Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
2001-03-29
2003-05-20
Killos, Paul J. (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C560S096000, C560S101000, C562S468000, C562S473000, C562S480000, C562S491000, C562S488000
Reexamination Certificate
active
06566548
ABSTRACT:
This a 371 of PCT/JP99/05538 Oct. 7, 1999.
FIELD OF INVENTION
The present invention relates to novel carboxylic acid derivatives, molecular compounds containing the said carboxylic acid derivatives as constituent compounds, and others. In more detail, the present invention relates to novel carboxylic acid derivatives having tetrakisphenyl skeleton and processes for the preparation thereof, molecular compounds containing the said carboxylic acid derivatives as constituent compounds and processes for the preparation thereof, and coordination compounds with the said carboxylic acid derivatives as ligands.
BACKGROUND ART
Molecular compounds are compounds that two or more compounds are bound through relatively weak interactions other than covalent bonds, represented by hydrogen bonds or van der Waals forces. The molecular compounds have a property to dissociate into the original individual constituent compounds by simple operations, and are expected to have applications to technological fields such as selective separation of useful substances, chemical stabilization, nonvolatilization, prolongation of release and powderization in recent years.
An actual example of the molecular compounds is a clathrate compound. For example, clathrate compounds of 5-chloro-2-methyl-4-isothiazolin-3-one or the like with 1,1,6,6-tetraphenyl-2,4-hexadiyn-1,6-diol or 1,1-di(2,4-dimethylphenyl)-2-propyn-1-ol have been described in Japanese Patent Laid-open No. Sho 61-53201, and with 1,1′-bis-2-naphthol in Japanese Patent Laid-open No. Sho 62-22701. Japanese Patent Laid-open No. Hei 3-279373 has reported clathrate compounds of bisphenol compounds and isothiazolone compounds. Furthermore, clathrate compounds of tetrakisphenols and various organic compounds have been disclosed in Japanese Patent Laid-open No. Hei 6-166646.
However, conventional technology has not yet found clathrate compounds with very satisfactory performances in selective separation of useful substances, chemical stabilization, nonvolatilization, prolongation of release, powderization and others, because of easy destruction due to changes in external factors such as heat or pH, easy dissociation in liquids and other problems.
It is an object of the present invention to provide novel molecular compounds containing carboxylic acid derivatives with tetrakisphenyl skeleton as constituent compounds and having excellent performance in such technological fields as selective separation of useful substances, chemical stabilization, nonvolatilization, prolongation of release and powderization, and novel coordination compounds useful as solid catalysts.
DISCLOSURE OF THE INVENTION
To solve the above-mentioned problems earnest studies were carried out. As a result it was found that a molecular compound containing, as a constituent compound, a carboxylic acid derivative with a specific tetrakisphenyl skeleton of which carboxyl groups forming rigid hydrogen bonds by two-point interactions are arranged divergently, exhibits extremely excellent performances in such technological fields as selective separation of useful substances, chemical stabilization, nonvolatilization, prolongation of release and powderization. Thus the present invention has been completed.
That is, the present invention relates to carboxylic acid derivatives represented by the following Formula (I) or (II) [wherein, in Formulae (I) and (II), X is (CH
2
)
n
or p-phenylene; n is 0, 1, 2 or 3; R
1
to R
8
and R
13
to R
20
are each hydrogen, C
1
to C
6
alkyl, C
2
to C
4
alkenyl, phenyl optionally substituted with C
1
to C
6
alkyl, halogen or C
1
to C
6
alkoxy; R
9
to R
12
and R
21
to R
24
are each hydrogen, C
1
to C
6
alkyl, C
2
to C
4
alkenyl, C
7
to C
12
aralkyl or alkali metal].
The present invention also relates to the said carboxylic acid derivatives represented by Formula (III) or (IV) below [wherein, in Formulae (III) and (IV), R
25
to R
32
and R
35
to R
42
are each hydrogen, C
1
to C
6
alkyl, C
2
to C
4
alkenyl, phenyl optionally substituted with C
1
to C
6
alkyl, halogen or C
1
to C
6
alkoxy; R
33
, R
34
, R
43
and R
44
are each hydrogen, C
1
to C
6
alkyl, C
2
to C
4
alkenyl, C
7
to C
12
aralkyl or alkali metal].
The present invention also relates to processes for the preparation of the carboxylic acid derivatives represented by the above Formula (I) or (II), particularly by Formula (III) or (IV), characterized by the use of 1,1-bis(3-carboxyphenyl)ketone derivatives or 1,1-bis(4-carboxyphenyl)ketone derivatives.
The present invention also relates to molecular compounds such as clathrate compounds containing the carboxylic acid derivatives of the above Formula (I) or (II), particularly Formula (III) or (IV), as constituent compounds, and to molecular compounds such as the said clathrate compounds containing, as constituent compounds, the said carboxylic acid derivatives and antibacterial agents, antifungal agents, insecticides, noxious insect repellents, perfumes, deodorants, anti-fouling agents, curing agents and curing accelerators for coating materials, plastics and adhesives, natural essential oils, antioxidants, vulcanization accelerators or organic solvents that react with the said carboxylic acid derivatives to form clathrate compounds, and processes for the preparation of any of the above-mentioned molecular compounds.
Further, the present invention relates to coordination compounds having, as ligands, the carboxylic acid derivatives of the said Formula (I) or (II) wherein R
9
to R
12
and R
21
to R
24
are hydrogen or alkali metal.
The molecular compounds of the present invention refer to compounds that two or more constituent compounds able to exist alone and stably are bound by relatively weak interactions other than covalent bonds, represented by hydrogen bonds or van der Waals forces, and include hydrates, solvates, adducts, clathrate compounds and the like.
In the carboxylic acid derivatives of Formulae (I), (II), (III) and (IV) of the present invention, actual examples of substituents represented by R
1
to R
8
, R
13
to R
20
, R
25
to R
32
and R
35
to R
42
include hydrogen; straight-chain, branched-chain or cyclic C
1
to C
6
alkyl such as methyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl and cyclohexyl; C
2
to C
4
alkenyl such as vinyl, allyl, isopropenyl, 1-propenyl, 2-butenyl, 3-butenyl and 1,3-butadienyl; phenyl optionally substituted with C
1
to C
6
alkyl such as phenyl and p-methylphenyl; halogen such as fluorine, chlorine, bromine and iodine; and C
1
to C
6
alkoxy such as methoxy, ethoxy and t-butoxy.
In the carboxylic acid derivatives of Formulae (I), (II), (III) and (IV) of the present invention, actual examples of substituents represented by R
9
to R
12
, R
21
to R
24
, R
33
, R
34
, R
43
and R
44
include hydrogen; C
1
to C
6
alkyl such as methyl, ethyl, n-propyl and n-butyl; C
2
to C
4
alkenyl such as vinyl, allyl, isopropenyl, 1-propenyl, 2-butenyl, 3-butenyl and 1,3-butadienyl; aralkyl such as benzyl; and alkali metal such as sodium and potassium.
Of the carboxylic acid derivatives of Formula (I) or (II) of the present invention, tetrakiscarboxyphenylethane and its derivatives represented by Formula (III) or (IV) are particularly preferred from the viewpoints of performances such as selective separation of useful substances, chemical stabilization, nonvolatilization, prolongation of release and powderization.
Examples of tetrakisphenylcarboxylates of the invention include tetrakis(4-carboxyphenyl)ethane, tetrakis(4-carboxyphenyl)ethane tetramethyl ester, tetrakis(4-carboxyphenyl)ethane tetraethyl ester, tetrakis(4-carboxyphenyl)ethane tetra-n-propyl ester, tetrakis(4-carboxyphenyl)ethane tetrabenzyl ester, tetrakis(3,5-dimethyl-4-carboxyphenyl)ethane, tetrakis(3,5-dimethyl-4-carboxyphenyl)ethane tetramethyl ester, tetrakis(3,5-dimethyl-4-carboxyphenyl)ethane tetraethyl ester, tetrakis(3,5-dimethyl-4-carboxyphenyl)ethane tetra-n-propyl ester, tetrakis(3,5-dimethyl-4-carboxyphenyl)ethane tetrabenzyl ester, tetrakis(4-carboxyphenyl)ethane tetras
Abe Satoru
Suzuki Hiroshi
Killos Paul J.
LaPointe Dennis G.
Nippon Soda Co. Ltd.
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