Amido compounds and process for producing the same

Details Amido compounds and process for producing the same Amido compounds and process for producing the same

2003-03-05

2003-12-02

McKane, Joseph K. (Department: 1626)

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

Reexamination Certificate

active

06657069

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to an intermediate useful for obtaining 3-oxopentanedicarboxylic acid amide compounds, a process for producing the same, and a process for producing 3-oxopentanedicarboxylic acid amide compounds using the above intermediate. The 3-oxopentanedicarboxylic acid amide compounds is beneficial as intermediates of fine chemicals such as medicinals and agrochemicals and beneficial as raw materials for polyamides.
BACKGROUND OF THE INVENTION
3-oxopentanedicarboxylic acid amide compounds are compounds useful as intermediates of fine chemicals, such as medicinals and agrochemicals, and as raw materials for polyamides.
As a process for synthesizing the compound, for example, Journal of the American Chemical Society, 1979, pages 2171-2181 discloses a process for producing methyl N-t-butyl-3-oxoglutaramate which comprises boiling mixture of dimethyl ester of 3-oxopentanedicarboxylic acid, p-toluenesulfonic acid and dioxane, and adding butylamine to the mixture dropwise for 9 hours. In this process, however, the conversion reaction of the ester into the amide proceeds slowly, and reaction operability is decreased. Moreover, in this process, since an ester amide is produced from a diester, by-products such as diamide tend to form. Thus, it is disadvantageous that the process is applied to an industrial production of an ester amide.
JOURNAL OF THE CHEMICAL SOCIETY, 1962, pages 3553-3561 discloses a process for synthesizing 3-oxopentanedicarboxylic acid amide carboxylic acid (in particular, &ggr;-(benzoylcarbamoyl)acetoacetic acid) which comprises synthesizing chloropyranooxazine from malonyl chloride or pyrone acid chloride and benzonitrile, hydrolyzing chloropyranooxazine to form hydroxypyranooxazine, and treating the resulting oxazine with an acid. This process is, however, disadvantageous in the efficient utilization of the reactants because of by-producing carbon dioxide. Moreover, when various substituents are introduced into 3-oxopentanedicarboxylic acid amide carboxylic acid, the reaction step comes complicated.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide amide compounds useful for producing 3-oxopentanedicarboxylic acid amide compounds in an industrially advantageous manner, a process for producing the same, and a process for producing 3-oxopentanedicarboxylic acid amide compounds using the same.
Another object of the invention is to provide novel 3-oxopentanedicarboxylic acid amide compounds.
As a result of intensive investigations made to solve the above problems, the present inventors found that, by using the specific amide compound, 3-oxopentanedicarboxylic acid amide compounds can be produced efficiently. These findings have now led to completion of the present invention.
Thus, the novel amide compounds of the present invention are represented by the following formula (1):
wherein R
1
, R
2
, R
3
and R
4
are the same or different, each represents a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, the hydrocarbon groups may optionally have a substituent, R
1
and R
2
may form a ring with an adjacent nitrogen atom, and R
3
and R
4
may form a ring with an adjacent carbon atom.
The amide compound (1) can be produced by reacting a halogen compound represented by the following formula (2) with carbon monoxide and an amine represented by the following formula (3). The reaction is carried out in the presence of a catalyst comprising at least one element selected from the group consisting of Group 8 elements, Group 9 elements and Group 10 elements of the Periodic Table of Elements. In the formula (2), X may be an iodine or bromine atom. A halogen compound of the formula (2) in which X is a fluorine or chlorine atom is reacted with carbon monoxide and the alcohol or water in the presence of at least one member selected from among iodinating agents and brominating agents.
wherein X is a halogen atom and R
1
, R
2
, R
3
and R
4
have the same meanings as defined above.
According to the present invention, a dicarboxylic acid amide compound represented by the following formula (5) can be produced by reacting the amide compound (1) with an alcohol or water represented by the following formula (4).
wherein R represents a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, the hydrocarbon groups may optionally have a substituent, and R
1
and R
2
have the same meaning as defined above.
The present invention also includes a novel dicarboxylic acid amide compound represented by the following formula (5a):
wherein R
1
represents a hydrogen atom, R
2
represents a cycloalkyl group, and R
5
represents an alkyl group, the cycloalkyl group and the alkyl group may optionally have a substituent.
DETAILED DESCRIPTION OF THE INVENTION
[Amide Compounds (1)]
Referring to the amide compound represented by the above formula (1), the aliphatic hydrocarbon groups represented by R
1
, R
2
, R
3
and R
4
may be either straight chain or branched chain hydrocarbon groups, and may be either saturated or unsaturated hydrocarbon groups. Examples of the aliphatic hydrocarbon groups include alkyl groups (preferably C
1-10
alkyl groups, more preferably C
1-6
alkyl groups, in particular C
1-4
alkyl groups), such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl groups; alkenyl groups (preferably C
2-6
alkenyl groups, in particular C
2-4
alkenyl groups), such as vinyl, allyl, isopropenyl, 1-butenyl and 2-butenyl groups; alkynyl groups (preferably C
2-6
alkynyl groups, in particular C
2-4
alkynyl groups), such as ethynyl, propynyl, 1-butynyl and 2-butynyl groups.
The alicyclic hydrocarbon groups may be saturated or unsaturated hydrocarbon groups. Examples of the alicyclic hydrocarbon groups include cycloalkyl groups (e.g., 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; cycloalkenyl groups (e.g., 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; cycloalkynyl groups (e.g., C
4-8
cycloalkynyl groups, in particular C
5-6
cycloalkynyl groups), such as cyclopentynyl, cyclohexynyl and cyclooctynyl groups.
Examples of the aromatic hydrocarbon groups include aryl groups (e.g., C
6-10
aryl groups), such as phenyl and naphthyl groups; aralkyl group groups (e.g., C
6-10
aryl-C
1-4
alkyl groups), such as benzyl and phenethyl groups.
The alicyclic hydrocarbon group and the aromatic hydrocarbon group may form a condensed ring with, for example, a heterocycle.
The hydrocarbon groups may have a substituent. As the substituent, there may be mentioned, halogen atoms, such as fluorine, chlorine and bromine atoms; C
1-4
alkyl groups such as methyl and ethyl groups; acyl groups [e.g. alkylcarbonyl group (e.g., C
1-4
alkyl-carbonyl groups) such as acetyl group; arylcarbonyl groups (e.g., C
6-10
aryl-carbonyl groups) such as benzoyl group], acyloxy groups [e.g., alkylcarbonyloxy groups (e.g., C
1-4
alkyl-carbonyloxy groups) such as acetyloxy group; arylcarbonyloxy groups (e.g., C
6-10
aryl-carbonyloxy groups) such as benzoyloxy group], alkoxy groups (e.g., C
1-4
alkoxy groups) such as methoxy and ethoxy groups; alkoxycarbonyl groups (C
1-4
alkoxy-carbonyl groups) such as methoxycarbonyl group; aryl groups (e.g., C
6-10
aryl groups) such as phenyl and naphthyl groups; aryloxy groups such as phenoxyl group; heterocyclic groups (e.g., 5- to 8-membered heterocyclic groups such as pyridyl, piridino, piperidyl and piperidino groups).
The ring formed by R
1
and R
2
together with an adjacent nitrogen atom includes a saturated or unsaturated heterocycle having at least one nitrogen atom as an ring-constituting atom, and may be either an aromatic or non-aromatic ring. As the het

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