C,N‐chelated organotin(IV) compounds as catalysts for transesterification and derivatization of dialkyl carbonates

The potential catalytic activity of selected C,N‐chelated organotin(IV) compounds (e.g. halides and trifluoroacetates) for derivatization of both dimethyl carbonate (DMC) and diethyl carbonate (DEC) was investigated. Some tri‐, di‐ and monoorganotin(IV) species (L^CN(n‐Bu)₂SnCl (1), L^CN(n‐Bu)₂SnCl.HCl (1a), L^CN(n‐Bu)₂SnI (2), L^CNPh₂SnCl (3), L^CNPh₂SnI (4), L^CN(n‐Bu)SnCl₂ (5), L^CNSnBr₃ (6) and [L^CNSn(OC(O)CF₃)]₂(μ‐O)(μ‐OC(O)CF₃)₂ (7)) bearing the L^CN moiety (L^CN = 2‐(N,N‐dimethylaminomethyl)phenyl‐) were assessed as catalysts for reactions of both DMC and DEC with various substituted anilines. The catalytic activities of 4 and 7 for derivatization of DMC with p‐substituted phenols were studied for comparison with the standard base K₂CO₃/Silcarbon K835 catalyst (catalyst 8). The composition of resulting reaction mixtures was monitored by multinuclear NMR spectroscopy, GC and GC‐MS techniques. In general, catalysts 1, 3 and 7 exhibited the highest catalytic activity for all reactions studied, while some of them yielded selectively carbonates, carbamates, lactam or substituted urea. Copyright © 2012 John Wiley & Sons, Ltd.     

From a 2,1-Benzazaarsole to Elusive 1-Arsanaphthalenes in One Step

The 2,1-benzazaarsole ( 1 ) showed a diene-like reactivity towards selected alkynes RC≡CR (R=CO₂Me, C₅F₄N) thus forming 1-arsa-1,4-dihydro-iminonaphthalenes 2 a and 3 a as hardly isolable intermediates, that underwent facile CH→NH proton migration leading to before elusive substituted 1-arsanaphthalenes 2 b and 3 b that could be completely structurally characterized.     

Optimal trade execution under endogenous pressure to liquidate: Theory and numerical solutions

We study optimal liquidation of a trading position (so-called block order or meta-order) in a market with a linear temporary price impact (Kyle, 1985). We endogenize the pressure to liquidate by introducing a downward drift in the unaffected asset price while simultaneously ruling out short sales. In this setting the liquidation time horizon becomes a stopping time determined endogenously, as part of the optimal strategy. We find that the optimal liquidation strategy is consistent with the square-root law which states that the average price impact per share is proportional to the square root of the size of the meta-order (Bershova & Rakhlin,2013; Farmer et?al., 2013; Donier et?al., 2015; Tóth (2016).Mathematically, the Hamilton–Jacobi–Bellman equation of our optimization leads to a severely singular and numerically unstable ordinary differential equation initial value problem. We provide careful analysis of related singular mixed boundary value problems and devise a numerically stable computation strategy by re-introducing time dimension into an otherwise time-homogeneous task.     

Properties of functions with monotone graphs

A metric space (X,d) is monotone if there is a linear order < on X and a constant c>0 such that d(x,y)≦cd(x,z) for all x<y<z∈X. Properties of continuous functions with monotone graph (considered as a planar set) are investigated. It is shown, for example, that such a function can be almost nowhere differentiable, but must be differentiable at a dense set, and that the Hausdorff dimension of the graph of such a function is 1.     

Human errors and reliability of test results in analytical chemistry

The present paper is a review of the main theoretical and technical aspects of human error treatment (error modelling, reduction and quantification) as applied in aviation, engineering, medicine and other fields. The aim of the review is to attract the attention of analysts and specialists in metrology and quality in chemistry to the human error problem and its influence on the reliability of test results of chemical composition and associated measurement uncertainty. Therefore, the subject of human error is interpreted in the review in application to the conditions of a chemical analytical laboratory.     

Expanding the structural chemistry of the weakly coordinating closo-carborane CB11H12 −: its monoiodo derivatives with and without C 5v symmetry

Two iodo derivatives of closo-CB₁₁H₁₂ ^?, i.e., 12-I-1-CB₁₁H₁₁ ^? (C _5v symmetry) and 7-I-1-CB₁₁H₁₁ ^? (C _s symmetry), were prepared (the latter for the first time) and the influence of differently positioned iodine substituents on the geometry of the CB₁₁ icosahedral core was structurally examined both by X-ray diffraction and quantum-chemical computation at the MP2 level. Observed and computed molecular geometries are in overall agreement. Supramolecular architectures of these two anionic substituted monocarboranes are shown. According to DFT computations at the ZORA-SO/BP86 level, the ¹¹B chemical shifts of the boron atoms to which iodine substituents are bonded are dominated by spin–orbit coupling. Different positions of iodine atoms in these two isomers may result in different acidities of the (C)-H atoms in the icosahedral bodies, as suggested by visually analyzing the corresponding lowest unoccupied molecular orbitals.     

Rapid determination of 5-hydroxymethylfurfural by DART ionization with time-of-flight mass spectrometry

DART (direct analysis in real time), a novel technique with wide potential for rapid screening analysis, coupled with high-resolution time-of-flight mass spectrometry (TOF-MS) has been used for quantitative analysis of 5-hydroxymethylfurfural (5-HMF), a typical temperature marker of food. The DART/TOF-MS method was optimised and validated. Quantification of 5-HMF was achieved by use of a stable isotope-labelled 5-HMF standard prepared from glucose. Formation of 5-HMF from saccharides, a potential source of overestimation of results, was evaluated. Forty-four real samples (honey and caramelised condensed sweetened milk) and 50 model samples of heated honey were analysed. The possibility of using DART for analysis of heated samples of honey was confirmed. HPLC and DART/TOF-MS methods for determination of 5-HMF were compared. The correlation equation between these methods was DART?=?1.0287HPLC?+?0.21340, R ²?=?0.9557. The DART/TOF-MS method has been proved to enable efficient and rapid determination of 5-HMF in a variety of food matrices, for example honey and caramel.     

Collision-Induced Dissociation of Diazirine-Labeled Peptide Ions. Evidence for Brønsted-Acid Assisted Elimination of Nitrogen

Gas-phase dissociations were investigated for several peptide ions containing the Gly-Leu* N-terminal motif where Leu* was a modified norleucine residue containing the photolabile diazirine ring. Collisional activation of gas-phase peptide cations resulted in facile N₂ elimination that competed with backbone dissociations. A free lysine ammonium group can act as a Brønsted acid to facilitate N₂ elimination. This dissociation was accompanied by insertion of a lysine proton in the side chain of the photoleucine residue, as established by deuterium labeling and gas-phase sequencing of the products. Electron structure calculations were used to provide structures and energies of reactants, intermediates, and transition states for Gly-Leu*-Gly-Gly-Lys amide ions that were combined with RRKM calculations of unimolecular rate constants. The calculations indicated that Brønsted acid-catalyzed eliminations were kinetically preferred over direct loss of N₂ from the diazirine ring. Mechanisms are proposed to explain the proton-initiated reactions and discuss the reaction products. The non-catalyzed diazirine ring cleavage and N₂ loss is proposed as a thermometer dissociation for peptide ion dissociations.