Version
1
CHEM
2OB3
Summer
2013
S.
Knight
&
G.
Bahun
Final Examination - August 8th, 6:00 - 9:00 p.m.
NAME________________________________________________
STUDENT NUMBER____________________________________
DO NOT OPEN THIS EXAM UNTIL INSTRUCTED TO DO SO.
THIS TEST CONSISTS OF 22 PAGES. You are responsible for ensuring that your copy of
the test paper is complete. Bring any discrepancy to the attention of the invigilator BEFORE
you begin writing the test. You are permitted to use molecular models and the standard
McMaster standard calculator (Casio FX 991). NO OTHER AIDS ARE ALLOWED!
Tables of spectral and other data are provided on pages 21 to 22.
THIS TEST IS IN TWO PARTS. PART I CONSISTS OF 20 MULTIPLE CHOICE
QUESTIONS (WORTH 2 MARKS EACH) TO BE ANSWERED ON THE SCANTRON
EXAMINATION SHEET. INSTRUCTIONS ARE PROVIDED ON PAGE 2.
PART II CONSISTS OF 6 QUESTIONS (TOTALLING 74 MARKS) . READ THE
QUESTIONS CAREFULLY. WRITE YOUR SOLUTIONS NEATLY IN THE SPACES
PROVIDED. NO OTHER FORMAT WILL BE ACCEPTED.
NOTE: IT IS EXTREMELY IMPORTANT TO MAKE SURE YOUR SCANTRON SHEET
IS PROPERLY COMPLETED, OTHERWISE YOU WILL LOSE MARKS.
Remember to ENTER YOUR VERSION NUMBER, which can be found on the top right hand
corner of this page, by filling in the BUBBLE in the “version” column provided. Finally,
BUBBLE in your STUDENT number. Now CHECK all of your entries.
Q21 Q22 Q23 Q24 Q25 Q26 TOTAL MC
11 12 19 9 10 14 74 40
An unexamined life is not worth living. –Socrates
Section 1: MULTIPLE CHOICE [Questions 1-20 are 2 marks each]
Question 1: Which epoxide(s) would form the following alcohol when combined with
CH3MgBr, followed by an acidic workup?
d) all of the above
e) none of the above
Question 2: How many resonance contributors are possible in the first step of toluene reacting
with SO3 during sulfonation of the aromatic ring (i.e. when toluene forms the sigma complex)?
a) 5
b) 6
c) 7
d) 8
e) 9
Question 3: How many UNIQUE products are formed from the following reaction sequence,
assuming NO oxygen attack takes place:
a) 1
b) 2
c) 3
d) 4
e) 6
Page 2 Continued on Next Page
Question 4: How many AROMATIC carbon AND hydrogen signals would you expect in the
NMR spectra of the following molecule:
# of C Signals # of H signals
a) 1 2
b) 3 4
c) 4 4
d) 6 6
e) 2 1
Question 5: Oxygen 18 (O18) is a common isotope used to label biological precursors. Which of
the following intermediates would you expect to form in the reaction provided?
A
B
C
D
E
Question 6: Which product would be formed from the following reaction sequence?
A
B
C
D
E
Page 3 Continued on Next Page
Question 7: Which of the following statements about glucose (shown below) is/are FALSE?
i. It is a pyranose ring.
ii. This projection represents the β-anomer.
iii. It is a non-reducing sugar.
iv. It would be significantly more stable as a 5-membered ring.
a) i, ii
b) iii, iv
c) i, iii
d) ii, iii, iv
e) i, iv
Question 8: Which of the following best represents a product of the Diels-Alder reaction given?
A
B
C
D
E
Page 4 Continued on Next Page
Question 9: Give the product of the following reaction sequence. Do not assume a ring is too
deactivated for a reaction to take place.
A
B
C
D
E
Question 10: Which of the following statements about the molecule shown below is TRUE.
i. When combined with CH3MgBr, addition will take place at carbon C.
ii. This molecule can be used in a Robinson Annulation.
iii. The molecule can act as a Michael acceptor.
iv. It can easily form an enolate in the presence of an alkoxide.
v. An enamine will add to carbon C.
a) i, iv
b) ii, iii, v
c) ii, iii
d) iii, v
e) iii, iv
Page 5 Continued on Next Page
Question 11: What is the product of the following reaction sequence?
A
B
C
D
E
Question 12: If Compound A were left in a solution of sulfuric acid and water for an extended
period of time, which of the following compounds (I-IV) would you expect to form?
a) I and II
b) I and IV
c) I, II, and IV
d) I, II, and III
e) II and III
Page 6 Continued on Next Page
Question 13: Which reagents would you use to synthesize this compound via an aldol
condensation?
A
C
B
D
E
Question 14: Which of the following radicals is MOST STABLE?
A
B
C
D
E
Question 15: What are the fundamental steps in any radical reaction, in the correct order?
a) Radicalization, Propagation, Halogenation, Termination.
b) Initiation, Termination, Polymerization, Alkylation.
c) Halogenation, Initiation, Propagation.
d) Initiation, Propagation, Termination.
e) Polymerization, Tautomerization, Alkylation, Transmogrification.
Page 7 Continued on Next Page
Question 16: The product of the following sequence of reactions is best described as:
a) An ester
b) An anhydride
c) An amide
d) An enamine
e) A thioester
Question 17: Which compound below could be formed when 4-methylbutan-2-one is treated
with a solution of D2SO4 in D2O at room temperature?
A
B
C
D
E
Question 18: How many unique products are formed from the following reaction?
a) 4
b) 6
c) 8
d) 12
e) 16
Page 8 Continued on Next Page
Question 19: Which of the following would combine to yield the Robinson Annulation product
shown?
A
B
C
D
E
Question 20: Which of the following reagents/conditions could be used to perform the following
synthesis?
a) i) SOCl2, Pyridine ii) Sodium Benzoate
b) DCC, CH2Cl2
c) 0.5 equiv. SOCl2, Pyridine
d) None of the above
e) All of the above
Section 2: WRITTEN ANSWER - Record your answer in the space provided
Page 9 Continued on Next Page
Question 21: You are given the Fischer projections of Tagatose and Mannose below. For each
sugar, indicate whether they are in the D- or L- configurations. Using the templates you are
given, provide the Haworth projection AND chair conformation of the MOST STABLE anomer
in aqueous solution. SHOW ALL HYDROGENS. [11 Marks]
Tagatose
Mannose
CIRCLE
CIRCLE
L
D
ONE
ONE
L
D
Page 10 Continued on Next Page
Question 22: Give all appropriate resonance structures to explain why very little of the meta-
product is observed when anisole reacts with an electrophile (E+). Give ONE reasons why. Use
curly arrows to show how you obtained each resonance structure ON THE TEMPLATES
PROVIDED. [12 marks]
Resonance Structure(s):
Ortho attack:
Meta attack:
Para attack:
Explanation for selectivity (ONE REASON):
Page 11 Continued on Next Page
Question 23: Give the final product and full mechanisms for each step in the following reaction,
using the space provided. You do not need to show resonance contributors. For step 2, showing
the mechanism at one centre is sufficient for full marks. Any tautomerizations do not need
mechanisms shown. [19 marks]
Steps 1-3:
Step 4:
Step 5:
Page 12 Continued on Next Page
Question 24: Given spectral data (without solvent peaks) for compounds A and B below,
provide a total synthesis of compound C from compounds A and B, and any reagent you require.
[9 marks]
Data for Compound A: Formula: C7H6O
IR Peaks:
i. Strong Peak @ ~1700 cm-1
ii. Cluster of medium peaks @ ~ 3025 cm-1
1
H NMR:
1
H
Singlet
2
H
Multiplet
2
H
Multiplet
1
H
Multiplet
13
C NMR - (ON NEXT PAGE)
Compound A:
5
Peaks
Total
Data for Compound B: Formula: C5H10O
IR Peaks:
i. Strong Peak @ ~1710 cm-1
ii. Cluster of medium peaks @ ~ 2920 cm-1
1
H NMR:
6H
Doublet
1H
Singlet
2H
Doublet
(2.3
ppm)
1H
Multiplet
(2.22
ppm)
13
C NMR:
Page 14 Continued on Next Page
Compound B:
4
Peaks
Total
Compound C:
Ph
Synthesis of C from A and B:
Page 15 Continued on Next Page
Question 25: The zombie apocalypse can be avoided with proper chemistry. Lead researchers at
McMaster have discovered that Penicillin Derivative "Z" (aptly named, indeed) has proven to be
an efficient antibiotic against the bacterium responsible for the so-called "zombie virus". Provide
reagents, solvents and conditions as appropriate in the following synthesis of Penicillin
Derivative "Z", using any reagent you deem appropriate. Or don't, but then you'll just be another
useless, smelly zombie. [10 marks + the fate of humanity]
STEP REAGENTS/ CONDITIONS STEP REAGENTS/ CONDITIONS
A E
B F
C G
D
Page 16 Continued on Next Page
Question 26: Choose 14 of the following 18 reactions and show the MAJOR product(s) formed
in the space provided. If no reaction occurs, write no reaction. THE FIRST 15 ANSWERS WILL
BE MARKED. If you do not wish to provide an answer, LEAVE THE SPACE BLANK or cross
out anything in the space [14 marks].
Page 17 Continued on Next Page
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The following space is for ROUGH WORK ONLY. THEY WILL NOT BE GRADED!
Page 19 Continued on Next Page
The following space is for ROUGH WORK ONLY. THEY WILL NOT BE GRADED!
Page 20 Continued on Next Page
Acid pKa
HI -9
HBr
-8
HCl
-7
H2SO4 -5.2
H3O+
-1.74
H3PO4
2.1
CH3CO2H 4.76
H2CO3 6.36
NH4+
9.24
HCO3-
10.33
H2O 15.7
CH3CH2OH 15.9
CH3C=OMe
20
HC CH
25
H2 35
NH3
38
CH2=CH
2 44
CH3CH3 51
Page 21 Continued on Next Page
IR
CORRELATION
CHART:
END
Page 22
