FACULTY OF ARTS AND SCIENCE

CHEMISTRY AND BIOCHEMISTRY DEPARTMENT

CONCORDIA UNIVERSITY

CHEMISTRY 222/4 SECTIONS 02 & 51

FINAL EXAMINATION

Instructors: Christopher J. Wilds and Sébastien Robidoux

Name: _____________________

Student ID: _____________________

Special Instructions:

- Molecular models and calculators are allowed

- There are twelve questions.
- You must answer the first three questions.
- For the last 9 questions you must answer only seven of them.
- All questions have equal mark value.
- If you require extra space you may write on the back of the sheet –
only this exam will be corrected!

GOOD LUCK!!!

MARKS:

Q1: / 10 Q2: / 10
Q3: / 10 Q4: / 10
Q5: / 10 Q6: / 10
Q7: / 10 Q8: / 10
Q9: / 10 Q10: / 10
Q11: / 10 Q12: / 10

TOTAL: / 100
Question 1. Give the structure of compound based on the mass, IR, 13C and proton NMR spectra shown
below. 13C NMR spectrum was acquired with broadband decoupling i.e. 13C-1H splitting is removed.
Provide a brief explanation of your reasoning.
Question 2. Predict the mononitration product of the following reaction. Explain your choice by providing
a complete mechanism with arrow pushing and showing all intermediates and all resonance forms. Suggest
which would be the major product and why.

HNO3
HO2C O CO2H
H2SO4

Question 3. Show how an ester, amide and carboxylic acid can be reduced in one step to an aldehyde,
amine and alcohol, respectively. Indicate the reagent(s) used and explain what is different in each reaction.

Question 4. Explain briefly and provide a structural example of the following:

a) an aldehyde can be converted reversibly to an acetal

b) an epoxide reacts irreversibly with a nucleophile

c) enolates are stabilized by resonance

Question 5. Indicate the product formed in each reaction. Provide a complete mechanism for one of the
reactions. Explain why the outcomes of two reactions are different.
O
H
CH3
CH3CH2OH

O
H
OH
CH3CH2OH
Question 6. Give the structure of compound based on the mass, IR, 13C and proton NMR spectra shown
below. 13C NMR spectrum was acquired with broadband decoupling i.e. 13C-1H splitting is removed.
Provide a brief explanation of your reasoning.
Question 7. How would you synthesize one of the following compounds from the indicated starting
material? Assume that ortho and para isomers can be separated. You are allowed to use any compound that
has a maximum of one carbon atom. You can use the starting material many times.

(a) (b)
CH3
O
O2N Br

Question 8. In class, we have seen the effects of various electron donating and withdrawing groups on the
reactivity of a benzene ring towards an electrophile. Which of the following two alkenes will react faster
with HBr? Explain your answer and draw the resonance structures of the carbocation intermediates.

CH CH2 CH CH2
or
H3CO O2N

Question 9. Tamoxifen is a drug used in the treatment of breast cancer. How would you prepare
tamoxifen from benzene, the following ketone, and any other reagents needed?

CH2CH3
C O C C

(CH3)2NCH2CH2O (CH3)2NCH2CH2O

tamoxifen

Question 10. What are the products A and B obtained in the reaction below? Explain their formation and
draw the reaction mechanism involved in their formation.

A. O 1. Na+ -C C CH3 B.
HBr

2. "mild" acid
 Question 11. Fill in the reagents A-J for the diagram below.

A conc.
NaBH4 HBr
B C D

ide
inim 1) Mg, ether
H2NNH2 ucc
- mos 2) CO2
OH, heat bro +
r N- ht 3) H2O, H3O
o lig
Br 2
E H
C C2H5
CO2H

SOCl2

excess
SOCl2 NH3 1. LiAlH 4
CH3CO2H G H I
2. H 2O, H 3O+

Question 12. Rank the following compounds in terms of acidity (1 being the highest and 3 being the
lowest). Explain their relative acidity and draw the relevant resonance structures.

O H
CO2H O CH3
CO2H

NO2
NO2