Selective hydroxylation of diamantane with 2,3,4,5,6-pentafluoroperbenzoic acid in the presence of molibdenum complexes

Article abstract of DOI:10.1134/S1070428016080054

Oxidation of diamantane with 2,3,4,5,6-pentafluoroperbenzoic acid catalyzed with complexes MoO(O₂)·2QOH, MoO(O₂)(H₂O)₂proceeds selectively affording diamantan-1-ol and diamantan-1-yl 2,3,4,5,6-pentafluorobenzoat

Full text of DOI:10.1134/S1070428016080054

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2016, Vol. 52, No. 8, pp. 1121–1125. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © R.I. Khusnutdinov, T.M. Oshnyakova, L.M. Khalilov, A.R. Baibuldina, U.M. Dzhemilev, 2016, published in Zhurnal Organicheskoi
Khimii, 2016, Vol. 52, No. 8, pp. 1131–1135.
Selective Hydroxylation of Diamantane
with 2,3,4,5,6-Pentafluoroperbenzoic Acid in the Presence
of Molibdenum Complexes
R. I. Khusnutdinov, T. M. Oshnyakova, L. M. Khalilov,
A. R. Baibuldina, and U. M. Dzhemilev*
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, pr. Oktyabrya 141, Ufa, 450075 Russia
*e-mail: ink@anrb.ru
Received May 18, 2016
Abstract—Oxidation of diamantane with 2,3,4,5,6-pentafluoroperbenzoic acid catalyzed with complexes
MoO(O2)·2QOH, MoO(O2)(H2O)2 proceeds selectively affording diamantan-1-ol and diamantan-1-yl 2,3,4,5,6-
pentafluorobenzoate.
DOI: 10.1134/S1070428016080054
In the molecule of the second specimen of the
homologous series of diamondoids, diamantane 1, two
types of tertiary carbon atoms are present: 6 medial
(С1, С2, С6, С7, С11, С12) and 2 apical (С4, С9) atoms.
Because of diverse surroundings they possess different
reactivity coming out in the synthesis of monosubs-
tituted derivatives of compound 1, which usually form
as a mixture of isomeric products of substitution in the
positions 1 and 4, the former prevailing [1]. This
occurs at the preparation of diamantanols by
diamantane 1 hydroxylation with various oxidants. The
ratio of isomers, diamantane-1- and -4-ols 2 and 3,
which are very difficultly separable, depends on the
nature of the oxidant.
limide and AIBN a mixture formed of compounds 2
and 3 in a ratio 3 : 1 [2]. The oxidation with lead tetra-
acetate in the environment of CF3COOH‒CH2Cl2 led
to the formation of the mixture of compounds 2 and 3
in a ratio 9 : 1. When the diamantane 1 oxidation with
Pb(OAc)4 is carried out with adding LiBr the fraction
of isomer 3 grows to 14% [3]. The oxidation of
diamantane 1 with m-chloroperbenzoic acid proceeds
sufficiently selectively giving compounds 2 and 3 in a
ratio 8 : 1 [4].
In the search for a reagent for the selective hydro-
xylation of diamantane 1 we studied its oxidation with
2,3,4,5,6-pentafluoroperbenzoic acid 4 in the presence
of catalysts, molybdenum complexes. Peracid 4 was
first obtained and investigated in [5, 6], and it was
successfully used for adamantane hydroxylation [7].
At diamantane 1 oxidation with oxygen in the
conditions of radical initiation using N-hydroxyphtha-
Scheme 1.
5
+
COOOH
F
OCOC6F5
OH
CH2Cl2 C2H4Cl2
60oC, 6 h
+
2
7
1.9 : 1
6
1
4
2
+
7
3.5 : 1
[Mo]–[1]–[4] 1 : 20 : 40
1121

KHUSNUTDINOV et al.
1122
Scheme 2.
COOOH
MoO(O2) 2QOH
5
+
F
CH2Cl2 C2H4Cl2,
60oC, 12 h
OCOC6F5
1
4
7
[5]–[1]–[4] 1 : 20 : 80
Peracid 4 (6% Oact) in the presence of molybdenum
oxo-peroxo complexes MoO(O2)·2QOH 5 (QOH is 8-
hydroxyquinoline) and MoO(O2)(H2O)2 6 oxidizes
diamantane 1 (60°С, 6 h) giving diamantan-1-ol 2 and
diamantan-1-yl 2,3,4,5,6-pentafluorobenzoate 7, and
their yields depend on the catalyst nature and the
reaction conditions (Scheme 1).
In the presence of MoO(O2)·2QOH 5 the conver-
sion of diamantane 1 reached 52%, in the presence of
MoO(O2)(H2O)2 6, 40%, and in the presence of Mo(CO)6
and MoO2(acac)2 the conversion of compound 1 did
not exceed 5%. Due to the limited solubility of
complexes 5 and 6 in the most organic solvents the
experiments were performed in the mixture dichlo-
romethane–1,2-dichloroethane. In this mixture
complexes 5 and 6 are completely soluble at 30‒40°С.
Scheme 3.
The reaction time increased to 12 h did not result in
a larger yield of alcohol 2. At 30°С the yield of
compound 2 was 30%. At the oxidation of diamantane
1 with 4-fold excess of peracid 4 (60°С, 12 h) in the
presence of complex 5 the only reaction product was
diamantan-1-yl 2,3,4,5,6-pentafluorobenzoate 7 in a
50% yield (Scheme 2).
COOOH
[Mo]_base
+
F
CH2Cl2 C2H4Cl2,
60oC, 6 h
OH
1
4
2
[Mo]–[1]–[4]–[base] 1 : 20 : 40 : 20
It is presumable that the cause of the incomplete
conversion of diamantane 1 is the decomposition of
complexes 5 and 6 by the action of strong 2,3,4,5,6-
pentafluorobenzoic acid formed in the course of the
reaction. Evidently, the deactivating effect of peracid 4
may be reduced with bases. Actually, the addition of
[Mo]
Base
NaHCO3
K2CO3
NaOAc
NaOAc
Yield 2, %
5
61
49
68
71
6
F2
C4
C3
C18
F1
F3
C5
C19
C17
C14
1.537
C2
C6
C7
O1
1.537
C1
C20
C16
C12
C11
C10
C1a5
1.537
1.524
C21
C8
F4
1.528
C13
O2
F5
1.535
C9
1.534
Fig. 1. Geometry of diamantan-1-yl 2,3,4,5,6-pentafluorobenzoate 7 from XRD data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 8 2016

SELECTIVE HYDROXYLATION OF DIAMANTANE WITH 2,3,4,5,6-PENTAFLUORO...
1123
Table 1. Bond lengths in the molecule of diamantan-1-yl
2,3,4,5,6-pentafluorobenzoate 7
NaHCO3, K2CO3, or NaOAc results in a considerable
increase in the yield of alcohol 2 (68%) with simulta-
neously the selectivity growing to 100% (Scheme 3).
Bond
d, Å
Bond
d, Å
The structure of diamantan-1-ol 2 was established
O1‒C1
O1‒C15
O2‒C15
C2‒C1
C2‒C3
C2‒C7
C3‒C4
C4‒C14
C4‒C5
C6‒C11
C6‒C5
C7‒C6
C7‒C8
C9‒C8
C9‒C10
C11‒C10
C12‒C1
1.4861(17)
1.3271(18)
1.2020(18)
1.537(2)
1.5370(18)
1.538(2)
1.535(2)
1.528(2)
1.529(3)
1.543(2)
1.527(3)
1.540(2)
1.535(2)
1.524(3)
1.534(3)
1.534(2)
1.5372(18)
C12‒C11
C12‒C14
C13‒C1
C13‒C9
C15‒C16
C16‒C17
C16‒C21
C18‒C17
C18‒C19
C19‒C20
C21‒C20
F1‒C17
F2‒C18
F3‒C19
F4‒C20
F5‒C21
1.540(2)
1.5380(19)
1.5284(17)
1.535(2)
1
from the H, 13C NMR spectra and by the comparison
of the 13С NMR spectra with published data [8, 9].
Another proof of the selective oxidation of compound
1 furnishing diamantan-1-ol 2 is provided by X-ray
diffraction (XRD) analysis of ester 7.
1.508(2)
According to XRD data compound 7 forms
colorless crystal of triclinic crystal system (Fig. 1).
Fragment C6F5CO is turned around the С1–О1 bond by
a torsion angle О1С15С16С21 ‒55.47(3)°. The bond
lengths and bond angles in ester 7 are compiled in
Tables 1 and 2.
1.3877(19)
1.385(2)
1.381(2)
1.379(3)
To establish the effect of the ester substituent on the
diamantane scaffold we performed XRD analysis of
diamantane 1 (Fig. 2).
1.371(2)
1.384(2)
1.337(2)
As seen from the comparison of the bond distances
in compounds 1 and 7 (Tables 1 and 3) the influence of
the residue of 2,3,4,5,6-pentafluorobenzoate on the
bond lengths in the diamantane scaffold is negligible.
1.3370(17)
1.339(2)
1.339(2)
Therefore 2,3,4,5,6-pentafluoroperbenzoic acid in
the presence of complexes MoO(O2)·2QOH 5,
MoO(O2)(H2O)2 6 selectively oxidized diamantane 1
1.3369(17)
Table 2. Bond angles in the molecule of diamantan-1-yl 2,3,4,5,6-pentafluorobenzoate 7
Angle
φ, deg
Angle
φ, deg
Angle
O1C15C16
O2C15O1
O2C15C16
C2C7C6
φ, deg
Angle
φ, deg
C15O1C1
C1C12C11
C1C12C14
C14C12C11
C1C2C7
121.00(10)
107.03(11)
110.82(12)
110.53(13)
107.67(11)
111.08(11)
110.66(13)
108.95(13)
111.76(10)
104.16(10)
109.21(11)
108.95(12)
112.01(11)
110.47(11)
F1C17C18
118.01(13)
110.38(11)
127.79(15)
121.82(14)
108.54(13)
110.92(13)
110.75(14)
109.28(12)
122.92(13)
119.88(12)
117.08(15)
120.30(17)
120.10(17)
119.60(14)
120.26(15)
C4C14C12
C8C9C13
C8C9C10
C10C9C13
F3C19C18
F3C19C20
C20C19C18
C9C8C7
110.03(12)
109.46(14)
110.02(16)
108.89(13)
120.07(16)
119.79(18)
120.13(17)
109.06(13)
120.40(16)
120.05(18)
119.54(16)
109.36(13)
110.02(14)
C18C17C16 121.72(15)
C14C4C3
C14C4C5
C5C4C3
C7C6C11
C5C6C7
C5C6C11
C12C11C6
109.09(14)
109.36(16)
109.40(14)
107.88(14)
110.32(14)
110.88(14)
108.73(13)
C8C7C2
C3C2C1
C8C7C6
C3C2C7
C4C3C2
C1C13C9
O1C1C12
O1C1C2
O1C1C13
C12C1C2
C13C1C12
C13C1C2
C17C16C15
C21C16C15
C21C16C17
F2C18C17
F2C18C19
C19C18C17
F1C17C16
F4C20C21
F4C20C19
C19C20C21
C11C10C9
C6C5C4
C10C11C12 110.92(14)
C10C11C6
F5C21C16
F5C21C20
110.66(14)
120.07(15)
118.01(14)
C20C21C16 121.92(14)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 8 2016

KHUSNUTDINOV et al.
1124
frequencies 500.17 (1Н) and 125.78 (13С) МHz from
solutions in CDCl3. Mass spectra were measured on an
instrument Shimadzu GCMS-QP2010Plus (capillary
column SPB-5 30 × 0.25 mm, carrier gas helium, ramp
from 40 to 300°С, heating rate 8 deg/min, vaporizing
temperature 280°С, ion source temperature 200°С,
ionizing energy 70 eV). Elemental analysis of samples
was determined on an analyzer Carlo Erba 1106. Reac-
tions progress was monitored and the purity of
obtained compounds checked by GLC on a chromato-
graph Shimadzu GC-9A, GC-2014 [column 2 m × 3 mm,
stationary phase silicone SE-30 (5%) on Chromaton N-
AW-HMDS, ramp from 50 to 270°С, heating rate
8 deg/min, carrier gas helium (47 mL/min)].
Table 3. Bond lengths and bond angles in the molecule of
diamantane 1
Bond
С1–С2
d, Å
Bond
С10–С11
С12–С14
С3–С4
d, Å
1.5317(10)
1.5317(10)
1.5317(10)
1.5317(10)
1.5317(10)
1.5327(13)
1.5327(13)
1.5327(13)
1.5327(13)
φ, deg
1.5327(13)
1.5327(13)
1.5250(12)
1.5250(12)
1.5250(12)
1.5250(12)
1.5250(12)
1.5250(12)
С1–С12
С2–С7
С6–С7
С4–С5
С11–С12
С1–С13
С2–С3
С4–С-14
С9–С8
С9–С10
С9–С13
С5–С6
The XRD analysis of diamantane 1 and diamantan-
1-yl 2,3,4,5,6-pentafluorobenzoate 7 was carried out
on an automatic four-circle diffractometer XCalibur
Eos (graphite monochromator, MoKα-radiation, λ
0.71073 Å, ω-scanning, 2θmax 62°). The collection and
processing of data was performed using software
CrysAlisPro Oxford Diffraction Ltd. The structures
were solved by the direct method and refined by full-
matrix least-squares method in the anisotropic
approximation for nonhydrogen atoms. Hydrogen
atoms were localized by the difference Fourier
synthesis and included in the refinement with fixed
thermal parameters and positions. The calculations
were performed applying SHELX program [10]. Cif-
files are deposited in Cambridge Crystallographic Data
Center under the numbers CCDC 935374 (1) and
CCDC 1469654 (7). The data are available free on
request at the address CCDC, 12, Union Road, Cam-
bridge, CB2 1EZ, UK (fax: +44-1223-336033, e-mail:
deposit@ccdc.cam.ac.uk) or on the site http://
www.ccdc.cam.ac.uk/data_request/cif.
С7–С8
Angle
Angle
С3С4С14
С5С4С14
С4С3С2
φ, deg
С2С1С12
С2С1С13
С12С1С13
С3С4С5
108.57(7)
110.42(9)
110.27(9)
109.18(6)
109.18(6)
109.18(6)
109.79(8)
to form diamantan-1-ol 2 and diamantan-1-yl 2,3,4,5,6-
pentafluorobenzoate 7 opening a simple and promising
way to the synthesis of difficultly available diamantine
derivatives substituted in the position 1.
EXPERIMENTAL
1H, 13С, and 19F NMR spectra were registered on a
spectrometer Bruker Avance-III 500 Ascend, operating
C4
C3
Oxo‒peroxo molibdenum complexes MoO(O2)·
2QOH 5 and MoO(O2)(H2O)2 6 were synthesized by
procedures [11, 12] respectively. 2,3,4,5,6-Pentafluo-
roperbenzoic acid 4 was prepared by ozonization of
commercial 2,3,4,5,6-pentafluorobenzaldehyde by the
method [5, 6].
C5
C14
C2
C6
C7
C12
1.532
C1
1.533
C11
Diamantan-1-ol (2). To a mixture of 0.013 mmol
of catalyst 5 and 6, 0.05 g (0.26 mmol) of diamantane
1, and 0.013 mmol of a base (NaHCO3, K2CO3,
NaOAc) in 2 mL of 1,2-dichloroethane at 30‒50°С
was added dropwise 0.12 g (0.52 mmol) of peracid 4 in
2 mL of CH2Cl2 within 1.5 h. On completing the
addition of acid 4 0.013 mmol of a base was added,
and the mixture was stirred for 4.5 h at 60°С. The
C8
C13
C10
C9
1.525
Fig. 2. Geometry of diamantane 1 from XRD data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 8 2016

SELECTIVE HYDROXYLATION OF DIAMANTANE WITH 2,3,4,5,6-PENTAFLUORO...
1125
organic layer was decanted and filtered through a bed
of Al2O3 (eluent CHCl3), the inorganic phase was
treated with 0.1 N H2SO4 and was extracted with
CHCl3. Both organic phases were combined, the
solvents were evaporated. The reaction products were
isolated by column chromatography on silica gel (60–
200 µm, 60 Å), eluents: hexane, ethyl acetate. Yield
71%, white crystals, Rf 0.67 (EtOAc), mp 291‒292°С
Crystallographic data: C21H19F5О2. М 398.37, a
7.7448(6), b 9.9926(8), c 12.7617(12) Å, V 858.25(14) Å3,
Z 2, dcalc 1.541 g/cm3, R 0.0524, wR2 0.1537.
The study was carried out under the financial
support of the Russian Foundation for Basic Research
(grant no. 14-03-97029 p_povolzh’e_a).
1
Structural studies were performed in the Center of
joint usage “Agidel” at the Institute of Petrochemistry
and Catalysis, Russian Academy of Sciences.
(292‒294°С [13]). Н NMR spectrum, δ, ppm: 1.25
br.s (1Н, OH), 1.43‒1.50 m (2Н, СН2), 1.58‒1.74 m
(13H, 5CH2, 3CH), 1.95 s (1Н, CH), 2.04‒2.10 m (2H,
2CH), 2.14‒2.17 m (1H, CH). 13C NMR spectrum, δ,
ppm: 25.37 (С4), 30.52 (С9), 32.62 (С3,14), 36.80 (С6),
37.60 (С8,10), 38.06 (С5), 40.03 (С7,11), 43.45 (С2,12),
46.46 (С13), 70.92 (С1). Mass spectrum, m/z (Irel, %):
204 (18.4) [M]+, 186 (77.2), 130 (44.2), 129 (33.9), 95
(96.6), 94 (100), 91 (36.8), 79 (27.2). Found, %: С
81.97; Н 9.90. C14H20О. Calculated, %: С 82.30; Н
9.87. M 204.31.
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To a mixture of 0.013 mmol of MoO(O2)·2QOH 5,
0.05 g (0.26 mmol) of diamantane 1 in 2 mL of 1,2-
dichloroethane at 30‒50°С was added dropwise a
solution of 0.12 g (0.52 mmol) of peracid 4 in 1.5 mL
of CH2Cl2 within 1.5 h, and the mixture was stirred for
4.5 h at 60°С. Then was added more 0.12 g of acid 4 in
1.5 mL of CH2Cl2 within 1.5 h at 30‒50°С, and the
mixture was stirred additionally for 4.5 h. After 12 h
the reaction mixture was filtered through a bed of
Al2O3 (eluent CHCl3). The reaction products were
isolated by column chromatography on silica gel (60–
200 µm, 60 Å), eluents: hexane, chloroform. Yield
50%, white crystals, Rf 0.63 (CHCl3), mp 127‒128°С.
1Н NMR spectrum, δ, ppm: 1.50‒1.53 m (2Н, 2СН2),
1.63‒1.65 m (2Н, 2СН2), 1.71‒1.79 m (4Н, 2СН,
2СН2), 2.06‒2.10 m (4Н, 2СН, 2СН2), 2.11‒2.20 m
(1Н, СН), 2.28‒2.29 m (2Н, СН2,), 2.42 s (2Н, 2СН).
13C NMR spectrum, δ, ppm: 24.92 (С4), 30.39 (С9),
32.49 (С3,14), 36.66 (С6), 37.11 (С8,10), 37.95 (С5),
40.28 (С2,12), 40.52 (С7,11), 40.69 (С13), 157.60 (С15).
19F NMR spectrum (CDCl3), δ, ppm: ‒160.76 (F2,6), ‒
105.70 (F4), ‒139.52 (F3,5). Mass spectrum, m/z (Irel, %):
[M]+ is absent, 212 (0.5), 186 (100), 130 (12), 129 (19.7),
95 (28.8), 94 (20.3), 91 (23.6), 79 (14.4). Found, %: С
63.20; Н 4.92. C21H19F5О2. Calculated, %: С 63.31; Н
4.81. M 398.36.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 8 2016