Carbonylation of chloroacetone to methyl acetoacetate

Article abstract of DOI:10.1023/A:1015042510988

Methyl acetoacetate was prepared by the selective carbonylation of chloroacetone in the presence of a homogeneous palladium catalyst at 100 °C and under a CO pressure of 1.5 MPa.

Full text of DOI:10.1023/A:1015042510988

Russian Chemical Bulletin, International Edition, Vol. 50, No. 11, pp. 2239—2241, November, 2001
2239
Carbonylation of chloroacetone to methyl acetoacetate
«
A. L. Lapidus, O. L. Eliseev, T. N. Bondarenko, O. E. Sizan, and A. G. Ostapenko
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
4
7 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 5328. E-mail: oleg@ioc.ac.ru
Methyl acetoacetate was prepared by the selective carbonylation of chloroacetone in the
presence of a homogeneous palladium catalyst at 100 °C and under a CO pressure
of 1.5 MPa.
Key words: chloroacetone, palladium catalysts, carbonylation; methyl acetoacetate,
acetoacetic ester.
The catalytic carbonylation of halogen-containing
compounds1,2 makes it possible to introduce the ester
group instead of the halogen atom into the substrate
molecule in one step using palladium,2a cobalt,2b—d or
iron2e catalysts. Esters of aromatic2a,d and aliphatic2b,d,e
acids and phenylacetic2a—c and malonic acids2b,c are
thus synthesized.
know, palladium catalysts were not applied earlier for
chloroacetone carbonylation. The only known example
for the carbonylation of α-haloketones on the Pd cata-
lysts is bromoacetophenone carbonylation in the pres-
ence of PdCl (PPh ) at 80 °Ñ and a CO pressure of
2
3 2
7
1.3 MPa. Methyl benzoylacetate was obtained in
64% yield within 48 h.
Acetoacetic ester is a large-scale commercial prod-
uct, which usually obtained by the Claisen condensation
of ethyl acetate. Another possible way for the synthesis
The purpose of this work is to study the carbonylation
of chloroacetone (1) in the presence of the Pd catalysts,
to develop a method for the synthesis of methyl acetoac-
etate (2), and to reveal the influence of the nature of the
catalyst and base precursors, temperature, and pressure.
3
of acetoacetic esters, the carbonylation of chloroacetone
(
(
1) in the presence of the corresponding alcohols
Scheme 1), is yet poorly studied.
Results and Discussion
Scheme 1
Preliminarily we tested the catalytic activities of
various palladium compounds. Tributylamine was used
as a base. The catalyst concentration was 1 mol.%. The
Cat
Cl
+
CO
+
ROH
B
O
PdCl and Pd(OAc) salts are inactive in this reaction
2
2
1
(
Table 1, entries 1 and 2). When using the Pd complexes
with the weakly coordinating ligands, PdCl (PhCN)2
2
and PdCl (ImH) , the yield of compound 2 was only
2
4
COOR
+
HCl•B
O
Table 1. Carbonylation of chloroacetone (1) in the presence of
R = Me (2), Alk
various palladium compounds
Cat is catalyst
Entrya
Catalyst
Conversion of 1b Yield of 2b
%)
B is base
(
The synthesis of acetoacetic esters by the carbonyla-
tion of chloroacetone in the presence of the cobalt
catalyst is licensed. The catalyst activity is low: at its
1
2
PdCl2
Pd(OAc)2
60
70
Traces
Traces
4
concentration of 10 mol.% the turnover number is at
most 1.4 per h. The kinetics of the carbonylation of
3
PdCl (PhCN)
65
62
5
5
2
2
4
PdCl (ImH)
2
4
5
6 c
PdCl (PPh )
3 2
Pd(dba) + 2 PPh
2 3
100
100
94
95
RCH Cl compounds, including chloroacetone, in the
presence of cobalt carbonyl, has been studied. The gas
2
2
5
phase carbonylation of halogen compounds, including
chloroacetone, over the supported rhodium catalyst, has
been investigated. However, the yield of acetoacetic
a
Experimental conditions: molar ratio Pd : 1 : NBu3
: 100 : 150, T = 110 °C, P = 1.5 MPa, 1 h.
=
1
6
b According to GLC data.
c
ester is only 2% under these conditions. As far as we
Dibenzylideneacetone is abbreviated as dba.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2138—2140, November, 2001.
066-5285/01/5011-2239 $25.00 © 2001 Plenum Publishing Corporation
1

2
5
240
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 11, November, 2001
Lapidus et al.
% (see Table 1, entries 3 and 4). In these cases, a great
Y (%)
1
00
amount of Pd black forms. The PdCl (PPh ) complex
2
3 2
exhibited a high activity. The yield of compound 2
reached 94% at a complete conversion of the substrate
8
6
4
2
0
0
0
0
(
see Table 1, entry 5 ). Similar results were obtained
when Pd(dba) with the addition of 2 mol.% PPh was
2
3
used (see Table 1, entry 6 ).
A stoichiometric amount of a base is needed for
binding the HCl evolved during the reaction. In the
absence of a base, the reaction did not occur (Table 2,
entry 1). The application of CaCO , K CO , or pyridine
3
2
3
7
0
90
110
T/°C
did not give positive results: only traces of compound 2
were formed (see Table 2, entries 2—5 ). In the presence
of NaOAc, product 2 was obtained in 15% yield, and in
Fig. 1. Influence of the reaction temperature on the yield of
compound 2 (Y ); molar ratio Pd : 1 : NBu = 1 : 100 : 150,
P = 1.5 MPa, 1 h.
3
the presence of Na CO the yield was 46% (see Table 2,
2
3
entries 6 and 7 ). Tributylamine is the most appropriate
base of those applied by us. In its presence, the yield of
ester 2 was 94% at 110 °Ñ (see Table 2, entry 8). The
concentration of tributylamine in the reaction mixture
affects the reaction rate. So, when the amount of NBu3
was decreased from 1.5 to 1.1 equiv. per substrate, the
yield of ester 2 lowered from 94 to 53% (see Table 2,
entries 8 and 9).
A study of the temperature dependence of the yield
of compound 2 (Fig. 1) showed that an increase in the
temperature from 60 to 130 °Ñ (at a pressure of 1.5
MPa) increases the yield of ester 2 from 15 to 97%, and
at 110 °Ñ the yield is 94%. Thus, the 110—130 °Ñ
temperature interval can be regarded as optimum.
The synthesis at atmospheric CO pressure is ineffi-
cient. At 60 °Ñ for 5 h compound 2 was obtained in
was 25% within 5 h (see Table 2, entry 13), and the
reaction could be continued, which is indicated by the
dynamics of CO absorption (Fig. 2).
The proposed mechanism for chloroacetone car-
bonylation is shown in Scheme 2. This mechanism is
similar to that proposed1a,b,2a for the carbonylation of
0
benzyl and aryl halides. The Pd complexes stabilized by
the PPh ligands are the true catalysts. Our data show
3
that the reaction does not virtually occur in the absence
of PPh . An alkylpalladium intermediate is formed by
3
the oxidative addition of compound 1 to the catalytic
complex. The next step is the migrative insertion of CO
resulting in the acylpalladium complex. Its alcoholysis
gives the reaction products and completes the catalytic
cycle. The base binds the hydrohalic acid that evolved
and also catalyzes, most likely, the alcoholysis of the
acylpalladium complex to afford the product.1a,b The
3
% yield only (see Table 2, entry 12). n-Butyl alcohol
(
b.p. 118 °Ñ) was used as an alcohol component to
dependence of the reaction rate on the NBu concentra-
increase the reaction temperature to 110 °Ñ if necessary.
3
tion indicates that the alcoholysis step is the limiting
stage in the case. However, the synthesis at an atmo-
spheric pressure results in a sharp decrease in the reac-
tion rate. Probably, under a low CO pressure the forma-
tion of the acyl complex becomes the limiting stage.
Under these conditions, the yield of butyl acetoacetate
Table 2. Carbonylation of chloroacetone (1) in the presence of
PdCl (PPh )
2
3 2
Entrya
Base
number of equiv.)
T/°C
P/MPa Yield of 2 b
V/mL
(
(%)
1 c
2 c
3 c
4
–
110
110
110
110
150
110
110
110
110
55
6.0
6.0
6.0
1.5
1.5
1.5
1.5
1.5
1.5
0.1
0.1
0
Traces
Traces
Traces
1.5
15
46
94
53
60
1
CaCO (1.1)
K CO (1.5)
Py (1.5)
Py (1.5)
NaOAc (1.5)
Na CO (1.5)
NBu (1.5)
NBu (1.1)
3
2
3
4
0
5
6
7
2
3
8
3
20
9
3
1
1
2 d
3 d,e
NBu (1.1)
NBu (1.1)
3
25
2
3
f
110
3
0
a
b
c
d
e
f
50
100
150
200
250
t/min
Molar ratio Pd : 1 = 1 : 100.
According to GLC data.
Duration of experiment is 3 h.
Fig. 2. Dynamics of CO absorption during carbonylation of
compound 1 according to the reaction CH COCH Cl + CO +
ROH → CH COCH COOR at an atmospheric pressure,
T = 60 °C, R = Me (1); T = 110 °C, R = Bu (2); V is the
volume of absorbed CO.
3
2
Catalyst Pd(dba) + 2 PPh , duration of experiment is 5 h.
2
3
3 2
BuOH was used instead of MeOH.
The yield of butyl acetoacetate is indicated.

Chloroacetone carbonylation
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 11, November, 2001 2241
Scheme 2
(0.126 mmol), the corresponding amount of the base, and
MeOH (25 mL) were loaded into a glass liner. The liner was
placed in the autoclave, which was purged with CO, closed,
and thermostated at a required temperature. Then CO was
introduced to achieve a necessary pressure, and the rotation of
the autoclave was switched on. After the end of the reaction,
the reaction mixture was analyzed by GLC. Ester 2 was
COOR
+
HCl•B
O
R = Me (2), Alk
Cl
1
isolated by distillation, b.p. 168—170 °Ñ. Í NMR, δ: 2.25 (s,
PdL2
O
3 Í, ÑÍ ÑÎ); 3.45 (s, 2 Í, ÑÍ ); 3.72 (s, 3 Í, ÎÑÍ ).
3
2
3
Carbonylation under atmospheric pressure was carried out
in a glass reactor equipped with a magnetic stirrer, reflux
condenser, jacket for heating, and burette for measuring ab-
sorbed CO.
ROH + B
1
References
Cl
Pd
L
O
O
O
Cl
Pd
L
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L
L
CO
L is PPh , CO
3
B is base
[
Russ. Chem. Rev., 1989, 58 (Engl. Transl.)].
Thus, we performed the selective carbonylation
of chloroacetone to methyl acetoacetate on the
PdCl (PPh ) catalyst. The reaction in the presence of
2
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3 2
NBu at 110—130 °Ñ and 1.5 MPa affords ester 2
3
selectively in 94—97% yield.
(
1
e) J. J. Brunet, C. Sidot, and P. Caubere, J. Org. Chem.,
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Experimental
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. Jpn. Pat., 58,154,535 (1983); Chem. Abstrs., 1983, 100, 34166.
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1
Í NMR spectra were recorded on a Bruker WM-250
mass spectrometer (250 MHz) using Me Si as internal stan-
4
dard and CDCl3 as solvent. GLC was carried out on an
Autokhrom UE5 PID instrument with a 30 m½0.25 mm quartz
capillary column, the SE-30 stationary phase, helium as carrier
gas, and n-octanol as internal standard.
The starting chloroacetone was prepared by the chlorina-
tion of acetone.8
1
00, 33956.
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6
6
7
8
. J. K. Stille and P. K. Wong, J. Org. Chem., 1975, 40, 532.
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Chloroacetone carbonylation under elevated pressure was
carried out in a steel rotating 150-mL autoclave heated with an
electric furnace. Compound 1 (1 mL, 12.6 mmol), the catalyst
Received February 12, 2001;
in revised form May 14, 2001