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具有共轭体系的酮类烯醇硅醚与全氟碘代烷的反应 总被引:1,自引:0,他引:1
应用连二亚硫酸钠的引发,通过全氟碘代烷与醛类,酮类烯醇硅醚的反应,合成α-全氟烷基羰基类化合物的方法。利用该方法,还可以用“一锅法”合成含氟β-二酮类化合物。本文报道了在类似的反应条件下,与苯环或双键共轭的烯醇硅醚和全氟碘代反应的结果。 相似文献
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稀土硝酸盐与穴醚(2.2)及穴醚(2.2.2)配合物的合成和性质 总被引:5,自引:0,他引:5
由三价稀土、镧、铕和镱的硝酸盐分别与穴醚(2.2),穴醚(2.2.2)反应,合成相应的五种固体配合物,并进行了元素分析,IR,NMR,TG,DTA,电化学等性质的研究。 相似文献
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新法合成酰胺荚醚萃取剂 总被引:1,自引:0,他引:1
采用混合酸酐法,通过氧杂单酰胺酸与二烷基胺反应,合成了3种酰胺荚醚萃取剂N,N,N'N'-四烷基-3-氧-戊二酰胺(烷基为正丁基、异丁基和正辛基),产率分别为84%,80%和57%.采用1H NMR和MS对合成的酰胺荚醚萃取剂的结构进行了表征. 相似文献
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Sandra Künzler Saskia Rathjen Anastasia Merk Dr. Marc Schmidtmann Prof. Dr. Thomas Müller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(66):15123-15130
A new NMR-based Lewis acidity scale is suggested and its application is demonstrated for a family of silyl Lewis acids. The reaction of p-fluorobenzonitrile (FBN) with silyl cations that are internally stabilized by interaction with a remote chalcogenyl or halogen donor yields silylated nitrilium ions with the silicon atom in a trigonal bipyramidal coordination environment. The 19F NMR chemical shifts and the 1J(CF) coupling constants of these nitrilium ions vary in a predictable manner with the donor capability of the stabilizing group. The spectroscopic parameters are suitable probes for scaling the acidity of Lewis acids. These new probes allow for the discrimination between very similar Lewis acids, which is not possible with conventional NMR tests, such as the well-established Gutmann–Beckett method. 相似文献
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Christopher Hubrich Axel Schulz Harald Brand Alexander Villinger 《Phosphorus, sulfur, and silicon and the related elements》2013,188(9):2179-2196
The silyl ethers (siloxanes) Me4? xSi(OC6H5CN)x (x = 1–4) (1–4), O(Si(OC6H4CN) (Me)2)2 (5), and Me3Si–O–C6F4CN (6) have been synthesized by the reaction of the respective p-hydroxybenzonitriles and chlorosilanes in the presence of N,N,N′,N′-tetramethylethylenediamine (TMEDA) as hydrogen chloride acceptor. All compounds have been fully characterized by CHN-analysis, melting point, IR, Raman, mass spectroscopy, and 1H, 13C, 29Si NMR spectroscopy. Furthermore, the crystal structures of these compounds—with the exception of Me2Si(OC6H5CN)2, which is a liquid—were determined by X-ray diffractometry. 相似文献
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Rhodium‐Catalyzed Dehydrogenative Silylation of Acetophenone Derivatives: Formation of Silyl Enol Ethers versus Silyl Ethers 下载免费PDF全文
Dr. Karin Garcés Dr. Ralte Lalrempuia Dr. Víctor Polo Dr. Francisco J. Fernández‐Alvarez Dr. Pilar García‐Orduña Prof. Fernando J. Lahoz Prof. Jesús J. Pérez‐Torrente Prof. Luis A. Oro 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(41):14717-14729
A series of rhodium–NSiN complexes (NSiN=bis (pyridine‐2‐yloxy)methylsilyl fac‐coordinated) is reported, including the solid‐state structures of [Rh(H)(Cl)(NSiN)(PCy3)] (Cy=cyclohexane) and [Rh(H)(CF3SO3)(NSiN)(coe)] (coe=cis‐cyclooctene). The [Rh(H)(CF3SO3)(NSiN)(coe)]‐catalyzed reaction of acetophenone with silanes performed in an open system was studied. Interestingly, in most of the cases the formation of the corresponding silyl enol ether as major reaction product was observed. However, when the catalytic reactions were performed in closed systems, formation of the corresponding silyl ether was favored. Moreover, theoretical calculations on the reaction of [Rh(H)(CF3SO3)(NSiN)(coe)] with HSiMe3 and acetophenone showed that formation of the silyl enol ether is kinetically favored, while the silyl ether is the thermodynamic product. The dehydrogenative silylation entails heterolytic cleavage of the Si?H bond by a metal–ligand cooperative mechanism as the rate‐determining step. Silyl transfer from a coordinated trimethylsilyltriflate molecule to the acetophenone followed by proton transfer from the activated acetophenone to the hydride ligand results in the formation of H2 and the corresponding silyl enol ether. 相似文献
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Sarah A. Weicker Prof. Dr. Douglas W. Stephan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(37):13027-13034
Silyl triflates of the form R4?nSi(OTf)n (n=1, 2; OTf=OSO3CF3) are shown to activate carbon dioxide when paired with bulky alkyl‐substituted Group 15 bases. Combinations of silyl triflates and 2,2,6,6‐tetramethylpiperidine react with CO2 to afford silyl carbamates via a frustrated Lewis pair‐type mechanism. With trialkylphosphines, the silyl triflates R3Si(OTf) reversibly bind CO2 affording [R′3P(CO2)SiR3][OTf] whereas when Ph2Si(OTf)2 is used one or two molecules of CO2 can be sequestered. The latter bis‐CO2 product is favoured at low temperatures and by excess phosphine. 相似文献
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(Methylchlorosilyl)methyldichlorophosphines have been synthesized by the reaction of [dimethy(diethylamino)silyl]- or [methyl-bis(diethylamino)silyl]methylmagnesium chlorides with PCl3 in ether at –40÷–20 °C and subsequent treatment of the reaction mixture with dry HCl. The structures of the compounds thus obtained have been studied by31P,1H, and13C NMR spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 989–990, May, 1993. 相似文献
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Synthesis,Structural Characterization and Reactivity of a Bis(phosphine)(silyl) Platinum(II) Complex
Yonghua Li Wenjin Zeng Wenyong Lai Shigeru Shimada Shi Wang Lianhui Wang Wei Huang 《中国化学》2015,33(10):1206-1210
Treatment of 1,2‐C6H4(SiH3)(SiH3) ( 1 ) with Pt(dmpe)(PEt3)2 (dmpe=Me2PCH2CH2PMe2) in the ratio of 1:1 leads to the complex {1,2‐C6H4(SiH2)(SiH2)}PtII (dmpe) ( 2 ), which can react with proton organic reagent bearing hydroxy group with low steric hindrance to form a tetra‐alkoxy substituted silyl platinum(II) compound ( 3 ). Compounds 2 and 3 are the very rare examples of silyl transition‐metal complexes derived from this chelating hydrosilane ligand. To the best of our knowledge, there are only 6 examples of silyl metal complexes prepared from this ligand with such structural features registered in the Cambridge Structural Database, among them, only one silyl platinum(II) compound is presented. The structures of complexes 2 and 3 were unambiguously determined by multinuclear NMR spectroscopic studies and single crystal X‐ray analysis. 相似文献
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N. Iranpoor H. Firouzabadi H. Bahador A. Jamalian 《Phosphorus, sulfur, and silicon and the related elements》2013,188(9):1972-1978
Silicaphosphite (silphos), [PCl3-n(SiO2)n], as a heterogeneous phosphorous compound, catalyzes the thiocyanation of benzylic alcohols and silyl and THP ethers in the presence of I2 and NH4SCN in refluxing CH3CN. The produced silphos oxide byproduct can be easily separated by a simple filtration. Silphos is also used for the efficient and selective deprotection of silyl and THP-ethers to their corresponding alcohols. 相似文献
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Ernest W. Colvin Albert K. Beck Bahram Bastani Dieter Seebach Yasushi Kai Jack D. Dunitz 《Helvetica chimica acta》1980,63(3):697-710
An efficient and flexible method for the preparation of silyl nitronates is described (see 1–10 ). NMR. spectral investigations indicate a rapid 1,3-silyl migration process, with an activation energy of about 10 kcal mol?1. X-ray crystallographic studies on the silyl nitronates 3 and 8 show structures that lean towards an SN2 retention pathway at silicon. 相似文献
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The reactions of silyl carbamates and silyl dithiocarbamates with different acid chlorides (carbamoyl/thiocarbamoyl chloride, chloroformates, etc.) have been studied. The obtained mixed anhydrides have different thermal stability. 相似文献