Studies on Development of High-sensitive Optical Purity Determination Reagents Using Optically Active Fluorescent Quinoxalines

光学活性荧光喹喔啉类高灵敏度光学纯度测定试剂的研制

• 批准号: 11650876
• 负责人: KATOH Akira
• 金额: $ 1.28万
• 依托单位: Seikei University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650876/
• 关键词: quinoxaline; fluorescent diastereomer; quantum yield; reversed-phase column; HPLC; detection limit; optical purity determination reagent; 蛍光量子収率; 蛍光; ナプロキセン; イブプロフェン

In this project, I investigated synthesis of optically active fluorescent quinoxalines and their application to high-sensitive optical purity determination reagents for racemic carboxylic acids.1. Chiral 2,3-dimorpholinoquinoxalines bearing amino acid residues at C-6 position were newly synthesized. 2. The derivatization of D,L-naproxen, -ibuprofen, and -2-phenylpropionic acid with chiral quinoxalines bearing L-amino acid residues was carried out by using the Mukaiyama method to give the diastereomers, which emitted intense fluorescence. 3. Fluorescence maxima of the diastereomers appeared around 440 nm when the excitation wavelength of about 370 nm was applied. 4. The fluorescence intensity in aqueous MeCN solution was remarkably decreased compared with that in MeCN.5. The quantum yield of fluorescence was measured to be 0.052 by using the relative quantum yield measurement with anthracene as a standard. 6. All the diastereomers derived from D,L-naproxen, -ibuprofen, and -2-phenylpropionic acid with chiral quinoxaline bearing the L-prolin residue were clearly separated within 16 min on reversed-phase (Finepak SIL C_<18>S) HPLC equipped with a fluorescence detector. 7. The detection limit of the diastereomer was estimated to be 5 pmol/10 μl injection volume on the S/N ratio of 5.In conclusion, optically active fluorescent quinoxalines bearing the amino acid residue were demonstrated to be applicable to new high-sensitive optical purity determination reagents for chiral carboxylic acids.

本课题研究了光学活性荧光喹喔啉的合成及其在高灵敏度外消旋羧酸光学纯度测定试剂中的应用。合成了一种新的手性2，3-二吗啉代喹喔啉衍生物。2.用Mukaiyama法将D，L-萘普生、-布洛芬和-2-苯基丙酸与带有L-氨基酸残基的手性喹喔啉衍生化，得到了发射强荧光的非对映体。3.当激发波长约为370 nm时，非对映体的荧光最大值出现在440 nm左右。4.在乙腈水溶液中的荧光强度显着降低相比，在乙腈。通过使用以蒽作为标准的相对量子产率测量，测得荧光的量子产率为0.052。6.所有衍生自D，L-萘普生，-布洛芬和-2-苯基丙酸与带有L-脯氨酸残基的手性喹喔啉的非对映体在配备有荧光检测器的反相（Finepak SIL C_ S）HPLC上在16 min内清楚地分离<18>。7.在S/N = 5的条件下，非对映体的检出限为5 pmol/10 μl进样体积。

项目成果

加藤明良: "The Ring-Opening Reaction of Benzimidazoles with 2-chloro- or 2,3-Dichloro-6'-nitroguinoxaline"Technical Reports of Seikei university. 37・1. 7-12 (2000)

加藤彰：“苯并咪唑类与2-氯-或2,3-二氯-6-硝基喹喔啉的开环反应”成惠大学技术报告37・1（2000）。

Akira Katoh, Thoru Yoshida, and Junko Ohkanda: "Synthesis of Quinoxaline Derivatives Bearing the Styryl And Phenylethynyl Groups and Application to a Fluorescence Derivatization Reagent"Heterocycles. 52. 911-920 (2000)

Akira Katoh、Thoru Yoshida 和 Junko Ohkanda：“带有苯乙烯基和苯乙炔基的喹喔啉衍生物的合成及其在荧光衍生化试剂中的应用”杂环。

加藤明良: "Synthesis of Quinoxaline Derivatives Bearing the Styryl and Phenyl ethynyl Groups and Application to a Fluorescence Derinatization Reagent"Heterocycles. 52・2. 911-920 (2000)

加藤彰：“带有苯乙烯基和苯基乙炔基的喹喔啉衍生物的合成及其在荧光脱氨基试剂中的应用”杂环52·2。

加藤明良: "Synthesis of Quinoxaline Derivatives Bearing the Styryl and Phenylethynyl Groups and Application to a Fluorescence Derivatization Reagent"Heterocycles. 52. 911-920 (2000)

Akira Kato：“带有苯乙烯基和苯乙炔基的喹喔啉衍生物的合成及其在荧光衍生试剂中的应用”杂环。 52. 911-920 (2000)

加藤明良: "6位にプロリン残基を含むキノキサリン類の蛍光キラル誘導体化試薬への応用"日本化学会第78春季年会講演予稿集II. 1127 (2000)

加藤彰：“6 位脯氨酸残基的喹喔啉在荧光手性衍生化试剂中的应用”日本化学会第 78 届春季年会记录 II 1127 (2000)。