Spectres de Masse de Derives de l'Atractyloside. Determination du Nombre de Substituants par Combinaison d'Acetylation et de Silylation

Different transformations of the functions fixed on a heterocyclic molecule were made. It is thus possible to quickly determine the number of functions of each type present in the molecule: e.g. (i) all the functions are silylated and (ii) the alcohols are acetylated whilst the sulfates and acids are silylated. Mass spectra of atractylate, apoatractylate and gummiferine have been studied and the substituents are counted and enumerated.     

Effects of methyl groups on the geometry and conformational equilibrium of 1,3-dioxanes

The geometries and energies of polymethyl-1,3-dioxanes were studied by molecular mechanics calculations. Buttressing effects of the Me groups are discussed. The chair/twist conformational equilibrium of 1,3-dioxanes having two syn-axial Me groups in the chair were calculated, and a twist form (the 1,4-twist) is found to be more stable than the chair only for 9 and 14, chair and 2,5-twist form are of comparable energies for 10 and 13, and the chair is considerably favored in 11 and 12. The chair/1,4-twist energy difference of 1 was calculated to be only 16.4 kJ mol^?1. Ring inversion of 1 goes through a transition state with C-C-C-O coplanar with a calculated activation enthalpy of 28.3 kJ mol^?1.     

Template synthesis in the nickel(II)–thiocarbohydrazide–propanone triple system

The complexing process proceeding in the Ni^II–thiocarbohydrazide (H₂N–H–NC(=S)–NH–NH₂)–propanone triple system in EtOH solution and nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix has been studied. It has been found that in the first case, template synthesis leading, as a minimum, to formation of three coordination compounds of Ni^II with (N,N,S,S)-donor tetradentate ligands having NiL¹, NiL² and NiL³compositions where L¹ is 4,6,6-trimethyl-2,3,7,8-tetraazanonen-3-di(thiohydrazide)-1,9, L² is 4,6,6,12-tetrametyl-1,9-dithio-2,3,7,8,10,11-hexaazatridekadien-3,11-hydrazide-1 and L³ is 2,8,10,10,16-pentamethyl-5,13-dithio-3,4,6,7,11,12,14,15-octaazaheptadekatrien-2,7,15 is observed, whereas in the gelatin-immobilized matrix, a complexing process in the system considered does not occur.     

Die Gasmolekeln Pd2Al2Cl10 und PdAlCl5 als Begleiter von PdAl2Cl8

Gas Molecules Pd₂Al₂Cl₁₀ and PdAlCl₅ as Accompanists of PdAl₂Cl₈ Mass spectrometric observations using a double cell showed that the reaction of gaseous Al₂Cl₆ with solid PdCl₂ besides the known gaseous complex PdAl₂Cl₈ gives PdAlCl₅ and the unexpected complex Pd₂Al₂Cl₁₀. For the equilibrium (with ΔCp? ?1 cal/K) ΔH°(298) = 7.5 kcal/Mol and ΔS°(298) = 5.3 ± 2 cl have been obtained.     

Physical and Chemical Properties of Dissolved Electrons (Excess Electrons)

Electrons produced in a gaseous, liquid, or solid solvent are called dissolved electrons or excess electrons. These excess electrons can exist as quasi-free particles of high mobility in a delocalized state, comparable with electrons in a metal; or as bound particles of low mobility they can be localized within narrow limits—in a solvent cavity formed by repulsive forces. Localized electrons can also be solvated like normal ions. Characteristically, such solvated electrons exhibit broad and extensive absorption spectra in the visible to near infrared spectral range. The localized and delocalized states of the excess electrons can be in equilibrium with each other, such that a continuous transition of the properties between the limiting extremes can be observed. The reactions of the excess electrons with suitable acceptors (substrates) are initiated by an attachment-detachment equilibrium A + e^? ? A^? which is followed by further chemical rearrangements. The rate constants of these reactions vary by more than 15 powers of ten depending on the substrates and the solvents. Most of the properties of excess electrons in solution can be interpreted by means of a model which is easily understandable but quantitatively evaluated only with considerable effort.     

Study of ion chromatographic behavior of inorganic and organic antimony species by using inductively coupled plasma mass spectrometric (ICP-MS) detection

An on-line method for the analysis of Sb(III), Sb(V) and trimethylstiboxide (TMSbO) is presented. The separation is performed using ion chromatography (IC) on a strong anion-exchange column with phthalic acid plus 2% acteone at pH 5 as mobile phase. The chromatographic system is coupled to an ICP-MS as detector. The influence of different complexing agents on the chromatographic behavior of the antimony species is studied. Rather stable complexes of Sb(III) seem to be formed with citrate and tartrate under the experimental conditions. TMSbO forms a dianionic species with citrate in contrast to the otherwise monoanionic complex. Received: 31 Juli 1997 / Revised: 8 December 1997 / Accepted: 11 December 1997     

Chemische Vitamin D<Subscript>3</Subscript>-Bestimmung in Lebertran

The different aspects of Vitamin D₃ determination and the data reported in the literature are discussed. The spectrophotometric determination of Vitamin D₃ in cod-liver oil is carried out after the alkaline saponification, extraction of unsaponified parts, precipitation of accompanying sterols and the column- and thin-layer chromatographic purification and separation of vitamin D₃ on 40 cm plates from other vitamins. The dyestuff α-naphtholbenzein is suited well as standard substance for the better location and identification of vitamin D₃ zone on the thin-layer plate. The results obtained from the chemical method were checked through the simultaneous biological determination.     

Sila-Analoga des Chlorphenoxamins und des Clofenetamins

Sila-analoguesA 2 andB 2 of two drugs from the benzhydryl ether class, chlorphenoxamine and clofenetamine, were synthesized for the first time by the steps shown in scheme 1. They and their precursors I–VI were characterized by their physical (Table 1) and chemical properties and their structures confirmed by n.m.r., mass and infrared spectrocopy (Tables 2–5). Their physiological effects were investigated and compared with those of the carbon analogues (Chapter 5).

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1. Mitt.:R. Tacke undU. Wannagat, Mh. Chem.106, 1005 (1975).

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Mit Auszügen aus der DissertationR. Tacke, Techn. Univ. Braunschweig 1974.     

Recent Applications of α-Metalated Isocyanides in Organic Synthesis

Being both nucleophilic and electrophilic, α-metalated isocyanides can add to polar double bonds, forming heterocycles. They are also synthons for α-metalated primary amines. This article describes recent or improved procedures for their use in organic synthesis: (1) In heterocyclic syntheses to give 2-oxazolines, 2-imidazolines, 2-thiazolines, oxazoles and oligooxazoles, thiazoles, triazoles, imidazolinones, pyrroles, 5,6-dihydro-1,3-oxazines and -thiazines, and (via cycloaddition with nitrones) 2-imidazolidinones. (2) In the field of formylaminomethylenation, for example transformation of estrone methyl ether and a keto sugar into the corresponding α-formylaminoacrylic esters, and the conversion of aldehydes and ketones by 3- and 4-pyridyl-methyl isocyanides into N-(1-pyridyl-1-alkenyl)formamides and their hydrolysis to 3- and 4-acylpyridines. (3) In connection with the use of α-metalated isocyanides as synthons for α-metalated primary amines, the author demonstrates how they may be used for preparation of 1,2- and 1,3-amino alcohols, 1,2-diamines, 2,3-diaminoalkanoic acids and for synthesis of higher amino acids starting from simple amino acids.     

Phase Equilibria and Critical Curves of Binary Ammonia–Hydrocarbon Mixtures

Liquid or dense supercritical ammonia has been suggested as an extraction fluid. It is indeed good solvent for very different classes of compounds, as can be seen from phase diagrams. Such diagrams for binary systems of ammonia and hydrocarbons are presented and discussed on the basis of their critical curves. Apparatus and methods for the measurement of phase equilibria and equation of state data of fluid mixtures at high pressure are described.