Über pflanzliche Herzgifte, XXIV. Mitteil.: Die quantitative Trennung und Identifizierung von Herzgiftglykosiden aus <i>Digitalis purpurea</i> und <i>lanata</i> durch “echte Verteilungschromatographie an Papier”

134

Screening of crude extracts of the bark of Annona bullata showed cytotoxic and pesticidal activities. By monitoring with brine-shrimp lethality, two novel, extremely potent acetogenins, bullatacin [1] and bullatacinone [2], were isolated. Spectral and chemical methods identified bullatacin as a diastereomer of asimicin. Bullatacinone represents bullatacin with the lactone cleaved and reformed at the 4-OH. Compounds 1 and 2 show selective cytotoxicities in human tumor cell lines, and certain susceptible cells give ED50 values as low as 10(-12)-10(-15) micrograms/ml. Bullatacin was pesticidal at concentrations as low as 1 ppm, but bullatacinone lacked pesticidal activities. The known compounds liriodenine and (-)-kaur-16-en-19-oic acid were also isolated and were lethal to brine shrimp but were not significantly cytotoxic.

mentioning

confidence: 99%

“…Bullatacinone [2] gave negative results with Kedde's reagent (15) indicating that there is no ,ß-unsaturated 7-lactone ring. Weak uv end absorption at a maximum of 203.5 nm (e = 3799) showed a lack of the conjugated unsaturation usually found in these acetogenins.…”

mentioning

confidence: 99%

Bullatacin and Bullatacinone: Two Highly Potent Bioactive Acetogenins from Annona bullata

Hui¹,

Rupprecht²,

Liu³

et al. 1989

134

“…A positive reaction of calocin (1) with NalCL (6) indicated the presence of a vicinal diol arrangement in the molecule. The diagnostic color tests for 2-deoxy sugar, viz., the Xanthydrol reaction (7,8) and Keller-Kiliani reaction (9), exhibited by 1 in conjunction with its molecular formula C27H44O6 indicated it to be a pregnane (C21) glycoside of a 2-deoxy hexose, commonly reported to occur in plants of Asclepiadaceae family (1,2). Its ir spectrum displayed absorption bands due to hydroxyl groups at 3430 cm-1, but the absence of absorption in the carbonyl region suggested that its pregnane genin presumably contained a -CHOH-CH3 chain at C-17.…”

Section: Resultsmentioning

confidence: 99%

Structure of Calocin

Srivastava¹,

Khare²,

Khare³

1982

“…The viscous mass was cooled and repeatedly triturated with absolute EtzO (to remove excess of phenylhydrazide), yielding a D-cymaronic acid phenylhydrazide (9) which crystallized from MeOH-Et20 as colorless needles (0.6 mg) mp 150-153°[lit (13) mp 155°}. l-Oleandronic acid phenylhydrazide (10).-A solution of 8 (2 mg) in absolute EtOH (0.05 ml) was mixed with freshly distilled phenylhydrazine (0.04 ml) and heated as for 7, affording L-oleandronic acid phenylhydrazide (10) which crystallized from MeOH-Et20 as colorless needles (1.2 mg) mp 135-136°[lit (14,15)…”

Section: Methodsmentioning

confidence: 99%

A Novel Pregnane Ester Tetraglycoside from Orthenthera viminea

Kaur¹,

Khare²,

Khare³

1985

A new pregnane ester tetraglycoside designated as orthenine (1) has been isolated from the dried twigs of Orthenthera viminea. Chemical and spectroscopic evidence is consistent with the structure 12-0-cinnamoyl sarcostin 3-0-a-L-oleandropyranosyl (li-»4)-Q-a-Loleandropyranosyl (li-»4)-0-a-L-oleandropyranosyl (1>-»4)-0-3-D-cymaropyranoside for orthenine.In previous communications, we have reported the isolation and structural elucidation of four novel oligosaccharides (1-5) and pregnane ester glycosides (6,7) from the twigs of Orthenthera viminea W. & A. (Asclepiadaceae). As a continuation of studies on this plant, we are presenting here spectral and chemical evidence for the structure of a new oligoglycoside, designated as orthenine (1). RESULTS AND DISCUSSIONOrthenine (1) mp 120-124°, {a]D + 115°, C58H88019, responded positively to the Liebermann Burchardt test (8), xanthydrol (9,10) and Keller-Kiliani reactions (11), indicating it to be a steroidal glycoside of a 2-deoxy sugar residue. The presence of a vicinal diol system in the molecule was indicated by its positive reaction with NaI04. In the 'H-nmr spectrum of 1 at 400 MHz, the presence of characteristic methylene signals in the regions 2.36-2.07 (4H) and 2.02-1.80 (4H), in conjunction with four secondary methyl group doublets (J=6 Hz) at 1.35 (3H), 1.33 (6H), and 1.24 (3H) and four methoxy group singlets at 3.46, 3.45, 3-40, and 3.39, provided evidence that 1 is a tetraglycoside of 2,6-dideoxy hexoses.Mild acid (0.025 M H2S04) hydrolysis ( 12) of 1 afforded a crystalline genin 2 and a mixture of two sugars. The separated sugars 5 and 6 displayed characteristic color tests of 2-deoxy sugars and were identified as D-cymarose (13) (2,6-dideoxy-3-O-methyl-Dribohexose) and L-oleandrose (14,15) (2,6-dideoxy-3-0-methyl-L-arabinohexose) (pc and {a]D). For further characterization, 5 and 6 were oxidized with bromine water to their lactones 7 and 8, respectively, which on treatment with phenylhydrazine yielded known crystalline derivatives, i.e., D-cymaronic acid phenylhydrazide (9) (13) and Loleandronic acid phenylhydrazide (10) (14,15). On the basis of the above results, 1 was