Chemistry 2301 August 2, 2012

Final Exam
Answer Key

Final Exam Mean: 77

Final Exam Median: 75
Final Exam St. Dev.: 28

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 1. (14 pts) For each of the pairs of acids (or bases) below,
 Draw the conjugate base (or acid).
 Circle whether you think the first acid (or base) is more or less acidic (or basic) than the
second.

Acid Conjugate Base Base Conjugate Acid

2 2
H H O H
H O
N N H
H H 3C CH 3
H H H 3C CH 3

is 3 3 is

MORE LESS MORE LESS

ACIDIC ACIDIC BASIC BASIC

than 2 than 2
H H
H H OH O
O H O
H H H3C CH 3 H3C CH 3

The two starting acids are ions, Of the cations on the right, the
and their relative acidity will upper cation is stabilized by
depend on the relative stability resonance, but the lower one is
of the charges. Nitrogen is less not. Because the upper cation
electronegative than oxygen, so is more stable, the upper base
the positive charge is more that produces it is more basic.
stably accommodated at
nitrogen. That makes nitrogen
less likely to give up the charge,
and the first acid less acidic.

Rubric:
2 points per conjugate acid/base structure. No partial credit.
3 points per circled more/less acidic/basic.

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2. (15 pts) For the anion drawn at right, in the boxes provided: H O H H
 Draw all significant resonance structures. In each structure,
H C C C C H
draw all atoms, bonds, lone pairs of electrons, and formal
charges. Then, circle which resonance structure you think H H
is the most significant, and which is the
least. Circle only one MOST and one atom hybridizations:
LEAST. 2
H sp
O H H 5
 Draw a Lewis wedge/dashed-bond structure
that illustrates the most stable three- 3 2 2 3
H sp
C sp C sp
N
C sp
C H
dimensional conformation of the molecule.
Draw all atoms, bonds, and charges, but
omit lone pairs. H H
 In the boxes provided, write the
hybridization state on any atom heavier than MOST or LEAST significant?
hydrogen. 2

3-dimensional representation resonance structure

3 3

O H H H O H H
H C C H C C C C H
C C H
H H
H H H
methyl groups
should be 180°
(trans-enolate)

MOST or LEAST significant?

Rubric:
-1 point for each trivial mistake in structure (left out an H, extra C, etc.)
Hybridizations: 1 point each. (5 points this part.)
3-D drawing: 3 points total.
1 point for flat enolate. (No groups in or out of molecule plane in the center.)
1 points for anti (180°) dihedral angle for methyl groups.
Anti conformation puts the largest groups farthest away from each other.
1 point for illustrating tetrahedral carbons correctly.
Tetrahedral centers are illustrated as having two
bonds in the plane of the page on one side of the
center, and two bonds out of the plane (one
forward, one back) on the other side.
correct incorrect

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 Resonance structures: 3 points each.
1 point for formal charges (both charges must be correct).
1 point for lone pairs (all must be correct).
1 point for bonds (all must be correct).
Resonance structures need not be in 3-D, or have correct bond angles.
Contributions (MOST/LEAST): 4 points for both correct. (2 points each.)
If you circle the same answer for both, no credit.

3. (12 pts) Each of the reactions below and on the next page is drawn with two possible
products. If one of the two products predominates, circle that preferred product. If the two
products are produced equally, circle “BOTH”. If neither product would result from the
reaction, circle “NEITHER”. Circle one answer only.

CH 3 CH 3 CH3
EtOH
Br
CH 3 
CH 3 CH3

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BOTH NEITHER
(equally)

These conditions—a weak base (EtOH) and heat—correspond to E1 elimination

conditions. E1 elimination, unlike E2, does not have the requirement that the leaving
group and the proton being removed be anti-coplanar. Instead, because the reaction
passes through a planar cation intermediate, the incoming base is free to take the
proton that leads to the most stable alkene product. In this case, that most stable
product is the tetrasubstituted alkene on the left.

Br
Br
CH 3 CH3
CH 3

H H H
CH3
CH 3 CH3
O Et O Et
H H

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 H CH 3
H 3C O O
H

mCPBA H CH 3 H 3C H
H3 C H H CH3
4
BOTH NEITHER
(equally)

meta-Chloroperxoybenzoic acid (mCPBA) can transfer a single oxygen atom to

either the top or bottom face of the starting alkene, to generate each of the two
products shown above in equal amounts:

Cl O

O H CH 3
O H H3 C H
O

H CH3
H 3C H
O O
H 3C H
O H
O H CH3 equals H 3C H
H CH3
Cl O

H 3C Br Br Br
Br2
H3C C C CH3 H 3C
CH 3
(1 equiv)
Br CH3 Br Br
4

BOTH NEITHER
(equally)

Adding one molecule of Br2 to the alkyne makes the resulting alkene less willing to
donate electrons to a second molecule of Br2. So the reaction stops reliably at the
mono-adduct.

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4. (15 pts) For each of the reactions on the following pages, fill in the empty box corresponding
to the major product. Wherever appropriate, illustrate stereochemistry in your drawings
(using wedge and dashed bonds). If multiple enantiomers or diastereomers are produced,
indicate this in the answer box (e.g., by writing “+ enantiomer”, etc.)

N Br
Br Br 5
(NBS) or
O

AIBN
(+ enantiomer)

NBS is a reagent that accomplishes allylic (or benzylic) radical bromination, by

abstraction of an H adjacent to a double bond, followed by reaction of the resulting
allylic radical with Br2. There are two H’s that could, in principle, be abstracted, but
the taking the tertiary H will lead to the more stable radical, and will be favored.

R H R
H abstracting here
leads to less stable
H H radical

Br Br Br Br

Br Br

Neither of the two radical structures shown above is any more stable that the other;
they are resonance structures, or just two ways of drawing the same structure, so
they have the same energy. As a result, the usual criterion that we would use to
predict product distributions in radical halogenations—relative stability of the
intermediate radicals—cannot be used to distinguish these two products, because

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they come from the same radical. That isn’t to say, however, that the two products
are made equally. The more highly substituted alkene, the product on the right,
would be more stable than the product on the left. Hammond’s postulate tells us that
this product, as a result, should be favored.

Rubric:
Br
5 points for correct structure.
We didn’t grade stereochemistry on this problem. If you
didn’t illustrate stereochemistry, you still got full credit.
3 points partial for allylic halogenation without generating 3
most stable alkene product.
Br

H2SO4 CH3
5
CH 3 H2O OH

These are the conditions for Markovnikov hydration (addition of H-OH) onto the
alkene. The -OH group ends up on the more substituted carbon.

Rubric:
5 points for correct structure.
CH 3
Illustrating in 3-D was fine, but unnecessary; the product has
no stereocenters.
2 points partial for anti-Markovnikov addition (any OH
stereochemistry) 2

5
O O
CH3O Na
H H

Br OCH 3

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 Normally, CH3O- would react with an alkyl halide via E2 elimination to generate an
alkene. However, in this case, there is no available proton on any carbon one carbon
away from the leaving group, a requirement of elimination. True, there is the
aldehyde H, but that’s attached to an sp2-hybridized center, and E2 does not occur
at sp2-hybridized centers. So, this reaction occurs via SN2.

Rubric:
5 points for correct structure.
4 points partial for writing “+ enantiomer”. Reaction is stereospecific.
3 points partial for incorrect stereochemistry, or for not indicating stereochemistry.
(You won’t lose a point for including “+ enantiomer” here—still 3 points.)

5. (8 pts) Each of the reactions below is drawn with two possible reaction conditions. If only
one of the two reaction conditions would generate the given molecule as the major product,
circle those conditions. If both sets of conditions would accomplish the reaction, circle
“BOTH”. If neither set of reaction conditions would succeed, circle “NEITHER”. Circle one
answer only.

1. (COCl)2, DMSO
Na2Cr2O7 -60 °C
H2SO4 2. Et3N
(Swern oxidation)
4

OH BOTH NEITHER O
would work would work

Both of these synthesis protocols accomplish oxidation. The first, chromate oxidation,
will oxidize anything as far as it can be oxidized (without breaking C-C bonds). The
secondary alcohol starting material can only be oxidized to a ketone, so chromate
will accomplish this oxidation. The second protocol, Swern oxidation, will only
oxidize an alcohol to an aldehyde or ketone. That’s exactly what’s happening here,
so the second protocol will work too.

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 Pd, BaSO4
Na, NH3 quinoline, H2 (g)
(Lindlar’s catalyst)

BOTH NEITHER
would work would work

Both of the reagent systems given reduce alkynes to alkenes and then stop. Neither
of them will reduce alkenes to anything.

6. (25 pts) When the epoxide-alcohol starting material below is deprotonated with NaH, the
resulting alkoxide reacts with itself to open the epoxide. That reaction, followed by acidic
workup, can produce two different products; the difference between the products is dictated
by which epoxide carbon is attacked by the alkoxide.
2. H3O+
intermediate product
O O A A
1. NaH
H CH 3 H CH3
H (-H2) H
O Na
2. H3O+
OH intermediate product
B B

In this problem, we will name the products A and B, which are formed by protonation of
intermediates A and B.

(a) Using “electron pushing”, draw a mechanism that illustrates the formation of
intermediates A and B from the alkoxide. I’ve drawn the starting material for you—just
add curved arrows to my structure. Then, draw the structures of intermediate A and
intermediate B. Wherever appropriate, illustrate stereochemistry.

O O
push
H CH3 electrons H CH3
here
H H
3 3
O O

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 intermediate A intermediate B
4 4
O CH 3 O
H
H
H CH 3
O H
O

These answers can be switched; the test-taker is free to define either

intermediate as “A” or “B”.

Rubric for part (a):

3 points for each set of electron-pushing arrows.
-2 points for one incorrect arrow. Arrow must start at an electron pair, and end
at nucleus or bond where electrons will newly interact.
-2 points for each error in charge, valency, structure, base, etc.
Minimum score for each mechanism is zero.
4 points for each intermediate.
-1 point for incorrect or unclear stereochemistry. Stereocenters don’t have to
be drawn like mine, but they do have to be correct.
-2 points for each clearly trivial structure mistake. (This includes leaving out or
adding a carbon.)

3 the
(b) Is intermediate A MORE LESS SAME intermediate B?
STABLE STABLE ENERGY (Circle one.)
than than as

gets credit if your definition of

A and B is opposite mine

Rubric for part (b):

3 points for the answer that matches answer to part (a).

(c) On the potential energy diagram below, draw two curves that represent the two reactions
you drew in part (a). The starting material (alkoxide) energy has already been drawn for
you—you need to connect this starting point to energies of the reaction transition states,
intermediate A, and intermediate B.

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 5

O
H
O
CH 3
H CH3 H
O intermediate
H
B
O
O CH 3
H
H
intermediate
O
A
E
starting alkoxide intermediates A/B
reaction coordinate

Rubric for part (c): (5 points total this part.)

You didn’t need to draw product structures, but you did need to make clear which
curve went to A and which to B.
1 point for correctly ordering intermediates A and B on the diagram.
Correct order depends on answer to (a). If (b) was incorrect, it seems unlikely
you will get this point.
1 point for each path having just one hump.
1 point for different transition state energies that match product energies.
(Hammond’s postulate applies here.)
1 point for both reactions being exothermic.
1 point for cyclobutane formation being close to thermoneutral.
(I.e., energy difference between starting material and intermediate B should
be less than difference between intermediates A and B.)

(d) How would the rate of the two reactions be affected if the starting O
material were a thiol instead of an alcohol? Assume that the
thiolate on the right has the same energy as the alkoxide above, H CH3
and that the sulfur-containing intermediates AS and BS are also the H
same energy as intermediates A and B. Would the thiolate react
S
3 the
FASTER SLOWER SAME RATE the alkoxide?
than than as (Circle one.)

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7. (16 pts) Draw a mechanism (using “electron pushing”) for each of the reactions shown below.
Draw each mechanistic step explicitly; don’t cheat by combining multiple processes in a
single step. Use only the molecules shown in the problem; don’t invoke generic species. (E.g.,
don’t use “H-A” as a generic acid.)

H2SO4
OH


Mechanism:

OSO 3H
H OSO 3H
H
O O

H 4 H 4

H
O
H 4 H
4 H O
CH3 H

The conditions given correspond to a typical E1 elimination reaction, and sure

enough a leaving group leaves to create an alkene in the product. But something
else is clearly going on here, in that the hydrocarbon backbone is rearranged in the
product. A 1,2-alkyl shift happens here to relieve the strain in the cyclobutane ring:

CH 3 CH 3 H
H H
H
H H equals
CH3

2° cation, 2° cation,
but strained not strained

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 Rubric: (16 points total this part)
Overall notes:
Must be these steps, in this order.
Overall, the minimum score for each step is zero; errors in a step cannot earn
you negative points that count against another, correct step.
Things that have left (e.g., -OSO3H) and spectators may be omitted.
-2 points, for each arrow in each step, for errors in drawing arrows. Arrow must
start at an electron pair, and end at nucleus or bond where electrons will
newly interact.
-2 points for each error in charge, valency, structure, base, etc.; if error
propagates, points are taken off only for initial error.
-4 points (out of 8) for combining two steps into one.
4 points per step.
2 points (out of 8) for beginning mechanism with –OH as leaving group. This
substitutes for first 2 steps.

8. (16 pts) For each set of starting materials and products shown below, propose a multistep
synthesis. In addition to the molecules shown, you can use any reagents and reactions we’ve
learned about in class. You might discover multiple answers to this problem; draw only your
best (one) synthetic route. Feel free to draw an incomplete route—we will give you partial
credit where we can.
OH O
Br
H3 C Br
H C C H

OH OTs H C C H
TsCl
1. NaNH2 or NaH
pyridine
2. X
use one
SOCl2 of these
pyridine here
PBr3
Cl
4 4

Br
C
C
H

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 HgSO4
H2SO4 O
C H2O
C H 3C
Br2 or NBS
H
4 4 h h

O
in either Br
order H3 C Br

This synthesis required 4 tasks, and there were some limitations to the order you did
them in.ly

1. Convert benzyl alcohol into something with a good leaving group (like a
tosylate or halide) that is compatible with an alkynyl anion. There are many ways
to do this, and we accepted all of them (including HBr or HCl, not shown above).
This must be done, because benzyl alcohol would just transfer a proton to an
alkynyl anion.

2. Generate an alkynyl anion, and combine it with the electrophile from step 1.

3. Convert the alkyne to a ketone. This could be done directly via Markovnikov
hydration (as I’ve shown above). But some of you chose to hydrogenate the
alkyne to the alkene, hydrate to the alcohol, and then oxidize the alcohol to the
ketone, and though this would be the long way, we still gave that route credit.

4. Halogenate the benzylic position twice. This would happen naturally if you ran
a bromination reaction (using Br2 or NBS) long enough, or you could sequentially
add single bromine atoms; we didn’t care, as long as the bromination would work.
You could also switch steps 3 and 4.

Rubric: (14 points total this part)

General notes:
-1 point for each minor error in structures or reagents; if error propagates, points are
taken off only for initial error.
-2 points if step reagents are incorrect, but reaction could otherwise be
accomplished with correct reagents.
-2 points if reagents are correct, but product is wrong. If this happened, and you
were led down an incorrect synthetic path by your mistake, you can also lose
later points.
4 points for each element.

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9. (29 pts) Acrylonitrile, the starting material on H2O
the right, can be polymerized into CH3CH2OH
polyacrylonitrile (a component of plastic
CN C5H9NO
consumer goods) by heating it in solvent, but 
heating acrylonitrile in a mixture of ethanol
and water generates a small molecule product instead. This product was isolated and
characterized by NMR and IR spectroscopy and mass spectrometry; the spectra of this
product are shown on the next two pages. High-resolution mass spectrometry determined an
exact mass of 99.06840 amu for the highest-mass (parent, M+) peak in the MS spectrum,
which corresponds to a molecular formula of C5H9NO.

Before we answer any questions about the unknown molecule, this problem already
tells us a couple of things. The molecular formula of our molecule changes from
C3H3N to C5H9NO, which means that the molecule picks up two carbons, an oxygen,
and some hydrogens, and it doesn’t lose its nitrogen atom. The molecule gets
substantially bigger, so something is clearly adding to this molecule. And our
reaction conditions make it look like that something needs to come either from water,
ethanol, or another molecule of starting material. (Given two carbons and an oxygen
being added, my bet is on ethanol.)
,

(a) Based on the features in the IR spectrum below, what functional groups would you
expect the unknown molecule to have? Circle all answers that apply.

H H H
H
C H
(sp) N
C(sp2) C(sp3) O

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or

C N C C C C C O C N

3 3

The IR spectrum really only has two important features: (1) no peaks above 2982
cm-1, which indicates no C(sp2)-H or C(sp)-H bonds; and (2) a peak at 2256 cm-1,
which the IR table tells us corresponds to either a –C≡N or a –C≡C– group. The
starting material already has a –C≡N group, so it seems likely that the reaction
doesn’t change the group that’s already there. The starting material also has C(sp2)-
H bonds which are gone in the product, so our reaction must be changing the alkene.

Rubric for part (a):

3 points for each correct circle.
-3 for each incorrect circle (up to 2; minimum score for this part is zero).

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(c) What is the structure of the product? In the box on the next page, draw the molecule’s
structure, including all hydrogens. Then, considering the 1H NMR spectrum,
 Circle each group of equivalent H’s;
 Assign a 1H chemical shift () to each circled group, within 0.05 ppm;
 Connect any pair of coupled, inequivalent groups of H’s with a double-headed arrow,
and then label that arrow
with the corresponding the product
(C5H9NO) 14
coupling constant (J).
J=  = 3.55 ppm  = 3.65 ppm
7.0 Hz
Format for answer to (c):
H H H H J = 6.3 Hz
 = 2.2 ppm
J = 7.0 Hz H CN
H H O
H
Cl Cl
H H H

H H H H  = 1.2 ppm  = 2.6 ppm

 = 3.8 ppm

The NMR spectrum tells us that our unknown molecule must have four different
(inequivalent) types of H’s, and the coupling constants tell us that two out of the
four are adjacent to each other, and the other two out of four are also adjacent.
Graphically, our molecule must look like this:

coupled with coupled with

J = 6.3 Hz J = 7.0 Hz

2 protons 2 protons 2 protons 3 protons

All of these H’s must be C(sp3)-H’s (from the IR data), and there are only 4
carbons to support them. (The fifth is in the –CN group.) That means our
molecule probably has these pieces:

H H C N H H
C C O C C H
H H (some kind H H
of oxygen)

I think the only way to put these together is in the product structure above, which
is the ethanol adduct of acylonitrile.

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 Rubric for part (c):
Structure need not be correct to receive points in this problem.
2 points for the correct molecule.
2 points for assigning each  value. (8 points total.) To get 2 points, circle must
include all equivalent protons for your structure, match the integration
intensity of the peak, and match the type of proton that would appear at that
frequency.
3.65, 3.55 ppm: Must be CHn protons adjacent to an O.
1 point partial for assigning each ppm value to the wrong number of H’s, or
with the wrong number of neighbors. If multiple inequivalent H’s are
labeled with the same  value, you get maximum 1 point partial credit for
each  value.
2.6 ppm: Must be two protons adjacent to CH2O protons.
1.3 ppm: -CH3 group that is part of an ethyl fragment.
1 point partial if methyl group has no neighboring H’s, or the wrong number.
2 points for each J assignment (4 points total.)
Circles need not be correct to get these points, but shift assignments of
coupled protons must be. Curved arrow only needs to connect one proton
with an adjacent partner.

(d) In an electron-ionization (EI) mass spectrometry experiment, parent ions often fragments
into daughter ions that give information about the parent’s molecular structure. In the EI
mass spectrum below, the parent mass peak at m/z = 99 corresponds to a radical cation
(M•+) that fragments into ions with mass 84 and 59. In the boxes below, draw the
structures of these ions. You do not need to do electron pushing to answer this question—
just draw the cations. On all ion structures, make sure to specifically illustrate where the
formal charge lies.

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 M•+ (C5H9NO+, m/z = 99)
3
N
C
loss of O loss of
+
m = 15; m = 40.
or
probably
loss of N+
C
–CH3 O

fragment ion with m/z = 84 fragment ion with m/z = 59

3 3

N
H 2C C CH2
O O

These fragments make sense in terms of the first of the two parent ions above:

N N
C C
O O
+ +

N
H 2C C CH2 N
H3C O O C
H2C

In each pair, only the cation is observed in the mass spectrum.

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Rubric for part (d):
PARENT:
Structure need not be correct to receive points in this problem.
3 points for any molecule that (i) has formula C5H9NO and (ii) has a lone-pair
electron on oxygen or chlorine removed (leaving a radical cation).
DAUGHTERS:
Structures need not be correct to receive points in this problem.
3 points for correct answer.
-or-
3 points for any fragments that are substructures of answer to (b), that have the
right mass, and that are drawn as cations.
-2 points for omitting positive charge.

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