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101.
Even though it was obtained in poor yield, p-tert-butylthiacalix[8]arene (TC8A) has been synthesized as a new member of thiacalix[n]arenes by the terephthalate-induced cyclization of a mixture of acyclic oligomers, which was obtained by the reaction between p-tert-butylphenol and sulfur with CaO in ethylene glycol/diphenyl ether system. Slow evaporation of the chloroform solution of TC8A afforded guest-free crystals consisting of TC8A itself. The close-packed crystal structure of TC8A resembles that of p-tert-butylcalix[8]arene (C8A) closely, containing a plated loop molecular structure.This revised version was published online in July 2005 with a corrected issue number.  相似文献   
102.
The oxygen ions of the β-VOPO4 catalyst were exchanged with an tracer by a reduction–oxidation method and by a catalytic oxidation of but-1-ene using 2. The bands at 992 and 900 cm−1 were more shifted to lower frequencies than those at 1076 and 1002 cm−1. Applying the correlation between the Raman bands and stretching vibrations in the literature, the exchanged oxygen species were estimated. The results suggest that the P–O–V vacancies corresponding to 992 and 900 cm−1 were responsible for reoxidation and the V=O oxygen corresponding to the 1002 cm−1 band of β-VOPO4 was not. The (VO)2P2O7 was oxidized to β-VOPO4 by O2 above 823 K. The insertion position of oxygen was determined at the bands at 992 and 900 cm−1 of β-VOPO4 using 2, which is the same as the exchanged position.  相似文献   
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Summary Catalytic combustion of toluene, propylene and CO over Pt/Al2O3 /Al catalyst was investigated. Strong inhibition effects are observed when the mixture of toluene, propylene and CO is oxidized. A reaction mechanism of catalytic combustion over Pt/Al2O/Al is proposed. The results from kinetic models are in good agreement with the experimental data.  相似文献   
106.
The partial molar volumes (Va) of 1-alkanols (carbon number, m=5, 6, 7) in - and -cyclodextrin (CD) solutions at 5.00 mmol kg–1 have been determined as a function of alkanol concentration (Ca) between 293.2 and 308.2 K by using a dilatometer. It has been observed that with an increase in Ca, Va increased in -CD solution but decreased in -CD solution, asymptotically to a value of Va in CD-free water. The dependence of Va on Ca provided the binding constant (K) of 1:1 complex, the volume change in complex formation, and the partial molar volume of complex itself. The complex formation mechanism has been discussed on the basis of these values and their carbon number dependences in the respect of geometric behavior, hydrophobic interaction, and van der Waals interaction. It is concluded that the CD cavity in water is not rigid but flexible for fitting in nicely with guest molecule.  相似文献   
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[reaction: see text] A concise and stereoselective synthesis of the chiral building block, dioxanylpiperidene 4 as a precursor for deoxyazasugars, starting from the Garner aldehyde 5 using catalytic ring-closing metathesis (RCM) for the construction of the piperidine ring is described. The asymmetric synthesis of 1-deoxygalactonojirimycin and its congeners 1-3 was carried out via the use of 4 in a highly stereocontrolled mode.  相似文献   
109.
We have developed new methods for preparing functionalized benzynes through deprotonative zincation as a key reaction using R2Zn(TMP)Li, and we also describes dramatic ligand effects on the benzyne formation. Deprotonative zincation of various meta-substituted bromobenzenes with Me2Zn(TMP)Li proved effective for the one-pot generation of various 3-functionalized benzynes, particularly those electrophilic substituents such as ester, amide, and cyano. On the other hand, zincation with tBu2Zn(TMP)Li, followed by electrophilic trapping (with I2) proved a powerful tool for the preparation of 1,2,3-trisubstituted aromatic compounds.8 The resultant 1,2,3-trisubstituted benzenes are available as precursors for generation of 3-substituted benzynes by halogen-zinc exchange reactions with Me3ZnLi. These methods offer far greater generality than previous methods for the synthesis of functionalized asymmetric benzynes, and should be of value in new syntheses of various natural products and functional materials. In addition, these results underline the utility of spectator ligands on the central metal of ate complexes as a tunable functionality in the development of new ate complex-promoted reactions.  相似文献   
110.
A new preparative method of β- and γ-alkoxy (acetoxy) ketones, which are important precursors of vinyl ketones and 1,4-diketones, respectively, is presented. With PdCl2/CuCl/O2 or PdCl2/p-benzoquinone catalyst system, internal olefins bearing allylic alkoxy or acetoxy group underwent regioselective oxidation to form the corresponding β-alkoxy or β-acetoxy ketones. Similarly, γ-acetoxy ketones were obtained from homoallyl acetates having internal olefins with high regioselectivity.  相似文献   
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