Synthesis of 1-, 2-Methoxy-, 1,3-Dimethoxyadamantanes And 1-, 4-Methoxydiadamantanes by Reaction of Adamantyl and Diadamantyl Halides with Dimethyl Carbonate in the Presence of Zeolite Catalysts

Article abstract of DOI:10.1134/S1070428018110180

1-, 2-Methoxy-, 1,3-dimethoxyadamantane, and 1-, 4-methoxydiadamantane were prepared by the reaction of adamantyl and diadamantyl halides with dimethyl carbonate in the presence of zeolite catalysts NiHY or FeHY free of binders. Optimum ratio of catalysts and reagents were found and the reaction conditions for the selective synthesis of methoxyadamantanoids were developed.

Full text of DOI:10.1134/S1070428018110180

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2018, Vol. 54, No. 11, pp. 1728–1730. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © R.I. Khusnutdinov, N.A. Shchadneva, Yu.Yu. Mayakova, 2018, published in Zhurnal Organicheskoi Khimii, 2018, Vol. 54, No. 11,
pp. 1710–1712.
SHORT
COMMUNICATIONS
Synthesis of 1-, 2-Methoxy-, 1,3-Dimethoxyadamantanes
And 1-, 4-Methoxydiadamantanes by Reaction of Adamantyl
and Diadamantyl Halides with Dimethyl Carbonate
in the Presence of Zeolite Catalysts
R. I. Khusnutdinova, N. A. Shchadnevaa, and Yu. Yu. Mayakovaa*
a Institute of Petrochemistry and Catalysis of the Russian Academy of Scientists,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
*e-mail: inklab4@gmail.com
Received May 8, 2018
Revised May 8, 2018
Accepted May 8, 2018
Abstract—1-, 2-Methoxy-, 1,3-dimethoxyadamantane, and 1-, 4-methoxydiadamantane were prepared by the
reaction of adamantyl and diadamantyl halides with dimethyl carbonate in the presence of zeolite catalysts
NiHY or FeHY free of binders. Optimum ratio of catalysts and reagents were found and the reaction conditions
for the selective synthesis of methoxyadamantanoids were developed.
DOI: 10.1134/S1070428018110180
Characteristic features of alkoxyadamantanes are
their high thermal stability, the resistance to the action
of light and to hydrolysis, antimicrobial properties.
Adamantane and diadamantane ethers are successfully
used as efficient additives increasing the oxidative
resistance of lubricating oils, hydraulic and
transmission fluids improving simultaneously their
rheological characteristics.
in the presence of micro-, macro-, and mesoporous
zeolites free of binders promoted by iron compounds
(FeHY) and nickel compounds (NiHY), as well as
NaY. These catalysts are prepared by soaking zeolites
HY with salts of Fe(III) or Ni followed by a thermal
treatment [5]. Meso and macro pores in the above
zeolites ensure the effective diffusion of the molecules
of reactants to the catalytically active sites and
backwards to the surface of granules. The
concentration of active sites in zeolites free of bindings
is essentially higher that in zeolites with bindings.
The known methods of alkoxyadamantanes
synthesis are complex limiting their practical
application.
A
method of 1-alkoxyadamantanes
preparation was described affording an 83–95% yield
by the photolysis of a mixture of 1-bromo- or 1-
iodoadamantane with alcohols, methanol, ethanol, and
2-propanol, at room temperature during 24 h [1, 2]. 1-
Alkoxyadamantanes can be prepared by the reaction of
1-chloroadamantane with alcohols in the presence of a
stoichiometric quantity of silver perchlorate. Since
AgClO4 is expensive this method is suitable only for
laboratory practice [3]. 1-Alkoxyadamantanes were
prepared in [4] by alcoholysis of 1-chloroadamantane
in the presence of palladium complexes.
The optimum conditions were determined by an
example of the reaction of 1-bromoadamantane 1 with
dimethyl carbonate: 150°С, 5 h. Dimethyl carbonate
was used in 5–50-fold excess since it served both as a
Scheme 1.
Hlg
OMe
O
O
[K] (5 wt %)
150oC, 5 h
+
O
We performed adamantane halides methoxylation
with a “green chemistry” reagent, dimethyl carbonate,
1, 2
7
[K] = NiHY, FeHY; Hlg = Br (1), Cl (2).
1728

SYNTHESIS OF 1-, 2-METHOXY-, 1,3-DIMETHOXYADAMANTANES
1729
Scheme 2.
Br
OMe
O
O
O
O
FeHY (5 wt %)
150oC, 5 h
+
+
Br
OMe
OMe
O
O
3
4
8
Br
FeHY (5 wt %)
150oC, 5 h
9
Scheme 3.
Br
OMe
O
O
FeHY (5 wt %)
150oC, 5 h
+
+
+
Br
OMe
O
5
9 : 1
6
10
9 : 1
11
[5, 6]–[(МеО)2СО]–[FeHY] = 1 : 20–50 : 0.05
reagent and a solvent. The yield of 1-methoxy-
adamantane 7 reached 80% at the use as catalysts of
NiHY and FeHY. Also 1-chloroadamantane is
sufficiently active in the reaction affording ether 7 in a
78% yield (Scheme 1). Catalysts NiHY or FeHY retain
the activity at a repeated application. The observed
reduction in the yield of ether 7 within 4 cycles was 2–
3%. Zeolite NaHY showed a low activity and the yield
of ether 7 in its presence did not exceed 33%.
NaY and HY samples are described in [10]. Samples
of zeolite НY promoted with various amounts of iron
oxide (FeНY) and nickel oxide (NiHY) were prepared
as follows: calcined zeolite HY (pores volume measured
by water absorption 0.5 cm3/g) was soaked with an
appropriate amount of solution of Fe(NO3)3·9H2O or
Ni(NO3)2·6H2O followed by thermal treatment at 120–
150°С (4 h) and 440–450°С (3 h) in air. We obtained
zeolite samples FeНY (5.0 wt % Fe) and NiHY (5.0 wt
% NiO).
The reaction of 1,3-dibromoadamantane 3 with
dimethyl carbonate in the presence of FeHY occurs at
both substituents affording 1,3-dimethoxyadamantane
8 in a high yield (82%). 2-Bromoadamantane 4 under
typical conditions provided 2-methoxyadamantane 9 in
a 76% yield (Scheme 2).
Reactions of dimethyl carbonate with haloada-
mantanoids. General procedure. In a stainless-steel
pressure microreactor of 17 mL capacity was charged
5 wt % of catalyst FeHY (or NiHY), 100 mmol of
haloadamantane (or halodiadamantane), and 400 mmol
of dimethyl carbonate, the reactor was tightly closed,
and the reaction mixture was heated for 5 h at 150°С.
On completing the reaction, the reactor was cooled to
room temperature, opened, the reaction mixture was
filtered through a layer of Al2O3. The unreacted
dimethyl carbonate was distilled off.
At 150°С within 5 h 1- (5) and 4- (6) bromodi-
adamantanes are brought in this reaction to give
methoxydiadamantanes 10 and 11 in an overall yield
of 75% (Scheme 3).
The structure of ethers 7–11 was established from
1
13
the H and C NMR spectra and the GC-MS data by
comparison with authentic samples and with the
published information [6–9].
1-Methoxyadamantane (7). Yield 80%, mp 67–
68°C (3.0 mm Hg) {67–68°С (3 mm Hg) [1]}. 1Н NMR
spectrum, δ, ppm: 1.53–1.66 m (6Н, CH2), 1.71 s (6Н,
13
Samples of micro-, macro-, and mesoporous
zeolite НY promoted with various amounts of metal
oxides. The conditions of the preparation of zeolites
СН2), 2.13 s (3Н, СН), 3.21 s (3H, OCH3). C NMR
spectrum, δ, ppm: 30.51 (С1, С3, С5), 36.65 (С4, С6,
С10), 41.32 (С2, С8, С9), 47.58 (ОСН3), 73.68 (С1) [6].
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 11 2018

KHUSNUTDINOV et al.
1730
2-Methoxyadamantane (8). Yield 76%, mp 58–
tane, were commercial products; 1- and 4-bromodi-
adamantanes were prepared by the procedure [9].
60°C (25.0 mm Hg). 1Н NMR spectrum, δ, ppm: 1.53–
1.66 m (6Н, C4H2), 1.71 s (6Н, С2Н2), 2.13 s (3Н,
С3Н), 3.31 s (3H, OCH3). 13C NMR spectrum, δ, ppm:
27.51 (С5, С7), 31.50 (С1, С3, С4, С9), 36.62 (С8, С10),
37.62 (С6), 56.88 (ОСН3), 83.18 (С2) [6].
ACKNOWLEDGMENTS
Structural studies were performed in the Center of
Joint Usage “Agidel” at the Institute of Petrochemistry
and Catalysis of the Russian Academy of Scientists.
1,3-Dimethoxyadamantane (9). Yield 82%, mp 58–
1
60°C (4.0 mm Hg). Н NMR spectrum, δ, ppm: 1.47
br.s (2H, С6H2), 1.64–1.66 m (8Н, CH2, CH2CH2,
CH2), 1.71 s (2Н, СН2), 2.30 br.s (2Н, СН), 3.22 s
(6H, OCH3). 13C NMR spectrum, δ, ppm: 30.81 (С5,
С7), 35.62 (С6), 40.10 (С4, С8, С9, С10), 36.62 (С8,
С10), 44.48 (С2), 48.80 (ОСН3), 74.62 (С1, С3) [7].
The authors are grateful to Dr.Chem.Sci. B.I.
Kutepov and Cand.Chem.Sci. A.N. Khazipova for
zeolite catalysts provided for the study.
The study was performed under the financial
support of the Russian Foundation for Basic Research
(grant no.17-43-020155 р_povolzh’e-а).
1-Methoxydiadamantane (10). Yield 80%, mp
114–115°С (115–116°С [10]). 13C NMR spectrum, δ,
ppm: 25.04 (С4), 29.65 (С9), 32.05 (С3, С14), 36.87
(С6), 37.29 (С8, С10), 38.84 (С5), 39.29 (С13), 39.57
(С2, С12), 39.77 (С7, С11), 46.35 (С2, С12), 47.58
(ОСН3), 73.68 (С1). Mass spectrum, m/z (Irel, %): 218
[М]+ (13), 207 (9), 188 (15), 187 (100) [8].
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Initial compounds, 1-bromoadamantane, 1-chloro-
adamantane, 2-bromoadamantane, 1,3-dibromoadaman-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 11 2018