Chemistry 2301 Thursday, August 4, 2011

Final Exam
Answer Key

Final Exam Mean: 121

Final Exam Median: 120
Final Exam St. Dev.: 37

1
 Multiple-Choice Problems
Please answer these problems on the bubble sheet.

hybridization hybridization hybridization

(2 pts each) For ethylformamidinium cation, hybridization #2 #3 #4

drawn at right: #1 (b) sp2 (b) sp2 (c) sp3
 For each atom marked “hybridization”, (b) sp2
H H H H H
indicate whether the atom is hybridized(a)
sp, (b) sp2, (c) sp3, or (d) none of these. H N C N C C H
 For each bond angle marked “angle”,
indicate whether the angle is closest to
angle
angle
H H
#5
(a) 109.5°, (b) 120°, or (c) 180°. #6
(b) 120°
(a) 109.5°

Although the nitrogen atom on the left end might look like it should be sp3 at first
glance (with its three  bonds and one lone pair), its hybridization lowers to sp2,
because the nitrogen has a lone pair and is adjacent to a multiple bond.

7. (3 pts) Of the resonance structures on the right, a. H H H H H

which contributes least to the overall electronics
in ethylformamidinium cation? H N C N C C H

H H

b. H H H H H c. H H H H H

H N C N C C H H N C N C C H

H H H H

All of these are valid resonance structures. Structures A and C have more bonds
than structure B, and they have filled octets where B does not. Admittedly, structures
A and C have a positive charge at a more electronegative atom, but Wade’s list of
priorities in making resonance structures says that this isn’t as important as bonds or
octets. So B is minor, and A and C are major.

2
8. (3 pts) Which of the structures below represents the most stable 3-dimensional conformation
of ethylformamidinium cation?

a. H H H b. H H

N N C N N C H
H C C H H C C
H
H H H H H H

c. H H H
d. H H

N N C H N C
H C C H C C H

H H N H H
H
H H

(2 pts each) Does the proton-transfer equilibrium for each acid-base pair shown below favor
products, or starting materials? (Is the acid strong enough to protonate the base?)

Does the equilibrium favor:

9.
H H conjugate a. products, or
O + N
acid-base b. starting
H H H H products materials?

H H
Both the starting material side and the O + N
product side have a cation--which side H H H H
accommodates the charge better?
Nitrogen is less electronegative than
oxygen, so it tolerates the charge
better, favoring the product side.

3
10. O O conjugate a. products, or
+ acid-base b. starting
H
F3 C O O CH 3 products materials?

O O
Again, both the starting material side + H
and the product side have an ion. Both F3 C O O CH 3
ions are stabilized by resonance, but the
trifluoroacetate anion on the product
side is also stabilized by induction from
the electronegative fluorine atoms. So
the equilibrium favors the product.

11. H
H H conjugate a. products, or
H H + H H acid-base b. starting
products materials?
H H H H H H

H H H
Both anions are primary carbanions, H H + H H
but the starting material cation is
stabilized by resonance. This H H H H H
H
equilibrium favors that cation.

chirality

(2 pts each) For each of the molecules drawn #12

on the right: b.(S)
 For each atom marked “chirality”, H CH3 14. Is this molecule
indicate whether the atom would be Br
labeled as (a) an (R)-chiral center, a. chiral, or
(b) an (S)-chiral center, or (c) not a Br b. achiral?
chiral center, according to the Cahn- H 3C H
Ingold-Prelog classification system. chirality

#13 This molecule has two

 Indicate whether the molecule would stereocenters with
be chiral or achiral. a.(R) opposite Cahn-Ingold-
Prelog assignments,
and exactly the same
groups attached. That
means the molecule is
meso, and achiral.

4
 chirality

#15
b.(S)
O
17. (2 pts) Are the methyl-group hydrogens 16. Is this molecule
in the structure on the right NH2 a. chiral, or
a. enantiotopic, HO b. achiral?
b. diastereotopic, or H 3C H
c. neither of the above? All molecules that have
only one stereocenter—
like this one—are chiral.

Two atoms are enantiotopic if replacing each one with a different atom—say, atom
“X”—would create two new enantiomers, usually by creating a new chiral center
where there wasn’t one before. That wouldn’t be true for any of the methyl group
protons; replacing any of them with “X” doesn’t create a new chiral center, and so
the protons aren’t enantiotopic.

Two atoms are diastereotopic if replacing them creates two diastereomers instead of
two enantiomers, again usually by creating a new chiral center. Once again, that
isn’t what happens here.

So the answer was “neither of the above”.

(4 pts each) 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,
answer with the corresponding letter. If both sets of conditions would accomplish the reaction,
answer (c) “BOTH”. If neither set of reaction conditions would succeed, answer (d) “NEITHER”.

18.
a. b.
HBr,
HBr
benzoyl peroxide
Br
c. d.
BOTH NEITHER
would work would work

HBr adds to alkenes with Markovnikov orientation (with Br at the more substituted
position), unless peroxide is added, in which case the HBr adds anti-Markovnikov.
Here, the product is anti-Markovnikov.

5
19.
a. b.
H2SO4, 1. Hg(OAc)2, H2O OH
H2O 2. NaBH4

c. d.
BOTH NEITHER
would work would work

Both of these sets of reagents add H-OH Markovnikov to the double bond. The first
set is not as clean as the second, but they both work.

20.
a. b.
KMnO4
mCPBA,
(cold, dilute
H2O OH
H3C CH3 in H2O/OH-)
CH3
c. d. H 3C
H H BOTH NEITHER
would work would work OH

Both of these sets of reagents perform dihydroxylation—they add an –OH group to

either side of an alkene. They differ in that mCPBA performs anti-dihydroxylation
(adding the two –OH groups to opposite faces of the alkene), while KMnO4 performs
syn-dihydroxylation (adding the two –OH groups to the same face of the alkene).
Here, even though the product is drawn to make it look like the –OH groups are on
the same side, they are on opposite sides of the starting material:

H3 C CH3 H 3C CH 3 H CH3
mCPBA HO HO
equals
OH OH
H2O
H H H H H3 C H

6
21. a. b.
Na, NH3 Pt, H2

c. d.
H3C C C CH3 BOTH NEITHER
would work would work

Both of these sets of reagents add H2 to alkynes. Na/NH3 adds only one molecule of
H2 to yield a trans-alkene as a product. Pt/H2, on the other hand, exhaustively
hydrogenates the alkyne all the way to an alkane.

22.
a. b.
1. CH3Li 1. CH3MgBr
(1 equiv) (1 equiv)
+
2. H3O 2. H3O+
O OH HO CH 3 OH
c. d.
H 3C BOTH NEITHER H 3C
would work would work

Although both alkylithium (R-Li) and Grignard (R-MgX) reagents will add to carbonyl
groups, they are also extremely basic. In the presence of even a weak acid, such as
an alcohol, either one will be protonated before it has a chance to react with the
carbonyl:
O O
H CH4 +
H3 C Li + O CH 3 O CH 3

Li

(4 pts each) Each of the reactions below is drawn with two possible products, marked (a) and (b).
If one of the two products predominates, answer with the letter corresponding to the correct
product. If the two products are produced equally, answer (c) BOTH. If neither product would
result from the reaction, answer (d) NEITHER.

7
23.
a. b. c.
Na2Cr2O7 O O BOTH
H2SO4 (equally)
OH
H OH
d.
NEITHER

Chromate is a strong reducing agent, and will oxidize the primary alcohol all the way
to the carboxylic acid.

24.
a. b. c.
BOTH
Br2 Br (equally)

h d.
Br NEITHER

Radical bromination replaces an H with a bromine atom at the most substituted

position (via the most stable radical intermediate).

25. O
pyridine
F + HO
Cl CH3
H
H 3C H

a. O b. O H 3C c.
H CH3 H BOTH
(equally)
H3 C H3 C
O O
d.
F H F H NEITHER

Combination of an acyl chloride with an alcohol to form an ester doesn’t change the
stereochemistry in either starting material.

8
32. (29 pts) For the reactions shown below, draw a mechanism that explains how the product is
generated from the starting material. In your answer, make sure that you:
 Draw each step of the mechanism separately;
 Use “electron pushing” to show where the electrons in each step go;
 Use only the molecules that you are given; do not invoke reactants or solvents that
aren’t in the problem.

CH3
Br CH 3
OH HBr

Mechanism:
Br
CH 3 CH 3 H
H Br CH3
O O
H H 4
4

resonance 2

Br CH 3 4 CH 3
Br

Resonance is not a mechanistic step per se—it’s just two ways of drawing the same
molecule. As a result, you did not need to push electrons to show resonance, or
even draw multiple resonance structures explicitly. You can integrate resonance into
a mechanistic step; for instance, you could have combined it with the departure of
H2O:

CH 3 H
4 + 2 CH 3
O
H

9
As long as resonance is in your answer somewhere—either integrated into a step, or
drawn explicitly—you get 2 points.
-
OH is a terrible leaving group. If you drew the first step as -OH leaving, you only got
4 points for that step (out of 8 for the combined first two steps).

Rubric: (14 points total this part)

Overall notes:
Things that have left (e.g., Br-) and spectators may be omitted until they are
needed.
-2 points, for each arrow in each step, for errors in drawing arrows. Arrow must
start at an electron pair, and end at nucleus where electrons will newly
interact. Can only lose points if you get them.
-2 points for each error in charge, valency, structure, base, etc.; if error
propagates, points are taken off only for initial error.
-2 points for each step combined with another, EXCEPT resonance. Combining
resonance with another step is just fine.

10
 O
Cl S CH 3
O O
HO
OH
N

My mechanism would be:

O
Cl S CH3
O

O 3
HO H
Cl O
HO
O S CH 3

H O

3 Both proton transfer

N and ejection of Cl
are extremely fast—
Cl O hard to say which
HO
O S CH 3 comes first. You
could order steps 2
O & 3 either way.
3

O
HO
O S CH 3
O
3 O
O S CH3
O

O H 3
N O
H N

11
The mechanism I’ve drawn invokes a five-coordinate sulfur atom as an intermediate
in the initial nucleophilic addition to TsCl. This is analogous to the tetrahedral carbon
intermediate that is observed when a nucleophile adds to a carbonyl C=O.
Researchers have observed the tetrahedral intermediate in C=O additions directly,
but not yet the S=O adduct; nevertheless, chemists usually infer the five-coordinate
adduct based on C=O chemistry.

But not Wade. Wade shows a different mechanism for tosylation of an alcohol on
page 470 of the text that does not involve a five-coordinate sulfur at the center--in
other words, that has the initial oxygen nucleophile directly displace chloride.

Wade’s mechanism would be:

O
Cl S CH3
O

O 6
HO H

O
HO
O S CH3

H O

4
N

O
HO
O S CH 3
O
3
O
O S CH3
O

3
O O H
H N
N

12
I think Wade is probably wrong, but he’s not definitively wrong, and so we accepted
either mechanism here.

Rubric: (15 points total this part)

Overall notes:
Things that have left (e.g., Cl-) and spectators may be omitted until they are
needed.
-2 points, for each arrow in each step, for errors in drawing arrows. Arrow must
start at an electron pair, and end at nucleus where electrons will newly
interact. Can only lose points if you get them.
-2 points for each error in charge, valency, structure, base, etc.; if error
propagates, points are taken off only for initial error.
-2 points for each step combined with another.

6 points total for substitution of chloride in TsCl by alcohol oxygen.

This must occur before deprotonation by pyridine; pyridine is not a strong enough
base to deprotonate an alcohol to any significant extent. However, we did not
take off these 6 points if you deprotonated first.
Substitution can be two-step (with addition to sulfonyl, followed by ejection of Cl)
or concerted.
3 points for first deprotonation by pyridine.
This must occur after attack on TsCl. (See note above about order of events.) No
partial credit for this step if out of order.
2 points partial for deprotonation with base other than pyridine (e.g. TsO-, Cl-).
3 points for intramolecular attack by other alcohol on tosylate.
Again, this must occur before deprotonation by pyridine, but you still get these
points if you put things out of order. (It’s the next ones you lose.)
3 points for second deprotonation by pyridine.
This must occur after attack by oxygen. See note above about order of events.
No partial credit for this step if out of order.
2 points partial for deprotonation with base other than pyridine (e.g. TsO-, Cl-).

13
33. (25 pts) Draw the missing reactant or product in the empty boxes. For products, give the
predominant, most favored product. Illustrate stereochemistry in your answer where
appropriate. For reactions that yield multiple enantiomers, draw only one enantiomer in the
box, and include the note “+ enantiomer”.

O H3C C C Na O
H 3C C
Na
C
H H CH 3 CH3

The acetylide anion adds to the epoxide at the O

less hindered carbon.
H3 C

Rubric: H C C CH 3
5 points.
Full credit for omitting Na+, or for protonating oxygen. (No proton source was
provided in the problem, but no points were taken off if you assumed one.)
-2 points for each trivial structural mistake (omitting a carbon, charge, etc.)
-2 points for omitting or incorrectly drawing stereochemistry in (any) product.
3 points partial for adduct at more substituted carbon of epoxide.

OH
Br2 CH 3
CH 3
H2O
Br
H

+ enantiomer

14
Here, formation of a bromonium ion is followed by addition of water to the more
substituted carbon:
H H
O
(from behind, SN2)

The more substituted carbon

CH3
CH 3 + accommodates more partial
positive charge, and is thus
Br Br Br preferentially attacked by H2O.
+

-
The other product enantiomer Br
H H
would be generated if the O OH
bromonium ion formed on the
underside of the starting material CH3 CH 3
(instead of the topside, shown
above). Br Br
H H

Rubric for this part:

5 points.
4 points partial for not writing “+ enantiomer”.
3 points partial for incorrect stereochemistry (syn adduct), indeterminate
stereochemistry (no wedges/dashes), or incorrect regiochemistry (Br at more
substituted carbon).
2 points partial for dibromide (any stereochemistry).
-2 points for each trivial structural mistake (omitting a carbon, charge, etc.)

NaBH4
CH3OH HO O
O O
O
O
+ enantiomer

15
NaBH4 is a mild reducing agent. It is strong enough to reduce ketones to alcohols,
but not esters. As a result, only the ketone is reduced.

Rubric for this part:

5 points.
No need to show stereochemistry in your answer, or to write “+ enantiomer”.
(Product is racemic, true, but drawing bond as a line would imply this.)
3 points partial for reducing ester (to anything) in addition to or instead of ketone.
-2 points for each trivial structural mistake (omitting a carbon, charge, etc.)

O 5
O
CH3 CH3O Na
H3 C CH3
H3 C

Br CH3
H 3C

In general, sodium methoxide is a strong base, and a better base than it is a

nucleophile, so it will react with the bromide via E2 if it can. There are two H’s on
carbons adjacent to ( to) the leaving group—the methyl hydrogen, and the single H
next to the carbonyl (C=O bond). The -carbonyl H would give the more substituted
(and resonance-stabilized) alkene product, so we’ll focus on it.

E2 requires anti-coplanar arrangement of the H being taken and the leaving group.
The way the molecule is drawn, the H and Br are not on opposite sides of the C-C
bond that connects them, so that bond will need to rotate to put them in position:

keeping all groups

rotate this that don’t change in
CH3O the same place…
bond
H CH 3 H CH 3
H 3C H H 3C H

H H 3C O CH3
O Br Br CH 3
O
CH3
CH3
same as prev. page, H and Br are
turned on its side anti-coplanar

16
Rubric for this part:
5 points for correct structure.
3 points partial for bromine elimination product O O
with wrong or unclear stereochemistry or CH3 CH3
wrong regiochemistry. H3 C H3 C
2 points partial for any bromine substitution 3
3 CH3 CH2
product.
-2 points for each clearly trivial structure
mistake. The answer that you intend needs
to be clear for you to get these points. O 2
CH3
H3 C (with any
stereochemistry
at –OCH3)
H 3 CO CH3

H 5
O H
Cl
O O
H 3C OH

 CH3
+ enantiomer

Acetic acid is a poor nucleophile, and the added heat tips us off that this should be
an SN1 or E1 reaction. There are no protons  to the Cl leaving group, so it cannot
be E1; this must be SN1. SN1 passes through an achiral carbocation intermediate,
which reacts to generate a racemic mixture of products:

H H H
H
Cl O O O O

CH3
+ CH3

(when acetic acid (when acetic acid

adds to top adds to bottom
face of cation) face of cation)

17
Rubric for this part:
5 points for correct structure and either (a) including “+ enantiomer” or (b) not
illustrating stereochemistry (which infers racemate).
4 points partial for omitting “+ enantiomer” from correct answer that shows
correct enantiomer only.
3 points partial for inversion of stereochemistry only (as if reaction were SN2).
-2 points for each clearly trivial structure mistake.

18
34. (32 pts)
(a)

Br Br
H 3C CH3 Br
H 3C CH 3 H 3C CH 2
Br Br

H H H H
H2 C CH3
Br

3 3
(or, could draw mirror
image of this one; any two
of these three receives full
credit)

Br CH 3
H H H3 C
H 3C CH3
Br Br
Br Br
H H H CH 2
H2 C
Br H H
H3 C CH 3 H 2
3 3
(again, could draw mirror
image of this one; any two
of these three receives full
credit)

-
(b) Of the four Newman projections you drew above, which would react the fastest with OH
in an SN2 reaction? Circle one Newman projection.
CH 3
Sure, the anti-conformer is Br H3 C
the most stable. But, the Br Br
H H
conformation with the least H CH 2
amount of steric hindrance
H H
opposite the leaving
H2 C H H
group—with the most
Br
room for OH- to H no steric hindrance
approach—will react the H3 C CH 3 from H
OH-
fastest. So:
OH- steric hindrance
from alkyl group
prevents approach

19
(c)
- - H 3 C CH 3
Br Br
Br

H 3C CH 2 H CH 2 Br
H H H H

CH3 3 H 3
HO HO
- -
steric
hindrance

- - Br
Br Br
CH 3 H
H CH 3
OR H 3C H
H CH3 H
H
OH Br
- - OH

E
2 for drawing one
step (hump) in
each direction
Ea
2 for right hump
Ea
lower than left
1 1 hump

H 3C CH3
Br Br

-
+ OH
H3C CH3 H3C CH 3
(starting
HO Br material) Br OH

- - 1
+ Br + Br

(product) (product)

reaction
coordinate

20
(d) In fact, both of these SN2 products are minor products of the reaction between one
equivalent of OH- and the starting material, because OH- is a stronger base than it is a
nucleophile. What molecule would be the preferred product of this reaction, and by what
mechanism would it be produced?

NaOH
H 3C CH3 (1 equiv)
Br Br
H3C CH3
E2 Br

2
by what
mechanism? 3
(not SN2)
Rubric:

for parts (a/b): (14 points)

3 points for each staggered Newman projection.
I have drawn one anti and one gauche, but could also draw two gauche. Any two
will do.
-1 point for each trivial structural mistake.
1 point partial on each rotamer if you omitted rest of chain (& just drew atoms on
the rotated bond)
2 points for circling any conformer where –Br is anti to an -H.

for part (c): (13 points)

3 points for each transition state structure:
Any conformation is acceptable.
1 point for backside attack by OH- on Br;
1 point for partial bonds;
1 point for partial charges.
-2 points if transition state doesn’t correspond to product (say, if TS for left
reaction was also drawn for right reaction), or if there is no clear difference
between the two TS structures. Only lose these points if you get them.
6 points for potential energy diagram:
2 points for drawing each process as a single (SN2) step;
2 points for drawing unhindered transition state as lower in energy than
neopentyl TS;
1 point for labeling Ea on each curve. (Curve does not have to be correct, and
relative heights can be wrong.)
1 point for circling right-hand product.

for part (d): (5 points)

3 points for correct product.
1 point partial for any alkene.
2 points for “E2”.

21
9. (14 pts) For the starting materials and product 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 H C C
HO

H H

One possible route:

Swern oxidation
(or Na2Cr2O7/H2SO4, 4 for preparing to
or PCC) receive alkynyl
OH O

1. NaNH2 (to
generate alkynyl 3 for combining
anion) fragments;
2. 3 for generating
O alcohol

(from above)
3. H3O+
H C C C C
OH

H2,
Lindlar’s
4 catalyst
(Pd/BaSO4,
quinoline)
HO

H H

22
 Rubric:
The synthesis requires four tasks: (a) getting cyclopenatnol ready to react with the
alkyne; (b) making the alkyne reactive (probably as an alkynyl anion), and
combining it with the cyclopentyl fragment; (c) creating the alcohol group in the
product (which could happen as a result of a and b, or could be done separately;
and (d) hydrogenating the alkyne to generate an alkene.
-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. (Especially relevant to hydrogenation step.)
-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.

Making cyclopentanol reactive towards alkyne (a): 4 points.

Lots of potential ways to do this. Some end up becoming alcohol in product, some do
not. Examples that would be worth full credit:
 Oxidation to ketone w/ Swern/chromate/PCC;
 Tosylation (TsCl/pyridine);
 Conversion to halide (SOCl2, PBr3, P/I2; 3 points partial for HX).

Deprotonating alkyne, and combining alkynylsodium with electrophile (b): 3 points.

1 points partial for deprotonation alone. There is no need to show alkynyl anion itself;
just “NaNH2” is enough.
Other 2 points awarded if alkynyl anion is combined with something—anything that
works—to form a C-C bond. So, combining alkynyl with ketone, tosylate, halide, or
epoxide—no matter whether points were awarded in part (a) or not—receive credit
here.
1 point partial of 3 above if combination would not work, but could if it were engineered
correctly.
H3O+ workup can be omitted (though, in real life, it couldn’t be).
Full credit for drawing parts 1-3 of this recipe as explicit steps, or combining them onto
the same arrow with numbers as I have. However, if you combine them on the
same arrow, you must have numbers; you can’t add all the reagents at the same
time.

Generating alcohol group (c): 3 points.

If answer used alkynyl + ketone, alcohol is generated automatically. 3 points for this.
If answer used alkynyl + cyclopentyl-LG, allylic halogenation (with NBS) followed by
SN2 with hydroxide is worth 1 point. The SN2 would not be clean, lots of E2.

Hydrogenation to cis-alkene (d): 4 points.

2 points partial for alternative hydrogenation protocol (Na/NH3, or Pt/H2).
2 points partial if you do this too early (before there are two substituents to be cis).

23
The spectra on this page correspond to a pure molecule, isolated from a chemical reaction. High-
resolution mass spectrometry determined an exact mass of 102.0681 amu for the highest-mass
(parent, M+) peak in the MS spectrum, which corresponds to a molecular formula of C5H10O2.

Transmittance

2896

1716 IR Spectrum

4000 3000 2000 1500 1000 500

 (wavenumbers, cm-1)

43
45 EI-Mass Spectrum
Relative Intensity

87

102 (M+)
15 31 71

10 20 30 40 50 60 70 80 90 100 110
m/z

1
H NMR Spectrum (300 MHz)
3
2 integral
6.6 Hz 6.6 Hz
3 (w/ relative
segment
2 heights)

TMS
3.7 3.6 2.8 2.7 2.6

8 7 6 5 4 3 2 1 0
δ (ppm)

24
(1 pt each) Based on the features in the IR spectrum, which of the following functional groups
would you expect the unknown molecule to have? Would the molecule contain a

26. a. Yes 29. H a. Yes

C H ? b. No ? b. No
(sp) O

27. H a. Yes 30. a. Yes

? b. No C C ? b. No
C(sp2 )

28. H 31. N a. Yes

a. Yes C ?
? b. No b. No
3
C(sp )

The IR spectrum really has only two features above 1500 cm-1—a peak at 1716 cm-1,
and a C-H peak below 3000 cm-1. The C-H peak has to be C(sp3)-H only; C(sp2)-H and
C(sp)-H would both be found above 3000 cm-1. The IR resonance chart says that the
peak at 1716 cm-1 is a C=O bond. (Sadly, problem #31 was supposed to ask you
whether a C=O was present, but I copied and pasted the list from a different test, and
didn’t replace the last item. Needless to say, a molecule that has no nitrogen atoms in it
cannot have a C≡N group in it.)

36. (26 pts)

(a) The mass spectrum shows a parent mass peak at m/z = 102, and two fairly high-mass
fragment ions at m/z = 87 and m/z = 71. For these fragment ions to be observed, the
parent molecule must have ejected neutral (invisible) fragments with mass (102 - 87) =
15 and (102 - 71) = 31 atomic mass units (amu). What do you think are the structures of
these neutral fragments?

neutral fragment with mass 15: neutral fragment with mass 31:

CH3 OCH3

4 4
2 if CH2OH

There is only one fragment formula, given the C, H, and O atoms we have to
work with in the parent, that adds to mass 15: CH3-. So, our molecule must have
a methyl group. There are two possible fragment structures with mass 31; we

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 ruled out the presence of an alcohol in problem 29, so the fragment must be
CH3O-. (We gave partial credit for the alcohol fragment HOCH2-.)

(b) The mass spectrum shows a small peak at m/z = 103, above the mass of the parent M+
peak (102). Assuming that the material is pure (i.e., that there are no higher-mass
contaminants in the sample), how is it possible that the mass of some molecules would be
higher than expected? Please be brief. You could probably answer this in 10 words or
less.

Any molecule that has one heavy isotope in it—say, where one of the carbons
is a 13C instead of a 12C (probability: 1 out of every 100 carbons), or one of the
hydrogens is an 2H instead of an 1H (probability: 1 out of every 10,000
hydrogens)—will show up in the mass spectrum as one a.m.u. higher than the
“parent” peak. For this molecule, with 5 carbons, the intensity of the m/z = 103
peak should be ~5% that of the m/z = 102 peak.
4

Rubric for part (b):

4 points for any answer that references a heavy isotope (or the words “heavy
isotope”).

(c) What is the structure of the molecule? In the box below, draw your molecule’s
structure again, including all hydrogens. Then circle each set of equivalent H’s, and label
each with its unique 1H NMR chemical shift.

your molecule
(C5H10O2)
 = 3.7 ppm  = 3.3 ppm
O H H H H

H C C
C C O H

H H H H

 = 2.2 ppm  = 2.7 ppm

10

The 1H NMR has many useful clues in it. Out of the four resonances, two are
multiplets—indicating H’s with neighbors, and presumably with each other as
neighbors—and two are singlets with intensity three, each indicating three

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 equivalent protons with no neighbors. We can already guess that one of those
singlets is from the -OCH3 group we predicted in part (b), and the other singlet is
probably another -CH3 group somewhere. Each of the other two resonances
represents two H’s with two neighboring H’s (because each multiplet is a triplet).
So that means our molecule has the following fragments:

O
H3C
C CH2 CH2 OCH3

Rubric for part (c):

2 points for correct structure.
Structure need not be correct to receive the other 8 points in this problem.
2 points for each  value. (8 points total this box.) To get full credit, circle must
include all equivalent protons for your structure, match the integration
intensity of the peak, match the type of proton that would appear at that
frequency, and  value must be within ±0.1 ppm of value shown above.

3.7, 3.3 ppm: Must be O-C-H protons.

1 point partial for if chemical shift matches proton type, but integral and/or
splitting do not match.

2.7, 2.2 ppm: Any proton adjacent to C=O.

1 point partial for if chemical shift matches proton type, but integral and/or
splitting do not match.
1 point partial if integral and splitting match, but chemical shift would normally
be for alkyl.

(d) Given your answer above, what is the fragment cation with m/z = 87
structure of the daughter (fragment) cation
in the mass spectrum that has m/z = 87? 4
You do not need to do electron pushing to
answer this question—just draw the cation. O
C CH3
O

Rubric for part (d):

4 points (full credit) for any structure that (i) is a cation; (ii) has mass 87; and (iii)
is related by bond cleavage to the answer written in part (c).
-2 points if any oxygen has an unfilled octet. Cleavage will prioritize putting
electrons on oxygen.

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