微波辅助下N-酰胺基-2-(4-氧代-4H-色烯-3-基)噻唑-4-酮类衍生物的平行合成及其杀虫活性

利用微波辅助组合平行合成技术, 色酮酰腙类衍生物与巯基乙酸发生缩合反应, 成功地构建了N-酰胺基-2-(4-氧代-4H-色烯-3-基)噻唑-4-酮类化合物库. 与常规加热方法相比较, 反应时间由原来的8 h缩短至9 min, 且收率大大提高. 同时, 在250 μg/mL下, 检测了其杀虫活性, 初步生物测试结果表明部分化合物对红蜘蛛显示出良好的杀虫活性.     

微波辅助合成5-亚甲基-2,3-二苯基-4-噻唑酮类衍生物

本文报道了一种通过微波辅助合成5-亚甲基-2,3-二苯基-4-噻唑酮类衍生物的新型方法。在以K2CO3 为碱、H2O 为溶剂、四丁基溴化铵（TBAB）为催化剂的条件下,2,3-二苯基-4-噻唑酮与取代醛在微波辅助下发生Knoevenagel 反应,生成5-亚甲基-2,3-二苯基-4-噻唑酮类衍生物,产率最高可达85%。     

新型含亲水基的噻唑烷-4-酮衍生物的合成及HIV逆转录酶抑制活性

在微波辐射条件下合成了系列C-2或N-3位含酯基的噻唑烷-4-酮衍生物,经水解或还原得到含亲水基如羧基、羟基的衍生物.化合物通过艾滋病毒逆转酶(HIV-RT)试剂盒(比色法)评价了其酶抑制活性.活性结果表明,部分化合物如8a,8b,9a,9b和14c能有效地抑制HIV逆转酶的活性.其中在N-3嘧啶环5位连有乙基的化合物8a和9a的活性最高,IC50值分别为3.02和3.06μmol·L-1.构效关系表明亲水性基团的引入对HIV逆转录酶抑制活性影响不大,而N-3位嘧啶基更有利于噻唑烷-4-酮抗HIV活性.     

苯乙烯基-β-萘噻唑染料的微波促进合成

在微波促进下,由2-甲基-β-萘噻唑和取代芳香醛在碱性条件下合成了一系列苯乙烯基-β-萘噻唑染料,该法操作简便,收率高.产物的结构经元素分析,1HMR,MS,IR,UV-vis确证.     

微波法合成2-羟乙基苯并[d]异噻唑-3(2H)-酮

以苯并异噻唑-3(2H)-酮(BIT)及氯乙醇为原料微波法合成了2-羟乙基苯并[d]异噻唑-3(2H)酮。考察了氢氧化钠量,氯乙醇用量,反应时间,反应温度对反应的影响,经正交实验设计得到了最佳反应条件,最佳反应条件下收率为83.3%。结果表明,与传统工艺相比,微波技术合成2-羟乙基苯并[d]异噻唑-3(2H)-酮的方法具有操作方便、收率高等特点,具有一定的应用价值。     

微波辐射下合成5-芳亚甲基-2,3-二芳基-4-噻唑啉酮类化合物

在水介质中,以四丁基溴化铵(TBAB)作催化剂,微波辐射下使芳醛与4-噻唑啉酮反应合成一系列5-芳亚甲基-2,3-二芳基-4-噻唑啉酮类化合物.该反应具有反应时间短、产率高、环境友好、后处理简便等优点.所有化合物均经IR,MS,1H NMR和元素分析确定.同时用X射线衍射法测定了化合物4a的晶体结构.     

新型N-3位酰胺连噻唑烷-4-酮二芳基衍生物的设计合成及HIV逆转酶抑制活性

以氨基酸酯为原料,在微波辐射条件下合成了系列N-3位含酯基的噻唑烷-4-酮衍生物,经水解并酰胺缩合制备了N-3位酰胺键连接嘧啶胺的二芳基噻唑烷-4-酮衍生物.化合物通过人类免疫缺陷病毒(HIV)逆转酶(RT)试剂盒(比色法)评价了其酶抑制活性.活性结果表明,部分化合物如5bb,5bc,5cb和5cc能有效地抑制HIV逆转酶的活性,IC_(50)值分别为4.15,3.53,4.61和4.06μmol/L.构效关系表明N-3位2个碳的柔性侧链以及亲脂基如甲基的引入将有利于化合物的抗HIV逆转录酶活性.     

4-(4-{5-[(二苄胺基甲酰)-甲基]-2-庚基-4-羰基-噻唑-3}-丁基)苯甲酸的合成研究

报道一个新型胰岛素增敏剂4-(4-{5-[(二苄胺基甲酰)-甲基]-2-庚基-4-羰基-噻唑-3}-丁基)苯甲酸的合成方法. 该化合物以对碘苯甲酸为原料, 经过羧基的保护、Heck反应、还原反应、Ing-Mnske反应、噻唑环合成、酰胺制备和羧酸保护基解除等一系列反应, 通过对反应条件的优化, 高产率合成4-(4-{5-[(二苄胺基甲酰)-甲基]-2-庚基-4-羰基-噻唑-3}-丁基)苯甲酸, 并对其中间体对碘苯甲酸叔丁酯的合成方法进行研究.     

钯催化的2-苯氧基吡啶导向的脱羧酯基化反应研究

发展了一种高效的通过钯催化导向碳-氢键活化的策略在苯环上引入酯基官能团的方法.草酸单乙酯钾盐在过硫酸钾和碳酸银的协同作用下脱羧生成酯基自由基,然后酯基自由基加成到钯环上,最后经过还原消除的过程实现了2-苯氧基吡啶苯环的邻位酯基化.该反应为合成一系列水杨酸乙酯衍生物提供了一种切实有效的途径.     

联吡啶还原合成吡啶基四氢吡啶和吡啶基六氢吡啶

吡啶基四氢吡啶衍生物(Ⅰ)和吡啶基六氢吡啶衍生物(Ⅱ)是α受体和HT1A受体类似物的结构组成部分,应用在药物合成中[1].Ⅰ和Ⅱ可通过环化反应、烷基化反应或联吡啶还原合成[2].环化反应或烷基化反应路线较长,且易形成含不饱和哌啶基吡啶的混合物,需要进一步的还原或纯化[2a];用Ni合金还原联吡啶只能直接合成吡啶基六氢吡啶,且反应时间长,收率低[2d];N-氧化联吡啶还原合成吡啶基六氢吡啶收率低,不适用于大量合成[2e].     

Amination of quinolones with morpholine derivatives

The aromatic nucleophilic substitution reaction of 7-chloroquinolone carboxylic acid and its ethyl ester with cyclic amines under microwave irradiation conditions was investigated. ¹H NMR spectroscopy was used to monitor the progress of the substitution reaction. The reaction proceeded in high yield with simple cyclic amines and was less efficient for sterically more demanding bimorpholine derivatives. A Pd-catalyzed amination of quinolone carboxylic acid ethyl ester with bimorpholine derivatives provided new C-7 bimorpholino-substituted quinolone derivatives.     

Microwave‐Assisted Solid‐Phase Synthesis of a 1,2‐Disubstituted Benzimidazole Library by Using a Phosphonium Linker

An efficient and rapid microwave‐assisted solid‐phase method for the synthesis of 5‐methyl‐1,2‐disubstituted benzimidazoles derivatives has been developed. The phosphonium linker, obtained by reaction between polymer‐supported triphenylphosphine and 4‐fluoro‐3‐nitrobenzyl iodide, underwent aromatic substitution with primary amines, followed by one‐pot reaction with aldehydes in the presence of SnCl₂·2H₂O, yielded the benzimidazole system under microwave irradiation. The final products were released from the resin with NaOH under microwave irradiation and were obtained in high purity and good overall yield.     

微波促进立体选择性合成烯丙酸酯类高碳糖衍生物

在微波促进下, 利用酮糖(1)及糖酸内酯(4)与叶立德(2, Ph₃PCHCOOEt)的Wittig反应, 立体选择性地合成了糖基烯丙酸酯类化合物(3和5), 反应效率显著提高, 反应时间由原来的20 h缩短为10 min; 并且研究了不同反应溶剂对反应立体选择性的影响. 提供了一种高效、 简便合成含有烯丙酸酯类高碳糖衍生物的方法.     

A Facile Synthesis of Ethyl 2,4-Dimethoxy-6-perfluoroalkyl-benzoates via Acyclic Precursors

Introduction Polysubstituted arenes are important intermediates in synthetic medicines and dyestuffs, and the fluorinated analogues are more attractive as a result of their lipo-philicity and the increment of activity.1,2 Therefore, to study the convenient and efficient synthesis of polysub-stituted arenes is valuable in organic synthetic method-ology. We have designed a simple synthesis of fluori-nated polysubstituted arenes through the intramolecular Wittig reaction of a new phosphorous ylid…     

微波辅助法合成Hantzsch酯

以芳香醛、乙酰丙酮及碳酸氢铵为原料,固载路易斯酸蒙脱土为催化剂,通过微波辅助法催化合成了5个Hantzsch酯类化合物,其结构经¹H NMR和IR确证。考察了催化剂、溶剂、温度、时间和氮源对产率的影响。结果表明：反应温度60 ℃,微波辐照时间10 min, n(芳香醛) :n(乙酰乙酸乙酯) :n(碳酸氢铵)=2.0:2.0:1.0,氯化镍固载蒙脱土为催化剂（10%）,产率高达97.8%。     

Efficient [bmIm]OH Catalyzed Diastereoselective Synthesis of Imidazopyridine via Microwave Activation in Aqueous Media

A novel, efficient, and diastereoselective synthesis of imidazopyridine with high atom economy under microwave activation and [bmIm]OH (1‐butyl‐3‐methylimidazolium hydroxide) promotion from readily available 2‐aminopyridine and phenyl acetylene ester has been developed in aqueous condition. The strategy involves acetylene activation by [bmIm]OH that allows facile heterocyclization via double hydroamination of 2‐aminopyridine with acetylene derivatives. The reaction rate increases enormously with microwave irradiation. The transformation proceeded smoothly and quantitatively. Furthermore [bmIm]OH was recycled and reused five times without any appreciable decrease in its reactivity and product yield.     

酸化蒙脱土/氯化锌催化叔丁醚和叔丁酯的合成

以酸化蒙脱土/氯化锌作为催化剂,二碳酸二叔丁酯与一系列酚、醇和羧酸类化合物在120 ℃封管条件下反应,合成了叔丁醚和叔丁酯类衍生物,方法简单,经济可靠,环境友好,后处理方便,收率为61%~75%,产物结构经¹H NMR,ESI-MS确证。 探讨了溶剂、温度、金属离子等因素对反应收率的影响,并提出了可能的反应机理。 为今后该类化合物的合成提供了一种新的方法。     

Polyimidines. IV. The synthesis and polymerization of 3,3-diphenyl-6-aminophthalide

The monomer 3,3-diphenyl-6-aminophthalide was synthesized in a 20% yield by the following sequence of reactions: nitration of phthalimide, hydrolysis and dehydration to 4-nitrophthalic anhydride, Friedel–Crafts reaction with benzene to 2-benzoyl-5-nitrobenzoic acid, cyclization with thionyl chloride to the pseudoacid chloride, Friedel–Crafts reaction with benzene, and, finally, reduction of the nitro group to the amino function with Adams catalyst. Although the five-substituted isomer is also possible, it was obtained in yields of only one-fifth to one-tenth of those for the 6-substituted isomer. The 3,3-diphenyl-6-aminophthalide underwent polymerization with difficulty to yield low-molecular-weight polyimidines (inherent viscosity up to 0.68 dl/g) in reasonable yields (32?88%). Because of the rigid character of the backbone and steric crowding, conditions for polymerization were rather severe: 1–2 days at 180–225°C in nitrobenzene or polyphosphoric acid or 350°C in a sealed tube. The addition of sand to the reactants in the sealed tubes caused an increase in yield and molecular weight. The polymers were subjected to thermogravimetric analysis in air and nitrogen. The temperatures at which a 10% weight loss occurred were as high as 440°C in air and 510°C in nitrogen. These stabilities were similar to those encountered for previously synthesized all-aromatic polyimidines.     

富马酸奈拉西坦的合成工艺改进

报道了一种合成富马酸奈拉西坦(7)的新工艺。以衣康酸二甲酯和苄胺为起始原料,经Michael加成和分子内环合反应制得1-苄基-5-氧代吡咯烷-3-羧酸甲酯(3); 3经NaBH₄还原得1-苄基-4-羟甲基-吡咯烷-2-酮(4); 4经甲磺酰化反应得1-苄基-5-氧代吡咯烷-3-羧酸甲磺酸酯(5); 5经氨解得奈拉西坦(6); 6与富马酸经成盐反应合成7,总收率78.4%,其结构经¹H NMR确证。     

Application of microwave method to the solid phase synthesis of pseudopeptides containing ester bond

A new procedure was developed for reducing the reaction time and improving the yield of esterification reaction in solid phase synthesis of pseudopeptides containing an ester bond by utilizing microwave irradiation. We selected a pseudodipeptide (Fmoc-LysΨ[COO]Leu-NH₂) and optimized the microwave-assisted esterification reaction in solid phase synthesis using Fmoc chemistry. For this, microwave-assisted esterification reactions with different reaction time, temperature, and solvents were performed using 1,3-diisopropylcarbodiimide (DIC) as the coupling reagent. We synthesized several pseudodipeptides containing an ester bond by using the optimized microwave irradiation method. The purity and yield of the pseudodipeptides synthesized in this way were better than those obtained without microwave irradiation. Furthermore, we applied this methodology for synthesizing pseudopeptides (6- and 12-mer) corresponding to the α helical peptide. The microwave-assisted esterification reaction afforded the target pseudopeptides with high yield (∼80%) and purity within 12 min, whereas the reaction without microwave irradiation afforded the target compound with poor yield (∼45%) and low purity.