In order to reveal the reactivity of a functional group in an aromatic compound having two substituents inthe aromatic ring, the hydrogen-isotope exchange reaction (T-H exchange reaction) between tritiated water vapor...In order to reveal the reactivity of a functional group in an aromatic compound having two substituents inthe aromatic ring, the hydrogen-isotope exchange reaction (T-H exchange reaction) between tritiated water vapor(HTO vapor) and 4-amino-2-methylbenzenesulfonic acid (and 5-amino-2-methylphenol) were dynamically observedat 50 (and 70 ) in a gas ℃ ℃ -solid system. Consequently, the fact that the specific activity of the acid increased withtime was obtained, and the T-for-H exchange reaction occurred. By applying the A"-McKay plot method to the dataobserved, the rate constant of each functional group for the reaction was obtained. After the additive property of theHammett’s rule was applied to this work, the new substituent constants were obtained. From the above-mentioned,the following four items have been confirmed: (1) the reactivity of the functional groups can be dynamically analyzed,and the A"-McKay plot method is useful to analyze the reactivity; (2) the additive property of the Hammett’s rule isapplicable to quantitative comparison of the reactivity of the functional groups; (3) the reactivity of the functionalgroups can be simultaneously analyzed by using the A"-McKay plot method in the T-H exchange reaction; and (4) themethod used in this work is also useful for analyzing the reactivity of a certain material having some kinds of functional groups.展开更多
Fluorine-containing halogenated fluorophenol may have effect as intermediate species involved in the formation of polyfluorinated dibenzo-p-dioxin/dibenzofurans （PFDDs/Fs）. The mechanism for the atomic H initiated r...Fluorine-containing halogenated fluorophenol may have effect as intermediate species involved in the formation of polyfluorinated dibenzo-p-dioxin/dibenzofurans （PFDDs/Fs）. The mechanism for the atomic H initiated reactions with complete series of nineteen fluorophenol congeners was studies using the density functional theory. At the MPWB1K,/6-31＋G（d,p） level, the geometries and frequencies of reactants, transition states, and products were obtained, and the accurate energetic values were acquired at the MPWB 1K/6-311 ＋G（3df,2p） level. The rate constants were evaluated by the canonical variational transition-state theory with the small curvature tunneling contribution over a wide temperature range of 600-1000 K. The study shows that the intramolecular hydrogen-bond in the ortho-substituted FPs as well as the inductive effect of the electron-withdrawing fluorine and steric repulsion of multiple substitutions may ultimately be responsible for the relative strength of the O-H bonds in FPs. The results can be used for further studies on PFDD/Fs formation mechanism.展开更多
文摘In order to reveal the reactivity of a functional group in an aromatic compound having two substituents inthe aromatic ring, the hydrogen-isotope exchange reaction (T-H exchange reaction) between tritiated water vapor(HTO vapor) and 4-amino-2-methylbenzenesulfonic acid (and 5-amino-2-methylphenol) were dynamically observedat 50 (and 70 ) in a gas ℃ ℃ -solid system. Consequently, the fact that the specific activity of the acid increased withtime was obtained, and the T-for-H exchange reaction occurred. By applying the A"-McKay plot method to the dataobserved, the rate constant of each functional group for the reaction was obtained. After the additive property of theHammett’s rule was applied to this work, the new substituent constants were obtained. From the above-mentioned,the following four items have been confirmed: (1) the reactivity of the functional groups can be dynamically analyzed,and the A"-McKay plot method is useful to analyze the reactivity; (2) the additive property of the Hammett’s rule isapplicable to quantitative comparison of the reactivity of the functional groups; (3) the reactivity of the functionalgroups can be simultaneously analyzed by using the A"-McKay plot method in the T-H exchange reaction; and (4) themethod used in this work is also useful for analyzing the reactivity of a certain material having some kinds of functional groups.
基金supported by the National Natural Science Foundation of China(No.21177077,21177076)the Independent Innovation Foundation of Shandong University(No.2012JC030)
文摘Fluorine-containing halogenated fluorophenol may have effect as intermediate species involved in the formation of polyfluorinated dibenzo-p-dioxin/dibenzofurans （PFDDs/Fs）. The mechanism for the atomic H initiated reactions with complete series of nineteen fluorophenol congeners was studies using the density functional theory. At the MPWB1K,/6-31＋G（d,p） level, the geometries and frequencies of reactants, transition states, and products were obtained, and the accurate energetic values were acquired at the MPWB 1K/6-311 ＋G（3df,2p） level. The rate constants were evaluated by the canonical variational transition-state theory with the small curvature tunneling contribution over a wide temperature range of 600-1000 K. The study shows that the intramolecular hydrogen-bond in the ortho-substituted FPs as well as the inductive effect of the electron-withdrawing fluorine and steric repulsion of multiple substitutions may ultimately be responsible for the relative strength of the O-H bonds in FPs. The results can be used for further studies on PFDD/Fs formation mechanism.
