共查询到20条相似文献,搜索用时 46 毫秒
1.
以脱镁叶绿酸-a甲酯为原料,利用Vilsmeier反应合成δ-(甲酰乙烯基)二氢卟吩衍生物.镍(II)脱镁叶绿酸-a甲酯和镍(II)红紫素-18与Vilsmeier试剂作用,生成了E环被打开的镍(II)δ-(甲酰乙烯基)红紫素-7-三甲酯和镍(II)δ-(甲酰乙烯基)二氢卟吩P6三甲酯.镍(II)N-乙酰氧基红紫素-18-酰亚胺和Vilsmeier试剂作用,生成了镍(II)δ-(甲酰乙烯基)-N-乙酰氧基红紫素-18-酰亚胺.当这些化合物脱去镍离子后,吸收波长明显红移,δ-(甲酰乙烯基)-N-乙酰氧基红紫素-18-酰亚胺的吸收波长达到742nm.同时保留了对δ-位再进行化学修饰的可能性.合成的新化合物均由核磁共振、红外光谱、元素分析和质谱予以证实. 相似文献
2.
以脱镁叶绿酸-a甲酯为原料,利用Vilsmeier反应合成б-(甲酰乙烯基)二氢卟吩衍生物.镍(II)脱镁叶绿酸-a甲酯和镍(II)红紫素-18与Vilsmeier试剂作用,生成了E环被打开的镍(II)б-(甲酰乙烯基)红紫素-7-三甲酯和镍(II)б-(甲酰乙烯基)二氢卟吩P6三甲酯.镍(II)N-乙酰氧基红紫素-18-酰亚胺和Vilsmeier试剂作用,生成了镍(II)б-(甲酰乙烯基)-N-_乙酰氧基红紫素-18-酰亚胺.当这些化合物脱去镍离子后,吸收波长明显红移,б-(甲酰乙烯基)-N-乙酰氧基红紫素-18-酰亚胺的吸收波长达到742 nm.同时保留了对б-位再进行化学修饰的可能性.合成的新化合物均由核磁共振、红外光谱、元素分析和质谱予以证实. 相似文献
3.
4.
5.
6.
7.
近几年,芳基甲酰甲酸开始作为一种新的酰基化试剂应用于有机合成中。与其他酰基化试剂相比,其可以通过脱羧过程以亲核试剂的形式参与反应,具有反应活性高、反应条件温和的特点,大大拓展了酰基化反应的应用范围。本文综述了近几年芳基甲酰甲酸在偶联反应和碳氢键活化反应研究中的新应用和新进展。 相似文献
8.
9.
甲酰胺是重要的化工原料,广泛应用于农药和医药生产中,其合成方法备受关注.目前,主要通过胺与不同甲酰化试剂(甲酸、甲酸盐、甲酰胺和CO2等)的N-甲酰化反应合成甲酰胺.但由于转酰化反应生成的副产物不可避免,原子经济性100%的直接甲酰化成为更理想的合成路径.典型的甲酰胺代表是N,N-二甲基甲酰胺(DMF),工业上通过CH3OH-NaOCH3催化剂催化二甲胺和CO直接甲酰化生成DMF.近年研究者发展了多种直接甲酰化的催化体系,例如N-杂环卡宾、KOH、K2CO3和Co@N掺杂碳催化剂和PdCo双金属催化剂等.本课题组也报道了Ru修饰的氧化铈(Ru/CeO2)和羟基磷灰石(Ru-HAP)催化的胺直接甲酰化(Green Chem.,2017,19,88-92和ChemCatChem,2021,13,41594163).然而,相较于伯胺,仲胺的直接甲酰化合成甲酰胺更加困难.因此,开发一种新的仲胺转化策略进而合成高附加值的甲酰胺非常必要.本文发展了一种基于羟基磷灰石负... 相似文献
10.
发展环状化合物的高效合成方法对药物分子、天然产物及其他功能有机分子的合成具有重要意义.近年来,叔膦促进下两种亲电试剂之间的环化反应,由于具有原料简单易得、反应条件温和、且无需金属参与等优点,同时为多种碳环及杂环化合物的合成提供了高效的新途径,因而受到了合成化学家的广泛关注.这类反应通常经过叔膦对亲电试剂进行亲核加成,产生两性离子活性中间体这一关键步骤来完成.根据两性离子的不同来源,综述了叔膦促进下缺电子联烯、Morita-Baylis-Hillman烯丙基化合物、缺电子烯烃与其他亲电试剂之间的环化反应. 相似文献
11.
12.
13.
The toxicity of inorganic trivalent arsenic for living organisms is reduced by in vivo methylation of the element. In man, this biotransformation leads to the synthesis of monomethylarsonic (MMA) and dimethylarsinic (DMA) acids, which are efficiently eliminated in urine along with the unchanged form (Asi). In order to document the methylation process in humans, the kinetics of Asi, MMA and DMA elimination were studied in volunteers given a single dose of one of these three arsenicals or repeated doses of Asi. The arsenic methylation efficiency was also assessed in subjects acutely intoxicated with arsenic trioxide (As2O3) and in patients with liver diseases. Several observations in humans can be explained by the properties of the enzymic systems involved in the methylation process which we have characterized in vitro and in vivo in rats as follows: (1) production of Asi metabolites is catalyzed by an enzymic system whose activity is highest in liver cytosol; (2) different enzymic activities, using the same methyl group donor (S-adenosylmethionine), lead to the production of mono- and di-methylated derivatives which are excreted in urine as MMA and DMA; (3) dimethylating activity is highly sensitive to inhibition by excess of inorganic arsenic; (4) reduced glutathione concentration in liver moderates the arsenic methylation process through several mechanisms, e.g. stimulation of the first methylation reaction leading to MMA, facilitation of Asi uptake by hepatocytes, stimulation of the biliary excretion of the element, reduction of pentavalent forms before methylation, and protection of a reducing environment in the cells necessary to maintain the activity of the enzymic systems. 相似文献
14.
Electrochemistry is one of the most advanced techniques for monitoring neurochemical activities in the living brain because electrochemical approaches bear the advantageous features of high spatial and temporal resolutions, which facilitate its tremendous potential in investigating the highly spatially heterogeneous brain system and the fast dynamics of neurochemical activities. On the other hand, since brain is the most complicated organ in the sense of its numerous kinds of neurochemical species, high selectivity is always required for any analytical methods that approach the brain. In this review, we will discuss various electrochemical methodologies to achieve selective detection of neurochemicals in mammalian brain and the strategies developed mainly by our group towards selective monitoring of both electrochemically active and inactive neurochemicals. At the end, we will discuss possible solutions towards brain mapping of neurochemical species and combination of neurochemical detection strategy with electrophysiology as the direction of future development of electroanalysis in living brain. 相似文献
15.
A. P. Grimanis N. Kalogeropoulos V. Kilikoglou M. Vassilaki-Grimani 《Journal of Radioanalytical and Nuclear Chemistry》1997,219(2):177-185
Neutron activation analysis (NAA) is a very sensitive and accurate multielement analytical method that is widely applied to the investigation of environmental and archaeological problems. The first part of this paper is a review of pollution studies of toxic trace elements in sediments, seawater and marine organisms of Saronikos Gulf, Greece by NAA. The second part of this paper is a review of provenance studies based on minor and trace element research in ancient ceramics, obsidian, flint, limestone, marble and lead by Instrumental NAA, performed at the NCSR Demokritos. 相似文献
16.
17.
In situ generation of reactive species within confined geometries, such as nanopores or nanochannels is of significant interest in overcoming mass transport limitations in chemical reactivity. Solvent electrolysis is a simple process that can readily be coupled to nanochannels for the electrochemical generation of reactive species, such as H(2). Here the production of hydrogen-rich liquid volumes within nanofluidic structures, without bubble nucleation or nanochannel occlusion, is explored both experimentally and by modeling. Devices comprised of multiple horizontal nanochannels intersecting planar working and quasi-reference electrodes were constructed and used to study the effects of confinement and reduced working volume on the electrochemical reduction of H(2)O to H(2) and OH(-). H(2) production in the nanochannel-embedded electrode reactor output was monitored by fluorescence emission of fluorescein, which exhibits a pH-dependent emission intensity. Initially, the fluorescein solution was buffered to pH 6.0 prior to stepping the potential cathodic of E(0)' for the generation of OH(-) and H(2). Because the electrochemical products are obtained in a 2:1 stoichiometry, local measurements of pH during and after the cathodic potential steps can be converted into H(2) production rates. Independent experimental estimates of the local H(2) concentration were then obtained from the spatiotemporal fluorescence behavior and current measurements, and these were compared with finite element simulations accounting for electrolysis and subsequent convection and diffusion within the confined geometry. Local dissolved H(2) concentrations were correlated to partial pressures through Henry's Law and values as large as 8.3 atm were obtained at the most negative potential steps. The downstream availability of electrolytically produced H(2) in nanochannels is evaluated in terms of its possible use as a downstream reducing reagent. The results obtained here indicate that H(2) can easily reach saturation concentrations at modest overpotentials. 相似文献
18.
19.
Reactions in droplets in microfluidic channels 总被引:5,自引:0,他引:5
Fundamental and applied research in chemistry and biology benefits from opportunities provided by droplet-based microfluidic systems. These systems enable the miniaturization of reactions by compartmentalizing reactions in droplets of femoliter to microliter volumes. Compartmentalization in droplets provides rapid mixing of reagents, control of the timing of reactions on timescales from milliseconds to months, control of interfacial properties, and the ability to synthesize and transport solid reagents and products. Droplet-based microfluidics can help to enhance and accelerate chemical and biochemical screening, protein crystallization, enzymatic kinetics, and assays. Moreover, the control provided by droplets in microfluidic devices can lead to new scientific methods and insights. 相似文献
20.