U-4C-3CR versus U-5C-4CR and stereochemical outcomes using suitable bicyclic β-amino acid derivatives as bifunctional components in the Ugi reaction

Intramolecular Ugi reactions with bicyclic β-amino acids have been performed and the effects of the configuration and N-alkylation have been studied. We have proven that preferential ring contraction or nucleophilic attack by the solvent depend not only on the presence of N-alkylation but also on the relative disposition of the carboxyl group and the amine. Excellent results in terms of stereoselectivity have been obtained in the case of N-alkyl-3-exo-amino-7-oxabicyclo[2.2.1]-2-endo-carboxylic acids.     

“逐步偶联聚合反应”在研制有序交联高分子及复合物中的应用

用“逐步偶联聚合反应”这一新的合成方法可制备不同等级的微观结构可控的有序交联网状高分子,包括可溶性的一维梯形或管状高分子、不溶性的二维或三维筛板状高分子,新型的反应性梯形聚硅氧烷包括氢梯、乙烯基或丙烯基梯、乙氧基梯及其共聚物是功能性梯形高分子的前体,由此衍生出“鱼骨形”和“划艇形”液晶和非线性高分子、盘状金属络合物液晶高分子以及管状聚硅氧烷。对功能化梯形降硅氧烷进行了有趣的应用探索,包括用于稳定液     

纳米多孔双金属氧化物在镍钛合金纤维上的原位生长及其对多环芳烃的选择性固相微萃取

采用阳极氧化法在镍钛合金(NiTi)纤维上原位生长了双金属氧化物纳米孔(NiTiONPs)涂层,通过扫描电镜(SEM)和能谱(EDS)考察了电解质组成和电压对形貌的影响。将NiTiONPs涂层的NiTi纤维与高效液相色谱-紫外检测器联用,研究了4种典型芳香分析物的萃取性能。结果表明,富含TiO2的NiTiONPs涂层对多环芳烃(PAHs)具有良好的萃取效率,尤其对苯并[a]芘的萃取选择性优于市售聚二甲基硅氧烷纤维和聚丙烯酸酯纤维。在优化条件下,PAHs的线性范围为0.05~200μg/L,相关系数均大于0.999,检出限为0.012~0.134μg/L。对单支纤维日内和日间分析的相对标准偏差(RSDs)分别为4.0%~5.5%和6.0%~6.8%,使用分批组装的5支纤维分析的RSDs为6.4%~7.6%。实际水样分析的加标回收率为84.5%~111.5%。所制备NiTi纤维至少可重复使用250次以上,重现性好。     

Condensed rare-earth metal-rich tellurides. Extension of layered Sc6PdTe2-type compounds to yttrium and lutetium analogues and to Y7Te2, the limiting binary member

Six isotypic R₆ZTe₂ phases have been synthesized in Ta at elevated temperatures and characterized by single crystal X-ray refinements for R=Y, Z=Rh, Pd, Ag, Y and for R=Lu, Z=Cu, Ag. All crystallize in the Sc₆PdTe₂-type structure, Pnma, Z=4, a∼21.5 Å, b∼4.1 Å, c∼11.4 Å. The results can be viewed as the replacement of Te3 atoms in the parent isotypic Sc₂Te (or in the hypothetical Y₂Te or Lu₂Te analogues) by the above the Z, the Y example giving the new binary phase Y₇Te₂. The shorter (and stronger) metal-metal bonds concentrate in the region of metal (Z, Y) substitution, as revealed by larger integrated crystal orbital Hamilton population (ICOHP) values derived from linear muffin-tin-orbital (LMTO) calculations. Partial densities-of-states data for Y₇Te₂ reflect a similar behavior. Individual R-R bond distances are seen to deviate appreciably from the more fundamental overlap population measures for each.     

Palladium-catalyzed direct coupling reaction of propargylic alcohols with arylboronic acids

The direct coupling of propargylic alcohols with arylboronic acids has been achieved using palladium catalyst. Various propargylic alcohols and arylboronic acids can be coupled to afford the corresponding allenic and propargylic arenes, which are selectively produced depending on the substituent on the propargylic alcohol, respectively.     

Thermodynamics of the conversion of aqueous glucose to fructose

The thermodynamics of the conversion of aqueous glucose to fructose has been investigated using both heat conduction microcalorimetry and high pressure liquid chromatography (HPLC). The reaction was carried out in both aqueous Tris/HCl buffer and in aqueous phosphate buffer in the pH range 7–8 using the enzyme glucose isomerase and the cofactors CoCl₂ and MgSO₄. The temperature range over which this reaction was investigated was 298.15–358.15 K. We have found that the enthalpy of reaction is independent of pH over the range investigated. A combined analysis of both the HPLC and microcalorimetric data leads to the following results at 298 15 K:ΔG° = 349 ± 53 J mol^-1, ΔH° = 2.78 ± 0.20 kJ mol^-1, and ΔC _p ^° = 76 ± 30 J mol^-1 K^-1. The stated uncertainties are based upon an analysis of both the random and systematic errors inherent in the measurements. Comparisons are made with literature data. The percent conversion of glucose to fructose has been calculated for the temperature range 300–373.15 K.     

ⅥB族金属叁键有机化合物的研究进展

本文对一类重要的ⅥB族金属叁键化合物R_2M_2(CO)_4(R为环戊二烯基及类环戊二烯基)近年来的研究成果进行了综述,综述重点是这类化合物的官能团M≡M参键的化学活性,全文包括R_2M_2(CO)_4的合成及结构,M≡M叁键与亲核试剂、与碳-碳重键,与氧或与金属羰基物等试剂的反应及其应用。     

Darstellung und Strukturen einiger N-(Tri-t-butoxysilyl)anilin-Derivate

Formation and Structures of N-(tri-t-butoxysilyl)aniline Compounds Para-substituted N-(tri-t-butoxysilyl)anilines (t-BuO)₃SiNRC₄H₄X-p, R = H, CH₃, with substituents of high electron affinity (X = CN, NO₂) were prepared by a one-pot reaction of tri-t-butoxychlorsilane, potassium t-butanolate and substituted anilines. Corresponding compounds with substituents of low electron affinity (X = OMe, H) preferably were prepared by metalation of anilines with sodium amide. Four crystal structures were determined. N-(tri-t-butoxysilyl)-p-nitro-aniline, N-methyl-(N-tri-t-butoxysilyl)-p-nitroaniline and N-(tri-t-butoxysilyl)-p-cyanoaniline crystallize at 298 K monoclinically, N-(tri-t-butoxysilyl)aniline crystallizes orthorhombically.     

锆对铂重整催化剂性能的影响规律

以正庚烷的转化为探针反应 ,研究了添加元素锆对铂重整催化剂性能的影响规律。结果表明 ,在 4 50℃和连续流动条件下 ,Pt/γ -Al2 O3催化剂中引入锆不仅能够提高铂催化剂的稳定性和芳构化产率、抑制氢解和异构化 ,而且能使铂催化剂保持初活性。锆含量在 0 .56%左右 ,其调变作用最为显著。     

SNAr reactions of β-substituted porphyrins and the synthesis of meso substituted tetrabenzoporphyrins

Reaction of 2,3,7,8,12,13,17,18-octaethylporphyrin with LiR reagents containing functional groups readily yields meso substituted derivatives suitable for further transformations with residues such as -p-C₆H₅Br, -p-C₆H₅-CCH, -p-C₆H₅-NH₂ or -(CH₂)₃-CHCH₂. Similar reactions of tetrabenzoporphyrin with alkyllithium reagents afforded the first entry into meso mono- and dialkylsubstituted tetrabenzoporphyrins while reaction of bicyclo[2.2.2]oct-type masked isoindole precursors with LiR followed by in situ retro-Diels-Alder reaction also afforded the 5-phenyl and 5,10-diphenyltetrabenzoporphyrins in high purity.