Peculiarities of electroreduction of trans-2-allyl-6-methyl(allyl,phenyl)-1,2,3,6-tetrahydropyridines

Electrochemical reduction of trans-2-allyl-6-R-1,2,3,6-tetrahydropyridines (R = Me, All, and Ph) on the mercury cathode in anhydrous DMF (with 0.1 M Bu₄NClO₄ as the supporting electrolyte) resulted in catalytic hydrogen evolution, while in the case of anhydrous DMF the electrochemical activity of the endocyclic double bond was dictated by the nature of the R substituent at the carbon atom neighboring the double bond. The electrocatalytic hydrogenation of the piperideines under study on the Ni (Ni_disp/Ni) cathode in 40% aqueous DMF in the presence of a tenfold excess of AcOH yielded the corresponding trans-2-propyl-6-R¹-piperidines (R¹ = Me, Pr, and Ph). Using trans-2,6-diallyl-1,2,3,6-tetrahydropyridine as an example, the conditions (with annealed copper as the cathode) for selective hydrogenation of the double bonds in allyl substituents with preservation of the endocyclic double bond were found.     

异硫氰酸荧光素标记抗体的固体基质室温磷光性质研究

研究了异硫氰酸荧光素（FITC）标记的羊抗人抗体（GAHAb-FITC)和兔抗羊抗体9RAGAb-FITC)，及其以三种免疫方式与人免疫球蛋白（IgG)反应所得免疫复合物在多种固体薄膜基质上发射室温磷光（RTP）的适宜条件及其光谱，强度和寿命等性质。研究发现，标记抗体及其免疫复合物保留了FITC优良的固体基质室温磷光性质，λ m0643em^(max)=525/650nm，其RTP强度与其浓度线性相关，并有很高的灵敏度，更为重要的是，免疫反应及其RTP检测能结合于同一基质，方便地相继完成，在聚酰胺膜（PM）上，以Pb(Ac)2为重原子微扰剂，稀释比为1：10（ψ）的GAHAb-FITC,RAGAb-FITC及其与人IgG形成的免疫复合物均能发射较强制 RTP信号并有较长的RTP寿命，本结果为建立相应的固体基质室温磷光免疫分析（SS-RTP-IA）新方法奠定了相应的实验基础。     

Design and chemical behavior of novel pyrimidine derivatives and their evaluation of cytotoxicity

Abstract

Diphenyl-4-thioxo-1,4-dihydropyrimidin-5-yl)ethan-1-one 4 was obtained upon the reaction of (phenylamino)but-2-enethioyl)benzamide 3 with sodium hydroxide. The reactions of 4 with several active species such as benzaldehyde, urea, malononitrile, ethyl cyanoacetate, hydrazine, and carbon disulfide were studied. The antitumor activities of some selective compounds were examined against two cell lines: Mammalian cell lines: A-549 cells (human lung cancer cell line) and MRC-5 cells (normal human lung fibroblast cell line); some of the compounds were highly efficient; compound 13 has the most effective anticancer activity.     

Effects of potassium on the reaction pathway of C3H7 species over Mo2C/Mo (1 0 0)

The adsorption and surface reactions of propyl iodide on clean and potassium-modified Mo₂C/Mo(1 0 0) surfaces have been investigated by thermal desorption spectroscopy (TPD), X-ray photoelectron spectroscopy (XPS) and high resolution electron energy loss spectroscopy (HREELS) in the 100-1200 K temperature range. This work is strongly related to the better understanding of the catalytic effect of Mo₂C in the conversion of hydrocarbons. Potassium was found to be an effective promoter: it induced the rupture of C-I bond in the adsorbed C₃H₇I even at 100 K. The extent of C-I bond scission varied approximately linearly with the concentration of K coverage at the adsorption temperature of 100 K. As revealed by HREELS and TPD measurements the primary products of the dissociation are C₃H₇ and I. The former one was stabilized by potassium and underwent dehydrogenation and hydrogenation to give propene and propane. The desorption of both compounds is reaction-limited process. A fraction of propyl groups was converted into di-σ-bonded propene, which was stable up to ∼380 K. The coupling reaction of propyl species was also facilitated by potassium and resulted in the formation of hexane and hexene with T_p ∼ 230-250 K. Hydrogen was released with T_p = 390 K, indicative of a desorption limited process. The effect of potassium was explained by the extended electron donation to adsorbed propyl iodide in one hand, and by the direct interaction between potassium and I on the other hand. This was reflected by the shift of the desorption of potassium from the coadsorbed layer at and above 1.0 ML to higher temperature, and by the coincidal T_p values (∼700 K) of potassium and iodine. The formation of KI was also supported by the appearance of a loss feature at 650 cm⁻¹ in the HREEL spectra attributed to a phonon mode of KI.     

SmI~2 引发异腈酸酯和异硫腈酸酯的反应

室温下SmI~2/ THF/ HMPA 体系可顺利地将异腈酸酯(RNCO)还原偶联成草酰胺衍生物(RNHCOCONHR),同样条件下, RNCO可以和PhCOCl, R^1X等发生交叉偶联得到酰胺; 而异硫腈酸酯在类似条件下却发生脱硫反应,得到异腈。     

双(1,4-二酰基氨基硫脲)化合物的合成

酰氨基硫脲及其相关化合物通常具有广泛的生物活性 ,如抗菌[1～ 3] ,抑制神经紧张[4] ,治疗血糖过低[5] ,植物生长调节[6～ 9] 等。迄今为止 ,鲜有关于双 (1 ,4 二酰基氨基硫脲 )合成的报道。为了考查该类化合物的生物活性 ,我们设计合成了一系列双 (1 ,4 二酰基氨基硫脲 )化合物 ,以下图所示的两条合成路线合成了该类化合物 :二酰氯 (1 )、异硫腈酸酰酯 (2 )等中间体可不经进一步纯化直接用于下一步反应。所生成的产物 3ａ 3ｆ、3′ｄ 3′ｇ经ＤＭＦ Ｈ2 Ｏ ＥｔＯＨ重结晶 ,产率达 81 %～ 98%。在合成化合物 (1 )时 ,对于一些用ＳＯＣｌ2 …     

铂氢化物的研究——Ⅰ.trans-PtHCl(PPh3)2的一种新的消去氯化氢反应

本文研究了铂氢化物trans-PtHCl(PPh)_2(Ⅰ)与异硫氰酸苯酯(PhNCS)的反应。和第Ⅷ族Ru、Os、Ir的氢化物与异硫氰酸酯(RNCS)的插入反应不同,(Ⅰ)与PhNCS在苯中回流反应,(Ⅰ)即消去氯化氢,而PhNCS则发生歧化反应,得到含dithiocarbonimibato配体的铂配合物,而trans-PtHCl-(Pcy_3)_2与PhNCS在同样条件下延长反应时间不发生反应,提出了可能的反应机理。     

Isothiocyanat-Komplexe von Kupfer (II) mit quadratisch-planarer und tetragonal-pyramidaler Koordination: Struktur,Phasenumwandlungen und Redoxverhalten

Isothiocyanate Complexes of Copper(II) with Square-Planar and Tetragonal-Pyramidal Coordination: Structure, Phase Transitions, and Redox-Properties In dependence on the kind and size of the counter-cations Cu²⁺-ions form isothiocyanate complexes with different coordination number and geometry. The structures of compounds with square-planar coordination [(NEt₄)₂[Cu(NCS)₄] · CHCl₃ (brown): Space group 14/mmm, Z = 2; a = 1204.3(2) pm, c = 1154.2(3) pm] and with tetragonal-pyramidal polyhedra [(NEt₄)₃[Cu(NCS)₅] · SM (green, SM: unidentified solvent molecule): Space group P2₁/c, Z = 4; a = 1154.2(6) pm, b = 2291.6(10) pm, c = 1739.9(9) pm, ß = 95.98(5)°] are reported. The green complex transforms into a brown compound at room-temperature; the transformation is (partly) reversibly. Solutions of NCS-anions and Cu²⁺ are redox unstable. The structure of a resulting product: (PPh₄)₂[Cu₂(NCS)₂] [Space group C2/c, Z = 4; a = 1235.4(1) pm, b = 1347.1(2) pm, c = 2953.4(11) pm, ß = 99.36(2)°] with Cu(I) dimers and two bridging NCS^- ligands is also reported.     

丙醇-硫酸铵双水相体系萃取金(Ⅲ)-氯化物-罗丹明B

水溶性聚合物如聚乙二醇 (ＰＥＧ )、吐温(Ｔｗｅｅｎ) 80的水溶液在电解质存在下萃取分离贵金属离子已有报道[1] ;小分子的有机物如乙醇、丙醇在硫酸铵、氯化钠等电解质存在下也能分为两相形成双水相体系 ,可应用于金属离子的分离[2 ] ;该类体系也可以用于萃取分离贵金属络阴离子[3,4] 。我们发现金 (Ⅲ )与氯离子在碱性染料罗丹明Ｂ(ＲｈＢ)参与下所形成的三元缔合物 ,可被丙醇 硫酸铵双水相体系定量萃取而与大量常见贱金属分离 ,体系同时具有溶剂萃取法及溶剂浮选法的优点 :既可以分离简单贵金属络阴离子[3,4] ,又可以分离贵金属三元缔…     

Synthesis and characterization of poly(urethane-sulfone)s

Eight poly(urethane-sulfone)s were synthesized from two sulfone-containing diols, 1,3-bis(3-hydroxypropylsulfonyl)propane (Diol-333) and 1,4-bis(3-hydroxypropylsulfonyl)butane (Diol-343), and three diisocyanates, 1,6-hexamethylene diisocyanate (HMDI), 4,4′-diphenylmethane diisocyanate (MDI), and tolylene diisocyanate (TDI, 2,4- 80%; 2,6-20%). As a comparison, eight polyurethanes were also synthesized from two alkanediols, 1,9-nonanediol and 1,10-decanediol, and three diisocyanates. Diol-333 and Diol-343 were prepared by the addition of 1,3-propanedithiol or 1,4-butanedithiol to allyl alcohol and subsequent oxidation of the resulting sulfide-containing diols. The homopoly(urethanesulfone)s from HMDI and MDI are semicrystalline, and are soluble in m-cresol and hot DMF, DMAC, and DMSO. The copoly(urethane-sulfone)s from a 1/1 molar ratio mixture of Diol-333 and Diol-343 with HMDI or MDI have lower crystallinity and better solubility than the corresponding homopoly(urethane-sulfone)s. The poly(urethane-sulfone)s from TDI are amorphous, and are readily soluble in m-cresol, DMF, DMAC, and DMSO at room temperature. Differential scanning calorimetry data showed that poly(urethane-sulfone)s have higher glass transition temperatures and melting points than the corresponding polyurethanes without sulfone groups. The rise in glass transition temperature is 20–25°C while the rise in melting temperature is 46–71°C. © 1994 John Wiley & Sons, Inc.