JP2891746B2 - New imidazole dyes - Google Patents
New imidazole dyesInfo
- Publication number
- JP2891746B2 JP2891746B2 JP12913290A JP12913290A JP2891746B2 JP 2891746 B2 JP2891746 B2 JP 2891746B2 JP 12913290 A JP12913290 A JP 12913290A JP 12913290 A JP12913290 A JP 12913290A JP 2891746 B2 JP2891746 B2 JP 2891746B2
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- Japan
- Prior art keywords
- group
- dye
- general formula
- atom
- represent
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Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は新規なイミダゾール系染料に関する。Description: TECHNICAL FIELD The present invention relates to a novel imidazole dye.
［発明の目的］ 本発明の目的は、カラー画像形成用、フイルター用等
として有用な新規なイミダゾール系染料を提供すること
にある。[Object of the Invention] An object of the present invention is to provide a novel imidazole dye useful for forming a color image, for filtering and the like.
［発明の構成］ 本発明に係るイミダゾール系染料は下記一般式［Ｉ］
で表される。[Structure of the Invention] The imidazole dye according to the present invention has the following general formula [I]
It is represented by
一般式［Ｉ］において、R1、R2およびR3は各々水素原
子または置換基を表す。 In the general formula [I], R 1 , R 2 and R 3 each represent a hydrogen atom or a substituent.
置換基としては、例えば、ハロゲン原子、アルキル
基、アルコキシ基、アリール基、アリールオキシ基、水
酸基、アミド基、ニトロ基、カルボン酸基、スルホン酸
基、アシル基を挙げることができる。Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amide group, a nitro group, a carboxylic acid group, a sulfonic acid group, and an acyl group.
Ｒは水酸基、アルキル基、アリール基、アルコキシ
基、アリールオキシ基，置換アミノ基を表す。R represents a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted amino group.
ＡおよびＢはそれぞれ、アルキル基、アリール基、ヘ
テロ環基、シアノ基、アシル基等の、炭素原子を介して
イミダゾール環に結合する有機基、アシルアミノ基、ア
ルコキシカルボニルアミノ基、アリールオキシカルボニ
ルアミノ基、スルホンアミド基、アニリノ基、ウレイド
基、アミノ基、ヘテロ環基等の、窒素原子を介してイミ
ダゾール環に結合する有機基、アルコキシ基、アリール
オキシ基、ヘテロ環オキシ基等の、酸素原子を介してイ
ミダゾール環に結合する有機基、アルキルチオ基、アリ
ールチオ基、ヘテロ環チオ基等の、硫黄原子を介してイ
ミダゾール環に結合する有機を表す。A and B each represent an organic group, such as an alkyl group, an aryl group, a heterocyclic group, a cyano group, or an acyl group, bonded to the imidazole ring via a carbon atom, an acylamino group, an alkoxycarbonylamino group, or an aryloxycarbonylamino group. , A sulfonamide group, an anilino group, a ureido group, an amino group, a heterocyclic group, etc., an organic group bonded to the imidazole ring through a nitrogen atom, an alkoxy group, an aryloxy group, a heterocyclic oxy group, etc. Represents an organic group bonded to the imidazole ring via a sulfur atom, such as an organic group, an alkylthio group, an arylthio group, or a heterocyclic thio group bonded to the imidazole ring through a sulfur atom.
これらＡ、Ｂ、Ｒ、R1、R2およびR3は更に置換基を有
してもよい。These A, B, R, R 1 , R 2 and R 3 may further have a substituent.
本発明のイミダゾール系染料の代表的例示化合物を次
に挙げる。Representative examples of the imidazole-based dye of the present invention are shown below.
一般式［Ｉ］で表される本発明のイミダゾール系染料
は、例えば下記一般式［II］で表わされる化合物と一般
式［III］で表わされる化合物とを酸化カップリング反
応させることにより容易に合成することができる。 The imidazole dye of the present invention represented by the general formula [I] can be easily synthesized, for example, by subjecting a compound represented by the following general formula [II] and a compound represented by the general formula [III] to an oxidative coupling reaction. can do.
式中、ＡおよびＢは一般式［Ｉ］におけるＡおよびＢ
と同義であり、Ｙは、一般式［III］で表わされる化合
物と酸化カップリングして染料を生成する際離脱する原
子又は基を表わし、水素原子、ハロゲン原子、または、
−Ｏ−、−Ｓ−、−Ｎ−を介して結合する有機残基が好
ましく、特に塩素原子は好ましい。 In the formula, A and B represent A and B in the general formula [I].
Y is an atom or a group which is eliminated when a dye is formed by oxidative coupling with the compound represented by the general formula [III], and a hydrogen atom, a halogen atom, or
An organic residue bonded through —O—, —S—, and —N— is preferable, and a chlorine atom is particularly preferable.
式中、Ｒ、R1、R2およびR3は一般式［Ｉ］における
Ｒ、R1、R2およびR3と同義である。 Wherein, R, R 1, R 2 and R 3 have the same meanings as R, R 1, R 2 and R 3 in the general formula [I].
即ち、本発明の一般式［Ｉ］で表されるイミダゾール
系染料は、 の反応によって合成できる。That is, the imidazole dye represented by the general formula [I] of the present invention is: Can be synthesized by the following reaction.
本発明の化合物は、一般式［Ｉ］のＲ、R1、R2、R3A
およびＢを種々変化することにより、微妙に色相を変化
させることが可能であり、フィルター染料として写真等
に用いたり、感熱転写プロセスやインクジェット方式、
カラー電子写真、印刷等における画像用染料として、ま
た銀塩方式のカラー写真用染料としても有用である。The compound of the present invention is a compound represented by the general formula [I]: R, R 1 , R 2 , R 3 A
By variously changing A and B, it is possible to slightly change the hue, and it is used as a filter dye for a photograph or the like, a thermal transfer process, an ink jet method,
It is also useful as a dye for images in color electrophotography, printing and the like, and also as a dye for silver salt type color photographs.
本発明の染料が銀塩写真のカラー画像を形成するため
に用いられるときは、前記一般式［II］で表される化合
物を感光性ハロゲン化銀写真材料中に含有させておき、
露光後、一般式［III］で表される化合物を含有する発
色現像液で現像することによりカラー画像を形成する。
また現像液中に一般的［II］で表される化合物と一般式
［III］で表される化合物をともに溶解させておき、カ
ラー画像を形成する外式発色法でもカラー画像を形成す
ることができる。When the dye of the present invention is used to form a color image of a silver salt photograph, the compound represented by the general formula [II] is contained in a photosensitive silver halide photographic material,
After exposure, a color image is formed by developing with a color developer containing a compound represented by the general formula [III].
It is also possible to dissolve both the compound represented by the general formula [II] and the compound represented by the general formula [III] in a developer and form a color image by an external color developing method for forming a color image. it can.
［実施例］ 実施例１ 原料（１）18.2gと原料（２）8.9gをクロロホルム150
mlに溶解して室温下に一晩放置する、析出している結晶
を除いてクロロホルムを留去して結晶を得る。水洗後ア
セトニトリルで洗浄して中間体（３）7.2gを得た。[Example] Example 1 18.2g of raw material (1) and 8.9g of raw material (2) were mixed with chloroform 150
After dissolving in water and leaving the mixture at room temperature overnight, chloroform is removed by removing the precipitated crystals to obtain crystals. After washing with water, washing with acetonitrile gave 7.2 g of intermediate (3).
中間体（３）7.2gをエタノール300mlに懸濁し、濃塩
酸50mlを加えると溶解する。この溶液を湯浴上で４時間
還流する。溶媒を留去して氷水100mlを加えると結晶が
析出する。結晶を取しアセトンで洗浄し、クリーム色
の中間体（４）の塩酸塩6.7gを得た。 The intermediate (3) (7.2 g) is suspended in ethanol (300 ml) and dissolved by adding concentrated hydrochloric acid (50 ml). The solution is refluxed for 4 hours on a water bath. When the solvent is distilled off and 100 ml of ice water is added, crystals precipitate. The crystals were collected and washed with acetone to obtain 6.7 g of a hydrochloride of a cream intermediate (4).
上記中間体（４）の塩酸塩5.2gをアセトニトリル170m
lに懸濁し、ピリジン4.0mlを加え、さらに8.0gの２−オ
クチルオキシ−５−ｔ−オクチルベンゼンスルホニルク
ロライドを加えて２時間還流する。反応液を一晩室温下
に放置すると結晶が析出する。結晶を取し、よく水洗
した後、アセトニトリルより再結晶しｍ、p125℃の中間
体（５）9.3gを得た。5.2 g of the hydrochloride of the above intermediate (4) was mixed with acetonitrile 170 m
The suspension was added with 4.0 ml of pyridine, and 8.0 g of 2-octyloxy-5-t-octylbenzenesulfonyl chloride was further added. The mixture was refluxed for 2 hours. When the reaction solution is left overnight at room temperature, crystals precipitate. The crystals were collected, washed well with water, and recrystallized from acetonitrile to obtain 9.3 g of an intermediate (5) having a melting point of 125 ° C.
中間体（５）3.5gと（６）2.1gを酢酸エチル200mlに
溶かし、10％炭酸カリウム水溶液200mlを加える。次に1
0％赤血塩水溶液50mlを加えて室温下１時間撹拌する。
反応後水層を捨て、酢酸エチル層をさらに水洗し、硫酸
マグネシウムで乾燥後、溶媒を留去して染料を得る。カ
ラムクロマトにより精製して目的物を得た。NMR,MASSス
ペクトルにより目的物であることを確認した。 Dissolve 3.5 g of intermediate (5) and 2.1 g of (6) in 200 ml of ethyl acetate and add 200 ml of 10% aqueous potassium carbonate solution. Then 1
Add 50 ml of 0% red blood salt aqueous solution and stir at room temperature for 1 hour.
After the reaction, the aqueous layer is discarded, the ethyl acetate layer is further washed with water, dried over magnesium sulfate, and the solvent is distilled off to obtain a dye. Purification by column chromatography gave the desired product. NMR and MASS spectra confirmed that the product was the desired product.
実施例２ 本発明の染料の例示化合物（４）、（８）、（13）、
（23）について、酢酸エチル溶媒中での最大吸収波長λ
maxを示す。Example 2 Exemplary compounds (4), (8), (13) of the dye of the present invention,
About (23), the maximum absorption wavelength λ in the ethyl acetate solvent.
Indicates max.
例示化合物 λmax（nm） 4 568.4 8 580.6 13 558.2 23 552.8 上記の様に、本発明の染料は極めて実用的な染料であ
る。また、上記から明らかなように、一般式［Ｉ］で表
される化合物の置換基Ｒ、R1、R2、ＡおよびＢは種々変
化させることによりその色相を微妙に変化させることが
できる。Exemplary compound λmax (nm) 4 568.4 8 580.6 13 558.2 23 552.8 As described above, the dye of the present invention is a very practical dye. Further, as is apparent from the above, the hue can be finely changed by variously changing the substituents R, R 1 , R 2 , A and B of the compound represented by the general formula [I].
実施例３ 厚さ６μｍのポリエチレンテレフタレートフィルムベ
ース上に下記組成の分散液Ａをワイヤーバーを用いて塗
布乾燥し感熱転写記録媒体試料１を作成した。次に比較
用染料（Ａ）に代えて本発明の化合物（４）、（８）
（13）および（34）を用いて試料２、３、４および５を
作成した。Example 3 A thermal transfer recording medium sample 1 was prepared by applying and drying a dispersion A having the following composition on a 6 μm thick polyethylene terephthalate film base using a wire bar. Next, compounds (4) and (8) of the present invention are used in place of the comparative dye (A).
Samples 2, 3, 4, and 5 were prepared using (13) and (34).
（分散液Ａ） 比較用染料（Ａ）1gおよびトリクレジルホスフェート
0.5gを酢酸エチル3mlに溶解後、10％ゼラチン水溶液12m
lおよび3.75％アルカノールXC（デュポン社製）水溶液
4.5mlを加え、超音波分散機によって約20分間分散を行
った。分散後、約80℃に加熱して酢酸エチルを除去し、
水を加えて全量を30mlとした。(Dispersion A) 1 g of comparative dye (A) and tricresyl phosphate
After dissolving 0.5g in ethyl acetate 3ml, 10% gelatin aqueous solution 12m
l and 3.75% alkanol XC (manufactured by DuPont) aqueous solution
4.5 ml was added, and the mixture was dispersed by an ultrasonic disperser for about 20 minutes. After dispersion, heat to about 80 ° C to remove ethyl acetate,
Water was added to bring the total volume to 30 ml.
得られた各試料を、サーマルヘッドを用いて普通紙に
熱転写したところ、いずれも赤紫の転写像が得られた
が、本発明化合物を用いた試料２、３、４および５から
得られた画像は、比較用染料（Ａ）と用いた試料１から
得られた画像に比べ高濃度で鮮かであった。When each of the obtained samples was thermally transferred to plain paper using a thermal head, a red-purple transfer image was obtained in each case. However, samples were obtained from Samples 2, 3, 4, and 5 using the compound of the present invention. The image was higher in density and sharper than the image obtained from Sample 1 using the comparative dye (A).
また、画像の自然光に対する強度も高かった。 The intensity of the image with respect to natural light was also high.
［発明の効果］ 本発明の染料は、モル吸光係数が大きく、また、耐光
性も優れている。 [Effect of the Invention] The dye of the present invention has a large molar extinction coefficient and excellent light fastness.
フロントページの続き (56)参考文献 特開 昭63−113077（ＪＰ，Ａ) 特開 平１−110565（ＪＰ，Ａ) 特開 平２−668（ＪＰ，Ａ) 特開 平２−28264（ＪＰ，Ａ) 特開 平２−48992（ＪＰ，Ａ) 特開 平２−53865（ＪＰ，Ａ) 特開 平２−53866（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C09B 55/00 - 57/00 ＣＡ（ＳＴＮ)Continuation of front page (56) References JP-A-63-113077 (JP, A) JP-A-1-110565 (JP, A) JP-A-2-668 (JP, A) JP-A-2-28264 (JP) JP-A-2-48992 (JP, A) JP-A-2-53865 (JP, A) JP-A-2-53866 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB Name) C09B 55/00-57/00 CA (STN)
Claims (1)
系染料 ［式中、R1、R2およびR3は各々水素原子、または置換基
を表す。Ｒは水酸基、アルキル基、アリール基、アルコ
キシ基、アリールオキシ基、置換アミノ基を表し、Ａお
よびＢはそれぞれ炭素原子、窒素原子、酸素原子または
硫黄原子を介してイミダゾール環に結合した有機基を表
す。］An imidazole dye represented by the following general formula [I]: [Wherein, R 1 , R 2 and R 3 each represent a hydrogen atom or a substituent. R represents a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted amino group, and A and B each represent an organic group bonded to an imidazole ring via a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. Represent. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12913290A JP2891746B2 (en) | 1990-05-21 | 1990-05-21 | New imidazole dyes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12913290A JP2891746B2 (en) | 1990-05-21 | 1990-05-21 | New imidazole dyes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0425567A JPH0425567A (en) | 1992-01-29 |
| JP2891746B2 true JP2891746B2 (en) | 1999-05-17 |
Family
ID=15001897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12913290A Expired - Fee Related JP2891746B2 (en) | 1990-05-21 | 1990-05-21 | New imidazole dyes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2891746B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2676663B2 (en) * | 1991-01-30 | 1997-11-17 | 富士写真フイルム株式会社 | Imidazole azomethine dye and thermal transfer dye donating material containing the same |
-
1990
- 1990-05-21 JP JP12913290A patent/JP2891746B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0425567A (en) | 1992-01-29 |
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