JP3611370B2 - Bisazo compounds and intermediates for their production - Google Patents

Description

【０００６】
（式中、Ａｒ¹，Ａｒ²，Ａｒ³，Ａｒ⁴は置換もしくは無置換のアリール基を表し、置換基は炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、フェニル基、ビフェニリル基、ナフチル基、アントリル基、ピレニル基であり、各々同一でも異なっていてもよい。Ｒはエチレン基−ＣＨ₂ＣＨ₂−又はビニレン基−ＣＨ＝ＣＨ−を表わす。）
【０００７】
【化８】

【０００８】
（式中、Ｒ^１は水素原子もしくはアルキル基を表す。Ｒはエチレン基−ＣＨ_２ＣＨ_２−又はビニレン基−ＣＨ＝ＣＨ−を表わす。）
【０００９】
【化９】

【００１０】
（式中、Ａｒ¹，Ａｒ²は置換もしくは無置換のアリール基を表し、置換基は炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、フェニル基、ビフェニリル基、ナフチル基、アントリル基、ピレニル基であり、各々同一でも異なっていてもよく、Ｒ²は水素原子、アルキル基、アルコキシ基、ハロゲン原子、ニトロ基もしくはジアルキルアミノ基を表し、Ｒはエチレン基−ＣＨ₂ＣＨ₂−又はビニレン基−ＣＨ＝ＣＨ−を表わす。ｎは水素原子以外の時に１〜３の整数を表し、ｎが複数の場合Ｒ₂はそれぞれ同一でも異なっていてもよい）
【００１１】
【化１０】

【００１２】
（式中、Ｒ^１は水素原子もしくはアルキル基を表す。Ｒはエチレン基−ＣＨ_２ＣＨ_２−又はビニレン基−ＣＨ＝ＣＨ−を表わす。）
【００１３】
【化１１】

【００１４】
（式中、Ａｒ¹，Ａｒ²は置換もしくは無置換のアリール基を表し、置換基は炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、フェニル基、ビフェニリル基、ナフチル基、アントリル基、ピレニル基であり、各々同一でも異なっていてもよい。Ｒはエチレン基−ＣＨ₂ＣＨ₂−又はビニレン基−ＣＨ＝ＣＨ−を表わす。）
【００１５】
【化１２】

【００１６】
（式中、Ｒ^１は水素原子もしくはアルキル基を表す。Ｒはエチレン基−ＣＨ_２ＣＨ_２−又はビニレン基−ＣＨ＝ＣＨ−を表わす。）
説明の順序が逆になるが、本発明の一般式Ｖで表される２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物は、下記一般式ＶＩＩで表されるアニリン化合物と、下記式ＶＩＩＩで表される２−ヒドロキシ−３−ナフトエ酸とを反応させることによって得ることができる。
【００１７】
【化１３】

【００１８】
（式中、Ａｒ¹，Ａｒ²は置換もしくは無置換のアリール基を表し、置換基は炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、フェニル基、ビフェニリル基、ナフチル基、アントリル基、ピレニル基であり、各々同一でも異なっていてもよい。Ｒはエチレン基−ＣＨ₂ＣＨ₂−又はビニレン基−ＣＨ＝ＣＨ−を表わす。）
【００１９】
【化１４】

【００２０】
実際には前記一般式Ｖで表される２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物の製造は、ベンゼン、トルエン、ジオキサンなどの有機溶媒に、前記式ＶＩＩＩで表される２−ヒドロキシ−３−ナフトエ酸を溶解もしくは分散しておき、これに五塩化リン、三塩化リン、塩化チオニルなどのハロゲン化剤を添加することにより酸ハロゲン化物とし、これを単離するか、もしくはそのまま前記一般式ＶＩＩで表されるアニリン化合物と反応させることにより得ることができる。
本発明の前記一般式Ｉ，ＩＩ，ＩＩＩおよびＩＶで表されるビスアゾ化合物は前述のように、積層型の電子写真感光体の電荷発生物質として有用であるが、更に樹脂中に電荷発生物質と電荷輸送物質とを分散させた単層型の感光層を有する電子写真感光体における電荷発生物質として、又、樹脂中に光導電性物質を分散させた感光層を有する電子写真用感光体における光導電性物質としても有用である。
本発明の一般式Ｉで表されるビスアゾ化合物は、下記一般式ＩＸで表されるビス（ジアゾニウム塩）化合物と、前記一般式Ｖで表される２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物とを反応させることによって得ることができる。
【００２１】
【化１５】

【００２２】
（式中、Ｘはアニオン官能基を表す。）
また、本発明の一般式ＩＩＩで表されるビスアゾ化合物は、前記一般式ＩＸで表されるビス（ジアゾニウム塩）化合物と前記一般式Ｖまたは下記一般式Ｘで表される２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物とを２段階に順次反応させるか、あるいは最初のカップリング反応によって得られる下記一般式ＸＩまたはＸＩＩのジアゾニウム塩化合物を単離した後、更にそれぞれに対応する２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物を反応させることによって得ることができる。
【００２３】
【化１６】

【００２４】
（式中、Ｒ^２は水素原子、アルキル基、アルコキシ基、ハロゲン原子、ニトロ基もしくはジアルキルアミノ基を表し、ｎは水素以外のときに整数を表し、ｎが複数の場合Ｒ^２はそれぞれ同一でも異なっていてもよい。）
【００２５】
【化１７】

【００２６】
（式中、Ａｒ¹，Ａｒ²は置換もしくは無置換のアリール基を表し、置換基は炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、フェニル基、ビフェニリル基、ナフチル基、アントリル基、ピレニル基であり、各々同一でも異なっていてもよく、Ｘはアニオン官能基を表す。Ｒはエチレン基−ＣＨ₂ＣＨ₂−又はビニレン基−ＣＨ＝ＣＨ−を表わす。）
【００２７】
【化１８】

【００２８】
（式中、Ｒ^２は水素原子、アルキル基、アルコキシ基、ハロゲン原子、ニトロ基もしくはジアルキルアミノ基を表し、ｎは水素以外のときに整数を表し、ｎが複数の場合Ｒ^２はそれぞれ同一でも異なっていてもよく、Ｘはアニオン官能基をあらわす）
実際には上記一般式Ｉで表されるビスアゾ化合物の製造は、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）やジメチルスルホキシド（ＤＭＳＯ）などの有機溶媒に、前記一般式Ｖで表される２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物を溶解しておき、これに前記一般式ＩＸで表されるビス（ジアゾニウム塩）化合物を添加し、酢酸ナトリウム水溶液や有機アミンのような塩基性物質を添加することによりカップリング反応を終了させる。この時の反応温度としては約−２０℃から約４０℃が好ましい。
また前記一般式ＩＩＩで表されるビスアゾ化合物はＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）やジメチルスルホキシド（ＤＭＳＯ）などの有機溶媒に、第１段階のカップリング反応に用いる前記一般式ＶまたはＸで表される２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物を溶解しておき、これに一般式ＩＸで表されるビス（ジアゾニウム塩）化合物を添加し、必要によって酢酸ナトリウム水溶液や有機アミンのような塩基性物質を添加することにより、第１段階のカップリング反応は終了する。
【００２９】
この時の反応温度としては約−２０℃から約４０℃が好ましい。第２段階のカップリング反応は、上記で得られた反応混合物に、更に第１段階のカップリング反応で用いたものとは異なる前記一般式ＶまたはＸの２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物を更に添加し、第１段階のカップリング反応と同様に必要によって、酢酸ナトリウム水溶液や有機アミンのような塩基性物質を添加することにより完了させるか、あるいは第１段階のカップリング反応混合物を必要によって水やあるいは希塩酸などの酸性水溶液を添加（この際には十分な冷却を行い、反応によって生成している前記一般式ＸＩまたはＸＩＩのジアゾニウム塩化合物を分解させないようにする必要がある。好ましくは１０℃以下で処理することが望ましい）し、一般式ＸＩまたはＸＩＩのジアゾニウム塩化合物を濾別して単離し、更にこのジアゾニウム塩化合物と、第１段階のカップリング反応で用いたものとは異なる一般式ＶまたはＸの２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物とを、第１段階のカップリング反応と同様に反応させることによって完了する。
いずれの方法によって行った反応混合物においても、反応終了後析出している結晶を濾取し、適切な方法により精製（例えば水及び／あるいは有機溶剤による洗浄、再結晶法など）することにより前記一般式ＩＩＩのビスアゾ化合物の製造は完了する。
【００３０】
前記一般式Ｉ，II，III，IV，Ｖ，VI，VII，IX，Ｘ，XIおよびXIIにおけるＲ¹，Ｒ²，Ａｒ¹，Ａｒ²，Ａｒ³及びＡｒ⁴あるいはそれらの置換基の具体例としては、アルキル基としてメチル基、エチル基、プロピル基、ブチル基を、アルコキシ基としてメトキシ基、エトキシ基、プロポキシ基、ブトキシ基を、ハロゲン原子としてフッ素、塩素、臭素、ヨウ素を、アリール基としてフェニル基、ビフェニリル基、ナフチル基、アントリル基、ピレニル基を、Ｒとしてエチレン基−ＣＨ₂ＣＨ₂−又はビニレン基−ＣＨ＝ＣＨ−を挙げることができる。また、前記一般式IX，XI及びXIIにおける
【００３１】
【数１】

【００３２】
はアニオン官能基を表すが、例えばテトラフルオロボレート、パークロレート、ヨーデイド、クロライド、ブロマイド、サルフェート、ヘキサフルオロホスフェート、ヘキサフルオロアンチモネート、パーヨーデイド、ｐ−トルエンスルホネート等が好ましい。
【００３３】
【実施例】
本発明の２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物及びそれを中間体として製造されるビスアゾ化合物は、上記の説明に従って容易に製造することができる。また本発明のビスアゾ化合物が電子写真用感光体において有効な材料であることを明らかにするために以下に実施例及び応用例を示すが、本発明はもとよりこれに限定されるものではない。
実施例１
２−ヒドロキシ−３−ナフトエ酸２．３４ｇ（１２．４ｍｍｏｌ）、４−（３−アミノフェネチル）−４’，４’’−ジメチルトリフェニルアミン４．８８ｇ（１２．４ｍｍｏｌ）を１，４−ジオキサン３０ｍｌに溶解し、室温にて三塩化リン０．８５ｇ（６．２ｍｍｏｌ）を１，４−ジオキサン５ｍｌにて希釈した溶液を１０分間かけ滴下し、３時間還流撹拌した。内容物を室温までに放冷し、これを氷水に開け炭酸ナトリウムにて中和を行った。生成している沈殿を濾別し、これを水洗、ついでメタノール洗浄後、減圧加熱乾燥することにより薄茶色の粗結晶６．７０ｇ（収率９５．７％）を得た。更にこれをシリカゲルカラムクロマト処理〔溶離液：トルエン／酢酸エチル＝５／１（体積比）〕し、ついで酢酸エチル／エタノール混合溶媒にて再結晶することにより、無色結晶の下記式１で表される目的物の２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物４．２０ｇ（収率６０．０％）を得た。
融点は１８１．０〜１８２．０℃であった。この２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物の赤外吸収スペクトル（ＫＢｒ錠剤法）を図１に示す。

【００３４】
【化１９】

【００３５】
実施例２
実施例１と同様な条件で他の２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物２を得た。得られた化合物の収率、融点、元素分析を表１に示す。また得られた化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）を図２に示す。
【００３６】
【化２０】

【００３７】
【表１】

【００３８】
実施例３
２−ヒドロキシ−３−〔３−（４−ジ−ｐ−トリルアミノフェネチル）フェニル〕カルバモイルナフタレン３．３８ｇ（６ｍｍｏｌ）をＤＭＦ２４０ｍｌに溶解し、室温にて９−フルオレノン−２，７−ビスジアゾニウムビステトラフルオロボレート１．２２ｇ（３ｍｍｏｌ）を加えた。次いで酢酸ナトリウム三水和物１．６３ｇ（１２ｍｍｏｌ）を水９ｍｌに溶解させたものを２０分間かけ滴下し、２時間室温にて撹拌した。生成している沈殿を濾別し、８０℃に加熱したＤＭＦ２５０ｍｌで３回洗浄し、次に水２５０ｍｌで２回洗浄した。１２０℃で減圧下に乾燥して、下記式３のビスアゾ化合物２．７８ｇ（収率６８．３％）を得た。融点は２８０℃以上であった。このビスアゾ化合物の赤外吸収スペクトル（ＫＢｒ錠剤法）を図３に示す。

【００３９】
【化２１】

【００４０】
実施例４
２−ヒドロキシ−３−（２−クロロフェニル）カルバモイルナフタレン０．８９ｇ（３ｍｍｏｌ）をＤＭＦ１２０ｍｌに溶解し、室温にて９−フルオレノン−２，７−ビスジアゾニウムビステトラフルオロボレート１．２２ｇ（３ｍｍｏｌ）を加えた。室温にて１０分間撹拌した後、２−ヒドロキシ−３−〔３−（４−ジ−ｐ−トリルアミノフェネチル）フェニル〕カルバモイルナフタレン１．６９ｇ（３ｍｍｏｌ）およびＤＭＦ１２０ｍｌを加え、次いで酢酸ナトリウム三水和物１．６３ｇ（１２ｍｍｏｌ）を水９ｍｌに溶解させたものを２０分間かけ滴下し、２時間室温にて撹拌した。生成している沈殿を濾別し、８０℃に加熱したＤＭＦ２４０ｍｌで３回洗浄し、次に水２４０ｍｌで２回洗浄した。１２０℃で減圧下に乾燥して、下記式４で表されるビスアゾ化合物２．０３ｇ（収率６１．９％）を得た。融点は２８０℃以上であった。このビスアゾ化合物の赤外吸収スペクトル（ＫＢｒ錠剤法）を図４に示す。

【００４１】
【化２２】

【００４２】
実施例５，６
実施例３もしくは４と同様な条件で、他のビスアゾ化合物５及び６を得た。得られた化合物の融点、元素分析値を表１に示す。また得られたビスアゾ化合物のそれぞれの赤外吸収スペクトル図（ＫＢｒ錠剤法）を図５，図６に示す。
【００４３】
【化２３】

【００４４】
実施例７
実施例１と同様な条件で他の２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物７を得た。得られた化合物の収率融点、元素分析を表１に示す。また得られた化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）を図７に示す。
【００４５】
【化２４】

【００４６】
実施例８，９
実施例３もしくは４と同様な条件で他のビスアゾ化合物８及び９を得た。得られた化合物の融点、元素分析値を表１に示す。また得られたビスアゾ化合物のそれぞれの赤外吸収スペクトル図（ＫＢｒ錠剤法）を図８及び９に示す。
【００４７】
【化２５】

【００４８】
実施例１０，１１
実施例３もしくは４と同様な条件で他のビスアゾ化合物１０及び１１を得た。得られた化合物の融点、元素分析値を表２に示す。また得られたビスアゾ化合物のそれぞれの赤外吸収スペクトル図（ＫＢｒ錠剤法）を図１０，１１に示す。
【００４９】
【化２６】

【００５０】
【表２】

【００５１】
実施例１２
実施例１と同様な条件で他の２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物を得た。得られた化合物の融点、元素分析値を表３に示す。また得られた化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）を図１２に示す。
【００５２】
【化２７】

【００５３】
【表３】

【００５４】
実施例１３〜１６
実施例３もしくは４と同様な条件で他のビスアゾ化合物１３〜１６を得た。得られた化合物の融点、元素分析値を表４に示す。また得られたビスアゾ化合物のそれぞれの赤外吸収スペクトル図（ＫＢｒ錠剤法）を図１３〜１６に示す。
【００５５】
【化２８】

【００５６】
【表４】

【００５７】
実施例１７，１８
実施例１と同様な条件で他の２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物を得た。得られた化合物の融点、元素分析値を表５に示す。また得られた化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）を図１７，１８に示す。
【００５８】
【化２９】

【００５９】
【表５】

【００６０】
応用例１
実施例３で得られた前式３のビスアゾ化合物７．５重量部及びポリエステル樹脂（東洋紡績社製バイロン２００）のテトラヒドロフラン溶液（固形分濃度０．５重量％）５００重量部をボールミル中で粉砕混合し、得られた分散液をアルミニウム蒸着したポリエステルベース（導電性支持体）のアルミニウム面上にドクターブレードを用いて塗布し、自然乾燥して、厚さ約１μｍの電荷発生層を形成した。
この電荷発生層上に電荷輸送物質として１−フェニル−３−（４−ジエチルアミノスチリル）−５−（４−ジエチルアミノフェニル）ピラゾリン１重量部、ポリカーボネート樹脂（帝人社製パンライトＫ−１３００）１重量部及びテトラヒドロフラン８重量部を混合溶解した溶液をドクターブレードを用いて塗布し、８０℃で２分間、次いで１２０℃で５分間乾燥して厚さ約２０μｍの電荷輸送層を形成して積層型の感光体を作成した。
上記のようにして作製した積層型の感光体について、静電複写紙試験装置〔（株）川口電気製作所製ＳＰ４２８型）を用いて、−６ＫＶのロナ放電を２０秒間行って負に帯電せしめた後、２０秒間暗所に放置し、その時の表面電位Ｖ_ｐｏ（Ｖ）を測定し、次いでタングステンランプによってその表面が照度４．５ｌｕｘになるように光を照射し、光減衰によってＶ_ｐｏが１／２になるまでの時間（ｓｅｃ）を求め、感光体の感度として半減露光量Ｅ_１／２（ｌｕｘ・ｓｅｃ）を算出した。Ｖ_ｐｏは−１０８６（Ｖ）、Ｅ_１／２は１．１１（ｌｕｘ・ｓｅｃ）であり、高感度な感光体であることがわかる。
【００６１】
応用例２
実施例４で得られた前式４で表されるビスアゾ化合物を用い、電荷輸送物質として４’−ジフェニルアミノ−α−フェニルスチルベンに変えた以外は、応用例１と同様にして感光体を作成し、測定を行った。Ｖ_ｐｏは−１１２２（Ｖ）、Ｅ_１／２は０．９１（ｌｕｘ・ｓｅｃ）であり高感度な感光体であることがわかる。
【００６２】
【発明の効果】
以上の説明からわかるように、本発明の２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物並びにビスアゾ化合物は容易に製造できる。又、応用例からも明らかなように本発明のビスアゾ化合物は高速度複写機などに実用的な高感度電子写真感光体における電荷発生物質として極めて有用である。
【図面の簡単な説明】
【図１】実施例１で得られた本発明の２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図２】実施例２で得られた本発明の２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図３】実施例３で得られた本発明のビスアゾ化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図４】実施例４で得られた本発明のビスアゾ化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図５】実施例５で得られた本発明のビスアゾ化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図６】実施例６で得られた本発明のビスアゾ化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図７】実施例７で得られた本発明の２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図８】実施例８で得られた本発明のビスアゾ化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図９】実施例９で得られた本発明のビスアゾ化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図１０】実施例１０で得られた本発明のビスアゾ化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図１１】実施例１１で得られた本発明のビスアゾ化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図１２】実施例１２で得られた本発明の２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図１３】実施例１３で得られた本発明のビスアゾ化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図１４】実施例１４で得られた本発明のビスアゾ化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図１５】実施例１５で得られた本発明のビスアゾ化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図１６】実施例１６で得られた本発明のビスアゾ化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図１７】実施例１７で得られた本発明の２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。
【図１８】実施例１８で得られた本発明の２−ヒドロキシ−３−フェニルカルバモイルナフタレン化合物の赤外吸収スペクトル図（ＫＢｒ錠剤法）である。[0001]
[Industrial application fields]
The present invention relates to bisazo compounds and to 2-hydroxy-3-phenylcarbamoylnaphthalene compounds which are intermediates for the production thereof. More particularly, it relates to a bisazo compound useful as an organic photoconductor.
[0002]
[Prior art]
Conventionally, it is known that a certain kind of azo compound is effective as a charge generation pigment used in a charge generation layer of a multilayer photoreceptor which is one form of an electrophotographic photoreceptor. As used herein, the term “layered photoreceptor” refers to a charge-generating pigment having the ability to generate charge carriers by light on a conductive support, by an appropriate method such as vacuum deposition, application of a pigment solution, or fine pigmentation in a resin solution. A charge generation layer is formed as a thin layer by applying a dispersion liquid in which particles are dispersed, and the charge carrier generated in the charge generation layer is efficiently injected onto the charge generation layer. The charge transport layer is a photoreceptor formed with a charge transport material and a binder resin. Conventionally, as azo compounds used in this type of photoreceptor, benzidine-based bisazo compounds described in, for example, JP-A-47-37543 and JP-A-52-55643. Alternatively, stilbene bisazo compounds described in JP-A-52-8832 are known.
However, a conventional multilayer photoreceptor using an azo compound is generally insufficient in sensitivity, and is insufficient as a photoreceptor for a high-speed copying machine.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a bisazo compound that is effective in an electrophotographic photoreceptor, particularly useful in the above-described laminated photoreceptor, and a 2-hydroxy-3-phenylcarbamoylnaphthalene compound that is an intermediate for producing the bisazo compound. There is to do.
[0004]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have synthesized a novel 2-hydroxy-3-phenylcarbamoylnaphthalene compound, synthesized a novel bisazo compound using this as an intermediate, and that the above problem can be achieved by this. The headline, the present invention has been reached.
That is, according to the present invention, bisazo compounds represented by the following general formulas I to IV are provided, and 2-hydroxy-3-phenyl represented by the general formulas V and VI, which are intermediates for producing the bisazo compounds. Carbamoylnaphthalene compounds are provided.
[0005]
[Chemical 7]

[0006]
(In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ represent a substituted or unsubstituted aryl group, and the substituent is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluorine atom, A chlorine atom, a bromine atom, an iodine atom, a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a pyrenyl group, each of which may be the same or different, and R is an ethylene group —CH ₂ CH ₂ — or a vinylene group —CH. = CH-)
[0007]
[Chemical 8]

[0008]
(Wherein R ¹ represents a hydrogen atom or an alkyl group. R represents an ethylene group —CH ₂ CH ₂ — or a vinylene group —CH═CH—).
[0009]
[Chemical 9]

[0010]
(In the formula, Ar ¹ and Ar ² represent a substituted or unsubstituted aryl group, and the substituent is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, An iodine atom, a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a pyrenyl group, each of which may be the same or different, and R ² is a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, or a dialkylamino group R represents an ethylene group —CH ₂ CH ₂ — or a vinylene group —CH═CH—, n represents an integer of 1 to 3 when other than a hydrogen atom, and when n is plural, R ₂ may be the same May be different)
[0011]
[Chemical Formula 10]

[0012]
(Wherein R ¹ represents a hydrogen atom or an alkyl group. R represents an ethylene group —CH ₂ CH ₂ — or a vinylene group —CH═CH—).
[0013]
Embedded image

[0014]
(In the formula, Ar ¹ and Ar ² represent a substituted or unsubstituted aryl group, and the substituent is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, An iodine atom, a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a pyrenyl group, which may be the same or different, and R represents an ethylene group —CH ₂ CH ₂ — or a vinylene group —CH═CH—; )
[0015]
Embedded image

[0016]
(Wherein R ¹ represents a hydrogen atom or an alkyl group. R represents an ethylene group —CH ₂ CH ₂ — or a vinylene group —CH═CH—).
Although the order of description is reversed, the 2-hydroxy-3-phenylcarbamoylnaphthalene compound represented by the general formula V of the present invention is represented by the aniline compound represented by the following general formula VII and the following formula VIII. It can be obtained by reacting with 2-hydroxy-3-naphthoic acid.
[0017]
Embedded image

[0018]
(In the formula, Ar ¹ and Ar ² represent a substituted or unsubstituted aryl group, and the substituent is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, An iodine atom, a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a pyrenyl group, which may be the same or different, and R represents an ethylene group —CH ₂ CH ₂ — or a vinylene group —CH═CH—; )
[0019]
Embedded image

[0020]
Actually, the production of the 2-hydroxy-3-phenylcarbamoylnaphthalene compound represented by the general formula V is carried out in an organic solvent such as benzene, toluene, dioxane or the like, by the 2-hydroxy-3-naphthoene represented by the formula VIII. An acid halide is obtained by dissolving or dispersing the acid, and adding a halogenating agent such as phosphorus pentachloride, phosphorus trichloride, thionyl chloride, etc. It can be obtained by reacting with the aniline compound represented.
As described above, the bisazo compounds represented by the general formulas I, II, III, and IV of the present invention are useful as charge generation materials for laminated electrophotographic photoreceptors. Light in an electrophotographic photoreceptor having a single layer type photosensitive layer in which a charge transport material is dispersed, and in an electrophotographic photoreceptor having a photosensitive layer in which a photoconductive substance is dispersed in a resin It is also useful as a conductive material.
The bisazo compound represented by the general formula I of the present invention comprises a bis (diazonium salt) compound represented by the following general formula IX and a 2-hydroxy-3-phenylcarbamoylnaphthalene compound represented by the general formula V. It can be obtained by reacting.
[0021]
Embedded image

[0022]
(In the formula, X represents an anionic functional group.)
Further, the bisazo compound represented by the general formula III of the present invention includes a bis (diazonium salt) compound represented by the general formula IX and 2-hydroxy-3- represented by the general formula V or the following general formula X. A phenylcarbamoylnaphthalene compound is reacted sequentially in two steps, or a diazonium salt compound of the following general formula XI or XII obtained by the first coupling reaction is isolated, and then the corresponding 2-hydroxy-3- It can be obtained by reacting a phenylcarbamoylnaphthalene compound.
[0023]
Embedded image

[0024]
(Wherein R ² represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group or a dialkylamino group, n represents an integer other than hydrogen, and when n is plural, R ² may be the same as each other) May be different.)
[0025]
Embedded image

[0026]
(In the formula, Ar ¹ and Ar ² represent a substituted or unsubstituted aryl group, and the substituent is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, An iodine atom, a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a pyrenyl group, each of which may be the same or different, and X represents an anionic functional group, and R represents an ethylene group —CH ₂ CH ₂ — or a vinylene group. -CH = CH- is represented.)
[0027]
Embedded image

[0028]
(Wherein R ² represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group or a dialkylamino group, n represents an integer other than hydrogen, and when n is plural, R ² may be the same as each other) May be different, X represents an anionic functional group)
Actually, the production of the bisazo compound represented by the above general formula I is carried out in an organic solvent such as N, N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) in the 2-hydroxy-form represented by the above general formula V. A 3-phenylcarbamoylnaphthalene compound is dissolved, a bis (diazonium salt) compound represented by the general formula IX is added thereto, and a basic substance such as an aqueous sodium acetate solution or an organic amine is added to the cup. Terminate the ring reaction. The reaction temperature at this time is preferably about -20 ° C to about 40 ° C.
The bisazo compound represented by the general formula III is represented by the general formula V or X used in the first-stage coupling reaction in an organic solvent such as N, N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO). 2-hydroxy-3-phenylcarbamoylnaphthalene compound is dissolved, and a bis (diazonium salt) compound represented by the general formula IX is added thereto, and if necessary, a basic solution such as aqueous sodium acetate or organic amine By adding the substance, the first-stage coupling reaction is completed.
[0029]
The reaction temperature at this time is preferably about -20 ° C to about 40 ° C. In the second-stage coupling reaction, the 2-hydroxy-3-phenylcarbamoylnaphthalene compound of the above general formula V or X is different from that used in the first-stage coupling reaction in the reaction mixture obtained above. To complete the addition of a basic substance such as an aqueous sodium acetate solution or an organic amine, if necessary, as in the first-stage coupling reaction, or a first-stage coupling reaction mixture is required. Water or an acidic aqueous solution such as dilute hydrochloric acid is added by (in this case, sufficient cooling is required so as not to decompose the diazonium salt compound of the general formula XI or XII generated by the reaction. And the diazonium salt compound of the general formula XI or XII is filtered off. In addition, the diazonium salt compound and a 2-hydroxy-3-phenylcarbamoylnaphthalene compound of the general formula V or X different from those used in the first-stage coupling reaction are coupled to the first-stage coupling. Complete by reacting in the same way as the reaction.
In any reaction mixture obtained by any method, the crystals precipitated after the completion of the reaction are collected by filtration and purified by an appropriate method (for example, washing with water and / or organic solvent, recrystallization method, etc.). The production of the bisazo compound of formula III is complete.
[0030]
Specific examples of R ¹ , R ² , Ar ¹ , Ar ² , Ar ³ and Ar ⁴ or their substituents in the general formulas I, II, III, IV, V, VI, VII, IX, X, XI and XII As an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group , an alkoxy group as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group as halogen atoms, fluorine, chlorine, bromine, iodine as an aryl group Examples of R include a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a pyrenyl group , and R may include an ethylene group —CH ₂ CH ₂ — or a vinylene group —CH═CH—. In the general formulas IX, XI and XII,
[Expression 1]

[0032]
Represents an anionic functional group. For example, tetrafluoroborate, perchlorate, iodide, chloride, bromide, sulfate, hexafluorophosphate, hexafluoroantimonate, periodide, p-toluenesulfonate and the like are preferable.
[0033]
【Example】
The 2-hydroxy-3-phenylcarbamoylnaphthalene compound of the present invention and the bisazo compound produced using it as an intermediate can be easily produced according to the above description. In order to clarify that the bisazo compound of the present invention is an effective material for an electrophotographic photoreceptor, examples and application examples will be shown below, but the present invention is not limited to these examples.
Example 1
2.34 g (12.4 mmol) of 2-hydroxy-3-naphthoic acid and 4.88 g (12.4 mmol) of 4- (3-aminophenethyl) -4 ′, 4 ″ -dimethyltriphenylamine were added to 1,4- A solution prepared by dissolving 0.85 g (6.2 mmol) of phosphorus trichloride in 5 ml of 1,4-dioxane was added dropwise over 10 minutes after dissolving in 30 ml of dioxane and stirred at reflux for 3 hours. The contents were allowed to cool to room temperature, opened in ice water, and neutralized with sodium carbonate. The produced precipitate was separated by filtration, washed with water, then washed with methanol, and dried by heating under reduced pressure to obtain 6.70 g (yield 95.7%) of light brown crude crystals. Further, this was subjected to silica gel column chromatography treatment (eluent: toluene / ethyl acetate = 5/1 (volume ratio)), and then recrystallized with a mixed solvent of ethyl acetate / ethanol, whereby colorless crystals represented by the following formula 1 were obtained. As a result, 4.20 g (yield 60.0%) of 2-hydroxy-3-phenylcarbamoylnaphthalene compound was obtained.
The melting point was 181.0-182.0 ° C. The infrared absorption spectrum (KBr tablet method) of this 2-hydroxy-3-phenylcarbamoylnaphthalene compound is shown in FIG.

[0034]
Embedded image

[0035]
Example 2
Other 2-hydroxy-3-phenylcarbamoylnaphthalene compound 2 was obtained under the same conditions as in Example 1. The yield, melting point, and elemental analysis of the obtained compound are shown in Table 1. Moreover, the infrared absorption spectrum figure (KBr tablet method) of the obtained compound is shown in FIG.
[0036]
Embedded image

[0037]
[Table 1]

[0038]
Example 3
2-Hydroxy-3- [3- (4-di-p-tolylaminophenethyl) phenyl] carbamoylnaphthalene 3.38 g (6 mmol) was dissolved in 240 ml of DMF, and 9-fluorenone-2,7-bisdiazonium bis was dissolved at room temperature. Tetrafluoroborate 1.22 g (3 mmol) was added. Next, 1.63 g (12 mmol) of sodium acetate trihydrate dissolved in 9 ml of water was added dropwise over 20 minutes, and the mixture was stirred at room temperature for 2 hours. The resulting precipitate was filtered off and washed three times with 250 ml DMF heated to 80 ° C. and then twice with 250 ml water. It dried under reduced pressure at 120 degreeC, and obtained 2.78 g (yield 68.3%) of the bisazo compound of the following formula 3. The melting point was 280 ° C. or higher. The infrared absorption spectrum (KBr tablet method) of this bisazo compound is shown in FIG.

[0039]
Embedded image

[0040]
Example 4
0.89 g (3 mmol) of 2-hydroxy-3- (2-chlorophenyl) carbamoylnaphthalene is dissolved in 120 ml of DMF, and 1.22 g (3 mmol) of 9-fluorenone-2,7-bisdiazonium bistetrafluoroborate is added at room temperature. It was. After stirring at room temperature for 10 minutes, 1.69 g (3 mmol) of 2-hydroxy-3- [3- (4-di-p-tolylaminophenethyl) phenyl] carbamoylnaphthalene and 120 ml of DMF were added, followed by sodium acetate trihydrate A solution prepared by dissolving 1.63 g (12 mmol) of the product in 9 ml of water was added dropwise over 20 minutes and stirred at room temperature for 2 hours. The resulting precipitate was filtered off and washed three times with 240 ml DMF heated to 80 ° C. and then washed twice with 240 ml water. It dried under reduced pressure at 120 degreeC, and obtained 2.03 g (yield 61.9%) of the bisazo compound represented by following formula 4. The melting point was 280 ° C. or higher. The infrared absorption spectrum (KBr tablet method) of this bisazo compound is shown in FIG.

[0041]
Embedded image

[0042]
Examples 5 and 6
Other bisazo compounds 5 and 6 were obtained under the same conditions as in Example 3 or 4. Table 1 shows melting points and elemental analysis values of the obtained compounds. Moreover, each infrared absorption spectrum figure (KBr tablet method) of the obtained bisazo compound is shown in FIG. 5, FIG.
[0043]
Embedded image

[0044]
Example 7
Other 2-hydroxy-3-phenylcarbamoylnaphthalene compound 7 was obtained under the same conditions as in Example 1. The yield melting point and elemental analysis of the obtained compound are shown in Table 1. Infrared absorption spectrum (KBr tablet method) of the obtained compound is shown in FIG.
[0045]
Embedded image

[0046]
Examples 8 and 9
Other bisazo compounds 8 and 9 were obtained under the same conditions as in Example 3 or 4. Table 1 shows melting points and elemental analysis values of the obtained compounds. Moreover, each infrared absorption spectrum figure (KBr tablet method) of the obtained bisazo compound is shown in FIGS.
[0047]
Embedded image

[0048]
Examples 10 and 11
Other bisazo compounds 10 and 11 were obtained under the same conditions as in Example 3 or 4. Table 2 shows melting points and elemental analysis values of the obtained compounds. Moreover, each infrared absorption spectrum figure (KBr tablet method) of the obtained bisazo compound is shown in FIGS.
[0049]
Embedded image

[0050]
[Table 2]

[0051]
Example 12
Other 2-hydroxy-3-phenylcarbamoylnaphthalene compounds were obtained under the same conditions as in Example 1. Table 3 shows melting points and elemental analysis values of the obtained compounds. FIG. 12 shows an infrared absorption spectrum (KBr tablet method) of the obtained compound.
[0052]
Embedded image

[0053]
[Table 3]

[0054]
Examples 13-16
Other bisazo compounds 13 to 16 were obtained under the same conditions as in Example 3 or 4. Table 4 shows melting points and elemental analysis values of the obtained compounds. Moreover, each infrared absorption spectrum figure (KBr tablet method) of the obtained bisazo compound is shown to FIGS.
[0055]
Embedded image

[0056]
[Table 4]

[0057]
Examples 17 and 18
Other 2-hydroxy-3-phenylcarbamoylnaphthalene compounds were obtained under the same conditions as in Example 1. Table 5 shows melting points and elemental analysis values of the obtained compounds. Moreover, the infrared absorption spectrum figure (KBr tablet method) of the obtained compound is shown in FIGS.
[0058]
Embedded image

[0059]
[Table 5]

[0060]
Application example 1
In a ball mill, 7.5 parts by weight of the bisazo compound of Formula 3 obtained in Example 3 and 500 parts by weight of a tetrahydrofuran solution (solid content concentration: 0.5% by weight) of polyester resin (Toyobo Co., Ltd. Byron 200) were pulverized. The resulting dispersion was applied onto an aluminum surface of a polyester base (conductive support) on which aluminum was vapor-deposited using a doctor blade, and then naturally dried to form a charge generation layer having a thickness of about 1 μm.
On the charge generation layer, 1 part by weight of 1-phenyl-3- (4-diethylaminostyryl) -5- (4-diethylaminophenyl) pyrazoline as a charge transport material, 1 part by weight of a polycarbonate resin (Tanjin Panlite K-1300) A solution in which 8 parts by weight of tetrahydrofuran and 8 parts by weight of tetrahydrofuran are mixed and dissolved is applied using a doctor blade, and dried at 80 ° C. for 2 minutes and then at 120 ° C. for 5 minutes to form a charge transport layer having a thickness of about 20 μm. A photoconductor was prepared.
The laminated type photoconductor produced as described above was negatively charged by performing a -6 KV Rona discharge for 20 seconds using an electrostatic copying paper testing apparatus (SP428 type manufactured by Kawaguchi Electric Co., Ltd.). after allowed to stand for 20 seconds the dark, to measure the surface potential _V po (V) at that time, then irradiated with light so that the surface of the tungsten lamp becomes illuminance 4.5lux, _{V po} by light attenuation 1 The time (sec) to reach / 2 was obtained, and the half exposure amount E _1/2 (lux · sec) was calculated as the sensitivity of the photoreceptor. V _po is −1086 (V) and E _1/2 is 1.11 (lux · sec), which indicates that the photoconductor is highly sensitive.
[0061]
Application example 2
A photoconductor was prepared in the same manner as in Application Example 1 except that the bisazo compound represented by the above formula 4 obtained in Example 4 was used and the charge transport material was changed to 4′-diphenylamino-α-phenylstilbene. And measured. V _po is −1122 (V) and E _1/2 is 0.91 (lux · sec), which indicates that the photoconductor is highly sensitive.
[0062]
【The invention's effect】
As can be seen from the above description, the 2-hydroxy-3-phenylcarbamoylnaphthalene compound and the bisazo compound of the present invention can be easily produced. As is clear from the application examples, the bisazo compound of the present invention is extremely useful as a charge generating material in a high-sensitivity electrophotographic photosensitive member practical for high-speed copying machines and the like.
[Brief description of the drawings]
1 is an infrared absorption spectrum (KBr tablet method) of the 2-hydroxy-3-phenylcarbamoylnaphthalene compound of the present invention obtained in Example 1. FIG.
2 is an infrared absorption spectrum (KBr tablet method) of the 2-hydroxy-3-phenylcarbamoylnaphthalene compound of the present invention obtained in Example 2. FIG.
FIG. 3 is an infrared absorption spectrum (KBr tablet method) of the bisazo compound of the present invention obtained in Example 3.
4 is an infrared absorption spectrum diagram (KBr tablet method) of the bisazo compound of the present invention obtained in Example 4. FIG.
FIG. 5 is an infrared absorption spectrum (KBr tablet method) of the bisazo compound of the present invention obtained in Example 5.
6 is an infrared absorption spectrum diagram (KBr tablet method) of the bisazo compound of the present invention obtained in Example 6. FIG.
7 is an infrared absorption spectrum (KBr tablet method) of the 2-hydroxy-3-phenylcarbamoylnaphthalene compound of the present invention obtained in Example 7. FIG.
8 is an infrared absorption spectrum diagram (KBr tablet method) of the bisazo compound of the present invention obtained in Example 8. FIG.
9 is an infrared absorption spectrum diagram (KBr tablet method) of the bisazo compound of the present invention obtained in Example 9. FIG.
10 is an infrared absorption spectrum diagram (KBr tablet method) of the bisazo compound of the present invention obtained in Example 10. FIG.
11 is an infrared absorption spectrum view (KBr tablet method) of the bisazo compound of the present invention obtained in Example 11. FIG.
12 is an infrared absorption spectrum diagram (KBr tablet method) of the 2-hydroxy-3-phenylcarbamoylnaphthalene compound of the present invention obtained in Example 12. FIG.
13 is an infrared absorption spectrum diagram (KBr tablet method) of the bisazo compound of the present invention obtained in Example 13. FIG.
14 is an infrared absorption spectrum diagram (KBr tablet method) of the bisazo compound of the present invention obtained in Example 14. FIG.
15 is an infrared absorption spectrum diagram (KBr tablet method) of the bisazo compound of the present invention obtained in Example 15. FIG.
16 is an infrared absorption spectrum diagram (KBr tablet method) of the bisazo compound of the present invention obtained in Example 16. FIG.
17 is an infrared absorption spectrum diagram (KBr tablet method) of the 2-hydroxy-3-phenylcarbamoylnaphthalene compound of the present invention obtained in Example 17. FIG.
18 is an infrared absorption spectrum (KBr tablet method) of the 2-hydroxy-3-phenylcarbamoylnaphthalene compound of the present invention obtained in Example 18. FIG.

Claims (6)

A bisazo compound represented by the following general formula I.

(In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ represent a substituted or unsubstituted aryl group, and the substituent is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluorine atom, A chlorine atom, a bromine atom, an iodine atom, a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a pyrenyl group, each of which may be the same or different, and R is an ethylene group —CH ₂ CH ₂ — or a vinylene group —CH. = CH-) A bisazo compound represented by the following general formula II.

(Wherein R ¹ represents a hydrogen atom or an alkyl group. R represents an ethylene group —CH ₂ CH ₂ — or a vinylene group —CH═CH—). A bisazo compound represented by the following general formula III.

(In the formula, Ar ¹ and Ar ² represent a substituted or unsubstituted aryl group, and the substituent is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, An iodine atom, a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a pyrenyl group, each of which may be the same or different, and R ² is a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, or a dialkylamino group R represents an ethylene group —CH ₂ CH ₂ — or a vinylene group —CH═CH—, n represents an integer of 1 to 3 when other than a hydrogen atom, and when n is plural, R ₂ may be the same May be different) A bisazo compound represented by the following general formula IV.

(Wherein R ¹ represents a hydrogen atom or an alkyl group. R represents an ethylene group —CH ₂ CH ₂ — or a vinylene group —CH═CH—). A 2-hydroxy-3-phenylcarbamoylnaphthalene compound represented by the following general formula V:

(In the formula, Ar ¹ and Ar ² represent a substituted or unsubstituted aryl group, and the substituent is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, An iodine atom, a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a pyrenyl group, each of which may be the same or different, and R represents an ethylene group —CH ₂ CH ₂ — or a vinylene group —CH═CH—; ) 2-hydroxy-3-phenylcarbamoylnaphthalene compound represented by the following general formula VI.

(Wherein R ¹ represents a hydrogen atom or an alkyl group. R represents an ethylene group —CH ₂ CH ₂ — or a vinylene group —CH═CH—).

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