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1.
The use of in situ generated (NHC)-Ni catalytic species (NHC = N-heterocyclic carbene) allows for the synthesis, in short reaction times, of a variety of tertiary alcohols from secondary alcohols through a domino oxidation-addition protocol. 相似文献
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Yu. N. Zhitnev E. A. Tveritinova S. A. Chernyak S. V. Savilov V. V. Lunin 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2016,90(6):1128-1131
Carbon nanotubes (CNTs) obtained via the catalytic pyrolysis of hexane at 750°C were studied as the catalysts in conversion of C2–C4 alcohols. The efficiency of CNTs as catalysts in dehydration and dehydrogenation of ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tert-butanol was studied by means of pulse microcatalysis. The surface and structural characteristics of CNTs are investigated via SEM, TEM, DTA, BET, and XPS. CNTs are shown to be effective catalysts in the conversion of alcohols and do not require additional oxidative treatment. The regularities of the conversion of aliphatic alcohols, related to the properties of the CNTs surface and the structure of the alcohols are identified. 相似文献
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The reduction of chiral tetracyclic lactams 1, 2 led to new functionalized derivatives 5–8 containing 3 or 5 stereogenic centers. Autoxidation of compound 5 was observed yielding an enantiopure peroxide 9, which in turn slowly converted into tertiary alcohol 10. 相似文献
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We report an efficient synthesis of the title compounds from alcohols and selenols. The scope and limitations of the new method are disclosed. 相似文献
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A combination of boron trifluoride etherate and halide ion is found to be an excellent reagent for the conversion of allyl, benzyl and tertiary alcohols to the halides. 相似文献
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Semiempirical (AM1) molecular orbital theory has been used to investigate the oxidation of alcohols at the active site of liver alcohol dehydrogenase (LADH). The model active site consists of a zinc dication coordinated to two methyl-mercaptans (Cys-46, Cys-176), an imidazole (His-67), and a water. An imidazole (His-51) hydrogen bonded to a hydroxy-acetate (Ser-48) forms the remote base. AM1 calculations that address the two distinct steps in the catalytic mechanism of ethanol oxidation by LADH are reported. These two steps are: (1) the deprotonation of ethanol by imidazole (His-51) via hydrogen-bonded hydroxy-acetate (Ser-48), creating a proton relay system; and (2) the rate-limiting hydride transfer step from ethanol C1 to nicotinamide adenine dinucleotide (NAD+), leading to product formation. Detailed calculations have been used to resolve the unsolved problems of mechanisms that have been suggested on the basis of kinetic data and crystal structures of several LADH complexes. We investigated two possible mechanisms for the deprotonation of ethanol, by zinc-bound OH? and by direct deprotonation of zinc-bound ethanol by imidazole via hydroxyacetate (Ser-48). Our calculations show that there is no need for LADH to activate a water molecule at the active site as in many other zinc enzymes. This result agrees with experimental evidence. Our calculations also indicate that substrates are bound in an inner-sphere-pentacoordinated complex to the active site zincion. In this case, spectroscopic investigations agree with our results but crystallographic data do not. The highest activation energy is found for the hydride transfer, in agreement with the experiment. Finally, we proposed an alternative mechanism for the mode of action of LADH based upon our results. © 1993 John Wiley & Sons, Inc. 相似文献
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Summary A method was developed for the conversion of tertiary acetylenic alcohols to unsaturated acids. 相似文献
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Dehkordi S. Saeid Saei Albadi Jalal Jafari Abbas Ali Samimi Heshmat Allah 《Research on Chemical Intermediates》2021,47(6):2527-2538
A copper-based magnetic nanocatalyst has been prepared by co-precipitation method and characterized by FESEM, EDS, TEM, XRD, XRF, ICP–OES, FTIR, and BET analysis. This new nanocatalyst displays a good activity toward the aerobic oxidation of a wide range of alcohols in water. Moreover, it is recyclable up to five following runs by simple filtration without any significant loss of its catalytic activity.
相似文献10.
The influence of various substituted (including halogenated) alcohols on the temperature of maximum density (TMD) of water has been investigated. Evaluation of the structural contribution to the shift in the TMD demonstrates that trifluoroethanol, hexafluoroisopropanol, and neopentyl alcohol are structure makers, whereas trichloroethanol and tribromoethanol are structure breakers. The results are discussed in terms of an excluded volume model. 相似文献
11.
The effect of a homologous series of cyclic monohydric alcohols (C4−C8) on the temperature of maximum density of water has been examined. The structural contribution to the shift in the temperature
of maximum density (TMD) is positive (increased structuredness) for alcohols up to C6 but becomes negative at C8. The behavior is compared with that of linear monohydric alcohols and Ω-diols. 相似文献
12.
Rama D. Nimmagadda 《Tetrahedron letters》2006,47(32):5755-5758
A novel one-pot reaction has been developed for the reduction of aldehydes, ketones and primary, secondary and tertiary alcohols into their corresponding alkyl function. This is also the first reported method which can efficiently reduce primary, secondary, or tertiary alcohols, without affecting carbon-carbon double bonds, into their corresponding alkyl function in high yields. The reduction utilises either diethylsilane or n-butylsilane as the reducing agent in the presence of the Lewis acid catalyst tris(pentafluorophenyl)borane. 相似文献
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Conclusions Ionization constants were obtained of 14 amino alcohols and one tertiary amine in 50% ethanol in the range of 10–25° and thermodynamic characteristics of the ionization process of the investigated ammonium ions were calculated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 669–671, March, 1976.The authors express their gratitude to S. V. Bogatkov for participation in discussion of the obtained results. 相似文献
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The effect of temperature and concentration on the structure of sec-butyl alcohol and isobutyl alcohol/water binary mixtures in the alcohol-rich region (mole fraction of water X(H2O) < 0.3) has been studied using Fourier transform (FT) near-infrared (NIR) spectroscopy. The experimental data were analyzed by a two-dimensional (2D) correlation approach and chemometric methods. It was found that molecules of both alcohols in the mixture with water are in the same environment as those in the pure alcohols. Even at very low water content (X(H2O) = 0.001) we did not observe water free from any specific interactions. The molecules of water are attached to the end free OH groups in the open chain associates of alcohol. In this way the structure of neat alcohol remains intact by addition of water. The water-alcohol interactions in sec-butyl alcohol and isobutyl alcohol/water mixtures are stronger than those in bulk water. The results obtained at higher water content or elevated temperatures indicate the possibility of water-water interaction. In the alcohol-rich region the hydrophobic effects are of minor importance and the structure and properties of these systems are determined by hydrogen bonding through the hydroxyl groups. Both alcohols behave similarly on the temperature or water content variation; the minor difference results from a different degree of self-association for sec-butyl alcohol and isobutyl alcohol. 相似文献
16.
E. A. Tveritinova Yu. N. Zhitnev S. A. Chernyak E. A. Arkhipova S. V. Savilov V. V. Lunin 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2017,91(3):448-454
Carbon nanomaterials with the structure of graphene and different compositions of the surface groups are used as catalysts for the conversion of С2–С4 aliphatic alcohols. The conversions of ethanol, propanol- 1, propanol-2, butanol-1, butanol-2, and tert-butanol on carbon nanotubes, nanoflakes, and nanoflakes doped with nitrogen are investigated. Oxidized and nonoxidized multiwalled carbon nanotubes, nanoflakes, and nanoflakes doped with nitrogen are synthesized. X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning and transmission electronic microscopies, Brunauer–Emmett–Teller method, derivatographic analyses, and the pulsed microcatalytic method are used to characterize comprehensively the prepared catalysts. It was established that all of the investigated carbon nanomaterials (with the exception of nondoped carbon nanoflakes) are bifunctional catalysts for the conversion of aliphatic alcohols, and promote dehydration reactions with the formation of olefins and dehydrogenation reactions with the formation of aldehydes or ketones. Nanoflakes doped with nitrogen are inert with respect to secondary alcohols and tert-butanol. The role of oxygen-containing and nitrogen-containing surface groups, and of the geometrical structure of the carbon matrix of graphene nanocarbon materials in the catalytic conversion of aliphatic alcohols, is revealed. Characteristics of the conversion of aliphatic alcohols that are associated with their structure are identified. 相似文献
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The enantiomeric separations of three pesticides fipronil (asymmetric nitrogen), isocarbophos (asymmetric phosphorus) and carfentrazone-ethyl (asymmetric carbon) were studied on cellulose-tri(3,5-dimethylphenylcarbamate) chiral stationary phase using high-performance liquid chromatography under normal phase. The mobile phase was n-hexane with alcohols including ethanol, n-propanol, iso-propanol, n-butanol and iso-butanol as polar modifiers. The flow rate was 1.0 mL/min with UV detection at 280, 225 and 230 nm for fipronil, isocarbophos and carfentrazone-ethyl respectively. The influence of the modifiers and their volume content and temperature from 0 to 50 degrees C on the separations was investigated. The chiral stationary phase showed excellent stereoselectivity for the two enantiomers of fipronil and isocarbophos and certain chiral recognition for carfentrazone-ethyl. Iso-propanol was more suitable for the chiral separation of isocarbophos and carfentrazone-ethyl, and iso-butanol was better for fipronil. The resolutions increased with the decreasing modifier content and temperature for all the three chiral pesticides. 相似文献
20.
The effect of temperature and concentration on the structure of tert-butyl alcohol/water binary mixtures in the alcohol-rich region (X(H2O) < 0.3) has been studied by using Fourier transform near-infrared (FT-NIR) spectroscopy. The obtained results demonstrate that the addition of a small amount of water to tert-butyl alcohol (2-methyl-2-propanol, abbreviated as TBA) leads to minor changes in the structure of neat TBA and suggest that molecules of TBA in the mixture are in the same environment as those in pure TBA. The bands of water are red-shifted in the mixture relative to bulk water, implying that the molecules of water in TBA are involved in stronger hydrogen bonding. The present experimental data give no evidence for the existence of nonbonded water in the mixture. Even at a very low content of water, the main NIR bands of water (nu(2) + nu(3) and nu(1) + nu(3)) have two components showing markedly different behavior upon an increase in temperature. From the power spectra, it is seen that the extent of intensity changes due to the free OH groups of TBA is smaller in the mixture relative to pure TBA. All of these results support the model of chain-end bonding of water molecules to TBA associates. An increase in X(H2O) reduces the population of nonbonded OH groups of TBA, yet both processes do not appear at the same rate. The amount of bonded OH groups of water increases faster than that of the nonbonded ones. It seems that the water-water interaction becomes more important as X(H2O) increases. At high alcohol content, the position of the CH alkyl stretching bands is constant, evidencing a negligible role of the hydrophobic hydration in the mixture. 相似文献