Structure,Chemical Bonding,and Properties of Sc2Ni2In

Sc₂Ni₂In was prepared by a reaction of the elemental components in an are furnace and subsequent annealing at 1070 K. Sc₂Ni₂In is a Pauli paramagnet and a poor metallic conductor with a specific resistivity of 224 mΩcm at room temperature. Its crystal structure was refined from X-ray powder data: P4/mbm, a = 716.79(1) pm, c = 333.154(8) pm, Z = 2, R_wp = 0.040, and R_B(I) = 0.026. Sc₂Ni₂In crystallizes with a ternary ordered version of the U₃Si₂-type structure. The nickel and indium atoms occupy [NiSc₆] trigonal prisms and [InSc₈] square prisms, respectively. These structural fragments are derived from the AlB₂ and CsCl-type structures. Semi-empirical band structure calculations reveal Sc₂Ni₂In to be a nickelide, and the strongest bonding interactions are found for the Sc? Ni contacts, followed by Sc? In and Ni? In. A rigidband model suggests the existence of the isotypic phase Sc₂Ni₂Sb.     

不分流进样/Cu~(2 )预柱-毛细柱GC/FTIR鉴定环境水中痕量有机污染物

本文介绍一种新的分离分析技术,即不分流进样/Cu~(2 )预柱-毛细柱GC/FTIR,它能彻底消除溶剂影响,实现大容量进样,系统灵敏度比现行GC/FTIR系统高约1～2个数量级。这种技术已成功地用于长江水中痕量有机污染物的分析。     

A one-step conversion of isoquinolinium salts into naphthalene derivatives1

Berberine chloride (1) upon treatment with NaOAc-Ac₂O yields naphthalene derivatives 4 and 5 In like fashion, 8 gives naphthalene 10; isoquinoline methiodide leads to β-naphthyl acetate; and 12 provides 14. The reaction has been extended to the 3-carbonyl pyridinium series where 3-acetylpyridine methiodide and 3-pyridinecarboxaldehyde methiodide furnish lactones 16 and 17, respectively. All these transformations proceed by initial nucleophilic attack of the acetic anhydride anion on the immonium carbon atom.     

“线上线下-虚实结合”在有机化学实验教学中的应用探索——以正溴丁烷的制备实验为例

In response to the impact of the Covid-19 epidemic on organic chemistry laboratory teaching, this article analyzes and discusses the current limitation of traditional organic chemistry laboratory teaching. Taking the "preparation of n-bromobutane" as an example, a new "online-offline and virtual-actual combination" teaching mode with the combination of "Tencent Meeting, MLabs, laboratory and WeChat group" is introduced. The practice of the new mode of teaching includes the following steps: pre-class online guiding by teacher, student preview and practice based on the virtual simulation platform, students and teacher discussion and operation in laboratory, and post-classcomprehensive assessment and Q&A", and good teaching effects have been received. It is significant in cultivating and improving the independent innovation and practical ability, and provides reference for the organic chemistry laboratory teaching reform and also lays a foundation for the construction of "outstanding course" of organic chemistry.     

Micellar effect on the electron transfer reaction of chromium(V) ion with organic sulfides

The rate of electron transfer from organic sulfides to [Cr^V(ehba)₂]⁻ (ehba-2-ethyl-2-hydroxy butyric acid) decreases with a decrease in the polarity of the medium. The anionic surfactant, SDS and the cationic surfactant, CTAB have different effects on the kinetics of this reaction. The micellar inhibition observed in the presence of SDS is probably due to the decrease in the polarity and the electrostatic repulsion faced by the anionic oxidant from the anionic micelle and the partition of the hydrophobic substrate between the aqueous and micellar phases. The micellar catalysis in the presence of CTAB is attributed to the increase in the concentration of both reactants in the micellar phase. This micellar catalysis is observed to offset the retarding effects of the less polar micellar medium and the unfavorable charge-charge interaction between the + charge developed on S center in the transition state and the cationic micelle. This catalysis is contrary to the enormous micellar inhibition observed with IO₄⁻, HSO₅⁻ and HCO₄⁻ oxidation of organic sulfides.     

Enantiomer separations with chromatographic supports based on β-cyclodextrin polymers immobilized on porous silica. Role of the polymer structure in separating ability

Summary Two -cyclodextrin (-CD)-containing polymers have been prepared either by condensation of -CD molecules with a bifunctional reagent or by grafting a -CD derivative on to a linear polymer (polyvinylimidazole). HPLC stationary phases were obtained by adsorption of the -CD polymers on to silica. The ability of these chromatographic supports to resolve racemic mixtures of organic compounds such as amino acid derivatives, phenylhydantoins, barbiturates, and hydroxycoumarin derivatives has been investigated. Results were found to depend on the chemical structure of the -CD polymers     

绿色合成氧化剂高铁酸盐

高铁酸盐是绿色、无污染、高选择性和高活性的强氧化剂，其氧化性能比KMn04、O3和Cl还强，可以氧化醇类、含氮化合物、甚至烃类等有机化合物，高铁酸盐在有机物氧化合成中的应用具有很好的发展前景。本文介绍了有关高铁酸盐的制备方法、性质及有机物氧化合成方面的研究进展。     

Determination of the Enthalpies of Vaporization of Cyclic Organic Peroxides by Correlation of Changes in Gas Chromatographic Retention Times

Liquid and solid cyclic peroxides derived from aliphatic ketones are explosive materials so their enthalpies of vaporization and other thermodynamic or condensed-phase properties cannot be measured directly. In this work the enthalpies of vaporization of peroxides at 298.15 K were estimated simply from gas chromatographic retention times measured at different temperatures. The technique correlates changes in the retention times of compounds whose enthalpies of vaporization are known (called the reference series), with those of the compounds of interest. If t _R′ is the adjusted retention time (retention time of each compound minus the retention time of unretained diethyl ether, used as solvent) a plot of ln t _R′ against 1/T for each compound (reference compounds and cyclic peroxides) results in a straight line (r ² > 0.99 for all compounds). The enthalpy of transfer from solution to the vapor state (Δ_sol^g H _m) can be obtained by multiplying the slope by the gas constant (R). A second plot correlates the enthalpies of transfer from solution to the vapor state (Δ_sol^g H _m), as measured by gas–liquid chromatography (GLC), with enthalpies of vaporization of reference materials (Δ_vap H _m at 298.15 K) available in the literature. C₉–C₁₅ fatty acid methyl esters and hydrocarbons were used as reference compounds. The enthalpies of vaporization of the cyclic organic peroxides were calculated from the equation of the line obtained in this second correlation, the slope of which was Δ_vap H _m (at 298.15 K)/Δ^g _sol H _m. The experiments were performed under isothermal conditions with a DB-5 capillary column, flame-ionization detection (FID), and nitrogen as carrier gas. The column temperature was varied over a range of at least 30–70 K between 403 and 473 K, with chromatograms being acquired at 10 K intervals. Enthalpies of vaporization of cyclic organic peroxides are not available in the literature, and the values given in this paper, obtained by gas chromatography, are the first to be reported.     

On the Importance of H-Bonding Interactions in Organic Ammonium Tetrathiotungstates

Summary. Four new organic ammonium tetrathiotungstates (N–Me–enH₂)[WS₄] (1), (N,N′-dm-1,3-pnH₂)[WS₄] (2), (1,4-bnH₂)[WS₄] (3), and (mipaH)₂[WS₄] (4), (N–Me–enH₂ = N-methylethylenediammonium, N,N′-dm-1,3-pnH₂ = N,N′-dimethyl-1,3-propanediammonium, 1,4-bnH₂ = 1,4-butanediammonium, and mipaH = monoisopropylammonium) were synthesized by the base promoted cation exchange reaction and characterized by elemental analysis, infrared, Raman, UV-Vis and ¹H NMR spectroscopy as well as single crystal X-ray crystallography. The structures of 1–4 consist of [WS₄]²⁻ tetrahedra which are linked to the organic ammonium cations via N–H⋯S hydrogen bonding. The strength and number of the S⋯H interactions affect the W–S bond lengths as evidenced by distinct short and long W–S bonds. The IR spectra exhibit splitting of the W–S vibrations, which can be attributed to the distortion of the [WS₄]²⁻ tetrahedron. From a comparative study of several known tetrathiotungstates it is observed that a difference of more than 0.033 ? between the longest and shortest W–S bonds in a tetrathiotungstate will result in the splitting of the asymmetric stretching vibration of the W–S bond.     

Photochemistry of β, γ-unsaturated ketones-V: The direct irradiation of some γ-phenyl β, γ-enones

The photochemistry of some members of the two series of γ-phenyl substituted acyclic β, γ-unsaturated ketones 1 and 2 upon direct irradiation with γ 310nm has been investigated, viz 1c–1h and 2b+2c.The alkyl substituted (E)-5-phenyl-4-penten-2-ones 1c–1h yield the corresponding 1,3-acyl shift products and (Z)-isomers, and 1g and 1h in addition two decarbonylated products. 2b only yields the (Z)-isomer and some benzaldehyde, but 2c yields the 1,3-acyl shift product, the ODPM product, three hydrocarbons formed by disproportionation of the allyl radical, and some benzaldehyde. The β-phenyl β, γ-UK 3a proved to be photostable. The 1,3-acyl shift products of 1c–1h result mainly from the singlet excited state in a cage radical process. The exclusive formation of the (E)-configuration of the 1,3-acyl shift product is explained in terms of conformational preference of the intermediate allyl radical. It is proposed that the formation of the (Z)-isomer proceeds from ¹T(π -π^*) which is populated according to

. Evidence is presented which supports the proposed mechanism.The β,γ-UK 2b containing a benzoyl moiety leads to a higher degree of (E)-(Z) isomerization than the corresponding 1d which has an acetyl moiety.The triplet energies of (E)- and (Z)-1h are 56 and ca 70 kcal/mol respectively.