Transformed steroids

Conclusions A synthesis was carried out for the 3-acetate of 16,23-oxido-21,24-dinorchol-5-en-3,17-diol-20-one and acetates of 16,23-oxido-21,24-dinorchol-5-en-3,17,20-triol, which are new polyhydrosteroids with an additional D-series E ring.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1156–1159, May, 1982.     

Reaction of ammonia with β,β′-dithioalkyl-α,α′-divinyl ketones

Conclusions Syntheses are reported for ,-dithioalkyldivinyl ketones, which react with ammonia to give -amino--thioalkyldivinyl ketones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2414–2415, October, 1988.The authors thank A. M. Kachurin for assistance in taking the spectra.     

Sodium Dithionite Reduction of 2S,5R-(-)-menthone and R-(+)-pulegone in the Presence of β-Cyclodextrin and Hydroxypropyl-β-cyclodextrin

Menthone on reduction with sodium dithionite,showed a good amount of mentholformation in the water/DMF system, withincreasing -cyclodextrin (-CD)concentration from 47.0% for 0.1 equivalent of-CD to 93.5% for 1 equivalentof -CD. Increasing hydroxypropyl--cyclodextrin(HP-CD) gave higher menthol/neomenthol (M/N) ratiosfrom 2.8 to 3.5. In the case of pulegone,increasing -CD showed an increase in the formationof menthols in thewater/DMF system from 13.3% for 0.1 equivalent of-CD to 78.1% for 1equivalent of -CD with greater proportions ofneomenthol and neoisomenthol.However, HP-CD which showed only marginalenhancement in the formationof menthol from menthone (32.1–41%), exhibiteda greater proportion of mentholformation in the case of pulegone (55.1%).However, the phase-transfer capabilityof HP-CD was not found to be significant.     

Triterpene Glycosides of Astragalus and Their Genins. LXI. Occurrence of Cycloartane 6-O-Monodesmosides

Cyclosiversigenin 6-O--L-rhamnopyranoside and 6-O--D-glucopyranoside were isolated fromAstragalus coluteocarpusBoiss. (Leguminosae) andAstragalus dissectusB. Fedtsch. et N. Ivanova, respectively. Cyclosiversigenin 5-O--L-rhamnopyranoside was shown to be an artifact forAstragalus coluteocarpus.Thus, the cyclosiversigenin 6-O--D-glucopyranoside that was isolated from certainAstragalusspecies is hypothesized also to be an artifact. Glycosylation of the 6 -hydroxyl group of cycloartanes by D-glucose and D-xylose, in contrast with other substituents, does not change the low-field position of the PMR signal of the 4-CH ₃ group (1.65 2.01 ppm) that is caused by the influence of deuteropyridine directly on the 6 -hydroxyl. Obviously one of the hydroxyls of the -D-glucopyranoside or -D-xylopyranoside residues has the same effect in this instance.     

Triterpene glycosides of Astragalus and their genins XLII. Cycloartanes of Astragalus tragacantha

Another six components ofAstragalus tragacantha Habl. have been identified on the basis of spectral characteristics and chemical transformations. We have previously described cyclocanthagenin and its 3-0--D-xylopyranoside — cyclocanthoside A — as products of the acid hydrolysis of cyclocanthoside D. Cyclocanthosides B, C, E, and G are here described for the first time and are (24S)-cycloartane-3,6,16,24,25-pentol 3-O-(4-O-acetyl--D-xylopyranoside) 6-O--D-glucopyranoside, (24S)-cycloartane-3,6,16,24,25-pentol 6-O-(6-O-acetyl--D-glucopyranoside) 3-O--D-xylopyranoside, (24S)-cycloartane-3,6, 16,24,25-pentol 6-O--D-glucopyranoside, and (24S)-cycloartane-3, 6, 16, 24, 25-pentol 6-O--D-glucopyranoside 3-O-[O--D-glucopyranosyl-(12)--D-xylopyranoside], respectively.Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Institute of Ecological Genetics, Moldavian Academy of Sciences, Kishenev. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 360–367, May–August, 1992.     

Dielectric constants of acetonitrile, γ-butyrolactone,propylene carbonate,and 1,2-dimethoxyethane as a function of pressure and temperature

The dielectric constants of 1,2-dimethoxyethane, acetonitrile, -butyrolactone, and propylene carbonate were determined from capacitance measurements extrapolated to infinite frequency; ln are reported as a function of pressure up to 80 MPa at 15, 25, 35, 45°C and as a function of temperature in the range 10 to 50°C at 0.10133 MPa. The variation of ln with temperature or pressure can be expressed by a second order polynomial expression. The isothermal compressibilities of the solvents were determined at 25°C from sound velocities, densities, and heat capacities. A simple correlation can be established between ln /P and for most aprotic solvent.     

Triterpenoid Glycosides of Fatsia japonica. II. Isolation and Structure of Glycosides from the Leaves

The previously known triterpenoid 3-O--L-arabinopyranosides of oleanolic and echinocystic acids and hederagenin, 3-O--D-glucopyranosyl-(12)-O--L-arabinopyranosides of oleanolic acid and hederagenin, in addition to 28-O--L-rhamnopyranosyl-(14)-O--D-glucopyranosyl-(16)-O--D-glucopyranosyl ethers of the 3-O--L-arabinopyranoside of hederagenin, and 3-O--D-glucopyranosyl-(12)-O--L-arabinopyranosides of oleanolic acid and hederagenin, respectively, are isolated from leaves ofFatsia japonica(Araliaceae). The structures of the glycosides are confirmed by chemical methods and ¹³ C NMR spectroscopy     

Research on vinyl ethers of the furan series VIII. Vinyl ethers of 2-(α-furyl)ethanols

Vinyl ethers of-furyl-,-(5-methylfuryl)-,-furfuryloxy-, and-tetrahydrofurfuryl-oxyethanols were synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1593–1595, December, 1971.     

Cardiac glycosides of Cheiranthus allioni. V

Conclusions Two additional cardiac glycosides, glucoerysimoside and glucoerysimosol, have been isolated from the seeds ofCheiranthus allioni Hort. Glucoerysimoside is strophanthidin 3-[O--D-digitoxopyranosyl-(4 1)-O--D-glucopyranosyl-(4 1)--D-glucopyranoside]. Glucoerysimosol is a new cardenolide having the same carbohydrate component, but its aglycone is strophanthidol. From these glycosides a new trisaccharide has been obtained which has been characterized as 4-O--cellobiosyl-D-digitoxose.Khar'kov Scientific-Research Institute of Pharmaceutical Chemistry. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 566–571, September–October, 1970.     

Ultrasonic study of the molecular encapsulation and the micellization processes of dodecylethyldimethylammonium bromide-water solutions in the presence of β-cyclodextrin or 2,6-di-o-methyl-β-cyclodextrin

Aqueous solutions of -cyclodextrin (-CD) or 2,6-di-o-methyl--cyclodextrin (DM--CD) and dodecylethyldimethylammonium bromide (D₁₂EDMAB) have been studied from speed of sound (u) data at 298.15 K, using a pulse-echo-overlap technique. The molecular encapsulation process of the surfactant monomer into the cyclodextrin cavity and its effect in the micellization process of the surfactant have been analyzed from theu measurements: I) as a function of [D₁₂EDMAB] in the presence of several initial cyclodextrin concentrations (-CD or.DM--CD); II) as a function of [cyclodextrin] (-CD or DM--CD), for an initial micellar solution of D₁₂EDMAB and; III) as a function of the [cyclodextrin]/[surfactant] stoichiometric concentrations. Both inclusion complexes formed (-CDD₁₂EDMAB) and (DM--CDD₁₂EDMAB) have stoichiometries of 11, and their association constantK have been determined using a model proposed in this work, based on the additivity of the different contributions of the involved species to the speed of sound. The apparent critical micellar concentration, cmc^*, of D₁₂EDMAB is found to increase linearly upon the addition of cyclodextrin (-CD or DM--CD). The free surfactant concentration in the micellar region, [D₁₂EDMAB]_f, decreases in the presence of -CD and slightly increases in the presence of DM--CD. The influence of the parcial methylation of the -cyclodextrin (-CDDM--CD) and of the polar head of the surfactant (D₁₂TAB D₁₂EDMAB) on the complextion and micellar parameters are also discussed.Supplementary material available: Tables of speed of sound (14 pages) are available from the authors.     

Studies on lanthanon(III) complexes ofN-methylisatin-β-amidinohydrazone

Summary The consecutive formation constants of 11 and 21 chelate species made by interaction ofN-methylisatin--amidinohydrazone (-MIAG) with tripositive lanthanons were determined potentiometrically at different ionic strengths (0.02, 0.05, 0.1 and 0.2 M NaClO₄) and at different temperatures (30, 40, 45 and 50 °C) in 50% v/v dioxan-H₂O. The formation constants log _n (calculated by a weighted least-squares method) for the complexes have been found to increase with the atomic number of the lanthanon, with a break at gadolinium. Thermodynamic parameters G, H and S of these complexation reactions were also evaluated.     

Rearrangement ofα -trifluoromethyl-β-dialkylamino-β-fluoroacrylic acid N.N-dialkylamides

Conclusions When heated in the presence of a catalytic amount of BF₃ etherate,-trifluoromethyl--diethylamino--fluoroacrylic acid N, N-dimethylamide is reversibly isomerized to-trifluoromethyl--dimethylamino--fluoroacrylic acid N, N-diethylamide. The methyl esters of-trifluoromethyl--diethylammo--fluoroacrylic acid and-trifluoromethyl--phenoxy--fluoroacrylic acid N,N-dimethylamide are not isomerized under the same conditions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No.1, pp.137–141, January, 1976.     

bis(α-oxy-β,β,β-Trichloroethyl)-phosphonic acid esters

Conclusions The reaction of hypophosphorus acid esters with chloral es studied. A series of esters of bis(-oxy-, , -trichloroethyl) phosphonic acid esters is obtained.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1633–1634, July, 1968.     

Neue Ergebnisse zur Polymorphic desβ-Naphthols und deren Auswirkung auf die Phasendiagramme der Naphthalingruppe

Zusammenfassung Die frühere Annahme, daß die beiden Modifikationen von-Naphthol den gleichen Schmelzpunkt besitzen und somit einen Grenzfall der Enantiotropie darstellen, wurde durch differentialthermoanalytische Untersuchungen widerlegt. Die beiden Modifikationen stehen zueinander im Verhältnis der Monotropie mit der allerdings nur geringen Schmelzpunktsdifferenz von 0,5°. Auch die IR-Spektren der beiden Kristallformen bestätigen das Vorliegen einer Monotropie.Für die Phasendiagramme der Naphthalingruppe, an denen-Naphthol beteiligt ist, ergeben sich Korrekturen. Da die instabile Mod. II die mit Naphthalin korrespondierende Kristallform ist, liegt in dem System Naphthalin--Naphthol keine lückenlose Mischkristallreihe vor (Typ. I, Roozeboom), sondern es wird eine Mischungslücke gebildet, denn das System besteht aus zwei Mischkristallphasen (Typ. IV). Auch im System-Naphthol--Naphthylamin tritt auf der-Naphtholseite eine bisher nicht erkannte Phasenüberschneidung auf und anstelle von Typ. III wird Typ. V (Roozeboom) gebildet.Schmelzdiagramme ohne Mischkristallbildung-Naphthol--Naphthol,-Naphthol--Naphthylamin) sind von einer Korrektur nur insofern betroffen, als die Kurvenäste der beiden Modifikationen des-Naphthols nicht von einem Punkt ausgehen und der stabile Kurvenast nicht als Mod. II, sondern als Mod. I bezeichnet werden muß.

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New results on the polymorphism of-naphthol and its effects on the phase diagrams of the naphthalene group

Summary The earlier assumption that the two modifications of-naphthol have the same melting point and thus constitute a borderline case of enantiotropy was disproved by differential thermoanalytic investigations. The two modifications only have the slight difference in melting point of 0.5°. The IR spectra of the two crystal forms confirm the presence of monotropy.There are corrections for the phase diagrams of the naphthalene group in which-naphthol is involved. Since the unstable modification III is the crystal form corresponding to naphthalene, there is no unbroken series of mixed crystals in the naphthalene--naphthol system (Type I, Roozeboom), but a mixing gap is formed since the system consists of two mixed crystal phases (Type IV). A phase overlap which had not been previously recognized also occurs on the side of-naphthol in the-naphthol--naphthylamine system; the Roozeboom Type V is formed instead of Type III. The melting diagrams of a mixed crystal formation (-naphthol--naphthol,-naphthol--naphthylamine) are affected by a correction only to the extent that the curve branches of the two modifications of-naphthol do not begin at one point and the stable branch of the curve must be designated not as modification II but as modification I.

     

Komplexe des Nickels mit p-Methylbenzamidoxim

Zusammenfassung Die Komplexbildung des p-Methylbenzamidoxims (pMB) mit Ni²⁺ wurde in neutraler und alkalischer Lösung spektrophotometrisch untersucht. In neutraler Lösung wird ein grüner Komplex 11 gebildet, dessen Bildungskonstante ₁=1,12 ist. In alkalischer Lösung werden zwei Komplexe (11 und 12) gebildet mit Bildungskonstanten ₁=4·10⁵ und ₂=0,2.

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Nickel complexes with p-methyl benzamide oxime

The complex formation of p-methyl benzamidoxime with Ni²⁺ was studied spectrophotometrically in neutral and in alkaline solution. A green complex 11 is formed in neutral solution. Its formation constant is ₁=1.12. In alkaline solution two complexes (11 and 12) are formed. Their formation constants are ₁=4·10⁵ and ₂=0,2 resp.

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Mit 6 Abbildungen     

Cardenolide glycosides ofCheiranthus allioni. XV. Glucocheiranthoside

Another new cardenolide glycoside has been isolated from the plantCheiranthus allioni Hort., and has been named glucocheiranthoside. Its chemical structure has been established as 3-(4-O--D-glucopyranosyl--D-gulmoethylpyranosyloxy)-14-hydroxy-19-oxo-5,14-card-20(22)-enolide.State Scientific Center for Drugs, Ukraine, 310085, Kharkov, USSR. ul. Astronomicheskaya, 33. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 269–271, March–April, 1994.     

Triterpeneglycosides of Astragalus and their genins. XXV. Cyclocanthoside D from Astragalus tragacantha

The epigeal part of the plant ofAstragalus tragacantha Habl. (Leguminosae) has yielded, together with cyclosieversigenin 3-O--D-xylopyranoside, a new glycoside of the cycloartane series — cyclocanthoside D, the structure of which has been established on the basis of chemical transformations and spectral characteristics as 24S-cycloartane-3,6,16,24,25-pentaol 16-O--D-glucopyranoside 3-O--D-xylopyranoside.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 73–76, January–February, 1988.     

Triterpene glycosides ofAstragalus and their genins XLV. The chemical transformation of cycloartanes 1. Synthesis of 25-norglycosides

Literature information is given on the current state of the study of the chemical transformation of cycloartane triterpenoids. A method has been developed for the transformation of the genin part of glycosides of 20,24-epoxycycloartan-25-ols with retention of the carbohydrate constituents. Three 25-norglycosides have been synthesized from natural cyclosieversigenin glycosides, namely 16-acetoxy-3,6-dihydroxy-20R,25-norcycloartan-20,24-olide 3-O-[O--L-arabinopyranosyl-(12)--D-xylopyranoside] 6-O--D-xylopyranoside (VIII), sodium 3,6,16,20-tetrahydroxy-20R,25-norcycloartan-24-oate 6-O--D-glucopyranoside 3-O--D-xylopyranoside (XII), and 20R,25-norcycloartane-3,6,16,20,24-pentaol 6-O--D-glucopyranoside 3-O--D-xylopyranoside (XIII).Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 710–718, September–October, 1993.     

Comparative study on inclusion complexations of antiinflammatory drug flurbiprofen with β-cyclodextrin and methylated β-cyclodextrins

Abstruct Some physicochemical properties of methylated -cyclodextrins, i.e., heptakis(2,6-di-O-methyl)--cyclodextrin (DM--CyD) and heptakis(2,3,6-tri-O-methyl)--cyclodextrin (TM--CyD) were compared with those of natural -cyclodextrin (-CyD). Inclusion behaviors of -CyD and methylated -CyDs in water and in solid state were studied by solubility analysis, spectroscopies (UV, CD,¹³C-NMR and IR), X-ray diffractometry and thermal analysis, using an antiinflammatory drug flurbiprofen (FP) as a guest molecule. The spectral data suggest that the inclusion mode of FP-TM--CyD is somewhat different from those of FP--CyD and FP-DM--CyD. The solid complexes of FP with - and methylated -CyDs were obtained in molar ratio of 11, and their dissolution behavior and release from suppository base were examined. The data are presented suggesting that DM--CyD is particularly useful for improving the pharmaceutical properties of FP in various dosage forms.     

Polyhydroxylated steroids from the starfishPatiria pectinifera

By chromatography on Polikhrom-1, silica gel, and Florisil, an ethanolic extract of the digestive organs of the starfishPatiria pectinifera has yielded the steroid polyols 5-cholestan-3,6,8,15,16,26-hexaol and 5-cholestan-3,4,6,7,8,15,16,26-octaol 6-(sodium sulfate). The structures of the compounds have been shown by spectral characteristics and chemical transformations.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 738–741, November–December, 1984.