聚乙烯基吡啶高氯酸盐作为高效固体酸催化剂在无溶剂条件下催化醛化学选择性制备二乙酸盐(英文)

Poly(4-vinylpyridinium) perchlorate has been used as a supported,recyclable,environmentally-benign catalyst for the formation of acylals from aliphatic and aromatic aldehydes in good to excellent yields under solvent-free conditions.Notably,the reaction conditions were tolerant of ketones.This methodology offers several distinct advantages,including its operational simplicity and high product yield,as well as being green in terms of avoiding the use of toxic catalysts and solvents.Furthermore,the catalyst can be recovered and reused several times without any loss in its activity.     

Enhanced Thermal Decomposition Properties and Catalytic Mechanism of Ammonium Perchlorate over CuO/MoS2 Composite

In this report, CuO/MoS₂ composites were successfully prepared by the hydrothermal method where nano‐sized CuO was uniformly distributed on the surface of hierarchical MoS₂ substrates (CuO/MoS₂ composites). Their physicochemical properties and catalytic performance in ammonium perchlorate (AP) decomposition were investigated and characterized by XRD, SEM, TEM, BET, XPS, TG/DSC and combustion measurement. The results showed that it could decrease AP decomposition temperature at high decomposition stage from 416.5 °C to 323.5 °C and increase the heat release from 378 J/g (pure AP) to 1340 J/g (AP with catalysts), which was better than pure CuO nanoparticles (345.5 °C and 1046 J/g). Meanwhile, it showed excellent performance in combustion reaction either in N₂ or air atmosphere. The results obtained by photocurrent spectra, photoluminescence spectra and time‐resolved fluorescence emission spectra indicated that loading CuO mediated the generation rate and combination rate of electrons and holes, thus tuning the catalytic performance on AP decomposition. This study proved that employing the supports that can synergistically interact with CuO is an efficient strategy to enhance the catalytic performance of CuO.     

An Efficient Deoxygenation of Heteroaromatic N-Oxides Using Zinc Dust/Ammonium Formate Reagent System

Abstract

Heteroaromatic N-oxides were readily and selectively deoxygenated to the corresponding bases with zinc/ammonium formate reagent system.     

Olefin Synthesis via,the Li-Derivative of N,N,N′,N′-Tetramethyldimides of Arylmethanephosphonic Acids

Abstract

The high erythro-stereoselective reaction of Li-tetramethyldiamides of arylmethanephosphonic acids with carbonyl compounds is used for synthesis of (Z)-alkenes by thermolysis of the erythro-adducts as well as in acidic media.     

Object and Mathematical Simulation of Ammonium Hexafluorosilicate Sublimation

An integration of different modelling methods including object and mathematical simulation are suggested for sublimation processes of inorganic fluorides to optimally simulate the real technological conditions. The paper presents the results of testing this methodology on ammonium hexafluorosilicate sublimation.     

Stark Hole-Burning Spectroscopy of Cresylviolet Perchlorate in Amorphous Hosts

Stark hole-burning spectroscopy is used to investigate the effective dipole moment change of cresylviolet perchlorate (CVP) in various glass and polymer hosts such as ethanol:methanol (EM), polyvinyl alcohol (PVA), poly (2-hydroxyethyl) methacrylate (PHEMA), polyvinylbutyral (PVB), and formamide. The strong correlation between effective dipole moment change of the guest molecule and the holeburning efficiencies of the host matrices illustrates the sensitivity of the dipole moment change as a direct measure of guest-host interactions. Hole-burning is found to be more efficient as the dipole induced reaction field increases. This relationship is discussed in terms of the unusual hole-burning mechanism suggested for this molecule. The effective dipole moment change of cresylviolet perchlorate ranges from 0.14 to 0.59 Debye.     

Synthesis and Application of N-Tosyl Piperidinyl-Containing α-Aminophosphonates

Abstract

A series of novel (4′-tosyl) piperidin-4-yl containing α-aminophosphonates were synthesized by a one-pot reaction, efficiently catalyzed by magnesium perchlorate, under solvent-free conditions from 1-tosylpiperidin-4-one, substituted aromatic amines, and diethyl phosphite (DEP). The synthesized compounds were characterized by IR, ¹H NMR, ¹³C NMR, ³¹P NMR, and HRMS spectroscopy. A single-crystal X-ray structure of diethyl 4-(2-chlorophenyl) amino-1-(4’-methylbezenesulfonyl) piperidin-4-yl-phosphonate (2a) was obtained, and some of the title compounds displayed insecticidal activities against Plutella xylostella.

Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures and tables.     

Facile Conversion of Epoxides to Thiiranes with Ammonium Thiocyanate Catalyzed with Oxalic Acid

Epoxids are efficiently converted to the corresponding thiiranes by ammonium thiocyanate (NH 4 SCN) in the presence of catalytic amounts of oxalic acid with excellent isolated yields under mild and nonaqueous reaction conditions. This conversion performed under both conventional heating and microwave conditions. Distinct rate enhancement is observed under microwave irradiation.     

Ammonium Ion Complexes of Tetraethyl Resorcarene: An Ab Initio Study

The complexation of various ammonium ions with a resorcarene host was evaluated by ab initio calculations. The approximations of the binding locations and the interaction energies for each guest are reported. The supramolecular complex formation also affects the conformation of the resorcarene host.     

Endo-cavity Complexes between Calix[6]arene Dianions and Aliphatic Ammonium Cations: Structure of a Hexylammonium Complex by X-ray Crystallography

The interactions of calix[6]arene and p-tert-butylcalix[6]arene with aliphatic amines in acetonitrile solution were studied by spectrophotometric titrations in the UV region and ¹H NMR spectrometry. Calix[6]arenes can undergo two deprotonations by aliphatic amines and the extent of the second proton transfer is mainly governed by the size of the α-substituent of the amine. ¹H NMR spectra show that the macrocycle adopts a 1,2,3-alternate conformation and that the α-hydrogens of the ammonium ions are shielded by the π-clouds of the aromatic rings. The X-ray crystal structure of the dihexylammonium complex of the p-tert-butylcalix[6]arene dianion, reported here, confirms the 1,2,3-alternate conformation and shows one of the two ammonium moieties encapsulated in the inner cavity of the macrocycle.