Alkaloids of Nitraria komarovii. XIII. Nitramine N-oxide and the structure of dehydroschoberine

Deoxyvasicinone, d-vasicinone, -peganine, deoxypeganine, nitraramine, dihydronitraraine, nitraroxine, tryptamine, schoberine, and two new bases have been isolated for the first time from the epigeal part of the plantNitraria komarovii. The structures of the new bases have been established on the basis of spectral characteristics and chemical transformations as nitraramine N-oxide and dehydroschoberine. Nitramidine, isoschoberine, nitraroxine, nitraraine, and tetramethylenetetrahydro--carboline N-oxide were isolated from the seeds with fruit.Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 39–43, January–February, 1993.     

Acid chlorides of unsaturated phosphonous acids

Summary The dichloride of -ethoxyvinyl-, -isooctyloxyvinyl-, and 2-chloro-3-methylbut-3-enylphosphonous acids have been synthesized and characterized for the first time. The diethyl ester of -ethoxyvinylphosphonous acid has been-obtained from the dichloride of -ethoxyvinylphosphonous acid.     

Synthesis of carboline bases

A study has been made of the condensation of serotonin with aldehydes to give the corresponding -carboline derivatives. In most cases the reaction was run under biological conditions (pH 5. 4, 36). The following aldehydes were reacted: acetaldehyde, butyraldehyde, isobutyraldehyde, benzaldehyde, n-octaldehyde, and formaldehyde. The corresponding -carboline derivatives are obtained from the first 5 of these. The reaction with formaldehyde leads to complete resinification.     

Reactions of Caryophyllene 4β,5α-Epoxide with Carbonyl Compounds on Clay

Products of reaction between caryophyllene 4,5-epoxide and carbonyl compounds (acrolein, crotonaldehyde, -methacrolein, and acetone) were synthesized on clay. Two diastereomers in reaction with each aldehyde and a single isomer with acetone were obtained. In reaction of the epoxide with acetone an isomerization product was isolated, 4,4,9-trimethyltricyclo[6.2.2.0^{1 , 5}]dodec-9-en-2-ol that was unknown before.     

Structure of ulososide A,a new triterpenoid glycoside from theUlosa sp. sponge

A new triterpenoid glycoside, (20S,22S,23R,24S)-3,22,23-trihydroxy-3-O-[O-(-D-glucuronopyranosyl)-(16)-(-D-glucopyranosyl)]-14-nor-24-methyllanost-8(9)-en-31-oic acid (ulososide A), has been isolated from the sponge Ulosa sp. and characterized.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1326–1329, July, 1994.     

7-Azaindole derivatives

The Bischler-Napiralski reaction is used to synthesize 1-phenyl-3, 9-dimethyl-5, 6-dihydro-12-aza--carboline, and its 5-methyl and 5-ethyl derivatives, from 1-phenyl-4-methyl-3-aminoalkyl-T-azaindoles. 5, 6-Dihydro-12-aza--carbolines prepared by sodium borohydride reduction are converted into 1-phenyl-3, 9-dimethyl-3, 4, 5, 6-tetrahydro-12-aza--carboline and its 5-methyl and 5-ethyl derivatives. 1-Phenyl-9-methyl-12-azaharman is synthesized by palladium dehydrogenation of 1-phenyl-3, 9-dimethyl-5, 6-dihydro-12-aza--carboline.For Part XVII see [1].     

Pyridine ketoximes as analytical reagents: The α and β isomers of 2,2′2-dipyridylglyoxime

Summary The preparation, separation, and characterization of the and isomers of 2,2-dipyridylglyoxime are described. The and configurations are assigned on the basis of NMR, IR, and chemical data. In addition, a method of assessment of purity is given.

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Zusammenfassung Herstellung, Trennung und Charakterisierung der - und -Isomeren des 2,2-Dipyridylglyoxims wurden beschrieben. Die beiden Konfigurationen wurden auf der Grundlage ihrer kernmagnetischen Resonanz, ihres IR-Spektrums und ihres chemischen Verhaltens gekennzeichnet. Außerdem wurde ihre Reinheitsprüfung beschrieben.

     

Ionotropic reactions of β-sultones

The reaction mechanism of-sultones are discussed; a scheme for the reactivity is proposed. Polyfluoro--sultones can undergo anionotropic reactions of the type Hydrogeneous-sultones under prototropic reactions:     

Neue Reagentien zum papierchromatographischen Nachweis von Aminosäuren, 3. Mitt.: Reaktionen des 1,8-Trimethylenchinisatins mit primären Aminoverbindungen

Zusammenfassung 1,8-Trimethylenchinisatin-hydrat (TMCH) reagiert mit Aminosäuren zum farblosen Bis-(2-oxo-4-hydroxy-1,8-trimethylen-1,2-dihydro-3-chinolinyl)-amin (2). Da2 bei der Dehydrierung in das Farbsalz5 übergeht, welches eine dem Ruhemann-Purpur analoge Struktur aufweist, ergeben sich neuartige Aspekte zur Deutung des Mechanismus der Ninhydrin-Reaktion.

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1.8-Trimethylenequinisatin hydrate (TMCH) reacts with amino acids yielding the colorless bis-(2-oxo-4-hydroxy-1.8-trimethylene-1.2-dihydro-3-quinolyl)-amine (2). Upon dehydrogenation of2 the dye salt5 is obtained. Because of the close relationship between5 and Ruhemann's purple a re-interpretation of the mechanism of the ninhydrin reaction could be made.

     

Triterpene Glycosides of Astragalus and Their Genins. LXVI. Cycloorbicoside C, a New Bisdesmoside

The new triterpene glycoside cycloorbicoside C was isolated from the aerial parts of Astragalus orbiculatus Ledeb. (Leguminosae) and was identified as (23R,24S)-16,23;16,24-diepoxycycloartan-3,25-diol 3-O--D-xylopyranoside 25-O--D-glucopyranoside.     

Binding of vitamin A byβ-cyclodextrin and heptakis(2,6-O-dimethyl)-β-cyclodextrin

Inclusion complexation of all-trans-retinol, retinal and retinoic acid with -cyclodextrin (-CD) and heptakis(2,6-O-dimethyl)--cyclodextrin (DM--CD) were investigated by means of UV-vis spectroscopy. The association constants (K _a) obtained for vitamin A with DM--CD is greater than with -CD. On the other hand, for the same host compoundK _a values of retinol, retinal and retinoic acid are very close to each other.     

Transformed steroids

Conclusions The addition of thioacetic acid to the ⁵ bonds of 16- and 16-mercapto-3-hydroxypregn-5-en-20-one 3,16-diacetates (II) and (III) under radical conditions gives not only trans-diaxial addition products-6,16- and 6,16-dimercapto-3-hydroxy-5o;-pregnan-20-one 3,6,16-triacetates (IV) and (V) -but also cis-addition products-6,16- and 6,16-dimercapto-3-hydroxy-5-pregnan-20-one 3,6,16-triacetates (VI) and (VII).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 405–411, February, 1969.     

Nitroderivate vonβ,β,β-Trihalo-α,α-bis-(4-alkoxybzw. 4-oxy-phenyl)-äthanen

Zusammenfassung Auf Grund von Modellbetrachtungen wurde die Existenz der in der Literatur beschriebenenOctanitro-Derivate von ,,-Trihalo-,-bis-(4-alkoxy-phenyl)-äthanen in Zweifel gezogen. Entsprechende Untersuchungen ergaben, daß es sich bei ihnen umTetranitro-Verbindungen handelt und daß es nicht möglich ist, diese DDT-Analogen mehr als vierfach zu nitrieren. Die Konstitution der Tetranitro-Verbindungen wurde durch Abbau bewiesen: Beim ,,-Trichlor-,-bis-(3,5-dinitro-4-methoxy-phenyl)-äthan (II) durch Überführung in das entsprechende Keton (VII), beim ,,-Trichlor-,-bis-(3,5-dinitro-4-äthoxy-phenyl)-äthan (IV) durch Entalkylierung und Methylierung zu II. Der Beweis der 3,3, 5,5-Stellung der Nitrogruppen in II und IV ist auch für andere Tetranitro-Derivate von ,,-Trihalo-,-bis-(4-X-phenyl)-äthanen (X=Substituenten I. Ordnung) von Bedeutung.Mitt. II der Reihe: Stereochemische Untersuchungen in der Diphenylmethanreihe.     

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.     

Three-component complexes of cyclodextrins. Exciplex formation in cyclodextrin cavity

The fluorescence quenching of naphthalene, 1-methylnaphthalene, and acenaphthene by trimethylamine (TMA) was studied in aqueous -cyclodextrin (-CD) solutions to know the structural requirements for guest molecules to form three-component complexes. The apparent rates for the fluorescence quenching of the naphthalene derivatives by TMA markedly increased in the presence of -CD. The fluorescence quenching of 1-methylnaphthalene and acenaphthene by TMA was accelerated by -CD more efficently than that of naphthalene. These results suggest the structures of the three-component complexes as the arene-capped -CD including TMA in its cavity.     

First synthesis and characterization of platinum(II) and palladium(II) complexes of some β-carboline hydrochloride alkaloids and their decomposition products in DMSO

Summary Platinum(II) and palladium(II) complexes of general formulatrans-[MCl₂LL] (M=Pt or Pd, L, L=-carboline; M=Pt, L=-carboline, L=ethene; -carboline alkaloids are harmaline, harmine, harmalol as hydrochloride derivatives) have been prepared for the first time. The structures were assigned and identified on the basis of their CHN analyses, i.r. and¹H n.m.r. spectra. The decomposition products of these complexes in DMSO have been described.     

Separation of diastereomers of a 1,3-disubstituted tetrahydro-β-carboline by capillary electrophoresis with β-cyclodextrin

Summary Capillary zone electrophoresis with -cyclodextrin as electrolyte additive has been investigated for the separation of the diastereomers of a 1,3-disubstituted tetrahydro--carboline. The effects of pH, buffer concentration, -cyclodextrin concentration and applied voltage on resolution were investigated. This study shows that optimizing the assay conditions leads to maximum chiral separation or resolution. The method enables further research on the quantitative analysis of these compounds.     

Study of hydrogen adsorption on iridium catalysts

The influence of dispersity on hydrogen adsorption on Ir black and Ir/C catalysts has been studied. It is shown that supported iridium reduces the heat of hydrogen adsorption as compared to Ir black. With decreasing catalyst dispersity, the amount of weakly bound hydrogen increases, while its adsorption heat decreases on all Ir catalysts.

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Ir- Ir/C-. , Ir-. C , Ir-.

     

Some Pharmaceutical Properties of a New Branched Cyclodextrin, 6-O-α-(4-O- α-D-Glucuronyl)-D-glucosylβ-cyclodextrin

Some physicochemical and biological properties of a new branched cyclodextrin, 6-O--(4-O--d-glucuronyl)-d-glucosyl--cyclodextrin GUG--CyD) were investigated. Further, theinteraction of GUG--CyD with several drugs was studied by the solubility and spectroscopic methods, and compared with those of parent -CyD and 6-O--maltosyl--CyD(₂--CyD).The hemolytic activity of GUG--CyD on rabbit erythrocytes was lower than those of -CyD and ₂--CyD. GUG--CyD and ₂--CyD showed negligible cytotoxicity on Caco-2 cells up to at least 0.1 M. The inclusion ability of GUG--CyD to neutral and acidic drugs was comparable to or slightly smaller than those of -CyD and ₂--CyD, probably because of a steric hindrance of the branched sugar. On the other hand, GUG--CyD showed greater affinity for the basic drugs, compared with -CyD and ₂--CyD, owing to the electrostatic interaction of its carboxylate anion with positive charge of basic drugs. Thus GUG--CyD may be useful as a safe solubilizing agent particularly for basic drugs.