Acid-base reactions induction

Proton acid-base reactions are not particularly sensitive to stoic compression, and hence provide a good measure of inductive effects. For acid-base character, three sets of reference reactions can be used. The easiest of these to perform experimentally requires an analogy be drawn between the relative pK values of a series of protonated annelated pyridines and the pK values of the analogous isoelectronic benzene. The second is a direct measure of the kinetic acidity of the a- and P-sites on a soies of annelated benzenes. The third is a related direct assessment of kinetic acidity by protodetritiation. 

We begin our study of mechanisms in the context of acid-base chemistry in Chapter 3. Acid-base reactions are fundamental to organic reactions, and they lend themselves to introducing several important topics that students need early in the course (1) curved arrow notation for illustrating mechanisms, (2) the relationship between free-energy changes and equilibrium constants, and (3) the importance of inductive and resonance effects and of solvent effects. 

Applying p/C Values in Organic Acid-Base Reactions 3. EFFECT QF STRUCTURE QN ACIDITY Effect of Periodic Trends on Acidity and Basicity Effect of Resonance on Acidity and Basicity Inductive Effects Effect of Hybridization on Acidity... 

Methyl ketones are degraded to the next lower carboxylic acid by reaction with hypochlorite or hypobromite ions. The initial step in these reactions involves base-catalyzed halogenation. The a-haloketones are more reactive than their precursors, and rapid halogenation to the trihalo compound results. Trihalomethyl ketones are susceptible to alkaline cleavage because of the inductive stabilization provided by the halogen atoms. 

Based on inductive arguments, would you expect boron trifluoride or trimethylboron to be the stronger acid in reaction with NH3 Is this the same order expected for reaction with the bulky bases in the preceding example ... 

The catalytic properties of these reduced species have been actively studied by Gillard and co-workers. Among other things, they have shown that H2 also initiates Delepine s reaction of [RhClj] ", that Oj dramatically impedes the catalyst, and that halide substitution at trans-[Rhpy4Cl2] (equation 167) is also catalyzed by primary and secondary alcohols. Consistent with the pseudo acid-base equilibrium (equation 164), the rate of catalyzed halide substitution is pH dependent, with little catalytic activity occurring in acidic solutions. There is an induction period for the reaction (the more alcohol in the solution the shorter the period), suggesting that deoxygenation of the solution must occur before the reduced catalyst can be effective. 

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