Ester and process for producing the same

Details Ester and process for producing the same Ester and process for producing the same

2000-11-03

2001-10-02

Lambkin, Deborah C. (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

Reexamination Certificate

active

06297388

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to 6-alkoxycarbonylmethyl-4H-1,3-dioxin-4-one derivatives, a process for producing the same, intermediates which are important in the process, and a process for producing 3-oxopentanedicarboxylic acid esters using the above derivatives.
BACKGROUND OF THE INVENTION
3-Oxopentanedicarboxylic acid esters are compounds useful as intermediates of fine chemicals, such as medicinals and agrochemicals, and as raw materials for polyesters.
Organic Syntheses, Collective Volume 1, page 10 and page 237, for instance, discloses a technique of producing 3-oxopentanedicarboxylic acid which comprises treating citric acid with fuming sulfuric acid to give acetonedicarboxylic acid and esterifying this dicarboxylic acid. In this process, however, the intermediate acetonedicarboxylic acid is unstable and readily undergoes decomposition by heat or by an acid or alkali, for instance. Therefore, when this process is conducted on an industrial scale, the yield of and the selectivity for the desired product 3-oxopentanedicarboxylic acid ester are low.
In Japanese Patent Publication No. 24461/1991 (JP-3-24461B) and Japanese Patent Application Laid-Open No. 78146/1983 (JP-59-78146A), there is reported a method of synthesizing 3-oxopentanedicarboxylic acid from diketene, an alkyl nitrite and carbon monoxide using a palladium catalyst. For obtaining the alkyl nitrite, however, it is in general necessary to react a nitrogen oxide, such as nitrogen monoxide, nitrogen dioxide, dinitrogen trioxide or dinitrogen tetraoxide, which requires care in handling, with an alcohol or water. This reduced the workability and reaction operability.
Therefore, these processes cannot be said to be advantageous from the industrial practicability viewpoint. Further, these processes are essentially incapable of synthesizing unsymmetrical diesters (namely diesters having a structure such that the two ester groups have different alkoxy moieties) and, even if they could be synthesized, they would be obtained only in the form of a mixture of unsymmetrical and symmetrical diesters.
In Swiss Patent No. 659060, a method is disclosed which uses an acetoacetate ester and a chloroformate ester as starting materials. However, this method uses liquid ammonia and sodium amide, which are not always easy to handle on an industrial scale, and, therefore, cannot be said to be an advantageous method from the industrial production viewpoint, either.
On the other hand, Chemistry Letters, 1990, volume 6, pages 901-904 and the Journal of Organic Chemistry, vol. 62, No. 21, page 7114 (1997), for instance, describe a ring-opening reaction of a 6-substituted-4H-1,3-dioxin-4-one under the action of an alcohol or water.
Further, in M. Hidai and M. Ichikawa: “Kagaku Seminar, 11, Kin'itsu Shokubai to Fukin'itsu Shokubai Nyumon—Korekarano Shokubai Kagaku (Seminar in Chemistry, 11, Homogeneous and Heterogeneous Catalysts, An Introduction—Catalytic Chemistry in the Future)”, published by Maruzen Co. (1983), page 49, for instance, there is described an ester synthesis by the carbonylation reaction of an aryl halide using a palladium catalyst.
However, there is no description of 6-alkoxycarbonylmethyl-4H-1, 3-dioxin-4-ones and there is no example known of the application of these reaction systems to 6-alkoxycarbonylmethyl-4H-1,3-dioxin-4-ones.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a process by which 3-oxopentanedicarboxylic acid esters can be produced in an industrially advantageous manner (e.g. safely and at low cost), and intermediates for use in that process.
Another object of the invention is to provide a process by which unsymmetrical 3-oxopentanedicarboxylic acid esters can be produced with good efficiency, and intermediates for use in that process.
A further object of the invention is to provide a process by which 3-oxopentanedicarboxylic acid esters can be produced with good efficiency, and intermediates for use in that process.
As a result of intensive investigations made to solve the above problems, the present inventors found that specific cyclic esters can be synthesized efficiently by reacting a specific halogen compound with carbon monoxide and an alcohol or water and, further, that 3-oxopentanedicarboxylic acid esters can be produced from these cyclic esters in an industrially advantageous manner. These findings have now led to completion of the present invention.
Thus, the cyclic esters of the present invention are represented by the following formula (1):
wherein R
1
, R
2
and R
3
are the same or different and each represents a hydrogen atom or a chain or cyclic aliphatic hydrocarbon group, which may optionally be further substituted.
In the above formula (1), R
1
may be a straight or branched C
1-4
alkyl group, a C
3-10
cycloalkyl group or a C
6-10
aryl-C
1-4
alkyl group and R
2
and R
3
are the same or different and each may be a hydrogen atom or a C
1-4
alkyl group.
The present invention also includes a process for producing the above cyclic esters which comprises the step of reacting a halogen compound represented by the formula (2) with carbon monoxide and an alcohol or water represented by the formula (3), as shown below:
wherein, X represents a halogen atom and R
1
, R
2
and R
3
are as above defined in the formula (1).
In this process, the reaction may be carried out in the presence of a catalyst comprising a platinum group metal (e.g. palladium) (a platinum group metal as a simple substance or a platinum group metal-containing compound).
The present invention further includes a process for producing dicarboxylic acid esters represented by the formula (5) which comprises the step of reacting the above cyclic esters with an alcohol or water represented by the formula (4), as shown below:
wherein, R
4
represents a hydrogen atom or a chain or cyclic aliphatic hydrocarbon group, which may optionally be substituted, and R
1
to R
3
are as above defined.
The present invention further includes halogen compounds represented by the formula (2) given below (in particular compounds in which X is a bromine or iodine atom). These compounds are useful as intermediates for the production of the above cyclic esters.
In the formula, X is a halogen atom and R
2
and R
3
are as above defined in the formula (1).
DETAILED DESCRIPTION OF THE INVENTION
Cyclic Esters
Referring to the cyclic esters (6-alkoxy-carbonylmethyl-4H-1,3-dioxin-4-one derivatives) represented by the above formula (1), the aliphatic chain hydrocarbon group represented by R
1
, R
2
and/or R
3
includes straight chain or branched chain hydrocarbon groups, for example alkyl, alkenyl, alkynyl groups. The aliphatic cyclic hydrocarbon group (alicyclic hydrocarbon group) includes saturated or unsaturated aliphatic cyclic groups, for example cycloalkyl, cycloalkenyl, cycloalkynyl groups.
Among the alkyl groups, there may be mentioned, for example, straight or branched C
1-10
alkyl groups (preferably C
1-6
alkyl groups, in particular C
1-4
alkyl groups), such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl groups.
Among the alkenyl groups, there may be mentioned, for example, straight or branched C
2-6
alkenyl groups (in particular C
2-4
alkenyl groups), such as vinyl, allyl, isopropenyl, 1-butenyl and 2-butenyl groups.
Among the alkynyl groups, there may be mentioned, for example, straight or branched C
2-6
alkynyl groups (in particular C
2-4
alkynyl groups), such as ethynyl, propynyl, 1-butynyl and 2-butynyl groups.
Among the cycloalkyl groups, there may be mentioned, for example, C
3-10
cycloalkyl groups, preferably C
4-8
cycloalkyl groups (in particular C
4-6
cycloalkyl groups), such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl groups.
Among the cycloalkenyl groups, there may be mentioned, for example, C
3-10
cycloalkenyl groups, preferably C
4-8
cycloalkenyl groups (in particular C
4-6
cycloalkenyl groups), such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl and cyclooctenyl groups.
Among the c

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