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51.
52.
Oleg Kadkin Christian NätherWilly Friedrichsen 《Journal of organometallic chemistry》2002,649(2):161-172
[3]Ferrocenophane (3a) reacts in a Gomberg reaction with diazotized p-nitroaniline to give a mixture of mono- and di-substituted products. The isomeric pairs of 3- and 2-(p-nitrophenyl)[3]ferrocenophanes (4 and 5), as well as 3,4′- and 3,4-bis-(p-nitrophenyl)[3]ferrocenophanes (6 and 7) were separated from the mixture by column chromatography on Al2O3 and characterized by means of mass, IR, UV, 1H-NMR spectroscopy, and by X-ray analysis (4 and 6). PM3/tm and density functional theoretical calculations on ferrocene (1) and ferrocenophane derivatives are reported. A refined X-ray structure determination of [3]ferrocenophane (3a) is given. 相似文献
53.
The preparation of four novel bridged piperazine building blocks is described: 3,7,9-triazabicyclo[3.3.1]nonane 1, 3-oxa-7,9-diazabicyclo[3.3.1]nonane 2, 3,6,8-triazabicyclo[3.2.2]nonane 3 and 3-oxa-6,8-diazabicyclo[3.2.2]nonane 4. The scaffold of 1 was synthesized from N,N′-dibromobenzenesulfonamide and ethyl acrylate. Compound 2 may be prepared from identical starting materials or alternatively from α,α′-diglycerol. Compounds 3 and 4 were identified as side products from possible aziridinium intermediates. 相似文献
54.
Feixue Gao Toshihiro Yamase Hideo Suzuki 《Journal of molecular catalysis. A, Chemical》2002,180(1-2):97-108
The H2O2-based epoxidation of bridged cyclic alkenes in a monophasic system containing low concentrations (<2 mM) of [Bu4nN]4[Pr2iNH3]2H[P{Ti(O2)}2W10O38]·H2O (1) (with two η2-peroxotitanium sites in the anion) has been studied in search of the catalytically active species involved. 31P NMR spectra of 1, measured under a variety of conditions, revealed that the active species was not hydroperoxotitanium complex [P{Ti(OOH)}2W10O38]7−or [P{Ti(OOH)}Ti(O2)W10O38]7−. The reaction pathways for the alkene epoxidation are discussed to understand the kinetics (especially the initial [H2O2] dependence). It was concluded that the net catalytic reaction for the epoxidation occurred through the two-electron oxidation at the hydroperoxotitanium site in the catalyst. 相似文献
55.
Klaus Burger Brigitte Helmreich Lothar Hennig Jan Spengler Fernando Albericio Annett Fuchs 《Monatshefte für Chemie / Chemical Monthly》2007,138(3):227-236
Summary. An efficient synthesis of 2-fluoro-3-(trifluoromethyl)furans was developed. Keystep of the reaction sequence is a [4 + 1]
cycloaddition reaction of tin(II)chloride to 4,4-bis(trifluoromethyl)-1-oxabuta-1,3-dienes. At elevated temperatures the tin
heterocycles are transformed into 1-aryl-4,4-difluoro-3-(trifluoromethyl)but-3-en-1-ones which on treatment with sodium hydride
in dry DMF give 2-fluoro-3-(trifluoromethyl)furans. The single fluorine bound to C-(2) can be readily replaced by various N-, O-, S-,
and C-nucleophiles and dinucleophiles. 相似文献
56.
Alper Tolga ?olak Okan Zafer Yeilel Tuncer H?kelek Ertan ahin 《Structural chemistry》2008,19(2):285-290
A novel metal–organic coordination polymer framework formulated as {[Zn(dipic)(μ-en)]·3H2O}
n
(1) (catena-poly-μ-ethylenediamine(dipicolinato)zinc(II) trihydrate) has been synthesized and characterized by spectral method (IR), elemental
analysis, thermal analysis (TG, DTG, DTA) and single crystal X-ray diffraction techniques. It crystallizes in the triclinic
system, space group P−1. The asymmetric unit contains three hydrogen-bonded water molecules and the Zn atom is five-coordinated by three N and
two O atoms. In fact, it is a new one-dimensional zinc complex with the peculiarity of having the ethylenediamine ligand very
unusually acting as bridge to form polymeric chains. In the crystal structure, intramolecular O–H···O and intermolecular O–H···O
and N–H···O hydrogen bonds result in the formation of a supramolecular structure, in which they seem to be effective in the
stabilization of the structure. 相似文献
57.
TS-1分子筛在H_2O_2参与的有机物分子选择氧化及环氧化反应中具有优异的催化性能,一直广受关注.目前,随着精细化工反应中大分子及液相反应的增多,目前工业上使用的微米级尺寸的沸石晶粒催化材料因其狭窄的孔道和较大的扩散阻力而越来越不能满足工业的实际生产需求与应用.小晶粒纳米沸石由于具有较大的外比表面积和较高的晶内扩散速率,因而在提高催化剂的利用率、增强大分子转化能力、减小深度反应、提高选择性以及降低结焦失活等方面均表现出优越的性能.然而,尺寸低于100 nm的沸石又存在着分离问题.因此,具有高催化活性、又能一步实现分离与回收的纳米沸石聚集体的合成,引起了人们的研究兴趣.目前可以通过使用聚苯乙烯球,球型阴离子交换树脂,硅烷化聚合物,聚合诱导胶体聚集(PICA)等实现纳米沸石聚集体材料的合成.其中采用有机硅烷化试剂来制备多级孔纳米沸石聚集体材料提供了一种新的路线.在沸石晶体表面修饰上有机硅烷化试剂,含Si–C键的有机硅烷化物种可以有效地阻止沸石颗粒的晶体生长,抑制形成大的沸石晶体,从而得到纳米粒子聚集体;同时有机硅烷化物种也对纳米沸石进行了表面改性,提高了其疏水性.特别是在有机相中硅烷化沸石可以形成小的、均匀的、聚集的疏水性的纳米沸石.同时,硅烷化试剂的本质和分子大小是沸石聚集体中多级孔大小的决定性因素.具有可调结构的多级孔沸石晶体可以通过在常规的碱性沸石合成混合物溶液中添加一个两性有机硅表面活性剂而合成.研究发现,固定在沸石纳米晶表面的机硅烷物种Si–C键能部分抑制纳米颗粒进一步聚集成较大的晶体,使用硅烷化晶种的方法可以合成具有高比表面的多级孔ZSM-5等沸石.然而,目前已报道的通过硅烷化晶种方法中得到的多级孔TS-1沸石材料的尺寸仅有100–150 nm,仍不利于分离和回收.近来桥联有机硅烷试剂进入人们的视野——通过干胶法合成多级孔β沸石,然而它们的尺寸也只有300–500 nm,反应分离和回收仍然非常困难.本文采用有机桥联硅烷化合物作为硅烷化试剂,将TS-1纳米沸石晶种或者晶体组装聚集成大的沸石聚集体.TEM和SEM结果表明,桥联有机硅烷在沸石晶体的聚集和后续的晶体生长中起到了非常有效的作用,成功地将100 nm左右的纳米沸石晶种或晶体桥联/组装成宏观大尺寸(5–40μm)的沸石聚集体.这些TS-1聚集体具有较好的机械强度,即使连续超声1 h也不会毁坏其结构,表明所得到的沸石材料可以在制备上解决分离困难并且在催化应用上容易回收.XRD,BET以及UV-Vis分析结果表明,引入在TS-1沸石晶种或者晶体溶液中有机硅烷试剂不会影响沸石的晶体结构、微孔体积以及Ti的配位状态.将H_2O_2作为氧化剂评价TS-1沸石聚集体和传统的纳米TS-1在烯烃环氧化反应中的催化性能,结果表明,硅烷化步骤对小分子己烯氧化的活性和选择性的影响不大,在环己烯大分子的氧化反应里表现出了较高的活性和选择性. 相似文献
58.
Jonathan Farjon Audrey Giros Sandrine Deloisy Luis Blanco Jérôme Hannedouche Emmanuelle Schulz Denis Merlet 《Magnetic resonance in chemistry : MRC》2013,51(4):230-233
A modified version of the IMPACT heteronuclear multiple bond correlation (HMBC) has allowed the characterization of an organosilane and a tetrasilylated yttrium complex. With the help of this sequence, an average gain in sensitivity close to 2 has been obtained compared with the standard HMBC experiment for disilanes as well as for yttrium complexes containing silylated ligands. This modified version of this long‐range correlation experiment opens the way for following kinetics in the range of a fraction of a minute and to study by NMR low concentrated samples and low abundant nuclei. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
59.
通过由Fe3(CO)12、RSH和Et3N所形成的[(μ-CO)(μ-RS)Fe2(CO)6]Et3NH于室温下分别与对或间苯二甲酰氯的原位反应,首次合成6个结构新颖的苯二甲酰基桥联铁硫配合物[(μ-RS)·Fe2(CO)6]2(μ-p-OCC6H4CO-p-μ)(R=Et,n-Bu,t-Bu)以及[(μ-RS)Fe2(CO)6]2(μ-m-OCC6H4CO-m-μ)(R=n-Pr,n-Bu,t-Bu).经元素分析、IR光谱及1HNMR表征了它们的结构,并讨论了产物的生成过程.此外,还提出了合成对苯二甲酰氯的一种新方法. 相似文献
60.
An unexpected compound, the aniline derived benzophenone imine, was isolated when tritylamine was treated with n-BuLi and alkyl halides, during the formation of N-alkyl tritylamines, in the process of preparing primary amines. A nucleophilic attack of the nitrogen anion of tritylamide on the adjacent C-bonded phenyl, either substituted or not, involving a bridging anionic intermediate, is proposed for this base-induced tritylamine rearrangement to produce the corresponding imine. Electron-withdrawing groups in the aromatic ring, favoring the negative charge development, affect the relative migratory tendencies. 相似文献