Rongalite/iodine-mediated C(sp)-H bond oximation and thiomethylation reaction of methyl ketones using copper nitrate as the [NO] reagent: synthesis of thiohydroximic acids.

In this work, a highly efficient rongalite/iodine-mediated oxime formation reaction for the preparation of thiohydroximic acids from methyl ketones by employing copper nitrate as the [NO] reagent has been developed. Notably, copper nitrate participated as both a catalyst and the mild oximation reagent in the transformation. This reaction is highly efficient and facile, with a broad substrate scope, especially for fused ring skeleton substrates, heterocyclic skeleton substrates, and acetyl-substituted natural products.

Copper-Catalyzed Multicomponent Coupling Reaction of Primary Aromatic Amines, Rongalite, and Alkynes: Access to -Aryl Propargylamines.

In this work, a practical copper-catalyzed multicomponent coupling reaction of primary aromatic amines, rongalite, and alkynes for the direct synthesis of -aryl propargylamines has been developed. This method could overcome the substrate limitation in A coupling reactions of primary aromatic amines, formaldehyde, and alkynes. Mechanistic studies revealed that rongalite acts as not only the active C1 unit but also the accelerator to activate the -generated -arylmethanimines for the coupling reaction with alkynes.

A viologen-derived luminescent material exhibiting photochromism, photocontrolled luminescence and selective detection of CrO in aqueous solution.

Stable viologen-derived multifunctional smart materials exhibit widespread practical applications in many areas. In this study, a viologen-derived material with 4-fold interpenetrating diamondoid network, {[Cd(1,4-ndc)(cpbpy)]·2HO}, was successfully constructed based on asymmetrical N-(3-carboxyphenyl)-4,4'-bipyridinium (cpbpy) and 1,4-naphthalenedicarboxylic acid (1,4-Hndc). The compound shows reversible photochromic behavior under a xenon lamp, which are proved by UV-vis spectra and EPR characterizations.

Synthesis of primary propargylic alcohols from terminal alkynes using rongalite as the C1 unit.

Here, an efficient leaving group-activated methylene alcohol strategy for the preparation of primary propargyl alcohols from terminal alkynes by employing the bulk industrial product rongalite as the C1 unit has been described. The reaction avoids the low-temperature reaction conditions and inconvenient lithium reagents required for the classical method of preparing primary propargylic alcohols. Preliminary mechanistic studies showed that the reaction may not proceed formaldehyde intermediates, but through the direct nucleophilic attack of the terminal alkyne on the carbon atom of rongalite by activation through SO as a leaving group.

Metal-promoted intermolecular electron transfer in tetrathiafulvalene-thiacalix[4]arene conjugates and tetrachlorobenzoquinone.

In this work, two series of tetrathiafulvalene (TTF) and thiacalix[4]arene (TCA) conjugates (TTF-TCA) were designed by CuAAC click reactions. The results obtained from NMR and (1)H NMR NOE indicated that their conformations of thiacalix[4]arene framework may prefer to 1,3-alternate. The cyclic voltammograms of four TTF-TCA compounds containing electroactive TTF units were provided.

A new two-dimensional manganese(II) coordination polymer based on thiophene-3,4-dicarboxylic acid.

A novel manganese coordination polymer, poly[(μ5-thiophene-3,4-dicarboxylato)manganese(II)], [Mn(C6H2O4S)]n, was synthesized hydrothermally using 3,4-thiophenedicarboxylate (3,4-tdc(2-)) as the organic linker. The asymmetric unit of the complex contains an Mn(2+) cation and one half of a deprotonated 3,4-tdc(2-) anion, both residing on a twofold axis. Each Mn(2+) centre is six-coordinated by O atoms of bridging/chelating carboxylate groups from five 3,4-tdc(2-) anions, forming a slightly distorted octahedron.

Bis(1,3,4-thia-diazol-2-yl) disulfide.

The title compound, C(4)H(2)N(4)S(4), lies about a twofold rotation axis situated at the mid-point of the central S-S bond. Each of two thia-diazole rings is essentially planar, with an rms deviation for the unique thia-diazole ring plane of 0.0019 (7) Å.

4-Bromo-5-[(2-bromo-ethyl)-sulfanyl]-1,3-dithiole-2-thione.

The title compound, C(5)H(4)Br(2)S(4), consists of a statistically planar, 4-bromo-1,3-dithiole-2-thione unit [maximum deviation from the ring plane 0.001 (2) Å], with a bromo-ethyl-sulfanyl substituent in the 5-position. In the crystal structure, weak inter-molecular S⋯S [3.

3-(2-Thioxo-1,3-dithiol-4-ylsulfan-yl)-propane-nitrile.

The title compound, C(6)H(5)NS(4), consists of a planar 2-thioxo-1,3-dithiol-4-ylsulfanyl unit [maximum deviation from the ring plane = 0.0325 (2) Å], with a cyano-ethyl-sulfanyl substituent in the 4-position. In the crystal structure, weak inter-molecular C-H⋯S hydrogen bonds together with S⋯N inter-actions [3.

Bis(calixcrown)tetrathiafulvalene receptors.

A new class of electroactive receptors has been synthesized, built by covalent association of five subunits: two calixarene platforms for spatial organization, two polyether 3D cavities for cation binding, and one electroactive TTF unit to probe the complexation event. Sodium complexation induces rigidification of the molecular assembly, as shown by 1H NMR titration and single-crystal X-ray crystallographic studies on free receptor 14 and a corresponding complex with two bound sodium atoms per receptor (15-(NaPF6)2). The calixarene units in these receptors change from a pinched cone conformation in the free ligand to a symmetrical cone in the complex.

Bis-calix[4]arenes bridged by an electroactive tetrathiafulvalene unit.

Syntheses of the first bis-calixarenes systems bridged by a tetrathiafulvalene (TTF) framework 5a,b have been carried out in good yields through triethyl phosphite-mediated dechalcogenation-dimerizations of the corresponding 1,3-dithiole-2-(thi)ones 3 or 4. X-ray structures of the calix[4]arene-TTF-calix[4]arene assembly 5b and of the calix[4]arene-thione intermediate 3b are analyzed and confirm the cone conformations adopted by the calix[4]arene parts, as it is also observed by (1)H NMR analysis of these systems. The solid-state organization in 5b leads to alternate layers of calixarene and TTF units.

Spectroscopic behavior on the formation complex of three double-armed calix[4]arene derivatives with lanthanoid nitrates in acetonitrile.

The complexation spectroscopic behavior of three p-tert-butylcalix[4]arene Schiff bases i.e. 5,11,17,23-tetra-tert-butyl-25,27-bis[2-[N-(3-nitrobenzylidene)amino]ethoxy]-26,28-dihydroxycalix[4]arene (1), 5,11,17,23-tetra-tert-butyl-25,27-bis[2-[N-(2-hydroxybenzylidene)amino]ethoxy]-26,28-dihydroxycalix[4]arene (2), and 5,11,17,23-tetra-tert-butyl-25,27-bis[2-[N-(2-hydroxy-3-methoxybenzylidene)amino]ethoxy]-26,28-dihydroxycalix[4]arene (3) with lanthanoid nitrates (Tb3+ and Eu3+) has been investigated in anhydrous acetonitrile at 25 degrees C by using UV-vis and FT-IR as well as fluorescence spectra.