Title of Invention

METHOD FOR PRODUCING A CARBONIC ESTER

Abstract A method for producing a carbonic ester, compris- ing : (1) performing a reaction between an organometal compound mixture and carbon dioxide, the organometal compound mixture comprising a reactive organometal com- pound and an unregenerable unreactive compound derived from the reactive organometal compound, to thereby ob- tain a reaction mixture containing a carbonic ester, the unregenerable unreactive compound, and a regener- able metamorphic organometal compound derived from the reactive organometal compound, (2) separating the reac- tion mixture into a first portion containing the car- bonic ester and the unregenerable unreactive compound, and a second portion containing the regenerable meta- morphic organometal compound, and (3) reacting the sec- ond portion of the reaction mixture with an alcohol to form an organometal compound mixture and water and re- moving the water from the organometal compound mixture, the organometal compound mixture comprising a reactive organometal compound and an unregenerable unreactive compound derived from the reactive organometal compound.
Full Text TITLE OF THE INVENTION
Method for producing a carbonic ester
BACKGROUND OF THE INVENTION
Field of the invention
The present@@@ invention relates to a method for pro-
ducing a carbonic ester from an organometal compound
and carbon dioxide. More particularly, the present in-
vention is concerned with a method for producing a car-
bonic ester, comprising the steps of: (1) performing a
reaction between a first organometal compound mixture
and carbon dioxide, wherein the first organometal com-
pound mixture comprises a mixture of a reactive or-
ganometal compound having in its molecule at least two
metal-oxygen-carbon linkages and an unregenerable unre-
active compound which is derived from the reactive or-
ganometal compound, to thereby obtain a reaction mix-
ture containing a carbonic ester formed by the reaction,
the unregenerable unreactive compound, and a regener-
able metamorphic organometal compound derived from the
reactive organometal compound, (2) separating the reac-
tion mixture into a first portion containing the car-
bonic ester and the unregenerable unreactive compound,
and a second portion containing the regenerable meta-
morphic organometal compound, and (3) reacting the sec-

ond portion of the reaction mixture with an alcohol to
form a second organometal compound mixture and water
and removing the water from the second organometal com-
pound mixture, wherein the second organometal compound
mixture comprises a mixture of a reactive organometal
compound having in its molecule at least two metal
-oxygen-carbon linkages and an unregenerable unreactive
compound which is derived from the reactive organometal
compound.
By the method of the present invention, a carbonic
ester can be produced in high yield from an organometal
compound having in its molecule at least two metal
-oxygen-carbon linkages and carbon dioxide. One advan-
tage of this method is that carbon dioxide has neither
toxicity nor corrosiveness and is inexpensive. Further,
the method of the present invention is advantageous not
only in that the organometal compound after use in this
method can be regenerated and recycled for reuse in the
method, but also in that the unregenerable unreactive
organometal compound formed in the method can be re-
moved from the reaction system, thereby realizing an
efficient and stable production of a carbonic ester.
Moreover, there is no need for the use of a large
amount of a dehydrating agent, thereby preventing oc-
currence of wastes derived from the dehydrating agent.

Therefore, the method of the present invention is com-
mercially very useful and has high commercial value.
Prior Art
A carbonic ester is a useful compound. For exam-
ple, a carbonic ester is used as additives for various
purposes, such as a gasoline additive for improving the
octane number of a gasoline, and a diesel fuel additive
for reducing the amount of particles in an exhaust gas
generated by the burning of a diesel fuel. A carbonic
ester is also used as an alkylation agent, a carbonyla-
tion agent, a solvent and the like in the field of the
synthesis of organic compounds, such as polycarbonate,
urethane, pharmaceuticals and agrichemicals. A car-
bonic ester is also used as an electrolyte for a lith-
ium battery, a raw material for producing a lubricant
oil and a raw material for producing a deoxidizer which
can be used for preventing boiler pipes from rusting.
As a conventional method for producing a carbonic
ester, there can be mentioned a method in which phos-
gene used as a carbonyl source is reacted with an alco-
hol, thereby producing a carbonic ester. Since phos-
gene used in this method is extremely harmful and
highly corrosive, this method is disadvantageous in
that the transportation and storage of phosgene need

detailed care and, also, there is a large cost for the
maintenance of production equipment and for assuring
safety. Further, this method poses a problem in that
it is necessary to dispose of hydrochloric acid pro-
duced as a waste by-product.
Another conventional method for producing a car-
bonic ester is an oxidative carbonylation method in
which carbon monoxide used as a carbonyl source is re-
acted with an alcohol and oxygen in the presence of a
catalyst, such as copper chloride, thereby producing a
carbonic ester. In this method, carbon monoxide (which
is extremely harmful) is used under high pressure;
therefore, this method is disadvantageous in that there
is a large cost for the maintenance of production
equipment and for assuring safety. In addition, this
method poses a problem in that a side reaction occurs,
such as oxidation of carbon monoxide to form carbon di-
oxide. For these reasons, it has been desired to de-
velop a safer and more efficient method for producing a
carbonic ester.
In these conventional methods in which phosgene or
carbon monoxide is used as a raw material, a halogen,
such as chlorine, is contained in the raw material it-
self or in the catalyst used. Therefore, in the case
of these methods, a carbonic ester obtained contains a

trace amount of a halogen which cannot be completely
removed by a simple purification step. When such car-
bonic ester is used as a gasoline additive, a light oil
additive or a material for producing electronic equip-
ment, there is a danger that the halogen contained in
the carbonic ester causes corrosion of equipment. For
reducing the amount of a halogen in the carbonic ester
to only a trace amount, it is necessary to perform a
thorough purification of the carbonic ester. For this
reason, it has been desired to develop a method for
producing a carbonic ester, which does not use any of a
halogen-containing raw material and a halogen
-containing catalyst.
On the other hand, a method has been put to prac-
tical use, in which carbon dioxide is reacted with eth-
ylene oxide or the like to obtain a cyclic carbonic es-
ter, and the obtained cyclic carbonic ester is reacted
with methanol, thereby producing dimethyl carbonate.
This method is advantageous in that carbon dioxide as a
raw material is harmless, and a corrosive substance,
such as hydrochloric acid, is substantially neither
used nor generated. However, this method poses the
following problems. Ethylene glycol is by-produced in
this method; therefore, from the viewpoint of cost re-
duction, it is necessary to find ways to effectively

utilize the by-produced ethylene glycol. Further, it
is difficult to perform safe transportation of ethylene
(which is a raw material for producing ethylene oxide)
and ethylene oxide. Therefore, for obviating the need
for the transportation, it is necessary that a plant
for producing a carbonic ester by this method be built
at a location which is adjacent to a plant for produc-
ing ethylene and ethylene oxide.
There is also known a method in which carbon diox-
ide used as a carbonyl source is subjected to an equi-
librium reaction with an alcohol in the presence of a
catalyst comprising an organometal compound having a
metal-oxygen-carbon linkage, thereby forming a carbonic
ester and water. This equilibrium reaction is repre-
sented by the following formula (3):

This method is advantageous in that carbon dioxide and
an alcohol as raw materials are harmless. However,

this method employs an equilibrium reaction in which a
carbonic ester and water are simultaneously formed as
products. Also in the case of the above-mentioned oxi-
dative carbonylation method using carbon monoxide, wa-
ter is formed. However, the oxidative carbonylation
method does not employ an equilibrium reaction. The
equilibrium of an equilibrium reaction using carbon di-
oxide as a raw material is thermodynamically biased to-
ward the original system. Therefore, the method using
the equilibrium reaction has a problem in that, for
producing a carbonic ester in high yield, it is neces-
sary that the carbonic ester and water as products be
removed from the reaction system. Further, there is
also a problem in that the water formed decomposes a
catalyst, so that not only is the reaction hindered,
but also the number of turnovers of the catalyst (i.e.,
the number of cycles of regeneration and reuse) is only
2 or 3. For solving this problem, various methods for
removing water (which is a product) by using a dehy-
drating agent have been proposed.
For example, there has been proposed a method in
which an alcohol and carbon dioxide are reacted with
each other in the presence of a metal alkoxide as a
catalyst, thereby forming a carbonic ester and water,
wherein a large amount of dicyclohexylcarbodiimide

(DCC) (which is an expensive organic dehydrating agent)
or the like is used as a dehydrating agent (see Collect.
Czech. Chem. Commun. Vol. 60, 687-692 (1995)). This
method has a problem in that the dehydrating agent af-
ter use cannot be regenerated, resulting in the occur-
rence of a large amount of a waste derived from the de-
hydrating agent.
Another method for producing a carbonic ester uses
a carboxylic acid orthoester as an organic dehydrating
agent (see Unexamined Japanese Patent Application Laid-
Open Specification No. Hei 11-35521). (In this patent
document, there are descriptions reading: "a carboxylic
acid orthoester is reacted with carbon dioxide" and "an
acetal is reacted with carbon dioxide". However, as a
result of recent studies in the art, it is generally
presumed that the actual reaction route is as follows.
"An alcohol and carbon dioxide are reacted with each
other to obtain a carbonic ester and water. The water
is reacted with a carboxylic acid orthoester.") This
method has problems in that a carboxylic acid or-
thoester (which is an expensive compound) is used as a
dehydrating agent, and methyl acetate is by-produced
(see "Kagaku Sochi (Chemical Equipment)", Vol. 41, No.2,
52-54 (1999)). Thus, this method is as defective as
the above-mentioned methods.

Further, another method uses a large amount of an
acetal as an organic dehydrating agent (see German Pat-
ent No. 4310109). There is also a patent document in
which it is described that an acetal and carbon dioxide
are reacted with each other by using, as a catalyst, a
metal alkoxide or dibutyltin oxide (see Unexamined
Japanese Patent Application Laid-Open Specification No.
2001-31629). (With respect to the reaction described
in the latter, as a result of recent studies in the art,
it is generally presumed that the actual reaction route
is as follows. "An alcohol and carbon dioxide are re-
acted with each other to obtain a carbonic ester and
water. The water is then reacted with an acetal.")
However, these patent documents do not teach or suggest
a method for efficiently producing an acetal without
forming a waste. Further, the methods disclosed in
these patent documents have a problem in that, when an
acetal is used as a dehydrating agent, large amounts of
by-products, such as a ketone and an aldehyde, are
formed as wastes.
The effects aimed at by the methods which employ
an organic dehydrating agent are to improve the number
of turnovers of a catalyst. However, an organic dehy-
drating agent is consumed in a stoichiometric amount in
accordance with the formation of a carbonic ester (and

water as a by-product), so that a large amount of an
organic dehydrating agent is consumed, thus forming a
large amount of a degeneration product of the organic
dehydrating agent. Therefore, it is necessary to per-
form an additional step of regenerating a large amount
of a degenerated organic dehydrating agent. Further,
in spite of the use of an organic dehydrating agent in
a large amount, the possibility still remains that de-
activation of a catalyst occurs. The reason is as fol-
lows. In the conventional method for producing a car-
bonic ester by using the equilibrium reaction of the
above-mentioned formula (3), carbon dioxide is in a su-
percritical state. In general, in supercritical carbon
dioxide, a catalyst exhibits poor solubility, and the
catalyst particles are likely to cohere together.
Therefore, there is a problem in that, when an organo-
tin compound (which is susceptive to polymerization) is
used as a catalyst in supercritical carbon dioxide, the
organotin compound as a catalyst is likely to be deac-
tivated due to its polymerization.
There has also been proposed a method which em-
ploys a solid dehydrating agent (see Applied Catalysis
Vol. 142. L1-L3 (1996)). However, this method has a
problem in that the solid dehydrating agent cannot be
regenerated, thus forming a large amount of a waste.

There is also known a method in which an alcohol
(methanol) and carbon dioxide are reacted with each
other in the presence of a metal oxide (dibutyltin ox-
ide) to thereby obtain a reaction mixture, and the ob-
tained reaction mixture is cooled and introduced into a
packed column containing a solid dehydrating agent,
thereby gradually displacing the equilibrium toward a
carbonic ester while effecting dehydration, to obtain a
carbonic ester (see Unexamined Japanese Patent Applica-
tion Laid-Open Specification No. 2001-247519). This
method is based on a technique in which a conventional
technique of using a dehydrating agent is combined with
the known phenomenon that the water adsorbability of a
conventional dehydrating agent (such as molecular
sieves) exhibits a temperature dependency. A dehydrat-
ing agent (such as molecular sieves) exhibits lower wa-
ter adsorbability at high temperatures than at low tem-
peratures. Therefore, for removing a trace amount of
water (by-product) from a reaction mixture which con-
tains a largely excess amount of a low molecular weight
alcohol used as a solvent, it is necessary to cool the
reaction mixture in which an equilibrium is achieved
under high temperature and pressure conditions, before
introducing the reaction mixture into a packed column
containing a solid dehydrating agent. In addition, for

increasing the conversion of an alcohol as a raw mate-
rial, it is necessary that the reaction mixture which
has been cooled and dehydrated in the packed column be
returned to high temperature and pressure conditions
which are necessary for the reaction. Thus, this
method has problems in that it is necessary to consume
an extremely large amount of energy for cooling and
heating, and a large amount of a solid dehydrating
agent is needed. This method is very widely used for
producing an aliphatic ester having a relatively large
equilibrium constant. However, in the production of a
carbonic ester from carbon dioxide and an alcohol,
wherein the equilibrium of the reaction is largely bi-
ased toward the original system, this method cannot be
suitably used because this method poses a serious prob-
lem that it is necessary to repeat the above-mentioned
operation which needs a very large consumption of en-
ergy for cooling and heating. Further, for regenerat-
ing a degenerated dehydrating agent which has adsorbed
water to saturation, it is generally necessary to cal-
cine the degenerated dehydrating agent at several hun-
dreds °C, thus rendering this method commercially dis-
advantageous. Furthermore, in this method, only one
(water) of the two products of an equilibrium reaction
is removed and, therefore, there is a problem in that,

when the equilibrium reaction progresses to increase
the carbonic ester concentration of the reaction system,
the reaction becomes unlikely to progress any more,
that is, this method is still under the restriction of
an equilibrium reaction. In addition, dibutyltin oxide,
which is used as a catalyst in this method, exhibits an
extremely poor solubility in methanol and, hence, al-
most all of dibutyltin oxide as a catalyst remains in
solid form in the reaction mixture. Therefore, when
the reaction mixture is cooled to room temperature in a
cooling step, the reaction mixture turns into a white
slurry, thus causing a problem in that, in a subsequent
dehydration step performed using a packed column con-
taining a dehydrating agent, the slurry causes clogging
of the packed column.
In general, a dehydration method in which water is
removed by distillation is well-known in the field of
organic synthesis reactions. However, in the field of
the production of a carbonic ester from carbon dioxide
and an alcohol, although "Study Report of Asahi Glass
Association for Promotion of Industrial Technology
(Asahi Garasu Kogyogijutsu Shoreikai Kenkyu Hokoku)",
Vol. 33, 31-45 (1978) states that "dehydration by dis-
tillation is now being studied", there have been no re-
ports or the like which state that a dehydration method

using distillation has been completed.
There has been a report which mentions a distilla-
tion separation of a carbonic ester from a reaction
mixture containing a metal alkoxide, wherein the reac-
tion mixture is obtained by reacting carbon dioxide and
an alcohol with each other in the presence of a metal
alkoxide catalyst; however, it is known in the art that,
when a metal alkoxide catalyst is used, a distillation
separation causes a reverse reaction, thus rendering it
difficult to recover a carbonic ester by distillation
separation (see "Journal of the Chemical Society of Ja-
pan (Nippon Kagaku Kaishi)", No. 10, 1789-1794 (1975)).
Especially, no method is known by which a carbonic es-
ter having a high boiling point can be separated in
high yield from a reaction mixture containing a metal
alkoxide.
On the other hand, a metal alkoxide is so unstable
that it is susceptive to deactivation due to the mois-
ture in the air. Therefore, in the above-mentioned
method, the handling of a metal alkoxide needs strict
care. For this reason, no conventional technique using
a metal alkoxide catalyst has been employed in the com-
mercial production of a carbonic ester. A metal alkox-
ide catalyst is an expensive compound, and no technique
is known for regenerating a deactivated metal alkoxide

catalyst.
There has been proposed a method for producing a
carbonic ester by using a dibutyltin dialkoxide as a
catalyst, in which, during the reaction, the catalyst
is formed from dibutyltin oxide (which is stable to
moisture) added to the reaction system (see Japanese
Patent No. 3128576). This method has a problem in that,
although dibutyltin oxide which is charged into the re-
action system is stable, the dibutyltin oxide is con-
verted, during the reaction, into a dibutyltin dialkox-
ide, which is unstable. Therefore, this method cannot
solve the above-mentioned problem of the instability of
a metal alkoxide catalyst. Specifically, this method
has a defect in that, once the reaction mixture is re-
moved from the reaction system for isolating the car-
bonic ester obtained as a reaction product, the unsta-
ble dibutyltin dialkoxide is deactivated and cannot be
regenerated by a conventional technique. Therefore, in
this method, there is no other choice but to discard
the dibutyltin dialkoxide catalyst (which is expensive)
as a waste after the reaction.
On the other hand, it is known that when a metal
alkoxide (e.g., a dialkyltin dialkoxide) is heated to
about 180 °C, the metal alkoxide suffers thermal dete-
rioration form a trialkyltin alkoxide and the like (see

"Kougyoukagakuzasshi (Journal of the Society of Chemi-
cal Industry)", Vol. 72, No. 7, pages 1543 to 1549
(1969)). It is also known that the trialkyltin alkox-
ide formed by the thermal deterioration has a very low
capability of forming a carbonic ester (see "J. Org.
Chem.", Vol. 64, pages 4506 to 4508 (1999)). It is
difficult (or substantially impossible) to regenerate a
dialkyltin dialkoxide having excellent activity from
the trialkyltin alkoxide. Further, the formation of
such degraded compound (i.e., an unregenerable unreac-
tive compound) poses a problem in that, when a metal
alkoxide is reused as a catalyst, the content of an ac-
tive catalyst in the metal alkoxide is decreased and,
hence, the reaction rate and the yield of a carbonic
ester are decreased, rendering a stable production of a
carbonic ester difficult. In such cases, for stabiliz-
ing the reaction rate and the yield of the carbonic es-
ter, a conventional method in which a small amount of a
fresh metal alkoxide is added to the reaction system is
employed. However, this method poses a problem in that,
when the addition of a fresh metal alkoxide is per-
formed while leaving the deterioration product formed
during the reaction as it is in the reaction system,
the deterioration product, which has a low catalyst ac-
tivity, accumulates in a large amount in the reaction

system. As apparent also from the above, there is no
conventional method in which a metal alkoxide is effec-
tively reused as a catalyst; in any of the conventional
methods for producing a carbonic ester, there is no
other choice but to discard the metal alkoxide as a
waste after the reaction, thus rendering the production
of a carbonic ester disadvantageously costly.
Thus, in the conventional methods for producing a
carbonic ester by using a metal alkoxide, carbon diox-
ide and an alcohol, when the metal alkoxide (which is
expensive) has lost its catalyst activity due to hy-
drolysis or the like, there is no way to easily and ef-
fectively regenerate and reuse the metal alkoxide.
Therefore, the conventional methods for producing a
carbonic ester is disadvantageous in that it is neces-
sary to use a large amount of an organic dehydrating
agent or a solid dehydrating agent in combination with
a small amount of a metal alkoxide.
As described hereinabove, the prior art techniques
for producing a carbonic ester have many problems and,
therefore, have not been put to practical use.
For solving these problems accompanying the prior
art, the present inventors have proposed in WO03/055840
a novel method for producing a carbonic ester. The es-
sential feature of the novel method resides in that the

method uses a reaction route in which an organometal
compound having a metal-oxygen-carbon linkage is used
in a large amount as a precursor of a carbonic ester
but not as a catalyst, and the organometal compound is
subjected to an addition reaction with carbon dioxide
to form an adduct, followed by a thermal decomposition
reaction of the adduct, to thereby obtain a reaction
mixture containing a carbonic ester. The present in-
ventors have found that a carbonic ester can be pro-
duced in high yield by the method. Most of the above-
mentioned problems of the prior art have been solved by
the method. However, even this method still poses a
problem in that an unregenerable unreactive organometal
compound is formed during the reaction and accumulates
in the reaction system.
SUMMARY OF THE INVENTION
In this situation, the present inventors have made
further extensive and intensive studies for solving the
above-mentioned problems. In their studies, the pre-
sent inventors have utilized the techniques of their
previous invention disclosed in WO03/055840. As a re-
sult , it has unexpectedly been found that the problems
can be solved by a method for producing a carbonic es-
ter, comprising the steps of: (1) performing a reaction

between a first organometal compound mixture and carbon
dioxide, wherein the first organometal compound mixture
comprises a mixture of a reactive organometal compound
having in its molecule at least two metal-oxygen-carbon
linkages and an unregenerable unreactive compound which
is derived from the reactive organometal compound, to
thereby obtain a reaction mixture containing a carbonic
ester formed by the reaction, the unregenerable unreac-
tive compound, and a regenerable metamorphic organome-
tal compound derived from the reactive organometal com-
pound, (2) separating the reaction mixture into a first
portion containing the carbonic ester and the unregen-
erable unreactive compound, and a second portion con-
taining the regenerable metamorphic organometal com-
pound, and (3) reacting the second portion of the reac-
tion mixture with an alcohol to form a second organome-
tal compound mixture and water and removing the water
from the second organometal compound mixture, wherein
the second organometal compound mixture comprises a
mixture of a reactive organometal compound having in
its molecule at least two metal-oxygen-carbon linkages
and an unregenerable unreactive compound which is de-
rived from the reactive organometal compound. The car-
bonic ester can be easily isolated from the first por-
tion of the reaction mixture by a conventional method.

such as distillation. The second organometal compound
mixture obtained in step (3) can be recovered and recy-
cled to step (1), wherein the second organometal com-
pound mixture is used in the above-mentioned reaction
for producing a carbonic ester. Based on these find-
ings, the present invention has been completed.
Accordingly, a primary object of the present in-
vention is to provide a method in which a reactive or-
ganometal compound used in the reaction can be reused
without the need for a large amount of a dehydrating
agent and by which commercial production of a carbonic
ester in high yield can be performed continuously and
repeatedly any number of times while removing an unre-
generable unreactive organometal compound from the re-
action system.
The foregoing and other objects, features and ad-
vantages of the present invention will be apparent from
the following detailed description taken in connection
with the accompanying drawings and the appended claims.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
In the drawings:
Fig. 1 is the 119Sn-NMR chart of the reactive or-
ganometal compound having a 2-ethylhexyloxy group used
in step (1) in Example 1; and

Fig. 2 is the 119Sn-NMR chart of the unregenerable
unreactive compound which is distilled off in step (2)
in Example 1.
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, there is provided a
method for producing a carbonic ester, comprising the
steps of:
(1) performing a reaction between a first or-
ganometal compound mixture and carbon dioxide, the
first organometal compound mixture comprising a mixture
of a reactive organometal compound having in its mole-
cule at least two metal-oxygen-carbon linkages and an
unregenerable unreactive compound which is derived from
the reactive organometal compound and which has in its
molecule at least three metal-carbon linkages,
to thereby obtain a reaction mixture containing a
carbonic ester formed by the reaction, the unregener-
able unreactive compound, and a regenerable metamorphic
organometal compound derived from the reactive or-
ganometal compound,
(2) separating the reaction mixture into a first
portion containing the carbonic ester and the unregen-
erable unreactive compound, and a second portion con-
taining the regenerable metamorphic organometal com-

pound, and
(3) reacting the second portion of the reaction
mixture with a first alcohol to form a second organome-
tal compound mixture and water and removing the water
from the second organometal compound mixture, the
second organometal compound mixture comprising a
mixture of a reactive organometal compound having in
its molecule at least two metal-oxygen-carbon linkages
and an unregenerable unreactive compound which is
derived from the reactive organometal compound and
which has in its molecule at least three metal-carbon
linkages.
For easy understanding of the present invention,
the essential features and various preferred embodi-
ments of the present invention are enumerated below.
1. A method for producing a carbonic ester, compris-
ing the steps of:
(1) performing a reaction between a first or-
ganometal compound mixture and carbon dioxide, the
first organometal compound mixture comprising a mixture
of a reactive organometal compound having in its mole-
cule at least two metal-oxygen-carbon linkages and an
unregenerable unreactive compound which is derived from
the reactive organometal compound and which has in its

molecule at least three metal-carbon linkages,
to thereby obtain a reaction mixture containing a
carbonic ester formed by the reaction, the unregener-
able unreactive compound, and a regenerable metamorphic
organometal compound derived from the reactive or-
ganometal compound,
(2) separating the reaction mixture into a first
portion containing the carbonic ester and the unregen-
erable unreactive compound, and a second portion con-
taining the regenerable metamorphic organometal com-
pound , and
(3) reacting the second portion of the reaction
mixture with a first alcohol to form a second organome-
tal compound mixture and water and removing the water
from the second organometal compound mixture, the
second organometal compound mixture comprising a
mixture of a reactive organometal compound having in
its molecule at least two metal-oxygen-carbon linkages
and an unregenerable unreactive compound which is
derived from the reactive organometal compound and
which has in its molecule at least three metal-carbon
linkages.
2. The method according to item 1 above, which fur-
ther comprises, after step (3), a step (4) in which the
second organometal compound mixture obtained in step

(3) is recovered and recycled to step (1).
3. The method according to item 1 or 2 above, wherein
the reactive organometal compound used in step (1) com-
prises at least one compound selected from the group
consisting of:
an organometal compound represented by the formula
(1):

M represents a metal atom selected from the
group consisting of elements belonging to Groups
4 and 14 of the Periodic Table, exclusive of
silicon;
1 2
each of R and R independently represents a
straight chain or branched C1-C12 alkyl group, a
C5-C12 cycloalkyl group, a straight chain or
branched C2-C12 alkenyl group, a C7-C20 aralkyl
group comprised of unsubstituted or substituted
C6-C19 aryl and alkyl selected from the group
consisting of straight chain or branched C1-C14

alkyl and C5-C14 cycloalkyl, or an unsubstituted
or substituted C6-C20 aryl group;
each of R3 and R4 independently represents a
straight chain or branched C1-C12 alkyl group, a
C5-C12 cycloalkyl group, a straight chain or
branched C2-C12 alkenyl group, or a C7-C20 aral-
kyl group comprised of unsubstituted or substi-
tuted C6-C19 aryl and alkyl selected from the
group consisting of straight chain or branched
Cl-C14 alkyl and C5-C14 cycloalkyl; and
each of a and b is an integer of from 0 to 2,
a + b = 0 to 2, each of c and d is an integer of
from 0 to 4, and a+b+c+d=4; and
an organometal compound represented by the formula

wherein:
each of M2 and M independently represents a
metal atom selected from the group consisting of
elements belonging to Groups 4 and 14 of the Pe-

riodic Table, exclusive of silicon;
each of R5,R6,R7and R8 independently repre-
sents a straight chain or branched C1-C12 alkyl
group, a C5-C12 cycloalkyl group, a straight
chain or branched C2-C12 alkenyl group, a C7-C20
aralkyl group comprised of unsubstituted or sub-
stituted C6-C19 aryl and alkyl selected from the
group consisting of straight chain or branched
C1-C14 alkyl and C5-C14 cycloalkyl, or an unsub-
stituted or substituted C6-C20 aryl group;
each of R and R independently represents a
straight chain or branched C1-C12 alkyl group, a
C5-C12 cycloalkyl group, a straight chain or
branched C2-C12 alkenyl group, or a C7-C20 aral-
kyl group comprised of unsubstituted or substi-
tuted C6-C19 aryl and alkyl selected from the
group consisting of straight chain or branched
C1-C14 alkyl and C5-C14 cycloalkyl; and
each of e, f, g and h is an integer of from 0
to 2, e+f=0 to 2, g+h = 0 to 2, each of i
and j is an integer of from 1 to 3, e+f+i=
3, and g + h + j = 3.
4. The method according to item 3 above, wherein each
of R3 and R4 in formula (1) and R9 and R10 in formula

(2) independently represents an n-butyl group, an iso-
butyl group, a straight chain or branched C5-C12 alkyl
group, or a straight chain or branched C4-C12 alkenyl
group.
5. The method according to item 3 above, wherein each
of M1 in formula (1) and M and M in formula (2)
represents a tin atom.
6. The method according to item 3 above, wherein the
reactive organometal compound used in step (1) is pro-
duced from an organotin oxide and an alcohol.

7. The method according to item 1 or 2 above, wherein,
in step (1). the reactive organometal compound is used
in at least one form selected from the group consisting
of a monomeric form, an oligomeric form, a polymeric
form and an associated form.
8. The method according to item 1 or 2 above, wherein,
in step (1), the reactive organometal compound is used
in an amount which is 1/50 to 1 time the stoichiometric
amount relative to the amount of the carbon dioxide.
9. The method according to item 1 or 2 above, wherein

the reaction in step (1) is performed at 20°C or
higher.
10. The method according to item 1 or 2 above, wherein
the reaction in step (1) is performed in the presence
of a second alcohol which is the same as or different
from the first alcohol used in step (3).
11. The method according to item 1 or 2 above, wherein,
in step (2), the separation of the reaction mixture
into the first portion and the second portion is per-
formed by at least one separation method selected from
the group consisting of distillation, extraction and
filtration.
12. The method according to item 1 or 2 above, wherein,
in step (2), the separation of the reaction mixture
into the first portion and the second portion is per-
formed in the presence of an alcohol which is the same
as or different from the first alcohol used in step (3).
13. The method according to item 1 or 2 above, wherein
the first alcohol used in step (3) is at least one al-
cohol selected from the group consisting of an alkyl
alcohol having a straight chain or branched C1-C12 al-

kyl group, a cycloalkyl alcohol having a C5-C12
cycloalkyl group, an alkenyl alcohol having a straight
chain or branched C2-C12 alkenyl group, and an aralkyl
alcohol having a C7-C20 aralkyl group comprised of un-
substituted or substituted C6-C19 aryl and alkyl se-
lected from the group consisting of straight chain or
branched C1-C14 alkyl and C5-C14 cycloalkyl.
14. The method according to item 13 above, wherein the
first alcohol has a boiling point which is higher than
the boiling point of water, as measured under atmos-
pheric pressure.
15. The method according to item 14 above, wherein the
first alcohol is at least one alcohol selected from the
group consisting of 1-butanol, 2-methyl-l-propanol, an
alkyl alcohol having a straight chain or branched C5-
C12 alkyl group, an alkenyl alcohol having a straight
chain or branched C4-C12 alkenyl group, a cycloalkyl
alcohol having a C5-C12 cycloalkyl group, and an aral-
kyl alcohol having a C7-C20 aralkyl group comprised of
unsubstituted or substituted C6-C19 aryl and alkyl se-
lected from the group consisting of straight chain or
branched C1-C14 alkyl and C5-C14 cycloalkyl.

16. The method according to item 1 or 2 above, wherein
the removal of the water in step (3) is performed by
membrane separation.
17. The method according to item 16 above, wherein the
membrane separation is pervaporation.
18. The method according to item 1 or 2 above, wherein
the removal of the water in step (3) is performed by-
distillation .
Hereinbelow, the present invention is described in
detail.
As described above, the conventional methods (ex-
clusive of the method proposed by the present inventors
in the above-mentioned WO03/055840) for producing a
carbonic ester employs an equilibrium reaction repre-
sented by the following formula (3):


mentioned WO03/055840), there can be mentioned a method
in which a dehydrating agent is used for a reaction
mixture containing the equilibrium reaction system
(represented by the formula (3) above), wherein the
equilibrium reaction system contains a product system
comprising a carbonic ester and water; and a method in
which a reaction mixture containing the above-mentioned
equilibrium reaction system is cooled and subjected to
a dehydration treatment in which the reaction mixture
is introduced into a packed column containing a solid
dehydrating agent, and circulated through the packed
column, so as to gradually dehydrate the equilibrium
reaction system to thereby suppress a decomposition re-
action of the catalyst and accumulate a carbonic ester
being formed in a trace amount.
On the other hand, the technical concept of the
method of the present invention is completely different
from the technical concept of the conventional methods.
The reaction performed in the method of the pre-
sent invention is basically the same as the reaction
performed in the method proposed by the present inven-
tors in the above-mentioned WO03/055840. Before ex-
plaining the method of the present invention, the es-
sence of the method of the above-mentioned WO03/055840
is briefly explained below.

The method of WO03/055840 is characterized in:
that a reaction route is used in which an or-
ganometal compound having a metal-oxygen-carbon linkage
is used in a large amount as a precursor of a carbonic
ester but not as a catalyst, and the organometal com-
pound is subjected to an addition reaction with carbon
dioxide to form an adduct, followed by a thermal decom-
position reaction of the adduct, to thereby obtain a
reaction mixture containing a carbonic ester (step (1)),
that step (1) is followed by an operation in which
the carbonic ester is separated from the reaction mix-
ture to obtain a residual liquid (step (2)), and
that step (2) is followed by a reaction of the re-
sidual liquid with an alcohol to thereby obtain a reac-
tion mixture comprising an organometal compound having
a metal-oxygen-carbon linkage and water, followed by
removal of the water from the reaction mixture by dis-
tillation or the like, to thereby obtain the organome-
tal compound, whereupon the obtained organometal com-
pound is recovered (step (3)),
followed by recycling the organometal compound to
step (1) for producing a carbonic ester.
The reactions in step (1) and step (3) of the
method of WO03/055840 are represented by the below-
mentioned formulae (4) and (5), respectively.


Thus, the method of WO03/055840 is a method in
which an organometal compound having a metal-oxygen
-carbon linkage is used mainly as a precursor of a car-
bonic ester, and the organometal compound is subjected
to an addition reaction with carbon dioxide to form an
adduct, followed by a thermal decomposition reaction of
the adduct, to thereby obtain a reaction mixture con-
taining a carbonic ester, whereupon the carbonic ester
is separated from the reaction mixture to obtain a re-
sidual liquid (containing a thermal decomposition prod-
uct of the adduct formed by the addition reaction of
the organometal compound having a metal-oxygen-carbon
linkage with carbon dioxide), followed by an operation
in which the residual liquid is reacted with an alcohol

to thereby regenerate an organometal compound having a
metal-oxygen-carbon linkage. The regenerated organome-
tal compound is recovered and recycled to the step of
producing a carbonic ester, and the cycle of these
steps is repeated so as to obtain a carbonic ester in a
desired amount.
In step (1) of the method of WO03/055840, at least
a part of the organometal compound having a metal
-oxygen-carbon linkage is converted into a thermal de-
composition product thereof and, hence, the reaction
mixture obtained in step (1) of the method of
WO03/055840 may or may not contain a residual part of
the organometal compound having a metal-oxygen-carbon
linkage used in step (1). Also, after completion of
step (2) of the method of WO03/055840, at least a part
of the organometal compound having a metal-oxygen
-carbon linkage is converted into a thermal decomposi-
tion product or hydrolysis product thereof and, hence,
the residual liquid obtained in step (2) of the method
of WO03/055840 may or may not contain a residual part
of the organometal compound having a metal-oxygen
-carbon linkage used in step (1). Anyway, an organome-
tal compound having a metal-oxygen-carbon linkage is
regenerated (resynthesized) before completion of step
(3) of the method of WO03/055840.

In the conventional methods using the equilibrium
reaction of the formula (3) above, the entire reaction
is held under equilibrium. By contrast, in the method
of the previous invention, the equilibrium reaction of
the formula (3) above can be effectively divided into
consecutive reactions which can be easily controlled,
thereby rendering it possible to efficiently produce a
carbonic ester while separating the carbonic ester and
water from the reaction system. Specifically, in step
(1) of the method of WO03/055840, a reaction can be
performed in the absence of water. In step (2) of the
method of WO03/055840, a reverse reaction of a carbonic
ester and other thermal decomposition products can be
prevented by separating a carbonic ester from the reac-
tion mixture. In step (3) of the method of WO03/055840,
after the regeneration of an organometal compound hav-
ing a metal-oxygen-carbon linkage, the organometal com-
pound can be recovered by removing water. Further, in
each step of the method of WO03/055840, the operation
conditions can be easily optimized by appropriately em-
ploying conventional techniques of chemical synthesis,
such as cooling, heating, stirring, pressurizing,
decompression and separation.
As mentioned above, the method of the present in-
vention has been completed as a result of the extensive

and intensive studies for improving the above-mentioned
method proposed by the present inventors in WO03/055840.
The method of WO03/055840 poses a problem in that an
unregenerable unreactive organometal compound (i.e., a
degraded compound) formed in the reaction gradually ac-
cumulates in the reaction system. However, this prob-
lem can be easily solved by the method of the present
invention. Generally, an organometal compound is sus-
ceptive to thermal deterioration. Therefore, when an
organometal compound which has been used is recycled,
the reaction system contains a mixture of an active or-
ganometal compound and an organometal compound having
an extremely low activity (i.e., unregenerable unreac-
tive organometal compound, which is a degraded com-
pound), wherein the ratio of the unregenerable unreac-
tive organometal compound to the active organometal
compound gradually becomes large. Therefore, for a
stable production of a carbonic ester, it is necessary
to continuously feed a fresh, active organometal com-
pound or a raw material thereof during the reaction.
In the field of the production of a carbonic ester from
carbon dioxide and an alcohol, it is difficult to sepa-
rate a degraded compound (derived from the organometal
compound) formed during the reaction. Although some
prior art documents concerning such method describe the

recycle of the organometal compound, there has been no
conventional technique for removing the degraded com-
pound (derived from the organometal compound) from the
reaction system. On the other hand, in the field of
the production of a carbonic ester in the presence of a
conventional catalyst, a method has been practiced in
which a part of the catalyst having been used for the
reaction for producing a carbonic ester is taken out
from the reaction system and a fresh catalyst is fed in
an amount which corresponds to the amount of the cata-
lyst having lost its catalyst activity. However, this
method poses a problem in that, for taking out the de-
activated catalyst, it is necessary to take out a part
of the active catalyst in an amount which is several
times or dozens of times the amount of the deactivated
catalyst. Therefore, when a reaction is performed by
using this method in the presence of an expensive cata-
lyst, the production cost becomes very high. Thus, it
is virtually impossible to practice this method on a
commercial scale. Accordingly, in this conventional
method, when a catalyst is recycled, it is important to
selectively remove the degraded compound from the reac-
tion system. As a result of their extensive and inten-
sive studies, the present inventors have found that the
degraded compound has physical properties (such as the

boiling point and the physical state, e.g., the solid
form or the liquid form) and chemical properties (such
as hydrolyzability) which are different from those of
the useful organometal compounds (i.e., a reactive or-
ganometal compound and a regenerable metamorphic or-
ganometal compound). Based on this finding, the pre-
sent inventors have completed the present invention,
which is directed to a method in which an organometal
compound can be repeatedly used while selectively with-
drawing at least a part of a degraded compound derived
from the reactive organometal compound.
The method of the present invention is a method
for producing a carbonic ester, comprising the step of:
(1) performing a reaction between a first or-
ganometal compound mixture and carbon dioxide, the
first organometal compound mixture comprising a mixture
of a reactive organometal compound having in its mole-
cule at least two metal-oxygen-carbon linkages and an
unregenerable unreactive compound which is derived from
the reactive organometal compound and which has in its
molecule at least three metal-carbon linkages,
to thereby obtain a reaction mixture containing a
carbonic ester formed by the reaction, the unregener-
able unreactive compound, and a regenerable metamorphic
organometal compound derived from the reactive or-

ganometal compound,
(2) separating the reaction mixture into a first
portion containing the carbonic ester and the unregen-
erable unreactive compound, and a second portion con-
taining the regenerable metamorphic organometal com-
pound, and
(3) reacting the second portion of the reaction
mixture with a first alcohol to form a second organome-
tal compound mixture and water and removing the water
from the second organometal compound mixture, the
second organometal compound mixture comprising a
mixture of a reactive organometal compound having in
its molecule at least two metal-oxygen-carbon linkages
and an unregenerable unreactive compound which is
derived from the reactive organometal compound and
which has in its molecule at least three metal-carbon
linkaheeinbelow, an explanation is given with respect
to the compounds used in the method of the present in-
vention.
In step (1) of the method of the present invention,
a reactive organometal compound having a metal-oxygen
-carbon linkage is used. The reactive organometal com-
pound used in step (1) of the method of the present in-
vention has in its molecule at least two metal-oxygen
-carbon linkages. As an example of such organometal

compound, there can be mentioned a reactive organometal
compound having at least two alkoxy groups. It is pre-
ferred that the reactive organometal compound used in
step (1) comprises at least one compound selected from
the group consisting of:
an organometal compound represented by the formula

wherein:
M1 represents a metal atom selected from the
group consisting of elements belonging to Groups
4 and 14 of the Periodic Table, exclusive of
silicon;
each of R1 and R2 independently represents a
straight chain or branched C1-C12 alkyl group, a
C5-C12 cycloalkyl group, a straight chain or
branched C2-C12 alkenyl group, a C7-C20 aralkyl
group comprised of unsubstituted or substituted

c6_c19 aryl and alkyl selected from the group
consisting of straight chain or branched C1-C14
alkyl and C5-C14 cycloalkyl, or an unsubstituted
or substituted C6-C20 aryl group;
each of R3 and R4 independently represents a
straight chain or branched C1-C12 alkyl group, a
C5-C12 cycloalkyl group, a straight chain or
branched C2-C12 alkenyl group, or a C7-C20 aral-
kyl group comprised of unsubstituted or substi-
tuted C6-C19 aryl and alkyl selected from the
group consisting of straight chain or branched
C1-C14 alkyl and C5-C14 cycloalkyl; and
wherein:
2 3
each of M and M independently represents a
each of a and b is an integer of from 0 to 2,
a + b = 0 to 2, each of c and d is an integer of
from 0 to 4, and a+b+c+d=4; and
an organometal compound represented by the formula


metal atom selected from the group consisting of
elements belonging to Groups 4 and 14 of the Pe-
riodic Table, exclusive of silicon;
each of R , R , R and R independently repre-
sents a straight chain or branched C1-C12 alkyl
group, a C5-C12 cycloalkyl group, a straight
chain or branched C2-C12 alkenyl group, a C7-C20
aralkyl group comprised of unsubstituted or sub-
stituted C6-C19 aryl and alkyl selected from the
group consisting of straight chain or branched
C1-C14 alkyl and C5-C14 cycloalkyl, or an unsub-
stituted or substituted C6-C20 aryl group;
each of R9 and R10 independently represents a
straight chain or branched C1-C12 alkyl group, a
C5-C12 cycloalkyl group, a straight chain or
branched C2-C12 alkenyl group, or a C7-C20 aral-
kyl group comprised of unsubstituted or substi-
tuted C5-C19 aryl and alkyl selected from the
group consisting of straight chain or branched
C1-C14 alkyl and C5-C14 cycloalkyl; and
each of e, f, g and h is an integer of from 0
to 2, e+f=0 to 2, g+h= 0 to 2, each of i
and 3 is an integer of from 1 to 3, e + f + i =
3, and g + h + j = 3.

The Periodic Table mentioned herein is as pre-
scribed in the IUPAC (International Union of Pure and
Applied Chemistry) nomenclature system (1989).
In the method of the present invention, the above-
mentioned organometal compound is used in at least one
form selected from the group consisting of a monomeric
form, an oligomeric form, a polymeric form and an asso-
ciated form.
Each of M in the organometal compound represented
2 3
by formula (1) above and M and M in the organometal
compound represented by formula (2) above independently
represents a metal atom selected from the group con-
sisting of elements belonging to Groups 4 and 14 of the
Periodic Table, exclusive of silicon. It is preferred
12 3
that each of M , M and M is a metal atom selected
from the group consisting of a titanium atom, a tin
atom and a zirconium atom. From the viewpoint of the
solubility in and reactivity with an alcohol, it is
12 3
more preferred that each of M , M and M is a tin atom.
Examples of R and R in the organometal compound
S (\ 7 ft
represented by formula (1) above and R , R , R and R
in the organometal compound represented by formula (2)
above include C1-C12 alkyl groups (which are aliphatic
hydrocarbon groups) and C5-C12 cycloalkyl groups (which
are alicyclic hydrocarbon groups), such as a methyl

group, an ethyl group, a propyl group, an n-butyl group
(and isomers thereof), a butyl group (and isomers
thereof), a pentyl group (and isomers thereof), a hexyl
group (and isomers thereof), a heptyl group (and iso-
mers thereof), an octyl group (and isomers thereof), a
nonyl group (and isomers thereof), a decyl group (and
isomers thereof), an undecyl group (and isomers
thereof), a dodecyl group (and isomers thereof), a 2-
butenyl group, a cyclobutenyl group, a cyclobutyl group,
a cyclopentyl group, a cyclohexyl group, a cyclopenta-
dienyl group and a cyclohexenyl group; C7-C20 aralkyl
groups, such as a benzyl group and a phenylethyl group;
and C5-C20 aryl groups, such as a phenyl group, a tolyl
group and a naphthyl group. Each of these hydrocarbon
groups may have an ether linkage. Moreover, each of
these hydrocarbon groups may be a halogenated hydrocar-
bon group (i.e., hydrocarbon group which has at least
one hydrogen atom thereof replaced by a halogen atom),
such as a nonafluorobutyl group or a heptafluorobutyl
group (and isomers thereof). However, R1, R2, R5, R6,
R7 and R8 are not limited to these examples. Of the
above-mentioned groups, lower alkyl groups are pre-
ferred, and straight chain or branched C1-C4 alkyl
groups are more preferred. Hydrocarbon groups having
more carbon atoms than mentioned above can also be used

as R1, R2, R5, R6. R7 and R8; however, when such groups
having a larger number of carbon atoms are used, there
is a danger that the fluidity of the organometal com-
pound and/or the productivity of a carbonic ester be-
comes low. Examples of R3 and R4 in the organometal
compound represented by formula (1) above and R9 and
R10 in the organometal compound represented by formula
(2) above include C1-C12 alkyl groups (which are ali-
phatic hydrocarbon groups) and C5-C12 cycloalkyl groups
(which are alicyclic hydrocarbon groups), such as a
methyl group, an ethyl group, a propyl group (and iso-
mers thereof), a butyl group (and isomers thereof), a
2-butenyl group, a pentyl group (and isomers thereof),
a hexyl group (and isomers thereof), an octyl group
(and isomers thereof), a nonyl group (and isomers
thereof), a decyl group (and isomers thereof), an unde-
cyl group (and isomers thereof), a dodecyl group (and
isomers thereof), a cyclopropyl group, a cyclobutyl
group, a cyclopentyl group, a cyclopentadienyl group, a
cyclohexyl group, a cyclohexenyl group, a methoxyethyl
group, an ethoxymethyl group and an ethoxyethyl group;
and C7-C20 aralkyl groups, such as a benzyl group and a
phenylethyl group. However, R3, R4 , R9 and R10 are not
limited to these examples. Of the above-mentioned
groups, preferred are organometal compounds in which

each of the corresponding alcohols (i.e., R3 OH, R4 OH,
R9 OH and R10 OH) has a boiling point higher than that of
water (wherein the boiling point is measured under at-
mospheric pressure). Further, from the viewpoint of
recycling the organometal compound regenerated in step
(3), it is most preferred that, in the organometal com-
pound represented by formula (1) and/or formula (2)
above, the alkyl or alkenyl moiety of each of the
alkoxy group is n-butyl, isobutyl, a straight chain or
branched C5-C12 alkyl or a straight chain or branched
C4-C12 alkenyl.
Examples of reactive organometal compounds repre-
sented by formula (1) above include alkoxytin compounds,
alkoxytitanium compounds and alkylalkoxytin compounds.
Specific examples of such organometal compounds include
tetramethoxytin, tetraethoxytin, tetrapropyloxytin (and
isomers thereof), tetrabutyloxytin (and isomers
thereof), tetrapentyloxytin (and isomers thereof), tet-
rahexyloxytin (and isomers thereof), tetraheptyloxytin
(and isomers thereof), tetraoctyloxytin (and isomers
thereof), tetranonyloxytin (and isomers thereof), di-
methoxydiethoxytin, tetramethoxytitanium, tetraeth-
oxytitanium, tetrapropyloxytitanium, tetraisopropy-
loxytitanium, tetrakis(2-ethyl-1-hexyloxy)titanium,
tetrabenzyloxytin, dimethoxydiethoxytin, diethoxydipro-

pyloxytin (and isomers thereof), dimethoxydihexyloxytin
(and isomers thereof), dimethyldimethoxytin, di-
methyldiethoxytin, dimethyldipropyloxytin (and isomers
thereof), dimethyldibutyloxytin (and isomers thereof),
dimethyldipentyloxytin (and isomers thereof), di-
me thy ldihexyloxy tin (and isomers thereof), dimethyldi-
heptyloxytin (and isomers thereof), dimethyldiocty-
loxytin (and isomers thereof), dimethyldinonyloxytin
(and isomers thereof), dimethyldidecyloxytin (and iso-
mers thereof), dibutyltin dimethoxide, dibutyltin di-
ethoxide, dibutyltin dipropoxide (and isomers thereof),
dibutyltin dibutoxide (and isomers thereof), dibutyltin
dipentyloxide (and isomers thereof), dibutyltin dihexy-
loxide (and isomers thereof), dibutyltin diheptyloxide
(and isomers thereof), dibutyltin dioctyloxide (and
isomers thereof), dibutyltin dinonyloxide (and isomers
thereof), dibutyltin didecyloxide (and isomers thereof),
dibutyltin dibenzyloxide, dibutyltin diphenylethoxide,
diphenyltin dimethoxide, diphenyltin diethoxide, di-
phenyltin dipropoxide (and isomers thereof), di-
phenyltin dibutoxide (and isomers thereof), diphenyltin
dipentyloxide (and isomers thereof), diphenyltin di-
hexyloxide (and isomers thereof), diphenyltin dihepty-
loxide (and isomers thereof), diphenyltin dioctyloxide
(and isomers thereof), diphenyltin dinonyloxide (and

isomers thereof), diphenyltin didecyloxide (and isomers
thereof), diphenyltin dibenzyloxide, diphenyltin di-
phenylethoxide, bis(trifluorobutyl)tin dimethoxide,
bis(trifluorobutyl)tin diethoxide,
bis(trifluorobutyl)tin dipropoxide (and isomers
thereof) and bis(trifluorobutyl)tin dibutoxide (and
isomers thereof).
Examples of reactive organometal compounds repre-
sented by formula (2) above include alkoxydistannoxanes
and aralkyloxydistannoxanes. Specific examples of such
organometal compounds include
1,1,3,3-tetramethyl-l,3-dimethoxydistannoxane,
1,1,3,3-tetramethyl-l,3-diethoxydistannoxane,
1,1,3,3-tetramethyl-l,3-dipropyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetramethyl-l,3-dibutyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetramethyl-l,3-dipentyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetramethyl-l,3-dihexyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetramethyl-l,3-diheptyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetramethyl-l,3-dioctyloxydistannoxane (and
isomers thereof).

1,1,3,3-tetramethyl-1,3-dinonyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetramethyl-1,3-didecyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetramethyl-1,3-dibenzyloxydistannoxane,
1,1,3,3-tetramethyl-1,3-diphenylethoxydistannoxane,
1,1,3,3-tetrabutyl-1,3-dimethoxydistannoxane,
1,1,3,3-tetrabutyl-l,3-diethoxydistannoxane,
1,1,3,3-tetrabutyl-l,3-dipropyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetrabutyl-1,3-dibutyloxydistannoxane (and iso-
mers thereof),
1,1.3,3-tetrabutyl-l,3-dipentyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetrabutyl-l,3-dihexyloxydistannoxane (and iso-
mers thereof),
1,1,3,3-tetrabutyl-1,3-diheptyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetrabutyl-l,3-dioctyloxydistannoxane (and iso-
mers thereof),
1,1,3,3-tetrabutyl-1,3-dinonyloxydistannoxane (and iso-
mers thereof),
1,1,3,3-tetrabutyl-1,3-didecyloxydistannoxane (and iso-
mers thereof),
1,1,3,3-tetrabutyl-1,3-dibenzyloxydistannoxane,

1,1,3, 3-tetrabutyl-l,3-diphenylethoxydistannoxane,
1,1,3,3-tetrapheny1-1,3-dimethoxydistannoxane,
1,1,3.3-tetraphenyl-l,3-diethoxydistannoxane,
1,1,3, 3-tetraphenyl-l,3-dipropyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetraphenyl-l,3-dibutyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetraphenyl-l,3-dipentyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetraphenyl-l,3-dihexyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetraphenyl-l.3-diheptyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetraphenyl-l,3-dioctyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetraphenyl-l,3-dinonyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetraphenyl-l,3-didecyloxydistannoxane (and
isomers thereof),
1,1,3,3-tetraphenyl-l,3-dibenzyloxydistannoxane,
1,1,3,3-tetraphenyl-l,3-diphenylethoxydistannoxane,
1,1,3,3-tetrakis(trifluorobutyl)-1,3
-dimethoxydistannoxane,
1,1,3,3-tetrakis(trifluorobutyl)-1,3
-diethoxydistannoxane,

1,1,3,3-tetrakis(trifluorobutyl)-1,3
-dipropyloxydistannoxane (and isomers thereof).
1,1,3,3-tetrakis(trifluorobutyl)-1,3
-dibutyloxydistannoxane (and isomers thereof),
1,1,3,3-tetrakis(pentafluorobutyl)-1,3
-dimethoxydistannoxane,
1,1,3,3-tetrakis(pentafluorobutyl)-1, 3
-diethoxydistannoxane,
1,1,3,3-tetrakis(pentafluorobutyl)-1,3
-dipropyloxydistannoxane (and isomers thereof),
1,1,3,3-tetrakis(pentafluorobutyl)-1,3
-dibutyloxydistannoxane (and isomers thereof),
1,1,3,3-tetrakis(pentafluorobutyl)-1,3
-dipentyloxydistannoxane (and isomers thereof),
1,1,3,3-tetrakis(pentafluorobutyl)-l,3
-dihexyloxydistannoxane (and isomers thereof),
1.1, 3,3-tetrakis(heptafluorobutyl)-1,3
-dimethoxydistannoxane,
1,1,3,3-tetrakis(heptafluorobutyl)-1,3
-diethoxydistannoxane,
1,1,3,3-tetrakis(heptafluorobutyl) -1,3
-dipropyloxydistannoxane (and isomers thereof),
1,1,3,3-tetrakis(heptafluorobutyl)-1,3
-dibutyloxydistannoxane (and isomers thereof).
The above-mentioned reactive organometal compounds

may be used individually or in combination. Further,
orgnometal compounds other than mentioned above or in-
organic metal compounds may be used in combination with
the above-mentioned reactive organometal compounds. As
a reactive organometal compound, those reactive or-
ganometal compounds which are commercially available
may be used. Alternatively, reactive organometal com-
pounds represented by formula (1) above may be obtained
by a conventional method (e.g., a method described in
Dutch Patent No. 6612421) in which dibutyltin oxide, an
alcohol having 4 or more carbon atoms and a solvent ex-
hibiting an azeotropy with water are mixed together to
effect a reaction, and the resultant is subjected to
distillation, thereby obtaining a fraction containing a
reactive organometal compound represented by formula
(1) above. The above-mentioned Dutch Patent No.
6612421 describes that this method cannot be employed
for obtaining an organometal compound having a C1-C3
alkoxy group and that an organometal compound having a
C1-C3 alkoxy group can be obtained from dibutyltin di-
chloride and sodium alcoholate. On the other hand, by
employing a method described in Japanese Patent Appli-
cation No. 2001-396537 or Japanese Patent Application
No. 2001-396545, there can be obtained an organometal
compound represented by formula (1) or (2) from a metal

oxide and an alcohol. By this method, there can be ob-
tained an organometal compound having a C1-C3 alkoxy
group, such as a methoxy group. For example, an or-
ganometal compound having a methoxy group can be ob-
tained from dibutyltin oxide, methanol and hexane. It
is known that, in such a case, methanol and hexane form
a minimum boiling azeotrope. However, the present in-
ventors have unexpectedly found that, by this method,
the removal of water can be performed, even though the
methanol/hexane mixture has a boiling point lower than
that of water. Based on this finding, the present in-
ventors have developed a method for producing an or-
ganometal compound from an alcohol having a boiling
point lower than that of water. An organometal com-
pound obtained from dibutyltin oxide and an alcohol
having a boiling point lower than that of water tends
to be comprised mainly of an organometal compound rep-
resented by formula (2). However, when it is desired
to obtain a large amount of an organometal compound
represented by formula (1), it can be achieved by sub-
jecting the above-mentioned organometal compound com-
prised mainly of an organometal compound represented by
formula (2) to distillation, thereby obtaining a frac-
tion comprising an organometal compound represented by
formula (1). Alternatively, an organometal compound

represented by formula (1) can be obtained by perform-
ing a reaction of dialkyltin dichloride and an alcoho-
late.
In the present invention, in connection with the
above-mentioned reactive organometal compound, the term
"regenerable metamorphic organometal compound derived
from the reactive organometal compound" and the term
"unregenerable unreactive (organometal) compound de-
rived from the reactive organometal compound" are used.
With respect to these terms, explanations are given be-
low. The reactive organometal compound used in the
present invention is an organometal compound having in
its molecule at least two metal-oxygen-carbon linkages.
In the present invention, the term "regenerable meta-
morphic organometal compound derived from the reactive
organometal compound" is used to indicate compounds
which are comprised mainly of the decomposition prod-
ucts formed by the thermal decomposition of the above
-mentioned adduct (CO2 adduct) formed by the reaction
of the reactive organometal compound with carbon diox-
ide, wherein the thermal decomposition products are
formed simultaneously with the formation of the car-
bonic ester. It is difficult to specify the detailed
structure of the regenerable metamorphic organometal
compound. However, as regenerable metamorphic or-

ganometal compounds, there can be also mentioned a hy-
drolysis product of the reactive organometal compound
and a hydrolysis product of the carbon dioxide adduct
of the reactive organometal compound.
On the other hand, the term "unregenerable unreac-
tive (organometal) compound derived from the reactive
organometal compound" (or simply "degraded compound")
is used to indicate compounds which are unregenerable
organometal compounds (formed by a thermal degradation
of the reactive organometal compound and/or the carbon
dioxide adduct thereof) having an extremely low activ-
ity. A degraded compound (i.e.. unregenerable unreac-
tive compound) is formed mainly in step (3). However,
a degraded compound is sometimes formed in a step for
producing the reactive organometal compound. As a rep-
resentative example of the degraded compound, there can
be mentioned a compound having, per metal atom in a
molecule thereof, at least three metal-carbon linkages.
As an example of such a compound, there can be men-
tioned a compound represented by the following formula
(6):


wherein:
M represents a metal atom selected from
the group consisting of elements belonging
to Groups 4 and 14 of the Periodic Table,
exclusive of silicon;
each of R11 , R12 and R13 independently
represents a straight chain or branched C1-
C12 alkyl group, a C5-C12 cycloalkyl group,
a straight chain or branched C2-C12 alkenyl
group, a C7-C20 aralkyl group comprised of
unsubstituted or substituted C6-C19 aryl and
alkyl selected from the group consisting of
straight chain or branched C1-C14 alkyl and
C5-C14 cycloalkyl, or an unsubstituted or
substituted C6-C20 aryl group;
R14 represents a straight chain or
branched C1-C12 alkyl group, a C5-C12
cycloalkyl group, a straight chain or

branched C2-C12 alkenyl group, or a C7-C2o
aralkyl group comprised of unsubstituted or
substituted C6-C19 aryl and alkyl selected
from the group consisting of straight chain
or branched C1-C14 alkyl and C5-C14 cycloal-
kyl; and
each of k, 1 and m is an integer of from
0 to 4, k+1+m=3 or 4, nisan integer
of 0 or 1, and k+1+m+n=4.
Specific examples of degraded compounds of formula
(6) above include tetraalkyltin and trialkyltin alkox-
ide. Further examples of degraded compounds (unreac-
tive compounds) include metal oxides, such as SnO2,
TiO2 and ZrO2.
The degraded compound (such as the above-mentioned
compound having, per metal atom in a molecule thereof,
at least three metal-carbon linkages) has physical and
chemical properties different from those of the useful
organometal compound (i.e., the reactive organometal
compound or the regenerable metamorphic organometal
compound). Specifically, the degraded compound is dif-
ferent from the useful organometal compound mainly in
that the degraded compound has a boiling point lower
than that of the useful organometal compound and is

less susceptible to hydrolysis than the useful or-
ganometal compound.
Hereinbelow, explanations are given with respect
to the alcohols used in the method of the present in-
vention.
In the method of the present invention, a first
alcohol is used in step (3). In addition, a second al-
cohol may be optionally used in step (1). Further, an
alcohol may be optionally used in step (2) (hereinafter,
this alcohol is frequently referred to as a "third al-
cohol" ) .
The first, second and third alcohols may be the
same or different from one another. Examples of such
alcohols include alkyl alcohols having a straight chain
or branched C1-C12 alkyl group, cycloalkyl alcohols
having a C5-C12 cycloalkyl group, alkenyl alcohols hav-
ing a straight chain or branched C2-C12 alkenyl group,
and aralkyl alcohols having a C7-C20 aralkyl group com-
prised of unsubstituted or substituted C5-C19 aryl and
alkyl selected from the group consisting of straight
chain or branched C1-C14 alkyl and C5-C14 cycloalkyl.
Specific examples of these alcohols include C1-C12
aliphatic alcohols and C5-C12 alicyclic alcohols, such
as methanol, ethanol, propanol, 2-propanol, 1-butanol,

2-butanol (and isomers thereof), 2-methyl-1-propanol,
2-methyl-2-propanol, cyclobutanol, 1-pentanol, 2
-pentanol (and isomers thereof), 3-pentanol, 3-methyl
-1-butanol, 2-methyl-l-butanol, 2-methyl-2-butanol (and
isomers thereof), 3-methyl-2-butanol (and isomers
thereof), cyclopentanol, 2-methyl-l-cyclobutanol (and
isomers thereof), 3-methyl-l-cyclobutanol (and isomers
thereof), 1-methyl-1-cyclobutanol (and isomers thereof),
cyclobutylmethanol (and isomers thereof), 1-hexanol, 2
-hexanol (and isomers thereof), 3-hexanol (and isomers
thereof), 4-methyl-1-pentanol (and isomers thereof), 3
-methyl-1-pentanol (and isomers thereof), 2-methyl-l
-pentanol (and isomers thereof), 2-ethyl-1-butanol, 3
-methyl-2-pentanol (and isomers thereof), 3-methyl-3
-pentanol (and isomers thereof), cyclohexanol, 1
-methyl-1-cyclopentanol (and isomers thereof), 2
-methyl-1-cyclopentanol (and isomers thereof), 2
-cyclobutylethanol (and isomers thereof), 1
-cyclobutylethanol (and isomers thereof), (1
-methylcyclobutyl)methanol (and isomers thereof), (2
-methylcyclobutyl)methanol (and isomers thereof), hep-
tanol (and isomers thereof), cyclohexylmethanol (and
isomers thereof), (methylcyclohexyl)methanol (and iso-
mers thereof), cyclohexylethanol (and isomers thereof),
(ethylcyclobutyl)methanol (and isomers thereof), (me-

thylcyclopropyl)ethanol (and isomers thereof), (ethyl-
cyclopropyl)methanol (and isomers thereof), octanol
(and isomers thereof), nonanol (and isomers thereof),
decanol (and isomers thereof), undecanol (and isomers
thereof), dodecanol (and isomers thereof), propenyl al-
cohol, butenyl alcohol (and isomers thereof), pentenyl
alcohol (and isomers thereof), cyclopentenol (and iso-
mers thereof), cyclopentadienyl alcohol, hexenol (and
isomers thereof) and cyclohexenol (and isomers
thereof); and aralkyl alcohols, such as benzyl alcohol
and phenylethyl alcohol.
Further, as the first, second and third alcohols,
polyhydric alcohols may be used. Examples of polyhy-
dric alcohols include polyhydric C1-C12 aliphatic alco-
hols and polyhydric C5-C12 alicyclic alcohols, such as
ethylene glycol, 1,3-propanediol, 1,2-propanediol,
cyclohexanediol and cyclopentanediol; and aralkyl alco-
hols, such as benzenedimethanol.
Among the above-mentioned alcohols, preferred are
C1-C8 primary or secondary monohydric alcohols, such as
methanol, ethanol, propanol, 2-propanol, 1-butanol, 2
-butanol (and isomers thereof), 2-methyl-1-propanol, 2
-methyl-2-propanol, cyclobutanol, 1-pentanol, 2
-pentanol (and isomers thereof), 3-pentanol, 3-methyl
-1-butanol, 2-methyl-1-butanol, 2-methyl-2-butanol (and

isomers thereof), 3-methyl-2-butanol (and isomers
thereof), cyclopentanol, 2-methyl-1-cyclobutanol (and
isomers thereof), 3-methyl-1-cyclobutanol (and isomers
thereof), 1-methyl-1-cyclobutanol (and isomers thereof),
cyclobutylmethanol (and isomers thereof), 1-hexanol, 2
-hexanol (and isomers thereof), 3-hexanol (and isomers
thereof), 4-methyl-1-pentanol (and isomers thereof), 3
-methyl-1-pentanol (and isomers thereof), 2-methyl-l
-pentanol (and isomers thereof), 2-ethyl-l-butanol, 3
-methyl-2-pentanol (and isomers thereof), 3-methyl-3
-pentanol (and isomers thereof), cyclohexanol, 1
-methyl-1-cyclopentanol (and isomers thereof), 2
-methyl-1-cyclopentanol (and isomers thereof), 2
-cyclobutylethanol (and isomers thereof), 1
-cyclobutylethanol (and isomers thereof), (1
-methylcyclobutyl)methanol (and isomers thereof), (2
-methylcyclobutyl)methanol (and isomers thereof), hep-
tanol (and isomers thereof), cyclohexylmethanol (and
isomers thereof), (methylcyclohexyl)methanol (and iso-
mers thereof), cyclohexylethanol (and isomers thereof),
(ethylcyclobutyl)methanol (and isomers thereof), (me-
thylcyclopropyl)ethanol (and isomers thereof), (ethyl-
cyclopropyl)methanol (and isomers thereof), octanol
(and isomers thereof) and hexenol; and C7-C8 primary or
secondary aralkyl alcohols, such as benzyl alcohol.

Among the above-mentioned alcohols, more preferred
are the alkyl alcohols, the cycloalkyl alcohols, the
alkenyl alcohols and the aralkyl alcohols, which have a
boiling point higher than that of water (wherein the
boiling point is measured under atmospheric pressure).
Examples of such alcohols include 1-butanol, 2-methyl
-1-propanol, an alkyl alcohol having a straight chain
or branched C5-C12 alkyl group, an alkenyl alcohol hav-
ing a straight chain or branched C4-C12 alkenyl group,
a cycloalkyl alcohol having a C5-C12 cycloalkyl group
and an aralkyl alcohol having a C7-C20 aralkyl group
comprised of unsubstituted or substituted C6-C19 aryl
and alkyl selected from the group consisting of
straight chain or branched C1-C14 alkyl and C5-C14
cycloalkyl. Among these alcohols, most preferred are
alkyl alcohols having a straight chain or branched C5-
Cg alkyl group.
Hereinbelow, explanations are given on the method
for analyses of the reactive organometal compound and
the degraded compound derived therefrom.
The reactive organometal compounds which are, re-
spectively, represented by formulae (1) and (2), and
the degraded compound (the unregenerable unreactive
compound) can be analyzed by, for example, the Sn-119
Nuclear Magnetic Resonance (119Sn-NMR) spectroscopy (see.

for example, U.S. Patent No. 5,545,600). However, in a
119Sn-NMR spectrum, a chemical shift value ascribed to
the structure of the organometal compound represented
by formula (1) largely varies depending, for example,
on the organometal compound content of the sample used
for the 119Sn-NMR analysis and on the presence or ab-
sence of an alcohol in the sample used for the 119Sn-NMR
analysis. Therefore, it is preferred that the analysis
of the organometal compound is performed by a method in
which the proton nuclear magnetic resonance (1H-NMR)
spectroscopy and the carbon-13 nuclear magnetic reso-
nance (13C-NMR) spectroscopy are used in combination
with the 119Sn-NMR spectroscopy. Table 1 below shows
119Sn-NMR data of examples of chemical shift values as-
cribed to the structure of a reactive orgnometal com-
pound represented by formula (1), which is produced
from 2-ethyl-1-hexanol and dibutyltin oxide. Table 2
below shows 119Sn-NMR data of examples of chemical shift
values ascribed to the structure of a degraded compound
(i.e., unregenerable unreactive organometal compound)
represented by formula (6). In the 119Sn-NMR chart of
the degraded compound, the chemical shift value as-
cribed to the structure of the degraded compound does
not depend very much on the degraded compound content
of the sample used for the 119Sn-NMR analysis, but

mainly on the types of alkyl groups and alkoxy group
contained in the degraded compound. The characteristic
feature of the 119Sn-NMR chart of the degraded compound
resides in that signals ascribed to the structure of
the degraded compound appear in the range of from 6 90
to 110 ppm.




With respect to each step of the method of the
present invention, detailed explanations are given be-
low.
In step (1) of the method of the present invention,
a reaction is performed between a first organometal
compound mixture and carbon dioxide, wherein the first
organometal compound mixture comprises a mixture of a
reactive organometal compound having in its molecule at
least two metal-oxygen-carbon linkages and an unregen-
erable unreactive compound which is derived from the
reactive organometal compound and which has in its
molecule at least three metal-carbon linkages, to
thereby obtain a reaction mixture containing a carbonic
ester formed by the reaction, the unregenerable unreac-
tive compound, and a regenerable metamorphic organome-
tal compound derived from the reactive organometal com-
pound. Step (1) of the method of the present invention
involves a reaction route in which a carbon dioxide ad-
duct of a reactive organometal compound having in its
molecule at least two metal-oxygen-carbon linkages is
formed, and the adduct formed is thermally decomposed
to obtain a carbonic ester. That is, in the reaction
route of step (1), carbon dioxide is addition-bonded to
a reactive organometal compound to form an adduct, and
the adduct is thermally decomposed. Differing from the

conventional methods, step (1) of the method of the
present invention is characterized in that an organome-
tal compound having in its molecule at least two metal
-oxygen-carbon linkages is reacted with a small
stoichiometric amount of carbon dioxide. In the con-
ventional methods, carbon dioxide under a high pressure
is reacted with an alcohol in the presence of a small
amount of a metal catalyst. As an example of such con-
ventional method, there can be mentioned a method in
which carbon dioxide is reacted with methanol in the
presence of dibutyltin dimethoxide (see Polyhedron, Vol.
19, pages 573-576 (2000)). In the conventional method
described in this literature, carbon dioxide under a
pressure of about 30 MPa is reacted with methanol at
180 °C in the presence of several millimoles of dibu-
tyltin dimethoxide. The exact amount of carbon dioxide
used in the reaction is not described in the above-
mentioned literature. However, it is considered that,
even if the partial pressure of methanol is subtracted,
the amount of carbon dioxide used in the reaction
should be as large as at least 100 times the
stoichiometric amount relative to the amount of the or-
ganometal compound having a metal-oxygen-carbon linkage.
By achieving the above-mentioned high pressure condi-
tions, the equilibrium is forcibly displaced toward a

carbonic ester, so that a carbonic ester can be pro-
duced in a yield which is higher than expected from the
amount of the catalyst. However, by the reaction of
carbon dioxide with methanol, free water is also pro-
duced, thus posing a serious problem in that the cata-
lyst is hydrolyzed by the free water. For solving this
problem, it is necessary to develop a method for dehy-
drating the reaction system. In the above-mentioned
literature, it is described that, under the above
-mentioned reaction conditions, dibutyltin oxide is
produced as a hydrolysis product of dibutyltin dimeth-
oxide and remains in the reaction system. Dibutyltin
oxide cannot be dissolved in a solvent at room tempera-
ture; however, in the method of the present invention,
even when the reaction mixture after completion of step
(1) is cooled to room temperature, the reaction mixture
generally remains in the form of a liquid. In this re-
spect, the reaction used in the method of the present
invention differs from the reaction used in the above
-mentioned conventional method in which a large amount
of carbon dioxide is used.
In the case of the conventional method, the reac-
tion system has a high carbon dioxide concentration and,
hence, the reaction is necessarily performed under high
pressure conditions. Therefore, when the reaction mix-

ture containing the produced carbonic ester is taken
out from the reactor, it is necessary to purge a large
amount of carbon dioxide from the reactor before taking
out the reaction mixture. Such necessity poses prob-
lems not only in that a large amount of carbon dioxide
is wasted, but also in that, if it is intended to reuse
the purged carbon dioxide, repressurization of the car-
bon dioxide becomes necessary and, hence, a large
amount of energy is consumed for the repressurization
of the carbon dioxide. Further, in the conventional
method, the following problem is also likely to occur.
It is known that, when the reaction system has a high
carbon dioxide concentration, the density of the carbon
dioxide gas layer increases, so that the carbon dioxide
dissolves not only a solvent and a catalyst but also
the produced carbonic ester, thereby forming a reaction
mixture comprised of a homogeneous mixture of carbon
dioxide, the solvent, the catalyst and the produced
carbonic ester. When the reaction mixture (homogeneous
mixture) is cooled to obtain a liquid reaction mixture,
the liquid reaction mixture contains carbon dioxide in
the form of liquid carbonic acid. Thus, it is ex-
tremely difficult to separate the produced carbonic es-
ter from the reaction mixture.
In step (1) of the method of the present invention.

it is preferred that carbon dioxide is used in an
amount which is 1 to 50 times, more advantageously 1 to
20 times, as large as the stoichiometric amount rela-
tive to the amount of the reactive organometal compound
having in its molecule at least two metal-oxygen-carbon
linkages. When the amount of carbon dioxide is large,
the reaction becomes a high pressure reaction, so that
not only does it become necessary to use a reactor hav-
ing high pressure resistance, but also a large amount
of carbon dioxide is wasted during purging of unreacted
carbon dioxide after completion of step (1). Therefore,
it is still more preferred that carbon dioxide is used
in an amount which is 1 to 10 times as large as the
stoichiometric amount relative to the amount of the re-
active organometal compound. In other words, in step
(1), it is preferred that the reactive organometal com-
pound is used in an amount which is 1/50 to 1 time,
more advantageously 1/20 to 1 time, as large as the
stoichiometric amount relative to the amount of carbon
dioxide. In the present invention, a carbon dioxide
adduct of the reactive organometal compound having in
its molecule at least two metal-oxygen-carbon linkages
can be easily obtained by contacting the reactive or-
ganometal compound with carbon dioxide. When the reac-
tion temperature is room temperature (20 °C), the car-

bon dioxide adduct is exothermically produced by con-
tacting the reactive organometal compound with a stream
of carbon dioxide having atmospheric pressure. In this
case, the carbon dioxide adduct can be obtained in a
yield of almost 100 %. In accordance with the eleva-
tion of the reaction temperature, the amount of the
carbon dioxide adduct produced becomes lowered; however,
even when the reaction temperature is high, the lower-
ing of the amount of the carbon dioxide adduct can be
suppressed by contacting the reactive organometal com-
pound with carbon dioxide having a high pressure. In
step (1), when the reactive organometal compound is
contacted with carbon dioxide having a high pressure,
it is difficult to determine the amount of the carbon
dioxide adduct produced; however, it is preferred that
the reaction of the reactive organometal compound with
carbon dioxide is performed under a desired pressure,
depending on the rate at which the carbonic ester is
produced and on the amount of the carbonic ester pro-
duced. The reaction pressure is generally from atmos-
pheric pressure to 200 MPa. It is preferred that the
amount of the carbonic ester obtained in step (1) is
100 % or less, more advantageously 50 % or less, based
on the stoichiometric amount relative to the amount of
the reactive organometal compound. The reason for this

is as follows. The reactive organometal compound used
in the method of the present invention is more suscep-
tible to hydrolysis than the carbonic ester produced.
Therefore, when the carbonic ester is obtained in an
amount which is 100 % or less, preferably 50 % or less,
based on the stoichiometric amount relative to the
amount of the reactive organometal compound, water
which is likely to hydrolyze the produced carbonic es-
ter does advantageously not occur in the reaction mix-
ture. On the other hand, in the case of the conven-
tional methods, the reaction is performed so that the
amount of the carbonic ester produced is more than
100 %, based on the stoichiometric amount relative to
the amount of the reactive organometal compound. As a
result, in the case of the conventional methods, the
generation of free water which is likely to hydrolyze
the produced carbonic ester poses a serious problem.
For preventing the produced carbonic ester from being
hydrolyzed, it is necessary to add a dehydrating agent
to the reaction system or to perform the reaction in
the presence of a dehydrating agent, wherein the dehy-
drating agent is selected from the group consisting of
a dehydrating agent which is more susceptible to hy-
drolysis than the reactive organometal compound, and a
solid dehydrating agent having high water adsorptivity.

Such use of a dehydrating agent is disadvantageous not
only in that a complicated step is needed, but also in
that the dehydrating agent is expensive. Therefore,
the conventional methods have not been practically em-
ployed as a method for producing a carbonic ester on a
commercial scale. By contrast, in the reaction route
of step (1) of the method of the present invention, the
main reaction is a decomposition reaction in which a
carbon dioxide adduct of the reactive organometal com-
pound having in its molecule at least two metal-oxygen
-carbon linkages is thermally decomposed to obtain a
carbonic ester. The thermal decomposition reaction is
performed at a temperature in the range of from 20 to
300 °C. In step (1) of the method of the present in-
vention, an alcohol exchange reaction or an ester ex-
change reaction may be performed together with the
above-mentioned decomposition reaction. Specifically,
for example, when step (1) is performed in the presence
of a second alcohol, an alcohol exchange reaction oc-
curs between an oxygen-carbon linkage of the second al-
cohol and an oxygen-carbon linkage of the reactive or-
ganometal compound having in its molecule at least two
metal-oxygen-carbon linkages, so that a carbonic ester
corresponding to the second alcohol can be obtained.
Alternatively, after the formation of a carbonic ester.

a second alcohol may be added to the reaction system to
perform an ester exchange reaction, thereby obtaining
another carbonic ester corresponding to the second al-
cohol .
With respect to step (1), more detailed explana-
tions are given below.
The studies by the present inventors have shown
that, in step (1), a carbonic ester is obtained by the
reaction between the reactive organometal compound and
carbon dioxide. Therefore, the use of a second alcohol
in step (1) is optional. However, from the viewpoint
of producing a carbonic ester in high yield, it is pre-
ferred to use a second alcohol in step (1). The reason
for this is as follows. The thermal decomposition re-
action in step (1) has a reverse reaction. When a sec-
ond alcohol is added to the reaction system, it is pos-
sible that another equilibrium reaction additionally
occurs between the second alcohol and a thermal decom-
position product other than the carbonic ester, thereby
improving the yield of the carbonic ester. The addi-
tion of a second alcohol for improving the yield of the
carbonic ester is especially effective when the reac-
tive organometal compound is comprised mainly of an or-
ganometal compound represented by formula (2). On the
other hand, when the reactive organometal compound is

comprised mainly of an organometal compound represented
by formula (1), the equilibrium of the thermal decompo-
sition reaction in step (1) is biased toward the prod-
uct system and, hence, the yield of the carbonic ester
is considerably high, so that, in some cases, the yield
of the carbonic ester cannot be further improved by the
addition of a second alcohol. When the second alcohol
contains a large amount of water, the yield of the car-
bonic ester is lowered. Therefore, it is preferred
that the amount of water contained in the second alco-
hol is not more than 0.1 times, more advantageously not
more than 0.01 times, as large as the stoichiometric
amount relative to the amount of the reactive organome-
tal compound. When the reaction in step (1) is per-
formed using an organometal compound represented by
formula (1), a carbon dioxide adduct of the organometal
compound represented by formula (1) is thermally decom-
posed to produce a carbonic ester. It is well known
that a carbonic ester is produced from a dimer of the
organometal compound represented by formula (1) (see
ECO INDUSTRY, Vol. 6, No. 6, pages 11-18 (2001)). In
the conventional method described in this literature, a
carbonic ester as well as dibutyltin oxide is produced
from a dimer of the organometal compound represented by
formula (1), wherein the amount of the carbonic ester

produced is two molecules per molecule of the dimer of
the organometal compound. The present inventors have
made extensive and intensive studies on the formation
of a carbonic ester from an organometal compound. As a
result, it has surprisingly been found that, when a
carbon dioxide adduct of a dimer of the organometal
compound represented by formula (1) is thermally decom-
posed, a carbonic ester is swiftly eliminated wherein
the amount of the carbonic ester eliminated is one
molecule per molecule of the carbon dioxide adduct, so
that an organometal compound represented by formula (2)
and/or a carbon dioxide adduct thereof can be obtained.
In this case, addition of an alcohol is not necessary.
Step (2) may be performed immediately after there are
obtained a carbonic ester and at least one compound se-
lected from the group consisting of an organometal com-
pound represented by formula (2) and a carbon dioxide
adduct thereof. Alternatively, step (2) may be per-
formed after a carbonic ester is further produced from
the obtained organometal compound represented by for-
mula (2) and/or the obtained carbon dioxide adduct
thereof. As mentioned above, it is preferred that the
reactive organometal compound used in step (1) com-
prises at least one compound selected from the group
consisting of organometal compounds respectively repre-

sented by formulae (1) and (2). It is more preferred
that at least a part of the reactive organometal com-
pound used in step (1) is an organometal compound rep-
resented by formula (1). It is still more preferred
that the reactive organometal compound used in step (1)
contains 5 mol % or more of an organometal compound
represented by formula (1), wherein the amount of the
organometal compound is expressed in terms of the
amount of a metal atom contained in the organometal
compound.
A solvent for the reactive organometal compound
may be used in step (1). The reactive organometal com-
pound used in the present invention is generally in the
form of a liquid. However, in some cases, the reactive
organometal compound is in the form of a solid. Fur-
ther, there is a case where the reactive organometal
compound turns into a solid form when the reactive or-
ganometal compound becomes a carbon dioxide adduct
thereof in step (1). Even when the reactive organome-
tal compound is in the form of a solid, a carbonic es-
ter can be produced in step (1). However, the fluidity
of the reactive organometal compound is sometimes im-
portant when the carbonic ester is continuously pro-
duced. Further, for improving the rate of the reaction
between the reactive organometal compound and carbon

dioxide, it is sometimes preferred that the reactive
organometal compound is in the form of a liquid. In
such cases, step (1) may be performed using a solvent
for the reactive organometal compound. As a solvent,
there can be used an alcohol having the same organic
group as in the carbonic ester produced. Alternatively,
an inert solvent can also be used. Examples of inert
solvents include hydrocarbons and ethers. Specific ex-
amples of inert solvents include C5-C20 saturated hydro-
carbons, such as pentane, hexane, cyclohexane, heptane,
octane and decane; C6-C20 aromatic hydrocarbons (which
may have a C1-C14 saturated alkyl group and/or a C5-C14
cycloalkyl group), such as benzene, toluene, xylene and
ethylbenzene; C6-C20 saturated alkyl ethers, such as
dipropyl ether, dibutyl ether and dihexyl ether; C4-C20
cycloalkyl ethers, such as tetrahydrofuran and dioxane;
and C7-C28 phenyl ethers (comprising a phenyl group hav-
ing a C0-C8 substituent group, and a group selected from
the group consisting of a C1-C14 alkyl group and a C5-C14
cycloalkyl group), such as anisole, ethyl phenyl ether,
isopropyl phenyl ether, benzyl methyl ether and 4
-methyl anisole.
The temperature employed for the reaction per-
formed in step (1) is generally in the range of from
room temperature (20 °C) to 300°C. When it is intended

to complete the reaction in a short period of time, it
is preferred to perform the reaction at 80 to 200 °C
for 10 minutes to 500 hours. When the reaction in step
(1) is performed at a high temperature (e.g., at 200 °C
or more), the 119Sn-NMR chart obtained with respect to
the reaction mixture after step (1) sometimes exhibits
a peak ascribed to a certain substance around 100 ppm,
wherein tetramethyltin is used as a reference in the
119Sn-NMR analysis. However, when the method of the
present invention is repeatedly performed, it is pre-
ferred that the reaction in step (1) is performed under
conditions wherein the formation of the above-mentioned
substance exhibiting a peak around 100 ppm can be sup-
pressed, or the reaction in step (1) is performed using
an additive for suppressing the formation of the above
-mentioned substance exhibiting a peak around 100 ppm.
With respect to the amount of carbon dioxide, when
the reaction in step (1) is performed at room tempera-
ture (20 °C), it suffices if carbon dioxide is used in
an amount which is the stoichiometric amount relative
to the amount of the reactive organometal compound used
in step (1). However, when the reaction in step (1) is
performed at a temperature which is higher than room
temperature (20 °C) under conditions wherein the amount
of carbon dioxide is the stoichiometric amount relative

to the amount of the reactive organometal compound used
in step (1), the rate of the addition bonding of carbon
dioxide to the reactive organometal compound sometimes
becomes very low, so that the rate of the formation of
the carbonic ester is markedly lowered. The pressure
employed for the reaction performed in step (1) is gen-
erally from atmospheric pressure to 200 MPa, preferably
from atmospheric pressure to 100 MPa, wherein, if de-
sired, the reaction may be performed while introducing
additional carbon dioxide into the reaction system or
withdrawing a part of carbon dioxide from the reaction
system. The introduction of additional carbon dioxide
into the reaction system may be performed either inter-
mittently or continuously.
In the method of the present invention, the reac-
tion system in step (1) may contain substances other
than mentioned above. Examples of other substances
which are useful in step (1) include those which func-
tion as a dehydrating agent in the reaction system. By
using a dehydrating agent in step (1), the reaction
system can be maintained non-aqueous. As a dehydrating
agent, any conventional organic dehydrating agent may
be used. Examples of dehydrating agents include acet-
als and orthoesters, such as orthotrimethyl acetate.
Further, dicyclohexylcarbodiimide and the like may also

be used as an organic dehydrating agent. Alternatively,
solid dehydrating agents, such as molecular sieves, may
be used as a dehydrating agent. When a solid dehydrat-
ing agent is used, it is preferred that the solid dehy-
drating agent is removed from the reaction system be-
fore step (3) is performed.
In step (1) of the method of the present invention,
an alcohol (second alcohol) is optionally used. From
the viewpoint of improving the purity of the carbonic
ester, as the second alcohol, it is preferred to use an
alcohol having an organic group which is the same as
the organic group of the oxy group (e.g., an alkoxy
group or an aralkyloxy group) of the reactive organome-
tal compound. When such an alcohol is used as the sec-
ond alcohol, it is preferred that the amount of the
second alcohol is 1 to 100,000 times the stoichiometric
amount relative to the amount of the reactive organome-
tal compound. On the other hand, when an alcohol hav-
ing an organic group different from that of the oxy
group of the reactive organometal compound is used as
the second alcohol or when, as the reactive organometal
compound, only an organometal compound of formula (2)
is used, the amount of the second alcohol is preferably
2 to 1,000 times, more preferably 10 to 1,000 times, as
large as the stoichiometric amount relative to the

amount of the reactive organometal compound. When an
alcohol having an organic group different from that of
the oxy group of the reactive organometal compound is
used as the second alcohol, an asymmetric carbonic es-
ter is produced in step (1). As mentioned below, when
a second alcohol is used in step (1), especially in the
case where the organometal compound represented by for-
mula (2) is used alone, the yield of the carbonic ester
is greatly improved. The above-mentioned preferred
amount of the second alcohol in the case where the or-
ganometal compound represented by formula (2) is used
alone, is determined from this viewpoint.
In the case where the below-mentioned step (4) is
followed by step (1), a second alcohol may be added to
the reaction system so that the amount of the second
alcohol falls within the above-mentioned preferred
range. Alternatively, in such case where step (4) is
followed by step (1), an alcohol may be removed from
the reaction system.
As mentioned above, in step (1) of the method of
the present invention, by performing a reaction between
a first organometal compound mixture comprising a mix-
ture of a reactive organometal compound and an unregen-
erable unreactive compound (which is derived from the
reactive organometal compound) and carbon dioxide.

there is obtained a reaction mixture containing a car-
bonic ester formed by the reaction, the unregenerable
unreactive compound (i.e., the degraded compound) and a
regenerable metamorphic organometal compound derived
from the reactive organometal compound.
When it is confirmed by the analysis of the reac-
tion mixture that a desired carbonic ester has been ob-
tained, step (1) is finished. For example, when the
carbonic ester is obtained in an amount which is 5 % or
more, based on the stoichiometric amount relative to
the amount of the reactive organometal compound, step
(1) may be finished. The reaction mixture may be taken
out from the reactor, either after the pressure in the
reactor is reduced to atmospheric pressure, or without
lowering the pressure in the reactor. When step (1),
step (2) and step (3) are performed in separate reac-
tors, the reaction mixture may be continuously circu-
lated by, for example, a method in which the reaction
mixture after step (3) is fed to the reactor for step
(1); the reaction mixture contained in the reactor for
step (1) is fed to the reactor for step (2); and the
reaction mixture contained in the reactor for step (2)
is fed to the reactor for step (3). The circulation of
the reaction mixture is preferred from the viewpoint of
reducing the amount of carbon dioxide purged from the

reactor (for step (1)) which has carbon dioxide filled
therein. The reaction mixture obtained at completion
of each step may be cooled or heated. When the reac-
tion mixture is cooled, the reaction mixture may be
forcibly cooled or allowed to cool spontaneously. As
described below, if desired, step (1) for synthesizing
a carbonic ester and step (2) for separating the syn-
thesized carbonic ester can be simultaneously performed.
Step (2) of the method of the present invention is
a step in which the reaction mixture obtained in step
(1) is separated into a first portion containing the
carbonic ester and the degraded compound (i.e., the un-
regenerable unreactive compound), and a second portion
containing the regenerable metamorphic organometal com-
pound. By such separation as to cause the degraded
compound derived from the reactive organometal compound
to be contained in the first portion containing the
carbonic ester (wherein the first portion is taken out
from the reaction system), it becomes possible to pre-
vent the degraded compound from accumulating in the re-
action system. Thus, all the problems of the conven-
tional methods have been solved by the method of the
present invention.
As described above, in the production of a car-
bonic ester from carbon dioxide and an alcohol by a

conventional method using the reaction of formula (3),
water as well as a carbonic ester is formed, and the
water is contacted with an adsorbent or a dehydrating
agent to remove the water from the reaction system,
thereby displacing the equilibrium of the reaction to-
ward the product system. Theoretically, the amount of
a carbonic ester produced can also be increased by con-
tinuously removing the produced carbonic ester from the
reaction system so as to displace the equilibrium of
the reaction toward the product system. However, in
the conventional method, when the produced carbonic es-
ter is removed from the reaction system, water produced
by the reaction accumulates in the reaction system. As
is well known in the art, if water accumulates in the
reaction system, the catalyst is hydrolyzed by the wa-
ter and loses its catalyst activity. The hydrolyzed
catalyst has very poor solubility in the solvent and,
hence, poses a problem in that, in a subsequent dehy-
dration step performed using an adsorption column, the
hydrolyzed catalyst causes clogging of the adsorption
column. Further, there has not been a method for re-
generating the catalyst which has lost its catalyst ac-
tivity by the hydrolysis thereof. For this reason, in
the conventional methods, it has been impossible to ef-
ficiently separate the produced carbonic ester from the

reaction mixture.
In step (2) of the method of the present invention,
a conventional method for separating the carbonic ester
from the reaction mixture can be used, so long as the
effect of the method of the present invention is not
impaired. For example, the separation of the carbonic
ester from the reaction mixture can be performed by any
of filtration, solvent extraction, distillation and
membrane filtration, each of which is well known in the
art. As a preferred example of an extraction solvent,
there can be mentioned a solvent having no reactivity
to the carbonic ester. Examples of such solvents in-
clude hydrocarbons, such as hexane and cyclohexane;
aromatic hydrocarbons, such as benzene, toluene and
chlorobenzene; and ethers, such as diethyl ether and
anisole. The distillation can be performed by any con-
ventional method. For example, the distillation can be
performed by any of a distillation under atmospheric
pressure, a distillation under reduced pressure, a dis-
tillation under superatmospheric pressure, and a thin
film distillation, each of which is well known in the
art. The temperature for the distillation varies de-
pending on the type of the carbonic ester to be pro-
duced, but it is preferred that the temperature is from
-20 to 200 °C. The distillation may be performed ei-

ther in the presence of a solvent or by extractive
distillation. On the other hand, as mentioned above,
when the distillation is performed under heating, the
separation of the carbonic ester by distillation is
sometimes accompanied by the following disadvantage.
When the distillation is performed under heating, a re-
verse reaction of a carbonic ester and other thermal
decomposition products in the equilibrium reaction is
sometimes caused to occur, thereby lowering the yield
of the carbonic ester. However, in such a case, when
the first portion containing a carbonic ester having a
high boiling point is separated from the reaction mix-
ture by distillation, the carbonic ester can be ob-
tained in high yield by separating the carbonic ester
from the reaction mixture at a rate which is higher
than the rate of the reverse reaction. For this pur-
pose, it is preferred to perform the distillation under
conditions wherein the distillation temperature and the
degree of pressure reduction are appropriately adjusted.
In step (2), if desired, a third alcohol may be
used. When a third alcohol is added to the reaction
system, an ester exchange reaction occurs between the
carbonic ester obtained in step (1) and the third alco-
hol to thereby obtain a carbonic ester which has a dif-
ferent number of carbon atoms from that of the carbonic

ester obtained in step (1). The amount of the third
alcohol used in step (2) is 1 to 1,000 times the
stoichiometric amount relative to the amount of the re-
active organometal compound used in step (1). The tem-
perature employed for the ester exchange reaction is
preferably in the range of from room temperature (about
20 °C) to 200 °C. Taking into consideration the desired
rate of the ester exchange reaction and the occurrence
of a decomposition reaction of the carbonic ester at a
high temperature, the temperature employed for the es-
ter exchange reaction is more preferably in the range
of from 50 to 150 °C. In the ester exchange reaction,
a conventional catalyst may be used. The ester ex-
change reaction and the separation of the carbonic es-
ter from the reaction mixture may be performed either
in a batchwise manner or simultaneously. As a method
for separating the first portion containing the car-
bonic ester from the reaction mixture after the ester
exchange reaction, any of the above-mentioned separa-
tion methods (such as filtration, solvent extraction,
distillation and membrane filtration) can be used.
By the method of the present invention, not only a
symmetric carbonic ester but also an asymmetric car-
bonic ester can be produced. In the case of the pro-
duction of an asymmetric carbonic ester by using a con-

ventional method, a symmetric carbonic ester is first
produced, and the produced symmetric carbonic ester is
then subjected to an ester exchange reaction to produce
an asymmetric carbonic ester. On the other hand, in
the method of the present invention, an asymmetric car-
bonic ester can be directly produced. Therefore, the
method of the present invention is advantageous from
the viewpoint of reducing the energy cost and reducing
the facility construction cost. In the method of the
present invention, an asymmetric carbonic ester can be
produced as follows. Explanations are given below,
taking as an example the case where the reactive
organometal compound has at least one type of alkoxy
group. When the reactive organometal compound used in
step (1) has two different types of alkoxy groups, an
asymmetric carbonic ester can be produced without use
of alcohols (as a second alcohol and a third alcohol)
in steps (1) and (2). On the other hand, when the or-
ganometal compound used in step (1) has only one type
of alkoxy group, an asymmetric carbonic ester can be
produced by performing step (1) in the presence of an
alcohol (second alcohol) having an organic group which
is different from the alkoxy group of the reactive or-
ganometal compound, or by performing step (2) in the
presence of an alcohol (third alcohol) having an or-

ganic group which is different from the alkoxy group of
the reactive organometal compound. Further, in each of
the case where the reactive organometal compound used
in step (1) has only one type of alkoxy group and the
case where the reactive organometal compound used in
step (1) has two different types of alkoxy groups, an
asymmetric carbonic ester can also be produced by per-
forming step (1) in the presence of two different alco-
hols (second alcohols), or by performing step (2) in
the presence of two different alcohols (third alcohols).
When two different alcohols are used, the stoichiomet-
ric ratio of the two alcohols varies depending on the
types of the two alcohols; however, the stoichiometric
ratio is generally in the range of from 2:8 to 8:2,
wherein each of the amounts of the two alcohols is ex-
pressed in terms of the stoichiometric amount relative
to the amount of the reactive organometal compound.
When it is intended to produce an asymmetric carbonic
ester in an amount which is larger than that of a sym-
metric carbonic ester, it is preferred that the
stoichiometric ratio of the two alcohols is as close to
1:1 as possible. Specifically, the stoichiometric ra-
tio of the two alcohols is preferably in the range of
from 3:7 to 7:3, more preferably in the range of from
4:6 to 6:4. When the production of an asymmetric car-

bonic ester is performed using two different alcohols
which are used in excess amounts (for example, amounts
each of which is at least 10 times the stoichiometric
amount relative to the amount of the reactive organome-
tal compound), it becomes possible to obtain an asym-
metric carbonic ester having two different types of
alkoxy groups corresponding to the two alcohols, irre-
spective of the type of the alkoxy group of the reac-
tive organometal compound used in step (1). The sepa-
ration of the first portion containing the asymmetric
carbonic ester from the reaction mixture can be per-
formed by any of the methods (such as filtration, sol-
vent extraction, distillation and membrane filtration)
described above in connection with step (2). In many
cases, not only an asymmetric carbonic ester but also a
symmetric carbonic ester is produced. In such cases,
the following operation may be performed. The asymmet-
ric and symmetric carbonic esters are separated from
the first portion. The asymmetric carbonic ester is
separated from the symmetric carbonic ester. The sym-
metric carbonic ester is either added to the second
portion containing the regenerable metamorphic compound,
followed by performing step (3), or returned to step
(1) or (2).
As mentioned above, in step (2) of the method of

the present invention, a mixture containing a degraded
compound derived from the reactive organometal compound
and the carbonic ester is separated from the reaction
mixture as the first portion. With respect to the re-
moval of the degraded compound, all of the degraded
compound may be removed or a part of the degraded com-
pound may be removed. The amount of the degraded com-
pound removed may vary depending on the size of the re-
actor and/or the number of turnovers (i.e., the number
of cycles of regeneration and reuse) of the reactive
organometal compound. It is preferred that 10 % or
more of the degraded compound is removed. It is more
preferred that 50 % or more of the degraded compound is
removed.
With respect to the separation method performed in
step (2) of the method of the present invention, more
detailed explanations are given below. The separation
of the reaction mixture obtained in step (1) into the
first portion and the second portion can be performed
by any of the above-mentioned conventional methods. As
preferred examples of such methods, there can be men-
tioned a method in which water is added to the reaction
mixture to effect a phase separation, and a method us-
ing distillation. Each of these methods are explained
below.

1) A separation method in which water is added to the
reaction mixture:
Water or a water-containing solvent is added to
the reaction mixture obtained in step (1) to form a
white slurry, and solids in the white slurry are re-
moved by filtration. By the filtration, the second
portion containing the regenerable metamorphic or-
ganometal compound can be obtained as a filtration
residue and the first portion containing the carbonic
ester and the degraded compound can be obtained as a
filtrate. With respect to the water used in this
method, there is no particular limitation; however, it
is preferred to use a distilled water or a deionized
water.
The amount of water used in step (2) is generally
1 to 100 times the stoichiometric amount relative to
the amount of the reactive organometal compound used in
step (1). The amount of water needed for separating
the second portion (containing the regenerable metamor-
phic organometal compound) from the reaction mixture by
phase separation is at most 1 times as large as the
stoichiometric amount relative to the amount of the re-
active organometal compound used in step (1).
In step (2), the temperature at which water is
added to the reaction mixture obtained in step (1) is

in the range of from a temperature (e.g., -20 °C) at
which the water is not frozen in the reaction mixture
to 100 °C, preferably from 0 to 100 °C, more preferably
from 10 to 80 °C. From the viewpoint of satisfactorily
suppressing the occurrence of the hydrolysis of the
carbonic ester, it is more preferred to adjust the tem-
perature of water to 10 to 50 °C. When water is used
in step (2), water may be used alone or in combination
with a solvent other than water. As a solvent other
than water, it is preferred to use a solvent which does
not react with the carbonic ester. In this case, when
water is used in the form of a solution thereof in an
alcohol which is the same as the second alcohol used in
step (1), the separation of the solvent by the distil-
lation becomes easy. When a third alcohol is used in
step (2) to perform an ester exchange reaction, it is
preferred that water is used in the form of a solution
thereof in an alcohol which is the same as the alcohol
present in the reaction mixture after the ester ex-
change reaction.
In step (2), when water is added to the reaction
mixture, it is possible that the degraded compound also
gradually undergoes hydrolysis, thus causing the so-
lidification of the degraded compound. Therefore, it
is preferred that, after the addition of water to the

reaction mixture, the resultant white slurry is sub-
jected to filtration as quickly as possible upon com-
pletion of the solidification of the second portion
containing the regenerable metamorphic organometal com-
pound. The period of time from the addition of water
to the filtration varies depending on the types of the
reactive organometal compound and alcohol used. When
the separation in step (2) is performed at room tem-
perature, the period of time is in the range of from 30
seconds to 60 minutes, preferably from 1 to 10 minutes.
2) A separation method using distillation
The reaction mixture obtained in step (1) is sub-
jected to distillation to thereby separate the reaction
mixture into the first portion containing the carbonic
ester and the degraded compound and the second portion
containing the regenerable metamorphic organometal com-
pound. Each of the carbonic ester and the degraded
compound has a boiling point lower than that of the re-
generable metamorphic organometal compound. Therefore,
the distillation can be performed by any conventional
method. For example, the distillation can be performed
by any of a distillation under superatmospheric pres-
sure, a distillation under reduced pressure, a distil-
lation under heating, a thin film distillation and a
pervaporation using a membrane, each of which is well

known in the art.
The temperature employed for the distillation is
not particularly limited so long as the degraded com-
pound has a vapor pressure at the temperature; however,
the temperature is preferably from -20 to 300 °C. From
the viewpoint of minimizing the loss of the carbonic
ester contained in the reaction mixture caused by the
above-mentioned reverse reaction, it is more preferred
that the temperature employed for distillation is from
-20 to 200 °C. For adjusting the temperature employed
for distillation, the distillation may be performed ei-
ther under superatmospheric pressure or under reduced
pressure. Further, the distillation may be performed
either in a continuous manner or in a batchwise manner.
The separation of the carbonic ester from the
first portion (containing the carbonic ester and the
unregenerable unreactive compound) obtained in step (2)
can be performed easily by any of the conventional
methods, such as adsorption, distillation, filtration
and membrane separation.
Step (3) is a step of synthesizing (regenerating)
a reactive organometal compound having in its molecule
at least two metal-oxygen-carbon linkages. The com-
pound in the second portion obtained in step (2) is
generally in the form of a transparent or opaque liquid.

For example, the second portion does not contain dibu-
tyltin oxide in the form of a solid (it should be noted
that dibutyltin oxide has no solubility in almost all
organic solvents at room temperature (20 °C) and, hence,
is in the form of a solid under such conditions). The
structure of the compound in the second portion has not
yet been identified. However, it has surprisingly been
found that, by performing the reaction in step (3) of
the method of the present invention, there can be ob-
tained a reactive organometal compound having in its
molecule at least two metal-oxygen-carbon linkages,
such as an organometal compound represented by formula
(1) or an organometal compound represented by formula
(2).
Step (3) comprises reacting the second portion (of
the reaction mixture) obtained in step (2) with a first
alcohol to form a second organometal compound mixture
and water and removing the water from the second or-
ganometal compound mixture, wherein the second or-
ganometal compound mixture comprises a mixture of a re-
active organometal compound having in its molecule at
least two metal-oxygen-carbon linkages and an unregen-
erable unreactive compound which is derived from the
reactive organometal compound. If desired, the method
of the present invention may further comprise, after

step (3), a step (4) in which the second organometal
compound mixture obtained in step (3) is recovered and
recycled to step (1).
Examples of first alcohols used in step (3) in-
clude those which are exemplified above. If desired,
prior to use of any of the above-mentioned alcohols,
distillation of the alcohol may be performed for puri-
fying the alcohol or adjusting the concentration of the
alcohol. From this viewpoint, it is preferred to use
an alcohol having a boiling point of 300 °C or lower as
measured under atmospheric pressure. From the view-
point of the ease in the removal of water in step (3),
it is more preferred to use at least one alcohol se-
lected from the group consisting of 1-butanol, 2
-methyl-1-propanol, an alkyl alcohol having five or
more carbon atoms, and an aralkyl alcohol having five
or more carbon atoms.
With respect to the structure of a reactive or-
ganometal compound obtained by using a polyhydric alco-
hol as a first alcohol in step (3), there is no par-
ticular limitation. For example, the organometal com-
pound may be comprised of at least one member selected
from the group consisting of a crosslinked product of
an organometal compound represented by formula (1) and
a crosslinked product of an organometal compound repre-

sented by formula (2).
The amount of the first alcohol used in step (3)
is preferably 1 to 10,000 times, more preferably 2 to
100 times, the stoichiometric amount relative to the
amount of the reactive organometal compound used in
step (1). When a sequence of steps (1) to (4) is re-
peated one or more times, it is sometimes possible that
an alcohol is present in the second portion obtained in
step (2). In such cases, an appropriate amount of an
alcohol may be added to the second portion so that the
amount of the alcohol in the second portion falls
within the above-mentioned range of the amount of the
first alcohol. Alternatively, the alcohol present in
the second portion may be removed.
The removal of water in step (3) can be performed
by any conventional method. For example, the removal
of water in step (3) can be performed by any of distil-
lation, a method using a dehydration column packed with
a solid dehydrating agent (such as molecular sieves),
and a method using membrane separation (such as per-
vaporation). Among them, distillation and a method us-
ing membrane separation (such as pervaporation) are
preferred. It is well known that pervaporation can be
used for the removal of water in an alcohol. In the
present invention, pervaporation can be preferably used.

In the case of an alcohol having a boiling point higher
than that of water, the removal of water in the alcohol
can also be easily performed by distillation under
heating. On the other hand, in the case of an alcohol
having a boiling point lower than that of water, the
removal of water in the alcohol can also be performed
by a distillation technique in which a solvent forming
an azeotropic mixture with water is used. As mentioned
above, the removal of water in the alcohol can be per-
formed by any of a method using a solid dehydrating
agent, distillation and membrane separation. However,
when it is desired to obtain the second organometal
compound mixture in a large amount in a short period of
time, it is preferred that the removal of water in the
alcohol is performed by distillation. The distillation
can be performed by any conventional method. For exam-
ple, the distillation can be performed by any of a dis-
tillation under atmospheric pressure, a distillation
under reduced pressure, a distillation under superat-
mospheric pressure, a thin film distillation and an ex-
tractive distillation, each of which is well known in
the art. The distillation can be performed at a tem-
perature of from -20oC to the boiling point of the
first alcohol used in step (3). It is preferred that
the distillation temperature is from 50°C to the boil-

ing point of the first alcohol used in step (3). Be-
fore or during the distillation, any desired substance
may be added to the second portion of the second por-
tion of the reaction mixture. The second portion of
reaction mixture may contain, for example, a solvent
which forms an azeotropic mixture with water from the
viewpoint of the ease in the removal of water in step
(3); or a solvent which enhances the hydrophobic prop-
erty of the second portion of the reaction mixture so
that the vapor-liquid equilibrium of the water formed
by the reaction in step (3) becomes advantageous. Fur-
ther, the second portion of the reaction mixture may
contain a solvent which adjusts the fluidity of the
second portion of the reaction mixture.
The temperature employed for the reaction per-
formed in step (3) varies depending on the type of the
first alcohol used; however, the temperature is gener-
ally from room temperature (about 20°C) to 300°C.
When the removal of water in step (3) is performed by
distillation, the temperature employed for the distil-
lation is not particularly limited so long as water has
a vapor pressure at the temperature. When it is in-
tended to complete the reaction in step (3) in a short
period of time under atmospheric pressure, it is pre-
ferred that the distillation is performed under condi-

tions wherein the temperature of the vapor formed by
distillation is the azeotropic temperature of water and
the first alcohol. When water and the first alcohol do
not form an azeotropic mixture, it is preferred that
the distillation is performed at the boiling point of
water. When it is intended to complete the reaction in
step (3) in a shorter period of time, the distillation
may be performed, using an autoclave, at a temperature
higher than the boiling point of the first alcohol or
water while gradually removing water in the vapor phase.
When the temperature employed for the reaction per-
formed in step (3) is extremely high, it is sometimes
possible that a thermal decomposition of the reactive
organometal compound occurs. In such cases, a liquid
containing water may be removed by reduced pressure
distillation or the like.
Even when the first alcohol does not form an
azeotropic mixture with water, water can be removed by
azeotropic distillation in which a solvent forming an
azeotropic mixture with water is used. This method is
preferred since water can be removed at a low tempera-
ture. Examples of solvents which form an azeotropic
mixture with water include unsaturated and saturated
hydrocarbons, such as hexane, benzene, toluene, xylene,
naphthalene; ethers, such as anisole and 1,4-dioxane;

and halogenated hydrocarbons, such as chloroform.
From the viewpoint of facilitating the separation
of water from the azeotropic mixture after azeotropic
distillation, it is preferred to use, as a solvent, an
unsaturated or saturated hydrocarbon in which water has
low solubility. When such a solvent is used, it is
necessary to use the solvent in an amount such that wa-
ter can be satisfactorily removed by azeotropic distil-
lation. It is preferred to use a distillation column
for the azeotropic distillation because the solvent can
be recycled to the reaction system after separating the
solvent from the azeotropic mixture in the distillation
column and, hence, the amount of the solvent can be re-
duced to a relatively small one.
By performing the reaction in step (3), there can
be obtained, for example, an organometal compound mix-
ture containing at least one reactive organometal com-
pound selected from the group consisting of an or-
ganometal compound represented by formula (1) and an
organometal compound represented by formula (2).
When the reaction in step (3) reaches a stage
where almost no water is generated, step (3) can be
finished. When a sequence of steps (1) to (4) is re-
peated one or more times, the amount of the carbonic
ester obtained in step (1) varies depending on the

amount of water which is removed in step (3). There-
fore, it is preferred that the amount of water removed
in step (3) is as large as possible.
Generally, the amount of water removed in step (3)
is 0.01 to 1 times as large as the amount of water pro-
duced by the reaction in step (3), wherein the amount
of water produced is theoretically calculated based on
the assumption that only an organometal compound repre-
sented by formula (1) is produced by the reaction in
step (3). In many cases, the amount of water removed
in step (3) is less than 1 times as large as the above
-mentioned theoretical amount of water produced by the
reaction in step (3). As a result of the studies made
by the present inventors, it has been found that, when
an organometal compound is produced from dibutyltin ox-
ide and an alcohol and a sequence of steps (1) to (4)
is repeated one or more times, the amount of water re-
moved in step (3) is less than the amount of water gen-
erated during the reaction in which the reactive or-
ganometal compound is produced from dibutyltin oxide
and an alcohol. When, in step (2), water is added to
the reaction system for separating the first portion
containing the carbonic ester and the degraded compound,
it is sometimes possible that a white solid containing
water is obtained and the amount of water removed in

step (3) is more than 1 times the above-mentioned theo-
retical amount of water produced by the reaction in
step (3). When a sequence of steps (1) to (4) is re-
peated one or more times, it is difficult to calculate
a theoretical amount of water produced by the reaction
performed in step (3) because the structure of the re-
generable metamorphic organometal compound contained in
the reaction mixture obtained in step (1) has not yet
been identified. In this case, the change (with time)
in the amount of water which is removed is measured.
When it is confirmed by the measurement that almost no
more water is removed, step (3) may be finished.
After completion of step (3), if desired, an ex-
cess amount of the alcohol may be removed. From the
viewpoint of improving the purity of the carbonic ester
obtained in step (1) in the case where a sequence of
steps (1) to (4) is repeated one or more times, it is
preferred to remove an excess amount of the alcohol.
When the same alcohol as used in step (3) is used in
step (1) in the case where a sequence of steps (1) to
(4) is repeated one or more times, the removal of the
alcohol after step (3) may not be performed. Further,
an appropriate amount of the alcohol may be added to
the reaction system after step (3).
The removal of an excess amount of the alcohol can

be performed as follows. When the second organometal
compound mixture obtained in step (3) is in the form of
a solid, the alcohol can be removed as a filtrate ob-
tained by filtration. On the other hand, when the sec-
ond organometal compound mixture obtained in step (3)
is in the form of a liquid, the removal of the alcohol
can be performed by a distillation under reduced pres-
sure, or by a method in which an inert gas, such as ni-
trogen, is introduced into the reactor so that the al-
cohol is removed in an amount which corresponds to the
vapor pressure of the alcohol. In the case of using an
inert gas, when the inert gas is not completely dried,
a disadvantage is likely to occur wherein the second
organometal compound mixture is hydrolyzed and decom-
posed into a metal oxide and an alcohol, so that the
amount of the carbonic ester obtained by the reaction
in step (1) in the case where a sequence of steps (1)
to (4) is repeated one or more times, becomes extremely
lowered. Steps (1) to (3) may be performed either in-
termittently or in a batchwise manner.
As described above, if desired, steps (1) and (2)
can be simultaneously performed. Also, if desired,
steps (2) and (3) can be simultaneously performed.
Further, steps (1) to (3) can also be simultaneously
performed. Further, when the method of the present in-

vention is repeated one or more times, if desired, step
(3) and step (1) of the subsequent cycle can be simul-
taneously performed. With respect to the cases where
these steps are simultaneously performed, explanations
are given below.
(The case where steps (1) and (2) are simultaneously
performed)
With respect to the reaction performed in step (1),
there are two cases: one (first case) is the case where
a liquid phase and a vapor phase are present during the
performance of the reaction in step (1), and the other
(second case) is the case where carbon dioxide is in a
supercritical state under high temperature and high
pressure conditions and the reaction mixture forms a
homogeneous mixture. Steps (1) and (2) can be simulta-
neously performed in the first case. In the first case,
the reaction temperature and reaction pressure vary
depending on the type of an alkoxy group contained in
the reactive organometal compound and the type of an
alcohol when an alcohol is used. However, the reaction
temperature is generally 200 °C or lower and the reac-
tion pressure is 8 MPa or less. The carbonic ester has
high solubility in carbon dioxide and, hence, a part of
the carbonic ester is dissolved in the vapor phase.

Therefore, by performing the reaction in step (1) while
withdrawing a part of the vapor phase, the first por-
tion (containing the carbonic ester and the unregener-
able unreactive compound) can be separated from the re-
action mixture.
(The case where steps (2) and (3) are simultaneously
performed)
Steps (2) and (3) can be simultaneously performed
when the reactive organometal compound is obtained from
an alcohol having a boiling point higher than that of
water, and a C1-C3 alkyl alcohol is used in step (1) or
(2). The separation of the carbonic ester, the de-
graded compound and water from the reaction mixture can
be performed by a method in which the reaction mixture
obtained in step (1) is placed under a stream of an in-
ert gas, such as carbon dioxide gas, thereby removing
the carbonic ester, the degraded compound and water
from the reaction mixture, in such a form as entrained
by the inert gas. The separation of the carbonic ester,
the degraded compound and water from the reaction mix-
ture can also be performed by a conventional method,
such as membrane separation. By such a method, the
carbonic ester, the degraded compound and water can be
continuously separated from the reaction mixture.

(The case where steps (1) to (3) are simultaneously
performed)
With respect to the reaction performed in step (1),
there are two cases: one (first case) is the case where
a liquid phase and a vapor phase are present during the
performance of the reaction in step (1), and the other
(second case) is the case where carbon dioxide is in a
supercritical state under high temperature and high
pressure conditions and the reaction mixture forms a
homogeneous mixture. Steps (1) to (3) can be simulta-
neously performed in the case where a liquid phase and
a vapor phase are present during the performance of the
reaction in step (1), the reactive organometal compound
is obtained from an alcohol having a boiling point
higher than that of water, and a C1-C3 alkyl alcohol
(preferably methanol or ethanol) is used. In this case,
the reaction temperature and reaction pressure vary de-
pending on the type of an alkoxy group contained in the
reactive organometal compound and the type of an alco-
hol when an alcohol is used. However, the reaction
temperature is generally 150°C or less and the reac-
tion pressure is generally 5 MPa or less. Water, the
carbonic ester and the degraded compound have high
solubility in carbon dioxide and, hence, a part of each

of the water, the carbonic ester and the degraded com-
pound is dissolved in the vapor phase. Therefore, by
performing the reaction in step (1) while withdrawing a
part of the vapor phase, the carbonic ester and the de-
graded compound can be separated from the reaction mix-
ture while regenerating the organometal compound. Fur-
ther, it is also possible to employ a method in which
the reaction is performed in a fixed-bed reactor con-
taining an organometal compound mixture, wherein the
organometal compound mixture is supported on a carrier
or in the form of a solid. In this method, carbon di-
oxide and a C1-C3 alcohol are introduced into the fixed
-bed reactor to effect a reaction, thereby obtaining a
carbonic ester, a degraded compound and water in such a
form as entrained by carbon dioxide gas. As a carrier
for supporting the organometal compound mixture, a con-
ventional carrier can be used.
(The case where step (3) and step (1) of the subsequent
cycle are simultaneously performed when the method of
the present invention is repeated one or more times)
When the method of the present invention is re-
peated one or more times, step (3) and step (1) of the
subsequent cycle can be simultaneously performed by a
method in which step (3) is performed in an atmosphere

of or in the presence of carbon dioxide gas. Specifi-
cally, step (3) and step (1) of the subsequent cycle
can be simultaneously performed by a method in which
the second portion (of the reaction mixture) obtained
in step (2) is reacted with a first alcohol to regener-
ate (resynthesize) a reactive organometal compound and
generate water, and the regenerated reactive organome-
tal compound is reacted with carbon dioxide to thereby
obtain a carbonic ester, wherein the water generated is
removed. Step (3) and step (1) of the subsequent cycle
can be simultaneously performed in the case where a
liquid phase and a vapor phase are present in the reac-
tion system. In this case, the reaction temperature
and reaction pressure vary depending on the type of an
alkoxy group contained in the reactive organometal com-
pound and the type of an alcohol used. However, the
reaction temperature is generally 200 °C or lower and
the reaction pressure is 1 MPa or less. It is pre-
ferred that step (3) and step (1) of the subsequent cy-
cle are performed simultaneously by reacting the reac-
tive organometal compound with carbon dioxide in the
presence of an alcohol having a boiling point higher
than 100°C (as measured under atmospheric pressure)
under conditions wherein the reaction temperature is
the same or lower than the boiling point of the alcohol

and the pressure is from atmospheric pressure to 0.5
MPa. It is more preferred that step (3) and step (1)
of the subsequent cycle are performed simultaneously by
a method in which carbon dioxide gas is introduced into
the second portion of the reaction mixture so that the
water generated is withdrawn from the reaction system
in such a form as entrained by carbon dioxide gas.
As mentioned above, the method of the present in-
vention may further comprise, after step (3), a step
(4) in which the second organometal compound mixture
obtained in step (3) is recovered and recycled to step
(1). A sequence of steps (1) to (4) can be repeated
one or more times. Prior to the recycle of the or-
ganometal compound to step (1), the organometal com-
pound may be cooled or heated. The step (4) can be
performed either continuously or in a batchwise manner.
In step (3), when the reaction of the second por-
tion of the reaction mixture with a first alcohol is
performed at a high temperature or for a prolonged pe-
riod of time, a problem arises in that the degraded
compound is formed in a large amount. Therefore, it is
preferred that the reaction in step (3) is performed
under conditions wherein the formation of the degraded
compound is suppressed as much as possible. The de-
graded compound (i.e., the unregenerable unreactive

compound) is formed by a disproportionation reaction
which is caused to occur when the organometal compounds
respectively represented by formulae (1) and (2) are
heated. In a carbon dioxide atmosphere, such dispro-
portination reaction progresses slowly and, hence, the
unregenerable unreactive compound is formed mainly in
this step (3). With respect to the degraded compound
formed and accumulated prior to the reaction of step
(3), and the degraded compound being formed during the
reaction in step (3), these degraded compounds can be
removed from the reaction system in step (3). The rea-
son is that the degraded compound represented by for-
mula (6) above has a boiling point lower than that of
the reactive organometal compound obtained by the reac-
tion of step (3). The removal of the degraded compound
from the reaction system in step (3) can be performed
by a conventional method, such as distillation or mem-
brane separation. For example, the distillation can be
preferably performed by any of a distillation under su-
peratmospheric pressure, a distillation under reduced
pressure, a distillation under heating and a thin film
distillation. The membrane separation can be preferably
performed by, for example, a pervaporation using a mem-
brane. From the viewpoint of minimizing the number of
steps of the removal method employed, it is more pre-

ferred that the removal of the degraded compound is
performed by a method in which, after the water is re-
moved in step (3), the degraded compound is distilled
off under greatly reduced pressure. The temperature
employed for the distillation is not particularly lim-
ited so long as the degraded compound has a vapor pres-
sure at the temperature; however, the temperature is
preferably from about 20 °C to 300 °C. When the distil-
lation is performed under heating at a high temperature,
there is a danger that the amount of the degradation
compound formed further increases. Therefore, it is
more preferred that the temperature employed for dis-
tillation is from 20 to 200 °C.
In the method of the present invention, a solid
degraded compound (other than the above-mentioned unre-
generable unreactive compound) which has in its mole-
cule at least three metal-carbon linkages is sometimes
formed. It is presumed that such solid degraded com-
pound is derived from a disproportionation reaction
product which is formed as a counterpart of the unre-
generable unreactive compound having in its molecule at
least three metal-carbon linkages. As an example of
such solid degraded compound, there can be mentioned a
metal oxide, such as titanium oxide or tin oxide.
These solid degraded compounds can be easily removed

from the reaction system by filtration. In step (1),
step (2) (in the case where water is not used) and step
(3), the reaction mixture is generally present in the
form of a homogeneous liquid. Therefore, when solid
degraded compounds are precipitated in the reaction
system as a result of a repetitious use of the or-
ganometal compound, the solid degraded compounds can be
removed by filtration. The filtration can be performed
by any of the conventional methods. For example, the
filtration can be performed by any of a filtration
under atmospheric pressure, a filtration under reduced
pressure, a filtration under superatmospheric pressure
and a centrifugation. When water intrudes into the re-
action system during the filtration, there is a danger
that the useful organometal compound is hydrolyzed and
solidified. Therefore, for preventing the useful or-
ganometal compound from being removed together with the
solid degraded compound, it is preferred that the fil-
tration is performed with a considerable care so as to
suppress the occurrence of the hydrolysis of the or-
ganometal compound.
Hereinbelow, explanations are given with respect
to the reaction vessels used in the method of the pre-
sent invention.
With respect to the type of the reaction vessel

used in each of steps (1), (2) and (3), there is no
particular limitation, and any conventional reaction
vessel can be used. Examples of conventional reaction
vessels include a stirring vessel, a multi-stage stir-
ring vessel and a continuous multi-stage distillation
column. These reaction vessels can be used individu-
ally or in combination. Using at least one of the
above-mentioned reaction vessels, steps (1) to (3) may
be performed in a batchwise or continuous manner. Spe-
cifically, with respect to steps (1) and (3), from the
viewpoint of efficiently displacing the equilibrium of
the reaction in the direction of the product system, it
is preferred to use a multi-stage distillation column.
It is more preferred that each of steps (1) and (3) is
continuously performed using a multi-stage distillation
column.
With respect to the multi-stage distillation col-
umn, there is no particular limitation so long as it is
a distillation column which has two or more theoretical
stages and which is capable of continuous distillation.
As such a multi-stage distillation column, any conven-
tional multi-stage distillation column which is gener-
ally used in the art can be used. Examples of such
multi-stage distillation columns include plate type
columns using a tray, such as a bubble-cap tray, a

sieve tray, a valve tray or a counterflow tray; and
packed type columns packed with any of various packings,
such as a Raschig ring, a Lessing ring, a Pall ring, a
Berl saddle, an Interlox saddle, a Dixon packing, a
McMahon packing, a Heli pack, a Sulzer packing and Mel-
lapak. Further, a mixed type of plate column and
packed column, which comprises both a plate portion and
a portion packed with packings, can also be preferably
used.

BEST MODE FOR CARRYING OUT THE INVENTION
Hereinbelow, the present invention will be de-
scribed in more detail with reference to the following
Examples, which should not be construed as limiting the
scope of the present invention.

(1) Nuclear Magnetic Resonance (NMR) analysis of an
organometal compound
Apparatus: JNM-A400 FT-NMR system (manufactured
and sold by JEOL Ltd., Japan)
Preparation of sample solutions for 1H-, 13C- and
119Sn-NMR analyses:
About 0.1 to 1 g of a reaction mixture was weighed,
and then 0.05 g of tetramethyltin and about 0.85 g of
deuterated chloroform were added thereto, thereby ob-
taining a sample solution for an NMR analysis.
(2) Gas chromatography (GC) analysis of a carbonic es-
ter
Apparatus: GC-2010 system (manufactured and sold
by Shimadzu Corporation, Japan),
(i) Preparation of a sample solution
0.06 g of a reaction mixture was weighed, and then
about 2.5 ml of dehydrated dimethylformamide or dehy-

drated acetonitrile was added thereto. Further, to the
resultant was added about 0.06 g of diphenyl ether as
an internal standard, thereby obtaining a sample solu-
tion for a GC analysis,
(ii) Conditions for a GC analysis
Column: DB-1 (manufactured and sold by J & W Sci-
entific, U.S.A.)
Liquid phase: 100 % dimethyl polysiloxane
Column length: 30 m
Column diameter: 0.25 mm
Film thickness: 1 µm
Column temperature: the temperature was elevated
from 50 °C to 300 °C at a rate of 10 °C/min.
Injection temperature: 300 °C
Detector temperature: 300 °C
Detector: FID (flame ionization detector)
(iii) Quantitative analysis
The quantitative analysis of a sample solution was
performed using a calibration curve obtained with re-
spect to standard samples.
(3) Calculation of the yield of a carbonic ester (i.e.,
dialkyl carbonate)
The yield of a dialkyl carbonate was expressed in
terms of the mol % of the dialkyl carbonate, based on

the molar amount of the organometal compound used in
step (1), wherein the amount of the organometal com-
pound is expressed in terms of the amount of a metal
atom contained therein.
Example 1
First, a reactive organometal compound having a 2-
ethylhexyloxy group was synthesized from dibutyltin ox-
ide and 2-ethyl-l-hexanol as follows.
Into a 1-liter four-necked flask equipped with a
cooling tube, a thermometer (for the measurement of the
internal temperature of the flask), a vacuum pump and a
vacuum controller (manufactured and sold by Okano Works,
Ltd., Japan) were charged 249 g (1.0 mol) of dibutyltin
oxide (manufactured and sold by Aldrich, U.S.A.), 650 g
(5.0 mol) of 2-ethyl-l-hexanol (manufactured and sold
by Aldrich, U.S.A.; a dehydrated grade). Further, a
stirrer was placed in the flask. The flask was im-
mersed in an oil bath. The atmosphere in the flask was
purged with nitrogen gas. Then, stirring of the con-
tents of the flask was started while heating. When the
internal temperature of the flask reached 172 °C, the
pressure in the flask was gradually reduced while with-
drawing a distillate (i.e., water and 2-ethyl-l
-hexanol) from the flask by means of a purge line, and

a reaction was performed for about 7 hours. By reduc-
ing the pressure in the flask, the pressure in the
flask was finally lowered to about 28 KPa. When the
distillate was almost thoroughly withdrawn from the
flask, the flask was taken out from the oil bath, and
the inside of the flask was cooled. Then, nitrogen gas
was introduced into the flask to elevate the pressure
in the flask to atmospheric pressure. By the above-
mentioned operation, 410 g of a viscous liquid was ob-
tained.
The distillate withdrawn from the flask was ana-
lyzed. As a result, it was found that the distillate
contained about 13 g of water. The above-obtained vis-
cous liquid was analyzed by 1H-, 13C- and 119Sn-NMR's.
As a result, it was found that the viscous liquid con-
tained 1,1,3,3-tetrabutyl-l,3-di(2-
ethylhexyloxy)distannoxane, dibutyltin di(2
-ethylhexyloxide) and tributyltin(2-ethylhexyloxide).
Step (1)
404 g of the above-obtained viscous liquid was
charged into a 500-ml autoclave (manufactured and sold
by Toyo Koatsu Co., Ltd., Japan) which had a carbon di-
oxide gas bomb connected thereto through a SUS tube and
a valve. The autoclave was sealed, and the atmosphere

in the autoclave was purged with nitrogen gas. Then,
the above-mentioned valve was opened to introduce car-
bon dioxide gas having a pressure of 4 MPa into the
autoclave. The introduction of carbon dioxide gas into
the autoclave was performed for 10 minutes while stir-
ring the contents of the autoclave, and, then, stopped
by closing the valve of the carbon dioxide gas bomb.
Subsequently, the internal temperature of the autoclave
was elevated to 120 oC while stirring. Then, a reac-
tion was performed for 3 hours while maintaining the
internal pressure of the autoclave at 4 MPa by means of
a back-pressure valve of the carbon dioxide gas bomb.
After the reaction, the inside of the autoclave was
cooled to about 30 °C, and carbon dioxide gas was gen-
tly purged therefrom through the purge line to lower
the pressure in the autoclave to atmospheric pressure,
thereby obtaining a transparent liquid as a reaction
mixture. It was found that the yield of di(2
-ethylhexyl) carbonate was 25 %. The reaction mixture
was analyzed by 1H-, 13C- and 119Sn-NMR' s. As a result,
it was confirmed that the reaction mixture contained
tributyltin(2-ethylhexyloxide) and a carbon dioxide ad-
duct thereof in a total amount of about 0.1 mol %.
These two compounds are unregenerable unreactive com-
pounds .

Step (2)
After step (1), a thin film distillation apparatus
(E-420; manufactured and sold by Shibata Scientific
Technology Ltd., Japan) having an internal temperature
of 130 ° C and an internal pressure of about 65 Pa was
connected to the autoclave through a liquid transfer-
ring pump (LC-10AT; manufactured and sold by Shimadzu
Corporation, Japan), and a distillation was performed
as follows. About 120 g of the reaction mixture ob-
tained in step (1) was charged into the thin film dis-
tillation apparatus through the liquid transferring
pump at a rate of 3 g/min to distill off the volatile
matter from the reaction mixture, followed by cooling,
thereby recovering about 14 g of the volatile matter in
a liquid form. It was found that about 50 % of the
di(2-ethylhexyl) carbonate contained in the reaction
mixture charged into the thin film distillation appara-
tus was distilled off as a volatile matter. The vola-
tile matter in a liquid form was analyzed by 1H-, 13C-
and 119Sn-NMR's. As a result, it was confirmed that the
volatile matter in a liquid form contained about 0.02
mol of tributyltin(2-ethylhexyloxide).
Step (3)

Into a 300-ml four-necked flask equipped with a
cooling tube, a thermometer (for the measurement of the
internal temperature of the flask), a vacuum pump and a
vacuum controller (manufactured and sold by Okano Works,
Ltd., Japan) were charged about 100 g of the distilla-
tion residue obtained by the above-mentioned distilla-
tion, 5 g (about 2 mmol) of dibutyltin oxide (manufac-
tured and sold by Aldrich, U.S.A.). and 216 g (1.7 mol)
of 2-ethyl-l-hexanol (manufactured and sold by Aldrich,
U.S.A.; a dehydrated grade). Further, a stirrer was
placed in the flask. The flask was immersed in an oil
bath. The atmosphere in the flask was purged with ni-
trogen gas. Then, stirring of the contents of the
flask was started while heating. When the internal
temperature of the flask reached 172 °C, the pressure
in the flask was gradually reduced while withdrawing a
distillate (i.e., water and 2-ethyl-l-hexanol) from the
flask by means of a purge line, and a reaction was per-
formed for about 7 hours. By reducing the pressure in
the flask, the pressure in the flask was finally low-
ered to about 28 KPa. When the distillate was almost
thoroughly withdrawn from the flask, the flask was
taken out from the oil bath, and the inside of the
flask was cooled. Then, nitrogen gas was introduced
into the flask to elevate the pressure in the flask to

atmospheric pressure. By the above-mentioned operation,
a viscous liquid was obtained.
The above-obtained viscous liquid was analyzed by
1H-, 13C- and 119Sn-NMR's. As a result, it was found
that the viscous liquid contained 1,1,3,3-tetrabutyl
-1,3-di(2-ethylhexyloxy)distannoxane, dibutyltin di(2
-ethylhexyloxide) and tributyltin(2-ethylhexyloxide).
Of these three compounds, the first two compounds are
regenerable metamorphic organometal compounds and the
last one compound is an unregenerable unreactive com-
pound.
The viscous liquid obtained in step (3) above was
recovered and recycled to step (1), and step (1) was
performed as follows.
79 g of the above-obtained viscous liquid was
charged into a 100-ml autoclave (manufactured and sold
by Toyo Koatsu Co., Ltd., Japan) which had a carbon di-
oxide gas bomb connected thereto through a SUS tube and
a valve. The autoclave was sealed, and the atmosphere
in the autoclave was purged with nitrogen gas. Then,
the above-mentioned valve was opened to introduce car-
bon dioxide gas having a pressure of 4 MPa into the
autoclave. The introduction of carbon dioxide gas into
the autoclave was performed for 10 minutes while stir-

ring the contents of the autoclave, and, then, stopped
by closing the valve of the carbon dioxide gas bomb.
Subsequently, the internal temperature of the autoclave
was elevated to 120 °C while stirring. Then, a reac-
tion was performed for 3 hours while maintaining the
internal pressure of the autoclave at 4 MPa by means of
a back-pressure valve of the carbon dioxide gas bomb.
After the reaction, the inside of the autoclave was
cooled to about 30 °C, and carbon dioxide gas was gen-
tly purged therefrom through the purge line to lower
the pressure in the autoclave to atmospheric pressure,
thereby obtaining a transparent liquid as a reaction
mixture. It was found that the yield of di(2
-ethylhexyl) carbonate was 25 %.
After step (1), a thin film distillation apparatus
(E-420; manufactured and sold by Shibata Scientific
Technology Ltd., Japan) having an internal temperature
of 130 ° C and an internal pressure of about 65 Pa was
connected to the autoclave through a liquid transfer-
ring pump (LC-10AT; manufactured and sold by Shimadzu
Corporation, Japan), and a distillation was performed
as follows. About 25 g of the reaction mixture ob-
tained in step (1) was charged into the thin film dis-
tillation apparatus through the liquid transferring
pump at a rate of 3 g/min to distill off the volatile

matter from the reaction mixture, followed by cooling,
thereby recovering about 14 g of the volatile matter in
a liquid form. It was found that about 50 % of the
di(2-ethylhexyl) carbonate contained in the reaction
mixture charged into the thin film distillation appara-
tus was distilled off as a volatile matter. The vola-
tile matter in a liquid form was analyzed by 1H-, 13C-
and 1 Sn-NMR's. As a result, it was confirmed that the
volatile matter in a liquid form contained about 0.005
mol of tributyltin(2-ethylhexyloxide).
Example 2
Synthesis of an organometal compound having a
hexyloxy group from dibutyltin oxide and hexanol was
performed as follows.
Into a 200-ml autoclave (manufactured and sold by
Toyo Koatsu Co., Ltd., Japan) were charged 24.9 g (100
mmol) of dibutyltin oxide (manufactured and sold by Al-
drich, U.S.A.) and 51.1 g (500 mmol) of hexanol (manu-
factured and sold by Aldrich, U.S.A.; a dehydrated
grade). The autoclave was sealed. The atmosphere in
the autoclave was purged with nitrogen gas. Then,
stirring of the contents of the autoclave was started,
and the internal temperature of the autoclave was ele-
vated to 160 °C. Then, the stirring was continued for

about 30 minutes. Thereafter, the valve of the purge
line of the autoclave was opened, and water and hexanol
was distilled off through the purge line over 4 hours
while blowing a small amount of nitrogen gas into the
bottom of the autoclave. After that period, there was
almost no distillate any more. Then, the inside of the
autoclave was cooled to about 30°C, and there was ob-
tained a viscous reaction mixture. 1H-, 13C- and 119Sn-
NMR analyses of the reaction mixture was performed.
The NMR analyses showed that the viscous reaction mix-
ture contained about 40 mmol of 1,1,3,3-tetrabutyl-1,3
-di-hexyloxy-di-stannoxane, about 6 mmol of dibutyltin
dihexyloxide and about 4 mml of tributyltin hexyloxide.
Step (1)
Into the above-mentioned 200-ml autoclave contain-
ing the reaction mixture (containing an organometal
compound having a hexyloxy group) was charged 61.5 g
(602 mmol) of hexanol (manufactured and sold by Aldrich,
U.S.A.; a dehydrated grade), and the autoclave was
sealed. Then, from a carbon dioxide gas bomb which was
connected to the autoclave through a SUS tube and a
valve, carbon dioxide gas having a pressure of 5 MPa
was introduced into the autoclave. Stirring of the
contents of the autoclave was started. 10 Minutes af-

ter the start of the stirring, the valve of the carbon
dioxide gas bomb was closed. Then, the internal tem-
perature of the autoclave was elevated to 180°C while
stirring. In this instant, the internal pressure of
the autoclave was about 7.5 MPa. Then, a reaction was
performed for 6 hours while maintaining the internal
pressure of the autoclave at about 7.5 MPa. Thereafter,
the inside of the autoclave was cooled to about 30 ° C
and the internal pressure of the autoclave was returned
to atmospheric pressure by gently purging the carbon
dioxide gas, and there was obtained a transparent reac-
tion mixture. In the reaction mixture, dihexyl carbon-
ate was obtained in a yield of 14 %.
Step (2)
After step (1), 10 g of hexanol containing 1 % of
water was gently added to the reaction mixture obtained
in step (1), and the resultant mixture was stirred for
about 1 minute. Then, the autoclave was opened, and it
was found that the mixture in the autoclave had turned
into a white slurry. The white slurry was subjected to
filtration using a membrane filter (H020A142C, manufac-
tured and sold by Advantec Toyo Kaisha, Ltd., Japan) to
thereby obtain white solids and a filtrate. The white
solids were washed 2 times with 20 ml of hexanol. The

filtrate was transferred into a 1-liter eggplant-shaped
flask and subjected to a distillation under heating in
an oil bath at 160 °C and under reduced pressure. By
the distillation, hexanol, tributyltin hexyloxide and
dihexyl carbonate were recovered as a distillate. The
yield of dihexyl carbonate was 13 %. It was found that
the distillate contained about 2 nutiol of tributyltin
hexyloxide. On the other hand, a viscous liquid re-
mained in the flask after completion of the distilla-
tion.
Step (3)
The white solids obtained in step (2) and the re-
sidual viscous liquid which remained in the flask after
the distillation performed in step (2), were charged
into a 200-ml autoclave (manufactured and sold by Toyo
Koatsu Co., Ltd., Japan). Further, 51.1 g (500 mmol)
of hexanol (manufactured and sold by Aldrich, U.S.A.; a
dehydrated grade) was charged into the autoclave, and
the autoclave was sealed. The atmosphere in the auto-
clave was purged with nitrogen gas. Then, stirring of
the contents of the autoclave was started, and the in-
ternal temperature of the autoclave was elevated to
160 °C. Then, the stirring was continued for about 30
minutes. Thereafter, the purge line of the autoclave

was opened, and water and hexanol were distilled off
through the purge line over 4 hours while blowing a
small amount of nitrogen gas into the bottom of the
autoclave. After that period, there was almost no dis-
tillate any more. Then, the inside of the autoclave
was cooled to about 30°C, and there was obtained a re-
action mixture. 1H-, 13C- and 119Sn-NMR analyses of the
reaction mixture was performed. The NMR analyses
showed that the reaction mixture contained about 40
mmol of 1,1,3,3-tetrabutyl-l,3-di-hexyloxy-di-
stannoxane, about 7 mmol of dibutyltin dihexyloxide and
about 4 mmol of tributyltin hexyloxide.
After step (3), step (1) was performed as follows.
Into the above-mentioned autoclave in which step
(3) was performed was charged 61.5 g (602 mmol) of hex-
anol (manufactured and sold by Aldrich, U.S.A.; a dehy-
drated grade). The autoclave was sealed. Then, from a
carbon dioxide gas bomb which was connected to the
autoclave through a SUS tube and a valve, carbon diox-
ide gas having a pressure of 5 MPa was introduced into
the autoclave. Stirring of the contents of the auto-
clave was started. 10 Minutes after the start of the
stirring, the valve of the carbon dioxide gas bomb was
closed. Then, the internal temperature of the auto-

clave was elevated to 180°C while stirring. In this
instant, the internal pressure of the autoclave was
about 7.5 MPa. Then, a reaction was performed for 6
hours while maintaining the internal pressure of the
autoclave at about 7.5 MPa. Thereafter, the inside of
the autoclave was cooled to about 30 ° C and the inter-
nal pressure of the autoclave was returned to atmos-
pheric pressure by gently purging the carbon dioxide
gas through the purge line, and there was obtained a
transparent reaction mixture. In the reaction mixture,
dihexyl carbonate was obtained in a yield of 14 %.
After step (1), 10 g of hexanol containing 1 % of
water was gently added to the reaction mixture obtained
in step (1), and the resultant mixture was stirred for
about 1 minute. Then, the autoclave was opened, and it
was found that the mixture in the autoclave had turned
into a white slurry. The white slurry was subjected to
filtration using a membrane filter (H020A142C. manufac-
tured and sold by Advantec Toyo Kaisha, Ltd., Japan) to
thereby obtain white solids and a filtrate. The white
solids were washed 2 times with 20 ml of hexanol. The
filtrate was transferred into a 1-liter eggplant-shaped
flask and subjected to a distillation under heating in
an oil bath at 160 "C and under reduced pressure. The

resultant flask was subjected to distillation under
heating and under reduced pressure. By the distilla-
tion, hexanol, tributyltin hexyloxide and dihexyl car-
bonate were recovered as a distillate. The yield of
dihexyl carbonate was 13 %. It was found that the dis-
tillate contained about 2 mmol of tributyltin hexylox-
ide.
Example 3
First, a reactive organometal compound having a 3
-methylbutoxy group was synthesized from dibutyltin ox-
ide and 3-methyl-1-butanol as follows.
Into a 1-liter four-necked flask equipped with a
cooling tube (which was connected with a vacuum con-
troller and a vacuum pump) and a Dean-Stark trap were
charged 70.5 g (0.28 mol) of dibutyltin oxide (manufac-
tured and sold by Aldrich, U.S.A.) and 502 g (5.7 mol)
of 3-methyl-1-butanol (manufactured and sold by Aldrich,
U.S.A.). Further, a stirrer was placed in the flask.
The flask was immersed in an oil bath having a
temperature of 140 °C. and the pressure in the flask
was gradually reduced to about 90 kPa while stirring
the contents of the flask. Then, the pressure in the
flask was further reduced to 85 kPa while stirring the
contents of the flask and withdrawing a distillate from

the flask, and a reaction was performed under 85 kPa
for 12 hours while further withdrawing a distillate
from the flask. Subsequently, unreacted components
(such as an unreacted alcohol) in the flask were dis-
tilled off from the flask over 30 minutes while gradu-
ally reducing the pressure in the flask to about 200 Pa.
The flask was taken out from the oil bath, and the in-
side of the flask was cooled. Then, nitrogen gas was
introduced into the flask to elevate the pressure in
the flask to atmospheric pressure. By the above
-mentioned operation, 127 g of a viscous liquid was ob-
tained.
The distillate withdrawn from the flask was ana-
lyzed. As a result, it was found that the distillate
contained about 260 mmol of water. The above-obtained
viscous liquid was analyzed by :H-, 13C- and 119Sn-NMR's.
As a result, it was found that the viscous liquid con-
tained dibutyltin bis(3-methylbutoxide), 1,1,3,3
-tetrabutyl-1,3-di(3-methylbutoxy)distannoxane and
tributyltin(3-methylbutoxide).
Step (1)
114 g of the above-obtained viscous liquid was
charged into a 200-ml autoclave (manufactured and sold
by Toyo Koatsu Co., Ltd., Japan) which had a carbon di-

oxide gas bomb connected thereto through a SUS tube and
a valve. The autoclave was sealed, and the atmosphere
in the autoclave was purged with nitrogen gas. Then,
the above-mentioned valve was opened to introduce car-
bon dioxide gas having a pressure of 5 MPa into the
autoclave. The introduction of carbon dioxide gas into
the autoclave was performed for 10 minutes while stir-
ring the contents of the autoclave, and, then, stopped
by closing the valve of the carbon dioxide gas bomb.
Subsequently, the internal temperature of the autoclave
was elevated to 120 °C while stirring. Then, a reac-
tion was performed for 4 hours while maintaining the
internal pressure of the autoclave at about 4 MPa.
During and after the reaction, samples of the re-
action mixture in the autoclave were taken out and ana-
lyzed. As a result, it was found that the reaction
mixture obtained 1 hour after the start of the reaction
contained di(3-methylbutyl) carbonate in a yield of
18 %, and that the reaction mixture obtained 4 hours
after the start of the reaction contained di(3
-methylbutyl) carbonate in a yield of 20.4 %.
After the reaction, the inside of the autoclave
was allowed to cool, and carbon dioxide gas was purged
therefrom.

Step (2)
After step (1), the contents of the autoclave were
allowed to cool to room temperature (about 20 °C) .
Then, the autoclave was opened to recover the reaction
mixture therefrom. The reaction mixture was charged
into a 300-ml eggplant-shaped flask equipped with a
cooling tube, a vacuum pump and a vacuum controller
(manufactured and sold by Okano Works, Ltd., Japan).
Further, a stirrer was placed in the flask. Then, the
flask was immersed in an oil bath having a temperature
of 140 °C.
A distillation was performed at 140 °C while stir-
ring the contents of the flask and gradually reducing
the pressure in the flask. During the distillation, 3
-methyl-1-butanol was first distilled off from the
flask and, then, di(3-methylbutyl) carbonate was dis-
tilled off from the flask. By the distillation, about
9 g of di(3-methylbutyl) carbonate and about 1 mmol of
tributyltin(3-methylbutoxide) were obtained.
Step (3)
Into a 1-liter four-necked flask equipped with a
cooling tube (which was connected with a vacuum con-
troller and a vacuum pump) and a Dean-Stark trap were
charged the distillation residue obtained in step (2)

above and 502 g (5.7 mol) of 3-methyl-1-butanol (manu-
factured and sold by Aldrich, U.S.A.). Further, a
stirrer was placed in the flask.
The flask was immersed in an oil bath having a
temperature of 140 °C, and the pressure in the flask
was gradually reduced to about 90 kPa while stirring
the contents of the flask. Then, the pressure in the
flask was further reduced to 85 kPa while stirring the
contents of the flask and withdrawing a distillate from
the flask, and a reaction was performed under 85 kPa
for 20 hours while further withdrawing a distillate
from the flask. Thereafter, unreacted components (such
as an unreacted alcohol) in the flask were distilled
off from the flask over 30 minutes while gradually re-
ducing the pressure in the flask to about 200 Pa,
thereby obtaining a reaction mixture. The reaction
mixture was analyzed by 1H-, 13C- and 119Sn-NMR's. As
a result, it was found that the reaction mixture con-
tained dibutyltin bis(3-methylbutoxide) and 1,1,3,3
-tetrabutyl-1,3-di(3-methylbutoxy)distannoxane. Fur-
ther, the reaction mixture also contained about 2 mmol
of tributyltin(3-methylbutoxide) . Subsequently, the
temperature of the oil bath was lowered so that the in-
ternal temperature of the flask became about 9 3 °C, and
a distillate was removed from the flask under a pres-

sure of 50 Pa. Then, the flask was taken out from the
oil bath, and the inside of the flask was cooled. Then,
nitrogen gas was introduced into the flask to elevate
the pressure in the flask to atmospheric pressure. By
this operation, 110 g of a viscous liquid was obtained.
The above-obtained viscous liquid was analyzed by
1H-, 13C- and 119Sn-NMR's. As a result, it was found
that the viscous liquid contained dibutyltin bis(3
-methylbutoxide) and 1,1,3,3-tetrabutyl-l,3-di(3
-methylbutoxy)distannoxane. It was also found that
about 1 mmol of tributyltin(3-methylbutoxide) was dis-
tilled off.
Step (1)
112 g of the above-obtained viscous liquid was
charged into a 200-ml autoclave (manufactured and sold
by Toyo Koatsu Co., Ltd., Japan) which had a carbon di-
oxide gas bomb connected thereto through a SUS tube and
a valve. The autoclave was sealed, and the atmosphere
in the autoclave was purged with nitrogen gas. Then,
the above-mentioned valve was opened to introduce car-
bon dioxide gas having a pressure of 5 MPa into the
autoclave. The introduction of carbon dioxide gas into
the autoclave was performed for 10 minutes while stir-
ring the contents of the autoclave, and, then, stopped

by closing the valve of the carbon dioxide gas bomb.
Subsequently, the internal temperature of the autoclave
was elevated to 120 °C while stirring. Then, a reac-
tion was performed for 4 hours while maintaining the
internal pressure of the autoclave at about 4 MPa.
During and after the reaction, samples of the re-
action mixture in the autoclave were taken out and ana-
lyzed. As a result, it was found that the reaction
mixture obtained 1 hour after the start of the reaction
contained di(3-methylbutyl) carbonate in a yield of
18 %, and that the reaction mixture obtained 4 hours
after the start of the reaction contained di(3
-methylbutyl) carbonate in a yield of 20.4 %.
After the reaction, the inside of the autoclave
was allowed to cool, and carbon dioxide gas was purged
therefrom.
Step (2)
After step (1), the contents of the autoclave were
allowed to cool to room temperature (about 20 °C) .
Then, the autoclave was opened to recover the reaction
mixture therefrom. The reaction mixture was charged
into a 300-ml eggplant-shaped flask equipped with a
cooling tube, a vacuum pump and a vacuum controller
(manufactured and sold by Okano Works, Ltd., Japan).

Further, a stirrer was placed in the flask. Then, the
flask was immersed in an oil bath having a temperature
of 140 °C.
A distillation was performed at 140 °C while stir-
ring the contents of the flask and gradually reducing
the pressure in the flask. During the distillation, 3
-methyl-1-butanol was first distilled off from the
flask and, then, di(3-methylbutyl) carbonate was dis-
tilled off from the flask. By the distillation, about
9 g of di(3-methylbutyl) carbonate and about 1 mmol of
tributyltin(3-methylbutoxide) were obtained.
Step (3)
Into a 1-liter four-necked flask equipped with a
cooling tube (which was connected with a vacuum con-
troller and a vacuum pump) and a Dean-Stark trap were
charged the distillation residue obtained in step (2)
above, 502 g (5.7 mol) of 3-methyl-l-butanol (manufac-
tured and sold by Aldrich, U.S.A.) and 1 g (4 mmol) of
dibutyltin oxide. Further, a stirrer was placed in the
flask.
The flask was immersed in an oil bath having a
temperature of 140 °C, and the pressure in the flask
was gradually reduced to about 90 kPa while stirring
the contents of the flask. Then, the pressure in the

flask was further reduced to 85 kPa while stirring the
contents of the flask and withdrawing a distillate from
the flask, and a reaction was performed under 85 kPa
for 20 hours while further withdrawing a distillate
from the flask. Thereafter, unreacted components (such
as an unreacted alcohol) in the flask were distilled
off from the flask over 30 minutes while gradually re-
ducing the pressure in the flask to about 200 Pa,
thereby obtaining a viscous reaction mixture. The vis-
cous reaction mixture was analyzed by 1H-, 13C- and
119Sn-NMR's. As a result, it was found that the reac-
tion mixture contained dibutyltin bis(3-methylbutoxide)
and 1,l,3,3-tetrabutyl-l,3-di(3-
methylbutoxy)distannoxane. Further, the reaction mix-
ture also contained about 2 mmol of tributyltin(3
-methylbutoxide). Subsequently, the temperature of the
oil bath was lowered so that the internal temperature
of the flask became about 93 oC, and a distillate was
removed from the flask under a pressure of 50 Pa. The
flask was taken out from the oil bath, and the inside
of the flask was cooled. Then, nitrogen gas was intro-
duced into the flask to elevate the pressure in the
flask to atmospheric pressure. By this operation, 110
g of a viscous liquid was obtained.
The above-obtained viscous liquid was analyzed by

1H-, 13C- and 119Sn-NMR's. As a result, it was found
that the viscous liquid contained dibutyltin bis(3
-methylbutoxide) and 1,1,3,3-tetrabutyl-l,3-di(3
-methylbutoxy)distannoxane. It was also found that
about 1 mmol of tributyltin(3-methylbutoxide) was dis-
tilled off.

INDUSTRIAL APPLICABILITY
By the method of the present invention, a carbonic
ester can be produced in high yield from an organometal
compound having in its molecule at least two metal
-oxygen-carbon linkages and carbon dioxide. It is ad-
vantageous that carbon dioxide has neither toxicity nor
corrosiveness and is inexpensive. Further, the method
of the present invention is advantageous not only in
that the organometal compound after use in this method
can be regenerated and recycled in the method, but also
in that an unregenerable unreactive organometal com-
pound formed can be removed from the reaction system,
thereby realizing an effective and stable production of
a carbonic ester. Further, there is no need for the
use of a large amount of a dehydrating agent, thereby
preventing occurrence of wastes derived from the dehy-
drating agent. Therefore, the method of the present
invention is commercially very useful and has high com-
mercial value.

WE CLAIM
1. A method for producing a carbonic ester, compris-
ing the steps of:
(1) performing a reaction between a first or-
ganometal compound mixture and carbon dioxide, said
first organometal compound mixture comprising a mixture
of a reactive organometal compound having in its mole-
cule at least two metal-oxygen-carbon linkages and an
unregenerable unreactive compound which is derived from
said reactive organometal compound and which has in its
molecule at least three metal-carbon linkages,
to thereby obtain a reaction mixture containing a
carbonic ester formed by the reaction, said unregener-
able unreactive compound, and a regenerable metamorphic
organometal compound derived from said reactive or-
ganometal compound,
(2) separating said reaction mixture into a first
portion containing said carbonic ester and said unre-
generable unreactive compound, and a second portion
containing said regenerable metamorphic organometal
compound, and
(3) reacting said second portion of said reaction
mixture with a first alcohol to form a second organome-
tal compound mixture and water and removing said water

from said second organometal compound mixture, said
second organometal compound mixture comprising a mix-
ture of a reactive organometal compound having in its
molecule at least two metal-oxygen-carbon linkages and
an unregenerable unreactive compound which is derived
from said reactive organometal compound and which has
in its molecule at least three metal-carbon linkages.
2. The method according to claim 1, which further
comprises, after step (3), a step (4) in which said
second organometal compound mixture obtained in step
(3) is recovered and recycled to step (1).
3. The method according to claim 1 or 2, wherein said
reactive organometal compound used in step (1) com-
prises at least one compound selected from the group
consisting of:
an organometal compound represented by the formula


wherein:
M represents a metal atom selected from the
group consisting of elements belonging to Groups
4 and 14 of the Periodic Table, exclusive of
silicon;
each of R1 and R2 independently represents a
straight chain or branched C1-C12 alkyl group, a
C5-C12 cycloalkyl group, a straight chain or
branched C2-C12 alkenyl group, a C7-C20 aralkyl
group comprised of unsubstituted or substituted
C5-C19 aryl and alkyl selected from the group
consisting of straight chain or branched C1-C14
alkyl and C5-C14 cycloalkyl, or an unsubstituted
or substituted C5-C20 aryl group;
each of R and R independently represents a
straight chain or branched C1-C12 alkyl group, a
C5-C12 cycloalkyl group, a straight chain or
branched C2-C12 alkenyl group, or a C7-C20 aral-
kyl group comprised of unsubstituted or substi-
tuted C5-C19 aryl and alkyl selected from the
group consisting of straight chain or branched
Cl-C14 alkyl and C5-C14 cycloalkyl; and
each of a and b is an integer of from 0 to 2,
a + b = 0 to 2, each of c and d is an integer of
from 0 to 4, and a+b+c+d=4; and


wherein:
2 3
each of M and M independently represents a
metal atom selected from the group consisting of
elements belonging to Groups 4 and 14 of the Pe-
riodic Table, exclusive of silicon;
each of R5 , R6, R7 and R8 independently repre-
sents a straight chain or branched C1-C12 alkyl
group, a C5-C12 cycloalkyl group, a straight
chain or branched C2-C12 alkenyl group, a C7-C20
aralkyl group comprised of unsubstituted or sub-
stituted C6-C19 aryl and alkyl selected from the
group consisting of straight chain or branched
C1-C14 alkyl and C5-C14 cycloalkyl, or an unsub-
stituted or substituted C6-C20 aryl group;
each of R9 and R10 independently represents a
straight chain or branched C1-C12 alkyl group, a
C5-C12 cycloalkyl group, a straight chain or

branched C2-C12 alkenyl group, or a C7-C20 aral-
kyl group comprised of unsubstituted or substi-
tuted C5-C19 aryl and alkyl selected from the
group consisting of straight chain or branched
C1-C14 alkyl and C5-C14 cycloalkyl; and
each of e, f, g and h is an integer of from 0
to 2, e+f=0 to 2, g + h = 0 to 2, each of i
and j is an integer of from 1 to 3, e+f+i=
3, and g + h + j = 3.
4. The method according to claim 3, wherein each of
R3 and R4 in formula (1) and R9 and R10 in formula (2)
independently represents an n-butyl group, an isobutyl
group, a straight chain or branched C5-C12 alkyl group,
or a straight chain or branched C4-C12 alkenyl group.
5. The method according to claim 3, wherein each of
M1 in formula (1) and M2 and M3 in formula (2) repre-
sents a tin atom.
6. The method according to claim 3, wherein said re-
active organometal compound used in step (1) is pro-
duced from an organotin oxide and an alcohol.
7. The method according to claim 1 or 2, wherein, in

step (1), said reactive organometal compound is used in
at least one form selected from the group consisting of
a monomeric form, an oligomeric form, a polymeric form
and an associated form.
8. The method according to claim 1 or 2, wherein, in
step (1), said reactive organometal compound is used in
an amount which is 1/50 to 1 time the stoichiometric
amount relative to the amount of said carbon dioxide.
9. The method according to claim 1 or 2, wherein said
reaction in step (1) is performed at 20 °C or higher.
10. The method according to claim 1 or 2, wherein said
reaction in step (1) is performed in the presence of a
second alcohol which is the same as or different from
said first alcohol used in step (3).
11. The method according to claim 1 or 2, wherein, in
step (2), said separation of said reaction mixture into
said first portion and said second portion is performed
by at least one separation method selected from the
group consisting of distillation, extraction and fil-
tration .

12. The method according to claim 1 or 2, wherein, in
step (2), said separation of said reaction mixture into
said first portion and said second portion is performed
in the presence of an alcohol which is the same as or
different from said first alcohol used in step (3).
13. The method according to claim 1 or 2, wherein said
first alcohol used in step (3) is at least one alcohol
selected from the group consisting of an alkyl alcohol
having a straight chain or branched C1-C12 alkyl group,
a cycloalkyl alcohol having a C5-C12 cycloalkyl group,
an alkenyl alcohol having a straight chain or branched
C2-C12 alkenyl group, and an aralkyl alcohol having a
C7-C20 aralkyl group comprised of unsubstituted or sub-
stituted C6-C19 aryl and alkyl selected from the group
consisting of straight chain or branched C1-C14 alkyl
and C5-C14 cycloalkyl.
14. The method according to claim 13, wherein said
first alcohol has a boiling point which is higher than
the boiling point of water, as measured under atmos-
pheric pressure.
15. The method according to claim 14, wherein said
first alcohol is at least one alcohol selected from the

group consisting of 1-butanol, 2-methyl-1-propanol, an
alkyl alcohol having a straight chain or branched C5-
C12 alkyl group, an alkenyl alcohol having a straight
chain or branched C4-C12 alkenyl group, a cycloalkyl
alcohol having a C5-C12 cycloalkyl group, and an aral-
kyl alcohol having a C7-C20 aralkyl group comprised of
unsubstituted or substituted C6-C19 aryl and alkyl se-
lected from the group consisting of straight chain or
branched C1-C14 alkyl and C5-C14 cycloalkyl.
16. The method according to claim 1 or 2, wherein said
removal of said water in step (3) is performed by mem-
brane separation.
17. The method according to claim 16, wherein said
membrane separation is pervaporation.
18. The method according to claim 1 or 2, wherein said
removal of said water in step (3) is performed by dis-
tillation.

A method for producing a carbonic ester, compris-
ing : (1) performing a reaction between an organometal
compound mixture and carbon dioxide, the organometal
compound mixture comprising a reactive organometal com-
pound and an unregenerable unreactive compound derived
from the reactive organometal compound, to thereby ob-
tain a reaction mixture containing a carbonic ester,
the unregenerable unreactive compound, and a regener-
able metamorphic organometal compound derived from the
reactive organometal compound, (2) separating the reac-
tion mixture into a first portion containing the car-
bonic ester and the unregenerable unreactive compound,
and a second portion containing the regenerable meta-
morphic organometal compound, and (3) reacting the sec-
ond portion of the reaction mixture with an alcohol to
form an organometal compound mixture and water and re-
moving the water from the organometal compound mixture,
the organometal compound mixture comprising a reactive
organometal compound and an unregenerable unreactive
compound derived from the reactive organometal compound.

Documents:

00034-kolnp-2005 abstract.pdf

00034-kolnp-2005 claims.pdf

00034-kolnp-2005 correspondence-1.1.pdf

00034-kolnp-2005 correspondence-1.2.pdf

00034-kolnp-2005 correspondence-1.3.pdf

00034-kolnp-2005 correspondence.pdf

00034-kolnp-2005 description(complete).pdf

00034-kolnp-2005 drawings.pdf

00034-kolnp-2005 form-1.1.pdf

00034-kolnp-2005 form-1.pdf

00034-kolnp-2005 form-13.pdf

00034-kolnp-2005 form-18.pdf

00034-kolnp-2005 form-2.pdf

00034-kolnp-2005 form-3.pdf

00034-kolnp-2005 form-5-1.1.pdf

00034-kolnp-2005 form-5.pdf

00034-kolnp-2005 gpa.pdf

00034-kolnp-2005 international search authority report.pdf

00034-kolnp-2005 others.pdf

00034-kolnp-2005 pct others.pdf

00034-kolnp-2005 pct request.pdf

00034-kolnp-2005 priority document.pdf

34-KOLNP-2005-FORM-27.pdf

34-kolnp-2005-granted-abstract.pdf

34-kolnp-2005-granted-claims.pdf

34-kolnp-2005-granted-correspondence.pdf

34-kolnp-2005-granted-description (complete).pdf

34-kolnp-2005-granted-examination report.pdf

34-kolnp-2005-granted-form 1.pdf

34-kolnp-2005-granted-form 13.pdf

34-kolnp-2005-granted-form 2.pdf

34-kolnp-2005-granted-form 3.pdf

34-kolnp-2005-granted-form 5.pdf

34-kolnp-2005-granted-gpa.pdf

34-kolnp-2005-granted-reply to examination report.pdf

34-kolnp-2005-granted-specification.pdf

34-kolnp-2005-granted-translated copy of priority document.pdf


Patent Number 231470
Indian Patent Application Number 34/KOLNP/2005
PG Journal Number 10/2009
Publication Date 06-Mar-2009
Grant Date 04-Mar-2009
Date of Filing 13-Jan-2005
Name of Patentee ASAHI KASEI CHEMICALS CORPORATION
Applicant Address 1-2, YURAKU-CHO 1-CHOME, CHIYODA-KU, TOKYO 100-8440
Inventors:
# Inventor's Name Inventor's Address
1 NOBUHISA MIYAKE 953,TSURUSHINDEN,TSURAJIMA-CHO,KURASHINDEN-SHI, OKAYAMA-KEN 712-8006
2 TOMONARI WATANABE 3-6-2,SAKURAMORI YAMATO-SHI,KANAGAWA-KEN 242-0028
PCT International Classification Number C07C 68/04
PCT International Application Number PCT/JP2003/010004
PCT International Filing date 2003-08-06
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2002-229385 2002-08-07 Japan