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Essential Organic Chemistry Paula Y. Bruice Second Edition
Essential Organic Chemistry Paula Y. Bruice Second Edition

Essential Organic Chemistry

Paula Y. Bruice Second Edition

Essential Organic Chemistry Paula Y. Bruice Second Edition

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Delocalized Electrons and Their Effect on Stability, Reactivity, and pK a

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-

other. Rather, it indicates that the actual structure lies somewhere between the struc- tures of the resonance contributors. Resonance structures are merely a convenient way

to show the

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 structure—the rhinoceros—looks like. Resonance contributors, like unicorns and dragons, are imaginary, not real. Only the resonance hybrid, like the rhinoceros, is real.

p electrons; they do not depict any real electron distribution.

they do not depict any real electron distribution. unicorn resonance contributor dragon resonance contributor
they do not depict any real electron distribution. unicorn resonance contributor dragon resonance contributor

unicorn resonance contributor

dragon resonance contributor

unicorn resonance contributor dragon resonance contributor rhinoceros resonance hybrid Electron delocalization is shown

rhinoceros

resonance hybrid

Electron delocalization is shown by

. Equilibrium is shown by two arrows pointing in opposite directions ( ).

double-headed arrows ( · )

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 sp 2 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

p electrons

little or no overlap with the other adjacent p orbital. Therefore, the eight

are not delocalized over the entire cyclooctatetraene ring, and its carbon–carbon bonds

do not all have the same length.

no overlap
no overlap

cyclooctatetraene

3-D Molecule:

Cyclooctatetraene

183

Delocalized Electrons and Their Effect on Stability, Reactivity, and pK a

4 HOW TO DRAW RESONANCE CONTRIBUTORS

We have seen that an organic compound with delocalized electrons is generally repre-

p electrons are

present in the molecule. For example, nitroethane is represented as having a nitrogen– oxygen double bond and a nitrogen–oxygen single bond.

sented as a structure with localized electrons to let us know how many

CH

O + N 3 CH 2 − O nitroethane
O
+
N
3 CH 2
O
nitroethane

However, the two nitrogen–oxygen bonds in nitroethane are actually identical; they each have the same bond length. A more accurate description of the molecule’s struc- ture is obtained by drawing the two resonance contributors. Both resonance contribu- tors show the compound with a nitrogen–oxygen double bond and a nitrogen–oxygen 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.

Delocalized electrons result from a p orbital overlapping the p orbitals of more than one adjacent atom.

− O O + + CH 3 CH 2 N CH 3 CH 2 N
O
O
+
+
CH 3 CH 2
N
CH 3 CH 2
N
O
O
resonance contributor
resonance contributor

The resonance hybrid, in contrast, shows that the p orbital of nitrogen overlaps the

p electrons are shared

by three atoms. The resonance hybrid also shows that the two nitrogen–oxygen bonds are identical and that the negative charge is shared equally by both oxygen atoms. Thus, we need to visualize and mentally average both resonance contributors to appre- ciate what the actual molecule—the resonance hybrid—looks like.

p orbital of each oxygen. In other words, it shows that the two

d− O + CH N 3 CH 2 O d− resonance hybrid
d−
O
+
CH
N
3 CH 2
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- cule—it becomes our first resonance contributor—and then we move the electrons, following the rules listed below, to generate the next resonance contributor.

To draw resonance contributors, move only P electrons or lone-pair electrons toward an sp 2 carbon.

184

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 of zero. (A net charge of zero does not necessarily mean that there is no charge on any of the atoms: a molecule with a positive charge on one atom and a nega- tive charge on another atom has a net charge of zero.)

Notice, as you study the following resonance contributors and practice drawing

p electrons or lone pairs) are always moved toward an

sp 2 carbon. Remember that an sp 2 carbon is either a positively charged carbon or a

them yourself, that the electrons (

Delocalized Electrons and Their Effect on Stability, Reactivity, and pK a

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 sp 2 carbon. A curved arrow can help you de- cide how to draw the second contributor. Remember that the tail of the curved arrow 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 sp 2 carbon + + CH 3 CH CH CHCH 3 CH 3 CH
an sp 2 carbon
+
+
CH 3 CH
CH
CHCH
3 CH 3 CH
CH
CHCH 3
resonance contributors
d +
d +
CH 3 CH
CH
CHCH 3

resonance hybrid

Let’s compare this carbocation with a similar compound in which all the electrons are

localized. The

carbon they would move toward is an sp 3 carbon; sp 3 carbons cannot accept electrons.

p electrons in the compound shown below cannot move because the

an sp 3 carbon cannot accept electrons + CH 2 CH CH 2 CHCH 3
an sp 3 carbon cannot
accept electrons
+
CH 2
CH
CH 2 CHCH 3

localized electrons

Tutorial: electrons + CH 2 CH CH 2 CHCH 3 localized electrons Drawing resonance contributors Tutorial: Localized

Drawing resonance contributors

Tutorial: localized electrons Tutorial: Drawing resonance contributors Localized and delocalized electrons In the next example, p

Localized and delocalized 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 sp 2
nance hybrid shows that the positive charge is shared by three carbons.
an sp 2 carbon
+
+
+
CH 3 CH
CH
CH
CH
CH 2
CH 3 CH
CH
CH
CH
CH
2 CH
3 CH
CH
CH
CH
resonance contributors
d +
d +
d +
CH 3 CH
CH
CH
CH
CH 2

resonance hybrid

CH 2

The resonance contributor for the next compound is obtained by moving lone-pair

electrons toward an sp 2 carbon. The sp 2 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 sp 3 carbon. lone-pair O
not delocalized because they would have to move toward an sp 3 carbon.
lone-pair
O
electrons
O −
O
C
C
C
+
R NH 2
R NH 2
R CH 2
NH 2
resonance contributors
an sp 2 carbon
d
O
an sp 3 carbon
cannot accept
electrons
C
d
+
R
NH 2

resonance hybrid

185

Delocalized Electrons and Their Effect on Stability, Reactivity, and pK a

For additional practice drawing resonance contributors, see Special Topics II in the Study Guide and Solutions Manual.

p electrons toward

an sp 2 carbon. Notice that the electrons move toward (not away from) the most elec-

The following resonance contributors are obtained by moving

tronegative atom (the oxygen). − O O CH 3 C CH CH 2 CH CH
tronegative atom (the oxygen).
O
O
CH 3 C
CH
CH 2
CH
CH
3 C
d
O
d +
CH 3 C
CH
CH 2

+

CH 2

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).

− + CH 2 CH OCH 3 CH 2 CH
+
CH
2 CH
OCH 3
CH
2 CH

OCH 3

Radicals can also have delocalized electrons. The resonance contributors are ob- tained by moving single electrons toward sp 2 carbons.

CH 3 CH CH CH 2 CH 3 CH CH CH 3
CH 3
CH
CH
CH 2
CH
3 CH
CH
CH 3

resonance contributors

d d CH 3 CH CH CH 2 resonance hybrid
d
d
CH 3
CH
CH
CH 2
resonance hybrid
PEPTIDE BONDS Every third bond in a protein is a peptide bond. A resonance contributor
PEPTIDE BONDS
Every third bond in a protein is a peptide bond. A
resonance contributor can be drawn for a peptide
bond by moving the lone pair on nitrogen toward
the sp 2 carbon.
Because of the partial double bond character of the peptide
bond, the carbon and nitrogen atoms and the two atoms bond-
ed to each are held rigidly in a plane, as represented below by
the blue and green boxes. This planarity affects the way
proteins fold, so it has important implications for the three-di-
mensional shape of these biological molecules.
O
R
O
R
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 pK a

PROBLEM 1

 

Which of the following compounds have delocalized electrons?

 

a.

NH 2

NH 2

e.

N

N

 

H

b.

 
CH 2 NH 2 f.

CH 2 NH 2

f.

CH 3 CH CHCH CHC

H

2

c.

O

O

g.

O «

O

«

 

d.

CH 2 CHCH 2 CH CH 2

h. CH 3 CH 2 NHCH 2 CH

CH

2

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- nance hybrid; and the more it contributes to the structure of the resonance hybrid, the more similar the contributor is to the real molecule. The examples that follow illus- trate these points. 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 charge—not a comfortable situation for an electronega- tive atom—and 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
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
O
O
C
C
R O
R
O
C
D

a carboxylate ion

The greater the predicted stability of the resonance contributor, the more it contributes to the structure of the resonance hybrid.

187