Direct N- and C-alkenylation of nitrogen-containing heterocycles with magnesium alkylidene carbenoids

Treatment of magnesium alkylidene carbenoids, which were generated from 1-chlorovinyl p-tolyl sulfoxides with isopropylmagnesium chloride at −78 °C in toluene, with N-lithio nitrogen-containing heterocycles gave N-alkenylated products in moderate to good yields. Also, the reaction of C-lithio indoles, which were generated from N-protected indoles, with magnesium alkylidene carbenoids gave C-2 or C-3 alkenylated products, corresponding to the protective group. The intermediate of these reactions were found to be the alkenyl anion, which could be trapped with electrophiles to give the heterocycles having fully substituted alkenes.     

NMR study of the stoichiometry,stability and exchange kinetics of complexation reaction between Pb2+ ion and 18-crown-6 in binary acetonitrile-water mixtures

Proton NMR was used to study the complexation reaction between lead ion and 18-crown-6 in a number of binary acetonitrile-water mixtures. Formation constant for the resulting 11 complexes in different solvent mixtures was determined by computer fitting of the chemical shift-mole ratio data. There is an inverse relationship between the complex stability and amount of water in the mixed solvent. The dissociative kinetics of the complex was studied by proton line-shape analysis. The Arrhenius plots showed a distinct isokinetic temperature at about 25°C at which the decomplexation rate is more or less independent of the solvent composition. the complexation rate and the activation parameters E _a , H and S, for the exchange have been determined and found to be strongly solvent dependent. There is actually a linear relationship between the mole fraction of acetonitrile in the mixed solvent and logarithm of the stability constant as well as activation parameters.     

Effect of aryl ligands on the chemical hardness of arylmercury cations

¹⁹F NMR spectroscopy was used to study the exchange reactions involving 4-fluorothiophenoxides, 4-nitrophenoxides, chlorides, and acetates of arylmercury and triphenylphosphinegold. The analysis of the data on equilibrium constants allows one to obtain information on the comparative chemical hardness of ArHg⁺ and Ph₃PAu⁺ cations. The increase in the electron-donating ability of aryl ligands enhances the chemical hardness of ArHg⁺ cations, their influence being best described by ⁰ constants of substituted phenyl groups.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1255–1260, May, 1996.     

Aryl-bis(triorganylphosphine)nickel phenoxides

Compounds of general formulatrans-ArNi(PR₃)₂OAr' (R = Et, cyclohexyl; Ar = 2-MeC₆H₄, 2-FC₆H₄; Ar' = 4-FC₆H₄, 4-NO₂C₆H₄) were synthesized by the reaction of Ar'OK with cationic nickel complexes generated by treatment of ArNi(PR₃)₂Cl with TlBF₄. Syntheses of 4-fluorophenoxide complexes, ArNi(PR₃)₂OC₆H₄F-4, additionally give some quantities oftrans-[ArNi(PR₃)₂OC₆H₄F-4][HOC₆H₄F-4] adducts. Exchange reactions MeC₆H₄Ni(PEt₃)₂OC₆H₄F-4 + XC₆H₄OH 2-MeC₆H₄Ni(PEt₃)₂OC₆H₄X + 4-FC₆H₄OH were studied in THF. The equilibrium is shifted to the right as the acidity of ArOH increases. A linear relationship between lgK _eq and pK _a of XC₆H₄OH in DMSO was found. A conclusion concerning the strong polarization of the Ni-O bond was made on the basis of an analysis of the chemical shifts of fluorine atoms in 2-MeC₆H₄Ni(PEt₃)₂OC₆H₄F-4.Translated fromIvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2266–2271, November, 1995.     

Magnetic exchange interactions in tetrabromocuprate compounds

Magnetic and structural data for 28 compounds containing the tetrabromocuprate ion are presented. The parameters which affect the strength and sign of the magnetic superexchange interaction via non-bonding contacts between bromide ions are described and a system for describing the topology of the interaction between tetrahedra is proposed. Analysis of the data suggests that the primary factors affecting the magnetic exchange are the Br?Br distance, the Cu-Br?Br angle and the Cu-Br?Br-Cu dihedral angle.     

离子交换法纯化重组类人胶原蛋白II的研究

用阳离子交换树脂CM-52分离纯化类人胶原蛋白II(HumanCollagen-likeBioproteinII,HCBII)。通过实验,分别确定了静态吸附和柱层析吸附的操作条件,即静态吸附:在pH4.0、NaCl0.15mol/L、进料浓度7g/L,处理量17.26ml/g树脂的条件下进行吸附,吸附时间为60min;柱层析:在pH4.0、NaCl0.15mol/L、进料浓度5g/L、流速5ml/min的条件下进行吸附。然后上柱,在pH4.0、NaCl0.30mol/L下进行脱附。实验表明,采用静态吸附的方式吸附HCBII,然后上柱洗脱,HCBII的吸附量可达到48.6mg/g树脂,回收率83.8%,操作时间短,分辨率高,最终纯化的HCBII达电泳纯,分子量为97kD。     

Theoretical Study on the Mass Transfer of Metal Ions in Ion Exchange Process

The kinetics of ion exchange between Ca2 , Mg2 , Co(Ⅱ), Cu(Ⅱ),Ni(Ⅱ), Fe(Ⅲ), y3 or Sm3 , respectively, in 0.50 mol/L HC1 and H on macrorecticular sulfonic ion exchange resin and the kinetics of the same reactions (M -H exchange) when Mn(Ⅱ) coexisted in resin phase as accelerating ion were studied. The accelerating effect manifested and its rule are consistent with the accelerating effect theory based on the concept concerned with adsorption electrical double layer which has been suggested in a previous paper published.     

Strategies for measurements of pseudocontact shifts in protein NMR spectroscopy.

Paramagnetic metal ions bound to proteins generate a dipolar field that can be accurately probed by pseudocontact shifts (PCS) displayed by the protein's nuclear spins. PCS are highly useful for determining the coordinates of individual spins in the molecule and for rapid structure determinations of entire protein-protein and protein-ligand complexes. However, PCS measurements require reliable resonance assignments for the molecule in its paramagnetic state and in a diamagnetic reference state. This article discusses different approaches for pairwise resonance assignments, with emphasis on a strategy which exploits chemical exchange between the two states.     

电位法测定异价阳离子通过阳离子交换膜时的选择透过性

从理论上导出了不等价的两种阳离子在通过阳离子交换膜时的选择透过性与膜电位的关系，并用电位法对一些不等价阳离子组合在两种商品膜中的选择透过性进行了测定。本方法测定结果与电渗析实际分离效果相符。     

合成CFC-12替代物HFC-134a的CrF3/AlF3催化剂的研究

考察了不同反应条件下ＨＣＦＣ－１３３ａ与ＨＦ在ＣｒＦ３／ＡｌＦ３催化剂作用下生成ＨＦＣ－１３４ａ的反应性能。需用ＧＣ－ＦＴＩＲ方法鉴定了产物的组成，探讨了副产物形成的原因，并进行了催化剂的稳定性试验。结果表明在ＨＦ／ＨＣＦＣ－１３３ａ流量比为１０和３５０℃和条件下，得到了较高的转化率和选择性。