碱性季铵盐“一锅法”催化合成四氢苯并[b]吡喃的水相反应研究

报道了以2-二甲氨乙基苄基二甲基氯化铵为催化剂,在水相介质中"一锅法"催化芳醛、丙二腈和5,5-二甲基-1,3-环己二酮合成2-氨基-3-氰基-4-芳基-7,7-二甲基-5-氧代-4H-5,6,7,8-四氢苯并[b]吡喃的方法.该法具有产率高、反应时间短、操作简便、对环境友好、催化剂可重复使用等优点.     

氨基安替比林分子原位烙印柱的制备及其水中结合性质的研究

实验采用原位聚合法以甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EDMA)为交联剂,偶氮二异丁扉(AIBN)为引发剂,正十二醇和甲苯为致孔剂直接在液相色谱柱中制备了氨基安替比林分子烙印柱．讨论了模板分子及其类似物在有机相和水相中的色谱行为及作用机理．实验表明,在水相中烙印柱具有很强的保留性能,氨基安替比林的保留因子可达到94．41．结果认为离子作用和疏水作用是使得氨基安替比林及类似物具有很强的保留性的重要原因,为研究模板聚合物的结合特性,采用前流分析法分别测定了氨基安替比林、氨基比林和安替比林在烙印柱上的吸附等温线．实验表明,分子烙印聚合物对烙印分子表现了较高的选择性,这和通过比较各物质在分子烙印柱和空白柱上保留因子所获得的结果一致．     

Scattering spectra and colour of disperse systems of low-absorptive particles

In this article, the results of calculations of scattering spectra of low-absorptive spherical particles are presented. It was obtained using different approximate and numerical methods. The comparative evaluations of application of single scattering approximation, the average field approximation and of the methods of computer modeling on the basis of Monte-Carlo method on various scattering multiplicity were performed. The comparison demonstrates the good agreement of calculated results with experimental scattering spectra of eye lens. By using the obtained spectral data the colour coordinates are calculated. The regularities of changes in colour characteristics in dependence of disperse system parameters are analyzed.     

有组织介质中的偶合反应Ⅱ.溶剂对偶合反应动力学的影响

本文采用连续流动装置,结合数学模型方法,测定了油溶性成色剂分别分散在邻苯二甲酸二丁酯(DBP)、N,N-二乙基十二烷基酰胺(DEDA)和磷酸三丁酯(TBP)三种溶剂中的油珠在明胶层中分别与彩色显影剂CD-2、CD-3、CD-4和CD-6的氧化产物QDI2、QDI3、QDI4、QDI6进行偶合反应的比速率常数,研究溶剂对油珠分散状成色剂的反应速率的影响。结果表明,溶剂对偶合反应速率的影响很大,一般来说,KDBP>KTBP≥KDEDA.对同一种成色剂而言,它分别与QDI2、QDI3、QDI4和QDI6进行偶合反应的比速率常数值可以表征各种显影剂氧化产物的活性。结果还表明,QDI2、QDI3、QDI4和QDI6的活性顺序随着成色剂溶剂的不同而不同。本文对上述实验结果进行了分析,并从有组织介质中的反应的角度进行了讨论。     

One-Pot Oxidation of Alanine and Its Ethyl Ester with a Mild Oxidant 4′-Methylazobenzene-2-sulfenyl Bromide

One-pot oxidation of alanine and its ethyl ester with a mild oxidant 4′-methylazobenzene-2-sulfenyl bromide is described. Using a nonreactively water-soluble electrophilic species, 4′-methylazobenzene-2-sulfenyl bromide, with L-alanine and its ethyl ester (in 3:1 molar proportions) in aqueous solution at room temperature, the corresponding sulfenimines are prepared. On hydrolysis in acidic medium at room temperature, these sulfenimines give ethanal and pyruvic acid respectively.

纯水中检测汞离子与银离子的菲啰啉类荧光探针

合成了菲啰啉类化合物探针1,并通过核磁共振波谱(NMR)、质谱(MS)、红外光谱(IR)对其结构进行了表征。利用荧光发射光谱考察了探针1对Hg~(2+)及Ag~+的识别性能。结果表明,探针1在纯水介质中以荧光猝灭的方式识别Hg~(2+)和Ag~+,其结合比分别为1∶1和2∶1,检测的线性范围分别为9.0×10~(-7)～1.1×10~(-5)和8.0×10~(-7)～7.0×10~(-6) mol/L,相关系数(r~2)均大于0.99,检出限均低至10~(-8)mol/L。根据探针1识别前后荧光强度的剧烈变化,建立了裸眼检测Hg~(2+)和Ag~+的可视化分析方法。通过等温量热滴定与~1H NMR滴定考察了识别过程的热力学参数和作用机理。该研究对生物体及环境领域中Hg~(2+)和Ag~+的实时监测具有潜在的应用价值。     

Pattern forming precipitation in gels due to coupling of chemical reactions with diffusion

Precipitate-forming chemical reactions have been studied in chemically cross-linked poly(vinyl alcohol) gel medium. One of the reactive components was incorporated into the gel, the other was allowed to diffuse into it. Depending on the experimental conditions the reaction-diffusion process often results in patterns of different type. Experiments performed in tubes and in thin layers were carried out in order to investigate the effects of various factors (cross-linking density, swelling degree as well as the concentrations of the outer and inner electrolytes) on the morphologies of the precipitate patterns. It was found that precipitation occurs not only in the Liesegang bands, but also between bands. Beside Liesegang-type structures, tree-like patterns have been observed, showing a characteristic periodicity in the density profile obtained by digitalized image analyses.     

Synthesis and structure of anhydrodimers of salicylaldehydes

Anhydrodimers have been synthesized by reactions of salicylaldehyde and 3,5-di-tert-butylsalicylaldehyde with SOCl₂ or PCl₅. A mechanism of condensation has been proposed, and the molecular structure of dibenzo-2,6,9-trioxabicyclo[3.3.1]nona-3,7-diene has been determined by X-ray structural analysis.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1549–1551, August, 1995.The work was supported by the Russian Foundation for Basic Research (Project No. 94-03-08653).     

附加试剂及反应介质对TPPFeCl催化环己烷仿生氧化反应性能的影响

研究了某些附加试剂及反应介质对四苯基卟吩合铁(Ⅲ)[TPPFeCl或(TPPFe)₂O]模拟细胞色素P-450催化PhIO羟化环己烷反应的影响。发现适量的异丙醇、吡啶及NaOH能促进反应,加入盐酸及增大介质的极性对反应不利。证明了副产物环己酮主要是由PhIO直接氧化主产物环己醇生成的,TPPFeCl的存在不利于酮的生成,醇的存在能延长催化剂的寿命。