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Observed Products (observed + products)

Distribution by Scientific Domains

Chemistry	80%

Selected Abstracts

Mechanism of Oxidation of (olefin)RhI and -IrI Complexes by H2O2

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2004
Peter H. M. Budzelaar
Abstract A DFT study of the oxidation of (tpa)MI(C2H4)+ and (dpa-R)MI(cod)+ complexes (M = Rh, Ir) by H2O2 indicates that the reaction starts with heterolytic cleavage of the peroxide O,O bond, leading to MIII(olefin)(OH)2+ species. These can then undergo cyclisation, followed by deprotonation to oxetanes. In the oxidation of COD complexes, further cyclisation to internal ethers has a modest barrier, and the observed products (ethers for Rh, oxetanes for Ir) are suggested to be the thermodynamic ones. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source]

Catalytic cleavage of methyl oleate or oleic acid

EUROPEAN JOURNAL OF LIPID SCIENCE AND TECHNOLOGY, Issue 1 2010
Angela Köckritz
Abstract Different reaction pathways are discussed for the Os-catalyzed oxidation of methyl oleate and oleic acid using O2/aldehyde as oxidation system. Monomethyl azelate and pelargonic acid were the main products obtained in yields of approximately 50,70% starting from methyl oleate. Besides, varying amounts of methyl 9,10-epoxystearate and methyl 9,10-dihydroxystearate were found as by-products. Azelaic acid and pelargonic acid were obtained exclusively from oleic acid used as reactant. Some mechanistic considerations led to the conclusion that the observed products are formed in parallel reaction paths. The effective oxidant for the scission of the C=C double bond seems to be very likely an in situ formed peracid generated by Os-catalysis from O2/aldehyde. Additional investigations concerning the cleavage of oleic acid and methyl oleate with in situ formed performic acid from H2O2/formic acid corroborate this assumption. [source]

Diradical-Promoted Two-Carbon Ring-Expansion Reactions by Thermal Isomerization: Synthesis of Functionalized Macrocyclic Ketones

HELVETICA CHIMICA ACTA, Issue 7 2004
Georg Rüedi
A new method for the smooth and highly efficient preparation of functionalized macrocyclic ketones has been developed. Pyrolysis of medium- and large-ring 3-vinylcycloalkanones by dynamic gas-phase thermo-isomerization (DGPTI) at 600,630° yielded, under insertion of a previously attached vinyl side chain by means of a 1,3-C shift, the corresponding ,,, -unsaturated cycloalkanones. The yield of the two-carbon ring-expanded ketones greatly depended on the relative ring strains of substrate and product (5,87%, cf. Table,5). The formation of minor amounts of one-carbon ring-expanded cycloalkenes (<10%) can be ascribed to a subsequent decarbonylation step. A reaction mechanism involving initial cleavage of the weakest single bond in the molecule has been established (cf. Scheme,6). Recombination within the generated diradical intermediate in terminal vinylogous position led to the observed products, while reclosure gave recovered starting material. Substituents on the vinyl moiety were transferred locospecifically into the ring-expanded products. An isopropenyl group did not significantly affect the isomerization process, whereas substrates bearing a prop-1-enyl group in , -position enabled competing intramolecular H-abstraction reactions, leading to acyclic dienones (cf. Schemes,9,11). DGPTI of the 13-membered analogue directly yielded 4-muscenone, which, upon hydrogenation, led to the valuable musk odorant (±)-muscone. Increasing the steric hindrance on the vinyl moiety gave rise to diminishing amounts of the desired ,,, -unsaturated cycloalkanones. This novel two-carbon ring-expansion protocol was also successfully applied to 3-ethynylcycloalkanones, giving rise to the corresponding ring-expanded cyclic allenes (cf. Scheme,13). [source]

Atmospheric chemistry of isopropyl formate and tert -butyl formate

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 8 2010
Andre Silva Pimentel
Formates are produced in the atmosphere as a result of the oxidation of a number of species, notably dialkyl ethers and vinyl ethers. This work describes experiments to define the oxidation mechanisms of isopropyl formate, HC(O)OCH(CH3)2, and tert -butyl formate, HC(O)OC(CH3)3. Product distributions are reported from both Cl- and OH-initiated oxidation, and reaction mechanisms are proposed to account for the observed products. The proposed mechanisms include examples of the ,-ester rearrangement reaction, novel isomerization pathways, and chemically activated intermediates. The atmospheric oxidation of isopropyl formate by OH radicals gives the following products (molar yields): acetic formic anhydride (43%), acetone (43%), and HCOOH (15,20%). The OH radical initiated oxidation of tert -butyl formate gives acetone, formaldehyde, and CO2 as major products. IR absorption cross sections were derived for two acylperoxy nitrates derived from the title compounds. Rate coefficients are derived for the kinetics of the reactions of isopropyl formate with OH (2.4 ± 0.6) × 10,12, and with Cl (1.75 ± 0.35) × 10,11, and for tert -butyl formate with Cl (1.45 ± 0.30) × 10,11 cm3 molecule,1 s,1. Simple group additivity rules fail to explain the observed distribution of sites of H-atom abstraction for simple formates. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 479,498, 2010 [source]

Modeling the Photochemistry of the Reference Phototoxic Drug Lomefloxacin by Steady-State and Time-Resolved Experiments, and DFT and Post-HF Calculations

CHEMISTRY - A EUROPEAN JOURNAL, Issue 2 2008
Mauro Freccero Prof.
Abstract The irradiation in water of 1-ethyl-6,8-difluoro-7(3-methylpiperazino)3-quinolone-2-carboxylic acid (lomefloxacin), a bactericidal agent whose use is limited by its serious phototoxicity (and photomutagenicity in the mouse), leads to formation of the aryl cation in position eight that inserts into the 1-ethyl chain. Trapping of the cation was examined and it was found that chloride and bromide straightforwardly add in position eight, but with iodide and with pyrrole the 1-(2-iodoethyl) and the 1-[2-(2-pyrrolyl)ethyl] derivatives are formed. Flash photolysis reveals the triplet of lomefloxacin, a short-lived species (,max=370,nm, ,=40,ns) that generates the triplet cation (,max=480,nm, ,,120,ns). The last intermediate is quenched both by halides and by pyrrole. DFT and post-HF methods have shown that the triplet is the lowest state of the cation (,GST=13.3,kcal,mol,1) and intersystem crossing (ISC) to the singlet has no role because a less endothermic process occurs, that is, intramolecular hydrogen abstraction from the N -ethyl chain (9.2,kcal,mol,1) that finally leads to cyclization. The halides form weak complexes with the triplet cation (kq from 4.9×108 for Cl, to 7.0×109,m,1,s,1 for I,). With Cl, and Br, ISC occurs in the complex along with C8X bond formation. However, this latter process is slow with bulky iodide and with neutral pyrrole, and in these cases moderately endothermic electron transfer (ca. 7,kcal,mol,1) yielding the 8-quinolinyl radical occurs. Hydrogen exchange leads to a new radical on the 1-ethyl chain and to the observed products. These findings suggest that the mutagenic activity of the DNA-intercalated drug involves attack of the photogenerated cation to the heterocyclic bases. [source]