4,6—二取代—3—酮—5硫酮—1,2,4—三嗪类化合物的质谱研究

1,2,4-三嗪类化合物具有抗癌、抗病毒、杀虫、抑制中枢神经系统等多种作用。前文用苯甲酰基硫代甲酰胺直接与氨基脲反应,制备了8种新的4,6-二取代-3-酮-5-硫酮-1,2,4-三嗪类化合物(a—h),本文测定了其电子轰击质谱、高分辨质谱及联动扫描质谱,以了解其质谱裂解途径。     

三嗪酮杀虫活性分子的合成及生物活性

为发展更加高效的三嗪酮杀虫活性分子,本文设计合成了16种氨基部分被取代的三嗪酮衍生物,并测试了其杀虫、抑菌活性。杀虫活性测试表明:在浓度为600mg·kg~(-1)时,化合物N-(苯基氧羰基)-N-(6-甲基-3-氧代-2,3-二氢-1,2,4-三嗪-4(5H)-基)氨基甲酸苯酯(3e,100%、100%、100%)的杀棉铃虫、玉米螟、粘虫活性高于吡蚜酮(20%,35%,50%)。在浓度为0.5mg·kg~(-1)时,化合物3e(60%)的杀蚊幼虫活性高于吡蚜酮(0)。抑菌活性测试表明:三嗪酮酰胺衍生物对玉米小斑病菌和西瓜炭疽病菌表现出较高的抑菌活性;而三嗪酮亚胺衍生物对小麦纹枯病菌表现出较高的抑菌活性。     

α-叔戊酰基硫代甲酰胺缩氨基脲环化反应

含1,2,4-三嗪结构的化合物具有抗病毒、调节植物生长等作用。本文用α-叔戊酰基硫代甲酰取代苯胺缩氨基脲环化得到4-取代苯基-6．叔丁基-5-硫酮-1,2,4三嗪-3-酮,进一步环化得到5诹代苯氨基-6-叔丁基-1,2,4-三嗪-3-酮。反应方程式如下：     

5-取代苯氨基-6-苯基-1,2,4-三嗪-3-酮的合成

苯甲铣基-N-取代茜基硫代甲酰胺与氨基脲缩合后,环化可何成4,6-二取代-5-硫酮-1,2,4-三嗪-3-酮.本文报道将其缩氨基脲中硫甲基化,然后在碱性条件下, 改变成环方式,合成九个5-取代苯氨基-6-苯基-1,1,4-三嗪1-3-酮.它们的结构经元素分析,红外,核磁,质谱等予以证实.探讨了两种不同成环原因.     

新型2H-噻唑[3,2-b][1,2,4]三嗪-3,7-二酮的超声辅助一锅法合成及乙酰胆碱酯酶抑制活性研究

以取代苯甲醛、溴乙腈和6-苄基-3-硫代-3,4-二氢-1,2,4-三嗪-5(2H)-酮为起始原料,在超声辅助下,一锅合成了9个新型6-苄基-2-亚苄基-2H-噻唑[3,2-b][1,2,4]三嗪-3,7-二酮类化合物,结构经_¹H NMR,_¹³C NMR和MS（ESI）表征并对其合成机理进行了初步研究。测试了目标化合物(4a~4i)的体外乙酰胆碱酯酶的抑制活性,其中4a和4d抑制活性最好,有进一步研究的价值。     

2′-芳基-3-(1,4,5,6-四氢-6-哒嗪酮-3-羰基)氨基硫脲及其环化产物的合成

以α-酮戊二酸为起始原料,合成了1,4,5,6-四氢-6-哒嗪酮-3-甲酰肼(2),然后将2与异硫氰酸芳基酯反应得到相应的芳基氨基硫脲衍生物3a～3f.用硫酸、醋酸汞或氢氧化钠分别将芳基氨基硫脲环化得到一系列新的1,3,4-噻二唑、1,3,4-噁二唑和1,2,4-三唑的衍生物.化合物的结构经元素分析,IR,1H NMR和MS谱得以证实.     

5-取代苯氨基-6-甲基-1,2,4-三嗪-3-硫酮的合成

含有 1 ,2 ,4 三嗪结构的化合物具有广泛的生理活性。我们曾用α 乙酰基硫代甲酰芳胺为原料 ,合成了一系列三嗪类和其它杂环化合物 ,其中1 ,2 ,4 三嗪类有 4,6 二取代 5 硫酮 1 ,2 ,4三嗪 3 酮[1 ,2 ] ,3 氨基 5 取代苯氨基 6 苯基 1 ,2 ,4 三嗪[3] 等化合物。本文以α 乙酰基硫代甲酰芳胺为原料 ,进一步合成 5 取代苯氨基 6 甲基 1 ,2 ,4 三嗪 3 硫酮。当乙酰基硫代甲酰芳胺 1 (ａ ｇ)与氨基硫脲 2反应时 ,首先生成缩氨基硫脲 3(ａ ｇ) ,然后环化得到 5 取代苯氨基 6 甲基 1 ,2 ,4 三嗪 3硫酮 4(ａ ｇ) ,合成中发现 ,4(ａ ｇ)可…     

1,2,4-苯并三嗪自由基的合成及应用研究进展

自由基拥有独特的成键方式和物理性质,化学性质活泼,是很多有机反应的中间体;稳定的自由基在电池、储能、生物等功能分子的构建中有潜在应用。而1,2,4-苯并三嗪自由基作为一种尤其稳定的自由基,其氧化还原电位可逆,电化学窗口较小,在可见光区域有较宽的吸收,电磁性质与结构有紧密的关系。1,2,4-苯并三嗪自由基特殊的性质使其在聚合物合成控制、光学探测器、电子器件、磁性材料中有广泛的应用前景。本文综述了1,2,4-苯并三嗪自由基不同的合成方法,介绍了近年来1,2,4-苯并三嗪自由基在各个方面的应用进展。最后对1,2,4-苯并三嗪自由基在功能材料开发中的应用前景进行了展望。      

烷基取代三唑硫酮席夫碱的合成和生物活性研究

用5-烷基-4-氨基-2,4-二氢-1,2,4-三唑-3-硫酮与取代芳醛在酸催化下反应合成了7个席夫碱, 化合物结构用¹H NMR, IR和元素分析进行了表征, 对植物病原菌的生物活性测试表明它们具有较好的生物活性.     

通过α-重氮-β-二酮与醛酮的环加成反应合成4H-1,3-二噁环己-5-烯-4-酮衍生物

研究了α-重氮-β-二酮与各类羰基化合物的环加成反应,合成了一系列4H-1,3-二噁环己-5-烯-4-酮衍生物.     

Preparation and properties of polyurethane networks based on α,ω-difunctional poly(hexafluoropropylene oxide)

Poly(hexafluoropropylene oxide), poly(HFPO), networks were prepared from functional polymers by end linking via urethane groups. The prepolymers were characterized by NMR spectroscopy and GPC. The networks were characterized by determination of the number of network chains from the shear modulus, and were snown to contain both trifunctional crosslinks and difunctional links. The properties of the networks were investigated by a range of techniques. Compared with fully-fluorinated networks formed via triazine cross-links, investigated previously, the urethane-linked networks were more readily prepared but were poorer elastomers, were less thermally stable, and were less resistant to swelling by common polar solvents. © 1995 John Wiley & Sons, Inc.     

IClO2异构化反应机理及电子密度拓扑研究

利用密度泛函理论方法研究了IClO2异构化反应机理. 优化得到了七种异构体, 其中OIClO和IClOO还未见报道, 对各异构体的热力学稳定性进行了比较. 找到了异构化过程的过渡态, 并通过内禀反应坐标(IRC)计算确认了各个异构体之间的相互转化关系. 从量子拓扑学的角度, 对典型异构化反应通道IRC途径上的各点进行了电子密度拓扑分析, 讨论了反应过程中化学键的断裂、生成以及化学键的变化规律, 找到了反应途径上的能量过渡态(ETS)和结构过渡态(STS).     

南瓜籽烘烤前后化学成分的分析

对烘烤前后南瓜籽中的化学成分进行分析并对比。采用同时蒸馏萃取装置萃取南瓜籽中的挥发性成分,采取超临界CO2萃取技术萃取南瓜籽油脂,并将其分为酸、碱、中性三个部分,用气相色谱-质谱联用方法分析其中化学成分并进行对比。结果表明,南瓜籽挥发性成分中含有多种醛类和酯类化合物,烘烤后产生了大量的烷基吡嗪,其在碱性部分中的相对含量比烘烤前提高14倍多,不饱和醛类化合物含量也有明显提高。南瓜籽油脂中的主要化学成分是油酸、亚油酸及其酯类。还含有生物活性功能成分如植物甾醇、角鲨烯和维生素E等。烘烤后除角鲨烯含量有所降低,维生素E、植物甾醇、亚麻酸等均有提高。     

云南菊科中草药中铅含量特征分析

论述了云南２７种菊科中草药及其水提取物中铅含量的特征。菊科植物及水提物中铅含量的频数分布为正偏态,两者的相关系数ｒ＝０．０９,未呈现显著的线性相关。提取率较高的山紫苑、佩兰、木香铅实际含量低;铅含量高的叶下花、狭叶兔耳风、臭灵丹提取率又较低,减少了人体对Ｐｂ的过量摄入。     

Reversed-phase high-performance liquid chromatographic, gel electrophoretic and size exclusion chromatographic studies of subunit structure of arachin and its molecular species

Arachin and its molecular species (arachin I and arachin II) were separated and isolated. The number and kind of subunits of arachin, arachin I and arachin II were determined. Studies were carried out under different experimental conditions using slab gel electrophoresis, size-exclusion chromatography and reversed-phase high-performance liquid chromatography. Gel electrophoresis was done under varying concentrations of resolving gel. Tube gel as well as slab gel electrophoresis were used and continuous as well as discontinuous buffer systems were used for both types of electrophoresis. In addition, the subunits were separated by reversed-phase HPLC using a gradient program. Arachin and arachin II were found to have 12 subunits each while arachin I showed six subunits. The subunits of arachin I were allowed to reconstitute by removing SDS. Eight combinations were tried for studying the reconstitution pattern. Molecular weight and weight ratio in each case were also determined.     

Manipulation of protein fingerprints during on-column fluorescent labeling: protein fingerprinting of six Staphylococcus species by capillary electrophoresis

Bacterial proteomes were analyzed by use of electrophoretically mediated microanalysis (EMMA) and field-enhanced stacking. A water-soluble protein fraction was injected onto a capillary. Next, a fluorogenic reagent was injected and allowed to react with the protein mixture, producing fluorescent products that were separated by submicellar capillary electrophoresis and detected by laser-induced fluorescence. By use of a low-ionic strength sample buffer and a brief electrophoretic step, slow moving anionic proteins were stacked at the reagent-sample interface and were preferentially labeled. By reversing the order of sample injection and labeling reagent, fast moving cationic proteins were preferentially labeled. By adjustment of the sample buffer pH, proteins with different isoelectric points were selectively labeled. Electrophoresis fingerprints were generated for the water-soluble protein fraction from six Staphylococcus species. The protein patterns produced were species-specific and were used to construct a phylogenetic tree.     

Simultaneous determination of residual antiparasitic lactones in bovine muscle and liver by liquid chromatography with fluorescence detection

Abamectin, doramectin, eprinomectin, ivermectin, milbemectin, and moxidectin in bovine muscle and liver were extracted with acetonitrile. The extracts were partitioned with n-hexane and then evaporated to dryness. The residue was cleaned up on Bond Elute NH2 cartridge, and the drugs were eluted from the cartridge with methanol-ethyl acetate (3 + 7). The eluate was evaporated to dryness, and residues were derivatized with N,N-dimethylformamide-acetic anhyride-1-methylimidazole. The derivatives were determined by liquid chromatography with fluorescence detection. Recoveries of the 6 drugs were 79.6-63.8% in muscle and 71.6-60.6% in liver at 0.01 ppm levels. The quantitation limits were 5 ppb for each drug.     

膜催化研究II. 多孔无要膜的制备与表征及其反应器对甲醇脱氢反应的促进作用

采用溶胶-凝胶法制备了多孔氧化铝膜, 并通过DSC、TGA、SEM、N~2吸附和气体透过率测定等手段, 对膜的性能进行了表征。结果表明, 用这种方法制备的多孔氧化铝膜是一种均匀无裂痕和具有较窄孔径分布(约4nm)的膜材料。将此多孔氧化铝膜制成膜反应器后, 用于甲醇催化脱氢制甲醛的反应, 发现甲醇转化率比常规反应器有较大幅度的提高。同时首次尝试采用溶胶-凝胶法将催化活性组分直接负载到多孔氧化铝膜上, 从而得到了一种具有催化活性的多孔膜, 并考察了它的反应活性。文中对由这两种多孔膜及钯/陶瓷复合膜制成的反应器的特点进行了比较。     

等离子体发射光谱法测定茶水中无机元素的含量

采用电感耦合等离子体发射光谱法对茶水中的无机元素进行分析,对其中的Cu、Zn、Mn、P、Fe5种元素进行定量,讨论了等离子体发射光谱法最佳实验条件及影响茶叶中无机元素浸出量的因素。Cu、Zn、Mn、P、Fe的回收率为92．5％～103．5％,测定结果的相对标准偏差为1．34％-4．5％（n=5）。     

碳苷研究 V: 用Grignard试剂合成取代苯酚中酚羟基的保护及脱保护

本文报道了一些取代苯酚的合成, 并探讨了用Grignard试剂合成取代苯酚中酚羟基的保护及脱保护的问题. 利用苄基和甲基作为酚羟基的保护基, 对文献报道的切断醚键脱保护方法进行了评价. 找到了两种新体系能在更温和条件下切断醚键的方法, 指出了它们的适用条件. 实验结果符合硬软酸碱理论.