D-奎尼酸: 一个多用途的手性合成子

综述了D-奎尼酸在各种环状和链状生物活性化合物合成中的应用。奎尼酸分子中特有的顺式γ-羟基羧酸的结构单元提供了区别分子中各种羟基,以及进行其它区域选择性和立体选择性控制的方便途径。奎尼酸的结构特征以及其价廉、易得的优点,使之成为一个有用的而且重要的手性合成子。     

二茂铁基Tamoxifen类似物的合成、结构与性质

合成了一系列二茂铁基Tamoxifen类似物并作了初步生化试验(RBA试验),研究了代表化合物二茂铁基羟基Tamoxifen的晶体结构和顺-反异构化。     

二(α-肟基丙酸根)合铜(Ⅱ)的固相合成、表征及热分解

Bis(2-hydroxyiminopropanoato) copper (Ⅱ) (［Cu(PAO)₂］·2H₂O) was synthesized by one step solid reaction between Cu(Ac)₂·H₂O and 2-hydroxyimino propanoic acid (HPAO) at 50℃. The complex was characterized by element     

三元混配M（ATP）（3,4—Lu）^2—配合物的稳定性研究

25℃下,用pH电位滴定法研究了二元M(3,4Lu)2 和三元混配M(ATP)(3,4Lu)2-配合物(ATP4-=三磷酸腺苷,3,4Lu=3,4二甲基吡啶,M2 =Co2 ,Ni2 ,Cu2 或Zn2 )在水溶液中的稳定性,三元混配配合物相对于二元配合物的稳定性用M(3,4Lu)2 M(ATP)2-=M(ATP)(3,4Lu)2- M2 的平衡常数ΔlogKM(=logKM(ATP)M(ATP)(3,4Lu)-logKMM(3,4Lu))表示,结果比统计值大,这可能主要归因于三元混配配合物分子内ATP4-与3,4Lu之间的σ-π协同效应及其芳环间的堆积作用,′HNMR谱研究确证了这种堆积作用的存在。     

Use of Tetramethylthiuram Disulfide in Synthesis of Nitrogen-containing Heterocyclic Compounds

We have developed a method for synthesis of aryl isothiocyanates by means of thiocarbamoylation of aromatic amines by tetramethylthiuram disulfide followed by degradation of the intermediate N₍₁₎-aryl-N,N-dimethylthiourea by concentrated HCl. We have shown that thiocarbamoylation of 4-amino-5-ethyl-4H-1,2,4-triazole-3-thiol occurs at the 2 position of the triazole ring, while thiocarbamoylation of 4-amino-3-methyl-6-phenyl-4,5-dihydro-1,2,4-triazin-5-one leads to the dihetaryl-substituted thiourea. We consider the possibility of using N₍₁₎-aryl-N,N-dimethylthioureas as analogs of isothiocyanates in reactions with N-nucleophiles.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 775–780, May, 2005.     

Ion-exchange selectivity of a network calixarene-containing polymer obtained by the template synthesis on Na<Superscript>+</Superscript>, K<Superscript>+</Superscript>, and Ba<Superscript>2+</Superscript> matrices

The ion-exchange equilibrium in network polymers obtained from cis-2,8,14,20-tetraphenyl-4,6,10,12,16,18,22,24-octahydroxycalix[4]arene by template synthesis on cations Na⁺, K⁺, and Ba²⁺ as matrices was studied. The selectivity coefficients of ion exchanges Ba²⁺-H⁺, Na⁺-H⁺, K⁺-H⁺, Na⁺-K⁺, and Na⁺-NH₄ ⁺ were determined. The template synthesis enhanced the affinity of the polymers to matrix-forming cations by 6–8 kJ mol⁻¹. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1919–1922, August, 2005.     

Application of Cyclodextrins to the Extraction of Antioxidant Compounds from Olive Oil

Olive oil contains powerful antioxidant compounds which impart stability, contribute to various properties of it, and are valuable from the nutritional point of view. Their extraction with as mild conditions as possible led to its investigation using cyclodextrins as a tool. The inclusion ability of α-, β-, and γ-CD was estimated, and it has been demonstrated that the small cavity of α-CD as well as the wide one of γ-CD could enclose less effectively the antioxidant compounds of olive oil than the intermediate in shape cavity of β-CD. The highest yields of antioxidant compounds were achieved when olive oil was mixed with a 2%aqueous solution of β-CD and the resulting precipitate was treated with ethyl alcohol.__________Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 18–21, January–February, 2005.     

Oxidation of α-methylstyrene on an MCM-22 encapsulated (<Emphasis Type="Italic">R,R</Emphasis>)-(−)-<Emphasis Type="Italic">N,N′</Emphasis>-bis(3,5-di-<Emphasis Type="Italic">tert</Emphasis>-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II) catalyst

(R, R)-(−)-N, N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II) was encapsulated into MCM-22 using the zeolite synthesis method. The encapsulated catalyst proved to be active in the oxidation of α-methylstyrene with NaOCl with higher specific activity than the homogeneous catalyst. At the same time, this encapsulated catalyst was completely inactive in the hydrolytic kinetic resolution of racemic styrene oxide. This observation is in a good correlation with the assumption of the cooperative bimetallic mechanism proposed by Annis and Jacobsen.     

Synthesis of 4-Hydroxy- and 4-Amino-2-Methyl-3-(2-Methylindol-3-Yl)methylquinolines and Their 6- and 8-Substituted Derivatives

A method has been developed for the synthesis of substituted 4-hydroxy- and 4-amino-2-methyl-3-(2-methylindol-3-yl)methylquinolines by treating the corresponding 4-hydroxy(chloro)-2-methyl-3-(3-oxobutyl)quinolines with phenylhydrazine hydrochloride. It was found that nucleophilic substitution occurred in the case of the 4-chloroquinolines together with subsequent rearrangement to give the 4-amino derivatives. The thiosemicarbazones of the corresponding 4-hydroxy-2-methyl-3-(3-oxobutyl)quinolines were also obtained.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 554–557, April, 2005.     

Flavonoids of <Emphasis Type="Italic">Scutellaria immaculata</Emphasis> Roots

(±)-5,2′-Dihydroxy-6,7,6′-trimethoxyflavanone, (-)-5,2′-dihydroxy-6,7,8,6′-tetramethoxyflavanone, chrysin, wogonin, apigenin, isoscutellarein, scutellarein, cosmosiin, and the new flavonoid wogonin-7-O-β-D-glucopyranoside, the structure of which was established using chemical transformations and spectral data, were isolated from Scutellaria immaculata roots.__________Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 26–28, January–February, 2005.