核磁共振碳谱的研究:烷烃化学位移和CSS与分子距边矢量λ

系统研究了核磁共振碳谱及其化学位移规律性.提出了一种新的分子图论参数:分子距离一边数矢量(λ或MDE矢量),并发现它与烷烃的¹³C NMR有良好的相关性。     

Selective Functional Transformation of 1,2-Diols Via Organophosphorus Reagents

A new synthesis of 1,3,2λ⁵-dioxaphospholanes was realized by direct reaction of dibromotriphenylphosphorane with 1,2-diols. Ring opening studies were performed with or without electrophilic activation (Lewis acids or hydrogen bonding) in order to substitute selectively one of the hydroxy function.     

Mono and Bisphosphonates from Perfluoro Olefins and Polyfunctional Fluoro Ketones. Syntheses,Molecular Structure and Derivatives

Perfluoroalkenyl phosphonates were formed along with Me₃SiF using CF₃CF=CF₂, CF₃CH=CF₂, F₅SCF=CF₂ or F₅SCH=CF₂ and silylated phosphites, (R¹O)₂POSiMe₃ (R¹=Et, SiMe₃). This straightforward method could be extended to perfluorobutadienes CF₂=C(R^F)C(R^F)=CF₂ (R^F F=F, CF₃). The formation of CF₃C(=O)P(=O)(OSiMe₃)₂ and further reactions to yield bisphosphonates will be described. Acetylphosphonates, R²C(=O)P(=O)(OSiMe₃)₂ (R²=CH₃, CF₃) reacted with the ketimine, CH₃C(=NiPr)Ph to give α-hydroxy-γ-imino phosphonates. Trifluoroacetylphenol and 2,6-bis(trifluoracetyl)-4-methyl-phenol have been proven to be versatile precursors for α-and γ-hydroxy phosphonates. Intermediates in these reactions were found to be cyclic λ⁵σ⁵P species.     

Synthesis and Study of the Thermal Epimerization of r -2-Ethoxy- cis -4- cis -5-Dimethyl-1,3,2-λ 3 -Dioxaphospholane Using 31 P NMR

The exclusive synthesis of r -2-ethoxy- cis -4- cis -5-dimethyl-1,3,2- u 3 -dioxaphospholane ( cis - 1 ) is reported. The kinetic measurements of the epimerization of cis - 1 to trans - 1 were performed by 31 P NMR from 50 to 80;C in toluene. The energy of activation (E a ) of the epimerization process was calculated from Arrhenius plot. The thermodynamic parameters of the transition state led us to conclude that the activation barrier of the inversion at phosphorus is driven by the enthalpy and by a large and negative entropy of activation.     

λ-Shaped azomesogens with polar chloro- and nitro-substituents

A new homologous series of λ-shaped mesogenic azo esters with polar chloro- and nitro- substituents has been synthesised by attaching a rigid 2-chloro-4-nitrophenylazo group to a resorcinol moiety by a central azo linkage. Both phenolic hydroxyl groups are esterified by 4-n-alkoxybenzoyl groups. All the compounds synthesised have been characterised using a combination of elemental analysis and standard spectroscopic methods. The mesomorphic properties of the compounds have been determined by polarising optical microscopy and differential scanning calorimetry. The lower members of the series are non-mesogenic, the middle members exhibit a nematic mesophase, and higher members exhibit a smectic A mesophase. The effect of polar chloro-, nitro-, and long lateral aromatic substituents, on mesomorphism is discussed.     

Radial Operators on the Weighted Bergman Spaces over the Polydisk

In this paper, we study radial operators in Toeplitz algebra on the weighted Bergman spaces over the polydisk by the(m, λ)-Berezin transform and find that a radial operator can be approximated in norm by Toeplitz operators without any conditions. We prove that the compactness of a radial operator is equivalent to the property of vanishing of its(0, λ)-Berezin transform on the boundary. In addition, we show that an operator S is radial if and only if its(m, λ)-Berezin transform is a separately radial function.     

A-调和方程弱解的新的加权积分不等式

研究形如div A(x,u(x))=0的A-调和方程,证明其弱解满足局部Arλ3(λ1,λ2,Ω)-权Caccioppoli型不等式,这可看作A-调和方程相应结果的推广.最后给出上述结果在拟正则映射中的应用.     

用基础解系解某些条件极值问题

通过对线性的目标函数在线性的约束条件下的极值问题的分析,得到这类极值问题一般是不能用拉格朗日乘数法求解.通过用基础解系的方法进行求解这类问题,实例表明,这种方法是可行有效的.     

Modulating the propeller-like shape of a tripodal C(CH2PPh2)3 fragment by the size of the substituent at the pivotal carbon atom in macrobicyclic tri-λ-phosphazenes

The chiral macrobicyclic tri-λ⁵-phosphazenes formed by tripod-tripod coupling of tris(3-azidobenzyl)amines and 1,1,1-tris[(diphenylphosphino)methyl]methanes present helical topologies as a result of combining two propeller-shaped tripodal fragments with the same sense of twist. The introduction of a series of R_piv substituents of increasing size at the pivotal carbon of the lower tert-butane fragment R_piv-C(CH₂PPh₂)₃ causes a gradual decrease of the helicity in the lower propeller. This phenomenon is revealed in their CDCl₃ solution NMR spectra, and the activation energies for the racemization process of the tri-λ⁵-phosphazenes were calculated by coalescence VT-NMR experiments.