Air‐Stable Solid Aryl and Heteroaryl Organozinc Pivalates: Syntheses and Applications in Organic Synthesis

A wide range of air‐stable, solid, polyfunctional aryl and heteroarylzinc pivalates were efficiently prepared by either magnesium insertion or Hal/Mg exchange followed by transmetalation with Zn(OPiv)₂ (OPiv=pivalate). By reducing the amount of LiCl the air stability could be significantly enhanced compared with previously prepared reagents. An alternative route is directed magnesiation using TMPMgCl ? LiCl (TMP=2,2,6,6‐tetramethylpiperidyl) followed by transmetalation with Zn(OPiv)₂ or, for very sensitive substrates, direct zincation by using TMPZnOPiv. These zinc reagents not only show excellent stability towards air, but they also undergo a broad range of C?C bond‐formation reactions, such as allylation and carbocupration reactions, as well as addition to aldehydes and 1,4‐addition reactions. Acylation reactions can be performed by using an excess of TMSCl to overcome side reactions of the omnipresent pivalate anion.     

Strong Direct Magnetic Coupling in a Dinuclear CoII Tetrazine Radical Single‐Molecule Magnet

The ligand‐centered radical complex [(CoTPMA)₂‐μ‐bmtz^.?](O₃SCF₃)₃ ? CH₃CN (bmtz=3,6‐bis(2′‐pyrimidyl)‐1,2,4,5‐tetrazine, TPMA=tris‐(2‐pyridylmethyl)amine) has been synthesized from the neutral bmtz precursor. Single‐crystal X‐ray diffraction studies have confirmed the presence of the ligand‐centered radical. The Co^II complex exhibits slow paramagnetic relaxation in an applied DC field with a barrier to spin reversal of 39 K. This behavior is a result of strong antiferromagnetic metal–radical coupling combined with positive axial and strong rhombic anisotropic contributions from the Co^II ions.     

The conversion of 2-(4-chloro-5H-1,2,3-dithiazolylideneamino)benzonitriles into 3-aminoindole-2-carbonitriles using triphenylphosphine

2-(4-Chloro-5H-1,2,3-dithiazolylideneamino)benzonitrile 1a reacts with triphenylphosphine (4 equiv) in the presence of water (2 equiv) to afford anthranilonitrile 2a, 3-aminoindole-2-carbonitrile 3a and (2-cyanoindol-3-yl)iminotriphenylphosphorane 4a, together with triphenylphosphine sulfide and oxide. The use of polymer bound triphenylphosphine provides cleaner reaction mixtures. 2-(4-Chloro-5H-1,2,3-dithiazolylideneamino)-4,5-dimethoxybenzonitrile 1h does not give the corresponding indole on treatment with triphenylphosphine but gives 6,7-dimethoxyquinazoline-2-carbonitrile 5 (15%) and 2-cyano-4,5-dimethoxy cyanothioformanilide 6 (36%). A total of seven new 3-aminoindole-2-carbonitriles 3a-g are prepared and fully characterised.     

Global existence for a nonlinear Schroedinger–Chern–Simons system on a surface

Global existence of regular solutions for a nonlinear Schroedinger–Chern–Simons system of equations on a two-dimensional compact Riemannian manifold is proved.     

Synthesis and characterization of a chlorofunctionalized unsaturated carbosilane oligomer

Acyclic diene metathesis (ADMET) polymerization offers a viable route for the synthesis of chlorofunctionalized unsaturated carbosilane oligomers. The Si Cl bond in unsaturated carbosilane monomers remains inert during metathesis and the use of a highly reactive molybdenum-based, Lewis acid-free alkylidene catalyst affords unsaturated chlorofunctionalized carbosilane oligomers with known vinyl end groups. The first synthesis of an unsaturated carbosilane oligomer functionalized with a Si Cl bond was performed. A chlorofunctionalized silacyclopentene product was also observed, due to a backbiting reaction. This new class of functionalized oligomers has a low glass transition temperature and sites of unsaturation which may be used for further reaction. ADMET chemistry now provides access to a variety of chlorofunctionalized unsaturated carbosilanes which can be used to tailor make hydrolytically stable carbosilane oligomers and polymers via nucleophilic grafting reactions.     

Effects of a Volatile Organic Compound Filter on Breath Profiles Measured by Secondary Electrospray High-Resolution Mass Spectrometry

Environmental volatile organic compounds (VOCs) from the ambient air potentially influence on-line breath analysis measurements by secondary electrospray ionization high-resolution mass spectrometry (SESI-HRMS). The aim of this study was to investigate how inhaling through a VOC filter affects the detected breath profiles and whether it is feasible to integrate such filters into routine measurements. A total of 24 adult participants performed paired breath analysis measurements with and without the use of an activated carbon filter for inspiration. Concordance correlation coefficients (CCCs) and the Bland–Altman analysis were used to assess the agreement between the two methods. Additionally, the effect on a selection of known metabolites and contaminants was analyzed. Out of all the detected features, 78.3% showed at least a moderate agreement before and after filter usage (CCC > 0.9). The decrease in agreement of the remaining m/z features was mostly associated with reduced signal intensities after filter usage. Although a moderate-to-substantial concordance was found for almost 80% of the m/z features, the filter still had an effect by decreasing signal intensities, not only for contaminants, but also for some of the studied metabolites. Operationally, the use of the filter complicated and slowed down the conductance of measurements, limiting its applicability in clinical studies.     

Pyridine Carboxamides Based on Sulfobetaines: Design,Reactivity, and Biological Activity

The synthesis of the products of the 1,3-propanesultone ring opening during its interaction with amides of pyridinecarboxylic acids has been carried out. The dependence of the yield of the reaction products on the position (ortho-, meta-, para-) of the substituent in the heteroaromatic fragment and temperature condition was revealed. In contrast to the meta- and para-substituted substrates, the reaction involving ortho-derivatives at the boiling point of methanol unexpectedly led to the formation of a salt. On the basis of spectroscopic, X-Ray, and quantum-chemical calculation data, a model of the transition-state, as well as a mechanism for this alkylation reaction of pyridine carboxamides with sultone were proposed in order to explain the higher yields obtained with the nicotinamide and its N-methyl analog compared to ortho or meta parents. Based on the analysis of ESP maps, the positions of the binding sites of reagents with a potential complexing agent in space were determined. The in silico evaluation of possible biological activity showed that the synthetized compounds revealed some promising pharmacological effects and low acute toxicity.     

Eine quantitative Bestimmung des Cumarins und der Melilots?ure im Melilotus officinalis

Ohne Zusammenfassung     

A study on m-chloroperbenzoic acid and lead tetraacetate oxidation of some 1-aroyl-4,5-dihydro-4,4-dimethyl-5-methylene-1H-pyrazoles

1-Aroyl-4,5-dihydro-5-methylene-1H-pyrazoles 1 are converted upon oxidation with m-chloroperbenzoic acid to the pyrazolones 2 . The same aroyl enamides 1 are also oxidized with LTA to form the acetoxy derivatives 7 and 8 . The reaction mechanisms are discussed.     

Solid-state photodimerization kinetics of alpha-trans-cinnamic acid to alpha-truxillic acid studied via solid-state NMR

The present work focuses on the topochemical photoconversion process in which alpha-trans-cinnamic acid becomes alpha-truxillic acid. This solid-state [2 + 2] cycloaddition reaction has previously been studied with X-ray diffraction, atomic force microscopy, and vibrational spectroscopy. However structural and kinetic details about the reaction are still debated. We present results from (13)C cross-polarization magic angle spinning solid-state NMR experiments that suggest that the Johnson, Mehl, Avrami, and Kolmogorov model of phase transformation kinetics can be applied to this system. The model elucidates parameters of the reaction, such as the nucleation rate, diffusion rate, and dimensionality of the reaction. From our data, it is concluded that this reaction follows one-dimensional growth with a decreasing nucleation rate.