JP3570649B2 - Hydroxyl group-containing amine compound and intermediate for producing the same - Google Patents

Description

【０００８】
【化１１】

【０００９】
【化１２】

【００１０】
【化１３】

【００１１】
【化１４】

【００１２】
【化１５】

【００１３】
【化１６】

【００１４】
【化１７】

【００１５】
【化１８】

式中、Ｒ_１、Ｒ_２は水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基を表わす。
Ａｒ_１、Ａｒ_２、Ａｒ_３、Ａｒ_６はそれぞれ独立にアリレン基を表わす。Ａｒ_４、Ａｒ_５、Ａｒ_７は、それぞれ独立に置換若しくは無置換のアリール基、置換若しくは無置換の複素環基を表わす。
Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９はハロゲン原子、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基を表わす。ａ、ｂ、ｃ、ｇは１〜４の整数であり、ｄ、ｅ、ｆは１〜５の整数である。Ｒ_１０はハロゲン原子、置換もしくは無置換のアルキル基及びアシル基を表わす。
【００１６】
以下、本発明のヒドロキシル基含有アミン化合物及びその製造中間体のエーテル基又はエステル基含有アミン化合物について更に詳細に説明する。
前記一般式（１）、（２）、（３）、（４）、（５）、（６）、（７）、（８）、及び（９）で表わされるアミン化合物において、Ｒ_１〜Ｒ_９が置換若しくは無置換のアルキル基である場合の具体例としては以下のものを挙げることができる。
Ｃ_１〜Ｃ_５直鎖又は分岐鎖のアルキル基であり、これらのアルキル基は更にフッ素原子、シアノ基、フェニル基又はハロゲン原子若しくはＣ_１〜Ｃ_５のアルキル基で置換されたフェニル基を含有していてもよい。具体的には、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基、ｓ−ブチル基、ｎ−ブチル基、ｉ−ブチル基、トリフルオロメチル基、２−シアノエチル基、ベンジル基、４−クロロベンジル基、４−メチルベンジル基等が挙げられる。
【００１７】
また、前記一般式（１）、（２）、（３）、（４）、（５）、（６）、（７）、（８）及び（９）で表わされるアミン化合物において、Ａｒ_４、Ａｒ_５、Ａｒ_７が置換若しくは無置換のアリール基である場合の具体例としては以下のものを挙げることができる。
フェニル基、ナフチル基、ビフェニリル基、ターフェニリル基、ピレニル基、フルオレニル基、９，９−ジメチル−２−フルオレニル基、アズレニル基、アントリル基、トリフェニレニル基、クリセニル基等が挙げられ、これらは低級アルキル基、低級アルコキシ基及びハロゲン原子を置換基として有していてもよい。また、下記一般式（１０）で表わされる基を挙げることができる。
【００１８】
【化１９】

式中、Ｘは−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−及び以下の２価基を表わす。
【００１９】
【化２０】

【００２０】
【化２１】

（ここで、Ｒ_１１、Ｒ_１２は水素原子、置換若しくは無置換のアルキル基、アルコキシ基、ハロゲン原子、置換若しくは無置換のアリール基、アミノ基、ニトロ基、シアノ基を表わし、ｎは１〜１２の整数、ｌは１〜３の整数を表わす。）
【００２１】
前記一般式（１０）中の２価の基Ｘにおいて、Ｒ_１１、Ｒ_１２が置換若しくは無置換のアルキル基の具体例は前記Ｒ_１〜Ｒ_９の定義と同様である。また、アミノ基の具体例としては、下記一般式で表わされる基が挙げられる。
【００２２】
【化２２】

（Ｒ_１３、Ｒ_１４は、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基を表わす。）
ここで、Ｒ_１３、Ｒ_１４において、置換若しくは無置換のアルキル基及び置換若しくは無置換のアリール基の具体例は前記Ｒ_１〜Ｒ_９の定義及び、前記Ａｒ_４、Ａｒ_５、及びＡｒ_７の定義と同様である。また、Ｒ_１３、Ｒ_１４は共同で環を形成しても良い。また、アリール基上の炭素原子と共同で環を形成しても良い。このような具体例としてはピペリジノ基、モルホリノ基、ユロリジル基等が挙げられる。
また、Ｒ_３〜Ｒ_１０がハロゲン原子の場合及び、Ｒ_１〜Ｒ_１４がハロゲン原子を有する基である場合のハロゲン原子としては、フッ素、塩素、臭素及びヨウ素が挙げられる。
【００２３】
また、前記一般式（１）、（２）、（３）、（４）、（５）、（６）、（７）、（８）、（９）で表わされるアミン化合物において、Ａｒ_４、Ａｒ_５、Ａｒ_７の置換若しくは無置換の複素環基の具体例としては、フラン、チオフェン、オキサゾール、ピリジン、ベンゾフラン、ベンゾチオフェン等から誘導される１価基が挙げられ、これらは低級アルキル基、低級アルコキシ基及びハロゲン原子を置換基として有していてもよい。
また、前記一般式（１）、（２）、（３）、（４）、（５）、（６）、（７）、（８）、（９）で表わされるアミン化合物において、Ａｒ_１、Ａｒ_２、Ａｒ_３、Ａｒ_６のアリレン基の具体例としては、前記アリール基から誘導される２価基を挙げることができる。
【００２４】
本発明に係わるヒドロキシル基含有アミン化合物は新規物質であり、以下にその製造方法を示す。即ち、前記一般式（１）〜（８）で表わされる化合物は、以下に示す一般式（９）で表わされる化合物のエーテルの開裂反応あるいはエステルの開裂反応により合成される。
【００２５】
【化２３】

式中、Ｒ_１、Ｒ_２は水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基を表わす。Ａｒ_１、Ａｒ_２、Ａｒ_３、Ａｒ_６はそれぞれ独立にアリレン基を表わす。
Ａｒ_４、Ａｒ_５、Ａｒ_７は、それぞれ独立に置換若しくは無置換のアリール基、置換若しくは無置換の複素環基を表わす。Ｒ_１０は置換若しくは無置換のアルキル基及びアシル基を表わす。（前記定義と同一）
【００２６】
該エーテルの開裂反応は、具体的には酸性試薬による方法と塩基性試薬による方法が挙げられる。
酸性試薬としては、臭化水素、ヨウ化水素、トリフルオロ酢酸、ピリジンの塩酸塩、濃塩酸、ヨウ化マグネシウムエチラート、塩化アルミニウム、臭化アルミニウム、三臭化ホウ素、三塩化ホウ素、三ヨウ化ホウ素等が、塩基性試薬としては、水酸化カリウム、水酸化ナトリウム、ナトリウム、リチウム、ヨウ化ナトリウム、ヨウ化リチウム、リチウムジフェニルホスフィド、ナトリウムチオラート等を挙げることができる。
溶媒としては無水酢酸、ジクロロメタン、テトラヒドロフラン（ＴＨＦ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、ピリジン、ブタノール等を挙げることができ、反応温度は用いる試薬の反応性によるが、一般的には、室温から２００℃の間で行われる。
【００２７】
前記一般式（９）で表わされる化合物は、以下に示す合成スキーム、即ち一般式（１１）で表わされる化合物と一般式（１２）で表わされる化合物とのＷｉｔｔｉｇ反応又は変法Ｗｉｔｔｉｇ反応により合成される。
【００２８】
【化２４】

【００２９】
ここで、Ｒ_１５の具体例としては、Ｃ_１〜Ｃ_５の直鎖又は分岐鎖のアルキル基、例えば、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基、ｓ−ブチル基、ｎ−ブチル基、ｉ−ブチル基、ｎ−ペンチル基等が挙げられる。上記反応において、好ましくは、以下に示す合成スキームに示される変法Ｗｉｔｔｉｇ反応により、一般式（１３）で表わされる化合物と一般式（１４）で表わされる化合物とから前記一般式（９）で表わされる化合物を高収率で合成することができる。
【００３０】
【化２５】

【００３１】
このときの反応は従来公知の方法でよく、例えば、ＤＭＦのような極性溶媒中にホスホネート化合物とホルミル化合物とを溶解させ、水冷下でカリウム−ｔ−ブチラートあるいはナトリウムメチラートのような強塩基化合物を少しずつ加えることにより容易に合成できる。また、一般式（１３）及び一般式（１４）で表わされる化合物は、それぞれ従来公知の方法で合成される。例えば、ホスホネート化合物の合成ではＥｕｒ．Ｊ．Ｍｅｄ．Ｃｈｅｍ．（１９９３）２８，ｐｐ．９４３−９４８に記載の方法によっても合成される。
【００３２】
本発明のヒドロキシル基含有アミン化合物は、電子写真感光体における光導電性素材として極めて有用であり、染料やルイス酸などの増感剤によって光学的或いは化学的に増感される。更にこのものは、有機顔料或いは無機顔料を電荷発生物質とする、いわゆる機能分離型における電荷輸送物質としてとりわけ有用である。
【００３３】
上記増感剤としては、例えば、メチルバイオレット、クリスタルバイオレット等のトリアリールメタン染料、ローズベンガル、エリスロシン、ローダミン等のキサンテン染料、メチレンブルー等のチアジン染料、２，４，７−トリニトロ−９−フルオレノン、２，４−ジニトロ−９−フルオレノン等が挙げられる。
【００３４】
また、有機顔料としてはシーアイピグメントブルー２５（ＣＩ Ｎｏ．２１１８０）、シーアイピグメントレッド４１（ＣＩ Ｎｏ．２１２００）、シーアイピグメントレッド３（ＣＩ Ｎｏ．４５２１０）等のアゾ顔料、シーアイピグメントブルー１６（ＣＩ Ｎｏ．７４１００）等のフタロシアニン系顔料、シーアイバットブラウン５（ＣＩ Ｎｏ．７３４１０）、シーアイバットダイ（ＣＩ Ｎｏ．７３０３０）等のインジゴ系顔料、アルゴスカーレットＢ、インダンスレンスカーレットＲ等のペリレン系顔料が挙げられる。また、セレン、セレン−テルル、硫化カドミウム、α−シリコン等の無機物質も使用できる。
【００３５】
また、ヒドロキシル基から誘導される種々の材料の製造、例えばポリカーボネート樹脂、ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂等の製造中間体としても有用である。
【００３６】
【実施例】
以下に実施例を示し、本発明を更に詳細に説明する。しかしながら本発明はこれら実施例に限定されるものではない。
【００３７】
実施例１
下記構造式（１５）で表わされる４−ホルミル−４’−メトキシ−４”−（２，２−ジフェニルビニル）トリフェニルアミン６９．４ｇ（０．０６×２×１．２ｍｏｌ）と下記構造式（１６）で表わされるビス（ホスホン酸エステル）３０．４ｇ（０．０６ｍｏｌ）をＤＭＦ５００ｍｌに溶解した。この溶液に、ｔ−ＢｕＯＫ２４．２ｇ（０．０６×２×１．２×１．２５ｍｏｌ）を１５〜２５℃を保ちながら添加した。３時間撹拌を行ない原料消失を確認後、反応物を水２０００ｍｌに注加した。酢酸エチルで抽出した後、シリカゲルカラムクロマト（展開溶媒、トルエン：ｎ−ヘキサン＝１：１）で精製を行ない目的物（１７）を６２．３ｇ（収率８９．９％）を得た。なお、この化合物は非晶質であった。
【００３８】
【化２６】

【００３９】
【化２７】

【００４０】
【化２８】

【００４１】
【表１】

【００４２】
実施例２
実施例１で得られた化合物（１７）５７．８ｇ（０．０５ｍｏｌ）とナトリウムチオエチラート３０ｇ（０．３６ｍｏｌ）を乾燥処理したＤＭＦ５００ｍｌに入れ、窒素気流下で８時間加熱還流した。室温まで放冷した後、内容物を氷水にあけ、濃塩酸により中和した。これを濾過、水洗後、シリカゲルカラムクロマト処理（展開溶媒、トルエン：酢酸エチル＝１０：１）し、黄色粉末５２．６ｇ（収率９３．３％）を得た。
【００４３】
【化２９】

この化合物は、非晶質であった。得られた化合物の赤外吸収スペクトル、元素分析の結果を図２に示す。
【００４４】
【表２】

【００４５】
応用例
ポリマー原料としての応用例
実施例２で得られたヒドロキシル基含有アミン化合物（１８）５．６４ｇ（０．００５ｍｏｌ）を脱水処理したＴＨＦ４０ｍｌに溶解させ、窒素ガス気流下において撹拌しながら、トリエチルアミンを１．５２ｇ（０．００５×３ｍｏｌ）加えた後にポリテトラメチレンエーテルグリコールビスクロロフォーメート（平均分子量２５０のポリテトラメチレンエーテルグリコールより調製）１．９２ｇ（０．００５×１．０５ｍｏｌ）を乾燥ＴＨＦ１０ｍｌにとかしたものを水冷下３０分かけて滴下した。滴下終了後、さらに２時間撹拌の後、メタノールに沈殿させ粗生成物を得た。これをさらに２回再沈をくりかえし、沈殿物を乾燥し、下記構造式のポリカーボネート樹脂を得た。
【００４６】
【化２５】

【００４７】
【発明の効果】
以上、詳細かつ具体的に説明したように、本発明により上記新規ヒドロキシル基含有アミン化合物及び上記新規アミン化合物が提供される。
本発明に係わるヒドロキシル基含有アミン化合物は、前記したように光導電性素材として有効に機能し、また染料やルイス酸などの増感剤によって光学的或いは化学的に増感されることから、電子写真感光体の感光層の電荷輸送物質等として好適に使用され、特に電荷発生層と電荷輸送層を２層に区分した、いわゆる機能分離型感光層における電荷輸送物質として有用なものである。
また、ヒドロキシル基から誘導される種々の材料の製造、例えばポリカーボネート樹脂、ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂等の製造中間体としても有用である。
【図面の簡単な説明】
【図１】本発明のアミン化合物（化合物Ｎｏ．１７）の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図２】本発明のアミン化合物（化合物Ｎｏ．１８）の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a hydroxyl group-containing amine compound which is also useful as an organic photoconductive material for electrophotography and as an intermediate for producing various materials derived from a hydroxyl group, and an amine compound which is also useful as an intermediate for producing the same. .
[0002]
[Prior art]
Conventionally, organic photoconductive materials for photoreceptors used in electrophotography include, for example, poly-N-vinylcarbazole, triphenylamine compounds (U.S. Pat. No. 3,180,730), and benzidine compounds (US Numerous proposals have been made, such as Japanese Patent No. 3,265,496, Japanese Patent Publication No. 39-11546, and Japanese Patent Application Laid-Open No. 53-27033.
[0003]
The "electrophotographic method" as used herein generally means that a photoconductive photoreceptor is first charged in a dark place, for example, by corona discharge, and then imagewise exposed to selectively discharge the charge in the exposed portion. This is one of the image forming methods in which an electrostatic latent image is obtained, and the latent image portion is visualized by a developing unit using toner or the like to form an image. The basic characteristics required of the photoreceptor in such an electrophotographic system include: 1) being charged to an appropriate potential in a dark place, 2) being less discharged in a dark place, and 3) being irradiated with light. To discharge the charge more quickly.
[0004]
Also, in recent years, polymer photoconductive materials (U.S. Pat. No. 4,801,517, U.S. Pat. No. 4,806,443, U.S. Pat. Japanese Patent Nos. 4,806,444, JP-A-3-221522, and JP-A-4-11627) have been proposed.
However, conventional low-molecular or high-molecular photoconductive materials do not always satisfy the above requirements.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel hydroxyl group-containing amine which is useful as a photoconductive material satisfying all basic electrophotographic properties, and is also useful as an intermediate for producing various materials derived from a hydroxyl group. An object of the present invention is to provide a novel amine compound which is also useful as a compound and a production intermediate thereof.
[0006]
[Means for Solving the Problems]
According to the present invention, a hydroxyl group-containing compound represented by the following general formulas (1), (2), (3), (4), (5), (6), (7), (8) and (9) An amine compound (including an amine compound containing an ether group or an ester group) is provided.
[0007]
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[0008]
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[0009]
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[0010]
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[0011]
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[0012]
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[0013]
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[0014]
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[0015]
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In the formula, R ₁ and R ₂ represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₆ each independently represent an arylene group. Ar ₄ , Ar ₅ and Ar ₇ each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.
R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ represent a halogen atom, a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. a, b, c, and g are integers of 1 to 4, and d, e, and f are integers of 1 to 5. R ₁₀ represents a halogen atom, a substituted or unsubstituted alkyl group or an acyl group.
[0016]
Hereinafter, the hydroxyl group-containing amine compound of the present invention and the ether group or ester group-containing amine compound as an intermediate for producing the same will be described in more detail.
In the amine compounds represented by the general formulas (1), (2), (3), (4), (5), (6), (7), (8), and (9), R _{1 to} R Specific examples of the case where ₉ is a substituted or unsubstituted alkyl group include the following.
A C ₁ -C ₅ linear or branched alkyl group, which further contains a fluorine atom, a cyano group, a phenyl group or a phenyl group substituted with a halogen atom or a C ₁ -C ₅ alkyl group; It may be. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-cyanoethyl group Benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group and the like.
[0017]
In the amine compounds represented by the general formulas (1), (2), (3), (4), (5), (6), (7), (8), and (9), Ar ₄ , Specific examples of the case where Ar ₅ and Ar ₇ are substituted or unsubstituted aryl groups include the following.
Phenyl group, naphthyl group, biphenylyl group, terphenylyl group, pyrenyl group, fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group and the like, and these are lower alkyl groups , A lower alkoxy group and a halogen atom as substituents. Further, a group represented by the following general formula (10) can be exemplified.
[0018]
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Wherein, X is -O -, - S -, - SO -, - SO 2 -, - CO- and represent divalent groups below.
[0019]
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[0020]
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(Where R ₁₁ and R ₁₂ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a halogen atom, a substituted or unsubstituted aryl group, an amino group, a nitro group, a cyano group, and n is 1 to 12 represents an integer, and 1 represents an integer of 1 to 3.)
[0021]
In the divalent group X in the general formula (10), specific examples of the substituted or unsubstituted alkyl group for R ₁₁ and R ₁₂ are the same as the definitions of R _{1 to} R ₉ . Specific examples of the amino group include groups represented by the following general formula.
[0022]
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(R ₁₃ and R ₁₄ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.)
Here, in R ₁₃ and R ₁₄ , specific examples of the substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group are the definitions of the above R _{1 to} R ₉ and those of the above Ar ₄ , Ar ₅ , and Ar ₇ Same as the definition. R ₁₃ and R ₁₄ may form a ring together. Further, a ring may be formed together with a carbon atom on the aryl group. Specific examples of such a group include a piperidino group, a morpholino group, a julolidyl group, and the like.
Further, when R _{3 to} R ₁₀ are a halogen atom and when R _{1 to} R ₁₄ are a group having a halogen atom, the halogen atom includes fluorine, chlorine, bromine and iodine.
[0023]
In the amine compounds represented by the general formulas (1), (2), (3), (4), (5), (6), (7), (8), and (9), Ar ₄ , Specific examples of the substituted or unsubstituted heterocyclic group of Ar ₅ and Ar ₇ include monovalent groups derived from furan, thiophene, oxazole, pyridine, benzofuran, benzothiophene, and the like. These are lower alkyl groups, It may have a lower alkoxy group and a halogen atom as substituents.
In the amine compounds represented by the general formulas (1), (2), (3), (4), (5), (6), (7), (8), and (9), Ar ₁ , Specific examples of the arylene group of Ar ₂ , Ar ₃ , and Ar ₆ include a divalent group derived from the aryl group.
[0024]
The hydroxyl group-containing amine compound according to the present invention is a novel substance, and its production method will be described below. That is, the compounds represented by the general formulas (1) to (8) are synthesized by an ether cleavage reaction or an ester cleavage reaction of the compound represented by the following general formula (9).
[0025]
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In the formula, R ₁ and R ₂ represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₆ each independently represent an arylene group.
Ar ₄ , Ar ₅ and Ar ₇ each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. R ₁₀ represents a substituted or unsubstituted alkyl group and an acyl group. (Same as above)
[0026]
Specific examples of the ether cleavage reaction include a method using an acidic reagent and a method using a basic reagent.
Examples of acidic reagents include hydrogen bromide, hydrogen iodide, trifluoroacetic acid, pyridine hydrochloride, concentrated hydrochloric acid, magnesium iodide ethylate, aluminum chloride, aluminum bromide, boron tribromide, boron trichloride, and triiodide. Examples of the basic reagent containing boron or the like include potassium hydroxide, sodium hydroxide, sodium, lithium, sodium iodide, lithium iodide, lithium diphenyl phosphide, and sodium thiolate.
Examples of the solvent include acetic anhydride, dichloromethane, tetrahydrofuran (THF), N, N-dimethylformamide (DMF), pyridine, butanol, and the like. The reaction temperature depends on the reactivity of the reagent to be used. To 200 ° C.
[0027]
The compound represented by the general formula (9) is synthesized by a synthesis scheme shown below, that is, a Wittig reaction or a modified Wittig reaction between the compound represented by the general formula (11) and the compound represented by the general formula (12). You.
[0028]
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[0029]
Here, specific examples of R ₁₅ include a C _{1 to} C ₅ linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, and a s. -Butyl group, n-butyl group, i-butyl group, n-pentyl group and the like. In the above reaction, the compound represented by the general formula (13) and the compound represented by the general formula (14) are preferably represented by the general formula (9) by a modified Wittig reaction represented by the following synthesis scheme. Can be synthesized in high yield.
[0030]
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[0031]
The reaction at this time may be a conventionally known method. For example, a phosphonate compound and a formyl compound are dissolved in a polar solvent such as DMF, and a strong base compound such as potassium-t-butylate or sodium methylate is cooled under water cooling. Can be easily synthesized by adding a little by little. The compounds represented by the general formulas (13) and (14) are each synthesized by a conventionally known method. For example, in the synthesis of phosphonate compounds, Eur. J. Med. Chem. (1993) 28 pp. 943-948.
[0032]
The hydroxyl group-containing amine compound of the present invention is extremely useful as a photoconductive material in an electrophotographic photoreceptor, and is optically or chemically sensitized by a sensitizer such as a dye or Lewis acid. Further, this is particularly useful as a charge transporting material of a so-called function separation type in which an organic pigment or an inorganic pigment is used as a charge generating material.
[0033]
Examples of the sensitizer include triarylmethane dyes such as methyl violet and crystal violet, xanthene dyes such as rose bengal, erythrosine and rhodamine, thiazine dyes such as methylene blue, 2,4,7-trinitro-9-fluorenone, 2,4-dinitro-9-fluorenone and the like.
[0034]
Examples of organic pigments include azo pigments such as C.I. Pigment Blue 25 (CI No. 21180), C.I. Pigment Red 41 (CI. No. 21200), C.I. Pigment Red 3 (CI. No. 45210), and C.I. Phthalocyanine pigments such as C.I. 74100), indigo pigments such as C.I. No. In addition, inorganic substances such as selenium, selenium-tellurium, cadmium sulfide, and α-silicon can also be used.
[0035]
It is also useful as an intermediate for producing various materials derived from hydroxyl groups, for example, polycarbonate resin, polyester resin, polyurethane resin, epoxy resin and the like.
[0036]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these examples.
[0037]
Example 1
69.4 g (0.06 × 2 × 1.2 mol) of 4-formyl-4′-methoxy-4 ″-(2,2-diphenylvinyl) triphenylamine represented by the following structural formula (15) and the following structural formula 30.4 g (0.06 mol) of bis (phosphonate) represented by (16) was dissolved in 500 ml of DMF, and 24.2 g (0.06 × 2 × 1.2 × 1.25 mol) of t-BuOK was added to this solution. Was added while maintaining the temperature at 15 to 25 ° C. After stirring for 3 hours to confirm that the raw materials had disappeared, the reaction product was poured into 2000 ml of water, extracted with ethyl acetate, and then subjected to silica gel column chromatography (developing solvent, toluene: n−). Purification was performed using hexane (1: 1) to obtain 62.3 g (yield: 89.9%) of the desired product (17), which was amorphous.
[0038]
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[0039]
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[0040]
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[0041]
[Table 1]

[0042]
Example 2
57.8 g (0.05 mol) of the compound (17) obtained in Example 1 and 30 g (0.36 mol) of sodium thioethylate were put in 500 ml of dried DMF, and the mixture was heated under reflux in a nitrogen stream for 8 hours. After allowing to cool to room temperature, the contents were poured into ice water and neutralized with concentrated hydrochloric acid. This was filtered, washed with water, a silica gel column chromatographed (eluent, toluene: ethyl acetate = 10: 1) to give a yellow Powder 5 2.6 g (93.3% yield).
[0043]
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This compound was amorphous. FIG. 2 shows the results of infrared absorption spectrum and elemental analysis of the obtained compound.
[0044]
[Table 2]

[0045]
Application Example Application Example as Polymer Raw Material 5.64 g (0.005 mol) of the hydroxyl-containing amine compound (18) obtained in Example 2 was dissolved in 40 ml of dehydrated THF, and triethylamine was stirred under a nitrogen gas stream while stirring. Was added, and 1.92 g (0.005 × 1.05 mol) of polytetramethylene ether glycol bischloroformate (prepared from polytetramethylene ether glycol having an average molecular weight of 250) was dried. What was dissolved in 10 ml of THF was added dropwise over 30 minutes while cooling with water. After completion of the dropwise addition, the mixture was further stirred for 2 hours and then precipitated in methanol to obtain a crude product. This was repeatedly reprecipitated twice, and the precipitate was dried to obtain a polycarbonate resin having the following structural formula.
[0046]
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[0047]
【The invention's effect】
As described above in detail and specifically, the present invention provides the novel hydroxyl group-containing amine compound and the novel amine compound.
The hydroxyl group-containing amine compound according to the present invention effectively functions as a photoconductive material as described above, and is sensitized optically or chemically by a sensitizer such as a dye or a Lewis acid. It is suitably used as a charge transporting substance in a photosensitive layer of a photographic photosensitive member, and is particularly useful as a charge transporting substance in a so-called function-separated type photosensitive layer in which a charge generating layer and a charge transporting layer are divided into two layers.
It is also useful as an intermediate for producing various materials derived from hydroxyl groups, for example, polycarbonate resin, polyester resin, polyurethane resin, epoxy resin and the like.
[Brief description of the drawings]
FIG. 1 is an infrared absorption spectrum (KBr tablet method) of an amine compound (Compound No. 17) of the present invention.
FIG. 2 is an infrared absorption spectrum (KBr tablet method) of the amine compound (Compound No. 18) of the present invention.

Claims (9)

A hydroxyl group-containing amine compound represented by the following general formula (1).

Wherein, R _1, R ₂ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group and Table Wa, the substituent of the alkyl group a fluorine atom, a cyano group, a phenyl group, or It is a phenyl group substituted with a halogen atom or a C _{1 to} C ₅ alkyl group, and the substituent of the aryl group is a C _{1 to} C ₅ alkyl group or a halogen atom. Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₆ each independently represent an arylene group.
_{Furthermore, Ar 4, Ar 5, Ar} 7 are independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group and Table Wa, substituents for the aryl group or the heterocyclic group may be substituted with lower alkyl A lower alkoxy group and a halogen atom. A hydroxyl group-containing amine compound represented by the following general formula (2).

In the formula, R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group and Table Wa, substituent a fluorine atom of the alkyl group, a cyano group, a phenyl group, or a halogen atom or a phenyl group substituted with an alkyl group of C ₁ -C _5, substituents for the aryl group is an alkyl group, or a halogen atom C ₁ -C _5. Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₆ each independently represent an arylene group.
_{Furthermore, Ar 4, Ar 5, Ar} 7 are independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group and Table Wa, substituents for the aryl group or the heterocyclic group may be substituted with lower alkyl A lower alkoxy group and a halogen atom. A hydroxyl group-containing amine compound represented by the following general formula (3).

In the formula, Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₆ each independently represent an arylene group. _{Furthermore, Ar 4, Ar 5, Ar} 7 are independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group and Table Wa, substituents for the aryl group or the heterocyclic group may be substituted with lower alkyl A lower alkoxy group and a halogen atom. A hydroxyl group-containing amine compound represented by the following general formula (4).

In the formula, Ar ₂ , Ar ₃ , and Ar ₆ each independently represent an arylene group. _{Ar 4,} Ar 5, Ar ₇ are independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group and Table Wa, substituents are lower alkyl of the aryl group or heterocyclic group, A lower alkoxy group and a halogen atom. R ₃ is a halogen atom, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group and Table Wa, substituent a fluorine atom of the alkyl group, a cyano group, a phenyl group, or a halogen atom or a phenyl group substituted with an alkyl group of C ₁ -C _5, substituents for the aryl group is an alkyl group, or a halogen atom C ₁ -C _5. a represents an integer of 1 to 4. A hydroxyl group-containing amine compound represented by the following general formula (5).

In the formula, Ar ₆ represents an arylene group. _{Ar 4,} Ar 5, Ar ₇ are independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group and Table Wa, substituents are lower alkyl of the aryl group or heterocyclic group, A lower alkoxy group and a halogen atom. R _{3, R 4,} R ₅ is a halogen atom, a hydrogen atom, a substituted or unsubstituted alkyl group, and Wa substituted or unsubstituted aryl group table, the substituent of the alkyl group a fluorine atom, a cyano group, a phenyl group Or a phenyl group substituted with a halogen atom or a C ₁ -C ₅ alkyl group, and the substituent of the aryl group is a C ₁ -C ₅ alkyl group or a halogen atom. a, b, and c represent an integer of 1 to 4. A hydroxyl-containing amine compound represented by the following general formula (6).

In the formula, Ar ₆ represents an arylene group. Ar _4, Ar ₅ each independently represent a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group and Table Wa, substituents are lower alkyl of the aryl group or heterocyclic group, a lower alkoxy group And a halogen atom. _{Also, R 3, R 4, R} 5, R 6 is a halogen atom, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group and Table Wa, the substituent of the alkyl group a fluorine atom, A cyano group, a phenyl group, or a phenyl group substituted with a halogen atom or a C _{1 to} C ₅ alkyl group, and the substituent of the aryl group is a C _{1 to} C ₅ alkyl group or a halogen atom. a, b, and c represent an integer of 1 to 4. d represents an integer of 1 to 5. A hydroxyl group-containing amine compound represented by the following general formula (7).

In the formula, Ar ₆ represents an arylene group. _{Also, R 3, R 4, R} 5, R 6, R 7, R 8 is a halogen atom, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group and Table Wa, and the alkyl group The substituent is a fluorine atom, a cyano group, a phenyl group, or a phenyl group substituted with a halogen atom or a C _{1 to} C ₅ alkyl group, and the substituent of the aryl group is a C _{1 to} C ₅ alkyl group, or It is a halogen atom. a, b, and c represent an integer of 1 to 4. d, e, and f represent an integer of 1 to 5. A hydroxyl group-containing amine compound represented by the following general formula (8).

_{Wherein, R 3, R 4, R} 5, R 6, R 7, R 8, R 9 is a halogen atom, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group and Table Wa, substituent fluorine atom of the alkyl group, a cyano group, a phenyl group, or a phenyl group substituted by a halogen atom or an alkyl group of C ₁ -C _5, the substituent of the aryl group of C ₁ -C ₅ It is an alkyl group or a halogen atom. a, b, c, and g represent an integer of 1 to 4. d, e, and f represent an integer of 1 to 5. An intermediate for producing a hydroxyl group-containing amine compound represented by the following general formula (9).

Wherein, R _1, R ₂ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group and Table Wa, substituent a fluorine atom of the alkyl group, a cyano group, a phenyl group, or a halogen It is a phenyl group substituted by an atom or a C ₁ -C ₅ alkyl group, and the substituent of the aryl group is a C ₁ -C ₅ alkyl group or a halogen atom. Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₆ each independently represent an arylene group.
_{Ar 4,} Ar 5, Ar ₇ are independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group and Table Wa, substituents are lower alkyl of the aryl group or heterocyclic group, A lower alkoxy group and a halogen atom. R ₁₀ represents a halogen atom , an unsubstituted alkyl group or an acyl group.

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