1－芳氧基乙酰基－4－邻氯苯甲酰基氨基硫脲衍生物的合成及其生物活性研究

于固－液相转移催化条件下，合成了１０个１－芳氧基乙酰基－４－邻氯苯甲酰基氨基硫脲衍生物，用元素分析、ＩＲ和￣１Ｈ－ＮＭＲ光谱确定了它们的结构。该类化合物对小麦幼苗生长具有明显的促进作用。     

Michael and ring expansion reactions of 6-carboethoxy-3,5-diaryl-2-cyclohexen-1-ones

When -keto-ester1 a was reacted with dimethyl acetylenedicarboxylate ring expansion occurred to give substituted cyclooctadienones.Michael reactions of the title compounds1 with unsaturated ketones gave adducts, some of which underwent further cyclization reactions. A new route to -tetralone ring system10 via cyclization of the intermediateMichael adduct9 is described.

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Michael- und Ringerweiterungsreaktionen von 6-Carboethoxy-3,5-diaryl-2-cyclohexen-1-onen

Zusammenfassung Bei der Reaktion von -Keto-ester1 a mit Dimethyl-acetylendicarboxylat wurden unter Ringerweiterung substituierte Cyclooctadienone erhalten. DieMichael-Reaktion der Titelverbindung1 mit ungesättigten Ketonen ergab Addukte, von denen einige weitere Cyclisierungsreaktionen eingingen. Es wird ein neuer Weg zum -Tetralonsystem10 über die Cyclisierung des intermediärenMichael-Addukts9 beschrieben.

     

The synthesis and electrochemistry of CpTiCl2(OR) (R = alkyl, aryl) complexes

The syntheses of several new CpTiCl₂(OR) (R = alkyl, aryl) complexes are described. It was possible to isolate pure product when the R group is substituted such as to cause steric crowding at the metal centre; for example, particularly good yields of the phenolate complexes were obtained when there were isopropyl substituents in the 2 and 6 positions of the phenolate. Electrochemical studies of the complexes in dry THF show that the Ti^III complexes are relatively stable, but only a diol complex could be reduced further to a Ti^II species. In general, the Ti^IV complexes undergo a reversible 1e⁻ reduction reaction. The chemistry is more complex if the electrolyte contains added water: both the Ti^IV and Ti^III complexes can react with water, the OR group being replaced by OH. The reaction is particularly rapid for the Ti^III alkoxide complexes.     

Synthesis, structures and spectroelectrochemistry of methyl-substituted bis(η-indenyl)iron(II) complexes

Several new methyl-substituted indenyl ferrocenes were prepared by metathesis reactions of the indenide (generated from the appropriate indene with BuLi) with ferrous chloride. The indenides used to prepare new ferrocenes were: 2-methyl-, 1,2-dimethyl-, 4,7-dimethyl-, 1,4,7-trimethyl-, and 1,3,4,7-tetramethyl-indenide. These indenyl ferrocenes, along with those prepared from indenide, 1-methylindenide, and 1,3-dimethylindenide, were then characterized by ¹H and ¹³C NMR, UV/visible spectroscopy, cyclic voltammetry and mass spectrometry. The cyclic voltammetry showed an additive relationship between oxidation potential and the number of methyl groups which is also position-dependent, whereas the UV/visible spectra showed two absorptions essentially unaffected by methyl substitution. Additionally, bis(2-methylindenyl)iron(II) and bis(4,7-dimethylindenyl)iron(II) were characterized by X-ray crystallography.     

Synthese und Kristallstrukturen der Phosphanimin-Komplexe MCl2(Me3SiNPMe3)2 mit M = Zn und Co,und CoCl2(HNPMe3)2

Syntheses and Crystal Structures of the Phosphaneimine Complexes MCl₂(Me₃SiNPMe₃)₂ with M = Zn and Co, and CoCl₂(HNPMe₃)₂ The molecular complexes MCl₂(Me₃SiNPMe₃)₂ (M = Zn, Co) have been prepared by the reaction of the dichlorides of zinc and cobalt with Me₃SiNPMe₃ in CH₃CN and CH₂Cl₂, respectively, whereas the complex CoCl₂(HNPMe₃)₂ has been prepared by the reaction of CoCl₂ with NaF in boiling acetonitrile in the presence of Me₃SiNPMe₃. All complexes were characterized by IR spectroscopy and by crystal structure determinations. The complexes MCl₂(Me₃SiNPMe₃)₂ crystallize isotypically. ZnCl₂(Me₃SiNPMe₃)₂: Space group P2₁2₁2₁, Z = 4, 2677 observed unique reflections, R = 0.024. Lattice dimensions at ?70°C: a = 1243.6; b = 1319.0; c = 1464.7 pm. CoCl₂(Me₃SiNPMe₃)₂: Space group P2₁2₁2₁, Z = 4, 3963 observed unique reflections, R = 0,071. Lattice dimensions at ?80°C: a = 1236.3; b = 1317.4; c = 1457.6 pm. CoCl₂(HNPMe₃)₂ · CH₂Cl₂: Space group Pbca, Z = 8, 1354 observed unique reflections, R = 0.055. Lattice dimensions at ?80°C: a = 1247.3; b = 998.4; c = 2882.4 pm. All complexes have monomeric molecular structures, in which the metal atoms are coordinated in a distorted tetrahedral fashion by the two chlorine atoms and by the nitrogen atoms of the phosphaneimine molecules.     

两组份互穿网络聚合物的合成研究

以蓖麻油聚氨酯和聚醚聚氨酯的不同重量比与光敏剂、催化剂、稀释剂、促进剂所组成的多相体系为反应物,分别在紫外光照射和加热的条件下合成网络Ⅰ和网络Ⅱ的互穿网络聚合物(IPN)。改变网络Ⅱ聚醚聚氨酯中各组份的摩尔比制得系列样品。红外光谱,应力-应变曲线和动态力学性能测定发现,样品的力学性能与两组份重量比和网络Ⅱ中不同组成都存在着一定关系。这些结果,为该体系IPN的合成和应用提供了一定依据。     

THE POLYMERIZATION OF AROMATIC AND HETEROCYCLIC DINITRILES

This review is a concise survey about the works in our laboratory on the polymerization of aromatic and heterocyclic dinitriles, including the polymerization kinetics and mechanism, synthesis of heterocyclic dinitriles, the structure of polymers, and the correlation between the structures of dinitriles and polymerization rates and thermal performances of Polymers.     

钛硅分子筛TS-1合成晶化气氛的影响

考察了不同晶化气氛(N2、H2、A ir、O2)对合成钛硅分子筛TS-1的影响,用XRD、IR和N2吸附/脱附对所合成的钛硅分子筛进行结构表征,发现在H2气氛下合成的TS-1结晶度最高,锐钛矿的含量最少;O2气氛下合成的TS-1中锐钛矿含量最高.以氯丙烯氧化为模型反应,考察了不同晶化气氛下合成的钛硅分子筛的催化活性和双氧水的利用效率.结果表明,在H2气氛下所合成的钛硅分子筛的双氧水的利用效率最高.     

From chiral and prochiral N-allylpyrroles to stereodefined pyrrole fused architectures: A particular application of the rhodium-catalyzed hydroformylation

We review our recent results on the rhodium-catalyzed hydroformylation of chiral and prochiral N-allylpyrroles as a synthetic route to stereodefined 5,6-dihydro- and 5,6,7,8-tetrahydroindolizines. The indolizine nucleus at different degrees of unsaturation is a building block of natural and synthetic target compounds; thus new approaches, especially if stereoselective and/or stereospecific, are highly desirable. The construction of the indolizine architectures reported here occurs by formation of a C8-C9 bond through intramolecular cyclization of the 4-pyrrolylbutanal intermediate.     

Synthesis and biological activity of novel 2-(3-trifluoromethylphenoxy)-4-trifluoromethylthiazole-5-carboxamide derivatives

Novel 2-(3-trifluoromethylphenoxy)-4-trifluoromethylthiazole-5-carboxamides were designed and synthesized utilizing ethyl 3-amino-4,4,4-trifluoro-2-butenoate as a starting material via six steps. Subsequently, their biological activities were evaluated in the greenhouse. Results indicated that several compounds have some insecticidal or fungicidal activity at 600 g ai/ha and 300 g ai/ha, respectively.