2OA3 Final Exam Spring 2021

© 2021 DEPARTMENT OF CHEMISTRY AND CHEMICAL BIOLOGY MCMASTER UNIVERSITY
CHEM 2OA3 (Spring 2021) – Final Exam

DATE – Thursday June 17th, 2021 from 7:00 − 9:30 PM
TEST DURATION – 150 minutes
SUBMISSION DEADLINE – 10:00 PM via Crowdmark
EXAM BOOKLET –Consists of 8 questions on 20 pages
LATE SUBMISSIONS WILL NOT BE ACCEPTED.
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answered. This document contains 8 questions on 20 pages.
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CHEM 2OA3: Final Exam
Q1 Q2 Q3 Q4 Q5 Q6 Q7 Q8 TOTAL
/17 /15 /12 /12 /18 /8 /14.5 /15 /111.5
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FINAL EXAM © 2021 DEPARTMENT OF CHEMISTRY AND CHEMICAL BIOLOGY MCMASTER UNIVERSITY PAGE 1 OF 20
Question 1. (17 marks) Answer the following questions pertaining to the structure of compound 1
shown below:
HO O
N
A Hd
H B C N
Hc
Et
Ha
D Hb
a
E 1
* H
OH
OH
HO
b
C
c
(a) How many primary, secondary and tertiary alcohol group(s) are present in compound 1?
Primary Secondary Tertiary
(b) Indicate the number of sp2 and sp hybridized carbon and heteroatoms that are present in
compound 1:
sp2 Carbon sp Carbon sp2 Heteroatom sp Heteroatom
(c) How many sp3 hybridized methylene group(s) are present in compound 1?
(d) How many chirality centre(s) are present in compound 1?
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(e) The carbon atom marked * is (CIRCLE your answer):
Achiral Chiral and R Chiral and S Chiral and syn Chiral and anti
(f) At pH 7, compound 1 exists predominantly as (CIRCLE your answer):
(A) A positively charged species, in which the most basic group is protonated
(B) A negatively charged species, in which the most acidic group is deprotonated
(C) A positively charged species, with two basic groups protonated
(D) The neutral structure shown above
(E) A zwitterion (having both a positive and negative charge, but neutral overall)
(g) The substituents (i.e., non-hydrogens) on ring D are best described as (CIRCLE your answer):
trans cis syn anti None of these
(h) Which of the ring(s) A-E has AT LEAST ONE pair of substituents that must be ECLIPSED? If none of
these rings have substituents that are eclipsed, then clearly indicate NONE.
(i) Indicate the MULTIPLICITIES for the hydrogens directly attached to ring C (Ha-d) (assume there is
no coupling due to hydrogens of any exchangeable groups, and assume simple splitting):
For Ha For Hb For Hc For Hd
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Question 2. (15 marks) Answer the questions below that relate to the structure and reactivity of the
following species:
NH2
Br
I
OH Cl
(a) Complete the structure below to show the correct Lewis structure for this compound in aqueous
acidic solution at pH 2. Be sure to clearly show all lone pairs of electrons and charges:
Br
I
O Cl
(b) Which is the best leaving group in this compound:
In an SN1 reaction In an SN2 reaction
(c) Which is the best nucleophile in this compound under the following reaction conditions:
Aqueous Acidic
Organic Solvent
Conditions
(i.e., DMSO)
(i.e., pH 2)
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(d) Based on your answers, propose the reaction product for the intramolecular reaction of this
species with silver nitrate in aqueous acidic conditions (at pH 2). Also, provide the mechanism for
the formation of this product (showing all atoms). Be sure to show all lone pairs, charges, curly
arrows, etc. to illustrate the movement of electrons in this reaction.
(e) Based on your answers, propose the reaction product for the intramolecular reaction of this
species in an organic solvent such as DMSO. Also, provide the mechanism for the formation of this
product (showing all atoms). Be sure to show all lone pairs, charges, curly arrows, etc. to illustrate
the movement of electrons in this reaction.
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Question 3. (12 marks) Answer the following questions about the reaction scheme shown below:
(a) Provide structures for products A-E. Make sure you show the stereochemistry for these products
where appropriate. Spectral data has been given to aid in the determination of these products.
1. Hg(OAc)2,
OH KOEt, EtOH (1 eq.)
heat (1 eq) 2. NaBH4
Br
A B
IR: 1630 cm-1 1H NMR: signal @ 3.5 ppm, 2H, q
H2SO4 (conc.),
heat
(1 eq.)
AgNO3, EtOH, HCl, cold, dark

cool (1 eq.)
E D C
1H NMR: signal @ 3.7 ppm, 4H, q 13C
MS: signals @ 176 + 178 NMR: signals @ 128 + 122 ppm
with a ratio of 3:1
(b) Which of the following describes the stereochemistry you expect for compound E (CIRCLE your
answer):
A mixture of 2 A mixture of 2
A single A racemic A meso
diastereomers, one of which diastereomers, both
enantiomer mixture compound
is chiral, the other meso of which are achiral
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Question 4. (12 marks) Draw the MAJOR product(s) for each reaction. Be sure to show all necessary
stereochemistry. If more than one enantiomer is produced, write “+En” beside your product.
Reaction Product(s)
1. NaH
(a) H
2. EtBr
O
1. O
(b) O H
2. H3O+
Br AgCN
(c)
1. BH3, THF
(d) H
2. H2O2, NaOH
1. O3
(e)
2. Me2S
AgNO3
Br
(f)
MeOH, cold
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Question 5. (18 marks) Answer the following questions about the reactions of Cl Ph
the compound shown alongside: Et 4
5
2
1
OH
(a) Assign absolute configuration (R, S or achiral) to each of the following chirality centres:
C1 C2 C4 C5
(b) What substituent(s) is/are trans to the OH group at C2 (not including hydrogens)? Clearly identify
the substituent(s) and the ring carbon(s) to which it is/they are attached:
(c) Complete the Conformer A template below to show the compound shown above in its chair
conformation. Be sure to use the carbon numbers as indicated on the structure above and the
template below, and show ALL hydrogen atoms on the ring. Then complete the Conformer B
template to show a ring flip of this compound.
Conformer A Conformer B
1 2
2
1 6 6
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(d) What substituent(s) has/have 1,3-diaxial interactions in your structure from Part (c) (not
including hydrogens)? Clearly identify the substituent(s) and the ring carbon(s) to which it/they is
attached:
Conformer A Conformer B
(e) Draw the MAJOR product(s) as a line diagram (not a chair or a boat conformer) of the following
reactions of this compound:
Reaction 1 Reaction 2
1. TsCl, pyridine H2SO4 (conc.),

Cl Ph
2. Heat, pyridine Et hot
4
5
2
1
OH
Reaction 3 Reaction 4
KOtBu, hot KOH, hot
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(f) Indicate which conformation(s) A and/or B is/are involved in the each of the four reactions of this
compound in Part (e) above. If neither of these conformers are involved in these reactions, clearly
indicate NEITHER. CIRCLE ONE answer for each reaction below:
Reaction 1 Reaction 2 Reaction 3 Reaction 4

Conformer A Conformer A Conformer A Conformer A
Conformer B Conformer B Conformer B Conformer B
Both Both Both Both
Neither Neither Neither Neither
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Question 6. (8 marks) In class, we studied elimination reactions to produce alkenes. This question
asks you to extend those ideas to a novel reagent, NaI, which can be used to eliminate bromine and
acetate groups from a 2-halo-ester as shown. This transformation proceeds in two steps, in which the
elimination reaction involves overall syn stereochemistry for the two groups that are eliminated.
Answer the following questions to derive a mechanism for this transformation. Note: −OAc =
−OC(O)CH3.
Br NaI
H O
Alkene
O
(loss of −Br
and −OAc)
(a) Provide a mechanism for the first step in this transformation which involves a substitution
reaction on the 2-halo-ester substrate. Use the template shown below and make sure to show all
curly arrows, charges, intermediates, lone pairs, etc.. Indicate the MAJOR product formed,
including stereochemistry, and be sure to keep the orientation of the product the same as for the
starting material.
Br
H O
O
(b) Provide a mechanism for the second step in this transformation starting from your product in
Part (a) which involves production of elemental iodine (I2). Indicate the MAJOR product formed,
including stereochemistry, and be sure to keep the orientation of the product the same as for the
starting material.
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(c) Based on your mechanism, would the opposite diastereomer of the 2-halo-ester substrate give you
the same product(s) or different product(s) in this transformation? What term BEST describes the
stereochemistry of the pair of elimination transformations involving the two diastereomers of
the 2-halo-ester substrate?
Same or Different Product(s) Stereochemistry
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Question 7. (14.5 marks) Sometimes, compounds react to give very different products than expected.
Consider the reactivity of 2-cyclobutyl-propene (shown below).
(a) Reaction with borane in THF, followed by H2O2/NaOH proceeds as expected. Draw the
EXPECTED product from the reaction of 2-cyclobutyl-propene with borane in THF, followed by
H2O2/NaOH.
(b) However, the ACTUAL product obtained in the hydration reaction with aqueous sulfuric acid is
shown below. For this reaction, think carefully about the bonds you need to make and break, then
use your knowledge of organic chemistry to propose a mechanism for this reaction, showing
EVERY STEP and INTERMEDIATE, ALL correct curly arrows and charges, and lone pairs when
they are involved in this mechanism.
OH
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(c) Draw a reaction co-ordinate diagram for the reaction described in Part (b). Make sure you label
the axes, that you have the correct number of transition states, intermediates, etc., that endo- and
exergonic reactions are shown correctly, and that you clearly show the activation energy (E a) for
this transformation. Assume that the overall reaction is spontaneous.
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Question 8. (15 marks) Answer the following question towards the identification of an unknown
compound given the MS, IR, 1H and 13C NMR spectra.
MS
IR
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13C NMR (Full spectrum shown)
1H NMR (Full spectrum shown)
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(a) Do the spectra show evidence that any functional groups are present that contain sp2 hybridized
atom(s), and if so, which signals show this evidence? Answer by completing the boxes and spaces
below (be specific and indicate the functional group/bond involved and where it is found in the
spectrum):
Yes No Evidence
IR ު ު
1H NMR ު ު
13C NMR ު ު
(b) Does the mass spectrum reveal the presence of heteroatom(s) (e.g., O, N, Cl, Br, etc.) in this
unknown compound? Be specific and indicate the signal(s) that support your answer.
(c) Determine the molecular formula for the unknown compound. How many degrees of
unsaturation (i.e., index of hydrogen deficiency) are present in the unknown compound?
Molecular Formula Degrees of Unsaturation
(d) How many hydrogen(s) are present in the signal at 1.8 ppm? How many neighbours does this
signal have?
Number of Hydrogen(s) Number of Neighbours
(e) What alkyl group(s) is/are present that account(s) for the 1H NMR coupled signals between 0
and 2.5 ppm in the unknown compound (e.g., CH3-CH-CH2-CH etc.)?
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(f) Draw the most likely structure of the unknown compound:
Unknown Compound
THE END
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Representative proton nmr chemical shifts

CHCl
CHBr
CHI
CHOH
CHOR CH CH3
CO2H CHC=C
CH-N CHC=O CH2 TMS
G
12-14 9.5 7-8 5-6 3-4 2-3 1 0.5 0
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IR CORRELATION CHART pKa TABLE
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=CH2 44
CH3CH3 51
1717

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© 2021 DEPARTMENT OF CHEMISTRY AND CHEMICAL BIOLOGY MCMASTER UNIVERSITY

CHEM 2OA3 (Spring 2021) – Final Exam

LATE SUBMISSIONS WILL NOT BE ACCEPTED.

CHEM 2OA3: Final Exam

/17 /15 /12 /12 /18 /8 /14.5 /15 /111.5

Primary Secondary Tertiary

sp2 Carbon sp Carbon sp2 Heteroatom sp Heteroatom

(d) How many chirality centre(s) are present in compound 1?

(e) The carbon atom marked * is (CIRCLE your answer):

(f) At pH 7, compound 1 exists predominantly as (CIRCLE your answer):

(C) A positively charged species, with two basic groups protonated

(D) The neutral structure shown above

trans cis syn anti None of these

For Ha For Hb For Hc For Hd

(b) Which is the best leaving group in this compound:

In an SN1 reaction In an SN2 reaction

AgNO3, EtOH, HCl, cold, dark

1. TsCl, pyridine H2SO4 (conc.),

KOtBu, hot KOH, hot

Reaction 1 Reaction 2 Reaction 3 Reaction 4

Conformer B Conformer B Conformer B Conformer B

Both Both Both Both

Neither Neither Neither Neither

Same or Different Product(s) Stereochemistry

1H NMR (Full spectrum shown)

Molecular Formula Degrees of Unsaturation

Number of Hydrogen(s) Number of Neighbours

(f) Draw the most likely structure of the unknown compound:

Representative proton nmr chemical shifts

IR CORRELATION CHART pKa TABLE

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