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    24 October 1987, Volume 8 Issue 10
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    Articles
    A Study of Oxidation of Complex of Cobalt(Ⅱ) with Bis(2-Ethylhexyl)Dithiophosphoric Acid
    Huang Jinwang, Xia Jingmou, Yang Xueqiang, Chen Meiyan, Ji Liangnian
    1987, 8(10):  863-866. 
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    The oxidation of the complex of cobalt (Ⅱ) with bis(2-ethylhexyl) dithio-phosphoric acid has been studied by means of UVspectra, infrared spectra, and magnetic susceptibility. The results revealed that there is a σ-π bond between cobaltous and sulfur atoms.The cause of oxidation of the complex was interpreted in terms of the electronegativity.
    Studies on the Syntheses and Structures of a Novel Family of Microporous Gallophosphates
    Feng Shouhua, Xu Ruren
    1987, 8(10):  867-868. 
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    A novel family of gallophosphate molecular sieves (namely GaPO4-Cn,n=1-12) was synthesized in R-Ga2O3-P2O5-H2O systems (R=organic templating agents.) and characterized by means of XRD, IR, chemical composition analysis, gas adsorption and MAS NMR techniques. The crystal structures of GaPO4-C3and GaPO4-C4were determined by Single Crystal X-ray Diffraction. The various gallophosphate molecular sieves have intracrystalline adsorption pore sizes from 3 to 6 Å.
    Studies on the Preparation and Characterization of the Adducts of the Ce(Ⅳ)-PMBP Coordination Compound
    Chen Botao, Wang Mingzhao
    1987, 8(10):  869-872. 
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    The coordination compound of cerium(Ⅳ) with PMBP(1-phenyl-3-methyl-4-benzoyl-pyrazolone-5), Ce(Ⅳ)A4(A:PMBP), and its adducts, CeA4·L(L=2, 2-dipyridine (Dipy), 1,10-phen-anthroline(Phen), tri-n-butylphosphine oxide(Tbpo) and triphenylphosphine oxide(Tppo) respectively) have been prepared. The molar conductiveties,thermogravimetric curves,IRspectra, electronic spectra and 1H-NMR spectra were examined. These desired adducts, CeA4·L, were confirmed by the above experimental data. The order of thermostability of adducts is CeA4·Phen> CeA4·Dipy>CeA4·Tbpo≈CeA4·Tppo.
    The Determination of Formation Constants of 1-Thio-β-D-Glucopyranose-M(Ⅱ) Coordination Compounds and the Probability as Detoxication Agent
    Guo Dewei, Fan Chunmei, Chen Jingtang, Liu Xueyuan, Chang Wei
    1987, 8(10):  873-875. 
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    The protonation constant of l-thio-β-D-glucopyrancse(L) and the stepwise formation constants of L-Pb(Ⅱ), L-Cd(Ⅱ) and L-Zn(Ⅱ) coordination compounds were determined at constant ionic strength(I=0.15), T=298.15K. The percentage of Pb (Ⅱ)or Cd(Ⅱ) present in ML2, in octanol was determined by atomic absorption Spectrophotometry. The probability of using it as detoxication agent is discussed,
    Cerium(Ⅲ)-Triethylenetetraminehexaacetic Acid (TTHA)Complex and Its Application to the Derivative Spectrophotometric Determination of Cerium in Mixture of Rare Earth Oxides
    Xu Zhongjun(Hsu Chung-gin), Pan Jiaomai
    1987, 8(10):  876-878. 
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    TTHAformed a 1:1 complex with cerium (Ⅲ ) at pH5.5 that showed an absorption maximum at 279 nm with a molar absorptivity of 8.18×102l·mol·cm-1. Most of the rare earths and scandium in 10-fold amounts do not interfere. The second-derivative spectrum recorded from 320 to 240nm can be used to determine 5-80ppm of cerium. The method was applied to the determination of cerium in the mixtures of rare earth oxides with satisfactory results.
    A Simple Analytical Method for Chromium Electroplating Solution
    Yong Ping, Wang Baojun, You Daheng
    1987, 8(10):  879-881. 
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    A new method for the complete analysis of chromium electroplating solution is described. Only a single acid-base titration was used. Results were calculated by a set of empirical equations,which were deduced by the author.
    Studies on Nicotine Graphite Coated-Membrane and PVC Membrane Selective Electrodes
    Dai Ziqin, Xie Jinlun, Su Xuesu, Li Wanyi
    1987, 8(10):  882-884. 
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    In this paper, the construction and analytical applications of tetraphenylboratc-nicotine graphite coated-membrane and PVCmembrane selective electrodes arc described, These electrodes exhibit, near-Nernstian response to nicotine from 10-4to 10-1M, in the pHrange of 6-7 and are sufficiently selective for the determination of nicotine in tobacco products without any prior separation. Comparing with all established methods, including liquid-membrane electrode method, this coated-membrane electrode potentiometric method is relatively simple, convenient and inexpensive construction, and gave satisfactory results.
    Studies on the Reaction of Amindines with α-Chloro-α,β-Unsaturated Nitriles
    Dong Lingjiao, Liu Simiag, Zhang Lihe, Wang Xu
    1987, 8(10):  885-890. 
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    In this paper the reactions of amindines with-α-chloro α,β- unsaturated nitriles are reported. The reaction products were separated by preparative TLCon silica gel and eluted with ethylacetate. Fifteen products were obtained, among them eleven compounds were unknown. Their structures were determined by UV, 1HNMR and MS. The result showed that different reaction products were obtained when different solvents were used.
    Effects of Solvents on UV Spectra and FL Spectra for 1,4-Bis(Benzoxazol-2-yl)Benzene and Its 5,5'-Disubstituted Derivatives
    Kao Chenheng, Zhang Dayang, Zhou Yimin, Yang Xuejin, Wang Hengyan, Zhang Yibao
    1987, 8(10):  891-896. 
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    The UV spectra of 1,4-Bis(benzoxazol-2-yl)benzene and seven 5, 5'-disubs-tituted derivatives in fifteen solvents were determined. The FLspectra of 1,4-bis-(benzoxazol-2-yl) benzene in nine solvents were also determined. By treating the data with dual regression analysis, as compared with by treating with mono-regression analysis, the better correlation coefficients were obtained. By introducing the degree of relative transformation, the solvent effects on the change of shape of fluorescence spectra have been discussed.
    Studies on Synthesis and Structure of 1,6-Di(p-Methoxyphenyl) Dodecamethyl Hexasilane
    Zhou Xiuzhong, Liu Gang, Xu Shansheng, Zhang Baoshen
    1987, 8(10):  897-900. 
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    The title compound was synthesized by the reaction of 1,6-dichlorodode camethyl hexasilane with the Grignard reagent of p-bromoanisole. The physical properties of this compound were reported and its structure was determined by four cycle diffractometer. The crystal is monoclinic system, space group P21/C,the parameters of crystal cell are: α=8.856(2)Å, b=11.886(2)Å, C=16.823(3)Å; β=99.04(Ⅰ)°; V=1749Å3, Z=2, Dc=l.077g·cm-3. The final Rfactor is 0.041. The structure analysis showed that the molecule is central symmetric. The stable conformation is staggered.The planes of benzene ring and Si(l)-Si(2)-Si(3) are almost perpendicular each other. In this case the σSi-Si-π interaction of benzene ring and σSi(1)-Si(2)bond is more favourable.
    The Syntheses of New Substituted Benzo-15-Grown-5 and Bis-Crown of Keto-Ether Type
    Li Ming, Li Gang
    1987, 8(10):  901-904. 
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    The condensation reaction of benzo-15-crown-5 with haloacetic acids in poly-phosphoric acid gave A, Band C. Compounds D, Eand Fwere obtained from benzo-15-crown-5 and unsaturated acids with polyphosphoric acid as catalyst in one step, Biscrown of keto-ether type Gwas prepared from Band catechol in (CH3)2CO and in the persence of K2CO3The seven products were characterized by elemental analysis, IR, mass spectrometry, and 13CNMR.
    The Formation of 1,4-Dianions of N-(Methylbenzylidene) Benzylamine
    Guan Yedi, Hu Chunye
    1987, 8(10):  905-910. 
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    The formation of 1,4-dianioh of N-(methylbenzylidene) benzylamine occurs in the reaction of this compound with 1 equiv of n-butyllithium plus 1 equiv of LDA in dry tetrahydrofuran. The obtained 1,4-dilithium salt can react with trimethylchlorosilane to give 1,4-dialkylsilyl derivatives.
    Alkylation of Some Aromatic Aldoximes
    Chen Qinghua, Wang Xueliang, Meng Min
    1987, 8(10):  911-913. 
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    Alkylation of Z and Earomatic aldoximes are regioselective. Zaldoximes form mainly N-alkylated products, while Ealdoximes form mainly O-alkylated ones. The reaction provides a convenient synthetic route for N-allkyl 1,3-dipolar nitrones and O-alkyl aldoximes.
    A Novel Synthesis of Flavanones
    Chen Junjie, Yang Weiwen, Pan Xinfu, Li Yulin, Tan Zhen
    1987, 8(10):  914-916. 
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    Herein, a new synthetic method of flavanones is reported. Phenylmethylene-propanedinitriles (1), resulted from Knoevenagel condensation of aromatic aldehydes with malononitrile, have been conveniently converted into a series of flavanones by the Hoesch acylation with phloroglucinol, followed by hydrolysis, decarboxylation, and cyclization. Ten flavanones were prepared with higher yield by this new method, among them seven are new compounds.
    A Study on the Interactions Between Coordination Compounds and Supports
    Wang Xin, Xin Xinquan, Dai Anbang
    1987, 8(10):  917-922. 
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    In this study the viewpoint is taken that the supported complexes react with active groups on the surface of support to form new entities which may be called surface complexes. Various interactions between the support and the solution of impregnation have been found, and these interactions may be divided into four classes, (1) those that there is no noticeable chemical interaction between the coordination compound and the support, except the physical adsorption; (2) those that the metal ion of the complex is anchored on the surface through the surface group as a ligand forming a surface complex, or the support provides the central ion for the formation of a surface polynuclear complex through the bridging ligand of the complex; (3) those that the surface of the support provides the central ion for ligands dissociated from the complex or for the solvent molecules; (4) those that the metal hydroxide might be formed, when the acidity of the cation of the support is weaker than that of the metal ion of the complex in aqueous solution.
    On Altering the Lanthanide Chelate Formation Constant Sequence to Improve Ac-Ln Separations in Cation Exchange Elutions
    Ling Daren, J. F. Powell
    1987, 8(10):  923-926. 
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    The philosophy of resolving actinon-lanthanon mixtures via cation-exchange elution with selective chelating agents is considered in view of the lanthanon chelate formation constant sequences obtained with various ligands derived from polyamino-polycarboxylic acid analogues of bis(2-amino-ethyl)ether-N N,N'N'-tetraacetic acid. Stability constant data and other characteristics of a newly synthesized variant, bis (2-aminoethyl)ether-N,N,N'-triacetic acid-N'-(3-propanoic acid) are reported. The possibility of its potential application is discussed for separation of actinon-lanthanon mixtures by ion exchange.
    The Topological Connection of the Coefficients of the Characteristic Polynomial and the Molecular Fragments
    Zhao Honggang, Chen Lianshan, Yang Kaihai, Cao Yang
    1987, 8(10):  927-931. 
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    In this paper, we have induced a connected formula of the coefficients αN-kof the characteristic polynomial and the zeroorder term's coefficient of the characteristic polynomail corresponding the K-order induced subgraph's molecular fragments. From this, we can evaluate αN-kand brought to light the contribution of the induced subgraph's molecular fragments for the molecular's stability and activity.
    Quantum Chemical Study of Complexes Between Some Nitriles and BH3
    Jiang Delin, Jie Caoxian, Yu Jianguo, Liu Ruozbuang
    1987, 8(10):  932-936. 
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    The effect of substituted group, the rule of complexing action between nitri-les and BH3, the comparison of donor's soft end-BH3complex with donor's Hard end-BH3complex have been studied by MNDO scheme of SCF method with AO as basis sets, and with MO of the isolated molecules as basis sets. The results showed that the relative order of complexing action mainly depends on the order of covalent interaction, rather than electrostatic interaction.
    Crystal and Molecular Structures of a Cluster Compound (Mo2FeS8O)[(C4H9)4N]3HOCH2CH3OH
    Yang Guangdi, Zhang Zhigui
    1987, 8(10):  937-941. 
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    The title compound was synthesized by reacting certain amount of (NH4)2-MoS4with FeCl3in HOCH2CH2OH-NaOCH2CH2ONa solution. The cluster compound crystallizes in the monoclinic space group p21/c with α=16.889(6)Å, b=16.617(8)Å, c=24.527(9)Å, β=99.66(3)°, V=6785.62Å3, Z=4. The structure was solved by combining pattcrson function analysis and fourier iteration technique, and refined by using blocked-least-squares program up to the final R=0.066 Rw=0.06.Comparison with related structure shows that the presence of HOCH2CH2OH in the crystals changes its structural symmetry remarkably.
    Syntheses and Behavior of Copolymers with Polypivalolactone as Hard Blocks
    Li Youxin, Jiang Shuojian, Feng Xinde
    1987, 8(10):  942-945. 
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    ABA triblock copolymers with polypivalolactone(PPVL) as hard blocks and with polyl, 2-propandiol adipic acid esters(PPA), polybutadienc(PBD) and hydro-genated polybutadiene(HPBD) as soft blocks such as PPVL-PPA-PPVL, PPVL-PBD-PPVLand PPVL-HPBD-PPVL, and ABC triblock copolymer with PPVL and polya-methylstyrene (PaMS) as hard blocks and PBDas soft block, such as PPVL-PBD-PaMS were synthesized. It was discovered that there existed linear relationships of 1/Tm(Tm, melting point of crystalline PPVLin copolymers) against [ssoft block][/PPVL].The effects of lowering Tms and dynamical properties by contents of soft blocks in copalymers are in the order of PPVL-PPA-PPVL> PPVL-HPBD-PPVL>PPVL-PBD-PPVL corresponding to the order compatibilities between soft and hard blocks. But the dynamical properties of PPVL-PBD-PaMS are -lower than that of PPVL-PBD-PPVL and PaMS-PBD-PaMS because it is imcompatible between crystalline PPVL and random PaMS blocks.
    Studies of Post-Crosslinking of Low Crosslinked Polystyrene (Ⅰ)
    Zhang Quanxing, Yan Husheng, He Binglin
    1987, 8(10):  946-951. 
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    Macroporous polymers were prepared with post-crosslinking of low crosslin-ked polystyrene and cyanuric chloride through Friedel-Crafts reactions. The authors studied thoroughly the effects of reaction conditions such as reaction temperature, reaction time, and reagent ratios on the pore structures of polymers. The surface area and pore volume of the resin prepared are high as 500m3/g and 0.3-0.5ml/g respectively, and the skeletal densities of the resins are even higher than 1.3g/ml. The resins have almost the same swelling coefficient in various solvents.
    The Average Molecular Weights of Nonlinear Polycondensate
    Zhao Donghui, Zhang Wanjin, Tang Xinyi
    1987, 8(10):  952-957. 
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    In this paper,the Tang Aoqing's methods are used to study the average molecular weights of Aa-Bb(B')bCc, Ddtype polycondensation system and obtain it's expressions of weight and number average molecular weight. The results show that experimental and theoretical values are coincident basically.
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