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81.
The lithium diisopropylamide-mediated 1,2-elimination of 1-bromocyclooctene to provide cyclooctyne is investigated using approximately 50 potentially hemilabile polyethers and amino ethers. Rate laws for selected ligands reveal chelated monomer-based pathways. The dependence of the rates on ligand structure shows that anticipated rate accelerations based on the gem-dimethyl effect are nonexistent and that substituents generally retard the reaction. With the aid of semiempirical and DFT computational studies, the factors influencing chelation are discussed. It seems that severe buttressing within chelates of the substitutionally rich ligands precludes a net stabilization of the chelates relative to nonchelated (eta(1)-solvated) forms. One ligand-MeOCH(2)CH(2)NMe(2)-appears to promote elimination uniquely by a higher-coordinate monomer-based pathway. 相似文献
82.
Veige AS Wolczanski PT Lobkovsky EB 《Angewandte Chemie (International ed. in English)》2001,40(19):3629-3632
83.
In this paper we study some mappings of skew ruled surfaces in simply isotropic space which preserve the generators. We study isometries, conformal mappings and mappings which preserve the area. Furthermore, we study mappings of surfaces in I
3
1 which preserve the asymptotic lines.Received December 18, 2001; in revised form July 12, 2002
Published online April 4, 2003 相似文献
84.
Václav Štengl Snejana Bakardjieva Natalie Murafa Eva Večerníková Jan Šubrt Vladimír Balek 《Journal of nanoparticle research》2007,9(3):455-470
A new method for preparation of titania nanowires with diameter around 10 nm and length up to 2–3 μm is described. The precursor
was prepared from sodium titanate by adding ethylene glycole (EG) and heating at temperature of 198°C for 6 h under reflux.
The sodium titanate glycolate formed by this way aggregated into 1D nanostructures and was subsequently transformed into titania
glycolate during a chemical treatment with 98% sulfuric acid. Titania nanowires with variable amount of anatase and rutile
were prepared by heating to temperatures in the range 350–1000°C. The precursor as well as titania based samples were characterized
by X-ray diffraction, Infrared spectroscopy, Scanning electron microscopy, High resolution transmission microscopy, Thermogravimetry,
Differential thermal analysis, Evolved gas analysis and Emanation thermal analysis. The nitrogen adsorption/desorption was
used for surface area and porosity determination. The photoactivity of the prepared titania samples was assessed by the photocatalytic
decomposition of 4-chlorophenol in an aqueous slurry under UV irradiation of 365 nm wavelength. 相似文献
85.
86.
87.
88.
Emil Gottlieb J. Neumann Lezé und Allard 《Fresenius' Journal of Analytical Chemistry》1893,32(1):252-253
Ohne Zusammenfassung 相似文献
89.
90.
Karel indel JiÍ Holubek Emil Svtek Olue Matouov Jiina Metyov Miroslav Protiva 《Journal of heterocyclic chemistry》1989,26(5):1325-1330
Reactions of dibenzo[b,e]thiepin-11(6H)-one (4) with 2-, 3- and 4-(dimethylaminomethyl)phenylmagnesium bromide afforded the tertiary alcohols 5a,b,c. The aldehydes 7 and 8 gave similarly the secondary alcohols 9a,b,c and 10c . Numerous attempts to prepare the corresponding ketones, especially by oxidation of 9a,b,c and 10c were unsuccessful. Only the oxidation of 9c with tetrabutylammonium chromate in chloroform afforded the desired ketone 16 . Its formation was accompanied by an important side reaction consisting in a cleavage of the “retro-ene-reaction” type leading to compound 11 and the aldehyde 13c which reacted with the chloroform present to give the alcohol 17 . Compounds 5a,b,c, 9a,b,c and 16 were tested as potential antidepressants but with the exception of some effects in the test of potentiation of yohimbine toxicity in mice, they proved inactive in this line. 相似文献