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金属羰基化合物

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Generally speaking, the reaction types involvingα-oxoketene--acetals mainly include the regioselective addition-aromatization with organometallic reagents, conjugate addition-cyclization with nitrogen nucleophilicspecies, nucleophilic reactions ofα-carbon, acting as odorless dithiol equivalentsin thioacetalization, Michael additions and [5+1] annulation, as well as the synthetic applications based on the above reactions.

一般来说,基于α-羰基二硫缩烯酮化学的反应主要为:与金属有机试剂的选择性加成反应,与氮亲核体的共轭加成反应,α-碳原子的亲核性及相关反应,烷硫基作为硫醇的替代试剂的应用,α-羰基二硫缩烯酮在碳环、杂环化合物合成中的应用等。

In the titration experiment of NMR and IR spectroscopy, we can understand how sensors binding with metal ions: the two carbonyl group and crown ether group cooperated in binding with metal ions. Furthermore, by altering the "oxygen" atoms of crown ether to "sulfur", we can change the binding affinity to the soft metal: cupper. It shows 60-fold enhancement of fluorescence.

在化合物2中,我们引进了硫原子在冠状醚中,则应对电子密度较低之金属有较好的结合能力,实验结果显示了此分子对铜离子有相当好的选择性和结合能力,萤光增加可达60倍;同时由红外光吸收光谱和核磁共振光谱滴定实验可确知,香豆素衍生物上的两个羰基对金属离子的选择性及结合上扮演相当重要的角色。

Based on the problem of various types of catalyst and according to the features of carbonylation catalysts reactions, our team has been designed a series of new metal complexes of benimidazoles, which can be used for carbonylation catalyst of industry. Seven new benzimidazole derivatives were prepared by the o-phenylenediamine、oxalic acid、glycolic acid、monomethyl monopotassium malonate、ethyl cyanoacetate、succinic anhydride. The structures of them were confirmed by IR、Elemental analsis. The crystal structures of d and e were determined by X-ray single crystal diffraction of Germanic Bruker Smart APEX II CCD. The catalysis of them was tested by carbonylation reactions.

本文设计以邻苯二胺和草酸、羟基乙酸、丙二酸单甲酯、氰基乙酸乙酯、丁二酸单甲酯为原料采用PPA催化和无机酸催化法,合成了4种苯并咪唑-2-羧酸衍生物并进行了表征;培养了2个化合物d、e的晶体并测定和讨论了晶体结构;制备了3种未见报道的苯并咪唑金属配合物,对配合物在羰基化法制醋酐-醋酸反应的催化作用进行了初步试验。

In the presence of catalytic rhodium acetate, ethyl 2-diazo-3-oxo-per fluoroalkanoates, reacted readily with nitriles to give a series of 5-fluoroalkyl substituted 1, 3oxazoles with high regio-selectivity through a metal carbenoid intermediate. The reactions of carbenoids with noncyclic vinyl ethers or cyclic vinyl ethers afforded dihydrofuroates in good to excellent yields. Interestingly, only vinyl C-H insertion compound was obtained concerning of the reaction of carbenoids with 2, 5dimethylfuran due to the steric hindrance of methyl group

醋酸铑分解2-重氮-3-氧代-全氟羧酸乙酯形成的金属卡宾作为1,3-偶极体,可以与一系列芳基或烷基取代的腈反应,高度区域选择性地生成一系列4-乙氧羰基-5-氟烷基取代的噁唑化合物;也可以与富电子的链状和环状的烯基醚反应,以优良的产率得到一系列氟烷基取代的二氢呋喃类化合物;而与2,5-二甲基呋喃的反应,由于甲基的位阻作用,只得到金属卡宾对呋喃3-位烯基碳氢键插入产物。

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