Page 718 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

700 O CCH 3 c) N
2
a) N NH
CHAPTER 7
Addition, Condensation O CCH 3
2
and Substitution
Reactions of Carbonyl d)
Compounds O CH CH CO H
2
2
2
2
b)
Cl O 2 C(CH 2 ) 3 N(CH 3 ) 2
OH
(a) (b)
log k obs
2
–1,0
1

log k obsd (min –1 ) –1 –2,0
0

–3,0
–2
–3
–4,0
–4
2 4 6 8 10 12
pH
–5
0 2 4 6 8 10
pH

(c) (d)

36
2 32
log k obsd (min –1 ) –2 0 k obs 24
28

20

–4 16
12
8
0 2 4 6 8 10 12
pH 4
0
8.0 8.4 8.8 9.2 9.6 10.0 10.4 10.4
pH

Fig. 7.P5. Reproduced from problem references 5 a–d by permission of the American Chemical Society.

7.6 Derive the general expression for the observed rate of hydrolysis of
compound 6-A as a function of pH. Assume that intramolecular general acid
catalysis outweighs specific acid catalysis in the region between pH 3 and pH 9.