中国化学快报

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SYNTHESES OF METHYL-AND ETHYL-VINYL SULFOXIDES AND THEIR APPLICATIONS TO MEMBRANE MATERIALS FOR GAS SEPARATION

Dong Lin JIANG, Yi Feng ZHANG, Hong Jie FU, Zhi Quan SHEN

中国化学快报. 1992, 3(02): 79-82.

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Methyl-and Ethyl-vinyl sulfoxides (MVSO and EVSO) were first synthesized from common organic reagents, i.e. sulfate, thiourea and ethylene oxide in excellent yields. A new facile method for oxidation of vinyl sulfides to corresponing vinyl sulfoxides was developed. Application of those vinyl sulfoxides for synthetic gas separation membranes was acheived and that showed the high permselectivities to SO₂, N₂ and SO₂/N₂ mixture gases.

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RELATIVE REACTIVITIES OF POLYHALOFLUOROALKANES TOWARD HALGPHILIC ATTACKS

Xing Ya LI, Ming Hu TU, Xi Kui JIANG

中国化学快报. 1992, 3(02): 83-86.

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Relative reactivities of polyhalofluoroalkanes toward bromophilic or chlorophilic attacks have been evaluated for the first time by comparing the rates of halophilic attacks by a carbanion derived from the addition of a nucleophile to an olefin with the rate of β-elimination of the same carbanion intermediate. Relative reactivity orders of some polybromofluoroalkanes and polychlorofluoroalkanes are CF₂Br₂ > CF₃CFBr₂~CF₂BrCF₂Br > CF₃CBr₃, and CCl₄ > CF₃CCl₃ > CF₂ClCCl₃ > CFCl₃ > CFCl₂CFCl₂~CF₂ClCFCl₂. Early transition states for halophilic attacks are speculated.

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HIGH NUCLEOPHILICITY OF FORMATE TOWARD POLYHALOFLUOROALKENES

Chang Ming HU, Ming Hu TU

中国化学快报. 1992, 3(02): 87-90.

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High nucleophilicity of formate toward polyhalofluoroalkenes under acidic condition is described. This reaction offers a convenient method for the synthesis of E-α,β-unsaturated polyhalofluorocarboxylic acids.

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A STEREOSELECTIVE TOTAL SYNTHESIS OF (S)-(+)-γ-CURCUMENE

Zhi Xian WANG, Zhong Ying CHEN

中国化学快报. 1992, 3(02): 91-92.

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The stereoselective total synthesis of (S)-(+)-γ-curcumene starting from p-bromo-phenylmethyl ether via an asymmetric Grignard cross-coupling reaction in 45%ee optical yield was described.

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SYNTHESIS,CHARACTERIZATION AND BIOLOGICAL ACTIVITY OF TRANSITION METAL COMPLEXES WITH 5-HYDROXY-7, 4'-DIMETHOXYFLAVONE

Fang Jie ZHANG, Shuang Xi WAN,G Yu Lin LI

中国化学快报. 1992, 3(02): 93-94.

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Complexes of Cu^Ⅱ, Ni^Ⅱ, Co^Ⅱ, Zn^Ⅱ, Fe^Ⅲ, Cr^Ⅲ, Cd^Ⅱ and Mn^Ⅱ with the natural product 5-hydroxy-7,4'-dimethoxyflavone (1) have been prepared and their probable structures were proposed on the basis of elemental analyses, thermal analyses and IR and UV spectral data. The ligand and all the complexes were tested in vitro for their antibacterial activity.

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PRELIMINARY STUDIES ON THE KINETIC RESOLUTION OF METHYL ERYTHRO-PHENYLGLYCERATE AND METHYL t-EPOXYCINNAMATE BY PLE

Jin Fa DU, Jin ZHOU, Liang HUANG

中国化学快报. 1992, 3(02): 95-96.

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PLE (pig liver esterase) catalyzed hydrolysis of the title compounds demonstrated that the α-carbon with S configuration hydrolyzed faster than the R configuration and α-carbon controlled the stereoselectivity. The preliminary results showed that the highest ee obtained were only 40-48%.

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ELECTROCARBOXYLATION OF ORGANIC COMPOUNDS WITH CARBON DIOXIDE CATALYZED BY METALLOPORPHYRINS (Ⅰ)——CATALYTIC ACTIVITIES OF METALLOPORPHYRINS FOR ELECTROCARBOXYLATION OF BENZYL CHLORIDE

Guo Dong ZHENG, Qing Da AN, Qing DING, Xiao HAN, Xi Zhang CAO

中国化学快报. 1992, 3(02): 97-98.

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The electrocarboxylation of benzyl chloride with CO₂ catalyzed by metalloporphyrins and the effects of different kinds of central metals and ligands on catalytic activities are reported. These metalloporphyrins whose central metals can form corresponding M (Ⅰ) complexes such as CoTPP, FeTPP have high activities. With water-soluble porphyrin ligands such as TPPS, TTMAPI, the corresponding metalloporphyrins have high catalytic activity. Electron-with-drawing groups on the porphyrin ring cause the lowering of activity.

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SCF-CNDO/2-CO STUDY ON NITROGEN-CONTAINING ANALOGS OF POLYACETYLENE

Jie FU, Yuan He HUANg, Ruo Zhuang LIU

中国化学快报. 1992, 3(02): 99-102.

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The electronic structures of polymethineimine (PMI), polyazine (PAZ) and polyazoethene(PAE) are studied on the basis of the tight-binding LCAO-8CF-CO calculations under the CNDO/2 approximations. Our result indicates that they are all poor candidates for new electric conducting materials as alternatives to polyacetylene (PA), and this is discussed in terms of the electronic structures.#br#PMI end PAZ have been synthesized successfully ^(1,2), and some of their properties have been investigated. In this article we intend to explain why and how degree of conjugation effects on their intrinsic electric conductivities by studying their electronic structures on the basis of the tight-binding LCAO-SCF-CO calculations including all valence atomic orbitals(AO'S) with complete neglect of differential overlap(CNDO/2) approximations^(3,4).

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STUDIES ON THE KINETICS AND INITIATION MECHANISM OF ACRYLAMIDE POLYMERIZATION USING CERIC/ACETOACETANILIDE SYSTEM AS INITIATOR

Jian Hua DONG, Kun Yuan QIU, Xin De FENG

中国化学快报. 1992, 3(02): 103-106.

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It is found that acetoacetanilide possesses very high promoting reactivity towards ceric ion in initiating polymerization of vinyl monomer. The kinetics of acrylamide polymerization and the activation energies were studied. The initiation mechanism of ceric/acetoacetanilide is proposed on the basis of experimental results of FT-IR and ESR.

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STUDY ON THE STRUCTURE AND PROPERTIES OF 4-(2-PYRIDYLAZO)-RESORCINOL(PAR) AND ITS DERIVATIVES

Feng Lin ZHAO, Ying LIANG, Yong Qing ZHANG, Shen Yang TONG

中国化学快报. 1992, 3(02): 107-108.

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The dissociation constants of the reagents were determined spectrophotometrically, the existential patterns of PAR in aqueousalcohol solution were studied by quantumchemical method, and the color reactions between these reagents and Nickel (Ⅱ) were investigated.

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APPLICATION OF MICROWAVE IRRADIATION TO THE SYNTHESIS OF SOME ALKALI METAL METAVANADATES

Wen Guo XU, Ai Min YU, Jun LIU

中国化学快报. 1992, 3(02): 109-110.

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Application of microwave irradiation to the syhthesis of some alkali metal metavanadates in a fraction of time required by the conventional synthetic method (2min for LiVO₃, 3.5min for NaVO₃) is described.

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A NOVEL GALLOTANNIN FROM RHODIOLA CRENULATA

Wen Sheng YU, Xin Min CHEN, Hong LI, Lei YANG, Yu Fei LI, Li Sheng DING

中国化学快报. 1992, 3(02): 111-112.

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A novel gallotannin, crenulatin (1), was isolated from the stem of Rhodiola crenulata, and its structure was determined by means of spectral analyses(including ¹H-¹H COSY, ¹H-¹³C COSY and ¹H-¹³C COLOC spectral measurements)and chemical evidence.

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STUDIES ON DITERPENE-QUINONES OF TRIPTERYGIUM REGELII SPRAGUE

Jian Hua SHEN, Bing Nan ZHOU

中国化学快报. 1992, 3(02): 113-116.

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Six new diterpene-quinones were isolated from the ethanol extract of the roots of Tripterygium regelii Sprague and their structures were elucidated through interpretation of their spectroscopic data and chemical correlations. The absolute configuration of triptoquinonoic acid A (1) was determined by X-ray crystallography.

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A NEW CYCLOARTANE TRITERPENE FROM ARTEMISIA ARGYI¹

Ren Xiang TAN, Zhong Jian JIA

中国化学快报. 1992, 3(02): 117-118.

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The chemical investigation of the aerial parts of Artemisia argyi gave α and β-amyrin, friedelin and a new cycloartane derivative whose structure was established, on the basis of its spectral and chemical evidences, as 3β-methoxy-9β, 19-cyclolanost-23(E)-en-25, 26-diol (1).

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CLEMOCHINENOSIDE A, A MACROCYCLIC COMPOUND FROM CLEMATIS CHINENSIS

Chun Qing SONG, Ren Sheng XU

中国化学快报. 1992, 3(02): 119-120.

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The structure of a new macrocyclic compound, clemochinenoside A obtained from Clematis chinensis was identified by NMR, FAB-MS, NOE and chemical hydrolysis.

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A NOVEL NEOLIGNAN, BIONDININ A, FROM MAGNOLIA BIONDII PAMP

Yu Liang MA, Gui Qiu HAN

中国化学快报. 1992, 3(02): 121-122.

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A novel neolignan, biondinin A, was isolated from the flower buds of Magnolia biondii Pamp. The structure was established as 3,3',4'-trimethoxy-4,9'-dihydroxy-6.8',9-O-7'-neolignan. It is the first reported neolignan possessing the skeleton of benzo-oxa-cyclooctane.

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CONFORMATIONAL CHANGE IN MESOGENIC CORES OF DISCOTIC LIQUID CRYSTALS

Xiao Zhen YANG, Qun LU, Ye CHAI, Shan Nong ZHU, Fu Zhou WU, Rong Ben ZHANG, Ying Yan JIANG

中国化学快报. 1992, 3(02): 123-126.

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Infrared spectra of bis (β-diketonato) copper (Ⅱ) complex liquid crystals with different flexible chain lengths (the carbon number=12 and 14) have been studied as a function of temperature. Conformational changes in mesogenic cores of the molecules have been characterized by using the out-of-plane bending vibration mode of aromatic C-H bonds. The result shows that for the phenylene rings and the chelate rings of the molecules there occurred an enhancement of extended conjugation of the two π-electron systems during phase transitions, which was also supported by UV measurements. It suggests that the big quasi-planar core structure in the discotic complex consisted of four phenylene rings and the central chelate rings is not maintained in every phase.

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EFFECT OF SOLVENT ON SURFACE ENHANCED RAMAN SCATTERING SPECTRA OF COLLOIDAL SILVER

Ren Ao GU, Zhang Fei HE, Xiao Kun HU, Ban Dong DING

中国化学快报. 1992, 3(02): 127-128.

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The effect of solvent on surface enhanced Raman scattering (SERS) of colloidal silver has been studied. Experiments show that the intensity of SERS is related to the polarity and molecular constitution of the solvent. The influence of solvent is due to the change of the adsorption quantity and adsorption intensity.

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INVESTIGATION OF THE MIDDLE REDOX PEAK OF POLYANILINE ON THE CYCLIC VOLTAMMOGRAM

Shao Jun DONG, Dong Bo ZHANG, Zhuang LI

中国化学快报. 1992, 3(02): 129-132.

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The middle peak which appeared frequently on the voltammetric curves has been interpreted as the degradation of the polymer, according to the results of anion effect. When α-CD (α-cyclodextrin) was added in the acidic solution of aniline to form aniline-α-CD complex, the middle peak became even higher during electrochemical polymorization. This suggests that the middle peak is mot originated from cross-link or ortho-polymerization in aqueous acidic solution.

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PROMOTION EFFECT OF PYRIDINE FOR THE DIRECT ELECTROCHEMISTRY OF CYTOCHROME C AT GOLD ELECTRODES

Chen Li ZHOU, Xiao Gang QU, Tian Hong LU, Shao Jun DONG, Therese M. COTTON

中国化学快报. 1992, 3(02): 133-134.

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It was found for the first time that the compounds with only one functional group, such as pyridine, can show the promotion effect for the electrochemical reaction of cytochrome C at gold electrodes.

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STUDY ON THE SECOND HARMONIC GENERATION OF SOME LANTHANIDE (Ⅲ) COORDINATION COMPOUNDS

Jia Fu WANG, Meng Hui CAI, Cheng YE, Zhi Ming FENG

中国化学快报. 1992, 3(02): 135-136.

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The measurements of second harmonic generation efficiencies of some coordination compounds of lanthanide (Ⅲ) carboxylates and β-diketonates have been reported. The results show thatmost of lanthanide cinnamate have SHG activity.

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SOLID STATE ²⁷AL MAS-NMR STUDY OF POLYOXY-ALUMINUM PILLARED MONTMORILLONITE

Si Fen XIANG, Tong Wen HUA, Qing JIANG, Lian Bo WANG

中国化学快报. 1992, 3(02): 137-138.

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Solid state magic-angle-spinning nuclear magnetic resonance spectroscopy (MAS-NMR) has been used to probe the signal of ²⁷Al in polyoxyaluminum pillared montmorillonite. The experimental results show that the polyhydroxy polymers are indeed the pillaring species.

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THE ELECTROCHEMICAL BEHAVIOUR OF THE NEW VANADIUM BRONZE (Li₃V₅O₁₅) CATHODE IN SECONDARY LITHIUM BATTERY

Shou Nan HUA, Neng Zuo JIANG

中国化学快报. 1992, 3(02): 139-140.

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A new kind of vanadium bronze with rich lithium (Li₅V₅O₁₅) was prepared from Li₂CO₃ and V₂O₅ at 680℃ for 24 hrs. The charge and discharge curves of bronze electrode were determined in organic electrolyte. One mole of this material could be incorporated up to 4 mole lithium at 0.2mA/cm² and 1.0V cut-off voltage, corresponding capacity about 340Ah/kg. Compared with the cell of Li/Li_1+xV₃O₅ the cell of Li/new bronze had higher capacity, smoother discberge curve, but lower plateau voltage (about 1.8V). The cycling behaviour of this material was good. The electrode insertion reaction was controlled by the lithium diffusion process in the bronze. This new bronze could be used for low voltage rechargeable lithium battery.

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STUDY ON THE nd^a METAL REPLACED YBa₂Cu_3-XM_XO_7-Y

Jian MENG, Yu Fang REN

中国化学快报. 1992, 3(02): 141-144.

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A systematic study of the structural and superconducting behavior of the high Tc compounds YBa₁Cu_1.9M_0.1O_7-y has been performed where M=Ti, V, Mn, Fe, Co, Ni, Zn, Zr, Nb, Mo, In and Sn. Structural analysis shows that most replacements somewhat modify the YBa₂Cu₃O_7-y lattice parameters in the orthorhombic structure, with the exception of Fe and Co which transit into tetragonal phase. Although the 1D Cu-O chains are destroyed, the depressed Tc remain within 73 to 76K in the case of Fe and Co. However. the substitution of Ni and Zn on the Cu₂ sites appears to strongly decrease Tc whereas their structure remains orthorhombic. This indicates that the 2D Cu-O planes play a very important role in the transportation of superconducting electrons but the 1D Cu-O chains play a role not only in supplying carrier number but also in coupling the Cu-O planes.

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STUDY OF THE FLUORESCENCE ENHANCEMENT IN THE SYSTEM OF EUROPIUM-OR SAMAR-IUM-TERBIUM-DIBENZOYLMETHANE-CETYLTRIMETHYLAMMONIUM BROMIDE-TRITON X-100 AND ITS APPLICATION

Zhi Kun SI, Gui Yun ZHU, Wei JIANG, Bin ZHANG, Ning SONG

中国化学快报. 1992, 3(02): 145-148.

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A fluorescence enhancement phenomenon on adding terbium to the Eu or Sm-DBM-CTMAB-Triton X-100 fluorescence system was observed. The fluorescence intensity of this system was 50 times greater than that of the system without terbium at pH 9.0. The fluorescence intensity is a linear function of the concentration of europium or samarium in the range of 1.0×10^-10-8.0×10^-6 mol/L and 1.0×10^-7-8.0×10^-6 mol/L, respectively. The deteetion limits for them were 1.0×10^-12 mol/L and 1.0×10^-9 mol/L, respectively. This system was used for the determination of europium or samarium in rare earth samples with satisfactory results.

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STUDY OF CARBON MONOXIDE HYDROGENATION OVER SUPPORTED IRON CLUSTER CATALYSTS

Jin Gang WU, Wei Xu ZHAI, You Mei HUANG, Shan Zhi WENG Lanzhou

中国化学快报. 1992, 3(02): 149-152.

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Fe₃ (CO)₁₂-derived Fe/r-AL₂O₃ and Fe/zeolite catalysts have higher catalytic activity than those derived from Fe(NO₃)₃. The existence of metal-metal bond in cluster species and the congruity of the adsorption of CO and H₂ are important for increasing the catalytic activity. Carbon deposition for Fe₅C(CO)₁₅-derived Fe/r-AL₂O₃ catalyst is discussed.

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MOLECULAR BEAM STUDIES ON OXIDATION OF CO ON Pd WITH DIFFERENT MIXED RATIOS OF P_CO TO P_O2

Guang Kang XI, Guo Hua LIU, Geng Yu CAO, Sheng Lin LI

中国化学快报. 1992, 3(02): 153-156.

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Here some steady-state experiments on oxidation of CO on Pd were performed on a molecular beam apparatus. It is found that the characteristics of the rate of CO₂ formation r versus substrate temperature T are dependent on the ratio P=P_CO/P_O2 in the mixed beam. These characteristics are related to the complicated interactions of co-adsorbed CO and O particles on Pd surface.

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1992年, 第3卷, 第02期　刊出日期：1992-02-20

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1992年, 第3卷, 第02期 刊出日期：1992-02-20

1992年, 第3卷, 第02期　刊出日期：1992-02-20