Syntheses and Characteristics of Near Infrared Absorbing Metal Complex Dyes with Quinoid Liqands

醌类配体近红外吸收金属配合物染料的合成及性能

• 批准号: 01550676
• 负责人: YOSHIDA Katsuhira
• 金额: $ 1.09万
• 依托单位: Kochi University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01550676/
• 关键词: Quinones; Functional Dye; Near-IR-absorbing Dye; Metallochromism; Chelate Complex; PPP-MO Calculation; 1,2-ナフトキノン; 5,8-キノリンジオン; 金属イオン指示薬

The first absorption band of some quinoid derivatives was found to be drastically shifted to longer wavelength with a large increase in the absorption absorption intensity by metal chelate complexation. Utilizing these properties, we designed some new near infrared absorbing metal complex dyes with quinoid ligands. The results are summarized as follows :1. The reaction of sodium 1, 2-naphthoquinone-4-sulfonate with various arylamines and 1, 1-bis[p- (dimethylamino) phenyl]ethylene were efficiently promoted by Ni (II) ion to give 4-aminated, 4-arylated, and 4-vinylated 1, 2-naphthoquinones in good yields. The products with strongly electrondonating 4-substituents were found to be suitable ligands for the synthesis of near infrared absorbing dyes.2. The Diels-Alder reacton of 5, 8-quinolinedione with p- (dimethylamino) -styrenes gave new two kinds of isomeric dyes which showed quite different metallochromic behaviors. Upon addition of metal salts, one of the two isomers showed drastic spectra changes to have an intense absorption band in near infrared region. The color-structure relations were investigated.

某些类醌衍生物经金属螯合作用后，其第一吸收带剧烈地向更长的波长偏移，吸收强度大大增加。利用这些性质，我们设计了一些新的近红外吸收类醌配体金属络合染料。研究结果总结如下：1。在Ni （II）离子的催化下，1,2 -萘醌-4-磺酸钠与各种芳胺和1,1 -双[对（二甲氨基）苯基]乙烯反应，得到了4-胺化、4-芳化和4-乙烯化的1,2 -萘醌，收率较高。发现具有强电子给性的4取代基的产物是合成近红外吸收染料的合适配体。5,8 -喹啉二酮与对（二甲胺）苯乙烯的Diels-Alder反应得到了两种新的异构体染料，它们表现出完全不同的金属变色行为。加入金属盐后，其中一种异构体的光谱发生了剧烈变化，在近红外区有较强的吸收带。研究了颜色结构关系。

项目成果

Katsuhira YOSHIDA: "New Near Infrared Absorbing Metal Complex Dyes:Synthesis and Metallochromic Properties of Two Isomeric Ligands,2ー(Dimethylamino)naphtho{〔1,2ーg〕 and 〔2,1ーg〕}quinolineー7,12ーdiones" Bull.Chem.Soc.Jpn.,. 63. 1748-1752 (1990)

Katsuhira YOSHIDA：“新型近红外吸收金属配合物染料：两种异构配体的合成和金属变色性能，2ー（二甲氨基）萘酚{〔1,2ーg〕和〔2,1ーg〕}喹啉ー7,12ー63. 1748-1752 (1990)

Katsuhira YOSHIDA: "The Effect of Metal Chelate Complexation on the Reactivity and Absorption Spectra of 1,2ーNaphthoquinones:New Types of Near I.r.Absorbing Metal Complex Dyes" J.Chem.Soc.,Perkin Trans.l. 1891-1895 (1990)

Katsuhira YOSHIDA：“金属螯合物络合对 1,2-萘醌的反应性和吸收光谱的影响：新型近红外吸收金属络合物染料”J.Chem.Soc.，Perkin Trans.l. 1891-1895 (1990) ）

Katsuhira YOSHIDA: "New Near Infrared Absorbing Metal Complex Dyes:Synthesis and Metallochromic Properties of Two Isomeric Ligands,2ー(Dimethylamino)naphtho{〔1,2ーg〕and〔2,1ーg〕}quinolineー7,12ーdiones" Bull.Chem.Soc.Jpn.,. 63. 1748-1752 (1990)

Katsuhira YOSHIDA：“新型近红外吸收金属配合物染料：两种异构配体的合成和金属变色性能，2ー（二甲氨基）萘酚{〔1,2ーg〕和〔2,1ーg〕喹啉ー7,12ー63. 1748-1752 (1990)

K. Yoshida, T. Koujiri, E. Sakamoto, and Y. Kubo: "New Near Infrared Absorbing Metal Complex Dyes : Synthesis and Metallochromic Properties of Two Isomeric Ligands, 2-(Dimethylamino) naphtho [1, 2-g] and [2, 1-g] quinoline-7, 12-diones." Bull. Chem. Soc.

K. Yoshida、T. Koujiri、E. Sakamoto 和 Y. Kubo：“新型近红外吸收金属络合物染料：两种异构配体 2-(二甲氨基) 萘酚 [1, 2-g] 和 [

Katsuhira YOSHIDA: "New Near Infrared Absorbing Metal Complex Dyes:Synthesis and Metallochromic Properties of Two Isomeric Ligands,2-(Dimethylamino)naphtho{〔1,2-g〕and〔2,1-g〕}quinoline-7,12-diones" Bull.Chem.Soc.Jpn.,. 63. (1990)

Katsuhira YOSHIDA：“新型近红外吸收金属配合物染料：两种异构配体2-（二甲氨基）萘酚{〔1,2-g〕和〔2,1-g〕}喹啉-7,12-的合成和金属变色性能63. (1990)