CHAPTER 2—ACIDS AND BASES; FUNCTIONAL GROUPS

2-1
(a) 2.4 D = 4.8 x δ x 1.23 Å
δ = 0.41, or 41% of a positive charge on carbon and 41% of a negative charge on oxygen
(b) O O

C C
R R R R
A B
Resonance form A must be the major contributor. If B were the major contributor, the value of the charge
separation would be between 0.5 and 1.0, meaning >50% of a positive charge on C and >50% of a negative
charge on O. Even though B is "minor", it is quite significant, explaining in part the high polarity of the
C=O.
2-2
Both NH3 and NF3 have a pair of nonbonding electrons on the nitrogen. In NH3, the direction of
polarization of the N—H bonds is toward the nitrogen; thus, all three bond polarities and the lone pair
polarity reinforce each other. In NF3, on the other hand, the direction of polarization of the N—F bonds is
away from the nitrogen; the three bond polarities cancel the lone pair polarity, so the net result is a very
small molecular dipole moment.

• • • •
polarities reinforce; polarities oppose;
large dipole moment small dipole moment
(1.50) N N (0.20)
H H F F
H F
2-3 Some magnitudes of dipole moments are difficult to predict; however, the direction of the dipole
should be straightforward, in most cases. Actual values of molecular dipole moments are given in
parentheses. (Each halogen atom has three nonbonded electron pairs, not shown below.) The C—H is
usually considered nonpolar. (Parts (a) and (b) are solved in the text.)
H
Cl H
(c) H (d) C F large dipole (1.81)
H C large dipole (1.54)
H
Cl
net
net
(e) F (f)
F
C net dipole = 0 O large dipole (1.70)
F
F
H CH3 net

(g) (h) (i)

O H
H C N N
C
net C
H CH3 net
large dipole (2.95) H H
large dipole (2.72) net
large dipole
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2-3 continued
(j) (k)
H H
small dipole (0.67) C C
N Cl H net
H3C CH3 net
CH3 large dipole (1.45)

(l) F (m)
Cl Be Cl
B F net dipole = 0

F In (l) and (m), the symmetry of the

molecule allows the individual
net dipole = 0 bond dipoles to cancel.

2-4 With chlorines on the same side of the double bond, the bond dipole moments reinforce each other,
resulting in a large net dipole. With chlorines on opposite sides of the double bond, the bond dipole
moments exactly cancel each other, resulting in a zero net dipole.
Cl Cl H Cl
net
large net dipole C C C C net dipole = 0
(2.40)
H H Cl H

2-5 Hydrogen bonds are shown as wavy bonds.

(a) + δ− δ+ (b)
δ H
CH3CH2 O δ− N δ+
δ+ δ+
−
O δ δ+ CH3CH2CH2 H
H
CH2CH3 H δ+
−
δ+ Nδ δ+
H CH2CH2CH3
H δ+

(c) (d)
O O
δ− H δ− H δ+
O
δ+
H H δ−
δ+ δ+ δ+ δ+ H H

O δ+ δ−
δ− CH3 H3C δ− δ+
H3C N
δ+ δ+ H3C δ+ N CH3
+ δ+
δ CH3 H3C
δ+ CH3
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2-6
(a) (CH3)2CHCH2CH2CH(CH3)2 has less branching and boils at a higher temperature than (CH3)3CC(CH3)3 .
(b) CH3(CH2)5CH2OH can form hydrogen bonds and will boil at a much higher temperature than
CH3(CH2)6CH3, which cannot form hydrogen bonds.
(c) CH3CH2CH2CH2OH can form hydrogen bonds and boils at a higher temperature than CH3CH2OCH2CH3.
(d) HOCH2(CH2)4CH2OH can form hydrogen bonds at both ends and has no branching; it will boil at a much
higher temperature than (CH3)3CCH(OH)CH3 .
(e) (CH3CH2CH2)2NH has an N—H bond and can form hydrogen bonds; it will boil at a higher temperature
than (CH3CH2)3N, which cannot form hydrogen bonds.
(f) The second compound shown (B) has the higher boiling point for two reasons: B has a higher molecular
weight than A; and B, a primary amine with two N—H bonds, has more opportunity for forming hydrogen
bonds than A, a secondary amine with only one N—H bond.
H
A N H B N
H
2-7
(a) CH3CH2OCH2CH3 can form hydrogen bonds with water and is more soluble than CH3CH2CH2CH2CH3,
which cannot form hydrogen bonds with water.
(b) CH3CH2CH2OH is more soluble in water because it has one fewer carbon than CH3CH2OCH2CH3 .
(c) CH3CH2NHCH3 is more water soluble because it can form hydrogen bonds with water; CH3CH2CH2CH3
cannot form hydrogen bonds.
(d) CH3CH2OH is more soluble in water. The polar O—H group forms hydrogen bonds with water,
overcoming the resistance of the nonpolar CH3CH2 group toward entering the water. In
CH3CH2CH2CH2OH, however, the hydrogen bonding from only one OH group cannot carry a four-carbon
chain into the water; this substance is only slightly soluble in water.
(e) Both compounds form hydrogen bonds with water at the double-bonded oxygen, but only the smaller
molecule (CH3COCH3) dissolves. The cyclic compound has too many nonpolar CH2 groups to dissolve.
2-8
1 mole HBr
(a) 5.00 g HBr x = 0.0618 moles HBr
80.9 g HBr
0.0618 moles HBr 0.0618 moles H3O + (100% dissociated)
0.0618 moles H3O + 1000 mL 0.618 moles H3O +
x =
100. mL 1L 1 L solution

pH = − log10 [ H3O+ ] = − log10 (0.618) = 0.209

(b) 1.50 g NaOH x 1 mole NaOH = 0.0375 moles NaOH

40.0 g NaOH
0.0375 moles NaOH 0.0375 moles −OH (100% dissociated)
0.0375 moles −OH 1000 mL 0.75 moles −OH
x = = 0.75 M
50. mL 1L 1 L solution
1 x 10−14 1 x 10−14
[ H3O+ ] = = = 1.33 x 10−14
[ −OH ] 0.75 (The number of decimal places
pH = − log10 [ H3 O+ ] = − log10 (1.33 x 10−14 ) = 13.88 in a pH value is the number of
significant figures.)
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2-9
(a) By definition, an acid is any species that can donate a proton. Ammonia has a proton bonded to
nitrogen, so ammonia can be an acid (although a very weak one). A base is a proton acceptor; that is, it
must have a pair of electrons to share with a proton. In theory, any atom with an unshared electron pair can
be a base. The nitrogen in ammonia has an unshared electron pair so ammonia is basic. In water, ammonia
is too weak an acid to give up its proton; instead, it acts as a base and pulls a proton from water to a small
extent.
(b) water as an acid: H2O + NH3 –OH + NH +
4

water as a base: H2O + HCl H3O+ + Cl–

(c) Hydronium acting as an acid in water solution will have this chemical equation:
H3O+ + H2O H3O+ + H2O [H3O+] [A–] [H3O+] [H2O]
Ka = = = [H2O]
HA A– [HA] [H3O+]
1000 g H2O 1 mole H2O
[H2O] = x = 55.55 M = Ka pKa = –log(55.55) = –1.74
1 L H2O 18.0 g H2O

(d) methanol as an acid: CH3OH + NH3 CH3O– + NH4+

methanol as a base: CH3OH + H2SO4 CH3OH2+ + HSO4–

2-10 Values are from Table 2-2, or, as noted, from Appendix 4 in the text.
(a) HCOOH + −CN HCOO− + HCN FAVORS Part (a) is already
stronger stronger weaker weaker PRODUCTS solved in the text.
acid base base acid
pKa 3.76 pKa 9.22

(b) CH3COO− + CH3OH CH3COOH + CH3O− FAVORS

weaker weaker stronger stronger REACTANTS
base acid acid base
pKa 15.5 pKa 4.74
(Appendix 4)

(c) (CH3)2CHOH + NaNH2 (CH3)2CHO− Na+ + NH3 FAVORS

stronger stronger weaker weaker PRODUCTS
acid base base acid
pKa ≈15.9 pKa 36
(estimated from Table 2-2)

(d) Na+ −OCH3 + HCN HOCH3 + Na+ –CN FAVORS

stronger stronger weaker weaker PRODUCTS
base acid acid base
pKa 9.22 pKa 15.5
(Appendix 4)

(e) HCl + CH3CH2OH CH3CH2OH2+ + Cl− FAVORS

stronger stronger weaker weaker PRODUCTS
acid base acid base
pKa –7 pKa –2.4
(Appendix 4)
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2-10 continued
(f) H3O+ + CH3O− H2O + CH3OH FAVORS
stronger stronger weaker weaker PRODUCTS
acid base base acid
pKa –1.7 pKa 15.5 (Appendix 4)

H
(g) N H + OH N + O FAVORS
H PRODUCTS
stronger stronger weaker weaker
base acid acid base
pKa 10.0 pKa 11.3
(Appendix 4) (Appendix 4)

H
(h) N H + COOH N + COO FAVORS
H PRODUCTS
stronger stronger weaker weaker
base acid acid base
pKa ≈ 4.7 pKa 11.3
(Appendix 4) (Appendix 4)
similar to CH3COOH

(i) SH + CH3CH2O CH3CH2OH + S FAVORS

PRODUCTS
stronger stronger weaker weaker
acid base acid base
pKa 7.8 pKa 15.9
(Appendix 4) (Appendix 4)

(j) C C + CH3CH3OH C CH + CH3CH2O FAVORS

PRODUCTS
stronger stronger weaker weaker
base acid acid base
pKa 15.9 pKa ≈ 25
(Appendix 4) (Appendix 4)
similar to HC CH

2-11 O O
(a) H3C C OH + B H B + H3C C O
strongest acid pKa 4.74

CH3CH2OH + B H B + CH3CH2O
pKa 15.9

CH3NH2 + B H B + CH3NH
weakest acid pKa 40
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2-11 continued
(b)
CH3NH2 + H A A + CH3NH3
strongest base pKa 10.7 weakest conjugate acid

CH3CH2OH + H A A + CH3CH2OH2
pKa –2.4
O OH

H3C C OH + H A A + H3C C OH strongest conjugate acid

weakest base pKa –6.1
2-12
First, review the structures and properties of the solvents in question.
CH3CH2CH2CH2CH3 CH3CH2OCH2CH3 CH3CH2OH H2O NH3
pentane diethyl ether ethanol water ammonia
•Pentane is a hydrocarbon, neither acidic nor basic. Any acid-base reaction can occur in hydrocarbons
without interacting with the solvent.
•Diethyl ether is not acidic, so reactions with strong bases are compatible, but it is weakly basic, so reactions
with very strong acids (stronger than pKa –3.6) will be leveled by the solvent.
•Ethanol is both acidic (pKa 15.9) and basic (pKa of the conjugate acid –2.4), so only acids and bases within
this range are possible without interaction with the solvent.
•Water is both acidic (pKa 15.7) and basic (pKa of the conjugate acid –1.7), so only acids and bases within
this range are possible without interaction with the solvent.
•Ammonia is both acidic (pKa 36, very weak) and basic (pKa of the conjugate acid 9.2), so only acids and
bases within this range are possible without interaction with the solvent.
This question is asking, "Are the ultimate products compatible with the solvents?" The reactants may be
leveled by the solvent, but as long as the products can exist within the pKa limits of the solvent, the solvent is
an acceptable choice.
CH3CH2CH2CH2CH3 CH3CH2OCH2CH3 CH3CH2OH H2O NH3
Reaction pentane diethyl ether ethanol water ammonia
(a) very strong base OK OK NO NO OK
HC CLi is a strong base from an acid of pKa 25. It is not compatible with alcohols and water.

(b) strong base OK OK NO NO OK

(CH3)3COLi is a strong base from an acid of pKa 18. It is not compatible with alcohols and water.
(c) very strong acid OK NO NO NO NO
The protonated ring compound has pKa –3.8. It is compatible only with pentane.
(d) strong base OK OK NO NO OK
also a reactant
(CH3)3CONa is a strong base from an acid of pKa 18. It is not compatible with alcohols and water.
(e) very strong acid OK NO NO NO NO
The protonated oxygen compound has pKa –7.3. It is compatible only with pentane.
(e) strong acid OK OK OK OK NO
The protonated oxygen compound has pKa 0.0. It is compatible with the four solvents except ammonia.

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2-13
favors
(a) CH3CH2 O H + CH3 N H CH3CH2 O + CH3 N H
PRODUCTS
stronger acid stronger base conjugate base
H
weaker base conjugate acid
more stable anion—
negative charge on the weaker acid
more electronegative atom
(b) F3CCOONa + Br3CCOOH F3CCOOH + Br3CCOONa favors
weaker base weaker acid conjugate acid conjugate base REACTANTS
more stable anion—F is stronger acid stronger base
more electronegative than Br
H
(c) CH3 O H + H2SO4 CH3 O H + HSO4– favors
PRODUCTS
stronger base stronger acid conjugate acid conjugate base
pKa –5 weaker acid weaker base
pKa –2.5

(d) Na O H + H S H H O H + Na S H favors
PRODUCTS
stronger base stronger acid conjugate acid conjugate base
weaker acid weaker base
H larger anion—size matters!

(e) CH3 N H + CH3 O CH3 N H + CH3 O H favors

PRODUCTS
H stronger base H conjugate acid
stronger acid conjugate base weaker acid
pKa 10.7 weaker base pKa 15.5

(f) BrCH2CH2OH + F3CCH2O– BrCH2CH2O– + F3CCH2OH favors

weaker acid weaker base conjugate base conjugate acid REACTANTS
more stable anion—F is stronger base stronger acid
more electronegative
than Br, especially 3 F
(g) NaOCH2CH3 + Cl2CHCH2OH HOCH2CH3 + Cl2CHCH2ONa favors
stronger base stronger acid conjugate acid conjugate base PRODUCTS
weaker acid weaker base
more stable anion—
2 Cl stabilize anion
(h) H2Se + NaNH2 NaHSe + NH3 favors
stronger acid stronger base conjugate base conjugate acid PRODUCTS
pKa 7.0 weaker base weaker acid
more stable anion— pKa 36
Se much larger than N
(i) CH3CHFCOOH + FCH2CH2COO– CH3CHFCOO– + FCH2CH2COOH favors
stronger acid stronger base conjugate base conjugate acid PRODUCTS
weaker base weaker acid
more stable anion—F is
closer to COO–
(j) CF3CH2O– + FCH2CH2OH CF3CH2OH + FCH2CH2O– favors
weaker base weaker acid conjugate acid conjugate base REACTANTS
more stable anion—3 F stronger acid stronger base
stabilizes anion better than
1F 45
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2-14
Three principles guide the effect of electron-withdrawing substituents on acid strength. Acidity is increased by:
1. increasing strength of electron-withdrawing substituents; for single atoms, this means more electronegative;
2. increasing number of electron-withdrawing substituents;
3. closer proximity of the electron-withdrawing substituents to the acidic group.
"Electron-Withdrawing Group" is abbreviated "EWG".

strongest acid weakest acid

two, strong EWG one, strong EWG one, moderate EWG one, moderate EWG
next to acid group next to acid group next to acid group farther from acid group

2-15 H3C H3C

stronger
(a) conjugate acid C O + H2O H3O+ + C O sp2
H H H weaker base
pKa –8.0
(b) H3C H H3C H
pKa –2.4
H C O + H2O H3O+ + H C O sp3
weaker
conjugate acid H H H stronger base

An atom with sp2 hybridization is less basic than the same atom with sp3 hybridization. Therefore,
the conjugate acid of the sp2 atom must be a stronger acid than the atom when sp3 hybridized.

2-16 NHCH3 NCH3

C N

strongest base, sp3 sp2 weakest base, sp

H A H A H A

H H
NHCH3 NCH3

C N H

weakest conjugate acid sp2 strongest conjugate acid

pKa 10.7 for pKa 5.5 for pKa –10.1 for really
H NHCH3 strong!
H3CC NH
H N CH3 C
H3C CH3
CH3 46
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2-17
When comparing basic atoms, sp3 atoms are stronger bases than sp2, which are stronger than sp.
Conjugate acids have the opposite order: H on sp is stronger than H on sp2, which is stronger than H on sp3.
(a) (b) OH O
C C

weaker base, sp stronger base, sp2

stronger base, sp3 weaker base, sp2
H A H A
H H A H A
OH2 OH
C C H

stronger conjugate acid weaker conjugate acid

weaker conjugate acid stronger conjugate acid

(c) (d) These structures are not the same comparison as

NH N in the other problems. They differ by a more
important feature than hybridization: an anion at
an sp3 carbon is always going to be a stronger
base than a neutral nitrogen.
stronger base, sp3 weaker base, sp2 H

H A H A
C N

NH2 NH stronger base, weaker base, neutral

anion and sp3 N and sp
H A
H A
weaker conjugate acid stronger conjugate acid H H

C N H

weaker conjugate acid stronger conjugate acid

2-18
Recall that for any conjugate acid-base pair, pKa + pKb = 14. Applying this to the structures in question:

HCN H+ + CN
hydrocyanic acid, cyanide ion, pKb = 4.78;
pKa = 9.22; weaker acid stronger conjugate base
HF H+ + F
hydrofluoric acid, fluoride ion, pKb = 10.83;
pKa = 3.17; stronger acid weaker conjugate base

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2-19
The resonance forms of acetamide show that the oxygen, not the nitrogen, is the likely site of protonation
because the oxygen has a higher electron density than nitrogen.
H H
O O O O
+ H3O+
C C C C
H3C NH2 H3C NH2 H3C NH2 H3C NH2

pKb = 14 Protonation on oxygen also maintains resonance

stabilization, unlike protonation on nitrogen
which interrupts resonance stabilization.
pKa = 14 – pKb = 14 – 14 = 0
2-20
Protonation could occur at either oxygen.
O O O
protonation on OH No resonance
C C C stabilization with
H3C OH H3C OH H3C OH
protonation at OH.
pKb = 20 H H
protonation insignificant
on =O contributor

H H H Protonation at this oxygen makes a

O O O
positive ion that is stabilized by
C C C resonance; both major resonance
H3C OH H3C OH H3C OH contributors are equivalent, especially
major minor major stabilizing. Moreover, all three atoms
in the pi system share in the
pKa = 14 – pKb = 14 – 20 = –6 delocalization of the positive charge.

2-21 The strength of an acid is determined by the stability of its conjugate base.
This problem analyzes resonance stabilization of conjugate bases, which in this problem are anions except
for part (g). The conjugate base that has more resonance forms that are significant contributors will be
more stable, and therefore its conjugate acid is the stronger acid.
Part (a) was solved in the textbook.
(b) The anion of the first structure has three significant resonance contributors, two of which are equivalent
(particularly stable) and with negatve charge on the more electronegative atoms; high stabilization of the
anion makes the first structure the stronger acid.
H

O O O C O O O

major minor major

See the next page for the resonance forms of the other conjugate base.
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2-21(b) continued
The anion obtained by removing the H+ from
O O O O the OH in the second structure gives only two
resonance forms, and only one has negative
charge on oxygen—not as stable as the first
C structure.
major minor H
However, there is another choice of which H+ to remove. Removing an H from the CH2 between the two
oxygens also gives a resonance-stabilized anion:
H H remove H H H

O C OH O C OH O C OH O C OH

C
H
minor major minor
Arguably, the CH is a better proton to remove than the OH because of greater resonance stabilization, but
either of the anions from the second structure is less stable than the anion from the first structure. The first
structure is still the stonger acid.
(c) The most acidic H+ from the first structure is the OH. F O no resonance forms;
The anion from removing this H+ is not stabilized by F is too far away to
resonance, and the F is too far away to have any significant stabilize anion
inductive effect.

The anion from the second structure has F F

two resonance forms, the second of which
is even more stable because of the O C O
electronegativity of F. Therefore, the
second structure is the stronger acid.

major better than minor because

of F electronegativity
(d) Removing an H+ from NH2 gives a highly stabilized anion:
O O O

C NH C NH C NH

second most significant least significant most significant

There are two choices for which H+ to remove from the second O
structure. If we want a direct comparison with the resonance-
stabilized anion directly above, we should look at removing an H+
from the N, giving this conjugate base with no resonance C NH
stabilization.

See the next page for the resonance forms of the other conjugate base.
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2-21(d) continued

O O O O

C NH2 C NH2 C NH2 C NH2

C C C C
H
H remove H H H
minor minor major

Although removing the CH2 proton gives a more stable conjugate base than removing the NH2 proton,
neither is better than the anion from the first structure. The first structure is the stronger acid.
(e) Remove the proton from the OH in each case. The first structure gives a resonance-stabilized
conjugate base, but only one of the resonance forms has the negative charge on an electronegative atom.
H
O C N O C C N O C N

C
H
major minor minor
From the second structure:
H

O O C O O

C C
C C C C
major N minor N minor N MAJOR N

Woo hoo! With the proper placement of the CN group, the negative charge can be delocalized onto the N
as well as the O, making this the more stable conjugate base. The second structure is the stronger acid.

(f) Remove the proton from the OH in each case. The first structure gives a resonance-stabilized conjugate
base in which the negative charge is delocalized onto both oxygen atoms—hard to beat.
O O O O

H
C C

O major O minor O minor O major

See the next page for the structure of the other conjugate base.

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2-21(f) continued O
The conjugate base of the second structure shows that
there is no resonance stabilization of the anion.
Therefore, the first structure is the stronger acid.

(g) The conjugate bases of these structures are not anions, yet the same principle applies: the stability of the
conjugate base determines the strength of the acid.
O O O
After one of the NH protons is
C
removed from the first structure, the
conjugate base is a structure that has
no charge and the NH2 is not HC
stabilized by resonance. NH2 NH2 NH2
major minor minor
After one of the NH protons is removed from the second structure, however, the conjugate base is highly
stabilized by resonance.
O O O O

C
NH2 NH2 NH2 NH2
major minor minor major—all atoms have octets
Because it has the more stable conjugate base, the second structure is the stronger acid.
(h)
After the OH proton is removed, the first
structure is stabilized by resonance only to a
small degree.
O C O

major H
minor—negative on less
electronegative atom
After one of the OH protons is removed from the second structure, however, the conjugate base is highly
stabilized by resonance.
H H
C C

O C O O O O

major H minor minor minor major

Because it has the more stable conjugate base, the second structure is the stronger acid.
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2-21 continued
(i) In both of these structures, removal of the OH proton results in a highly stabilized anion.
O O O O

H H H C H

O C O O O

major H minor minor major

AHA! The second
O O structure does not have
this "extra" resonance
H form.
H H C

O O
major minor
Resonance forms of the anion of the second structure show that the negative charge is never delocalized
on the C=O group.

H O H O H O H O H O

H H
C C

O C O O O O

major H minor minor minor major

The first structure has the extra resonance form where the negative charge is delocalized onto the C=O,
resulting in greater stability. The first structure is the stronger acid.

Note to the student: Resonance is your friend. Many, if not most, of the effects of structure on
stability and reactivity are based on resonance, and understanding how to draw resonance forms, and
when to apply the concept of resonance, is a critical tool in your success in solving problems.

2-22
The more stable the anion, the less basic it will be. This is the corollary of: a stronger acid has a weaker
conjugate base, because a stronger acid has a more stable conjugate base.
(b) The first structure has its negative charge delocalized by resonance.
H

O O O C O O O

major minor major

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2-22(b) continued
The negative charge in the second structure is
O O O O only slightly stabilized by one minor resonance
contributor.

C
major minor H

Because the first structure is more stable because of greater resonance delocalization of the negative charge,
the second structure will be the stronger base. Note that this is the same as problem 2-21(b), just from
the other side of the equation.
(c) The first structure has N N N
the negative charge O O O O O O
delocalized onto two
oxygens and a nitrogen:

The second structure has

the negative charge O O O O
delocalized onto one
oxygen and a carbon: NH C NH
major
H minor
Because the first structure is more stable because of greater resonance delocalization of the negative charge,
the second structure will be the stronger base.
(d) Even though there is resonance between the NO2
C=C and the NO2 group, the first structure has
the negative charge on oxygen that is not
delocalized by resonance.

O O O
The second structure has
the negative charge N N N
delocalized onto two O C O O
oxygens:
O O O
major minor major

Because the second structure is more stable because of greater resonance delocalization of the negative
charge, the first structure will be the stronger base.

(e) As shown on the next page, the negative charge in both structures is highly delocalized by resonance,
but only the second structure has the negative charge on the oxygen and the nitrogen. Because the second
structure is more stable, the first structure will be the stronger base.

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2-22(e) continued
First structure:
H H
C C

NC O NC C O NC O NC O NC O
major H minor minor major
minor
Second structure:

N N N N N
C C H C C C
C C

O C O O O O
major H minor minor major
minor
N
C
This is the extra
resonance form that
makes this structure more O
stable. major

The first structure will be the stronger base.

2-23 Solutions for (a) and (b) are presented in the Solved Problem in the text. Here, the newly formed
bonds are shown in bold. H
Curved arrows that show
(c) H B H + CH3 O CH3 electron movement are
H B H
shown here and in the text
H Lewis base—
Lewis acid—electrophile nucleophile
CH 3 O CH 3 in red. Arrows within
resonance forms that show
imaginary movement are in
(d) O O green in the text, and in
black here.
CH3 C H + O H CH3 C H
Lewis base— The problem asks for the imaginary
Lewis acid—electrophile nucleophile O H movement of electrons in the resonance
forms.
(e) Brønsted-Lowry—proton transfer
H O H O H O

H C C H + O H H C C H H C C H + H O H
base—
H nucleophile
acid—electrophile
CH3

(f) CH3 N H + CH3 Cl CH3 N H + Cl

H Lewis acid—
electrophile H
Lewis base—
nucleophile 54
Copyright © 2017 Pearson Education, Ltd.
2-23 continued
F F
H
(g) CH3 C CH2 + B F CH3 C C B F
H H2
Lewis base— F F
nucleophile Lewis acid—
electrophile same
F CH3 F
H H2 H H2
(h) CH3 C CH2 + CH3 C C B F H3C C CH2 C C B F
H H
Lewis base— F F
nucleophile Lewis acid—
electrophile

O O
(i)

Cl Cl
O The problem asks for the imaginary movement of
OH H electrons in the resonance forms.

OCH3 OCH3 OCH3

(j) C C

O O
O N O N N

O O

2-24 H H
H C H H H H H H H H H H
(a) H C C H (b) H C C C C C H (c) H C C C C C C H
H C C H alkane H H H H H H H H H
H C C H alkene alkyne
H C H H H
H H (Usually, we use the term "alkane"
only when no other groups are present.)

H H H H H H H
(d) H C C C C (e) H C C C C H (f) H C C C H
C C
H C C H C C H C C
H C C H H C H
H H
HH H
H H cycloalkane and alkene
cycloalkyne and (a "cycloalkene" would aromatic hydrocarbon
cycloalkene have the C=C in the ring) and alkyne

continued on page 57 55
Copyright © 2017 Pearson Education, Ltd.
 WHAT IS THE FUNCTIONAL GROUP?
DOES THE STRUCTURE HAVE ANY PI BONDS?

NO YES

DOES THE STRUCTURE HAVE O OR N? DOES THE STRUCTURE HAVE O OR N?

NO YES NO YES

ALKANE— DOES THE ALKENE DOES THE

no functional group STRUCTURE HAVE O? STRUCTURE HAVE O?
OR C C
NO YES NO YES
ALKYL HALIDE
OR
AMINE ALCOHOL ALDEHYDE

56
ALKYNE NITRILE
C X O
C C C N
C N C OH
C
X = F, Cl, Br, I OR H
BENZENE CARBOXYLIC ACID KETONE
OR (AROMATIC)
O O

Copyright © 2017 Pearson Education, Ltd.

ETHER C H C
O C C
C O C
this chart! Use it as an aid as you are becoming familiar with the functional groups.

AMIDE ESTER ACID CHLORIDE

This chart depicts only the most O O O
common functional groups.
There are many more! C C C C
N O Cl
called acid derivatives
groups are present in a molecular structure. This page is called a "concept map" that prompts you with a
Note to the student: One of the most fundamental skills in organic chemistry is to identify what functional

series of questions about a structure, leading to the determination of the functional group. Do not memorize
2-24 continued
H H H H H H
HH H H H
H C C C C H (h) H H (i) H C C
(g) H C C C C H
C C C C H
C H C C
H C C H H C C C
C H
H
C C H H H C C H
H H H H
H H H H H
cycloalkene and alkene cycloalkane and alkane aromatic hydrocarbon
and cycloalkene
2-25 H
H H O H H O H H O H H
(a) H C C C H (b) H C C C C H (c) H C C C C H
alkene and aldehyde H H H H H H H
alcohol ketone
H H H H H H
(d) (e) H C H O (f) H O H ether and
H C C O C C H H C C C O H H C C alkene
H H H C C H H C C
ether and alkene H C H H C H
H H H H
carboxylic acid
H O H
H H H H C O H
C H H
(g) H C O (h) H C (i) C
C C C C C C H
H H H H
C C C C C C
H H H H H H
H H H H H H
alkene and ketone aldehyde alcohol
2-26
H H O H H H H H H H O H
(a) H C C C N C H (b) H C C N C C H (c) H C C C O C H
H H H H H H H H H H C H
amide amine HH H ester
H H H O H H H H H H H
(d) H C C C C Cl (e) H C C O C C H (f) H C C C C N
H alkene and H H H H H H H
acid chloride ether nitrile

HH H O O H H H
(g) H C H H O (h) H C (i) H C H H C
(j)
C O C C H C N C H
H C C C C C O H H H
C C C O H C C HH
H C H H H H H C H
HH H H H H H H
carboxylic acid cycloalkene and cyclic ketone
cyclic ester and ether cyclic amine

57
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2-26 continued
O O
H H H O H
(k) H C (l) H C (m) H C
H C N C H cyclic H C N C C H H C O cyclic ester
H C C H H amide H C C H H H C C H
H C H H C H H C H
H H H H H amide H H
H C H H H
O O H
(n) H N H (o) H C
H C C C H C C C C H
H
H C C H cyclic amine C C H
H C H and aldehyde H H
H H H cycloalkene
and ketone
2-27 When the identity of a functional group depends on several atoms, all of those atoms should be
circled. For example, an ether is an oxygen between two carbons, so the oxygen and both carbons should
be circled. A ketone is a carbonyl group between two other carbons, so all those atoms should be circled.
O
(a) CH2 CHCH2COOCH3 (b) CH3 O CH3
aldehyde
ester (c) CH3 C H
alkene ether
O
C OCH3 amine O
O (e) CH3 N CH3 (f) R C O H
(d) CH3 C NH2 H carboxylic acid
R is the symbol that organic chemists use to
amide represent alkyl groups. Sometimes, when the
identity of the group does not matter, aryl groups or
others can also be included in the R abbreviation.

aromatic
(g) CH2OH (h) C N (i)
O ketone
alcohol nitrile
alkene

(j) aromatic
ketone (k) ether
(also includes two alcohol (In later chapters, you will CH3
adjacent carbons) learn that the OH group on a CH3
CH2OH benzene ring is a special CH3 O
alcohol functional group called a C16H33
O "phenol". For now, it fits the
HO broad definition of an alcohol.)
OH HO
ketone
alcohol
alcohol CH3

O
alkene
58 This group is represented by C16H33 in the problem.
Copyright © 2017 Pearson Education, Ltd.
2-28
The triple bond between C and N is highly polarized: H3C C N H3C C N
A B
3.6 D = 4.8 x δ x 1.16 Å
δ = 0.65, or 65% of a positive charge on carbon and 65% of a negative charge on nitrogen
Resonance form B must be the major contributor. If A were the major contributor, the value of the charge
separation would be between 0.0 and 0.5, meaning <50% of a positive charge on C and <50% of a negative
charge on N.
2-29 Some magnitudes of dipole moments are difficult to predict; however, the direction of the dipole should
be straightforward in most cases. Actual values of molecular dipole moments are given in parentheses. (The
C—H bond is usually considered nonpolar.)
H2
(a) (b) C H
CH3 CH 3 H 3 C O
N N
or net
C C
H CH3 H CH3 large dipole moment (2.6)
net net
large dipole moment large dipole moment
(e)
Br N N
Br
(c) C (d) C C
Br O
C C
Br
C C C
net dipole moment = 0 net N N
CH3 CH3
Electron pairs on
bromines are not shown. large dipole moment (2.89)

net dipole moment = 0

(f) H (g) (h)
CH2 Cl
N
CH2 C
CH2 CH2 O
net
CH2 C net
CH2 CH2 C net
CH2 H
CH2 CH3 NH2
moderate dipole moment moderate dipole moment large dipole moment (3.76)
Electron pairs on
chlorine are not shown.

2-30 CO2 is linear; its bond dipoles cancel, so it has no net dipole. O3 is bent, so its bond dipoles do not
cancel.

59
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2-31
2-31
(a) Can hydrogen bond with itself and with water. (b) Can hydrogen bond only with water.
(c) Can hydrogen bond with itself and with water. (d) Can hydrogen bond only with water.
(e) Cannot hydrogen bond: no N or O. (f) Cannot hydrogen bond: no N or O.
(g) Can hydrogen bond only with water. (h) Can hydrogen bond with itself and with water.
(i) Can hydrogen bond only with water. (j) Can hydrogen bond only with water.
(k) Can hydrogen bond only with water. (l) Can hydrogen bond with itself and with water.
Water solubility depends on the number of carbons and the number of hydrogen-bonding groups in a
molecule, and to a lesser extent, on the shape of the molecule and its ability to form hydrogen bonds. A
structure with one hydrogen-bonding group can carry in three carbons for sure, called "miscible", meaning
completely soluble; four carbons will be partially soluble—these are borderline cases and are the most
difficult to predict; five or more carbons will be only slightly soluble, which is sometimes called "insoluble".
•completely soluble, miscible: (c) 3C; (g) 3C; (h) 3C; (i) 3C; (l) 2C;
•moderately soluble, possibly miscible: (a), (j), (k)—each has one H-bonding group and 4C;
•slightly soluble, "insoluble": (b) 6C; (d) 6C; (e) and (f) have no H-bonding group.

2-32
As summarized in the solution to problem 2-31, water solubility depends on the number of carbons and the
number of hydrogen-bonding groups in a molecule. A structure with one hydrogen-bonding group can
carry in three carbons for sure, called "miscible", meaning completely soluble; four carbons will be
partially soluble; five or more carbons will be only slightly soluble, which is sometimes called "insoluble".
(a) The first structure with 5 carbons and no hydrogen-bonding group is completely insoluble in water.
The second structure has 4 carbons and 1 oxygen; it is miscible with water because oxygen's electron pairs
can form hydrogen bonds with water.
(b) The first structure with 5 carbons and 1 oxygen is partially soluble in water (tetrahydropyran, 8 g/100
mL water). The second structure has 4 carbons and 2 oxygens; it is miscible with water.
(c) The first structure with 4 carbons and 1 oxygen is miscible with water. The second structure with 5
carbons and 1 oxygen is only partially soluble in water (2-methyltetrahydrofuran, 14 g/100 mL).
(d) The first structure with 5 carbons and no hydrogen-bonding group is completely insoluble in water.
The second structure has 6 carbons and 1 oxygen; it is partially soluble in water.
(e) The first structure with 5 carbons and 1 oxygen is slightly soluble in water. The second structure has 5
carbons and two bromines—which do not form hydrogen bonds—and is completely insoluble in water.
(f) The first structure with 5 carbons and 1 oxygen is partially soluble in water (tetrahydropyran, 8 g/100
mL water). The second structure has 4 carbons and 1 oxygen; it is miscible with water because the electron
pairs on oxygen are exposed and can readily form hydrogen bonds with water.

2-33 The boiling point of ethanol is much higher because these molecules can form hydrogen bond with
each other, thus requiring more energy to separate one molecule from another. Dimethyl ether molecules
cannot form hydrogen bond with each other, so it is relatively easy to separate them.

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2-34
N CH3 N H O OH

N-methylpyrrolidine piperidine tetrahydropyran cyclopentanol

b.p. 81 °C b.p. 106 °C b.p. 88 °C b.p. 141 °C
(a) Piperidine has an N—H bond, so it can hydrogen bond with other molecules of itself.
N-Methylpyrrolidine has no N—H, so it cannot hydrogen bond and will require less energy (lower boiling
point) to separate one molecule from another.

(b) Two effects need to be explained: 1) Why does cyclopentanol have a higher boiling point than
tetrahydropyran? and 2) Why do the oxygen compounds have a greater difference in boiling points than the
analogous nitrogen compounds?
The answer to the first question is the same as in (a): cyclopentanol can hydrogen bond with its
neighbors while tetrahydropyran cannot.
The answer to the second question lies in the text, Table 2-1, that shows the bond dipole moments for
C—O and H—O are much greater than C—N and H—N; bonds to oxygen are more polarized, with greater
charge separation than bonds to nitrogen.
How is this reflected in the data? The boiling points of tetrahydropyran (88 °C) and
N-methylpyrrolidine (81 °C) are close; tetrahydropyran molecules would have a slightly stronger dipole-
dipole attraction, and tetrahydropyran is a little less "branched" than N-methylpyrrolidine, so it is reasonable
that tetrahydropyran boils at a slightly higher temperature. The large difference comes when comparing the
boiling points of cyclopentanol (141 °C) and piperidine (106 °C). The greater polarity of O—H versus N—H
is reflected in a more negative oxygen (more electronegative than nitrogen) and a more positive hydrogen,
resulting in a much stronger intermolecular attraction. The conclusion is that hydrogen bonding due to O—H
is much stronger than that due to N—H.
(c) Resonance plays a large role in the properties of amides.

O CH3 O CH3 O CH3 O CH3

H C N H C N H3C C N H3C C N
CH3 CH3 H H
N,N-dimethylformamide, b.p. 150 °C N-methylacetamide, b.p. 206 °C
The first structure has no hydrogen bonding because it has no O—H or N—H bond, but it is a highly polar
structure and has a large dipole moment, so its dipole-dipole intermolecular force is very high. The second
structure has hydrogen bonding because of the N—H bond in addition to the strong dipole-dipole interaction,
reflected in its higher boiling point. Both amides boil higher than the four at the beginning of the problem
because of the dipole-dipole interactions that are accentuated by the resonance forms.
2-35 Higher-boiling compounds are the ones described.
(a) CH3CH2CH(OH)CH3 can form hydrogen bonds with other molecules of itself.
(b) CH3CH2CH2CH2CH2CH3 has a higher molecular weight than CH3CH2CH2CH2CH3.
(c) CH3CH2CH2CH2CH2CH3 has less branching than (CH3)2CHCH2CH2CH3.
(d) (CH3)2CHCH2CH2CH2Cl has a higher molecular weight AND a dipole-dipole interaction compared with
(CH3)2CHCH2CH2CH3.
(e) (f) O
NH
has two sites for hydrogen bonding, not
can form hydrogen bonds
NH just one, and a very strong dipole
with other molecule of itself because of resonance.
(actual bp 81°C; the other
structure has bp 72°C).
61
Copyright © 2017 Pearson Education, Ltd.
2-36 The strength of the acid depends on the stability of the conjugate base. The two primary factors
governing the strength of organic acids are resonance and inductive effects; of these two, resonance is
usually the stronger and more important effect.
Any organic structure with an —SO3H in it is a very strong acid because the anion has three significant
resonance contributors. An organic structure with —COOH is moderately strong since the conjugate base
has two significant resonance contributors. A structure with a simple —OH does not have any resonance
stabilization of the conjugate base, so it is the weakest acid. Within each group, inductive effects from an
electronegative atom like Cl will have a small effect.
CH3CH2CH2OH > CH3CH2CH2COOH > ClCH2CH2CH2COOH > CH3CH2CHClCOOH > CH3CH2CH2SO3H
(b) (c) (e) (d) (a)
weakest acid Cl further from COOH Cl closer to COOH strongest acid

2-37 These pKa values from the text, Table 2-2 and Appendix 4, provide the answers. The lower the
pKa, the stronger the acid.
least acidic most acidic
CH4 < NH3 < H2O < HCN < HCOOH < HF < H2SO4
50 36 15.7 9.22 3.76 3.17 –5

2-38 Conjugate bases of the weakest acids will be the strongest bases. The pKa values of the conjugate
acids are listed here. (The relative order of some bases was determined from the pKa values in Appendix 4
of the textbook.)
least basic most basic
HSO4− < H2O < CH3COO− < NH3 < CH3O− ~ NaOH < −NH
2
from –5 from –1.7 from 4.74 from 9.4 from 15.5 from 15.7 from 36

2-39
(a) pKa = − log10 Ka = − log10 (5.2 x 10−5 ) = 4.3 for phenylacetic acid
for propionic acid, pKa 4.87: Ka = 10−4.87 = 1.35 x 10−5
(b) Phenylacetic acid is 3.9 times stronger than propionic acid.
5.2 x 10−5
= 3.9
1.35 x 10−5
(c)
CH2COO– + CH3CH2COOH CH2COOH + CH3CH2COO–
weaker acid stronger acid
Equilibrium favors the weaker acid and base. In this reaction, reactants are favored.

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 #3
2-40
(a) #1 NH #2

CH3 N C NH2

H+ to #1 H H+ to #2
H+ to #3

H NH NH
NH2
CH3 N C NH2 CH3 N C NH3
CH3 N C NH2
H H
no other significant H no other significant
resonance forms resonance forms

NH2 NH2 NH2

CH3 N C NH2 CH3 N C NH2 CH3 N C NH2

H H H
(b) Protonation at nitrogen #3 gives four resonance forms that delocalize the positive charge over all three
nitrogens and a carbon—a very stable condition. Nitrogen #3 will be protonated preferentially, which we
interpret as being more basic.

2-41 The critical principle: the strength of an acid is determined by the stability of its conjugate base.
(a) conjugate bases
W O X O Y O Z O
C C C OH C
CH2 NH N O

O O O O
C C C OH C
CH2 NH N O

(b) X is a stronger acid than W because the more electronegative N in X can support the negative charge better
than carbon, so the anion of X is more stable than the anion of W.
(c) Y is a stronger acid than X because the negative charge in Y is stabilized by the inductive effect from the
electronegative oxygen substituent, the OH.

(d) Z is a stronger acid than Y because of two effects: O is more electronegative than N and can support the
negative charge of the anion better, plus the anion of Z has two EQUIVALENT resonance forms, which is
particularly stable.

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2-42
(a) H2SO4 + CH3COO– HSO4– + CH3COOH

(b) CH3COOH + (CH3)3N CH3COO– + (CH3)3N H

O O
(c) C O H + –OH C O– + H2O

O O

(d) HO C OH + 2 –OH –O C O– + 2 H2O

(e) H2O + NH3 HO– + +NH

4

(f) (CH3)3N H + –OH (CH3)3N + H2O

(g) HCOOH + CH3O– HCOO– + CH3OH

(h) NH3CH2COOH + 2 –OH NH2CH2COO– + 2 H2O

2-43 Values are from Appendix 4 in the text. The side of the equation with the weaker acid and base is
favored.
OH O

(a) + + FAVORS
REACTANTS
N O2N N O2N
weaker weaker stronger
base acid H base
pKa 7.1 stronger
acid
pKa 5.2

COOH COO

(b) + + FAVORS
PRODUCTS
N O2N N O2N
stronger stronger weaker
base acid H base
pKa 3.4 weaker
acid
pKa 5.2

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2-43 continued

(c) + NaNH2 + NH3 FAVORS

N N PRODUCTS
weaker
stronger Na+ acid
H base
pKa 36
stronger weaker
acid base
pKa 17
Na+
O O

(d) H3C C NH2 + NaOCH2CH3 H3C C NH + HOCH2CH3 FAVORS

REACTANTS
weaker weaker stronger stronger but not by much
acid base base acid
pKa 16 pKa 15.9

The reaction in part (d) merits comment. Only 0.1 pKa units separates the two acids in this equation.
When pKa values are measured in solvents other than water (any pKa value higher than 15.7), the
experimental error increases. Without specifying that these two pKa values were measured in the
same solvent, it is difficult to give the difference of 0.1 pKa units much credence. Conclusion: the
two sides of the equation are fairly equally matched, and the products and reactants would probably
be close to 50:50. In one solvent, reactants may be favored, and in a different solvent, products
favored.
O OH

(e) H3C C NH2 + HCl (aq) H3C C NH2 + Cl FAVORS

PRODUCTS
stronger stronger weaker weaker
base acid: in water, acid base
leveled to H3O+ pKa 0.0
pKa –1.7

Recall from problem 2-19 that the site of protonation of the reactant is the O, not the N.

Na+
O O O O
(f) C C + NaOH (aq) C C + H2O FAVORS
H3C C OEt H3C C OEt PRODUCTS
H2 stronger H weaker
base acid
stronger weaker pKa 15.7
acid base
pKa 10.7 Et = ethyl, CH2CH3

The most acidic proton in the reactant is the CH between the two C=O because of resonance
stabilization of the resultant anion by both C=O. See the solutions to problems 1-8(g) or 1-43(c) for
similar examples.

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2-44 Note that this question is asking for the strength of the aqueous solution (pH), not just the strength of the
acid.
H2SO4 > HI = HBr > HCOOH > CH3COOH > HCN > NH4Cl
lowest pH, pKa = 3.76 pKa = 4.74 pKa = 9.22 highest pH,
equivalent—
strongest acid weakest acid
both leveled
to H3O +

Explanation: For acids weaker than water, the pH of the aqueous solution will follow the sequence of
the pKa values: the higher the pKa, the less they ionize in water. For acids stronger than water, they
will be leveled to hydronium ion, H3O+, so 1 molar solutions of HI and HBr would be completely
ionized, giving [H+] = 1M. The exception is H2SO4 because it is a diprotic acid: the first proton is
100% ionized, but the second proton (HSO4–) has pKa 2.0, higher than water but still a strong acid, so
some portion of it will also be ionized in excess of the first proton, making this aqueous solution the
strongest acid = lowest pH, with [H+] > 1M.
2-45 (a) conjugate bases
O O O O
C C C O F3C C
H3C O F3C O H3C O C O
H2

The negative charge cannot

be delocalized by resonance
O O in either of these two O
structures.
C C F3C C
H3C O F3C O C O
H2
CH3CH2 O

(b) O O O O

F3C
C
O
> F3C
C
C
O
>HC C
O H
> C
C
O
O > CH3CH2 O
3 3
H2
most stable— delocalization of weak least stable—no
delocalization of delocalization of negative charge by delocalization of delocalization of
negative charge by negative charge by resonance only negative charge negative charge
both resonance and resonance and a by induction only
induction weaker inductive
(electronegative F) effect as F atoms
are farther away

(c) The strongest acid will have the most stable conjugate base. The actual pKa values (some from text
Appendix 4) are listed beneath each acid.
O O O O

F3C
C
OH
>
F3C
C
C
OH H3C
> C
OH H3C
C >
O
OH >
CH3CH2OH
H2 weakest acid
strongest acid pKa 15.9
pKa 0.2 pKa 3.07 pKa 4.74 pKa 8.2

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2-46
(a) conjugate acids H O H
The oxygen is more basic
N C than the nitrogen in this
structure. See the solution to
H CH3 Problem 2-19.

H H
CH3CH2 N H H O H H OH CH3CH2 O H H NH2

H N C minor
H CH3

H O H
N C
H CH3

(b) order of decreasing stability (pKa values from Appendix 4 in the text)
H H
H O H
H NH2 > H OH > CH3CH2 N H > N C >
CH3CH2 O H
most stable— neutral H H CH3 least stable—positive
neutral molecule molecule
with less polar positive charge on less positive charge on more charge on more
pKa 15.7 electronegative atom electronegative atom electronegative atom
NH bonds, lower
electronegativity pKa 10.7 but resonance stabilized pKa –2.4
pKa 0.0
pKa 36

(c) The weakest conjugate acid will form the strongest conjugate base.
H O
NH2 > OH > CH3CH2 N H > N C > CH3CH2 O H
strongest base H H CH3 weakest base

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2-47
(a) conjugate bases
O O O O
O
C C S H3C S O
H3C O H3C NH H3C O F S O
O
O

O O O O
O
C C S H3C S O
H3C O H3C NH H3C O F S O
O
O
O
O
H3C S O
F S O
O
O

(b) O O O O O
F S O > H3C S O > H3C
S
O
> H3C
C
O
>HC 3
C
NH
O O
delocalization of delocalization of least stable—
most stable— delocalization of negative charge by negative charge by delocalization of
delocalization of negative charge by two resonance forms two equivalent negative charge by
negative charge by three resonance and induction (S resonance forms two resonance
three resonance forms and more electronegative forms, although
forms and induction (S more than C) non-equivalent
induction (F and S electronegative
more electro- than C)
negative than C)

(c) The strongest acid will have the most stable conjugate base. The pKa values are listed beneath each acid.
O O O O O
F S OH > H3C S OH > H3C
S
OH
> H3C
C
OH
> H3C
C
NH2
O O weakest acid
pKa 2.3 pKa 4.74
strongest acid pKa –1.2 pKa 16
pKa < –5

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2-48
Of all the substituent groups in organic molecules, the nitro group, NO2, is the best electron-withdrawing
group. Not only does it have three electronegative atoms that can stabilize negative charge by induction,
but it also has very strong resonance stabilization. Adding just one nitro group to methane increase the
acidity by 40 pKa units!
O O
CH3
H2C N H2C N
no stabilization;
one of the strongest O O
bases known
one nitro group—strong stabilization

O O O
N O N O N O
H C H C H C
N O N O N O
O O O

two nitro groups—very strong stabilization

O O O O
O N O O N O O N O O N O
N C N C N C N C
O N O O N O O N O O N O
O O O O

three nitro groups—maximum stabilization—essentially zero negative charge on central C

Each subsequent substitution of H by NO2 increases the amount of the delocalization of the electron pair
on C, stabilizing the anion.

2-49
(a) CH3OH + CH3CH2Li CH3O–Li+ + CH3CH3
(b) The conjugate acid of CH3CH2Li is CH3CH3. Text Appendix 4 gives the pKa of CH3CH3 as 50, one
of the weakest acids known. The conjugate base of one of the weakest acids known must be one of the
strongest bases known.

2-50 The newly formed bond is shown in bold.

(a) CH3 O + CH3 Cl CH3 O CH3 + Cl

nucleophile electrophile
Lewis base Lewis acid
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2-50 continued
(b) CH3 O CH3 + H O H CH3 O CH3 + H O H

H3C nucleophile CH3

electrophile Lewis base
Lewis acid
(c)
O H O

H C H + N H H C H

H H N H
electrophile
Lewis acid nucleophile
Lewis base H
H

(d) CH3 NH2 CH3CH2 Cl CH3 N CH2CH3 + Cl

nucleophile electrophile H
Lewis base Lewis acid
H
O O O O

(e) CH3 C CH2 H O S OH CH3 C CH3 O S OH

nucleophile
Lewis base O O
electrophile plus resonance forms
Lewis acid
CH3 Cl

(f) (CH3)3C Cl + AlCl3 H3C C + Cl Al Cl

nucleophile electrophile
Lewis base CH3 Cl
Lewis acid
This may also be written in two steps: association of the Cl with Al, and a second step where
the C—Cl bond breaks.

O O

(g) CH3 C CH2 + O H CH3 C CH2 + H O H

electrophile H nucleophile
Lewis acid Lewis base
F
(h) F B F CH2 CH2 F B CH2 CH2
F nucleophile F
electrophile Lewis base
Lewis acid

(i) BF3 CH2 CH2 + CH2 CH2 BF3 CH2 CH2 CH2 CH2
electrophile nucleophile
Lewis acid Lewis base

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2-51 In each product, the new bond is shown in bold.
H
(a) CH3 N CH3 + H Cl CH3 N CH3 + Cl
Lewis H Lewis H
base— acid—
nucleophile electrophile
CH3
(b) CH3 N CH3 + H3C Cl CH3 N CH3 + Cl
Lewis Lewis
base— H acid— H
nucleophile electrophile
H
O O
(c) CH3 C H + H Cl CH3 C H + Cl
Lewis Lewis
base— acid—
nucleophile electrophile

O O
(d) CH3 C H + O CH3 CH3 C H
Notice in parts (d) and (e) that the
Lewis Lewis O identical reactants can generate two
acid— base—
electrophile nucleophile
CH3 separate products.

H O O
H
(e) H C C H + O CH3 C C H + H O CH3
Lewis Lewis H
acid— H base—
electrophile nucleophile
2-52 In each product, the new bond is shown in bold.
In each case, look for the atom that is the most positive because of induction or resonance, or is the most
electron deficient (like boron with an empty orbital).
(a) O O Resonance forms show that the C in a C=O group always
C has some (+) charge; this carbon is an electrophile.
Nucleophiles will be attracted to it as shown here and in
parts (e) and (f).

The Na+ is a spectator ion

O O
C and plays no active role in
+ O CH2CH3 these reactions. It is not
O CH2CH3 shown here to avoid clutter.
Lewis
base—
nucleophile
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2-52 continued
H H
(b) H N H + O CH2CH3 H N + H O CH2CH3
H H

Br H
(c) H3C C H + O CH2CH3 H3C C O CH2CH3 + Br

H H
H H
(d) H B + O CH2CH3 H B O CH2CH3
H H
(e) As shown in 2-51(d) and (e), there can be more than one reaction pathway. NaOCH2CH3 is a strong base
and can quickly remove a proton from acetic acid, CH3COOH. In addition, the reaction can occur at the C=O
(see 2-52(a)) of acetic acid, although more slowly than proton removal which is one of the fastest reactions
known.
O O
1) C H + O CH2CH3 H O CH2CH3 + C
H3C O H3C O
(draw the other resonance form)
O O
2) C H + O CH2CH3 C H
H3C O H3C O
O CH2CH3
(f) As shown in 2-51(d) and (e), and 2-52(e) above, there can be more than one reaction pathway. Draw
important resonance forms to reveal where the sites of (+) and (–) charge are.
H H H
H C O H C O H C O
C C C
site 1
H H H site 2

H H
H C O + O CH2CH3 H C O
1)
C C
O CH2CH3
H H
H
H H C O This is the most significant
2) resonance contributor.
H C O + O CH2CH3 C
Draw the other one.
C H O CH2CH3
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2-53 In each product, the new bond is shown in bold.
In each case, look for an unshared electron pair, or an electron pair in a double or triple bond, to make a
molecule nucleophilic. An arrow showing electron movement must always begin at an unshared
electron pair or a bond. F

O F O B F
(a) + B F
F F
F F
F B
(b) F
+ B
F F C
H
F F
B
O F O F CH3 F CH3 F

(c) + B (d) N + B H3C N B F

F F H3C CH3 F F
CH3 F
H F H F

(e) H3C O + B H3C O B F

C F F C
H2 H2 F

F F

(f) S + B H3C S B F
H3C CH3 F F
CH3 F

2-54 (a) Ascorbic acid has four OH groups that could act as acids. The ionization of each shows that one
gives a more stable conjugate base.
OH

OH 2 1
O localized negative charge—
O no resonance forms
O
O
O HO OH
OH
1 HO OH
2 O
3 4

ascorbic acid O localized negative charge—

O no resonance forms
OH
HO OH
continued on next page 73
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2-54(a) continued
OH 2 OH OH

O 3 O O
O O O
OH OH OH C
1 HO OH O OH O OH
3 4

three resonance forms, two OH

with negative charge on
4
oxygen O
O
OH
O OH
OH OH

O O
O O
OH OH C two resonance forms, one with
HO O HO O negative charge on oxygen

(b) The ionization of the OH labeled "3" produces a conjugate base with three resonance forms, two of which
have negative charge on oxygen. This OH is the most acidic group in ascorbic acid.
(c) The conjugate base of acetic acid, the acetate ion, CH3COO– , has two resonance forms (see the solution
to problem 2-47), each of which has a C=O and a negatively charged oxygen, similar to two of the resonance
forms of the ascorbate ion. The acidity of these two very different molecules is similar because the
stabilization of the conjugate base is so similar. The strength of an acid is determined by the stability of its
conjugate base.
Note to the student: Organic chemistry professors will ask you to "explain" questions, that is, to explain a
certain trend in organic structures or behavior of an organic reaction. The professor is trying to determine
two things: 1) Does the student understand the principle underlying the behavior? 2) Does the student
understand how the principle applies in this particular example?
To answer an "explain" question, somewhere in your answer should be a statement of the principle,
like: "The strength of an acid is determined by the stability of its conjugate base." From there, show
through a series of logical steps how the principle applies, like drawing resonance forms to show which
acid has the most stable conjugate base through resonance or induction. Answering these questions is
like crossing a creek on stepping stones. Each phrase or sentence is a step to the next stone. When strung
together, the steps bridge the gap between the principle and the observation.

2-55 The examples here are representative. Your examples may be different and still be correct. What is
important in this problem is to have the same functional group.
(a) alkane: hydrocarbon (b) alkene: contains a (c) alkyne: contains a
with all single bonds; can be carbon-carbon double bond carbon-carbon triple bond
acyclic (no ring) or cyclic
H H H H H

H C C C H H C C C H H C C C H

H H H H H H H
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2-55 continued
(d) alcohol: contains an (e) ether: contains an (f) ketone: contains a carbonyl
OH group on a carbon oxygen between two carbons group between two carbons
H H H H H O H
H C C O H H C O C H H C C C H
H H H H H H
(g) aldehyde: contains (h) aromatic hydrocarbon: (i) carboxylic acid: contains a
a carbonyl group with a a cyclic hydrocarbon with carbonyl group with an OH
hydrogen on one side alternating double and single group on one side
H H O bonds H O
H C C C H H C C O H
H H H
(j) ester: contains a carbonyl (k) amine: contains a nitrogen (l) amide: contains a carbonyl
group with an O—C on one side bonded to one, two, or three group with a nitrogen on one side
carbons
H O H H H or R group H O H or R group
H C C O C H H C N H or R group H C C N H or R group
H H H H
(m) nitrile: contains the carbon-nitrogen triple bond: H3C C N

O O O aldehyde
2-56 ether
(a) (b) (c)
C OH C
H
O ether
carboxylic acid
alkene
alkene
O
(d) (e) O (f) O (g) CH2OCH3
ketone ether
O NH aromatic
alkene
aromatic amide (cyclic) C N
ester (cyclic)
nitrile
(h) NH2 O (i) H
HN C COOH carboxylic acid
CH3 CH C OCH3 amine 2
H2C OH alcohol
amine ester
2-57
(a) penicillin G
O amide thioether ("Thio" means sulfur replaces oxygen. This
group is listed on the inside front cover of the text.)
CH2 C NH
S

aromatic N
O carboxylic acid
amide COOH
(cyclic) 75
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2-57 continued
(b) dopamine
alcohol aromatic (In later chapters, you will learn that the
HO
OH group on a benzene ring is a special
NH2 functional group called a "phenol". For
alcohol amine
now, it fits the broad definition of an
HO CH2 CH2 alcohol.)

(c) capsaicin
aromatic amide
ether O
alkene
H3CO
N
H

HO (In later chapters, you will learn that the

alcohol OH group on a benzene ring is a special
functional group called a "phenol". For
now, it fits the broad definition of an
alcohol.)
(d) thyroxine
aryl iodide—
I (four of these) I aromatic amine "Aryl" iodides are attached
to aromatic rings.
NH2
alcohol
HO O CH C COOH
ether H carboxylic acid
I aromatic I

(e) testosterone OH alcohol

ketone

O
alkene

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