ANSWER KEY Page 1 of 6

ANSWER KEY

University of Manitoba - Department of Chemistry

CHEM 2220 - Introductory Organic Chemistry II - Term Test 2

Thursday, March 13, 2008

This is a 2-hour test, marked out of 50 points total. Part marks are available on all questions.
Put all answers in the spaces provided. If more space is required you may use the backs of the exam pages but be sure to
indicate that you have done so. A spectroscopic data sheet is attached at the end of the exam.

1. (5 MARKS) Write a stepwise mechanism to explain the surprising result of the following reduction
using sodium borohydride. Assume a normal aqueous workup follows the reaction, but you do not
have to show the steps in this workup.

O O
O NaBH4, MeOH
O

O acid workup
OH

O Na
BH3
O O O O
O O
H O Na
O
O BH2
BH3
Na O O
BH3
Na

This is Groutas problem #80. The key idea is that sodium

BH3
borohydride will reduce a ketone easily but will react
slowly or not at all with an ester. O O O BH3
There are several ways you could represent this process. I H O
H
have chosen to keep the boron coordinated to the alkoxide
O O
formed in the reduction and to move it through the
mechanism. As your textbook shows on page 577 Notice that the 7-membered ring must adopt a
however, at any point the solvent could exchange with the boat-like geometry because the alkene group
needs to be planar.
alkoxide and this would release the boron to the solution.
The overall idea would still be the same. The conditions
are basic, so the alcohol would be deprotonated and would
attack the carbonyl. Look at Groutas for a “bare bones”
version of this mechanism. Full marks will be given for
any reasonable representation of this alkoxide pathway.
One thing students should be clear about: NaBH4 is a
hydride donor and NOT an acid (proton donor).
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2. (8 MARKS) When N,N-dimethylaniline is treated with 1 equivalent of Br2, the product is almost
exclusively p-bromo-N,N-dimethylaniline. However, when N,N-dimethylaniline is nitrated using a
mixture of nitric acid and sulfuric acid the product is predominantly m-nitro-N,N-dimethylaniline.
Briefly explain why the regioselectivity of these two electrophilic aromatic substitution reactions is
different. A mechanism may be helpful to illustrate your explanation.

N N N N
HNO3/H2SO4 Br2
+ + small amount of ortho
CH2Cl2 isomer
NO2
NO2 Br
minor major
The bromination gives us the para product which is what we expect from an
electron-donating substituent like dimethylamino. Note that the conditions of the
bromination are not strongly acidic, although as the reaction proceeds there will be a
buildup of HBr. Fox and Whitesell (pp 545-546) note that if you use an excess of Br2,
you can form 2,4,6-tribromoanilines, but that the rate of each successive bromination
decreases due to protonation of the amino group by the HBr formed.

The anomaly is the nitration. Notice that this reaction occurs under VERY strongly acidic
conditions. The dimethylamino group in the substrate is basic, and under these conditions
it will certainly be protonated.
H
N N
HNO3/H2SO4

The protonated ammonium ion is no longer electron-donating but rather it is very

electron-withdrawing due to its positive charge. It therefore behaves as a deactivating
meta-director, and the major nitrated product is thus the meta isomer..
The minor para product arises from nitration of the small amount of unprotonated
dimethylaniline present in the mixture.
You did not have to write mechanisms but of course if you did you could show that the
cationic nitrogen would destabilize the intermediate ion formed during ortho or para nitration,
while its effect on the ion formed in meta nitration would be less significant.

H H H H
N N N N
NO2
H

H NO2 H NO2

H H H
N N N

NO2 NO2 NO2

H H H

Fox and Whitesell mention the effects of protonating the nitrogen of an aniline
compound during electrophilic aromatic substitution at the bottom of page 545, and the
tetrasubstituted ammonium ion is listed among the “Moderately and strongly
deactivating meta directors” in Table 11.1.
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3. (8 MARKS) Propose a sequence of reactions that accomplish a feasible synthesis of 1-ethoxy-2-

methyl-4-nitrobenzene starting from ethoxy-benzene (several steps are necessary). For each
reaction, clearly show the reagent(s) required and what product will be formed. You do not have to
provide mechanisms.
Attention! There is more than one way to realize this synthesis.

O O
CH3

ethoxy-benzene NO2
1-ethoxy-2-methyl-4-nitrobenzene
Here is one way:

O CH3Cl O
O
AlCl3
CH3
+

CH3 O
separate
isomers CH3
HNO3/H2SO4

NO2
nitration para to the
strongest activating group.
Would also form isomer
with nitro ortho to OEt.
Note that you cannot do a Friedel-Crafts reaction after installing the nitro group.

In questions of this type, there are always several possible answers and
we cannot list every one. Any sequence of reactions that would actually
work will be given full marks.

The key thing to watch here is the sequence of installing the groups
because strong electron withdrawing groups will prevent alkylation or
acylation. This puts limits on the number of possibilities.
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4. (24 MARKS) Provide the necessary reagents/solvents or starting materials or products to

correctly complete the following reactions. Mechanisms are NOT required. Give product
stereochemistry where appropriate. Some transformations may require more than one step!

O
CH3 1. KMnO4, heat
H3O+ OH
2. Cl2, AlCl3
Cl
a. (2 Marks)

Thionyl chloride is discussed on

pp. 606-608 in the text. You
SOCl2 could also have used oxalyl
chloride, which is featured in
OH Cl question 12.18 at the end of the
chapter.
b. O O (2 Marks)

The use of acetals and

ketals to protect a
O carbonyl is in the text pp.
592-593. The cyclic
O O 1) NaBH4, MeOH ketal formed from
ethylene glycol is the
2) H3O+ HO
subject of Exercise 12.16.
O
IR: 3400, 1715 cm-1
c. (4 Marks)

For enamine formation, see

Fox and Whitesell pp. 595-
O 597. This reaction is similar to
N
H N problems 12.6b and 12.7h at
the end of the chapter.
pTsOH
d. (2 Marks)
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Hg(OAc)2 (cat.)
dil. aq. H2SO4
O NaBH4,
EtOH OH

e.
(4 Marks)

1) NaNO2, HCl
Sn/HCl or Zn/HCl
(aq.)
NO2 NH2 Br
or H2, Pd or Pt

2) Cu2Br2

f. (4 Marks)

O This reaction appears in

1. LiAlH4, ether H the text at the top of page
NH 2. H , H2O N 581.

g. (2 Marks)

Reductive amination is in
CH3NH2, H3O the text on pp 594-595.
CH3
O NaBH3CN HN For similar cases see
H Exercise 12.19 on p. 595.

h. (4 Marks)
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5. (5 MARKS) The spectra of an unknown organic compound A having the formula C15H14O3 are
shown below. What was the structure of compound A?

IR

1
H NMR

Molecular Formula gives us 9

degrees of unsaturation!
13 IR: probable carbonyl ca.
C NMR
1600-1650. Note also very
weak C-H stretch region, no
OH.

Structure:
O

H3C CH3
O O

13
A
C NMR: ONLY 6 distinct carbon types: Symmetry. Carbonyl at 195 – probably
ketone. Also shows peak at ca. 58 – likely C next to oxygen. Four peaks in aryl region.
1
H NMR: only 3 signals in a 2:2:3 (4:4:6) ratio. Singlet at ca. 3.9 integrating for 3 (6) is
certainly OCH3. “Doublets” at 6.9 and 7.8 indicate para-disubstituted benzene ring.
Symmetry means there are TWO benzene rings and TWO OCH3 groups, but only ONE
ketone carbonyl.