Diterpenoids of Isodon macrophylla

Two new ent‐abietane diterpenoids, macrophynin E ( 1 ) and macrophynin F ( 2 ), and a known related ent‐abietanoid (?)‐lambertic acid ( 3 ), together with four known ent‐kauranoids, were isolated from the roots and aerial parts of Isodon macrophylla, respectively. The structures of the new compounds were elucidated on the basis of spectroscopic‐data analysis and chemical correlations.     

Scanning tunneling microscopy of prochiral anthracene derivatives on graphite: chain length effects on monolayer morphology

The morphology of monolayers formed upon adsorption of prochiral 1,5-substituted anthracene derivatives on highly oriented pyrolytic graphite is investigated using scanning tunneling microscopy at the liquid-solid interface. The adsorption orientation of these prochiral anthracene derivatives positions one of their enantiotopic faces in contact with the graphite. The molecules adsorb in rows with contact between adjacent anthracenes. The anthracene side chains extend perpendicular to the direction of the row repeat. All molecules within a single row adsorb via the same enantiotopic face. Anthracenes with side chains containing an even number of non-hydrogenic atoms (C, S) form monolayers in which molecules in adjacent rows adsorb via opposite enantiotopic faces. Anthracenes with side chains that contain an odd number of non-hydrogenic atoms form two-dimensional chiral domains in which all rows contain molecules adsorbed via the same enantiotopic face. This chain length effect on monolayer morphology represents a generalized example of structural effects previously observed in alkanoic acid monolayers formed on HOPG. The variation of the STM current with position in the vicinity of the anthracenes indicates that the highest occupied molecular orbital is the predominant mediator of tunneling for the aromatic group.     

Poly（meta-phenylene） Derivative with Rigid Twisted Biphenyl Units in Backbone： Synthesis, Structural Characterization, Photophysical Properties and Electroluminescence

A soluble poly(meta-phenylene)derivative with rigid twisted biphenyl unit was synthesized by the Yamamoto coupling reaction.The polymer is soluble in common organic solvents,and the number-average molecular weight is about 6500.The UV-Vis and quantum chemical calculation indicate that the different conformation segments named "conformers" exist in the polymer backbones;it was also further confirmed by the single crystal X-ray diffraction study of the dimeric model compound.The π-π transition of biphenyl segments of twisted and planar conformations made the polymer exhibit a strong absorption around 256 nm and a weak absorption at about 300 nm.Furthermore,the polymer exhibits a strong UV photoluminescence at 372 nm when the excitation wavelengths are longer than 300 nm.The ultraviolet-emitting electroluminescence(EL)device with the single layer structure shows EL λmax of the derivative at 370 nm.     

Electrophilic monofluoromethylation of O-, S-, and N-nucleophiles with chlorofluoromethane

CH₂ClF has been found to be a useful electrophilic monofluoromethylating agent for a variety of O-, S-, and N-nucleophiles. The reaction is not sensitive to the radical scavenger such as nitrobenzene, which strongly supports an S_N2 mechanism rather than an SET mechanism. Although most of these products (fluoromethyl ethers, sulfides, and amines) can be isolated with good purity, some of these compounds do intend to decompose (via defluorination) during storage. The electrophilic monofluoromethylation of carbon-nucleophiles was attempted with CH₂ClF, CH₂FI, or FCH₂OTs as monofluoromethylating agents, but with no success.     

Helical structures architecture of l-{2-(4-hydroxy-phenyl)-1-[(pyren-1-ylmethyl)-carbamoxyl]-ethyl}-carbamic acid tert-butyl ester

A new pyrenemethylamine substituted l-Boc-tyrosine derivative was synthesized and characterized. UV-vis, FL, CD, and light scattering experiments proved that the chiral molecules were able to self-assemble for formation of new aggregate structure. The SEM and AFM images indicated that the helical wires could be fabricated by π-π stacking interaction between adjacent pyrene molecules.     

Three New Neolignans from the Aril of Myristica fragrans

Three new neolignans, named 1‐deoxycarinatone ( 1 ), isodihydrocarinatidin ( 2 ), and isolicarin A ( 3 ), together with the known neolignan (+)‐dehydrodiisoeugenol ( 4 ), were isolated from mace (the aril of Myristica fragrans Houtt .). Their structures were elucidated as 2‐[(1S)‐2‐(4‐hydroxy‐3‐methoxyphenyl)‐1‐methylethyl]‐6‐methoxy‐4‐(prop‐2‐enyl)phenol ( 1 ), 4‐[(2R,3R)‐2,3‐dihydro‐7‐methoxy‐3‐methyl‐5‐(prop‐2‐enyl)benzofuran‐2‐yl]‐2‐methoxyphenol ( 2 ), and 4‐{(2S,3R)‐2,3‐dihydro‐7‐methoxy‐3‐methyl‐5‐[(1E)‐prop‐1‐enyl]benzofuran‐2‐yl}‐2‐methoxyphenol ( 3 ) on the basis of spectroscopic data.     

Oxidative Methyl Esterification of Primary Alcohols with Iodine‐Mediated Poly[4‐(Diacetoxyiodo)Styrene]

An operationally simple oxidative methyl esterification of primary alcohols in good yields using an iodine‐mediated poly[4‐(diacetoxyiodo)styrene] in methanol at room temperature is described. The polymeric reagent can be regenerated and reused as an environmentally benign reagent.     

CuI催化的酰胺和溴苯的偶联反应研究

本文报道了一种新的催化体系 (CuI / 氨基酸 / K₃PO₄) 催化胺和芳香溴代化合物之间的交叉偶联反应，对于不同的底物都以较好的产率得到了产物。该反应操作简单，适用性广，并且试剂价格便宜。     

Controlling the size of nanostructures in thin films via blending of block copolymers and homopolymers

The effects of molecular weight and concentration of poly (methyl methacrylate) (PMMA) homopolymer or symmetric short polystyrene-block-poly (methyl methacrylate) (PS-b-PMMA) diblock copolymer on the size of the nanostructures of its blends with symmetric long PS-b-PMMA diblock copolymer have been investigated by atomic force microscopy. By careful controlling of the film thickness, solvent selectivity, and annealing time, PMMA cylindrical microdomains oriented normal to the film surface were obtained in all thin films. With the addition of both low- and high-molecular-weight PMMA homopolymers, the cylindrical domain sizes increased although it was less obvious for the lower molecular weight homopolymer. In contrast to the homopolymer, adding the short chain diblock copolymer resulted in a decrease in the cylindrical domain size, which was ascribed to the reduction of the interfacial tension and increase in the stretching energy.     

MCM-41分子筛负载钼钴系催化剂的噻吩HDS研究

通过氧吸附量、噻吩吸附热及反应速率常数的测定，研究了MoO3/MCM-41、MoO3-CoO(NiO)/MCM-41系列催化剂，发现，对于MoO3/MCM-41催化剂，当MoO3的质量分数（以MCM－41为底数，即MCM－41＝1g时，MoO3含量为0．15g，下同）从15％增加到20％时，其噻吩的加氢硫（HDS）活性增大，至25％时活性下降，所对应的氧吸附量（mL/g催化剂）也是先增大后减少，并且两者有很好的线性对应关系，而且噻吩吸附热则基本保持不变，采用不同的MoO3-CoO(NiO)浸渍顺序制备的MoO3-CoO(NiO)/MCM-41催化剂中，先浸渍CoO(NiO）再浸渍MoO3的催化剂，其噻吩HDS活性明显优于对其它浸渍顺序制备的催化剂，同时催化剂的氧吸附量和噻吩吸附热也最大。