- Total-deuteration tert butyl alcohol preparation method
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The invention discloses a total-deuteration tert butyl alcohol preparation method which comprises the following steps: firstly, making deuterium methyl magnesium iodide and deuteration acetone performGrignard reaction in anhydrous tetrahydrofuran under the existence of anhydrous manganese chloride; then hydrolyzing a reaction product under the acid condition to generate total-deuteration tert butyl alcohol, wherein the acid condition is formed by a heavy water solution which deuteration acid is added in. The total-deuteration tert butyl alcohol preparation method disclosed by the invention has the advantages of moderate reaction condition, high reaction yield, ability in obtaining abundant total-deuteration tert butyl alcohol and simpleness in technological operation.
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Paragraph 0025-0027; 0029; 0031; 0033; 0035
(2018/07/06)
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- Kinetic Isotope Effects for Hydrogen Abstraction from a Series of Cycloalkanes and Branched Alkanes by Hydrogen Atoms in the Gaseous Phase
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Hydrogen atoms produced in the radiolysis of water vapor were used to determine the kinetic isotope effects for the reactions H(.) + RH(RD) -> H2(RD) + R(.) H(KD)>, where RH is a perprotiated alkane and RD is the corresponding perdeuterated alkane.The alkanes studied include a homologous series of cycloalkanes, cyclopentane through cyclododecane, and isobutane, 2,3-dimethylbutane, 2,3,4-trimethylpentane, and neopentane.The results were expressed in terms of the Arrhenius-type equation kH/kD = AH/AD expD-EH)(kJ mol-1)/RT>, over the temperature range of 363-463 K.The values for the ratio AH/AD range from 0.32 to 0.75, and the activation energy differences ED-EH vary from 6.8 to 11.0 kJ/mol, depending on the molecular structures of the reactants.The variation in the values of ED-EH was correlated with the bond dissociation energies of the C-H bond being broken.Theoretical calculations based on transition-state theory combined with the London-Eyring-Polanyi-Sato potetial energy surfaces could reproduce the major features of the experimental results when tunnel effects were taken into consideration.
- Fujisaki, Noboru,Ruf, Amanz,Gaeumann, Tino
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p. 1605 - 1610
(2007/10/02)
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- DEHYDRATION OF ALCOHOLS ON ALUMINA-12
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Primary kinetic isotope effects of the dehydration from the gas phase of tertiary, secondary and iso-butanol on alumina have been easured between 120 and 230 C. The deuteration on the hydroxyl group does not give rise to an isotope effect, whereas substitution of the !-proton by deuterium produces an appreciable effect. Below 200 C primary, secondary, and tertiary alcohols are dehydrated via reaction intermediates over alumina which presumably contain a certain degree of ionic contributions. With increasing temperature these ionic contributions are favored.
- KNOEZINGER H,SCHEGLILA A
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p. 252 - 263
(2007/10/05)
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