铜催化下格氏试剂与α,ω-二溴代烷的偶合反应

七十年代发展了铜催化下格氏试剂与卤代物、磺酸酯、酰卤的选择性交叉偶合反应,以后对这类反应并未深入研究。我们以几种铜     

铜催化下格氏试剂与酰卤的选择性偶合: 直链酮化合物的合成

在一般情况下,格氏试剂与酰卤偶合反应难以控制在酮阶段,往往得到叔醇。在较低温度下有机铜试剂与酰卤偶合可高产率地得到酮,所以用固体铜盐CuX(X=Cl、Br、I)作为格氏试剂与酰卤偶合的催化剂,可以提高反应的选择性,从而提高酮的产率。但固体铜盐的催化反应仅适合于空间位阻较大的脂肪酮和某些芳香酮的制备,对于直链脂肪酮的制备则产率很低。我们采用可溶性铜络合物Li_2Cucl_4(四氯合铜酸锂)等作催化剂,在均相溶液中反应,有效地提高了催化效果及反应的选择性,从而使格氏试剂与酰卤的偶合反应成功地用于直链脂肪酮的制备,产率良好。     

Synthesis of macrocycles via cobalt-mediated [2 + 2 + 2] cycloadditions

We investigated the formation of macrocycles from alpha,omega-diynes in cobalt-mediated co-cyclotrimerization reactions. Long-chain alpha,omega-diynes underwent metal-mediated [2 + 2 + 2] cycloadditions with nitriles, cyanamides, or isocyanates in the presence of CpCo(CO)2 (Cp = cyclopentadienide) to yield pyridine-containing macrocycles, i.e., meta- and para-pyridinophanes, such as 5m/5p, 35m/35p, and 41m/41p. The regioselectivity of these reactions was affected by the length and type of linker unit between the alkyne groups, as well as by certain stereoelectronic factors. An analogous alpha,omega-cyano-alkyne, 28, combined with an alkyne to yield two isomeric meta-pyridinophanes, such as 5m and 29m, and an ortho cycloadduct (benzannulation product), such as 29o. We developed a reaction protocol for these cobalt-based [2 + 2 + 2] cycloadditions that involves markedly improved conditions such that this process offers a convenient, flexible synthetic approach to macrocyclic pyridine-containing compounds. For example, diyne 6 reacted with p-tolunitrile in 1,4-dioxane to give 7p and 7m (7:1 ratio) in 87% yield at a moderate temperature of ca. 100 degrees C in 24 h without photoirradiation or syringe-pump addition. Isocyanates were also effective reactants, as exemplified by the formation of 44p almost exclusively (44p:44m > 50:1) in 64% yield from diyne 8 and 2-phenylethylisocyanate. By using this improved protocol we were able to co-cyclotrimerize long-chain alpha,omega-diynes with alkynes in certain cases to demonstrate a successful macrocyclic variant of the Vollhardt reaction. For instance, diyne 6 reacted with dipropylacetylene to give paracyclophane 57p and benzannulene 57o (2:1 ratio) in 29% yield.     

Silica-metalloporphyrins hybrid materials: preparation and catalysis to hydroxylate cyclohexane with molecular oxygen

Three types of novel silica-metalloporphyrins hybrid materials, Si-S-APTCPPFe, Si-S-APTCPPMn and Si-S-APTCPPCo, were prepared at room temperature by sol–gel method involving a thiol-ene polymerization reaction of 5-(4-allyloxy)phenyl-10,15,20-tri(4-chlorophenyl)porphyrin (APTCPP) with 3-mercaptopropyltrimethoxysilane (MPS). The hybrid materials were characterized by XRD, SEM, FT–IR, UV–Vis and TG, and were investigated as catalysts for the aerobic oxidation of cyclohexane. It is found that these hybrid materials are more efficient catalysts than the analogous non-supported metalloporphyrins for cyclohexane hydroxylation in metalloporphyrin–O₂–ascrobate system and the metal ion in the porphyrins significantly affected the catalytic efficiencies of these hybrid materials.     

Preparation of Lewis acid ionic liquids for one-pot synthesis of benzofuranol from pyrocatechol and 3-chloro-2-methylpropene

Several Lewis acid ionic liquids (LAILs) with different acidic scales were synthesised and used as catalysts for the synthesis of benzofuranol by condensation of pyrocatechol and 3-chloro-2-methylpropene in one pot. The catalytic activity of these ionic liquids was correlated with their Lewis acidity. Low to moderate conversion with excellent selectivity to benzofuranol was obtained in the presence of the appropriate LAILs. Compared to the two-step synthetic method currently used in industry, a higher yield plateau (81.1%) of benzofuranol was achieved in the presence of [BMIm][AlCl₄] IL as catalyst at 418 K after 4 h. Furthermore, the catalyst is readily separated from the resultant products via decantation and could be reused after treatment in vacuum.     

激子旋转弛豫对低掺杂卟啉侧链聚合物荧光衰变过程的影响

利用激子旋转扩散理论研究了一类低掺杂卟啉侧链聚合物中卟啉侧链基团的旋转对其发光动力学过程的影响.研究表明,卟啉侧链基团的旋转行为是导致激发态无辐射能量弛豫的重要途径.基团旋转越容易,能量弛豫速度越快,这可导致一个快速的荧光衰变动力学过程.在卟啉低掺杂浓度和聚合物分子链间距离较大的情况下,卟啉侧链基团的旋转成为影响荧光寿命和发光效率的主要因素.对实验测得的两种样品的荧光弛豫过程进行了拟合,理论结果与实验结果符合较好. 关键词： 激子旋转弛豫 瞬态荧光 卟啉侧链聚合物     

F(o)rster双分子猝灭作用对卟啉侧链聚合物荧光衰变的影响

通过采用时间分辨荧光光谱技术测量了一种卟啉侧链聚合物薄膜:卟啉丙烯酸酯-苯乙烯共聚物poly[porphyrin acrylate-styrene] (P[(por)A-S])在高激发密度下的瞬态荧光特性.实验发现,P[(por)A-S]样品的荧光衰减随聚合物分子浓度的增大而加快.利用Frster机制的双分子猝灭理论对其浓度猝灭的原因进行了分析,理论结果与实验结果符合较好.研究表明,在高激发密度的情况下,Frster机制的双分子作用是加快卟啉侧链聚合物初始荧光衰减和降低其发光效率的主要因素.     

Synthesis,characterization and visible-light photocatalytic activity of TiO2–SiO2 composite modified with zinc porphyrins

Three types of silica gel supported titanium dioxide particles immobilizing Zn(II) carboxylphenyl porphyrins appending p-CH₃, p-H and p-Cl phenyl substituents (designated as ZnMP–TiO₂–SiO₂, ZnPP–TiO₂–SiO₂ and ZnCP–TiO₂–SiO₂, respectively) have been synthesized and characterized using SEM, XRD, IR, AFS, DRS, UV–Vis, XPS and TG. The photodegradation of α-terpinene in aqueous suspension was used to determine the photocatalytic activity of TiO₂–SiO₂ samples which had been impregnated with Zn(II) porphyrins, as sensitizers. The experimental results confirmed that the photocatalytic activitys of these composites are much higher than those of the nonmodified TiO₂–SiO₂ under visible light irradiation and follow the order of ZnMP–TiO₂–SiO₂ > ZnPP–TiO₂–SiO₂ > ZnCP–TiO₂–SiO₂.     

60 A GeV?16 O诱发乳胶核反应慢粒子产生研究

对60AGeV^16O诱发乳胶核反应靶核碎片多重数分布及其关联进行了实验研究,并与FRITOF1．7加级联机制模型和DIUNUC2．0模型计算结果进行了比较／。     

Styrene-hydroxyethyl methacrylate copolymer-supported porphyrinatomanganese(III) complexes: synthesis and catalytic cyclohexane hydroxylation with molecular oxygen

Two new styrene-hydroxyethyl methacrylate copolymers containing immobilized porphyrinatomanganese(III) were prepared and characterized as microspheres by SEM, UV–Vis, FT-IR, and TG-DTG. Their catalytic activities have been investigated for the hydroxylation of cyclohexane in the presence of molecular oxygen under mild conditions. The copolymer microspheres proved to be more efficient catalysts than the corresponding non-supported porphyrinatomanganese(III) complex. The alkylated polymer microspheres with porphyrinatomanganese(III) had the highest catalytic activity, which may be attributable to the hydrophobic microenvironment around the porphyrinatomanganese(III) centers, resulting from the alkyl groups.