Transformed steroids. 114. Direction of opening oxide ring of 16,17α-epoxy-17β-phenylandrost-4-en-3-one

Conclusions Starting with androst-5-en-3-ol-17-one, we synthesized 16,17-epoxy-17-phenylandrost-4-en-3-one. Cleavage of 17-C-O bond, adjacent to the phenyl ring, occurs during its nucleophilic opening, accompanied by 1,2-migration of the angular 18-CH₃ group.See [1] for Communication 113.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1889–1893, August, 1980.     

Triterpene glycosides of Thalictrum squarrosum. II. Molecular and crystal structure of squarrofuric acid

The structure of squarrofuric acid (an artifactual genin fromThalictrum squarrosum) has been confirmed by x-ray structural analysis and the configurations of the C13, C14, C17, C20, and C22 asymmetric centers have been established, which has enabled this compound to be assigned to the lanostane series with the following structure: 3,30-dihydroxy-20(S),22(S)-22,25-epoxylanost-9(11)-en-21-oic acid.Novosibirsk Institute of Organic Chemistry, Siberian Branch of the USSR Academy of Science. Irkutsk Institute of Organic Chemistry, Siberian Branch of the USSR Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 533–537, July–August, 1987.     

Sterols and sterol glycosides of Bryonia alba

Summary It has been shown that the roots ofBryonia alba contain cholest-7-en-3-ol, 24-methylcholest-7-en-3-ol, 24-ethylcholest-7-en-3-ol, 24-methylenecholest-7-en-3-ol, 24-ethylidenecholest-7-en-3-ol, 24-ethyl-4-methylcholest-7-en-3-ol, 24-ethylidene-4-methylcholest-7-en-3-ol, and also previously undescribed 3-O--glucopyranosides of the above-mentioned sterols.A. L. Mndzhoyan Institute of Fine Organic Chemistry, Academy of Sciences of the Armenian SSR, Erevan. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 353–360, May–June, 1977.     

Synthesis of uzarigenin

Conclusions The aglycone uzarigenin has been synthesized from 3-hydroxy-5-pregn-16-en-20-one acetate.Institute of the Chemistry of Plant Substances, Academy of Sciences of the UzbekSSR. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 545–552, September–October, 1970.     

Heterogenization of palladium(II) chelates on a sibunite

Summary Heterogenized palladium(II) chelates have been prepared by a sibunite treatment of acetone or aqueous solutions of palladium complexes with alizarin red C, 4- anilino-pent-3-en-2-one,N, N-bis(acetylacetone)ethylenediamine, 1-phenyl-4-methylpent-4-en-1,3-dione and 1-phenyl-3-anilino-4-methylpent-4-en-1-one. The catalytic properties of these chelates in chloronitrobenzene hydrogenation have been studied. It was found that the catalytic activity approaches 159 mol H₂ (mol Pd min)^–1 depending on the chlorine atom position in the aromatic ring and the nature of the solvent. The catalysts do not lose their activity after five cycles. The products of chloronitrobenzene hydrogenation are chloroanilines (up to 90%), azo- and azoxychlorobenzenes (5–7%) as a result of incomplete reduction as well as small quantities (2–5%) of dehalogenated azo-, azoxybenzenes and aniline.     

Polyfunctional triterpenoids from the bark of Yeddo spruce

The composition of the polyfunctional triterpenoids of an extract of the Yeddo spruce has been studied. Five serratene triterpenoids have been isolated: 21-hydroxyserrat-14-en-3-one (I), 3-hydroxyserrat-14-en-21-one (II), serratenediol (III), episerratenediol (XII), and diepiserratenediol (V) in the form of its acetate. The structures of the compounds were confirmed by¹³C NMR spectra and XSA.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 662–667, November–December, 1992.     

Saponins of dioscorea XV. Caucasosaponin and caucasoprosapogenin fromD. caucasica

Summary Two new saponins have been isolated from the rhizomes ofD. caucasica: the water-soluble caucasosaponin—a rhamnosotriglucoside of 25 D-22-spirost-22-en-3-ol—and the water insoluble caucasoprosapogenin—a glucosotrioside of 25 D-22-spirost-5-en-3-ol-, and also the previously known rhamnosidodiglucoside of 25 D-22-spirost-5-en-3-ol—gracillin.Khimiya Prirodnykh Soedinenii, Vol. 3, No. 4, pp. 237–241, 1967     

Synthesis of (24R)-3β-hydroxystigmast-5-en-7-one

The natural compound (24R)-3-hydroxystigmast-5-en-7-one has been synthesized from -sitosterol.Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus', 220141, Belarus', Minsk. Ul. Akad. Kuprevicha, 5/2. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 484–487, July–August, 1999.     

Triterpene glycosides ofAstragalus and their genins LIII. Chemical transformation of cycloartanes III. Modification of ackendoside D

The 17E- and 17Z- isomers of 3-[O--L-arabinopyranosyl-(12)-ß-D-xylophranosyloxy]-6-(-D-xylopy-ranosyloxy)-25-norcycloart-17-en-16-on-24-oic acid have been synthesized in four stages from askendoside D.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 89 14 75. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 565–567, July–August, 1996. Original article submitted January 15, 1996.     

Transformed steroids. 161. Reactivity of 17-spirooxetane-20-ketosteroids towards opening of the four-membered ring

Conclusions Replacement of the 20-oxo group in 17,21-epoxypregn-5-en-3-ol-20-one by the hydrazono-group affects the cleavage of the oxetane ring by thiocyanic acid, reaction occurring preferentially by introduction of^–NCS at C¹⁷ with consequent expansion of the four-membered ring to a six-membered ring with the formation of the [17; 21]-1,3-tetrahydrooxazine-2-thione.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1393–1396, June, 1987.     

β,β-Dimethylacrylic acid

A method has been developed for obtaining ,-dimethylacrylic acid from 3-methylbut-3-en-1-ol — a multitonnage product of the production of isoprene by the Prins method.Institute of Organic Chemistry, Academy of Sciences of the Armenian SSR, Erevan. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 313–314, May–June, 1991.     

Transformed steroids

Conclusions The opening of the three-membered ring of 16, 17-methylenepregn-5-en-3-ol-20-one by nucleophilic reagents in the presence of H₂SO₄, proceeds regiospecifically, depending on the nature of the nucleophilic reagent.See [1] for Communication 118.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 658–662, March, 1980.     

Structure of a pentacyclic triterpene alcohol fromCentaurea aquarrosa

Summary The structure of a previously unknown pentacyclic triterpene isolated fromCentaurea squarrosa Willd. has been established. It is urs-20(3)-en-3-ol (I).A. L. Mndzhoyan Institute of Fine Organic Chemistry, Academy of Sciences of the Armeniam SSR, Erevan. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 59–69, January–February, 1977.     

Structure of ergolide

The epigeal part ofErigeron khorassanicus Boiss. has yielded a new sesquiterpene lactone of the pseudoguaiane type — ergolide C₁₇H₂₂O₅, mp 179–180°C (ethanol) [] _D ²⁰ +123° (c 4.88; ethanol). On the basis of chemical transformations and spectral characteristics, its structure and configuration have been established as 6-acetoxy-4-oxo-1,7H,6,8,10H-pseudoguai-11(13)-en-8,12-olide.Institute of the Chemistry of Plant Substances of the Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 568–571, September–October, 1986.     

Metabolic Studies of Clostebol Acetate in Horses

Clostebol acetate (4-chlorotestosterone acetate) is a synthetic anabolic steroid which may be used to enhance performance in racehorses. Studies on the in vitro biotransformation of clostebol acetate with horse liver microsomes were carried out. Six metabolites (C1 – C6) were detected. They were 4-chlorotestosterone (C1), 4-chloroandrost-4-en-3-ol-17-one (C2), 4-chloroandrost-4-ene-3,17-diol (C3), 4-chloroandrost-4-ene-3,17-dione (C4), 4-chloroandrost-4-en-6-ol-3,17-dione (C5) and 6-hydroxy-4-chlorotestosterone (C6). Clostebol acetate (350 mg) was administered orally to 2 thoroughbred geldings. The parent drug was not detected in post-administration urine, and only three metabolites C1, C3, and 4-chloroandrostane-3,17-diol (C7) were observed. The metabolic pathway for clostebol acetate is postulated. These studies have shown that metabolites C3 and C7 could be used as potential screening targets for controlling the abuse or misuse of clostebol acetate in racehorses.     

Glycosides of marine invertebrates. XIII. New holothurinogenins of holothurin B1 fromHolothuria floridana

We have isolated for the first time the native aglycone of a triterpene glycoside of the holoturin series — holothurin B₁ — and have established its structure as holost-9-ene-3,12,17-triol. The structures of two new holostane derivatives have been established — holosta-8,11-diene-3,17-diol and 3,17-dihydroxyholost-9-en-12-one. A scheme of transformation of the native genin of holothurin B₁ under the conditions of the acid splitting of the glycoside has been put forward.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 323–327, May–June, 1982.     

Transformed steroids. 185. Use of the Nicholas reaction for regio- and stereo-selective transformation of 16α,17a-epoxy-17Β-ethynyl-androstanes into 16α,17α-cis-disubstituted steroids

The HBF₄·Et₂O-catalyzed methanolysis reactions of the 16, 17-oxides of 17-ethy-nylandrost-4-en-3-one and its dicobalt hexacarbonyl complex were studied. It was shown that these reactions proceed with the same regiodirectivity of the oxide ring opening at the tertiary center but with a different mode of stabilization of the intermediates formed. The reaction of the free oxide proceeds without the inclusion of the external nucleophile and is concluded by the Wagner-Meerwein rearrangement; the C¹⁷-carbocation formed in the Co-coordinated oxide is stabilized by the addition of the methoxide ion and the elimination of a proton or of water. The opening of the oxide ring of dicobalt tetracarbonyl 16, 17-epoxy-17-ethynylandrost-4-en-3-one can be realized with decomplexation accompanied by carbonylation and heterocyclization.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp.1180–1184, May, 1991.     

Oxidative transformations of labdane diols. III. Preparation of acids with a strobane skeleton from larixol

It has been shown that the oxidation of larixol with chromic acid mixture forms methyl 6-oxo-8,13-epoxystroban-14-oate, methyl 6-oxo-8,13-epoxystroban-14-oate, and 6,13-dioxo-14,15-bisnorlabd-7-en-17-oate.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 697–703, November–December, 1986.