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.
雑誌名
Analytical Sciences
巻
36
号
8
ページ
997 - 1001
発行年
2020-08-10
出版者
日本分析化学会
出版者別言語
The Japan Society for Analytical Chemistry
ISSN
09106340
EISSN
13482246
DOI
10.2116/analsci.20P031
権利
c 2020 by The Japan Society for Analytical Chemistry
Long-wavelength Fluorogenic Derivatization of Aryl Halides Based on the Formation of Stilbene by Heck Reaction with Vinylbenzenes
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