Synthesis of 3-(adamantan-1-yl)pentane-2,4-dione from 1-bromo(chloro, hydroxy)adamantane and acetylacetone in the presence of metal complex catalysts

Article abstract of DOI:10.1134/S1070428014100030

3-(Adamantan-1-yl)pentane-2,4-dione has been synthesized in high yield by reaction of 1-bromo-, 1-chloro-, or 1-hydroxyadamantane with acetylacetone in the presence of manganese or iron compounds.

Full text of DOI:10.1134/S1070428014100030

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 10, pp. 1409–1411. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © R.I. Khusnutdinov, K.S. Kislitsina, N.A. Shchadneva, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 10,
pp. 1427–1429.
Synthesis of 3-(Adamantan-1-yl)pentane-2,4-dione
from 1-Bromo(chloro, hydroxy)adamantane and Acetylacetone
in the Presence of Metal Complex Catalysts
R. I. Khusnutdinov, K. S. Kislitsina, and N. A. Shchadneva
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
e-mail: ink@anrb.ru
Received January 23, 2014
Abstract—3-(Adamantan-1-yl)pentane-2,4-dione has been synthesized in high yield by reaction of 1-bromo-,
1-chloro-, or 1-hydroxyadamantane with acetylacetone in the presence of manganese or iron compounds.
DOI: 10.1134/S1070428014100030
Adamantyl-substituted β-dicarbonyl compounds, in
particular 3-(adamantan-1-yl)pentane-2,4-dione (I) can
be used as starting compounds for the synthesis of
five-membered nitrogen heterocycles exhibiting
diverse biological activity [1–3]. There are numerous
published data on the synthesis, properties, and pos-
sible uses of 3-(adamantan-1-yl)pentane-2,4-dione (I).
However, known methods for the preparation of com-
pound I are complicated, and they require harsh condi-
tions (180°C, 24–48 h) [3–6]. For example, diketone I
can be obtained by alkylation of adamantan-1-ol (IIa)
or nitrate derived therefrom with acetylacetone in
nitromethane in the presence of concentrated sulfuric
or perchloric acid [6]; this synthesis releases a lot of
inorganic and acidic wastes at the isolation step. The
synthesis of I via exchange reaction of 1-bromoada-
mantane (IIb) with Co(acac)2, Cu(acac)2, and
Pd(acac)3 [3–5] is not less difficult because of the
necessity of using stoichiometric amounts of solid
organic substances.
pentane-2,4-dione (I) by reaction of compounds IIa–
IIc with acetylacetone in the presence of metal com-
plex catalysts, Fe(acac)3 and Mn(acac)3 (Scheme 1).
The reactions were carried out at a II–acetylacetone–
catalyst ratio of 100:(100–300):(1–3) at 110–140°C,
the reaction time being 1–6 h. Acetylacetone was taken
in excess, for it acted simultaneously as reagent and
solvent. The use of other catalysts, such as Co(acac)2,
Cu(acac)2, Pd(acac)3, and Mo(CO)6, was inefficient.
The results of some experiments are collected in
table. The most efficient catalyst was Fe(acac)3 (run
nos. 12, 18) which ensured up to 93% yield of 3-(ada-
mantan-1-yl)pentane-2,4-dione. Manganese(III) acetyl-
acetonate was less active than Fe(acac)3. Under the
optimal conditions, the yield of I in the presence of
Mn(acac)3 was 86%. The highest yield (93%) was
attained when 1-bromoadamantane (IIb) was used as
starting compound (run no. 18). The yield of I in
the reaction with 1-chloroadamantane (IIc) was 75%
(run no. 15).
In the present communication we describe a simple
procedure for the preparation of 3-(adamantan-1-yl)-
Adamantan-1-ol (IIa) reacted with acetylacetone
only in the presence of HBr (5 mol %) as promotor. By
Scheme 1.
Me
O
Fe(acac)3, Mn(acac)3
110–140°C, 1–6 h
O
O
O
+
+
Me
Me
X
OH
Me
IIa–IIc
I
IIa
X = OH (a), Br (b), Cl (c).
1409

KHUSNUTDINOV et al.
1410
Reaction of 1-bromo-, 1-chloro-, and 1-hydroxyadamantanes IIa–IIc with acetylacetone in the presence of manganese and
iron compounds
Product composition, %
Run
no.
Ratio II–acetyl- Tempera- Reaction Conversion
acetone–catalyst ture, °C time, h of IIa–IIc, %
Catalyst (initial compound no.)
I
IIa–IIc
–
tars
–
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
No catalyst (IIb)
No catalyst (IIb)
Mn(acac)3 (IIb)
Mn(acac)3 (IIb)
Mn(acac)3 (IIa) + 5 mol % HBr
Mn(acac)3 (IIc)
Mn(acac)3 (IIb)
Mn(acac)3 (IIb)
Mn(acac)3 (IIb)
Mn(acac)3 (IIb)
Mn(acac)3 (IIb)
Fe(acac)3 (IIb)
Fe(acac)3 (IIb)
Fe(acac)3 (IIb)
Fe(acac)3 (IIc)
Fe(acac)3 (IIb)
Fe(acac)3 (IIb)
Fe(acac)3 (IIb)
100:150:3
100:150:3
100:150:3
100:100:3
100:100:3
100:100:3
100:100:3
100:100:3
100:150:3
100:150:3
100:150:3
100:150:3
100:150:3
100:150:3
100:150:3
100:150:3
100:150:3
100:150:3
110
140
140
140
140
140
110
110
110
110
110
140
140
140
140
110
110
110
6
3
3
2
3
6
4
6
1
2
6
.00.5
1
3
6
1
3
6
010
025
100
099
070
091
100
090
023
090
100
100
100
100
089
025
100
100
10
15
67
66
60
75
85
71
09
76
86
89
82
77
75
15
87
93
–
–
10
14
–
23
20
–
10
10
10
14
07
08
10
15
20
14
10
10
05
07
05
09
–
07
06
01
03
03
11
–
03
02
analogy with the data of [3–5], diketone I can be
synthesized by reaction of stoichiometric amounts of
1-bromoadamantane (IIb) and Fe(acac)3 or Mn(acac)3
without addition of acetylacetone.
the IR spectrum indicated diketone structure of com-
pound I.
Thus, we have proposed a simple procedure for the
synthesis of 3-(adamantan-1-yl)pentane-2,4-dione (I)
with the use of accessible metal complex catalysts
Fe(acac)3 and Mn(acac)3.
The formation of adamantan-1-ol (IIa) as by-prod-
uct may be rationalized by the presence of water in the
initial acetylacetone. In the reaction with acetylacetone
preliminarily thoroughly dried and distilled over 3-Å
molecular sieves the amount of IIa in the product was
reduced to a minimum value (±5%; run no. 18). Water
may also appear in the reaction mixture as a result of
concurrent self-condensation of acetylacetone with
formation of a dimer. The latter was detected in
a blank experiment, and its formation was confirmed
by GLC analysis and IR and mass spectra of the reac-
tion mixtures.
The structure of compound I was proved by IR and
1H and 13C NMR spectroscopy, mass spectrometry, and
comparison with published data [3, 7]. The IR spec-
trum of I contained absorption bands in the region
1750–1780 cm–1 due to stretching vibrations of the
carbonyl groups (diketone tautomer). The presence of
a signal at δC 204.34 ppm (C=O) in the 13C NMR
spectrum and the absence of OH absorption band in
EXPERIMENTAL
The IR spectra were recorded on a Bruker Vertex
79V spectrometer from samples pelleted with KBr or
1
13
dispersed in mineral oil. The H and C NMR spectra
were recorded on a Bruker Avance-400 spectrometer at
400.13 and 100.62 MHz, respectively, using CDCl3 as
solvent and tetramethylsilane as internal reference. The
mass spectra were obtained on a Shimadzu GCMS-
QP2010Ultra spectrometer coupled with a gas chro-
matograph (Supelco PTE-5 column, 60 m×0.25 mm;
carrier gas helium; oven temperature programming
from 40 to 280°C at a rate of 8 deg/min; injector tem-
perature 260°C, ion source temperature 200°C; elec-
tron impact, 70 eV). GLC analyses were carried out on
a Carlo Erba GC 6000 Vega Series 2 gas chromato-
graph equipped with a 3-m steel column packed with
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 10 2014

SYNTHESIS OF 3-(ADAMANTAN-1-YL)PENTANE-2,4-DIONE
1411
13
PEG-6000 (15%) on Chromaton N-AW-HMDS; oven
temperature programming from 50 to 180°C at a rate
of 8 deg/min; carrier gas helium, flow rate 47 mL×
min–1). The elemental compositions were determined
on a Carlo Erba 1108 analyzer.
3-(Adamantan-1-yl)pentane-2,4-dione (I). a. Gen-
eral procedure. A glass ampule was charged with
Mn(acac)3 or Fe(acac)3, 1-hydroxyadamantane (IIa),
1-bromoadamantane (IIb), or 1-chloroadamantane
(IIc), and acetylacetone, and the ampule was sealed
and heated for 1–6 h at 110–140°C in a high-pressure
reactor. When the reaction was complete, the reactor
was cooled to 20°C, the ampule was opened, the mix-
ture was extracted with methylene chloride, and the
product was isolated by column chromatography on
silica gel using hexane–ethyl acetate as eluent. Yield
71–93% (calculated on IIa–IIc), mp 55–57°C.
b. Optimal procedure. A glass ampule was charged
with 0.3 mmol of Fe(acac)3, 10 mmol of 1-bromoada-
mantane (IIb), and 15 mmol of acetylacetone. The
ampule was sealed and heated for 6 h at 110°C in
a high-pressure reactor. When the reaction was com-
plete, the reactor was cooled to 20°C, the ampule was
opened, the mixture was extracted with methylene
chloride, and the product was isolated by column chro-
matography on silica gel using hexane–ethyl acetate as
eluent. Yield 93%. IR spectrum, ν, cm–1: 2911, 2849
(C–H); 1707, 1739 (C=O). 1H NMR spectrum, δ, ppm:
1.61–1.69 m (12H, CH2), 1.95 s (3H, CH), 2.17 s (6H,
CH3), 3.51 s (1H, CH). C NMR spectrum, δC, ppm:
28.56 (C3, C5, C7), 33.01 (CH3), 36.51 (C4, C6, C9),
38.42 (C2, C8, C10), 40.35 (C1), 78.12 (C3′), 204.34
(C=O). Mass spectrum, m/z (Irel, %): 234 (2.5) [M]+,
192 (13.2) [M – 42]+, 135 (100) [M – 99]+, 117 (11.9),
107 (6.35), 92 (18.57), 79 (16.38), 77 (7.27), 67 (6.52).
Found, %: C 76.86; H 9.49. C15H22O2. Calculated, %:
C 76.88; H 9.46. M 234.1619.
This study was performed under financial support
by the President of the Russian Federation (fellowship
for young scientists and post-graduate students, project
no. SP-4426.2013.4).
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