826 CHAPTER 18 • THE CHEMISTRY OF ARYL HALIDES, VINYLIC HALIDES, AND PHENOLS.

TRANSITION-METAL CATALYSIS

PROBLEM
18.2 Arrange the following compounds according to increasing rate of elimination with NaOC2H5
in C2H5OH. What is the product in each case?

$ ) $ ) $ ) $ )
Ph Ph Ph Br Ph Ph H Br

) $ ) $ ) $ ) $
CAC CAC CAC CAC
H Br H Ph H Cl H Ph
A B C D

LACK OF REACTIVITY OF VINYLIC AND

18.3 ARYL HALIDES UNDER S N 1 CONDITIONS
Recall that tertiary and some secondary alkyl halides undergo nucleophilic substitution and
elimination reactions by the SN1 and E1 mechanisms (Sec. 9.6). For example, tert-butyl bro-
mide undergoes a rapid solvolysis in ethanol to give both substitution and elimination products.

" " " $

CH3 CH3 CH3 H3C
H3C L C L Br3
2 H3C L C| 3 Br3
2 _ H3C L C L OC2H5 + 23
C A CH2 + HBr
C2H5OH

)
C2H5OH
" 2 55 °C " 2 " 2
CH3 CH3 CH3 H3C
(72%) (28%) (18.6)

Vinylic and aryl halides, however, are virtually inert to the conditions that promote SN1 or E1
reactions of alkyl halides. Certain vinylic halides can be forced to react by the SN1–E1 mech-
anism under extreme conditions, but such reactions are relatively uncommon.

"
CH3

H2C A C L Br + C2H5OH
55 °C
no reaction (18.7)

cL Br + C2H5OH
55 °C
no reaction (18.8)

To understand why vinylic and aryl halides are inert under SN1 conditions, consider what
would happen if they were to undergo the SN1 reaction. If a vinylic halide undergoes an SN1
reaction, it must ionize to form a vinylic cation.

$
R
|
R L C A CH2 3 Br 2 3_
) 2
C A CH2 (18.9)
3 Br 3
Further Exploration 18.1 a vinylic cation
2
Vinylic Cations

A vinylic cation is a carbocation in which the electron-deficient carbon is also part of a dou-
ble bond. An orbital diagram of a vinylic cation is shown in Fig. 18.2a. The electron-deficient
carbon is connected to two groups, the R group and the other carbon of the double bond.
Hence, the geometry at this carbon is linear (Sec. 1.3B) and the electron-deficient carbon is
therefore sp-hybridized. Notice that the vacant 2p orbital is not conjugated with the p-electron
system of the double bond; in order to be conjugated, it would have to be coplanar with the
double-bond p system. Vinylic cations are considerably less stable than alkyl carbocations be-
cause their sp hybridization has a higher energy than the sp2 hybridization of alkyl cations (the
 18.3 LACK OF REACTIVITY OF VINYLIC AND ARYL HALIDES UNDER S N 1 CONDITIONS 827

H
H
H2C C R
H H
2p orbitals of the H
double bond these three carbons
cannot become co-linear

H
H C empty
2p orbital
C empty sp2 orbital
R

sp-hybridized carbon

(a) vinylic cation (b) aryl cation

Figure 18.2 Lewis structures and corresponding orbital diagrams of vinylic and aryl cations. The thin gray lines
indicate orbital overlap. (a) A vinylic cation. In this cation, the empty 2p orbital of the cation (blue) is oriented at
right angles to the 2p orbitals of the p bond. The carbon with the empty 2p orbital is sp-hybridized. (b) Phenyl
cation, the simplest aryl cation. The electron-deficient carbon and the two adjacent carbons cannot become co-
linear. Consequently, the empty orbital (blue) is not a true 2p orbital; it has more s character than the empty orbital
in the vinylic cation.

same reason that alkynes are less stable than isomeric dienes), and because the electron-with-
drawing polar effect of the double bond discourages formation of positive charge at a vinylic
carbon. Hence, one reason that vinylic halides do not undergo the SN1 reaction is the instabil-
ity of the vinylic cations that would necessarily be involved as reactive intermediates.
The second reason that vinylic halides do not undergo the SN1 reaction is that carbon–halo-
gen bonds are stronger in vinylic halides than they are in alkyl halides. A vinylic
carbon–halogen bond involves an sp2 carbon orbital, whereas an alkyl carbon–halogen bond
involves an sp3 carbon orbital. Hence, a vinylic carbon–halogen bond has more s character.
Recall that bonds with more s character are stronger (Eq. 14.26, p. 664). Consequently, it takes
more energy to break the carbon–halogen bond of a vinylic halide. This additional energy is
reflected in a smaller rate of ionization.
SN1 reactions of aryl halides would involve aryl cations as reactive intermediates.

21 3
M |
Br
i i + 3 Br
_
12 3 (18.10)

phenyl cation
(an aryl cation)

An aryl cation is a carbocation in which the electron-deficient carbon is part of an aromatic

ring. An orbital diagram of an aryl cation is shown in Fig. 18.2b. Because the electron-defi-
cient carbon in an aryl cation is bonded to two groups, it prefers a linear geometry; but this
geometry is impossible, because it would introduce too much strain in the six-membered ring.
Consequently, the vacant orbital cannot become a 2p orbital, and must remain an sp2 orbital.
828 CHAPTER 18 • THE CHEMISTRY OF ARYL HALIDES, VINYLIC HALIDES, AND PHENOLS. TRANSITION-METAL CATALYSIS

Because an aryl cation is forced to assume a nonoptimal geometry and hybridization, it has a
very high energy. The electron-withdrawing polar effect of the ring double bonds also desta-
bilizes an aryl cation, just as a double bond destabilizes a vinylic cation. Thus, SN1 reactions
of aryl halides do not occur because they would require the formation of carbocation interme-
diates—aryl cations—with very high energy.
Note that an aryl cation is quite different from the cation formed in electrophilic aromatic substitu-
tion (Eq. 16.9a, p. 753), in which the carbocation intermediate is stabilized by resonance. In an aryl
cation, the empty orbital is not part of the ring p-electron system but is orthogonal (at right angles)
to it. Hence, this carbocation is not resonance-stabilized.
The first direct observation of an aryl cation (the phenyl cation, Eq. 18.10) was reported in 2000
by chemists at the Ruhr-Universität in Bochum, Germany, who trapped the cation at 4 K and ob-
served it spectroscopically. Thus, aryl cations are known species. However, they are far too unstable
to form from aryl halides under typical SN1 conditions.

PROBLEM
18.3 Within each series, arrange the compounds according to increasing rates of their reactions by
the SN1–E1 mechanism. Explain your reasoning.

" " "

(a) Br Br Br
cL C A CH2 0L CH L CH3 cL CH L CH3

A B C

"
(b) Cl
Cl
kL CH L CH3 kL Br

A B C

NUCLEOPHILIC AROMATIC SUBSTITUTION

18.4 REACTIONS OF ARYL HALIDES
Although aryl halides do not undergo nucleophilic substitution reactions by SN1 and SN2
mechanisms, aryl halides that have one or more nitro groups ortho or para to the halogen un-
dergo nucleophilic substitution reactions under relatively mild conditions.

O2N LvL F + K| CH3O_ O2N LvL OCH3 + K| F_

67 °C, 10 min
CH3OH
(18.11)

p-fluoronitrobenzene p-nitroanisole
(93% yield)

) )
NO2 NO2

O2N LvL Cl + 3 NH3 O2N LvL NH

2 2 + HCl
170 °C, 6 h
(pressure)
(18.12)

1-chloro-2,4-dinitrobenzene 2,4-dinitroaniline
(70% yield)