CEM2008S 2012 Tutorial 2 ANSWERS

1.

In each of the following, draw the structures which are the immediate outcome of the electron-flow process indicated by the curly arrows: (a)

The strength of the carboxylic acid is related to the stability of the carboxylate which is the conjugate base formed when the acid loses its proton. This carboxylate is stabilized by electron-withdrawing groups on the adjacent carbon: the electronwithdrawing effect increases with increasing number of Cl groups on C-2.

(b)

(c)

3. (d)
O O O O

Consider the aromatic compounds 1, 2 and 3 shown below, and answer the questions which follow:
H H

H H

H H

EtO

H EtOH H

(e)

1 pKa = 40

2 pKa = 33

3 pKa = 23

a. Sketch out the expected reactions between a very strong base (B ) and each of the structures, showing the structure of the conjugate base formed in each case. (Draw resonance forms where appropriate.) 2. Draw the full reaction of acetic acid with water (shown below), clearly label the acid, base, conjugate acid and conjugate base, and then provide an explanation for the change in pKa with increasing number of chlorine substituents on C-2:

H H

etc. etc.

b. With reference to your answer to (a) above, identify which of the compounds is the stronger acid, and explain why. The strength of the acids is in the order 3 > 2 > 1. The acid strength is related to the stability of the conjugate bases formed in the reaction: these are stabilized by resonance in the aromatic systems, with planar fused ring system in 1 offering the most resonance forms, hence the greatest stabilization. 4. (a) Draw the resonance form of ethyl acetate that results from the electron-flow indicated below: 5.

(c) On the basis of your answers to (a) and (b) above, predict which of the two compounds in (b) is the weaker acid (has higher pKa) and suggest reasons for this. The second one (ethyl acetate) is the weaker carbon acid. The strength of the acid is related to the stability of the conjugate base which in turn relates to the extent to which the anion is stabilized by resonance as shown. In the case of ethyl acetate, the carbonyl carbon is less positive, as discussed in (a) above, so that the donation of the anion towards this is less likely than in the ketone.

Using Newman diagrams, draw the three possible staggered conformations of the structure shown below, and identify which is the most and which the least stable.

(b) Draw the anions formed, and resonance structures of these, in these reactions involving a strong base: