Di and monocarbonyl complexes of rhodium(I) containing singly charged bidentate ligands

Summary A series of neutral square planar rhodium(I) dicarbonyls containing singly charged bidentate ligands (salicylaldoxime, -benzoinoxime, -furildioxime, -benzildioxime, dimethylglyoxime, cupferron) has been prepared from three sources: (i) tetracarbonyl--dichlorodirhodium(I), (ii) solutions of hydrated rhodium chloride in DMF held under reflux and (iii) a carbonylated solution of hydrated rhodium chloride in boiling absolute alcohol. These dicarbonyls react with triphenylphosphine,-arsine and -stibine to yield monocarbonyl derivatives. The monocarbonyls form 1 : 1 adducts with TCNE. All complexes have been characterized by elemental analysis, i.r. and uv-visible spectra.     

Investigations in the field of lipids

Summary 1. The synthesis of the following neutral plasmalogens has been effected: -O-(octadec-1-enyl)-, distearoylglycerol, -O-(octadec-1-enyl)-, -dipalmitoylglycerol, -O-(hexadec-1-enyl)-, -distearoylglycerol, and -O-(pentadec-1-enyl)-, -dipalmitoylglycerol.2. During the synthesis, the following compounds were isolated and characterized by their physicochemical constants: the -octadec-1-enyl ether of glycerol, -(2-hydroxyoctadecyl) , -isopropylideneglyceryl ether, the tosylate of -(2-hydroxyoctadecyl) , -isopropylideneglyceryl ether, and -O-(2-tosyloxyoctadecyl) glycerol.3. The IR spectra of the -octadec-1-enyl ether of glycerol and the neutral plasmalogens have been studied.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 6, pp. 367–371, 1966     

Influence of sodium on the catalytic properties of bismuth-molybdenum oxide catalysts

In the ammoxidation of propylene, the presence of a normal NaBi(MoO₄)₂ phase in bismuth molybdenum oxide catalysts decreases the acrylonitrile yield due to its oxidation

---

NaBi(MoO₄)₂ -- .

     

Polyhydroxysteroids from the Far-Eastern starfishCtenodiscus crispatus

Four new polyhydroxysteroids, 5-cholesta-3,5,6,15,16,25,26-heptaol, 24-ethyl-5-cholesta-3,5,6,15,28,29-heptaol-29-sulfate, (22E)-24-methyl-5-cholest-22-ene-3,5,6,15,25,26-hexaol-26-sulfate, 24-propyl-5-cholesta-3,5,6,8,15,28,29-heptaol, and the known 5-cholesta-3,5,6,15,16,26-hexaol, have been isolated from the starfishCtenodiscus crispatus.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1821–1825, October, 1994.     

<Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR spectra of some drimanic sesquiterpenoids

One- and two-dimensional homo- and heteronuclear correlation proton, carbon, proton—proton, and proton—carbon NMR spectra of fifteen drimanic sesquiterpenoids: 11,12-dibromodrima-5,8-dien-7-one, drim-8-en-7-one, 11-hydroxydrim-8-en-7-one, 11,12-dihydroxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 8,9-epoxydriman-7-one, 8,9-epoxydriman-7-ol, 11,12-diacetoxydrim-8-en-7-ol, drimane-7,8,11-triol, 7,8-isopropylidenedioxydriman-11-al, 9, 11-dihydroxydrim-7-en-6-one, drimane-7,8,9-triol, drimane-7,8,11-triol, and drim-8-ene-7,11,12-triol were studied. The proton and carbon chemical shifts were assigned.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2589–2594, December, 2004.     

Synthesis and Dehydrohalogenation of 3 β-Chloro-5 α,7 α-dibromo-6-ketosteroids of the Stigmastane and Cholestane Series

3-Chloro-5,7-dibromo-6-ketosteroids 5a and 5b are synthesized from -sitosterol (1a) and cholesterol (1b). Dehydrohalogenation of these forms 7-bromo-2,4-dien-6-ones (6a-b), 2,4-dien-6-ones (7a-b), and 14-hydroperoxy-2,4,7-trien-6-ones (8a-b). Woodward hydroxylation of dienone 6a produces 2-iodo-7-bromo-3-acetoxy-⁴-6-ketone 9 and 7-bromo-2,3-diacetoxy-⁴-6-ketone 10. 2-Iodo-3-acetoxy-^4,7,14-trien-6-one 11 is prepared analogously from trienone 8a.     

The determination of nitrogen in zirconium by charged-particle activation analysis

Summary The determination of nitrogen in zirconium by charged-particle activation analysis is described. The¹⁴N(,n)¹³N and the¹⁴N(p,)¹¹C reactions were used. The¹³N activity was separated from matrix activity as ammonia by steam-distillation after dissolution of the sample in dilute hydrofluoric acid. The¹¹C activity was separated as carbon dioxide by dissolution of the sample in a mixture of concentrated sulphuric acid, sodium fluoride and potassium periodate, followed by oxidation of the evolved gases with a copper oxideiron oxide-kaolin mixture and trapping of the carbon dioxide in dilute sodium hydroxide solution. The chemical yield of both separations was investigated. The nuclear interference of boron can be neglected, in view of the low boron content. Alpha- and proton-activation yielded the following results for BCR reference materials (alpha-activation results first): CRM 21: 24.6±3.3 and 25.9±0.8g/g (certified value: 26.4±2.5g/g); CRM 56: 12.0±1.1 and 10.5±0.3g/g (certified value: 11.7±1.7g/g); CRM 57: 11.2±0.3g/g (alpha-activation) (certified value: 11.9±1.8g/g).

---

Die Bestimmung von Stickstoff in Zirkonium durch Aktivierungsanalyse mit geladenen Teilchen

Zusammenfassung Folgende Kernreaktionen wurden angewendet:¹⁴N(,n)¹³N und¹⁴N(p,)¹¹C. Nach dem Auflösen der Probe in verdünnter Flußsäure wurde die¹³N-Aktivität als Ammoniak durch Wasserdampfdestillation von der Aktivität der Matrix abgetrennt. Die¹¹C-Aktivität wurde als Kohlendioxid abgetrennt. Nach dem Auflösen der Probe in einer Mischung aus konzentrierter Schwefelsäure, Natriumfluorid und Kaliumperjodat wurden die entstehenden Gase durch eine Mischung aus Kupferoxid-Eisenoxid-Kaolin oxydiert. Dann folgte die Absorption von Kohlendioxid in verdünnter Natronlauge. Die chemische Ausbeute beider Trennungen wurde untersucht. Der Borgehalt in den Proben ist so klein, daß eine Störreaktion von Bor zu vernachlässigen ist. Folgende Ergebnisse wurden mit einigen BCR-Referenzproben mit Alpha- und Protonenaktivierung erhalten: CRM 21: 24,6 ± 3,3 und 25,9 ± 0,8g/g (gesicherter Wert: 26,4 ± 2,5g/g) CRM 56: 12,0 ± 1,1 und 10,5 ± 0,3g/g (gesicherter Wert: 11,7 ± 1,7g/g) CRM 57: 11,2 ± 0,3g/g (Alpha-Aktivierung) (gesicherter Wert: 11,9 ±1,8g/g)

     

Eine Methode zur quantitativen Bestimmung von Methoxylgruppen nach Zeisel mit kleinsten Substanzmengen

Zusammenfassung Es wird eine Variation des Zeisel-Verfahrens zur quantitativen Bestimmung von Methoxylgruppen beschrieben. Als Vorlage zur Absorption des bei der Methoxylspaltung entstehenden Methyljodids wird Picolin verwendet. Es bildet sich quantitativ N-Methyl--picoliniumjodid, das colorimetrisch bestimmt werden kann. Die Methode hat eine Fehlerbreite von maximal ±5%. Die Nachweisgrenze liegt bei 1 g N-Methyl--picolin.FräuleinMaria Kroczek wird für geschickte technische Assistenz herzlich gedankt.     

Synthesis of triterpene glycosides

Summary The acyl -D-glucopyranoside, the acyl -D-xylopyranoside, the acyl D- and L--arabinopyranosides, and the acyl -D-lactoside of 18-glycyrrhetic acid, and also the acyl -D-lactoside of 18-glycyrrhetic acid have been synthesized. The acid and alkaline hydrolysis of the compounds obtained has been studied.Khimiya Prirodnykh Soedinenii, Vol. 4, No. 1, pp. 13–19, 1968     

Semi-preparative liquid-chromatographic separation of all four stereoisomers of α-bisabolol on tribenzoylcellulose

Summary A semi-preparative low-pressure liquid-chromatographic procedure using tribenzoylcellulose has been developed for the separation and isolation of the four -bisabolol stereoisomers. Stereochemical assignments were made by HPLC-polarimeter coupling and by using the authentical isomers. This method can be applied to the quality control of chamomile preparations, as it allows the detection of adulterations resulting from admixtures of synthetic -bisabolol. In addition, the isolation of all four -bisabolol stereoisomers from commercially available synthetic -bisabolol has been made possible.