Chapter 2

Electronic effects
1) Draw curve arrows in order to convert the structures on the left into the structures on the right.

a) /+
a)

b) b)

Lone pair/ Lone pair/

c)

c)

/+ Lone pair/+

d) d)
e)
e)

Lone pair/ 
Lone pair/ 
-/ 
-/ 
2) Draw resonance contributors for each of the following species. Indicate the most
stable resonance contributor. Justify your answer.

less stable
more stable
because it has
does not have
separated charges
separated charges
and an atom with incomplete octet.
b)
c)
 c)

more stable less stable less stable less stable more stable
does not have does not have
separated charges separated charges
 2.3 Use the curved-arrow formalism to derive the major resonance structures for
each of the following species. Determine which if any structure is the most
important one in each case. Lone pair/ 

d) a)
most stable
negative charge
on the most
Lone pair/  electronegative
element (Oxygen)
e) Lone pair/  Lone pair/ 

c)

Lone pair/ 
Lone pair/ 

negative charge on the more

electronegative element
 2.3 Use the curved-arrow formalism to derive the major resonance
structures for each of the following species. Determine which if any
structure is the most important one in each case.
f) b)

/+ /+

1st structure
3) Classify the following acids by decreasing order.

a) CH3 – CO2H ; b) CH3 – HN – CH2 – CO2H ; c) CH3 – CH2 – CO2H ;

d) H2N – CH2 – CO2H ; e) CH3 – CH(CH3) – CH2 – CO2H

d > b > a > c > e

EWG Weak EWG Weakest EDG Weak EDG EDG
-I -I +I +I +I
4) In each of the following pairs, indicate the strongest acid. Briefly justify your answer.
more acidic
a) CH3-CH2-CH2-OH or (CH3)2CH-OH

CH3-CH2-CH2-O- (CH3)2CH-O-

The strength of an acid depends on the stability of its conjugate base.

The more stable base has the stronger conjugate acid.

The alkyl group can donate electrons inductively (hyperconjugation)

and destabilizes the conjugate base.
b) m-NO2-C6H4-OH or p-NO2-C6H4-OH

EWG increase acidity by

stabilizing conjugate base

EWG inductive

EDG decrease acidity by EWG inductive

destabilizing conjugate base EWG resonance

The p-nitro substituent decreases the pKa both by resonance electron

withdrawal and by inductive electron withdrawal.

The m-nitro substituent can decrease the pKa only by inductive electron
withdrawal. Therefore, the para isomer is the strongest acid.
c) p-CHO-C6H4-OH or p-CH3O-C6H4-OH Stronger acid

EWG
resonance and
inductive

EDG resonance
EWG inductive

A formyl (HC=O) substituent attached to a A methoxy (CH3O) substituent attached

benzene ring withdraws electrons by resonance to a benzene ring withdraws electrons
and withdraws electrons inductively inductively (through the σ bonds)
because oxygen is more electronegative
than carbon. The group also donates
electrons by resonance (through the π bonds)
5) In each of the following pairs, indicate the strongest base. Briefly justify your answer.

a) C6H5-NH2 or C6H11-NH2
lone pair is has the greater electron
delocalized density on its nitrogen
because the lone pair cannot
be delocalized.
stronger base

b) CH3-CO-CH2-NH2 or CH3-CH2-CO-NH2

lone pair lone pair is

is localized delocalized
stronger base
 EWG
resonance and inductive

EWG inductive
Stronger base

From the meta position only the inductive effect of C=O is operative; and from the
para and ortho positions, both inductive and resonance effects are operative.
6) Rank the following compound from least acidic to most acidic and attribute to each
its pKa value. Approximate pka values: 5- 7- 9 and 10.

pKa = 7 pKa = 9 pKa = 10 pKa = 5

The carboxylic acid (d) is the most acidic because its conjugate base
has greater delocalization energy than does the conjugate base of phenol (c).
NO2 substituent is EWG (by both inductive and resonance in para position) and only by
inductive in meta position. Electron withdrawing substituent increase the acidity of a
compound by stabilizing its conjugate base.
7) In each2.7ofIn each
the of the following
following pairs, identify
pairs, identify the molecule
the molecule with the
having the smallest pKa.
lowest pKa and give a brief (1-2 words) explanation.
Justify briefly your answer.

sp2 2 sp3
sp lowest pKa ,
more acidic

A B

A is the stronger acid because its hydrogen is attached to an sp2 hybridized nitrogen,
which is more electronegative than the sp3 nitrogen.
An H attached
AntoHan sp2 hybridized
attached to an sp2nitrogen
hybridized
is more
nitrogen
acidic
is more acidic
than an H attached
than antoHan sp 3 nitrogen.
attached to an sp3 nitrogen.
A has the lowest pKa
 C D
D is the
stronger acid

conj. base:
C’ D’

localized electrons delocalized electrons, more

stable conjugate base.
C=O is EWG (resonance)

Alternative explanation: the C=O is EWG (inductive), decreasing electron

density on the nitrogen which stabilize the conj. base D’.
 E F

conj.
base

E’ F’
delocalized electrons delocalized electrons
Explanation: conj. base of E has more resonance structures, is
more stable E is more acidic than F.
Alternative explanation: sp2 is more
Alternative explanation: electronegative
iin E, CH2 bonded to two sp2 carbons.
in F, CH2 bonded to one sp3 carbon and one sp2 carbon. than sp3
sp2 is more electro(-) than sp3
E is more acidic than F
8) Rank the2.8
following
In each ofmolecules from
the following sets,strongest
arrange thetocompounds
weakest acid. Justify
in order your answer briefly.
of increasing
acidity. Explain your choices.
a)
a)

EDG EWG EWG

inductive inductive inductive

I J K

Electron withdrawing groups (inductive) increase acidity

Electron donating groups (inductive) decrease acidity
in NO2, N has full (+) charge
NO2 is more withdrawing by inductive than OCH3

Increasing acidity I < J< K

 Conj. Bases:
a)

I’ J’ K’
EDG EWG EWG
inductive inductive inductive

EWG(Inductive) increases acidity by stabilizing conjugate bases

NO2 more withdrawing by inductive than OCH3

EDG (Inductive) decreases acidity by destabilizing conjugates bases

Increasing acidity: I < J< K

b)
+
CH3NH—CH2CH2 —OH; CH3NH—CH2CH2CH2—OH; (CH3)3N—CH2CH2—OH

EWG EWG EWG

inductive inductive inductive
L M N

EWG(Inductive) increase acidity by stabilizing conjugate bases

(CH3)3N+ is more withdrawing (inductive) than CH3NH in L

CH3NH is more withdrawing than NH2CH2 in M
because Nitrogen is more electronegative than Carbon
Electron withdrawing (inductive) effect decreases with distance

Increasing acidity M < L< N

c)

O P Q R

An electron-withdrawing substituent (Cl) makes the carboxylic acid more acidic, because
it stabilizes its conjugate base by decreasing the electron density around the oxygen atom.

The greater the number of electron-withdrawing chlorine atoms equidistant

from the OH group, the stronger the acid.

Acidity: O < P < Q < R

9) Rank the following molecules from least basic to most basic. Justify your answer briefly.

EDG least basic two

inductive EDG
inductive
most basic

Alkyl groups donate electrons inductively (hyperconjugation) and increase

electron density on nitrogen. The basicity of the nitrogen increases.
 EWG A B A stronger C
EDG
inductive EWG
inductive
inductive

EWG (Inductive) decrease electron density and decrease basicity

EDG (Inductive) increase electron density and increase basicity
NH3+ more electron-withdrawing by inductive than C=O therefore
decreasing basicity

Electron density on N: C < A < B

Basicity: C < A < B
 A B C
has the greater electron
density on its nitrogen
because the lone pair
cannot be delocalized.
delocalized stronger base
localized
electrons electrons

Electron density on N: A < B < C

Basicity: A < B < C
2 resonance
structures
5 resonance
structures
10) Compare the acidity of the following compounds

a) O2N – CH = CH – CH = CH – CH = CH – CH2OH
b) O2N – CH2 – CH2 – CH2 – CH2 – CH2 – CH2OH
c) O2N – CH2 – CH2 – CH2OH

NO2 can withdraw electrons only inductively in b) and c). The closer the NO2 substituent is to
the acidic proton, the more it can decrease the electron density around the oxygen because
it has to exert its effect through fewer bonds. Therefore, the closer it is, the more it stabilizes
the conjugate base and increases the acidity of its conjugate acid.
c) is more acidic than b)

NO2 can withdraw electrons both inductively and by resonance in a) therefore a) is the most acidic

acidity: a) > c) > b)

11) Rank the following anions by increasing order of basicity. Justify your answer briefly.

A B C

In A there are two CH3 EDG (inductive).

In B there is one CH3 EDG (inductive).
In C there are three C2H5 EDG (inductive).

EDG (Inductive) increase electron density increases basicity

Electron density on Oxygen: C > A > B

Basicity: C > A > B
b)
a)

A B C

Host elements are in the same row:

The most electronegative element is the least basic

electronegativity order : F > O > C

Increasing basicity: C < A < B

c)

X Y Z
sp sp3 sp2

Same host element (carbon) with different hybridization

The more electronegative element is the least basic
electronegativity order: sp > sp2 > sp3

Increasing basicity X<Z<Y

d)

A B C

Because oxygen is more electronegative than nitrogen

B is more basic than A
A and C have the same host element
+
In C there is NH3 (EWG Inductive) which decreases
electron density on oxygen making C less basic than A.
A is more basic than C

Increasing basicity: C < A < B

 12) Identify the most acidic hydrogen in each compound and briefly explain your answer.

In a) The most acidic hydrogen is Ha because when the carboxylic acid loses the
Ha proton, the electrons left behind are shared by two oxygens (the electrons are delocalized).

In b) The most acidic hydrogen is Hd because when vitamin C loses the

Hd proton, the electrons left behind can be delocalized. Three resonance structures can
be shown for the conjugate base. In two of these the negative charge is on an oxygen.
If you are thinking of Ha you also get 3 resonance structures but with negative charge
on oxygen in one of them only.
13) Identify the most acidic proton in each of the compounds and justify briefly your answer.

The most acidic H

are shown in red.
When one of these
red protons is lost,
the negative charge
in conjugate base
can be delocalized.
most acidic H is shown
in red.When the one of
red protons is lost, the
negative charge in conjugate
base can be delocalized.

most acidic H is shown in

red. It is attached to an
electronegative element in
e) and f)
 14) Compare the basicity of the following compounds:
A B C D E

localized
electrons
EWG
EWG
inductive EWG most basic
Inductive
and Inductive
resonance and
EDG
EWG decreases electron resonance
density and decreases basicity
EDG increases electron
density and increases basicity Electron density on N: E > D > A > B > C
Basicity: E > D > A > B > C
 Explain why?
15)

A
B

a) The nitrogen in A is less basic because the lone pair (in a p orbital)
is delocalized onto the ring, so it is not available to be protonated.
In B the nitrogen lone pair (in an sp2 orbital and is not a part of
the π-conjugated system) cannot be delocalized.

b) The vinylic lone pair is in an sp2 orbital and is vinylic

not a part of the π-conjugated system. The allylic
lone pair in an p orbital and is a part of the
π-conjugated system ( delocalized). allylic
16) Discuss the value of pKa values, of benzoic acid PhCOOH, p-hydroxybenzoic acid and
pmethoxybenzoic acid.

Both OH and OCH3 donate electrons by

resonance and withdraw electrons inductively.
But the pKa values suggest that the OCH3
is more donating than the OH because of
most acidic least acidic the presence of CH3 group.

Electrons donating groups decrease

acidity by destabilizing the conjugate base.
 17) Rank the following carbocations in order of increasing stability.

a) C H b) H3C C H c) H C CH d) H C CH CH e) H3C CH2

2 2 2
CH3

secondary benzylic secondary vinylic primary allylic primary

stabilized by resonance stabilized by resonance

stability: c < e < b < d < a

18) Classify the compound below as : acid, base, nucleophile (and) or electrophile:

a) CH3 – NH2 b) CH3 – C ≡ C – H c) CH3 – C ≡ C –

d) H – CN e) CN– f) BF3

a) CH3 – NH2 acid, base, and nucleophile

b) CH3 – C ≡ C – H acid
c) CH3 – C ≡ C – base, and nucleophile
d) H – CN acid
e) CN– base, and nucleophile
f) BF3 acid, and electrophile
19) In each of the following pairs specify the most stable species?

primary carbocation secondary carbocation

more stable

delocalized electrons localized electrons

more stable

secondary benzylic radical Primary radical

stabilized by resonnance
more stable
 stabilized by resonnance secondary carbocation
more stable

primary carbocation primary carbocation

more stable Cl withdraws electron inductively
and destabilizes the carbocation

CH3 donates electron inductively CF3 withdraws electron inductively

and destabilizes the carbanion and stabilizes the carbanion
more stable
stabilized by resonnance secondary carbocation
more stable

localized electrons
delocalized electrons
more stable
20) In each of the following pairs specify the most stable species?

delocalized electrons
inside the ring and
outside the ring
delocalized electrons
only inside the ring

delocalized electrons:
conj. (+)/π,
more stable
tertiary benzylic carbocation tertiary carbocation
stabilized by resonnace destabilized by an
electron-withdrawing
group C=O
c)

delocalized electrons
c) conj. (+)/π,
only 2 resonance structures

delocalized electrons
conj. (+)/π/ π in the ring
more resonance structures
more stable
not aromatic aromatic
less stable more stable
 C D
e)

delocalized electrons
delocalized electrons conj. lone pair/ π
conj. lone pair/ π
D is more stable than C,
(-) charge on more electro(-)
element
 delocalized electrons localized electrons
more stable

delocalized electrons onto delocalized electrons on

one of the carbonyl oxygens both of the carbonyl oxygens
more stable
 Ch. II Choose the correct answer (A, B, C or D) (one choice only):

1- A 8- B

2- A 9- C

3- B 10- C

4- D 11- A

5- A 12- D

6- D 13- B

7- A