84847-60-9Relevant academic research and scientific papers
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
Cycloaddition between Carbonyl Oxides and Dicarbonyl Compounds: Isolation and Characterization of Novel Polycyclic 1,2,4,6-Tetroxepane Derivatives
McCullough, Kevin J.,Sugimoto, Toshiya,Tanaka, Shogo,Kusabayashi, Shigekazu,Nojima, Masatomo
, p. 643 - 652 (2007/10/02)
Formaldehyde O-oxide reacts with dicarbonyl compounds to produce mono-ozonides formed by conventional cycloadditions to an aldehyde carbonyl group of the substrate, and/or polycyclic 1,2,4,6-tetroxepane derivatives arising from formal cycloadditions involving both carbonyl groups.Similar reactions between the more highly substituted carbonyl oxides, benzaldehyde and octanal O-oxides, and dicarbonyl compounds yielded the corresponding mono-ozonides as the sole isolable cycloaddition products.In certain favorable cases, mono-ozonides could undergo acid-catalysed intramolecular rearrangement to the corresponding 1,2,4,6-tetroxepanes.X-Ray crystallographic analyses of two 1,2,4,6-tetroxepanes, 6a and 13b, are recorded.
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,
Ozonolysis of a Series of 1-Substituted Indenes. The Substituent Steric Effects on Ozonide Exo/Endo Ratios
Miura, Masahiro,Nojima, Masatomo,Kusabayashi, Shigekazu,McCullough, Kevin J.
, p. 2932 - 2936 (2007/10/02)
The ozonolysis of a series of disubstituted (1,2 and 1,3) and trisubstituted (1,2,3) indenes 1-28 in carbon tetrachloride at 20 deg C has been investigated.The major product in each case was the corresponding bicyclic ozonide, usually obtained as a mixtur
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.
Acidolysis of Ozonides. An ab Initio Study
Miura, Masahiro,Nagase, Shigeru,Nojima, Masatomo,Kusabayashi, Shigekazu
, p. 2366 - 2370 (2007/10/02)
As the model species of the intermediates which may participate in the acidolysis of ozonides, seven species 14-20 have been investigated with the ab initio SCF-MO method at the split-valence 4-31G level.On the basis of both the relative stabilities and the charge distributions of these species, we have attempted to provide insight into the apparently complicated experimental observations.
