杂环酰胺类化合物合成研究进展

杂环酰胺类化合物是一类具有良好生物活性的化合物,因其作用机制新颖、环境友好在医药,农药等领域备受关注。目前该类化合物的分子设计及合成研究是农药创制的热点之一。本文对合成杂环酰胺类化合物的新方法进行了回顾和展望。     

含氟吡啶杂环酰胺类化合物的合成及生物活性

为了寻找具有生物活性的新化合物,以氟乙酸甲酯、氰乙酰胺和甲酸乙酯为起始原料,经环合、氯化、水解、酰氯化等反应合成了一系列含氟吡啶杂环酰胺类化合物,其结构均经1H NMR、13C NMR、IR和MS确证.初步生物活性测试结果表明,部分化合物对菌虫表现出一定的活性.化合物2f对孑孓(Culex piipiens)在50 mg/L时有100%的死亡率,在250 mg/L时对黄瓜白粉病菌(Sphaerotheca fuliginea)也有21%的抑制活性.     

氨基酸酰胺的制备

氨基酸酰胺是一类很重要的中间体和合成试剂。由它可以合成噻唑氨基酸及(口恶)唑啉肽类等具有强抗肿瘤活性的化合物。由氨基酸制备相应酰胺的方法有。(1)先转化为相应的酯,再氨解制得。但对α-位空间位阻大的氨基酸不够理想。(2)先转化为酸酐,如与氯代甲酸异丁酯作用得混合酸酐,氨解,一般说产率较高。     

含氨基酸结构的磺酰胺衍生物合成与生物活性

采用分子杂交策略，设计合成15个氨基酸结构的磺酰胺衍生物进行抗菌活性评价。首先，苯磺酰氯与氨基酸反应制得苯磺酰氨基酸（中间体Ⅰ），然后，以芳香醛、亚磷酸酯、乙酸铵和三氟甲磺酸铝为原料，一锅法制得α-氨基膦酸酯（中间体Ⅱ），最后，中间体Ⅰ与Ⅱ缩合，制得目标物，经1H NMR 、13C NMR和MS确认结构。结果表明，该类化合物对大肠杆菌（E. coli）和耐氟喹诺酮大肠杆菌（FREC）活性最为显著。其中，化合物Ⅲb〔{(2-氟苯基) [2-(苯基磺酰氨基)苯丙酰氨基]甲基}膦酸二乙酯〕、Ⅲc〔{(2-氟苯基) [2-(苯基磺酰氨基)苯丙酰氨基]甲基}膦酸二乙酯〕、Ⅲh〔{(2-氟苯基) [2-(苯基磺酰基氨)异戊酰氨基]甲基}膦酸二乙酯〕和Ⅲm〔{(苯基) [2-(苯基磺酰基氨)乙酰氨基]甲基}膦酸二乙酯〕对E. coli的MIC（Minimum Inhibitory Concentration）均为16 μg/mL，化合物Ⅲn〔{(2-氟苯基) [2-(苯基磺酰氨基)乙酰氨基]甲基}膦酸二乙酯〕对E. coli的MIC为8 μg/mL，抗菌活性不低于对照药苯唑西林；化合物Ⅲb、Ⅲh、Ⅲm和Ⅲn对FREC的MIC分别为32、32、32和16 μg/mL，优于对照药苯唑西林和诺氟沙星。     

酰胺类化合物合成方法研究综述

酰胺类化合物作为有机化合物中重要且常见的一类化合物,在药物研发、生产中扮演着重要的角色,对于其合成方法的研究在医药研发、应用领域中有着积极的现实意义。在酰胺类化合物的传统合成方法中,通常主要采用羧酸类衍生物同胺类直接偶联进行,往往在安全性、经济性、绿色性方面应用受限。随着社会经济的快速发展,科学技术的不断进步,不断涌现出一些新的方法、技术,应用于酰胺类化合物的合成中,极大地丰富了酰胺键构建方法。本文总结以往酰胺类化合物合成方法的相关报道,以期为今后酰胺类化合物合成的有效进行提供一定依据。     

芳香酰胺类化合物的合成研究

首先以芳基酮为起始原料,在乙醇溶液中,与盐酸羟胺反应,合成了不同结构的酮肟中间体,接着以磷酸-醋酐作为催化剂,通过发生Beckmann重排反应,合成了几种芳香酰胺类化合物。所有产品均经核磁共振氢谱、碳谱、红外光谱、熔点等手段进行了表征,最后讨论了芳环上取代基对酰胺产物产率的影响,根据Beckmann重排机理,进一步分析了酰胺异构体的形成过程和原因。     

酰胺类化合物的合成及农药生物活性研究进展

酰胺基团在农药合成中应用广泛,近年来研究人员在化合物结构中引入酰胺基团,合成了一系列具有广泛生物活性的农药小分子。综述了酰胺类化合物合成及农药活性研究中的应用,并对其发展前景进行了展望。     

3,4-二氯吡唑酰胺类化合物合成及其杀虫活性

以氯虫苯甲酰胺为先导化合物,通过在其吡唑环上引入氯原子,合成了1 1个吡唑酰胺类新化合物。所有化合物通过~1HNMR、元素分析进行了结构表征,并初步测定了化合物对二化螟的杀虫活性。在0.1 mg/L质量浓度下,部分新化合物对二化螟的生物活性显著高于氯虫苯甲酰胺。     

4-取代苯乙炔的简便制备方法

采用4-(4-丙基环己基)苯乙酮为原料,与Vilamerier试剂反应得到β-氯代丙烯醛衍生物,在碱性条件下消除一氧化碳和氯化氢得到4-(反式-4-丙基环己基)苯乙炔,两步反应的总收率为51.8%,色谱纯度达到97%.此法反应步骤少、反应条件温和、原料价廉易得、总成本低,适合规模化生产.     

超短多壁碳纳米管组装管的简易制备

以质量分数为10%的过氧化氢溶液为氧化剂,以1 mol/L的硫酸为酸性介质,常温下放置48 h,即可以简单地将冗长团聚的多壁碳纳米管切割成超短碳纳米管的组装管.碳纳米管组装管的长度为50～800 mm,超短碳纳米管的长度为8～15 mm.碳纳米管被切短后没有引入取代官能团.     

酸性氧化电位水制备新工艺

对EOW制备工艺中离子膜类型、电解方式和碱性水回流3个方面进行了考察,发现利用均相阴离子交换膜代替均相阳离子交换膜,可以有效地提高电解效率,原因在于阴离子膜可以有效地阻止H 的反渗透;采用阴、阳电解槽同时加入电解质溶液并采用阴离子膜的电解方式最优;当回流比在40%～60%时可以得到合格的EOW,回流比为80%时得到EOW的pH值超出范围;回流比对EOW的ORP值和ACC值影响不大.设计了EOW制备的新工艺,提高了制备效率和电极使用寿命,减少了碱性水的排放.     

A novel way to prepare anion exchangers based on crosslinked polystyrene

A novel method for preparing anion exchangers based on crosslinked polystyrene is proposed which comprises first acetylation of crosslinked polystyrene by Friedel-Crafts reaction, then reductive amination of acetylated products by Leuckart reaction. Aminated products, if desired, are readily converted to corresponding tertiary amino anion exchangers or optionally quaternized to form corresponding strong base, quaternary ammonium anion exchangers. The new method, overcome the toxic problem of classic chloromethylation process, is safe, economical and convenient. Received: 29 September 1997/Revised version: 4 November 1997/Accepted: 12 November 1997     

A simple method to prepare hybrid hydroxyapatite scaffold mimicking nature bone

The physio-chemical properties of natural bone are significantly determined by the biological environment. Thus, it is desirable to prepare advanced bone tissue engineered scaffold by mimicking nature bone formation process. In this study, we proposed a new simple method (physio-chemical mixing) to prepare a hybrid hydroxyapatite (HA) scaffolds mimicking nature bone. Nano powder phases constitution was studied by SEM, XRD, and TEM. The results founded that the simple method could affect the physio-chemical properties (i.e., compositions and morphologies) of HA scaffolds. Moreover, the scaffolds prepared could have mimicked the nature bone.     

A facile way to prepare crystalline platelets of block copolymers by crystallization-driven self-assembly

Poly(ε-caprolactone)-block-poly[2-(dimethylamino)ethyl methacrylate] (PCL-b-PDMAEMA) block copolymers were applied to fabricate elongated polymer platelets with axial length of 5–20 μm and thickness of ca. 10 nm by crystallization-driven self-assembly (CDSA). The block copolymer platelets composed of a crystallized PCL layer sandwiched between two PDMAEMA layers were obtained spontaneously by adding methanol, a selective solvent of PDMAEMA, into the block copolymer solution of THF at 25 °C. Therefore, this is a facile approach to generate lamellar nanoobjects of block copolymers. Effects of the block copolymer compositions on the morphologies of platelets were investigated. The presence of PDMAEMA segments along the lamellar surfaces was further confirmed by loading gold nanoparticles. Moreover, PEO-b-PCL-b-PDMAEMA triblock terpolymer could form spindle platelets by this approach. The crystalline platelets were characterized by the transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD).     

A simple process to prepare nitrogen-modified few-layer graphene for a supercapacitor electrode

We report a simple approach to prepare the nitrogen-modified few-layer graphene (FLG) directly from graphite flakes. With the aid of melamine, graphite flakes can be directly ultrasonicated into FLG in acetone. The subsequent annealing process further transforms the melamine absorbed on the surface of graphene into melon (C₆N₉H₃)_x, which is one type of condensation product of melamine, and simultaneously dopes the graphene with nitrogen. When tested as a supercapacitor electrode, the nitrogen-modified FLG shows a much higher specific capacitance (e.g., 227 F/g at 1A/g) than that of reduced graphene oxide (rGO) (e.g., 133 F/g at 1A/g).     

Spinodal dewetting–A simple method to prepare conjugated polymer array

A novel, simple method was developed to prepare conjugated polymer array in a large scale by using a spinodal dewetting technique. Mica, silicon, and glass were selected as substrates. The results show that with a suitable concentration of poly(9,9‐dihexylfluorene) (PF) in volatile organic solvent the polymer forms different sizes of array on the substrates. Atomic force microscopy measured the three‐dimensional structure of the arrays, and the relative FFT and PSD analyses reveal the detail information of the dewetting process and the array formation mechanism. The size of spots in the arrays is controlled by the evaporation speed of solvent and concentration of the PF solutions. The photoluminescence of PF arrays were also measured. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1412–1417, 2005     

简便测定L-半胱氨酸含量的方法

目前有22种氨基酸可由发酵法制得,只有胱氨酸和L-半胱氨酸不能用发酵法生产.而L-半胱氨酸可由胱氨酸还原而来,其化学反应式为: