Oximates Br0nsted-type plots

A different type of solvent effect on reactivity was observed by Terrier and coworkers for the reaction of oximates with the bis(4-nitrophenyl) phenylphosphonate (BPNPPP) . As shown in Figure 7, the Br0nsted-type plot is bell-shaped, i.e. oximates with pTsTa > 9 exhibiting lower reactivity than more weakly basic oximates . ... 

FIGURE 7. Br0nsted-type plot for the reaction of the oximates with the bis(4-nitrophenyl) phenyl-phosphonate at 25 °C in aqueous solution. From Terrier et al, Chem. Commun., 600 (2003). Reproduced by permission of The Royal Society of Chemistry... 

FIGURE 3.2 Br0nsted plot for the dehydration of acetone hydrate in acetone, catalyzed by acid. The logarithm of the catalytic rate constant is plotted versus the negative of the dissociation constant of the acid. Points are shown for 32 carboxylic acids and 15 phenols. The point labeled 47 represents 2,4-dinitrophenol. Acids of other types (e.g., oximes) fell much further off the line (see Section 3.6.3). Source Bell and Higginson (1949) by permission of the Royal Society of London. 

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