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21.
A versatile π-extension reaction was developed based on the three-component cross-coupling of aryl halides, 2-haloarylcarboxylic acids, and norbornadiene. The transformation is driven by the direction and subsequent decarboxylation of the carboxyl group, while norbornadiene serves as an ortho-C−H activator and ethylene synthon via a retro-Diels–Alder reaction. Comprehensive DFT calculations were performed to account for the catalytic intermediates.  相似文献   
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Journal of Solid State Electrochemistry - Manganese phosphate (Mn3(PO4)2) particles decorated polyaniline (PANI) have been proposed as a promising electrode material for supercapacitors. Mn3(PO4)2...  相似文献   
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The synthesis and reactivity of a silyliumylidene cation stabilized by an amidinate ligand and 4‐dimethylaminopyridine (DMAP) are described. The reaction of the amidinate silicon(I) dimer [ L Si:]2 ( 1 ; L =PhC(NtBu)2) with one equivalent of N‐trimethylsilyl‐4‐dimethylaminopyridinium triflate [4‐NMe2C5H4NSiMe3]OTf and two equivalents of DMAP in THF afforded [ L Si(DMAP)]OTf ( 2 ). The ambiphilic character of 2 is demonstrated from its reactivity. Treatment of 2 with 1 in THF afforded the disilylenylsilylium triflate [ L′ 2( L )Si]OTf ( 3 ; L′ = L Si:) with the displacement of DMAP. The reaction of 2 with [K{HB(iBu)3}] and elemental sulfur in THF afforded the silylsilylene [ L SiSi(H){(NtBu)2C(H)Ph}] ( 4 ) and the base‐stabilized silanethionium triflate [ L Si(S)DMAP]OTf ( 5 ), respectively. Compounds 2 , 3 , and 5 have been characterized by X‐ray crystallography.  相似文献   
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A homologous series of oligo(amide–triazole)s (OAT) [ OAT‐CO2H‐2 n and OAT‐COPrg‐(2 n +1) ] with an increasing number of primary amide (CONH) and triazole hydrogen‐bonding functionalities was prepared by an iterative synthetic procedure. It was found that their self‐assembly and thermoreversible gelation strength had a strong correlation to the number of hydrogen‐bonding moieties in the oligomers. There also existed a threshold value of the number of CONH units, above which all the oligomers became organogelators. Hence, oligomers with ≤4 CONH units are devoid of intermolecular hydrogen bonding and also non‐organogelating, whereas those that contain >4 CONH units show intermolecular association and organogelating properties. For the organogelators, the Tgel value increases monotonically with increasing number of CONH units. On the basis of FTIR measurements, both the CONH and triazole C? H groups were involved in the hydrogen‐bonding process. A mixed xerogel that consisted of a 1:1 weight ratio of two oligomers of different lengths ( OAT‐CO2H‐6 and OAT‐CO2H‐12 ) was found to show microphase segregation according to differential scanning calorimetry, thus indicating that oligomers that bear a different number of hydrogen‐bonding units exhibited self‐sorting to maximize the extent of intermolecular hydrogen bonding in the xerogel state.  相似文献   
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A general method for the preparation of 2‐(N‐Substituted)‐2‐imidazolines and 2‐(N‐Substituted)‐1,4,5,6‐tetrahydropyrimidines is described. These heterocycles can be synthesized from their respective anilines with 2‐chloro‐2‐imidazoline or 2‐chloro‐1,4,5,6‐tetrahydropyrimidine, generated in situ from imidazolidin‐2‐one and tetrahydropyrimidin‐2(1H)‐one activated by dimethyl chlorophosphate, in good to excellent yields.  相似文献   
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Well-characterized pure-substance reference materials for the use as calibrants are essential to establish the metrological traceability of the results of chemical measurements. Normally, the characterization of this type of reference material is conducted through a thorough purity assessment of the compound concerned. For this reason, studies on purity assessment, especially for neat organic compounds, continues as an important part of work being undertaken by metrological institutions around the world. Among others, the need for certified pure reference standards continues to increase for residues analysis in foods, particularly for those compounds which have been banned for food safety reasons, but their residues in foods are still monitored under food surveillance program in many countries. In this respect, avoparcin serves as a very good example where testing laboratories have difficulties in obtaining traceable and comparable results on determination of avoparcin in food matrix samples due, in part, to the unavailability of certified pure-substance reference material as calibrant. In this study, it was attempted to assess the purity of a commercially available test material of avoparcin using the mass balance approach. The objective of this paper is to share the difficulties encountered during the course of purity assessment and how they were addressed. As expected, the most challenging part of work was to identify and estimate the amount of unknown impurities, both organic and inorganic-related ones, given the chemical structure and properties of avoparcin. For instance, avoparcin exists in two forms in the test material, i.e., α- and β-avoparcin, and they were found to be susceptible to hydrolysis under certain conditions.  相似文献   
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香港花岗岩风化分级化学指标体系与风化壳分带   总被引:5,自引:1,他引:5  
火成岩的化学风化过程实质上就是碱、碱土金属组分水解淋失与脱硅富铁铝化的地球化学过程。不同风化程度的岩石处于整个化学风化过程的不同阶段,因而具有不同的化学成分和风化度指标。笔者在对香港九龙两个地方5个钻孔共计150件不同深度、不同风化程度的样品化学全分析结果与岩土风化程度宏观判别结果的相互对比、选择和确认的基础上,建立了香港地区花岗岩风化岩土风化程度工程分级的化学指标体系。这一研究成果的提出不仅有利于提高花岗岩风化岩土工程分类的科。学性、可靠性和实用性,而且可以为风化岩土工程特性与风化作用关系研究提供理论依据。  相似文献   
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