Essential Organic Chemistry

Bruice
Second Editon
Essential Organic Chemistry

Paula Y. Bruice
Second Edition
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 Delocalized Electrons and Their Effect on Stability, Reactivity, and pKa

Resonance contributors are shown with a double-headed arrow between them. The
double-headed arrow does not mean that the structures are in equilibrium with one an-
Electron delocalization is shown by
other. Rather, it indicates that the actual structure lies somewhere between the struc- double-headed arrows ( ) .
tures of the resonance contributors. Resonance structures are merely a convenient way Equilibrium is shown by two arrows
to show the p electrons; they do not depict any real electron distribution. pointing in opposite directions ( ).
The following analogy illustrates the difference between resonance contributors
and the resonance hybrid. Imagine that you are trying to describe to a friend what a
rhinoceros looks like. You might tell your friend that a rhinoceros looks like a cross
between a unicorn and a dragon. Like resonance contributors, the unicorn and the
dragon do not really exist. Furthermore, like resonance contributors, they are not in
equilibrium: a rhinoceros does not change back and forth between the two forms,
looking like a unicorn one instant and a dragon the next. The unicorn and the dragon
are simply ways to represent what the actual structurethe rhinoceroslooks like.
Resonance contributors, like unicorns and dragons, are imaginary, not real. Only the
resonance hybrid, like the rhinoceros, is real.

unicorn dragon
resonance contributor resonance contributor

rhinoceros
resonance hybrid

Electron delocalization is most effective if all the atoms sharing the delocalized
electrons lie in or close to the same plane, so that their p orbitals can maximally over-
lap. For example, cyclooctatetraene is not planar; its sp2 carbons have bond angles of
120, whereas a planar eight-member ring would have bond angles of 135. Because
the ring is not planar, a p orbital can overlap with one adjacent p orbital, but it can have
little or no overlap with the other adjacent p orbital. Therefore, the eight p electrons
are not delocalized over the entire cyclooctatetraene ring, and its carboncarbon bonds
do not all have the same length.

3-D Molecule:
Cyclooctatetraene

no overlap

cyclooctatetraene

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 Delocalized Electrons and Their Effect on Stability, Reactivity, and pKa

4 HOW TO DRAW RESONANCE CONTRIBUTORS

We have seen that an organic compound with delocalized electrons is generally repre-
sented as a structure with localized electrons to let us know how many p electrons are
present in the molecule. For example, nitroethane is represented as having a nitrogen
oxygen double bond and a nitrogenoxygen single bond.
O
+
CH3CH2 N

O
nitroethane

However, the two nitrogenoxygen bonds in nitroethane are actually identical; they
each have the same bond length. A more accurate description of the molecules struc-
ture is obtained by drawing the two resonance contributors. Both resonance contribu-
tors show the compound with a nitrogenoxygen double bond and a nitrogenoxygen
single bond, but they indicate that the electrons are delocalized by depicting the dou-
ble bond in one contributor as a single bond in the other.

O O
+ +
CH3CH2 N CH3CH2 N

O O
resonance contributor resonance contributor

The resonance hybrid, in contrast, shows that the p orbital of nitrogen overlaps the
p orbital of each oxygen. In other words, it shows that the two p electrons are shared
by three atoms. The resonance hybrid also shows that the two nitrogenoxygen bonds
Delocalized electrons result from a p
are identical and that the negative charge is shared equally by both oxygen atoms.
orbital overlapping the p orbitals of Thus, we need to visualize and mentally average both resonance contributors to appre-
more than one adjacent atom. ciate what the actual moleculethe resonance hybridlooks like.
d
O
+
CH3CH2 N
O
d
resonance hybrid

Rules for Drawing Resonance Contributors

To draw a set of resonance contributors, we first draw a Lewis structure for the mole-
culeit becomes our first resonance contributorand then we move the electrons,
following the rules listed below, to generate the next resonance contributor.
1. Only electrons move. Atoms never move.
2. Only p electrons (electrons in p bonds) and nonbonding electrons can move;
s electrons never move.
3. The total number of electrons in the molecule does not change. Therefore, each
of the resonance contributors for a particular compound must have the same net
charge. If one has a net charge of zero, all the others must also have net charges
To draw resonance contributors, move only
of zero. (A net charge of zero does not necessarily mean that there is no charge
P electrons or lone-pair electrons toward on any of the atoms: a molecule with a positive charge on one atom and a nega-
an sp2 carbon. tive charge on another atom has a net charge of zero.)
Notice, as you study the following resonance contributors and practice drawing
them yourself, that the electrons (p electrons or lone pairs) are always moved toward an
sp2 carbon. Remember that an sp2 carbon is either a positively charged carbon or a

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 Delocalized Electrons and Their Effect on Stability, Reactivity, and pKa

double-bonded carbon. Electrons cannot be moved toward an sp 3 carbon because

an sp 3 carbon has a complete octet so it cannot accommodate any more elec-
trons.
The following carbocation has delocalized electrons. To draw its resonance contrib-
utor, we move the p electrons toward an sp2 carbon. A curved arrow can help you de- Tutorial:
cide how to draw the second contributor. Remember that the tail of the curved arrow Drawing resonance contributors
shows where the electrons start from and the head of the arrow shows where the elec-
trons are going. The resonance hybrid shows that the positive charge is shared by two
carbons.

an sp2 carbon

+ +
CH3CH CH CHCH3 CH3CH CH CHCH3
resonance contributors

d+ d+
CH3CH CH CHCH3
resonance hybrid

Lets compare this carbocation with a similar compound in which all the electrons are Tutorial:
Localized and delocalized
localized. The p electrons in the compound shown below cannot move because the electrons
carbon they would move toward is an sp3 carbon; sp3 carbons cannot accept electrons.

an sp3 carbon cannot

accept electrons

+
CH2 CH CH2CHCH3
localized electrons

In the next example, p electrons again move toward a positive charge. The reso-
nance hybrid shows that the positive charge is shared by three carbons.

an sp2 carbon

+ + +
CH3CH CH CH CH CH2 CH3CH CH CH CH CH2 CH3CH CH CH CH CH2
resonance contributors

d+ d+ d+
CH3CH CH CH CH CH2
resonance hybrid

The resonance contributor for the next compound is obtained by moving lone-pair
electrons toward an sp2 carbon. The sp2 carbon can accommodate the new electrons
by breaking a p bond. The lone-pair electrons in the example, on the right below, are
not delocalized because they would have to move toward an sp3 carbon.

lone-pair
O electrons O O
C C + C
R NH2 R NH2 R CH2 NH2
an sp2 carbon resonance contributors
an sp3 carbon
d cannot accept
O electrons
C d+
R NH2
resonance hybrid

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 Delocalized Electrons and Their Effect on Stability, Reactivity, and pKa

The following resonance contributors are obtained by moving p electrons toward

an sp2 carbon. Notice that the electrons move toward (not away from) the most elec-
tronegative atom (the oxygen).

O O
+
For additional practice drawing resonance CH3C CH CH2 CH3C CH CH2
contributors, see Special Topics II in the
d
Study Guide and Solutions Manual.
O
d+
CH3C CH CH2
resonance hybrid

The only time you move electrons away from the most electronegative atom in
order to arrive at a resonance contributor is when that is the only way electrons can be
moved. In other words, movement of electrons away from the most electronegative
atom is better than no movement at all, because electron delocalization makes a mole-
cule more stable (as you will see in Section 5).
+
CH2 CH OCH3 CH2 CH OCH3

Radicals can also have delocalized electrons. The resonance contributors are ob-
tained by moving single electrons toward sp2 carbons.

CH3 CH CH CH2 CH3 CH CH CH3

resonance contributors
d d
CH3 CH CH CH2
resonance hybrid

PEPTIDE BONDS
Every third bond in a protein is a peptide bond. A Because of the partial double bond character of the peptide
resonance contributor can be drawn for a peptide bond, the carbon and nitrogen atoms and the two atoms bond-
bond by moving the lone pair on nitrogen toward ed to each are held rigidly in a plane, as represented below by
the sp2 carbon. the blue and green boxes. This planarity affects the way
proteins fold, so it has important implications for the three-di-
O R O R mensional shape of these biological molecules.

C CH C +
CH
CH N CH N
R H R H
peptide bond

H O R H O R H O R H O
N C CH N C CH N C CH N C
CH N C CH N C CH N C CH
R H O R H O R H O R
a segment of a protein

186
 Delocalized Electrons and Their Effect on Stability, Reactivity, and pKa

PROBLEM 1
Which of the following compounds have delocalized electrons?
a. e.
NH2
N
H
b.
CH2NH2 f. CH3CH CHCH CHCH2

c. g.

O O

d. CH2 CHCH2CH CH2 h. CH3CH2NHCH2CH CH2

PROBLEM 2
For the compounds in Problem 1 that have delocalized electrons, draw their resonance
contributors.

5 THE PREDICTED STABILITIES OF

RESONANCE CONTRIBUTORS
All resonance contributors do not necessarily contribute equally to the resonance hy-
brid. The degree to which each resonance contributor contributes depends on its pre-
dicted stability. Because resonance contributors are not real, their stabilities cannot be
measured. Therefore, the stabilities of resonance contributors have to be predicted
based on molecular features found in real molecules. The greater the predicted stabil-
ity of the resonance contributor, the more it contributes to the structure of the reso-
The greater the predicted stability of the
nance hybrid; and the more it contributes to the structure of the resonance hybrid, the resonance contributor, the more it
more similar the contributor is to the real molecule. The examples that follow illus- contributes to the structure of the
trate these points. resonance hybrid.
The two resonance contributors for a carboxylic acid are shown below, labeled A
and B. Structure B has two features that make it less stable than structure A: one of its
oxygen atoms has a positive chargenot a comfortable situation for an electronega-
tive atomand the structure has separated charges. A molecule with separated
charges has a positive charge and a negative charge that can be neutralized by the
movement of electrons. Resonance contributors with separated charges are relatively
unstable (relatively high in energy) because energy is required to keep the opposite
charges separated. Structure A, therefore, is predicted to be more stable than structure
B. Consequently, A makes a greater contribution to the resonance hybrid, so the reso-
nance hybrid looks more like A than like B.

O O separated
charges
C C +
R OH R OH
A B
a carboxylic acid

The two resonance contributors for a carboxylate ion are shown next.

O O
C C
R O R O
C D
a carboxylate ion

187