Diastereoselective ring-closing metathesis: synthesis of P-stereogenic phosphinates from prochiral phosphinic acid derivatives

[reaction: see text] The preparation of phosphorus-containing trienes featuring two diastereotopic vinyl moieties followed by a diastereoselective ring-closing metathesis is described. This methodology allowed for the synthesis of novel highly functionalized P-stereogenic heterocycles featuring both an exo- and an endocyclic double bond. An investigation into the factors influencing the diastereochemical outcome of the ring-closing metathesis is also presented, revealing that the geometry of the double bonds conjugated to phosphorus is important and that 1,3-stereoinduction is superior to 1,4-stereoinduction for these reactions.     

Triphenylphosphan-Nickel(0)-Komplexe mit Isocyanid-Liganden — [(RNC)nNi(PPh3)4–n] (n = 1–3)

Triphenylphosphane Nickel(0) Complexes with Isocyanide Ligands — [(RNC)_nNi(PPh₃)_4–n] (n = 1–3) Synthesis and properties of the isocyanide triphenylphosphane nickel(0) complexes [(RNC)Ni(PPh₃)₃], [(RNC)₂Ni(PPh₃)₂] and [(RNC)₃Ni(PPh₃)] (R = ^tBu, Cy, PhCH₂, p-TosCH₂) are described. I.r. and ³¹P n.m.r. spectra were recorded and the X-ray crystal structure of [(PhCH₂NC)₂Ni(PPh₃)₂] was determined.     

Mass spectrometric studies of organophosphorus compounds: III—Remarkable migration of chalcogen on electron impact of organophosphorus compounds

The mass spectra of several dibenzo (d.f)-1,3,2,-dioxaphosphorepines of the type where X=0, S, Se and R=2,2′-biphenylylene, have been studied. Dibenzochalcogen ions [RX]⁺˙ stemming directly from [M]⁺˙ were observed with high intensities, indicating specific migration of X from phosphorus to carbon with simultaneous destruction of the dioxaphosphorepine ring. Simple cleavage of P? Y as usually observed in similar organophosphorus compounds is not a common process here.     

Evaluation of a retention model in comprehensive two-dimensional gas chromatography

Modeling the retention in comprehensive two-dimensional gas chromatography (GC x GC) was achieved using retention indices obtained in conventional GC. Predicted results were compared with experimental data obtained in the two-dimensional separation of a synthetic hydrocarbon mixture. This proved to be helpful in optimizing the operating conditions of GC x GC separation of a complex petroleum sample and in identifying chemical families.     

Über die Uranylverbindungen des Natrium-cyklohexyldithiocarbaminats

Zusammenfassung Na-cyklohexyldithiocarbaminat reagiert im p_H-Bereich 6,6 bis 7,2 mit Uranylsalzen unter Bildung eines in Wasser mit gelber Farbe lösliehen Komplexes, der bei p_H 6,6 ein Absorptionsmaximum bei 392 bis 394 nm besitzt. Die wäßrige Lösung wird durch Zusatz von Alkalilauge bis zum p_H 8 bis 9 momentan entfärbt.Es wird ein Kaliumdoppelsalz KUO₂(S₂HCNC₆H₁₁)₃ · 3 H₂O beschrieben; ferner wird über die Umwandlung des Calciumdoppelsalzes beim Kochen mit NaOH berichtet.

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Summary Sodium cyolohexyldithiooarbamate reacts, in the p_H range 6.6 to 7.2, with uranium salts to yield a complex which gives a yellow aqueous solution. The absorption maximum is at 392–394 nm at p_H 6.6. The aqueous solution loses its color immediately when caustic alkali is added to raise the p_H to 8 or 9.A potassium double salt, KUO₂(S₂HCNC₆H₁₁)₃ · 3 H₂O is described. A report is also given of the transformation of the calcium double salt on boiling with NaOH.

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Résumé Le dithiocarbamate de cyclohexylsodium réagit dans le domaine de p_H 6,6 à 7,2 sur les sels d'uranyle avec formation d'un complexe coloré en jaune, soluble dans l'eau, qui possède à p_H 6,6 un maximum d'absorption pour 392–394 nm. Par addition de lessive alcaline jusqu'à p_H 8 à 9 on décolore momentanément la solution aqueuse.On décrit un sel double de potassium KUO₂(S₂HCNC₆H₁₁)₃ · 3 H₂O; on rend compte, de plus, de la transposition du sel double de calcium par chauffage avec la soude.

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Gewidmet zur 100. Wiederkehr des Geburtstages vonFriedrich Emich.     

Über magnetische Beeinflussung der Polarisation der Resonanzfluoreszenz

1. Historical remarks concerning magnetic influence on the polarization of resonance fluorescence and its explanation as the Zeeman effect. 2. Rotation of the plane of polarization of the resonance fluorescence of Hg by weak magnetic fields and determination of the lifetime of the excited state. 3. Experiments concerning the excitation of the resonance fluorescence of Hg by light with different kinds and directions of polarization.     

Comparison between the adsorption behaviors of an organic cation and an organic anion on several reversed-phase liquid chromatography adsorbents

Adsorption data of an organic cation (propranololium chloride) and an organic anion (sodium 1-naphthalene sulfonate) were measured by frontal analysis on two RPLC adsorbents, Symmetry-C18 and XTerra-C18, with aqueous solutions of methanol as the mobile phases. The influence of supporting neutral salts on the adsorption behavior of these two ions are compared. The Henry constants are close (H approximately 5). The four sets of isotherm data are all well accounted for using the bi-Moreau model. However, the isotherms of the two ions behave differently at high concentrations. The initial behaviors of all the isotherms are antilangmuirian but remain so in a much wider concentration range for the cation than for the anion, due to its stronger adsorbate-adsorbate interactions on the low-energy adsorption sites. The retention times of both ions increase with increasing concentration of neutral salt in the mobile phase, suggesting the formation of ion-pair complexes, with Cl- for the cation and with Na+ for the anion. The adsorbate-adsorbate interactions vanish in the presence of salt and the bi-Moreau isotherm model tends toward a bi-Langmuir model. Differences in adsorption behavior are also observed between the cation and the anion when bivalent inorganic anions and cations, respectively, are dissolved in the mobile phase. High concentration band profiles of 1-naphthalene sulfonic acid are langmuirian, except in the presence of a trivalent cation, while those of propranolol are antilangmuirian under certain conditions even with uni- or divalent cations.     

电解池电阻和容抗的快速测定仪

利用锁定放大器, 恒电势仪, 压控频率正弦波信号发生器等组装成电解池电阻和容抗的快速测定仪。可以快速地自动测是和绘出阻抗谱图和电阻/容抗～时间图。采用微小恒定振幅正弛交流电流(<10 μA)作为微扰, 数据可能较为可靠。给出了线路及所需滤波器元件的数据, 说明仪器各部份之间的干扰可以减少。测定了滴汞电极在1 mol L~(-1)Na_2SO_4溶液中及1 mol L~(-1)Na_2SO_4被正庚醇饱和的溶液中的微分电容～电势数值。证明仪器工作良好。另外, 从实验数据和理论分析, 均表明D.C.Grahame的被广泛引用的有关经典数据有误。本文做了修正。还测定了半导体氧化铁电极在光照下黑暗中的阻抗谱图和氧化银电极充电和停止充电后开路下的电阻～时间图, 显示了仪器在电化学研究中利用的可能性。     

Influence of structural changes on the ion selectivities of magnesium ionophores based on malonic acid diamides

In an investigation of octamethylene bis(malonic acid diamides) and their selectivities for magnesium, it was found that presence of secondary amides within the particular ionophore played a considerable role in the enhancement of magnesium selectivity. Similar effects in other ionophores, i.e. tris(malonic acid diamides), were thus systematically looked at with the help of selectivity measurements with the hope of optimizing the number of secondary and tertiary amides so as to improve the magnesium selectivity. The syntheses of several investigated tris(malonic acid diamide) isologues are equally reported.Deceased in November 1992