The long-wavelength fluorogenic derivatization method for aryl halides was developed based on stilbene formation by the Heck coupling reaction between aryl halides and vinylbenzenes in the presence of palladium(II) acetate as a catalyst. Fluorescent maximum wavelengths of the derivative obtained by the proposed reaction were 365 – 450 nm, which were 50 – 100 nm longer than those of the biphenyl derivatives formed with our previously developed fluorogenic derivatization method. Also, by the investigation using vinylbenzenes containing electron-donating or -withdrawing functional groups, it was found that an internal charge transfer system could contribute to extend the emission wavelength of the derivative. Furthermore, the proposed reaction was applied to develop a pre-column derivatization HPLC with fluorescence detection method for aryl bromides using 4-vinylanisole. p-Substituted aryl bromide derivatives (i.e., p-bromobenzonitrile, p-bromoanisole, bromobenzene, p-bromobenzoic acid ethyl ester, p-bromotoluene) were successfully detected within 40 min with the detection limit of 0.007 – 0.264 μM. Despite the short reaction time of 10 min, the reaction yields for p-bromoanisole and bromobenzene were good at 101 and 87%, respectively.

以芳基卤化物与乙烯基苯在乙酸钯(II)催化剂存在下发生Heck偶联反应生成二苯乙烯为基础，建立了芳基卤化物的长波长荧光衍生方法。通过该反应获得的衍生物的荧光最大波长为365-450 nm，比我们之前开发的荧光衍生方法形成的联苯衍生物长50-100 nm。此外，通过使用含有给电子或吸电子官能团的乙烯基苯的研究，发现内部电荷转移系统有助于延长衍生物的发射波长。此外，所提出的反应还被应用于开发一种柱前衍生高效液相色谱法，该高效液相色谱法采用 4-乙烯基茴香醚荧光检测芳基溴化物。40分钟内成功检测出对取代芳基溴化物衍生物（即对溴苯甲腈、对溴苯甲醚、溴苯、对溴苯甲酸乙酯、对溴甲苯），检测限为0.007 – 0.264 μM。尽管反应时间很短，只有 10 分钟，但对溴苯甲醚和溴苯的反应产率分别为 101% 和 87%。