八十年代海洋天然有机化学的进展

八十年代以来,海洋天然有机化学仍然继续发展,大量新的化合物,尤其是具有生理活性的化合物不断出现,海洋天然物的生物合成和人工合成研究也有新的进展。在海洋生物中,研究得最多的是海藻和海绵,其次便是珊瑚。     

生物检材中乌头类生物碱的检验

 用薄层 (TLC)、高效液相 光电二极管阵列检测器 (HPLC/DAD)、动物实验等方法对生物检材中乌头生物碱进行检验 ,并对这些方法进行比较。结果发现 ,TLC法为此类药物检验筛选的首选方法 ,最小检出量为 0 3μg。在进行HPLC检测时 ,以乌头生物碱的特征紫外吸收光谱和动物实验结果为重要的定性手段 ,其特征吸收波长为 (2 2 8± 2 )nm和 (2 75± 2 )nm。乌头生物碱在 2mg/L～ 5 0mg/L时其峰面积与质量浓度有很好的线性 ,相关系数为 0 9996。经实际案件证明 ,方法准确、灵敏 ,可用于生物检材中乌头类生物碱的检验。     

Synthesis of the marine furanoditerpene (−)-marginatone

A synthesis of the marine labdane furanoditerpene (−)-marginatone 1 has been accomplished by a short sequence of reactions starting from (+)-coronarin E 5. The key step is the stereocontrolled-intramolecular electrophilic cyclisation of the (+)-dihydrocoronarin E 6, to the tetracyclic marginatane skeleton 7, which is subsequently functionalized by allylic oxidation to give 1. As (+)-coronarin E 5 was previously synthesized from (−)-sclareol 10, the herein reported preparation constitutes the first formal total synthesis of (−)-marginatone 1, by which its absolute configuration has been confirmed.     

Synthesis and thermal decomposition of ditetrazol-5-ylamine

Ditetrazol-5-ylamine (DTA) was synthesized from cyanuric chloride in four steps. The thermal decomposition of DTA in the solid state was studied by thermogravimetry, volumetry, mass spectrometry, IR spectroscopy, and calorimetry. Under isothermal conditions at 200–242 °C, thermal decomposition obeys the first order autocatalytic kinetics. The kinetic and activation parameters of DTA decomposition were determined. The composition of gaseous reaction products and the structure of condensed residue were studied. The thermal effect of thermal DTA decomposition is 281.4 kJ mol⁻¹. The nitrogen content in a mixture of gaseous products formed by the reaction in a temperature interval of 200–242 °C exceeds 97 vol.%. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1660–1664, July, 2005.     

Conductivity studies on some alkali metal iodides in aqueous N,N-dimethylformamide solutions at 298.15K

Summary Conductance measurements for NaI, KI, RbI, and CsI in water/N,N-dimethylformamide mixtures over the whole composition range at 298.15K are reported. The data were analyzed employing theFuoss-Justice equation in terms of limiting molar conductances (_o),Walden products (_o), and association constants (K _A). The results indicate that the salts are weakly associated in the above solvent mixture. Variation in theWalden products with solvent composition are briefly discussed. The results were also compared with values reported previously for some alkali metal chlorides and bromides.

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Untersuchungen zur elektrischen Leitfähigkeit einiger Alkalimetalliodide in wäßrigen N,N-Dimethylformamidlösungen bei 298.15K

Zusammenfassung Die elektrische Leitfähigkeite von NaI, KI, RbI und CsI wurde in N,N-Dimethylformamid-Wasser-Mischungen verschiedener Zusammensetzung bei 298.15K gemessen. Die erhaltenen Daten wurden analysiert und bezüglich der Grenzäquivalenzleitfähigkeiten (_o), derWalden-Produkte (_o) und der Assoziationskonstanten (K _A) ausgewertet. Die Ergebnisse zeigen, daß diese Salze in den verwendeten Lösungsmittelgemischen nur schwach assoziiert sind. Die Änderungen derWalden-Produkte in Abhängigkeit der Lösungsmittelzusammensetzung werden kurz diskutiert. Abschließend werden die Resultate mit Ergebnissen früherer Messungen, in denen das Verhalten von Alkalimetallchloriden und Alkalimetallbromiden untersucht wurde, verglichen.

     

亚甲胺叶立德参与的[3＋2]环加成反应的最新进展

综述了亚甲胺叶立德的制备、它参与的[3＋2]环加成反应的反应机理、反应选择性及在天然产物全合成中的应用等方面的最新进展.     

Physico-chemical aspects of polyethylene processing in an open mixer. Part 23: Mechanisms and kinetics of trans-vinylene group consumption

There are many potential reactions for trans-vinylene groups in oxidizing polyethylene melts. The main possibilities are reactions with peroxy radicals, molecular oxygen, hydroperoxides and peracids. These different reactions can all contribute to the removal of trans-vinylene groups to some extent. This is especially so, for the reactions with hydroperoxides that have been found to be the dominant reactions with vinylidene and vinyl groups in the low temperature range. The reaction with peroxy radicals is thought to be as important relatively as with vinylidene groups. Therefore, the importance of the reaction is decreasing with increasing temperature. However, the most characteristic reaction for trans-vinylene groups can be detected without any doubt only in the advanced stages of processing. It is mechanical stress induced oxygen addition to the double bond. The discussion shows that the reaction should be important from the beginning of processing. The reaction cannot operate with vinyl and vinylidene groups, which are not part of the polyethylene main chain. After oxygen addition to the trans-vinylene group, the “ene” reaction yields an allylic hydroperoxide so that the double bond is not immediately removed. It is acid catalyzed hydroperoxide decomposition that leads to chain scission with aldehyde formation at the new chain ends.     

New compounds obtained by enzymatic oxidation of phloridzin

Oxidation of phloridzin was studied in a model system in the presence of apple polyphenol oxidase. In addition to 3-hydroxy phloridzin, two major oxidation products were purified by reversed phase HPLC at the semi-preparative scale. Their structures were elucidated by UV, ESI-MSⁿ and NMR spectroscopies. The first compound was a colourless product, whose novel structure strongly differs from its precursor showing a biphenyl moiety and a propionic acid chain. The second product was an oxidised form of the first one and corresponded to a stable yellow pigment with two isomeric forms. A mechanism of formation of these products, which implied successive oxidation and nucleophilic addition steps was proposed.