6.16.

Metal ions such as Zn2+ , Ni2+ , and Cu2+ enhance the rate of general base- 625
catalyzed enolization of 2-acetylpyridine by a several orders of magnitude.
PROBLEMS
Account for this effect.
6.17. The C(2) equatorial hydrogen is selectively removed when 1,3-dithianes are
deprotonated. Furthermore, if the resulting carbanion is protonated, there is a
strong preference for equatorial protonation, even though it leads to the less stable
axial orientation for the 2-substituent. Discuss the relevance of these observations
to the structure of the sulfur-stabilized carbanion in MO terminology.

Hax
Hax – Hax
base CH3 *H+ CH3 S
CH3 S S *Heq
Heq S S
S CH3 CH3
CH3

6.18. a. It is found that when 2-methyl-2-butene is converted to a dianion, it first

gives the 2-methylbutadiene dianion 18-A, but this is converted to the more
stable anion 18-B, which can be referred to as a “methyltrimethylenemethane
dianion. Does simple HMO theory offer an explanation for this result?

H– H
CH3 CH3 H
H CH3
CH3 H –
CH3 –
– H H H
H H
18-A 18-B

b. The HMO diagrams of several conceivable dianions that might be formed

from double deprotonation of 2-methyl-1,5-hexadiene are given. On the basis
of these diagrams, which dianion would be expected to be most stable?

–
– 2–
– –
2 – CH3
CH3
C D E F
α – 1.8β α – 1.9β
α – 1.4β α – 1.7β α – 1.3β α – 1.2β
α–β α – 0.5β
α α
α α + 0.5β
α+β α + 1.2β
α + 1.4β α + 1.3β
α + 1.8β α + 1.9β
α + 1.7β

6.19. Which of the two possible structures for the dimer of methylketene is in best
accord with the observed pK of 2.8? Explain.

CH3CH CH3 CH3 OH

O
O O CH3