Steroids of the spirostan and furostan series from Nolina microcarpa IV. Structures of nolinogenin,nolinospiroside B,and nolinofuroside B

A glycoside has been isolated from the plantNolina microcarpa S. Wats. (family Dracaenaceae) which has been called nolinofuroside B and has the structure of 6-methoxy-3,5-cyclo-(25S)-furostan-1,22,26-triol 1-O--D-fucopyranoside 26-O--D-glucopyranoside (I). Enzymatic hydrolysis of the bioside (I) yielded nolinospiroside B (III) and nolinogenin (IV). The latter is 6-methoxy-3,5-cyclo-(25S)-spirostan-6-ol, and glycoside (III) is its 1-O--D-fucopyranoside.M. V. Frunze Simferopol' State University. Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 218–224, March–April, 1992.     

Molecular and crystal structure of the sequiterpene lactone austricin

An x-ray structural study has been made of the sesquiterpene lactone austricin: diffractometer, MoK radiation, 1147 reflections, direct method, R=0.045. The spatial structure of the molecule has been determined. The conformation of the pentane carbocycle is 1-envelope, of the heptane ring 1,10, 7-chair, and of the lactone ring 7-envelope. The lactone ring is trans-linked with the guaiane skeleton.Institute of Organic Synthesis and Coal Chemistry, Kazakh SSR Academy of Sciences, Karaganda. A. N. Nesmeyanov Institute of Heteroorganic Compounds, USSR Academy of Sciences, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 788–791, November–December, 1989.     

Veränderung des thermischen Verhaltens von Kaolinit durch mechanische Aktivierung

Zusammenfassung Es ist bekannt, daß die Eigenschaften von Kaolinit nicht nur durch eine Kalzinierung oberhalb 600 °C, sondern auch durch intensive mechanische Beanspruchung stark verändert werden können. Die durch eine Intensivmahlung erzeugte Reaktivitätssteigerung kann durch eine Verbesserung der Säurelösbarkeit des Al₂O₃-Anteiles, das veränderte thermische Verhalten und strukturelle Veränderungen gekennzeichnet werden. In der vorliegenden Arbeit geht es um einen Beitrag zur methodischen Aufklärung der strukturellen und thermischen Veränderungen von Kaolinit, insbesondere durch Einsatz thermoanalytischer und IR-spektroskopischer Methoden. Als intensives Zerkleinerungsaggregat wurde eine Scheibenschwingmühle eingesetzt.

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It is already known that the properties of kaolinite can be changed substantially not only by calcination above 600° but also by intensive mechanical stress.A reactivity increase induced by intensive grinding can be characterized by an increase of acid solubility of the Al₂O₃ content, by changed thermal behaviour and by structural changes. The paper presented contributes to the methodic explanation of structural and thermal changes of kaolinite, especially by the use of thermoanalytical and IR spectroscopic methods. The intensive grinding was performed in a vibration-disc mill.

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Résumé Il est déjà connu que les propriétés de la kaolinite peuvent être profondément modifiées non seulement par calcination au-dessus de 600 °C, mais aussi par contrainte mécanique intense.Une augmentation de la réactivité induite par broyage intense peut être caractérisée par une augmentation de la teneur en Al₂O₃ déterminée par solubilité en milieu acide, par le changement du comportement thermique et par des modifications structurales. Le présent article contribue à l'explication méthodique des changements structuraux et thermiques de la kaolinite, spécialement à l'aide des méthodes d'analyse thermique et de spectroscopie infrarouge. Le broyage intense a été effectué dans un broyeur à disques vibrants.

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, 600°, . l₂₃ , . . .

     

Karakanine — A new alkaloid from the epigeal part of Aconitum karakolicum

A new alkaloid, which has been called karakanine, has been isolated from the total alkaloids of the epigeal part ofAconitum karakolicum. The structure of karakanine as 8,14-dihydroxy-16-methoxy-4-methyl-N-ethyl-1,19-epoxyaconitane has been proposed on the basis of a study of its IR, PMR, mass, and¹³C NMR spectra, and has been confirmed by its conversion into karakoline.Institute of Chemistry of Plant Substances, Uzbekistan Republic Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedeninii, No. 1, pp. 62–64, January–February, 1993.     

A new steroid glycoside from the starfishPatiria pectinifera

From the glycoside fraction of the starfishPatiria pectinifera, after its desulfation, an artefactural glycoside has been obtained: 29(-L-arabinofuranosyloxy)-5-stigmastane-3,6,8,15,16-pentaol (I). The structure of (I) was shown by¹H and¹³C NMR spectra and mass spectra and by acetylation and high-temperature hydrogenation.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Institute of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 356–361, May–June, 1985.     

Minor polyhydroxysteroids from the starfish Crossaster papposus

Minor polyhydroxysteroids from the starfishCrossaster papposus have been isolated and characterized: 5-cholestane-3,6,8,15,16,26-hexanol and 24-methyl-5-cholesta-14,22E-diene-3,6,8,26-tetraol 26-O-(3-O-methyl--D-glucopyranoside) (crossasteroside P₃). The structures of the compounds were established on the basis of spectral methods.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, p. 218–221, March–April, 1990.     

Retro-michael reaction of 28-methoxy-18,19-secolupane-18,19-dione derivatives

The interactions with KOH in boiling diethyleneglycol of 3,28-dimethoxy- and 3-acetoxy-28-methoxy-18,19-secolupane-18,19-diones have been studied. In the first case, 3-methoxy-19,20,21,22,29,30-hexanor-18,19-seco(17H)lupan-18-one and the corresponding 18-ol were isolated from the mixture of products, and in the second case 3-hydroxy-19,20,21,22,29,30-hexanor-18,19-seco(17H)lupan-18-one — which was also obtained by an analogous reaction from 3-acetoxy-18,19-secolupan-18,19-dione — and 3-hydroxy-19,20,21,22,28,29,30-heptanor-18,19-secolupan-18-one. Thus, it has been found that in this case the retro-Michael reaction is accompanied by 28-demethoxylation and partially by 28-demethoxy-methylation.Pacific Ocean Institute of Bioorganic Chemistry, Far-Eastern Branch, Russian Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 210–215, March–April, 1992.     

Gomphacil — A cardenolide glycoside ofGomphocarpus fruticosus

The leaves ofGomphocarpus fruticosus (L.) R.Br. have yielded the new acetylated glycoside gomphacil, which is (3-O-1,2-O-2)-(3-acetoxy-2-hydroxy-4,6-dideoxyhexulosido)-14-hydroxy-5-card-20(22)-enolide.State Scientific Center for Drugs, Ukraine, 310085, Kharkov, ul. Astronomicheskaya, 33. Ukrainian Pharmaceutical Academy, 310002, Kharkov, ul. Pushkinskaya, 53. Translated from Khimiya Prirodnykh Soedinenii, Vol. 33, No. 1, pp. 71–73, January–February, 1997.     

Über die Darstellung von α-Brom-hydrozimtsäure- und α-Brom-γ-phenylbuttersäure-methylester und deren Umsetzung zu α-Oximino-estern

Zusammenfassung Die Bromierung von Hydrozimtsäure und -Phenylbutter-säure verläuft anomal. Hydrozimtsäure wird außer in -Stellung zur Carboxylgruppe auch in -Stellung bromiert, so daß nach der Veresterung ein Gemisch von - und -Brom-ester entsteht. Die Bromierung der -Phenylbuttersäure ergibt nur geringe Mengen an -Brom-ester und führt in der Hauptsache durch Ringschluß zu bromierten Naphthalinderivaten. Die -Brom-ester dieser Säuren können über die entsprechenden Malonsäuren in reiner Form gewonnen werden. Durch Umsetzung mit Natriumnitrit werden die beiden Brom-ester in -Oximino-ester übergeführt. Bei der Hydrozimtsäure entstehen dabei eineanti- und einesyn-Form mit unterschiedlichen chemischen und physikalischen Eigenschaften.

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The bromination of hydrocinnamic acid and -phenyl butyric acid proceeds anomalously. Hydrocinnamic acid is brominated both in -position and -position to the carboxyl group. Esterification gives a mixture of - and -brominated ester. The bromination of -phenyl-butyric acid only yields small amounts of -brominated ester. It mainly gives brominated derivatives of naphthaline by cyclization. The -brominated esters of both acids can be obtained in pure form via the corresponding malonic acids. By reaction with sodium nitrite the brominated esters are converted into -oximino esters. In the case of hydrocinnamic acid ananti-form and asyn-form are produced with different chemical and physical properties.

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Mit 1 Abbildung     

A structural investigation of a D-glucan fromYersinia pseudotuberculosis of serotype VI

It has been established that an -D-glucan isolated fromYersinia pseudotuberculosis, serotype VI, is branched and contains -14- and -16-bound D-glucopy-ranose residues in the main chain and the side chains, respectively.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostock. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 151–154, March–April, 1981.