234 Ind. Eng. Chem. Prod. Res. Dev.

1985, 24, 234-239

Vapor Phase Carbonylation of Organic Compounds over Supported

Transition-Metal Catalyst. 3. Kinetic Analysis of Methanol
Carbonylation with Nickel-Active Carbon Catalyst
Kohjl Omata, Kaoru Fujimoto,- Tsutomu Shlkada, and Hlro-o Tomlnaga
Department of Synthetic Chemistry, Faculty of Engineering, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan

Overall kinetics of vapor phase carbonylation of methanol and the related compounds such as methyl acetate,
dimethyl ether, etc. on a nickel-active carbon catalyst was explored to simulate variable product profiles based
on a complex reaction network. The initial step of methanol conversion was comprised of carbonylation to methyl
acetate and dehydration to dimethyl ether in parallel. Methyl iodide was essential to both of the reactions. The
reaction order of the carbonylation with respect to methyl iodide was nearly zero or 0.1 and the apparent activation
energy was 21.6 kcal/mol, which was 1.5 times higher than that on a supported rhodium catalyst. Dimethyl ether
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was found to be successively carbonylated to form methyl acetate. Methyl acetate was further carbonylated to
acetic anhydride, which was rapidly hydrolyzed to acetic acid. Hydrolysis of methyl acetate to acetic acid and
methanol proceeded also on the carrier. Carbonylation of methyl acetate was strongly suppressed by methyl acetate
Itself and the carbonylation of methanol and dimethyl ether was also thought to be suppressed by methyl acetate.
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A reaction model was developed which accounted for the inhibition by methyl acetate and experimental product
pattern over a wide range of feed gas ratios and methanol conversion.

Introduction stream at its vapor pressure. Carbon monoxide was pu-

The kinetics of vapor phase carbonylation of methanol
(MeOH) to methyl acetate (AcOMe) and acetic acid (Ac-
OH) on supported rhodium metal and rhodium ion cata-
lysts have been studied by several researchers (Fujimoto
et al., 1977; Robinson et al., 1972; Takahashi et al., 1979).
The reaction orders observed with respect to methyl iodide
(Mel) partial pressure on those catalysts are mostly first
order, suggesting that cleavage of the C-I bond of Mel is
the rate-determining step as is the case for the rhodium
complex catalyst (Roth et al., 1971). It has also been
suggested that AcOH is formed via acetyl iodide and its
subsequent hydrolysis on the rhodium complex catalyst
(Forster, 1976, 1979).
The vapor phase carbonylation of methanol on nickel-
active carbon (Ni/AC) catalysts has been studied under
both atmospheric (Inui et al., 1981,1982) and pressurized
conditions (Fujimoto et al., 1982,1983a). Under moder-
ately pressurized conditions, the catalyst exhibits high
activity and the selectivities to carbonylated products
(AcOMe and AcOH). The carbonylation reaction is fa-
vored by a high CO/MeOH ratio in the feed and a high
reaction pressure. It has been indicated that, on the
nickel-active carbon catalyst, AcOMe is the primary
product which gives AcOH successively (Fujimoto et al.,
1982).
In the present study, a reaction network for methanol
carbonylation is postulated and the kinetic parameters of
each reaction step are determined to simulate the observed
product yield over a wide range of methanol conversion.
Experimental Section
Kinetic studies were conducted in a stainless steel tu-
bular reactor of differential type, with an inner diameter
of 4 mm, which was placed vertically in a heated fluidized
sand bath. The reaction temperature was measured with
a thermocouple inserted directly in the catalyst bed. A
vaporizer, which was maintained at 150 °C, was located
at the top of the reactor for mixing and preheating the
rified over an active carbon and zeolite (molecular sieve
5A; MS5A) and hydrogen was purified with 1 wt % Pd/
A1203 and MS5A. An integration type reactor heated in
the sand bath was also employed to survey the product
yield over a wide range of MeOH conversion. It consisted
of 5 tubular reactors (inner diameter of 4 or 6 mm) con-
nected in series with five tubes having sampling ports. As
the diameter of each reactor is small and the flow rate is
high, the back mixing of reactants and products can be
neglected even at high conversion levels.
The details of the catalyst and its preparation have been
described in a previous paper (Fujimoto et al., 1982). The
carrier was a commercially available active carbon (Takeda
Shirasagi C, charcoal base, activated with steam, specific
surface area 1200 m2/g, particle size 40-60 mesh) and the
nickel source was nickel(II) acetate. The loading was 2.5
wt % as metal. An Rh on AC catalyst (Rh 0.1 wt %) was
prepared from rhodium(III) chloride by a similar proce-
dure. Rh on AC was reduced in flowing hydrogen at 400
°C for 1 h prior to the reaction.
After the catalyst bed had been heated to the prescribed
temperature in flowing nitrogen, liquid reactants and CO
were supplied to start the reaction. The reaction rapidly
reached steady state within 1 h and no change of activity
was observed during the experimental run (Fujimoto et
al., 1982). Reaction conditions were as follows: total
pressure, 10 atm; temperature, 210-280 °C. The small part
of the reaction mixture was sampled in the gas phase with
a hot syringe and analyzed by gas chromatography using
a flame ionization detector and a stainless steel column
packed with FFAP, which was supported on Chromosorb
W AW and treated with H3P04.
The reaction rate was defined as follows.
(1) Methanol conversion
11
Cmm
µ ""
x x ( )
W/Fm 2

reactants. Liquid reactants (MeOH, Mel, AcOMe, AcOH,

and water) were fed with microfeeders into the vaporizer.
Cmd ,11 X
r° ~

Dimethyl ether (DME) was supplied with a nitrogen 100 W/Fu 2

0196-4321/85/1224-0234$01.50/0 © 1985 American Chemical Society

 Ind. Eng. Chem. Prod. Res. Dev., Vol. 24, No. 2, 1985 235

where rM and rD are the rates of AcOMe and DME for-

mation, respectively. CMM and Cmd are the conversion of
MeOH to AcOMe (%) and that of MeOH to DME (%),
respectively. W is the catalyst weight (g) and FM is the
feed rate of MeOH (mmol/h).
(2) Dimethyl ether conversion
1
((o\
- _ V
X
M
100 W/Fo
where CDM is the conversion of DME to AcOMe (%) and
Fd is the feed rate of DME (mmol/h).
(3) Methyl acetate conversion
Cma
rA =
ttt- X X n (4) Figure 1. Transient response of methane formation. Catalyst: 2.5
100 W/Fma wt % Ni/AC. Reaction conditions: temp, 250 °C; Pc0, 7.6 atm;
PmcOh. 1.8 atm; PMeI, 0.6 atm.
where rA, CMA, and FMA are the rate of AcOH formation,
the conversion of AcOMe to AcOH (%), and the feed rate
of AcOMe (mmol/h), respectively. In carbonylation n is
2 and in the other case, 1.
(4) Acetic acid conversion
Cam 1
= x ®
w?Fk
where CAM and FA are the conversion of AcOH to AcOMe
(%) and the feed rate of AcOH (mmol/h), respectively.
The conversion was calculated based on the assumption
that the methyl group in the reactant is retained in the
products.
Assessment of Reaction Pathways
Reaction Network. In our previous paper (Fujimoto carbon. Catalyst: 2.5 wt % Ni/AC. Reaction conditions: temp, 250
et al., 1983a), the product yields plotted against methanol °C; Pc0, 2.2 atm; PMe0H, 2.2 atm; PMeI, 0.23 atm.
conversion clearly demonstrated that the main primary
products are AcOMe and DME which are successively Hydrogen iodide thus formed is quickly converted to
converted to AcOH, the final product. methyl iodide by eq 17 to be described below.
2CH3OH + CO —
CH3COOCH3 + H20 (6) Source of Methane. Under usual reaction conditions
used in this work the yield of methane was less than 2%.
2CH3OH —
(CH3)20 + H20 (7) However, methane formation should be as small as pos-
It has also been demonstrated that the Ni/AC catalyzes sible. Hence the cause of methane formation was explored
the carbonylations of DME and AcOMe to form AcOMe on Ni/AC. When MeOH and CO were introduced over
and acetic anhydride (Ac20), respectively (Shikada et al., the catalyst in the absence of Mel, the product was hy-
1983). In the presence of MeOH, both of these reactions drogen alone. When Mel was added to the above feed,
may possibly proceed. DME, AcOMe, and methane were formed instead of hy-
drogen. The dynamic response is shown in Figure 1. It
(CH3)20 + CO —
CH3COOCH3 (8) is clear that methane appeared while hydrogen disappeared
CH3COOCH3 + CO —
(CH3C0)20 (9) by the addition of Mel and that the rate of methane for-
mation is about equal to that of hydrogen. Since methane
However, no Ac20 was experimentally detected, presum- formation is about equal to that of hydrogen. Since
ably because of its hydrolysis to AcOH. methanol is known to be decomposed to carbon monoxide
(CH3C0)20 + H20 — 2CH3COOH (10) and hydrogen on nickel catalyst (Suehiro et al., 1983), the
above-mentioned methane formation can be interpreted
Combination of reactions 9 and 10 results in as follows

CH3COOCH3 + CO + H20 —
2CH3COOH (11)
CH3OH —
2H2 + CO (15)
Methyl acetate is supposed to be directly hydrolyzed to CH3I + H2 —
CH4 + HI (16)
AcOH and MeOH on active carbon, and the reverse re-
action, the esterification of AcOH, may also proceed. CH3OH + HI —
CH3I + H20 (17)
CH3COOCH3 + H20 — CH3COOH + CH3OH (12) Results and Discussion
CHaCOOH + CH3OH — CH3COOCH3 + H20 (13) Based on the above reaction network, the kinetics of the
Route of Dimethyl Ether Formation. DME is one respective step reactions was experimentally studied. The
results are to be summarized and discussed below.
of the major primary products of methanol reaction on
Reaction of Methanol. In Figure 2 methanol con-
Ni/AC catalyst. The rate depends on the partial pressure version and selectivities of AcOMe and DME were plotted
of Mel and is not influenced by the presence of nickel
against the time factor. Products other than DME and
(Fujimoto et al., 1983a). The reaction is inferred to be AcOMe are negligible at an early stage of methanol con-
catalyzed by active carbon in the following way version. As is expected, the conversion of methanol in-
CH3OH + CHaI CH3OCH3 + HI
—
(14) creased linearly with time factor, and the selectivities of
236 Ind. Eng. Chem. Prod. Res. Dev., Vol. 24, No. 2, 1985
Partial Pressure of CO and MeOH
Figure 3. Rate of dimethyl ether formation from methanol. Cata-
lyst: 2.5 wt % Ni/AC. Reaction conditions: temp, 250 °C; PMeI, 0.42
atm.; (O) Pco, 4.0 atm; (·) PMeoh, 2.0 atm.
Partial Pressure of Mel (atm)
0.I 0,2
Partial Pressure or C3 ana MeOH
Figure 4. Rate of methyl acetate formation from methanol
nickel-active carbon. Catalyst: 2.5 wt % Ni/AC. Reaction condi-
tions: temp, 250 °C; (·) Pco, 4.0 atm; PMe!, 0.42 atm; (9) PMe0H, 2.0
atm; PMeI, 0.42 atm; PMe0H, 2.0 atm; Pco> 4.0 atm.
(©)
AcOMe and DME formations were constant. Extrapola-
tion of selectivities to zero percent of MeOH conversion
gives finite values, approximately 50%, respectively, under
this set of reaction conditions, suggesting that AcOMe and
DME are initially formed in parallel. This reaction path
is consistent with the observation that the DME formation
proceeds on active carbon (Fujimoto et al., 1983a).
Mel is indispensable for both reactions, that is, the rate
of DME formation is 0.6 order with respect to the partial
pressure of Mel (Fujimoto et al., 1983a) and 1.2 order with
MeOH as exemplified in Figure 3. The reaction orders
suggest that the reaction at a high MeOH/CO ratio pro-
duces DME with high selectivity. In contrast, the rate of
AcOMe formation is 0.7, 0.6, and 0.1 order with respect
to the partial pressures of CO, MeOH, and Mel, respec-
tively, as can be seen in Figure 4. The temperature de-
pendence of the AcOMe formation is shown in Figure 5.
The apparent activation energy is calculated as 21.6
kcal/mol. Thus, the rate equation of AcOMe formation
is expressed as
rM =
ksP\ieillPco°'7PMeOH0,6: AE
Kinetics of methanol conversion over Rh/AC are shown
in Figures 5 and 6. As might be anticipated, the exper-
imental rate expression of DME formation was same as
in the case of Ni/AC and thus they are not shown in the
figures. On the other hand, the kinetics of AcOMe for-
mation over the Rh/AC are greatly different from that on
thee Ni/AC catalyst and are expressed in the following
equation.
rM(Rh) =
^RRMeI0'7-PcO0'3-PMeOH0'6;
=
(atm
Figure 5. Arrhenius plot of methanol carbonylation. Catalyst: (·)
2.5 wt % Ni/AC; (O) 0.1 wt % Rh/AC. Reaction conditions: Pco,
4.0 atm; Pm<¡0h, 2.0 atm; (·) PMeI, 0.64 atm; (O) PMeI, 0.42 atm.
Partial Pressure of Mel (atm)
0,4
0.1 0,2 0,3 0.5
(atm
Partial Pressure of CO ana MeOH
over
Figure 6. Rate of methyl acetate formation from methanol over
Rh-active carbon. Catalyst: 0.1 wt % Rh/AC. Reaction conditions:
temp, 280 °C; (·) Pco, 4.0 atm; PMel, 0.42 atm; (9) µß , 2.0 atm;
PMei, 0.42 atm; (&copy;) PMb0h, 2.0 atm; Pco, 4.0 atm.
In the case of a homogeneous reaction with rhodium com-
plex catalyst, the dependence of the rate on the promoter
concentration is first order and the activation energy is 14.7
kcal/mol at about 180 °C (Hjortkjaer and Jensen, 1976).
Even in the present case, where the system is a solid-
catalyzed gas-phase reaction at temperature from 250 to
280 °C, the reaction order of Mel is close to 1.0 (0.7) and
that of CO is close to 0 (0.3). The marked difference
between Ni/AC and Rh/AC is the reaction order with
respect to the partial pressure of Mel and the activation
energy. The former is supposed to be correlated with the
affinity between metal and Mel; that is, Mel reacts more
easily with Ni under the reaction conditions. The com-
parison of the rate equations (18) and (19) suggest that the
rhodium catalyst is active at low temperature and low
pressure; however, the nickel catalyst is highly active at
higher temperature and lower promoter concentration.
Reaction of Dimethyl Ether. DME is a major by-
product at the early stage of MeOH reaction over Ni/AC
catalyst. The yield increased at first and then decreased
= 21.6 kcal/mol with methanol conversion. It was presumed that DME was
(18) either hydrolyzed to MeOH or carbonylated to AcOMe.
However, the contribution of the hydrolysis has been ex-
perimentally confirmed to be quite small. Namely, con-
version of DME to MeOH is about 1% under the following
conditions: partial pressure PNa = 3.9, PDMe = 0.7, PMeI
=
0.3, Ph2o = 2.0 atm, temperature = 250 °C, while the
conversion of DME to AcOMe is about 11% when CO was
supplied instead of N2 under the same conditions.
Therefore the rate of reaction of DME to AcOMe via
MeOH is negligible.
When DME is carbonylated over Ni/AC, the yield of
10.8 kcal/mol (19) AcOMe has been found to depend strongly on the Mel/

Partial Pressure of Mel (atm)
0,05 0.1 0,2 0.3 0,5
Figure 7. Rate of dimethyl ether carbonylation. Catalyst: 2.5 wt
% Ni/AC. Reaction conditions: temp, 250 °C; (C) Pco 4.8 atm;
Pdme, 0.8 atm; (e) Pco, 3.9 atm; PMeI, 0.3 atm.; (O) PDMB, 0.8 atm;
PMel, 0.3 atm.
Partial Pressure of AcOMe and H20 (atm)
Figure 8. Rate of acetic acid formation from methyl acetate.
Catalyst: active carbon. Reaction conditions: temp, 250 °C; (O)
PH2o, 1.2 atm; (·) PAcom., 0.9 atm.
DME ratio and the CO/DME ratio under a high partial
pressure of DME (Shikada et al., 1983). Since the partial
pressure of DME was always lower than 1 atm during
methanol carbonylation, the rate of carbonylation of DME
was examined but under low DME pressure. From the
data shown in Figure 7, the reaction order with respect to
the partial pressures of Mel, DME, and CO are calculated
as 0.5,0.6, and 0.5, respectively. The characteristics of the
carbonylation of DME compared with those of MeOH
show greater dependence on the partial pressure of Mel.
Since chemical adsorption of Mel to Ni/AC is supposed
to be the prerequisite to the carbonylation, the higher
dependence on Mel in the case of DME carbonylation
suggests that the successive reactions are faster than those
in the case of carbonylation of MeOH. That is, the rate-
determining step is different between the carbonylations
of MeOH and DME.
Reaction of AcOMe. The yield of AcOMe, the main
primary product, decreases at high methanol conversion
levels while AcOH increased with methanol conversion.
The fact implies that AcOMe is successively converted to
AcOH (Fujimoto et al., 1983a). There may be two possible
routes of AcOH formation from AcOMe. The first route
is the hydrolysis of AcOMe (direct hydrolysis) and the
second one is the carbonylation of AcOMe to Ac20 and its
successive hydrolysis to AcOH (indirect hydrolysis). Figure
8 shows the effects of the partial pressure of water and
AcOMe on the hydrolysis of AcOMe in the absence of Mel.
The order of the reaction was found to be 0.7 and 0.3 with
respect to AcOMe and H20, respectively.
The rate of AcOH formation from AcOMe is shown in
Figure 9 as functions of the partial pressure of CO, AcOMe,
and Mel in the presence of water. The figure indicates
Ind. Eng. Chem. Prod. Res. Dev., Vol. 24, No. 2, 1985 237
Partial Pressure of AcOMe (atm)
0 0,2 0,4 0.6 0,8 1,0
0 0.02 0.04
Partial Pressure of Mel (atm)
Figure 9. Rate of acetic acid formation from methyl acetate under
carbonylation conditions. Catalyst: 2.5 wt % Ni/AC. Reaction
conditions: temp, 250 °C; (») PMeI, 0.01 atm; PAcoMe» 0.6 atm; PH2o>
0.6 atm; (C) PH2o, 0.6 atm; PAcoMe, 0.6 atm; Pco, 2.8 atm; (·) PMei,
0.02 atm; Ph2o> 1-8 atm; Pco, 7.4 atm.
Figure 10. Rate of methyl acetate formation from methanol and
acetic acid. Catalyst: active carbon. Reaction conditions: temp, 250
°C; (O) Pacoh, 0.8 atm; (·) Pµ. , 0.3 atm.
that the rate is 2.7,1, and -1.7 order with respect to partial
pressure of CO, Mel, and AcOMe, respectively. The strong
self-inhibition effect of AcOMe upon AcOH formation
should be noted, possibly because of stronger adsorption
of AcOMe on Ni/AC than other reactants.
It has been reported already by the present authors that
Ac20 is formed from AcOMe over Ni/AC catalyst in a
water-free system (Shikada et al., 1983). Although the rate
of Ac20 formation was not high (Fujimoto et al., 1983a),
the added water markedly accelerated the rate of AcOH
formation and reduced the formation of Ac20. The sig-
nificant consumption of CO and the slight formation of
methanol indicate that the main route of AcOH formation
can be attributed not to hydrolysis of AcOMe but to the
carbonylation of AcOMe and its successive hydrolysis. In
the methanol carbonylation system, the vapor pressure of
water is always higher than that of AcOMe due to the
coproduction of water in AcOMe and DME formation, and
the partial pressure of CO is also high. Therefore the
contribution of the route through Ac20 formation (defined
as indirect hydrolysis) to the rate of AcOH formation
should be more significant.
Thus, it could be concluded that the AcOH formation
in the absence of Mel or CO in Figure 9 is attributed to
the direct hydrolysis catalyzed by active carbon, and that
the increase in the rate with increasing Mel or CO partial
pressure is attributed to indirect hydrolysis.
Reaction of AcOH. AcOH forms AcOMe by esterifi-
cation with MeOH on active carbon (Figure 10). The rate
238 Ind. Eng. Chem. Prod. Res. Dev., Vol. 24, No. 2, 1985

Figure 11. Reaction path of acetic acid synthesis catalyzed by

nickel-active carbon.

Table I. Experimental Rate Equation of Methanol

Carbonylation Catalyzed by Nickel-Active Carbon
reaction reaction dependence on rate
no. path partial pressure constant"
1 2MeOH + CO — p
~Mel
O.lp 0.6 p“ 0.7
9
MeOH ~CO CO/MeCH-1/1 CO/MeOH-50/L
AcOMe + H20
2MeOH DME + Figure 12. Results of simulation. Parameter: klt 9; k2,11; ks, 15;
PMel °'ß 11
-»
2 MeOH1'2
h2o ft4, 11; k¡, 35; ks, 0.1 mmol/(h g atm”). Mel, 5 mol % in MeOH.
3 DME + CO -* P MeI°'°P DMEU'bP COU'6 15
AcOMe
p 0.3 p 0.7
4 AcOMe + H20 —
Oi20 •‘AcOMe 11
AcOH + MeOH
5 AcOH + MeOH — p 0.3 p 0.9
35
*AcOH rMeOH
AcOMe + H20
6 p l.op
rCO p‘AcOMe
2.7 -1.7 15
AcOMe+H20+CO *
Mel
-»
2AcOH
"In mmol/(h g of cat. atm*), where x is the sum of the order of
dependence on the partial pressure of reactants.

with respect to the

is not large but the order is 0.3 and 0.9
partial pressure of AcOH and MeOH, respectively.
The Simulation of Reaction Network. The reaction
network and kinetic parameters which have been obtained
by use of the differential reactor are summarized in Figure Figure 13. Results of modified simulation. The parameters are
11 and Table I. Numerical calculation of simultaneous same as shown in Figure 12.
differential equations was performed as functions of the
time factor (W/F). They were solved by the conventional be expressed by eq 22 for both carbonylation of MeOH and
fourth-order Runge-Kutta method. In the calculation, the DME.
rate for indirect hydrolysis of AcOMe is expressed by (20)
instead of the power rate law a =
1/(1 + 5.0 PAc0Me3) (22)

PacOMb"1'7
=
6.0/(1 + 5.0P AcOMe3)
Simulation was tried by use of the rate constants in
Table I, but the calculated yields of AcOMe and AcOH
were not in good agreement with the experimental ones.
The discrepancy should be attributed to the evaluation of
the rate constant k6 (indirect hydrolysis of AcOMe) be-
cause the measurement of the reaction rate was performed
in the absence of methanol, of which the vapor pressure
is large at the early stage of methanol carbonylation.
Probably the AcOH formation is suppressed by methanol
by the reaction (Keim, 1983)
CH3COOCOCH3 + 2CH3OH
—
2CH3COOCH3 + H20
(21)
Accordingly, the rate constant K6 was adjusted arbitrarily
to give good agreement with the observed yields in case
of the feed ratio of CO/MeOH being 10/1. The compar-
ison is presented in Figure 12 with experimental data
measured in the multistage reactor shown in the figure.
For the feed ratio of CO/MeOH as 10/1, fairly good
fitting is achieved at the rate constant k6 of 0.1 mmol/h
g atom3,7 while the fitting was quite poor for the feed ratio
of CO/MeOH being 1/1.
It is reasonable to assume that AcOMe, which shows a
marked inhibitive effect on the carbonylation, might
suppress the carbonylations of both MeOH and DME as
well, due to its strong adsorption on the catalyst. Because
of the lack of quantitative data on the inhibition, an ap-
proximation was made that the effects are the same as that
for AcOMe carbonylation. The correction factor (a) could
(20) The simulation employing the above correction factor
is illustrated in Figure 13. Remarkable improvement in
the fitting of calculated data to the experimental results
for the two experimental runs was attained. Comparison
of the data in Figures 12 and 13 suggested that the in-
hibition by AcOMe is not serious when the feed ratio of
CO/MeOH is high. Not only the initial low partial pres-
sure of AcOMe but also the rapid consumption of AcOMe
by indirect hydrolysis accelerated by the high CO partial
pressure may be the cause for the above.
It is also suggested by both the experiment and calcu-
lation that the low CO/MeOH ratio in the feed is to be
preferred for the selective synthesis of AcOMe since little
AcOH is produced during the reaction. Although DME
is produced, it can be recycled with unchanged MeOH and
CO after separation from AcOMe.
Conclusion
Complex reaction kinetics of the vapor phase carbony-
lation of methanol over nickel on active carbon catalyst
was elucidated by a reaction network consisting of the
primary step comprising carbonylation to methyl acetate
and dehydration to dimethyl ether. The latter compound
is successively carbonylated to methyl acetate. The sec-
ondary step is the formation of acetic acid from methyl
acetate by hydrolysis ether directly or indirectly via acetic
anhydride. The kinetics of the relevant single reactions
were explored separately. The overall reaction of methanol
to acetic acid was successfully simulated by the reaction
network and the kinetic laws were explored taking into
account the self-inhibition of methyl acetate.
 Ind. Eng. Chem. Prod. Res. Dev. 1985, 24, 239-242 239

Registry No. Ni, 7440-02-0; MeOH, 67-56-1; AcOMe, 79-20-9;
Mel, 74-88-4; AcOH, 64-19-7; Rh, 7440-16-6; DME, 115-10-6;
carbon, 7440-44-0.
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Fujlmoto, K.; Shlkada, T.; Mlyauchl, M.; Tominaga, H. Chem. Lett. 1983b,
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Robinson, K. K.; Hershman, A.; Craddock, J. H.; Roth, J. F. J. Catal. 1972,
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Received for review October 25, 1984
Accepted February 8, 1985

Improvement of the Process in the Synthesis of 2-Oxazoiidinones

from 2-Amino Alcohols and Carbon Dioxide by Use of
Triphenylstibine Oxide as Catalyst
Haruo Matsuda, Aklo Baba, Ryoki Nomura,* Masakunl Korl, and Sachiko Ogawa

Department of Applied Chemistry, Faculty of Engineering, Osaka University, Yamada-Oka, Osaka 565, Japan

Organoantimony compounds, especially triphenylstibine oxide, could catalyze the cyclocondensation of 2-amino
alcohols (1) and carbon dioxide (C02) to give 2-oxazolidinones (2) in aprotic media. Molecular Sieves 3A assisted
the catalysis by triphenylstibine oxide. The new catalyst system consisting of triphenylstibine oxide and Molecular
Sieves 3A synerglstlcally gave 2 in good yields and selectivities. Thus, 3-alkyl-2-oxazolidinones were prepared
in 80-94% yields at 130-160 °C, and trans-hexahydro-3-methylbenzoxazolidinone (2h) was stereoselectively
obtained from trans -2-methylaminocyclohexanol (1h).

Introduction Scheme I
In the recent reports, 3-substituted 2-oxazolidinones
R2 H R2 H
have been stated to be useful substances as synthetic
reagents (Joniteau et al., 1980; Meyers, 1974), antibacterials + C02 R1—j l^-R3
R1—j—^—R3
(Fuggit and Luckenbach, 1982), fungicides (Scholl, 1977),
inhibitors (Strolin-Brendett, 1983), additives (Heiss and
Robert, 1978), and others (Dyne and Swern, 1966a). Ac-
cordingly, many synthetic routes have been developed to 2
produce 2-oxazolidinones. Among the methods already where R, R1, R\ R3 , , , H, a; H, Me, , H, b; Me,
=

reported, it is suggested that the direct condensation be-
tween 2-amino alcohols and carbon dioxide (C02) in the
production of 2-oxazolidinones has the large advantage of
simplicity in the process (Dyne and Swern, 1966b). Nev-
ertheless, only limited attempts have been done to improve
such a direct cyclourethanization reaction.
Uncatalyzed synthesis of 2-oxazolidinones (Steele, 1959;
Lyne, 1961) has to be carried out under severe conditions,
and produces relatively low yields of 2-oxazolidinones; e.g.,
3-methyl-2-oxazolidinone was synthesized in 58% yield at
160 °C for 20 h with water as a solvent. On the other hand,
mild conditions without a lessening of the yields are re-
alized by the use of more than an equivalent of high-energy
phosphorus compounds (Akasaki et al., 1977, 1978) or
carbodiimides (Dozen and Ukita, 1982) as condensating
agents. However, the application of these methods results
in significant cost and may generate wasteful byproducts
from the condensing agents. In addition, nothing has been
explored to catalyze the condensation using organo-
, , H, c; Me, Me, , H, d; Me, Et, , H, e; Me, Me, Me,
H, f; Me, -fCH2-h, H, g; Me, H, -(CH2br, h; Et, Me, , H, i;
Bu, Me, , H, j; CH2CH2OH, , , H, k.
metallics, and the development of effective catalyst for the
cyclourethanization has been required.
In the course of our studies on utilization of the orga-
noantimony compounds as catalysts (Nomura et al., 1980,
1983; Matsuda et al., 1984), it was reported that tri-
phenylstibine oxide was easily converted into antimony
alkoxide moieties in the polymerization of ethylene oxide
and that the resulting antimony alkoxides constituted an
active species for both initiation and propagation. For
example, the addition of an equimolar amount of ethanol
to triphenylstibine oxide caused the formation of tri-
phenylantimony diethoxide (Ph3Sb(OEt)2), which can
accelerate the polymerization of ethylene oxide (Nomura
et al., 1983). We consider that once the antimony amino
alkoxide moiety was formed, it could easily added to C02

0196-4321 /85/1224-0239301.50/0 &copy; 1985 American Chemical Society