Synthesis of functionalized 3-arylpyridazines via Pd-catalyzed decarboxylative cross-coupling of pyridazine-3-carboxylic acids

An efficient and general protocol for the decarboxylative cross-coupling of pyridazine-3-carboxylic acids with aryl-bromides has been described. This method provides a new avenue for the synthesis of 3-arylpyridazines via decarboxylative cross-coupling strategy by employing the dual-catalyst system of Pd(PPh₃)₄/Cu₂O in the presence of Li₂CO₃ at 160 °C in DMA.     

DBSA-catalyzed hydrolysis of chain α-oxo ketene dithioacetals in water: Aqueous synthesis of β-ketothioesters

In this paper, we wish to report an environment friendly synthetic method for β-ketothioesters from a dodecylbenzenesulfonic acid (DBSA)-catalyzed hydrolysis reaction of chain α-oxo ketene dithioacetals in water. It was shown that the hydrolysis reaction of chain α-oxo ketene dithioacetals could efficiently occur in the presence of 7.5?mol% DBSA at 100?°C in water, affording the desired β-keto thioesters in excellent yields.     

Preparations and photophysical properties of thermally activated delayed fluorescence materials based on N-phenyl-phenothiazine-S,S-dioxide

Four compounds (TM-1～4) based on N-(4-trifluoromethylphenyl)phenothiazine-S,S-dioxide and N-[3,5-bis(trifluoromethyl)phenyl]phenothiazine-S,S-dioxide are synthesized by Buchwald-Hartwig cross coupling reaction. The effect of different substituents in acceptors on the electronic, photophysical and electrochemical properties are studied by UV–Vis, fluorescence spectroscopy, cyclic voltammetry curves and theoretical calculations. The energy gaps (ΔE_ST) between singlet excited states (S₁) and triplet excited states (T₁) of these compounds decrease by addition of one para-substituted CF₃ or two meta-substituted CF₃ on N-phenyl in order to enhance the electron-withdrawing capability of the acceptors. Small ΔE_ST of these compounds range from 0.09 eV to 0.18 eV. TM-2～4 exhibit thermally activated delayed fluorescence (TADF) characteristics with short delayed fluorescence lifetimes (τ_d) within 0.69-1.16 μs. TM-3 emits blue light with an emission wavelength of 475 nm.     

Transition-metal-free trifluoromethylthiolation and difluoromethylthiolation of thiols with trifluoromethanesulfonyl chloride and difluoromethanesulfonyl chloride

Triphenylphosphine-mediated metal-free trifluoromethylthiolation and difluoromethylthiolation of thiols by CF₃SO₂Cl and CHF₂SO₂Cl to synthesize trifluoromethyl disulfides and difluoromethyl disulfides, respectively, was achieved at room temperature. Iodine generated in situ from iodide facilitated this reaction via the formation of iodotriphenylphosphonium iodide which could serve as a reducing agent in this transformation. Readily available reagents and mild reaction conditions without transition-metals allow this protocol to be more practical than traditional methods.     

A zinc(II) benzenetricarboxylate metal organic framework with unusual adsorption properties,and its application to the preconcentration of pesticides

The authors describe a zinc(II) benzenetricarboxylate (Zn-BTC) based metal-organic framework (MOF) with chrysanthemum-like structure, and its application to the adsorption of pesticides from real water samples. The Zn-BTC MOF was characterized by XRD, TGA, SEM, nitrogen adsorption-desorption analysis and FT-IR spectroscopy. The MOF was used in dispersive solid-phase extraction of six aromatic pesticides from various wastewater samples prior to their quantification by HPLC. Extraction times, extraction temperature, amount of adsorbent, and oscillation rate were optimized. Under the optimal conditions, the method has relative standard deviations (RSDs) of 6.1–10.1%, and good linearity (correlation coefficients higher than 0.9974). The LODs and LOQs for seven pesticides are found to be 0.20–1.60 μg·L^?1 and 0.66–5.28 μg·L^?1, respectively. The RSDs of within batch extraction are 1.6–9.5% and 3.9–12%.

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Graphical abstract Schematic of a zinc-benzenetricarboxylate (Zn-BTC) based metal-organic framework (MOF) for use as an adsorbent of dispersive solid phase extraction (DSPE) of pesticides prior to their determination by HPLC.

     

Universal arcs in local tournaments

An arc $uv$ of a digraph $D$ is called universal if $uv$ and $w$ are in a common cycle for any vertex $w$ of $D$. In this paper we characterize local tournaments whose every arc is universal.     

Infinite Horizon Controlled Diffusions with Randomly Varying and State-Dependent Discount Cost Rates

This work focuses on optimal controls of diffusions in an infinite horizon. It has several distinct features in contrast to the existing literature. The discount factor is allowed to be randomly varying and state dependent. The existence and uniqueness of the viscosity solution to the associated Hamilton–Jacobi–Bellman equation are established. The verification theorem is also obtained. Because closed-form solutions are virtually impossible to obtain in most cases, we develop numerical methods. Using the Markov chain approximation methods, numerical schemes are constructed; viscosity solution methods are used to prove the convergence of the algorithm. In addition, examples are given for demonstration purpose.     

Maxima and minima of independent and non-identically distributed bivariate Gaussian triangular arrays

In this paper, joint limit distributions of maxima and minima on independent and non-identically distributed bivariate Gaussian triangular arrays is derived as the correlation coefficient of ith vector of given nth row is the function of i/n. Furthermore, second-order expansions of joint distributions of maxima and minima are established if the correlation function satisfies some regular conditions.     

Infrared and NMR Spectroscopic Fingerprints of the Asymmetric H7+O3 Complex in Solution

Infrared (IR) absorption in the 1000–3700 cm⁻¹ range and ¹H NMR spectroscopy reveal the existence of an asymmetric protonated water trimer, H₇⁺O_3, in acetonitrile. The core H₇⁺O₃ motif persists in larger protonated water clusters in acetonitrile up to at least 8 water molecules. Quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) simulations reveal irreversible proton transport promoted by propagating the asymmetric H₇⁺O₃ structure in solution. The QM/MM calculations allow for the successful simulation of the measured IR absorption spectra of H₇⁺O₃ in the OH stretch region, which reaffirms the assignment of the H₇⁺O₃ spectra to a hybrid-complex structure: a protonated water dimer strongly hydrogen-bonded to a third water molecule with the proton exchanging between the two possible shared-proton Zundel-like centers. The H₇⁺O₃ structure lends itself to promoting irreversible proton transport in presence of even one additional water molecule. We demonstrate how continuously evolving H₇⁺O₃ structures may support proton transport within larger water solvates.