期刊
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
卷 2017, 期 37, 页码 5617-5626出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejoc.201701009
关键词
6,8-Rearrangement; Cyclodextrins; Suzuki-Miyaura reaction; Photochemistry; Kinetics
资金
- Associated Laboratory for Sustainable Chemistry-Clean Processes and Technologies-LAQV
- Fundacao para a Ciencia e Tecnologia
- Ministerio da Educacao e Ciencia [UID/QUI/50006/2013]
- European Regional Development Fund under the PT Partnership Agreement [POCI-01-0145 FEDER-007265]
- National Portuguese NMR Network [RECI/BBB-BQB/0230/2012]
- FCT [SFRH/BPD/84805/2012]
- [NORTE-01-0145-FEDER-000011]
8-Phenyl-5,7-dihydroxyflavylium and 8-methyl-5,7-dihydroxyflavylium were synthesized to observe the 6,8-rearrangement. 8-Phenyl and 8-methyl residues were introduced by Suzuki-Miyaura reaction of 8-iodochrysin, then reduced by LiAlH4 to give the corresponding 3-deoxyanthocyanidins. At pH 1.0 the stable form is the 8-substituted flavylium cation in both compounds. At higher pH values the quinoidal bases are the stable species and some evidence for the 6,8-rearrangement was obtained, but the respective spectral variations are very small. This was overcome by using a modified cyclodextrin (captisol), which favors the formation of the trans-chalcone at the expense of the quinoidal bases. The trans-chalcone was isolated and dissolved in CD3OD/DCl (pD < 1) to give a mixture of the two flavylium isomers. This was confirmed by ESI-MS analysis (recorded in positive ion mode) of the two isomers after separation by HPLC, which gave the same peak ([M](+) m/z 253). The 6-isomer slowly reverts to the most stable 8-isomer. The 6,8-rearrangement was also observed after irradiation of the trans-chalcone (in the presence of captisol) at pH 5. Acidification of this photostationary state gave a mixture of both flavylium cations. The UV/Vis absorption of the flavylium cation (6-isomer) was blueshifted in comparison to the 8-isomer.
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