically important alcohol 1.
In fact, acid 3 in the presence of RuCl3·3H2O
oxidized adamantane (2) in methylene chloride at
40°C (6 h) with formation of adamantan-1-ol (1). The
conversion of 2 [ratio 2–3 (12% Oact)–RuCl3·3H2O
1:2:0.03] was 62%, and the selectivity for 1 was 85%.
No reaction occurred in the absence of RuCl3·3H2O. It
should be noted that the catalyst is poorly soluble in
methylene chloride, and it gradually dissolved during
the process; the mixture became homogeneous after
1 h. Blank experiments showed that ruthenium(III)
chloride catalyzes decomposition of acid 3. According
to the iodometric titration data, at 40°C the concentra-
tion of 3 in 30 min decreases by 0.01 mg/mL, i.e., the
rate of decomposition of 3 in the absence of a substrate
is fairly low. Therefore, the oxidation of 2 was carried
out by gradually adding a solution of acid 3 in meth-
ylene chloride or methylene chloride–ethyl acetate
mixture. Raising the catalyst concentration to 5 mol %
increased the conversion of 2 to 89%, but the yield of
alcohol 1 decreased to 60% due to side formation of
adamantan-1-yl 2,3,4,5,6-pentafluorobenzoate (4).
Ester 4 undergoes hydrolysis in 0.1 N NaOH at 100°C
O
CH2Cl2, 40°C
Conversion 89%
+
OH
O
C6F5
RuCl3· 3H2O, 6 h
1
2:1
4
+
C6F5CO3H
CH2Cl2–EtOAc (8:1), 50°C
Conversion 95%
1
+
4
2
3
1:15
123

KHUSNUTDINOV, OSHNYAKOVA
124
(5 h) to give adamantan-1-ol (1) and pentafluoroben-
zoic acid. Thus, the overall selectivity for alcohol 1
approaches 100%.
o-F), –150.69 (1F, p-F), –139.82 (2F, m-F). Mass spec-
trum, m/z (Irel, %): 346 (1) [M]+, 39 (14), 40 (10),
41 (28), 53 (10), 55 (15), 56 (16), 65 (6), 67 (20),
77 (18), 78 (14), 79 (44), 81 (10), 91 (28), 92 (88),
93 (50), 94 (14), 107 (13), 117 (11), 119 (13),
134 (100), 135 (44), 166 (12), 194 (36), 195 (3),
211 (2). Found, %: C 58.90; H 4.40. C17H15F5O2.
Calculated, %: C 58.96; H 4.37. M 314.30.
To examine the effect of the temperature, some ex-
periments were run in a mixture of methylene chloride
with ethyl acetate which readily dissolves RuCl3·3H2O
(CH2Cl2–EtOAc 8:1). Furthermore, addition of ethyl
acetate made it possible to carry out the oxidation at
higher temperature. For instance, the conversion of 2
was 95% in 6 h at 50°C, and the major product was
ester 4. Further raising the temperature was undesir-
able since vigorous decomposition of acid 3 was
observed at 60°C. Increase in the amount of the cata-
lyst to 10 mol % also resulted in reduced conversion of
adamantane (2) due to strong decomposition of 3 by
the action of RuCl3·3H2O.
A solution of 0.33 g (1.47 mmol) of acid (3) in
3 mL of methylene chloride or in a mixture of 2 mL of
methylene chloride and 0.5 mL of ethyl acetate was
added dropwise over a period of 2 h to a mixture of
0.0077 g (0.037 mmol) of RuCl3 ·3H2O and 0.1 g
(0.73 mmol) of adamantane in 2 mL of methylene
chloride, heated to 40°C. The mixture was stirred for
4 h at 40 or 50°C and filtered through a layer of Al2O3,
the sorbent was washed with chloroform, and the prod-
ucts were isolated by silica gel column chromatog-
raphy (60–200 μm, 60 Å) using chloroform as eluent.
Acid 3 was prepared by ozonolysis of commercial
2,3,4,5,6-pentafluorobenzaldehyde in CCl4 [7].
1
The H and 13C NMR spectra were recorded on
a Bruker Avance-400 spectrometer from 400.13 and
100.62 MHz, respectively, using CDCl3 as solvent. The
mass spectra were obtained on a Shimadzu GCMS-
QP2010Plus instrument (SPB-5 capillary column,
30 m×0.25 mm; carrier gas helium; oven temperature
programming from 40 to 300°C at a rate of 8 deg/min,
injector temperature 280°C, ion source temperature
200°C; electron impact, 70 eV). The elemental compo-
sitions were determined on a Carlo Erba 1106 analyzer.
The progress of reactions and the purity of products
were monitored by GLC on Shimadzu GC-9A and GC-
2014 instruments (2 m×3-mm column packed with
5% of SE-30 on Chromaton N-AW-HMDS; oven tem-
perature programming from 50 to 270°C at a rate of
8 deg/min; carrier gas helium, flow rate 47 mL/min).
Ester 4, 0.2 g, was hydrolyzed by heating in 20 mL
of 0.1 N NaOH under reflux. When the reaction was
complete, adamantan-1-ol (1) was isolated by extrac-
tion with chloroform (3×30 mL).
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77 (9), 79 (8), 94 (14), 95 (100), 96 (7), 109 (5).
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Adamantan-1-yl 2,3,4,5,6-pentafluorobenzoate
(4). Yield 89%, white crystals, Rf 0.53 (CHCl3),
1
mp 84°C (sublimes). H NMR spectrum, δ, ppm:
1.73 m (6H, CH2), 2.15 m (3H, CH), 2.25 m (6H,
13
CH2). C NMR spectrum, δC, ppm: 85.16 (C1), 41.36
(C2, C8, C10), 30.99 (C3, C5, C7), 36.00 (C4, C6, C9),
110.13 (Ci), 136.28 and 138.56 (Cm), 141.30 and
143.61 (Cp), 143.85 and 146.14 (Co), 157.40 (C=O).
19F NMR spectrum (CDCl3), δF, ppm: –160.98 (2F,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 1 2015