Two isomeric butadiene–N‐(acetoxy­phenyl)maleimide Diels–Alder adducts: supramolecular structure directed by C—H⋯X (X = O and π) hydrogen bonds and perpendicular dipole carbonyl–carbonyl inter­actions

The mol­ecular and supramolecular structures of 2‐(1,3‐dioxo‐2,3,3a,4,7,7a‐hexa­hydro‐1H‐isoindol‐2‐yl)phenyl acetate, C₁₆‐H₁₅NO₄, (I), and its para isomer, 4‐(1,3‐dioxo‐2,3,3a,4,7,7a‐hexa­hydro‐1H‐isoindol‐2‐yl)phenyl acetate, (II), are reported. The torsion angle between the succinimide and benzene rings depends on the position of the acet­oxy substitution [89.7 (1) and 61.9 (1)° for (I) and (II), respectively]. The twist of the acet­oxy group relative to the mean plane of the benzene ring is almost independent of the acet­oxy position [66.0 (1) and 70.0 (1)°]. Packing inter­actions for both compounds include soft C—H⋯X (X = O and Ph) inter­actions, forming chains of centrosymmetric dimers and inter­linked chains for (I) and (II), respectively. In addition, three perpendicular dipole C=O⋯C=O inter­actions contribute to the supramolecular structure of (II).     

Poly[tetra‐μ‐aqua‐hexa­aquadi‐μ3‐malon­ato‐dinitratodibarium(II)nickel(II)]

The title complex, [Ba₂Ni(C₃H₂O₄)₂(NO₃)₂(H₂O)₁₀]_n, has a two‐dimensional layer structure. The Ni atom lies on a crystallographic centre of symmetry in an octa­hedral NiO₆ environment, and is coordinated by four malonate O atoms in a planar arrangement and by two water mol­ecules in axial positions. The coordination of the unique Ba atom involves two nitrate O atoms, five water mol­ecules and three malonate O atoms.     

A unique tautomer of 1‐n‐hexyl‐3‐phenyl‐1H‐pyrazol‐5‐ol

In the title compound, C₁₅H₂₀N₂O, the bond distances and angles are consistent with the presence of the hydroxy tautomer. This tautomer was unambiguously determined by the clear presence of a H atom bonded to oxygen, as well as the total absence of any residual electron density around the N atom in the heterocycle, thus precluding any possibility of desmotropism.     

聚醚桥连二异羟肟酸单核和双核过渡金属配合物催化PNPP水解

Two polyether bridged dihydroxamic acids and their mono-and binuclear manganese(Ⅱ), zinc(Ⅱ) complexes have been synthesized and employed as models to mimic hydrolase in catalytic hydrolysis of p-nitrophenyl picolinate (PNPP). The reaction kinetics and the mechanism of hydrolysis of PNPP have been investigated. The kinetic mathematical model for PNPP cleaved by the complexes has been proposed. The effects of the different central metal ion, mono-and binuclear metal, the pseudo-macrocyclic polyether constructed by polyethoxy group of the complexes, and reactive temperature on the rate for catalytic hydrolysis of PNPP have been examined. The results showed that the transition metal dthydroxamates exhibited high catalytic activity to the hydrolysis of PNPP, the catalytic activity of binuclear complexes was higher than that of mononuclear ones, and the pseudo-macrocyclic polyether might synergetically activate H20 coordinated to metal ion with central metal ion together and promote the catalytic hydrolysis of PNPP.     

新型除草剂及其杂质的LC-MS和GC-MS分析

High performance liquid chromatography (HPLC) and electrospray ionization mass spectrometry (ESI-MS) have been utilized to analyze the synthesized 2-(2-arylaminomethylphenoxy)pyrimidine derivatives, which are a new kind of environmentally benign herbicides and have passed the temporary pesticide registration. The identification of main product and impurities has been achieved according to the UV and mass spectra. Moreover, one impurity, introduced by the raw material in the last step of the synthetic route, was identified by GC-MS analysis. It can be concluded that the combination of chromatography and mass spectrometry, including LC-MS and GC-MS, provided a vital tool of the pesticide science.     

Isomeric [RuCl2(dmso)2(indazole)2] complexes: ruthenium(II)-mediated coupling reaction of acetonitrile with 1H-indazole

Reaction of the antitumor complex trans-[Ru(III)Cl4(Hind)2]- (Hind = indazole) with an excess of dimethyl sulfoxide (dmso) in acetone afforded the complex trans,trans,trans-[Ru(II)Cl2(dmso)2(Hind)2] (1). Two other isomeric compounds trans,cis,cis-[Ru(II)Cl2(dmso)2(Hind)2] (2) and cis,cis,cis-[Ru(II)Cl2(dmso)2(Hind)2] (3) have been obtained on refluxing cis-[Ru(II)Cl(2)(dmso)(4)] with 2 equiv. of indazole in ethanol and methanol, respectively. Isomers 1 and 2 react with acetonitrile yielding the complexes trans-[Ru(II)Cl2(dmso)(Hind){HN=C(Me)ind}].CH3CN (4.CH3CN) and trans,cis-[Ru(II)Cl2(dmso)2{HN=C(Me)ind}].H2O (5.H2O), respectively, containing a cyclic amidine ligand resulting from insertion of the acetonitrile C triple bond N group in the N1-H bond of the N2-coordinated indazole ligand in the nomenclature used for 1H-indazole. These are the first examples of the metal-assisted iminoacylation of indazole. The products isolated have been characterized by elemental analysis, IR spectroscopy, UV-vis spectroscopy, electrospray mass-spectrometry, thermogravimetry, differential scanning calorimetry, 1H NMR spectroscopy, and solid-state 13C CP MAS NMR spectroscopy. The isomeric structures of 1-3 and the presence of a chelating amidine ligand in 4 and 5 have been confirmed by X-ray crystallography. The electrochemical behavior of 1-5 and the formation of 5 have been studied by cyclic voltammetry.     

Synthesis of Some Novel 3,6‐Bis(1,2,3‐triazolyl)‐s‐triazolo[3,4‐b]‐1,3,4‐thiadiazole Derivatives

The cyclization of 1‐amino‐2‐mercapto‐5‐[1‐(4‐ethoxyphenyl)‐5‐methyl‐1,2,3‐triazol‐4‐yl]‐1,3,4‐triazole which was synthesized from p‐ethoxyaniline with various triazole acid in absolute phosphorus oxychloride yields 3,6‐bis(1,2,3‐triazolyl)‐s‐triazolo[3,4‐b]‐1,3,4‐thiadiazole derivatives 9a?j , and their structures are established by MS, IR, CHN and ¹H NMR spectral data.     

Hydrogen bonding and π–π stacking in 6‐hydroxy­biochanin A monohydrate

In the lattice of the title compound (systematic name: 5,6,7‐trihydroxy‐4′‐meth­oxy­isoflavone monohydrate), C₁₆H₁₂O₆·H₂O, the isoflavone mol­ecules are linked into chains through R₄³(17) motifs composed via O—H⋯O and C—H⋯O hydrogen bonds. Centrosymmetric R₄²(14) motifs assemble the chains into sheets. Hydrogen‐bonding and aromatic π–π stacking inter­actions lead to the formation of a three‐dimensional network structure.     

Tris（2,2＇-bipyridyl） Ruthenium（Ⅱ） Doped Silica Film Modified Indium Tin Oxide Electrode and Its Electrochemiluminescent Properties

An approach was reported to synthesize silica hybridized ruthenium bipyridyl complex through amidation reaction by covalent attachment of bis（bipyridyl）-4,4＇-dicarboxy-2,2＇-bipyridyl-ruthenium to （3-aminopropyl）-triethoxysilane. The hybrid complex then was gelatinized through acid catalytic hydrolysis method and a sol-gel modified indium tin oxide electrode was prepared via spin coating technique. As prepared indium tin oxide electrode possesses good stability therein with excellent electrochemiluminescence behavior.     

Manipulating the Through‐Space Spin–Spin Interaction of Organic Radicals in the Confined Cavity of a Self‐Assembled Cage

We show a new approach to manipulating the through‐space spin–spin interaction by utilizing the confined cavity of a self‐assembled M₆L₄ coordination cage. The coordination cage readily encapsulates stable organic radicals in solution, which brings the spin centers of the radicals closer to each other. In sharp contrast to the fact that the radical in solution in the absence of the cage is in a doublet state, in the presence of the cage through‐space spin–spin interaction is induced through cage‐encapsulation effects in solution as well as in the solid state, resulting in the triplet state of the complex. These results were confirmed by ESR spectroscopy and X‐ray crystallography. The quantity of triplet species generated by encapsulation in the cage increases with increasing affinity of the radicals to the cage. We estimated the affinity between several types of guests and the cage in solution by cyclic voltammetry. We also demonstrate that the through‐space interaction of organic radicals within the self‐assembled coordination cage can be controlled by external stimuli such as heat or pH.