Synthesis of 1-(2-oxopropyl)adamantane from 1-bromo(chloro)adamantanes and isopropenyl acetate in the presence of iron and manganese compounds

Article abstract of DOI:10.1134/S1070428014090061

An efficient procedure has been developed for the synthesis of 1-(2-oxopropyl)adamantane by reaction of 1-bromo(chloro)adamantanes with isopropenyl acetate in the presence of manganese and iron compounds.

Full text of DOI:10.1134/S1070428014090061

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 9, pp. 1272–1275. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © R.I. Khusnutdinov, N.A. Shchadneva, K.S. Kislitsina, V.A. Veklov, B.I. Kutepov, 2014, published in Zhurnal Organicheskoi Khimii,
2
014, Vol. 50, No. 9, pp. 1289–1292.
Synthesis of 1-(2-Oxopropyl)adamantane
from 1-Bromo(chloro)adamantanes and Isopropenyl Acetate
in the Presence of Iron and Manganese Compounds
R. I. Khusnutdinov, N. A. Shchadneva, K. S. Kislitsina, V. A. Veklov, and B. I. Kutepov
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
e-mail: ink@anrb.ru
Received January 29, 2014
Abstract—An efficient procedure has been developed for the synthesis of 1-(2-oxopropyl)adamantane by
reaction of 1-bromo(chloro)adamantanes with isopropenyl acetate in the presence of manganese and iron
compounds.
DOI: 10.1134/S1070428014090061
1
-(2-Oxopropyl)adamantane (I, adamantylacetone)
reactant and solvent. The best catalysts turned out to be
iron(III) and manganese(III) acetylacetonate com-
plexes which are readily soluble in isopropenyl acetate
(Table 1). Under the optimal conditions, the conver-
sion of 1-haloadamantanes III and IV attained 99%,
the selectivity for ketone I being 70% (Scheme 1).
According to the GC/MS data, apart from the major
product (ketone I), the reaction mixture contained
adamantane (V), admantan-1-yl acetate (VI), 3-(ada-
mantan-1-yl)pentane-2,4-dione (VII), and acetic acid
is an important adamantane derivatives which is used
in veterinary for the treatment of Newcastle disease
and is a starting material in the preparation of
pesticides, polymeric materials, and lubricant additives
[
1, 2]. 1-Adamantylacetone (I) can be obtained via
a multistep procedure from (1-adamantyl)acetyl
chloride [1] or by reaction of 1-bromoadamantane with
isopropenyl acetate (II) in the presence of 2 equiv of
AlBr as catalyst [3, 4].
3
(
1–2%) (Table 1). Klimochkin et al. [5] presumed that
We have synthesized ketone I by reacting 1-bromo-
and 1-chloroadamantanes III and IV with isopropenyl
acetate (II) in the presence of metal complex catalysts,
iron and manganese compounds, at 110–140°C. The
reaction time was 4–6 h, and the ratio III (IV)–II–
catalyst was 1:(3–5):(3–5 mol %). Isopropenyl acetate
was taken in excess since it simultaneously acted as
the formation of adamantane (V) as by-product is the
result of stabilization of intermediate carbenium ion
via intermolecular hydride transfer.
Taking into account the presence of acetic acid
among the products (which is likely to be formed by
hydrolysis of initial isopropenyl acetate), the formation
Scheme 1.
Fe(acac) or Mn(acac) (3–5 mol %)
3
3
CH2
OAc
110–140°C, 4–6 h
O
+
+
X
Me
Me
III, IV
I
V
+
+
+
AcOH
Ac
OAc
Ac
VI
VII
III, X = Br; IV, X = Cl.
1
272

SYNTHESIS OF 1-(2-OXOPROPYL)ADAMANTANE
1273
Table 1. Synthesis of (1-adamantyl)acetone (I) in the presence of iron and manganese compounds
Initial
compound
no.
Catalyst, amount,
mol % (relative
to 1-AdX)
Product composition, %
Ratio
Tempera-
ture, °C
Conversion
Time, h
1
-AdX–II
of 1-AdX, %
I
V
–
8
5
5
4
3
2
2
1
1
5
5
VI
03
04
01
06
05
07
08
01
05
10
10
10
VII
–
tars
–
1:5
1:5
1:5
1:3
1:3
1:3
1:3
1:3
1:5
1:5
1:3
1:3
110
110
110
130
130
140
140
140
130
130
140
140
6
6
6
6
6
4
4
6
6
6
4
4
23
99
94
99
99
99
99
93
73
95
93
94
11
72
72
67
71
59
64
45
52
65
52
55
09
10
13
15
13
22
15
45
05
09
16
11
III
Mn(acac)
3
, 5
05
03
06
06
08
10
–
Fe(acac)
Fe(acac)
3
, 5
, 5
3
Mn(acac)
Fe(acac) , 3
Mn(acac) , 3
Fe (CO) , 8
Mn(acac) , 3
3
, 5
3
3
2
9
3
10
10
10
13
IV
Fe(acac)
Fe(acac)
3
, 3
, 5
3
Mn(acac) , 5
3
Table 2. Synthesis of (1-adamantyl)acetone (I) in the presence of MnCl
2
·4H
2
O/SiO
2
a
Initial
compound no.
Catalyst sample no. and amount
(relative to 1-AdX)
Conversion
of 1-AdX, %
Temperature, °C
Time, h
Yield of I, %
IV
1, 10 wt %
140
140
140
140
140
150
140
140
140
140
140
130
150
3
3
3
2
2
2
3
3
3
2
2
3
2
087
100
100
100
100
100
090
100
100
095
100
080
100
83
94
96
1
2
2
3
2
, 20 wt %
, 10 wt %
, 20 wt %
, 10 wt %
, 10 wt %
b
c
c
c
c
82
80
95
90
95
96
80
84
80
97
III
1, 10 wt %
1
2
2
3
3
2
, 20 wt %
, 10 wt %
, 20 wt %
, 10 wt %
, 10 wt %
, 10 wt %
b
c
c
c
c
a
The procedure for the preparation of the catalyst is given in Experimental.
No loss in the catalytic activity was observed after 5 cycles.
A part of the initial compound was converted into higher oligomers.
b
c
of acetate VI may be rationalized by reaction of
Furthermore, according to the GLC data, under the
reaction conditions isopropenyl acetate undergoes iso-
merization into acetylacetone [6], and the latter reacts
with III to give 2 to 16% of 3-(adamantan-1-yl)pen-
tane-2,4-dione (VII).
1
-bromoadamantane (III) with acetic acid. This was
confirmed by special experiment: by heating a mixture
of compound III and acetic acid in the presence of
Fe(acac) we obtained acetate VI in quantitative yield.
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014

1
274
KHUSNUTDINOV et al.
The results were unsatisfactory in the presence of
100.62 MHz using CDCl as solvent. The elemental
3
other catalysts, in particular Co(acac) , Cu(acac) ,
analyses were obtained on a Carlo Erba 1106 analyzer.
2
2
Pd(acac) , and Fe (CO) . The yield of I strongly
The progress of reactions and the purity of the isolated
compounds were monitored by GLC on a Khrom-5
chromatograph equipped with a flame-ionization
detector and 1.2-m×3-mm and 3-m×3-mm columns;
stationary phase 5% of SE-30 on Chromaton-N-HMDS
(0.125–0.160 mm), oven temperature programming
from 50 to 280°C at a rate of 8 deg/min; carried gas
helium, flow rate 50 mL/min.
3
2
9
depends on the presence of traces of water. When the
reaction was carried out with freshly prepared and
thoroughly dried catalyst (water content ≤0.005%), the
yield of 1-adamantylacetone (I) was the maximum
(
70%), and the concentration of by-products was
minimal. The catalytic activity of Mn(acac) and
3
Fe(acac) decreases after prolonged storage, presum-
3
ably due to absorption of atmospheric moisture.
The reactions were carried out in glass ampules.
Silica-supported MnCl ·4H O was prepared by the
When methylene chloride, chloroform, or carbon
tetrachloride was used as solvent, the yield of I did not
exceed 30%, the conversion of II and III being 40–
0%; the overall yield of by-products reached 50%.
The reaction of 1-bromo- or 1-chloroadamantane
2
2
impregnation method.
Synthesis of 1-(1-adamantyl)propan-2-one (I) in
the presence of homogeneous metal complex cata-
7
lysts. A glass ampule was charged with Mn(acac) or
3
with isopropenyl acetate was more selective in the
presence of a heterogeneous catalyst, silica-supported
manganese(II) chloride tetrahydrate MnCl ·4 H O/
Fe(acac) ], haloadamantane III or IV, and isopropenyl
3
acetate (II), and the ampule was sealed and heated for
4–6 h at 110–140°C in a high-pressure reactor. When
the reaction was complete, the ampule was cooled to
20°C and opened, the liquid reaction mixture was
treated with methylene chloride, and the products were
isolated by column chromatography on silica gel using
hexane–ethyl acetate as eluent. Yield of I 45–70% (cal-
culated on the initial haloadamantane).
2
2
SiO in an amount of 10–20 wt % with respect to com-
2
pound III; the concentration of MnCl in the catalyst
2
was 10–25%. The conversion of haloadamantanes III
and IV at 130–150°C was complete in a shorter time
(
2–3 h; Scheme 2), and the only product was 1-ada-
mantylacetone (I), while the catalyst did not lose its
activity after 5 cycles (Table 2). An important advan-
tage of heterogeneous catalysis is the absence of the
effect of water content of the catalyst on the reaction
course.
Preparation of heterogeneous manganese-con-
taining catalysts. Sample no. 1. A solution of 1.15 g of
MnCl ·4H O in 18 mL of water was mixed with 10 g
2
2
of finely ground silica (GOST 3956-76; 45–200 μm).
The resulting paste was kept for 0.5 h and dried for
Scheme 2.
1
6
–2 h at 130–150°C. The catalyst (11.15 g) contained
CH2
OAc
.6 wt % of MnCl , 89.7 wt % of silica, and 3.7%
+
2
Me
of water.
Br
Sample no. 2 was prepared in a similar way from
III
2
.36 g of MnCl ·4H O in 18 mL of water and 9.9 g of
2
2
MnCl ·4H O/SiO
2
2
2
1
30–150°C, 2–3 h
O
silica. Yield 12.3 g; the catalyst contained 12.2 wt % of
MnCl , 80.5 wt % of silica, and 7.3% of water.
2
Me
Sample no. 3 was prepared in a similar way from
I
2
.50 g of MnCl ·4H O in 20 mL of water and 7.2 g of
2
2
silica. Yield 10 g; the catalyst contained 16.0 wt % of
Thus the use of iron and manganese compounds as
catalysts instead of aluminum(III) bromide ensures
preparation of (1-adamantyl)acetone (I) in high yield
and with minimum catalyst consumption.
MnCl , 72.0 wt % of silica, and 12.0% of water.
2
Synthesis of 1-(1-adamantyl)propan-2-one (I) in
the presence of heterogeneous manganese-contain-
ing catalysts. A glass ampule was charged with
EXPERIMENTAL
MnCl
2
·4H
2
O/SiO (sample nos. 1–3), haloadamantane
2
III or IV, and isopropenyl acetate (II), and the ampule
was sealed and heated for 2–3 h at 130–150°C in
a high-pressure reactor. The ampule was cooled to
20°C and opened, the liquid phase was separated from
The IR spectrum was recorded in Nujol on a Bruker
1
3
Vertex 70V spectrometer. The C NMR spectrum was
obtained on a Bruker Avance-400 spectrometer at
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014

SYNTHESIS OF 1-(2-OXOPROPYL)ADAMANTANE
1275
the catalyst by decanting and filtered through a layer of
alumina, the sorbent was washed with hexane, the
solvent was distilled off, and the residue was distilled
under reduced pressure. Yield of I 80–99% (calculated
on the initial haloadamantane).
no. 13-03-12027 ofi_m) and by the Council for Grants
at the President of the Russian Federation (project
no. SP-4426.2013.4).
REFERENCES
Fresh portions of initial compounds II and III were
added to sample no. 3, and the synthesis was per-
formed as described above 5 times more.
1
2
. Moiseev, I.K., Makarova, N.V., and Zemtsova, M.N.,
Russ. J. Org. Chem., 2001, vol. 37, p. 453.
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Zaved., Ser. Khim. Khim. Tekhnol., 2010, vol. 53,
no. 2, p. 3.
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Novikova, G.A., Izv. Volgogr. Gos. Tekhn. Univ., 2004,
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. Klimochkin, Yu.N., Tilli, T.S., and Moiseev, I.K.,
Zh. Org. Khim., 1988, vol. 24, p. 1780.
1
-(1-Adamantyl)propan-2-one (I) was isolated by
column chromatography on silica gel using hexane–
ethyl acetate as eluent and was additionally purified by
vacuum distillation. bp 97–98°C (1 mm). IR spectrum:
3
4
–
1
13
ν 1710 cm (C=O). C NMR spectrum, δ , ppm:
C
1
2
8
9
3
5
7
3
3.26 (C ), 42.42 (C , C , C ), 28.55 (C , C , C ),
4
6
10
3
2
6.70 (C , C , C ), 58.01 (1-AdCH ), 28.65 (CH ),
2
3
5
6
08.59 (C=O). Found, %: C 80.97; H 10.45. C H O.
13
20
Calculated, %: C 81.20; N 10.48.
. Chernykh, S.P., Novye protsessy organicheskogo sinteza
(New Processes in Organic Synthesis), Moscow:
Khimiya, 1989, p. 400.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014