16187-15-8Relevant articles and documents
MECHANISM OF THE OZONOLYSIS OF PROPENE IN THE LIQUID PHASE.
Choe,Srinivasan,Kuczkowski
, p. 4703 - 4704 (1983)
Propylene was ozonized in isobutane, hlorodifluoromethane, and methyl chloride solvents. Propylene ozonide, ethylene ozonide, and 2-butene ozonide (cis and trans isomers) were obtained in ratios of about 82:16:2. The amount of butene ozonide increased while that of ethylene ozonide usually decreased for reactions in the presence of added acetaldehyde. The cis-trans stereochemistry of the butene cross ozonide from propylene was studied at various conditions. Usually the cis isomer was preferentially formed, but addition of acetaldehyde could alter this. The cis-(trans-butene ozonide ratio was 67/33 when formed from cis- or trans-2-butene in CHClF//2 and 50/50 as a cross ozonide from trans-2-pentene. The kinetic secondary isotope effects upon ozonolysis of propene-2-d//1 (k//H/k//D equals 0. 88 (6) and propene-1-d//1 (0. 88 (8) were evaluated. These results are discussed with reference to the Criege mechanism of ozonolysis. 37 refs.
High-Field Rapid Injection NMR: Observation of Unstable Primary Ozonide Intermediates
McGarrity, John F.,Prodolliet, Jacques
, p. 4465 - 4470 (2007/10/02)
A "rapid injection" NMR system is described for use on a 360-MHz superconducting spectrometer.The major advantages of the high-field sytem over our original system are increased sensitivity, resolution, and rapidity.The technique was used to study the ozonolysis of tetramethylethylene and (briefly) cis-but-2-ene, particularly the decomposition of the corresponding primary ozonides 2 and 4, with half-lives of 0.74 and 0.06 s, respectively, at -92 deg C.It was found that the decomposition of 2 in CD2Cl2 (a) had Δ H(excit) = 39 kJ/mol and Δ S(excit) = 28 J/(molK), (b) was unaffected by the presence of TCNE, but (c) was acid-catalyzed.The effects of substituents, solvent, and acid catalysts on the decomposition of primary ozonides are discussed.