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Catalysis Communications 9 (2008) 680–684

www.elsevier.com/locate/catcom

Methoxycarbonylation of ketones with dimethyl carbonate

over solid base
a,b
Dudu Wu , Xin Fu a,b, Fukui Xiao a, Junping Li a, Ning Zhao a,
Wei Wei a,*, Yuhan Sun a,*
a
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
b
Graduate University of Chinese Academy of Sciences, Beijing 100039, China

Received 17 April 2007; received in revised form 7 August 2007; accepted 13 August 2007
Available online 17 August 2007

Abstract

The methoxycarbonylation of various ketones with dimethyl carbonate was carried out in the presence of solid base catalysts. The
results showed that the reaction scope seemed to be limited to the ketones with Ha and the main by-products were methylation and aldol
condensation products. The reactivity of aliphatic and aromatic ketones for the methoxycarbonylation was closely related to their acid-
ities. Basic catalysts were supposed to activate ketones via the abstraction of Ha by base sites. As a result, solid base with moderate
strength such as MgO facilitated the reaction.
 2007 Elsevier B.V. All rights reserved.

Keywords: b-Ketoesters; Ketones; Dimethyl carbonate; Solid bases

1. Introduction presence of a base, DMC could also react with a number

b-Ketoesters are compounds of growing interest because
of their applications in agrochemicals, pharmaceuticals,
and medical industries [1]. The traditional methods for the
synthesis of b-ketoesters are those through Michael addi-
tion reactions and Claisen condensation reactions [2,3].
However, the former route suffered from a lack of economic
feasibility because of both rigorous reaction conditions and
expensive reagents, and the latter encountered the separa-
tion, liquid waste treatment and corrosion problems due
to the use of homogeneous catalysts (usually CH3ONa).
As an environmentally benign building block, dimethyl
carbonate (DMC) has been expected to be an eco-friendly
alternative to both methyl halide and phosgene for methyl-
ation and carbonylation process, respectively [4–7]. In the
*
Corresponding authors. Tel.: +86 351 4049612; fax: +86 351 4041153
(Y. Sun, W. Wei).
E-mail addresses: weiwei@sxicc.ac.cn (W. Wei), yhsun@sxicc.ac.cn (Y.
Sun).
of nucleophilic substrates, such as ketones, amines, oximes,
indoles and phenols to produce the methoxycarbonylation
products [8–16]. In the 1970s, Ruset firstly reported the
synthesis of carbomethoxycyclohexanone from cyclohexa-
none and organic carbonates over NaH [17]. Later, the
reaction of aromatic ketones (especially phenyl benzophe-
none) and aliphatic ketones with DMC using a K2CO3 cat-
alyst was carried out by Selva et al. [18]. Furthermore,
DMC could also react with alicyclic ketones to give
dimethyl esters in the presence of homogenous catalysts
such as Cs2CO3-crown ether, CH3ONa and organic amines
[19–21]. However, the above methods had some obvious
disadvantages such as the separation and reutilization
problems of homogenous catalysts.
For quite a long time, solid bases, as one of the econom-
ically and ecologically significant catalysts, have become
more important research topic. They are non-corrosive,
present fewer disposal problems, and can also be designed
to give high performance. Thus, solid bases as catalysts
were used for the first time to prepare b-ketoesters from

1566-7367/$ - see front matter  2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2007.08.004
 D. Wu et al. / Catalysis Communications 9 (2008) 680–684
various ketones and DMC in the present work and the
plausible reaction mechanism was also discussed.
2. Experimental
2.1. Catalyst preparation
CaO, MgO and ZrO2 were prepared by thermal decom-
position of calcium carbonate at 800 C for 2 h, magnesium
hydroxide at 500 C for 5 h, zirconium hydroxide at 500 C
for 5 h under nitrogen atmosphere, respectively. Lanthana
(La2O3, Tianjin Kermel Chemical Reagent Co., Ltd.) and
alumina (Al2O3, Tianjin Kermel Chemical Reagent Co.,
Ltd.) were purchased and treated in N2 at 700 and
500 C for 5 h before use, respectively. Hb was obtained
by calcining the ammonium form (NH4-Beta, Shanghai
Chemical Reagent Co., China) in the air at 550 C for 3 h.
In order to obtain the MgO surface with different basi-
city, a series of Al/MgO samples with different molar ratios
was prepared by incipient impregnation. Typically, a cer-
tain amount of aluminum isopropoxide was dissolved in
30 mL of benzene at 50 C. Then the solution was quickly
added into Mg(OH)2, dried at 100 C overnight and ther-
mally decomposed in N2 at 500 C for 5 h to get the
impregnated catalyst.
2.2. Characterization
The specific surface area of samples was obtained by the
BET method. The samples were degassed at 350 C for 5 h
under vacuum (10 6 Torr) prior to the measurement, and
nitrogen adsorption/desorption isotherms were obtained
at 196 C on a Micromeritics ASAP-2000 instrument
(Norcross, GA).
CO2-temperature programmed desorption (CO2-TPD)
measurement was performed using Ar as a carrier gas. Cat-
alyst samples (0.10 g, 40–60 mesh) were pretreated in Ar at
500 C for 2 h. After the samples were cooled down to
room temperature, CO2 was pulsed to the reactor till the
saturation. Once physically adsorbed CO2 was purged off
by the carrier gas, the CO2-TPD experiments were carried
out from 20 to 800 C with a heating rate of 10 C/min
under Ar flow (50 mL/min), and the effluent was detected
by a Balzers OmnistarTM mass spectrometer.
In-situ FTIR investigations were made using a Nicolet
Magna 550 Fourier-transform infrared spectrometer (at a
resolution of 4 cm 1). The measurement was carried out
on self-supporting wafers (15 mg) in an inverted T-shaped
cell with CaF2 windows. Prior to the measurement, the
samples were pretreated in vacuum at 500 C for 5 h, and
the spectrum of the pretreated catalysts was obtained after
the samples were cooled to room temperature. After that,
the temperature was increased to 250 C, and the adsor-
bates (dimethyl carbonate and acetone) were introduced
into the cell for 5 h, and the resulting spectrum was
recorded after the samples were cooled to room tempera-
ture by removing excess gas by evacuation.
681
2.3. Catalytic reaction
The methoxycarbonylation of ketones with dimethyl
carbonate was carried out in an autoclave with a strong
magnetic stirring. The products were identified by HP-
6890 equipped with a HP-5MS capillary column and HP-
5973 mass selective detector, and analyzed using a gas
chromatograph with a flame ionization detector equipped
with a HP-5 column afterPthe catalyst filtration. The selec-
tivity was defined as Mi/P Mi · 100%, where Mi was the
weight of product i and Mi was the total weight of the
products.
3. Results and discussion
3.1. Methoxycarbonylation of ketones with DMC
Several kinds of ketones were chosen to assess the scope
of methoxycarbonylation over solid base and acid catalysts
(see Table 1). In the absence of catalyst, no products were
detected (entries 1 and 8). Only the aldol condensation
products of ketones and a trace amount of b-ketoesters
were detected over solid acids catalyst such as Hb and
Al2O3 (entries 2–3 and 9), which suggested that solid acids
were inactive towards the methoxycarbonylation reaction.
However, different b-ketoesters and their derivatives were
obtained over solid base catalysts such as MgO, CaO,
La2O3, etc., and the main side-reaction were methylation
and aldol condensation.
The reaction of aliphatic ketones with DMC produced
the corresponding b-ketoesters (entries 4–8 and 15–16).
Methyl acetoacetate could be obtained by the reaction
of acetone or acetylacetone with DMC, while methyl 2-
methylpropionoacetate was formed from the reaction of
3-pentanone with DMC. When aromatic substituted
ketone (such as acetophenone) was employed as the
starting materials, the reaction produced the b-ketoester
derivative (methyl benzoate) with high yield (entry 17).
But it was worthy noting that when the substituted
ketones without any Ha (e.g., diphenylketone) were used,
no products were obtained at all (entry 20), suggesting
that the scope of the methoxycarbonylation of DMC
with ketones seemed to be limited to the ketones with
Ha.
Dimethyl pimelate was produced via the reaction of
cyclohexanone with DMC. Selva reported that the yield
of dimethyl pimelate from the reaction of cyclohexanone
with DMC reached 11% by using K2CO3 as the catalyst,
and similar result was obtained with MgO as the catalyst
in the present work (entry 10) [18]. However, with the rise
of reaction temperature, MgO showed higher dimethyl
pimelate yield (entry 12), which might be due to the further
conversion of carbomethoxycyclohexanone to dimethyl
pimelate [19]. In addition, substituted dimethyl pimelate
could also be obtained from the reaction of substituted
cyclohexanone with DMC (entries 18–19), although the
yields were slightly low.
682 D. Wu et al. / Catalysis Communications 9 (2008) 680–684

Table 1
The methoxycarbonylation of ketones with dimethyl carbonate over solid bases
Entry Series of ketone Catalyst Reaction temperature (C) Ketone conversion (%) Selectivity of b-ketoesters (%)
1 Acetone – 240 – –
2 Acetone Hbb 240 61.6 Traces
3 Acetone Al2O3b 240 10.2 Traces
4 Acetone ZrO2b 260 18.4 Methyl acetoacetate (6.98)
5 Acetone MgOb 260 32.3 Methyl acetoacetate (52.8)
6 Acetone La2O3b 260 6.47 Methyl acetoacetate (62.6)
7 Acetone CaOb 260 21.2 Methyl acetoacetate (65.1)
8 Cyclohexanone – 260 – –
9 Cyclohexanone Al2O3a 260 57.0 Traces
10 Cyclohexanone MgOc 200 11.0 Carbomethoxycyclohexanone (34.6)
11 Cyclohexanone ZrO2a 260 41.2 Dimethyl pimelate (12.0)
12 Cyclohexanone MgOa 260 83.6 Dimethyl pimelate (51.8)
13 Cyclohexanone La2O3a 260 19.2 Dimethyl pimelate (38.2)
14 Cyclohexanone CaOa 260 71.7 Dimethyl pimelate (50.5)
15 3-Pentanone MgOb 260 35.9 Methyl propionate (53.9)
Methyl 2-methylpropionoacetate (27.6)
16 Acetylacetone MgOb 200 93.8 Methyl acetate (73.9)
Methyl acetoacetate (19.4)
17 Acetophenone MgOa 260 72.0 Methyl benzoate (59.8)
Methyl acetate (27.3)
18 2-Methyl cyclohexanone MgOa 260 41.1 2-Methyl dimethyl pimelate (38.9)
19 2,6-Dimethyl cyclohexanone MgOa 260 25.5 2,6-Dimethyl dimethyl pimelate (58.8)
20 Diphenylketone MgOa 260 – –
a
Reaction conditions: acetone:DMC = 1:4, time = 5 h and catalyst wt% = 1.5%.
b
Reaction conditions: acetone:DMC:cat = 1:20:2 and time = 11.4 h.
c
Reaction conditions: acetone:DMC = 1:4, time = 5 h and catalyst wt% = 1.7%.

According to the above results, it was likely that the 4.00E-013

methoxycarbonylation of ketones with DMC was closely 3.50E-013

a CaO
b MgO
related to the ability of Ha abstraction, i.e., the acidity of c La2O3
3.00E-013
aromatic and aliphatic ketones (see Table 2) [22,23]. Obvi- a d ZrO2

ously, the reactivity appeared to parallel with the acidity of 2.50E-013 b

ketones. Thus, acetylacetone showed the highest reactivity
2.00E-013
among aromatic and aliphatic ketones. However, cyclohex-
anone with low acidity (pKa = 26.4) [22] also showed high 1.50E-013

reactivity. This might be due to the presence of the ring 1.00E-013 d c

strains, which is under investigation in our laboratory.
5.00E-014

3.2. Basic properties and catalytic performance 0.00E+000

-5.00E-014
Fig. 1 depicts the CO2 desorption profiles on CaO, 0 100 200 300 400 500 600 700 800 900
MgO, La2O3 and ZrO2. It was found that CaO exhibited Temperature(°C)
the strong basic sites with a sharp desorption peak at
Fig. 1. CO2-TPD profiles of solid bases.
550 C. MgO showed three desorption peaks, respectively,
suggesting that MgO had both weak and moderate
strength basic sites. ZrO2 had only weak basic sites with Table 3
CO2 desorption peak at 170 C, and La2O3 showed relative Surface area and CO2 uptake of solid bases
strong basicity. The basicity (i.e., the basic sites amount per Catalyst BET surface area (m2/g) CO2 uptake
unit area of catalysts) followed the order of CaO >
mmol/g mmol/m2
MgO > La2O3 > ZrO2 (see Table 3). Based on the results
in Table 1 (entries 4–7 and 11–14), it was found that ZrO2 33.4 3.22E 03 9.64E 05
MgO 10.1 1.78E 02 1.76E 03
La2O3 4.8 1.69E 03 3.52E 04
CaO 9.1 6.37E 02 7.00E 03
Table 2
pKa values of various ketones
MgO with the moderately strong basic sites exhibited the
Ketone Acetylacetone Acetophenone Acetone 3-Pentanone
highest ketones conversion along with the high b-ketoesters
pKa 13.3 24.7 26.5 27.1
yields. ZrO2 showed the lowest b-ketoesters yields due to
 D. Wu et al. / Catalysis Communications 9 (2008) 680–684 683

the lowest basicity and basic strength. With a relative weak

60
basicity, La2O3 displayed the lower b-ketoesters yields than Yield of methyl benzoate
Yield of methyl acetoacetate
MgO. CaO showed lower ketone conversion and b-ketoest-
50
ers selectivity despite its high basicity compared to MgO.
This could be attributed to the acid strength of Ca cation,
40
which was too weak to stabilize the carbanion species, and

Yield (%)
then CaO showed to be less active towards the activation of
30
ketones [24]. Thus, both basicity and basic strength played
an important role in the reaction, and the basic sites of 20
moderate strength were effective for the methoxycarbony-
lation of ketones with DMC. 10
In order to further clarify the effect of basic strength on
the catalytic performance, a series of MgO with different Al 0
contents were prepared to supply the different amount of 0.000 0.002 0.004 0.006 0.008 0.010 0.012 0.014 0.016
moderate base sites (see Fig. 2). It was found that the addi- Basicity (mmol / g)

tion of alumina did not change the basic strength of MgO,
but decreased the number of moderate basic sites with the
increase of the Al contents. When a series of MgO catalysts
were employed in the reaction of alicyclic ketone (acetone),
a good linear correlation was observed between the methyl
Fig. 3. The relationship between the yield of methyl acetoacetate or
methyl benzoate and the basicity over Al/MgO.
~

1729
1768

1229
acetoacetate yield and the amount of moderate base sites

1199
1177
(see Fig. 3). The similar linear correlation was also
obtained between the methyl benzoate yield and the mod-

1716
erate base sites when the aromatic ketone (acetophenone)
Transmittance

was used as the feed. Thus, the methoxycarbonylation of

1261
ketones with DMC over solid base could be closely related
to the moderate base sites.
3602

d
3.3. The plausible reaction mechanism
c

In-situ FTIR measurement of adsorbed acetone and b

2962

DMC on MgO was carried out to investigate the plausible a

~
reaction mechanism of ketones with DMC (see Fig. 4). The 4000 3500 3000 2500 2000 1200 1000 800 600 400
adsorption bands at 2962 and 1261 cm 1 were discerned Wavenumbers (cm-1)
after the sample was pretreated in vacuum at 500 C (see
Fig. 4. FTIR spectra of the reactants adsorbed on MgO catalyst: (a) MgO
Fig. 4), which were due to the evaporation of high vacuum pretreated in vacuum, (b) adsorption of dimethyl carbonate on MgO at
silicone grease in the T-shaped cell. At 250 C, no adsorp- 250 C, (c) adsorption of acetone on MgO at 250 C and (d) coadsorption
tion bands were detected for dimethyl carbonate adsorbed of dimethyl carbonate and acetone on MgO at 250 C.
on MgO, indicating that dimethyl carbonate was hardly
activated by the base surface. However, when acetone
was admitted to the cell, some bands were detected at
2.50E-013
3602, 1716 and 1229 cm 1, respectively (see Fig. 4). The
a Al/MgO(0.01) broad band around 3602 cm 1 could be assigned to the
b Al/MgO(0.05)
2.00E-013
c Al/MgO(0.1) OH stretching vibration due to the formation of acetone
d Al/MgO(0.2) H-bonded to MgO oxygen atoms, while the C@O stretch-
1.50E-013
e Al/MgO(0.3)
ing vibration at 1716 cm 1 and the CAC:AC stretching
a vibration at 1229 cm 1 indicated that acetone remained
its framework after adsorption over solid base catalysts.
1.00E-013
c b These illustrated that acetone was activated via the abstrac-
tion of Ha by base sites, and then formed acetonyl species
5.00E-014
over solid base. FTIR spectra of co-adsorbed reactants
d showed the bands at 1721 and 1771 cm 1, which could be
0.00E+000 e ascribed to C@O stretching vibration of ketoesters. And
the bands at 1179 and 1193 cm 1, assigned to CAOAC
0 100 200 300 400 500 600 stretching vibration of ester groups, were also detected
Temperature (°C)
(see Fig. 4). Because dimethyl carbonate was hardly
Fig. 2. CO2-TPD profiles of MgO with different Al contents. adsorbed on solid base after evacuation, these new bands
684 D. Wu et al. / Catalysis Communications 9 (2008) 680–684

H3CO OCH3 alysts. The reactivity of aliphatic and aromatic ketones for
H3C CH2 H3 C CH2 H3C CH2 OCH3
C methoxycarbonylation was found to relate with the acidity
α C C
C H C of ketones. Compared with ZrO2, La2O3 and CaO, moder-
O
O O H
α O O CH3OH ate base such as MgO appeared favorable to the reaction.
The in- situ FTIR measurement revealed that the reaction
Mn+ O2-
Mn+ O2- Mn+ O2- occurred via abstracting Ha from ketones by basic sites.
Scheme 1. The plausible mechanism of the methoxycarbonylation of
Acknowledgements
acetone with dimethyl carbonate.

The authors acknowledge the financial support from

suggested the formation of methyl acetoacetate. Therefore,
State Key Program for Development and Research of Chi-
the plausible mechanism of the reaction from acetone with
na (No. 2006BAC02A08) and Program of Knowledge
DMC over solid base catalysts could be proposed in
Innovation of Institute of Coal Chemistry, Chinese Acad-
Scheme 1. To begin with, a acetonyl anion was generated
emy of Sciences.
due to the abstraction of the a-proton (Ha) from the ace-
tone by the base site, and the acetonyl anion and proton
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