Convenient Synthesis of Chiral Cyclophanes that Can Coordinate to Metals
摘要:
Optically pure cyclophanes possessing a 1,3-dicarbonyl moiety were conveniently synthesized from alkanedioyl dichloride in four steps. The intramolecular [4+2]cycloaddition of bis(acylketene)s generated by thermal decomposition of bis(4,6-dioxo-1,3-dioxane) proceeded smoothly, giving cyclophane pyranones in high yields. The compounds possessing 7-10 bridging methylenes were resolved by imine formation with (R)-1-phenylethylamine, followed by basic hydrolysis. These cyclophanes are optically active versions of acetylacetone or salicylaldehyde and formed complexes with metals such as copper and europium. X-ray analysis of the chiral copper complex indicated the pentacoordinated structure of the copper metal with syn configuration of the two bridging chains.
[EN] POLYMERS AND POLYMERIC NANOGELS WITH HYDROPHILICS ENCAPSULATION AND RELEASE CAPABILITIES AND METHODS THEREOF<br/>[FR] POLYMÈRES ET NANOGELS POLYMÈRES À CAPACITÉS D'ENCAPSULATION ET DE LIBÉRATION D'AGENTS HYDROPHILES, ET PROCÉDÉS ASSOCIÉS
申请人:UNIV MASSACHUSETTS
公开号:WO2016044663A1
公开(公告)日:2016-03-24
The invention provides pH- or redox-responsive and charge-neutral polymeric nanogels that stably encapsulate a biomolecule at one pH or redox condition and then release it at a different pH or redox condition, and compositions and methods of preparation and use thereof
[EN] PHOSPHINYL AMIDINE COMPOUNDS, METAL COMPLEXES, CATALYST SYSTEMS, AND THEIR USE TO OLIGOMERIZE OR POLYMERIZE OLEFINS<br/>[FR] COMPOSÉS DE PHOSPHINYLAMIDINE, COMPLEXES DE MÉTAL, SYSTÈMES DE CATALYSEUR, ET LEUR UTILISATION POUR OLIGOMÉRISER OU POLYMÉRISER DES OLÉFINES
申请人:CHEVRON PHILLIPS CHEMICAL CO
公开号:WO2011082192A1
公开(公告)日:2011-07-07
N2-phosphinyl amidine compounds, N2-phosphinyl amidinates, N2-phosphinyl amidine metal salt complexes, N2-phosphinyl amidinate metal salt complexes are described. Methods for making N2-phosphinyl amidine compounds, N2-phosphinyl amidinates, N2-phosphinyl amidine metal salt complexes, and N2-phosphinyl amidinate metal salt complexes are also disclosed. Catalyst systems utilizing the N2-phosphinyl amidine metal salt complexes and N2-phosphinyl amidinate metal salt complexes are also disclosed along with the use of the N2-phosphinyl amidine compounds, N2-phosphinyl amidinates, N2-phosphinyl amidine metal salt complexes, and N2-phosphinyl amidinate metal salt complexes for the oligomerization and/or polymerization of olefins.
The achiral liquid crystalline materials showing two B4 (HN) phases have been found to exhibit strong gelation ability for various organic solvents with reversible sol–gel phase transition. The gel is formed by helical tubules, which build entangled 3D network, encapsulating the solvent. The equilibrium of left- and right-handed tubules is preserved in the gel, even if the chiral solvent is used.
Doubly Strapped Redox-Switchable 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoids: Promising Platforms for the Evaluation of Paratropic and Diatropic Ring-Current Effects
position of the methylene units; it decreased with increase in separation from the π-plane and central axis of the porphyrin ring. The NMR experiments also revealed that the degree of the diatropic ring currents was clearly related to the π-electron density of the porphyrin ring; the ring-current effects decreased as the charge increased from 0 to +2. These findings are also qualitatively supported by
本文提出了一系列新的化学稳定且可氧化还原转换的20π,19π和18π5,10,15,20-四芳基-5,15-二氮杂卟啉类化合物(TADAP),在二氮杂卟啉环的上方和下方都有两个烷基链带。三种类型的双重捆扎TADAPs的制备为使用镍(II)络合物内消旋- ñ - (2,6-二羟基苯基) -取代的TADAP和相应的脂族二酸作为前体。理论计算表明,无论其氧化态如何,所有捆绑的TADAP都具有基本平坦的π平面。发现烷基链带对DAP环的光学和电化学性质有轻微影响,特别是在氧化形式下。1个1 H NMR光谱用于评估20πTADAP的抗芳烃特性和18πTADAP指示剂的芳烃特性,并且观察到它们分别对亚甲基质子的化学位移表现出副热带和变径环电流效应。在空间上分开的烷基链。屏蔽和脱屏蔽的程度取决于亚甲基单元的位置。随着与卟啉环的π平面和中心轴的分离的增加,它降低。NMR实验还表明,变径环电流的程度与卟啉环的