三组分串联反应合成苯并硫氮杂卓衍生物

以原位生成的芳基重氮盐为自由基源,在无过渡金属条件下,以单质硫作为硫源,利用碘化钾促进的2-(1H-吡咯-1-基)苯胺/单质硫/炔三组分自由基串联反应,经过自由基型的单质硫插入/加成/环化等过程,成功构建了20个苯并硫氮杂卓衍生物,通过¹HNMR、¹³CNMR和HR-MS对产物的结构进行确证。反应产率为45%~73%,底物适用范围较广并具有良好的官能团兼容性。通过自由基捕获实验结合液质分析,推测了反应过程可能产生的中间体。     

Polymeric Nanocapsule from Silica Nanoparticle@Cross-linked Polymer Nanoparticles via One-Pot Approach

A facile strategy was developed here to prepare cross-linked polymeric nanocapsules (CP nanocapsules) with silica nanoparticles as templates. The silica nanoparticle@cross-linked polymer nanoparticles were prepared by the encapsulation of the silica nanoparticles by the one-pot approach via surface-initiated atom transfer radical polymerization of hydroxyethyl acrylate in the presence of N,N′-methylenebisacrylamide as a cross-linker from the initiator-modified silica nanoparticles. After the silica nanoparticle templates were etched with hydrofluoric acid, the CP nanocapsules with particle size of about 100 nm were obtained. The strategy developed was confirmed with Fourier transform infrared, thermogravimetric analysis and transmission electron microscopy.     

A Microfluidic Approach to Synthesize Monodisperse Poly (2-Hydroxyethyl Methacrylate) Based Spherical Microgels via Water in Water Emulsion Technique

Monodisperse spherical microdroplets of poly(2-hydroxyethyl methacrylate) (p-HEMA) were prepared by in situ UV photopolymerization process via water-in-water emulsion technique in a 3-dimentional flow-focusing microfluidic device. Due to very low interfacial tension of dispersed and continuous phases and hence their high miscibility, the microdroplets formation was assisted via a mechanical forcing with a Piezoelectric buzzer. The effects of forcing frequency and flow rate ratio on microgels size and their monodispersity were monitored by an optical microscope. The p-HEMA based microgels were characterized by FT-IR to follow the extent of photopolymerization process. The results showed that the solvent- and surfactant-free p-HEMA based monodisperse spherical microgels in the range of 19–112 µm with variation of less than 10% could be successfully synthesized at the forcing frequency of 2–40 Hz. The developed rapid microfluidic approach for synthesis of p-HEMA based spherical microgels can be used as a versatile and highly biocompatible route in green chemistry.     

一种一锅法合成2,3-二苯基苯并呋喃的方法研究

2-炔基苯甲醚在碘存在下进行亲电环化反应得到3-碘代苯并呋喃衍生物,而后在水相中与硼酸酯进行钯催化的串联Suzuki反应,一锅法得到2,3-二苯基苯并呋喃的衍生物。并对反应机理进行了初步探索。     

氨曲南的制备新工艺

以头孢他啶侧链酸(ATTBA)为原料,首次采用酰氯法制备氨曲南,即在双(三氯甲基)碳酸酯(BTC)/三苯基氧膦(TPPO)体系作用下,现场制备酰氯盐酸盐中间体,再与trans-3(S)-氨基-4-甲基-2-氧代-1-氮杂环丁烷基磺酸反应,最后脱保护得氨曲南,总收率为40.6％.     

合成邻苯二甲酰亚胺的新工艺

以N ,N 二甲基甲酰胺作为溶剂 ,探索了苯酐和尿素反应生产邻苯二甲酰亚胺的适宜工艺条件。结果表明最优的配比是苯酐∶尿素∶溶剂 =1∶0 .6∶2 ,溶剂可以重复使用。同原工艺相比 ,新工艺能够降低生产成本 ,减少环境污染     

1种聚合硫酸铁合成的新方法

介绍了1种聚合硫酸铁合成的新工艺.以硫酸亚铁、硫酸、双氧水为原料,采用催化氧化法工艺路线制备了聚合硫酸铁,并进行了去浊率和脱色率试验.结果表明:合成聚合硫酸铁时,55 g的硫酸亚铁加入H2O2和浓硫酸的体积分别为13.50 mL和3.40 mL时最佳;对于浊度为100NTU的高岭土去浊率94%,对某印染废水的脱色率为92%～95%;产品质量指标达到和超过国家标准要求.生产设备投资小、产品稳定性好,无二次污染,适合中小型企业投资生产.     

制备球形KDNBF的新方法

介绍了一种制备球形KDNBF的新方法。通过使用PVA、吐温80、司盘、NaCMC、糊精、Triton X等表面活性剂，可以控制KDNBF的结晶形状，在这些表面活性剂中，吐温80的效果最好。制备出的KDNBF用FT-IR、DSC和元素分析等方法进行了表征。     

环氧丙烷嵌入乙酸酐合成1,2-丙二醇二乙酸酯的绿色化学途径

用Mg-Al基复合物催化环氧丙烷(PO)一步嵌入乙酸酐(AA)合成了1,2-丙二醇二乙酸酯(PGDA),经红外光谱、电喷雾质谱鉴定得到了预期产物。研究了反应温度、n(PO)/n(AA)、PO滴加或一次性投入方式对单PO加成选择性的影响。实验结果表明,当Mg-Al基复合物用量为1.6 g/100 g AA,n(PO)/n(AA)=1,以0.75g/min滴加PO,反应温度130~135℃时,单PO加成选择性达到w(PGDA)=98.2%。与传统合成二元醇二酯的方法相比,该路线无需过量加入AA原料,亦不生成副产物,是一条具有工业化前景的合成二元醇二酯的高原子经济性的绿色化学途径。     

一乙醇胺合成草甘膦的新工艺

研究了一种新的制备草甘膦的工艺：在合适的反应条件下，加入-乙醇胺、甲醛、亚磷酸三甲酯生成一种混合物，再在适当的条件下水解该混合物，生成N-(膦酰基甲基)乙醇胺及其盐，在同一浴中，N-(膦酰基甲基)乙醇胺及其盐用Raney Cu催化氧化，再水解得到草甘膦。草甘膦的平均收率可达80％。     

A Simple Method to Synthesize Cadmium Hydroxide Nanobelts

Cd(OH)₂ nanobelts have been synthesized in high yield by a convenient polyol method for the first time. XRD, XPS, FESEM, and TEM were used to characterize the product, which revealed that the product consisted of belt-like crystals about 40 nm in thickness and length up to several hundreds of micrometers. Studies found that the viscosity of the solvent has important influence on the morphology of the final products. The optical absorption spectrum indicates that the Cd(OH)₂ nanobelts have a direct band gap of 4.45 eV.     

A Chemical Co-Reduction Route to Synthesize Nanocrystalline Vanadium Carbide

Nanocrystalline vanadium carbide (VC) was synthesized via a chemical co-reduction process, in which VCl₄ and CCl₄ were used as the vanadium source and the carbon source, respectively, and metallic Na as a reductant in an autoclave at 500°C for 12 h. X-ray powder diffraction indicated that the product was an NaCl type of VC with a cell constant a =4.171 Å. A transmission electron microscopy image showed the VC particles were 10–40 nm in size. X-ray photoelectron spectrum and Raman spectrum showed the surface covered with oxide and graphite. The formation of nanocrystalline VC was discussed based on thermodynamics.     

一种合成氟喹诺酮DW286的新方法

DW286是吉米沙星的甲基衍生物,该产品的体内外抗多种革兰阳性致病菌的活性普遍优于第三代氟喹诺酮.但目前对其合成工艺的研究较少,且普遍存在合成步骤较多、污染严重等缺点.采用常规方法(甲基化、还原、保护、氧化、肟化、脱保护等)得到了侧链化合物3-甲基-3-(氨甲基)-4-(甲氧亚胺基)吡咯烷盐酸盐,然后将其与萘啶酸母核缩合制备标题化合物.该合成方法简单易行,具有进一步的研究价值.     

聚丙烯成核剂NA-11合成的新方法

对聚丙烯成核剂2,2'-亚甲基-双(4,6-二叔丁基苯酚)磷酸钠(NA-11)的合成工艺进行了优化.以2,4-二叔丁基苯酚和甲醛为原料,通过酚醛缩合反应,合成了中间物2,2'-亚甲基-双(4,6-二叔丁基)苯酚,其收率为95.1%,纯度为98.9%.中间化合物与三氯氧磷在乙腈中,室温下反应1 h,回流水解0.5 h,得到2,2'-亚甲基-双(4,6-二叔丁基苯酚)磷酸酯,其收率为90.2%,纯度为94.8%,与文献工艺相比较收率提高了1倍.在甲醇中,磷酸酯与氢氧化钠反应,生成2,2'-亚甲基-双(4,6-二叔丁基苯酚)磷酸钠,产物收率为99.5%,纯度为99.9%,以2,4-二叔丁基苯酚计的总收率为84.6%.     

溶胶-凝胶法制备锑掺杂氧化锡纳米粉体

以金属锡粉和三氧化二锑为金属原料,制备得到柠檬酸锡、锑的配合物溶液,向其中加入乙腈,形成溶胶-凝胶过程。对洗涤后的凝胶进行不同温度热处理得到锑掺杂氧化锡纳米粉体。随着锑掺杂量的增加,纳米粉体的晶粒减小,比表面积增加,晶胞参数也发生相应变化。随着热处理温度的升高,纳米颗粒长大,比表面积减小,高锑掺杂量的氧化锡纳米粉体显示出结晶性下降的趋势。     

Tandem Aldol-Michael Reactions in Aqueous Diethylamine Medium: A Greener and Efficient Approach to Bis-Pyrimidine Derivatives

A simple protocol, involving the green synthesis for the construction of novel bis-pyrimidine derivatives, 3a–i and 4a–e are accomplished by the aqueous diethylamine media promoted tandem Aldol-Michael reaction between two molecules of barbituric acid derivatives 1a,b with various aldehydes. This efficient synthetic protocol using an economic and environmentally friendly reaction media with versatility and shorter reaction time provides bis-pyrimidine derivatives with high yields (88%–99%).     

Manganese‐Promoted Regioselective Ring‐Opening of 2,3‐Epoxy Acid Derivatives: A New Route to α‐Hydroxy Acid Derivatives

A simple and general methodology directed towards the synthesis 3‐aryl‐2‐hydroxy amides, or esters with total regioselectivity from the easily available 2,3‐epoxy amides or esters, promoted by active manganese is described. Utilizing enantiopure epoxy amides as starting materials, the corresponding 3‐aryl‐2‐hydroxy amides in enantiopure form are also available. Some synthetic applications of selected examples of 3‐aryl‐2‐hydroxy carboxylic acid derivatives are shown. A mechanism has been proposed to explain this novel reaction.     

Rheomolding: A New Process to Mold Polymeric Materials

Polymer processing is an engineering field which deals with the conversion of synthetic high polymers into shaped articles ready for use. Impressive developments in the field of polymer processing in the last 20 years or so were precicipitated by the need to process plastic materials with an ever-increasing rate of production within stringent quality requirements. One of the most interesting methods for shaping plastic products is molding which involved all the possible ways for stuffing molds with thermoplastic or thermosetting polymers. Injection molding, compression molding, and transfer molding have now become some of today's routine approaches to plastics shaping.     

提高海密梯克磁力泵运行可靠性的办法和途径

简述了海密梯克磁力泵的特点，分析了该泵运行中常见故障问题的原因，并为确保和提高海密梯克磁力泵平稳运行可靠性，提出了相应措施和途径。