Acid-catalyzed reactions proton exchange

A similar conclusion was reached" for the isohypophosphite anion (P(ni)-O-P(V), 02P(H)-0-P0p. In the acid-catalyzed reaction, as with other phosphates, reaction rates are higher for more highly protonated species. Semi-quantitative studies of the exchange of this anion with orthophosphate show that pyrophosphate is not formed . 

The specific acid-catalyzed reaction behaves in many respects like the water reaction. Thus, unusually large negative entropies of activation are found for all but those substrates which react by the acylium ion path (Schaleger and Long, 1963). At least two water molecules are involved in the transition state, the presence of at least five exchangeable hydrogens in the transition state, is deduced from solvent isotope effects in mixed water-heavy water (Salomaa et al., 1964). From the dependence of both acid-catalyzed exchange and hydrolysis in concentrated sulfuric acid on the activity of water. Lane (1964) concluded that two water molecules must be involved in the transition state. Except for the extra proton, the transition states for the acid-catalyzed and water reactions are very probably similar. 

The hydration reaction has been extensively studied because it is the mechanistic prototype for many reactions at carbonyl centers that involve more complex molecules. For acetaldehyde, the half-life of the exchange reaction is on the order of one minute under neutral conditions but is considerably faster in acidic or basic media. The second-order rate constant for acid-catalyzed hydration of acetaldehyde is on the order of 500 M s . Acid catalysis involves either protonation or hydrogen bonding at the carbonyl oxygen. 

Propylene glycol, glycolysis of polyurethanes with, 572 Propylene oxide (PO), glycolysis of polyurethanes with, 572-573 Propylene oxide (PO) polyols, 211, 223 Proton exchange membrane fuel cells (PEMFCs), 272-273 Proton NMR integrations, 386. See also H NMR spectroscopy Protonic acids, reactions catalyzed by, 67-68... 

The observation of a primary solvent deuterium isotope effect (kH/fa>) = 2-4 on the specific acid-catalyzed hydrolysis of vinyl ethers provides evidence for reaction by rate-determining protonation of the alkene.69 Values of kHikD 1 are expected if alkene hydration proceeds by rate-determining addition of solvent to an oxocarbenium ion intermediate, since there is no motion of a solvent hydron at the transition state for this step. However, in the latter case, determination of the solvent isotope effect on the reaction of the fully protonated substrate is complicated by the competing exchange of deuterium from solvent into substrate (see above). 

Hirschler and Hudson (36/6), however, favor the opinion that Bronsted sites are exclusively responsible for the activity of silica-alumina. In studying the adsorption of perylene and of triphenylmethane, they concluded that carbonium ions are not formed by a hydride abstraction mechanism as claimed by Leftin (362). Instead, triphenylmethane is oxidized by chemisorbed oxygen to triphenylcarbinol in a photo-catalyzed reaction, followed by reaction with a Bronsted acid giving water and a triphenylmethyl carbonium ion. After treatment with anhydrous ammonia, the organic compound was recovered by extraction as triphenylcarbinol. About thirteen molecules of ammonia per assumed Lewis site were required to poison the chemisorption of trityl ions. The authors explain the selective inhibition of certain catalyzed reactions by alkali by assuming that only certain of the acidic protons will ion-exchange with alkali ions. 

A variety of protonic and Lewis acids initiate the cationic polymerization of lactams [Bertalan et al., 1988a,b Kubisa, 1996 Kubisa and Penczek, 1999 Puffr and Sebenda, 1986 Sebenda, 1988]. The reaction follows the mechanism of acid-catalyzed nucleophilic substitution reactions of amides. More specibcally, polymerization follows an activated monomer mechanism. Initiation occurs by nucleophilic attack of monomer on protonated (activated) monomer (XXIV) to form an ammonium salt (XXV) that subsequently undergoes proton exchange with monomer to yield XXVI and protonated monomer. The conversion of XXIV to XXV involves several steps—attachment of nitrogen to C+, proton transfer from... 

This analogy is plausible on energetic grounds, since the decreased base strength of the proton acceptor should be approximately compensated by the increased acid strength of the proton donor. In view of the different species involved, however, it is reasonable to expect appreciable differences in the configurations of the transition states and hence in the activation barriers for the two paths. Therefore, the failure to observe an acid-catalyzed exchange reaction cannot be taken as conclusive evidence in favor of the alternative (hydride ion) mechanism. 

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