Hydroalumination of a Chlorotrialkynylsilane: Spontaneous Stepwise 1,3‐Dyotropic Rearrangement via an Intermediate Silyl Cation

A new functionalised alkynylsilane, Cl‐Si(C?C‐CMe₃)₃ ( 3 ), was obtained by a facile multistep synthesis. Treatment of 3 with equimolar quantities of the hydrides H‐M(CMe₃)₂ (M=Al, Ga) gave the mixed alkenyl‐di(alkynyl)silanes, in which the chlorine atom adopts a bridging position between the aluminium and silicon atoms. Dual hydrogallation of 3 resulted in the formation of a di(alkenyl)‐alkynylsilane containing two gallium atoms, one of which is coordinated to the chlorine atom, and the second is bonded to the α‐carbon atom of the remaining alkynyl group. A tert‐butylsilane was unexpectedly formed by a unique 1,3‐dyotropic chlorine–tert‐butyl exchange for the corresponding dialuminium compound. One aluminium atom is bonded to a tert‐butyl group, a terminal chlorine atom and the α‐carbon atom of the ethynyl moiety; the second is coordinatively unsaturated, with two terminal tert‐butyl substituents. High‐level quantum‐chemical calculations favour a stepwise dyotropic rearrangement with an intermediate cationic silicon species over a simultaneous tert‐butyl–chlorine migration via a five‐coordinate silicon atom in the transition state.     

Doubly-charged gas phase cations

Unique features of doubly-charged stable organic ions are examined and the results correlated with experimental observations. Self-consistent field molecular orbital methods are used to compute structures and stabilities of C_nH ₂ ²⁺ (n=2–9) ions which are prominent in electron impact ionization of hydrocarbon molecules. A simple curve crossing model is employed to rationalize charge transfer reactions of these ions.     

液相色谱-质谱法测定不粘锅特富龙涂层中全氟辛酸铵残留

报道了一种基于快速溶剂提取(ASE)-液相色谱-串联质谱(LC-MS/MS)法定量测定不粘锅特富龙涂层中全氟辛酸铵(APFO)残留分析方法。采用乙腈快速溶剂提取不粘锅涂层中的APFO残留,以乙腈和10mmol/L乙酸铵水溶液为流动相,经高效液相色谱分离,以多极反应监测(MRM)测定。本方法在0.5~100μg/L内线性良好(R2=0.9995);检出限1 ng/g;方法回收率在80.5%~124.6%之间,相对标准偏差为1.33%~9.30%。本方法准确、快速、简便,可用于不粘锅涂层中APFO残留的检测。     

Lipophilic aminimides possessing an additional ligating group as extractants for heavy metal cations

The title compounds were prepared in good yields by Slagel's method. All compounds obtained were used as agents for liquid-liquid extraction. They showed high affinity for certain heavy metal cations and their extractability depended to a great extent on the ligand structure. This dependence is believed to be due to the chelation of the metal cations between the imino nitrogens and the additional ligating site.     

A convenient preparation of 2-thioxo-4(3H)-quinazolinones

A simple method is described for the preparation of 3-aryl-2-thioxo-4(3H)-quinazolinones (4) by the reaction of anthranilic acids and ammonium or triethylammonium N-aryl-dithiocarbamates in ethanol. The method is also applicable to the preparation of 3-ethyl-2-thioxo-4(3H)-quinazolinone.     

Reindarstellung von Lanthan- und Praseodym-Ammoniumdoppelnitraten durch fraktionierte Kristallisation in großem Maßstab

Summary Lanthanum ammonium nitrate of purity 97%, containing 34.1 kgRE ₂O₃, was crystallized fractionally and yielded 32.5 kg oxide of purity better than 99.9% (the larger part was 99.99% pure). Out of mixtures with 66% Pr there resulted praseodymium ammonium nitrate containing 13.45 kg oxide of purity better than 99.5%. The effective separation factors are discussed, showing a better efficiency of the ammonium than of the magnesium double nitrates for the separation of praseodymium and lanthanum.

     

Comparison of 1300 nm quantum well lasers using different material systems

The band structure and material gain are calculated for 1300-nm band quantum well lasers of GaInNAs, AlGaInAs and GaInAsP material systems. The material compositions for each system are carefully chosen for comparison. The calculated results show that the peak gain is around the same in spite of the difference in band structures for the three systems.     

Solvation effects on cation–π interactions: a test study involving the quaternary ammonium ion

Water solvation effects on theoretical binding energies of the tetramethylammonium cation with benzene, phenol and indole have been analyzed as a prototype of biological cation– interactions. Solvent effects were introduced in the quantum chemical computations either by considering molecules belonging to the first solvation of the tetramethylammonium or by a polarizable continuum model. Our results show that the calculated binding energies are reduced by about three quarters with respect to the corresponding gas-phase results, but the sequence benzene<phenol<indole is preserved, in accordance with the concept of cation– interactions. Similar results are obtained for the interaction of tetramethylammonium with the benzene–indole pair.Contribution to the Jacopo Tomasi Honorary Issue     

Note on the use of reciprocity of chiral recognition in designing liquid chromatographic chiral stationary phases

The effect of methanol, acetone and acetonitrile on the sensitivity, selectivity and the detection limits (LODs) of the determination of chromium species by ion chromatography was investigated. A collinear dual-beam thermal lens spectrometer was used for the direct detection of chromium complexes [pre-column derivatized Cr(III)–pyridine-2,6-dicarboxylic acid, and post-column derivatized Cr(VI)–1,5-diphenylcarbazide] following the ion chromatographic separation on a Dionex HPIC-CS5A solvent compatible column. Different amounts of organic solvents were added directly to the eluent (up to 30%) and to the post-column reagent (up to 60%) to improve the thermooptical properties of the solvents. Consequently, the sensitivity of the technique was increased by a factor of 2–3 and LODs of 0.1 and 10 μg dm⁻³ were achieved for Cr(VI) and Cr(III), respectively, when the eluent reaching the detector contained 30% of acetonitrile. The addition of organic solvents also resulted in significant changes in retention times, which improved the Cr(III)/Cr(VI) separation.