中国化学快报

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Indium-Mediated Addition of α-Bromoketone to Aldimines

Pei Pei SUN, Yong Min ZHANG

中国化学快报. 1997, 8(04): 267-268.

摘要 ( )

可视化

The addition reaction of ω-bromoacetophenone to aldimines by indium metal in THF-H₂O gave β-aminoketones.

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Stereochemistry of Thionation Reaction of 1,3,2-Dioxaphosphorinan-2-ones with Lawessen's Reagent

Rui Lian SHAO, Wei Shi MIAO, Guang Fu YANG

中国化学快报. 1997, 8(04): 269-270.

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The stereochemistry of thionation reaction of 2-substituted-4-aryl-5,5-dimethyl-1.3.2-dioxaphosphorian-ones 1_a-f with Lawessen's reagent (LR) was reported in this paper.The results indicated that the thionation reaction of LR proceeded predominantly with retention of configuration.The mechanism leading to retention was proposed by assuming a cyclic pentacoordinated intermidiate.

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A Simple and Novel Ipso-Bromination of 1-Bromomethyl-4-t-butyl-2,6-dimethylbenzene

Wen Chun ZHANG, Zhong Heng YU

中国化学快报. 1997, 8(04): 271-274.

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A novel ipso electrophlic substitution of 1-bromomethyl-4-t-butyl-2,6-dimethylbenzene 1 with nitric acid in alcohol,which gives ipso-bromination product of 1-bromo-4-t-butyl-2,6-dimethylbenzene 2,is described,and a possible mechanism for this reaction is investigated.

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Synthesis and Structure of 2,3-Tetra-Methylene-5,6-Trimethylene-4-Pyrone

Fan XU, Xue Qin CAO, Zhi Gang YAO, Zheng Bai CAO, Jian CHEN

中国化学快报. 1997, 8(04): 275-276.

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The title compound was synthesized by the reaction of adipyl chloride with cyclohexanone piperidine enamine and its structure was finally confirmed by the single-crystal determination in addition to conventional IR,¹HNMR and elemental analysis.

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Chemistry of Taxoid Sinenxan A:(Ⅰ) Epimerization of the 14β-hydroxyl Group

Guang Yan HUANG, Ji Yu GUO, Xiao Tian LIANG

中国化学快报. 1997, 8(04): 277-280.

摘要 ( )

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Compound 2 with 14β-hydroxyl group was successfully converted into its epimerized α-counterpart via oxidation-reduction.The elimination product (6) was auto-oxidized to epoxide 8,even in the solid state.

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A New Asymmetric Synthesis of (+)-(3R,4S,5R,7S)-Neoclausenamide via Intramolecular Nucleophilic Attack of Carbon Anion onto Cyclic Sulfate

Jian Qiang WANG, Zhu Shou LUO, Wei Sheng TIAN

中国化学快报. 1997, 8(04): 281-284.

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An intramolecular nucleophilic substitution of carbon anion to cyclic sulfate was first employed in asymmetric synthesis of (+)-(3R,4S,5R,7S)-neoclausenamide 1 which is a novel hepatoprotective lactam isolated from the dry leaves of Chinese folk medicine Clausena lansium (Lour) Skeel.The regioselectivity of β-attack to this cyclic sulfate,just like its epoxide counterpart,was attributed to the increased reactivity of β-position by the phenyl group.

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Syntheses of New Crowned Indolinospirobenzopyrans

Xin Yan WU, Cheng Tai WU

中国化学快报. 1997, 8(04): 285-288.

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Two new indolinospirobenzopyrans bearing monoaza-benzo-15-C-5 were synthesized.And they were determined by IR,¹H NMR and MS.

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First Preparation and Reactivity of γ-Oxo Vinyliminophosphorane

Ming Wu DING, Wen Fan HUNG, Hai Yang TU, Tian Jie WU

中国化学快报. 1997, 8(04): 289-290.

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The γ-oxo vinyliminophosphorane 3 was prepared for the first time from the Staudinger reaction of vinyl azide 2 and triphenylphosphine.The reactivity of 3 was studied.

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Synthetic Studies on Diarylheptanoids——Syntheses of 1,7-Bis(4-Hydroxyphenyl)-1,4,6-Heptatriene-3-One and Acetogenin G

Shi Jun DA, Ying LI, Chu Sheng HUANG, Xiao Hong LI, Yu Lin LI

中国化学快报. 1997, 8(04): 291-292.

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The two new diarylheptanoids,1,7-bis(4-hydroxyphenyl)-1,4,6-heptatriene-3-one (1) and aecrogenin G (2) were synthesized starting from 4-hydroxybenzaldehyde (3) and acetone.

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Total Synthesis of Antitumor constituent Howiinol A

Shao Yi SUN, De Quan YU

中国化学快报. 1997, 8(04): 293-294.

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Howiinol A,an active antitumor constituent from the root and stem bark of Goniothamus howii Meer.(Annoaceae) has been synthesized in nine steps from α-D-glucoheptonic γ-lactone with an overall yield of 12.4%;The absolute configuration of natural howiinol A is further confirmed.

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Studies on Semisynthesis and Anibacterial Activity of 7 β-(5-Methyl-1-Aryl-1H-1,2,3-Triazoly-4-Carboxamido) Cephalosporins

Zi Yi ZHANG, Yu Xiang LIANG, Zuo Wu GUAN

中国化学快报. 1997, 8(04): 295-298.

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Nine new derivatives of 7 β-(5-methyl-1-aryl-1H-1,2,3-triazoly-4-carboxamido) cephalosporins were synthesized by acylation of 7 β-amino group of 7-ACA,7-ADCA and 7-ACT with 5-methyl-1-aryl-1H-1,2,3-triazoly-4-formyl chloride.The structure of the compounds were confirmed by elementary analysis IR,¹HNMR and FAB-MS.Some of them showed significant antibacterial activity.

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The Hydrolysis of RNA by Histidine

Xiang Hong LI, Rong WAN, Yu Fen ZHAO

中国化学快报. 1997, 8(04): 299-302.

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The cleavage activity of histidine on RNA and DNA was tested.It was found that histidine could cleave RNA,but not DNA.The cleavage mechanism was proposed to be involved in the hydrolysis of the phosphodiester backbone.

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Formation of Oligosaccharide from Monosaccharide by Pentacoordinate Oxyphosphorane

Dong Yan QIN, Yong JU, Yu GUO, Yu Fen ZHAO, Qin Zhu WANG

中国化学快报. 1997, 8(04): 303-304.

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Oxyphosphorane reacted with glucose to give disaccharide which was confirmed by FAB-MS and ¹³C-NMR.The mechanism for formation of oligosaccharides through the participation of phosphorus was proposed.

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Synthesis of New Benzyl Substituted Titanocene Complexes and Their Novel Intramolecular Cyclization

Yan Long QIAN, Ji Ming YANG, Wei Quan SUN, Yuan LING, Ji Ling HUANG

中国化学快报. 1997, 8(04): 305-308.

摘要 ( )

可视化

the synthesis of seven new benzyl substituted titanocene complexes and their novel intramolecular cyclization promoted by halides is reported.

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The Intercalative Binding Between Rivanol and DNA

Wen You LI, Jin Gou XU, Xiang Qun GUO, Qing Zhi ZHU, Yi Bing ZHAO

中国化学快报. 1997, 8(04): 309-312.

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可视化

Rivanol(RVN) binds to the double helical DNA with a high affinity.Strong hypochromism and appreciable red shifts in the absorption spectra can be observed when RVN binds to CT DNA.The results of absorption spectra,KI quenching studies,fluorescence polarization measurements,competitive binding studies,and thermal denaturation experiments suggested that the interaction between RVN and DNA be intercalative.

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Melaxillarinine,a New Bisindole Alkaloid from Melodinus axillaris

Ke Xu YAN, Xiao Zhang FENG

中国化学快报. 1997, 8(04): 313-314.

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A new bisindole alkaloid,melaxillarinine,was isolated from the roots of Melodinus axillaris.Its structure was established on the basis of spectral analysis.

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A New Benzofuranosesquiterpene Dimer from Ligularia Virgaurea

Bin Gui WANG, Zhong Jian JIA

中国化学快报. 1997, 8(04): 315-316.

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A new benzofuranosesquiterpene dimer,named virgaurin B,has been isolated from the roots of Ligularia virgaurea and its structure has been elucidated by spectroscopic evidence.

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New Prenylated flavonol from Hypericum japonicum

Qing Li WU, Yong Hong LIAO, Sheng Ping WANG, Li Wei WANG, Yu Xiu FENG, Jun Shan YANG, Pei Gen XIAO, Shao Liang HONG

中国化学快报. 1997, 8(04): 317-318.

摘要 ( )

可视化

One new prenylated flavonol,7,8-(2",2"-dimethylpyrano)-5,3',4'-trihydroxy-3-methoxylflavone was isolated from Hypericum japonicum.The chemical structure was determined by spectroscopic methods.

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Kinetics of Protonolysis of o-Substituted Phenylmercuric Chlorides by HCl(NaI) in Ethanol

Yu Lan WANG, Yang Jie WU

中国化学快报. 1997, 8(04): 319-322.

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可视化

The kinetics of protonolysis of o-substituted phenylmercuric chlorides,o-XC₆H₄HgCl (X=H, CH₃, CH₃O, C₂H₅O, CF₃, COOC₂H₅, Cl, Br, F, NO₂), by hydrochloric acid in the presence of sodium iodide as catalyst have been studied in ethanol.The reaction has been found to be second order overall,first order in each reactant.The rate constants k measured at the same temperature may be arranged in the following order: C₂H₅O > CH₃O > CH₃ > H > CO₂C₂H₅ > F > Cl > Br > CF₃ > NO₂.

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Theoretical Study on the Structures,Vibrational Spectra,and the Nature of the Intermediate Hydrogen Bond of Schiff Bases

Yong ZHANG, Cun Yuan ZHAO, Xiao Zeng YOU

中国化学快报. 1997, 8(04): 323-326.

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可视化

Semi-empirical method PM3 was used to study the geometry and vibrational spectrum of N-(2-hydroxy-1-naphthyl-methylene)-1-pyrenamine (NPY) with the intermediate hydrogen bond.Results are comparable to experimentations.Based on results of both NPY and its model,N-(2-hydroxy-1-naphthyl-methylene) aniline.it was found that the N-(2-hydroxy-1-naphthyl-methylene) group is principally responsible for the special hydrogen bonding through conjugation effect.

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Local Dielectric Constant of the Solvent Shell Surrounding Ethyl Acetoacetate in Cosolvent-Modified Supercritical Carbon Dioxide

Jie LU, Jie KE, Bu Xing HAN, Hai Ke YAN

中国化学快报. 1997, 8(04): 327-330.

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The enol contents and equilibrium constants for keto-enol tautomerism of ethyl acetoacetate in supercritical (SC) CO₂ with and without cosolvent ethanol and in various liquid solvents were investigated by UV spectroscopy.The local dielectric constant about the solute in SC CO₂/ethanol system was obtained through the correlation between Gibbs free energy of tautomerism and Onsager-Kirkwood solvent quantin.The great difference between local dielectric constant and that calculated from homogeneous dielectric medium theory suggests clustering of the cosolvent around the solute.

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Study on New Spectrophotometric Determination of Vanadium(V) with Chlorpromazine

Yu Biao WANG, Qian Rong LI

中国化学快报. 1997, 8(04): 331-334.

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By using chlorpromazine as a new color reagent,spectrophotometric reactions with vanadium(Ⅴ) have been studied.In the medium of 0.25 mol·L^-1 of H₂SO₄,chlorpromazine reacts with vanadium(Ⅴ) at room temperature to form a bright red complex,which exhibits a maximum absorption at 520 nm.Beer's law is obeyed in the concentration range of 0-2 μg and 2-40 μg V(Ⅴ)/10mL with molar absorptivities of 5.10×10³ and 1.02×10⁴L·mol^-1·cm^-1,respectively.

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Datection of Carboxylic Acid Vapours Using Piezoelectric Crystals with Crown Ether Coatings

Li Shi WANG, Hong Mei WEI, Wei Qi MA, Bao Gui ZHANG, Jian Xing FENG, Guo Xi WANG

中国化学快报. 1997, 8(04): 335-338.

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This work describes three crown ether-coated piezoelectric crystal sensors for detection of carboxylic acid vapours.All three have excellent reproducibility and stability (lasting for at least 100 days).Two of them show good sensitivity (137-1500Hz/mg/L) and high selectivity.Cis-diamino-dibenzo-18-crown-6 can be used as the coating material for the detection of formic acid.The effect of crown ethers structure on the detection sensitivity and selectivity for acid vapours was discussed.

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Comparison of Four Deoxygenation Techniques for Cyclodextrin Induced Room Temperature Phosphorescence

Hai Rong ZHANG, Yan Sheng WEI, Wei Jun JIN, Chang Song LIU

中国化学快报. 1997, 8(04): 339-342.

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The traditional deoxygenation techniques for cyclodextrin induced room temperature phosphorescence (CD-RTP) include N₂(g) purging and Na₂SO₃ chemical deoxygenation.In this paper,with 1-bromocyclohexane (1-BrCH) as an external heavy atom perturber,7,8-benzoquinoline (7,8-BQ) was used as a model compound,hydrogen and carbon dioxide are used for deoxygenation in CD-RTP and compared with two traditional deoxygenation techniques.The results show that the new deoxygenation techniques have obvious advantages such as simpler facilities,faster speed of deoxygenation and wider acidity range etc.

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Abnormal IR Spectra of CO Adsorbed on the Surface of Glass Carbon Electrode Modified with Polypyrrole Film with Platinum Microparticles

Hui YANG, Tian Hong LU, Kuau Hong XUE, Guo Qiang LU, Shen Pei CHEN, Shi Gang SUN

中国化学快报. 1997, 8(04): 343-344.

摘要 ( )

可视化

Abnormal IR spectra of CO adsorbed at the surface of glass carbon electrode modified with polypyrrole film with Pt microparticles are reported.

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Molecular Imprinting of (R)-(+)-α-Methylbenzylamine for Chiral Stationary Phase

Zi Hui MENG, Liang Mo ZHOU, Qing Hai WANG, Dao Qian ZHU

中国化学快报. 1997, 8(04): 345-346.

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可视化

A new type of molecular imprinting stationary phase was prepared by using R-(+)-α-methylbenzylamine as the print molecule.Experiments of high performance liquid chromatography show that the new stationary phase has high enantio-selectivity and discriminates (R,S)-(±)-α-methylbenzylamine successfully with α value of 1.67.

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CAS-MCSCF Study on the Ground State of the Ditungsten Molecule(W₂)

GUO Liang LI, Xue Yan TU, Shu Shan DAI

中国化学快报. 1997, 8(04): 347-350.

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可视化

Complete active space multiconfiguration self-consistent-field (CAS-MCSCF) calculations are carried out on the ground state(¹∑_g⁺) of W₂.The spectroscopic properties (R_e=2.078A. D_e=4.224eV and ω_e=304.3cm^-1) and the potential energy curve of the ¹∑_g⁺ state are reported.The calculations predict the W-W bond order of 5.02.

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Electronic Structure Calculation for Co₆(μ₆-C)(μ₃-S)₂(CO)₁₂ Cluster

Wen LI, Ye LIU, Yuan Qi YIN

中国化学快报. 1997, 8(04): 351-352.

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The electronic structure of Co₆(μ₆-C)(μ₃-S)₂(CO)₁₂ molecule has been calculated by DV-Xα method.The results show that the reaction mechanism of CS₂ and Co₂(CO)₈ in synthesis seems only to undergo the additive and decarbonyl processes.The other result worthy of being mentioned is the calculated atomic charges that are Co0.3+,S1.29+,μ₆-C1.16-,C0.06- and O0.21-.S atom has not only the positive charge but also four times as much as that of Co atom.This is not in accordance with the electronegativities of 1.7 and 2.5 respectively for Co and S atom.

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The Synthesis,Luminescence and Energy Transfer of the Binary and Ternary Complexes of Rare Earth with Aminobenzoic Acids and 1,10-Phenanthroline

Bing YAN, Hong Jie ZHANG, Jia Zuan NI

中国化学快报. 1997, 8(04): 353-356.

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可视化

Thirteen kinds of binary and ternary complexes of rare earth (Gd,Eu,Tb) with ortho (para) aminobenzoic acid and 1,10——phenanthroline were synthesized and characterized.The phosphorescence spectra and lifetimes of gadolinium complexes were measured and the lowest triplet state energies of ligands and the energy transfer efficiencies between ligands were determined.The luminescence properties and intramolecular energy transfer of these complexes were studied in details.

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Investigation of the Interaction between Nafion and Several Trisbipyridyl Complexes by Spectroscopic Method

Yan Bing ZU, Pei Fang LIU, Chuan Sin CHA, Xi LI

中国化学快报. 1997, 8(04): 357-360.

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In this paper,evidences of strong interaction between several tris-bipyridyl complexes and Nafion matrix are provided by UV-VIS and FTIR spectra.The studied counterions also show electrosiatic interaction with the bonded -SO₃^- groups,as indicated by the shifting of γ_Sso₃^- to lower wave number.The most probable location of these complexes seems to be near the interface between the fluorocarbon back bone and the ionic cluster region.

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1997年, 第8卷, 第04期　刊出日期：1997-04-20

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1997年, 第8卷, 第04期 刊出日期：1997-04-20

1997年, 第8卷, 第04期　刊出日期：1997-04-20