Solidago altissima L.から単離されたアセチレン類およびテルペン類の特性

[Synopsis] Four acetylenes and three terpenoids were isolated from Solidago altissima L. and characterized by MS, \u27H-NMR and ^C-NMR spectroscopy as methyl (Z)-decaene-4,6,8-triynoate (Zdehydromatricaria ester, 1), methyl 10-[(Z)-2-methyl-2-butenoyloxy]-(2Z,84-2,8-decadiene-4,6-diyoate (2), (4Z-2,4-decadiene-6,8-diyn-4-olide (Z-dehydromatricaria lactone, 3), (4E)-2,4-decadiene-6,8-diyn-4-olide (E-dehydromatricaria lactone, 4), 13E,7 α-acetoxyl kolavenic acid (solidagonic acid, 5), kolavenol (6), and D:C-friedours-7-en-3 β-ol (ilexol, 7). The polyacetylenes could be easily detected as yellowish brown spots on TLC plate following irradiation with blue black light for two to three minutes. The Z and E isomers of dehydromatricaria lactones were easily differentiated based on differences in melting points and chemical shifts of ^1H- and ^C-NMR spectroscopy. Bioassay of these compounds on the germination of lettuce seeds showed that compounds 1, 2, 3, 4, and 5 exhibited growth inhibitory activity, whereas compound 7 did not exhibit the activity. This study presents the first isolation of (E)-dehydromatricaria lactone from Solidago altissima L. in nature. （摘要） Solidago altissima L..から単離した4種のアセチレンおよび3種のテルペン、methyl (z)-decaene-4,6,8-triynoate (Z-dehydromatricaria ester, 1), methyl 10-[(Z)-2-methy 1-2-butenoyloxy]-(2Z,8Z)-2,8-decadiene-4,6-diyoate (2), (4Z)-2,4-decadiene-6,8-diyn-4-olide (Z-dehydromatricaria lactone, 3), (4E)-2,4-decadiene-6,8-diyn-4-olide (E-dehydromatricaria lactone, 4) 13E,7 α-acetoxyl kolavenic acid (solidagonic acid, 5) kolavenol (6), D:C-friedours-7-en-3β-ol (ilexol, 7)について発芽に対する影響をレタスを用いて検討した。その結果、化合物 1,2,3,4 および5は生長阻害作用を示し、化合物7は活性を示さなかった。ポリアセチレンは、TLC上で2, 3分ブルーブラックライトの照射によって黄茶色のスポットとして、容易に確認できた。 Dehydromatricaria lactones のZ体およびE体は、融点の違い、また、^1H-および^C-NMRのケミカルシフトの違いによって、容易に確認できた。なお、単離した成分のうち、（E)-dehydromatricaria lactone (4)は天然物としてSolidago altissima L. から初めて見出した成分である

Syntheses and Characterization of Co(III) Binuclear Complexes Linked by Bis(catecholate) ; [Co_2(dmbpy)_4(thBu)]^<2+> and [Co_2(dcbpy)_4(thBu)]^<2+> (dmbpy ＝ 4,4\u27-dimethyl-2,2\u27-bipyridine, dcbpy ＝ 4,4\u27-diethylcarboxylate-2,2\u27-bipyridine, thBu = 3,3\u27,4,4\u27-tetrahydroxylate-5,5\u27-di-tert-butylbenzaldazine)

Binuclear complexes of cobalt(III) have been prepared with 3,3\u27,4,4\u27-tetrahydroxy-5,5\u27-di-t-butylbenzaldazine (H_4thBu) as bis(catecholate) ligand, and ancillary ligand, 4,4\u27-dimethyl-2,2\u27-bipyridine (dmbpy) and 4,4\u27-diethylcarboxylate-2,2\u27-bipyridine (dcbpy). The complexes were characterized by ^1H-NMR spectra, electrochemical measurements and UV-Vis spectra. In [Co_2(dmbpy)_4(thBu)]^, electrochemical oxidation of the complexes occurs at the bridges as two closely spaced one-electron couples (E_=74mV and 236 mV vs. Fc/Fc^＋). Chemical oxidation of [Co_2(dmbpy)_4(thBu)]^ using Ag^＋ is observed new absorbance peak at 526 nm however, is not remarkable change as [Co_2(dpa)_4(thBu)]^ (dpa = 2,2\u27-dipyridylamine) that have been described in our later paper. On the other hand, [Co_2(dcbpy)_4(thBu)]^ has never appeared new absorbance peaks under the same oxidation condition. Thus the chemical oxidation behavior and electrochemical property were correlated with the pKa of the N-N ancillary ligands. In this report we discuss the effect of two different nitrogen-donor ancillary ligands on the oxidation behavior of binuclear Co(III) complexes