铜(Ⅱ)-羟肟络合物的电子自旋共振谱研究

本文报导芳香族羟肟铜(Ⅱ)络合物的电子自旋共振(ESR)谱的研究。讨论了这类配位体上取代基的电子效应对络合物中铜(Ⅱ)的超精细分裂常数A_(Cu)值的影响,以及A_(Cu)值与这些配位体萃取铜的分配系数的关系。     

Synthesis and Structures of the Novel Pyridoxal Oxime Derivatives

Novel pyridoxal oxime derivatives were prepared and characterized by means of IR, ¹H and ¹³C NMR spectroscopy. The crystal structures of the 3-hydroxy-4-hydroxyiminomethyl-5-hydroxymethyl-1,2-dimethylpyridinium iodide 1 and 3-hydroxy-4-hydroxyiminomethyl-5-hydroxymethyl-1,2-dimethylpyridinium chloride monohydrate 2 were determined by X-ray analysis. The both compounds crystallize in the triclinic crystal system, space group P . Crystal data: 1 a = 6.286(2) Å, b = 8.748(4) Å, c = 11.736(4) Å, = 104.02(3)°, = 94.70(3)°, = 107.44(6)°, V = 589.0(4) ų, Z = 2, R = 0.0526; 2 a = 6.8980(5) Å, b = 8.6409(6) Å, c = 11.1777(6) Å, = 111.138(5)°, = 93.114(6)°, = 105.158(5)°, V = 591.57(7) ų, Z = 2, R = 0.0492. The bond distances and angles in both structures agree very well. The main difference between these structures was observed in the orientation of the hydroxymethyl group with respect to the pyridinium ring. In the both structures intramolecular hydrogen bond forming six-membered ring were observed. The intermolecular OsI hydrogen bonds in the crystal structure of the compound 1 form dimers. In the crystal structure of compound 2, the water molecules and chlorines build eight-membered rings, which are also connected to pyridinium cations by OsCl and OsO intermolecular hydrogen bonds forming a three-dimensional network.     

加料方式及底物浓度对Ti-MWW催化剂上环己酮氨肟化反应的影响

 研究了加料方式和底物浓度对钛硅分子筛Ti-MWW催化环己酮液相氨肟化反应的影响. 结果表明,加料方式对 Ti-MWW 催化环己酮氨肟化过程有重要影响,过氧化氢的浓度对反应过程也有一定的影响. 在过氧化氢缓慢加入反应体系的情况下,环己酮转化率和环己酮肟选择性都高于99%, 而且该反应过程以水作溶剂,对环境友好.     

Facile synthesis of chiral 2-formyl-1,1′-binaphthyl via lipase-catalyzed acylation and hydrolysis of 1,1′-binaphthyl oximes

Lipase-catalyzed acylation of 2-hydroxyiminomethyl-1,1′-binaphthyl [(±)-1] and hydrolysis of 2-acetoxyiminomethyl-1,1′-binaphthyl [(±)-2] yielded optically active oximes 1 and 2 with high enantiomeric excess. Successful synthesis of the optically active aldehyde 4 from chiral O-acetyl oxime 2 occurred without a decrease of enantiomeric excess.     

环己酮肟在改性氧化锆催化剂上的Beckmann重排反应Ⅴ.活化焙烧温度对B2O3/ZrO2催化剂的影响

 采用BET，XRD，TG－DTA，FT－IR，XPS和NH3－TPD等分析手段，研究了活化焙烧温度（500～800℃）对B2O3／ZrO2催化剂织构／结构、表面性质和环己酮肟气相重排反应的影响．催化剂活化焙烧温度升高促进了ZrO2向单斜晶相转化，同时活性组分氧化硼由以BO4为主要结构单元的物种转变为以BO3为基本结构单元的B2O3，导致催化剂比表面积、孔体积以及表面酸量减小，ZrO2与B2O3之间的相互作用减弱．700℃活化焙烧的催化剂表面拥有最大比例的中强酸中心，而且Beckmann反应的活性稳定性最高．这些结果表明，活化焙烧温度对B2O3／ZrO2催化剂上气相重排反应的影响主要是通过改变催化剂中B原子的配位状态和表面酸性实现的．     

高效液相色谱手性固定相法分离取代环己酮及取代环己醇的对映体

在4种自制的涂敷型纤维素衍生物手性柱，即纤维素三苯甲酸酯(CTB)、纤维素三(4-甲基苯甲酸酯)(CTMB)、纤维素三苯基氨基甲酸酯(CTPC)和纤维素三(3，5-二甲基苯基氨基甲酸酯)(CDMPC)与小分子的Prikle型(S，S)-Whelk—O1手性柱上对取代环己酮及取代环己醇进行了对映体分离。研究了溶质的立体结构因素对手性分离的影响，并初步探讨、比较了溶质在这两种手性柱上的手性识别的机理。结果发现，在(S，S)-Whelk—O1柱上溶质与固定相之间的吸引作用是手性识别的主要原因，而对于纤维素衍生物手性柱，溶质的空间结构在手性空腔中的空间适应性可能是手性识别的关键。     

Some chemical reactions in the polydiphenylenesulfophthalide—aniline—cyclohexanone system

Two main reactions were observed in the polydiphenylenesulfophthalide—aniline—cyclohexanone ternary system by¹³C NMR and IR spectroscopy: (1) condensation of aniline and cyclohexanone to give the corresponding anil; (2) opening of the sulfophthalide ring in the polymer under the action of aniline. Both reactions also take place in the corresponding binary mixtures, and they should be taken into account in studies of the color and paramagnetic centers in this ternary system. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 546–547, March, 1998.     

一种1,10菲啰啉-5,6-二酮及其单肟的高效合成方法

1,10菲啰啉5,6二酮(2)与1,10菲啰啉5,6二酮单肟(3)作为稠杂环共轭配体,既具有良好的配位特性,又是重要的有机合成反应中间体。由化合物2和它的衍生物与金属离子形成的配合物可以用于抗肿瘤药物、DNA探针、非线性光学材料、超分子组装分子骨架、自旋交叉配合物等许多领域。化合物3则用于有机光致变色化合物螺噁嗪的合成。化合物2无法直接用氧化剂氧化1,10菲啰啉(1)得到。它最初是从化合物1用混酸硝化制备5硝基1,10菲啰啉的废水中分离得到的,产率1%。Amouyal等[1]改进此方法,将产率提高到20%。随着应用研究的需求,对它的合成研究一直没有间…     

Electrosynthesis of adipic acid by undivided cell electrolysis

A preparative method for synthesis of adipic acid in 47% yield was developed. The method is based on cyclohexanol oxidation in an undivided cell on the NiOOH electrode in aqueous alkali. A possibility of the step-by-step process was studied: oxidation of cyclohexanol to cyclohexanone (75% yield) and subsequent oxidation of cyclohexanone to adipic acid (52% yield). The electrosynthesis of adipic acid is accompanied by the formation of minor amounts (up to 10%) of glutaric and succinic acids.     

Carbon-carbon bond construction on solid support: triethylborane-induced radical reactions of oxime ethers

The triethylborane-induced solid-phase radical reaction was studied. The solid-phase radical reaction of oxime ether anchored to Wang resin proceeded smoothly to give the α-amino acid derivatives. The carbon-carbon bond-forming radical reaction of TentaGel OH resin-bound glyoxylic oxime ether proceeded even in aqueous media.