691889-72-2Relevant academic research and scientific papers
Cyclic mechanism in the trapping of carbonyl oxides with alcohols and carboxylic acids
Hanaki, Hiroshi,Fukatsu, Yuta,Harada, Masaki,Sawaki, Yasuhiko
, p. 2559 - 2561 (2004)
The reaction of diphenylcarbonyl oxide with alcohols and carboxylic acids, which has been classified as a nucleophilic trapping, is shown to be in the reactivity order: AcOH?MeOHCF3CH2OHEtOH?t-BuOH. A laser-flash spectroscopy indicated that the reaction of carboxylic acids is very fast, that is, one-tenth of the diffusion rate. These results suggest that the hydroxyl compounds react as an acid and a nucleophile at the same time and the major reaction is via the seven- and five-membered cyclic mechanism for RCO2H and ROH, respectively.
Kinetics, mechanism, and products of the reaction of diphenylcarbonyl oxide with carboxylic acids
Nazarov, A. M.,Khursan, S. L.,Chainikova, E. M.,Komissarov, V. D.
, p. 608 - 615 (2007/10/03)
The kinetics of the reactions of acetic, benzoic, formic, oxalic, malic, tartaric, trifluoroacetic, and hydrochloric acids with diphenylcarbonyl oxide Ph2COO was studied. The carbonyl oxide Ph2COO was generated by flash photolysis of diphenyldiazomethane Ph2CN2 in solutions of acetonitrile and benzene at 295 K. The apparent rate constants of the reaction range from 4.6 108 for (COOH)2 in MeCN to 7.5 109 L mol-1 s-1 for acetic acid in a benzene solution. The reaction mechanism was proposed, according to which at the first stage the carbonyl oxide is reversibly solvated by the solvent. Then the solvated carbonyl oxide reacts with the acid molecule by the mechanism of insertion at the O-H bond.
