Transition‐Metal‐Free Trifluoromethylthiolation of N‐Heteroarenes

A general and efficient methodology for the direct transition metal free trifluoromethylthiolation of a broad range of biologically relevant N‐heteroarenes is reported employing abundant sodium chloride as the catalyst. This method is operationally simple, exhibits high functional group tolerance, and does not require protecting groups.     

Chemoselective tetrahydropyranylation of alcohols and phenols using polystyrene supported aluminium chloride as a catalyst

A simple, efficient and highly chemoselective method for tetrahydropyranylation of alcohols and phenols has been developed by their reaction with 3,4-dihydro-2H-pyran at room temperature in the presence of a catalytic amount of polystyrene supported AlCl₃. The method is also highly selective for monoprotection of symmetrical diols.     

Diisobutylaluminium hydride (DIBAL-H) as a molecular scalpel: a new mechanistic proposal for a spiroketal rearrangement

Taking advantage of our knowledge of the capacity of DIBAL-H to de-O-alkylate, we propose an alternative mechanism for a spiroketal rearrangement described by E. Suàrez. We also show that this proposal can account for the formation of the secondary product, whose original structure we propose to correct.     

Studies of photooxidative degradation of poly(vinyl chloride)/poly(ethylene oxide) blends

The photooxidative degradation of blends (in a full range of compositions) of amorphous poly(vinyl chloride) (PVC) with semicrystalline poly(ethylene oxide) (PEO) in the form of thin films is investigated using absorption spectroscopy (UV–visible and Fourier transform infrared) and atomic force microscopy (AFM). The amount of insoluble gel formed as a result of photocrosslinking is estimated gravimetrically. It is found that the PVC/PEO blendsí susceptibility to photooxidative degradation differs from that pure of the components and depends on the blend composition and morphology. Photoreactions such as degradation and oxidation are accelerated whereas dehydrochlorination is retarded in blends. The photocrosslinking efficiency in PVC/PEO blends is higher than in PVC; moreover, PEO is also involved in this process. AFM images showing the lamellar structure of semicrystalline PEO in the blend lead to the conclusion that the presence of PVC does not disturb the crystallization process of PEO. The changes induced by UV irradiation allow the observation of more of the distinct PEO crystallites. This is probably caused by recrystallization of short, more mobile chains in degraded PEO or by partial removal of the less stable amorphous phase from the film surface. These results confirm previous information on the miscibility of PVC with PEO. The mechanism of the interactions between the components and the blend photodegradation are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 585–602, 2004     

Synthesis and characterization of N-3-phenyl-2-propenoyl amino acids

Three N-3-phenyl-2-propenoyl amino acids were synthesized through interaction between 3-phenyl-2-propenoyl chloride and amino acids in alkaline with a high Yield.Structure of the products were identified by elemental analysis,IR and NMR spectroscopy.     

Nickel Chloride Promoted Glaser Coupling Reaction in Hot Water

A Glaser coupling reaction of terminal alkynes in the presence of nickel chloride withoutany organics and bases in hot water has been developed, which produces the correspondinghomo-coupling products in good yields.     

Hydroxylation-induced modifications of the Al2O3/NiAl(0 0 1) surface at low water vapour pressure

STM, STS, LEED and XPS data for crystalline θ-Al₂O₃ and non-crystalline Al₂O₃ ultra-thin films grown on NiAl(0 0 1) at 1025 K and exposed to water vapour at low pressure (1 × 10⁻⁷-1 × 10⁻⁵ mbar) and room temperature are reported. Water dissociation is observed at low pressure. This reactivity is assigned to the presence of a high density of coordinatively unsaturated cationic sites at the surface of the oxide film. The hydroxyl/hydroxide groups cannot be directly identify by their XPS binding energy, which is interpreted as resulting from the high BE positions of the oxide anions (O_1s signal at 532.5-532.8 eV). However the XPS intensities give evidence of an uptake of oxygen accompanied by an increase of the surface coverage by Al³⁺ cations, and a decrease of the concentration in metallic Al at the alloy interface. A value of ∼2 for the oxygen to aluminium ions surface concentration ratio indicates the formation of an oxy-hydroxide (AlO_xOH_y with x + y ∼ 2) hydroxylation product. STM and LEED show the amorphisation and roughening of the oxide film. At P(H₂O) = 1 × 10⁻⁷ mbar, only the surface of the oxide film is modified, with formation of nodules of ∼2 nm lateral size covering homogeneously the surface. STS shows that essentially the valence band is modified with an increase of the density of states at the band edge. With increasing pressure, hydroxylation is amplified, leading to an increased coverage of the alloy by oxy-hydroxide products and to the formation of larger nodules (∼7 nm) of amorphous oxy-hydroxide. Roughening and loss of the nanostructure indicate a propagation of the reaction that modifies the bulk structure of the oxide film. Amorphisation can be reverted to crystallization by annealing under UHV at 1025 K when the surface of the oxide film has been modified, but not when the bulk structure has been modified.     

铁基添加剂增强细水雾灭火性能的实验研究

采用实验模拟的方法,研究了添加氯化亚铁的细水雾在不同添加剂浓度、不同喷头压力下,熄灭不同性质的液体池火的性能。实验结果表明:添加有氯化亚铁的细水雾,其灭火性能发生了显著变化。存在一个最佳的灭火浓度,其对应的灭火时间最短,耗水量最少,灭火效率最高。细水雾喷头的工作压力和燃料的性质也对细水雾的灭火性能有影响:工作压力越大,细水雾的平均灭火时间越短。在相同的实验条件下,细水雾扑灭煤油池火的时间要短于扑灭酒精池火的时间。     

Poly(vinyl chloride)-paste/clay nanocomposites: Investigation of thermal and morphological characteristics

The paper concentrates on poly(vinyl chloride) - PVC - from the point of nanocomposite characterisation through thermal degradation of samples, evolution of the changes caused by elevating temperature using TGA, FTIR and Congo Red methods combined with morphological characterisation by XRD and TEM analyses. A novel method of PVC-paste/nanocomposite preparation while processing was used. During preparation, PVC plasticizer was mixed with clay, both natural and organophilic, and the suspension was then compounded with the other components. Two factors were followed: effect of shearing alone, and in combination with temperature. As is presented, the type of nano-filler and its chemical modifier have obvious influence on final properties either thermal or morphological. Presented contribution follows previous part of investigation and brings further information from PVC-paste/nanocomposite field.