Table of Content

24 August 1992, Volume 8 Issue 3

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Articles

Synthesis and Characterization of a Novel Zeolite CJS-4

ZHAO Da-qing, QIU Shi-lun, PANG Wen-qin

1992, 8(3):  185-187. 

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A novel zeolite, denoted as CJS-4, has been synthesized from nonalkaline medium by using 4,4'-trimethylenebis(1-methylpiperidine) or 1,4-diazoniabicyclo(2,2,2) octane as template agent, respectively. The precursors were characterized by means of powder X-ray diffraction, scanning electron microscopy, thermal analysis, gas adsorption and high resolution solid state NMR of ¹³C and ²⁹Si.

Spectroscopic Characterization of Mo-Co-S and Mo-Fe-S Complexes-derived Catalysts for Desulfurization and Denitrification

LIN Guo-dong, LIU Yu-da, YANG Yi-quan, ZHANG Hong-bin

1992, 8(3):  188-195. 

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The characteristic studies, by means of LR, UV-Vis and XPS spectroscopies, of the preparation process of Mo-Co-Sand Mo-Fe-Scatalysts for HDS and HDN, derived from (NH₄)₂MoS₄-CoCl₂and (NH₄)₂MoS₄-FeCl₂complexes supported on γ-Al₂O₃, respectively, indicate that the catalytically essential moiety on the surface of the catalysts is dominantly some sulfido-bimetallic species with such a structural unit (M'=Co or Fe), and both Co and Fe, served as promoters, can donate electrons to Mo probably via bridging-S. The nature of active-sites and the mechanism of promotion are discussed according to the results.

Synthesis, Structure and Properties of Nqvel Dicopper(Ⅱ) Complex [Cu(oxpn)Cu(tmen)₂]·(ClO₄)₂

LIAO Dai-zheng, LIU Zong-ming, JIANG Zong-hui, WANG Geng-lin, YAO Xin-kan, WANG Hong-gen

1992, 8(3):  196-201. 

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The copper(Ⅱ) complex, [Cu(oxpn)Cu(tmen)₂](ClO₄)₂was synthesized, where oxpn is N, N'-bis (3-aminopropyl) oxamido and tmen is N, N, N'N'-tetram-ethylethylenediamine. The crystal is triclinic, space group P1, a=1.2349(2), b=1.3093(2), c=1. 3855(2) nm, α=61.88(1), β=69.49(1), γ=57.91(1)°, V=1. 6589 nm³, Z=2. Both copper(Ⅱ) ions are in a square pyramidal coordination environment, and linked by oxamido bridge. The distance between them is 0. 526 nm. Variable temperature (4. 2-300 K) magnetic susceptibility data for this complex show that there exists a relatively large antiferromagnetic exchange interaction between the two copper(Ⅱ) ions with a Jvalue of -740. 40 cm^-1.

Physico-Chemical Characterization of Yu Guo Beads(1100～771 B. C.) in China

PENG Zi-cheng, LI Ping, ZHOU Tai-xi, LI Xue-ming, LU Lian-cheng, HU Zhi-sheng

1992, 8(3):  202-206. 

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When was the earliest glass produced in China? This has still been a question so far. Some archaeologists have thought that Yu Guo beads are real glass, the earliest glass(1100～771 B. C.) in China. However, more details of scientific investigations in this paper show that Yu Guo beads are mainly made of clastic quartz (>95%) with a small amount of clay and sintered under the low temperature(500～600℃). It is not a glassy body, but a kind of polycrystal ornaments.

Actional Mechanism of Trifluoroacetic Acid for the Separation of Biopolymers by Reversed-phase Liquid Chromatography

SHI Ya-li, GENG Xin-du

1992, 8(3):  207-211. 

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The present paper covers the actional mechanism of trifluoroacetic acid for the separation of biopolymers investigated by using the parameters of stoichiometric displacement model for retention(SDM-R) in reversed-phase liquid chromatography. It was found that the trifluoroacetic acid(TFA) may participate in, or stimulate the association among displacing agent molecules in mobile phase, and decrease the affinity of both the associate molecules of the displacing agent and the TFA-protein ion-pairing. The former dominates over the separation selectivity of biopolymers as the concentration of TFAis lower than a given value, and the two contrary functions partly offset to each other and the latter dominates as its concentration is greater than the given value.

Syntheses and Characterization of Heterocyclic Compounds of Zirconium (Ⅳ)

WANG Ji-tao, ZHANG Yun-wen, XIU Yu-ming, LI Jiang-sheng, GONG You-sheng

1992, 8(3):  212-218. 

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The Zr-H bond of zirconocene hydridochloride was heterolyzed at room temperature by five compounds containing nitrogen and hydroxyl group to give Cp(Q)₂ZrCl(1) (Cp=cyclopentadienyl and Q=8-quinolinoyl), Cp(Q-Me)₂ZrCl(2), Cp(5,7-Br₂Q)₂ZrCl(3), Cp₂(2-pyridoyl)ZrCl(4), and Cp(2-aminoethanoyl)₂ZrCl(5), which were characterized by elemental analysis, IR, and ¹HNMR spectroscopy. The molecular structure of 1 was confirmed by X-ray diffraction determination. The crystal of 1 crystallized monoclinically, space group P2₁/n a= 0.9004(2), b=1.3961(2), c=1. 6056(2) nm, β=99. 48(1)°, V=1. 9906 nm³, Z=4, and D_c=1. 582 g/cm³. The coordination polyhedron around the Zr atom can be described as a distorted octahedron. The Zr-N bonds of 0. 2364(3) and 0. 2377(4) nm suggest that they are coordination bonds. The two planar 8-quinolinoyl groups as bidentate ligands chelate with Zr atom, forming a dihedral angle of 108. 4(1)°.

Syntheses and Olfactory Characters of Some Endo-α-Substituted-Bicyclo[2. 2. 2]-Octenyl (or Octanyl) Methanols

TANG Shi-xiong, CAO Yu-rong, WANG Xiu-ling, XUE Jie-you, WANG Xiao-lan

1992, 8(3):  219-223. 

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Sixteen title compounds were synthesized, twelve of which are new ones. Their structures were determined by ¹H NMR, IR and MS, the refractive indices or melting points were measured. Odors of all the title compounds were evaluated and the structure-odor relationship was briefly discussed.

Chemistry and Application of Phosphonium and Arsonium Ylide(ⅩⅧ)--Stereoselective Syntheses of (Z)-3-Perfluoroalkyl--4-(3-Carboethoxy-2-f uranyl)-3-Butenoates

DING Wei-yu, CAO Wei-guo, ZHU Dian-kui, TONG Wei-qi

1992, 8(3):  224-230. 

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The stereoselective syntheses of (Z)-methyl 3-perfluoroalkyl-4-(3-carboethoxy-2-furanyl)-3-butenoates 5a-c were investigated. The reaction of (3-carboethoxy-2-fu-ranyl)-methyltriphenylphosphonium bromide 1 with methyl 2-perfluoroalkynoates 2a-c in the presence of K₂CO₃at room temperature gives two adducts, (E)-methyl 3-per-fluoroalkyl-4-(3-carboethoxy-2-furanyl)-2-triphenylphosphoranylidene-3-butenoates 3a-c and (E)-methyl 3-perfluoroalkyl-4-(3-carboethoxy-2-furanyl)-4-triphenylphos-phoranylidene-2-butenoates 4a-c. (Z)-Methyl 3-perfluoroalkyl-4-(3-carboethoxy-2-furanyl)-3-butenoates 5a-c can be synthesized stereoselectively with high yields when an aqueous DMFsolution of 3c, 4c or a mixture of 3a-b and 4a-b was heated at 140℃ for 8 h.

Stereochemical Effects in Mass Spectrometry (Ⅶ)--Negative Ion Fast Atom Bombardment Mass Spectro-metry of Saccharides with Areneboronic Acids as Reagents

YANG Hou-jun, CHEN Yao-zu, ZHAO Fan-zhi, LI Hai-quan, ZHAI Jian-jun, CHEN Nen-yu

1992, 8(3):  231-238. 

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1-Naphthylboronic acid and 2, 4-dimethylphenylboronic acid can react stereospecif-ically with hydroxy groups of saccharides on the probe tip of a fast atom bombardment mass spectrometer to form characteristic negatively-charged boronate ions. On the basis of the relative abundances of these characteristic ions, the epimers of mono- and di-saccharides may be distinguished. This approach was proved to be a simple and effective means for identifying sugars. The collisional activation moss spectra of these characteristic ions are also discussed.

Syntheses and Structures of Sil abridged Hafnocene Dichlorides

ZHOU Xiu-zhong, WANG Ying, XU Shan-sheng, WANG Hong-gen, YAO Xin-kai

1992, 8(3):  239-246. 

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The present paper covers three silabridged hafnocene dichlorides(1, 2 and 3) prepared by sequential reactions of α, ω-dichloropermethyl polysilane with cyclopentadienyl sodium, n-butyl lithium and hafnium tetrachloride. Their structures were characterized by elemental analyses, UV, ¹H(¹³C) NMR and MS. Furthermore the crystal and molecular structures of 1 and 2 were determined by X-ray diffraction method. The crystal of 1 is monoclinic, space group C2/c with a=1. 3401(4), b=0. 9977(3), c=1. 0922(4) nm; β=94. 07(1)° V=3. 6342 nm³, Z=2, D_c= 2.155 g·cm^-3. The final deviation factor R=0. 064. The crystal of 2 is monoclinic, space group P2₁/c with a=0.0847(1), b=1.5181(1), c=2.9824(2) nm; β= 94. 07(1)°, V=3.634 nm³; D_c= l. 805 g·cm^-3. The final deviation factor R=0. 033. The relationship between the silabridged structure and spectral properties is also discussed.

Crystal and Molecular Structures of Two Derivatives of 1, 3a, 5-Trisubstituted-3a,4,5,11-Tetrahydro-1,2,4-Oxadiazolino[5,4-d] [1, 5]Benzothiazepine

JIANG Li-hong, LIU Shen-ping, LI Gen-pei, WU Hai-tao, JIN Sheng

1992, 8(3):  247-252. 

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The structures of two derivatives of the title compound [C₂₄H₂₂N₂OS, M_r= 386. 5 for (1); C₂₅H₂₂N₂O₃S, M_r= 430. 5 for (2)] were determined by using X-ray single-crystal strcuture analysis method. The final discrepancies are R=0. 071 and 0. 077, respectively, for the reflections measured on a four-circle diffractometer. The space group for compound (1) is Pbca with a=1. 6639(4), b=2.0286(3), c= 1.1742(1) nm, V=3. 964(1) nm³, F(000)=1632e, Z=8; and (2) belongs to P2₁/n space group, and the cell dimensions are a=1. 1115(4), b=0. 8932(7), c=2. 186(3) nm, β=97. 52 (1)°, V=2.151(4) nm³, F(000)=904 e, Z=4.The molecular backbones are very similar, each is a tricyclic system. The central seven-membered ring is in a twisted-boat conformation, and is cis-fused to 1,2,4-oxa-diazolino ring, while the latter moiety is in an envelope form. There are conjugated but non-coplanar effects in each structure. All bond lengths and angles in the molecules are normally acceptable. The crystal structure on the whole is completely stabilized by Van der Waals interactions.

Studies on the Properties of Schiff Base Type of Aryl mercury Compounds(Ⅰ)--¹H NMR Spectra of Some Schiff Base Type Aryl mercury Compounds and Substituted Benzyl ideneanilines

WU Yang-jie, DING Kui-ling, YU Zheng-yan, WU Dong-hui, SHEN Lian-fang

1992, 8(3):  253-257. 

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1HNMR spectra of 16 Schiff base type of arylmercury compounds and 4 -substituted benzylideneanilines have been studied. It was found that the p-substituents of the N-phenyl ring do not affect the δ values of methine proton, whereas the o-substitutents influence the δ values of methine proton, whereas the o-substituents influence the δ values of methine proton significantly. These changes can be reasonably interpreted in terms of the steric inhibition of o-substituents and intramolecular coordination of imino nitrogen with mercury. The influence of the m-or p-substituent of the C-phenyl ring on the δ values of methine proton exhibited a linear correlation with Hammett constants σ_p or σ_m. It was also confirmed that in the molecules of Schiff base type of arylmercury compounds there exists an intramolecular coordination via a four-membered ring.

Studies on the Synthesis and Structure of Cycl opentadienylruthenium Derivatives--Crystal and Molecular Structure of (η⁵-C₅Me₄Et)₂Ru

LAI Lu-hua, ZHANG Zhen-ying, SHAO Mei-cheng

1992, 8(3):  258-261. 

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The title compound was synthesized by refluxing RuCl₃with cyclopentadiene in methanol. It crystallizes in space group C₅-P_nwith cell dimensions: a=0. 9735(4) nm, b=0. 8604(3) nm, c=1. 2261(6) nm, β=94. 83(3), and Z=2. Structure was solved by Patterson method and Fourier functions, and was refined to final Rvalue of 0. 0365 based on 1872 observable reflections. In contrast to the staggered conformation of decamethylferrocene, this molecule adopts the eclipsed comformation. The conformation difference was explained by the polarizability and metal atom size.

Studies on the New Constituents of Sal via Miltiorrhiza Bunge

CEN Ying-zhou, WU Qiu-ming

1992, 8(3):  262-266. 

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Two novel constituents were isolated from the roots of Chinese medicinal herbs, Salvia miltiorrhiza. Their structures were determined by spectroscopic technique. The compounds were named 13,14-dihydroxy-15-methyl-benzo[2,3-a]-7,7-dimethyl-12-oxa-tricyclo[4,4,2^1.4,0]dodecane(1) and 16-methyl-tropono[2,3-c]-7,7-dimethyl-12-oxa-tricyclo[4,4,2^1.4,0]dodecane(2).

Studies on Single-Ion Conducting Polymer with Pendant Sulfonate Group

ZHANG Sheng-shui, WAN Guo-xiang

1992, 8(3):  267-272. 

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The present paper narrates the single-ion conduction of the network polymer with lithium sulfonate as pendant group studied by using DC polarization. The Willianms-Landel-Ferry parameters, calculated from the temperature dependence of conductivity, agree reasonably well with universal values, verifying the influence of segmental motion on conductivity. Additional confirmation was obtained from a Vogel-Tammann-Fulcher plots. The battery composed of (Li/this film/PAn) performs better characteristics than other systems using polymer solid electrolytes.

Radiation Crosslinking of Pol ysulfone-Pol ysiloxane Multiblock Copolymers

CHEN Xin-fang, ZHANG Chun-shan, CHUI Zhan-chen, LI Bin-yao

1992, 8(3):  273-277. 

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In this paper the effects of irradiation on the structures and properties of polysul-fone-polysiloxane multiblock copolymers and its important applied prospects are studied in detail.

Synthesis, Purification and Characterization of Amphiphilic and Microphase Separated Graft Copolymer Polystyrene-g-Poly(ethylene oxide)

QIU Yong-xing, YU Xiao-jie, FENG Lin-xian, YANG Shi-lin

1992, 8(3):  278-286. 

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The present paper covers the poly (ethylene oxide) macromer with vinyl benzyl terminal group (PEO-VB) prepared by deactivation of the alkoxide function of mono-functional "living" PEOchains with vinyl benzyl chloride (VBC). The obtained macromers were subjected to careful purification and detailed characterization. Anew kind of amphiphilic polystyrene-g-poly(ethylene oxide) (PS-g-PEO) with both mi-crophase separated and PEO side chains was synthesized from radical copolymerization of PEO-VB macromer with styrene monomer. An improved purification method, referred as "selective dissolvation", was established for the isolation of graft copolymers from the grafting products, and the purity and yield of the purified copolymers were satisfactory. The well-defined structure of the purified copolymers was confirmed by IR, ¹H NMR and GPC. The bulk composition of the graft copolymers was determined by a well-established first derivative UVspectrometry. Various experimental parameters controlling the copolymerization were also studied. The results indicate that the feed ratio of macromer to styrene (M/S) was the most important factor in determining the composition of the copolymers. Thus a series of PS-g-PEO with a wide range of bulk compositions were obtained simply by adjusting the value of M/S. As clearly indicated by transmission electron microscopy, this amphiphilic graft copolymers may readily form microphase separated structures.

Twin Bifurcation Phenomena and Isolas of Multiple-Steady-States Transition in Nonideal Chemical Reaction-Diffusion Systems

LUO Jiu-li, LI Chun, TU Juan

1992, 8(3):  287-297. 

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The present paper narrates the influence of nonideality of externally controlled components on multiple-steady-state transitions studied by using the regular solution model. Under certain conditions the splitting of the original cusp causes "twin" bifurcation points accompanied by isolas which could shrink to an elliptic singular point or a cusp, or even collapse to a hyperbolic singular point in the different cases.

A New Group Theoretical Approach to the Nonorthogonal Problem in Valence Bond Theory

LI Jia-bo, WU Wei

1992, 8(3):  298-300. 

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There has been a very significarnt resurgence of interest in ab initio valence bond calculations recently. This is because the VBcalculation based on nonorthogonal basis can provide intuitive understanding about many very important phenomena in chemistry.

A Study on Bilirubin Radical Cation Generated by One-Electron Oxidation

GUO Qing-xiang, YANG Li, LIU Bo, LIU You-cheng

1992, 8(3):  301-304. 

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Bilirubin (BR) is generally regarded as a toxic compound when accumulated at an abnormally high concentration in biological tissues, and in fact a normal adult man produces about 300 mg of BRa day.