JP2007186493A - Bisaminophenol compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bisaminophenol compound which can be converted into resins having low specific dielectric constants. <P>SOLUTION: This bisaminophenol compound having a structure in which two groups each having an aminohydroxyphenyl group are bound to a group comprising a diamondoid structure. The bisaminophenol compound is preferably a compound represented by the general formula (1) [X is a group comprising a diamond structure; (n) is 0 or 1; Y is H, an alkyl group, or a group comprising a diamondoid structure]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to bisaminophenol compounds.

Bisaminophenols with two aminophenol structures in one molecule are used as raw materials for aromatic polyamide resins, polyimide resins, polybenzoxazole resins, etc., and resins with various structures are synthesized according to their use. Is being used.
When these resins are used as insulating films for semiconductors, they are characterized by a low relative dielectric constant compared to inorganic insulating films such as oxide films. Has been widely studied. In addition, a polyimide resin is widely known as a material for forming an insulating film (see, for example, Patent Document 1). However, semiconductor devices have been increased in speed, miniaturization, high integration, and low power consumption. In order to cope with such high performance, there has been a problem that the relative dielectric constant is still not sufficient.
JP-A-5-121396

  An object of the present invention is to provide a bisaminophenol compound that can be converted into a low dielectric constant resin under such circumstances.

（式中のＸは、ダイヤモンドイド構造より構成される基を示し、ｎは、０または１を示し、Ｙは水素原子またはアルキル基またはダイヤモンドイド構造より構成される基を示す。）
（３） 前記ビスアミノフェノール化合物は、前記一般式（１）におけるフェニレン基上の置換基として、アルキル基またはダイヤモンドイド構造より構成される基を有するものである、第（２）項に記載のビスアミノフェノール化合物。
（４） 前記ビスアミノフェノール化合物は、前記一般式（１）におけるＹ及び／又はフェニレン基上の置換基として、ダイヤモンドイド構造より構成される基を有するものである、第（２）項又は第（３）項に記載のビスアミノフェノール化合物、
（５） 前記ビスアミノフェノール化合物は、前記一般式（１）におけるＹとして、ダイヤモンドイド構造より構成される基を有するものである、第（２）項乃至第（４）項のいずれか１項に記載のビスアミノフェノール化合物、
（６） 前記ビスアミノフェノール化合物は、前記一般式（１）におけるｎとして、０である、第（２）項乃至第（５）項のいずれか１項に記載のビスアミノフェノール化合物、
（７） 前記ビスアミノフェノール化合物は、前記一般式（１）におけるＸとして、置換基を有しても良いアダマンチル基を有するものである、第（２）項乃至第（６）項のいずれか１項に記載のビスアミノフェノール化合物、
（８） 前記ビスアミノフェノール化合物は、前記一般式（１）におけるＸとして、置換基を有しても良いビアダマンチル基を有するものである、第（２）項乃至第（７）項のいずれか１項に記載のビスアミノフェノール化合物、
（９） 前記置換基は、アルキル基である、第（７）項又は第（８）項に記載のビスアミノフェノール化合物、
（１０） 前記置換基を有しても良いビアダマンチル基が、テトラメチルビアダマンチル基である第（８）項に記載のビスアミノフェノール化合物、
を提供するものである。 That is, the present invention
(1) A bisaminophenol compound having a structure in which two groups having an aminohydroxyphenyl group are bonded to a group composed of a diamondoid structure,
(2) The bisaminophenol compound according to item (1), wherein the bisaminophenol compound is represented by the general formula (1),

(In the formula, X represents a group composed of a diamondoid structure, n represents 0 or 1, and Y represents a hydrogen atom, an alkyl group or a group composed of a diamondoid structure.)
(3) The bisaminophenol compound according to (2), wherein the bisaminophenol compound has a group composed of an alkyl group or a diamondoid structure as a substituent on the phenylene group in the general formula (1). Bisaminophenol compound.
(4) The bisaminophenol compound has a group composed of a diamondoid structure as a substituent on Y and / or a phenylene group in the general formula (1), the item (2) or the item The bisaminophenol compound according to item (3),
(5) The bisaminophenol compound, as Y in the general formula (1), has a group composed of a diamondoid structure, any one of items (2) to (4) A bisaminophenol compound,
(6) The bisaminophenol compound according to any one of (2) to (5), wherein n in the general formula (1) is 0,
(7) Any of (2) to (6), wherein the bisaminophenol compound has an adamantyl group which may have a substituent as X in the general formula (1). The bisaminophenol compound according to item 1,
(8) Any of the items (2) to (7), wherein the bisaminophenol compound has a beadamantyl group which may have a substituent as X in the general formula (1). The bisaminophenol compound according to claim 1,
(9) The bisaminophenol compound according to (7) or (8), wherein the substituent is an alkyl group,
(10) The bisaminophenol compound according to item (8), wherein the biadamantyl group which may have a substituent is a tetramethylbiadamantyl group,
Is to provide.

  According to the present invention, it is possible to provide a bisaminophenol compound that can be suitably used as a raw material for a polymer having a low relative dielectric constant.

  The present invention is a bisaminophenol compound having a structure in which two groups having an aminohydroxyphenyl group are bonded to a group composed of a diamondoid structure, wherein the two aminohydroxyphenyl groups are composed of a diamondoid structure. Two of the structure directly bonded to the group, the group having the aminohydroxyphenyl group, and the group having the aminohydroxyphenyl group and a linking group such as an aromatic group such as a phenylene group and an oxyphenylene group, And those having a structure bonded to a group composed of a diamondoid structure via the. As what has such a structure, what has a structure represented by the said General formula (1) is mentioned, for example. These can be suitably used as a raw material for a polymer having a low relative dielectric constant.

  In the present invention, the diamondoid structure is a polycyclic structure having an adamantane structure as a minimum unit, and as a group constituted from this structure, specifically, an adamantyl group, a diamantyl group, a triamantyl group, a tetramantyl group, Examples include a pentamantyl group, a hexamantyl group, a heptamantyl group, an octamantyl group, a nonamantyl group, a decamantyl group and an undecamantyl group, and further includes a group having a plurality of groups having the polycyclic skeleton structure. Examples include biadamantyl group, triadamantyl group, tetraadamantyl group, pentaadamantyl group, hexaadamantyl group, heptaadamantyl group, octaadamantyl group, nonaadamantyl group, decaadamantyl group, undecaadamantyl group, etc. Not intended to be constant. With these, a resin having a low relative dielectric constant can be obtained, and among them, an adamantyl group and a biadamantyl group are more preferable.

  The hydrogen atom in the diamondoid structure may be substituted with an aliphatic group, an aromatic group and a fluorine atom. Examples of the aliphatic group that may be substituted with the hydrogen atom include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; and an alkoxy group such as a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Alkenyl groups such as vinyl group, propenyl group and butenyl group; alkynyl groups such as ethynyl group, propynyl group and butynyl group; alicyclic groups such as cyclopentyl group, cyclohexyl group, adamantyl group, diamantyl group and biadamantyl group Examples of the aromatic group that may be substituted for the hydrogen atom include, but are not limited to, a phenyl group, a naphthyl group, a phenoxy group, and a naphthoxy group. It is not something. Moreover, the hydrogen atom in the aliphatic group and aromatic group which may be substituted with the hydrogen atom may be substituted with a fluorine atom. With these, a resin having solubility and heat resistance can be obtained, and among these, an alkyl group is more preferable. In the case of the above biadamantyl group, a biadamantyl group having an alkyl substituent substituted with the above alkyl group can be exemplified, and specific examples thereof include a tetramethylbiadamantyl group substituted with four alkyl groups and the like. Can be mentioned.

The bisaminophenol compound represented by the general formula (1) has a group composed of a diamondoid structure as X in the formula, and Y in the formula represents a hydrogen atom, an alkyl group or diamond. It has a group composed of an id structure.
The bisphenol compound of the present invention may have a group composed of an alkyl group or a diamondoid structure as a substituent on the phenylene group in the general formula (1).
In the compound represented by the general formula (1), when the resin is used, the diamond is used as a group composed of the diamondoid structure as Y and as a substituent on the phenylene group in order to lower the dielectric constant. It is preferable to have a group composed of an idoid structure or a group composed of the diamondoid structure as a substituent on the Y and phenylene groups.
In addition, in the bisaminophenol compound represented by the general formula (1), the group composed of the diamondoid structure as a substituent on the X, Y and phenylene groups includes the group composed of the diamondoid structure. The same can be mentioned.
In the bisaminophenol compound represented by the general formula (1), examples of the alkyl group as a substituent on Y and the phenylene group include, but are not limited to, a methyl group, an ethyl group, a propyl group, and a butyl group. Is not to be done.

  Specific examples of the bisaminophenol compound of the present invention include, among these, compounds in which n is 0 in the general formula (1), for example, 3,3′-bis (3-amino-4-hydroxyphenyl)- 1,1′-biadamantane, 3,3′-bis (3-amino-4-hydroxy-5-methylphenyl) -1,1′-biadamantane, 3,3′-bis (5-amino-4-) Hydroxy-2-methylphenyl) -1,1′-biadamantane, 3,3′-bis (3-amino-4-hydroxyphenyl) -5,5 ′, 7,7′-tetramethyl-1,1 ′ -Biadamantane, 3,3'-bis (3-amino-4-hydroxy-5-methylphenyl) -5,5 ', 7,7'-tetramethyl-1,1'-biadamantane, 3,3' -Bis (5-amino-4-hydroxy-2) Methylphenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane, 1,3-bis (3-amino-4-hydroxyphenyl) -diamantane, 1,3-bis (3 -Amino-4-hydroxy-5-methylphenyl) -diamantane, 1,3-bis (5-amino-4-hydroxy-2-methylphenyl) -diamantane, 1,3-bis (3-amino-4-hydroxy) Phenyl) -triamantane, 1,3-bis (3-amino-4-hydroxy-5-phenyl) -triamantane, 1,3-bis (5-amino-4-hydroxy-2-phenyl) -triamantane, 2,2-bis (5-amino-4-hydroxy-3- (1-adamantyl) phenyl) adamantane, 2,2-bis (5-amino-4-hydroxy-3- (3- (1, '-Biadamantyl) phenyl) adamantane, 2,2-bis (5-amino-4-hydroxy-3- (7- (3,3', 5,5'-tetramethyl-1,1'-biadamantyl)) ) Phenyl) adamantane, 2,2-bis (5-amino-4-hydroxy-3- (3,5-dimethyl-1-adamantyl) phenyl) adamantane, 3,3′-bis (3-amino-4-hydroxy) -5- (3,5-dimethyl-1-adamantyl) phenyl) -1,1'-biadamantane, 3,3'-bis (3-amino-4-hydroxy-5- (3,5-dimethyl-1) -Adamantyl) phenyl) -5,5 ', 7,7'-tetramethyl-1,1'-biadamantane, 3,3'-bis (3-amino-4-hydroxy-5- (3- (5 5 ', 7,7'-tetramethyl)- 1,1′-biadamantyl) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane, 4,4-bis (5-amino-4-hydroxy-3- (1) -Adamantyl) phenyl) -1,1'-biadamantane, 4,4-bis (5-amino-4-hydroxy-3- (3- (1,1'-biadamantyl) phenyl) -1,1'- Biadamantane, 4,4-bis (5-amino-4-hydroxy-3- (3,5-dimethyl-1-adamantyl) phenyl) -1,1′-biadamantane, 4,4-bis (5-amino) -4-hydroxy-3- (7- (3,3 ′, 5,5′-tetramethyl-1,1′-biadamantyl)) phenyl) -1,1′-biadamantane, 4,4-bis ( 5-Amino-4-hydroxy-3- (1-adamantyl) fe ) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane, 4,4-bis (5-amino-4-hydroxy-3- (3- (1,1′-bi) Adamantyl) phenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane, 4,4-bis (5-amino-4-hydroxy-3- (3,5-dimethyl-1) -Adamantyl) phenyl) -3,3 ', 5,5'-tetramethyl-1,1'-biadamantane and 4,4-bis (5-amino-4-hydroxy-3- (7- (3,3) ', 5,5'-tetramethyl-1,1'-biadamantyl)) phenyl) -3,3', 5,5'-tetramethyl-1,1'-biadamantane, and the like. However, it is not limited to these.

In addition, in the structure represented by the general formula (1), among these, as the compound in which n is 1 in the general formula (1), for example, 1,3-bis (4- (4-amino-3-hydroxyphenoxy) ) Phenyl) -adamantane, 1,3-bis (4- (4-amino-3-hydroxyphenoxy) phenyl) -5,7-dimethyladamantane, 3,3′-bis (4- (4-amino-3-) Hydroxyphenoxy) phenyl) -1,1'-biadamantane, 3,3'-bis (4- (4-amino-3-hydroxyphenoxy) phenyl) -5,5 ', 7,7'-tetramethyl-1 , 1′-Biadamantane, 1,3-bis (4- (4-amino-3-hydroxyphenoxy) phenyl) -diamantane, 1,3-bis (4- (4-amino-3-hydroxyphenoxy) phenyl) -G Amantane, 3,3′-bis (4- (2- (1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -1,1′-biadamantane, 3,3′-bis (4- ( 2- (1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane, 1,3-bis (4- ( 2- (1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -diamantane, 1,3-bis (4- (2- (1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -Triamantane, 3,3'-bis (4- (2- (3,5-dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -1,1'-biadamantane, 3, 3'-bis (4 (2- (3,5-dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane, 1, 3-bis (4- (2- (3,5-dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -diamantane, 1,3-bis (4- (2- (3,5 -Dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -triamantane, 3,3'-bis (4- (2- (3- (1,1'-biadamantyl)))-4 -Amino-3-hydroxyphenoxy) phenyl) -1,1'-biadamantane, 3,3'-bis (4- (2- (3- (1,1'-biadamantyl))-4-amino-3 -Hydroxyphenoxy) phenyl) -5,5 ', 7,7′-tetramethyl-1,1′-biadamantane, 1,3-bis (4- (2- (3- (1,1′-biadamantyl))-4-amino-3-hydroxyphenoxy) Phenyl) -diamantane, 1,3-bis (4- (2- (3- (1,1′-biadamantyl))-4-amino-3-hydroxyphenoxy) phenyl) -triamantane, 3,3′- Bis (4- (2- (3- (5,5 ′, 7,7′-tetramethyl) -1,1′-biadamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -1,1 ′ -Biadamantane, 3,3'-bis (4- (2- (3- (5,5 ', 7,7'-tetramethyl) -1,1'-biadamantyl) -4-amino-3-hydroxy Phenoxy) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane, 1 , 3-Bis (4- (2- (3- (5,5 ', 7,7'-tetramethyl) -1,1'-biadamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -diamantane 1,3-bis (4- (2- (3- (5,5 ′, 7,7′-tetramethyl) -1,1′-biadamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -Triamantane, 3,3'-bis (4- (6- (1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -1,1'-biadamantane, 3,3'-bis (4 -(6- (1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -5,5 ', 7,7'-tetramethyl-1,1'-biadamantane, 1,3-bis (4 -(6- (1-adamantyl) -4-amino-3-hydroxyphenoxy ) Phenyl) -diamantane, 1,3-bis (4- (6- (1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -triamantane, 3,3′-bis (4- (6- (3,5-Dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -1,1′-biadamantane, 3,3′-bis (4- (6- (3,5-dimethyl) -1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane, 1,3-bis (4- (6- (3,5-dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -diamantane, 1,3-bis (4- (6- (3,5-dimethyl-1-adamantyl) -4 -Amino-3-hydro Ciphenoxy) phenyl) -triamantane, 3,3′-bis (4- (6- (3- (1,1′-biadamantyl))-4-amino-3-hydroxyphenoxy) phenyl) -1,1 '-Biadamantane, 3,3'-bis (4- (6- (3- (1,1'-biadamantyl))-4-amino-3-hydroxyphenoxy) phenyl) -5,5', 7, 7'-tetramethyl-1,1'-biadamantane, 1,3-bis (4- (6- (3- (1,1'-biadamantyl))-4-amino-3-hydroxyphenoxy) phenyl) -Diamantane, 1,3-bis (4- (6- (3- (1,1'-biadamantyl))-4-amino-3-hydroxyphenoxy) phenyl) -triamantane, 3,3'-bis ( 4- (6- (3- (5,5 ′, 7,7′-tetramethyl) -1 1′-biadamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -1,1′-biadamantane, 3,3′-bis (4- (6- (3- (5,5 ′, 7, 7′-tetramethyl) -1,1′-biadamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane, 1 , 3-Bis (4- (6- (3- (5,5 ′, 7,7′-tetramethyl) -1,1′-biadamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -diamantane 1,3-bis (4- (6- (3- (5,5 ′, 7,7′-tetramethyl) -1,1′-biadamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -Triamantane, 2,2-bis (4- (4-amino-3-hydroxyphenoxy) ) Phenyl) adamantane, 2,2-bis (4- (4-amino-3-hydroxyphenoxy) phenyl) -5,7-dimethyladamantane, 2,2-bis (4- (4-amino-3-hydroxyphenoxy) ) -3- (1-adamantyl) phenyl) adamantane, 2,2-bis (4- (4-amino-5-hydroxy-2- (1-adamantyl) phenoxy) phenyl) adamantane, 2,2-bis (4 -(4-Amino-5-hydroxy-2- (1-adamantyl) phenoxy) -3- (1-adamantyl) phenyl) adamantane, 2,2-bis (4- (4-amino-3-hydroxyphenoxy)- 3- (3- (1,1′-biadamantyl) phenyl) adamantane, 2,2-bis (4- (4-amino-3-hydroxyphenoxy) -3- (3 5-dimethyl-1-adamantyl) phenyl) adamantane, 2,2-bis (4- (4-amino-5-hydroxy-2- (3,5-dimethyl-1-adamantyl) phenoxy) phenyl) adamantane, 2, 2-bis (4- (4-amino-5-hydroxy-2- (3,5-dimethyl-1-adamantyl) phenoxy) -3- (3,5-dimethyl-1-adamantyl) phenyl) adamantane, 2, 2-bis (4- (4-amino-3-hydroxyphenoxy) -3- (7- (3,3 ′, 5,5′-tetramethyl-1,1′-biadamantyl)) phenyl) adamantane, 3 , 3′-bis (3- (3,5-dimethyl-1-adamantyl) -4- (4-amino-3-hydroxyphenoxy) phenyl) -1,1′-biadamantane, 3,3′-bis ( 3- ( , 5-dimethyl-1-adamantyl) -4- (4-amino-3-hydroxyphenoxy) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane, 3,3 ′ -Bis (3- (3- (5,5 ', 7,7'-tetramethyl) -1,1'-biadamantyl) -4- (4-amino-3-hydroxyphenoxy) phenyl) -5,5 ', 7,7'-tetramethyl-1,1'-biadamantane, 3,3'-bis (3- (3- (5,5', 7,7'-tetramethyl) -1,1'- Biadamantyl) -4- (6- (3,5-dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1 ′ -Biadamantane, 3,3'-bis (3-methyl-4- (4-amino-3-hydroxyphenoxy) fe ) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane, 3,3′-bis (3- (1-butyl) -4- (4-amino-3-hydroxyphenoxy) ) Phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane, 3,3′-bis (3- (1-hexyl) -4- (4-amino-3-hydroxy) Phenoxy) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane, 3,3′-bis (3- (3,5-dimethyl-1-adamantyl) -4- ( 4-amino-3-hydroxy-6- (1-hexyl) phenoxy) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane, 4,4-bis (4- ( 4-amino-3-hydroxyphenoxy) phenyl) -1,1′-biadamantane, 4,4-bis (4- ( -Amino-3-hydroxyphenoxy) -3- (1-adamantyl) phenyl) -1,1'-biadamantane, 4,4-bis (4- (4-amino-5-hydroxy-2- (1-adamantyl) ) Phenoxy) phenyl) -1,1'-biadamantane, 4,4-bis (4- (4-amino-5-hydroxy-2- (1-adamantyl) phenoxy) -3- (1-adamantyl) phenyl) -1,1'-biadamantane, 4,4-bis (4- (4-amino-3-hydroxyphenoxy) -3- (3- (1,1'-biadamantyl) phenyl) -1,1'- Biadamantane, 4,4-bis (4- (4-amino-3-hydroxyphenoxy) -3- (3,5-dimethyl-1-adamantyl) phenyl) -1,1′-biadamantane, 4,4- Bis (4- (4-Ami No-5-hydroxy-2- (3,5-dimethyl-1-adamantyl) phenoxy) phenyl) -1,1′-biadamantane, 4,4-bis (4- (4-amino-5-hydroxy-2) -(3,5-dimethyl-1-adamantyl) phenoxy) -3- (3,5-dimethyl-1-adamantyl) phenyl) -1,1'-biadamantane, 4,4-bis (4- (4- Amino-3-hydroxyphenoxy) -3- (7- (3,3 ′, 5,5′-tetramethyl-1,1′-biadamantyl)) phenyl) -1,1′-biadamantane, 4,4 -Bis (4- (4-amino-3-hydroxyphenoxy) phenyl) -3,3 ', 5,5'-tetramethyl-1,1'-biadamantane, 4,4-bis (4- (4- Amino-3-hydroxyphenoxy) -3- (1-adamanti) ) Phenyl) -3,3 ', 5,5'-tetramethyl-1,1'-biadamantane, 4,4-bis (4- (4-amino-5-hydroxy-2- (1-adamantyl) phenoxy) ) Phenyl) -3,3 ', 5,5'-tetramethyl-1,1'-biadamantane, 4,4-bis (4- (4-amino-5-hydroxy-2- (1-adamantyl) phenoxy) ) -3- (1-adamantyl) phenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane, 4,4-bis (4- (4-amino-3-hydroxyphenoxy) ) -3- (3- (1,1′-biadamantyl) phenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane, 4,4-bis (4- (4 -Amino-3-hydroxyphenoxy) -3- (3,5-dimethyl-1-adamantyl) Phenyl) -3,3 ', 5,5'
Tetramethyl-1,1′-biadamantane, 4,4-bis (4- (4-amino-5-hydroxy-2- (3,5-dimethyl-1-adamantyl) phenoxy) phenyl) -3,3 ′ , 5,5'-tetramethyl-1,1'-biadamantane, 4,4-bis (4- (4-amino-5-hydroxy-2- (3,5-dimethyl-1-adamantyl) phenoxy)- 3- (3,5-Dimethyl-1-adamantyl) phenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane and 4,4-bis (4- (4-amino- 3-hydroxyphenoxy) -3- (7- (3,3 ′, 5,5′-tetramethyl-1,1′-biadamantyl)) phenyl) -3,3 ′, 5,5′-tetramethyl- 1,1'-biadamantane, etc., but are not limited thereto. Is not something

As a typical example of the method for producing a bisaminophenol compound of the present invention, a bisaminophenol compound having a structure represented by the general formula (1) can be synthesized by the following route, for example.
When n is 0 in the general formula (1), first, an alicyclic compound containing a diamondoid structure is halogenated using a halogenating agent such as bromine or iodine to form the diamondoid structure. To obtain a dihalogenated compound containing
In the halogenation reaction, when a solvent is used, the type thereof is not particularly limited, but acetic acid, hexane, pentane, or the like is preferable. In particular, when bromine is used, the reaction may be performed without a solvent. In order to promote the reaction, a catalyst may be used. As the catalyst, Lewis acid catalysts such as aluminum chloride and aluminum bromide are preferable, but the catalyst may be used without a catalyst. The amount of the catalyst to be used is desirably 2 equivalents or more and 100 equivalents or less, preferably 3 equivalents or more and 50 equivalents or less, with respect to the compound containing the diamondoid structure. Although it does not specifically limit as reaction temperature depends on the activity of reaction which each compound has, -50 degreeC or more and 100 degrees C or less are preferable. Moreover, as reaction time, 1 hour or more and 100 hours or less are preferable, More preferably, it is 24 hours or more and 100 hours or less.

  Of the dihalogenated compounds containing a group composed of the diamondoid structure, brominated compounds are those described in the literature (T. Gund, P. Schleyer, G. Unruh, G. Gleicher, Journal of Organic Chemistry, Vol. 39). , 2995-3003, 1974).

Next, by performing Friedel-Crafts reaction between the dihalogenated compound containing a group composed of the diamondoid structure obtained above and a hydroxybenzene compound such as phenol, m-cresol and o-cresol, diamondoid is obtained. A bis (hydroxyphenyl) compound containing a group composed of the structure is obtained.
As a method for synthesizing a bis (hydroxyphenyl) compound containing a group composed of the above diamondoid structure, literature (Der-Jang Liaw, Been-Yang Liaw, Macromol. Chem. Phys., 200, 1326-1332, 1999) can also be synthesized by a dehydration condensation reaction using an acid catalyst between an adamantanone compound and the hydroxybenzene compound.

Examples of the adamantanone compound include 2-adamantanone, 1,3-dimethyl-2-adamantanone, 1,3-dimethyl-4-adamantanone, 1,3-dimethyl-6-adamantanone and 1- ( 1-adamantyl) -2-adamantanone and the like. Examples of the acid catalyst include sulfuric acid and hydrochloric acid.
Here, as said hydroxybenzene compound, when Y in General formula (1) is a hydrogen atom, it is preferable to use a phenol.

  Moreover, when Y in General formula (1) is an alkyl group, it is preferable to use an alkylhydroxybenzene compound as said hydroxybenzene compound. For example, when Y in the general formula (1) is a methyl group, it is preferable to use m-cresol or o-cresol, and when Y is a butyl group, o-butylphenol or m-butylphenol is preferably used.

  When Y in the general formula (1) is a group composed of a diamondoid structure, a bis (hydroxyphenyl) compound containing a group composed of a diamondoid structure obtained by using phenol as the hydroxybenzene compound; By performing a Friedel-Crafts reaction with a halogenated compound containing a group composed of a diamondoid structure, a hydrogen atom on the target hydroxyphenyl group was substituted with a group composed of the diamondoid structure A bis (hydroxyphenyl) compound containing a group composed of a diamondoid structure is obtained. The halogenated compound containing a group constituted by the diamondoid structure can be synthesized in the same manner as the dihalogenated compound containing a group constituted by the diamondoid structure.

  In the Friedel-Crafts reaction, when a solvent is used, the type thereof is not particularly limited, but benzene, toluene, xylene, acetonitrile, nitromethane, and the like are preferable, but the solvent may be used without a solvent. The amount of the solvent used is preferably from 0.5 to 50 times by weight, more preferably from 0.5 to 10 times by weight, relative to the raw material used for this reaction. In the Friedel-Crafts reaction, it is preferable to use a catalyst for promoting the reaction, and as such a catalyst, Lewis acid catalysts such as aluminum chloride and aluminum bromide are preferable. Good. The amount of the catalyst used is desirably 0.05 equivalent times or more and 10 equivalent times or less, preferably 0.05 equivalent times or more and 1 equivalent time or less, more preferably based on the dihalogenated compound. 0.05 equivalent times or more and 0.5 equivalent times or less. The reaction temperature is not particularly limited because it depends on the activity of the reaction of each compound, but is preferably −20 ° C. or higher and 200 ° C. or lower. When the reaction is performed without a catalyst, the reaction temperature is 100 ° C. or higher and 200 ° C. or lower. preferable. The reaction time is 1 hour or more and 100 hours or less, more preferably 1 hour or more and 48 hours or less. The molar ratio of the bisphenol compound used in this reaction is preferably 2 equivalents or more and 200 equivalents or less, more preferably 10 equivalents or more and 100 equivalents or less, relative to the dihalogenated compound.

Next, using a nitrating agent such as sulfuric acid and nitric acid, the hydroxyphenyl group of the bis (hydroxyphenyl) compound containing the group composed of the diamondoid structure obtained above is nitrated to form the diamondoid structure A bis (nitrohydroxyphenyl) aromatic compound containing a group is obtained.
Subsequently, this is dispersed or dissolved in a suitable solvent such as tetrahydrofuran, ethanol or N, N-dimethylformamide and treated with palladium-activated carbon or platinum-activated carbon at room temperature under a hydrogen atmosphere, or The target bisaminophenol compound can be obtained by treating with tin or tin chloride under acidic conditions.

  In the case where n in the general formula (1) is 1, bis (hydroxyphenyl) containing a group composed of a diamondoid structure obtained in the synthesis in the case where the compound in the general formula (1) is 0 Using this compound and a fluorinated nitrophenol compound or chlorophenol nitrophenol compound in which the phenolic hydroxyl group is protected with a benzyl group, using a base such as potassium carbonate in a solvent such as N, N-dimethylformamide To obtain a nitrohydroxyphenoxy aromatic compound containing a group composed of a diamondoid structure in which a phenolic hydroxyl group is protected with a benzyl group.

  Here, in the synthesis when n is 1, as the bis (hydroxyphenyl) compound containing a group composed of the diamondoid structure, all the substituents on the phenylene group in the general formula (1) are hydrogen atoms. In the case of using a compound obtained by a synthesis method in which n in the general formula (1) is 0 and Y is a hydrogen atom, and having an alkyl group as a substituent on the phenylene group in the general formula (1), A group composed of a diamondoid structure is used as a substituent on the phenylene group in the general formula (1) using a compound obtained by a synthesis method in which n in the general formula (1) is 0 and Y is an alkyl group. When it has, it is obtained by the synthesis method in the case where n in the general formula (1) is 0 and Y in the general formula (1) is a group composed of a diamondoid structure Bis containing group composed from Iyamondoido structure may be used (hydroxyphenyl) compounds.

  In the etherification reaction, the reaction temperature is preferably 50 ° C. or higher and 150 ° C. or lower, more preferably 100 ° C. or higher and 150 ° C. or lower. The reaction time is 1 hour or more and 100 hours or less, more preferably 24 hours or more and 100 hours or less.

  In a suitable solvent such as tetrahydrofuran, ethanol or N, N-dimethylformamide, the nitrohydroxyphenoxy aromatic compound containing a group composed of a diamondoid structure in which the phenolic hydroxyl group obtained above is protected with a benzyl group is obtained. The target bisaminophenol compound can be obtained by treating the dispersed or dissolved product with palladium-activated carbon or platinum-activated carbon at room temperature in a hydrogen atmosphere.

  Examples of the alicyclic compound containing the diamondoid structure include adamantane, diamantane, triamantane, tetramantane, pentamantane, hexamantane, heptamantane, octamantane, nonamantane, decamantane, undecamantan, biadamantane, triadamantane, Tetraadamantane, pentaadamantane, hexaadamantane, heptaadamantane, octaadamantane, nonaadamantane, decaadamantane, undecaadamantane, vidiamantane, tridiamantane, tetradiamantane, pentadiamantane, hexadiamantane, heptadiamantane, octadiamantane And compounds having a polycyclic skeleton structure such as nonadiamantane, decadiamantane and undecadiamantane. Although it is not intended to be limited thereto. The hydrogen atom in the diamondoid structure of these alicyclic compounds is an aliphatic group, an aromatic group, or a fluorine atom that may be substituted for the hydrogen atom in the diamondoid structure in the group composed of the diamondoid structure. It may be replaced.

  Examples of the fluorinated nitrophenol compound or chlorinated nitrophenol compound in which the phenolic hydroxyl group is protected with a benzyl group include 2-benzyloxy-4-fluoronitrobenzene, 3 when Y in the general formula (1) is a hydrogen atom. -Benzyloxy-4-fluoronitrobenzene, 2-benzyloxy-6-fluoronitrobenzene, 3-benzyloxy-6-fluoronitrobenzene, 2-benzyloxy-4-chloronitrobenzene, 3-benzyloxy-4-chloronitrobenzene, 2 When Y in the general formula (1) is an alkyl group, such as -benzyloxy-6-chloronitrobenzene and 3-benzyloxy-6-chloronitrobenzene, 3-methyl-2-benzyloxy-4-fluoronitrobenzene, 5-methyl -2- Benzyloxy-4-fluoronitrobenzene, 6-methyl-2-benzyloxy-4-fluoronitrobenzene, 3- (1-butyl) -2-benzyloxy-4-fluoronitrobenzene, 5- (1-butyl) -2-benzyl In the case where oxy-4-fluoronitrobenzene, 6- (1-butyl) -2-benzyloxy-4-fluoronitrobenzene, or the like, or Y in the general formula (1) is a group composed of a diamondoid structure, 3- (1 -Adamantyl) -2-benzyloxy-4-fluoronitrobenzene, 5- (1-adamantyl) -2-benzyloxy-4-fluoronitrobenzene, 6- (1-adamantyl) -2-benzyloxy-4-fluoronitrobenzene, 3- (3,5-Dimethyl-1-adamantyl) -2-benzylo Ci-4-fluoronitrobenzene, 5- (3,5-dimethyl-1-adamantyl) -2-benzyloxy-4-fluoronitrobenzene, 6- (3,5-dimethyl-1-adamantyl) -2-benzyloxy- 4-fluoronitrobenzene, 3- (1-diamantyl) -2-benzyloxy-4-fluoronitrobenzene, 5- (1-diamantyl) -2-benzyloxy-4-fluoronitrobenzene, 6- (1-diamantyl) -2 -Benzyloxy-4-fluoronitrobenzene, 3- (1-triamantyl) -2-benzyloxy-4-fluoronitrobenzene, 5- (1-triamantyl) -2-benzyloxy-4-fluoronitrobenzene, 6- (1- Triamantyl) -2-benzyloxy-4-fluoronitrobenzene, 3- (3- (1,1′-biadamantyl))-2-benzyloxy-4-fluoronitrobenzene, 5- (3- (1,1′-biadamantyl))-2-benzyloxy-4-fluoro Nitrobenzene, 6- (3- (1,1′-biadamantyl))-2-benzyloxy-4-fluoronitrobenzene, 3- (3- (5,5 ′, 7,7′-tetramethyl-1,1) '-Biadamantyl))-2-benzyloxy-4-fluoronitrobenzene, 5- (3- (5,5', 7,7'-tetramethyl-1,1'-biadamantyl))-2-benzyloxy -4-fluoronitrobenzene, 6- (3-((5,5 ', 7,7'-tetramethyl-1,1'-biadamantyl))-2-benzyloxy-4-fluoronitrobenzene, 2- (1 -Adamantyl -3-benzyloxy-4-fluoronitrobenzene, 4- (1-adamantyl) -3-benzyloxy-4-fluoronitrobenzene, 5- (1-adamantyl) -3-benzyloxy-4-fluoronitrobenzene, 3- ( 1-adamantyl) -2-benzyloxy-6-fluoronitrobenzene, 4- (1-adamantyl) -2-benzyloxy-6-fluoronitrobenzene, 5- (1-adamantyl) -2-benzyloxy-6-fluoronitrobenzene 2- (1-adamantyl) -3-benzyloxy-6-fluoronitrobenzene, 4- (1-adamantyl) -3-benzyloxy-6-fluoronitrobenzene and 5- (1-adamantyl) -3-benzyloxy- 6-fluoronitrobenzene, etc.

The bisaminophenol compound obtained above can be converted into a polyamide resin, a polyimide resin precursor, a polybenzoxazole resin, and the like by a condensation reaction with a carboxylic acid compound.
Examples of the carboxylic acid compound include benzenedicarboxylic acid, naphthalene dicarboxylic acid, benzenetetracarboxylic acid and naphthalenetetracarboxylic acid, and carboxylic acid chlorinated compounds or carboxylic acid benzotriazole esterified compounds. It is not limited.

Examples are given below to illustrate the present invention, but the present invention is not limited thereby.
The obtained compound was subjected to mass spectrometry and elemental analysis for property evaluation. The measurement conditions for each characteristic were as follows.
[Test method]
(1) Mass spectrometry (MS): Measured by a field desorption method using a JMS-700 type manufactured by JEOL Ltd.
(2) Elemental analysis: Measured using a Model 2400 manufactured by PERKIN ELMER.
(3) Dielectric constant: Using an automatic mercury probe CV measuring device SSM495 manufactured by Nippon SSM Co., Ltd., heat the measurement sample obtained below in an atmosphere at a temperature of 22 ° C. and a humidity of 45%. The relative dielectric constant of the cured film (film thickness 1 μm) was measured. The coating was made by applying a coating varnish consisting of a sample for measurement and N-methylpyrrolidone on a silicon wafer by spin coating to obtain a uniform film thickness, followed by heating and drying at 150 ° C. for 10 minutes, Was heated at 350 ° C. for 60 minutes using an oven in which the oxygen concentration was controlled to 100 ppm or less. The measurement sample was produced as follows. First, a bisaminophenol compound (3 mmol) and 20 mL of N-methylpyrrolidone were charged into a 100 mL flask, and 0.61 g (3 mmol) of isophthalic acid dichloride was added while stirring at 10 ° C. under a nitrogen stream, Was stirred at 20 ° C. for 24 hours. The reaction solution was added to 500 mL of ion exchange water, and the solid recovered by filtration was further washed with stirring in 500 mL of ion exchange water for 1 hour. Further, a sample obtained by drying under reduced pressure at 60 ° C. for 2 days was used as a measurement sample.

[Example 1]
[Synthesis of 3,3′-bis- (3-amino-4-hydroxy-phenyl) -1,1′-biadamantane]
(1) Synthesis of 3,3′-bis (4-hydroxy-phenyl) -1,1′-biadamantane To a four-necked 10 L Separa flask equipped with a thermometer, stirrer, nitrogen inlet tube and reflux tube, the above T. T. 64.5 g (0.15 mol) of 3,3′-dibromo-1,1′-biadamantane obtained by the method of Gund and 1032 g (10.95 mol) of phenol were charged and heated to reflux at 155 ° C. for 30 minutes. Then, after cooling to room temperature, 4.3 L of methanol was added and heated to reflux at 55 ° C. for 10 minutes. The precipitate was collected by filtration, and the solid was washed away with methanol. The product was dried under reduced pressure at 60 ° C. for 24 hours to obtain 64.2 g of the product (yield 93.7%).

(2) Synthesis of 3,3′-bis- (3-nitro-4-hydroxy-phenyl) -1,1′-biadamantane In a four-necked 1 L flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer, 45.46 g (0.100 mol) of 3,3′-bis (4-hydroxy-phenyl) -1,1′-biadamantane obtained by the above method and 600 mL of dichloromethane were charged, and nitrogen was allowed to flow into the flask. The flask was cooled in a methanol / ice bath and 27.30 g (0.260 mol) of a 60% nitric acid aqueous solution was added dropwise with stirring. Subsequently, the mixture was stirred at an internal temperature of 0 ° C. or lower for 30 minutes, then replaced with a water / ice bath and stirred at 0 to 5 ° C. for 2 hours. Further, the water / ice bath was removed and stirred at room temperature for 2 hours. The reaction solution was filtered, and the yellow solid obtained as a filtrate was washed with 1000 mL of ion-exchanged water three times and dried under reduced pressure at 60 ° C. for 1 day, whereby 3,3′-bis- (3-nitro-4 31.04 g of (hydroxy-phenyl) -1,1′-biadamantane was obtained (57% yield).

(3) Synthesis of 3,3′-bis- (3-amino-4-hydroxy-phenyl) -1,1′-biadamantane 3,3′-bis- (3-nitro-4-) obtained above Hydroxy-phenyl) -1,1'-biadamantane (31.04 g, 0.057 mol), 10% palladium activated carbon (2.42 g, 0.00114 mol), and N, N-dimethylformamide (380 mL) at room temperature under hydrogen atmosphere Stir for hours. After stirring for 15 minutes in a 50 ° C. hot water bath, the reaction solution was filtered. The filtrate was dropped into 1200 mL of ion-exchanged water, and the precipitated solid was washed 3 times with a mixed solution of 620 mL of methanol and 620 mL of ion-exchanged water, and dried under reduced pressure at 60 ° C. for 2 days. 23.21 g of 3′-bis- (3-amino-4-hydroxy-phenyl) -1,1′-biadamantane was obtained (yield 84%).
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Skin color solid MS (FD) (m / z): 484 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 79.30; H, 8.32; N, 5.78; O, 6.60, measured value (/%): C, 79.17; H, 8 .20; N, 5.95; O, 6.68
The measurement results of relative permittivity are shown below.
Dielectric constant: 2.8

[Example 2]
[Synthesis of 3,3′-bis (3-amino-4-hydroxy-phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane]
(1) Synthesis of 3,3′-bis (4-hydroxy-phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane Thermometer, stirrer, nitrogen introduction tube and reflux tube In a four-necked 5 L Separa flask equipped with 3,4 ′ g (0.1 mol) of 3,3′-dibromo-5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane obtained by the method of Gund and 688 g (7.3 mol) of phenol were obtained. The mixture was heated to reflux at 155 ° C. for 30 minutes. Thereafter, after cooling to room temperature, 4.3 L of pure water was added and heated to reflux at 80 ° C. for 10 minutes. The precipitate was collected by filtration, the solid was mixed with 7 L of pure water, stirred for 10 minutes, and then collected by filtration. By drying under reduced pressure at 60 ° C. for 24 hours, 50.6 g of 3,3′-bis (4-hydroxy-phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane was obtained ( Yield 99.0%).

(2) Synthesis of 3,3′-bis (3-nitro-4-hydroxy-phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane thermometer, nitrogen introduction tube, Into a four-necked 1 L flask equipped with a stirrer, the 3,3′-bis (4-hydroxy-phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-bihydrate obtained above was added. Adamantane 51.08 g (0.100 mol) and 770 mL of dichloromethane were charged, and nitrogen was allowed to flow into the flask. The flask was cooled in a methanol / ice bath, and 25.20 g (0.240 mol) of a 60% aqueous nitric acid solution was added dropwise with stirring. Subsequently, the mixture was stirred at an internal temperature of 0 ° C. or lower for 30 minutes, then replaced with a water / ice bath, stirred at 0 to 5 ° C. for 3 hours, further removed from the water / ice bath, and stirred at room temperature for 15 minutes. The reaction solution was filtered, and the yellow solid obtained as a filtrate was washed with 1500 mL of ion-exchanged water three times and dried under reduced pressure at 60 ° C. for 1 day, whereby 3,3′-bis (3-nitro-4- Hydroxy-phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane (35.44 g) was obtained (yield 59%).

(3) Synthesis of 3,3′-bis (3-amino-4-hydroxy-phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane 3, 3'-bis (3-nitro-4-hydroxy-phenyl) -5,5 ', 7,7'-tetramethyl-1,1'-biadamantane 35.44 g (0.059 mol) and 10% palladium on activated carbon 2 .50 g (0.00118 mol) and 420 mL of N, N-dimethylformamide were stirred at room temperature for 26 hours in a hydrogen atmosphere. Then, after stirring for 15 minutes in a 50 degreeC hot water bath, the reaction liquid was filtered. The filtrate was dropped into 1420 mL of ion-exchanged water, and the precipitated solid was washed three times with a mixed solution of 710 mL of methanol and 710 mL of ion-exchanged water, and dried under reduced pressure at 60 ° C. for 2 days. Amino-4-hydroxy-phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane 5.74 g was obtained (yield 18%).
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Skin color solid MS (FD) (m / z): 540 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 79.96; H, 8.95; N, 5.18; O, 5.92, Actual value (/%): C, 79.87; H, 8 .83; N, 5.25; O, 6.05
The measurement results of relative permittivity are shown below.
Dielectric constant: 2.7

[Example 3]
[Synthesis of 3,3′-bis (4- (4-amino-3-hydroxy-phenoxy) phenyl) -1,1′-biadamantane]
(1) Synthesis of 3,3′-bis (4- (4-nitro-3-benzyloxy-phenoxy) -phenyl) -1,1′-biadamantane A thermometer, a stirrer, a nitrogen introduction tube and a reflux tube are provided. Into a four-necked 1 L Separa flask, 45.45 g (0. 3) of 3,3′-bis (4-hydroxy-phenyl) -1,1′-biadamantane obtained by the method of (1) of Example 1 was used. 1 mol), 55.6 g (0.225 mol) of 2-benzyloxy-4-fluoronitrobenzene, 55.3 g (0.400 mol) of potassium carbonate, and 590 ml of N, N′-dimethylformamide were charged and heated to reflux at 135 ° C. for 4 hours. . Then, after cooling to room temperature, the precipitate was collected by filtration. The solid collected by filtration was mixed with 1800 ml of pure water, stirred for 30 minutes, and then collected by filtration. The solid collected by filtration was mixed with 1800 ml of methanol, stirred for 30 minutes, and then collected by filtration. By drying under reduced pressure at 60 ° C. for 24 hours, 69.1 g of the product was obtained (yield 76.0%).

(2) Synthesis of 3,3′-bis (4- (4-amino-3-hydroxy-phenoxy) -phenyl) -1,1′-biadamantane In a 1 L eggplant flask, the 3,3 ′ obtained above -Bis (4- (4-nitro-3-benzyloxy-phenoxy) phenyl) -1,1'-biadamantane 90.9 g (0.1 mol), 2.12 g (0.002 mol) of 10% palladium on activated carbon, tetrahydrofuran After charging 576 mL and a stir bar, the inside of the flask was replaced with hydrogen gas. While stirring the hydrogen pressure inside the flask at 50 psi for 72 hours at 20 ° C., the reaction solution was filtered. The filtrate was added to 3.6 L of ion exchange water, and the solid was reprecipitated and collected. The obtained solid was stirred and washed twice in 13.6 L of ion-exchanged water for 30 minutes and dried under reduced pressure at room temperature for 24 hours to obtain 58.2 g of a dark red powder product (yield 87). 0.0%).
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Dark red solid MS (FD) (m / z): 669 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 79.01; H, 7.23; N, 4.19; O, 9.57, measured value (/%): C, 79.17; H, 7 .12; N, 4.25; O, 9.46
The measurement results of relative permittivity are shown below.
Dielectric constant: 2.8

[Example 4]
[Synthesis of 3,3′-bis (4- (6- (1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -1,1′-biadamantane]
(1) Synthesis of 5- (1-adamantyl) -2-benzyloxy-4-fluoronitrobenzene In a 300 mL eggplant flask, 87.3 g (779 mmol) of 3-fluorophenol, 83.8 g (389 mmol) of 1-bromoadamantane, toluene 60 mL and a stirring bar were added, and stirring was performed at 140 ° C. for 24 hours under a nitrogen stream. The reaction solution was allowed to stand at room temperature, and the precipitated solid was collected by filtration. The recovered solid was washed with cold toluene and then dried under reduced pressure at 60 ° C. to obtain 63.2 g of 4- (1-adamantyl) -3-fluorophenol.
Next, 63.2 g (236 mmol) of 4- (1-adamantyl) -3-fluorophenol obtained above, 300 mL of dichloromethane, 24.5 g (236 mmol) of 60% nitric acid aqueous solution, and a stirrer were added to a 500 mL eggplant flask. And stirred at 10 ° C. for 1 hour. After adding 100 mL of 1% aqueous sodium hydrogen carbonate solution to the reaction solution, the organic layer was recovered using a separatory funnel, and the solvent was removed under reduced pressure. The obtained solid was recrystallized from 1200 mL of 2-propanol to obtain 39.5 g of 5- (1-adamantyl) -2-hydroxy-4-fluoronitrobenzene.
Next, in a 500 mL eggplant flask, 30.1 g (103 mmol) of 5- (1-adamantyl) -2-hydroxy-4-fluoronitrobenzene obtained above, 26.5 g (155 mmol) of benzyl bromide, 42.2 g of potassium carbonate (305 mmol), 200 mL of acetonitrile, and a stirring bar were added, and the mixture was stirred at 100 ° C. for 5 hours. The reaction solution was filtered and allowed to stand at room temperature, and the precipitated solid was collected by filtration. The recovered solid was washed with cold acetonitrile, and then dried under reduced pressure at 60 ° C. to obtain 27.8 g of 5- (1-adamantyl) -2-benzyloxy-4-fluoronitrobenzene.

(2) Synthesis of 3,3′-bis (4- (6- (1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -1,1′-biadamantane of Example 3 (1) In the synthesis, instead of 55.6 g (0.225 mol) of 2-benzyloxy-4-fluoronitrobenzene, 92.1 g of 5- (1-adamantyl) -2-benzyloxy-4-fluoronitrobenzene obtained above ( Except that 0.225 mol) was used, synthesis was performed by the method described in (1) to (2) of Example 3 to obtain a target product.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Dark red solid MS (FD) (m / z): 937 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 82.01; H, 8.17; N, 2.99; O, 6.83, Measured value (/%): C, 81.97; H, 8 .23; N, 2.75; O, 7.05
The measurement results of relative permittivity are shown below.
Dielectric constant: 2.8

[Example 5]
[Synthesis of 3,3′-bis (4- (4-amino-3-hydroxyphenoxy) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane]
In Example 3, (1), instead of 3,3′-bis (4-hydroxy-phenyl) -1,1′-biadamantane 45.45 g, 3,3 obtained in Example 2 (1) The reaction was conducted in the same manner as in Example 3 except that 51.08 g of '-bis (4-hydroxy-phenyl) -5,5', 7,7'-tetramethyl-1,1'-biadamantane was used. , 3′-bis (4- (4-amino-3-hydroxyphenoxy) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane was obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Brown solid MS (FD) (m / z): 725 (M ⁺ )
Elemental analysis: theoretical value (/%): C, 79.52; H, 7.79; N, 3.86; O, 8.83, measured value (/%): C, 79.97; H, 7 .53; N, 3.75; O, 8.75
The measurement results of relative permittivity are shown below.
Dielectric constant: 2.8

[Example 6]
[3,3′-bis (4- (4-amino-3-hydroxy-6- (3,5-dimethyl-1-adamantyl) -phenoxy) phenyl) -5,5 ′, 7,7′-tetramethyl Synthesis of -1,1′-biadamantane (1) Synthesis of 5- (3,5-dimethyl-1-adamantyl) -2-benzyloxy-4-fluoronitrobenzene In (1) of Example 4, 1-bromo Synthesis was performed in the same manner except that 1-bromo-3,5-dimethyladamantane was used instead of adamantane, and 5- (3,5-dimethyl-1-adamantyl) -2-benzyloxy-4-fluoronitrobenzene was synthesized. Got.

(2) 3,3′-bis (4- (4-nitro-3-benzyloxy-6- (3,5-dimethyl-1-adamantyl) -phenoxy) phenyl-5,5 ′, 7,7′- Synthesis of tetramethyl-1,1′-biadamantane 3,3 obtained by the method of (1) of Example 2 was added to a four-necked 2 L Separa flask equipped with a thermometer, a stirrer, a nitrogen introduction tube and a reflux tube. '-Bis (4-hydroxy-phenyl) -5,5', 7,7'-tetramethyl-1,1'-biadamantane 51.08 g (0.1 mol), 5- (5) obtained in (1) above. 3,5-dimethyl-1-adamantyl) -2-benzyloxy-4-fluoronitrobenzene 83.95 g (0.205 mol), potassium carbonate 55.3 g (0.400 mol), and N, N′-dimethylformamide 1000 ml were charged. 4 hours at 135 ° C After cooling to room temperature, the reaction solution was mixed with 10 L of pure water, stirred for 30 minutes, and filtered.The filtered solid was mixed with 10 L of methanol, stirred for 30 minutes, and then filtered. The product was dried under reduced pressure at 60 ° C. for 24 hours to obtain 109.6 g of the product (yield: 85.0%).

(3) 3,3′-bis (4- (4-nitro-3-hydroxy-6- (3,5-dimethyl-1-adamantyl) -phenoxy) phenyl) -5,5 ′, 7,7′- Synthesis of tetramethyl-1,1′-biadamantane To a 4-neck 2 L Separ flask equipped with a thermometer, a stirrer and a nitrogen introduction tube, 3,3′-bis (4- (4-Nitro-3-benzyloxy) -6- (3,5-dimethyl-1-adamantyl) phenoxy) phenyl-5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane128. 97 g (0.1 mol), trimethylsilyl iodide 160 g (0.8 mol) and 1290 ml of chloroform were charged and stirred at 25 ° C. for 17 hours. Thereafter, 215 ml of methanol was added and stirred for 10 minutes. The reaction solution was washed in this order with 1290 ml of 5 wt% aqueous sodium hydrogen sulfite solution, 1290 ml of 5 wt% aqueous sodium hydrogen carbonate solution and 1290 ml of pure water. The organic layer after washing was distilled off under reduced pressure to obtain a solid. This solid was dried under reduced pressure at 60 ° C. for 24 hours to obtain 85.4 g of a product (yield 77.0%).

(4) 3,3′-bis (4- (4-amino-3-hydroxy-6- (3,5-dimethyl-1-adamantyl) phenoxy) phenyl-5,5 ′, 7,7′-tetramethyl Synthesis of -1,1'-biadamantane Into a four-necked 10 L flask equipped with a thermometer, a Dimroth condenser, and a nitrogen inlet, 3,3'-bis (4- (4-nitro-3) obtained above -Hydroxy-6- (3,5-dimethyl-1-adamantyl) phenoxy) phenyl-5,5 ', 7,7'-tetramethyl-1,1'-biadamantane 110.95 g (0.1 mol), dichloromethane 1760 ml was added and stirred at room temperature until completely dissolved, then 700 ml of acetonitrile and 410 ml of pure water were added, and stirring was continued at room temperature under a nitrogen stream. .9 g (1.2 mol), 1,1′-dioctyl-4,4′-bipyridium 5.42 g (0.01 mol), potassium carbonate 124.38 g (0.9 mol) dissolved in 2600 ml of water, The solution was gradually added dropwise using a dropping funnel, reacted for 6 hours at 35 ° C., and then the organic solvent layer was extracted using a separatory funnel, purified by column operation, and dried under reduced pressure at room temperature for 24 hours. Gave 87.1 g of product (yield 83.0%).
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Skin color solid MS (FD) (m / z): 993 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 82.21; H, 8.52; N, 2.82; O, 6.44, measured value (/%): C, 82.43; H, 8 .83; N, 2.38; O, 6.36
The measurement results of relative permittivity are shown below.
Dielectric constant: 2.7

[Example 7]
[Synthesis of 2,2-bis (5-amino-4-hydroxy-3- (3,5-dimethyl-1-adamantyl) phenyl) adamantane]
(1) Synthesis of 2,2-bis (4-hydroxy-3- (3,5-dimethyl-1-adamantyl) phenyl) adamantane A four-neck equipped with a thermometer, a Dimroth condenser, a stirrer and a nitrogen inlet To a 1 L flask, 70 g (219 mmol) of 2,2-bis (4-hydroxyphenyl) adamantane obtained by the above Der-Jang Liaw method, 375 g (1530 mmol) of 1-bromo-3,5-dimethyladamantane, anhydrous iron trichloride 7 g (44 mmol) and 140 mL of acetonitrile were added, and the mixture was heated to reflux at 120 ° C. for 3 hours. After adding 500 mL of water to the reaction solution, extraction was performed 3 times with 500 mL of hexane using a separatory funnel. The collected hexane solution was washed with 100 mL of brine and then dried over 200 g of sodium sulfate. Into an open column (inner diameter: 10 cm, silica gel height: 20 cm) packed with silica gel for column chromatography and hexane, the hexane solution obtained above was charged, and after flowing 3 L of hexane, developed with a mixed solvent of hexane and ethyl acetate, The obtained solid was recrystallized with acetone to obtain 35 g (yield 25%) of the desired 2,2-bis (4-hydroxy-3- (3,5-dimethyl-1-adamantyl) phenyl) adamantane. It was.

(2) Synthesis of 2,2-bis (4-hydroxy-3- (3,5-dimethyl-1-adamantyl) -5-nitrophenyl) adamantane 4 equipped with a thermometer, dropping funnel, stirrer and nitrogen inlet tube In a 1-L flask with one neck, 35 g (54 mmol) of 2,2-bis (4-hydroxy-3- (3,5-dimethyl-1-adamantyl) phenyl) adamantane obtained above and 100 mL of toluene were added and stirred at room temperature. Dissolved. Next, after cooling the reaction solution to 5 ° C. using an ice bath, 14 g (133 mmol) of a 60% nitric acid aqueous solution was added dropwise over 30 minutes, followed by stirring at room temperature for 1 hour. 1 L of methanol was added to the reaction solution in a slurry state, and the solid was recovered by filtration. The obtained solid was washed with hot methanol and then dried under reduced pressure at 100 ° C. for 24 hours to obtain the desired 2,2-bis (4-hydroxy-3- (3,5-dimethyl-1-adamantyl) -5. 36 g (yield 90%) of -nitrophenyl) adamantane were obtained.

(3) 2,2-bis (5-amino-4-hydroxy-3- (3,5-dimethyl-1-adamantyl) phenyl) adamantane Into a 1 L eggplant flask, 2,2-bis (4 After introducing -hydroxy-3- (3,5-dimethyl-1-adamantyl) -5-nitrophenyl) adamantane 36 g (49 mmol), 10% palladium activated carbon 5 g (5 mmol), tetrahydrofuran 200 mL and a stirrer, Replaced with hydrogen gas. The flask was stirred at 20 ° C. for 72 hours while maintaining the hydrogen pressure inside the flask at 50 psi. After the reaction solution was filtered to remove the catalyst, the filtrate was concentrated to 100 g using an evaporator and poured into 2 L of ion-exchanged water. The precipitated solid was washed with ion-exchanged water and then dried under reduced pressure at 100 ° C. for 48 hours to give 2,2-bis (5-amino-4-hydroxy-3- (3,5-dimethyl-1-adamantyl). ) Phenyl) adamantane (30 g, yield 90%) was obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Light brown solid MS (FD) (m / z): 674 (M +)
Elemental analysis: Theoretical value (/%): C, 81.85; H, 9.26; N, 4.15; O, 4.74, measured value (/%): C, 81.30; H, 9 .39; N, 4.20; O, 4.99
The measurement results of relative permittivity are shown below.
Relative permittivity: 2.6

[Example 8]
[Synthesis of 2,2-bis (4- (4-amino-3-hydroxyphenoxy) -3- (3,5-dimethyl-1-adamantyl) phenyl) adamantane]
In Example 3 (1), 45.45 g of 3,3′-bis (4-hydroxy-phenyl) -1,1′-biadamantane was obtained by the method of Example 7 (1). 2,2-bis (4- (4-amino-3) was prepared in the same manner as in Example 3 except that 64 g of bis (4-hydroxy-3- (3,5-dimethyl-1-adamantyl) phenyl) adamantane was used. 70 g of (hydroxyphenoxy) -3- (3,5-dimethyl-1-adamantyl) phenyl) adamantane were obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Light brown solid MS (FD) (m / z): 859 (M +)
Elemental analysis: Theoretical value (/%): C, 81.08; H, 8.21; N, 3.26; O, 7.45, Actual value (/%): C, 80.11; H, 8 .49; N, 3.50; O, 7.40
The measurement results of relative permittivity are shown below.
Relative permittivity: 2.6

[Example 9]
[2,2-bis (4- (4-amino-5-hydroxy-2- (3,5-dimethyl-1-adamantyl) phenoxy) -3- (3,5-dimethyl-1-adamantyl) phenyl) adamantane Synthesis]
In Example 6 (2), 51.08 g of 3,3′-bis (4-hydroxy-phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane was used. 2 In the same manner as in Example 6 except that 64 g of 2,2-bis (4-hydroxy-3- (3,5-dimethyl-1-adamantyl) phenyl) adamantane obtained by the method of (1) was used. 80 g of 2-bis (4- (4-amino-5-hydroxy-2- (3,5-dimethyl-1-adamantyl) phenoxy) -3- (3,5-dimethyl-1-adamantyl) phenyl) adamantane Obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Light brown solid MS (FD) (m / z): 1183 (M +)
Elemental analysis: Theoretical value (/%): C, 83.20; H, 9.03; N, 2.37; O, 5.41, Actual value (/%): C, 83.55; H, 9 .09; N, 2.29; O, 5.00
The measurement results of relative permittivity are shown below.
Relative permittivity: 2.6

[Example 10]
[Synthesis of 2,2-bis (5-amino-4-hydroxy-3- (7- (3,3 ′, 5,5′-tetramethyl-1,1′-biadamantyl)) phenyl) adamantane]
(1) Synthesis of 2,2-bis (4-hydroxy-3- (7- (3,3 ′, 5,5′-tetramethyl-1,1′-biadamantyl)) phenyl) adamantane Thermometer, Dimroth To a four-necked 1 L flask equipped with a condenser, a stirrer and a nitrogen inlet tube was added 70 g (219 mmol) of 2,2-bis (4-hydroxyphenyl) adamantane, 7-bromo-3,3 ′, 5,5′- Tetramethyl-1,1′-biadamantane (625 g, 1530 mmol), anhydrous iron trichloride (7 g, 44 mmol) and mesitylene (1000 mL) were added, heated at 120 ° C. for 3 hours, and then cooled to room temperature. The reaction solution obtained above was put into an open column (inner diameter: 10 cm, silica gel height: 20 cm) packed with silica gel for column chromatography and dichloromethane, and developed with a mixed solvent of dichloromethane and ethyl acetate. 21 g (yield 10%) of -bis (4-hydroxy-3- (7- (3,3 ′, 5,5′-tetramethyl-1,1′-biadamantyl)) phenyl) adamantane were obtained.

(2) Synthesis of 2,2-bis (4-hydroxy-3- (7- (3,3 ′, 5,5′-tetramethyl-1,1′-biadamantyl))-5-nitrophenyl) adamantane To a 4-neck 1 L flask equipped with a thermometer, a dropping funnel, a stirrer, and a nitrogen introduction tube, 2,2-bis (4-hydroxy-3- (7- (3,3 ′, 5,5) obtained above) was added. '-Tetramethyl-1,1'-biadamantyl)) phenyl) adamantane (21 g, 22 mmol) and acetonitrile (200 mL) were added and stirred and dissolved at room temperature. Next, the reaction solution was cooled to 5 ° C. using an ice bath, and 6 g (57 mmol) of a 60% nitric acid aqueous solution was added dropwise over 30 minutes, followed by stirring at room temperature for 1 hour. 1 L of water was added to the reaction solution in a slurry state, and the solid was collected by filtration. The obtained solid was washed with hot methanol and then dried under reduced pressure at 100 ° C. for 24 hours to obtain the desired 2,2-bis (4-hydroxy-3- (7- (3,3 ′, 5,5 ′). -Tetramethyl-1,1'-biadamantyl))-5-nitrophenyl) adamantane 20g (yield 86%) was obtained.

(3) Synthesis of 2,2-bis (5-amino-4-hydroxy-3- (7- (3,3 ′, 5,5′-tetramethyl-1,1′-biadamantyl)) phenyl) adamantane Into a 1 L eggplant flask, 2,2-bis (4-hydroxy-3- (7- (3,3 ′, 5,5′-tetramethyl-1,1′-biadamantyl))-5 obtained above was added. -Nitrophenyl) Adamantane 20 g (19 mmol), 10% palladium on activated carbon 2 g (2 mmol), tetrahydrofuran 200 mL and a stirrer were added, and the flask interior was replaced with hydrogen gas. The flask was stirred at 20 ° C. for 72 hours while maintaining the hydrogen pressure inside the flask at 50 psi. After the reaction solution was filtered to remove the catalyst, the filtrate was concentrated to 100 g using an evaporator and poured into 2 L of ion-exchanged water. The precipitated solid was washed with ion-exchanged water and then dried under reduced pressure at 100 ° C. for 48 hours, whereby 2,2-bis (5-amino-4-hydroxy-3- (7- (3,3 ′, 5 , 5′-tetramethyl-1,1′-biadamantyl)) phenyl) adamantane (15 g, yield 79%).
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Light brown solid MS (FD) (m / z): 999 (M +)
Elemental analysis: Theoretical value (/%): C, 84.11; H, 9.88; N, 2.80; O, 3.02, Actual value (/%): C, 83.99; H, 9 .94; N, 2.60; O, 3.37
The measurement results of relative permittivity are shown below.
Dielectric constant: 2.5

[Example 11]
[2,2-bis (4- (4-amino-3-hydroxyphenoxy) -3- (7- (3,3 ′, 5,5′-tetramethyl-1,1′-biadamantyl)) phenyl] Synthesis of adamantane]
In (3) of Example 3, 45.45 g of 3,3′-bis (4-hydroxy-phenyl) -1,1′-biadamantane was obtained by the method of Example 10 (1). Except for using 64 g of bis (4-hydroxy-3- (7- (3,3 ′, 5,5′-tetramethyl-1,1′-biadamantyl)) phenyl) adamantane, the same as in Example 3. 2,2-bis (4- (4-amino-3-hydroxyphenoxy) -3- (7- (3,3 ′, 5,5′-tetramethyl-1,1′-biadamantyl)) phenyl) 70 g of adamantane was obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Light brown solid MS (FD) (m / z): 1183 (M +)
Elemental analysis: Theoretical value (/%): C, 83.20; H, 9.03; N, 2.37; O, 5.41, Actual value (/%): C, 83.01; H, 8 .93; N, 2.33; O, 5.63
The measurement results of relative permittivity are shown below.
Relative permittivity: 2.6

[Example 12]
[3,3′-bis (3-amino-4-hydroxy-5- (3,5-dimethyl-1-adamantyl) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′- Synthesis of Biadamantane]
(1) 3,3′-bis (4-hydroxy-3- (3,5-dimethyl-1-adamantyl) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane Synthesis of 3,3′-bis (4-hydroxy-phenyl)-obtained by the method of Example 2 (1) into a 4-neck 1 L flask equipped with a thermometer, a Dimroth condenser, a stirrer, and a nitrogen inlet tube 5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane 100 g (196 mmol), 1-bromo-3,5-dimethyladamantane 375 g (1530 mmol), anhydrous iron trichloride 7 g (44 mmol) and mesitylene 200 mL was added and heated to reflux at 120 ° C. for 3 hours. The reaction solution obtained above was put into an open column (inner diameter: 10 cm, silica gel height: 20 cm) packed with silica gel for column chromatography and hexane, and after flowing 3 L of hexane, developed with a mixed solvent of dichloromethane and ethyl acetate, By recovering the eluate containing the target product, the desired 3,3′-bis (4-hydroxy-3- (3,5-dimethyl-1-adamantyl) phenyl) -5,5 ′, 7,7 32 g (yield 20%) of '-tetramethyl-1,1'-biadamantane was obtained.

(2) 3,3′-bis (4-hydroxy-3- (3,5-dimethyl-1-adamantyl) -5-nitrophenyl) -5,5 ′, 7,7′-tetramethyl-1,1 Synthesis of '-biadamantane Into a 4-neck 1 L flask equipped with a thermometer, a dropping funnel, a stirrer and a nitrogen introduction tube, the 3,3'-bis (4-hydroxy-3- (3,5- Dimethyl-1-adamantyl) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane (32 g, 38 mmol) and acetonitrile (200 mL) were added and stirred and dissolved at room temperature. Next, after cooling the reaction solution to 5 ° C. using an ice bath, 10 g (95 mmol) of a 60% nitric acid aqueous solution was added dropwise over 30 minutes, followed by stirring at room temperature for 1 hour. 1 L of water was added to the reaction solution in a slurry state, and the solid was collected by filtration. The obtained solid was washed with hot methanol and then dried under reduced pressure at 100 ° C. for 24 hours to obtain the desired 3,3′-bis (4-hydroxy-3- (3,5-dimethyl-1-adamantyl)- 5-nitrophenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane (33 g, yield 95%) was obtained.

(3) 3,3′-bis (3-amino-4-hydroxy-5- (3,5-dimethyl-1-adamantyl) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1 Synthesis of '-biadamantane Into a 1 L eggplant flask, the 3,3'-bis (4-hydroxy-3- (3,5-dimethyl-1-adamantyl) -5-nitrophenyl) -5,5 obtained above was added. ', 7,7'-Tetramethyl-1,1'-biadamantane 33 g (36 mmol), 10% palladium activated carbon 5 g (5 mmol), tetrahydrofuran 300 mL and a stirrer were added, and the flask interior was replaced with hydrogen gas. The flask was stirred at 20 ° C. for 72 hours while maintaining the hydrogen pressure inside the flask at 50 psi. The reaction solution was filtered to remove the catalyst, and then the filtrate was concentrated to 150 g using an evaporator and poured into 2 L of ion-exchanged water. The precipitated solid was washed with ion-exchanged water and then dried under reduced pressure at 100 ° C. for 48 hours, whereby 3,3′-bis (3-amino-4-hydroxy-5- (3,5-dimethyl-1- Adamantyl) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane (28 g, yield 90%) was obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Light brown solid MS (FD) (m / z): 865 (M +)
Elemental analysis: Theoretical value (/%): C, 83.28; H, 9.78; N, 3.24; O, 3.70, measured value (/%): C, 83.10; H, 9 .70; N, 3.32; O, 3.50
The measurement results of relative permittivity are shown below.
Relative permittivity: 2.6

[Example 13]
[3,3′-bis (3- (3,5-dimethyl-1-adamantyl) -4- (4-amino-3-hydroxyphenoxy) phenyl) -5,5 ′, 7,7′-tetramethyl- Synthesis of 1,1'-biadamantane]
In Example 3, (1), 3,3′-bis (4-hydroxy-phenyl) -1,1′-biadamantane (45.45 g) was obtained by the method of Example 12 (1). -Implemented except for 83 g of bis (4-hydroxy-3- (3,5-dimethyl-1-adamantyl) phenyl) -5,5 ', 7,7'-tetramethyl-1,1'-biadamantane Analogously to Example 3, 3,3′-bis (3- (3,5-dimethyl-1-adamantyl) -4- (4-amino-3-hydroxyphenoxy) phenyl) -5,5 ′, 7, 30 g of 7′-tetramethyl-1,1′-biadamantane was obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Light brown solid MS (FD) (m / z): 1049 (M +)
Elemental analysis: Theoretical value (/%): C, 82.40; H, 8.84; N, 2.67; O, 6.10, Actual value (/%): C, 82.52; H, 8 .39; N, 2.59; O, 6.30
The measurement results of relative permittivity are shown below.
Relative permittivity: 2.6

[Example 14]
[3,3′-bis (3-amino-4-hydroxy-5- (3- (5,5 ′, 7,7′-tetramethyl) -1,1′-biadamantyl) phenyl) -5,5 Synthesis of ', 7,7'-tetramethyl-1,1'-biadamantane]
In Example 12 (1), except that 375 g of 1-bromo-3,5-dimethyladamantane was changed to 625 g of 7-bromo-3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane. In the same manner as in Example 12, 3,3′-bis (3-amino-4-hydroxy-5- (3- (5,5 ′, 7,7′-tetramethyl) -1,1′-bi 15 g of adamantyl) phenyl) -5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane was obtained.
The results of appearance, mass spectrometry and elemental analysis are shown below. These data indicate that the obtained compound is the target product.
Appearance: Light brown solid MS (FD) (m / z): 1189 (M +)
Elemental analysis: Theoretical value (/%): C, 84.79; H, 10.17; N, 2.35; O, 2.69, measured value (/%): C, 84.99; H, 10 .00; N, 2.14; O, 2.80
The measurement results of relative permittivity are shown below.
Relative permittivity: 2.6

[Comparative Example 1]
(Synthesis of 1,3-bis (4-amino-3-hydroxyphenoxy) benzene)
A 300 mL eggplant flask was charged with 9.9 g of 1,3-dihydroxybenzene, 44.4 g of 2-benzyloxy-4-fluoronitrobenzene, 37.3 g of potassium carbonate, 150 mL of N, N-dimethylformamide and a stirrer, and a nitrogen stream Under stirring at 135 ° C. for 12 hours. After the reaction solution was filtered, it was added to 1 L of ion exchange water. The precipitated solid was collected by filtration, further stirred in 1 L of ion exchange water for 1 hour, and then dried under reduced pressure to obtain 42.3 g of 1,3-bis (4-nitro-3-benzyloxyphenoxy) benzene. Obtained.
Next, in a 300 mL eggplant flask, 42.0 g of 1,3-bis (4-nitro-3-benzyloxyphenoxy) benzene obtained above, 2.00 g of 10% palladium-activated carbon, 200 mL of N, N-dimethylformamide. And a stirring bar was added, and the mixture was stirred at 25 ° C. for 24 hours in a hydrogen atmosphere. After the reaction solution was filtered, it was added to 1 L of ion exchange water. The precipitated solid was collected by filtration, further stirred in 1 L of ion exchange water for 1 hour, and then dried under reduced pressure to obtain 30.5 g of 1,3-bis (4-amino-3-hydroxyphenoxy) benzene. It was.
The measurement results of relative permittivity are shown below.
Relative permittivity: 3.1

[Comparative Example 2]
(Synthesis of 2,7-bis (4-amino-3-hydroxyphenoxy) naphthalene)
In Comparative Example 1, 2,7-bis (4-amino-3-) was obtained in the same manner as in Comparative Example 1, except that 9.9 g of 1,3-dihydroxybenzene was changed to 14.4 g of 2,7-dihydroxynaphthalene. 20.2 g of hydroxyphenoxy) naphthalene were obtained.
The measurement results of relative permittivity are shown below.
Relative permittivity: 3.1

  As is clear from the above, it was shown that the bisaminophenol compound provided by the present invention can be suitably used as a raw material for a polymer having a low relative dielectric constant.

Claims (10)

  A bisaminophenol compound having a structure in which two groups having an aminohydroxyphenyl group are bonded to a group composed of a diamondoid structure. The bisaminophenol compound according to claim 1, wherein the bisaminophenol compound is represented by the general formula (1).

(In the formula, X represents a group composed of a diamondoid structure, n represents 0 or 1, and Y represents a hydrogen atom, an alkyl group or a group composed of a diamondoid structure.)   The bisaminophenol compound according to claim 2, wherein the bisaminophenol compound has a group composed of an alkyl group or a diamondoid structure as a substituent on the phenylene group in the general formula (1).   The bisaminophenol compound according to claim 2 or 3, wherein the bisaminophenol compound has a group composed of a diamondoid structure as a substituent on Y and / or a phenylene group in the general formula (1). Phenolic compounds.   The bisaminophenol compound according to any one of claims 2 to 4, wherein the bisaminophenol compound has a group composed of a diamondoid structure as Y in the general formula (1).   The bisaminophenol compound according to any one of claims 2 to 5, wherein n in the general formula (1) is 0.   The bisaminophenol compound according to any one of claims 2 to 6, wherein the bisaminophenol compound has an adamantyl group which may have a substituent as X in the general formula (1). .   The bisaminophenol compound according to any one of claims 2 to 7, wherein the bisaminophenol compound has a beadamantyl group which may have a substituent as X in the general formula (1). Compound.   The bisaminophenol compound according to claim 7 or 8, wherein the substituent is an alkyl group.   The bisaminophenol compound according to claim 8, wherein the biadamantyl group which may have a substituent is a tetramethylbiadamantyl group.