Microstructure of polymers obtained by cationic polymerization of endo-dicyclopentadiene

endo-Dicyclopentadiene (DCPD) was polymerized by various cationic initiating systems in different solvents. IR and ¹H NMR results show that four types of structural units are formed due to the corresponding addition modes: the addition on the norbornenic (NB) double bond generates unit I and rearranged unit II, while the addition on the cyclopentenic (CP) double bond produces unit III and rearranged unit IV. The reaction medium has a stronger effect on the microstructure of the polymer (PDCPD) than initiating systems. The polymers prepared in toluene and n-hexane contain all four structural units, while the polymer produced in methylene chloride is composed of structural units II and IV. © 1996 John Wiley & Sons, Inc.     

Silicalite-1的后处理对其催化环己酮肟气相Beckmann重排反应性能的影响

 研究了silicalite-1分子筛的不同后处理方法对其催化环己酮肟Beckmann重排制己内酰胺性能的影响,这些方法包括水(或氨)蒸气处理以及在碱性、酸性或中性条件下用NH4NO3处理. 结合XRD,FT-IR和 29Si MAS NMR表征结果对silicalite-1催化剂的活性中心进行了探讨. 结果表明,碱性条件下用NH4NO3进行后处理对提高分子筛的催化性能最为有利. 分子筛上无规则排布的末端硅羟基数量的减少,以及具有相互氢键作用的邻式硅羟基的产生是其催化性能提升的主要原因.     

钴催化的高效贝克曼重排反应

利用廉价易得的氟硼酸钴水合物, 在温和、 无添加剂的空气条件下, 高效催化酮肟衍生物的贝克曼重排反应, 底物的普适性和官能团的兼容性均较理想, 产物收率最高达97%. 基于该高活性的氟硼酸钴水合物, 实现了10 g级二苯甲酮肟的贝克曼重排反应, 收率为71%. 同时, 也实现了钴催化酮类衍生物和盐酸羟胺的一步法贝克曼重排反应, 产物最高收率为94%, 反应体系中无溶剂及添加剂, 反应体系的原子经济性和底物普适性较好.     

A Diels-Alder reaction / oxa-Michael addition / acyloin rearrangement cascade on tropolonic substrates

We describe a novel pericyclic/anionic cascade reaction on tropolonic substrates that combines a Diels-Alder reaction, an oxa-Michael addition, and an acyloin rearrangement to afford tricyclic α-hydroxy-β-methoxyketones. Spectroscopic, crystallographic, and mechanistic studies indicate that the process requires stabilization of reaction intermediates through intramolecular H-bonding to take place, and suggest that the conjugate addition step involves a catalytic cycle with initial formation of an ammonium enolate and sustained by an alkoxide ion pair. Given the rich functionality and structural complexity generated in a single step, the process could be exploited in the preparation of natural product-like compound libraries.     

Stable meso‐Aryl β‐Alkyl Hybrid Sapphyrin with a Warped π‐Conjugation Circuit and Neo‐Confused Sapphyrin–Silver(I) Complex

A meso‐aryl and β‐alkyl substituted sapphyrin and its rhodium(I) and silver complexes were synthesized. This sapphyrin was so stable that the non‐inverted and warped structure could be analyzed by X‐ray crystallography even in its neutral state. Its bis‐rhodium(I) complex has a more planar structure than the sapphyrin with enhanced aromaticity over the conjugation circuit. On the other hand, silver metalation of the sapphyrin caused a marked core rearrangement into a neo‐confused sapphyrin derivative with a C(α)?N bond and a twisted macrocycle.     

An Infrared Spectroscopic Study on the Hofmann- and en-Td-type Clathrates: Mn(NH3)2Zn(CN)4 .2benzene and Mn(ethylenediamine)Zn(CN)4.2benzene

Infrared spectra of Mn(NH₃)₂Zn(CN)₄.2C₆H₆ andMn(ethylenediamine)Zn(CN)₄.2C₆H₆ are reported. The spectral data suggest that these compounds are similar in structure toHofmann-T_d-type and the en-T_d-type clathrates,respectively. There is good evidence for H-bonding from ammoniaN–H to benzene as a to H-bond.     

环己酮肟在B2O3/Al2O3-TiO2催化剂上的气相Beckmann重排反应

制备了B2O3/Al2O3-TiO2复合载体催化剂,并考察了其对环己酮肟气相Beckmann重排制己内酰胺反应的催化性能. 结果表明,载体中TiO2的含量、B2O3的负载量、载体的预处理温度及催化剂的焙烧温度等均对催化剂的性能产生明显的影响. 当载体中TiO2含量为60%,B2O3负载量为20%,催化剂经350 ℃焙烧时,环己酮肟的气相Beckmann重排反应的转化率和选择性很高. 用BET,NH3-TPD,XRD和IR等方法对催化剂的织构、表面酸性和晶相等进行了表征,并与催化剂的活性进行了关联,表明催化剂表面中等强度的酸中心浓度与催化剂的选择性具有对应关系.     

二氯亚甲基环己烷的卤化反应和2-取代二氯亚甲基环己烷的构象

多卤代烃在有机反应机理和结构研究中有着重要意义,作为一个有用的合成中间体,其制备也受到人们重视。我们在此报道二氯亚甲基环已烷(1)与氯及溴的反应和其它有关反应的实验结果。 1 于氯作用,主要得到加成产物1—氯—1—     

N,N′-双-(2-羟基苯亚甲基)-烷基(芳基)甲二胺类化合物质谱研究

本文对双Schiff碱类化合物的质谱进行了研究,由于其结构的特殊性,质谱的裂解过程中出现一些特殊的碎片离子,它包括羟基氢的迁移、双键的转换以及分子结构重排等,为研究这类化合物的结构和性质提供了重要的信息。