LGK974的合成工艺研究

LGK974是一种高度特异性和有效的Porcupine抑制剂。设计了一条新的合成路线,以2-氨基-5-溴吡啶、2-氯-3-甲基吡啶、2-氨基吡嗪和2-甲基-6-氯吡啶为起始原料,采用汇聚法,经取代、Suzuki、酰胺化等10步反应合成了LGK974,总收率11.5%,其结构经^1H NMR、^13C NMR和MS(ESI-TOF)确证。     

芳香甲（乙）酯）铵盐的酰胺化与酰亚胺化

用热分析方法得出,由芳香酸甲酯或乙酯与4,4’-二氨基二苯甲烷制备的铵盐的酰胺化,酰亚胺化反应,较芳香酸的铵盐更易进行,反应温度和表观活化能均比四酸铵盐时低。由铵盐生成的聚酰亚胺具有很好的热氧化稳定性。     

金属卟啉配合物催化3β-取代的Δ~5甾体衍生物立体选择性环氧化及酰胺化反应研究

研究了 5 ,10 ,15 ,2 0 (2 ,6 二氯苯基 ) 卟啉锰及其钌配合物 [Mn(TDCPP)Cl,Ru(TDCPP)CO]这类非手性的催化剂催化3 β 取代的Δ5 甾体衍生物的非对映选择性环氧化及酰胺化反应 .     

苯胺和苯酚与环酐的酰胺化及酯化反应

研究了环酐与苯胺和苯酚的酰胺化及酯化反应, 优化了酰胺化及酯化反应条件. 结果表明, 环酐的分子结构直接影响反应结果, 当酸酐分子存在共轭结构时以N-芳基内酰胺为主要产物. 关键中间体及最终化合物的结构经核磁共振氢谱、 碳谱及红外光谱确证.     

Comparative Catalytic Activity of Group 9 [Cp*MIII] Complexes: Cobalt‐Catalyzed CH Amidation of Arenes with Dioxazolones as Amidating Reagents

A procedure for the [Cp*Co^III]‐catalyzed direct C? H amidation of arenes with dioxazolone has been developed. This reaction proceeds under straightforward and mild conditions with a broad range of substrates, including anilides. A comparative study on the catalytic activity of Group 9 [{Cp*MCl₂}₂] complexes revealed the unique efficiency of the cobalt catalyst.     

Microwave-Promoted Syntheses of Pyridine Carboxamides and tert-Carboximides from Novel 6-Acetylpyridine-2-carboxylic Acid

A novel 6-acetylpyridine-2-carboxylic acid (4) was obtained occasionally during the synthesis of asymmetric ethyl 6-acetylpyridine-2-carboxylate (3) from 2,6-dipiclinic acid (1). Compounds 3 and 4 could transform mutually under some specific conditions. Two reactions of distinctive types occurred when they reacted with the aromatic amines as precursors, due to different functional groups on the 2-position of pyridine in the molecules of 3 and 4: one was Schiff base condensation and the other was an amidation reaction. From the latter reaction, two series of new compounds, pyridine carboxamides (5a–d) and pyridine tert-carboximides (6a–h), resulted. The relevant reaction mechanism is discussed in detail.     

新型甘草次酸酰胺杂环衍生物的合成及其抗结核活性

以18β-甘草次酸为原料,经过多步酰胺化反应合成了14个含不同杂环的新型甘草次酸多酰胺衍生物(11a～11n),收率78.6%～92.3%,其结构经1H NMR,13C NMR和IR表征。其中11i和11n的初步抑菌活性测试结果表明,杂环酰胺基团对甘草次酸衍生物的抗结核活性具有明显的增效作用。     

基于C-H键活化的铜催化二苄胺氧化酰胺化反应

基于铜催化的C-H键活化构建了一类高效的二苄胺氧化酰基化生成N-苄基苯甲酰胺的反应. 该反应使用CuBr作为催化剂, 二乙酸碘苯作为氧化剂, 在温和条件下生成两种酰胺, 总产率最高可达92.0%. CuBr催化剂价廉易得, 催化活性高. 同时这也是首次使用二乙酸碘苯作为氧化剂, 通过二苄胺的直接氧化酰基化反应合成N-苄基苯甲酰胺.     

Reduction‐Triggered Transformation of Disulfide‐Containing Micelles at Chemically Tunable Rates

A dilemma exists between the circulation stability and cargo release/mass diffusion at desired sites when designing delivery nanocarriers and in vivo nanoreactors. Reported herein are disulfide‐crosslinked (DCL) micelles exhibiting reduction‐triggered switching of crosslinking modules and synchronized hydrophobic‐to‐hydrophilic transition. Tumor cell targeted DCL micelles undergo cytoplasmic milieu triggered disulfide cleavage and self‐immolative decaging reactions at chemically adjustable rates, generating primary amine moieties. Extensive amidation reactions with neighboring ester moieties then occur because of the high local concentration and suppression of the apparent amine pK_a value within the hydrophobic cores, thus leading to the transformation of crosslinking modules and formation of tracelessly crosslinked (TCL) micelles, with hydrophilic cores, inside live cells. We further integrate this design principle with theranostic nanocarriers for selective intracellular drug transport guided by enhanced magnetic resonance (MR) imaging performance.     

Preparation and characterization of benzoyl‐hydrazide‐derivatized poly(lactic acid) and γ‐cyclodextrin inclusion complex and its effect on the performance of poly(lactic acid)

A nucleating agent, benzyl‐hydrazide‐derivatized poly(lactic acid) (PLA) and γ‐cyclodextrin inclusion complex (PLA‐IC‐BH), was synthesized through a series of reactions. Poly(lactic acid) and γ‐cyclodextrin inclusion complex (PLA‐IC) was first obtained by ultrasonic co‐precipitation, which was then subjected to carboxylation, acylation, and amidation using benzoyl hydrazine and thionyl chloride. The composition and structure of PLA‐IC‐BH was confirmed by ¹H nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, and X‐ray diffraction. PLA/PLA‐IC‐BH composites were prepared by melt blending and a hot‐press forming process. Mechanical properties, thermal stabilities, and crystallization behaviors of PLA/PLA‐IC‐BH samples were investigated by thermogravimetric analysis, differential scanning calorimetry (DSC), polarized optical microscopy (POM), rheological analysis, and so on. Mechanical testing and thermogravimetric analysis showed that the tensile strengths, impact properties, and thermal stabilities of PLA/PLA‐IC‐BH composites were improved significantly compared to pure PLA and PLA/PLA‐IC. DSC results showed that crystallinity of PLA was increased from 5.17% to 38.93% after introduction of PLA‐IC‐BH. POM results showed that PLA‐IC‐BH acted as a nucleating agent for PLA and enhanced its crystallization rate. Rotational rheological behaviors of PLA/PLA‐IC‐BH demonstrated that incorporation of PLA‐IC‐BH increased the rigidity of the network structure of the PLA matrix. Compared to those of PLA, the maximum torque and apparent viscosity of PLA/PLA‐IC‐BH composites were increased by 55.56% and 25.59%, respectively. Copyright © 2017 John Wiley & Sons, Ltd.