Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2003-02-07
2004-04-13
Shippen, Michael L. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
Reexamination Certificate
active
06720460
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to novel hydroxyphenyl adamantanes which are useful as excellent materials in improving heat resistance and mechanical strength of epoxy resins, photosensitive resins, aromatic polycarbonate resins, or the like.
More specifically, the present invention relates to novel 1,3-bis(hydroxyphenyl)adamantanes and methods for the production thereof.
Further, the present invention also relates to novel 1,3,5-tris(4-hydroxyphenyl)adamantanes and methods for the production thereof.
2. Description of the Related Art
Hydroxyphenyl adamantanes, namely bisphenols and trisphenols having an adamantane ring skeleton, are desired to be highly heat resistant. One of such adamantane bisphenols already known is 1,3-bis(4-hydroxyphenyl)-5,7-dimethyl adamantane which is synthesized using 1,3-dibromo-5,7-dimethyl adamantane and phenol as raw materials as described in U.S. Pat. No. 3,594,427. Further, 1,3-bis(4-hydroxyphenyl)adamantane which is synthesized using 1,3-adamantane-diol and phenol as raw materials is described in Japanese Patent Application Laid-open No. 2000-143566. Furthermore, 2,2-bis(4′-hydroxyphenyl)adamantane which is synthesized using 2-adamantanone and phenol as raw materials is described in Japanese Patent Application Laid-open No. H10-130371.
However, these known adamantane bisphenols are those which have no substituent group in their hydroxyphenyl groups.
In recent years, characteristic requirements for compounds used as materials for resins such as epoxy resins, photosensitive resins, aromatic polycarbonate resins, or the like have been increasingly heightened and diversified and accordingly, also as for adamantane bisphenols, those having various substituent groups such as alkyl group substituents bonded to hydroxyphenyl groups are desired. However, such compounds and industrially advantageous methods for producing such compounds are not known.
On the other hand, as for compounds having three functional groups on an adamantane ring, 1,3,5-tribromo adamantane and a process for the production of adamantane-1,3-5-triol by using this adamantane as a raw material are described in Japanese Patent Application Laid-open No. H02-196477. Further, a higher carboxylic acid triester of adamantane-1,3,5-triol is described in Japanese Patent Application Laid-open No. H02-104553.
However, trisphenols in which three hydroxyphenyl groups are bonded to an adamantane ring and methods for producing such compounds are not known.
SUMMARY OF THE INVENTION
An object of the present invention is to provide novel 1,3-bis(hydroxyphenyl)adamantanes which are useful as raw material compounds for resins having high heat resistance, and methods for the production thereof. Further, an object of the present invention is to provide novel 1,3,5-tris(4-hydroxyphenyl)adamantanes which are useful as raw material compounds for resins having high thermal resistance, and methods for the production thereof.
Novel hydroxyphenyl adamantanes of the present invention are represented by the following general formula (1):
wherein R is an alkyl group; cycloalkyl group or phenyl group; m is 0 or an integer 1 or 2; l is 0 or 1; when l is 1, hydroxy groups of substituted hydroxyphenyl groups at positions 1 and 3 are together in para-position; n is 0 or an integer 1, 2 or 3; and when l is 0, n is an integer 1, 2 or 3.
Further, 1,3-bis (hydroxyphenyl)adamantanes of the present invention are 1,3-bis(hydroxyphenyl)adamantanes represented by the following general formula (2) in which 4-hydroxyphenyl groups having substituent groups are bonded to positions 1 and 3 of the adamantane ring:
In the general formula (2) above, R is an alkyl group, cycloalkyl group or phenyl group, n is an integer 1, 2 or 3, and m is 0 or an integer 1 or 2.
Further, these compounds can be efficiently produced by reacting a 1,3-adamantane-diol and substituted phenols in the presence of an acid catalyst under reaction conditions which are industrially feasible without difficulty.
Further, the abovementioned 1,3,5-tris(4-hydroxyphenyl)adamantanes of the present invention are 1,3,5-tris(4-hydroxyphenyl)adamantanes represented by the following general formula (3) in which 4-hydroxyphenyl groups with or without substituent groups are bonded at positions 1, 3 and 5 of the adamantane ring:
In the general formula (3) above, R is an alkyl group, cycloalkyl group or phenyl group, n is 0 or an integer 1, 2 or 3, and m is 0 or an integer 1 or 2.
These novel 1,3,5-(4-hydroxyphenyl)adamantanes can be efficiently produced by reacting a 1,3,5-adamantane-triol and phenols in the presence of an acid catalyst under reaction conditions which are industrially feasible without difficulty.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Novel hydroxyphenyl adamantanes of the present invention are represented by the following general formula (1):
In the hydroxyphenyl adamantanes represented by the general formula (1) above, R is an alkyl group, cycloalkyl group, or phenyl group, and when R is an alkyl group, the alkyl group is preferably a straight chain or branched chain alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Examples of such groups include a methyl group, ethyl group, propyl group, and butyl group. The propyl group or butyl group can be a straight chain or branched chain. Further, when R is a cycloalkyl group, a cycloalkyl group having 5 to 6 carbon atoms is preferable, and examples of such groups include a cyclopentyl group and cyclohexyl group. Further, m is 0 or an integer 1 or 2, preferably 0.
l is 0 or 1; when l is 1, hydroxyl groups of substituted hydroxyphenyl groups at positions 1 and 3 are together in para-position; n is 0 or an integer 1, 2 or 3; and when l is 0, n is an integer 1, 2 or 3. Further, when n is 2 or 3, R can be either the same or different, and accordingly hydroxyphenyl adamantanes of the present invention represented by the general formula (1) above can specifically be 1,3-bis(hydroxyphenyl)adamantanes represented by the general formula (2) above and 1,3,5-tris(4-hydroxyphenyl)adamantanes represented by the general formula (3) above.
Examples of the abovementioned 1,3-bis(hydroxyphenyl)adamantanes according to the present invention include 1,3-bis(2-methyl-4-hydroxyphenyl)adamantane, 1,3-bis(3-methyl-4-hydroxyphenyl)adamantane, 1,3-bis(4-methyl-2-hydroxyphenyl)adamantane, 1,3-bis(5-methyl-2-hydroxyphenyl)adamantane, 1,3-bis(3-ethyl-4-hydroxyphenyl)adamantane, 1,3-bis(3-isopropyl-4-hydroxyphenyl)adamantane, 1,3-bis(3-s-butyl-4-hydroxyphenyl)adamantane, 1,3-bis(3-t-butyl-4-hydroxyphenyl)adamantane, 1,3-bis(3,6-dimethyl-4-hydroxyphenyl)adamantane, 1,3-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane, 1,3-bis(3,6-dimethyl-2-hydroxyphenyl)adamantane, 1,3-bis(2,3,5-trimethylhydroxyphenyl)adamantane, 1,3-bis(2,3,6-trimethyl-4-hydroxyphenyl)adamantane, 1,3-bis(3,4,6-trimethyl-2-hydroxyphenyl)adamantane, 1,3-bis(3-cyclohexyl-4-hydroxyphenyl)adamantane, 1,3-bis(2-methyl-5-cyclohexyl-4-hydroxyphenyl)adamantane, 1,3-bis(3-phenyl-4-hydroxyphenyl)adamantane, 1,3-bis(3-methyl-4-hydroxyphenyl)-5,7-dimethyladamantane, 1,3-bis(3-isopropyl-4-hydroxyphenyl)-5,7-dimethyladamantane, 1,3-bis(3,6-dimethyl-4-hydroxyphenyl)-5,7-dimethyladamantane, 1,3-bis(2,3,5-trimethyl-4-hydroxyphenyl)-5,7-dimethyladamantane, 1,3-bis(2,3,6-trimethyl-4-hydroxyphenyl)-5,7-dimethyladamantane, 1,3-bis(3-cyclohexyl-4-hydroxyphenyl)-5,7-dimethyladamantane, 1,3-bis(2-methyl-5-cyclohexyl-4-hydroxyphenyl)-5,7-dimethyladamantane, 1,3-bis(3-phenyl-4-hydroxyphenyl)-5,7-dimethyladamantane, 1,3-bis(3-methyl-4-hydroxyphenyl)-4-methyladamantane, 1,3-bis(3-isopropyl-4-hydroxyphenyl)-4-methyl-adamantane, 1,3-bis(3,6-dimethyl-4-hydroxyphenyl)-4-methyl-adamantane, 1,3-bis(2,3,5-trimethyl-4-hydroxyphenyl)-4-methyl-adamantane, 1,3-bis(2,3,6-trimethyl-4-hydroxyphenyl)-4-methyl-adamantane, 1,3-bis(2-methyl-5-cyclohexyl-4-hydroxyphenyl)-4-methyl-adamantane, and 1,3-bis(3-phenyl-4-hydroxyphenyl)-4-methyl-adamantane.
Furthermore, examples of the abovementioned 1,3,5-tris(4-hy
Ekawa Kenji
Hazama Miwa
Watanabe Kentaro
Yao Kazuhiko
Yoshikawa Akira
Honshu Chemical Industry Co. Ltd.
Knobbe Martens Olson & Bear LLP
Shippen Michael L.
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