Organic compounds -- part of the class 532-570 series – Organic compounds – Four or more ring nitrogens in the bicyclo ring system
Reexamination Certificate
2002-04-09
2003-08-12
Solola, Taofiq (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Four or more ring nitrogens in the bicyclo ring system
Reexamination Certificate
active
06605717
ABSTRACT:
TECHNICAL FIELD
The present invention relates to optically active &bgr;-type tris-(2,3-epoxypropyl)-isocyanurate which is an optically active epoxy compound useful as a raw material for e.g. an optical resolution agent, a high polymer catalyst or a nonlinear material such as a nonlinear optical material, or as a crosslinking agent for a compound or a polymer reactive to an epoxy group, a method for producing it, and a method for producing a high melting point type tris-(2,3-epoxypropyl)-isocyanurate obtained by mixing two enantiomers of the optically active &bgr;-type tris-(2,3-epoxypropyl)-isocyanurate thus produced, useful as a high polymer material to be used for the field of electricity and electronic industry materials, or as a crosslinking agent for different compounds or for a reactive high polymer.
BACKGROUND ART
To obtain an optically active epoxy compound, a method by asymmetric epoxidation of an olefin has conventionally been known. However, a special and expensive catalyst may be required in this method, or no epoxy compound having a high optical purity tends to be obtained in this method when it is attempted to derive a multifunctional epoxy compound. On the other hand, e.g. an asymmetric resolution method has been known wherein a racemic modification is resolved kinetically by e.g. an enzyme. In this method, it is troublesome to select an enzyme and its conditions, as it is a kinetic resolution method, there is a limit to the optical purity of the compound to be obtained, and no epoxy compound having a high optical purity tends to be obtained when it is attempted to drive a multifunctional epoxy compound, similarly to the above asymmetric epoxidation. From such reasons, no method has been known to produce a multifunctional epoxy compound such as (2R,2′R,2″R)-tris-(2,3-epoxypropyl)-isocyanurate or (2S,2′S,2″S)-tris-(2,3-epoxypropyl)-isocyanurate with a high optical purity. At the same time, no method has been known to optically resolve tris-(2,3-epoxypropyl)-isocyanurate.
Tris-(2,3-epoxypropyl)-isocyanurate has conventionally been known, however, no resolution method nor synthesis method has been known with respect to (2R,2′R,2″R)-tris-(2,3-epoxypropyl)-isocyanurate and (2S,2′S,2″S)-tris-(2,3-epoxypropyl)-isocyanurate, and accordingly, no example has been reported which discloses these substances themselves which are optically active substances.
A tris-(2,3-epoxypropyl)-isocyanurate has three asymmetric carbon atoms. A racemic mixture of (2R,2′R,2″R)-tris-(2,3-epoxypropyl)-isocyanurate and (2S,2′S,2″S)-tris-(2,3-epoxypropyl)-isocyanurate, of which the three asymmetric carbon atoms are coordinate, is commonly called &bgr;-type, and is known to provide a crystal having a high melting point of a level of 150° C. This is because a pair of these two enantiomers forms a molecular lattice having six strong hydrogen bonds, and this molecular lattice forms a crystal lattice having high-level hydrogen bonds with other molecular lattices.
On the other hand, a mixture of (2R,2R,2S)-tris-(2,3-epoxypropyl)-isocyanurate and (2S,2S,2R)-tris-(2,3-epoxypropyl)-isocyanurate, of which only one of the three asymmetric carbon atoms has different optical anisotropy, is commonly called &agr;-type, and provides only a low melting point of a level of 100° C. as it does not have a crystal structure as mentioned above.
Since a high melting point type tris-(2,3-epoxypropyl)-isocyanurate not only has a high melting point but has an extremely low solubility in various solvents as compared with e.g. &agr;-type one, when it is used in a form of a one-pack type reactive mixture as a crosslinking agent for different compounds or for a reactive high polymer, the reaction does not proceed during storage until forcible curing under heating. Accordingly, it is used widely in the field of e.g. electricity and electronic industry materials. The method for producing this high melting point type tris-(2,3-epoxypropyl)-isocyanurate is described in e.g. Journal of Thermal Analysis, Vol. 36 (1990) p1819 or Collected papers of High Polymers, Vol. 47, No. 3 (1990) p169, however, there is a drawback such that chlorous impurities derived from decomposed products or epichlorohydrin used as a material are likely to be contained. Further, by the above method, &agr;-type tris-(2,3-epoxypropyl)-isocyanurate as an impurity is likely to be incorporated, and accordingly, it is necessary to make a sacrifice of yield to increase the purity of the high melting point type tris-(2,3-epoxypropyl)-isocyanurate. As the proportion of &agr;-type to &bgr;-type as high melting point type, present in the tris-(2,3-epoxypropyl)-isocyanurate obtained by a conventional method, is originally 3:1, the above method is extremely inefficient industrially.
DISCLOSURE OF THE INVENTION
It is to provide (2R,2′R,2″R)-tris-(2,3-epoxypropyl)-isocyanurate and (2S,2′S,2″S)-tris-(2,3-epoxypropyl)-isocyanurate, as optically active &bgr;-type tris-(2,3-epoxypropyl)-isocyanurate which is an optically active epoxy compound useful as a high polymer material for e.g. an optical resolution agent or a nonlinear material such as a nonlinear optical material, or as a crosslinking agent for a compound or a high polymer reactive with an epoxy group, a method for efficiently producing it with a high optical purity, and a method for efficiently producing a high melting point type tris-(2,3-epoxypropyl)-isocyanurate with a high purity.
The first aspect of the present invention resides in (2R,2′R,2″R)-tris-(2,3-epoxypropyl)-isocyanurate,
The second aspect of the present invention resides in (2S,2′S,2″S)-tris-(2,3-epoxypropyl)-isocyanurate,
The third aspect of the present invention resides in a method for producing optically active &bgr;-type tris-(2,3-epoxypropyl)-isocyanurate, which comprises reacting isocyanuric acid with an optically active epihalohydrin,
The fourth aspect of the present invention resides in the method for producing optically active &bgr;-type tris-(2,3-epoxypropyl)-isocyanurate according to the above third aspect, which comprises reacting isocyanuric acid with an optically active epihalohydrin by using, as a catalyst, at least one compound selected from the group consisting of a tertiary amine, a quaternary ammonium salt, a tri-substituted phosphine and a quaternary phosphonium salt, to form a 2-hydroxy-3-halopropyl ester of isocyanuric acid, and adding an alkali metal hydroxide or an alkali metal alcoholate to the obtained 2-hydroxy-3-halopropyl ester of isocyanuric acid,
The fifth aspect of the present invention resides in the method for producing optically active &bgr;type tris-(2,3-epoxypropyl)-isocyanurate according to the above third or fourth aspect, wherein 1 mol of isocyanuric acid and from 3 to 60 mol of the optically active epihalohydrin are reacted,
The sixth aspect of the present invention resides in the method for producing optically active &bgr;-type tris-(2,3-epoxypropyl)-isocyanurate according to any one of the above third to fifth aspects, wherein the water content in the reaction mixed liquid is brought to be less than 1% when 1 mol of isocyanuric acid and the optically active epihalohydrin are reacted,
The seventh aspect of the present invention resides in the method for producing optically active &bgr;-type tris-(2,3-epoxypropyl)-isocyanurate according to any one of the above third to sixth aspects, which comprises, after the formation of the 2-hydroxy-3-halopropyl ester of isocyanuric acid, recovering the optically active epihalohydrin used in an excessive amount by a distillation method, adding a solvent for dilution, and adding an alkali metal hydroxide or an alkali metal alcoholate,
The eighth aspect of the present invention resides in the method for producing optically active &bgr;-type tris-(2,3-epoxypropyl)-isocyanurate according to any one of the above third to seventh aspects, which comprises, after the formation of the 2-hydroxy-3-halopropyl ester of isocyanuric acid, recovering the optically acti
Aoki Atsumi
Hidaka Motohiko
Ikeda Hisao
Nissan Chemical Industries Ltd.
Solola Taofiq
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