- Aqueous Oxidations Started by TiO2 Photoinduced Holes Can Be a Rate-Determining Step
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In aqueous TiO2 photocatalytic hydroxylation of weakly polar aromatics, a series of inverse H/D KIEs of 0.7–0.8 were observed, which is different than the normal H/D kinetic isotope effects (KIEs) usually observed for polar aromatics. This result indicated that the oxidation started by photo-induced hvb + can be the rate-determining step.
- Gong, Yuanzheng,Yang, Chun,Ji, Hongwei,Chen, Chuncheng,Ma, Wanhong,Zhao, Jincai
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supporting information
p. 2048 - 2051
(2017/08/23)
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- A convenient method for palladium-catalyzed reductive deuteration of organic substrates using deuterated hypophosphite in D2O
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A convenient method for the deuteration of organic substrates using deuterated hypophosphite as the deuterium source was investigated. Transfer deuteration of organic substrates, such as aromatic halides, alkenes, alkynes, epoxides, and O-benzyl derivativ
- Oba, Makoto
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p. 215 - 219
(2015/05/20)
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- PREPARATION OF DEUTERIATED 1-PHENYLETHANOLS BY REDUCTIVE DEHALOGENATION OF THE CORRESPONDING HALOGENOACETOPHENONES WITH RANEY ALLOYS IN AN ALKALINE DEUTERIUM OXIDE SOLUTION
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Deuteriated 1-phenylethanols were prepared by reductive dehalogenation of the corresponding halogenoacetophenones with Raney Ni-Al and Cu-Al alloys in 5percent NaOD-D2O solution.It was found that the Ni-Al alloy introduced greater than expected numbers of deuterium atoms in the phenyl ring, but the expected deuteriated 1-phenylethanols were obtained in high yield and in high isotopic purity when Raney Cu-Al alloy was used.
- Tashiro, Masashi,Mataka, Shuntaro,Nakamura, Hiroshi,Nakayama, Kouji
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p. 179 - 182
(2007/10/02)
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- A Study of Gaseous Benzenium and Toluenium Ions generated from 1,4-Dihydro- and 1-Methyl-1,4-dihydro-benzoic Acids
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Gaseous benzenium C6H7(1+) (1) and toluenium C7H9(1+) (2) ions have been generated by mass spectrometric loss of .CO2H from the corresponding 1,4-dihydrobenzoic acids (3) and (4), and their fragmentations after ca. 10 μs have been investigated by means of mass-analysed ion kinetic energy (MIKE) spectrometry of some 2H and 13C labelled analogues.Metastable C6H7(1+) ions eliminate H2 after proton randomization, whereas metastable C7H9(1+) ions expel both H2 and CH4 after incomplete proton equilibration.In particular, 40percent of C7H9(1+) ions randomize all their carbon and hydrogen atoms prior to loss of CH4, and 60percent of C7H9(1+) ions lose the original methyl group along with a hydrogen atom from the (proton-equilibrated) benzenium ring, accompanied by a slow and incomplete exchange between the hydrogen atoms of the ring and the methyl group.It is suggested that loss of both CH4 and H2 occur via the (ipso-)toluenium ion (2).The role of a non-classical C7H9(1+) isomer, phenylmethonium ion (6), is discussed since striking similarities are found compared * adducts from ion-molecule reactions described in the literature.
- Kuck, Dietmar,Schneider, Jens,Gruetzmacher, Hans-Friedrich
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p. 689 - 696
(2007/10/02)
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- Preparation of All the Possible Ring-deuteriated Benzoic Acids by Reductive Dehalogenation of the Corresponding Halogenobenzoic Acids with Raney Alloys in an Alkaline Deuterium Oxide Solution
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All the possible undeuteriated benzoic acids were prepared mainly by treatment of the corresponding bromobenzoic acid with Raney Cu-Al alloy in 10percent NaOD-D2O solution. 5>Benzoic acid was obtained from pentafluorobenzoic acid by a similar reaction.However, only 4>benzoic acid was prepared by decarboxylation of 4>phthalic acid.
- Tashiro, Masashi,Nakayama, Kouji,Fukata, Gouki
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p. 2315 - 2318
(2007/10/02)
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