含偶氮聚四氢呋喃的合成及分解

<正> 本文以4,4′-偶氮二异氰基戊酰氯(ACVCl)与SbCl_5引发体系,低温下进行THF聚合,合成出主链中含有一个偶氮基的聚四氢呋喃(简称AZO-PTHF)。该聚合物中的AZO基和通常低分子偶氮化合物一样可在受热时发生分解反应,生成大分子游离基,因此可作为高分子引发剂引发乙烯基单体聚合。ESR波谱分析表明,该聚合物在40°C左右热分解产生游离基。     

New methods of preparation of nitrile oxides and the corresponding disubstituted furoxans by interaction of N2O4 with salts of substituted dinitromethanes

A new method of generation of nitrile oxides through interaction of N₂O₄ with salts of substituted dinitromethanes (1) has been worked out. It has been shown by¹H,¹³C,¹⁴N NMR spectroscopy that this reaction proceeds via dinitronitrosomethyl intermediates (one of these has been isolated), and that the reaction is feasible only for substituents capable of conjugation with the nitrile oxide fragment. On the basis of cyclodimerization of the obtained nitrile oxides, preparative methods of synthesis of symmetrically substituted furoxans have been developed.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 147–151, January, 1993.     

氢化物负压发生,夹带氧气的真空无火焰原子吸收测量技术测定砷、锑、硒和锡

在负压氢化物发生器中用1％NaBH_4将砷、锑、硒和锡还原成氢化物后,加入一定量氧气,用真空泵将氧与氢化物的混合物吸入到电热石英管中,同时用原子吸收仪器测定。加入的氧与来自硼氢化钠分解产生的氢反应,生成气态水分子,因而消除了氢对测量元素的干扰。     

Picoline as ligand with antimony trichloride and triiodide adducts

Solid adducts SbX₃·L-pic (X=Cl, I and L=α-, β- and γ-picolines) were synthesized and characterized by elemental analysis, ¹H and ¹³C NMR, IR spectroscopy and thermal analysis. The infrared spectroscopy and the magnetic resonance for ¹H and ¹³C nuclei of these compounds suggest that the ligands coordinate through nitrogen atom. Kinetic studies were accomplished by means of thermogravimetric data, through isothermal and non-isothermal techniques. The best adjusting models for adducts thermal decomposition were R¹ for isothermal and R₁ and R₂ for the non-isothermal methods. The energy of activation values obtained by isothermal method indicate the following orders of thermal stability for adducts: i) SbCl₃·α-pic>SbCl₃·β-pic>SbCl₃·γ-pic and ii) SbI₃·β-pic>SbI₃·γ-pic>SbI₃·α-pic. The activation energy values obtained by non-isothermal were higher than those from isothermal methods, showing the order of stability:iii) SbCl₃·α-pic<SbCl₃·β-pic<SbCl₃·γ-pic and iv) SbI₃·β-pic>SbI₃·α-pic=SbI_3··γ-pic. These obtained data through R₁ model presented the kinetic compensation effect for trichloride adducts, which could be associated to both isothermal and non-isothermal processes. This revised version was published online in August 2006 with corrections to the Cover Date.     

Determination of As,Sb and Bi in high-purity copper by electrothermal atomic absorption spectrometry

As, Sb and Bi were determined in copper electric cables by atomic absorption spectrometry with electrothermal atomization in a graphite furnace. The interferences in the determination of As, Sb and Bi caused by eleven cationic species and six types of acid were studied. The different volatilization of the copper matrix in comparison to the analyte was studied, as a means of increasing the analyte signal/non-specific absorption signal ratio.     

TRANSMISSION ELECTRON MICROSCOPY OF SEGMENTED POLYURETHANES WITH RUTHENIUM TETROXIDE AS A STAINING AGENT

Microphase separation and lamellar structure of segmented polyether- and polyester-polyurethanes have been investigated by means of transmission electron microscopy with the ruthenium tetroxide staining technique. The results show that the RuO_4 staining technique is simpler and may give better image contrast than other staining methods for this polymer. Microphase separation and lamellar structure of segmented polyether-and polyester-polyurethanes were directly observed and discussed.     

The OsO4-mediated oxidative cleavage of olefins catalyzed by alternative osmium sources

The OsO₄-mediated oxidative cleavage of olefins is compatible with alternative, easier-to-handle osmium sources. Four different osmium sources were employed with favorable results.     

固固反应合成三碘化锑、三碘化铋的硫脲配合物(英文)

通过三碘化锑和三碘化铋与硫脲间的室温固固反应合成了三碘化锑、三碘化铋的硫脲配合物 ,其组成通式为 :M(CS(NH2 ) 2 ) 3 I3 (M =Sb ,Bi) .两种配合物的晶体结构均属于单斜晶系 ,锑配合物Sb(CS(NH2 ) 2 ) 3 I3 的晶胞参数为 :a =1.4 772nm ,b=1.6 5 82nm ,c =2 .0 6 74nm ,β =90 .81°,铋配合物Bi(CS(NH2 ) 2 ) 3 I3 的晶胞参数为 :a =1.4 0 10nm ,b =2 .0 16 8nm ,c =2 .0 397nm ,β =90 .84° .远红外光谱表明硫脲中的N原子而非硫原子参与了配位