有机磷化合物的研究 XVI. 磷化合物的长碳链烷基及烷氧基的P常数与基团连通性

在测定一系列具长碳链一元烷基磷(膦)酸pK~a值的基础上,求得十八个烷基及烷氧基的σ^p常数,并首次讨论与确定了σ^p值与基团连通性参数之间的关系,这些长碳链烷基及烷氧基σ^p值的求得有助于研究酸性磷(膦)酸酯萃取金属反应的结构-性能定量关系。     

有机磷化合物的研究XVII.烯丙基膦酸酯碳阴离子的烷基化反应

本文研究了烯丙基膦酸二乙酯碳阴离子与烷基碘及三甲基氯硅烷的反应.探讨了亲电试剂,溶剂和配合剂对反应区域选择性的影响.     

某些芳香族羟肟一过渡金属配合物的红外光谱

The preparation and infrared spectroscopic studies of coordination compounds of salicylaldoxime, 2-hydroxy-acetophenone oxime, 2-hydroxy-benzophenone oxime and 2-hydroxy-4-methoxy-benzophenone oxime with copper (II), nickel (II), cobalt (II) and iron (II) have been described. The frquency of the C=N stretching vibration is usually higher in the complex than that in the ligand. The higher the frequency of the C=N vibration is, the larger the stability constant of the complex will be, but there is no quantitative relationship. In the case of complexes of salicylaldoxime with Cu, Ni, Co and Fe, &CC=N values are correlated linearly with the ionization potentials of the central metal ions. The frequency of the OH stretching vibration is closely related to the geometric configuration of the complex. Thus aromatic hydroxyoximes form coordination compound with Co (II) and Fe (II) with cis configuration possessing six membered stronger hydrogen bonding ring. This is indicated in the infrared spectra by the complete absence of the absorption band due to the OH stretching vibration, or by the appearance of an extremely broad and flat band of very low intensity. However, Cu (II) or Ni (II) complex possesses trans configuration with five membered hydrogen-bonding bridge showing characteristic OH absorption band in the infrared region. The &COH of complex investigated is closely related to the polar nature of the substituents on the benzene ring. By examining the spectra of Cu-63 and Cu-65 complexes with 2-hydroxy-4(5)-substituted benzophenone oximes, the characteristic frequencies of M -- O and M -- N in the far infrared region were assigned for a series of aromatic hydroxyoxime-transition metal complexes.     

分子内氢键 Ⅰ.分子内氢键的PMO研究

脂肪族化合物的分子内氢键与分子间氢键无论在性质和强度上都没有明显的区别,而在共轭体系中的分子内氢键强度却可成倍地大于类似官能团间的分子间氢键,这为应用PMO方法来研究含杂交替烃体系中的分子内氢键提供了可能性.观察到如下规律:对于相同官能团的一系列化合物,分子内氢键的强度主要决定于给予原子上的电荷密度,电荷密度越大,内氢键越强;在非键分子轨道系数相同的情况下,共轭体系越大,内氢键越强.当分子中有脂并环取代基时不服从上述规律.这种脂并环取代基有时会增强内氢键的强度.     

有机磷化合物的研究 XXV: 溶剂性质对烯丙在膦酸酯碳阴离子和芳醛反应区域选择性的影响

本文研究烯丙基膦酸二乙酯碳阴离子和苯甲醛, 对甲基苯甲醛的反应, 考察了溶剂对反应区域选择性的影响.     

有机磷化合物的研究XIX.III亚磷酸二烷基酯钠的相转移催化P-烷基化反应

Sodium dialkyl phosphite reacts with non-activated alkyl halide in the presence of crown ether to give dialkyl alkyl phosphonate in moderate yield. Little or no reaction takes place in the absence of crown ether under the same conditions. In all cases, crown ether was present in catalytic amts. indicating that it behaves as a phase transfer catalyst between solid and liquid phases. The influences of structures of crown ethers, alkyl halides, dialkyl phosphites and the nature of solvent on the P-alkylation of sodium dialkyl phosphite have been investigated.     

一元烷基磷(膦)酸酯萃取钴,镍反应中取代基空间效应的经验参数

本文在考察一元烷基磷(膦)酸酯萃取钴、镍反应平衡常数与取代基结构的定量关系的基础上,提出了酸性磷(膦)酸酯萃取钴、镍反应中反映取代基结构空间效应为主的经验参数EPA[Co]和EPA[NI],这些新标度的建立,不仅使我们可用关系式来描述萃取钴、镍的反应性与取代基结构效应的关系,而且也为选择高效镍、钴分离萃取剂提供了新途径。     

重水在咪唑N-烷基化相转移催化反应中的影响

咪唑及其衍生物在相转移催化剂(PTC)存在下和烷基卤进行N-烷基化反应能得到较好的结果,但重水在此反应中的影响,至今未见文献记载.作者为进一步探讨在相转移催化剂存在下吡唑、咪唑及其衍生物N-烷基化反应机制,采用重水作为相转移反应体系的水相,观察其对反应的影响.     

Studies on organophosphorus compounds 104. Reaction of carbanions derived from alkylphosphonates

Structural effect of substituents directly bonded to carbanions bearing a phosphorate moiety is examined. Nucleophihc addition of phosphonate carbanion to 1-nitroalkene followed by subsequent reaction with chlorotrimethylsilane leads to a series of 2-isoxazoline based on the formation of an alkene and silyl nitronate as a 1,3-dipole. On the other hand, addition of carbanion derived from isocyanomethylphosphonate to nitroalkene with the formation of nitronate followed by intromolecular cyclization provides substituted phosphoryl pyrroles.