JP2005015750A - Perimidine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment that efficiently absorbs visible light and near infrared light and has attractive properties, for example, high extinction coefficient, high storage stability, high solubility and the like. <P>SOLUTION: The perimidine compound is represented by general formula (1) (wherein R1 and R2 are mutually independent and H, an alkyl, a substituted or unsubstituted aryl, an alkoxyalkyl or an aralkyl; R3, R4 are each an alkyl, R3 and R4 may be linked to form a ring; n is an integer of 0-5, m is an integer of 0-2; A is a divalent atomic group that forms a conjugate system together with an adjacent atomic group; W, X, Y, Z are mutually independent and each represent H, an alkyl group or a halogen atom). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

［Ｒ１、Ｒ２は互いに独立に水素原子、アルキル基、置換または非置換のアリール基、アルコキシアルキル基、アラルキル基のいずれかを表す。Ｒ３、Ｒ４はアルキル基を表す。Ｒ３、Ｒ４は連結して環を形成してもよい。ｎは０〜５の整数を表す。ｍは０〜２の整数を表す。Ａは隣接する原子団とともに共役系を形成する２価の原子団を表す。Ｗ、Ｘ、Ｙ、Ｚは互いに独立に水素原子、アルキル基、ハロゲン原子のいずれかを表す］
【０００８】
一般式（１）におけるＲ１、Ｒ２のアルキル基の例としては、炭素数１〜１８の直鎖または分岐のアルキル基、シクロヘキシル基、シクロヘキシルメチル基が挙げられ、同様に置換または非置換のアリール基の例としては、フェニル基、トリル基、クロロフェニル基、メトキシフェニル基が、アルコキシアルキル基の例としては、炭素数１〜１２のアルコキシアルキル基が、アラルキル基の例としては、ベンジル基等が挙げられる。本発明の化合物を低極性の溶剤に溶かして用いる場合にはＲ１、Ｒ２は炭素数の多いアルキル基であることが好ましく、高極性の溶剤に溶かして用いる場合にはＲ１、Ｒ２が炭素数の少ないアルキル基かアルコキシアルキル基であることが好ましい。また強い耐光性を要求される用途に用いる場合にはＲ１、Ｒ２が置換または非置換のフェニル基であることが好ましい。
【０００９】
一般式（１）におけるＲ３、Ｒ４のアルキル基の例としては炭素数１〜１０の直鎖または分岐のアルキル基が挙げられる。Ｒ３、Ｒ４が連結して環を形成した例としては、それらがシクロペンタン環、シクロヘキサン環等を形成したものが挙げられる。それらのシクロアルカン環がさらに単数あるいは複数のメチル基、エチル基、プロピル基、ブチル基、ペンチル基等で置換されたものも挙げられる。
【００１０】
一般式（１）におけるＷ、Ｘのアルキル基の例としては、炭素数１〜１０の直鎖または分岐のアルキル基が挙げられる。
一般式（１）におけるＡの例としては、下記一般式（２）〜（７）で表されるものが挙げられる。
【化１５】

［Ｘ１、Ｘ２は互いに独立にシアノ基、アルコキシカルボニル基、カルボキシル基、アシル基のいずれかを表す］
【００１１】
【化１６】

［Ｒ５は水素原子またはアルキル基を表す。Ｘ３、Ｘ４は互いに独立にシアノ基、アルコキシカルボニル基、カルボキシル基、アシル基のいずれかを表す］
【００１２】
【化１７】

［Ｘ５、Ｘ６，Ｘ７は互いに独立にシアノ基、アルコキシカルボニル基、カルボキシル基、アシル基のいずれかを表す］
【００１３】
【化１８】

［Ｒ６，Ｒ７は互いに独立に水素原子またはアルキル基を表す。Ｘ８、Ｘ９は互いに独立にシアノ基、アルコキシカルボニル基、カルボキシル基、アシル基のいずれかを表す］
【００１４】
【化１９】

［Ｒ８は水素原子、アルキル基、フッ化アルキル基、ハロゲン原子、シアノ基、アルコキシカルボニル基、カルボキシル基、アシル基のいずれかを表す］
【００１５】
【化２０】

［環Ａ１は、置換基を有する含窒素複素環を表す］
【００１６】
一般式（２）におけるＸ１、Ｘ２のアルコキシカルボニル基の例としては、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ブトキシカルボニル基、オクチルオキシカルボニル基、ドデシルオキシカルホニル基等が挙げられ、アシル基の例としては、アセチル基、プロピオニル基、ブチリル基、トリフルオロアセチル基、ベンゾイル基等が挙げられる。
【００１７】
一般式（３）におけるＲ５のアルキル基の例としては、炭素数１〜１８の直鎖または分岐または環状のアルキル基が挙げられる。Ｘ３、Ｘ４のアルコキシカルボニル基の例としては、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ブトキシカルボニル基、オクチルオキシカルボニル基、ドデシルオキシカルボニル基が挙げられ、アシル基の例としては、アセチル基、プロピオニル基、ブチリル基、トリフルオロアセチル基、ベンゾイル基等が挙げられる。
【００１８】
一般式（４）におけるＸ５、Ｘ６、Ｘ７のアルコキシカルボニル基の例としては、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ブトキシカルボニル基、オクチルオキシカルボニル基、ドデシルオキシカルボニル基が挙げられ、アシル基の例としては、アセチル基、プロピオニル基、ブチリル基、トリフルオロアセチル基、ベンゾイル基等が挙げられる。
【００１９】
一般式（５）におけるＲ６，Ｒ７のアルキル基の例としては、炭素数１〜１８の直鎖または分岐または環状のアルキル基が挙げられる。Ｘ８、Ｘ９のアルコキシカルボニル基の例としては、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ブトキシカルボニル基、オクチルオキシカルボニル基、ドデシルオキシカルボニル基が挙げられ、アシル基の例としては、アセチル基、プロピオニル基、ブチリル基、トリフルオロアセチル基、ベンゾイル基等が挙げられる。
【００２０】
一般式（６）におけるＲ８のアルキル基の例としては、炭素数１〜１８の直鎖または分岐のアルキル基、シクロプロピル基、シクロヘキシル基、シクロヘキシルメチル基等の環状のアルキル基が挙げられ、フッ化アルキル基の例としては、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、１，１−ジフルオロエチル基、２，２，２−トリフルオロエチル基等が挙げられる。アルコキシカルボニル基の例としては、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ブトキシカルボニル基、オクチルオキシカルボニル基、ドデシルオキシカルボニル基が挙げられ、アシル基の例としては、アセチル基、プロピオニル基、ブチリル基、トリフルオロアセチル基、ベンゾイル基等が挙げられる。
【００２１】
一般式（７）の原子団の例としては、具体的には下記一般式（８）〜（１３）で表されるものが挙げられる。
【００２２】
【化２１】

［Ｒ１１は水素原子、アルキル基、置換または非置換のアリール基、置換または非置換のヘテロアリール基のいずれかを表す。Ｒ１２はアルキル基、フッ化アルキル基、シアノ基、カルボキシル基、アルコキシカルボニル基、置換または非置換のアリール基、置換または非置換のヘテロアリール基のいずれかを表す］
【００２３】
【化２２】

［Ｒ１３は水素原子、アルキル基のいずれかを表す。Ｒ１４はアルキル基、フッ化アルキル基、置換または非置換のアリール基、置換または非置換のヘテロアリール基のいずれかを表す。Ｒ１５はシアノ基、カルボキシル基、アルコキシカルボニル基のいずれかを表す］
【００２４】
【化２３】

［Ｒ１６は水素原子、アルキル基、置換または非置換のアリール基、置換または非置換のヘテロアリール基、カルボキシメチル基、カルボキシエチル基、アルコキシカルボニルメチル基、アルコキシカルボニルエチル基のいずれかを表す。Ｙ１は酸素原子または硫黄原子を表す］
【００２５】
【化２４】

［Ｒ１７は水素原子、アルキル基、置換または非置換のアリール基、置換または非置換のヘテロアリール基、カルボキシメチル基、カルボキシエチル基、アルコキシカルボニルメチル基、アルコキシカルボニルエチル基のいずれかを表す。Ｘ１０、Ｘ１１は互いに独立にシアノ基、アルコキシカルボニル基、カルボキシル基、アシル基のいずれかを表す］
【００２６】
【化２５】

［Ｒ１８は水素原子、アルキル基、置換または非置換のアリール基、置換または非置換のヘテロアリール基、カルボキシメチル基、カルボキシエチル基、アルコキシカルボニルメチル基、アルコキシカルボニルエチル基のいずれかを表す。Ｒ１９はシアノ基、カルボキシル基、アルコキシカルボニル基のいずれかを表す。Ｒ２０はアルキル基を表す］
【００２７】
【化２６】

［Ｒ２１，Ｒ２２は互いに独立に水素原子、アルキル基、置換または非置換のアリール基、置換または非置換のヘテロアリール基、カルボキシメチル基、カルボキシエチル基、アルコキシカルボニルメチル基、アルコキシカルボニルエチル基のいずれかを表す。Ｙ２は酸素原子または硫黄原子を表す］
【００２８】
一般式（８）におけるＲ１１のアルキル基の例としてはメチル基、エチル基、プロピル基、ブチル基、オクチル基、ドデシル基等が挙げられ、置換または非置換のアリール基、置換または非置換のヘテロアリール基の例としてはフェニル基、アルキルフェニル基（例えばトリル基、エチルフェニル基等）、アルコキシフェニル基（例えばメトキシフェニル基、エトキシフェニル基等）、フッ化アルキルフェニル基（例えばトリフルオロメチルフェニル基、ペンタフルオロエチルフェニル基が挙げられる）、ハロゲン化フェニル基（例えばフッ化フェニル基、クロロフェニル基、ブロモフェニル基等）、ピリジル基、アルキルピリジル基（例えばメチルピリジル基、エチルピリジル基等）、チエニル基、アルキルチエニル基（例えばメチルチエニル基、エチルチエニル基等）、ピリミジル基、ピラジル基、トリアジル基、チアゾリル基、カルボキシフェニル基、アルコキシカルボニルフェニル基（例えばメトキシカルボニルフェニル基、エトキシカルボニルフェニル基等）、シアノフェニル基、スルホフェニル基等が挙げられる。Ｒ１２のうちアルキル基の例としてはメチル基、エチル基、プロピル基、ブチル基、オクチル基、ドデシル基等が挙げられ、フッ化アルキル基の例としては、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、１，１−ジフルオロエチル基、２，２，２−トリフルオロエチル基等が挙げられ、アルコキシカルボニル基の例としては、メトキシカルボニル基、エトキシカルボニル基、ブトキシカルボニル基、オクチルオキシカルボニル基等が挙げられ、置換または非置換のアリール基、置換または非置換のヘテロアリール基の例としてはフェニル基、アルキルフェニル（例えばトリル基、エチルフェニル基等）基、ハロゲン化フェニル（例えばフッ化フェニル基、クロロフェニル基、ブロモフェニル基等）基、フッ化アルキルフェニル（例えばトリフルオロメチルフェニル基、ペンタフルオロエチルフェニル基等）基、アルコキシフェニル基（例えばメトキシフェニル基、エトキシフェニル基等）、ピリジル基、アルキルピリジル基（例えばメチルピリジル基、エチルピリジル基等）、チエニル基、アルキルチエニル基（例えばメチルチエニル基、エチルチエニル基等）等が挙げられる。
【００２９】
一般式（９）におけるＲ１３のアルキル基の例としてはメチル基、エチル基、プロピル基、ブチル基、オクチル基、ドデシル基等が挙げられ、Ｒ１４のうちアルキル基の例としてはメチル基、エチル基、プロピル基、ブチル基、オクチル基、ドデシル基等が挙げられ、フッ化アルキル基の例としては、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、１，１−ジフルオロエチル基、２，２，２−トリフルオロエチル基等が挙げられ、置換または非置換のアリール基、置換または非置換のヘテロアリール基の例としはフェニル基、アルキルフェニル基（例えばトリル基、エチルフェニル基等）、アルコキシフェニル基（例えばメトキシフェニル基、エトキシフェニル基等）、フッ化アルキルフェニル基（例えばトリフルオロメチルフェニル基、ペンタフルオロエチルフェニル基等）、ハロゲン化フェニル基（例えばフッ化フェニル基、クロロフェニル基、ブロモフェニル基等）、シアノフェニル基、アミノフェニル基（例えばアミノフェニル基、Ｎ，Ｎ−ジメチルアミノフェニル基等）、チエニル基、アルキルチエニル基（例えばメチルチエニル基、エチルチエニル基等）、アルコキシカルボニルフェニル基（例えばメトキシカルボニルフェニル基、エトキシカルボニルフェニル基等）、ピリジル基、アルキルピリジル基（例えばメチルピリジル基、エチルピリジル基等）等が挙げられ、Ｒ１５のうちアルコキシカルボニル基の例としては、メトキシカルボニル基、エトキシカルボニル基、ブトキシカルボニル基、オクチルオキシカルボニル基等が挙げられる。
【００３０】
一般式（１０）におけるＲ１６のアルキル基の例としてはメチル基、エチル基、プロピル基、ブチル基、オクチル基、ドデシル基等が挙げられ、置換または非置換のアリール基、置換または非置換のヘテロアリール基の例としては、フェニル基、アルキルフェニル基（例えばトリル基、エチルフェニル基等）、アルコキシフェニル基（例えばメトキシフェニル基、エトキシフェニル基等）、フッ化アルキルフェニル基（例えばトリフルオロメチルフェニル基、ペンタフルオロエチルフェニル基等）、ハロゲン化フェニル基（例えばフッ化フェニル基、クロロフェニル基、ブロモフェニル基等）、シアノフェニル基、カルボキシフェニル基、アルコキシカルボニルフェニル基（例えばメトキシカルボニルフェニル基、エトキシカルボニルフェニル基等）、チエニル基、アルキルチエニル基（例えばメチルチエニル基、エチルチエニル基等）、ピリジル基、アルキルピリジル基（例えばメチルピリジル基、エチルピリジル基等）等が挙げられる。
【００３１】
一般式（１１）におけるＲ１７のアルキル基の例としてはメチル基、エチル基、プロピル基、ブチル基、オクチル基、ドデシル基等が挙げられ、置換または非置換のアリール基、置換または非置換のヘテロアリール基の例としては、フェニル基、アルキルフェニル基（例えばトリル基、エチルフェニル基等）、アルコキシフェニル基（例えばメトキシフェニル基、エトキシフェニル基等）、フッ化アルキルフェニル基（例えばトリフルオロメチルフェニル基、ペンタフルオロエチルフェニル基等）、ハロゲン化フェニル基（例えばフッ化フェニル基、クロロフェニル基、ブロモフェニル基等）、シアノフェニル基、カルボキシフェニル基、アルコキシカルボニルフェニル基（例えばメトキシカルボニルフェニル基、エトキシカルボニルフェニル基等）、チエニル基、アルキルチエニル基（例えばメチルチエニル基、エチルチエニル基等）、ピリジル基、アルキルピリジル基（例えばメチルピリジル基、エチルピリジル基等）等が挙げられ、Ｘ１０，Ｘ１１のアルコキシカルボニル基の例としては、メトキシカルボニル基、エトキシカルボニル基、ブトキシカルボニル基、オクチルオキシカルボニル基等が挙げられ、アシル基の例としては、アセチル基、プロピオニル基、ブチリル基、トリフルオロアセチル基、ベンゾイル基等が挙げられる。
【００３２】
一般式（１２）におけるＲ１８のアルキル基の例としてはメチル基、エチル基、プロピル基、ブチル基、オクチル基、ドデシル基等が挙げられ、置換または非置換のアリール基、置換または非置換のヘテロアリール基の例としてはフェニル基、アルキルフェニル基（例えばトリル基、エチルフェニル基等）、アルコキシフェニル基（例えばメトキシフェニル基、エトキシフェニル基等）、フッ化アルキルフェニル基（例えばトリフルオロメチルフェニル基、ペンタフルオロエチルフェニル基等）、ハロゲン化フェニル基（例えばフッ化フェニル基、クロロフェニル基、ブロモフェニル基等）、ピリジル基、アルキルピリジル基（例えばメチルピリジル基、エチルピリジル基等）、チエニル基、アルキルチエニル基（例えばメチルチエニル基、エチルチエニル基等）、ピリミジル基、ピラジル基、トリアジル基、チアゾリル基、カルボキシフェニル基、アルコキシカルボニルフェニル基（例えばメトキシカルボニルフェニル基、エトキシカルボニルフェニル基等）、シアノフェニル基、スルホフェニル基等が挙げられる。
【００３３】
一般式（１３）におけるＲ２１，Ｒ２２のアルキル基の例としてはメチル基、エチル基、プロピル基、ブチル基、オクチル基、ドデシル基等が挙げられ、置換または非置換のアリール基、置換または非置換のヘテロアリール基の例としてはフェニル基、アルキルフェニル基（例えばトリル基、エチルフェニル基等）、アルコキシフェニル基（例えばメトキシフェニル基、エトキシフェニル基等）、フッ化アルキルフェニル基（例えばトリフルオロメチルフェニル基、ペンタフルオロエチルフェニル基等）、ハロゲン化フェニル基（例えばフッ化フェニル基、クロロフェニル基、ブロモフェニル基等）、ピリジル基、アルキルピリジル基（例えばメチルピリジル基、エチルピリジル基等）、チエニル基、アルキルチエニル基（例えばメチルチエニル基、エチルチエニル基等）、ピリミジル基、ピラジル基、カルボキシフェニル基、アルコキシカルボニルフェニル基（例えばメトキシカルボニルフェニル基、エトキシカルボニルフェニル基等）、シアノフェニル基等が挙げられる。
【発明の効果】
【００３４】
本発明の化合物は分子構造中にペリミジン骨格を有し、可視光や近赤外光を効率よく吸収する色素であり、高い吸光係数、高い保存安定性、高い溶解性等、色素としての好ましい性質を有するため、産業上、利用価値の高いものである。
【発明の実施の形態】
【００３５】
本発明の化合物のうち、ポリメチン鎖の途中にチオフェン環を含まないものはたとえば下記に示すスキームに従って合成することができる。
【化２７】

上式におけるペリミジン環は、たとえば前記非特許文献３に記載の方法によって合成でき、ペリミジン化合物のホルミル体はたとえば前記非特許文献４に記載の方法によって合成することができる。このホルミル体を起点とするポリメチン鎖の延長は、たとえばウイティッヒ リアククション、ホーナー エモンズ リアクション（Ｗｉｔｔｉｇ Ｒｅａｃｔｉｏｎ、Ｈｏｒｎｅｒ−Ｅｍｍｏｎｓ Ｒｅａｃｔｉｏｎ）を応用することによって行うことができる。ここでＲ５１はアルキル基、フェニル基等を表し、Ｒ５２、Ｒ５３はアルキル基であり、連結して環を形成していてもよい。この操作を繰り返すことによりポリメチン鎖をさらに延長していくことが可能である。そうして得られたホルミル体を活性メチレンまたは活性メチルを有する化合物と反応させることにより、本発明のペリミジン化合物を容易に得ることができる。
【００３６】
上記ホルミル化合物と活性メチレンまたは活性メチル化合物との反応は、一般にクネベナゲル（Ｋｎｏｅｖｅｎａｇｅｌ）反応として知られている反応の条件に準じて行えばよく、たとえばアルコール、アセトニトリル、ベンゼン、トルエン等を反応溶媒として用いることができ、このとき反応促進剤としてピペリジン、ピロリジン、水酸化ナトリウム、酢酸アンモニウム、硫酸、酢酸等を用いることもできる。
【００３７】
本発明の化合物のうち、ポリメチン鎖の途中にチオフェン環を含むものはたとえば次のような方法によって合成することができる。そうして得られたホルミル体を活性メチレンまたは活性メチルを有する化合物と反応させることにより、本発明のペリミジン化合物を容易に得ることができる。ここで下記式におけるＲ５４はアルキル基、フェニル基等を表す。
【００３８】
【化２８】

上記の二つの合成法により合成できる一般式（１）の化合物の例として次のようなものが挙げられる。
【００３９】
【表１】

【表２】

【表３】

【表４】

【表５】

【表６】

【表７】

【実施例】
【００４０】
以下、本発明を実施例によりさらに具体的に説明する。
実施例１
（１）１，８−ジアミノナフタレン１６．３ｇ、アセトン１８ｇをベンゼン２８０ｍｌに溶解させ、ｐ−トルエンスルホン酸１水和物４ｇを加え室温で１８時間攪拌した。反応液を重曹水で洗浄、乾燥、濃縮し下記構造式（１４）の２，２−ジメチル−２，３−ジヒドロ−１Ｈ−ペリミジン１５．７ｇ得た。
【００４１】
【化２９】

（２）２，２−ジメチル−２，３−ジヒドロ−１Ｈ−ペリミジン１．８ｇをＤＭＦ２５ｍｌに溶解させ炭酸カリウム４．１ｇ、ヨウ化エチル６．２ｇを加え、６０℃で１５時間攪拌した。反応液を水に排出し、酢酸エチルで抽出。乾燥後、濃縮しシリカゲルカラムクロマトグラフィーにより精製し下記構造式（１５）の１，３−ジエチル−２，２−ジメチル−２，３−ジヒドロ−１Ｈ−ペリミジン２．１ｇを得た。
【００４２】
【化３０】

（３）１，３−ジエチル−２，２−ジメチル−２，３−ジヒドロ−１Ｈ−ペリミジン２ｇをＤＭＦ２５ｍｌに溶解させ、０℃でオキシ塩化リン１．３ｇを滴下した。反応終了後、水に排出し中和し酢酸エチルで抽出した。抽出液を水洗、乾燥、濃縮したのち、シリカゲルカラムクロマトグラフィーにより精製し下記構造式（１６）の１，３−ジエチル−２，２−ジメチル−２，３−ジヒドロ−６−ホルミル−１Ｈ−ペリミジン１．４５ｇを得た。
【００４３】
【化３１】

（４）１，３−ジエチル−２，２−ジメチル−２，３−ジヒドロ−６−ホルミル−１Ｈ−ペリミジン０．５ｇとマロノニトリル０．１３ｇをエタノール１０ｍｌに溶解させ、ピペリジンを３滴加え室温で３時間攪拌した。反応液を濾過し得られた結晶をメタノールで洗浄して黒紫色の例示化合物Ａ−１を０．４２ｇ得た。
【００４４】
λｍａｘ＝５１５ｎｍ（ε＝２９０００）（メタノール中）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、３００ＭＨｚ）：δ１．２３（ｔ、３Ｈ、Ｊ＝７．１Ｈｚ）、１．３６（ｔ、３Ｈ、Ｊ＝７．１Ｈｚ）、１．６０（ｓ、６Ｈ）、３．５３（ｑ、２Ｈ、Ｊ＝７．１Ｈｚ）、３．６６（ｑ、２Ｈ、Ｊ＝７．１Ｈｚ）、６．５３（ｄ、１Ｈ、Ｊ＝９．０Ｈｚ）、６．６８（ｄ、１Ｈ、Ｊ＝７．９Ｈｚ）、７．３０（ｄ、１Ｈ、Ｊ＝８．３Ｈｚ）、７．４６（ｄｄ、１Ｈ、Ｊ＝７．９、８．３Ｈｚ）、８．２５（ｓ、１Ｈ）、８．５６（ｄ、１Ｈ、Ｊ＝９．０Ｈｚ）
^１３Ｃ−ＮＭＲ（ＣＤＣｌ_３，７５ＭＨｚ）：１３．５，１３．９，２５．０，４０．７、４１．６，７０．３，７３．５，１０３．５，１０７．７，１１１．１，１１４．１，１１４．９，１１６．０，１１７．１，１３０．５，１３２．６，１３４．３，１４２．６，１４８．６，１５３．２
【００４５】
実施例２
実施例１（３）で得られた１，３−ジエチル−２，２−ジメチル−２，３−ジヒドロ−６−ホルミル−１Ｈ−ペリミジン１．０ｇとシアノ酢酸０．４ｇをエタノール１２ｍｌに溶解させ、触媒量のピペリジンを加え６０℃で１５時間攪拌した。希塩酸に排出し抽出、乾燥、濃縮しクロロホルムで精製することにより例示化合物Ａ−４を０．５１ｇ得た。
【００４６】
λｍａｘ＝４９５ｎｍ（ε＝１８０００）（メタノール中）
ＬＣ／ＭＳ：３５０（Ｍ＋Ｈ^＋）
^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６、３００ＭＨｚ）：δ１．１７（ｔ、３Ｈ、Ｊ＝７．０Ｈｚ）、１．２６（ｔ、３Ｈ、Ｊ＝７．０Ｈｚ）、１．５４（ｓ、６Ｈ）、３．５１（ｑ、２Ｈ、Ｊ＝７．０Ｈｚ）、３．６６（ｑ、２Ｈ、Ｊ＝７．０Ｈｚ）、６．６０−６．７５（ｍ、２Ｈ）、７．３１（ｄ、１Ｈ、Ｊ＝８．１Ｈｚ）、７．４６（ｄｄ、１Ｈ、Ｊ＝８．１、８．１Ｈｚ）、８．２７（ｓ、１Ｈ）、８．４８（ｄ、１Ｈ、Ｊ＝８．８Ｈｚ）、８．７６（ｓ、１Ｈ）
【００４７】
実施例３
実施例１（３）で得られた１，３−ジエチル−２，２−ジメチル−２，３−ジヒドロ−６−ホルミル−１Ｈ−ペリミジン０．７６ｇと３−シアノ−１−フェニル−５−ピラゾロン０．５ｇをエタノール５０ｍｌに溶解させ５０℃で３時間攪拌した。反応液を濾過しメタノールで洗浄して例示化合物Ｂ−１を０．７ｇ得た。
λｍａｘ＝６０１ｎｍ（ε＝４６０００）（メタノール中）
ＬＣ／ＭＳ：４５０（Ｍ＋Ｈ^＋）
【００４８】
実施例４
実施例３で用いた３−シアノ−１−フェニル−５−ピラゾロンの代わりに３−カルボキシ−１−フェニル−５−ピラゾロンを用いる以外は実施例３と同様にして反応させ、反応液を濾過して得られた濾液をシリカゲルカラムクロマトグラフィーにより精製し例示化合物Ｂ−２を得た。
【００４９】
λｍａｘ＝５８７ｎｍ（ε＝３５０００）（メタノール中）
ＬＣ／ＭＳ：４６９（Ｍ＋Ｈ^＋）
^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６、３００ＭＨｚ）：δ１．１８（ｔ、３Ｈ、Ｊ＝７．０Ｈｚ）、１．３２（ｔ、３Ｈ、Ｊ＝７．０Ｈｚ）、１．６０（ｓ、６Ｈ）、３．５６（ｑ、２Ｈ、Ｊ＝７．０Ｈｚ）、３．７８（ｑ、２Ｈ、Ｊ＝７．０Ｈｚ）、６．７３−６．８２（ｍ、２Ｈ）、７．２１−７．２９（ｍ、１Ｈ）、７．４５−７．６２（ｍ、５Ｈ）、７．９７−８．０６（ｍ、２Ｈ）、９．３５（ｓ、１Ｈ）、９．９１（ｂｒ、１Ｈ）
^１３Ｃ−ＮＭＲ（ＤＭＳＯ−ｄ_６、７５ＭＨｚ）：８．６，９．２，１９．５，３５．８，３６．０，６９．３，９９．４，１０２．７，１０６．４，１０８．３、１０８．６，１１２．３，１１４．８，１２０．４，１２４．０，１２６．６，１３１．２，１３４．１，１３４．６．１３６．９，１３７．９，１４０．３，１４５．２，１５７．７，１５８．５
【００５０】
実施例５
実施例３で用いた３−シアノ−１−フェニル−５−ピラゾロンの代わりにロダニン−３−酢酸を用いる以外は実施例３と同様にして例示化合物Ｃ−１を得た。λｍａｘ＝５３９ｎｍ（ε＝３１０００）（メタノール中）
ＬＣ／ＭＳ：４５６（Ｍ＋Ｈ^＋）
【００５１】
実施例６
実施例１（３）で得られた１，３−ジエチル−２，２−ジメチル−２，３−ジヒドロ−６−ホルミル−１Ｈ−ペリミジン０．３ｇをエタノール６ｍｌに溶解させ、この溶液に３−エチルロダニン０．１９ｇを加え、さらにピペリジン０．０９ｇを加え室温で４時間攪拌した。反応液を濃縮しシリカゲルカラムクロマトグラフィーにて精製し例示化合物Ｃ−２を得た。
λｍａｘ＝５３７ｎｍ（ε＝２７０００）（メタノール中）
ＬＣ／ＭＳ：４２６（Ｍ＋Ｈ^＋）
【００５２】
実施例７
実施例１（３）で得られた１，３−ジエチル−２，２−ジメチル−２，３−ジヒドロ−６−ホルミル−１Ｈ−ペリミジン０．２８ｇとバルビツール酸０．１５ｇをエタノール７ｍｌに溶解させ室温で３時間攪拌した。反応液を濾過しメタノールで洗浄して例示化合物Ｅ−１を０．２７ｇ得た。
【００５３】
λｍａｘ＝５６０ｎｍ（ε＝３５０００）（メタノール中）
ＬＣ／ＭＳ：３９３（Ｍ＋Ｈ^＋）
^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６、３００ＭＨｚ）：δ１．１７（ｔ、３Ｈ、Ｊ＝７．０Ｈｚ）、１．２８（ｔ、３Ｈ、Ｊ＝７．０Ｈｚ）、１．５６（ｓ、６Ｈ）、３．５３（ｑ、２Ｈ、Ｊ＝７．０Ｈｚ）、３．７０（ｑ、２Ｈ、Ｊ＝７．０Ｈｚ）、６．６１（ｄ、２Ｈ、Ｊ＝９．２Ｈｚ）、６．７１（ｄ、１Ｈ、Ｊ＝８．０Ｈｚ）、７．３２（ｄ、１Ｈ、Ｊ＝８．０Ｈｚ）、７．４９（ｄｄ、１Ｈ、Ｊ＝８．０、８．０Ｈｚ）、８．９２（ｓ、１Ｈ）、９．０３（ｄ、１Ｈ、Ｊ＝９．２Ｈｚ）、１０．７１（ｂｒ、１Ｈ）、１０．８８（ｂｒ、１Ｈ）
^１３Ｃ−ＮＭＲ（ＤＭＳＯ−ｄ_６、７５ＭＨｚ）：８．６，９．１，１９．５，３５．６，３６．０，６８．９，９８．０，１０１．９，１０４．１，１０６．８，１０８．２，１１０．９，１２５．９，１３１．２，１３４．０，１３７．８，１４３．８，１４５．６，１５７．７，１６０．３
【００５４】
実施例８
実施例１（３）で得られた１，３−ジエチル−２，２−ジメチル−２，３−ジヒドロ−６−ホルミル−１Ｈ−ペリミジン０．２８ｇと３−エトキシカルボニル−２−（４−シアノフェニル）−５−ピロリノン０．２９ｇをエタノール１５ｍｌに溶解させ６２％硫酸０．１ｍｌを加えた。４５℃で１時間攪拌した。反応液を水に排出し中和後、濾過しメタノールで洗浄して例示化合物Ｆ−３を０．４３ｇ得た。
λｍａｘ＝５５５ｎｍ（ε＝３３０００）（メタノール中）
【００５５】
実施例９
実施例３で用いた３−シアノ−１−フェニル−５−ピラゾロンの代わりに１，３−インダンジオンを用いる以外は実施例３と同様にして合成し、シリカゲルカラムクロマトグラフィーにて精製し例示化合物Ｇ−１を得た。
λｍａｘ＝５７６ｎｍ（ε＝４８０００）（メタノール中）
【００５６】
ＬＣ／ＭＳ：４１１（Ｍ＋Ｈ^＋）
^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６、３００ＭＨｚ）：δ１．１８（ｔ、３Ｈ、Ｊ＝７．０Ｈｚ）、１．３２（ｔ、３Ｈ、Ｊ＝７．０Ｈｚ）、１．５９（ｓ、６Ｈ）、３．５５（ｑ、２Ｈ、Ｊ＝７．０Ｈｚ）、３．７６（ｑ、２Ｈ、Ｊ＝７．０Ｈｚ）、６．７４（ｄ、２Ｈ、Ｊ＝９．０Ｈｚ）、７．４９−７．６３（ｍ、２Ｈ）、７．７４−７．８８（ｍ、４Ｈ）、８．４６（ｓ、１Ｈ）、９．５９（ｄ、１Ｈ、Ｊ＝９．０Ｈｚ）
^１３Ｃ−ＮＭＲ（ＤＭＳＯ−ｄ_６、７５ＭＨｚ）：８．６，９．１，１９．５，３５．７，３６．０，６９．０，９９．０，１０２．２，１０６．３，１０８．４，１１１．４，１１５．４，１１７．０，１１７．１，１２６．２，１２９．５，１２９．８．１３１．０，１３４．１，１３４．２，１３５．９，１３６．８，１３７．８，１４４．３，１８４．０，１８６．１
【００５７】
実施例１０
【化３２】

実施例１（３）で得られた１，３−ジエチル−２，２−ジメチル−２，３−ジヒドロ−６−ホルミル−１Ｈ−ペリミジン０．２ｇと上記構造式（１７）のピラン化合物（たとえばＪ．Ｏｒｇ．Ｃｈｅｍ．，３９，７，９８９，（１９７４）に記載の方法に準じて合成できる）０．１５ｇをエタノール３ｍｌに溶解させピペリジン０．０７ｇを加え、７０℃で６時間攪拌した。反応液を濃縮後、シリカゲルカラムクロマトグラフィーにて精製しメタノールで洗浄して例示化合物Ｈ−１を０．０６ｇ得た。
【００５８】
λｍａｘ＝５３７ｎｍ（ε＝３９０００）（メタノール中）
ＬＣ／ＭＳ：４３７（Ｍ＋Ｈ^＋）
蛍光極大波長λｅｍ＝７２３ｎｍ（励起波長λｅｘ＝６００ｎｍ、メタノール中）
λｅｍ＝７０７ｎｍ（λｅｘ＝５７５ｎｍ、アセトン中）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、３００ＭＨｚ）：δ１．２４（ｔ、３Ｈ、Ｊ＝７．１Ｈｚ）、１．３３（ｔ、３Ｈ、Ｊ＝７．１Ｈｚ）、１．５６（ｓ、６Ｈ）、２．４０（ｓ、３Ｈ）、３．５１（ｑ、２Ｈ、Ｊ＝７．１Ｈｚ）、３．６０（ｑ、２Ｈ、Ｊ＝７．１Ｈｚ）、６．４５−６．７０（ｍ、５Ｈ）、７．３８−７．５３（ｍ、２Ｈ）、７．７３（ｄ、１Ｈ、Ｊ＝８．４Ｈｚ）、８．１５（ｄ、１Ｈ、Ｊ＝１５．５Ｈｚ）
^１３Ｃ−ＮＭＲ（ＣＤＣｌ_３，７５ＭＨｚ）：１３．７，１４．０，２０．０，２４．９，４０．５，４１．６，５６．９，７２．８，１０３．７，１０５．４，１０６．１，１０６．７，１１１．９，１１３．４，１１５．１，１１５．８，１１５．９，１１８．５，１２７．５，１２８．５，１３３．１，１３５．６，１４２．５，１４４．７，１５６．５，１６０．８，１６１．６
【００５９】
実施例１１
【化３３】

実施例１０で用いたピラン化合物の代わりに上記構造式（１８）のピラン化合物を用いること以外は実施例１０と同様にして合成し、例示化合物Ｈ−２を得た。
λｍａｘ＝５２３ｎｍ（メタノール中）
λｅｍ＝７１４ｎｍ（λｅｘ＝５８６ｎｍ、メタノール中）
λｅｍ＝６９７ｎｍ（λｅｘ＝５６５ｎｍ、アセトン中）
【００６０】
実施例１２
【化３４】

実施例１（３）で得られた１，３−ジエチル−２，２−ジメチル−２，３−ジヒドロ−６−ホルミル−１Ｈ−ペリミジン０．２８ｇと上記構造式（１９）の２，３−ジシアノ−５−エトキシカルボニル−６−メチルピラジン（たとえばＤｙｅｓ ａｎｄ Ｐｉｇｍｅｎｔｓ，４０，１１，（１９９８）に記載の方法で合成できる）０．２６ｇをトルエン１０ｍｌに溶解させ、この溶液に酢酸２滴、ピペリジン１滴を加え、１００℃で１８時間攪拌した。反応液を濃縮後、シリカゲルカラムクロマトグラフィーにて精製しメタノールで洗浄して例示化合物Ｉ−１を得た。
【００６１】
λｍａｘ＝５９９ｎｍ（ε＝３８０００）（メタノール中）
ＬＣ／ＭＳ：４８１（Ｍ＋Ｈ^＋）
^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６、３００ＭＨｚ）：δ１．１８（ｔ、３Ｈ、Ｊ＝７．０Ｈｚ）、１．２６（ｔ、３Ｈ、Ｊ＝７．０Ｈｚ）、１．３９（ｔ、３Ｈ、Ｊ＝７．１Ｈｚ）、１．５３（ｓ、６Ｈ）、３．５１（ｑ、２Ｈ、Ｊ＝７．０Ｈｚ）、３．６３（ｑ、２Ｈ、Ｊ＝７．０Ｈｚ）、４．４９（ｑ、２Ｈ、Ｊ＝７．１Ｈｚ）、６．６５（ｄ、１Ｈ、Ｊ＝８．５Ｈｚ）、６．６６（ｄｄ、１Ｈ、Ｊ＝０．９、７．５Ｈｚ）、７．４６（ｄｄ、１Ｈ、Ｊ＝７．５、８．５Ｈｚ）、７．４６（ｄｄ、１Ｈ、Ｊ＝０．９、８．５Ｈｚ）、７．５６（ｄ、１Ｈ、Ｊ＝１５．０Ｈｚ）、７．９５（ｄ、１Ｈ、Ｊ＝８．５Ｈｚ）、８．７５（ｄ、１Ｈ、Ｊ＝１５．０Ｈｚ）
【００６２】
実施例１３
（１）イソホロン７．２５ｇをマロノニトリル１０ｇを混合し、ピペジリン０．３ｍｌを加え８０℃で１４時間攪拌した。放冷後、シリカゲルカラムクロマトグラフィーにて精製して下記構造式（２０）に示したジシアノ化合物を６．５ｇ得た。
【００６３】
【化３５】

（２）実施例１（３）で得られた１，３−ジエチル−２，２−ジメチル−２，３−ジヒドロ−６−ホルミル−１Ｈ−ペリミジン０．２８ｇと上記の（１）で得られたジシアノ化合物０．２３ｇをエタノール５ｍｌに溶解させ、ピペリジン０．１ｇを加え、７５℃で１５時間攪拌した。反応液を放冷し濾過により得られた結晶をシリカゲルカラムクロマトグラフィーにて精製しメタノールで洗浄して例示化合物Ｊ−１を０．１５ｇ得た。
【００６４】
λｍａｘ＝５７８ｎｍ（ε＝３００００）（メタノール中）
ＬＣ／ＭＳ：４５１（Ｍ＋Ｈ^＋）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、３００ＭＨｚ）：δ１．０９（ｓ、６Ｈ）、１．２４（ｔ、３Ｈ、Ｊ＝７．１Ｈｚ）、１．３３（ｔ、３Ｈ、Ｊ＝７．１Ｈｚ）、１．５５（ｓ、６Ｈ）、２．５４（ｓ、２Ｈ）、２．５６（ｓ、２Ｈ）、３．５１（ｑ、２Ｈ、Ｊ＝７．１Ｈｚ）、３．５９（ｑ、２Ｈ、Ｊ＝７．１Ｈｚ）、６．５４（ｄ、１Ｈ、Ｊ＝８．６Ｈｚ）、６．６４（ｄｄ、１Ｈ、Ｊ＝０．９，７．５Ｈｚ）、６．７６（ｓ、１Ｈ）、６．９５（ｄ、１Ｈ、Ｊ＝１５．８Ｈｚ）、７．４１（ｄｄ、１Ｈ、Ｊ＝７．５，８．５Ｈｚ）、７．４８（ｄｄ、１Ｈ、Ｊ＝０．９，８．５Ｈｚ）、７．７７（ｄ、１Ｈ、Ｊ＝８．６Ｈｚ）、７．８１（ｄ、１Ｈ、Ｊ＝１５．８Ｈｚ）
^１３Ｃ−ＮＭＲ（ＣＤＣｌ_３，７５ＭＨｚ）：１３．７，１４．０，２４．９，２８．１，３２．０，３９．４，４０．５，４１．７，４３．０，７２．８，７５．０，１０４．０，１０６．７，１１１．９，１１３．７，１１４．５，１１５．２，１１９．８，１２１．３，１２５．６，１２７．３，１２８．３，１３３．０，１３４．９，１４２．５，１４４．３，１５５．６，１６９．１
【００６５】
実施例１４
（１）１，８−ジアミノナフタレン１０ｇ、シクロヘキサノン６．２ｇをトルエン１４０ｍｌに溶解させ、水を除去しながら４時間加熱還流した。反応液を放冷したのち、濾過した濾液を濃縮した。得られた結晶をヘキサン／酢酸エチル系にて再結晶して下記構造式（２１）のベージュ色の結晶を９．２ｇ得た。
【００６６】
【化３６】

（２）上記で得られた式（２１）で表されるペリミジン化合物８．７ｇをＤＭＦ１００ｍｌに溶解させ炭酸カリウム１９．１ｇ、ヨウ化エチル２４ｇを加え、６０℃で２１時間攪拌した。反応液を水に排出し、酢酸エチルで抽出。水洗、乾燥後、濃縮しシリカゲルカラムクロマトグラフィーにより精製し、下記構造式（２２）の薄い緑色のタール状物質を５．４ｇ得た。
【００６７】
【化３７】

（３）（２）で得られた式（２２）で表されるペリミジン化合物５．４ｇをＤＭＦ５５ｍｌに溶解させ、０℃でオキシ塩化リン２．９ｇを滴下し、同温度で２時間攪拌した。反応終了後、水に排出し中和後酢酸エチルで抽出した。抽出液を水洗、乾燥、濃縮したのち、シリカゲルカラムクロマトグラフィーにより精製し、下記構造式（２３）の黄色タール状のアルデヒド体を５．２ｇを得た。
【００６８】
【化３８】

（４）（３）で得られた式（２３）で表されるアルデヒド体０．１７ｇとマロノニトリル０．０４ｇをエタノール４ｍｌに溶解させ、触媒量のピペリジンを加え３時間攪拌した。反応液を濃縮しシリカゲルカラムクロマトグラフィーにより精製して例示化合物Ａ−５を得た。
λｍａｘ＝５０６ｎｍ（ε＝４４０００）（メタノール中）
ＬＣ／ＭＳ：３７１（Ｍ＋Ｈ^＋）
【００６９】
実施例１５
実施例１４（３）で得られたアルデヒド体０．４５ｇと３−カルボキシ−１−フェニル−５−ピラゾロン０．３３ｇをエタノール７ｍｌに溶解させ、６０℃で３時間攪拌した。反応液を濾過し、濾液を濃縮したのちシリカゲルカラムクロマトグラフィーにて精製しヘキサンで洗浄して例示化合物Ｂ−９を０．１２ｇ得た。
λｍａｘ＝５７４ｎｍ（ε＝５６０００）（メタノール中）
ＬＣ／ＭＳ：５０９（Ｍ＋Ｈ^＋）
【００７０】
実施例１６
実施例１４（３）で得られたアルデヒド体０．３６ｇと３−シアノ−１−フェニル−５−ピラゾロン０．２０ｇをエタノール１０ｍｌに溶解させ、６０℃で２時間攪拌した。反応液を濾過し、得られた結晶をメタノールで洗浄して例示化合物Ｂ−１０を０．２８ｇ得た。
λｍａｘ＝５８５ｎｍ（ε＝７６０００）（メタノール中）
ＬＣ／ＭＳ：４９０（Ｍ＋Ｈ^＋）
【００７１】
実施例１７
【化３９】

（１）実施例１（３）で得られたアルデヒド体１ｇをＤＭＦ３０ｍｌに溶解させ、上記構造式（２４）で表されるリン化合物３．８ｇを加えた。この溶液にナトリウムメトキシドの２８％メタノール溶液１．１ｇを室温で滴下。滴下終了後、室温で２時間攪拌し水に排出した。酢酸エチルで抽出したのち、水洗、乾燥、濃縮した。得られたオイル状化合物に１１％塩酸５ｍｌを加え室温で３０分攪拌した。反応液を水に排出し酢酸エチルで抽出、水洗、乾燥、濃縮して得られたオイル状化合物をシリカゲルカラムクロマトグラフィーにて精製し下記構造式（２５）のアルデヒド体１ｇを得た。
【００７２】
【化４０】

（２）（１）で得られた式（２５）で表されるアルデヒド体０．９ｇとマロノニトリル０．２５ｇをエタノール１０ｍｌに溶解させた。この溶液にピペリジン１滴をエタノール０．５ｍｌに溶解させた溶液を５滴加え、室温で１時間攪拌した。反応液を濾過し得られた結晶をメタノールで洗浄し例示化合物Ａ−８を０．８６得た。
【００７３】
λｍａｘ＝５７６ｎｍ（ε＝４８０００）（メタノール中）
ＬＣ／ＭＳ：３５７（Ｍ＋Ｈ^＋）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、３００ＭＨｚ）：δ１．２３（ｔ、３Ｈ、Ｊ＝７．１Ｈｚ）、１．３５（ｔ、３Ｈ、Ｊ＝７．１Ｈｚ）、１．５８（ｓ、６Ｈ）、３．５２（ｑ、２Ｈ、Ｊ＝７．１Ｈｚ）、３．６４（ｑ、２Ｈ、Ｊ＝７．１Ｈｚ）、６．５３（ｄ、１Ｈ、Ｊ＝８．８Ｈｚ）、６．６６（ｄｄ、１Ｈ、Ｊ＝３．６，５．３Ｈｚ）、７．１６（ｄｄ、１Ｈ、Ｊ＝１２．０，１４．５Ｈｚ）、７．４４（ｄ、１Ｈ、Ｊ＝３．６Ｈｚ）、７．４５（ｄ、１Ｈ、Ｊ＝５．３Ｈｚ）、７．５５（ｄ、１Ｈ、Ｊ＝１２．０Ｈｚ）、７．９２（ｄ、１Ｈ、Ｊ＝１４．５Ｈｚ）、７．９４（ｄ、１Ｈ、Ｊ＝８．８Ｈｚ）？
^１３Ｃ−ＮＭＲ（ＣＤＣｌ_３，７５ＭＨｚ）：１３．６，１４．０，２５．０，４０．６、４１．６，７３．２，７３．８，１０４．０，１０７．３，１１１．５，１１３．８，１１４．７，１１５．７，１１７．５，１１７．７，１２９．６，１３０．６，１３３．９，１４２．６，１４６．９，１４７．６，１６０．３
【００７４】
実施例１８
実施例１７（１）で得られたアルデヒド体０．３ｇをエタノール５ｍｌに溶解させ、この溶液に３−カルボキシ−１−フェニル−５−ピラゾロン０．２４ｇを加え４５℃で２時間攪拌した。放冷後、析出した結晶を濾取しエタノールで洗浄することにより例示化合物Ｂ−１３を０．２９ｇ得た。
λｍａｘ＝６８２ｎｍ（ε＝６５０００）（メタノール中）
ＬＣ／ＭＳ：４９５（Ｍ＋Ｈ^＋）
【００７５】
実施例１９
【化４１】

（１）実施例１（３）で得られたアルデヒド体３．５ｇをＴＨＦ３０ｍｌに溶解させ、上記構造式（２６）で表されるリン化合物４．４ｇを加えた。この溶液にカリウムｔ−ブトキシド１．７ｇのＴＨＦ懸濁液を５℃で１時間かけて滴下し、同温度で１時間攪拌した。反応終了後、水に排出し酢酸エチルで抽出した。有機層を水洗、乾燥、濃縮したのち、シリカゲルカラムクロマトグラフィーにて精製し下記構造式（２７）の茶色オイル４．３ｇを得た。
【００７６】
【化４２】

（２）（１）で得られた式（２７）で表される化合物４ｇをＴＨＦ６０ｍｌに溶解させ窒素置換。０℃まで冷却したのち、１．６Ｍのｎ−ブチルリチウム８．３ｍｌを１時間かけて滴下し同温度で１時間攪拌した。０℃においてＤＭＦ２．４ｇを加え２時間攪拌した。反応液を水に排出し酢酸エチルで抽出し、有機層を水洗、乾燥、濃縮したのち、シリカゲルカラムクロマトグラフィーにて精製し下記構造式（２８）で表されるアルデヒド体０．５ｇを得た
【００７７】
【化４３】

（３）（２）で得られたアルデヒド体０．６ｇをエタノール１０ｍｌに溶解させマロノニトリル０．１２ｇを加えた。この溶液にピペリジン１滴を加え７５℃で２時間攪拌した。反応液を濃縮しシリカゲルカラムクロマトグラフィーにて精製したのち、ヘキサンで洗浄し例示化合物Ａ−１０を０．１７ｇ得た。
【００７８】
λｍａｘ＝５８８ｎｍ（ε＝５３０００）（メタノール中）
ＬＣ／ＭＳ：４３９（Ｍ＋Ｈ^＋）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、３００ＭＨｚ）：δ１．２３（ｔ、３Ｈ、Ｊ＝７．１Ｈｚ）、１．３１（ｔ、３Ｈ、Ｊ＝７．１Ｈｚ）、１．５５（ｓ、６Ｈ）、３．５０（ｑ、２Ｈ、Ｊ＝７．１Ｈｚ）、３．５７（ｑ、２Ｈ、Ｊ＝７．１Ｈ）、６．５２（ｄ、１Ｈ、Ｊ＝８．５Ｈｚ）、６．６４（ｄ、１Ｈ、Ｊ＝７．３Ｈｚ）、７．１０（ｄ、１Ｈ、Ｊ＝４．０Ｈｚ）、７．１３（ｄ、１Ｈ、Ｊ＝１５．８Ｈｚ）、７．４２（ｄｄ、１Ｈ、Ｊ＝７．３，８．２Ｈｚ）、７．５１（ｄ、１Ｈ、Ｊ＝８．２Ｈｚ）、７．５６（ｄ、１Ｈ、Ｊ＝４．０Ｈｚ）、７．６６（ｓ、１Ｈ）、７．７１（ｄ、１Ｈ、Ｊ＝８．５Ｈｚ），７．９２（ｄ、１Ｈ、Ｊ＝１５．８Ｈｚ）
^１３Ｃ−ＮＭＲ（ＣＤＣｌ_３，７５ＭＨｚ）：１３．８、１４．０，２４．９，４０．６，４１．７，７２．７，７３．５，１０３．９，１０６．８，１１２．４，１１４．１，１１５．０，１１５．３，１１６．８，１２０．０，１２５．５，１２６．７，１２８．２，１３２．３，１３２．８，１３３．０，１４０．５，１４２．４，１４３．８，１４９．７，１５７．７
【００７９】
実施例２０
実施例１９（２）で得られたアルデヒド体０．３５ｇをアセトニトリル８ｍｌに溶解させ、この溶液にシアノ酢酸エチル０．１２ｇ、さらにピペリジン０．０９ｇを加え室温で１．５時間攪拌した。反応液を濃縮しシリカゲルカラムクロマトグラフィーにて精製して例示化合物Ａ−１１を０．４ｇ得た。
λｍａｘ＝５５７ｎｍ（メタノール中）
ＬＣ／ＭＳ：４８６（Ｍ＋Ｈ^＋）
【００８０】
実施例２１
実施例２０で得られたエステル体０．３ｇをエタノール２０ｍｌに加え、５０℃まで昇温し、１０％水酸化ナトリウム水溶液１ｇを加えた。同温度で１時間攪拌した。放冷後水に排出し、塩酸でｐＨ３に調製した。析出した結晶を濾過により得、シリカゲルカラムクロマトグラフィーにて精製して例示化合物Ａ−１２を０．１ｇ得た。
λｍａｘ＝５４１ｎｍ（ε＝２４０００）（メタノール中）
ＬＣ／ＭＳ：４５８（Ｍ＋Ｈ^＋）
【００８１】
実施例２２〜２３
実施例１（３）で得られたアルデヒド体と対応するシアノ酢酸エステルを用いて実施例２０と同様に反応させることにより例示化合物Ａ−２、Ａ−３を得た。
【００８２】
実施例２４〜３５
実施例１（３）で得られたアルデヒド体と対応する活性メチレン化合物を用いて実施例３と同様に反応させることにより例示化合物Ｂ−３〜Ｂ−８、Ｃ−３〜Ｃ−６、Ｄ−１，Ｄ−２を得た。
Ｃ−３〜Ｃ−６を合成する際に用いるロダニン誘導体については、たとえば特開平０８−２６９３４５に記載の方法をもちいて合成することができる。
【００８３】
実施例３６〜３７
実施例１（３）で得られたアルデヒド体と対応するバルビツール酸化合物を用いて実施例７と同様に反応させ例示化合物Ｅ−２、Ｅ−３を得た。
【００８４】
実施例３８〜４０
実施例１（３）で得られたアルデヒド体と対応するピロリノン化合物を用いて実施例８と同様に反応させることにより例示化合物Ｆ−１、Ｆ−２、Ｆ−４を得た。
【００８５】
実施例４１
実施例１７（１）で得られたアルデヒド体と３−エチルロダニンをエタノール中で加熱することにより例示化合物Ｃ−８を得た。
【００８６】
実施例４２〜４３
実施例１７（１）で得られたアルデヒド体と対応する活性メチレン化合物を実施例７と同様に室温で攪拌することにより例示化合物Ｄ−４，Ｅ−５を得た。
【００８７】
実施例４４〜４５
実施例１７（１）で得られたアルデヒド体と対応するピロリノン化合物を用いて実施例８と同様に反応させることにより例示化合物Ｆ−６、Ｆ−７を得た。
【００８８】
実施例４６〜４８
実施例１９（２）で得られたアルデヒド体と対応する活性メチレン化合物を溶媒をｎ−プロパノールにし反応温度を７０〜９０℃にする以外は実施例３と同様にして例示化合物Ｂ−１４、Ｄ−５，Ｅ−６を得た。
【００８９】
実施例４９
実施例１７（１）で得られたアルデヒド体０．５ｇとシアノ酢酸０．１９ｇをエタノール７ｍｌに溶解させた。この溶液にピペリジン１滴をエタノール０．５ｍｌに溶解させた溶液を５滴加え、６５℃で１５時間攪拌した。反応液を希塩酸に排出し酢酸エチルで抽出した。この有機層を乾燥、濃縮し、シリカゲルカラムクロマトグラフィーにより精製して例示化合物Ａ−９を得た。
【００９０】
実施例５０
（１）実施例１（１）で得られたペリミジン化合物２．８ｇをＤＭＦ４０ｍｌに溶解させ、炭酸カリウム７．４ｇ、１−ヨードドデカン１７ｇを加えた。これを７０℃まで昇温し、同温度で１６時間攪拌した。反応液を水に排出し酢酸エチルで抽出した。この有機層を水洗、乾燥、濃縮後、シリカゲルカラムクロマトグラフィーにより精製し得られたオイルをＤＭＦ１００ｍｌに溶解させ、０℃にてオキシ塩化リン２．４ｇを滴下した。０℃で１時間攪拌したのち、反応液を水に排出した。これを中和し酢酸エチルで抽出、水洗、乾燥、濃縮したのちシリカゲルカラムクロマトグラフィーにより精製し下記構造式（２９）で表されるアルデヒド化合物を３．５ｇ得た。
【００９１】
【化４４】

（２）上記の（１）で得られたアルデヒド体０．３ｇをエタノール３ｍｌに溶解させ、マロノニトリル０．０４ｇを加えた。この溶液にピペリジン０．０５ｇを加え室温で５時間攪拌した。反応液を濃縮し、シリカゲルカラムクロマトグラフィーにより精製して例示化合物Ａ−６を０．２８ｇ得た。
【００９２】
実施例５１
実施例２０で用いたアルデヒド体の代わりに実施例５０（１）で得られたアルデヒド体を用いる以外は実施例２０と同様にして例示化合物Ａ−７を得た。
【００９３】
実施例５２〜５５
実施例５０（１）で得られたアルデヒド体と対応する活性メチレン化合物を用いて実施例３と同様に反応させることにより例示化合物Ｂ−１１、Ｂ−１２，Ｃ−７，Ｄ−３を得た。
【００９４】
実施例５６
実施例７におけるアルデヒド体の代わりに実施例５０（１）で得られたアルデヒド体を用いる以外は実施例７と同様にして例示化合物Ｅ−４を得た。
【００９５】
実施例５７
実施例８におけるアルデヒド体の代わりに実施例５０（１）で得られたアルデヒド体を用い、３−エトキシカルボニル−２−（４−シアノフェニル）−５−ピロリノンの代わりに３−エトキシカルボニル−２−フェニル−５−ピロリノンを用いる以外は実施例８と同様にして例示化合物Ｆ−５を得た。
【００９６】
以上の実施例により得られた化合物についてのメタノール中での吸収極大波長λｍａｘを以下の表に示す。
【表８】

【表９】

比較例
【００９７】
【化４５】

比較例として上記の一般式（３０）で示される化合物を上記の実施例と同様な方法を用いて以下の比較例化合物１〜１２を合成した。ここでＲ６０、Ｒ６１はアルキル基を表す。ｎ、ｍ、Ａ、Ｙ、Ｚは一般式（１）の場合と同じ意味を有する。
【００９８】
比較例１
【化４６】

比較例２
【化４７】

比較例３
【化４８】

比較例４
【化４９】

比較例５
【化５０】

比較例６
【化５１】

比較例７
【化５２】

比較例８
【化５３】

比較例９
【化５４】

比較例１０
【化５５】

比較例１１
【化５６】

比較例１２
【化５７】

以上の実施例、比較例で得た化合物のメタノール中での吸収極大波長λｍａｘを、前記一般式（１）におけるｎ、ｍの値とともに下表に示す。ｎは炭素鎖の長さを表すので、これにより本発明の化合物が、比較例の化合物より短い炭素鎖で比較例と同等もしくはそれ以上の波長の光を吸収し、同じ炭素数なら長波長の光を吸収することが確認された。
【００９９】
【表１０】

さらに比較例１３として実施例７と同様な方法を用いて下記構造の化合物を合成、この化合物と実施例７で得られた化合物について乳酸エチルに対する溶解性を比較検討した。
【０１００】
比較例１３
【化５８】

その結果は次表の通りであり、本発明のベリミジン骨格を有する化合物は、乳酸エチルに対する溶解性においても優れた色素であることが確認された。
【表１１】

【図面の簡単な説明】
【図１】実施例１で得た化合物Ａ−１の赤外吸収スペクトル（ＫＢｒ）
【図２】実施例１で得た化合物Ａ−１の可視吸収スペクトル（メタノール）
【図３】実施例３で得た化合物Ｂ−１の赤外吸収スペクトル（ＫＢｒ）
【図４】実施例３で得た化合物Ｂ−１の可視吸収スペクトル（メタノール）
【図５】実施例１０で得た化合物Ｈ−１の赤外吸収スペクトル（ＫＢｒ）
【図６】実施例１０で得た化合物Ｈ−１の可視吸収スペクトル（メタノール）
【図７】実施例１０で得た化合物Ｈ−１の蛍光スペクトル（アセトン）BACKGROUND OF THE INVENTION
[0001]
The present invention relates to a novel compound having a perimidine skeleton. The compound of the present invention is a pigment that absorbs visible light or near-infrared light, and is used for dyes for fibers, dyes for resins, dyes for writing instruments, dyes for printing, pigments for color filters, optical recording materials, thermal recording materials, light. It can be used as a sensitizer, an electrophotographic material, an electroluminescent element material, a photoelectric conversion material, a photothermal conversion material, a dye laser material, and the like.
[Prior art]
[0002]
A dye having a polymethine chain is well known as a dye that absorbs light from the visible part to the near infrared part. Since these polymethine dyes generally have a large extinction coefficient and the absorption wavelength varies depending on the length of the polymethine chain, they have the advantage of being adaptable to light of various wavelengths with the same molecular structure. On the other hand, these dyes have a drawback that the storage durability such as weather resistance is deteriorated particularly when the polymethine chain has a long structure. Although it cannot be generally stated, in the case of a merocyanine type dye, the wavelength to be shifted becomes smaller as the polymethine chain is lengthened, and the absorption spectrum tends to become broader, and it is difficult to obtain sharp absorption with a long wavelength dye. In addition, if the polymethine chain is lengthened, there is a problem that the number of production steps increases accordingly.
[0003]
Thus, the problem caused by lengthening the polymethine chain is not only the absorption wavelength but also the fluorescence wavelength. Some polymethine dyes fluoresce at room temperature, but as the polymethine chain is lengthened, harmful effects such as lowering of light emission efficiency, lowering of durability, and increase in the number of manufacturing processes increase. There are few dyes suitable for practical use in materials emitting light in the wavelength range.
[Patent Document 1]
JP 58-11118 A
[Patent Document 2]
Japanese Patent Laid-Open No. 62-295963
[Patent Document 3]
JP 63-40143 A
[Patent Document 4]
JP-A-63-75065
[Patent Document 5]
Japanese Patent Laid-Open No. 06-329654
[Patent Document 6]
JP 2000-267227 A
[Patent Document 7]
JP 2001-76775 A
[Patent Document 8]
USP 3852683 Specification
[Non-Patent Document 1]
Journal of the Chemical Society Communications, Chemical Communications, 90, (1993), Alex KY. Others
[Non-Patent Document 2]
Soybean and Pigments (Dyes and Pigments) 40, 11, (1998), Jae-yun Jaung and others
[Non-Patent Document 3]
Journal of Organic Chemistry. , 51, 370, (1986), Rolf
Gleiter and others
[Non-Patent Document 4]
Chemistry of Heterocyclic Compounds, 35 (3), 319, (1999), A.C. F. Pozharskii and others
[Problems to be solved by the invention]
[0004]
In order to alleviate the disadvantages of such polymethine dyes, the present invention has attempted to design a molecular structure that can absorb light of a long wavelength with a short polymethine chain.
[Means for Solving the Problems]
[0005]
The compound of the present invention contains a perimidine skeleton in the molecular structure, and absorbs light of a long wavelength with a smaller methine number than a conventional polymethine dye due to the strong electron donating property of the perimidine skeleton and the effect of expanding the conjugated system. be able to.
Further, among the compounds of the present invention, there are fluorescent dyes, and the luminous ability in that case has an advantage that light having a long wavelength can be emitted with a small number of methines.
[0006]
Among the compounds of the present invention, compounds in which A is represented by the general formulas (2) and (3) are likely to emit fluorescence, and in particular, a compound having the structure of the general formula (3) has high luminous ability and has a longer wavelength than red. Can emit fluorescent light.
[0007]
The compound of the present invention is represented by the following general formula (1).
Embedded image

[R1 and R2 each independently represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, an alkoxyalkyl group or an aralkyl group. R3 and R4 represent an alkyl group. R3 and R4 may be linked to form a ring. n represents an integer of 0 to 5. m represents an integer of 0-2. A represents a divalent atomic group that forms a conjugated system with an adjacent atomic group. W, X, Y, and Z each independently represent a hydrogen atom, an alkyl group, or a halogen atom]
[0008]
Examples of the alkyl group represented by R1 and R2 in the general formula (1) include a linear or branched alkyl group having 1 to 18 carbon atoms, a cyclohexyl group, and a cyclohexylmethyl group. Similarly, a substituted or unsubstituted aryl group. Examples of the alkyl group include a phenyl group, a tolyl group, a chlorophenyl group, and a methoxyphenyl group. Examples of the alkoxyalkyl group include an alkoxyalkyl group having 1 to 12 carbon atoms. Examples of the aralkyl group include a benzyl group. It is done. When the compound of the present invention is used by dissolving in a low polarity solvent, R1 and R2 are preferably alkyl groups having a large number of carbon atoms. When used by dissolving in a high polarity solvent, R1 and R2 are those having a carbon number. It is preferable that there are few alkyl groups or alkoxyalkyl groups. In addition, when used in applications requiring strong light resistance, R1 and R2 are preferably substituted or unsubstituted phenyl groups.
[0009]
As an example of the alkyl group of R3 and R4 in General formula (1), a C1-C10 linear or branched alkyl group is mentioned. Examples where R3 and R4 are linked to form a ring include those in which they form a cyclopentane ring, a cyclohexane ring or the like. Those in which the cycloalkane ring is further substituted with one or more methyl group, ethyl group, propyl group, butyl group, pentyl group and the like are also included.
[0010]
As an example of the alkyl group of W and X in General formula (1), a C1-C10 linear or branched alkyl group is mentioned.
Examples of A in the general formula (1) include those represented by the following general formulas (2) to (7).
Embedded image

[X1 and X2 each independently represent any of a cyano group, an alkoxycarbonyl group, a carboxyl group, and an acyl group]
[0011]
Embedded image

[R5 represents a hydrogen atom or an alkyl group. X3 and X4 each independently represent any of a cyano group, an alkoxycarbonyl group, a carboxyl group, and an acyl group]
[0012]
Embedded image

[X5, X6, and X7 each independently represent any of a cyano group, an alkoxycarbonyl group, a carboxyl group, and an acyl group]
[0013]
Embedded image

[R6 and R7 each independently represents a hydrogen atom or an alkyl group. X8 and X9 each independently represent any of a cyano group, an alkoxycarbonyl group, a carboxyl group, and an acyl group]
[0014]
Embedded image

[R8 represents any one of a hydrogen atom, an alkyl group, a fluorinated alkyl group, a halogen atom, a cyano group, an alkoxycarbonyl group, a carboxyl group, and an acyl group]
[0015]
Embedded image

[Ring A1 represents a nitrogen-containing heterocyclic ring having a substituent]
[0016]
Examples of the alkoxycarbonyl group of X1 and X2 in the general formula (2) include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, a dodecyloxycarbonyl group, and the like. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a trifluoroacetyl group, and a benzoyl group.
[0017]
As an example of the alkyl group of R5 in General formula (3), a C1-C18 linear, branched or cyclic alkyl group is mentioned. Examples of the alkoxycarbonyl group of X3 and X4 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, and a dodecyloxycarbonyl group. Examples of the acyl group include an acetyl group. , Propionyl group, butyryl group, trifluoroacetyl group, benzoyl group and the like.
[0018]
Examples of the alkoxycarbonyl group of X5, X6 and X7 in the general formula (4) include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group and a dodecyloxycarbonyl group. Examples of the group include an acetyl group, a propionyl group, a butyryl group, a trifluoroacetyl group, and a benzoyl group.
[0019]
As an example of the alkyl group of R6 and R7 in General formula (5), a C1-C18 linear, branched or cyclic alkyl group is mentioned. Examples of the alkoxycarbonyl group of X8 and X9 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, and a dodecyloxycarbonyl group. Examples of the acyl group include an acetyl group. , Propionyl group, butyryl group, trifluoroacetyl group, benzoyl group and the like.
[0020]
Examples of the alkyl group represented by R8 in the general formula (6) include a linear or branched alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group such as a cyclopropyl group, a cyclohexyl group, and a cyclohexylmethyl group. Examples of the alkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a 1,1-difluoroethyl group, a 2,2,2-trifluoroethyl group, and the like. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, and a dodecyloxycarbonyl group. Examples of the acyl group include an acetyl group, a propionyl group, Examples include butyryl group, trifluoroacetyl group, and benzoyl group.
[0021]
Specific examples of the atomic group represented by the general formula (7) include those represented by the following general formulas (8) to (13).
[0022]
Embedded image

[R11 represents any of a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group. R12 represents an alkyl group, a fluorinated alkyl group, a cyano group, a carboxyl group, an alkoxycarbonyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.
[0023]
Embedded image

[R13 represents either a hydrogen atom or an alkyl group. R14 represents any of an alkyl group, a fluorinated alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group. R15 represents any of a cyano group, a carboxyl group, and an alkoxycarbonyl group]
[0024]
Embedded image

[R16 represents any of a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a carboxymethyl group, a carboxyethyl group, an alkoxycarbonylmethyl group, and an alkoxycarbonylethyl group. Y1 represents an oxygen atom or a sulfur atom]
[0025]
Embedded image

[R17 represents any one of a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a carboxymethyl group, a carboxyethyl group, an alkoxycarbonylmethyl group, and an alkoxycarbonylethyl group. X10 and X11 each independently represent any of a cyano group, an alkoxycarbonyl group, a carboxyl group, and an acyl group]
[0026]
Embedded image

[R18 represents any one of a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a carboxymethyl group, a carboxyethyl group, an alkoxycarbonylmethyl group, and an alkoxycarbonylethyl group. R19 represents any of a cyano group, a carboxyl group, and an alkoxycarbonyl group. R20 represents an alkyl group]
[0027]
Embedded image

[R21 and R22 are each independently a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a carboxymethyl group, a carboxyethyl group, an alkoxycarbonylmethyl group, or an alkoxycarbonylethyl group. Represents Y2 represents an oxygen atom or a sulfur atom]
[0028]
Examples of the alkyl group represented by R11 in the general formula (8) include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and a dodecyl group. A substituted or unsubstituted aryl group, a substituted or unsubstituted hetero group, and the like. Examples of the aryl group include a phenyl group, an alkylphenyl group (eg, tolyl group, ethylphenyl group), an alkoxyphenyl group (eg, methoxyphenyl group, ethoxyphenyl group), and a fluorinated alkylphenyl group (eg, trifluoromethylphenyl group). , Pentafluoroethylphenyl group), halogenated phenyl group (for example, fluorinated phenyl group, chlorophenyl group, bromophenyl group, etc.), pyridyl group, alkylpyridyl group (for example, methylpyridyl group, ethylpyridyl group, etc.), thienyl Groups, alkyl thienyl groups (eg methyl thienyl) Group, ethyl thienyl group, etc.), pyrimidyl group, pyrazyl group, triazyl group, thiazolyl group, carboxyphenyl group, alkoxycarbonylphenyl group (eg methoxycarbonylphenyl group, ethoxycarbonylphenyl group etc.), cyanophenyl group, sulfophenyl group Etc. Examples of the alkyl group in R12 include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and a dodecyl group. Examples of the fluorinated alkyl group include a trifluoromethyl group, a pentafluoroethyl group, Examples include heptafluoropropyl group, 1,1-difluoroethyl group, 2,2,2-trifluoroethyl group, etc. Examples of alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxy Examples of the substituted or unsubstituted aryl group and the substituted or unsubstituted heteroaryl group include a phenyl group, an alkylphenyl (eg, tolyl group, ethylphenyl group, etc.) group, and a halogenated phenyl (eg, fluorine). Phenyl group, chlorophenyl group, bromophenyl group, etc.) group, fluorine Alkylphenyl (for example, trifluoromethylphenyl group, pentafluoroethylphenyl group, etc.) group, alkoxyphenyl group (for example, methoxyphenyl group, ethoxyphenyl group, etc.), pyridyl group, alkylpyridyl group (for example, methylpyridyl group, ethylpyridyl group, etc.) ), Thienyl group, alkylthienyl group (for example, methylthienyl group, ethylthienyl group, etc.) and the like.
[0029]
Examples of the alkyl group represented by R13 in the general formula (9) include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and a dodecyl group. Examples of the alkyl group in R14 include a methyl group and an ethyl group. Propyl group, butyl group, octyl group, dodecyl group, etc., and examples of the fluorinated alkyl group include trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, 1,1-difluoroethyl group, 2 2,2-trifluoroethyl group and the like, and examples of the substituted or unsubstituted aryl group and the substituted or unsubstituted heteroaryl group include a phenyl group and an alkylphenyl group (for example, a tolyl group and an ethylphenyl group). , Alkoxyphenyl groups (for example, methoxyphenyl group, ethoxyphenyl group, etc.), fluorinated alkylphenyl groups (for example, Fluoromethylphenyl group, pentafluoroethylphenyl group, etc.), halogenated phenyl group (eg, fluorinated phenyl group, chlorophenyl group, bromophenyl group, etc.), cyanophenyl group, aminophenyl group (eg, aminophenyl group, N, N- Dimethylaminophenyl group, etc.), thienyl group, alkylthienyl group (eg, methylthienyl group, ethylthienyl group, etc.), alkoxycarbonylphenyl group (eg, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, etc.), pyridyl group, alkylpyridyl group ( For example, a methylpyridyl group, an ethylpyridyl group, etc.) and the like. Examples of the alkoxycarbonyl group in R15 include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, and the like. It is.
[0030]
Examples of the alkyl group represented by R16 in the general formula (10) include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a dodecyl group, and the like. A substituted or unsubstituted aryl group, a substituted or unsubstituted hetero group, and the like. Examples of the aryl group include a phenyl group, an alkylphenyl group (for example, a tolyl group and an ethylphenyl group), an alkoxyphenyl group (for example, a methoxyphenyl group, an ethoxyphenyl group), and a fluorinated alkylphenyl group (for example, trifluoromethylphenyl). Group, pentafluoroethylphenyl group, etc.), halogenated phenyl group (eg, fluorinated phenyl group, chlorophenyl group, bromophenyl group, etc.), cyanophenyl group, carboxyphenyl group, alkoxycarbonylphenyl group (eg, methoxycarbonylphenyl group, ethoxy) Carbonylpheny Group), a thienyl group, alkylthienyl group (e.g. methylthienyl group, Echiruchieniru group), a pyridyl group, alkylpyridyl group (e.g. methylpyridyl include ethylpyridyl group) and the like.
[0031]
Examples of the alkyl group represented by R17 in the general formula (11) include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and a dodecyl group. A substituted or unsubstituted aryl group, a substituted or unsubstituted hetero group, and the like. Examples of the aryl group include a phenyl group, an alkylphenyl group (for example, a tolyl group and an ethylphenyl group), an alkoxyphenyl group (for example, a methoxyphenyl group, an ethoxyphenyl group), and a fluorinated alkylphenyl group (for example, trifluoromethylphenyl). Group, pentafluoroethylphenyl group, etc.), halogenated phenyl group (eg, fluorinated phenyl group, chlorophenyl group, bromophenyl group, etc.), cyanophenyl group, carboxyphenyl group, alkoxycarbonylphenyl group (eg, methoxycarbonylphenyl group, ethoxy) Carbonylpheny Group), thienyl group, alkylthienyl group (for example, methylthienyl group, ethylthienyl group, etc.), pyridyl group, alkylpyridyl group (for example, methylpyridyl group, ethylpyridyl group, etc.) and the like, and alkoxycarbonyl of X10 and X11 Examples of the group include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, and the like. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a trifluoroacetyl group, and a benzoyl group. Etc.
[0032]
Examples of the alkyl group represented by R18 in the general formula (12) include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a dodecyl group, and the like. A substituted or unsubstituted aryl group, a substituted or unsubstituted hetero group, and the like. Examples of the aryl group include a phenyl group, an alkylphenyl group (eg, tolyl group, ethylphenyl group), an alkoxyphenyl group (eg, methoxyphenyl group, ethoxyphenyl group), and a fluorinated alkylphenyl group (eg, trifluoromethylphenyl group). , Pentafluoroethylphenyl group, etc.), halogenated phenyl group (eg, fluorinated phenyl group, chlorophenyl group, bromophenyl group, etc.), pyridyl group, alkylpyridyl group (eg, methylpyridyl group, ethylpyridyl group, etc.), thienyl group, An alkyl thienyl group (eg methyl thienyl group, Tilthienyl group, etc.), pyrimidyl group, pyrazyl group, triazyl group, thiazolyl group, carboxyphenyl group, alkoxycarbonylphenyl group (eg methoxycarbonylphenyl group, ethoxycarbonylphenyl group etc.), cyanophenyl group, sulfophenyl group and the like. .
[0033]
Examples of the alkyl group represented by R21 and R22 in the general formula (13) include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and a dodecyl group. A substituted or unsubstituted aryl group, a substituted or unsubstituted group, and the like. Examples of the heteroaryl group include a phenyl group, an alkylphenyl group (eg, tolyl group, ethylphenyl group), an alkoxyphenyl group (eg, methoxyphenyl group, ethoxyphenyl group), and a fluorinated alkylphenyl group (eg, trifluoromethyl). Phenyl group, pentafluoroethylphenyl group, etc.), halogenated phenyl group (eg, fluorinated phenyl group, chlorophenyl group, bromophenyl group, etc.), pyridyl group, alkylpyridyl group (eg, methylpyridyl group, ethylpyridyl group, etc.), thienyl Groups, alkyl thienyl groups (eg methyl thienyl) Group, Echiruchieniru group), pyrimidyl group, pyrazinyl group, carboxyphenyl group, alkoxycarbonyl phenyl group (e.g. methoxycarbonylphenyl group, ethoxycarbonylphenyl group), and the like cyanophenyl group.
【The invention's effect】
[0034]
The compound of the present invention has a perimidine skeleton in the molecular structure and is a dye that efficiently absorbs visible light and near-infrared light, and has preferable properties as a dye such as a high extinction coefficient, high storage stability, and high solubility. Therefore, it is highly useful in industry.
DETAILED DESCRIPTION OF THE INVENTION
[0035]
Among the compounds of the present invention, those not containing a thiophene ring in the middle of the polymethine chain can be synthesized, for example, according to the scheme shown below.
Embedded image

The perimidine ring in the above formula can be synthesized, for example, by the method described in Non-Patent Document 3, and the formyl form of the perimidine compound can be synthesized, for example, by the method described in Non-Patent Document 4. The extension of the polymethine chain starting from this formyl body can be carried out, for example, by applying Wittig Reaction, Horner Emmons Reaction (Wittig Reaction, Horner-Emmons Reaction). Here, R51 represents an alkyl group, a phenyl group or the like, and R52 and R53 are alkyl groups, which may be linked to form a ring. By repeating this operation, the polymethine chain can be further extended. The perimidine compound of the present invention can be easily obtained by reacting the thus obtained formyl form with a compound having active methylene or active methyl.
[0036]
The reaction of the above formyl compound with active methylene or active methyl compound may be carried out according to the reaction conditions generally known as Knoevenagel reaction. For example, alcohol, acetonitrile, benzene, toluene or the like is used as a reaction solvent. In this case, piperidine, pyrrolidine, sodium hydroxide, ammonium acetate, sulfuric acid, acetic acid and the like can also be used as a reaction accelerator.
[0037]
Among the compounds of the present invention, those containing a thiophene ring in the middle of the polymethine chain can be synthesized, for example, by the following method. The perimidine compound of the present invention can be easily obtained by reacting the thus obtained formyl form with a compound having active methylene or active methyl. Here, R54 in the following formula represents an alkyl group, a phenyl group, or the like.
[0038]
Embedded image

Examples of the compound of the general formula (1) that can be synthesized by the above two synthesis methods include the following.
[0039]
[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

【Example】
[0040]
Hereinafter, the present invention will be described more specifically with reference to examples.
Example 1
(1) 16.3 g of 1,8-diaminonaphthalene and 18 g of acetone were dissolved in 280 ml of benzene, 4 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at room temperature for 18 hours. The reaction solution was washed with aqueous sodium bicarbonate, dried and concentrated to obtain 15.7 g of 2,2-dimethyl-2,3-dihydro-1H-perimidine represented by the following structural formula (14).
[0041]
Embedded image

(2) 2,2-Dimethyl-2,3-dihydro-1H-perimidine (1.8 g) was dissolved in DMF (25 ml), potassium carbonate (4.1 g) and ethyl iodide (6.2 g) were added, and the mixture was stirred at 60 ° C. for 15 hours. Drain the reaction mixture into water and extract with ethyl acetate. After drying, it was concentrated and purified by silica gel column chromatography to obtain 2.1 g of 1,3-diethyl-2,2-dimethyl-2,3-dihydro-1H-perimidine represented by the following structural formula (15).
[0042]
Embedded image

(3) 1,3-Diethyl-2,2-dimethyl-2,3-dihydro-1H-perimidine (2 g) was dissolved in DMF (25 ml), and 1.3 g of phosphorus oxychloride was added dropwise at 0 ° C. After completion of the reaction, the reaction mixture was discharged into water, neutralized and extracted with ethyl acetate. The extract was washed with water, dried, concentrated, purified by silica gel column chromatography, and 1,3-diethyl-2,2-dimethyl-2,3-dihydro-6-formyl-1H-perimidine represented by the following structural formula (16) 1.45 g was obtained.
[0043]
Embedded image

(4) 0.5 g of 1,3-diethyl-2,2-dimethyl-2,3-dihydro-6-formyl-1H-perimidine and 0.13 g of malononitrile are dissolved in 10 ml of ethanol, and 3 drops of piperidine are added at room temperature. Stir for 3 hours. Crystals obtained by filtering the reaction solution were washed with methanol to obtain 0.42 g of black purple exemplified compound A-1.
[0044]
λmax = 515 nm (ε = 29000) (in methanol)
¹ H-NMR (CDCl ₃ , 300 MHz): δ 1.23 (t, 3H, J = 7.1 Hz), 1.36 (t, 3H, J = 7.1 Hz), 1.60 (s, 6H), 3.53 (q, 2H) , J = 7.1 Hz), 3.66 (q, 2H, J = 7.1 Hz), 6.53 (d, 1H, J = 9.0 Hz), 6.68 (d, 1H, J = 7. 9 Hz), 7.30 (d, 1 H, J = 8.3 Hz), 7.46 (dd, 1 H, J = 7.9, 8.3 Hz), 8.25 (s, 1 H), 8.56 ( d, 1H, J = 9.0 Hz)
¹³ C-NMR (CDCl ₃ 75 MHz): 13.5, 13.9, 25.0, 40.7, 41.6, 70.3, 73.5, 103.5, 107.7, 111.1, 114.1, 114. 9, 116.0, 117.1, 130.5, 132.6, 134.3, 142.6, 148.6, 153.2
[0045]
Example 2
1.0 g of 1,3-diethyl-2,2-dimethyl-2,3-dihydro-6-formyl-1H-perimidine obtained in Example 1 (3) and 0.4 g of cyanoacetic acid were dissolved in 12 ml of ethanol. Then, a catalytic amount of piperidine was added and stirred at 60 ° C. for 15 hours. It was discharged into dilute hydrochloric acid, extracted, dried, concentrated and purified with chloroform to obtain 0.51 g of Exemplified Compound A-4.
[0046]
λmax = 495 nm (ε = 18000) (in methanol)
LC / MS: 350 (M + H ⁺ )
¹ H-NMR (DMSO-d ₆ 300 MHz): δ 1.17 (t, 3H, J = 7.0 Hz), 1.26 (t, 3H, J = 7.0 Hz), 1.54 (s, 6H), 3.51 (q, 2H) , J = 7.0 Hz), 3.66 (q, 2H, J = 7.0 Hz), 6.60-6.75 (m, 2H), 7.31 (d, 1H, J = 8.1 Hz) 7.46 (dd, 1H, J = 8.1, 8.1 Hz), 8.27 (s, 1H), 8.48 (d, 1H, J = 8.8 Hz), 8.76 (s, 1H)
[0047]
Example 3
0.76 g of 1,3-diethyl-2,2-dimethyl-2,3-dihydro-6-formyl-1H-perimidine obtained in Example 1 (3) and 3-cyano-1-phenyl-5-pyrazolone 0.5 g was dissolved in 50 ml of ethanol and stirred at 50 ° C. for 3 hours. The reaction solution was filtered and washed with methanol to obtain 0.7 g of Exemplified Compound B-1.
λmax = 601 nm (ε = 46000) (in methanol)
LC / MS: 450 (M + H ⁺ )
[0048]
Example 4
The reaction was conducted in the same manner as in Example 3 except that 3-carboxy-1-phenyl-5-pyrazolone was used instead of 3-cyano-1-phenyl-5-pyrazolone used in Example 3, and the reaction solution was filtered. The filtrate obtained was purified by silica gel column chromatography to obtain exemplary compound B-2.
[0049]
λmax = 587 nm (ε = 35000) (in methanol)
LC / MS: 469 (M + H ⁺ )
¹ H-NMR (DMSO-d ₆ , 300 MHz): δ 1.18 (t, 3H, J = 7.0 Hz), 1.32 (t, 3H, J = 7.0 Hz), 1.60 (s, 6H), 3.56 (q, 2H) , J = 7.0 Hz), 3.78 (q, 2H, J = 7.0 Hz), 6.73-6.82 (m, 2H), 7.21-7.29 (m, 1H), 7 .45-7.62 (m, 5H), 7.97-8.06 (m, 2H), 9.35 (s, 1H), 9.91 (br, 1H)
¹³ C-NMR (DMSO-d ₆ , 75 MHz): 8.6, 9.2, 19.5, 35.8, 36.0, 69.3, 99.4, 102.7, 106.4, 108.3, 108.6, 112. 3, 114.8, 120.4, 124.0, 126.6, 131.2, 134.1, 134.6.136.9, 137.9, 140.3, 145.2, 157.7, 158.5
[0050]
Example 5
Exemplified compound C-1 was obtained in the same manner as in Example 3, except that rhodanine-3-acetic acid was used instead of 3-cyano-1-phenyl-5-pyrazolone used in Example 3. λmax = 539 nm (ε = 31000) (in methanol)
LC / MS: 456 (M + H ⁺ )
[0051]
Example 6
0.3 g of 1,3-diethyl-2,2-dimethyl-2,3-dihydro-6-formyl-1H-perimidine obtained in Example 1 (3) was dissolved in 6 ml of ethanol. Ethyl rhodanine (0.19 g) was added, piperidine (0.09 g) was further added, and the mixture was stirred at room temperature for 4 hours. The reaction solution was concentrated and purified by silica gel column chromatography to obtain exemplary compound C-2.
λmax = 537 nm (ε = 27000) (in methanol)
LC / MS: 426 (M + H ⁺ )
[0052]
Example 7
Dissolve 0.28 g of 1,3-diethyl-2,2-dimethyl-2,3-dihydro-6-formyl-1H-perimidine obtained in Example 1 (3) and 0.15 g of barbituric acid in 7 ml of ethanol. And stirred at room temperature for 3 hours. The reaction solution was filtered and washed with methanol to obtain 0.27 g of Exemplified Compound E-1.
[0053]
λmax = 560 nm (ε = 35000) (in methanol)
LC / MS: 393 (M + H ⁺ )
¹ H-NMR (DMSO-d ₆ , 300 MHz): δ 1.17 (t, 3H, J = 7.0 Hz), 1.28 (t, 3H, J = 7.0 Hz), 1.56 (s, 6H), 3.53 (q, 2H) , J = 7.0 Hz), 3.70 (q, 2H, J = 7.0 Hz), 6.61 (d, 2H, J = 9.2 Hz), 6.71 (d, 1H, J = 8. 0 Hz), 7.32 (d, 1H, J = 8.0 Hz), 7.49 (dd, 1H, J = 8.0, 8.0 Hz), 8.92 (s, 1H), 9.03 ( d, 1H, J = 9.2 Hz), 10.71 (br, 1H), 10.88 (br, 1H)
¹³ C-NMR (DMSO-d ₆ 75 MHz): 8.6, 9.1, 19.5, 35.6, 36.0, 68.9, 98.0, 101.9, 104.1, 106.8, 108.2, 110. 9, 125.9, 131.2, 134.0, 137.8, 143.8, 145.6, 157.7, 160.3
[0054]
Example 8
0.28 g of 1,3-diethyl-2,2-dimethyl-2,3-dihydro-6-formyl-1H-perimidine obtained in Example 1 (3) and 3-ethoxycarbonyl-2- (4-cyano Phenyl) -5-pyrrolinone 0.29 g was dissolved in ethanol 15 ml, and 62% sulfuric acid 0.1 ml was added. Stir at 45 ° C. for 1 hour. The reaction solution was discharged into water, neutralized, filtered, and washed with methanol to obtain 0.43 g of Exemplified Compound F-3.
λmax = 555 nm (ε = 33000) (in methanol)
[0055]
Example 9
Example compound synthesized in the same manner as in Example 3 except that 1,3-indandione was used instead of 3-cyano-1-phenyl-5-pyrazolone used in Example 3, and purified by silica gel column chromatography. G-1 was obtained.
λmax = 576 nm (ε = 48000) (in methanol)
[0056]
LC / MS: 411 (M + H ⁺ )
¹ H-NMR (DMSO-d ₆ , 300 MHz): δ 1.18 (t, 3H, J = 7.0 Hz), 1.32 (t, 3H, J = 7.0 Hz), 1.59 (s, 6H), 3.55 (q, 2H) , J = 7.0 Hz), 3.76 (q, 2H, J = 7.0 Hz), 6.74 (d, 2H, J = 9.0 Hz), 7.49-7.63 (m, 2H) 7.74-7.88 (m, 4H), 8.46 (s, 1H), 9.59 (d, 1H, J = 9.0 Hz)
¹³ C-NMR (DMSO-d ₆ , 75 MHz): 8.6, 9.1, 19.5, 35.7, 36.0, 69.0, 99.0, 102.2, 106.3, 108.4, 111.4, 115. 4, 117.0, 117.1, 126.2, 129.5, 129.8.131.0, 134.1, 134.2, 135.9, 136.8, 137.8, 144.3, 184.0, 186.1
[0057]
Example 10
Embedded image

0.2 g of 1,3-diethyl-2,2-dimethyl-2,3-dihydro-6-formyl-1H-perimidine obtained in Example 1 (3) and a pyran compound of the above structural formula (17) (for example, J. Org. Chem., 39, 7, 989, which can be synthesized according to the method described in (1974) was dissolved in 3 ml of ethanol, 0.07 g of piperidine was added, and the mixture was stirred at 70 ° C. for 6 hours. The reaction solution was concentrated, purified by silica gel column chromatography and washed with methanol to obtain 0.06 g of Exemplified Compound H-1.
[0058]
λmax = 537 nm (ε = 39000) (in methanol)
LC / MS: 437 (M + H ⁺ )
Fluorescence maximum wavelength λem = 723 nm (excitation wavelength λex = 600 nm in methanol)
λem = 707 nm (λex = 575 nm in acetone)
¹ H-NMR (CDCl ₃ 300 MHz): δ 1.24 (t, 3H, J = 7.1 Hz), 1.33 (t, 3H, J = 7.1 Hz), 1.56 (s, 6H), 2.40 (s, 3H) ), 3.51 (q, 2H, J = 7.1 Hz), 3.60 (q, 2H, J = 7.1 Hz), 6.45-6.70 (m, 5H), 7.38-7 .53 (m, 2H), 7.73 (d, 1H, J = 8.4 Hz), 8.15 (d, 1H, J = 15.5 Hz)
¹³ C-NMR (CDCl ₃ 75 MHz): 13.7, 14.0, 20.0, 24.9, 40.5, 41.6, 56.9, 72.8, 103.7, 105.4, 106.1, 106. 7, 111.9, 113.4, 115.1, 115.8, 115.9, 118.5, 127.5, 128.5, 133.1, 135.6, 142.5, 144.7, 156.5, 160.8, 161.6
[0059]
Example 11
Embedded image

Example compound H-2 was obtained in the same manner as in Example 10 except that the pyran compound of the above structural formula (18) was used instead of the pyran compound used in Example 10.
λmax = 523 nm (in methanol)
λem = 714 nm (λex = 586 nm in methanol)
λem = 697 nm (λex = 565 nm in acetone)
[0060]
Example 12
Embedded image

0.28 g of 1,3-diethyl-2,2-dimethyl-2,3-dihydro-6-formyl-1H-perimidine obtained in Example 1 (3) and 2,3- 0.26 g of dicyano-5-ethoxycarbonyl-6-methylpyrazine (for example, synthesized by the method described in Dies and Pigments, 40, 11, (1998)) is dissolved in 10 ml of toluene, and 2 drops of acetic acid, piperidine are added to this solution. One drop was added and stirred at 100 ° C. for 18 hours. The reaction solution was concentrated, purified by silica gel column chromatography, and washed with methanol to give Exemplary Compound I-1.
[0061]
λmax = 599 nm (ε = 38000) (in methanol)
LC / MS: 481 (M + H ⁺ )
¹ H-NMR (DMSO-d ₆ 300 MHz): δ 1.18 (t, 3H, J = 7.0 Hz), 1.26 (t, 3H, J = 7.0 Hz), 1.39 (t, 3H, J = 7.1 Hz), 1 .53 (s, 6H), 3.51 (q, 2H, J = 7.0 Hz), 3.63 (q, 2H, J = 7.0 Hz), 4.49 (q, 2H, J = 7. 1 Hz), 6.65 (d, 1 H, J = 8.5 Hz), 6.66 (dd, 1 H, J = 0.9, 7.5 Hz), 7.46 (dd, 1 H, J = 7.5 8.5 Hz), 7.46 (dd, 1 H, J = 0.9, 8.5 Hz), 7.56 (d, 1 H, J = 15.0 Hz), 7.95 (d, 1 H, J = 8.5 Hz), 8.75 (d, 1H, J = 15.0 Hz)
[0062]
Example 13
(1) 7.25 g of isophorone was mixed with 10 g of malononitrile, 0.3 ml of pipediline was added, and the mixture was stirred at 80 ° C. for 14 hours. After allowing to cool, the product was purified by silica gel column chromatography to obtain 6.5 g of a dicyano compound represented by the following structural formula (20).
[0063]
Embedded image

(2) 0.28 g of 1,3-diethyl-2,2-dimethyl-2,3-dihydro-6-formyl-1H-perimidine obtained in Example 1 (3) and the above (1) Then, 0.23 g of the dicyano compound was dissolved in 5 ml of ethanol, 0.1 g of piperidine was added, and the mixture was stirred at 75 ° C. for 15 hours. The reaction solution was allowed to cool and the crystals obtained by filtration were purified by silica gel column chromatography and washed with methanol to obtain 0.15 g of Exemplified Compound J-1.
[0064]
λmax = 578 nm (ε = 30000) (in methanol)
LC / MS: 451 (M + H ⁺ )
¹ H-NMR (CDCl ₃ , 300 MHz): δ 1.09 (s, 6H), 1.24 (t, 3H, J = 7.1 Hz), 1.33 (t, 3H, J = 7.1 Hz), 1.55 (s, 6H) ), 2.54 (s, 2H), 2.56 (s, 2H), 3.51 (q, 2H, J = 7.1 Hz), 3.59 (q, 2H, J = 7.1 Hz), 6.54 (d, 1H, J = 8.6 Hz), 6.64 (dd, 1H, J = 0.9, 7.5 Hz), 6.76 (s, 1H), 6.95 (d, 1H) , J = 15.8 Hz), 7.41 (dd, 1 H, J = 7.5, 8.5 Hz), 7.48 (dd, 1 H, J = 0.9, 8.5 Hz), 7.77 ( d, 1H, J = 8.6 Hz), 7.81 (d, 1H, J = 15.8 Hz)
¹³ C-NMR (CDCl ₃ 75 MHz): 13.7, 14.0, 24.9, 28.1, 32.0, 39.4, 40.5, 41.7, 43.0, 72.8, 75.0, 104. 0, 106.7, 111.9, 113.7, 114.5, 115.2, 119.8, 121.3, 125.6, 127.3, 128.3, 133.0, 134.9, 142.5, 144.3, 155.6, 169.1
[0065]
Example 14
(1) 10 g of 1,8-diaminonaphthalene and 6.2 g of cyclohexanone were dissolved in 140 ml of toluene and heated to reflux for 4 hours while removing water. The reaction solution was allowed to cool, and the filtered filtrate was concentrated. The obtained crystals were recrystallized from a hexane / ethyl acetate system to obtain 9.2 g of beige crystals of the following structural formula (21).
[0066]
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(2) 8.7 g of the perimidine compound represented by the formula (21) obtained above was dissolved in 100 ml of DMF, 19.1 g of potassium carbonate and 24 g of ethyl iodide were added, and the mixture was stirred at 60 ° C. for 21 hours. Drain the reaction mixture into water and extract with ethyl acetate. After washing with water, drying, concentration and purification by silica gel column chromatography, 5.4 g of a light green tar-like substance having the following structural formula (22) was obtained.
[0067]
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(3) 5.4 g of the perimidine compound represented by the formula (22) obtained in (2) was dissolved in 55 ml of DMF, 2.9 g of phosphorus oxychloride was added dropwise at 0 ° C., and the mixture was stirred at the same temperature for 2 hours. After completion of the reaction, the reaction mixture was discharged into water, neutralized and extracted with ethyl acetate. The extract was washed with water, dried and concentrated, and then purified by silica gel column chromatography to obtain 5.2 g of a yellow tar-like aldehyde of the following structural formula (23).
[0068]
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(4) 0.17 g of the aldehyde represented by the formula (23) obtained in (3) and 0.04 g of malononitrile were dissolved in 4 ml of ethanol, a catalytic amount of piperidine was added, and the mixture was stirred for 3 hours. The reaction solution was concentrated and purified by silica gel column chromatography to obtain exemplary compound A-5.
λmax = 506 nm (ε = 44000) (in methanol)
LC / MS: 371 (M + H ⁺ )
[0069]
Example 15
0.45 g of the aldehyde obtained in Example 14 (3) and 0.33 g of 3-carboxy-1-phenyl-5-pyrazolone were dissolved in 7 ml of ethanol, and the mixture was stirred at 60 ° C. for 3 hours. The reaction solution was filtered, the filtrate was concentrated, purified by silica gel column chromatography, and washed with hexane to obtain 0.12 g of Exemplified Compound B-9.
λmax = 574 nm (ε = 56000) (in methanol)
LC / MS: 509 (M + H ⁺ )
[0070]
Example 16
0.36 g of the aldehyde obtained in Example 14 (3) and 0.20 g of 3-cyano-1-phenyl-5-pyrazolone were dissolved in 10 ml of ethanol, and the mixture was stirred at 60 ° C. for 2 hours. The reaction solution was filtered, and the resulting crystals were washed with methanol to obtain 0.28 g of Exemplified Compound B-10.
λmax = 585 nm (ε = 76000) (in methanol)
LC / MS: 490 (M + H ⁺ )
[0071]
Example 17
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(1) 1 g of the aldehyde obtained in Example 1 (3) was dissolved in 30 ml of DMF, and 3.8 g of the phosphorus compound represented by the structural formula (24) was added. To this solution, 1.1 g of 28% methanol solution of sodium methoxide was added dropwise at room temperature. After completion of dropping, the mixture was stirred at room temperature for 2 hours and discharged into water. After extraction with ethyl acetate, the mixture was washed with water, dried and concentrated. To the obtained oily compound, 5 ml of 11% hydrochloric acid was added and stirred at room temperature for 30 minutes. The reaction solution was discharged into water, extracted with ethyl acetate, washed with water, dried and concentrated. The oily compound obtained was purified by silica gel column chromatography to obtain 1 g of an aldehyde of the following structural formula (25).
[0072]
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(2) 0.9 g of the aldehyde represented by the formula (25) obtained in (1) and 0.25 g of malononitrile were dissolved in 10 ml of ethanol. To this solution, 5 drops of a solution of 1 drop of piperidine dissolved in 0.5 ml of ethanol was added and stirred at room temperature for 1 hour. The crystal obtained by filtering the reaction solution was washed with methanol to obtain 0.86 of Exemplified Compound A-8.
[0073]
λmax = 576 nm (ε = 48000) (in methanol)
LC / MS: 357 (M + H ⁺ )
¹ H-NMR (CDCl ₃ , 300 MHz): δ 1.23 (t, 3H, J = 7.1 Hz), 1.35 (t, 3H, J = 7.1 Hz), 1.58 (s, 6H), 3.52 (q, 2H) , J = 7.1 Hz), 3.64 (q, 2H, J = 7.1 Hz), 6.53 (d, 1H, J = 8.8 Hz), 6.66 (dd, 1H, J = 3. 6, 5.3 Hz), 7.16 (dd, 1 H, J = 12.0, 14.5 Hz), 7.44 (d, 1 H, J = 3.6 Hz), 7.45 (d, 1 H, J = 5.3 Hz), 7.55 (d, 1 H, J = 12.0 Hz), 7.92 (d, 1 H, J = 14.5 Hz), 7.94 (d, 1 H, J = 8.8 Hz) ?
¹³ C-NMR (CDCl ₃ 75 MHz): 13.6, 14.0, 25.0, 40.6, 41.6, 73.2, 73.8, 104.0, 107.3, 111.5, 113.8, 114. 7, 115.7, 117.5, 117.7, 129.6, 130.6, 133.9, 142.6, 146.9, 147.6, 160.3
[0074]
Example 18
0.3 g of the aldehyde obtained in Example 17 (1) was dissolved in 5 ml of ethanol, 0.24 g of 3-carboxy-1-phenyl-5-pyrazolone was added to this solution, and the mixture was stirred at 45 ° C. for 2 hours. After allowing to cool, the precipitated crystals were collected by filtration and washed with ethanol to obtain 0.29 g of Exemplary Compound B-13.
λmax = 682 nm (ε = 65000) (in methanol)
LC / MS: 495 (M + H ⁺ )
[0075]
Example 19
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(1) 3.5 g of the aldehyde obtained in Example 1 (3) was dissolved in 30 ml of THF, and 4.4 g of the phosphorus compound represented by the structural formula (26) was added. To this solution, a THF suspension of 1.7 g of potassium t-butoxide was added dropwise at 5 ° C. over 1 hour, followed by stirring at the same temperature for 1 hour. After completion of the reaction, the reaction mixture was discharged into water and extracted with ethyl acetate. The organic layer was washed with water, dried and concentrated, and then purified by silica gel column chromatography to obtain 4.3 g of a brown oil of the following structural formula (27).
[0076]
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(2) 4 g of the compound represented by the formula (27) obtained in (1) was dissolved in 60 ml of THF and replaced with nitrogen. After cooling to 0 ° C., 8.3 ml of 1.6M n-butyllithium was added dropwise over 1 hour and stirred at the same temperature for 1 hour. At 0 ° C., 2.4 g of DMF was added and stirred for 2 hours. The reaction solution was discharged into water and extracted with ethyl acetate. The organic layer was washed with water, dried and concentrated, and then purified by silica gel column chromatography to obtain 0.5 g of an aldehyde represented by the following structural formula (28).
[0077]
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(3) 0.6 g of the aldehyde obtained in (2) was dissolved in 10 ml of ethanol, and 0.12 g of malononitrile was added. One drop of piperidine was added to this solution and stirred at 75 ° C. for 2 hours. The reaction solution was concentrated and purified by silica gel column chromatography, and then washed with hexane to obtain 0.17 g of Exemplified Compound A-10.
[0078]
λmax = 588 nm (ε = 53000) (in methanol)
LC / MS: 439 (M + H ⁺ )
¹ H-NMR (CDCl ₃ 300 MHz): δ 1.23 (t, 3H, J = 7.1 Hz), 1.31 (t, 3H, J = 7.1 Hz), 1.55 (s, 6H), 3.50 (q, 2H) , J = 7.1 Hz), 3.57 (q, 2H, J = 7.1H), 6.52 (d, 1H, J = 8.5 Hz), 6.64 (d, 1H, J = 7. 3 Hz), 7.10 (d, 1 H, J = 4.0 Hz), 7.13 (d, 1 H, J = 15.8 Hz), 7.42 (dd, 1 H, J = 7.3, 8.2 Hz) ), 7.51 (d, 1H, J = 8.2 Hz), 7.56 (d, 1H, J = 4.0 Hz), 7.66 (s, 1H), 7.71 (d, 1H, J = 8.5 Hz), 7.92 (d, 1H, J = 15.8 Hz)
¹³ C-NMR (CDCl ₃ 75 MHz): 13.8, 14.0, 24.9, 40.6, 41.7, 72.7, 73.5, 103.9, 106.8, 112.4, 114.1, 115. 0, 115.3, 116.8, 120.0, 125.5, 126.7, 128.2, 132.3, 132.8, 133.0, 140.5, 142.4, 143.8, 149.7, 157.7
[0079]
Example 20
0.35 g of the aldehyde obtained in Example 19 (2) was dissolved in 8 ml of acetonitrile, and 0.12 g of ethyl cyanoacetate and 0.09 g of piperidine were added to this solution, followed by stirring at room temperature for 1.5 hours. The reaction solution was concentrated and purified by silica gel column chromatography to obtain 0.4 g of exemplary compound A-11.
λmax = 557 nm (in methanol)
LC / MS: 486 (M + H ⁺ )
[0080]
Example 21
0.3 g of the ester obtained in Example 20 was added to 20 ml of ethanol, the temperature was raised to 50 ° C., and 1 g of a 10% aqueous sodium hydroxide solution was added. Stir at the same temperature for 1 hour. After cooling, it was discharged into water and adjusted to pH 3 with hydrochloric acid. The precipitated crystals were obtained by filtration and purified by silica gel column chromatography to obtain 0.1 g of exemplary compound A-12.
λmax = 541 nm (ε = 24000) (in methanol)
LC / MS: 458 (M + H ⁺ )
[0081]
Examples 22-23
Exemplified compounds A-2 and A-3 were obtained by reacting in the same manner as in Example 20 using the corresponding cyanoacetate and the aldehyde obtained in Example 1 (3).
[0082]
Examples 24-35
Exemplified compounds B-3 to B-8, C-3 to C-6, D were reacted in the same manner as in Example 3 using the corresponding active methylene compound obtained in Example 1 (3). -1, D-2 was obtained.
The rhodanine derivative used when synthesizing C-3 to C-6 can be synthesized, for example, using the method described in JP-A-08-269345.
[0083]
Examples 36-37
Example compounds E-2 and E-3 were obtained by reacting in the same manner as in Example 7 using the barbituric acid compound corresponding to the aldehyde obtained in Example 1 (3).
[0084]
Examples 38-40
Exemplified compounds F-1, F-2 and F-4 were obtained by reacting in the same manner as in Example 8 using the corresponding pyrrolinone compound obtained in Example 1 (3).
[0085]
Example 41
Illustrative compound C-8 was obtained by heating the aldehyde compound and 3-ethylrhodanine obtained in Example 17 (1) in ethanol.
[0086]
Examples 42-43
Exemplified compounds D-4 and E-5 were obtained by stirring the active methylene compound corresponding to the aldehyde obtained in Example 17 (1) at room temperature in the same manner as in Example 7.
[0087]
Examples 44-45
Exemplified compounds F-6 and F-7 were obtained by reacting in the same manner as in Example 8 using the corresponding pyrrolinone compound obtained in Example 17 (1).
[0088]
Examples 46-48
Exemplified compounds B-14 and D were obtained in the same manner as in Example 3 except that the active methylene compound corresponding to the aldehyde compound obtained in Example 19 (2) was made into n-propanol and the reaction temperature was changed to 70 to 90 ° C. -5 and E-6 were obtained.
[0089]
Example 49
0.5 g of the aldehyde obtained in Example 17 (1) and 0.19 g of cyanoacetic acid were dissolved in 7 ml of ethanol. To this solution, 5 drops of a solution of 1 drop of piperidine dissolved in 0.5 ml of ethanol was added and stirred at 65 ° C. for 15 hours. The reaction solution was discharged into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was dried, concentrated, and purified by silica gel column chromatography to give exemplary compound A-9.
[0090]
Example 50
(1) 2.8 g of the perimidine compound obtained in Example 1 (1) was dissolved in 40 ml of DMF, and 7.4 g of potassium carbonate and 17 g of 1-iodododecane were added. This was heated up to 70 degreeC and stirred at the same temperature for 16 hours. The reaction solution was discharged into water and extracted with ethyl acetate. The organic layer was washed with water, dried, concentrated, and then purified by silica gel column chromatography. The oil obtained was dissolved in 100 ml of DMF, and 2.4 g of phosphorus oxychloride was added dropwise at 0 ° C. After stirring at 0 ° C. for 1 hour, the reaction solution was discharged into water. This was neutralized, extracted with ethyl acetate, washed with water, dried, concentrated, and purified by silica gel column chromatography to obtain 3.5 g of an aldehyde compound represented by the following structural formula (29).
[0091]
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(2) 0.3 g of the aldehyde obtained in (1) above was dissolved in 3 ml of ethanol, and 0.04 g of malononitrile was added. Piperidine 0.05g was added to this solution, and it stirred at room temperature for 5 hours. The reaction solution was concentrated and purified by silica gel column chromatography to obtain 0.28 g of exemplary compound A-6.
[0092]
Example 51
Exemplified compound A-7 was obtained in the same manner as in Example 20, except that the aldehyde compound obtained in Example 50 (1) was used instead of the aldehyde compound used in Example 20.
[0093]
Examples 52-55
Exemplified compounds B-11, B-12, C-7, and D-3 were obtained by reacting in the same manner as in Example 3 using the corresponding active methylene compound obtained in Example 50 (1). It was.
[0094]
Example 56
Exemplified compound E-4 was obtained in the same manner as in Example 7, except that the aldehyde compound obtained in Example 50 (1) was used instead of the aldehyde compound in Example 7.
[0095]
Example 57
The aldehyde compound obtained in Example 50 (1) was used in place of the aldehyde compound in Example 8, and 3-ethoxycarbonyl-2 was substituted for 3-ethoxycarbonyl-2- (4-cyanophenyl) -5-pyrrolinone. Exemplified compound F-5 was obtained in the same manner as in Example 8, except that -phenyl-5-pyrrolinone was used.
[0096]
The absorption maximum wavelength λmax in methanol for the compounds obtained in the above examples is shown in the following table.
[Table 8]

[Table 9]

Comparative example
[0097]
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As comparative examples, the following compounds of comparative examples 1 to 12 were synthesized from the compounds represented by the above general formula (30) using the same method as in the above examples. Here, R60 and R61 represent an alkyl group. n, m, A, Y, and Z have the same meaning as in the general formula (1).
[0098]
Comparative Example 1
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Comparative Example 2
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Comparative Example 3
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Comparative Example 4
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Comparative Example 5
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Comparative Example 6
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Comparative Example 7
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Comparative Example 8
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Comparative Example 9
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Comparative Example 10
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Comparative Example 11
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Comparative Example 12
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The absorption maximum wavelength λmax in methanol of the compounds obtained in the above Examples and Comparative Examples is shown in the following table together with the values of n and m in the general formula (1). Since n represents the length of the carbon chain, the compound of the present invention absorbs light of a wavelength equal to or longer than that of the comparative example with a carbon chain shorter than that of the comparative example. It was confirmed to absorb light.
[0099]
[Table 10]

Further, as Comparative Example 13, a compound having the following structure was synthesized in the same manner as in Example 7, and the solubility of this compound and the compound obtained in Example 7 in ethyl lactate was compared.
[0100]
Comparative Example 13
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The results are as shown in the following table, and it was confirmed that the compound having a berimidine skeleton of the present invention is an excellent dye in solubility in ethyl lactate.
[Table 11]

[Brief description of the drawings]
1 is an infrared absorption spectrum (KBr) of Compound A-1 obtained in Example 1. FIG.
2 is a visible absorption spectrum (methanol) of Compound A-1 obtained in Example 1. FIG.
3 shows an infrared absorption spectrum (KBr) of compound B-1 obtained in Example 3. FIG.
4 is a visible absorption spectrum (methanol) of Compound B-1 obtained in Example 3. FIG.
5 shows an infrared absorption spectrum (KBr) of compound H-1 obtained in Example 10. FIG.
6 is a visible absorption spectrum (methanol) of Compound H-1 obtained in Example 10. FIG.
7 is a fluorescence spectrum (acetone) of Compound H-1 obtained in Example 10. FIG.

Claims (7)

A perimidine compound represented by the following general formula (1).

[R1 and R2 each independently represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, an alkoxyalkyl group or an aralkyl group. R3 and R4 represent an alkyl group. R3 and R4 may be linked to form a ring. n represents an integer of 0 to 5. m represents an integer of 0-2. A represents a divalent atomic group that forms a conjugated system with an adjacent atomic group. W, X, Y, and Z each independently represent a hydrogen atom, an alkyl group, or a halogen atom] The perimidine compound according to claim 1, wherein W and X are hydrogen atoms. The perimidine compound according to claim 1, wherein W and X are hydrogen atoms, and Y and Z are hydrogen atoms. The perimidine compound according to claim 1, wherein W and X are hydrogen atoms, Y and Z are hydrogen atoms, R1 and R2 are alkyl groups, and n is an integer of 0 to 3. The perimidine compound according to any one of claims 1 to 4, wherein A is any one of atomic groups represented by the following general formulas (2) to (7).

[X1 and X2 each independently represent any of a cyano group, an alkoxycarbonyl group, a carboxyl group, and an acyl group]

[R5 represents a hydrogen atom or an alkyl group. X3 and X4 each independently represent any of a cyano group, an alkoxycarbonyl group, a carboxyl group, and an acyl group]

[X5, X6, and X7 each independently represent any of a cyano group, an alkoxycarbonyl group, a carboxyl group, and an acyl group]

[R6 and R7 each independently represents a hydrogen atom or an alkyl group. X8 and X9 each independently represent any of a cyano group, an alkoxycarbonyl group, a carboxyl group, and an acyl group]

[R8 represents any one of a hydrogen atom, an alkyl group, a halogen atom, a fluorinated alkyl group, a cyano group, an alkoxycarbonyl group, a carboxyl group, and an acyl group]

[Ring A1 represents a nitrogen-containing heterocyclic ring having a substituent] The perimidine compound according to claim 5, wherein the atomic group of the formula (7) is any one of the atomic groups represented by the general formulas (8) to (13).

[R11 represents any of a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group. R12 represents an alkyl group, a fluorinated alkyl group, a cyano group, a carboxyl group, an alkoxycarbonyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[R13 represents either a hydrogen atom or an alkyl group. R14 represents any of an alkyl group, a fluorinated alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group. R15 represents any of a cyano group, a carboxyl group, and an alkoxycarbonyl group]

[R16 represents any of a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a carboxymethyl group, a carboxyethyl group, an alkoxycarbonylmethyl group, and an alkoxycarbonylethyl group. Y1 represents an oxygen atom or a sulfur atom]

[R17 represents any one of a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a carboxymethyl group, a carboxyethyl group, an alkoxycarbonylmethyl group, and an alkoxycarbonylethyl group. X10 and X11 each independently represent any of a cyano group, an alkoxycarbonyl group, a carboxyl group, and an acyl group]

[R18 represents any one of a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a carboxymethyl group, a carboxyethyl group, an alkoxycarbonylmethyl group, and an alkoxycarbonylethyl group. R19 represents any of a cyano group, a carboxyl group, and an alkoxycarbonyl group. R20 represents an alkyl group]

[R21 and R22 are each independently a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a carboxymethyl group, a carboxyethyl group, an alkoxycarbonylmethyl group, or an alkoxycarbonylethyl group. Represents Y2 represents an oxygen atom or a sulfur atom] R11 is a hydrogen atom, alkyl group, phenyl group, alkylphenyl group, alkoxyphenyl group, fluorinated alkylphenyl group, halogenated phenyl group, pyridyl group, alkylpyridyl group, thienyl group, alkylthienyl group, carboxyphenyl group, alkoxycarbonyl Any of phenyl group, cyanophenyl group, sulfophenyl group, pyrimidyl group, pyrazyl group, triazyl group, thiazolyl group, and R12 is a hydrogen atom, an alkyl group, a fluorinated alkyl group, a cyano group, a carboxyl group, an alkoxycarbonyl group , Phenyl group, alkylphenyl group, fluorinated alkylphenyl group, alkoxyphenyl group, halogenated phenyl group, pyridyl group, alkylpyridyl group, thienyl group, alkylthienyl group, and R14 is an alkyl group, fluorinated alkyl Group, phenyl group, alkylphenyl group, alkoxyphenyl group, fluorinated alkylphenyl group, halogenated phenyl group, alkoxycarbonylphenyl group, cyanophenyl group, aminophenyl group, pyridyl group, alkylpyridyl group, thienyl group, alkylthienyl R16 is a hydrogen atom, alkyl group, phenyl group, alkylphenyl group, fluorinated alkylphenyl group, alkoxyphenyl group, halogenated phenyl group, cyanophenyl group, carboxyphenyl group, carboxymethyl group, carboxy Any one of an ethyl group, an alkoxycarbonylphenyl group, an alkoxycarbonylmethyl group, and an alkoxycarbonylethyl group, and R17 is a hydrogen atom, an alkyl group, a phenyl group, an alkylphenyl group, a fluorinated alkylphenyl group, Any one of a ruxoxyphenyl group, a halogenated phenyl group, a cyanophenyl group, a carboxyphenyl group, a carboxymethyl group, a carboxyethyl group, an alkoxycarbonylphenyl group, an alkoxycarbonylmethyl group, and an alkoxycarbonylethyl group, and R18 is a hydrogen atom Alkyl group, phenyl group, alkylphenyl group, alkoxyphenyl group, fluorinated alkylphenyl group, halogenated phenyl group, cyanophenyl group, sulfophenyl group, carboxyphenyl group, alkoxycarbonylphenyl group, pyridyl group, alkylpyridyl group, Thienyl group, alkylthienyl group, pyrimidyl group, pyrazyl group, triazyl group, thiazolyl group, carboxymethyl group, carboxyethyl group, alkoxycarbonylmethyl group, alkoxycarbonylethyl R21 and R22 are each independently a hydrogen atom, alkyl group, phenyl group, alkylphenyl group, halogenated phenyl group, carboxyphenyl group, fluorinated alkylphenyl group, alkoxyphenyl group, alkoxycarbonylphenyl group Or a cyanophenyl group, a carboxymethyl group, a carboxyethyl group, an alkoxycarbonylmethyl group, or an alkoxycarbonylethyl group.

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