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    1998年 第19卷 第S1期    刊出日期:1998-12-31
    Plenary, Keynote and Invited Lectures
    Nature's Strategy for Making Unusual Sugars
    Hung-wen Liu
    1998, 19(S1):  1-1. 
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    The deoxy sugars are an important class of carbohydrates that are derived from common sugars by the replacement of one or more hydroxyl groups with hydrogen atoms. Such a substitution generally causes a critical alteration of the biological role of the resulting sugar, and olso induces a fundamental change in the metabolic fate of the product. Particularly notable are the 3,6-dideoxyhexoses found in the lipo-polysaccharides of gram-negative bacteria and the 2,6- and 4,6-dideoxyhexoses found in many bioactive secondary metabolites. Intrigued by the great variety of the biological activities and structural features of deoxy sugars, we have undertaken an investigation into the biosynthesis of this important class of molecules. In the past few years we have focused our efforts on the formation of ascarylose, a 3,6-dideoxy sugar, and other related deoxy sugars from Yersinia pseudotuberculosis. The first part of this presentation will cover the establishment of the course of each multi-step biotransformation and the characterization of the key enzymes involved in this pathway.
    The Development of "Caged" Substrates for the Studies of Rapid Electron Transfer and Early Events in Protein Folding
    Sunney I. Chan
    1998, 19(S1):  2-2. 
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    In recent years,the applications of photolabile compounds, or compounds that unmask a function group upon absorption of light, have become more diverse. Since such compounds can provide an effective means of orthogonal protection, they have been used to facilitate the synthesis of complex, polyfunctional organic molecules. These materials have also been used to "cage" compounds by protection of an essential functional group, so that a chemical reaction may be initiated by a pulse of light. In this manner, mixing difficulties can be circumvented in kinetics measurements. Applications of this method include the photolysis of caged ATP for studies of muscle fiber contraction, where diffusion of ATP into the muscle fiber is, slow; of caged fluorescent probes that only emit light after photolysis; and even of caged enzymes by incorporating photolabile groups on essential side chains.
    Opportunities In Interfacial Area Between Organic and Materials Chemistry
    Luping Yu
    1998, 19(S1):  3-4. 
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    It is well recognized that the current trend in organic chemistry is diverged into two frontiers: biochemistry and materials chemistry. This talk presents our recent research effort in the interfacial area between organic and materials chemistry. The major theme of our research is focused upon the rational design, synthesis and characterization of novel functional and multifunctional polymers and molecules. Typical examples of current projects are: 1). Development of polymerization methodologies: a). exploration of palladium catalyzed reactions for polycondensations, b). living ring-opening polymerization of cyclic lactone to form thioester-functionalized polyesters for chemo-ligation, 2). Design, synthesis and physical studies of photorefractive polymers, 3). Second order nonlinear optical polymers, 4). Conjugated diblock polymers for the formation of self-assembled, nano-sized electroactive materials, 5). High-performance light emitting diodes from new conjugated polymers, 6). Conjugated liquid crystalline polymers, 7). Architectural controls of polymer microstructures, including synthesis of dendritic polyphenylenevinylenes, 8). Metal-containing functional polymers. 9) Biocompatible polymers.
    若干具有复杂结构的寡糖及其缀合物的合成
    惠永正
    1998, 19(S1):  5-6. 
    摘要 ( 242 )   PDF (94KB) ( 79 )  
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    通过化学合成手段得到一定量的具有特殊活性的寡糖或其缀合物,及其改变结构的类似物不但有助于阐明糖基在生命过程中的作用,同时亦对有机合成化学提出了挑战,对生命科学和有机化学的发展都有很大的意义。我们实验室运用己有的和发展了的合成方法学对若干具有重要活性的复杂寡糖和中药活性成分的皂甙进行了合成,在这里报导了三个目标分子的工作结果。
    Biotransformation In Enantioselective Synthesis of Optically Active Compounds
    Lin Guo-qiang
    1998, 19(S1):  7-8. 
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    Transformation catalyzed by enzymes and microorganisms (biotransformation) is now well recognized as valuable tool in preparation of chiral intermediates. In this presentation the microbial reduction by G38, a fungus isolated from soil, PPL catalyzed acylation of a meso-diol and synthesis of (R)-cyanohydrins by (R)-oxynitrilase under microaqueous medium were described.
    Recent Progress in the Synthetic Applications of Substituted Furans and Pyrroles
    Henry N. C. Wong
    1998, 19(S1):  9-9. 
    摘要 ( 218 )   PDF (52KB) ( 67 )  
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    In this lecture, I would like to present efficient synthetic routes towards the total synthesis of syringolide 1 (2)1,2 and secosyrin 1 (3),1 employing 2,4-disubstituted furan 1 as a common precursor. A modified total synthesis of prehispanolone (6)3 from (S)-(+)-Wieland-Miescher ketone (4) via hispanolone (5) will also be discussed. Our methodology for the synthesis of 3,4-disubstituted-lH-pyrroles4 and for the generation of 3,4-didehydrothiophene5 has also guided us to the successful identification of 1-tert-butoxycarbonyl-3,4-didehydro-1H-pyrrole (7),which is presumably the most strained heterocyclic cumulene ever recorded.
    Total Synthesis of (-)-α-Pinguisene
    沙晉康, 程平昌
    1998, 19(S1):  10-10. 
    摘要 ( 287 )   PDF (25KB) ( 167 )  
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    In previous work from our laboratory, we demonstrated that α-carbonyl radical cyclization reactions can serve efficiently as key steps in total synthesis of natural products.1 In this presentation,we report the total synthesis of (-)-α-pinguisene from enone 1 via α-carbonyl radical cyclization.
    Development of (S)-Malimide as A Versatile Chiron for the Synthesis of 2-Pyrrolidinone-related Compounds
    黄墙虽, ZHENG Xiao, TANG Xu, LIU Xiu-Ping, WANG Shi-Li, YE Jian-Liang
    1998, 19(S1):  11-12. 
    摘要 ( 285 )   PDF (86KB) ( 78 )  
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    Selectivity, efficiency and flexibility are three major goals in organic synthesis. A good flexible synthetic method would allow the preparation of different class of compounds as well as their homologous in a straightforward way. The development of flexible synthetic methodology is particularly important in view of both providing compounds for screening ligands, bioactive compounds, drugs candidates, agrochemical candidates, etc. and providing methods for combinatorial chemistry.
    Combination of electrochemistry and the concurrent reduction and substitution chemistry to provide a facile and versatile tool for preparing functional polyanilines
    Chien-Chung Han, Wen-Da Hseih, Jiann-Yeh
    1998, 19(S1):  13-13. 
    摘要 ( 289 )   PDF (40KB) ( 95 )  
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    Polyaniline as the first commercially available conducting polymer has recently received great attention from both academic and industrial communities. Although there have been quite a few reports on substituted polyanilines, none of them are concerning about the amino- and alkylthio-substituted polyanilines. Unlike other substituted polyanilines, the attempts in synthesizing poly(alkylthioaniline) directly from the alkylthioaniline monomer via chemical and electrochemical oxidative-coupling chemistry were all fail. On the other hand,we have recently discovered that the amino and alkylthio functional groups can be easily introduced to the backbone of emeraldine polyaniline via the concurrent reduction and substitution chemistry. Further combination of electrochemistry and the concurrent reduction and substitution chemistry can provide us a facile and versatile tool for preparing functional polyanilines. Different functional groups can be introduced sequentially to the same polymer backbone. The concentrations of each substituents can be easily controlled. This new process provides us a useful utility for tailoring the molecular and the electronic structures of polyanilines to render them with appropriate and possibly new material properties suitable for many different potential applications.
    Theoretical Studies of β-Peptide Models
    Yun-Dong Wu, De-Ping Wang
    1998, 19(S1):  14-15. 
    摘要 ( 240 )   PDF (91KB) ( 89 )  
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    Recently, the β-peptides, which consist entirely of β-amino acids instead of α-amino acids, have received intensive attention because of their interesting secondary structures.1-3 Depending upon side chain substitution pattern, β-sheets, 14-helices, and 12-helices all have been observed.1 Due to great variety of substitution patterns,the easiness of formation of secondary structures with even 4-6 residues compared to about 15 for natural peptides,and ready formation of cyclic compounds that stack into tube structures,4 β-peptides have generated great excitement. In addition,β-amino acids also frequently occur in natural products, especially cyclic peptides. It has been found that β-amino acids have excellent stability toward proteases. Therefore, they have wide applications in drug development.6
    Asymmetric Synthesis of Natural Eudesmane Acids
    Yulin Li, Zhaoming Xiong
    1998, 19(S1):  16-17. 
    摘要 ( 295 )   PDF (90KB) ( 86 )  
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    Eudesmane derivatives constitute a group of natural compounds widely distributed in the plant kingdom. These kinds of compounds exhibit considerable biological activities such as antifeedant,cell growth inhibitory and plant growth regulating activities,1 and consequently efficient synthesis of those compounds are a synthetic challenge that has received much attention in the past decades. In recent years a number of eudemane acids have been isolated from natural sources.2 However the synthesis of this particular kind of compound have received little attention. In association with our synthesis work on eudesmane-type sesquiterpenes, we have been interested in studying on the synthetic approaches to this kind of compound, in particular the synthesis of compounds 1-6.
    Cooperative Binding Behavior of Ureyleno Compounds
    Man-kit Leung
    1998, 19(S1):  18-18. 
    摘要 ( 263 )   PDF (51KB) ( 102 )  
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    Since the discovery of crown ethers few decades ago, the synthesis and chemistry of macrocyclic compounds has attracted considerable attention due to their unusual ability to act as hosts to both neutral and ionic species. The study of host-guest phenomenon provides fundamentals of understanding about enzyme-substrate interactions in biological systems. Recent investigations disclosed that the binding power of a host is governed by the size, the shape, the rigidity, and the noncovalent interactions of the cavity. Important is the fact that highly flexible hosts often make binding entropically unfavorable. To tune the binding ability of a host, one should carefully design the host with appropriate rigidity. Despite of the fact that urea units and cyclic derivatives thereof are known to possess powerful ligating abilities which are due primarily to their highly polarized carbonyl groups, macrocycles incorporating urea as the binding groups have received limited attention compared to their polyoxa, polyoxo,and polyaza congeners.
    Ketone Catalyzed Oxidation Reactions
    Dan Yang
    1998, 19(S1):  19-19. 
    摘要 ( 262 )   PDF (39KB) ( 102 )  
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    Dioxiranes are important oxidants for organic reactions such as epoxidation, heteroatom oxidation and oxygenation of C-H bonds. We have developed a mild and general method for epoxidation of olefins using dioxiranes generated in situ from ketones and Oxone. This method has not only extended the synthetic utility of dioxiranes, but also allowed us to discover a series of novel cyclic ketones for catalytic oxidation. In particular, we have demonstrated the potential of chiral ketones for catalytic asymmetric epoxidation of trans-olefins and trisubstituted olefins. We have also explored the potential of ketones in catalyzing oxidation of unactivated C-H bonds and decomposition of peroxynitrite.
    Bile Acid Derivatives in the Preparation of New Synthetic Polymers
    X. X. Zhu, H. Y. Liu, A. Benrebouh, S. Gouin, Y. H. Zhang
    1998, 19(S1):  20-20. 
    摘要 ( 264 )   PDF (47KB) ( 110 )  
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    Bile acids are compounds stored in the gallbladder and help in the digestion of fats and lipids in the gastro-intestinal tract. These amphiphilic compounds can interact favorably with both hydrophilic and hydrophobic molecules. To improve the biocompatibility of the polymers used in biomedical and pharmaceutical applications, we have synthesized various derivatives of bile acids and used them in the preparation of new polymeric materials, including both polyaddition and polycondensation products. The use of the bile acid derivatives should improve the biocompatibility of the polymers, especially when they are used in the gastrointestinal tract. Even in case of decomposition, these derivatives are not expected to cause serious problems of toxicity. We have used bile acids in the preparation of both stable polymers (hydrogels) and degradable ones (polyanhydrides).
    Attractive π-Interaction as an Efficient Control Element for Acyclic Stereocontrol
    Teck-Peng Loh
    1998, 19(S1):  21-22. 
    摘要 ( 329 )   PDF (80KB) ( 86 )  
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    During the course of our synthetic studies of a natural product, an indium-mediated allylation reaction in aqueous media has been developed as the key step for the assembly of the advanced intermediate 2 (Scheme 1) in our strategy. The reaction proceeds with very high diastereoselectivity (>99% de), a result rare for acyclic molecules in the absence of obvious steric interaction or intramolecular chelation.1 The interlocking physical, chemical and computational studies undertaken supported a π-stacking effect between the phenyl ring with the ketone.
    C2, Symmetric Dibenzosuberanes as Templates for the Chirality Determination of Helicenes and Their Applications as Optically Switchable Memory Device
    Y. C. Chou, J. I. Gao, C. T. Chen
    1998, 19(S1):  23-24. 
    摘要 ( 247 )   PDF (99KB) ( 91 )  
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    We have recently developed a new type of chiral templates, dibenzosuberanes. Thess C2, symmetric diaryl modifiers have been successfully applied to the synthesis of chiral triarylcarbenium ions. They can serve as catalysts in the asymmetric Mukaiyama aldol reactions with moderate enantioselectivities of up to 50% [1]. We have subsequently found that one major side reaction between the catalyst and the substrate-silyl ketene acetal which releases extra silyl-X species is responsible for the erosion of asymmetric induction. The dibenzosuberane scaffold was found essential to prevent this type of side reaction. For the selection of carbenium counter ions, we have resorted to the chloride in order to completely suppress the undesired silyl catalysis [2].
    A Total Synthesis of RA-VII
    Jieping Zhu
    1998, 19(S1):  25-25. 
    摘要 ( 338 )   PDF (30KB) ( 100 )  
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    RA-VII (1) and related bicyclic hexapeptides, isolated from Rubiaceous plants, Rubia akame,showed potent antitumor activity and in fact, RA-VII is currently undergoing phase Ⅱ clinical trial in Japan. It inhibit protein synthesis through binding,to eukaryotic 80S ribosomes, resulting in inhibition of aminoacyl-tRNA binding formation and peptidyl-tRNA translocation. The complex molecular architecture and interesting biological activity made these compounds attractive synthetic targets.
    Development of Methods for Diastereo- and Enantioselective Synthesis of Hydroxyl amine Derivatives
    Kang Zhao
    1998, 19(S1):  26-26. 
    摘要 ( 241 )   PDF (49KB) ( 81 )  
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    N-alkyl hydroxylamines add to conjugated alkenoates in a "concerted" fashion with high stereoselectivity and the esulting intermediates can be easily derivatized to several classes of biologically interesting molecules such as the analogs of aminosugar and nucleoside. For example, high stereoselectivity was observed in the addition of hydroxylamine derivatives to acyclic a,b-unsaturated esters. The adducts were subsequently cyclized under mild conditions to afford a single isomer of isoxazolidin-5-ones which were converted to class of isoxazoline and isoxazolidine derivatives for the studies of their antiviral activity.
    Green Chemistry and Glycochemistry
    Peng George Wang
    1998, 19(S1):  27-28. 
    摘要 ( 326 )   PDF (130KB) ( 202 )  
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    With the increasing environmental concerns and the regulatory constraints faced in the chemical and pharmaceutical industries, development of environmentally benign organic reactions (also called Green Chemistry) has become a crucial and demanding research area in modem organic chemical research. Our contribution to this rapidly growing field involves use of certain lanthanide salts such as lanthanide(Ⅲ) trifluoromethanesulfonates as stable Lewis acids in protic solvent such as water or alcohols to catalyze a variety of organic transformations under nearly neutral conditions. This benign approach has the potential to replace many traditional reaction systems which are either conducted in strong acidic conditions or in environmentally less-friendly solvents. For example, aza Diels-Alder (DA) reaction in aqueous solution conveniently combines three reactant components (an aldehyde, an amine salt and a diene) in aqueous solution and generates nitrogen-containing heterocyclic products. However, this reaction is limited to either the smallest aldehyde or activated aldehydes such as glyoxylates. We have found that lanthanide(Ⅲ) triflates catalyze the aza DA reactions of a larger,inactivated aldehyde and an amine hydrochloride with a diene in aqueous solution[1]. Other examples of application of lanthanide triflates in protic solvents include Chicliibabin pyridine synthesis[2],condensation of indoles with aldehydes or ketones[3], and use of ion-exchange resin supported lanthanide catalysts[4].
    Organic Synthesis Chemistry
    A Straightforward Synthesis of Polythiophene-fused-3-sulfolenes from Methyl 3-Hydroxy-4,6-dihydrothieno[3,4-b]thiophene-2-carboxylate
    Hsi-Hwa Tso, Honru Tsay
    1998, 19(S1):  29-29. 
    摘要 ( 228 )   PDF (28KB) ( 71 )  
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    A straightforward synthesis of substituted polythiophene-fused-3-sulfolenes from the readily prepared methyl 3-hydroxy-4,6-dihydrothieno[3,4-b]thiophene-2-carboxylate will be presented. Upon thermolysis in the presence of N-phenylmaleimide, these new substrates serve as precursors of reactive polythiophene o-quinodimethanes to give the corresponding Diels-Alder adducts in high yields.
    Efficient Transformation of Nitrile into Amide under Mild Condition
    Manas K. Basu, Fen-Tair Luo
    1998, 19(S1):  30-30. 
    摘要 ( 307 )   PDF (55KB) ( 76 )  
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    Transformation of various kinds of nitriles into the corresponding amides or amide salts was performed in good yields by the addition of two equiv of chlorotrimethylsilane and three equiv of water at 0℃ to room temperature. Hydrogen halide generated in situ by TMSX and water is an important reaction especially when HX is needed in requisite amount and under dry reaction conditions. As part of our endeavor to utilize HX thus generated, we have found TMSC1 and water can be used for transformation of nitriles into amides under very mild reaction conditions and with satisfactory yields. Interestingly, under the condition of hydration of nitrile, ester of carboxylic acid remains intact. Although there are several reports in the literature to bring about the same transformation, however, a new approach is still significant and needed. Moreover, most of the reported methods have not been proven in general and practical in scope. This paper reports the hydration of a series aliphatic as well as aromatic nitriles into amides at 0℃ to room temperature for only two to four hours. Solvent is not needed in this transformation. Attempts to use THF, MeNO2, or CH2Cl2 as the solvent results in poor yields. Protonation of the nitrile by HCl, generated in situ from TMSC1 and half equiv of H2O, and followed by nucleophilic attack by another equiv of H2O to form the amide salt seems to be the possible pathway for this reaction. Ideally, the molar ratio for RCN/TMSC1/H2O is 1:1:1.5. Use of little excess of the reagents (0.2 to 0.5 equiv) leads to completion of this reaction in 10 to 12 h. To compensate the escape of HCl generated in situ, one more equiv of HCl is generally used in this reaction. No further hydrolysis of amide to the carboxylic acid was observed in the presence of one more equiv of water.
    Misenine,a Novel Macrocyclic Alkaloid with an Unusual Skeleton from the Mediterranean Sponge Reniera sp
    Yuewei Guo, Enrico Trivellone, Gennaro Scognamiglio, Guido Cimino
    1998, 19(S1):  31-32. 
    摘要 ( 344 )   PDF (77KB) ( 84 )  
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    PolycycJic marine alkaloids containing 3-alkylpyridine or partially reduced 3-alkylpyridine as basic building blocks represent an emerging and intriguing group of bioactive natural products from marine sponges. Since halitoxin,2 the first example of this kind of alkaloid, was reported in 1978, many related alkaloids have been discovered from sponges of the order Haplosclerida. All of these alkaloids, in spite of formally exhibiting quite different frameworks, could biogeneticaliy derive from bis-3-alkylpyridine or reduced bis-3-alkylpyridine units. In the last decade, the knowledge of this fascinating group of compounds has increased remarkably. A recent review has exhaustively studied occurrence, distribution, plausible biogenetic origin and relatedness, as well as biological activities, of 3-alkylpyridine derived marine alkaloids.3
    A Novel Rearrangement Cyclization of 3-Amino-2-benzyl-6-hydrazino-1,2,4-triazin-5-one
    Long-Chih Hwang
    1998, 19(S1):  33-33. 
    摘要 ( 295 )   PDF (31KB) ( 81 )  
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    A facile ring closure reaction with the N-l nitrogen of the 1,2,4-triazine ring occurs when 3-amino-6-hydrazino-1,2,4-triazin-5-one(1) is refluxed in either acid, orthoester/dimethylformamide, carbon disulfide, cyanogen bromide or nitrous acid. 3-amino-2-benzyl-6-hydrazino-1,2,4-triazin-5-one(2), containing the benzyl group on the 2-position of 1, can not be cyclized under the above reaction conditions except refluxed with carbon disulfide in pyridine-water(1:1), which will pass through a novel rearrangement cyclization to afford a bicycloheterocyclic compound,6-amino-3-benzylmercapto-1,2,4-triazolo[3,4-f][l,2,4]triazin-8(7H)-one(3). The mechanisms of their ring closure and rearrangement cyclization will be presented in detail.
    ENE REACTION WITH PUMMERER-TYPE REACTION INTERMEDIATE OF α-(METHYLTHIO)ACETIC ACID PYRROLIDIDE:SYNTHESIS OF ACHILLEA AMIDE AND TRICHONINE
    Kuo-Hui Sun, Huey-Min Wang, Ling-Ching Chen
    1998, 19(S1):  34-34. 
    摘要 ( 227 )   PDF (38KB) ( 96 )  
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    The dienamide group is an important structural feature of a number of natural products, which have been reported to be biologically active, especially as insecticides. Several methods for their synthesis have appeared involving Wittig reaction, elimination reaction, and amidation of corresponding dienoic acids or esters. Achillea amide [(E,E)-2,4-tetradecadienoic acid pyrrolidide] and Trichonine [(E,E)-2,4-eicosadienoic acid pyrrolidide)] which are naturally occurring insecticides isolated from Achillea nana and P. trichostachyon leaves, respectively. Severál methods have reported successful syntheses of unsaturated pyrrolidine amides. In this work we wish to report that the Pummerer-type reaction intermediate 2 derived from α-(methylthio)acetic acid pyrrolidide (1) and phenyliodine(Ⅲ) bis(trifluoroacetate) (PIFA) undergoes an ene reaction with 1-alkenes to give the ene adducts 3. Also reported is its application to the synthesis of Achillea amide (4) and Trichonine (5).
    Methoxide Promoted Anionic Cyclization of 2-Alkynylbenzonitrile:A New Synthesis of 3-Substituted Isoqunolin-1-one
    Ming-Jung Wu, Li-Juan Chang, Chi-Fong Lin
    1998, 19(S1):  35-35. 
    摘要 ( 321 )   PDF (34KB) ( 60 )  
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    The treatment of 2-(2-alkylethynyl)benzonitrile with sodium methoxide in methanol gave 3-alkyl-l(2H)-isoquinolinone in modest yield. Under the same reaction conditions methanolysis of 2-(2-arylethynyl)benzonitrile lead to the formation of 3-alkylidene isoindol-1-one. Partially hydrolysis of 2-(l-hexynyl)benzonitrile to the corresponding benzamide,followed by the treatment of the benzamide with sodium methoxide gave 3-pentylidene isoindol-1-one in 11% yield. This result suggests that benzamide is not the intermediate of the formation of isoquinolinone. The more plausible mechanism of this methanolysis process is involving the iminium anion cycloaromatization to form 2-methoxyisoquinoline and subsequent hydrolyze to isoquinolinone. In one case,2-methoxyisoquinoline product was isolated.
    A General and Facile Synthesis of l,3-Diaryl-4-pyrazoleacetic Acids and Its Application in the Synthesis of SDZ RGU 825
    Daqiang Xu, Kapa Prasad, Oljan Repic, Thomas J. Blacklock
    1998, 19(S1):  36-37. 
    摘要 ( 337 )   PDF (81KB) ( 63 )  
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    1,3-Diaryl-4-pyrazoleacetic acids and derivatives exhibit multiple biological activities.1 For example, Lonazolac® is listed in Merck index as an antiinflammatory and analgesic agent. We were interested in this type of compounds for their potential applications in anti-diabetics. One of the leading candidates, SDZ RGU 825,has been shown to enhance whole-body glucose disposal without increasing insulin secretion. Therefore, it was developed for treatment of "non-insulin-dependent diabetes mellitus",the type Ⅱ diabetics.
    A NEW Method for the Synthesis of Polyether Bridged Azulenes:Reactions of Conjugated Keto-carbenes in the Photolysis of the Corresponding Azulenoquinone Diazides
    Yun-Shan Lin, Shuan-Ya Jiang, Shih-Jue Lin, Tian-Chuan Huang, Yuan L. Chow
    1998, 19(S1):  38-39. 
    摘要 ( 338 )   PDF (69KB) ( 79 )  
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    Photolysis of 1,4-quinone diazides has been known to generate conjugated keto-carbenes that may exist in the triplet and singlet states of ground as well as lowest excited levels with energy levels closely packed to one another. We used the diazides of 1,3-disubstituted 2,4-azulenoquinones as the model compound to demonstrate their singlet state reactivity in electirophilic reactions in competition to other reactions. Under the optimum conditions, the keto-carbenes reacts with cyclic ethers or amines repetitively to give polyether bridged azulene derivatives.
    OXIDATION OF HYDROCARBONS UNDER THE MILD CONDITIONS
    Yasuhiko KURUSU
    1998, 19(S1):  40-41. 
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    The oxidation of organic substrates leads to the production of many functionalised molecules which are of great commercial and synthetic importance. The conventional mode of oxidation which involves stoichiometric ammount of Cr or Mn salts has been staked out because of the environmental hazadrous process. The transition to cleaner, safer, and more efficient plants is a new paradigm in the synthetic organic chemistry. Nowadays, hydrogen peroxide and oxygen as oxidizing agents were extreamely valuable and attractive. It is increasingly recognized, when polymers are used as supports for catalysts or organic reagents, the reactivity and selectivity of the supported catalysts or reagents may be seriously changed by so-called "polymer effects". As metal catalyzed oxidation of organic substrates with oxygen, we arc planing the incorporation of transition metals into polymer. In oxidaton organic compound has little resistant, so syntheses of organic-inorganic hybrid polymer from silica gel and montmorillonite by the modification with silane coupling reagents and the complexation of transition metal ions into hybrid polymer obtained above were investigated.
    Regioselective Formation of Enediynes via Intramolecular Trapping of Allylic Cations
    戴偉民, 李玉霞
    1998, 19(S1):  42-43. 
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    Enediynes are a novel class of naturally occurring antitumor antibiotics capable of causing DNA strand cleavage by hydrogen atom abstraction from the deoxyribose backbone. During the past decade, numerous synthetic methods have been developed to synthesize the naturally occurring and the "designed" enediynes for biomedical studies. Recently, we have succeeded in assembling the cis-enediynes 2 by a novel and high-yielding allylic rearrangement under mild reaction conditions (Eq 1).1-3 This methodology has been used to synthesize a 10-membered ring enediyne3 which exhibits DNA cleavage activity.
    Preparation of 2,6-Diisopropylnaphthalene(2,6-DIPN) by the Shape-Selective Isopropylation of Naphthalene over Synthetic Mordenite
    TIAN Zheng-Hua, WANG Wen-Han, ZHANG Xiao-Hui, SONG Ren-Feng
    1998, 19(S1):  44-45. 
    摘要 ( 270 )   PDF (103KB) ( 84 )  
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    2,6-DIPN is a precursor of 2,6-naphthalene dicarboxylic acid (2,6-NDA) which is an important monomer for making advanced polyester materials and liquid crystalline polymers. The more advanced method for preparing 2,6-NDA is the direct oxidation of 2,6-dialkylnaphthalene (2,6-DAN). Since isopropyl group is more hindered than methyl and ethyl group, a β-selective isopropylation could be expected in case of using shape selective zeolite catalysts instead of the conventional Friedel-Crafts alkylation. A particularly preferred catalyst is synthetic Mordenite having a specific Si/Al ratio, which results in a high selectivity of 2,6-DIPN. It is more beneficial to the separation and purification of 2,6-DIPN from its isomers. In this paper the study on isopropylation of naphthalene over various zeolites and different dealuminated H-mordenites (HM) is reported.
    Production and Study of Monoclonal Antiidiotypic Antibody with a Catalytic activity similar to Carboxypeptidase A
    DU Mei, JIN Sheng, GUO Zheng quan
    1998, 19(S1):  46-47. 
    摘要 ( 311 )   PDF (92KB) ( 116 )  
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    Catalytic antibody(abzynie) is a new class of biocatalysts. Combining the specificity and the enormous molecular diversity of the antibody with high catalytic efficiency of enzyme to produce catalytic antibody, that is a new method of designing protein. A method of producing catalytic antibody developped recently is to produce antiidiotypic antibody. As the "internal images" of the antigen structure, the antiidiotypic antibody can exhibit the properties similar to the antigen1. To produce the antiidiotypic antibody of the natural enzyme, we may obtain the catalytic antibody whose structure and catalytic activity are similar to the natural euzyme. A. Friboulet et al successfully produced the antiidiotypic catalytic antibody of acetylcholinesterase, whose catalytic activity approaches the natural acetylcholinesterase2. Carboxypeptidase (CPA) has peptidase and esterase activities, to produce the antiidiotypic antibody of CPA, we may obtain the catalytic antibody which catalyze the hydrolysis of amide bond and highly efficiently catalyze the hydrolysis of ester bond. Therefore, this research work is very significant. In this report, we produced a monoclonal antiidiotypic antibody with a catalytic activity similar to the esterase activity of CPA and studied it's kinetic property.
    Direct Trapping of Ketene Intermediate by Internal Nucleophile:A New Approach for the Synthesis of γ-Lactams
    Yihua Hou, Jianbo Wang
    1998, 19(S1):  48-49. 
    摘要 ( 399 )   PDF (101KB) ( 68 )  
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    The application of Wolff rearrangement of the diazoketones derived from α-amino acids has been well documented.1 It has been generally observed that if the rearrangement is performed in aqueous solution, homologated acid is the expected products, while if the reaction is run in methanol or ammonia, the corresponding homologated ester or amide will be obtained. In connection with other synthetic work, we unexpectedly observed that the Wolff rearrangement of diazoketone 1 in anhydrous methanol gave exclusively γ-lactam 3 in excellent yield.(Scheme 1) The formation of this intramolecular cyclization product was apparently due to the nucleophilic attack of the intermediate ketene 2 by the tosyl protected amino group. Although the solvent methanol can serve as nucleophile, the exclusive formation of γ-lactam indicates the intermolecular nucleophilic attack of the ketene intermediate 2 by methanol is not effective enough to compete with intramolecular nucleophilic attack by the tosyl protected amino group. This observation aroused our interest in the generality of this reaction and its potential as a novel method for the direct synthesis of γ-lactams. We report here the results of the investigation of Wolff rearrangement of several diazoketones derived from N-tosyl protected α-amino acids and β-amino acids.
    A Linear Free Energy Correlation Study of Rh(Ⅱ)-Mediated Carbenoid Intramolecular C-H Insertion
    Fengting Liang, Bei Chen, Jianbo Wang
    1998, 19(S1):  50-51. 
    摘要 ( 332 )   PDF (109KB) ( 108 )  
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    The reaction mechanism of Rh(Ⅱ)-mediated carbenoid intramolecular C-H insertion have been intensively investigated. The reaction has been observed to be affected by the electrophilicity of the Rh(Ⅱ)-carbene intermediate, the substituents on the carbon at which the C-H insertion occurs, and steric and conformational factors.1 It has been well documented that the electronic property of the ligands of the Rh(Ⅱ) catalyst has marked influence over the electrophylicity of Rh(Ⅱ)-carbene intermediate. In addition, the α-substituent on the carbenoid carbon are expected to exert similar affect on the reactivity of Rh(Ⅱ)-carbene. According to the reaction mechanism proposed by Doyle, an electron-donating α-substituent decreases the electrophilicity of the Rh(Ⅱ)-carbene complex and causes the C-H insertion to occur with a later transition state,while an electron withdrawing α-substituent operates in the opposite way. However, this prediction is still lack of solid support by experimental data. Most of the studies on the electronic effects have so far been concentrated on electron-withdrawing α-substituent, such as ester or acetyl group. The α-substituent effect, although important, is generally subtle and may be readily overridden by other effects, such as steric and conformational effects. This makes it difficult to accurately evaluate the α-substituenteffect.
    Study on the Non-enzymic Catalytic Enantioselective Methanolysis of 4-benzyl-2-phenyl-5(4H)-oxazolone
    Wenting Hua, Lunjia Xie
    1998, 19(S1):  52-53. 
    摘要 ( 259 )   PDF (96KB) ( 75 )  
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    Dynamic-kinetic resolution is different from kinetic resolution1. In ideal case,dynamic-kinetic resolution can convert racemic substrate to product with 100% yield and >99% e.e. whereas kinetic resolution can only converted racemic substrate to enantiomeric pure product with 50% yield.
    Synthesis and Characterization of Macrocycles Containing 1,3,4-Oxadiazole
    Wenting Hua, Shu Wang
    1998, 19(S1):  54-55. 
    摘要 ( 234 )   PDF (65KB) ( 108 )  
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    The design of molecules with delocalized π-electronic structures which are useful as organic conductor and light-emitting diodes(LEDs) has attracted much attention.[1-2] We have synthesized some conjugated Schiff base macrocycles containing 1,3,4-oxadiazole(such as compound 1) and after being doped with I2,they showed electrical conductivity in the region of semiconductor.[3] To continue this work and understand the relationship between molecular structure and solid state properties, we designed other conjugated schiff base macrocycle containing 1,3,4-oxadiazole.
    Application Studies of Antigenic Peptides
    Jiaxi Xu
    1998, 19(S1):  56-57. 
    摘要 ( 198 )   PDF (103KB) ( 56 )  
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    The region of an antigen that is recognized by a paratope is called an antigenic determinant or epitope. Antigenic peptide presented epitope is very important to many fields, such as detecting diseases, developing synthetic peptide vaccines. Herein we reported antigenic peptide applications in HEV diagnosis, protein detection in gene expression product of transgenic tobacco and synthetic peptide vaccine against schistosomiasis.
    新手性源5-(1-(艹孟)氧基)-3-溴-2(5H)-呋喃酮的不对称双Michael加成/分子内亲核取代反应的研究
    黄慧, 陈庆华
    1998, 19(S1):  58-59. 
    摘要 ( 330 )   PDF (116KB) ( 153 )  
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    新型手性试剂的合成及其在不对称和天然产物合成中的应用乃是当今有机化学中非常活跃的研究领域。近几年来,利用天然手性助剂薄菏醇、冰片制备具有重要合成价值的手性源,用于不对称反应以及立体选择性合成某些生物活性化合物引起人们重视。在以往研究工作的基础上,我们深入研究了具有独特结构性能的5-(l-(艹孟)氧基)-3-溴-2(5H)-呋喃酮新手性源(5a)的合成方法及其串联的双Michael加成/分子内亲核取代反应。3-溴呋喃酮新手性试剂5a制备方法简便,化学产率较髙,光学纯度单一。由于5-(1-(艹孟)氧基)-3二溴呋喃酮5a具有独特的结构性能,它可以作为稳定的Michael受体,能够发生串联的双Michael加成/分子内亲核取代反应。同时,由于(艹孟)氧基的立体专一性控制,生成了一般合成方法难以合成的手性的丁内酯并螺-环丙烷类化合物。此新手性源的合成及其不对称螺-环丙化反应的研究,为进一步合成一系列新的光学活性环丙烷化合物提供了简便有效的途径。
    ASYMMETRIC ADDITION OF (+)-CAMPHOR SULFINIMINES WITH DIETHYLALUMINUM CYANIDE
    Li Yan, Zhu Wei, Cheng Zhi-Yong, Yang Gui-Shu
    1998, 19(S1):  60-61. 
    摘要 ( 234 )   PDF (67KB) ( 66 )  
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    The development of new and improved methods for the asymmetric synthesis of α-amino acids is of considerable current interest because of their importance in biological systems and their exceptional utility as chiral building blocks. Of the many methods used to prepare α-amino acids, the asymmetric Strecker synthesis should hold particular prominence because of its simplicity1. Recently, F. A. Davis and his coworkers reported that diethylaluminum cyanide (Et2AlCN) adds to enantiopure p-tolylsulfinimines to give α-sulfinamino nitriles at 82-84% diastereoselectivity. Treatment of α-sulfinamino nitriles with acid removes the chiral auxiliary p-tolylsulfinyl group and hydrolyzes the nitrile to give α-amino acids without epimerization2. This research was quoted in Highlight by Chemistry & Industry as an improved asymmetric Strecker synthesis3. However, the diastereoselectivity of this addition reaction needs to be improved more high, and moreover, the preparation of p-tolylsulfinimines from nonracemic p-tolylsulfinamides and aldehydes needs strong organic metallic bases2b, so it is desirable to design an easier prepared and effective optical sulfinimines.
    3,5-二氯4-氰基异噻唑的结构修饰及其产物的生物活性
    杨小平, 李正名, 梁鑫淼
    1998, 19(S1):  62-63. 
    摘要 ( 290 )   PDF (96KB) ( 100 )  
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    3,5-二氯4-氰基异噻唑是一重要的中间体,已有研究表明,其环上两个氯原子的活性存在差异,5位氯原子较活泼可以被亲核试剂取代,但3位氯原子却表现出强烈的惰性,在亲核反应中表现出有趣的区域选择性。
    The Synthesis of 1,3-Dithiole Derivatives by Using Bun3P·CS2 Adduct
    Xiaodong Chen, Yuxiu Liu, Ruzhen Cao, Lunzu Liu
    1998, 19(S1):  64-65. 
    摘要 ( 264 )   PDF (51KB) ( 64 )  
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    The red crystalline adducts formed between trialkylphosphines and carbon disulfide were confirmed to be l,3-dipolar structure by X-ray diffraction in 1961.[1] Despite the apparent synthetic potential of the 1,3-dipolar structure, studies on its cycloaddition have only been restricted in electron-deficient alkynes as dipolarophiles.[2-5] However, reactions with electron-rich alkynes have received little attention.
    Cycloaddition of Bun3P·CS2 with Azo Compounds
    Xiaodong Chen, Yuxiu Liu, Ruzhen Cao, Lunzu Liu
    1998, 19(S1):  66-67. 
    摘要 ( 241 )   PDF (42KB) ( 60 )  
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    Cycloadditions of Bun3P·CS2 Ⅰ with electron-deficient alkynes have been studied, but reactions with double bonds have only been confined to maleic anhydride, N-phenylmaleimide[1] and norbomene analogs[2]. In this paper we describe the first examples of cycloadditions of Ⅰ to heteroatom double bonds.
    Synthesis of 2-ethyl-3-Hydroxy-4-Pyridone Nucleosides
    Chen Weimin, Zeng Longmei
    1998, 19(S1):  68-69. 
    摘要 ( 211 )   PDF (79KB) ( 62 )  
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    The hydroxypyridones were found to have wide biological activities such as they can be used as iron chelators for the treatment of iron overload of transfusion-dependant patients[1]. Some hydroxypyridones were discovered to possess moderate reproducible activity against murine P-388 leukemia[2] and showed antimalarial activity[3]. Besides some nucleoside of hydroxypyridones exhibit antitumor activity[4]. The 2-ethyl-3-hydroxy-4-pyridone nucleosides were synthesized by direct condensation of the silylated 2-ethyl-3-hydroxy-4-pyridone with 1,2,3,5-tetra-o-acetyl-β-D-ribofuranose using trimethylsilyl triflate(Me3SiOTf) as catalyst. Deblocking of the protected ribofuranosyl nucleosides was performed by the standard methods.
    卡维地洛的合成工艺及晶体结构
    陈卫民, 陈望忠, 曾陇梅, 徐继红, 万山河
    1998, 19(S1):  70-71. 
    摘要 ( 331 )   PDF (61KB) ( 245 )  
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    卡维地洛是一种β-受体和α1-受体阻断剂,临床上用于治疗高血压、心衰等疾病。我们首先在国内开发出该药。在已有文献的基础上,对其全合成工艺进行了研究,并作出了合理的改进。
    The Synthesis and Crystal Structure of Triphenyltin-2-(l,1-dithioalkyl)methylene-3-oxo-5-aryl-4-pentenicate
    Sun Zhen-gang, Li Jian-xin, Liu Qun
    1998, 19(S1):  72-73. 
    摘要 ( 287 )   PDF (66KB) ( 98 )  
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    Triorganotin compounds are a kind of organotin complexes with high biological activities. Some of triphenyltin derivatives such as triphenyltin acetate and triphenyltin hydroxide have been used as agricultural chemicals[1]. α-Oxo ketene dithioacetals is a kind of important polyfunctionai intermediates in organic synthesis and is widely studied in recent years[2]. Some of α-oxo ketene dithioacetal derivatives, such as 1,3-dithio-2-cyclopentylene-dithiopropylacrylate has also been used as agricultural chemicals. But it is no reports about the work combined both trialkyltin derivatives and α-oxo ketene dithioacetals together.
    膦催化下α-溴甲基丙烯酸酯对C60的[3+2]环加成反应
    张丹维, 舒联合, 吴世晖, 吴厚铭, 徐静斐
    1998, 19(S1):  74-75. 
    摘要 ( 339 )   PDF (67KB) ( 70 )  
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    在碳60官能化修飾研究工作中,我們曾實現了在三丁基膦催化下碳60與2,3-丁二烯羧酸酯的反應,得到了碳60駢環戊烯羧酸酯。[1] Zhang等曾報道三苯基膦和碳酸鉀共同催化下α-溴甲基丙烯酸酯對缺電子烯烴發生[3+2]環加成反應生成環戊烯基羧酸酯衍生物。[2] 本文報道在相同的條件下碳60與α-溴甲基丙烯酸酯的反應。
    过渡金属盐及络合物在乙苯液相氧化中的催化作用
    姜恒, 马学良, 宫红
    1998, 19(S1):  76-77. 
    摘要 ( 301 )   PDF (108KB) ( 96 )  
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    有机化合物中的C-H键选择性官能团化是有机合成中具有挑战性的课题之一。在不同的氧源(如H2O2、NaOCl、TBHP、RCOOOH、O2等)作用下,许多过渡金属络合物可以选择性氧化有机物[1]。显然,由于分子氧廉价易得并且在氧化过程中对环境没有污染,所以分子氧是氧化反应的最理想的氧源。由于分子氧较难活化以及选择性方面的原因,在温和条件下过渡金属催化的分子氧选择性氧化过程受到了广泛的关注[2]。有关乙苯的液相催化氧化已有一些报道,比较有代表性的有以[W10O32]4-和 CoC12·6H2O为催化剂的光催化氧化过程[3,4]、负载型的Ru络合物催化剂[5]以及在己醛存在下以Fe盐或Ru盐为催化剂的氧化过程[6]。本文在温和条件下(常压、110℃), 考察了不同过渡金属盐及络合物在乙苯液相氧化中的催化作用,着重考察了催化反应机理。
    Facile Total Synthesis of Three Natural 1,7-Diaryl-4-hepten-3-ones
    Chusheng Huang, Xihui Chen, Yulin Li, Hongxing Liu
    1998, 19(S1):  78-79. 
    摘要 ( 290 )   PDF (74KB) ( 97 )  
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    Linear 1,7-diarylheptanoids (Ar1-C7-Ar2) are a large group of interesting natural products isolated from plants belonging to Alinia,Curcuma, Zingiber, Alnua,Centridobium and Acer genera used as traditional medicines in some oriental countries1. Pharmacological experiments exhibited that some of them had many physiological actions such as anti-inflammatory, antifungicial, antioxidative,antihepatotoxic activities and so on2. Three natural compounds 13, 24 and 35 (gingerone C) having 1,7-diaryl-4-hepten-3-one skeleton were isolated from the rhizomes of Alpinia offocinarum, the wood of Alnus japonica and the rhizomes of Zingiber officinale respectively. Their structures were elucidated as 1,7-diphenylhept-4-en-3-one(1), 1,7-bis(4-hydroxyphenyl)hept-4-en-3-one(2) and 1-(3-hydroxyl-4-methoxyphenyl)-7-(4-hydroxyphenyl)hept-4-en-3-one(3) by spectral method. Herein, we wish to report facile total synthesis of these three natural compounds. Their synthetic routes were shouwn in scheme.
    Facile Synthesis of (±)-2,6-Dimethethyl-6-hydroxy-2,7-octadienoic Acid and its Methyl Ester and Amide (Acacialactam)
    Chusheng Huang, Xihui Chen, Ying Li, Yulin Li, Hongxing Liu
    1998, 19(S1):  80-81. 
    摘要 ( 228 )   PDF (81KB) ( 67 )  
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    The monoterpenoid acid 1, which is a component of some traditional medicine such as Gymnocladus chinensis baillon in glycoside form,1 was recently isolated from Artemisia sieberi in Iran in free form.2. Its structure has been established to be (E)-2,6-dimethyl-6-hydroxy-2,7-octadienoic acid (1) by chemical and spectroscopic analysis. Its methyl ester derivative 2,was isolated from the antibacterial extracts of the leaves of Piper aduncum3 as well. Acacialactam, a natural product isolated from the seeds of Acacia concinna DC.(Legunninosae) used in folk medicine of several tropical countries for treating some skin diseases, was assigned structure 4 by Sekine et al4 on the basis of its physical and spectral properties.
    Study on the Synthesis of Poly(p-Phenylene Vinylene) Derivatives by Dehydrochlorination
    Jianying WANG, Yinkui Li, Wenxiang HU, Yongfu LONG, Guangyou ZHANG
    1998, 19(S1):  82-83. 
    摘要 ( 402 )   PDF (126KB) ( 155 )  
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    The synthesis of poly(p-phenylene vinylene) (PPV) and its derivatives have aroused great interest[1],since Burroughes[2] discovered that PPV showed excellent electroluminescent (EL) properties. The conventional polymerization reactions, such as dehydrochlorination reaction,Wittig reaction and et al, usually afforded insoluble and/or infusible PPV and its derivatives, which shows inferior mechanical properties. Though the precursor polymer route can circumvent the insolubility of PPV, the strategy needs muti-step reaction and high temperature which affords the low yield and other disadvantageous[3]. So the synthesis of soluble PPV derivatives with high yield are very fascinating.
    Synthesis of 1,4-Bis(chloromethyl) Benzene with Different Alkoxy-Substituents
    Jianying WANG, Yinkui LI, Wenxiang HU, Yongfu LONG, Shengjian TAN
    1998, 19(S1):  84-85. 
    摘要 ( 344 )   PDF (101KB) ( 102 )  
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    l,4-Bis(chloromethyl) benzene (BCMB) and its derivatives are very important intermediates of much synthetic reaction. Especially, they can be used to synthesize poly(p-phenylene vinylene) (PPV) and its alkoxy derivatives, which have aroused significant interest in recent years[l,2]. So people pays close attention to the synthesis of BCMB derivatives. There are several methods to synthesize BCMB derivatives, such as applying HCHO or (HCHO)n with concentrated hydrochloric acid or anhydrous HCl in the presence of zinc chloride, adopting (HCHO)n with hydrochloric acid in acetic acid aqueous, or utilizing HCHO reacts with hydrochloric acid and bubbles anhydrous HCl which was so called Wood method[3].The methods mentioned above usually affored low yield of BCMB substituted by long alkoxy group, while the synthesis of BCMB with long alkoxy-substituents are the essential for the synthesis of soluble PPV derivatives[4,5].
    褪黑素的设计合成及应用研究
    胡文祥, 王建营, 谭生建, 张向先
    1998, 19(S1):  86-87. 
    摘要 ( 523 )   PDF (131KB) ( 157 )  
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    褪黑素(melktonin),又名松果体素或褪黑激素,是脊椎动物脑中松果腺体合成和分泌的一种吲哚类激素,化学名称是N-乙酰基-5-甲氧基色胺。近20年国内外对此激素研究应用表明:褪黑素在动物体内的合成和分泌主要是由松果体和视网膜感受外界光的昼夜节律来调节的。松果体分泌出来的褪黑素可以调节其它激素,使其它激素维持正常的浓度及循环,而其它激素则控制人体的机能。褪黑素通过影响其它激素,间接地控制人体全身的机能,从而成为人体的重要信息物质之一。人到中年后,其分泌量下降, 于是等待褪黑素供给的器官或组织,也跟着老化而发生故障,从而产生许多生理功能失调现象,诸如睡眠障碍、精力与免疫力下降等,外源给入褪黑素可改善上述症状。褪黑素因其具有的催眠和抗衰老等重要生理作用和几乎无副作用,将成为人类二十一世纪关注的热点之一,现已作为一种新药品和保健食品风靡全球。
    Synthesis And 3D-QSAR of Substituted Hydroxycarboxylates
    Wenxiang HU, Momen LU, Yunzhang RAN, Liuhong YUN, Jianying WAN, G Jiaju ZHOU, Qian XIE
    1998, 19(S1):  88-89. 
    摘要 ( 145 )   PDF (109KB) ( 52 )  
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    Soman is a neural organophosphorus agent. The prophylatic and treatment of soman caused neural disease is very difficult. Hence research or discovery of potent antisoman drugs is very important in life science and the protective medicine against chemical weapons. Most of anticholinergic compounds are only muscarinic receptor antagonists with very weak affinity to nicotinic receptor. Therefore they have poor efficiency against soman poisoning.
    茄酸和茄酸乙酯的全合成研究
    贾春晓, 毛多斌, 候守君, 李银奎, 张峻松
    1998, 19(S1):  90-91. 
    摘要 ( 238 )   PDF (90KB) ( 98 )  
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    茄酸(Solanic acid,I)化学名称是2-异丙基-5-氧代己酸,该物质及其醋类(Solanic acid esters)是烟草香味的重要来源,是烟草在调制、陈化、加工等一系列工序处理中由烟叶中的西柏烯类(Cembrenoids)降解转化而成。茄酸及其乙酯(Ⅱ)具有酸、甜气息,加入卷烟中可以起到明显增加烟香,醇和烟气,大幅度提高卷烟的香味品质的作用[1]。随着低焦油卷烟的发展以及卷烟产品的升级换代,烟草工业对茄酸及其酯类的需求日益迫切, 因此,开发此类香味物质具有重要的应用价值和社会价值。
    A Convenient One-Pot Synthsis of Substituted Furans from Propargylic Dithioacetal
    Chin Fa Li, Tien-Yau Luh
    1998, 19(S1):  92-92. 
    摘要 ( 270 )   PDF (20KB) ( 69 )  
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    The reactions of propargylic dithioactals with organocuprate reagent have recently been explored from our laboratory.1 In this paper, we report the reactions of propargylic dithioactals 1 with organocuprate reagents followed by treatment with an aldehyde to afford the corresponding substituted furans 2.
    Novel Oxidative Coupling of 2-Naphthols to 1,1'-Bi-2-naphthols Catalysed by Solid Lewis Acids Using Atmospheric Oxygen as Oxidant
    Tong-Shuang Li, Hui-Yun Duan, Bao-Zhi Li, Brij B. Tewari, Sheng-Hui Li
    1998, 19(S1):  93-94. 
    摘要 ( 256 )   PDF (85KB) ( 65 )  
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    l,l'-Bi-2-naphthol derivatives have wide applications as chiral inducing agents for asymmetric synthesis.1 There are many good methods for resolution of racemic binaphthols to give enantiomeric binaphthols.2 Therefore, it is essential to established simple, convenient, economically and environmental-friendly methods for preparation of racemic l,l'-binaphthol derivatives. A number of methods have been developed for the oxidative coupling of 2-naphthols usually by using Fe3+, Cu2+ or Mn3+ as oxidants. The reaction were carried out in organic solvent,3a in solid state3b and in aqueous Fe3+ solution.3c However, all those cases by employing excess, usually 2 equivalents of oxidant. The excess Fe3+, Cu2+ and the resulted Fe2+, Cu+ and HCl were not acceptable from a view point of environmental protection. Recently, Sakamoto et at4 and Kantam et at5 independently reported two catalytic oxidative coupling procedure for preparation of l,l'-binaphthols using aerial oxygen as oxidant and Cu2+-exchanged montmorillonite as catalysts. However, both procedures were by using some toxic chlorobenzene as solvent and long reaction time (>2 h) and high temperature(>140℃) were needed. Consquently, there is still a great demand for catalytic oxidative coupling 2-naphthols to generate binaphthols under mild conditions, environmentally friendly procedure and rapid process. Herein we report novel oxidative coupling of to 1,1-bi-2-naphthols (2a, 2b) catalysed by a number of supported reagents using aerial oxygen as oxidant. The results are listed in Table 1.
    Unexpected Products from the Reaction of Naphthols with Cholesterol Catalysed by Montmorillonite K 10
    Tong-Shuang Li, Li-Jun Li
    1998, 19(S1):  95-96. 
    摘要 ( 171 )   PDF (97KB) ( 71 )  
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    Under catalysis of montmorillonites, arenes could be cholesterylated by cholesterol (1) via a Friedel-Crafts alkylation.1 When phenols were employed as substrates for that reaction, aryl cholesteryl ethers were obtained instead of aryl cholestenes.2 However, β-naphthol (2a) and α-naphthol (2b) gave obviously different products. We report here the identification of these unexpected products from the reaction of 2 with 1 catalysed by montmorillonite K 10.
    Novel Enone-benzene Rearrangement of 4,4-Dialkylcholest-5-en-3-ones to Ring-B Aromatic Steroidal Hydrocarbons Catalysed by p-Toluenesulfonic acid
    Hui-Yun Duan, Tong-Shuang Li
    1998, 19(S1):  97-98. 
    摘要 ( 235 )   PDF (84KB) ( 66 )  
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    Under acidic conditions, α,α-dimethyl-β,γ-unsaturated cyclohexanones undergoes an enone-benzene rearrangement leading to aromatic derivatives1-4. We recently run an enone-benzene rearrangement of 4,4-dimethyl-cholest-5-en-3-one (1a) catalysed by montmorillonite K-10 to give 1,3,4-trimethyl-19-norcholesta-1,3,5(10)-triene (2a) in moderate yield accompanying intractable mixture of hydrocarbons as by products5. Repetition of this reaction by employing TsOH as a catalyst, 2a was obtained in 65% yield and a new product, 6-methyl-3-isopropyl-A,19-dinorcholesta-6,8,10(5)-triene (3a), was also isolated in 25% yield. The formation of 3a has not been reported in earlier studies1-5. Herein we report the novel enone-benzene rearrangement of 4,4-dialkylcholest-5-en-3-ones (1a~d) leading to ring-B aromatic steroidal hydrocarbons (3a~d) catalysed by TsOH (Scheme 1).
    Synthesis of Allobetulin, 28-Oxyallobetulin and Related Biomarkers from Betulin and Betulinic Acid Catalysed by Solid Acids
    Jian-Xin Wang, Tong-Shuang Li, Xue-Jing Zheng
    1998, 19(S1):  99-100. 
    摘要 ( 329 )   PDF (69KB) ( 146 )  
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    Betulin (1a) is an abundant natural product in the birch bark. Betulin itself currently has little usage. However, allobetulin (2a) has been used as an important intermediate in the further transformation of triterpenoids and as a sample for biological studies.1 For example, allobetulin was further transformed to a highly active antifeedant for heliothis zea larvae. Some biomarkers (3a,b; 4a,b) with the same or similar structure as ring-E of 2a were identified in a brown coal.3 Consequently, the conversion of 1a to synthetically, biologically and geochemically more important 2a is of great significance. The transformation of 1a to 2a was reported as early as 1922 by Schulze et al in which betulin was isomerized by formic acid, involving formation and hydrolysis of allobetulin formate, to give 2a in moderate yield.4
    Synthesis of Alkyl Bromide by the Method of Phase Transfer Catalysis
    Chuanxin Zhang, Wanling Si, Baoguo Guo
    1998, 19(S1):  101-102. 
    摘要 ( 178 )   PDF (113KB) ( 74 )  
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    Phase transfer catalysis is one of the most active techniques used in organic synthesis[1]. The process is versatile, fast, inexpensive, involves smooth work-up, give good yield and needs less drastic condition compared to conventional methods of synthesis. The technique has a very broad scope of application[2], surprised, few are have been devised for synthesizing alkyl bromides. Alkyl bromides are important materials in organic synthesis and in agricultural chemical purpose, as well as widely used in the oil field gas exploration and water treatment[3].
    STUDIES ON THE CHEMICAL CONSTITUTIONS OF SONCHUS ARVENSIS L
    Gui-Rong QU, Hong-min ZHANG, Xin-Ying ZHANG, Bai-Gen XIA
    1998, 19(S1):  103-104. 
    摘要 ( 276 )   PDF (68KB) ( 65 )  
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    Sonchus arvensis L. is one of perennial herbaceous plants of the composite family. It is abundant in China. It has the efficacy of for the treatment of fever, carbuncles and inflammation. Thirty-four compounds have been isolated and reported from the plant. In this paper, from the extraction of petroleum ether of sonchus arvensis L.,three chemical substances were isolated. By means of chemical and spectroscopic (IR, 1H-NMR, 13C-NMR, 1H-1H COSY, MS) analysis, they were identified as n-hexacosanol (Ⅰ), α-amyrin (Ⅱ) and santoman (Ⅲ). Among them Ⅱ and Ⅲ are the first time isolated from this genus.
    Fe2(SO4)3·xH2O CATALYTIC ESTERIFICATION OF MANDELIC ACID WITH ALCOHOLS
    Hui Gong, Gui-Sheng Zhang, Huai-Zhou Li
    1998, 19(S1):  105-106. 
    摘要 ( 177 )   PDF (68KB) ( 56 )  
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    Mandelates have played an important role in organic synthesis and are used in artificial flavorings and perfumes. Mandelates may be prepared as follows:1). Direct esterification of mandelic acid with alcohols in the presence of sulfuric acid1,2 or 2,2-dimethoxypropane and sulfuric acid;3 2). Treatment mandelic acid and iodide in the presence of sodium hydrogen carbonate;4 3). Treatment mandelic acid and alcohols with thionyl chloride.5 But these methods have some advantages and are not universally applicable. For example, the direct esterification catalyzed by sulfuric acid is not suitable for acid sensitive compounds and has the disadvantages of the corrosivity of strong acid and usually accompanying side reactions such as carbonization,oxidation, etherification, etc. We now reported the catalytic esterification of mandelic acid with a serious of alcohols using Fe2(SO4)3·xH2O as a new convenient catalyst.
    氯铬酸铵/氧化铝对扁桃酸酯的氧化研究
    贡辉, 张贵生, 李怀洲
    1998, 19(S1):  107-108. 
    摘要 ( 195 )   PDF (70KB) ( 86 )  
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    苯甲酰甲酸酯是重要的有机合成中间体,常用作不对称合成试剂.。文献[1-6]报道了合成苯甲酰甲酸酯的几种方法。这些方法各存在一些缺点,如试剂昂贵,反应步骤多,操作困难,收率低等。文献[5,6]报道了氧化相应的扁桃酸酯合成苯甲酰甲酸甲酯和乙酯的方法,反应简单,收率良好,但没有报道其它酯的合成方法。
    A New Method for Preparing Amine Azo Compounds
    Qing-zhi Zhang, Xie Fei, Shen-song Zhang
    1998, 19(S1):  109-110. 
    摘要 ( 182 )   PDF (69KB) ( 72 )  
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    In previous work, we have found that DMF is a good absorbent of NO2, The resulting product DMF-NO2 can be used as a mild and selective oxidant to oxidize acetals and oximes to corresponding aldehydes or ketones. Now,we find that it is also effective to covert substituted aniline compounds into corresponding amino azo compounds.
    二取代苯基卡巴腙的合成新方法
    时蕾, 贾学顺, 王玉炉
    1998, 19(S1):  111-112. 
    摘要 ( 210 )   PDF (54KB) ( 98 )  
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    二苯基卡巴腙是一种重要的有机分析试剂,常用于测定和检出多种金属离子.1文献报道的合成方法一般是用氧化剂对二苯基卡巴肼进行氧化脱氢制得,但产率偏低,操作较烦.2,3 近来,我们用相转移催化法对二取代苯基卡巴肼脱氢,高产率地制得双(取代苯基)羰基二偶氮化合物.4 但是相转移催化法不能得到单侧脱氢产物. 本文首次用价廉易得的三氯化铁为氧化剂,控制其与二取代苯基卡巴肼的摩尔比, 在酸性介质中反应,高产率地制备出8个二取代苯基卡巴腙化合物.该方法反应时间短, 条件温和,现象明显,操作简便.产物结构已经元素分析,IR, NMR,谱证实.
    A SIMPLE, EFFICIENT AND NEW METHOD FOR PREPARING AZO UREAS
    Cailan Wang, Yulu Wang, Xiaoyang Wang, Jianping Li, Hong Wang
    1998, 19(S1):  113-114. 
    摘要 ( 284 )   PDF (94KB) ( 72 )  
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    Azo compounds are widely utilized as dyes and analytical reagents.They can also be used as materials for non-linear optics and for storage optical information in laser dish[1]. Recently, many noteworthy studies have shown that azobenzene derivatives possess excellent optical memory and photoelectric properties[2]. The preparation of ordinary azo compounds has been described in many references. However, those compounds generally bear alkyl or aryl groups on both sides of the azo linkage (-N=N-).
    Studies on Oxidation of Active α-H of Aromatic Hydrocarbon by CAN/NaBrO3/H2O System
    Jian-Ge Wang, Guan Huang, Qi-Zeng Shi, Kun Cai
    1998, 19(S1):  115-116. 
    摘要 ( 289 )   PDF (56KB) ( 99 )  
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    Cerium ammonium nitrate (CAN) is an expensive and powerful selective oxidant. It has played an important role in organic synthesis. Because it is a single electron oxidant,many organic reactions need large quantities of it. The application of CAN in organic synthesis in the oxidation of alkyl aromatics has so far been limited. In this paper, we wish to report a new method of oxidation of active α-H of aromatic hydrocarbon by CAN/NaBrO3/H2O system. Only catalytic amount of CAN was needed in this method and the selectivity was improved as well.
    The Synthesis of New Type Diazo Compounds by 4-hydroxy-2,2,6,6-Tertramethyl-1-Piperidinyloxy 1 as The Phases Transfer Dehydrogenation Catalyst
    Xiao-Yang Wanga, Jian-Ping Li, YI-Yang Shenc, Hong Wang, Yu-Lu Wang, Zi-Yi Zhang
    1998, 19(S1):  117-118. 
    摘要 ( 356 )   PDF (94KB) ( 51 )  
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    It is well known that 4-hydroxy-2,2,6,6-tertramethyl-1-piperidinyloxyl is a stable nitroxyl radical. It can be used as antioxidants1 and spin labeled compounds to mark protein, biomembrance and nucleic acid etc. Furthermore, as an efficient inhibitor, it can prevent olefin polymerizing by free radical. However, using 4-hydroxy-2,2,6,6-tertramethyl-1-piperidinyloxyl as the phase transfer catalyst has not been reported so far.
    TRIMETHYLAMMONIUM CHLOROCHROMATE ADSORBED ON ALUMINA AS A NEW REAGENT FOR THE CLEAVAGE OF OXIMES AND P-NITROPHENYLHYDRAZONES
    Gui-Sheng Zhang, De-Hong Yang, Mi-Feng Chen, Xiao-Yun Dang
    1998, 19(S1):  119-120. 
    摘要 ( 355 )   PDF (57KB) ( 113 )  
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    Derivatives of carbonyl compounds such as oximes and p-nitrophenylhydrazones have played an important role in the protection of carbonyl compounds,as they are highly crystalline and stable compounds. They are also very extensively used for the characterization and purification of carbonyl compounds. Regeneration of carbonyl compounds from their derivatives under mild condition is an important process in synthetic organic chemistry.
    STUDIES ON SULFINATODEHALOGENATION:THE REACTION OF POLYFLUOROALKYL IODIDES WITH 4-PENTENOIC ACID COMPOUNDS
    WU Fan-Hong, HUANG Wei-Yuan
    1998, 19(S1):  121-122. 
    摘要 ( 353 )   PDF (56KB) ( 46 )  
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    The radical addition of polyfluoroalkyl iodides to carbon-carbon multiple bonds is one of the most important and general methods for synthesis of a variety of fluorine-containing organic compounds.[1] Studies in our laboratory on stulfinatodehalogenation reaction showed that sodium dithionite was a excellent initiation reagent for the addition of polyfluoroalkyl iodides, bromides and halocarbons to alkenes, alkynes and conjugated dienes effectively under mild conditions.[2]
    A Catalytic Enantioselective Synthesis of Biologically Interesting Cyclopropane Amines
    Fu-Chang Shu, Chun-Xiao Xu, Qi-Lin Zhou
    1998, 19(S1):  123-124. 
    摘要 ( 204 )   PDF (78KB) ( 54 )  
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    The synthesis of cyclopropane amine has attracted considerable interest from organic chemists because of the biologically importance and its occurrence in numerous natural products1. Several synthetic cyclopropane amines have been used as drugs, e.g. the monoamine oxidase inhibitor tranylcypromine (1)2. However, it has been found that two enantiomers of chiral cyclopropane amine have different pharmacological effects3,which demands organic chemists to develop efficient methods to prepare them enantioselectively. Previous synthesis of enantiomerically pure cyclopropane amines involves resolution of racemic cyclopropane carboxylic acid followed by Curtius degradation4.
    Reductive Coupling Reaction of Carbonyl Compounds In a TiCl4/Ga Bimetal Redox System
    Xiao-Lin Zhang, Ming Li
    1998, 19(S1):  125-126. 
    摘要 ( 264 )   PDF (69KB) ( 66 )  
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    For about 20 yeers the chemisty of low-valent titanium complexes has received great attention1 and now many of the reactions involving them are commonly used in synethesis2. The reactivity, of the low-valent titanium slurries, obtained after reduction of titanium trichloride or titanium tetrachloride by means of strong reducting agents such as magnesium, zinc in tetrahydrofuran has also been studied3-4. In 1995,we reported that carbonyl compounds react with ethyl trichloracetate and iodoacetonitrile in a PbCl2/Ga bimetal redox system5. Herein, we report reductive coupling reaction of carbonyl compound to afford E-alkenes with TiCl4/Ga bimetal redox system. Simplicity of produre and moderate to excellent yields of product.
    Synthesis, Chemistry and Applications of Heterocyclic Cage Compounds (V)
    吳宗益, 林輝章,嚴嘉蕙, 葉青芳, 陳志豪, 吳献仁
    1998, 19(S1):  127-128. 
    摘要 ( 281 )   PDF (78KB) ( 93 )  
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    The synthesis and chemistry of polycyclic cage compounds have attracted considerable attention in recent years.1 The vast majority of the work reported in this area has dealt with caybocyclic cage compounds. On the other hand, the synthesis and chemistry of heterocyclic cage compounds have received less attention. Recently, we have accomplished the synthesis of a series of oxa-cage compounds and performed the chemical transformations of these oxa-cage compounds.2 As part of a program that involves the synthesis,chemistry and applications of heterocyclic cage compounds we report here the synthesis of heterocyclic cage compounds 1-12. We also wish to report the applications of compounds 7-12 on the π-facial selectivities. Studies on the cation-binding properties of compounds 1 and 2 and other oxa-cages are undertaken.
    Synthesis and Structure-Activity Relationships of Anticholinergics of Dibenzo[b,e] oxepin(thiepin) Hydroxycarboxylates
    Gao Shouhai, Yun Liuhong
    1998, 19(S1):  129-130. 
    摘要 ( 396 )   PDF (87KB) ( 76 )  
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    In order to investigate the relationships between the conformations of tricyclic hydroxycarboxylates and their anticholinergic activities, and to explore the effects of changing the linking groups between the two benzene rings in tricyclic compounds on anticholinergic activities and on the selectivity to the central nicotinic receptor, a series of new tricyclic anticholinergic compounds-dibenzo[b,e]oxepin (thiepin) hydroxycarboxylates (Fig. 1) were designed and synthesized.
    Synthesis And Biological Activities of 4-Neoalkyl-2,6,7-Trioxa-1-PhosphabicycIo[2.2.2] Octanes
    ShuXin LI, WenXiang HU, HuaTang XU, JianYing WANG, Shengian TAN
    1998, 19(S1):  131-132. 
    摘要 ( 226 )   PDF (71KB) ( 67 )  
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    4-Alkyl derivatives of 2,6,7-trioxa-1-phosphabicyclo[2.2.2] octanes are extensively used for spectroscopic studies and are candidates for use as flame retardants, vinyl resin stabilizers and antioxidants[1-4]. Bicyclic phosphates are antagonist of GABA receptor, further research show that these compounds act on the chloride ion channel connecting with GABA receptor. So bicyclic phosphate can act as drugs to probe the Cl- channel. Our preliminary pharmacological results indicate that these bicyclic phosphorus compounds should be handled with great care because of their high toxicity to mammals. Some derivatives of bicyclic phosphates have been prepared in our laboratory.
    ACCELERATED APPROACH TO THE SYNTHESIS OF METHOXYCARBONYL-TERMINATED POLYETHER DENDRIMERS
    LI Xiao-Hong, CAO Xiao-Ping, ZHOU Wei-Gang, NIE Kai-Sheng
    1998, 19(S1):  133-134. 
    摘要 ( 266 )   PDF (97KB) ( 139 )  
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    Dendrimers are macromolecules that radiate out from a central core, with the number of branch points on a given arm increasing exponentially from the core to the periphery.1 Because of their novel properties, dendrimers have found many uses, including as unimolecular micelles, novel amphiphiles, and complexation agents.2 These and other applications will benefit from more efficient methods of dendrimer preparation. The synthesis of dendrimer can be divided into both the divergent approach developed by Tomalia3 and Newkome,4 and the convergent method of Frechet.5 The convergent method was adopted in the synthesis of our target methoxycarbonyl-terminated polyether dendrimers. This method has the advantage over the divergent one in that the number of reaction in each step is restricted to a fixed small number irrespective of dendrimer generation, therefore completion of the reaction in each step can be controlled and monitored and large excess of reagent is not required even in the preparation of higher generation dendrimers.
    2-溴-4,4'-二硝基-3'-二烷基(芳基)锍-2'-联苯酚内盐的结构及性质的研究
    侯自杰, 王素芳, 孙海鹰
    1998, 19(S1):  135-136. 
    摘要 ( 212 )   PDF (71KB) ( 122 )  
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    最近我们通过胺诱导的3,7-二硝基二苯并溴五环盐(1)与亚砜的反应合了一系列结构新颖的苯并锍酚内盐3a-e(式1)。3的结构最初是通过其元素分析及各种谱学分析数据建立的,其后我们培养出3a及3d的单晶,进行了X-Ray晶体及分子结构分析,其结果进一步确证了这一结构。
    3,7-二硝基二苯并溴五环硫酸氢盐与亚砜反应的研究
    侯自杰, 王素芳
    1998, 19(S1):  137-138. 
    摘要 ( 287 )   PDF (66KB) ( 84 )  
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    前不久我们报道了3,7-二硝基二苯并溴五环硫酸氢盐(1)的合成、结构、生物 活性及其与一些亲核试剂的反应1,2。最近我们在研究1与一些胺类化合物在二甲基亚砜中进行的反应时发现二甲基亚砜参与了反应且反应结果与胺/1 (摩尔比)密切相关。当胺/1 >5时反应主产物为相应的亲核取代产物2a-d,而当胺/1=1时无论使用何种胺反应的主产物均为一种红色结晶,经1HNMR,1CNMR,EIMS,IR及元素分析确定其为一种结构新颖的苯并锍酚内盐3a
    The First Efficient Approach from α-(-)-Santonin to Dihydroagarofuran Sesquiterpene
    Biangdong Sun, Yongqiang Tu, Wujiong Xia, Bin Wu
    1998, 19(S1):  139-139. 
    摘要 ( 277 )   PDF (39KB) ( 100 )  
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    The naturally occurring dihydroagarofuran compounds have been demonstrated to show some important bioactive activities, such as insect antifeedant, antitumor activities.1 Synthetic research of this kind of compounds have been attracting the increasing interest of organic chemists. Because a total synthesis of polyol skeleton involved too many steps,2 our synthetic efforts are focusing on search for a short and efficient approach and thus, we begin with readily available α-(-)-santonin(1). The creative key steps include generation of C5-OH, the stereochemical reversion at C-7 and the cyclization of tetrahydrofuran. A successful approach is shown in the following scheme.
    Didemnaketals 类似物的合成研究-(3R,5R,6S)-3,7-二甲基-5,6-二羟基辛醛中间体的手性合成
    王平珍, 涂永强, 贾彦兴, 别平彦, 刘增路
    1998, 19(S1):  140-141. 
    摘要 ( 363 )   PDF (56KB) ( 114 )  
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    Didemnaketals类化合物(1和2)是一类具有明显抗爱滋病活性的海洋天然产物[1]。为探讨这类化合物的合成及生物活性,我们最近开展了其类似物3的合成研究。根据反合成分析,目标分子3的合成最终可以归结为4和5的合成。本摘要主要介绍片段4的合成,其中最关键的问题是建立三个手性中心(C-3, C-5,C-6)。为此,我们选择了分子中具有一个手性甲基的天然薄荷酮6作为起始原料,经两步反应得到环氧化合物[2,3],再经重排开环反应成功地建立了第二个手性中心(C-5)。9经过两步反应, 最后用NaBH4还原得立体控制产物13,从而又成功地建立了第三个手性中心(C-6)。由于化合物12自发地形成具有一个手性中心的六员环半缩醛结构,因而我们得到的13是一对差向异构体。目前我们已经顺利地得到了标题化合物4。
    A Novel Cyclization of Squalene Initiated by Radical Cation
    Wei Wang, Qing-Xiang Guo, Wei Yu, You-Cheng Liu
    1998, 19(S1):  142-143. 
    摘要 ( 292 )   PDF (92KB) ( 78 )  
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    Squalene 1 is recognized as the precursor of sterols and polycyclic triterpenoids that play important roles in numerous life processes1. In view of the fact that the cyclization of hexa-1, 5-diene by γ-irradiation2 and some isoprenoid polyenes by photochemical method3 through radical cation intermediates have been reported and that tris (p-bromophenyl)ammoniumyl hexachloroantimonate (TBPA+SbCl6, 2) could oxidize olfines to the corresponding radical cations that underwent pericyclic reactions4, we thought it might be worthwhile to try the biomimetic cyclization of squalene initiated by radical cations. Previously we5 have reported the cyclization of geraniol and nerol to cis-p-mentha-2,8-dien-l-ol by reaction with 2. Herein, we report the cyclization of 1 initiated by 2 in dry dichloromethane to give 20-R-protosta-5,24-diene 3a and 20-S-protosta-5,24-diene 3b in the ratio of 1:1 with the total yield of 20%(Scheme 1).
    Synthesis of 6-aryl-3-cinchophenyl-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles
    Peng-Fei XU, Lin-Mei ZHANG, Xin-Ping HUI, Zi-Yi ZHANG
    1998, 19(S1):  144-145. 
    摘要 ( 257 )   PDF (83KB) ( 60 )  
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    In recent years, fused heterocycles have been found to possess many unique properties in synthesis and pharmacology. Especially, 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles derivatives have been attracting much attention of chemists and pharmacologists because of their broad-spectrum biological activities such as antibacterial1, hypotensive and CNS depressant2 activities. We have prepared some 3,6-substituted 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles and found that these compounds exhibited antimacrobial, insecticidal and promote plant growth.3-5 Cinchophen had been used widely as medicine in clinic,but has been obsolete in recent years due to its by-effect. In order to seek for other uses of cinchophen, as a continuation of our preceeding studies, we used cinchophen as the starting material to synthesize ten new 6-aryl-3-cinchophenyl-l,2,4-triazolo[3,4-b]-l,3,4-thiadiazoles 5a-j. Compound 1 was prepared by the reaction of cinchophen and ethanol in the presence of sulfuric acid. 1 then reacted with hydrazine hydrate in absolute ethanol to give 2 which yielded 3 on treatment with CS2 and KOH. On refluxing of 3 with excess hydrazine hydrate, 4 was obtained. 4 reacted with various substituted benzoic acids in the presence of POCl3 to afifort 5a-j.
    Studies on Semisynthesis and Antibacterial Activities of 7β-(l-aryl-5-methyl-l,2,3-triazol-4-acylamido)-3-(2-substituted-1,3,4-oxadizol-5-thiomethyl) Cephalosporin
    Xin-Ping HUI, Peng-Fei XU, Lan HAO, Zi-Yi ZHANG, Zuo-Wu GUAN
    1998, 19(S1):  146-147. 
    摘要 ( 241 )   PDF (94KB) ( 112 )  
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    Cephalosporin derivatives have been a subject in the field of β-lactam antibiotics due to their broad-spectrum biological activities in recent years. Chemical manipulation of the C-3 and 7β-position in the cephalosporin molecule has resulted in the discovery of numerous novel antibiotics. In general, the C-3 position of the cephalosporin were substituted with heterocyclyl sulfurs or nitrogens and the 7β-position were substituted with heterocycles or aryl1. The side chain at 7β-position determined their antibacterial activities and antibacterial spectrum, moreover, the substituted groups at C-3 position not only affect pharmacokinetic properties, but antibacterial activities and antibacterial spectrum as well.2 Roche Reiner company found that the activities of cephalosporin can be improved by changing the R of RCONH- at 7β-position of 7ACA and introducing various thioazoleheterocycles into C-3 position of it.3 It is no doubt that these heterocycles increased their activities and wided their antibacterial spectrum. In the course of our studies on the modification of cephalosporin, our efforts have been focused on introducing heterocycles into C-3 and 7β-position of 7ACA with the hope of achieving better antibiotics.
    Synthesis of 6-(1-Aryl-5-methyl-1,2,3-triazol-4-yl)-3-(4-Pyridyl)-s-Triazolo[3,4-b]-l,3,4-Thiadiazoles
    Xiao-Wen Sun, Yan Zhang, Zi-Yi Zhang
    1998, 19(S1):  148-149. 
    摘要 ( 225 )   PDF (100KB) ( 89 )  
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    A survey of literature1 revealed that s-triazolo[3,4-b]-1,3,4-thiadiazole, an interesting fused system of s-triazole and 1,3,4-thiadiazole rings, has received much attention during recent years on account of its prominent utilizations as antifungal, antiinflammatory, antiviral, analgesic and anthelmintic agents probably resulting from its planner and compact structure. Our earlier work on the synthesis of this class of heterocycles showed antibacterial, herbicidal and plant growth regulative properties2-3 for the compounds. 1,2,3-Triazole derivatives have found their wide use in medicine, agriculture and industry4-5. Incorporation of 1,2,3-triazole moiety into the 6-position of this ring system may lead to achieving compounds of better biological activities. In view of the above findings coupled with scanty reports on these condensed compounds carrying 6-heterocyclic groups, we wish to report here the condensation of 4-amino-5-mercapto-3-(4-pyridyl)-l,2,4-triazole(2) with 1-aryl-4-carboxy-5-methyl-1,2,3-triazoles(1a-j) as a part of our continuing interest in this area.
    Regioselective Synthesis of Two Novel 2-geranyloxyacetophenones
    Haifu GUO, Chusheng HUANG, Wenfei TAN, Yulin LI
    1998, 19(S1):  150-151. 
    摘要 ( 271 )   PDF (80KB) ( 88 )  
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    The phenols containing geranyl units1 are a large group of interesting natural products exhibited many physiological actions as antiflammatory, antibacterial and antioxidative activities2. Two novel acetophenones 1 and 2 were recently isolated from the fruits of Evodia merrillii, a small folk medicinal tree widely distributed in Taiwan3. Their structures were elucidated as 2-(1'-geranyl)-4,6-dihydroxyacetophenone 1 and 2-(1'-geranyloxy)-2,6,α-trihydroxyacetophenone 2 by means of spectroscopic data. So far as we know, the total synthesis of them have not been reported yet. Herein, we wish to report the first total synthesis of 1 and 2,starting from 2,4,6-trihydroxyacetophenone.
    Total Synthesis of C-8-Geranylflavonoids
    Chusheng HUANG, Zhe ZHANG, Yulin LI
    1998, 19(S1):  152-153. 
    摘要 ( 239 )   PDF (88KB) ( 60 )  
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    Geranylflavonoids are interesting natural products isolated in recent years from some traditional medicinal plants. Some of these flavanoids have been reported to exhibit hypotensive, antibacterial and antitumor effects1. With respect to the synthesis of geranylflavonoids, only the 8-geranylflavanone skeleton as found in compounds 12, 23 and 34 has not been yet prepared.
    The Total Synthesis of (±)-13-Hydroxyneocembrene
    Yacheng Xing, Wen Cen, Ying Li, Jiong Lan, Yulin Li
    1998, 19(S1):  154-155. 
    摘要 ( 206 )   PDF (72KB) ( 83 )  
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    (13S)-hydroxyneocembrene(18), a cembranoid which was isolated in 1988 from soft coral Sarcophyton trocheliophorum1, has been shown to be an effective inductor of the release of labeled glucose from the lecithincholesterol liposomes and have cytostatic activities2. The geometrical structure and absolute configuration of 18 have been defined to be 1S, 2E, 7E, 11E, 13S. Herein, we report the total synthesis of (±)-13hydroxyneocembrene(18).
    First Total Synthesis of the (±)-Preverecynarmin
    Jiong Lan, Zuosheng Liu, Yulin Li, Wen Cen, Yacheng Xing
    1998, 19(S1):  156-157. 
    摘要 ( 203 )   PDF (84KB) ( 89 )  
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    The preverecynarmin(12), (+)-(1E,3E,7E,11E)-cembra-3,7,11-tetraen-6yl acetate,was first isolated in 1990 from both Armina maculata and its prey,the pennatulacean coral Veretillum cynomorium with other there briarane diferpenoids and cembene-C((1E,3E,7E,11E)-cembra-l,3,7,11-tetraen1. As far as we known, the bioactive test and total synthesis of 12 have not been reported yet. Herein we wish to describe the first total synthesis of (±)-preverecynarmin (12).
    First Total Synthesis of 4,5-Secoeudesmane-type and Iphionane-type Compounds——Synthesis of 4,5-Dioxo-seco-γ-eudesmol and 5β,11-Dihydroxyiphionan-4-one
    Zhaoming XIONG, Gang ZHOU, Xiaolei GAO, Yonggang CHEN, Yulin LI
    1998, 19(S1):  158-159. 
    摘要 ( 245 )   PDF (91KB) ( 75 )  
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    4,5-Secoeudesmane-type and iphionane-type compounds are sesquiterpenes with new carbon skeletons found in natrual sources in recent years.1-6 The Co-occurence of 4,5-secoeudesmanes, iphionanes and eudesmanes as natrual products suggests that 4,5-secoeudesmanes, iphionanes most likely are generated biogenetically from eudesmanes, and iphionanes are formed biogenetically by aldol reaction of 4,5-dioxosecoeudesmanes.1,4,6,7 The study on the synthesis of this two kind of new sesquiterpenes has not been reported in the literature.
    Facile One-pot Transformation of 2,3-Epoxy Alcohols into Allylic Alcohols
    Zuosheng LIU, Jiong LAN, Yulin LI
    1998, 19(S1):  160-161. 
    摘要 ( 260 )   PDF (82KB) ( 64 )  
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    Optically-active allylic alcohols have been frequently used as chiral building blocks for the preparation of optically pure compounds.1 There are at present various methods for the synthesis of optically active allylic alcohols including the kinetic resolution racemic allylic alcohols,2 reductive rearrangement of 2,3-epoxy alcohol by metal, halide and telluium-based chemistry.3 To our knowledge, One-pot Transformation of 2,3-epoxy alcohols into allylic alcohols, especially via epoxy iodides,is limited to Dorta's method3 using a Ph3P,iodine, imidazole,2,6-lutidine and water system. The original Dorta's method can be successfully applied to the formation of tertiary allylic alcohols, but give unsatisfactory results in formation of secondary allylic alcohols.
    First Total Synthesis of (-)-4-O-(6'-Hydroxy-7'(9')-Dehydro-6',7,-Dihydrogeranyl)-Coniferyl Alcohol
    Zuo Sheng LIU, Chu Sheng HUANG, Jiong LAN, Yu Lin LI
    1998, 19(S1):  162-163. 
    摘要 ( 221 )   PDF (87KB) ( 83 )  
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    Some Ligularia species have long used as folk remedies due to their antibiotic, antiphlogistic and antitumor activities.1 Compound 1,2 a novel coniferyl alcohol, was isolated from ligularia duciformis(Compoitae). The geometrical structure of 1,determined by spectroscopic techniques, was corresponded to 4-o-(6,-hydroxy-7'(9')-dehydro-6',7'-dihydrogeranyl)-coniferyl alcohol. But its absolute configuration at C-6,has not yet been determined. Herein, we report the total synthesis of (6'S)-(-)-1 from Geraniol 2 through 9 steps (Scheme 1).
    First Total Synthesis of (±)-Ponganone Ⅲ
    Wenfei Tan, Erqing Tang, Chusheng Huang, Yulin Li, Wen Cen, Yacheng Xing
    1998, 19(S1):  164-165. 
    摘要 ( 296 )   PDF (61KB) ( 73 )  
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    In recent years, the synthesis and pharmacology of pyranoflavanoids have been extensively investigated due to their wide range of pharmacological properties[1-3]. Ponganone Ⅲ[4],a new natural pyranoflavanone isolated from the Pongamia pinnala, was identified as (2S)-3',4'-dimethoxy-6',6"-dimethylpyrano-[2",3":7,8]-flavanone (2) on the basis of spectra data. Its precursor,3,4-dimethoxy-2'-hydroxy-6",6"-dimethylchromeno-[2",3":4',3']-chalcone (1) is also a new natural product[5] isolated from the roots of Lonchocarpus subglaucescent. Their total synthesis have not been reported. Herein, we wish to report the first total synthesis of compounds 1 and 2 in order to confirm the proposed structure and further more to evaluate its biological activities.
    Facile Synthesis of 6β-Hydroxy-7α(H)-eudesma-4-en-3-one and β-Cyperone
    Gang ZHOU, Zhao Ming XIONG, Yong Gang CHEN, Yu Lin Ll
    1998, 19(S1):  166-167. 
    摘要 ( 304 )   PDF (95KB) ( 60 )  
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    Eudesmane derivatives have been drawing considerable attention due to their wide spectrum of biological proerties, particulaly antifeedant, cell growth inhibitory and plant growth regulating activities.1 In recent years a number of C-6 oxyfunctionalized eudesmanes and β-dihydroagarofurans,such as compounds 3-6,have been isolated from nature sources. However the reports on the synthesis of this particular kind of compounds are few and the reported syntheses are generally by synthetic methodology starting from α-santonin 22. Our interest of study on the synthesis of this kind of compounds prompted us to investigate a new synthetic route from cheap material (+)-dihydrocarvone 7.
    Total Synthesis and Stereochemistry of 13-Hydroxy-α-eudesmol
    Yonggang Chen, Zhaoming Xiong, Gang Zhou, Lijun Liu, Yulin Li
    1998, 19(S1):  168-169. 
    摘要 ( 221 )   PDF (102KB) ( 69 )  
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    Recently, 13-hydroxy-α-eudesmol 1a was first isolated from C. uncata Cunn. by King and Robinson et aL and its structure was determined by high field NMR techniques, however, the absolute configuration of C-11 remained unsolved. Herein, we report the first total synthesis and determination of the stereochemistry of 13-hydroxy-α-eudesmol. In our synthesis (+)-α-selinene has also been accomplished.
    N-芳基-二茂铁甲酰烯胺的合成
    边占喜,李保国,郭灵通
    1998, 19(S1):  170-171. 
    摘要 ( 235 )   PDF (93KB) ( 63 )  
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    含二茂铁基的烯胺及其过渡金属络合物前人做过一些工作[1-4]。但二茂铁甲酰烯胺类衍生物未见文献报道。我们考虑二茂铁甲酰烯胺及其络合物的应用前景,研究了二茂铁甲酰烯胺类化合物的合成方法及其络合性质。由二茂铁甲酰丙酮[5]与取代苯胺缩合,得到了十种不同N-芳基-二茂铁甲酰烯胺:FcCOCH=C(CH3)-NHC6H4X 其中:X=H; O-, m-, p-OH; m-, p-OCH3; O-, p-Cl; m-, p-NO2着重研究了取代基的种类与位置对缩合反应的影响。
    二茂铁异羟肟酸-稀土螯合物的合成与表征
    边占喜,张生,李保国
    1998, 19(S1):  172-173. 
    摘要 ( 265 )   PDF (100KB) ( 76 )  
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    异羟肟酸类过渡金属及稀土配合物前人做过一些工作[1-2],但二茂铁异羟肟酸稀土配合物未见文献报道。考虑到二茂铁衍生物做为燃速催化剂和反应中间体及稀土配合物的荧光性能等应用前景,我们以二茂铁异羟肟酸(FHA) FcCONHOH(1)为配体, 合成了十四种稀土螯合物(2-15)其中2-15代表的稀土金属依次为 La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu。并对配体和螯合物进行了元素分析、热分析、IR谱和1HNMR谱表征。

    Synthesis of a New Conformational Constrained Cyclic Peptide Containing Pyridine and Cystine
    Hai Huang, Jinpei Cheng, Xiaohu Gao, Linjing Mu, Xubo Hu
    1998, 19(S1):  174-175. 
    摘要 ( 209 )   PDF (98KB) ( 97 )  
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    As a class of peptide series, cyclic peptides have aroused great interest in the past few years. They are found to possess many biological functions such as membrane transport, antibiotics, toxins, hormones and so on1. Similar to the well-known macrocyclic compounds such as the crown ethers, cyclodextrins and calix arenes, they are found to be good host molecules as well in recognizing ions and small molecules2. Recently, much progress has been made on the synthesis of conformational constrained cyclopeptides in this laboratory. Because introducing a rigid subunit to the backbone of cyclic peptides can largely reduce their, conformational complications and enhance their recognition affinities, Ranganathan3 and Cheng4,5 and co-workers have synthesized some series of cyclic peptides analogues containing adamantane and benzene, respectively. These pseudocyclopeptides all showed good affinity to form complexes with ions and small molecules.
    Design and Synthesis of Calix[4] arene-Constrained Cyclopeptide
    Xubo Hu, Jin-Pei Cheng, Xinxin Han, Linjing Mu, Hai Huang, Jianming Lu
    1998, 19(S1):  176-177. 
    摘要 ( 228 )   PDF (93KB) ( 78 )  
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    There have been great continuing interests in cyclic peptides in the past two decades. Apart from being useful tools for identifying the functional conformations of bioactive peptides, and guiding the rational design of peptidomimetic drugs, cyclic peptides serve as templates in the de novo design[1] of artificial proteins and as models[2] for the study of prepefence in protein secondary structure. They also play an important role in ion transport across biological membranes,[3] and can self-assemble size-adjustable nanotubes.[4] However, study on their molecular recognitions for ions[5] and neutral molecules, especially for organic compounds,[6,7] which are believed to be one of the most attractive properties, were hampered by their considerable large degree of the freedom of the cavities.
    Synthesis and Complexation of Phosphorus- and Selenium-Containing Macrocycles
    Jinliang Li, Changqiu Zhao, Yongmei Wang, Jiben Meng
    1998, 19(S1):  178-178. 
    摘要 ( 203 )   PDF (50KB) ( 73 )  
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    A facile synthesis method for SePSe-containing macrocycles was developed. The macrocycles were obtained by one-pot reaction. The powder selenium was reduced by potassium borohydride in absolute alcohol to produce potassium diselenide,which reacted with bis(o-bromomethylphenyl)phenylphosphine oxide 1 to give the intermediate, 1-phenyl-2,3:8,9-dibenzo-5,6-diselena-1-phosphacyclononadiene 1-oxide 2, and its oligomer. Without isolation, the mixture was treated with potassium borohydride and sodium hydroxide to produce diselenide anion, then allowed to react with alkyl dibromide to give SePSe-containing macrocycles (shown as Scheme 1). A medium-sized eight-membered heterocycle, l-phenyl-2,3:7,8-dibenzo-5-selena-1-phosphacyclooctadiene 1-oxide 4 was obtained surprisingly. The formation of heterocycle 4 was due to the presence of potassium selenide when selenium was reduced by potassium borohydride. The attempts to isolate the intermediate 2 were totally unsuccessful. When the alkyl dibromide was the 1,2-dibromoethane, the expected macrocycle was not obtained, with deposition of red selenium and extrusion of ethylene. The similar case was reported by Pinto B. M. in 1989.
    固体酸催化合成富马酸二甲酯的研究
    袁忠勇, 魏荣宝, 王敬中, 李赫咺
    1998, 19(S1):  180-181. 
    摘要 ( 206 )   PDF (107KB) ( 81 )  
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    富马酸二甲酯是80年代国内外研究开发的新型防腐防霉剂[1],具有毒性低,耐热性能好,能在pH=3~8范围内使用等特点,广泛用于食品、饲料、粮食、化妆品、纺织品、制药等行业。因其用量小,毒性低,在国外已广泛被使用,特别是在饲料方面。目前,生产上合成富马酸二甲酯多以硫酸和盐酸或磷酸和盐酸的混合酸为催化剂,在马来酸(或顺酐)和甲醇反应体系中进行异构酯化而制得。然而用硫酸盐酸混合酸做催化剂对设备严重腐浊,污染环境,后处理麻烦,且易发生副反应。本文采用固体酸催化剂 HZSM-5分子筛,用顺酐与甲醇反应,一步催化合成富马酸二甲酯,并对其反应机制作了推理。
    Studies on Synthesis and Biological Activities of Di-heterocyclic Compounds Containing Pyrazole
    CHEN Hansong, LI Zhengming
    1998, 19(S1):  182-183. 
    摘要 ( 227 )   PDF (70KB) ( 62 )  
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    Pyrazole derivatives were reported to show a broad spectrum of biological activities. Some of these compounds exhibited fungicidal, herbicidal and insecticidal properties. For instance, Fipronil (MB46030) is a new pyrazole insecticide that provides excellent control of many soil and foliar insects on a wide variety of crops and noncrops[1]. And ET-751 is a new 3-phenylpyrazole herbicide, its primary use is for the post-emergence control broad-leaved weeds in cereals[2].These observations and our interest in looking for bio-active compounds prompted us to study pyrazole derivatives further.
    A Preliminary Study of the Reaction of 5-Pyrazole Hydrazide and Malononitrile Derivatives
    CHEN Hansong, LI Zhengming
    1998, 19(S1):  184-185. 
    摘要 ( 279 )   PDF (66KB) ( 66 )  
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    The reaction of alkyl hydrazine with ethoxymethylenemalononitrile (EMM) is a routine reaction, the corresponding product, pyrazole ring, will be obtained usually, For example, p-chlorophenylhydrazine with EMM[1].However, 5-pyrazole hydrazide[2] is different. When they reacted with EMM on condition that either reflux or room temperature, l,2-bis(5-pyrazolylcarbonyl)hydrazine (3),the abnormal products, instead of 5-amino-4-cyano-1-pyrazolylcarbonyl-1H-pyrazole(4) were formed (see Scheme 1).
    Synthesis of Novel Derivatives of 1,5-Dihydro-4,6-dithio-l,3,5,2-triazaphosphorine-2-oxide from N,N-bis(2-chloroethyl)diisocyanato phosphoramide
    You Huang, Ruyu Chen
    1998, 19(S1):  186-187. 
    摘要 ( 295 )   PDF (66KB) ( 115 )  
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    Cancer is one of the most serious disease of human beings, and studies on antitumor drugs are still challenging scientists to look for new highly active compounds with low toxicity in this field. Cyclophosphamide (Endoxan), one of the most effective antitumor agents has been widely used in cancer chemotherapy1. However, acrolein, from its metabolysis of hepatic mixed function oxidases in the liver, is toxic to the urinary system2, hence,its clinical usage is restricted. With references to our previous works3,4,we designed and synthesized a novel type of compounds Ⅰ with a nitrogen mustard group attached to the phosphorus atom of the heterocyclic ring in which the nitrogen atom at position 5 is from a α-substituted amino acid ester.
    Synthesis of 1-(2'-Alkylthioethoxy)methyl Uracil and Thymine Derivatives
    Xuejun Liu, Ruyu Chen
    1998, 19(S1):  188-189. 
    摘要 ( 239 )   PDF (73KB) ( 94 )  
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    There is a serious need for compounds that are effective in the treatment of cancer and virus (HIV. Human Immunodeficiency Virus,etc.). Among the large number of nucleoside analogs which have been synthesized and evaluated(1-2) recently several 5'-alkylthio nucleosides have been reported to exhibit good antitumor and antiviral activities(3-4). Their anticancer mechanism involves blocking cancer cell proliferation and inhibiting the cytoplasmic isozyme(C-TK)(5), one isozyme of thymine kinase, which predominates in human tumor cell lines(6). As we know, many acylic nucleoside analogs have appeared good biological activities(7). It is reported that they can also act on some thymine kinases and end up the propagation of the viral DNA chain(8).
    Synthesis of Some 5'-Thiophosphononucleosides
    CHI GUOCHEN, CHEN RUYU
    1998, 19(S1):  190-191. 
    摘要 ( 209 )   PDF (56KB) ( 101 )  
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    A series of 5'-diethoxythiophosphononucleosides involving diastereomers were synthesized, which as isomers of nucleotides were anticipated to possess potential biological activities.
    新型吡唑基缩胺脲类化合物的合成与生物活性
    刘莹,陈卫强,金桂玉
    1998, 19(S1):  192-193. 
    摘要 ( 285 )   PDF (83KB) ( 72 )  
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    吡唑类化合物具有较好的杀虫、杀菌和除草活性,由于它高效、低毒以及吡唑环上取代基多方位变换,因而具有广阔的开发前景,近年来已出现了多种含吡唑基的商品化品种。另外缩胺脲类化合物作为新开发的杀节肢动物的药剂之一,因其杀虫活性高而越来越受到关注。为了寻找新的具有生物活性的化合物,本文以取代吡唑Ⅰ为原料,与水合肼反应形成腙Ⅱ,然后与异硫氰酸酯反应,合成了一系列含取代吡唑基的新型缩胺脲类化合物Ⅲ。
    SYNTHESIS OF SOME NEW TYPE CHRYSANTHEMIC ESTER
    Liao Xiangjun, Zhang Chunxiang, Wang Likun, Dai Jianming, Liu Zhun
    1998, 19(S1):  194-195. 
    摘要 ( 237 )   PDF (44KB) ( 75 )  
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    Not only is Cantharidinum considered the active principle of antineoplastic drug in Chinese traditional medicine[1], but also it and its natrii-cantharidas can be used herbicide and defoliant for legume plants. Seen from the structure of nor-cantharidinamine, it is a five-membered ring glutarimide,which is an active group in pesticide.
    SYNTHESIS OF CYCLIC N-(2,4-DICHLOROPHENOXYACETYL)-O-DICARBOXIMIDES
    Liao Xiangjun, Huang Guiqin, Zhang Chunxiang, Wang Likun, Liu Zhun
    1998, 19(S1):  196-197. 
    摘要 ( 277 )   PDF (45KB) ( 60 )  
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    Cantharidinum is not only considered the active principle of antineoplastic drug in Chinese traditional medicine[1], but also it and its natrii-cantharidas can be used herbicide and defoliant for legume plants. Seen from the structure of nor-cantharidinamine, it is a five-membered ring glutarimide,which is an active group in pesticide.In 1986,Lacova,M. Reported that the cyclic N-(aryloxyacetyl)-O-dicarboximides exhibited herbicide and fungicide activity[2],but as now there is no report that reports the synthesis and pesticide activity of the cyclic N-(2,4-dichlorophenoxyacetyl)-O-dicarboximides[2].So we base on the derivative of nor-dehydrocantharidin and 2,4-dichlorophenoxyactic acid to make 6 compounds be synthesized,which were characterized elemental analysis, HNMR,MS.Pesticide activities of these compounds are being tested.
    Combinatorial Synthesis of O-Pyrimidinyl Substituted Methyl-α-D-Glucopyranosides
    Yun Liao, Zheng-Ming Li, Henry N. C. Wong
    1998, 19(S1):  198-199. 
    摘要 ( 319 )   PDF (61KB) ( 59 )  
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    Within last decade, many pyrimidinyl oxy substituted alcohols, aldehydes and carboxylic derivatives had been found with prominent bio-activities such as high herbicidal activities with wide spectrum. After extensively study of the relationship between structures and bioactivities, A brand-new scaffold combining both pyrimidinyl and glucoside moieties was designed and other building blocks were further introduced with the help of polymer-supported regioselective protecting groups. As shown below, a combinatorial synthesis was carried out by applying "mix-split" method to produce the following series of small compounds libraries both in solid-phase and liquid phase.
    Design,Synthesis and Activities of Cyanouracils Photosystem Ⅱ Inhibitors Basen on D1 Protein
    Huayin Liu, Huifen Tan, Huazheng Yang
    1998, 19(S1):  200-201. 
    摘要 ( 196 )   PDF (75KB) ( 66 )  
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    The study on the interaction between protein target and little molecules can help design new drugs, which have more selective and higher activities. A large number of inhibitors,including ureas, triazines and phenols etc.,are known to block photosystem Ⅱ by displacing plastoquinone from the QB-binding niche of the D1 protein in the reaction center. The X-ray crystall structure of D1 protein in high plant is unknown, but the X-ray crystal structure of L protein of photosynthetic reaction centre of Rps. Viridis has already proved in 80'. Based on this structure, the 3D-structure of Pisnm Saihmm 32Kdal (Dl) was constructed by homology modeling method, and the properties, such as steric, hydrophobic, electrostatic properties of active sites region of the Dl protein were also characterized by Grid Search method with probes of CH3E, H2O, NT and proton.The detail proposal of the model will be shown elsewhere.
    Design, Synthesis and Activities of Cyanoacrylates Photosystem Ⅱ Inhibitors Basen on D1 Protein
    Huayin Liu, Huifen Tan, Huazheng Yang
    1998, 19(S1):  202-203. 
    摘要 ( 290 )   PDF (104KB) ( 154 )  
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    Photosynthesis is a particularly attractive target for the design of potential commercial herbicides. Since photosynthesis is a mechanism that occurs in plants only, all inhibitors are in theory nontoxic to mammals. A large number of inhibitors, including ureas, triazines and phenols etc., are known to block photosystem Ⅱ by displacing plastoquinone from the QB-binding niche of the D1 protein in the reaction center. The X-ray study by Deisenhofer et al. of the photosystem of Rps viridis was an important milestone, since it initiated molecular modeling studies in academia and instustry in order to find new PS Ⅱ inhibitors.
    从L-丝氨酸合成手性环状磷脂的替加氟(Tegafor)和尿苷缀合物
    唐除痴, 陈文彬,张成祥,贺峥杰,周正洪,陈茹玉
    1998, 19(S1):  204-205. 
    摘要 ( 240 )   PDF (61KB) ( 92 )  
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    磷脂不仅具有广泛的生物、生理活性,而旦也可以作为药物的有效载体。由药物与磷脂组成的缀合物作为前药,经磷脂的载体功能到达作用部位,再被降解释放出药物分子和磷脂分子,发挥药物作用,达到提高疗效、降低毒性的目的。
    The Chlorination of O-Alkyl S-Alkyl(aryl) Thiophosphoric(-nic) Acid Derivatives with Phosphorus Oxychloride——A New Convenient Method for Synthesis of Chiral S-Alkyl(aryl) Thiophosphoro(-no) Chloridates
    Chu-Chi Tang, Zheng-Jie He, Wen-Bing Chen, Fu-Peng Ma, Zheng-Hong Zhou
    1998, 19(S1):  206-207. 
    摘要 ( 268 )   PDF (81KB) ( 121 )  
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    In our laboratory, the isomerization/chlorination of a variety of O,O-dialkyl phosphoro(-no)thionates 1 with phosphorus oxychloride have been systematically studied. It was found that when R' equals aryloxy[1], alkylthio[2], arylthio[2], dialkylamino[3], phenyl[4], methyl[5],and nitrogen heterocyclic group[6] in 1,respectively, this reaction can proceed smoothly and gives the desired products 2 and 3. Hence, it provides a general synthitic method for S-alkyl thiophosphoro(-no)chloridates, especially for the asymmetric ones.
    A Novel Tandem Reaction for the Synthesis of Fused Pyrazoles
    Zhongwen Wang, Zhengming Li
    1998, 19(S1):  208-209. 
    摘要 ( 261 )   PDF (69KB) ( 85 )  
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    Some of the fused heterocyclic compounds are important pharmaceuticals and agrochemicals. Study on their synthetic methodology is also very important in heterocyclic chemistry. The synthesises of 1H-pyrazole[5,1-b]thiazole[1-2] and lH-thieno[2,3-c]pyrazole[3-5] were reported by fewer literatures.
    Regioselective Addition of 5-Amino-l,2,4-Triazoles and Its Analogues with Arylsulfonyl Isocyanates
    Guang-Fu YANG, Hua-Zheng YANG
    1998, 19(S1):  210-211. 
    摘要 ( 252 )   PDF (83KB) ( 54 )  
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    5-Amino-3-benzyl (aryl)thio-1,2,4-triazoles and its analogues (pyrazole) 1 are important intermediates for the syntheses of a lot of biological active compounds[1,2]. In our previous paper[3], we reported the regioselective addition of 1 with aryl isocyanates and the experimental results showed that the orientation of the addition of 5-amino-3-benzyl (aryl)thio-1,2,4-triazoles and its analogues with the aryl isocyanates can be directed by controlling the reaction temperature.The 1-position adduct 2 was obtained regiospecifically below 120℃, whereas the 5-position adduct 3 was obtained selectively when the reaction temperature was raised to 170℃ (Scheme 1).
    Synthesis of Ethyl 2-Cyano-3-Methylthio-3'-Arylaminoacrylate From Low Nucleophilic Amine
    Huazheng Yang, Huayin Liu, Kai Chen
    1998, 19(S1):  212-213. 
    摘要 ( 234 )   PDF (97KB) ( 63 )  
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    The synthesis of ketene N,S-acetals has attracted a considerable attention as building blocks in organic synthesis, especially in the preparation of heterocycles[1]. The addition reaction of ketene S,S-acetals with highly nucleophilic amines, such as alkylamines, can easily afford the corresponding ketene N,S-acetals, under gentle condition, which could be converted into conjugated ketene aminals by reaction with a second equivalent of the same or a different amine[2,3]. However, this addition reaction with low nucleophilic amines, such as arylamine or heterocyclic amine, can hardly give the corresponding ketene N,S-acetals under gentle conditions. If under powerful condition,such as refluxing, the addition reaction affords a mixture of the N,S-acetals and conjugated ketene aminals[4]. Recent studies showed that this addition reaction with low nucleophilic amines affords the corresponding ketene N,S-acetals in the presence of a catalyst[5].
    一类新型ALS抑制剂的分子设计、合成及生物活性
    杨光富, 杨华铮
    1998, 19(S1):  214-215. 
    摘要 ( 154 )   PDF (95KB) ( 84 )  
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    嘧啶(硫)醚类化合物是继磺酰脲和稠杂磺酰胺类除草剂之后的所开发出的又一类以乙酰乳酸合成酶(ALS)为作用靶标的超高效除草剂[1]。与磺酰脲(胺)类除草剂相比较,这类除草剂的结构变化则更为灵活,合成也相对较为容易,因而近年来关于这类除草剂的专利文献不断见诸报道,已经成为当前除草剂研究中的一大热点。
    “Approximation”-Novel Methodology to Identify the Active Components from Compounds Library
    YU Ai-Ming, TAN Hui-Fen, YANG Hua-Zheng, ZHANG Zheng-Pu
    1998, 19(S1):  216-217. 
    摘要 ( 186 )   PDF (87KB) ( 64 )  
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    Combinatorial chemistry has been regarded as one of the most efficient method in medicinal chemistry. Identification of active compounds from compounds library is one of the main steps of combinatorial chemistry. Many approaches have been developed for this purpose, such as deconvolution[1] positional scanning[2], SURF[3],orthogonal library[4], indexed library[5], core molecule library[6] etc. Actually, all the methods are based on the rule of determining the structure of "Active Components" or "Active Compounds"(AC) from "Active Compounds Library"(ACL) by identifying "Active Building Blocks"(ABB). In this way, more efficient method named "Approximation" was developed by reducing the ABB by half in every steps, which was depicted as below by taking "8ҿ8" library as a example.
    The Synthesis of Novel ALS Inhibitors N-(Substituted Phenyl Alkoxy Phosphonyl)-N'-(4,6-Disubstituted Pyrimidin-2-yl) Ureas
    Guo-Feng ZHAO, Yong-Hong LI, Hua-Zheng YANG
    1998, 19(S1):  218-219. 
    摘要 ( 248 )   PDF (109KB) ( 56 )  
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    Sulfonylurea herbicides are a new class of herbicides discovered in the mid-1970's[1],whose mode of action has been established as the inhibition of ALS[2]. Much attention has been focused on this kind of compound, since they have unprecedented use rates, a high degree of selectivity, and excellent environmental safety. Numerous modifications of the structure of this class of herbicides have been reported.
    The Synthesis of Novel ALS Inhibitors N-(Substituted Benzyl Alkoxyl Phosphonyl)-N'-(4,6-Disubstituted Pyrimidin-2-yl) Ureas
    GuO-Feng Zhao, Xiao-Mao ZOU, Yong-Hong Li, Hua-Zheng Yang
    1998, 19(S1):  220-221. 
    摘要 ( 212 )   PDF (100KB) ( 67 )  
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    Sulfonylurea herbicides are a new class of herbicides discovered in the mid-1970's[1],whose mode of action has been established as the inhibition of ALS (acetolactate synthase)[2]. Much attention has been focused on this kind of compound, since they have unprecedented use rates,a high degree of selectivity, and excellent environmental safety. Numerous modifications of the structure of this class of herbicides have been reported.
    The Synthesis and Bioactivity of New Thiosemicarbazides and Thiadiazole Derivatives Including Substituted Pyrazolyl group
    Guo-Feng ZHAO, Lin ZHANG, Yu FU, Gui-Yu JIN
    1998, 19(S1):  222-223. 
    摘要 ( 322 )   PDF (77KB) ( 71 )  
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    Thiosemicarbazide derivatives have excellent biological activities, for example, insecticidal, plant-growth regulating activity, which can be cyclized to give heterocyclic compounds having potent activity. The bioactivities of thiosemicarbazide derivatives are directly related to the substutients on 1- and 4-position.
    Studies on Bioactive Selenium-containing Organophosphorus Compounds: Synthesis of 1-Aminoalkanephosphonate Derivatives of Benzisoselenazolone and Their Antitumor Activity
    Jia Zhou, Ru-Yu Chen
    1998, 19(S1):  224-225. 
    摘要 ( 301 )   PDF (103KB) ( 95 )  
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    Various selenium-containing compounds are widely used as reagents and intermediates in organic synthesis.1 In recent years biologically active organoselenium compounds have begun to attract considerable interest due to their unique and diverse potential pharmacological importance such as broad spectrum antitumor and antiviral activities, and some of them are even many times more active than their thio analogues.2,3 It was found that benzisoselenazolones[e.g.,Ebselen, 2-phenyl-1,2-benzisoselenazol-3(2H)-one], are effective for the treatment of diseases caused by cell damage owing to increased formation of active oxygen metabolites4 and these pharmacological effects are mainly attributed to the glutathione peroxidase (GSH-Px) like properties.5
    Synthesis of Phosphonodipeptide Derivatives of Exo-(7-oxa)bicyclo[2.2.1]heptane(or exo-Bicyclo[2.2.1]hept-5-ene)-2,3-dicarboxylic Anhydride
    ZHOU Zheng-Hong, CHEN Ru-Yu
    1998, 19(S1):  226-227. 
    摘要 ( 276 )   PDF (60KB) ( 69 )  
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    Cantharidin, exo-4a,7a-dimethyl-4,7-epoxyhexahydroisobenzofuran-l,3-dione (1),has displayed significant antitumer activities in vitro and in vivo. The adverse effects on urinary and gastrointestinal tracts prevent it to be accepted by the clinic. The structural modification of cantharidin was suggested by us with the aim to decrease its toxicity and maintain or increase its activity. Organophosphorous-containing molecules of pharmaceutical use, such as the α-aminophosphonic acid dipeptide, alaphosphin (2), which inhibits alanine racemase[2],are becoming increasingly important. We therefore designed and synthesized a series of phosphonodipeptide derivatives with α-aminoalkylphosphonate in N-terminal of exo-(7-oxa)bicyclo[2.2.1]heptane(or exo-bicyclo[2.2.l]hept-5-ene)-2,3-dicarboxylic anhydride, which might be interesting to people researching in the areas of chemistry, biochemistry and pharmacology.
    Synthesis of 1,2-Cyclic Monoacyl-rac-Glycerothio-phosphates of Cantharidin Analogs
    ZHOU Zheng-Hong, CHEN Ru-Yu
    1998, 19(S1):  228-229. 
    摘要 ( 339 )   PDF (60KB) ( 101 )  
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    Mylabris, the dried body of the Chinese blister beetle, has been used as Chinese medicine for over 2000 years. Its active constituent, cantharidin, has anti tumor activities and causes leukocytosis. The synthesis of cyclic glycerophospholipid containing cantharidin analogs has so far not been reported in literature. The conjugates of this type are not only new prodrugs of cantharidin antitumor agents but also may generate two cytotoxic groups against different target sites inside a neoplastic cell. Such types of compounds may be of interest in chemistry, biochemistry and pharmacology. This paper deals with the synthesis of 1,2-cyclic monoacyl-rac-glycerothiophosphates of cantharidin analogs as new models of phospholipids.
    核苷五配位磷化合物的合成及酯交换反应的研究
    周宜遂, 洪翌飞, 宋延林, 赵玉芬
    1998, 19(S1):  230-231. 
    摘要 ( 239 )   PDF (61KB) ( 96 )  
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    RNA和DNA是生命体中的遗传物质,RNA由于2'-羟基的存在使它与DNA相比具有不稳定性。一般认为,RNA在水解、自切割和酶解等生命过程中,都经过了一个由2'-羟基进攻磷原子生成的五配位磷中间体[1][2]。关于该中间体的研究对 了解上述生命过程有着重要的意义。因此近年来,人们合成了许多五配位磷中间体的模型化合物用来研究其反应性质及构象转化的过程[3][4]。但是,这些模型物一般都只含有一个核苷残基,因此与RNA实际反应中经历的五配位磷中间体还有较大差异。基于以上认识,我们首先合成了含一个核苷残基的三配位磷化合物1a和1b, 然后与联苯甲酰反应生成含核苷残基的五配位磷化合物2a和2b,并通过了31P-NMR,31H-NMR,13C-NMR等手段对它们的结构进行了确认。
    A New Method for the Synthesis of Oligo-peptides
    Hegui Gong, Zhaolong Li, Hua Fu, Yufen Zhao
    1998, 19(S1):  232-233. 
    摘要 ( 340 )   PDF (85KB) ( 63 )  
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    It was discovered that polypeptides were formed by self-assembly of N,O-bis(trimethylsilyl)amino acids with the assistance of O-phenylene phosphorochloridate.[1] There were three steps involved in the self organization reactions, the activation of amino acid, the elongation of peptide chain and the termination of the chain reaction,among which the activation of amino acid -the formation of imino (alkyl)acetoxyphosphoranes was the key step. The formation process of the penta-coordinated phosphorus intermediates was showed in scheme 1.[2,3,4] Through further studies of the mechanism of self-assembly reaction, it was found that carbonyl groups of the intermediates attacked by the neuclophilic groups were direct reson of the formation of peptides. However, the peptides in the solution were very difficult to be separated and analyzed.
    Synthesis of Phosphopeptides with Enzymatic Protecting Group
    Yan-Mei LI, Yu-Fen Zhao, Herbert Waldmann
    1998, 19(S1):  234-235. 
    摘要 ( 252 )   PDF (61KB) ( 91 )  
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    Reversible protein phosphorylation is widely recognized as an important mechanism for the regulation of many cellular processe[1]. For the study of the roles of the phosphoproteins in biological processes, structurally well-defined compounds are often needed, which contain the characteristic structural units of the parent biomacromolecules, i.e. the linkage regions between the peptide chain and phosphoric acid esters.
    Synthesis of Nα, Nε-Bis(O-deoxythymin-3'-ylO-isopropyl phosphoryl) Lysine Methyl Ester
    Bo Han, Yu Chen, Yu-Fen Zhao
    1998, 19(S1):  236-237. 
    摘要 ( 235 )   PDF (85KB) ( 71 )  
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    The report of Lienhard and Secemski1 on the potent inhibition of adenylate kinase by the dinucleoside analogue of adenosine, P1, P5-di(adenosine-5')pentaphosphate (Ap5A), stimulated our synthesis of Nα, Nε-bis(O-deoxythymin-3'yl O-isopropyl phosphoryl) lysine methyl ester (BTPL) as a potential inhibitor of the metabolic pathway concerned with the biosynthesis of DNA-thymine. To our knowledge, it's the first example of lysine linked two nucleotides through P-N bond.
    长链烷氧基亚磷酸酯及N-磷酰化氨基酸的合成
    邓昌慧, 李艳梅, 周洲, 许宁, 赵玉芬
    1998, 19(S1):  238-239. 
    摘要 ( 257 )   PDF (88KB) ( 66 )  
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    亚磷酸酯在有机合成中有着重要的作用,被广泛使用为磷酰化试剂,例如应用于P-O、P-N键的形成,氨基的保护等1,在制药、化学工业上有着重要的用途。N-磷酰化氨基酸具有一些有趣的仿生化性质,如自身活化成酯、磷上酯交换、N→O的磷酰基迁移、成肽反应等等2。对红细胞膜的流动性、植物细胞膜的水透性及溶质透性均有影响,对DNA、RNA也有切割作用,自身也形成稳定的LB膜。使得它在有机合成、医药、化妆品、生物试剂等方面均有一定的应用价值。
    SYNTHESIS OF PORPHYRIN NITROGEN MUSTARDS AND THEIR ANTI-TUMOR ACTIVITIES
    Zhi-Long Chen, Jin-Rong Chen, Wei-Qin Wan, De-Yu Xu
    1998, 19(S1):  240-241. 
    摘要 ( 339 )   PDF (114KB) ( 63 )  
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    With the development of laser medicine and technology in light-conducted fiber and endoscope, photodynamic therapy (PDT) obtained regulatory approvals in the United States and elsewhere to cure malignent tumors in skin, esophagi, bronchi and bladder for it's selective tumoricidal effects without the serious side effects of conventional therapy in a variety of tumors. We focused our attention on both the alleviation of patient's suffering from damages of normal tissues in chemotherapy and the eliminating of cutaneous photosensitivity as well as the enhancement of the depth of tumor necrosis which is generally not more than 8-10 nm even under the maximum safe light dose in PDT. Thus, a series of new compounds porphyrin nitrogen mustards, namely, 2,7,12,18-tetramethyl-13,17,di[3-N,N-di(2-chloroethyl) amino propyl] porphin (I1) and 2,7,12,18-tetramethyl-3,8-di(l-alkyloxyethyl)-13,17-bis[3-N, N-di(2-chloroethyl)amino propyl]porphin (I2-8) were synthesized(I) by introducing the alkylating agent nitrogen mustard into the periphery of porphyrin(Scheme 1). The mean overall yield of I2-8 is 13%.
    SYNTHESIS OF MESO-TETRA(SUBSTITUTED PHENYL) PORPHIN NITROGEN MUSTARDS WITH POYENTIAL ANTI-TUMOR ACTIVITIES
    Zhi-Long Chen, Jin-Rong Chen, Wei-Qin Wan, De-Yu Xu
    1998, 19(S1):  242-243. 
    摘要 ( 308 )   PDF (104KB) ( 70 )  
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    With the development of laser medicine and technology in light-conducted fiber and endoscope, photodynamic therapy (PDT) obtained regulatory approvals in the United States and elsewhere to cure malignent tumors in skin,esophagi, bronchi and bladder. PDT is based on the ability of some porphyrins and porphyrin-like chromophores to be accumulated selectivity in tumor tissues; tumor necrosis can be obtained by irradiation of the neoplastic area with light of the appropriate wavelength. Until now a few thousand patients have been successfully treated by PDT worldwide. Hematoporphyrin derivatives (HpD) is a complex mixture of porphins which could retain in skin and the cutaneous photosensitivity lasting for 6 to 8 weeks after the treatment was resulted in.To alleviate patient's suffering from damages of normal tissues in chemotherapy and eliminate cutaneous photosensitivity as well as enhance the depth of tumor necrosis, we synthesized a series of new compounds by introducing the antitumor group nitrogen mustard into the periphery of meso-tetraphenyl porphins.
    The synthesis of fungicidal 4-(1-methyl-3-trifluoromethyl)pyazolylcarbonyl hydrazines
    Li Bin, Man Ying, Li Zhi-Nian
    1998, 19(S1):  244-244. 
    摘要 ( 305 )   PDF (36KB) ( 53 )  
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    Many heterocyclic amides possess good fungicidal activity. It is found that the 4-(l-methyl-3-trifluoromethyl)pyazolyl amides Ⅰ controlled a number of crop diseases(1). But little 4-(1-methyl-3-trifluoromethyl)pyazolylcarbonyl hydrazines are investigated in the literature.
    The synthesis of herbicidal 4-pyrimidinyl sulfonylureas
    Li Bin, Man Ying, Guo Gui-Wen
    1998, 19(S1):  245-245. 
    摘要 ( 206 )   PDF (36KB) ( 52 )  
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    A number of 2-pyrimidinyl sulfonylureas are commercialized ALS-inhibiting herbicides to control broad-spectrum weeds in various crops when applied at very low dosage (5-50g/ha)(1).But little 4-pyrimidinyl sulfonylureas are investigated in the literature.
    The synthesis of herbicidal methyl 2,6-bis(4,6-dimethoxy-2-pyrimidinyIoxy) benzoate
    Li Bin Man Ying, Zhang Zong-Jian
    1998, 19(S1):  246-246. 
    摘要 ( 203 )   PDF (42KB) ( 60 )  
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    The pyrimidinyl carboxys as ALS-inhibiting herbicides were discovered in 1987 to control broad-spectrum weeds especially to barnyard grass in rice and cotton when applied at very low dosage (10-150g/ha)(1)(2). Three this kind of compounds are commercialized recently. The synthesis of methyl 2,6-bis(4,6-dimethoxy-2-pyrimidinyloxy) benzoate is not reported in the literature.
    The synthesis of herbicidal 2-phenylthio-pyrimidinones
    Li Bin, Man Ying, Guo Gui-Wen
    1998, 19(S1):  247-247. 
    摘要 ( 178 )   PDF (37KB) ( 56 )  
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    Many pyrimidinones possess good broad-spectrum herbicidal activity at 500g/ha(1). The 2-phenylamino-pyrimidinone I kills barnyard completely at 250g/ha pre-emergencet(2). But little 2-phenylthio-pyrimidinones are investigated in the literature.
    Synthesis of Some Novel 3-Pyrazolyl-1,2,4-oxadiazoles
    Liu Changling, Lei Xin, Zhang Lixin, Li Bin
    1998, 19(S1):  248-248. 
    摘要 ( 183 )   PDF (36KB) ( 40 )  
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    Compound Ⅰ was discovered in our synthesis program, which has good insecticidal and acaricidal activities, but not good enough compared with fenpyroximate[1]. In order to discover new and more active compounds, Compound Ⅰ was used as lead and the following compounds Ⅱ were designed and synthesized. Their structures were confirmed by IR, 1HNMR and MS. Their screenings are under progress.
    Synthesis of Some Novel Pyrazolecarbaldehydeoxime Derivatives(Ⅲ)
    Liu Changling, Lei Xin, Zhang Lixin, Li Bin
    1998, 19(S1):  249-249. 
    摘要 ( 199 )   PDF (43KB) ( 112 )  
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    Pyrazolecarbaldehyde oximes compound,fenpyroximate, is very good acaricide, and compound (Ⅰ) was discovered in our synthesis program, which has good insecticidal and acaricidal activity, but not good enough compared with fenpyroximate. In order to discover new and more active compounds used as pesticide,compound (Ⅰ) was used as lead and the following compounds (Ⅱ) were designed and synthesized. Their structures were confirmed by IR, 1HNMR and MS. Their screenings are under progress.
    Synthesis of Some Novel Methoxyacrylates and Their Biological Activities
    Liu Changling, Liu Xiaonan, Lei Xin, Zhang Lixin, Li Bin, Steve H Shaber, Richard M Jacobson
    1998, 19(S1):  250-250. 
    摘要 ( 221 )   PDF (43KB) ( 51 )  
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    Methoxyacrylate fungicides which came from natural product have an excellent,broad spectrum of activities, highly safety and selective to target because of their unique mode of action-inhibit mitochonidrial respiration by blocking electron transfer between cytochrome b and cytochrome c1, so more attention was paid by many companies in agrochemicals and at least 300 patents was applied until now. For the action of blocking electron transfer,some one suggests this kind of chemicals should not only work on fungi,but also on insects (sure) and weeds. Up to now,no herbicidal activity was reported. So the following compounds Ⅰ (X=O,NR,in patent:X=O,S rarely X=N) were designed and synthesized by introduced some fragment of herbicide.
    Synthesis of Some Novel Oxime Derivatives and Fungicidal Activity
    Liu Changling, Lei Xin, Li Zhinian, Li Bin, Zhang Lixin
    1998, 19(S1):  251-251. 
    摘要 ( 191 )   PDF (38KB) ( 49 )  
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    Some compounds containing oxime type such as fenpyroximate have good activity used as pesticide. In order to discover new lead, the novel compound (Ⅰ-Ⅴ) were designed and synthesized. Their structures were confirmed by IR, 1HNMR and MS.
    Synthesis of Some Novel Pyrazolecarbaldehydehydrazones Derivatives
    Liu Changling, Liu Xiaonan, Lei Xin, Li Bin, Zhang Lixin
    1998, 19(S1):  252-252. 
    摘要 ( 224 )   PDF (32KB) ( 45 )  
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    The compounds of general structure(Ⅰ) have good insectidal activities, which were published recently(JP06-247969,JP07-101930A, JP07-138233A, JP07-165697A, etc.). In order to discover new lead, the following compounds (Ⅱ), novel pyrazolecarbaldehydehydrazone derivatives, were designed and synthesized by introducing the active group pyrazole into the structure(Ⅰ) instead of the benzene ring. Their screenings are under progress.
    Enantiospecitic Synthesis of 1N-Sulfa-3-Nitro-4-(l,2-Acetonide)-2-Azetidmones
    Henguang Li, Rugang Xie, Tong Wua, Jian Hu, Yiemin Lei
    1998, 19(S1):  253-254. 
    摘要 ( 249 )   PDF (72KB) ( 70 )  
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    β-lactams are not only to be excellent antibiotics used widely in clinic treatment of many bacteria infected disease but also express some other potential physiology activities, such as antifungal, enzyme inhibition, antineoplastic agent,hypocholesterolemic agent1). In fact,there are much more methods in the synthesis of derivatives β-lactam2). In the course of our synthetic studies towards a series novel β-lactam analogs we have required a variety of higher optic purity key intermediates. Hear we would like to report the quite easy and versatile way by the cycloaddition of chiral alkene and chlorosulfonyl isocyanate (CSI) to produce those importent mono-ring compounds3).
    Spiral Cyclization of a-Carbonyl Radicals
    沙晉康, 何文岳, 林景宏, 林世民
    1998, 19(S1):  255-255. 
    摘要 ( 277 )   PDF (31KB) ( 56 )  
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    α-Carbonyl radicals cyclization reactions have been applied successfully toward total synthesis of several natural products,such as modhephene,1 (-)-dendrobine,2 and (-)-5-oxosiphiperfol-6-ene.3
    Anionic Cyclization Approach to Hexahydrobenzo[b] furan-3-one and Hexahydro-1H-3-indolone:Application to Total Syntheses of Natural Products
    沙晉康, 黃士榮, 黃建銘, 戴多士, 洪安威
    1998, 19(S1):  256-256. 
    摘要 ( 242 )   PDF (28KB) ( 67 )  
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    Hexahydrobenzo[b]furan-3-one(3) and hexahydro-1H-3-indolone (4) are potentially useful intermediates for total synthesis of natural products, such as the hexahydrobenzofuran unit (5) of avermectins and pancracine (6). Anionic cyclization approach toward (3) and (4) have been developed. Their application to the total synthesis of (5) and (6) will be presented.
    Synthesis of p-Aminophenyl Heteroaromatic Pyrroles
    沙晉康, 陳良吉
    1998, 19(S1):  257-257. 
    摘要 ( 221 )   PDF (24KB) ( 63 )  
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    Three general methods for synthesis of heteroaromatic pyrroles were reported recently from our laboratory.1 Application of these methods to the preparation of p-aminophenyl heteroaromtic pyrroles 3 will be discussed. Potential use of p-aminophenyl substituted heteroaromatic pyrroles 3 as electroluminescent materials is under current investigation.
    双分子络合维生素B12模型化合物的合成
    冯亚青, 董宁, 张卫红
    1998, 19(S1):  258-259. 
    摘要 ( 286 )   PDF (83KB) ( 66 )  
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    B12是人体中不可缺少的维生素[1,2],近20年来对这类化合物的研究引起人们广泛的兴趣[3-5]。为研究维生素B12结构与性能的关系,我们以维生素VB12为原料合成了VB12模型分子4f[6,7],以研究Co-N键的强弱。揭示在人体中的生物催化作用。在我们合成工作中意外地发现了VB12模型分子具有双分子络合现象,在一定条件下合成了VB12分子络合物5b-5f。为研究B12化学提供了一类新型模型分子。
    A New Procedure for Preparing 7-Nitro-l,3-benzodioxane and Its Application in the Synthesis of Phosphonates
    Li Chunbao, Wang Yonghuei, Wang Tianyu, Li Nan, Yu Zhifang
    1998, 19(S1):  260-260. 
    摘要 ( 241 )   PDF (38KB) ( 60 )  
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    The reproducible yield of 7-nitro-1,3-benzodioxane (2) from the reaction of 3-nitrophenol and 40% formaldehyde catalyzed by sulfuric acid is less than 1%[1]. By replacing formaldehyde with triformol, followed by treatment of the crude product with 10% NaOH solution, we have improved the yield to 12%. An orthogonal design experiment was carried out to optimize the conditions[2].
    Synthesis of N,N-Bis(4-pyridinyl)piperazine (Bis-DMAP) as Novel Supernucleophilic Reagent
    Huang Ji-Tao, Zhang Jia-Qi, Zheng Si-Hua, He Jia-Qi
    1998, 19(S1):  261-262. 
    摘要 ( 302 )   PDF (87KB) ( 59 )  
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    In the late 1960's,4-(N,N-dimethylamino)pyridine (1,DMAP) and 4-pyrrolidinopyridine (2, PPY) as high efficient supernucleophilic catlyst the benzoylation of m-chloroaniline were found independently by two research groups.[1,2]
    A Study of Surfactants'Role in the Synthetic System of Anthraquinone-Series Colors
    Sun Jiyou, Cao Aili, Zheng Yazi, Xue Bing, Zhang Jiaqi
    1998, 19(S1):  263-264. 
    摘要 ( 218 )   PDF (111KB) ( 43 )  
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    Solubility of dyes has been paid attention to since successive dyeing and printing operation of dyes widely applied in textile industry is carried out. However, solubility improvement of the studied dyes has seldom been reported with consideration of added relevant surfactants in the synthetic system of the dyes.
    双羟甲基冠醚的合成
    郭艳玲
    1998, 19(S1):  265-266. 
    摘要 ( 202 )   PDF (79KB) ( 55 )  
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    在冠醚分子中引入取代基是合成新冠醚和改进冠醚性能的重要途径。羟甲基取代冠醚不仅是取代冠醚的重要类型之一,而且冠醚分子中的羟甲基又为引入新的取代基起一种桥梁作用。文献中对各种单羟甲基取代冠醚的合成报道较多,[1-3] 但对双羟甲基冠醚的合成还未见报道。
    N,N-二(邻硝基苯氨基乙基)甘氨酸糖酯的合成
    陈洪, 戴志群, 曲凡歧, 黄筱玲
    1998, 19(S1):  267-268. 
    摘要 ( 268 )   PDF (128KB) ( 61 )  
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    在筛选抗植物病毒剂的研究中发现N,N-二(邻硝基苯氨基乙基)甘氨酸具有较好的抑制烟草花叶病毒(TMV)的活性,为提高其抗病毒活性,根据一些糖酯具有生理活性,而且它们的活性和药理性质都比同系物非糖酯要好,因此决定合成标题酸的酯基葡萄糖、乳糖、半乳糖和木糖酯,这些酯均为新化合物。
    The Reaction of Japanese Reagent with Aminoacetamide with Alkyl Group
    Liang Nian HE, Ren-Xi ZHUO, Ai-Hong Luo, Fei CAI, Kai LI
    1998, 19(S1):  269-270. 
    摘要 ( 175 )   PDF (78KB) ( 35 )  
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    2,4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide1,commonly known as Lawesson's reagent (LR,1a),and Japanese Reagent (1b),are not only thiating agent for diverse carbonyl compounds1-3, but also they undergoes ring-closure reactions with contain substrates containing two functional groups to give phosphorus heterocycles which contain phosphonothioyliene {C6H4-P(S)〈} moiety. These heterocyclic compounds are of potential interest as herbicides,insecticides,and fungicides4,5. Glycinamides are known as biologically active materials, for example, herbicides, plant-growth regulator6. In order to look for potent herbicides7 and to extent the use of Japanese Reagent to other bifunctional substrates,its reactions with 3-alkyl-glycinamides 2 have been investigated and found to give new phosphorus heterocycles which possess Significant selective herbicidal activity against rape. Here are our results.
    Study on the Reaction of Tricovalent Chlorophosphines with Aldehydes Containing Withdrawing Electron Groups
    Liang Nian HE, Ren Xi ZHUO
    1998, 19(S1):  271-272. 
    摘要 ( 211 )   PDF (63KB) ( 47 )  
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    α-Polychloroalkyl phosphoric dichlorides and their derivatives 2,3,4 has insecticidal activity1-4 and may be used as an intermediate to make other insecticides by reaction with alcohol, phenol, thiophenol or mercaptan. They can be prepared by various conventional methods of preparing phosphorus thioesters. Here we wish to report the addition reaction of tricovalent chlorophosphines with aldehydes containing withdrawing electron groups and its application in preparing of polychloroalkyl phosphorus dichlorides and their derivatives. The process can be represented by the following equation.
    Trimethylaluminium Mediated Rearrangement-addition Reaction of Trisubstituted Gibberellin Epoxides
    Anqi Chen, Christine L. Willisb
    1998, 19(S1):  273-274. 
    摘要 ( 199 )   PDF (100KB) ( 69 )  
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    The gibberellins (GAs) are a group of naturally-occurring tetracyclic diterpenoid plant growth hormones which are essential to the normal growth and development of plants. Over one hundred different GAs have been identified to date and most of these compounds are present in Nature only in minute quantities. Among the biosynthetic pathways of the gibberellins, the oxidation and subsequent removal of carbon-20 in C20-GAS (e.g. 1 and 2) to form C19-GAs (e.g. 3 and 4) is one of the most important process in which GA 20-oxidases are involved1 (Scheme 1). During the course of our investigation into this process, we needed to have access to C20-GAS such as (2) from a more abundant C19-GA such as GA3 (5). A successful route for such transformation may then be adapted for the synthesis of isotopically-labelled C20-GAS for biological studies.
    Migration of Double Bond of Alkene in the Reaction of Iron-Catalyzed Olefination from Sulfonylcarbanion
    Jin Li-ren
    1998, 19(S1):  275-276. 
    摘要 ( 331 )   PDF (67KB) ( 44 )  
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    Sulfonylcarbanion can be converted into alkene by elimination(1)(eq 1),mix-coupling(2) (eq 2) or homocoupling(3) (eq 3) under iron catalysis. Besides desired alkenes, isomerized alkenes were detected in the reaction of elimination or mix-coupling. However, no migration of double bond in alkene was found in homocoupling reaction. Some experimental results were obtained to discuss the alkene isomerism in the iron-catalyzed sulfonylcarbanion olefination and some evidences were given to support the proposed mechanism of iron-catalyzed sulfonylcarbanion olefination.
    新型光活性多羟基氮杂核苷类似物的合成
    靳立人, 叶剑良, 谢泳, 施江洪, 许炳雄, 黄培强
    1998, 19(S1):  277-278. 
    摘要 ( 223 )   PDF (88KB) ( 45 )  
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    研究开发新的抗癌、抗病毒药物的有效途径之一是设计、合成以及生物活性评价新型结构的核苷类似物。根据核苷结构的特点,核苷类似物的研究包括碱基改造和糖基改造两个方面。现已报道的糖基结构改造的核苷类似物基本分为含氧杂环、碳环、其它杂环(如:含氮杂环,含硫杂环等)以及无环类似物等(1)。由于可利用天然单糖作为原料,获得光活性的含多个手性碳的含氧杂环核苷类似物相对较容易;而其它杂环的光活性核苷类似物,则因涉及至少两个手性碳原子的引入,合成难度增加。本文首次报道了用光活性的苹果酸和酒石酸为起始原料,成功地合成了光活性多羟基氮杂核苷类似物(Ⅰ,Ⅱ)。
    在FAP存在下氯仿对α-β-不饱和羰基化合物的Michael加成反应
    廖联安, 李正名
    1998, 19(S1):  279-280. 
    摘要 ( 342 )   PDF (74KB) ( 61 )  
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    含三氯甲基的化合物是精细有机合成的重要中间体,因为三氯甲基能进行多种的官能团转移。通常直接引入三氯甲基的方法是氯仿与羰基化合物在碱存在下进行亲核加成而得[1];而氯仿与α,β-不饱和羰基化合物通过Michael加成,引入三氯甲基,尚未见过文献报道。作者在前文[2,3]已报道了在附载型氟离子试剂KF/Al2O3/PEG 4000(简称FAP)的存在下,硝基烷可与α,β-不饱和羰基化合物顺利地进行Michael加成反应,并且发现FAP具有很强的喊性和弱的亲核性。据文献报道[7],KF/Al2O3是环境友好的碱性催化剂,可催化多种有机反应的进行。而作者发现,FAP的表面碱性比KF/Al2O3高。因此,作者用FAP做碱,考察氯仿与不饱和羰基化合物的Michael加成;实验发现,可顺利得到含三氯甲基的Michael加成产物,用GC跟踪反应没有发现产生的三氯甲基负离子进一步衰减为二氯卡宾,与双键加成生成三员环化合物。并且用过的FAP经lmmHg,150℃重新活化2小时后可重新使用,不影响反应效果。
    Studies on the Bicyclolphosphite of Saccharides
    Cao Linghua, Sun Guanzhong, Liu Yuting
    1998, 19(S1):  281-282. 
    摘要 ( 219 )   PDF (66KB) ( 43 )  
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    Bicyclophosphitication of saccharide was used for synthesis of optically active organic phosphor compounds widely. The sugars contained phosphite ring are the inductor in stereochemistry. The nucleophilic subsitution on tetrahedron-phosphor atom is provided with specific stereo-direction. These compounds, with highly stereoselectivity, and can be used as the highly selectivity reagent for organic reactions.
    A NEW METHOD OF SYNTHESIS β-D-MANNOPYRANOSIDE BY STEREOCONTROLLED PROCEDURE
    Jian-Xin YU, Fang-Min LIU, Jin-Xiu SU, Wen-Jie LU, Yan-Ping LI, Yu-Ting LIU, Xu-Li TANG, Ying DONG, Meng-Shen CAI
    1998, 19(S1):  283-284. 
    摘要 ( 358 )   PDF (112KB) ( 45 )  
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    The β-D-mannopyranoside bond is an important structural element of N-glycoproteins, widespread in multicellular organisms as serum, cytosol, and membrane compounds[1]. However, as both the neighboring group assistance and steric repulsion as well as the anomeric effect uniformly favor the formation of α-D-mannopyranoside, the β-D-mannopyranosyl linkage still remains especially difficult to be constructed.
    Synthesis of Heterocyclic Compounds from 2-Phenyl-l,2,3-Triazole-4-Formylhydrize
    LIU Fang-ming, YU Jian-xin, LU Wen-jie, LIU Gang, LIU Yu-ting, Xu-Li TANG, CHEN Yao-zu
    1998, 19(S1):  285-286. 
    摘要 ( 208 )   PDF (90KB) ( 56 )  
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    Many compounds containing the 1,3,4-oxadiazole and/or1,2,3(or 4)-triazole and thiadiazole ring system are reported to possess antibacterial[1], antiinflammatory[2], anticonrulsant[3],CNS stimulant[4] and pesticidal[5] activities and excellent anthelmintic properties[6,7]. In view of this and the results of the combined different nuclei system in a molecular always enhancing the therapeutic activities,the present work deals with the synthesis of the combined different pharmacologically active nuclei system mentioned above in a molecular through some new method.
    含硫表面活性剂研究——3烷硫(烷亚砜、烷砜)基-2-羟丙基磺酸钠的合成
    曲荣君, 孙言志, 王春华, 刘庆俭
    1998, 19(S1):  287-288. 
    摘要 ( 280 )   PDF (98KB) ( 74 )  
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    分子中分别含有-SOn-(n=0, 1, 2)结构[1]和羟丙基结构[2]的表面活性剂均表现出一些独特的表面活性。为研究这两种结构之间是否存在协同效应,本文设计合成了在分子中同时含有上述两种结构的六种新化合物,其结构经IR、1HNMR表征,并对 其表面活性作了初步测定。
    Asymmetric Diels-AIder Reactions of (E)-1-Phenylsufonyl-3-alken-2-ones with Open Ring Diene Catalyzed by a Chiral Titanium Catalyst
    PEI WEN
    1998, 19(S1):  289-290. 
    摘要 ( 260 )   PDF (81KB) ( 62 )  
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    We have reported the reactions of (E)-1-phenylsufonyl-3-alken-2-ones 1, as useful chelating dienophile, with cyclopentadiene catalyzed by a chiral titanium catalyst. The Diels-Alder adduct was prepared in 90% yield and 100% enantioselectivity1. Our continuing interest has been focused on utilization of the sulfonyl-functionalized bidentate chelating enone 1 as prochiral substrate in catalytic asymmetric reaction. This led us further investigate the expanding utilization of the substrate 1 in the asymmetric Diels-AIder reaction. Here the reaction of (E)-l-phealy-sufonyl-3-alken-2-ones 1 with open ring dienes was proceeded by the use of the chiral titanium catalyst.
    Synthesis, Characterization and Xerographic Performance of the Triazo Pigments from Tris(4-amino)triphenylamine
    Jinhong Pan, Zhongping Huang, Yuhong Zhang, Qingsen Yu, Guoqiang Cai
    1998, 19(S1):  291-292. 
    摘要 ( 250 )   PDF (119KB) ( 83 )  
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    As the era for digital printer has come since the 1990s,the investigation into a highly photosensitive charge generator materials(CGM) suitable for IR photoreceptor is concerned.1-2 This research focuses on the triphenylamine triazo pigments, which exhibit a broad spectral response(450-800mn) and an excellent photosensitivity, especially in the near red-infrared region where solid-state diode laser emit(450-800nm). They are particularly potential CGM for laser printer and digital printer.
    N1位取代的喹诺酮类化合物分子设计与合成研究
    王国平, 朱龙观,俞庆森
    1998, 19(S1):  293-294. 
    摘要 ( 207 )   PDF (100KB) ( 40 )  
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    在抗感染化疗药物研究领域中,喹诺酮类抗菌药由于有许多优良特性,近年来得到迅速发展。喹诺酮类的基本骨架如图1。而1位取代基的演变实际是喹诺酮类化合活性改进的写照。N1位早期研究表明以乙基及与其体积相似的乙烯基为最佳,大于或小于乙烯基均使活性降低。本文通过对15个N1位取代的该类化合物的抗菌活性进行定量构效关系研究,得到4个QSAR关系式,并对所设计的新化合物进行活性预测、合成、抗菌活性测定。结果表明,新化合物具有良好活性,且实验值与预测值基本相符。
    CONDENSATION REACTION OF α-AROYL-α-ACETYL KETENE CYCLIC DITHIOACETALS WITH AROMATIC ALDEHYDES
    XIE Zhongwei, ZHANG Shujia, CHEN yaozu
    1998, 19(S1):  295-296. 
    摘要 ( 247 )   PDF (47KB) ( 46 )  
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    As a versatile three-carbon syntho,α-oxoketene cyclic acetals 1 have been applied in many fields. In order to study the structure and application of 1, we performed that α-aroyl-α-acetyl ketene cyclic dithioacetals 2 or 3 condensed with aromatic aldehydes catalyzed by sodium ethoxide and fifteen new condensation products 4 and 5 were obtained.
    SYNTHESIS OF CHIRAL DERIVATIZATION REAGENT L-SERINE METHYLESTER HYDROCHLORIDE SALT
    Xu Xiuzhu, Xu Genliang
    1998, 19(S1):  297-297. 
    摘要 ( 324 )   PDF (51KB) ( 64 )  
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    In order to increase stereoselective activity of pharmaceuticals, decrease side effects from the use of medecines and monitor the quality control in drug production, analysts have shown universal solicitude for optical separation[1].
    Synthesis and Identification of 2-(4-hydroxyphenoxy) Propionic Acid
    Shi jie-hua, Xu Xiu-zhu
    1998, 19(S1):  298-299. 
    摘要 ( 288 )   PDF (61KB) ( 62 )  
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    The synthesis of 2-(4-hydroxyphenoxy) propionic acid, useful as an important intermediate for herbicides, had been reported[1-3]. In this paper, The synthesis of 2-(4-hydroxyphenoxy)propionic acid had been studied by the reacting hydroquinone with cheap 2-chloropropionic acid in the presence of base.
    Synthesis and Characterization of 1-[2-(N,N-dimethyl-amino)ethyl]-1H-tetrazol-5-thiol
    祝一锋, 单尚, 胥洪原, 石明孝
    1998, 19(S1):  300-301. 
    摘要 ( 279 )   PDF (60KB) ( 45 )  
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    l-[2-(N,N-dimethyl-amino)ethyl]-1H-tetrazol-5-thiol is an important intermediate.It is widely used as cephalosporin CS derivative.This paper has developed a new synthetic pathway to give it by six steps.The experimental procedures are shown the following.
    Synthesis and Characterization of 2-[(3-Aminophenyl)sulfonyl] ethanol Hydrogen Sulfate
    单尚, 祝一锋, 胡耿源
    1998, 19(S1):  302-303. 
    摘要 ( 240 )   PDF (104KB) ( 56 )  
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    2-[(3-Aminophenyl)sulfonyl] ethanol hydrogen sulfate (APSES) is an important intermediate for reactive dyes.It can be used to synthesize KN type reactive dyes, which have broad colour spectra,good water solubility, excellent adaptability for different dye technique,etc. Synthesis of APSES were currently developed by Kato Kuniok et al[1] and Sanki[2].Kato had attempted to synthesize of APSES by reaction of sodium benzenesulfinate as raw material with ethylene oxide to obtain 2-phenylsulfonyl ethanol(PSE). The PSE could further be nitrated and hydrogenated to obtain 2-[(3-aminophenyl)sulfonyl]ethanol (APSE). Finally,APSE was reacted with oleum to obtain 2-[(3-aminophenyl) sulfonyl] ethanol hydrogen sulfate (APSES). Sanki had discoved a new synthetic method for the PSE. The PSE was prepared by first reaction of thiophenol as raw material with chloroethanol, and then by oxidation with hydrogen peroxide.The above mentioned two methods are not easily be adopted in industries at home. The shortage and cost of the thiophenol and sodium benzenesulfinate are mainly limited. We modificated a new synthetic pathway for APSES by five steps. The experimental procedures are shown the following.
    缩胺硫脲的合成及其抗癌活性的研究
    孙楠, 胡惟孝, 杨忠愚
    1998, 19(S1):  304-305. 
    摘要 ( 193 )   PDF (111KB) ( 45 )  
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    缩胺硫脲是一类结构新颖,具有多种生物活性的新化合物(Ⅰ1-12)。首先用硫酸二甲酯代替文献中的碘甲烷,与肼、二硫化碳在氢氧化钾作用下生成肼基二硫代甲酸甲酯(Ⅱ),产率60%。Ⅱ与2-乙酰取代基或苯甲醛缩合反应生成3-(1-取代乙撑)肼基二硫代甲酸甲酯(Ⅲ),产率54.0-91.6%。Ⅲ与1-取代哌嗪反应生成Ⅰ1-12,产率41.7-83.8%。
    四嗪衍生物的合成及其抗癌性能研究
    周茂, 蔡志彬, 杨忠愚, 胡惟孝
    1998, 19(S1):  306-307. 
    摘要 ( 169 )   PDF (96KB) ( 107 )  
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    标题化合物是一类结构新颖,具有一定生物活性的新化合物(Ⅰ1-7)。它由3,6-二甲基-1,6-二氢-1,2,4,5-四嗪(Ⅱ)在对二甲胺基吡啶(DMAP)催化下,与取代苯异氰酸酯(Ⅲ)反应生成。
    Syntheses of Chiral Fused Heterocyclic Compounds Containing l,2,4-Triazole Ring
    Wang Zhongyi, You Lingfeng, You Tianpa, Shi Haijian, Shi Haoxin
    1998, 19(S1):  308-309. 
    摘要 ( 229 )   PDF (80KB) ( 56 )  
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    The chemistry of life is based considerably on chirality. Consequently, stereospecificity has to be regarded as an especially important characteristic of biological systems. The influence of stereospecificity of the biological activities of enzyme inhibitors or compounds binding to receptor is a well known fact in the field of drug action[1]. s-Triazoles and l,3,4-thiadiazoles are reported to exhibit broad spectrum of biological and pesticidal activities[2-3].In recent years, bridge head nitrogen heterocycles have received much attention as anthelmintic agents, however, it is not observed that the syntheses of chiral fused heterocyclic compounds containing s-triazoles and l,3,4-thiadiazoles. In order to study the relationship between stereochemistry and the performance of fungicides, we have synthesized a series of (s)-1,2-di(3-aryl-s-triazolo[3,4-b][1,3,4] thiadiazolo-6-yl) ethylamine and (s)-1-(3-aryl-s-triazolo[3,4-b][l,3,4] thiadiazolo-6-yl) ethylamine by the condensation of 3-aryl-4-amino-5-mercapto-1,2,4-triazoles with L-aspartic acid and L-alanine in the presence of phosphorusoxychloride.
    Synthetic and Conformational Studies of Bridged β-Cyclodextrin Dimers
    Xiao-Qi Zheng, Qing-Xiang Guo, Li Yang, You-Cheng Liu
    1998, 19(S1):  310-311. 
    摘要 ( 217 )   PDF (83KB) ( 59 )  
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    Cyclodextrins (CD) have been found wide applications in the artificial enzymes[1] due to their ability of recognizing and binding a variety of organic and inorganic substrates in aqueous solution. In some cases, however, their binding capacity and selectivity are not good enough to make them useful (Ka~102-104L/mol). Breslow et.al[2,3] have reported that the bridged cyclodextrin dimers can complex some kinds of substrates strongly (Ka~106-1011L/mol) because of their more recognition sites. Recently, we synthesized a series of bridged β-CD dimers. It has been observed that the conformation of the dimers changed markedly upon the solvents.
    Mechanism of Reduction of 1,1-Dinitro-2,2-diphenylethylene by 1-Benzyl-1,4-dihydronicotinamide
    Hong-Yi Wang, Xiao-Qing Zhu, You-Cheng Liu, Shi-Dong Chu, Qing-Xiang Guo
    1998, 19(S1):  312-313. 
    摘要 ( 276 )   PDF (81KB) ( 53 )  
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    1-Benzyl-1,4-dihydronicotinamide (BNAH) is widely used as a model to mimic coenzyme NAD(P)H reductions1. The interest continues in distinguishing whether the formal hydride transfer from BNAH to the substrate takes place by a one-step hydride transfer or by an e-H+-e or e-H sequence2,3.
    N-Arylimine 1,4-Cycloaddition Reaction. Preparation of Substituted Hexahydrofuro[3,2c] Quinolines from Shiff Bases and 2,3-Dihydrofuran
    Jun ZHAO, Shu Feng CHEN, Xiao Tian LIANG
    1998, 19(S1):  314-315. 
    摘要 ( 218 )   PDF (54KB) ( 50 )  
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    The synthesis of nitrogen heterocycles through cycloaddition reaction of imines has stimulated much preparative and mechanistic work. 1,2The reaction of Shiff bases with electro-rich olefins has been utilized for the systhesis of quinoline derivatives. 3This paper introduces Lewis acid catalyzed cycloaddition reactions of N-arylideneaniline(Ⅰ) with 2,3-dihydrofuran(Ⅱ), which gives a pair of epimers dl-2,3,3a,4,5,9b-hexahydro-4-arylfuro[3,2-c]quinolines (Ⅲ and Ⅲ') and a few of their corresponding aromatized compounds.(Ⅳ)
    A Novel Desilylating Method for tert-Butyldimethylsilyl,tert-Butyldiphenylsilyl and Triisopropylsilyl Ethers
    Adam Shih-Yuan Lee, Jiun-Jie Shie, Hsiu-Chih Yeh
    1998, 19(S1):  316-316. 
    摘要 ( 223 )   PDF (45KB) ( 47 )  
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    In order to synthesize complicated medicinal compounds, chemists have developed increasingly satisfactory protective groups and effective methods for the formation and cleavage of protected compounds. The selective method to remove protective groups is an important tool in organic synthesis. Transformation of an alcohol to its corresponding silyl ether is a common and useful method for protecting hydroxyl groups. Within the silyl ethers,tert-butyldimethylsilyl,tert-butyldiphenylsilyl and triisopropylsilyl ethers are the most commonly used protecting groups. The cleavage of the Si-O bonds of these silyl ethers is typically performed with fluoride ion or under harsh acidic or basic conditions. Herewith, we wish to report a highly efficient and mildly acidic desilylating method for tert-butyldimethylsilyl,tert-butyldiphenylsilyl and triisopropylsilyl ethers.
    Thiophenes from Dienediones
    Chi Wi Ong, Po Chuen Shieh
    1998, 19(S1):  317-317. 
    摘要 ( 212 )   PDF (25KB) ( 65 )  
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    Our previous studies have demonstrate the usefulness of dienedione as versatile intermediates for the synthesis of cyclopentenone and arylfuran. The dienedione moiety may serve as a four carbon unit which can undergo consecutive nucleophilic addition reaction to form heterocycles. Herein we report our investigation on the addition of sulfur to the four carbon unit of dienedione for the synthesis of 2,5-disubstituted thiophenes. The regioselectivity of the reaction under various conditions will also be discussed.
    Synthesis of 4-phenylethoxyquinazoline Fungicides/Insecticides
    J. Tai, G. Roth, J. Ringer, W. Wu
    1998, 19(S1):  318-318. 
    摘要 ( 268 )   PDF (28KB) ( 39 )  
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    Recently, 4-phenylethoxyquinzoline and its analogues have been found to have both fungicidal and insecticidal activities. The synthesis of these compounds involves the construction of the quinazoline ring, preparation of the side chain, and coupling the side chain with 4-chloroquinazoline and its analogs.
    Organometallic Chemistry
    Characterization of Mass Spectra of Isomeric Dodecenols
    Xiao Junhua, Wu Haifeng, Wang Guijie, Yuan Gu
    1998, 19(S1):  319-320. 
    摘要 ( 211 )   PDF (107KB) ( 53 )  
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    The components of some insect sex pheromones are aliphatic long-chain unsaturated acetates, alcohols and aldehydes. For example, some isomers of dodecenols are the main components of sex pheromones of some noctuid moths (Δ7), olethreutine species (Δ8 and Δ9)1 and so on. Identification of the structure, especially the position of the double bond, is a very important job. GC-MS is a good method to analyze the ng quantity of sample, which is the level of nature sex pheromones. However, the double bond of straight olefinic components has a strong tendency to migrate along the carbon chain prior to fragmentation under electron impact ionization conditions. So the spectra of isomers are very similar and difficult to be identified by the normal mass spectrometry. In this paper, we develop a new method to identify the isomers of dodecenol based on the sum of the intensity ratios of pairs of fragments.
    Study on Reactivity of Five-co-ordinate Bicycloazastannoxides. Ⅲ. Bromination with Bromine
    Yang Xiao Ping, Wang Ji Tao
    1998, 19(S1):  321-322. 
    摘要 ( 184 )   PDF (72KB) ( 49 )  
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    In earlier our studies, we have determined that the structure of pentacoordinate bicycloazastannoxides with Schifibase derived from amino acids is similar to that of the metal vitamin B6 chelates by X-ray method[l-3]. Recently we investigated the condensation of pentacoordinate bicycloazastannoxides with aldehydes[4] and first determined the thermodynamic α-CH acidity (pKa value) of pentacoordinate bicycloazastannoxides by the accurate spectrophotometeric method for relative equilibrium acidities of weak carbon acids in dimethyl sulfoxide[5]. It was found that the effect of the effect of α-CH acidity and stability of α-carbanions on condensation is important. The bulkiness of the amino acid moieties affects the α-CH acidity directly, and the effect of the bulkiness of amino acid moieties on.their α-CH acidities was interpreted by the Taft equation.
    Study on Reactivity of Five-co-ordinate Bicycloazastannoxides.IV. Michael Addition with Activated Olefins
    Yang Xiao Ping, Wang Ji Tao
    1998, 19(S1):  323-324. 
    摘要 ( 189 )   PDF (67KB) ( 37 )  
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    In view of the large number of vitamin B6 related enzymes, one of the important features of the mechanism is the formation of an α-carbanion in the presence of a base catalyst[l,2]. The α-position may be the active site of the enzyme. As known, the most popular synthetic route consists of the conversion of a suitable derivation into a carbanion, followed by reaction with an electrophile. For five-co-ordinate bicycloazastannoxides, the coordination between a metal Sn atom and a Schifibase ligand increases the αCH acidity and stabilized the incipient carbanion[4]. But their electrophilic reactions on α-position have received less attention[3].
    Sythesis of Novel O-(Alkylamido-phenyl) phos phoryl choline as Phospholipase A2 Inhibitors
    Yin Wang, Gui Jun Yu, Zhai Ming Zhu, Wen Sheng Guo, Yan Liu
    1998, 19(S1):  325-326. 
    摘要 ( 194 )   PDF (65KB) ( 57 )  
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    Some novel O-(Alkylamido-phenyl) phosphorylcholines were synthesized, and their construction were confirmed with IR and 1H NMR. Some of them have the property of inhibiting the phospholipase A2.
    三(2-甲基-2-苯基丙基)锡衍生物的合成及生物活性研究
    张招贵, 黄艳琴, 邹阳, 张树奎, 陈学仁, 谢庆兰
    1998, 19(S1):  327-327. 
    摘要 ( 231 )   PDF (38KB) ( 122 )  
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    三(2-甲基-2-苯基丙基)锡氧化物(Torque,苯丁锡,[(C6H5CMe2CH2)3Sn]2O)是-个已商品化的有机锡杀螨剂[1]。为了研究三烃基锡衍生物中阴离子配体对生物活性的影响,本文用苯丁锡与酚或羧酸反应,合成了四个系列的含氧三(2-甲基-2-苯基丙基)锡衍生物。
    两种新型有机硅莰烯衍生物的合成研究
    张招贵, 郭青山, 涂卫红
    1998, 19(S1):  328-329. 
    摘要 ( 268 )   PDF (91KB) ( 45 )  
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    松节油是我国一种丰富的天然可再生资源,产量居世界首位,但我国的松节油高值化利用还很落后。应用现代有机化学的新成果,将天然可再生资源进行化学转化,以期形成高值的精细化学产品,并进而推动有机合成化学,天然有机化学的发展,这是有机化学发展的一个重要方向,在我国具有重要的意义。莰烯是由松节油中的α-蒎烯异构而成的烯烃。本文利用莰烯为原料,合成了一种新型硅烷偶联剂和一种新型烷基改性硅油。
    Effect of Axial Ligands on Monooxygenation of Cyclohexane Catalyzed by A Dimanganese Schiff Base Complex
    CHEN Xin-Bin, GUI Ming-De, ZHU Shen-Jie
    1998, 19(S1):  330-331. 
    摘要 ( 223 )   PDF (66KB) ( 54 )  
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    There are many dimetalloenzymes in nature[1]. To mimic these enzymes, we synthesized a new dimanganese Schiff base complex-Bis[N,N'-ethylene-2,2,-(phenylmethylene)-bis(3,4-dimethylpyrrole-5-aldimino)] dimanganese Mn2L (shown in Fig.1). Its structure was confirmed by IR, UV-Vis, 1HNMR and elemental analysis. It can catalyze monooxygenation of cyclohexane with PhIO as an oxidant.
    新型富勒烯C60有机钴配合物(η2-C60)(η5-RC5H4)CoPPh3 (R=H,CO2Et)的合成及性质研究
    宋礼成, 路国梁, 朱应怀, 刘鹏肿, 田建国, 李加
    1998, 19(S1):  332-333. 
    摘要 ( 269 )   PDF (72KB) ( 103 )  
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    鉴于富勒烯C60所具有的缺电子烯烃的特性1以及CpCo(PPh3)2可与烯或炔反应生成钴杂环有机化合物,2,3 因此我们设想如果用C60代替烯、炔,令其与η5-RC5H4Co(PPh3)2(1) 或η5-RC5H4Co(PPh3)(PhC≡CPh)(2)反应,则应得到一类新型的富勒烯C60有机钴杂环化合物。然而与这一设想不同的是,上述反应并未得到预期的C60钴杂环有机物,所得到的却是另一类新型的有机钴C60衍生物(η2-C60)(η5-RC5H4)CoPPh3(3).此外,我们发现当32同I2反应时,可生成C60或PhC≡CPh配体被I2置换产物η5-RC5H4Co(PPh3)I2(4)。
    Synthesis and Characterization of Some Novel Organochromium Fullerene-C60 Derivatives
    Song Li-Cheng, Zhu Ying-Huai, Liu Pong-Chung, Tian Jian-Guo, Li Ga
    1998, 19(S1):  334-335. 
    摘要 ( 187 )   PDF (87KB) ( 66 )  
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    Although the organotransition metal fullerene-C60 derivatives have been intensively studied, no report regarding organochromium complexes containing a direct chromium to C60 bond has appeared in literatures.1 Now, we report preliminarily the synthesis, characterization and properties of the first such chromium complexes, namely single isomer fac-Cr(CO)3(dppe)(η2-C60) and the isomer mixture of fac- and mer-Cr(CO)3(dppe)(η2-C60).
    新奇二茂铁甲基氮C60衍生物的合成、结构
    朱应怀,宋礼成
    1998, 19(S1):  336-337. 
    摘要 ( 241 )   PDF (80KB) ( 98 )  
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    尽管目前人们对富勒烯[C60]的过渡金属有机物研究较多[1],但通过氮卡宾方式连接的C60二茂铁衍生物尚未见报道。鉴于对C60反应的浓厚兴趣及二茂铁的广泛应用价值[2]我们 利用C60的缺电子性[3]将其与二茂铁甲基氮卡宾进行[1+2]环加成反应,分离并表征了一种具有齿轮式结构的新奇C60二茂铁衍生物(CpFeC5H4CH2N)5C60(l)。
    首例阳离子型茂铁(Ⅰ)富勒辉[C60]衍生物的合成、结构
    朱应怀,宋礼成
    1998, 19(S1):  338-339. 
    摘要 ( 370 )   PDF (84KB) ( 59 )  
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    自富勒烯被宏观量制备以来[1],人们对C60与过渡金属配合物反应性作了广泛研究,已合成出许多C60过渡金属有机物,如(η2-C60)Pt(PPh3)2[2], (η2-C60)Fe(CO)4[3]等。但至今尚未见阳离子型茂铁(Ⅰ)富勒烯衍生物的报道。本文首次通过选择性配体置换方法分离并表征了首例阳离子型茂铁(Ⅰ)富勒烯衍生物[CpFe(CO)2]4+C60[BF4]4-(1)。
    Reaction of 1,2-bis(cyclopentadienyl)tetramethyl digermane with Ru3(CO)12
    Yongqiang Zhang, Baiquan Wang, Shansheng Xu, Xiuzhong Zhou
    1998, 19(S1):  340-341. 
    摘要 ( 190 )   PDF (91KB) ( 83 )  
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    We have recently reported a novel rearrangement reaction involving an intramolecular metathesis between M-M and Fe-Fe bonds in the dinuclear iron complexes (Me2MMMe2)[η5-C5R4)Fe(CO)]2(μ-CO)2 (M=Si, Ge; R=H, Me):[1-5].In order to extend the applied range of the rearrangement reaction we tried to synthesize the digermyl briged diruthenium analogues. The results showed a great difference between them.
    Electrochemical behavior of alkyl-bridged biferrocene derivatives
    Yao-feng Yuan, Ling-yun Zhang, Ai-guo Hu, Wan-yi Liu, Zhong Cao, Ji-tao Wang
    1998, 19(S1):  342-342. 
    摘要 ( 318 )   PDF (34KB) ( 49 )  
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    Compounds containing two or more ferrocenyl groups are well-known precursors for mix-valent compounds[1-2]. It was believed that the interaction between the ferrocenyl groups are facilitated by the conjugate bridge between them. Many such researches were reported. In this paper, we report the electrochemical behavior of alkyl-bridged biferrocene, their acylation derivatives and corresponding reduction products, and transition metal complexes with alkyl-bridged biferrocenyl aryl hydrazone and β-alkyl-bridged-α,β-unsaturated ketones. Though the bridging alkyl group prevents conjugation between the two ferrocenyl group, they show characteristics of mix-valence species. The extent of interaction between the two ferrocenyl groups is influenced by the distance between the iron atoms, the substituents on the cyclopentadienyl ring, transition metal ions and their coordination modes.
    Intramolecular hydrogen bonding studies in mono-, bis and poly-[N-formyl-N'-aryl(alkyl) substituted thiourea] ferrocene derivatives
    Yao-feng Yuan, Ling-yun Zhang, Ai-guo Hu, Su-ming Ye, Bin Wang, Ji-tao Wang
    1998, 19(S1):  343-344. 
    摘要 ( 168 )   PDF (99KB) ( 53 )  
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    For several years, we have been engaged in the synthesis and coordination chemistry of ferrocenyl-containing acyl thiourea derivatives[1-2].The existence of intramolecular hydrogen bond is another interesting problem to be investigated. A series of ferrocene derivatives containing N-formyl-N'-aryl (alkyl) thiourea side chains were synthesized by treating mono- or bis ferrocenoyl isothiocyanate with various amines. It was found that intramolecular hydrogen bond between the carbonyl oxygen and the hydrogen atom on N' is common in this kind of compound. The introduction of a ferrocene fragment into the molecule often leads to its better crystallizability.
    Synthesis, structures and reactivities of poly(pyrazol-1-yl) alkane tetracarbonylmolybdenum (tungsten):x-ray crystal structures of (CH2)2(3,5-Me2Pz)2W(CO)4 and CH2(3,5-Me2Pz)2W(Cl)(CO)3(SnCl3)(Pz:pyrazolyl)
    Tang Liangfu, Xu Yuming, Wang Zhihong, Wang Jitao
    1998, 19(S1):  345-346. 
    摘要 ( 361 )   PDF (103KB) ( 77 )  
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    Since S. Trofimenko introduced these isosteric and isoelectronic ligands with poly(1-pyrazolyl)borates[1],the poly (pyrazolyl)alkane ligands have attracted much attention. Their coordinating behaviour with transition and main group metals has been extensively investigated in recent years[2]. The coordinating behaviour of bis(3,5-dimethylpyrazol-1-yl)ethane is often different from other poly(pyrazolyl) alkanes[3]. The VIB metals carbonyl complexes bonded with poly (pyrazolyl)alkanes have novel structures and unusual reactivities[4,5,6],which encourages us to investigate M-Sn bimetallic complexes with poly(pyrazolyl)alkanes. In this paper, we report the synthesis, characterization and reactivities of poly (pyrazol-1-yl)alkane tetracarbonylmolybdenum (tungsten) with R'SnCl3(R'=Ph,Cl).
    AN EFFICIENT SYNTHESIS OF ALIPHATIC α-ORGANOTHIO ALDOXIME
    Xin Liu, RuiLan Shao, RunQiu Huang
    1998, 19(S1):  347-348. 
    摘要 ( 286 )   PDF (78KB) ( 89 )  
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    The importance of the aliphatic α-organothio aldoxime compound 3 in the preparation of various pesticides is well established. Molecules comprising the α-organothio oxime moiety have been reported to exhibit insecticidal,nematocidal,miticidal activities.[1-2] In the synthesis of the compound 3,the chlorination of the corresponding aliphatic aldoxime 1 is the key step.In conventional methods, the aliphatic aldoxime 1 is chlorinated by chlorine,then the resulting hydroxime acid chloride 2 is treated with sodium alkyl mercaptide to obtain the desired compounds 3[3]. Although free Cl2 is the most common chlorinating agent,it is laborious to determine the accurate amount that has been absorbed,and the high reactivity of Cl2 always leads to side reactions. In connection with an our ongoing research project, we require an efficient and simple method for the synthesis of the compound 3.An improved synthesis process according to the following scheme is reported in this paper.
    Synthesis of Phosphorus Derivatives of Pyrazolo[3,4-d]pyrimidine
    Li Zaiguo, Huang Runqiu, Li Huiying, Liu Xin
    1998, 19(S1):  349-350. 
    摘要 ( 296 )   PDF (92KB) ( 39 )  
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    Pyrazolo[3.4-d]pyrimidines are of considerable chemical and pharmacological importance as purine analogs[1]. Various related compounds of these also show anti-tumor, anti-leukemic and antiviral activities[2,3]. In addition,α-aminoalkylphosphonic acid are well known for their wide range of biological activities. They serve in agrochemistry as antifungal agents, herbicides and plant regulators[4]. Recently, it was discovered that some derivatives of α-aminoalkylphosphonic acid also exhibit good antiphytoviral activity[5]. As an extension of our studies on plant virucides, we now wish to report the synthesis of some novel phosphorus derivatives of pyrazolo[3,4-d]pyrimidine-6-ones 4,which may have antiviral activity.
    Synthesis of 3-(α-Phenyl-phosphonomethyl)-quinazoline-2,4(1H,3H)-diones
    Li Zaiguo, Huang Runqiu, Li Huiying, Liu Xin
    1998, 19(S1):  351-352. 
    摘要 ( 227 )   PDF (83KB) ( 45 )  
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    α-Aminoalkylphosphonic acids have attracted much attention due to their wide range of biological activities. They serve for inhibiting enzyme activity, bacterial growth and in agrochemistry as antifungal agents, herbicides and plant regulators[1]. In a recent report, α-aminoalkylphosphonates showed very good inhibitory effects against plant virus[2]. At the same time, some derivatives of quinazoline-2,4(1H,3H)-dione also exhibit antiphytoviral activity[3,4]. Considering the wide applications of such compounds, we designed to synthesize some novel quinazoline-2,4(1H,3H)-diones with α-amino-alkylphosphonates moiety, e.g. 3-(α-phenyl-phosphonomethyl)quinazoline-2,4(1H,3H)-dione 4 (scheme Ⅰ).
    Synthesis and Characterization of Solid Supports Containing silicon
    Li Jing, Liao Xiangjun, Liu Hua, Xie Qinglan, Zhao Jun
    1998, 19(S1):  353-354. 
    摘要 ( 182 )   PDF (43KB) ( 47 )  
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    Combinatorial chemistry has been a new field of chemistry since 1990's.[1][2] More than 90% of researchers play their emphases on the studies of the solid supports such as P-(CH2)n-N and P-(CH2)n-O(n=1,2,3), but only a couple researchers play their emphases on the studies of the P-(CH2)n-Si(n=1,2,3). Because of the characteristic of the Si-Ar bond, we devise a series of the solid supports containing Si-Ar bond.These solid supports containing silicon were synthesized in two methods. At the same time,we also synthesized the monomer of the solid supports containing silicon or tin. The structures of these compounds were characterized by IR, elemental analysis.The synthetic routes of the solid supports containing silicon are shown in scheme 1 and the synthetic routes of the monomer of the solid supports containing silicon or tin are shown in scheme 2.
    Synthese,Structure and Acaricidal Activity of Triorganyl Chlorostannanes/Containing Silicon
    Liu Hua, Chen Xue-Ren, Wang Ji-Tao, Xie Qing-Lan, Li Jing
    1998, 19(S1):  355-355. 
    摘要 ( 207 )   PDF (41KB) ( 36 )  
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    The drug molecule is called as silα-drug if one carbon atom is substituted by silicon atom in the organic-drugs. Generally, drugs of this kind have low toxicity and pro-long efficiency. People have designed many methods in order to decrease the toxicity of organotin compounds and organosilicon has proved to be effective. Torque[1] is a new acaricide made by Shell company in America, its structure is[(PhMe2CCH2)3SnI2O. R. Tacke[2] from Germany synthesized the compounds (PhMe2SiCH2)3SnX[X=HO, (PhMe2SiCH2)3SnO] and tested the acaricidal activity of[(PhMe2EICH2)3Sn]2O (EI=C, Si) in 1986. He proved that the silyl-derivatives of Torque were highly effective acaricides.
    Synthesis of Novel Organogermanium Sesquioxides and Reactivities of 3-(Trichlorogermyl)propanoic Acid
    Wang Qingmin, Zeng Xianshun, Cui Tao, Zeng Qiang
    1998, 19(S1):  356-357. 
    摘要 ( 199 )   PDF (112KB) ( 49 )  
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    During the past two decades, carboxyethylgermanium sesquioxide Ge-132[O3(GeCH2CH2COOH)2] and its derivatives have attracted considerable attention because these organogermanium sesquioxides exhibited anticancer activities[1,2]. In 1993, Kurono et al. have synthesized phosphonoethylgermanium sesquioxide[O3/2GeCH2CH2PO(OH)2], which possesses higher antitumor activity than Ge-132[3]. Encouraged by these promising results, we developed the idea that the incorporation of a germanium residue into α-aminophosphonic acids and their derivatives, which have antibacteria and antitumor activities[4,5], would enhance their antitumor activities to a significant degree, while their toxicity would be reduced at the same time. Therefore, we designed and synthesized a series of novel organogermanium sesquioxides containing α-aminophosphonate groups by the hydrolysis of O,O-diphenyl N-trichlorogermyl propiono-α-aminophosphonates.
    Synthesis of Novel Organogermanium Compounds containing Phosphoryl Groups and Bioactivities of Products
    Wang Qingmin, Zeng Xianshun, Cui Tao, Zeng Qiang
    1998, 19(S1):  358-359. 
    摘要 ( 207 )   PDF (90KB) ( 38 )  
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    The β-trialkylgermanyl propanoic acid、β-triphenylgermanyl propanoic acid and their derivatives exhibit anti-inflaxnmatory and antibacteria activities[1]. And both phosphonic acids and their derivatives have bioactivities, e.g. antibacteria[2]、antitumor[3],etc. But synthesis and bioactivities of organogermanium compounds containing phosphoryl structures have seldom been reported. In order to look for new compounds having potent efficient anticancer and antiinflammatory activities, We designed and synthesized organogermanium compounds containing phosphoryl groups Ⅰ and Ⅱ,and studied the methods of synthesis, as well as structures and properties of the products.
    Synthesis and crystal structure of a novel mercapto-organotin complex:[Et3NH][Ph2SnCl(μ2-SCH2COO-)]
    Xueqing Song, Qinglan Xie, Jing Li, Xiaoniu Fang
    1998, 19(S1):  360-360. 
    摘要 ( 236 )   PDF (49KB) ( 66 )  
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    A novel complex[Et3NH][Ph2SnCl(μ2-SCH2COO-)],has been unexpectedly obtained by the reaction of Ph3SnCl and HSCH2COOH in 2:1 molar ratio in the presence of organic base Et3N.
    Synthesis, structures and in vitro anticancer activity of some germanium-substituted di-n-butyltin dipropionates
    Xueqing Song, Zhiqiang Yang, Qinglan Xie, Jinshan Li, Xiaoniu Fang
    1998, 19(S1):  361-361. 
    摘要 ( 301 )   PDF (53KB) ( 50 )  
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    Organotin and organogermanium compounds are extensively studied for their wide range of biological activity. To link biological active properties of organotin and organogermanium, sixteen new germanium-substituted di-n-butyltin dipropionates with the form (R3GeCHR1CHR2COO)2SnBu2n·H2O were synthesized.
    一种简便合成含膦酰基杂环化合物的方法
    邹小毛, 陈凯, 杨华铮
    1998, 19(S1):  362-363. 
    摘要 ( 267 )   PDF (58KB) ( 59 )  
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    含膦酰基芳环及杂环化合物是一类具有较高生物活性的化合物。如1970年德国专利报导[1],3-吡唑基膦酸醋具有杀虫、杀蹒活性;1976年Ravlenko.A.F.等报导[2],4-吡啶膦酸酯能够促进燕麦的根部生长。这些研究都表明由于杂环化合物和有机磷化合物在生物体中特殊作用,使得膦酰基化合物确实具有特定的生物活性,在农药、医药领域具有较大的潜在开发价值。因此研究其合成方法具有重要的作用。从总体上来说,其合成大致可分为两大类:一类是利用杂环化合物的特殊性质,与含磷化合物(主要是三、四配位磷化合物)发生反应,使杂环带上膦酰基。另一类是利用开链前提含膦酰基的合成子与不同试剂作用,通过环合成来构选杂环。从而合成含膦酰基杂环化合物。我们为了合成特定的含膦酰基杂环化合物,即在邻位要有吸电子基团的膦酰基杂环化合物,采用合成子的方法虽可以合成,但步骤多,合成难度大。鉴于我们要合成杂环的性质,我们用四配位的膦酸酯作为亲核试剂来合成我们的目的产物。
    3-苄硫基-5-重氮基-4-乙氧羰基吡唑的合成、晶体结构的确定及反应活性的研究
    邹小毛, 陈凯, 杨华铮
    1998, 19(S1):  364-365. 
    摘要 ( 736 )   PDF (70KB) ( 75 )  
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    吡唑类衍生物是一类具有很好生物活性的化合物,具有很高除草或杀虫活性的吡唑类化合物文献中已有大量的报导[1]。因此研究其合成方法显得很重要。我们最初希望通过5-氨基-3-苄硫基-4-乙氧羰基吡唑经重氮化反应去氨基制备3-苄硫基-4-乙氧羰基吡唑,然后继续衍生化合成系列吡唑类化合物。
    Cp2TiCl2/M(Zn,Mg) system promoted the addition reactions, enyne cyclization reactions and applied in the synthesis of (+)-Goniopypyrone
    Hong-ming Li, Hong-Liang Sun, Zong-Bao Zhao, Yi-Ke Ni, Chang-Qing Wei, Gao-sheng Yang, Min Yang, Gang Zhao, Yu Ding
    1998, 19(S1):  366-366. 
    摘要 ( 174 )   PDF (37KB) ( 52 )  
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    In the course of our ongoing projects. It has been focused on the studies of carbon-carbon formation using redox system such as Cp2TiCl2/M(Zn,Mg) and LnCl3/Zn. This paper deals with our research progess on exploring reactions for the syntheses of useful building block, intermediates and natural products.
    Study on the α-Thiocarbonylthioformamide Ⅰ-Comparison with α-carbonylthioformamide
    Jian Ping Zou, Zhong E Lu, Run Sun Zeng, Bei Zhao, Ke Qian Ghen
    1998, 19(S1):  367-368. 
    摘要 ( 215 )   PDF (71KB) ( 56 )  
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    α-Carbonylthioformamide 1 and α-thiocarbonylthioformamide 1 were synthesized by Adiwidjaja in 19801. However, there is no report of these compounds related their properties and reaction activities2. Compound 1 has two possible sites for nucleophilic attack. In our previous works., it was used to synthesize a lot of heterocyclic compounds (Scheme l)3-6.
    Study on'the α-Thiocarbonylthioformamide Ⅱ——Dehydrogenation of tetrahydronaphthalene
    Run Sun Zeng, Jian Ping Zou, Zhong E Lu, Jian Feng Ge, Ke Qian Chen
    1998, 19(S1):  369-370. 
    摘要 ( 206 )   PDF (47KB) ( 35 )  
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    α-Thiocarbonylthioformamides were synthesized in 1980[1-3]. Authors first explored their dehydrogenation reaction at high temperature. In our initial experiment, α-Thiobenzoylthioformmorpholine(l) was heated with diethyl acetylene dicarboxylate in tetrahydronaphthalene(2). The reaction is shown as following.
    Study on the α-Thiocarbonylthioformamide Ⅲ——Reaction with trimethyl phosphite
    Run Sun Zeng, Jian Ping Zou, Zhong E Lu, Xiang Shan Wang, Ke Qian Chen
    1998, 19(S1):  371-372. 
    摘要 ( 253 )   PDF (56KB) ( 53 )  
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    α-Thiocarbonylthioformamide is a stable and almost unexplored class of compounds1 which attracts us to study their properties and reactions. According to literature three-valenced phosphorus compound is easy to react with thiirane2 and thiocarbonate3 to form C=C double bond. So we want to explore the reaction of α-thiocarbonylthioformamide with three-valenced phosphorus compound. In initial experiment, we explored the reaction of α-thiobenzoylthioformmorpholine (1a) with trimethyl phosphite in dry diethyl ether at room temperature.
    Study on the Reaction of α-Ketohemithioacetal
    Jian Ping ZOU, Run Sheng ZENG, Li Hua QIU, Bei Zhao, Ke Qian Chen
    1998, 19(S1):  373-374. 
    摘要 ( 263 )   PDF (73KB) ( 42 )  
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    Aromatic α-sulfinyl carboxylic acids can be rearranged to hemithioacetals or other derivatives of glyoxylic acid under the action of acid reagents was first reported by Pummerer1. Later, Russell and coworkers applied this rearrangement to β-ketosulfoxides, synthesized α-ketohemithioacetal2, which can be transformed to α-keto alcohol, α-keto aldehyde and α-hydroxy alcohol, α-hydroxy acid3. Furthermore, Hall and Poet reported that α-ketohemithio-acetal can be rearranged to the corresponding α-hydroxythioester in the presence of magnesium nitrate and sodium acetate or tertiary amine4. However, few reports of reaction of α-ketohemithioacetal can be seen in literature.
    Synthesis and Spectroscopic Characterization of Transition Metal Complexes of Maleionitriledithiolate and 4,4'-Dimethano-2,2'-bipyridine
    PENG Zheng-he, FANG Chen-jie, PAN Qing-cai, WEI Yi-hai, QIN Zi-bin
    1998, 19(S1):  375-376. 
    摘要 ( 223 )   PDF (106KB) ( 46 )  
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    Transition metal complexes with a tetragonal planar structure of a dithiolene and a diimine have excellent electronic functions due to the intramolecular charge transfer from a ligand to other ligand (LL'CT)[1-3]. Our interest is in the metal complexes of the dicyno-dithiolene and some diimine such as substituted and unsubstituted phenanthrolines and bipyridines. In the present work we studied synthesis, characterization, photo-physical and photochemical properties of the title complexes M(mnt)(dmbpy),M=Mn,Fe,Co, Ni, Cu,Zn.
    Synthesis and Spectroscopic Characterization of Transition Metal Complexes of Maleionitriledithiolate and 5-Nitro-Phenanthroline
    PENG Zheng-he, PAN Qing-cai, REN Xiao-ming, FANG Chen-jie, QIN Zi-bin
    1998, 19(S1):  377-378. 
    摘要 ( 233 )   PDF (113KB) ( 128 )  
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    The dithiolenes and diimines and their metal complexes are an important research field in the organic and coordination chemistry[1-3]. Transition metal complexes of a dithiolene and a diimine have excellent electronic functions due to the intramolecular charge transfer from a ligand to other ligand (LL'CT)[3], in which are interested authors[4,5]. Recently we have been studied in detail the synthesis and properties of the title complexes M(mnt)(5-NO2-phen), M=Mn, Fe, Co, Ni, Cu, Zn. The structure and properties of the M(mnt)(5-NO2-phen) were characterized by the elemental analysis, TDA-TG, MASS, IR, UV-Vis, fluorescence and EPR spectra,molar conductivity and magnetic susceptibility. In the present abstract we report only the synthesis and spectroscopic characterization of these complexes.
    Theoretical Studies on Copper, Nickel Complexes of Corrole and Isocorrole
    Di-Fei Wang, Kyle W. K.. Chan, Yun-Dong Wu, Emanuel Vogel
    1998, 19(S1):  379-380. 
    摘要 ( 236 )   PDF (96KB) ( 61 )  
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    Corrole 2, an analogue of porphyrin 1, is also a fascinating molecule. It can be considered as an intermediate in the biosynthesis of corrin 3,the chromophore of Vitamin B12, Similar to porphyrin, corrole also has 18 electrons in the π-system of the ring and is aromatic. Recently, isocorrole 4, another compound in the corrole family, was synthesized by Vogel's group[1].One important feature of corrole and isocorrole is the possible formation of tri-anion, and thus the ability to stabilise high-oxidation-state metal cations.
    Resolution of Cycloplatinated Ferrocenylketimines
    Wu Yang-Jie, Ding Li, Wang Wen-Ling, Du Chen-Xia, Song Qiu-Ling
    1998, 19(S1):  381-382. 
    摘要 ( 188 )   PDF (103KB) ( 46 )  
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    Ferrocene derivatives especially the chiral and optically active 1,2-disubstituted ferrocenes are the most extensively investigated metallocenes. The common way to obtain the planar chirality in the ferrocene moiety is the usage of a chiral precursor. Sokolov et al have reported the asymmetric cyclopalladation with the salts of optically active carboxylic acids as nucleophilic catalysts, however, this method was suitable only when the reaction experienced the diastereomeric transition states[1]. The only report,of the resolution of cyclometallated ferrocene derivatives was given by Nonoyama and his coworkers[2]. They resolved dimethyl-aminomethylferrocene to optically pure enantiomers using the (S)-proline as chiral auxiliary and separated the diastereomers by solubility difference.
    Red Light Emitting Devices Based on Organo-lanthanide(Ⅲ) Complex
    Yu Gui, Wu Xia, Liu Yunqi, Wang Mingzhao, Ji Linpei, Zhu Daoben
    1998, 19(S1):  383-384. 
    摘要 ( 290 )   PDF (63KB) ( 49 )  
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    An organic electroluminescent devices with Eu3+-complex as an emitter was fabricated. A device structure of ITO/emitting/electron transport layer/Al was empolyed. Its color was red.
    Physical Organic Chemistry
    CAGED CHOLINERGIC LIGANDS AND PHOTOREGULATION OF CHOLINESTERASE ACTIVITIES
    Ling Peng, Maurice Goeldner
    1998, 19(S1):  385-385. 
    摘要 ( 220 )   PDF (60KB) ( 46 )  
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    Photolabile precursors of biologically interesting molecules, or "caged" compounds can provide control of temporal and spatial release of desired molecules by rapid photolysis, and are thus important tools in the study of fast biological processes. Acetylcholinesterase (AChE) is a particularly fast enzynie which hydrolyses the neurotransmitter acetylcholine with a turnover number approaching 20000 s-1. Knowledge of the 3-D structure of AChE[1] has permitted a better understanding of structure-function relationships in the cholinesterases, but has also raised cogent new questions concerning the traffic of substrate and products to and from the active site. Time-resolved crystallography would present an ideal approach to investigate this issue at the atomic level and in real time,provided that suitable probes, which regulate the enzymatic activity by temporally and spatially controled release of enzyme substrates or product.
    The Anomalous Triplet Exciplex Emission of 4-phenylbenzophenones with Amines
    Chch-Yung Liu, Tai-Shan Fang
    1998, 19(S1):  386-387. 
    摘要 ( 222 )   PDF (73KB) ( 40 )  
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    Structured phosophorescence with 20μs life time[480nm, 510nm (max),550nm] from 4-phenyl-benzophenone (4-PBP) was quenched by trieyhylamine (TEA) in benzene. An Anomalous exciplex emission with strutureless peaking at 647nm and 30μs life time. A quenching mechanism has been shown to involve a mixed (π,π*) and (n,π*) triplet of 4-PBP to form an exciplex with the grond state of TEA.
    Application of P-31 NMR to the Study of Phosphorylated/Cellulose and Lignocellulosic Materials(Wood)
    Chen-lan Wang
    1998, 19(S1):  388-388. 
    摘要 ( 267 )   PDF (27KB) ( 45 )  
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    Phosphorylation of cellulose and wood(also named as lignocellulosic material) is one of the potential methods for chemical modification of these natural polymers. In this research, α-cellulose and wood meals (extracts free) were mixed with certain organophosphoryl chloride compounds, producing the corresponding phosphorylated derivatives. A series of model chemicals (e.g. ethylene glycol, glucose, cellobiose, phenols,guaiacol, etc.) were converted to the same derivatives as references. The phosphorylated products were examined by using P-31 NMR spectroscopy to analyze their structural characteristics.
    The constituents of the South American liverwort Lepicolea ochroleuca
    劉惠儒, 吳嘉麗
    1998, 19(S1):  389-389. 
    摘要 ( 194 )   PDF (30KB) ( 69 )  
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    Ten terpenoids 1-10 were isolated from the South American liverwort Lepicolea ochroleuca, collected at Chile, South America. Compounds 1 and 2 were the major components and the others were just minor. Among them, compounds 8-10 were novel. Their structures were established by spectral analysis.
    SOME INTERESTING FINDINGS FROM TAIWANESE LIVERWORTS
    吴嘉丽, 刘惠儒, 张人坚, 陈羿维, 刘创勋
    1998, 19(S1):  390-390. 
    摘要 ( 295 )   PDF (29KB) ( 51 )  
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    Here we wish to report some interesting new compounds identified from our recent studies on the constituents of liverworts from Taiwan.
    Screening of Antioxidants and Antiozonants and Their Protection Mechanisms
    Xian-Man Zhang
    1998, 19(S1):  391-392. 
    摘要 ( 218 )   PDF (91KB) ( 98 )  
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    Antioxidants and antiozonants have been widely used in polymer industry because addition of a small amount of antioxidants and/or antiozonants could prevent the degradation caused by oxygen and/or ozone from atmospheric air and significantly increase the service life-time of polymer products.1 The related degradation is also responsible for foodstuff deterioration, and for ageing and cancer of the biological systems.1b
    双区理论——结构生理效应间关系的理论处理所揭示的致癌机理
    戴乾圜
    1998, 19(S1):  393-394. 
    摘要 ( 265 )   PDF (181KB) ( 66 )  
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    作者的集体借分子结构与生理效应之间关系的研究方法,将环境致癌剂的分子结构与其致癌性能之间的关系解释成为一种分子结构与其特定的双官能化学活性之间的关系,提出了化学致癌作用的机理,命名为双区理论。近来,作者实验室用实验方法,对双区理论作出了若干证明,国外工作对之也有所证明。本文综述双区理论及其进展。
    对称二烷基亚硝胺第二活性区对DNA烷化作用机理的AM1研究
    周志刚, 钟儒刚, 谷峻战, 戴乾圜
    1998, 19(S1):  395-396. 
    摘要 ( 219 )   PDF (137KB) ( 49 )  
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    多年来的实验结果表明,多数亚硝基化合物(NCC)是明显致癌的,有些是强烈致癌的。NCC是一种间接致癌剂,需要通过代谢而发挥致癌作用。一般认为NCC在混合功能氧化酶作用下经代谢α-位羟基化,脱去一侧烃基形成具有亲电活性中心的烷基重 氮化合物作为"最终致癌剂"并烷化DNA而引发癌症[1]。但是单纯用α-位代谢的活性未能满意地解释NCC的结构变化对其致癌活性的影响。我们实验室将"双区理论"的观点应用于NCC致癌机理的研究,提出了NCC经代谢形成具有两个亲电活性中心的最终致癌剂,在DNA互补碱基对间形成横向交联而发挥致癌作用的观点,用模式识别方法对153种当时已有动物致癌活性试验数据的NCC进行5级致癌强度分类,得到了判对率为97.3%的良好一致性。并且提出,在单氧酶作用下,NCC羟基化的β-位或有邻基参与作用的γ-位可以作为第二个亲电活性中心[2-3]。这一观点不仅在结构致癌活性关系研究中发挥了重要作用,而且正在被越来越多的实验结果所证实[4]
    1,3-丁二烯代谢产物与DNA烷化作用和交联的AM1研究
    周志刚, 戴乾圜, 钟儒刚
    1998, 19(S1):  397-398. 
    摘要 ( 171 )   PDF (142KB) ( 65 )  
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    近年来的研究表明,作为合成橡胶和塑料工业的重要化工原料和香烟烟雾及汽车尾气中环境污染物的1,3-丁二烯(BD)是强致突剂和致癌剂,能引发啮齿动物多种肿瘤[1]。并逐渐被认定对人有致癌作用[2]。分子生物学实验表明:BD本身是不致癌的, 但能在体细胞内经细胞色素P450代谢为1,2-环氧-3,4-丁烯(EB)、1,2-二羟基-3,4-环氧丁烷(DiolEB)和1,2,3,4-二环氧丁烷(DEB)等活性物[3]。其中DEB是明确致突和致癌的,可直接引发细胞突变。哺乳动物细胞体外实验表明:DEB可引起染色体突变和姊妹染色体交换,并能引起人体细胞广泛的突变[4],但对DEB活性的分子机制知之甚少。EB和DiolED在一些实验中有弱致突性,在另一些实验中显阴性,其致癌性尚无定论,有待于进一步实验研究。
    糖酶的分子设计及其三维构效关系研究
    胡文祥, 曹晔, 恽榴红
    1998, 19(S1):  399-400. 
    摘要 ( 260 )   PDF (163KB) ( 58 )  
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    人类不断探索酶的种类、结构与功能、催化机理及其应用,可以更好地了解免疫反应、生理生化反应、甚至生命起源与生命进化的奥秘,构筑化学通向生命科学的宏伟桥梁。仿生酶(即模拟酶)催化研究和应用具有悠久的历史,佩德森(Charles Pedersen, 1904~)、莱恩(Jean-Marie Lehn 1939~)合成了模拟酶冠醚类低分子量有机化合物, 克拉姆(Donald Cram,1919~)提出了主宾化学概念,三人共享1987年度诺贝尔化学奖,将模拟酶研究推向一个新高潮。
    3D-SAR And A novel Molecular Pharmacology Model of Cholinergic And Anticholinergic Drugs
    Wenxiang HU, Liuhcmg YUN, Jianying WANG, Jianshe WANG, Shengjian TAN
    1998, 19(S1):  401-402. 
    摘要 ( 273 )   PDF (121KB) ( 63 )  
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    Anticholinergic drugs have been widely used for many years in neurological research field and clinicial therapy of many dieases, such as parkinsonism stomachache and the organophosphorus agents poisoning. It is important that investigating the conformation-activity relationship (CAR), 3D-QSAR and molecular pharmacology of these compounds to aid in die design highly selective drugs and explain many phenomena understood difficultly,including the similar biological effects for various compounds and different effects for a single compound.
    Substituent Effects And Structure-Reactivity Relationship of Organophosphorus Compounds
    Wenxiang HU, Chengye YUAN, Shushen LI, Jianying WANG
    1998, 19(S1):  403-404. 
    摘要 ( 192 )   PDF (116KB) ( 83 )  
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    To evaluate the substituent effect in organophosphorus compounds, a series of model compounds, namely 4-substituted-2,6,7-trioxa-1-phosphabicyclo[2.2.2] octane-1-oxides, alkyl hydrogen p-substituted phenyl-phosphonates, dialkyl p-substituted phenylphosphonates, as well as alkyl hydrogen alkylphosphonates, were synthesized and studied. Since in these compounds the substituents are located far away from reaction centre and the contribution of the steric effect of substituents can thus be eliminated, the substituent polar effect was evaluated based on 31P NMR, pKa and charge density of phosphoryl oxygen of these compounds calculated by the quantum mechanies MNDO method. The results showed that the polar effects of substituent in carboxylic and organophosphorus esters are similar, and the variation in polar effect among the alkyl groups is not significant. In the meantime, some steric parameters Esp of substituents were suggested for organophosphorus compounds, which are different from the Taft's Es and Charton's υ parameters[1,2].
    Determination of Aldehydes and Ketones Pollutants in Ambient and Polluted Air by HPLC with Precolumn Chemical Derivatization
    Qingtao PENG, Wenxiang HU, Runwu CAO
    1998, 19(S1):  405-406. 
    摘要 ( 225 )   PDF (111KB) ( 76 )  
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    In the last years, aldehydes and ketones have been the pollutants constantly in air with the development of the chemical industry. Most of aldehydes and ketones are toxic or carcinogenic. There are six carbonyl compounds in the pollutants with the maximum permission concentration, which limited by our state standard in residential area, workshop air and surface water formulated in 1979. In New Clean Air Act of America, there are 189 toxic and harmful pollutants including nine carbonyl compounds.Therefore, it is extremely necessary to study the sampling process and analytical method of aldehydes and ketones. At present, the main domestic analytical methods are colorimetric method and titrimetric method. In addition, ion chromatography and gas chromatography are also adopted. These methods can only be used for the analysis of one or two kinds of aldehydes and ketones. The absorbent solutions in these methods includes acidic sulfate, potassium hydroxide,water and weak acid. Because the reaction of these absorbent solutions and carbonyl compounds has no specificity, the selectivity and sensitivity of these methods are often low. Thus, the application of these methods in analysis of actual samples are limited greatly.
    The Determination of T-2 Toxins by HPLC with Chemical Derivatization and Fluorescence Detection
    Wenxiang HU, Qingtao PENG, Shenjian TAN, Jianshe WANG, Xunsheng SHAO, Peirang Chen, Ye CAO
    1998, 19(S1):  407-408. 
    摘要 ( 206 )   PDF (113KB) ( 43 )  
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    Even though many pharmaceuticals show native chromophoric properties, there are also many important compounds, such as anticholinergic drugs, toxins, steroids and anticancer agents, which are not chromophoric and can not be determined by usual spectra analysis. T-2 toxin is one kind of the compounds. The detection of these compounds by HPLC imposes severe limitation on sensitivity and ofen togather with unacceptable constraints on mobile phase selection. Precolumn or postcolumn derivatization technology by using chromophoric group is often an inexpensive but effective way to overcome this problem, which make these compounds chromophoric and then enhance detcetability of them. For trace analysis, there is a balance to be attained between rigour of sample cleanup and selectivity of detection. Derivatization of target compounds of pharmaceuticals interest offers significant advantages, such as improving selectivity and thus reducing the complexity of the sample cleanup required.
    The Calculation for the Molecular Position Electronegativity of Organic Molecules
    Han Chang-Ri
    1998, 19(S1):  409-410. 
    摘要 ( 242 )   PDF (77KB) ( 64 )  
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    The molecular position electronegativity (MPEN) is a new concept and based on the auther's studying of group electronegativity[1,2]. MPEN represents the power of attracting an electron of the center atom situated different molecular environment. MPEN is defined as the electronegativity of the center atom situated different molecular environment and this is affectde by neighbors of the center atom.
    A NEW METHOD FOR THE PREPARATION OF CARBONYL DIAZO COMPOUNDS
    XueShun Jia, Lei SHI, DongLan Ma, YuLu WANG
    1998, 19(S1):  411-412. 
    摘要 ( 162 )   PDF (53KB) ( 48 )  
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    Azo compounds are very important in organic chemistry. In resent years, some notoworthy studies show that azobenzene derivatives possess very good optic remembering and photoelectric properties, optical switching and image storage by means of azobenzene liquid crystal film.1,2 We have reported some new methods for the Azo compounds3. In this paper, We describe a new oxidation system KCIO3/H2SO4 catalyzed by FeSO4 to synthesis diazo compounds (ArN=NCON=NAr) in short time and good yield for the first time.
    Stereochemistry of the Heterocyclic Alcohols Containing Piperidine Unit
    Gao Shouhai, Hu Wenxiang, Yun Liuhong
    1998, 19(S1):  413-414. 
    摘要 ( 209 )   PDF (87KB) ( 49 )  
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    The stereochemistry of the heterocyclic alcohols (R1-OH~R4-OH,see Fig.1) containing piperidine unit has been studied on the basis of the calculations of molecular mechanics and quantum chemistry. The calculations of alcohols (R1-OH~R4-OH) and their carboxylate derivatives were carried out, and the results of these calculations were listed in Tab.1 and Tab.2. It was showed that there existed the non-classical orbital super-conjugated interactions between the nitrogen atom and oxygen atom which caused the conformations to be more stable when the hydroxylic group lay at axial than at equatorial with respect to the piperidine ring in compounds (R1-OH) and (R3-OH). If the axial hydrogen atoms at C2 and C6 positions in the piperidine ring were substituted, or the molecular existed in the polar solutions, this non-classical orbital super-conjugated interactions would be much weak even diminished. In this case,the conformations were more stable when the hydroxylic group at equatorial than at axial in these compounds. These consistented with the experimental results.
    Structural characterization of a glucan from Angelica sinesis (Oliv) Diels
    Chen Li, Cheng-Gang Huang, Zhi-Xiao Li, Yao-Zu Chen
    1998, 19(S1):  415-415. 
    摘要 ( 192 )   PDF (56KB) ( 64 )  
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    Angelica sinesis (Oliv) Diels is a traditional Chinese drug used clinically in the treatment of gynecological diseases. Its polysaccharide fraction been reported to have several immunomodulating, antitumor, antiradiation activities[1] and a recent paper showed it could obviously act on the hemopoietic system[2]. Haruki Y. et al. have elucidated the chemical structure of a α(1→4) linked D-glucan from Angelica acutiloba[3]. We now describe the structure of a water soluble glucan, AS-1, which was isolated and purified from the water extract of Angelica sinesis (Oliv) Diels. It is only composed of D-glucose and its mean molecular weight is estimated to be 5.3×105. The absorption peak of 846cm-1 on IR, the chemical shift of δ 99.98 ppm for C-1,and the 168 Hz of 1JC-H suggested that the D-glucose residues were α-linked. Methylation analysis (Table 1),periodate oxidation, Smith degradation, 1H NMR and 13C NMR (Table 2) showed that it is α(l→6) linked D-glucan to which are attached two glucosyl side chains, Glc-(l→3)-Glc→1 and Glc-(1→4)-Glc→1, both at 3-O of the glucosyl residues of every 14th glucose units of the main chain. The structure was further proved by using HMBC,HMQC and DQF-COSY techniques. The details of its pharmacological results will be published elsewhere.
    Studies on Isothermal Vapor-Liquid Equilibrium for Styrene-Cumene Binary System
    Yu Shuxian, Deng Fengjie, Xu Min, Yu Zubing, Han Shijun
    1998, 19(S1):  416-417. 
    摘要 ( 247 )   PDF (90KB) ( 56 )  
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    This dissertation has studied the isothermal vapor-liquid equilibrium(VLE) in associating system of styrene-cumene at 353.15K and 373.15K by using a modified Rose still. The pressures are indirectly measured from the boiling points of pure waler in a separate inclined cbulliometer with a pump-like stirrer. The experimental data are well correlated with Wilson equation.
    Effect and Solvent Effect on Monooxygenation of Cyclohexane Catalyzed by A Dimanganese Schiff Base Complex
    CHEN Xin-Bin, GUI Ming-De, ZHU Shen-Jie
    1998, 19(S1):  418-419. 
    摘要 ( 239 )   PDF (68KB) ( 45 )  
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    A new dimanganese Schiff base complex-Bis[N,N'-ethylene-2,2,-(phenylmethylene) bis (3,4-dimethyl pyrrole-5-aldimino)] dimanganese Mn2L was synthesized and used as a catalyst for PhIO oxidizing cyclohexane to cyclohexanone and cyclohexanol. This paper reports temperature effect and solvent effect on the reaction.
    Heterolytic and homolytic bond dissociation energies of the N-NO bonds in N-nitroso diethyl phosphoramidates
    Kun Wang, Jinpei Cheng, Chongjie Zhu, Feng Gao
    1998, 19(S1):  420-421. 
    摘要 ( 268 )   PDF (86KB) ( 63 )  
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    Interest in nitric oxide(NO) as a biological radical in affecting human life has increased dramatically over the last twenty years.[1] It has been implicated in diverse physiological process, including vasodilatory and antiplatelet effects, macrophage-induced cytotoxicity, and neurotransmission.
    The First Titration Calorimetric Determination of Iron-Carbon Bond Dissociation Energy
    Jiantao Guo, Jin-Pei Cheng
    1998, 19(S1):  422-423. 
    摘要 ( 240 )   PDF (95KB) ( 72 )  
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    Organometallic Chemistry is one of the most rapid growing areas in modern chemistry in the past a few decades. Interest in deepening a more fundamental understanding of the fabulous chemistries in this exciting area has led us to explore the information regarding to the M-C bonding energetics where M represents a metal atom, since breaking or forming a metal-carbon bond is an integral part of many key steps in organometallic reactions. Although scientists have a high desire for and have actually made considerable efforts determining metal-carbon bond strengths, the bond dissociation energy data of metal-carbon bond are still very scarce[1-3].
    Carbon-halogen Bond Cleavage Energies of Alkyl Halides and Haloalkyl Radical Anions in Solution
    Lijuan Wang, Jinpei Cheng
    1998, 19(S1):  424-425. 
    摘要 ( 229 )   PDF (96KB) ( 47 )  
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    Radical anions are intermediates in a variety of processes:dissolving metal reductions, cathodic reductions(1),homogeneous redox reactions, SRN2 reactions(2) and nucleophilic substitions(3). Several techniques ranging from pulse rediolysis, near-infrared spectroscopy, derivative linear-sweep voltammetry, and electron spin resonance spectroscopy have been employed to study the characteristic properties of the radical anions. The most characteristic property for the radical anions derived from organic halides, in particular, has been known to be the severe weakening of the carbon-halogen bond and consequently the ease of its dissociative cleavage to form halide ion and radical (eq.l) or to form halogen atom and anion (eq.2) as seen in the key step of the SRN1 mechanism.
    Metal Ions Transport across Liquid Organic Membranes by Cyclic Peptides
    Linjing Mu, Jin-pei Cheng, Hai Huang, Ning Zhang, Jianming Lu, Xubo Hu
    1998, 19(S1):  426-427. 
    摘要 ( 232 )   PDF (85KB) ( 65 )  
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    Valinomycin is one of the most "important" antibiotic-ionophore. It is known to form more or less stable equimolar complexes with alkali ion in neutral solvents[1] Some synthetic carriers showing similar properties have also become known, among them, the most frequently seen are compounds like depsipeptides, cyclic polyethers and polythioethers[2]. These compounds are able to complex with alkali and alkaline-earth ions and make them soluble in nonpolar media. Such quality has attracted great research interest. In this note, we report our recent investigation on the migration of alkali and alkaline-earth metal ions across an organic phase as influence by cyclopeptides cyclo-(Pro-Gly)3,4 synthesized in this laboratory.
    Determination of N-NO Bond Heterolysis and Homolysis Energies of Nitrosoureas and Nitrosothioureas
    Jin-Pei Cheng, Ming Xian, Xiaoqing Zhu, Yongkai Sun, Linjing Mu
    1998, 19(S1):  428-429. 
    摘要 ( 180 )   PDF (97KB) ( 84 )  
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    There is currently great interest in the chemistry of nitric oxide (NO) following many important discoveries showing that NO is involved in a range of human physiological processes.1 Among ocean of researches in this area, some attention has been paid on the release of NO from aromatic N-nitrosoureas,not only from the point of view of their potential therapeutical use as alternative NO-releasing drugs,2 but also with regard to their possible involvement in vivo as potential NO-storage and transport vehicles.3 Thus, the cytoxicity mediated by NO is expected to be potent in aromatic N-nitrosoureas having NO-releasing ability. For NO-donor compounds, homolytic cleavage energy of N-NO bond (ΔHhomo) is considered a good measure of their NO-releasing ability. Here, we provide a method to derive the ΔHhomo data and present some results showing structure influence on the N-NO bond strengthes for several series of disubstituted ureas and thioureas.
    Cyclopeptides incorporating pyridine subunit as new receptors for phosphomonoester
    Linjing Mu, Jinpei Cheng, Hai Huang, Xiaohu Gao, Jianming Lu
    1998, 19(S1):  430-431. 
    摘要 ( 226 )   PDF (86KB) ( 124 )  
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    Phosphates play a crucial role in a wide range of biological processes. Numerous efforts have been devoted to molecular recognition, transport and catalytic hydrolysis of phosphate1-4. Recent reports have shown that molecules containing several hydrogen-bonding group directed into a cleft or cavity can effectively recognize phosphate5,6. We now report a new family of pseudo-cyclopeptides 1-4 as receptors for phosphomonoester, which were synthesized by the reaction of pyridine 2,6-dicarbonyl dichloride with cystine bis-peptides(H2N-Xaa-Cyst-Xaa-NH2) dimethylester leading to a variety of 1+1 cystine-based cyclic peptides with the general structure cyclo(Py-CONH-Xaa-Cyst-Xaa-NHCO-) (Cyst=L-cystine dimethyl ester; Xaa=amino acid X) and identified by conventional spectroscopic methods7.
    Hantzsch ester衍生物及其离子基N(C)-H键断裂能量及在其反应机理研究中的应用
    鲁云, 刘端, 赵炳筠, 朱晓晴, 程津培
    1998, 19(S1):  432-433. 
    摘要 ( 463 )   PDF (80KB) ( 100 )  
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    NAD(P)H辅酶氧化还原反应模拟研究在生物有机化学中一直占有显著的位置。Hantzsch 1,4-二氢吡啶作为NAD(P)H辅酶的一种类似物,不仅在有机合成、医药、生化等方面,而且在辅酶NAD(P)H模拟反应研究中均具有广泛的应用[1]。虽然Hantzsch 1,4-二氢吡啶与生物活性分子的反应已进行了大量的研究,但其反应机理即Hantzsch 1,4-二氢吡啶中1位N-H键和4位C-H键孰先孰后断裂仍存在较大争议。若能测得Hantzsch 1,4-二氢吡啶及其离子基中N-H和C-H键的断裂能,应能为阐释其反应机理提供有说服力的依据。
    有机硒修饰β-环糊精分子识别的圆二色谱研究
    韩宝航, 刘育, 和田健彦, 井上佳久
    1998, 19(S1):  434-435. 
    摘要 ( 342 )   PDF (80KB) ( 129 )  
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    目前作为新兴交叉学科的超分子化学已成为研究热点,超分子体系的分子识别作为分子组装和组装体功能的基础正在得到广泛而深入的研究。近来我们合成了多种有机硒修饰环糊精,研究了它们与某些脂肪直链醇及氨基酸的分子识别,给出了有意义的结果。本文利用圆二色谱技术研究了苄基硒修饰β-环糊精对环醇及某些天然手性醇的分子识别,发展了曲线拟合法求解主-客体键合常数的方法,并与Benesi-Hildebrand方程所得结果进行了比较。
    有机硒修饰β-环糊精的合成及其对氨基酸的手性识别研究
    厉斌, 刘育
    1998, 19(S1):  436-437. 
    摘要 ( 304 )   PDF (69KB) ( 70 )  
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    天然及化学修饰环糊精的分子识别研究是当今化学的前沿领域之一。我们曾报导了磷酰基、吡啶基、苯胺基等多种化学修饰β-环糊精对于氨基酸的分子识别研究, 得到了有意义的结果。(1-3)最近我们合成了一系列新型的6位单取代有机硒修饰β-环糊精,并报导了它们对脂肪醇的分子识别性能。(4)本文中我们研究了有机硒修饰β-环糊精对于氨基酸的分子识别能力和对映体选择性。
    环糊精2位衍生物的合成及其分子识别研究
    刘育, 尤长城, 和田健彦, 井上佳久
    1998, 19(S1):  438-439. 
    摘要 ( 303 )   PDF (80KB) ( 93 )  
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    环糊精是一类由D㈩-吡喃葡萄糖残基通过α-1,4-糖苷键键合成环的截锥状化合物,其具有疏水的空腔和亲水的表面,通过化学修饰,能够更加广泛地应用于科学和技术的多个领域。化学修饰主要是将特定的功能基引人到环糊精的边缘上,以提高其子识别能力和生物模拟酶等重要性能。[1]然而,由于合成的方便性,一般都在环糊精的主面,即6位的羟基上进行化学修饰,关于次面,即2,3位羟基修饰的研究报道还不多。[2-4]在目前的研究中,我们报道一些2位取代β-环糊精的合成及其对氨基酸生物小分子识别作用的初步结果。
    色氨酸修饰β-环糊精的合成及其分子识别机理研究
    刘育, 孙世新, 韩宝航, 和田健彦, 井上佳久
    1998, 19(S1):  440-441. 
    摘要 ( 250 )   PDF (78KB) ( 83 )  
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    环糊精通过化学修饰引入特定的功能基不仅可以改变原有的分子键合能力,而且还可以扩展对客体分子的手性对映体的选择性。[1-3]近来,我们报道了含吡啶基、磷酰基、有机硒、喹啉基、呋喃基、芴基等修饰β-环糊精的合成及对一些模型底物的分子识别,给出了有意义的结果。[4]在目前的研究中,我们报道L-色氨酸修饰β-环糊精的合成和对客体金刚烷醇的分子识别机理。
    β-环糊精修饰氯化血红素的合成、表征及人工酶性质
    沈含熙, 毛陆原
    1998, 19(S1):  442-443. 
    摘要 ( 276 )   PDF (102KB) ( 85 )  
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    血红素是含有铁卟啉的天然化合物。以天然的或人工的金属卟啉模拟过氧化物酶是近年来研究的活跃领域[1]。本研究认为,β-环糊糈(βCD)在结合某些酶底物或药物有更合适的空腔尺寸,将氯化髙铁血红素(Hemin)共价结合上去在仿生化学中有广泛的应用。本文用DCC缩合法合成了βCD-Hemin,作为过氧化物酶的底物的共受体,并将其均相催化动力学性质与天然酶(HRP)、氯化血红素辅基模型进行比较,应用光谱法通过监测在弱酸性介质中H2O2氧化隐色孔雀绿(MGL)生成孔雀绿(MG)染料的变化过程,来研究其仿生催化反应机理。
    β-环糊精修饰氯化血红素在弱碱介质中的仿酶性质研究
    毛陆原, 沈含熙
    1998, 19(S1):  444-445. 
    摘要 ( 269 )   PDF (111KB) ( 85 )  
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    将β-环糊精共价结合的氯化血红素(βCD-Hemin)作为过氧化物酶底物的共受体, 将其均相催化动力学性质与天然酶HRP或锰卟啉等辅基模型物进行比较,应用光谱法通过测量H2O2、苯酚和4-氨基安替比林(AAP)作用生成醌式染料的反应来研究其仿生催化机理。
    Free radical telluroacylative addition of telluroesters to terminal alkynes
    Chang-Qiu Zhao, Xian Huang, Jin-Liang Li, Ji-Ben Meng, Yong-Mei Wang
    1998, 19(S1):  446-447. 
    摘要 ( 198 )   PDF (85KB) ( 58 )  
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    Vinyl selenides and tellurides are important precursors of many kinds of organic compounds, particular the substituted alkenes that occurred in many biologically active compounds as skeleton structures. Thus the study of vinyl selenides and tellurides has attracted considerable attention in recent years. The bifunctional addition reactions involving selenium and tellurium moieties are the latest methods for preparation of vinyl selenides with various functional groups. Recently we have reported the selenocarbonylation of alkynes with selenoesters catalyzed by cuprous halides. Nevertheless the similar bifunctional addition involving tellurium atoms has not been reported. Considering the C-Te bonds are easier to be broken than corresponding C-Se bonds, the vinyl tellurides containing electron-withdrawing groups may have particular reactivity and application in the preparation of substituted alkenes. Herein we describe the synthesis of β-aryltelluro-α,β-unsaturated ketones via bifunctional addition.
    Structural Analysis of Simvastatin
    Zuo Yumin, Xu Jie, Ren Sumei
    1998, 19(S1):  448-449. 
    摘要 ( 240 )   PDF (104KB) ( 53 )  
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    Compactin(1) and lovastatin(2) are potent inhibitors of cholesterol biosynthesis in humans, and the more active semisynthetic derivative simvastatin(3) are pharmacologically useful compounds for lowering of serum cholesterol levels, The structure of simvastatin and related compounds is shown in Fig.1. It contains a hexahydronaphthalene ring system, a β-hydroxylactone and dimethylbutyrate structural unit.
    New Method for Developing ALS Enzyme Inhibitor
    LIU Jie, LI Zhengming
    1998, 19(S1):  450-451. 
    摘要 ( 235 )   PDF (73KB) ( 45 )  
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    Following with the rapid development of computer technology, Computer Aided Molecular Design (CAMD) has become a focus of attention in assisting the molecular design of some novel agrochemicals.
    A Novel Nucleophilic Substitution of 3-Halo-6-phenoxypyridazines
    Ren Kangtai, Li Huiying, Qi Jun, Song Honghai, Wang Xiang, Yang Huazheng
    1998, 19(S1):  452-453. 
    摘要 ( 215 )   PDF (93KB) ( 50 )  
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    Pyridazines have been found wide application in chemistry of pharmaceuticals and agrochemicals[1,2], therefore methods of direct introduction of substituents into pyridazine ring are of great interest[3]. Pyridazine belongs to highly electrophilic heterocycles, it shall undergo various nucleophilic substitution with X-、O-、S-、C- and H- anions[4].
    Microwave Assisting Solid Phase Organic Reactions-Approach to the Efficient Solid Phase Organic Synthesis
    YU Ai-Ming, YANG Hua-Zheng, ZHANG Chun-Xiang, LIU Zhun, ZHANG Zheng-Pu
    1998, 19(S1):  454-455. 
    摘要 ( 235 )   PDF (95KB) ( 48 )  
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    Solid phase organic synthesis provides a rapid mean for the preparation of compounds libraries, and has been successfully used for the construction of both oligometric compounds and small molecule compounds libraries[1]. That leads the resurgence of interest in solid phase organic synthesis, which encourages organic chemists to develop new reliable reactions, linkers and analytical techniques.
    中草药黄芪、黄芹中非淀粉多糖的含量分析
    田福利, 许辉, 张雪梅
    1998, 19(S1):  456-457. 
    摘要 ( 364 )   PDF (122KB) ( 87 )  
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    中草药黄芪是豆科植物膜荚黄芪Astragalus membranaceus (Fisch) Bge.和蒙古黄芪 A.mongholicus Bge.的干燥根,含有皂甙类、黄酮甙类及糖类,及多种氨基酸和微量元素。近年来越来越多的文献表明,其多糖含量较高,具有降压、利尿、强心,提高机体免疫的功能和抗衰老作用[1],并广泛应用于心血管疾病。由于对黄芪作用的不断认识,黄芪用量逐渐增加,并广泛用于饮料、补品、化妆品、茶叶等工业中。天然多糖具有非特异性免疫功能与抗衰老等诸多药理作用。本文采用糖醇乙酸酯衍生化、气相色谱法测定了中草药黄芪和黄芹中可溶性非淀粉多糖(SNSP)和不可溶性非淀粉多糖(INSP)的含量及各组成单糖的含量。该实验结果可为进一步深入研究中草药黄芪、黄芹的药理学作用,提供重要的理论依据。
    有机化合物中功能团电负性的估算
    曹宝亮
    1998, 19(S1):  458-459. 
    摘要 ( 601 )   PDF (96KB) ( 197 )  
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    在无机化学中,元素的电负性是指元素的原子在分子内吸引电子的能力。这种能力的大小决定该原子在分子内是正性还是负性,以及所形成的化学键的极性。目前虽然还无法直接测定元素的电负性,但其相对值却是比较完整的。在有机化学中,有机化合物的性质往往取决于化合物的功能团,而功能团的相对电负性是影响其性质的一个主要因素。关于有机物功能团的相对电负性这一问题, 不少人曾做了大量的工作,他们用不同的方法对有机物功能团的电负性进行了经验估算,集累了部分数据。
    An ab initio Research on the Pentacoordinate Carboxylic-phosphoric Anhydride
    ZHONG Rugang, LI Zhao-Long, ZHAO Yu-Fen, DAI Qianhuan
    1998, 19(S1):  460-461. 
    摘要 ( 375 )   PDF (119KB) ( 51 )  
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    It is well known that phosphorylated peptides involve in a lot of biological processes, such as metabolism, membrane transportation, muscle contractility,cell cycle control, and so on[1] Some recent researches revealed a new respect of this kind of compounds. An N-phosporyl-α-amino acid can react with an n-peptide to form an 1(n+l)-peptide and react with an n-(desoxy-)ribotide to form an (n+1)-(desoxy-)ribotide in aqueous solution at about 38℃, as shown in Fig.1. However, N-phosporyl-β-amino acids can not react with the same substrates at the same conditional[2].
    A theoretical Research on Two Type Compouds Derived from 5λ5-phospha-spiro[4.4]nonane
    ZHONG Rugang, LU Hai-Yan, ZHAO Yu-Fen, DAI Qianhuan
    1998, 19(S1):  462-463. 
    摘要 ( 333 )   PDF (86KB) ( 51 )  
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    Two kinds of derivatives of 5λ5-phospha-spiro[4.4]nonane, which are similar in structure, have very different properties. l,4,6-Trioxa-9-aza-5λ5-phospha-spiro[4.4]nonane-7-one (1) are easily hydrolyze in aqueous solution at room temperature as general pentacoordinate phosphorus compounds do. But the other derivative, l,6-Dioxa-4,9-diaza-5λ5-phospha-spiro[4.4]nonane-2,7-dione (2) are unusually stable in the same condition.
    糖类化合物的快原子轰击质谱研究
    吴毅为, 胡文祥
    1998, 19(S1):  464-465. 
    摘要 ( 268 )   PDF (121KB) ( 81 )  
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    人类在探索生命科学的进程中,对糖、蛋白质及核酸这三类基本生命物质的研究日益深入。近年来,随着分子生物学特别是细胞生物学的高速发展,糖类化合物在生命科学中所起的作用也得到了高度重视。糖不仅作为能量物质(葡萄糖、淀粉、糖原)和结构物质(几丁质、纤维素)为人们所熟知,它的其它诸多生理、生化功能,如携带和传递生物信息,调节细胞的生长发育、分化代谢及免疫反应等,均逐渐被掲示和认识。
    Synthesis and Molecular Recognition of Novel Cleft-type Receptors
    Shu-hua Chen, Dong-Hong Li, Fang Li, Hua-Ming Zhao
    1998, 19(S1):  466-467. 
    摘要 ( 280 )   PDF (71KB) ( 47 )  
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    A novel type of molecular cleft has been designed and synthesized from estrogen and approprite spacer groups such as xylylene or pyridine dimethylene. These receptor compounds 1a-d and 2a-d have been characterized by Mass spectra,1H-NMR spectra,IR spectra and elemental analyses. The structures of the receptors are shown in scheme 1. Their molecular recognition properties for the aromatic amine and aromatic amino acids have been investigated by UV-visble spectrophotometric titration. The titration data were analyzed by using the Benesi-Hildebrand equation[1].
    Synthesis of Calix[6]arene-Porphyrin Receptors and Study on their Catalytic Performance in Epoxidation of Styrene
    Donghong Li, Shuhua Chen, Huaming Zhao
    1998, 19(S1):  468-469. 
    摘要 ( 242 )   PDF (90KB) ( 54 )  
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    The artificial receptors with multiple recognition site had been synthesized by linking two unsymmetrical monofunctionalized porphyrin to p-tert-butyl calix[6]-arene via two flexible chain, followed by inserting metal ion into the porphyrin species.The structures (see Fig 1) of these calix[6]arene-diporphyrins and their metal complexes were confirmed by UV-vis spectra, IR spectra, mass spectra, 1NMR spectra(600 MHz) and/or 13C NMR. Their conformations were investigated preliminarily by UV-vis spectra and computer simulation. In constrast with the correspounding porphyrin monomer, the soret bond of calix[6]arene-diporphyrins in UV-vis spectra showed hypsochromic shift. This phenomenon suggested that two porphyrin rings maintain a face to face parallel conformation, as confirmed by computer simulation that showed the conformation energy is the lowest as two porphyrin rings hold such a conformation. Besides, simplicity of the 1NMR spectra indicates that the conformation of calix[6]arene-diporphyrin possesses high symmetry. Therefore,the calix[6]arene must be cone conformation.
    Hydrolysis of Lipophilic Amino Acid Esters Catalyzed by Metallomicelles
    Xiao-Qi Yu, Jing Song You, Qing-Xiang Xiang, Qian-Shun Yan, Ru-Gang Xie
    1998, 19(S1):  470-471. 
    摘要 ( 183 )   PDF (98KB) ( 55 )  
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    Metallomicelles as the model of hydrolytic metalloenzymes have begun recently1. Examples are the metal-ion complexes of lipophilic imidazoles2 and pyridines3 co-micelled with surfactants. Herein we report the complexes of a novel macrocyclic 12-membered di-oxotetraamine ligand bearing bis-hydroxy groups as functional pendants which can mimic the catalytic function of carboxypeptidase A in micellar media.
    双芳乙烯基吡啶盐的合成及其光化学反应
    郑艳, 张文勤, 王淑丽
    1998, 19(S1):  472-473. 
    摘要 ( 235 )   PDF (92KB) ( 54 )  
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    反-4-芳乙烯基吡啶类化合物在稀酸(盐酸或硫酸)的水溶液中经历激发单线态历程,几乎定量地生成"头碰尾"的二聚体[1][2][3]。但由于单线态反应为双分子历程,只有在反应物浓度较高时才能顺利进行光二聚反应,而在浓度较低时则主要进行顺反异构化反应。为此,我们用不同长度的亚烷基碳链将两个反-4-芳乙烯基吡啶单体的吡啶环一端连接起来,得到了四种二溴化-α,ω-亚烷基-双[反-4-(2-苯基乙烯基)吡啶盐], 简称PEPyR(I)。
    新型冠醚有机硅聚合物和聚乙二醇有机硅聚合物的相转移催化性能研究
    郭艳玲, 王世润
    1998, 19(S1):  474-475. 
    摘要 ( 358 )   PDF (95KB) ( 56 )  
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    相转移催化反应是一种有机合成新技术,用途甚广。用小分子季铵盐、季磷盐、聚乙二醇、冠醚等作相转移催化剂时,反应一般在互不相溶的两相系统(液-液)或(液-固)中进行。用不溶性聚合物作相转移催化剂时,反应在三相系统(液-液-固)或(液 -固-固)中进行,故后者称为三相催化剂(简称TPC)。由于三相催化剂有易于从反应体系中分离及回收后重复利用之优点,因此受到人们的重视。[1-2]
    The Competition between the SRN1 and the SNAr on the β-position of Porphyrin Ring
    Chen Zhangping, Chen Yangsheng, Jiang Zhongxing, Zai Baoping, Wu Xuanjie
    1998, 19(S1):  476-477. 
    摘要 ( 307 )   PDF (92KB) ( 53 )  
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    In our recently reports, a series of amphipathic β-substituted porphyrins are synthesized, And their LB films show some novel properties.[1] During the preparation of the intermediate of amphipathic porphyrins by the reaction of 2-nitro-5, 10,15,20-tetraphenylporphyrinato copper (Ⅱ) 1 with phenoxide ion 2(eq.l), we found that the product distribution mainly relied on if the electron acceptor was added and which solvent was used. Here we will first report the influence of p-dinitrobenzene (P-DNB) to the above reaction,the influence of the solvents to this reaction and the reaction of 2-naphoxide with 1 will be reported elsewhere.
    纳米TiO2异相光催化降解2,6-二甲酚中间过程的UV吸收光谱和荧光光谱示踪研究
    马万红, 蔡汝秀
    1998, 19(S1):  478-479. 
    摘要 ( 464 )   PDF (102KB) ( 164 )  
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    用半导体纳米材料(如TiO2,SnO2,CdS等)进行光降解消除污染物因其能最大限度利用太阳能和降解完全(有机质最终全部转化为CO2,H2O等)以及降解速率高的特点被认为是环境科学的新领域。异相光催化降解是有机物作为电子供体捕获TiO2表面光生空穴自身被氧化降解的过程,因TiO2价带空穴所具有强的氧化性,一般有机物都可进行光化学反应[1]。这一过程总是以一系列的中间反应步骤所构成,中间体形成的峰形动力学曲线及其异于原初态的光谱特性对揭示光催化降解动力学过程至为重要。本文主要对2,6-二甲酚-纳米TiO2悬浮体系光降解动态分子光谱进行示踪研究。
    Photosensitization of Two-dimensional Conjugated Polymers of Iron(Ⅱ)-and Cobalt(Ⅱ)-porphyrazine with Sulfur Bridges to CdS-PVA Film
    PENG Zheng-he, CHEN Xiao-gui, WANG Zheng-ping, WEI Yi-hai, QIN zi-bin
    1998, 19(S1):  480-481. 
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    Metal-porphyrazines (MPzs) and their polymers exhibit high thermal stability and unique photoelectric functions due to the macrocyclic planar structure and a delocalized π-electron system of the porphyrazine[1-3]. We have been found that the metal-thioporphyrazines (MSxPzs) and their conjugated polymers (PMSxPzs) have usually peculiar a gas-sensitivity, photosensitivity and electrocatalytic activity[5-8]. In the present abstract we report briefly photosensitization of the title polymers PMS8Pz (see Scheme 1) to the CdS-PVA film.
    The Studies of Fast Atom Bombardment Mass Spectrometry of Melezitose Derivatives
    Cao Linghua, Sun Guanzhong, Liu Yuting, Dou Hui, Wang Wei
    1998, 19(S1):  482-483. 
    摘要 ( 208 )   PDF (91KB) ( 37 )  
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    Melezitose is a kind of nonreducing sugar, its structure is 3-(α-D-glucopyranosyl)-β-D-fructofuranosyl-α-D-glucopyranose, it is a principal constituent of Alhagi pseudalhagi Desv.manna, which is used as a drug in Uygur medicine.
    The photoconductive properties of bisazo pigments from 1,5-diaminoanthraquinone
    Zhang Yu-Hong, Ruan Jian-Li, Lu Wen-Li, Yu Qing-Sen
    1998, 19(S1):  484-485. 
    摘要 ( 231 )   PDF (102KB) ( 41 )  
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    The photoconductive properties of azo compounds were reported as early as 1969 by Rau[1] who observed photocurrents from thinlayers of 1-phenylazo naphthol. From then on, thousands of pigments of a variety structures have been synthesized and studied[2].The pigments absorb and photorespond in the visible region are not usable in the xerographic printers which use the long wavelength illuminators, such as light-emitting diodes(660-700nm) and solid state diode lasers(700-850nm). So the need of laser addressable photoconductors is obvious and the various strcture IR photoconductors were studied intensely in recent years[3-5].
    植物样品中生长激素的色谱法分离和测定
    方能虎, 何友昭, 邵学广, 曹心德, 赵贵文
    1998, 19(S1):  486-487. 
    摘要 ( 326 )   PDF (87KB) ( 81 )  
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    本文运用反相HPLC技术,以梯度洗脱,峰面积法定量,建立了一种生长素(IAA)、赤霉素(GAs)和细胞分裂素(ZT)等三种植物生长激素同时测定的快速、简便的方法。并应用于萌发水稻中三种生长激素的测定。结果令人满意。
    多種有機鏈烯正離子自由基的研究
    石型
    1998, 19(S1):  488-488. 
    摘要 ( 319 )   PDF (22KB) ( 48 )  
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    本文報導在經過氧氣高溫處理後的H-ZSM-5沸石所生成的多種開鏈及閉環的鏈烯正離子基衍生物,利用計算機模擬了解在沸石孔洞内的化學吸附情形,同時幫助判定正確的超精細偶合常數。本文提出一個數學物理方程式,他能解釋分子的對稱性及這些正自由基的幾何形狀。
    Theoretical Studies of Azulene and Its Derivatives
    Bo-Cheng Wang, Pei-Yu Wang
    1998, 19(S1):  489-489. 
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    The results of ab initio calculation with STO-3G and 6-31G basis set on the azulene and its derivatives (included azulenequinones, diazoazulenequinones and polyether bridged azulenes) are presented in accordance with considerations of structures and bonding. Azulene is a nonalternant aromatic compound with ten π electrons and it has either Cs or symmetry dgpend on the different carbon and carbon bonding. The calculation results indicate that Cs symmetry is the ground state structure of azulene. TTie simple MO and CIS calculations describe the excited state of azulene.
    Electrooxidation of Azulene Compounds
    Arh-Hwang Chen
    1998, 19(S1):  490-490. 
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    Azulenoid, a parent structure of bicyclo[5,3,0] decapentaene with 10 π-electrons, is a class of the fused bicyclic compounds, non-benzenoid hydrocarbons. It is essentially used for the dye materials, the medical treatment of inflammation and hypertension and the development of liquid crystals. More recently, azulopquinones have been found to exhibit a significant antitumor activity. In the early organic electrochemical studies, azulene was first known the oxidation potential, 0.91 V vs SCE in acetic acid. The reversible and irreversible reduction potential,-1.6 V and -2.6 V vs Ag/AgCl in liquid methyl amine and dimethyl amine, respectively, were measured by Heinze et al in 1989 using cyclovoltammetric method. The conducting polymers were successfully developed from azulene and 4,6,8-trimethylazulene via electropolymeriztion by Waltman et al in 1986. Recently in 1993, Shono et al revealed that azulene was easily reduced to 5,5'-biazulene or consequently to react with alkyl halides producing 1,1'-dialkyl-5,5'-biazulene.