84810-25-3Relevant academic research and scientific papers
Structure-reactivity relationships in (2-hydroxyethyl)benzophenone photoremovable protecting Groups
Pirrung, Michael C.,Roy, Biswajit Gopal,Gadamsetty, Surendra
experimental part, p. 3147 - 3151 (2010/05/18)
A detailed study of substituent effects on the photochemical conversion of esters of (2-hydroxyethyl)benzophenone to the carboxylic acid was performed with the aim of improving on the reactivity of the parent, which was first reported decades ago. Over 20
18O-tracer studies of Fe(II)-induced decomposition of 1,2,4-trioxolanes (ozonides) derived from cyclopentenes and indenes. Inner-sphere electron transfer reduction of the peroxide linkage
Abe, Manabu,Inakazu, Tomoyasu,Munakata, Johichi,Nojima, Masatomo
, p. 6556 - 6562 (2007/10/03)
Fe(II)-induced decomposition of 1,2,4-trioxolanes (ozonides) 1 and 2 is studied in detail. The inner-sphere electron transfer reduction, which is sensitive to steric effects, is proposed to be a reasonable mechanism for the peroxide decomposition, i.e., the selective generation of one of the two possible Fe(III)-complexed oxy radicals. The fate of the oxy radical species is revealed in detail by using 18O-tracer studies in the reduction of 18O-labeled ozonides 1a and 2a, in which the ethereal oxygens are labeled by 18O atom (18O, 77%) and also by the reduction in the presence of H218O (18O, 10%). The results of the 18O-tracer studies are consistent with the regioselective generation of the Fe(III)-complexed oxy radical species.
Ozonolyses of 1-Alkyl-Substituted 3-Methylindenes. Remarkable Effects of the Substituent Steric Bulk and the Stereochemistry of the Carbonyl Oxide Intermediates on the Efficiency of Ozonide Formation
Kawamura, Shin-Ichi,Takeuchi, Rika,Masuyama, Araki,Nojima, Masatomo,McCullough, Kevin J.
, p. 5617 - 5622 (2007/10/03)
Ozonolyses of 3-methyl- and 3-isopropyl-l-methylindenes (1a,b) in ether gave mainly the corresponding oligomers 3a,b, while in the case of 3-phenyl- and 3-tert-butyl-1-methylindenes (1c,d), the corresponding exo-endo mixtures of ozonides 2c,d were obtaine
Ozonolysis of 1-Methylindenes. Solvent, Temperature, and Substituent Electronic Effects on the Ozonide Exo/Endo Ratio
Miura, Masahiro,Fujisaka, Tomohiro,Nojima, Masatomo,Kusabayashi, Shigekazu,McCullough, Kevin J.
, p. 1504 - 1509 (2007/10/02)
The ozonolyses of 1-methyl-3-aryl-, 1,2-dimethyl-3-aryl-, and 1-methyl-2,3-diarylindenes (1a-e, 4a-e, 7a-e, 7a',b',d') in various solvents at several temperatures have been undertaken.The data revealed the following. (a) The ozonolysis of indenes 1c, 4c,
Synthesis, X-ray Analysis, and Acidolysis of exo- and endo-1-Methylindene Ozonides
Miura, Masahiro,Ikegami, Akio,Nojima, Masatomo,Kusabayashi, Shigekazu,McCullough, Kevin J.,Nagase, Shigeru
, p. 2414 - 2426 (2007/10/02)
Ozonolyses of 2,3-disubstituted 1-methylindenes gave mixtures of the corresponding exo and endo ozonides.The structures of endo-1-methyl-3-phenylindene ozonide (3a) and exo-1-methyl-2,3-diphenylindene ozonide (2b) were determined by the X-ray analysis.Acidolysis of exo- and endo-1-methylindene ozonides 2a-d and 3a-d under several conditions revealed some characteristic features. (a) Antimony pentachloride or chlorosulfonic acid catalyzed the interconversion of the exo-endo ozonide isomers, the ratio in equilibrium being ca. 7:3 for all the pairs. (b) In the reaction of 3-methyl-substituted indene ozonides 2c,d and 3c,d in acetic-d3 acid-d a rapid hydrogen-deuterium exchange on the bridgehead methyl was observed. (c) In methylene chloride or acetic acid the ozonides decomposed very slowly, yielding the mixtures of rearranged products 4 and 5, carboxylic acid 6, and diketone 7; both the rate of decomposition and the product distribution being a marked function of the structure of the ozonides. (d) Methanol accelerated the decomposition of ozonides, the disappearance following pseudo-first-order kinetics.The rate decreased in the order 3a > 2a > 2b > 2c ca. 3c > 3b.This order was significantly different from the order observed in the reaction in acetic acid: 3b > 3c > 2b > 2c > 3a > 2a. (e) Reduction by AlHCl2 gave a mixture of 3,4-dihydro-1H-2-benzopyrans 19 - 22, the composition being significantly varied depending on the stereochemistry of the ozonides. (f) Treatment of 2a or 3a with bis(α-hydroxy-4-methylbenzyl)peroxide (31) gave two stereoisomeric peroxides 32a and 33a in roughly equal amounts.In contrast, the reaction of an exo ozonide 2d with a mixture of p-tolualdehyde and 30percent H2O2 (an equivalent of 31) afforded exclusively the corresponding exo peroxide 32d, while the endo isomer 3d gave predominantly the endo peroxide 33d.
