CHEM212 Practice Problems 1.

(1) Drawing Lewis and Kekule Structures

(a) Complete the following Kekule structures by adding in all of the non-bonding
electrons (leave the bonding electrons as drawn). Pay close attention to the formulas
given to determine the total number of VEs that will be present in molecules/ions
(remember to take ionic charges into account when counting VEs). Include non-zero
formal charges on the diagrams. You may find the Khan Academy videos on drawing
resonance structures helpful: https://www.khanacademy.org/science/organic-
chemistry/organic-structures/formal-charge-resonance/v/resonance-intro-jay
(i) Formula = C3H6O

(ii) Formula = CH3CO2-

(iii) Formula = C3H5+

(iv) Formula = C3H5-

(v) Formula = C4H6O

(f) Cyclopentadienyl ion, Formula = C5H5-

The cyclopentadienyl ion has two more possible resonance structures in addition to those
drawn above. Using the templates given below, draw them.

(g) C6H6Br+ (an intermediate in the bromination of benzene)

(h) C6H5O-
(b) Redraw all of the structures above as skeletal structures.
(c) Draw the relationships between each set of the above resonance forms by using curved
arrows to show how pairs of electrons move from one atom or bond in order to form the next
resonance structure.
(2) (a) Draw the three resonance structures for cyanate ion (OCN -), and rank the resonance
structures in terms of their contributions to the overall resonance hybrid. (b) Compare your
answer to (a) with the answer you would obtain when considering the resonance structures of
thiocyanate ion.
(3) Draw Kekule structures for each of the following:

(a) HO- (b) Br- (c) CH3NO2 (d) H2CO (e) CH3O-

(4) Each of the following are associated with two resonance structures. Draw them, and use
curved arrows to indicate the electron motions that relate the structures to each other.
+ -
(a) Allyl cation, CH2=CH-CH2 (b) Allyl anion, CH2=CH-CH2 (c) Benzene (C6H6) (d)
Formate (methanoate) ion (e) The enolate ion produced from deprotonation of acetaldehyde
-
(HC(=O)CH2 ) (f) nitromethane (CH3NO2)
Acids and Bases
(1) Draw at least one Kekule structure for the conjugate base of each of the following Bronsted-
Lowry acids. The acidic protons are shown in bold. Some of the conjugate bases will have more
than one possible Kekule structure (thats part of the point!)
(a) HCl (b) H2O (c) NH3 (d) CH4 (e) HCO2H (f) CH3OH (g) HNO3 (h) acetone (CH3(CO)CH3).
(2) Draw a reasonable Kekule structure for the conjugate acid of each of the following bases
(there may be more than one).
(a) CN-- (b) NO3- (c) OH- (d) I- (e) HSO4- (f) H2O (g) (CH3)NH2

The following table provides pKa values for various acids. Use the table to provide answers to
questions x y.

Acid pKa Acid pKa

CH3CH2OH 16 10.68

(ethyl acetoacetate)

4.78 20

2.59 25

2.78 25

(ethyl acetate)

2.90 16

(cyclopentadiene)

3.12 CH4 50
 13 CH3-NO2 10.2

(ethyl malonate)

(3) What is the trend in pKa values for the series fluoroacetic acid, chloroacetic acid,
bromoacetic acid, iodoacetic acid and acetone. Explain this trend in pK a values.
(4) Compare the pKa values of acetone and acetonitrile (CH3CN). Using resonance structures for
the conjugate bases of the two acids, explain the difference in pKa values.
(5) Considering that it is a carbon acid (i.e. the acidic proton comes off of a C atom), the pKa of
cyclopentadiene is extremely low (pKa = 16). Bearing in mind your answer to Question I(d),
explain why cyclopentadiene is unusually acidic.
(6) Explain the difference in pKa values between ethyl acetate, ethyl acetoacetatem and ethyl
malonate.
(7). Which of the acids in the table would be efficiently turned into their conjugate bases by
ethoxide ion?
(8) The PKa of diisopropyl amine is 35, which means that its conjugate base (aka LDA) is a very
strong base. Would any of the acids in the table NOT be deprotonated by LDA?
(9) Would the conjugate base of acetone be stable if it was dissolved in ethanol? Explain why or
why not.

Acids, Bases, Nucleophiles and Electrophiles

A summary of the connections between acid strength, CB strength, leaving group ability
and nucleophile strength:

Conjugate Leaving Group Nucleophile

Acid pKa
Base Strength Ability of CB Strength of CB
Strong Acid
Weak CB Good Leaving Weak
Group Nucleophile

Weak Acid Strong CB Poor Leaving Strong

Group Nucleophile

(1) Draw arrow-pushing mechanisms for the following reactions:

(a)
 - -
HO: H Cl H O H :Cl

(b)
H H
H H
- -
HO: Cl HO :Cl
H H

(c)
O O
-
H Br :Br
-
O OH

(d)
O O
-
Br :Br
-
O O

In (a), the hydroxide ion is acting as: (underline all that apply):
Lewis Acid Bronsted Acid Lewis Base Bronsted Base Nucleophile
Electrophile
In (a), the hydrochloric acid molecule is acting as: (underline all that apply):
Lewis Acid Bronsted Acid Lewis Base Bronsted Base Nucleophile
Electrophile
In (b), the hydroxide ion is acting as: (underline all that apply):
Lewis Acid Bronsted Acid Lewis Base Bronsted Base Nucleophile
Electrophile
In (b), the chloromethane molecule is acting as: (underline all that apply):
Lewis Acid Bronsted Acid Lewis Base Bronsted Base Nucleophile
Electrophile
In (c), the acetate ion is acting as (underline all that apply):
 Lewis Acid Bronsted Acid Lewis Base Bronsted Base Nucleophile
Electrophile
In (c), the hydrobromic acid molecule is acting as (underline all that apply):
Lewis Acid Bronsted Acid Lewis Base Bronsted Base Nucleophile
Electrophile
In (d), the acetate ion is acting as (underline all that apply):
Lewis Acid Bronsted Acid Lewis Base Bronsted Base Nucleophile
Electrophile
In (d), the bromoethane molecule is acting as (underline all that apply):
Lewis Acid Bronsted Acid Lewis Base Bronsted Base Nucleophile
Electrophile
(Hopefully, comparison of (a) and (b) or (c) and (d) will reinforce the connection between
acids, bases, nucleophiles and electrophiles)

(2) The numbers shown beneath the nucleophiles and the leaving groups represent the
pKas of their respective conjugate acids. Based on those numbers, do you expect the
reactions to proceed as written, or would they be more likely to proceed in the reverse
direction? Explain briefly how you arrived at your answer.

H H
H H
H
(a) HO- + Cl O + Cl-
H H

15.
pKa -7
7

H H
H H
(b) CN- + OH NC + OH-
H H

15.
pKa 9.3
8
 H H
H H
(c) CN- + OAc NC + AcO-
H H

pKa 9.2 4.78

(AcO- = acetate ion)

H H
H H H
+
(d) HS-- + N H HS + NH3
H H H

pKa 9.2 9.2

(3) The following reactions do not occur as written. In each case, indicate why.
(a)
Br
- + + Br-

Cl SN2 OH
-
+ OH + Cl-
(b)

(b)

SN2 CN
OH + NC
- + HO-

(c)

Br SN2 OH
-
+ OH + Br-

(4) Draw the products from the following reactions, paying careful attention to stereochemistry.
Assign R or S designations to any chirality centers that are present in the molecules.
(a)