- Asymmetric Nitrogen-containing dimer from aerial parts of mercurialis leiocarpa and its synthesis by mimicking generation process through radical intermediates
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An asymmetric nitrogen-containing dimer, leiocarpanine A, was isolated from the aerial part of Mercurialis leiocarpa as a new compound. The new generation process of leiocarpanine A was estimated and a concise synthesis of leiocarpanine A could be detailed based on mimicking the generation process through the radical intermediates. In general, a lot of reaction step and organic reagents are required for the synthesis of asymmetric nitrogen-containing dimers. However, our new synthesis method enables a concise synthesis of asymmetric nitrogen-containing dimers through radical intermediates by only liquid-separation. This synthetic method provides a rapid and concise pathway to construct a library of nitrogen-containing dimers that might be useful for drug discovery. In addition, it is useful to elucidate the generation process of leiocarpanine A.
- Ino, Sayaka,Kondo, Yuto,Matsuda, Hisashi,Nakamura, Seikou,Nakashima, Souichi,Yamashita, Haruka,Yamashita, Masayuki
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p. 520 - 525
(2020/07/31)
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- Chemistry of hermidin: Insights from extraction experiments with the main Alkaloid of mercurialis perennis L. Tracked by GC/MS and LC/MSn
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Hermidin (1), a piperidine-2,3-dione alkaloid, has been previously detected as a lipophilic constituent in Mercurialis perennis L. and other Mercurialis species. Because of strong electronwithdrawing effects of its carbonyl groups, an acidic H-atom is easily subtracted from 1, whereas the latter shows high reactivity towards oxidation reactions or the attack of C-nucleophilic agents. To obtain a better understanding of possible chemical pathways upon extraction of root parts of M. perennis, the products obtained with different solvents from 1 were investigated. Extraction of M. perennis with aqueous MeOH or EtOH yielded a mixture of hermidin quinone (3), 5-hydroxy-4-methoxy-5- (alkoxycarbonyl)-1-methyl-3-pyrrolin-2-ones, 7 and 8, and d,l- And meso-isochrysohermidins, 5 and 6, all of them being investigated by GC/MS and LC/MSn. The latter compounds were supposedly formed by free-radical reactions, followed by spontaneous benzilic acid rearrangement and esterification. Furthermore, extraction of M. perennis with aqueous Me2CO produced an aldol condensation product, the known alkaloid speranskatine A (9a), which was identified by NMR after chromatographic purification. In a similar manner, a CH2 homolog of speranskatine A (10a) was obtained as a novel compound when ethyl methyl ketone (=butan-2-one; EtCOMe) instead of Me2CO was used for extraction. Consequently, 1 easily undergoes artefact formation upon extraction of plant material with polar or slightly polar solvents.
- Lorenz, Peter,Conrad, Jürgen,Duckstein, Sarina,Kammerer, Dietmar R.,Stintzing, Florian C.
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p. 1606 - 1623
(2015/02/19)
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- Isolation, Structure, and Synthesis of Hermidin, a Chromogen from Mercurialis perennis L.
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Hermidin has been isolated from Mercurialis perennis L. as a colourless, crystalline compound, shown by synthesis to be 5-hydroxy-4-methoxy-1-methylpyridine-2,6(1H,3H)-dione (2), which in aqueous solution exist as a dihydroxy-4-methoxy-1-methylpyridin-2(1H)-one (3) or (4).Oxidation of hermidin with nitric acid affords 4-methoxy-1-methylpyridine-2,3,6-trione (16).When equimolecular amounts of the latter and hermidin in aqueous solution are mixed an immediate deep blue solution containing an ion-radical (17) results.Oxidation of hermidin by air in methanolic solution gives 5,5'-dihydroxy-4,4'-dimethoxy-1,1'-dimethyl-3,3'-bipyridine-2,2',6,6'-(1H,1'H,3H,3'H)-tetraone (18), and in pyridine solution 4,4'-dimethoxy-1,1'-dimethyl-3,3'-bipyridine-2,2',5,5',6,6'-hexaone (23).Knackmuss' conclusions on the oxidation of 3,6-dihydroxy-4-methylpyridin-2(1H)-one (26) have been re-interpreted. 3,4-Dihydroxy-5-methoxy-1-methylpyridin-2(1H)-one (7) has been synthesized.
- Swan, George A.
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p. 1757 - 1766
(2007/10/02)
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