2′,4′,5,7-Tetrahydroxyisoflavone was partially benzoylated with benzoyl chloride to give 7-benzoyloxy-2′, 4′,5-trihydroxyisoflavone. The condensation of the 7-(benzoyloxy)isoflavone with 2-methyl-3-buten-2-ol, followed by the hydrolysis of the resultant 3′-(3-methyl-2-butenyl)isoflavone gave licoisoflavone A. Its 5′-(3-methyl-2-butenyl) isomer was also synthesized from 5-benzoyloxy-2′,4′,7-trihydroxyisoflavone in a similar manner.

Reactions of benzyne with several pyridinium N-imines were examined. 2-o-Aminophenylpyridine derivatives 6, pyrido[1,2-b]indazoles (7), indazolo[2,3-a]quinoline (17), and indazolo[3,2-a]isoquinoline (18) were obtained by the reactions of benzyne with the corresponding ylides 5, 10, 15, and 16, respectively.

The condensation of 7-benzoyloxy-4′-hydroxyisoflavone with 2-methyl-3-buten-2-ol gave 7-benzoyloxy-4′-hydroxy-3′-(3-methyl-2-butenyl)isoflavone. The hydrolysis of the alkylated isoflavone with dilute alkali afforded neobavaisoflavone [7,4′-dihydroxy-3′-(3-methyl-2-butenyl)isoflavone], which was then converted into isoneobavaisoflavone on heating with formic acid. 7-Benzyloxy-4′-hydroxyisoflavone was condensed with 2-methyl-3-buten-2-ol to give a chroman derivative, which was then converted into isoneobavaisoflavone by hydrolysis. 3′-(3-Methyl-2-butenyl)-5,7,4′-trihydroxyisoflavone was also synthesized from 7-benzoyloxy-5,4′-dihydroxyisoflavone in a similar manner.

Zephyranthes Candida, Rutin, Kaempferol-3-0-rhamnoglucoside Kaempferol-3-O-rhamnoglucoside, a flavonoid glycoside, was isolated from fresh withe petals of Zephyranthes Candida.Zephyranthes Candida Herb, belonging to Amarylidaceae (Japanese name: Tamasudare) bears white flowers in fall. From the petals of the plant the iso lation o f rutin has already been reported [1 ]. We now isolated an additional flavonoid in the fully ex amination of the same source, which was identified as kaempferol-3-0-rhamnoglucoside.The flavonoid fraction isolated from the methanol extract was chromatographed over a silica-gel col umn with methyl ethyl ketone-water to give two flavonoids, less polar (m. p. 210 -2 0°C ) [2 ] and more polar (m. p. 180 -9 0°C ). The more polar component was identified as rutin based on the agreement with the mixed m. p., TLC and U V spec trum with those o f the authentic sample.The less polar component gave kaempferol (m. p. 273 -5 °C ) [2 ], glucose [TLC , phenyl osazone (m. p. 201 -2 °C ) ] , and rhamnose [TLC , phenyl osazone (m. p. 179 -8 0°C ) ] by acid hydrolysis, and exhaustive methylation of the less polar com ponent with diazomethane followed by acid hydro lysis gave kaempferol 5,7,4/-trimethyl ether. Besides, the m. p. 191 -4 °C for anhydrous materials of this flavonoid corresponded to that of the kaempferol-3-0-/?-rutinoside synthesized by Vermes et al. [3 ], and the N M R spectrum of its nonaacetate was superimposable with that of rutin decaacetate in the sugar Requests for reprints should be sent to Dr. M . Nakayama,

One of us has reported1 that hibalactone (I), C20H16O6, m.p. 146-146.5°, [ ]23 -87°( chloroform), isolated from young leaves of chyabohiba, nikohiba or Chamaecyparis obtusa (Cupressiacenae),2 has the structure shown in Cmpd. I. This structure was established by the production of piperonylic acid, piperonal and oxalic acid either by permanganate oxidation or ozonolysis, by hydrogenation (Raney nickel or sodium amalgam) to ( + )-isohinokinin3 (major product) and ( -)-hinokinin3 (minor product) by spectroscopic evidence pointing to an ,/3-unsaturated lactone structure, and by studies of the hydrolysis, nitration and bromination products of I.