JP2003165918A - Pyrrole compound - Google Patents
Pyrrole compoundInfo
- Publication number
- JP2003165918A JP2003165918A JP2001402309A JP2001402309A JP2003165918A JP 2003165918 A JP2003165918 A JP 2003165918A JP 2001402309 A JP2001402309 A JP 2001402309A JP 2001402309 A JP2001402309 A JP 2001402309A JP 2003165918 A JP2003165918 A JP 2003165918A
- Authority
- JP
- Japan
- Prior art keywords
- group
- substituted
- unsubstituted
- alkyl
- alkyl group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Plural Heterocyclic Compounds (AREA)
- Pyrrole Compounds (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は分子内にピロール骨
格を有する新規な化合物に関するものである。本発明の
化合物は可視・近赤外領域の光を吸収する色素であり、
繊維用染料、プラスチック着色材、光記録用色素、カラ
ーフィルター用色素、熱転写記録用色素、光増感色素、
光熱変換色素等として利用可能なものである。TECHNICAL FIELD The present invention relates to a novel compound having a pyrrole skeleton in the molecule. The compound of the present invention is a dye that absorbs light in the visible / near infrared region,
Dyes for fibers, plastic colorants, dyes for optical recording, dyes for color filters, dyes for thermal transfer recording, photosensitizing dyes,
It can be used as a photothermal conversion dye or the like.
【0002】[0002]
【従来の技術】可視領域から近赤外領域に吸収をもつ有
機色素の代表的なものとして、ジフェニルメタン系色
素、トリフェニルメタン系色素、シアニン色素などのカ
チオン染料系の化合物が知られている。これらの色素の
多くは吸光係数が高く、色調が鮮明であるという長所を
もつが、一方で耐光性等の保存安定性が悪いという欠点
があった。またこれらの色素の多くは、水溶性は高いが
有機溶剤への溶解度は低いので、適用可能な用途が限定
され、また有機溶剤を用いた精製が難しいため、電子材
料や感光材料等、高純度が要求される材料としては利用
しにくいという問題もあった。これに対し、上記カチオ
ン系色素と類似のπ電子共役系を持ち、かつ有機溶剤へ
の溶解性が比較的高いタイプの色素としてメロシアニン
色素類が知られている。これらは電荷を中和するための
カウンターイオンを外部に持たず、分子内で電荷が中和
されているため、有機溶剤との親和性は比較的高いが十
分ではなく、吸光係数も分極の大きなシアニン色素類と
比べると小さいことが多く、またシアニン色素と同様、
安定性、耐久性に乏しいという欠点があった。2. Description of the Related Art Cationic dye compounds such as diphenylmethane dyes, triphenylmethane dyes, and cyanine dyes are known as typical organic dyes having absorption in the visible region to the near infrared region. Many of these dyes have the advantages of high absorption coefficient and clear color tone, but on the other hand, they have the drawback of poor storage stability such as light resistance. In addition, many of these dyes have high water solubility but low solubility in organic solvents, so their applicable applications are limited, and since purification using organic solvents is difficult, high purity materials such as electronic materials and photosensitive materials can be obtained. There is also a problem that it is difficult to use it as a material required for. On the other hand, merocyanine dyes are known as a type of dye having a π-electron conjugated system similar to the above cationic dye and having a relatively high solubility in an organic solvent. These do not have counter ions for neutralizing the charge on the outside, and the charge is neutralized in the molecule, so their affinity with organic solvents is relatively high but not sufficient, and the extinction coefficient also has a large polarization. Often smaller than cyanine dyes, and like cyanine dyes,
It had the drawback of poor stability and durability.
【0003】[0003]
【発明が解決しようとする課題】本発明は、上記色素が
有する有機溶剤への難溶性や耐久性の低さといった課題
を解決する有力な手段を与えるものである。DISCLOSURE OF THE INVENTION The present invention provides a powerful means for solving the problems such as poor solubility in organic solvents and low durability of the above dyes.
【0004】[0004]
【課題を解決するための手段】本発明の化合物は、分子
内にピロール骨格を有し、その部分が分子内の他の部分
とともにπ電子共役系を形成することを特徴とする。ピ
ロール骨格とその周辺部に陰電荷が分布するので、カウ
ンターアニオンを持たなくても分子内で電荷が中和され
る。したがって有機溶剤に対する溶解度が良好で、有機
溶剤を用いた精製操作すなわち再結晶やカラムクロマト
グラフィ等による精製も容易である。またメロシアニン
色素の多くがそうであるように酸素原子の部分に陰電荷
が局在するということもないので、分子の安定性が高く
耐光性も良好である。本発明の化合物はまた上記のよう
な特色を生かして、カウンターイオンなしで中性分子と
して単離することもできるが、必要に応じて酸性物質や
塩基性物質と塩を形成させて単離することも可能であ
り、用途に応じた柔軟な利用形態をとることができる。The compound of the present invention is characterized in that it has a pyrrole skeleton in the molecule, and that part forms a π-electron conjugated system with other parts in the molecule. Since the negative charge is distributed in the pyrrole skeleton and its peripheral portion, the charge is neutralized in the molecule even without the counter anion. Therefore, the solubility in an organic solvent is good, and the purification operation using an organic solvent, that is, the purification by recrystallization or column chromatography is easy. In addition, unlike most merocyanine dyes, the negative charge is not localized at the oxygen atom portion, so that the molecule has high stability and good light resistance. The compound of the present invention can also be isolated as a neutral molecule without a counter ion by utilizing the characteristics as described above, but it is isolated by forming a salt with an acidic substance or a basic substance as necessary. It is also possible to adopt a flexible usage pattern according to the application.
【0005】また本発明の化合物の中には、溶媒やpH
等、色素が置かれた環境によって色相が変わるものがあ
り、ソルバトクロミズム、サーモクロミズム、エレクト
ロクロミズム等の機能をもつ色素として利用することが
できる。本発明の化合物の中には、逆にそういった環境
によって変化しない安定な色相のものもあり、このよう
な点に関しても用途に合わせた幅広い選択が可能であ
る。本発明の化合物は下記一般式(1)で表されるもの
である。Some of the compounds of the present invention include solvents and pH.
For example, some pigments have different hues depending on the environment in which they are placed, and can be used as pigments having functions such as solvatochromism, thermochromism, and electrochromism. On the contrary, some of the compounds of the present invention have stable hues which do not change due to such an environment, and in this respect, a wide selection can be made according to the application. The compound of the present invention is represented by the following general formula (1).
【0006】[0006]
【化11】 [Chemical 11]
【0007】[式中、Xはアルコキシカルボニル基、シ
アノ基、カルボキシル基のいずれかを表す。Yは置換ま
たは非置換のアルキル基、置換または非置換のアリール
基、置換または非置換のピリジル基のいずれかを表す。
Zはハロゲン原子、置換または非置換のアリールオキシ
基、置換または非置換のアルキルチオ基、置換または非
置換のアリールチオ基、置換または非置換のピリジルチ
オ基、置換または非置換のチアゾリルチオ基、置換また
は非置換のイミダゾリルチオ基、置換または非置換のト
リアゾリルチオ基、置換または非置換のテトラゾリルチ
オ基、置換または非置換のキノリルチオ基、置換または
非置換のベンゾチアゾリルチオ基、置換または非置換の
ベンゾキサゾリルチオ基、置換または非置換のベンゾイ
ミダゾリルチオ基のいずれかを表す。Q1、Q2は、双
方が互いに独立に下記一般式(1−1)〜(1−5)の
いずれかで表される置換基を表すか、または一方のみが
下記一般式(1−1)〜(1−5)のいずれかで表され
る置換基であり、他方は、水素原子、置換または非置換
のアリール基、1位及び2位がアルキル基またはアリー
ル基によって置換された3−インドリル基のいずれかを
表す][In the formula, X represents an alkoxycarbonyl group, a cyano group or a carboxyl group. Y represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted pyridyl group.
Z is a halogen atom, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted pyridylthio group, a substituted or unsubstituted thiazolylthio group, a substituted or unsubstituted Imidazolylthio group, substituted or unsubstituted triazolylthio group, substituted or unsubstituted tetrazolylthio group, substituted or unsubstituted quinolylthio group, substituted or unsubstituted benzothiazolylthio group, substituted or unsubstituted benzoxazolylthio group Represents a substituted or unsubstituted benzimidazolylthio group. Q1 and Q2 each independently represent a substituent represented by any one of the following general formulas (1-1) to (1-5), or only one of the following general formulas (1-1) to (1-5). (1-5) is a substituent represented by any one of the above, and the other is a 3-indolyl group in which a hydrogen atom, a substituted or unsubstituted aryl group, and 1- and 2-positions are substituted with an alkyl group or an aryl group. Represents either of]
【0008】[0008]
【化12】 [Chemical 12]
【0009】[式中、L1は、二級または三級アミノ
基、ピロリジノ基、ピペリジノ基、モルホリノ基のいず
れかを表す。L2〜L5は互いに独立に水素原子、ハロ
ゲン原子、置換または非置換のアルキル基、置換または
非置換のアルコキシ基、置換または非置換のアミノ基、
置換または非置換のアシル基、水酸基、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][In the formula, L1 represents any of a secondary or tertiary amino group, a pyrrolidino group, a piperidino group and a morpholino group. L2 to L5 each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group,
Represents a substituted or unsubstituted acyl group, hydroxyl group, carboxyl group, or alkoxycarbonyl group]
【0010】[0010]
【化13】 [Chemical 13]
【0011】[L11〜L12は互いに独立にアルキル
基、置換または非置換のアリール基のいずれかを表す][L11 to L12 each independently represent an alkyl group or a substituted or unsubstituted aryl group]
【0012】[0012]
【化14】 [Chemical 14]
【0013】[Q3、Q4は互いに独立に、水素原子、
置換または非置換のアリール基、1位及び2位がアルキ
ル基またはアリール基によって置換された3−インドリ
ル基のいずれかを表す。Q3、Q4は同時に水素原子に
はならないものとする。nは0〜2の整数を表す][Q3 and Q4 are independently of each other a hydrogen atom,
It represents a substituted or unsubstituted aryl group, and a 3-indolyl group substituted at the 1-position and 2-position with an alkyl group or an aryl group. It is assumed that Q3 and Q4 do not become hydrogen atoms at the same time. n represents an integer of 0 to 2]
【0014】[0014]
【化15】 [Chemical 15]
【0015】[L21はアルキル基を表す][L21 represents an alkyl group]
【0016】[0016]
【化16】 [Chemical 16]
【0017】[L31はアルキル基を表す]一般式
(1)で表される化合物のさらに具体的な例としては、
下記一般式(2)〜(5)で表されるものが挙げられ
る。[L31 represents an alkyl group] More specific examples of the compound represented by the general formula (1) include:
Examples include those represented by the following general formulas (2) to (5).
【0018】[0018]
【化17】 [Chemical 17]
【0019】[式中、X、Y、Zは一般式(1)におけ
る場合と同じ置換基を表す。R1は、一般式(1)の
(1−1)におけるL1と同じであり、二級または三級
アミノ基、ピロリジノ基、ピペリジノ基、モルホリノ基
のいずれかを表す。R2〜R10は互いに独立に、水素
原子、ハロゲン原子、置換または非置換のアルキル基、
置換または非置換のアルコキシ基、置換または非置換の
アミノ基、置換または非置換のアシル基、水酸基、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わ
す][In the formula, X, Y and Z represent the same substituents as in the general formula (1). R1 is the same as L1 in (1-1) of the general formula (1) and represents any of a secondary or tertiary amino group, a pyrrolidino group, a piperidino group and a morpholino group. R2 to R10 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted acyl group, a hydroxyl group, a carboxyl group, or an alkoxycarbonyl group]
【0020】[0020]
【化18】 [Chemical 18]
【0021】[式中、X、Y、Zは一般式(1)の場合
と同じ置換基を表す。R21は一般式(2)のR1の場
合と同じ置換基を表す。R22〜R25は一般式(2)
のR2〜R10の場合と同じ置換基を表す。R11、R
12は互いに独立に置換または非置換のアルキル基、置
換または非置換のアリール基のいずれかを表す][In the formula, X, Y and Z represent the same substituents as in the case of the general formula (1). R21 represents the same substituent as in the case of R1 in the general formula (2). R22 to R25 are represented by general formula (2)
Represents the same substituents as in R2 to R10. R11, R
12 independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group]
【0022】[0022]
【化19】 [Chemical 19]
【0023】[式中、X、Y、Zは一般式(1)の場合
と同じ置換基を表す。R31〜R34は互いに独立に置
換または非置換のアルキル基、置換または非置換のアリ
ール基のいずれかを表す][In the formula, X, Y and Z represent the same substituents as in the case of the general formula (1). R31 to R34 each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group]
【0024】[0024]
【化20】 [Chemical 20]
【0025】[式中、X、Y、Zは一般式(1)の場合
と同じ置換基を表す。R41は一般式(2)のR1の場
合と同じ置換基を表す。R42〜R45は一般式(2)
のR2〜R10の場合と同じ置換基を表す。Q5、Q6
は水素原子、置換または非置換のアリール基、1位及び
2位がアルキル基またはアリール基によって置換された
3−インドリル基のいずれかを表す。nは0または1を
表す][In the formula, X, Y and Z represent the same substituents as in the case of the general formula (1). R41 represents the same substituent as in the case of R1 in the general formula (2). R42 to R45 are represented by general formula (2)
Represents the same substituents as in R2 to R10. Q5, Q6
Represents a hydrogen atom, a substituted or unsubstituted aryl group, or a 3-indolyl group substituted at the 1-position and 2-position with an alkyl group or an aryl group. n represents 0 or 1]
【0026】前記一般式(2)の化合物は、一般式
(1)の化合物におけるQ1、Q2の一方が(1−1)
式の置換基であり、他方が置換または非置換のアリール
基である場合の化合物に相当するものである。前記一般
式(3)の化合物は、一般式(1)の化合物におけるQ
1、Q2の一方が(1−1)式の置換基であり、他方が
(1−2)式の置換基である場合の化合物に相当するも
のである。また前記一般式(4)の化合物は、一般式
(1)の化合物におけるQ1、Q2の双方が互いに独立
に(1−2)式の置換基である場合の化合物に相当する
ものである。前記一般式(5)の化合物は、一般式
(1)の化合物におけるQ1、Q2の一方が(1−3)
式の置換基であり、他方が水素原子、置換または非置換
のアリール基、1位及び2位がアルキル基またはアリー
ル基によって置換された3−インドリル基のいずれかで
ある場合の化合物に相当するものである。In the compound of the general formula (2), one of Q1 and Q2 in the compound of the general formula (1) is (1-1).
It is a substituent of the formula and corresponds to a compound when the other is a substituted or unsubstituted aryl group. The compound of the general formula (3) is Q in the compound of the general formula (1).
This corresponds to a compound in which one of 1 and Q2 is a substituent of formula (1-1) and the other is a substituent of formula (1-2). The compound of the general formula (4) corresponds to the compound of the compound of the general formula (1) in which both Q1 and Q2 are independently the substituent of the formula (1-2). In the compound of the general formula (5), one of Q1 and Q2 in the compound of the general formula (1) is (1-3).
Corresponding to a compound represented by the formula, wherein the other is a hydrogen atom, a substituted or unsubstituted aryl group, and the 1- and 2-positions are either an alkyl group or a 3-indolyl group substituted with an aryl group. It is a thing.
【0027】これら一般式(1)(2)(3)(4)又
は(5)におけるXの例としては、カルボキシル基、シ
アノ基、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、
ペンチルオキシカルボニル基、ヘキシルオキシカルボニ
ル基、ヘプチルオキシカルボニル基、オクチルオキシカ
ルボニル基、ノニルオキシカルボニル基、デシルオキシ
カルボニル基、2,2,2−トリフルオロエトキシカル
ボニル基、2,2,3,3,3−ペンタフルオロプロポ
キシカルボニル基、2,2,3,3−テトラフルオロエ
トキシカルボニル基、フェノキシカルボニル基、メチル
フェノキシカルボニル基、ジメチルフェノキシカルボニ
ル基、トリメチルフェノキシカルボニル基、クロロフェ
ノキシカルボニル基、フルオロフェノキシカルボニル
基、ブロモフェノキシカルボニル基、トリフルオロメチ
ルフェノキシカルボニル基などが挙げられる。Examples of X in these general formulas (1), (2), (3), (4) or (5) include a carboxyl group, a cyano group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group and a butoxycarbonyl group. ,
Pentyloxycarbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 2,2,3,3,3 3-pentafluoropropoxycarbonyl group, 2,2,3,3-tetrafluoroethoxycarbonyl group, phenoxycarbonyl group, methylphenoxycarbonyl group, dimethylphenoxycarbonyl group, trimethylphenoxycarbonyl group, chlorophenoxycarbonyl group, fluorophenoxycarbonyl group , A bromophenoxycarbonyl group, a trifluoromethylphenoxycarbonyl group and the like.
【0028】Yの例としては、炭素数1〜18の直鎖も
しくは分岐のアルキル基、シクロヘキシル基、トリフル
オロメチル基、フェニル基、メチルフェニル基、エチル
フェニル基、プロピルフェニル基、ジメチルフェニル
基、トリメチルフェニル基、メトキシフェニル基、エト
キシフェニル基、トリフルオロメチルフェニル基、フル
オロフェニル基、クロロフェニル基、ブロモフェニル
基、ヨードフェニル基、シアノフェニル基、カルボキシ
フェニル基、カルバモイルフェニル基、ジメチルアミノ
フェニル基、ジエチルアミノフェニル基、ジブチルアミ
ノフェニル基、ナフチル基、ピリジル基、メチルピリジ
ル基などが挙げられる。Examples of Y include linear or branched alkyl groups having 1 to 18 carbon atoms, cyclohexyl groups, trifluoromethyl groups, phenyl groups, methylphenyl groups, ethylphenyl groups, propylphenyl groups, dimethylphenyl groups, Trimethylphenyl group, methoxyphenyl group, ethoxyphenyl group, trifluoromethylphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, cyanophenyl group, carboxyphenyl group, carbamoylphenyl group, dimethylaminophenyl group, Examples thereof include a diethylaminophenyl group, a dibutylaminophenyl group, a naphthyl group, a pyridyl group and a methylpyridyl group.
【0029】Zの例としては、フッ素原子、塩素原子、
臭素原子、ヨウ素原子、メチルチオ基、エチルチオ基、
プロピルチオ基、ブチルチオ基、ペンチルチオ基、ヘキ
シルチオ基、ヘプチルチオ基、オクチルチオ基、シクロ
ヘキシルチオ基、フェニルチオ基、トリルチオ基、ジメ
チルフェニルチオ基、トリメチルフェニルチオ基、t−
ブチルフェニルチオ基、2−メチル−5−t−ブチルフ
ェニルチオ基、メトキシフェニルチオ基、エトキシフェ
ニルチオ基、ヒドロキシフェニルチオ基、クロロフェニ
ルチオ基、フルオロフェニルチオ基、ペンタフルオロフ
ェニルチオ基、ブロモフェニルチオ基、ヨードフェニル
チオ基、シアノフェニルチオ基、トリフルオロメチルフ
ェニルチオ基、カルボキシフェニルチオ基、カルボキシ
メチルチオ基、カルボキシエチルチオ基、メトキシカル
ボニルメチルチオ基、エトキシカルボニルメチルチオ
基、ピリジルチオ基、メチルピリジルチオ基、ニトロピ
リジルチオ基、イミダゾリルチオ基、N−メチルイミダ
ゾリルチオ基、ベンゾイミダゾリルチオ基、N−メチル
ベンゾイミダゾリルチオ基、トリアゾリルチオ基、N−
メチルトリアゾリルチオ基、テトラゾリルチオ基、フェ
ニルテトラゾリルチオ基、チアゾリルチオ基、ジメチル
チアゾリルチオ基、ベンゾチアゾリルチオ基、メトキシ
ベンゾチアゾリルチオ基、エトキシベンゾチアゾリルチ
オ基、ニトロベンゾチアゾリルチオ基、ベンゾキサゾリ
ルチオ基、フェノキシ基、トリフルオロメチルフェノキ
シ基、ペンタフルオロフェノキシ基、シアノフェノキシ
基等が挙げられる。Examples of Z include a fluorine atom, a chlorine atom,
Bromine atom, iodine atom, methylthio group, ethylthio group,
Propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, cyclohexylthio group, phenylthio group, tolylthio group, dimethylphenylthio group, trimethylphenylthio group, t-
Butylphenylthio group, 2-methyl-5-t-butylphenylthio group, methoxyphenylthio group, ethoxyphenylthio group, hydroxyphenylthio group, chlorophenylthio group, fluorophenylthio group, pentafluorophenylthio group, bromophenyl Thio group, iodophenylthio group, cyanophenylthio group, trifluoromethylphenylthio group, carboxyphenylthio group, carboxymethylthio group, carboxyethylthio group, methoxycarbonylmethylthio group, ethoxycarbonylmethylthio group, pyridylthio group, methylpyridylthio group Group, nitropyridylthio group, imidazolylthio group, N-methylimidazolylthio group, benzimidazolylthio group, N-methylbenzimidazolylthio group, triazolylthio group, N-
Methyltriazolylthio group, tetrazolylthio group, phenyltetrazolylthio group, thiazolylthio group, dimethylthiazolylthio group, benzothiazolylthio group, methoxybenzothiazolylthio group, ethoxybenzothiazolylthio group, nitrobenzothiazolylthio group , Benzoxazolylthio group, phenoxy group, trifluoromethylphenoxy group, pentafluorophenoxy group, cyanophenoxy group and the like.
【0030】一般式(1)(2)(3)(4)又は
(5)において、好ましくはXはアルコキシカルボニル
基またはシアノ基であり、Yは非置換またはフッ素によ
って置換されたアルキル基、非置換またはシアノ基もし
くはジアルキルアミノ基によって置換されたフェニル
基、非置換またはアルキル基によって置換されたピリジ
ル基のいずれかであり、Zは塩素原子、非置換またはカ
ルボキシル基によって置換されたアルキルチオ基、非置
換またはアルキル基もしくはカルボキシル基によって置
換されたフェニルチオ基、非置換またはアルキル基もし
くはアリール基によって置換されたイミダゾリルチオ
基、非置換またはアルキル基によって置換されたトリア
ゾリルチオ基、非置換またはアルキル基もしくはアルコ
キシ基によって置換されたベンゾチアゾリルチオ基、非
置換またはアルキル基もしくはアルコキシ基によって置
換されたベンゾキサゾリルチオ基、非置換またはアルキ
ル基、アルコキシ基もしくはニトロ基によって置換され
たベンゾイミダゾリルチオ基のいずれかである。ここに
おいて、更に好ましくはYは非置換もしくはフッ素によ
って置換された炭素数4以下のアルキル基または非置換
のフェニル基であり、Zは塩素原子、非置換またはカル
ボキシル基によって置換されたアルキルチオ基、非置換
または炭素数4以下のアルキル基もしくはカルボキシル
基によって置換されたフェニルチオ基、非置換または炭
素数4以下のアルキル基によって置換されたイミダゾリ
ルチオ基、非置換または炭素数4以下のアルキル基によ
って置換されたトリアゾリルチオ基、非置換またはメチ
ル基もしくは炭素数4以下のアルコキシ基によって置換
されたベンゾチアゾリルチオ基、非置換またはメチル基
もしくは炭素数4以下のアルコキシ基によって置換され
たベンゾキサゾリルチオ基、非置換またはメチル基もし
くは炭素数4以下のアルコキシ基によって置換されたベ
ンゾイミダゾリルチオ基のいずれかである。In the general formulas (1), (2), (3), (4) and (5), X is preferably an alkoxycarbonyl group or a cyano group, Y is an unsubstituted or fluorine-substituted alkyl group, It is either a phenyl group substituted or substituted by a cyano group or a dialkylamino group, a pyridyl group unsubstituted or substituted by an alkyl group, Z is a chlorine atom, an alkylthio group substituted by a unsubstituted or carboxyl group, a non- Phenylthio group substituted or substituted by alkyl group or carboxyl group, imidazolylthio group unsubstituted or substituted by alkyl group or aryl group, triazolylthio group unsubstituted or substituted by alkyl group, unsubstituted or alkyl group or alkoxy group Replaced by Down zone benzothiazolylthio group, unsubstituted or alkyl or benzoxathiol benzoisothiazolyl thio group substituted by an alkoxy group, an unsubstituted or alkyl group, or a benzimidazolyl thio group substituted by an alkoxy group or a nitro group. Here, more preferably, Y is an unsubstituted or fluorine-substituted alkyl group having 4 or less carbon atoms or an unsubstituted phenyl group, and Z is an alkylthio group substituted by a chlorine atom, an unsubstituted or a carboxyl group, or a non-substituted phenyl group. A phenylthio group substituted or substituted by an alkyl group or a carboxyl group having 4 or less carbon atoms, an imidazolylthio group unsubstituted or substituted by an alkyl group having 4 or less carbon atoms, an unsubstituted or substituted by an alkyl group having 4 or less carbon atoms A triazolylthio group, a benzothiazolylthio group which is unsubstituted or substituted by a methyl group or an alkoxy group having 4 or less carbon atoms, and a benzoxazolylthio group which is unsubstituted or substituted by a methyl group or an alkoxy group having 4 or less carbon atoms, Unsubstituted or methyl group or carbon number It is either benzimidazolyl thio group substituted by an alkoxy group.
【0031】一般式(2)におけるR1の例としては二
級アミノ基、三級アミノ基、ピロリジノ基、ピペリジノ
基、モルホリノ基が挙げられ、二級または三級アミノ基
における置換基の例としては炭素数1〜18の直鎖もし
くは分岐のアルキル基、シクロペンチル基、シクロヘキ
シル基、フェニル基、メチルフェニル基、ジメチルフェ
ニル基、トリメチルフェニル基、メトキシフェニル基、
エトキシフェニル基、クロロフェニル基、ブロモフェニ
ル基、トリフルオロメチルフェニル基、ベンジル基、メ
トキシエチル基、エトキシエチル基、メトキシプロピル
基、エトキシプロピル基、ブトキシエチル基、メトキシ
エトキシメチル基、エトキシエトキシエチル基、シアノ
エチル基、シアノプロピル基等が挙げられる。一般式
(2)におけるR2〜R10の例としては、水素原子、
フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数
1〜4の直鎖もしくは分岐のアルキル基、トリフルオロ
メチル基、メトキシ基、エトキシ基、プロポキシ基、ブ
トキシ基、ペンチルオキシ基、ヘキシルオキシ基、ヘプ
チルオキシ基、オクチルオキシ基、アセチル基、水酸
基、カルボキシル基、メトキシカルボニル基、エトキシ
カルボニル基、ジメチルアミノ基、ジエチルアミノ基、
ジプロピルアミノ基、ジブチルアミノ基、ジペンチルア
ミノ基、ジヘキシルアミノ基、アセチルアミノ基、ベン
ゾイルアミノ基、アニリノ基、N−メチルアニリノ基等
があげられる。一般式(2)において、好ましくはR
1、R6はジアルキルアミノ基であり、R2〜R5、R
7〜R10は水素原子である。Examples of R1 in the general formula (2) include a secondary amino group, a tertiary amino group, a pyrrolidino group, a piperidino group and a morpholino group, and examples of the substituent in the secondary or tertiary amino group include A linear or branched alkyl group having 1 to 18 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, a methoxyphenyl group,
Ethoxyphenyl group, chlorophenyl group, bromophenyl group, trifluoromethylphenyl group, benzyl group, methoxyethyl group, ethoxyethyl group, methoxypropyl group, ethoxypropyl group, butoxyethyl group, methoxyethoxymethyl group, ethoxyethoxyethyl group, Examples thereof include a cyanoethyl group and a cyanopropyl group. Examples of R2 to R10 in the general formula (2) include a hydrogen atom,
Fluorine atom, chlorine atom, bromine atom, iodine atom, linear or branched alkyl group having 1 to 4 carbon atoms, trifluoromethyl group, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group , Heptyloxy group, octyloxy group, acetyl group, hydroxyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, dimethylamino group, diethylamino group,
Examples thereof include dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, acetylamino group, benzoylamino group, anilino group and N-methylanilino group. In the general formula (2), preferably R
1, R6 are dialkylamino groups, R2 to R5, R
7 to R10 are hydrogen atoms.
【0032】一般式(3)におけるR21〜R25の例
としては一般式(2)におけるR2〜R10と同じもの
が挙げられる。一般式(3)におけるR11〜R12及
び一般式(4)におけるR31〜R34の例としては、
炭素数1〜18の直鎖もしくは分岐のアルキル基、シク
ロヘキシル基、フェニル基、トリル基、ベンジル基、シ
アノエチル基等が挙げられる。一般式(3)において、
好ましくはR21はジアルキルアミノ基であり、R22
〜R25は水素原子であり、R11またはR12は非置
換のアルキル基または非置換のフェニル基である。Examples of R21 to R25 in the general formula (3) include the same ones as R2 to R10 in the general formula (2). Examples of R11 to R12 in the general formula (3) and R31 to R34 in the general formula (4) are:
Examples thereof include a linear or branched alkyl group having 1 to 18 carbon atoms, a cyclohexyl group, a phenyl group, a tolyl group, a benzyl group and a cyanoethyl group. In the general formula (3),
Preferably R21 is a dialkylamino group, R22
~ R25 is a hydrogen atom, and R11 or R12 is an unsubstituted alkyl group or an unsubstituted phenyl group.
【0033】一般式(5)におけるR41の例としては
一般式(2)におけるR1と同じものが挙げられる。一
般式(5)におけるR42〜R45の例としては、一般
式(2)におけるR2〜R10と同じものが挙げられ
る。Q5、Q6の例としては、水素原子、フェニル基、
ナフチル基、(ジアルキルアミノ)フェニル基、メチル
フェニル基、ジメチルフェニル基、トリメチルフェニル
基、エチルフェニル基、プロピルフェニル基、ブチルフ
ェニル基、メトキシフェニル基、エトキシフェニル基、
プロポキシフェニル基、ブトキシフェニル基、ペンチル
オキシフェニル基等が挙げられる。一般式(5)におい
て、好ましくは、R41はジアルキルアミノ基であり、
R42〜R45は水素原子であり、Q5、Q6が互いに
独立に、非置換またはアルキル基、アルコキシ基もしく
はジアルキルアミノ基のいずれかによって置換されたフ
ェニル基である。ここにおいて、更に好ましくはQ5、
Q6は互いに独立に、ジアルキルアミノ基によって置換
されたフェニル基、または水素原子である。Examples of R41 in the general formula (5) include the same as R1 in the general formula (2). Examples of R42 to R45 in the general formula (5) include the same ones as R2 to R10 in the general formula (2). Examples of Q5 and Q6 are hydrogen atom, phenyl group,
Naphthyl group, (dialkylamino) phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, methoxyphenyl group, ethoxyphenyl group,
Examples include propoxyphenyl group, butoxyphenyl group, pentyloxyphenyl group and the like. In the general formula (5), R41 is preferably a dialkylamino group,
R42 to R45 are hydrogen atoms, and Q5 and Q6 are each independently a phenyl group which is unsubstituted or substituted by any of an alkyl group, an alkoxy group or a dialkylamino group. Here, more preferably Q5,
Q6 is, independently of each other, a phenyl group substituted with a dialkylamino group, or a hydrogen atom.
【0034】[0034]
【発明の実施の形態】以上をさらに具体的に例示する
と、前記の一般式(1)及び(2)〜(5)においてそ
れぞれの置換基が下記第1表〜第3表に示すようなもの
である化合物が挙げられる。More specifically, the substituents in the above general formulas (1) and (2) to (5) are as shown in Tables 1 to 3 below. And a compound that is
【0035】[0035]
【表1】 [Table 1]
【0036】[0036]
【表2】 [Table 2]
【0037】[0037]
【表3】 [Table 3]
【0038】[0038]
【表4】 [Table 4]
【0039】[0039]
【表5】 [Table 5]
【0040】本発明のピロール化合物のうち、一般式
(1)におけるZがハロゲン原子であるものは、たとえ
ば下記のようなスキーム1〜3のいずれかにより合成す
ることができる。またZがハロゲン原子でXがシアノ基
であるものはスキーム1〜3の他、スキーム4によって
も合成することができる。Among the pyrrole compounds of the present invention, those in which Z in the general formula (1) is a halogen atom can be synthesized, for example, by any of the following schemes 1 to 3. Further, those in which Z is a halogen atom and X is a cyano group can be synthesized not only by schemes 1 to 3 but also by scheme 4.
【0041】[0041]
【化21】 [Chemical 21]
【0042】これらの反応経路において出発物質となる
ピロリノン化合物は、公知の文献たとえば「Annal
en der Chemie」260巻137−160
頁(1890年)、「Tetrahedron Let
ters」23巻、15号、1597−1600頁(1
982年)、「Synthesis」615頁(197
6年)等に記載の方法等で容易に合成することができ
る。反応式で示すと下記スキーム5のようになる。The pyrrolinone compounds used as starting materials in these reaction routes are known in the literature, for example, "Annal.
en der Chemie "260 volumes 137-160
Page (1890), "Tetrahedron Let
ters ”, Vol. 23, No. 15, pp. 1597-1600 (1
982), "Synthesis", page 615 (197).
6 years) and the like can be easily synthesized. The reaction scheme is shown in Scheme 5 below.
【0043】[0043]
【化22】 [Chemical formula 22]
【0044】式中、Rはアルキル基、アリール基等を表
し、Lはハロゲン原子を示す。最初の反応で、アシル酢
酸エステルまたはアシルアセトニトリルとハロゲン化酢
酸エステルを反応させてエステル化合物を作るが、この
ときの反応溶媒にはアルコール系、エーテル系、アミド
系、スルホキシド系、ケトン系、ニトリル系等の各種溶
媒を用いることができる。この反応は塩基で促進され、
たとえば各種ナトリウム塩、カリウム塩等の一般的な無
機塩基の他、金属アルコラートやピリジン、トリアルキ
ルアミン、環状イミン等の有機性の塩基を用いることが
できる。得られたエステル化合物に、アンモニアガスや
アンモニウム塩たとえば酢酸アンモニウム等を作用させ
て環化させることができる。このときの反応溶媒には、
アルコールや酢酸等を用いることができる。In the formula, R represents an alkyl group, an aryl group or the like, and L represents a halogen atom. In the first reaction, an acyl acetate ester or an acylacetonitrile is reacted with a halogenated acetate ester to form an ester compound, and the reaction solvent at this time is an alcohol type, an ether type, an amide type, a sulfoxide type, a ketone type, a nitrile type. Various solvents such as can be used. This reaction is promoted by base,
For example, in addition to common inorganic bases such as various sodium salts and potassium salts, organic bases such as metal alcoholates, pyridine, trialkylamines and cyclic imines can be used. The obtained ester compound can be cyclized by acting ammonia gas or an ammonium salt such as ammonium acetate. The reaction solvent at this time is
Alcohol or acetic acid can be used.
【0045】こうして得られたピロリノン化合物は分子
内に活性メチレンをもつので、スキーム1〜3に示すよ
うに、カルボニル化合物やベンズヒドロール化合物等の
求電子剤と容易に付加もしくは縮合反応を起こす。この
反応は硫酸、塩酸、酢酸、スルホン酸、酸無水物、ハロ
ゲン化リン、ハロゲン化ホスホリル、金属ハロゲン化
物、ハロゲン化チオニル、ポリリン酸等の酸や脱水剤に
よって促進される。このときハロゲン性の試薬を使う
と、付加もしくは縮合反応とハロゲン化を一浴で行うこ
ともできる。スキーム2〜3における酸化反応にはクロ
ラニル、過酸化水素、過塩素酸、ヨウ素、塩化第二鉄、
過マンガン酸カリウム等の一般的な酸化剤や空気酸化法
を用いることができる。スキーム1〜4におけるハロゲ
ン化剤としては、ハロゲン化リン、ハロゲン化ホスホリ
ル、ハロゲン化チオニル等を用いることができる。Since the pyrrolinone compound thus obtained has active methylene in the molecule, as shown in Schemes 1 to 3, it easily causes an addition or condensation reaction with an electrophile such as a carbonyl compound or a benzhydrol compound. This reaction is promoted by acids such as sulfuric acid, hydrochloric acid, acetic acid, sulfonic acid, acid anhydrides, phosphorus halides, phosphoryl halides, metal halides, thionyl halides and polyphosphoric acid, and dehydrating agents. At this time, if a halogenating reagent is used, the addition or condensation reaction and the halogenation can be carried out in one bath. The oxidation reaction in Schemes 2-3 includes chloranil, hydrogen peroxide, perchloric acid, iodine, ferric chloride,
A general oxidant such as potassium permanganate or an air oxidation method can be used. As the halogenating agent in Schemes 1 to 4, phosphorus halide, phosphoryl halide, thionyl halide and the like can be used.
【0046】以上のスキーム1〜4のいずれかの方法に
よりZがハロゲンであるピロール化合物が得られるが、
これらは活性水素をもった化合物たとえばフェノール、
チオール類と容易に反応して、Zがアリールオキシ基、
アルキルチオ基、アリールチオ基、複素環チオ基等とな
った化合物を与える。このときの反応溶媒にはアルコー
ル系、エーテル系、アミド系、スルホキシド系、ケトン
系、ニトリル系等の各種溶媒を用いることができる。こ
のとき塩基を加えると反応が促進され、たとえば各種ナ
トリウム塩、カリウム塩等の一般的な無機塩基の他、金
属アルコラートやピリジン、トリアルキルアミン、環状
イミン等の有機性の塩基を用いることができる。A pyrrole compound in which Z is a halogen is obtained by any of the above schemes 1 to 4,
These are compounds with active hydrogen such as phenol,
Easily reacts with thiols, and Z is an aryloxy group,
A compound having an alkylthio group, an arylthio group, a heterocyclic thio group or the like is provided. At this time, various solvents such as alcohol, ether, amide, sulfoxide, ketone and nitrile can be used as the reaction solvent. At this time, the reaction is promoted by adding a base, and for example, in addition to general inorganic bases such as various sodium salts and potassium salts, organic bases such as metal alcoholates, pyridine, trialkylamines and cyclic imines can be used. .
【0047】[0047]
【実施例】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)反応容器に、4,4’−ビス(ジメチルアミノ)ベ
ンズヒドロール2.7g、エタノール40ml、及び下
式で示される3−エトキシカルボニル−2−フェニル−
5−オキソ−4,5−ジヒドロ−1H−ピロール(化合
物M1とする)2.3gを仕込んだ。EXAMPLES The present invention will be described in more detail below with reference to examples. Example 1 1) In a reaction vessel, 2.7 g of 4,4'-bis (dimethylamino) benzhydrol, 40 ml of ethanol, and 3-ethoxycarbonyl-2-phenyl- represented by the following formula.
2.3 g of 5-oxo-4,5-dihydro-1H-pyrrole (designated as compound M1) was charged.
【0048】[0048]
【化23】 [Chemical formula 23]
【0049】この混合物を撹拌しながら室温で62%硫
酸5mlを滴下した後、加熱して溶媒の還流温度で6時
間攪拌した。加熱を止め冷却した後、反応液を別容器の
水500mlに撹拌しながら注加した。そこにクロロホ
ルムを加え撹拌後、クロロホルム層を除去し残った水層
に水酸化ナトリウム水溶液を加え中和すると結晶が析出
した。濾過して得られた結晶をn−ヘキサンとメタノー
ルで順次洗浄後、乾燥して4−[ビス(4−ジメチルア
ミノフェニル)メチル]−3−エトキシカルボニル−2
−フェニル−5−オキソ−4,5−ジヒドロ−1H−ピ
ロールの緑白色結晶2.7gを得た。LC/MSで48
4の質量を示すピークを確認した。なお、この場合のL
C/MSは酢酸を含む溶媒を用いた化学イオン化法によ
るポジティブイオンモードで分析しているため、化合物
がプロトン化されたものの質量、すなわち化合物の分子
量より1大きい値(MH+)が検出されている。以後の
分析においても同様である。While stirring the mixture, 5 ml of 62% sulfuric acid was added dropwise at room temperature, and then the mixture was heated and stirred at the reflux temperature of the solvent for 6 hours. After stopping the heating and cooling, the reaction solution was poured into 500 ml of water in another container while stirring. Chloroform was added thereto, the mixture was stirred, the chloroform layer was removed, and the remaining aqueous layer was neutralized with an aqueous sodium hydroxide solution to precipitate crystals. The crystals obtained by filtration are washed successively with n-hexane and methanol and then dried to give 4- [bis (4-dimethylaminophenyl) methyl] -3-ethoxycarbonyl-2.
2.7 g of green-white crystals of -phenyl-5-oxo-4,5-dihydro-1H-pyrrole were obtained. 48 by LC / MS
The peak showing the mass of 4 was confirmed. In this case, L
Since C / MS is analyzed in the positive ion mode by the chemical ionization method using a solvent containing acetic acid, the mass of the compound protonated, that is, a value (MH + ) larger than the molecular weight of the compound by 1 is detected. There is. The same applies to subsequent analyzes.
【0050】2)反応容器に1)で得られた結晶1.9
0g、エタノール30ml、トルエン20mlを仕込み
撹拌しながら40℃に昇温した。ここにクロラニル1.
45gを少しずつ加えた後、温度を50℃に上げ1.5
時間撹拌後、放冷した。反応液を濃縮後、酢酸エチルを
加え撹拌して析出した結晶を濾取、乾燥して4−[ビス
(4−ジメチルアミノフェニル)メチリデン]−3−エ
トキシカルボニル−2−フェニル−5−オキソ−4,5
−ジヒドロ−1H−ピロールの赤色結晶1.6gを得
た。LC/MSで482(MH+)の質量を示すピーク
を確認した。2) 1.9 crystals obtained in 1) in a reaction vessel
0 g, 30 ml of ethanol and 20 ml of toluene were charged and the temperature was raised to 40 ° C. with stirring. Chloranil 1.
After adding 45 g little by little, raise the temperature to 50 ° C.
After stirring for an hour, the mixture was allowed to cool. The reaction mixture was concentrated, ethyl acetate was added and the mixture was stirred and the precipitated crystals were collected by filtration and dried to give 4- [bis (4-dimethylaminophenyl) methylidene] -3-ethoxycarbonyl-2-phenyl-5-oxo-. 4,5
1.6 g of red crystals of dihydro-1H-pyrrole were obtained. A peak showing a mass of 482 (MH + ) was confirmed by LC / MS.
【0051】3)反応容器に2)で得られた結晶0.3
g、トルエン13mlを仕込み撹拌しながら塩化ホスホ
リル3.3mlを滴下した。加熱して70℃にして1時
間撹拌後、加熱を止め反応液を放冷し、水、クロロホル
ムを加え、水酸化ナトリウム水溶液で中和してしばらく
攪拌した後、有機層を分取し水洗、濃縮して下記構造式
で示される2−クロロ−3−[ビス(4−ジメチルアミ
ノフェニル)メチリデン]−4−エトキシカルボニル−
5−フェニル−3H−ピロール(化合物A1)の黒緑色
結晶0.30gを得た。LC/MSで500(MH+)
の質量を示すピークを確認した。3) 0.3 crystal in the reaction vessel obtained in 2)
g and 13 ml of toluene were charged, and 3.3 ml of phosphoryl chloride was added dropwise with stirring. After heating to 70 ° C. and stirring for 1 hour, heating was stopped and the reaction solution was allowed to cool, water and chloroform were added, neutralized with aqueous sodium hydroxide solution and stirred for a while, then the organic layer was separated and washed with water, 2-Chloro-3- [bis (4-dimethylaminophenyl) methylidene] -4-ethoxycarbonyl-concentrated and represented by the following structural formula
0.30 g of black-green crystals of 5-phenyl-3H-pyrrole (Compound A1) was obtained. 500 (MH + ) by LC / MS
The peak showing the mass of was confirmed.
【0052】[0052]
【化24】 [Chemical formula 24]
【0053】この化合物はクロロホルム、アセトン、テ
トラヒドロフランのいずれの溶剤にも1%以上溶解し
た。この化合物の極大吸収波長(λmax)は538n
m、608nmであった。またNMR分析の結果は次の
ようであった。1H−NMR(CDCl3,300MH
z,ppm),:δ0.85(t,J=7.2Hz,3
H),3.29(s,12H),3.67(q,J=
7.14Hz,2H),6.92(d,J=9.2H
z,4H),7.27−7.40(m,3H),7.4
9(d,J=9.2Hz,4H),7.80(d,J=
6.8Hz,2H)。この化合物の赤外吸収スペクトル
(KBr)を後記図1に示す。This compound was dissolved in 1% or more of any solvent of chloroform, acetone and tetrahydrofuran. The maximum absorption wavelength (λmax) of this compound is 538n.
m, 608 nm. The results of NMR analysis were as follows. 1 H-NMR (CDCl 3 , 300 MH
z, ppm), δ 0.85 (t, J = 7.2 Hz, 3
H), 3.29 (s, 12H), 3.67 (q, J =
7.14 Hz, 2H), 6.92 (d, J = 9.2H)
z, 4H), 7.27-7.40 (m, 3H), 7.4.
9 (d, J = 9.2 Hz, 4H), 7.80 (d, J =
6.8 Hz, 2H). The infrared absorption spectrum (KBr) of this compound is shown in FIG. 1 below.
【0054】実施例2(実施例1とは別の合成法による
化合物A1の合成)
反応容器に塩化ホスホリル50ml、化合物M1を6.
1g、4,4’−ビス(ジメチルアミノ)ベンゾフェノ
ン7.1gを仕込み、50〜60℃で4時間攪拌した
後、加熱を止め放冷した反応液を別容器の冷水300m
lに少しずつ滴下し、その後、水酸化ナトリウム水溶液
を加え中和して3時間撹拌した後、クロロホルムで抽出
した。有機層を水洗、脱水、濃縮後、得られたタール状
物質にトルエンとヘキサンの混合溶剤を加えかき混ぜた
後、デカンテーションで上澄み液を除き残留物にヘキサ
ンを加えて結晶を析出させた。濾過して得られた結晶を
ヘキサンとトルエンの混合溶媒中で加熱しながらしばら
く撹拌した後、放冷して濾過、乾燥して黒緑色結晶7.
3gを得た。この化合物は実施例1の3)で得た化合物
と、LC分析の保持時間、LC/MS分析値、NMR分
析値、赤外吸収スペクトル、可視吸収スペクトルが一致
しており同一化合物であることが確認された。また元素
分析値は次のようであった。
C% H% N% O% Cl%
分析値71.46 6.03 8.13 6.76 6.80
計算値72.06 6.05 8.40 6.40 7.09
(C30H30ClN3O2として)Example 2 (Synthesis of Compound A1 by a Synthesis Method Different from Example 1) 50 ml of phosphoryl chloride and 6.
1 g and 4,4′-bis (dimethylamino) benzophenone (7.1 g) were charged, the mixture was stirred at 50 to 60 ° C. for 4 hours, the heating was stopped, and the reaction liquid was allowed to cool.
Then, the mixture was added dropwise to 1 liter, neutralized with an aqueous sodium hydroxide solution, stirred for 3 hours, and then extracted with chloroform. The organic layer was washed with water, dehydrated and concentrated, and then a mixed solvent of toluene and hexane was added to the obtained tar-like substance and the mixture was stirred, and then the supernatant was removed by decantation and hexane was added to the residue to precipitate crystals. The crystals obtained by filtration are stirred for a while while being heated in a mixed solvent of hexane and toluene, then allowed to cool, filtered and dried to give black-green crystals 7.
3 g was obtained. This compound has the same retention time for LC analysis, LC / MS analysis value, NMR analysis value, infrared absorption spectrum, and visible absorption spectrum as those of the compound obtained in 3) of Example 1, and thus is the same compound. confirmed. The elemental analysis values were as follows. C% H% N% O% Cl% analytical value 71.46 6.03 8.13 6.76 6.80 calculated value 72.06 6.05 8.40 6.40 7.09 (C 30 H 30 ClN 3 O 2 )
【0055】実施例3
反応容器に、実施例2と同様にして得た化合物A1を
1.0g、N,N−ジメチルホルムアミド(以下DMF
と略)6ml、無水炭酸カリウム0.55gを仕込み撹
拌しながら4−t−ブチルチオフェノール0.35gを
少しずつ加えた後、室温で1.5時間撹拌した。反応液
を水200mlに注加し析出した結晶を濾過して分離し
ヘキサンで洗浄、乾燥して下記構造式で示される化合物
の黒緑色結晶0.56gを得た。Example 3 In a reaction vessel, 1.0 g of the compound A1 obtained in the same manner as in Example 2 was added and N, N-dimethylformamide (hereinafter referred to as DMF).
6 ml and 0.55 g of anhydrous potassium carbonate were charged, 0.35 g of 4-t-butylthiophenol was added little by little while stirring, and the mixture was stirred at room temperature for 1.5 hours. The reaction solution was poured into 200 ml of water, and the precipitated crystal was filtered, separated, washed with hexane and dried to obtain 0.56 g of a black green crystal compound of the following structural formula.
【0056】[0056]
【化25】 [Chemical 25]
【0057】LC/MSで630(MH+)のピークを
確認した。この化合物のメタノール溶液のλmaxは6
17nmであった。また元素分析値は次のようであっ
た。
C% H% N% O% S%
分析値75.11 6.22 7.10 5.84 5.44
計算値76.28 6.88 6.67 5.08 5.09
(C40H43N3O2Sとして)A peak of 630 (MH + ) was confirmed by LC / MS. Λmax of methanol solution of this compound is 6
It was 17 nm. The elemental analysis values were as follows. C% H% N% O% S% Analytical value 75.11 6.22 7.10 5.84 5.44 Calculated value 76.28 6.88 6.67 5.08 5.09 (C 40 H 43 N As 3 O 2 S)
【0058】実施例4
反応容器に実施例2と同様にして得た化合物A1を1.
0g、DMF2ml、炭酸カリウム0.55gを仕込み
撹拌しながら4−メルカプト安息香酸0.32gを1時
間で加えた。さらに1時間撹拌後、反応液を濾過し濾液
をエバポレーターで濃縮し残留物に食塩水を加え析出し
た結晶を濾別し少量の水で洗浄した。結晶を乾燥後、ア
セトンとメタノールの混合溶媒に溶かして不溶物を濾別
し濾液を濃縮して得られた結晶をヘキサンにほぐして濾
別、乾燥して下記構造式の化合物A3の黒緑色結晶1.
1gを得た。LC/MSで618(MH+)のピークを
確認した。この化合物はメタノールに1%以上溶解し
た。この化合物のメタノール溶液のλmaxは620n
mでありその波長でのモル吸光係数εは100000で
あった。またアセトン溶液のλmaxは521nm(ε
=65000)でありその吸収ピークの610nm付近
に肩があった。この化合物のメタノール溶液の可視吸収
スペクトルを図3に示す。またDSC分析で発熱ピーク
が観測されそのピーク温度は250℃、発熱量は110
J/g(窒素雰囲気下)であった。Example 4 Into a reaction vessel, the compound A1 obtained in the same manner as in Example 2 was added.
0 g, DMF (2 ml) and potassium carbonate (0.55 g) were charged, and 4-mercaptobenzoic acid (0.32 g) was added over 1 hour while stirring. After stirring for an additional 1 hour, the reaction solution was filtered, the filtrate was concentrated with an evaporator, brine was added to the residue, and the precipitated crystals were separated by filtration and washed with a small amount of water. After the crystals were dried, they were dissolved in a mixed solvent of acetone and methanol, the insoluble matter was filtered off, the filtrate was concentrated, and the crystals obtained were disentangled in hexane, filtered off, and dried to obtain black green crystals of compound A3 of the following structural formula. 1.
1 g was obtained. A peak of 618 (MH + ) was confirmed by LC / MS. This compound was dissolved in methanol at 1% or more. Λmax of the methanol solution of this compound is 620n
m and the molar extinction coefficient ε at that wavelength was 100,000. The λmax of the acetone solution is 521 nm (ε
= 65000) and there was a shoulder near the absorption peak at 610 nm. The visible absorption spectrum of a methanol solution of this compound is shown in FIG. An exothermic peak was observed by DSC analysis, the peak temperature was 250 ° C, and the calorific value was 110.
It was J / g (under nitrogen atmosphere).
【0059】[0059]
【化26】 [Chemical formula 26]
【0060】実施例5
実施例2と同様にして得た化合物A1の結晶0.5g、
炭酸カリウム0.28g、2−メルカプトベンゾチアゾ
ール0.8g、DMF5mlを混合し80〜90℃で3
時間撹拌後、約200mlの水で希釈、撹拌、濾過、乾
燥して粗結晶を得た。これをシリカゲルカラムクロマト
グラフィで精製して(展開溶媒クロロホルム:メタノー
ル=30:1〜10:1)下記構造式で表される化合物
A5の結晶0.56gを得た。この化合物のλmaxは
メタノール中で625nm、アセトン中で520nmで
あった。Example 5 0.5 g of crystals of compound A1 obtained in the same manner as in Example 2,
0.28 g of potassium carbonate, 0.8 g of 2-mercaptobenzothiazole and 5 ml of DMF were mixed and the mixture was mixed at 80 to 90 ° C.
After stirring for an hour, the mixture was diluted with about 200 ml of water, stirred, filtered, and dried to obtain crude crystals. This was purified by silica gel column chromatography (developing solvent chloroform: methanol = 30: 1 to 10: 1) to obtain 0.56 g of a crystal of compound A5 represented by the following structural formula. The λmax of this compound was 625 nm in methanol and 520 nm in acetone.
【0061】[0061]
【化27】 [Chemical 27]
【0062】実施例6
実施例2と同様にして得られた化合物A1の結晶0.2
5g、メタノール2ml、炭酸カリウム0.69g、チ
オグリコール酸ナトリウム塩0.57gを混合し70℃
で9時間撹拌後、反応液を濃縮し水を加え濾過して粗結
晶0.22gを得た。これをシリカゲルカラムクロマト
グラフィで精製して(展開溶媒クロロホルム−メタノー
ル)前記第1表に示す化合物A4の黒緑色結晶0.24
gを得た。この化合物のλmaxはメタノール中で59
8nm、アセトン中で531nmであった。Example 6 0.2 crystal of compound A1 obtained in the same manner as in Example 2
5 g, 2 ml of methanol, 0.69 g of potassium carbonate, 0.57 g of sodium thioglycolic acid salt are mixed and mixed at 70 ° C.
After stirring for 9 hours, the reaction mixture was concentrated, water was added, and the mixture was filtered to obtain 0.22 g of crude crystals. This was purified by silica gel column chromatography (developing solvent chloroform-methanol) to give a black green crystal of compound A4 shown in Table 1 (0.24).
g was obtained. The λmax of this compound is 59 in methanol.
8 nm, 531 nm in acetone.
【0063】実施例7
実施例2の化合物M1の代わりに同モル数の3−メトキ
シカルボニル−2−(4−シアノフェニル)−5−オキ
ソ−4,5−ジヒドロ−1H−ピロールを用いた他は実
施例2と同様に操作して前記第1表の化合物A11の結
晶6.7gを得た。この化合物のメタノール溶液のλm
axは557nmであった。この溶液に少量の塩酸を加
えるとλmaxは618nmにシフトした。Example 7 In place of the compound M1 of Example 2, the same mole number of 3-methoxycarbonyl-2- (4-cyanophenyl) -5-oxo-4,5-dihydro-1H-pyrrole was used. Was operated in the same manner as in Example 2 to obtain 6.7 g of crystals of the compound A11 in Table 1 above. Λm of methanol solution of this compound
ax was 557 nm. When a small amount of hydrochloric acid was added to this solution, λmax shifted to 618 nm.
【0064】実施例8
実施例2と同様にして得られた化合物A1の結晶0.1
5g、t−ブチルアルコール5ml、カリウムt−ブト
キシド0.15gを混合し、還流温度まで昇温して6時
間撹拌した。カリウムt−ブトキシド0.07gを追加
し、更に1時間撹拌後、反応液を放冷し、水を加え希硫
酸で弱酸性にしてクロロホルムで抽出した。有機層を濃
縮し、残留物をヘキサンでほぐし濾過した。結晶を乾燥
して前記第1表に示す化合物A12の青黒色結晶0.1
0gを得た。この化合物のλmaxは600nm(メタ
ノール)であった。LC/MSで472(MH+)のピ
ークを確認した。NMR分析結果は次のようであった。
1H−NMR(DMSO−d6):δ2.89(s,1
2H),6.71(d,J=9Hz,4H),7.16
(d,J=9.0Hz,4H),7.36(t,J=
7.5Hz,1H),7.47(t,J=7.6Hz,
2H),8.13(d,J=7.4Hz,2H),1
2.85(s,1H)。Example 8 Crystal of compound A1 obtained in the same manner as in Example 2 0.1
5 g, 5 ml of t-butyl alcohol, and 0.15 g of potassium t-butoxide were mixed, the temperature was raised to the reflux temperature, and the mixture was stirred for 6 hours. After adding 0.07 g of potassium t-butoxide and further stirring for 1 hour, the reaction solution was allowed to cool, water was added to make it weakly acidic with dilute sulfuric acid, and the mixture was extracted with chloroform. The organic layer was concentrated, the residue was triturated with hexane and filtered. The crystals were dried to give blue-black crystals of compound A12 shown in Table 1 above 0.1
0 g was obtained. The λmax of this compound was 600 nm (methanol). A peak of 472 (MH + ) was confirmed by LC / MS. The NMR analysis results were as follows.
1 H-NMR (DMSO-d6): δ 2.89 (s, 1
2H), 6.71 (d, J = 9Hz, 4H), 7.16
(D, J = 9.0 Hz, 4 H), 7.36 (t, J =
7.5 Hz, 1 H), 7.47 (t, J = 7.6 Hz,
2H), 8.13 (d, J = 7.4Hz, 2H), 1
2.85 (s, 1H).
【0065】実施例9
反応容器に塩化ホスホリル8mlを仕込み撹拌しながら
4,4’−ビス(ジメチルアミノ)ベンゾフェノン1.
0gを加え、さらに3−エトキシカルボニル−2−メチ
ル−5−オキソ−4,5−ジヒドロ−1H−ピロール
0.99gを少しずつ加えた。その後、昇温して40〜
50℃で1.5時間撹拌した後、3−エトキシカルボニ
ル−2−メチル−5−オキソ−4,5−ジヒドロ−1H
−ピロール0.33gを追加し50〜60℃で1.5時
間撹拌した。加熱を止め放冷し冷水100mlに滴下し
クロロホルムを加え水酸化ナトリウム水溶液で中和して
一晩撹拌した。クロロホルム層を分取し水洗後、脱水、
濃縮した。残留物をアセトン、ヘキサンの混合溶媒でほ
ぐし上澄み液を捨てた後、ヘキサンを加え結晶化し濾
過、乾燥して前記第1表に示す化合物A13の結晶1.
5gを得た。Example 9 Phosphoryl chloride (8 ml) was charged into a reaction vessel and stirred to obtain 4,4'-bis (dimethylamino) benzophenone.
0 g was added, and 0.99 g of 3-ethoxycarbonyl-2-methyl-5-oxo-4,5-dihydro-1H-pyrrole was added little by little. Then, raise the temperature to 40 ~
After stirring for 1.5 hours at 50 ° C., 3-ethoxycarbonyl-2-methyl-5-oxo-4,5-dihydro-1H
-Pyrrole 0.33g was added and it stirred at 50-60 degreeC for 1.5 hours. The heating was stopped, the mixture was allowed to cool, added dropwise to 100 ml of cold water, chloroform was added, the mixture was neutralized with an aqueous sodium hydroxide solution, and the mixture was stirred overnight. The chloroform layer is separated, washed with water, dehydrated,
Concentrated. The residue was triturated with a mixed solvent of acetone and hexane, the supernatant was discarded, hexane was added, and the mixture was crystallized, filtered and dried to give a crystal of compound A13 shown in Table 1.
5 g was obtained.
【0066】実施例10
化合物M1を1.2g、4,4’−ビス[N−メチル−
N−(4−メトキシフェニル)アミノ]ベンゾフェノン
2.3g、塩化ホスホリル15mlを混合し撹拌しなが
ら昇温した。80℃で3時間、105℃で9時間撹拌し
た後、放冷して冷水に排出した。水酸化ナトリウムで中
和しクロロホルムを加え撹拌後、有機層を分取し活性白
土を加え撹拌、濾過した。濾液を濃縮し乾燥して、前記
第1表に示す化合物A9の黒紫色結晶0.66gを得
た。Example 10 1.2 g of compound M1, 4,4'-bis [N-methyl-
2.3 g of N- (4-methoxyphenyl) amino] benzophenone and 15 ml of phosphoryl chloride were mixed and heated with stirring. After stirring at 80 ° C for 3 hours and at 105 ° C for 9 hours, the mixture was allowed to cool and discharged into cold water. After neutralizing with sodium hydroxide and adding chloroform, the mixture was stirred, the organic layer was separated, activated clay was added, and the mixture was stirred and filtered. The filtrate was concentrated and dried to obtain 0.66 g of black violet crystals of compound A9 shown in Table 1 above.
【0067】実施例11
化合物M1を0.71g、4,4’−ビス(N−フェニ
ル−N−メチルアミノ)ベンゾフェノン1.2gを塩化
ホスホリル20mlと混合し75℃で4時間撹拌した
後、放冷した。反応液を冷水に滴下し水酸化ナトリウム
水溶液で中和し析出した結晶を濾別した。結晶をトルエ
ンに溶解し活性白土を加え撹拌、濾過した。活性白土層
に吸着された色素をクロロホルム、アセトン、DMFを
用いて脱着し、水で希釈後、トルエンで抽出し濃縮して
前記第1表に示す化合物A10の黒紫色結晶0.96g
を得た。LC/MSで624(MH+)のピークを確認
した。またDSC分析で発熱ピークが観測されピーク温
度は260℃、発熱量は186J/g(窒素雰囲気下)
であった。この化合物のλmaxはメタノール中で53
5nm、メタノールと酢酸の混合溶媒中で617nmで
あった。Example 11 0.71 g of compound M1 and 1.2 g of 4,4'-bis (N-phenyl-N-methylamino) benzophenone were mixed with 20 ml of phosphoryl chloride and stirred at 75 ° C. for 4 hours and then released. Chilled The reaction solution was added dropwise to cold water, neutralized with an aqueous sodium hydroxide solution, and the precipitated crystals were separated by filtration. The crystals were dissolved in toluene, activated clay was added, and the mixture was stirred and filtered. The dye adsorbed on the activated clay layer was desorbed with chloroform, acetone and DMF, diluted with water, extracted with toluene and concentrated to give 0.96 g of black violet crystals of compound A10 shown in Table 1 above.
Got A peak of 624 (MH + ) was confirmed by LC / MS. An exothermic peak was observed by DSC analysis, the peak temperature was 260 ° C, and the exothermic amount was 186 J / g (in a nitrogen atmosphere).
Met. The λmax of this compound is 53 in methanol.
5 nm and 617 nm in a mixed solvent of methanol and acetic acid.
【0068】実施例12
3−ヘプチルオシカルボニル−2−メチル−5−オキソ
−4,5−ジヒドロ−1H−ピロール0.16g、4,
4’−(ジメチルアミノ)ベンゾフェノン0.13g、
塩化ホスホリル1mlを混合し撹拌しながら昇温した。
70℃で3時間撹拌した後、放冷し水に排出しクロロホ
ルムを加え水酸化ナトリウムで中和してしばらく撹拌し
た。有機層を抽出、不溶分を濾去した後、濃縮、乾燥し
て前記第1表に示す化合物A15の青黒色結晶0.12
gを得た。Example 12 3-heptyl oxycarbonyl-2-methyl-5-oxo-4,5-dihydro-1H-pyrrole 0.16 g, 4,
0.13 g of 4 '-(dimethylamino) benzophenone,
1 ml of phosphoryl chloride was mixed and heated with stirring.
After stirring at 70 ° C. for 3 hours, the mixture was allowed to cool, discharged into water, chloroform was added, and the mixture was neutralized with sodium hydroxide and stirred for a while. The organic layer was extracted, the insoluble matter was removed by filtration, then concentrated and dried to give a blue-black crystal of Compound A15 shown in Table 1 0.12.
g was obtained.
【0069】実施例13
実施例12の3−ヘプチルオキシカルボニル−2−メチ
ル−5−オキソ−4,5−ジヒドロ−1H−ピロールに
代えて、3−エトキシカルボニル−2−(4−シアノフ
ェニル)−5−オキソ−4,5−ジヒドロ−1H−ピロ
ールを用い、他は実施例12と同様に操作して前記第1
表に示す化合物A11の黒紫色結晶を得た。この化合物
のλmaxはメタノール中で557nm、メタノールと
酢酸の混合溶媒中で618nmであった。Example 13 In place of 3-heptyloxycarbonyl-2-methyl-5-oxo-4,5-dihydro-1H-pyrrole of Example 12, 3-ethoxycarbonyl-2- (4-cyanophenyl) is used. Using 5-5-oxo-4,5-dihydro-1H-pyrrole, the same procedure as in Example 12 was repeated except that the above-mentioned first compound was used.
Black purple crystals of compound A11 shown in the table were obtained. The λmax of this compound was 557 nm in methanol and 618 nm in a mixed solvent of methanol and acetic acid.
【0070】実施例14
実施例5の2−メルカプトベンゾチアゾールの代わりに
2−メルカプトベンゾキサゾールを用い、他は実施例5
と同様に操作して前記第1表に示す化合物A6の黒緑色
結晶を得た。この化合物のλmaxは623nm(メタ
ノール)であった。Example 14 In place of the 2-mercaptobenzothiazole of Example 5, 2-mercaptobenzoxazole was used, and the other conditions of Example 5 were used.
The same procedure as described above was performed to obtain black green crystals of compound A6 shown in Table 1. The λmax of this compound was 623 nm (methanol).
【0071】実施例15
反応容器に化合物A1を0.50g、DMF3ml、無
水炭酸カリウム0.55gを仕込み撹拌しながら2−メ
ルカプト安息香算0.23gを少しずつ加えた後、室温
で1時間。70〜80℃で4時間撹拌した。反応液を水
に注加し析出した結晶を濾過して分離し少量のメタノー
ルで洗浄、乾燥して前記第1表に示す化合物A29の黒
緑色結晶0.24gを得た。この化合物のλmaxは6
13nm(メタノール)であった。Example 15 To a reaction vessel, 0.50 g of compound A1, 3 ml of DMF and 0.55 g of anhydrous potassium carbonate were charged, and 0.23 g of 2-mercaptobenzoate was added little by little while stirring, and then at room temperature for 1 hour. It stirred at 70-80 degreeC for 4 hours. The reaction solution was poured into water, and the precipitated crystals were separated by filtration, washed with a small amount of methanol and dried to obtain 0.24 g of black green crystals of compound A29 shown in Table 1 above. Λmax of this compound is 6
It was 13 nm (methanol).
【0072】実施例16
実施例2の4,4’−ビス(ジメチルアミノ)ベンゾフ
ェノンの代わりに4,4’−ビス(ジエチルアミノ)ベ
ンゾフェノンを用いて前記第1表に示す化合物A7の黒
緑色結晶7.5gを得た。この化合物のλmaxは62
1nm(メタノール)であった。Example 16 Black green crystals 7 of compound A7 shown in Table 1 above were replaced with 4,4'-bis (diethylamino) benzophenone in place of 4,4'-bis (dimethylamino) benzophenone of Example 2. 0.5 g was obtained. Λmax of this compound is 62
It was 1 nm (methanol).
【0073】実施例17
反応容器に3−シアノ−2−フェニル−5−オキソ−
4,5−ジヒドロ−1H−ピロール0.69g、4,
4’−ビス(ジメチルアミノ)ベンゾフェノン1.0
g、塩化ホスホリル20mlを仕込み撹拌しながら75
℃に昇温した。2時間撹拌した後、加熱を止め放冷後、
反応液を冷水に少しずつ加え、水酸化ナトリウム水溶液
で弱アルカリ性とした後、クロロホルムで抽出した。有
機層を乾燥後、濃縮し、得られた結晶をクロロホルムに
溶解し、活性白土を加え撹拌した。濾過して活性白土層
を分離しそれにDMFを加えて撹拌した後、活性白土を
濾去し、濾液に水、トルエンを加え撹拌した。有機層を
分取、濃縮して前記第1表に示す化合物A21の黒紫色
結晶0.74gを得た。LC/MSで453(MH+)
のピークを確認した。NMRの分析結果は次のようであ
った。1H−NMR(CDCl3):δ3.14(s,
12H),6.74(d,J=8.9Hz,4H),
7.26−7.42(m,7H),8.22(d,J=
7.4Hz,2H)。この化合物のλmaxは565n
m(メタノール)であった。Example 17 3-Cyano-2-phenyl-5-oxo-in a reaction vessel
4,5-dihydro-1H-pyrrole 0.69 g, 4,
4'-bis (dimethylamino) benzophenone 1.0
g, 20 ml of phosphoryl chloride, and with stirring, 75
The temperature was raised to ° C. After stirring for 2 hours, stop heating and allow to cool,
The reaction solution was added little by little to cold water, made weakly alkaline with an aqueous sodium hydroxide solution, and then extracted with chloroform. The organic layer was dried and then concentrated, and the obtained crystals were dissolved in chloroform, activated clay was added, and the mixture was stirred. The activated clay layer was separated by filtration, DMF was added thereto and the mixture was stirred, then the activated clay was filtered off, and water and toluene were added to the filtrate and the mixture was stirred. The organic layer was separated and concentrated to obtain 0.74 g of black purple crystals of compound A21 shown in Table 1 above. 453 (MH + ) by LC / MS
Was confirmed. The NMR analysis results were as follows. 1 H-NMR (CDCl 3 ): δ3.14 (s,
12H), 6.74 (d, J = 8.9Hz, 4H),
7.26-7.42 (m, 7H), 8.22 (d, J =
7.4 Hz, 2H). Λmax of this compound is 565n
It was m (methanol).
【0074】実施例18
実施例17で得た化合物A21の結晶0.45g、2−
メルカプトベンゾチアゾール0.84g、DMF5m
l、炭酸カリウム0.30gを混合し60〜70℃で5
時間撹拌した。反応液を放冷後、水で希釈し析出した結
晶を濾別、乾燥後、カラムクロマトグラフィで精製して
第1表に示す化合物A22の結晶0.21gを得た。こ
の化合物のλmaxは594nm(メタノール)であっ
た。Example 18 0.45 g of crystals of the compound A21 obtained in Example 17, 2-
Mercaptobenzothiazole 0.84g, DMF5m
1 and 0.30 g of potassium carbonate were mixed, and the mixture was mixed at 60 to 70 ° C.
Stir for hours. The reaction solution was allowed to cool, diluted with water, the precipitated crystals were filtered off, dried and purified by column chromatography to obtain 0.21 g of the compound A22 crystals shown in Table 1. The λmax of this compound was 594 nm (methanol).
【0075】実施例19
実施例2の4,4’−ビス(ジメチルアミノ)ベンゾフ
ェノンに代えて、同モル数の4−(ジメチルアミノ)−
4’−メトキシベンゾフェノンを用い、他は実施例2と
同様に操作して第1表に示す化合物A19の赤黒色結晶
を得た。Example 19 In place of 4,4'-bis (dimethylamino) benzophenone of Example 2, the same mole number of 4- (dimethylamino)-was used.
Using 4'-methoxybenzophenone, the same operation as in Example 2 was carried out otherwise to obtain red-black crystals of compound A19 shown in Table 1.
【0076】実施例20
実施例2の4,4’−ビス(ジメチルアミノ)ベンゾフ
ェノンに代えて、同モル数の4,4’−ビス(ジヘキシ
ルアミノ)ベンゾフェノンを用い、他は実施例2と同様
に操作して第1表に示す化合物A14の黒緑色結晶を得
た。Example 20 In place of 4,4'-bis (dimethylamino) benzophenone of Example 2, the same mol number of 4,4'-bis (dihexylamino) benzophenone was used, and the same as Example 2 except for the above. After that, black green crystals of compound A14 shown in Table 1 were obtained.
【0077】実施例21
1)無水酢酸35ml、3,3−ビス(4−ジメチルア
ミノフェニル)−2−プロペナール3.5g、化合物M
1の結晶2.7gを混合し、60〜70℃で19時間撹
拌したのち反応液を放冷し濾過して得られた結晶を水、
メタノールで洗浄、乾燥して、4−[3,3−ビス(4
−ジメチルアミノフェニル)−2−プロペニリデン]−
3−エトキシカルボニル−2−フェニル−5−オキソ−
4,5−ジヒドロ−1H−ピロールの赤黒色結晶4.9
gを得た。LC/MSで508(MH+)のピークを確
認した。Example 21 1) Acetic anhydride 35 ml, 3,3-bis (4-dimethylaminophenyl) -2-propenal 3.5 g, compound M
2.7 g of the crystals of No. 1 were mixed and stirred at 60 to 70 ° C. for 19 hours, and then the reaction solution was allowed to cool and filtered, and the obtained crystals were water,
After washing with methanol and drying, 4- [3,3-bis (4
-Dimethylaminophenyl) -2-propenylidene]-
3-ethoxycarbonyl-2-phenyl-5-oxo-
Red-black crystal of 4,5-dihydro-1H-pyrrole 4.9
g was obtained. A peak of 508 (MH + ) was confirmed by LC / MS.
【0078】2)上記1)で得た結晶4.9g、トルエ
ン110mlを混合し撹拌しながら塩化ホスホリル40
mlを2時間で滴下した。続いて90℃まで昇温し、同
温度で5時間撹拌後、加熱を止め塩化ホスホリル10m
lを20分かけて追加し再度、昇温し90℃で1.5時
間撹拌した。加熱を止め反応液を冷水に少しずつ滴下し
た後、水酸化ナトリウム水溶液で中和して1時間撹拌
後、析出した結晶を濾取、水洗した。この結晶をメタノ
ールに溶かし不溶分を濾別し、濾液を濃縮して得られた
結晶をヘキサンとアセトンの混合溶剤で洗浄、乾燥して
下記構造式で示される化合物B1の黒緑色結晶3.2g
を得た。2) 4.9 g of the crystals obtained in 1) above and 110 ml of toluene were mixed and stirred with phosphoryl chloride 40.
ml was added dropwise over 2 hours. Subsequently, the temperature was raised to 90 ° C., and after stirring at the same temperature for 5 hours, the heating was stopped and phosphoryl chloride 10 m
1 was added over 20 minutes, the temperature was raised again, and the mixture was stirred at 90 ° C. for 1.5 hours. After stopping the heating, the reaction solution was gradually added dropwise to cold water, neutralized with an aqueous sodium hydroxide solution and stirred for 1 hour, and then the precipitated crystals were collected by filtration and washed with water. The crystals were dissolved in methanol, the insolubles were filtered off, the filtrate was concentrated, the crystals obtained were washed with a mixed solvent of hexane and acetone, and dried to give 3.2 g of black green crystals of compound B1 represented by the following structural formula.
Got
【0079】[0079]
【化28】 [Chemical 28]
【0080】この化合物のメタノール中でのλmaxは
640nmであり、pH依存性はほとんどなかった。ま
たアセトン中でのλmaxは639nmであり、メタノ
ール中とほとんど差はなかった。DSC分析では発熱ピ
ークが観測されピーク温度は194℃、発熱量は108
J/g(窒素雰囲気下)であった。LC/MSで526
のピーク(MH+)を確認した。また元素分析、NMR
分析の結果は下記のようであった。
C% H% N% O% Cl%
分析値72.61 6.11 7.90 5.86 7.11
計算値73.06 6.13 7.99 6.08 6.74
(C32H32ClN3O2として)1
H−NMR(CDCl3):δ1.07(t,J=
6.0Hz,3H),3.08(s,12H),4.1
6(q,J=6.6,2H),6.73(d,J=8.
3,4H),7.27−7.40(m,7H),7.7
7(d,J=7.9Hz,1H),7.78(d,J=
8.3Hz,1H),7.97(br,2H)。The λmax of this compound in methanol was 640 nm, and there was almost no pH dependence. Further, λmax in acetone was 639 nm, which was almost the same as that in methanol. An exothermic peak was observed by DSC analysis, the peak temperature was 194 ° C., and the calorific value was 108.
It was J / g (under nitrogen atmosphere). 526 by LC / MS
Was confirmed (MH + ). Elemental analysis, NMR
The results of the analysis were as follows. C% H% N% O% Cl% Analytical value 72.61 6.11 7.90 5.86 7.11 Calculated 73.06 6.13 7.99 6.08 6.74 (C 32 H 32 ClN 3 O 2 ) 1 H-NMR (CDCl 3 ): δ1.07 (t, J =
6.0 Hz, 3H), 3.08 (s, 12H), 4.1
6 (q, J = 6.6, 2H), 6.73 (d, J = 8.
3,4H), 7.27-7.40 (m, 7H), 7.7.
7 (d, J = 7.9 Hz, 1H), 7.78 (d, J =
8.3 Hz, 1H), 7.97 (br, 2H).
【0081】実施例22
実施例21で得た化合物B1の結晶0.80g、DMF
7ml、無水炭酸カリウム0.42gを混合し撹拌しな
がら4−メルカプト安息香酸0.25gを15分で加
え、その後1時間撹拌した。反応液に水20mlを滴下
し希硫酸でpH4程度にして撹拌、濾過した。結晶を乾
燥して第2表に示す化合物B5を1.1g得た。この化
合物はメタノールに1%以上溶解した。メタノール溶液
のλmaxは648nmであった。Example 22 0.80 g of crystals of the compound B1 obtained in Example 21, DMF
7 ml and 0.42 g of anhydrous potassium carbonate were mixed, and 0.25 g of 4-mercaptobenzoic acid was added over 15 minutes while stirring, and then stirred for 1 hour. 20 ml of water was added dropwise to the reaction solution, pH was adjusted to about 4 with diluted sulfuric acid, and the mixture was stirred and filtered. The crystals were dried to obtain 1.1 g of compound B5 shown in Table 2. This compound was dissolved in methanol at 1% or more. The λmax of the methanol solution was 648 nm.
【0082】実施例23
1)3−メトキシカルボニル−2−(4−シアノフェニ
ル)−5−オキソ−4,5−ジヒドロ−1H−ピロール
0.26g、3,3−ビス(4−ジメチルアミノフェニ
ル)−2−プロペナール0.29g、エタノール3m
l、62%硫酸0.2mlを混合し6時間撹拌後、希水
酸化ナトリウムで中和し、濾過して赤黒色結晶0.46
gを得た。Example 23 1) 0.26 g of 3-methoxycarbonyl-2- (4-cyanophenyl) -5-oxo-4,5-dihydro-1H-pyrrole, 3,3-bis (4-dimethylaminophenyl) ) -2-Propenal 0.29 g, ethanol 3 m
1, 62% sulfuric acid (0.2 ml) were mixed and the mixture was stirred for 6 hours, neutralized with dilute sodium hydroxide, and filtered to give red-black crystals 0.46.
g was obtained.
【0083】2)上記1)で得られた結晶0.4g、塩
化ホスホリル16ml、ピリジン2mlを混合し撹拌し
ながら昇温した。80℃で1h撹拌後、反応液を冷水に
排出し水酸化ナトリウムで中和しクロロホルムで抽出し
有機層を濃縮、乾燥して前記第2表に示す化合物B2の
黒紫色結晶0.2gを得た。この化合物のλmaxは6
45nm(メタノール)であった。2) 0.4 g of the crystals obtained in 1) above, 16 ml of phosphoryl chloride and 2 ml of pyridine were mixed and the temperature was raised with stirring. After stirring at 80 ° C. for 1 hour, the reaction solution was discharged into cold water, neutralized with sodium hydroxide, extracted with chloroform, the organic layer was concentrated and dried to obtain 0.2 g of black-purple crystals of compound B2 shown in Table 2 above. It was Λmax of this compound is 6
It was 45 nm (methanol).
【0084】実施例24
1)化合物M1を0.12g、3,3−ビス(4−ピロ
リジノフェニル)−2−プロペナール0.17gを無水
酢酸1.5mlに懸濁させ撹拌しながら昇温した。70
℃で3時間撹拌後、放冷し析出した結晶を濾取した。黒
褐色結晶0.22gを得た。Example 24 1) 0.12 g of compound M1 and 0.17 g of 3,3-bis (4-pyrrolidinophenyl) -2-propenal were suspended in 1.5 ml of acetic anhydride and the temperature was raised with stirring. . 70
After stirring at 0 ° C for 3 hours, the mixture was allowed to cool and the precipitated crystals were collected by filtration. 0.22 g of blackish brown crystals were obtained.
【0085】2)上記1)で得られた結晶0.10gを
トルエン2ml、塩化ホスホリル0.8mlと混合し撹
拌しながら昇温した。90℃で1時間撹拌後、反応液を
濾過して結晶を得た。これを水洗後、乾燥して前記第2
表に示す化合物B3の緑褐色結晶0.10gを得た。L
C/MSで578(MH+)のピークを確認した。この
化合物のλmaxは647nm(メタノール)であっ
た。2) 0.10 g of the crystals obtained in 1) above were mixed with 2 ml of toluene and 0.8 ml of phosphoryl chloride and the temperature was raised with stirring. After stirring at 90 ° C. for 1 hour, the reaction solution was filtered to give crystals. After washing with water and drying, the second
0.10 g of green-brown crystals of compound B3 shown in the table was obtained. L
A peak of 578 (MH + ) was confirmed by C / MS. The λmax of this compound was 647 nm (methanol).
【0086】実施例25
1)反応容器に4−(ジメチルアミノ)ベンズアルデヒ
ド3.2g、化合物M1を4.9g、エタノール60m
l、62%硫酸3mlを仕込み室温で0.5時間、60
℃で3時間撹拌した。反応液を放冷し、水を加え水酸化
ナトリウム水溶液で中和して濾過して、下記化学式で示
される4−(4−ジメチルアミノベンジリデン)−3−
エトキシカルボニル−2−フェニル−5−オキソ−4,
5−ジヒドロ−1H−ピロール(化合物M2)の赤色結
晶7.7gを得た。Example 25 1) 4- (Dimethylamino) benzaldehyde 3.2 g, compound M1 4.9 g, ethanol 60 m in a reaction vessel.
1, 62% sulfuric acid 3 ml was charged, and the mixture was stirred at room temperature for 0.5 hours, 60
The mixture was stirred at 0 ° C for 3 hours. The reaction solution is allowed to cool, water is added thereto, the solution is neutralized with an aqueous sodium hydroxide solution, and filtered to give 4- (4-dimethylaminobenzylidene) -3- represented by the following chemical formula.
Ethoxycarbonyl-2-phenyl-5-oxo-4,
7.7 g of red crystals of 5-dihydro-1H-pyrrole (compound M2) were obtained.
【0087】[0087]
【化29】 [Chemical 29]
【0088】2)上記1)で得た結晶0.5g、N−メ
チル−2−フェニルインドール0.3g、トルエン7.
5ml、塩化ホスホリル7.5ml、ピリジン0.5m
lを順に加え昇温し60−70℃で90分撹拌した後、
反応液を氷水に滴下し水酸化ナトリウム水溶液で中和し
た。クロロホルムで抽出し、乾燥、濃縮して0.61g
の結晶を得た。
3)上記2)で得られた結晶0.61gにエタノール1
0ml、クロラニル0.37を加え昇温して50〜60
℃で5時間撹拌した。反応液に水を加え、水酸化ナトリ
ウム水溶液でアルカリ性としクロロホルムで抽出した。
有機層に活性白土を加えて撹拌、濾過し濾液を濃縮し
た。カラムクロマトグラフィで精製して下記構造式で示
される化合物C2の黒色結晶0.24gを得た。この化
合物のλmaxは586nm(メタノール)であった。2) 0.5 g of the crystals obtained in 1) above, 0.3 g of N-methyl-2-phenylindole, and 7.
5 ml, phosphoryl chloride 7.5 ml, pyridine 0.5 m
1 was added in sequence and the temperature was raised and stirred at 60-70 ° C. for 90 minutes,
The reaction solution was added dropwise to ice water and neutralized with an aqueous sodium hydroxide solution. Extract with chloroform, dry and concentrate to 0.61g
Was obtained. 3) Ethanol 1 was added to 0.61 g of the crystals obtained in 2) above.
Add 0 ml and chloranil 0.37 and raise the temperature to 50-60.
The mixture was stirred at 0 ° C for 5 hours. Water was added to the reaction solution, which was made alkaline with an aqueous sodium hydroxide solution and extracted with chloroform.
Activated clay was added to the organic layer, and the mixture was stirred, filtered, and the filtrate was concentrated. Purification by column chromatography gave 0.24 g of black crystals of compound C2 represented by the following structural formula. The λmax of this compound was 586 nm (methanol).
【0089】[0089]
【化30】 [Chemical 30]
【0090】実施例26
反応容器に1,2−ジクロロエタン10ml、ピリジン
0.3ml、塩化ホスホリル1.9gを仕込み撹拌しな
がら、実施例25の1)と同様にして得た化合物M2の
結晶1.8gを15分で仕込み、続いて1,1−ビス
(4−ジメチルアミノフェニル)エテン1.3gを50
分で仕込んだ。3時間撹拌した後、反応液を冷水200
mlに滴下した後、クロロホルムを加え水層を水酸化ナ
トリウム水溶液で中和して1時間撹拌後、水層を捨て再
び水を加え1時間撹拌した。有機層を分取しそれを撹拌
しながらそこにクロラニル1.2gを0.5時間で加
え、さらに1時間撹拌した。反応液を濃縮し残留物に酢
酸エチル約50mlを加え撹拌、濾過した。得られた結
晶をトルエン約100mlに分散し撹拌後、濾過、乾燥
して粗製品結晶2.4gを得た。これをシリカゲルカラ
ムで精製して(展開溶媒クロロホルム:メタノール=5
0:1〜5:1)、下記構造式で示される化合物の精製
品1.0gを得た。Example 26 1,2-dichloroethane (10 ml), pyridine (0.3 ml) and phosphoryl chloride (1.9 g) were charged into a reaction vessel, and the mixture was stirred, and crystals of compound M2 obtained in the same manner as in Example 25 1) 1. 8 g was charged in 15 minutes, followed by 50 g of 1.3-g 1,1-bis (4-dimethylaminophenyl) ethene.
Prepared in minutes. After stirring for 3 hours, the reaction solution was cooled to 200 mL with cold water.
After adding dropwise to ml, chloroform was added and the aqueous layer was neutralized with an aqueous sodium hydroxide solution and stirred for 1 hour. Then, the aqueous layer was discarded, water was added again, and the mixture was stirred for 1 hour. The organic layer was separated, 1.2 g of chloranil was added thereto with stirring for 0.5 hour, and the mixture was further stirred for 1 hour. The reaction solution was concentrated, about 50 ml of ethyl acetate was added to the residue, and the mixture was stirred and filtered. The obtained crystals were dispersed in about 100 ml of toluene, stirred, filtered and dried to obtain 2.4 g of crude product crystals. This was purified with a silica gel column (developing solvent chloroform: methanol = 5).
0: 1 to 5: 1), 1.0 g of a purified product of the compound represented by the following structural formula was obtained.
【0091】[0091]
【化31】 [Chemical 31]
【0092】LC/MSで645(MH+)のピークを
確認した。NMR分析結果は次のようであった。1H−
NMR(CDCl3):δ0.94(t,3H),3.
13(s,18H),3.85(q,2H),6.63
(d,4H),6.68(d,2H),7.21−7.
31(m,3H),7.40−7.45(m,3H),
7.50(d,2H),7.60(d,2H)。この化
合物のメタノール中でのλmaxは665nm(ε=6
1000)と715nm(ε=57000)であった。
この化合物の赤外吸収スペクトルを図2に示す。A peak at 645 (MH + ) was confirmed by LC / MS. The NMR analysis results were as follows. 1 H-
NMR (CDCl 3 ): δ 0.94 (t, 3H), 3.
13 (s, 18H), 3.85 (q, 2H), 6.63
(D, 4H), 6.68 (d, 2H), 7.21-7.
31 (m, 3H), 7.40-7.45 (m, 3H),
7.50 (d, 2H), 7.60 (d, 2H). Λmax of this compound in methanol is 665 nm (ε = 6
1000) and 715 nm (ε = 57,000).
The infrared absorption spectrum of this compound is shown in FIG.
【0093】実施例27
実施例26の1,1−ビス(4−ジメチルアミノフェニ
ル)エテンの代わりに1−(4−ジメチルアミノフェニ
ル)−1−(4−メトキシフェニル)エテンを用い、他
は実施例26と同様に操作して下記構造の化合物B16
を得た。この化合物のλmaxは739nm(メタノー
ル)であった。この化合物の可視・近赤外吸収スペクト
ルを図4に示す。Example 27 1- (4-Dimethylaminophenyl) -1- (4-methoxyphenyl) ethene was used instead of 1,1-bis (4-dimethylaminophenyl) ethene of Example 26, Compound B16 having the following structure was prepared by the same procedure as in Example 26.
Got The λmax of this compound was 739 nm (methanol). The visible / near infrared absorption spectrum of this compound is shown in FIG.
【0094】[0094]
【化32】 [Chemical 32]
【0095】実施例28
1)反応容器に化合物M1を5.4g、5,5−ビス
(4−ジメチルアミノフェニル)−2,4−ペンタジエ
ナール7.5g、無水酢酸70mlを仕込み、50〜6
0℃で20時間撹拌後、放冷した。析出した結晶を濾過
して分離し、クロロホルムに溶解して、水酸化ナトリウ
ム水溶液及び水で洗浄後、濃縮して黒紫結晶7.1gを
得た。LC/MSで534(MH+)のピークを確認し
た。Example 28 1) A reaction vessel was charged with 5.4 g of the compound M1, 7.5 g of 5,5-bis (4-dimethylaminophenyl) -2,4-pentadienal and 70 ml of acetic anhydride, and the mixture was heated to 50- 6
After stirring at 0 ° C for 20 hours, the mixture was allowed to cool. The precipitated crystals were separated by filtration, dissolved in chloroform, washed with an aqueous sodium hydroxide solution and water, and then concentrated to obtain 7.1 g of black purple crystals. A peak of 534 (MH + ) was confirmed by LC / MS.
【0096】2)反応容器に1,2−ジクロロエタン2
ml、塩化ホスホリル0.3ml、N,N−ジメチルア
ニリン0.24gを仕込み撹拌しながら、上記1)で得
た4−[5,5−ビス(4−ジメチルアミノフェニル)
−2,4−ペンタジエニリデン]−3−エトキシカルボ
ニル−2−フェニル−5−オキソ−4,5−ジヒドロ−
1H−ピロール0.53gを30分で仕込んだ。室温で
3時間撹拌した後、反応液を氷水100mlに滴下した
後、クロロホルムを加え水層を水酸化ナトリウム水溶液
で中和して1時間撹拌した。有機層を分取し水洗、乾燥
後、濃縮した。残留物にエタノール10mlを加え撹拌
しながらクロラニル0.22gを加え、2時間撹拌し
た。反応液を濃縮し残留物に酢酸エチルを加え撹拌、濾
過した。得られた結晶を酢酸とトルエンの混合溶媒に分
散し撹拌後、濾過、乾燥して粗製品の青黒色結晶0.5
0gを得た。これをシリカゲルカラムで精製して(展開
溶媒クロロホルム:メタノール=20:1〜5:1)、
下記構造式で示される化合物の精製品0.13gを得
た。LC/MSで672(MH+)のピークを確認し
た。この化合物のメタノール溶液のλmaxは806n
m(ε=100000)であった。この化合物の可視・
近赤外吸収スペクトルを図5に示す。またNMR分析の
結果は次のようであった。1H−NMR(CDC
l3):δ0.89(t,3H),3.09(s,6
H),3.12(s,12H),3.89(q,2
H),6.65(d,2H),6.77(d,4H),
7.14(d,1H),7.22−7.44(m,9
H),7.57(d,2H),7.74(d,2H)。2) 1,2-dichloroethane 2 in the reaction vessel
ml, phosphoryl chloride 0.3 ml, and N, N-dimethylaniline 0.24 g were charged and stirred to obtain 4- [5,5-bis (4-dimethylaminophenyl) 4- [5,5-bis (4-dimethylaminophenyl)]
-2,4-Pentadienylidene] -3-ethoxycarbonyl-2-phenyl-5-oxo-4,5-dihydro-
0.53 g of 1H-pyrrole was charged in 30 minutes. After stirring at room temperature for 3 hours, the reaction solution was added dropwise to 100 ml of ice water, chloroform was added, and the aqueous layer was neutralized with an aqueous sodium hydroxide solution and stirred for 1 hour. The organic layer was separated, washed with water, dried, and concentrated. To the residue was added 10 ml of ethanol, 0.22 g of chloranil was added with stirring, and the mixture was stirred for 2 hours. The reaction mixture was concentrated, ethyl acetate was added to the residue, and the mixture was stirred and filtered. The crystals obtained were dispersed in a mixed solvent of acetic acid and toluene, stirred, filtered, and dried to give crude product blue-black crystals 0.5.
0 g was obtained. This was purified with a silica gel column (developing solvent chloroform: methanol = 20: 1 to 5: 1),
0.13 g of a purified product of the compound represented by the following structural formula was obtained. A peak of 672 (MH + ) was confirmed by LC / MS. Λmax of the methanol solution of this compound is 806n
It was m ((epsilon) = 100000). The visibility of this compound
The near infrared absorption spectrum is shown in FIG. The results of NMR analysis were as follows. 1 H-NMR (CDC
l 3 ): δ 0.89 (t, 3H), 3.09 (s, 6)
H), 3.12 (s, 12H), 3.89 (q, 2)
H), 6.65 (d, 2H), 6.77 (d, 4H),
7.14 (d, 1H), 7.22-7.44 (m, 9
H), 7.57 (d, 2H), 7.74 (d, 2H).
【0097】[0097]
【化33】 [Chemical 33]
【0098】実施例29
1)5,5−ビス(4−ジメチルアミノフェニル)−
2,4−ペンタジエナール5.0g、DMF140m
l、1,3−ジオキサン−2−イルメチルトリブチルホ
スホニウムブロミド6.3gを混合、撹拌しながら28
%ナトリウムメチラート−メタノール溶液5.4gを1
5分で滴下した。その後、3時間撹拌した後、水100
0mlに注入し、酢酸エチルで抽出した。有機層を脱
水、濃縮してアセタール化合物10gを得た。これを希
塩酸中で撹拌して加水分解した後、水酸化ナトリウムで
中和し、酢酸エチルで抽出、水洗、脱水、濃縮して目的
とする7,7−ビス(4−ジメチルアミノフェニル)−
2,4,6−ヘキサトリエナール5.3gを得た。
2)上記1)で得たアルデヒド化合物5.3g、化合物
M1を3.6g、エタノール40ml、希硫酸2mlを
混合し5時間撹拌後、希水酸化ナトリウムで中和し濾
過、乾燥して目的とする4−[7,7−ビス(4−ジメ
チルアミノフェニル)−2,4,6−ヘプタトリエニリ
デン]−3−エトキシカルボニル−2−フェニル−5−
オキソ−4,5−ジヒドロ−1H−ピロール3.7gを
得た。
3)反応容器にジクロロメタン4ml、塩化ホスホリル
0.6ml、N,N−ジメチルアニリン0.48gを仕
込み撹拌しながら、2)で得たピロリノン化合物1.1
gを0.5時間で加えた。4時間撹拌した後、反応液を
氷水に滴下し、クロロホルムを加え水酸化ナトリウム水
溶液で中和して3時間撹拌した。有機層を分取し水洗、
脱水した後、クロラニル0.5gを加え一晩撹拌した。
反応液を濃縮し残留物に酢酸エチルを加え撹拌、濾過し
た。得られた粗結晶を乾燥後、シリカゲルカラムで精製
して(展開溶媒クロロホルム−メタノール)、第2表に
示す化合物B14の結晶0.051gを得た。Example 29 1) 5,5-bis (4-dimethylaminophenyl)-
5.0 g of 2,4-pentadienal, 140 m of DMF
l, 1,3-dioxan-2-ylmethyltributylphosphonium bromide (6.3 g) was mixed and stirred with 28
1% 5.4 g of sodium methylate-methanol solution
It was added dropwise in 5 minutes. Then, after stirring for 3 hours, water 100
It was poured into 0 ml and extracted with ethyl acetate. The organic layer was dehydrated and concentrated to obtain 10 g of acetal compound. This is stirred in dilute hydrochloric acid for hydrolysis, then neutralized with sodium hydroxide, extracted with ethyl acetate, washed with water, dehydrated and concentrated to give the desired 7,7-bis (4-dimethylaminophenyl)-
5.3 g of 2,4,6-hexatrienal was obtained. 2) 5.3 g of the aldehyde compound obtained in 1) above, 3.6 g of compound M1, 40 ml of ethanol and 2 ml of dilute sulfuric acid were mixed and stirred for 5 hours, then neutralized with dilute sodium hydroxide, filtered and dried to obtain the desired 4- [7,7-bis (4-dimethylaminophenyl) -2,4,6-heptatrienylidene] -3-ethoxycarbonyl-2-phenyl-5-
3.7 g of oxo-4,5-dihydro-1H-pyrrole was obtained. 3) Dichloromethane (4 ml), phosphoryl chloride (0.6 ml) and N, N-dimethylaniline (0.48 g) were charged into a reaction vessel, and the mixture was stirred, and the pyrrolinone compound 1.1 obtained in 2) was used.
g was added in 0.5 hours. After stirring for 4 hours, the reaction solution was added dropwise to ice water, chloroform was added, and the mixture was neutralized with an aqueous sodium hydroxide solution and stirred for 3 hours. Separate the organic layer and wash with water,
After dehydration, 0.5 g of chloranil was added and stirred overnight.
The reaction mixture was concentrated, ethyl acetate was added to the residue, and the mixture was stirred and filtered. The obtained crude crystals were dried and then purified with a silica gel column (developing solvent chloroform-methanol) to obtain 0.051 g of crystals of compound B14 shown in Table 2.
【0099】実施例30
反応容器に実施例26で得た化合物B10を0.1g仕
込みDMF0.4ml、無水炭酸カリウム0.06gと
混合し室温で撹拌しながら4−メルカプト安息香酸0.
03gを加えた。3時間撹拌後、水で希釈、濾過して前
記第2表に示す化合物B18の結晶0.047gを得
た。この化合物のλmaxは664nmと720nm
(メタノール)であった。Example 30 0.1 g of the compound B10 obtained in Example 26 was charged in a reaction vessel, mixed with 0.4 ml of DMF and 0.06 g of anhydrous potassium carbonate, and stirred at room temperature with 4-mercaptobenzoic acid (0.1%).
03 g was added. After stirring for 3 hours, the mixture was diluted with water and filtered to obtain 0.047 g of crystals of compound B18 shown in Table 2 above. Λmax of this compound is 664 nm and 720 nm
(Methanol).
【0100】実施例31
実施例22の4−メルカプト安息香酸を4−t−ブチル
チオフェノールに代えた他は実施例22と同様の操作に
より前記第2表に示す化合物B19の結晶を得た。Example 31 Crystals of the compound B19 shown in Table 2 above were obtained by the same procedure as in Example 22 except that 4-mercaptobenzoic acid in Example 22 was replaced with 4-t-butylthiophenol.
【0101】実施例32
反応容器に1,2−ジクロロエタン6ml、ピリジン
0.6ml、塩化ホスホリル2ml、N,N−ジブチル
アニリン0.80gを仕込み撹拌しながら、実施例25
の1)と同様にして得た化合物M2の結晶1.1gを少
しずつ仕込んだ。その後、室温で1時間、50〜60℃
で2時間撹拌した後、放冷し、反応液を冷水500ml
に滴下しクロロホルムを加え水酸化ナトリウムで中和し
て3時間撹拌した。有機層を分取、水洗した後、クロラ
ニル0.74gを加え、3時間撹拌した。反応液を濃縮
し残留物に酢酸エチルとヘキサンを加え、上澄み層を除
去した後、ヘキサンを加え、濾過して1.6gの粗結晶
を得た。これをシリカゲルカラムクロマトグラフィで精
製して前記第1表に示す化合物A18の結晶0.57g
を得た。この化合物のλmaxは620nm(メタノー
ル)であった。Example 32 Example 25 was prepared by charging 6 ml of 1,2-dichloroethane, 0.6 ml of pyridine, 2 ml of phosphoryl chloride and 0.80 g of N, N-dibutylaniline into a reaction vessel while stirring.
1.1 g of crystals of compound M2 obtained in the same manner as in 1) above were charged little by little. Then, at room temperature for 1 hour at 50-60 ° C
After stirring for 2 hours at room temperature, the reaction mixture is allowed to cool and the reaction solution is cooled with 500 ml of cold water.
Was added dropwise to the mixture, chloroform was added, and the mixture was neutralized with sodium hydroxide and stirred for 3 hours. The organic layer was separated and washed with water, 0.74 g of chloranil was added, and the mixture was stirred for 3 hours. The reaction solution was concentrated, ethyl acetate and hexane were added to the residue, the supernatant layer was removed, hexane was added, and filtration was performed to obtain 1.6 g of crude crystals. This was purified by silica gel column chromatography to give 0.57 g of crystals of compound A18 shown in Table 1 above.
Got The λmax of this compound was 620 nm (methanol).
【0102】実施例33
1)反応容器に3−シアノ−4,5−ジヒドロ−5−オ
キソ−2−フェニルピロール1.0g、4−ジメチルア
ミノベンズアルデヒド0.81g、エタノール15ml
を仕込み撹拌しながら62%硫酸0.5mlを滴下し
た。60℃で2時間撹拌した後、放冷し、反応液を濾過
し、得られた結晶を水洗いし乾燥して、3−シアノ−4
−(4−ジメチルアミノベンジリデン)−2−フェニル
−5−オキソ−4,5−ジヒドロ−1H−ピロールの赤
茶色結晶0.90gを得た。Example 33 1) In a reaction vessel, 1.0 g of 3-cyano-4,5-dihydro-5-oxo-2-phenylpyrrole, 0.81 g of 4-dimethylaminobenzaldehyde and 15 ml of ethanol were placed.
Then, 0.5 ml of 62% sulfuric acid was added dropwise with stirring. After stirring at 60 ° C for 2 hours, the mixture was allowed to cool, the reaction solution was filtered, and the obtained crystals were washed with water and dried to give 3-cyano-4.
0.90 g of red-brown crystals of-(4-dimethylaminobenzylidene) -2-phenyl-5-oxo-4,5-dihydro-1H-pyrrole were obtained.
【0103】2)反応容器に、上記で得られた結晶0.
85g、ジクロロエタン15ml、塩化ホスホリル3m
l、ピリジン0.4ml、1,1−ビス(4−ジメチル
アミノフェニル)エテン0.71gを順に加え55℃で
1時間撹拌した。反応液を水に排出しクロロホルムを加
え攪拌した後、有機層を除去した。水層に水酸化ナトリ
ウム水溶液を加えてアルカリ性にしてクロロホルムで抽
出した。有機層に活性白土を加えて撹拌、濾過して濾液
を濃縮した。2) In a reaction vessel, the crystals of
85 g, dichloroethane 15 ml, phosphoryl chloride 3 m
1, pyridine 0.4 ml, and 1,1-bis (4-dimethylaminophenyl) ethene 0.71 g were sequentially added, and the mixture was stirred at 55 ° C. for 1 hour. The reaction solution was discharged into water, chloroform was added and the mixture was stirred, and then the organic layer was removed. Aqueous sodium hydroxide solution was added to the aqueous layer to make it alkaline and extracted with chloroform. Activated clay was added to the organic layer, and the mixture was stirred, filtered, and the filtrate was concentrated.
【0104】3)上記2)の生成物0.87gにエタノ
ール10mlを加えクロラニル0.37gを加え60℃
で2時間撹拌した。放冷後、反応液に水を加え水酸化ナ
トリウム水溶液でアルカリ性としクロロホルムで抽出し
た。有機層を脱水、濃縮し残留物をヘキサンでほぐし濾
過した。前記第2表に示す化合物B20の青黒色結晶
0.18gを得た。この化合物のλmaxは648nm
と722nm(メタノール)であった。3) To 0.87 g of the product of 2) above, 10 ml of ethanol was added, and 0.37 g of chloranil was added, and the temperature was 60 ° C.
It was stirred for 2 hours. After allowing to cool, water was added to the reaction solution, which was made alkaline with an aqueous sodium hydroxide solution and extracted with chloroform. The organic layer was dried and concentrated, and the residue was triturated with hexane and filtered. 0.18 g of blue-black crystals of compound B20 shown in Table 2 above was obtained. Λmax of this compound is 648 nm
And 722 nm (methanol).
【0105】実施例34
1)1−エチル−2−メチル−3−ホルミルインドール
2.8g、化合物M1を3.5g、エタノール38m
l、62%硫酸2.1mlを混合し、室温で2時間、4
0〜50℃で2時間撹拌した。反応液を放冷後、水10
mlを加え、濾過、乾燥して、下記構造式で示される化
合物M3の赤橙色結晶5.3gを得た。Example 34 1) 1-Ethyl-2-methyl-3-formylindole 2.8 g, compound M1 3.5 g, ethanol 38 m
1, 62% sulfuric acid 2.1 ml were mixed, and the mixture was stirred at room temperature for 2 hours,
The mixture was stirred at 0 to 50 ° C for 2 hours. After allowing the reaction solution to cool, water 10
ml was added, and the mixture was filtered and dried to obtain 5.3 g of a red-orange crystal of compound M3 represented by the following structural formula.
【0106】[0106]
【化34】 [Chemical 34]
【0107】2)反応容器に1,2−ジクロロエタン8
ml、ピリジン0.8ml、塩化ホスホリル6.0gを
仕込み撹拌しながら、上記1)で得た4−(1−エチル
−2−メチル−3−インドリルメチリデン)−3−(エ
トキシカルボニル)−2−フェニル−5−オキソ−4,
5−ジヒドロ−1H−ピロール1.6gを仕込み、続い
て1−エチル−2−メチルインドール0.9gを仕込ん
だ。40〜50℃で7時間撹拌した後、反応液を冷水2
00mlに滴下し、クロロホルムを加え水層を水酸化ナ
トリウム水溶液で中和して1時間撹拌後、水層を捨て再
び水を加え1時間撹拌した。有機層を分取しそれを撹拌
しながらそこにクロラニル0.8gを0.5時間で加
え、その後2時間撹拌した。反応液を濃縮し残留物に酢
酸エチルとヘキサンを加え撹拌、濾過した。得られた結
晶をトルエンとヘキサンの混合溶媒に分散し撹拌後、濾
過、乾燥して粗製品結晶2.1を得た。これをシリカゲ
ルカラムで精製して(展開溶媒クロロホルム−メタノー
ル)、下記構造式で示される化合物C1の赤黒色結晶
0.24gを得た。この化合物のλmaxは488nm
(メタノール)であった。NMR分析の結果は次のよう
であった。1H−NMR(CDCl3):δ0.47
(t,3H),1.41−1.55(m,6H),2.
33(s,3H),2.67(s,3H),3.54
(q,1H),3.57(q,1H),4.21−4.
38(m,4H),6.73−6.90(m,3H),
7.13−7.39(m,8H),7.96(d,2
H)。2) 1,2-dichloroethane 8 in a reaction vessel
ml, pyridine 0.8 ml, and phosphoryl chloride 6.0 g were charged and stirred to obtain 4- (1-ethyl-2-methyl-3-indolylmethylidene) -3- (ethoxycarbonyl)-. 2-phenyl-5-oxo-4,
1.6 g of 5-dihydro-1H-pyrrole was charged, followed by 0.9 g of 1-ethyl-2-methylindole. After stirring at 40 to 50 ° C. for 7 hours, the reaction solution was mixed with cold water 2
The mixture was added dropwise to 00 ml, chloroform was added, the aqueous layer was neutralized with an aqueous sodium hydroxide solution, and the mixture was stirred for 1 hour. The organic layer was separated, 0.8 g of chloranil was added thereto with stirring over 0.5 hours, and the mixture was stirred for 2 hours. The reaction mixture was concentrated, ethyl acetate and hexane were added to the residue, and the mixture was stirred and filtered. The obtained crystals were dispersed in a mixed solvent of toluene and hexane, stirred, filtered and dried to obtain crude product crystals 2.1. This was purified with a silica gel column (developing solvent chloroform-methanol) to obtain 0.24 g of red-black crystals of compound C1 represented by the following structural formula. Λmax of this compound is 488 nm
(Methanol). The results of NMR analysis were as follows. 1 H-NMR (CDCl 3 ): δ0.47
(T, 3H), 1.41-1.55 (m, 6H), 2.
33 (s, 3H), 2.67 (s, 3H), 3.54
(Q, 1H), 3.57 (q, 1H), 4.21-4.
38 (m, 4H), 6.73-6.90 (m, 3H),
7.13-7.39 (m, 8H), 7.96 (d, 2)
H).
【0108】[0108]
【化35】 [Chemical 35]
【0109】実施例35
実施例34で得た化合物C1を0.40g、DMF4m
l、炭酸カリウム0.19gを混合し撹拌しながら、4
−t−ブチルチオフェノール0.12gを滴下した。3
時間撹拌後、別容器の水に注加し析出した結晶を濾別
し、ヘキサンで洗浄、乾燥した。前記第3表に示す化合
物C3の赤黒色結晶0.36g得た。この化合物のλm
axは489nm(メタノール)であった。Example 35 0.40 g of the compound C1 obtained in Example 34 and DMF4m
1 and 0.19 g of potassium carbonate are mixed and stirred while 4
0.12 g of -t-butylthiophenol was added dropwise. Three
After stirring for an hour, the mixture was poured into water in another container, and the precipitated crystals were separated by filtration, washed with hexane and dried. 0.36 g of red-black crystals of compound C3 shown in Table 3 above was obtained. Λm of this compound
The ax was 489 nm (methanol).
【0110】実施例36
1)実施例25の1)の操作におけるジメチルアミノベ
ンズアルデヒドの代わりに、同モル数の4−ジメチルア
ミノシンナムアルデヒドを用い、他は実施例25の1)
と同様に操作して、下記化学式で示される化合物M4の
赤黒色結晶7.5gを得た。Example 36 1) Instead of dimethylaminobenzaldehyde in the operation of 1) of Example 25, the same molar number of 4-dimethylaminocinnamaldehyde was used, and otherwise 1) of Example 25.
The same operation as in (1) to give 7.5 g of a red-black crystal of compound M4 represented by the following chemical formula.
【0111】[0111]
【化36】 [Chemical 36]
【0112】2)反応容器に1,2−ジクロロエタン6
ml、ピリジン0.6ml、塩化ホスホリル2ml、
N,N−ジメチルアニリン0.72gを仕込み撹拌しな
がら、上記1)の操作で得た化合物M4の結晶1.2g
を少しずつ仕込んだ。その後、室温で1時間、40〜5
0℃で2時間撹拌した後、放冷し、反応液を冷水に滴下
しクロロホルムを加え水酸化ナトリウムで中和して一晩
撹拌した。有機層を分取、水洗した後、クロラニル0.
75gを加え、2時間撹拌した。反応液を濃縮し残留物
に酢酸エチルを加え濾過して粗結晶を得た。これをシリ
カゲルカラムクロマトグラフィで精製して前記第1表に
示す化合物B22の青黒色結晶0.21gを得た。2) 1,2-dichloroethane 6 was added to the reaction vessel.
ml, pyridine 0.6 ml, phosphoryl chloride 2 ml,
1.2 g of crystals of the compound M4 obtained by the above operation 1) while charging 0.72 g of N, N-dimethylaniline and stirring
I prepared it little by little. Then, at room temperature for 1 hour, 40-5
After stirring at 0 ° C. for 2 hours, the mixture was allowed to cool, the reaction mixture was added dropwise to cold water, chloroform was added, the mixture was neutralized with sodium hydroxide, and the mixture was stirred overnight. The organic layer was separated and washed with water, and then chloranil 0.
75 g was added and stirred for 2 hours. The reaction mixture was concentrated, ethyl acetate was added to the residue, and the mixture was filtered to give crude crystals. This was purified by silica gel column chromatography to obtain 0.21 g of blue-black crystals of compound B22 shown in Table 1 above.
【0113】実施例37
実施例3の操作において、4−t−ブチルチオフェノー
ルの代わりに同モル数の2,4,6−トリメチルチオフ
ェノールを用い、他は実施例3と同様に操作して前記第
1表に示す化合物A25を得た。Example 37 The same procedure as in Example 3 was carried out except that the same mole number of 2,4,6-trimethylthiophenol was used in place of 4-t-butylthiophenol in the operation of Example 3. The compound A25 shown in Table 1 above was obtained.
【0114】実施例38〜40
実施例5の操作において、2−メルカプトベンゾチアゾ
ールの代わりに同モル数の2−メルカプトピリジン、1
−メチル−2−メルカプトイミダゾール、4−シアノフ
ェノールをそれぞれ用い、他は実施例5と同様に操作し
て前記第1表に示す化合物A26〜A28をそれぞれ得
た。Examples 38-40 In the procedure of Example 5, instead of 2-mercaptobenzothiazole, the same mole number of 2-mercaptopyridine, 1
-Methyl-2-mercaptoimidazole and 4-cyanophenol were used, respectively, and otherwise the same operation as in Example 5 was carried out to obtain compounds A26 to A28 shown in Table 1 above.
【0115】実施例41〜42
実施例3の操作において、化合物A1の代わりに化合物
A13を用い、4−t−ブチルチオフェノールの代わり
に1−オクタンチオール、2−メルカプト−5−メトキ
シベンゾチアゾールをそれぞれ用い、他は実施例3と同
様に操作して、前記第1表に示す化合物A30〜A31
をそれぞれ得た。Examples 41 to 42 In the procedure of Example 3, compound A13 was used in place of compound A1, 1-octanethiol and 2-mercapto-5-methoxybenzothiazole were used in place of 4-t-butylthiophenol. Compounds A30 to A31 shown in Table 1 above were used, respectively, and the same operation as in Example 3 except for the above.
Respectively obtained.
【0116】実施例43
1)N−エチル−3−ホルミルカルバゾール4.4g、
化合物M1を4.6g、エタノール50ml、62%硫
酸2.8mlを混合し室温で1時間、50℃で3時間撹
拌後、希水酸化ナトリウムで中和して濾過、乾燥して下
記構造の化合物の赤橙色結晶8.5gを得た。Example 43 1) 4.4 g of N-ethyl-3-formylcarbazole,
Compound M1 (4.6 g), ethanol (50 ml) and 62% sulfuric acid (2.8 ml) were mixed, stirred at room temperature for 1 hour and at 50 ° C. for 3 hours, neutralized with diluted sodium hydroxide, filtered and dried to obtain a compound having the following structure. 8.5 g of red-orange crystals of
【0117】[0117]
【化37】 [Chemical 37]
【0118】2)塩化ホスホリル14ml、1,2−ジ
クロロエタン7ml、N,N−ジブチルアニリン2.9
g、上記1)で得たピロリノン化合物3.1gを混合し
室温で20時間撹拌した。その後、冷水500mlに滴
下し水酸化ナトリウムで中和し、クロロホルムを加え、
有機層を分取、濃縮した。残分にヘキサンを加え結晶を
濾別、風乾して淡黄褐色結晶4.5gを得た。
3)上記2)で得た化合物4.5gをクロロホルム50
mlに溶解し、クロラニル1.7gを加え、室温で2時
間撹拌後、溶媒を留去し酢酸エチルとヘキサンの混合溶
媒を加えて晶析、濾過した。これをカラムクロマトグラ
フィで精製して下記化学式で示される化合物C5の黒紫
色結晶2.6gを得た。この化合物のλmaxは556
nm(メタノール)であった。2) Phosphoryl chloride 14 ml, 1,2-dichloroethane 7 ml, N, N-dibutylaniline 2.9
g, and 3.1 g of the pyrrolinone compound obtained in 1) above were mixed and stirred at room temperature for 20 hours. Then, add dropwise to 500 ml of cold water, neutralize with sodium hydroxide, add chloroform,
The organic layer was separated and concentrated. Hexane was added to the residue, and the crystals were separated by filtration and air-dried to obtain 4.5 g of pale yellowish brown crystals. 3) Chloroform 50 was added to 4.5 g of the compound obtained in 2) above.
It was dissolved in ml, 1.7 g of chloranil was added, and the mixture was stirred at room temperature for 2 hours, then the solvent was distilled off, a mixed solvent of ethyl acetate and hexane was added, and crystallization and filtration were performed. This was purified by column chromatography to obtain 2.6 g of a black-purple crystal of compound C5 represented by the following chemical formula. The λmax of this compound is 556
nm (methanol).
【0119】[0119]
【化38】 [Chemical 38]
【0120】実施例44
実施例26の1,1−ビス(4−ジメチルアミノフェニ
ル)エテンに代えて、1,1−ビス(1−メチル−2−
フェニル−3−インドリル)エテンを用い、他は実施例
26と同様に操作して前記第3表に示す化合物C6を得
た。この化合物のλmaxは728nm(メタノール)
であった。Example 44 In place of 1,1-bis (4-dimethylaminophenyl) ethene of Example 26, 1,1-bis (1-methyl-2-)
Phenyl-3-indolyl) ethene was used and the same operation as in Example 26 was carried out otherwise to obtain Compound C6 shown in Table 3 above. Λmax of this compound is 728 nm (methanol)
Met.
【0121】実施例45
1)1,2−ジクロロエタン6ml、ピリジン0.6m
l、塩化ホスホリル2ml、N−メチルテトラヒドロキ
ノリン0.87gを仕込み撹拌しながら、実施例36の
1)で得た化合物M4の結晶1.2gを少しずつ仕込ん
だ。その後、室温で1時間、40〜50℃で2時間撹拌
した後、放冷し、反応液を冷水に滴下しクロロホルムを
加え水酸化ナトリウムで中和して一晩撹拌した。有機層
を分取、水洗しクロラニル0.75gを加え1時間撹拌
した。反応液から不溶物を濾別した後、濃縮し残留物に
酢酸エチルを加え濾過して粗結晶を得た。これをカラム
クロマトグラフィで精製して前記第1表に示す化合物C
7の青黒色結晶0.17gを得た。Example 45 1) 1,2-Dichloroethane 6 ml, pyridine 0.6 m
1, phosphoryl chloride 2 ml, and N-methyltetrahydroquinoline 0.87 g were charged, and while stirring, 1.2 g of the crystal of the compound M4 obtained in 1) of Example 36 was charged little by little. Then, the mixture was stirred at room temperature for 1 hour and at 40 to 50 ° C. for 2 hours, then allowed to cool, the reaction solution was added dropwise to cold water, chloroform was added, and the mixture was neutralized with sodium hydroxide and stirred overnight. The organic layer was separated, washed with water, added with 0.75 g of chloranil, and stirred for 1 hour. The insoluble material was filtered off from the reaction solution, concentrated, and ethyl acetate was added to the residue to obtain a crude crystal. This was purified by column chromatography to obtain compound C shown in Table 1 above.
0.17 g of blue-black crystals of 7 was obtained.
【0122】実施例46
1)ピコリノイル酢酸ブチル28.7g、アセトン13
0ml、無水炭酸カリウム17.9g、ブロモ酢酸メチ
ル19.9gを混合し、溶媒の還流温度で4時間撹拌し
た。反応液を放冷後、水300mlにあけ酢酸エチルで
抽出し、硫酸マグネシウムで乾燥した後、濃縮して下記
化学式で示される化合物の粗製品21gを得た。Example 46 1) 28.7 g of butyl picolinoyl acetate, acetone 13
0 ml, anhydrous potassium carbonate 17.9 g and methyl bromoacetate 19.9 g were mixed, and the mixture was stirred at the reflux temperature of the solvent for 4 hours. The reaction solution was allowed to cool, poured into 300 ml of water, extracted with ethyl acetate, dried over magnesium sulfate, and concentrated to obtain 21 g of a crude product of a compound represented by the following chemical formula.
【0123】[0123]
【化39】 [Chemical Formula 39]
【0124】2)上記1)で得た化合物21g、エタノ
ール45ml、酢酸アンモニウム25gを混合し、溶媒
の還流温度で4時間撹拌した。反応液を水400mlに
あけ酢酸エチル少量を加え、析出した結晶を濾別、乾燥
して、下記化学式で示されるピロリノン化合物6.2g
を得た。LC/MSで261(MH+)の質量を示すピ
ークを確認した。2) 21 g of the compound obtained in 1) above, 45 ml of ethanol and 25 g of ammonium acetate were mixed and stirred at the reflux temperature of the solvent for 4 hours. The reaction solution was poured into 400 ml of water, a small amount of ethyl acetate was added, and the precipitated crystals were separated by filtration and dried to give 6.2 g of a pyrrolinone compound represented by the following chemical formula.
Got A peak showing a mass of 261 (MH + ) was confirmed by LC / MS.
【0125】[0125]
【化40】 [Chemical 40]
【0126】3)上記2)で得たピロリノン化合物2.
9g、4−ジメチルアミノベンズアルデヒド1.9g、
エタノール31ml、62%硫酸1.8mlを混合し室
温で5時間攪拌した。反応液を水酸化ナトリウム水溶液
で中和し濾過して結晶を乾燥して、下記化学式で示され
るピロリノン化合物3.0gを得た。LC/MSで39
2(MH+)の質量を示すピークを確認した。3) The pyrrolinone compound obtained in 2) above.
9 g, 4-dimethylaminobenzaldehyde 1.9 g,
Ethanol 31 ml and 62% sulfuric acid 1.8 ml were mixed and stirred at room temperature for 5 hours. The reaction solution was neutralized with an aqueous sodium hydroxide solution, filtered, and the crystals were dried to obtain 3.0 g of a pyrrolinone compound represented by the following chemical formula. 39 by LC / MS
A peak showing a mass of 2 (MH + ) was confirmed.
【0127】[0127]
【化41】 [Chemical 41]
【0128】4)1,2−ジクロロエタン7.8ml、
塩化ホスホリル1.5g、ピリジン0.23ml、及び
上記3)で得たピロリノン化合物1.5gを混合し攪拌
しながら1,1−ビス(4−ジエチルアミノフェニル)
エテン1.2gを1時間で加え、その後、室温で20時
間撹拌した。反応液を冷水200mlに滴下しクロロホ
ルムを加え、水酸化ナトリウムで中和して2時間撹拌し
た。有機層を分取し水洗後、クロラニル0.86gを3
0分で加え1時間攪拌した。反応液を濃縮して残留物に
酢酸エチルを加えて晶析、濾過した。得られた粗結晶を
シリカゲルカラムクロマトグラフィで精製して下記化学
式で示される化合物B15の青黒色結晶0.17gを得
た。LC/MSで730(MH+)の質量を示すピーク
を確認した。λmaxは674nm(メタノール)であ
った。4) 7.8 ml of 1,2-dichloroethane,
Phosphoryl chloride (1.5 g), pyridine (0.23 ml), and the pyrrolinone compound (1.5 g) obtained in 3) above were mixed and stirred with 1,1-bis (4-diethylaminophenyl).
Ethene (1.2 g) was added over 1 hour, and then the mixture was stirred at room temperature for 20 hours. The reaction solution was added dropwise to 200 ml of cold water, chloroform was added, the mixture was neutralized with sodium hydroxide and stirred for 2 hours. Separate the organic layer, wash with water, and add 0.86 g of chloranil to 3 parts.
The mixture was added at 0 minutes and stirred for 1 hour. The reaction solution was concentrated and ethyl acetate was added to the residue for crystallization and filtration. The obtained crude crystals were purified by silica gel column chromatography to obtain 0.17 g of a blue-black crystal of compound B15 represented by the following chemical formula. A peak showing a mass of 730 (MH + ) was confirmed by LC / MS. λmax was 674 nm (methanol).
【0129】[0129]
【化42】 [Chemical 42]
【0130】実施例47Example 47
【0131】[0131]
【化43】 [Chemical 43]
【0132】上記化学式(M6)で示される公知のピロ
ロピロール化合物0.5g、塩化ホスホリル6mlを混
合し110℃で3時間攪拌後、60℃まで冷却しN,N
−ジメチルアニリン1mlを加え同温度で4時間攪拌し
た。加熱をやめ室温まで放冷し、氷水に滴下しクロロホ
ルムを加え水酸化ナトリウムで水層を中和した後、有機
層を分取、濃縮しシリカゲルクロマトグラフィにより精
製して黒紫色結晶0.1gを得た。この化合物は可視吸
収スペクトル、IR、LC/MS、NMRの分析結果が
実施例17で得た化合物A21と一致しており同一化合
物であることが確認された。0.5 g of a known pyrrolopyrrole compound represented by the above chemical formula (M6) and 6 ml of phosphoryl chloride were mixed and stirred at 110 ° C. for 3 hours, and then cooled to 60 ° C. N, N.
-1 ml of dimethylaniline was added and stirred at the same temperature for 4 hours. After stopping heating, the mixture was allowed to cool to room temperature, added dropwise to ice water, chloroform was added to neutralize the aqueous layer with sodium hydroxide, the organic layer was separated, concentrated and purified by silica gel chromatography to obtain 0.1 g of black-purple crystals. It was This compound was confirmed to be the same compound because the analytical results of visible absorption spectrum, IR, LC / MS, and NMR were the same as those of the compound A21 obtained in Example 17.
【0133】実施例48Example 48
【0134】[0134]
【化44】 [Chemical 44]
【0135】上記化学式で示される公知のピロロピロー
ル化合物(M7)1.0g、塩化ホスホリル15mlを
混合し110℃で3時間攪拌後、60℃まで冷却しN,
N−ジメチルアニリン2mlを滴下し60℃で4時間攪
拌した。室温まで放冷後、氷水に滴下しクロロホルムを
加え水酸化ナトリウムで中和して有機層を分取、濃縮
後、シリカゲルカラムクロマトグラフィで精製して第1
表に示す化合物A20の紫色結晶0.56gを得た。1.0 g of the known pyrrolopyrrole compound (M7) represented by the above chemical formula and 15 ml of phosphoryl chloride were mixed and stirred at 110 ° C. for 3 hours, then cooled to 60 ° C. and N,
2 ml of N-dimethylaniline was added dropwise and stirred at 60 ° C. for 4 hours. After cooling to room temperature, the mixture was added dropwise to ice water, chloroform was added, and the mixture was neutralized with sodium hydroxide to separate and concentrate the organic layer, which was then purified by silica gel column chromatography.
0.56 g of purple crystals of Compound A20 shown in the table were obtained.
【0136】LC/MS:410(MH+)、λma
x:577nm(クロロホルム),594nm(メタノ
ール),610nm(フィルム)、IR(KBr):2
205cm−1、1H−NMR(CDCl3):δ3.
17(s,6H),6.74(d,2H),7.31−
7.66(m,10H),8.22(d,2H)。元素
分析:C=75.79%,H=5.11%,N=9.9
3%,Cl=8.51%(計算値C=76.18%,H
=4.92%,N=10.25%,Cl=8.65%、
C26H20N3Cl)。LC / MS: 410 (MH + ), λma
x: 577 nm (chloroform), 594 nm (methanol), 610 nm (film), IR (KBr): 2
205 cm < -1 >, < 1 > H-NMR (CDCl3) :( delta) 3 .
17 (s, 6H), 6.74 (d, 2H), 7.31-
7.66 (m, 10H), 8.22 (d, 2H). Elemental analysis: C = 75.79%, H = 5.11%, N = 9.9
3%, Cl = 8.51% (calculated value C = 76.18%, H
= 4.92%, N = 10.25%, Cl = 8.65%,
C 26 H 20 N 3 Cl) .
【0137】実施例49
前記ピロロピロール化合物(M7)0.052g、塩化
ホスホリル1mlを混合し110℃で3時間攪拌後、6
0℃まで冷却し1−(4−ジメチルアミノフェニル)−
1−(4−メトキシフェニル)エテン0.091gを加
え60℃で3時間攪拌した。室温まで放冷後、氷水に滴
下しクロロホルムを加え水酸化ナトリウムで中和して有
機層を分取、濃縮後、シリカゲルカラムクロマトグラフ
ィで精製して第2表に示す化合物B24の黒紫色結晶
0.025gを得た。LC/MS:542(MH+)、
λmax:656nm(クロロホルム)。Example 49 0.052 g of the above-mentioned pyrrolopyrrole compound (M7) and 1 ml of phosphoryl chloride were mixed and stirred at 110 ° C. for 3 hours.
After cooling to 0 ° C, 1- (4-dimethylaminophenyl)-
1- (4-Methoxyphenyl) ethene (0.091 g) was added, and the mixture was stirred at 60 ° C for 3 hr. After cooling to room temperature, the mixture was added dropwise to ice water, chloroform was added, and the mixture was neutralized with sodium hydroxide to separate the organic layer, concentrated and purified by silica gel column chromatography to give compound B24 shown in Table 2 black purple crystals. 025g was obtained. LC / MS: 542 (MH + ),
λmax: 656 nm (chloroform).
【0138】実施例50
実施例49の操作において、1−(4−ジメチルアミノ
フェニル)−1−(4−メトキシフェニル)エテン0.
091gの代わりに1−エチル−2−フェニルインドー
ル0.080gを用い、他は実施例49と同様に操作し
て第3表に示す化合物C8の黒紫色結晶0.065gを
得た。LC/MS:510(MH+)、λmax:55
6nm(クロロホルム)。元素分析:C=80.11
%,H=4.72%,N=7.91%,Cl=6.76
%(計算値C=80.07%,H=4.74%,N=
8.24%,Cl=6.95%、C34H24N3C
l)。Example 50 In the procedure of Example 49, 1- (4-dimethylaminophenyl) -1- (4-methoxyphenyl) ethene 0.
0.080 g of 1-ethyl-2-phenylindole was used instead of 091 g, and the same operation as in Example 49 was carried out otherwise to obtain 0.065 g of black-purple crystals of compound C8 shown in Table 3. LC / MS: 510 (MH + ), λmax: 55
6 nm (chloroform). Elemental analysis: C = 80.11
%, H = 4.72%, N = 7.91%, Cl = 6.76
% (Calculated value C = 80.07%, H = 4.74%, N =
8.24%, Cl = 6.95%, C 34 H 24 N 3 C
l).
【0139】実施例51
実施例49の操作において、1−(4−ジメチルアミノ
フェニル)−1−(4−メトキシフェニル)エテン0.
091gの代わりにN,N−ジブチルアニリン0.07
2gを用い、他は実施例49と同様に操作して第1表に
示す化合物A24の黒緑色結晶0.040gを得た。L
C/MS:494(MH+)、λmax:592nm
(クロロホルム)、1H−NMR(CDCl3):δ=
0.99(6H,t),1.34−1.46(4H,
m),1.62−1.72(4H,m),3.37−
3.50(4H,m),6.71(2H,d),7.3
2−7.66(10H,m),8.22(2H,d)。Example 51 In the procedure of Example 49, 1- (4-dimethylaminophenyl) -1- (4-methoxyphenyl) ethene 0.
N, N-dibutylaniline 0.07 instead of 091 g
The same procedure as in Example 49 was carried out except that 2 g was used to obtain 0.040 g of a black green crystal of compound A24 shown in Table 1. L
C / MS: 494 (MH + ), λmax: 592 nm
(Chloroform), 1 H-NMR (CDCl 3 ): δ =
0.99 (6H, t), 1.34 to 1.46 (4H,
m), 1.62-1.72 (4H, m), 3.37-
3.50 (4H, m), 6.71 (2H, d), 7.3
2-7.66 (10H, m), 8.22 (2H, d).
【0140】実施例52
実施例48で得た化合物A20を0.50gをDMF5
mlに溶解し、無水炭酸カリウム0.25gを加え攪拌
しながらt−ブチルチオフェノール0.32gを少しず
つ滴下した。その後30分攪拌して水に注加しクロロホ
ルムで抽出した。有機層を重曹水で洗浄、硫酸マグネシ
ウムで乾燥後、濃縮した。カラムクロマトグラフィで精
製して第1表で示す化合物A23の紫色結晶0.30g
を得た。LC/MS:540(MH+)、λmax:5
62nm(CHCl3),1H−NMR(CDC
l3):δ1.29(s,9H),3.15(s,6
H),6.75(d,2H),7.25−7.64
(m,14H),8.15(d,2H)。Example 52 0.50 g of the compound A20 obtained in Example 48 was added to DMF5.
It was dissolved in ml, 0.25 g of anhydrous potassium carbonate was added, and 0.32 g of t-butylthiophenol was added dropwise little by little with stirring. Then, the mixture was stirred for 30 minutes, poured into water, and extracted with chloroform. The organic layer was washed with aqueous sodium hydrogen carbonate, dried over magnesium sulfate, and concentrated. 0.30 g of purple crystals of compound A23 shown in Table 1 after purified by column chromatography
Got LC / MS: 540 (MH + ), λmax: 5
62 nm (CHCl 3 ), 1 H-NMR (CDC
l 3 ): δ1.29 (s, 9H), 3.15 (s, 6)
H), 6.75 (d, 2H), 7.25-7.64.
(M, 14H), 8.15 (d, 2H).
【0141】比較例1
下記化学式で示される化合物につき溶解度を測定した。
この化合物はメタノール、アセトン、酢酸エチル、クロ
ロホルムのいずれの溶剤に対しても溶解度は0.1%以
下であった。Comparative Example 1 The solubility of a compound represented by the following chemical formula was measured.
This compound had a solubility of 0.1% or less in any solvent such as methanol, acetone, ethyl acetate and chloroform.
【0142】[0142]
【化45】 [Chemical formula 45]
【0143】次に本発明の化合物につき塗布膜の耐光性
試験を行った結果を以下に示す。
実施例X−1
前記実施例2で得た色素化合物A1を0.5g、ガラス
瓶に仕込み、10%ポリビニルアルコール水溶液10
g、水7.0g、ガラスビーズ20gを加えペイントシ
ェーカーで30分振とうして色素を分散させた。この分
散液を中性紙の上にワイヤーバーを用いて塗布、風乾し
て、色素塗布量が0.6g/m2である塗布紙を得た。
塗布面の色相は青黒色であった。Next, the results of the light resistance test of the coating film of the compound of the present invention are shown below. Example X-1 0.5 g of the dye compound A1 obtained in Example 2 was charged in a glass bottle, and 10% polyvinyl alcohol aqueous solution 10 was added.
g, 7.0 g of water, and 20 g of glass beads were added, and the mixture was shaken for 30 minutes with a paint shaker to disperse the dye. This dispersion was applied onto a neutral paper using a wire bar and air-dried to obtain a coated paper having a dye coating amount of 0.6 g / m 2 .
The hue of the coated surface was bluish black.
【0144】実施例X−2
実施例X−1における化合物A1の代わりに実施例4で
得た化合物A3を用い、他は実施例X−1と同様に操作
して色素塗布紙を得た。塗布面の色相は青黒色であっ
た。Example X-2 A dye-coated paper was obtained in the same manner as in Example X-1, except that the compound A3 obtained in Example 4 was used instead of the compound A1 in Example X-1. The hue of the coated surface was bluish black.
【0145】実施例X−3
実施例X−1における化合物A1の代わりに実施例11
で得た化合物A10を用い、他は実施例X−1と同様に
操作して色素塗布紙を得た。塗布面の色相は青黒色であ
った。Example X-3 Example 11 in place of the compound A1 in Example X-1
Using the compound A10 obtained in 1. above, the same operation as in Example X-1 was carried out otherwise to obtain a dye-coated paper. The hue of the coated surface was bluish black.
【0146】実施例X−4
実施例X−1における化合物A1の代わりに実施例26
で得た化合物B10を用い、他は実施例X−1と同様に
操作して色素塗布紙を得た。塗布面の色相は黒紫色であ
った。この塗布膜の可視・近赤外吸収スペクトルを図6
に示す。Example X-4 Example 26 in place of the compound A1 in Example X-1
Using the compound B10 obtained in 1. above, the same operation as in Example X-1 was carried out to obtain a dye-coated paper. The hue of the coated surface was black purple. The visible / near infrared absorption spectrum of this coating film is shown in FIG.
Shown in.
【0147】比較例X−1
実施例X−1における化合物A1の代わりに、下記化学
式で表される色素を用い、他は実施例X−1と同様に操
作して色素塗布紙を得た。塗布面の色相は青紫色であっ
た。Comparative Example X-1 A dye-coated paper was obtained in the same manner as in Example X-1, except that the dye represented by the following chemical formula was used instead of the compound A1 in Example X-1. The hue of the coated surface was bluish purple.
【0148】[0148]
【化46】 [Chemical formula 46]
【0149】上記実施例X−1〜X−4及び比較例X−
1で得た色素塗布紙をカーボンアークを光源とするフェ
ードテスターで7時間露光して露光前後の吸光度を測定
した。その結果を下表に示す。Examples X-1 to X-4 and Comparative Example X-
The dye-coated paper obtained in 1 was exposed for 7 hours with a fade tester using a carbon arc as a light source, and the absorbance before and after the exposure was measured. The results are shown in the table below.
【0150】[0150]
【表6】 [Table 6]
【0151】以上の実施例から、本発明のピロール化合
物が可視領域から近赤外領域まで様々な吸収波長を持ち
うる色素であり、有機溶剤に対する溶解度も良く、耐光
性も良好であることが確認された。From the above examples, it was confirmed that the pyrrole compound of the present invention is a dye that can have various absorption wavelengths from the visible region to the near infrared region, has good solubility in organic solvents and good light resistance. Was done.
【0152】[0152]
【発明の効果】本発明は新規なピロール化合物を提案す
るものであり、これらの化合物は高い吸光係数、高溶解
性、高耐光性など色素としての優れた性質を有してお
り、産業上、利用価値の高いものである。INDUSTRIAL APPLICABILITY The present invention proposes a novel pyrrole compound, and these compounds have excellent properties as a dye, such as high extinction coefficient, high solubility, and high light resistance. It has high utility value.
【図1】実施例1で得た化合物A1の赤外吸収スペクト
ル(KBr)1 is an infrared absorption spectrum (KBr) of compound A1 obtained in Example 1. FIG.
【図2】実施例26で得た化合物B10の赤外吸収スペ
クトル(KBr)FIG. 2 Infrared absorption spectrum (KBr) of compound B10 obtained in Example 26.
【図3】実施例4で得た化合物A3の可視吸収スペクト
ル(メタノール溶液)FIG. 3 is a visible absorption spectrum of the compound A3 obtained in Example 4 (methanol solution).
【図4】実施例27で得た化合物B16の可視・近赤外
吸収スペクトル(メタノール溶液)FIG. 4 is a visible / near infrared absorption spectrum of the compound B16 obtained in Example 27 (methanol solution).
【図5】実施例28で得た化合物B13の可視・近赤外
吸収スペクトル(メタノール溶液)FIG. 5: Visible / near infrared absorption spectrum of compound B13 obtained in Example 28 (methanol solution).
【図6】実施例26で得た化合物B10を実施例X−4
の方法で塗布したときの塗布膜の可視・近赤外吸収スペ
クトルFIG. 6 shows the compound B10 obtained in Example 26 as Example X-4.
And near-infrared absorption spectra of coating film coated by the method
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) C07D 403/06 C07D 403/06 413/12 413/12 417/12 417/12 // C09K 3/00 105 C09K 3/00 105 Fターム(参考) 4C063 AA01 AA03 BB01 BB03 BB08 CC06 CC08 CC12 CC14 CC25 CC52 CC62 DD04 EE10 4C069 AD02 BA08 BC01 BC15 4H056 CA01 CC02 CC06 CC08 CE02 CE03 CE06 DD03 DD29 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C07D 403/06 C07D 403/06 413/12 413/12 417/12 417/12 // C09K 3/00 105 C09K 3/00 105 F term (reference) 4C063 AA01 AA03 BB01 BB03 BB08 CC06 CC08 CC12 CC14 CC25 CC52 CC62 DD04 EE10 4C069 AD02 BA08 BC01 BC15 4H056 CA01 CC02 CC06 CC08 CE02 CE03 CE06 DD03 DD29
Claims (12)
物。 【化1】 [式中、Xはアルコキシカルボニル基、シアノ基、カル
ボキシル基のいずれかを表す。Yは置換または非置換の
アルキル基、置換または非置換のアリール基、置換また
は非置換のピリジル基のいずれかを表す。Zはハロゲン
原子、置換または非置換のアリールオキシ基、置換また
は非置換のアルキルチオ基、置換または非置換のアリー
ルチオ基、置換または非置換のピリジルチオ基、置換ま
たは非置換のチアゾリルチオ基、置換または非置換のイ
ミダゾリルチオ基、置換または非置換のトリアゾリルチ
オ基、置換または非置換のテトラゾリルチオ基、置換ま
たは非置換のキノリルチオ基、置換または非置換のベン
ゾチアゾリルチオ基、置換または非置換のベンゾキサゾ
リルチオ基、置換または非置換のベンゾイミダゾリルチ
オ基のいずれかを表す。Q1、Q2は、双方が互いに独
立に下記一般式(1−1)〜(1−5)のいずれかで表
される置換基を表すか、または一方のみが下記一般式
(1−1)〜(1−5)のいずれかで表される置換基で
あり、他方は、水素原子、置換または非置換のアリール
基、1位及び2位がアルキル基またはアリール基によっ
て置換された3−インドリル基のいずれかを表す] 【化2】 [式中、L1は、二級または三級アミノ基、ピロリジノ
基、ピペリジノ基、モルホリノ基のいずれかを表す。L
2〜L5は互いに独立に水素原子、ハロゲン原子、置換
または非置換のアルキル基、置換または非置換のアルコ
キシ基、置換または非置換のアミノ基、置換または非置
換のアシル基、水酸基、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] 【化3】 [L11〜L12は互いに独立にアルキル基、置換また
は非置換のアリール基のいずれかを表す] 【化4】 [Q3、Q4は互いに独立に、水素原子、置換または非
置換のアリール基、1位及び2位がアルキル基またはア
リール基によって置換された3−インドリル基のいずれ
かを表す。Q3、Q4は同時に水素原子にはならないも
のとする。nは0〜2の整数を表す] 【化5】 [L21はアルキル基を表す] 【化6】 [L31はアルキル基を表す]1. A pyrrole compound represented by the following general formula (1). [Chemical 1] [In the formula, X represents an alkoxycarbonyl group, a cyano group, or a carboxyl group. Y represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted pyridyl group. Z is a halogen atom, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted pyridylthio group, a substituted or unsubstituted thiazolylthio group, a substituted or unsubstituted Imidazolylthio group, substituted or unsubstituted triazolylthio group, substituted or unsubstituted tetrazolylthio group, substituted or unsubstituted quinolylthio group, substituted or unsubstituted benzothiazolylthio group, substituted or unsubstituted benzoxazolylthio group Represents a substituted or unsubstituted benzimidazolylthio group. Q1 and Q2 each independently represent a substituent represented by any one of the following general formulas (1-1) to (1-5), or only one of the following general formulas (1-1) to (1-5). (1-5) is a substituent, and the other is a 3-indolyl group in which a hydrogen atom, a substituted or unsubstituted aryl group, and 1- and 2-positions are substituted with an alkyl group or an aryl group. Represents any of the following] [In the formula, L1 represents any of a secondary or tertiary amino group, a pyrrolidino group, a piperidino group, and a morpholino group. L
2 to L5 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted acyl group, a hydroxyl group, a carboxyl group, Represents any of alkoxycarbonyl groups] [L11 to L12 each independently represent an alkyl group or a substituted or unsubstituted aryl group] [Q3 and Q4 each independently represent a hydrogen atom, a substituted or unsubstituted aryl group, or a 3-indolyl group substituted at the 1-position and 2-position with an alkyl group or an aryl group. It is assumed that Q3 and Q4 do not become hydrogen atoms at the same time. n represents an integer of 0 to 2] [L21 represents an alkyl group] [L31 represents an alkyl group]
物。 【化7】 [式中、Xはアルコキシカルボニル基、シアノ基、カル
ボキシル基のいずれかを表す。Yは置換または非置換の
アルキル基、置換または非置換のアリール基、置換また
は非置換のピリジル基のいずれかを表す。Zはハロゲン
原子、置換または非置換のアリールオキシ基、置換また
は非置換のアルキルチオ基、置換または非置換のアリー
ルチオ基、置換または非置換のピリジルチオ基、置換ま
たは非置換のチアゾリルチオ基、置換または非置換のイ
ミダゾリルチオ基、置換または非置換のトリアゾリルチ
オ基、置換または非置換のテトラゾリルチオ基、置換ま
たは非置換のキノリルチオ基、置換または非置換のベン
ゾチアゾリルチオ基、置換または非置換のベンゾキサゾ
リルチオ基、置換または非置換のベンゾイミダゾリルチ
オ基のいずれかを表す。R1は、二級または三級アミノ
基、ピロリジノ基、ピペリジノ基、モルホリノ基のいず
れかを表す。R2〜R10は互いに独立に、水素原子、
ハロゲン原子、置換または非置換のアルキル基、置換ま
たは非置換のアルコキシ基、置換または非置換のアミノ
基、置換または非置換のアシル基、水酸基、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わす]2. A pyrrole compound represented by the following general formula (2). [Chemical 7] [In the formula, X represents an alkoxycarbonyl group, a cyano group, or a carboxyl group. Y represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted pyridyl group. Z is a halogen atom, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted pyridylthio group, a substituted or unsubstituted thiazolylthio group, a substituted or unsubstituted Imidazolylthio group, substituted or unsubstituted triazolylthio group, substituted or unsubstituted tetrazolylthio group, substituted or unsubstituted quinolylthio group, substituted or unsubstituted benzothiazolylthio group, substituted or unsubstituted benzoxazolylthio group Represents a substituted or unsubstituted benzimidazolylthio group. R1 represents any of a secondary or tertiary amino group, a pyrrolidino group, a piperidino group, and a morpholino group. R2 to R10 are each independently a hydrogen atom,
Represents a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted acyl group, a hydroxyl group, a carboxyl group or an alkoxycarbonyl group]
物。 【化8】 [式中、Xはアルコキシカルボニル基、シアノ基、カル
ボキシル基のいずれかを表す。Yは置換または非置換の
アルキル基、置換または非置換のアリール基、置換また
は非置換のピリジル基のいずれかを表す。Zはハロゲン
原子、置換または非置換のアリールオキシ基、置換また
は非置換のアルキルチオ基、置換または非置換のアリー
ルチオ基、置換または非置換のピリジルチオ基、置換ま
たは非置換のチアゾリルチオ基、置換または非置換のイ
ミダゾリルチオ基、置換または非置換のトリアゾリルチ
オ基、置換または非置換のテトラゾリルチオ基、置換ま
たは非置換のキノリルチオ基、置換または非置換のベン
ゾチアゾリルチオ基、置換または非置換のベンゾキサゾ
リルチオ基、置換または非置換のベンゾイミダゾリルチ
オ基のいずれかを表す。R21〜R25は互いに独立
に、水素原子、ハロゲン原子、置換または非置換のアル
キル基、置換または非置換のアルコキシ基、置換または
非置換のアミノ基、置換または非置換のアシル基、水酸
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。R11、R12は互いに独立に置換または非
置換のアルキル基、置換または非置換のアリール基のい
ずれかを表す]3. A pyrrole compound represented by the following general formula (3). [Chemical 8] [In the formula, X represents an alkoxycarbonyl group, a cyano group, or a carboxyl group. Y represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted pyridyl group. Z is a halogen atom, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted pyridylthio group, a substituted or unsubstituted thiazolylthio group, a substituted or unsubstituted Imidazolylthio group, substituted or unsubstituted triazolylthio group, substituted or unsubstituted tetrazolylthio group, substituted or unsubstituted quinolylthio group, substituted or unsubstituted benzothiazolylthio group, substituted or unsubstituted benzoxazolylthio group Represents a substituted or unsubstituted benzimidazolylthio group. R21 to R25 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted acyl group, a hydroxyl group, a carboxyl group. Represents an alkoxycarbonyl group. R11 and R12 each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group]
物。 【化9】 [式中、Xはアルコキシカルボニル基、シアノ基、カル
ボキシル基のいずれかを表す。Yは置換または非置換の
アルキル基、置換または非置換のアリール基、置換また
は非置換のピリジル基のいずれかを表す。Zはハロゲン
原子、置換または非置換のアリールオキシ基、置換また
は非置換のアルキルチオ基、置換または非置換のアリー
ルチオ基、置換または非置換のピリジルチオ基、置換ま
たは非置換のチアゾリルチオ基、置換または非置換のイ
ミダゾリルチオ基、置換または非置換のトリアゾリルチ
オ基、置換または非置換のテトラゾリルチオ基、置換ま
たは非置換のキノリルチオ基、置換または非置換のベン
ゾチアゾリルチオ基、置換または非置換のベンゾキサゾ
リルチオ基、置換または非置換のベンゾイミダゾリルチ
オ基のいずれかを表す。R31〜R34は互いに独立に
置換または非置換のアルキル基、置換または非置換のア
リール基のいずれかを表す]4. A pyrrole compound represented by the following general formula (4). [Chemical 9] [In the formula, X represents an alkoxycarbonyl group, a cyano group, or a carboxyl group. Y represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted pyridyl group. Z is a halogen atom, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted pyridylthio group, a substituted or unsubstituted thiazolylthio group, a substituted or unsubstituted Imidazolylthio group, substituted or unsubstituted triazolylthio group, substituted or unsubstituted tetrazolylthio group, substituted or unsubstituted quinolylthio group, substituted or unsubstituted benzothiazolylthio group, substituted or unsubstituted benzoxazolylthio group Represents a substituted or unsubstituted benzimidazolylthio group. R31 to R34 each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group]
物。 【化10】 [式中、Xはアルコキシカルボニル基、シアノ基、カル
ボキシル基のいずれかを表す。Yは置換または非置換の
アルキル基、置換または非置換のアリール基、置換また
は非置換のピリジル基のいずれかを表す。Zはハロゲン
原子、置換または非置換のアリールオキシ基、置換また
は非置換のアルキルチオ基、置換または非置換のアリー
ルチオ基、置換または非置換のピリジルチオ基、置換ま
たは非置換のチアゾリルチオ基、置換または非置換のイ
ミダゾリルチオ基、置換または非置換のトリアゾリルチ
オ基、置換または非置換のテトラゾリルチオ基、置換ま
たは非置換のキノリルチオ基、置換または非置換のベン
ゾチアゾリルチオ基、置換または非置換のベンゾキサゾ
リルチオ基、置換または非置換のベンゾイミダゾリルチ
オ基のいずれかを表す。R41は二級または三級アミノ
基、ピロリジノ基、ピペリジノ基、モルホリノ基のいず
れかを表す。R42〜R45は互いに独立に、水素原
子、ハロゲン原、置換または非置換のアルキル基、置換
または非置換のアルコキシ基、置換または非置換のアミ
ノ基、置換または非置換のアシル基、水酸基、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。Q
5、Q6は水素原子、置換または非置換のアリール基、
1位及び2位がアルキル基またはアリール基によって置
換された3−インドリル基のいずれかを表す。nは0ま
たは1を表す]5. A pyrrole compound represented by the following general formula (5). [Chemical 10] [In the formula, X represents an alkoxycarbonyl group, a cyano group, or a carboxyl group. Y represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted pyridyl group. Z is a halogen atom, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted pyridylthio group, a substituted or unsubstituted thiazolylthio group, a substituted or unsubstituted Imidazolylthio group, substituted or unsubstituted triazolylthio group, substituted or unsubstituted tetrazolylthio group, substituted or unsubstituted quinolylthio group, substituted or unsubstituted benzothiazolylthio group, substituted or unsubstituted benzoxazolylthio group Represents a substituted or unsubstituted benzimidazolylthio group. R41 represents any of a secondary or tertiary amino group, a pyrrolidino group, a piperidino group, and a morpholino group. R42 to R45 each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted acyl group, a hydroxyl group, a carboxyl group. Represents an alkoxycarbonyl group. Q
5, Q6 is a hydrogen atom, a substituted or unsubstituted aryl group,
1-position and 2-position represent either a 3-indolyl group substituted by an alkyl group or an aryl group. n represents 0 or 1]
基であり、Yが非置換またはフッ素によって置換された
アルキル基、非置換またはシアノ基もしくはジアルキル
アミノ基によって置換されたフェニル基、非置換または
アルキル基もしくはニトロ基によって置換されたピリジ
ル基のいずれかであり、Zが塩素原子、非置換またはカ
ルボキシル基によって置換されたアルキルチオ基、非置
換またはアルキル基もしくはカルボキシル基によって置
換されたフェニルチオ基、非置換またはアルキル基もし
くはアリール基によって置換されたイミダゾリルチオ
基、非置換またはアルキル基によって置換されたトリア
ゾリルチオ基、非置換またはアルキル基もしくはアルコ
キシ基によって置換されたベンゾチアゾリルチオ基、非
置換またはアルキル基もしくはアルコキシ基によって置
換されたベンゾキサゾリルチオ基、非置換またはアルキ
ル基、アルコキシ基もしくはニトロ基によって置換され
たベンゾイミダゾリルチオ基のいずれかである請求項1
〜5のいずれかに記載のピロール化合物。6. X is an alkoxycarbonyl group or cyano group, Y is an unsubstituted or fluorine-substituted alkyl group, a phenyl group unsubstituted or substituted with a cyano group or a dialkylamino group, an unsubstituted or alkyl group. Or a pyridyl group substituted by a nitro group, Z is a chlorine atom, an alkylthio group unsubstituted or substituted by a carboxyl group, a phenylthio group unsubstituted or substituted by an alkyl group or a carboxyl group, unsubstituted or Imidazolylthio group substituted by alkyl group or aryl group, triazolylthio group unsubstituted or substituted by alkyl group, benzothiazolylthio group unsubstituted or substituted by alkyl group or alkoxy group, unsubstituted or alkyl Or benzoxathiol benzoisothiazolyl thio group substituted by an alkoxy group, an unsubstituted or alkyl group, claim 1 is either benzoimidazolylthio group substituted by an alkoxy group or a nitro group
The pyrrole compound according to any one of to 5.
R2〜R5、R7〜R10が水素原子であり、Xがアル
コキシカルボニル基またはシアノ基であり、Yが非置換
またはフッ素によって置換されたアルキル基、非置換ま
たはシアノ基もしくはジアルキルアミノ基によって置換
されたフェニル基、非置換またはアルキル基によって置
換されたピリジル基のいずれかであり、Zが塩素原子、
非置換またはカルボキシル基によって置換されたアルキ
ルチオ基、非置換またはアルキル基もしくはカルボキシ
ル基によって置換されたフェニルチオ基、非置換または
アルキル基もしくはアリール基によって置換されたイミ
ダゾリルチオ基、非置換またはアルキル基によって置換
されたトリアゾリルチオ基、非置換またはアルキル基ま
たはアルコキシ基によって置換されたベンゾチアゾリル
チオ基、非置換またはアルキル基またはアルコキシ基に
よって置換されたベンゾキサゾリルチオ基、非置換また
はアルキル基、アルコキシ基もしくはニトロ基によって
置換されたベンゾイミダゾリルチオ基のいずれかである
請求項2記載のピロール化合物。7. R1 and R6 are dialkylamino groups,
R2 to R5, R7 to R10 are hydrogen atoms, X is an alkoxycarbonyl group or a cyano group, Y is unsubstituted or substituted with a fluorine-substituted alkyl group, unsubstituted or substituted with a cyano group or a dialkylamino group A phenyl group, a pyridyl group which is unsubstituted or substituted by an alkyl group, Z is a chlorine atom,
Unsubstituted or substituted by a carboxyl group, alkylthio group, unsubstituted or substituted by an alkyl group or carboxyl group, phenylthio group, unsubstituted or substituted by an alkyl group or aryl group, imidazolylthio group, unsubstituted or substituted by an alkyl group Triazolylthio group, substituted or benzothiazolylthio group substituted with an alkyl or alkoxy group, benzoxazolylthio group unsubstituted or substituted with an alkyl or alkoxy group, unsubstituted or alkyl group, alkoxy group or The pyrrole compound according to claim 2, which is any of a benzimidazolylthio group substituted by a nitro group.
2〜R25が水素原子であり、R11またはR12が非
置換のアルキル基または非置換のフェニル基であり、X
がアルコキシカルボニル基またはシアノ基であり、Yが
非置換またはフッ素によって置換されたアルキル基、非
置換またはシアノ基もしくはジアルキルアミノ基によっ
て置換されたフェニル基、非置換またはアルキル基によ
って置換されたピリジル基のいずれかであり、Zが塩素
原子、非置換またはカルボキシル基によって置換された
アルキルチオ基、非置換またはアルキル基もしくはカル
ボキシル基によって置換されたフェニルチオ基、非置換
またはアルキル基もしくはアリール基によって置換され
たイミダゾリルチオ基、非置換またはアルキル基によっ
て置換されたトリアゾリルチオ基、非置換またはアルキ
ル基もしくはアルコキシ基によって置換されたベンゾチ
アゾリルチオ基、非置換またはアルキル基もしくはアル
コキシ基によって置換されたベンゾキサゾリルチオ基、
非置換またはアルキル基、アルコキシ基もしくはニトロ
基によって置換されたベンゾイミダゾリルチオ基のいず
れかである請求項3記載のピロール化合物。8. R21 is a dialkylamino group, R2
2 to R25 are hydrogen atoms, R11 or R12 is an unsubstituted alkyl group or an unsubstituted phenyl group, and X
Is an alkoxycarbonyl group or a cyano group, and Y is an alkyl group which is unsubstituted or substituted by fluorine, a phenyl group which is unsubstituted or substituted by a cyano group or a dialkylamino group, a pyridyl group which is unsubstituted or substituted by an alkyl group Z is a chlorine atom, an alkylthio group unsubstituted or substituted by a carboxyl group, a phenylthio group unsubstituted or substituted by an alkyl group or a carboxyl group, unsubstituted or substituted by an alkyl group or an aryl group By an imidazolylthio group, a triazolylthio group which is unsubstituted or substituted by an alkyl group, a benzothiazolylthio group which is unsubstituted or substituted by an alkyl group or an alkoxy group, unsubstituted or by an alkyl group or an alkoxy group Conversion benzo hexa benzoisothiazolyl thio group,
The pyrrole compound according to claim 3, which is either a benzimidazolylthio group which is unsubstituted or substituted by an alkyl group, an alkoxy group or a nitro group.
は非置換のフェニル基であり、Xがアルコキシカルボニ
ル基またはシアノ基であり、Yが非置換またはフッ素に
よって置換されたアルキル基、非置換またはシアノ基も
しくはジアルキルアミノ基によって置換されたフェニル
基、非置換またはアルキル基によって置換されたピリジ
ル基のいずれかであり、Zが塩素原子、非置換またはカ
ルボキシル基によって置換されたアルキルチオ基、非置
換またはアルキル基もしくはカルボキシル基によって置
換されたフェニルチオ基、非置換またはアルキル基もし
くはアリール基によって置換されたイミダゾリルチオ
基、非置換またはアルキル基によって置換されたトリア
ゾリルチオ基、非置換またはアルキル基もしくはアルコ
キシ基によって置換されたベンゾチアゾリルチオ基、非
置換またはアルキル基もしくはアルコキシ基によって置
換されたベンゾキサゾリルチオ基、非置換またはアルキ
ル基、アルコキシ基もしくはニトロ基によって置換され
たベンゾイミダゾリルチオ基のいずれかである請求項4
記載のピロール化合物。9. R31 to R34 each represents an unsubstituted alkyl group or an unsubstituted phenyl group, X represents an alkoxycarbonyl group or a cyano group, and Y represents an unsubstituted or fluorine-substituted alkyl group, an unsubstituted or It is either a phenyl group substituted by a cyano group or a dialkylamino group, a pyridyl group unsubstituted or substituted by an alkyl group, and Z is a chlorine atom, an alkylthio group unsubstituted or substituted by a carboxyl group, unsubstituted or Phenylthio group substituted by alkyl or carboxyl group, imidazolylthio group unsubstituted or substituted by alkyl group or aryl group, triazolylthio group unsubstituted or substituted by alkyl group, unsubstituted or substituted by alkyl group or alkoxy group A substituted benzothiazolylthio group, a benzoxazolylthio group which is unsubstituted or substituted by an alkyl group or an alkoxy group, and a benzimidazolylthio group which is unsubstituted or substituted by an alkyl group, an alkoxy group or a nitro group. Item 4
The described pyrrole compound.
42〜R45が水素原子であり、Q5、Q6が互いに独
立に、非置換またはアルキル基、アルコキシ基もしくは
ジアルキルアミノ基のいずれかによって置換されたフェ
ニル基であり、Xがアルコキシカルボニル基であり、Y
が非置換またはフッ素によって置換されたアルキル基、
非置換またはシアノ基もしくはジアルキルアミノ基によ
って置換されたフェニル基、非置換またはアルキル基に
よって置換されたピリジル基のいずれかであり、Zが塩
素原子、非置換またはカルボキシル基によって置換され
たアルキルチオ基、非置換またはアルキル基もしくはカ
ルボキシル基によって置換されたフェニルチオ基、非置
換またはアルキル基もしくはアリール基によって置換さ
れたイミダゾリルチオ基、非置換またはアルキル基によ
って置換されたトリアゾリルチオ基、非置換またはアル
キル基もしくはアルコキシ基によって置換されたベンゾ
チアゾリルチオ基、非置換またはアルキル基もしくはア
ルコキシ基によって置換されたベンゾキサゾリルチオ
基、非置換またはアルキル基、アルコキシ基もしくはニ
トロ基によって置換されたベンゾイミダゾリルチオ基の
いずれかである請求項5記載のピロール化合物。10. R41 is a dialkylamino group,
42 to R45 are hydrogen atoms, Q5 and Q6 are each independently a phenyl group which is unsubstituted or substituted by any of an alkyl group, an alkoxy group or a dialkylamino group, X is an alkoxycarbonyl group, and Y
Is an alkyl group which is unsubstituted or substituted by fluorine,
An alkylthio group, which is either a phenyl group unsubstituted or substituted by a cyano group or a dialkylamino group, a pyridyl group unsubstituted or substituted by an alkyl group, and Z is a chlorine atom, unsubstituted or substituted by a carboxyl group, A phenylthio group which is unsubstituted or substituted by an alkyl group or a carboxyl group, an imidazolylthio group which is unsubstituted or substituted by an alkyl group or an aryl group, a triazolylthio group which is unsubstituted or substituted by an alkyl group, an unsubstituted or alkyl group or alkoxy A benzothiazolylthio group substituted by a group, a benzoxazolylthio group unsubstituted or substituted by an alkyl or alkoxy group, unsubstituted or substituted by an alkyl group, an alkoxy group or a nitro group Pyrrole compound of claim 5, wherein either the benzoimidazolylthio group.
アミノ基によって置換されたフェニル基、または水素原
子である請求項10記載のピロール化合物。11. The pyrrole compound according to claim 10, wherein Q5 and Q6 each independently represent a phenyl group substituted by a dialkylamino group or a hydrogen atom.
された炭素数4以下のアルキル基または非置換のフェニ
ル基であり、Zが塩素原子、非置換またはカルボキシル
基によって置換されたアルキルチオ基、非置換または炭
素数4以下のアルキル基もしくはカルボキシル基によっ
て置換されたフェニルチオ基、非置換または炭素数4以
下のアルキル基によって置換されたイミダゾリルチオ
基、非置換または炭素数4以下のアルキル基によって置
換されたトリアゾリルチオ基、非置換またはメチル基も
しくは炭素数4以下のアルコキシ基によって置換された
ベンゾチアゾリルチオ基、非置換またはメチル基もしく
は炭素数4以下のアルコキシ基によって置換されたベン
ゾキサゾリルチオ基、非置換またはメチル基もしくは炭
素数4以下のアルコキシ基によって置換されたベンゾイ
ミダゾリルチオ基のいずれかである請求項7〜11のい
ずれかに記載のピロール化合物。12. Y is an alkyl group having 4 or less carbon atoms, which is unsubstituted or substituted with fluorine, or an unsubstituted phenyl group, and Z is an alkylthio group, which is substituted with a chlorine atom, an unsubstituted group or a carboxyl group, and an unsubstituted group. Or a phenylthio group substituted by an alkyl group having 4 or less carbon atoms or a carboxyl group, an imidazolylthio group unsubstituted or substituted by an alkyl group having 4 or less carbon atoms, unsubstituted or substituted by an alkyl group having 4 or less carbon atoms Triazolylthio group, benzothiazolylthio group unsubstituted or substituted with a methyl group or an alkoxy group having 4 or less carbon atoms, non-substituted or benzoxazolylthio group substituted with a methyl group or an alkoxy group having 4 or less carbon atoms, Substituted or methyl group or alco having 4 or less carbon atoms Pyrrole compound according to any one of claims 7-11 is either benzoimidazolylthio group substituted by Shi group.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004083170A2 (en) * | 2003-03-19 | 2004-09-30 | Ciba Specialty Chemicals Holding Inc. | Compounds, a process for their preparation and their use as dyes and pigments |
JP2005015750A (en) * | 2003-06-24 | 2005-01-20 | Yamada Chem Co Ltd | Perimidine compound |
JP2009108112A (en) * | 2007-10-26 | 2009-05-21 | Konica Minolta Holdings Inc | Method for producing monomethine compound and monomethine compound |
JP2014177037A (en) * | 2013-03-14 | 2014-09-25 | Yamamoto Chem Inc | Heat-sensitive chromogenic compositions and heat-sensitive recording materials using said compositions |
JP2015168725A (en) * | 2014-03-05 | 2015-09-28 | 東洋インキScホールディングス株式会社 | Pigment additive, pigment composition using the same, coloring composition, and color filter |
-
2001
- 2001-11-30 JP JP2001402309A patent/JP4164633B2/en not_active Expired - Fee Related
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004083170A2 (en) * | 2003-03-19 | 2004-09-30 | Ciba Specialty Chemicals Holding Inc. | Compounds, a process for their preparation and their use as dyes and pigments |
WO2004083170A3 (en) * | 2003-03-19 | 2005-04-28 | Ciba Sc Holding Ag | Compounds, a process for their preparation and their use as dyes and pigments |
JP2005015750A (en) * | 2003-06-24 | 2005-01-20 | Yamada Chem Co Ltd | Perimidine compound |
JP4531360B2 (en) * | 2003-06-24 | 2010-08-25 | 山田化学工業株式会社 | Perimidine compounds |
JP2009108112A (en) * | 2007-10-26 | 2009-05-21 | Konica Minolta Holdings Inc | Method for producing monomethine compound and monomethine compound |
JP2014177037A (en) * | 2013-03-14 | 2014-09-25 | Yamamoto Chem Inc | Heat-sensitive chromogenic compositions and heat-sensitive recording materials using said compositions |
JP2015168725A (en) * | 2014-03-05 | 2015-09-28 | 東洋インキScホールディングス株式会社 | Pigment additive, pigment composition using the same, coloring composition, and color filter |
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