Effect of pressure on the low-temperature reaction of ethylene with N2O4

Calorimetric monitoring of the autoclave reaction N₂O₄ + C₂H₄ at –85 to +10 °C under argon pressure 10–30 bar revealed that the exothermic chemical reaction started at temperatures above –52 °C at 10 bar, whereas an intensive exothermic reaction started at –85 °C and pressure of 30 bar. IR study showed that oligo/polynitroethylene was formed at 30 bar, while carbonyl and hydroxy compound as well as nitrate R–ONO₂ formation occurred upon processing at 10 bar.     

Highly diastereoselective multicomponent synthesis of polysubstituted 2-hydroxy-2-trifluoromethylpiperidineswith four and five stereogenic centers

The Michael–Mannich cascade cyclization of cyano olefins, ethyl 4,4,4-trifluoro-3-oxobutanoate, aromatic aldehydes and ammonium acetate provides convenient stereoselective formation of ethyl 5,5-dicyano-4,6-diaryl-2-hydroxy-2-(trifluoromethyl)piperidine-3-carboxylates with fourstereogenic centers and dialkyl 4,6-diaryl-5-cyano-2-hydroxy-2-(trifluoromethyl)piperidine-3,5-dicarboxylates with five stereogenic centers. Ammonium acetate plays dual role, acting as a base and as a nitrogen source.     

A branch-and-bound method for the minimum k−enclosing ball problem

The minimum k-enclosing ball problem seeks the ball with smallest radius that contains at least k of m given points. This problem is NP-hard. We present a branch-and-bound algorithm on the tree of the subsets of k points to solve this problem. Our method is able to solve the problem exactly in a short amount of time for small and medium sized datasets.     

Pd0‐Catalyzed Intramolecular α‐Arylation of Sulfones: Domino Reactions in the Synthesis of Functionalized Tetrahydroisoquinolines

A new strategy for the synthesis of tetrahydroisoquinolines based on the Pd⁰‐catalyzed intramolecular α‐arylation of sulfones is reported. The combination of this Pd‐catalyzed reaction with intermolecular Michael and aza‐Michael reactions allows the development of two‐ and three‐step domino processes to synthesize diversely functionalized scaffolds from readily available starting materials.     

Chain transfer to solvent in BN 2-vinylnaphthalene radical polymerization

The synthesis of vinyl alcohol copolymers is limited due to the poor radical reactivity of vinyl acetate (VAc), the traditional precursor to polyvinyl alcohol (PVA). Main group monomers such as BN 2-vinylnaphthalene (BN2VN) have attracted attention as alternatives to VAc to form side chain hydroxyls via oxidation, but outstanding questions of molecular weight control remain. Herein we report systematic investigation of solvent, temperature, and initiator concentration as factors influencing BN2VN degree of polymerization. We find increased chain transfer to toluene, hypothesized to arise from differences in radical stabilization and reactivity by aromatic and BN aromatic rings. As a result of these combined efforts, high molecular weight (M_w ~ 10⁵ g mol⁻¹) BN2VN homopolymers and BN2VN-styrene copolymers were obtained.     

Selective Catalytic Isomerization of β-Pinene Oxide to Perillyl Alcohol Enhanced by Protic Tetraimidazolium Nitrate

A series of tetraimidazolium salts with different anions was prepared and applied in the isomerization of β-pinene oxide. After examining the activity of different catalysts, a remarkable enhancement of the selectivity of perillyl alcohol (47 %) was obtained over [PEimi][HNO₃]₄ under mild reaction conditions and using DMSO as the solvent. Furthermore, noncovalent interactions between solvent molecules and the catalyst were found by FT-IR spectroscopy and confirmed by computational chemistry. The homogeneous catalyst showed excellent stability and was reused up to six times without significant loss.     

Bimetallic Covalent Organic Frameworks for Constructing Multifunctional Electrocatalyst

Covalent organic frameworks (COFs) are a new class of crystalline porous polymers comprised mainly of carbon atoms, and are versatile for the integration of heteroatoms such as B, O, and N into the skeletons. The designable structure and abundant composition render COFs useful as precursors for heteroatom-doped porous carbons for energy storage and conversion. Herein, we describe a multifunctional electrochemical catalyst obtained through pyrolysis of a bimetallic COF. The catalyst possesses hierarchical pores and abundant iron and cobalt nanoparticles embedded with standing carbon layers. By integrating these features, the catalyst exhibits excellent electrochemical catalytic activity in the oxygen reduction reaction (ORR), with a 50 mV positive half-wave potential, a higher limited diffusion current density, and a much smaller Tafel slope than a Pt-C catalyst. Moreover, the catalyst displays superior electrochemical performance toward the hydrogen evolution reaction (HER), with overpotentials of −0.26 V and −0.33 V in acidic and alkaline aqueous solution, respectively, at a current density of 10 mA cm⁻². The overpotential in the catalysis of the oxygen evolution reaction (OER) was 1.59 V at the same current density.     

Chromatography-Free Multicomponent Synthesis of Thioureas Enabled by Aqueous Solution of Elemental Sulfur

The development of a new three-component chromatography-free reaction of isocyanides, amines and elemental sulfur allowed us the straightforward synthesis of thioureas in water. Considering a large pool of organic and inorganic bases, we first optimized the preparation of aqueous polysulfide solution from elemental sulfur. Using polysulfide solution, we were able to omit the otherwise mandatory chromatography, and to isolate the crystalline products directly from the reaction mixture by a simple filtration, retaining the sulfur in the solution phase. A wide range of thioureas synthesized in this way confirmed the reasonable substrate and functional group tolerance of our protocol.     

Thermally induced solid-state transformation of cimetidine. A multi-spectroscopic/chemometrics determination of the kinetics of the process and structural elucidation of one of the products as a stable N3-enamino tautomer

Exposure of cimetidine (CIM) to dry heat (160–180 °C) afforded, upon cooling, a glassy solid containing new and hitherto unknown products. The kinetics of this process was studied by a second order chemometrics-assisted multi-spectroscopic approach. Proton and carbon-13 nuclear magnetic resonance (NMR), as well as ultraviolet and infrared spectroscopic data were jointly used, whereas multivariate curve resolution with alternating least squares (MCR-ALS) was employed as the chemometrics method to extract process information. It was established that drug degradation follows a first order kinetics.