新型手性α,α-二烃基-5-氧代-2-吡咯烷甲醇的合成

以L-谷氨酸为手性原料,经过环化、酯化和格氏加成反应合成了6个未见文献报道的手性α,α-二烃基-5-氧代-2-吡咯烷甲醇,其结构经比旋光度,1H NMR,IR和元素分析表征.     

取代吲哚-3-甲酸类化合物的合成

吲哚-3-甲酸是一种重要的有机中间体,被广泛应用于医药与农药的合成.以取代邻硝基甲苯为原料,与N,N-二甲基甲酰胺二甲基缩醛(DMFDMA)反应制得取代2-硝基-β-二甲氨基苯乙烯,再经铁粉和冰乙酸还原环合生成取代吲哚,取代吲哚与三氟乙酸酐经酰化、碱性条件下水解制得5种取代吲哚-3-甲酸类化合物,该合成方法操作简单,条件温和,收率较高.     

新型5-取代吲哚-3-甲酰胺化合物的合成

以5-取代吲哚为原料,经维尔斯迈尔-哈克反应制得5-取代吲哚-3-甲醛(2a~2e); 2a~2e在DMF催化下,与盐酸羟胺反应制得5-取代吲哚-3-甲腈（3a~3e）; 3a~3e在H₂O₂和NaOH溶液中水解合成了5-取代吲哚-3-甲酰胺（4a~4e, 4b~4e为新化合物）,产率62.0%~75.0%,其结构经¹H NMR, ¹³C NMR和ESI-MS表征。     

N-取代-α-氧代环十二烷基磺酰胶的合成及其杀菌活性

以易得的环十二酮为原料，由磺化获得中间体α-氧代环十二烷基磺酸后，再经生成磺酰、氯和胺化反应合成了一系列N-取代-α-氧代环十二烷基磺酰胺（Ⅲ）．生物活性测定结果表明，它们对小麦赤霉病菌（Gibberellazeae）的生长具有抑制作用，其中活性最高的是氮上取代有一氯苯基的化合物（Ⅲ7、Ⅲ8），通过构象分析讨论了它们的结构-活性关系．     

N-咔唑-二硫代甲酸-4-苯乙烯基甲酯的合成、晶体结构及热稳定性

近年来,可逆加成-断裂链转移聚合(Reversible addition-fragmentation chain transfer polymerization) :RAFT聚合这一活性/可控自由基聚合方式成为高分子化学研究的热点之一[1-2],并被应用于纳米材料[3]、生物医药[4]等领域.研究RAFT聚合的首要问题是合成高活性的RAFT试剂,最常用的RAFT试剂是具有二硫代酯结构的化合物[Z-C(S)-S-R].     

取代苯甲酰胺基硫代甲酸-(5-取代苯基-2-呋喃)-甲酯的合成及杀菌活性

为了发现高效、低毒的农药先导化合物,以真菌几丁质为研究对象,以取代苯甲酸、5-取代苯基-2-呋喃甲醇为起始原料,设计合成了23个新型取代苯甲酰胺基硫代甲酸-(5-取代苯基-2-呋喃)-甲酯,其结构经IR,1H NMR和元素分析确证.初步生测结果表明,在50 μg/mL浓度下,化合物对黄瓜褐斑菌、黄瓜灰霉菌、黄瓜枯萎菌表现出明显的防效,尤其对于黄瓜灰霉菌,大部分化合物的防效优于对照药剂40％菌核净WP.     

3-哌啶甲酸及其衍生物的合成与应用研究进展

3-哌啶甲酸及其衍生物是重要的药物中间体, 具有很高的生物活性. 综述了3-哌啶甲酸及其羧基酯化、不饱和、不同位置取代与多取代衍生物的合成方法, 并对3-哌啶甲酸及其衍生物在合成γ-氨基丁酸(GABA)摄入抑制剂、抗肿瘤药、生长激素促分泌素、消炎药物、心血管药物、促智药物、抗流感病毒、骨疾病等药物中的应用进行了概述.     

微波辐射下5-取代-2-硫代海因衍生物的合成

微波辐射下, 由硫氰酸铵与α-氨基酸通过两步反应合成了11种5-取代-2-硫代海因衍生物, 并用¹H NMR, IR和元素分析确证了中间产物和终产物的结构. 对比常规加热方法, 微波辐射具有反应时间短(4 min), 每步反应产率高(85%～93%)的优点. 同时对合成化合物2h的反应历程进行了讨论.     

一种新的合成12-氧代-1,15-十五内酰胺的方法

设计了一种新的合成12-氧代-1,15-十五内酰胺(4)的方法, 即以α-硝基环十二酮(1)为原料, 经与丙烯腈的Michael加成, 氰基选择性还原为氨基后扩环, 再经Nef反应合成了4, 总收率为28%.     

多取代2-吡喃酮-3-甲酸的合成与表征

吡喃酮类衍生物是一类具有生物活性的六元杂环化合物,同时,许多吡喃酮类化合物还是重要的有机合成中间体,广泛应用到医药,农药的合成中。本论文以氢氧化钠为碱,2-二乙硫基亚甲基乙酰乙酰苯胺和丙二腈合成了一系列新型多取代2-吡喃酮-3-甲酸,通过核磁共振、质谱分析对所得化合物的结构进行表征,并对该反应合成机理进行了探讨。该合成方法条件温和、操作安全、收率高。     

4-氧代-3（4H）-喹唑啉-5-羧酸的合成

以2-氨基-6-甲基苯甲酸为起始原料,通过合环反应生成两种4-氧代-3(4H)-喹唑啉-5-羧酸衍生物(1a, 1b), 1a, 1b分别经高锰酸钾氧化合成了4-氧代-3(4H)-喹唑啉-5-羧酸（2a, 2b）,其结构经¹H NMR, ¹³C NMR和MS表征。研究了投料比｛r［n(高锰酸钾) :n(5-甲基-3(4H)-喹唑啉-4-酮)］｝和反应温度等对收率的影响。结果表明：在最佳反应条件（r=7:1,中性高锰酸钾氧化,于90 ℃反应）下合成2总收率可达66%。     

5-卤代-1H-1,2,4-三氮唑-3-羧酸乙酯及其衍生物的合成

以5-氨基-1H1,2,4-三氮唑-3-羧酸乙酯为原料,经Sandmeyer反应合成了5-X-1H-1,2,4-三氮唑-3-羧酸乙酯(X=C1,Br,I)(1a-1c),1a-1c再分别与α-2′,4′-二氟苯乙酮反应合成了3个5-卤代-1-1H-1,2,4-三氮唑-3-羧酸乙酯衍生物(2a-2c),其结构通过元素分析,IR,UV和^1H NMR进行了表征。     

Enantioselective,Decarboxylative (3+2)-Cycloaddition of Azomethine Ylides and Chromone-3-Carboxylic Acids

Herein, we describe the synthesis of a variety of chiral hybrid pyrrolidine-chromanone polycyclic derivatives. A convenient (3+2)-annulation of azomethine ylides with chromone-3-carboxylic acid realized under Brønsted base catalysis produced highly functionalized products in high yields with good stereoselectivities through asymmetric, intermolecular, and decarboxylative (3+2)-cyclization.     

Zur Reaktivität 4,5-ungesättigter 3-Oxoalkannitrile gegenüberMichael-Acceptoren

The 3-oxonitrile1 as well as the 2-benzylidene-3-oxonitrile4 on reaction with benzylidenemalononitrile or malononitrile, respectively, afford 2-amino-4H-pyran derivative3 in high yield. In contrast, reactions of1 and4 with ethyl benzylidenecyanoacetate (6) or ethylcyanoacetate, respectively, predominantly lead to a carbocyclic compound, which is also obtained as main product on attempted condensation of1 with benzaldehyde. Based on spectroscopic data, structure5 is proposed for the novel compound; its formation is interpreted in terms of piperidine-catalysed addition of1 to4 and subsequent intramolecularMichael addition. Reaction mechanisms for the conversion of1 and6 or4 and ethylcyanoacetate to5 are discussed.

Herrn Univ. Prof. Dr. Dr. h c.K. Kratzl zum 70. Geburtstag gewidmet.     

Doubly Decarboxylative Synthesis of 4-(Pyridylmethyl)chroman-2-ones and 2-(Pyridylmethyl)chroman-4-ones under Mild Reaction Conditions

The doubly decarboxylative Michael–type addition of pyridylacetic acid to chromone-3-carboxylic acids or coumarin-3-carboxylic acids has been developed. This protocol has been realized under Brønsted base catalysis, providing biologically interesting 4-(pyridylmethyl)chroman-2-ones and 2-(pyridylmethyl)chroman-4-ones in good or very good yields. The decarboxylative reaction pathway has been confirmed by mechanistic studies. Moreover, attempts to develop an enantioselective variant of the cascade are also described.     

Synthesis and Crystal Structure of a One-dimensional Infinite Chain Organotin Complex [(n-Bu)_3Sn(OCOC_5H_4NO)]_n

1 INTRODUCTION Organotin esters of carboxylic acid are widely used as biocides and fungicides and as homogeneous cata- lysts in industry[1~3]. In recent years, the pharmaceu- tical properties of carboxylic acid have been investi- gated for the antitumour activity[4~6]. In general, bio- cidcal activities of organotin complexes are greatly influenced by the molecular structures and coordina- tion numbers of the tin atom[7, 8]. It is revealed that organotin complexes containing carboxylate l…     

Pulse Voltammetric Determination of Thiazolidine-4-Carboxylic Acids

Abstract

The electrochemical behaviour of thiazolidine-4-carboxylic acid (thioproline, Thz) and its derivatives 2-propyl-thiazolidine-4-carboxylic acid (PrThz) and 2-tetrahydroxybutyl-thiazolidine-4-carboxylic acid (AThz) has been studied by cyclic, normal and reverse pulse, differential pulse and Osteryoung square wave voltam-metrics. Anodic waves, resulting from the formation of adsorbed mercury thiazolidates, were obtained for all the compounds at mercury electrodes in acetate and phosphate buffers at pH from 3.8 to 8. the initially formed mercury compounds rapidly transform into the final products accumulating on the electrode surface. the oxidation products inhibit the anodic processes and distorted voltammetric curves were obtained at the covered electrodes. Various effects of these processes in various pulse voltammetric techniques were evident. Normal pulse voltammograms were least affected by the product transformations. Osteryoung square wave voltammetry permitted very fast determinations of Thz derivatives.     

一维链状有机锡配合物[Ph3Sn(OCOC5H4NO)]n的合成和晶体结构

有要锡配合物因基具有很强的生物活性以及多变的结构而日益受到人们的关注[1～4].有关该化合物的结构研究表明,中心锡原子的配位形式决定于直接与锡原子相连接的烃基的结构和羧酸基配体的类型[5～7].为了进一步探索有机锡羧配合物的结构类型、羧酸配体中带额外孤电子对的杂原子与锡原子的作用方式,本文合成了一个有机锡羧酸配合物[Ph3Sn(OCOC5H4NO)]n,并用X-射线衍射单晶结构分析方法测定了它的晶体结构.     

Aqueous Synthesis of N-Phenyl/alkyl-2-quinolinone-3-carboxylic Acids from Coumarin-3-carboxylic Acids

An efficient, ecofriendly aqueous synthesis of aromatic/aliphatic amines with coumarin-3-carboxylic acid in a one pot reaction in a sealed tube or InCl₃/ H₂O in open vessel to afford N-phenyl/alkyl-2-quinolinones is achieved. This method provides high yield of products in shorter time, making it a useful process for the synthesis of structurally diversified 2-quinolinones from corresponding coumarins.