Chemistry 233

Chapter 11 Problem Set – Pt. 1 (Substitution Reactions)

1. Consider the SN2 reaction shown below and answer the following questions.
acetone
Br + NaSCH 3 S + +
CH 3 Na Br
A. Write the rate law for the reaction.

B. Identify the nucleophile and the electrophile in the reaction.

C. State how each of the following factors would affect the rate of the reaction.
a. Increasing the concentration of 1-bromopropane.

b. Decreasing the concentration of NaSCH3 by one-half.

c. Changing 1-bromopropane to 2-bromopropane.

d. Changing 1-bromopropane to 1-iodopropane.

e. Changing NaSCH3 to CH3OH.

2. Consider the SN1 reaction shown below and answer the following questions.
Br + O +
HOCH 3 CH 3 HBr
Ph Ph
A. Write the rate law for the reaction.

B. Identify the nucleophile, the electrophile, and the reaction solvent.

C. State how each of the following factors would affect the rate of the reaction.
a. Increasing the concentration of the alkyl halide.

b. Increasing the concentration of HOCH3.

c. Replacing HOCH3 with NaOCH3.

d. Changing the alkyl halide from a bromide to an iodide.

e. Changing the alkyl halide to 1-bromopropane.

Page 1 of 5
 Chem. 233 – Chapter 11 - Pt. 1 Problem Set
3. For each of the following pairs, circle the one that will proceed faster by an SN2 reaction mechanism.

F vs Br

Br vs Br

Cl Cl
vs

Br + NaSCH 3 vs Br + HSCH 3

Br + NaF vs Br + NaI
polar protic solvent polar protic solvent

Br + NaF vs Br + NaI
polar aprotic solvent polar aprotic solvent

Cl Cl
+ NaOH vs + NaSCH 3

polar aprotic solvent polar aprotic solvent

Br + KI (high conc) vs Br + KI (low conc)

4. For each of the following pairs, circle the one that will proceed faster by an SN1 reaction mechanism.

Br vs
Br

Br Br
vs

vs
Cl I

I + NH 3 vs I + NH 2

+ HOEt vs + HOEt (1 equiv)

Br (Solvent) Br THF (solvent)

+ vs +
Cl OH Cl OH
(low conc) (high conc)

Page 2 of 5
 Chem. 233 – Chapter 11 - Pt. 1 Problem Set
5. Explain why the two reactions below provide constitutionally different products.
NaOCH 3

Br OCH3

HOCH 3 H 3CO

Br

6. Assuming each reaction below undergoes nucleophilic substation, predict the mechanism (SN1 or
SN2) and draw the major product. Include stereochemistry where appropriate.

NaOH

Br

NaOH
Br Acetone

NaCN
I DMSO

NH 3
Cl

Br NaSCH 3
DMF

Br HO

I
OCH3
DMSO

I
HOCH 3

Page 3 of 5
 Chem. 233 – Chapter 11 - Pt. 1 Problem Set
Br HSEt
DMSO

I
HOCH 3

I OH
H

Br H 2O

Br H 2O

HO
Br

Br OCH3
DMSO

7. The compound below can undergo an intramolecular nucleophilic substitution via an SN2
mechanism. Draw the product and the mechanism by which it is formed.
Cl DMF
N
H

8. Explain why the reaction below does not provide any products from nucleophilic substation.
+ Na O No Substitution Reaction
Br
(NaOt-Bu)

Page 4 of 5
 Chem. 233 – Chapter 11 - Pt. 1 Problem Set
9. Predict the product(s), with correct stereochemistry for each of the following substitution reactions
involving an alcohol starting material.
1. TsCl
OH Pyr
(a)
2. NaBr

OH HBr
(b)

HI
(c) OH

HBr
(d)
OH

1. TsCl
Pyr
(e) OH
2. NaBr

NaI
(f) OH
THF

10. Show the complete electron pushing mechanism for the reaction in question 9a.

11. Show the complete electron pushing mechanism for the reaction in question 9d.

Page 5 of 5