三芳基膦配体的合成研究

从间溴苯酚出发, 利用新的合成方法经五步反应合成了一系列具有不同烷氧基的芳基膦配体. 改进后的方法可方便地通用于在苯环上具有各种不同基团基的膦配体衍生物的合成, 且有原料易得、操作简单、产率较高的优点.     

Synchrotron diffraction studies of TiC/FeTi cermets obtained by SHS

TiC/FeTi composites have been obtained in situ by Self-propagating High-temperature Synthesis (SHS) of an intimate mixture of compacted powders of elemental carbon, titanium and iron. The reaction has been followed in real time by X-ray diffraction at the ESRF. The mechanism of the reaction is discussed in terms of the formation of a liquid phase corresponding to the eutectic of the Fe/Ti system prior to the TiC synthesis. Temperatures of reaction have been estimated by correlating thermal expansion coefficients with diffraction peaks shifts. The microstructures obtained by this method, suitable for cutting tools and wear resistant applications, are presented.     

N- and O-Alkylation of 3-indolylcyclopropylacetic acid derivatives

2,2-Dimethyl-3-(2-methyl-3-indolyl)cyclopropylacetic acid, its amide and esters, and the corresponding alcohol, viz., the product of ester reduction by LiAlH₄, were synthesized. The chemoselectivity of N- and O-alkylation of these compounds was studied. Selective monoalkylation at the nitrogen atom of the heterocycle, O-alkylation to the side chain, or dialkylation at both nucleophilic sites can be carried out under conditions of phase-transfer catalysis. The N-acylation at the indole fragment of nitrile of this acid occurs only under the Vilsmeier—Haak formylation conditions.     

有机锡试剂在有机合成中的某些新应用

本文阐述有机锡试剂在有机台成巾的一些新应用。在钯催化下,有机锡试剂与亲电试剂进行偶联,条件温和,收率高。有机锡试剂促进醇醛缩合,可用于不对称合成中。     

Syntheses of macrocyclic bisbibenzyls on solid support

We describe a route for the polymer supported total synthesis of the cyclic bisbibenzyls of the isoplagiochin type found in liverworts. TentaGel^® resins were used as solid support for a sequence involving Suzuki, Wittig and hydrogenation protocols. The polymer linked intermediates could be characterized by HR-MAS NMR. This route is to be extended to the synthesis of small libraries of differently halogenated derivatives.     

Synthesis and Characterization of the Isocyanide Ligated Centered Zirconium Halide Cluster [(Zr6Be)Cl12(CNXyl)6]

The first isocyanide ligated hexanuclear zirconium halide cluster is reported. The unoxidized [(Zr₆Be)Cl₁₂(CNXyl)₆] (CNXyl = 2,6-dimethylphenyl isocyanide) was obtained from the solid state precursor K₃Zr₆Cl₁₅Be by dissolution in CH₃CN in the presence of CNXyl. The CNXyl ligands occupy all the axial positions on the cluster. The compound was recrystallized from CH₂Cl₂ and Et₂O. [(Zr₆Be)Cl₁₂(CNXyl)₆].2CH₂Cl₂ crystallizes in the space group (#2) with a = 12.092(5) Å, b=12.728(5) Å, c = 14.102(8) Å, = 104.98(4)°, =107.11°, = 100.94°, V = 1919(2) ų, Z = l, R = 11.3% and R _W = 27.0%. For the bound isocyanide ligands, v _CN increases to 2140 cm^–1.     

New synthetic route to diaminonitropyrazoles as precursors of energetic materials

Treatment of nitropyrimidine derivatives with (N-substituted) hydrazines (2 equiv.) gave 1-(substituted)-3,5-diamino-4-nitropyrazole, providing a very mild conversion of pyrimidines into pyrazoles. This reaction provided a convenient route to precursors for new efficient and insensitive explosives.     

A New Approach to α—Bromochalcones

α-Bromo benzolymethylene triphenylphosphorane 3 has been synthesized by the reaction of benzoylmethylene triphenylphosphorane 1 with N-bromosuccinimide in the yield of 87% and can react with aromatic aldehydes 4 to give α-bromochalcones 5 in good yields.     

2-甲基-6-对甲苯基-1,6-庚二烯的合成

以对甲苯乙酮(1)为原料,经烯醇硅醚化,Lewis酸催化Michael加成反应和Wittig反应,合成了新倍半萜烯化合物2-甲基-6-对甲苯基-1,6-庚二烯。     

Synthesis of 1-triphenylgermylpropiono-4-substituted semicarbazides,thiosemicarbazides and their heterocyclic derivatives

Twenty-one new organogermanium compounds with the formulae Ph₃GeCHR¹CH₂CONHNHC(X)NHR² (1) (R¹=H, Ph; = Ph, p-CH₃Ph, O -CH₃Ph, p-ClPh, COPh, X = S, O) and (R¹ = H, Ph; R² = Ph, p-CH₃Ph, o-CH₃Ph, p-ClPh; X=S, O) were synthesized and characterized by elemental analysis, ¹H NMR, IR, MS and X-ray diffraction techniques. Compounds l were prepared by the reactions of Ph₃GeCHR¹CH₂CONHNH₂ with R²NCX in chloroform in 77-94% yields, and 2 were obtained by refluxing l with sodium hydroxide (8%) with yields of 55-94%.