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Cover Picture: Asymmetric Synthesis of Both Enantiomers of Disparlure (Chin. J. Chem. 1/2012)
- Page: 1
- First Published: 16 January 2012

The cover picture shows a new and expeditious approach for the synthesis of disparlure and its enantiomer. The disparlure is the sex pheromone of the Gypsy moth Porthetria dispar L., which is used to monitor the Gypsy moth and protect plants against these pests. Starting from propargyl alcohol, and on the basis of Zhou's modified Sharpless asymmetric epoxidation, the sex pheromone of the Gypsy moth, disparlure and its enantiomer have been synthesized, each in six steps, with overall yields of 29% and 27% (ee>98%), respectively. The use of the sequential coupling tactic renders the method flexible, which is applicable to the synthesis of other cis-epoxy pheromones. More details are discussed in the article by Zheng et al. on page 23–28.
Masthead
Editorial
Chinese Journal of Chemistry: Entering the Third Decade in 2012
- Pages: 3-4
- First Published: 16 January 2012
Contents
(Contents: Chin. J. Chem. 1/2012)/(Graphical Abstracts: Chin. J. Chem. 1/2012)
- Pages: 5-13
- First Published: 16 January 2012
Further Masthead Information
Full Paper
Direct α-Alkylation of Aldehydes by Brønsted-Acid Catalysis
- Pages: 15-18
- First Published: 23 December 2011
Communication
Effect of Device Fabrication Conditions on Photovoltaic Performance of Polymer Solar Cells Based on Poly(3-hexylthiophene) and Indene-C70 Bisadduct
- Pages: 19-22
- First Published: 16 January 2012

Power conversion efficiency of the polymer solar cells based on poly(3-hexylthiophene) (P3HT) as donor and indene-C70 bisadduct (IC70BA) as acceptor reached 5.82% with open circuit voltage of 0.81 V, short circuit current of 11.37 mA/cm2 and fill factor of 64.0%, under the irradiation of AM1.5, 100 mW/cm2, at the optimized conditions of 188-nm-thick active layer of P3HT:IC70BA (1:1, w:w) blend film and pre-thermal annealing at 150°C for 10 min.
Full Papers
Asymmetric Synthesis of Both Enantiomers of Disparlure
- Pages: 23-28
- First Published: 23 December 2011

Starting from propargyl alcohol (12), and on the basis of Zhou's modified Sharpless asymmetric epoxidation, the sex pheromone of the Gypsy moth, disparlure (+)-8 and its enantiomer (−)-8 have been synthesized, each in six steps, with overall yields of 29% for (+)-8 and 27% for (−)-8 (ee>98%). The use of the sequential coupling tactic renders the method flexible, which is applicable to the synthesis of other cis-epoxy pheromones.
CuCl-Catalyzed Aerobic Oxidation of Allylic and Propargylic Alcohols to Aldehydes or Ketones with 1:1 Combination of Phenanthroline and Bipyridine as the Ligands
- Pages: 29-34
- First Published: 16 January 2012
Synthesis and Anti-tumor Evaluation of B-ring Modified Caged Xanthone Analogues of Gambogic Acid
- Pages: 35-42
- First Published: 23 December 2011

Two new series of B-ring modified caged xanhone analogues of Gambogic acid analogues were designed and synthesized utilizing a Claisen/Diel-Alder cascade reaction. These compounds were evaluated for their in vitro anti-tumor activities against A549, MCF-7, SMMC-7721 and BGC-823 cancer cell lines by MTT assay. The structure-activity relationship (SAR) was also discussed.
Molecularly Imprinted Polymer for Solid-Phase Extraction of Ecteinascidin 743 from Sea Squirt
- Pages: 43-46
- First Published: 16 January 2012

Ecteinascidin 743 from sea squirt is one of the most original anti-tumoral activity compounds, as proven by the Natural Cancer Institute. Ecteinascidin 743 could be obtained with traditional liquid extraction, but it should be purified and separated from the extract. A molecularly imprinted solid-phase extraction procedure was developed for the selective separation.
Retracted: A Facile Synthetic Route to New Fluorinated Building-Blocks of 1-Fluoroalkynes and 1-Fluorodiynes
- Pages: 47-52
- First Published: 16 January 2012
Orthogonal Enzymatic Reactions to Control Supramolecular Hydrogelations
- Pages: 53-58
- First Published: 23 December 2011
A New Nanocatalytic Spectrophotometric Assay for Cationic Surfactant Using Phosphomolybdic Acid-Formic Acid-Nanogold as Indicator Reaction
- Pages: 59-64
- First Published: 23 December 2011
A Green Route for the One-Pot Synthesis of 1,2-Disubstituted Benzimidazoles Using Iron(III) Phosphate under Solventless Conditions
- Pages: 65-70
- First Published: 16 January 2012

1,2-Disubstituted benzimidazoles are selectively synthesized in high yields under extremely mild conditions via the condensation of o-phenylenediamine derivatives with aldehyde derivatives using catalytic amount of iron(III) phosphate under solvent-free conditions. The use of readily available iron(III) phosphate as a reusable and recyclable catalyst makes this process quite simple, convenient, and environment-friendly.
Synthesis, Structure Elucidation and H+/K+-ATPase Inhibitory Activity of Bisabolangelone Reduction Derivatives
- Pages: 71-76
- First Published: 23 December 2011

Nine bisabolangelone reduction derivatives were synthesized and characterized. Preliminarily H+/K+-ATPase activity evaluation indicated compounds II and IV exhibited better inhibitory activities against H+/K+-ATPase than bisabolangelone and the commercial omeprazole with the IC50 of 23.21 and 65.32 μmol/L, respectively.
Synthesis and Antimicrobial Activity of New 2,5-Disubstituted 1,3,4-Oxadiazoles and 1,2,4-Triazoles and Their Sugar Derivatives
- Pages: 77-83
- First Published: 23 December 2011

A series of new 2,5-disubstituted-1,3,4-oxadiazole and 1,2,4-triazole derivatives were synthesized by heterocyclization of acid hydrazide 1 and thiosemicarbazide derivative 2. Furthermore the acyclic C-nucleoside analogs were also prepared by cyclization of their corresponding sugar hydrazones by reaction with acetic anhydride.
Theoretical Study of the Radical Scavenging Activity of Shikonin and Its Derivatives
- Pages: 84-90
- First Published: 23 December 2011
Photochemical Studies on 5-Methylbicyclo[1.1.1]pentane Derivatives: p-Orbital Overlap Controlled Enantioselectivity
- Pages: 91-95
- First Published: 16 January 2012
![Photochemical Studies on 5-Methylbicyclo[1.1.1]pentane Derivatives: p-Orbital Overlap Controlled Enantioselectivity](/cms/asset/dd61ef45-65ec-48a8-b563-f5803087edce/mcontent.jpg)
The first example of the p-orbital overlap controlled enantioselectivity of Norrish type II photocyclization reaction was described. Irradiation of 5-methyl bicyclo[1.1.1]pentanyl ketone with UV in the solid state as well as in the acetonitrile solution afforded the Norrish/Yang photocyclization compound as the sole product. Solid-state asymmetric photochemical studies using ionic chiral auxiliary technique led to the enantioselectivity as high as 60%. The results were rationalized by X-ray single crystal structure.
A Facile One-pot Synthesis of α-Halo,α-allylic Aldehydes from α,α-Dihalo Ketones Utilizing Allylic Zinc Bromide
- Pages: 96-102
- First Published: 16 January 2012

An efficient synthesis of various α-halo,α-allylic aldehydes from α,α-dihalo ketones using both cyclic (3-bromocyclohex-1-ene zinc bromide and (Z)-3-bromocyclobut-1-ene zinc bromide) and acyclic (allylzinc bromide and cinnamylzinc bromide) type of allylic organozinc bromide with DMF as base is described. A possible reaction mechanism is also proposed.
Electrochemiluminescence of SDBS-Ru(bpy)32+-CPM System and Its Application
- Pages: 103-108
- First Published: 23 December 2011

The additions of surfactants have obvious influence to the electrochemical and electrochemiluminescence (ECL) intensity of Ru(bpy)32+-chlorpheniramine maleate (CPM) system at the Au electrode. When the concentration of SDBS is 0.7 mmol·L−1, enhancement of the ECL intensity was 14-fold at Au electrode. Base on this, an ECL method was established for efficient and simple determination of CPM at Au electrode with high sensitivity and wide linear range. The enhanced effect of SDBS on ECL intensity of other eleven kinds of tertiary amines-Ru(bpy)32+ systems was universal in either GC electrode or Au electrode, while the enhancement of ECL intensity was higher in Au electrode than that in GC electrode.
Kinetics of the Reaction of 2-Chloro-3,5-dinitrobenzotriflouride with Aniline in Toluene and Methanol-Toluene Mixed Solvents
- Pages: 109-114
- First Published: 16 January 2012
Molecular Dynamics Simulation of Diffusion of Vitamin C in Water Solution
- Pages: 115-120
- First Published: 16 January 2012

Under different temperatures and concentrations, the diffusion of Vitamin C (VC) in water solution was examined by molecular dynamics simulation. The diffusion coefficients were calculated based on the Einstein equation. The influences of temperature, concentration, and simulation time on the diffusion coefficient were discussed.
DFT Studies of Ag-Loading Intrinsic and Functionalized Single-Walled Carbon Nanotubes
- Pages: 121-126
- First Published: 16 January 2012
Photocatalytic Degradation of Imidacloprid by Phosphotungstic Acid Supported on a Mesoporous Sieve MCM-41
- Pages: 127-132
- First Published: 16 January 2012

Solid catalysts consisting of polyoxometalates (POM) namely phosphotungstic acid H3PW12O40 (HPW) supported on a mesoporous sieve MCM-41 have been prepared and characterized. The HPW/MCM-41 with different HPW loadings from 10 to 60 wt% possess large specific surface area and rather uniform mesopores. Keggin structure of HPW retains on the prepared composite catalysts. The photocatalytic performance of HPW/MCM-41 was examined by degradation of a durable pesticide imidacloprid. It is found that the prepared photocatalysts exhibit high activity under irradiation of 365 nm monochromatic light.
Molecular and Mesoscopic Dynamics Simulations on the Compatibility of PLA/Plasticizer Blends
- Pages: 133-138
- First Published: 16 January 2012

The compatibility of the blend systems for olyactic acid (PLA)/tributyl citrate (TBC) and PLA/glycerol has been studied by molecule and mesoscopic dynamics methods. The results from glass transition temperature simulations showed that the compatibility of PLA/TBC system was better than that of PLA/glycerol, which were consistent with the conclusion obtained from the pair correlation functions. Besides, the behaviors of phase state distribution and evolution process were investigated by mesoscopic dynamics method as well. The results indicated that citrate ester was a better plasticizer than glycerol for PLA.
β-Alanine-DBU: A Highly Efficient Catalytic System for Knoevenagel-Doebner Reaction under Mild Conditions
- Pages: 139-143
- First Published: 16 January 2012

A mild and efficient Knoevenagel-Doebner reaction from malonic acid and a wide range of aldehydes was catalyzed by a catalytic system consisting of β-alanine and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), affording the corresponding (E)-α,β-unsaturated carboxylic acids in good to excellent yields and with high stereoselectivity. The advantage of the method is that the reaction could proceed smoothly at ambient temperature so that it can tolerate a variety of functional groups and avoid unnecessary side reactions.
Preparation of Mesoporous 1,4-Phenylene-silica Nanorings through a Dual-templating Approach
- Pages: 144-150
- First Published: 16 January 2012

Mesoporous 1,4-phenylene-silica nanorings were prepared using cetyltrimethylammonium bromide (CTAB) and (S)-2-methyl-1-butanol as a chiral dopant in concentrated aqueous NH3 solutions. Transmission electron microscopy images of the samples indicated that the nanorings were formed by bending nanorods 360(. With increasing the stirring speed or the (S)-2-methyl-1-butanol/CTAB molar ratio, the morphologies of mesoporous 1,4-phenylene-silicas changed from helical nanofibers to nanorings, and then to nano-saddles. Circular dichroism spectra of these hybrid silicas indicated that they were chiral.
Nanoporous Pt Catalyst Modified by Sn Electrodeposition for Electrochemical Oxidation of Formaldehyde
- Pages: 151-156
- First Published: 16 January 2012

A novel titanium-supported nanoporous Pt catalyst (nanoPt/Ti) was fabricated using a hydrothermal method and the nanoPt/Ti electrode was then modified with limited amounts of tin particles generated by cyclic potential scans to synthesize a Sn-modified nanoporous Pt catalyst (Sn/nanoPt/Ti). Compared to nanoPt/Ti, formaldehyde electrooxidation on Sn/nanoPt/Ti displays a dramatic improvement at the most negative potentials.
Evaluation and Comparison of a 3,5-Dimethylphenyl Isocyanate Teicoplanin with Phenyl Isocyanate Teicoplanin Chiral Stationary Phase Using RP-HPLC
- Pages: 157-162
- First Published: 16 January 2012

Two chiral stationary phases (CSP), phenylisocyanate teicoplanin CSP (Phe-TE), and 3,5-dimethylphenyl isocyanate teicoplanin CSP (DMP-TE) were prepared from the macrocyclic glycopeptide teicoplanin CSP (TE) using derivative agents, phenyl isocyanate or 3,5-dimethylphenyl isocyanate, respectively. The evaluation and comparison of these two self-made CSP were performed using HPLC enantiomeric separations. Eight α-amino acids reached enantioseparation using the RPLC mobile phase. The chiral selectivity factor for six α-amino acids on DMP-TE is somewhat bigger than that on Phe-TE CSP under RP mode.
Nitrite Ionic Liquids (IL-ONO and [bmim]NO2) as Effective Nitrosonium Sources for the Synthesis of α-Oximinoketones under Mild Heterogeneous Conditions
- Pages: 163-166
- First Published: 16 January 2012
Fabrication of a Sensitive Electrochemical Biosensor for Detection of DNA Hybridization Based on Gold Nanoparticles/CuO Nanospindles Modified Glassy Carbon Electrode
- Pages: 167-172
- First Published: 16 January 2012
A Novel Sandwich-type Dinuclear Complex for High-capacity Hydrogen Storage
- Pages: 173-176
- First Published: 16 January 2012

From density functional theory calculations, we predicted that the sandwich-type dinuclear organometallic compounds Cp2Ti2 and Cp2Sc2 can adsorb up to eight hydrogen molecules respectively, corresponding to a high gravimetric storage capacity of 6.7% and 6.8% (w), respectively. These sandwich-type organometallocenes are favorable for reversible adsorption and desorption of hydrogen at ambient conditions.
Synthesis, Characterization and Ion Exchange Properties of a New Composite of Inorganic Ion Exchanger: Polyacrylonitrile Cerium(IV) Molybdophosphate
- Pages: 177-182
- First Published: 16 January 2012
Spectrofluorimetric and Spectrophotometric Stability-Indicating Methods for the Analysis of Veralipride in Presence of Its Degradants and in Spiked Human Plasma
- Pages: 183-189
- First Published: 16 January 2012
Notes
N-Heterocyclic Carbene-Catalyzed [2+2+2] Annulation of Allenoates with Trifluoromethylketones
- Pages: 190-194
- First Published: 23 December 2011
Synthesis of 2,2-Bis-C-functionalized Chain Glucosid-3-ketals
- Pages: 195-198
- First Published: 23 December 2011
Methenamine as an Efficient Ligand for Copper-catalyzed Coupling of Phenols with Aryl Halides
- Pages: 199-203
- First Published: 23 December 2011

Methenamine was found to be an efficient, inexpensive and facile ligand for the CuX-catalyzed O-arylation of phenols with aryl iodides and bromides. The present protocol is applicable to a variety of phenols and aryl iodides containing electron-withdrawing, electron-donating, and sterically demanding substrate combinations under mild conditions.
Erratum
Erratum: Aldol Condensation and Michael Addition of 4,4-Dimethylcyclohexane-1,3-dione and Aromatic Aldehydes. Unconventional Substituent Effects
- Page: 204
- First Published: 16 January 2012